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Synlett 2004(7): 1191-1194  
DOI: 10.1055/s-2004-822929
LETTER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Highly Conjugated Two-Dimensional Molecular Scaffolds via Pd-Catalyzed Reactions on a Tetraphenylethylene Core

Saumitra Sengupta*
Department of Chemistry, Jadavpur University, Kolkata 700 032, India
Fax: +91(33)24146266; e-Mail: jusaumitra@yahoo.co.uk;
Further Information

Publication History

Received 30 December 2003
Publication Date:
10 May 2004 (online)

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Abstract

A facile synthesis of ethylene centered highly conjugated two-dimensional molecular scaffolds is described via Pd-catalyzed coupling reactions (Sonogashira and Heck reactions) on a tetraphenylethylene core.

Key words

tetraphenylethylene - Sonogashira coupling - Heck ­reaction - two-dimensional conjugation

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13

A mixture of tetraphenylethylene (0.11 g, 0.33 mmol), I2 (0.23 g, 0.80 mmol) and PhI(OAc)2 (0.31 g, 0.80 mmol) in dry CHCl3 (7 mL) was stirred at r.t. in the dark for 60 h. The reaction mixture was filtered and the residue washed with cold benzene. It was then recrystallized from CCl4 to give the tetraiodide 5 (80%); mp >250 °C. UV/Vis (CHCl3):
λ = 265 (ε = 38250 dm3mol-1cm-1), 330 (ε = 17375
dm3mol-1cm-1) nm. 1H NMR (300 MHz, CDCl3): δ = 6.78 (d, 8 H, J = 7.7 Hz), 7.40 (d, 8 H, J = 7.7 Hz).

15

Compound 8: IR (CHCl3): 3000, 2910, 2090, 1480 cm-1. 1H NMR (300 MHz, DMSO-d 6): δ = 3.24 (s, 4 H), 6.90 (d, 8 H, J = 8 Hz), 7.12 (d, 8 H, J = 8 Hz). C34H20 requires C, 95.32; H, 4.67%. Found: C, 95.16; H, 4.71; Compound 9: IR (CHCl3): 3300, 3000, 1605, 1450 cm-1. 1H NMR (300 MHz, DMSO-d 6): δ = 4.26 (d, 8 H, J = 5.4 Hz), 5.31 (t, 4 H, J = 5.4 Hz), 6.94 (d, 8 H, J = 7.8 Hz), 7.22 (d, 8 H, J = 7.8 Hz). Compound 10: IR (CHCl3): 3000, 2930, 1700, 1650, 1600, 1465 cm-1. 1H NMR (300 MHz, DMSO-d 6): δ = 4.31 (s, 8 H), 7.04 (d, 8 H, J = 8 Hz), 7.32 (d, 8 H, J = 8 Hz), 7.50-7.82 (m, 8 H), 7.86-8.30 (m, 16 H), 8.70 (br s, 4 H). C82H52O8 requires C, 84.53; H, 4.46%. Found: C, 84.19; H, 4.66. Compound 11: IR (CHCl3): 2920, 1708, 1630, 1360, 1305 cm-1. 1H NMR (300 MHz, DMSO-d 6): δ = 1.33 (t, 12 H, J = 7 Hz), 4.20 (q, 8 H, J = 7 Hz), 6.56 (d, 4 H, J = 15 Hz), 7.07 (d, 8 H, J = 8 Hz), 7.40 (d, 8 H, J = 8Hz), 7.78 (d, 4 H, J = 15 Hz).