Radical addition reactions. Part II. The addition of ethyl cyanoacetate to conjugated olefins
Document Type
Article
Publication Date
1-1-1968
Abstract
The addition of ethyl cyanoacetate, catalysed by t-butyl peroxide at 155-160°, to a series of conjugated olefins XCH:CHY, namely dimethyl fumarate (X = Y = CO2Me), methyl crotonate (X = Me, Y = CO 2Me), β-methyl-styrene, methyl cinnamate, benzylideneacetone, and cis- and trans-cinnamonitrile (X = Ph, Y = Me, CO2Me, Ac, or CN, respectively), gives mainly the 1:1-adduct, XCHR·CH2Y (R = CH(CN)·CO2Et), in the first two cases, and XCH 2·CHRY in the others, in yields of 26, 53, 42, 31, 16, 26, and 20%, respectively. Isomerisation of cis-cinnamonitrile to the trans-isomer under the conditions of the reaction is interpreted as due to the reversibility of the addition step. This, however, does not occur in the addition of butanal to the same nitrile, which gives PhCH2·CH(CN)·COPr n (40%).
Keywords
Radical addition reactions, ethyl cyanoacetate, conjugated olefins
Divisions
CHEMISTRY
Publication Title
Journal of the Chemical Society C: Organic
Publisher
Royal Society of Chemistry
Additional Information
Huang, R.L., Ong, C.-O., Ong, S.H. Department of Chemistry, University of Malaya, Malaysia.