Amide formation formic acid

Ai -Cyclopropoxymethyl-7V-methyl amides of formic acid and acetic acid have been obtained in moderate yield by treating the corresponding trimethylsiloxycyclopropanes with mixtures of ethyl azidoformate and dimethylformamide (e.g. formation of 6) and Af,Af-dimethylacet-amide, respectively, at 120 C. Presumably, the reaction involves a singlet nitrene species. 

Lithium aluminum hydride reduction of 7V-formylcorydamine afforded the tertiary base 5, and sodium formate-formic acid formylation of corydamine produced material identical with A -formylcorydamine, thus completing the structural elucidation of this amidic alkaloid (Scheme 22.2). ... 

Ethonam (99), an imidazole derivative with a very different substitution pattern, is also reported to possess antifungal activity. To prepare it, alkylation of aminotetralin 94 with methylchloro-acetate gives the glycine derivative 95. Heating with formic acid then affords the amide 96 this compound is then reacted with ethyl formate to yield hydroxymethylene ester 97. Reaction with isothio-cyanic acid gives the imidazole-2-thiol 98. (The... 

Oie, T., G. H. Loew, S. K. Burt, J. S. Binkley, and R. D. MacElroy. 1982. Ab Initio Study of Catalyzed and Uncatalyzed Amide Bond Formation as a Model for Peptide Bond Formation Ammonia-Formic Acid and Ammonia-Glycine Reactions. Int. J. Quantum Chem. Quantum Biol. Symp. 9, 223-245. 

As mentioned above, the bis-amides 9a are used as precursors in the synthesis of Af-acylenamines. The conditions used for this reaction depend on the purpose of the synthesis and are described in numerous works, and reviewed in a series of articles35-37. The acid catalyst is usually concentrated sulfuric acid, but a successful application of 85% phosphoric, chlorosulfonic, methanesulfonic and formic acids was reported, and reactions were also conducted in the presence of anhydrous hydrogen chloride35. The solvents used are usually glacial acetic acid and chlorinated hydrocarbons. It is believed that the water necessary for the formation of the bis-amides under anhydrous conditions is obtained from conversion of the carboxylic acid to the anhydride, or even the sulfuric acid35. 

Wiberg, K. B., and Laidig, K. E., Barriers to rotation adjacent to double bonds. 3. The C—O barrier in formic acid, methyl formate, acetic acid, and methyl acetate. The origin of ester and amide resonance", J. Am. Chem. Soc. 109, 5935-5943 (1987). 

Interaction of 258 with anilines or five-membered nitrogen heterocycles produced 265 and 266 via an aminoalkylation . Bicyclic derivatives 267-271 with an aminal structure resulted from the interaction of 258 with amides, urethanes, imides, ureas, amines or hydrazines. Finally, 272 was formed with carbon acids and a reduction to 273 occurred with the sodium salt of formic acid " . It is not yet totally clear whether an iminium ion is involved in the formation of 259-273. The yields of isolated products varied from 45 to 95 %. 

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