Redox-transfer. Part VII. Addition of ethylene and butadiene to functionally substituted aromatic sulphonyl chlorides

Abstract

Application of the copper chloride-catalysed addition of substituted aromatic sulphonyl chlorides to ethylene and butadiene is extended to sulphonyl chlorides carrying bromine, carboxy-, chloromethyl, chlorosulphonyl, and 2-chloroethylsulphonyl substituents. Several ethylene adducts are further transformed by chlorosulphonation. dehydrochlorination, and oxidation of a methyl to a carboxy-group.The cis-rrans-isomerisation of but-2-ene by toluene-p-sulphonyl chloride a t 100" is discussed. The isomerisation has a radical-chain character, is strongly retarded by chloride ions, and is completely inhibited by norbornadiene.

Towards the development of highly active copper catalysts for atom transfer radical addition (ATRA) and polymerization (ATRP)‡

“…Alkyl halides are typically polyhalogenated alkanes (Asscher & Vofsi, 1961;Freidlina & Velichko, 1977;Julia et al, 1979a;Truce & Wolf, 1971), benzylic halides (Baban & Caronna et al, 1977;Minisci, 1975), N-haloamines (Minisci, 1975), α-halonitriles (Julia et al, 1979b;Miniotte et al, 1975), α-haloacetates (Julia et al, 1979a;Murai et al, 1964), α-haloaldehydes (Bellus, 1985;Martin et al, 1985;Steiner et al, 1982) and alkylsulfonyl halides (Amiel, 1974;Asscher & Vofsi, 1961;Block et al, 1986;Kamigata et al, 1983;Sinnreich & Asscher, 1972;Truce & Wolf, 1971). Alkenes, on the other hand, range from relatively free-radical polymerization inactive (α-olefins such as 1-hexene, 1-octene or 1-decene) to highly active (styrenes, (meth)acrylates, acrylonitrile or vinyl acetate).…”

Structural and Mechanistic Aspects of Copper Catalyzed Atom Transfer Radical Polymerization

“…Complexes of copper [8,9,10,11,12] , iron [8,13,14,15] , ruthenium [16,17,18] , and nickel [19,20,21] were found to be particularly active catalysts for ATRA. Apart from controlling product distribution, great progress has also been made in utilizing a variety of halogenated compounds (alkyl and aryl halides [22,23,24] , N -chloroamines [24] , alkylsulfonyl halides [8,25,26,27,28,29] , and polyhalogenated compounds [8,14,29,30] ), as well as alkenes (styrene, alkyl acrylates, and acrylonitrile). Therefore, transition metal-catalyzed (TMC) ATRA became a broadly applicable synthetic tool [4,10,18,19,31] .…”

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.…”