CS238443B1 - 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane production method - Google Patents

Abstract

The invention relates to the preparation of 1,3,5,7-tetranitro-1,3,5,7-tetraazacycloctane nitrating cleavage of 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacycloctane, code DADN, nitric acid containing oxide nitric acid, into the reaction system added nitromo-zinc in an amount of 0.5 to 10 wt. to the starting weight Ḑadnā. The procedure is applicable in the production of octogen development of new production processes of this substance.

Description

The present invention relates to a process for the preparation of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane, called octogen, by nitrolysis of 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane nitric acid containing nitric oxide, in the presence of nitrurea in the reaction mixture.

A common process for the production of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane, called octogen and designated HMX, is by nitrolysis of hexamethylenetetramine and / or 1,5-methano-3,7-dinitro-1. 3,5,7-tetraazacyclooctane (termed DPT) - see bibliography in E. Ju. Orlova: Octogen - termostojkoe vzryvčatoe veščestvo; Izdat. Nedra, Moscow, 1978. In the last decade, however, attention has been directed to processes for the production of octogen via 1,5-dialkanoyl-3,7-methano-1,3,5,7-tetraazacyclooctanes: their preparation is described, for example, in: VI Siele, M. Warmann and Ε. E. Gilbert, J. Heterocycl. Chem. 1974, 11, 237; US Pat. 3,850,923 and 3,849,414.

A very technically attractive method of octogen synthesis is the application of 1,5-diacetyl-3,7-dinitro-1,3,5,7-tatraazacyclooctane, referred to as DADN, as a starting substance (U.S. Pat. No. 3,939,148). DADN results from hexamethylenetetramine via 1,5-diacetyl-3,7-methano-1,3,5,7-tetraazacyclooctane in yields of 91-98% over theory (U.S. Pat. Nos. 3,850,923 and 3,926,953). Nitrolysis of DADN with nitric acid containing up to 50 wt. nitric oxide, depending on the reaction conditions and, to a small extent, the nitric oxide source, provides octogen at 41-98% yield compared to theory (U.S. Pat. No. 3,939,148). A disadvantage of this described DADN nitrolysis process is that fresh distilled anhydrous nitric acid needs to be applied in large excess over theory to ensure high process yield (U.S. Pat. No. 3,939,148). Thus, for example, to obtain 1 wt. 34.5% by weight of octogen of 100% purity and 98% of theory. % of freshly distilled nitric acid and 11.5 wt. % of phosphorus pentoxide

The major side reaction of DADN nitrolysis is the cleavage of 1,3,5,7-tetraazacyclooctane skeleton. In addition to the reaction conditions in the general sense, the course of this undesired reaction also depends on the kind of nitric oxide source, a combination of nitric acid and phosphorus pentoxide or sulfur trioxide or trifluoroacetic anhydride or a solution of nitrogen dioxide in nitric acid - U.S. Pat. 3,939,148).

According to the latest knowledge, the yield and safety of the nitrous cleavage and / or nitration process of amines, their N-substituted derivatives and amides, to cyclic nitramines is favorably influenced by the presence of some additives in the reaction mixture (cf. , 213,509, 214,311, 218,703, and others), which function here essentially as third generation catalysts. For the purposes of the present invention, the production of octogen is carried out by nitrous cleavage of 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane with nitric oxide-containing nitric acid, in the presence of nitrurea, added to the reaction system in an amount of 0, 05 to 10% by weight, calculated on the weight of the reaction of 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane.

An advantage of the process of the present invention is that freshly distilled nitric acid is not required, while increasing the yield of the process. The presence of nitro-urea in the reaction mixture very strongly eliminates the development of nitrogen oxides, potentially increasing process safety (named oxides being catalysts of undesired oxidation processes in the reaction system).

The higher effect achieved for the purposes of the present invention has not been described so far in the literature; it is illustrated by the following examples, which in no way exclude the possible variability of the process according to the invention.

Example 1

K 200 volume, part by volume of nitric acid 98.1% with a content below 0.3% by weight. of analytical nitric acid, presented in the nitration apparatus, 100 wt. parts of phosphorus pentoxide. Into the resulting solution, 20 wt. parts of 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane (DADN) and the temperature of the reaction mixture is carefully raised to 54-57 ° C for 30 minutes. Thereafter, the contents of the nitration apparatus are poured into 1500 volumes, parts of 20-22 ° C hot water, and the resulting supernatant is filtered. The product on the filter is washed with water until the filtrate reacts neutrally and is then 3 hours. dried at 90 to 95 ° C. The technical octogen thus obtained can be freed from very small amounts of by-products by heating it in 70% nitric acid.

15 masses result. parts of octogen, m.p. 278-281 ° C; the yield represents 73.58% of theory.

Example 2

The procedure of Example 1 was followed, except that the DADN applied contained 2 wt. parts of nitro-urea; the reaction is characterized by a very reduced evolution of nitrogen oxides over the course of Example 1.

16 masses result. parts of octogen, m.p. 282-283 ° C; the yield is 78.43% of the theory of very pure product (achieved by adding 10% by weight of nitro urea to the DADN bait).

Example 3

K 110 volume, part by volume of nitric acid) of the same quality as in Example 1, under the same conditions as in Example 1, SO 2 masses are dosed. parts by weight of phosphorus pentoxide and then into the resulting solution 10 wt. DADN parts one time. After stirring for 30 minutes at 59 to 61 ° C, the reaction mixture is lumped into 1000 volumes, parts of water about 20 ° C warm and the resulting supernatant is worked up as in Example 1.

Amount of nitro urea in DADN mass wt. % for bait parts

Ḑadnā

This basic procedure is repeated with the application of DADN containing a certain amount of nitrosourea. The results are presented by the following overview:

Yield of octogen mass. % versus part theory

Uncorrected octogen melting point (° C)

0.00 0.0 8.4 82,35 279-280 0.05 0.5 8.6 84.10 280 to 281.5 0.50 5.0 8.7 85,29 279 to 280.5

SUBJECT

Claims (1)

Process for producing 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane by nitration of 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane with nitric acid containing nitric oxide characterized in that the lysis nitro-invention process is carried out in the presence of nitrourea in an amount of 0.5 to 10% by weight to the reaction system. to the mass of the starting 1,5-diacetyl 1-3,7-dinitro-1,3,5,7-tetraazacyclooctane.