Dimethyl maleic anhydride

Similar products have been isolated from the photocycloaddition of dimethyl-maleic anhydride to isoprene.(97>... 

A simple procedure to prepare 5-aryl- and 5-pyridyl-2-furaldehydes from inexpensive, commercially available 2-furaldehyde diethyl acetal was reported. The reaction proceeded in a four-step, one-pot procedure and the yield of coupling step was usually between 58-91% <02OL375>. A facile route to 3,4-furandicarboxylic acids was developed. DDQ-oxidation of 2,5-dihydrofuran derivatives, which were produced from dimethyl maleic anhydride, furnished the desired esters of furan-3,4-dicarboxylic acid <02S1010>. The furan-fused tetracyclic core of halenaquinol and halenaquinone possessing antibiotic, cardiotonic, and protein tyrosine kinase inhibitory activities was synthesized. Intramolecular cycloaddition of an o-quinodimethane with furan gave the adduct as a single isomer via an enrfo-transition state, which was converted to trisubstituted furan by oxidation-elimination reactions <02T6097>. 

Olefinic dienophiles such as maleic anhydride and maleimide add to 4,6-dimethyl-2-pyrone to afford mono Diels-Alder adducts. These on irradiation afford, by a photo-decarboxylation, a diene which can be trapped by a dienophile to afford the products (311). - - Acetone-sensitized photoaddition of the oxazolones (312) to maleic and dimethyl maleic anhydride yields the adducts (313). - ... 

BenzolMfurans yielded (2 + 2)-cycloadducts (191) with dimethyl-maleic anhydride, via excitation of an initially formed charge-transfer complex, together with oxetans.218 Similar (2 + 2)-cycloadducts (192) were obtained from quinones and benzoU>] furan and some of its derivatives.143,200 Irradiation of W-acyl-l//-indoles in the presence of olefins, either with or without acetophenone as a sensitizer, produced a series of (2 + 2)-cycloadducts 193, usually as a mixture of exo- and endoisomers.219 The olefins that give a (2 + 2)-cycloadduct are either electron-rich olefms, such as ethyl vinyl ether and vinyl acetate, or... 

The direct synthesis of cantharidin by a Diels-Alder reaction of furan with dimethyl maleic anhydride 6 is not possible. However, cycloaddition can be carried out with 2,5-dihydrothiophene-3,4-dicarboxylic acid anhydride 8 as dienophile. The cycloadduct 9 exolendo mixture 85 15) is subsequently hydrogenated and the tetrahydrothiophene ring in 10 is cleaved by a reductive desulfurization [17] ... 

A number of attempts were made to prepare H-H poly(methyl methacrylate). Initial attempts to prepare alternating copolymers of ethylene and 2,3-dimethyl maleic anhydride were made, under our reaction conditions all attempts have failed as yet. Other work on copolymerization of 2,3-dimethylmaleic anhydride with more electron-rich monomer, gave indications that this polymerization could be successfully carried out under the proper conditions as steric hindrance does not appear to be the reason for the unsuccessful alternating polymerization involving 2,3-dimethyl maleic anhydride. 

H. Kamada, Tsutsumi, Y. Sato-Kamada, K. Yamamoto, Y. Yoshioka, Y. Okamoto, T. Nakagawa, S. Nagata and T. Mayumi, Synthesis of a poly(vinylpyrrolidone-co-dimethyl maleic anhydride) co-polymer and its application for renal drug targeting, Nat. Biotechnol, 21, 399 04 (2003). 

In 1980 W.G. Dauben et al. [9] drew attention to the fact that they had succeeded in synthesizing cantharidin, essentially in line with the approach of v. Bruchhausen and Bersch. Furan (1) and a latent version 2 of dimethyl maleic anhydride afforded a mixture of 3 and 4 as the major and minor components respectively (Fig. 3). After removal of the minor adduct and catalytic hydrogeno-lysis of the major adduct, cantharidin was isolated in high yield. To make the Diels/Alder reaction go reliably, high pressure conditions had to be used. 

The direct synthesis of cantharidin via Diels-Alder reaction of furan with dimethyl maleic anhydride (7) is not possible. However, cycloaddition can be carried out with... 

Jurczak has shown that 3,4-dimethoxyfuran 35 is a more active diene tiran furan, and employed in the synthesis of dimethoxycantharidin 41 [24]. Its higher reactivity overcomes the low reactivity of dimethyl maleic anhydride and high pressure cycloaddition with 35 could be achieved under 22kbar at room temperature (Scheme 10). Reactions performed at lower pressures, e.g., lOkbar, neither at room temperature nor at 60°C afforded (even after 16h of pressurization) the cycloadduct. Reaction was stereospecific, since no endo-adduct could be detected. Hydrogenation of the adduct 40 in the presence of 10% Pd/C gave 41. 

Schenck, G. O., Hartmann, W., and Steinmetz, R., Four-membered ring synthesis by the photosensitized cycloaddition of dimethyl maleic anhydride to olefins, Chem. Ber., 96, 498,1963. 

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