Diallylmalonic acid

Spira d.4imonaietraene (5). This elusive spiro compound has now been synthesized from the diacid chloride of diallylmalonic acid (I). This substance is treated in methylene chloride solution containing several mole equivalents of nitrotnethane with aluminum chloride at 25° to give, after hydrolysis with aqueous ammonium chloride, spiro[4.4]-nona-2,6-diene-l,5-dionc (2) in 51% yield. Reduction of (2) with aluminum hydride... 

The formation of 5-V compatible with the spectral evidence involves addition of the initiator radical to the double bond of 5-1 in the sense opposite to the way normally found with monoolefins. Therefore, it may be concluded that the species present is a five-membered cyclic radical. Another evidence for the formation of a five-membered cyclic radical from diallylmalonic acid was obtained from the studies of its reactions with amino and phenyl radicals in the flow systems. 

Fig. 35. ESR spectrum for radical formed from diallylmalonic acid and OH...

The following German patents have also been taken out for alipliatic acid mercurials Ibid, 246207, behenolic acid esters, stearolio acid ester. Ibid, 264267, aryl hydroxy fatty acids. Ibid, 279199, aminometiiane disulphonic acid. Ibid., 228877, oleic acid ethyl ester, triolein. Ibid., 387850 American Patent, 1457675 diethyl diallylmalonate, diallyb barbituric acid, ethyl dialiylacetate, diethjri o-phenylenediacrylate, diplienio acid and ethyl diphenylamine-2-ca.rboxylate. 

Lewis acids as cocatalysts are effective for Pd-catalyzed cycloisomerization. The reaction of diallylmalonate 36 in the presence of AgOTf afforded 63 with high selectivity [31]. Asymmetric cyclization of 1,6-diene 36 was carried out using PdCl2(MeCN)2-AgBF4 in the presence of a chiral ligand [32]. Cycloisomerization... 

Simple butyrolactones can be prepared in ca. 40% yield by cyclization of both /3y- and y5-unsaturated acids using lithium tetrachloropalladate. A general route to y-methylenebutyrolactones, based on the iodolactonization technique, has been developed (Scheme 16). Yields throughout are good, and by extending the reaction to diallylmalonic esters bis-lactones (35) can be obtained. 

The sodium salts of members of the iW -disubstituted series (265) react readily with benzoyl chloride, bromine, chloramine, or tosyl azide to give 3-substituted derivatives, the diazo-compounds (277) providing access to still further examples. The 3,3 -diallyl derivatives (278) are obtained through condensation of o-diamino-aromatics with diethyl diallylmalonate directly. Hydration of (278a) and (278b) afforded the lactone (279), whereas with sulphuric acid (278a) gave (280). ... 

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