CS227907B1 - Process for preparing 1,3,5,7-tetranitro-1,3,5,7-tetraazacycloctane - Google Patents

Abstract

The invention entitled "Process for the production of 1,3,-5,7-tetranitro-1,3.5,7-tetraazacyclooctane" deals with the production of the title compound under Bachmann's conditions in an acetic anhydride environment and in the presence of urea-formaldehyde condensate, while the yield and safety of the process are affected to a significant extent.

Description

(54) Method for producing 1,3,5,7-tetranitro-1,3,5,7-tetraazacycloctane

SUMMARY OF THE INVENTION The present invention is directed to a process for the preparation of 1,3,5,7-tetranitro-1,3,5,7-tetraazacycloctocane under the Bachmann conditions in acetic anhydride and in the presence of urea-formaldehyde condensate, whereby yield and safety are substantially affected. process.

The invention relates to a process for the preparation of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane by nitration cleavage of 1,5-endomethylene-3,7-dinitro-1,3,5,7-tetraazacyclooctane in acetic anhydride medium wherein the conditions are chosen to substantially increase the yield and process safety.

Nitrile cleavage of 1,5-endomethylan-3,7-dinitro-1,3,5,7-tetraazacyclooctane, referred to as DPT, to 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane, called also octogen and commonly referred to as HMX code, can be realized with 99% nitric acid, ammonium nitrate solution in fuming nitric acid and conversely ammonium nitrate solution in vapouric nitric acid in acetic anhydride (S. Ju. Orlova et al .: Oktogen - tormostojoji vzryvčatoje veščestvo (Izdat. Nedra, 1975).

Similar to the nitrolysis of hexamethylenetetramine, the presence of ammonium salts in the reaction mixture favorably results in the formation of cyclic nitramines, i.e., octogen. In this case, too, there is no uniformity of views on the mechanism of action of ammonium salts in nitrolysis (cf. author's certificate no. 227 903, no. 206 382, no. 227 905 and no. 227 906, Ju. Orlova et al .: Octogen - termostojkoje vzryvčatoje vščestvo (Izdat. Nedra, 1975).

According to the latest knowledge, the presence of urea and / or urea-formaldehyde condensates and / or urea-formaldehyde condensates positively influences the formation of cyclic nitramines in the nitrolysis of hexamethylenetetramine. as well as other acid amides and their derivatives (Czech author's certificate no. 227 903, no. 206 382, no. 227 905 and no. 227 906).

Urea was applied in the nitrolysis of 1,5-diacetyl-3,7-endomethylene-1,3,5,7-tetraazacyclooctane in sulfuric acid to 1,5-diacetyl-3,7-dinitro-1,3,5,7 -tetraazacyclooctane (U.S. Pat. No. 3,926,953), in the manufacture of 1,5-endomethylene-3,7-dinitro-1,3,5,7-tetraazacyclooctane (U.S. Pat. No. 206,382) and Production of 1,3,5-trinltro-1,3,5-triazaeyclohexane (Czechoslovakian Certificate No. 227 905), other acid amides, resp. their derivatives, have been applied in the preparation of 1,3,5-trinitro-1,3,5-triaazacyclohexone by nitrolysis of hexamethylenetetramine (Czechoslovakian Author's Certificate No. 227 906).

Urea-formaldehyde condensates increase the nitrolysis yield of hexamethylenetetramine to

1,3,5-trinitro-1,3,5-triazacyclohexane (US Patent Nos. 227 903 and 227 905). The mechanism of action of these additives in the process of nitrous cleavage of hexamethylenetetramine has been suggested by hypothesis in two works (cf. author's certificate no. 227 903 and é "227 905).

According to the published data (U.S. Patent No. 97,100 and U.S. Patent No. 227,903), the presence of urea and / or urea-monofonaaldehyde condensates in the nitrolysis mixture increases their stability and hence their safety.

The present invention relates to a process for the preparation of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane by nitration of 1,5-endomethylene-3,7-dinitro-1,3,5,7-tetraazacyclooctane in acetic anhydride medium according to the invention. is that the nitrolysis process is carried out in the presence of urea-formaldehyde condensate added in an amount of 0.01 to 15.00% by weight, preferably 1 to 10% by weight, calculated on the weight of 1,5-endomethylene-3,7-dinitro- 1,3,5,7-tetraazacyclooctane.

An advantage of the present invention is an increase in the yield of proees available and the safety of nitrolysis by an additive, moreover, a process in the presence of urea-formaldehyde condensate produces a purer product than nitrolysis without the addition of this additive. Said new and higher effect in the process of producing 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane by nitrolysis of 1,5-endomethylene-3,7-dinitro-1,3,5,7-tetraazacyclooctane was not So far, in literature I have a sledge and documenting! the following examples.

Example 1

Into a suspension of 10 wt. parts of 1,5-endomethylene-3,7-dinitro-1,3,5,7-tetraazacyclooctane (0.046 kmol) in 46.2 parts by volume of acetic anhydride (0.394 kmol), presented and milled in the nitration apparatus, are dosed with solution 11, 3 wt. parts by weight of ammonium nitrate (0.138 kmol) in 13.4 parts by volume of nitric acid 99, 19% (0.318 kmol) containing 0.19 wt. analytical nitric acid. The ammonium nitrate solution is metered such that the temperature of the reaction mixture does not fall below 66 ° C and does not rise above 71 ° C (i.e., 11 min).

After dosing, a 15-minute reaction is carried out. The reaction mixture was then cooled to 25 ° C and filtered. The acidic product on the filter is suspended in 20 parts by volume of about 5% aqueous ammonia and after stirring for 10 minutes, it is filtered, washed with water and finally with 20 parts by volume of methanol. 9.9 masses result. % of 1,3,5,7-tetranitro-1,3,5,7-tetraazacycloocttene (octogen), in which melting point gpeeification showed that a small fraction of crystals melted in the range 254-269 ° C, the remainder being 282.5-283.5 ° C with decomposition. The crude product yield corresponds to 72.9% of theory.

Example 2

The procedure of Example 1 was followed except that the suspension was suspended before the ammonium nitrate solution was dosed. 0.1 wt. works of urea-formaldehyde condensate o 1 prepared in the sense of the. of the certificate No. 227 901) with a specific surface area of 11.4 m .g. 10.8 wt. parts octogen, mp 282.5 to 283.5 ^U C with decomposition. The product yield corresponds to 79.6% of theory.

Example 3

The procedure is as in Example 1, except that 0.2% by weight of the suspension is added to the suspension before the ammonium nitrate solution is added. parts of urea-formaldehyde condensate, as in Example 2. 12.7 wt. parts of octogen, m.p. 282-283 ° C with decomposition. The product yield corresponds to 93.6% of theory.

Example 4

The procedure is as in Example 1, except that urea-formaldehyde condensate of the same quality and origin as the condensate in Example 2 is added to the suspension in an amount of 1% by weight before the ammonium nitrate solution is dosed. dlel. 1C, 9 wt. parts of octogen having a melting point of 281.5 ° C to 281.5 ° C from decomposition. The product yield corresponds to 80.3% of theory.

Example 5

The procedure is as described in Example 1, except that 1,5-endomethylene-3,7-dinitro-1,3,5,7-tetraazacyclooctane obtained by nitrolysis of hexamethylenetetramine in the presence of urea-formaldehyde condensate in the reaction mixture is introduced for nitrolysis, (no. author's certificate No. 206 382), this 1,5-endo-ethylene-3,7-dinitro-1,3,5,7-tetraa-acyclooctane contains 1.6 wt. said additive. 11.9 wt. 282 DEG-293.5 DEG C. with decomposition. The product yield corresponds to 89.1% of theory, calculated on pure, reacted 1,5-endomethylene-3,7-dinitro-1,3,5,7-tetraazacyclooctane.

Example 6

The procedure is as in Example 1, except that before the ammonium nitrate solution aa is added to the present suspension! add urea-formaldehyde condensate in an amount of 0.15 wt. dlela. The condensate is obtained by curing the precondensate with 2.2 mol of formaldehyde and 1 mol of urea (curing by catalysing ammonium nitrate at 100 ° C). 12.6 wt. Mp 232-233 ° C. The product yield corresponds to 92.8% of theory.

Claims (1)

OBJECT OF THE INVENTION Method of production of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane by nitration 1,5-ethoxyethylan-3,7-dinitro-1,3,5,7-tetraazaeyclooctane in a formic anhydride, characterized in that the nitrolysis process is carried out in the presence of urea-formaldehyde condensate added in an amount of 0.01 to 15, ft0% by weight %, preferably 1 to 10% by weight, calculated on the weight of 1,5-endomethylene-3,7-dinitro-1,3,5,7-tetraazacyclooctane.