Several synthetic routes were designed to prepare 1,3,5-tris[(4-ethynylphenyl)ethynyl]benzene. The synthetic routes and reaction conditions were contrasted and discussed, when multiple Sonogashira reactions were occurred between multifunctional alkyne-terminal compounds and aromatic bromine compounds, the different substitution degree compounds with similar polarity were obtained, and they were difficult to separate. Whereas the reactions between multifunctional alkyne-terminal compounds and aromatic iodine compounds can avoid this situation. 1,3,5-Tribromobenzene reacted with 3-methylbutynol to afford 1,3,5-tris(3'-hydroxy-3'-methyl-but-1'-ynyl)benzene, then 1,3,5-triethynylbenzene was obtained by the cleavage reaction of the compound in presence of potassium hydroxide and toluene. On the other hand, using 4-iodoaniline and trimethyl silyl acetylene as raw materials, 4-trimethylsiylethynyl iodobenzene was synthesized by diazo reaction and halogenation. Therefore, 1,3,5-tris[(4'-ethynylphenyl)ethynyl]benzene was prepared by the cleavage reaction of the 1,3,5- triethynylbenzene and 4-trimethylsiylethynyl iodobenzene. The structures of the target compound and intermediates were confirmed by 1H NMR, 13C NMR techniques and element analysis.
[1] Toshiki, A.; Takashi, K.; Masahiro, T. Polymer 2006, 47(14), 4867.
[2] Fu, H. J.; Huang, Y. D.; Liu, L. Mater. Sci. Technol. 2004, 20(11), 1654.
[3] Devadoss, C.; Bharathi, P.; Moore, J. S. J. Am. Chem. Soc. 1996, 118(40), 9635.
[4] Wang, P. W.; Liu, Y. J.; Devadoss, C.; Bharathi, P.; Moore, J. S. Adv. Mater. 1996, 8(3), 237.
[5] Hu, Q. S.; Pugh, V.; Sabat, M.; Pu, L. J. Org. Chem. 1999, 64(20), 7528.
[6] Pugh, V. J.; Hu, Q. S.; Pu, L. Angew. Chem., Int. Ed. 2000, 39(20), 3638.
[7] Pugh, V. J.; Hu, Q. S.; Zuo, X.; Lewis, F. D.; Pu, L. J. Org. Chem. 2001, 66(18), 6136.
[8] Luing, U.; Eggert, J. P. W.; Hagemann, K. Eur. J. Org. Chem. 2006, 2747.
[9] Kaneko, T.; Horie, T.; Asano, M.; Aoki, T.; Oikawa, E. Macromolecules 1997, 30(10), 3118.
[10] Kaneko, T.; Horie, T.; Asano, M.; Matsumoto, S.; Yamamoto, K.; Aoki, T.; Oikawa, E. Polym. Adv. Technol. 2000, 11(8～12), 685.
[11] Kaneko, T.; Yamamoto, K.; Asano, M.; Teraguchi, M.; Aoki, T. J. Membrane Sci. 2006, 278(1～2), 365.
[12] Hawker, C. J.; Frechet, J. M. J. J. Am. Chem. Soc. 1990, 112, 7638.
[13] Moore, J. S. Acc. Chem. Res. 1997, 30, 402.
[14] Wang, C. Y.; Zhong, H. B.; Li, S. S.; Shen, Y. J. Chin. J. Chem. 2010, 28(5), 699.
[15] Ji, X. Y.; Zhang, J.; Tang, C. L.; Wang, J. Chin. J. Org. Chem. 2011, 31(1), 126 (in Chinese). (纪宪勇, 张婧, 汤灿林, 王杰, 有机化学, 2011, 31(1), 126.)
[16] Chandra, K. L.; Zhang, S.; Gorman C. B. Tetrahedron 2007, 63, 7120.
[17] McDonagh, A. M.; Powell, C. E.; Morrall, J. P.; Cifuentes, M. P.; Humphrey, M. G. Organometallics 2003, 22(7), 1402.
[18] Li, J.; Huang, P. Beilstein J. Org. Chem. 2011, 7, 426.
[19] Yoosaf, K.; Llanes-Pallas, A.; Marangoni, T.; Belbakra, A.; Marega, R.; Botek, E.; Champagne, B.; Bonifazi, D.; Armaroli, N. Chem. Eur. J. 2011, 17, 3262.
[20] Ishizaki, M.; Hoshino, O. Tetrahedron 2000, 56(45), 8813
[21] Hsung, R. P.; Chidsey, C. E. D.; Sita, L. R. Organometallics 1995, 14, 4808.
