Synthesis of Functional 2‐Substituted 1,3‐Dinitroimidazolidines

Abstract

Three new functional 2‐substituted 1,3‐dinitroimidazolidines were synthesized herein. A synthetic strategy is suggested for structurally different α,α‐dinitraminocarboxylic acids via condensation of glyoxylic acid ethyl ester with amine or amide derivatives. Alkali‐ and acid‐catalyzed hydrolyses of ethyl 1,3‐dinitroimidazolidine‐2‐carboxylate were studied. A series of hydrolysis products were isolated. The Curtius rearrangement of 1,3‐dinitroimidazolidine‐2‐carboxylic acid to 2‐isocyanato‐1,3‐dinitroimidazolidine was carried out. Hydrolyses of 1,3‐dinitroimidazolidine‐2‐carbonyl azide and 2‐isocyanato‐1,3‐dinitroimidazolidine were studied. 1,3‐Dinitroimidazolidine‐2‐amine was captured as 1,3‐bis(1,3‐dinitroimidazolidin‐2‐yl)urea.

Synthesis of Diaminoacetic Acid Derivatives as a Promising Scaffold for the Synthesis of Polyheterocyclic Cage Compounds

“…We previously revealed a negative inductive effect of two nitro groups in bis­(nitroamino)­acetic acid derivatives on the progress of the Curtius, Hofmann, or Schmidt rearrangement . In this regard, we decided to examine the progress of the said rearrangements using other cyclic and polycyclic diaminoacetic acid derivatives with substituents having a lower negative inductive effect.…”

“…Previously, we indirectly corroborated the possible transformation of the carboxyl group in the bis(nitroamino)acetic acid moiety (Scheme 2) into the amino group. 7 1,3-Bis(1,3dinitroimidazolidin-2-yl)urea (1) (37.5% yield) was prepared by reacting 1,3-dinitroimidazolidine-2-amine with 2-isocyanato-1,3-dinitroimidazolidine (2) (Scheme 2).…”