Effect of conditions of synthesis on the yield, molecular weight and structure of oligoarylenes synthesized in the presence of aluminium chloride and cupric chloride

1,1‘-Binaphthyl Dimers, Oligomers, and Polymers: Molecular Recognition, Asymmetric Catalysis, and New Materials

“…The resulting materials contained a mixture of 1,1‘-, 1,2‘-, or 2,2‘-binaphthyl units. The binaphthyl composition depended on both the catalyst and oxidant. − These naphthyl polymers generally had a dark color (e.g., dark purple) and high spin density, indicative of polynuclear aromatic structure formation during radical cation polymerization.…”

Dehydro coupling of aromatic nuclei by catalyst-oxidant systems: poly(p-phenylene)

“…For example, mixtures of m-terphenyl and naphthalene,173 benzene,174 or bi-phenyl175,176 afforded soluble, fusible copolymers from reaction with A1C13/CuC12173,175 or AlCl3/02.176 Similarly, soluble copolymers of naphthalene and benzene were obtained via oxidative coupling with A1C13/ CuCl2. 145,177,178 The copolymers generally retain the good thermal stability of PPP, but are more processable. More highly condensed aromatics (anthracene, phenanthrene, pyrene) were also copolymerized with benzene in the presence of A1C13/CuC12 to yield tractable products.179 A novel coupling system comprised of Mo03/02 in liquid HF was employed for the copolymerization of naphthalene with biphenyl or p-terphenyl.…”

Coupling of aromatic nuclei. 20. Mixed dehydrotrimerization of biphenyl-mesitylene by aluminum chloride-cupric chloride

“…Fraction C was recrystallized from methanol. Cooling in a methanol-dry ice bath yielded white crystals: mp 66-68 °C; mass spectrum m/e 272 (10 eV), 273 (33), 272 (M+, 100), 271 (16), 257 (42), 242 (27), 241 (25), 181 (13), 279 (17), 165 (19), 149 (21), 91 (13), 85 (17), 83 (15), 71 (23); NMR 0.81 (d, impurity), 1.2-1.4 (m, impurity), 2.01 (s, 6, 0-CH3), 2.29 (s, 3, p-CHg), 2.S-2.7 (m, impurity), 3.9-4.2 (m, impurity), 6.85 (s, 2, (CH3)3C6H2), 7.10-7.66 (m, aromatic hydrogens).…”

“…Fraction E (1) was recrystallized from hexane. Cooling in a methanol-dry ice bath precipitated white needles: mp 233-235.5 °C; a methanol-dry ice bath precipitated white needles: mp 233-235.5 °C; NMR 2.01 (s, 12,0-CH3), 2.29 (s, 6, p-CH3), 6.85 (s, 8, (CH3)3C6H2), and 7.14-7.75 (AB pattern, 8, J = 4 Hz, CgH^; mass spectrum m/e 390 (10 eV), 391 (29), 390 (M+, 100), 375 (21), 360 (18), 345 (13), 330 (7), 315 (6), 272 (7), 209 (13), 195 (35), 187 (14), 181 (17), 180 (31), 179 (29), 172 (14), 165 (17), 91 (10); IR (KBr) 1600 (w), 1390 (w), 1370 (w), 1100 (w), 1478 (m), 1000 (m), 845 (m), 817 (s), 742 (w), 734 (w); UV Xmax (cyclohexane) 267.5 nm (log e 4.46). When petroleum ether (bp 30-60 °C) was added to fraction H, an insoluble shiny, white crystalline solid was isolated, mp 283-285 °C.…”

“…(16) J. W. Knapczyk, J. J. Lubinkowski, and W. E. McEwen, Tetrahedron Lett., 3739(1972). (17) We have pointed out in a previous paper3 that ordinarily the material balance in reactions of diphenyliodonium salts with nucleophiles is excellent only when at least 1 equiv of 1,1-diphenylethylene is present in the reaction mixture. Among other effects, this olefin inhibits destruction of iodobenzene by a free-radical chain reaction.…”