Imidoylketene dimerization and rearrangement

被引：21

作者：

George, L ^{[1
]}

Bernhardt, PV ^{[1
]}

Netsch, KP ^{[1
]}

Wentrup, C ^{[1
]}

机构：

[1] Univ Queensland, Dept Chem, Sch Mol & Microbial Sci, Brisbane, Qld 4072, Australia

来源：

ORGANIC & BIOMOLECULAR CHEMISTRY | 2004年 / 2卷 / 23期

关键词：

D O I：

10.1039/b412530d

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

FVT of pyrroledione 10 affords the NH-imidoylketene 11, which is characterized by its matrix isolation IR spectrum ( 2117 cm 1). On warming above 170 K, 11 dimerizes to the oxazinone 13, the X-ray crystal structure of which is reported. Imidoylketene 11 also undergoes a (reversible) 1,3-phenyl shift to afford the detectable alpha-oxoketenimine 16 (2062 cm(-1)) which at FVT temperatures above 400degreesC, isomerizes to 2-cyano-2-phenylacetophenone 18 (optimally at 700degreesC). Moreover, imidoylketene 11 can cyclize to azetinone 19, detectable at FVT temperatures up to 570degreesC, which undergoes cycloreversion to diphenylacetylene 20 and isocyanic acid (HNCO) 21. Energy profiles calculated at the B3LYP/6-31G** level for the unsubstituted imidoylketene, the diphenylimidoylketene 11 and the N-tert-butylimidoylketene are also reported.

引用

页码：3518 / 3523

页数：6

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