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A. Tomkeviciene et al. / Reactive & Functional Polymers 71 (2011) 796–802
1.2 mmol), sodium tert-butoxide (2.7 g, 28.2 mmol) and dry tolu-
ene (40 ml) were used. The crude product was purified by column
chromatography using an eluent mixture of hexane and acetone in
volume ratio of 5:1. The yield was 49% (0.9 g) of yellow crystals
(FW = 428 g/mol, m.p.: 162–163 °C).
secondary amine, and purified by column chromatography using
an eluent mixture of hexane and acetone in volume ratio of 20:1.
The yield was 53% of compound 2c (FW = 430 g/mol, m.p.: 132–
133 °C).
1H NMR spectrum (300 MHz, CDCl3, d, ppm): 3.10 (s, 4H,
CH2ACH2), 4.03–4.10 (m, 3H, CH@CH2, NCH2), 4.18 (dd,
J1 = 14.3 Hz, J2 = 2.6 Hz, 1H, CH@CH2), 4.54 (t, J = 5.9 Hz, 2H,
OCH2), 6.45 (dd, J1 = 14.3 Hz, J2 = 7.0 Hz, 1H, OACH@), 6.94 (dd,
J1 = 8.8 Hz, J2 = 2.6 1H, Ar), 7.14–7.58 (m, 13H, Ar), 7.93 (d,
J = 7.7 Hz, 1H, Ar).
1H NMR spectrum (300 MHz, CDCl3, d, ppm): 4.01–4.04 (m, 3H,
CH = CH2, NCH2), 4.18 (dd, J1 = 14.3 Hz, J2 = 2.2 Hz, 1H, CH = CH2),
4.48 (t, J = 6.2 Hz, 2H, OCH2), 6.45 (dd, J1 = 14.6 Hz, J2 = 7.0 Hz, 1H,
OACH@), 6.57 (dd, J1 = 8.8 Hz, J2 = 2.6 Hz, 1H, Ar), 6.90 (s, 2H, Ar),
6.98 (d, J = 2.6 Hz, 1H, Ar), 7.12–7.17 (m, 2H, Ar), 7.36–7.69 (m,
10H, Ar), 7.86 (d, J = 7.7 Hz, 1H, Ar).
13C NMR spectrum (75.4 MHz, CDCl3, d, ppm): 31.6 (2CH2), 42.5
(NCH2), 66.0 (CH@CH2), 87.2 (OCH2), 104.9 (CH@CH2), 108.8, 109.1,
114.4, 118.6, 120.7, 123.1, 123.8, 125.8, 126.8, 127.4, 130.6, 131.2,
134.7, 138.8, 141.6.
13C NMR spectrum (75.4 MHz, CDCl3, d, ppm): 42.4 (NCH2), 65.9
(CH@CH2), 87.2 (OCH2), 103.0 (CH@CH2), 108.7, 112.5, 118.5,
120.7, 123.06, 123.4, 125.7, 127.3, 130.2, 130.9, 131.4, 134.8,
137.2, 141.3, 143.4, 144.6, 151.6.
IR (KBr, cmꢂ1): 3048 (CAH, Ar); 2936, 2916, 2870 (CAH); 1612,
1606 (C@C), 1488, 1467 (CAC, Ar); 1321 (CAN); 1148 (CAOAC);
811, 778, 744 (CAH, Ar).
IR (KBr, cmꢂ1): 3049 (CAH, Ar); 2921, 2868 (CAH); 1610 (C@C),
1485, 1461 (CAC, Ar); 1307 (CAN); 1095 (CAOAC); 800, 736 (CAH,
Ar).
MS (APCl+, 20 V, m/z): 431 ([M+H]+, 100%).
MS (APCl+, 20 V, m/z): 429 ([M+H]+, 35%).
Elemental analysis. Calcd for C30H26N2O (%): C 83.69, H 6.09, N
6.51; found (%): C 83.30, H 6.41, N 6.37.
Elemental analysis. Calcd for C30H24N2O (%): C 84.08, H 5.65, N
6.54; found (%): C 86.99, H 6.19, N 6.92.
Poly{3-[dibenz(b,f)azepinyl]-9-[(3-methyloxetane-3-
yl)methyl]carbazole} (3) 3-[Dibenz(b,f)azepinyl]-9-[(3-methyloxe-
tane-3-yl)methyl]carbazole (1b, 0.5 g, 1.1 mmol) was dissolved in
2 ml of dichloroethane under nitrogen. Then BF3ꢀO(C2H5)2
3-[10,11-Dihydrodibenz(b,f)azepinyl]-9-(2-ethylhexyl)carbazole
(2a) was prepared according to the same procedure as described
for 1a, using 10,11-dihydro-5H-dibenz(b,f)azepine as secondary
amine, and purified by column chromatography using an eluent
mixture of hexane and acetone in volume ratio of 10:1. The yield
was 37% of compound 2a (FW = 472 g/mol, m.p.: 94–95 °C).
1H NMR spectrum (300 MHz, CDCl3, d, ppm): 0.96 (t, J = 7.3 Hz,
6H, CH3), 1.31–1.50 (m, 8H, CH2), 2.07–2.02 (m, 1H, CH), 3.11 (s,
4H, CH2ACH2), 4.20 (q, 2H, NCH2), 6.96 (dd, J1 = 8.4 Hz,
J2 = 2.0 Hz, 1H, Ar), 7.15 (t, J = 7.3 Hz, 1H, Ar), 7.26–7.59 (m, 12H,
Ar), 7.94 (d, J = 7.7 Hz, 1H, Ar).
(0.055 mmol, 6.4 ll) was added to the solution and the reaction
mixture was stirred for 24 h at 60 °C under argon. After the reac-
tion the initiator was neutralized by ammonia solution. Then the
solvent was removed by evaporation. The product was dissolved
in a small amount of THF and precipitated into methanol. After
Soxhlet extraction (24 h) by methanol and re-precipitation, the
yield of polymer 3 was 89% (0.45 g).
1H NMR spectrum (300 MHz, CDCl3, d, ppm): 0.61–1.09 (m, 3H,
CH3), 2.93–3.41 (m, 4H, OCH2, NCH2), 3.91–4.28 (m, 2H, OCH2),
6.28–7.85 (m, 17H, Ar).
13C NMR spectrum (75.4 MHz, CDCl3, d, ppm): 11.2 (CH3), 14.4
(CH3), 23.4 (CH2), 24.7 (CH2), 29.2 (CH2), 31.3 (CH2), 31.65
(2CH2), 39.8 (CH), 47.7 (NCH2), 105.0, 109.0, 109.3, 114.4, 118.1,
120.6, 122.8, 123.5, 125.6, 126.7, 127.3, 130.6, 131.2, 135.2, 138.8.
IR (KBr, cmꢂ1): 3048 (CAH, Ar); 2953, 2930, 2870 (CAH); 1485,
1459, 1440 (CAC, Ar); 1321 (CAN); 774, 744 (CAH, Ar).
MS (APCl+, 20 V, m/z): 473 ([M+H]+, 100%).
IR (KBr, cmꢂ1): 3049 (CAH, Ar); 2871 (CAH); 1488, 1464 (CAC,
Ar); 1319 (CAN); 1119 (CAOAC); 795, 743 (CAH, Ar).
Poly{3-[10,11-dihydrodibenz(b,f)azepinyl]-9-[(3-methyloxetane-
3-yl)methyl]carbazole} (4) was prepared using 3-[10,11-dihydrodi-
benz(b,f)azepinyl]-9-[(3-methyloxetane-3-yl)methyl]carbazole
Elemental analysis. Calcd for C34H36N2 (%): C 86.40, H 7.68, N
5.93; found (%): C 86.34, H 8.12, N 5.82.
(2b) (0.4 g, 0.9 mmol) and cationic initiator BF3ꢀO(C2H5)2 (5.2
ll,
0.045 mmol) by the same procedure as described for polymer 3.
After Soxhlet extraction (24 h) by methanol and re-precipitation,
the yield of polymer 4 was 55% (0.22 g).
3-[10,11-Dihydrodibenz(b,f)azepinyl]-9-[(3-methyloxetane-3-
yl)methyl]carbazole (2b) was synthesized according to the same
procedure as described for 1b, using 10,11-dihydro-5H-
dibenz(b,f)azepine as secondary amine, and purified by column
chromatography using using an eluent mixture of hexane and ace-
tone in volume ratio of 20:1. The yield was 67% of yellow crystals
(FW = 444 g/mol, m.p.: 208–209 °C).
1H NMR spectrum (300 MHz, CDCl3, d, ppm): 0.84–1.20 (m, 3H,
CH3), 2.80–3.10 (m, 4H, CH2ACH2), 3.14–3.59 (m, 4H, OCH2, NCH2),
4.00–4.49 (m, 2H, OCH2), 6.59–7.96 (m, 15H, Ar).
IR (KBr, cmꢂ1): 3049 (CAH, Ar); 2925, 2873 (CAH); 1487, 1464,
1448 (CAC, Ar); 1320 (CAN); 1110 (CAOAC); 774, 744 (CAH, Ar).
Poly{3-[dibenz(b,f)azepinyl]-9-[2-(vinyloxy)ethyl]carbazole} (5)
was prepared using 3-[Dibenz(b,f)azepinyl]-9-[2-(vinyloxy)
1H NMR spectrum (300 MHz, DMSO-d6, d, ppm): 1.33 (s, 3H,
CH3), 2.97 (s, 4H, CH2ACH2), 4.16 (d, J = 5.9 Hz, 2H, OCH2), 4.40
(s, 2H, NCH2), 4.59 (d, J = 5.9 Hz, 2H, OCH2), 6.79 (dd, J1 = 8.8 Hz,
J2 = 2.2 Hz, 1H, Ar), 7.07 (t, J = 7.7 Hz, 1H, Ar), 7.22–7.55 (m, 12H,
Ar), 7.81 (d, J = 7.7 Hz, 1H, Ar).
ethyl]carbazole (1c) (0.3 g, 0.7 mmol) and BF3ꢀO(C2H5)2 (4
ll,
0.035 mmol) by the same procedure as described for polymer 3.
After Soxhlet extraction (24 h) by methanol and re-precipitation,
the yield of polymer 5 was 30% (0.12 g).
13C NMR spectrum (75.4 MHz, DMSO-d6, d, ppm): 23.5 (CH3),
31.4 (2CH2), 43.1 (CH), 48.6 (NCH2), 80.1 (OCH2 in oxetane ring),
105.1, 110.3, 110.9, 115.1, 119.0, 120.7, 122.4, 123.3, 126.3,
127.2, 127.9, 130.3, 131.7, 135.7, 138.5.
1H NMR spectrum (300 MHz, CDCl3, d, ppm): 1.54–1.81 (m, 2H,
CH2), 3.65–4.54 (m, 4H, OCH2, NCH2), 4.98–5.02 (m, 1H, OCH),
6.27–8.27 (m, 17H, Ar).
IR (KBr, cmꢂ1): 3053 (CAH, Ar); 2954, 2925, 2874 (CAH); 1488,
1466, 1456 (CAC, Ar); 1317 (CAN); 1062 (CAOAC); 781, 751 (CAH,
Ar).
IR (KBr, cmꢂ1): 3051, 3021 (CAH, Ar); 2927 (CAH); 1488 (CAC,
Ar); 1319 (CAN); 1115 (CAOAC); 797, 763, 746 (CAH, Ar).
Poly{3-[10,11-dihydrodibenz(b,f)azepinyl]-9-[2-(vinyl-
MS (APCl+, 20 V, m/z): 445 ([M+H]+, 100%).
oxy)ethyl]carbazole} (6) was prepared using 3-[10,11-Dihydrodi-
benz(b,f)azepinyl]-9-[2-(vinyloxy)ethyl]carbazole (2c) (0.35 g,
Elemental analysis. Calcd for C31H28N2O (%): C 83.75, H 6.35, N
6.30; found (%): C 82.52, H 6.41, N 6.27.
3-[10,11-Dihydrodibenz(b,f)azepinyl]-9-[2-(vinyloxy)ethyl]carba-
zole (2c) was synthesized according to the same procedure as de-
scribed for 1c, using 10,11-dihydro-5H-dibenz(b,f)azepine as
0.81 mmol) and BF3ꢀO(C2H5)2 (4.7
ll, 0.04 mmol) by the same pro-
cedure as described for polymer 3. After Soxhlet extraction (24 h)
by methanol and re-precipitation, the yield of polymer 6 was
67% (0.23 g).