NoVel Diethynylcarbazole Macrocycles
3H), 0.29 (s, 9H). 13C NMR (CDCl3, 100 MHz): δ 140.6, 140.4,
130.1, 129.8, 124.7, 124.3, 122.4, 122.3, 113.8, 113.4, 108.93,
108.86, 106.6, 92.2, 92.1, 83.2, 65.9, 43.4, 32.1, 31.8, 29.8, 29.71,
29.65, 29.6, 29.49, 29.45, 29.0, 27.3, 22.8, 14.3, 0.3. FT-IR (KBr):
ν 3356 (br) (H-O-), 3049, 2925, 2853, 2223 (CtC), 2151 (Ct
C), 1628, 1600, 1561, 1484, 1461, 1379, 1353, 1286, 1248, 1229,
1192, 1151, 1063, 888, 845, 806, 760 cm-1. EI MS: m/z (%) 569
(14) [M+], 551 (11) [M+ - H2O], 511 (100) [M+ - H2O - C3H4].
HRMS (FAB, [M+]) calcd for C38H55NOSi, 569.4047; found,
569.4040.
1379, 1354, 1285, 1239, 1211, 1152, 879, 806, 745 cm-1. MALDI-
TOF MS: m/z 656.3 [M+]. HRMS (FAB, [M+]) calcd for
C46H44N2O2, 656.3397; found, 656.3391.
4,4′-[6,6′-(Buta-1,3-diyne-1,4-diyl)bis(9-hexadecylcarbazole-
6,3-diyl)]bis(2-methylbut-3-yn-2-ol) (10b). Compound 10b was
prepared according to the procedure used for compound 10a. 10b
1
was isolated as a light yellow solid (80%). Mp 103-105 °C. H
NMR (CDCl3, 400 MHz): δ 8.26 (s, 2H), 8.16 (s, 2H), 7.67 (d, 3J
3
3
) 8.4 Hz, 2H), 7.56 (d, J ) 8.4 Hz, 2H), 7.34 (t, J ) 8.4 Hz,
3
4H), 4.27 (t, J ) 6.9 Hz, 4H), 2.06 (s, 2H), 1.86-1.84 (m, 4H),
1.68 (s, 12H), 1.33-1.23 (m, 52H), 0.88 (t, 3J ) 6.8 Hz, 6H). 13
C
4-[6-Ethynyl-9-butylcarbazol-3-yl]-2-methylbut-3-yn-2-ol (9a).
NaOH aqueous solution (5.0 M, 4 mL) was added to a stirred
solution of 8a (4.01 g, 10 mmol) in tetrahydrofuran (15 mL) and
methanol (20 mL). After complete consumption of the starting
material (18 h), the reaction mixture was diluted with diethyl ether
and water. The phases were separated. The aqueous phase was
washed with diethyl ether, and the combined organic phase was
washed with saturated brine. The organic phase was dried over
MgSO4, and the solvent removed. The residual material was purified
by column chromatography on silica gel (petroleum ether/dichlo-
romethane 1:5) to give 9a (2.57 g, 78%) as a yellow oil. 1H NMR
(CDCl3, 600 MHz): δ 8.21 (d, 5J ) 1.0 Hz, 1H), 8.15 (d, 5J ) 0.9
Hz, 1H), 7.59 (m, 1H), 7.54-7.52 (m, 1H), 7.34-7.32 (m, 2H),
NMR (CDCl3, 100 MHz): δ 140.7, 140.4, 130.4, 129.9, 125.1,
124.2, 122.5, 122.2, 113.6, 112.4, 109.1, 108.9, 92.4, 83.2, 82.6,
73.1, 65.8, 43.3, 32.0, 31.8, 29.79, 29.71, 29.65, 29.58, 29.5, 29.4,
29.0, 27.3, 22.8, 14.2. FT-IR (KBr): ν 3336 (br) (H-O-), 3056,
2924, 2852, 2222 (CtC), 2140 (CtC), 1628, 1597, 1566, 1483,
1380, 1352, 1286, 1232, 1151, 1133, 882, 806, 722 cm-1. MALDI-
TOF MS: m/z 992.7 [M+]. HRMS (FAB, [M+]) calcd for
C70H92N2O2, 992.7153; found, 992.7142.
1,4-Bis(6-ethynyl-9-butylcarbazol-3-yl)buta-1,3-diyne (11a).
KOH (0.034 g, 0.6 mmol) was added to a stirred solution of 10a
(0.131 g, 0.2 mmol) in methanol (2 mL) and toluene (20 mL). The
mixture was refluxed for 6 h. And then it was diluted with
dichloromethane and water. The phases were separated. The organic
phase was dried over MgSO4 and filtered. The filtrate was
concentrated and purified by column chromatography on silica gel
(petroleum ether/dichloromethane 1:1) to give 11a (0.104 g, 96%)
as a light yellow solid. Mp 70-72 °C. 1H NMR (CDCl3, 400
MHz): δ 8.28 (s, 2H), 8.24 (s, 2H), 7.68-7.61 (m, 4H), 7.38-
3
4.27 (t, J ) 7.2 Hz, 2H), 3.08 (s, 1H), 2.08 (s, 1H), 1.84-1.82
3
(m, 2H), 1.67 (s, 6H), 1.38-1.36 (m, 2H), 0.94 (t, J ) 7.4 Hz,
3H). 13C NMR (CDCl3, 100 MHz): δ 140.4, 140.2, 129.9, 129.7,
124.6, 124.0, 122.2, 122.1, 113.3, 112.4, 108.8, 92.3, 84.9, 83.1,
75.5, 65.7, 42.8, 31.7, 30.9, 20.4, 13.8. FT-IR (KBr): ν 3357 (br)
(H-O-), 3291 (H-Ct), 3053, 2960, 2931, 2871, 2224 (CtC),
2102 (CtC), 1628, 1599, 1568, 1484, 1457, 1379, 1354, 1286,
1239, 1212, 1151, 1133, 1067, 883, 808, 748 cm-1. EI MS: m/z
(%) 329 (7) [M+], 268 (100) [M+ - H2O - C3H7]. HRMS (FAB,
[M+]) calcd for C23H23NO, 329.1774; found, 329.1774.
3
7.34 (m, 4H), 4.30 (t, J ) 7.2 Hz, 4H), 3.09 (s, 2H), 1.87-1.84
(m, 4H), 1.43-1.37 (m, 4H), 0.96 (t, 3J ) 7.3 Hz, 6H). 13C NMR
(CDCl3, 100 MHz): δ 140.9, 140.8, 130.6, 130.3, 125.3, 124.9,
122.5, 122.3, 113.0, 112.7, 109.2, 109.1, 84.8, 82.6, 75.7, 73.1,
43.2, 31.2, 20.6, 14.0. FT-IR (KBr): ν 3284 (H-O-), 3053, 2961,
2928, 2866, 2136 (CtC), 2099 (CtC), 1623, 1593, 1479, 1453,
1377, 1348, 1262, 1209, 1096, 1024, 876, 804, 749 cm-1. MALDI-
TOF MS: m/z 540.1 [M+]. HRMS (FAB, [M+]) calcd for C40H32N2,
540.2560; found, 540.2562.
4-[6-Ethynyl-9-hexadecylcarbazol-3-yl]-2-methylbut-3-yn-2-
ol (9b). Compound 9b was prepared according to the procedure
1
used for compound 9a. 9b was isolated as a yellow oil (95%). H
NMR (CDCl3, 400 MHz): δ 8.21 (d, 5J ) 1.2 Hz, 1H), 8.15 (d, 5J
) 1.2 Hz, 1H), 7.61-7.59 (m, 1H), 7.54-7.52 (m, 1H), 7.34-
7.31 (m, 2H), 4.26 (t, 3J ) 7.2 Hz, 2H), 3.08 (s, 1H), 2.04 (s, 1H),
1.84 (m, 2H), 1.67 (s, 6H), 1.31-1.22 (m, 26H), 0.88 (t, 3J ) 7.0
Hz, 3H). 13C NMR (CDCl3, 100 MHz): δ 140.7, 140.4, 130.1,
129.9, 124.8, 124.3, 122.4, 122.3, 113.5, 112.6, 108.9, 92.3, 84.9,
83.2, 75.5, 65.9, 43.3, 32.0, 31.8, 29.8, 29.7, 29.65, 29.58, 29.48,
29.44, 29.0, 27.3, 22.8, 14.2. FT-IR (KBr): ν 3361 (br) (H-O-),
3311 (H-Ct), 3050, 2925, 2853, 2227 (CtC), 2104 (CtC), 1629,
1600, 1569, 1484, 1461, 1379, 1353, 1287, 1229, 1153, 1060, 883,
1,4-Bis(6-ethynyl-9-hexadecylcarbazol-3-yl)buta-1,3-diyne (11b).
Compound 11b was prepared according to the procedure used for
compound 11a. 11b was isolated as a light yellow solid (96%).
1
5
Mp 75-76 °C. H NMR (CDCl3, 400 MHz): δ 8.27 (d, J ) 1.1
Hz, 2H), 8.23 (s, 2H), 7.67-7.60 (m, 4H), 7.37-7.33 (m, 4H),
4.28 (t, 3J ) 7.2 Hz, 4H), 3.09 (s, 2H), 1.88-1.84 (m, 4H), 1.37-
1.23 (m, 52H), 0.88 (t, J ) 7.1 Hz, 6H). 13C NMR (CDCl3, 100
3
MHz): δ 140.9, 140.8, 130.6, 130.3, 125.3, 124.9, 122.5, 122.3,
113.0, 112.7, 109.2, 109.1, 84.9, 82.6, 75.7, 73.2, 43.5, 32.1, 29.8,
29.7, 29.69, 29.6, 29.52, 29.48, 29.0, 27.4, 22.8, 14.3. FT-IR
(KBr): ν 3311 (H-Ct), 3288 (H-Ct), 3063, 2922, 2851, 2134
(CtC), 2104 (CtC), 1628, 1596, 1565, 1482, 1380, 1352, 1287,
1238, 1149, 1126, 884, 806, 722 cm-1. MALDI-TOF MS: m/z
876.6 [M+]. HRMS (FAB, [M+]) calcd for C64H80N2, 876.6316;
found, 876.6322.
807, 725 cm-1. EI MS: m/z (%) 497 (20) [M+], 479 (40) [M+
-
H2O], 439 (100) [M+ - H2O - C3H4]. HRMS (FAB, [M+]) calcd
for C35H47NO, 497.3652; found, 497.3648.
4,4′-[6,6′-(Buta-1,3-diyne-1,4-diyl)bis(9-butylcarbazole-6,3-
diyl)]bis(2-methylbut-3-yn-2-ol) (10a). A solution of 9a (1.077
g, 3.27 mmol) in pyridine (6 mL) was added to a suspension of
CuCl (3.237 g, 32.7 mmol) and Cu(OAc)2‚H2O (6.529 g, 32.7
mmol) in pyridine (40 mL). The mixture was stirred at 60 °C for
19 h and then filtered. After removal of the solvent, the mixture
was diluted with dichloromethane and water. The phases were
separated. The organic layer was extracted with water. The
combined organic layer was dried over MgSO4 and filtered. The
filtrate was concentrated and subjected to column chromatography
on silica gel (ethyl acetate/petroleum ether 1:2) to afford 10a as a
light yellow solid (0.859 g, 80%). Mp 174-175 °C. 1H NMR
(CDCl3, 400 MHz): δ 8.26 (s, 2H), 8.15 (s, 2H), 7.67-7.64 (m,
Macrocycle 2b. A solution of 11b (0.175 g, 0.2 mmol) in
tetrahydrofuran (50 mL) was added slowly to a suspension of Pd-
(PPh3)2Cl2 (0.014 g, 0.02 mmol), CuI (0.0057 g, 0.03 mmol), and
I2 (0.025 g, 0.1 mmol) in diisopropylamine (200 mL) and
tetrahydrofuran (200 mL) at 50 °C. Upon completion of the slow
addition (21 h), the reaction mixture was stirred for an additional
12 h. After removal of the solvent and filtration, the residual
material was recrystallized from dichloromethane to afford 2b as
a light yellow solid (0.062 g, 35%). Mp 120 °C. 1H NMR (CDCl3,
3
3
3
2H), 7.56-7.53 (m, 2H), 7.34 (t, J ) 8.3 Hz, 4H), 4.28 (t, J )
7.2 Hz, 4H), 2.08 (s, 2H), 1.86-1.83 (m, 4H), 1.68 (s, 12H), 1.42-
400 MHz): δ 8.31 (s, 8H), 7.66-7.64 (m, 8H), 7.35 (d, J ) 8.5
Hz, 8H), 4.27 (t, 3J ) 7.2 Hz, 8H), 1.88-1.85 (m, 8H), 1.34-1.24
1.36 (m, 4H), 0.95 (t, J ) 7.3 Hz, 6H). 13C NMR (CDCl3, 100
(m, 104H), 0.88 (t, J ) 7.0 Hz, 12H). 13C NMR (CDCl3, 100
3
3
MHz): δ 140.9, 140.6, 130.6, 130.0, 125.3, 124.4, 122.6, 122.4,
113.7, 112.6, 109.3, 109.1, 92.4, 83.2, 82.6, 73.1, 65.9, 43.3, 31.8,
31.2, 20.6, 14.0. FT-IR (KBr): ν 3331 (br) (H-O-), 3056, 2959,
2931, 2213 (CtC), 2137 (CtC), 1628, 1597, 1562, 1482, 1458,
MHz): δ 140.8, 130.4, 125.5, 122.5, 113.0, 109.2, 82.5, 73.3, 43.5,
32.1, 29.9, 29.8, 29.7, 29.6, 29.5, 29.1, 27.4, 22.9, 14.3. FT-IR
(KBr): ν 2924, 2853, 2141 (CtC), 2100 (CtC), 1626, 1595, 1560,
1484, 1462, 1381, 1354, 1285, 1262, 1149, 1131, 1093, 879, 805,
J. Org. Chem, Vol. 71, No. 19, 2006 7431