Methyl acrylate, viii

As was noted previously, Hine and Bailey (16, 17) have obtained correlation of rate data for the reaction of tra s-3-substituted acrylic acids and diphenyl-diazomethane with the Hammett equation. Bowden has reported correlation of rate data for the reaction of tra s-3-substituted acrylic acids with diphenyl-diazomethane (59) and the alkaline hydrolysis of trans-3-substituted methyl acrylates (69) with the Hammett equation. Sufficient data are available for nine sets of rate studies. The sets studied are reported in Table VIII. The results of the correlations are given in Table IX. Of the nine sets studied, seven gave... 

The reaction of benzyl chloride with metallic nickel in the presence of methyl acrylate was carried out at 85°C, and the expected addition product methyl 4-phenylbutanoate was formed in 17% yield (Equation 7.12). The reaction with acrylonitrile gave 4-phenylbutanenitrile in 14% yield together with cis- and tra 5-4-phenyl-2-butenenitriles, 4-cyano-6-phenylhexanenitrile, and 2-ben-zyl-4-phenylbutanenitrile (Equation 7.13). The results suggest the presence of a benzylnickel(II) chloride complex (1), which could have been formed by the oxidative addition of benzyl chloride to the metallic nickel (Scheme 7.7). The complex (I) would then be expected to add to the electron-deficient olefins, affording the addition product (111) via intermediate complex (IV). The formation of cis- and tra s-4-phenyl-2-butenenitrile (V) is reasonably explained by the reductive elimination of nickel hydride from intermediate (IV), which is analogous to the substitution reaction of olefins with alkylpalladium compound [158] and to the addition-elimination reaction of bis(triphenylphosphine) phenylnickel(II) bromide with methyl acrylate to yield methyl cinnamate [130]. Furthermore, intermediate (IV) seems to add another molecule of acrylonitrile to give the 1 2 adduct 4-cyano-6-phenylhexanenitrile (VI). 2-Benzyl-4-phenylbutanenitrile (VIII) would be formed by the metathesis of complex IV and the benzylnickel chloride (I). 

Of the dienes, butadiene appears to have been the earliest to have been evaluated. Although it allowed accelerated sulphur vulcanization this was to the detriment of heat and oil resistance. More recently, non-conjugated dienes such as those used with EPDM rubbers have been quoted in the patent literature. These include dicyclopentadiene and methyl cyclopentadiene. A French patent (Tellier and Grimaud, 1968) quotes the use of tetrahydrobenzyl acrylate (VIII). 

Polymers of the lower n-alkyl acrylates have found some commercial use. The lowest member of the series, poly(methyl acrylate) has poor low temperature properties and is water-sensitive and its use is therefore restricted to such applications as textile sizes and leather finishes. Ethyl acrylate and butyl acrylate are the most commonly used major components of commercial acrylate rubbers. At the present time, most commercial acrylate rubbers are copolymers of either ethyl or butyl acrylate with an alkoxy acrylate such as methoxyethyl acrylate (VIII) and ethoxyethyl acrylate (IX). The presence of a proportion of longer side-chains gives a rubber with improved low temperature flexibility. 

A recent paper by a Rusian team [18] describe tte use of a few new surfiners, one being cationic, namely JV-decylaceto-2-methyl-5 vinylpyridinium bromide (V), and the others being anioic, namely decyl (or dodecyl), sodium ethyl sulfonate, methacrylamides (VI), decyl (or dodecyl)-phenyl (Na or K sulfonate) acrylate (VII), and decyl ester of sodium (or K or NH4) sulphocin-namic acid (VIII). These surfmers were used for emulsion polymerization of styrene, butylacrylate or chloroprene, in the presence of KPS or AIBN without any other surfactants. It should be noted that the consumption of these surfactants take place early in the polymerization process which is faster than in... 

With poly(acrylates), on the other hand, the methyl groups are absent (structure VIII), so there are hydrogens available to shift. Bond dissociation produces a secondary free radical, which can be stabilized by the 1-5 H shift to a tertiary free radical. 

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