SYNTHESIS OF SUCCINIC ACID AND ITS SUBSTITUTED DERIVATIVES IN REACTIONS OF ACYLATE α-CARBANIONS WITH SODIUM CHLOROACETATE

DOI: 
10.6060/tcct.20165910.5399

Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2016. V. 59. N 10. P. 19-23

Most approaches to the synthesis of dicarboxylic acids lead to formation of symmetrically substituted dicarboxylic acids. Interaction of iodoacetic acid salt with metallated cyclopropylacetic acid at -78 °C gives asymmetrically substituted 2-cyclopropylsuccinic acid with high yield (93%). Industrially available monochloroacetic acid is more attractive precursor for creating preparative methods of synthesis of asymmetrically substituted derivatives of succinic acid. Thus, it is expected that the substitution of the chlorine will proceed less efficiently than iodine. The possibility of synthesis of asymmetrically substituted succinic acids based on sodium chloroacetate and different metallated carboxylic acids have been studied. The conditions in which sodium chloroacetate effectively reacts with α-carbanions of lithium acylates have been found. Interaction of α -carbanions of lithium acylates generated from acetic, butyric, isobutyric, valeric, isovaleric and phenylacetic acids with lithium diisopropylamide with sodium chloroacetate in tetrahydrofurane medium at normal conditions under argon atmosphere during 24 hours, leads to formation of succinic acid (68% yield), and asymmetrically substituted 2-ethylsuccinic, 2,2-dimethylsuccinic, 2-propylsuccinic, 2-isopropylsuccinic and 2-phenylsuccinic acids with 58, 27, 46, 38 and 96% yields, respectively.Yields of dicarboxylic acids depend on α -carbanions structure. Increase in chain size and branching of the alkyl substituent in α-carbanions, as well as the transition from α-carbanions with anionic center at the primary α- carbon atom to α-carbanion with an anionic center at the secondary and then tertiary α- carbon atom leads to reduction of dicarboxylic acids yields. Reaction with metallated phenylacetic acid gives most effective yield.

Key words: dicarboxylic acids, metallation, nucleophilic substitution, sodium chloroacetate, CH-acids

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2016, Т. 59, № 10, Стр. 19-23

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