Asahara Haruyasu, Arikiyo Keita, Nishiwaki Nagatoshi
School of Environmental Science and Engineering, Kochi University of Technology, Tosayamada, Kami, Kochi 782-8502, Japan ; Research Center for Material Science and Engineering, Kochi University of Technology, Tosayamada, Kami, Kochi 782-8502, Japan.
School of Environmental Science and Engineering, Kochi University of Technology, Tosayamada, Kami, Kochi 782-8502, Japan.
Beilstein J Org Chem. 2015 Jul 23;11:1241-5. doi: 10.3762/bjoc.11.138. eCollection 2015.
N-Methylated amides (N,4-dimethylbenzamide and N-methylcyclohexanecarboxamide) were systematically subjected to chemical transformations, namely, N-tosylation followed by nucleophilic substitution. The amide function was converted to the corresponding carboxylic acid, esters, amides, aldehyde, and ketone upon treatment with hydroxide, alkoxide, amine, diisobutylaluminium hydride and Grignard reagent, respectively. In these transformations, N-methyl-N-tosylcarboxamides behave like a Weinreb amide. Similarly, N-methyl-5-phenylisoxazole-3-carboxamide was converted into 3-functionalized isoxazole derivatives. Since the amide was prepared by the cycloaddition reaction of ethynylbenzene and N-methylcarbamoylnitrile oxide, the nitrile oxide served as the equivalent of the nitrile oxides bearing a variety of functional groups such as carboxy, alkoxycarbonyl, carbamoyl, acyl and formyl moieties.
N-甲基化酰胺（N,4-二甲基苯甲酰胺和N-甲基环己烷甲酰胺）系统地进行了化学转化，即先进行N-甲苯磺酰化，然后进行亲核取代。酰胺官能团分别用氢氧化物、醇盐、胺、二异丁基氢化铝和格氏试剂处理后，转化为相应的羧酸、酯、酰胺、醛和酮。在这些转化中，N-甲基-N-甲苯磺酰基羧酰胺的行为类似于Weinreb酰胺。同样，N-甲基-5-苯基异恶唑-3-甲酰胺转化为3-官能化异恶唑衍生物。由于该酰胺是通过乙炔基苯与N-甲基氨基甲酰腈氧化物的环加成反应制备的，腈氧化物相当于带有各种官能团如羧基、烷氧羰基、氨基甲酰基、酰基和甲酰基部分的腈氧化物。
