E. Juskelyte et al. / Reactive & Functional Polymers 70 (2010) 81–87
83
(eluent:ethylacetate/hexane, 1:2). The yield of compound 5a was
61% (0.5 g). 1H NMR (300 MHz, CDCl3), d (ppm): 2.53 (q, 1H,
OCH2, (HA), JAX = 2.8 Hz, JAB = 7.3 Hz), 2.78 (t, 1H, CH2O (HA),
JAX = 4.5 Hz, JAB = 8.7 Hz), 3.29–3.36 (m, 1H, ACHO), 4.35 (dd, 1H,
one proton of NCH2, (HA), JAX = 5 Hz, JAB = 15.7 Hz), 4.60 (dd, 1H, an-
other proton of NCH2, (HB), JBX = 3.3 Hz, JAB = 15.3 Hz), 7.8 (dd, 1H,
2-HHt, JAX = 1.6 Hz, JAB = 8.6 Hz), 8.06 (d, 1H, 5-HHt, J = 7.7 Hz), 8.2
(s, 1H, 4-HHt), 7.1–7.5 (m, 15H, ACH Ar.). IR (KBr), (cmꢀ1): 3420,
were added to the reaction flask. The reaction mixture was re-
fluxed for 24 h. When the reaction was finished, the solvent was
evaporated, and the crude product was purified by column chro-
matography (eluent:ethylacetate/hexane, 1:2). The yield of com-
pound 7a was 29% (0.4 g). 1H NMR (300 MHz, CDCl3), d (ppm):
3.09–3.26 (m, 4H, SCH2), 3.3 (s, 2H, OH), 3.69–3.76 (m, 2H, ACH),
4.37 (dd, 2H, one proton of NCH2, (HA), JAX = 4.6 Hz, JAB = 15.7 Hz),
4.6 (dd, 2H, another proton of NCH2, (HB), JBX = 2.8 Hz,
3050
700
m
(CH Ar.); 2922
m
(CH Aliph.), 1589, 1493
m
(C@C Ar.), 747,
JAB = 15.8 Hz), 7.80 (d, 2H, 2-HHt, J = 8.6 Hz), 8.07 (d, 2H, 5-HHt
J = 7.8 Hz), 8.23 (s, 2H, 4-HHt), 6.81–8.45 (m, 38H, ACH Ar.). IR
(KBr), (cmꢀ1): 3550, 3341
(OH), 3049 (CH Ar.); 1588, 1493,
1475 (C@C Ar.); 746,
(CH Ar.). MS (APCl+, 20 V), m/z (%):
,
c
(CH Ar.). MS (APCI+, 20 V), m/z (%): 418 ([M + H]+, 100). Ele-
mental analysis calculated for C28H23N3O: C, 80.55%; H, 5.55%, N,
10.06%. Found: C, 80.56%; H, 5.54%, N, 10.03%.
m
m
m
c
1088 ([M + H]+, 10). Elemental analysis calculated for
C68H58N6O2S3: C, 75.11%; H, 5.38%, N, 7.73%. Found: C, 75.22%; H,
5.32%, N, 7.65%.
2.2.6. 9-(Oxiranylmethyl)carbazol-3-yl-carbaldehyde N-methyl-N-
phenylhydrazone (5b)
Compound 4 (0.5 g, 1.98 mmol) and N-methyl-N-phenylhydr-
azine (0.36 g, 2.98 mmol) were dissolved in 20 ml of methanol
and stirred at 65 °C for 22 h. After the reaction the solvent was
evaporated. The crude product was purified by column chromatog-
raphy (eluent:ethylacetate/hexane, 1:2), crystallized from metha-
nol, and dried. The yield of compound 5b was 34% (0.5 g). M.p.
151 °C (DSC). 1H NMR (300 MHz, CDCl3), d (ppm): 2.54 (q, 1H,
one proton of OCH2, (HA), JAX = 2.5 Hz, JAB = 4.7 Hz), 2.78 (t, 1H, an-
other proton of CH2O, JBX = 4.1 Hz, JAB = 8.7 Hz), 3.32 (m, 1H,
ACHO), 3.44 (s, 3H, ACH3), 4.35 (dd, 1H, one proton of NCH2,
(HA), JAX = 5 Hz, JAB = 15.7 Hz), 4.59 (dd, 1H, another proton of
2.2.10. 1,3-Di({3-[(2,2-diphenylhydrazine-1-
ylidene)methyl]carbazole-9-yl}-2-hydroxypropylsulfanyl)benzene
(7b)
Compound 7b was synthesized by the similar procedure as
compound 7a, only 1,3-benzenedithiol was used instead of 4,4‘-
thiobisbenzenethiol and the reaction time was 5 h. The yield of
compound 7b was 42%. 1H NMR (300 MHz, DMSO), d (ppm):
3.05–3.24 (m, 4H, SCH2), 3.99–4.14 (m, 2H, ACH), 4.3 (dd, 2H,
one proton of NCH2, (HA), JAX = 6 Hz, JAB = 14 Hz), 4.5 (dd, 2H, an-
other proton of NCH2, (HB), JBX = 4.4 Hz, JAB = 14 Hz), 5.49 (d, 2H,
NCH2, (HB), JBX = 3.3 Hz, JAB = 15.7 Hz), 7.9 (dd, 1H, 2-HHt
JAX = 1.6 Hz, JAB = 8.5 Hz), 8.12 (d, 1H, 5-HHt, J = 7.3 Hz), 8.3 (s, 1H,
4-HHt), 6.7–7.7 (m, 10H, ACH Ar.). IR (KBr), (cmꢀ1): 3430, 3048
(CH, Ar.); 2993, 2922 (CH, Aliph.); 1589, 1499 (C@C, Ar.); 746
(CH Ar.). MS (APCI+, 20 V), m/z (%): 356 ([M + H]+, 100). Elemental
,
J = 5.1 Hz, OH), 7.85 (d, 2H, 2-HHt, J = 7.4 Hz), 8.17 (d, 2H, 5-HHt
J = 7.7 Hz), 8.27 (s, 2H, 4-HHt), 7.01–7.64 (m, 38H, ACH Ar.). IR
(KBr), (cmꢀ1): 3428
(OH), 3049 (CH, Ar.); 1589, 1493, 1463
(C@C, Ar.); 746
,
m
m
m
m
m
m
c
(CH, Ar.). MS (APCl+, 20 V), m/z (%): 980
c
([M + H]+, 10). Elemental analysis calculated for C62H54N6O2S2: C,
76.04%; H, 5.56%, N, 8.58%. Found: C, 76.13%; H, 5.62%, N, 8.49%.
analysis calculated for C23H21N3O: C, 77.72%; H, 5.96%, N, 11.82%.
Found: C, 77.78%; H, 5.89%, N, 11.76%.
2.2.7. Poly[9-(oxiranylmethyl)carbazol-3-yl-carbaldehyde N,N-
diphenylhydrazone] (6a)
2.2.11. 4,40-Di({3-[(2-methyl,2-phenylhydrazine-1-
ylidene)methyl]carbazole-9-yl}-2-
Dry dichloromethane (0.28 ml) was added to a flask with com-
pound 5a (0.1 g, 0.28 mmol) under nitrogen. The flask was placed
in the bath of dry ice with isopropanol and cooled down to
ꢀ70 °C. Then 0.2 ml of 1 M solution of BF3(C2H5)2O in dichloro-
methane were added. The reaction was carried out for 5 h. Then
few drops of triethylamine (TEA) were added. The reaction mixture
was concentrated and precipitated into methanol. The formed
white precipitates were filtered, washed with methanol two times,
and dried at room temperature. The yield of polymer 6a was 50%
(0.05 g). 1H NMR (300 MHz, CDCl3), d (ppm): 3.3–4.5 (m, 5H),
7.8–8.2 (m, 3H, 2, 4, 5-HHt), 6.9–7.5 (m, 15H, ACH Ar.). IR (KBr),
hydroxypropylsulfanyl)diphenylsulfane (8a)
Compound 8a was synthesized by the same procedure as com-
pound 7a, only compound 5b was used instead of compound 5a.
The yield of compound 8a was 19.6%. 1H NMR (300 MHz, DMSO),
d (ppm): 3.09–3.26 (m, 4H, SCH2), 3.40 (s, 6H, CH3), 4.09 (m, 2H,
ACH), 4.41 (dd, 2H, one proton of NCH2, (HA), JAX = 7.4 Hz,
JAB = 15.4 Hz), 4.55 (dd, 2H, another proton of NCH2, (HB),
JBX = 5 Hz, JAB = 15 Hz), 5.52 (d, 2H, JAX = 5.5 Hz, OH), 7.87 (d, 2H,
2-HHt, J = 7.32 Hz), 8.18 (d, 2H, 5-HHt, J = 7.7 Hz), 8.4 (s, 2H, 4-
HHt), 6.85–7.61 (m, 28H, ACH Ar.). IR (KBr), (cmꢀ1): 3340
3048 (CH, Ar.); 2963, 2923 (CH, Aliph.); 1596, 1492, 1465
(C@C, Ar.); 746
m (OH),
m
m
m
(cmꢀ1): 3564
1590, 1493
m
(OH), 3054
m
(CH Ar.); 2932, 2871
m (CH Aliph.),
c
(CH, Ar.). MS (APCl+, 20 V), m/z (%): 964
([M + H]+, 10). Elemental analysis calculated for C58H54N6O2S3: C,
72.32%; H, 5.65%, N, 8.72%. Found: C, 72.41%; H, 5.58%, N, 8.67%.
m
(C@C Ar.), 747,
c (CH Ar.).
2.2.8. Poly[9-(oxiranylmethyl)carbazol-3-yl-carbaldehyde N-methyl-
N-phenylhydrazone] (6b)
6b was synthesized from 9-(oxiranylmethyl)carbazol-3-yl-carb-
aldehyde N-methyl-N-phenylhydrazone 5b (0.27 g, 0.76 mmol)
using 0.2 ml of 1 M solution of BF3(C2H5)2O in dichloromethane as
initiator by the same way as polymer 6a. The yield polymer 6b
was 26% (0.07 g). 1H NMR (300 MHz, CDCl3), d (ppm): 3.0–4.5 (m,
5H), 7.8–8.5 (m, 3H, 2, 4, 5-HHt), 6.7–7.8 (m, 10H, ACH Ar.). IR
2.2.12. 1,3-Di({3-[(2-methyl,2-phenylhydrazine-1-
ylidene)methyl]carbazole-9-yl}-2-hydroxypropylsulfanyl)benzene
(8b)
Compound 8b was synthesized by the same procedure as com-
pound 7a, only compound 5b was used instead of compound 5a
and 1,3-benzenedithiol was used instead of 4,40-thiobisbenzeneth-
iol. The yield of compound 8b was 24%. 1H NMR (300 MHz, CDCl3),
d (ppm): 2.78–3.06 (m, 4H, SCH2), 3.37 (s, 6H, ACH3), 3.70–3.74 (m,
2H, ACH), 4.25–4.30 (m, 4H, NCH2), 6.81–8.30 (m, 30H, ACH Ar.).
(KBr), (cmꢀ1): 3324
(CH, Aliph.); 1597, 1493
(CAO); 749 (CH, Ar.).
m
(OH), 3051
m
(CH, Ar.); 2972, 2933, 2877
m
m
m
(C@C, Ar.); 1111, 1084, 1062, 1030
c
IR (KBr), (cmꢀ1): 3380
(CH, Aliph.); 1596,1568, 1491, 1462
m
(OH), 3048
m
(CH, Ar.); 2960, 2926
m
2.2.9. 4,40-Di({3-[(2,2-diphenylhydrazine-1-ylidene)methyl]carbazole-
9-yl}-2-hydroxypropylsulfanyl)diphenylsulfane (7a)
m
(C@C, Ar.); 746
c
(CH, Ar.).
MS (APCl+, 20 V), m/z (%): 856 ([M + H]+, 10). Elemental analysis
calculated for C52H50N6O2S2: C, 73.04%; H, 5.89%, N, 9.83%. Found:
C, 73.18%; H, 5.81%, N, 9.76%.
Compound 5a (0.52 g, 1.24 mmol), 4,40-thiobisbenzenethiol
(0.14 g, 0.6 mmol), triethylamine (0.2 ml), and 2-butanone (7 ml)