Mechanistic studies on the Wolff rearrangement: the chemistry and spectroscopy of some. alpha.-keto carbenes

RJ McMahon, OL Chapman, RA Hayes…

文献索引：McMahon, Robert J.; Chapman, Orville L.; Hayes, Richard A.; Hess, Thomas C.; Krimmer, Hans-Peter Journal of the American Chemical Society, 1985 , vol. 107, # 25 p. 7597 - 7606

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被引用次数: 108

摘要

Abstract: Photochemical extrusion of dinitrogen from diazo ketones 1-4 matrix isolated in argon at 10-15 K produces a-ketocarbenes 5, 6, and 8. UV-vis, infrared, and electron spin resonance spectroscopy identify the a-ketocarbenes, which are further characterized by trapping with carbon monoxide and dioxygen. Excitation (To-T,) of the a-ketocarhcies leads to rapid ring contraction of 5-9 and slow ring contraction of 6-10 and 8-12. This trend ...