RU2520964C1 - Method of obtaining 1,1,2,2-tetrakis-(nitroxymethyl)-1,2-dinitroethane - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to the field of organic synthesis, namely to a method of obtaining 1,1,2,2-tetrakis-(nitroxymethyl)-1,2-dinitroethane, which can be applied as an explosive substance. In accordance with the claimed method 1,1,2,2-tetrakis-(nitroxymethyl)-1,2-dinitroethane is obtained from 5,5'-bis-(2,2-dimethyl-5-nitro-1,3-dioxane) by hydrolysis, with hydrolysis and nitration being carried out in one stage by processing with the concentrated nitric acid.

EFFECT: method makes it possible to obtain 1,1,2,2-tetrakis-(nitroxymethyl)-1,2-dinitroethane in one stage with good output.

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Description

The invention relates to organic synthesis, in particular to a method for producing 1,1,2,2-tetrakis- (nitroxymethyl) -1,2-dinitroethane, which can be used as an explosive.

A known two-stage method for producing 1,1,2,2-tetrakis- (nitroxymethyl) -1,2-dinitroethane (1) (US Patent No. 2012/0108838 A1 of May 3, 2012) by hydrolysis of 5.5'-bis- (2 , 2-dimethyl-5-nitro-1,3-dioxane) (2) to 1,1,2,2-tetrakis- (hydroxymethyl) -1,2-dinitroethane (3) followed by nitration:

According to the patent, the first stage of the process - hydrolysis of compound 2 is carried out according to the method:

Through a suspension of 25.6 g (0.08 mol) of compound 2 in 200 ml of methanol, gaseous hydrogen chloride was bubbled to saturation, the reaction vessel was plugged and left at room temperature for 48 hours. After removal of the volatile components, the residue was triturated with hot chloroform and 8.1 g (85%) of compound 3 were obtained with a melting point of 100-102 ° C.

The second stage of the process - nitration of compound 3 is carried out according to the method:

50 ml of acetic acid and 50 ml of acetic anhydride are mixed, the resulting solution is cooled to 0 ° C. Then, with stirring, 34 g of 98% nitric acid are added dropwise at such a rate that the temperature of the reaction mixture is not higher than 5 ° C. The reaction mixture was stirred at 0 ° C for 20 minutes, 12 g (0.05 mol) of compound 3 was added portionwise, stirred at 0 ° C for 2 hours, and the temperature was raised to 20 ° C, and stirred at this temperature for 1 hour. Then the reaction mixture was poured with stirring in 200 ml of ice water. The precipitate formed is filtered off, washed with water and 20 g of crude product 1 are obtained, crystallization of which from isopropyl alcohol gives 18 g (85%) of compound 1 with a melting point of 85-86 ° C.

This method is accepted by us as the closest analogue.

The disadvantages of the analogue are:

- two-stage process;

- the use of corrosive hydrogen chloride;

- the duration of the hydrolysis of product 2;

- the need to remove volatile components;

- the need for washing the precipitate with hot chloroform;

- the use of a precursor - acetic anhydride;

- the danger of the nitration process due to the formation of acetyl nitrate during the reaction.

An object of the invention is to develop a method for producing 1,1,2,2-tetrakis- (nitroxymethyl) -1,2-dinitroethane (1), devoid of the above disadvantages.

The technical result is achieved by the fact that the hydrolysis and nitration of 5,5'-bis- (2,2-dimethyl-5-nitro-1,3-dioxane) (2) is carried out in one stage by treating it with concentrated nitric acid.

Distinctive features of the invention are:

- one-step process;

- the exclusion from the process of substances such as corrosive hydrogen chloride, the precursor of acetic anhydride and toxic chloroform and methanol;

- the exception of the stage of hydrolysis and distillation of volatile components;

- the exception of the stage of processing the precipitate after distillation of the volatile components by hot chloroform;

- simplicity of the process.

The method for producing 1,1,2,2-tetrakis- (nitroxymethyl) -1,2-dinitroethane is illustrated by the following example.

In a flask equipped with a mechanical stirrer and reflux condenser, 33 ml (49.5 g, 0.78 mol) of 98% nitric acid are charged, 2.4 g (0) are added portionwise with stirring and a temperature of -2 ÷ -10 ° C. , 0075 mol) of 5.5'-bis- (2,2-dimethyl-5-nitro-1,3-dioxane) (2) for 15 minutes. Then the reaction mixture is stirred at a temperature of -5 ÷ 0 ° C for 3 hours and poured into 167 ml of cold water. Precipitated light gray crystals are filtered off, washed with water, and dried in air. Allocate 2.2 g (70%) of the crude product with so pl. 74 ° C. After recrystallization from isopropyl alcohol, the yield of product 1 is 2.1 g (67%), so pl. 84 ° C.

The IR and ¹ H NMR spectra of compound 1 are consistent with those given in US Pat.

Claims (1)

A method for producing 1,1,2,2-tetrakis- (nitroxymethyl) -1,2-dinitroethane from 5.5'-bis- (2,2-dimethyl-5-nitro-1,3-dioxane) by stepwise hydrolysis and nitration of the hydrolysis product, characterized in that the hydrolysis and nitration of the product is carried out in one stage by processing it with concentrated nitric acid.