DD217225A1 - PROCESS FOR THE PREPARATION OF GLYCOPYRANOSYL THIOMETHYLENE CYANESE ACESEUREDERIVATES - Google Patents

Abstract

The invention relates to processes for the preparation of Glycopyranosylthiomethylencyanessigsaeurederivaten. The aim of the invention is to develop a process for the preparation of acetylated b-D-Glycopyranosylthio-methylthio-methylencyanessigsaeureestern. The glycopyranosylthiomethylencyanessigsaeurederivate of the general formula III in which R is an alkyl radical and the acetylated bD-Glycopyranosylrest has the gluco- or galacto configuration can, by reacting the Bromomethylencyanessigsaeureester the general formula I, in which R is as defined above, with the acetylated bD Glycopyranosylmercaptanen the general formula II can be prepared with the gluco- or galacto configuration. These Glycopyranosylthiomethylencyanessigsaeurederivate can be used as organic intermediates for further syntheses. They are particularly suitable for the preparation of specific S-glycosides.

Description

, Λ

Process for the preparation of Glycopyranosylthiomethylencyanessigsäurederivaten

Field of application of the invention

The invention relates to a process for the preparation of acetylated .beta.-D-glycopyranosylthio-methyltihio-methylenecanoic acid esters.

These glyoopyranosylthiomethylenecyanoacetic acid derivatives can be used as organic intermediates for further syntheses. They are particularly suitable for the preparation of specific S-glycosides.

Characteristic of the known technical solutions

Acetylated ß-D-Glycopyranosylthio-methylthio-methylencyanessigsäureester are not yet known.

Object of the invention

The aim of the invention is to develop a process for the preparation of acetylated .beta.-D-glycopyranosylthio-methylthio-methylenecanoic acid esters.

Explanation of the essence of the invention

The Glycopyranosylthiomethylencyanessigsäurederivate the general formula III, in which Rx is an alkyl radical and

the acetylated .beta.-D-glycopyranosyl radical has the gluco-or, galacto configuration, can be obtained by reacting the Bromomethylencyanessigsäureester the general '"formula I, in the R v / ie

is defined above »be prepared with the acetylated ß ~ -D-Glycopyranosylmercaptanen the general formula II with the gluco- or galacto configuration.

The reactions are carried out in an organic solvent, preferably in dimethylformamide, in the presence of bases, preferably of potassium carbonate. The reaction temperatures are i0-50 ° C. The reaction times range from 15 minutes to 2 hours. It is expedient to stir / to shake the reaction mixtures. After completion of the reaction, the reaction mixture is diluted with water and acidified with mineral acid. The precipitated products III are filtered off, washed with water and recrystallized after drying from organic solvents for further purification.

Embodiments Example 1

(2,3,4 »6-tetra-0-acetyl-D-E-glucopyranosylthio) methylthiomethylencyanessigsäure-methylester

A mixture of O, Oo5 rnol methyl bromo-methylthio-methylene cyanoacetate, 0.005 mol 2,3,4} 6 ~ tetra-0-acetyl-ß-D-glucopyranosylmercaptans 1 g of potassium carbonate and 10 ml of dimethylformamide is 30 minutes hot 20 ⁰ C. The mixture is then poured with stirring into 200 ml of water and acidified with dilute mineral acid. The precipitate is filtered off, washed with water, dried and recrystallized from isopropanol

Yield: 52 $ d.Th. M.p. 127-129 ⁰ C

₁ S ₂ (919.6) BerV C 46.23 H 4.85 N 2.70 S 12.34 Gef. C 46.30 H 5.05 N 2.53 S 12.09

Embodiment 2.

 ('2,3,4', 6-T etra-O-acetyl-β-D-gaiacto-pyranosylthio) -methylthiomethj'-lenoyl acetic acid methyl ester

0.005 mol of methyl brothi-methylthio-methylenecanoacetate and 0.005 mol of 2,3,4,6-tetra-O-aoetyl-.beta.-D-galactopyranosyl

mercaptan are reacted as described in Example 1

Yield: 61 # d.Th. Schrap. 124-127 ⁰ C

C ₂₀ H ₂₅ NO ₁₁ S ₂ (519.6) Ber. C 46 | 23 H 4,85 N 2,70 S 12,34

Gef. C 46.00 H 4.91 N 2.66 S 12.20

Embodiment 3

(2,3,4,6-Tetra-0-acetyl-ß ~ D-glucopyranosylthio) methylthiornethylenoyanessigsäure ethyl ester

0.005 mol of methyl bromide-methylthio-cyano-cyanoacetate and 0.005 mol of 2,3,4,6-tetra-O-acetyl-.beta.-D-glucopyranosylmercaptan are reacted as described in Example 1.

Yield: 58 $ d.Th. M.p. 118-120 ⁰ C

C ₂₁ H ₂₇ NO ₁₁ S ₂ (533.6) Calcd. H 2.62 S 12.02

Gef. N 2.45 S 11.86

Claims (1)

R elease , A process for the preparation of glycopyranosylthiomethylene. Cyanoacetic acid derivatives of the general formula ΙΪΙ in which R is an alkyl radical and the acetylated .beta.-D-glycopyranosyl radical has the gluco or gaaoto configuration, characterized in that bromomethylenecyanoacetic acid ester of the general formula I where R.sup.a is as in is reacted with the acetylated .beta.-D-GrlycopyranoSylmercaptanen the general formula II with the Gluoo- or · Galaoto configuration » For this 1 page formulas