Fluorescence properties of novel 6-butyl-2,3-dicyano-7-methyl-6H-1,4- diazepine styryl dyes containing ethyleneglycol units

Article abstract of DOI:10.1016/j.tet.2010.09.103

The fluorescence properties of novel 6-butyl-2,3-dicyano-7-methyl-6H-1,4- diazepine styryl dyes having mono-, di-, tri-, and tetra(ethyleneglycol) units were examined. The mono(ethylenglycol) derivative was solid at room temperature, whereas the di-, tri-

Full text of DOI:10.1016/j.tet.2010.09.103

Tetrahedron 66 (2010) 9396e9400
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Fluorescence properties of novel 6-butyl-2,3-dicyano-7-methyl-6H-1,4-diazepine
styryl dyes containing ethyleneglycol units
*
Masaki Matsui , Kazuna Noguchi, Yasuhiro Kubota, Kazumasa Funabiki
Department of Materials Science and Technology, Faculty of Engineering, Gifu University, 1-1 Yanagido, Gifu 501-1193, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 21 July 2010
Received in revised form 28 September 2010
Accepted 28 September 2010
Available online 21 October 2010
The fluorescence properties of novel 6-butyl-2,3-dicyano-7-methyl-6H-1,4-diazepine styryl dyes having
mono-, di-, tri-, and tetra(ethyleneglycol) units were examined. The mono(ethylenglycol) derivative was
solid at room temperature, whereas the di-, tri-, and tetra(ethylenglycol) derivatives were oily. The
monoethyleneglycol derivative showed weak aggregation-induced emission enhancement with fluo-
rescence maximum at 649 nm, which comes from J-aggregates. The fluorescence of oily di-, tri-, and tetra
(ethyleneglycol) derivatives in neat form was very weak. No aggregation-induced emission enhancement
was observed for the oily derivatives.
Keywords:
Fluorescence
Ethyleneglycol unit
Styryl dye
Ó 2010 Elsevier Ltd. All rights reserved.
Diazepine
Aggregation induced emission
enhancement
1. Introduction
6-butyl-2,3-dicyano-7-methyl-6H-1,4-diazepine styryl dyes having
mono-, di-, tri-, and tetraEG units.
2,3-Dicyano-7-methyl-6H-1,4-diazepine styryl dyes are unique
compounds having non-planar carbon atom at the 6-position.
These dyes show red fluorescence in the solid state.1 In a series of
our study on the fluorescence properties of diazepine styryl dyes,
we suspected that, when ethyleneglycol (EG) units are introduced
into the molecule, these dyes can be soluble in water and the solid-
state fluorescence intensity may be enhanced due to bulky EG
units. However, we found that these EG derivatives were scarcely
soluble in water. Interestingly, the di-, tri-, and tetraEG derivatives
were oily at room temperature, whereas the monoEG derivative
was solid. To our knowledge, no clear differences between the
fluorescence properties in the solid and neat form as well as be-
tween the fluorescence from suspension and emulsion have been
reported so far. We serendipitously found the different fluorescence
behavior of oily derivatives from solid ones. Meanwhile, aggrega-
tion-induced emission enhancement (AIEE) has been reported not
only for siloles2 and tetraarylethylenes3 but also for dyes, such as
BODIPY,4 4-dicyanomethylene-2,6-distyryl-4H-pyrans,5 polyenes,6
and Sudan II.7 Therefore, it is of significance to find new AIEE
dyes. We could find that suspended monoEG derivative showed
weak AIEE. We report herein the fluorescence properties of
2. Results and discussion
2.1. Synthesis of 6-butyl-2,3-dicyano-7-methyl-6H-1,4-
diazepine styryl dyes 3
6-Butyl-2,3-dicyano-7-methyl-6H-1,4-diazepine styryl dyes 3
were synthesized as shown in Scheme 1. 6-Butyl-2,3-dicyano-5,7-
dimethyl-6H-1,4-diazepine (1) was allowed to react with 4-for-
mylanilines containing EG units 2 in the presence of piperidine to
provide 3.
Scheme 1. Reagents and conditions: 1 (1.1 equiv), 2 (1.0 equiv), piperidine, THF, reflux,
24 h.
* Corresponding author. E-mail address: matsuim@gifu-u.ac.jp (M. Matsui).
0040-4020/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2010.09.103

M. Matsui et al. / Tetrahedron 66 (2010) 9396e9400
9397
2.2. Solubility of 6-butyl-2,3-dicyano-7-methyl-6H-1,4-
2.5. Fluorescence spectra of 6-butyl-2,3-dicyano-7-methyl-
diazepine styryl dyes
6H-1,4-diazepine styryl dyes in solid and neat form
The solubility of 3 is shown in Table 1. These compounds were
scarcely soluble in water at 25 ꢀC. The solubility of 3 in methanol
was higher with increasing number of EG units. Compound 3e was
most soluble in methanol, there being 5.3 g dmꢁ3, followed by in
ethanol, 1-propanol, 2-propanol, 1-butanol, and EG.
The fluorescence spectra of 3a and 3b in the solid state and
those of 3c, 3d, and 3e in neat form are depicted in Fig. 3. Com-
pounds 3a and 3b showed Fmax at 683 and 649 nm, respectively,
there being more bathochromic than those in ethanol (622 and
623 nm) due to intermolecular interactions in the solid state.
Table 1
Physical properties of 6-butyl-2,3-dicyano-7-methyl-6H-1,4-diazepine styryl dyes 3
Compd
Solubility in methanola
In ethanolb
lmax )/nm
Solid state
g dmꢁ3 (mmol dmꢁ3
)
(
3
Fmax/nm
Ffc
lex
(
3)/nm
Fmax/nm
Ffc
0.03
d
3a
3b
3c
3d
3e
0.43 (1.1)
0.50 (1.1)
2.5 (4.7)
3.9 (6.3)
492 (46600)
484 (42400)
481 (40400)
484 (44300)
481 (45600)
622
623
623
627
621
0.04
0.04
0.04
0.04
0.04
570
590
683
649
0.06
<0.01e
0.01e
590e
590e
573e
681e
689e
665e
5.3 (7.4), 5.1 (7.2)f, 4.8 (6.6)g
<0.01e
4.7 (6.6)h, 4.5 (6.3)i, 0.51 (0.72)j
a
Measured at 25 ꢀC.
b
c
d
e
f
Measured at the concentration of 1.0ꢂ10ꢁ5 mol dmꢁ3 at 25 ꢀC.
Determined by absolute PL quantum yield measurement system C9920-02.
Obtained by measuring diffuse reflectance spectra given in KubelkaeMunk units.
In neat form.
In ethanol.
In 1-propanol.
In 2-propanol.
In 1-butanol.
In ethyleneglycol.
g
h
i
j
2.3. UVevis absorption and fluorescence spectra of 6-butyl-
2,3-dicyano-7-methyl-6H-1,4-diazepine styryl dyes in solution
The UVevis absorption and fluorescence spectra of 3 in ethanol
are shown in Fig. 1. The results are also summarized in Table 1. They
showed UVevis absorption maximum (lmax) at around 485 nm
with molar absorption coefficient
(3)
in the range of
40,400e46,600. The fluorescence maximum (Fmax) was observed at
around 625 nm with fluorescence quantum yield (Ff) 0.04. Thus, no
significant differences in the UVevis absorption and fluorescence
spectra were observed among 3a, 3b, 3c, 3d, and 3e in ethanol.
Fig. 2. DSC of 3c, 3d, and 3e. A sample was chilled to ꢁ150 ꢀC for 20 min, then heated
to room temperature at the rate of 10 ꢀC minꢁ1. DDSC means derivative differential
scanning calorimetry.
Fig. 1. UVevis absorption and fluorescence spectra of 3 in ethanol. Measured on
1ꢂ10ꢁ5 mol dmꢁ3 of substrate at 25 ꢀC. Solid and dotted lines represent UVevis
absorption and fluorescence spectra, respectively.
2.4. Thermal analysis of oily derivatives
Though compounds 3a and 3b were solid, 3c, 3d, and 3e were
oily. The DSC of 3c, 3d, and 3e are shown in Fig. 2. They showed
endothermic peak at ꢁ0.7, ꢁ25.4, and ꢁ30.6 ꢀC, respectively. These
peaks correspond to the melting point. When 3d was chilled from
room temperature to ꢁ120 ꢀC, the exothermic peak was observed
at around ꢁ30 ꢀC. Then, by heating this sample, endothermic peak
was observed at around ꢁ30 ꢀC as shown in Fig. S1 in the
Supplementary data.
Fig. 3. Excitation and fluorescence spectra of 3. Compounds 3a and 3b were measured
in the solid state. Compounds 3c, 3d, and 3e were measured in neat form.

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M. Matsui et al. / Tetrahedron 66 (2010) 9396e9400
Interestingly, the Fmax of 3b was most hypsochromic among 3a, 3b,
3c, 3d, and 3e. Furthermore, the Ff of 3b in the solid state (0.06) was
larger than that in ethanol (0.04), suggesting AIEE.
In Fig. 1, no significant differences in the UVevis absorption
spectra of 3a and 3b between in ethanol (viscosity: 1.06 cp at 25 ꢀC)
and in diEG (30 cp at 25 ꢀC)8 were observed. Nevertheless, the
fluorescence of 3a in diEG was significantly more intense than that
in ethanol, indicating that the inhibition of free rotation in the
phenylene ring could exhibit stronger fluorescence. Furthermore,
the fluorescence of 3b in diEG was more intense than that of 3a.
These results indicate that the AIEE of 3b could come from not only
free rotation inhibition of the phenylene ring but also that of ether
linkages in the solid state.
The Fmax of 3c, 3d, and 3e in neat form was observed in the range
of 665e689 nm. Their Ff was very low (<0.01). The fluorescence
intensity in neat form and solid state is affected by molecular
packing and rigidity of the fluorophore. It is clear that the melting
point of oily derivatives is lower than the solid derivatives. The
probability of the internal conversion from the first excited singlet
state to the ground state of oily compounds can be larger than that
of solid ones. Therefore, usually, the fluorescence intensity of oily
derivative is less than that of solid ones.
The reflection, fluorescence, and excitation spectra of 3b in po-
tassium bromide are shown in Fig. 4. The reflection band became
broad at higher concentration, indicating the formation of aggre-
gates. The Fmax showed slight bathochromic shift from 620 to
649 nm with increasing concentration of 3b. The fluorescence in-
tensity gradually increased with increasing concentration of 3b
from 0.01 to 10% of 3b. At 100% 3b, the intensity slightly decreased.
The excitation maximum at around 520 nm caused bathochromic
shift at higher concentration. These results suggest that the fluo-
rescence of 3b in the solid state results from J-aggregates.
Fig. 5. Picture of 3b and 3e in methanol/water mixed solvent upon green laser irra-
diation. Measured on 1ꢂ10ꢁ5 mol dmꢁ3 of substrate.
absorption, fluorescence, and excitation spectra of 3b are shown in
Fig. 6. Fig. 6a and b depict that the UVevis absorption band be-
comes broad by adding water. The amount of dissolved 3b in
methanol/water mixed solvent gradually decreased from 0 to 50%
water content, and then by adding more water, the shoulder peak at
around 570 nm gradually increased, indicating the formation of J-
aggregates. Fig. 6c and d exhibit that the Fmax caused slight bath-
ochromic shift by adding water. The excitation spectra also became
broad by adding water, which is similar to the UVevis absorption
spectra. Fig. 6e depicts that the fluorescence intensity gradually
decreased by adding water up to 50%, then slightly increased up to
water content 95%.
Fig. 4. (a) Reflection and (b) excitation and fluorescence spectra of 3b in potassium
bromide. Solid and dotted lines in Fig 4b represent excitation and fluorescence spectra,
respectively.
2.6. AIEE test for 3b and 3e
In the course of this study, we found that compounds 3 were
scarcely soluble in water. When the aqueous mixture of 3 was fil-
tered through the membrane filter (0.45 mm), the substrate was
recovered on the filter surface. This could be attributed to the low
content ratio of hydrophilic EG units in the molecule. Fig. 5 shows
color change of 3b and 3e in methanol/water mixed solvent upon
green laser irradiation. Both compounds 3b and 3e show red
emission in methanol, indicating that these compounds are com-
pletely soluble in methanol. By adding water, green light scattering
gradually increased. At 95% water content, only green light scat-
tering was observed. This result indicates that they were not sol-
uble in the mixed solvent even at low concentration of 3b
1.0ꢂ10ꢁ5 mol dmꢁ3. At 95% water content, compound 3b showed
stronger scattering than 3e. Solid 3b and oily 3e could form sus-
pension and emulsion in the mixed solvent, respectively. Stronger
scattering of laser could occur on the surface of suspension than
that on emulsion.
Fig. 6. (a) UVevis absorption of 3b, (b) normalized UVevis absorption spectra of 3b,
(c) excitation and fluorescence spectra of 3b, (d) normalized excitation and fluores-
cence spectra of 3b, and (e) relationship between fluorescence intensity and water
content of 3b in methanol/water mixed solvent. Measured on 1ꢂ10ꢁ5 mol dmꢁ3 of
substrate at 25 ꢀC. Solid and dotted lines in Fig. 6c and d represent excitation and
fluorescence spectra, respectively.
The UVevis absorption and fluorescence spectra of 3b and 3e in
various solvents are shown in Figs. S2 and S3 in the Supplementary
data, respectively. The fluorescence intensity of 3b and 3e increased
as polar was the solvent. Therefore, a small amount of 3b dissolved
in methanol/water mixed solvent may enhance the emission.
Next, the differences of fluorescence behavior between 3b and
3e in methanol/water mixed solvent were examined. The UVevis

M. Matsui et al. / Tetrahedron 66 (2010) 9396e9400
9399
However, though the fluorescence intensity of 3e also increased in
polar solvent, this compound did not show increased fluorescence
intensity in methanol/water mixed solvent as indicated in Fig. 7e.
Furthermore, the increase in the fluorescence intensity of 3b is
proportional to the formation of J-aggregates whose Ff in the solid
state is larger than that in methanol as shown in Fig. 6a, b, and e.
These results indicate that the increased fluorescence intensity in
methanol/water mixed solvent results from AIEE and not from
solvent effects.
bathochromic shift in Fmax was observed in the mixed solvent. As
no remarkable bathochromic shift in the excitation spectra was
observed for 3e, in comparison with those of 3b, the fluorescence
could mainly comes from the monomer form. The fluorescence
intensity of 3e gradually decreased by adding water as shown in
Fig. 7e.
Thus, solid compound 3b formed suspension in methanol/water
mixed solvent to exhibit weak AIEE. Meanwhile, oily compound 3e
formed emulsion in the mixed solvent not to show AIEE.
2.7. X-ray crystallography of 3b
The X-ray crystallography of 3b was performed. The result is
indicated in Fig. 8. Molecules form a pair of head-to-tail dimer, the
ꢀ
intermolecular distance being 3.65 A. Weak
p/p-interactions are
observed between the pair of molecules. The dimers are packed in
parallel. Weak CH/ interactions are observed between adjacent
p
molecules A and D. The transition moment of the dimer is 1.23 D by
the DFT calculations (B3LYP/6-31G(d,p)) (Supplementary data
Fig. S1). The slip angle is calculated to be 12.5ꢀ. It is reported that
when the slip angle is smaller than 54.7ꢀ, the UVevis absorption
band could cause bathochromic shift.9 The enhancement of solid-
state fluorescence by J-aggregates has been reported.10 Thus,
compound 3b could form J-aggregates in the solid state to show
bathochromic and more intense fluorescence in the solid state than
in solution.
Fig. 7. (a) UVevis absorption spectra of 3e, (b) normalized UVevis absorption spectra
of 3e, (c) excitation and fluorescence spectra of 3e, (d) normalized excitation and
fluorescence spectra of 3e, and (e) relationship between fluorescence intensity and
water content of 3e in methanol/water mixed solvent. Measured on
2.5ꢂ10ꢁ5 mol dmꢁ3 of substrate at 25 ꢀC. Solid and dotted lines in Fig. 7c and d rep-
resent excitation and fluorescence spectra, respectively.
Siloles and tetraarylethylenes can show AIEE because of
inhibition of C-aromatic bond rotation.2a In the case of 3b, the
C-aromatic and CeO bonds rotation could be inhibited in the solid
state to show AIEE. As compound 3b is soluble in 100% methanol, the
emission from the solution is observed. When water is added to
the methanol solution, compound 3b forms suspension, and at the
same time, the amount of 3b dissolved in methanol decreases.
The fluorescence intensity of the solvent depends on the balance
between the amount of dissolved 3b and that of suspended 3b. The
amount of 3b dissolved in methanol decreases until 50% water
content as shown in Fig. 6a. Then, byadding more water, the amount
of J-aggregates gradually increases as depicted in Fig. 6b. The
relationship between the size of produced dye particle and water
content is shown in Fig. S4. Interestingly, the size of the aggregates in
80% water content was bigger than that in 50% water content to
enhance the fluorescence intensity. However, the difference of Ff of
3b between in the solid state and solution is much smaller than that
of siloles and tetraarylethylenes. Therefore, the increase in the
fluorescence intensity of 3b by adding water is not so drastic as
siloles and tetraarylethylenes.
Fig. 8. X-ray crystallography of 3b.
3. Conclusion
The fluorescence properties of non-planar and novel 6-butyl-
2,3-dicyano-7-methyl-6H-1,4-diazepine styryl dyes having mono-,
di-, tri-, and tetraEG units were examined. They are scarcely soluble
in water. The tetraEG derivative showed the highest solubility in
methanol. Among the EG derivatives, the monoEG derivative 3b is
solid at room temperature. This compound showed Fmax at 649 nm
with Ff 0.06, which is larger than that in ethanol. This compound
formed suspension in methanol/water mixed solvent and exhibited
weak AIEE due to the inhibition of free rotation of phenylene and
ether moieties. This fluorescence could come from J-aggregates.
Meanwhile, the di-, tri-, and tetraEG derivatives are oily at room
The UVevis absorption and fluorescence spectra of 3e in
methanol/water mixed solvent are shown in Fig. 7. Fig. 7a and
b indicate that oily 3e showed no drastic aggregation formation
even in 95% water content. Fig. 7c and d depict that no drastic
temperature. Their fluorescence was very weak (Ff<0.01) in neat
from. They formed emulsion in methanol/water mixed solvent and
showed no AIEE.

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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
version at doi:10.1016/j.tet.2010.09.103.
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
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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.;
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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.
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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,