A facile route to the synthesis of 1,4-pyranonaphthoquinone derivatives under microwave irradiation without catalyst

Article abstract of DOI:10.1002/jhet.153

(Chemical Equation Presented) A series of 1,4-pyranonaphthoquinone derivatives were synthesized via the reaction of arylidenemalononitrile and 2-hydroxynaphthalene-1,4-dione in the mixed solvent of N,N-dimethylformamide and glacial acetic acid (HOAc) under microwave irradiation without catalyst. This protocol has the notable advantages of short reaction time, high yield, and convenient operation.

Full text of DOI:10.1002/jhet.153

832
A Facile Route to the Synthesis of 1,4-Pyranonaphthoquinone
Derivatives under Microwave Irradiation without Catalyst
Vol 46
Xing-Han Wang,a Xiao-Hong Zhang,a Shu-Jiang Tu,a* Feng Shi,a Xiang Zou,b
Shu Yan,a Zheng-Guo Han,a Wen-Juan Hao,a Xu-Dong Cao,a
and Shan-Shan Wua
aSchool of Chemistry and Chemical Engineering, Xuzhou Normal University, Key Laboratory of
Biotechnology for Medicinal Plant, Xuzhou, Jiangsu, 221116, People’s Republic of China
bDepartment of Chemistry, Lianyungang Teachers College, Lianyungang,
People’s Republic of China
*E-mail: laotu2001@263.net
Received July 18, 2008
DOI 10.1002/jhet.153
Published online 25 August 2009 in Wiley InterScience (www.interscience.wiley.com).
A series of 1,4-pyranonaphthoquinone derivatives were synthesized via the reaction of arylidenemalo-
nonitrile and 2-hydroxynaphthalene-1,4-dione in the mixed solvent of N,N-dimethylformamide and gla-
cial acetic acid (HOAc) under microwave irradiation without catalyst. This protocol has the notable
advantages of short reaction time, high yield, and convenient operation.
J. Heterocyclic Chem., 46, 832 (2009).
INTRODUCTION
and coworkers [15a] have reported the reaction of 2-
hydroxynaphthalene-1,4-dione and arylidenemalononi-
trile in methanol with Et3N as catalyst under reflux con-
dition. However, this protocol has drawbacks such as:
(a) narrow application scope of substrates, (b) poor to
moderate yields, (c) prolonged reaction time, (d) drastic
reaction conditions and tedious work up. Therefore, the
development of a relatively convenient method to pre-
pare these compounds is still desirable.
Organic reactions under microwave irradiation (MWI)
have attracted considerable attention in the past decade
for the efficient and friendly synthesis of various organic
compounds [1]. More attractively, many reactions that
typically required hours or days with conventional heat-
ing could be realized in several minutes utilizing MWI
[2]. The use of MWI for the formation of carbon-heter-
oatom and carbon-carbon bonds has been successfully
demonstrated [3].
Herein, we wish to report an efficient synthetic route
to 1,4-Pyranonaphthoquinone derivatives by the reaction
of arylidenemalononitrile and 2-hydroxynaphthalene-1,4-
dione. The reaction was carried out in the mixed solvent
of DMF and HOAc under MWI without catalyst
(Scheme 1).
Pyran derivatives are important compounds, which
exhibit antibacterial activity [4,5], antiproliferation [6]
and antitumor activities [7], hypotensive effect [8], anti-
allergic effect [9,10], and biological activities of local
anesthetic and antiarrhythmic [11]. Derivatives of 1,4-
naphthoquinone possess potent and versatile biological
activity, such as antiallergic and anticancer activities
[12]. And they are also used as inhibitors of KB cells
[13]. Derivatives of 1,4-pyranonaphthoquinone, possess-
ing both pyran ring and 1,4-naphthoquinone motif were
evaluated against human cancer cell lines, which are KB
(human epidermoid carcinoma), HeLa (human cervical
carcinoma) and HepG2 (human hepatocellular carci-
noma) cell lines employing the MTT colorimetric
method [14].
RESULTS AND DISCUSSION
Choosing an appropriate solvent is of crucial impor-
tance for successful MW promoted synthesis in view of
a rapid rise of temperature in the reaction mixture. To
search for the optimum solvent, different organic sol-
vents such as ethanol, HOAc, DMF and mixed solvent
of DMF, and HOAc were tested in the synthesis of 3c
at 100oC under MW irradiation (initial power 200 W
and maximum power 250 W). As shown in Table 1, we
could see the reaction in the mixed solvent of DMF and
Due to their diverse biological activities, several
groups [15] have been interested in the synthesis of
derivatives of this structural type. For example, Abboub
C
V
2009 HeteroCorporation

September 2009 A Facile Route to the Synthesis of 1,4-Pyranonaphthoquinone Derivatives under
Microwave Irradiation without Catalyst
833
Scheme 1
Table 2
Temperature optimization of synthesis 3c.
Entry
Temp (ꢀC)
Time (min)
Yield (%)
1
2
3
4
5
6
100
110
120
130
140
150
6
5
5
4
4
3
83
86
90
95
95
93
HOAc (the preferred volume ratio is 2:1) gave the best
result (Table 1, Entry 5).
Moreover, to further optimize the reaction tempera-
ture, the synthesis of 3c was performed in the mixed
solvent of DMF and HOAc (2:1, V/V) at the tempera-
tures ranging from 100 to 150ꢀC in the increment of
10ꢀC each time at 250 W. As illustrated in Table 2,
when the temperature was increased from 100 to 130ꢀC,
the yield of 3c obviously improved. However, no signifi-
cant increase in the yield of 3c was observed as the
reaction temperature was raised from 130 to 150ꢀC.
Therefore, the temperature of 130ꢀC was chosen for all
further microwave-assisted reactions.
1662 and 1636 cmꢁ1 due to C¼¼O groups. The 1H
NMR spectrum of 3b showed a singlet at d 7.36 corre-
sponding to proton from NH2, and a singlet at d 4.65
due to CH.
In summary, we have developed a rapid and facile
method for the synthesis of highly functionalized 1,4-
pyranonaphthoquinone derivatives of potential biological
importance in excellent yields. Particularly, this protocol
offers increased safety for small-scale high-speed syn-
thesis, and the series of 1,4-pyranonaphthoquinone
derivatives may provide expansive foreground for bio-
medical scopes.
Under these optimized reaction conditions [mixed sol-
vent (VDMF/VHOAc: 2:1, 1.5 mL), 130ꢀC], a series of
compounds 3 were synthesized with this simple proce-
dure. The results were summarized in Table 3. As
shown in Table 3, the applicability of this methodology
is broad, not only to arylidenemalononitrile either with
electron-donating groups or with electron-withdrawing
groups, but also to heterocyclic arylidenemalononitrile
(Table 3, entry 15). Therefore, we concluded that the
electronic nature of the substituent has no significant
effect on this reaction.
EXPERIMENTAL
MWI was carried out with an EmrysTM Creator microwave
oven from Personal Chemistry, Uppsala, Sweden. Melting
points were determined in open capillaries and were uncor-
rected. IR spectra were recorded on a FTIR-Tensor 27 spec-
trometer in KBr. 1H NMR spectra were measured on a DPX
400 MHz spectrometer using TMS as an internal standard and
DMSO-d6 as solvent. 13C NMR spectra were measured on a
DPX 100 MHz spectrometer using TMS as an internal stand-
ard and DMSO-d6 as solvent. Elemental analysis was
The proposed mechanism of this reaction may undergo
a simple addition and cyclization progress (Scheme 2).
The addition between arylidenemalononitrile 1 and 2-
hydroxynaphthalene-1,4-dione 2 occurs to generate 4,
which subsequently undergoes intramolecular cyclization
and isomerisation to afford final products 3.
All the products were characterized by Mp, IR, 1H
NMR, and 13C NMR spectral data, as well as by ele-
mental analysis. The IR spectrum of compound 3b
showed strong absorptions at 3413 and 3329 cmꢁ1 due
to libration of NH2 group, 2196 cmꢁ1 due to CN group,
Table 3
Physical data of products 3.
Time Yield
(min) (%) Mp (ꢀC)
Entry Product
Ar
4-FC6H4
4-ClC6H4
1
2
3
3a
3b
3c
3d
3e
3f
5
5
4
6
6
4
5
5
5
4
6
4
5
6
6
92
93
95
81
83
94
90
84
87
86
81
80
88
85
82
286–288
278–280
291–294
257–259
254–257
247–248
>300
295–297
281–283
293–295
270–272
237–239
>300
4-BrC6H4
4
5
4-CH3OC6H4
4-CH3C6H4
4-NO2C6H4
2-ClC6H4
3-NO2C6H4
3,4-OCH2OC6H3
2,4-Cl2C6H3
3,4-(CH3O)2C6H3
4-OH-3-NO2C6H3
C6H5
Table 1
6
Solvent optimization of synthesis 3c.
7
8
3g
3h
3i
Entry
Solvent
Ethanol
HOAc
Time (min)
Yield (%)
9
1
2
3
4
5
6
10
7
8
72
74
70
76
83
78
10
11
12
13
14
15
3j
3k
3l
3m
3n
3o
DMF
DMF/HOAc(1:1)
DMF/HOAc(2:1)
DMF/HOAc(3:1)
6
6
6
3,4,5-(CH3O)3C6H2
Thien-2-yl
290–293
274–276
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

834
X.-H. Wang, X.-H Zhang, S.-J. Tu, F. Shi, X.Zou, S. Yan, Z.-G. Han,
W.-J. Hao, X.-D. Cao, and S.-S. Wu
Vol 46
Scheme 2
C20H11ClN2O3: C, 66.22; H, 3.06; N, 7.72. Found: C, 66.43;
H, 3.05; N, 7.74.
2-Amino-4-(4-bromophenyl)-5,10-dihydro-5,10-dioxo-4H-
benzo [g]chromene-3-carbonitrile (3c). This compound was
obtained according to above general procedure; ir (potassium
bromide): 3406, 3326, 2194, 1665, 1603 cmꢁ1; 1H nmr (DMSO-
d6): d 8.07–8.04 (m, 1H, ArH), 7.89–7.83 (m, 3H, ArH), 7.50 (d,
2H, J ¼ 8.4 Hz, ArH), 7.39 (s, 2H, NH2), 7.31 (d, 2H, J ¼ 8.4
Hz, ArH), 4.63 (s, 1H, CH); 13C NMR (100 MHz) (d, ppm):
182.52, 176.78, 158.30, 149.04, 143.01, 134.51, 134.14, 131.40,
130.97, 130.63, 130.02, 126.04, 125.78, 121.31, 120.20, 119.15,
57.00, 36.06. Anal. Calcd. for C20H11BrN2O3: C, 58.99; H, 2.72;
N, 6.88. Found: C, 59.16; H, 2.73; N, 6.86.
2-Amino-5,10-dihydro-4-(4-methoxyphenyl)-5,10-dioxo-4H-
benzo[g]chromene-3-carbonitrile (3d). This compound was
obtained according to above general procedure; ir (potassium
bromide): 3396, 3329, 2204, 1672, 1635 cmꢁ1
;
1H nmr
(DMSO-d6): d 8.06–8.04 (m, 1H, ArH), 7.87–7.83 (m, 3H,
ArH), 7.30 (s, 2H, NH2), 7.22 (d, 2H, J ¼ 8.4 Hz, ArH), 6.86
(d, 2H, J ¼ 8.8 Hz, ArH), 4.56 (s, 1H, CH), 3.71 (s, 3H,
OCH3); 13C NMR (100 MHz) (d, ppm): 182.58, 176.88,
158.29, 148.55, 135.64, 134.49, 134.09, 131.02, 130.56,
128.82, 128.29, 126.02, 125.76, 122.25, 119.37, 113.93, 57.70,
55.04, 35.67. Anal. Calcd. for C21H14N2O4: C, 70.39; H, 3.94;
N, 7.82. Found: C, 70.62; H, 3.95; N, 7.87.
2-Amino-5,10-dihydro-5,10-dioxo-4-p-tolyl-4H-benzo[g]-
chromene-3-carbonitrile (3e). This compound was obtained
according to above general procedure; ir (potassium bromide):
3404, 3327, 2197, 1662, 1603 cmꢁ1 1H nmr (DMSO-d6): d
;
determined with
instrument.
a
Perkin-Elmer 240c elemental analysis
General procedure for 2-arylidenemalononitrile (1). A
mixture of aromatic aldehyde (5 mmol), malononitrile (5
mmol), and ethanol (2 mL) was added to a 10 mL reaction
vessel of the monomodal EmrysTM Creator microwave synthe-
sizer and allowed to react under MWI at 150 W power and
100ꢀC for 2–3 min. The reaction mixture was cooled to room
temperature, then filtered to give the crude product, which was
further purified by recrystallization from EtOH (95%).
General procedure for 2-Amino-5,10-dihydro-5,10-dioxo-
8.06–8.04 (m, 1H, ArH), 7.87–7.83 (m, 3H, ArH), 7.32 (s, 2H,
NH2), 7.19 (d, 2H, J ¼ 8.0 Hz, ArH), 7.11 (d, 2H, J ¼ 7.6
Hz, ArH), 4.57 (s, 1H, CH), 2.25 (s, 3H, CH3); 13C NMR (100
MHz) (d, ppm): 182.53, 176.86, 158.29, 148.73, 140.63,
136.25, 134.51, 134.10, 131.01, 130.58, 129.12, 127.56,
126.03, 125.77, 122.16, 119.33, 57.59, 36.09, 20.59. Anal.
Calcd. for C21H14N2O3: C, 73.68; H, 4.12; N, 8.18. Found: C,
73.88; H, 4.11; N, 8.20.
2-Amino-5,10-dihydro-4-(4-nitrophenyl)-5,10-dioxo-4H-benzo
[g]chromene-3-carbonitrile (3f). This compound was obtained
according to above general procedure; ir (potassium bromide):
3421, 3328, 2201, 1673, 1604 cmꢁ1 1H nmr (DMSO-d6): d
;
4-aryl-4H-benzo-[g]chromene-3-carbonitrile
derivatives
(3). The reactions were performed in a 10 mL EmrysTM reac-
tion vial, arylidenemalononitrile 1 (1 mmol), 2-hydroxynaph-
thalene-1,4-dione 2 (1 mmol), and DMF/HOAc (1.5 mL) (2:1,
V/V) were mixed and then capped. The mixture was irradiated
for a given time at 130ꢀC under MWI (initial power 200 W
and maximum power 250 W). Upon completion, monitored by
TLC, the reaction mixture was cooled to room temperature,
then filtered to give the crude product, which was further puri-
fied by recrystallization from EtOH (95%) to give pure 2-
amino-5,10-dihydro-5,10-dioxo-4-aryl-4H-benzo[g]chromene-
3-carbonitrile derivatives 3.
8.21–8.19 (m, 1H, ArH), 8.11 (d, 1H, J ¼ 8.4 Hz, ArH), 8.06
(d, 1H, J ¼ 7.6 Hz, ArH), 7.88–7.84 (m, 4H, ArH), 7.63 (t,
1H, J ¼ 8.0 Hz, ArH), 7.49 (s, 2H, NH2), 4.88 (s, 1H, CH);
13C NMR (100 MHz) (d, ppm): 182.56, 176.75, 158.46,
149.37, 147.94, 145.81, 134.77, 134.47, 134.14, 130.97,
130.05, 126.02, 125.79, 122.49, 120.58, 119.01, 56.63, 36.33.
Anal. Calcd. for C20H11N3O5: C, 64.35; H, 2.97; N, 11.26.
Found: C, 64.51; H, 2.96; N, 11.29.
2-Amino-4-(4-fluorophenyl)-5,10-dihydro-5,10-dioxo-4H-benzo
[g]chromene-3-carbonitrile (3a). This compound was obtained
according to above general procedure; ir (potassium bromide):
3407, 3324, 2210, 1667, 1635 cmꢁ1 1H nmr (DMSO-d6): d
;
8.06–8.04 (m, 1H, ArH), 7.88–7.83 (m, 3H, ArH), 7.38 (t, 2H, J
¼ 5.6 Hz, ArH), 7.35 (s, 2H, NH2), 7.13 (t, 2H, J ¼ 8.8 Hz,
ArH), 4.65 (s, 1H, CH); 13C NMR (100 MHz) (d, ppm): 182.55,
176.81, 162.37, 159.96, 158.28, 148.92, 139.82, 134.49, 134.12,
130.99, 130.64, 129.73, 129.65, 121.62, 119.24, 115.35, 57.33,
35.79. Anal. Calcd. for C20H11FN2O3: C, 69.36; H, 3.20; N,
8.09. Found: C, 69.54; H, 3.19; N, 8.11.
2-Amino-4-(4-chlorophenyl)-5,10-dihydro-5,10-dioxo-4H-benzo
[g]chromene-3-carbonitrile (3b). This compound was obtained
according to above general procedure; ir (potassium bromide):
3413, 3329, 2196, 1662, 1636 cmꢁ1 1H nmr (DMSO-d6): d
;
8.06–8.05 (m, 1H, ArH), 7.88–7.84 (m, 3H, ArH), 7.38 (s, 4H,
ArH), 7.36 (s, 2H, NH2), 4.65 (s, 1H, CH); 13C NMR (100
MHz) (d, ppm): 182.53, 176.78, 158.31, 149.03, 142.59,
134.51, 134.14, 131.67, 130.98, 130.63, 129.65, 128.47,
126.03, 125.78, 121.37, 119.16, 57.07, 36.98. Anal. Calcd. for
2-Amino-4-(2-chlorophenyl)-5,10-dihydro-5,10-dioxo-4H-
benzo[g]chromene-3-carbonitrile (3g). This compound was
obtained according to above general procedure; ir (potassium
bromide): 3434, 3327, 2192, 1663, 1635 cmꢁ1
;
1H nmr
(DMSO-d6): d 8.08–8.06 (m, 1H, ArH), 7.87–7.84 (m, 3H,
ArH), 7.45–7.40 (m, 2H, ArH), 7.37 (s, 2H, NH2), 7.26–7.24
(m, 2H, ArH), 5.15 (s, 1H, CH); 13C NMR (100 MHz) (d,
ppm): 182.39, 176.78, 158.40, 149.52, 140.92, 134.57, 134.15,
132.01, 130.93, 130.57, 130.50, 129.38, 128.67, 127.79,
126.06, 125.80, 121.29, 118.77, 56.33, 33.55. Anal. Calcd. for
C20H11ClN2O3: C, 66.22; H, 3.06; N, 7.72. Found: C, 66.41;
H, 3.07; N, 7.70.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

September 2009 A Facile Route to the Synthesis of 1,4-Pyranonaphthoquinone Derivatives under
Microwave Irradiation without Catalyst
835
2-Amino-5,10-dihydro-4-(3-nitrophenyl)-5,10-dioxo-4H-
benzo[g] chromene-3-carbonitrile (3h). This compound
was obtained according to above general procedure; ir (potas-
;
sium bromide): 3421, 3328, 2202, 1671, 1639 cmꢁ1 1H nmr
2-Amino-5,10-dihydro-5,10-dioxo-4-phenyl-4H-benzo[g]-
chromene-3-carbonitrile (3m). This compound was obtained
according to above general procedure; ir (potassium bromide):
;
3401, 3325, 2200, 1671, 1636 cmꢁ1 1H nmr (DMSO-d6): d
(DMSO-d6): d 8.21–8.18 (m, 1H, ArH), 8.11 (d, 1H, J ¼ 7.6
Hz, ArH), 8.07 (d, 1H, J ¼ 7.6 Hz, ArH), 7.87–7.84 (m, 4H,
ArH), 7.63 (t, 1H, J ¼ 8.0 Hz, ArH), 7.49 (s, 2H, NH2), 4.88
(s, 1H, CH); 13C NMR (100 MHz) (d, ppm): 182.57, 176.76,
158.44, 149.37, 147.93, 145.82, 134.79, 134.47, 134.14,
130.96, 130.73, 130.05, 126.02, 125.79, 122.49, 122.16,
120.54, 119.03, 56.59, 36.32. Anal. Calcd. for C20H11N3O5: C,
64.35; H, 2.97; N, 11.26. Found: C, 64.51; H, 2.98; N, 11.23.
2-Amino-4-(benzo[d][1,3]dioxol-5-yl)-5,10-dihydro-5,10-
dioxo-4H-benzo[g]chromene-3-carbonitrile (3i). This com-
pound was obtained according to above general procedure; ir
8.07–8.05 (m, 1H, ArH), 7.90–7.83 (m, 3H, ArH), 7.34 (s, 2H,
NH2), 7.31 (d, 4H, J ¼ 4.4 Hz, ArH), 7.23–7.22 (m, 1H,
ArH), 4.61 (s, 1H, CH); 13C NMR (100 MHz) (d, ppm):
182.53, 176.84, 158.37, 148.91, 143.55, 134.51, 134.12,
131.03, 130.63, 128.56, 127.65, 127.05, 126.05, 125.79,
122.04, 119.27, 57.54, 36.50. Anal. Calcd. for C20H12N2O3: C,
73.16; H, 3.68; N, 8.53. Found: C, 73.38; H, 3.69; N, 8.51.
2-Amino-5,10-dihydro-4-(3,4,5-trimethoxyphenyl)-5,10-dioxo-
4H-benzo[g]chromene-3-carbonitrile (3n). This compound was
obtained according to above general procedure; ir (potassium
bromide): 3418, 3327, 2196, 1662, 1634 cmꢁ1
;
1H nmr
1
(potassium bromide): 3427, 3396, 2207, 1673, 1637 cmꢁ1; H
(DMSO-d6): d 8.07–8.05 (m, 1H, ArH), 7.92–7.84 (m, 3H,
ArH), 7.30 (s, 2H, NH2), 6.57–6.55 (m, 2H, ArH), 4.57 (s, 1H,
CH), 3.74 (s, 6H, 2OCH3), 3.62 (s, 3H, OCH3); 13C NMR
(100 MHz) (d, ppm): 182.64, 176.88, 158.29, 152.87, 149.00,
139.28, 136.59, 134.43, 134.04, 131.08, 130.72, 125.99,
125.82, 121.48, 119.35, 105.13, 59.89, 57.54, 55.99, 36.76.
Anal. Calcd. for C23H18N2O6: C, 66.02; H, 4.34; N, 6.70.
Found: C, 66.24; H, 4.35; N, 6.72.
2-Amino-5,10-dihydro-5,10-dioxo-4-(thiophen-2-yl)-4H-benzo
[g]chromene-3-carbonitrile (3o). This compound was obtained
according to above general procedure; ir (potassium bromide):
3409, 3328, 2196, 1665, 1638 cmꢁ1 1H nmr (DMSO-d6): d
;
8.05–8.04 (m, 1H, ArH), 7.98–7.96 (m, 1H, ArH), 7.88–7.86
(m, 2H, ArH), 7.49 (s, 2H, NH2), 7.40 (d, 1H, J ¼ 4.0 Hz,
ArH), 7.01 (d, 1H, J ¼ 3.2 Hz, ArH), 6.95 (t, 1H, J ¼ 2.8 Hz,
ArH), 4.97 (s, 1H, CH); 13C NMR (100 MHz) (d, ppm):
182.38, 176.81, 158.93, 148.18, 147.10, 134.69, 134.29,
130.91, 130.48, 127.18, 126.16, 125.92, 125.41, 125.35,
121.87, 119.19, 57.10, 31.17. Anal. Calcd. for C18H10N2O3S:
C, 64.66; H, 3.01; N, 8.38; S, 9.59. Found: C, 64.83; H, 3.00;
N, 8.35; S, 9.61.
nmr (DMSO-d6): d 8.06–8.04 (m, 1H, ArH), 7.89–7.83 (m,
3H, ArH), 7.29 (s, 2H, NH2), 6.89–6.86 (m, 1H, ArH), 6.83
(d, 1H, J ¼ 8.0 Hz, ArH), 6.78 (d, 1H, J ¼ 7.6 Hz, ArH),
5.97 (s, 2H, CH2), 4.55 (s, 1H, CH); 13C NMR (100 MHz) (d,
ppm): 182.59, 176.84, 158.21, 148.82, 147.39, 146.23, 137.66,
134.45, 134.07, 131.04, 130.67, 126.00, 125.77, 121.75,
120.98, 119.29, 112.71, 108.13, 100.97, 57.70, 36.12. Anal.
Calcd. for C21H12N2O5: C, 67.74; H, 3.25; N, 7.52. Found: C,
67.94; H, 3.26; N, 7.50.
2-Amino-4-(2,4-dichlorophenyl)-5,10-dihydro-5,10-dioxo-4H-
benzo[g]chromene-3-carbonitrile (3j). This compound was
obtained according to above general procedure; ir (potassium
bromide): 3467, 3341, 2202, 1671, 1632 cmꢁ1
;
1H nmr
(DMSO-d6): d 8.08–8.06 (m, 1H, ArH), 7.88–7.85 (m, 3H,
ArH), 7.60–7.58 (m, 1H, ArH), 7.49 (d, 1H, J ¼ 8.4 Hz,
ArH), 7.42 (s, 2H, NH2), 7.33 (d, 1H, J ¼ 8.4 Hz, ArH), 5.14
(s, 1H, CH); 13C NMR (100 MHz) (d, ppm): 182.43, 176.73,
158.37, 149.63, 140.21, 134.57, 134.20, 132.92, 132.26,
131.94, 130.89, 130.59, 128.66, 127.97, 126.07, 125.80,
120.70, 118.69, 55.77, 33.15. Anal. Calcd. for C20H10Cl2N2O3:
C, 60.48; H, 2.54; N, 7.05. Found: C, 60.67; H, 2.55; N, 7.02.
2-Amino-5,10-dihydro-4-(3,4-dimethoxyphenyl)-5,10-dioxo-
4H-benzo[g]chromene-3-carbonitrile (3k). This compound
was obtained according to above general procedure; ir (potas-
Acknowledgment. We thank the National Natural Science
Foundation of China (No. 20672090), the Natural Science Foun-
dation of the Jiangsu Province (No. BK2006033) for financial
support, Six Kinds of Professional Elite Foundation of the Jiangsu
Province (No. 06-A-039), the Qing Lan Project (No. 08QLT001),
and the Open Foundation of Jiangsu Key Laboratory for Chemis-
try of Low-Dimensional Materials (No. JSKC07035).
sium bromide): 3418, 3324, 2195, 1688, 1632 cmꢁ1 1H nmr
;
(DMSO-d6): d 8.06–8.04 (m, 1H, ArH), 7.90–7.83 (m, 3H,
ArH), 7.28 (s, 2H, NH2), 6.88–6.86 (m, 2H, ArH), 6.80 (d,
1H, J ¼ 8.4 Hz, ArH), 4.56 (s, 1H, CH), 3.72 (s, 3H, OCH3),
3.70 (s, 3H, OCH3); 13C NMR (100 MHz) (d, ppm): 182.62,
176.91, 158.27, 148.66, 148.63, 147.96, 136.22, 134.47,
134.06, 131.07, 130.62, 126.01, 125.78, 122.04, 119.89,
119.38, 111.95, 111.68, 57.70, 55.62, 55.52, 36.05. Anal.
Calcd. for C22H16N2O5: C, 68.04; H, 4.15; N, 7.21. Found: C,
68.26; H, 4.16; N, 7.23.
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