Synthesis and nitration of condensation products of sulfamates with aliphatic amines and formaldehyde

Abstract

A method for the synthesis of 5-alkyl-l,3-dinitro-I,3,5-triazacyclohexanes and linear polynitramines was proposed. It includes the reaction ofaliphatic amines with sulfamates and formaldehyde and nitration of the reaction products. The yield and composition of nitramino derivatives depend on the conditions of the condensation and nitration.

Straightforward Three-Component Synthesis of N′,N′′-Disubstituted N-Alkyl-1,3,5-Triazinanes

“…The reported methods have various disadvantages; some give mixtures of products, others require water-soluble starting materials, and some involve relatively harsh conditions that are not tolerated by some functional groups. [6][7][8] For instance, three N-tert-butyl-N′,N′′-sulfonyltriazinanes have been synthesized from N-tert-butylmethanimine and various sulfonamides in refluxing benzene in the presence of an equimolar quantity of acetic anhydride (Figure 1). 8 Moreover, possible applications of such triazinanes in both organic synthesis and as bioactive substances remain underexplored.…”

Sulfamic Acid and Its N- and O-Substituted Derivatives

“…They probed the reaction of N -alkylsulfamates with urea and formaldehyde giving 1-( N -alkylnitroaminomethyl)-3-nitroureas, RN(NO 2 )CH 2 NHCONHNO 2 , and with guanidine, nitroguanidine, H 2 NC(NNO 2 )NH 2 , 3,4-diaminofurazan, and 3-amino-4-methylfurazan giving various nitroproducts, for example, nitroguanidine gave H 2 NC(NNO 2 )NHCH 2 N(NO 2 )Me. Reaction of aliphatic amines with N -alkylsulfamates and formaldehyde in HNO 3 and acetic anhydride resulted in formation of 5-alkyl-1,3-dinitro-1,3,5-triazacyclohexanes 26 and linear nitramines 27 in reasonable yields . Nitration in HNO 3 /H 2 SO 4 of β-hydroxyalkylsulfamates gave β-nitroxyalkylnitramines, RN(NO 2 )CH 2 CH(ONO 2 )R, and nitration of the dinitroalkylsulfamates 28 , obtained from reaction of gem -dinitroalkanes, RC(NO 2 ) 2 CH 2 OH, and alkylsulfamates, gave the β-nitramino derivatives 29 …”

“…Reaction of aliphatic amines with N-alkylsulfamates and formaldehyde in HNO 3 and acetic anhydride resulted in formation of 5-alkyl-1,3-dinitro-1,3,5-triazacyclohexanes 26 and linear nitramines 27 in reasonable yields. 130 Nitration in HNO 3 /H 2 SO 4 of β-hydroxyalkylsulfamates gave β-nitroxyalkylnitramines, RN-(NO 2 )CH 2 CH(ONO 2 )R, 131 and nitration of the dinitroalkylsulfamates 28, obtained from reaction of gem-dinitroalkanes, RC(NO 2 ) 2 CH 2 OH, and alkylsulfamates, gave the β-nitramino derivatives 29. 132 Reaction of 3-(ω-haloalkoxy)-2-hydroxypropylsulfamates with amines or ammonia gave the corresponding diaminohydroxyethers, Scheme 4.…”