CS227913B1 - Production 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 - Google Patents

Abstract

The invention relates to a process for producing 1,3,5,7- -tetranitro-1,3,5,7-tetraesacyclooctane nitrolysis 1,5-diacetyl-3,7-dinitro-1,3,5, - 7-tetraazaecyclooctane with nitric acid contain nitric oxide, river production soothing from the process of non-electrolysis is carried out in the presence of urea into the nitrolysis system added in amount 0.05 to 10.0 wt.%, Calculated on weight to the recurring 1,5-diaoethyl-3,7-dinltro-1,3,5,7-tetraazacycloctane.

Description

The present invention relates to the preparation of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane by nitrolysis

1,5-acetyl-3,7-dihydro-1,3,5,7-tetraazacyclooctane with a mixture of nitric acid and nitric oxide, wherein the reaction conditions are chosen such that they favorably influence the economics of the process.

1,3,5,7-tetranitro-1,3,5-7-tetraazecyclooctane, also aspirated octogane and designated HMX, is conveniently produced by nitrolysis of hexamethylantetramine, preferably in acetic acid and acetic anhydride, or by nitrolysis of 1,5-endomethylan -3,7-dinitro-1,3-5,7-tetraazacyclooctane (Orlova E. Ju. Et al .: Oktogen - thermostasis in water,

Izdat. Nedra. Moscow, 1978).

In recent years, however, data have been reported in octane production processes, also based on hexamethylanetetramine, which, however, is first converted to 1,5-dialkanoyl-3,7-endomethylene-1,3,5,7-tetraazacyclooctene (Slele VI, Warman M., Gilbert EE:

J. Heteroeyel. Chem. 1974, 11, 237; OSA pat. no. No. 3,850,923) and the melt is then further nitrolyzed to octogane. Processes based on this basis show a higher yield of purer 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane than classical nitrolysis of hexamethylantetramine.

The octogane synthesis method, starting from 1,5-diacetyl-3,7-endoraethylene-1,3,5,7-tetraazacycloctocane (U.S. Nos. 3,849,414 and 3,850,923), appears to be very attractive in practice, which is nitrolysed in sulfuric acid medium at very high yields to 1,5-di-ethyl-3,7-dinitro-1,3,5,7-tetraazacycloctane, designated DABN (U.S. Pat. No. 3,926,953), which is then nitrolized with nitration mixtures containing up to 50 wt. nitric oxide, to octogane (U.S. Pat. No. 3,939,148).

The yields of 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane, calculated on the incoming hexamethylanetetramine, are reported to be 91-98% of theory (U.S. Pat. No. 3,850,923 and U.S. Pat. 3,926,953) and the nitrolysis yield of said compound to octogane is 41-98%, depending on the reaction conditions, relative to theory (U.S. Patent No. 3,939,148).

A disadvantage of the known process of nitrolysis of 1,5-diacetyl-3,7-dinotro-1,3,5,7-tetraazaeyklooktan is that a large excess of freshly distilled anhydrous nitric acid over theory is required to ensure a high octogan yield (U.S. Pat. 3,939,148), e.g. to achieve a 98% yield of pure octogane is 1 wt. DADN consumed 33.7 wt. parts by weight of anhydrous duic acid and 11.23 wt. parts of phosphorus pentoxide.

In response! nitrous cleavage of 1,5-diacetyl-3,7-dlnitro-1,3,5,7-tetraazacyclooctane by mixtures containing nitric oxide depending on the reaction conditions, but not least on the source of this oxide (a combination of nitric acid and phosphoric acid; or sulfur trioxide or trifluoroacetic anhydride or a solution of nitric oxide in nitromethane or nitric acid (U.S. Pat. No. 3,939,148) also causes cleavage of the 1,3,5,7-tetraazacyclooctocane skeleton.

This undesired reaction in the case of the synthesis of other cyclic ntramines can be suppressed by a component capable of exiting acidolytic equilibria on the side of the products of these reagents and, on the other hand, exhibiting a higher affinity for nitrogen oxides than nitroles. compound. Recent evidence (U.S. Pat. No. 3,926,953, U.S. Author's Certificate No. 206,382, No. 227,906, and No. 213,509) is a component such as urea.

SUMMARY OF THE INVENTION 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 an acid The nitrous oxide-containing reaction is carried out in such a way that the nitrolysis process takes place in the presence of urea to the nitrolysis system added in an amount of 0.05 to 10.0% by weight, preferably in an amount of 0.5 to 5.0% by weight, calculated on the reaction of taken 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacycloctane.

The advantage of this invention in addition to the already mentioned economic effect is potentially the possibility of heightening and stability of the reaction mixture and hence process safety, since the stabilizing effect of urea and its derivatives in nitrolytic reactions is well known (U.S. Pat. No. 97,100; , Denkstein J .: Coll., Czech, Chem. Commun., 1960, 25, 1070, Czechoslovakian Author's Certificate No. 227 903 and others.

The novel and higher effect achieved according to the invention has not been described in the literature and is documented by the following examples.

'EXAMPLE

210 obj. parts by weight of nitric acid 97.15% with a content below 0.2% by weight. of analytical nitric acid (i.e. 307 pbw of anhydrous nitric acid) was cooled to -10 ° C while stirring. 120 wt. parts of phosphorus pentoxide such that the temperature of the resulting mixture does not exceed 25 ° C. After the introduction of phosphorus pentoxide, the mixture is heated to a temperature of 33 to 36 ° C at this temperature, while stirring, 20 wt. parts of 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane.

Thereafter, the resulting reaction mixture is heated to 58-62 ° C over a period of 4 to 6 minutes and maintained at this temperature range for 15 minutes. After this time, the mixture is poured into 500 vol. parts of cold water. The suspension thus formed is brought to boiling and maintained there until the nitrogen oxides cease to escape (about 20 to 30 minutes).

After cooling the suspension to 18-25 ° C, the product is isolated by filtration and washed on the filter with water to neutralize the filtrate. After drying at 90 to 95 ° C, the melting point is determined for the octogen thus obtained. This basic procedure is repeated several times with the addition of a certain amount of urea to the present nitric acid in addition to the 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazaeyclooctane being metered. The results are represented by tabs.

Depending on the amount of urea added to the reaction system, it is apparent that the optimum addition of urea is 1.7 to 2.5% by weight, calculated on the weight of 1,5-diacetyl-3,7-dlaitro-1,3,5,7 -tetraazacykleoktánu. Furthermore, it is apparent from this dependence that under the experimental conditions up to 85.26% can be achieved compared to the theory of pure octogen yield at 15.35 wt. parts by weight of nitric acid as anhydrous, 6 parts by weight, parts by weight of phosphorus pentoxide and 0.02 parts by weight; parts of urea per 1 wt. parts reacted with 1,5-diacetyl-3,7-dinitro-1,3,5,7-tetraazacyclooctane.

Claims (1)

SUBJECT OF THE INVENTION Method 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, characterized by: The nitrolysis process is carried out in the presence of urea in the nitrolysis system added in an amount of 0.05 to 10.0% by weight, preferably in an amount of 0.5 to 5.0 K by weight, calculated on the weight of the reaction taken into account. 5-diacetyl-3,7-dlnitro 1,3,5,7-tetraasacyclooctane.