Synthesis, isolation, characterization and reactivity of ortho-substituted phenyl alkyne oligomers and macrocycles.

摘要

The synthesis, isolation and characterization of a series of ortho substituted phenyl alkyne linear oligomers and macrocycles are described. The syntheses of these compounds were achieved using Hagihara's catalytic Stephens-Castro coupling reaction of iodoarenes and terminal acetylenes. The linear oligomers were then reacted with 1,2-diiodobenzene to synthesize the macrocycles HBC {dollar}{lcub}{dollar}1,2:5,6:9,10:13,14:17,18:21,22- hexabenzo-3,7,11,15,19,23-hexadehydro (24) annulene{dollar}{rcub}{dollar}, OBC {dollar}{lcub}{dollar}1,2:5,6:9,10:13,14:17, 18:21,22:25,26:29,30-octabenzo-3,7,11,15,19,23,27,31-octadehydro (32) annulene{dollar}{rcub}{dollar}, and DBC {dollar}{lcub}{dollar}1,2: 5,6: 9,10: 13,14: 17,18: 21,22: 25,26: 29,30: 33,34: 37,38-decabenzo-3,7,11,15,19,23,27,31,35,39-decadehydro (40) annulene{dollar}{rcub}{dollar} and DODECA {dollar}{lcub}{dollar}1,2: 5,6: 9,10: 13,14: 17,18: 21,22: 25,26: 29,30: 33,34: 37,38: 41,42: 45,46-dodecabenzo-3, 7, 11, 15, 19, 23, 27, 31, 35, 39,43,47-dodecadehydro (48) annulene{dollar}{rcub}{dollar}. The crystal structures of DBC and DODECA are also included.; The synthesis, isolation, characterization and crystal structures of three cyclic strained diacetylenes are described {dollar}{lcub}{dollar}1,2:5,6:9,10-tribenzo-3,7,11,13-tetradehydro (14) annulene, 1,2:5,6:9,10: 13,14-tetrabenzo-3,7,11,15,17-pentadehydro (18) annulene, 1,2:5,6:9,10: 13,14:17,18-pentabenzo-3,7,11,15,19,23,25-hepta dehydro (26) annulene{dollar}{rcub}{dollar}. They were synthesized via an intramolecular Hay coupling reaction. Crystals of the tribenzo compound changed from yellow to a violet color with a metallic luster when exposed to light which is evidence for a 1,4 topochemical polymerization. DSC, TGA and solid state NMR spectra of the violet compound is also presented.; The reaction chemistry of HBC with lithium and thermal reactions of the DODECA are described. The reactions of 1,2-bis ((2-ethynylphenyl) ethynyl) benzene with 1, 2, 3 and 4 equivalents of Co{dollar}sb2{dollar}(CO){dollar}sb8{dollar} are described. Four acetylene bonds are present, but only two unique compounds were formed.; A poly-Bergman reaction was attempted using a {dollar}rm RuCp(PMesb3)sb2sp{lcub}+{rcub}(PFsb6)sp{lcub}-{rcub}{dollar} complex bound to an oligomer. The synthesis, crystal structure and reactivity of bis ({dollar}etasp5{dollar}-2,4-cyclopentadien-1-y1) ({dollar}mu{dollar}- (1, 2-phenylene bis (2, 1-ethynediyl-2, 1-phenylene-2-ethenyl-1-ylidene))) tetrakis (trimethylphosphine) di-ruthenium is described.; The syntheses of poly(methylphenyl)silane and polyphosphazene are described. Poly(methylphenyl) silane was grafted with 1,2-bis ((2-ethynylphenyl) ethynyl) benzene. Phosphonitrilic chloride trimer was reacted with one half equivalent of the lithium dianion of 1,2-bis ((2-ethynylphenyl) ethynyl) benzene.