Journal of Organic Chemistry p. 2976 - 2984 (1980)
Update date:2022-09-26
Topics:
McDonald, Richard N.
Cousins, Raymond C.
The synthesis of certain phenyl-substituted derivatives of the isomeric trans-β-chlorostyrene oxides (6) and α-chlorostyrene oxides (7) are reported.The kinetics of rearrangement of 6 (X = p-CH3, H, p-Br, m-Cl, p-NO2) to phenylchloroacetaldehydes (12) in CCl4 buffered by Na2HPO4 and 7 (X = p-CH3, H, p-NO2) to ω-chloroacetophenones in CCl4 were determined by following the rates of disappearance of the α-chloro epoxide and formation of the α-chloro carbonyl product.These substituent effects at 130 deg C were correlated with ?+ constants, yielding ρ values of-3.5 and -0.57 for the rearrangements of 6 and 7, respectively.In nitrobenzene solvent, the kC6H5NO2/kCCl4 for 6 was 180 and for 7 was 1740, the latter solvent effect attributed to nucleophilic solvent participation.It was concluded that these thermal rearrangements of 6 and 7 occur by disrotatory Cβ-O bond heterolysis to yield the corresponding α-keto carbonium-chloride ion pairs.
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