Methyl itaconate

The 3-exo cychsation of ester-substituted 3-butenyl radicals is important in the rearrangement of 2-methyleneglutamate to 3-methyl itaconate catalysed by a-methyleneglutamate mutase. Newcomb and co-workers have applied laser flash photolysis to cleverly designed precursors to show that an ester group at the 1-position of 3-buten-l-yl accelerates the 3-exo cychsation by a factor of about 3, but that the same substituent at the 3-position slows the process by a factor of about 50 [45]. 

Methyl o-iodobenzoate, 130, 132 Methyl isobutyl ketone, 652 Methyl itaconate, 366... 

Continuous enantioselective hydrogenation of C=C double bond in methyl itaconate (Figure 12.9) over (Sa, Rc)-l-naphtyl-QUINAPHOS (phosphine-phosphoroamidatE ligand) (Figure 12.10) catalyst immobilized on [CjmimKNTfjj-silica was demonstrated [20]. 

Methyleneglutarate mutase interconverts 2-methyleneglutarate and (if)-3-methyl-itaconate (Table 1, entry 3) in a radical reaction, induced by the 5 -deoxyadenosyl radical (from 2), and involves the rearrangement between a... 

Propargyl chloride Methyl itaconate 66 % - -methyl-3-chlorobut-3-enoic acid-1 (traces) [566]... 

Poly(itaconic acid) has also been prepared in a 0.2M/liter aqueous solution using potassium persulfate at 50 C over a 5-hr period under reduced pressure. After the polymer is reprecipitated twice into methanol-ethyl acetate, a polymer is isolated with a molecular weight of 1.64 x 10, determined by vapor pressure osmometry of a methanolic solution of the methyl ester prepared from the polymer [49]. Unfortunately Tsuchida and coworkers did not report on the quantitative extent to which poly(methyl itaconate) had been formed from this polymer (presumably by reaction with diazomethane). Consequently, there is little in the literature to confirm or dispute the paper by Braun and Azis el Sayed [97], which offered evidence that during the free-radical polymerization of itaconic acid, carbon dioxide evolves to a considerable extent. During the process, it seems that hydroxyl and formyl radicals are generated and incorporated in the macromolecule. It is proposed by these authors that the homopolymer of itaconic acid contains virtually no itaconic acid repeat units but rather intramolecular lactone rings and acetal- or hemiacetal-like moieties. Since the polymer remains soluble in the reaction solvent (dioxane). 

The Cu-catalysed (3-6 mol%) addition of l,l,l-trichloro-2,2,2-trifluoroethane to methyl itaconate leads to the 1 1 adduct 85 in 57 % yield. Double HCl elimination with triethylamine affords the diene 86 (Z = 17 83). Refluxing of 86 in mesitylene leads to elimination of MeCl and formation of 87 in 62 % yield [37] (Scheme 27). 

Poly(di-n-methyl itaconate) Chromatography Tetrahydrofiiran SEC, dtrastyragel 1365... 

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