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Tetrahedron Ldtera, 1970, 232 233 3816. 249 A. C. Hopkinson and P. A. H. Wyatt, J . Chem. Soc. 630. 46) by assuming an additive effect of the individual groups on the benzene ring. u+ constants for the p-benzyP6 and allyl groupse6ehave been determined by kinetic studies on the solvolysis of 2-p-benzylphenyl-2-chloropropane and allyl substituted cumyl p-nitrobenzoates. Solvolysie rates for l-arylethyl acetatese6' and 1-(2-thienyl)ethyl and 1-(3-thienyl)ethyl p-nitrobenzoates2K8have been correlated against u+ constants.

From the nature of the products the cyclopropyl moiety still appeared to control product formation, indicating that the charge still tends to reside primarily at C-2 rather than at the tertiary centre stabilized by the p-anisyl group. PNBO & y M e __+ y% MeO> OH OPNB (114) 166 B. Fraser-Reid and B. Radatua, Can. J . , 48,2146 (1970). A. Nishimura, M. Ohts, and H. Kato, Bull. Soc. Japan, 48,1630 (1970). Bozimo, and P. Wolf, Tetrahedron Letteru, 1970,2396. 168 168 R. Maurin and M. Bertrand, TetraMrm Letter4 1970,1307.

Japan. 42, 3034 (1969). 197 P. Q. Geesmen end J. H. Dygoa, Tetrahedron Lettcre, 1970,4746. 138 P. Q. Owman and J. H. Dygoe, Tetrahedron Letlers, 1970,4749. 180 0. D. Sergent end M. J. Herriaon, T e t d t d m Lc(ler8,1970,3699. 189 D. J. 130 M. 1 I CH2' I CH2+ CHnX order of reactivity. I4l As the temperature was raised from 0 to 95", the two methyl bands began to broaden a t 35" and coalesced a t 85". 9 kcal mole-', and this coalescence mechanism was concluded ta be due to rotation about the C=C bond.

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