65112-55-2Relevant articles and documents
INTERMOLECULAR IMIDOYLATION REACTION OF THE CARBOXAMIDE GROUP
Mazurkiewicz, Roman
, p. 439 - 450 (2007/10/02)
Reactions of N-monosubstituted benzamides with Ph3PBr2 and Et3N in refluxing CH2Cl2 for 0.5 - 5 hours give good yields of N,N'-disubstituted-N-acylamidines.The latter compounds may be regarded as intermolecular N-imidoylation products of the amide group.Under the same reaction conditions, N-monosubstituted amides containing C-H bonds adjacent to the carbonyl function and N-monosubstituted formamides are dehydrated to ketenimines and isonitriles, respectively.Treatment of N-methyl-benzamide with Ph3PBr2 and Et3N leads to the formation of an intermediate whose ir spectrum is consistent with the N,N,N-triethyl-N'-methylbenzamidinium salt structure.A substance with identical spectroscopic characteristics was obtained on treatment of N-methyl-α-bromobenzylideneammonium bromide with Et3N.Products of the reaction of 5- and 6-membered lactams with Ph3PBr2 and Et3N are inactive as imidoylating agents; consequently, these lactams do not undergo self-condensation to N-imidoylation products, but they can participate in the imidoylation reactions as nucleophiles subjected to imidoylation.In contrast to the 5- and 6-membered lactams, ε-caprolactam undergoes self-condensation to the expected N-imidoylation product.Possible mechanistic pathways for the imidoylation reaction of the amide group have been suggested.
