DD232707A1 - PROCESS FOR PREPARING SUBSTITUTED GLYCOPYRANOSYLTHIO-2,5-DIHYDRO-BENZ (B) (1.4) OXAZEPINE CARBOXYLIC ACID ESTERS - Google Patents

Abstract

The invention relates to a process for the preparation of substituted glycopyranosylthio-2,5-dihydro-benz (b) (1,4) oxazepincarbonsaeureestern. The aim of the invention is to develop a process for the preparation of substituted glycopyranosylthio-2,5-dihydro-benz (b) (1,4) -oxazepinecarboxylic acid esters. The substituted glycopyranosylthio-2,5-dihydro-benz (b) (1,4) -oxazepinecarboxylic acid esters of general formula III in which R is an alkyl radical and the acetylated bD-glycopyranosyl radical has the gluco or galacto configuration by reacting the 4,5-dihydro-benz (b) (1,4) oxazepinecarboxylic acid ester of the general formula I in which R has the above meaning, with acetohalogenoses of the general formula II with the gluco or galacto configuration in the presence of Bases are produced. The substituted glycopyranosylthio-2,5-dihydro-benz (b) (1,4) -oxazepinecarboxylic acid esters can be used as organic intermediates. They are particularly suitable for the preparation of specific S-glycosides.

Description

Field of application of the invention

The invention relates to a process for the preparation of 2-imino-4 -, (tetra-0-acetyl-β-D-glycopyranosylthio) -2,5-dihydroberiz [b] [1,4] oxazepine-3-carboxylic acid esters.

These substituted glycopyranosylthio-2,5-dihydro-benz- [b] [1,4] oxazepinecarboxylic acid esters can be used as organic intermediates. They are particularly suitable for the preparation of specific S-glycosides.

Characteristic of the known technical solutions

2-Imino-4- (tetra-O-acetyl-O-D-glycopyranosylthio) -2,5-dihydro-benz [b] [1,4] oxazepine-3-carboxylic acid esters are not yet known.

Object of the invention

The aim of the invention is to develop a process for the preparation of substituted glycopyranosylthio-2,5-dihydro-benz [b] [1,4] oxazepinecarboxylic esters.

Explanation of the essence of the invention

The substituted Glycopyranosylthio- ^ S-dihydro-benztbKi ^ loxazepincarbonsäureester of the general formula III in which R is an alkyl radical and the acetylated ß-D-Glycopyranosylrest has the gluco- or galacto configuration can be prepared by reacting the 4,5-dihydroxy benz [b] [1,4] oxazepine-carboxylic acid ester of the general formula I, in which R has the above meaning, with acetohalogenoses of the general formula II with the glucose or galacto configuration in the presence of bases.

The reactions are carried out in an organic solvent, preferably in alcohols, in the presence of bases soluble in these alcohols, preferably sodium alcoholates. It is expedient to use those alcohols and sodium alcoholates which have the same radical R as the substituted 4,5-dihydrobenz [b] [1,4] oxazepinecarboxylic acid ester used.

The reaction temperatures are around 20 ° C. The reaction times are 6-8 hours. After completion of the reaction, the reaction mixture is cooled. The crystallizing acetylated S-glycosides are filtered off, washed with water and alcohols and recrystallized from alcohols for further purification.

Embodiments Example 1

4- (Tetra-O-acetyl- / 3-D-glycopyranosylthio) -2-imino-2,5-dihydrobenz [b] [1,4] oxazepine-3-carboxylic acid methyl ester Dissolve 0.23 g (0.01 sodium in 15 ml of absolute methanol, successively adding 2.50 g (0.01 mol) of 2-amino-4-thioxo-4,5-dihydrobenz [b] [1,4] oxazepine while shaking to complete dissolution 3-carboxylic acid methyl ester and 4.11 g of a-acetobromoglucose and allowed 8 hrs. At 20 ⁰ C stand. After cooling to 5 ⁰ C, the precipitated crystals are filtered off, washed with water and recrystallized from ethanol

 Yield: 19% d. Th. Schmp. 173-175 ° C

[a] j! ² ' ⁵ = -49.76 ° (C = 1.07, in acetone)

C ₂₅ H ₂₈ N ₂ O ₁₂ S (580.3) Ber. C 51.74 H 4.86 N 4.82

C, 51.70 H, 4.83, N, 5.12

Embodiment 2

4- (Tetra-O-acetyl-1-galactopyranosylthio) -2-imino-2,5-dihydro-benz [b] [1,4] oxazepine-carboxylic acid methyl ester 2.50 g (0.01 mol) 2 -Amino-4-thioxo-4,5-dihydric-benz [b] [1,4] -oxazepin-3-carboxylic acid methyl ester and 4.11g (0.01 mol) of a-Acetobromgalactose are reacted as in Example 1 described. Discharge: 12% d.Th. Mp. 105-108X

19 ία] = -5.66 ° (c = 1.09, in acetone)

C ₂₅ H ₂₈ N ₂ O ₁₂ S (580.3) Ber. C 51.74 H 4.86 N 4.82

Gef. C 51.36 H 5.20 N 4.76

Ausfümungsbeis'pieTä """""*""~"'"~ ~ · ~ ·" - "

4- (Tetra-O-acetyl-i3-D-glucopyranosylthio) -2-imino-2,5-dihydro-benz [b] [1,4] oxazepine-carboxylic acid ethyl ester 2.64g (0.01 mol) 2 Amino-4-thioxo-4,5-dihydro-benz [b] [1,4] oxazepine-3-carboxylic acid ethyl ester and 4.11 g (0.01 mol) of α-acetobromo-glucose are reacted as in Example 1 described. Yield: 37% d. Th. Mp. 128-130X;

20 [a] = -56.6 ° (C = 1.0, in acetone)

C ^ H ₃₀ N ₂ O ₁₂ S (594.6) Ber. C 52.52 H 5.09 N 4.71

Gef. C 52.24 H 5.00 N 4.80

-Ü- / IO Oö

Embodiment 4

4- (Tetra-0-acetyi- / 3-D-galactopyranosylthio) -2-imino-2,5-dihydro-benz [b] [1,4] oxazepine-carboxylic acid ethyl ester 2,64g (0,01 mol) 2-Amino-4-thioxo-4,5-dihydro-benz [b] [1,4] oxazepine-3-carboxylic acid ethyl ester and 4.11 g (0.01 mol) of α-acetobromo-galactose are reacted as in the working example 1 described. Ausb.:25%d.Th. Mp 154-156 ° C

20 [a] = -22.32 ° (c = 1.1, in acetone)

C ₂₆ H ₃₀ N ₂ O ₁₂ S (594.6) Calcd. C 52.52 H 5.09 N 4.71

Gef. C 52.51 H 5.21 N 4.57

  IT

σ-coon

-C

,He

CH (OAc) CH (OAc) CH (OAc)

CH ₂ OAc II

HO ^- BTa ⁺ (ROE ^

- ITABr

- HOH

 σ

C-COOH

 σ

III

CH (OAc) j CH (OAc) CH (OAc);

HC

CH ₂ OAc

Claims (1)

-1- 71558 Invention claim: A process for the preparation of substituted glycopyranosylthio-2,5-dihydro-benz [b] [1,4] oxazepine carboxylic acid esters of the general formula III in which R is an alkyl radical and the acetylated / 3-D-glycopyranosyl radical is the gluco or galacto configuration characterized in that 4,5-dihydro-benz [b] [1,4] oxazepincarbonsäureester of the general formula I, in which R has the above meaning, with acetohalogenoses of the general formula II with the gluco- or. Galacto configuration can be implemented in the presence of bases. For this 1 page formulas