5317-66-8Relevant academic research and scientific papers
Chlorinations with Carbon Tetrachloride under Conditions of Phase Transfer Catalysis
Lauritzen, Stein Erik,Roemming, Christian,Skatteboel, Lars
, p. 263 - 268 (2007/10/02)
Anion of ketones, sulfones and esters were α-chlorinated by carbon tetrachloride under conditions of phase transfer catalysis (PTC).Alcohols were unreactive.The observed products show that secondary reactions took place in many cases.The chlorination of the sulfone cis-2,5-diphenyltetrahydrothiophene-1,1-dioxide (1) occurred with inversion to give trans-2,5-dichloro-2,5-diphenyltetrahydrothiophene-1,1-dioxide (2).The structures of cis-1 and trans-2 were determined by X-ray diffraction.The reaction conditions are also applicable to brominations using bromotrichloromethane.
Molecular Rearrangements. 13. Kinetics and Mechanism of Rearrangements of Some Ring-Substituted α-Chlorostyrene Oxides and trans-β-Chlorostyrene Oxides.
McDonald, Richard N.,Cousins, Raymond C.
, p. 2976 - 2984 (2007/10/02)
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.
