.beta.-D-phenylthioxylosides, their method of preparation and their use as therapeutic agents

The present invention relates, by way of novel industrial products, to the .beta.-D-phenylthioxyloside compounds of the formula ##STR1## in which: X represents a sulfur atom or an oxygen atom; PA0 R.sub.1, R.sub.2 and R.sub.3, which are identical or different, each represent a hydrogen atom, a nitro group, a cyano group, a group --CO--R (in which R represents a C.sub.1 -C.sub.4 alkyl group or a trifluoromethyl group), an amino group, an acetamido group (NHCOCH.sub.3), a C.sub.1 -C.sub.4 alkoxy group, a trifluoromethyl group or a phenyl group substituted by one or more cyano, nitro or trifluoromethyl groups, it being possible for R.sub.1 and R.sub.2, taken together, to form, with the phenyl group to which they are bonded, a .beta.-naphthalenyl group which is unsubstituted or substituted by one or more cyano, nitro or trifluoromethyl groups; and PA0 Y represents the hydrogen atom or an aliphatic acyl group. These compounds are useful as therapeutic agents, especially as venous antithrombotics.

The present invention relates, by way of novel industrial products, to the 
.beta.-D-phenylthioxyloside compounds of formula I below. It further 
relates to their method of preparation and their use in therapy as 
antithrombotics, especially venous antithrombotics. 
European patent document B-0051023 has already disclosed benzoylphenyloside 
and .alpha.-hydroxybenzylphenyloside derivatives as ulcer inhibitors, 
platelet aggregation inhibitors, antithrombotics and cerebral oxygenators. 
Also, European patent document A-0133103 has disclosed benzylphenylosides 
which are useful as hypocholesterolemics and hypolipidemics, some of these 
compounds, in particular the product of Example 1, having antithrombotic 
effects as well. 
It has now just been found that the .beta.-D-phenylthioxyloside compounds 
according to the invention, which are structurally different from the 
known products of the prior art, are useful in the treatment and 
prevention of diseases associated with circulatory disorders, especially 
as venous antithrombotics. 
The compounds according to the invention unexpectedly have antithrombotic 
properties which are greatly superior to those of the known products of 
the prior art; reference is made in this connection to the results of the 
comparative experiments collated in Table I below. 
The novel products according to the invention are selected from the group 
consisting of the .beta.-D-phenylthioxylosides of the formula 
##STR2## 
in which: X represents a sulfur atom or an oxygen atom; 
R.sub.1, R.sub.2 and R.sub.3, which are identical or different, each 
represent a hydrogen atom, a nitro group, a cyano group, a group --CO--R 
(in which R represents a C.sub.1 -C.sub.4 alkyl group or a trifluoromethyl 
group), an amino group, an acetamido group (NHCOCH.sub.3), a C.sub.1 
-C.sub.4 alkoxy group, a trifluoromethyl group or a phenyl group 
substituted by one or more cyano, nitro or trifluoromethyl groups, it 
being possible for R.sub.1 and R.sub.2, taken together, to form, with the 
phenyl group to which they are bonded, a .beta.-naphthalenyl group which 
is unsubstituted or substituted by one or more cyano, nitro or 
trifluoromethyl groups; and 
Y represents the hydrogen atom or an aliphatic acyl group. 
The hydroxyl groups of the .beta.-D-thioxylose residue are capable of being 
acylated, especially acetylated. The present invention therefore includes 
the derivatives of formula I in which the hydroxyl groups of the 
.beta.-D-thioxylose residue are acylated, especially acetylated. 
Among the aliphatic acyl groups which are suitable according to the 
invention, there may be mentioned those which contain a total of 2 to 5 
carbon atoms, the preferred aliphatic acyl group being CH.sub.3 CO. 
C.sub.1 -C.sub.4 alkyl group is understood here as meaning a linear or 
branched hydrocarbon radical containing 1 to 4 carbon atoms, the preferred 
alkyl group being the methyl group. 
C.sub.1 -C.sub.4 alkoxy group is understood here as meaning an alkoxy group 
in which the linear or branched hydrocarbon radical contains 1 to 4 carbon 
atoms, the preferred alkoxy group being the methoxy group. 
The preferred compounds according to the invention are the compounds of 
formula I in which: 
X represents a sulfur atom or an oxygen atom; 
R.sub.1 represents the hydrogen atom; 
at least one of the radicals R.sub.2 and R.sub.3 represents a cyano group 
or R.sub.2 represents the hydrogen atom and R.sub.3 represents a 4-acetyl 
group, a 4-acetamido group or a 2-nitro group; and 
Y represents the hydrogen atom or a C.sub.2 -C.sub.5 aliphatic acyl group. 
The compounds of formula I and the corresponding acylated compounds can be 
prepared by means of a glycosylation reaction which comprises: 
(i) reacting a compound of the formula 
##STR3## 
in which X, R.sub.1, R.sub.2 and R.sub.3 are as defined above, with a 
thioxylose derivative selected from the group consisting of: 
(i) the acylthioxylosyl halides of the formula 
##STR4## 
(ii) the peracylated thioxyloses of the formula 
##STR5## 
and (iii) the acylthioxylosyl trichloroacetimidates of the formula 
##STR6## 
in which Hal represents a halogen atom such as Cl or Br (the bromine atom 
being the preferred halogen atom here) and Y represents an acyl group, 
especially an aliphatic acyl group containing a total of 2 to 5 carbon 
atoms and preferably the acetyl group, 
in an inert solvent, at a rate of 1 mol of II to about 0.6 to 1.2 mol of 
compound III, IV or V, in the presence of an acid acceptor and/or a Lewis 
acid; and 
(ii) if necessary, carrying out a deacylation reaction at a temperature in 
the range from 0.degree. C. to the reflux temperature in the range from 
0.degree. C. to the reflux temperature of the reaction medium, in a 
C.sub.1 -C.sub.4 lower alcohol (preferably methanol), in the presence of a 
metal alcoholate (preferably magnesium methylate or sodium methylate), to 
give a compound of formula I in which Y is H. 
Compounds III, IV and V can be in the .alpha. or .beta. configuration or in 
the form of an anomeric mixture of both configurations. 
The glycosylation reactions of phenols and thiophenols II were carried out 
either starting from compound III in the presence of a catalyst such as 
salts or oxides of silver, mercury or zinc, or starting from compound V in 
the presence of a Lewis acid, especially boron trifluoride etherate or 
zinc chloride, or starting from compound IV in the presence of a Lewis 
acid. 
According to one preferred way of carrying out the invention, it is 
recommended to condense 1 mol of phenol or thiophenol II with about 1.1 to 
1.2 mol of acylthioxylosyl halide III in an inert solvent selected from 
polar or apolar solvents (for example dimethylformamide, tetrahydrofuran, 
dioxane, acetonitrile, nitromethane, benzene, toluene, xylenes and 
mixtures thereof), in the presence of mercuric cyanide. 
It will be advantageous to use 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide in a 
benzene/nitromethane mixture (1/1 v/v), in the presence of 1.1 to 1.3 mol 
of mercuric cyanide, at a temperature in the range from 0.degree. C. to 
the reflux temperature of the reaction medium, preferably at about 
40.degree.-50.degree. C., for 1 to 4 hours, preferably for about 2 hours. 
According to a second preferred way of carrying out the invention, it is 
recommended to condense 1 mol of phenol or thiophenol II with about 1.1 to 
1.2 mol of acylthioxylosyl halide III in an inert solvent (for example 
methylene chloride or acetonitrile), in the presence of silver imidazolate 
and zinc chloride. 
It will be advantageous to use 2,3,4-tri-O-acetyl-5-thio-D-xylopyranosyl 
bromide in methylene chloride or a methylene chloride/acetonitrile 
mixture, in the presence of 1.5 to 1.7 mol of silver imidazolate and 2 to 
2.2 mol of zinc chloride, at a temperature in the range from 0.degree. C. 
to the reflux temperature of the reaction medium, preferably at about 
40.degree.-60.degree. C., for 24 to 48 hours. 
According to a third preferred way of carrying out the invention, it is 
recommended to condense 1 mol of phenol or thiophenol II with about 0.6 to 
1 mol of acylthioxylosyl halide III in an inert solvent (for example 
toluene and/or acetonitrile), in the presence of zinc oxide. 
It will be advantageous to use 2,3,4-tri-O-acetyl-5-thio-D-xylopyranosyl 
bromide in a toluene/acetonitrile mixture, in the presence of 0.5 to 1.2 
mol of zinc oxide, at a temperature in the range from room temperature to 
the reflux temperature of the reaction medium, preferably at about 
40.degree.-60.degree. C., for 18 to 48 hours. 
According to a fourth preferred way of carrying out the invention, it is 
recommended to condense 1 mol of phenol or thiophenol II with about 1.1 to 
1.3 mol of acylthioxylosyl trichloroacetimidate in an inert solvent (for 
example methylene chloride), in the presence of boron trifluoride 
etherate. 
It will be advantageous to use 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl trichloroacetimidate in 
methylene chloride, in the presence of 0.1 to 0.4 mol of boron trifluoride 
etherate dissolved in methylene chloride, or zinc chloride, at a 
temperature in the range from -40.degree. C. to room temperature 
(15.degree.-25.degree. C.), preferably at about -20.degree. C. to 
0.degree. C., for 1 to 5 hours. 
In all cases the glycosylation reaction yields a mixture of the isomers of 
.alpha. and .beta. configuration in variable proportions. 
The isomer of .beta. configuration is isolated by the methods known to 
those skilled in the art, for example fractional crystallization or 
chromatography, especially flash chromatography (i.e. chromatography on a 
silica column, under pressure, according to the technique described by W. 
C. STILL et al. in J. Org. Chem. (1978), 42 (no. 14) 2923). 
If appropriate, the derivatives obtained are subjected to deacylation, more 
particularly to deacetylation, which is carried out at a temperature in 
the range from 0.degree. C. to the reflux temperature of the reaction 
medium, in a C.sub.1 -C.sub.4 lower alcohol, in the presence of the 
corresponding metal alcoholate. Preferably, methanol will be chosen as the 
lower alcohol and sodium or magnesium methanolate as the metal alcoholate. 
If desired, the deacylation reaction can be carried out after glycosylation 
without isolation of the intermediate acylated compound formed. 
It is also possible to carry out the deacylation reaction enzymatically, 
for example using pork liver esterase. 
The acylthioxylosyl halides of formula III of .beta. configuration in which 
Y represents an aliphatic acyl group containing 2 to 5 carbon atoms are 
novel compounds. 
The acylthioxylosyl trichloroacetimidates of formula V in which Y 
represents an aliphatic acyl group containing 2 to 5 carbon atoms are 
novel compounds. 
To obtain the intermediate thiophenols of formula II in which X=S, it is 
recommended to: 
(i) condense dimethylaminothiocarbamoyl chloride of the formula 
##STR7## 
in a strong basic medium, with a phenol of the formula 
##STR8## 
in which R.sub.1, R.sub.2 and R.sub.3 are as defined above, to give a 
compound of the formula 
##STR9## 
in which R.sub.1, R.sub.2 and R.sub.3 are as defined above; 
(ii) subject the resulting compound of formula VII to a Newmann 
rearrangement (J. Org. Chem. (1966) 31, p. 3980), by heating, to give a 
compound of the formula 
##STR10## 
in which R.sub.1, R.sub.2 and R.sub.3 are as defined above; and 
(iii) treat the resulting compound of formula VIII with a metal alcoholate, 
preferably sodium or magnesium methanolate, in a C.sub.1 -C.sub.4 lower 
alcohol, preferably methanol, dimethylformamide or dioxane, to give a 
thiophenol of formula II in which X=S. 
The intermediate thiophenols can also be obtained by the nucleophilic 
substitution of an appropriate halogenobenzene according to the method 
described by L. TESTAFERRI in Tetrahedron Letters, vol. 21, p. 3099-3100 
(1980) or according to the method described by Paolo BATTISTONI in 
Gazzetta Chimica Italiana, 110, p. 301 (1980). 
The following thiophenols are novel compounds: 
3,5-bis(trifluoromethyl)benzenethiol, 3-cyano-4-mercaptobenzonitrile, 
6-mercaptonaphthalene-2-carbonitrile and 
3,5-dicyano-2-mercaptobenzonitrile. 
The following dimethylthiocarbamates are novel compounds: 
O-4-trifluoromethylphenyl dimethylthiocarbamate, O-3-cyanophenyl 
dimethylthiocarbamate, O-2-cyanophenyl dimethylthiocarbamate, 
O-2-(6-cyanonaphthalenyl)dimethylthiocarbamate, O-3,4,5-trimethoxyphenyl 
dimethylthiocarbamate, O-2-trifluoromethylphenyl dimethylthiocarbamate, 
O-3,5-bis(trifluoromethyl)phenyl dimethylthiocarbamate, 
O-2,4-dicyanophenyl dimethylthiocarbamate, O-4-(4-cyanophenyl)phenyl 
dimethylthiocarbamate, O-2,4,6-tricyanophenyl dimethylthiocarbamate, 
S-4-trifluoromethylphenyl dimethylthiocarbamate, S-3-cyanophenyl 
dimethylthiocarbamate, S-2-cyanophenyl dimethylthiocarbamate, 
S-2-(6-cyanonaphthalenyl)dimethylthiocarbamate, S-3,4,5-trimethoxyphenyl 
dimethylthiocarbamate, S-2-trifluoromethylphenyl dimethylthiocarbamate, 
S-3,5-bis(trifluoromethyl)phenyl dimethylthiocarbamate, 
S-2,4-dicyanophenyl dimethylthiocarbamate, S-4-(4-cyanophenyl)phenyl 
dimethylthiocarbamate and S-2,4,6-tricyanophenyl dimethylthiocarbamate. 
According to the invention, a therapeutic composition is proposed which 
contains, in association with a physiologically acceptable excipient, at 
least one compound selected from the group consisting of the products of 
formula I. Of course, in such a composition, the active ingredient is 
present in a therapeutically effective amount. 
The compounds of formula I are useful in therapy as antithrombotics. They 
are particularly useful in the prevention and treatment of disorders of 
the venous circulation. 
According to the invention, it is recommended to use a substance belonging 
to the group consisting of the compounds of formula I in order to obtain 
an antithrombotic drug for use in therapy to combat disorders of the 
venous circulation. 
Further characteristics and advantages of the invention will be understood 
more clearly from the following description of Preparatory Examples, which 
in no way imply a limitation and are given by way of illustration, and 
results of pharmacological experiments. 
In the following Preparatory Examples, the .alpha. or .beta. configuration 
has been specified in the compound names in cases where said configuration 
was determined. Where the configuration is not indicated, this means that 
the corresponding product is an anomeric mixture of the .alpha. and .beta. 
configurations in proportions which were not determined.

PREATION I 
Preparation of 4-cyanophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 1a) 
Under an inert atmosphere, a mixture of 70 ml of anhydrous benzene, 70 ml 
of nitromethane and 15 g of a 0.4 nm molecular sieve (marketed by E. 
MERCK) is stirred at room temperature (15.degree.-25.degree. C.) for 0.25 
h and 12 g (47.10.sup.-3 mol) of Hg(CN).sub.2 are then added. After the 
resulting mixture has been stirred for 10 minutes at room temperature, 
16.9 g (47.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide and then 6 g 
(43.10.sup.-3 mol) of 4-mercaptobenzonitrile are added in small portions. 
When the addition is complete, the reaction mixture is heated at 
40.degree.-50.degree. C. for 8 hours and then filtered on Celite.RTM. 
(i.e. diatomaceous silica for filtration). The residue is washed several 
times with ethyl acetate. The organic phase is collected and washed 
successively with a 1N aqueous solution of hydrochloric acid, a 1N aqueous 
solution of sodium hydroxide and a saturated solution of sodium chloride 
and then with water until the pH of the washings is neutral; it is dried 
over magnesium sulfate and filtered and the solvent is evaporated off. The 
crude product obtained is recrystallized from an ethyl acetate/petroleum 
ether mixture to give 8.65 g (yield: 49%) of the product of .beta. 
configuration. 
M.p.=155.degree. C. 
[.alpha.].sub.D.sup.20 C. =+37.degree. (c=0.5; CHCl.sub.3) 
PREATION II 
Preparation of 4-cyanophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 1a) 
A suspension of 625 mg (1.76.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-D-xylopyranosyl bromide, 200 mg (1.48.10.sup.-3 
mol) of 4-mercaptobenzonitrile and a 400 pm molecular sieve in 10 ml of 
acetonitrile is stirred in the presence of 605 mg (4.4.10.sup.-3 mol) of 
zinc chloride and 310 mg (1.8.10.sup.-3 mol) of silver imidazolate, in the 
absence of light, under an inert atmosphere. After heating at 50.degree. 
C. for 3 h, the reaction mixture is filtered on Celite.RTM. in ethyl 
acetate. The filtrate is washed with a 1N solution of hydrochloric acid, 
water, a 1N solution of sodium hydroxide, water and finally a saturated 
solution of sodium chloride, dried over magnesium sulfate and evaporated 
under reduced pressure. After purification by chromatography on silica gel 
using a hexane/ethyl acetate mixture (3/1 v/v) as the eluent, and 
precipitation in ether, 100 mg (yield: 17%) of the expected product are 
obtained. 
M.p.=155.degree. C. 
PREATION III 
Preparation of 4-cyanophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 1a) 
A suspension of 192 mg (0.44.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl trichloroacetimidate, 71 
mg (0.52.10.sup.-3 mol) of 4-mercaptobenzonitrile, 20 mg (0.15.10.sup.-3 
mol) of zinc chloride and a 400 pm sieve in 2 ml of acetonitrile is 
stirred for 4 h under an inert atmosphere. The reaction mixture is then 
filtered on Celite.RTM. in ethyl acetate and subsequently washed with a 1N 
solution of sodium hydroxide, water and finally a saturated solution of 
sodium chloride, dried over magnesium sulfate and evaporated under reduced 
pressure. After precipitation in ether, 42 mg (yield: 23%) of the expected 
product are obtained. 
M.p.=155.degree. C. 
PREATION IV 
Preparation of 4-cyanophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 1a) 
A suspension of 16.9 g (47.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide, 6 g 
(43.10.sup.-3 mol) of 4-mercaptobenzonitrile and 3.5 g (43.10.sup.-3 mol) 
of zinc oxide (ZnO) in 120 ml of anhydrous toluene and 120 ml of 
acetonitrile is stirred under an inert atmosphere, in the presence of a 
molecular sieve (1 mm), for 18 hours, at 50.degree. C. After the reaction 
medium has been filtered on Celite.RTM. in ethyl acetate, the organic 
phase obtained is washed with a 1N solution of HCl twice, a 1N solution of 
sodium hydroxide and finally water, dried over magnesium sulfate and 
evaporated under reduced pressure. After precipitation in ether, 11.30 g 
(yield: 64%) of the expected product are obtained. 
M.p.=155.degree. C. 
PREATION V 
Preparation of 4-cyanophenyl 1,5-dithio-.beta.-D-xylopyranoside (Example 1) 
Under a nitrogen atmosphere, 8.5 g (21.10.sup.-3 mol) of 4-cyanophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 1a) are 
suspended in 100 ml of methanol, and 2 ml of sodium methylate (8% w/v of 
Na in methanol) are then added. The reaction medium is stirred at room 
temperature until the starting material has completely dissolved (2 hours) 
and is then neutralized by the addition of Amberlite.RTM. IR 120 H.sup.+ 
resin. The methanol is evaporated off under reduced pressure; the crude 
product obtained is recrystallized from an ethanol/water mixture (65/25 
v/v) to give 5.3 g (yield: 89.7%) of the expected product. 
M.p.=175.degree. C. 
[.alpha.].sub.D.sup.20.degree. C. =+35.8.degree. (c=0.5; CH.sub.3 OH) 
PREATION VI 
Preparation of 4-nitrophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 2a) 
If the procedure described in Preparation I is followed starting from 6 g 
(38.10.sup.-3 mol) of 4-nitrobenzenethiol, 10.7 g (42.10.sup.-3 mol) of 
mercuric cyanide, Hg(CN).sub.2, and 15.1 g (42.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide, 10.8 g (yield: 
66%) of the expected product are obtained. 
M.p.=182.degree. C. 
[.alpha.].sub.D.sup.20.degree. C. =+50.8.degree. (c=0.64; CHCl.sub.3) 
PREATION VII 
Preparation of 4-nitrophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 2a) 
If the procedure described in Preparation IV is followed starting from 6 g 
(38.10.sup.-3 mol) of 4-nitrobenzenethiol, 15.1 g (42.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide and 3.2 g 
(39.10.sup.-3 mol) of zinc oxide (ZnO), 13 g (yield: 79%) of the expected 
product are obtained after precipitation in ether. 
M.p.=182.degree. C. 
PREATION VIII 
Preparation of 4-nitrophenyl 1,5-dithio-.beta.-D-xylopyranoside (Example 2) 
If the procedure described in Preparation V is followed starting from 10.3 
g (24.10.sup.-3 mol) of 4-nitrophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 2a), 5.4 g 
(yield: 74%) of the expected product are obtained after recrystallization 
from an ethanol/water mixture (1/1 v/v). 
M.p.=168.degree. C. 
[.alpha.].sub.D.sup.20.degree. C. =+54.degree. (c=0.64; CH.sub.3 OH) 
PREATION IX 
Preparation of 2-naphthalenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 3a) 
If the procedure described in Preparation I is followed starting from 6.8 g 
(42.4.10.sup.-3 mol) of naphthalene-2-thiol, 10.8 g (42.4.10.sup.-3 mol) 
of mercuric cyanide, Hg(CN).sub.2, and 12 g (33.2.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide, 5.84 g (yield: 
40%) of the expected product are obtained. 
M.p.=151.degree. C. 
[.alpha.].sub.D.sup.20.degree. C. =-41.5.degree. (c=1.6; CHCl.sub.3) 
PREATION X 
Preparation of 2-naphthalenyl 1,5-dithio-.beta.-D-xylopyranoside (Example 
3) 
If the procedure described in Preparation V is followed starting from 5.8 g 
(13.10.sup.-3 mol) of 2-naphthalenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.alpha.-D-xylopyranoside (Example 3a), 3.45 
g (yield: 86%) of the expected product are obtained after 
recrystallization from an ethanol/water mixture (4/1 v/v). 
M.p.=163.degree.-164.degree. C. 
[.alpha.].sub.D.sup.20.degree. C. =+31.1.degree. (c=0.9; CH.sub.3 OH) 
PREATION XI 
Preparation of O-4-trifluoromethylphenyl dimethylthiocarbamate 
10 g (62.10.sup.-3 mol) of 4-trifluoromethylphenol are added to a solution 
of 3.63 g (65.10.sup.-3 mol) of potassium hydroxide in 100 ml of water and 
100 ml of acetone. The mixture obtained is stirred for 45 minutes at room 
temperature and then cooled to 0.degree. C. before the addition of 8.77 g 
(71.10.sup.-3 mol) of dimethylthiocarbamoyl chloride. The resulting 
reaction medium is subsequently stirred for 4 hours at room temperature 
and then hydrolyzed. The expected product is extracted with ethyl acetate. 
The resulting organic phase is washed with a 1N aqueous solution of sodium 
hydroxide, then a 1N aqueous solution of hydrochloric acid and finally 
water, after which it is dried and evaporated under reduced pressure to 
give 17 g (quantitative yield) of the expected product. 
PREATION XII 
Preparation of S-4-trifluoromethylphenyl dimethylthiocarbamate 
Under a nitrogen atmosphere, 17 g (68.10.sup.-3 mol) of 
O-4-trifluoromethylphenyl dimethylthiocarbamate are heated at 220.degree. 
C. for 5 hours. After purification by flash chromatography using a 
toluene/ethyl acetate mixture (8/1 v/v) as the eluent, 13 g (yield: 80%) 
of the expected product are obtained. 
PREATION XIII 
Preparation of 4-trifluoromethylbenzenethiol 
Under a nitrogen atmosphere, 12 g (48.10.sup.-3 mol) of 
S-4-trifluoromethylphenyl dimethylthiocarbamate are dissolved in 125 ml of 
dimethylformamide. The solution obtained is cooled to 0.degree. C. and 25 
ml of an 18% solution of sodium methylate in methanol are then added. 
After stirring for 1.5 hours, the reaction medium is hydrolyzed in a 1N 
hydrochloric acid/ice mixture and then extracted with ethyl acetate. The 
organic phase obtained is washed with water, dried over magnesium sulfate 
and then evaporated under reduced pressure. 6.2 g (yield: 67%) of the 
expected product are obtained after purification by flash chromatography 
using a hexane/ethyl acetate mixture (8/1 v/v) as the eluent. 
PREATION XIV 
Preparation of 4-trifluoromethylphenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 4a) 
If the procedure described in Preparation I is followed starting from 5.58 
g (32.10.sup.-3 mol) of 4-trifluoromethylbenzenethiol, 8.87 g 
(35.10.sup.-3 mol) of mercuric cyanide, Hg(CN).sub.2, and 12.3 g 
(35.10.sup.-3 mol) of 2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl 
bromide, 6.2 g (yield: 40%) of the expected product are obtained. 
M.p.=160.degree. C. 
[.alpha.].sub.D.sup.20.degree. C. =+16.degree. (c=0.5; CHCl.sub.3) 
PREATION XV 
Preparation of 4-trifluoromethylphenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 4a) 
If the procedure described in Preparation IV is followed starting from 5.6 
g (32.10.sup.-3 mol) of 4-trifluoromethylbenzenethiol, 12.3 g 
(35.10.sup.-3 mol) of 2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl 
bromide and 2.55 g (32.10.sup.-3 mol) of zinc oxide (ZnO), 7.4 g (yield: 
48%) of the expected product are obtained after precipitation in ether. 
M.p.=160.degree. C. 
PREATION XVI 
Preparation of 4-trifluoromethylphenyl 1,5-dithio-.beta.-D-xylopyranoside 
(Example 4) 
If the procedure described in Preparation V is followed starting from 6.2 g 
(14.10.sup.-3 mol) of 4-trifluoromethylphenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 4a), 2.05 g 
(yield: 45%) of the expected product are obtained after purification by 
flash chromatography using a CHCl.sub.3 /CH.sub.3 OH mixture (4/1 v/v) as 
the eluent. 
M.p.=128.degree.-130.degree. C. 
[.alpha.].sub.D.sup.23.degree. C. =+10.degree. (c=0.5; CH.sub.3 OH) 
PREATION XVII 
Preparation of O-3-cyanophenyl dimethylthiocarbamate 
If the procedure described in Preparation XI is followed starting from 15 g 
(126.10.sup.-3 mol) of 3-hydroxybenzonitrile, 17.9 g (145.10.sup.-3 mol) 
of dimethylthiocarbamoyl chloride and 7.4 g (132.10.sup.-3 mol) of 
potassium hydroxide, 29 g (quantitative yield) of the expected product are 
obtained. 
M.p.=108.degree. C. 
PREATION XVIII 
Preparation of S-3-cyanophenyl dimethylthiocarbamate 
If the procedure described in Preparation XII is followed starting from 29 
g (141.10.sup.-3 mol) of O-3-cyanophenyl dimethylthiocarbamate, 19 g 
(yield: 65.5%) of the expected product are obtained. 
M.p.=104.degree. C. 
PREATION XIX 
Preparation of 3-mercaptobenzonitrile 
If the procedure described in Preparation XIII is followed starting from 19 
g (92.10.sup.-3 mol) of O-3-cyanophenyl dimethylthiocarbamate, 10.3 g 
(yield: 83.1%) of the expected product, melting at 91.degree.-95.degree. 
C., are obtained. 
PREATION XX 
Preparation of 3-cyanophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 5a) 
If the procedure described in Preparation I is followed starting from 9.3 g 
(67.10.sup.-3 mol) of 3-mercaptobenzonitrile, 18 g (73.10.sup.-3 mol) of 
mercuric cyanide, Hg(CN).sub.2, and 26.14 g (73.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide, 8.55 g of the 
expected product are obtained. 
M.p.=133.degree. C. 
[.alpha.].sub.D.sup.20.degree. C. =+0.9.degree. (c=0.44; CHCl.sub.3) 
PREATION XXI 
Preparation of 3-cyanophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 5a) 
If the procedure described in Preparation IV is followed starting from 10.3 
g (74.1.10.sup.-3 mol) of 3-mercaptobenzonitrile, 28.94 g (81.5.10.sup.-3 
mol) of 2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide and 6.05 
g (74.3.10.sup.-3 mol) of zinc oxide (ZnO), 9.6 g (yield: 31%) of the 
expected product are obtained. 
M.p.=133.degree. C. 
PREATION XXII 
Preparation of 3-cyanophenyl 1,5-dithio-.beta.-D-xylopyranoside (Example 5) 
If the procedure described in Preparation V is followed starting from 8.50 
g (20.10.sup.-3 mol) of 3-cyanophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside, 3.10 g (yield: 
54.3%) of the expected product are obtained after recrystallization from 
methanol. 
M.p.=194.degree.-195.degree. C. 
[.alpha.].sub.D.sup.20.degree. C. =-5.4.degree. (c=0.48; CH.sub.3 OH) 
PREATION XXIII 
Preparation of O-2-cyanophenyl dimethylthiocarbamate 
If the procedure described in Preparation XVI is followed starting from 15 
g (126.10.sup.-3 mol) of 2-hydroxybenzonitrile, 17.9 g (145.10.sup.-3 mol) 
of dimethylthiocarbamoyl chloride and 7.4 g (126.10.sup.-3 mol) of 
potassium hydroxide, 24.1 g (yield: 94%) of the expected product are 
obtained. 
M.p.=112.degree. C. 
PREATION XXIV 
Preparation of S-2-cyanophenyl dimethylthiocarbamate 
If the procedure described in Preparation XII is followed starting from 28 
g (136.10.sup.-3 mol) of O-2-cyanophenyl dimethylthiocarbamate, 20 g 
(yield: 71.4%) of the expected product are obtained. 
M.p.=70.degree. C. 
PREATION XXV 
Preparation of 2-mercaptobenzonitrile 
If the procedure described in Preparation XIII is followed starting from 20 
g (97.10.sup.-3 mol) of S-2-cyanophenyl dimethylthiocarbamate, 10.9 g 
(yield: 83.2%) of the expected product are obtained in the form of an oil. 
n.sub.D =1.496 
PREATION XXVI 
Preparation of 2-cyanophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 6a) 
If the procedure described in Preparation I is followed starting from 9.70 
g (72.10.sup.-3 mol) of 2-mercaptobenzonitrile, 19.45 g (77.10.sup.-3 mol) 
of mercuric cyanide, Hg(CN).sub.2, and 27.4 g (77.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide, 14.7 g (yield: 
50%) of the expected product are obtained. 
M.p.=160.degree. C. 
[.alpha.].sub.D.sup.20.degree. C. =-45.5.degree. (c=0.4; CHCl.sub.3) 
PREATION XXVII 
Preparation of 2-cyanophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 6a) 
If the procedure described in Preparation IV is followed starting from 10.7 
g (79.2.10.sup.-3 mol) of 2-mercaptobenzonitrile, 30.2 g (85.10.sup.-3 
mol) of 2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide and 6.3 
g (77.4.10.sup.-3 mol) of zinc oxide (ZnO), 19.3 g (yield: 60%) of the 
expected product are obtained after crystallization from ether. 
M.p.=160.degree. C. 
PREATION XXVIII 
Preparation of 2-cyanophenyl 1,5-dithio-.beta.-D-xylopyranoside (Example 6) 
If the procedure described in Preparation V is followed starting from 14.5 
g (35.10.sup.-3 mol) of 2-cyanophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 6a), 8.39 g 
(yield: 84.6%) of the expected product are obtained after 
recrystallization from methanol. 
M.p.=118.degree.-119.degree. C. 
[.alpha.].sub.D.sup.20.degree. C. =+12.5.degree. (c=0.52; CH.sub.3 OH) 
PREATION XXIX 
Preparation of 2-nitrobenzenethiol 
15.24 g (63.4.10.sup.-3 mol) of sodium sulfide (Na.sub.2 S.9H.sub.2 O) are 
added to a solution of 10 g (63.4.10.sup.-3 mol) of 2-chloronitrobenzene. 
The solution obtained is stirred at room temperature for 12 hours. The 
reaction medium is hydrolyzed in an ice/1N hydrochloric acid mixture. The 
yellow precipitate formed is filtered off and the mother liquors are 
extracted with ethyl acetate. The resulting organic phase is washed with 
water until the pH of the washings is neutral, dried over magnesium 
sulfate and evaporated under reduced pressure to give 5.2 g of an oil, 
which are added to the 3.8 g of precipitate. These 9 g of resulting 
product are purified by chromatography on silica using a hexane/acetone 
mixture (95/5 v/v) as the eluent to give 6.02 g (yield: 61%) of the 
expected product. 
PREATION XXX 
Preparation of 2-nitrophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 7a) 
If the procedure described in Preparation I is followed starting from 6 g 
(38.7.10.sup.-3 mol) of 2-nitrobenzenethiol, 10.75 g (42.5.10.sup.-3 mol) 
of mercuric cyanide, Hg(CN).sub.2, and 15.12 g (42.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide, 8 g (yield: 
48%) of the expected product are obtained. 
M.p.=176.degree. C. 
[.alpha.].sub.D.sup.20.degree. C. =+15.degree. (c=0.5; CH.sub.2 Cl.sub.2 
/CH.sub.3 OH (1/1 v/v)) 
PREATION XXXI 
Preparation of 2-nitrophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 7a) 
If the procedure described in Preparation IV is followed starting from 6.1 
g (39.3.10.sup.-3 mol) of 2-nitrobenzenethiol, 15.40 g (43.3.10.sup.-3 
mol) of 2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide and 3.68 
g (45.2.10.sup.-3 mol) of zinc oxide (ZnO), 9.87 g (yield: 58%) of the 
expected product are obtained. 
PREATION XXXII 
Preparation of 2-nitrophenyl 1,5-dithio-.beta.-D-xylopyranoside (Example 7) 
If the procedure described in Preparation V is followed starting from 8 g 
(18.6.10.sup.-3 mol) of 2-nitrophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 7a), 4.68 g 
(yield: 83.2%) of the expected product are obtained after 
recrystallization from methanol. 
M.p.=185.degree. C. 
[.alpha.].sub.D.sup.20.degree. C. =+12.4.degree. (c=0.5; CH.sub.2 Cl.sub.2 
/CH.sub.3 OH (1/1 v/v)) 
PREATION XXXIII 
Preparation of O-2-(6-cyanonaphthalenyl)dimethylthiocarbamate 
2.85 g (51.10.sup.-3 mol) of potassium hydroxide pellets are added to a 
suspension of 8.05 g (47.10.sup.-3 mol) of 
2-hydroxynaphthalene-6-carbonitrile in 50 ml of acetone and 90 ml of 
water. The reaction mixture is heated at 50.degree. C. for thirty minutes, 
with vigorous stirring. The mixture is then cooled to 0.degree. C. and 
6.46 g (52.10.sup.-3 mol) of dimethylthiocarbamoyl chloride in 80 ml of 
acetone are added dropwise. When the addition is complete, the reaction 
medium is stirred for three hours at room temperature. It is concentrated 
by evaporation under reduced pressure and then hydrolyzed. 11.3 g (yield: 
94%) of the expected product are obtained after filtration of the 
precipitate. 
M.p.=153.degree.-154.degree. C. 
PREATION XXXIV 
Preparation of S-2-(6-cyanonaphthalenyl)dimethylthiocarbamate 
Under a nitrogen atmosphere, 10 g (39.10.sup.-3 mol) of 
O-2-(6-cyanonaphthalenyl)dimethylthiocarbamate are heated at 250.degree. 
C. for six hours, with stirring. The disappearance of the starting 
material is monitored by thin layer chromatography using an ethyl 
acetate/toluene mixture (1/4 v/v) as the eluent. 7.6 g (yield: 76%) of the 
expected product are obtained. 
M.p.=166.degree.-168.degree. C. 
PREATION XXXV 
Preparation of 6-mercaptonaphthalene-2-carbonitrile 
Under a nitrogen atmosphere, 7.15 g (27.9.10.sup.-3 mol) of 
O-2-(6-cyanonaphthalenyl)dimethylthiocarbamate are suspended in 50 ml of 
dioxane, with stirring, and 16 ml (55.8.10.sup.-3 mol) of sodium methylate 
(8% w/v solution of Na in methanol) are then added to the mixture. The 
reaction medium is stirred at 21.degree. C. for two hours and monitored by 
thin layer chromatography using an ethyl acetate/toluene mixture (1/3 v/v) 
as the eluent. The reaction medium is hydrolyzed in an ice/concentrated 
HCl mixture and the precipitate formed is filtered off to give 5.4 g 
(yield: 100%) of the expected product. 
M.p.=113.degree.-115.degree. C. 
PREATION XXXVI 
Preparation of 2-(6-cyanonaphthalenyl) 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 8a) 
If the procedure described in Preparation I is followed starting from 5 g 
(27.10.sup.-3 mol) of 6-mercaptonaphthalene-2-carbonitrile, 7.5 g 
(29.10.sup.-3 mol) of mercuric cyanide, Hg(CN).sub.2, and 12 g 
(32.10.sup.-3 mol) of 2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl 
bromide, 1.6 g (yield: 12.9%) of the expected product are obtained. 
M.p.=228.degree.-230.degree. C. 
[.alpha.].sub.D.sup.23.degree. C. =+73.4.degree. (c=0.5; CHCl.sub.3) 
PREATION XXXVII 
Preparation of 2-(6-cyanonaphthalenyl) 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 8a) 
If the procedure described in Preparation IV is followed starting from 5 g 
(27.10.sup.-3 mol) of 6-mercaptonaphthalene-2-carbonitrile, 12 g 
(32.4.10.sup.-3 mol) of 2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl 
bromide and 2.2 g (27.10.sup.-3 mol) of zinc oxide (ZnO), 1.5 g of the 
expected product are obtained after precipitation in ether. 
M.p.=228.degree.-230.degree. C. 
PREATION XXXVIII 
Preparation of 2-(6-cyanonaphthalenyl) 1,5-dithio-.beta.-D-xylopyranoside 
(Example 8) 
If the procedure described in Preparation V is followed starting from 1.27 
g (2.76.10.sup.-3 mol) of 2-(6-cyanonaphthalenyl) 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 8a), 0.340 
g (yield: 37%) of the expected product is obtained after recrystallization 
from a methanol/chloroform mixture (1/1 v/v). 
M.p.=226.degree.-228.degree. C. 
[.alpha.].sub.D.sup.24.degree. C. =+45.9.degree. (c=0.3; DMSO) 
PREATION XXXIX 
Preparation of phenyl 2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside 
(Example 9a) 
If the procedure described in Preparation I is followed starting from 4 g 
(36.3.10.sup.-3 mol) of benzenethiol, 14 g (39.4.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-xylopyranosyl bromide and 10 g 
(39.10.sup.-3 mol) of mercuric cyanide (Hg(CN).sub.2), 7.3 g of the 
expected product are obtained after crystallization from ether. 
M.p.=130.degree. C. 
[.alpha.].sub.D.sup.20.degree. C. =+14.6.degree. (c=0.5; CHCl.sub.3) 
PREATION XL 
Preparation of phenyl 2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside 
(Example 9a) 
If the procedure described in Preparation IV is followed starting from 4 g 
(36.3.10.sup.-3 mol) of benzenethiol, 15 g (42.3.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide and 3 g 
(36.8.10.sup.-3 mol) of zinc oxide (ZnO), 4.5 g (yield: 32.29%) of the 
expected product are obtained after crystallization from ether. 
M.p.=130.degree. C. 
PREATION XLI 
Preparation of phenyl 1,5-dithio-.beta.-D-xylopyranoside (Example 9) 
If the procedure described in Preparation V is followed starting from 6.9 g 
(18.10.sup.-3 mol) of phenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 9a), 3.7 g 
(yield: 80%) of the expected product are obtained after recrystallization 
from an ethanol/water mixture (50/10 v/v). 
M.p.=150.degree.-151.degree. C. 
[.alpha.].sub.D.sup.20.degree. C. =-6.degree. (c=0.5; CH.sub.3 OH) 
PREATION XLII 
Preparation of 3,4,5-trimethoxyphenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 10a) 
If the procedure described in Preparation I is followed starting from 11.35 
g (57.10.sup.-3 mol) of 3,4,5-trimethoxybenzenethiol, 14.32 g 
(57.10.sup.-3 mol) of mercuric cyanide, Hg(CN).sub.2, and 22.15 g 
(62.10.sup.-3 mol) of 2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl 
bromide, 7.52 g (yield: 28%) of the expected product are obtained. 
M.p.=101.degree. C. 
[.alpha.].sub.D.sup.25.degree. C. =-43.degree. (c=0.2; CH.sub.3 OH) 
PREATION XLIII 
Preparation of 3,4,5-trimethoxyphenyl 1,5-dithio-.beta.-D-xylopyranoside 
(Example 10) 
If the procedure described in Preparation V is followed starting from 4.65 
g (9.8.10.sup.-3 mol) of 3,4,5-trimethoxyphenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 10a), 2.4 g 
(yield: 70%) of the expected product are obtained after recrystallization 
from a methanol/water mixture (1/1 v/v). 
M.p.=166.degree. C. 
[.alpha.].sub.D.sup.20.degree. C. =-12.degree. (c=0.2; CH.sub.3 OH) 
PREATION XLIV 
Preparation of 4-acetylphenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 11a) 
If the procedure described in Preparation I is followed starting from 1.03 
g (6.7.10.sup.-3 mol) of 4-mercaptoacetophenone, 1.72 g (6.8.10.sup.-3 
mol) of mercuric cyanide, Hg(CN).sub.2, and 2.65 g (7.5.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide, 0.36 g (yield: 
12.5%) of the expected product is obtained. 
M.p.=122.degree. C. 
[.alpha.].sub.D.sup.22.degree. C. =+46.5.degree. (c=0.29; CHCl.sub.3) 
PREATION XLV 
Preparation of 4-acetylphenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 11a) 
If the procedure described in Preparation IV is followed starting from 1.27 
g (8.43.10.sup.-3 mol) of 4-mercaptoacetophenone, 3.27 g (9.2.10.sup.-3 
mol) of 2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide and 0.68 
g (8.35.10.sup.-3 mol) of zinc oxide (ZnO), 0.42 g (yield: 11%) of the 
expected product is obtained. 
M.p.=122.degree. C. 
PREATION XLVI 
Preparation of 4-acetylphenyl 1,5-dithio-.beta.-D-xylopyranoside (Example 
11) 
If the procedure described in Preparation V is followed starting from 0.34 
g (0.8.10.sup.-3 mol) of 4-acetylphenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 11a), 0.12 
g (yield: 50%) of the expected product is obtained after recrystallization 
from a methanol/water mixture (1/1 v/v). 
M.p.=175.degree. C. 
[.alpha.].sub.D.sup.25.degree. C. =+34.degree. (c=0.2; CH.sub.3 OH) 
PREATION XLVII 
Preparation of 3-nitrophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 12a) 
If the procedure described in Preparation I is followed starting from 10 g 
(64.5.10.sup.-3 mol) of 3-nitrobenzenethiol, 16.29 g (64.5.10.sup.-3 mol) 
of mercuric cyanide (Hg(CN).sub.2) and 25.2 g (70.9.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide, 7.44 g (yield: 
27%) of the expected product are obtained after purification by flash 
chromatography using a toluene/ethyl acetate mixture (9/1 v/v) as the 
eluent, followed by crystallization from ether. 
M.p.=121.degree. C. 
[.alpha.].sub.D.sup.20.degree. C. =+1.8.degree. (c=0.5; CH.sub.3 OH) 
PREATION XLVIII 
Preparation of 3-nitrophenyl 1,5-dithio-.beta.-D-xylopyranoside (Example 
12) 
If the procedure described in Preparation V is followed starting from 7.18 
g (16.7.10.sup.-3 mol) of 3-nitrophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 12a), 3.9 g 
(yield: 77%) of the expected product are obtained. 
M.p.=152.degree.-154.degree. C. 
[.alpha.].sub.D.sup.20.degree. C. =-3.6.degree. (c=0.5; CH.sub.3 OH) 
PREATION IL 
Preparation of O-2-trifluoromethylphenyl dimethylthiocarbamate 
If the procedure described in Preparation XI is followed starting from 3.95 
g (24.3.10.sup.-3 mol) of 2-trifluoromethylphenol, 1.43 g (25.6.10.sup.-3 
mol) of potassium hydroxide and 3.46 g (28.10.sup.-3 mol) of 
dimethylthiocarbamoyl chloride, 5.37 g (yield: 89%) of a yellow oil are 
obtained. 
n.sub.D.sup.24.5.degree. C. =1.528 
PREATION L 
Preparation of S-2-trifluoromethylphenyl dimethylthiocarbamate 
If the procedure described in Preparation XII is followed starting from 
5.37 g (21.5.10.sup.-3 mol) of O-2-trifluoromethylphenyl 
dimethylthiocarbamate, 3.2 g (yield: 60%) of the expected product are 
obtained after purification by flash chromatography using a toluene/ethyl 
acetate mixture (98/2 v/v) as the eluent. 
n.sub.D.sup.25.degree. C. =1.5182 
PREATION LI 
Preparation of 2-trifluoromethylbenzenethiol 
If the procedure described in Preparation XIII is followed starting from 
2.72 g (10.9.10.sup.-3 mol) of S-2-trifluoromethylphenyl 
dimethylthiocarbamate, 2 g (quantitative yield) of the expected product 
are obtained. 
PREATION LII 
Preparation of 2-trifluoromethylphenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 13a) 
If the procedure described in Preparation I is followed starting from 1.8 g 
(10.10.sup.-3 mol) of 2-trifluoromethylbenzenethiol, 2.55 g (10.10.sup.-3 
mol) of mercuric cyanide (Hg(CN).sub.2) and 3.95 g (11.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide, 1.53 g (yield: 
34%) of the expected product are obtained. 
M.p.=152.degree. C. 
[.alpha.].sub.D.sup.20.degree. C. =+64.degree. (c=0.5; CH.sub.3 OH) 
PREATION LIII 
Preparation of 2-trifluoromethylphenyl 1,5-dithio-.beta.-D-xylopyranoside 
(Example 13) 
If the procedure described in Preparation V is followed starting from 1.38 
g (3.10.sup.-3 mol) of 2-trifluoromethylphenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 13a), 0.75 
g (yield: 75%) of the expected product is obtained after recrystallization 
from a methanol/water mixture (1/1 v/v). 
M.p.=114.degree.-115.degree. C. 
[.alpha.].sub.D.sup.20.degree. C. =+34.degree. (c=0.5; CH.sub.3 OH) 
PREATION LIV 
Preparation of 4-(4-iodophenyl)benzonitrile 
A mixture of 15 g (33.2.10.sup.-3 mol) of 4,4'-diiodo-1,1'-biphenyl, 3.13 g 
(34.9.10.sup.-3 mol) of mercuric cyanide and 2.75 g (34.9.10.sup.-3 mol) 
of pyridine is heated at 200.degree. C. for 15 minutes and 6 ml of 
dimethylformamide are then added to the mixture. After cooling, the 
reaction medium is hydrolyzed with a 1N aqueous solution of hydrochloric 
acid. The expected product is extracted with ethyl acetate. The organic 
phase obtained is washed with water until the pH of the washings is 
neutral, dried over magnesium sulfate and evaporated under vacuum. 3.28 g 
(yield: 33%) of a yellow solid are obtained after purification by flash 
chromatography using a chloroform/toluene mixture (1/1 v/v) as the eluent. 
M.p.=162.degree.-168.degree. C. 
PREATION LV 
Preparation of 4-(4-mercaptophenyl)benzonitrile 
3.25 g (10.8.10.sup.-3 mol) of 4-(4-iodophenyl)benzonitrile are dissolved 
in 50 ml of hexamethylphosphoramide, and 3.05 g (43.4.10.sup.-3 mol) of 
sodium thiomethylate are then added to the solution. The reaction mixture 
is heated at 100.degree. C. for 1.5 hours and then, after cooling, 
hydrolyzed in a 1N hydrochloric acid/ice mixture. The expected product is 
extracted with ethyl acetate. The resulting organic phase is washed with 
water until the pH of the washings is neutral, dried over magnesium 
sulfate and then evaporated under reduced pressure to give 2.4 g 
(quantitative yield) of a pale yellow solid. 
M.p.=105.degree.-115.degree. C. 
PREATION LVI 
Preparation of 4-(4-cyanophenyl)phenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 14a) 
If the procedure described in Preparation I is followed starting from 2.3 g 
(10.9.10.sup.-3 mol) of 4-(4-mercaptophenyl)benzonitrile, 4.26 g 
(11.9.10.sup.-3 mol) of 2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl 
bromide and 2.75 g (10.9.10.sup.-3 mol) of mercuric cyanide 
(Hg(CN).sub.2), 0.540 g (yield: 10%) of the expected product is obtained 
after purification by flash chromatography using methylene chloride as the 
eluent. 
M.p.=150.degree. C. 
[.alpha.]D.sup.20.degree. C. =+10.2.degree. (c=0.5; CHCl.sub.3) 
PREATION LVII 
Preparation of 4-(4-cyanophenyl)phenyl 1,5-dithio-.beta.-D-xylopyranoside 
(Example 14) 
If the procedure described in Preparation V is followed starting from 0.340 
g (70.1.10.sup.-3 mol) of 4-(4-cyanophenyl)phenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 14a) and 17 
ml of sodium methylate (8% w/v solution of Na in methanol), 0.200 g 
(yield: 80%) of the expected product is obtained after purification by 
recrystallization from methanol. 
M.p.=168.degree. C. 
[.alpha.]D.sup.20.degree. C.=+5.4.degree. (c=0.5; CH.sub.3 OH/CH.sub.3 Cl 
(1/1 v/v)) 
PREATION LVIII 
Preparation of O-3,5-bis(trifluoromethyl)phenyl dimethylthiocarbamate 
0.975 g (17.4.10.sup.-3 mol) of potassium hydroxide pellets is dissolved in 
60 ml of water, 3.81 g (16.5.10.sup.-3 mol) of 
3,5-bis(trifluoromethyl)benzenethiol are then added and the mixture 
obtained is stirred for 20 minutes at room temperature. A solution of 2.35 
g (19.10.sup.-3 mol) of dimethylthiocarbamoyl chloride in 60 ml of acetone 
is then added dropwise, after which the resulting solution is stirred for 
30 minutes at room temperature. The reaction medium is hydrolyzed in a 
mixture of ice and 1N hydrochloric acid and then extracted with ethyl 
acetate. The organic phase is washed with water until the pH of the 
washings is neutral, dried over magnesium sulfate, decolorized with animal 
charcoal and evaporated under reduced pressure to give 4.81 g of the 
expected product (yield: 92%) in the form of a pale yellow solid. 
M.p.=71.degree.-80.degree. C. 
PREATION LIX 
Preparation of S-3,5-bis(trifluoromethyl)phenyl dimethylthiocarbamate 
4.81 g (15.10.sup.-3 mol) of O-3,5-bis(trifluoromethyl)phenyl 
dimethylthiocarbamate are heated at 200.degree.-210.degree. C. for 2 hours 
to give 2.81 g (yield: 58.4%) of the expected product in the form of a 
yellow oil. 
nD.sup.25.degree. C.=1.4710 
PREATION LX 
Preparation of 3,5-bis(trifluoromethyl)benzenethiol 
2.25 g (7.1.10.sup.-3 mol) of S-3,5-bis(trifluoromethyl)phenyl 
dimethylthiocarbamate are dissolved in 2.2 ml of anhydrous 
dimethylformamide. The resulting solution is cooled to 0.degree. C. before 
the addition of 4 ml (14.10.sup.-3 mol) of sodium methylate dissolved in 
methanol, and is then stirred at 0.degree. C. for 10 minutes. The reaction 
medium is subsequently hydrolyzed with an ice/water/1N HCl mixture and 
then extracted with methylene chloride. The organic phase obtained is 
washed with a saturated solution of sodium chloride, dried over magnesium 
sulfate and evaporated under reduced pressure to give 1.74 g (yield: 100%) 
of the expected product in the form of a yellow oil, which crystallizes 
and dimerizes under the action of heat. 
Melting point of the dimer=71.degree. C. 
PREATION LXI 
Preparation of 3,5-bis(trifluoromethyl)phenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 15a) 
If the procedure described in Preparation I is followed starting from 1.6 g 
(6.5.10.sup.-3 mol) of 3,5-bis(trifluoromethyl)benzenethiol, 1.64 g 
(6.5.10.sup.-3 mol) of mercuric cyanide, Hg(CN).sub.2, and 2.54 g 
(7.5.10.sup.-3 mol) of 2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl 
bromide, 1.2 g (yield: 35.7%) of the expected product are obtained. 
M.p.=201.degree. C. 
[.alpha.]D.sup.20.degree. C.=+6.degree. (c=0.5; CHCl.sub.3) 
PREATION LXII 
Preparation of 3,5-bis(trifluoromethyl)phenyl 
1,5-dithio-.beta.-D-xylopyranoside (Example 15) 
If the procedure described in Preparation V is followed starting from 1.1 g 
(2.1.10.sup.-3 mol) of 3,5-bis(trifluoromethyl)phenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside, 0.600 g (yield: 
72%) of the expected product is obtained after recrystallization from a 
methanol/water mixture (1/1 v/v). 
M.p.=157.degree.-158.degree. C. 
[.alpha.]D.sup.20.degree. C.=+3.degree. (c=0.5; CH.sub.3 OH) 
PREATION LXIII 
Preparation of 3-cyano-4-mercaptobenzonitrile 
Under argon, 3.03 g (12.10.sup.-3 mol) of 3-cyano-4-iodobenzonitrile and 
3.36 g (48.10.sup.-3 mol) of sodium thiomethylate are dissolved in 80 ml 
of anhydrous hexamethylphosphoramide and the solution obtained is then 
heated at 80.degree. C. for 45 minutes. The resulting reaction medium is 
hydrolyzed in an ice/1N HCl mixture and then extracted with methylene 
chloride. The organic phase is washed with water and then dried over 
magnesium sulfate and evaporated under reduced pressure to give 1.55 g 
(yield: 81%) of the expected product. 
M.p.=180.degree. C. 
PREATION LXIV 
Preparation of 2,4-dicyanophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 16a) 
If the procedure described in Preparation I is followed starting from 1.5 g 
(9.10.sup.-3 mol) of 3-cyano-4-mercaptobenzonitrile, 2.78 g (11.10.sup.-3 
mol) of mercuric cyanide, Hg(CN).sub.2, and 3.66 g (11.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide, 1.65 g (yield: 
40.5%) of the expected product are obtained. 
M.p.=228.degree. C. 
[.alpha.]D.sup.20.degree. C.=-14.degree. (c=0.39; CHCl.sub.3) 
PREATION LXV 
Preparation of 2,4-dicyanophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 16a) 
If the procedure described in Preparation IV is followed starting from 1.6 
g (9.73.10.sup.-3 mol) of 3-cyano-4-mercaptobenzonitrile, 4.07 g 
(11.45.10.sup.-3 mol) of 2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl 
bromide and 0.84 g (10.10.sup.-3 mol) of zinc oxide (ZnO), 2.08 g (yield: 
47%) of the expected product are obtained. 
M.p.=228.degree. C. 
PREATION LXVI 
Preparation of 2,4-dicyanophenyl 1,5-dithio-.beta.-D-xylopyranoside 
(Example 16) 
If the procedure described in Preparation V is followed, except that the 
reaction is carried out at 0.degree. C., starting from 1.5 g (34.10.sup.-3 
mol) of 2,4-dicyanophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 16a), 0.71 
g (yield: 67%) of the expected product is obtained after chromatography on 
silica using a CH.sub.2 Cl.sub.2 /CH.sub.3 OH mixture (8/1 v/v) as the 
eluent. 
M.p.=180.degree.-181.degree. C. 
[.alpha.]D.sup.20.degree. C.=+42.7.degree. (c=0.48; CH.sub.3 OH) 
PREATION LXVII 
Preparation of 3,5-dicyano-2-mercaptobenzonitrile 
If the procedure described in Preparation LV is followed starting from 6 g 
(26.10.sup.-3 mol) of 2-bromo-3,5-dicyanobenzonitrile and 6 g 
(86.10.sup.-3 mol) of sodium thiomethylate, 6 g (quantitative yield) of 
the expected product are obtained in the form of an oil. 
nD.sup.29.5.degree. C.=1.5012 
PREATION LXVIII 
Preparation of 2,4,6-tricyanophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 17a) 
If the procedure described in Preparation I is followed starting from 4.8 g 
(258.10.sup.-3 mol) of 3,5-dicyano-2-mercaptobenzonitrile (Example 17a), 
9.71 g (258.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide and 6.57 g 
(8.6.10.sup.-3 mol) of mercuric cyanide (Hg(CN).sub.2), 2 g (yield: 17%) 
of the expected product are obtained after crystallization from ether. 
M.p.=221.degree. C. 
[.alpha.]D.sup.20.degree. C.=+84.6.degree. (c=0.325; CHCl.sub.3) 
PREATION LXIX 
Preparation of 2,4,6-tricyanophenyl 1,5-dithio-.beta.-D-xylopyranoside 
(Example 17) 
0.600 g (1.30.10.sup.-3 mol) of 2,4,5-tricyanophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside is suspended in 120 
ml of 0.1M Na.sub.2 HPO.sub.4 /NaH.sub.2 PO.sub.4 buffer (pH: 7.35) and 3 
drops of Triton.RTM. X100 (marketed by SIGMA). 30 drops of pork liver 
esterase [Sigma type I, 3.2M suspension in (NH.sub.4).sub.2 SO.sub.4 ] 
(marketed by SIGMA) are then added and the resulting mixture is stirred at 
30.degree.-35.degree. C. for 12 hours. A further 20 drops of pork liver 
esterase and 10 drops of Triton.RTM. X100 are added; finally, after 
stirring for 24 hours, 30 drops of pork liver esterase are added. The pH 
is kept at 7.4 by the addition of 1N sodium hydroxide solution throughout 
the experiment. After stirring for 84 hours, the reaction mixture is 
cooled and the expected product is extracted with ethyl acetate. The 
resulting organic phase is washed with brine and then dried over magnesium 
sulfate and evaporated under reduced pressure. 100 mg (yield: 23%) of the 
expected product are obtained in the form of a foam after purification by 
flash chromatography using a CHCl.sub.3 /CH.sub.3 OH mixture (98/2 v/v, 
then 95/5 v/v) as the eluent. It is a hydrated product containing 1.3 
H.sub.2 O per molecule. 
M.p.=86.degree.-96.degree. C. 
[.alpha.]D.sup.20.degree. C.=0.degree. (c=0.165; CH.sub.3 OH) 
PREATION LXX 
Preparation of 4-aminophenyl 1,5-dithio-.beta.-D-xylopyranoside (Example 
18) 
170 mg of 10% palladium-on-charcoal are added to a solution of 1.7 g 
(5.61.10.sup.-3 mol) of 4-nitrophenyl 1,5-dithio-.beta.-D-xylopyranoside 
in 150 ml of methanol. The reaction medium is kept under hydrogen pressure 
(3.5.10.sup.5 Pa) at room temperature for 3 days. Repeat amounts of 170 mg 
of 10% palladium-on-charcoal are added after stirring for 3 hours, 4 
hours, 12 hours and 24 hours. The mixture obtained is filtered, the 
solvent is evaporated off under reduced pressure and the residue obtained 
is purified by flash chromatography using a CHCl.sub.3 /CH.sub.3 OH 
mixture (9/1 v/v) as the eluent, and is then recrystallized from water to 
give 0.7 g (yield: 46%) of the expected product. 
M.p.=163.degree.-166.degree. C. 
[.alpha.]D.sup.23.degree. C.=-74.degree. (c=0.102; DMSO) 
PREATION LXXI 
Preparation of 4-acetamidophenyl 
2,3,4-tri-O-acetyl-1,5dithio-.beta.-D-xylopyranoside (Example 19a) 
If the procedure described in Preparation IV is followed starting from 4.5 
g (27.10.sup.-3 mol) of N-(4-mercaptophenyl)acetamide, 11.43 g 
(32.10.sup.-3 mol) of 2,3,4-tri-O-acetyl-5-thio-D-xylopyranosyl bromide 
and 2.16 g (27.10.sup.-3 mol) of zinc oxide (ZnO), 3 g (yield: 25%) of the 
expected product are obtained after recrystallization from a 
toluene/isopropyl ether mixture. 
M.p.=168.degree.-174.degree. C. 
[.alpha.]D.sup.23.degree. C.=+8.degree. (c=0.5; CHCl.sub.3) 
PREATION LXXII 
Preparation of 4-acetamidophenyl 1,5-dithio-.beta.-D-xylopyranoside 
(Example 19) 
If the procedure described in Preparation V is followed starting from 1.05 
g (2.38.10.sup.-3 mol) of 4-acetamidophenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 19a), 0.61 
g (yield: 81%) of the expected product is obtained after recrystallization 
from 70 ml of water. 
M.p.=226.degree.-233.degree. C. 
[.alpha.]D.sup.23.degree. C.=-25.25.degree. (c=0.59; DMSO) 
PREATION LXXIII 
Preparation of 4-trifluoroacetylphenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 20a) 
If the procedure described in Preparation I is followed starting from 9.03 
g (43.8.10.sup.-3 mol) of 2,2,2-trifluoro-1-(4-mercaptophenyl)ethanone, 
11.5 g (45.5.10.sup.-3 mol) of mercuric cyanide and 17.1 g (48.2.10.sup.-3 
mol) of 2,3,4-tri-O-acetyl-1-bromo-5-thio-D-xylopyranoside, 4.79 g (yield: 
22%) of the expected product are obtained after purification by flash 
chromatography using a toluene/ether mixture (8/2 v/v) as the eluent, and 
recrystallization from ether. 
M.p.=143.degree.-148.degree. C. 
[.alpha.]D.sup.24.degree. C.=+59.3.degree. (c=0.28; CHCl.sub.3) 
PREATION LXXIV 
Preparation of 4-trifluoroacetylphenyl 1,5-dithio-.beta.-D-xylopyranoside 
(Example 20) 
If the procedure described in Preparation V is followed starting from 3.65 
g (7.6.10.sup.-3 mol) of 4-trifluoroacetylphenyl 
2,3,4-tri-O-acetyl-1,5-dithio-.beta.-D-xylopyranoside (Example 20a), 1.4 g 
(yield: 52%) of the expected product are obtained after purification by 
recrystallization from a toluene/n-propyl alcohol/hexane mixture. 
M.p.=133.degree.-134.degree. C. 
[.alpha.]D.sup.22.degree. C.=+15.degree. (c=0.31; CH.sub.3 OH) 
PREATION LXXV 
Preparation of 3-aminophenyl 1,5-dithio-.beta.-D-xylopyranoside (Example 
21) 
If the procedure described in Preparation LXX is followed starting from 2.9 
g (9.6.10.sup.-3 mol) of 3-nitrophenyl 1,5-dithio-.beta.-D-xylopyranoside, 
1.2 g (yield: 46%) of the expected product are obtained after purification 
by flash chromatography using a CHCl.sub.3 /CH.sub.3 OH mixture as the 
eluent (solvent proportions from 95/5 to 92/8 v/v), and precipitation in a 
CH.sub.3 OH/ether mixture. 
M.p.=128.degree.-132.degree. C. 
[.alpha.]D.sup.25.degree. C.=+3.5.degree. (c=0.31; CH.sub.3 OH) 
PREATION LXXVI 
Preparation of 4-cyanophenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside (Example 22a) 
A suspension of 6.5 g (12.3.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide, 6 g 
(50.4.10.sup.-3 mol) of 4-hydroxybenzonitrile, 6.9 g (50.5.10.sup.-3 mol) 
of zinc chloride and 4.4 g (25.1.10.sup.-3 mol) of silver imidazolate in 
200 ml of anhydrous methylene chloride is stirred at 40.degree. C., under 
an inert atmosphere, in the absence of light and in the presence of a 
molecular sieve (400 pm). After 7 h at this temperature, 6.9 g 
(50.5.10.sup.-3 mol) of zinc chloride, 4.4 g (25.1.10.sup.-3 mol) of 
silver imidazolate and 6.5 g (18.3.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide are added. The 
reaction medium is left overnight under these conditions and 6.5 g 
(12.3.10.sup.-3 mol) of 2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl 
bromide are then added. After 24 h, the reaction mixture is filtered on 
Celite.RTM. , washed with a 1N aqueous solution of hydrochloric acid and 
then water and dried over magnesium sulfate. After evaporation under 
reduced pressure, the residue is purified by chromatography on silica gel 
using a hexane/ethyl acetate mixture (3/1 v/v) as the eluent. 8.1 g 
(yield: 41%) of the expected product are obtained by crystallization from 
ethanol. 
M.p.=145.degree.-148.degree. C. 
[.alpha.]D.sup.21.degree. C.=-29.degree. (c=0.47; CHCl.sub.3) 
PREATION LXXVII 
Preparation of 2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranosyl bromide 
3.50 ml of a 30% solution of hydrobromic acid in glacial acetic acid are 
added at 10.degree. C. to a solution of 2.10 g (6.3.10.sup.-3 mol) of 
1,2,3,4-tetra-O-acetyl-5-thio-D-xylopyranose in 10 cm.sup.3 of 
dichloroethane. After 2 to 3 h, the reaction medium is hydrolyzed, washed 
with a solution of sodium bicarbonate and dried over sodium sulfate 
(Na.sub.2 SO.sub.4) and the solvent is evaporated off to dryness under 
reduced pressure. 0.87 g (yield: 39%) of the expected product is obtained 
after precipitation in ether. 
M.p.=175.degree. C. 
[.alpha.]D.sup.21.degree. C.=-67.degree. (c=0.56; CHCl.sub.3) 
PREATION LXXVIII 
Preparation of 4-cyanophenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside (Example 22a) 
A suspension of 0.5 g (1.4.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-D-xylopyranosyl bromide, 0.25 g (2.1.10.sup.-3 
mol) of 4-hydroxybenzonitrile and 170 mg (2.1.10.sup.-3 mol) of zinc oxide 
(ZnO) in 4 ml of anhydrous toluene and 4 ml of acetonitrile is stirred at 
50.degree. C., under an inert atmosphere, in the presence of a molecular 
sieve (1 nm), for 48 h. The reaction medium is subsequently filtered on 
Celite.RTM. in ethyl acetate and then washed with a 1N aqueous solution of 
hydrochloric acid, water, a 1N solution of sodium hydroxide and then a 
saturated solution of NaCl. The solution obtained is dried over sodium 
sulfate and the solvent is evaporated off under reduced pressure. The 
residue obtained is purified by chromatography on silica gel using a 
hexane/ethyl acetate mixture (2/1 v/v) as the eluent to give 194 mg 
(yield: 35%) of the expected product. 
M.p.=145.degree.-148.degree. C. 
PREATION LXXIX 
Preparation of 2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranose 
22 ml (0.2 mol) of benzylamine are added under an inert atmosphere to a 
solution of 15 g (44.8.10.sup.-3 mol) of 
1,2,3,4-tetra-O-acetyl-5-thio-D-xylopyranose in 450 ml of ether. After 7 
hours at room temperature (15.degree.-25.degree. C.), the reaction mixture 
is concentrated under reduced pressure and the residue is dissolved in 
methylene chloride and washed with a 1N solution of hydrochloric acid, a 
saturated solution of ammonium chloride and then water. The solution 
obtained is dried over sodium sulfate and the solvent is evaporated off 
under reduced pressure. 6.2 g (yield: 47%) of the expected product are 
obtained after purification by chromatography on silica gel using a 
hexane/ethyl acetate mixture (3/2 v/v) as the eluent, and crystallization 
from an ethyl acetate/hexane mixture, said product having the following 
physical characteristics: 
M.p.=115.degree. C. 
[.alpha.]D.sup.21.degree. C. =+131.degree. (c=0.34; CHCl.sub.3) 
PREATION LXXX 
Preparation of 2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl 
trichloroacetimidate 
1.5 ml (15.10.sup.-3 mol) of trichloroacetonitrile and 70 mg of NaH 
(2.3.10.sup.-3 mol of NaH in 80% dispersion) are added to a solution of 1 
g (3.42.10.sup.-3 mol) of 2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranose 
in 10 ml of methylene chloride. After 4 h at room temperature, the 
reaction medium is filtered on silica in methylene chloride and then 
purified by chromatography on silica gel using a hexane/ethyl acetate 
mixture (3/1 v/v) as the eluent. 790 mg (yield: 53%) of the expected 
product are obtained after crystallization from an ethyl acetate/hexane 
mixture. 
M.p.=110.degree. C. 
[.alpha.]D.sup.21.degree. C. =+227.degree. C. (c=0.42; CHCl.sub.3) 
PREATION LXXXI 
Preparation of 4-cyanophenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside (Example 22a) 
1 ml of a 0.1M solution of boron trifluoride etherate in methylene chloride 
is added at -15.degree. C., under an inert atmosphere, to a suspension of 
250 mg (0.57.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl trichloroacetimidate, 57 
mg (0.48.10.sup.-3 mol) of 4-hydroxybenzonitrile and a molecular sieve (1 
nm) in 10 ml of methylene chloride. The reaction medium is allowed to 
return gradually to 0.degree. C. and, after a reaction time of 3 h, is 
neutralized with sodium bicarbonate. The reaction mixture is then washed 
with water and dried over magnesium sulfate, MgSO.sub.4, and the solvent 
is evaporated off under reduced pressure. 150 mg (yield: 80%) of the 
expected product are obtained after purification by chromatography on 
silica gel using a hexane/ethyl acetate mixture (2/1 v/v) as the eluent. 
M.p.=145.degree.-148.degree. C. 
PREATION LXXXII 
Preparation of 4-cyanophenyl 5-thio-.beta.-D-xylopyranoside (Example 22) 
1.5 ml of a solution of sodium methylate in methanol (8% w/v of Na) are 
added under an inert atmosphere to a suspension of 10 g (25.4.10.sup.-3 ) 
of 4-cyanophenyl 2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside in 200 
ml of methanol. The reaction mixture is stirred at room temperature for 30 
min, neutralized by the addition of Amberlite.RTM. IR 120 H.sup.+ resin 
and filtered. After evaporation to dryness, the residue is crystallized 
from methanol to give 8.8 g (yield: 73%) of the expected product. 
M.p.=179.degree.-186.degree. C. 
[.alpha.]D.sup.21.degree. C. =-108.6.degree. (c=0.48; CH.sub.3 OH) 
PREATION LXXXIII 
Preparation of 4-nitrophenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside (Example 23a) 
A suspension of 5.6 g (15.8.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide, 2 g 
(14.3.10.sup.-3 mol) of 4-nitrophenol, 4 g (29.3.10.sup.-3 mol) of zinc 
chloride and 3.8 g (21.7.10.sup.-3 mol) of silver imidazolate in 80 ml of 
anhydrous methylene chloride is stirred at 50.degree. C., under an inert 
atmosphere, in the absence of light and in the presence of a molecular 
sieve (400 pm). After 48 h at this temperature, the reaction mixture is 
filtered on Celite.RTM., washed with a 1N aqueous solution of hydrochloric 
acid, then a 1N solution of sodium hydroxide and finally water and dried 
over magnesium sulfate (MgSO.sub.4). After evaporation to dryness, the 
residue is purified by chromatography on silica gel using a hexane/ethyl 
acetate mixture (3/1 v/v) as the eluent. 1.5 g (yield: 25%) of the 
expected product are obtained by precipitation in ether. 
M.p.=212.degree. C. 
[.alpha.]D.sup.21.degree. C. =-78.degree. (c=0.5; CHCl.sub.3) 
PREATION LXXXIV 
Preparation of 4-nitrophenyl 5-thio-.beta.-D-xylopyranoside (Example 23) 
0.2 ml of a solution of sodium methylate in methanol (8% w/v of Na) is 
added under an inert atmosphere to a suspension of 1.1 g (2.6.10.sup.-3 
mol) of 4-nitrophenyl 2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside in 
30 ml of methanol. After complete solubilization (2 h), the reaction 
mixture is neutralized by the addition of Amberlite.RTM. IR 120 H.sup.+ 
resin and then filtered. 620 mg (yield: 79%) of the expected product are 
obtained after evaporation to dryness and lyophilization. 
M.p.=130.degree.-132.degree. C. 
[.alpha.]D.sup.21.degree. C. =-77.3.degree. (c=0.49; CH.sub.3 OH) 
PREATION LXXXV 
Preparation of 4-acetylphenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside (Example 24a) 
If the procedure described in Preparation LXXXIII is followed starting from 
2 g (14.7.10.sup.-3 mol) of 1-(4-hydroxyphenyl)ethanone, 2.8 g 
(16.10.sup.-3 mol) of silver imidazolate, 5.74 g (16.1.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide and 4 g 
(29.3.10.sup.-3 mol) of zinc chloride in 100 ml of methylene chloride, 
0.96 g (yield: 18%) of the expected product is obtained after purification 
by chromatography on silica gel using a toluene/ethyl acetate mixture (6/1 
v/v) as the eluent. 
M.p.=156.degree. C. 
[.alpha.]D.sup.21.degree. C. =-77.degree. (c=0.5; CHCl.sub.3) 
PREATION LXXXVI 
Preparation of 4-acetylphenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside (Example 24a) 
If the procedure described in Preparation LXXXI is followed starting from 
380 mg (0.882.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl trichloroacetimidate, 
100 mg (73.5.10.sup.-3 mol) of 1-(4-hydroxyphenyl)ethanone and 1.47 ml of 
a 0.1M solution of boron trifluoride etherate in methylene chloride, 140 
mg (yield: 47%) of the expected product are obtained after crystallization 
from ether. 
M.p.=156.degree. C. 
PREATION LXXXVII 
Preparation of 4-acetylphenyl 5-thio-.beta.-D-xylopyranoside (Example 24) 
If the procedure described in Preparation LXXXIV is followed starting from 
0.9 g (2.2.10.sup.-3 mol) of 4-acetylphenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside and 0.8 ml of a solution 
of sodium methylate in methanol (8% w/v of Na), reacted in 50 ml of 
methanol for 1 h, 0.55 g (yield: 88%) of the expected product is obtained 
after lyophilization. 
M.p.=195.degree.-198.degree. C. 
[.alpha.]D.sup.21.degree. C. =-84.5.degree. (c=0.49; CH.sub.3 OH) 
PREATION LXXXVIII 
Preparation of 3-acetylphenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside (Example 25a) 
If the procedure described in Preparation LXXXIII is followed starting from 
3.45 g (25.3.10.sup.-3 mol) of 1-(3-hydroxyphenyl)ethanone, 6 g 
(16.9.10.sup.-3 mol) of 2,3,4-tri-O-acetyl-5-thio-D-xylopyranosyl bromide, 
3 g (17.10.sup.-3 mol) of silver imidazolate and 4.6 g (33.7.10.sup.-3 
mol) of zinc chloride in 90 ml of methylene chloride and 30 ml of 
acetonitrile, 0.96 g (yield: 14%) of the expected product is obtained 
after purification by chromatography on silica gel using a toluene/ethyl 
acetate mixture (6/1 v/v) as the eluent, and crystallization from ether. 
M.p.=150.degree.-153.degree. C. 
[.alpha.]D.sup.21.degree. C. =-81.5.degree. (c=0.5; CHCl.sub.3) 
PREATION LXXXIX 
Preparation of 3-acetylphenyl 5-thio-.beta.-D-xylopyranoside (Example 25) 
If the procedure described in Preparation LXXXIV is followed starting from 
1.36 g (3.3.10.sup.-3 mol) of 3-acetylphenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside and 0.2 ml of a solution 
of sodium methylate in methanol (8% w/v of Na), reacted in 50 ml of 
methanol for 30 min, 0.8 g (yield: 85%) of the expected product is 
obtained after crystallization from an ethanol/ether mixture. 
M.p.=166.degree.-174.degree. C. 
[.alpha.]D.sup.21.degree. C. =-109.degree. (c=0.42; CH.sub.3 OH) 
PREATION XC 
Preparation of 2-cyanophenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside (Example 26a) 
If the procedure described in Preparation LXXXIII is followed starting from 
2 g (16.8.10.sup.-3 mol) of 2-hydroxybenzonitrile, 4.4 g (25.1.10.sup.-3 
mol) of silver imidazolate, 6.5 g (18.3.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide and 4.6 g 
(33.6.10.sup.-3 mol) of zinc chloride in 80 ml of methylene chloride, 1.32 
g (yield: 20%) of the expected product are obtained after purification by 
chromatography on silica gel using a toluene/ethyl acetate mixture (6/1 
v/v) as the eluent, and precipitation in ether. 
M.p.=176.degree. C. 
[.alpha.]D.sup.21.degree. C. =-160.degree. (c=0.45; CHCl.sub.3) 
PREATION XCI 
Preparation of 2-cyanophenyl 5-thio-.beta.-D-xylopyranoside (Example 26) 
If the procedure described in Preparation LXXXIV is followed starting from 
1.26 g (3.2.10.sup.-3 mol) of 2-cyanophenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside and 0.2 ml of a solution 
of sodium methylate in methanol (8% w/v of Na), reacted in 70 ml of 
methanol for 30 min, 0.75 g (yield: 88%) of the expected product is 
obtained after precipitation in ether and lyophilization. 
M.p.=130.degree.-132.degree. C. 
[.alpha.]D.sup.21.degree. C. =-68.8.degree. (c=0.485; CH.sub.3 OH) 
PREATION XCII 
Preparation of 3-cyanophenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside (Example 27a) 
If the procedure described in Preparation LXXXIII is followed starting from 
2 g (16.8.10.sup.-3 mol) of 3-hydroxybenzonitrile, 2.9 mg (16.5.10.sup.-3 
mol) of silver imidazolate, 6.5 g (18.3.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide and 4.6 g 
(33.6.10.sup.-3 mol) of zinc chloride in 80 ml of methylene chloride, 2.2 
g (yield: 33%) of the expected product are obtained after purification by 
chromatography on silica gel using a hexane/ethyl acetate mixture (3/1 
v/v) as the eluent, and precipitation in ether. 
M.p.=148.degree.-151.degree. C. 
[.alpha.]D.sup.21.degree. C. =-82.degree. (c=0.31; CHCl.sub.3) 
PREATION XCIII 
Preparation of 3-cyanophenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside (Example 27a) 
If the procedure described in Preparation LXXVIII is followed starting from 
0.5 g (1.4.10.sup.-3 mol) of 2,3,4-tri-O-acetyl-5-thio-D-xylopyranosyl 
bromide, 0.25 g (2.1.10.sup.-3 mol) of 3-hydroxybenzonitrile and 170 mg 
(2.1.10.sup.-3 mol) of zinc oxide (ZnO) in 4 ml of anhydrous toluene and 4 
ml of acetonitrile, 138 mg (yield: 25%) of the expected product are 
obtained after purification by chromatography on silica gel using a 
hexane/ethyl acetate mixture (2/1 v/v) as the eluent, and precipitation in 
ether. 
M.p.=148.degree.-151.degree. C. 
PREATION XCIV 
Preparation of 3-cyanophenyl 5-thio-.beta.-D-xylopyranoside (Example 27) 
If the procedure described in Preparation LXXXIV is followed starting from 
2.12 g (5.4.10.sup.-3 mol) of 3-cyanophenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside and 0.2 ml of a solution 
of sodium methylate in methanol (8% w/v of Na), reacted in 60 ml of 
methanol for 30 min, 1.22 g (yield: 85%) of the expected product are 
obtained after precipitation in ether and lyophilization. 
M.p.=130.degree.-135.degree. C. 
[.alpha.]D.sup.21.degree. C. =-107.4.degree. (c=0.47; CH.sub.3 OH) 
PREATION XCV 
Preparation of 2-nitrophenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside (Example 28a) 
If the procedure described in Preparation LXXXIII is followed starting from 
2 g (14.4.10.sup.-3 mol) of 2-nitrophenol, 2.5 g (14.2.10.sup.-3 mol) of 
silver imidazolate, 6 g (15.7.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide and 4 g 
(29.3.10.sup.-3 mol) of zinc chloride in 80 ml of methylene chloride, 0.91 
g (yield: 15%) of the expected product is obtained after purification by 
chromatography on silica gel using a hexane/ethyl acetate mixture (2/1 
v/v) as the eluent, and precipitation in ether. 
M.p.=148.degree. C. 
[.alpha.]D.sup.21.degree. C. =-102.8.degree. (c=0.40; CHCl.sub.3) 
PREATION XCVI 
Preparation of 2-nitrophenyl 5-thio-.beta.-D-xylopyranoside (Example 28) 
If the procedure described in Preparation LXXXIV is followed starting from 
0.85 g (2.05.10.sup.-3 mol) of 2-nitrophenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside and 0.1 ml of a solution 
of sodium methylate in methanol (8% w/v of Na), reacted in 50 ml of 
methanol for 30 min, 0.4 g (yield: 68%) of the expected product is 
obtained after precipitation in ether and lyophilization. 
M.p.=137.degree.-140.degree. C. 
[.alpha.]D.sup.21.degree. C. =-117.degree. (c=0.35; CH.sub.3 OH) 
PREATION XCVII 
Preparation of 2-acetylphenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside (Example 29a) 
If the procedure described in Preparation LXXXIII is followed starting from 
3.45 g (25.3.10.sup.-3 mol) of 1-(2-hydroxyphenyl)ethanone, 6 g 
(16.9.10.sup.-3 mol) of 2,3,4-tri-O-acetyl-5-thio-D-xylopyranosyl bromide, 
3 g (17.10.sup.-3 mol) of silver imidazolate and 4.6 g (33.7.10.sup.-3 
mol) of zinc chloride in 90 ml of methylene chloride and 30 ml of 
acetonitrile, 0.92 g (yield: 13.5%) of the expected product is obtained 
after purification by chromatography on silica gel using a toluene/ethyl 
acetate mixture (6/1 v/v) as the eluent, and crystallization from ether. 
M.p.=112.degree. C. 
[.alpha.]D.sup.21.degree. C. =-100.degree. (c=0.42; CHCl.sub.3) 
PREATION XCVIII 
Preparation of 2-acetylphenyl 5-thio-.beta.-D-xylopyranoside (Example 29) 
If the procedure described in Preparation LXXXIV is followed starting from 
0.88 g (2.1.10.sup.-3 mol) of 2-acetylphenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside and 0.1 ml of a solution 
of sodium methylate in methanol (8% w/v of Na), reacted in 50 ml of 
methanol for 30 min, 0.51 g (yield: 84%) of the expected product is 
obtained after purification by chromatography on silica gel using a 
chloroform/methanol mixture (12/1 v/v) as the eluent, and lyophilization. 
M.p.=102.degree.-105.degree. C. 
[.alpha.]D.sup.21.degree. C. =-90.degree. (c=0.44; CH.sub.3 OH) 
PREATION IC 
Preparation of 2-(6-cyanonaphthalenyl) 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside (Example 30a) 
If the procedure described in Preparation LXXXIII is followed starting from 
1.69 g (10.10.sup.-3 mol) of 6-hydroxynaphthalene-2-carbonitrile, 1.75 g 
(10.10.sup.-3 mol) of silver imidazolate, 3.87 g (11.1.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide and 2.7 g 
(19.7.10.sup.-3 mol) of zinc chloride in 80 ml of methylene chloride, 0.72 
g (yield: 16%) of the expected product is obtained after purification by 
chromatography on silica gel using a hexane/ethyl acetate mixture (3/1 
v/v) as the eluent, and precipitation in ether. 
M.p.=194.degree. C. 
[.alpha.]D.sup.21.degree. C. =-57.4.degree. (c=0.5; CHCl.sub.3) 
PREATION C 
Preparation of 2-(6-cyanonaphthalenyl) 5-thio-.beta.-D-xylopyranoside 
(Example 30) 
If the procedure described in Preparation LXXXIV is followed starting from 
0.92 g (2.1.10.sup.-3 mol) of 2-(6-cyanonaphthalenyl) 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside and 0.2 ml of a solution 
of sodium methylate in methanol (8% w/v of Na), reacted in 40 ml of 
methanol with the addition of tetrahydrofuran until solubilization is 
complete, 0.59 g (yield: 90%) of the expected product is obtained after 
precipitation in ether and crystallization from methanol. 
M.p.=209.degree.-214.degree. C. 
[.alpha.]D.sup.21.degree. C. =-83.degree. (c=0.2; CH.sub.3 OH) 
PREATION CI 
Preparation of 2-(1-cyanonaphthalenyl) 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside (Example 31a) 
If the procedure described in Preparation LXXXIII is followed starting from 
5 g (29.5.10.sup.-3 mol) of 2-hydroxynaphthalene-1-carbonitrile, 4.8 g 
(32.7.10.sup.-3 mol) of silver imidazolate, 10.5 g (29.5.10.sup.-3 mol) of 
2,3,4-tri-O-acetyl-5-thio-.alpha.-D-xylopyranosyl bromide and 12 g 
(88.10.sup.-3 mol) of zinc chloride in 200 ml of methylene chloride, 3.85 
g (yield: 29.4%) of the expected product are obtained after purification 
by chromatography on a silica column using a hexane/ethyl acetate mixture 
(7/3 v/v) as the eluent, followed by washing with ether. 
M.p.=192.degree. C. (decomposition) 
[.alpha.]D.sup.24.degree. C.=-141.6.degree. (c=0.3; CHCl.sub.3) 
PREATION CII 
Preparation of 2-(1-cyanonaphthalenyl) 5-thio-.beta.-D-xylopyranoside 
(Example 31) 
If the procedure described in Preparation LXXXIV is followed starting from 
3 g (6.76.10.sup.-3 mol) of 2-(1-cyanonaphthalenyl) 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside and 1.2 ml of a solution 
of sodium methylate in methanol (8% w/v of Na), reacted in 70 ml of 
methanol for 3.5 h, 1.30 g (yield: 59%) of the expected product are 
obtained after recrystallization from a methanol/water mixture (5/1 v/v). 
M.p.=163.degree.-164.degree. C. 
[.alpha.]D.sup.24.degree. C. =+13.degree. (c=0.29; CH.sub.3 OH) 
PREATION CIII 
Preparation of 4-acetamidophenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside (Example 32a) 
30 mg of 10% palladium-on-charcoal are added to a solution of 150 mg 
(0.36.10.sup.-3 mol) of 4-nitrophenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside in acetic anhydride, 
under a nitrogen atmosphere, and the reaction mixture obtained is then 
kept under hydrogen pressure (3.5.10.sup.5 Pa) at 50.degree. C. for 15 
hours. After filtration, the mixture is evaporated to dryness under 
reduced pressure and the residue obtained is purified by chromatography 
using a methylene chloride/methanol mixture (98/2 v/v) as the eluent to 
give 80 mg (yield: 51%) of the expected product. 
M.p.=166.degree. C. 
[.alpha.]D.sup.25.degree. C. =-34.degree. (c=0.25; CHCl.sub.3) 
PREATION CIV 
Preparation of 4-acetamidophenyl 5-thio-.beta.-D-xylopyranoside (Example 
32) 
If the procedure described in Preparation LXXXIV is followed starting from 
1.2 g (2.8.10.sup.-3 mol) of 4-acetamidophenyl 
2,3,4-tri-O-acetyl-5-thio-.beta.-D-xylopyranoside and 70 .mu.l of a 
solution of sodium methylate in methanol (8% w/v of Na), reacted in 100 
cm.sup.3 of methanol, 0.7 g (yield: 83%) of the expected product is 
obtained after purification by flash chromatography using a methylene 
chloride/methanol mixture (93/7 v/v) as the eluent. 
M.p.=238.degree. C. 
[.alpha.]D.sup.25.degree. C. =-48.3.degree. (c=0.145; DMSO) 
Without implying a limitation, the compounds according to the invention 
have been collated in Tables I and I bis given below, Table I relating to 
the compounds of formula I having a phenylthioxyloside structure and Table 
I bis relating to the compounds of formula I having a 
naphthalenylthioxyloside structure. 
The antithrombotic activity of the products according to the invention was 
demonstrated by means of the following operating protocol for venous 
thrombosis: 
A venous stasis under hypercoagulation is produced according to the 
technique described by WESSLER et al. (J. Applied Physiol. 1959, p. 
943-946). As in the technique described by J. HAUPMAN et al. (Thrombosis 
and Haemostasis 43(2), 1980, p. 118), the hypercoagulant used is a 
solution of activated factor X (Xa) supplied by Flow Laboratories (71 Knat 
per 12.5 ml of physiological serum). 
The study is performed on unfasted male Wistar rats weighing 250 to 280 g, 
divided into groups of 10 animals each. The products to be tested are 
administered orally as a suspension in PEG 400. A thrombosis is induced 4 
hours after this treatment and the thrombus formed is removed and weighed. 
The results obtained at doses of 3 mg/kg or 12.5 mg/kg, administered 
orally, have been collated in Table II. The results obtained with the 
known products of the above-mentioned prior art have also been collated in 
this Table. 
The venous antithrombotic activity of the products according to the 
invention is distinctly superior to that of the known products of the 
prior art. 
TABLE I 
______________________________________ 
##STR11## (I) 
Ex. X Y R.sub.1 R.sub.2 
R.sub.3 
______________________________________ 
1a S COCH.sub.3 
4-CN H H 
1 S H 4-CN H H 
2a S COCH.sub.3 
4-NO.sub.2 H H 
2 S H 4-NO.sub.2 H H 
4a S COCH.sub.3 
4-CF.sub.3 H H 
4 S H 4-CF.sub.3 H H 
5a S COCH.sub.3 
3-CN H H 
5 S COCH.sub.3 
3-CN H H 
6a S COCH.sub.3 
2-CN H H 
6 S H 2-CN H H 
7a S COCH.sub.3 
2-NO.sub.2 H H 
7 S H 2-NO.sub.2 H H 
9a S COCH.sub.3 
H H H 
9 S H H H H 
10a S COCH.sub.3 
3-OCH.sub.3 4-OCH.sub.3 
5-OCH.sub.3 
10 S H 3-OCH.sub.3 4-OCH.sub.3 
5-OCH.sub.3 
11a S COCH.sub.3 
4-COCH.sub.3 
H H 
11 S H 4-COCH.sub.3 
H H 
12a S COCH.sub.3 
3-NO.sub.2 H H 
12 S H 3-NO.sub.2 H H 
13a S COCH.sub.3 
2-CF.sub.3 H H 
13 S H 2-CF.sub.3 H H 
14a S COCH.sub.3 
##STR12## H H 
14 S H 
##STR13## H H 
15a S COCH.sub.3 
3-CF.sub.3 5-CF.sub.3 
H 
15 S H 3-CF.sub.3 5-CF.sub.3 
H 
16a S COCH.sub.3 
2-CN 4-CN H 
16 S H 2-CN 4-CN H 
17a S COCH.sub.3 
2-CN 4-CN 6-CN 
17 S H 2-CN 4-CN 6-CN 
18 S H 4-NH.sub.2 H H 
19a S COCH.sub.3 
4-NHCOCH.sub.3 
H H 
19 S H 4-NHCOCH.sub.3 
H H 
20a S COCH.sub.3 
4-COCF.sub.3 
H H 
20 S H 4-COCF.sub.3 
H H 
21 S H 3-NH.sub.2 H H 
22a O COCH.sub.3 
4-CN H H 
22 O H 4-CN H H 
23a O COCH.sub.3 
4-NO.sub.2 H H 
23 O H 4-NO.sub.2 H H 
24a O COCH.sub.3 
4-COCH.sub.3 
H H 
24 O H 4-COCH.sub.3 
H H 
25a O COCH.sub.3 
3-COCH.sub.3 
H H 
25 O H 3-COCH.sub.3 
H H 
26a O COCH.sub.3 
2-CN H H 
26 O H 2-CN H H 
27a O COCH.sub.3 
3-CN H H 
27 O H 3-CN H H 
28a O COCH.sub.3 
2-NO.sub.2 H H 
28 O H 2-NO.sub.2 H H 
29a O COCH.sub.3 
2-COCH.sub.3 
H H 
29 O H 2-COCH.sub.3 
H H 
32a O COCH.sub.3 
4-NHCOCH.sub.3 
H H 
32 O H 4-NHCOCH.sub.3 
H H 
______________________________________ 
bis 
##STR14## 
Ex. X Y R.sub.4 R.sub.5 
______________________________________ 
8 S H H CN 
8a S COCH.sub.3 H CN 
30 O H H CN 
30a O COCH.sub.3 H CN 
31 O H CN H 
31a O COCH.sub.3 CN H 
______________________________________ 
TABLE II 
______________________________________ 
% inhibition at 
% inhibition at 
Example 12.5 mg/kg 3 mg/kg 
______________________________________ 
1a 90 30 
1 90 53 
2 78 35 
3 38 -- 
4 66 -- 
5 79.5 28 
6 88.6 35 
7 96.7 33 
8 94.7 31 
9 .sup. 11 (1) 
-- 
10a 62 -- 
10 36.5 -- 
11 98.3 47 
12 69 -- 
13 23 -- 
14 86 27 
16a 72.8 -- 
16 99.5 42.5 
17 40 8 
18 93 30 
19a -- 66 
19 93 61 
20 -- 49 
21 -- 31 
22a -- 66 
22 -- 57 
23a -- 44 
23 94 37.5 
24 100 55 
25a -- 52 
25 -- 44.5 
26 96 63.5 
27a -- 57 
27 98 66 
28 94 51 
29 -- 26 
30 -- 51 
31a -- 44.5 
31 -- 28 
A .sup. 14 (2) 
B 5.5 
______________________________________ 
A: comparative product described in Example 1 of European patent document 
A0133103 
B: comparative product described in Example 97 of European patent documen 
B0051023 
(1) 82 to 50 mg/kg administered orally 
(1) 77 to 50 mg/kg administered orally