CS219191B1 - A method of making a mixture of cyclic nitramines - Google Patents

Abstract

The invention relates to a method for the production of a mixture of cyclic nitramines by nitration cleavage of hexamethylenetetramine in an environment created by acetic acid and acetic anhydride. The essence of the invention is to increase the yield of nitrate cleavage, which is achieved by the presence of tetrahydroimidazo[4,5-d]-imidazole-2,5(1Hs3H)dione.

Description

3 219191

BACKGROUND OF THE INVENTION The present invention relates to a process for the preparation of a mixture of cyclic nitramines by nitration of hexamethylenetetramine in an acid-acetic and acetic anhydride medium, the conditions being modified to positively influence the yield of the reaction.

According to the latest knowledge, the formation of cyclic nitramines is favorably influenced in the nitration of hexamethylenetetramine, in the reaction mixture, by the presence of urea, urea-formaldehyde condensates, and the like. and other amide acids of their derivatives applied individually, or mixtures of multiple substances. [čs. author's certificate. 227 903, No. 206 382 No. 2 2 7 9 0 5; No> 2 2 7 9 0 6, No. 2 2 7 9 i 1, No. 2 1 3 5 0 9, No. 2 14 3 1 . The mechanism of action of additives in the process of nitration cleavage of hexamethylenetetraamine was in the form of a hypothesis outlined in two examples [MS. copyright certificate 2 2 7903 'al. 227 905 J.

According to the present invention, a process for the preparation of a mixture of cyclic nitramines by nitration of hexamethylenetetramine in an environment formed by acetic acid and acetic anhydride is carried out by the process of nitration cleavage in the presence of tetrahydroimidazo [4,5-d] imidazole-2,5 (1H, 3H) -dione added to the reaction system simultaneously or sequentially in an amount of 0.01 to 50.00% by weight, preferably 0.47 to 30.00% by weight of the weight of the hexa-methylenetetramine reacted. The advantage of the procedure for the so-called; Bachmann's terms of the invention are an increase in process yield, hence an increase in the use of methylene base hexamethylenetetramine. The reaction according to the invention results in a mixture of 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), 1,3,5,7-tetranitro-1,3,5,7-tetraazacycloctane (HMX) and 1,4-dinitro-tetrahydroimidazo [4,5-d] imidazole-2,5 (1H, 3H) -dione (DINGU), which is suitable for the production of a mixture of hexotols and diclone. octols (Belgian Patent No. 863,738).

As is evident from the exemplary part of the present invention for the use of methylene base for the formation of cyclic nitramines, the latter is achieved in the latter by the latter in the hexamethylenetetramine (HMT) nitrile mixture with tetrahydimidimido [4,5-d] imidazole-2,5 (1H, 3H) dione. about 0.5 to 5.0 wt. As follows from the work of MS. author's certificate no. 2 9 9 6 1 is characterized by a mixture of said type and stability of agglomeration.

The higher effect achieved in the sense of the present invention has not been described in the literature so far and is illustrated by the following examples. Example 1 10 g of hexamethylenetetramine containing 0.32 wt. moisture (0.071 mol of hexamethylenetetramine) is dissolved in 17 ml of 97.2% acetic acid (0.288 mol of acetic acid); this solution is hereinafter referred to as "solution A". Solution B is prepared by dissolving 18 g of ammonium nitrate with 0.8% by weight. of moisture (0.221 ammonium nitrate) in 13 ml of 98.3% acid-nitric acid (0.306 mol of nitric acid) with a content of 0.1 wt. analytical nitrous acid.

Into the nitration apparatus with propeller stirrer by jacket cooling, resp. by heating, 42 ml of 99.8% acetic anhydride (0.444 mol of acetic anhydride) are added. With continuous stirring and temperature ranging from 50 to 55 ° C, the solutions A and B are fed into the acetic anhydride at the same time for 10 to 12 minutes. After their addition, the temperature of the mixture is raised to 70 to 72 ° C and maintained at a temperature of up to 76 ° C for 30 minutes. . Thereafter, the reaction mixture is poured into 180 ml of water 65-70 ° C and the resulting suspension is refluxed for 30 minutes. After cooling to 20-25 ° C, the suspension is then filtered, the product on the filter is washed with a water-neutral filtrate reaction and dried at 90-100 ° C. The process is repeated 4 times with 10 g of a hexamethylenetetramine mixture with a certain amount of tetrahydroimidazo [4,5-d] imidazole-2,5 (1H, 3H) -dione. The results of each nitrolysis are presented in Table 1. Example 2

The procedure is as in Example 1, but with the difference that a weight of 9.5 g of hexamethylenetetramine (0.067 mol of HMT) is used. A further process, wherein 0.5 g of tetrahydroimidazo [4,5-d] imidazole-2,5 (1H, 3H) -dione is added to the present acetic anhydride, and only then is the dosing of the solutions A and II started. B. Produces 11.9g product with 12.4% by weight. 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) and 0.84 wt. 1,4-dinitro-tetrahydroimidazo [4,5-d] imidazol-2,5 (1H, 3H) -dione (DINGU). Yield Yield makes 12.25% versus theory, yield HMX7.31% and RDX 68.90% versus theory. The use of HMT methylene base is 39.3% over theory.

Claims (1)

Table 1 2Ϊ9Ϊ91 Glycoluril content of HMT (% w / w) Amount of product (g) Starting point of melting point CO Content of the product in the product (% w / w) HMX DINGU YieldDINGUnder theory (% w / w) Component Compound (% w / w) HMX RDX thylene base in HMT opposite theory (% by weight) 0.00 11.8 197.0 3.8 '0.00 0.00 2.13 71.84 37.34 0.47 14.8 188.0 9.2 0 , 33 65.79 6.47 85.19 46.91 1.03 15.1 191.0 7.3 0.66 59.45 5.25 88.93 47.96 4.85 14.4 198.0 4.1 2.08 37.90 2.90 89.90 46.88 30.00 11.6 192.0 4.8 4.30 10.20 3.61 95.56 50.19 ARTICLE Method of producing a mixture of cyclic by nitraminoin cleavage of hexamethylenetetramine in a medium formed by acetic acid and acetic anhydride, characterized in that the nitration process is carried out in the presence of tetrahydroimidazo [455-d] imidazole-2,5 (1H, 3H) -dione, OF THE INVENTION introduced into the reaction system at one time, or at a rate of 0.01 to 50.00% by weight, preferably in an amount of 0.47 to 30.00% by weight. weighted into the reaction of hexa-methylenetetramine.