Hetero-Oligopolyphenylenes
FULL PAPER
MgSO4, and reduced in vacuo. Column chromatography (SiO2, diethyl
ether) was used to separate the products. Unreacted starting material 11
(Rf =0.5), monosubstituted 13 (Rf =0.4), and disubstituted 14 (Rf =0.3)
were collected. Recrystallization from acetone/water yielded colorless
crystals. Yield: 0.075 g, 38% of 13 and 0.064g, 30% of 14.
(s, 9H; CH3), 1.23 ppm (s, 9H; CH3); 13C NMR (100 MHz, CDCl3,
218C): d=184.9 (1C; C=O), 159.9 (1C; Cquat/aryl), 157.3, 157.2 (2C; C2,
C12), 155.9, 155.8 (1C; C1, C13), 153.3, 151.1, 150.9 (1C; Cquat/aryl), 148.2
(2C; Caryl), 144.6, 141.8, 140.5, 140.3, 135.8, 135.1, 133.7, 132.5, 132.2,
131.8 (Cquat/aryl), 129.4(2C), 128.9 (2C), 128.8 (2C), 125.5 (2C), 12.47
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Compound 13: m.p. 253–2558C; 1H NMR (400 MHz, CDCl3, 218C): d=
(1C), 123.8 (2C), 114.7 (1C), 108.8 (1C) (Caryl), 55.1 (1C; CH3), 34.2,
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34.0 (1C; Cquat/alkyl), 30.8, 30.6 ppm (3C; CH3); IR (KBr disk): n˜ =3040
8.77, 8.76 (s, 1H; Haryl), 8.21, 8.20 (s, 2H; Haryl), 7.05 (d, J(H,H)=8.5 Hz,
2H; Haryl), 6.99 (m, 6H; Haryl), 6.78 (d, 3J(H,H)=8.5 Hz, 2H; Haryl), 6.70
(CHaromatic), 2960, 2906, 2868 (CH3), 1663 (C=O), 1604(C =C), 1549 (C=
N), 1399 (CH3), 1244 cmÀ1 (O CH3); ESI-MS (toluene): m/z (%): calcd:
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(m, 6H; Haryl), 1.74(s, 1H; OH), 1.57 (s, 6H; CH3), 1.15 ppm (s, 18H;
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695.9; found: 695.3 (100) [M+H]+; ESI-MS (toluene): m/z: calcd for
C47H43N4O2: 695.3386; found: 695.3411 [M+H]+.
CH3); 13C NMR (100 MHz, CDCl3, 218C): d=157.4, 157.3 (2C; Caryl),
155.6, 155.5 (1C; Caryl), 149.34 (1C), 149.27 (1C), 141.24 (1C), 141.20
(1C), 140.8 (1C), 138.9 (1C), 137.8 (1C), 134.50 (2C), 134.47 (1C), 133.4
(1C), 133.3 (1C) (Cquat/aryl), 132.0 (2C), 130.3 (2C), 130.1 (4C), 130.0
(2C), 129.7 (2C) (Caryl), 129.60, 129.57 (1C; Cquat/aryl), 124.11, 124.08 (2C;
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10-acetoxy-1,4-bis-(4-tert-butylphenyl)-2,3-dipyrimidyl-7-methoxytriphe-
nylene (17): Five drops of H2SO4 (20%) in acetic anhydride was added
to a hot solution of 16 (50 mg; 0.072 mmol) in acetic anhydride (4mL).
The reaction was heated on a water bath for 1 h and then allowed to
stand overnight. After this time, the reaction mixture was poured onto
ice and then warmed to 808C. The yellow solid was filtered off, washed
with water, and purified by column chromatography (SiO2, toluene:
MeOH 9:1), to produce 17 as a pale yellow crystalline product. Yield:
38 mg, 72%; m.p. 282–2848C; 1H NMR (400 MHz, CDCl3, 218C): d=
8.85, 8.84(s, 1H; H1 and H14), 8.09 (s, 5H; H2, H13 and H7), 7.74(d,
4J(H,H)=2.05 Hz, 1H; H8), 7.64(d, 3J(H,H)=8.88 Hz, 1H; H5), 7.54(d,
3J(H,H)=8.87 Hz, 1H; H10), 7.21 (d, 3J(H,H)=8.19 Hz, 4H; H4 and
H12), 6.94(app. d, 3J(H,H)=8.19 Hz, 2H; H3), 6.93 (app. d, 3J(H,H)=
8.19 Hz, 2H; H11), 6.81 (dd, J(H,H)=2.7–9.6 Hz, 1H; H6), 6.68 (dd,
C
aryl), 119.88, 119.79 (1C; Cquat/aryl), 93.4, 81.5 (1C; C C ), 65.1 (1C),
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33.8 (2C) (Cquat/alkyl), 31.0 (2C; CH3), 30.6 ppm (6C; CH3); ESI-MS
(CH3CN) m/z (%): calcd: 812.8; found: 812.6 (100) [M+H]+; ESI-MS
(CH3CN): m/z: calcd for C51H48BrN4O2: 811.3011 [M+H]+; found:
811.3002.
Compound 14: m.p. 264–2668C; 1H NMR (400 MHz, CDCl3, 218C): d=
8.76 (s, 2H; Haryl), 8.20 (s, 4H; Haryl), 6.98 (m, 8H; Haryl), 6.77 (d,
3
3J(H,H)=8.0 Hz, 4H; Haryl), 6.71 (d, J(H,H)=8.5 Hz, 4H; Haryl), 1.97 (s,
2H; OH), 1.58 (s, 12H; CH3), 1.16 ppm (s, 18H; CH3); 13C NMR
(100 MHz, CDCl3, 218C): d=157.4(4C; C aryl), 155.5 (2C; Caryl), 149.2,
141.3, 141.1, 140.0, 134.5, 133.4, 133.3 (2C; Cquat/aryl), 130.4, 130.2, 130.0,
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J(H,H)=2.7–9.6 Hz, 1H; H9), 3.95 (s, 3H; OCH3), 2.37 (s, 3H;
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124.1 (4C; Caryl), 119.7 (2C; Cquat/aryl), 93.2, 81.6 (2C; C C ), 65.4, 33.8
COOCH3), 1.27 ppm (s, 18H; CH3); 13C NMR (100 MHz, CDCl3,
218C): d=169.4(1C; C =O), 158.5 (1C; Cquat/aryl), 158.15, 158.10 (2C; C2
or C13), 155.80, 155.77 (1C; C1 or C14), 150.7, 150.6, 149.4, 138.3, 138.2,
138.0, 137.8 (1C; Cquat/aryl), 134.3 (br, 2C; Cquat/aryl), 133.1, 133.0, 132.6,
132.5, 131.9 (1C; Cquat/aryl), 131.46, 131.43 (2C; C3 or C11), 131.37 (1C;
C10), 131.2 (1C; C5), 131.0, 128.2 (1C; Cquat/aryl), 125.84, 125.81 (2C; C4
or C12), 124.0 (1C; Cquat/aryl), 119.6 (1C; C6), 115.6 (1C; C7), 114.5 (1C;
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(2C; Cquat/alkyl), 30.0 (4C;
CH3), 30.6 ppm (6C; CH3); ESI-MS
(CH3CN) m/z (%): calcd: 816.1; found: 815.4(100) [ M+H]+; ESI-MS
(CH3CN): m/z: calcd for C56H55N4O2: 815.4323; found: 815.4334
[M+H]+.
1,2-di(2-thienyl)-3,4,5,6-tetra-(4-tert-butylphenyl)benzene (15): Di(2-thie-
nyl)acetylene (69.5 mg, 0.37 mmol), tetra(4-tert-butyl)cyclopentadienone
(200 mg, 0.33 mmol), and benzophenone (1 g) were combined and heated
to reflux for 1 h. Purification by column chromatography (SiO2, diethyl
ether:hexane 1:9) and recrystallization from hexane yielded the product
as a white powder. Yield: 190 mg, 75%; m.p. 270–2718C; 1H NMR
(400 MHz, CDCl3, 218C): d=7.02 (dd, J(H,H)=1.0–5.0 Hz, 2H; Hthienyl),
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C9), 106.0 (1C; C8), 55.4(1C; OCH3), 34.5 (2C; Cquat/alkyl), 31.2 (6C;
CH3), 21.2 ppm (1C; COOCH3); IR (KBr disk): n˜ =3030 (CHaromatic),
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2958, 2903, 2868 (CH3), 1770 ( CO O ), 1614(C =C), 1550, 1509 (C=N),
1422 (CH3), 1391 ( C CH3), 1367 ( O CO CH3), 1238, 1187 cmÀ1
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(O CH3); ESI-MS (CHCl3): m/z (%): calcd: 737.9; found: 737.3 (100)
3
6.92 (d, J(H,H)=8.5 Hz, 4H; H11), 6.83 (d, 3J(H,H)=8.0 Hz, 4H; H10),
[M+H]+; ESI-MS (CHCl3); calcd for C49H45N4O3: [M+H]+ m/z:
6.81 (d, 3J(H,H)=8.0 Hz, 4H; H8), 6.66 (d, 3J(H,H)=8.5 Hz, 4H; H7),
6.63 (dd, J(H,H)=3.5–5.0 Hz, 2H; Hthienyl), 6.51 (dd, J(H,H)=1.0–3.5 Hz,
2H; Hthienyl), 1.16 (s, 18H; H16), 1.11 ppm (s, 18H; Halkyl); 13C NMR
(100 MHz, CDCl3, 218C): d=147.6 (2C; C14), 147.2 (2C; C13), 141.6
(2C; C3), 141.4, 141.4 (2C; Cquat/aryl), 137.1 (2C; C5), 137.0 (2C; C4),
133.4(2C; C quat/thienyl), 130.4(4C; C7), 130.0 (4C; C8), 128.6, 125.1, 125.0
(2C; Cthienyl), 122.9 (4C; C11), 122.7 (4C; C10), 33.7 (2C; C quat/alkyl), 33.6
737.3492; found: 737.3495.
Acknowledgements
We thank Dr. John OꢁBrien and Dr. Thomas McCabe for technical assis-
tance. D.J.G. thanks Enterprise Ireland award IF-2001\369 for financial
support. C.M.F. would like to acknowledge generous funding from
IRCSET PD 02101.
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(2C; C15), 30.8 (6C; C16), 30.7 ppm (6C; CH3); IR (KBr disk): n˜ =
3031 (CHaromatic), 2958, 2901, 2866 (CH3), 1510, 1461, 1390, 1362, 1269,
1019, 827, 699 cmÀ1; ESI-MS (CHCl3): m/z (%): calcd: 793.4; found:
793.4(100) [ M+Na]+; elemental analysis calcd (%) for C54H58S2 (771.1):
C 84.10, H 7.58; found: C 84.10, H 7.62.
1’,4’-bis-(4-tert-butylphenyl)-2’,3’-dipyrimidyl-7’-methoxy-6-oxospiro[cy-
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[2] a) M. Wind, U.-M. Wiesler, K. Saalwächter, K. Müllen, and H. W.
Spiess, Adv. Mater. 2001, 13, 752–756; b) V. Perec, C.-H. Ahn, G.
Ungar, D. J. P. Yeardley, M. Mçller, S. S. Sheiko, Nature 1998, 391,
161–164.
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[4] a) S. L. Gilat, A. Adronov, J. M. F. Frꢂchet, Angew. Chem. 1999, 111,
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clohexa-1,4-diene-3,9’-fluorene] (16):
A solution of iron(iii) chloride
(2.252 g; 13.883 mmol) in nitromethane (6 mL) was added dropwise to a
stirred solution of 10 (100 mg; 0.141 mmol) in freshly distilled dichloro-
methane (20 mL) under argon. An argon stream was bubbled through
the mixture throughout the course of the reaction. After stirring for an-
other 30 min, the reaction was quenched with methanol (6 mL). The re-
sulting mixture was poured into water and extracted with dichlorome-
thane. The organic washings were combined, dried over MgSO4, and re-
duced. The extract was purified by column chromatography (SiO2, dieth-
yl ether) and recrystallized from dichloromethane to afford colorless
crystals of 16. Yield: 84mg, 86%; m.p. >3008C; 1H NMR (400 MHz,
CDCl3, 218C): d=8.78, 8.73 (s, 1H; H1, H13), 8.31, 8.29 (s, 2H; H2,
3
3
H12), 7.40 (d, J(H,H)=8.0 Hz, 2H; Haryl), 7.17 (d, J(H,H)=8.0 Hz, 2H;
3
3
Haryl), 7.09 (d, J(H,H)=8.0 Hz, 2H; Haryl), 6.91 (d, J(H,H)=8.0 Hz, 2H;
aryl), 6.62 (dd, J(H,H)=2.5–8.5 Hz, 1H; H8), 6.57 (d, 4J(H,H)=2.5 Hz,
H
1H; H7), 6.51 (d, 3J(H,H)=9.5 Hz, 2H; Haryl), 6.32 (d, 3J(H,H)=8.5 Hz,
1H; H9), 6.08 (d, 3J(H,H)=10.0 Hz, 2H; Haryl), 3.72 (s, 3H; CH3), 1.34
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Chem. Eur. J. 2006, 12, 3043 – 3052
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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