Dicarboxylic acid monoesters anhydrides

The mechanochemical technique has also been applied to the asymmetric opening of me o-anhydrides, catalyzed by the cinchona alkaloid quinidine (Scheme 8.4). A simple procedure affords the optically active dicarboxylic acid monoesters in high yields. Even mixtures of purely solid substrates react under these conditions, and no solvent is required, which significantly simplifies the product isolation step. ... 

Triphenylmethylsodium Dicarboxylic acid monoesters from dicarboxylic acid anhydrides... 

Dicarboxylic acid chloride esters from dicarboxylic acid anhydrides via dicarboxylic acid monoesters with cis-frcms-rearrangement... 

Aspartic acid y -esters—Dicarboxylic acid monoesters from dicarboxylic acid anhydrides. A soln. of 0.054 mole maleic anhydride in ahs. methanol refluxed 30 min., excess methanol distilled in vacuo, the monomethyl maleate thus obtained cooled in ice-water, pyridine followed by 0.05 mole isobutylamine added. 

TriphenylmethyIs odium Dicarboxylic acid monoesters from dicarboxylic acid anhydrides Phthalic acid monoesters of tert. alcohols... 

The formation of relatively ill-defined catalysts for epoxide/C02 copolymerization catalysts, arising from the treatment of ZnO with acid anhydrides or monoesters of dicarboxylic acids, has been described in a patent disclosure.968 Employing the perfluoroalkyl ester acid (342) renders the catalyst soluble in supercritical C02.969 At 110°C and 2,000 psi this catalyst mixture performs similarly to the zinc bisphenolates, producing a 96 4 ratio of polycarbonate polyether linkages, with a turnover of 440 g polymer/g [Zn] and a broad polydispersity (Mw/Mn>4). Related aluminum complexes have also been studied and (343) was found to be particularly active. However, selectivity is poor, with a ratio of 1 3.6 polycarbonate polyether.970... 

MixedPhosphonate Esters. Unsaturated, mixed phosphonate esters have been prepared from monoesters of 1,4-cyclohexanedimethanol and unsaturated dicarboxylic acids. For example, maleic anhydride reacts with this diol to form the maleate, which is treated with benzenephosphonic acid to yidd an unsaturated product. These esters have been used as flame-retardant additives for thermoplastic and thermosetting resins (97). 

Monoesters of symmetric dicarboxylic acids can be prepared either by monoesterification of a diacid [1] or by monosaponification of a diester. Dicarboxylic acids which can form five- or six-membered cyclic anhydrides are readily transformed into monoesters via these intermediates, but for diacids which cannot be converted into such cyclic anhydrides monosaponification of diesters seems to be more reliable than selective monoesterification. Monoesters or monoamides of succinic, maleic, glutaric, or related diacids can be rather unstable, because of the dose proximity of a carboxyl group (see Section 3.3). 

The usual range of carboxylic acid derivatives can be prepared and interconverted. Both carboxylic acid and ester functions are capable of reduction by lithium aluminum hydride to alcohols, or by controlled potential reduction to aldehydes. Attempts to form the anhydride from imidazole-4,5-dicarboxylic acid by heating with acetic anhydride failed. Instead, compound (199) is formed. This product forms the monoester (200) when heated with methanol and the hydrazide (201) when treated similarly with hydrazine (Scheme 107) (75S162). The corresponding l-methyl-4,5-dicarboxylic acid loses the 4-carboxyl group when heated with acetic anhydride, but in boiling aniline it is transformed into the 1-methyl-4-carboxanilide (79H(12)186). 

The use of cyclic anhydrides of dicarboxylic acids gave monoesters of the dicar-boxylic acids.1912-1915 Maleic anhydride reacted with slurried starch within 30 min at 45 °C at pH 7.5-8.5.1916 Another procedure involved the blending of an acetone suspension of starch with maleic anhydride, followed by evaporation of the acetone, the addition of sodium hydroxide powder, and heating the blend at 120 °C for 7 h.1917... 

Carboxylic anhydrides and alkylcadmiums give ketones in 50-70% yield 359 this reaction is also smooth with Grignard reagents, especially at low temperatures (—70°).365 Oxo carboxylic acids are obtained when alkylcadmiums or alkylzincs are treated with cyclic acid anhydrides359,366,367 or when a monoester monochloride of a dicarboxylic acid reacts with an isoalkyl-magnesium bromide.368 (The oxo group can be reduced by Clemmensen s... 

The dienophilic properties of vinylene carbonate (1,3-dioxol-2-one, 6) have been repeatedly exploited for the synthesis of cyclic polyols. Recently a number of ribofuranose derivatives have been synthesized starting from 6. The known adduct 7, obtained from 6 and furan, was c/r-hydroxylated, and after acetonation was hydrolyzed with base and cleaved with permanganate to give the dicarboxylic acid 8. The corresponding anhydride 9 gave, on treatment with trimethylsilyl azide, the isocyanate 10, which in turn was converted into the carbonate 11 on addition of methanol. The monoester 12, obtained in the reaction of anhydride 9 with isopropanol, was effectively resolved into enantiomers by the use of brucine or (/ )-l-(2-naphthyl)ethylamine. ... 

The diol 4 had never been described in the literature before we used it in the synthesis of 1. Initially, we tried to synthesize it using an enantioselective Diels-Alder reaction between a chiral fumarate equivalent 5 (Scheme 10.1) and butadiene 6, followed by double-bond dihydroxylation [41]. However, a more effective protocol for large-scale synthesis could finally be based on the procedure shown in Scheme 10.2, leading to enantiomericaUy pure (lS,2S)-cyclohex-4-ene-1,2-dicarboxylic acid 7 [42]. Here, a Bolm desymmetrization of tetrahydrophthahc anhydride 8 using quinine leads to monoester 9 in 89% ee. The monoester 9, in turn, can be epimerized to the trans isomer 10 which is hydrolyzed to obtain 7, after crystallization. This intermediate is the starting material for the synthesis of 4 and of other conformationally constrained DCCHD to be used as monosaccharide mimics [43, 44]. Our current best protocol for the large-scale synthesis of 7 is reported at the end of this chapter. 

The first synthesis of 4-pyrone derivatives with two CF3 groups was reported in 1988 by Lee and co-workers [22]. Acetone dicarboxylic acid monomethyl ester 47 reacted with isobutylene in sulfuric acid to form 48. Subsequent reaction with MgCL and trifluoroacetic anhydride led to pyrone 49. This compound was converted to the monoester 50, which gave pyrone 51. The latter was reacted with ammonia in methanol to form 4-hydroxypyridine 52 [22] (Scheme 15). 

Scheme 6.11 Enantioselective ling opening of meso anhydrides affords chiral monoesters of valuable dicarboxylic acids in excellent enantioselectivity using the sulfoneunide catalyst 77...

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