R. Krupke, M. Mayor et al.
FULL PAPER
3058.86 (22), 3057.85 (48), 3056.85 (82), 3055.85 (100), 3054.84 N,NЈ-Bis[9-({4-[4-(4-iodo-2,5-dihexyloxyphenyl)ethynyl-2,5-di-
(90), 3053.84 (40). UV/Vis: λmax (ε, 103 m–1 cm–1) = 609 (27.2), 563
(15.1), 415 (204) nm. GPC (oligopore 6 μm, toluene, UV/Vis photo-
diode array detector): Area = 99.5% (at 12.34 min).
hexyloxyphenyl]ethynyl-2,5-dihexyloxyphenyl}ethynyl)phenanthren-
yl]-2-(3,5-di-tert-butylbenzylsulfanyl)-6-(3,5-di-tert-butylbenzyl-
amine)-1,4,5,8-tetracarboxylic Acid Naphthalenediimide (5): Pink
acetylene 19 (25.0 mg, 0.0272 mmol, 1.0 equiv.) and yellow iodide
41 (68.0 mg, 0.0564 mmol, 2.07 equiv.) were dissolved in THF
(28 mL) and diisopropylamine (2.8 mL). The mixture was degassed
for 15 min, and then Pd(PPh3)4 (7 mg, 0.0061, 22 mol-%) and CuI
(1 mg, 20 mol-%) were added. It was then stirred for 15 h at room
temperature. The reaction mixture was evaporated and purified by
CC (silica gel, 2ϫ12 cm, hexane/CH2Cl2 = 1:2 to 1:5) to give com-
pound 5 as a reddish solid (31 mg, 0.0101 mmol, 37%). Rf = 0.70
(CH2Cl2/hexane = 5:1). 1H NMR (600 MHz, CDCl3, 25 °C): δ =
N,NЈ-Bis[9-({4-[4-(4-iodo-2,5-dihexyloxyphenyl)ethynyl-2,5-di-
hexyloxyphenyl]ethynyl-2,5-dihexyloxyphenyl}ethynyl)phenanthren-
yl]-2,6-bis(3,5-di-tert-butylbenzylsulfanyl)-1,4,5,8-tetracarboxylic
Acid Naphthalenediimide (4): Violet acetylene 18 (16.5 mg,
0.0176 mmol, 1.0 equiv.) and yellow iodide 41 (44 mg,
0.0365 mmol, 2.07 equiv.) were dissolved in THF (25 mL) and di-
isopropylamine (2 mL). The mixture was degassed for 15 min, then
Pd(PPh3)4 (5 mg, 0.0043 mmol, 24 mol-%) and CuI (0.7 mg,
20 mol-%) were added. It was then stirred for 21 h at room tem-
perature. The reaction mixture was evaporated and purified by CC
(silica gel, 1ϫ12 cm, hexane/CH2Cl2 = 1:2 to 1:10) to give com-
pound 4 as a reddish solid (16 mg, 0.0051 mmol, 29%). Rf = 0.86
(CH2Cl2). 1H NMR (600 MHz, CDCl3, 25 °C): δ = 8.95 (s, 2 H,
3
9.98 (s, 1 H, NH), 8.88 (s, 1 H, NDI), 8.73 (d, JH,H = 7.7 Hz, 2
3
H, phenanthrene), 8.71 (d, JH,H = 8.1 Hz, 2 H, phenanthrene),
3
8.68 (d, JH,H = 8.3 Hz, 2 H, phenanthrene), 8.44 (s, 1 H, NDI),
3
8.09 (s, 2 H, phenanthrene), 7.88 (d, JH,H = 7.5 Hz, 2 H, phen-
anthrene), 7.74–7.66 (m, 10 H), 7.61 (t, 3JH,H = 7.5 Hz, 2 H, phen-
3
3
NDI), 8.73 (d, JH,H = 7.8 Hz, 2 H, phenanthrene), 8.71 (d, JH,H
3
anthrene), 7.38 (s, 1 H, NDI substituent), 7.34 (d, JH,H = 8.2 Hz,
3
= 8.7 Hz, 2 H, phenanthrene), 8.67 (d, JH,H = 8.3 Hz, 2 H, phen-
4
2 H, phenyl), 7.33 (d, JH,H = 1.3 Hz, 1 H, NDI substituent), 7.32
3
anthrene), 8.08 (s, 2 H, phenanthrene), 7.87 (d, JH,H = 7.3 Hz, 2
(d, 3JH,H = 8.3 Hz, 2 H, phenyl), 7.30 (d, 4JH,H = 1.4 Hz, 2 H, NDI
H, phenanthrene), 7.71 (d, 3JH,H = 8.3 Hz, 4 H, phenyl), 7.73–7.66
4
substituent), 7.22 (d, JH,H = 1.4 Hz, 2 H, NDI substituent), 7.16
3
(m, 6 H, phenanthrene), 7.61 (t, JH,H = 7.6 Hz, 2 H, phen-
(s, 2 H, OPE), 7.08 (s, 2 H, OPE), 7.05 (m, 8 H, OPE) 4.70 (d,
4
anthrene), 7.34 (d, JH,H = 1.6 Hz, 2 H, NDI substituent), 7.33 (d,
3
3JH,H = 5.3 Hz, 2 H, N-CH2), 4.39 (s, 2 H,S-CH2) 4.11 (t, JH,H
=
3JH,H = 8.5 Hz, 4 H, phenyl), 7.30 (d, JH,H = 1.5 Hz, 4 H, NDI
4
6.6 Hz, 8 H, OCH2), 4.09–4.03 (m, 16 H, OCH2), 2.00 (quint.,
3JH,H = 7.1 Hz, 4 H, CH2), 1.88 (m, 20 H, CH2), 1.57 (m, 24 H,
CH2), 1.37 (m, 48 H, CH2), 1.31 (s, 18 H, tBu), 1.30 (s, 18 H,
tBu), 0.911 (m, 30 H, CH3), 0.908 (m, 6 H, CH3) ppm. 13C NMR
(151 MHz, CDCl3, 25 °C): δ = 166.496 (1 C, Cq, C=O), 166.301 (1
C, Cq, C=O), 162.784 (1 C, Cq, C=O), 162.393 (1 C, Cq, C=O),
153.993 (2 C, Cq, C-O), 153.602 (8 C, Cq, C-O), 153.406 (2 C, Cq,
C-O), 151.257 (1 C, Cq, N-C), 151.257 (4 C, Cq, NDI substituent),
144.42 (1 C, Cq, S-C), 135.237 (1 C, Cq, NDI substituent), 134.847
(1 C, Cq, phenyl), 134.456 (1 C, Cq, phenyl), 133.675 (1 C, Cq,
NDI substituent), 132.435 (2 C, Ct, phenyl), 132.269 (2 C, Ct,
phenyl), 131.33 [2 C, Cq, C(phenanthrene)], 131.273 [2 C, Ct,
CH(phenanthrene)], 131.135 [2 C, Cq, C(phenanthrene)], 130.158
[2 C, Cq, C(phenanthrene)], 128.45 (1 C, Ct, NDI), 128.45 (4 C,
Ct, phenyl), 128.367 [2 C, Ct, CH(phenanthrene)], 127.228 (1 C,
Cq, NDI), 127.205 [2 C, Ct, CH(phenanthrene)], 127.205 [2 C, Ct,
CH(phenanthrene)], 127.032 [2 C, Cq, C(phenanthrene)], 126.79 [4
C, Ct, CH(phenanthrene)], 126.707 [2 C, Ct, CH(phenanthrene)],
126.641 (1 C, Cq, NDI), 123.906 (2 C, Cq, phenyl), 123.552 (2 C,
Ct, NDI substituent), 123.32 (1 C, Cq, NDI), 122.473 [2 C, Ct,
CH(phenanthrene)], 122.39 [2 C, Ct, CH(phenanthrene)], 122.141
(1 C, Ct, NDI substituent), 121.975 (2 C, Ct, NDI substituent),
121.725 (1 C, Ct, NDI substituent), 121.562 (1 C, Cq, NDI),
120.314 (1 C, Ct, NDI), 119.999 [2 C, Cq, C(phenanthrene)],
119.804 (1 C, Cq, NDI), 116.91 [8 C, Ct, CH(OPE)], 116.827 [2 C,
Ct, CH(OPE)], 116.27 [2 C, Ct, CH(OPE)], 114.333 [2 C, Cq,
C(OPE)], 113.943 [8 C, Cq, C(OPE)], 113.747 [2 C, Cq, C(OPE)],
100.853 (1 C, Cq, NDI), 94.015 (2 C, Cq, CϵC), 93.429 (2 C, Cq,
CϵC), 91.671 (2 C, Cq, CϵC), 91.476 (6 C, Cq, CϵC), 90.89 (2
C, Cq, CϵC), 87.178 (2 C, Cq, CϵC), 69.797 (2 C, Cs, O-CH2),
69.722 (2 C, Cs, O-CH2), 69.662 (4 C, Cs, O-CH2), 69.56 (2 C, Cs,
O-CH2), 69.376 (2 C, Cs, O-CH2), 48.086 (1 C, Cs, N-CH2), 37.875
(1 C, Cs, S-CH2), 34.82 (4 C, Cq, tBu), 31.667 (2 C, Cs, CH2 alkyl
β), 31.635 (8 C, Cs, CH2 alkyl β), 31.596 (2 C, Cs, CH2 alkyl β),
31.394 (12 C, Cp, tBu), 29.531 (2 C, Cs, CH2 alkyl γ), 29.304 (8 C,
Cs, CH2 alkyl γ), 29.277 (2 C, Cs, CH2 alkyl γ), 25.784 (2 C,Cs,
CH2 alkyl δ), 25.749 (2 C, Cs, CH2 alkyl δ), 25.689 (8 C, Cs, CH2
alkyl δ), 22.648 (12 C, Cs, CH2 alkyl ε), 14.053 (10 C, Cs, CH3
alkyl), 14.01 (2 C, Cs, CH3 alkyl) ppm. MS (MALDI-TOF): found
substituent), 7.16 (s, 2 H, OPE), 7.08 (s, 2 H, OPE), 7.05 (s, 2 H,
OPE), 7.042 (m, 4 H, OPE), 7.038 (s, 2 H, OPE), 4.43 (s, 4 H, S-
3
CH2), 4.11 (t, JH,H = 6.6 Hz, 8 H, OCH2), 4.09–4.03 (m, 16 H,
3
OCH2), 2.00 (quint., JH,H = 7.1 Hz, 4 H, CH2), 1.88 (m, 20 H,
CH2), 1.57 (m, 24 H, CH2), 1.37 (m, 48 H, CH2), 1.30 (s, 36 H,
tBu), 0.91 (m, 30 H, CH3), 0.87 (m, 6 H, CH3) ppm. 13C NMR
(151 MHz, CDCl3, 25 °C): δ = 163.4 (2 C, Cq, C=O), 162.3 (2 C,
Cq, C=O), 153.9 (2 C, Cq, C-O), 153.8 (2 C, Cq, C-O), 153.5 (8
C, Cq, C-O), 151.2 (4 C, Cq, NDI substituent), 149.4 (2 C, Cq, C-
S), 134.0 (2 C, Cq, phenyl), 133.2 (2 C, Cq, NDI substituent), 132.4
(4 C, Ct, phenyl), 131.3 (2 C, Ct, phenanthrene), 131.1 (2 C, Cq,
phenanthrene), 131.0 (2 C, Cq, phenanthrene), 130.1 (2 C, Cq,
phenanthrene), 128.8 (2 C, Ct, NDI), 128.5 (4 C, Ct, phenyl), 128.4
(2 C, Ct, phenanthrene), 127.2 (2 C, Ct, phenanthrene), 126.81 (2
C, Cq, phenanthrene), 126.8 (4 C, Ct, phenanthrene), 126.7 (2 C,
Ct, phenanthrene), 125.3 (2 C, Cq, NDI), 124.4 (2 C, Cq, phenyl),
123.8 (2 C, Cq, NDI), 123.5 (4 C, Ct, NDI substituent), 122.5 (2
C, Ct, phenanthrene), 122.4 (2 C, Ct, phenanthrene), 122.2 (2 C,
Ct, phenanthrene), 121.9 (2 C, Ct, NDI substituent), 119.7 (2 C,
Cq, phenanthrene), 118.9 (2 C, Cq, NDI), 117.0 [8 C, Ct,
CH(OPE)], 116.8 [2 C, Ct, CH(OPE)], 116.3 [2 C, Ct, CH(OPE)],
114.5 [2 C, Cq, C(OPE)], 114.2 [2 C, Cq, C(OPE)], 114.1 [4 C, Cq,
C(OPE)], 113.6 [2 C, Cq, C(OPE)], 113.5 [2 C, Cq, C(OPE)], 93.8
(2 C, Cq, CϵC), 93.2 (2 C, Cq, CϵC), 91.5 (6 C, Cq, CϵC), 91.4
(2 C, Cq, CϵC), 90.6 (2 C, Cq, CϵC), 87.9 (2 C, Cq, CϵC), 69.82
(2 C, Cs, OCH2), 69.75 (2 C, Cs, OCH2), 69.7 (4 C, Cs, OCH2),
69.6 (2 C, Cs, OCH2), 69.4 (2 C, Cs, OCH2), 38.2 (2 C, Cs, S-CH2),
34.8 (4 C, Cq, tBu), 31.6 (12 C, Cs, alkyl-β-CH2), 31.4 (12 C, Cp,
tBu), 29.5 (2 C, Cs, alkyl-γ-CH2), 29.3 (10 C, Cs, alkyl-γ-CH2),
25.79 (2 C, Cs, alkyl-δ-CH2), 25.75 (2 C, Cs, alkyl-δ-CH2), 25.70 (8
C, Cs, alkyl-δ-CH2), 22.7 (12 C, Cs, alkyl-ε-CH2), 14.1 (10 C, Cp,
alkyl-CH3),14.0 (10 C, Cp, alkyl-CH3) ppm. MS (MALDI-TOF):
m/z (%) = 3093.10 (13), 3092.09 (27), 3091.08 (58), 3090.10 (94),
3089.11 (100), 3088.11 (81), 3087.10 (37)[M]+; calcd. for
C208H242N2O16S2: 3093.78 (12), 3092.78 (28), 3091.78 (57), 3090.77
(15), 3089.77 (100), 3088.77 (90), 3087.76 (40). UV/Vis: λmax (ε,
103 m–1 cm–1) 530 (29.7), 497 (17.8), 415 (223) nm. GPC (oligopore
6 μm, toluene, UV/Vis photodiode array detector): Area = 99.0%
(at 12.30 min).
494
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Eur. J. Org. Chem. 2011, 478–496