Synthesis and photophysical properties of N-styrylazinones

Article abstract of DOI:10.1002/jhet.5570440435

(Chemical Equation Presented) N-Styrylazinones and 1-styrylbenzotriazine were synthesized, and their photophysical properties were investigated. (Z)- and/or (E)-N-Styrylazinones (or azine) 4 were prepared from the corresponding heterocycles 1 and benzaldehyde (3) by four methods. The absorption maxima of (Z)- and/or (E)-4a - 4j were measured in four solvents. Their absorption maxima showed a moderate dependence upon solvents. The absorption maxima of (Z)-isomers were blue-shifted as compared the corresponding (E)-isomers. Emission maxima, fluorescence band half-widths, 0,0 transition energies, Stokes shifts, and quantum yields of (Z)- and/or (E)-4a, 4b, 4d, 4e and 4j were measured in organic solvents. The fluorescence spectra show moderate solvatochroism. The fluorescence properties of N-styrylheterocycles vary with every heterocycles.

Full text of DOI:10.1002/jhet.5570440435

Jul-Aug 2007
951
Synthesis and Photophysical Properties of N-Styrylazinones
Su-Dong Cho, Jaeyoung Hwang, Ho-Kyun Kim, Heung-Sup Yim, Jeum-Jong Kim,
Sang-Gyeong Lee and Yong-Jin Yoon*
Department of Chemistry &Research Institute of Natural Science, Graduate School for Molecular Materials and
Nanochemistry, Gyeongsang National University, Jinju 660-701, Korea
E-mail;yjyoon@gnu.ac.kr
Received July 17, 2007
Het
Het
Method A - D
Het
+
N
Ph
N
N
H
E-formPh
Z-form
1
4
O
N
N
O
O
O
O
O
Cl
Cl
MeO
=
Het
N
N
N
N
N
N
N
N
N
S
N
O2
a
b
c
d
f
e
O
N
O
N
N
N
N
O
N
O
O
g
j
h
i
N-Styrylazinones and 1-styrylbenzotriazine were synthesized, and their photophysical properties were
investigated. (Z)- and/or (E)-N-Styrylazinones (or azine) 4 were prepared from the corresponding
heterocycles 1 and benzaldehyde (3) by four methods. The absorption maxima of (Z)- and/or (E)-4a – 4j
were measured in four solvents. Their absorption maxima showed a moderate dependence upon solvents.
The absorption maxima of (Z)-isomers were blue-shifted as compared the corresponding (E)-isomers.
Emission maxima, fluorescence band half-widths, 0,0 transition energies, Stokes shifts, and quantum yields
of (Z)- and/or (E)-4a, 4b, 4d, 4e and 4j were measured in organic solvents. The fluorescence spectra show
moderate solvatochroism. The fluorescence properties of N-styrylheterocycles vary with every
heterocycles.
J. Heterocyclic Chem., 44, 951 (2007).
involvement of the (nꢀ*) excited state [28,37]. Thus,
compounds such as N-styrylazines and N-styrylazinones
containing Het-N-CH=CH-Ar moiety may possess
photophysical properties suitable for fluorescent probe
and sensor molecules. Also the derivatization of N-
styrylazinones to useful derivatives containing various
substituents on the phenyl ring and/or heterocycles is
easy. The fluorescent properties of N-styrylazinones have
not been reported, although some fluorescent probes not
been reported, although some fluorescent probes
containing styryl moiety have been synthesized [20-29].
Here we report on the synthesis and photophysical
properties of some N-styrylazinones, focusing on the
photophysical properties and potent fluorescent probes.
INTRODUCTION
The development of luminescent molecules is an active
field of research in supramolecular chemistry [1-8]. An
important area within this field is the development of
luminescent chemosensors [6-8] because those sensors
have the advantage of possessing high sensitivity and
selectivity, as well as providing on-line and real time
analysis thus revolutionizing the field of chemical
analysis [9-25]. However, the development of useful
fluorescent probe is difficult because of the lack of
flexible design strategies. At present, design is largely
empirical.
Organic molecules that contain styryl moiety are an
important class of fluorescent molecules, which show a
number of attractive photochemical and electro-optical
properties [20,26-36]. The substitution of one phenyl ring
of stilbene with a heterocyclic acceptor (pyridine)
significantly affected the photophysical and photo-
chemical behavior of these systems, because of the
RESULTS AND DISCUSSION
As part of our research program for the search of novel
fluorescent molecules, we attempted to synthesize some
N-styrylheteocycles. Although synthetic methods leading

952
S.-D. Cho, J. Hwang, H.-K. Kim, H.-S. Yim, J.-J. Kim, S.-G. Lee and Y.-J. Yoon
Vol 44
Scheme 1
1) CH2O, H2O, refux
Het
Het
N
2) SOCl2, DMF, CH2Cl2, rt to 30oC
82 - 92%
N
H
CH2Cl
1
2
O
O
O
O
O
Cl
Cl
MeO
N
N
N
N
N
N
N
N
Het =
Het =
N
b
N
c
a
d
e
O
O
O
N
N
N
N
N
N
S
O
N
O
O2
O
f
g
h
i
j
to some styryldiazines and few styrylazinones have been
reported [38-51], they have some disadvantages such as
low selectivity and low yield. Therefore, we tried
synthesis of N-styrylazinones according to the synthetic
sequence outlines depicted in Schemes 2-4.
2-chloromethyl-4,5-dichloropyridazin-3(2H)-one (2e)
and benzaldehyde (3) according to Method B gave
isomeric compounds (Z)-4e (5%) and (E)-4e (55%)
(Scheme 3). However, 4h and 4j could also not
synthesized by Method B. On the other hand,
isomerizations of (Z)-isomers to the corresponding (E)-
isomers on TLC were detected. In order to synthesize
selectively (E)-4a, 4b, 4d, 4h and 4j isomers,
therefore, we tried the synthesis by Method C [47].
Direct reaction of azinones 1a, 1b, 1d and 1j except for
benzotriazole (1h) with (E)-ꢀ-bromostylene (5) in the
N-Chloromethylheterocycles 2a
- 2i were firstly
prepared from heterocycles 1a – 1i in 82 – 92% yields
according to the method described in the literature
(Scheme 1) [52,53], whereas N-chloromethyl-2-pyridone
(1j) could not be prepared from 2-pyridone by the same
method.
Scheme 2
Het
N
Het
N
Het
N
Method A
+
1) P(OEt)3, refux
2) C6H5CHO (3), t-BuOK, solvent, reflux
CH2Cl
2
(Z)-4
(E)-4
O
O
O
O
O
Cl
Cl
MeO
N
N
N
O
N
N
N
N
N
Het =
Het =
N
b
N
c
e
a
O
d
O
N
N
N
N
N
N
S
O
N
O
O2
O
j
f
g
h
i
(Z)-and/or (E)-N-Styrylheterocycles for 4a–4d, 4f, 4g
and 4i were synthesized from the corresponding N-
chloromethyl derivatives 2 and benzaldehyde (3) by
Method A (Table 1), whereas 2-styryl-4,5-dichloropyri-
dazin-3(2H)-one (4e), 1-styrylbenzotriazole (4h) and N-
styryl-2-pyridone (4j) could not be prepared by this
Method. The main products in the Method A were the
(E)-isomers.
presence of potassium carbonate gave selectively the
corresponding (E)-N-styrylazinones 4a (89%), 4b
(82%), 4d (79%) and 4j (94%) (Scheme 4). On the
other hand, coupling of benzotriazole (1h) with
compound 5 by Method C gave (E)-1-styrylbenzo-
triazole (4h, 10%) and (E)-2-styrylbenzotriazole (5%),
whereas compound (E)-4h was synthesized selectively
from {[1H-benzo[d][1,2,3]triazol-1-yl]methyl}triphenyl-
phosphonium chloride and benzaldehyde (3) in 67%
yield by Method D (Scheme 4).
Therefore, we attempted the synthesis of (Z)- and/or
(E)-4e, 4h and 4j by using Method B. Coupling of

Jul-Aug 2007
Synthesis and Photophysical Properties of N-Styrylazinones
953
Scheme 3
Cl
N
Cl
Cl
N
Cl
N
N
Cl
Cl
O
Method B
N
+
N
O
O
1) NaI, CH3CN, refux
2) PPh3, CH3CN, reflux
3) C6H5CHO (3), t-BuOK, CH3CN,
reflux
CH2Cl
2e
(Z)-4e (5%)
(E)-4e (55%)
Scheme 4
Het
N
Het
Method C
N
H
(E)-C6H5CH=CHBr (5)
K2CO3, DMF, refux
79 - 94%
(E)-4
1
O
O
O
O
N
N
MeO
N
N
N
N
N
N
Het =
N
a
b
j
d
h
N
N
N
N
N
Method D
1) PPh3, CH3CN, reflux
N
2) C6H5CHO (3), THF, t-BuOK, rt
CH2Cl
(E)-4h (65%)
2h
Table 1
Synthesis of (Z)-and/or (E)-N-Styrylheterocycles 4a~4j
Products (4)
(Z)-isomer (%)a
Entry
Heterocycles (1)
Method
Time (h)
(E)-isomer (%) a
O
1
2
3
4
A
C
A
C
2
(Z)-4a (4)
(E)-4a (43)
(E)-4a (89)
(E)-4b (55)
(E)-4b (82)
NH
N
23
2.5
24
__
O
(Z)-4b (trace)
NH
__
N
O
NH
5
A
1.5
(Z)-4c (5)
(E)-4c (44)
N
N
MeO
6
7
A
C
1
(Z)-4d (3)
(E)-4d (47)
(E)-4d (79)
O
N
24
__
H
Cl
Cl
8
B
2
(Z)-4e (5)
(E)-4e (55)
N
O
N
H
O
NH
9
A
A
5
1
__
(E)-4f (42)
(E)-4g (56)
S
O2
O
NH
10
(Z)-4g (10)
O

954
S.-D. Cho, J. Hwang, H.-K. Kim, H.-S. Yim, J.-J. Kim, S.-G. Lee and Y.-J. Yoon
Vol 44
Table 1
Synthesis of (Z)-and/or (E)-N-Styrylheterocycles 4a~4j
Products (4)
(Z)-isomer (%)a
Entry
11
Heterocycles (1)
Method
Time (h)
38
(E)-isomer (%) a
(E)-4h (10) c
N
N
C
D
__
12
48
__ b
__ b
(E)-4h (67)
N
H
13
14
A
C
0.5
(E)-4i(65)
O
N
H
O
25
__b
(E)-4j (94)
O
N
H
Table 2
Long Wavelength Absorption Maxima for (Z)- and/or (E)-4a~4j at Room Temperaturea
ꢀabs max(ꢁ, ꢂꢃ1cmꢃ1)
Compound
THF
CH2Cl2
CH3CN
MeOH
(Z)-4a
(E)-4a
(E)-4b
(Z)-4c
(E)-4c
(Z)-4d
(E)-4d
(Z)-4e
(E)-4e
(Z)-4f
(E)-4f
(Z)-4g
(E)-4g
(E)-4h
(E)-4i
(E)-4j
325.5(12702)
350.0(19852)
324.0(12369)
352.0(2295)
310.0(8056)
322.0(12618)
343.5(9878)
338.0(8110)
371.5(8515)
305.0(15483)
300.0(8140)
261.0(14053)
283.0(28628)
316.0(16461)
331.0(15850)
348.5(16509)
316.5(8601)
348.5(12977)
322.0(14320)
352.5(3125)
297.5(9126)
317.0(8755)
338.5(11188)
332.5(6074)
371.0(6283)
305.0(13577)
300.0(10179)
261.5(15578)
284.0(27204)
299.5(14593)
334.0(16720)
345.0(14850)
319.5(4791)
343.5(16585)
321.0(12396)
346.5(3965)
305.0(8151)
315.5(9389)
338.0(7698)
328.0(5962)
365.0(5978)
304.5(15061)
298.5(8423)
258.5(14976)
281.5(29090)
311.5(7325)
331.0(16950)
344.0(16610)
317.0(10219)
342.5(17964)
319.5(14761)
348.0(4039)
305.0(10316)
310.5(9048)
332.0(14074)
326.5(8167)
365.0(14556)
305.0(18793)
268.0(21709)
266.5(18143)
281.0(22546)
305.0(10520)
332.0(13710)
336.5(12927)
aData were collected from sample solution prepared under atmosphere without degassing or inert gas bubbling. The unit of ꢀabsmax is nm.
All the compounds in this report gave satisfactory
corresponding (E)-isomers, a change consistent with
deconjugation of heterocycles, carbon-carbon double
bond and phenyl chromophores. This deconjugation may
arise from twisting about the C-N bond between the
heterocycle and vinyl group [27], and it may also depend
on the kind of heterocycles for N-styrylheterocycles.
Their absorption maxima showed moderate dependence
on solvents, but they did not show regularity on the
dielectric constants of solvents. Among all the
compounds, (E)-2-styrylpyridazin-3(2H)-one [(E)-4e]
showed the longest wavelength absorbance maxima at ca
365.0-371.0 nm in four solvents. The fluorescence spectra
for (Z)- and/or (E)-N-styrylazinones were measured in
methylene chlorides, tetrahydrofuran, acetonitrile, and
methanol under neutral conditions. The corresponding
fluorescence maxima (ꢀfmax) for (Z)- and/or (E)-4a, 4b,
4d, 4e and 4j are reported in Table 3.
analytical and spectroscopic data in full accordance with
the assigned structures. The (Z)- and (E)- isomers were
easily distinguished by the coupling constants of the vinyl
protons (3J(Z) = 8.43 – 9.47 Hz; 3J(E) = 14.18 – 15.26 Hz).
The ultraviolet spectra of (Z)- and (E)-N-styrylazinones
were measured in methylene chloride, tetrahydrofuran,
acetonitrile and methanol. All the compounds in four
solvents display a single, intense and long-wavelength
absorption band. The corresponding absorption maxima
(ꢀabs) for (Z)- and/or (E)-4a–4j are reported in Table 2.
The characteristic features of these compounds are that
(E)-isomers absorb at longer wavelength than their
corresponding (Z)-isomers for N-styryldiazinones (4a and
4e) and N-styrylazinones (4d and 4g), whereas N-
styryltriazinone, (Z)-4c absorb at longer wavelength than
their corresponding (E)-isomers.
The ultraviolet maximum for the (Z)-isomers of 4a, 4d,
4e and 4g are blue-shifted as compared to the
The kind of nitrogen-heterocycles affects the fluores-
cence properties of N-styrylazinones. N-Styryldiazinones

Jul-Aug 2007
Synthesis and Photophysical Properties of N-Styrylazinones
955
Table 3
Emission Maxima, Fluorescence Band Half-width (ꢂꢃ1/2), 0,0 Transition (ꢄ0,0 ), Stokes (ꢂꢃst) and Quantum yield (ꢅ) for (Z)-
and/or (E)- 4a, 4b, 4d, 4e and 4ja
max
ꢂꢃ1/2
ꢄf
ꢄ0,0
ꢂꢃst
Entry
Compound
Quantum
(cm-1)
Yield(ꢅ)e
(nm)c
(cm-1)d
THF
460.5
457.5
406.5
430.0
425.0
499.0
489.0
418.0
CH2Cl2
460.0
457.5
410.5
420.5
413.0
497.0
491.0
417.5
CH3CN
460.5
458.0
407.5
417.0
428.0
507.0
494.0
414.5
MeOH
461.5
456.5
412.5
407.5
418.0
501.0
488.0
413.0
1
2
3
4
5
6
7
8
(Z)-4a
(E)-4a
(E)-4b
(Z)-4d
(E)-4d
(Z)-4e
(E)-4e
(E)-4j
3956
3928
4637
4090
4356
3642
3465
3301
388
398
359
369
379
395
429
386
9583
7278
6613
7715
6221
10764
7154
4944
0.7034
0.5229
0.7914
0.8963
0.4842
0.2566
0.2610
0.6059
aData were collected from sample solution prepared under atmosphere without degassing or inert gas bubbling at room temperature. The unit of
max
ꢄabs is nm. Fluorescence band half-width (ꢂꢃ1/2), 0,0 transition (ꢄ0,0), and Stokes shifts (ꢂꢃst) were measured in acetonitrile at room temperature.
c
d
bNot available. The value of ꢄ0,0 was obtained from the intersection of normalized absorption and fluorescence spectra. ꢂꢃst = ꢃsabs - ꢃf. eQuantum
yield of the emission is evaluated in acetonitrile at 25°C, the quantum yield values is that relative to 9,10-diphenylanthracene (1.00 x 10-4M) in
acetonitrile (from 352 nm excitation wavelength, ꢅ = 0.95).
[(Z)-4a, (E)-4a, (E)-4b, (Z)-4e and (E)-4e] and N-
styrylpyridones [(Z)-4d, (E)-4d and (E)-4j] showed the
available emission spectra (Table 4), whereas the
remaining compounds 4c, and 4f-4i did not give an
available emission spectrum. The relationship between
structure and fluorescence for 4a-4j is show in Figure 1.
Six membered-azinone derivatives containing one or two
Nsp2 atoms at ꢀ- or ꢁ-position of amide nitrogen such as
4a, 4b, 4d, 4e and 4j are fluorescent, whereas N-styryl-
azinones containing 1,2,3-triazine (4c, 4h) and azin-1,3-
diones (4g, 4i) and N-styrylsaccharin (4f) are not
fluorescent. Their emission maxima showed moderate
solvatochroism, but they did not show regularity on the
dielectric constants of solvents. The maxima of
fluorescence of (Z)-4a, (Z)-4d, (E)-4a, (E)-4b, (E)-4d and
(E)-4j appeared at 406.5-461.5 nm in four solvents,
whereas the maxima of fluorescence of pyridazinone
derivatives (Z)- and (E)-4e appeared at 488.0-507.0 nm in
the same solvents. Fluorescence band half-width
(ꢂꢃ1/2), 0,0 transition (ꢄ0,0), Stokes shifts (ꢂꢃst) and
X
N
ꢁ
Y
ꢀ
C
4a
4b
4d
4e
4j
UV
Y ꢀ
X ꢁ
C
C
N
C
N
C
C
C
ꢀ
Y
X
ꢁ
O
N
R
O
N
R
HC CH
R =
Fluorescent
UV
N
N
N
or
or
N
O
N
O
N
R
O
O
N
O
N
R
O
R
R
4c
4i
R =
HC CH
Not Fluorescent
O
O
UV
N
N
or
N
R
N
N
or
R
N
N
X
N
X
R
R
X= SO2
4f
4g
4h
Not Fluorescent
R =
HC CH
X= C=O
Figure 1. Relationship between the structures and the fluorescence.

956
S.-D. Cho, J. Hwang, H.-K. Kim, H.-S. Yim, J.-J. Kim, S.-G. Lee and Y.-J. Yoon
Vol 44
recorded on a 300 MHz spectrometer with chemical shift values
reported in ꢄ (ppm) relative to an internal standard (TMS).
Infrared spectra were obtained on an infrared spectrophotometer.
Elemental analyses were performed with a Perkin Elmer 240 C.
Open-bed chromatography was carried out on silica gel (70 – 230
mesh, Merck) using gravity flow. The column was packed as
slurries with the elution solvent. UV spectra were measured on a
Shimadzu PC-2401 double beam spectrophotometer. Fluorescence
quantum yield (ꢀf ) of fluorescence for (Z)- and/or (E)-
isomers 4a, 4b, 4d, 4e and 4j are presented in Table 3.
Among the eight compounds, the value of ꢁ0,0 for (E)-4e is
the largest. Compared with three isomeric pairs of (Z)-
/(E)-4a, (Z)-/(E)-4d and (Z)-/(E)-4e, the Stokes shifts of
(Z)-isomers are larger than the corresponding (E)-isomers.
The Stokes shifts of (Z)-4e is the largest. The quantum
yields (ꢀf) of (Z)-4a and (Z)-4d also are larger than those
of their (E)- 4a and (E)-4d, whereas the quantum yield
(ꢀf) of (Z)-4e is smaller than that of (E)-4e.
This paper described the synthesis of nine isomeric N-
styrylazinones and the investigation results of their optical
spectroscopic properties. Nine N-chloromethylazinones
except for 2-pyridone was prepared from the corre-
sponding azinones in good to excellent yields. (Z)-and/or
(E)-N-Styrylazinones (or azine) for 4a–4d, 4f, 4g and 4i
were prepared from the corresponding N-chloromethyl
derivatives and benzaldehyde. Also, compounds (E)-4a,
4b, 4d and 4j synthesized selectively from the corre-
sponding nitrogen-heterocylces and (E)-ꢂ-bromostylene
(5) in good to excellent yields. Compound (E)-4h was
synthesized selectively from {[1H-benzo[d][1,2,3]triazol-
1-yl]methyl}triphenylphosphonium chloride and benz-
aldehyde (3) in 67% yield.
All the compounds in four solvents displayed a single
intense long-wavelength absorption band. Their absorption
maxima showed moderate dependence upon solvents. The
absorption maxima of (Z)-isomers are blue-shifted as
compared to the corresponding (E)-isomers. This blue shift
is attributed to the deconjugation that twisted the C-N bond
between the heterocycle and the vinyl group. The
decojugation depends on the kind of heterocycles. The
fluorescence spectra are in a normal Gaussisan shape except
for (E)-4d and (E)-4j, showing moderate solvatochroism.
The kind of heterocycle affects the fluorescence properties
of N-styrylheterocycles. According to the relationship
between structure and fluorescence for 4a-4j, six
membered-azinone derivatives containing one or two Nsp2
atoms at ꢃ- or ꢂ-position of amide nitrogen such as 4a, 4b,
4d, 4e and 4j are fluorescent, whereas N-styrylazinones
containing 1,2,3-triazine (4c, 4h) and azin-1,3-diones (4g,
4i) and N-styrylsaccharin (4f) are not fluorescent. These
results may be a guide-line for the development of
fluorescent molecules containing styryl moiety. N-
Styryldiazinones 4a, 4b and 4e and N-styrylpyridones 4d
and 4j may be show potential for application as
spectroscopic or fluorescent probes. Further work including
the tuning of photophysical properties, the photoisomer-
ization and application as fluorescence sensor are under way
in our laboratory.
spectra were recorded on
a PerkinElmer LS50B spectro-
fluorometer at room temperature. Quantum yield of the emission
is evaluated in acetonitrile at 25°C, the quantum yield values are
that relative to 9,10-diphenylanthrancene (1.00 x 10-4 M) in
acetonitrile (from 352 nm extraction wavelength, ꢀ = 0.95).
Typical process of N-chlormethylheterocycles. A mixture
of nitrogen heterocycles 1 (340 mmol) and distilled water (350
ml) was stirred for 10 minutes at room temperature. After adding
formaldehyde solution (36%, 70 ml), the solution was refluxed
for 1.5 hours. After cooling to 5 – 10 °C, the resulting precipitate
was collected by filtration, washed with cold water (0 – 5 °C,
200 ml) and dried in air to give the corresponding N-
hydroxymethylheterocycles 2. A solution of thionyl chloride
(357 mmol) in methylene chloride (50 ml) was added slowly to
the mixture of the resulting N-hydroxymethylheterocycle,
methylene chloride (550 ml) and dimethylformamide (360 ml)
for 30 minutes at room temperature with stirring. The resulting
mixture was stirred for 2 hours at room temperature. After
cooling to 0 °C, water (200 ml) was added slowly. And the
solution was neutralized to pH 6.7 – 7.4 by using saturated
solution of NaHCO3 (50 ml). The organic layer was separated
and then dried over anhydrous magnesium sulfate. The resulting
organic solution was evaporated under reduced pressure. The
residue was washed with n-hexane (100 ml) to give N-
chloromethylheterocycles 2.
N-Chloromethylphthalazin-1(2H)-one (2a). Yield 87%.
White crystal (diethyl ether/n-hexane = 1:2, v/v). mp 146 -147
°C (lit.[54] mp 146 -147 °C); tlc (CH2Cl2) Rf = 0.5; ir (KBr)
1
3100, 1700, 1600, 1580, 1360, 1260, 1180, 1160, 960 cm-1; H
nmr (CDCl3): ꢄ 7.76 ppm (s, 1H); 13C nmr (CDCl3) ꢄ 134.8,
137.0, 137.5, 153.8 ppm. Anal. Calcd. for C4HCl3N2O: C 24.09,
H 0.51, N 14.05; Found: C 24.10, H 0.53, N 14.07.
N-Chloromethylquinazolin-4(3H)-one (2b). Yield 89%.
White crystal (diethyl ether/n-hexane = 1:2, v/v). mp 114 -115 °C
(lit.[55] mp 119 °C); tlc (CH2Cl2) Rf = 0.29; ir (KBr) 3102, 2968,
1
1708, 1636, 1490, 1312, 1280, 1200, 1174, 790 cm-1; H nmr
(DMSO-d6): ꢄ 5.99 (s, 2H), 7.60 – 7.67 (m, 1H), 7.72 – 7.75 (m,
1H), 7.88 – 7.96 (m, 1H), 8.20 – 8.24 (m, 1H), 8.65 ppm (s, 1H);
13C nmr (DMSO-d6) ꢄ 54.23, 121.48, 126.80, 127.82, 128.35,
135.71, 147.39, 147.58, 159.55 ppm. Anal. Calcd. for C4HCl3N2O:
C 24.09, H 0.51, N 14.05; Found: C 24.07, H 0.49, N 14.06.
3-Chloromethyl-1,2,3-benzotriazin-4(3H)-one (2c). Yield
86%. White crystal (diethyl ether/n-hexane = 1:2, v/v). mp 127 -
128 °C (lit.[56] mp 125 °C); tlc (CH2Cl2) Rf = 0.5; ir (KBr)
1
3082, 3014, 2988, 1700, 1464, 1306, 1060, 922, 780 cm-1; H
nmr (CDCl3): ꢄ 6.18 (s, 2H), 7.82 – 7.88 (m, 1H), 7.98 – 8.03
(m, 1H), 8.17 – 8.20 (m, 1H), 8.36 – 8.39 ppm (m, 1H); 13C nmr
(CDCl3) ꢄ 55.66, 119.56, 125.38, 128.91, 133.12, 135.59,
143.81, 154.60 ppm. Anal. Calcd. for C8H6ClN3O: C 49.12, H
3.09, N 21.48; Found: C 49.10, H 3.06, N 21.50.
EXPERIMENTAL
N-Chloromethyl-3-methoxypyrid-2(1H)-one (2d). Yield
82%. White crystal (diethyl ether/n-hexane = 1:3, v/v). mp 108 -
109 °C; tlc (EtOAc/CH2Cl2=1:1, v/v) Rf = 0.43; ir (KBr) 3102,
2984, 1680, 1620, 1274, 1240, 760, 696 cm-1; 1H nmr (CDCl3): ꢄ
General. Melting points were determined with a capillary
apparatus and are uncorrected. 1H and 13C nmr spectra were

Jul-Aug 2007
Synthesis and Photophysical Properties of N-Styrylazinones
957
3.93 (s, 3H), 5.73 (s, 2H), 6.19 (t, J = 7.19 Hz, 1H), 6.58 (dd, J =
1.57, 7.4 Hz, 1H), 7.01 (dd, J = 1.62, 7.03 Hz, 1H) ppm; 13C nmr
(CDCl3) ꢀ 55.47, 55.97, 106.17, 112.44, 126.95, 150.09, 157.41
ppm. Anal. Calcd. for C7H8ClNO2: C 48.43, H 4.64, N 8.07;
Found: C 48.40, H 4.62, N 8.06.
4,5-Dichloro-2-chloromethylpyridazin-3(2H)-one (2e). Yield
92%. White crystal (diethyl ether/n-hexane = 1:5, v/v). mp 69 - 70
°C (lit. [54] mp 70 - 71 °C); tlc (CH2Cl2) Rf = 0.65; ir (KBr) 3046,
2984, 1670, 1292, 1122, 964 cm-1; 1H nmr (CDCl3): ꢀ 5.83 (s, 2H),
7.88 ppm (s, 1H); 13C nmr (CDCl3) ꢀ 58.40, 134.87, 137.23,
137.34, 155.58 ppm. Anal. Calcd. for C5H3Cl3N3O: C 28.13, H
1.42, N 13.12; Found: C 28.10, H 1.41, N 13.09.
N-Chloromethylsaccharin (2f). Yield 89%. White crystal
(diethyl ether/n-hexane = 1:1, v/v). mp 146 -147 °C (lit. [57] mp
145-146 °C); tlc (CH2Cl2) Rf = 0.41; ir (KBr) 3062, 1736, 1286,
1202 cm-1; 1H nmr (CDCl3): ꢀ 5.58 (s, 2H), 7.79 – 8.15 ppm (m,
4H); 13C nmr (CDCl3) ꢀ 45.32, 121.26, 125.70, 126.30, 134.75,
135.65, 137.48, 157.48 ppm. Anal. Calcd. for C8H6ClNO3S: C
41.48, H 2.61, N 6.05; Found: C 41.45, H 2.60, N 6.01.
evaporated to give (Z)-and/or (E)-4a–4d, 4f, 4g and 4i,
respectively.
(Z)-2-Styrylphthalazin-1(2H)-one [(Z)-4a]. Pale yellow
crystal (diethyl ether/n-hexane = 1:2, v/v). mp 133 -134 °C; tlc
(CH2Cl2) Rf = 0.41; ir (KBr) 3100, 3050, 1660, 1500, 1460,
1420, 1360, 1340, 1260, 1180, 1140, 1040, 960, 920, 780, 740,
700, 600 cm-1; 1H nmr (CDCl3): ꢀ 6.49 (d, J = 9.47 Hz, 1H), 7.18
– 7.23 (m, 6H), 7.66 – 7.69 (m, 1H), 7.75 – 7.85 (m, 2H), 8.08
(s, 1H), 8.46 – 8.49 ppm (m, 1H); 13C nmr (CDCl3) ꢀ 124.19,
126.32, 127.03, 127.59, 127.93, 127.98, 129.22, 129.59, 131.89,
133.53, 134.46, 138.28, 158.85 ppm. Anal. Calcd. for
C16H12N2O: C 77.40, H 4.87, N 11.28; Found: C 77.42, H 4.91,
N 11.30.
(Z)-3-Styryl-1,2,3-benzotriazin-4(3H)-one [(Z)-4c]. White
crystal (diethyl ether/n-hexane = 1:2, v/v). mp 164 -165 °C; tlc
(CH2Cl2) Rf = 0.68; ir (KBr) 3134, 2968, 1718, 1472, 1322, 1104,
1080, 980, 794, 706 cm-1; 1H nmr (CDCl3): ꢀ 7.26 – 7.32 (m, 1H),
7.35 – 7.40 (m, 2H), 7.53 – 7.59 (m, 3H), 7.78 – 7.83 (m, 1H),
7.91 – 7.97 (m, 1H), 8.17 – 8.23 (m, 2H), 8.39 ppm (dd, J = 1.39,
7.90 Hz, 1H); 13C nmr (CDCl3) ꢀ 119.52, 121.51, 122.73, 125.61,
126.61, 126.94, 128.26, 128.78, 128.85, 132.76, 134.95, 135.06,
143.27, 153.74 ppm. Anal. Calcd. for C15H11N3O: C 72.28, H 4.45,
N 16.86; Found: C 72.20, H 4.43, N 16.84.
N-Chloromethylphthalimide (2g). Yield 90%. White crystal
(diethyl ether/n-hexane = 1:2, v/v). mp 131 -133 °C (lit. [57] mp
130 -132 °C); tlc (CH2Cl2) Rf = 0.73; ir (KBr) 3058, 1762, 1466,
1
1428, 1382, 1308, 936, 730 cm-1; H nmr (CDCl3): ꢀ 5.49 (s,
2H), 7.78 – 7.83 (m, 2H), 7.91 – 7.95 ppm (m, 2H); 13C nmr
(CDCl3) ꢀ 44.80, 124.24, 131.81, 134.83, 166.14 ppm. Anal.
Calcd. for C9H6ClNO2: C 55.26, H 3.09, N 7.16; Found: C
55.23, H 3.08, N 7.14.
(Z)-3-Methoxy-1-styrylpyrid-2(1H)-one [(Z)-4d]. Pale yellow
crystal (diethyl ether/n-hexane = 1:2, v/v) mp 164 -165 °C; tlc
(CH2Cl2/ethyl acetate = 20:1, v/v) Rf = 0.17; ir (KBr) 3100, 3050,
2980, 1680, 1620, 1570, 1500, 1480, 1460, 1420, 1340, 1280,
1240, 1190, 1160, 1060, 960, 950, 890, 870, 800, 740, 700 cm-1;
1H nmr (CDCl3): ꢀ 3.84 (s, 3H), 5.96 (t, J = 7.21 Hz, 2H), 6.50 (d,
J = 9.26 Hz, 3H), 6.59 (dd, J = 1.59, 7.02 Hz, 1H), 6.70 (dd, J =
1.61, 7.02 Hz, 1H), 6.97 (d, J = 9.26 Hz, 1H), 7.12 – 7.16 (m, 2H),
7.22 – 7.26 ppm (m, 3H); 13C nmr (CDCl3) ꢀ 55.87, 105.07,
112.35, 124.77, 126.93, 128.15, 128.15, 128.20, 128.56, 128.86,
133.04, 150.21, 157.91 ppm. Anal. Calcd. for C14H13NO2: C 73.99,
H 5.77, N 6.16; Found: C 73.97, H 5.74, N 6.15.
(Z)-N-Styrylphthalimide [(Z)-4g]. Yellow crystal (diethyl
ether/n-hexane = 1:2, v/v). mp 121 -122 °C; tlc (CH2Cl2) Rf =
0.67; ir (KBr) 3150, 3090, 1720, 1680, 1620, 1500, 1480, 1460,
1400, 1305, 1260, 1180, 1120, 1080, 1020, 980, 920, 800, 780,
740, 720, 700 cm-1; 1H nmr (CDCl3): ꢀ 6.31 (d, J = 9.12 Hz, 1H),
6.68 (d, J = 9.12 Hz, 1H), 7.21 – 7.26 (m, 5H), 7.71 – 7.74 (m,
2H), 7.83 – 7.86 ppm (m, 2H); 13C nmr (CDCl3) ꢀ 116.32,
123.73, 128.01, 128.24, 130.06, 132.16, 134.32, 135,06, 166.34
ppm. Anal. Calcd. for C16H11NO2: C 77.10, H 4.45, N 5.62;
Found: C 77.08, H 4.44, N 5.59.
(E)-2-Styrylphthalazin-1(2H)-one [(E)-4a]. Pale yellow
crystal (diethyl ether/n-hexane = 1:2, v/v). mp 138 -139 °C; tlc
(CH2Cl2) Rf = 0.72; ir (KBr) 3100, 3050, 1730, 1680, 1660,
1620, 1500, 1460, 1400, 1360, 1320, 1280, 1190, 1140, 1120,
1080, 1040, 960, 900, 800, 760, 750, 700 cm-1; 1H nmr (CDCl3):
ꢀ 7.23 – 7.27 (m, 2H), 7.33 – 7.38 (m, 2H), 7.52 – 7.54 (m, 2H),
7.70 – 7.73 (m, 1H), 7.75 – 7.82 (m, 2H), 8.27 (s, 1H), 8.36 (dd,
J = 14.37 Hz, 1H), 8.46 – 8.49 ppm (m, 1H); 13C nmr (CDCl3) ꢀ
118.49, 124.70, 126.45, 126.63, 127.33, 127.46, 127.88, 128.72,
129.02, 132.06, 133.44, 135.88, 137.72, 157.53 ppm. Anal.
Calcd. for C16H12N2O: C 77.40, H 4.87, N 11.28; Found: C
77.37, H 4.85, N 11.26.
(E)-3-Styrylquinazolin-4(3H)-one [(E)-4b]. Light yellow
crystal (diethyl ether/n-hexane = 1:3, v/v). mp 159 -160 °C; tlc
(CH2Cl2) Rf = 0.46; ir (KBr) 3100, 3050, 1680, 1610, 1570, 1480,
1460, 1440, 1360, 1320, 1300, 1280, 1240, 1180, 1160, 1100,
1020, 980, 950, 880, 780, 750, 690 cm-1; 1H nmr (CD3OD +
1-Chloromethylbenzotriazole (2h). Yield 92%. White
crystal (diethyl ether/n-hexane = 1:1, v/v). mp 136 -137 °C (lit.
[58] mp 136 -139 °C); tlc (CH2Cl2) Rf = 0.51; ir (KBr) 3050,
1
2984, 1624, 1506, 1460, 1296, 1238, 1080, 754, 700 cm-1; H
nmr (CDCl3): ꢀ 6.41 (s, 2H), 7.42 – 7.47 (m, 1H), 7.56 – 7.61
(m, 1H), 7.66 – 7.69 (m, 1H), 8.08 – 8.11 ppm (m, 1H); 13C nmr
(CDCl3) ꢀ 53.45, 109.57, 120.51, 124.87, 128.60, 132.05,
146.53 ppm. Anal. Calcd. for C7H6ClN3: C 50.17, H 3.61, N
25.07; Found: C 50.16, H 3.58, N 25.08.
N-Chloromethyl-1,8-naphthalimide (2i). Yield 91%. White
crystal (diethyl ether/n-hexane = 1:2, v/v). mp 215-216 °C; tlc
(CH2Cl2) Rf = 0.64; ir (KBr) 3074, 3008, 1708, 1678, 1585, 1359,
1308, 1232, 1170, 946, 781 cm-1; 1H nmr (CDCl3): ꢀ 6.00 (s, 2H),
7.77 (t, J = 8.04 Hz, 2H), 8.24 (d, J = 8.26 Hz, 2H), 8.62 ppm (d, J
= 7.32 Hz, 2H); 13C nmr (CDCl3) ꢀ 47.63, 121.79, 127.08, 131.69,
131.91, 134.77 ppm. Anal. Calcd. for C9H6ClNO2: C 63.56, H
3.28, N 5.70; Found: C 63.53, H 3.27, N 5.69.
Typical Process of N-styrylheterocycles.
Method A. A mixture of N-chloromethylheterocycles (204.5
mmol) and triethylphosphate (215 mmol) was refluxed for 3
hours. After cooling to room temperature, excess triethyl-
phosphate was evaporated under reduced pressure to give crude
product. A solution of the crude product and toluene (50 ml) for
N-chloromethylphthalimide or tetrahydrofuran (50 ml) for N-
chloromethylphthalazin-1(2H)-one, N-chloromethylquinazolin-
4(3H)-one, 3-chloromethyl-1,2,3-benzotriazin-4(3H)-one, N-
chloromethyl-3-methoxy-2(1H)-pyridone and N-chloromethyl-
saccharin was stirred for 30 minutes at room temperature. After
adding slowly t-butoxide (1.3 g, 11.6 mmol) at room
temperature, the mixture was refluxed for 3 hours. The solvent
was evaporated. The residue was applied to the top of an open-
bed silica gel column (10 x 2.5 cm). The column was eluted with
ethyl acetate/methylene chloride (1:10, v/v). Fractions
containing (Z)-isomer or (E)-isomer were combined and

958
S.-D. Cho, J. Hwang, H.-K. Kim, H.-S. Yim, J.-J. Kim, S.-G. Lee and Y.-J. Yoon
Vol 44
CDCl3): ꢀ 7.24 (d, J = 14.81 Hz, 1H), 7.28 – 7.42 (m, 3H), 7.53 –
7.61 (m, 3H), 7.73 – 7.87 (m, 3H), 8.30 (dd, J = 1.14 Hz, 8.00 Hz,
1H), 8.54 ppm (s, 1H); 13C nmr (CD3OD + CDCl3) ꢀ 121.26,
122.87, 124.07, 126.60, 127.00, 127.81, 128.40, 128.69, 134.34,
134.78, 143.77, 146.99, 160.20 ppm. Anal. Calcd. for C16H12N2O:
C 77.40, H 4.87, N 11.28; Found: C 77.38, H 4.83, N 11.27.
Method B.
A
mixture of 2-chloromethyl-4,5-dichloro-
pyridazin-3(2H)-one (3 g, 14.055 mmol), sodium iodide (2.45 g,
14.76 mmol) and acetonitrile (50 ml) was refluxed for 2 hours.
After cooling to 30–40 °C, triphenylphosphine (4.07 g, 15.51
mmol) was added to the reaction solution. And the mixture was
then refluxed for 2 hours. Benzaldehyde (1.5 g, 14.10 mmol)
and potassium t-butoxide (2.05 g, 95%, 17.21 mmol) were added
to the reaction solution. The resulting mixture was refluxed for
additional 1 hour. After evaporating the solvent was stirred for
20 minutes, then filtered by using Celite 545 and washed with
methylene chloride (50 ml). The organic layer was separated and
dried over anhydrous magnesium sulfate. The organic solution
was evaporated under reduced pressure and the resulting residue
was applied to the top of an open-bed silica gel. The column was
eluted with methylene chloride/n-hexane (1: 5, v/v). Fractions
containing (Z)- 4e or (E)- 4e were combined and evaporated to
give (Z)- 4e or (E)- 4e, respectively.
(Z)-4,5-Dichloro-2-styrylpyridazin-3(2H)-one [(Z)-4e]. Pale
yellow crystal (diethyl ether/n-hexane = 1:2, v/v). mp 110 -111
°C; tlc (CH2Cl2) Rf = 0.58; ir (KBr) 3100, 3060, 3000, 1660,
1580, 1500, 1460, 1400, 1370, 1340, 1305, 1280, 1220, 1180,
1165, 1140, 980, 900, 840, 800, 780, 760, 700, 640 cm-1; 1H nmr
(CDCl3): ꢀ 6.58 (d, J = 9.43 Hz, 1H), 7.00 (d, J = 9.43 Hz, 1H),
7.11 – 7.16 (m, 2H), 7.22 – 7.31 (m, 3H), 7.67 ppm (s, 1H); 13C
nmr (CDCl3) ꢀ 125.46, 126.72, 128.19, 128.27, 128.90, 133.41,
(E)-3-Styryl-1,2,3-benzotriazin-4(3H)-one [(E)-4c]. Yellow
crystal (diethyl ether/n-hexane = 1:4, v/v). mp 175 -176 °C; tlc
(CH2Cl2) Rf = 0.45; ir (KBr) 3100, 3050, 1705, 1690, 1660,
1620, 1600, 1500, 1480, 1460, 1340, 1320, 1280, 1220, 1200,
1120, 1100, 1080, 1040, 1000, 980, 900, 860, 780, 760, 700, 620
cm-1; 1H nmr (DMSO-d6 + CDCl3): ꢀ 6.38 (d, J = 14.69 Hz, 1H),
7.15 – 7.22 (m, 1H), 7.27 – 7.32 (m, 2H), 7.36 – 7.39 (m, 2H),
7.44 – 7.49 (m, 2H), 7.51 – 7.57 (m, 1H), 7.72 (d, J = 14.07 Hz,
1H), 7.90 ppm (d, J = 7.13 Hz, 2H); 13C nmr (DMSO-d6
+
CDCl3) ꢀ 117.99, 127.25, 129.46, 130.49, 131.27, 132.44,
132.51, 135.86, 137.40, 140.35, 169.60 ppm. Anal. Calcd. for
C15H11N3O: C 72.28, H 4.45, N 16.86; Found: C 72.27, H 4.41,
N 16.85.
(E)-3-Methoxy-1-styrylpyridin-2(1H)-one [(E)-4d]. Pale
yellow crystal (diethyl ether/n-hexane = 1:3, v/v). mp 165 -166
°C; tlc (CH2Cl2/ethyl acetate = 20:1, v/v) Rf = 0.29; ir (KBr)
3105, 3080, 3000, 2950, 1680, 1620, 1570, 1520, 1480, 1400,
1
1280, 1220, 1085, 1000, 880, 780, 760, 720, 680 cm-1; H nmr
(CDCl3): ꢀ 3.83 (s, 3H), 6.19 (t, J = 7.28 Hz, 1H), 6.60 (d, J =
7.37 Hz, 1H), 6.65 (d, J = 14.85 Hz, 1H), 7.25 – 7.30 (m, 2H),
7.32 – 7.37 (m, 2H), 7.46 (d, J = 7.95 Hz, 2H), 8.04 ppm (d, J =
14.85 Hz, 1H); 13C nmr (CDCl3) ꢀ 55.97, 105.62, 111.61,
120.66, 123.59, 125.80, 126.69, 128.09, 128.78, 134.82, 150.36,
157.07 ppm. Anal. Calcd. for C14H13NO2: C 73.99, H 5.77, N
6.16; Found: C 73.96, H 5.75, N 6.13.
(E)-2-Styrylsaccharine [(E)-4f]. White crystal (diethyl ether:
n-hexane = 1:2, v/v). mp 163 -164 °C; tlc (CH2Cl2) Rf = 0.78; ir
(KBr) 3095, 3010, 1740, 1642, 1600, 1485, 1450, 1350, 1300,
1285, 1180, 1120, 1090, 1060, 940, 840, 800, 750, 650 cm-1; 1H
nmr (CDCl3): ꢀ 7.10 (d, J = 15.19 Hz, 1H), 7.20 – 7.48 (m, 7H),
7.84 – 7.98 (m, 3H), 8.11 – 8.14 ppm (m, 1H); 13C nmr (CDCl3)
ꢀ 115.35, 121.08, 121.34, 125.61, 126.51, 126.67, 128.26,
128.81, 134.64, 134.69, 135.14, 137.59, 156.67 ppm. Anal.
Calcd. for C15H11NSO3: C 63.14, H 3.89, N 4.91; Found: C
63.12, H 3.86, N 4.90.
134.53, 135.85, 136.60, 155.83 ppm. Anal. Calcd.
C12H8N2Cl2O: C 53.96, H 3.02, N 10.49; Found: C 53.93, H
3.00, N 10.41.
for
(E)-4,5-Dichloro-2-styrylpyridazin-3(2H)-one [(E)-4e]. Pale
yellow crystal (diethyl ether/n-hexane = 1:2, v/v). mp 161 -162
°C; tlc (CH2Cl2) Rf = 0.74; ir (KBr) 3108, 1664, 1592, 1300,
1238, 1134, 958, 898, 742, 696 cm-1; 1H nmr (CDCl3): ꢀ 7.26 (d,
J = 14.18 Hz, 1H), 7.28 – 7.38 (m, 3H), 7.47 – 7.50 (m, 2H),
7.86 (s, 1H), 8.10 ppm (d, J = 14.35 Hz, 1H); 13C nmr (CDCl3) ꢀ
122.21, 124.13, 127.02, 128.49, 128.88, 134.49, 134.56, 135.94,
136.04, 154.68 ppm. Anal. Calcd. for C12H8N2Cl2O: C 53.96, H
3.02, N 10.49; Found: C 53.93, H 3.00, N 10.41.
Method C. A mixture of heterocycles 1 (0.011 mol), (E)-ꢀ-
bromostyrene (1.94 g, 0.013 mol), anhydrous potassium
carbonate (3.34 g, 0.024 mol) and anhydrous dimethylform-
amaide (20 ml) was refluxed for 23–38 h under nitrogen. After
cooling to room temperature, the reaction mixture was poured
into ice water with stirring. The precipitate was collected by
filtration, dried in air and recrystallized in suitable solvent to
give (E)-4a (89%), (E)-4b (82%), (E)-4d (79%), (E)-4h (10%)
and (E)-4j (94%).
(E)-N-Styrylphthalimide [(E)-4g]. Yellow crystal (diethyl
ether: n-hexane = 1:2 v/v). mp 187 -188 °C; tlc (CH2Cl2) Rf =
0.80; ir (KBr) 3150, 3090, 1740, 1680, 1630, 1490, 1480, 1405,
1240, 1200, 1140, 1050, 1040, 980, 920, 820, 780, 740, 705
1
cm-1; H nmr (CDCl3): ꢀ 7.25 – 7.30 (m, 1H), 7.34 – 7.39 (m,
(E)-1-Styrylpyridin-2(1H)-one [(E)-4j]. Pale yellow crystal
(diethyl ether/n-hexane = 1:2, v/v). mp 150-151 °C; tlc (CH2Cl2)
Rf = 0.15; ir (KBr) 3132, 2986, 1680, 1608, 1544, 1408, 1360,
3H), 7.48 – 7.50 (m, 2H), 7.66 (d, J = 15. 16 Hz, 1H), 7.75 –
7.79 (m, 2H), 7.88 – 7.92 ppm (m, 2H); 13C nmr (CDCl3) ꢀ
105.62, 111.61, 120.66, 123.59, 125.80, 126.69, 128.09, 128.78,
134.82, 150.36, 157.07 ppm. Anal. Calcd. for C16H11NO2: C
77.10, H 4.45, N 5.62; Found: C 77.10, H 4.41, N 5.57.
(E)-N-Styryl-1,8-naphthalimide [(E)-4i]. Thin yellow
crystal (diethyl ether/n-hexane = 1:1 v/v). mp 168-169 °C; tlc
(CH2Cl2) Rf = 0.56; ir (KBr) 3060, 3028, 1705, 1671, 1666,
1582, 1369, 1352, 1304, 1231, 1178, 940, 893, 778 cm-1; 1H nmr
(DMSO-d6): ꢀ 7.32 (d, J = 15.05 Hz, 1H), 7.33 – 7.35 (m, 1H),
7.39 – 7.44 (m, 2H), 7.45 (d, J = 14.94 Hz, 1H), 7.55 (d, J = 7.44
Hz, 2H), 7.85 (t, J = 7.47 Hz, 2H), 8.43 (d, J = 8.26 Hz, 2H),
8.47 ppm (d, J = 7.25 Hz, 2H); 13C nmr (CDCl3) ꢀ 120.71,
122.50, 126.69, 127.07, 127.88, 127.93, 128.67, 131.52, 131.66,
134.14, 136.05 ppm. Anal. Calcd. for C20H13NO2: C 80.25, H
4.38, N 4.68; Found: C 80.19, H 4.36, N 4.68.
1
1282, 1152, 976, 770, 706 cm-1; H nmr (CDCl3): ꢀ 6.24 (t, J =
6.96 Hz, 1H), 6.59 (d, J = 8.84 Hz, 1H), 6.67 (d, J = 14.84 Hz,
1H), 7.26 – 7.38 (m, 4H), 7.46 – 7.48 (m, 2H) 7.61 (dd, J = 1.78,
7.04 Hz, 1H), 7.98 ppm (d, J = 14.84 Hz, 1H); 13C nmr (CDCl3)
ꢀ 105.62, 111.61, 120.66, 123.59, 125.80, 126.69, 128.09,
128.78, 134.82, 150.36, 157.07 ppm. Anal. Calcd. for C13H11NO:
C 79.16, H 5.62, N 7.10; Found: C 79.13, H 5.58, N 7.11.
Method D. A mixture of N-chloromethylbenzotriazole (2h,
15.0 mmol), triphenylphosphine (16.5 mmol) and acetonitrile
(60 ml) was refluxed for 48 hours. After cooling to 20~30 °C,
The ((1H-benzo[d][1,2,3]triazol-1-yl)methyl)triphenylphospho-
nium chloride was collected by filtration, washed with dichloro-
methane(30ml x 2) and dried at room temperature. To a solution

Jul-Aug 2007
Synthesis and Photophysical Properties of N-Styrylazinones
959
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of the crude product and tetrahydrofuran (50 ml or toluene) was
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(E)-1-Styrylbenzotiriazole [(E)-4h]. White crystal (diethyl
ether /n-hexane = 1:5, v/v). mp 115 -116 °C (lit. [59] mp 116-
117 °C); tlc (CH2Cl2/n-hexane = 2:1, v/v) Rf = 0.16. IR (KBr)
3062, 3024, 1652, 1486, 1452, 1163, 1056, 941, 744, 690 cm-1;
1H nmr (CDCl3): ꢀ 7.29 – 7.58 (m, 8 H), 7.71 – 7.58(m, 1H),
7.89(d, J = 14.64 Hz, 1H), 8.07 – 8.10 ppm (m, 1H); 13C nmr
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128.29, 128.48, 129.01, 131.50, 134.34, 146.34 ppm. Anal.
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Acknowledgment. This work was supported by Korea
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