Author:
Veedu Rakesh N.,Kvaskoff David,Wentrup Curt
Abstract
The matrix photolyses of 3-phenyl-, 3-pyridyl, and 3,4-diphenylsydnones 16, 19, and 22 were investigated by matrix-isolation infrared spectroscopy. The formation of the neutral, bicyclic lactone valence isomers postulated by Earl – the oxadiazabicyclo[2.1.0]pentanones exo-17 and exo-20 – was clearly observed in the first two cases and is also likely in the case of exo-23 (C=O absorptions in the IR at 1881, 1886, and 1874 cm–1, respectively). The efficient photodecomposition of sydnones to carbodiimides RN=C=NR′ (18, 21, and 24) and CO2 was established in all three cases. The formation of benzonitrile 27 and azacycloheptatetraene 29 in the matrix photolysis of diphenylsydnone 22 is indicative of diphenylnitrile imine PhCNNPh 26 as an intermediate (2340 cm–1). Neither bicyclic lactones nor carbodiimides have been observed previously in sydnone photochemistry. A general reaction mechanism for the formation of carbodiimides, nitrile imines, and photochromism is put forward.
Cited by
23 articles.
订阅此论文施引文献
订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献