CS238442B1 - Process for producing 1,3,5,7-tetranitro-1,3,5,7-tetraazacycloctane - Google Patents

Abstract

The invention concerns the production of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane, called octogen, by nitration cleavage of 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane, called DADN, with nitric acid containing nitric oxide, with dicyandiamide added to the reaction system in an amount of 0.05 to 11 wt. %, calculated on the initial amount of DADN. The process is applicable in the production of octogen, but is of particular importance for the development of new processes for the production of this substance.

Description

(54) Production method for 1,3,5,7-tetranitro-1,3,5,7-tetraazacycloctocane

The present invention relates to the production of 1,3,5,7-tetranitro 1,3,5,7-tetraazacyclooctane, called octogen, by nitration cleavage of 1,5-diacetyl-3,7-dinitrO-1,3,5,7-tetraazacyclooctane, % of DADN, a nitric oxide-containing nitric acid, and 0.05 to 11% by weight of dicyandiamide, calculated on the starting amount of DADN, is added to the reaction system. The process is applicable in the production of octogen but is of particular importance for the development of new processes for the manufacture of this substance.

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

A common process for the production of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane, also called octogen, also referred to as HMX code, consists in nitrolysis of hexamethylenetetramine and / or 1,5-methano-3,7-dinitro- 1,3,5,7-tetraazacyclooctane (bibliography see E. Ju. Orlova: Oktogen - termostojkoe vzryvčatoe vsechestvo: Izdat. Nedra, Moscow, 1987). In the last decade, however, attention has been increasingly focused on the processes by which octogen is obtained through 1,5-dialkanoyl-3,7-methano-1,3,5,7-tetraazacycloctocanes; their preparation is described, for example, in V.I. Siele, M.Warmann and E.E. Gilbert: J. Heterocycl. Chem. 1974, 11, 237; U.S. Pat. 3,850,923 and 3,849,414.

A method of octogen synthesis starting from 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacycloctocane as an intermediate (U.S. Pat. No. 3,939,148) appears to be very attractive. This intermediate 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); its codename is DADN. Nitrolysis of 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane with nitric acid containing up to 50% by weight of nitric acid. nitric oxide, depending on the reaction conditions and to a small extent on the nitric oxide source, provides octogen in 41 to 98% yield compared to theory (U.S. Pat. No. 3,939,148). A disadvantage of this known nitrolysis process of DADN is that fresh distilled anhydrous nitric acid must be applied in large excess over theory to ensure high octogen recovery (U.S. Pat. No. 3,939,148). Thus, for example, 34.5 wt.% Are required to obtain 1 wt.% Of the 100% octogen and an 98% yield. % of freshly distilled nitric acid and 11.5 wt. % of phosphorus pentoxide.

The major side reaction of the nitrolysis of 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane is the cleavage of the 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 nitrogen dioxide source (a combination of nitric acid and phosphorus pentoxide or sulfur trioxide or trifluoroacetic anhydride or a solution of nitrogen dioxide in nitric acid - see US Pat. ).

Recent knowledge is the yield and safety of the nitrous cleavage and / or nitration process of amines, their N-derivatives and amides, to cyclic nitramines favorably affected by the presence of certain additives (see, for example, US Patent Nos. 206 382, 213 509, 214 311, 218 703 and others) that I figure here! essentially as third generation catalysts. For the purposes of the present invention, the production of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane is accomplished by nitration of 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane by acid nitric oxide containing nitric oxide in the presence of dicyanide added to the reaction system in an amount of 0.05 to 11.0% by weight, calculated on the weight of the reaction taken 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, and an increase in yield is achieved.

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 variability of the production method 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. 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 (all previous operations). with good mixing). Thereafter, the nitration apparatus content is loaded into · 1500 volumes, 20 to 22 ° C parts of warm water, and the resulting mixture is filtered.

Filter Product! The reaction mixture is washed with water until the filtrate is neutralized and then dried at 90-95 ° C for 3 hours. The technical octogen thus obtained can be freed of very small amounts of by-products by heating it in suspension in 70% nitric acid.

This basic procedure is repeated with the application of the starting DADN, modified with a certain amount of dicyandiamide. Tabular dams present the results:

Quantity of dicyandiamide DADN wt. wt. % for long DADN bait

Yield of octogen mass. % versus part theory

Uncorrected octogen melting point (° C)

0.00 0.0 15.0 73.58 278—281 0.10 0.5 15.6 76.60 277,5—280 0.40 2,0 16.5 80.88 276—279 1.00 5.0 17.0 83.33 275—278 2.00 10.0 15.5 75.98 274—277

Example 2

K 110 vol. 80 parts by weight of nitric acid of the same quality as in Example 1 are dosed under the same conditions as in Example 1. parts by weight of phosphorus pentoxide, and then to the resulting solution 10 wt. DADN parts. After stirring for 30 minutes at 59 to 61 ° C, the reaction mixture is poured into 1000 volumes, parts of water about 20 ° C warm. The resulting suspension is treated as in Example 1. 8.4 wt. parts of octogen, m.p. 279 DEG-280 DEG C. with decomposition; said yield represents 82.35% compared to theory.

Example 3

The procedure is as in Example 2, except that the starting DADN applied contains 0.8 parts by weight of dicyandiamide. The reaction resulted in 8.5 wt. parts of octogene, m.p. 280 ^DEG- 281 ^DEG C. with decomposition; said yield represents 83.33% of theory [i.e. when applied at 8% wt. Dicyandiamide (DADN).

Claims (1)

SUBJECT Process for the preparation of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane by nitration cleavage of 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane with nitric acid characterized in that the nitrolysis process is carried out in the presence of diamine dicyanase to the reaction system added in an amount of 0.05 to 11.0% by weight, preferably in an amount of 0.5 to 10% by weight. calculated on the weight of the reaction taken from 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane.