J. P. Rabe, K. Müllen et al.
FULL PAPER
30.6, 30.3, 23.7, 15.0; FD-MS: m/z ꢀ%): 1353.4 [M] ꢀ100); anal. calcd ꢀ%)
pressure. The residue was purified by column chromatography on silica gel
with petroleum ether/carbon disulfide 3:1 and hot toluene/petroleum ether
1:1 to afford 16 ꢀ87 mg, 17%) as yellow crystals. 1H NMR ꢀ500 MHz, 50%
CDCl3/CS2): d 8.27 ꢀs, 2H), 8.26 ꢀs, 2H), 8.19 ꢀs, 2H), 8.17 ꢀs, 4H), 8.14 ꢀs,
2H), 4.76 ꢀm, 1H), 2.98 ꢀt, J 8.4 Hz, 4H), 2.93 ꢀt, J 8.4 Hz, 2H), 2.91 ꢀt,
J 8.4 Hz, 4H), 2.39 ± 2.32 ꢀm, 2H), 2.16 ± 2.08 ꢀm, 2H), 2.00 ± 1.88 ꢀm,
14H), 1.85 ± 1.77 ꢀm, 2H), 1.76 ± 1.24 ꢀm, 90H), 0.892 ꢀt, J 6.6 Hz, 15H);
13C NMR ꢀ125 MHz, 50% CDCl3/S2): d 155.57, 139.31, 139.14, 131.22,
129.42, 129.31, 129.20, 129.13, 129.10, 123.08, 122.79, 121.13, 120.89, 120.72,
120.67, 119.78, 119.19, 118.67, 118.48, 109.00, 75.35, 37.26, 37.23, 32.46, 32.43,
32.38, 32.32, 32.04, 30.19, 30.16, 30.04, 30.00, 29.93, 29.85, 29.53, 26.17, 24.06,
for C90H112Br2: C 79.86, H 8.34, Br 11.81; found: C 79.77, H 8.22, Br 11.32.
2-?N-Undecyl)amino-5,8,11,14,17-pentadodecylhexa-peri-hexabenzocoro-
nene ?15a) as an example for the synthesis of amino-substituted hexa-peri-
hexabenzocoronenes: A mixture of 2-bromo-5,8,11,14,17-pentadodecyl-
hexa-peri-hexabenzocoronene ꢀ2a) ꢀ104 mg, 0.0718 mmol), undecylamine
ꢀ0.45 mL, 358 mg, 2.09 mmol), sodium tert-butoxide ꢀ242 mg, 2.52 mmol),
trisꢀdibenzylideneacetone)-dipalladiumꢀ0) ꢀ7.1 mg, 0.0078 mmol), and ꢀR)-
BINAP ꢀꢀR)-ꢀ)-2,2'-bisꢀdiphenylphosphino)-1,1'-binaphthyl) ꢀ13 mg,
0.021 mmol) in toluene ꢀ10 mL) was heated at 808C for 4 h under an
argon atmosphere. The resulting mixture was purified by column chroma-
tography on silica gel with hot toluene/petroleum ether to afford the
4-undecylaminohexabenzocoronene ꢀ83 mg, 75%) as yellow crystals.
22.89, 14.20; FD-MS: m/z ꢀ%): 1462.0 [M] ꢀ100); anal. calcd ꢀ%) for
C
108H148O: C 88.70, H 10.20; found: C 88.27, H 10.22.
2-Methoxycarbonyl-5,8,11,14,17-pentadodecylhexa-peri-hexabenzocoro-
nene ?18a) as an example for the synthesis of methylester-substituted hexa-
peri-hexabenzocoronenes: A mixture of 2-bromo-5,8,11,14,17-pentadode-
cylhexa-peri-hexabenzocoronene ꢀ10) ꢀ530 mg, 0.367 mmol), triphenyl-
phosphine ꢀ100 mg, 0.383 mmol), triethylamine ꢀ1.06 g, 10.1 mmol), meth-
anol ꢀ703 mg, 21.9 mmol), and trans-dichlorobisꢀtriphenylphosphine)palla-
diumꢀii) ꢀ131 mg, 0.186 mmol) in tetrahydrofuran ꢀ20 mL) was stirred at
1008C for 5 d under a carbon monoxide atmosphere ꢀ5 atm) in a 40 mL
autoclave. After cooling the reaction mixture the solvent was removed
under reduced pressure. The residue was purified by column chromatog-
raphy on silica gel with hot toluene/petroleum ether to afford 2-methoxy-
carbonyl-5,8,11,14,17-pentadodecylhexa-peri-hexabenzocoronene ꢀ325 mg,
62%) as orange yellow crystals.
Compound 15a: 1H NMR ꢀ500 MHz, 50% CDCl3/CS2): d 8.30 ꢀs, 4H),
8.26 ꢀs, 2H), 8.20 ꢀs, 2H), 7.97 ꢀs, 2H), 7.38 ꢀs, 2H), 3.23 ꢀt, J 6.6 Hz, 2H),
2.97 ꢀt, J 8.7 Hz, 4H), 2.95 ꢀt, J 8.7 Hz, 2H), 2.85 ꢀt, J 7.8 Hz, 4H),
2.00 ± 1.78 ꢀm, 12H), 1.68 ± 1.22 ꢀm, 106H), 0.95 ± 0.85 ꢀm, 18H); 13C NMR
ꢀ125 MHz, 50% CDCl3/CS2): d 145.79, 139.31, 139.13, 139.03, 130.52,
129.56, 129.50, 129.31, 129.04, 123.25, 123.15, 123.11, 120.80, 120.68, 119.69,
119.31, 118.31, 118.09, 117.68, 105.49, 44.19, 37.35, 37.20, 32.56, 32.42, 32.07,
32.03, 30.30, 30.24, 30.18, 30.05, 30.00, 29.92, 29.89, 29.84, 29.55, 29.51, 27.77,
22.85, 22.81, 14.15; FD-MS: m/z ꢀ%): 1533.1 [M] ꢀ100); anal. calcd ꢀ%) for
C
113H161N: C 88.50, H 10.58, N 0.91; found: C 88.25, H 10.16, N 0.87.
Compound 15b: 1H NMR ꢀ500 MHz, 50% CDCl3/CS2): d 8.58 ꢀs, 2H),
8.55 ꢀs, 2H), 8.51 ꢀs, 2H), 8.28 ꢀs, 2H), 7.67 ꢀs, 2H),7.36 ꢀs, 2H), 3.72 ꢀm,
2H), 3.28 ꢀt, J 7.2 Hz, 4H), 3.09 ꢀt, J 8.0 Hz, 4H), 3.02 ꢀt, J 8.1 Hz,
4H), 2.02 ± 1.92 ꢀm, 12H), 1.86 ± 1.20 ꢀm, 102H), 0.90 ± 0.85 ꢀm, 18H);
13C NMR ꢀ125 MHz, 50% CDCl3/CS2): d 145.60, 139.09, 139.01, 130.54,
130.26, 129.54, 129.51, 129.47, 129.33, 123.51, 123.40, 120.86, 120.79, 120.73,
118.78, 118.54, 118.34, 117.91, 105.67, 105.44, 44.12, 37.37, 37.27, 32.58, 32.47,
32.05, 30.22, 30.05, 30.02, 29.95, 29.86, 29.54, 27.73, 22.90, 14.21; FD-MS:
Compound 18a: 1H NMR ꢀ500 MHz, 50% CDCl3/CS2): d 8.47 ꢀs, 2H),
7.80 ꢀs, 2H), 7.74 ꢀs, 2H), 7.71 ꢀs, 2H), 7.66 ꢀs, 2H), 7.63 ꢀs, 2H), 4.14 ꢀs, 3H),
2.76 ꢀt, J 8.1 Hz, 2H), 2.66 ꢀt, J 8.1 Hz, 4H), 2.59 ꢀt, J 8.1 Hz, 4H),
1.88 ꢀq, J 8.1 Hz, 2H), 1.83 ± 1.72 ꢀm, 8H), 1.64 ± 1.23 ꢀm, 90H), 0.93 ± 0.88
ꢀm, 15H); 13C NMR ꢀ125 MHz, 50% CDCl3/CS2): d 167.15, 139.16,
138.90, 128.93, 128.62, 128.52, 128.46, 128.26, 126.43, 125.15, 121.89, 120.65,
120.49, 120.41, 120.25, 119.28, 119.04, 118.22, 117.31, 51.86, 37.24, 37.12,
37.03, 32.49, 32.41, 32.37, 32.07, 31.96, 30.39, 30.34, 30.12, 30.08, 30.05, 29.98,
m/z ꢀ%): 1534.2 [M] ꢀ100); anal. calcd ꢀ%) for C112H160N2: C 87.66, H
10.51, N 1.83; found: C 87.64, H 10.53, N 1.81.
Compound 15c: 1H NMR ꢀ500 MHz, 50% CDCl3/CS2): d 8.46 ꢀs, 4H),
8.30 ꢀs, 4H), 7.73 ꢀs, 4H), 3.85 ꢀbrm, 2H), 3.37 ꢀt, J 6.6 Hz, 4H), 3.01 ꢀt,
J 7.7 Hz, 8H), 1.98 ± 1.85 ꢀm, 12H), 1.59 ± 1.32 ꢀm, 104H), 0.90 ± 0.85 ꢀm,
18H); 13C NMR ꢀ125 MHz, 50% CDCl3/CS2): d 145.2, 138.5, 130.0, 129.0,
128.7, 122.8, 120.2, 118.4, 117.8, 117.4, 105.0, 43.4, 36.4, 31.5, 31.2, 31.1, 29.3,
29.89, 29.55, 22.86, 14.18; FD-MS: m/z ꢀ%): 1422.3 [M] ꢀ100); anal. calcd
ꢀ%) for C104H140O2: C 87.83, H 9.92; found: C 87.63, H 9.03.
Compound 18b: 1H NMR ꢀ250 MHz, CD2Cl2/CS2): d 7.83 ꢀs, 2H), 7.78 ꢀs,
2H), 7.61 ꢀs, 2H), 7.50 ꢀs, 2H), 7.36 ꢀs, 2H), 7.25 ꢀs, 2H), 3.99 ꢀs, 3H), 2.71 ꢀt,
J 7.5 Hz, 4H), 2.49 ꢀt, J 7.2 Hz, 4H), 1.91 ± 1.25 ꢀm, 80H), 1.03 ± 0.88 ꢀm,
12H); 13C NMR ꢀ125 MHz, CD2Cl2/CS2): d 167.23, 140.36, 140.21, 129.76,
129.64, 129.21, 128.79, 128.50, 126.41, 122.41, 122.21, 121.92, 121.61, 121.45,
119.66, 119.40, 118.43, 52.81, 38.56, 38.29, 33.61, 33.37, 31.94, 31.90, 31.66,
29.2, 29.1, 29.0, 28.9, 28.6, 26.8, 22.0, 13.3; FD-MS: m/z ꢀ%): 1534.2 [M]
ꢀ100); anal. calcd ꢀ%) for C112H160N2: C 87.66, H 10.51; found: C 87.72, H
10.41.
31.56, 31.52, 31.43, 31.10, 24.50, 15.72; FD-MS: m/z ꢀ%): 1311.9 [M] ꢀ100);
2-Piperidino-5,8,11,14,17-pentadodecylhexa-peri-hexabenzocoronene
?17): A mixture of 2-bromo-5,8,11,14,17-pentadodecylhexa-peri-hexaben-
zocoronene ꢀ2a) ꢀ107 mg, 0.074 mmol), piperidine ꢀ0.21 mL, 181 mg,
2.12 mmol), sodium tert-butoxide ꢀ242 mg, 2.52 mmol), trisꢀdibenzylide-
neacetone)dipalladiumꢀ0) ꢀ7.9 mg, 0.0086 mmol), and ꢀR)-BINAP ꢀꢀR)-
ꢀ)-2,2'-bisꢀdiphenylphosphino)-1,1'-binaphthyl) ꢀ16 mg, 0.026 mmol) in
toluene ꢀ10 mL) was heated at 808C for 4 h under an argon atmosphere.
The resulting mixture was purified by column chromatography on silica gel
with hot toluene/petroleum ether to afford 17 ꢀ83 mg, 78%) as yellow
crystals. 1H NMR ꢀ500 MHz, 50% CDCl3/CS2): d 8.25 ꢀs, 2H), 8.22 ꢀs,
2H), 8.16 ꢀs, 2H), 8.15 ꢀs, 2H), 8.11 ꢀs, 2H), 8.10 ꢀs, 2H), 3.57 ꢀt, J 5.3 Hz,
4H), 2.95 ꢀt, J 8.1 Hz, 4H), 2.875 ꢀt, J 7.5 Hz, 4H), 2.86 ꢀt, J 7.5 Hz,
2H), 2.10 ± 2.04 ꢀm, 4H), 1.98 ± 1.83 ꢀm, 12H), 1.66 ± 1.23 ꢀm, 90H), 0.92 ±
0.85 ꢀm, 15H); 13C NMR ꢀ125 MHz, 50% CDCl3/CS2): d 149.80, 139.26,
139.05, 130.45, 129.47, 129.33, 129.11, 123.21, 122.88, 120.89, 120.76, 120.64,
119.34, 119.22, 119.19, 118.54, 118.46, 109.95, 51.64, 37.35, 37.28, 32.62, 32.46,
32.04, 30.22, 30.05, 30.00, 29.92, 29.84, 29.51, 26.63, 24.79, 22.82, 14.16; FD-
anal. calcd ꢀ%) for C94H118O4: C 86.06, H 9.07; found: C 86.03, H 8.98.
2-Cyano-5,8,11,14,17-pentadodecylhexa-peri-hexabenzocoronene ?19a): A
mixture of 2-bromo-5,8,11,14,17-pentadodecylhexa-peri-hexabenzocoro-
nene ꢀ315 mg, 0.219 mmol) and copper cyanide ꢀ4.10 g, 45.7 mmol) in N-
methyl-2-pyrrolidinone ꢀ30 mL) was heated at 1858C for 20 h under an
argon atmosphere. The reaction mixture was poured into 10% ammonium
hydroxide solution. The precipitated crystals were collected by filtration,
washed with water and purified by column chromatography on silica gel
with CS2/petroleum ether 1:1 and toluene/petroleum ether 1:1 to afford the
2-cyano-5,8,11,14,17-pentadodecylhexa-peri-hexabenzocoronene ꢀ184 mg,
61%) as yellow crystals. 1H NMR ꢀ500 MHz, 50% CDCl3/CS2): d 7.92 ꢀs,
2H), 7.76 ꢀs, 2H), 7.35 ꢀs, 2H), 7.16 ꢀs, 2H), 7.08 ꢀs, 2H), 6.82 ꢀs, 2H), 2.89 ꢀt,
J 8.2 Hz, 2H), 2.66 ꢀt, J 8.2 Hz, 4H), 2.17 ꢀt, J 8.2 Hz, 4H), 1.97
ꢀquint, J 8.2 Hz, 2H), 1.80 ꢀquint, J 8.2 Hz, 4H), 1.71 ± 1.25 ꢀm, 94H),
0.98 ± 0.87 ꢀm, 15H); 13C NMR ꢀ125 MHz, 50% CDCl3/CS2): d 139.44,
138.82, 138.57, 128.75, 128.14, 127.76, 127.60, 127.53, 125.92, 124.25, 121.37,
121.30, 121.12, 120.68, 120.35, 120.29, 120.15, 119.98, 119.22, 118.67, 117.80,
117.36, 115.43, 107.19, 37.27, 37.09, 36.41, 32.68, 32.45, 32.08, 31.98, 31.81,
30.43, 30.36, 30.24, 30.20, 30.16, 30.11, 30.07, 30.04, 30.01, 29.92, 29.58, 22.91,
MS: m/z ꢀ%): 1446.6 [M] ꢀ100); anal. calcd ꢀ%) for C107H147N: C 88.80, H
10.24, N 0.97; found: C 88.21, H 10.26, N 0.91.
2-Cyclohexyloxyhexabenzocoronene ?16): After stirring
a mixture of
14.21; FD-MS: m/z ꢀ%): 1388.4 [M] ꢀ100); anal. calcd ꢀ%) for C103H137N: C
cyclohexanol ꢀ1.14 g, 11.4 mmol) and sodium hydride ꢀ338 mg, 14.1 mmol),
in toluene ꢀ50 mL) at room temperature for 1 h, 2-bromo-5,8,11,14,17-
pentadodecylhexa-peri-hexabenzocoronene ꢀ2a) ꢀ503 mg, 0.348 mmol),
trisꢀdibenzylideneacetone)dipalladiumꢀ0) ꢀ33 mg, 0.036 mmol), and ꢀR)-
BINAP ꢀꢀR)-ꢀ)-2,2'-bisꢀdiphenylphosphino)-1,1'-binaphthyl) ꢀ67 mg,
0.11 mmol) was added to the mixture. The resulting mixture was stirred
at 808C for 2 h under an argon atmosphere. The reaction mixture was
poured into water and extracted with hot toluene. The organic phase was
washed with water, dried ꢀMgSO4), and concentrated under reduced
89.05, H 9.94, N 1.01; found: C 88.41, H 10.03, N 0.90.
Acknowledgements
Financial support by the European Commission ꢀTMR-Program Sisitomas)
and by the Volkswagen Stiftung is gratefully acknowledged.
4340
ꢁ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
0947-6539/00/0623-4340 $ 17.50+.50/0
Chem. Eur. J. 2000, 6, No. 23