Succinaldehyde esters

Alternatively, the gem-dibromo group represents a masked carbonyl group. Thus treatment of (8) with. sodium methoxide gives (9) when this is allowed to react with methanolic silver nitrate, the bromine atoms are replaced by methoxyl groups to generate the succinaldehyde ester (10). Hydrolysis of (10) leads to the aldehyde (11). Reduction with tris(triphenylphosphine)chlororhodium (1, 1252 2, 448-453 3, 325-329 this volume) effects decarbonylation to give (12). 

A general approach to chiral 3-alkyl-succinaldehyde-esters (114) is outlined in Scheme 37. For simple alkyl groups, chemical yields are ca. 70% but, more significantly, optical yields are ca. 90% in addition the starting chiral pyrrolidine can be recycled. A route to 3-aroylpropionates, apparently superior to the methods of Stetter and Hauser (which have aryl aldehyde cyanohydrins as intermediates), has been developed (Scheme 38). ... 

Butanediol. 1,4-Butanediol [110-63-4] tetramethylene glycol, 1,4-butylene glycol, was first prepared in 1890 by acid hydrolysis of N,]S3-dinitro-l,4-butanediamine (117). Other early preparations were by reduction of succinaldehyde (118) or succinic esters (119) and by saponification of the diacetate prepared from 1,4-dihalobutanes (120). Catalytic hydrogenation of butynediol, now the principal commercial route, was first described in 1910 (121). Other processes used for commercial manufacture are described in the section on Manufacture. Physical properties of butanediol are Hsted in Table 2. 

Methylsuccinic acid has been prepared by the pyrolysis of tartaric acid from 1,2-dibromopropane or allyl halides by the action of potassium cyanide followed by hydrolysis by reduction of itaconic, citraconic, and mesaconic acids by hydrolysis of ketovalerolactonecarboxylic acid by decarboxylation of 1,1,2-propane tricarboxylic acid by oxidation of /3-methylcyclo-hexanone by fusion of gamboge with alkali by hydrog. nation and condensation of sodium lactate over nickel oxide from acetoacetic ester by successive alkylation with a methyl halide and a monohaloacetic ester by hydrolysis of oi-methyl-o -oxalosuccinic ester or a-methyl-a -acetosuccinic ester by action of hot, concentrated potassium hydroxide upon methyl-succinaldehyde dioxime from the ammonium salt of a-methyl-butyric acid by oxidation with. hydrogen peroxide from /9-methyllevulinic acid by oxidation with dilute nitric acid or hypobromite from /J-methyladipic acid and from the decomposition products of glyceric acid and pyruvic acid. The method described above is a modification of that of Higginbotham and Lapworth. ... 

Succinaldehyde, 7, 41 Succinic acid, 5, 10, 8, 13 Succinic ester (ethyl), 5, 10 Sulfonation, with chlorosulfomc acid, 5, 3... 

Mukaiyama et al. 200) synthesized optically active 3-substituted succinialdehyde acid esters (204) via a Michael-addition. The methyl ester of fumaraldehydic acid was converted into the corresponding aminal (203) by treatment with the (S)-proline-derived chiral diamine (99). The Michael-addition of Grignard reagent to the aminal, followed by hydrolysis produced stereoselectivily 3-substituted succinaldehydic acid ester (204) in good yield. 

Diastereoselective 1,4- (conjugate) additions of Grignard reagents to a chiral a,3-unsaturated aminals afford optically active 3-substituted succinaldehydic acid methyl esters with 85-93% ee (eq 4). ... 

Asymmetric Synthesis of 3-Substituted Succinaldehydic Acid Methyl Esters... 

Butane, 1-chloro-. See Butyl chloride Butanedial. See Succinaldehyde Butanediaoic acid, sulfo-, 1-ester with N-(2-hydroxyethyl) dodecanamide, disodium salt. See Disodium lauramido MEA-sulfosuccinate... 

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