9400
M. Matsui et al. / Tetrahedron 66 (2010) 9396e9400
4. Experimental
111.8, 115.5, 115.6, 119.7, 119.7, 122.5, 130.8, 147.7, 150.4, 150.6, 154.2;
EIMS (70 eV) m/z (rel intensity) 623 (Mþ, 19), 490 (100); EIHRMS
m/z 623.3694 (Mþ), calcd for C34H49N5O6, 623.3683.
4.1. General
Melting points were measured with a Yanaco MP-13 micro-
melting-point apparatus. NMR spectra were obtained by a JEOL ECX
400P spectrometer. MS spectra were measured with a JEOL MSta-
tion 700 spectrometer. UVevis absorption, reflection, and fluores-
cence spectra were taken on Hitachi U-3500, U-4000, and F-4500
spectrophotometers, respectively. Fluorescence quantum yields
were measured by a Hamamatsu Photonics Absolute PL Quantum
Yield Measurement System C9920-02. 6-Butyl-2,3-dicyano-5,7-
dimethyl-6H-1,4-diazepine (1),1 4-formylanilines,5 and 6-butyl-
2,3-dicyano-5-[4-(diethylamino)styryl]-7-methyl-6H-1,4-diazepine
(3a)1 were synthesized as described in the literature.
4.1.5. 6-Butyl-2,3-dicyano-5-{4-[bis(2,5,8,11-tetraoxa-13-tridecanyl)
amino]styryl}-7-methyl-6H-1,4-diazepine (3e). Yield 24%; ꢁ30.6 ꢀC;
IR (KBr)
n
2222 cmꢁ1
;
1H NMR (CDCl3)
d
¼1.00 (t, J¼7.1 Hz, 3H),
1.26e1.27 (m, 1H), 1.42e1.48 (m, 4H), 2.05 (s, 3H), 2.21e2.38 (m,
2H), 3.38 (s, 6H), 3.54 (t, J¼5.7 and 5.7 Hz, 4H), 3.59e3.64 (m, 28H),
6.33 (d, J¼15.1 Hz, 1H), 6.71 (d, J¼8.9 Hz, 2H), 7.40 (d, J¼8.9 Hz, 2H),
7.66 (d, J¼15.1 Hz, 1H); 13C NMR (CDCl3)
¼13.9, 21.6, 22.6, 26.5,
d
30.0, 50.9, 57.4, 59.0, 68.3, 70.5, 70.5, 70.5, 70.5, 70.7, 71.9, 110.6,
111.8, 115.5, 115.6, 119.6, 119.6, 122.5, 130.8, 147.8, 150.4, 150.7, 154.3;
EIMS (70 eV) m/z (rel intensity) 711 (Mþ, 19), 534 (100); FABHRMS
m/z 712.4292 (MHþ), calcd for C38H58N5O8, 712.4285.
4.1.1. Synthesis of 6-butyl-2,3-dicyano-7-methyl-6H-1,4-diazepine
styryl dyes 3. To a THF solution of 6-butyl-2,3-dicyano-5,7-di-
methyl-6H-1,4-diazepine (1, 251 mg, 1.1 mmol) and 4-(dia-
lkylamino)benzaldehydes 2 (1 mmol) was added piperidine (5
drops). The mixture was refluxed for 24 h. After the reaction was
completed, the solvent was removed in vacuo. The product was
purified by column chromatography (SiO2, 3b/CH2Cl2/
MeOH¼100:1, 3c/CH2Cl2/MeOH¼90:1, 3d/CH2Cl2/MeOH¼80:1, 3e/
CH2Cl2/MeOH¼60:1).
4.2. X-ray crystallography of 3b
Single crystals were obtained by diffusion method using
dichloromethane and hexane. The diffraction data were collected
by using graphite monochromated Mo K
ꢀ
a
radiation (
l
¼0.71069 A).
The structure was solved by direct methods SIR97 and refined by
fill-matrix least-squares calculations. Crystal data for 3b:
C26H33N5O2, Mw¼447.57, triclinic, Pꢁ1, Z¼2, a¼9.342(4), b¼10.214
(4), c¼14.951(6) A, Dcalcd¼1.227 g cmꢁ3, T¼127 K, 9952 reflections
ꢀ
were collected, 5489 unique (Rint¼0.080), 302 parameters,
R1¼0.0616, wR2¼0.1322. The crystallographic data (CCDC 782741)
have been deposited at the CCDC, 12 Union Road, Cambridge CB2
1EZ, UK.
4.1.2. 6-Butyl-2,3-dicyano-5-{4-[bis(2-methoxyethyl)amino]styryl}-
7-methyl-6H-1,4-diazepine (3b). Yield 20%; mp 136e138 ꢀC; IR
(KBr)
n
2223 cmꢁ1
;
1H NMR (CDCl3)
d
¼1.00 (t, J¼6.9 Hz, 3H), 1.26
(m, 1H), 1.42e1.53 (m, 4H), 2.04 (s, 3H), 2.17e2.37 (m, 2H), 3.35 (s,
6H), 3.56 (t, J¼5.4 Hz, 4H), 3.64 (t, J¼5.4 Hz, 4H), 6.33 (d, J¼15.1 Hz,
1H), 6.71 (d, J¼9.2 Hz, 2H), 7.41 (d, J¼9.2 Hz, 2H), 7.67 (d, J¼15.1 Hz,
Supplementary data
1H); 13C NMR (CDCl3)
d
¼13.9, 21.6, 22.6, 26.5, 30.0, 51.0, 57.4, 59.1,
Transition dipole moment of 3b calculated by the TDDFT/B3LYP/
6-31G(d,p) level and X-ray crystallographic data of 3b. Supple-
mentary data associated with this article can be found in the online
70.0, 110.7, 111.8, 115.5, 115.6, 119.7, 119.7, 122.6, 130.8, 147.7, 150.4,
150.7, 154.2; EIMS (70 eV) m/z (rel intensity) 447 (Mþ, 14), 402
(100); EIHRMS m/z 447.2680, calcd for C26H33N5O2, 447.2634.
4.1.3. 6-Butyl-2,3-dicyano-5-(4-{bis[2-(2-methoxyethoxy)ethyl]
References and notes
amino}styryl)-7-methyl-6H-1,4-diazepine (3c). Yield 15%; ꢁ0.7 ꢀC;
IR (KBr)
n
2222 cmꢁ1
;
1H NMR (CDCl3)
d
¼1.00 (t, J¼6.9 Hz, 3H),
1. Horiguchi, E.; Matsumoto, S.; Funabiki, K.; Matsui, M. Bull. Chem. Soc. Jpn. 2005,
78, 1167.
1.25e1.27 (m, 1H), 1.42e1.54 (m, 4H), 2.05 (s, 3H), 2.17e2.34 (m,
2H), 3.38 (s, 6H), 3.52 (t, J¼5.8 and 5.8 Hz, 4H), 3.60 (t, J¼5.8, 5.8 Hz,
4H), 3.65 (m, 8H), 6.33 (d, J¼15.1 Hz,1H), 6.71 (d, J¼9.0 Hz, 2H), 7.40
2. (a) Hong, Y.; Lam, J. W. Y.; Tang, B. Z. Chem. Commun. 2009, 4332, references
cited therein; (b) Yuan, W. Z.; Lu, P.; Chen, S.; Lam, J. W. Y.; Wang, Z.; Liu, Y.;
Kwok, H. S.; Ma, Y.; Tang, B. Z. Adv. Mater. 2010, 22, 2159; (c) Luo, J.; Xie, Z.; Lam,
J. W. Y.; Cheng, L.; Chen, H.; Qiu, C.; Kwok, H. S.; Zhan, X.; Liu, Y.; Zhu, D.; Tang,
B. Z. Chem. Commun. 2001, 1740.
(d, J¼9.0 Hz, 2H), 7.66 (d, J¼15.1 Hz, 1H); 13C NMR (CDCl3)
¼13.9,
d
21.6, 22.6, 26.5, 30.0, 51.0, 57.4, 59.1, 68.3, 70.7, 72.0, 110.7, 111.8,
115.5, 115.6, 119.7, 119.7, 122.6, 130.8, 147.7, 150.4, 150.6, 154.2; EIMS
(70 eV) m/z (rel intensity) 535 (Mþ, 15), 446 (100); FABHRMS m/z
536.3241 (MHþ), calcd for C30H42N5O4, 536.3237.
3. Zhao, Z.; Chen, S.; Lam, J. W. Y.; Jim, C. K. W.; Chan, C. Y. K.; Wang, Z.; Lu, P.;
Deng, C.; Kwok, H. S.; Ma, Y.; Tang, B. Z. J. Phys. Chem. C 2010, 114, 7963.
4. Hu, R.; Lager, E.; Aguilar-Aguilar, A.; Liu, J.; Lam, J. W. Y.; Sung, H. H. Y.; Williams,
I. D.; Zhong, Y.; Wong, K. S.; Pena-Cabrera, E.; Tang, B. Z. J. Phys. Chem. C 2009,
113, 15845.
€
5. Tong, H.; Dong, Y.; Hauûler, M.; Hong, Y.; Lam, J. W. Y.; Sung, H. H.-Y.; Williams,
4.1.4. 6-Butyl-2,3-dicyano-5-[4-(bis{2-[2-(2-methoxyethoxy)ethoxy]
ethyl}amino)styryl]-7-methyl-6H-1,4-diazepine (3d). Yield 10%;
I. D.; Kwok, H. S.; Tang, B. Z. Chem. Phys. Lett. 2006, 428, 326.
6. Shimizu, M.; Tatsumi, H.; Mochida, K.; Shimono, K.; Hiyama, T. Chem.dAsian J.
2009, 4, 1289.
7. Yu, H.; Qi, L. Langmuir 2009, 25, 6781.
8. Solvent Handbook; Asahara, T., Tokura, N., Okawara, M., Kumanotani, J., Senoo,
M., Eds.; Kohdansya: Tokyo, 1976.
ꢁ25.4 ꢀC; IR (KBr)
n
2222 cmꢁ1; 1H NMR (CDCl3)
d
¼1.00 (t, J¼6.9 Hz,
3H), 1.26e1.27 (m, 1H), 1.42e1.56 (m, 4H), 2.05 (s, 3H), 2.17e2.38
(m, 2H), 3.37 (s, 6H), 3.53 (t, J¼5.5 and 5.5 Hz, 4H), 3.61e3.65 (m,
20H), 6.33 (d, J¼15.1 Hz, 1H), 6.71 (d, J¼8.7 Hz, 2H), 7.40 (d,
9. Kasha, M.; Rawls, H. R.; El-Bayoumi, M. A. Pure Appl. Chem. 1965, 11, 371.
10. (a) Kaiser, T. E.; Wang, H.; Stepanenko, V.; Wurthner, F. Angew. Chem., Int. Ed.
€
J¼8.7 Hz, 2H), 7.66 (d, J¼15.1 Hz, 1H); 13C NMR (CDCl3)
¼13.9, 21.6,
d
2007, 46, 5541; (b) An, B.-K.; Kwon, S.-K.; Jung, S.-D.; Park, S. Y. J. Am. Chem. Soc.
2002, 124, 14410.
22.6, 26.5, 30.0, 51.0, 57.4, 59.0, 68.3, 70.5, 70.5, 70.7, 71.9, 110.6,