Redox transfer. Part VIII. Addition of benzenesulphonyl chloride and carbon tetrachloride to substituted styrenes: a kinetic study

Abstract

A kinetic study of the copper chloride-catalysed addition of benzenesulphonyl chloride to a number of styrenes carrying substituents of widely different electronegativity shows that the overall rates are very little affected by the substituent. This rules out the possibility of a concerted reaction, in which the olefin should participate in the rate-determining step, and confirms a redox chain mechanism. The lack of stereospecificity of the addition of carbon tetrachloride to norbornene points to the same conclusion. P-Methylstyrene reacts much more slowly with benzenesulphonyl chloride than the other styrenes. This is attributed to an unfavourable equilibrium for sulphonyl radical addition to this olefin. Carbon tetrachloride adds a t the same rate to different olefins, including P-methylstyrene, in accord with the redox chain mechanism.

Radical ring‐opening polymerization of five‐membered cyclic vinyl sulfone using p‐toluenesulfonyl halides

“…Aryl‐ and alkylsulfonyl halides undergo bond homolysis,14 and the resulting sulfonyl radicals are subsequently added to substituted and unsubstituted olefins 15–24. Percec pointed out that the homolysis of the sulfonyl halide can be initiated thermally 25.…”

Cascade synthesis of new aryl 2-phenylallyl sulfones from α-methylstyrene and aromatic mono- and bis-sulfonyl chlorides

“…Liberation of hydrogen chloride was observed throughout the reaction, and the only final products were unsatu-DOI: 10.1134/S1070428010030085 rated sulfones IIIa-IIIm (Schemes 1, 2). According to published data, in all analogous reactions studied previously dehydrohalogenation of the primary adduct was a separate step which was carried out by the action of triethylamine in benzene at room temperature [1][2][3][4]. Elimination of hydrogen chloride from adducts IIa-IIm followed Hofmann's rather than Saytzeff's rule, and the products were less substituted allylic sulfones IIIa-IIIm instead of expected more substituted vinyl sulfones like IV.…”

“…In the present work we examined addition of various aromatic mono-and bis-sulfonyl chlorides Ia-Im to α-methylstyrene under standard conditions for the reactions of sulfonyl chlorides with alkenes, including substituted styrenes [3,4]. The reactions were carried out by heating the reactants in boiling acetonitrile in the presence of copper(II) chloride and triethylamine hydrochloride.…”

“…Later on, this general and convenient method for the preparation of β-halo sulfones, as well as of α,β-unsaturated sulfones via subsequent dehydrochlorination, has been extensively developed in a number of studies. Additions of sulfonyl chlorides and iodides to activated and nonactivated alkenes [1][2][3][4][5][6][7][8], conjugated dienes and trienes [2], allenes [3], acetylenes [9,10], styrenes having various substituents in the aromatic ring [3], β-methylstyrene [4], etc., have been reported. However, there are no published data on analogous reactions with α-methylstyrene.…”

Investigation on chain transfer reaction of benzene sulfonyl chloride in styrene radical polymerization

“…[1][2][3][4][5][6][7][8][9][10][11][12][13] Recently, sulfonyl chlorides have been used as efficient initiators for transition metal catalyzed atom transfer radical polymerization (ATRP). [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28] However, as far as we know, there is only one paper in the literature dealing with the chain-transfer reaction of sulfonyl chlorides in the free radical polymerization.…”