RU2327693C1 - Method of obtaining 2,4-bis(1,3,5-dithiazanine-5-yl)-4-oxo-oleic acid - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: 2,4-bis(1,3,5-dithiazanine-5-yl)-4-oxo-oleic acid has formula:

including reaction a water solution formaldehyde saturated with hydrogen sulphide with a water solution of monoamide of α-aminosuccinic acid.

EFFECT: the acid can be used as a pharmacologically active compound, as well as selective sorbents and extractant of noble and precious metals.

1 cl, 1 dwg, 1 ex

Description

The present invention relates to the field of organic chemistry, and in particular to a method for the synthesis of 2,4-bis (1,3,5-dithiazinan-5-yl) -4-oxo-butyric acid of the formula (1):

The presented compound can find application as a modified selective sorbent and extractant of noble and precious metals (Murinov Yu.I., Maistrenko V.N., Afzaletdinova N.G. Extraction of metals by S, N-organic compounds. M. Nauka. 1993, 192 ), as well as a pharmacologically active compound (Z. Brzozowski, F. Saczewski and M. Gdaniec. Bioorganic & Medicinal Chemistry, 2003, No. 11, p.3673-3681).

The synthesis of 2,4-bis (1,3,5-dithiazinan-5-yl) -4-oxo-butyric acid is not described in the literature. From the literature it is known that when using the reagent CH ₂ OH ₂ S in a ratio of 3: 2 with respect to amino acids, the reaction proceeds with the formation of the major product of perhydro-1,3,5-dithiazine 2 and minor 1,3,5-oxathiazine 3, tritiolane and tetratiepane (R.V. Kunakova, S.R. Khafizova, Yu.S.

Also, 1,3,5-dithiazinane cycles can be prepared by reacting amino acids with sodium hydrosulfide and formaldehyde (A.N. Kurchan, A. G. Kutateladze. Org. Lett., 2002, 4 (23), 4129-4131). The obtained compounds have high complexing properties with respect to noble metals, in particular, the Ag 2- [1,3,5-dithiazin-5yl] acetic acid capacity is 0.9 g / g (S.R. Khafizova, V.R. Akhmetova, G.R. Nadyrgulova, Petrochemistry, 2005, T45, No. 5, 345-349).

The literature describes the thiomethylation reaction of bifunctional ethylenediamine with the selective formation of predominantly 5- (1,3,5-dithiazin-5-yl) ethyl-1,3,5-dithiazine (3), the content of which in the reaction mixture at 80 ° С is ~ 90%, along with thiazetidine (4) during the mixing of diamine with formaldehyde and subsequent bubbling of the reaction mixture with hydrogen sulfide (S.R. Khafizova, V.R. Akhmetova, T.V. Tyumkina and others. Izvestiya AN, ser. Chem., 2005 No. 2, 423-427).

By the methods listed above, 2,4-bis (1,3,5-dithiazinan-5-yl) -4-oxo-butyric acid cannot be obtained.

The objective of the invention is to obtain 2,4-bis (1,3,5-dithiazinan-5-yl) -4-oxo-butyric acid by one-reactor condensation of α-amino-succinic acid monoamide with formaldehyde and hydrogen sulfide.

The synthesis of 2,4-bis (1,3,5-dithiazinan-5-yl) -4-oxo-butyric acid is proposed by reacting an aqueous solution of α-amino-succinic acid monoamide with a mixture of hydrogen sulfide-formalin (37%) at a molar ratio of α-amino-succinic acid monoamide : formaldehyde: hydrogen sulfide = 1: 6: 4, a temperature of 40 ° C and constant stirring for 6 hours. As a result, 2,4-bis (1,3,5-dithiazinan-5-yl) -4-oxo-butyric acid (1) is formed in 65% yield, which is a crystalline product with mp 147-149 ° C. The reaction proceeds according to the scheme:

When carrying out the reaction at 80 ° C, the formation of crystalline hydrate of the starting molecule with water is observed, and when carrying out the reaction at 20 ° C, the conversion reaches 40%.

The advantages of the proposed method

Based on the proposed method, it is possible to selectively obtain 2,4-bis (1,3,5-dithiazinan-5-yl) -4-oxo-butyric acid, the synthesis of which has not been previously described in the literature. The proposed method is technologically simple, water is used as a solvent, the process does not require energy and toxic waste is not generated.

The environmental degradation characteristic of recent decades in a number of regions of the Russian Federation is largely due to the extraction and processing of sulfur dioxide and gas. Highly toxic hydrogen sulfide released during this process is usually burnt, which leads to the emission of billions cubic meters of acid gas into the atmosphere, or is used to produce elemental sulfur, the quality and quantity of which poses new problems, but already with its utilization. At the same time, hydrogen sulfide is an extremely interesting compound from a chemical point of view. Its involvement in the field of organic chemistry contributes to the solution of both environmental problems and the creation of new practically useful technologies of the future.

The method is illustrated by an example.

EXAMPLE. 6 moles of formaldehyde (4.42 ml. 37% aqueous solution) are placed in a glass reactor equipped with a magnetic stirrer, a reflux condenser, a gas tube and a dropping funnel at a temperature of 40 ° С, and a formaldehyde solution is bubbled into hydrogen sulfide for 30 minutes. Then, the prepared aqueous solution (1 mol (1.32 grams)) of α-amino-succinic acid monoamide (asparagine) is added dropwise to the reactor with formalin saturated with hydrogen sulfide and stirred for 6 hours, maintaining the required temperature (40 ° C). After filtration, crystalline 2,4-bis (1,3,5-dithiazinan-5-yl) -4-oxo-butyric acid is isolated in 65% yield.

Claims (1)

The method of obtaining 2,4-bis (1,3,5-dithiazinan-5-yl) -4-oxo-butyric acid of the formula:

consisting in the fact that an aqueous solution of formaldehyde saturated with hydrogen sulfide interacts with an aqueous solution of α-amino-succinic acid monoamide.