Diallyl succinate

Copolymeis of diallyl succinate and unsatuiated polyesters cured by x rays provide wear-resistant coatings of MMA dental polymers (76). 

Figure 2. Relationship between the percentage of hh linkage and the content of uncyclized unit, 100 — fe, obtained for cyclopolymerizations in benzene solutions at 80°C. Key O, diallyl phthalate O, diallyl succinate and , diallyl cis-i 2-cyclo-hexanedicarboxylate. (Reproduced, with permission, from Ref. 21. Copyright 1981, J. Polym. Sci. Polym. Lett. Ed.)...

Using differential scanning calorimetry, studies on the isothermal bulk polymerization of diallyl fumarate, diallyl maleate, and diallyl succinate were carried out. 

At constant initiator concentration and using a programmed heating cycle, the heats of polymerization for diallyl fiunarate was foimd to be — 126.4 kJ/mole ( — 30.2 kcal/mole) for diallyl maleate —82.9kJ/mole (—19.8 kcal/mole) and for diallyl succinate —90.8 kJ/mole ( — 21.7 kcal/mole) [121]. 

Stoltz et al. reported enantioselective synthesis of (—)-cyanthiwigin F via double decarboxylative asymmetric allylation of bis(allyl P-ketocarboxylates) (Scheme 8.10) [34]. Initially, two molecules of diallyl succinate (57) was condensed under basic conditions to give a cyclic bis(P-ketoester), which was then methylated to afford an isomeric mixture of 58. Subsequent treatment with a chiral palladium catalyst induced double decarboxylation of those allyl P-ketoester moieties to afford a chiral cyclohexan-l,4-dione 59 (99% ee) along with its meso isomer. The enantiomeric excess of the product was enhanced through the double asymmetric allylation reaction. The cyclo-hexanedione 59 was converted into (-)-cyanthiwigin F through further six steps. 

Brian M. Stoltz of Caltech prepared (Nature 2008,453,1228) the diester 33 by dimerization of diallyl succinate followed by methylation. Pd-mediated rearrangement delivered 34, the central ring of (-)-Cyanthiwigin 35, in high de and ee. 

Indium-mediated allylation of cyclic and acyclic acid anhydrides gives w-diallyl esters.203,204 Examples are shown in Scheme 48 the allylation of succinic anhydride or phthalic anhydride with allyl bromide in DMF in the presence of indium metal results in the formation of diallylbutenolides or diallylphthalides. In contrast, monoallylated hydroxy esters are formed exclusively with y-substituted allylic halides. 

Because of the ease of synthesis and industrial importance of diallyl esters much of the research has dealt with the behavior of the isomeric phthalates. Some other dicarboxylic acid esters have been studied by Simpson and Holt [41]. The kinetics of the poljmierization of the diallyl esters of oxalic, malonic, succinic, adipic, and sebacic acid have also been considered. In previous kinetie studies, no differentiation was made between the behavior of the uncyclized monomer (or its free radical) and of the cyclic free-radicals. A priori, differences should have been presumed, but evidently Matsumoto and Oiwa [46] were the first seriously to attempt a kinetic analysis based on the concept that the linear and the cyclic units are two different species. In effect, these two species copolymerize with each other. However, the analysis has not been carried so far as to determine reactivity ratios. 

Garcia-Martinez, J.A., Zhang, T.M., Villanueva-Penacarrillo, M.L., et al. (1997) In vivo stimulation of insulin release by the monoethyl, monopropyl, monoisopropyl, monoallyl and diallyl esters of succinic acid. Research Communications in Molecular Pathology and Pharmacology, 95,209-216. 

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