PAPER
Synthesis of Tribenzohexadehydro[12]annulene and Its Derivatives
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1H NMR (CDCl3): d = 0.951 (t, J = 7.3 Hz, 6 H), 0.954 (t, J = 7.3
Hz, 6 H), 1.37-1.42 (m, 8 H), 1.52-1.59 (m, 8 H), 2.56-2.60 (m, 8
H), 3.26 (s, 2 H), 7.31 (s, 2 H), 7.35 (s, 2 H).
13C NMR (CDCl3): d = 13.98, 22.70, 22.72, 32.06, 32.12, 33.01,
33.03, 79.99, 82.64, 91.00, 121.52, 123.60, 132.84, 133.20, 141.11,
141.64.
(5) (a) Haley, M. M.; Brand, S. C.; Pak, J. J. Angew. Chem., Int.
Ed. Engl. 1997, 36, 836. (b) Diederich, F. In Modern
Acetylene Chemistry; Stang, P. J.; Diederich, F., Eds.; VCH:
Weinheim, 1995, 443.
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Müllen, K.; Pakula, T. J. Am. Chem. Soc. 2003, 125, 1682.
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Adachi, K.; Araki, S.; Sonoda, M.; Hirose, K.; Naemura, K.
J. Am. Chem. Soc. 2002, 124, 7266. (c) Tanatani, A.; Mio,
M. J.; Moore, J. S. J. Am. Chem. Soc. 2002, 124, 5350.
(d) Nakamura, K.; Okubo, H.; Yamaguchi, M. Org. Lett.
2001, 3, 1097. (e) Allen, M. T.; Diele, S.; Harris, K. D. M.;
Hegmann, T.; Kariuki, M.; Lose, D.; Preece, J. A.;
Tschierske, C. J. Mater. Chem. 2001, 11, 302.
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Angew. Chem. Int. Ed. 2003, 42, 5597. (b) Kawase, T.;
Seirai, Y.; Darabi, H. R.; Oda, M.; Sarakai, Y.; Tashiro, K.
Angew. Chem. Int. Ed. 2003, 42, 1659. (c) Kawase, T.;
Tanaka, K.; Fujiwara, N.; Darabi, H. R.; Oda, M. Angew.
Chem. Int. Ed. 2003, 42, 1624.
(8) (a) Campbell, I. D.; Eglinton, G.; Henderson, W.; Raphael,
R. A. J. Chem. Soc., Chem. Commun. 1966, 87.
(b) Solooki, D.; Ferrara, J. D.; Malaba, D.; Bradshaw, J. D.;
Tessier, C. A.; Youngs, W. J. Inorg. Synth. 1997, 31, 122.
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Tetrahedron Lett. 1998, 39, 4701.
MS (EI): m/z (%) = 450 (100, M+), 365 (25), 293 (6).
HRMS–FAB: m/z calcd for C34H42: 450.3287; found: 450.3291.
Annulenoannulene 2c
To a mixture of 1,2,4,5-tetraiodobenzene (227 mg, 0.39 mmol),
K2CO3 (324 mg, 2.34 mmol), CuI (148 mg, 0.78 mmol) and PPh3
(614 mg, 2.34 mmol) was added a solution of 8c (352 mg, 0.78
mmol) in DMF (2 mL) under argon. The mixture was stirred for 20
h at 160 °C. The mixture was poured into sat. aq NH4Cl solution (25
mL) and extracted with CS2 (3 × 30 mL). The combined organic
phase was washed with sat. aq NaCl solution (20 mL) and dried
over MgSO4. The solvent was removed under reduced pressure, and
the residue was separated by column chromatography on Al2O3
(hexane-benzene, 4:1) to give 2c (3 mg, 1%) as yellow crystals; mp
>250 °C.
1H NMR (CS2/CD2Cl2, 1:1): d = 1.02-1.05 (m, 24 H), 1.44-1.51
(m, 16 H), 1.58-1.64 (m, 16 H), 2.60 (t, J = 7.6 Hz, 16 H), 7.08 (s,
4 H), 7.09 (s, 4 H), 7.17 (s, 2 H).
13C NMR (CS2/CD2Cl2, 1:1): d = 13.97, 22.58, 22.67, 31.91, 31.97,
32.88, 32.89, 79.98, 82.53, 91.00, 121.57, 123.61, 132.70, 133.07,
140.89, 141.41.
(11) (a) Staab, H. A.; Graf, F. Tetrahedron Lett. 1966, 751.
(b) Staab, H. A.; Graf, F. Chem. Ber. 1970, 103, 1107.
(12) Miljani, O. S.; Vollhardt, K. P. C.; Whitener, G. D. Synlett
2003, 29.
(13) Sonogashira, K. In Comprehensive Organic Synthesis, Vol.
3; Pergamon Press: Oxford, 1990, 521.
UV/VIS (CH2Cl2): lmax (log e) = 252 (4.32), 310 (4.98), 345 (5.03),
399 (3.81), 440 (3.49), 454 (3.41), 486 nm (3.11).
LDTOF-MS: m/z 970 (M+).
(14) 1,4-bis(2-bromophenyl)-1,3-butadiyne was obtained in 33%
yield: Vorasingha, A. Dissertation; Tokyo Metropolitan
University: Japan, 1999.
Acknowledgment
(15) (a) Okuro, K.; Furuune, M.; Miura, M.; Nomura, M.
Tetrahedron Lett. 1992, 33, 5363. (b) Okuro, K.; Furuune,
M.; Enna, M.; Miura, M.; Nomura, M. J. Org. Chem. 1993,
58, 4716.
The authors are grateful to Prof. Yoshito Tobe for fruitful discussi-
ons. This work has been supported in part by CREST of JST (Japan
Science and Technology Corporation).
(16) Kehoe, J. M.; Kiley, J. H.; English, J. J.; Johnson, C. A.;
Petersen, R. C.; Haley, M. M. Org. Lett. 2000, 2, 969.
(17) 1-Iodo-2-bromo-4,5-dibutylbenzene was prepared by
bromination of 1,2-dibutylbenzene with Br2 (63%), followed
by iodination with I2 and H5IO6 in AcOH-H2SO4-H2O
(64%).
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Synthesis 2004, No. 9, 1527–1531 © Thieme Stuttgart · New York