KINETICS OF METHANOLYSIS OF AND OF SODIUM METHOXIDE INDUCED ELIMINATION FROM SUBSTITUTED BENZYLDIMETHYLCARBINYL CHLORIDES

Rates of methanolysis of a series of substituted benzyldimethylcarbinyl chlorides at three temperatures obey the Hammett equation with ρ ca. -0.9. ΔS‡ is in most cases about -4 gibbs/mol. Rates of reactions of ρ-nitro- and 3, 5-dichlorobenzyldimethylcarbinyl chlorides with NaOMe in MeOH to form isomeric olefins have been measured. When taken in conjunction with literature data, our measurements for ArCH=CMe2 formation necessitate use of μ for ρ-NO2 to give good Hammett correlation, with ρ +1.2. For formation of ArCH2C(Me)=CH2, ρ is essentially zero (−0.07). The data for the NaOMe reactions are successfully interpreted in terms of variable transition state E2 theory, but do not support an alternative theory that postulates attack of base on an ion pair. © 1979, American Chemical Society. All rights reserved.