Synthesis of Extended Triphenylenes
FULL PAPER
Phenanthro
CsF (159 mg, 1.05 mmol) was added to
0.070 mmol), 1 (83 mg, 0.28 mmol), and [Pd
A
8, 303; e) M. Bendikov, F. Wudl, D. F. Perepichka, Chem. Rev. 2004,
104, 4891; f) A. C. Grimsdale, K. Müllen, Angew. Chem. 2005, 117,
5732; Angew. Chem. Int. Ed. 2005, 44, 5592.
a
AHCTREUNG
in CH3CN/THF 4:1 (1.4 mL), and the mixture was stirred at room tem-
perature for 14 h. After this time, the resulting suspension was treated
withCH 2Cl2 (2 mL) and centrifuged. The pellet was washed with H2O
(2 mL) and CH2Cl2 (22 mL) and dried under vacuum. The resulting
highly insoluble white solid (16 mg) was mainly composed of polycyclic
arene 22a.[20] 1H NMR (750 MHz, 353 K, C2D2Cl4): d=9.92 (s, 2H), 8.98
(d, J=8.0 Hz, 4H), 8.72 (d, J=8.0 Hz, 4H), 7.81 (dd, J=7.4 Hz, 4H),
7.76 ppm (dd, J=7.4 Hz, 4H); MALDI-TOF MS: m/z (%): 678 (3, 40),
528 (23a, 100), 378 (22a, 48); UV/Vis (CH2Cl2): lmax (e)=332 (6000), 294
(12100), 259 nm (9100 molÀ1 dm3 cmÀ1).
[2] a) M. Müller, C. Kubel, K. Müllen, Chem. Eur. J. 1998, 4, 2099;
ˇ
´
b) Z. Wang, Z. Tomovic, M. Kastler, R. Pretsch, F. Negri, V. Enkel-
mann, K. Müllen, J. Am. Chem. Soc. 2004, 126, 7794.
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Zhang, G. Sonmez, J. Yamada, F. Wudl, Org. Lett. 2003, 5, 4433;
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Commun. 2004, 581.
2,3,6,7-Tetrakis
powdered anhydrous CsF (159 mg, 1.05 mmol) was added to a solution of
7b (59 mg, 0.070 mmol), 1 (83 mg, 0.28 mmol), and [Pd(PPh3)4] (40 mg,
0.035 mmol) in CH3CN/CH2Cl2 3:1 (1.4 mL), and the mixture was stirred
at room temperature for 14 h. After this time, the solvent was removed
under reduced pressure and the resulting residue was purified by column
chromatography (silica gel; hexane, then CH2Cl2/hexane 1:3 to 1:1), af-
fording 22b (23 mg, 42%) as a white solid, 2,3,6,7,16,17,20,21-octakis-
A
G
[4] a) S. Chandrasekhar, B. K. Sadashiva, K. A. Suresh, Pramana 1977,
9, 471; b) S. Chandrasekhar, Liq. Cryst. 1993, 14, 3; c) for a recent
review of the synthesis of triphenylenes see: D. PØrez, E. Guitiµn,
Chem. Soc. Rev. 2004, 33, 274–283.
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[6] For a recent review of palladium-catalyzed cycloaddition reactions
of arynes see: E. Guitiµn, D. PØrez, D. PeÇa in Topics in Organome-
tallic Chemistry, Vol. 14 (Ed.: J. Tsuji), Springer, Weinheim, 2005,
pp. 109–146.
(hexyloxy)pentabenzo[a,c,h,m,o]pentaphene (23b, 4 mg, 9%) and 19b
(0.6 mg, 2%). Data for 22b: M.p. 190–1938C; 1H NMR (300 MHz,
CDCl3): d=9.63 (s, 2H), 8.87 (dd, J=8.1, 1.1 Hz, 2H), 8.66 (dd, J=8.1,
1.1 Hz, 2H), 8.26 (s, 2H), 7.85 (s, 2H), 7.77–7.66 (m, 4H), 4.36 (t, J=
6.5 Hz, 4H), 4.27 (t, J=6.6 Hz, 4H), 2.07–1.92 (m, 8H), 1.71–1.59 (m,
8H), 1.49–1.38 (m, 16H), 1.00–0.93 ppm (m, 12H); 13C NMR (75 MHz,
CDCl3): d=150.0 (2C), 149.2 (2C), 130.1 (2C), 130.0 (2C), 128.2 (2C),
127.8 (2C), 127.35 (2CH), 127.29 (2CH), 124.7 (2C), 123.7 (2C), 123.5
(2CH), 123.3 (2CH), 117.0 (2CH), 107.9 (2CH), 107.4 (2CH), 69.8
(2CH2), 69.7 (2CH2), 31.8 (2CH2), 31.7 (2CH2), 29.5 (2CH2), 29.4
(2CH2), 25.94 (2CH2), 25.88 (2CH2), 22.71 (2CH2), 22.68 (2CH2),
14.07 ppm (2CH3); MS (FAB+): m/z (%): 778 (100); HRMS (FAB+):
m/z: calcd for C54H66O4 778.4961; found: 778.4967; UV/Vis (CH2Cl2): lmax
(e)=336 (sh, 39900), 319 (52300), 301 (75700), 275 (sh, 50100), 266 nm
(52900 molÀ1 dm3 cmÀ1). Data for 23b: m.p. 95–2178C;[23] 1H NMR
(300 MHz, 298 K, CDCl3, 5.0 mM): d=9.51 (s, 2H), 9.38 (s, 2H), 8.73 (m,
2H), 8.22 (s, 2H), 8.07 (s, 2H), 7.81 (s, 2H), 7.76 (s, 2H), 7.73 (m, 2H),
4.38 (t, J=6.1 Hz, 4H), 4.31 (t, J=6.6 Hz, 4H), 4.26 (t, J=6.7 Hz, 4H),
4.22 (t, J=6.3 Hz, 4H), 2.04–1.95 (m, 16H), 1.70–1.59 (m, 16H), 1.47–
1.39 (m, 32H), 1.01–0.91 ppm (m, 24H); 13C NMR (75 MHz, 298 K,
CDCl3, 15.1 mm): d=150.1 (2C), 149.95 (2C), 149.88 (2C), 149.5 (2C),
148.9 (2C), 148.8 (2C), 130.2 (2C), 127.8 (2C), 127.6 (2C), 127.4 (2C),
127.0 (2CH), 124.7 (2C), 124.1 (2C), 123.5 (2C), 123.3 (2CH), 116.6
(2CH), 116.3 (2CH), 108.1 (2CH), 107.1 (2CH), 107.0 (2CH), 106.8
(2CH), 69.6 (2CH2), 69.4 (4CH2), 69.3 (2CH2), 31.95 (2CH2), 31.85
(2CH2), 31.80 (4CH2), 29.9 (2CH2), 29.6 (2CH2), 29.54 (2CH2), 29.48
(2CH2), 29.2 (2CH2), 26.03 (2CH2), 25.98 (2CH2), 25.90 (2CH2), 22.75
(4CH2), 22.71 (4CH2), 14.11 (4CH3), 14.08 ppm (4CH3); MS (FAB+):
m/z (%): 1329 (62); MALDI-TOF HRMS: m/z: calcd for C90H120O8:
1328.8978; found: 1328.8975; UV/Vis (CHCl3): lmax (e)=380 (sh, 34600),
350 (68900), 324 (sh, 73300), 310 (93900), 284 (87600), 257 nm (sh,
68500 molÀ1 dm3 cmÀ1).
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Acknowledgements
Financial support from the Spanish Ministry of Education and Science
(MEC, BQU2000-0464 and CTQ2004-05752), FEDER and Xunta de Ga-
licia (DXID, 01PXI20902PN and 05PXIC20904PN) is gratefully acknowl-
edged. C. Romero and D. PeÇa thank the MEC for the award of an FPU
fellowship and a Ramón y Cajal research contract, respectively.
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Chem. Eur. J. 2006, 12, 5677 – 5684
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5683