# Patent

## Title
Tubular reactor method for conducting heterogeneous reactions

## Abstract

are useful for dyeing and printing fibers, threads and textile materials, particularly those containing or consisting of natural or synthetic polyamide, cotton, polyacrylonitrile, leather or fiber blends such as cotton-polyester, polyester-wool and polyacrylonitrile-wool.

## Background
The invention relates to water-soluble azo compounds which contain basic groups and are free from sulphonic acid groups which compounds are metal-free or are in 1:1 or 1:2 metal complex form. These compounds are suitable for use as dyestuffs.

According to the invention there is provided monoazo and disazo compounds in metal-free form or in 1:1 or 1:2 metal complex form which in metal-free form correspond to formula I

in which tetrahydronaphthalene series, pyrazol-5-one, pyridine, pyridone, barbituric acid, quinoline, isoquinoline, benzene- or naphthalene- or tetrahydronaphthalene-azo-benzene or -azo-naphthalene, or of the acetoacetamide series,

each W.sub.2, independently, is a divalent bridging group,

each Z, independently, is a water solubilising protonable amine group, a quaternary ammonium group, a hydrazinium group or a ternary sulphonium group, bound to the carbon atom of a triazine or pyrimidine group which therefore constitutes part of a fibre-reactive grouping is excluded;

which compound is in free base form, salt form or acid addition salt form formed by the addition of dilute aqueous organic or mineral acids, and mixtures of compounds of formula I.

Preferably, D is the radical of a diazo component of the benzene or naphthalene series in which the group --W.sub.1 --SO.sub.2 CH.dbd.CH.sub.2 is preferably bound in the 3- or 4-position of any phenyl group; on any naphthyl group --W.sub.1 --SO.sub.2 CH.dbd.CH.sub.2 is particularly preferred in the 4-position. D is further unsubstituted or may contain one or two further substituents conventional in the chemistry of fibre-reactive azo compounds (with the exception of sulphonic acid groups) including any metallisable substituent in the ortho position to a carbon atom bound to the azo group, such as a hydroxy, amine, substituted amine, methoxy or carboxy group.

K is preferably the radical of a coupling component of the aminobenzene, phenol, aminophenol, aminonaphthalene, naphthol or aminonaphthol series or of the naphthalene series containing any other substituent enabling the coupling; of the 1-arylpyrazol-5-one, aminopyridine, hydroxypyridone, barbituric acid, N-alkyl or N-aryl substituted acetoacetamide, benzene- or naphthalene-azo-benzene, benzene-azo-naphthalene or tetrahydronaphthalene-azo-benzene series.

Additionally to the n groups --W.sub.2 --Z K is further unsubstituted or may contain one or two further substituents conventional in the chemistry of basic azo compounds including those substituents which enable the metallisation and therefore are in the ortho position to a carbon atom bound to the azo group.

n is preferably 1 or 2.

W.sub.1 is preferably a direct bond; a C.sub.1-6 alkylene or C.sub.2-6 alkenylene group which groups are straight chain or branched, unsubtituted or monosubstituted by hydroxy, halogen, cyano, C.sub.1-4 alkoxy or phenyl and in which the carbon chains may be interrupted by one or two hetero atoms; --CONH--X--, --CO--X--, --SO.sub.2 NH--X--, --NHCO--x--, --NH--X-- or --NHNHCO--X--, in which X is C.sub.1-6 alkylene or C.sub.2-6 alkenylene and which groups are bound to the --SO.sub.2 -- group by a carbon atom of X; --CH.sub.2 CONHCH.sub.2 -- or --CH.sub.2 NHCOCH.sub.2 --.

Each W.sub.2, independently, has preferably one of the significances of W.sub.1 except a direct bond where Z is attached to a carbon atom of X.

Each Z, independently, is preferably a water-solubilising protonatable amino group or a quaternary ammonium group; preferably Z is a primary amino group, a secondary or tertiary aliphatic, cycloaliphatic, aromatic or saturated or partially unsaturated heterocyclic amino group in which latter group the N-atom or a carbon atom is attached to W.sub.2 ; or a quaternary ammonium group corresponding to the above.

In the specification any halogen means fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.

The term "basic groups" also includes quaternary ammonium groups, hydrazinium groups and ternary sulphonium groups.

Any alkyl, alkylene or alkenylene present may be linear or branched unless indicated otherwise. The alkyl group of any alkoxy group is linear or branched unless indicated to the contrary.

In any hydroxy substituted alkyl, alkylene or alkenylene group which is attached to a nitrogen atom the hydroxy group is bound to a carbon atom other than to the C.sub.1 -atom.

Any aliphatic amino group as Z is preferably a mono-C.sub.1-4 -alkyl- or a di-(C.sub.1-4 alkyl)-amino grpoup. The alkyl group may be monosubstituted by halogen, hydroxy, cyano, C.sub.1-4 alkoxy or phenyl. Any cycloaliphatic amino group is preferably C.sub.5-6 cycloalkylamino, the cycloalkyl group of which may be substituted by one or two C.sub.1-2 alkyl groups.

Any aromatic amino group is preferably phenylamino, the phenyl ring of which is unsubstituted or substituted by one or two groups selected from halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, hydroxy and phenoxy.

Any heterocyclic amino group as Z in which the N-atom or a carbon atom is attached to W.sub.2 is preferably a saturated, unsaturated or partially unsaturated 5- or 6-membered ring which contains one or two hetero atoms and may be further substituted by one or two C.sub.1-4 alkyl groups.

1:1 and 1:2 metal complexes of compounds of formula I according to invention, preferably in the 1:1 metal complex form, correspond to formula II or III ##STR1## in which W.sub.1, W.sub.2, D, Z and n are as defined above, Me is copper, chromium, cobalt, nickel or iron for 1:1 metal complexes (Me is preferably copper in this case) or Me is chromium or cobalt for 1:2 metal complexes, naphthalene series, ortho position to the carbon atom attached to the azo group either hydrogen or a metallisable group resulting in Y.sub.1 (--O-- or --COO--) and Y.sub.2 /Y.sub.3 (--O--, --NH-- or --N<), respectively, naphthalene or tetrahydronaphthalene series containing in an ortho position to the carbon atom attached to the group --N.dbd.N--K.sub.1 either hydrogen or a metallisable group resulting in Y.sub.2,

Preferred compounds or complexes according to the invention correspond in metal-free form to formula Ia,

in which ##STR2## in which each of R.sub.1 and R.sub.2, independently, is hydrogen, halogen, hydroxy, cyano, nitro, trifluoromethyl, carboxy, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, phenoxy, the phenyl ring of which is unsubstituted or substituted by up to three halogen atoms; sulphonamido, --SO.sub.2 NHC.sub.1-4 alkyl, --SO.sub.2 N(C.sub.1-4 alkyl).sub.2, --SO.sub.2 C.sub.1-4 alkyl, --NHCOC.sub.1-4 alkyl, benzamido or phenylamino, alkoxy, phenoxy, phenylamino, --NHC.sub.1-4 alkyl, --N(C.sub.1-4 alkyl).sub.2, --NHCOC.sub.1-4 alkyl or benzamido, group which groups are unsubstituted or monosubstituted by halogen, hydroxy, C.sub.1-4 alkoxy or phenyl, and in which the --C--C-- chains may be interrupted by an N, O or S atom; --NH--X.sub.a --CONH--X.sub.a --; --NHCO--X.sub.a --; --CO--X.sub.a --; --SO.sub.2 NH--X.sub.a --; --NHNHCO--X.sub.a --; --CH.sub.2 CONHCH.sub.2 -- or --CH.sub.2 NHCOCH.sub.2 --, W.sub.1a is attached to the SO.sub.2 -group by a carbon atom of X.sub.a, corresponds to a group (c) to (i): ##STR3## in which R.sub.4 is hydrogen, halogen, hydroxy, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, --NHCOC.sub.1-4 alkyl, --NHCONH.sub.2, --SO.sub.2 NH.sub.2, --SO.sub.2 NHC.sub.1-4 alkyl, --SO.sub.2 N(C.sub.1-4 alkyl).sub.2, --NHCO(CH.sub.2).sub.1-4 --Z.sub.1 or --SO.sub.2 N[(CH.sub.2).sub.1-4 --Z.sub.1 ].sub.2, substituted by one or two hydroxy groups or by a phenyl group, halogen or cyano; --(CH.sub.2).sub.1-4 --NHCO(CH.sub.2).sub.1-4 --Z.sub.1 or C.sub.1-6 alkylene-Z.sub.1, in which the alkylene group may be substituted by one or two hydroxy groups, substituted by one or two hydroxy groups or by a phenyl group, halogen or cyano; --COCH.sub.2 --Z.sub.1, C.sub.1-8 alkylene--Z.sub.1 in which the alkylene group may be substituted by one or two hydroxy groups and in which the alkylene chain may be interrupted by atom groups, such as --NH--, --NCH.sub.3, --S--, --O--, --NHCO or --OCO--; or ##STR4## each Z.sub.1, independently, Q and Q.sub.1 are as defined below;

(d) is a group of formulae (d.sub.1) to (d.sub.5), where (d.sub.1) to (d.sub.3) are naphthol groups of the formulae ##STR5## in which R.sub.8a is ##STR6## R.sub.8b is --NHCO(CH.sub.2).sub.1-4 --Z.sub.1, --SO.sub.2 NH(CH.sub.2).sub.1-4 --Z.sub.1 or ##STR7## R.sub.8c is --NHCO(CH.sub.2).sub.1-4 --Z.sub.1, --NH(CH.sub.2).sub.1-4 --Z.sub.1 or ##STR8## and Q, Q1 and Z.sub.1 are as defined below;

(d.sub.4) is an aminonaphthyl group of the formulae ##STR9## in which Z.sub.1, Q and Q.sub.1 are as defined below;

and (d.sub.5) is a naphthyl group of the formula ##STR10## in which one of the R.sub.8d "s is hydrogen and the other is --CONH(CH.sub.2).sub.1-4 --Z.sub.1, --NHCO(CH.sub.2).sub.1-4 --Z.sub.1, --SO.sub.2 NH(CH.sub.2).sub.1-4 --Z.sub.1, --NH(CH.sub.2).sub.1-4 --Z.sub.1 or ##STR11## t is 0 or 1 and Q, Q.sub.1 and Z.sub.1 are as defined below;

(e) is a group of the formula ##STR12## in which R.sub.9 is C.sub.1-4 alkyl, --COOH or --COOC.sub.1-4 alkyl, ##STR13## each of R.sub.11 and R.sub.12, independently, is hydrogen, halogen, nitro, amino, cyano, hydroxy, C.sub.1-4 alkyl or C.sub.1-4 alkoxy, ##STR14## W.sub.2a has one of the significances of W.sub.1a defined above except a direct bond, where Z.sub.1 is attached to a carbon atom of X.sub.a, and

(f) is a group of the formula ##STR15## in which R.sub.14 is hydrogen, C.sub.1-4 alkyl, phenyl, benzyl or cyclohexyl, ##STR16## R.sub.16 is hydrogen, ##STR17## C.sub.1-4 alkyl unsubstituted or monosubstituted by OH, CN, halogen or C.sub.1-4 alkoxy; C.sub.1-6 alkylene--Z.sub.1, ##STR18## t is 0 or 1, and Q, Q.sub.1, Z.sub.1 and A.sup..crclbar. are as defined below;

(g) is a group of the formula ##STR19## in which R.sub.17 is C.sub.1-6 alkylene--Z.sub.1 or ##STR20## R.sub.11, R.sub.12 and R.sub.13 are as defined above and Z.sub.1 is as defined below; ##STR21## in which R.sub.14 is as defined above,

each R.sub.19, independently, is hydrogen, a C.sub.1-4 alkyl group which is unsubstituted or monosubstituted by hydroxy or C.sub.1-4 alkoxy; or C.sub.1-6 alkylene--Z.sub.1, cyclohexylamino, C.sub.1-4 alkylamino, di(C.sub.1-4 alkyl)amino or Q; ammonium group --N.sup..sym. R.sub.22 R.sub.23 R.sub.24 A.sup..crclbar., heterocyclic ring of the formula ##STR22## or a corresponding protonatable or quaternary 5- or 6-membered unsaturated or partially unsaturated heterocyclic ring, C.sub.2-4 alkyl monosubstituted by hydroxy, C.sub.1-4 alkoxy, halogen or cyano; phenyl-C.sub.1-4 alkyl, the phenyl group of which is unsubstituted or substituted by one to three groups selected from chlorine, C.sub.1-4 alkyl and C.sub.1-4 alkoxy, or C.sub.5-6 cycloalkyl, or form a heterocyclic ring of the formula ##STR23## in which U is the direct bond, --CH.sub.2 --, --O--, --S--, --SO.sub.2 --, --SO--, --NH--, --N(C.sub.1-4 alkyl)-- or --N.sup..sym. (C.sub.1-4 alkyl).sub.2 -- A.sup..crclbar.,

each of R.sub.22 and R.sub.23 has independently one of the cyclic or non-cyclic significances of R.sub.20 and R.sub.21 except hydrogen, and attached, form a pyridinium group unsubstituted or substituted by one or two methyl groups, or a ring of the formula ##STR24## in which R.sub.24, U and A.sup..crclbar. are as defined above, R.sub.25 is hydrogen or C.sub.1-4 alkyl and

each R.sub.26, independently, is C.sub.1-4 alkyl;

(i) is a group of formulae (i.sub.1) to (i.sub.4) ##STR25## in which M is ##STR26## each of R.sub.4 and R.sub.5, independently, is as defined above and R.sub.6, R.sub.7, Q, Q.sub.1 and Z.sub.1 are as defined above.

More preferred are compounds or complexes according to the invention containing one or two protonatable amino groups or quaternary ammonium groups as defined above which correspond in metal-free form to formula Ib or Ic ##STR27## in which t is 0 or 1, ##STR28## R.sub.1a is hydrogen, halogen, C.sub.1-2 alkyl, C.sub.1-2 alkoxy, --OH, --COOH, --CN, phenoxy, the phenyl group of which may be substituted by one to three chlorine atoms, --SO.sub.2 NH.sub.2, --SO.sub.2 NHC.sub.1-2 alkyl, --SO.sub.2 N(C.sub.1-2 alkyl).sub.2, --NHCOCH.sub.3 or phenylamino, (e.sub.1), (f.sub.1), (g.sub.1), (i.sub.2a), (i.sub.3a) or (i.sub.4a), ##STR29## in which R.sub.4a is hydrogen, chlorine, C.sub.1-2 alkyl, C.sub.1-2 alkoxy, --NHCOC.sub.1-2 alkyl, --NHCONH.sub.2 or --NHCO(CH.sub.2).sub.1-4 --Z.sub.2, --C.sub.2 H.sub.4 CN, --C.sub.2 H.sub.4 Cl, C.sub.1-4 alkylene--Z.sub.2, --CH.sub.2 CH(OH)CH.sub.2 --Z.sub.2 or --(CH.sub.2).sub.2-3 --NHCOCH.sub.2 --Z.sub.2, H.sub.4 Cl, C.sub.2 H.sub.4 CN, C.sub.1-4 alkylene--Z.sub.2, --CH.sub.2 CH(OH)CH.sub.2 --Z.sub.2, --(CH.sub.2).sub.2-3 --OCH.sub.2 CH(OH)CH.sub.2 --Z.sub.2, --(CH.sub.2).sub.2-3 --NHCOCH.sub.2 --Z.sub.2, --COCH.sub.2 --Z.sub., ##STR30## in which R.sub.8a ' is ##STR31## R.sub.8b ' is ##STR32## R.sub.8c ' is ##STR33## one of the groups R.sub.8d ' is hydrogen and the other is ##STR34## in which R.sub.10a is ##STR35## each of R.sub.11a and R.sub.12a, independently, is hydrogen, chlorine, methyl or methoxy, ##STR36## in which R.sub.14a is hydrogen, methyl, ethyl or benzyl, ##STR37## in which R.sub.17a is ##STR38## and R.sub.11a, R.sub.12a and R.sub.13a are as defined above; ##STR39## in which Ma is ##STR40## R.sub.4a, R.sub.5a, R.sub.6a and R.sub.7a are as defined above and Z.sub.2 is as defined below; phenylamino or Q.sub.a ; R.sub.23a R.sub.24a A.sup..crclbar.,

each of R.sub.20a and R.sub.21a, independently, is hydrogen, C.sub.1-2 alkyl, unbranched hydroxy-C.sub.2-3 alkyl or benzyl or both R.sub.20a and R.sub.21a, together with the N-atom to which they are attached, form a pyrrolidine, piperidine, morpholine, piperazine or N-methylpiperazine group, cyclic significances of R.sub.20a and R.sub.21a except hydrogen, and are attached, for a pyridinium group unsubstituted or substituted by one or two methyl groups.

In a compound of formula Ib the positions for R.sub.1a, R.sub.2a and the group --(CH.sub.2).sub.t --SO.sub.2 --CH.dbd.CH.sub.2 (.dbd.R) preferably are as follows:

(i) R.sub.1a =R.sub.2a =H: it is in the 3- or 4-position;

(iii) R.sub.1a and R.sub.2a .noteq.H:

Most preferred are compounds or complexes according to the invention which, in metal-free form, correspond to formula Id, ##STR41## in which t is 0 or 1, ##STR42## in which R.sub.4b is hydrogen, methyl, --NHCOCH.sub.3 or --NHCOCH.sub.2 --Z.sub.3, H.sub.4 CN, --CH.sub.2).sub.2-3 --Z.sub.3, --CH.sub.2 CH(OH)CH.sub.2 --Z.sub.3 or --C.sub.2 H.sub.4 NHCOCH.sub.2 --Z.sub.3, ##STR43## in which R.sub.3a is hydrogen or hydroxy, ##STR44## R.sub.8b " is ##STR45## R.sub.8c " is --NH(CH.sub.2).sub.2-3 --Z.sub.3, --NHCOCH.sub.2 --Z.sub.3 or ##STR46## in which R.sub.15b is hydrogen, --CONH.sub.2 or --CH.sub.2 NHCOCH.sub.2 --Z.sub.3, ##STR47## A.sup..crclbar. is an equivalent of a non-chromophoric anion, each Q.sub.b and Q.sub.1b, independently, is a group --NH(CH.sub.2).sub.2-3 --Z.sub.3, R.sub.23b R.sub.24b A.sup..crclbar.,

each of R.sub.20b and R.sub.21b is methyl or ethyl or both R.sub.20b and R.sub.21b, together with the N-atom to which they are attached, form a piperdine, morpholine, piperazine or N-methylpiperazine ring; each of R.sub.22b and R.sub.23b is methyl or ethyl or both R.sub.22b and R.sub.23b, together with the N-atom to which they are attached, has one of the cyclic significances of R.sub.20b and R.sub.21b, are attached, form a pyridinium group unsubstituted or substituted by one or two methyl groups.

In a compound of formula Id the group --(CH.sub.2).sub.t 13 SO.sub.2 CH.dbd.CH.sub.2 is preferably

(i) in the 3- or 4-positon when R.sub.1b =R.sub.2b =hydrogen;

(ii) in the 4- or 5-position when one of R.sub.1b and R.sub.2b is hydrogen and the other is other than hydrogen;

(iii) in the 4-position when R.sub.1b and R.sub.2b are both other than hydrogen;

more preferably t is 0.

In the compounds of formula I the anions A.sup..crclbar. can be any non-chromophoric anions such as those conventional in basic dyestuff chemistry. Suitable anions include chloride, bromide, sulphate, bisulphate, methylsulphate, aminosulphonate, perchlorate, benzenesulphonate, oxalate, maleate, acetate, propionate, lactate, succinate, tartrate, malate, methanesulphonate and benzoate as well as complex anions, for example zinc chloride double salts and anions of boric acid, citric acid, glycolic acid, diglycolic acid and adipic acid or addition products of ortho boric acids with polyalcohols with at least one cis diol group present. These anions can be exchanged for each other by ion exchange resins or on reaction with acids or salts (for example via the hydroxide or bicarbonate) or according to the method given in German Offenlegungsschrift Nos. 20 01 748 or 20 01 816.

Compounds of formula I can be prepared by reacting a diazotised compound of formula IV

with a compound of formula V

and optionally converting the obtained metal-free compound of formula I into the corresponding 1:1 or 1:2 metal complex.

Diazotisation and coupling reactions may be effected in conventional manner. The conditions of any coupling reaction e.g., temperature and pH, depend on each particular coupling component used in the preparation process.

A compound of formula I can also be prepared by splitting off a compound H-B from a compound of formula VI, --Z).sub.n                                                VI

in which B is a group which under the reaction conditions is split off, such as --OSO.sub.3 H, --OPO.sub.3 H.sub.2, halogen, --OCOCH.sub.3, --SSO.sub.3 H, amino, lower alkyl substituted amino or a lower alkyl substituted quaternary ammonium group.

This reaction is carried out in accordance with known methods. Advantageously, splitting off is effected in an aqueous alkaline medium in the presence of a basic compound such as sodium hydroxide, where the pH is in the range of 6 to 13, especially 10 to 11.

The starting compounds of formulae IV, V and VI are either known or may be prepared in accordance with known methods from available starting materials.

Compounds of formula I containing metallisable groups in an ortho position to the carbon atom attached to the azo group may be converted into metal complexes by reacting the metal-free compound of formula I with a metal-donating compound which is employed in such an amount to provide at least one equivalent of metal per equivalent of monoazo compound to be metallised.

Metallisation is carried out in accordance with known methods.

For example, metal complexes of formula II or III can be prepared by reacting a compound of formula IIa or IIIa ##STR48## in which Y.sub.1a is H, OH, C.sub.1-4 alkoxy or COOH,

and each of Y.sub.1a, Y.sub.2a and Y.sub.3a is in an ortho position to the azo group, with a metal-donating compound in such an amount to provide at least one equivalent of metal per equivalent of monoazo compound to be metallised to obtain a 1:1 or 1:2 metal complex.

Preferred is the 1:1 metallisation and more preferred the preparation of 1:1 copper complexes. Suitably, the preferred 1:1 copper complexes are prepared either by oxidative coppering, preferably at 40.degree.-70.degree. C. and at pH 4-7 in the presence of copper(II) salts or using copper powder in the presence of hydrogen peroxide or other conventional oxidising agents; or preferably by demethylation coppering, preferably at pH 3-4 and at elevated to boiling temperature in the presence of copper(II) salts.

The compounds of formula I in metal-free form or in 1:1 or 1:2 metal complex form may be isolated in accordance with known methods.

Those compounds of formula I containing basic groups may be converted into water-soluble salts by reacting with at least stoichiometric amounts of an inorganic mineral acid such as hydrochloric acid, sulphuric acid, phosphoric acid or preferably an organic acid such as formic acid, acetic acid, lactic acid, citric acid, glycolic acid or methanesulphonic acid.

The metal-free compounds of formula I and 1:1 and B 1:2 metal complexes thereof in their acid addition salt form or as quaternary ammonium salt (hereinafter referred to as the dyes of formula I) are useful as dyestuffs for dyeing and printing fibres, threads or textile materials particularly natural or synthetic polyamide materals, for example wool, silk, nylon etc. which preferably can be dyed by exhaustion using a long or short liquor at room to boiling temperature.

Printing can be carried out by impregnation with a printing paste which can be prepared by known methods.

Furthermore, the dyes of formula I can be used for dyeing or printing cotton, polyacrylonitrile or fibre blends, such as cotton-polyester, polyester-wool or polyacrylonitrile-wool fibre blends. The dyes of formula I are also well suited for dyeing or printing leather including low affinity vegetable-tanned leather, in accordance with known methods.

The resulting dyeings and prints on the different substrates show good fastness properties.

The dyes of formula I have good solubility properties in particular good cold water solubility. They build-up well, migrate well and have notable equalising properties particularly on wool or synthetic polyamide substrate even without using any levelling agent; they give high exhaust and fixation yields. The portion of unfixed dyestuff can be easily washed off the substrate. The resulting dyeings and prints are brilliant and show notably good light fastness properties; on exposure to light for a long time the shade of the dyeing fades tone in tone. Furthermore, the dyeings made with the dyestuffs according to the invention have good wet fastness properties. Any aftertreatment with ammonia usually carried out for fibre-reactive dyeings on wool to improve the wet fastnesses is unnecessary. The dyeing process therefore is gentle on the wool-fibres.

The dyes of formula I are also well suited for dyeing in combination. The thus obtained dyeings have good fastness properties.

The following Examples further serve to illustrate the invention. In the Examples all parts and percentages are by weight or volume and the temperatures given are in degrees centigrade unless indicated to the contrary.

21.8 Parts of 1-amino-2-chloro-4-vinylsulphonylbenzene are dissolved in 500 parts of glacial acetic acid at 70.degree.. To this solution 38 parts of 30% hydrochloric acid and then a solution of 6.9 parts of sodium nitrite in 25 parts of water are added whilst cooling with ice. After one hour any excess nitrous acid is decomposed by the addition of 0.5 parts of sulphamic acid. The resulting suspension is added dropwise to a solution consisting of 27.6 parts of the coupling component of the formula ##STR49## in 1200 parts of water within one hour. The pH of the coupling mixture is kept at 3.0 to 3.5 by the addition of sodium acetate. After three hours the dark-red solution is adjusted to a volume of 2.5 liters. The thus obtained dyeing solution containing the dye-stuff of the formula ##STR50## dyes wool a red shade. This dyestuff has notably good levelling properties. The resulting wool dyeings have good light and wet fastness properties.

31.6 Parts of 1-amino-2-chloro-4-(2'-sulphatoethyl)sulphonylbenzene (which is prepared in accordance with known methods) are dissolved in 800 parts of water and 35 parts of a 30% hydrochloric acid solution and are diazotised at 0.degree. to 5.degree. by the addition of 6.9 parts of sodium nitrite in 25 parts of water. After one hour any excess nitrous acid is decomposed by the addition of 0.5 parts of sulphamic acid. The clear solution of the diazonium salt is added to a solution containing 27.6 parts of the coupling component of the formula ##STR51## in 1000 parts of water. The pH of the coupling mixture is kept at 3.0 to 3.5 by the addition of solid sodium acetate. After three hours the dark-orange solution containing the dyestuff corresponding to the formula ##STR52## in which A.sup..crclbar. is the anion of the reaction medium, is adjusted to a volume of 2.5 liters by the addition of water. Adjusting the pH of this solution at 10 to 11 by the addition of sodium hydroxide solutin the dyestuff corresponding to the formula ##STR53## in which A.sup..crclbar. is as defined above, is obtained which dyes wool as well as silk a billiant orange shade. These dyeings show good fastness properties.

In the intermediate monoazo compound of Example 2 any further group to be split off can be used instead of the group --OSO.sub.3 H, for example, a chlorine, bromine, tosyl or ammonium group.

When using an equimolar amount of the diazonium salt of 1-amino-2-methyl-4-vinylsulphonylbenzene (prepared in accordance with the method given in Example 1) which is coupled with a solution of 26 parts of the coupling component of the formula ##STR54## dissolved in 500 parts of water and 100 parts of glacial acetic acid an orange mixture is obtained. After a short time the dyestuff precipitates and is filtered from the suspension and dried. The dyestuff having the formula ##STR55## is obtained in form of the acid addition salt with acetic acid which dyes polyester as well as polyester/cotton fibre blends or synthetic polyamides a scarlet shade. The dyeings have good fastness properties.

Further compounds according to the invention and corresponding to formula (1) ##STR56## in which the symbols are defined in Table 1 below can be prepared by a method analogous to that of Examples 1 to 3 from appropriate starting compounds.

In the last column of this Table 1 and also of all the following Tables 2 to 9 the shade of the dyeings on natural or synthetic polyamide fibres is given whereby

Generally, in the Tables any A.sup..crclbar. is the anion of the reaction medium or is one of the anions indicated in the description above. Likewise, any basic groups may be in free base form or in form of the acid addition salt with those acids of the medium used in the preparation process. __________________________________________________________________________ compounds of formula (1) position of                               shade on Ex. No. R.sub.1 SO.sub.2 CHCH.sub.2 R.sub.4     R.sub.6 R.sub.7        PA __________________________________________________________________________ 4   H   4        H           C.sub.2 H.sub.5 ##STR57##     d 5   CH.sub.3 5        CH.sub.3    C.sub.2 H.sub.5 ##STR58##     e 6   CN  4        CH.sub.3    C.sub.2 H.sub.5 ##STR59##     e 7   Cl  4        CH.sub.3    C.sub.2 H.sub.5 ##STR60##     e 8   OCH.sub.3 5        CH.sub.3    C.sub.2 H.sub.5 ##STR61##     f 9   OCH.sub.3 5        H           C.sub.2 H.sub.5 ##STR62##     f 10   CN  4        CH.sub.3    C.sub.2 H.sub.5 C.sub.2 H.sub.4 N(CH.sub.3).sub.2 e 11   Cl  4        CH.sub.3    same as R.sub.7 C.sub.2 H.sub.4 N(CH.sub.3).sub.2 d 12   H   3        CH.sub.3    same as R.sub.7 C.sub.2 H.sub.4 N(CH.sub.3).sub.2 c 13   H   3        H           same as R.sub.7 C.sub.2 H.sub.4 N(CH.sub.3).sub.2 c 14   OCH.sub.3 5        H           same as R.sub.7 C.sub.2 H.sub.4 N(CH.sub.3).sub.2 d 15   H   3        H           C.sub.2 H.sub.5 C.sub.2 H.sub.4 N(CH.sub.3).sub.2 d 16   Cl  4        CH.sub.3    C.sub.2 H.sub.5 C.sub.2 H.sub.4 N(C.sub.2 H.sub.5).sub .2             e 17   Cl  4        H           C.sub.2 H.sub.4 CN C.sub.2 H.sub.4 N(C.sub.2 H.sub.5).sub .2             d 18   CN  5        NHCOCH.sub.3 C.sub.2 H.sub.5 ##STR63##     d 19   H   3        H           same as R.sub.7 ##STR64##     c 20   Cl  4        H           same as R.sub.7 ##STR65##     d 21   OCH.sub.3 5        CH.sub.3    same as R.sub.7 ##STR66##     f 22   OCH.sub.3 5        H           same as R.sub.7 ##STR67##     f 23   Cl  4        H           C.sub.2 H.sub.4 CN ##STR68##     d 24   Br  4        H           C.sub.2 H.sub.5 ##STR69##     d 25   Cl  4        CH.sub.3    C.sub.2 H.sub.5 ##STR70##     f 26   Cl  4        H           same as R.sub.7 ##STR71##     e 27   Cl  5        CH.sub.3    CH.sub.3 ##STR72##     e 28   Cl  4        CH.sub.3    C.sub.2 H.sub.5 ##STR73##     e 29   H   4        CH.sub.3    C.sub.2 H.sub.5 ##STR74##     d 30   H   4        H           C.sub.2 H.sub.5 ##STR75##     d 31   OCH.sub.3 4        NHCONH.sub.2 C.sub.2 H.sub.5 ##STR76##     f 32   OCH.sub.3 5        NHCOCH.sub.3 C.sub.2 H.sub.5 ##STR77##     f 33   H   4        H           C.sub.2 H.sub.5 ##STR78##     c 34   H   4        CH.sub.3    C.sub.2 H.sub.5 ##STR79##     d 35   H   3        CH.sub.3    C.sub.2 H.sub.5 ##STR80##     c 36   H   3        H           C.sub.2 H.sub.5 ##STR81##     c 37   Cl  4        CH.sub.3    C.sub.2 H.sub.5 ##STR82##     d 38   OCH.sub.3 5        H           C.sub.2 H.sub.5 ##STR83##     d 39   OCH.sub.3 5        CH.sub.3    C.sub.2 H.sub.5 ##STR84##     d 40   H   4        CH.sub.3    C.sub.2 H.sub.5 ##STR85##     c 41   H   3        NHCOCH.sub.3 C.sub.2 H.sub.5 ##STR86##     e 42   Cl  4        CH.sub.3    same as R.sub.7 ##STR87##     d 43   H   4        CH.sub.3    C.sub.2 H.sub.5 ##STR88##     d 44   Cl  4        CH.sub.3    C.sub.2 H.sub.5 ##STR89##     d 45   Cl  4        H           C.sub.2 H.sub.5 ##STR90##     d 46   Cl  4        CH.sub.3    C.sub.2 H.sub.5 ##STR91##     e 47   Cl  5        CH.sub.3    C.sub.2 H.sub.5 ##STR92##     e 48   Cl  4        CH.sub.3    C.sub.2 H.sub.5 ##STR93##     f 49   Cl  4        CH.sub.3    same as R.sub.7 ##STR94##     f 50   H   4        NHCOCH.sub.3 C.sub.2 H.sub.5 ##STR95##     f 51   H   4        CH.sub.3    C.sub.2 H.sub.5 ##STR96##     f 52   H   4        H           C.sub.2 H.sub.5 ##STR97##     f 53   H   3        H           C.sub.2 H.sub.5 ##STR98##     e 54   OCH.sub.3 5        CH.sub.3    C.sub.2 H.sub.5 ##STR99##     f 55   OCH.sub.3 5        H           C.sub.2 H.sub.5 ##STR100##    f 56   Cl  4        CH.sub.3    C.sub.2 H.sub.5 ##STR101##    e 57   Cl  4        CH.sub.3    C.sub.2 H.sub.5 ##STR102##    e 58   Cl  4        CH.sub.3    C.sub.2 H.sub.5 ##STR103##    e 59   Cl  4        NHCOCH.sub.3 H ##STR104##    e 60   Cl  4        CH.sub.3    C.sub.2 H.sub.5 ##STR105##    d 61   H   4        H           C.sub.2 H.sub.5 C.sub.3 H.sub.6 N(C.sub.2 H.sub.5 ).sub.2        d 62   H   3        CH.sub.3    C.sub.2 H.sub.5 C.sub.3 H.sub.6 N(CH.sub.3).sub.2 d 63   CH.sub.3 4        CH.sub.3    C.sub.2 H.sub.5 C.sub.3 H.sub.6 N(CH.sub.3).sub.2 e 64   Cl  4        NHCOCH.sub.2 N(CH.sub.3).sub.2 C.sub.2 H.sub.5 C.sub.2 H.sub.5 f 65   Cl  4        NHCOC.sub.2 H.sub.4 N(C.sub.2 H.sub.5).sub.2 C.sub.2 H.sub.5 C.sub.2 H.sub.5 f 66   Cl  4        NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 C.sub.2 H.sub.5 C.sub.2 H.sub.5 f 67   Cl  5        H           C.sub.2 H.sub.5 ##STR106##    e 68   Cl  4        H           C.sub.2 H.sub.5 ##STR107##    f 69   Cl  4        H           C.sub.2 H.sub.5 C.sub.2 H.sub.4 NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 f 70   Cl  4        CH.sub.3    C.sub.2 H.sub.5 C.sub.2 H.sub.4 NHCOCH.sub.2 N(C.sub.2 H.sub. 5).sub.2 f 71   H   4        CH.sub.3    C.sub.2 H.sub.5 C.sub.2 H.sub.4 NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 f 72   Cl  4        H           C.sub.2 H.sub.5 C.sub.2 H.sub.4 NHCOCH.sub.2 N(CH.sub. 3).sub.2       f 73   Cl  4        CH.sub.3    C.sub.2 H.sub.5 C.sub.2 H.sub.4 NHCOCH.sub.2 N(CH.sub. 3).sub.2       f 74   Cl  5        H           C.sub.2 H.sub.5 C.sub.2 H.sub.4 NHCOCH.sub.2 N(CH.sub. 3).sub.2       f 75   OCH.sub.3 5        NHCOCH.sub.3 H     COCH.sub.2 N(C.sub.2 H.sub.5).sub.2 b 76   Cl  4        NHCOCH.sub.3 H     COCH.sub.2 N(C.sub.2 H.sub.5).sub.2 c 77   H   3        NHCOCH.sub.3 H ##STR108##    b __________________________________________________________________________

By a method analogous to that of Examples 1 to 3 further compounds corresponding to formula (2) ##STR109## in which the symbols are listed in Table 2 below may be prepared using appropriate starting compounds. compounds of formula (2)    position of      shade on Ex. No. R.sub.1 W W S O.sub.2 CHCH.sub.2 R.sub.2 R.sub.4 R.sub.5 R.sub.6 R.sub.7 PA              78 Br direct bond 4 Br CH.sub.3 H C.sub.2 H.sub.5 C.sub.3 H.sub.6 N(C.sub.2 H.sub.5).sub.2 d 79 Br direct bond 4 Br H H C.sub.2 H.sub.5 C.sub.3 H.sub.6 N(C.sub.2 H.sub.5).sub.2 d  80 CN direct bond 4 H CH.sub.3 OCH.sub.3 C.sub.2 H.sub.5 ##STR110## f  81 CN direct bond 5 H H OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR111## f  82 CH.sub.3 direct bond 5 H NHCOCH.sub.3 OCH.sub.3 same as R.sub.7 ##STR112## e  83 CH.sub.3 direct bond 5 H NHCOCH.sub.3 OC.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR113## e  84 H direct bond 3 H CH.sub.3 OCH.sub.3 C.sub.2 H.sub.5 ##STR114## e  85 H CH.sub.2 3 H CH.sub.3 OCH.sub.3 C.sub.2 H.sub.5 ##STR115## c  86 Br direct bond 4 Cl NHCOCH.sub.3 OC.sub.2 H.sub.5 H ##STR116## k  87 Br direct bond 4 Br NHCOCH.sub.3 OC.sub.2 H.sub.5 H ##STR117## k 88 Br direct bond 4 Br NHCOCH.sub.3 H H ##STR118## d  89 Br direct bond 4 Br CH.sub.3 H C.sub.2 H.sub.5 ##STR119## d 90 Br direct bond 4 CN NHCOCH.sub.3 H H ##STR120## l  91 Cl direct bond 4 CN NHCOCH.sub.3 OC.sub.2 H.sub.5 H ##STR121## j  92 Br direct bond 4 Cl NHCOCH.sub.3 OC.sub.2 H.sub.5 H ##STR122## K  93 Cl direct bond 4 H NHCOCH.sub.3 OC.sub.2 H.sub.5 H ##STR123## f  94 Br direct bond 4 Br NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 OCH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 m 95 H CH.sub.2  4 H CH.sub.3 H C.sub.2 H.sub.5 C.sub.2 H.sub.4 N(C.sub.2 H.sub.5).sub.2 d 96 H CH.sub.2 3 H H H C.sub.2 H.sub.5 ##STR124## c  97 Cl CH.sub.2 4 H CH.sub.3 H C.sub.2 H.sub.5 ##STR125## d

When an equimolar amount of the diazonium salt prepared as described in Example 1 is coupled at pH 8 with 33 parts of a compound of the formula ##STR126## in 300 parts of water an orange dyestuff is obtained corresponding to the formula ##STR127## in acid addition salt form (depending on the reaction medium) which dyes wool as well as polyester/cotton fibre blends a brilliant orange shade.

An equimolar amount of the diazonium salt solution of 1-amino-4-vinylsulphonylbenzene prepared by a method analogous to that described in Example 1 is added dropwise to 27.2 parts of a compound of the formula ##STR128## dissolved in 300 parts of acetic acid and 700 parts of water within 45 minutes whilst cooling with ice. Coupling is effected at pH 3.0 to 3.5 which is kept by the addition of sodium acetate. After three hours the resulting dark-blue solution is adjusted to a volume of 2.5 liters by adding the corresponding amount of water. This solution contains the dyestuff corresponding to the formula ##STR129## in acid addition salt form which dyes wool a reddish-blue shade.

By a method analogous to that of Examples 1 to 3 and 99 further compounds according to the invention may be prepared from appropriate starting compounds. These dyestuffs correspond

(i) to formula (3) ##STR130## in which the symbols are defined in Table 3 below;

(ii) to formula (4) ##STR131## in which the symbols are defined in Table 4 below;

(iii) to formula (5) ##STR132## in which the symbols are defined in Table 5 below.

The groups Z.sub.t1 and Z.sub.t2 used in Tables 3 to 5 are defined as follows: __________________________________________________________________________ compounds of formula (3) position of                                      shade on Ex. No. R.sub.1 SO.sub.2 CHCH.sub.2 R.sub.23 R.sub.24              R.sub.26       PA __________________________________________________________________________ 100  Cl  5        OH ##STR133##           H              e 101  H   3        OH ##STR134##           H              d 102  CN  4        OH ##STR135##           H              e 103  OCH.sub.3 4        OH ##STR136##           H              e 104  CH.sub.3 4        OH ##STR137##           H              d 105  1:1 copper complex of Example 103                    h 106  OCH.sub.3 4        OH ##STR138##           H              e 107  Cl  4        OH ##STR139##           H              e 108  1:1 copper complex of Example 106                    h 109  Cl  5        OH ##STR140##           H              e 110  OCH.sub.3 4        NH.sub.2 H                     CH.sub.2 NHCOCH.sub.2 N(CH.sub. 3).sub.2       d 111  CH.sub.3 4        NH.sub.2 H                     CH.sub.2 NHCOCH.sub.2 N(CH.sub. 3).sub.2       d 112  H   4        NH.sub.2 H                     CH.sub.2 NHCOCH.sub.2 N(CH.sub. 3).sub.2       d 113  Cl  5        NH.sub.2 H                     CH.sub.2 NHCOCH.sub.2 N(CH.sub. 3 ).sub.2      d 114  H   4        OH COZ.sub.t1            H              d 115  OCH.sub.3 5        OH COZ.sub.t1            H              e 116  Cl  4        OH COZ.sub.t1            H              d 117  1:1 copper complex of Example 114                    g 118  1:1 copper complex of Example 115                    h __________________________________________________________________________ __________________________________________________________________________ compounds of formula (4) position of                                      shade on Ex. No. R.sub.1 SO.sub.2 CHCH.sub.2 R.sub.2 R.sub.23 R.sub.25    R.sub.27   R.sub.28   R.sub.29 PA __________________________________________________________________________ 119  CN  4        H OH H           SO.sub.2Z.sub.t1 H          H m 120  Cl  5        H OH H           SO.sub.2Z.sub.t1 H          H m 121  H   3        H OH H           SO.sub.2Z.sub.t1 H          H m 122  OCH.sub.3 4        H OH H           SO.sub.2Z.sub.t1 H          H m 123  CH.sub.3 4        H OH H           SO.sub.2Z.sub.t1 H          H m 124  1:1 copper complex of Example 122                    g 125  OCH.sub.3 5        H OH H           H ##STR141## H m 126  Cl  5        H OH H           H ##STR142## H m 127  1:1 copper complex of Example 125                    g 128  CN  4        H OH H           H ##STR143## H m 129  Cl  4        H H Z.sub.t1    H          H          H g 130  Cl  4        H H NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 H          H          H m 131  OCH.sub.3 5        H H NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 H          H          OH m 132  H   3        H H ##STR144## H          H          H m 133  Cl  4        H H ##STR145## H          H          OH m 134  Cl  4        H H ##STR146## H          H          OH n 135  Br  4        Br H ##STR147## H          H          OH n 136  Br  4        Cl OH H ##STR148## H          H n __________________________________________________________________________ __________________________________________________________________________ compounds of formula (5) Ex. No. R.sub.1 R.sub.23 R.sub.24      R.sub.25    shade on PA __________________________________________________________________________ 137  H   H  H             Z.sub.t1    g 138  OCH.sub.3 H  H             Z.sub.t1    g 139  H   H  H             NHC.sub.2 H.sub.4 N(C.sub.2 H.sub.5).sub.2 g 140  H   H  H ##STR149## g 141  H   OH COZ.sub.t1    H           g 142  OCH.sub.3 OH COZ.sub.t1    H           g 143  1:1 copper complex of Example 142 1 144  OCH.sub.3 OH COZ.sub.t2    H           g 145  1:1 copper complex of Example 144 l 146  H   OH ##STR150##   H           g __________________________________________________________________________

18.3 Parts of 1-amino-3-vinylsulphonylbenzene are stirred into 300 parts glacial acetic acid at 20.degree.. To this mixture 35 parts of 30% hydrochloric acid are added. Diazotisation is effected employing 6.9 parts of sodium nitrite in 25 parts of water and cooling with ice. After one hour any excess nitrous acid is decomposed by the addition of a small amount of sulphamic acid. The coupling reaction is carried out in accordance with conventional methods at pH 3 to 4 using a compound of the formula ##STR151##

The resulting dyestuff which coresponds to the formula ##STR152## in acid addition salt form dyes wool a yellow shade. The dyeings show good light and wet fastness properties.

By a method according to Examples 1 to 3 and 147 further dyestuffs may be prepared from appropriate starting compounds. They correspond to formula (6) ##STR153## in which the symbols are as defined in Table 6 below.

In Table 6 --Z.sub.t1 is a group --NHC.sub.3 H.sub.6 N(C.sub.2 H.sub.5).sub.2. __________________________________________________________________________ compounds of formula (6) Ex. No. R.sub.1 W      position of WSO.sub.2 CHCH.sub.2 R.sub.13 (position)  shade on __________________________________________________________________________ PA 148  Cl  direct bond 4 ##STR154##          b 149  H   direct bond 4 ##STR155##          b 150  H   direct bond 3 ##STR156##          b 151  H   CH.sub.2 4 ##STR157##          b 152  H   direct bond 3                NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 (p)                  b 153  Cl  direct bond 4                NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 (m)                  b 154  Cl  direct bond 4                NHCOCH.sub. 2 N(C.sub.2 H.sub.5).sub.2 (p)                  b 155  Cl  CH.sub.2 5                NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 (p)                  b 156  H   direct bond 3                NHCOCH.sub.2 N(CH.sub.3).sub.2 bp) 157  Cl  direct bond 4 ##STR158##          b 158  H   direct bond 4 ##STR159##          b 159  H   CH.sub.2 4 ##STR160##          b 160  OCH.sub.3 direct bond 5 ##STR161##          b 161  1:1 copper complex of Example 160                brownish-yellow 162  CH.sub.3 direct bond 5                COZ.sub.t1 (m)       b 163  H   direct bond 4                COZ.sub.t1 (p)       b 164  Cl  direct bond 5 ##STR162##          b 165  H   direct bond 3 ##STR163##          b 166  H   direct bond 3 ##STR164##          b __________________________________________________________________________

An equimolar amount of the diazonium salt as described in Example 147 is coupled with a solution of 55 parts of a compound having the formula ##STR165## in 500 parts of water. The dyestuff obtained which corresponds to the formula ##STR166## in acid addition salt form dyes wool in greenish-yellow shades.

By a method according to that of Examples 1 to 3 and 167 further dyestuffs may be prepared from appropriate starting compounds which are listed in Table 7 below. They correspond to formula (7) ##STR167## in which the symbols are defined in Table 7. __________________________________________________________________________ compounds of formula (7) Ex. No. R.sub.1 position of SO.sub.2 CHCH.sub.2 R.sub.12 R.sub.13 (position) shade on PA __________________________________________________________________________ 168  Cl  4             H   NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 a4) 169  CH.sub.3 5             H   NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 a4) 170  H   4             H   NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 a4) 171  H   4             OCH.sub.3 NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 a5) 172  H   3             H   NHCOCH.sub.2 N(CH.sub.3).sub.2 a3) 173  Cl  4             H ##STR168##       a 174  CN  4             H ##STR169##       a 175  Cl  4             H ##STR170##       a 176  H   3             OCH.sub.3 ##STR171##       a 177  CH.sub.3 5             H ##STR172##       a 178  Cl  4             H   CONHC.sub.3 H.sub.6 N(C.sub.2 H.sub.5).sub.2 (3)               a 179  Cl  4             OCH.sub.3 CONHC.sub.3 H.sub.6 N(C.sub.2 H.sub.5).sub.2 (5)               a 180  OCH.sub.3 4             H   CONHC.sub.3 H.sub.6 N(C.sub.2 H.sub.5).sub.2 (3)               a 181  H   3             H   CONHC.sub.3 H.sub.6t N(C.sub.2 H.sub.5).sub.2 (3)               a 182  H   4             H ##STR173##       a 183  Cl  4             H ##STR174##       a 184  CN  5             H ##STR175##       a 185  H   3             H ##STR176##       a __________________________________________________________________________

When the diazonium salt as defined in Example 1 is coupled with a compound of the formula ##STR177## a dyestuff is obtained having the formula ##STR178## in acid addition salt form which dyes polyacrylonitrile a greenish-yellow shade.

By a method analogous to that of Examples 1 to 3 and 186 further compounds may be prepared from appropriate starting compounds. The resulting dyestuffs correspond to formula (8) ##STR179## in which the symbols are defined in Table 8 below. In this Table 8 Z.sub.t1 is a group --NHC.sub.3 H.sub.6 N(C.sub.2 H.sub.5).sub.2 and Z.sub.t2 is a group --NHC.sub.3 H.sub.6 N(CH.sub.3).sub.2. __________________________________________________________________________ compounds of formula (8) Ex.         position of                                  shade on No. R.sub.1 W   WSO.sub.2 CHCH.sub.2 R.sub.15        R.sub.16          PAC __________________________________________________________________________ 187 Cl  direct bond 4 ##STR180##     H                 brownish- yellow 188 CN  direct bond 5 ##STR181##     C.sub.3 H.sub.6 N(C.sub.2 H.sub.5). sub.2             a 189 OCH.sub.3 direct bond 5 ##STR182##     C.sub.3 H.sub.6 N(C.sub.2 H.sub.5). sub.2             a 190 H   direct bond 4 ##STR183##     C.sub.3 H.sub.6 N(C.sub.2 H.sub.5). sub.2             a 191 Cl  direct bond 4 ##STR184##     C.sub.3 H.sub.6 N(C.sub.2 H.sub.5). sub.2             a 192 Cl  direct 4          CN              C.sub.3 H.sub.6 N(C.sub.2 H.sub.5). sub.2             a bond 193 OCH.sub.3 direct 5          CN              C.sub.3 H.sub.6 N(C.sub.2 H.sub.5). sub.2             b bond 194 Cl  direct 4          CONH.sub.2      C.sub.3 H.sub.6 N(C.sub.2 H.sub.5). sub.2             a bond 195 Cl  direct 4          CONH.sub.2      C.sub.3 H.sub.6 N(CH.sub.3).sub.2 a bond 196 H   direct 3          CONH.sub.2      C.sub.3 H.sub.6 N(CH.sub.3).sub.2 a bond 197 OCH.sub.3 direct 5          CONH.sub.2      C.sub.3 H.sub.6 N(CH.sub.3).sub.2 a bond 198 H   CH.sub.2 4          CONH.sub.2      C.sub.3 H.sub.6 N(CH.sub.3).sub.2 a 199 H   CH.sub.2 4          CONH.sub.2 ##STR185##       a 200 H    CH.sub.2 4          H ##STR186##       a 201 Cl  direct bond 4          CN ##STR187##       b 202 Cl  direct 4          H               C.sub.3 H.sub.6 N(CH.sub.3).sub.2 a bond 203 H   direct 3          H               C.sub.3 H.sub.6 N(CH.sub.3).sub.2 a bond 204 OCH.sub.3 direct 5          H               C.sub.3 H.sub.6 N(CH.sub.3).sub.2 a bond 205 H   CH.sub.2 4          H               C.sub.3 H.sub.6 N(CH.sub.3).sub.2 a 206 H   CH.sub.2 4          H ##STR188##       a 207 Cl  direct bond 4          H ##STR189##       a 208 H   direct bond 3          H ##STR190##       a 209 Cl  direct bond 5          CONH.sub.2 ##STR191##       a 210 Cl  direct 4          CH.sub.2 NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 C.sub.2 H.sub.5   a bond 211 H   direct 4          CH.sub.2 NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 C.sub.2 H.sub.5   a bond 212 H   direct 3          CH.sub.2 NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 H                 a bond 213 CH.sub.3 direct 4          CH.sub.2 NHCOCH.sub.2 N(C.sub.2 H.sub.5 H.sub.2           a bond 214 OCH.sub.3 direct 4          CH.sub.2 NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 H                 a bond 215 H   CH.sub.2 4          CH.sub.2 NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 H                 a 216 H   CH.sub.2 4          CH.sub.2 NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 C.sub.2 H.sub.5   a 217 H   direct 3          CH.sub.2 NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 C.sub.3 H.sub.6 N(C.sub.2 H.sub.5). sub.2             a bond 218 Cl  direct 4          CH.sub.2 NHCOCH.sub.2 N(C.sub.2 H.sub.5).sub.2 C.sub.3 H.sub.6 N(C.sub.2 H.sub.5). sub.2             a bond 219 Cl  direct bond 4 ##STR192##     C.sub.2 H.sub.5   a 220 H   direct bond 3 ##STR193##     C.sub.2 H.sub.5   a 221 H   direct bond 4 ##STR194##     H                 a 222 Cl  direct bond 5 ##STR195##     C.sub.3 H.sub.6 N(CH.sub.3).sub.2 a 223 H   direct bond 4 ##STR196##     C.sub.3 H.sub.6 N(CH.sub.3).sub.2 a 224 Cl  direct bond 4 ##STR197##     C.sub.2 H.sub.5   a 225 H   direct bond 4 ##STR198##     C.sub.2 H.sub.5   a 226 H   direct bond 3 ##STR199##     H                 a 227 H   direct  bond 4 ##STR200## ##STR201##       a 228 Cl  direct bond 4 ##STR202## ##STR203##       a 229 H   direct bond 4 ##STR204##     C.sub.3 H.sub.6 N(CH.sub.3).sub.2 a 230 H   CH.sub.2 4 ##STR205##     C.sub.3 H.sub.6 N(CH.sub.3).sub.2 a 231 H   direct bond 3 ##STR206## ##STR207##       a 232 H   direct 4          CH.sub.2 NHCOCH.sub.2 N(CH.sub.3).sub.2 C.sub.3 H.sub.6 N(CH.sub.3).sub.2 a bond 233 Cl  direct 4          CH.sub.2 NHCOCH.sub.2 N(CH.sub.3).sub.2 C.sub.2 H.sub.5   a bond __________________________________________________________________________

The coupling compounds used for the preparation of the dyestuffs of Examples 210 to 233 in Table 8 can be obtained by reacting a halogen containing compound of Example 1 of DE-OS No. 22 37 006 with a secondary or tertiary amine such as dimethyl- or diethylamine, morpholine or trimethylamine in accordance with known methods.

20 Parts of 1-amino-3-(2'-hydroxyethyl)sulphonylbenzene are diazotised in accordance with the method described in Example 1. This diazonium salt is coupled with 27 parts of a compound of the formula ##STR208## in 200 parts of water and 30 parts of glacial acetic acid. A compound having the formula ##STR209## is obtained which precipitates in alkaline medium, and is separated by filtration and dried. The product is added to 250 parts of concentrated sulphuric acid at 0.degree. to 5.degree. whilst stirring vigorously. The temperature is allowed to rise slowly to 20.degree.. Subsequently, the dark reaction mixture is poured onto 100 parts of ice. The pH is adjusted to ca. 10 with the addition of a 30% sodium hydroxide solution, the dyestuff precipitates increasingly and is separated by filtration after two hours. A dyestuff having the formula ##STR210## in acid addition salt form is obtained which dyes natural and synthetic polyamide fibres a bright golden-yellow shade.

By a method analogous to that described in Example 234 the vinylsulphonyl group can be introduced into any diazo component disclosed in the Examples hereinbefore.

The diazonium salt solution prepared in Example 99 is added dropwise at 0.degree. to 5.degree. to a solution of 15.3 parts of 2,5-dimethoxyaniline in 50 parts of glacial acetic acid and 150 parts of water within 30 minutes. The product which precipitates is filtered, washed with water and dried.

3.8 Parts of the above product are suspended in 50 parts of warm acetic acid and 5.8 parts of a 30% hydrochloric acid are added. To the resulting red solution a solution of 0.69 parts of sodium nitrite in 10 parts of water is added dropwise. The suspension is stirred for one hour at 0.degree. to 5.degree.. Subseqently, any excess nitrous acid is decomposed by the addition of a small amount of sulphamic acid. The diazonium suspension is then added to a mixture containing 2.9 parts of a compound of the formula ##STR211## in 60 parts of methanol and 40 parts of water. Stirring is effected for a further two hours. The pH is kept at ca. 3 during coupling by the addition of sodium acetate and is subsequently adjusted to 4.5. The resulting disazo dyestuff which precipitates is filtered, washed and dried. It corresponds to the formula ##STR212## in acid addition salt form and dyes wool a reddish-blue shade.

By a method analogous to that of Example 235 further disazo compounds may be prepared from appropriate starting compounds. They correspond to formula (9) ##STR213## in which the symbols are defined in Table 9 below.

In any middle component MK*) denotes the carbon atom bound to --N.dbd.N--KK. __________________________________________________________________________ compounds of formula (9) Ex. No. R.sub.1 position of SO.sub.2 CHCH.sub.2 MK       KK                  shade on __________________________________________________________________________ PA 236  H 3 ##STR214## ##STR215##         l 237  H 3 ##STR216## ##STR217##         l 238  Cl 4 ##STR218## ##STR219##         l 239  Cl 4 ##STR220## ##STR221##         l 240  Cl 4 ##STR222## ##STR223##         l 241  H 4 ##STR224## ##STR225##         j 242  Cl 4 ##STR226## ##STR227##         l 243  H 3 ##STR228## ##STR229##         l 244  1:1 copper complex of Example 239 (spanning MKNNKK) i 245  1:1 copper complex of Example 240 (spanning MKNNKK) o 246  H 3 ##STR230## ##STR231##         l 247  H 3 ##STR232## ##STR233##         l 248  H 3 ##STR234## ##STR235##         m 249  H 3 ##STR236## ##STR237##         m __________________________________________________________________________

In the following examples the application of the dyestuffs of this invention is illustrated.

To a dyebath of 25.degree. containing in 1000 parts of water 0.2 parts of the dyestuff of Example 1, 20 parts of wool-gaberdine are added. The pH of the bath is adjusted to 4-5. The dyebath is heated to 98.degree. within 60 minutes, and dyeing is effected at this temperature for 60 minutes. The water that evaporates during dyeing is continuously replaced. Subsequently, the dyed wool fabric is removed from the liquor and is added to a fresh bath containing in 1000 parts of water 5 parts of acetic acid (100%). The bath is heated at the boil for 30 minutes. After rinsing and drying a red wool dyeing is obtained showing a high degree of levelness and having good light and wet fastness properties.

To a dyebath of 25.degree. containing in 1000 parts of water 0.4 parts of the dyestuff of Example 3, 20 parts of synthetic polyamide fabric, for example nylon 66 yarn, are added. Dyeing is effected in analogous manner to the method described in Application Example A. After rinsing and drying a level scarlet polyamide dyeing is obtained having good wet fastness properties.

To a dyebath of 25.degree. containing in 1000 parts of water 0.1 parts of the dyestuff of Example 4, 20 parts of unloaded natural silk fabric are added. Dyeing is effected in accordance with the method described in Application Example A with the exception that the silk dyeing is treated for only 15 minutes in the fresh bath. After rinsing and drying an orange dyeing is obtained having good wet fastness properties.

A polyester-cotton fibre blend (50:50) is padded with a liquor consisting of:

at 25.degree.. The fabric is squeezed to reduce the total pick-up to ca. 80%, is dried at 100.degree. and is then treated for 90 seconds at 210.degree. for fixation. Subsequently, the dyeing is treated with a bath containing in 1000 parts aqueous liquor

at 85.degree.. In order to remove any excess dyestuff the dyeing is rinsed with cold water and is then treated with an aqueous solution of 90.degree. containing in 1000 parts

for 5 minutes. Finally, the dyeing is rinsed with cold water. An orange dyeing is obtained having good light and wet fastness properties. In this dyeing both fibre portions are dyed on-tone having the same depth.

Any one of the dyestuffs of Examples 2 and 5 to 249 which are in acid addition salt form or in quaternary ammonium salt form may be used in place of the dyestuffs of Examples 1, 3 and 4 in any one of Application Examples A to D. List of maximum absorption wavelengths (.lambda..sub.max. in nanometer nm) available for the dyestuffs of Examples 1 to 249. Measurement was carried out in demineralised water. Ex. No.  .lambda..sub.max. Ex. No.  .lambda..sub.max. Ex. No. .lambda..sub.max. Ex. No. .lambda..sub.max. ______________________________________ 1   499    46       491    98    488  204    410 2   452    51       488    99    587  205    420 3   495    52       483   114    463  206    422 7   470    53       478   115    478  234    438 8   476    54       496   117    560  235    604 9   473    55       491   118    538  236    575 11   439    56       497   125    488  237    598 12   428    57       497   127    522  238    597 13   426    58       499   129    554  242    553 14   443    59       495   137    524  243    567 16   472    60       498   141    538  244    560 17   361    61       472   143    568  245    575 19   433    64       515   147    402  246    579 20   438    65       516   148    393  247    559 21   468    66       516   154    396  248    569 22   465    69       490   157    395  249    573 23   372    70       491   159    398 24   454    71       489   160    398 25   495    72       490   165    396 28   472    73       491   167    379 29   468    74       489   183    414 30   468    75       378   187    419 33   454    76       371   193    441 34   452    77       372   195    413 35   442    79       460   196    413 36   438    88       465   197    432 37   452    89       461   198    415 38   463    90       537   199    417 39   465    91       564   200    418 44   465    92       564   202    414 45   462    93       510   203    408 ______________________________________

## Claims

1. A metal-free compound of the formula a 1:1 or 1:2 metal complex of a metallizable metal-free compound of said formula or an acid addition salt of a metal-free compound of said formula or of a 1:1 or 1:2 metal complex of a metallizable metal-free compound of said formula, wherein ##STR238## wherein each of R.sub.1 and R.sub.2 is independently hydrogen, halo, hydroxy, cyano, nitro, trifluoromethyl, carboxy, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, phenoxy, phenoxy substituted by 1 to 3 halo substituents, sulfamoyl, C.sub.1-4 alkylsulfamoyl, di-(C.sub.1-4 alkyl)sulfamoyl, C.sub.1-4 alkylsulfonyl, (C.sub.1-4 alkyl)carbonylamino, benzamido or phenylamino, alkoxy, phenoxy, phenylamino, C.sub.1-4 alkylamino, di-(C.sub.1-4 alkyl)amino, (C.sub.1-4 alkyl)carbonylamino or benzamido, and alkenylene; linear or branched C.sub.1-6 alkylene or linear or branched C.sub.2-6 alkenylene monosubstituted by halo, hydroxy, C.sub.1-4 alkoxy or phenyl; linear or branched alkylene or linear or branched alkenylene having a maximum of 6 carbon atoms which is interrupted by a nitrogen, oxygen or sulfur atom; linear or branched alkylene or linear or branched alkenylene having a maximum of 6 carbon atoms which is monosubstituted by halo, hydroxy, C.sub.1-4 alkoxy or phenyl and interrupted by a nitrogen, oxygen or sulfur atom; --NH--X.sub.a --; --CONH--X.sub.a --; --NHCO--X.sub.a --; --CO--X.sub.a --; --SO.sub.2 NH--X.sub.a --; --NHNHCO--X.sub.a --; --CH.sub.2 --CONH--CH.sub.2 -- or --CH.sub.2 --NHCO--CH.sub.2 --, wherein C.sub.2-4 alkenylene, X.sub.a radical is attached to the CH.sub.2 .dbd.CH--SO.sub.2 -- group, and ##STR239## wherein M is ##STR240## wherein R.sub.4 and R.sub.5 are as defined below, R.sub.4 is hydrogen, halo, hydroxy, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, (C.sub.1-4 alkyl)carbonylamino, ureido, sulfamoyl, C.sub.1-4 alkylsulfamoyl, di-(C.sub.1-4 alkyl)sulfamoyl, --NHCO--(CH.sub.2).sub.p --Z.sub.1 or --SO.sub.2 N[(CH.sub.2).sub.p --Z.sub.1 ].sub.2, hydroxy, phenyl, halo or cyano or disubstituted by hydroxy; --(CH.sub.2).sub.p --NHCO--(CH.sub.2).sub.p --Z.sub.1 ; --W.sub.3 --Z.sub.1 or linear or branched C.sub.1-6 alkylene-Z.sub.1 the alkylene radical of which is substituted by 1 or 2 hydroxy groups, hydroxy, phenyl, halo or cyano or disubstituted by hydroxy; --CO--CH.sub.2 --Z.sub.1 ; linear or branched C.sub.1-8 alkylene-Z.sub.1 ; linear or branched C.sub.1-8 alkylene-Z.sub.1 the alkylene radical of which is substituted by 1 or 2 hydroxy groups; linear or branched alkylene-Z.sub.1 the alkylene radical of which has a maximum of 8 carbon atoms and is interrupted by --NH--, --NCH.sub.3 --, --S--, --O--, --NHCO-- or --OCO--; linear or branched alkylene-Z.sub.1 the alkylene radical of which has a maximum of 8 carbon atoms and is substituted by 1 or 2 hydroxy groups and interrupted by --NH--, --NCH.sub.3 --, --S--, --O--, --NHCO-- or --OCO--; or ##STR241## R.sub.8a is --CONH--(CH.sub.2).sub.p --Z.sub.1, ##STR242## R.sub.8b is --NHCO--(CH.sub.2).sub.p --Z.sub.1, --SO.sub.2 NH--(CH.sub.2).sub.p --Z.sub.1 or ##STR243## R.sub.8c is --NHCO--(CH.sub.2).sub.p --Z.sub.1, --NH--(CH.sub.2).sub.p --Z.sub.1 or ##STR244## one R.sub.8d is hydrogen and the other is --CONH--(CH.sub.2).sub.p --Z.sub.1, --NHCO--(CH.sub.2).sub.p --Z.sub.1, --SO.sub.2 NH--(CH.sub.2).sub.p --Z.sub.1, --NH--(CH.sub.2).sub.p --Z.sub.1 or ##STR245## R.sub.14 is hydrogen, C.sub.1-4 alkyl, phenyl, benzyl or cyclohexyl, R.sub.15 is hydrogen, cyano, carbamoyl, sulfamoyl, pyridinium A.sup..crclbar. or --CH.sub.2 --NHCO--CH.sub.2 --Z.sub.1, monosubstituted by hydroxy, cyano, halo or C.sub.1-4 alkoxy; --W.sub.3 --Z.sub.1 ; ##STR246## R.sub.17 is --W.sub.3 --Z.sub.1 or ##STR247## wherein each of R.sub.11 and R.sub.12 is independently hydrogen, halo, nitro, amino, cyano, hydroxy, C.sub.1-4 alkyl or C.sub.1-4 alkoxy, and ##STR248## R.sub.18 is hydrogen, cyano or carbamoyl, each R.sub.19 is independently hydrogen; C.sub.1-4 alkyl; C.sub.1-4 alkyl monosubstituted by hydroxy or C.sub.1-4 alkoxy; or --W.sub.3 --Z.sub.1, and ##STR249## wherein each Q is independently --NH--(CH.sub.2).sub.q --Z.sub.1, phenoxy, phenylamino, cyclohexylamino, C.sub.1-4 alkylamino, di-(C.sub.1-4 alkyl)amino or --NH--(CH.sub.2).sub.q --Z.sub.1, and branched C.sub.1-6 alkylene or linear or branched C.sub.2-6 alkenylene monosubstituted by halo, hydroxy, C.sub.1-4 alkoxy or phenyl; linear or branched alkylene or linear or branched alkenylene having a maximum of 6 carbon atoms which is interrupted by a nitrogen, oxygen or sulfur atom; linear or branched alkylene or linear or branched alkenylene having a maximum of 6 carbon atoms which is monosubstituted by halo, hydroxy, C.sub.1-4 alkoxy or phenyl and interrupted by a nitrogen, oxygen or sulfur atom; --NH--X.sub.a --; --CONH--X.sub.a --; --NHCO--X.sub.a --; --CO--X.sub.a --; --SO.sub.2 NH--X.sub.a --; --NHNHCO--X.sub.a --; --CH.sub.2 --CONH--CH.sub.2 -- or --CH.sub.2 --NHCO--CH.sub.2 --, branched C.sub.2-4 alkenylene, X.sub.a radical is attached to the Z.sub.1 group, alkylene, ##STR250## wherein each of R.sub.20 and R.sub.21 is independently hydrogen; C.sub.1-4 alkyl; C.sub.2-4 alkyl monosubstituted by hydroxy, C.sub.1-4 alkoxy, halo or cyano; C.sub.5-6 cycloalkyl; phenyl(C.sub.1-4 alkyl) or phenyl(C.sub.1-4 alkyl) the phenyl group of which is substituted by 1 to 3 substituents selected from chloro, C.sub.1-4 alkyl and C.sub.1-4 alkoxy, or --NR.sub.20 R.sub.21 is ##STR251## wherein U is a direct bond, --CH.sub.2 --, --O--, --S--, --SO--, --SO.sub.2 --, --NH--, --N(C.sub.1-4 alkyl) or --N.sup..sym. (C.sub.1-4 alkyl).sub.2 A.sup..crclbar., alkyl monosubstituted by hydroxy, C.sub.1-4 alkoxy, halo or cyano; C.sub.5-6 cycloalkyl; phenyl(C.sub.1-4 alkyl) or phenyl(C.sub.1-4 alkyl) the phenyl group of which is substituted by 1 to 3 substituents selected from chloro, C.sub.1-4 alkyl and C.sub.1-4 alkoxy, substituted by 1 or 2 methyl groups or ##STR252## wherein R.sub.24 and U are as defined above, R.sub.25 is hydrogen or C.sub.1-4 alkyl, ##STR253## is a 5- or 6-membered saturated, partially unsaturated or unsaturated protonatable heterocyclic ring, with the proviso that when it is a saturated ring, b is 1, ##STR254## is a 5 or 6-membered saturated, partially unsaturated or unsaturated quaternized heterocyclic ring, with the proviso that Ka contains 1 to 4 Z.sub.1 groups and each hydroxy substituent on an alkyl group, alkylene radical or alkenylene radical attached to a nitrogen atom is attached to a carbon atom other than a carbon atom directly attached to the nitrogen atom, or a mixture thereof.

2. A metal-free compound according to claim 1, or an acid addition salt thereof.

3. A 1:1 or 1:2 metal complex according to claim 1, or an acid addition salt thereof.

4. A metal-free compound according to claim 1 having the formula ##STR255## a 1:1 or 1:2 metal complex of a metallizable metal-free compound of either of said formulae or an acid addition salt of a metal-free compound of either of said formulae or of a 1:1 or 1:2 metal complex of a metallizable metal-free compound of either of said formulae, ##STR256## wherein Ma is ##STR257## wherein R.sub.4a and R.sub.5a are as defined below, R.sub.4a is hydrogen, chloro, C.sub.1-2 alkyl, C.sub.1-2 alkoxy, (C.sub.1-2 alkyl)carbonylamino, ureido or --NHCO--(CH.sub.2).sub.p --Z.sub.2, 2-chloroethyl, 2-cyanoethyl, ##STR258## R.sub.7a is hydrogen, C.sub.1-2 alkyl, benzyl, 2-hydroxyethyl, 2-chloroethyl, 2-cyanoethyl, ##STR259## R.sub.8 '.sub.a is --CONH--(CH.sub.2).sub.p --Z.sub.2 or ##STR260## R.sub.8 '.sub.b is --NHCO--(CH.sub.2).sub.p --Z.sub.2, --SO.sub.2 NH--(CH.sub.2).sub.r --Z.sub.2 or ##STR261## R.sub.8 '.sub.c is --NHCO--(CH.sub.2).sub.u --Z.sub.2, --NH--(CH.sub.2).sub.r --Z.sub.2, ##STR262## wherein u is 1, 2 or 3, one R.sub.8 '.sub.d is hydrogen and the other is --CONH--(CH.sub.2).sub.p --Z.sub.2, --NHCO--(CH.sub.2).sub.p --Z.sub.2, --NH--(CH.sub.2).sub.p --Z.sub.2 or ##STR263## each of R.sub.11a and R.sub.12a is independently hydrogen, chloro, methyl or methoxy, or ##STR264## R.sub.14a is hydrogen, methyl, ethyl or benzyl, R.sub.15a is hydrogen, carbamoyl or --CH.sub.2 --NHCO--CH.sub.2 --Z.sub.2, and ##STR265## Kc is ##STR266## R.sub.1a is hydrogen; halo; C.sub.1-2 alkyl; C.sub.1-2 alkoxy; hydroxy; carboxy; cyano; phenoxy; phenoxy substituted by 1 to 3 chloro substituents; sulfamoyl; C.sub.1-2 alkylsulfamoyl; di-(C.sub.1-2 alkyl)sulfamoyl; acetamido or phenylamino, phenoxy, phenylamino or --NH--(CH.sub.2).sub.p --Z.sub.2, and --N.sup..sym. R.sub.22a R.sub.23a R.sub.24a A.sup..crclbar., C.sub.1-2 alkyl, n-C.sub.2-3 hydroxyalkyl or benzyl, or or N-methylpiperazino, n-C.sub.2-3 hydroxyalkyl or benzyl, and substituted by 1 or 2 methyl groups or ##STR267## wherein U' is a direct bond, --CH.sub.2 --, --O--, --NH-- or --NCH.sub.3 --, and with the provisos that (1) Kb contains 1 or 2 groups selected from Z.sub.2, pyridyl-2, pyridyl-4, 1-methylpyridinium-2 A.sup..crclbar. and 1-methylpyridinium-4 A.sup..crclbar. and (2) any hydroxy substituent on an alkyl group attached to a nitrogen atom is attached to a carbon atom other than the carbon atom directly attached to the nitrogen atom.

5. A metal-free compound according to claim 4 having the formula ##STR268## or an acid addition salt thereof.

6. A metal-free compound according to claim 5, or an acid addition salt thereof, wherein hydrogen and is in the 2-position and the CH.sub.2 .dbd.CH--SO.sub.2 --(CH.sub.2).sub.t -- group is in the 4- or 5-position or and R.sub.2a is in the 2-position and the other is in the 6-position, and the CH.sub.2 .dbd.CH--SO.sub.2 --(CH.sub.2).sub.t -- group is in the 4-position.

7. A metal-free compound according to claim 4 having the formula ##STR269## or an acid addition salt thereof.

8. A 1:1 or 1:2 metal complex according to claim 4 or an acid addition salt thereof.

9. A metal-free compound according to claim 4 having the formula ##STR270## a 1:1 or 1:2 metal complex of a metallizable metal-free compound of said formula or an acid addition salt of a metal-free compound of said formula or of a 1:1 or 1:2 metal complex of a metallizable metal-free compound of said formula, ##STR271## wherein R.sub.3a is hydrogen or hydroxy, R.sub.4b is hydrogen, methyl, acetamido or --NHCO--CH.sub.2 --Z.sub.3, ##STR272## R.sub.7b is ##STR273## R.sub.8 ".sub.a is ##STR274## R.sub.8 ".sub.b is ##STR275## R.sub.8 ".sub.c is ##STR276## R.sub.15b is hydrogen, carbamoyl or --CH.sub.2 --NHCO--CH.sub.2 --Z.sub.3, and R.sub.16b is hydrogen, --(CH.sub.2).sub.r --Z.sub.3 or ##STR277## R.sub.1b is hydrogen, chloro, bromo, cyano, methyl or C.sub.1-2 alkoxy, R.sub.2b is hydrogen, chloro or bromo, and t is 0 or 1, wherein each Q.sub.b and Q.sub.1b is independently --NH--(CH.sub.2).sub.r --Z.sub.3, wherein each Z.sub.3 is independently --NR.sub.20b R.sub.21b or --N.sup..sym. R.sub.22b R.sub.23b R.sub.24b A.sup..crclbar., N-methylpiperazino, substituted by 1 or 2 methyl groups or ##STR278## wherein U" is --CH.sub.2 --, --O--, --NH-- or --NCH.sub.3 --, and R.sub.24b is as defined above, wherein each A.sup..crclbar. is independently a non-chromophoric anion, with the proviso that Kd contains 1 or 2 groups selected from Z.sub.2, Z.sub.3, pyridyl-2, pyridyl-4, 1-methylpyridinium-2 A.sup..crclbar. and 1-methylpyridinium-4 A.sup..crclbar..

10. A metal-free compound according to claim 9, or an acid addition salt thereof.

11. A metal-free compound according to claim 10.

12. The metal-free compound according to claim 11 having the formula ##STR279## wherein A.sup..crclbar. is a non-chromophoric anion.

13. The metal-free compound according to claim 11 having the formula ##STR280##

14. The metal-free compound according to claim 11 having the formula ##STR281## wherein A.sup..crclbar. is a non-chromophoric anion.

15. The metal-free compound according to claim 11 having the formula ##STR282## wherein A.sup..crclbar. is a non-chromphoriic anion.

16. The metal-free compound according to claim 11 having the formula ##STR283##

17. A 1:1 or 1:2 metal complex according to claim 9, or an acid addition salt thereof.

18. A 1:1 or 1:2 metal complex according to claim 17.