School of Environmental Science and Engineering, Kochi University of Technology, Tosayamada Kami, Kochi, 782-8502, Japan.
Org Biomol Chem. 2011 Apr 21;9(8):2832-9. doi: 10.1039/c0ob01005g. Epub 2011 Feb 24.
A nitrile oxide containing a carbamoyl group is readily generated upon the treatment of 2-methyl-4-nitro-3-isoxazolin-5(2H)-one with water under mild reaction conditions, even in the absence of special reagents. The obtained nitrile oxide undergoes cycloaddition with dipolarophiles, alkynes and alkenes, to afford the corresponding isoxazol(in)es, which are useful intermediates in the synthesis of polyfunctionalized compounds. A plausible mechanism underlying the formation of the nitrile oxide is proposed, which involves an anomalous hydration/dehydration sequence. DFT calculations were also performed to support this mechanism.
在温和的反应条件下，即使没有特殊试剂，2-甲基-4-硝基-3-异恶唑啉-5(2H)-酮与水反应也会迅速生成含有氨基甲酰基的腈氧化物。所得的腈氧化物与偶极子、炔烃和烯烃进行环加成反应，生成相应的异恶唑啉（in），它们是多功能化合物合成中的有用中间体。提出了一个合理的腈氧化物形成机制，其中涉及异常的水合/脱水序列。还进行了 DFT 计算来支持该机制。
