N. Miyaki et al., PALLADIUM-CATALYZED 3-COMPONENT COUPLING - POLYMERIZATION OF DIYNE, ARYL DIHALIDE, AND HYDRIDE, Polymer bulletin, 39(6), 1997, pp. 677-684
The palladium-catalyzed three-component coupling reaction of acetylene
s, aryl halides, and hydride and it's application to polymer synthesis
are described. The coupling reaction of 1,2-diphenylacetylene, iodobe
nzene, and sodium diethyl benzylmalonate was carried out at 80 degrees
C for 48 h in 1,4-dioxane with Pd(OAc)(2)/tri-o-tolylphosphine, from
which triphenylethylene was obtained in 71% isolated yield. The benzyl
ic hydrogen of sodium diethyl benzylmalonate was supposed to be a hydr
ide source in the present reaction by detecting diethyl benzalmalonate
in the reaction system. Based on the results, the coupling polymeriza
tion of 1,2-bis(4-phenylethynylphenyl)ethane, 4,4'-diiodobiphenyl, and
sodium diethyl benzylmalonate was carried out at 80 degrees C for 48
h to produce a polymer (M-n=8500, M-W/M-n=3.0) in high yield. Using va
rious aryl dihalides, the corresponding polymers having trisubstituted
ethylene units were also obtained in high yields.