Reaction of 6-aryl- or styryl-4-methylsulfanyl-2-oxo-2H-pyrans with active methylene compounds and fluorescence properties of the products

Article abstract of DOI:10.1002/jhet.5570450133

(Chemical Equation Presented)New 2-pyrone derivatives, dialkyl 3-cyano-6-phenyl-2-oxo-2H-pyran-4-ylmalonates and alkyl 3-cyano-6-phenyl-2-oxo- 2H-pyran-4-ylacetates, which were easily prepared by the reaction of 6-aryl-4-methyl-sulfanyl-2-oxo-2H-pyran-3-c

Full text of DOI:10.1002/jhet.5570450133

Jan-Feb 2008
265
Reaction of 6-Aryl- or Styryl-4-methylsulfanyl-2-oxo-2H-pyrans
with Active Methylene Compounds and Fluorescence
Properties of the Products
Naoko Mizuyama,a Yuka Murakami,a Takatoshi Nakatani,a Keiko Kuronita,a
Shinya Kohra,aKazuo Ueda,a Kyoko Hiraoka,a and Yoshinori Tominaga,a*
aFaculty of Environmental Studies of Nagasaki University, 1-14,
Bunkyo-machi, Nagasaki 852-8521, Japan,
ae-mail:ytomi@nagasaki-u.ac.jp
Received October 11, 2006
ROOC COOR
SMe
COOR
COOR
K2CO3
CN
O
CN
O
+
+
in DMSO
O
O
n
n
n
R2N
R2N
Ph
ROOC
SMe
O
N
COOR
K2CO3
CN
O
OH
in DMSO
COOPh
O
O
n
R2N
R2N
New 2-pyrone derivatives, dialkyl 3-cyano-6-phenyl-2-oxo-2H-pyran-4-ylmalonates and alkyl 3-cyano-
6-phenyl-2-oxo-2H-pyran-4-ylacetates, which were easily prepared by the reaction of 6-aryl-4-methyl-
sulfanyl-2-oxo-2H-pyran-3-carbonitriles with active methylene compounds in the presence of potassium
carbonate, show fluorescence emission radiation. The light-emitting region of dimethyl 3-cyano-6-(4-N,N-
dimethylamino)styryl-2-oxo-2H-pyran-4-ylmalonate (7h) was 620 nm in dichloromethane, making this
compound a typical red fluorescent compound. Methyl 8-hydroxy-6-methyl-1-oxo-3-phenyl-1H-pyrano-
[3,4-c]pyridine-5-carboxylate deriv-atives also showed fluorescence in the solid state. This is the first
example of fluorescence in fused 2-pyrone derivatives.
J. Heterocyclic Chem., 45, 265 (2008).
en-2-ones (2m-o) with synthesized 2H-pyrone derivatives
bearing an active methylene group at the 4 position by the
displacement of a 4-methylsulfanyl group with active
methylene compounds.
INTRODUCTION
Pyrones and fused pyrones are important in designing
luminescent materials for organic light-emitting diodes
(OLED), dye lasers, and luminescent labeling reagents for
HPLC or capillary electrophoresis [1]. 2H-Pyrones
containing aryl groups at position 6 continue to attract
considerable attention in both synthetic and materials
chemistry, and are highly interesting materials for
applications in optoelectronic devices such as displays
[2]. It has been reported that 6-aryl- or styryl-4-methyl-
sulfanyl-2H-pyrones are easily prepared by the reaction of
ketene dithioacetal with active methylene compounds in
the presence of powdered sodium [3] and the resulting
compounds are also useful synthetic intermediates for 6-
aryl- and 6-styryl-4-alkoxy- or 4-amino-2-oxo-2H-pyran-
3-carbonitriles [4,5]. In the field of organic electron
luminescence, a red color is most desired. Compound 4-
(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-
4H-pyran (DCM) and other 4H-pyran derivatives are
important and well-known red materials in organic EL
substances [6,7]. To prepare our final target compound 7h
possessing red fluorescence, we The previous procedure
for preparing 3a-l can be applied to 6-styryl-2H-pyrones.
The reaction of 4-(N,N-disubstitutedaminophenyl)but-3-
MeOOC
COOMe
CN
NC
CN
O
O
Me
O
Me2N
Me2N
DCM
7h
Figure 1
RESULTS AND DISCUSSION
Synthesis of 2H-Pyrones and Fused 2H-Pyrone. The
2H-pyrone derivatives (3a-l) used in this study were
easily prepared by the reaction of the corresponding aryl
acetyl compounds (2a-l) with ketene dithioacetal (1a)
[4b,d]. Methyl 6-aryl-4-methylsulfanyl-2-oxo-2H-pyran-
3-carboxylates (4a-d) were also prepared from 1b and
arylacetyl compounds (2a, c, f, l). Because compounds
4a-d were not very active against nucleophiles, the

266
N. Mizuyama, Y. Murakami, T. Nakatani, K. Kuronita, S. Kohra, K. Ueda, K. Hiraoka, Y. Tominaga
Vol 45
4-sulfinyl compounds 5a-c, obtained by the oxidation of
5a-c with m-chloroperbenzoic acid or hydrogen peroxide,
were used in the reaction with active methylene
compounds (See Figure 2).
The previous procedure for preparing 3a-l can be
applied to 6-styryl-2H-pyrones. The reaction of 4-(N,N-
disubstituted aminophenyl)but-3-en-2-ones (2m-o) with
methyl 3,3-bis(methylsulfanyl)-2-cyanoacrylate (1a) was
carried out in the presence of sodium hydroxide as the
base to give the desired products, 6-[2-(4-N,N'-di-
substituted aminophenyl)vinyl]-4-methylsulfanyl-2-oxo-
2H-pyran-3-carbonitriles (3m-o) in 32, 26, and 29%
yields, respectively (Scheme 1).
X
O
MeS
MeS
COOMe
Ar
1a, b
2a-l
1a: X=CN
b: X=COOMe
2a: Ar=C6H5-
Scheme 1
b: Ar=C6H4 (OMe)(2)
c: Ar=C6H4--OMe(4)
d: Ar=C6H3 (OMe)2(2,4)
O
CN
MeS
MeS
-
e: Ar=C6H3-(OMe)2(2,4)
+
COOMe
f: Ar=C6H3 (OMe)2(3,4)
R2N
SMe
-
g: Ar=C6H2 (OMe)3(3,4,5)
1a
2m-o
CN
-
h: Ar=C6H4 (NM2)(4)
m: NR2=NMe2
n: NR2=NEt2
o: NR2=NPh2
i: Ar=C6H4-CN(4)
j: Ar=2-naphthyl
k: Ar=2-thienyl
O
O
SMe
R
CN
3a-l
l: Ar=C6H3-(O-CH2-O)(3,4)
O
O
10%HCl
NaOH
in DMSO
R2N
3m-o
O
SMe
COOMe
SMe
m: NR2=NMe2
n: NR2=NEt2
o: NR2=NPh2
COOMe
O
O
O
O
R
R
It is well known that the reaction of ketene dithioacetals
with active methylene compounds smoothly progresses in
the presence of potassium carbonate as a base to give the
corresponding mono-substituted products in good yield.
The reaction of compound 3 with active methylene
compounds was carried out under these experimental
conditions. The reaction of 3a, c, g, j, and l with methyl
or ethyl malonates (6a, b) in the presence of potassium
5a, b
4a-c
4a: Ar=C6H5-
5a: Ar=C6H5-
b: Ar=C6H4-(OMe)(4)
b: Ar=C6H4 (OMe)(4)
c: Ar=C6H3 (OMe)2(3,4)
d: Ar=C6H3-(O-CH2-O)(3,4)
Figure 2
Table 1. Synthesis of Dialkyl 3-Cyano-6-phenyl-2-oxo-2H-pyran-4-ylmalonates.
COOR3
COOR3
SMe
CN
HC
O
K2CO3
10% HCl
COOR3
COOR3
CN
R1
R2
ꢀ
H2C
O
O
R1
R2
in DMSO
O
n
6a, b
n
7a-h
3a, c, g, j, l
No.
R1
R2
R3
n
Yield(%)
mp(°C)
Appearance
7a
b
c
d
e
f
g
h
H
H
H
H
H
H
H
H
OMe
OMe
NMe2
NMe2
Me
Et
Me
Et
Me
Et
0
0
0
0
0
0
159-160
158-159
182-183
194-198
198-199
194-198
174-175
97
82
81
72
77
74
83
pale yellow needles
pale yellow needles
yellow needles
pale yellow needles
red needles
red needles
yellow needles
Me
thienyl
0
1
H
NMe2
84
200-202
black red needles
Me

Jan-Feb 2008
Reaction of 6-Aryl- or Styryl-4-methylsulfanyl-2-oxo-2H-pyrans with Active Methylene
Table 2. Synthesis of Dialkyl 3-Methoxycarbonyl-6-phenyl-2-oxo-2H-pyran-4-ylmalonates.
267
COOR3
COOR3
O
HC
SMe
O
COOMe
COOMe
K2CO3
10% HCl
COOR3
COOR3
R1
R2
R1
R2
ꢀ
H2C
O
O
O
in DMSO
6a, b
5a-c
No.
7i-m
R1
R2
R3
Yield(%)
mp(°C)
Appearance
7i
j
k
l
H
H
H
H
H
H
OMe
OMe
Me
Et
Me
Et
88
80
90
79
53
120-121
80-90
120-121
89-92
143-146
yellow needles
yellow needles
yellow needles
yellow needles
yellow needles
-O-CH2-O-
m
Me
Table 3. Synthesis of 1H-pyrano[3,4-c]pyridines
R3
SMe
R2
N
CN
R2
K2CO3
10% HCl
+
O
R1
R3
O
O
in DMSO
H
R1
O
O
O
3a, c, d, e, g
6c, d
8a-h
R1
Yield(%)
Mp(°C)
No.
R2
R3
COOMe
COOMe
COOEt
COOEt
COOEt
COOEt
COOEt
SO2-C6H4-Me(4)
Me
Me
8a
b
c
d
e
f
g
h
C6H5
C6H4-OMe(4)
C6H5
C6H4-OMe(4)
C6H3-OMe2(2,4)
C6H3-OMe2(3,4)
C6H4-NMe2(4)
C6H4-OMe(4)
52
30
70
31
30
28
9
>300
296-297
295-297
287-288
298-299
303-304
298-299
260-270
Me
Me
Me
Me
Me
Me
22
Me
N
SMe
CN
O
K2CO3
in DMSO
O
H
+
O
O
O
O
O
R
3a, c
6c
R
8i, j
3a: R=H
c: R=OMe
8i: R=H
j: R=OMe
carbonate in DMSO gave the corresponding dialkyl
3-cyano-6-phenyl- or 6-styryl-2-oxo-2H-pyran-4-yl-malo-
nates (7a-h) in 72-97% yields, respectively (shown in
Table 1).
Similarly, dialkyl 3-methoxycarbonyl-6-phenyl-2-oxo-
2H-pyran-4-ylmalonates (7i-m) were readily obtained
from 6-aryl-4-sulfinyl-2H-pyran-2-ones (5a-c) and active
methylene compounds (6a, b) in good yields (shown in
Table 2).
On the other hand, the reactions of 3a c, d, e, g with
methyl or ethyl acetoacetates (6c, d) under the same
reaction conditions did not give the corresponding
displacement products 7a-e. The products of these
reactions were determined to be 8-hydroxy-6-methyl-3-
phenyl-1-oxo-1H-pyrano[3,4-c]pyridine-5-carboxylates
(8a-h) (in Table 3) by spectroscopic (IR, UV, NMR, and
MS) and elemental analyses. In the NMR spectra of 8a-h,
the hydroxy protons at position 8 appear at 12.0-12.5 ppm
due to hydrogen bonding with a O=C group. In the case of
8i and f, the hydroxy protons were not shown due to
1
strong hydrogen bonds in the H-NMR spectra. In the
final step of this reaction, the reaction mixture was
acidified with 10% HCl solution and then the
intermediates, e.g., 3, were treated with concentrated HCl
to give separable mixtures of 8, 9, and 10. These
compounds were easily separated by their differential
solubilities in solvents such as dichloromethane, DMF,
and ethanol to give compounds 8, 9 and 10, respectively.
The structures of these compounds were determined by
spectroscopic (IR, NMR, UV, and MS) and elemental

268
N. Mizuyama, Y. Murakami, T. Nakatani, K. Kuronita, S. Kohra, K. Ueda, K. Hiraoka, Y. Tominaga
Vol 45
Table 4. Synthesis of 1H-pyrano[3,4-c]pyridines
R3
R3
R2
SMe
O
R2
CH2-R2
CN
O
CN
N
R2
10% HCl c-HCl
K2CO3
+
O
OH
R1
R3
6c, d, f
in DMSO
O
R1
R1
O
O
O
O
R1
O
O
O
3a, c, e, g
8a, c, d, g, h
9a-e
10a-g
R3
R1
R2
9 Yield(%)
10 Yield(%)
Entry
8 Yield(%)
-- --
1
2
3
4
5
6
7
8
9
C6H5
C6H5
C6H4-OMe(4)
C6H3(OMe)2(3,4) COOEt
C6H4-NMe2(4)
C6H5
C6H4-OMe(4)
C6H5
C6H4-OMe(4)
Me
Me
Me
Me
Me
Ph
10a 60
10b 36
10c 22
10d 45
COOMe
COOEt
COOEt
8a 10
8c 12
8d 30
9a 11
9b 21
9c 14
-- --
9d 11
9e 14
-- --
-- --
8g
9
10e
2
COOEt
COOEt
COOEt
SO2-C6H4-Me(4)
-- --
-- --
-- --
10b 69
10c 43
10f 66
10g 18
Ph
Me
SO2-C6H4-Me(4) Me
8h 22
-- --
Scheme 2. Reaction Pathway
R2
SMe
R2
O
O
CN
R2
K2CO3
R3
in DMSO
cHCl
10%HCl
CN
C
N
+
R1
O
O
R1
O
O
R1
O
O
O
6
3
R3
R3
R2
R3
H2O
H2O
O
R2
R2
NH2
O
O
O
NH
C
O
N
R1
O
O
R1
O
R1
O
O
R3
R3
R3
OH
R2
R2
R2
O
O
H2O
NH
NH
O
O-
CN
O
R1
O
R1
O
R1
O
O
-R3-COOH
R3
R3
R2
R2
O
O
CH2-R2
CN
N
O
O
OH
R1
R1
O
O
O
R1
O
8
9
10
analyses. The reaction pathway of each product (8, 9, 10)
is shown in Scheme 2.
The above reaction of 2-pyrones with active methylene
compounds in the presence of potassium carbonate

Jan-Feb 2008
Reaction of 6-Aryl- or Styryl-4-methylsulfanyl-2-oxo-2H-pyrans with Active Methylene
269
Table 5. Synthesis of Biaryl Derivatives from 2-Pyrones
SMe
SMe
X
X
CN
CN
NaOH
DMSO
+
O
O
NH2
R
R
CN
3a-d, f, 4a-c
Aryl
6f
11a-j
X
Yield(%)
Appearance
mp (°C)
No.
CN
85
76
colorless needles
colorless needles
colorless needles
coloroless prisms
colorless leaflets
pale yellow needles
240-242
216-219
212-213
259-261
263-265
257-259
C6H5
C6H4-OMe(2)
3a
b
c
CN
CN
CN
CN
C6H4-OMe(4)
-
99
85
90
73
d
C6H3 (OMe)2(2,4)
-
C6H2 (OMe)3(3,4,5)
e
CN
C6H4-NMe2(4)
-
f
g
h
i
CN
94
80
68
74
colorless needles
colorless needles
colorless needles
colorless needles
312-314
138-140
124-126
182-184
C6H4 (CN)(4)
C6H5
COOMe
COOMe
COOMe
C6H4-OMe(4)
C6H3O-CH2-O-
j
Scheme 3. Reaction Pathway
proceeds first with carbon nucleophilic attack at position 4,
followed by displacement of the methylsulfanyl group to
give the corresponding 4-substituted 2-pyrone derivatives.
Electron donating and accepting substituents are
recognized as molecular subunits that display non-linear
optical properties due to their high polarizability. These
molecules not only exhibit optical properties but also
display diverse pharmacological activities. Ram et al.
have reported the synthesis of biaryl compounds by the
reaction of 2H-pyrone derivatives (3) with malononitrile
in the presence of potassium hydroxide [8]. This reaction
proceeds initially by carbanion attack at position 6 with
ring opening followed by ring transformation to yield
biaryl compounds. While this reaction conveniently
synthesizes polyfunctionalized biaryl compounds, the
yield is low. We reexamined our reaction conditions to
increase the yield of products. Compound 3a was allowed
to react with malononitrile (6f) in the presence of
powdered sodium hydroxide in DMSO at room
temperature for 5 hours. The reaction mixture was poured
+into a large amount of water and stirred at room
temperature for about 12 hours until nso more products
precipitated. The product was recrystallized from
methanol to give colorless needles, mp 240-242 °, in 85%
yield. The structure of this compound was determined to
be 4-amino-5-methylsulfanyl-biphenyl-2,4-di-carbonitrile
(11a), which was identical spectroscopically with the
compound prepared by Ram. Similarly, other new
biphenyl compounds (11b-j) were synthesized from the
corresponding 4-methylsulfanyl-2-oxo-2H-pyran-3-carbo-
nitriles (3b-d, f, 4a-c) and 6f under similar reaction
conditions. In reactions of 4a b, and c with 6f, 3-amino-
biphenyl-4-carboxylates (11a-j) were also obtained in 73-
99% yield (see Table 5).
SMe
CN
CN
CN
NaOH
+
R1
O
in DMSO
O
3a
6f
SMe
MeS
CN
CN
O-
R1
O
O
R1
NC
O
CN
CN
-
CN
MeS
MeS
CN
CN
-
R1
NC
R1
NC
-O
O
CN
CN
SMe
CN
SMe
CN
CN
R1
R1
NH2
NH
CN
11a
Fluorescence properties. The UV-vis absorption and
fluorescence emission radiation of the 4-substituted 2-
oxo-2H-pyran-3-carbonitriles and 3-carboxylates and
fused 2H-pyrones were analyzed. DCM and AlQ3[tris(8-
hydroxy-quinolinato)aluminum] were used as standards
for absorption and fluorescence spectra. The measure-
ments of both absorption and fluorescence spectra were

270
N. Mizuyama, Y. Murakami, T. Nakatani, K. Kuronita, S. Kohra, K. Ueda, K. Hiraoka, Y. Tominaga
Vol 45
performed in dichloromethane and ethanol solutions at
room temperature. The spectroscopic properties,
absorption maxima (ꢀmax), molar absorptivities (ꢁ), fluor-
escence maxima (Em max) and relative fluorescent
intensities (RI) are described in part of Experimental. The
aryl and styryl moieties bearing N,N-disubstituted amino
groups at position 6 of the 2-pyrone derivatives fulfill the
important condition for fluorescent expression.
Compounds (3l-m) showed longer wavelength shifts in
comparison with the most basic 2-pyrone, 4-methyl-
appreciable fluorescence emission radiation in the solid
state. In a similar case with compound 3, 3-phenyl
pyrano[3,4-c]pyridin-1-one bearing electron-donating
groups such as a methoxy group on the phenyl group
showed strong fluorescence. For example, ethyl
8-hydroxy-3-(2,4-dimethoxyphenyl)-6-methyl-1-oxo-1H-
pyrano[3,4-c]pyridine-5-carboxylate (8e) showed fluor-
escence emission radiation at 490 nm with a relative
intensity of 4.88 in the solid state. The reason why the
fluorescence of these chemical compounds increases
seems to be the strong packing by the flat molecules due
to hydrogen bonding of a –C=O----H-O- system. This fact
suggests the possibility of developing fluorescence in
other fused 2H-pyrone derivatives. Biaryl derivatives
(11a-j) showed weak fluorescence emission radiation in
the solid state.
In conclusion, new 2-pyrone derivatives, dialkyl
3-cyano-2-oxo-6-phenyl-2H-pyran-4-ylmalonates and
alkyl 3-cyano-2-oxo-6-phenyl-2H-pyran-4-ylacetates, which
were easily prepared by the reaction of 6-aryl-4-methyl-
sulfanyl-2-oxo-2H-pyran-3-carbonitriles with active
methylene compounds in the presence of potassium
carbonate, show fluorescence emission radiation. Methyl
8-hydroxy-6-methyl-1-oxo-3-phenyl-1H-pyrano[3,4-c]-
pyridine-5-carboxylate derivatives also showed fluor-
escence in the solid state. This is the first example of
fluorescence in fused 2-pyrone derivatives.
sulfanyl-6-phenyl-2-oxo-2H-pyan-3-carbonitrile
(3a).
However, their relative fluorescence intensities have a
tendency to decrease, while the ꢁ values increase in the
absorption spectra. In general, 4-amino-6-aryl-2-oxo-2H-
pyran-3-carbonitriles show stronger intensity than the
corresponding 4-methylsulfanyl compounds and their
light-emission regions show a 40-50 nm blue shift. On the
other hand, 4-substituted compounds (7 and 9) show a
small batho-chromic shift and stronger fluorescence
emission radiation than that of compound 3 in the solid
state. In particular, the light-emitting region of compound
7h was 620 nm in dichloromethane, making this
compound a typical red fluorescent compound (See
Figure 3). Compounds 7e, f also showed red fluorescence
in ethanol solution and can be used as a fluorescence
reagent in an oxalate chemiluminescence system.
1000
EXPERIMENTAL
900
DCM
3h
800
Identifications of compounds and measurements of properties
were carried out by general procedures using the following
equipment. All melting points were determined in a capillary
tube and are uncorrected. The infrared (IR) spectra were
recorded in potassium bromide pellets on JASCO 810 or
Shimazu IR-460 spectrometer, and the ultraviolet (UV)
absorption spectra were determined in 95% ethanol on a Hitachi
323 spectrometer. The fluorescence spectra were determined on
Shimazu RF-1500. The nuclear magnetic resonance (NMR)
spectra were obtained on Gemini 300NMR (300 MHz) and
500NMR (500 MHz) spectrometers with tetramethylsilane as an
internal standard. The mass spectra (MS) were recorded on
7e
700
3m
600
7h
500
400
300
200
100
0
JEOL DX-303 mass spectrometers.
Microanalyses were
performed by Y. Ohwatari on a Perkin Elmer 2002 at Nagasaki
University. All chemicals were reagent grade and used without
further purification unless otherwise specified.
400
450
500
550
600
650
700
750
Fluorescent Wavelength (nm)
Method of Measurement of Fluorescence.
Figure 3. Comparison og fluorescent intensity of 2H-
pyrone with that of DCM in CH2Cl2 solution.
In solid states. A powder sample of subject compound is
heaped in the tray. After covering the sample with quartz plate,
this part was fixed in fluorescence spectrometer. After fixing the
fluorescent wavelength, the excitation spectrum was determined
by the scanning with the fluorescent wavelength. Similarly,
Fluorescent spectrum was obtained after scanning with the
excitation wavelength. After obtaining these results, the
excitation wavelength was decided and the fluorescence
spectrum was measured.
The fluorescence emission radiation of fused pyrones
such as compounds 8 and 9 were analyzed. The 1H-
pyrano[3,4-c]pyridin-1-one derivatives (8) exhibit moder-
ately strong fluorescent radiation, while the 1H,8H-
pyrano[3,4-c]pyran-1,8-dione derivatives (9) did not show

Jan-Feb 2008
Reaction of 6-Aryl- or Styryl-4-methylsulfanyl-2-oxo-2H-pyrans with Active Methylene
271
The fluorescent relative intensity was determined by using
AlQ3 as standard sample. Fluorescence of standard sample and
all subject compounds were measured on 272 nm excitation.
In solution. The concentration of measuring samples in the
excitation wavelength region was adjusted under 0.05 on the
molar absorption. The fluorescence spectra in solution were
obtained in a manner similar to that described for the
measurement in the solid states. Relative intensity of
fluorescence in solution was determined by using DCM as a
standard compound. Fluorescence of standard sample and all
subject compounds were measured on 366 nm excitation.
6-(4-N,N-Dimethylamino)styryl-4-methylsulfanyl-2-oxo-2H-
pyran-3-carbonitrile (3m). A mixture of 1.89 g (10 mmoles) of
2l, 2.03 g (10 mmoles) of 1a, 0.8 g (20 mmoles) powdered
sodium hydroxide, and 40 ml of DMSO was stirred at room
temperature for 1 hour. The reaction mixture was poured into
500 ml of ice-water and stirred at room temperature for 2 hours.
The brown precipitates that appeared were collected by
filtration, washed with water, and recrystallized from a mixture
of dichloromethane and methanol to give 0.998 g (3.20 mmoles,
32% yield) of black violet leaflets, mp 280-284°; ir(potassium
bromide) ꢀ cm-1: 2202(CN), 1705(C=O), 1595, 1560, 1465,
1360, 1162); uv(EtOH) ꢁ nm(log ꢂ): 253 (4.19), 309 (4.29), 374
(3.67), 397 (3.64), 513 (4.67); fluorescence (EtOH):Ex: 366 nm;
Em: 624 nm. (CH2Cl2): Ex: 541nm, Em:612 nm: RI=1.25. 1H
nmr(CDCl3) ꢃ: 2.65(s, 3, SMe), 3.10(s, 6, 2xNMe2), 6.12(s, 1, 6-
H), 6.44(d, 1, =CH, J=15.7 Hz), 6.72(d, 2, 3', 5'-H, J=9.1 Hz),
7.48(d, 2, 2', 6'-H, J=9.1 Hz), 7.68 (d, 2, =CH, J=15.7 Hz); ms:
m/z 312 (M+, 100), 284(6), 241(5), 209(15), 174(16), 44(35).
Anal. Calcd for C17H16N2O2S: C, 65.36; H, 5.16; N, 8.97. Found.
C, 65.19; H, 5.14; N, 8.88.
bromide) ꢀ cm-1: 2205 (CN), 1720 (CO), 1590, 1565, 1494,
1460, 1330, 1280; uv (EtOH) ꢁ nm(log ꢂ): 305 (4.48), 502
(4.19); fluorescence (EtOH): Em, 285 nm; Ex, 620 nm(weak);
1H nmr (CDCl3) ꢃ: 2.62 (s, 3, SMe), 6.18 (s, 1, 5-H), 6.48 (d, 1,
=CH, J=15.1 Hz), 6.75-7.40 (m, 14, phenyl-H), 7.61 (d, 1, =CH,
J=15.1 Hz); ms: m/z 437 (M++1, 12), 436 (M+, 38), 313 (8), 298
(7), 53 (33), 42 (100). Anal. Calcd for C27H20N2O2S: C, 74.29;
H, 4.62; N, 6.42. Found. C, 74.22; H, 4,71; N, 6,43.
Dimethyl 3-Cyano-2-oxo-6-phenyl-2H-pyran-4-yl-
malonate (7a). This compound (0.635 g, 1.94 mmoles) was
prepared in 97% yield from 3a (0.487 g, 2.0 mmoles) and
dimethyl malonate (6a)(0.528 g, 4.0 mmoles) by the previous
method [4d]. This product was recrystallized from methanol to
give pale yellow needles, mp 159-160°; ir(potassium bromide)
ꢄmax cm-1: 3450 (OH, br), 2210 (CN), 1750 (CO), 1620, 1530;
uv(EtOH) ꢁmax nm (log ꢂ): 256 (3.93), 372 (4.35); fluorescence
1
(solid): Ex, 337 nm; Em, 479 nm; RI=7.51; H nmr(CDCl3) ꢃ:
3.90 (s, 6, OMeX2), 5.09 (s, 1, CH), 6.76 (s, 1, 5-H), 7.58 (m, 3,
3', 4', 5'-H), 7.92 (m, 2, 2', 6'-H); ms m/z: 328 (M++1, 19), 327
(M+, 100), 295 (75), 267 (47), 105 (82), 77 (56). Anal. Calcd. for
C17H13NO6: C, 62.39 ; H, 4.00 ; N, 4.28. Found: C, 62.33; H,
3.84; N, 4.30.
Diethyl 3-Cyano-2-oxo-6-phenyl-2H-pyran-4-ylmalonate
(7b). A mixture of 0.486 g(2.0 mmoles) of 3a, 0.64 g (4.0
mmoles) of diethyl malonate (6b), and 0.936 g (3 mmoles) of
potassium carbonate in 20 ml of DMSO was stirred for 2 hours
at room temperature. The reaction mixture was poured into 200
ml of ice-water and acidified with 10% hydrochloric acid. The
precipitate that appeared was collected by filtration, washed with
water, and recrystallized from ethanol to give 0.582 g(1.64
mmoles, 82% yield) of colorless needles, mp 158-159°;
ir(potassium bromide) ꢄ cm-1: 2230 (CN), 1740 (CO), 1530;
uv(EtOH) ꢁ nm(log ꢂ): 290 (4.50), 324 (4.40), 390 (4.25);
6-(4-N,N-Diethylamino)styryl-4-methylsulfanyl-2-oxo-2H-
pyran-3-carbonitrile (3n). A mixture of 2.17 g (10 mmoles) of
2m, 2.03 g (10 mmoles) of 1a, 0.8 g (20 mmoles) powdered
sodium hydroxide, and 40 ml of DMSO was stirred at room
temperature for 1 hour. The reaction mixture was poured into
500 ml of ice-water and stirred at room temperature for 10
hours. The brown oil that appeared were collected and
crystallized by the treatment with methanol to give 0.892 g (2.62
mmoles, 26% yield) of black solids. An analytical sample was
recrystallized from a mixture of dichloromethane and methanol
to give black violet leaflets, mp 242-246°; ir(potassium bromide)
ꢄ cm-1: 2202 (CN), 1700 (CO), 1590, 1560, 1460, 1180; uv
(EtOH) ꢁ nm(log ꢂ):252 (4.09), 315 (4.25), 374 (3.52), 397
(3.42), 529 (4.69); fluorescence (CH2Cl2): Em: 550 nm; Ex: 613
1
fluoresence (solide): Ex, 263 nm; Em, 470 nm; RI=4.30; H
nmr(CDCl3) ꢃ: 1.34(t, 6-CH2-CH3, J=7.2 Hz,), 4.29 (m, 4, O-
CH2-), 5.02 (s, 1, CH), 7.17 (s, 1, 5-H), 7.48-7.58 (m, 3, phenyl-
H), 7.88-7.92 (m, 2, phenyl-H); ms :m/z 356 (M++1, 23), 355
(M+, 100), 309 (11), 281 (51), 255 (16), 238 (18), 211 (16), 105
(81), 77 (46). Anal. Calcd for C19H17NO6: C, 64.22; H, 4.82; N,
3.94. Found. C, 64.32; H, 4.82; N, 3.86.
Dimethyl 3-Cyano-6-(4-methoxyphenyl)-2-oxo-2H-pyran-
4-ylmalonate (7c). A mixture of 0.546 g(2.0 mmoles) of 3d,
0.53 g (4.0 mmoles) of 6a, and 0.936 g (3.0 mmoles) of
potassium carbonate in 20 ml of DMSO was stirred for 2 hours
at room temperature. The reaction mixture was poured into 200
ml of ice-water and acidified with 10% hydrochloric acid. The
precipitate that appeared was collected by filtration, washed with
water, and recrystallized from methanol to give 0.577 g(1.62
mmoles, 81% yield) of colorless needles, mp 180-183°;
ir(potassium bromide) ꢀ cm-1: 2220 (CN), 1750 (CO), 1515;
uv(EtOH) ꢁ nm(log ꢂ): 255 (3.93), 372 (4.35); fluoresence
1
nm. RI=0.65; H nmr (CDCl3) ꢃ: 1.21 (t, 6, N-CH2-CH3, J=7.1
Hz), 2.61 (s, 3, SMe), 3.43 (q, 4, N-CH2-, J=7.1 Hz), 6.07 (s, 1,
5-H), 6.37 (d, 1, =CH, J=15.7 Hz), 6.65 (d, 2, 3', 5'-H, J=9.1
Hz), 7.42 (d, 2, 2', 6'-H, J=9.1 Hz), 7.63 (d, 1, =CH, J=15.7 Hz);
ms: m/z 340 (M+, 76), 325 (100), 297 (3), 158 (6). Anal. Calcd
for C19H20N2O2S: C, 67.03; H, 5.92; N, 8.23. Found. C, 66.89;
H, 5.96; N, 8.20.
1
(solid): Ex, 270 nm; Em, 512 nm; RI=1.15; H nmr(CDCl3) ꢃ:
6-(4-N,N-Diphenylamino)styryl-4-methylsulfanyl-2-oxo-2H-
pyran-3-carbonitrile(3o). A mixture of 3.13 g(10 mmoles) of
2n, 2.03 g (10 mmoles) of 1a, 0.8 g (20 mmoles) powdered
sodium hydroxide, and 40 ml of DMSO was stirred at room
temperature for 1 hour. The reaction mixture was poured into
500 ml of ice-water and stirred at room temperature for 2 hours.
The brown precipitates that appeared were collected by
filtration, washed with water, and recrystallized from a mixture
of dichloromethane and methanol to give 1.25 g (2.87 mmoles,
29% yield) of red brown leaflets, mp 210-216°; ir(potassium
3.86 (s, 6, OMe), 3.90 (s, 3, OMe), 5.03 (s, 1, CH), 7.00 (d, 2, 3',
5'-H, J=8.5 Hz), 7.03 (s, 1, 5-H), 7.87 (d, 2, 2', 6'-H, J=8.5 Hz);
ms: m/z 358 (M++1, 21), 357 (M+, 100), 329 (11), 297 (13), 13
(32). Anal. Calcd for C18H15NO7: C, 60.51; H, 4.23; N, 3.92.
Found. C, 60.49; H, 4.23; N, 4.11.
Diethyl 3-Cyano-6-(4-methoxyphenyl)-2-oxo-2H-pyran-4-
ylmalonate (7d). A mixture of 0.546 g (2.0 mmoles) of 3d, 0.64
g (4.0 mmoles) of 6b, and 0.936 g (3.0 mmoles) of potassium
carbonate in 20 ml of DMSO was stirred for 2 hours at room
temperature. The reaction mixture was poured into 200 ml of

272
N. Mizuyama, Y. Murakami, T. Nakatani, K. Kuronita, S. Kohra, K. Ueda, K. Hiraoka, Y. Tominaga
Vol 45
ice-water and the whole was acidified with 10% hydrochloric
acid. The precipitate that appeared was collected by filtration,
washed with water, and recrystallized from methanol to give
0.553 g(1.44 mmoles, 72% yield) of pale yellow needles, mp
194-198°; ir(potassium bromide) ꢀ cm-1: 2210 (CN), 1735 (CO),
1605, 1505; uv(EtOH) ꢁ nm(log ꢂ): 249 (4.25), 291 (4.33), 339
(4.44); fluoresence (solide): Ex, 272 nm; Em, 506 nm; RI=0.47;
1H nmr(CDCl3) ꢃ: 1.33 (t, 6, O-CH2-CH3, J=7.1 Hz), 3.90 (s, 6,
OMe), 4.31 (m, 4, O-CH2-), 5.00 (s, 1, CH), 7.00 (d, 2, 3', 5'-H,
J=9.3 Hz), 7.04 (s, 1, 5-H), 7.86 (d, 2, 2', 6'-H, J=9.3 Hz); ms:
m/z 386 (M++1, 23), 385 (M+, 100), 357 (6), 297 (13), 340 (5),
311 (12), 135 (33). Anal. Calcd for C20H19NO7: C, 62.33; H,
4.97; N, 3.63. Found. C, 62.43; H, 4.98; N, 3.50.
7.69 (dd, 1, 5'-H, J=1.3, 5.0 Hz), 7.78 (dd, 1, 3'-H, J=1. 3, 3.9
Hz); ms: m/z 334 (M++1, 19), 333 (M+, 100), 301 (15), 273
(28), 111 (72), 59 (22). Anal. Calcd for C15H11NO6S: C, 54.05;
H, 3.333; N, 4.20. Found. C, 53.93; H, 3.33; N, 4.23.
Dimethyl 3-Cyano-6-(4-N,N-dimethylamino)styryl-2-oxo-
2H-pyran-4-ylmalonate (7h). A mixture of 0.624 g (2.0
mmoles) of 3k, 0.66 g (5.0 mmoles) of 6a, 5.5 g (4.0 mmoles) of
potassium carbonate, and 20 ml of DMSO was stirred for 2
hours at room temperature. The reaction mixture was poured
into 200 ml of ice-water, and the whole was neutralized with
10% hydrochloric acid. The precipitates that appeared were
collected by filtration to give black solid. After air drying, the
product was recrystallized from methanol to give 0.667 g (1.68
mmoles, 84%) of black crystals, mp 200-202°; ir(potassium
bromide) ꢀ cm-1: 2215 (CN), 1755, 1740, 1720 (CO), 1600,
1500; uv(EtOH) ꢁ nm(log ꢂ): 278 (3.94), 320 (4.08), 539 (4.70);
Dimethyl 3-Cyano-6-(4-N,N-dimethylaminophenyl)-2-oxo-
2H-pyran-4-ylmalonate (7e).
A mixture of 0.508 g(2.0
mmoles) of 3i, 0.53 g (4.0 mmoles) of 6a, and 0.936 g (3.0
mmoles) of potassium carbonate in 20 ml of DMSO was stirred
for 2 hours at room temperature. The reaction mixture was
poured into 200 ml of ice-water and the whole was acidified
with 10% hydrochloric acid. The precipitate that appeared was
collected by filtration, washed with water, and recrystallized
from methanol to give 0.512 g(1.38 mmoles, 69% yield) of red
needles, mp 198-199°; ir(potassium bromide) ꢀ cm-1: 2220
(CN), 1745 (CO), 1502, 1210; uv(EtOH) ꢁ nm (log ꢂ): 292
(3.98), 488 (4.78); fluoresence (solid): Ex, 272 nm; Em, 610 nm;
RI=0.70; 1H nmr(CDCl3) ꢃ: 3.12 (s, 6, NMe2), 3.85 (s, 6, OMe),
4.99 (s, 1, -CH-), 6.69 (d, 2, 3', 5'-H, J=9.3 Hz), 6.89 (s, 1, 5-H),
7.79 (d, 2, 2', 6'-H, J=9.3 Hz); ms: m/z 371 (M++1, 21), 370 (M+,
93), 342 (11), 148 (28), 43 (100). Anal. Calcd for C19H18N2O6:
C, 61.62; H, 4.90; N, 7.56. Found. C, 61.47; H, 5.09; N, 7.61.
Diethyl 3-Cyano-6-(4-N,N-dimethylaminophenyl)-2-oxo-
2H-pyran-4-ylmalonate (7f). A mixture of 0.508 g(2.0 mmoles)
of 3i, 0.64 g (4.0 mmoles) of 6b, and 0.936 g (3.0 mmoles) of
potassium carbonate in 20 ml of DMSO was stirred for 2 hours
at room temperature. The reaction mixture was poured into 200
ml of ice-water and the whole was acidified with 10%
hydrochloric acid. The precipitate that appeared was collected
by filtration, washed with water, and re-crystallized from
methanol to give 0.589 g(1.48 mmoles, 74% yield) of orange red
needles, mp 194-198°; ir(potassium bromide) ꢀ cm-1: 2220
(CN), 1735 (CO), 1515; uv(EtOH) ꢁ nm(log ꢂ): 264 (4.24), 379
(4.56); fluoresence (solid): Ex, 272 nm; Em, 590 nm; RI=0.12;
1H nmr(CDCl3) ꢃ: 1.33 (t, 6, O-CH2-CH3, J=7.2 Hz), 3.11 (s, 6,
NMe2), 4.30 (m, 4, O-CH2-), 4.96 (s, 1, CH), 6.69 (d, 2, 3', 5'-H,
J=9.3 Hz), 6.91 (s, 1, 5-H), 7.79 (d, 2, 2', 6'-H, J=9.3 Hz); ms:
m/z 399 (M++1, 25), 398 (M+, 100), 148 (17), 43 (91). Anal.
Calcd for C21H22N2O6: C, 63.31; H, 5.57; N, 7.03. Found. C,
63.36; H, 5.57; N, 6.78.
Dimethyl 3-Cyano-6-thien-2-yl-2-oxo-2H-pyran-4-ylmalo-
nate (7g). A mixture of 0.498 g(2.0 mmoles) of 3j, 0.53 g (4.0
mmoles) of 6a, and 0.936 g (3.0 mmoles) of potassium
carbonate in 20 ml of DMSO was stirred for 2 hours at room
temperature. The reaction mixture was poured into 200 ml of
ice-water and the whole was acidified with 10% hydrochloric
acid. The precipitate that appeared was collected by filtration,
washed with water, and re-crystallized from methanol to give
0.552 g(1.66 mmoles, 83% yield) of yellow needles, mp 174-
175°. ir(potassium bromide) ꢀ cm-1: 2230 (CN), 1750, 1735
(CO), 1525; uv(EtOH) ꢁ nm(log ꢂ): 249 (4.23), 255 (4.25), 261
(4.21), 296 (4.35), 348 (4.40); fluoresence (solid): Ex, 267 nm;
Em, 527 nm; RI=2.47; 1H nmr(CDCl3) ꢃ: 3.86 (s, 6, OMe), 5.02
(s, 1, -CH-), 6.94 (s, 1, 5-H), 7.20 (dd, 1, 4'-H, J=3.9, 5.0 Hz),
1
fluoresence(CH2Cl2): Ex, 553 nm; Em, 620 nm. RI=0.44; H
nmr(CDCl3) ꢃ: 3.07 (s, 6, NMe2), 3.04 (s, 3, OMe), 4.95 (s, 1, -
CH-), 6.08 (s, 1, 5-H), 6.45 (d, 1, -CH, J=15.4 Hz), 6.67 (d, 2, 3',
5'-H, J=9.0 Hz), 7.44 (dd, 2, 2', 6'-H, J=2.2, 9.0 Hz), 7.63 (d, 1,
=CH, J=15.4 Hz); ms: m/z 397 (M++1, 16), 396 (M+, 65), 312
(27), 174 (6), 83 (6), 44 (100). Anal . Calcd for C21H20N2O6: C,
63.63; H, 5.09; N, 7.07. Found: C, 63.73, H, 4.98; N, 6.98.
Dimethyl 3-Methoxycarbonyl-2-oxo-6-phenyl-2H-pyran-4-
ylmalonate (7i). This compound (0.639 g, 1.76 mmoles) was
prepared in 88% yield from 5a (0.585 g, 2.0 mmoles) and 6a
(0.528 g, 4.0 mmoles) by the previous method [4d]. This
compound was recrystallized from methanol to give pale yellow
needle, mp 120-121°; ir(potassium bromide) ꢀ
(OH, br), 1750 (CO), 1730 (CO), 1710 (CO), 1625, 1540;
cm-1: 3450
max
uv(EtOH) ꢁ max nm(log ꢂ): 253 (4.26), 352 (4.27); fluorescence
1
(solid): Ex, 336 nm; Em, 470 nm; RI=4.16; H nmr(CDCl3) ꢃ:
3.82 (s,6,2xOMe), 3.94 (s, 3, OMe), 5.17 (s, 5, -CH-), 6.91 (s, 1,
5-H), 7.40-7.52 (m, 3, phenyl-H), 7.81-7.92 (m, 2, phenyl-H);
ms m/z : 361 (M++1, 2), 360 (M+, 12), 246 (85), 214 (38), 146
(35), 105 (100), 77 (47). Anal. Calcd. for C18H16O8: C, 60.00; H,
4.48. Found: C, 60.01; H, 4.46.
Diethyl 3-Methoxycarbonyl-2-oxo-6-phenyl-2H-pyran-4-
ylmalonate (7j). This compound (0.621 g, 1.6 mmoles) was
synthesized in 80% yield from 5a (0.585 g, 2.0 mmoles) and 6b
(0.641g, 4.0 mmoles) in manner similar to that described for the
preparation of 7i. An analytical sample was recrystallized from
ethanol to give colorless needles, mp 80-90°; ir(potassium
bromide) ꢀ max cm-1: 3450 (OH, br), 1760 (CO), 1730 (CO), 1720
(CO), 1620, 1540; uv(EtOH) ꢁ
nm(log ꢂ): 249 (4.30), 347
max
(4.36); fluorescence (solid): Ex, 341 nm; Em, 472 nm; RI=3.24;
1H nmr(CDCl3) ꢃ: 1.31 (t, 6, O-CH2-CH3, J=7.2 Hz), 3.95 (s, 3,
OMe), 4.26 (q, 2, O-CH2-, J=7.2Hz), 4.28 (q, 2, O-CH2-,
J=7.2Hz), 5.11 (s, 1, CH), 6.95 (s, 1, 5-H), 7.42-7.50 (m, 3,
phenyl-H), 7.86 (m, 2, phenyl-H); ms m/z: 388 (M+, 100), 360
(30), 314 (15), 283 (15), 242 (32). Anal. Calcd. for C20H20O8: C,
61.85; H, 5.19. Found: C, 62.06; H, 5.08.
Dimethyl 3-Methoxycarbonyl-6-(4-methoxyphenyl)-2-oxo-
2H-pyran-4-ylmalonate (7k). A mixture of 0.58 g (2.0 mmoles)
of 5b, 0.53 g (4.0 mmoles) of 6a, and 0.936 g (3.0 mmoles) of
potassium carbonate in 20 ml of DMSO was stirred for 2 hours
at room temperature. The reaction mixture was poured into 200
ml of ice-water and the whole was acidified with 10%
hydrochloric acid. The precipitate that appeared was collected
by filtration, washed with water, and re-crystallized from
methanol to give 0.392 g (0.972 mmole, 49% yield) of yellow
needles, mp 143-146°; ir(potassium bromide) ꢀ cm-1: 1750

Jan-Feb 2008
Reaction of 6-Aryl- or Styryl-4-methylsulfanyl-2-oxo-2H-pyrans with Active Methylene
273
(CO), 1512, 1542, 1516; uv(EtOH) ꢀ nm(log ꢁ): 264 (4.06), 380
(4.37); fluoresence (solid): Ex, 337 nm; Em, 477 nm; RI=6.74;
1H nmr(CDCl3) ꢂ: 3.83 (s, 3, OMe), 3.88 (s, 3, OMe), 3.93 (s, 3,
OMe), 5.22 (s, 1, -CH-), 6.79 (s, 1, CH), 6.97 (d, 2, 3', 5'-H,
J=9.3 Hz), 7.83 (d, 2, 2', 6'-H, J=9.3 Hz); ms: m/z 391 (M++1,
21), 390 (M+, 100), 362 (62), 330 (78), 135 (77), 77 (13). Anal.
Calcd for C19H18O9: C, 58.46; H, 4.65. Found. C, 58.37; H, 4.56.
Diethyl 3-Methoxycarbonyl-6-(4-methoxyphenyl)-2-oxo-
2H-pyran-4-ylmalonate (7l). A mixture of 0.584 g (2.0
mmoles) of 5b, 0.64 g (4.0 mmoles) of 6b, and 0.936 g (3.0
mmoles) of potassium carbonate in 20 ml of DMSO was stirred
for 2 hours at room temperature. The reaction mixture was
poured into 200 ml of ice-water and the whole was acidified
with 10% hydrochloric acid. The precipitate that appeared was
collected by filtration, washed with water, and recrystallized
from ethanol to give 0.598 g (1.58 mmoles, 79% yield) of
yellow needles, mp 89-92°; ir(potassium bromide) ꢃ cm-1: 1750,
1730 (CO), 1538, 1515; uv(EtOH) ꢀ nm(log ꢁ): 261 (3.75), 381
(4.25); fluoresence (solid): Ex, 332 nm; Em, 479 nm; RI=4.20;
1H nmr(CDCl3) ꢂ: 1.31 (t, 6, O-CH2-CH3, J=7.1 Hz), 3.88 (s, 6,
OMe), 3.93 (s, 3, OMe), 4.28 (m, 4, O-CH2-), 5.15 (s, 1, CH),
6.82 (s, 1, 5-H), 6.97 (d, 2, 3', 5'-H, J=9.3 Hz), 7.82 (d, 2, 2', 6'-
H, J=9.3 Hz); ms: m/z 418 (M+, 100), 390 (32), 272 (11), 135
(71), 45 (100). Anal. Calcd for C21H22O9: C, 60.26; H, 5.30.
Found. C, 60.31; H, 5.28.
284 (15), 281 (11), 280 (38), 253 (13), 252 (58), 105 (64), 77
(27). Anal. Calcd. for C17H13NO5: C, 65.59; H, 4.21; N, 4.50.
Found: C, 65.34; H, 4.29; N, 4.44.
Methyl 8-Hydroxy-3-(4-methoxyphenyl)-6-methyl-1-oxo-
1H-pyrano[3,4-c]pyridine-5-carboxylate (8b). This compound
(0.203 g, 0.59 mmole) was synthesized in 30% yield from 3c
(0.547 g, 2.0 mmoles), 6c (0.464 g, 4.0 mmoles), and K2CO3
(0.691 g, 5.0 mmoles) to that described for 8a. This compound
was recrystallized from methanol to give pale yellow needles,
mp 296-297°; ir(potassium bromide) ꢃ max cm-1: 3450 (OH, br),
1755 (CO), 1706 (CO), 1648, 1635, 1580; uv(EtOH) ꢀ
nm(log ꢁ): 276 (4.48), 366 (4.60); fluorescence (solid): Ex, 335
max
1
nm; Em, 468 nm; RI=3.93; H nmr(CDCl3) ꢂ: 2.39 (s, 3, 6-Me),
3.85 (s, 3, OMe), 3.90 (s, 3, OMe), 7.09 (m, 3, CH), 7.84 (m, 2,
3', 5'-H), 12.3 (s, 1, OH); ms m/z: 342 (M++1, 21), 341 (M+,
100), 313 (36), 135 (33), 78 (27). Anal. Calcd. for C18H15NO6: C,
63.34; H, 4.43; N, 4.10. Found: C, 63.14; H, 4.29; N, 4.04.
Ethyl 8-Hydroxy-6-methyl-1-oxo-3-phenyl-1H-pyrano[3,4-
c]pyridine-5-carboxylate (8c). This compound (0.452 g, 1.4
mmoles) was synthesized in 70% yield from 3a (0.487 g, 2.0
mmoles), ethyl acetoacetate (6d)(0.691 g, 5.0 mmoles), and
potassium carbonate (0.691 g, 5.0 mmoles) to that described for
8a. This compound was recrystallized from ethanol to give
colorless needles, mp 295-296°; ir(potassium bromide) ꢃ
max
cm-1: 3450 (OH, br), 1775 (CO), 1720 (CO), 1650, 1625, 1580;
uv(EtOH) ꢀ max nm(log ꢁ): 349 (4.25); fluorescence (solid): Ex,
340 nm; Em, 460 nm; RI=3.99; 1H nmr(CDCl3) ꢂ: 1.34 (t, 3, O-
CH2-CH3, J=7.0 Hz), 2.42 (s, 3, Me), 4.38 (q, 2, O-CH2-, J=7.0
Hz), 7.26 (s, 1, CH), 7.58 (m, 3, 3', 4', 5'-H), 7.87 (m, 2, 2', 6'-
H), 12.20 (s, 1, OH); ms m/z: 326 (M++1, 20), 325 (M+, 100),
280 (39), 252 (31), 105 (50). Anal. Calcd. for C18H15NO5: C,
66.46; H, 4.65; N, 4.31. Found: C, 66.39; H, 4.56; N, 4.31.
Ethyl 8-Hydroxy-3-(4-methoxyphenyl)-6-methyl-1-oxo-1H-
pyrano[3,4-c]pyridine-5-carboxylate (8d). This compound
(0.221 g, 0.622 mmole) was synthesized in 31% yield from 3c
(0.547 g, 2.0 mmoles), 6d (0.521 g, 4.0 mmoles), and potassium
carbonate (0.691 g, 5.0 mmoles) to that described for 7a. This
compound was recrystallized from methanol to give pale yellow
Dimethyl 6-Benzo[1,3]dioxol-5-yl-3-methoxy-carbonyl-2-
oxo-2H-pyran-4-ylmalonate (7m). This compound (0.429 g,
1.06 mmoles) was synthesized in 53% yield from 5c (0.673 g,
2.0 mmoles) and 6a (0.528g, 4 mmoles) in manner similar to
that described for the preparation of 7i. An analytical sample
was recrystallized from methanol to give yellow needles, mp
143-146°; ir(potassium bromide) ꢃ
(CO), 1680 (CO), 1620, 1600; uv(EtOH) ꢀ
cm-1: 1780 (CO), 1735
max
nm(log ꢁ): 244
max
(4.27), 249 (4.28), 254 (4.29), 383 (4.36); fluorescence (solid):
Ex, 331 nm; Em, 504 nm; RI=0.87; 1H nmr(CDCl3) ꢂ: 3.82 (s, 6,
2xOMe), 3.96 (s, 3, OMe), 5.20 (s, 1, -CH-), 6.06 (s, 2, O-CH2-
O), 6.76 (s, 1, 5-H), 6.89 (d, 1, J=8.3 Hz, 5'-H), 7.30 (d, 1, 2'-H,
J=1.8 Hz), 7.45 (dd, 1, 6'-H, J=1.8, 8.3 Hz); ms m/z: 404 (M+,
100), 376 (41), 373 (22), 344 (43), 341 (21), 290 (43)0, 258
(46), 190 (44), 149 (93). Anal. Calcd. for C19H16O10: C, 56.44; H,
3.99. Found: C, 56.68; H, 3.79.
needles, mp 287-288°; ir(potassium bromide) ꢃ
cm-1: 3450
max
(OH, br), 2220 (CN), 1750 (CO), 1515; uv(EtOH) ꢀ max nm(log
ꢁ): 247 (4.05), 190 (4.30), 345 (4.34), 372 (4.36); fluorescence
1
Methyl 8-Hydroxy-6-methyl-1-oxo-3-phenyl-1H-pyrano-
[3,4-c]pyridine-5-carboxylate (8a). Potassium carbonate (0.691
g, 5.0 mmoles) was added to the soulution of 3a (0.487 g, 2.0
mmoles) and methyl acetoacetate (6c)(0.464 g, 4.0 mmoles) in
20 ml of DMSO. After stirring at room temperature for 2 hours,
the reaction mixture was poured into 200 ml of ice water and
then acidified with 10% hydrochloric acid. The caramel oil
product that appeared was collected by decantation and washed
several tomes with water. This crude product was dissolved in
100 ml of methanol and this methanol solution was refluxed for
2 hours. After removal of the solvent by rotary evaporation, the
residue was crystallized by treating with 10~20 ml of methanol.
The resulting precipitate was collected by filtration and
recrystallized from methanol to give 0.324 g (1.04 mmoles) of
8a as pale yellow crystals, mp >300°, in 52% yield. ir(potassium
(solid): Ex, 339 nm; Em, 496 nm; RI=2.45; H nmr(CDCl3) ꢂ:
1.34 (t, 3, O-CH2-CH3, J=7.3 Hz), 2.40 (s, 3, Me), 3.85 (s, 3,
OMe), 4.38 (q, 2, O-CH2-CH3, J=7.3 Hz), 7.11 (d, 2, 3', 5'-H,
J=8.8Hz), 7.13 (s, 1, CH), 7.83 (d, 2, 2', 6'-H, J=8.8 Hz), 12.25
(s, 1, OH); ms m/z: 356 (M++1, 10), 355 (M+, 45), 355 (16), 313
(15), 135 (35). Anal. Calcd. for C19H17NO6: C, 64.22; H, 4.82; N,
3.94. Found: C, 64.20; H, 4.71; N, 3.80.
Ethyl 8-Hydroxy-3-(2,4-dimethoxyphenyl)-6-methyl-1-oxo-
1H-pyrano[3,4-c]pyridine-5-carboxylate (8e). This compound
(0.234 g, 0.61 mmole) was synthesized in 31% yield from 3e
(0.607 g, 2.0 mmoles), 6d (0.521 g, 4.0 mmoles), and potassium
carbonate (0.691 g, 5.0 mmoles) to that described for 8a. This
compound was recrystallized from ethanol to give pale yellow
needles, mp 298-299°; ir(Potassium bromide) ꢃ
cm-1: 3450
max
(OH, br), 1755 (CO), 1718 (CO), 1640, 1610, 1579, 1560, 1530,
1505; uv(EtOH) ꢀ nm(log ꢁ): 274 (4.42), 377 (4.51);
bromide) ꢃ
cm-1: 3450 (OH, br), 1755 (CO), 1710 (CO),
max
max
1
1648, 1620, 1585, 1530; uv(EtOH) ꢀ max nm(log ꢁ): 268 (5.23),
346 (5.23); fluorescence (solid): Ex, 345 nm; Em, 462 nm;
fluorescence (solid): Ex, 336 nm; Em, 490 nm; RI=4.88; H
nmr(CDCl3) ꢂ: 1.34 (t, 3, O-CH2-CH3, J=7.4 Hz), 2.37 (s, 3,
Me), 3.86 (s, 3, OMe), 3.92 (s, 3, OMe), 4.36 (q, 2, 1/2O-CH2-
CH3, J=7.4 Hz), 6.73 (d, 1, 3'-H, J=1.0 Hz), 7.76 (d, 1, 6'-H,
J=9.4 Hz), 12.20 (brs, 1, OH); ms m/z: 386 (M++1, 23), 385 (M+,
1
RI=1.23; H nmr(CDCl3+CF3COOH) ꢂ: 2.62 (s, 3, 6-Me), 4.03
(s, 3, OMe), 7.41 (s, 1, 4-H), 7.44-7.59 (m, 3, phenyl-H), 7.85-
7.92 (m, 2, phenyl-H); ms m/z: 312 (M++1, 40), 311 (M+, 100),

274
N. Mizuyama, Y. Murakami, T. Nakatani, K. Kuronita, S. Kohra, K. Ueda, K. Hiraoka, Y. Tominaga
Vol 45
100), 340 (13), 285 (10), 165(33). Anal. Calcd. for C20H19NO7:
C, 62.33; H, 4.97; N, 3.63. Found: C, 62.45; H, 4.94; N, 3.82.
Ethyl 8-Hydroxy-3-(3,4-dimethoxyphenyl)-6-methyl-1-oxo-
1H-pyrano[3,4-c]pyridine-5-carboxylate (8f). This compound
(0.217 g, 0.56 mmole) was synthesized in 28% yield from 3e
(0.607 g, 2.0 mmoles), 6d (0.521 g, 4.0 mmoles), and potassium
carbonate (0.691 g, 5.0 mmoles) to that described for 8a. This
compound was recrystallized from ethanol to give yellow
stirring at room temperature for 2 hours. The reaction mixture
was poured into 200 ml of ice water and then acidified with 10%
hydrochloric acid. This product was recrystallized with methanol
to give 0.274 g(1.1 mmoles, 55% yield) of pale yellow crystals,
mp >260°; ir(potassium bromide) ꢀ max cm-1: 3500 (OH, br), 1750
(CO), 1735 (CO), 1640, 1600; uv(EtOH) ꢁ
nm(log ꢂ): 260
max
(4.19), 347 (4.39); fluorescence (solid): Ex, 319 nm; Em, 468 nm;
RI=0.22; 1H nmr(CDCl3) ꢃ: 2.59 (s, 3, Me), 6.67 (s, 1, 5-H), 6.97
(s, 1, 4-H), 7.57 (m, 3, 3',4', 5'-H), 7.90 (m, 2, 2', 6'-H); ms m/z:
254 (M++1, 19), 253 (M+, 100), 225 (24), 176 (25), 105 (13), 77
(18). Anal. Calcd. for C15H11NO3(C30H22N2O6ꢀH2O): C, 68.70;
H, 4.61; N, 5.34. Found: C, 68.77; H, 4.56; N, 5.24.
needles, mp 303-304°; ir(potassium bromide) ꢀ
(OH, br), 1775 (CO), 1718 (CO), 1640, 1620, 1570; uv(EtOH) ꢁ
cm-1: 3450
max
nm(log ꢂ): 269 (4.38), 273 (4.43); fluorescence (solid): Ex,
max
343 nm; Em, 495 nm; RI=2.08; 1H nmr(CDCl3) ꢃ: 1.35 (t, 3/2H,
1/2O-CH2-CH3, J=7.1 Hz), 1.36(t, 3/2H, 1/2O-CH2-CH3, J=7.1
Hz), 2.46 (s, 3/2H, 1/2Me), 2.50 (s, 3/2H, 1/2Me), 3.85 (s, 3,
OMe), 3.86 (s, 3, OMe), 4.40 (q, 2/2H, 1/2O-CH2-CH3, J=7.1
Hz), 4.42 (q, 2/2H, 1/2O-CH2-CH3, J=7.1 Hz), 7.10-7.17 (m, 2,
5, 5'-H), 7.33 (d, 1/2H, 2'-H, J=2.0 Hz), 7.38 (d, 1/2H, 2'-H,
J=2.0 Hz), 7.47 (dd, 1/2H, 6'-H, J=2.0, 9.0 Hz), 7.58 (dd, 1/2H,
6'-H, J=2.0, 9.0 Hz), 12.25 (s, 1/2H, OH); ms m/z: 386 (M++1,
58), 385 (M+, 100), 357 (11), 165 (36), 44 (20). Anal. Calcd. for
C20H19NO7: C, 62.33; H, 4.97; N, 3.63. Found: C, 62.02; H,
4.93; N, 3.30.
8-Hydroxy-6-methyl-3-(4-methoxyphenyl)-1H-pyrano[3,4-
c]pyridine-1-one (8j). This compound (0.470 g, 1.66 mmoles
was prepared in 83% yeld from 3b (0.547 g, 2.0 mmoles) and 6f
(0.400g, 4.0 mmoles) in a manner similar to that described from
the preparation of 8a. An analytical sample was recrystallized
from methanol to give pale yellow needles mp >323°;
ir(potassium bromide) ꢀꢀ
cm-1: 3450 (OH, br), 1760 (CO),
max
1590, 1510; uv(EtOH) ꢁ max nm(log ꢂ): 271 (4.34), 363 (4.57);
1
fluorescence (solid): Ex, 337 nm; Em, 495 nm; RI=0.40; H
nmr(CDCl3) ꢃ: 2.25 (s, 3, Me), 3.84 (s, 3, OMe), 6.12 (s, 1, 5-
H), 7.03 (s, 1, 4-H), 7.10 (d, 2, J=8.8Hz, 3', 5'-H), 7.86 (d, 2,
J=8.8 Hz, 2', 6'-H); ms m/z: 284 (M++1, 18), 283 (M+, 100), 255
(70), 212 (18), 135 (16), 127 (14), 77 (12). Anal. Calcd. for
C16H13NO4: C, 67.84; H, 4.63; N, 4.94. Found: C, 67.55; H,
4.65; N, 4.89.
Ethyl 8-Hydroxy-3-(4-N,N-dimethylaminophenyl)-6-methyl-
1-oxo-1H-pyrano[3,4-c]pyridine-5-carboxylate (8g). This
compound (0.066 g, 0.18 mmole) was synthesized in 9% yield
from 3g (0.573 g, 2.0 mmoles), 6d (0.521 g, 4.0 mmoles), and
potassium carbonate (0.691 g, 5.0 mmoles) to that described for
8a. This compound was recrystallized from ethanol to give
yellow needles, mp 298-299°; ir(potassium bromide) ꢀ max cm-1:
3450 (OH, br), 1755 (CO), 1700 (CO), 1640, 1600, 1570, 1520;
The reaction of 6-Aryl-3-cyano-2H-pyran-2-ones (3a-c, e)
with active methylene compounds (6c,d,f). Potassium
carbonate (0.691 g, 5.0 mmoles) was added to the soulution of
3a (0.487 g, 2.0 mmoles) and 6c (0.464 g, 4.0 mmoles) in 20 ml
of DMSO. This mixture was stirring at room temperature for 2
hours, poured into 200 mL of ice water and then acidified with
10% hydrochloric acid. The product that appeared was collected
by decantation and washed several times with water. The crude
product was dissolved in a solution of 150 ml of ethanol and 10
ml of concentrated-HCl solution. The solution was refluxed for
30 min. After removal of the solvent by rotary evaporation, the
residue was crystallized by treatment with 10~20 ml of ethanol.
The resulting precipitate was collected by filtration and washed
with 50 mL of dichloromethane. This compound (8a) was
recrystallized from DMF to give coloreless needles, mp >300°.
Dichloromethane in the above filtrate was removed by rotary
evaporation to give 10a which was easily purified by
recrystallization with ethanol. In the reaction of 3a with 6d
under similar reaction conditions, a separable mixture of 8c, 9a,
and 10b was obtained, which was easily separated by
recrystallization with ethanol. Though compound 9a was not so
soluble in ethanol, compound 10b was easily solved in ethanol.
Compound 9a was recrystallized from DMF to give pure
compound, mp 152-155°, for elemental analysis. Compound 10b
was easily recrystallized from ethanol to give pale yellow
needles, mp 145-147°. The yields of each products were shown
in Table 4.
uv(EtOH) ꢁ
nm(log ꢂ): 270 (4.32), 305 (4.16), 434 (4.61);
max
fluorescence (solid): Ex, 331 nm; Em, 540 nm; RI=0.36;
fluorescence (CH2Cl2): Ex, 441 nm; Em, 515 nm; 1H
nmr(CDCl3) ꢃ: 1.34 (t, 3, O-CH2-CH3, J=7.0 Hz), 2.37 (s, 3,
Me), 3.03 (s, 6, NMe2), 4.37 (q, 2, O-CH2-CH3, J=7.0 Hz), 6.82
(d, 2, 3', 5'-H, J=9.1Hz), 6.99 (s, 1, 5-H), 7.70 (d, 2, 2', 6'-H,
J=9.1 Hz), 12.10 (brs, 1/2H, 1/2OH); ms m/z: 369 (M++1, 25),
368 (M+, 100), 340 (17), 148 (28), 44 (56). Anal. Calcd. for
C20H20N2O5: C, 65.21; H, 5.47; N, 7.60. Found: C, 65.24; H,
5.41; N, 7.48.
8-Hydroxy-3-(4-methoxyphenyl)-6-methyl-1-oxo-5-tolyl-
methyl-1H-pyrano[3,4-c]pyridine (8h). This compound (0.192
g, 0.44 mmole) was synthesized in 22% yield from 3b (0.547 g,
2.0 mmoles), 4-toluenesulfonylacetoacetate(6e) (0.691 g, 5.0
mmoles), and potassium carbonate (0.691 g, 5.0 mmoles) to that
described for 8a. This compound was recrystallized from
ethanol to give pale yellow needles, mp 260-270°; ir(potassium
bromide) ꢄ
1555, 1505; uv(EtOH) ꢁ
cm-1: 3450 (OH, br), 1760 (CO), 1640, 1600,
max
nm(log ꢂ): 295 (4.40), 301 (4.40),
351 (4.06), 372 (4.15); fluorescence (solid): Ex, 345 nm; Em,
max
1
493 nm; RI=3.40; H nmr(CDCl3) ꢃ: 2.43 (s, 3, 6-Me), 2.91 (s,
3, p-Me), 3.93 (s, 3, OMe), 7.03 (d, 2, 3', 5'-H, J=9.1 Hz), 7.38
(d, 1, 2'', 6''-H, J=8.3 Hz), 7.80 (d, 1, 2', 6'-H, J=9.1 Hz), 7.83 (d,
1, 3'', 5''-H, J=8.3 Hz), 8.05 (s, 1, 5-H); ms m/z: 438 (M++1, 18),
437 (M+, 51), 372 (13), 345 (31), 344 (13), 273 (25), 239 (16),
238 (55), 237 (29), 140 (51), 135 (100), 134 (25), 91 (13), 77
(12), 57 (12). Anal. Calcd. for C23H19NO6S: C, 63.15; H, 4.38;
N, 3.20. Found: C, 63.02; H, 4.19; N, 3.02.
8-Hydroxy-6-methyl-3-phenyl-1H-pyrano[3,4-c]-pyridin-1-
one (8i). Potassium carbonate (0.691 g, 5.0 mmoles) was added to
the soulution of 3a (0.487 g, 2.0 mmoles) and acetylacetone (6f)
(0.400 g, 4.0 mmoles) in 20 ml of DMSO. This mixture was
Ethyl 1,8-Dioxo-3-methyl-6-phenyl-1H,8H-pyrano-[3,4-c]-
pyran-4-carboxylate (9a). This compound (0.072g, 0.22
mmole) was obtained 11 % yield by the above method from 3a
(0.487 g, 2.0 mmoles) and 6d (0.521 g, 4.0 mmoles) to give pale
yellow leaflets mp 152-155°; ir(potassium bromide) ꢀ max cm-1:
1780 (CO), 1705 (CO), 1623, 1585, 1575; uv(EtOH) ꢁ
nm(log ꢂ): 261 (4.45), 334 (4.39), 359 (4.30); fluorescence
max
1
(solid): Ex, 337 nm; Em, 457 nm; RI=0.82; H nmr(CDCl3) ꢃ:

Jan-Feb 2008
Reaction of 6-Aryl- or Styryl-4-methylsulfanyl-2-oxo-2H-pyrans with Active Methylene
275
1.46(t, 3, O-CH2-CH3, J=7.1 Hz), 2.56 (s, 3, Me), 4.48 (q, 2, O-
CH2-CH3, J=7.1 Hz), 4.80 (s, 2, CH2), 7.53 (m, 3, 3',4', 5'-H),
7.92 (m, 2, 2', 6'-H); ms m/z: 327 (M++1, 16), 326 (M+, 84), 298
(22), 283 (22), 105 (100), 77 (57). Anal. Calcd. for C18H14NO6:
C, 66.26; H, 4.32. Found: C, 66.15; H, 4.17.
O-CH2-CH3, J=7.1 Hz), 7.00 (d, 2, 3', 5'-H, J=9.1 Hz), 7.04 (s, 1,
5-H), 7.48-7.60 (m, 3, 3'', 4'', 5''-H), 7.92 (d, 2, 2', 6'-H, J=9.1
Hz); ms m/z: 419 (M++1, 5), 418 (M+, 20), 314 (20), 313 (100),
285 (17), 135 (69), 105 (14), 77 (25), 44 (15). Anal. Calcd. for
C24H18O7: C, 68.90; H, 4.34. Found: C, 68.73; H, 4.17.
Ethyl 1,8-Dioxo-6-(4-methoxyphenyl)-3-methyl-1H,8H-
pyrano[3,4-c]pyran-4-carboxylate (9b). This compound (0.152
g, 0.42 mmole) was prepared in 21% yield from 3c (0.547 g, 2.0
mmoles) and 6d (0.521 g, 4.0 mmoles) in manner similar to that
described for the preparation of 9a. An analytical sample was
recrystallized with DMF to give pale yellow needles, mp 215-
219°; ir(potassium bromide) ꢀ max cm-1: 1800 (CO), 1785 (CO),
1710 (CO), 1580, 1560; uv(EtOH) ꢁ max nm(log ꢂ): 277 (4.26),
343 (4.31), 395 (4.43); fluorescence (solid): Ex, 343 nm; Em,
Methyl 3-Cyano-2-oxo-6-phenyl-2H-pyran-4-ylacetate (10a).
This compound (0.323 g 0.120 mmole) was separated by th
recrystallization with ethanol from a mixture of 8a and 10a
which were obtained by the reaction of 3a (0.487 g, 2.0 mmoles)
and 6c (0.464 g, 4.0 mmoles). An analytical sample was
recrystallized from ethanol to give pale yellow leaflets, mp 196-
201°; ir(potassium bromide) ꢀ max cm-1: 2220 (CN), 1740 (CO),
1720 (CO), 1620, 1540; uv(EtOH) ꢁ max nm(log ꢂ): 290 (4.11),
370 (4.22); Fluorescence (solid): Ex, 348 nm; Em, 474 nm;
RI=1.00; 1H nmr(CDCl3) ꢃ: 3.81 (s, 3, OMe), 3.84 (s, 2, -CH2-),
6.87 (s, 1, 5-H), 7.54 (m, 3, 3', 4', 5'-H), 7.87 (m, 2, 2', 6'-H); ms
m/z: 270 (M++1, 14), 269 (M+, 84), 241 (25), 154 (20), 127 (20),
105 (100), 77 (62). Anal. Calcd. for C15H11NO4: C, 66.91; H,
4.12; N, 5.20. Found: C, 66.78; H, 3.85; N, 5.17.
1
472 nm; RI=1.38; H nmr(CDCl3) ꢃ: 1.45 (t, 3, O-CH2-CH3,
J=7.1 Hz), 2.54 (s, 3, Me), 3.90 (s, 3, OMe), 4.87 (q, 2, O-CH2-
CH3, J=7.1 Hz), 7.00 (d, 2, 3', 5'-H, J=9.1Hz), 7.26 (s, 1, 5-H),
7.90 (d, 2, 2', 6'-H, J=9.1 Hz); ms m/z: 356 (M+, 87), 328 (22),
311 (11), 135 (100), 77 (13), 43 (24). Anal. Calcd. for C19H16O7:
C, 64.04; H, 4.53. Found: C, 64.02; H, 4.40.
Ethyl 6-(3,4-Dimethoxyphenyl)-1,8-dioxo-3-methyl-1H,
8H-pyrano[3,4-c]pyran-4-carboxylate (9c). This compound
(0.108 g, 0.28 mmole) was prepared in 14% yield from 3e
(0.607 g, 2.0 mmoles) and ethyl acetoacetate(6d) (0.521 g, 4.0
mmoles) in a manner similar to that described for the
preparation of 9a. An analytical sample was recrystallized from
DMF to give yellow crystals, mp 213-217°; ir(potassium
bromide) ꢀ max cm-1: 1783 (CO), 1720 (CO), 1579; uv(EtOH) ꢁ
Ethyl 3-Cyano-2-oxo-6-phenyl-2H-pyran-4-ylacetate (10b).
This compound (0.391 g, 1.38 mmoles) was separated from a
mixture of 8c, 9a and 10bwhich was prepared from 3a (0.487 g,
2.0 mmoles) and 6d (0.769 g, 4.0 mmoles). An analytical
sample was recrystallized from ethanol to give pale yellow
leaflets, mp 145-147°; ir(potassium bromide) ꢀ
(CN), 1740 (CO), 1720 (CO), 1620, 1530; uv(EtOH) ꢁ
cm-1: 2220
max
max
nm(log ꢂ): 291 (4.71), 359 (4.32); fluorescence (solid): Ex, 322
nm; Em, 482 nm; RI=8.72; 1H nmr(CDCl3) ꢃ: 1.33 (t, 3, O-CH2-
CH3, J=7.3 Hz), 3.82 (s, 2, -CH2-), 4.26 (q, 2, O-CH2-CH3, J=7.3
Hz), 6.88 (s, 1, 5-H), 7.54 (m, 3, 3', 4', 5'-H), 7.87 (m, 2, 2', 6'-
H); ms m/z: 284 (M++1, 18), 283 (M+, 100), 211 (29), 183 (28),
105 (87), 77 (65). Anal. Calcd. for C16H13NO4: C, 67.84; H,
4.63; N, 4.94. Found: C, 67.84; H, 4.57; N, 5.15.
nm(log ꢂ): 279 (4.44), 347 (4.36), 404 (4.48); fluorescence
1
max
(solid): Ex, 341 nm; Em, 542 nm; RI=0.14; H nmr(CDCl3) ꢃ:
1.48 (t, 3, O-CH2-CH3, J=7.1 Hz), 2.55 (s, 3, Me), 3.97 (s, 3,
OMe), 3.98 (s, 3, OMe), 4.47 (q, 2, O-CH2-CH3, J=7.1 Hz), 6.96
(d, 1, 5'-H, J=8.5 Hz), 7.17 (s, 1, 5-H), 7.41 (d, 1, 2'-H, J=2.2
Hz), 7.53 (dd, 1, 6'-H, J=2.2, 8.5Hz); ms m/z: 387 (M++1, 22),
386 (M+, 100), 165 (60), 135 (11), 97 (17), 85 (14). Anal. Calcd.
for C20H18O8: C, 62.17; H, 4.70. Found: C, 61.91; H, 4.61.
Ethyl 3-Cyano-6-(4-methoxyphenyl)-2-oxo-2H-pyran-4-
ylacetate (10c). This compound (0.269 g 0.86 mmole) was
separated from a mixture of 8d, 9b and 10c which was prepared
from 3b (0.547 g, 2.0 mmoles) and 6d(0.769 g, 4 mmoles). An
analytical sample was recrystallized from ethanol to give yellow
Ethyl 1,8-Dioxo-3,6-diphenyl-1H,8H-pyrano[3,4-c]-pyran-
4-carboxylate (9d). This compound (0.085 g, 0.22 mmole) was
prepared in 11% yield from 3a (0.487 g, 2.0 mmoles) and 6g
(0.769 g, 4.0 mmoles) in a manner simila to tha described for the
preparation 9a. An analytical sample was recrystallized from
DMF to give pale yellow needles, mp 195-196°; ir(potassium
bromide) ꢀ max cm-1: 1793 (CO), 1778 (CO), 1728 (CO), 1625,
1585, 1563; uv(EtOH) ꢁ max nm(log ꢂ): 276 (4.25), 354 (4.40);
leaflets, mp 172-173°; ir(potassium bromide) ꢀ
cm-1: 2220
max
(CN), 1740 (CO), 1720 (CO), 1620, 1610, 1540, 1515;
uv(EtOH) ꢁ nm(log ꢂ): 291 (4.80), 329 (4.70), 359 (4.54);
max
1
fluorescence (solid): Ex, 342 nm; Em, 513 nm; RI=2.32; H
nmr(CDCl3) ꢃ: 1.32 (t, 3, O-CH2-CH3, J=7.3 Hz), 3.79 (s, 2, -
CH2-), 3.90 (s, 3, OMe), 4.25 (q, 2, O-CH2-CH, J=7.3 Hz3), 6.76
(s, 1, 5-H), 7.99 (d, 2, 3', 5'-H, J=9.1 Hz), 7.93 (d, 2, 2', 6'-H,
J=9.1 Hz); ms m/z: 314 (M++1, 19), 313 (M+, 100), 285 (14),
135 (22). Anal. Calcd. for C17H15NO5: C, 65.17; H, 4.83; N,
4.47. Found: C, 65.39; H, 4.66; N, 4.44.
1
fluorescence (solid): Ex, 337 nm; Em, 476 nm; RI=0.62; H
nmr(CDCl3) ꢃ: 0.99 (t, 3, O-CH2-CH3, J=7.1 Hz), 4.17 (q, 2, O-
CH2-CH3, J=7.1 Hz), 7.17 (s, 1, 5-H), 7.43-7.60 (m, 6, phenyl-
H), 7.65 (m, 2, 2', 6'-H), 7.95 (m, 2, 2'', 6''-H); ms m/z: 389
(M++1, 14), 388 (M+, 55), 360 (23), 255 (11), 105 (100), 77 (55).
Anal. Calcd. for C23H16O6: C, 71.13; H, 4.15. Found: C, 71.06;
H, 4.06.
Ethyl 3-Cyano-6-(3,4-dimethoxyphenyl)-2-oxo-2H-pyran-
4-ylacetate (10d). This compound (0.309 g, 0.90 mmole) was
separated in 45% yield from a mixture of 9c and 10d which was
prepared from 3e (0.607 g, 2.0 mmoles) and 6d (0.521 g, 4.0
mmoles). An analytical sample was recrystallized from ethanol
to give orange needles, mp 165-166°; ir(potassium bromide) ꢀ
Ethyl 1,8-Dioxo-6-(4-methoxyphenyl)-3-phenyl-1H,8H-
pyrano[3,4-c]pyran-4-carboxylate (9e). This compound (0.117
g, 0.28 mmole) was prepared in 14% yield from 9b (0.547 g, 2.0
mmoles) and ethyl benzoylacetate (6g) (0.769 g, 4.0 mmoles) in
a manner similar to that described for the preparation of 9a. An
analytical sample was recrystallized from DMF to give yellow
cm-1: 2220 (CN), 1740 (CO), 1718 (CO), 1610, 1600, 1505;
max
uv(EtOH) ꢁ
nm(log ꢂ): 292 (5.10), 231 (5.05), 386 (4.91);
max
fluorescence (solid): Ex, 347 nm; Em, 567 nm; RI=0.15; 1H
nmr(CDCl3) ꢃ: 1.33 (t, 3, O-CH2-CH3, J=7.0 Hz), 3.80 (s, 2, -
CH2-), 4.26 (q, 2, O-CH2-CH3, J=7.0 Hz), 6.78 (s, 1, 5-H), 6.95
(d, 1, 5'-H, J=8.8 Hz), 7.35 (d, 1, 2'-H, J=2.4 Hz), 7.51 (dd, 1, 6'-
H, J=2.4 Hz); ms m/z: 344 (M++1, 20), 343 (M+, 100), 256 (20),
165 (19), 129 (11), 73 (13), 69 (16), 57 (14). Anal. Calcd. for
needles, mp 212-213°; ir(potassium bromide) ꢀ
cm-1: 1790
max
(CO), 1718 (CO), 1605 (CO), 1585, 1565, 1505; uv(EtOH) ꢁ max
nm(log ꢂ): 283 (4.59), 359 (4.61), 400 (4.54); fluorescence
1
(solid): Ex, 337 nm; Em, 531 nm; RI=0.51; H nmr(CDCl3) ꢃ:
1.01 (t, 3, O-CH2-CH3, J=7.1 Hz), 3.90 (s, 3, OMe), 4.16 (q, 2,

276
N. Mizuyama, Y. Murakami, T. Nakatani, K. Kuronita, S. Kohra, K. Ueda, K. Hiraoka, Y. Tominaga
Vol 45
C18H17NO6: C, 62.97; H, 4.99; N, 4.08. Found: C, 62.73; H,
5.02; N, 3.89.
(CN), 1656, 1560, 1543, 1286; uv(EtOH) ꢁ max nm(log ꢂ):252
(4.08), 306 (4.04), 252 (4.56) ; fluorescence (solid): Ex, 347
nm; Em, 430 nm; RI=0.25; 1H nmr(CDCl3) ꢃ: 2.57 (s, 3,
SMe), 5.26 (brs, 2, NH2), 6.56 (s, 1, 6-H), 7.48 (m, 5,
phenyl-H); ms m/z: 266 (M++1, 24), 265 (M+, 100), 232 (20),
206 (12).
Ethyl 3-Cyano-6-(4-N,N-dimethylaminophenyl)-2-oxo-2H-
pyran-4-ylacetate (10e). This compound (0.013 g, 0.04 mmole)
was separated in 2% yield from a mixture of 8g and 10e which
was prepared from 3g (0.573 g, 2.0 mmoles) and ethyl
acetoacetate(6d) (0.521 g, 4.0 mmoles). An analytical sample
was recycclazed from ethanol to give red needles, mp 174-178°;
ir(potassium bromide) ꢀ max cm-1: 2220 (CN), 1725 (CO), 1700
3-Amino-2'-methoxy-5-methylsulfanyl-biphenyl-2,4-dicarbo-
nitrile (11b). This compound (1.084 g, 3.81 mmoles) was
prepared in 76% yield from 3b (1.37 g, 5.0 mmoles) and 6h
(0.506 g, 10.0 mmoles) in a manner similar to that described for
the preparation of 11a. An analytical sample was re-crystallized
from DMF to give colorless needles, mp 216-219°; ir(potassium
bromide) ꢀ max cm-1: 3465 (NH), 3352 (NH), 3231, 2221 (CN),
(CO), 1600, 1550; uv(EtOH) ꢁ
nm(log ꢂ): 285 (4.20), 325
max
(3.89), 471 (4.80); fluorescence (solid): Ex, 343 nm; Em, 612
nm; RI=0.04; fluorescence (CH2Cl2): Ex, 476 nm; Em, 531 nm;
1H nmr(CDCl3) ꢃ: 1.32 (t, 3, O-CH2-CH3, J=7.1 Hz), 3.11 (s, 6,
NMe2), 3.74 (s, 2, -CH2-), 4.24 (q, 2, O-CH2-CH3, J=7.1 Hz),
6.64 (s, 1, 5-H), 6.69 (d, 2, 2', 6'-H, J=9.0 Hz), 7.77 (d, 2, 3', 4'-
H, J=9.0 Hz); ms m/z: 327 (M++1, 22), 326 (M+, 100), 298 (15),
225 (12), 148 (40), 44 (30). Anal. Calcd. for C18H18N2O4: C,
66.25; H, 5.56; N, 8.58. Found: C, 65.96; H, 5.55; N, 8.45.
3-Cyano-6-phenyl-4-toluenesulfonylmethyl-2H-pyran-2-one
(10f). This compound (0.482 g, 1.32 mmoles) was prepared in
66% yield from 3a (0.487 g, 2.0 mmoles) and 6e (0.849 g, 4.0
mmoles) in a manner similar to that described for the
preparation of 10a. An analytical sample was re-crystallized
from methanol to give pale yellow needles, mp 267-268°;
ir(potassium bromide) ꢀ max cm-1: 1765, 1740, 1705 (CO), 1615,
1
2206 (CN), 1635, 1566, 1543, 1289, 752; H nmr(CDCl3) ꢃ:
2.53(s, 3, SMe), 5.18 (brs, 2, NH2), 6.52 (s, 1, 6-H), 7.06 (m, 2,
phenyl-H), 7. 21 (m, 2, phenyl-H), 7.42 (m, 1, phenyl-H); ms
m/z: 296 (M++1, 41), 295 (M+, 100), 280 (32), 248 (28), 233
(38). Anal. Calcd. for C16H13N3OS: C, 65.06; H, 4.44; N, 14.23.
Found: C, 64.98; H, 4.51 N, 14.31.
3-Amino-4'-methoxy-5-methylsulfanyl-biphenyl-2,4-dicarbo-
nitrile (11c). This compound (1.46 g, 4.9 mmoles) was prepared
in 98% yield from 3c (1.37 g, 5.0 mmoles) and 6h (0.51 g, 7.7
mmoles) in a manner similar to that described for the
preparation of 11a. An analytical sample was re-crystallized
from DMF to give colorless needles, mp 200-202[4f: mp 212-
213°]; ir(potassium bromide) ꢀ max cm-1: 3454 (NH), 3335 (NH),
2223 (CN), 2206 (CN), 1644, 1567, 1515, 1255; uv(EtOH) ꢁ max
nm(log ꢂ):255 (4.48), 293 (4.18), 316 (4.17), 362 (4.13);
1515; uv(EtOH) ꢁ
nm(log ꢂ): 359 (4.13); fluorescence
max
1
(solid): Ex, 342 nm; Em, 464 nm; RI=5.20; H nmr(CDCl3) ꢃ:
2.47 (s, 3 Me), 4.46 (s, 2, -CH2-), 7.08 (s, 1, 5-H), 7.40 (d, 2, 3'',
5''-H, J=8.2 Hz), 7.54 (m, 3, 3', 4', 5'-H), 7.77 (d, 2, 2'', 6''-H,
J=8.2 Hz), 7.91 (d, 2, 2', 6'-H, J=6.9 Hz); ms m/z: 366 (M++1,
15), 365 (M+, 65), 155 (100), 105 (12), 91 (93), 77 (18). Anal.
Calcd. for C20H15NO4S: C, 65.74; H, 4.14; N, 3.83. Found: C,
65.87; H, 3.97; N, 3.78.
1
fluorescence (solid): Ex, 365 nm; Em, 422 nm; RI=0.13; H
nmr(CDCl3) ꢃ:2.57 (s, 3, SMe), 3.87 (s, 3, OMe), 5.12 (brs, 2,
NH2), 6.54 (s, 1, 6-H), 7.02 (d, 2, 2', 6'-H, J=9.0 Hz), 7.49 (d, 2,
3', 5'-H, J=9.0 Hz); ms m/z: 296 (M++1, 20), 295 (M+, 100), 262
(9), 236 (11).
3-Cyano-6-(4-methoxyphenyl)-4-toluenesulfonyl-methyl-2H-
pyran-2-one (10g). This compound (0.142 g 0.3 mmoles) was
separated in 18% yield from a mixture of 8a and 10g which was
prepared from 3c (0.547 g, 2.0 mmoles) and 4-toluene-
sulphonylacetoacetone (6e) (0.849 g, 4.0 mmoles). An analytical
sample was recyclized with ethanol to give yellow needles, mp
3-Amino-2',4'-dimethoxy-5-methylsulfanyl-biphenyl-2,4-
dicarbonitrile (11d). This compound (0.555 g, 1.69 mmoles)
was prepared in 85% yield from 3d (0.60 g, 2.0 mmoles) and 6h
(0.198 g, 3.0 mmoles) in a manner similar to that described for
the preparation of 11a. An analytical sample was recrystallized
from DMF to give colorless needles, mp 259-261°; ir(potassium
bromide) ꢀ max cm-1: 3406 (NH), 3344 (NH), 3247, 2221 (CN),
2206 (CN), 1655, 1614, 1562, 1541, 1211, 831; uv(EtOH) ꢁ max
nm(log ꢂ): 298 (3.87), 325 (3.86), 359 (3.92) ; fluorescence
278-280°; ir(potassium bromide) ꢀ
1600, 1530, 1505; uv(EtOH) ꢁ
cm-1: 1720 (CO), 1615,
max
nm(log ꢂ): 312 (4.36), 319
(4.35), 388 (4.37); fluorescence (solid): Ex, 340 nm; Em, 497
max
1
1
nm; RI=0.08; H nmr(CDCl3) ꢃ: 2.48 (s, 3, Me), 3.92 (s, 3,
(solid): Ex, 334 nm; Em, 428 nm; RI=0.13; H nmr(CDCl3) ꢃ:
OMe), 4.43 (s, 2, -CH2-), 6.97 (s, 1, 5-H), 7.02 (d, 2, 3', 5'-H,
J=9.1 Hz), 7.40 (d, 2, 3'', 5''-H, J=8.5Hz), 7.75 (d, 2, 2'', 6''-H,
J=8.5 Hz), 7.88 (d, 2, 2', 6'-H, J=9.1 Hz); ms m/z: 396 (M++1,
24), 395 (M+, 94), 155 (71), 149 (54), 135 (54), 91 (100). Anal.
Calcd. for C21H17NO5S: C, 63.79; H, 4.33; N, 3.54. Found: C,
63.52; H, 4.30; N, 3.50.
2.56 (s, 3, SMe), 3.84 (s, 3, OMe), 3.92 (s, 3, OMe), 6,53 (s, 1,
6-H), 6.62 (s, 1, 3'-H), 6.64 (d, 1, 5'-H, J=8.7 Hz), 7.18 (d, 1, 6'-
H, J=8.7 Hz); ms m/z: 326 (M++1, 59), 325 (M+, 100, 310 (10),
278 (18), 263 (16), 248 (10). Anal. Calcd for C17H15N3O2S: C,
62.75; H, 4.65; N, 12.91. Found: C, 62.58; H, 4.75; N, 12.86.
3-Amino-3',4',5'-trimethoxy-5-methylsulfanyl-biphenyl-2,4-
dicarbonitrile (11e). This compound (0.642 g, 1.81 mmoles) was
prepared in 90% yield from 3f (0.666 g, 2.0 mmoles) and 6h (0.20
g, 3.0 mmoles) in a manner similar to that described for the
preparation of 11a. An analytical sample was re-crystallized from
DMF to give colorless needles, mp 263-265°; ir(potassium
3-Amino-5-methylsulfanyl-biphenyl-2,4-dicarbonitrile (11a).
A mixure of 3a (0.481 g, 2.0 mmoles), malononitrile
(6h)(0.40 g, 6.1 mmoles), powdered sodium hydroxide (0.20
g, 5.0 mmoles), and 20 ml of DMSO was stirred for 5 hours
at room temperature. The color of the reaction mixture was
changed from yellow to red brown. The reaction mixture was
poured into 300 ml of water and this solution was stirred for
4-20 hours at room temperature The precipitate that appeared
was collected by filtration. After drying in air, the product
was recrystallized from methanol or ethanol to give pure
products (0.446g, 1.68 mmoles) as colorless needles, in 84%
yield, mp 240-242°[4f: mp 243-244°]; ir(potassium bromide)
bromide) ꢀ
cm-1: 3404 (NH), 3338 (CN), 3246, 2219 (CN),
max
1648, 1585, 1542, 1282, 1240, 1124, 995; uv(EtOH) ꢁ max nm(log
ꢂ):254 (4.68), 308 (4.32), 365 (4.31) ; fluorescence (solid): Ex,
1
368 nm; Em, 434 nm; RI=0.13; H nmr(CDCl3) ꢃ:2.60 (s, 3,
SMe), 3.93 (s, 6, 2xOMe), 3.98 (s, 3, 0Me), 6.57 (s, 1, 6-H), 6.73
(s, 2, 2', 6'-H); ms m/z: 356 (M++1, 30), 355 (M+, 100), 340 (29),
312 (17), 282 (10). Anal. Calcd. for C18H17N3O3S: C, 60.83; H,
4.82; N, 11.82. Found: C, 60.53; H, 4.87; N, 11.64.
ꢀ
cm-1: 3395 (NH), 3345 (NH), 3248, 2222 (CN), 2217
max

Jan-Feb 2008
Reaction of 6-Aryl- or Styryl-4-methylsulfanyl-2-oxo-2H-pyrans with Active Methylene
277
3-Amino-4'-N,N-dimethylamino-5-methylsulfanyl-biphenyl-
2,4-dicarbonitrile (11f). This compound (0.675 g, 2.19
mmoles) was prepared in 73% yield from 3g (0.858 g, 3.0
mmoles) and 6h (0.504 g, 7.6 mmoles) in a manner similar to
that described for the preparation of 11a. An analytical sample
was re-crystallized from DMF to give colorless needles; mp
g, 4.0 mmoles) in a manner similar to that described for the
preparation of 11a. An analytical sample was re-crystallized
from DMF to give colorless needles; mp 196-198°; ir(potassium
cm-1: 3464 (NH), 3352 (NH), 2208 (CN), 1676
bromide) ꢀ
(CO), 1564, 1503, 1274, 1243.; uv(EtOH) ꢁ max nm(log ꢂ):254
max
1
(4.51), 316 (4.18), 368 (4.12); H nmr(CDCl3) ꢃ: 2.44 (s, 3,
257-259°; ir(potassium bromide) ꢀ
cm-1: 3454 (NH), 3335
SMe), 3.97 (s, 3, OMe), 6.04 (s, 2, O-CH2-O), 6.41 (brs, 2,
NH2), 6.49 (s, 1, 6-H), 6.91 (d, 1, 5'-H, J=8.2 Hz), 7.00 (d, 1, 2'-
H, J=1.6 Hz), 7.04 (dd, 1, 6'-H, J=1.6, 8.2 Hz); ms m/z: 343
(M++1, 9), 342 (M+, 43), 311 (10), 310 (24), 262 (96), 234 (100).
Anal. Calcd for C17H14N2O4S: C, 59.64; H, 4.12; N, 8.18. Found.
C, 59.66; H, 4.11 N, 8.09.
max
(NH), 3235, 2221 (CN), 2206 (CN), 1644, 1610, 1566, 1527,
1365, 1201, 805; uv(EtOH) ꢁ nm(log ꢂ):264 (4.58), 379
max
(4.51) ; fluorescence (solid): Ex, 375 nm; Em, 523 nm; RI=0.12;
1H nmr(DMSO-d6) ꢃ: 2.60 (s, 3, SMe), 3.33 (s, 6, NMe2), 6.60
(brs, 2, NH2), 6.52 (s, 1, 6-H), 6.81 (d, 2, 3', 5'-H, J=9.0 Hz),
7.48 (d, 2, 2', 6'-H, J=9.0 Hz); ms m/z: 309 (M++1, 222), 308
(M+, 100), 307 (39), 249 (10). Anal. Calcd for C17H16N4S: C,
66.21, H, 5.23; N, 16.17. Found: C, 66.12; H, 5.22; N, 16.32.
3-Amino-4'-cyano-5-methylsulfanyl-biphenyl-2,4-dicarbo-
nitrile (11g). This compound (0.545 g, 1.88 mmoles) was
prepared in 94% yield from 3h (0.534 g, 2.0 mmoles) and 6h
(0.198 g, 3.0 mmoles) in a manner similar to that described for
the preparation of 11a. An analytical sample was re-crystallized
from DMF to give colorless needles; mp 312-314°; ir(potassium
REFERNCES AND NOTES
[1] a) C. W. Tang and S. A. van Slyke, Appl.Phys.Lett., 1987, 51,
913; b) C. W. Tang and S. A.van Slyke, and C. H. Chen, J. Appl. Phy.,
1989, 65, 3610; c) M. Matsuoka, J. Soc. Dyers and Colourists, 1989,
105, 167; d) K. Shirai, A.Yanagisawa, H. Takahashi, K. Fukunishi, and
M. Matsuoka, Dyes and Pigments, 1998, 39, 49; e) K. Shirai, M.
Matsuoka, and K. Fukunishi, Dyes and Pigments, 2000, 47, 107; f) K.
Takahashi, K. Seto, T. Yamaguchi, J. Nakamura, C. Yokoe, and K.
Murata, Chem. Lett., 2004, 8, 1042; g) U. H. F. Bunz, Chem. Rev., 2000,
100, 1605; h) M. Irie, Chem. Rev., 2000, 100, 1685; i) J. A. Delaire and
K. Nakatani, Chem. Rev., 2000, 100, 1817.
[2] a) K. Hirano, S. Minakata, and M. Komatsu, Chem. Lett.,
2001, 8; b) K. Hirano, S. Minakata, and M. Komatsu, Bull. Chem. Soc.
Jpn., 2001, 74, 1567; c) J. Yu and Y. Shirota, Chem. Lett., 2002, 984.
[3] N. Mizuyama, Y. Murakami, S. Kohra, K. Ueda, K. Hiraoka,
J. Nagaoka, Y. Shigemitsu, and Y. Tominaga, J. Heterocycl. Chem.,
2007, 44, 115.
[4] a) Y. Tominaga, A. Ushirogouchi, Y. Matsuda, and G.
Gobayashi, Heterocycles, 1977, 8, 193; b) Y. Tominaga, Y. Matsuda,
and G. Kobayashi, Chem. Pharm. Bull., 1984, 32, 1665; c) Y. Tominaga,
A. Ushirogouchi, Y. Matsuda, and G. Kobayashi, Chem. Pharm. Bull.,
1984, 32, 3384; d) Y. Tominaga, A. Ushirogouchi, and Y. Matsuda, J.
Heterocycl. Chem., 1987, 24, 1557; e) V. J. Ram and N. Agarwal,
Tetrahedron. Lett., 2001, 42, 7127; f) N. Agarwal, A. S. Saxena ,
Farhanullah, A. Goel and V. J Ram, Tetrahedron, 2002, 58, 8793.
[5] N. Mizuyama, Y. Murakawa, S. Kohra, K. Ueda, K. Hiraoka,
J. Nagaoka, K. Hiraoka, Y. Shigemitsu, and Y. Tominaga, Heterocycles,
2006, 68, 1105.
[6] a) C. H. Chen, C. W. Tang, J. Shi, and K. P. Klubeck,
Macromol. Symp., 1997, 125, 1; b) V. Bulivic, A. Shoustikov, M. A.
Baldo, E. Bose, V. G. Kozlov, M. E. Thompson, and S. R. Forrest,
Chem. Phys. Lett., 1998, 287, 455; c) C. H. Chen, C. W. Tang, J. Shi,
and K. P. Klubeck, Thin Solid Films., 2000, 363, 327; d) Y. Hamada, H.
Kanno, T. Tsujioka, H. Takahashi, and T. Usuki, Appl. Phys. Lett., 2000,
75, 1682; e) D. H. Hwang, J. D. Lee, M. J. Lee, and C. Lee, Curren.
Appl. Phys., 2005, 5, 244; f) B. C. Wang, H. R. Liao, W. H. Chen, Y. M.
Chou, J. T. Yeh, and J. C. Chang, J. Mol. Struct., 2005, 716, 19.
[7] J. Kido, H. Hayase, K. Hongawa, K. Nagai, and K. Okuyama,
Appl. Phys. Lett., 1994, 65, 2124; b) G. E. Jabbour J. F. Wang, B.
Kippelen, and N. Peyghambarian, Jpn. J. Appl. Phys., 1999, 38, L1553;
c) H. Rudmann and M. F. Rubner, J. Appl. Phys., 2001, 90, 4338; d) F.
Gao and A. J. Bard, J. Am. Chem. Soc., 2000, 122, 7426; e) X. H. Zhang,
B. J. Chen. X. Q. Lin, O. Y. Wong, C. S. Lee, H. L. Hwong, S. T. Lee, and
S. K. Wu, Chem. Mater, 2001, 13, 1565; f) Y. Sakakibara, S. Okutsu, T.
Enokita, and T. Tani, Appl. Phys. Lett, 1999, 74, 2587; g) L. C. Picciolo,
H. Murata, and Z. H. Kafafi, Appl. Phys. Lett., 2001, 78, 2378 .
bromide) ꢀ
cm-1: 3454 (NH), 3366 (NH), 2231 (CN), 2214
max
(CN), 2207 (CN), 1650, 1618, 1567, 1541, 1291, 830; 1H
nmr(CDCl3 +CF3COOH) ꢃ: 2.61 (s, 3, SMe), 6.54 (s, 1, 6-H),
7.67 (d, 2, 3', 5'-H, J=8.7 Hz), 7.88 (d, 2, 2', 6'-H, J=8.7 Hz); ms
m/z: 291 (M++1, 20), 290 (M+, 100), 289 (6), 257 (12), 231 (8).
Anal. Calcd for C16H10N4S: C, 66.19; H, 3.47; N, 19.30. Found:
C, 65.97; H, 3.67; N, 19.01.
Methyl 3-Amino-2-cyano-5-methylsulfanyl-biphenyl-4-
carboxylate (11h). This compound (0.74 g, 1.59 mmoles) was
prepared in 80% yield from 4a (0.55 g, 2.0 mmoles) and 6h
(0.30 g, 4.0 mmoles) in a manner similar to that de-scribed for
the preparation of 11a. An analytical sample was re-crystallized
from DMF to give colorless needles, mp 138-140°[4f: mp 169-
170°]; ir(potassium bromide) ꢀ max cm-1: 3445 (NH), 3343 (NH),
2210 (CN), 1671 (CO), 1597, 1427, 1335, 1266, 704; uv(EtOH)
ꢁ
nm(log ꢂ):252 (4.52), 308 (4.01), 368 (4.03); 1H
max
nmr(CDCl3) ꢃ: 2.44 (s, 3, SMe), 3.98 (s, 3, OMe), 6.41 (brs, 2,
NH2), 6.55 (s, 1, 6-H), 7.43-7.59 (m, 5, phenyl-H); ms m/z: 299
(M++1, 19), 298 (M+, 100), 267 (26), 266 (65), 69 (11), 59 (17).
Methyl 3-Amino-2-cyano-4'-methoxy-5-methyl-sulfanyl-
biphenyl-4-carboxylate (11i). This compound (1.12 g, 3.412
mmoles) was prepared in 68% yield from 4b (1.53 g, 5.0
mmoles) and 6h (0.462 g, 7.0 mmoles) in a manner similar to
that described for the preparation of 11a. An analytical sample
was recrystallized from DMF to give colorless needles; mp 124-
126°; ir(potassium bromide) ꢀ max cm-1: 3457 (NH), 3341 (NH),
2210 (CN), 1690 (CO), 1603, 1512 1260; uv(EtOH) ꢁ max nm(log
ꢂ):254 (4.46), 312 (4.13), 369 (4.07); fluorescence (solid): Ex,
1
372 nm; Em, 435 nm; RI=0.15; H nmr(CDCl3) ꢃ: 2.44 (s, 3,
SMe), 3.87 (s, 3, OMe), 3.95 (s, 3, OMe), 6.41 (brs, 2, NH2),
6.52 (s, 1, 6-H), 7.01 (d, 2, 3', 5'-H, J=8.9 Hz), 7.52 (d, 2, 2', 6'-
H, J=8.9 Hz); ms m/z: 329 (M++1, 21), 328 (M+, 100), 297 (25),
210 (10), 179 (14), 45 (12). Anal. Calcd for C17H16N2O3S: C,
62.18; H, 4.91; N, 8.53. Found. C, 61.96; H, 4.88; N, 8.55.
Methyl 6-Amino-4-benzo[1.3]dioxol-5-yl-5-cyano-2-(sulfanyl)-
benzoate (11j). This compound (0.507 g, 1,47 mmoles) was
prepared in 74% yield from 4c (0.64 g, 2.0 mmoles) and 6h (0.3
[8] N. Agarwal, A. S. Saxena, Farhanullah, A. Goel and V. J.
Ram, Tetrahedron, 2002, 58, 8793.