Dicarboxylic acid esters cyclic

Russell and coworkers147 had found that treatment of dimsyl anion 88 or of a similar methylsulfonyl carbanion with 1,2-, 1,3- and 1,4-dicarboxylic acid esters can give five- to seven-membered cyclic compounds. By this type of cyclization, they prepared ninhydrin hydrate 106 from diethyl phthalate148,149. 

Which isomer of (LXIII) is actually formed remains an open question. In addition to the expected cyclic and open-chain products, two isomeric dicarboxylic acid esters are produced. These result from the reaction of the allyl intermediate with a second molecule of acrylic ester, followed by... 

Patty, F.A., Editor (1963) Aromatic and Cyclic Dicarboxylic Acid Esters. Industrial Hygiene and Technology. Volume II, Interscience Publishers. 

Table 11.1-7. a-Chymostrypsin-catalyzed enantiotopos-differentiating hydrolysis of prochiral cyclic dicarboxylic acid esters, acyclic dicarboxylic acid esters and cyclic diol diacetates and enantiomer-differentiating hydrolysis of racemic carboxylic acid esters in aqueous solution. 

Because of the ease of synthesis and industrial importance of diallyl esters much of the research has dealt with the behavior of the isomeric phthalates. Some other dicarboxylic acid esters have been studied by Simpson and Holt [41]. The kinetics of the poljmierization of the diallyl esters of oxalic, malonic, succinic, adipic, and sebacic acid have also been considered. In previous kinetie studies, no differentiation was made between the behavior of the uncyclized monomer (or its free radical) and of the cyclic free-radicals. A priori, differences should have been presumed, but evidently Matsumoto and Oiwa [46] were the first seriously to attempt a kinetic analysis based on the concept that the linear and the cyclic units are two different species. In effect, these two species copolymerize with each other. However, the analysis has not been carried so far as to determine reactivity ratios. 

Cyclic 2-acyl-j -diketones from dicarboxylic acid esters... 

Reaction of a-diketones with lead tetraacetate Dicarboxylic acid esters from cyclic a-diketones... 

The scope of this reaction is similar to that of 10-21. Though anhydrides are somewhat less reactive than acyl halides, they are often used to prepare carboxylic esters. Acids, Lewis acids, and bases are often used as catalysts—most often, pyridine. Catalysis by pyridine is of the nucleophilic type (see 10-9). 4-(A,A-Dimethylamino)pyridine is a better catalyst than pyridine and can be used in cases where pyridine fails. " Nonbasic catalysts are cobalt(II) chloride " and TaCls—Si02. " Formic anhydride is not a stable compound but esters of formic acid can be prepared by treating alcohols " or phenols " with acetic-formic anhydride. Cyclic anhydrides give monoesterified dicarboxylic acids, for example,... 

So far, various dicarboxylic acid derivatives, dicarboxylic acids, their activated and non-activated esters, cyclic acid anhydrides, and polyanhydrides have been polymerized with glycols through lipase catalysis to give polyesters. 

Various combinations of dicarboxylic acid derivatives and glycols enzymatically afforded polyesters under mild reaction conditions. Dicarboxylic acids as well as derivatives, activated and non-activated esters, cyclic acid anhydride, and polyanhydrides, were found to be useful as monomer for the enzymatic synthesis of polyesters. 

A substituted acetamidomalonic ester, tetraethyl 1 -acetamido-4-hydroxy-butane-l,l,3,3-tetracarboxylate, was used in the preparation of cis- and frans-pyrrolidine-2,4-dicarboxylic acids, cyclic analogs of glutamic acid (91TL3049). 

Cyclic mew-configurated 1,2-dicarboxylic acid dimethyl esters are excellent substrates for pig liver esterase90. Cyclopropanedicarboxylales have been studied not only for synthetic reasons, but also so that an active-site and/or substrate model of pig liver may be developed13 5. The results obtained, compounds 11-17, are a good demonstration of the scope and limitation of PLE in asymmetric synthesis. Enantiomeric excesses of the monoesters can be determined by conversion into the amides with (S)-l-phenylethylamine and analysis either by GC or H-NMR spectroscopy, whereas the absolute configuration rests on chemical correlation. 

The acyloin condensation was used in an ingenious manner to prepare the first reported catenane (see p. 91).727 The catenane (39) was prepared by a statistical synthesis (p. 91) in the following manner An acyloin condensation was performed on the diethyl ester of the C34 dicarboxylic acid (tetratriacontandioic acid) to give the cyclic acyloin 37. This was reduced by a Clemmensen reduction with DCI in D20 instead of HC1 in H20, thus producing a C34 cycloalkane containing deuterium (38) 728... 

Despite earlier observations,624 625 ozonolysis of cyclic olefins in MeOH or in mixed solvents (ethers or esters and MeOH) followed by isomerization in the presence of Lindlar Pd and hydrogen does not give directly dicarboxylic acids. Instead, mainly the corresponding dialdehydes are formed.626 The best method of synthesis of dicarboxylic acids is ozonolysis of cycloalkenes in a mixture of acetic acid and formic acid followed by further oxidation with oxygen 626... 

The acid esters of 1,2-dicarboxylic acids are conveniently prepared by heating the corresponding cyclic anhydride with one molar proportion of the alcohol (see the preparation of alkyl hydrogen phthalates from phthalic anhydride and their use in the resolution of racemic alcohols, Section 5.19). 

The intramolecular Wurtz-type coupling of dihaloorganic compounds with use of metallic zinc is a classical synthetic route to cyclic compounds. For example, cyclopropane derivatives can be prepared from 1,3-dihalo-propanes (29, 189a, 248, 451), and cyclobutane derivatives from 1,4-dihalobutanes (71). These reactions presumably proceed via the intermediate formation of organozinc compounds. The reaction of diethylzinc with esters of a,a -dibrominated aliphatic dicarboxylic acids leads to the... 

The ability to accept electrons from donors is particularly pronounced in acrylic acid derivatives [85] its alkyl esters [78, 87, 88], acrylonitrile [88], acrylamide, hydroxylacrylates [85], and further in styrenes substituted with an electronegative atom or group m-nitrostyrene, 2,6-dichlorostyrene [86], / -nitrostyrene [89] bicyclobutane-1-carbonitrile [89] lactones /J-propio-Iactone [85], sulfolactone vinyl ketones [87] unsaturated dicarboxylic acids and their derivatives diethyl fumarate, fumaronitrile [90], ROOC—N— N—COOR [86], cyclic anhydrides of diacids [91 ], particularly maleic anhydride [78, 92] ethylenes substituted with electronegative groups [93, 95]... 

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