The Radical Addition Reaction of Esters to Hexafluoropropene

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  • エステル類とヘキサフルオロプロペンとのラジカル付加反応

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γ-Ray induced addition reaction of 19 kinds of esters to hexafluoropropene was carried out as a part of studies on synthetic aspects of free-radical addition to fluoroolefins. Esters RCOOR' (R, R' -=CH3, CH2CH3, CH2CH2CH3, CH(CH3)2, CH2CH2CH2CH3, CH2CH(CH3)2 ), [1a-j], gave in considerable yields the corresponding 1: 1 adducts which c onsisted of several isomeric esters carrying a fluoroalkyl-side chain at different positions. The ratios of isomers of the 1: 1 adducts indicated the following trends of apparent addition reactivities of the carbon atoms in an ester molecule: (1 ) -CH>>CH2 >-CH3, ( 2 ) the carbons in the alkoxyl group (R'O) were more reactive than those in the acyl group (RCO), and ( 3 ) the carbons with increased distance from the carbonyl group showed much increased reactivities. The last two trends, ( 2 ) and ( 3 ), were opposite to those reported in radical addition reactions of esters to alkenes. Whereas diethyl carbonate [1r] reacted similarly, esters containing an electronegative group RCOOCH2CH2 (R=CH2F, CHClF, CH2Cl, CHCl2, CCl3, CH2CN, C6H5), [1k-q], either gave the 1: 1 adducts in much lower yields or gave no adducts at all, suggesting that the electro negative groups decrease reactivity for addition. γ-Butyrolactone [1 / s] gave no adduct.

Journal

  • NIPPON KAGAKU KAISHI

    NIPPON KAGAKU KAISHI 1976 (6), 949-955, 1976-06-10

    The Chemical Society of Japan

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