Sulfinates vinyl substitutions

VINYL SUBSTITUTION WITH ORGANIC HALIDES, DIAZONIUM SALTS, ACID CHLORIDES, SULFINATE SALTS AND TRIFLATES... 

J Vinyl Substitutions with Carboxylic Acid Halides, Aryl Sulfinates and Arylsulfonyl Chlorides... 

Simple unsaturated sulfides cannot be used in place of enamines in cycloaddition reactions with sulfines leading to thietane dioxide derivatives. " Alkyl, vinyl, and cycloalkylvinyl sulfides, which carry a C=C double bond, are considerably less nucleophilic than the enamines and thus do not partake in cycloadditions to sulfene. But when the more electrophilic methylsulfonyl sulfene is used in association with an unsaturated sulfide substituted with a strong electron donating alkylamino group, the formation of thietane dioxides 72 is successful. 

Sulfones (55) are generally prepared by the oxidation of the appropriate sulfides (2) (Scheme 26).7 The oxidation is generally performed by treatment with peroxycarboxylic acids, but other oxidants may be used (see Chapter 10, p. 195). Diarylsulfones are often obtained by the Friedel-Crafts reaction, and special methods are available for the synthesis of substituted sulfones such as vinyl, hydroxy and halosulfones (see Chapter 10, p. 197). Sulfonyl ethers (56) can be prepared by reaction of a suitable chloroether (57) with the appropriate - sodium sulfinate (58) (Scheme 27). 

A versatile non-Friedel-Crafts approach to naphthols is provided by condensation of the toluic acid sulfoxide with substituted acrylates or methyl vinyl ketone. Sequential conjugate addition and acylation of the first formed anion leads to the tetralone. Pyrolysis leads to aromatiza-tlon by loss of sulfinic acid. 

The reaction of peroxyesters, hydroperoxides or peroxides, which are more storage stable than BP, with tertiary amines is generally too slow to give a sufficiently rapid cure for acrylic resins. Composite mixes containing t-butyl perbenzoate, -butyl hydroperoxides or dicumyl peroxide-tertiary amines do not harden for days. Many other redox systems have been suggested for vinyl polymerizations, only a few have been employed in dental resins. Substitution of 2 toluene sulfinic acid or sulfinic acid derivatives for tertiary amines yields colorless products (38-42). Most of these compounds have poor shelf-life. They readily oxidize in air to sulfonic acids which do not activate polymerization. Lauroyl peroxide in conjunction with a metal mercaptide (such as the zinc hexadecyl mercaptide) and... 

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