Glutaric esters dicarboxylation

Ring condensations with oxalic estor are Dilceto-cyclopentane dicarboxylic ester from oxalic and glutaric esters 25 COOCjH5 CHj—COOCjHj... 

The rates of alkaline hydrolysis of methyl pyridazine-3- and -4-carboxylate were correlated with those of pyridinecarboxylates and benzoates. Diethyl pyridazine-4,5-dicarboxylate (214) reacts with 1,3-diphenylguanidine in the presence of sodium hydride to give the spiro compounds 215, the structure of which was determined by X-ray analysis. Related spiro compounds were obtained from the above ester and esters of glutaric or acetonedicar-boxylic acids. 5-Aminopyridazine-4-carboxylic acid is simply synthesized from the 5-carboxamido analog by Hofmann rearrangement. ... 

Oxalic esters added in small amounts, with ice-salt cooling, under H2, to Na-ethoxide in ether, then glutaric acid ester added, refluxed 1 hr., the ether distilled off, the mixture heated to 105°, and the resulting Na-compound decomposed in cold 20%-H2SO4 —diethyl cyclopentane-l,2-dione-3,5-dicarboxylate. Y 65 %. (G. Hesse and H. Bucking, A. 563, 31 (1949) f. e. s. G. Hesse and K. W. F. Bockmann, A. 563,37 (1949).)... 

Values of the ratio kp/ /2kt are given in Table 18. The absolute rate coefficients of cumylperoxy radical reactions with various esters were measured by Agabekov et al. (see Table 19). It is of interest to note that the reactivity of the esters of monocarboxylic acids is much greater than that of dicarboxylic esters (compare, for example, propionates and glutarates). 

Two variations of the malonic ester synthesis make use of dihaloalkanes. In the first of these, two molar equivalents of sodiomalonic ester are allowed to react with a dihaloalkane. Two consecutive alkylations occur, giving a tetraester hydrolysis and decarboxylation of the tetraester yield a dicarboxylic acid. An example is the synthesis of glutaric acid ... 

Acyclic weso-dicarboxylic esters with a succinic and glutaric acid backbone were also good substrates for PLE [224] and a-chymotrypsin (Scheme 2.28) [225]. Interestingly, an additional hydroxy group in the substrate led to an enhancement of the chiral recognition process in both cases. 

Dicarboxylic. .. s. Succin. .. y-Dicarboxylic. . . s. Glutar. . . Dicarboxylic acid amide esters... 

Gassman and Creary have reported that the centra bond of succinic esters can be cleaved with sodium in liquid ammonia. This method gives dimethyl glutarate from dimethyl cis- and trans-cyclopropane-l,2-dicarboxylates. The C-1—C-2 cleavage of a 1,2-diphenylcycIopropane which is part of a more complex, tricyclic compound has been effected by lithium in ammonia. Although it is known that lithium-ammonia reduction of a cyclopropyl ketone cleaves the bond which will allow tlw best overlap with the carbonyl Tt-system, the steric course of protonation at the f(-carbon has not, until recently, been known. Reduction of (301) at — 78 °C gives (302X the product with inversion, and (303),... 

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