- vic-Dichlorination of olefins with sodium chlorite, Mn(acac)3, and moist alumina in dichloromethane
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Aliphatic, alicyclic, and aromatic alkenes underwent smooth vicdichlorination upon treatment with a reagent combination of NaClO2, Mn(acac)3 catalyst, and chromatographic neutral alumina preloaded with a small amount of water in dichloromethane under mild conditions.
- Yakabe, Shigetaka,Hirano, Masao,Morimoto, Takashi
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- Reaction of Styrene with Chlorine Dioxide
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Reaction of styrene with chlorine dioxide under various conditions selectively produces 1-phenyl- 2-chloroethanone, with 1-phenyl-2-chloroethanol, 2-hydroxy-1-phenylethanone, (1,2-dichloroethyl)benzene, (2-chloro-1-phenyl)ethene, and (1,2,2-trichloroethyl
- Loginova,Chukicheva, I. Yu.,Kuchin
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p. 825 - 828
(2018/06/14)
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- Use of a fluorous bridge for diffusion controlled uptake of molecular chlorine in chlorine addition to alkenes
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Fluorous solvent was used for passive transport of molecular chlorine from one side of the U-tube to the other, where addition of chlorine to alkenes was quantitative and diffusion controlled.
- Iskra, Jernej,Stavber, Stojan,Zupan, Marko
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p. 2496 - 2497
(2007/10/03)
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- Quaternary ammonium polychlorides as efficient reagents for chlorination of unsaturated compounds
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Chlorination of unsaturated compounds by benzyltributylammonium polychlorides results in higher yields of addition products compared to those obtained with molecular chlorine.
- Zelikman,Tyurin,Smirnov,Zyk
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p. 1541 - 1546
(2007/10/03)
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- Reaction of α,β-Unsaturated Carboxylic Acids with Manganese(III) Acetate in the Presence of Chloride Ion
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The reaction of 3-phenylpropenoic acids with manganese(III) acetate - Cl- complex yielded 1,2,2-trichloro-1-phenylethanes, 1-acetoxy-2,2-dichloro-1-phenylethanes, and 2,2-dichloro-1-phenylethanols. (E)-2,3-Diphenylpropenoic acids gave 2,2-dichloro-1,2-diphenylethanones and 2-acetoxy-1,2-diphenylethanones. 3,3-Diphenylpropenoic acids yielded 2,2-dichloro-1,1-diphenylethenes, 1-acetoxy-2,2-dichloro-1,1-diphenylethanes, 2,2-dichloro-1,1-diphenyl-1-ethanols, and 2-hydroxy-2,2-diphenylethanal.Fluorenylideneacetic acid gave 9-chloro-9-(dichloromethyl)fluorene, 9-acetoxy-9-(dichloromethyl)fluorene, and 9-fluorenone. 1-Cyclohexenecarboxylic acid yielded 1,2-dichlorocyclohexanecarboxylic acid and 1-acetoxy-2-chlorocyclohexanecarboxylic acid.The reaction can be explained in terms of a free-radical mechanism involving manganese(III) acetate - Cl- complexation, addition of Cl. radical, decarboxylation, and the oxidation of chloroethenes which are the reaction intermediates.
- Yonemura, Hiroshi,Nishino, Hiroshi,Kurosawa, Kazu
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p. 3153 - 3160
(2007/10/02)
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- Synthetic Applications of Conjugated Azocarbinols. Radical Chain Hydrophenylation and Hydrocyclohexenylation of Haloethenes
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2-(Phenylazo)-2-propanol (5) and (phenylazo)diphenylmethanol (6) decompose in solution by process involving phenyl radicals.Similarly, 1-(1-azocyclohexenyl)cyclohexanol (7) decomposes to generate the 1-cyclohexenyl radical.Evidence for radical intermediates includes the formation of chlorobenzene and 1-chlorocyclohexene, respectively, from decomposition of 5 (or 6) and 7 in CCl4.Evidence for induced, chain decomposition by radical abstraction of hydroxyl hydrogen, in concert with breaking of at least one C-N bond of the azo function, includes faster decomposition in CCl4 than in benzene, acceleration of decomposition in CCl4 by thiophenol, and acceleration of decomposition in benzene by trityl radicals.That decomposition mechanism is supported also by the finding that methyl ethers and acetate esters of the azoalcohols decompose much more slowly than the alcohols themselves.Phenyl radicals from either 5 or 6, and 1-cyclohexenyl radicals from 7, can be trapped with some alkene by addition.Such radical adducts subsequently pick up a hydrogen atom, presumably by abstracting from the hydroxyl group of the azocarbinol in concert with C-N bond breaking.The overall processes, then, are hydrophenylation of alkenes with 5 and 6 and hydro-1-cyclohexenylation of alkenes with 7 by a radical chain mechanism.The processes are of preparative value only in cases of alkene substrates which are neither highly polymerizable nor prone to radical attack on allylic substituents.Several highly halogenated compounds prepared by treatment of haloethenes with 6 or 7 are reported.The reaction between 5 and benzaldehyde, to form acetone and 1-benzoyl-2-phenylhydrazine, was found to be second order overall, first order in 5 and first order in benzaldehyde between 0.4 M and neat benzaldehyde.This result does not appear to be compatible with a mechanism involving decomposition of 5 to acetone and phenyldiazene, with subsequent reaction of the latter with benzaldehyde.
- Chang, Yau-Min,Profetto, Ralph,Warkentin, John
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p. 7189 - 7195
(2007/10/02)
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