OXIDATIONS OF ALKENES CATALYZED BY A MN(III) PORPHYRIN AND CATIONIC POLYMER LATEXES

Three types of cationic polymer latexes were prepared by emulsion copolymerization of vinylbenzyl chloride, divinylbenzene and a third monomer, vinyl octadecyl ether, styrene, or n-decyl methacrylate, followed by quaternization with trimethylamine. The latexes had 44-71 nm diam and polydispersity indices of 1.06-1.10. Vinyl octadecyl ether did not copolymerize but hydrolyzed under the polymerization conditions to produce 1-octadecanol, which as a coemulsifier gave highly viscous latexes. The tetraanion 5,10,15,20-tetrakis(2,6-dichloro-3-sulfonatophenyl)porphinatomanganese(III) chloride bound irreversibly to the cationic latexes and was an active catalyst for oxidations of alkenes by sodium hypochlorite and potassium peroxymonosulfate in the absence of added organic solvent. The porphyrin catalyst in the latexes was more active than in solution. Porphyrin catalysis gave epoxides concurrently with competing uncatalyzed hypochlorous acid oxidations to complex mixtures of allylic chlorides, allylic alcohols, alpha-beta-unsaturated ketones, and chlorohydrins.