104944-99-2Relevant articles and documents
CHARACTERISTICS OF THE ADDITION OF ORGANIC DISELENIDES TO THE ETHERATES OF CHLORO- AND DICHLOROACETYLENES
Martynov, A. V.,Mirskova, A. N.,Voronkov, M. G.
, p. 841 - 848 (2007/10/02)
The reaction of diorganic diselenides with chloro- and dichloroacetylenes in diethyl ether leads to the formation of 2-chloro- and 1,2-dichlorovinyl selenides respectively in addition to 1,2-bis(organoseleno)chloro- and 1,2-bis(organoseleno)-1,2-dichloroethylenes.In addition, the appearance of the products from the reaction of diethyl ether with dichloroacetylene and with the diorganic diselenides was observed, i.e., 3-ethoxy-1,2-dichloro-1-butene, bis(1,2-dichloro-1-buten-3-yl) ether, 1-phenylselenodiethyl ether, and 1-alkylseleno-3-ethoxy-1,2-dichloro-1-butenes.In addition to disproportionation of the chloroacetylene, accompanied by the generation of a proton, the reactions leading to the last two compounds are evidently responsible for the appearance of 2-chloro- and 1,2-dichlorovinyl selenides in the reaction mixtures.Arguments are presented in favor of a free-radical mechanism, including the formation of the organoselenyl radical.
CHLOROVINYLATION OF BENZENESELENOL AND ORGANIC DISELENIDES BY CHLORO- AND DICHLOROACETYLENES
Martynov, A. V.,Mirskova, A. N.,Voronkov, M. G.
, p. 1326 - 1328 (2007/10/02)
Mixtures of the Z and E isomers of unsaturated organic selenides and 1,2-bis(organoseleno)mono(di)chloroethylenes were obtained by the addition of benzeneselenol and organic diselenides to the etherates of chloro- and dichloroacetylene
SELENYLATION OF TRI- AND TETRACHLOROETHYLENE BY ORGANIC DISELENIDES UNDER CONDITIONS OF PHASE-TRANSFER CATALYSIS
Martynov, A. V.,Mirskova, A. N.,Voronkov, M. G.
, p. 1602 - 1608 (2007/10/02)
The selenylation of tetrachloroethylene by organic diselenides under the conditions of phase-transfer catalysis leads to the formation of 1,2-bis(organoseleno)-1,2-dichloroethylenes in 50percent solution of sodium hydroxide and to a mixture of trichlorovi
REACTION OF BENZENESELENOL WITH TRI- AND TETRACHLOROETHYLENES UNDER CONDITIONS OF PHASE-TRANSFER CATALYSIS
Martynov, A. V.,Mirskova, A. N.,Kalikhman, I. D.,Voronkov, M. G.
, p. 454 - 462 (2007/10/02)
The reaction of benzeneselenol with trichloroethylene in concentrated sodium hydroxide solution, catalyzed by ammonium salts, leads to Z-phenyl α,β-dichlorovinyl selenide with an equimolar ratio of the catalyst and the selenol or to a mixture of the Z and E isomers with a ratio of 1:10.In addition to the expected trichlorovinyl selenide PhSeCCl=CCl2, the analogous reaction with tetrachloroethylene also gives a mixture of the Z and E isomers of α,β-dichlorovinyl selenides and, in addition, 1,2-bis(phenylseleno)-1,2-dichloroethylene PhSeCCl=CClSePh.If trialkylbenzylammonium chlorides R3PhCH2N(1+)*Cl(1-) are used as catalyst, phenyl benzyl selenide PhSeCH2Ph is formed as a side product.The results of the reaction in the case of trichloroethylene are explained by the addition of the selenolate ion to the CClCCl, generated from the trichloroethylene in situ, and isomerization of the initially formed Z-phenyl α,β-dichlorovinyl selenide to the thermodynamically more stable E isomer.In the case of tetrachloroethylene they are explained by the usual addition-elimination mechanism with the formation of trichlorovinyl selenide, accompanied by reductive dechlorination of the CCl2=CCl2 to CHCl=CCl2 by the selenolate and subsequent reaction of the selenolate with CHCl=CCl2.
