One-pot combinatorial synthesis of benzo[4,5]imidazo-[1,2-a]thiopyrano[3,4- d]pyrimidin-4(3H)-one Derivatives

Article abstract of DOI:10.1002/cjoc.201180308

A series of novel fused tetracyclic benzo[4,5]imidazo[1,2-a]thiopyrano[3,4- d]pyrimidin-4(3H)-one derivatives were synthesized via the reaction of aryl aldehyde, 2H-thiopyran-3,5(4H,6H)-dione, and 1H-benzo[d]imidazol-2-amine in glacial acetic acid. This p

Full text of DOI:10.1002/cjoc.201180308

FULL PAPER
One-pot Combinatorial Synthesis of Benzo[4,5]imidazo-
[1,2-a]thiopyrano[3,4-d]pyrimidin-4(3H)-one Derivatives
Shen, Shidea(沈士德)
Zhang, Honghongb(张红红)
Yang, Weihuab(杨伟华)
Yu, Chenxiab,c(于晨侠)
Yao, Changsheng*,b,c(姚昌盛)
a Xuzhou Institute of Architectural Technology, Xuzhou, Jiangsu 221116, China
b School of Chemistry & Chemical Engineering, Xuzhou Normal University, Xuzhou, Jiangsu 221116, China
c Key Laboratory of Biotechnology for Medicinal Plants, Xuzhou Normal University, Xuzhou,
Jiangsu 221116, China
A series of novel fused tetracyclic benzo[4,5]imidazo[1,2-a]thiopyrano[3,4-d]pyrimidin-4(3H)-one derivatives
were synthesized via the reaction of aryl aldehyde, 2H-thiopyran-3,5(4H,6H)-dione, and 1H-benzo[d]imidazol-2-
amine in glacial acetic acid. This protocol features mild reaction conditions, high yields and short reaction time.
Keywords benzo[4,5]imidazo[1,2-a]thiopyrano[3,4-d]pyrimidin-4(3H)-one, multicomponent reactions, combi-
natorial chemistry
Introduction
method to synthesize benzo[4,5]imidazo[1,2-a]thiopy-
rano[3,4-d]pyrimidin-4(3H)-one derivatives 4 via a
three-component reaction of aryl aldehyde 1, 2H-
thiopyran-3,5(4H,6H)-dione (2), and 1H-benzo[d]-imi-
dazol-2-amine (3) in glacial acetic acid (Scheme 1).
Thiopyran and fused thiopyran derivatives belong to
the most common heterocyclic compounds. They play
an important role in the field of medicinal chemistry and
argrochemistry because of their potential biological ac-
tivities, such as weed control and antitumor activity.1,2
Benzo[4,5]imidazo[1,2-a]pyrimidine derivatives can be
used as inhibitor of cell proliferation,3 lymphocyte spe-
cific kinase,4 DNA-topoisomerase and protein kinase.5,6
The compounds with thiopyran and pyrimidine core unit
have important biological activities, such as anti-HIV
virus, antibacterial and fungicidal activity,7 neuroleptic
activity.8 However, to the best of our knowledge, there
has been no report on the synthesis of imidazo[1,2-a]-
thiopyrano[3,4-d]pyrimidine derivatives. Considering
the biological significance of scaffolds of thiopyran and
imidazo[1,2-a]pyrimidine, developing a simple and
convenient approach for the synthesis of these fused
S,N-containing compounds is still desirable. In recent
years, multi-component reactions (MCRs) are very use-
ful for the combinatorial chemistry as powerful tools
due to their valuable features such as atom-economy,
environmental friendliness, straightforward reaction
condition, and the opportunity to construct target com-
pounds by the introduction of several diversity elements
in a single chemical operation.9 By now, many organic
transformations have been reported to proceed effi-
ciently by multi-component reactions. To continue our
work on the synthesis of heterocyclic compounds via
MCR,10 herein we shall report an efficient and easy
Scheme 1
O
H
N
HOAc
+
+
ArCHO
1
NH2
S
N
O
3
2
Ar
O
N
S
N
N
H
4
Results and discussion
The effect of solvent on the reaction was initially
examined using the reaction of 2 (1 mmol), 3 (1 mmol)
with phenyl aldehyde 1a (1 mmol) as a model reaction
at 50 ℃. It was found that the reaction in glacial acetic
acid (Table 1, Entry 1) gave higher yield than those in
other solvents. So glacial acetic acid was used as the
optimal solvent to synthesize the target compounds.
To screen the optimal temperature in glacial acetic
acid, the previous reaction was performed at 20, 40, 50,
60, and 70 ℃, resulting in the isolation of 4a in 40%,
*
E-mail: csyao@xznu.edu.cn; Tel.: 0086-0516-83403165; Fax: 0086-0516-83403165
Received January 21, 2011; revised March 5, 2011; accepted April 12, 2011.
Project supported by the Major Basic Research Project of the Natural Science Foundation of the Jiangsu Higher Education Institutions
(09KJA430003), Natural Science Foundation of Xuzhou City (XM09B016), Graduate Foundation of Xuzhou Normal University (09YLB030) and
Qing Lan Project (08QLT001).
Chin. J. Chem. 2011, 29, 1727— 1731
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1727

Shen et al.
FULL PAPER
Table 1 Solvent effect on the synthesis of 4a
same conditions. However, when the aliphatic and het-
eroaromatic aldehydes were used to this reaction, no
expected product was obtained.
All of the products were characterized by FTIR, H
NMR, and HRMS.
A possible mechanism for the formation of the
products 4 was outlined in Scheme 2. In the initial step,
the condensation of aryl aldehyde 1 and 1H-benzo[d]-
imidazol-2-amine (3) gave Schiff base 5. The addition
of 2 to Schiff base 5, followed by elimination, furnished
the intermediate 8. Michael addition between
1H-benzo[d]-imidazol-2-amine (3) and 8 afforded the
intermediate product 9, which upon isomerization, intra-
molecular cyclization and dehydration gave the final
product 4.
Entry
Solvent
HOAc
Time/h
Yielda/%
1
8
8
8
8
8
8
82
50
73
70
60
70
1
2
CHCl3
3
EtOH
4
CH3CN
DMF
5
6
Solvent-free
a Isolated yield.
78%, 82%, 75% and 56% yields (Table 2, Entries 1—5),
respectively. As shown in Table 2, 50 ℃ was the suit-
able temperature for this reaction from the viewpoint of
yield.
Scheme 2
Table 2 Temperature optimization for synthesis of 4a
H
Yielda/%
N
-H2O
Entry
Temp./℃
Time/h
+
NH2
HO
ArCHO
HOAc
N
1
20
40
50
60
70
20
10
8
40
78
82
75
56
1
3
2
S
3
H
O
N
4
8
2
N CHAr
S
HOAc
5
6
N
a Isolated yield.
5
S
Based on the optimized reaction conditions, a series
of benzo[4,5]imidazo[1,2-a]thiopyrano[3,4-d]pyrimi-
din-4(3H)-one derivatives were synthesized successfully.
As shown in Table 3, the reactions at 50 ℃ in glacial
acetic acid gave the corresponding products in moderate
to good yields. The results revealed that not only elec-
tron-rich aryl aldehyde (such as a methoxy group), but
also electron-deficient aryl aldehyde (such as a nitro
group, halogen) in the multi-component reaction af-
forded the corresponding product efficiently under the
H
N
H
N
O
O
HO
O
H+
NH
NH
S
Ar
Ar
N
N
6
7
N
Ar
NH2
N
H
O
O
H+
HO
Ar
O
H+
N
S
8
NH
HN
9
Table 3 Synthesis of compound 4
S
Time/h Yielda/% m.p./℃
S
OH
NH
Entry Compd.
Ar
O
H+
H+
1
2
4a
4b 4-BrC6H4
4c 2-FC6H4
4d 4-FC6H4
C6H5
8
8
82
82
77
80
73
75
84
85
85
84
76
80
85
295—297
292—294
＞300
O
O
NH2
Ar
N
N
Ar
N
3
7
N
4
7
＞300
11
5
4e
4f
2-ClC6H4
3-ClC6H4
3,4-Cl2C6H3
8
193—295
292—293
283—285
292—293
293—296
＞300
10
6
8
S
7
4g
7
O
Ar
NH
8
4h 3-NO2C6H4
6
-H2O
H+
N
N
9
4i
4j
4-NO2C6H4
4-CH3C6H4
7
10
11
12
13
10
10
9
4k 3-CH3OC6H4
4l 4-CH3OC6H4
4m 3,4,5-(CH3O)3C6H2
273—274
280—282
284—286
4
10
To test the proposed mechanism, the intermediate 5a,
N-benzylidene-1H-benzo[d]imidazol-2-amine was pre-
a Isolated yield.
1728
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© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2011, 29, 1727— 1731

Synthesis of Benzo[4,5]imidazo-[1,2-a]thiopyrano[3,4-d]pyrimidin-4(3H)-one Derivatives
pared via the condensation of benzaldehyde and
1H-benzo[d]imidazol-2-amine under the same condi-
tions. It could react with 2 to give the expected product
4a with slightly lower yield (76%) than the one-pot re-
action (82%). The fact supported the supposed reaction
pathway (Scheme 3).
a]-thiopyrano[3,4-d]pyrimidin-4(3H)-one (4a): 1H
NMR (CDCl3) δ: 11.47 (s, 1H, NH), 7.38 (d, J＝7.6 Hz,
1H, ArH), 7.34 (d, J＝7.2 Hz, 2H, ArH), 7.30 (d, J＝8.0
Hz, 1H, ArH), 7.26 (t, J＝7.6 Hz, 2H, ArH), 7.17 (t, J＝
7.2 Hz, 1H, ArH), 7.07 (t, J＝7.6 Hz, 1H, ArH), 6.99 (t,
J＝7.6 Hz, 1H, ArH), 6.50 (s, 1H, CH), 3.96 (d, J＝17.2
Hz, 1H, CH2), 3.60 (d, J＝17.2 Hz, 1H, CH2), 3.54 (d,
J＝16.0 Hz, 1H, CH2), 3.14 (d, J＝16.0 Hz, 1H, CH2);
IR (KBr) v: 3200, 2847－, 1639, 1616, 1592, 1567, 1350,
1273, 742, 512 cm 1; HRMS (ESI) calcd for
C19H16N3OS [M＋H]＋ 334.1014, found 334.1012.
5-(4-Bromophenyl)-5,12-dihydro-1H-benzo[4,5]imi-
dazo[1,2-a]thiopyrano[3,4-d]pyrimidin-4(3H)-one (4b):
1H NMR (DMSO-d6) δ: 11.50 (s, 1H, NH), 7.46 (d, J＝
8.0 Hz, 2H, ArH), 7.39 (d, J＝8.0 Hz, 1H, ArH),
7.31—7.28 (m, 3H, ArH), 7.08 (d, J＝7.6 Hz, 1H, ArH),
7.00 (d, J＝7.6 Hz, 1H, ArH), 6.51 (s, 1H, CH), 3.94 (d,
J＝16.8 Hz, 1H, CH2), 3.59 (d, J＝17.2 Hz, 1H, CH2),
3.53 (d, J＝16.0 Hz, 1H, CH2), 3.14 (d, J＝16.0 Hz, 1H,
CH2); IR (KBr) v: 3211－, 1636, 1602, 1555, 1357, 1270,
1010, 747, 513 cm 1; HRMS (ESI) calcd for
C19H15BrN3OS [M＋H]＋ 412.0119, found 412.0115.
5-(2-Fluorophenyl)-5,12-dihydro-1H-benzo[4,5]imi-
dazo[1,2-a]thiopyrano[3,4-d]pyrimidin-4(3H)-one (4c):
1H NMR (CDCl3) δ: 11.55 (s, 1H, NH), 7.47 (s, 1H,
ArH), 7.41 (d, J＝8.0 Hz, 1H, ArH), 7.35 (d, J＝7.6 Hz,
1H, ArH), 7.31—7.22 (m, 3H, ArH), 7.09 (t, J＝8.0 Hz,
1H, ArH), 7.02 (t, J＝7.6 Hz, 1H, ArH), 6.55 (s, 1H,
CH), 3.95 (d, J＝16.8 Hz, 1H, CH2), 3.63 (d, J＝17.2
Hz, 1H, CH2), 3.54 (d, J＝16.0 Hz, 1H, CH2), 3.16 (d,
J＝16.4 Hz, 1H, CH2); IR (KBr) v: 3399, 2872, 1638,
Scheme 3
O
H
N
HOAc
+
N
CH
S
N
O
5a
2
S
NH
N
N
O
4a
Conclusion
In summary, we have developed a simple and effi-
cient method for synthesis of a series of benzo[4,5]-
imidazo[1,2-a]thiopyrano[3,4-d]pyrimidin-4(3H)-one
derivatives via a one-pot multi-component reaction in
acidic media. This procedure features short reaction
time, generally good to excellent yields, easily available
starting materials, and operational simplicity (only one
pot).
－1
1616, 1592, 1570, 1359, 1268, 1206, 757, 510 cm ;
＋
Experimental
HRMS (ESI) calcd for C19H15FN3OS [M ＋ H]
352.0920, found 352.0917.
Reaction progress was monitored with analytical
TLC on 0.25 mm silica gel precoated glass plates with a
fluorescent indicator UV254. Melting points were de-
termined in open capillaries and are uncorrected. IR
spectra were recorded on a TENSOR 27 spectrometer in
5-(4-Fluorophenyl)-5,12-dihydro-1H-benzo[4,5]imi-
dazo[1,2-a]thiopyrano[3,4-d]pyrimidin-4(3H)-one (4d):
1H NMR (CDCl3) δ: 11.49 (s, 1H, NH), 7.41—7.38 (m,
3H, ArH), 7.31 (d, J＝7.6 Hz, 1H, ArH), 7.09 (t, J＝8.8
Hz, 3H, ArH), 7.00 (t, J＝7.6 Hz, 1H, ArH), 6.53 (s, 1H,
CH), 3.95 (d, J＝16.8 Hz, 1H, CH2), 3.61 (dd, J1＝1.2
Hz, J2＝16.8 Hz, 1H, CH2), 3.54 (dd, J1＝0.8 Hz, J2＝
16.0 Hz, 1H, CH2), 3.15 (dd, J1＝1.2 Hz, J2＝16.0 Hz,
1H, CH2); IR (KBr) v: 3210, 3024, 2843, 1641, 1618
1
KBr. H NMR spectra were measured on a DPX 400
spectrometer operating at 400 MHz, using CDCl3 or
DMSO-d6 as solvent and TMS as an internal standard.
HRMS (ESI) were determined by using micro-
TOF-QIIHRMS/MS instrument (Bruker). Solvents and
commercial reagents of analytical reagent grade were
purchased and used without any further purification.
－1
1593, 1572, 1512, 1348, 1273, 1229, 744, 527 cm ;
＋
HRMS (ESI) calcd for C19H15FN3OS [M ＋ H]
352.0920, found 352.0917.
General procedure for the synthesis of 5-aryl-5,12-
dihydro-1H-benzo[4,5]imidazo[1,2-a]thiopyrano[3,4-
d]pyrimidin-4(3H)-one
5-(2-Chlorophenyl)-5,12-dihydro-1H-benzo[4,5]imi-
dazo[1,2-a]thiopyrano[3,4-d]pyrimidin-4(3H)-one (4e):
1H NMR (CDCl3) δ: 11.63 (s, 1H, NH), 7.54 (s, 1H,
ArH), 7.39 (d, J＝7.6 Hz, 1H, ArH), 7.35 (t, J＝8.0 Hz,
1H, ArH), 7.29 (t, J＝7.2 Hz, 1H, ArH), 7.23 (t, J＝7.6
Hz, 1H, ArH), 7.14 (d, J＝7.6 Hz, 1H, ArH), 7.08 (t,
J＝7.2 Hz, 1H, ArH), 6.99 (t, J＝7.2 Hz, 1H, ArH),
6.72 (s, 1H, CH), 3.93 (d, J＝16.8 Hz, 1H, CH2), 3.62
(d, J＝16.8 Hz, 1H, CH2), 3.49 (d, J＝16.4 Hz, 1H,
CH2), 3.13 (d, J＝16.0 Hz, 1H, CH2); IR (KBr) v: 3216,
Aryl aldehyde 1 (1 mmol), 2H-thiopyran-3,5-
(4H,6H)-dione (2, 1 mmol), 1H-benzo[d]imidazol-2-
amine (3, 1 mmol) and HOAc (10 mL) were mixed and
then stirred at 50 ℃ for 6—10 h. After completion of
the reaction (monitored by TLC), the reaction mixture
was poured into water. After filtration, the solid product
was recrystallized from ethanol (95%) to give pure
product 4.
－1
2899, 1638, 1615, 1565, 1350, 1268, 738, 524 cm ;
HRMS (ESI) calcd for C19H15ClN3OS [M ＋ H] ＋
5-Phenyl-5,12-dihydro-1H-benzo-[4,5]imidazo[1,2-
Chin. J. Chem. 2011, 29, 1727— 1731
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
1729

Shen et al.
FULL PAPER
368.0624, found 368.0612.
(s, 3H, CH3); IR (KBr) v: 3200, 3099, 2751, 1639, 1556,
－1
5-(3-Chlorophenyl)-5,12-dihydro-1H-benzo[4,5]-imi-
dazo[1,2-a]thiopyrano[3,4-d]pyrimidin-4(3H)-one (4f):
1H NMR (CDCl3) δ: 11.57 (s, 1H, NH), 7.56 (t, J＝7.2
Hz, 1H, ArH), 7.39 (d, J＝8.0 Hz, 1H, ArH), 7.28—
7.23 (m, 1H, ArH), 7.16—7.14 (m, 2H, ArH), 7.11—
7.06 (m, 2H, ArH), 7.00 (t, J＝7.2 Hz, 1H, ArH), 6.63
(s, 1H, CH), 3.95 (d, J＝17.6 Hz, 1H, CH2), 3.62 (d, J＝
17.2 Hz, 1H, CH2), 3.52 (d, J＝16.0 Hz, 1H, CH2), 3.14
(d, J＝16.0 Hz, 1H, CH2); IR (KBr) v: 3243, 3047, 1589,
1515, 1456, 1355, 1269, 736, 515＋cm ; HRMS (ESI)
calcd for C20H18N3OS [M ＋ H]
348.1171, found
348.1160.
5-(3-Methoxyphenyl)-5,12-dihydro-1H-benzo[4,5]-
imidazo[1,2-a]thiopyrano[3,4-d]pyrimidin-4(3H)-one
1
(4k): H NMR (CDCl3) δ: 11.47 (s, 1H, NH), 7.38 (t,
J＝7.6 Hz, 2H, ArH), 7.16 (t, J＝8.0 Hz, 1H, ArH),
7.08 (t, J＝7.6 Hz, 1H, ArH), 7.00 (t, J＝7.6 Hz, 1H,
ArH), 6.94 (s, 1H, ArH), 6.83 (d, J＝8.0 Hz, 1H, ArH),
6.75 (d, J＝8.0 Hz, 1H, ArH), 6.49 (s, 1H, CH), 3.95 (d,
J＝16.8 Hz, 1H, CH2), 3.69 (s, 3H, OCH3), 3.60 (d, J＝
17.2 Hz, 1H, CH2), 3.54 (d, J＝16.4 Hz, 1H, CH2), 3.14
(d, J＝16.0 Hz, 1H, CH2); IR (KBr) v: 3396, 2836, 1637,
1611, 1593, 1571, 1455, 1349, 1257, 745, 694, 51＋5
－1
1636, 1589, 1556, 1353, 1266, 794, 745, 517 cm ;
HRMS (ESI) calcd for C19H15ClN3OS [M ＋ H] ＋
368.0624, found 368.0617.
5-(3,4-Dichlorophenyl)-5,12-dihydro-1H-benzo-[4,5]-
imidazo[1,2-a]thiopyrano[3,4-d]pyrimidin-4(3H)-one
1
－1
(4g): H NMR (CDCl3) δ: 11.60 (s, 1H, NH), 7.74 (s,
cm ; HRMS (ESI) calcd for C20H18N3O2S [M＋H]
1H, ArH), 7.53 (d, J＝8.4 Hz, 1H, ArH), 7.41 (d, J＝8.0
Hz, 1H, ArH), 7.36 (d, J＝8.0 Hz, 1H, ArH), 7.22 (d,
J＝8.4 Hz, 1H, ArH), 7.11 (t, J＝7.6 Hz, 1H, ArH),
7.03 (t, J＝7.6 Hz, 1H, ArH), 6.57 (s, 1H, CH), 3.94 (d,
J＝16.8 Hz, 1H, CH2), 3.63 (d, J＝17.2 Hz, 1H, CH2),
3.54 (d, J＝16.0 Hz, 1H, CH2), 3.15 (d, J＝16.0 Hz, 1H,
CH2); IR (KBr) v: 3293, 2886, 1635, 1604, 1560, 1353,
364.1120, found 364.1112.
5-(4-Methoxyphenyl)-5,12-dihydro-1H-benzo[4,5]-
imidazo[1,2-a]thiopyrano[3,4-d]pyrimidin-4(3H)-one
(4l): 1H NMR (CDCl3) δ: 11.37 (s, 1H, NH), 7.38 (t, J＝
8.0 Hz, 1H, ArH), 7.31 (d, J＝8.0 Hz, 1H, ArH), 7.26 (d,
J＝8.4 Hz, 2H, ArH), 7.07 (t, J＝7.6 Hz, 1H, ArH),
6.99 (t, J＝7.6 Hz, 1H, ArH), 6.80 (d, J＝8.8 Hz, 2H,
ArH), 6.45 (s, 1H, CH), 3.95 (d, J＝16.8 Hz, 1H, CH2),
3.66 (s, 3H, OCH3), 3.59 (d, J＝16.0 Hz, 1H, CH2),
3.53 (d, J＝16.0 Hz, 1H, CH2), 3.13 (d, J＝16.0 Hz, 1H,
CH2); IR (KBr) v: 3320, 2905, 1638, 1614, 1567, 1512,
－1
1264, 1031, 746, 512 cm ; HRMS (ESI) calcd for
C19H14Cl2N3OS [M＋H]＋ 402.0235, found 402.0209.
5-(3-Nitrophenyl)-5,12-dihydro-1H-benzo[4,5]imida-
zo[1,2-a]thiopyrano[3,4-d]pyrimidin-4(3H)-one (4h):
1H NMR (CDCl3) δ: 11.65 (s, 1H, NH), 8.29 (s, 1H,
ArH), 8.06 (d, J＝8.0 Hz, 1H, ArH), 7.72 (d, J＝7.6 Hz,
1H, ArH), 7.57 (t, J＝8.0 Hz, 1H, ArH), 7.41 (d, J＝8.0
Hz, 1H, ArH), 7.34 (d, J＝7.6 Hz, 1H, ArH), 7.09 (t,
J＝8.0 Hz, 1H, ArH), 7.00 (t, J＝7.6 Hz, 1H, ArH),
6.74 (s, 1H, CH), 3.96 (d, J＝16.8 Hz, 1H, CH2), 3.64
(d, J＝16.8 Hz, 1H, CH2), 3.54 (d, J＝16.0 Hz, 1H,
CH2), 3.16 (d, J＝16.0 Hz, 1H, CH2); IR (KBr) v: 3228,
3053, 2915, 1638, 1589, 1556, 1348, 1271, 1212, 748,
－1
1351, 1253, 1178, 1031, 839, 744, 531 cm ; HRMS
(ESI) calcd for C20H18N3O2S [M ＋ H] ＋ 364.1120,
found 364.1117.
5-(3,4,5-Trimethoxyphenyl)-5,12-dihydro-1H-benzo-
[4,5]imidazo[1,2-a]thiopyrano[3,4-d]pyrimidin-4(3H)-
1
one (4m): H NMR (CDCl3) δ: 11.45 (s, 1H, NH), 7.53
(d, J＝7.6 Hz, 1H, ArH), 7.39 (d, J＝8.0 Hz, 1H, ArH),
7.09 (t, J＝7.6 Hz, 1H, ArH), 7.04 (t, J＝7.6 Hz, 1H,
ArH), 6.67 (s, 2H, ArH), 6.48 (s, 1H, CH), 3.95 (d, J＝
16.8 Hz, 1H, CH2), 3.69 (s, 6H, 2OCH3), 3.65 (d, J＝
17.2 Hz, 1H, CH2), 3.57 (s, 3H, OCH3), 3.55 (d, J＝
16.0 Hz, 1H, CH2), 3.19 (d, J＝16.0 Hz, 1H, CH2); IR
(KBr) v: 3350, 2942, 2838, 1645, 1614, 1593, 1573,
－1
730 cm ; HRMS (ESI) calcd for C19H15N4O3S [M＋
H]＋ 379.0865, found 379.0824.
5-(4-Nitrophenyl)-5,12-dihydro-1H-benzo[4,5]imi-
dazo[1,2-a]thiopyrano[3,4-d]pyrimidin-4(3H)-one (4i):
1H NMR (CDCl3) δ: 11.62 (s, 1H, NH), 8.14 (d, J＝8.8
Hz, 2H, ArH), 7.62 (d, J＝8.4 Hz, 2H, ArH), 7.41 (d,
J＝8.0 Hz, 1H, ArH), 7.29 (d, J＝8.0 Hz, 1H, ArH),
7.10 (d, J＝7.6 Hz, 1H, ArH), 7.00 (t, J＝7.6 Hz, 1H,
ArH), 6.69 (s, 1H, CH), 3.97 (d, J＝16.8 Hz, 1H, CH2),
3.62 (d, J＝17.2 Hz, 1H, CH2), 3.55 (d, J＝16.0 Hz, 1H,
CH2), 3.15 (dd, J1＝1.2 Hz, J2＝16.0 Hz, 1H, CH2); IR
(KBr) v: 3217, 1637, 160－3, 1589, 1556, 1520, 1349,
1272, 828, 745, 511＋ cm 1; HRMS (ESI) calcd for
C19H15N4O3S [M＋H] 379.0865, found 379.0833.
5-(p-Tolyl)-5,12-dihydro-1H-benzo-[4,5]imidazo-
[1,2-a]thiopyrano[3,4-d]pyrimidin-4(3H)-one (4j): 1H
NMR (CDCl3) δ: 11.40 (s, 1H, NH), 7.37 (d, J＝8.0 Hz,
1H, ArH), 7.28 (d, J＝7.6 Hz, 1H, ArH), 7.22 (d, J＝8.0
Hz, 2H, ArH), 708—7.04 (m, 3H, ArH), 6.98 (t, J＝7.6
Hz, 1H, ArH), 6.45 (s, 1H, CH), 3.94 (d, J＝16.8 Hz,
1H, CH2), 3.59 (d, J＝17.2 Hz, 1H, CH2), 3.53 (d, J＝
16.0 Hz, 1H, CH2), 3.12 (d, J＝16.0 Hz, 1H, CH2), 2.18
－1
1349, 1241, 1127, 1006, 736, 510 ＋cm ; HRMS (ESI)
calcd for C22H22N3O4S [M ＋ H] 424.1331, found
424.1325.
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