42
C. Wang et al. / Dyes and Pigments 94 (2012) 40e48
2.2.7. 4-(10,11-Dihydro-5H-dibenzo[b,f]azepin-5-yl)benzaldehyde (9)
Phosphorus oxychloride (0.55 mL, 5.89 mmol) was added
dropwise to DMF (10 mL) at 0 ꢁC, and the mixture was stirred for
1 h at this temperature. Compound 3 (795 mg, 2.93 mmol) was
added and the reaction mixture was heated to 80 ꢁC for 8 h. The
mixture was subsequently cooled to room temperature, poured
into ice water, carefully neutralized with NaOH and extracted with
DCM. The combined organic extract was dried over anhydrous
MgSO4 and filtered. Solvent was removed by rotary evaporation
and the residue was purified by column chromatography on silica
(DCM/PE ¼ 1/1, v/v) to give a yellow solid, 9 (720 mg, 2.41 mmol,
47.8%). 1H NMR (400 MHz, DMSO,
d
): 9.82 (s, 1H), 7.89 (d, J ¼ 3.0 Hz,
1H), 7.56 (dd, J ¼ 15.9, 7.4 Hz, 6H), 7.46 (t, J ¼ 6.9 Hz, 2H), 7.29 (d,
J ¼ 8.0 Hz, 3H), 7.16 (d, J ¼ 16.1 Hz, 1H), 7.09 (d, J ¼ 16.1 Hz, 1H), 6.94
(s, 2H), 6.14 (d, J ¼ 8.2 Hz, 2H).
2.2.12. 3-(5-(4-(10,11-Dihydro-5H-dibenzo[b,f]azepin-5-yl)phenyl)
thiophen-2-yl)-2-cyanoacrylic acid (IDB-1)
A mixture of compound 7 (120 mg, 0.31 mmol), 2-cyanoacetic
acid (29 mg, 0.34 mmol), piperidine (0.5 mL) and THF (15 mL)
was heated to reflux under nitrogen atmosphere for 6 h. Solvent
was removed by rotary evaporation and the residue was purified by
column chromatography on silica (DCM/ethanol ¼ 20/1, v/v) to give
a red solid, IDB-1 (99 mg, 0.22 mmol, 71.3%). 1H NMR (400 MHz,
82.1%). 1H NMR (400 MHz, CDCl3,
d): 9.73 (s, 1H), 7.61 (d, J ¼ 9.0 Hz,
2H), 7.43e7.34 (m, 2H), 7.32e7.21 (m, 6H), 6.64 (d, J ¼ 8.9 Hz, 2H),
3.00 (s, 4H).
DMSO,
7.44e7.40 (m, 2H), 7.39e7.27 (m, 7H), 6.50 (d, J ¼ 8.9 Hz, 2H), 2.95
(s, 4H). 13C NMR (100 MHz, DMSO,
): 149.40, 148.99,142.46,137.66,
d
): 7.96 (s,1H), 7.58 (d, J ¼ 3.8 Hz,1H), 7.47 (d, J ¼ 8.9 Hz, 2H),
2.2.8. 4-(5H-Dibenzo[b,f]azepin-5-yl)benzaldehyde (10)
d
The synthesis method resembled that of compound 9 and the
crude compound was purified by column chromatography on silica
(DCM/PE ¼ 1/1, v/v) to yield a yellow solid, 10 (985 mg, 3.32 mmol,
136.39, 134.31, 131.13, 129.33, 127.60, 127.32, 126.96, 122.35, 122.10,
118.49, 112.43, 29.93. HRMS (ESI, m/z): [M þ H]þ calcd for
C28H21N2O2S, 449.1324; found, 449.1321.
78.4%). 1H NMR (400 MHz, CDCl3,
d): 9.69 (s, 1H), 7.55e7.46 (m, 8H),
7.43e7.37 (m, 2H), 6.86 (s, 2H), 6.35 (d, J ¼ 8.9 Hz, 2H).
2.2.13. 3-(5-(4-(5H-Dibenzo[b,f]azepin-5-yl)phenyl)thiophen-2-
yl)-2-cyanoacrylic acid (ISB-1)
2.2.9. 5-(2-(4-(10,11-Dihydro-5H-dibenzo[b,f]azepin-5-yl)phenyl)
vinyl)thiophen [41]
The synthesis method resembled that of compound IDB-1 and
the crude compound was purified by column chromatography on
silica (DCM/ethanol ¼ 20/1, v/v) to yield a red solid, ISB-1 (102 mg,
A
mixture of compound 9 (650 mg, 2.17 mmol), t-BuOK
(292 mg, 2.61 mmol) and dry THF (20 mL) was stirred at ambient
temperature under nitrogen atmosphere for 1 h. 2-Thienylmethyl
triphenylphosphonium chloride (1290 mg, 3.25 mmol) was dis-
solved in THF and added dropwise to the solution, and the reaction
mixture was stirred for 1 h at ambient temperature, whereupon
the mixture was heated to reflux for 24 h. The reaction mixture
was allowed to cool to ambient temperature and a molar excess of
water was added. The mixture was concentrated by rotary evap-
orator and the water phase was extracted with DCM. The organic
phase was dried over MgSO4, filtered through a plug of silica gel
0.23 mmol, 72.3%). 1H NMR (400 MHz, DMSO,
d): 8.35 (s, 1H), 7.88
(d, J ¼ 4.1 Hz, 1H), 7.68e7.53 (m, 6H), 7.52e7.39 (m, 5H), 6.96 (s,
2H), 6.21 (d, J ¼ 8.9 Hz, 2H). 13C NMR (100 MHz, DMSO,
d): 163.95,
153.64, 149.61, 145.76, 141.55, 141.14, 135.55, 132.80, 130.51, 130.30,
130.16, 129.67, 127.69, 127.06, 122.74, 122.23, 117.06, 111.82. HRMS
(ESI, m/z): [M ꢀ H]ꢀ calcd for C28H17N2O2S, 445.1011; found,
445.1006.
2.2.14. 3-(5-(4-(10,11-Dihydro-5H-dibenzo[b,f]azepin-5-yl)styryl)
thiophene-2-yl)-2-cyanoacrylic acid (IDB-2)
(DCM) and
a
crude intermediate was obtained (720 mg,
The synthesis method resembled that of compound IDB-1 and
the crude compound was purified by column chromatography on
silica (DCM/ethanol ¼ 10/1, v/v) to yield a red solid, IDB-2 (90 mg,
1.90 mmol). The crude product was used in the next step without
further purification.
0.19 mmol, 68.7%). 1H NMR (400 MHz, DMSO,
d): 8.14 (s, 1H), 7.65
2.2.10. 5-(2-(4-(10,11-Dihydro-5H-dibenzo[b,f]azepin-5-yl)phenyl)
vinyl)thiophen-2-carbaldehyde (11) [41]
(d, J ¼ 3.9 Hz, 1H), 7.44e7.33 (m, 6H), 7.30 (ddd, J ¼ 13.9, 7.0, 1.8 Hz,
4H), 7.24e7.16 (m, 2H), 7.00 (d, J ¼ 16.1 Hz, 1H), 6.44 (d, J ¼ 8.9 Hz,
5-(2-(4-(10,11-Dihydro-5H-dibenzo[b,f]azepin-5-yl)phenyl)
2H), 2.94 (s, 4H). 13C NMR (100 MHz, DMSO,
d): 164.11, 149.70,
vinyl)thiophen (720 mg, 1.90 mmol) was dissolved in dry THF
(20 mL) and was cooled to ꢀ78 ꢁC under nitrogen atmosphere. n-
Butyl lithium (0.75 mL, 2.5 M hexane solution) was added dropwise
over 10 min and the mixture was stirred at ꢀ78 ꢁC for 1 h. The
mixture was allowed to warm to 0 ꢁC and stirred for 30 min. The
mixture was once again cooled to ꢀ78 ꢁC and DMF (0.17 mL,
2.09 mmol) was added. The reaction mixture was allowed to warm to
ambient temperature and stirred for 2 h. The reaction was quenched
by the addition of aqueous HCl (10%, 100 mL) and extracted with
DCM.Thecombined organicextractwasdried overanhydrous MgSO4
and filtered. Solvent was removed by rotary evaporation and the
residue was purified by column chromatography on silica (DCM/
PE ¼ 1/1, v/v) to give an orange solid, 11 (347 mg, 0.85 mmol, 45.0%).
148.87, 142.55, 142.05, 137.68, 137.42, 134.10, 131.32, 131.12, 129.39,
128.15, 127.54, 127.29, 125.83, 125.61, 118.73, 117.17, 112.21, 29.94.
HRMS (ESI, m/z): [M þ H]þ calcd for C30H23N2O2S, 475.1480; found,
475.1485.
2.2.15. 3-(5-(4-(5H-dibenzo[b,f]azepin-5-yl)styryl)thiophene-2-yl)-
2-cyanoacrylic acid (ISB-2)
The synthesis method resembled that of compound IDB-1 and
the crude compound was purified by column chromatography on
silica (DCM/ethanol ¼ 10/1, v/v) to yield a purple solid, ISB-2
(103 mg, 0.22 mmol, 70.5%). 1H NMR (400 MHz, DMSO,
d): 13.59 (s,
1H), 8.40 (s, 1H), 7.88 (d, J ¼ 4.1 Hz, 1H), 7.58 (tt, J ¼ 7.8, 4.1 Hz, 6H),
7.50e7.41 (m, 2H), 7.31 (dd, J ¼ 6.4, 5.0 Hz, 3H), 7.21 (d, J ¼ 16.1 Hz,
1H), 7.08 (d, J ¼ 16.1 Hz, 1H), 6.95 (s, 2H), 6.14 (d, J ¼ 8.9 Hz, 2H). 13C
1H NMR (400 MHz, CDCl3,
d): 9.77 (s,1H), 7.52 (d, J ¼ 3.9 Hz,1H), 7.42
(d, J ¼ 7.6 Hz, 2H), 7.29e7.18 (m, 6H), 7.11 (d, J ¼ 8.7 Hz, 2H), 7.06 (d,
J ¼ 3.9 Hz,1H), 6.63 (d, J ¼ 12.0 Hz,1H), 6.53 (d, J ¼ 8.7 Hz, 2H), 6.45(d,
J ¼ 12.0 Hz, 1H), 3.00 (s, 4H).
NMR (100 MHz, DMSO, d): 163.86, 153.32, 149.14, 146.30, 141.76,
141.52, 135.63, 133.06, 132.91, 130.50, 130.31, 130.11, 129.78, 128.10,
127.59, 126.05, 125.82, 116.80, 116.73, 111.55. HRMS (ESI, m/z):
[M ꢀ H]ꢀ calcd for C30H19N2O2S, 471.1167; found, 471.1156.
2.2.11. 5-(2-(4-(5H-Dibenzo[b,f]azepin-5-yl)phenyl)vinyl)thiophen-
2-carbaldehyde (12)
2.3. Theoretical calculation
The synthesis method resembled that of compound 11 and the
crude compound was purified by column chromatography on silica
(DCM/PE ¼ 1/1, v/v) to yield a yellow solid, 12 (298 mg, 0.79 mmol,
Density functional theory (DFT) calculations were conducted by
using the B3LYP hybrid functional for the geometry optimizations.