J. Su et al. / Dyes and Pigments 146 (2017) 92e102
95
2
.4. Molecular modeling
2.5.3. C3, (E)-2-(((2-styrylphenyl)amino)methyl)phenol
-((E)-((2-((E)-Styryl)phenyl)imino)methyl)phenol
2
(0.2
g,
*
*
6
-31G
employed to conduct molecular modeling. Geometry optimization
of enol and keto tautomers in ground state (S ) was performed by
using B3LYP method based on HF (Hartree-Fock) level [33], while
CIS (single-excitation configuration interaction) was used to obtain
Basis set in Gaussian 09 program package was
0.478 mmol) and dry ethanol 50 ml were placed into a dry round-
bottomed flask, the mixture was stirred vigorously and so dium
borohydride (0.17 g, 4.78 mmol) in 20 ml dry ethanol was added
dropwise from a constant pressure burette at room temperature
under protection of argon. The mixed solution was stirred for
2e3 h. After the reaction, the solvent was evaporated under vac-
0
1
optimized geometries in the first singlet excited state (S ) of the
molecules. DFT and TD-DFT (time-dependence DFT) method at HF
and CIS levels were utilized to compute the energies of optimized
uum. Recrystallization from CH
material as faint yellow solid (yield, 65%, m.p., 179.9e181.5 C). H
NMR (500 MHz, DMSO-d (ppm): 9.549 (s, -OH, 1H), 7.663e7.647
2 2
Cl and cyclohexane gave pure
ꢃ
1
geometries of S
single-point calculation//optimization method) [34]. The organic
solvents were used as the media for theoretical computation.
0
and S
1
respectively such as DFT//HF or TDDFT//CIS
6
) d
(
(d, J ¼ 8.0 Hz, Ar-H, 2H), 7.539e7.507 (d, J ¼ 16.0 Hz, CH¼CH, 1H),
7.460e7.445 (d, J ¼ 7.5 Hz, Ar-H, 1H), 7.390 (t, J ¼ 7.75 Hz, Ar-H, 2H),
7
.263e7.233 (t, J ¼ 7.5 Hz, Ar-H, 1H), 7.152e7.138 (d, J ¼ 7.0 Hz, Ar-H,
2.5. Synthesis of the studied dyes
1H), 7.043e6.968 (m, Ar-H, 3H), 6.807e6.785 (d, J ¼ 11.0 Hz,
CH¼CH, 1H) 6.721e6.692 (t, J ¼ 7.25 Hz, Ar-H, 1H), 6.582e6.552 (t,
J ¼ 7.5 Hz, CH¼CH, 1H), 6.429e6.413 (d, J ¼ 8.0 Hz, Ar-H, 1H), 6.224
Synthesis routes of the studied dyes were presented in Scheme
13
1. All the dyes were synthesized in our laboratory firstly. Synthesis
2 6
(s, -NH-, 1H), 4.309 (s, -CH -, 2H). C NMR (125 MHz, DMSO-d )
and molecular structural characterization of the intermediates
were shown in Supplementary materials. Preparation details and
chemical structural characterization of the studied target dyes C1-
C9 were described in the followings.
d (ppm): 155.347, 146.240, 138.247, 129.158, 128.987, 128.487,
128.101, 127.743, 127.592, 126.954, 126.255, 126.118, 124.779,
ꢂ1
122.514, 119.222, 116.413, 115.269, 111.245, 41.745. FT-IR (cm ):
3416.70, 3224.46, 3208.79, 3182.08, 3158.37, 3139.87, 3095.77,
3027.95, 2854.84, 1597.40, 1492.52, 1456.11, 1398.70, 1325.76,
2
.5.1. C1, 2-((E)-((2-((E)-styryl)phenyl)imino)methyl)phenol
-Styrylaniline (0.976 g, 5 mmol) and 2-hydroxybenzaldehyde
1.220 g, 10 mmol) in 100 ml dry ethanol were added into three-
1246.82, 1103.79, 963.64, 753.72, 692.16. MS (ESI) m/z:calcd for
þ
2
21
C H19NO [MþH] 302.15, found 302.43. Elementary analysis, Anal.
(
Calcd for C21
H19NO: C, 83.70; H, 6.35; N, 4.64. Found: C, 83.82; H,
necked flask. The reaction mixture was stirred at room tempera-
ture under argon protection for 12 h. After the reaction, the solvent
was evaporated under vacuum. Recrystallization from ethanol and
cyclohexane gave pure material as faint yellow solid (yield, 62%,
6.24; N, 4.77.
2.5.4. C4, 2-((E)-((3-((E)-styryl)phenyl)imino)methyl)phenol
Synthetic procedure and method of C4 were the same as
described in synthesis of C1, in which 2-styrylaniline was replaced
by 3-styrylaniline. Crude product was further purified to afford the
desired product as faint yellow needle solid (yield 65%, m.p.,
ꢃ
1
m.p., 183.6e185.5 C). H NMR (500 MHz, CDCl
s, -OH, 1H), 8.526 (s, N¼CH, 1H), 7.720e7.702 (m, Ar-H, 1H),
.550e7.482 (m, Ar-H, 3H), 7.400e7.368 (m, Ar-H, 2H), 7.349e7.208
m, Ar-H, 5H), 7.106e7.051 (m, Ar-H, 2H; CH¼CH, 1H), 6.978e6.921
3 1
-d ) d (ppm): 13.199
(
7
ꢃ
1
(
(
1
1
1
182.3e183.4 C). H NMR (600 MHz, DMSO-d ) d (ppm): 13.106 (s,
6
1
3
m, CH¼CH, 1H). C NMR (125 MHz, CDCl
61.331, 146.965, 137.444, 133.477, 132.553, 130.758, 128.879,
28.804, 127.952, 127.141, 126.888, 126.653, 126.021, 124.148,
3
-d1)
d
(ppm):163.488,
-OH, 1H), 8.997 (s, N¼CH, 1H), 7.691e7.677 (d, J ¼ 7 Hz, Ar-H, 2H),
7.644e7.632 (d, J ¼ 6 Hz, Ar-H, 1H), 7.603e7.590 (d, J ¼ 6.5 Hz, Ar-H,
2H), 7.445e7.431 (d, J ¼ 7 Hz, Ar-H, 2H), 7.407e7.352 (m, Ar-H, 3H),
ꢂ1
13
19.553, 119.303, 119.148, 117.440. FT-IR (cm ): 3438.8, 3058.3,
7.281e7.242 (m, Ar-H, 3H), 6.977e6.939 (m, CH¼CH, 2H). C NMR
3
025.0, 2982.2, 2923.9, 1610.4, 1589.8, 1577.3, 1559.6, 1494.4,
6
(151 MHz, DMSO-d ) d (ppm): 163.247, 160.754, 147.503, 137.455,
1
476.2, 1451.3, 1279.2, 963.7, 909.7, 852.9, 757.1, 692.6. MS(ESI) m/
136.405, 133.707, 132.974, 129.162, 129.031, 128.131, 128.002,
126.941, 122.298, 119.816, 119.605, 117.034, 109.985. FT-IR (cm ):
3447.6, 3086.0, 3051.5, 3023.9, 2985.0, 2922.3, 2852.3, 2788.8,
2715.9, 2662.6, 1953.3, 1911.2, 1880.4, 1804.7, 1621.2, 1597.1, 1568.9,
þ
ꢂ1
z:calcd for C21
analysis, Anal. Calcd for C21
C, 84.34; H, 5.65; N, 4.59.
H17NO [MþH] 300.13, found 300.40. Elementary
H17NO: C, 84.26; H, 5.72; N, 4.67. Found:
1489.4, 1455.9, 1448.9, 1407.8, 1363.0, 1336.4, 1319.7, 1283.9, 1218.7,
2
.5.2. C2, (E)-1-phenyl-N-(2-((E)-styryl)phenyl)methanimine
-Styrylaniline (0.30 g, 1.53 mmol) and benzaldehyde (0.194 g,
.836 mmol) were added into three-necked flask containing 100 ml
1193.1,1171.0,1150.2,1112.3,1074.4,1032.1, 981.1, 971.2, 955.1, 937.0,
2
911.9, 865.3, 848.6, 827.1, 772.9, 740.3, 720.9, 692.4, 661.8, 618.7,
þ
1
557.2. MS(ESI) m/z:calcd for C21
300.33. Elementary analysis, Anal. Calcd for C21
5.72; N, 4.68. Found, C, 84.31; H, 5.63; N. 4.74.
H
17NO [MþH] 300.37, found
dry ethanol. The reaction mixture was stirred at room temperature
under argon protection for 12 h. After the reaction, the solvent was
H17NO: C, 84.25; H,
evaporated under vacuum. Recrystallization from CH
2 2
Cl and
cyclohexane gave pure material as faint yellow solid (yield, 48%,
m.p., 178.6e180.5 C). H NMR (400 MHz, DMSO-d ) d (ppm): 8.610
6
2.5.5. C5, (E)-1-Phenyl-N-(3-((E)-styryl)phenyl)methanimine
Synthetic procedure and method of C5 were the same as
described in synthesis of C2, in which 2-styrylaniline was replaced
by 3-styrylaniline. Crude product was further purified to afford the
desired product as faint yellow needle solid (yield, 65%, m.p.,
ꢃ
1
(
s, N¼CH, 1H), 8.057e8.041 (m, Ar-H, 2H), 7.834e7.816 (d,
J ¼ 7.2 Hz, Ar-H, 1H), 7.679e7.560 (m, Ar-H, 6H), 7.417e7.354(m, Ar-
H, 3H), 7.327e7.266 (m, Ar-H, 2H; CH¼CH, 1H), 6.183e7.164(m,
13
ꢃ
1
CH¼CH, 1H). C NMR (151 MHz, DMSO-d
6
)
d
(ppm): 161.049,
195.4e197.4 C). H NMR (600 MHz, DMSO-d ) d (ppm): 8.661 (s,
6
1
49.747, 137.770, 136.558, 132.030, 131.080, 129.868, 129.374,
N¼CH, 1H), 7.933e7.920 (t, J ¼ 3.25, Ar-H, 2H), 7.649e7.636(d,
J ¼ 6.5 Hz, Ar-H, 2H), 7.595e7.582 (d, J ¼ 6.5 Hz, Ar-H, 2H),
7.514e7.503(d, J ¼ 5.5 Hz, Ar-H, 3H), 7.372e7.347 (t, J ¼ 6.25 Hz, Ar-
H, 2H), 7.299e7.285 (d, J ¼ 7 Hz, CH¼CH, 2H),7.259e7.247 (t,
1
29.223, 129.204, 129.158, 128.074, 126.788, 126.566, 126.180,
ꢂ1
1
25.020, 119.182. FT-IR (cm ): 3432.3, 3229.0, 3080.1, 3059.8,
023.6, 2892.2, 1943.5, 1919.6, 1886.0, 1810.8, 1623.0, 1587.7, 1575.7,
493.5, 1476.8, 1449.9, 1372.8, 1330.8, 1310.1, 1259.9, 1220.0, 1193.1,
3
1
1
3
J ¼ 3 Hz, Ar-H, 3H). C NMR (151 MHz, DMSO-d
6
) d (ppm):160.645,
1
167.0, 1094.6, 1072.0, 1047.7, 1024.0, 966.7, 881.8, 862.8, 760.4,
150.953, 137.553, 136.510, 135.509, 131.913, 129.268, 129.145,
129.116, 128.454, 128.341, 128.011, 127.834, 126.871, 122.015. FT-IR
(cm ): 3446.6, 3100.0, 3077.6, 3058.4, 3026.1, 2923.2, 2853.0,
þ
7
2
6
23.8, 688.4. MS(ESI) m/z:calcd for C21
84.40. Elementary analysis, Anal. Calcd for C21
.04; N, 4.94. Found: C, 89.13; H, 5.95; N, 5.02.
H17N [MþH] 284.14, found
ꢂ1
H17N: C, 89.02; H,
2371.0, 1942.1,1869.2, 1737.4, 1622.8, 1571.9, 1498.9, 1448.0, 1365.0,