12
Journal of Chemistry
HR-ESI-MS: ꢇꢈ/ calcd for [M + H]+ = C H N S 649.1772;
ꢅ ppm 8.35 (s, 2 H), 8.13 (br. s., 1 H), 7.73 (dd, ꢆ = 8.39, 1.70 Hz,
2 H), 7.44 (d, ꢆ = 8.53 Hz, 2 H), 7.38 (d, ꢆ = 3.48 Hz, 2 H),
44 28
2
2
found 649.1775. Anal. calcd. for C H N S : C, 81.47; H, 4.35;
44 28
2
2
N, 4.32; S, 9.86. Found: C, 81.45; H, 4.32; N, 4.28; S, 9.82.
7.30 (d, ꢆ = 5.04 Hz, 2 H), 7.23 (dd, ꢆ = 10.36, 8.53 Hz, 1
H), 7.12–7.16 (m, 2 H); 13C NMR (100 MHz, CDCl ) ꢅ 145.5,
3
4.2.10. Preparation of P5. e compound was prepared
from 2 eq of 3-(thiophene-2-yl)-9H-carbazole 7 (0.12 g,
0.48 mmol) and 1 eq of 4,4-diiodo-2ꢀ2-dimethyl-1,1-biphenyl
3 (0.10 g, 0.23 mmol) as a pale yellow solid (0.05 g, 35%). 1H
139.4, 128.0, 126.7, 124.9, 123.9, 123.8, 122.3, 118.0, 111.1. HR-ESI-
MS ꢇꢈ/ calcd for [M + H]+ = C H NS 332.0569; found
20 13
2
332.0569. Anal. calcd. for C H NS : C, 72.52; H, 3.95; N,
20 13
2
4.23; S, 19.30. Found: C, 72.49; H, 3.91; N, 4.19; S, 19.27.
NMR (400 MHz, CDCl ) ꢅ ppm 8.42 (s, 2 H), 8.24 (d, ꢆ =
3
4.2.14. Preparation of P7. e compound was prepared
from 2 eq of 3,6-di(thiophen-2-yl)-9H-carbazole 9 (0.43 g,
1.30 mmol) and 1 eq of 4,4-diiodobiphenyl 2 (0.25 g,
0.60 mmol). Recrystallization from absolute ethanol gave
7.46 Hz, 2 H), 7.75 (d, ꢆ = 8.56 Hz, 2 H), 7.46–7.60 (m, 12 H),
7. 41 (dd, ꢆ = 3.55, 1.10 Hz, 2 H), 7.36 (td, ꢆ = 7.43, 0.92 Hz, 2
H), 7.31 (dd, ꢆ = 5.14, 1.10 Hz, 2 H), 7.16 (dd, ꢆ = 5.14, 3.55 Hz,
2 H), 2.33 (s, 6 H); 13C NMR (100 MHz, CDCl ) ꢅ ppm 145.6,
3
1
141.4, 140.4, 140.1, 138.0, 136.7, 130.8, 128.3, 128.0, 126.8, 126.3,
124.6, 124.2, 123.9, 123.3, 122.3, 120.5, 120.2, 117.9, 110.3, 110.1,
20.2. HR-ESI-MS: ꢇꢈ/ calcd for [M + H]+ = C H N S
P7 as a pale yellow solid (1.0 g, 75%). H NMR (600 MHz,
CDCl ) ꢅ ppm 8.44 (s, 4 H), 7.98 (d, ꢆ = 8.44 Hz, 3 H), 7.76
3
46 32
2
2
(d, ꢆ = 8.07 Hz, 8 H), 7.53 (d, ꢆ = 8.44 Hz, 4 H), 7.43 (dd,
677.2085; found 677.2080. Anal. calcd. for C H N S : C,
46 32
2
2
ꢆ = 3.48, 1.10 Hz, 4 H), 7.32 (dd, ꢆ = 5.13, 0.92 Hz, 4 H), 7.16
(dd, ꢆ = 4.95, 3.48 Hz, 5 H); 13C NMR (100 MHz, CDCl )
81.65; H, 4.77; N, 4.14; S, 9.45. Found: C, 81.62; H, 4.74; N,
4.10; S, 9.41.
3
ꢅ ppm 145.3, 140.8, 139.4, 137.0, 128.7, 128.1, 127.3, 127.3, 125.0,
124.0, 123.9, 122.5, 118.0, 110.4. Mp 268∘C. HR-APCI-MS: ꢇꢈ/
calcd for [M + H]+ = C H N S 813.1526; found 813.1522.
4.2.11. Preparation of P6. e compound was prepared
from 2 eq of 3-(thiophene-2-yl)-9H-carbazole 7 (0.16 g,
0.60 mmol) and 1 eq of 1,4-diiodobenzene 4 (0.10 g,
0.30 mmol). Purification by column chromatography (silica,
chloroform-hexane) gave P6 as a pale yellow solid (0.08 g,
52 32
2
4
Anal. calcd. for C H N S : C, 76.85; H, 3.97; N, 3.45; S,
52 32
2
4
15.74. Found: C, 76.82; H, 3.95; N, 3.41; S, 15.70.
4.2.15. Preparation of P8. e compound was prepared
from 2.2 eq of 3,6-di(thiophen-2-yl)-9H-carbazole 9 (0.17 g,
0.05 mmol) and 1 eq of 4,4-diiodo-2ꢀ2-dimethyl-1,1-biphenyl
3 (0.10 g, 0.02 mmol). Purification by column chromatogra-
phy (silica, dichloromethane-hexane) gave P8 as a white solid
48%). 1H NMR (600 MHz, CDCl ) ꢅ ppm 8.42 (s, 2 H), 8.25
3
(d, ꢆ = 7.52 Hz, 2 H), 7.87 (s, 4 H), 7.77 (dd, ꢆ = 8.53, 1.74 Hz,
2 H), 7.60 (t, ꢆ = 8.60 Hz, 4 H), 7.52 (td, ꢆ = 7.50, 1.00 Hz, 2
H), 7.42 (dd, ꢆ = 3.48, 1.10 Hz, 2 H), 7.39 (t, ꢆ = 6.97 Hz, 2 H),
7. 32 (dd, ꢆ = 5.04, 1.01 Hz, 2 H), 7.16 (dd, ꢆ = 5.14, 3.48 Hz,
(0.01 g, 60%). 1H NMR (400 MHz, CDCl ) ꢅ ppm 8.45 (s, 4
2 H); 13C NMR (100 MHz, CDCl ) ꢅ ppm 128.3, 128.1, 127.2,
3
3
H), 7.69–7.83 (m, 6 H), 7.49–7.63 (m, 6 H), 7.37–7.49 (m, 6 H),
7.29–7.35 (m, 4 H), 7.11–7.19 (m, 4 H), 1.28 (s, 6 H). 13C NMR
126.5, 124.8, 124.1, 124.0, 123.5, 122.4, 120.6, 120.6, 118.0, 110.1,
109.9. HR-ESI-MS: ꢇꢈ/ calcd for [M + H]+ = C H N S
38 24
2
2
(100 MHz, CDCl ) ꢅ ppm 145.6, 145.4, 142.1, 141.8, 140.9, 128.1,
3
573.1459; found 573.1484. Anal. calcd. for C H N S : C,
38 24
2
2
124.9, 124.2, 124.0, 123.9, 123.6, 122.4, 122.3, 118.0, 111.4, 110.4,
79.72; H, 4.22; N, 4.89; S, 11.17. Found: C, 79.69; H, 4.20; N,
20.2. HR-ESI-MS: ꢇꢈ/ calcd for [M + H]+ = C H N S
54 36
2
4
4.86; S, 11.13.
841.1841; found 841.1842. Anal. calcd. for C H N S : C,
54 36
2
4
77.14; H, 4.32; N, 3.33; S, 15.21. Found: C, 77.12; H, 4.30; N,
3.29; S, 15.18.
4.2.12. 3,6-Diiodocarbazole (8) [61]. Carbazole 1 (12.23 g,
73 mmol) was dissolved in boiling glacial acetic acid
(300 mL), and KI (15.84 g, 95 mmol) was added. e solution
was cooled, ground potassium iodate (23.42 g, 150 mmol) was
added, and the mixture was then boiled until it acquired
a clear straw-colored tint (10 min). e hot solution was
decanted from the undissolved potassium iodate, and it was
allowed to cool to 45∘C. e faintly brown plates were rapidly
filtered off and recrystallized from alcohol, and the solution
was allowed to cool to 45∘C and filtered, yielding 5.75 g of 8
as a brown solid (18.79%): mp 202∘C (mplit. 202∘C), 1H NMR
4.2.16. Preparation of P9. e compound was prepared from
2 eq of 3,6-di(thiophen-2-yl)-9H-carbazole
9
(0.21 g,
0.60 mmol) and 1 eq of 1,4-diiodobenzene 4 (0.10 g,
0.30 mmol). Purification by column chromatography (silica,
chloroform-hexane) gave P9 as a pale yellow solid (0.1 g,
50%). 1H NMR (400 MHz, CDCl ) ꢅ ppm 8.46 (s, 4 H), 7.90
3
(s, 4 H), 7.79 (dd, ꢆ = 8.50, 1.65 Hz, 4 H), 7.60 (d, ꢆ = 8.44 Hz,
4 H), 7.44 (d, ꢆ = 3.55 Hz, 4 H), 7.33 (d, ꢆ = 4.52 Hz, 4
H), 7.17 (dd, ꢆ = 4.95, 3.61 Hz, 4 H). 13C NMR (100 MHz,
(400 MHz, CDCl ) ꢅ ppm 8.34 (s, 2 H), 8.16 (br. s., 1 H), 7.70
3
(dd, ꢆ = 8.53, 1.63 Hz, 2 H), 7.23 (d, ꢆ = 8.41 Hz, 2 H); 13C
CDCl ) ꢅ ppm 145.2, 140.6, 129.5, 128.3, 128.1, 127.5, 125.1,
3
124.1, 124.0, 122.6, 118.1, 110.3. HR-ESI-MS: ꢇꢈ/ calcd for [M
NMR (100 MHz, CDCl ) ꢅ 138.5, 134.8, 129.4, 124.5, 112.7 and
3
+ H]+ = C H N S 737.1213; found 737.1210. Anal. calcd.
82.5. Maldi-Tof MS: ꢇꢈ/ calcd for [M+] = C H I N 418.867;
46 28
2
4
12 7 2
found 418.868. Anal. calcd. for C H I N: C, 34.40; H, 1.68; I,
for C H N S : C, 75.01; H, 3.83; N, 3.80; S, 17.36. Found: C,
12 7 2
46 28
2
4
60.58; N, 3.34. Found: C, 34.38; H, 1.65; I, 60.55; N, 3.30.
74.99; H, 3.80; N, 3.77; S, 17.32.
4.2.13. 3,6-Di(thiophen-2-yl)-9H-carbazole (9). e com-
Competing Interests
pound was prepared from 3,6-diiodocarbazole 8 as a white
solid (0.70 g, 59%): mp 127∘C. 1H NMR (600 MHz, CDCl )
e authors declare no competing financial interests.
3