Spectroscopic detection of an ...



Title Spectroscopic detection of an arylchlorocarbene-ethyl acetate carbonyl ylide and subsequent oxirane formation
Author(s) J. E. Chateauneuf, Michael T. H. Liu
Journal Journal of the American Chemical Society
Date 1991
Volume 113
Issue 17
Start page 6585
End page 6588
Abstract Laser flash photolysis of 3-chloro-3-(p-nitrophenyl)diazirine (1) generates the corresponding ground-state singlet carbene (lambda-max = 310 nm), which reacts with ethyl acetate to form a carbonyl ylide of the ester (lambda-max = 490 nm). The absolute rate constant for ylide formation in CH2Cl2 is k = (2.85 +/- 0.17) X 10(6) M-1 s-1. Subsequent cyclization of the ylide to the corresponding oxirane (lambda-max = 350 nm) occurs with a rate constant of 1.26 x 10(6) S-1 (21-degrees-C) in ethyl acetate with Arrhenius activation parameters for oxirane formation of E(act) = 6.68 +/- 0.19 kcal/mol and log A (s-1) = 11.08 +/- 0.15. The carbonyl ylide is also intercepted with the dipolarophile, diethyl fumarate, with a rate constant of (1.04 +/- 0.07) x 10(7) M-1 s-1. Additionally, solvent polarity effects on (p-nitrophenyl)chlorocarbene reactivity and spectroscopic evidence of oxirane formation (lambda-max = 350 nm) from the related acetone ylide of (p-nitrophenyl)chlorocarbene are presented.

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