Substituent effects on the rate of carbene formation by the pyrolysis of rigid aryl substituted diazomethanes

NC Mathur, MS Snow, KM Young, JA Pincock

Index: Mathur, Naresh C.; Snow, Miles S.; Young, Kent M.; Pincock, James A. Tetrahedron, 1985 , vol. 41, # 8 p. 1509 - 1516

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Citation Number: 34

Abstract

Rate constants for the pyrolysis of 1-diazo-4, 4-dimethyl-1, 4-dihydronaphthalenes, 4a–4e, have been measured in methanol: 6% triethylamine. In contrast to non-rigid cases, like diphenyldiazomethanes, where all para substituents show a rate increase compared to hydrogen, these rates show a linear Hammett correlation for para substituents with σ+=— 0.84. This observation is rationalized by a non-linear process for loss of nitrogen leading ...