Dimethyl 3-glutarate

Dimethyl glutarate at 300 MHz is an X2A2X2 system, which can be written as A2X4 and gives a quintet and a triplet. Less electronegative substituents in place of the COOMe groups result in a complex A2B4 spectrum. 

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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). 

Esters of higher diacids (e.g., dimethyl glutarates) have also proven quite informative. Thus, dimethyl 3-hydroxyglutarate (7.31) was hydrolyzed by PLE to the monoester of (S)-configuration (7.32), but the ee was low (ca. 20%) [55]. In contrast, a-chymotrypsin yielded the (R)-monoester with ee values of 60-70%, indicating large differences in the active sites of these... 

Polyketide synthesis. Polyketides (2) are obtained on reaction of the sodium lithium dianion (1) of methyl acetoacetate with dimethyl glutarates. When refluxed with Ca(OAc)2 in CH3OH, 2 cyclizes to l-oxo-l,2,3,4-tetrahydronaphthalenes in 30-75% yield.1... 

Glularic Acid. Until 1990-1991 glularic acid was available commercially from DuPont as a by-product in the production of adipic acid. It is no longer available, but DuPont produces dimethyl glutaratc and mixtures of dimethyl succinate and dimethyl glutarate. as well as mixtures of dimethyl glutarate and dimethyl adipate. 

Other Organic Removers. Concerns over the reported toxicity and carcinogenicity of methylene chlonde have stimulated research for alternative solvents in remover formulas. N-Methylpyrrolidinone and dibasic esters (dimethyl glutarate or dimethyl adipate) have been used in removers. They remove single-component finishes but work much more slowly than methylene chloride, petroleum, and oxygenate group removers. They haw little success on epoxy and catalyzed finishes. 

Dimethyl Pimelate The next higher homologue, dimethyl pimelate, returns us to an odd number of methylene groups, hence to a first-order spectrum. (See dimethyl glutarate with three methylene groups in Section 3.11.2.2). 

Dimethyl glutarate (0.6 mol) was added to 400 ml of methanol and treated with an aqueous solution of hydroxylamine (50 wt% in water 1.34 mol). The reaction stirred for 85 hours at ambient temperature, and the product was precipitated by introducing 400 ml of ethanol. The precipitate was isolated, and washed three times with ethanol, and vacuum-dried at 40°C for 48 hours the product was isolated in 66% yield as a white powder. 

The synthesis has been reported of the D-homo-c-nor-derivative (132) from the keto-ester (129). Stobbe condensation of 2-(l-methoxycarbonylethyl)-4,5-benzindan-l-one (129) with dimethyl glutarate afforded an acid which on hydrolysis-decarboxylation and subsequent esterification provided the diester (130). Catalytic hydrogenation of (130), followed by base hydrolysis, gave the diacid (131), which on pyrolysis yielded the tetracyclic keto-derivative (132). ... 

The highly enantioselective transformation of dimethyl meso-2,4-dimethyl-glutarate into its half ester had been performed only by a microorganism, Gliocraudiumroseum (81JA3580), and no report of a chemical chiral induction had been published before our success. 

Similarly, dimethyl cis- and /ra 5-l,2-cyclopropanedicarboxylate (2) gave dimethyl glutarate (3) upon reduction with sodium in liquid ammonia. 

Pyrolytic scission of cyclobutenes leads to a diene which promises to be useful in a Diels Alder approach to catechols. Heating of the sllyl derivative of the acyloin product from dimethyl glutarate in the presence of dlenophiles affords adducts of the transient diene. The adduct obtained with dimethyl acetylene dicarboxylate was converted in several steps to phthalic acid derivative. ... 

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