ChemInform Abstract: DERIVATIVES OF NITRAMINOMETHYLOLS. II. CHLORINATION OF N‐HYDROXYMETHYLETHYLENEDINITRAMINE BY THIONYL CHLORIDE

Aliphatic nitramino alcohols and their derivatives

“…39,40, 67 In the presence of aprotic acids, chloromethylnitramines alky lated benzene 67 and added to alkenes affording γ chloro alkylnitramines (Scheme 54). 68…”

“…The significant achievement in the chemistry of the functionalized nitramines was the synthesis of N alkyl N vinylnitramines from 2 nitroxyethyl and 2 chloroethyl nitramines. 13, 67 Study of the geometry, 82 electronic structure, the IR, UV, and 1 H NMR spectra (see Ref. 13) as well as the reactivity of N vinylnitramines provided valuable infor mation about structure and electronic effects of the nitr amine group as well as opened new prospects in chemistry of nitramines.…”

“…84, 85 Dichlorocyclopropyl fragment possessed high chemi cal stability and remained unchanged in various chemical reactions (Scheme 57). 84 N Dichlorocyclopropyl N methylnitramine with stands the treatment with acids and alkali metal alkoxides. In contrast, heating of N dibromocyclopropyl N meth ylnitramine with methanolic sodium methoxide resulted in a mixture of cis and trans isomers of N (2 bromocy clopropyl) N methylnitramine.…”

“…13, 81 The specific synthetic methods toward 1 chloro 3 nitro 3 azaalkanes are the decomposition of 1 acetoxy 2,5 dinitro 2,5 diazaalkanes using hydrochlo ric acid 6 and treatment of 1,4 dinitro 1,4 diazaalkanes with thionyl chloride. 67 1 Chloro 3 nitro 3 azaalkanes are of interest as nitr aminoalkylating agents. The chlorine atom could be substi tuted by the amino, 12 hydrazino, 12 azido 13,79 and alkoxy 12,41 groups.…”

Efficient synthesis of N-(chloromethyl)nitramines via TiCl4-catalyzed chlorodeacetoxylation

“…1). It has been reported that reagents such as acetyl chloride/ZnCl 2 (5 examples), 33 acetyl chloride/AlCl 3 (3 examples), 34 and thionyl chloride in the presence of a catalyst, H 2 SO 4 or H 2 SO 2 /AcOH (10 examples) [35][36][37][38][39]41 can be used for this conversion. Compounds 1 were also prepared by treating a mixture of N-chloro-Nnitroalkylamine 4 and paraform with hydrogen chloride in 1,4-dioxane (6 examples).…”