Amines nitroguanidines

Nitrogen triiodide a-Nitroguanidine Nitromethane Acids, bromine, chlorine, hydrogen sulfide, ozone Complex salts of mercury and silver Acids, alkylmetal halides, hydroxides, hydrocarbons, organic amines, formaldehyde, nitric acid, perchlorates... 

The previous review1 has treated in detail only the following amines methylamine, dimethylamine, trimethylamine, 2-aminoethanol, ethylenediamine, nitroguanidine and similar ones. In the period of the present review, some simple molecules of interest have been treated such as the aminoethanol series, including mono-, di- and tri-substituted derivatives, as well as a number of derivatives of guanidine. These will be dealt with for purposes of internal comparison. 

Compounds of type (XVIII) have been prepared by reduction of a nitroguanidine [199], by reaction of an amine with 5-methylisothiosemicarbazide [131,194,199,200], or by reaction of hydrazine with a substituted S-methyliso-thiouronium salt [131, 193]. 

This method is commonly applied to the nitration of primary amines (3) and in particular the preparation of nitroguanidine, nitrourea etc., as well as in the nitration of secondary amines (4) ... 

Another method of dehydration of the amine nitrate is based on treatment with concentrated sulphuric acid. This is used commercially in manufacturing such primary amines as nitroguanidine (p. 31). 

In the presence of primary aliphatic amines in aqueous solution nitroguanidine undergoes decomposition according to equation (22). Ammonia is then evolved, and nitrocyanamide combines with the amine to form alkylnitroguanidine, e.g. N-methyl-N -nitroguanidine ... 

Individual amines and their nitrated derivs used in expl, propellent and pyrotechnic compns are described separately under their own names, such as cyclonite, nitroguanidine, tetryl, etc... 

In the absence of ammonia and in the presence of a primary aliphatic amine, nitroguanidine in aqueous solution dearranges in the second of the above-indicated modes, ammonia is liberated, and the nitrocyanamide combines with the amine to form an alkylnitroguanidine. 

The structure of the N-alkyl,N -nitroguanidine is demonstrated by the fact that it yields the amine and nitrous oxide on hydrolysis, indicating that the alkyl group and the nitro group are attached to different nitrogen atoms. 

N-Allylguanidine A zide, QH,Ne—was not found in Beil or CA through 1956 N-Allyl-N -nitroguonidine or l-Allyl-3-3-nitroguanidine, CH, CH. CH,. NH. C( NH) NH.NO, mw 144.14, N 38.87% crysts, mp 107-8°. Can be prepd by the interaction allyl-amine and N-methyl-N1 -nitroguanidine by the method B of Ref 3. This high nitrogen compd which may be suitable as a component of propellants was also prepd at the US Naval Powder Factory and described in coni rept (Ref 2)... 

Several lesser known nitrating agents, which can find practical use on a laboratory scale are metal nitrates in the presence of acetic acid or acetic anhydride, described by Menke [2], tetranitromethane and hexanitroethane in an alkaline medium, used by Schmidt [3], Mid nitroguanidine in solution in sulphuric acid, used for the nitration of aromatic amines Mid phenols. 

Crysts, mp 141.2° with decompn. Can be prepd by treating a soln of 2-nittamino-A -in)idazo-line in 70% nitric acid with NaNO,. Treating l-nitroso-2-nitramino -A -imidazoline with aromatic amines in aq ethanol at 30° gave l-substituted-2-nitramino-AMmidazoIines and 1,2-disub stituted-3-nitroguanidines... 

N-Methyl-N-nitroso-N -nitroguanidine added at 22 to a mixture of an ethereal p-methoxyaniline soln. and water, worked up after the gas evolution has ceased N-(p-methoxyphenyl)-N -nitroguanidine. Y 92.5%.—The reaction time varies from several hrs. to several days depending on the amine and the solvent used. The more basic amines react faster. (F. e. s. A. F. McKay, Am. Soc. 71,1968 (1949).)... 

The reaction of nitroguanidine with amines has been reviewed by McKay.1159... 

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