SU1490113A1 - Method of producing bis-(2,2,2-trinitroathyl)thionocarbonate - Google Patents

Abstract

The invention relates to derivatives of thionogolic acid, in particular the preparation of bis- (2,2,2-trinitroethyl) -thion carbonate, used as an energy-intensive substance. The synthesis of the latter is carried out in methylene chloride environment by the interaction of 2,2,2-trinitroethanol with thiophosgene in the presence of pyridine with a ratio of reagents and base of 2: 1-1.2: 2-2.4, respectively, and a temperature of from -20 to -30 ° C. These conditions increase the yield of the target product from 20 to 60%, reduce the reaction time from 14 days. up to 1-1.5 hours. 1 tab.

Description

The invention relates to an improved process for the preparation of bis- (2,2,2-trinitroethyl) -thiocarbonate of formula (NOj), C 1, which can be used in the art as an intermediate substance for the preparation of plasticizers

The purpose of the invention is to increase the yield of bis- (2,2,2-trinitraethyl) -ionium carbonate and reduce the reaction time for its production, which is achieved by the interaction of 2,2,2-trinitrosanthol with thiophosgene (thiocarbonyl chloride) in a mixture with pyridine at a molar ratio of 2: (1-1.2): (2-2.4) and temperature (-20) - (- 30) s.

The invention is illustrated by examples.

Example 1 A solution of 11.5 g (0.1 mol) of thiocarbonyl chloride (thiophosgene) in 250 ml of methylene chloride is placed in a reactor equipped with a thermometer, a stirrer and an addition funnel in 250 ml of methylene chloride and a solution of 15.8 g is added dropwise at -20 ° C.

(0.2 mol) pyridine in 60, nl methylene chloride. After stirring at -20 ° C for 5 minutes, a solution of 36.2 g (0.2 mol) of 2,2,2-trinitroethanol in 60 ml of methylene chloride is added dropwise. After a period of 30 minutes, the product is purified, for which with stirring

and a temperature of -20 seconds was added dropwise with 30 ml of concentrated sulfuric acid. Stirring is continued for 5 minutes, the organic phase containing the desired product is separated and washed with another 2x30 ml of sulfuric acid, and then 3x10 ml with a 2% soda solution in water.

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The solution is shaken with activated carbon, filtered and distilled in vacuo. The solid residue is recrystallized from carbon tetrachloride. The output of 20.1 g (53%) of the original 2,2,2-trinitroethanol, so pl. 91-92 S.

The results obtained according to the proposed method of example 1, depending on the conditions of the process, are tabulated.

An analysis of the table below shows that the optimal ratio of reagents 2,2,2-trinitroethanol, thiocarbonyl pyridine is in the range of 2: (1-1.2): (2-2.4).

This is illustrated by examples 1, 2, 7, 8, 9, 11, 12, in which, under conditions of sufficient temperature and time, the reaction of 1-1 is realized, the yield of the target product is 53-60%. Exceeding (examples 4, 5) or lowering (examples 3, 6) the proportion of any reagent can either reduce the yield (examples 3, 5, 6) or does not contribute to its increase (example 4) compared with the examples given.

Optimum temperatures and reaction times are located in the intervals of (-20) - (- 30) ° C and 1-1.5 hours, respectively (examples 1, 2, 4, 7, 8, 11, 12).

A further decrease in temperature increases the reaction time and does not contribute to an increase in yield (with

measures 9), increasing the temperature above the specified limit (example 10) reduces the yield and purity, which is expressed in the color of the product. A reaction time of less than 1 hour is negatively predicted at the product outlet (Example 13), an increase in time in excess of 1.5 hours at the output almost does not affect (Example 12). Thus, in comparison with the known solution, the proposed method allows to obtain bis- (2,2,2-trinitroethyl) -thion carbonate with a yield of up to 60% (versus 20% in the known); reduce the reaction time to 1-1.5 hours (against 14 days).

Claims (1)

Invention Formula The method of producing bis- (2,2,2-trinitroethyl) -thioncarbonate by reacting 2,2,2-trinitroethanol with a thiocarbonyl derivative in a methyl methyl chloride medium, in order to increase the yield of the target product and reducing the process time, thiophosgene is used as a thiocarbonyl derivative in a mixture with pyridine at a molar ratio of 2.2.2-trinitroethanol – thiophosgene – pyridine, equal to 2: (1-1.2) :( 2-2.4) and the process carried out at a temperature of from -20 to -30 ° C. 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.12 0.9 0.15 0.11 0.11 0.10 0.11 0.11 0.11 0.11 0.11 0.11