Synthesis of Polyaromatic Hydrocarbons from BisACHTUNTRGNEU(GN biaryl)diynes
COMMUNICATION
[4] a) E. Clar, The Aromatic Sextet, Wiley, New York, 1972; b) E. Clar,
Polycyclic Hydrocarbons, Vol. 1–2, Academic, London, 1964.
[5] a) T. C. Wu, C. H. Chen, D. Hibi, A. Shimizu, Y. Tobe, Y. T. Wu,
49, 7059–7062; b) X. Zhang, X. Jiang, K. Zhang, L. Mao, J. Luo, C.
Experimental Section
Synthesis of compound 1a: Nitrogen was bubbled through a mixing solu-
tion of toluene (80 mL), EtOH (20 mL), and water (20 mL) for 30 min.
1,4-Bis(2-bromo-4-tert-butylphenyl)buta-1,3-diyne (2.34 g, 4.96 mmol),
[Pd
ACHTUNGTRENNUNG
butylnaphthalen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
9.95 mmol) were added to this solution. The mixture was heated at 808C
for 24 h. The solution was extracted three times with ethyl acetate. After
removal of the solvent in vacuo, the crude material was purified by
column chromatography (dichloromethane/hexane=1:10) to afford com-
pound 1a (2.1 g, 63%) as a yellow solid.
[6] a) M. Bendikov, H. M. Duong, K. Starkey, K. N. Houk, E. A. Carter,
Hirao, M. Nakano, A. Shimizu, E. Botek, B. Champagne, D. Shiomi,
K. Sato, T. Takui, K. Matsumoto, H. Kurata, T. Kubo, J. Am. Chem.
Yakushi, M. Nakano, D. Shiomi, K. Sato, T. Takui, Y. Morita, K. Na-
M. R. Philpott, S. Vukovic, W. A. Lester, T. A. Cui, Y. Kawazoe,
[7] a) T. A. Chen, T. J. Lee, M. Y. Lin, S. M. A. Sohel, E. W. G. Diau,
Shaibu, S. H. Lin, C. Y. Lin, K. T. Wong, R. S. Liu, J. Org. Chem.
Synthesis of compound 2a: A reaction tube containing PtCl2 (20 mg,
0.07 mmol) was dried in vacuo for 1 h, and vacuum was filled with nitro-
gen with a nitrogen balloon. To this round bottom flask was added com-
pound 1a (500 mg, 0.74 mmol) and toluene (74 mL), and the mixture was
stirred at 258C for 5 min before it was heated at 908C for 24 h. After re-
moval of the solvent in vacuo, the crude material was purified by column
chromatography (dichloromethane/hexane=1:5) to afford compound 2a
(440 mg, 88%) as a yellow solid.
Synthesis of compound 3a: Methanesulfonic acid (1 mL) was added, by
using a syringe, to a mixture of bichrysene 2a (65 mg, 0.096 mmol) and
DDQ (46 mg, 0.2 mmol) in dry CH2Cl2 (10 mL) at 08C under argon at-
mosphere. After 30 min, the mixture was quenched with saturated
NaHCO3 solution (10 mL), and then extracted with CH2Cl2 twice. The
combined extracts were washed with brine and dried over MgSO4. After
removal of the solvent in vacuo, the crude material was purified by
column chromatography (dichloromethane/hexane=1:5) to afford com-
pound 3a (61 mg, 95%) as an orange solid.
[9] CCDC-818107 (3a) contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge from
c.uk/data_request/cif.
[10] a) J. C. Fetzer, Large (C^24) Polycyclic Aromatic Hydrocarbons:
Chemistry and Analysis, Wiley, New York, 2000, p. 6; b) R. A. Pas-
[11] a) R. Chaudhuri, M. Y. Hsu, C. W. Li, C. I Wang, C. J. Chen, C. K.
3053–3056; b) C. W. Li, C. I Wang, H. Y. Liao, R. Chaudhuri, R. S.
Acknowledgements
This work was supported by funds from National Science Council,
Taiwan.
[12] For compound 3e, we envisage that the two cove regions have the
same stereochemistry as that of 3a; hence, the chirality of fjord
region is dependent on the cove stereochemistry because the A-ring
should have the three hydrogen atoms coplanar with the benzene
ring. Therefore an alteration of the cove chirality is always accompa-
nied by the change of fjord chirality.
Keywords: aromaticity · hydrocarbons · oxidation · synthetic
methods · UV/Vis spectroscopy
[1] a) L. Schmidt-Mende, A. Fechtenkçtter, K. Mꢂllen, E, Moons,
de Craats, N. Stutzmann, O. Bunk, M. M. Nielsen, M. D. Watson, K.
Mꢂllen, H. D. Chanzy, H. Sirringhaus, R. H. Friend, Adv. Mater.
Watson, K. Mꢂllen, J. P. Rabe, Phys. Rev. Lett. 2004, 92, 188303.
[2] a) T. Bçhme, C. D. Simpson, K. Mꢂllen, J. P. Rabe, Chem. Eur. J.
3096; c) F. Dçtz, J. D. Brand, S. Ito, L. Gherghel, K. Mꢂllen, J. Am.
Received: April 7, 2011
Published online: June 7, 2011
Chem. Eur. J. 2011, 17, 8023 – 8027
ꢀ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
8027