The invention relates to cytostatics which, by modification with sugar, are tumor-specific. Suitable spacers ensure serum stability and at the same time an intracellular action.

BACKGROUND OF THE INVENTION
 This application is a 371 of PCT/EP96/01279, which was filed on Mar. 11,
 1996.
 1. Field of the Invention
 The invention relates to cytostatics which, due to modification with
 carbohydrates, are tumour-specific. Suitable spacers ensure serum
 stability and at the same time an intracellular action.
 2. Description of Related Art
 Chemotherapy of tumour diseases is accompanied by usually serious side
 effects caused by the toxicity of chemotherapeutics on proliferating cells
 of other tissue. For many years, scientists have been addressing the
 problem of improving the selectivity of the active compounds used. One
 approach which is often followed is the synthesis of prodrugs, which are
 liberated more or less selectively in the target tissue, for example by a
 change in the pH (Tietze et al., for example DE-4 229 903), by enzymes
 (for example glucuronidases; Jacquesy et al., EP-511 917; Bosslet et al.,
 EP-595 133) or by antibody-enzyme conjugates (Bagshawe et al. WO 88/07378;
 Senter et al., U.S. Pat. No. 4,975,278; Bosslet et al., EP-595 133).
 Problems of these approaches are, inter alia, the lack of stability of the
 conjugates in other tissues and organs and, in particular, the ubiquitous
 distribution of the active compound, which follows extracellular
 liberation of the active compound in the tumour tissue.
 The pronounced lectin pattern on the surfaces of tumour cells (Gabius;
 Onkologie 12, (1989), 175) opens up the chief possibility of addressing
 these specifically on tumour cells by linking the corresponding
 carbohydrate units to cytostatics. These perspectives are limited by the
 fact that lectins with similar carbohydrate specificities (galactose,
 lactose, mannose, N-acetyl-glucosamine, fucose and the like) also occur in
 other tissues, in particular in the liver (Ashwell et al., Annu. Rev.
 Biochem. 46 (1982), 531; Stahl et al. Proc. Natl. Acad. Sci. U.S.A. 74
 (1977), 1521; Hill et al., J. Biol. Chem. 262 (1986), 7433; Jansen et al.,
 J. Biol. Chem. 266 (1991), 3343). A significant concentration of
 glycoconjugates containing the active compound in the liver and other
 lectin-rich organs must consequently be expected if such non-modified
 sugars are used.
 The heterocyclic amine batracyline (1) shows a good antitumoural action in
 various intestinal cancer models (U.S. Pat. No. 4,757,072).
 ##STR1##
 Peptide conjugates of (1) with a good in vitro action and more favourable
 solubility properties (U.S. Pat. No. 4,180,343) are tolerated more poorly
 than batracyline in animal studies. The fucose conjugates described in
 EP-501 250 become very highly concentrated in the liver.
 Quinolone-a (2),
 7-[(3aRS,4RS,7aSR)-4-amino-1,3,3a,4,7,7a-hexahydro-isoindol-2-yl]-8-chloro
 1-cyclopropyl-6-fluoro-1,4-dihydro4-oxo-3-quinolinecarboxylic acid also
 shows, in addition to its outstanding antibacterial activity, a very good
 activity against various tumour cell lines (EP-520 240, JP-4 253 973).
 However, this is faced with considerable toxicological problems (for
 example genotoxicity, bone marrow toxicity, high acute toxicity in vivo
 and the like).
 ##STR2##
 BRIEF SUMMARY OF THE INVENTION
 By a novel modification of cytostatics, we have found, surprisingly, a new
 class of conjugates which are distinguished by the following properties: A
 novel linkage of carbohydrates with cytostatics (for example batracyline,
 quinolone-a) leads to glycoconjungates which are serum-stable. The action
 does not depend on extracellular liberation of the active compound. The in
 vitro activities against various tumour cell lines are comparable to that
 of the cytostatic on which they are based. The cell-specific absorption
 depends on the carbohydrate.
 The cell and tissue selectivity (in particular tumour to liver) is
 significantly improved by the regioselective modifications in the
 carbohydrate part of the conjugates described.
 In vivo, the conjugates according to the invention are distinguished by a
 significantly improved tolerance compared to the active compound and the
 corresponding peptide conjugates.
 Furthermore, in comparison with the cytostatics on which they are based,
 the conjugates according to the invention show considerably improved
 solubility properties.

DETAILED DESCRIPTION OF THE INVENTION
 The compounds according to the invention are described by the following
 general formula:
EQU K-Sp-L-AA1-AA2-C (I)
 where
 K=an unsubstituted or regioselectively modified carbohydrate radical,
 Sp=optionally substituted arylene or alkylene,
 ##STR3##
 where
 R=chlorine or hydroxyalkylamino, the linkage to Sp being via the NH group.
 AA1 is an amino acid radical in the D or L configuration, which optionally
 carries a second grouping K-Sp-L-, in which K, Sp and L, independently of
 the other grouping K-Sp-L-, can have the abovementioned meanings, or a
 direct bond. An amino acid radical can be linked to L both via the
 .alpha.-amino group and, where appropriate, via side chain amino or
 hydroxyl functions, and also via both functions. If AA1 carries further
 functional groups, these can be present in deblocked form or in a form
 protected with known protective groups. Suitable protective groups are,
 for example, acetyl, allyloxycarbonyl, benzyloxycarbonyl,
 fluorenylmethoxycarbonyl, t-butoxycarbonyl, allyl, benzyl, methyl or
 tert-butyl.
 AA2 is an amino acid radical in the D or L configuration, which optionally
 carries a second grouping K-Sp-L-, in which K, Sp and L, independently of
 the other grouping K-Sp-L-, can have the abovementioned meanings, or a
 direct bond. An amino acid radical can be linked to AA1 both via the
 .alpha.-amino group and, where appropriate, via side chain amino or
 hydroxyl functions, and also via both functions. If AA2 carries further
 functional groups, these can be present in deblocked form or in a form
 protected with known protective groups. Suitable protective groups are,
 for example, benzyloxycarbonyl, acetyl, allyloxycarbonyl,
 fluorenylmethoxycarbonyl, t-butoxycarbonyl, allyl, benzyl, methyl or
 tert-butyl.
 C=radicals of a cytostatic or of a cytostatic derivative, which can
 additionally carry an amino or hydroxyl group. C can be an intercalating
 substance, a topoisomerase inhibitor, an antimetabolite, an alkylating
 agent, a tubulin inhibitor, a tyrosine phosphokinase inhibitor, a protein
 kinase-C-inhibitor or an active compound with another or an unknown
 cytostatic or cytotoxic action mechanism. C can be, for example, a
 nucleoside, an endiine antibiotic, a quinolone- or
 naphthyridone-carboxylic acid or a cytotoxic peptide antibiotic, for
 example from the class of dolastatins. C can be batracyline, quinolone-a,
 5-fluorouracil, cytosine arabinoside, methotrexate, etoposide,
 camptothecin, daunomycin, doxorubicin, taxol, vinblastine, vincristine,
 dynemycin, calicheamycin, esperamycin, quercetin, suramin, erbstatin,
 cyclophosphamide, mitamycin C, melphalan, cisplatin, bleomycin,
 staurosporin or another active compound having an antineoplastic action.
 The structural element -Sp-L-AA1-AA2- in total represents the spacer which
 connects K and C.
 Preferred compounds of the formula (I) are those in which
 K=a carbohydrate radical having the general formula
 ##STR4##
 wherein
 A=methyl, hydroxymethyl, carboxyl and esters and amides derived therefrom,
 alkoxymethyl, acyloxymethyl or carboxyalkyloxymethyl and esters and amides
 derived therefrom. A can also be CH.sub.2 --B, wherein B in turn can be a
 carbohydrate radical of the general formula (II) linked via the anomeric
 centre.
 R.sub.2, R.sub.3, R.sub.4 =individually or together at the same time, H,
 hydroxyl, alkyloxy, carboxyalkyloxy and esters and amides derived
 therefrom, hydroxyalkyloxy, aminoalkyloxy, acyloxy,
 carboxyalkylcarbonyloxy, sulphato, phosphate, halogen or another
 carbohydrate radical (II) modified in the same framework and linked via
 the anomeric centre. R.sub.2 can additionally also be amino or acylamino.
 Two of the radicals R.sub.2, R.sub.3 or R.sub.4 together can also denote an
 epoxide group.
 The stereochemistry on the anomeric centre of the carbohydrate structural
 unit can be .alpha. or .beta.. The gluco, manno, galacto, gulo, rhamno or
 fuco configuration can result from the stereochemistry on the other
 centres.
 Sp=an arylene radical which is modified with K and L in the ortho-, meta-
 or para-position and furthermore can also carry 1 to 4 further
 substituents which, independently of one another or in an identical
 manner, can be H, methyl, methoxy, hydroxyl, carboxyl, methoxycarbonyl,
 cyano, nitro, halogen, sulphonyl or sulphonamide;
 Sp can also be a linear or branched alkylene radical.
 ##STR5##
 where
 R=chlorine or hydroxyalkylamino,
 AA1 is an amino acid radical in the D or L configuration, which optionally
 carries a second grouping K-Sp-L-, in which K, Sp and L, independently of
 the other grouping K-Sp-L-, can have the abovementioned meanings, or a
 direct bond. An amino acid radical can be linked with L both via the
 .alpha.-amino group and, where appropriate, via side chain amino or
 hydroxyl functions and also via both functions. If AA1 carries further
 functional groups, these can be present in deblocked form or in a form
 protected with known protective groups. Suitable protective groups are,
 for example, acetyl, allyloxycarbonyl, benzyloxycarbonyl,
 fluorenylmethoxycarbonyl, t-butoxycarbonyl, allyl, benzyl, methyl or
 tert-butyl.
 AA2 is an amino acid radical in the D or L configuration, which optionally
 carries a second grouping K-Sp-L-, in which K, Sp and L, independently of
 the other grouping K-Sp-L-, can have the abovementioned meanings, or a
 direct bond. An amino acid radical can be linked with AA1 both via the
 .alpha.-amino group and, where appropriate, via side chain amino or
 hydroxyl functions, and also via both functions. If AA2 carries further
 functional groups, these can be present in deblocked form or in a form
 protected with known protective groups. Suitable protective groups are,
 for example, benzyloxycarbonyl, allyloxycarbonyl, acetyl,
 fluorenylmethoxycarbonyl, t-butoxycarbonyl, allyl, benzyl, methyl or
 tert-butyl.
 C can be, for example, the radical of a nucleoside, an endiine antibiotic
 or a cytotoxic peptide antibiotic, for example from the class of
 dolastatins, or a quinolone- or naphthyridonecarboxylic acid as defined
 below. C can be, for example, batracyline, 5-fluorouracil, cytosine
 arabinoside, methotrexate, etoposide, camptothecin, daunomycin,
 doxorubicin, taxol, vinblastine, vincristine, dynemycin, calicheamycin,
 esperamycin, quercetin, suramin, erbstatin, cyclophosphamide, mitamycin C,
 melphalan, cisplatin, bleomycin, staurosporin or another active compound
 having an antineoplastic action. The cytostatic is linked with AA2 via
 amino or hydroxyl functions.
 Especially preferred compounds of the formula (I) are those in which
 K=a carbohydrate radical of the general formula
 ##STR6##
 wherein
 A=methyl, hydroxymethyl, carboxyl and methoxycarbonylmethyl and CH.sub.2
 --B, wherein B in turn can be a carbohydrate radical of the general
 formula (II) linked via the anomeric centre.
 R.sub.2, R.sub.3 and R.sub.4 =individually or together at the same time, H,
 hydroxyl, C.sub.1 -C.sub.3 -alkyloxy, carboxy-C.sub.1 -C.sub.3 -alkyloxy
 and C.sub.1 -C.sub.3 -alkyl esters and amides derived therefrom,
 hydroxyalkyloxy, acyloxy, carboxy-(C.sub.1 -C.sub.3 -alkyl)-carbonyloxy,
 sulphato or another carbohydrate radical in position R.sub.3 or R.sub.4
 linked via the anomeric centre.
 Two of the radicals R.sub.2, R.sub.3 and R.sub.4 together can also denote
 an epoxide group.
 The stereochemistry on the anomeric centre can be .alpha. or .beta.. The
 D-manno, D-galacto, L-gulo, D-gluco, L-rhamno or L-fuco configuration can
 result from the stereochemistry on the other centres.
 Sp=an arylene radical which is modified with K and L in the ortho- or
 para-position and furthermore can also carry, in addition to hydrogen
 atoms, a further substituent, which can be methoxy, nitro or chlorine;
 ##STR7##
 where
 R=chlorine or hydroxyalkylamino.
 AA1 is an amino acid radical, such as lysine, alanine, aspartic acid,
 glutamic acid, glycine, ornithine, tyrosine, valine or serine in the D or
 L configuration, or a direct bond. The amino acid radical can be linked
 with L both via the .alpha.-amino group and, where appropriate, via the
 side chain amino functions, and also via both functions, and thus
 optionally carries a further grouping K-Sp-L-, which is identical to or
 different from the first. If AA1 carries further functional groups, these
 are preferably deblocked.
 AA2 is an amino acid radical, such as alanine, lysine, glycine, serine,
 ornithine or diaminopropionic acid in the D or L configuration, or a
 direct bond. The amino acid radical can be linked with AA1 both via the
 .alpha.-amino group and, where appropriate, via the side chain amino
 functions, and also via both functions, and can thus optionally carry a
 further grouping K-Sp-L-, which is identical to or different from the
 first. If AA2 carries further functional groups, these are preferably
 deblocked.
 C can be batracyline, methotrexate, quinolone-a, etoposide, melphalan,
 taxol, camptothecin, daunomycin or doxorubicin or a quinolone- or
 naphthyridonecarboxylic acid as defined below. The cytostatic is linked
 with AA2 via an amino or hydroxyl function.
 The quinolone- or naphthyridonecarboxylic acid structural units C used as
 educts can be represented by the general structure of the formula (III)
EQU T-Q (III)
 in which
 Q denotes a radical of the formulae
 ##STR8##
 wherein
 R.sup.a represents alkyl which has 1 to 4 carbon atoms and is optionally
 mono- or disubstituted by halogen or hydroxyl, vinyl, cycloalkyl which has
 3 to 6 carbon atoms and is optionally substituted by 1 or 2 fluorine
 atoms, bicyclo[1.1.1]pent-1-yl, 1,1-dimethylpropargyl, 3-oxetanyl,
 methoxy, amino, methylamino, dimethylamino or phenyl which is optionally
 mono- or disubstituted by halogen, amino or hydroxyl, or, together with
 R.sup.e, can also form a bridge described for that radical,
 R.sup.b represents hydroxyl, alkoxy having 1 to 3 carbon atoms or
 nitromethyl,
 R.sup.c represents hydrogen or methyl or, together with R.sup.g, can also
 form a bridge described for that radical,
 R.sup.d represents hydrogen, CH.sub.3, CH.sub.2 F or .dbd.CH.sub.2,
 X.sup.1 represents hydrogen, halogen or nitro,
 X.sup.2 represents hydrogen, halogen, amino, hydroxyl, methoxy, mercapto,
 methyl, halogenomethyl or vinyl,
 Y represents N or C--R.sup.e, wherein
 R.sup.e represents hydrogen, halogen, CF.sub.3, OCH.sub.3, OCHF.sub.2,
 CH.sub.3, CN, CH.dbd.CH.sub.2 or C.dbd.CH, or, together with R.sup.a, can
 also form a bridge of the structure --*O--CH.sub.2 --CH--CH.sub.3,
 --*S--CH.sub.2 --CH.sub.2 --, --*S--CH.sub.2 --CH--CH.sub.3, --*CH.sub.2
 --CH.sub.2 --CH-CH.sub.3 or --*O--CH.sub.2 --N--R.sup.f, wherein the atom
 marked with is linked with the carbon atom of Y and wherein
 R.sup.f denotes hydrogen, methyl or formyl, and
 D represents N or C--R.sup.g, wherein
 R.sup.g represents hydrogen, halogen, CF.sub.3, OCH.sub.3, OCHF.sub.2 or
 CH.sub.3, or, together with R.sup.c, can also form a bridge of the
 structure --*O--CH.sub.2 --, --*NH--CH.sub.2 --, --*N(CH.sub.3)--CH.sub.2
 --, --*N(C.sub.2 H.sub.5)--CH.sub.2 --, --*N(C.sub.3 H.sub.5)--CH.sub.2 --
 or --*S--CH.sub.2 --, wherein the atom marked with * is linked with the
 carbon atom of D,
 n denotes 1, 2 or 3 and
 T denotes a radical of the formula
 ##STR9##
 wherein
 R.sup.h represents
 ##STR10##
 wherein
 R.sup.k represents hydrogen or methyl and
 R.sup.i represents hydrogen, C.sub.1 -C.sub.3 -alkyl or cyclopropyl.
 Compounds of the formula (III) which are particularly preferred as the
 cytostatic C are those in which
 Q denotes a radical of the formula
 ##STR11##
 wherein
 R.sup.a represents alkyl which has 2 to 4 carbon atoms and is optionally
 substituted by 1 fluorine atom, cyclopropyl which is optionally
 substituted by 1 fluorine atom or phenyl which is optionally mono- or
 disubstituted by fluorine,
 R.sup.b represents hydroxyl or alkoxy having 1 or 2 carbon atoms,
 R.sup.c represents hydrogen or methyl, or, together with R.sup.g, can form
 a bridge described for that radical,
 X.sup.1 represents fluorine,
 X.sup.2 represents hydrogen or amino,
 Y represents N or C--R.sup.e, wherein
 R.sup.e represents hydrogen, fluorine, chlorine, CF.sub.3, OCH.sub.3,
 OCHF.sub.2 or C.ident.CH, or, together with R.sup.a, can form a bridge of
 the structure --*O--CH.sub.2 --CH--CH.sub.3 or --*O--CH.sub.2
 --N--R.sup.f, wherein the atom marked with * is linked with the carbon
 atom of Y and wherein R.sup.f denotes methyl,
 D represents N or C--R.sup.g, wherein
 R.sup.g represents hydrogen, fluorine, chlorine, CF.sub.3, OCH.sub.3 or
 CH.sub.3, or, together with R.sup.e, also form a bridge of the structure
 --*O--CH.sub.2 --, --*N--CH.sub.2 --, --N(CH.sub.3)--CH.sub.2 -- or
 --*S--CH.sub.2 --, wherein the atom marked with is linked with the carbon
 atom of D, and
 T denotes a radical of the formula
 ##STR12##
 wherein
 R.sup.h represents
 ##STR13##
 wherein
 R.sup.k represents hydrogen or methyl, and
 R.sup.i represents hydrogen or methyl.
 Glycoconjugates with camptothecin or derivatives thereof are likewise
 particularly preferred.
 The compounds of the general formula I in which K, Sp and L denote hydrogen
 and
 C represents camptothecin are furthermore of particular importance. These
 substances are new and can be reacted as intermediate products to give
 further derivatives of the general formula I, and in turn also show an
 interesting pharmaceutical action spectrum, in particular as cytostatics.
 The compounds according to the invention can be in stereoisomeric forms,
 for example as enantiomers or diastereomers, or in the form of mixtures
 thereof, for example as a racemate. The invention relates both to the pure
 stereoisomers and to mixtures thereof.
 If necessary, the stereoisomer mixtures can be separated into the
 stereoisomerically uniform constituents in a known manner, for example, by
 chromatography or by crystallization processes.
 The compounds according to the invention can also be in the form of their
 salts. Salts with organic or inorganic bases or acids and inner salts may
 be mentioned in general here.
 The acids which can be added on include, preferably, hydrogen halide acids,
 such as, for example, hydrochloric acid and hydrobromic acid, in
 particular hydrochloric acid, and furthermore phosphoric acid, nitric
 acid, sulphuric acid, mono- and bifunctional carboxylic acids and
 hydroxycarboxylic acids, such as, for example, acetic acid, maleic acid,
 malonic acid, oxalic acid, gluconic acid, succinic acid, fumaric acid,
 tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid,
 and sulphonic acids, such as, for example, p-toluenesulphonic acid,
 1,5-naphthalene-disulphonic acid or camphorsulphonic acid.
 Physiologically acceptable salts can likewise be metal or ammonium salts of
 the compounds according to the invention which have a free carboxyl group.
 Particularly preferred salts are, for example, sodium, potassium,
 magnesium or calcium salts, and ammonium salts which are derived from
 ammonia or organic amines, such as, for example, ethylamine, di- or
 triethylamine, di- or triethanolamine, dicyclohexylamine,
 dimethylaminoethanol, arginine, lysine, ethylenediamine or phenethylamine.
 EXAMPLE SERIES A
 Biological Testing
 EXAMPLE A.1
 Growth Inhibition Test for Determination of the Cytotoxic Properties of
 Glycoconjugates of Batracyline and of Quinolone-a
 The human colon cell lines SW 480 and HT 29 (ATCC no. CCL 228 and HBT-38)
 and the mouse melanoma cell line B 16 F 10 were cultured in Roux dishes in
 RPMI 1640 medium with addition of 10% FCS. The cultures were then
 trypsinized and taken up in RPMI plus 10% FCS to a cell count of 50,000
 cells/ml. 100 .mu.l of cell suspension/well were introduced into a 96
 microwell plate and incubated for 1 day at 37.degree. C. in a CO.sub.2
 incubating cabinet. A further 100 .mu.l of RPMI medium and 1 .mu.l of
 dimethyl sulphoxide with the test substances were then added. The growth
 was checked after day 3 and day 6. 40 .mu.l of MTT solution
 (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazoline bromide) with an
 initial concentration of 5 mg/ml of H.sub.2 O were added to each
 microwave. The plate was incubated for 5 hours in a CO.sub.2 incubating
 cabinet at 37.degree. C. The medium was then sucked off and 100 .mu.l of
 i-propanol/well were added. After shaking for 30 minutes with 100 .mu.l of
 H.sub.2 O, the extinction was measured at 540 nm with a Titertek Multiskan
 MCC/340 (Flow).
 The cytotoxic action of the glycoconjugates of batracyline described is
 shown in Table 1a as the IC.sub.50 value in each case for the SW 480 and
 HT 29 cell lines.
 The IC.sub.50 values for the quinolone-a glycoconjugates on the SW 480, HT
 29 and B 16 F 10 cell lines are summarized in Table 1b.
 TABLE 1a
 IC.sub.50 [.mu.M] IC.sub.50 [.mu.M]
 Substance SW 480 HT 29
 Batracyline 25 20
 3.2 100 75
 3.4 100 65
 3.7 55 n.m
 3.9 40 55
 3.10 100 125
 3.11 85 n.m.
 3.14 40 n.m.
 3.18 15 n.m.
 3.19 75 n.m.
 3.20 100 n.m.
 3.21 90 n.m.
 3.23 50 n.m.
 3.24 95 n.m.
 3.26 50 n.m.
 3.27 110 n.m.
 3.28 60 n.m.
 3.29 110 n.m.
 3.30 &gt;250 n.m.
 3.33 90 70
 4.1 25 30
 4.3 20 20
 4.4 30 25
 4.5 15 15
 4.6 10 10
 4.7 15 15
 4.8 50 40
 4.9 20 30
 4.10 30 30
 4.11 15 15
 4.12 15 9
 5.1 55 45
 5.2 20 55
 5.6 &gt;250 n.m.
 5.8 100 &gt;250
 5.9 70 70
 5.12 20 20
 5.13 20 40
 5.14 20 30
 5.15 &gt;250 70
 5.19 35 25
 5.20 50 30
 5.21 60 80
 5.22 30 40
 5.23 25 35
 6.2 40 50
 6.3 70 105
 6.7 60 &gt;250
 6.10 50 50
 6.12 35 50
 6.15 &gt;250 &gt;250
 6.20 80 n.m.
 6.21 150 n.m.
 6.23 107 45
 6.25 50 40
 6.28 40 25
 6.29 95 130
 6.30 60 70
 6.32 60 60
 6.34 50 n.m.
 6.35 20 n.m.
 6.36 70 70
 6.40 170 60
 6.43 90 80
 6.46 120 100
 6.59 50 50
 6.60 50 40
 6.80 40 25
 6.81 30 30
 6.82 125 n.m.
 6.83 90 n.m.
 6.85 22 n.m.
 7.1 40 40
 7.2 40 30
 7.3 50 n.m.
 7.5 80 n.m.
 7.7 100 &gt;250
 7.8 40 30
 7.11 30 25
 7.12 10 10
 8.10 70 n.m.
 8.11 45 n.m.
 8.12 30 n.m.
 TABLE 1b
 IC.sub.50 [.mu.M] IC.sub.50 [.mu.M] IC.sub.50 [.mu.M]
 Substance SW 480 HT 29 B 16 F 10
 10.1 50 &gt;250 15
 10.2 4 3 5
 10.3 5 4 0.7
 11.2 30 n.m. 9
 11.6 8 9 5
 11.7 12 13 15
 11.8 12 16 15
 11.9 12 12 9
 11.10 8 20 2
 11.16 10 10 1.5
 11.17 75 75 8
 11.18 4.5 3.5 0.5
 12.1 1 1.5 0.1
 12.2 4 n.d. 0.8
 12.3 2 n.d. 0.3
 12.5 1 4 0.2
 12.6 4 7 0.3
 12.7 60 &gt;250 20
 12.8 8 7 1
 12.9 4 8 2
 12.10 15 15 4
 12.11 2 2 0.5
 12.12 8 13 0.5
 12.13 35 100 1
 12.14 1 2 0.3
 12.15 0.3 1 0.1
 14.1 0.8 1 1.5
 14.2 1 6 1.5
 14.3 8 4 4
 14.4 1.5 1 0.4
 15.1 20 20 2
 15.2 50 70 15
 16.1 50 100 200
 16.2 50 60 80
 17.1 10 5 5
 17.2 4 4 4
 18.1 0.03 0.01 0.2
 18.2 0.02 0.02 0.2
 18.4 0.02 0.02 0.3
 18.5 0.2 0.2 1
 18.9 0.08 0.06 0.7
 18.14 0.015 0.01 0.08
 The dependence of the biological action on the carbohydrate is additionally
 demonstrated by the inactivity of the carbohydrate-free comparison
 compounds N-[N.sup..alpha.,N.sup..epsilon.
 -bis-(4-hydroxyphenylamino-thiocarbonyl)-lysyl]-batracyline and
 N-[N.sup..alpha.,N.sup..epsilon.
 -bis-(4-hydroxyphenylamino-thiocarbonyl)-lysyl-D-alanyl]-batracyline and
 N-[N.sup..alpha.,N.sup..epsilon.
 -bis-(4-hydroxyphenylamino-thiocarbonyl)-D-lysyl-quinolone-a (IC.sub.50
 values&gt;250), on which Example series 5, 6 and 11 are based.
 EXAMPLE A.2
 In Vitro Investigation of the Cleavability of the Glycoconjugates
 Cleavage Kinetics With Human Blood
 1.225 ml of human blood are incubated together with 1.25 ml of PBS and 25
 .mu.l of a substrate stock solution (1 mg/ml in 3% dimethyl sulphoxide in
 PBS) at 37.degree. C. After 1 hour and 24 hours, samples of in each case 1
 ml are taken, mixed with 1 ml of ethanol and left to stand at 4.degree. C.
 for 20 minutes. After centrifugation (5 minutes at 3500 rpm), 100 .mu.l of
 supernatant are taken for the HPLC analysis.
 Cleavage Kinetics With Cells
 2.25 ml of PBS are incubated together with 225 .mu.l of a cell suspension
 (30 mg/ml) and 25 .mu.l of substrate stock solution (1 mg/ml in 3%
 dimethyl sulphoxide in PBS) at 37.degree. C. After 1 hour and 24 hours,
 samples of in each case 1 ml are taken, mixed with 1 ml of ethanol and
 left to stand at 4.degree. C. for 20 minutes. After centrifugation (5
 minutes at 3500 rpm), 100 .mu.l of supernatant are taken for the HPLC
 analysis.
 HPLC Conditions
 Apparatus:
 Waters unit
 Column:
 Bischoff Hypersil OCS RP 18 5 .mu.m 250.times.4 mm
 Eluent:
 A: 10 mM potassium phosphate buffer, pH 4.5
 B: 80% acetonitrile/20% water
 Flow:
 1 ml/minute
 Wavelength:
 372 nm
 Gradient:
 0 minute 10% B
 10 minutes 60% B
 15 minutes 60% B
 18 minutes 10% B
 20 minutes 60% B
 Eluent for Quinolone-a Conjugates
 A: 100% methanol
 B: 10 mM potassium phosphate buffer, pH 2.2;
 10 mM heptanesulphonic acid
 TABLE 2a
 % cleavage in % cleavage in % cleavage in
 Exam- human blood SW-480 hepatoma
 ple 1 hour 24 hours 1 hour 24 hours 1 hour 24 hours
 3.4 n.d. n.d. 74* n.d. 98* n.d.
 3.9 0 54* 28* 100* 32* 100*
 4.4 0 0 0 0 0 0
 5.9 0 0 0 0 0 0
 6.2 n.d. n.d. 0 0 0 0
 6.12 n.d. n.d. 0 0 0 0
 7.3 0 0 0 0 0 0
 *Cleavage product is N-[D-alanyl]-batracyline
 TABLE 2b
 % cleavage in % cleavage in % cleavage in
 Exam- human blood SW-480 hepatoma
 ple 1 hour 24 hours 1 hour 24 hours 1 hour 24 hours
 11.2 0 0 0 0 0 0
 11.6 0 11% 0 8% 0 12%
 11.7 0 0 0 0 0 0
 12.1 0 0 0 0 0 0
 12.3 0 0 0 0 0 0
 12.8 0 0 0 0 0 0
 EXAMPLE A.3
 Investigation of Organ Distribution
 Athymic naked mice (strain NMRI nu/nu) bred in "Drug Development
 Laboratory, Oncotest GmbH", Prof. H. H. Fiebig, Freiburg, were used for
 all the experiments. The animals were kept in Macrolon cages under laminar
 flow conditions. Tissue of the cell line SW 480 which had been grown
 beforehand in several passages in the naked mice, was used as the tumour
 material.
 Two tumours per animal were implanted subcutaneously in the two flanks of
 the naked mice 6 to 8 weeks old. The animals were kept for 26 to 27 days
 until the time of randomization. The average tumour size was then 500 mg,
 corresponding to a tumour diameter of about 10 mm.
 The pharmacokinetics themselves proceeded as follows: the substance to be
 investigated was injected into the naked mice and the mice were then put
 back in the cages until samples were taken after 1/2 hour and after 4
 hours. The taking of samples itself began with sampling of blood. For
 this, the mouse was anaesthetized by means of anaesthetic ether (duration
 1/2 to one minute). 0.5 hour and 4 hours after injection of the substance,
 the abdominal cavity was opened and the mouse was exsanguinated under
 anaesthesia via the Vena cava caudalis in the course of 1 to 2 minutes and
 then sacrificed by breaking its neck. As a result, central circulatory
 arrest occurred and organ perfusion was suppressed. The individual organs
 were then exposed and removed, an operation which took about 5 minutes.
 Immediately thereafter, the organ samples and then the remainder of the
 body were weighed and frozen in liquid nitrogen.
 The substance "conjugate 1" is administered i.p. in an amount of 300 mg/kg
 of body weight and the substance "conjugate 2" is administered i.v. into
 the tail vein in an amount of 100 mg/kg. 5 animals are used per substance
 and time.
 The distribution results are summarized in Table 3 for conjugate 1 and in
 Table 4 for conjugate 2.
 A. Calibration Series
 5, 10, 50, 100 and 200 .mu.g of substance, dissolved in ethanol/water (1:1,
 v/v) were added to 1 g of bovine liver. The samples were then ground in a
 mortar with 1 g of sea sand and 2.5 ml of cooled ethanol/water (1:1, v/v)
 and centrifuged at 3500 rpm for 2 minutes. After removal of the
 supernatant, the residue was again mixed with 2.5 ml of ethanol/water and
 centrifuged and the supernatants were combined. In each case 100 .mu.l
 were taken and analyzed by HPLC.
 HPLC Conditions
 Apparatus:
 Waters unit
 Column:
 Bischoff Hypersil OCS RP 18 5 .mu.m 250.times.4 mm
 Eluent:
 A: 80% acetonitrile/20% water
 B: 10 mM potassium phosphate buffer, pH 4.5
 Gradient:
 0 minute 90% B
 10 minutes 40% B
 15 minutes 40% B
 18 minutes 90% B
 20 minutes 90% B
 Flow:
 1 ml/minute
 Wavelength:
 372 nm
 B. Working up of the Organs
 The organs were worked up analogously to A, the entire organs being broken
 down with 2.5 ml of ethanol/water and extracted.
 C. Working up of the Blood
 The amount of blood taken was mixed with 2 ml of ethanol/water (1:1, v/v)
 and centrifuged for 2 minutes at 3500 rpm, and the supernatant was
 decanted. 2 ml of ethanol/water (1:1, v/v) were again added to the
 residue, the mixture was centrifuged and the supernatants were combined.
 In each case 100 .mu.l of the combined supernatants were analyzed by HPLC.
 The HPLC conditions used under A were used.
 ##STR14##
 TABLE 3
 Evaluation of organ samples
 Mean 1 hour Mean 4 hours
 Organ Substance (.mu.g/g of organ) (.mu.g/g of organ)
 Blood Conjugate 1 31.2 --
 Batracyline -- --
 Tumour Conjugate 1 56.6 24.4
 Batracyline -- --
 Liver Conjugate 1 770 126
 Batracyline 34.1 22.4
 Kidney Conjugate 1 81 78.4
 Batracyline 26.1 27.5
 Brain Conjugate 1 -- --
 Batracyline -- --
 TABLE 4
 Evaluation of organ samples
 Mean 0.5 hour Mean 4 hours
 Organ Substance (.mu.g/g of organ) (.mu.g/g of organ)
 Blood Conjugate 2 6.5 --
 Batracyline -- --
 Tumour Conjugate 2 2.0 --
 Batracyline 2.5 3.12
 Liver Conjugate 2 0.9 1.2
 Batracyline -- --
 Kidney Conjugate 2 17.5 0.5
 Batracyline 10.7 0.8
 Brain Conjugate 2 -- --
 Batracyline -- --
 EXAMPLE A.4
 Determination of the Acute Toxicity of Glycoconjugates of Batracyline
 (Single Administration)
 The acute toxicity of the batracyline derivatives was determined on nu/nu
 naked mice.
 The substances administered i.v., as aqueous solutions, and the substances
 administered i.p., as solutions in dimethyl sulphoxide, were injected once
 in concentrations of up to 400 mg of substance per kg of mouse.
 The individual dose tolerated was calculated from the decrease in the
 weight of the animals up to 21 days after administration and from the
 number of animals surviving.
 The individual dose of the substances which can be tolerated can be seen
 from Table 5.
 For substances 3.16; 3.33; 3.9; 6.12; 6.14; 6.2; 6.81; and 8.2 it was more
 than 200 mg of substance per kg of mouse. For substances 3.33; 6.12; 6.14;
 6.2; and 6.81, still no acute toxicity was to be detected even with a dose
 of 400 mg/kg.
 In contrast, sugar-free lysyl-D-alanyl-batracyline (2.13) was already
 significantly toxic at individual doses of between 25 and 50 mg/kg of
 mouse.
 TABLE 5
 Maximum individual dose of batracyline derivatives and quinolone-a
 derivatives which can be tolerated
 Individual dose tolerated in mg/kg of mouse
 Example i.p. i.v.
 2.13 50 25
 3.4 200 &lt;100
 (2 animals died)
 3.9 200 200
 3.16 &gt;200 n.d.
 3.33 n.m. &gt;400
 6.2 &gt;400 n.m.
 6.12 n.m. &gt;400
 6.14 &gt;400 n.m.
 6.81 n.m. &gt;400
 8.2 &gt;200 n.d.
 Quinolone-a n.d. &lt;25
 12.3 n.d. &gt;200
 EXAMPLE A.5
 Determination of the Acute Toxicity After Several Administrations
 The substances were administered partly i.v. and partly i.p., either daily
 on days 1 to 4 and 7 to 10 or on days 1, 5 and 9. The dosages were 400,
 200 and 100 mg/kg/day. The evaluation was made according to the decrease
 in weight up to day 21 and according to the number of surviving animals.
 For the experiments, 5 animals were employed per substance and dose. The
 results are summarized in Table 6.
 TABLE 6
 Maximum tolerable dose with multiple administrations
 Administration Dosage on day MTD mg/kg day
 3.9 i.v. 1-4, 7-10 .about.50
 1-4 .about.100
 3.33 i.v. 1, 5, 9 &gt;400
 6.2 i.p. 1-4, 7-10 .about.400
 1, 5, 9 &gt;400
 6.12 i.v. 1-4, 7-10 &gt;400
 1, 5, 9 &gt;400
 6.14 i.p. 1, 5, 9 &gt;400
 6.81 i.v. 1-4, 7-10 .about.200
 &gt;400
 Batracyline i.p 1, 5, 9 -100
 EXAMPLE A.6
 Haematopoietic Activity of Glycoconjugates of Quinolone-a in Comparison
 With the Active Compound on Which They Are Based
 Material and Methods
 In vitro:
 Bone marrow cells are flushed out of the femur of mice. 10.sup.5 cells are
 incubated in McCoy SA medium (0.3% agar) together with recombinant murine
 GM-CSF (Genzyme; parent cell colony formation) and the substances
 (10.sup.-4 to 100 .mu.g/ml) at 37.degree. C. and 7% CO.sub.2. 7 days
 later, the colonies (&lt;50 cells) and clusters (17-50 cells) are counted.
 In vivo:
 Mice are treated subcutaneously with 1, 3, 10 or 30 mg/kg of the compounds.
 At various times (3, 24, 48, 72 p. inj.) the femurs are removed and the
 bone marrow cells isolated. 2.times.10.sup.5 cells are incubated with
 GM-CSF as described above and, after 7 days, the colonies and clusters are
 counted.
 Results
 As shown in Table 7, the glycoconjugates investigated show an inhibition of
 bone marrow parent cell proliferation which is reduced by a factor of
 10.sup.5 to 10.sup.3 compared with quinolone-a.
 In vivo also, no inhibition in parent cell proliferation was to be observed
 by compound 12.3 up to 30 mg/kg, compared with quinolone-a. A massive
 suppression of parent cell proliferation was already induced with 3 mg/kg
 of quinolone-a (FIG. 1).
 TABLE 7
 CSF-induced proliferation of bone marrow parent cells of the mouse
 Examples IC.sub.50 [.mu.g/ml]
 Quinolone-a 0.0002
 11.2 22.5
 11.7 2.9
 12.1 0.21
 12.3 0.27
 12.6 0.3
 12.8 0.3
 14.1 2.9
 14.2 3.6
 14.4 3.6
 EXAMPLE A.7
 Antineoplastic Activity of Quinolone-a Conjugates
 The in vitro activity of glycoconjugates of quinolone-a was determined on
 human tumour xenografts in a two-layer soft agar culture system according
 to Hamburger and Salmon (Science 197: 461-463).
 The solid tumours were initially grown in the athymic naked mouse (NMRI
 nu/nu), obtained by surgery and comminuted mechanically. Individual cells
 were then obtained by incubation in an enzyme mixture of collagenase
 0.05%, DNAse 0.07% and hyaluronidase 0.1% in RPMI at 37.degree. C. for 30
 minutes. The cells were washed 2.times. and then passed through a sieve of
 200 .mu.m and 20 .mu.m mesh width.
 The following culture method was used:
 The base layer comprises 0.2 ml of Iscoves's Modified Dulbeccos Medium with
 20% foetal calf serum and 0.7% agar. 40,000 to 200,000 cells in 0.2 ml of
 the same medium and 0.4% agar were applied to this layer in 24 multiwell
 plates. The cytostatic substances were added in 0.2 ml of medium.
 The cultures were incubated at 37.degree. C. in a 7% CO.sub.2 atmosphere
 for 6 to 15 days. The colonies which had grown were then counted under an
 inverting microscope, the living colonies being stained with a tetrazolium
 chloride dyestuff 24 hours before the evaluation.
 The effect of the active compound is expressed in per cent of surviving
 colonies compared with the colony count of untreated plates (T/C=colony
 count treated.times.100/control count untreated).
 A substance is active if the T/C value is .ltoreq.30%.
 This value is shown as the IC.sub.70 value in .mu.g/ml in Table 8.
 TABLE 8
 IC.sub.70 /.mu.g/ml
 Example 11.7 12.1 12.3 12.5 Quinolone-a
 CXF 280 &gt;100 70 5 &lt;0.3 6
 HT 29 56 6 5 11 20
 SW 480 18 8 11 10 3
 LXFL 529 4 0.9 2 2 3
 LXFS 538 18 0.4 0.5 &lt;0.3 &lt;0.3
 MEXF 989 3 &lt;0.3 &lt;0.3 0.5 &lt;0.3
 OVXF 899 234 45 162 55 2
 OVXF 1023 136 12 10 9 0.5
 EXAMPLE A.8
 In Vivo Tests
 Method
 Mice are inoculated with 5.times.10.sup.6 B16F10 tumour cells on day 0. The
 animals in which tumour cells are transplanted develop solid peritoneal
 tumours and are then treated daily with test substances or with the
 vehicle control. In the control group, 50% of the animals usually die
 between day 14 and 20. The test substances are administered in buffer or
 an organic solvent system comprising 20% methanol and 20% dimethyl
 sulphoxide in 0.7% sodium chloride solution.
 The administration of the vehicle showed no influence on the survival time
 of the animals. The therapeutic result arises from the prolonging of the
 survival time of the treated animals. The tolerance of the compounds is
 analysed in parallel on animals which do not carry tumours. A therapeutic
 index can be estimated from the tolerance and prolonging of the survival
 time.
 TABLE 9
 % survivors
 Day 0 Day 20 Day 25 Day 30 Day 35
 Control 100 70 30 10 10
 11.12
 1 mg/kg 100 90 60 30 30
 11.12
 (100 mg/kg) 100 100 100 90 90
 Quinolone-a 100 100 100 60 40
 (0.1 mg/kg)
 Etoposide 100 90 80 80 70
 (5 mg/kg)
 Table 9 shows the therapeutic activity of the compound from Example 11.12
 on mice in which a B16F10 tumour was transplanted.
 EXAMPLE A.9
 In Vivo Inhibition of Tumour Growth Using a Naked Mouse Model
 Material
 Athymic naked mice (NMRI nu/nu strain) were used for all the in vivo
 experiments for investigation of the inhibition of tumour growth. The
 large-cell lung carcinoma LXFL 529 selected was developed by serial
 passage in naked mice. The human origin of the tumour was demonstrated by
 isoenzymatic and immunohistochemical methods.
 Experimental Set-up
 The tumour was implanted subcutaneously in both flanks of nu/nu naked mice
 6 to 8 weeks old. Treatment was started, regardless of the doubling time,
 as soon as the tumours had reached a diameter of 5-7 mm. The mice were
 allocated to the treatment group and the control group (5 mice per group
 with 8-10 evaluable tumours) by randomization. The individual tumours of
 the control group all grew progressively.
 The size of the tumours was measured in two dimensions by means of a
 sliding gauge. The tumour volume, which correlates well with the cell
 count, was then used for all the evaluations. The volume was calculated
 according to the equation "length.times.breadth.times.breadth/2"
 ([a.times.b.sup.2 ]/2, a and b represent two diameters at right angles).
 The values of the relative tumour volume (RTV) were calculated for each
 individual tumour by dividing the tumour size on day X with the tumour
 size on day 0 (at the time of randomization). The mean RTV values were
 then used for the further evaluation.
 The inhibition of the increase in the tumour volume (tumor volume of the
 test group/control group, T/C, in per cent) was the concluding measurement
 value.
 Treatment
 All the compounds were administered according to an intermittent plan in
 each case on day 1, 5 and 9. Furthermore, all the compounds were
 administered intraperitoneally (i.p.) using water as the solvent.
 TABLE 10
 Dose.sup.a) Survival time Number of Relative tumour volume
 Optimum
 Treatment [mg/kg/day] (days) tumours [% of day 0].sup.b)
 T/C.sup.b)
 Control -- 19 &gt;21 10 1552
 100%
 group &gt;21 &gt;21
 14
 12.6 100 23 &gt;26 8 300.7
 19.4%
 26 &gt;26
 &gt;26
 12.8 50 &gt;21 &gt;21 9 502.2
 32.3%
 &gt;21 &gt;21
 &gt;21
 12.14 25 23 &gt;26
 19 26 8 519.5
 33.5%
 &gt;26
 a) maximum tolerated dose (MTD)
 b) on day 19
 In this test, the camptohecin compounds of Example series 18 as a rule
 showed a comparable or better action.
 EXAMPLES SERIES B
 Synthesis Examples
 EXAMPLE 1.1
 p-Aminophenyl 2-O-methyl-.beta.-L-fucoside
 ##STR15##
 1.1.a) p-Nitrophenyl 3,4-O-isopropylidene-.beta.-L-fucoside
 65 mg of p-toluenesulphonic acid and, at 30 minute intervals, 5.times.100
 .mu.l of 2-methoxypropene are added to a solution of p-nitrophenyl
 .beta.-L-fucoside (750 mg, 2.63 mmol) in 40 ml of
 dimethylformamide/dioxane 1:2 at 0.degree. C. After the mixture has been
 stirred at 20.degree. C. for 16 hours, it is concentrated and the residue
 is purified by flash chromatography (methylene chloride/methanol 99:1).
 After concentration, 710 mg (83%) of a white solid are obtained.
 1.1.b) p-Nitrophenyl 2-O-methyl-3,4-O-isopropylidene-.beta.-L-fucoside
 100 mg (0.307 mmol) of the compound from Example 1.1.a are initially
 introduced into 10 ml of tetrahydrofuran together with 96 .mu.l of methyl
 iodide, and 11 mg of sodium hydride (80% strength) are then added in
 portions. After the mixture has been stirred at 20.degree. C. for 3 hours,
 it is topped up with a further 96 .mu.l of methyl iodide and 11 mg of
 sodium hydride. After further stirring at 20.degree. C. for 16 hours, a
 little water and 100 ml of methylene chloride are added. The batch is
 extracted by shaking twice with water, the organic phase is concentrated
 and the product is then purified by column chromatography (petroleum
 ether/ethyl acetate 8:1). Yield: 78 mg (75%).
 1.1) p-Aminophenyl 2-O-methyl-.beta.-L-fucoside
 78 mg (0.23 mmol) of p-nitrophenyl
 2-O-methyl-3,4-O-isopropylidene-.beta.-L-fucoside are stirred in 3 ml of
 80% strength acetic acid at 20.degree. C. for 16 hours. The acetic acid is
 then removed in vacuo, 10 ml of methanol are added to the batch and, after
 addition of platinum dioxide, hydrogenation is carried out in a hydrogen
 atmosphere under a slightly increased pressure. The suspension is filtered
 over Celite and the material on the filter is washed with methanol. After
 purification by chromatography (methylene chloride/methanol 97.5:2.5), 77
 mg (80%) of the target product are obtained. [TLC: methylene
 chloride/methanol 9:1 R.sub.f =0.42].
 EXAMPLE 1.2
 p-Aminophenyl 3-O-methyl-.beta.-L-fucoside
 ##STR16##
 1.2.a) p-Nitrophenyl 3-O-Methyl-.beta.-L-fucoside
 784 g (31.5 mmol) of dibutyltin oxide are added to 6 g (21 mmol) of
 p-nitrophenyl .beta.-L-fucoside in 300 ml of absolute methanol and the
 mixture is heated under reflux for 2 hours. It is then concentrated and
 the residue is dried and then taken up in 300 ml of dimethylformamide.
 After addition of 15.7 ml of methyl iodide, the batch is stirred at
 70.degree. C. for 40 hours. The solvent is removed in vacuo and the
 residue is taken up in 300 ml of methylene chloride. The suspension is
 filtered, the solution which remains is concentrated again and the residue
 is subjected to flash chromatography (methylene chloride/methanol 99:1).
 After concentration, 381.5 mg (61%) of the target product are obtained.
 1.2) p-Aminophenyl 3-O-methyl-.beta.-L-fucoside
 3.81 g (12.73 mol) of p-nitrophenyl 3-O-methyl-.beta.-L-fucoside are
 hydrogenated analogously to example 1.1. Yield: 3 g (88%). [TLC: methylene
 chloride/methanol 9:1 R.sub.f =0.53].
 EXAMPLE 1.3
 p-Aminophenyl 3-O-methyl-.alpha.-L-fucoside
 ##STR17##
 Preparation analogous to Example 1.2 starting from p-nitrophenyl
 .alpha.-L-fucoside. Yield: 63% over 2 stages. [TLC methylene
 chloride/methanol 9:1 R.sub.f =0.39].
 EXAMPLE 1.4
 p-Aminophenyl 4-O-methyl-.beta.-L-fucoside
 ##STR18##
 1.4.a) p-Nitrophenyl 2-O-benzyl-4-O-acetyl-.beta.-L-fucoside
 31 mg of p-toluenesulphonic acid and 1134 mg (7 mmol) of triethyl
 orthoacetate are added to 1 g (3.5 mmol) of p-nitrophenyl
 .beta.-L-fucoside in 100 ml of absolute tetrahydrofuran. After the mixture
 has been stirred at 20.degree. C. for 15 minutes, the solvent is distilled
 off in vacuo. The residue is taken up in 50 ml of tetrahydrofuran and 3 ml
 of dimethylformamide, and 4165 .mu.l of benzyl bromide and 210 mg of
 sodium hydride (60% strength) are added. After the mixture has been
 stirred at 20.degree. C. for 1 hour, 10 ml of 80% strength acetic acid are
 added, the mixture is concentrated and the residue is purified by flash
 chromatography (methylene chloride/methanol 99:1). After concentration and
 drying, 1236 mg (85%) of the target product are obtained.
 1.4.b) p-Nitrophenyl 2-O-benzyl-3-O-acetyl-4-O-methyl-.beta.-L-fucoside
 1000 mg (2.39 mmol) of p-nitrophenyl
 2-O-benzyl-4-O-acetyl-.beta.-L-fucoside are dissolved in 60 ml of benzene.
 After addition of 2988 .beta.l of methyl iodide and 1109 mg of silver
 oxide, the batch is heated under reflux for 8 hours. The product mixture
 formed is separated into the components by flash chromatography (methylene
 chloride/methanol 99:1). 239 mg (23%) of p-nitrophenyl
 2-O-benzyl-3-O-acetyl-4-O-methyl-.beta.-L-fucoside are isolated, in
 addition to 653 mg (63%) of the isomeric p-nitrophenyl
 2-O-benzyl-3-O-methyl-4-O-acetyl-.beta.-L-fucoside, as a white solid.
 1.4) p-Aminophenyl 4-O-methyl-.beta.-L-fucoside
 224 mg (0.52 mmol) of p-nitrophenyl
 2-O-benzyl-3-O-acetyl4-O-methyl-.beta.-L-fucoside are dissolved in 20 ml
 of methanol, and 390 .mu.l of a 1N sodium methylate solution are added.
 After the mixture has been stirred at 20.degree. C. for 16 hours, it is
 neutralized with 80% strength acetic acid and concentrated and the residue
 is taken up in methylene chloride. The organic phase is washed with 1N
 sodium bicarbonate solution and with water, dried and concentrated. The
 residue is taken up in 20 ml of methanol and hydrogenated over
 palladium/active charcoal analogously to Example 1.1. After concentration,
 the product is taken up in water and lyophilized. 119 mg (88%) of a white
 amorphous solid are isolated. [TLC: methylene chloride/methanol 9:1
 R.sub.f =0.38].
 EXAMPLE 1.5
 p-Aminophenyl 3-O-n-propyl-.beta.-L-fucoside
 ##STR19##
 1.5.a) p-Nitrophenyl 2-O-benzyl-3-O-n-propyl-4-O-acetyl-.beta.-L-fucoside
 Analogously to Example 1.4.b, the isomeric 3- and 4-propylation products
 are prepared from compound 1.4.a with propyl iodide and separated by
 chromatography. p-Nitrophenyl
 2-O-benzyl-3-O-n-propyl-4-O-acetyl-.beta.-L-fucoside is obtained in a 49%
 yield, in addition to p-nitrophenyl
 2-O-benzyl-3-O-acetyl-4-O-n-propyl-.beta.-L-fucoside in a 29% yield.
 1.5.b) p-Aminophenyl 3-O-n-propyl-.beta.-L-fucoside
 Synthesis from Example 1.5.a) fraction 1 analogously to Example 1.4. Yield:
 78% [TLC methylene chloride/methanol 9:1 R.sub.f =0.42].
 EXAMPLE 1.6
 p-Aminophenyl 3-deoxy-.beta.-L-fucoside
 ##STR20##
 1.6.a) p-Nitrophenyl 3,6-dideoxy-3-chloro-4-O-acetyl-.beta.-L-guloside
 31 mg of p-toluenesulphonic acid and 1134 mg (7 mmol) of triethyl
 orthoacetate are added to 1 g (3.5 mmol) of
 p-nitrophenyl-.beta.-L-fucoside in 100 ml of tetrahydrofuran. After the
 mixture has been stirred at 20.degree. C. for 15 minutes, the solvent is
 distilled off in vacuo. 100 ml of a saturated solution of hydrogen
 chloride in methylene chloride are added. After a reaction time of 10
 minutes, the mixture is concentrated and the product is purified by flash
 chromatography (methylene chloride/methanol 99:1). 793 mg (65%) of the
 target product are obtained. [TLC: methylene chloride/methanol 97.5:2.5
 R.sub.f =0.36].
 1.6.b) p-Nitrophenyl 3,6-dideoxy-3-chloro-.beta.-L-guloside
 375 mg (1.08 mmol) of p-nitrophenyl
 3,6-dideoxy-3-chloro-4-O-acetyl-.beta.-L-guloside are dissolved in 25 ml
 of methanol, and 10 drops of 1N sodium methylate solution are added. After
 20 minutes, the mixture is acidified with acetic acid and concentrated and
 the residue is partitioned between 400 ml of methylene chloride and 60 ml
 of water. The organic phase is dried and concentrated and the residue is
 precipitated from methylene chloride/ether. 315 mg (96%) of the target
 product are obtained.
 1.6) p-Aminophenyl 3-deoxy-.beta.-L-fucoside
 315 mg (1.04 mmol) of p-nitrophenyl 3,6-dideoxy-3-chloro-.beta.-L-guloside
 are dissolved in 40 ml of methanol, 200 mg of palladium-on-active charcoal
 and 290 .mu.l of triethylamine are added and hydrogenation is carried out
 in a hydrogen atmosphere under a slightly increased pressure for 4 days.
 The suspension is filtered, washed and concentrated and the product is
 purified by flash chromatography (methylene chloride/methanol 97.5:2.5).
 160 mg (65%) of the deoxy compound are obtained. [TLC: methylene
 chloride/methanol 95:5 R.sub.f =0.18].
 EXAMPLE 1.7
 p-Aminophenyl 3,4-dideoxy-.beta.-L-fucoside
 ##STR21##
 400 mg (1.16 mmol) of p-nitrophenyl
 3,6-dideoxy-3-chloro-4-O-acetyl-.beta.-L-guloside (Example 1.6.a) are
 dissolved in 55 ml of methanol, 323 .mu.l of triethylamine are added and
 hydrogenation is carried out in a hydrogen atmosphere under a slightly
 increased pressure over palladium/active charcoal (10%). After the mixture
 has been stirred at 20.degree. C. for 16 hours, it is filtered over
 Celite, the material on the filter is rinsed, the filtrate is concentrated
 and the residue is taken again in 100 ml of methanol. 1.5 ml of a 1N
 sodium methylate solution are added and the mixture is stirred at room
 temperature for 16 hours. It is neutralized with acetic acid and
 concentrated, and the products formed are separated by flash
 chromatography (methylene chloride/methanol 97.5:2.5). After concentration
 of the corresponding fractions and reprecipitation from methanol/ether,
 120 mg (46%) of the target compound [TLC methylene chloride/methanol 95:5
 R.sub.f =0.31] are obtained, in addition to 77 mg (28%) of p-aminophenyl
 3-deoxy-.beta.-L-fucoside [TLC: methylene chloride/methanol 95:5 R.sub.f
 =0.18].
 EXAMPLE 1.8
 p-Aminophenyl 3,4-epoxy-.beta.-L-fucoside
 ##STR22##
 80 mg (0.23 mmol) of p-nitrophenyl
 3,6-dideoxy-3-chloro-4-O-acetyl-.beta.-L-guloside (Example 1.6.a) are
 taken up in 10 ml of methanol, and 345 .mu.l of 1N sodium methylate
 solution are added. After ultrasonic treatment for 1 hour, the mixture is
 acidified with 80% strength acetic acid and concentrated and the residue
 is chromatographed with methylene chloride/methanol 99:1. After
 concentration of the relevant fractions, the residue is taken up in
 methanol and hydrogenation is carried out over palladium/active charcoal
 analogously to Example 1.1. 46 mg (75%) of the target compound are
 obtained. FAB-MS: m/e=238=M+1.
 EXAMPLE 1.9
 p-Aminophenyl 4-deoxy-.beta.-L-fucoside
 ##STR23##
 This compound was prepared analogously to the instructions of T. Lindhorst
 and J. Thiem in Carbohydr. Res. 209 (1991), 119 starting from
 p-nitrophenyl-.beta.-L-fucoside via p-nitrophenyl
 2,3-di-O-benzoyl4,6-dideoxy4-iodo-.beta.-L-fucoside. [TLC: methylene
 chloride/methanol 90:10 R.sub.f =0.3].
 EXAMPLE 1.10
 p-Aminophenyl 3-O-carboxymethyl-.beta.-L-fucoside
 ##STR24##
 1.10.a) p-Nitrophenyl 3-O-methoxycarbonylmethyl-.beta.-L-fucoside
 1 g (3.5 mmol) of p-nitrophenyl .beta.-L-fucoside and 1.3 g (5.2 mmol) of
 dibutyltin oxide are heated under reflux in 50 ml of methanol for 2 hours.
 The solution is concentrated, the residue is taken up in 50 ml of dioxane,
 2 ml of methyl bromoacetate and 100 mg of tetrabutylammonium iodide are
 added and the mixture is heated under reflux for 16 hours. The solvent is
 evaporated off and the product is purified by flash chromatography
 (methylene chloride/methanol 99:1). After the corresponding fractions have
 been concentrated and the residue has been reprecipitated from
 methanol/ether, 455 mg (37%) of the target compound are obtained.
 1.10) p-Aminophenyl 3-O-carboxymethyl-.beta.-L-fucoside
 282 mg (0.79 mmol) of p-nitrophenyl
 3-methoxycarbonylmethyl-.beta.-L-fucoside are dissolved in 20 ml of
 methanol, and 440 .mu.l of a 2N lithium hydroxide solution are added.
 After the mixture has been stirred at 20.degree. C. for 2 hours, it is
 brought to pH 3 with acid ion exchanger SC108 and filtered. 250 mg of
 palladium-on-active charcoal are added to the filtrate. Hydrogenation is
 then carried out with hydrogen under a slightly increased pressure for 1.5
 hours and the catalyst is removed and washed with methanol. Concentration
 of the mixture, taking up the residue in water and freeze drying leads to
 the target product in an 86% yield (212 mg). [TLC:
 acetonitrile/water/acetic acid 5:1:0.2 R.sub.f =0.24].
 EXAMPLE 1.11
 p-Aminophenyl 3-O-methoxycarbonylmethyl-.beta.-L-fucoside
 ##STR25##
 250 mg (0.7 mmol) of p-nitrophenyl
 3-methoxycarbonylmethyl-.beta.-L-fucoside (Example 1.10.a) are dissolved
 in 20 ml of methanol and hydrogenation is carried out with hydrogen over
 palladium-on-active charcoal under a slightly increased pressure for 1.5
 hours. The catalyst is removed and washed with methanol. Concentration,
 taking up in water and freeze drying lead to 195 mg (85%) of the target
 product. [TLC methylene chloride/methanol 9:1 R.sub.f =0.43; FAB-MS:
 m/e=328=M+1.]
 EXAMPLE 1.12
 p-Aminophenyl 3-O-hydroxyethyl-.beta.-L-fucoside
 ##STR26##
 1.12.a) p-Nitrophenyl 3-O-hydroxyethyl-.beta.-L-fucoside
 1000 mg (2.8 mmol) of p-nitrophenyl
 3-methoxycarbonylmethyl-.beta.-L-fucoside are dissolved in a mixture of
 160 ml of tetrahydrofuran and 40 ml of water, and 53 mg of sodium
 borohydride are added. After 10 minutes, the solvent is evaporated off and
 the residue is purified by flash chromatography (methylene
 chloride/methanol 95:5). After the corresponding fractions have been
 concentrated, the residue has been taken up in water and the mixture has
 been freeze dried, 362 mg (40%) of the target product are obtained.
 1.12) p-Aminophenyl 3-O-hydroxyethyl-.beta.-L-fucoside
 After hydrogenation of 362 mg of the compound from Example 1.12.a)
 analogously to Example 1.1, 270 mg (82%) of the target product are
 obtained. [TLC: acetonitrile/water 10:1 R.sub.f =0.43].
 EXAMPLE 1.13
 p-Aminophenyl 2-O-carboxymethyl-.beta.-L-fucoside
 ##STR27##
 1.13.a) p-Nitrophenyl 2-O-methoxycarbonylmethyl-.beta.-L-fucoside
 250 mg (0.88 mmol) of p-nitrophenyl P-L-fucoside are dissolved in 25 ml of
 absolute tetrahydrofuran and 3 ml of dimethylformamide. 80 mg (2.64 mmol)
 of 80% strength sodium hydride are added and, after the mixture has been
 stirred at 20.degree. C. for 10 minutes, 35 .mu.l of benzyl bromoacetate
 are added. 3 further additions of 35 .mu.l each of benzyl bromoacetate are
 made at intervals of 10 minutes. The mixture is subsequently stirred for
 30 minutes and quenched with methanol. After a further 10 minutes, it is
 acidified with 5 ml of 80% strength acetic acid. The mixture is
 concentrated and the residue is subsequently distilled with methylene
 chloride. Purification by means of flash chromatography is started with
 the mobile phase system methylene chloride/methanol/glacial acetic acid
 90:10:1. The ratio in the same system is later changed to 80:20:2. After
 the corresponding fractions have been concentrated, the residues are
 digested with ether and 157 mg (42%) of the target compound are obtained
 from the early eluate. [TLC: acetonitrile/water/glacial acetic acid
 5:1:0.2 R.sub.f =0.65]. The isomeric 3-O-alkylated compound is obtained
 from the late eluates (33%). [TLC: acetonitrile/water/glacial acetic acid
 5:1:0.2 R.sub.f =0.54].
 1.13) p-Aminophenyl 2-O-carboxymethyl-.beta.-L-fucoside
 Hydrolysis and hydrogenation of 150 mg of p-nitrophenyl
 2-O-methoxycarbonylmethyl-.beta.-L-fucoside by the procedure described in
 Example 1.10 leads to 109 mg of the target product in an 83% yield [TLC:
 acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.35].
 EXAMPLE 1.14.a
 Synthesis of the regioisomeric monosuccinylation products of p-nitrophenyl
 .beta.-L-fucoside
 1100 mg (3.86 mmol) of p-nitrophenyl .beta.-L-fucoside are dissolved in 50
 ml of pyridine, and 580 mg (5.79 mmol) of succinic anhydride are added.
 After the mixture has been stirred at 20.degree. C. for 16 hours, it is
 concentrated and the residue is subsequently distilled twice with
 methylene chloride. The product is precipitated from methylene
 chloride/ether and 1 g of a substance mixture which cannot be separated is
 obtained. This is taken up in methanol/water, and 846 mg (2.6 mmol) of
 caesium carbonate are added. The solvent is evaporated off and the residue
 is subsequently distilled with dimethylformamide. The residue is taken up
 in dimethylformamide, and 618 .mu.l of benzyl bromide are added. After
 ultrasonic treatment for 1 hour, the caesium bromide is filtered off and
 the filtrate is concentrated. The residue is partitioned between 500 ml of
 ethyl acetate and 50 ml of water. The organic phase is dried and
 concentrated. Separation of the components by flash chromatography is
 achieved in the mobile phase system methylene chloride/methanol 99:1. This
 gives:
 Fraction 1: 87 mg (4.8%) of p-nitrophenyl
 3-O-(3-benzyloxycarbonyl-propionyl)-.beta.-L-fucoside [TLC: methylene
 chloride/methanol 95:5 R.sub.f =0.45].
 Fraction 2: 27 mg (1.5%) of p-nitrophenyl
 2-O-(3-benzyloxycarbonyl-propionyl)-.beta.-L-fucoside [TLC: methylene
 chloride/methanol 95:5 R.sub.f =0.34].
 Fraction 3: 190 mg (10.3%) of p-nitrophenyl
 4-O-(3-benzyloxycarbonyl-propionyl)-.beta.-L-fucoside [TLC: methylene
 chloride/methanol 95:5 R.sub.f =0.28].
 EXAMPLE 1.14
 p-Aminophenyl 3-O-succinyl-.beta.-L-fucoside
 ##STR28##
 85 mg (0.17 mmol) of fraction 1 from Example 1.14.a are dissolved in 5 ml
 of tetrahydrofuran and 1 ml of water. 20 mg of platinum dioxide are added
 and hydrogenation is carried out for 8 hours. The catalyst is filtered off
 and washed with tetrahydrofuran/water and the filtrate is concentrated.
 The residue is taken up in water and lyophilized. 57 mg (94%) of the
 target product are obtained. [TLC: acetonitrile/water/glacial acetic acid
 5:1:0.2 R.sub.f =0.65].
 EXAMPLE 1.15
 p-Aminophenyl 2-O-succinyl-.beta.-L-fucoside
 ##STR29##
 Fraction 2 from Example 1.14.a is hydrogenated analogously to the
 instructions in Example 1.14. Yield: 16 mg (87%) [TLC:
 acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.62].
 EXAMPLE 1.16
 p-Aminophenyl 4-O-succinyl-.beta.-L-fucoside
 ##STR30##
 Fraction 3 from Example 1.14.a is hydrogenated analogously to the
 instructions in Example 1.14. Yield: 125 mg (88%) [TLC:
 acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.63].
 EXAMPLE 1.17
 p-Aminophenyl 3,4-di-O-methyl-.beta.-L-fucoside
 ##STR31##
 1.17.a) p-Nitrophenyl 2-O-benzyl-3,4-O-isopropylidene-.beta.-L-fucoside
 377 mg (1.16 mmol) of the compound from Example 1.1.a are dissolved in 30
 ml of absolute tetrahydrofuran, 690 .mu.l of benzyl bromide and 52 mg of
 sodium hydride are added in succession and the mixture is stirred at
 20.degree. C. The mixture is topped up with a further 690 .mu.l of benzyl
 bromide and sodium hydride after 4 and 6 hours. The batch is worked up
 analogously to Example 1.1.b. 245 mg (51%) of the target compound are
 obtained.
 1.17.b) p-Nitrophenyl 2-O-benzyl-3,4-di-O-methyl-.beta.-L-fucoside
 245 mg (0.59 mmol) of p-nitrophenyl
 2-O-benzyl-3,4-O-isopropylidene-.beta.-L-fucoside are stirred in 80%
 strength acetic acid at 20.degree. C. for 16 hours. The mixture is
 concentrated and the residue is stirred with ether/pentane. After the
 mixture have been filtered with suction and the residue dried, the product
 which remains is taken up in 20 ml of absolute tetrahydrofuran, 45 mg of
 80% strength sodium hydride are added and, after 15 minutes, 160 .mu.l of
 methyl iodide are injected in. After the mixture has been stirred at
 20.degree. C. for 20 hours, it is quenched with methanol and glacial
 acetic acid and concentrated and the residue is partitioned between
 methylene chloride and water. The organic phase is dried and concentrated
 and the residue is then purified by flash chromatography (methylene
 chloride/methanol 100:1). After concentration and drying of the
 corresponding fractions, 188 mg (79%) of the target product are obtained.
 1.17) p-Aminophenyl 3,4-di-O-methyl-.beta.-L-fucoside
 180 mg (0.45 mmol) of the compound from Example 1.17.b are hydrogenated in
 a mixture of 15 ml of methanol and 3 ml of methylene chloride at room
 temperature for 2 days, after addition of 50 mg of palladium-on-active
 charcoal. The catalyst is filtered off, the filtrate is concentrated and
 the residue is purified by flash chromatography (methylene
 chloride/methanol 97.5:2.5). 86 mg (68%) of the target compound are
 obtained. [TLC: methylene chloride/methanol 95:5 R.sub.f =0.21].
 EXAMPLE 1.18
 p-Aminophenyl 3-O-carbamoylmethyl-.beta.-L-fucoside
 ##STR32##
 100 mg (0.305 mmol) of the compound from Example 1.11 are dissolved in 10
 ml of methanol, and 0.5 ml of 17% strength ammonium hydroxide solution is
 added. After 4 hours, the mixture is concentrated and the residue is taken
 up in water and lyophilized. 95 mg (quantitative) of the target compound
 are obtained. [TLC: acetonitrile/water 10:1 R.sub.f =0.43].
 EXAMPLE 1.19
 p-Aminophenyl 2-O-hydroxyethyl-.beta.-L-fucoside
 ##STR33##
 This compound was prepared analogously to Examples 1.12.a and 1.12 starting
 from 200 mg (0.56 mmol) of p-nitrophenyl
 2-O-methoxycarbonylmethyl-.beta.-L-fucoside (Example 1.13.a). Yield: 76 mg
 (45% over 2 stages) [TLC: methylene chloride/methanol 9:1 R.sub.f =0.2].
 EXAMPLE 1.20
 p-Aminophenyl 3,6-dideoxy-3-chloro-.beta.-L-guloside
 ##STR34##
 50 mg (0.165 mmol) of the compound from Example 1.6.b are hydrogenated in 5
 ml of methanol over palladium/active charcoal for 1 hour. The catalyst is
 filtered off and rinsed, the filtrate is concentrated and the residue is
 taken up in water and lyophilized. 45 mg (89%) of the target compound are
 obtained. [TLC: methylene chloride/methanol 9:1 R.sub.f =0.35].
 EXAMPLE 1.21
 p-Aminophenyl .alpha.-L-rhamnoside
 ##STR35##
 This compound was prepared analogously to Example 1.1 starting from 300 mg
 of p-nitrophenyl .alpha.-L-rhamnoside (Sigma). Yield: 96%
 EXAMPLE 1.22
 p-Aminophenyl 3-O-carboxymethyl-.alpha.-L-rhamnoside
 ##STR36##
 1.22.a) p-Nitrophenyl 3-O-methoxycarbonylmethyl-.alpha.-L-rhamnoside
 481 mg (1.63 mmol) of p-nitrophenyl .alpha.-L-rhamnoside are taken up in 30
 ml of methanol, and 629 mg (2.45 mmol) of dibutyltin oxide are added. The
 mixture is heated under reflux for 2 hours and concentrated and the
 residue is taken up in 30 ml of dioxane. 85 mg of tetrabutyl-ammonium
 iodide and 950 .mu.l of methyl bromoacetate are added and the mixture is
 heated under reflux for 16 hours. If appropriate, it is topped up with a
 further 1 ml of methyl bromoacetate and the reaction time is prolonged.
 The mixture is concentrated and the residue is purified by flash
 chromatography. p-Nitrophenyl
 3-O-methoxycarbonylmethyl-.alpha.-L-rhamnoside is eluted with methylene
 chloride/methanol 99:1 and, after drying, 408 mg (70%) are obtained. [TLC:
 methylene chloride/methanol 95:5 R.sub.f =0.36].
 1.22) p-Aminophenyl 3-O-carboxymethyl-.alpha.-L-rhamnoside
 Synthesis completely analogously to Example 1.10 starting from
 p-nitrophenyl 3-O-methoxycarbonylmethyl-.alpha.-L-rhamnoside. The target
 product is obtained in an 80% yield. [TLC: acetonitrile/water/glacial
 acetic acid 5:1:0.2 R.sub.f =0.26].
 EXAMPLE 1.23
 p-Aminophenyl .beta.-D-galactopyranoside
 ##STR37##
 p-Nitrophenyl .beta.-D-galactopyranoside (3.0 g, 10 mmol) is dissolved in
 methanol/water 1:1 (50 ml) and, after addition of palladium-on-active
 charcoal (10% of Pd, 200 mg), hydrogenation is carried out in a hydrogen
 atmosphere under a slightly increased pressure for 3 hours. The suspension
 is filtered over Celite and the material on the filter is washed with hot
 methanol/water 1:1 (100 ml). Concentration of the filtrate in vacuo and
 recrystallization from methanol gives colourless crystals (2.11 g, 78%);
 TLC [methanol]: R.sub.f =0.62; [.alpha.].sup.20 =-39.5.degree.
 (c=1.0/H.sub.2 O); melting point=166.degree. C.
 EXAMPLE 1.24
 p-Aminophenyl 2-O-methyl-.beta.-D-galactopyranoside
 ##STR38##
 1.24.a) p-Nitrophenyl 6-O-triphenylmethyl-.beta.-D-galactopyranoside
 A solution of p-nitrophenyl .beta.-D-galactopyranoside (9.0 g, 30 mmol),
 chlorotriphenylmethane (16.7 g, 60 mmol) and N,N-dimethylaminopyridine
 (609 mg, 5 mmol) in absolute pyridine (100 ml) is heated at 60.degree. C.
 for 4 hours. After concentration in vacuo, the residue is purified by
 flash chromatography [petroleum ether/ethyl acetate 2:1.fwdarw.3:2, in
 each case with 0.5% of triethylamine]. Colourless crystals (9.23 g, 57%)
 are obtained; TLC [methylene chloride/methanol/ammonia (25%) 15:3:0.2]:
 R.sub.f =0.55; melting point=82.degree. C.
 1.24.b) p-Nitrophenyl
 3,4-O-isopropylidene-6-O-triphenylmethyl-.beta.-D-galactopyranoside
 Dimethoxypropane (400 ml) and a catalytic amount of
 (.+-.)-camphor-10-sulphonic acid (400 mg, 1.7 mmol) are added to the above
 compound (8.7 g, 16 mmol). After 1 hour at room temperature, the reaction
 is ended by addition of triethylamine (240 ml, 1.7 mmol) and the mixture
 is concentrated in vacuo. Flash chromatography [petroleum ether/ethyl
 acetate 2:1] gives a colourless foam (6.2 g, 66%); TLC [petroleum
 ether/ethyl acetate 1:1]: R.sub.f =0.46; [.alpha.].sup.20 =-42.1.degree.
 (c=0.94/CH.sub.2 Cl.sub.2).
 1.24.c) p-Nitrophenyl
 2-O-methyl-3,4-O-isopropylidene-6-O-triphenylmethyl-.beta.-D-galactopyrano
 side
 Compound 1.24.b (5.83 g, 10 mmol) is dissolved in dimethylformamide (100
 ml), and methyl iodide (2.5 ml, 40 mmol) and, in portions, an 80% strength
 suspension of sodium hydride in mineral oil (450 mg, 15 mmol) are added.
 After 2 hours at room temperature, the reaction is ended by dropwise
 addition of methanol (10 ml) and the mixture is concentrated in vacuo. The
 residue is taken up in methylene chloride (1000 ml) and the solution is
 stirred vigorously with water (500 ml). The organic phase is dried over
 magnesium sulphate (50 g) and concentrated in vacuo and the residue is
 purified by flash chromatography [petroleum ether/ethyl acetate
 12:1.fwdarw.8:1]. A colourless foam (4.72 g, 79%) is obtained; TLC
 [petroleum ether/ethyl acetate 1:1]: R.sub.f =0.72; [.alpha.].sup.20
 =-35.7.degree. (c=1.0/CH.sub.3 OH).
 1.24.d) p-Nitrophenyl 2-O-methyl-.beta.-D-galactopyranoside
 99% strength trifluoroacetic acid (20 ml) is added to a solution of the
 above compound (4.48 g, 7.5 mmol) in methylene chloride (200 ml) and the
 mixture is stirred at room temperature for 3 hours. After the mixture has
 been concentrated in vacuo, the residue is purified by flash
 chromatography [petroleum ether/ethyl acetate 5:1.fwdarw.2:1]. Colourless
 crystals (1.09 g, 46%) are obtained; TLC [methylene
 chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.42; melting point
 177.degree. C.
 1.24) p-Aminophenyl 2-O-methyl-.beta.-D-galactopyranoside
 Compound 1.24.d (946 mg, 3 mmol) is dissolved in methanol (50 ml) and,
 after addition of water (0.5 ml) and basic Raney nickel (about 200 mg),
 hydrogenation is carried out in a hydrogen atmosphere under a slightly
 increased pressure for 2 hours. The suspension is filtered over Celite and
 the material on the filter is washed thoroughly with methanol (100 ml).
 Concentration of the filtrate in vacuo gives a brownish foam (579 mg,
 68%); TLC [methylene chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f
 =0.28; [.alpha.].sup.20 =-39.3.degree. (c=0.15/CH.sub.3 OH).
 EXAMPLE 1.25
 p-Aminophenyl 3-O-methyl-.beta.-D-galactopyranoside
 ##STR39##
 1.25.a) p-Nitrophenyl 3-O-methyl-.beta.-D-galactopyranoside
 Dibutyltin oxide (1.87 g, 7.5 mmol) is added to a solution of p-nitrophenyl
 .beta.-D-galactopyranoside (1.5 g, 5.0 mmol) in absolute methanol (40 ml)
 and the mixture is heated under reflux. After 3 hours, it is concentrated
 in vacuo and the residue is dried under an oil pump vacuum for 1 hour. It
 is taken up in absolute dioxane (40 ml), methyl iodide (1.9 ml, 30 mmol)
 is added to the resulting solution and the batch is stirred at a bath
 temperature of 100.degree. C. for 16 hours. The solvent is then distilled
 off in vacuo and the residue is purified by flash chromatography [ethyl
 acetate/petroleum ether 2:1.fwdarw.ethyl acetate]. Colourless crystals
 (1.32 g, 84%) are obtained; TLC [methylene chloride/methanol/ammonia (25%)
 15:3:0.2]: R.sub.f =0.34; melting point=196.degree. C.; [.alpha.].sup.20
 =-53.3.degree. (c=1.0/CH.sub.3 OH).
 1.25) p-Aminophenyl 3-O-methyl-.beta.-D-galactopyranoside
 The above compound (946 mg, 3 mmol) is reduced as described in Example 1.24
 and the product is worked up. Brownish crystals (656 mg, 77%) are
 obtained; TLC [methylene chloride/methanol/ammonia (25%) 15:3:0.2]:
 R.sub.f =0.21; melting point=196.degree. C.; [.alpha.].sup.20
 =-25.2.degree. (c=1.0/CH.sub.3 OH).
 EXAMPLE 1.26
 p-Aminophenyl 4-O-methyl-.beta.-D-galactopyranoside, acetate
 ##STR40##
 1.26.a) p-Nitrophenyl 3-O-benzyl-.beta.-D-galactopyranoside
 Dibutyltin oxide (1.87 g, 7.5 mmol) is added to a solution of p-nitrophenyl
 .beta.-D-galactopyranoside (1.5 g, 5.0 mmol) in absolute dioxane (40 ml)
 and the mixture is heated under reflux. After 3 hours, benzyl bromide (3.6
 ml, 30 mmol) are added to the solution obtained and the batch is stirred
 under reflux for a further 48 hours. The solvent is then distilled off in
 vacuo and the residue is purified by flash chromatography (ethyl
 acetate/petroleum ether 2:1.fwdarw.1:1]. Colourless crystals (1.58 g 81%)
 are obtained; TLC [methylene chloride/methanol/ammonia (25%) 15:3:0.2]:
 R.sub.f =0.69; melting point=127.degree. C.
 1.26.b) p-Nitrophenyl
 3-O-benzyl-4,6-O-isopropylidene-.beta.-D-galactopyranoside
 Compound 1.26.a (6.26 g, 16 mmol) is reacted as described in Example
 1.24.b. After flash chromatography [petroleum ether/ethyl acetate
 5:1.fwdarw.3:1], a colourless foam (6.54 g, 95%) is obtained; TLC
 [petroleum ether/ethyl acetate 1:1]: R.sub.f =0.34; [.alpha.].sup.20
 =-38.9.degree. (c=1.0/CH.sub.2 Cl.sub.2).
 1.26.c) p-Nitrophenyl
 2,3-di-O-benzyl-4,6-O-isopropylidene-.beta.-D-galactopyranoside
 Compound 1.26.b (4.31 g, 10 mmol) is dissolved in dimethylformamide (100
 ml), and benzyl bromide (12 ml, 100 mmol) and, in portions, an 80%
 strength suspension of sodium hydride in mineral oil (450 mg, 15 mmol) are
 added. After 2 hours at room temperature, the reaction is ended by
 dropwise addition of methanol (10 ml) and the mixture is concentrated in
 vacuo. The residue is taken up in methylene chloride (1000 ml) and the
 solution is stirred vigorously with water (500 ml). The organic phase is
 dried over magnesium sulphate (50 g) and concentrated in vacuo and the
 residue is purified by flash chromatography [petroleum ether/ethyl acetate
 20:1.fwdarw.15:1.fwdarw.10:1]. A colourless oil (2.72 g, 52%), which is
 still contaminated, is obtained; TLC [petroleum ether/ethyl acetate 1:1]:
 R.sub.f =0.62.
 1.26.d) p-Nitrophenyl 2,3-di-O-benzyl-.beta.-D-galactopyranoside
 The above compound (2.6 g, 5 mmol) is reacted as described in Example
 1.24.d. After concentration in vacuo and extraction of the residue by
 boiling with diethyl ether, colourless crystals (805 mg, 33%) are
 obtained; TLC [petroleum ether/ethyl acetate 1:1]: R.sub.f =0.23; melting
 point=160.degree. C.
 1.26.e) p-Nitrophenyl
 2,3-di-O-benzyl-6-O-triphenylmethyl-.beta.-D-galactopyranoside
 Compound 1.26.d (722 mg, 1.5 mmol) is tritylated as described in Example
 1.24.a. After flash chromatography [petroleum ether/ethyl acetate
 15:1.fwdarw.10:1.fwdarw.5:1], a colourless foam (880 mg, 81%) is obtained;
 TLC [petroleum ether/ethyl acetate 2:1]: R.sub.f =0.79; [.alpha.].sup.20
 =-25.3.degree. (c=0.3/CH.sub.2 Cl.sub.2).
 1.26.f) p-Nitrophenyl
 2,3-di-O-benzyl-4-O-methyl-6-O-triphenylmethyl-.beta.-D-galactopyranoside
 The above compound (724 mg, 1 mmol) is methylated as described in Example
 1.24.c. After flash chromatography [petroleum ether/ethyl acetate
 10:1.fwdarw.5:1], a colourless foam (662 mg, 90%) is obtained; TLC
 [petroleum ether/ethyl acetate 5:1]: R.sub.f =0.66; [.alpha.].sup.20
 =-38.7.degree. (c=0.2/CH.sub.2 Cl.sub.2).
 1.26) p-Aminophenyl 4-O-methyl-.beta.-D-galactopyranoside, acetate
 The above compound (590 mg, 0.8 mmol) is dissolved in 90% strength acetic
 acid (50 ml) and, after addition of palladium-on-active charcoal (10% of
 Pd, 200 mg), hydrogenation is carried out in a hydrogen atmosphere under a
 slightly increased pressure for 16 hours. The suspension is filtered over
 Celite and the material on the filter is washed thoroughly with methanol
 (100 ml). Concentration of the filtrate in vacuo and reprecipitation of
 the residue from diethyl ether/petroleum ether gives colourless crystals
 (253 mg, 92%); TLC [methylene chloride/methanol 5:1]: R.sub.f =0.12.
 EXAMPLE 1.27
 p-Aminophenyl 6-O-methyl-.beta.-D-galactopyranoside
 ##STR41##
 1.27.a) Benzylation of compound 1.24.b
 Compound 1.24.b (5.84 g, 10 mmol) is benzylated as described in Example
 1.26.c. After flash chromatography [petroleum ether/ethyl acetate
 15:1.fwdarw.12:1.fwdarw.5:1.fwdarw.ethyl acetate, in each case with 0.5%
 of triethylamine], two product fractions are obtained:
 Fraction 1: p-nitrophenyl
 2-O-benzyl-3,4-O-isopropylidene-6-O-triphenylmethyl-.beta.-D-galactopyrano
 side; yellowish foam (1.71 g, 25%); TLC [petroleum ether/ethyl acetate
 2:1]: R.sub.f =0.72; [.alpha.].sup.20 =-8.1.degree. (c=1.0/CH.sub.2
 Cl.sub.2).
 Fraction 2: p-nitrophenyl
 2-O-benzyl-3,4-O-isopropylidene-.beta.-D-galactopyranoside; yellowish oil
 (806 g, 19%); TLC [petroleum ether/ethyl acetate 2:1]: R.sub.f =0.45;
 [.alpha.].sup.20 =+2.8.degree. (c=1.2/CH.sub.3 OH).
 1.27.b) p-Nitrophenyl
 2-O-benzyl-3,4-O-isopropylidene-6-O-methyl-.beta.-D-galactopyranoside
 Fraction 2 from Example 1.27.a (777 mg, 1.8 mmol) is methylated as
 described in Example 1.24.c. After flash chromatography [petroleum
 ether/ethyl acetate 10:1.fwdarw.8:1], a brownish oil (730 mg, 91%) is
 obtained; TLC [petroleum ether/ethyl acetate 2:1]: R.sub.f =0.54;
 [.alpha.].sup.20 =-11.6.degree. (c=1.1/CH.sub.2 Cl.sub.2).
 1.27.c) p-Nitrophenyl 2-O-benzyl-6-O-methyl-.beta.-D-galactopyranoside
 The above compound (668 mg, 1.5 mmol) is reacted as described in Example
 1.24.d. Concentration of the filtrate in vacuo and extraction of the
 residue by boiling with a little diethyl ether gives, after cooling to
 room temperature, pale beige crystals (388 mg, 64%); TLC [petroleum
 ether/ethyl acetate 1:1]: R.sub.f =0.15; melting point=143.degree. C.
 1.27) p-Aminophenyl 6-O-methyl-.beta.-D-galactopyranoside
 Compound 1.27.c (324 mg, 0.8 mmol) is reduced for 16 hours as described in
 Example 1.24. After concentration of the filtrate in vacuo and extraction
 of the residue by boiling with a little diethyl ether, beige crystals (184
 mg, 81%) are obtained; TLC [ethyl acetate]: R.sub.f =0.05; melting
 point=115.degree. C. (decomposition).
 EXAMPLE 1.28
 p-Aminophenyl 2,3-di-O-methyl-.beta.-D-galactopyranoside
 ##STR42##
 1.28.a) Isopropylidenation of p-nitrophenyl .beta.-D-galactopyranoside
 Anhydrous toluenesulphonic acid (500 mg) is added to a solution of
 p-nitrophenyl .beta.-D-galactopyranoside (7.5 g, 25 mmol) in absolute
 acetone (1000 ml). Acetone (250 ml) is distilled off under normal pressure
 in the course of 30 minutes and, immediately thereafter, the mixture is
 neutralized by addition of potassium carbonate (500 mg). After
 concentration in vacuo, the residue is stirred with diethyl ether (1000
 ml). The mixture is filtered, the filtrate is concentrated and the residue
 is purified by flash chromatography [petroleum ether/ethyl acetate
 2:1.fwdarw.1:1.fwdarw.3:2]. Two product fractions are obtained by this
 procedure:
 Fraction 1: p-Nitrophenyl 3,4-O-isopropylidene-.beta.-D-galactopyranoside;
 colourless foam (3.74 g, 44%); TLC [methylene chloride/methanol/ammonia
 (25%) 15:3:0.2]: R.sub.f =0.59; [.alpha.].sup.20 =-54.2.degree.
 (c=0.38/CH.sub.3 OH).
 Fraction 2: p-Nitrophenyl 4,6-O-isopropylidene-.beta.-D-galactopyranoside;
 colourless foam (4.3 g, 50%); TLC [methylene chloride/methanol/ammonia
 (25%) 15:3:0.2]: R.sub.f =0.54; [.alpha.].sup.20 =-81.0.degree.
 (c=0.31/CH.sub.3 OH).
 1.28.b) p-Nitrophenyl
 2,3-di-O-methyl-4,6-O-isopropylidene-.beta.-D-galactopyranoside
 Fraction 2 from Example 1.28.a (4.1 g, 12 mmol) is methylated as described
 in Example 1.24.c. After flash chromatography [petroleum ether/ethyl
 acetate 5:1.fwdarw.2:1], a colourless foam (2.93 g, 66%) is obtained; TLC
 [[petroleum ether/ethyl acetate 1:1]: R.sub.f =0.42; [.alpha.].sup.20
 =-52.6.degree. (c=0.34/CH.sub.3 OH).
 1.28.c) p-Nitrophenyl 2,3-di-O-methyl-.beta.-D-galactopyranoside
 The above compound (2.77 g, 7.5 mmol) is reacted as described in Example
 1.24.d. After 1 hour at room temperature, the mixture is concentrated in
 vacuo and the residue is dried under an oil pump vacuum for 1 hour.
 Digestion with diethyl ether/petroleum ether 1:1 (100 ml) gives colourless
 crystals (1.11 g, 45%); TLC [ethyl acetate]: R.sub.f =0.24; melting
 point=156.degree. C.
 1.28) p-Aminophenyl 2,3-di-O-methyl-.beta.-D-galactopyranoside
 Compound 1.28.c (989 mg, 3 mmol) is reduced as described in Example 1.24. A
 colourless oil (396 mg, 44%) is obtained; TLC [methylene
 chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.50; [.alpha.].sup.20
 =-19.4.degree. (c=0.16/CH.sub.3 OH).
 EXAMPLE 1.29
 p-Aminophenyl 2,4-di-O-methyl-.beta.-D-galactopyranoside
 ##STR43##
 1.29.a) Tritylation of Compound 1.26.a
 Compound 1.26.a (11.7 g, 30 mmol) is tritylated as described in Example
 1.24.a. After flash chromatography [petroleum ether/ethyl acetate
 10:1.fwdarw.7:1.fwdarw.5.1, in each case with 0.5% of triethylamine], two
 products are obtained:
 Fraction 1: triphenylmethyl
 2-O-(p-nitrophenyl)-3-O-benzyl-6-O-triphenylmethyl-.beta.-D-galactopyranos
 ide, colourless foam (8.5 g, 32%); TLC [petroleum ether/ethyl acetate 2:1]:
 R.sub.f =0.68; [.alpha.].sup.20 =+42.8.degree. (c=1.0/CH.sub.2 Cl.sub.2).
 Fraction 2: p-nitrophenyl
 3-O-benzyl-6-O-triphenylmethyl-.beta.-D-galactopyranoside, colourless foam
 (9.0 g, 47%); TLC [petroleum ether/ethyl acetate 2:1]: R.sub.f =0.22;
 [.alpha.].sup.20 =-22.6.degree. (c=1.03/CH.sub.2 Cl.sub.2).
 1.29.b) p-Nitrophenyl
 2,4-di-O-methyl-3-O-benzyl-6-O-triphenylmethyl-.beta.-D-galactopyranoside
 Fraction 2 from Example 1.29.a (7.6 g, 12 mmol) is methylated as described
 in Example 1.24.c. After flash chromatography [petroleum ether/ethyl
 acetate 15:1.fwdarw.10:1], a colourless foam (7.07 g, 89%) is obtained;
 TLC [petroleum ether/ethyl acetate 2:1]: R.sub.f =0.79; [.alpha.].sup.20
 =-35.8.degree. (c=1.09/CH.sub.3 OH).
 1.29.c) p-Aminophenyl 2,4-di-O-methyl-3-O-benzyl-.beta.-D-galactopyranoside
 The above compound (6.0 g, 9 mmol) is hydrogenated for 48 hours as
 described in Example 1.26. Colourless crystals (1.39 g, 40%) are obtained;
 TLC [ethyl acetate/petroleum ether 2:1]: R.sub.f =0.20; melting
 point=148.degree. C.
 1.29) p-Aminophenyl 2,4-di-O-methyl-.beta.-D-galactopyranoside
 Compound 1.29.c (779 mg, 2 mmol) is hydrogenated for 5 days as described in
 Example 1.24. After evaporation of the combined filtrates in vacuo and
 extraction of the residue by boiling with diethyl ether (2.times.50 ml),
 slightly greenish crystals (391 mg, 65%) are obtained; TLC [ethyl
 acetate]: R.sub.f =0.16; melting point=260.degree. C. (decomposition).
 EXAMPLE 1.30
 p-Aminophenyl 2,6-di-O-methyl-.beta.-D-galactopyranoside
 ##STR44##
 1.30.a) p-Nitrophenyl
 2,6-di-O-methyl-3,4-O-isopropylidene-.beta.-D-galactopyranoside
 Fraction 1 from Example 1.28.a (4.1 g, 12 mmol) is methylated as described
 in Example 1.24.c. After flash chromatography [petroleum ether/ethyl
 acetate 10:1.fwdarw.8:1.fwdarw.5:1], a colourless oil (3.25 g, 73%) is
 obtained; TLC [petroleum ether/ethyl acetate 1:1]: R.sub.f =0.65.
 1.30.b) p-Nitrophenyl 2,6-di-O-methyl-.beta.-D-galactopyranoside
 The above compound (2.77 g, 7.5 mmol) is reacted as described in Example
 1.24.d. After flash chromatography [ethyl acetate/petroleum ether 2:1],
 colourless crystals (1.63 g, 66%) are obtained; TLC [ethyl acetate]:
 R.sub.f =0.31; melting point=222.degree. C.
 1.30) p-Aminophenyl 2,6-di-O-methyl-.beta.-D-galactopyranoside
 Compound 1.30.b (989 mg, 3 mmol) is reduced as described in Example 1.24. A
 colourless oil (597 mg, 66%) is obtained; TLC [methylene
 chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.56; [.alpha.].sup.20
 =-53.1.degree. (c=0.49/CH.sub.3 OH).
 EXAMPLE 1.31
 p-Aminophenyl 3,4-di-O-methyl-.beta.-D-galactopyranoside, acetate
 ##STR45##
 1.31.a) p-Nitrophenyl
 2,6-di-O-benzyl-3,4-O-isopropylidene-.beta.-D-galactopyranoside
 Fraction 1 from Example 1.28.a (4.1 g, 12 mmol) is benzylated as described
 in Example 1.26.c. After flash chromatography [petroleum ether/ethyl
 acetate 6:1], a yellowish oil (5.3 g, 85%) is obtained; TLC [ethyl
 acetate/petroleum ether 2:1]: R.sub.f =0.76; [.alpha.].sup.20
 =+8.8.degree. (c=1.2/CH.sub.3 OH).
 1.31.b) p-Nitrophenyl 2,6-di-O-benzyl-.beta.-D-galactopyranoside
 The above compound (4.69 g, 9 mmol) is reacted as described in Example
 1.24.d. After 30 minutes at room temperature, the mixture is concentrated
 in vacuo and the residue is dried under an oil pump vacuum for 1 hour.
 Recrystallization from ethanol gives colourless crystals (2.89 g, 67%);
 TLC [ethyl acetate/petroleum ether 2:1]: R.sub.f =0.42; melting
 point=133.degree. C.; [.alpha.].sup.20 =-64.2.degree. (c=1.0/CH.sub.3 OH).
 1.31.c) p-Nitrophenyl
 2,6-di-O-benzyl-3,4-di-O-methyl-.beta.-D-galactopyranoside
 The above compound (2.4 g, 5 mmol) is methylated as described in Example
 1.24.c. After recrystallization from ethanol/n-hexane, colourless crystals
 (1.74 g, 69%) are obtained; TLC [petroleum ether/ethyl acetate 1:1]:
 R.sub.f =0.74; melting point=149.degree. C.
 1.31) p-Aminophenyl 3,4-di-O-methyl-.beta.-D-galactopyranoside, acetate
 Compound 1.31.c (1.52 g, 3 mmol) is hydrogenated as described in Example
 1.26. Colourless crystals (664 mg, 62%) are obtained; TLC [methylene
 chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.47; melting
 point=140.degree. C. (decomposition).
 EXAMPLE 1.32
 p-Aminophenyl 3,6-di-O-methyl-.beta.-D-galactopyranoside
 ##STR46##
 1.32.a) p-Nitrophenyl
 3-O-methyl-6-O-(tert-butyldimethylsilyl)-.beta.-D-galactopyranoside
 Imidazole (1 g, 15 mmol) and tert-butyldimethylsilyl chloride (1.25 g, 8
 mmol) are added to a solution of compound 1.25.a (1.58 g, 5 mmol) in
 dimethylformamide (150 ml) and the mixture is stirred at room temperature
 for 24 hours. The reaction is then interrupted by addition of water (100
 ml). The mixture is diluted with methylene chloride (1000 ml) and the
 organic phase is washed with water (2.times.1000 ml), dried over magnesium
 sulphate (20 g) and concentrated in vacuo. After flash chromatography
 [petroleum ether/ethyl acetate 15:1.fwdarw.10:1.fwdarw.5:11, a yellowish
 foam (826 mg, 38%), which is still slightly contaminated, is obtained; TLC
 [ethyl acetate]: R.sub.f =0.59; [.alpha.].sup.20 =-56.3.degree.
 (c=1.0/CH.sub.2 Cl.sub.2).
 1.32.b) p-Nitrophenyl
 2,4-di-O-benzyl-3-O-methyl-6-O-(tert-butyldimethylsilyl)-.beta.-D-galactop
 yranoside
 The above compound (773 mg, 1.8 mmol) is benzylated as described in Example
 1.26.c. After flash chromatography [petroleum ether/ethyl acetate
 30:1.fwdarw.5:1], a colourless foam (810 mg, 74%) is obtained; TLC
 [petroleum ether/ethyl acetate 5:1]: R.sub.f =0.58.
 1.32.c) p-Nitrophenyl 2,4-di-O-benzyl-3-O-methyl-.beta.-D-galactopyranoside
 Compound 1.32.b (732 mg, 1.2 mmol) is dissolved in tetrahydrofuran (6 ml)
 and a 1M solution of tetrabutylammonium fluoride in tetrahydrofuran (2.4
 ml) is added at 0.degree. C. The mixture is stirred at room temperature
 for 40 minutes and then concentrated in vacuo. After flash chromatography
 [petroleum ether/ethyl acetate 5:1.fwdarw.3:1.fwdarw.2:1], colourless
 crystals (512 mg, 86%) are obtained; TLC [petroleum ether/ethyl acetate
 1:1]: R.sub.f =0.36; melting point=177.degree. C.
 1.32.d) p-Nitrophenyl
 2,4-di-O-benzyl-3,6-di-O-methyl-.beta.-D-galactopyranoside
 The above compound (446 mg, 0.9 mmol) is methylated as described in Example
 1.24.c. After flash chromatography [petroleum ether/ethyl acetate
 20:1.fwdarw.10:1.fwdarw.8:1, a colourless oil (401 mg, 87%) is obtained;
 TLC [petroleum ether/ethyl acetate 1:1]: R.sub.f =0.70; [.alpha.].sup.20
 =-56.5.degree. (c=0.96/CH.sub.2 Cl.sub.2).
 1.32) p-Aminophenyl 3,6-di-O-methyl-.beta.-D-galactopyranoside
 Compound 1.32.d (357 mg, 0.7 mmol) is hydrogenated as described in Example
 1.24. After evaporation of the combined filtrates in vacuo and extraction
 of the residue by boiling with diethyl ether (20 ml), colourless crystals
 (207 mg, 99%) are obtained; TLC [petroleum ether/ethyl acetate 1:1]:
 R.sub.f =0.02; melting point=&gt;280.degree. C. (decomposition).
 EXAMPLE 1.33
 p-Aminophenyl 4,6-di-O-methyl-.beta.D-galactopyranoside
 ##STR47##
 1.33.a) p-Nitrophenyl
 2,3-di-O-benzyl-4,6-di-O-methyl-.beta.-D-galactopyranoside
 Compound 1.26.d (2.4 g, 5 mmol) is methylated as described in Example
 1.24.c. After flash chromatography [petroleum ether/ethyl acetate
 5:1.fwdarw.3:1], colourless crystals (1.89 g, (74%) are obtained; TLC
 [petroleum ether/ethyl acetate 1:1]: R.sub.f =0.76; melting
 point=177.degree. C.
 1.33) p-Aminophenyl 4,6-di-O-methyl-.beta.-D-galactopyranoside
 Compound 1.33.a (1.53 g, 3 mmol) is hydrogenated as described in Example
 1.24. Colourless crystals (890 mg, 99%) are obtained; TLC [methanol/ethyl
 acetate 1:1]: R.sub.f =0.71; melting point=180.degree. C. (decomposition).
 EXAMPLE 1.34
 p-Aminophenyl 2,3,4-tri-O-methyl-.beta.-D-galactopyranoside
 ##STR48##
 1.34.a) p-Nitrophenyl
 2,3,4-tri-O-methyl-6-O-triphenylmethyl-.beta.-D-galactopyranoside
 Compound 1.24.a (1.63 g, 3 mmol) is methylated as described in Example
 1.24.c. After flash chromatography [petroleum ether/ethyl acetate
 5:1.fwdarw.3:1], a colourless foam (1.24 g, 71%) is obtained; TLC
 [petroleum ether/ethyl acetate 1:1]: R.sub.f =0.54; [.alpha.].sup.20
 =-53.6.degree. (c=0.3/CH.sub.3 OH).
 1.34.b) p-Nitrophenyl 2,3,4-tri-O-methyl-.beta.-D-galactopyranoside
 The above compound (1.17 g, 2 mmol) is reacted as described in Example
 1.24.d. After flash chromatography [petroleum ether/ethyl acetate
 3:1.fwdarw.2:1], colourless crystals (468 mg, 68%) are obtained; TLC
 [petroleum ether/ethyl acetate 1:1]: R.sub.f =0.12; melting
 point=104.degree. C.; [.alpha.].sup.20 =-68.2.degree. (c=0.47/CH.sub.3
 OH).
 1.34) p-Aminophenyl 2,3,4-tri-O-methyl-.beta.-D-galactopyranoside
 Compound 1.34.b (343 mg, 1 mmol) is reduced as described in Example 1.24.
 Beige crystals (224 mg, 71%) are obtained; TLC (methylene
 chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.67; melting
 point=138.degree. C.
 EXAMPLE 1.35
 p-Aminophenyl 2,3,6-tri-O-methyl-.beta.-D-galactopyranoside
 ##STR49##
 1.35.a) p-Nitrophenyl 2,3,6-tri-O-methyl-.beta.-D-galactopyranoside
 Compound 1.30.b (2.63 g, 3 mmol) is methylated selectively as described in
 Example 1.25.a. After flash chromatography [petroleum ether/ethyl acetate
 5:1.fwdarw.2:1], a brownish oil (890 mg, 32%) is obtained; TLC [ethyl
 acetate]: R.sub.f =0.37; [.alpha.].sup.20 =-63.3.degree. (c=0.9/CH.sub.2
 Cl.sub.2).
 1.35) p-Aminophenyl 2,3,6-tri-O-methyl-.beta.-D-galactopyranoside
 The above compound (858 mg, 2.5 mmol) is reduced as described in Example
 1.24. A beige foam (519 mg, 66%) is obtained; TLC [ethyl acetate]: R.sub.f
 0.23; [.alpha.].sup.20 =-34.5.degree. (c=0.86/CH.sub.3 OH).
 EXAMPLE 1.36
 p-Aminophenyl 2,4,6-O-methyl-.beta.-D-galactopyranoside
 ##STR50##
 1.36.a) p-Nitrophenyl
 2,4,6-tri-O-methyl-3-O-benzyl-.beta.-D-galactopyranoside
 Compound 1.26.a (1.96 g, 5 mmol) is methylated as described in Example
 1.24.c. After flash chromatography [petroleum ether/ethyl acetate
 10:1.fwdarw.8:1], colourless crystals (1.47 g, 68%) are obtained; TLC
 [petroleum ether/ethyl acetate 2:1]: R.sub.f =0.46; melting
 point=164.degree. C.
 1.36) p-Aminophenyl 2,4,6-tri-O-methyl-.beta.-D-galactopyranoside
 The above compound (1.3 g, 3 mmol) is reduced as described in Example 1.26.
 Colourless crystals (642 mg, 68%) are obtained; TLC [ethyl
 acetate/petroleum ether 2:1]: R.sub.f =0.12; melting point=147.degree. C.
 (decomposition).
 EXAMPLE 1.37
 p-Aminophenyl 3,4,6-tri-O-methyl-.beta.-D-galactopyranoside
 ##STR51##
 1.37.a) p-Nitrophenyl 2-O-benzyl-.beta.-D-galactopyranoside
 Fraction 1 from Example 1.27.a (1.17 g, 2 mmol) is reacted as described in
 Example 1.24.d. After flash chromatography [petroleum ether/ethyl acetate
 3:1.fwdarw.2:1], colourless crystals (468 mg, 68%) are obtained; TLC
 [petroleum ether/ethyl acetate 1:1]: R.sub.f =0.12; melting
 point=104.degree. C.; [.alpha.].sup.20 =-68.2.degree. (c=0.47/CH.sub.3
 OH).
 1.37.b) p-Nitrophenyl
 2-O-benzyl-3,4,6-tri-O-methyl-.beta.-D-galactopyranoside
 The above compound (391 mg, 1 mmol) is methylated as described in Example
 1.24.c. After flash chromatography [petroleum ether/ethyl acetate
 10:1.fwdarw.5:1], pale yellow crystals (303 mg, 70%) are obtained; TLC
 [ethyl acetate]: R.sub.f =0.81; [.alpha.].sup.20 =-76.5.degree.
 (c=1.1/CH.sub.2 Cl.sub.2).
 1.37) p-Aminophenyl 3,4,6-tri-O-methyl-.beta.-D-galactopyranoside
 Compound 1.37.b (260 mg, 0.6 mmol) is hydrogenated as described in Example
 1.24. Beige crystals (161 mg, 86%) are obtained; TLC [ethyl acetate]:
 R.sub.f =0.20; melting point=132.degree. C.
 EXAMPLE 1.38
 p-Aminophenyl 2,3,4,6-tetra-O-methyl-.beta.-D-galactopyranoside
 ##STR52##
 1.38.a) p-Nitrophenyl 2,3,4,6-tetra-O-methyl-.beta.-D-galactopyranoside
 p-Nitrophenyl .beta.-D-galactopyranoside (904 mg, 3 mmol) is methylated as
 described in Example 1.24.c. After flash chromatography [petroleum
 ether/ethyl acetate 8:1.fwdarw.6:1.fwdarw.4:1.fwdarw.2:1], a colourless,
 waxy solid (633 mg, 59%) is obtained; TLC [ethyl acetate]: R.sub.f =0.67;
 [.alpha.].sup.20 =-55.7.degree. (c=0.9/CH.sub.2 Cl.sub.2).
 1.38) p-Aminophenyl 2,3,4,6-tetra-O-methyl-.beta.-D-galactopyranoside
 Compound 1.33.a (536 mg, 1.5 mmol) is hydrogenated as described in Example
 1.24. After evaporation of the combined filtrates in vacuo and extraction
 of the residue by boiling with diethyl ether (20 ml), colourless crystals
 (412 mg, 84%) are obtained; TLC [ethyl acetate]: R.sub.f =0.42; melting
 point=204.degree. C. (decomposition).
 EXAMPLE 1.39
 p-Aminophenyl .alpha.-D-mannopyranoside
 ##STR53##
 p-Nitrophenyl .alpha.-D-mannopyranoside (3.0 g, 10 mmol) is hydrogenated as
 described in Example 1.23. The precipitation from methanol/diethyl ether
 gives colourless crystals (2.03 g, 75%); TLC [methanol]: R.sub.f =0.69;
 [.alpha.].sup.20 =+102.7.degree. (c=1.0/H.sub.2 O); melting
 point=161.degree. C.
 EXAMPLE 1.40
 p-Aminophenyl 3-O-methyl-.alpha.-D-mannopyranoside
 ##STR54##
 1.40.a) p-Nitrophenyl 6-O-triphenylmethyl-.alpha.-D-mannopyranoside
 p-Nitrophenyl .alpha.-D-mannopyranoside (3.0 g, 10 mmol) is tritylated as
 described in Example 1.24.a. Colourless crystals (4.35 g, 80%) are
 obtained; TLC [methylene chloride/methanol/ammonia (25%) 15:3:0.2]:
 R.sub.f =0.52; [.alpha.].sup.20 =+104.0.degree. (c=1.0/CH.sub.3 OH);
 melting point=102-104.degree. C.
 1.40.b) p-Nitrophenyl
 3-O-methyl-6-O-triphenylmethyl-.alpha.-D-mannopyranoside
 The above compound (2.72 g, 5 mmol) is reacted with methyl iodide (2 ml, 30
 mmol) as described in Example 1.26.a. After flash chromatography
 [petroleum ether/ethyl acetate 2:1] and reprecipitation from
 ethanol/n-hexane, colourless crystals (1.83 g, 66%) are obtained; TLC
 [methylene chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.68;
 [.alpha.].sup.20 =+106.4.degree. (c=1.0/CH.sub.3 OH); melting
 point=104.degree. C.
 1.40) p-Aminophenyl 3-O-methyl-.alpha.-D-mannopyranoside
 Compound 1.40.b (1.4 g, 2.5 mmol) is dissolved in methanol (50 ml) and,
 after addition of palladium-on-active charcoal (10% of Pd, 300 mg),
 hydrogenation is carried out in a hydrogen atmosphere under a slightly
 increased pressure for 24 hours. The suspension is filtered over Celite
 and the material on the filter is washed thoroughly with methanol (100
 ml). After concentration of the filtrate in vacuo, the residue is
 extracted with water (50 ml), the mixture is filtered and the filtrate is
 lyophilized. A brownish amorphous solid (709 mg, 99%) is obtained; TLC
 [methylene chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.33;
 [.alpha.].sup.20 =+92.9.degree. (c=1.1/CH.sub.3 OH).
 EXAMPLE 1.41
 p-Aminophenyl 2,3-di-O-methyl-.alpha.-D-mannopyranoside
 ##STR55##
 1.41.a) p-Nitrophenyl 4,6-O-benzylidene-.alpha.-D-mannopyranoside
 Benzaldehyde dimethyl acetal (3.2 ml, 21.4 mmol) and a 54% strength
 solution of tetrafluoboric acid in diethyl ether (2.7 ml, 20 mmol) are
 added to a solution of p-nitrophenyl .alpha.-D-mannopyranoside (6.0 g, 20
 mmol) in dimethylformamide (120 ml). The mixture is stirred at room
 temperature for 5 hours, the reaction is then interrupted by addition of
 triethylamine (2.8 ml, 20 mmol) and the mixture is concentrated in vacuo.
 After flash chromatography [toluene.fwdarw.toluene/ethanol 20:1],
 colourless crystals (6.48 g, 83%) are obtained; TLC [methylene
 chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.82; [.alpha.].sup.20
 =+170.7.degree. (c=1.0/CH.sub.2 Cl.sub.2); melting point=116.degree. C.
 1.41.b) p-Nitrophenyl
 2,3-di-O-methyl-4,6-O-benzylidene-.alpha.-D-mannopyranoside
 The above compound (3.9 g, 10 mmol) is methylated as described in Example
 1.24.c. After flash chromatography [petroleum ether/ethyl acetate
 20:1.fwdarw.7:1] and reprecipitation from ethyl acetate/n-hexane, a
 colourless foam (3.2 g, 77%) is obtained; TLC [ethyl acetate/petroleum
 ether 2:1]: R.sub.f =0.67; [.alpha.].sup.20 =+167.30 (c=1.05/CH.sub.3 OH).
 1.41) p-Aminophenyl 2,3-di-O-methyl-.alpha.-D-mannopyranoside
 Compound 1.41.b (1.25 g, 3 mmol) is hydrogenated as described in Example
 1.26. After flash chromatography [ethyl acetate/petroleum ether
 2:1.fwdarw.ethyl acetate, in each case with 0.5% of triethylamine], a
 reddish-brown foam (480 mg, 53%) is obtained; TLC [methylene
 chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.31; [.alpha.].sup.20
 =+83.6.degree. (c=0.76/CH.sub.3 OH).
 EXAMPLE 1.42
 ##STR56##
 1.42.a) p-Nitrophenyl 3-O-methoxycarbonylmethyl-.alpha.-D-galactopyranoside
 Dibutyltin oxide (9.3 g, 37.5 mmol) is added to a solution of p-nitrophenyl
 .beta.-D-galactopyranoside (7.53 g, 25 mmol) in absolute dioxane (180 ml)
 and the mixture is heated under reflux. After 4 hours, methyl bromoacetate
 (8.3 ml, 90 mmol) and tetrabutylammonium iodide (9.25 g, 25 mmol) are
 added to the solution obtained and the batch is stirred under reflux for a
 further 3 hours. The solvent is then distilled off in vacuo and the
 residue is purified by flash chromatography [methylene chloride/methanol
 50:1.fwdarw.20:1]. In addition to some by-products, the compound 1.42.a is
 obtained as colourless crystals (4.05 g, 43%); TLC [methylene
 chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.54; [.alpha.].sup.20
 =-62.0.degree. (c=1.0/CH.sub.3 OH); melting point 176.degree. C.
 1.42) p-Aminophenyl 3-O-methoxycarbonylmethyl-.beta.-D-galactopyranoside
 Compound 1.42.a (3.73 g, 10 mmol) is hydrogenated as described in Example
 1.24. After reprecipitation from ethanol/-hexane, colourless crystals
 (2.98 g, 87%) are obtained; TLC [methylene chloride/methanol/ammonia (25%)
 15:3:0.2]: R.sub.f =0.39; [.alpha.].sup.20 =-36.3.degree. (c=1.07/CH.sub.3
 OH); melting point=155.degree. C.
 EXAMPLE 1.43
 ##STR57##
 1.43.a) p-Nitrophenyl 3-O-carboxymethyl-.beta.-D-galactopyranoside, sodium
 salt
 A solution of sodium hydroxide (400 mg, 10 mmol) in water (5 ml) is added
 to a solution of compound 1.42.a (3.73 g, 10 mmol) in methanol (100 ml)
 and the mixture is stirred at room temperature for 2 hours. After
 concentration in vacuo, the residue is dried under an oil pump vacuum for
 2 hours and ethanol (100 ml) is then added. The mixture is boiled under
 reflux for 5 minutes and, after cooling in an ice-bath, the solid is
 filtered off to give colourless crystals (3.66 g, 96%); TLC [methanol]:
 R.sub.f =0.62; [.alpha.].sup.20 =-50.0.degree. (c=1.0/CH.sub.3 OH);
 melting point=180-185.degree. C.
 1.43) p-Aminophenyl 3-O-carboxymethyl-.beta.-D-galactopyranoside, sodium
 salt
 The above compound (3.05 g, 8 mmol) is hydrogenated as described in Example
 1.24. After extraction by boiling with ethanol (50 ml), colourless
 crystals (2.03 g, 72%) are obtained; TLC [methanol]: R.sub.f =0.70;
 [.alpha.].sup.20 =-22.4.degree. (c=1.0/CH.sub.3 OH); melting
 point=180-182.degree. C.
 EXAMPLE 1.44
 p-Aminophenyl 3-O-carbamoylmethyl-.beta.-D-galactopyranoside
 ##STR58##
 1.44.a) p-Nitrophenyl 3-O-carbamoylmethyl-.beta.-D-galactopyranoside
 A 25% strength aqueous solution of ammonia (10 ml) is added to a solution
 of compound 1.42.a (373 mg, 1 mmol) in methanol (30 ml) and the mixture is
 stirred at room temperature for 15 minutes. After concentration in vacuo,
 the residue is dried under an oil pump vacuum for 2 hours and ethanol (30
 ml) is then added. The mixture is boiled under reflux for 5 minutes and
 filtered, after cooling in an ice-bath, to give colourless crystals (306
 mg, 85%); TLC [methylene chloride/methanol/ammonia (25%) 15:3:0.2]:
 R.sub.f =0.14; [.alpha.].sup.20 =-41.7.degree. (c=1.0/CH.sub.3 OH);
 melting point=229.degree. C. (decomposition).
 1.44) p-Aminophenyl 3-O-carbamoylmethyl-.beta.-D-galactopyranoside
 The above compound (287 mg, 0.8 mmol) is hydrogenated as described in
 Example 1.24. After reprecipitation from methanol/diethyl ether,
 colourless crystals (207 mg, 79%) are obtained; TLC [methylene
 chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.10; melting
 point=205.degree. C. (decomposition).
 EXAMPLE 1.45
 p-Aminophenyl 3-O-(N-methyl-carbamoylmethyl)-.beta.-D-galactopyranoside
 ##STR59##
 1.45a) p-Nitrophenyl
 3-O-(N-methyl-carbamoylmethyl)-.beta.-D-galactopyranoside
 A 30% strength aqueous solution of methylamine (10 ml) is added to a
 solution of compound 1.42.a (373 mg, 1 mmol) in methanol (30 ml) and the
 mixture is stirred at room temperature for 2 hours. After concentration in
 vacuo, the residue is dried under an oil pump vacuum for 2 hours and then
 recrystallized from ethanol. Colourless crystals (372 mg, 100%) are
 obtained; TLC [methylene chloride/methanol/ammonia (25%) 15:3:0.2]:
 R.sub.f =0.33; [.alpha.].sup.20 =-36.7.degree. (c=1.0/CH.sub.3 OH);
 melting point=205.degree. C.
 1.45) p-Aminophenyl
 3-O-(N-methyl-carbamoylmethyl)-.beta.-D-galactopyranoside
 Compound 1.45.a (298 mg, 0.8 mmol) is hydrogenated as described in Example
 1.24. After reprecipitation from methanol/diethyl ether, colourless
 crystals (180 mg, 66%) are obtained; TLC [methylene
 chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.16; melting
 point=239.degree. C.
 EXAMPLE 1.46
 p-Aminophenyl 3-O-(N-propyl-carbamoylmethyl)-.beta.-D-galactopyranoside
 ##STR60##
 1.46.a) p-Nitrophenyl
 3-O-(N-propyl-carbamoylmethyl)-.beta.-D-galactopyranoside
 Compound 1.42.a (373 mg, 1 mmol) is reacted with n-propylamine (823 .mu.l,
 10 mmol) as described in Example 1.45.a. After concentration in vacuo, the
 residue is reprecipitated from ethanol/n-hexane. Colourless crystals (340
 mg, 85%) are obtained; TLC [methylene chloride/methanol/ammonia (25%)
 15:3:0.2]: R.sub.f =0.49; [.alpha.].sup.20 =-32.4.degree. (c=1.0/CH.sub.3
 OH); melting point=155.degree. C.
 1.46) p-Aminophenyl .sup.3
 -O-(N-propyl-carbamoylmethyl)-.beta.-D-galactopyranoside
 Compound 1.46.a (320 mg, 0.8 mmol) is hydrogenated as described in Example
 1.24. After reprecipitation from methanol/diethyl ether, colourless
 crystals (188 mg, 63%) are obtained; TLC [methylene
 chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.31; melting
 point=154.degree. C.
 EXAMPLE 1.47
 p-Aminophenyl 3-O-(N-butyl-carbamoylmethyl)-.beta.-D-galactopyranoside
 ##STR61##
 1.47.a) p-Nitrophenyl
 3-O-(N-butyl-carbamoylmethyl)-.beta.-D-galactopyranoside
 Compound 1.42.a (373 mg, 1 mmol) is reacted with n-butylamine (900 .mu.l,
 10 mmol) as described in Example 1.45.a. After concentration in vacuo, the
 residue is reprecipitated from ethanol/n-hexane. Colourless crystals (413
 mg, 100%) are obtained; TLC [methylene chloride/methanol/ammonia (25%)
 15:3:0.2]: R.sub.f =0.51; [.alpha.].sup.20 =-26.8.degree. (c=1.0/CH.sub.3
 OH); melting point=92.degree. C.
 1.47) p-Aminophenyl
 3-O-(N-butyl-carbamoylmethyl)-.beta.-D-galactopyranoside
 Compound 1.47.a (332 mg, 0.8 mmol) is hydrogenated as described in Example
 1.24. After reprecipitation from ethanol/n-hexane, colourless crystals
 (105 mg, 34%) are obtained; TLC [methylene chloride/methanol/ammonia (25%)
 15:3:0.2]: R.sub.f =0.32; melting point=135.degree. C.
 EXAMPLE 1.48
 p-Aminophenyl 3-O-methoxycarbonylmethyl-.alpha.-D-mannopyranoside
 ##STR62##
 1.48.a) p-Nitrophenyl
 3-O-methoxycarbonylmethyl-6-O-triphenylmethyl-.alpha.-D-mannopyranoside
 Compound 1.40.a (13.6 g, 25 mmol) is reacted as described in Example
 1.42.a. After flash chromatography [petroleum ether/ethyl acetate 10:1],
 in addition to some by-products, colourless crystals (2.79 g, 18%) are
 obtained; TLC [ethyl acetate/petroleum ether 2:1]: R.sub.f =0.50; melting
 point=95-97.degree. C.
 1.48) p-Aminophenyl 3-O-methoxycarbonylmethyl-.alpha.-D-mannopyranoside
 Compound 1.48.a (1.23 g, 2 mmol) is hydrogenated as described in Example
 1.40 and the product is worked up. A brownish amorphous solid (250 mg,
 36%) is obtained; TLC [methylene chloride/methanol/ammonia (25%)
 15:3:0.2]: R.sub.f =0.45.
 EXAMPLE 1.49
 p-Aminophenyl 3-O-carboxymethyl-.alpha.-D-mannopyranoside
 ##STR63##
 1.49.a) p-Nitrophenyl
 3-O-benzoxycarbonylmethyl-6-O-triphenylmethyl-.alpha.-D-mannopyranoside
 Compound 1.40.a (13.6 g, 25 mmol) is reacted with benzyl bromoacetate (14.4
 ml, 90 mmol) as described in Example 1.42.a. After flash chromatography
 [petroleum ether/ethyl acetate 20:1.fwdarw.10:1], in addition to some
 by-products, a yellowish foam (5.0 g, 29%) is obtained; TLC [ethyl
 acetate/petroleum ether 2:1]: R.sub.f =0.66; [.alpha.].sup.20
 =+74.8.degree. (c=1.0/CH.sub.2 Cl.sub.2).
 1.49) p-Aminophenyl 3-O-carboxymethyl-.alpha.-D-mannopyranoside
 The above compound (2.08 g, 3 mmol) is hydrogenated for 36 hours as
 described in Example 1.40. After concentration of the filtrate, the
 residue is reprecipitated from ethanol/n-hexane. Washing with ethyl
 acetate and renewed reprecipitation from ethanol/diethyl ether gives
 colourless crystals (495 mg, 50%); TLC [methanol]: R.sub.f =0.53; melting
 point=205-207.degree. C.
 EXAMPLE 1.50
 p-Aminophenyl 3-O-carbamoylmethyl-.alpha.-D-mannopyranoside
 ##STR64##
 1.50.a) p-Nitrophenyl
 3-O-carbamoylmethyl-6-O-triphenylmethyl-.alpha.-D-mannopyranoside
 Compound 1.49.a (1.04 g, 1.5 mmol) is reacted as described in Example
 1.44.a. After drying under an oil pump vacuum, the residue is purified by
 flash chromatography [petroleum ether/ethyl acetate 2:3]. Colourless
 crystals (561 mg, 62%) are obtained; TLC [methylene
 chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.67; [.alpha.].sup.20
 =+91.3.degree. (c=1.0/CH.sub.2 Cl.sub.2); melting point=125-127.degree. C.
 1.50) p-Aminophenyl 3-O-carbamoylmethyl-.alpha.-D-mannopyranoside
 The above compound (541 g, 0.9 mmol) is hydrogenated for 48 hours as
 described in Example 1.40. After concentration of the filtrate, the
 residue is washed thoroughly with methanol to give colourless crystals
 (134 mg, 45%); TLC [methylene chloride/methanol/ammonia (25%) 15:3:0.2]:
 R.sub.f =0.21; melting point=126-128.degree. C.
 EXAMPLE 1.51
 p-Aminophenyl 3-deoxy-.beta.-D-galactopyranoside
 ##STR65##
 1.51.a) p-Nitrophenyl 2,6-di-O-benzyl-4-O-acetyl-.beta.-D-galactopyranoside
 Triethyl orthoacetate (3 ml, 16.3 mmol) and toluenesulphonic acid (20 mg)
 are added to a solution of compound 1.31.b (2.7 g, 5.6 mmol) in methylene
 chloride (20 ml). After 30 minutes at room temperature, the batch is
 diluted with methylene chloride (200 ml) and washed with saturated sodium
 bicarbonate solution (50 ml), the organic phase is dried over magnesium
 sulphate and, after filtration, the filtrate is concentrated in vacuo. The
 resulting colourless foam is dissolved in 80% strength acetic acid (15
 ml). After a further 30 minutes at room temperature, the batch is poured
 into saturated sodium bicarbonate solution (200 ml) and extracted with
 chloroform (3.times.75 ml), the combined organic phases are washed with
 water (100 ml) and dried over magnesium sulphate and, after filtration,
 the filtrate is concentrated in vacuo. Reprecipitation from
 ethanol/petroleum ether gives colourless crystals (2.43 g, 83%); TLC
 [ethyl acetate/petroleum ether 2:1]: R.sub.f =0.64; [.alpha.].sup.20
 =-62.1.degree. (c=1.0/CH.sub.2 Cl.sub.2); melting point=83.degree. C.
 1.51.b) p-Nitrophenyl
 2,6-di-O-benzyl-3-O-trifluoromethanesulphonyl-4-O-acetyl-.beta.-D-galactop
 yranoside
 A solution of trifluoromethanesulphonic anhydride (2 ml, 11.8 mmol) in
 methylene chloride (30 ml) is added dropwise to a solution of compound
 1.51.a (2.3 g, 4.4 mmol) in a mixture of methylene chloride (30 ml) and
 pyridine (3 ml) at -20.degree. C., under argon. After 1 hour at
 -20.degree. C., the batch is poured into saturated sodium bicarbonate
 solution (200 ml), the organic phase is separated off and dried over
 magnesium sulphate and, after filtration, the filtrate is concentrated in
 vacuo. After flash chromatography [toluene.fwdarw.toluene/ethyl acetate
 20:1], colourless crystals (2.39 g, 83%) are obtained; TLC [toluene/ethyl
 acetate 5:1]: R.sub.f =0.55; [.alpha.].sup.20 =-61.4.degree.
 (c=1.0/CH.sub.2 Cl.sub.2); melting point=105.degree. C.
 1.51.c) p-Nitrophenyl 2,6-di-O-benzyl-3-deoxy-.beta.-D-galactopyranoside
 The above compound (1.31 g, 2 mmol) is dissolved in toluene (25 ml), and
 tetrabutylammonium tetraborohydrate (1.54 g, 6 mmol) is added. After 2
 hours at 80.degree. C., the batch is diluted with methylene chloride (200
 ml) and washed once with water (50 ml), the organic phase is dried over
 magnesium sulphate and, after filtration, the filtrate is concentrated in
 vacuo. After flash chromatography [toluene/ethyl acetate 7:1], colourless
 crystals (596 mg, 64%) are obtained; TLC [toluene/ethyl acetate 5:1]:
 R.sub.f =0.10; [.alpha.].sup.20 =-81.3.degree. (c=1.0/CH.sub.2 Cl.sub.2);
 melting point=114.degree. C.
 1.51) p-Aminophenyl 3-deoxy-.beta.-D-galactopyranoside
 Compound 1.51.c (465 mg, 1 mmol) is hydrogenated for 6 hours as described
 in Example 1.40. After concentration of the filtrate, the residue is
 reprecipitated from ethanol/petroleum ether to give colourless crystals
 (206 mg, 81%); TLC [methylene chloride/methanol/ammonia (25%) 15:3:0.2]:
 R.sub.f =0.22.
 EXAMPLE 1.52
 p-Aminophenyl 3,4-dideoxy-.beta.-D-galactopyranoside
 ##STR66##
 1.52.a) p-Nitrophenyl
 2,6-di-O-benzyl-3,4-di-O-trifluoromethanesulphonyl-.beta.-D-galactopyranos
 ide
 Compound 1.31.b (2.12 g, 4.4 mmol) is reacted with
 trifluoromethanesulphonic anhydride (4 ml, 23.6 mmol) as in Example
 1.51.b. After flash chromatography [toluene.fwdarw.toluene/ethyl acetate
 50:1], a yellowish oil (2.75 g, 84%) is obtained; TLC [toluene/ethyl
 acetate 5:1]: R.sub.f =0.67; [.alpha.].sup.20 =-22.5.degree.
 (c=1.0/CH.sub.2 Cl.sub.2).
 1.52.b) p-Nitrophenyl
 2,6-di-O-benzyl-3,4-dideoxy-.beta.-D-galactopyranoside
 Compound 1.52.a (1.49 g, 2 mmol) is reacted with tetrabutylammonium
 tetraborohydrate (2.31 g, 9 mmol) as in Example 1.51.c. After flash
 chromatography [toluene.fwdarw.toluene/ethyl acetate 50:1], colourless
 crystals (629 mg, 70%) are obtained; TLC [toluene/ethyl acetate 5:1]:
 R.sub.f =0.53; [.alpha.].sup.20 =-79.1.degree. (c=1.0/CH.sub.2 Cl.sub.2);
 melting point=89.degree. C.
 1.52) p-Aminophenyl 3,4-dideoxy-.beta.-D-galactopyranoside
 Compound 1.52.b (450 mg, 1 mmol) is hydrogenated for 5 hours as described
 in Example 1.40. After concentration of the filtrate, the residue is
 reprecipitated from ethanol/petroleum ether to give colourless crystals
 (183 mg, 76%); TLC [methylene chloride/methanol/ammonia (25%) 15:3:0.2]:
 R.sub.f =0.47; [.alpha.].sup.20 =115.1.degree. (c=1.0/CH.sub.3 OH);
 melting point=187.degree. C.
 EXAMPLE 1.53
 p-Aminophenyl 6-O-acetyl-.beta.-D-galactopyranoside
 ##STR67##
 1.53.a) p-Nitrophenyl 6-O-acetyl-.beta.-D-galactopyranoside
 A freshly prepared solution of pyridine (2 ml, 25 mmol) and acetyl chloride
 (1.85 ml, 26 mmol) in acetonitrile (20 ml) is added dropwise to a solution
 of p-nitrophenyl .beta.-D-galactopyranoside (7.53 g, 25 mmol) in absolute
 acetonitrile (80 ml) at 0.degree. C. The mixture is stirred at 0.degree.
 C. for 30 minutes and then concentrated in vacuo.
 After flash chromatography [methylene chloride/methanol 50:1.fwdarw.20:1],
 colourless crystals (4.02 g, 47%) are obtained; TLC [methylene
 chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.50.
 1.53) p-Aminophenyl 6-O-acetyl-.beta.-D-galactopyranoside
 Compound 1.53.a (1.72 g, 5 mmol) is hydrogenated for 2 hours as described
 in Example 1.40. After concentration of the filtrate, the residue is
 reprecipitated from methanol/diethyl ether to give colourless crystals
 (1.34 g, 86%); TLC [methylene chloride/methanol/ammonia (25%) 15:3:0.2]:
 R.sub.f =0.34; [.alpha.].sup.20 =41.0.degree. (c=0.56/CH.sub.3 OH);
 melting point=180.degree. C. (decomposition).
 EXAMPLE 1.54
 p-Aminophenyl 3,4-di-O-methoxycarbonylmethyl-.beta.-D-galactopyranoside
 ##STR68##
 1.54.a) Acylation of compound 1.24.a
 Compound 1.24.a (1.36 g, 3 mmol) is dissolved in dimethylformamide (25 ml)
 and methyl bromoacetate (1 ml, 10.6 mmol) and, in portions, an 80%
 strength suspension of sodium hydride in mineral oil (300 mg, 10 mmol) are
 added. After 3.5 hours at room temperature, methyl bromoacetate (250
 .mu.l, 2.65 mmol) and sodium hydride in mineral oil (75 mg, 2.5 mmol) are
 again added. After a further 2 hours, the reaction is ended by dropwise
 addition of methanol (5 ml) and the mixture is concentrated in vacuo. The
 residue is taken up in methylene chloride (250 ml) and the solution is
 stirred vigorously with water (100 ml). The organic phase is dried over
 magnesium sulphate (10 g) and concentrated in vacuo and the residue is
 purified by flash chromatography [petroleum ether/ethyl acetate
 10:1.fwdarw.7:1.fwdarw.5:1.fwdarw.3:1]. Three product fractions are
 obtained:
 Fraction 1: p-nitrophenyl
 2,3,4-tri-O-methoxycarbonylmethyl-.beta.-D-galactopyranoside; colourless
 foam (401 mg, 21%); TLC [petroleum ether/ethyl acetate 1:1]: R.sub.f
 =0.47; [.alpha.].sup.20 =-51.9.degree. (c=0.26/CH.sub.3 OH).
 Fraction 2: not identified; colourless foam (88 mg); TLC [petroleum
 ether/ethyl acetate 1:1]: R.sub.f =0.39; [.alpha.].sup.20 =-61.5.degree.
 (c=0.26/CH.sub.3 OH).
 Fraction 3: p-nitrophenyl
 3,4-di-O-methoxycarbonylmethyl-.beta.-D-galactopyranoside; colourless foam
 (275 mg, 16%); TLC [petroleum ether/ethyl acetate 1:1]: R.sub.f =0.30;
 [.alpha.].sup.20 =-38.6.degree. (c=0.28/CH.sub.3 OH).
 1.54) p-Aminophenyl
 3,4-di-O-methoxycarbonylmethyl-.beta.-D-galactopyranoside
 Fraction 3 from Example 1.54.a (206 mg, 0.3 mmol) is hydrogenated for 16
 hours as described in Example 1.40. After concentration of the filtrate,
 the residue is extracted by boiling with diethyl ether (20 ml) to give
 grey crystals (45.6 mg, 37%); TLC [petroleum ether/ethyl acetate 1:1]:
 R.sub.f =0.22; melting point=155.degree. C. (decomposition).
 EXAMPLE 1.55
 p-Aminophenyl 2,3,4-tri-O-methoxycarbonylmethyl-.beta.-D-galactopyranoside
 ##STR69##
 Fraction 1 from Example 1.54.a (380 mg, 0,5 mmol) is hydrogenated for 16
 hours as described in Example 1.40. After concentration of the filtrate,
 the residue is extracted by boiling with diethyl ether (20 ml) to give a
 yellow-brown oil (46.8 mg, 19%); TLC [petroleum ether/ethyl acetate 1:1]:
 R.sub.f =0.29; melting point=106.degree. C. (decomposition).
 EXAMPLE 1.56
 p-Aminophenyl 4-O-(.beta.-D-galactopyranosyl)-.beta.-D-glucopyranoside
 ##STR70##
 p-Nitrophenyl 4-O-(.beta.-D-galactopyranosyl)-.beta.-D-galactopyranoside
 (4.63 g, 10 mmol) is hydrogenated as described in Example 1.23. Colourless
 crystals (3.04 g, 70%) are obtained; TLC [methanol]: R.sub.f =0.55,
 melting point=235-237.degree. C. (decomposition).
 EXAMPLE 1.57
 p-Aminophenyl
 4-O-(3'-sulphato-.beta.-D-galactopyranosyl)-.beta.-D-glucopyranoside,
 sodium salt
 ##STR71##
 1.57.a) p-Nitrophenyl
 4-O-(3',4'-O-isopropylidene-.beta.-D-galactopyranosyl)-.beta.-D-glucopyran
 oside
 Dimethoxypropane (400 ml) and a catalytic amount of
 (.+-.)-camphor-10-sulphonic acid (400 mg, 1.7 mmol) are added to
 p-nitrophenyl 4-O-(.beta.-D-galactopyranosyl)-.beta.-D-galactopyranoside
 (23.2 g, 50 mmol). After 3 days at room temperature, the reaction is ended
 by addition of triethylamine (240 .mu.l, 1.7 mmol), the mixture is
 concentrated in vacuo and the residue is dried under an oil pump vacuum
 for 2 hours. The resulting crystals are taken up in methanol/water 10:1
 (500 ml) and the mixture is boiled under reflux for 6 hours. After
 concentration in vacuo and flash chromatography [methylene
 chloride/methanol 25:1.fwdarw.10:1, in each case with 0.5% of
 triethylamine], colourless crystals (15.2 g, 60%) are obtained; TLC
 [methylene chloride/methanol 5:1]: R.sub.f =0.49; melting
 point=253-255.degree. C. (decomposition).
 1.57.b) p-Nitrophenyl
 2,3,6-tri-O-benzoyl-4-O-(2',6'-di-O-benzoyl-3',4'-O-isopropylidene-.beta.-
 D-galactopyranosyl)-.beta.-D-glucopyranoside
 Benzoyl chloride (50 ml, 430 mmol) is slowly added dropwise to a solution
 of compound 1.57.a (15.1 g, 30 mmol) in pyridine (300 ml) at 0.degree. C.
 in the course of 30 minutes. The mixture is then stirred at room
 temperature for a further 2 hours and the batch is subsequently poured
 into ice-water (2000 ml), while stirring. After 15 minutes, the crystals
 which have precipitated out are filtered off and taken up in methylene
 chloride (1500 ml). The solution is washed with water (2.times.500 ml) and
 1N sodium bicarbonate solution (2.times.500 ml), the organic phase is
 dried over magnesium sulphate (50 g) and concentrated in vacuo and the
 residue is purified by recrystallization from methanol. Colourless
 crystals (26.7 g, 87%) are obtained; TLC [methylene chloride/methanol
 50:1]: R.sub.f =0.49; [.alpha.].sup.20 =+23.6.degree. (c=1.08/CH.sub.2
 Cl.sub.2); melting point=272-274.degree. C.
 1.57.c) p-Nitrophenyl
 2,3,6-tri-O-benzoyl-4-O-(2',6'-di-O-benzoyl-.beta.-D-galactopyranosyl)-.be
 ta.-D-glucopyranoside
 99% strength trifluoroacetic acid (20 ml) is added to a solution of
 compound 1.57.b (20.5 g, 20 mmol) in methylene chloride (400 ml) and the
 mixture is stirred at room temperature for 20 minutes. The solution is
 then washed with 1N sodium bicarbonate solution (2.times.200 ml), the
 organic phase is dried over magnesium sulphate (10 g) and concentrated in
 vacuo and the residue is purified by reprecipitation from methylene
 chloride/diethyl ether. Colourless crystals (18.0 g, 91%) are obtained;
 TLC [methylene chloride/methanol 20:1]: R.sub.f =0.18; melting
 point=234.degree. C.
 1.57.d) p-Nitrophenyl
 2,3,6-tri--benzoyl-4-O-(2',6'-di-O-benzoyl-4'-O-acetyl-.beta.-D-galactopyr
 anosyl)-.beta.-D-glucopyranoside
 Compound 1.57.c (5.5 g, 5.6 mmol) is reacted as described in Example
 1.51.a. After flash chromatography [petroleum ether/ethyl acetate
 3:1.fwdarw.1:1], colourless crystals (4.03 g, 70%) are obtained; TLC
 [methylene chloride/methanol 20:1]: R.sub.f =0.67; melting
 point=118.degree. C.
 1.57.e) p-Nitrophenyl
 2,3,6-tri-O-benzoyl4-O-(2',6'-di-O-benzoyl-3'-sulphato-4'-O-acetyl-.beta.-
 D-galactopyranosyl)-.beta.-D-glucopyranoside, sodium salt
 Sulphur trioxide-pyridine complex (4.5 g, 28 mmol) is added to a solution
 of compound 1.57.d (3.59 g, 3.5 mmol) in pyridine (200 ml) and the mixture
 is stirred first at 60.degree. C. for 2 hours and then at room temperature
 for 16 hours. The reaction is then ended by dropwise addition of methanol
 (50 ml) and the mixture is concentrated in vacuo. The residue is purified
 by flash chromatography [methylene chloride/methanol 10:1]. A solid
 product is obtained and is taken up in methylene chloride/methanol 1:1
 (200 ml), and Amberlite IR120 (Na.sup.+ form, 10 g) is added. This mixture
 is stirred at room temperature for 1 hour and filtered and the filtrate is
 concentrated in vacuo. Colourless crystals (3.64 g, 92%) are obtained; TLC
 [methylene chloride/methanol 2:1]: R.sub.f =0.87; melting
 point=168.degree. C.
 1.57.f) p-Nitrophenyl
 4-O-(3'-sulphato-.beta.-D-galactopyranosyl)-.beta.-D-glucopyranoside,
 sodium salt
 Compound 1.57.e (3.4 g, 3 mmol) is dissolved in absolute methanol (150 ml),
 sodium methylate (200 mg) is added and the mixture is stirred at
 60.degree. C. for 7 hours. After cooling to room temperature, the mixture
 is neutralized with Lewatit SC108 (H.sup.+ form) and then filtered. The pH
 of the filtrate is increased to pH 7-8 by dropwise addition of IN sodium
 hydroxide solution, the mixture is evaporated in vacuo and reprecipitation
 of the residue from methanol/diethyl ether gives slightly brownish
 crystals (1.30 g, 77%); TLC [methylene chloride/methanol 2:1]: R.sub.f
 =0.55; melting point=230.degree. C. (decomposition).
 1.57) p-Aminophenyl
 4-O-(3'-sulphato-.beta.-D-galactopyranosyl)-.beta.-D-glucopyranoside,
 sodium salt
 The above compound (1.13 g, 2 mmol) is reduced as described in Example
 1.24. After extraction of the residue by boiling with diethyl ether (50
 ml), colourless crystals (983 mg, 92%) are obtained; TLC [methylene
 chloride/methanol 2:1]: R.sub.f =0.22; melting point=176.degree. C.
 (decomposition).
 EXAMPLE 1.58
 p-Aminophenyl
 4-O-(3'-O-methyl-.beta.-D-galactopyranosyl)-.beta.-D-glucopyranoside
 ##STR72##
 1.58.a) Selective methylation of p-nitrophenyl
 4-O-(.beta.-D-galactopyranosyl)-.beta.-D-glucopyranoside
 p-Nitrophenyl 4-O-(.beta.-D-galactopyranosyl)-.beta.-D-glucopyranoside (2.3
 g, 5 mmol) is methylated as described in Example 1.25.a. Flash
 chromatography [methylene chloride/methanol 20:1.fwdarw.10:1.fwdarw.5:1]
 gives two products:
 Fraction 1: p-nitrophenyl
 2-O-methyl-4-O-(3'-O-methyl-.beta.-D-galactopyranosyl)-.beta.-D-glucopyran
 oside; colourless crystals (264 mg, 11%); TLC [methylene chloride/methanol
 5:1]: R.sub.f =0.46; [.alpha.].sup.20 =-73.9.degree. (c=1.0/CH.sub.3 OH);
 melting point=228.degree. C. (decomposition).
 Fraction 2: p-nitrophenyl
 4-O-(3'-O-methyl-.beta.-D-galactopyranosyl)-.beta.-D-glucopyranoside;
 colourless crystals (1.0 g, 42%); TLC [methylene chloride/methanol 5:1]:
 R.sub.f =0.29; [.alpha.].sup.20 =-65.3.degree. (c=1.1/CH.sub.3 OH);
 melting point=220.degree. C.
 1.58) p-Aminophenyl
 4-O-(3'-O-methyl-.beta.-D-galactopyranosyl)-.beta.-D-glucopyranoside
 Fraction 2 from Example 1.58.a (955 mg, 2 mmol) is reduced as described in
 Example 1.24. After washing with diethyl ether (50 ml), colourless
 crystals (894 mg, 100%) are obtained; TLC [methylene chloride/methanol
 5:1]: R.sub.f =0.08; melting point=129.degree. C. (decomposition).
 EXAMPLE 1.59
 p-Aminophenyl
 2-O-methyl-4-O-(3'-O-methyl-.beta.-D-galactopyranosyl)-.beta.-D-glucopyran
 oside
 ##STR73##
 Fraction 1 from Example 1.58.a (246 mg, 0.5 mmol) is reduced as described
 in Example 1.24. After washing with diethyl ether (20 ml), colourless
 crystals (186 mg, 81%) are obtained; TLC [methylene chloride/methanol
 5:1]: R.sub.f =0.13; [.alpha.].sup.20 =-3.6.degree. (c=1.0/CH.sub.3 OH);
 melting point=105.degree. C.
 EXAMPLE 1.60
 p-Aminophenyl
 4-O-(3',4'-di-O-methyl-.beta.-D-galactopyranosyl)-.beta.-D-glucopyranoside
 ##STR74##
 1.60.a) p-Nitrophenyl
 2,3,6-tri-O-benzyl-4-O-(2',6'-di-O-benzyl-3',4'-O-isopropylidene-.beta.-D-
 galactopyranosyl)-.beta.-D-glucopyranoside
 Compound 1.57.a (5.0 g, 10 mmol) is reacted with benzyl bromide (30 ml, 250
 mmol) for 16 hours as described in Example 1.26.c. After concentration in
 vacuo, the residue is taken up in ethyl acetate (300 ml) and the solution
 is washed with water (200 ml). The organic phase is dried over magnesium
 sulphate (10 g) and concentrated in vacuo and the residue is purified by
 flash chromatography [methylene chloride/petroleum ether
 5:1.fwdarw.methylene chloride]. A brownish oil (5.3 g, 56%) is obtained;
 TLC [methylene chloride/methanol 50:1]: R.sub.f =0.70; [.alpha.].sup.20
 =-23.2.degree. (c=1.08/CH.sub.2 Cl.sub.2).
 1.60.b) p-Nitrophenyl
 2,3,6-tri-O-benzyl-4-O-(2',6'-di-O-benzyl-5-D-galactopyranosyl)-.beta.-D-g
 lucopyranoside
 The above compound (4.77 g, 5 mmol) is reacted as described in Example
 1.57.c. After concentration in vacuo and reprecipitation from diethyl
 ether/petroleum ether, colourless crystals (3.94 g, 86%) are obtained; TLC
 [methylene chloride/methanol 50:1]: R.sub.f =0.36; melting
 point=116.degree. C.
 1.60.c) p-Nitrophenyl
 2,3,6-tri-O-benzyl-4-O-(2',6'-di-O-benzyl-3',4'-di-O-methyl-.beta.-D-galac
 topyranosyl)-.beta.-D-glucopyranoside
 Compound 1.60.b (1.8 g, 2 mmol) is methylated as described in Example
 1.24.c. Reprecipitation from methylene chloride/petroleum ether gives
 colourless crystals (1.55 g, 82%); TLC [methylene chloride/methanol 50:1]:
 R.sub.f =0.74; melting point=161-162.degree. C.
 1.60) p-Aminophenyl
 4-O-(3',4'-di-O-methyl-.beta.-D-galactopyranosyl)-.beta.-D-glucopyranoside
 Compound 1.60.c (1.41 g, 1.5 mmol) is dissolved in methanol (50 ml) and
 after addition of palladium hydroxide-on-charcoal (moist, 20% of Pd, 500
 mg), hydrogenation is carried out in a hydrogen atmosphere under a
 slightly increased for 6 days. The suspension is filtered over Celite and
 the material on the filter is washed thoroughly with methanol (100 ml).
 Concentration of the filtrate in vacuo and washing of the residue with
 methylene chloride gives brownish crystals (425 mg, 61%); melting
 point=124.degree. C. (decomposition).
 EXAMPLE 2.1
 N-Alanyl-batracyline
 ##STR75##
 2.1.a) N-[N-(tert-Butoxycarbonyl)-alanyl]-batracyline
 N-(tert-Butoxycarbonyl)-alanine (3.3 g, 17.5 mmol) and
 2-isobutoxy-1-isobutoxycarbonyl-1,2-dihydro-quinoline (6.8 ml, 23 mmol)
 are dissolved in 100 ml of methylene chloride. After the mixture has been
 stirred at room temperature for 20 minutes, a solution of batracyline (4.1
 g, 16.5 mmol) in absolute dimethylformamide (350 ml) is added and the
 batch is stirred at room temperature for a further 48 hours. It is then
 concentrated to 50 ml in vacuo and the concentrate is topped up to 300 ml
 with ethyl acetate and immediately heated at the boiling point for 10
 minutes. The mixture is then allowed to cool to room temperature and is
 filtered and the material on the filter is extracted by boiling again with
 ethyl acetate (200 ml). Cooling to 0.degree. C., while stirring, and
 filtration gives yellow crystals (6.18 g, 84%); TLC [ethyl acetate]:
 R.sub.f =0.57; melting point=246-247.degree. C. (decomposition).
 2.1) N-Alanyl-batracyline
 A solution of compound 2.1.a (10.5 g, 25 mmol) in anhydrous trifluoroacetic
 acid (150 ml) is stirred at room temperature for 15 minutes. After the
 batch has been concentrated to 30 ml in vacuo, it is poured into saturated
 sodium bicarbonate solution (1000 ml) while stirring vigorously. Stirring
 is continued for 10 minutes, the mixture is filtered and the residue is
 washed with water, a little isopropanol and diethyl ether. The product is
 obtained in yellow crystals (7.15 g, 89%); TLC [ethyl acetate]: R.sub.f
 =0.06; melting point=261-262.degree. C. (decomposition).
 EXAMPLE 2.2
 N-[Lysyl-alanyl]-batracyline, di-trifluoroacetate
 ##STR76##
 2.2.a)
 N-[N.alpha.,N.epsilon.-Di-(tert-butoxycarbonyl)-lysyl-alanyl]-batracyline
 N,N-Di-(tert-butoxycarbonyl)-lysine (2.1 g, 6 mmol) and .sup.2
 -isobutoxy-1-isobutoxy-carbonyl-1,2-dihydro-quinoline (2.4 ml, 8 mmol) are
 dissolved in 20 ml of methylene chloride. After the mixture has been
 stirred at room temperature for 20 minutes, a solution of compound 2.1
 (1.6 g, 5 mmol) in dimethylformamide (40 ml) is added and the batch is
 stirred at room temperature for a further 16 hours. It is then
 concentrated in vacuo and the residue is purified by flash chromatography
 [petroleum ether/ethyl acetate 2:1.fwdarw.1:1.fwdarw.ethyl acetate].
 Yellow crystals (2.89 g, 89%) are obtained; TLC [ethyl acetate]: R.sub.f
 =0.52; melting point=203-204.degree. C.
 2.2) N-[Lysyl-alanyl]-batracyline, di-trifluoroacetate
 Anhydrous trifluoroacetic acid (10 ml) is added to a suspension of the
 above compound (2.6 g, 4 mmol) in methylene chloride (25 ml) and the
 resulting solution is stirred at room temperature for 30 minutes. After
 concentration in vacuo, the residue is crystallized by addition of diethyl
 ether (100 ml). The precipitate is filtered off and washed intensively
 with diethyl ether. Yellow crystals (2.68 g, 99%) are obtained; TLC [ethyl
 acetate]: R.sub.f =0.05; melting point=144-146.degree. C. (decomposition).
 EXAMPLE 2.3
 N-[D-Alanyl]-batracyline
 ##STR77##
 2.3.a) N-[N-Benzyloxycarbonyl-D-alanyl]-batracyline
 N-Benzyloxycarbonyl-D-alanine (3.9 g, 17.5 mmol) is reacted as described in
 Example 2.1.a and the product is worked up. The resulting yellow crystals
 (6.4 g, 80%) are separated off by filtration, the combined filtrates are
 concentrated in vacuo and the residue is purified by flash chromatography
 [petroleum ether/ethyl acetate 3:2.fwdarw.1:1]. A further 1.35 g (17%) are
 obtained; TLC [ethyl acetate]: R.sub.f =0.45; melting point=256.degree.
 C.; [.alpha.].sup.20 =+75.1.degree. (c=1.0/CH.sub.2 Cl.sub.2)+0.5%
 CH.sub.3 OH).
 2.3) N-[D-Alanyl]-batracyline
 Compound 2.3.a (11.4 g, 25 mmol) is dissolved in a 33% strength solution of
 hydrogen bromide in glacial acetic acid (100 ml). After 30 minutes at room
 temperature, the batch is concentrated to 30 ml in vacuo and the
 concentrate is then poured into saturated sodium bicarbonate solution
 (1000 ml), while stirring vigorously. Stirring is continued for 10
 minutes, the mixture is filtered and the residue is washed with water, a
 little isopropanol and diethyl ether. The product is obtained in yellow
 crystals (7.87 g, 98%); TLC [ethyl acetate]: R.sub.f =0.06; melting
 point=267.degree. C. (decomposition).
 EXAMPLE 2.4
 N-[N.sup..alpha. -(tert-Butoxycarbonyl)-lysyl-D-alanyl]-batracyline
 ##STR78##
 2.4.a) N-[N.sup..alpha. -(tert-Butoxycarbonyl)-N.sup..epsilon.
 -(fluorenyl-9-methoxycarbonyl)-lysyl-D-alanyl]-batracyline
 N.sup..alpha. -(tert-Butoxycarbonyl)-N.sup..epsilon.
 -(fluorenyl-9-methoxycarbonyl)-lysine (5.3 g, 11.3 mmol) and
 2-isobutoxy-1-isobutoxycarbonyl-1,2-dihydro-quinoline (4 ml, 14 mmol) are
 dissolved in 40 ml of methylene chloride. After the mixture has been
 stirred at room temperature for 20 minutes, a solution of compound 2.3
 (3.2 g, 10 mmol) in dimethylformamide (80 ml) is added and the batch is
 stirred at room temperature for a further 16 hours. It is then
 concentrated in vacuo and the residue is suspended in methylene chloride
 (100 ml). The resulting suspension is topped up with diethyl ether (300
 ml). After filtration and washing of the material in the filter with
 diethyl ether, yellow crystals (5.65 g, 65%) are obtained; TLC [ethyl
 acetate]: R.sub.f =0.45; melting point=186.degree. C.
 2.4) N-[N.sup..alpha. -(tert-Butoxycarbonyl)-lysyl-D-alanyl]-batracyline
 The above compound (5.6 g, 7.3 mmol) is dissolved in dimethylformamide (50
 ml). After addition of piperidine (50 ml), the mixture is stirred at room
 temperature for 3 hours and then concentrated in vacuo and the residue is
 purified by flash chromatography [methylene chloride/methanol/ammonia
 (25%) 15:3:0.1.fwdarw.15:5:0.1]. Yellow crystals (2.5 g, 62%) are
 obtained; melting point=217.degree. C. (decomposition).
 EXAMPLE 2.5
 N-[N.sup..alpha.
 -(Fluorenyl-9-methoxycarbonyl)-lysyl-D-alanyl]-batracyline,
 trifluoroacetate
 ##STR79##
 2.5.a) N-[N.sup..alpha. -(Fluorenyl-9-methoxycarbonyl)-N.sup..epsilon.
 -(tert-butoxycarbonyl)-lysyl-D-alanyl]-batracyline
 N.sup..alpha. -(Fluorenyl-9-methoxycarbonyl)-N.sup..epsilon.
 -(tert-butoxycarbonyl)-lysine (5.3 g, 11.3 mmol) is reacted as described
 in Example 2.4.a and the product is purified. Yellow crystals (7.0 g, 80%)
 are obtained; TLC [ethyl acetate]: R.sub.f =0.51; melting
 point=223.degree. C.
 2.5) N-[N.sup..alpha.
 -(Fluorenyl-9-methoxycarbonyl)-lysyl-D-alanyl]-batracyline,
 trifluoroacetate
 Compound 2.5.a (6.17 g, 8 mmol) is reacted as described in Example 2.2.
 After concentration in vacuo, the residue is reprecipitated from methylene
 chloride/diethyl ether to give yellow crystals (6.08 g, 97%); TLC [ethyl
 acetate]: R.sub.f =0.05; melting point=224.degree. C. (decomposition).
 EXAMPLE 2.6
 N-[N.sup..epsilon.
 -(Fluorenyl-9-methoxycarbonyl)-lysyl-D-alanyl]-batracyline,
 trifluoroacetate
 ##STR80##
 Compound 2.4.a (6.17 g, 8 mmol) is reacted as described in Example 2.2.
 After concentration in vacuo, the residue is reprecipitated from methylene
 chloride/diethyl ether to give yellow crystals (5.97 g, 95%); TLC [ethyl
 acetate]: R.sub.f =0.04; melting point=188.degree. C. (decomposition).
 EXAMPLE 2.7
 N-[Lysyl-D-asparagyl]-batracyline, di-trifluoroacetate
 ##STR81##
 2.7.a) N-[N-(Fluorenyl-9-methoxycarbonyl)-D-asparagyl-(.beta.-tert-butyl
 ester)]-batracyline
 N-(Fluorenyl-9-methoxycarbonyl)-D-asparagyl-(.beta.-tert-butyl ester) (7.2
 g, 17.5 mmol) is reacted as described in Example 2.1.a. After
 concentration in vacuo, the residue is taken up in methylene chloride
 (1000 ml) and the mixture is washed with 1N hydrochloric acid (2.times.200
 ml) and with 1N sodium bicarbonate solution (1.times.200 ml). After drying
 over magnesium sulphate (20 g), filtration, concentration to 100 ml and
 addition of petroleum ether, compound 2.7.a is obtained in the form of
 yellow crystals (9.7 g, 86%); TLC [ethyl acetate]: R.sub.f =0.71; melting
 point=195.degree. C.
 2.7.b) N-[D-Asparagyl-(.beta.-tert-butyl ester)]-batracyline
 The above compound (6.4 g, 10 mmol) is dissolved in methylene chloride (100
 ml). After addition of morpholine (50 ml), the mixture is stirred at room
 temperature for 5 hours and then concentrated in vacuo and the residue is
 purified by flash chromatography [ethyl acetate/petroleum ether
 4:1.fwdarw.ethyl acetate.fwdarw.ethyl acetate/ethanol 10:1]. Yellow
 crystals (3.44 g, 82%) are obtained; TLC [ethyl acetate]: R.sub.f =0.21;
 melting point=209.degree. C. (decomposition).
 2.7.c) N-[N.sup..alpha.,N.sup..epsilon.
 -Di-(tert-butoxycarbonyl)-lysyl-D-asparagyl-(.beta.-tert-butyl
 ester)-batracyline
 Compound 2.7.b (2.1 g, 5 mmol) is reacted as described in Example 2.2.a.
 Yellow crystals (1.71 g, 46%) are obtained; TLC [ethyl acetate]: R.sub.f
 =0.61; melting point=142.degree. C.
 2.7) N-[Lysyl-D-asparagyl]-batracyline, di-trifluoroacetate
 Compound 2.7.c (1.65 g, 2.2 mmol) is reacted as described in Example 2.2
 and the product is purified. Yellow crystals (1.5 g, 95%) are obtained;
 TLC [methanol/acetic acid 10:1]: R.sub.f =0.29; melting
 point=154-155.degree. C. (decomposition).
 EXAMPLE 2.8
 N-[Lysyl-D-glutamyl]-batracyline, di-hydrobromide
 ##STR82##
 2.8.a) N-[N-(tert-Butoxycarbonyl)-D-glutamyl-(.beta.-benzyl
 ester)]-batracyline
 N-(tert-Butoxycarbonyl)-D-glutamyl-(.beta.-benzyl ester) (5.9 g, 17.5 mmol)
 is reacted as described in Example 2.1.a. After concentration in vacuo,
 the residue is purified by flash chromatography [petroleum ether/ethyl
 acetate 1:1] to give yellow crystals (9.45 g, 95%); TLC [ethyl acetate]:
 R.sub.f =0.61; [.alpha.].sup.20 =+53.1.degree. (c=1.0/CH.sub.2 Cl.sub.2);
 melting point=159.degree. C.
 2.8.b) N-[D-Glutamyl-(.beta.-benzyl ester)]-batracyline
 Compound 2.8.a (9.1 g, 10 mmol) is dissolved in formic acid (100 ml) and
 the solution is stirred at room temperature for 6 hours. After
 concentration in vacuo, the residue is taken up in methanol (100 ml) and
 the pH of the solution is increased to pH 8 by careful addition of 25%
 strength aqueous ammonia solution. After renewed concentration in vacuo,
 subsequent flash chromatography [ethyl acetate/ethanol 10:1] gives a
 yellow oil (4.2 g, 56%); TLC [ethyl acetate]: R.sub.f =0.06.
 2.8.c) N-[N.sup..alpha.,N.sup..epsilon.
 -Di-(tert-butoxycarbonyl)-lysyl-D-glutamyl-(.beta.-benzyl
 ester)]-batracyline
 The above compound (3.75 g, 8 mmol) is reacted as described in Example
 2.2.a and the product is purified. A yellow amorphous solid (2.26 g, 35%)
 is obtained; TLC [ethyl acetate]: R.sub.f =0.40; [.alpha.].sup.20
 =+32.1.degree. (c=1.2/CH.sub.2 Cl.sub.2).
 2.8) N-[Lysyl-D-glutamyl]-batracyline, di-hydrobromide
 Compound 2.8.c (2.0 g, 2.5 mmol) is dissolved in a 33% strength solution of
 hydrogen bromide in glacial acetic acid (50 ml). After 1 hour at room
 temperature, the batch is concentrated in vacuo and the residue is washed
 thoroughly with diethyl ether. The product is obtained in yellow-red
 crystals (1.63 g, 98%); melting point=207-209.degree. C. (decomposition).
 EXAMPLE 2.9
 N-[Lysyl-glycyl]-batracyline, di-trifluoroacetate
 ##STR83##
 2.9.a) N-[N-(tert-Butoxycarbonyl)-glycyl]-batracyline
 N-(tert-Butoxycarbonyl)-glycine (3.07 g, 17.5 mmol) is reacted as described
 in Example 2.1.a. After 3 days at room temperature, the mixture is
 concentrated in vacuo and the residue is taken up in ethanol (200 ml).
 After the mixture has been stirred under reflux for 30 minutes and
 filtered, after cooling, the target compound is obtained in the form of
 yellow crystals (4.73 g, 66%); TLC [ethyl acetate]: R.sub.f =0.44; melting
 point=279.degree. C. (decomposition).
 2.9.b) N-Glycyl-batracyline, hydrochloride
 The above compound (4.1 g, 10 mmol) is dissolved in methylene chloride
 (1200 ml), while heating in an ultrasonic bath. After addition of hydrogen
 chloride in diethyl ether (100 ml), the mixture is stirred at room
 temperature for 30 minutes and concentrated in vacuo, and ethanol (200 ml)
 is added to the residue. After the mixture has been stirred under reflux
 for 10 minutes and filtered, after cooling, the product is obtained in the
 form of yellow crystals (3.21 g, 94%); melting point 297-299.degree. C.
 (decomposition).
 2.9.c) N-[N.sup..alpha.,N.sup..epsilon.
 -Di-(tert-butoxycarbonyl)-lysyl-glycyl]-batracyline
 N,N-Di-(tert-butoxycarbonyl)-lysine (2.1 g, 6 mmol) and
 2-isobutoxy-1-isobutoxycarbonyl-1,2-dihydro-quinoline (2.4 ml, 8 mmol) are
 dissolved in 20 ml of methylene chloride. After the mixture has been
 stirred at room temperature for 20 minutes, a solution of compound 2.9.b
 (1.71 g, 5 mmol), ethyldiisopropylamine (0.86 ml, 5mmol) and
 dimethylformamide (40 ml) is added and the batch is stirred at room
 temperature for a further 16 hours. It is then concentrated in vacuo and
 the residue is purified by flash chromatography [ethyl acetate/petroleum
 ether 1:1.fwdarw.ethyl acetate]. Yellow crystals (1.69 g, 53%) are
 obtained; TLC [ethyl acetate]: R.sub.f =0.31; melting point=211 .degree.
 C. (decomposition).
 2.9) N-[Lysyl-glycyl]-batracyline, di-trifluoroacetate
 Compound 2.9.c (1.4 g, 2.2 mmol) is reacted as described in Example 2.2 and
 the product is purified. Yellow crystals (1.33 g, 91%) are obtained;
 melting point=153.degree. C. (decomposition).
 EXAMPLE 2.10
 N-[Lysyl-seryl]-batracyline, di-trifluoroacetate
 ##STR84##
 2.10.a) N-[N-(tert-Butoxycarbonyl)-seryl]-batracyline
 N-(tert-Butoxycarbonyl)-serine (3.6 g, 17.5 mmol) is reacted as described
 in Example 2.1.a. After 48 hours, the mixture is concentrated to 100 ml in
 vacuo and 21 of methylene chloride are added to the concentrate. The
 resulting solution is washed with water (1.times.500 ml), with 0.5 N
 hydrochloric acid (2.times.250 ml) and with saturated sodium bicarbonate
 solution (1.times.250 ml). Drying over magnesium sulphate (50 g),
 distilling off the solvent in vacuo and flash chromatography [petroleum
 ether/ethyl acetate 1:1] of the residue gives compound 2.10.a (4.6 g, 64%)
 in the form of yellow crystals; TLC [ethyl acetate/acetic acid 100:1]:
 R.sub.f =0.38; melting point=219.degree. C. (decomposition);
 [.alpha.].sup.20 =-61.0.degree. (c=0.5/CH.sub.2 Cl.sub.2 +0.5% CH.sub.3
 OH).
 2.10.b) N-Seryl-batracyline, hydrochloride
 Concentrated hydrochloric acid (10 ml) is added to a suspension of the
 above compound (4.6 g, 10.4 mmol) in dioxane (70 ml), while stirring, and
 the mixture is then stirred vigorously at room temperature for 1 hour. It
 is subsequently concentrated in vacuo and the residue is dried under an
 oil pump vacuum for 2 hours. After addition of ethanol (100 ml), the
 mixture is boiled under reflux for 15 minutes. Cooling and filtration with
 suction give orange crystals (1.97 g, 96%); TLC [ethyl acetate]: R.sub.f
 =0.05; [.alpha.].sup.20 =+51.8.degree. (c=1.0/H.sub.2 OH); melting
 point&gt;270.degree. C. (decomposition).
 2.10.c) N-[N.sup..alpha.,N.sup..epsilon.
 -Di-(tert-butoxycarbonyl)-lysyl-seryl]-batracyline
 Compound 2.10.b (1.86 g, 5 mmol) is reacted as described in Example 2.9.c.
 After flash chromatography [ethyl acetate/petroleum ether 2:1.fwdarw.ethyl
 acetate], yellow crystals (1.18 g, 36%) are obtained; TLC [ethyl
 acetate/acetic acid 100:1]: R.sub.f =0.24; melting point=188.degree. C.
 (decomposition); [.alpha.].sup.20 =-13.1.degree. (c=0.5/CH.sub.2 Cl.sub.2
 +0.5% CH.sub.3 OH).
 2.10) N-[Lysyl-seryl]-batracyline, di-trifluoroacetate
 Compound 2.10.c (1.0 g, 1.5 mmol) is reacted as described in Example 2.2
 and the product is purified. Yellow crystals (1.0 g, 96%) are obtained;
 TLC [methylene chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.10;
 melting point=188-190.degree. C. (decomposition).
 EXAMPLE 2.11
 N-[Lysyl-D-seryl]-batracyline, di-hydrobromide
 ##STR85##
 2.11.a)
 N-[N-(Fluorenyl-9-methoxycarbonyl)-O-(tert-butyl)-D-seryl]-batracyline
 N-(Fluorenyl-9-methoxycarbonyl)-O-(tert-butyl)-D-serine (6.7 g, 17.5 mmol)
 is reacted as described in Example 2.1.a. Concentration in vacuo and flash
 chromatography [petroleum ether/ethyl acetate 1:1] give the compound
 2.11.a (5.64 g, 52%) in the form of yellow crystals; TLC [methylene
 chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.87; melting
 point=225-226.degree. C. (decomposition).
 2.11.b) N-[O-(tert-Butyl)-D-seryl]-batracyline
 The above compound (2.89 g, 4.7 mmol) is reacted as described in Example
 2.7.b. Flash chromatography [petroleum ether/ethyl acetate
 3:2.fwdarw.ethyl acetate] gives the product as yellow crystals (1.15 g,
 62%); TLC [ethyl acetate]: R.sub.f =0.11; melting point=197.degree. C.
 2.11.c) N-[N.sup..alpha.,N.sup..epsilon.
 -Di-(tert-butoxycarbonyl)-lysyl-O-(tert-butyl)-D-seryl]-batracyline
 The above compound (1.1 g, 2.8 mmol) is reacted as described in Example
 2.2.a. Yellow crystals (1.94 g, 96%) are obtained; TLC [ethyl acetate]:
 R.sub.f =0.59; melting point=208.degree. C.
 2.11.d) N-[Lysyl-O-(tert-butyl)-D-seryl]-batracyline, di-trifluoroacetate
 Compound 2.11.c (1.08 g, 1.5 mmol) is reacted as described in Example 2.2
 and the product is purified. Yellow crystals (1.1 g, 98%) are obtained;
 TLC [methanol/acetic acid 10:1]: R.sub.f =0.30; melting point=128.degree.
 C.
 2.11) N-[Lysyl-D-seryl]-batracyline, di-hydrobromide
 Compound 2.11.d (1.05 g, 1.4 mmol) is reacted as described in Example 2.8
 and the product is purified. Yellow-red crystals (846 mg, 96%) are
 obtained; melting point=247-248.degree. C.
 EXAMPLE 2.12
 N-[Lysyl-D-threonyl]-batracyline, di-hydrobromide
 ##STR86##
 2.12.a)
 N-[N-(Fluorenyl-9-methoxycarbonyl)-O-(tert-butyl)-D-threonyl]-batracyline
 N-(Fluorenyl-9-methoxycarbonyl)-O-)tert-butyl)-D-threonine (6.96 g, 17.5
 mmol) is reacted as described in Example 2.1.a. Concentration in vacuo and
 flash chromatography [petroleum ether/ethyl acetate 1:1] give the compound
 2.12.a (7.45 g, 68%) in the form of yellow crystals; TLC [ethyl acetate]:
 R.sub.f =0.63; melting point=225-226.degree. C.
 2.12.b) N-1O-(tert-Butyl)-D-threonyl]-batracyline
 Compound 2.12.a (3.8 g, 6 mmol) is reacted as described in Example 2.7.b.
 After concentration in vacuo, the product is obtained as yellow crystals
 (1.9 g, 78%); TLC [ethyl acetate]: R.sub.f =0.21; melting
 point=110-111.degree. C.
 2.12.c) N-[N.sup..alpha.,N.sup..epsilon.
 -Di-(tert-butoxycarbonyl)-lysyl-O-(tert-butyl)-D-threonyl]-batracyline
 Compound 2.12.b (1.8 g, 4.5 mmol) is reacted as described in Example 2.2.a.
 Yellow crystals (2.6 g, 79%) are obtained; TLC [ethyl acetate]: R.sub.f
 =0.59; melting point=112.degree. C.
 2.12.d) N-[Lysyl-O-(tert-butyl)-D-threonyl]-batracyline,
 di-trifluoroacetate
 The above compound (2.5 g, 3.4 mmol) is reacted as described in Example 2.2
 and the product is purified. Yellow crystals (2.5 g, 96%) are obtained;
 TLC [methanol/acetic acid 10:1]: R.sub.f =0.30; melting point=142.degree.
 C. (decomposition).
 2.12) N-[Lysyl-D-threonyl]-batracyline, di-hydrobromide
 Compound 2.12.d (2.29 g, 3 mmol) is reacted as described in Example 2.8 and
 the product is purified. Yellow-red crystals (1.86 g, 97%) are obtained;
 melting point=232.degree. C. (decomposition).
 EXAMPLE 2.13
 N-[Lysyl-D-alanyl]-batracyline, di-trifluoroacetate
 ##STR87##
 2.13.a) N-[N.sup..alpha.,N.sup..epsilon.
 -Bis-(tert-butoxycarbonyl)-lysyl-D-alanyl]-batracyline
 6 g (17.3 mmol) of N.sub..alpha.,N.sup..epsilon.
 -bis-(tert-butoxycarbonyl)-lysine are dissolved in 75 ml of
 dimethylformamide, and 3 g (26 mmol) of N-hydroxysuccinimide and 4.29 g
 (20.8 mmol) of N,N'-dicyclohexylcarbodiimide are added at 0.degree. C.
 After 3 hours, the urea formed is filtered off, 5 g (15.6 mmol) of
 N-[D-alanyl]-batracyline (Example 2.3) are added to the filtrate and the
 mixture is stirred at 20.degree. C. for 16 hours. Residual urea is
 filtered off and discarded. The filtrate is concentrated, the residue is
 stirred with methanol and the mixture is filtered. The filtrate is
 concentrated again and the residue is treated again with methanol. The
 mixture is again filtered and the filter residues are combined. They are
 dissolved in methylene chloride/methanol 10:1 and the product is
 precipitated with ether. 8.22 g (81%) of the crystalline target product
 are obtained.
 2.13) N-[Lysyl-D-alanyl]-batracyline, di-trifluoroacetate
 Preparation from 8.2 g of compound 2.13.a analogously to Example 2.2.
 Yield: 7.58 g (89%)
 EXAMPLE 2.14
 N-[N.sup..epsilon. -(Fluorenyl-9-methoxycarbonyl)-lysyl]-batracyline,
 trifluoroacetate
 ##STR88##
 2.14.a) N-[N.sup..alpha. -(tert-Butoxycarbonyl)-N.sup..epsilon.
 -(fluorenyl-9-methoxycarbonyl)-lysyl]-batracyline
 Preparation analogously to Example 2.4.a from N.sup..alpha.
 -(tert-butoxycarbonyl)-N.sup..epsilon.
 -(fluorenyl-9-methoxycarbonyl)-lysine and batracyline. Yield: 78%
 2.14) N-[N.sup..epsilon. -(Fluorenyl-9-methoxycarbonyl)-lysyl]-batracyline,
 trifluoroacetate
 Preparation analogously to Example 2.5 from compound 2.14.a. Yield: 90%
 EXAMPLE 2.15
 N-[Lysyl-N.sup..epsilon. -(fluorenyl-9-methoxycarbonyl)-lysyl]-batracyline,
 di-trifluoroacetate
 ##STR89##
 2.15.a) N-[N.sup..alpha.,N.sup..epsilon.
 -Di-(tert-butoxycarbonyl)-lysyl-N.sup..epsilon.
 -(fluorenyl-9-methoxycarbonyl)-lysyl]-batracyline
 3240 mg (4.54 mmol) of compound 2.14 are dissolved in 50 ml of
 dimethylformamide, and 2550 mg (5.45 mmol) of
 N.sup..alpha.,N.sup..epsilon. -di-(tert-butoxycarbonyl)-lysine
 p-nitrophenyl ester and 938 .mu.l of ethyldiisopropylamine are added. The
 mixture is stirred at 20.degree. C. for. 16 hours and concentrated and the
 residue is initially stirred with ether. The mixture is filtered and the
 filter residue is stirred again, with methanol/ether 1:1. 3881 mg (92%) of
 the target product are obtained in this way after filtration with suction
 and drying.
 2.15) N-[Lysyl-N.sup..epsilon.
 -(fluorenyl-9-methoxycarbonyl)-lysyl]-batracyline, di-trifluoroacetate
 Deblocking of compound 2.15.a with anhydrous trifluoroacetic acid/methylene
 chloride 1:1 analogously to Example 2.2. Yield: 95% [TLC: methylene
 chloride/methanol/ammonia (17%) 15:6:0.6 R.sub.f =0.08]
 EXAMPLE 2.16
 N-[Lysyl-N.sup..beta.
 -(fluorenyl-9-methoxycarbonyl)-.alpha.,.beta.-diaminopropionyl]-batracylin
 e, di-trifluoroacetate
 ##STR90##
 This peptide conjugate was prepared analogously to Examples 2.14 and 2.15
 via 4 stages from batracyline and N.sup..alpha.
 -(tert-butoxycarbonyl)-N.sup..beta.
 -(fluorenyl-9-methoxycarbonyl)-diaminopropionic acid. [TLC: methylene
 chloride/methanol/glacial acetic acid 5:1:0.2 R.sub.f =0.15]
 EXAMPLE 2.17
 N-[Lysyl]-batracyline
 ##STR91##
 Splitting off of Fmoc analogously to Example 2.4 from N-[N.sup..epsilon.
 -(fluorenyl-9-methoxycarbonyl)-lysyl]-batracyline trifluoroacetate
 (Example 2.14). Yield: 65%
 EXAMPLE 2.18
 N-[Seryl-D-alanyl]-batracyline, trifluoroacetate
 ##STR92##
 2.18.a) N-[N-(tert-Butoxycarbonyl)-seryl-D-alanyl]-batracyline
 Preparation analogously to Example 2.13.a from
 N-(tert-butoxycarbonyl)-serine and N-[D-alanyl]-batracyline (Example 2.3).
 Yield: 77%
 2.18) N-[Seryl-D-alanyl]-batracyline, trifluoroacetate
 Preparation analogously to Example 2.2 from compound 2.18.a. Yield: 98%
 EXAMPLE 2.19
 N-[D-Alanyl-D-alanyl]-batracyline, trifluoroacetate
 ##STR93##
 Preparation via 2 stages analogously Example 2.18.
 EXAMPLE 2.20
 M-[Glutamyl-D-alanyl]-batracyline
 ##STR94##
 Preparation via 2 stages analogously to Example 2.18 starting from
 N-tert-butoxycarbonyl-glutamyl-.delta.-tert-butyl ester and
 N-[D-alanyl]-batracyline (Example 2.3). After splitting off of the Boc,
 the mixture is concentrated, the residue is taken up in water, the pH is
 brought to 7 with 0.1 N sodium hydroxide solution and the betaine is
 filtered off with suction.
 EXAMPLES 3.1-3.34
 General Formula
 ##STR95##
 EXAMPLE 3.1
 N-{N.sup..epsilon.
 -[O-(.beta.-L-Fucosyl)-4-hydroxy-phenylaminothio-carbonyl]-lysyl-D-alanyl}
 -batracyline
 3.1.a) N-{N.sup..alpha. -(tert-Butoxycarbonyl)-N.sup..epsilon.
 -[O-(.beta.-L-fucosyl)-4-hydroxy-phenylaminothiocarbonyl]-lysyl-D-alanyl}-
 batracyline
 Thiophosgene (34 .mu.l, 0.44 mmol) is added to 55 mg (0.22 mmol) of
 p-aminophenyl .beta.-L-fucoside in 10 ml of dioxane/water 1:1, while
 stirring. After 10 minutes, the mixture is concentrated in vacuo and the
 residue is dried under a high vacuum for 1 hour. The isothiocyanate
 obtained is then coupled in absolute dimethylformamide with 109 mg (0.21
 mmol) of N-[N.sup..alpha.
 -(tert-butoxycarbonyl)-lysyl-D-alanyl]-batracyline (Example 2.4) in the
 presence of 115 .mu.l of ethyldiisopropylamine. After the crude product
 has been precipitated twice from methanol/isopropanol, 132 mg (75%) of the
 target product are obtained. [TLC: methylene chloride/methanol 9:1 R.sub.f
 =0.151.
 3.1) N-{N.sup..epsilon.
 -O-(.beta.-L-Fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl-D-alanyl}-
 batracyline
 127 mg (0.15 mmol) of the compound from Example 3.1.a are stirred in 10 ml
 of methylene chloride with 6 ml of anhydrous trifluoroacetic acid at
 0.degree. C. for 2 hours. The mixture is concentrated, the residue is
 subsequently distilled three times with 5 ml of methylene chloride and the
 product is chromatographed with methylene chloride/methanol/ammonia (17%)
 15:2:0.2. After subsequent freeze drying, 80 mg (71%) of the target
 product are obtained: [TLC: methylene chloride/methanol/ammonia (17%
 15:4:0.4 R.sub.f =0.3].
 Analogously to Example 3.1, the following glycoconjugates are prepared from
 the partly protected peptide conjugate in Example 2.4 or from the isomeric
 N-[N.sup..alpha. -(tert-butoxycarbonyl)-lysyl-alanyl]-batracyline, which
 is to be prepared analogously:
 EXAMPLE 3.2
 N-{N.sup..epsilon.
 -O-(2-O-Methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl
 -D-alanyl}-batracyline
 Educt:
 carbohydrate from Example 1.1
 Flash chromatography purification of the intermediate stage with methylene
 chloride/methanol 95:5 and of the final stage with methylene
 chloride/methanol/ammonia (17%) 15:2:0.2. Yield: 55% [TLC: methylene
 chloride/methanol/glacial acetic acid 5:1:0.2 R.sub.f =0.4].
 EXAMPLE 3.3
 N-{N.sup..epsilon.
 -[O-(2-O-Methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysy
 l-alanyl}-batracyline
 Educt:
 carbohydrate from Example 1.1
 Purification of the into mediate stage by precipitation from methylene
 chloride/methanol 1:1 with ether and flash chromatography purification of
 the final stage with methylene chloride/methanol/ammonia (17%) 15:2:0.2.
 Yield: 65% [TLC: methylene chloride/methanol/ammonia (17%) 15:2:0.2
 R.sub.f =0.21].
 EXAMPLE 3.4
 N-{N.sup..epsilon.
 -[O-(3-O-Methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysy
 l-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate from Example 1.2
 Flash chromatography purification of the intermediate stage with methylene
 chloride/methanol 97.5:2.5 and precipitation of the final stage from
 methanol with ether; yield: 59% [TLC: methylene chloride/methanol/ammonia
 (17%) 15:2:0.2 R.sub.f =0.19].
 EXAMPLE 3.5
 N-{N.sup..epsilon.
 -[O-(3-O-Methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysy
 l-alanyl}-batracyline
 Educt:
 carbohydrate from Example 1.2
 Purification of the intermediate stage by precipitation from methylene
 chloride/methanol 1:1 with ether and flash chromatography purification of
 the final stage with methylene chloride/methanol/ammonia (17%) 15:2:0.2.
 Yield: 36% [TLC: methylene chloride/methanol/ammonia (17%) 15:4:0.5
 R.sub.f =0.57].
 EXAMPLE 3.6
 N-{N.sup..epsilon.
 -[O-(3-O-Methyl-.alpha.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lys
 yl-D-alanyl}-batracyline
 Educt:
 carbohydrate from Example 1.3
 Purification of the intermediate stage by precipitation from methanol with
 ether and flash chromatography purification of the final stage with
 methylene chloride/methanol/ammonia (17%) 15:2:0.2. Yield: 44% [TLC:
 methylene chloride/methanol/ammonia (17%) 15:2:0.2 R.sub.f =0.15].
 EXAMPLE 3.7
 N-{N.sup..epsilon.
 -[O-(3-Deoxy-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl-D
 -alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate from Example 1.6
 Flash chromatography purification of the intermediate stage with methylene
 chloride/methanol 95:5 and precipitation of the final stage from methanol
 with ether. Yield: 35% [TLC: acetonitrile/water/glacial acetic acid
 5:1:0.2 R.sub.f =0.42].
 EXAMPLE 3.8
 N-{N.sup..epsilon.
 -[O-(3,4-Epoxy-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl
 -D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate from Example 1.8
 Flash chromatography purification of the intermediate stage with methylene
 chloride/methanol 95:5. Several precipitations of the final stage from
 methanol with ether and subsequent stirring with ethyl acetate. [TLC:
 acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.49].
 EXAMPLE 3.9
 N-{N.sup..epsilon.
 -[O-(3-O-Carboxymethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbony
 l]-lysyl-D-alanyl}-batracyline, sodium salt
 Educt:
 carbohydrate from Example 1.10
 Purification of the intermediate stage by stirring with methanol and
 completion of the precipitation with ether. Flash chromatography
 purification of the final stage with methylene chloride/methanol/ammonia
 (17%) 15:3:0.3; later in the same system with 15:6:0.6. The corresponding
 fractions are concentrated, the residue is taken up in water and the pH is
 brought to 7 with 0.1N sodium hydroxide solution. The mixture is filtered
 with suction, the filter residue is taken up in dimethylformamide/water
 1:3 and one equivalent of a 0.1N sodium hydroxide solution is added. The
 mixture is concentrated and the sodium salt is taken up in water and
 lyophilized. Yield: 43%. [TLC: methylene chloride/methanol/ammonia (17%)
 15:4:0.5 R.sub.f =0.15].
 EXAMPLE 3.10
 N-{N.sup..epsilon.
 -[O-(3-O-Carbamoylmethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbo
 nyl]-lysyl-D-alanyl}-batracyline, sodium salt
 Educt:
 carbohydrate from Example 1.18
 Purification of the intermediate stage by stirring with methanol and
 completion of the precipitation with ether. Flash chromatography
 purification of the final stage with methylene chloride/methanol/ammonia
 (17%) 15:2:0.2. [TLC: methylene chloride/methanol/ammonia (17%) 15:3:0.3
 R.sub.f =0.38]; melting point: 190.degree. C. (decomposition).
 EXAMPLE 3.11
 N-{N.sup..epsilon.
 -[O-(4-O-Methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysy
 l-D-alanyl}-batracyline, acetate
 Educt:
 carbohydrate from Example 1.4
 Flash chromatography purification of the intermediates stage with methylene
 chloride/methanol 95:5 and of the final stage with methylene
 chloride/methanol/ammonia (17%) 15:2:0.2. After the concentration, one
 equivalent of glacial acetic acid and 10 ml of water are added to the
 residue and the mixture is lyophilized. Yield: 52% [TLC:
 acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.43]. FAB-MS:
 m/z=760=M+1.
 EXAMPLE 3.12
 N-{N.sup..epsilon.
 -[O-(.alpha.-D-Glucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl-D-alany
 l}-batracyline, trifluoroacetate
 Educt:
 p-aminophenyl .alpha.-D-glucoside
 Purification of the intermediate stage and of the final stage by stirring
 with methanol and completion of the precipitation with ether. Yield: 83%
 [TLC: methylene chloride/methanol/ammonia (17%) 15:8:0.8 R.sub.f =0.48].
 EXAMPLE 3.13
 N-{N.sup..epsilon.
 -[O-(.alpha.-D-Glucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl-alanyl}
 -batracyline, trifluoroacetate
 Educt:
 p-aminophenyl .alpha.-D-glucoside
 Analogous preparation to that of the isomer in Example 3.12
 EXAMPLE 3.14
 N-{N.sup..epsilon.
 -[O-(3-O-Methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thiocarbo
 nyl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 3.14.a) N-{N.sup..alpha. -(tert-Butoxycarbonyl)-N.sup..epsilon.
 -[O-(3-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thiocarbo
 nyl]-lysyl-D-alanyl}-batracyline
 Thiophosgene (33.5 ml, 0.44 mmol) is added to a solution of compound 1.25
 (62.8 mg, 0.22 mmol) in dioxane/water 1:1 (10 ml), while stirring. After
 10 minutes, the mixture is concentrated in vacuo and the residue is dried
 under an oil pump vacuum for 1 hour. The isothiocyanate obtained is
 dissolved in absolute dimethylformamide (10 ml), and compound 2.4 (109.7
 mg, 0.2 mmol) and ethyldiisopropylamine (0.5 ml) are added. The mixture is
 stirred at room temperature for 16 hours and then concentrated in vacuo
 and the residue is purified by flash chromatography [methylene
 chloride/methanol 20:1]. Yellow crystals (108.3 mg, 62 %) are obtained;
 TLC [methylene chloride/methanol 5:1]: R.sub.f =0.42]; melting
 point=194-195.degree. C. (decomposition).
 3.14) N-{N.sup..epsilon.
 -[O-(3-O-Methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thiocarbo
 nyl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 The tert-butoxycarbonyl group is split off from compound 3.14.a (105.1 mg,
 0.12 mmol) as described in Example 2.2. After concentration in vacuo and
 reprecipitation from methanol/diethyl ether, yellow crystals (57.4 mg,
 54%) are obtained; TLC [methylene chloride/methanol 5:1]: R.sub.f =0.16;
 melting point=188-189.degree. C. (decomposition).
 The following glycoconjugates are prepared analogously to Example 3.14.a
 and 3.14 from peptide conjugate 2.4 (in each case 109.7 mg, 0.2 mmol):
 EXAMPLE 3.15
 N-{N.sup..epsilon.
 -[O-(.beta.-D-Galactopyranosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl-
 D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate 1.23 (59.7 mg, 0.22 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol 10:1] gives yellow crystals (79.5 mg, 46%); TLC
 [methanol]: R.sub.f =0.74; melting point=182.degree. C.
 Purification of the end product as described in Example 3.14 gives yellow
 crystals (77.1 mg, 44%); TLC [methanol]: R.sub.f =0.27; melting
 point=191-192.degree. C. (decomposition).
 EXAMPLE 3.16
 N-{N.sup..epsilon.
 -[O-(3,4-Di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thio
 carbonyl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate 1.31 (79 mg, 0.22 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol 30:1.fwdarw.20:1] gives yellow crystals (150.7 mg, 85%);
 TLC [methylene chloride/methanol 10:1]: R.sub.f =0.35; melting
 point=197-199.degree. C. (decomposition).
 Purification of the end product as described in Example 3.14 gives yellow
 crystals (137 mg, 76%); TLC [methylene chloride/methanol 10:1]: R.sub.f
 =0.13; melting point=184-186.degree. C. (decomposition).
 EXAMPLE 3.17
 N-{N.sup..epsilon.
 -[O-(3-O-Methoxycarbonylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenyl
 amino-thiocarbonyl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate 1.42 (75.5 mg, 0.22 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol 30:1.fwdarw.25:1] gives yellow crystals (124.1 mg, 66%);
 TLC [methylene chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.50;
 melting point=165.degree. C.
 Purification of the end product as described in Example 3.14 gives yellow
 crystals (107.8 mg, 57%); TLC [methylene chloride/methanol 4:1]: R.sub.f
 =0.53; melting point=183.degree. C. (decomposition).
 EXAMPLE 3.18
 N-{N.sup..epsilon.
 -[O-(3-O-Carboxymethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-th
 iocarbonyl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 compound 1.43 (77.3 mg, 0.22 mmol)
 Purification of the intermediate stage by reprecipitation from
 ethanol/diethyl ether gives the sodium salt as yellow crystals (172 mg,
 91%); TLC [methanol]: R.sub.f =0.71; melting point=225-228.degree. C.
 Purification of the end product as described in Example 3.14 gives yellow
 crystals (136.5 mg, 73%); TLC [methanol]: R.sub.f =0.12; melting
 point=217-220.degree. C. (decomposition).
 EXAMPLE 3.19
 N-{N.sup..epsilon.
 -[-(3-O-Carbamoylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-t
 hiocarbonyl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate 1.44 (72.2 mg, 0.22 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol 10:1] gives yellow crystal (137.7 mg, 75%); TLC
 [methylene chloride/methanol 4:1]: R.sub.f =0.41; melting
 point=198-201.degree. C. (decomposition).
 Purification of the end product as in Example 3.14 gives yellow crystals
 (140.2 mg, 75%); TLC [methylene chloride/methanol 4:1]: R.sub.f =0.16;
 melting point=188-190.degree. C. (decomposition).
 EXAMPLE 3.20
 N-{N.sup..epsilon.
 -[O-(3-O-(N-Methyl-carbamoylmethyl)-.beta.-D-galactopyranosyl)-4-hydroxy-p
 henylamino-thiocarbonyl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate 1.45 (75.3 mg, 0.22 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol/ammonia (25%) 7:1:0.1] gives yellow crystals (158.4 mg,
 85%); TLC [methylene chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f
 =0.25; melting point=161-163.degree. C. (decomposition).
 Purification of the end product as described in Example 3.14 gives yellow
 crystals (132.5 mg, 70%); TLC [methylene chloride/methanol/ammonia (25%)
 15:3:0.2]: R.sub.f =0.10; melting point=191-193.degree. C.
 (decomposition).
 EXAMPLE 3.21
 N-{N.sup..epsilon.
 -[O-(3-O-(N-Propyl-carbamoylmethyl)-.beta.-D-galactopyranosyl)-4-hydroxy-p
 henylamino-thiocarbonyl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate 1.46 (81.5 mg, 0.22 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol/ammonia (25%) 8:1:0.1] gives yellow crystals (153.1 mg,
 80%); TLC [methylene chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f
 =0.33; melting point=187.degree. C. (decomposition).
 Purification of the end product as described in Example 3.14 gives yellow
 crystals (154.9 mg, 79%); TLC [methylene chloride/methanol/ammonia (25%)
 15:3:0.2]: R.sub.f =0.21; melting point=179.degree. C.
 EXAMPLE 3.22
 N-{N.sup..epsilon.
 -[O-(3-O-(N-Butyl-carbamoylmethyl)-.beta.-D-galactopyranosyl)-4-hydroxy-ph
 enylamino-thiocarbonyl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate 1.47 (84.6 mg, 0.22 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol 12:1] gives yellow crystals (132.7 mg, 68%); TLC
 [methylene chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.54;
 melting point=180-182.degree. C.
 Purification of the end product as described in Example 3.14 gives yellow
 crystals (115.2 mg, 58%); TLC [methylene chloride/methanol/ammonia (25%)
 15:3:0.2]: R.sub.f =0.30; melting point=176.degree. C.
 EXAMPLE 3.23
 N-{N.sup..epsilon.-[O-(
 3,4-Dideoxy-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thiocarbonyl]
 -lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate 1.52 (52.6 mg, 0.22 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol 25:1] gives yellow crystals (127.4 mg, 77%); TLC
 [methylene chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.60;
 melting point=166-167.degree. C.
 Purification of the end product as described in Example 3.14 gives yellow
 crystals (103.1 mg, 61%); TLC [methylene chloride/methanol/ammonia (25%)
 15:3:0.2]: R.sub.f =0.44; melting point=173-175.degree. C.
 (decomposition).
 EXAMPLE 3.24
 N-{N.sup..epsilon.
 -[O-(6-O-Acetyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thiocarbo
 nyl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate 1.53 (78.2 mg, 0.22 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol 25:1] gives yellow crystals (88.3 mg, 49%); TLC
 [methylene chloride/methanol 4:1]: R.sub.f =0.61; melting
 point=196-199.degree. C. (decomposition).
 Purification of the end product as described in Example 3.14 gives yellow
 crystals (89.6 mg, 49%); TLC [methylene chloride/methanol 4:1]: R.sub.f
 =0.31; melting point=186.degree. C. (decomposition).
 EXAMPLE 3.25
 N-{N.sup..epsilon.
 -[O-(.alpha.-D-Mannopyranosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl-D
 -alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate 1.39 (59.7 mg, 0.22 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol 10:1] gives yellow crystals (101.7 mg, 59%); TLC
 [methanol]: R.sub.f =0.79; melting point=180.degree. C. (decomposition).
 Purification of the end product as described in Example 3.14 gives yellow
 crystals (103.1 mg, 59%); TLC [methanol]: R.sub.f =0.34; melting
 point=177-178.degree. C. (decomposition).
 EXAMPLE 3.26
 N-{N.sup..epsilon.
 [O-(3-O-Methyl-.alpha.-D-mannopyranosyl)-4-hydroxy-phenylamino-thiocarbony
 l]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate 1.40 (62.8 mg, 0.22 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol 20:1] gives yellow crystals (56.6 mg, 32%); TLC
 [methylene chloride/methanol 5:1]: R.sub.f =0.38; melting
 point=191-192.degree. C. (decomposition).
 Purification of the end product as described in Example 3.14 gives yellow
 crystals (46.6 mg, 26%); TLC [methylene chloride/methanol 5:1]: R.sub.f
 =0.13; melting point=190-191 .degree. C. (decomposition).
 EXAMPLE 3.27
 N-{N.sup..epsilon.
 -[O-(2,3-Di-O-methyl-.alpha.-D-mannopyranosyl)-4-hydroxy-phenylamino-thioc
 arbonyl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate 1.41 (66 mg, 0.22 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol 25:1] gives yellow crystals (77.8 mg, 44%); TLC
 [methylene chloride/methanol 4:1]: R.sub.f =0.65; melting
 point=182-183.degree. C. (decomposition).
 Purification of the end product as described in Example 3.14 gives yellow
 crystals (66.1 mg, 37%); TLC [methylene chloride/methanol 4:1]: R.sub.f
 =0.40; melting point=181.degree. C.
 EXAMPLE 3.28
 N-{N.sup..epsilon.
 -[O-(3-O-Methoxycarbonylmethyl-.alpha.-D-mannopyranosyl)-4-hydroxy-phenyla
 mino-thiocarbonyl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate 1.48 (75.5 mg, 0.22 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol 18:1] gives yellow crystals (62.1 mg, 33%); TLC
 [methylene chloride/methanol/ammonia (25%) 15:3:0.2]: R.sub.f =0.66;
 melting point=165.degree. C.
 Purification of the end product as described in Example 3.14 gives yellow
 crystals (57.6 mg, 30%); TLC [methylene chloride/methanol/ammonia (25%)
 15:3:0.2]: R.sub.f =0.43; melting point=183-184.degree. C.
 EXAMPLE 3.29
 N-{N.sup..epsilon.
 -[O-(3-O-Carboxymethyl-.alpha.-D-mannopyranosyl)-4-hydroxy-phenylamino-thi
 ocarbonyl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate 1.49 (77.3 mg, 0.22 mmol)
 Purification of the intermediate stage by reprecipitation from
 ethanol/diethyl ether gives the sodium salt as yellow crystals (173.4 mg,
 92%); TLC [methanol]: R.sub.f =0.57; melting point=201-205.degree. C.
 (decomposition).
 Purification of the end product as described in Example 3.14 gives yellow
 crystals (171.7 mg, 92%); TLC [methanol]: R.sub.f =0.29; melting
 point=196-198.degree. C. (decomposition).
 EXAMPLE 3.30
 N-{N.sup..epsilon.
 -[O-(3-O-Carbamoylmethyl-.alpha.-D-mannopyranosyl)-4-hydroxy-phenylamino-t
 hiocarbonyl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate 1.50 (72.2 mg, 0.22 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol 10:1] gives yellow crystals (106.6 mg, 58%); TLC
 [methylene chloride/methanol 4:1]: R.sub.f =0.34; melting
 point=192-194.degree. C. (decomposition).
 Purification of the end product as described in Example 3.14 gives yellow
 crystals (107.7 mg, 58%); TLC [methylene chloride/methanol 4:1]: R.sub.f
 =0.13; melting point=186-187.degree. C. (decomposition).
 EXAMPLE 3.31
 N-{N.sup..epsilon.
 -[O-(3,4-Di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thio
 carbonyl]-lysyl-D-alanyl}-batracyline
 3.31.a) N-{N.sup..alpha. -(Fluorenyl-9-methoxycarbonyl)-N.sup..epsilon.
 -[O-(3,4-di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thio
 carbonyl]-lysyl-D-alanyl}-batracyline
 Thiophosgene (33.5 ml, 0.44 mmol) is added to a solution of compound 1.31
 (79 mg, 0.22 mmol) in dioxane/water 1:1 (10 ml). After 10 minutes, the
 mixture is concentrated in vacuo and the residue is dried under an oil
 pump vacuum for 1 hour. The isothiocyanate obtained is dissolved in
 absolute dimethylformamide (10 ml), and compound 2.5 (157 mg, 0.2 mmol)
 and ethyldiisopropylamine (0.5 ml) are added. The mixture is stirred at
 room temperature for 16 hours and then concentrated in vacuo and the
 residue is taken up in methylene chloride/methanol 1:1. The product is
 precipitated by addition of diethyl ether and washed with a little
 ice-cold methanol. Yellow crystals (191 mg, 94%) are obtained; TLC
 [methylene chloride/methanol 10:1]: R.sub.f =0.35; melting
 point=203.degree. C. (decomposition).
 3.31) N-{N.sup..epsilon.
 -[-(3,4-Di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thioc
 arbonyl]-lysyl-D-alanyl}-batracyline
 The fluorenyl-9-methoxycarbonyl group is split off from compound 3.31.a
 (182.2 mg, 0.18 mmol) as described in Example 2.4. After concentration in
 vacuo and dissolving in methanol/methylene chloride 1:1, the product is
 precipitated by addition of diethyl ether. Yellow crystals (127.1 mg, 89%)
 are obtained; TLC [methanol]: R.sub.f =0.46; melting point=158.degree. C.
 The following glycoconjugates are prepared analogously to Examples 3.31.a
 and 3.31 from peptide conjugate 2.5 (in each case 157 mg, 0.2 mmol):
 EXAMPLE 3.32
 N-{N.sup..epsilon.
 -[O-(3-O-(Piperidyl-N)-carbonylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy
 -phenylamino-thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Educt:
 carbohydrate 1.42 (75.5 mg, 0.22 mmol)
 Purification of the intermediate stage as described in Example 3.31.a;
 yellow crystals (191.2 mg, 91%) are obtained; TLC [methylene
 chloride/methanol 10:1]: R.sub.f =0.28; melting point=208.degree. C.
 (decomposition).
 Purification of the end product as described in Example 3.31 gives yellow
 crystals (155.8 mg, 88%); TLC [methanol]: R.sub.f =0.47; melting
 point=120.degree. C. (decomposition).
 EXAMPLE 3.33
 N-{N.sup..epsilon.
 -[O-(3-O-Carboxymethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-th
 iocarbonyl]-lysyl-D-alanyl}-batracyline, sodium salt
 Educt:
 carbohydrate 1.43 (77.3 mg, 0.22 mmol)
 Purification of the intermediate stage as described in Example 3.31.a;
 yellow crystals (192 mg, 90%) are obtained; TLC [ethanol/methanol 1:1]:
 R.sub.f =0.05; melting point=211-213.degree. C. (decomposition).
 Purification of the end product as described in Example 3.31 gives yellow
 crystals (110.6 mg, 66%); TLC [methanol]: R.sub.f =0.33; melting
 point=233-235.degree. C. (decomposition).
 EXAMPLE 3.34
 N-{N.sup..epsilon.
 -[O-(3-O-Carbamoylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-
 thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Educt:
 carbohydrate 1.44 (72.2 mg, 0.22 mmol)
 Purification of the intermediate stage as described in Example 3.31.a;
 yellow crystals (159.2 mg, 76%) are obtained; TLC [methylene
 chloride/methanol 10:1]: R.sub.f =0.04; melting point=177.degree. C.
 (decomposition).
 Purification of the end product as described in Example 3.31 gives yellow
 crystals (125.1 mg, 76%); TLC [methanol]: R.sub.f =0.48; melting
 point=106.degree. C. (decomposition).
 EXAMPLES 4.1-4.12
 General Formula
 ##STR96##
 EXAMPLE 4.1
 4.1.a) N-{N.sup..alpha.
 -[O-(.beta.-L-Fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-N.sup..epsilon.
 -(fluorenyl-9-methoxycarbonyl)-lysyl-D-alanyl}-batracyline
 140 mg (0.55 mmol) of p-aminophenyl .beta.-L-fucoside are first converted
 into the isothiocyanate in accordance with the instructions in Example
 3.1.a and the product is then coupled with 430 mg (0.55 mmol) of
 N-[N.sup..epsilon.
 -(fluorenyl-9-methoxycarbonyl)-lysyl-D-alanyl]-batracyline
 trifluoroacetate (Example 2.5) in the presence of 375 .mu.l of
 ethyldiisopropylamine. After precipitation from methanol/methylene
 chloride, the crude product is purified by flash chromatography
 (acetonitrile/water 10:1). After the residue has been stirred with ether,
 358 mg (67%) of the target product are obtained. [TLC: acetonitrile/water
 10:1 R.sub.f =0.48].
 4.1)
 N-{N.alpha.-[O-(.beta.-L-Fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysy
 l-D-alanyl}-batracyline
 356 mg (0.37 mmol) of the compound from Example 4.1.a are dissolved in 10
 ml of dimethylformamide and 5 ml of piperidine and the solution is stirred
 at 20.degree. C. for 1 hour. It is concentrated and the residue is
 chromatographed with methylene chloride/methanol/ammonia (17%) 15:6:0.6.
 The target product is obtained in a 46% yield. [TLC: methylene
 chloride/methanol/ammonia (17%) 15:4:0.5 R.sub.f =0.11].
 The following glycoconjugates are prepared analogously to Examples 4.1 from
 the partly protected peptide conjugate 2.5:
 EXAMPLE 4.2
 N-{N.sup..alpha.
 -[O-(3-O-Carboxymethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbony
 l]-lysyl-D-alanyl}-batracyline, sodium salt
 Educt:
 carbohydrate from Example 1.10
 Chromatographic purification of the intermediate stage with methylene
 chloride/methanol/ammonia (17%) 15:3:0.3; later in the same system
 15:4:0.5.
 Purification of the end product at the betaine stage by stirring with
 water; subsequent conversion into the sodium salt with 0.1N sodium
 hydroxide solution and freeze drying from dioxane/water. Yield: 65%;
 melting point: 220.degree. C.
 EXAMPLE 4.3
 N-{N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysy
 l-D-alanyl}-batracyline
 Educt:
 carbohydrate from Example 1.2
 Purification of the intermediate stage by precipitation with methylene
 chloride with ether; purification of the end product by several
 precipitations from dimethylformamide with ether. Yield: 88% [TLC:
 acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.28].
 EXAMPLE 4.4
 N-{N.sup..alpha.
 -[O-(4-O-Methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysy
 l-D-alanyl}-batracyline
 Educt:
 carbohydrate from Example 1.4
 Purification of the intermediate stage by several precipitations from
 methylene chloride/methanol 1:1 with ether; column chromatography
 purification of the end product [methylene chloride/methanol/ammonia (17%)
 15:8:0.8], precipitation from methylene chloride/methanol 1:1 with ether.
 Yield: 74% [TLC: methylene chloride/methanol/ammonia (17%) 10:10:1 R.sub.f
 =0.19].
 EXAMPLE 4.5
 N-{N.sup..alpha.
 -[O-(3,4-Di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thio
 carbonyl]-lysyl-D-alanyl}-batracyline
 4.5.a) N-{N.sup..alpha.
 -[O-(3,4-Di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thio
 carbonyl-N.sup..epsilon.
 -(fluorenyl-9-methoxycarbonyl)]-lysyl-D-alanyl}-batracyline
 Thiophosgene (33.5 ml, 0.44 mmol) is added to a solution of compound 1.31
 (79 mg, 0.22 mmol) in dioxane/water 1:1 (10 ml). After 10 minutes, the
 mixture is concentrated in vacuo and the residue is dried under an oil
 pump vacuum for 1 hour. The isothiocyanate obtained is dissolved in
 absolute dimethylformamide (10 ml), and compound 2.6 (157 mg, 0.2 mmol)
 and ethyldiisopropylamine (0.5 ml) are added. The mixture is stirred at
 room temperature for 16 hours and then concentrated in vacuo. Several
 reprecipitations of the residue from methylene chloride/methanol 1:1 by
 means of diethyl ether and final washing with a little ice-cold methanol
 gives yellow crystals (198 mg, 98%); TLC [methylene chloride/methanol
 10:1]: R.sub.f =0.23; melting point=175.degree. C.
 4.5) N-{N.sup..alpha.
 -[O-(3,4-Di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thio
 carbonyl]-lysyl-D-alanyl}-batracyline
 The fluorenyl-9-methoxycarbonyl group is split off from compound 4.5.a
 (172.1 mg, 0.17 mmol) as described in Example 2.4. After concentration in
 vacuo and dissolving in methanol/methylene chloride 1:1, the product is
 precipitated by addition of diethyl ether. Yellow crystals (114.5 mg, 85%)
 are obtained; TLC [methylene chloride/methanol 1:1]: R.sub.f =0.16;
 melting point=206.degree. C. (decomposition).
 The following glycoconjugates are prepared analogously to Example 4.5.a and
 4.5 from peptide conjugate 2.6 (in each case 157 mg, 0.2 mmol):
 EXAMPLE 4.6
 N-{N.sup..alpha.
 -[O-(.beta.-D-Galactopyranosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl-
 D-alanyl}-batracyline
 Educt:
 carbohydrate 1.23 (59.7 mg, 0.22 mmol)
 Purification of the intermediate stage as described in Example 4.5.a;
 yellow crystals (185.8 mg, 94%) are obtained; TLC [methylene
 chloride/methanol 10:1]: R.sub.f =0.09; melting point=182.degree. C.
 (decomposition).
 Purification of the end product as described in Example 4.5 gives yellow
 crystals (134.3 mg, 88%); TLC [methylene chloride/methanol 1:1]: R.sub.f
 =0.04; melting point=221.degree. C. (decomposition).
 EXAMPLE 4.7
 N-{N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thiocarbo
 nyl]-lysyl-D-alanyl}-batracyline
 Educt:
 carbohydrate 1.25 (62.8 mg, 0.22 mmol)
 Purification of the intermediate stage as described in Example 4.5.a;
 yellow crystals (193.5 mg, 97%) are obtained; TLC [methylene
 chloride/methanol 10:1]: R.sub.f =0.27; melting point=178.degree. C.
 (decomposition).
 Purification of the end product by flash chromatography [methylene
 chloride/methanol 2:1.fwdarw.1:1] gives yellow crystals (130.5 mg, 84%);
 TLC [methylene chloride/methanol 1:1]: R.sub.f =0.09; melting
 point=206.degree. C. (decomposition).
 EXAMPLE 4.8
 N-{N.sup..alpha.
 -[O-(3-O-Methoxycarbonylmethyl-[-D-galactopyranosyl)-4-hydroxy-phenylamino
 -thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Educt:
 carbohydrate 1.42 (75.5 mg, 0.22 mmol)
 Purification of the intermediate stage as described in Example 4.5.a;
 yellow crystals (209.8 mg, 99%) are obtained; TLC [methylene
 chloride/methanol 10:1]: R.sub.f =0.32; melting point=235.degree. C.
 (decomposition).
 Purification of the end product as described in Example 4.5 gives yellow
 crystals (164.3 mg, 99%); TLC [methylene chloride/methanol 1:1]: R.sub.f
 =0.05; melting point=217.degree. C. (decomposition).
 EXAMPLE 4.9
 N-{N.sup..alpha.
 -[O-(3-O-Carboxymethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-th
 iocarbonyl]-lysyl-D-alanyl}-batracyline, sodium salt
 Educt:
 carbohydrate 1.43 (77.3 mg, 0.22 mmol)
 Purification of the intermediate stage as described in Example 4.5.a;
 yellow crystals (210.3 mg, 99%) are obtained; TLC [methylene
 chloride/methanol 10:1]: R.sub.f =0.02; melting point=185.degree. C.
 After purification of the product as described in Example 4.5, the residue
 is suspended in water (10 ml), and 0.05 N sodium hydroxide solution is
 added dropwise to the suspension, while stirring, until a clear solution
 forms (pH&lt;10). Lyophilization of the filtered solution gives a yellow
 amorphous solid (150.8 mg, 90%); TLC [methylene chloride/methanol 1:1]:
 R.sub.f =0.04.
 EXAMPLE 4.10
 N-{N.sup..alpha.
 -[-(3-O-Carbamoylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-t
 hiocarbonyl]-lysyl-D-alanyl}-batracyline
 Educt:
 carbohydrate 1.44 (72.2 mg, 0.22 mmol)
 Purification of the intermediate stage as described in Example 4.5.a;
 yellow crystals (152.7 mg, 73%) are obtained; TLC [methylene
 chloride/methanol 10:1]: R.sub.f =0.11; melting point=229.degree. C.
 (decomposition).
 After purification of the product as described in Example 4.5, the residue
 is suspended in water/dioxane 1:1 (20 ml). Lyophilization of the filtered
 solution gives a yellow amorphous solid (98.4 mg, 61%); TLC [methylene
 chloride/methanol 1:1]: R.sub.f =0.10; [.alpha.].sup.20 =+44.9.degree.
 (c=0.2/H.sub.2 O).
 EXAMPLE 4.11
 N-{N-[O-(.alpha.-D-Mannopyranosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysy
 l-D-alanyl}-batracyline
 Educt:
 carbohydrate 1.39 (59.7 mg, 0.22 mmol)
 Purification of the intermediate stage as described in Example 4.5.a;
 yellow crystals (179.6 mg, 91%) are obtained; TLC [methylene
 chloride/methanol 10:1]: R.sub.f =0.07; melting point=176.degree. C.
 (decomposition).
 Purification of the end product as described in Example 4.5 gives yellow
 crystals (137.5 mg, 90%); TLC [methylene chloride/methanol 1:1]: R.sub.f
 =0.09; melting point=213.degree. C. (decomposition).
 EXAMPLE 4.12
 N-{N.sup..alpha.
 -[O-(3-O-Methyl-.alpha.-D-mannopyranosyl)-4-hydroxy-phenylamino-thiocarbon
 yl]-lysyl-D-alanyl}-batracyline
 Educt:
 carbohydrate 1.40 (62.8 mg, 0.22 mmol)
 Purification of the intermediate stage as described in Example 4.5.a;
 yellow crystals (94.2 mg, 48%) are obtained; TLC [methylene
 chloride/methanol 10:1]: R.sub.f =0.13; melting point=173.degree. C.
 (decomposition).
 Purification of the end product as described in Example 4.5 gives yellow
 crystals (66.6 mg, 43%); TLC [methylene chloride/methanol 1:1]: R.sub.f
 =0.07; melting point=215.degree. C. (decomposition).
 EXAMPLES 5.1-5.23
 General Formula
 ##STR97##
 EXAMPLE 5.1
 N-{N.sup..alpha.
 -[O-(3-O-Carboxymethyl-.beta.-L-fucosyl)-4-hydroxyphenylaminothiocarbonyl]
 -N.sup..epsilon.
 -[O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxyphenylaminothiocarbonyl]-lysyl-
 D-alanyl}-batracyline
 30 .mu.l (0.18 mmol) of thiophosgene are added to 50 mg (0.16 mmol) of
 p-aminophenyl 3-O-carboxymethyl-.beta.-L-fucoside (Example 1.10) in 10 ml
 of dioxane/water 1:1, while stirring. After 10 minutes, the mixture is
 concentrated and the residue is dried under a high vacuum for 1 hour. The
 isothiocyanate obtained is then coupled in absolute dimethylformamide with
 109 mg (0.144 mmol) of the conjugate from Example 3.4 in the presence of
 82 .mu.l of ethyldiisopropylamine. The mixture is concentrated and the
 residue is purified by flash chromatography [methylene
 chloride/methanol/ammonia (17%) 15:4:0.5]. The substance obtained after
 concentration is lyophilized from water. Yield: 89 mg (56%). [TLC:
 methylene chloride/methanol/ammonia (17%) 15:6:0.6 R.sub.f =0.22].
 The following conjugates with mixed substituents are prepared analogously
 to Example 5.1:
 EXAMPLE 5.2
 N-{N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-L-fucosyl)-4-hydroxyphenylamino-thiocarbonyl]-N.
 sup..epsilon.
 -[O-(3-O-carboxymethyl-.beta.-L-fucosyl)-4-hydroxyphenylamino-thiocarbonyl
 ]-lysyl-D-alanyl}-batracyline
 Educts:
 carbohydrate from Example 1.2, conjugate from Example 3.10
 Purification by precipitation of the crude product from methanol with
 ether. Yield: 78% [TLC: acetonitrile/water/glacial acetic acid 5:1:0.2
 R.sub.f =0.45].
 EXAMPLE 5.3
 N-{N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-L-fucosyl)-4-hydroxyphenylamino-thiocarbonyl]-N.
 sup..epsilon.-[
 4-hydroxyphenylamino-thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Educts:
 conjugate from Example 4.3, 4-hydroxy-aniline
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:2:0.21; yield: 60% [TLC: methylene chloride/methanol/ammonia
 (17%) 15:2:0.2 R.sub.f =0.31].
 EXAMPLE 5.4
 N-{N.sup..alpha.
 -[O-(3-O-Carboxymethyl-.beta.-L-fucosyl)-4-hydroxyphenylamino-thiocarbonyl
 ]-N.sup..epsilon.
 -[4-hydroxyphenylamino-thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Educts:
 conjugate from Example 4.2, 4-hydroxy-aniline
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:4:0.5]. The residue is then stirred with methanol/ether. Yield:
 55% [TLC: methylene chloride/methanol/ammonia (17%) 15:6:0.6 R.sub.f
 =0.3].
 EXAMPLE 5.5
 N-{N.sup..alpha.
 -[O-(4-O-Methyl-.beta.-L-fucosyl)-4-hydroxyphenylamino-thiocarbonyl]-N.
 sup..epsilon.
 -[4-hydroxyphenylamino-thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Educts:
 conjugate from Example 4.4, 4-hydroxy-aniline
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:2:0.2]. The residue is then precipitated from methanol/methylene
 chloride with ether. Yield: 49% melting point: 128.degree. C. [TLC:
 methylene chloride/methanol/ammonia (17%) 15:2:0.2 R.sub.f =0.26].
 EXAMPLE 5.6
 N-{N.sup..alpha. -[4-Hydroxyphenylamino-thiocarbonyl]-N.sup..epsilon.
 -[O-(4-O-methyl-.beta.-L-fucosyl)-4-hydroxyphenylamino-thiocarbonyl]-lysyl
 -D-alanyl}-batracyline
 Educts:
 conjugate from Example 3.11, 4-hydroxy-aniline
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:2:0.2]. The residue is then lyophilized from water/dioxane.
 Yield: 50% [TLC: methylene chloride/methanol/ammonia (17%) 15:2:0.2
 R.sub.f =0.291.
 EXAMPLE 5.7
 N-{N.sup..alpha. -[4-Hydroxyphenylamino-thiocarbonyl]-N.sup..epsilon.
 -[O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxyphenylamino-thiocarbonyl]-lysyl
 -D-alanyl}-batracyline
 Educts:
 conjugate from Example 3.4, 4-hydroxy-aniline
 Precipitate the residue from methanol with ether. Yield: 76% [TLC:
 methylene chloride/methanol/ammonia (17%) 15:2:0.2 R.sub.f =0.26].
 EXAMPLE 5.8
 N-{N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-L-fucosyl)-4-hydroxyphenylamino-thiocarbonyl]-N.
 sup..epsilon.
 -[4-hydroxyethylamino-2-[O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxyphenylam
 ino]triazin-6-yl]]-lysyl-D-alanyl}-batracyline
 Educts:
 conjugate from Example 8.10, carbohydrate from Example 1.2
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:2:0.2]. Yield: 9% FAB-MS: m/z=1165=M+1 [TLC: methylene
 chloride/methanol/ammonia (17%) 15:3:0.3 R.sub.f =0.27].
 EXAMPLE 5.9
 N-{N.sup..alpha.
 -[O-(3-O-Carboxymethyl-.beta.-L-fucosyl)-4-hydroxyphenylaminothiocarbonyl]
 -N.sup..alpha. -[acetyl]-lysyl-D-alanyl batracyline
 Educts:
 N-[N.sup..epsilon. -(acetyl)-lysyl-D-alanyl]-batracyline, carbohydrate from
 Example 1.10
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:2:0.2; later in the same system 15:4:0.5]. The residue is then
 freeze dried from water. Yield: 46% [TLC: acetonitrile/water/glacial
 acetic acid 5:1:0.2 R.sub.f =0.31].
 EXAMPLE 5.10
 N-{N-[O-(4-O-Methyl-.beta.-L-fucosyl)-4-hydroxyphenylamino-thiocarbonyl]-N.
 sup..epsilon. -[acetyl]-lysyl-D-alanyl}-batracyline
 10 .mu.l of acetic anhydride are added to 51 mg (0.067 mmol) of the
 conjugate from Example 4.4 in 5 ml of dimethylformamide and the mixture is
 stirred at room temperature for 30 minutes. It is concentrated and the
 residue is precipitated from methanol with ether. Yield: 46 mg (86%) [TLC:
 acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.6].
 EXAMPLE 5.11
 N-{N.sup..alpha.
 -[O-(.beta.-L-Fucosyl)-4-hydroxyphenylamino-thiocarbonyl]-N.sup..epsilon.
 -[succinyl]-lysyl-D-alanyl}-batracyline, sodium salt
 3 mg of succinic anhydride are added to 20 mg (0.027 mmol) of the conjugate
 from Example 4.1 in 2 ml of dimethylformamide and the mixture is stirred
 at room temperature for 6 hours. It is concentrated and the residue is
 precipitated from methanol with ether. The residue is taken up in water,
 and 27 .mu.l of a 0.1N sodium hydroxide solution are added. Yield: 20 mg
 (86%); [TLC: methylene chloride/methanol/glacial acetic acid 80:20:2
 R.sub.f =0.2].
 EXAMPLE 5.12
 N-{N.sup..alpha.
 -[O-(3-O-Methoxycarbonylmethyl-.beta.-D-galactopyranosyl)-4-hydroxyphenyla
 mino-thiocarbonyl]-N.sup..epsilon.
 -[O-(3,4-di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thio
 carbonyl]-lysyl-D-alanyl}-batracyline
 Carbohydrate 1.42 (37.7 mg, 0.11 mmol) is reacted with peptide conjugate
 3.31 (79 mg, 0.1 mmol) as described in Example 3.31.a. After concentration
 in vacuo and flash chromatography [methylene chloride/methanol
 20:1.fwdarw.10:1], yellow crystals (52.9 mg, 45%) are obtained; TLC
 [methylene chloride/methanol 10:1]: R.sub.f =0.14; melting
 point=178.degree. C. (decomposition).
 EXAMPLE 5.13
 N-{N.sup..alpha.
 -[-(3-O-Carboxymethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylaminothio
 carbonyl]-N.sup..epsilon.
 -[O-(3,4-di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thio
 carbonyl]-lysyl-D-alanyl}-batracyline, sodium salt
 Carbohydrate 1.43 (38.6 mg, 0.11 mmol) is reacted with peptide conjugate
 3.31 (79 mg, 0.1 mmol) as described in Example 3.31.a. After concentration
 in vacuo and dissolving in methanol/methylene chloride 1:1, the product is
 precipitated by addition of diethyl ether. The residue is suspended in
 water (10 ml), and 0.05 N sodium hydroxide solution is added dropwise to
 the suspension, while stirring, until a clear solution forms (pH&lt;10).
 Lyophilization of the filtered solution gives a yellow amorphous solid
 (87.9 mg, 74%); TLC [ethanol]: R.sub.f =0.17; [.alpha.].sup.20
 =+56.0.degree. (c=0.1/H.sub.2 O).
 EXAMPLE 5.14
 N-{N.sup..alpha.
 -[O-(3-O-Carboxymethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-th
 iocarbonyl]-N.sup..epsilon.
 -[O-(3,4-di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thio
 carbonyl]-lysyl-D-alanyl}-batracyline
 Carbohydrate 1.44 (36.1 mg, 0.11 mmol) is reacted with peptide conjugate
 3.31 (79 mg, 0.1 mmol) as described in Example 3.31.a. After concentration
 in vacuo and dissolving in methanol/methylene chloride 1:1, the product is
 precipitated by addition of diethyl ether. Yellow crystals (45.9 mg, 39%)
 are obtained; TLC [ethanol]: R.sub.f =0.38; melting point=219.degree. C.
 (decomposition).
 EXAMPLE 5.15
 N-{N.sup..alpha.
 -[O-(3,4-Di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thio
 carbonyl]-N.sup..epsilon.
 -[O-(3-O-(piperidyl-N)-carbonylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy
 -phenylamino-thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Carbohydrate 1.31 (39.5 mg, 0.11 mmol) is reacted with peptide conjugate
 3.32 (88.7 mg, 0.1 mmol) as described in Example 3.31.a. After
 concentration in vacuo and flash chromatography [methylene
 chloride/methanol 20:1.fwdarw.10:1], yellow crystals (38.8 mg, 32%) are
 obtained; TLC [methylene chloride/methanol 5:1]: R.sub.f =0.79; melting
 point=205.degree. C. (decomposition).
 EXAMPLE 5.16
 N-{N.sup..alpha.
 -[O-(3-O-Carboxymethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-th
 iocarbonyl]-N.sup..epsilon.
 -[O-(3-O-(piperidyl-N)-carbonylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy
 -phenylamino-thiocarbonyl]-lysyl-D-alanyl}-batracyline, sodium salt
 Carbohydrate 1.43 (38.6 mg, 0.11 mmol) is reacted with peptide conjugate
 3.32 (88.7 mg, 0.1 mmol) as described in Example 3.31.a. After
 concentration in vacuo and dissolving in methanol/methylene chloride 1:1,
 the product is precipitated by addition of diethyl ether. The residue is
 suspended in water (10 ml), and 0.05N sodium hydroxide solution is added
 dropwise to the suspension, while stirring, until a clear solution forms
 (pH&lt;10). Lyophilization of the filtered solution gives a yellow amorphous
 solid (90.3 mg, 71%); TLC [ethanol]: R.sub.f =0.05; [.alpha.].sup.20
 =+39.0.degree. (c=0.1/H.sub.2 O).
 EXAMPLE 5.17
 N-{N.sup..alpha.
 -[O-(3-O-Carbamoylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-
 thiocarbonyl]-N.sup..epsilon.
 -[O-(3-O-(piperidyl-N)-carbonylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy
 -phenylamino-thiocarbonyl-lysyl-D-alanyl}-batracyline
 Carbohydrate 1.44 (36.1 mg, 0.11 mmol) is reacted with peptide conjugate
 3.32 (88.7 mg, 0.1 mmol) as described in Example 3.31.a. After
 concentration in vacuo and dissolving in methanol/methylene chloride 1:1,
 the product is precipitated by addition of diethyl ether. Yellow crystals
 (44.8 mg, 36%) are obtained; TLC [ethanol]: R.sub.f =0.06; melting
 point=223.degree. C. (decomposition).
 EXAMPLE 5.18
 N-{N-.sup..alpha.
 [O-(3,4-Di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thioc
 arbonyl]-N.sup..epsilon.
 -[O-(3-O-carboxymethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-th
 iocarbonyl]-lysyl-D-alanyl}-batracyline, sodium salt
 Carbohydrate 1.31 (39.5 mg, 0.11 mmol) is reacted with peptide conjugate
 3.33 (84.2 mg, 0.1 mmol) as described in Example 3.31.a. After
 concentration in vacuo, methanol/methylene chloride 1:1 (20 ml) is added
 to the residue and the product is precipitated by addition of diethyl
 ether. The residue is suspended in water (10 ml), and 0.05N sodium
 hydroxide solution is added dropwise to the suspension, while stirring,
 until a clear solution forms (pH&lt;10). Lyophilization of the filtered
 solution gives a yellow amorphous solid (80.7 mg, 68%); TLC [ethanol]:
 R.sub.f =0.09; [.alpha.].sup.20 =+35.0.degree. (c=0.1/H.sub.2 O).
 EXAMPLE 5.19
 N-{N.sup..alpha.
 -[O-(3-O-Methoxycarbonylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenyl
 amino-thiocarbonyl]-N.sup..epsilon.
 -[O-(3-O-carboxymethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-th
 iocarbonyl]-lysyl-D-alanyl}-batracyline, sodium salt
 Carbohydrate 1.42 (37.7 mg, 0.11 mmol) is reacted with peptide conjugate
 3.33 (84.2 mg, 0.1 mmol) as described in Example 3.31.a. After
 concentration in vacuo, methanol/methylene chloride 1:1 (20 ml) is added
 to the residue and the product is precipitated by addition of diethyl
 ether. The residue is suspended in water (10 ml), and 0.05N sodium
 hydroxide solution is added dropwise to the suspension, while stirring,
 until a clear solution forms (pH&lt;10). Lyophilization of the filtered
 solution gives a yellow amorphous solid (87.5 mg, 71%); TLC [ethanol]:
 R.sub.f =0.10; [.alpha.].sup.20 =+24.6.degree. (c=0.11/H.sub.2 O).
 EXAMPLE 5.20
 N-{N.sup..alpha.
 -[O-(3-O-Carbamoylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-
 thiocarbonyl]-N.sup..epsilon.
 -[O-(3-O-carboxymethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-th
 iocarbonyl]-lysyl-D-alanyl}-batracyline, sodium salt
 Carbohydrate 1.44 (36.1 mg, 0.11 mmol) is reacted with peptide conjugate
 3.33 (84.2 mg, 0.1 mmol) as described in Example 3.31.a. After
 concentration in vacuo, methanol/methylene chloride 1:1 (20 ml) is added
 to the residue and the product is precipitated by addition of diethyl
 ether. The residue is suspended in water (10 ml), and 0.05N sodium
 hydroxide solution is added dropwise to the suspension, while stirring,
 until a clear solution forms (pH&lt;10). Lyophilization of the filtered
 solution gives a yellow amorphous solid (78.6 mg, 65%); TLC [ethanol]:
 R.sub.f =0.11; [.alpha.].sup.20 =-44.0.degree. (c=0.13/H.sub.2 O).
 EXAMPLE 5.21
 N-{N.sup..alpha.
 -[O-(3,4-Di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thio
 carbonyl]-N.sup..epsilon.
 -[O-(3-O-carbamoylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-
 thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Carbohydrate 1.31 (39.5 mg, 0.11 mmol) is reacted with peptide conjugate
 3.34 (81.9 mg, 0.1 mmol) as described in Example 3.31.a. After
 concentration in vacuo and flash chromatography
 [ethanol.fwdarw.ethanol/methanol 2:1], yellow crystals (17.4 mg, 15%) are
 obtained; TLC [ethanol]: R.sub.f =0.20; melting point &gt;290.degree. C.
 (decomposition).
 EXAMPLE 5.22
 N-{N.sup..alpha.
 -[O-(3-O-Methoxycarbonylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenyl
 amino-thiocarbonyl]-N.sup..epsilon.
 -[O-(3-O-carbamoylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-
 thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Carbohydrate 1.42 (37.7 mg, 0.11 mmol) is reacted with peptide conjugate
 3.34 (81.9 mg, 0.1 mmol) as described in Example 3.31.a. After
 concentration in vacuo and dissolving in methanol/methylene chloride 1:1,
 the product is precipitated by addition of diethyl ether. Yellow crystals
 (72 mg, 60%) are obtained; TLC [ethanol]: R.sub.f =0.21; melting point
 222.degree. C. (decomposition).
 EXAMPLE 5.23
 N-{N.sup..alpha.
 -[O-(3-O-Carboxymethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-th
 iocarbonyl]-N.sup..epsilon.
 -[O-(3-O-carbamoylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-
 thiocarbonyl]-lysyl-D-alanyl}-batracyline, sodium salt
 Carbohydrate 1.43 (38.6 mg, 0.11 mmol) is reacted with peptide conjugate
 3.34 (81.9 mg, 0.1 mmol) as described in Example 3.31.a. After
 concentration in vacuo, and dissolving in methanol/methylene chloride 1:1,
 the product is precipitated by addition of diethyl ether. The residue is
 suspended in water (10 ml), and 0.05N sodium hydroxide solution is added
 dropwise to the suspension, while stirring, until a clear solution forms
 (pH&lt;10). Lyophilization of the filtered solution gives a yellow amorphous
 solid (78.2 mg, 65%); TLC [ethanol]: R.sub.f =0.07; [.alpha.].sup.20
 =+33.0.degree. (c=0.1/H.sub.2 O).
 EXAMPLES 6.1-6.89
 General Formula
 ##STR98##
 EXAMPLE 6.1
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(2-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-
 lysyl-D-alanyl}-batracyline
 Thiophosgene (30 .mu.l, 0.4 mmol) is added to a solution of compound 1.1
 (50 mg, 0.19 ml) in dioxane/water 1:1 (10 ml), while stirring. After 10
 minutes, the mixture is concentrated in vacuo and the residue is dried
 under an oil pump vacuum for 1 hour. The isothiocyanate obtained is
 dissolved in absolute dimethylformamide (10 ml), and compound 2.13 (61 mg,
 0.09 mmol) and ethyldiisopropylamine (0.5 ml) are added. The mixture is
 stirred at room temperature for 16 hours and then concentrated in vacuo
 and the residue is purified by flash chromatography [methylene
 chloride/methanol/ammonia (17%) 15:2:0.2]. The residue is precipitated
 from methanol with ether. 48 mg (50%) of the target product are obtained
 as yellow crystals.
 The following glycoconjugates are prepared analogously to Example 6.1 from
 the peptide conjugate in Example 2.13 or the L-alanyl isomer (Example
 2.2):
 EXAMPLE 6.2
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-
 lysyl-D-alanyl}-batracyline
 Educt:
 100 mg (0.38 mmol) of carbohydrate from Example 1.2
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:0.5:0.05; later 15:1:0.1 in the same system]; subsequent
 precipitation from methylene chloride/methanol/ether. Yield: 59%. Melting
 point 178.degree. C. (decomposition) [TLC: acetonitrile/water 10:1 R.sub.f
 =0.51].
 EXAMPLE 6.3
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(4-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-
 lysyl-D-alanyl}-batracyline
 Educt:
 115 mg (0.44 mmol) of carbohydrate from Example 1.4
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:2:0.2]; subsequent precipitation from methylene chloride/methanol
 (1:1)/ether. Yield: 58%. Melting point 176.degree. C. (decomposition)
 [TLC: acetonitrile/water 10:1 R.sub.f =0.52].
 EXAMPLE 6.4
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-
 lysyl-alanyl}-batracyline
 Educt:
 115 mg (0.44 mmol) of carbohydrate from Example 1.2
 Purification by precipitation from methylene chloride/methanol (1:
 1)/ether. Yield: 93%. Melting point 192.degree. C. (decomposition) [TLC:
 acetonitrile/water 10:1 R.sub.f =0.46].
 EXAMPLE 6.5
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.alpha.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]
 -lysyl-D-alanyl}-batracyline
 Educt:
 100 mg (0.38 mmol) of carbohydrate from Example 1.3
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:1:0.1]; precipitation from methylene chloride/methanol
 (1:1)/ether. Melting point: 178.degree. C. (decomposition); FAB-MS:
 m/z=1071=M+1.
 EXAMPLE 6.6
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-n-propyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl
 ]-lysyl-alanyl}-batracyline
 Educt:
 38 mg (0.127 mmol) of carbohydrate from Example 1.5
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:1:0.1]; precipitation from methylene chloride/methanol
 (1:1)/ether. Yield: 42%, melting point: 167-170.degree. C.
 (decomposition), [TLC: methylene chloride/methanol/ammonia (17%) R.sub.f
 =0.34].
 EXAMPLE 6.7
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-n-propyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl
 ]lysyl-D-alanyl}-batracyline
 Educt:
 40 mg (0.167 mmol) of carbohydrate from Example 1.6
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:2:0.2]; precipitation from methanol/ether. Yield: 81% [TLC:
 acetonitrile/water 10:1 R.sub.f =0.46].
 EXAMPLE 6.8
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3,4-dideoxy-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]
 -lysyl-D-alanyl}-batracyline
 Educt:
 41 mg (0.183 mmol) of carbohydrate from Example 1.7
 Purification by flash chromatography [methylene chloride/methanol 95:5];
 freeze drying from water/dioxane. Yield: 60% [TLC: methylene
 chloride/methanol 9:1 R.sub.f =0.22].
 EXAMPLE 6.9
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-hydroxyethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbon
 yl]-lysyl-D-alanyl}-batracyline
 Educt:
 75 mg (0.25 mmol) of carbohydrate from Example 1.12
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:2:0.2; later in the same system 15:4:0.5]. Precipitation from
 methanol/ether. Yield: 66%; [TLC: acetonitrile/water 10:1 R.sub.f =0.28].
 EXAMPLE 6.10
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(2-hydroxyethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbon
 yl]-lysyl-D-alanyl}-batracyline
 Educt:
 50 mg (0.167 mmol) of carbohydrate from Example 1.19
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:3:0.3]; precipitation from methanol/ether; freeze drying from
 water/dioxane. Yield: 72%; [TLC: acetonitrile/water/glacial acetic acid
 5:1:0.2 R.sub.f =0.39].
 EXAMPLE 6.11
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(2-O-carboxymethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocar
 bonyl]-lysyl-D-alanyl}-batracyline, di-sodium salt
 Educt:
 50 mg (0.16 mmol) of carbohydrate from Example 1.13
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:8:0.8; later in the same system 15:10:1]. Digest the residue with
 ether, subsequent freeze drying from water/dioxane. Conversion into the
 di-sodium salt with 2 equivalents of a 0.1N sodium hydroxide solution,
 subsequently freeze drying from water. Yield: 49% [TLC:
 acetonitrile/water/glacial acetic acid 5:1:0.5 R.sub.f =0.38]. MS-FAB:
 FAB.sup.- ; m/z=1157=M-2Na.sup.+ +H.sup.+.
 EXAMPLE 6.12
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carboxymethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocar
 bonyl]-lysyl-D-alanyl}-batracyline, di-sodium salt
 Educt:
 200 mg (0.64 mmol) of carbohydrate from Example 1.10
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:4:0.5; later in the same system 15:8:0.8; and finally 15:10:1].
 Digest the residue with ether, subsequently freeze drying from
 water/dioxane 1:1. Conversion into the di-sodium salt with 2 equivalents
 of a 0.1N sodium hydroxide solution, subsequently freeze drying from
 water. Yield: 59%; [TLC: methylene chloride/methanol/ammonia (17%) R.sub.f
 =0.1].
 EXAMPLE 6.13
 N-[N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carbamoylmethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thioc
 arbonyl]-lysyl-D-alanyl}-batracyline
 Educt:
 60 mg (0.19 mmol) of carbohydrate from Example 1.18
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:3:0.3]. Precipitate the residue from methylene chloride/methanol
 (1:1) with ether, filter off with suction and subsequently freeze drying
 from water/dioxane 1:1. Yield: 36% [TLC: acetonitrile/water/glacial acetic
 acid 5:1:0.2 R.sub.f =0.461. Melting point: 190.degree. (decomposition).
 EXAMPLE 6.14
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl-D-ala
 nyl}-batracyline
 Educt:
 100 mg (0.39 mmol) of p-aminophenyl .beta.-L-fucoside
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:2:0.2; later in the same system 15:4:0.5]. Precipitate the
 residue from dimethylformamide with ether, filter off with suction. Yield:
 48%; melting point: 195-198.degree. C.
 EXAMPLE 6.15
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(.alpha.-L-rhamnosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl-D-
 alanyl}-batracyline
 Educt:
 158 mg (0.61 mmol) of carbohydrate from Example 1.21
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:3:0.3; later in the same system 15:4:0.5]. Lyophilize the residue
 from water/dioxane. Yield: 87% [TLC: methylene chloride/methanol/ammonia
 (17%) 15:4:0.5 R.sub.f =0.25].
 EXAMPLE 6.16
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carboxymethyl-.alpha.-L-rhamnosyl)-4-hydroxy-phenylamino-thio
 carbonyl]-lysyl-D-alanyl}-batracyline, di-sodium salt
 Educt:
 200 mg (0.64 mmol) of carbohydrate from Example 1.22
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:4:0.5; later in the same system 15:8:0.8; and finally 15:10:1].
 Digest the residue with ether, subsequently freeze drying from
 water/dioxane 1:1.
 The following glycoconjugates which contain a completely deblocked lysine
 structural unit on the amino end are prepared analogously to Example 6.1
 from various peptide conjugates of batracyline:
 EXAMPLE 6.17
 N-{N.sup..alpha.,N.sup..epsilon. -Bis-[O
 -(3-O-carboxymethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-
 lysyl-glycyl}-batracyline, di-sodium salt
 Educts:
 32 mg (0.1 mmol) of carbohydrate from Example 1.10
 32 mg (0.045 mmol) of N-[lysyl-glycyl]-batracyline, di-trifluoroacetate
 (Example 2.9)
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:8:0.8; later in the same system 15:15:1.51. Precipitation from
 dimethylformamide/methanol (1:1) with ether, subsequent freeze drying from
 water/dioxane. Conversion into the di-sodium salt with 2 equivalents of a
 0.1N sodium hydroxide solution, subsequently freeze drying from water.
 Yield: 25%; [TLC: methylene chloride/methanol/ammonia (17%) 15:8:0.8
 R.sub.f =0.19]. FAB-MS: m/z=1189=M+1.
 EXAMPLE 6.18
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-
 lysyl-glycyl}-batracyline
 Educts:
 60 mg (0.22 mmol) of carbohydrate from Example 1.2
 66 mg (0.1 mmol) of N-[lysyl-glycyl]-batracyline, di-trifluoroacetate
 (Example 2.9)
 Purification by flash chromatography [methylene chloride/methanol/glacial
 acetic acid 90:10:1]; precipitation from methanol with ether, subsequently
 freeze drying from water/dioxane. Yield: 68% [TLC: methylene
 chloride/methanol/glacial acetic acid 80:20:2 R.sub.f =0.62].
 EXAMPLE 6.19
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl-lysyl
 }-batracyline
 6.19.a) N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl-N.
 sup..epsilon. -(fluorenyl-9-methoxycarbonyl)-lysyl}-batracyline
 Educts:
 297 mg (1 mmol) of p-aminophenyl .beta.-L-fucoside
 66 mg (0.1 mmol) of N-[lysyl-N.sup..epsilon.
 -(fluorenyl-9-methoxycarbonyl)-lysyl]-batracyline, di-trifluoroacetate
 (Example 2.15)
 206 .mu.l of ethyldiisopropylamine
 Purification by two precipitations from methanol/methylene chloride (1:1)
 with ether, washing of the filter residue with ether. Yield: 89% [TLC:
 methylene chloride/methanol/ammonia (17%) 15:4:0.5 R.sub.f =0.31].
 6.19) N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl-lysyl
 }-batracyline
 515 mg (0.39 mmol) of the compound from Example 6.19.a are dissolved in 5
 ml of dimethylformamide and 5 ml of piperidine and the solution is stirred
 at 20.degree. C. for 30 minutes. The batch is concentrated and the residue
 is digested with ether. The mixture is filtered with suction and the
 filter residue is taken up in dimethylformamide. After precipitation with
 ether and rinsing off the filter residue, 335 mg (78%) of crystalline
 target product remain. FAB-MS: m/z=1100=M+1.
 EXAMPLE 6.20
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-
 lysyl-diaminopropionyl}-batracyline
 6.20.a) N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-1O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-
 lysyl-N.sup..beta. -(fluorenyl-9-methoxycarbonyl)-diaminopropionyl
 }-batracyline
 Synthesis analogous to Example 6.19:
 Educts:
 60 mg (0.22 mmol) of carbohydrate from Example 1.2
 100 mg (0.1 1 mmol) of N-[lysyl-N.sup..beta.
 -(fluorenyl-9-methoxycarbonyl)-diamino-propionyl]-batracyline,
 di-trifluoroacetate (Example 2.16)
 76 .mu.l of ethyldiisopropylamine
 Purification by two precipitations from methanol with ether, washing of the
 filter residue with ether. Yield: 105 mg (73%).
 6.20) N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-
 lysyl-diaminopropionyl}-batracyline
 103 mg (0.079 mmol) of the compound from Example 6.20.a are deblocked with
 piperidine analogously to Example 6.19. Purification by flash
 chromatography (methylene chloride/methanol/ammonia (17%) 15:3:0.3; later
 in the same system 15:6:0.6). Freeze drying from water/dioxane. Yield:
 21%; [TLC: acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.32].
 EXAMPLE 6.21
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carboxymethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocar
 bonyl]-lysyl-diaminopropionyl}-batracyline, di-sodium salt
 This compound was prepared analogously to Example 6.20 via 2 stages,
 starting from the carbohydrate from Example 1.10 and the peptide conjugate
 from Example 2.16. Chromatographic purification can be omitted since
 by-products can be removed by digestion with methanol and ether. The
 product is then converted into the di-sodium salt with 2 equivalents of a
 0.1N sodium hydroxide solution. Yield: 66% over 2 stages. [TLC:
 acetonitrile/water/glacial acetic acid 10:3:1.5 R.sub.f =0.3].
 EXAMPLE 6.22
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-
 lysyl-seryl}-batracyline
 Educt:
 60 mg (0.22 mmol) of carbohydrate from Example 1.2
 76 mg (0.11 mmol) of N-[lysyl-seryl]-batracyline, di-trifluoroacetate
 (Example 2.10)
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:2:0.2]; precipitation from methylene chloride/methanol/ether.
 Yield: 26%. [TLC: acetonitrile/water 10:1 R.sub.f =0.39].
 EXAMPLE 6.23
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-
 lysyl-D-seryl}-batracyline
 Educt:
 60 mg (0.22 mmol) of carbohydrate from Example 1.2
 69 mg (0.11 mmol) of N-[lysyl-D-seryl]-batracyline, di-hydrobromide
 (Example 2.11)
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:2:0.2]; freeze drying from dioxane/water. Yield: 29%. [TLC:
 acetonitrile/water 10:1 R.sub.f =0.36].
 EXAMPLE 6.24
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-
 lysyl}-batracyline
 Educt:
 80 mg (0.3 mmol) of carbohydrate from Example 1.2
 53 mg (0.14 mmol) of N-[lysyl]-batracyline (Example 2.17)
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:1:0.1; later in the same system 15:2:0.2]; precipitation from
 methanol/ether. Yield: 26%. [TLC: methylene chloride/methanol/ammonia
 (17%) 15:2:0.2 R.sub.f =0.22].
 EXAMPLE 6.25
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carboxymethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocar
 bonyl]-lysyl}-batracyline
 Educt:
 60 mg (0.19 mmol) of carbohydrate from Example 1.10
 24 mg (0.063 mmol) of N-[lysyl]-batracyline (Example 2.17)
 Purification by flash chromatography [methylene chloride/methanol/ammonia
 (17%) 15:2:0.2]; later in the same system 15:4:0.5; freeze drying from
 water. Yield: 26%. [TLC: acetonitrile/water/glacial acetic acid 5:1:0.2
 R.sub.f =0.25].
 EXAMPLE 6.26
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3,4-di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-
 thiocarbonyl]-lysyl}-batracyline
 Thiophosgene (33.5 .mu.l, 0.44 mmol) is added to a solution of compound
 1.31 (79 mg, 0.22 mmol) in dioxane/water 1:1 (10 ml), while stirring.
 After 10 minutes, the mixture is concentrated in vacuo and the residue is
 dried under an oil pump vacuum for 1 hour. The isothiocyanate obtained is
 dissolved in absolute dimethylformamide (10 ml), and compound 2.17 (37.7
 mg, 0.1 mmol) and ethyldiisopropylamine (0.5 ml) are added. The mixture is
 stirred at room temperature for 16 hours and then concentrated in vacuo
 and the residue is purified by flash chromatography [methylene
 chloride/methanol 30:1.fwdarw.20:1.fwdarw.10.1]. Yellow crystals (56.7 mg,
 53%) are obtained; TLC [ethyl acetate/ethanol 2:1]: R.sub.f =0.72; melting
 point=125.degree. C. (decomposition).
 EXAMPLE 6.27
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methoxycarbonylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-ph
 enylamino-thiocarbonyl]-lysyl}-batracyline
 Compound 1.42 (75.5 mg, 0.22 mmol) is reacted with peptide conjugate 2.17
 (37.7 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 30:1.fwdarw.20:1.fwdarw.10.1]
 gives yellow crystals (51.1 mg, 44%); TLC [ethanol]: R.sub.f =0.80;
 melting point=176.degree. C. (decomposition).
 EXAMPLE 6.28
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carboxymethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamin
 o-thiocarbonyl]-lysyl}-batracyline, di-sodium salt
 Compound 1.43 (77.3 mg, 0.22 mmol) is reacted with peptide conjugate 2.17
 (37.7 mg, 0.1 mmol) as described in Example 6.26. Purification by
 reprecipitation from methanol/methylene chloride 1:1 with diethyl ether
 gives yellow crystals (53 mg, 47 %); TLC [methanol]; R.sub.f =0.75;
 melting point=&gt;260.degree. C. (decomposition).
 EXAMPLE 6.29
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carbamoylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylam
 ino-thiocarbonyl]-lysyl}-batracyline
 Compound 1.44 (72.2 mg, 0.22 mmol) is reacted with peptide conjugate 2.17
 (37.7 mg, 0.1 mmol) as described in Example 6.26. Purification by
 reprecipitation from methanol/methylene chloride 1:1 with diethyl ether
 gives yellow crystals (55.6 mg, 48%); TLC [ethanol]: R.sub.f =0.09;
 melting point=206.degree. C. (decomposition).
 EXAMPLE 6.30
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thioc
 arbonyl]-lysyl-seryl}-batracyline
 Compound 1.25 (62.8 mg, 0.22 mmol) is reacted with peptide conjugate 2.10
 (69.3 mg, 0.1 mmol) as described in Example 6.26. After concentration in
 vacuo, the residue is taken up in methylene chloride/methanol 1:1 (10 ml)
 and the product is precipitated by addition of diethyl ether (15 ml) and
 washed with a little ice-cold methanol. Yellow crystals (46 mg, 41%) are
 obtained; TLC [ethyl acetate/ethanol 2:11: R.sub.f =0.12; melting
 point=190-191.degree. C.
 EXAMPLE 6.31
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl
 -seryl}-batracyline
 p-Aminophenyl .beta.-L-fucopyranoside (56.2 mg, 0.22 mmol) is reacted with
 peptide conjugate 2.10 (69.3 mg, 0.1 mmol) as described in Example 6.26.
 Purification by flash chromatography [ethyl acetate.fwdarw.ethanol] and
 reprecipitation from methanol/methylene chloride 1:1 with diethyl ether
 give yellow crystals (73.8 mg, 70%); TLC [ethanol]: R.sub.f =0.15; melting
 point=123.degree. C.
 EXAMPLE 6.32
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3,4-di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-
 thiocarbonyl]-lysyl-seryl}-batracyline
 Compound 1.31 (79 mg, 0.22 mmol) is reacted with peptide conjugate 2.10
 (69.3 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [ethyl acetate.fwdarw.ethyl acetate/ethanol 7:1] gives
 yellow crystals (43.8 mg, 38%); TLC [ethyl acetate/ethanol 2:1]: R.sub.f
 =0.31; melting point=176.degree. C.
 EXAMPLE 6.33
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[-(3-O-methoxycarbonylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phe
 nylamino-thiocarbonyl]-lysyl-seryl}-batracyline
 Compound 1.42 (75.5 mg, 0.22 mmol) is reacted with peptide conjugate 2.10
 (69.3 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [ethyl acetate.fwdarw.ethyl acetate/ethanol 3:1] gives
 yellow crystals (46.2 mg, 37%); TLC [ethyl acetate/ethanol 2:1]: R.sub.f
 =0.12; melting point=161.degree. C.
 EXAMPLE 6.34
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carboxymethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamin
 o-thiocarbonyl]-lysyl-seryl}-batracyline, di-sodium salt
 Compound 1.43 (77.3 mg, 0.22 mmol) is reacted with peptide conjugate 2.10
 (69.3 mg, 0.1 mmol) as described in Example 6.26 and the product is
 purified. Yellow crystals (39.2 mg, 31%) are obtained; TLC [methanol]:
 R.sub.f =0.77; melting point=213-215.degree. C. (decomposition).
 EXAMPLE 6.35
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carbamoylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylam
 ino-thiocarbonyl]-lysyl-seryl}-batracyline
 Compound 1.44 (72.2 mg, 0.22 mmol) is reacted with peptide conjugate 2.10
 (69.3 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [ethyl acetate/ethanol 2:1] gives yellow crystals (66.1 mg,
 53%); TLC [ethyl acetate/ethanol 2:1]: R.sub.f =0.14; melting
 point=192.degree. C. (decomposition).
 EXAMPLE 6.36
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.alpha.-D-mannopyranosyl)-4-hydroxy-phenylamino-thioca
 rbonyl]-lysyl-seryl}-batracyline
 Compound 1.40 (62.8 mg, 0.22 mmol) is reacted with peptide conjugate 2.10
 (69.3 mg, 0.1 mmol) as described in Example 6.26 and the product is
 purified. Yellow crystals (48.9 mg, 44%) are obtained; TLC [ethyl
 acetate/ethanol 2:1]: R.sub.f =0.10; melting point=204.degree. C.
 EXAMPLE 6.37
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(2,3-di-O-methyl-.alpha.-D-mannopyranosyl)-4-hydroxy-phenylamino-t
 hiocarbonyl]-lysyl-seryl}-batracyline
 Compound 1.41 (66 mg, 0.22 mmol) is reacted with peptide conjugate 2.10
 (69.3 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [ethyl acetate.fwdarw.ethyl acetate/ethanol 7:1] gives
 yellow crystals (52 mg, 45%); TLC [ethyl acetate/ethanol 2:1]: R.sub.f
 =0.28; melting point=164-165.degree. C.
 EXAMPLE 6.38
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(.beta.-O-(.beta.-D-galactopyranosyl)-.beta.-D-glucopyranosyl)-4-h
 ydroxy-phenylamino-thiocarbonyl]-lysyl-seryl}-batracyline
 Compound 1.56 (95.4 mg, 0.22 mmol) is reacted with peptide conjugate 2.10
 (69.3 mg, 0.1 mmol) as described in Example 6.26. After concentration in
 vacuo, the product is washed thoroughly with hot methanol (50 ml). Yellow
 crystals (6.16 mg, 44%) are obtained; TLC [methanol]: R.sub.f =0.32;
 melting point=222.degree. C. (decomposition).
 EXAMPLE 6.39
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl
 -D-seryl}-batracyline
 p-Aminophenyl .beta.-L-fucopyranoside (56.2 mg, 0.22 mmol) is reacted with
 peptide conjugate 2.11 (62.6 mg, 0.1 mmol) as described in Example 6.26.
 Purification by flash chromatography [ethyl acetate.fwdarw.ethanol] and
 reprecipitation of the residue from methanol/methylene chloride 1:1 with
 diethyl ether give yellow crystals (50.9 mg, 48%); TLC [ethanol]: R.sub.f
 =0.14; melting point=133.degree. C.
 EXAMPLE 6.40
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3,4-di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-
 thiocarbonyl]-lysyl-D-seryl}-batracyline
 Compound 1.31 (79 mg, 0.22 mmol) is reacted with peptide conjugate 2.11
 (62.6 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [ethyl acetate.fwdarw.ethyl acetate/ethanol 5:1] gives
 yellow crystals (53.8 mg, 47%); TLC [ethyl acetate/ethanol 2:1]: R.sub.f
 =0.38; melting point=145-146.degree. C.
 EXAMPLE 6.41
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methoxycarbonylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-ph
 enylamino-thiocarbonyl]-lysyl-D-seryl}-batracyline
 Compound 1.42 (75.5 mg, 0.22 mmol) is reacted with peptide conjugate 2.11
 (62.6 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [ethyl acetate.fwdarw.ethyl acetate/ethanol 3:1] gives
 yellow crystals (52.4 mg, 42%); TLC [ethyl acetate/ethanol 2:1]: R.sub.f
 =0.12; melting point=168.degree. C.
 EXAMPLE 6.42
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carboxymethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamin
 o-thiocarbonyl]-lysyl-D-seryl}-batracyline, di-sodium salt
 Compound 1.43 (77.3 mg, 0.22 mmol) is reacted with peptide conjugate 2.11
 (62.6 mg, 0.1 mmol) as described in Example 6.26 and the product is
 purified. Yellow crystals (69.2 mg, 55%) are obtained; TLC [methanol]:
 R.sub.f =0.71; melting point=214-216.degree. C. (decomposition).
 EXAMPLE 6.43
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carbamoylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylam
 ino-thiocarbonyl]-lysyl-D-seryl}-batracyline
 Compound 1.44 (72.2 mg, 0.22 mmol) is reacted with peptide conjugate 2.11
 (62.6 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [ethyl acetate/ethanol 2:1] gives yellow crystals (46.4 mg,
 38%); TLC [ethyl acetate/ethanol 2:1]: R.sub.f =0.10; melting
 point=173.degree. C.
 EXAMPLE 6.44
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl
 -D-asparagyl}-batracyline
 p-Aminophenyl .beta.-L-fucopyranoside (56.2 mg, 0.22 mmol) is reacted with
 peptide conjugate 2.11 (72.1 mg, 0.1 mmol) as described in Example 6.26.
 Purification by reprecipitation from methanol/methylene chloride 1:1 with
 diethyl ether gives yellow crystals (69.4 mg, 64%); TLC [ethanol]: R.sub.f
 =0.14; melting point=185-187.degree. C.
 EXAMPLE 6.45
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3,4-di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-
 thiocarbonyl]-lysyl-D-asparagyl}-batracyline
 Compound 1.31 (79 mg, 0.22 mmol) is reacted with peptide conjugate 2.7
 (72.1 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [ethyl acetate/acetic acid 200:1.fwdarw.ethyl
 acetate/ethanol 3:1] gives yellow crystals (99.5 mg, 85%); TLC [ethanol]:
 R.sub.f =0.59; melting point=149.degree. C. (decomposition).
 EXAMPLE 6.46
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carboxymethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamin
 o-thiocarbonyl]-lysyl-D-asparagyl}-batracyline, di-sodium salt
 Compound 1.43 (77.3 mg, 0.22 mmol) is reacted with peptide conjugate 2.7
 (72.1 mg, 0.1 mmol) as described in Example 6.26. Purification by
 reprecipitation from methanol/methylene chloride 1:1 with diethyl ether
 gives yellow crystals (93.4 mg, 73%); melting point=220.degree. C.
 (decomposition).
 EXAMPLE 6.47
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carbamoylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylam
 ino-thiocarbonyl]-lysyl-D-asparagyl}-batracyline
 Compound 1.44 (72.2 mg, 0.22 mmol) is reacted with peptide conjugate 2.7
 (72.1 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [ethyl acetate/ethanol/acetic acid 400:100:2] gives yellow
 crystals (69.7 mg, 57%); TLC [ethanol]: R.sub.f =0.11; melting
 point=111.degree. C.
 EXAMPLE 6.48
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl
 -D-asparagyl}-batracyline, sodium salt
 Compound 6.44 (21.7 mg, 20 mmol) is suspended in water (10 ml), and 0.05N
 sodium hydroxide solution is added dropwise to the suspension, while
 stirring, until a clear solution forms (pH&lt;10). Lyophilization of the
 filtered solution gives a yellow amorphous solid (20.6 mg, 93%).
 EXAMPLE 6.49
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3,4-di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-
 thiocarbonyl]-lysyl-D-asparagyl}-batracyline, sodium salt
 Compound 6.45 (23.5 mg, 20 mmol) is reacted as described in Example 6.48
 and the product is worked up. A yellow amorphous solid (23.9 mg, 100%) is
 obtained.
 EXAMPLE 6.50
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carboxymethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamin
 o-thiocarbonyl]-lysyl-D-asparagyl}-batracyline, tri-sodium salt
 Compound 6.46 (25.6 mg, 20 .mu.mol) is dissolved in water (10 ml), and
 0.05N sodium hydroxide solution is added dropwise to the solution, while
 stirring, until pH 8 is reached. Lyophilization of the filtered solution
 gives a yellow amorphous solid (24 mg, 92%).
 EXAMPLE 6.51
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carbamoylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylam
 ino-thiocarbonyl]-lysyl-D-asparagyl}-batracyline, sodium salt
 Compound 6.47 (24.7 mg, 20 .mu.mol) is reacted as described in Example 6.48
 and the product is worked up. A yellow amorphous solid (23.0 mg, 92%) is
 obtained.
 EXAMPLE 6.52
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl
 -D-glutamyl}-batracyline
 p-Aminophenyl .beta.-L-fucopyranoside (56.2 mg, 0.22 mmol) is reacted with
 peptide conjugate 2.8 (66.8 mg, 0.1 mmol) as described in Example 6.26.
 Purification by flash chromatography [ethyl acetate/acetic acid
 200:1.fwdarw.ethyl acetate/ethanol/acetic acid 10:1:0.1] gives yellow
 crystals (39.5 mg, 36%); TLC [ethanol]: R.sub.f =0.09; melting
 point=138-139.degree. C. (decomposition).
 EXAMPLE 6.53
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carboxymethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamin
 o-thiocarbonyl]-lysyl-D-glutamyl}-batracyline, di-sodium salt
 Compound 1.43 (77.3 mg, 0.22 mmol) is reacted with peptide conjugate 2.8
 (66.8 mg, 0.1 mmol) as described in Example 6.26 and the product is
 purified. Yellow crystals (97.4 mg, 75%) are obtained; melting
 point=180.degree. C. (decomposition).
 EXAMPLE 6.54
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-O-(3-O-carboxymethyl-.beta.-D-galatopyranosyl)-4-hydroxy-phenylamino-
 thiocarbonyl]-lysyl-D-glutamyl}-batracyline, tri-sodium salt
 Compound 6.53 (25.6 mg, 20 .mu.mol) is reacted as described in Example 6.50
 and the product is worked up. A yellow amorphous solid (24.3 mg, 92%) is
 obtained; [.alpha.].sup.20 =+20.0.degree. (c=0.26/H.sub.2 O).
 EXAMPLE 6.55
 N-N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl
 -glycyl}-batracyline
 p-Aminophenyl .beta.-L-fucopyranoside is reacted with peptide conjugate 2.9
 (66.2 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [ethyl acetate.fwdarw.ethanol] gives yellow crystals (62.2
 mg, 60%); TLC [ethanol]: R.sub.f =0.12; melting point=176.degree. C.
 EXAMPLE 6.56
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-p-D-galactopyranosyl)-4-hydroxy-phenylamino-thiocarbon
 yl]-lysyl-glycyl}-batracyline
 Compound 1.25 (62.8 mg, 0.22 mmol) is reacted with peptide conjugate 2.9
 (66.2 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [ethyl acetate/ethanol 10:1.fwdarw.2:1] gives yellow
 crystals (56.2 mg, 52%); TLC [ethyl acetate/ethanol 2:1]: R.sub.f =0.22;
 melting point=197.degree. C.
 EXAMPLE 6.57
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3,4-di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-
 thiocarbonyl]-lysyl-glycyl}-batracyline
 Compound 1.31 (79 mg, 0.22 mmol) is reacted with peptide conjugate 2.9
 (66.2 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [ethyl acetate/ethanol 10:1.fwdarw.3:1] gives yellow
 crystals (26.2 mg, 23%); TLC [ethyl acetate/ethanol 2:1]: R.sub.f =0.39;
 melting point=209.degree. C.
 EXAMPLE 6.58
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methoxycarbonylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-ph
 enylamino-thiocarbonyl]-lysyl-glycyl}-batracyline
 Compound 1.42 (75.5 mg, 0.22 mmol) is reacted with peptide conjugate 2.9
 (66.2 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [ethyl acetate/ethanol.fwdarw.10:1] gives yellow crystals
 (22 mg, 18%); TLC [ethyl acetate/ethanol 2:1]: R.sub.f =0.06; melting
 point=194-195.degree. C. (decomposition).
 EXAMPLE 6.59
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carboxymethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamin
 o-thiocarbonyl]-lysyl-glycyl}-batracyline, di-sodium salt
 Compound 1.43 (77.3 mg, 0.22 mmol) is reacted with peptide conjugate 2.9
 (66.2 mg, 0.1 mmol) as described in Example 6.26. After concentration in
 vacuo, the product is washed thoroughly with methanol, methylene chloride
 and diethyl ether. Yellow crystals (86.8 mg, 71%) are obtained; melting
 point=230-232.degree. C. (decomposition).
 EXAMPLE 6.60
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-10-(3-O-carbamoylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylam
 ino-thiocarbonyl]-lysyl-glycyl}-batracyline
 Compound 1.44 (72.2 mg, 0.22 mmol) is reacted with peptide conjugate 2.9
 (66.2 mg, 0.1 mmol) as described in Example 6.26. After concentration in
 vacuo, and washing with methanol, methylene chloride and diethyl ether,
 yellow crystals (40.9 mg, 35%) are obtained; TLC [ethyl acetate/ethanol
 2:1]: R.sub.f =0.05; melting point=214-216.degree. C. (decomposition).
 EXAMPLE 6.61
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.epsilon.-D-mannopyranosyl)-4-hydroxy-phenylamino-thio
 carbonyl]-lysyl-glycyl}-batracyline
 Compound 1.40 (62.8 mg, 0.22 mmol) is reacted with peptide conjugate 2.9
 (66.2 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [ethyl acetate/ethane 10:1.fwdarw.2:1] gives yellow
 crystals (72.2 mg, 66%); TLC [ethyl acetate/ethanol 2:1]: R.sub.f =0.18;
 melting point=175.degree. C.
 EXAMPLE 6.62
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(2,3-di-O-methyl-.alpha.-D-mannopyranosyl)-4-hydroxy-phenylamino-t
 hiocarbonyl]-lysyl-glycyl}-batracyline
 Compound 1.41 (66 mg, 0.22 mmol) is reacted with peptide conjugate 2.9
 (66.2 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [ethyl acetate/ethanol 10:1.fwdarw.3:1] gives yellow
 crystals (66.6 mg, 60%); TLC [ethyl acetate/ethanol 2:1]: R.sub.f =0.41;
 melting point=173.degree. C.
 EXAMPLE 6.63
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[-(.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl-
 D-threonyl}-batracyline
 p-Aminophenyl .beta.-L-fucopyranoside (56.2 mg, 0.22 mmol) is reacted with
 peptide conjugate 2.12 (64 mg, 0.1 mmol) as described in Example 6.26.
 Purification by flash chromatography [ethyl acetate.fwdarw.ethanol] and
 reprecipitation of the product from methanol/methylene chloride 1:1 with
 diethyl ether give yellow crystals (30.5 mg, 28%); TLC [ethanol]: R.sub.f
 =0.10; melting point=172.degree. C.
 EXAMPLE 6.64
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thiocarbonyl]-ly
 syl-D-alanyl}-batracyline
 Compound 1.23 (59.7 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 10:1.fwdarw.1:1] gives yellow
 crystals (68.3 mg, 64%); TLC [methylene chloride/methanol 1:1]: R.sub.f
 =0.49; melting point=222-224.degree. C. (decomposition).
 EXAMPLE 6.65
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(2-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thioc
 arbonyl]-lysyl-D-alanyl}-batracyline
 Compound 1.24 (62.8 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by
 reprecipitation from methanol/methylene chloride 1:1 with diethyl ether
 gives yellow crystals (69.6 mg, 63%); TLC [ethanol]: R.sub.f =0.24;
 melting point=208.degree. C. (decomposition).
 EXAMPLE 6.66
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-3-O-methyl-.beta.-D-galactopyranosyl)-4hydroxy-phenylamino-thiocar
 bonyl]-lysyl-D-alanyl}-batracyline
 Compound 1.25 (62.8 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 15:1.fwdarw.10:1.fwdarw.5:1]
 gives yellow crystals (94.3 mg, 85%); TLC [methylene chloride/methanol
 5:1]: R.sub.f =0.16; melting point=212.degree. C. (decomposition).
 EXAMPLE 6.67
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(4-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thioc
 arbonyl]-lysyl-D-alanyl}-batracyline
 Compound 1.26 (62.8 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 15:1.fwdarw.10:1.fwdarw.5:1]
 gives yellow crystals (52.6 mg, 48%); TLC [methylene chloride/methanol]:
 R.sub.f =0.88; melting point=192.degree. C. (decomposition).
 EXAMPLE 6.68
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(6-O-methyl-.beta.-D-galactopyranosyl)-4hydroxy-phenylamino-thioca
 rbonyl]-lysyl-D-alanyl}-batracyline
 Compound 1.27 (62.8 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by
 reprecipitation from methanol/methylene chloride 1:1 with diethyl ether
 gives yellow crystals (96.7 mg, 88%); TLC [methylene chloride/methanol
 5:1]: R.sub.f =0.04; melting point=210.degree. C. (decomposition).
 EXAMPLE 6.69
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(2,3-di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-
 thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Compound 1.28 (65.9 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 20:1] gives yellow crystals
 (57.4 mg, 51%); TLC [methylene chloride/methanol 5:1]: R.sub.f =0.40;
 melting point=148.degree. C. (decomposition).
 EXAMPLE 6.70
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(2,4-di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-
 thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Compound 1.29 (65.9 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 20:1.fwdarw.15:1.fwdarw.10:1]
 gives yellow crystals (74.2 mg, 65%); TLC [methylene chloride/methanol
 5:11: R.sub.f =0.40; melting point=140.degree. C. (decomposition).
 EXAMPLE 6.71
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(2,6-di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-
 thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Compound 1.30 (65.9 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 20:1.fwdarw.15:1] gives yellow
 crystals (43.9 mg, 40%); TLC [methylene chloride/methanol 5:1]: R.sub.f
 =0.43; melting point=229.degree. C. (decomposition).
 EXAMPLE 6.72
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3,4-di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-
 thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Compound 1.31 (79 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 10:1] gives yellow crystals
 (66.2 mg, 59%); TLC [methylene chloride/methanol/ammonia (25%) 15:3:0.2]:
 R.sub.f =0.39; melting point=184.degree. C.
 EXAMPLE 6.73
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3,6di-O-methyl-D-galactopyranosyl)-4-hydroxy-phenylamino-thiocarb
 onyl]-lysyl-D-alanyl}-batracyline
 Compound 1.32 (65.9 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 15:1.fwdarw.10:13 gives yellow
 crystals (57.1 mg, 50%); TLC [methylene chloride/methanol 5:1): R.sub.f
 =0.42; melting point=190.degree. C. (decomposition).
 EXAMPLE 6.74
 N{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(4,6-di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-
 thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Compound 1.33 (79 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 20:1.fwdarw.10:1.fwdarw.5:1]
 gives yellow crystals (47.0 mg, 42%); TLC [methylene chloride/methanol
 5:1]: R.sub.f =0.39; melting point=169.degree. C.
 EXAMPLE 6.75
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(2,3,4-tri-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylami
 no-thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Compound 1.34 (69 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 30:1] gives yellow crystals
 (83.8 mg, 72%); TLC [methylene chloride/methanol 10:1]: R.sub.f =0.36;
 melting point=165.degree. C. (decomposition).
 EXAMPLE 6.76
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[(O-(2,3,6-tri-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylam
 ino-thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Compound 1.35 (69 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by
 reprecipitation from methanol/methylene chloride 1:1 with diethyl ether
 gives yellow crystals (105 mg, 91%); TLC (methylene chloride/methanol
 5:1]: R.sub.f =0.48; melting point=194.degree. C. (decomposition).
 EXAMPLE 6.77
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(2,4,6-tri-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylami
 no-thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Compound 1.36 (69 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 30:1.fwdarw.10:1] gives yellow
 crystals (67 mg, 58%); TLC (methylene chloride/methanol 5:1]: R.sub.f
 =0.54; melting point=228.degree. C. (decomposition).
 EXAMPLE 6.78
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3,4,6-tri-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylami
 no-thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Compound 1.37 (69 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by
 reprecipitation from methanol/methylene chloride 1:1 with diethyl ether
 gives yellow crystals (109.3 mg, 94%); TLC [methylene chloride/methanol
 5:1]: R.sub.f =0.52; melting point=180.degree. C. (decomposition).
 EXAMPLE 6.79
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(2,3,4,6-tetra-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-pheny
 lamino-thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Compound 1.38 (69 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by
 reprecipitation from methanol/methylene chloride 1:1 with diethyl ether
 gives yellow crystals (99.2 mg, 84%); TLC [methylene chloride/methanol
 10:1]: R.sub.f =0.73; melting point=188.degree. C. (decomposition).
 EXAMPLE 6.80
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methoxycarbonylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-ph
 enylamino-thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Compound 1.42 (75.5 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by
 reprecipitation from methanol/methylene chloride 1:1 with diethyl ether
 gives yellow crystals (22 mg, 18%); TLC [methylene chloride/methanol 5:1]:
 R.sub.f =0.33; melting point=194-195.degree. C. (decomposition).
 EXAMPLE 6.81
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carboxymethyl-.beta.-D-galactopyranosyl)-4hydroxy-phenylamino
 -thiocarbonyl]-lysyl-D-alanyl}-batracyline, di-sodium salt
 Compound 1.43 (77.3 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26 and the product is
 purified. Yellow crystals (99.7 mg, 81%) are obtained; TLC [methanol]:
 R.sub.f =0.80; melting point=230.degree. C. (decomposition).
 EXAMPLE 6.82
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carbamoylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylam
 ino-thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Compound 1.44 (72.2 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 7:1] gives yellow crystals
 (29.4 mg, 25%); TLC [methylene chloride/methanol 3:1]: R.sub.f =0.23;
 melting point=201-202.degree. C.
 EXAMPLE 6.83
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3,4-O-dideoxy-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-th
 iocarbonyl]-lysyl-D-alanyl}-batracyline
 Compound 1.52 (52.6 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 17:1] gives yellow crystals
 (38.8 mg, 37%); TLC [methylene chloride/methanol/ammonia (25%) 15:3:0.2]:
 R.sub.f =0.40; melting point=175.degree. C.
 EXAMPLE 6.84
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(.alpha.-D-mannopyranosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lys
 yl-D-alanyl}-batracyline
 Compound 1.39 (59.7 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 10:1.fwdarw.1:1] gives yellow
 crystals (52 mg, 48%); TLC [methylene chloride/methanol 1:1]: R.sub.f
 =0.19; melting point 196.degree. C.
 EXAMPLE 6.85
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3,4-di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-
 thiocarbonyl]-lysyl-alanyl}-batracyline
 Compound 1.31 (79 mg, 0.22 mmol) is reacted with peptide conjugate 2.2
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 10:1] gives yellow crystals
 (77.6 mg, 69%); TLC [methylene chloride/methanol/ammonia (25%) 15:3:0.2]:
 R.sub.f =0.33; melting point=186.degree. C.
 EXAMPLE 6.86
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(4-O-.beta.-D-galactopyranosyl)-.beta.-D-glucopyranosyl)-4-hydroxy
 -phenylamino-thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Compound 1.56 (95.4 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. After concentration in
 vacuo, the residue is washed thoroughly with hot methanol (50 ml). Yellow
 crystals (102.8 mg, 73%) are obtained; TLC [methanol]: R.sub.f =0.27;
 melting point=225-226.degree. C. (decomposition).
 EXAMPLE 6.87
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(4-O-(3'-sulphato-.beta.-D-galactopyranosyl)-D-glucopyranosyl)-4-h
 ydroxy-phenylamino-thiocarbonyl]-lysyl-D-alanyl}-batracyline, disodium salt
 Compound 1.57 (117.8 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by
 reprecipitation from methanol/methylene chloride 1:1 with diethyl ether
 gives yellow crystals (152.8 mg, 95%); melting point=232.degree. C.
 (decomposition).
 EXAMPLE 6.88
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(4-O-(3'-O-methyl-.beta.-D-galactopyranosyl)-.beta.-D-glucopyranos
 yl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl-D-alanyl}-batracyline
 Compound 1.58 (98.4 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by
 reprecipitation from methanol/methylene chloride 1:1 with diethyl ether
 gives yellow crystals (118.2 mg, 83%); TLC [methylene chloride/methanol
 1:1]: R.sub.f =0.58; melting point=221.degree. C. (decomposition).
 EXAMPLE 6.89
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(2-O-methyl-4-O-(3'-O-methyl-.beta.-D-galactopyranosyl)-.beta.-D-g
 lucopyranosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl-D-alanyl}-batracyl
 ine
 Compound 1.59 (101.5 mg, 0.22 mmol) is reacted with peptide conjugate 2.13
 (67.7 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 15:1.fwdarw.10:1.fwdarw.5:1]
 gives yellow crystals (101.3 mg, 70%); TLC [methylene chloride/methanol
 2:1]: R.sub.f =0.58; melting point=233.degree. C. (decomposition).
 EXAMPLES 7.1-7.13
 General Formula
 ##STR99##
 The following glycoconjugates are prepared analogously to Example 4.1.a)
 starting from other amino acid or peptide conjugates of batracyline or
 from batracyline:
 EXAMPLE 7.1
 N-{N-(O-(3-O-Methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-D
 -alanyl}-batracyline
 Educts:
 carbohydrate from Example 1.2, amino acid conjugate from Example 2.3
 Purification by flash chromatography (methylene chloride/methanol/ammonia
 (17%) 15:1:0.1). Freeze drying from dioxane/water. Yield: 42% [TLC:
 methylene chloride/methanol/ammonia (17%) 15:2:0.2): R.sub.f =0.31].
 EXAMPLE 7.2
 N-{N-[O-(3-O-Carboxymethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarb
 onyl]-D-alanyl}-batracyline, sodium salt
 Educts:
 carbohydrate from Example 1.10, amino acid conjugate from Example 2.3
 Purification by flash chromatography (methylene chloride/methanol/ammonia
 (17%) 15:3:0.3). Freeze drying from dioxane/water and subsequent
 conversion into the sodium salt with 0.1N sodium hydroxide solution.
 Yield: 43% [TLC: methylene chloride/methanol/ammonia (17%) 15:4:0.5]:
 R.sub.f =0.14].
 EXAMPLE 7.3
 N-{N-[O-(.beta.-L-Fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-seryl-D-alan
 yl]-batracyline
 Educts:
 p-aminophenyl .beta.-L-fucoside, amino acid conjugate from Example 2.18
 Purification by flash chromatography (methylene chloride/methanol/ammonia
 (17%) 15:3:0.3). Freeze drying from dioxane/water. Yield: 93% [TLC:
 methylene chloride/methanol/ammonia (17%) 15:3:0.31: R.sub.f =0.28]
 FAB-MS: m/z=705=M+1.
 EXAMPLE 7.4
 N-{N-[O-(.beta.-Fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-D-alanyl-D-ala
 nyl}-batracyline
 Educts:
 p-aminophenyl .beta.-L-fucoside, amino acid conjugate from Example 2.19
 Purification by digestion with methanol and precipitation from
 methanol/methylene chloride with ether. Yield: 65% [TLC:
 acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.78].
 EXAMPLE 7.5
 N-{N-[O-(.beta.-L-Fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-glutamyl-D-a
 lanyl}-batracyline
 Educts:
 p-aminophenyl .beta.-L-fucoside, amino acid conjugate from Example 2.20
 Purification by flash chromatography (methylene chloride/methanol/ammonia
 (17%) 15:4:0.4; later in the same system 15:6:0.6). Freeze drying from
 dioxane/water. Yield: 92% [TLC: methylene chloride/methanol/ammonia (17%)
 15:8:0.8: R.sub.f =0.55].
 EXAMPLE 7.6
 N-[O-(3-O-Carboxymethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thio-carbon
 yl]-batracyline
 250 mg (1 mmol) of batracyline are dissolved in 50 ml of dioxane and, after
 addition of 184 .mu.l of thiophosgene, the mixture is stirred at
 20.degree. C. for 2 hours. It is concentrated and the residue is digested
 with ether and filtered. The filter residue is dried under a high vacuum
 for 16 hours and then taken up in 30 ml of dimethylformamide. 312 mg (1
 mmol) of the carbohydrate from Example 1.10 and 500 .mu.l of
 ethyldiisopropylamine are added and the mixture is treated with ultrasound
 for 4 hours. It is then concentrated and the residue is purified by flash
 chromatography (methylene chloride/methanol/ammonia (17%) 15:2:0.2; later
 in the same system 15:6:0.6). The relevant fractions are concentrated and
 lyophilized from dioxane/water. Yield: 363 mg (60%) [TLC: methylene
 chloride/methanol/ammonia (17%) 15:6:0.6 R.sub.f =0.38].
 EXAMPLE 7.7
 N-[O-(3-O-Methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-batr
 acyline
 Preparation analogously to Example 7.6 starting from batracyline and
 carbohydrate from Example 1.2.
 Purification by flash chromatography (methylene chloride/methanol/ammonia
 (17%) 15:1:0.1); yield: 58% [TLC: methylene chloride/methanol/ammonia
 (17%) 15:2:0.2 R.sub.f =0.39]. FAB-MS: m/z=561=M+1.
 EXAMPLE 7.8
 N-{N-[O-(3,4-Di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-t
 hio-carbonyl]-D-alanyl}-batracyline
 Compound 1.31 (37.5 mg, 0.11 mmol) is reacted with peptide conjugate 2.3
 (32 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 30:1] gives yellow crystals
 (49.3 mg, 75%); TLC [ethyl acetate/ethanol 2.1]: R.sub.f =0.81; melting
 point=185.degree. C. (decomposition).
 EXAMPLE 7.9
 N-{N-[O-(2,3,4-Tri-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamin
 o-thio-carbonyl]-D-alanyl]-batracyline
 Compound 1.34 (34.5 mg, 0.11 mmol) is reacted with peptide conjugate 2.3
 (32 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 40:1-15:1] gives yellow
 crystals (54.9 mg, 81%); TLC [methylene chloride/methanol 20:1]: R.sub.f
 =0.15; melting point=190.degree. C. (decomposition).
 EXAMPLE 7.10
 N-{N-[O-(3-O-Methoxycarbonylmethyl-.beta.-D-galactopyranosyl)-4hydroxy-phen
 ylamino-thiocarbonyl]-D-alanyl}-batracyline
 Compound 1.42 (37.8 mg, 0.11 mmol) is reacted with peptide conjugate 2.3
 (32 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 20:1.fwdarw.10:1] gives yellow
 crystals (44.3 mg, 63%); TLC [ethanol]: R.sub.f =0.85; melting
 point=195.degree. C. (decomposition).
 EXAMPLE 7.11
 N-{N-[O-(3-O-Carboxymethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino
 -thiocarbonyl]-D-alanyl}-batracyline, sodium salt
 Compound 1.43 (38.6 mg, 0.11 mmol) is reacted with peptide conjugate 2.3
 (32 mg, 0.1 mmol) as described in Example 6.26. Purification by
 reprecipitation from methanol/methylene chloride 1:1 with diethyl ether
 gives yellow crystals (63.8 mg, 89%); TLC [ethanol]: R.sub.f =0.15;
 melting point=217.degree. C. (decomposition).
 EXAMPLE 7.12
 N-{N-[O-(3-O-Carbamoylmethyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylami
 no-thiocarbonyl]-D-alanyl}-batracyline
 Compound 1.44 (37.8 mg, 0.11 mmol) is reacted with peptide conjugate 2.3
 (32 mg, 0.1 mmol) as described in Example 6.26. Purification by flash
 chromatography [methylene chloride/methanol 20:1.fwdarw.10:1.fwdarw.5:1]
 gives yellow crystals (20 mg, 29%); TLC [ethanol]; R.sub.f =0.15; melting
 point=184.degree. C. (decomposition).
 EXAMPLE 7.13
 N-(N-[O-(.beta.-L-Fucopyranosyl)-4-hydroxy-phenylamino-thiocarbonyl]-D-alan
 yl}-batracyline
 p-Aminophenyl .beta.-L-fucopyranoside (28.1 mg, 0.11 mmol) is reacted with
 peptide conjugate 2.3 (32 mg, 0.1 mmol) as described in Example 6.26.
 Purification by flash chromatography [ethyl acetate/petroleum ether
 2:1.fwdarw.5:1] gives yellow crystals (49.8 mg, 81%); TLC [ethanol]:
 R.sub.f =0.50; meting point -173.degree. C.
 EXAMPLES 8.1-8.12
 General Formula
 ##STR100##
 EXAMPLE 8.1
 N-{N.sup..epsilon.
 -[2-Chloro-4-[O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino]-triaz
 in-6-yl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 8.1.a) N-{N.sup..alpha. -tert-Butoxycarbonyl]-N.sup..epsilon.
 -[2-chloro-4-[0-3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino]-triazi
 n-6-yl]-lysyl-D-alanyl}-batracyline
 265 mg (0.98 mmol) of p-aminophenyl 3-O-methyl-.beta.-L-fucoside (Example
 1.2) and 181 mg (0.98 mmol) of cyanuric chloride are taken up in 50 ml of
 dioxane/water 1:1 and the mixture is cooled to -5.degree. C. and, after
 addition of 83 mg of sodium bicarbonate, stirred at this temperature for
 15 minutes. 538 mg (0.98 mmol) of N-[N.sup..alpha.
 -(tert-butoxycarbonyl)-lysyl-D-alanyl]-batracyline (Example 2.4),
 dissolved in 14 ml of dimethylformamide, and a further 83 mg of sodium
 bicarbonate are then added and the mixture is allowed to come to room
 temperature. After stirring at 20.degree. C. for 16 hours, the mixture is
 concentrated and the residue is treated with water. The mixture is
 filtered with suction and the filter residue is dried under a high vacuum
 to give 890 mg (96%) of the target product. [TLC: methylene
 chloride/methanol 10:1 R.sub.f =0.26].
 8.1) N-{N.sup..epsilon.
 -[2-Chloro-4-[O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino]-triaz
 in-6-yl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 100 mg (0.11 mmol) of the compound from ample 8.1.a are stirred in a
 mixture of 5 ml of anhydrous trifluoroacetic acid and 5 ml of methylene
 chloride at 0.degree. C. for 30 minutes. The mixture is concentrated and
 the residue is purified by flash chromatography (methylene
 chloride/methanol/ammonia 17%) 15:1.5:0.15. Subsequent precipitation from
 methanol/ether leads to 41 mg (95%) of the target product [TLC: methylene
 chloride/methanol/ammonia (17%) 15:2:0.2 R.sub.f =0.263 FAB-MS:
 m/z=829=M+1.
 EXAMPLE 8.2
 N-{N.sup..epsilon.
 -[4-Hydroxyethylamino-2-[O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenyla
 mino]-triazin-6-yl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 8.2.a) N-[N.sup..alpha. -[tert-Butoxycarbonyl]-N.sup..epsilon.
 -4-hydroxyethylamino-2-[O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenylam
 ino]-triazin-6-yl]-lysyl-D-alanyl]-batracyline
 100 mg (0.11 mmol) of the compound from Example 8.1.a are dissolved in 3 ml
 of dioxane. 60 mg of potassium carbonate and 6.5 ml of a 0.1N solution of
 ethanolamine in dioxane are added and the mixture is stirred at 80.degree.
 C. for 18 hours. It is then concentrated and the residue is stirred with
 water. The mixture is filtered and the filter residue is purified by flash
 chromatography (methylene chloride/methanol/ammonia (17%) 15:1:0.1). After
 concentration of the relevant fractions and drying under a high vacuum, 83
 mg (80%) of the target compound are obtained [TLC: methylene
 chloride/methanol/ammonia (17%) 15:2:0.2 R.sub.f =0.23].
 8.2) N-{N.sup..alpha.
 -[4-Hydroxyethylamino-2-10-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenyla
 mino-triazin-6-yl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 67 mg (0.07 mmol) of the compound from Example 8.2.a are deblocked
 analogously to Example 8.1. Purification is carried out by flash
 chromatography (methylene chloride/methanol/ammonia (17%) 15:2:0.2).
 Subsequent precipitation from methanol/ether leads to the target product
 in a 90% yield. FAB-MS: m/z=854=M+1.
 The following glycoconjugates are prepared analogously to Example 8.1:
 EXAMPLE 8.3
 N-{N.sup..alpha.
 -[2-Chloro-4-[-(2-O-methyl-.beta.-L-fucosyl)-4hydroxy-phenylamino]-triazin
 -6-yl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate from Example 1.1;
 Yield: 76%; FAB-MS: m/z=829=M+1.
 EXAMPLE 8.4
 N-{N.sup..epsilon.
 -[2-Chloro-4-O-(.beta.L-fucosyl)-4-hydroxy-phenylamino]-triazin-6-yl]-lysy
 l-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 p-aminophenyl .beta.-L-fucoside;
 Yield: 36%; FAB-MS: n/z=815=M+1.
 [TLC: methylene chloride/methanol/ammonia (17%) 15:4:0, R.sub.f =0.44].
 EXAMPLE 8.5
 N-{N.sup..epsilon.
 -[2-Chloro-4-[O-(3-deoxy-.beta.-L-fucosyl)-4-hydroxy-phenylamino]-triazin-
 6-yl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate from Example 1.6;
 Yield: 56%; FAB-MS: m/z=799=M+1;
 [TLC: acetonitrile/water/glacial acetic acid 15:1:0.2 R.sub.f =0.54].
 The following glycoconjugates are prepared analogously to Examples 8.1.a,
 8.2.a and 8.2 from the batracyline-peptide conjugate in Example 2.4 or
 from the L-alanyl isomer which is to be prepared in a corresponding
 manner:
 EXAMPLE 8.6
 N-{N.sup..epsilon.
 -[4-Hydroxyethylamino-2-[O-(2-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenyla
 mino]-triazin-6yl]-lysyl-D-allyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate from Example 1.1;
 Yield: 78%; FAB-MS: m/z=854=M+1;
 [TLC: methylene chloride/methanol/ammonia (17%) 15:4:0.5 R.sub.f =0.33].
 EXAMPLE 8.7
 N{N.sup..epsilon.
 -[4-Hydroxyethylamino-2-[O-(deoxy-.beta.-L-fucosyl)-4-hydroxy-phenylamino]
 -triazin-4-yl-lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate from Example 1.4;
 Yield: 38%; [TLC: methylene chloride/methanol/ammonia (17%) 15:4:0.5
 R.sub.f =0.4].
 EXAMPLE 8.8
 N-{N.sup..epsilon.
 -[4-Hydroxyethylamino-2-[O-(3-deoxy-.beta.-L-fucosyl)-4-hydroxy-phenylamin
 o]-triazin-6-yl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate from Example 1.6;
 Yield: 77%; FAB-MS: m/z=824=M+1;
 [TLC: methylene chloride/methanol/ammonia (17%) 15:4:0.5 R.sub.f =0.37].
 EXAMPLE 8.9
 N-{N.sup..epsilon.
 -[4-Hydroxyethylamino-2-[O-(.beta.-L-fucosyl)-4-hydroxy-phenylamino]-triaz
 in-6-yl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 p-aminophenyl .beta.-L-fucoside;
 Yield: 52%; FAB-MS: m/z=840=M+1;
 [TLC: methylene chloride/methanol/ammonia (17%) 15:4:0.5 R.sub.f =0.30].
 EXAMPLE 8.10
 N-{N.sup..epsilon.
 -[4-Hydroxyethylamino-2-[O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenyla
 mino]-triazin-6-yl]-lysyl-D-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate from Example 1.2;
 Yield: 88%;
 [TLC: methylene chloride/methanol/ammonia (17%) 15:3:0.3 R.sub.f =0.35].
 EXAMPLE 8.11
 N-{N.sup..epsilon.
 -[4-Hydroxyethylamino-2-[O-(2-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenyla
 mino]-triazin-6-yl]-lysyl-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate from Example 1.1;
 Yield: 58%;
 [TLC: methylene chloride/methanol/ammonia (17%) 15:4:0.5 R.sub.f =0.40].
 EXAMPLES 8-12
 N-{N.sup..epsilon.
 -[4-Hydroxyethylamino-2-[O-(4-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenyla
 mino]-triazin-6-yl]-lysyl-alanyl}-batracyline, trifluoroacetate
 Educt:
 carbohydrate from Example 1.4;
 Yield: 66%;
 FAB-MS: m/z=854=M+1;
 [TLC: methylene chloride/methanol/ammonia (17%) 15:4:0.5 R.sub.f =0.37].
 EXAMPLE 9.1
 N-[D-Alanyl]-quinolone-a, trifluoroacetate
 ##STR101##
 9.1.a) N-[N-(tert-Butoxycarbonyl)-D-alanyl}-quinolone-a
 N-(tert-Butoxycarbonyl)-D-alanine (3.6 g, 19.2 mmol) and
 2-isobutoxy-1-isobutoxycarbonyl-1,2-dihydro-quinoline (5.8 g, 19.2 mmol)
 are dissolved in 200 ml of dimethylformamide. After the mixture has been
 stirred at room temperature for 8 hours, quinolone-a (4 g, 9.6 mmol) and
 3.3 ml of ethyldiisopropylamine are added and the batch is treated with
 ultrasound for 10 hours. It is concentrated, the residue is taken up in
 methylene chloride and the product is precipitated with ether. After
 filtration, washing with ether and drying under a high vacuum, 4.58 g
 (81%) of the target product, which is reacted without further
 purification, are obtained.
 9.1) N-[D-Alanyl]-quinolone-a, trifluoroacetate
 4.56 g (7.75 mmol) of the compound from Example 9.1.a are dissolved in 50
 ml of methylene chloride and 50 ml of anhydrous trifluoroacetic acid at
 0.degree. C. and the solution is stirred at this temperature for 1 hour.
 It is concentrated, the residue is subsequently distilled with methylene
 chloride and the product is precipitated from methanol with ether. 4.07 g
 (87%) of the crystalline target product are obtained. [TLC:
 acetonitril/water/glacial acetic acid 5:1:0.2 R.sub.f =0.34].
 EXAMPLE 9.2
 N-[Alanyl]-quinolone-a, trifluoroacetate
 ##STR102##
 The synthesis proceeds in an identical manner to that of the isomer in
 Example 9.1.
 EXAMPLE 9.3
 N-[Lysyl-D-alanyl]-quinolone-a, di-trifluoroacetate
 ##STR103##
 9.3.a) N-[N.sup..alpha.,N.sup..epsilon.
 -Bis-(tert-butoxycarbonyl)-lysyl-D-alanyl]-quinolone-a
 341 mg (0.984 mmol) of N.sup..alpha.,N.sup..epsilon.
 -bis-(tert-butoxycarbonyl)-lysine are dissolved in 10 ml of
 dimethylformamide, and 200 mg (1.48 mmol) of N-hydroxybenzotriazole and
 227 mg (1.18 mmol) of N'-(3-dimethylaminopropyl)-N-ethylcarbodiimide
 hydrochloride are added at 0.degree. C. After the mixture has been stirred
 at 10.degree. C. for 3 hours, 432 mg (0.82 mmol) of the compound from
 Example 9.1 are added and the mixture is stirred at 20.degree. C. for a
 further 2 hours. It is concentrated and the residue is stirred three times
 with 50 ml of water. The residue is then taken up in methylene chloride
 and the mixture is dried over sodium sulphate. Precipitation with ether
 leads to 516 mg (78%) of the target product. [TLC: acetonitrile/water 10:1
 R.sub.f =0.55].
 9.3) N-[Lysyl-D-alanyl]-quinolone-a, di-trifluoroacetate
 Deblocking of 512 mg (0.63 mmol) of the compound from Example 9.3.a
 analogously to Example 9.1. Precipitation from ethyl acetate with ether.
 Yield: 479 mg (90%); [TLC: acetonitrile/water/glacial acetic acid 10:3:1.5
 R.sub.f =0.3].
 EXAMPLE 9.4
 N-[Lysyl-alanyl]-quinolone-a, di-trifluoroacetate
 The synthesis proceeds in an identical manner to that of the isomer in
 Example 9.3.
 EXAMPLE 9.5
 N-[N.sup..alpha. -(tert-Butoxycarbonyl)-lysyl-D-alanyl]-quinolone-a
 ##STR104##
 9.5.a) N-[N.sup..alpha. -(tert--Butoxycarbonyl)-N.sup..epsilon.
 -(fluorenyl-9-methoxycarbonyl)-lysyl-D-alanyl]-quinolone-a
 1.57 g (3.36 mmol) of N.sup..alpha. -(tert-butoxy-carbonyl)-N.sup..epsilon.
 -(fluorenyl-9-methoxycarbonyl)-lysine are dissolved in 25 ml of
 dimethylformamide, and 600 mg (5.04 mmol) of N-hydroxysuccinimide and 820
 mg (4.03 mmol) of N,N'-dicyclohexylcarbodiimide are added at 0.degree. C.
 After 3 hours, the urea formed is filtered off, 1.5 g (2.86 mmol) of the
 compound from Example 9.1 are added to the filtrate and the mixture is
 stirred at room temperature for 16 hours. Residual urea is filtered off
 and the filtrate is purified by flash chromatography (methylene
 chloride/methanol 97.5:2.5; later in the same system 90:10]. The product
 is then precipitated from methylene chloride/methanol 1:1 with ether.
 Yield: 1.5 g (56%) [TLC: methylene chloride/methanol 9:1 R.sub.f =0.47].
 9.5) N-[N.sup..alpha. -(tert-Butoxycarbonyl)-lysyl-D-alanyl]-quinolone-a
 Splitting off of Fmoc from Example 9.5.a) with piperidine in
 dimethylformamide. Precipitation of the crude product from
 dimethylformamide with ether. Yield: 72% [TLC: acetonitrile/water/glacial
 acetic acid 5:1:0.2 R.sub.f =0.43].
 EXAMPLE 9.6
 N-[N.sup..epsilon.
 -(Fluorenyl-9-methoxycarbonyl)-lysyl-D-alanyl]-quinolone-a,
 trifluoroacetate
 ##STR105##
 Splitting off of Boc from Example 9.5.a) analogously to Example 9.1.
 Precipitation of the crude product from methanol/ether. Yield: 80% [TLC:
 methylene chloride/methanol/ammonia (17%) 15:4:0.5 R.sub.f =0.36].
 EXAMPLE 9.7
 N-[N.sup..alpha. -(tert-Butoxycarbonyl)-lysyl-alanyl-quinolone-a
 The synthesis proceeds in an identical manner to that of the isomer in
 Example 9.5.
 EXAMPLE 9.8
 N-[Lysyl]-quinolone-a, di-trifluoroacetate
 ##STR106##
 9.8.a) N-[N.sup..alpha.,N.sup..epsilon.
 -Bis-(tert-butoxycarbonyl)-lysyl]-quinolone-a
 1317 mg (3.8 mmol) of N.sup..alpha.,N.sup..epsilon.
 -bis-(tert-butoxycarbonyl)-lysine are linked with quinolone-a in
 accordance with the instructions in Example 9.1.a. Purification is carried
 out by flash chromatography [methylene chloride/methanol/ammonia (17%)
 15:1:0.1]. 1010 mg (71%) of the target product are obtained.
 9.8) N-[Lysyl]-quinolone-a, di-trifluoroacetate
 1005 mg (1.347 mmol) of the compound from Example 9.8.a are deblocked
 analogously to Example 9.1. After precipitation from methylene
 chloride/methanol 1:1 with ether, 966 mg (93%) of the crystalline target
 product are obtained. [TLC: acetonitrile/water/glacial acetic acid 10:5:3
 R.sub.f =0.33].
 EXAMPLE 9.9
 N-[D-Lysyl]-quinolone-a, di-trifluoroacetate
 The synthesis proceeds in an identical manner to that of the isomer in
 Example 9.8.
 EXAMPLE 9.10
 N-[N.sup..alpha. -(tert-Butoxycarbonyl-lysyl]-quinolone-a
 ##STR107##
 9.10.a) N-[N.sup..alpha. -tert-Butoxycarbonyl)-N.sup..epsilon.
 -(fluorenyl-9-methoxycarbonyl)-lysyl]-quinolone-a
 1350 mg (2.88 mmol) of N.sup..alpha. -(tert-butoxycarbonyl)-N.sup.68
 -(fluorenyl-9-methoxycarbonyl)-lysine are linked with quinolone-a in
 accordance with the instructions in Example 9.8.a. Purification is carried
 out by flash chromatography [methylene chloride/methanol/ammonia (17%)
 15:1:0.1; later in the same system 15:2:0.2]. 1025 mg (82%) of the target
 product are obtained.
 9.10) N-[N.sup..alpha. -(tert-Butoxycarbonyl)-lysyl]-quinolone-a
 Splitting off of Fmoc from Example 9.10.a analogously to Example 9.5. Two
 precipitations of the crude product from methanol with ether. Yield: 86%
 [TLC: acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.48].
 EXAMPLE 9.11
 N-[N.sup..epsilon. -(Fluorenyl-9-methoxycarbonyl)-lysyl]-quinolone-a,
 trifluoroacetate
 ##STR108##
 Splitting off of Boc from Example 9.10.a analogously to Example 9.1. Two
 precipitations of the crude product from methanol/ether. Freeze drying
 from dioxane/water. Yield: 92% [TLC: methylene chloride/methanol/ammonia
 (17%) 15:4:0.5 R.sub.f =0.44].
 EXAMPLES 10.1-10.3
 General Formula
 ##STR109##
 EXAMPLE 10.1
 N-{N.sup..epsilon.
 -[O(3-O-Carboxymethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl
 ]-lysyl-D-alanyl}-quinolone-a
 10.1.a) N-{N.sup..alpha. -(tert-Butoxycarbonyl)-N.sup..epsilon.
 -[O-(3O-carboxymethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl
 ]-lysyl-D-alanyl}-quinolone-a
 47 .mu.l (0.28 mmol) of thiophosgene are added to 78 mg (0.25 mmol) of
 p-aminophenyl 3-O-carboxymethyl-.beta.-L-fucoside (Example 1.10) in 15 ml
 of dioxane/water 1:1, while stirring. After the mixture has been stirred
 at 20.degree. C. for 10 minutes, it is concentrated and the residue is
 dried under a high vacuum for 1 hour. The isothiocyanate obtained is then
 coupled in absolute dimethylformamide with 180 mg (0.25 mmol) of
 N-[N.sup..alpha. -(tert-butoxycarbonyl)-lysyl-D-alanyl)-quinolone-a
 (Example 9.5) in the presence of 86 .mu.l of ethyldiisopropylamine. After
 two precipitations of the crude product from methylene chloride/ether,
 subsequent stirring with water and freeze drying from dioxane/water, 210
 mg (78%) of the target product are obtained. [TLC:
 acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.62].
 10.1) N-{N.sup..epsilon.
 -[O-(3-O-Carboxymethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbony
 l]-lysyl-D-alanyl}quinolone-a
 208 mg (0.193 mmol) of the compound from Example 1.0.a are stirred with 10
 ml of anhydrous trifluoroacetic acid in 10 ml of methylene chloride at
 0.degree. C. for 1 hour. The mixture is concentrated and the residue is
 subsequently distilled with 15 ml of methanol and chromatographed with
 methylene chloride/methanol/ammonia (17%) 10:10:0.8. After subsequent
 precipitation from dimethylformamide with ether, 52 mg (28%) of the target
 product are obtained. [TLC: acetonitrile/water/glacial acetic acid 5:1:0.2
 R.sub.f =0.53].
 The following glycoconjugates are prepared analogously to Example 10.1 from
 the partly protected peptide conjugates in Examples 9.5, 9.7 and 9.10:
 EXAMPLE 10.2
 N-{N.sup..epsilon.
 -[O-(3-O-Methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysy
 l-alanyl}-quinolone-a
 Educts:
 carbohydrate from Example 1.2; peptide conjugate from Example 9.7
 Purification of the intermediate stage by several precipitations from
 methanol with ether. Flash chromatographic purification of the final stage
 with methylene chloride/methanol/ammonia (17%) 15:4:0-5; later in the same
 system with 15:8:0.8. Yield: 20% [TLC: methylene chloride/methanol/ammonia
 (17%) 15:8:0.8 R.sub.f =0.15].
 EXAMPLE 10.3
 N-{N.sup..epsilon.
 -[O-(3-O-Methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysy
 l}-quinolone-a
 Educts:
 carbohydrate from Example 1.2; amino acid conjugate from Example 9.10
 Purification of the intermediate stage by precipitation from methanol with
 ether. Flash chromatography purification of the final stage with methylene
 chloride/methanol/ammonia (17%) 15:8:0.8. Yield: 39% [TLC:
 acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.33].
 EXAMPLES 11.1-11.18
 General Formula
 ##STR110##
 EXAMPLE 11.1
 N-{N.sup..alpha.,N.sup..epsilon. -Bis
 [O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl
 -D-alanyl}-quinolone-a
 50 mg (0.19 mmol) of p-aminophenyl 3-O-methyl-.beta.-L-fucoside (Example
 1.2) are first converted into the isothiocyanate in accordance with the
 instructions in Example 10.1.a and the product is then coupled in 5 ml of
 dimethylformamide with 68 mg (0.08 mmol) of
 N-[lysyl-D-alanyl]-quinolone-a, di-trifluoroacetate (Example 9.3) in the
 presence of 55 .mu.l of ethyldiisopropylamine. The mixture is stirred at
 room temperature for 16 hours and concentrated and the residue is purified
 by flash chromatography [methylene chloride/methanol/glacial acetic acid
 85:15:1.5]. 62 mg (63%) of the target product are subsequently obtained by
 precipitation from methanol with ether. [TLC: methylene
 chloride/methanol/glacial acetic acid 80:20:2 R.sub.f =0.5] MS-MALDI:
 m/z=1242=M+1.
 The following glycoconjugates are prepared analogously to Example 11.1 from
 the peptide conjugates in Examples 9.3, 9.4, 9.8 and 9.9:
 EXAMPLE 11.2
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-
 lysyl-alanyl}-quinolone-a
 Educts:
 50 mg (0.19 mmol) of carbohydrate from Example 1.2;
 0.08 mmol of peptide conjugate from Example 9.4
 Purification by flash chromatography [methylene chloride/methanol/glacial
 acetic acid 90:10:1] and precipitation from methanol with ether. Yield:
 79% [TLC: acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.42].
 EXAMPLE 11.3
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carboxymethyl-.beta.-L-fucosyl)-4hydroxy-phenylamino-thiocarb
 onyl]-lysyl-alanyl}-quinolone-a
 Educts:
 52 mg (0.166 mmol) of carbohydrate from Example 1.10;
 0.07 mmol of peptide conjugate from Example 9.4
 Purification by flash chromatography [methylene chloride/methanol/glacial
 acetic acid 80:20:2] and stirring of the residue with methanol [TLC:
 acetonitrile/water/glacial acetic acid 10:3:1.5 R.sub.f =0.62].
 EXAMPLE 11.4
 N-{N.sup..alpha.,N.sup..epsilon. -Bis-[
 O-(3-O-carboxymethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]
 -lysyl-D-alanyl}-quinolone-a
 Educts:
 44 mg (0.14 mmol) of carbohydrate from Example 1.10;
 0.06 mmol of peptide conjugate 9.3
 Purification by flash chromatography [methylene chloride/methanol/glacial
 acetic acid 80:20:2] and stirring of the residue with methanol. Yield:
 57%; [TLC: acetonitrile/water/glacial acetic acid 10:3:1.5 R.sub.f =0.62].
 EXAMPLE 11.5
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(.alpha.-L-rhamnosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl-al
 anyl}-quinolone-a
 Educts:
 44 mg (0.166 mmol) of carbohydrate from Example 1.21;
 0.07 mmol of peptide conjugate from Example 9.4
 Purification by flash chromatography [methylene chloride/methanol/glacial
 acetic acid 80:20:1] and stirring of the residue with methanol/ether.
 Yield: 90 mg (89%); [TLC: acetonitrile/water/glacial acetic acid 5:1:0.2
 R.sub.f =0.51] MS-ESI: m/z=1212=M+1.
 EXAMPLE 11.6
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-
 lysyl}-quinolone-a
 Educts:
 70 mg (0.258 mmol) of carbohydrate from Example 1.2;
 0.11 mmol of amino acid conjugate from Example 9.8
 Purification by flash chromatography [methylene chloride/methanol/glacial
 acetic acid 90:10:1] and precipitation from methylene chloride/methanol
 1:1 with ether. Stirring of the residue with water. Yield: 41%. [TLC:
 acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.65].
 EXAMPLE 11.7
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3--methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-D
 -lysyl}-quinolone-a
 Educts:
 50 mg (0.19 mmol) of carbohydrate from Example 1.2;
 0.08 mmol of amino acid conjugate from Example 9.9
 Purification by flash chromatography [methylene chloride/methanol/glacial
 acetic acid 90:10:1] and precipitation from methylene chloride/methanol
 1:1 with ether. Stirring of the residue with water. Yield: 67%. [TLC:
 acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.65] MS-FAB:
 m/z=1169=M+1.
 EXAMPLE 11.8
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carboxymethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocar
 bonyl]-lysyl}-quinolone-a, di-sodium salt
 Educts:
 50 mg (0.16 mmol) of carbohydrate from Example 1.10;
 0.07 mmol of amino acid conjugate from Example 9.8
 After concentration of the reaction batch, taking up of the residue in 10
 ml of dimethylformamide and addition of 8 ml of a 0.1N sodium hydroxide
 solution, the mixture is stirred at 20.degree. C. for 2 hours. After
 renewed concentration, the residue is taken up in water and the pH is
 brought to 5. The product is lyophilized and digested with methanol and
 then with methanol/ether. 68 mg (65%) of the target compound are thus
 obtained. [TLC: acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f
 =0.26].
 EXAMPLE 11.9
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carboxymethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocar
 bonyl]-D-lysyl}-quinolone-a, di-sodium salt
 Educts:
 100 mg (0.32 mmol) of carbohydrate from Example 1.10;
 0.13 mmol of amino acid conjugate from Example 12.9
 After concentration of the reaction batch, taking up of the residue in 10
 ml of dimethylformamide and addition of 16 ml of a 0.1N sodium hydroxide
 solution, the mixture is stirred at 20.degree. C. for 2 hours. After
 renewed concentration, the residue is taken up in water and the pH is
 brought to 5. The product is lyophilized and digested with methanol and
 then with methanol/ether. 160 mg (77%) of the target compound are thus
 obtained. Melting point: 218-220.degree. C. [TLC:
 acetonitrile/water/glacial acetic acid 10:3:1.5 R.sub.f =0.69].
 EXAMPLE 11.10
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.alpha.-L-fucosyl)-4hydroxy-phenylamino-thiocarbonyl]-
 D-lysyl}-quinolone-a
 Educts:
 50 mg (0.19 mmol) of carbohydrate from Example 1.3;
 0.08 mmol of amino acid conjugate from Example 9.9
 Preparation analogously to Example 11.7. Purification by flash
 chromatography [methylene chloride/methanol/ammonia (17%) 10:10:1] and
 subsequent precipitation from methylene chloride/methanol 1:1 with ether.
 Yield: 66%. [TLC: acetonitrile/water/glacial acetic acid 5:1:0.2: R.sub.f
 =0.62].
 EXAMPLE 11.11
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-O-(.alpha.-L-rhamnosyl)-4-hydroxy-phenylamino-thiocarbonyl]-D-lysyl}-
 quinolone-a
 Educts:
 50 mg (0.19 mmol) of carbohydrate from Example 1.21;
 0.08 mmol of amino acid conjugate from Example 9.9
 Preparation analogously to Example 11.7. Yield: 57%. [TLC:
 acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.63].
 EXAMPLE 11.12
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-
 D-lysyl}-quinolone-a, sodium salt
 58 mg (0.05 mmol) of the compound from Example 11.7 are suspended in water
 and converted into the sodium salt with one equivalent of a 0.1N sodium
 hydroxide solution. After freeze drying, 60 mg of the target compound are
 obtained.
 EXAMPLE 11.13
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thioc
 arbonyl]-lysyl}-quinolone-a, sodium salt
 Thiophosgene (33.5 ml, 0.44 mmol) is added to a solution of compound 1.25
 (62.8 mg, 0.22 mmol) in dioxane/water 1:1 (10 ml), while stirring. After
 10 minutes, the mixture is concentrated in vacuo and the residue is dried
 under an oil pump vacuum for 1 hour. The isothiocyanate obtained is
 dissolved in absolute dimethylformamide (10 ml), and compound 9.8 (77.4
 mg, 0.1 mmol) and ethyldiisopropylamine (0.5 ml) are added. The mixture is
 stirred at room temperature for 16 hours and then concentrated in vacuo
 and the residue is purified by flash chromatography (methylene
 chloride/methanol/ammonia (25%) 10:10:1.fwdarw.methanol/ammonia (25%)
 20:1]. Yellow crystals are obtained and are suspended in water (10 ml).
 0.05N sodium hydroxide solution is added dropwise to the suspension, while
 stirring, until a clear solution forms (pH&lt;10). Lyophilization of the
 filtered solution gives a yellow amorphous solid (39.7 mg, 32%);
 [.alpha.].sub.D.sup.20 =+25.8.degree. (c=0.26/H.sub.2 O).
 EXAMPLE 11.14
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(4-O-(3'-O-methyl-.beta.-D-galactopyranosyl)-.beta.-D-glucopyranos
 yl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl}-quinolone-a, sodium salt
 Compound 1.58 (98.4 mg, 0.22 mmol) is reacted with peptide conjugate 9.8
 (77.4 mg, 0.1 mmol) as described in Example 11.13 and the product is
 purified. A yellow amorphous solid (62.5 mg, 40%) is obtained;
 [.alpha.].sub.D.sup.20 =+12.9.degree. (c=0.26/H.sub.2 O).
 EXAMPLE 11.15
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(2-O-methyl-4-O-(3'-O-Methyl-.beta.-D-galactopyranosyl)-.beta.-D-g
 lucopyranosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysyl}-quinolone-a,
 sodium salt
 Compound 1.59 (101.5 mg, 0.22 mmol) is reacted with peptide conjugate 9.8
 (77.4 mg, 0.1 mmol) as described in Example 11.13. Purification by
 reprecipitation from methanol/methylene chloride 1:1 with diethyl ether
 and extraction by boiling with ethanol gives yellow crystals, which are
 converted into the sodium salt as described. A yellow amorphous solid
 (51.1 mg, 32%) is obtained; [.alpha.].sub.D.sup.20 =+27.9.degree.
 (c=0.24/H.sub.2 O).
 EXAMPLE 11.16
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thioc
 arbonyl]-D-lysyl}-quinolone, sodium salt
 Compound 1.25 (62.8 mg, 0.22 mmol) is reacted with peptide conjugate 9.9
 (77.4 mg, 0.1 mmol) as described in Example 11.13 and the product is
 purified. A yellow amorphous solid (77.3 mg, 63%) is obtained;
 [.alpha.].sub.D.sup.20 =-23.8.degree. (c=0.63/H.sub.2 O).
 EXAMPLE 11.17
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.alpha.-D-mannopyranosyl)-4-hydroxy-phenylamino-thioca
 rbonyl]-D-lysyl}-quinolone-a, sodium salt
 Compound 1.40 (62.8 mg, 0.22 mmol) is reacted with peptide conjugate 9.9
 (77.4 mg, 0.1 mmol) as described in Example 11.13 and the product is
 purified. A yellow amorphous solid (33.6 mg, 27%) is obtained;
 [.alpha.].sub.D.sup.20 =+0.7.degree. (c=0.28/H.sub.2 O).
 EXAMPLE 11.18
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(4-O-(3'-O-methyl-.beta.-D-galactopyranosyl)-.beta.-D-glucopyranos
 yl)-4-hydroxy-phenylamino-thiocarbonyl]-D-lysyl}-quinolone-a, sodium salt
 Compound 1.58 (98.4 mg, 0.22 mmol) is reacted with peptide conjugate 9.9
 (77.4 mg, 0.1 mmol) as described in Example 11.13 and the product is
 purified. A yellow amorphous solid (63.0 mg, 41%) is obtained;
 [.alpha.].sub.D.sup.20 =-21.8.degree. (c=0.22/H.sub.2 O).
 EXAMPLES 12.1-12.15
 General Formula
 ##STR111##
 EXAMPLE 12.1
 N-{N'-[O-(3-O-Methyl-.beta.-L-fucosyl)-4hydroxy-phenylamino-thiocarbonyl]-D
 -alanyl}-quinolone-a
 447 mg (1.66 mmol) of p-aminophenyl 3-O-methyl-.beta.-L-fucoside (Example
 1.2) are first converted into the isothiocyanate in accordance with the
 instructions in Example 10.1.a and the product is then coupled in 40 ml of
 dimethylformamide with 1 g (1.66 mmol) of N-[D-alanyl]-quinolone-a,
 trifluoroacetate (Example 9.1) in the presence of 568 .mu.l of
 ethyldiisopropylamine The mixture is stirred at room temperature for 2
 hours and concentrated and the residue is purified by several
 precipitations from methylene chloride/methanol 1:1 with ether. The filter
 residue is then stirred twice more with water. 876 mg (66%) of the target
 product are obtained. Melting point: 198.degree. C.; [TLC:
 acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.63].
 The following glycoconjugates are prepared analogously to Example 12.1 from
 the amino acid conjugates in Examples 9.1 and 9.2:
 EXAMPLE 12.2
 N-{[N'-[O-(3-O-Methyl-.beta.-L-fucosyl)-4hydroxy-phenylamino-thiocarbonyl]-
 alanyl}-quinolone-a
 Educt:
 25 mg (0.092 mmol) of carbohydrate from Example 1.2
 Purification by flash chromatography (methylene chloride/methanol/glacial
 acetic acid 90:10:1], precipitation from methylene chloride/methanol 1:1
 with ether and stirring of the filter residue with water. Yield: 53 mg
 (52%). [TLC: acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f
 =0.65].
 EXAMPLE 12.3
 N-{N'-[O-(3-O-Carboxymethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocar
 bonyl]-D-alanyl}-quinolone-a, mono-sodium salt
 Educts:
 523 mg (1.67 mmol) of carbohydrate from Example 1.10;
 840 mg (1.39 mmol) of the compound from Example 12.1
 After a reaction time of 6 hours, the mixture is concentrated and the
 residue is stirred with water. Flash chromatography [methylene
 chloride/methanol/ammonia (17%) 15:8:0.8; later in the same system 10:1:1]
 follows freeze drying from dioxane/water. The product is then taken up in
 water, one equivalent of a 0.1N sodium hydroxide solution is added and
 lyophilization is again carried out. Yield: 525 mg (45%). [TLC:
 acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.39].
 EXAMPLE 12.4
 N-{N'-[O-(.alpha.-L-Rhamnosyl)-4-hydroxy-phenylamino-thiocarbonyl]-D-alanyl
 }-quinolone-a
 Educt:
 20 mg (0.076 mmol) of carbohydrate from Example 1.21
 Purification by flash chromatography [methylene chloride/methanol/glacial
 acetic acid 90:10:1] and precipitation from methanol with ether. Yield: 20
 mg (34%). [TLC: acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f
 =0.42].
 The following glycoconjugates are prepared from partly protected
 N-(lysyl)-quinolone-a conjugates and N-(lysyl-D-alanyl)-quinolone-a
 conjugates:
 EXAMPLE 12.5
 N-{N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysy
 l}-quinolone-a
 12.5.a) N-{N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-N-.
 sup..epsilon. -[fluorenyl-9-methoxycarbonyl]-lysyl}-quinolone-a
 92 mg (0.34 mmol) of p-aminophenyl 3-O-methyl-.beta.-L-fucoside (Example
 1.2) are first converted into the isothiocyanate in accordance with the
 instructions in Example 10.1.a and the product is then coupled in 20 ml of
 dimethylformamide with 300 mg (0.34 mmol) of N-[N.sup..epsilon.
 -(fluorenyl-9-methoxycarbonyl)-lysyl]-quinolone-a, trifluoroacetate
 (Example 9.11) in the presence of 116 .mu.l of ethyldiisopropylamine. The
 mixture is stirred at room temperature for 16 hours and concentrated and
 the residue is purified by precipitation from methylene chloride with
 ether. The filter residue is then stirred further with water and
 lyophilized from dioxane/water. 290 mg (79%) of the target product are
 obtained. [TLC: acetonitrile/water 10:1 R.sub.f =0.6].
 12.5) N-{N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-lysy
 l}-quinolone-a
 288 mg (0.267 mmol) of the compound of Example 12.5.a are dissolved in 20
 ml of methylene chloride, and 8 ml of piperidine are added. After the
 mixture has been stirred at 20.degree. C. for 30 minutes, it is
 concentrated and the residue is precipitated from methylene chloride with
 ether. The product is purified by flash chromatography [methylene
 chloride/methanol/ammonia (17%) 10:10:2]. The residue is stirred with
 ether and lyophilized from water. 90 mg (39%) of the target product are
 obtained. [TLC: methylene chloride/methanol/ammonia (17%) 10:10:5 R.sub.f
 =0.4].
 The following glycoconjugates are prepared analogously to Examples 12.5
 from the conjugates in Example 9.11 and 9.6:
 EXAMPLE 12.6
 N-{N.sup..alpha.
 -[O-(3-O-Carboxymethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbony
 l]-lysyl}-quinolone-a, di-sodium salt
 Educts:
 63 mg (0.2 mmol) of carbohydrate from Example 1.10;
 158 mg (0.18 mmol) of compound from Example 9.11
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol/ammonia (17%) 15:4:0.5; later in the same system
 10:10:1] and of the final stage by stirring several times with methanol
 and washing of the filter residue with ether. Yield: 44%. The product is
 then suspended in water, the di-sodium salt is prepared with 2 equivalents
 of a 0.1N sodium hydroxide solution and the solution is lyophilized. [TLC:
 acetonitrile/water/glacial acetic acid 10:3:1.5 R.sub.f =0.34].
 EXAMPLE 12.7
 N-{N.sup..alpha.
 -[O-(3-O-Carboxymethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbony
 l]-lysyl-D-alanyl}-quinolone-a
 Educts:
 147 mg (0.47 mmol) of carbohydrate from Example 1.10;
 448 mg (0.47 mmol) of compound from Example 9.6
 Purification of the intermediate stage by two precipitations from methylene
 chloride/methanol 1:1 with ether; stirring of the filter residue with
 water (yield: 92%). Purification of the final stage by flash
 chromatography [methylene chloride/methanol/ammonia (17%) 10:10:2];
 precipitation from dimethylformamide with ether. Yield: 59%. [TLC:
 acetonitrile/water/glacial acetic acid 10:3:1.5 R.sub.f =0.4].
 EXAMPLE 12.8
 N-{N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-D-galactopyranosyl4-hydroxy-phenylamino-thio-carbon
 yl]-lysyl}-quinolone-a, hydrochloride
 Educts:
 compound 1.25 (62.8 mg, 0.22 mmol);
 peptide conjugate 9.11 (180.0 mg, 0.2 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol 10:1.fwdarw.7:1.fwdarw.2:1]. Yellow crystals (145.7 mg,
 67%) are obtained; TLC [methylene chloride/methanol 5:1]: R.sub.f =0.48.
 The fluorenyl-9-methoxycarbonyl group is then split off as described in
 Example 4.5 and the product is purified. Yellow crystals are obtained and
 are suspended in water (10 ml). 0.1N hydrochloric acid is added dropwise
 to the suspension, while stirring, until a clear solution forms (pH&gt;3).
 Lyophilization of the filtered solution gives a yellow amorphous solid
 (119.4 mg, 66%); [.alpha.].sub.D.sup.20 =+33.8.degree. (c=0.28/H.sub.2 O).
 EXAMPLE 12.9
 N-{N.sup..alpha.
 -[O-(3,6-Di-O-methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thio
 carbonyl]-lysyl}-quinolone-a, hydrochloride
 Educts:
 compound 1.32 (65.9 mg, 0.22 mmol);
 peptide conjugate 9.11 (180.0 mg, 0.2 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol 10:1.fwdarw.7:1.fwdarw.1:1]. Yellow crystals (115.0 mg,
 52%) are obtained; TLC [methylene chloride/methanol 5:1]: R.sub.f =0.44.
 The fluorenyl-9-methoxycarbonyl group is then split off as described in
 Example 4.5 and the product is purified. Yellow crystals are obtained and
 are suspended in water (10 ml). 0.1N hydrochloric acid is added dropwise
 to the suspension, while stirring, until a clear solution forms (pH&gt;3).
 Lyophilization of the filtered solution gives a yellow amorphous solid
 (94.3 mg, 51%); [.alpha.].sub.D.sup.20 =+44.2.degree. (c=0.34/H.sub.2 O).
 EXAMPLE 12.10
 N-{N.sup..alpha.
 -[O-(3-O-Methyl-.alpha.-D-mannopyranosyl)-4-hydroxy-phenylamino-thio-carbo
 nyl]-lysyl}-quinolone-a, hydrochloride
 Educt:
 compound 1.40 (62.8 mg, 0.22 mmol);
 peptide conjugate 9.11 (180.0 mg, 0.2 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol 10:1.fwdarw.5:1.fwdarw.1:1]. Yellow crystals (96.7 mg,
 44%) are obtained; TLC [methylene chloride/methanol 5:1]: R.sub.f =0.47.
 The fluorenyl-9-methoxycarbonyl group is then split off as described in
 Example 4.5 and the product is purified. Yellow crystals are obtained and
 are suspended in water (10 ml). 0.1N hydrochloric acid is added dropwise
 to the suspension, while stirring, until a clear solution forms (pH&gt;3).
 Lyophilization of the filtered solution gives a yellow amorphous solid
 (78.2 mg, 43%); [.alpha.].sub.D.sup.20 =-157.2.degree. (c=0.30/H.sub.2 O).
 EXAMPLE 12.11
 N-{N.sup..alpha.
 -[O-(4-O-(3'-O-Methyl-.beta.-D-galactopyranosyl)-.beta.-D-glucopyranosyl)-
 4-hydroxy-phenylamino-thiocarbonyl]-lysyl}-quinolone-a hydrochloride
 Educts:
 compound 1.58 (98.4 mg, 0.22 mmol);
 peptide conjugate 9.11 (180.0 mg, 0.2 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol/ammonia (25%)
 20:10:1.fwdarw.10:10:1.fwdarw.methanol/ammonia (25%) 20:1]. Beige crystals
 (132.1 mg, 53%) are obtained; TLC [methylene chloride/methanol/ammonia
 (25%) 10:10:3]: R.sub.f =0.60. The fluorenyl-9-methoxycarbonyl group is
 then split off as described in Example 4.5 and the product is purified.
 Yellow crystals are obtained and are suspended in water (10 ml). 0.1N
 hydrochloric acid is added dropwise to the suspension, while stirring,
 until a clear solution forms (pH&gt;3). Lyophilization of the filtered
 solution gives a yellow amorphous solid (90.0 mg, 42%);
 [.alpha.].sub.D.sup.20 =+192.2.degree. (c=0.27/H.sub.2 O).
 The following glycoconjugates are prepared in accordance with the
 instructions in Example 12.1 starting from unsubstituted quinolone-a:
 EXAMPLE 12.12
 N-[O-(3-O-Carboxymethyl-.beta.-L-fucosyl)-4hydroxy-phenylamino-thiocarbonyl
 -quinolone-a, di-sodium salt
 Educts:
 78.5 mg (0.25 mmol) of carbohydrate from Example 1.10;
 70 mg (0.167 mmol) of quinolone-a
 After a reaction time of 6 hours, the mixture is concentrated, the residue
 is taken up in dimethylformamide and the mixture is stirred with 4 ml of a
 0.1N sodium hydroxide solution for 1 hour. Purification by flash
 chromatography [methylene chloride/methanol/ammonia (17%) 15:4:0.5. The pH
 is brought to 7 with a 0.1N sodium hydroxide solution and lyophilization
 is carried out. Yield: 60 mg (44%). [TLC: acetonitrile/water/glacial
 acetic acid 5:1:0.2 R.sub.f =0.42] FAB-MS: m/z=773=M-2Na.sup.+ +3H.sup.+.
 EXAMPLE 12.13
 N-[O-(3-O-Methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-quin
 olone-a
 Educts:
 32 mg (0.12 mmol) of carbohydrate from Example 1.2;
 50 mg (0.12 mmol) of quinolone-a
 Reaction time of 2 hours; purification by flash chromatography [methylene
 chloride/methanol/glacial acetic acid 9:10:1]; precipitation from
 methylene chloride/methanol 1:1 with ether. Yield: 59 mg (51%). [TLC:
 acetonitril/water 10:1 R.sub.f =0.43].
 EXAMPLE 12.14
 N-{N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-quin
 olone-a, hydrochloride
 86 mg (0.1 mmol) of the compound from Example 12.5 are taken up in water
 and converted into the salt with one equivalent of 0.1N hydrochloric acid.
 After freeze drying, 88 mg of the target compound are obtained.
 EXAMPLE 12.15
 N-{N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-diam
 ino-propionoyl)-quinolone-a, hydrochloride
 The glycoconjugate 12.5 is prepared analogously to Example 12.14 via
 several stages starting from N.sup..alpha.
 -(tert-butoxycarbonyl)-N.sup..beta.
 -(fluorenyl-9-methoxycarbonyl)-L-diaminopropionic acid and quinolone-a
 [TLC: acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.3].
 EXAMPLE 13
 General Formula
 ##STR112##
 EXAMPLE 13.1
 N-{N'-[O-(3-O-Methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]-
 D-alanyl}-quinolone-b
 13.1.a) Quinolone-b:
 4-amino-7-[(3aRS,4RS,7aSR)-4-amino-1,3,3a,4,7,7a-hexa-hydro-isoindol-2-yl]
 -1-cyclopropyl-6-fluoro-1,4-dihydro-8-methoxy-4-oxo-3-quinolinecarboxylic
 acid
 170 mg (1.5 mmol) of 1,4-diazabicyclo[2.2.2]octane and 152 mg (1.1 mmol) of
 (3aRS,4RS,7aSR -4-amino-1,3,3a,4,7,7a-hexahydro-isoindole are added to 310
 mg (I mmol) of
 5-amino-1-cyclopropyl-6,7-difluoro-1,4-dihydro-8-methoxy4-oxo-3-quinolinec
 arboxylic acid in a mixture of 4 ml of acetonitrile and 2 ml of
 dimethylformamide and the mixture is heated under reflux for 1 hour. It is
 concentrated in vacuo, the residue is stirred with about 20 ml of water
 and the residue which has precipitated is filtered off with suction and
 dried at 100.degree. C. in vacuo.
 Yield: 301 mg (70% of theory), Melting point: 237-239.degree. C. (with
 decomposition).
 13.1.b) N-[D-Alanyl]-quinolone-b, trifluoroacetate
 The target compound is prepared analogously to Example 9.1 starting from
 compound 13.1.a and N-(tert-butoxycarbonyl)-D-alanine.
 13.1)
 N-{N'-(O-(3-O-Methyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbonyl]
 -D-alanyl}-quinolone-b
 The target compound is prepared analogously to Example 12.1 starting from
 compound 13.1.b and p-aminophenyl 3O-methyl-.beta.-L-fucoside (Example
 1.2).
 EXAMPLE 14
 General Formula
 ##STR113##
 Quinolone-c:
 8-(2amino-5-methyl-8-azabicyclo[4.3.
 0]non-3-en-8-yl)-1-methyl-7-fluoro-5-oxo-5H-thiazolo[3,2-a]quinoline-4-car
 boxylic acid
 EXAMPLE 14.1
 N-{-N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-D-galactopyranosyl)-4hydroxy-phenylamino-thio-carbo
 nyl]-lysyl}-quinolone-c, hydrochloride
 14.1.a) N-[N.sup..epsilon.
 -(Fluorenyl-9-methoxycarbonyl)-lysyl]-quinolone-c, trifluoroacetate
 Educts:
 N.sup..alpha. -(tert-butoxycarbonyl)-N.sup..epsilon.
 -(fluorenyl-9-methoxycarbonyl)-lysine
 (1.4 g, 3.0 mmol);
 quinolone-c (820 mg, 1.9 mmol)
 The preparation of the intermediate product is carried out analogously to
 Example 9.1.a. Reprecipitation from ethanol/diethyl ether gives pale
 yellow crystals (1.37 g, 82%), from which compound 14.1.a is liberated
 analogously to Example 9.1.b. Orange crystals (1.25 g, 74%) are obtained;
 TLC [methylene chloride/methanol/ammonia (25%) 30:10:1]: R.sub.f =0.7;
 melting point 180.degree. C.
 14.a) N-{N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thiocarbo
 nyl]-lysyl}-quinolone-c, hydrochloride
 Compound 1.25 (62.8 mg, 0.22 mmol) is reacted with peptide conjugate 14.1.a
 (178.4 mg, 0.2 mmol) analogous to Example 12.5. Purification of the
 intermediate stage is carried out by flash chromatography [methylene
 chloride/methanol/ammonia (25%) 30:6:1.fwdarw.30:10:1]. Pale yellow
 crystals (97.0 mg, 44%) are obtained; TLC [methylene
 chloride/methanol/ammonia (25%) 30:10:1]: R.sub.f =0.23. The
 fluorenyl-9-methoxycarbonyl group is then split off as described and the
 product is purified. Yellow crystals are obtained and are suspended in
 water (10 ml). 0.1N hydrochloric acid is added dropwise to the suspension,
 while stirring, until a clear solution forms (pH&gt;3). Lyophilization of the
 filtered solution is a yellow amorphous solid (75.8 mg, 41%);
 [.alpha.].sub.D.sup.20 =+12.5.degree. (c=0.27/H.sub.2 O).
 The following glycoconjugates are prepared analogously to Example 14.1 from
 peptide conjugate 14.1.a:
 EXAMPLE 14.2
 N-{N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thio-carbony
 l]-lysyl}-quinolone-c, hydrochloride
 Educts:
 compound 1.2 (59.5 mg, 0.22 mmol)
 peptide conjugate 14.1.a (178.4 mg, 0.2 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol/ammonia (25%) 30:6:1.fwdarw.30:10:1]. Pale yellow
 crystals (146.6 mg, 67%) are obtained; TLC [methylene
 chloride/methanol/ammonia (25%) 30:6:1]: R.sub.f =0.48. The
 fluorenyl-9-methoxycarbonyl group is then split off as described and the
 product is converted into the hydrochloride. A yellow amorphous solid
 (107.7 mg, 60%) is obtained; [.alpha.].sub.D.sup.20 =+51.6.degree.
 (c=0.36/H.sub.2 O).
 EXAMPLE 14.3
 N-{N.sup..alpha.
 -[O-(3-O-Carboxymethyl-.beta.-L-fucosyl)-4-hydroxy-phenylamino-thiocarbony
 l]-lysyl}-quinolone-c, di-sodium salt
 The glycoconjugate 14.4 is prepared analogously to Example 12.6 via several
 stages starting from compound 14.1.a [FAB-MS: m/z=911=M-2Na+3H].
 EXAMPLE 14.4
 N-{N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocarbonyl
 ]-D-lysyl}-quinolone-c, hydrochloride
 The conjugate is prepared analogously to the isomer in Example 14.2
 (FAB-MS: m/z=867=M+H].
 EXAMPLE 15
 General Formula
 ##STR114##
 Quinolone-d:
 4-(2-amino-8-azabicyclo[4.3.
 0]non-4-en-8-yl)-1-cyclopropyl-6,8-difluoro-1,4-dihydro-4-oxo-quinoline-3-
 carboxylic acid
 EXAMPLE 15.1
 N-{N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thiocarbo
 nyl]-lysyl}-quinolone-d, hydrochloride
 15.1.a) N-[N.sup..epsilon.
 -(Fluorenyl-9-methoxycarbonyl)-lysyl]-quinolone-d, trifluoroacetate
 N.sup..alpha. -(tert-Butoxycarbonyl)-N.sup..epsilon.
 -(fluorenyl-9-methoxycarbonyl)-lysine (1.4 g, 3.0 mmol) is reacted with
 quinolone-d, hydrochloride (1.28 mg, 2.8 mmol) as described in Example
 9.1.a. Reprecipitation from methylene chloride/methanol 1:1 with diethyl
 ether gives beige crystals (1.97 g, 83%), from which compound 15.1.a is
 liberated analogously to Example 9.1.b. Beige crystals (1.7 g, 70%) are
 obtained; TLC [methylene chloride/methanol/ammonia (25%) 28:14:1]: R.sub.f
 =0.60; melting point=215.degree. C.
 15.1) N-{N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thio-carb
 onyl]-lysyl}-quinolone-d, hydrochloride
 Compound 1.25 (62.8 mg, 0.22 mmol) is reacted with peptide conjugate 15.1.a
 (173.2 mg, 0.2 mmol) analogously to Example 12.5. Purification of the
 intermediate stage is carried out by flash chromatography [methylene
 chloride/methanol/ammonia (25%) 28:14:1.fwdarw.methanol/ammonia (25%)
 20:1]. Beige crystals (140.8 mg, 65%) are obtained; TLC [methylene
 chloride/methanol/ammonia (25%) 28:14:1]: R.sub.f =0.06. The
 fluorenyl-9-methoxycarbonyl group is then split off as described and the
 product is purified. Beige crystals are obtained and are suspended in
 water (10 ml). 0.1N hydrochloric acid is added dropwise to the suspension,
 while stirring, until a clear solution forms (pH&gt;3). Lyophilization of the
 filtered solution gives a yellow amorphous solid (102.6 mg, 57%);
 [.alpha.].sub.D.sup.20 =-49.0.degree. (c=0.26/H.sub.2 O).
 The following glycoconjugates are prepared analogously to Example 15.1 from
 peptide conjugate 15.1.a:
 EXAMPLE 15.2
 N-{N.sup..alpha.
 -[O-(4-O-(3'-O-Methyl-.beta.-D-galactopyranosyl)-.beta.-D-glucopyranosyl)-
 4-hydroxy-phenylamino-thiocarbonyl]-lysyl}-quinolone-d, hydrochloride
 Educts:
 compound 1.58 (98.4 mg, 0.22 mmol)
 peptide conjugate 15.1.a (173.2 mg, 0.2 mmol)
 Purification of the intermediate stage by flash chromatography [methylene
 chloride/methanol/ammonia (25%)
 20:10:1.fwdarw.10:10:1.fwdarw.methanol/ammonia (25%) 20:1]. Beige crystals
 (106.5 mg, 43%) are obtained; TLC [methylene chloride/methanol/ammonia
 (25%) 10:10:3]: R.sub.f =0.51. The fluorenyl-9-methoxycarbonyl group is
 then split off as described and the product is converted into the
 hydrochloride. A yellow amorphous solid (82.0 mg, 39%) is obtained;
 [.alpha.].sub.D.sup.20 =+22.8.degree. (c=0.29/H.sub.2 O).
 EXAMPLE 16
 Glycoconjugates With Melphalan
 General Formula
 ##STR115##
 EXAMPLE 16.1
 N-{N'-[O-3-O-Methyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocarbo
 nyl]-D-alanyl}-melphalan
 16.1.a) N-tert-Butoxycarbonyl-D-alanyl-melphalan
 114 mg (0.6 mmol) of N-tert-butoxycarbonyl-D-alanine are dissolved in 10 ml
 of dimethylformamide, and 138 mg of
 N'-(3-dimethylaminopropyl)-N-ethyl-carbodiimide, hydrochloride and
 1-hydroxy-benzotriazole are added at 0.degree. C. After 10 minutes, 153 mg
 of melphalan are added and the mixture is stirred at room temperature for
 16 hours. It is concentrated and the residue is partitioned between
 methylene chloride and water. The organic phase is washed, dried over
 sodium sulphate and concentrated and the residue is then subjected to
 flash chromatography with methylene chloride/methanol/ammonia (17%)
 15:2:0.2.fwdarw.15:4:0.5. 134 mg (56%) of the target compound are obtained
 [TLC: methylene chloride/methanol/ammonia (17%) 15:4:0.5 R.sub.f =0.45].
 16.1)
 N-{N'-[O-(3-O-Methyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocar
 bonyl]-D-alanyl}-melphalan
 Splitting off of the protective group and coupling with the carbohydrate
 are carried out as described in Examples 9.1 and 12.1. [TLC:
 acetonitrile/water 10:1 R.sub.f =0.26; FAB-MS: m/z=685=M-H.
 EXAMPLE 16.2
 N-{N'-[O-(3-O-Methyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocarb
 onyl]-alanyl-alanyl}-melphalan
 This compound can be prepared analogously to Example 16.1 via several
 stages (TLC: acetonitrile/water 10:1 R.sub.f =0.2; FAB-MS: m/z=756=M-H).
 EXAMPLES 17
 Glycoconjugates With Doxorubicin (Adriamycin)
 General Formula
 ##STR116##
 EXAMPLE 17.1
 N-{N'-[O-(3--Methyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocarbo
 nyl]-alanyl-alanyl}-doxorubicin
 17.1.a)
 N-[O-(3-O-Methyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocarbony
 l]-alanyl-alanine
 160 mg (1 mmol) of alanyl-alanine are taken up in 20 ml of dioxane/water
 1:1, and 1 ml of Hunig base is added. 1.2 mmol of p-aminophenyl
 3-O-methyl-.beta.-L-fucoside (Example 1.2) are first converted into the
 isothiocyanate in accordance with instructions 10.1.a and the product is
 then added to the solution of the dipeptide. The mixture is stirred at
 room temperature for 16 hours and the residue is purified by flash
 chromatography (acetonitrile/water 15:1). After concentration of the
 corresponding fractions, the product is precipitated from methanol/ether.
 Yield: 267 mg (57%).
 17.1)
 N-{N'-[O-(3-O-Methyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocar
 bonyl]-alanyl-alanyl}-doxorubicin
 48 mg (0.1 mmol) of the compound from Example 17.1.a are dissolved in 10 ml
 of dimethylformamide, and 23.1 mg of
 N'-(3-dimethylaminopropyl)-N-ethyl-carbodiimide, hydrochloride and 21 mg
 of 1-hydroxy-benzotriazole are added. After 5 minutes, 30 mg of
 doxorubicin and 35 .mu.l of Hunig base are added and the mixture is
 stirred at room temperature for 30 minutes. It is concentrated and the
 residue is purified by flash chromatography (methylene chloride/methanol
 88:12). The corresponding fractions are concentrated and the residue is
 lyophilized from dioxane/water. 20 mg (40%) of the target compound are
 obtained. [TLC: methylene chloride/methanol 10:1 R.sub.f =0.17; ESI:
 m/z=997=M+H].
 EXAMPLE 17.2
 N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-L-fuccopyranosyl)-4-hydroxy-phenylamino-thiocar
 bonyl]-D-lysyl-alanyl}-doxorubicin
 17.2.a) N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocarb
 onyl]-D-lysyl-alanine
 580 mg (1.31 mmol) of the bis-trifluoroacetate of D-lysyl-alanine are
 linked with 2.2 equivalents of the carbohydrate from Example 1.2 in the
 presence of 1.3 ml of Hunig base as described in Example 17.1.a.
 Purification by flash chromatography is carried out with
 acetonitrile/water 10:1. 446 mg (41%) of the target compound are obtained.
 17.2) N-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocarb
 onyl]-D-lysyl-alanyl}-doxorubicin
 Linking of 59 mg of the compound from Example 17.2.a with 20 mg of
 doxorubicin is carried out as described in Example 17.1. 15 mg of the
 conjugate are obtained. [TLC: methylene chloride/methanol 85:15 R.sub.f
 =0.43; FAB-MS: m/z=1365=M+H].
 EXAMPLES 18
 Glycoconjugates With Camptothecin
 General Formula
 ##STR117##
 EXAMPLE 18.1
 20-O-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocarb
 onyl]-lysyl-alanyl}-camptothecin
 18.1.a) 20-O-(Alanyl)-camptothecin, trifluoroacetate
 500 mg (1.44 mmol) of camptothecin are dissolved in 20 ml of
 dimethylformamide, and 50 mg of 4-dimethylaminopyridine and
 N-tert-butoxycarbonyl-alanine N-carboxy-anhydride are then added. After 3
 hours, a further 775 mg of
 N-tert-butoxycarbonyl-alanine-N-carboxy-anhydride are added and the
 suspension is treated with ultrasound for 16 hours. The mixture is
 concentrated, the crude material is taken up in 50 ml of methylene
 chloride, and 5 ml of trifluoroacetic acid are added at 0.degree. C. After
 the mixture has been stirred for 30 minutes, it is concentrated again and
 the product is purified by flash chromatography (acetonitrile/water 20:1).
 The corresponding fractions are collected and concentrated and the residue
 is lyophilized from dioxane/water. 712 mg (93%) of the target compound are
 obtained [FAB-MS: m/z=420=M+H].
 18.1.b) 20-O-(Lysyl-alanyl)-camptothecin, bis-trifluoroacetate
 The conjugate from Example 18.1.a is linked with
 N.sup..alpha.,N.sup..epsilon. -bis-(tert-butoxycarbonyl)-lysine in
 accordance with the standard instructions and the product is then
 deblocked. The target compound is obtained in a 65% yield.
 18.1) 20-O-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocarb
 onyl]-lysyl-alanyl}-camptothecin
 p-Aminophenyl 3-O-methyl-.beta.-L-fucoside (Example 1.2) is linked with the
 conjugate of Example 1 8.1.b analogously to the instructions in Example
 11.1. Yield: 40% [TLC: acetonitrile/water 10:1 R.sub.f =0.44].
 EXAMPLE 18.2
 20-O-{N.sup..alpha.
 -[O-(3-O-Carboxymethyl-.beta.-fucopyranosyl)-4hydroxy-phenylamino-thiocarb
 onyl]-lysyl-alanyl}-camptothecin
 18.2.a) 20-O-[N-(Fluorenyl-9-methoxycarbonyl)-lysyl-alanyl]-camptothecin,
 trifluoroacetate
 The conjugate from Example 18.1.a is linked with N.sup..alpha.
 -(tert-butoxycarbonyl)-N.sup..epsilon.
 -(fluorenyl-9-methoxycarbonyl)-lysine in accordance with the standard
 instructions and the product is then deblocked on the .alpha.-amino
 function. The target compound is obtained in a 24% yield. [TLC:
 acetonitrile/water 20.1 R.sub.f =0.15].
 18.2.b) 20-O-(N.sup..alpha.
 -[O-(3-O-Carboxymethyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thioc
 arbonyl]-N.sup..epsilon.
 -[fluorenyl-9-methoxycarbonyl]-lysyl-alanyl}-camptothecin
 The compound from Example 18.1.a is modified with the carbohydrate
 derivative from Example 1.10 analogously to Example 12.6 and 12.5. The
 crude product can be purified by digestion with water and is then
 lyophilized from dioxane/water and employed in the next stage without
 further characterization.
 18.2) 20-O-{N.sup..alpha.
 -[O-(3-O-Carboxymethyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thioc
 arbonyl]-lysyl-alanyl}-camptothecin
 The conjugate 18.2.b is deblocked with piperidine in dimethylformamide.
 After 30 minutes, the mixture is concentrated and the residue is digested
 twice with methylene chloride. It is then taken up in dimethylformamide
 and precipitated with methanol/ether. The product is filtered off with
 suction, washed with ether and then lyophilized from dioxane/water. Yield:
 86% [TLC: acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.17].
 EXAMPLE 18.3
 20-O-{N.sup..alpha.
 -[O-3-O-Carboxymethyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thioca
 rbonyl]-lysyl-alanyl}-camptothecin, sodium salt
 62 mg (0.074 mmol) of the conjugate from Example 18.2 are taken up in
 dioxane/water and converted into the sodium salt with one equivalent of a
 0.1N sodium hydroxide solution. Yield: quantitative [TLC:
 acetonitrile/water/glacial acetic acid 5:1:0.2 R.sub.f =0.17].
 The following glycoconjugates of camptothecin are prepared analogously to
 Examples 18.1 and 18.2:
 EXAMPLE 18.4
 20-O-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocarb
 onyl]-lysyl-D-alanyl}-camptothecin
 EXAMPLE 18.5
 20-O-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-methyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocarb
 onyl]-lysyl-valinyl}-camptothecin
 EXAMPLE 18.6
 20-O-{N.sup..alpha.
 -[O-3-O-Carboxymethyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thioca
 rbonyl]-lysyl-valinyl}-camptothecin
 EXAMPLE 18.7
 20-O-{N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thio-carb
 onyl]-lysyl-valinyl}-camptothecin
 EXAMPLE 18.8
 20-O-{N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-D-galactopyranosyl)-4-hydroxy-phenylamino-thio-carb
 onyl]-lysyl-alanyl}-camptothecin
 EXAMPLE 18.9
 20-O-{N.sup..alpha.
 [O-(3-O-Carboxymethyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thioca
 rbonyl]-lysyl-valinyl}-camptothecin, hydrochloride
 Compound 18.6 is converted into the hydrochloride with one equivalent of
 0.01N hydrochloric acid.
 EXAMPLE 18.10
 20-O-{N.sup..alpha.
 [O-(3-O-Carboxymethyl-.beta.-fucopyranosyl)-4-hydroxy-phenylamino-thiocarb
 onyl]-lysyl-alanyl}-camptothecin, hydrochloride
 Compound 18.2 is converted into the hydrochloride with one equivalent of
 0.01N hydrochloric acid.
 EXAMPLE 18.11
 20-O-{N.sup..alpha.
 [O-(3-O-Carboxymethyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thioca
 rbonyl]-lysyl-phenylalanyl}-camptothecin, hydrochloride
 EXAMPLE 18.12
 20-O-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carboxymethyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-t
 hiocarbonyl]-lysyl-alanyl}-camptothecin, sodium salt
 EXAMPLE 18.13
 20-O-{N.sup..alpha.,N.sup..epsilon.
 -Bis-[O-(3-O-carboxymethyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-t
 hiocarbonyl]-lysyl-valinyl}-camptothecin, sodium salt
 EXAMPLE 18.14
 20-O-{N.sup..alpha.
 -[O-(3-O-Methyl-.beta.-L-fucopyranosyl)-4-hydroxy-phenylamino-thiocarbonyl
 ]-lysyl-alanyl}-camptothecin, hydrochloride