Roderic P. Quirk, Deanna L. Gomochak, Chrys Wesdemiotis and Mark A. Arnould
The functionalization of polymeric organolithium compounds with 3,4-epoxy-1-butene in benzene at room temperature yielded the corresponding butene-ol-functionalized polymers in a 95 wt % yield with 5 wt % of the unfunctionalized polymer isolated. For poly(styryl)lithium, the functionalized product corresponded to approximately equal amounts of 1,4-, 3,4-, and 4,3-addition, as determined by quantitative 13C NMR and attached-proton-test 13C NMR analysis. The 1,4-addition product was obtained in high yields for poly(butadienyl)lithium and poly(isoprenyl)lithium chain ends, at a low temperature (6 °C), by use of inverse addition or by the addition of triethylamine (20 equiv). Dehydration of the butene-ol-functionalized polymer produced the corresponding diene-functionalized macromonomer. All products were characterized by 1H and 13C NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.