26
M. Reig et al. / Dyes and Pigments 137 (2017) 24e35
mineral oil), bromoethane (90
m
L, 1.21 mmol) and anhydrous DMF
124.6, 123.9, 123.3, 121.4, 120.3, 114.0, 110.0, 91.7, 88.1, 38.2,
þ
(
8 mL). The crude was purified by flash column chromatography
14.1 ppm. HRMS (ESI-MS) (m/z): calcd for C22
H
18N (M þ H)
1
using hexane as the eluent to give compound 1 (237 mg, 86%). H
NMR (400 MHz, Acetone-d
¼ 8.45 (d, J ¼ 1.8 Hz, 1H), 8.23 (d,
J ¼ 7.5 Hz, 1H), 7.78 (dd, J ¼ 8.5 Hz, J ¼ 1.8 Hz, 1H), 7.61 (d, J ¼ 8.5 Hz,
H), 7.58 (d, J ¼ 8.3 Hz, 1H), 7.50e7.45 (m, 2H), 7.39 (dd, J ¼ 5.1 Hz,
J ¼ 1.2 Hz, 1H), 7.25e7.21 (m, 1H), 7.13 (dd, J ¼ 5.1 Hz, J ¼ 3.6 Hz, 1H),
296.1434, found: 296.1442. Anal. Calcd for C22
5.80; N, 4.74; found: C, 89.25; H, 6.14; N, 4.87.
H17N: C, 89.46; H,
6
) d
1
2.2.6. Synthesis of 9-ethyl-3,6-di-2-thienyl-9H-carbazole (4)
Prepared according to the general procedure for the alkylation
reaction using as starting materials 3,6-di-2-thienyl-9H-carbazole
(119 mg, 0.36 mmol), NaH (22 mg, 0.55 mmol, 60% dispersion in
mineral oil), bromoethane (41 ml, 0.55 mmol) and anhydrous DMF
(3 mL). The crude was purified by flash column chromatography
13
4
(
1
.52 (q, J ¼ 7.2 Hz, 2H), 1.42 (t, J ¼ 7.2 Hz, 3H) ppm. C NMR
100 MHz, Acetone-d
¼ 146.4, 141.4, 140.4, 129.0, 126.9, 126.5,
24.9, 124.5, 124.2, 123.7, 122.9, 121.4, 119.9, 118.3, 110.1, 109.9, 38.1,
6
) d
þ
1
2
5
4.1 ppm. HRMS (ESI-MS) (m/z): calcd for C18
78.0998, found: 278.0998. Anal. Calcd for C18
.45; N, 5.05; S, 11.56; found: C, 77.90; H, 5.37; N, 4.77; S, 11.24.
H
16NS (M þ H)
H
15NS: C, 77.94; H,
using a mixture of hexane and dichloromethane (10: 1 v/v) as the
1
eluent to give compound 4 (85 mg, 66%). H NMR (400 MHz, DMSO-
d
6
)
d
¼ 8.59 (d, J ¼ 1.8 Hz, 2H), 7.78 (dd, J ¼ 8.5 Hz, J ¼ 1.8 Hz, 2H),
2.2.3. Synthesis of 3-[2-(2-thienyl)ethynyl]-9H-carbazole
7.66 (d, J ¼ 8.5 Hz, 2H), 7.55 (dd, J ¼ 3.6 Hz, J ¼ 1.1 Hz, 2H), 7.50 (dd,
J ¼ 5.1 Hz, J ¼ 1.1 Hz, 2H), 7.16 (dd, J ¼ 5.1 Hz, J ¼ 3.6 Hz, 2H), 4.47 (q,
3
-Ethynyl-9H-carbazole (474 mg, 2.48 mmol), CuI (61 mg,
.32 mmol) and Pd(PPh Cl (84 mg, 0.12 mmol) were mixed in
mL of anhydrous THF under a nitrogen atmosphere. Then, trie-
13
0
8
3
)
2
2
J ¼ 7.1 Hz, 2H), 1.34 (t, J ¼ 7.1 Hz, 3H) ppm. C NMR (100 MHz,
CDCl
3
)
d
¼ 145.8, 140.1, 128.1, 126.1, 124.8, 123.9, 123.5, 122.3, 118.2,
thylamine (1.21 mL, 8.68 mmol) and 2-iodothiophene (0.60 mL,
.43 mmol) were added and the mixture was stirred at room
109.1, 37.9, 14.0 ppm. HRMS (ESI-MS) (m/z): calcd for C22
H18NS
2
þ
5
(M þ H) 360.0875, found: 360.0865. Anal. Calcd for C22
H17NS
2
: C,
temperature overnight. After, the solvent was distilled off under
reduced pressure and the crude was purified by flash column
chromatography using a mixture of hexane and dichloromethane
73.50; H, 4.77; N, 3.90; S, 17.84; found: C, 73.28; H, 4.97; N, 4.13; S,
17.76.
(
5: 1 v/v) as the eluent to give 3-[2-(2-thienyl)ethynyl]-9H-carba-
2.2.7. Synthesis of 9-(2-ethylhexyl)-3,6-di-2-thienyl-9H-carbazole
(5)
Prepared according to the general procedure for the alkylation
reaction using as starting materials 3,6-di-2-thienyl-9H-carbazole
(119 mg, 0.36 mmol), NaH (17 mg, 0.43 mmol, 60% dispersion in
1
zole (309 mg, 46%). H NMR (400 MHz, Acetone-d
1
6
)
d
¼ 10.58 (s,
H), 8.34 (s, 1H), 8.21 (d, J ¼ 7.8 Hz, 1H), 7.58e7.54 (m, 3H), 7.51 (dd,
J ¼ 5.2 Hz, J ¼ 0.9 Hz, 1H), 7.46e7.42 (m, 1H), 7.33 (dd, J ¼ 3.6 Hz,
J ¼ 0.9 Hz, 1H), 7.26e7.22 (m, 1H), 7.10 (dd, J ¼ 5.2 Hz, J ¼ 3.6 Hz,1H)
1
3
ppm. C NMR (100 MHz, Acetone-d
6
)
d
¼ 141.4, 140.8, 132.2, 129.7,
mineral oil), 2-ethylhexyl bromide (76 mL, 0.43 mmol) and anhy-
drous DMF (6 mL). The crude was purified by flash column chro-
1
28.2, 128.0, 127.2, 124.6, 124.5, 124.2, 123.4, 121.3, 120.3, 113.6,
1
C
12.1, 112.0, 95.3, 81.0 ppm. HRMS (ESI-MS) (m/z): calcd for
matography using a mixture of hexane and dichloromethane (9: 1
v/v) as the eluent to give compound 5 (90 mg, 56%). H NMR
þ
1
18
H12NS (M þ H) 274.0685, found: 274.0685.
(
400 MHz, Acetone-d
6
)
d
¼ 8.55 (d, J ¼ 1.5 Hz, 2H), 7.79 (dd,
2.2.4. Synthesis of 9-ethyl-3-[2-(2-thienyl)ethynyl]-9H-carbazole
J ¼ 8.5 Hz, J ¼ 1.5 Hz, 2H), 7.57 (d, J ¼ 8.5 Hz, 2H), 7.48 (d, J ¼ 3.6 Hz,
2H), 7.39 (d, J ¼ 5.0 Hz, 2H), 7.13 (dd, J ¼ 5.0 Hz, J ¼ 3.6 Hz, 2H), 4.31
(d, J ¼ 7.5 Hz, 2H), 2.16e2.08 (m, 1H), 1.48e1.19 (m, 8H), 0.93 (t,
(2)
Prepared according to the general procedure for the alkylation
13
reaction using as starting materials 3-[2-(2-thienyl)ethynyl]-9H-
carbazole (164 mg, 0.60 mmol), NaH (36 mg, 0.90 mmol, 60%
dispersion in mineral oil), bromoethane (67
anhydrous DMF (6 mL). The crude was purified by flash column
J ¼ 7.4 Hz, 3H), 0.83 (t, J ¼ 7.2 Hz, 3H) ppm. C NMR (100 MHz,
CDCl
3
)
d
¼ 145.8, 141.0, 128.1, 126.0, 124.7, 123.8, 123.3, 122.2, 118.1,
mL, 0.90 mmol) and
109.6, 47.8, 39.6, 31.2, 29.0, 24.6, 23.2, 14.2, 11.1 ppm. HRMS (ESI-
MS) (m/z): calcd for C28
Anal. Calcd for C28 29NS
þ
H
30NS
2
(M þ H) 444.1814, found: 444.1817.
chromatography using a mixture of hexane and dichloromethane
H
2
: C, 75.80; H, 6.59; N, 3.16; S, 14.45; found:
1
(
(
9: 1 v/v) as the eluent to give compound 2 (99 mg, 55%). H NMR
400 MHz, Acetone-d
C, 75.87; H, 7.20; N, 3.23; S, 13.29.
6
)
d
¼ 8.35 (s, 1H), 8.23 (d, J ¼ 7.8 Hz, 1H),
7
.64e7.59 (m, 3H), 7.53e7.49 (m, 2H), 7.34 (dd, J ¼ 3.6 Hz, J ¼ 1.0 Hz,
2.2.8. 9-(3,5-Di-tert-butylphenyl)-3,6-di-2-thienyl-9H-carbazole
(6)
1
H), 7.28e7.24 (m, 1H), 7.10 (dd, J ¼ 5.2 Hz, J ¼ 3.6 Hz, 1H), 4.50 (q,
13
J ¼ 7.2 Hz, 2H), 1.41 (t, J ¼ 7.2 Hz, 3H) ppm. C NMR (100 MHz,
Acetone-d
¼ 141.4, 140.7, 132.3, 129.7, 128.2, 128.0, 127.2, 124.6,
24.5, 123.9, 123.2, 121.5, 120.3, 113.5, 110.1, 110.0, 95.2, 81.1, 38.2,
A
mixture of 3,6-di-2-thienyl-9H-carbazole (381 mg,
mmol), 1-bromo-3,5-di-tert-butylbenzene (937 mg,
3.48 mmol), anhydrous K CO (339 mg, 2.45 mmol) and Cu powder
6
)
d
1.15
1
2
3
þ
14.1 ppm. HRMS (ESI-MS) (m/z): calcd for C20
H
16NS (M þ H)
(10 mg, 0.16 mmol) was refluxed in anhydrous DMF (5 mL) under
nitrogen atmosphere for 24 h. After, the reaction mixture was
filtered through Celite and diluted with water. The aqueous layer
was extracted with dichloromethane and the organic layer was
3
5
02.0998, found: 302.1011. Anal. Calcd for C20H15NS: C, 79.70; H,
.02; N, 4.65; S, 10.64; found: C, 79.37; H, 5.20; N, 4.87; S, 10.40.
2.2.5. Synthesis of 9-ethyl-3-(2-phenylethynyl)-9H-carbazole (3)
2 4
dried over Na SO , filtered off and the solvent was distilled off
Prepared according to the general procedure for the alkylation
under reduced pressure. The crude was purified by flash column
reaction using as starting materials 3-(2-phenylethynyl)-9H-
carbazole (182 mg, 0.68 mmol), NaH (40 mg, 1.00 mmol, 60%
chromatography using a mixture of hexane and dichloromethane
(10: 1 v/v) as the eluent to give compound 6 (320 mg, 54%). H NMR
1
dispersion in mineral oil), bromoethane (75
anhydrous DMF (6 mL). The crude was purified by flash column
chromatography using a mixture of hexane and dichloromethane
m
L, 1.00 mmol) and
(400 MHz, CDCl
3
)
d
¼ 8.41 (d, J ¼ 1.8 Hz, 2H), 7.71 (dd, J ¼ 8.5 Hz,
J ¼ 1.8 Hz, 2H), 7.53 (t, J ¼ 1.8 Hz,1H), 7.43 (d, J ¼ 8.5 Hz, 2H), 7.41 (d,
J ¼ 1.8 Hz, 2H), 7.38 (dd, J ¼ 3.6 Hz, J ¼ 1.1 Hz, 2H), 7.28 (dd,
J ¼ 5.1 Hz, J ¼ 1.1 Hz, 2H), 7.13 (dd, J ¼ 5.1, Hz, J ¼ 3.6 Hz, 2H), 1.41 (s,
1
(
9: 1 v/v) as the eluent to give compound 3 (136 mg, 68%). H NMR
13
(
1
7
400 MHz, Acetone-d
H), 7.65 (dd, J ¼ 8.5 Hz, J ¼ 1.5 Hz, 1H), 7.63e7.56 (m, 4H),
.53e7.49 (m, 1H), 7.45e7.36 (m, 3H), 7.28e7.24 (m, 1H), 4.52 (q,
6
)
d
¼ 8.36 (d, J ¼ 1.5 Hz,1H), 8.23 (d, J ¼ 7.8 Hz,
18H) ppm. C NMR (100 MHz, CDCl
3
)
d
¼ 152.9, 145.7, 141.1, 136.8,
128.2, 127.0, 125.0, 124.0, 123.8, 122.4, 121.6, 121.1, 118.0, 110.6, 35.3,
þ
31.6 ppm. HRMS (ESI-MS) (m/z): calcd for C34
520.2127, found: 520.2148. Anal. Calcd for C34 33NS
6.40; N, 2.69; S, 12.34; found: C, 78.52; H, 6.46; N, 2.47; S, 12.42.
H
34NS
2
(M þ H)
13
J ¼ 7.2 Hz, 2H), 1.42 (t, J ¼ 7.2 Hz, 3H) ppm. C NMR (100 MHz,
H
2
: C, 78.57; H,
Acetone-d
6
) d
¼ 141.4, 140.6, 132.1, 130.0, 129.4, 128.8, 127.2, 124.8,