摘要:

It has been found possible to convert diethanolamine to β,β-dinitroxydiethylnitramine by inclusion of hydrogen chloride or one of its salts as catalyst. The structure of this powerful explosive has been demonstrated by an alternative synthesis involving nitrosation of dinitroxydiethylammonium nitrate, followed by subsequent oxidation of dinitroxydiethylnitrosamine to the corresponding nitramine. The nitrosamine, which is unstable in boiling water, is evidently an impurity in the crude nitramine. It may be removed from the stable nitramine by blowing the suspension of molten crude product with steam. The pure explosive is a stable low-melting solid with power and detonation rate higher than those of nitroglycerin. Its insensitiveness to impact as compared with nitroglycerin recommends it as a replacement for the latter substance in explosive compositions.

ISSN:1923-4287    

DOI:10.1139/cjr48b-011

出版商:NRC Research Press    

年代:1948

数据来源: NRC

摘要:

Titration of a series of secondary amines with sulphuric or perchloric acid in acetic acid shows that those amines which do not require a chloride catalyst for their nitrations are more weakly proton-accepting than the amines which cannot be nitrated without catalyst. The weak proton-acceptance of imino-bis-acetonitrile which can be nitrated without catalyst is further typified by its tendency to co-ordinate with itself in 16% association in acetic acid solution. By contrast, dibutylamine, which cannot be nitrated without catalyst, is not associated in this medium.

ISSN:1923-4287    

DOI:10.1139/cjr48b-012

出版商:NRC Research Press    

年代:1948

数据来源: NRC

摘要:

A series of secondary amines, the proton-attracting ability of which had previously been determined, have been converted to their nitramines with nitric acid and acetic anhydride. The gradation in ease of nitration has been found to vary inversely with the proton-attracting ability of the amine. Nitration becomes so difficult at an amine strength corresponding to that of diethanolamine that nitric acid and acetic anhydride alone are ineffective; a chloride catalyst must be used. The amount of this catalyst must be increased as the proton-attracting ability of the amine becomes greater until a full equivalent is required for adequate yield from the strongest amine in the series, diisopropylamine. As the nitration in the series becomes more difficult, side reactions become apparent such as nitrosation, acetylation, and fission of the secondary amine to primary amine and aldehyde. The extent of nitrosation is dependent on the concentration of catalyst, although nitrosation is not catalyzed by presence of chloride. This implies that hydrogen chloride generates nitrous acid in the reaction mixture. Acetylation is independent of presence or concentration of catalyst, but it does not occur during the formation of dicyclohexylnitramine or diisopropylnitramine. This is thought to be owing to steric hindrance from the secondary alkyl groups in these amines. Since nitracidium perchlorate has been found to be ineffective as a catalyst for this nitration, it is doubtful that nitryl chloride is the active form of the catalyst except in so far as it exists in the form of chlorine nitrite. Evidence has accumulated to show that electropositive chlorine is the effective catalyst, and that it is formed by a modification of the aqua regia reaction.

ISSN:1923-4287    

DOI:10.1139/cjr48b-013

出版商:NRC Research Press    

年代:1948

数据来源: NRC

摘要:

The nitration of lysidine with acetic anhydride, nitric acid, and a chloride catalyst does not yield the expected nitrolysidine. The product, instead, is 1,3-dinitroimidazolidone-2 when little or no chloride is used. A new compound is produced when a full equivalent of hydrogen chloride is included. This new compound is thought to be 1,3-dinitro-2-chloromethyl-2-acetoxylimidazolidine. Its decomposition products are ethylenedinitramine and chloroacetic acid. It is believed to be cyclic because the linear isomer, N-acetyl-N′-chloroacetylethylenedinitramine has been prepared and found not to be identical. The formation of dinitrochloromethylacetoxylimidazolidine in the nitration mixture suggests that it is formed by addition of chlorine acetate. This compound has been prepared, characterized, and found to add to allylbenzene. Since it will convert dicyclohexylamine to the chloramine it is postulated as a temporal ingredient of the catalyzed nitration mixture.

ISSN:1923-4287    

DOI:10.1139/cjr48b-014

出版商:NRC Research Press    

年代:1948

数据来源: NRC