- DOPING-ADDITION OF ARENESULFENYL CHLORIDES TO OLEFINS IN THE PRESENCE OF PERCHLORIC ACID AND THE LITHIUM PERCHLORATE. CRITERIA OF LIMITING VARIANTS IN MECHANISM OF THESE REACTIONS
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The addition of perchloric acid in the addition reactions of sulfenyl chlorides to olefins gives rise to a doping effect, which exceeds the analogous effect of lithium perchlorate.Analysis of the dependence of rate of the model reactions and the yields of the doping products on the perchloric acid and lithium perchlorate concentrations showed that the doping additions can operate by two mechanisms, i.e., by the mechanism of a normal salt effect in the controlling state and by a mechanism of ion-pair exchange in the subsequent fast stages.
- Kartashov, V. R.,Sorobogatova, E. V.,Grudzinskaya, E. Yu.,Zefirov, N. S.,Caple, R.
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p. 2231 - 2242
(2007/10/02)
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- REACTION OF SULFENYL HALIDES WITH ALKENES IN THE PRESENCE OF PERCHLORIC ACID
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In the reaction of 2,4-dinitrobenzenesulfenyl chloride and benzenesulfenyl chloride with cyclohexane, propene, and styrene in acetic acid in the presence of perchloric acid the corresponding solvent adducts are formed with yields of 47-75percent.The effect of the perchloric acid on the rate of the reaction of 2,4-dinitrobenzenesulfenyl chloride with cyclohexene is described by an equation for homogeneous catalysis.On the basis of the kinetic data two possible schemes are proposed for the effect of perchloric acid on the formation of the solvent adducts, i.e., a mechanism of homogeneous catalysis and by an ion-exchange mechanism in the noncontrolling stages of the reaction.
- Grudzinskaya, E. Yu.,Skorobogatova, E. V.
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p. 1710 - 1713
(2007/10/02)
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- REACTION OF THIOCYANOGEN CHLORIDE AND DITHIOCYANOGEN WITH CYCLOPROPENE HYDROCARBONS
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The reactions of dithiocyanogen and thiocyanogen chloride with 3,3-dimethylcyclopropene take place as trans-addition.The addition of thiocyanogen chloride to propene and 1-methylcyclopropene leads to the preferential formation of regioisomers according to the Markovnikov rule (in contrast to sulfenyl chlorides) and, in the latter case, is characterized by the formation of the products from opening of the three-membered ring to a larger degree than the analogous addition of sulfenyl chlorides.Dithiocyanogen and, particularly, thiocyanogen chloride exhibit greater effective electrophilicity than sulfenyl chlorides.
- Kartashov, V. R.,Skorobogatova, E. V.,Afanas'ev, P. S.,Akimkina, N. F.,Grudzinskaya, E. Yu.,Zefirov, N. S.
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p. 472 - 476
(2007/10/02)
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