Glutaric acid esters

Acryhc esters dimerize to give the 2-methylene glutaric acid esters catalyzed by tertiary organic phosphines (37) or organic phosphorous triamides, phosphonous diamides, or phosphinous amides (38). Yields of 75—80% dimer, together with 15—20% trimer, are obtained. Reaction conditions can be varied to obtain high yields of trimer, tetramer, and other polymers. 

Fig. 13.3 Signaling pathways involved in oxidized phospholipid-induced apoptosis in mammalian smooth muscle and endothelial cells. AIF, apoptosis inducing factor Apaf-1, apoptosis activating factor 1 aSM, acid sphingomyelinase Az-PC azelaoyl acid ester of lyso-PC Cyt c, cytochrome c G-PC, glutaric acid ester of lyso-PC IM, intermembrane space of the mitochondria JNK, c-Jun N-terminal kinase OV-PC, 5-oxovaleric acid ester of lyso-PC p38, p38 mitogen-activated protein kinase PM, plasma membrane...

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).)... 

Intramolecular hydrolysis is substantially faster than the intermolecular reaction (Table 2.6). The effective molarity sharply increases when the reactive carboxylate anion is in close proximity to the ester carbonyl group and, by its presence, retards the mobility of the carbonyl group. Thus, the effective molarity increases (Table 2.6) as the C—C bond mobility decreases. Two bonds can rotate in a glutaric acid ester, whereas only one can... 

The water solubiUty of glutaric acid fosters its toxicity. Glutaric acid is a known nephrotoxin. Renal failure has been documented ia rabbits adruinistered sodium glutarate subcutaneously (124). Dibasic ester (Du Pont), which contains primarily dimethyl glutarate, has low acute toxicity by inhalation and by ingestion, and is moderately toxic via dermal absorption. The acid is both a dermal and ocular irritant of humans. The ester is a severe skin irritant and may cause a rash ia humans (120). 

Accelerations (or decelerations) imposed by the cycloamyloses on the rate of an intramolecular reaction may be derived from a conformational effect. The rate of an intramolecular reaction depends not only on the proximity of the reactive groups but also on their relative orientation. For example, Bruice and Bradbury (1965) have shown that the rates of formation of cyclic anhydrides from mono esters of 3-substituted glutaric acids depend on the size of the substituent at the 3-position. This observation was interpreted as a change in the ground state population of reactive and non-reactive conformers as the 3-substituents are varied (Scheme IX). Reason-... 

Rates of Hydrolysis of Mono-p-Carboxyphenyl Esters of 3-Substituted Glutaric Acids in the Absence and Presence of Cycloheptaamylose at pH 9.4 and 30° ... 

In another example of intramolecular participation, the attack of the carboxylate ion group of mono-p-carboxyphenyl esters of substituted glutaric acids, the rate of anhydride formation is sharply reduced by /3-CD (VanderJagt et al., 1970). Apparently, the substrates bind to /3-CD in a conformation that is unsuitable for reaction. At the same time, the large rate reductions must also mean that the transition state of the reaction cannot be bound by /3-CD in such a way as to be significantly stabilized. 

Glutaric acid, p-carboxyphenyl esters of 3-substituted, conformational effects on cy-cloamylose reactions, 23 245 Glyceraldehyde, 32 348 Glycerol, 32 352... 

HN C6H.6N( 0)2 mw 126.12, plates (from, w), mp 300° (dec) si sol in ale hot w insol in usual solvents. Prepd by boiling with soda soln jS-hydroxy/3-amino-glutaric acid ethyl ester amide, or by heating at 130°2,4 6-trihydroxypyridine and ammonium acetate... 

Similarly, glutaryl acylase was used as a biocatalyst in the synthesis of amides of glutaric acid derivatives using the acyl donor as the liquid phase in which the undissolved nucleophile was suspended [33]. In another example, immobilized lipase was used in a medium composed solely of substrate to resolve racemic ketoprofen esters via hydrolysis [36]. 

Biocatalysis plays a central role in the manufacturing of statin side chains (Figure 6.2). A first set of approaches exploits enzymatic desymmetrization reactions, for example, of the methoxyacetyl ester of glutaric acid diethyl ester with commercially available a-chymotrypsin as explored by Ciba SC with a yield of 94% and enantiomeric excess of up to 98% [1]. In the optimized procedure, the substrate was available in a concentration of 1 M at an enzyme/substrate ratio of 7% (wt/wt), and the reaction took approximately a day. The subsequent steps to the final acetonide also involved a pig-liver esterase (PLE) catalyzed selective hydrolysis of the methoxyacetyl group (Figure 6.2a). 

Dimethyl 1,3-acetonedicarhoxylate Glutaric acid, 3-oxo-, dimethyl ester (8) Pentanedloic acid, 3-oxo-, dimethyl ester (9) (1830-54-2)... 

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