16, 1,5-bis(3,5-bis(octyloxy)phenyl)anthracene-2,3,6,7-tetra-
carbaldehyde: Starting from tetraol 15¢, the synthesis of crude
tetraldehyde 16 was carried out according to general procedure
20, diethyl 6-(3,5-bis(octyloxy)benzoyl)-1-(3,5-bis(octyloxy)-
phenyl)-7-formylnaphthalene-2,3-dicarboxylate: The unidirec-
tional elongated product 20 was synthesized according to general
procedure C from 12. To ensure the right stochiometry the purity
of starting dialdehyde 12 was calibrated with 1H NMR using
1,4-dimethoxybenzene as an internal standard. 1.2 equivalents of
diethyl maleate were used in the reaction. The crude mixture was
purified by flash chromatography (CH2Cl2–hexane = 2/1) to give
pure product (52%). IR (KBr) n/cm-1: 1063, 1169, 1263, 1443,
1
E. H NMR (400 MHz, CDCl3): d 0.85 (t, J = 6.8 Hz, 12H),
1.16–1.49 (m, 40H), 1.74–1.83 (m, 8H), 3.98 (t, J = 6.8 Hz, 8H),
6.55 (d, J = 2.0 Hz, 4H), 6.67 (t, J = 2.0 Hz, 2H), 8.45 (s, 2H),
8.51 (s, 2H), 10.12 (s, 2H), 10.62 (s, 2H); 13C NMR (100 MHz,
CDCl3): d 14.08, 22.64, 26.05, 29.22, 29.36, 31.79, 68.42, 101.62,
109.61, 130.88, 130.97, 131.65, 132.67, 133.46, 133.57, 135.80,
148.72, 160.56, 192.10, 193.40.
1
1593, 1728, 2856, 2927; H NMR (500 MHz, CDCl3): d 0.84–
17, 5,12-bis(3,5-bis(octyloxy)phenyl)pentacene-2,3,9,10-tetra-
carbonitrile: Starting from crude tetraldehyde 16, the synthesis of
pentacene tetranitrile 17 was accomplished according to general
procedure C and purified by flash chromatography (CH2Cl2–
hexane = 3/2) under nitrogen atmosphere to give the pure product
(overall yield from 15 over three steps = 19%). IR (KBr) n/cm-1:
835, 1056, 1168, 1435, 1601, 2228, 2855, 2926; 1H NMR (400 MHz,
CDCl3): d 0.83–0.85 (m, 12H), 1.25–1.52 (m, 40H), 1.80–1.82 (m,
8H), 4.00–4.03 (m, 8H), 6.57 (s, 4H), 6.77 (s, 2H), 8.25 (s, 2H), 8.41
(s, 2H), 8.75 (s, 2H), 8.89 (s, 2H); 13C NMR (100 MHz, CDCl3):
d 14.02, 22.58, 26.03, 29.16, 29.23, 29.32, 31.74, 68.42, 101.48,
108.02, 109.71, 115.88, 116.11, 127.24, 128.68, 129.72, 130.74,
130.77, 131.25, 137.21, 137.72, 138.50, 141.53, 160.81; HRMS.
(FAB, M+), C70H82O4N4, Calc: 1042.6336, Found: 1042.6327.
18, tetraethyl 5,12-bis(3,5-bis(octyloxy)phenyl)pentacene-
2,3,9,10-tetracarboxylate: Starting from crude tetraldehyde 16,
the synthesis of pentacene tetraester 18 was achieved according
to general procedure C, but diethyl maleate (3 eq) was used
instead of fumaronitrile. The crude mixture was purified by flash
chromatography (CH2Cl2–hexane = 3/2) to give the product with
minor impurities (overall yield from 15 over three steps = 17%).
IR (KBr) n/cm-1: 1114, 1167, 1270, 1366, 1590, 1727, 2856, 2927;
1H NMR (400 MHz, CDCl3): d 0.82–0.85 (m, 12H), 1.23–1.45
(m, 50H), 1.75–1.82 (m, 10H), 3.93–4.01 (m, 8H), 4.32 (q, J =
6.8 Hz, 4H), 4.39 (q, J = 6.8 Hz, 4H), 6.62 (s, 4H), 6.72 (s, 2H),
8.07 (s, 2H), 8.36 (s, 2H), 8.68 (s, 2H), 8.75 (s, 2H); 13C NMR
(100 MHz, CDCl3): d 14.01, 14.10, 14.14, 22.57, 26.01, 29.16,
29.25, 29.31, 29.63, 31.73, 60.60, 61.49, 68.26, 101.35, 109.80,
127.14, 127.85, 128.15, 128.28, 129.79, 129.95, 130.11, 130.66,
132.36, 138.99, 139.47, 160.43, 167.16, 167.97, 172.27; HRMS.
(FAB, M+), C78H102O12, Calc: 1230.7371, Found: 1230.7388.
19, N,N¢-bis-n-dodecyl- 5,12-bis(3,5-bis(octyloxy)phenyl)-
pentacene-2,3,9,10-bisimide: Starting from crude tetraldehyde
16, the synthesis of pentacene diimide 19 was achieved according
to general procedure C, but N-n-dodecyl-maleimide (3 eq) was
used instead of fumaronitrile. The crude mixture was purified by
flash chromatography (CH2Cl2–hexane = 1/2) to give the pure
product (overall yield from 15 over three steps = 57%). IR (KBr)
n/cm-1: 1169, 1391, 1435, 1600, 1707, 1760, 2854, 2925; 1H NMR
(400 MHz, CDCl3): d 0.82–0.86 (m, 18H), 1.22–1.31 (m, 68H),
1.42–1.48 (m, 12H), 1.66–1.68 (m, 6H), 1.77–1.85 (m, 10H),
3.73 (t, J = 7.2 Hz, 4H), 4.01 (t, J = 6.4 Hz, 8H), 6.61 (d, J =
2.0 Hz, 4H), 6.74 (t, J = 2.0 Hz, 2H), 8.23 (s, 2H), 8.39 (s, 2H),
8.77 (s, 2H), 8.79 (s, 2H);13C NMR (100 MHz, CDCl3): d 14.01,
22.58, 25.54, 26.02, 26.86, 28.37, 29.16, 29.26, 29.32, 29.42, 29.54,
29.63, 31.73, 31.83, 38.40, 67.89, 68.27, 101.21, 109.73, 125.50,
126.24, 126.40, 128.50, 128.76, 129.69, 130.43, 130.76, 131.19,
131.99, 138.75, 142.23, 160.61, 167.43, 167.51; HRMS. (MALDI,
[M+H]+), C94H133N2 O8, Calc: 1418.0062, Found: 1418.0068.
0.87 (m, 12H), 1.07 (t, J = 7.0 Hz, 6H), 1.23–1.29 (m, 32H),
1.37–1.42 (m, 8H), 1.69–1.79 (m, 8H), 3.91–3.94 (m, 8H), 4.14
(q, J = 7.0 Hz, 2H), 4.41 (q, J = 7.0 Hz, 2H), 6.49 (d, J = 2.0 Hz,
2H), 6.56 (t, J = 2.0 Hz, 1H), 6.65 (t, J = 2.0 Hz, 1H), 6.86 (d,
J = 2.0 Hz, 2H), 8.03 (s, 1H), 8.26 (s, 1H), 8.59 (s, 1H), 9.96 (s,
1H);13C NMR (125 MHz, CDCl3): d 13.99, 22.57, 25.93, 25.96,
29.08, 29.12, 29.15, 29.24, 29.27, 31.73, 61.43, 61.98, 68.22, 68.38,
101.82, 106.56, 108.12, 108.96, 128.58, 130.09, 131.06, 133.00,
133.21, 133.59, 133.64, 135.06, 136.86, 137.71, 138.79, 140.37,
160.07, 160.34, 165.10, 167.72, 190.25, 195.73; HRMS. (FAB, M+),
C62H88O10, Calc: 992.6377, Found: 992.6387.
20¢, (4-(3,5-bis(octyloxy)phenyl)-7-((3,5-bis(octyloxy)phenyl)-
(hydroxy)methyl)naphthalene-2,3,6-triyl)trimethanol: The reduc-
tion of 20 to tetraol 20¢ was carried out according to general
procedure D. IR (KBr) n/cm-1: 1056, 1166, 1385, 1459, 1595,
1
2856, 2926, 3339; H NMR (400 MHz, CDCl3): d 0.83–0.86 (m,
12H), 1.19–1.34 (m, 32H), 1.35–1.46 (m, 8H), 1.69–1.77 (m, 8H),
3.85–3.93 (m, 8H), 4.49 (d, J = 12.4 Hz, 1H), 4.58(d, J = 12.4 Hz,
1H), 4.66 (s, 2H), 4.92 (s, 2H), 6.07 (s, 1H), 6.36 (s, 1H), 6.39
(s, 1H), 6.50 (s, 2H), 6.52 (s, 1H), 7.39 (s, 1H), 7.75 (s, 1H),
7.81 (s, 1H); 13C NMR (125 MHz, CDCl3): d 14.04, 22.61, 26.02,
29.19, 29.25, 29.35, 31.77, 60.67, 64.51, 65.05, 68.09, 68.21, 75.09,
100.22, 100.52, 105.04, 108.79, 128.48, 128.65, 129.02, 131.87,
132.46, 134.66, 136.67, 138.01, 140.02, 140.22, 140.41, 144.99,
160.23, 160.43; HRMS. (MALDI, [M–OH+H]+), C58H88O7, Calc:
896.6530, Found: 896.6538.
21, 7-(3,5-bis(octyloxy)benzoyl)-4-(3,5-bis(octyloxy)phenyl)-
naphthalene-2,3,6-tricarbaldehyde: Starting from 20¢, the
synthesis of crude trialdehyde intermediate 21 was carried out
according to general procedure E. 1H NMR (400 MHz, CDCl3):
d 0.83–0.86 (m), 1.23–1.40 (m), 1.71–1.79 (m), 3.83–3.99 (m),
6.53–6.66(m), 6.86–6.87(m), 8.09 (s, 1H), 8.35 (s, 1H), 8.39 (s,
1H), 9.99 (s, 1H), 10.08 (s, 1H), 10.60 (s, 1H); 13C spectrum can
not be obtained due to rapid decomposition; HRMS. (FAB,
[M+H]+), C58H81O8, Calc: 905.5931, Found: 905.5927.
22,
1,6-bis(3,5-bis(octyloxy)phenyl)tetracene-2,3,8,9-tetra-
carbonitrile: The synthesis of tetracene tetranitrile 22 was
accomplished according to general procedure C and the crude
product was purified by flash chromatography (CH2Cl2–hexane =
1/1) to give the pure tetracene product (overall yield from 20
over three steps = 52%). IR (KBr) n/cm-1: 1056, 1169, 1378,
1436, 1592, 2231, 2855, 2926; 1H NMR (400 MHz, CDCl3):
d 0.83–0.86(m, 12H), 1.16–1.38 (m, 32H), 1.40–1.51 (m, 8H),
1.78–1.83 (m, 8H), 3.96–4.04 (m, 8H), 6.50 (d, J = 2.0 Hz, 2H),
6.60 (d, J = 2.0 Hz, 2H), 6.71 (t, J = 2.0 Hz, 1H), 6.74 (t, J =
2.0 Hz, 1H), 8.32 (s, 1H), 8.44 (s, 1H), 8.49 (s, 1H), 8.62 (s, 1H),
8.74 (s, 1H), 8.78 (s, 1H);13C NMR (125 MHz, CDCl3): d 14.01,
22.58, 26.00, 29.16, 29.30, 29.63, 31.74, 68.47, 101.52, 102.63,
108.38, 108.82, 108.99, 109.01, 109.53, 109.62, 115.12, 115.62,
4516 | Org. Biomol. Chem., 2011, 9, 4507–4517
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The Royal Society of Chemistry 2011
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