DD248591A1 - PROCESS FOR PREPARING SUBSTITUTED OXAZOLIDINE-5-YL POLYOLS - Google Patents

Abstract

The present invention relates to a process for the preparation of substituted oxazolidin-5-yl-polyols. The aim of the invention is to produce a large number of optically pure representatives of the previously unknown substance class of substituted oxazolidin-5-yl-polyols. The object is achieved by reacting N-substituted guanyldithiocarbimide diesters with amino-sugar alcohols. The representatives of the class of substances according to the invention are potential biocides which have a particular interest in the production of pharmaceuticals. The advantage of the invention is the direct synthesis of a large number of optically pure representatives of these hitherto unknown oxazolidin-5-yl-polyols from technically easily accessible starting materials.

Description

Field of application of the invention

The invention relates to a process for the preparation of substituted oxazolidin-5-yl-polyols. The representatives of this class of substances are of particular interest as intermediates for the preparation of pharmaceuticals and, provided with a wide variety of substituents, can be used to control animal and plant pests.

Characteristic of the known technical solutions

In the technical and patent literature, neither the substance class of the substituted oxazolidin-5-yl-polyols with corresponding substituent pattern has been described nor a suitable method that allows access to this interesting class of substances

 The process according to the invention provides a surprising access to this hitherto unknown substance class.

Object of the invention

The aim of the invention is to make the substance class of the substituted oxazolidin-5-yl-polyoie accessible by a suitable method. By using technically readily available starting materials, the process should lead to a large number of differently substituted representatives of these substituted oxazolidin-5-yl-polyols.

Explanation of the essence of the invention

The object is achieved in that N-substituted guanyl-Dithiocarbimidsäurediester of formula 1, in which X is a nitro or cyano group and R ^{1 is} substituted or unsubstituted alkyl or aralkyl radicals, with amino-sugar alcohols of the formula 2, in the R ^{2 is} substituted or unsubstituted alkyl or aralkyl radicals and η is 2, 3 or 4, directly to the substituted oxazolidin-5-yl-polyols of the formula 3 in which X, R ² and η have the above meaning, be implemented ,

R ² HN-CH,

NH ₀ j '

/ _SR 1 λ. HIGH

^y (HO-CH) _n - ^{2 r1sH}

'SR ¹ ' I

^b HO-CHo

XNC. _X ° ^ CH- (CH-OH) -CH OH ₀

e = c; ²

The reactions are in polar solvents, preferably in alcohols having 1 to 4 carbon atoms, at 60 ⁰ C to 120 ° C.

carried out. v.

The reaction products crystallize directly from the reaction solution in high purity. They can be purified by recrystallization from ethanol or DMF / ethanol.

The advantage of the invention is the direct synthesis of a large number of optically pure representatives of previously unknown substituted oxazolidin-5-yl-polyols with corresponding substituent pattern. The starting compounds used are substances which are technically accessible without much effort. The invention is explained with reference to exemplary embodiments, without being limited thereto.

embodiment

1. 3-Methyl-2- (N-nitroguanyl-imido) -5 (S) -1,3-oxazolidin-5-yl-D-arabo-tetritol

To 0.01 mol of N-nitroguanyl-dithiocarbimic acid dimethyl ester in 40 ml of ethanol are added 0.01 mol of 1-deoxy-1-methylaminoglucitol and the solution is refluxed for 6 hours under reflux. The reaction solution is then concentrated to about half the volume, the crystallized after cooling products crystallized and recrystallized from DMF / ethanol. Mp: 175-177 ° C (dec.) Yield: 65.4% d. Th. (2.0 g)

2. 2- (N -cyanoguanyl-imido) -3-methyl-5 (S) -1,3-oxazolidin-5-yl-D-arabo-tetritol

As in Example 1. 0.01 mol of N-cyanoguanyl-dithiocarbimic acid dimethyl ester with 0.01 mol of 1-deoxy-i-methylaminoglucitol

reacted. __

The crude product is purified by recrystallization from ethanol. ~~

M.p .: 99-101 ⁰ C (decomp.) Yield: 82.3% d. Th. (2.3 g)

3. 3-Methyl-2- (N-nitroguanyl-imido) -5 (R) -1,3-oxazolididin-5-yl-D-arabo-tetritol

The conversion of 0.01 mol of N-nitroguanyl-dithiocarbimic acid dimethyl ester with 0.01 mol of 1-deoxy-1-methylaminomannitol and the purification of the crude product is carried out analogously to Example 1.

Mp .: 181 ⁰ C (decomp.) Yield: 60.6% d. Th: (1.8 g)

4. 2- (N-cyanoguanyl-imido) -3-methyl-5 (S) -1,3-oxazolidin-5-yl-D-lyxo-tetritol

The conversion of 0.01 mol of N-cyanoguanyl-dithiocarbimic acid with 0.01 mol of 1-deoxy-i-methylaminogalactitol and the purification of the crude product is carried out analogously to Example 2.

Mp .: 192 ⁰ C (decomp.) Yield: 77.8% d. Th. (2.2 g)

5. 2- (N-Cyanoguanyl-imido) -3-methyl-5 (R) -1,3-oxazolidin-5-yl-D-arabo-tetritol

The conversion of 0.01 mol of N-cyanoguanyl-dithiocarbimic acid dimethyl ester with 0.01 mol of 1-deoxy-1-methylaminomannitol and the purification of the crude product is carried out analogously to Example 2.

Mp: 118 ° C (dec.) Yield: 76.4% d. Th. (2.1 g)

Claims (1)

A process for preparing substituted oxazolidin-5-yl-polyols of the formula 3 in which X is a nitro or cyano group, R ^{2 is} substituted or unsubstituted alkyl or aralkyl radicals and η is 2, 3 or 4, characterized N-substituted guanyl-dithiocarbimic diester of the formula 1, in which R ^{1 is} substituted or unsubstituted alkyl or aralkyl radicals and X has the above meaning, with amino-sugar alcohols of the formula 2 in which R ² and η have the above meaning.
2.Verfahren according to item 1, characterized in that the reactions in polar solvents, preferably in alcohols having 1 to 4 carbon atoms, at temperatures between 60 ⁰ C and 12O ⁰ C are performed.