Succinaldehydic acid

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. 

An interesting aspect of the Bi-mediated Barbier-type allylation is that the reaction can be conducted in aqueous media. When the reaction is carried out using metallic bismuth powder in water, addition of an equimolar amount of potassium fluoride improves the yield of homoallyl alcohol (Equation (40)).74 The reaction is also compatible with hydroxyl and carboxyl groups of the carbonyl substrates. When succinaldehydic acid, 4-oxopentanoic acid,... 

Bourguignon, J. J. and Wermuth, C. Cj., Lactone chemistry synthesis of p-substituted, f functionali/.ed butanolides and butenolides and succinaldehydic acids from glyoxylic acid, J. Orfi. Chen, 46, 4889. 1981. 

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... 

Succinaldehydic acid, SCI. Succinic semialdehyde. 3-Formylpropionic acid. y-Oxobutanoic acid [692-29-5]... 

The preparation of butyric-4-C acid (50% yield) involves a two-step synthesis starting viuth glutamic-l,2-C acid (Mosbach et at., 195i). The procedure requires a deamination to succinaldehydic acid which is followed by a modified Wolff-Kishner reduction. In the first step the doubly labeled glutamic acid loses one labeled C moiety to become a singly labeled aldehyde. The unstable intermediary succinaldehydic acid is prepared as needed. Coon and Abrahamsen (1952) and Zabin and Bloch (1951) prepared butyric-3-C add from ethyl-l-G iodide in yields of 41 and 51%, respectively. 

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. ... 

BerL Ber., abbrev. (Berliner Berichte) Berickte der deutscken chemiachen Gesellscka/t. Berliner-blau, n. Berlin blue, Prussian blue, -blaus ure, /. hydrocyanic acid, -braun, n. Prussian brown, -griin, n. Prussian green, -rot, n. Berlin red (a red lake color), -saure,/. prussic acid, -weiss, n. a kind of white lead. Bernstein, m. amber. — schwarzer —, jet. Bernstein-, amber succinic, succinyl, succino-. -alaun, m. aluminous amber, -aldehyd, n. succinaldehyde. bemateinartig, a. amber-like. 

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

The original Robinson synthesis (66) of tropinone (124), which consists of a reaction between succinaldehyde (140), methylamine (141), and the calcium salt of acetonedicarboxylic acid (142), proceeds in low yield (Scheme 2). However, it has the great merit of being the pioneering achievement in the field of biomimetic syntheses of natural products. 

The domino approach is also used by Nature for the synthesis of several alkaloids, the most prominent example being the biosynthesis of tropinone (0-16). In this case, a biomimetic synthesis was developed before the biosynthesis had been disclosed. Shortly after the publication of a more than 20-step synthesis of tropinone by Willstatter [14], Robinson [15] described a domino process (which was later improved by Schopf [16]) using succinaldehyde (0-13), methylamine (0-14) and acetonedicarboxylic acid (0-15) to give tropinone (0-16) in excellent yield without isolating any intermediates (Scheme 0.5). 

Take the total amount of succinaldehyde (obtained from 4 of the above syntheses combined) and without further treatment or purification (this had better be 15.5 g of succindialdehyde) put into an Erlenmeyer flask of 4-5 liters capacity. Add 21.6 g of methylamine hydrochloride, 46.7 g of acetonedicarboxylic acid, and enough water to make a total volume of 2 liters. Adjust the pH to 8-10 by slowly adding a saturated solution of disodium phosphate. The condensate of this reaction (allow to set for about 6 days) is extracted with ether, the ethereal solution is dried over sodium sulphate and distilled, the product coming over at 113° at 25 mm of pressure is collected. Upon cooling, 14 g of tropinone crystallizes in the pure state. Tropinone can also be obtained by oxidation of tropine with potassium dichromate, hut I could not find the specifics for this operation. 

Another interesting example is the synthesis of 77-(2-thiazolyl)-nortropinon 121. Stoll and co-authors [175] described the synthesis of this drug-like product via the legendary first total synthetic approach proposed by Robinson in 1917 [176] for the natural alkoloid tropinone, also well known as a good example of biomimetic reaction. In this tandem treatment, 2-aminothiazole was reacted with succinaldehyde and acetonedicarboxylic acid yielding 77-(2-thiazolyl)-nortropinon 121 in moderate yields (Scheme 58). 

Monoacetals of substituted succinaldehydes (162), readily prepared by hydroformylation of optically active a,(3-unsaturated aldehyde acetals, were used to synthesize 3-substituted thiophenes having an optically active substituent (163). In these cases, while the use of hydrogen sulfide and HC1 in methanol at room temperature was more convenient, comparison with formation of (163) by the Paal synthesis from an appropriately substituted succinic acid salt gave products having about the same amount of racemization (73JOC2361). 

Limpricht,1 in 1873, prepared furan by heating barium 2-furancarboxylate with soda lime. It has since been prepared by the dry distillation of barium 2-furancarboxylate 2 in small amounts by distillation of calcium succinate 3 by the destructive distillation of resinous pine wood 4 by heating succinaldehyde with water at 1800 0 and by heating 2-furancarboxylic acid in a sealed tube.2... 

The hydrolysis of succinaldehyde dioxime must be carried out with care because of the instability of the dialdehyde. This step has been accomplished in 60% yield by treating the dioxime with ethyl nitrite in dioxane or with sodium nitrite in dilute sulfuric acid. ° ... 

Aldehyde dehydrogenases transform aldehydes into carboxylic acids (e.g. succinaldehyde dehydrogenase). As with alcohol dehydrogenases, the key step of the reaction is the cleavage of the a-C — H bond, with a hydride transfer to NAD-. ... 

A special circumstance in the use of alternative aldehydes like glyoxalic acid glutaraldehyde, glyoxal, succinaldehyde, etc., is the position of chemical equilibrium in the reaction with the polyhydroxy compounds. In the case of some aldehydes, it lies far to the right and gives a quantitative reaction. In other words, the backward reaction—splitting-off of aldehyde—is not observed because the thermodynamic stability of the intermediates than with formaldehyde-based aminoplast resin systems. 

Dicarbonyl Compounds. Glyoxal in neutral solution reacts with PH3 in the presence of PtC and hydroquinone to give a compound whose elemental analysis corresponded approximately to the formula (CH(OH)2CHOH)3P [133]. The reaction, carried out in a suitable mole ratio in a mixture of THF and concentrated hydrochloric acid, failed to give a spirocyclic phosphonium salt [134]. However, succinaldehyde and glutaraldehyde, reacted with PH3 in a mixture of THF and concentrated hydrochloric acid at 20 to 30 C for 2 h, form the corresponding spirocyclic phosphonium salts [134, 138]. PH3 reacts with 2,4-pentanedione in 4 to 6 N HCl to... 

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... 

Sucaryl Sucaryl acid. See Cyclamic acid Sucaryl calcium. See Calcium cyclamate Sucaryl sodium. See Sodium cyclamate Succidet NES. See Disodium laureth sulfosuccinate Succinaldehyde... 

Succinic anhydride, (1-octenyl)-. See 1-Octenylsuccinic anhydride Succinic anhydride, (tetrapropenyl). See Tetrapropenyl succinic anhydride Succinic dialdehyde. See Succinaldehyde Succinic dinitrile. See Succinonitrile Succinic imide. See Succinimide Succinic peroxide. See Succinic acid peroxide Succinimide... 

DL-Diepoxybutane Methacrylic acid Methyl acrylate Methyl acrylate polymer Succinaldehyde Vinyl acetate (C4H602)x... 

Examples of SB formation are outlined in Figure 1.28. The reaction of 4-aminobutanal and succinaldehyde yields an SB which is the intermediate of dialdehyde amine, likely a precursor of the pyrrolizidine ring system. Another example is the piperidine-2-carboxylic acid (a precursor of anabasine) obtained from a-keto- -aminocapronic acid. 

The Robinson-Schopf condensation is a tandem process most notably recognized as the reaction between one molecule of succinaldehyde (1), methyl amine (2), and acetone dicarboxylic acid 3 to give the bicyclic product tropinone (4) in a one-pot procedure. 

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