6-oxocyclohexa-2,4-dienylideneketene:: A highly reactive α-oxoketene

被引：36

作者：

Liu, RCY

Lusztyk, J

McAllister, MA

Tidwell, TT

Wagner, BD

机构：

[1] Natl Res Council Canada, Steacie Inst Mol Sci, Ottawa, ON K1A 0R6, Canada

[2] Univ Toronto, Dept Chem, Toronto, ON M5S 3H6, Canada

[3] Univ N Texas, Dept Chem, Denton, TX 76203 USA

[4] Univ Prince Edward Isl, Dept Chem, Charlottetown, PE C1A 4P3, Canada

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1998年 / 120卷 / 25期

关键词：

D O I：

10.1021/ja980060t

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The title ketene 2 has been generated by laser flash photolysis and observed in solution for the first time, using time-resolved infrared spectroscopy. The kinetics of the reactivity of 2 with H2O, MeOH, and Et2NH with relative reactivities of 1.0, 2.0, and 73 have been measured. These are the first direct measurements of the reactivities of a ketene with these different nucleophiles under the same conditions. Ab initio molecular orbital calculations indicate the hydration occurs by in-plane attack of the H2O molecule on the ketenyl carbonyl through a pseudopericyclic transition state with assistance by coordination to the keto-carbonyl.

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页码：6247 / 6251

页数：5

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