Allene-1,3-dicarboxylic acids

G. Gustavson, N. Demjanov,/. Prakt. Chem. 1888, 38, 201-207 in fact, the first allene to be synthesized was allene-1,3-dicarboxylic acid (glutinic acid B. S. Burton, H. v. Pech-man, Ber. Dtsch. Chem. Ces. 1887, 20,145-149), but its structure was only correctly assigned 67years later E. R. H. Jones,... 

As a first approach to the synthesis of nagilactone 296, a norditer-penoid isolated from Podocarpaceae, which inhibit the expansion and mitosis of plant cells, an intramolecular Diels-Alder reaction of allene 1,3-dicarboxylic acid esters was used. The cyclization of 297 afforded the 8-lactone 298, rather than the y-lactone 299 [85JCS(P1)747]. 

Anodic oxidation of N, N.-dimethylaniline in methanol yields the -methoxylated derivative (72), which reacts with substituted alkenes in the presence of Lewis acid to give a wide range of tetrahydroquinolines (e.g. 73).94- The adduct (75) from N-methylaniline and allene-1,3-dicarboxylic acid dimethyl ester (7 ) can be converted into the 4-quinolone (76) on treatment with polyphosphoric acid. 95 The use of nitrobenzenes as quinoline precursors is exemplified by the reaction sequence depicted in Scheme 17. The transition-metal-catalysed transformation is thought to involve the reduction of the nitrobenzene to the corresponding aniline via a nitrene intermediate.96... 

Allene 1,3-dicarboxylic acids (11) are available by carboxylation of the acetylenic dianions (10) (Scheme 11). The overall yields are only moderate (ca. 30%) but the simplicity of the procedure somewhat compensates for this. Both possible acetylenic mono-acids are also formed. When the dianion of but-2-ynoic acid is generated using Bu"Li-TMEDA as base reagent, it can be regioselectively... 

If two equivalents of the reagents are used, disubstitution to ECeC-CH(E)R occurs in most cases, but interestingly the reaction of LiCeCCH(Li)R with an excess of COj gives mainly the allenic dicarboxylic acids. These are probably the result of a rapid isomerization of the primary dilithium salt of the acetylenic diacid during the work-up or during the reaction of the dilithio compound with COj ... 

Penta-2,3-diendioic acid 1,3-allene-dicarboxylic acid) (71) Total electron density 367, 368,... 

The first allenic dicarboxylic acid, named glutinic acid (2,3-pentadienedioic acid) was isolated from Alnus glutinosa (Betulaceae). 

Since 3-methylenecyclobutane-l,2-dicarboxylic anhydride is easily converted to 3-methyl-2-cydobutene-l,2-dicarboxylic acid, it is an intermediate to a variety of cyclobutenes. The dimethyl ester of 3-methylenecyclobutane-l,2-dicarboxylic acid is also a versatile compound on pyrolysis it gives the substituted allene, methyl butadienoate, and on treatment with amines it gives a cyclobutene, dimethyl 3-methyl-2-cyclobutene-l,2-di-carboxylate. ... 

Chiral Lewis acids are also applicable in the deracemization of racemic allene dicarboxylates 289. Treatment of dimethylallene-l,3-dicarboxylate 289 with a chiral organoeuropium reagent, (+)-Eu(hfc)3, gave the corresponding optically active allene in 79% ee (Scheme 4.76) [118]. Unfortunately the chiral allene could not be isolated from the reaction mixture without loss of its optical purity. 

Anodic oxidation of 1,2-dicarboxylic acids as their alkali metal salts in concentrated aqueous solution gives the alkene with the loss of two molecules of carbon dioxide [125]. Succinic acid affords etltene and methylsuccinic acid ptopene [50]. Allene is obtained from itaconic acid and the isomeric methylmaleic and methyl-fumaric acids give propyne... 

A number of chiral allenes, such as the following dicarboxylic acid, have been prepared and resolved. 

Moore JM, Allen AC, Cooper DA (1984) Determination of manufacturing impurities in heroin by capillary gas chromatography with electron capture detection after deri-vatization with heptafluorobutyric anhydride. Anal Chem 56 642-646 Moore JM, Cooper DA, Lurie IS, Kram TC, Carr S, Harper C, Yeh J (1987) Capillary gas chromatographic-electron capture detection of coca-leaf-related impurities in illicit cocaine 2,4-diphenylcyclobutane-l,3-dicarboxylic acids, 1,4-diphenylcyclo-butane-2,3-dicarboxylic acids and their alkaloidal precursors, the truxillines. J Chromatogr 410 297-318... 

Homophthalic acid esters from 1,3-cyclohexadienes and allene-l,3-dicarboxylic acid esters... 

Crabbe has described what appears to be a simple, general one-pot procedure for the homologation of substituted acetylenes to the corresponding allenes (80). The acetylenic compound is heated with formaldehyde, di-isopropylamine, and copper(l) bromide under reflux in dioxan or THF for several hours. Yields range from fair to excellent. The reaction has been shown to tolerate a wide range of functionality such as alcohols, esters, and ethers. Indeed, the best yields are obtained when an oxygen function is vicinal to the acetylene. 1,3-Dilithioalk-l-ynes have been shown to act as precursors to allene-l,3-dicarboxylic acids (81) on... 

A full report has been published on the preparation and synthetic applications of the acetylenic dianions (35) of note here is their use in the preparation of allene-l,3-dicarboxylic acids (36). Kolbe co-electrolysis of 5-alkynoic adds, RC=C(CH2)3C02H, with half-esters of diadds Me02C(CH2) C02H followed by saponification gives the coupled product (37) in 45—50% yield. Alternative conditions have been reported for the preparation of oi-acetylenic acids from o>-iodoacids (esp. from fatty acids) using the lithium acetylide-ethylenediamine complex in HMPA. ... 

Conjugated dienesand allene react with carbon dioxide in the presence of nickel (o) catalysts to give eight- and five-membered ring metallacycles, respectively. Hydrolysis of the eight-membered ring metallacycle 28 with MeOH/HCl affords the c/x-dicarboxylic acid ester 29. 

The first synthesis of derivatives (77) of pentatetraene-carboxylic acid has been reported using a Wittig reaction of 1-H-allene-l,3-dicarboxylate monoester chlorides (76) in the presence of triethylamine.60 In one case an intermediate was obtained and was converted to (77) by further treatment with base. The reaction of carbon suboxide with phosphonium ylides has also... 

The Michael addition of 6-aminouracils to dimethyl allene-l,3-dicarboxylate in methanol or dimethyl sulfoxide provides a pentenedioic acid side chain in the 5-position capable of further elaboration (Z-isomer in methanol, -isomer in dimethyl sulfoxide). Heating these adducts of 6-aminouracil or its 1-methyl derivative in dimethylformamide gives the corresponding pyri-do[2,3-d]pyrimidine-2,4,7(l//,3//,8//)-triones 7. 44... 

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