Reagents for Bioorganic Synthesis. 2. Methyl N-(Dicarboxymethyl)methanimidate

Article abstract of DOI:10.1021/jo00225a026

Preparation, properties, and reactions of the reagent methyl N-(dicarbomethoxymethyl)methanimidate (1) are reported.Dropwise addition of dimethyl aminomalonate to refluxing trimethyl orthoformate/TFA afforded 1.Treatment of 1 with ammonia and various primary amines gave the corresponding unsubstituted and 1-substituted 4-carbomethoxy-5-hydroxyimidazoles 7-12, either as the parent hydroxy compounds (a) or as the (alkyl)ammonium salts (b).The reaction of 1 with water and sodium hydrosulfide provided dimethyl N-formylaminomalonate (13) and dimethyl N-(thioformyl)aminomalonate (14), respectively.The reaction of 1 with excess sodium hydrosulfide resulted in the formation of methyl N-(thioformyl)aminoacetate (17).Conversions of methylammonium 4-carbomethoxy-1-methylimidazol-5-olate (8b) and benzylammonium 4-carbomethoxy-1-benzylimidazol-5-olate (9b) into 5-(benzylamino)-4-(benzylcarbamoyl)-1-methylimidazole (18) and 1-benzyl-5-(benzylamino)-4-(benzylcarbamoyl)imidazole (19), respectively, were each accomplished in a single-pot procedure, employing phenylphosphonic dichloride as the key reagent.