Aldol-type reactions Methyl acrylate

The diazabicyclooctane (DABCO) catalysed aldol type reaction of acrylic esters with aldehydes has now been extended to use methyl... 

Chromium carbene complexes, 82 Methyl acrylate, 183 (2R,4R)-Pentanediol, 237 Titanium(IV) chloride, 304 Nitroaldols Nitromethane, 199 Intramolecular reactions Methyl acrylate, 183 Other aldol-type reactions Bis(2-pyridinethiolato)tin(II), 40 Alkoxycarbonylation (see Carboalkoxy-lation)... 

Although ketones are not generally considered to be reactive carbonyl partners in MBH reactions (except under high pressure), the enhanced reactivity of certain a-diketones towards aldol-type reactions make them suitable partners for reaction with MBH-type vinyl carbanion equivalents. Indeed, a-keto esters have been found to possess the requisite reactivity and are very reactive electrophiles for the MBH reaction of acrylate, methyl vinyl ketone, acrylonitrile and acrolein in the presence of a tertiary amine, such as DABCO (Scheme 1.66). " ... 

Polymerizations of vinyl ketones such as methyl vinyl ketone are also complicated by nucleophilic attack of the initiator and propagating carbanion at the carbonyl group although few details have been established [Dotcheva and Tsvetanov, 1985 Hrdlovic et al., 1979 Nasrallah and Baylouzian, 1977]. Nucleophilic attack in these polymers results in addition, while that at the ester carbonyl of acrylates and methacrylates yields substitution. The major side reaction is an intramolecular aldol-type condensation. Abstraction of an a-hydrogen from a methyl group of the polymer by either initiator or propagating carbanion yields an a-carbanion that attacks the carbonyl group of the adjacent repeat unit. 

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