SYNOPSIS
7,7-Bis(methoxycarbonyl) -, 7,7-bis( ethoxycarbonyl) -, and 7,7-bis( isopropoxycarbonyl) -1,4benzoquinone methides (4a, 4b, and 4c) were successfully prepared as pure, isolable yelloworange needles. The values of the first reduction potential for 4a, 4b, and 4c were measured in dichloromethane containing tetrabutylammonium perchlorate by cyclic voltammetry to be 4 . 5 4 , -0.55, and -0.55 V, respectively, indicating that the alkyl groups do not significantly affect their electron-accepting properties. An anionic initiator butyllithium induced the homopolymerizations of 4a-c at O"C, but a cationic initiator boron trifluoride etherate did not of 4a-c at 0Β°C. Compounds 4a and 4b homopolymerized with a radical initiator 2,2'-azobis(isobutyronitri1e) (AIBN), but 4c did not, probably due to a larger steric hindrance effect of the isopropyl group compared with methyl and ethyl groups. Homopolymerizable compound 4a copolymerized with styrene in benzene in the presence of AIBN in a random fashion to give the monomer reactivity ratios rl (4a) = 2.40 f 0.40 and r2 (styrene) = 0.01 0.02 a t 60Β°C and the Q and e values of 4a were 21.2 and t1.13, respectively, indicating that 4a is a highly conjugative and electron-accepting monomer, while the nonhomopolymerizable compound 4c copolymerized with styrene in a perfectly alternating fashion in benzene in the presence of AIBN a t 60Β°C. No copolymerizations of 4a or 4c with 7,7,8,8tetracyanoquinodimethane took place in dichloromethane in the presence of AIBN at 60Β°C.