Synthesis of functionalized thiophenes by four-component reactions of 1,3-thiazolidinedione, aromatic aldehydes, cyanoacetamide and cyclic secondary amines

Article abstract of DOI:10.1002/cjoc.201180417

The polysubstituted thiophene derivatives were conveniently prepared by the four-component reactions of 1,3-thiazolidinedione, aromatic aldehydes, cyanoacetamide and cyclic secondary amines such as pyrrolidine, morpholine and piperidine. The reaction mech

Full text of DOI:10.1002/cjoc.201180417

FULL PAPER
Synthesis of Functionalized Thiophenes by Four-component
Reactions of 1,3-Thiazolidinedione, Aromatic Aldehydes,
Cyanoacetamide and Cyclic Secondary Amines
Yao, Rong(姚荣)
Xia, Eryan(夏二艳)
Sun, Jing(孙晶)
Yan, Chaoguo*(颜朝国)
College of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou 225002, China
The polysubstituted thiophene derivatives were conveniently prepared by the four-component reactions of
1,3-thiazolidinedione, aromatic aldehydes, cyanoacetamide and cyclic secondary amines such as pyrrolidine, mor-
pholine and piperidine. The reaction mechanism is believed to involve domino reactions of Knoevenagel condensa-
tion, Michael addition, ring-opening and recyclization of 1,3-thiazolidinedione.
Keywords multicomponent reaction, domino reaction, thiophene, cyanoacetamide, 1,3-thiazolidinedione
Introduction
reactions.
As one kind of main heterocyclic compounds, thio-
phene and its substituted derivatives possess useful bio-
logical activities and exhibit extensive applications in
material and pharmaceutical sciences.1-4 Though various
methods for preparation of thiophenes have been estab-
lished, the elaboration of the existing thiophene skeleton
with multiple substituents at the specific positions is still
a challenging work.5-11 Gewald’s reaction might be one
of the most convenient and well-established method for
preparing polysubstituted thiophenes which involves
multicomponent reaction of a ketone, an activated nitrile
with elemental sulfur in the presence of base cata-
lyst.12-14 In the past two decades, multicomponent reac-
tion has become one of the most attractive synthetic
method because they offer significant advantages over
conventional linear-step syntheses due to their flexible,
convergent and atom efficient nature.15-19 Recently, we
developed an unprecedented and efficient synthetic
protocol for the polysubstituted dihydrothiophens via
domino reaction of 1,3-thiazolidinedione, malononitrile,
aromatic aldehydes and amines.20-22 The reaction
showed very interesting molecular diversity when one
or two reaction components were changed. The reac-
tions of ethyl cyanoacetate and pivaloylacetonitrile still
gave the corresponding functionalized dihydrothio-
phenes.23,24 On the other hand, the reactions of
cyanoacetamide yielded ammonium S— S bond linked
pyridinedionates as main products when diethylamine,
di-i-propylamine were used as the amine compounent.25
In order to examine the substrate scope and limitation of
this novel domino reaction, we wish to report the
preparation of polysubstituted thiophene derivatives by
using cyclic secondary amines in the multicomponent
Results and discussion
According to the previously established reaction
conditions,25 the four-component reaction of 1,3-thia-
zolidinedione, aromatic aldehydes, cyanoacetamide and
cyclic secondary amines such as pyrrolidine in acetoni-
trile was carried out at room temperature. Unfortunately,
the outcome was a complicated mixture of products
from which the desired product could not be separated
in most cases. Then the reaction condition of the
four-component reaction was examined with regard to
solvents, temperature and adding sequences of sub-
strates. But the results are still very disappointing. In
another previous report we have demonstrated that the
arylamine could take part in the four component reac-
tion by adding triethylamine as base catalyst.21 Thus
triethylamine was added in the above four-component
reaction and the reaction mixture was heated at 50— 60
℃ for 2 d. The four-componet reaction now proceeds
very smoothly and after workup one kind of polysubsti-
tuted thiophenes 1a— 1d were successfully obtained in
moderate yields (32%— 40%). Then other cyclic secon-
dary amine such as piperidine, morphiline also gave the
corresponding functionalized thiophenes 1e— 1k under
the same reaction condition. It should be noticed that the
dehydrogenated thiophens were produced as main
products, while in the reactions of malononitirile and
pivaloylacetonitrile only dihydrothiophenes were ob-
tained. The direct formation of thiophene derivatives is
obviously due to oxidative dehydrogenation of the ini-
tially formed dihydrothiophene intermediates in the
relatively longer heating process in air (two days). Try-
*
E-mail: cgyan@yzu.edu.cn; Tel.: 0086-0514-87975531; Fax: 0086-0514-87975520
Received April 6, 2011; revised May 20, 2011; accepted July 11, 2011.
Project supported by the National Natural Science Foundation of China (No. 20972132).
Chin. J. Chem. 2011, 29, 2461— 2464
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
2461

Yao et al.
FULL PAPER
ing to prepare dihydrothiophens by the reaction of
cyanoacetamide in nitrogen atmospheres was not suc-
cessful. Thus our present protocol provides an conven-
ient method for the synthesis of polysubstituted thio-
phenes. On the other hand, the reactivity of other
amines such as diethylamine, benzylamine, aniline and
toludine are also tested. It is a pity that these reactions
gave very complicated mixtures, from which no main
product could be separated. The structures of 1a— 1k
1
were fully determined by H NMR and 13C NMR, MS,
IR spectra, elemental analysis and were further con-
firmed by single-crystal X-ray diffraction determination
of one representative compound 1j (Figure 1).
Table 1 The synthesis of thiophenes 1a— 1k via four-compo-
nent reactions
O
Et3N/CH3CN
+
+
+
ArCHO
CNCH2CONH2
NHR2
NH
S
50 ℃
Figure 1 Molecular structure of thiophene 1j.
O
H2N
O
O
C
O
C
S
H
Scheme 1 Proposed mechanism for the four-component reac-
NR2
N
tion
NH2
Ar
C
N
O
B:
C
Entry
Compd
1a
R2NH
Ar
Yield/%
32
ArCHO +
O
ArCH C
N
CONH2
NH2
1
2
(CH2)4NH
(CH2)4NH
(CH2)4NH
(CH2)4NH
(CH2)5NH
(CH2)5NH
C6H5
A
1b
1c
p-CH3C6H4
p-ClC6H4
p-ClC6H4
C6H5
36
3
40
NH
NH2
S
Ar
4
1d
1e
34
O
R2NH
O
5
33
O
NH
CN
B:
S
6
1f
p-CH3C6H4
36
O
7
1g
O(CH2)4NH C6H5
30
B
NH2
8
1h
1i
O(CH2)4NH p-CH3C6H4
O(CH2)4NH p-FC6H4
O(CH2)4NH p-ClC6H4
O(CH2)4NH p-BrC6H4
34
NH2
O
Ar
Ar
O
HN
O
9
32
O
NH
O
NR2
10
11
1j
42
-
C
N
S
S
H2N
NR2
O
1k
40
D
C
NH2
Ar
To explain the formation of the functionalized thio-
phenes via this domino multicomponent reaction, we
outlined tentatively a plausible reaction mechanism
based on the previously proposed mechanism for the
formation of dihydrothiophenes20 (Scheme 1). Firstly,
the basic catalytic Knoevenagel condensation of cyano-
acetamide with aromatic aldehyde gives arylidene-
cyanoacetamide (A). Secondly, Michael addition of the
carbanion of 1,3-thiazolidinedione to arylidene cyano-
acetamide (A) yields intermediate (B). Thirdly, the cy-
clic secondary amine attacks the carbonyl group of
1,3-thiazolidinedione to open its ring and cause the
formation of a sulfide anion (C). Fourthly, the in-
tramolecular addition of sulfide anion to the cyano
group in intermediate (C) yields a dihydrothiophene
derivative (D). At last thiophene 1 is produced by dehy-
drogenation process in air.
O
H
[O]
N
O
NR2
S
O
H2N
1
In summary, we have developed our previously re-
ported four-component reaction to cyclic secondary
amines and found interesting molecular diversity of the
reaction. The domino reactions of cyanoacetamide,
aromatic aldehydes, 1,3-thiazolidinedione and cyclic
secondary amines yielded the polysusbtituted thio-
phenes. The simple procedure, mild conditions, high
efficiency of bond formation of this reaction make it an
attractive convenient protocol for the synthesis of thio-
phene derivatives even though the yields of the products
is relatively lower. Further expansion of the reaction
scope and synthetic applications of this methodology
are in progress in our laboratory.
2462
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© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2011, 29, 2461— 2464

Synthesis of Functionalized Thiophenes by Four-component Reactions
Experimental
CONH2), 3.03 (s, 2H, CH2), 2.68 (s, 2H, CH2), 1.67 (s,
4H, CH2); 13C NMR (DMSO-d6, 150 MHz) δ: 166.6,
163.2, 150.7, 140.9, 134.3, 131.7, 122.0, 114.0, 110.3,
45.4, 25.0, 23.8; IR (KBr) v: 3489, 3392, 3301, 1708,
1632, 1580, 1509, 1475, 1422, 1400, 1299, 1248, 1171,
General procedure for the synthesis of polysubsti-
tuted thiophenes (1a— 1k)
A mixture of aromatic aldehyde (4.0 mmol), cyano-
acetamide (4.0 mmol, 0.34 g) and cyclic secondary
amine (4.0 mmol) in acetonitrile (5.0 mL) was stirred at
room temperature until the aldehyde disppeared by TLC
analysis. Then 1,3-thiazolidinedione (4.0 mmol, 0.47 g)
and triethylamine (1.0 mmol) were added and the
reaction was stirred at 50 ℃ for an additional 48 h. The
resulting precipitate was collected by filtration and
washed with acetonitrile. Recrystallization from a
mixture of acetonitrile and DMF gave the pure product.
－1
1091, 1012, 89＋5, 859, 787, 756 cm ; MS m/z (%):
436.78 ([M－1] , 100). Anal. calcd for C17H17BrN4O3S:
C 46.69, H 3.92, N 12.81; found C 46.33, H 4.25, N
12.50.
1
1e: White solid, yield 33%, m.p.＞250 ℃; H NMR
(DMSO-d6, 600 MHz) δ: 7.99 (s, 2H, NH2), 7.77 (brs,
1H, NH), 7.56—7.52 (m, 3H, ArH), 7.42—7.40 (m, 2H,
ArH), 6.95 (s, 1H, CONH2), 4.65 (s, 1H, CONH2), 2.93
(s, 4H, CH2), 1.46—1.43 (m, 2H, CH2), 1.29 (brs, 4H,
1
13
1a: White solid, yield 32%, m.p. 236—238 ℃; H
CH2); C NMR (DMSO-d6, 150 MHz) δ: 166.8, 164.4,
NMR (DMSO-d6, 600 MHz) δ: 7.97 (s, 2H, NH2), 7.69
(brs, 1H, NH), 7.55—7.51 (m, 3H, ArH), 7.40 (d, J＝
7.2 Hz, 2H, ArH), 6.94 (s, 1H, CONH2), 4.62 (s, 1H,
CONH2), 3.34 (s, 2H, CH2), 3.06 (s, 2H, CH2), 1.63 (s,
4H, CH2); 13C NMR (DMSO-d6, 150 MHz) δ: 166.8,
164.4, 160.9, 150.1, 141.7, 135.1, 129.4, 129.3, 129.1,
113.9, 109.5, 45.7, 45.6, 45.1, 45.0, 23.8; IR (KBr) v:
3475, 3385, 3306, 3267, 2972, 2870, 1710, 1631, 1576,
1478, 1419, 1364, 1299, 1249, 1230, 1173, 1093, 946,
161.2, 151.1, 141.9, 135.1, 130.0, 129.3, 129.2, 129.1,
113.5, 109.3, 44.3, 25.2, 23.6, 23.1; IR (KBr) v: 3481,
3403, 3372, 3296, 2938, 2853, 1709, 1633, 1575, 1483,
1411, 1362, 1305, 1244, 1221, 1175, 1139, 1126－, 1084,
1
1035, 939, 924, 893, 853, 83＋9, 814, 787, 755 cm ; MS
m/z (%): 371.78 ([M－1] , 100). Anal. calcd for
C18H20N4O3S: C 58.05, H 5.41, N 15.04; found C 57.74,
H 5.71, N 14.68.
1
1f: White solid, yield 36%, m.p. 240—241 ℃; H
＋
－1
864, 834, 787, 758 cm ; MS m/z (%): 357.70 ([M－1] ,
100). Anal. calcd for C17H18N4O3S: C 56.97, H 5.06, N
15.63; found C 56.78, H 5.40, N 15.17.
NMR (DMSO-d6, 600 MHz) δ: 8.02 (s, 2H, NH2), 7.59
(brs, 1H, NH), 7.37 (d, J＝7.8 Hz, 2H, ArH), 7.30 (d,
J＝7.8 Hz, 2H, ArH), 6.94 (s, 1H, CONH2), 4.64 (s, 1H,
CONH2), 2.92 (s, 4H, CH2), 2.38 (s, 3H, CH3),
1.45—1.44 (m, 2H, CH2), 1.27 (s, 4H, CH2); 13C NMR
(DMSO-d6, 150 MHz) δ: 166.9, 164.6, 160.9, 150.9,
141.8, 138.9, 131.9, 130.0, 129.2, 113.6, 109.2, 44.5,
44.3, 25.2, 23.6, 23.1, 20.8; IR (KBr) v: 3483, 3401,
3379, 3301, 3270, 2943, 2858, 1704, 1631, 1573, 1484,
1409, 1361, 1302, 1244, 1217, 1170, 1139, 1088, 932,
1
1b: White solid, yield 36%, m.p. 240—242 ℃; H
NMR (DMSO-d6, 600 MHz) δ: 8.00 (s, 2H, NH2), 7.37
(d, J＝7.2 Hz, 2H, ArH), 7.30 (d, J＝7.8 Hz, 2H, ArH),
6.93 (brs, 1H, CONH2), 4.63 (brs, 1H, CONH2), 3.33 (s,
2H, CH2), 3.07 (s, 2H, CH2), 2.37 (s, 3H, CH3), 1.64 (s,
4H, CH2); 13C NMR (DMSO-d6, 150 MHz) δ: 166.9,
164.7, 160.7, 150.0, 141.6, 138.9, 132.0, 130.0, 129.3,
114.0, 109.3, 45.1, 20.8; IR (KBr) v: 3474, 3377, 3302,
3264, 2969, 2872, 1710, 1631, 1574, 1481, 1421－, 1364,
＋
－1
895, 849, 776, 757 cm ; MS m/z (%): 385.50 ([M－1] ,
100). Anal. calcd for C19H22N4O3S: C 59.05, H 5.74, N
14.50; found C 59.27, H 6.03, N 14.22.
1
1300, 1249, 1230, 1171, 109＋2, 843, 789, 758 cm ; MS
1
m/z (%): 371.78 ([M－1] , 100). Anal. calcd for
C18H20N4O3S: C 58.05, H 5.41, N 15.04; found C 57.82,
H 5.77, N 14.75.
1g: White solid, yield 30%, m.p.＞250 ℃; H NMR
(DMSO-d6, 600 MHz) δ: 7.98 (s, 3H, NH, NH2), 7.52 (s,
3H, ArH), 7.38 (brs, 2H, ArH), 6.96 (s, 1H, CONH2),
4.68 (s, 1H, CONH2), 3.39 (s, 4H, CH2), 2.92 (s, 4H,
1
1c: White solid, 40%, m.p. 246—247 ℃; H NMR
13
(DMSO-d6, 600 MHz) δ: 8.33 (brs, 1H, NH), 7.71 (s,
2H, NH2), 7.53 (d, J＝8.4 Hz, 2H, ArH), 7.32 (d, J＝7.8
Hz, 2H, ArH), 6.96 (brs, 1H, CONH2), 5.04 (brs, 1H,
CONH2), 3.03 (brs, 2H, CH2), 2.70 (s, 2H, CH2), 1.66 (s,
4H, CH2); 13C NMR (DMSO-d6, 150 MHz) δ: 166.7,
163.4, 162.0, 150.7, 140.8, 133.9, 133.5, 131.4, 131.0,
128.6, 114.1, 110.2, 45.4, 44.9, 23.6; IR (KBr) v: 3490,
3392, 3305, 3268, 3089, 2971, 1871, 1708, 1631, 1576,
1475, 1423, 1299, 1249, 1229, 1172, 1088, 1017, 940,
CH2); C NMR (DMSO-d6, 150 MHz) δ: 166.8, 164.5,
161.5, 151.5, 142.2, 135.1, 130.0, 129.4, 129.3, 129.1,
128.9, 113.4, 109.4, 65.6, 64.7, 44.6, 44.0; IR (KBr) v:
3478, 3399, 3308, 2968, 1711, 1632, 1576, 1483, 1410,
1300, 1265, 1221, 1173, 1112, 1026, 928, 836, 788, 752
＋
－1
cm ; MS m/z (%): 373.46 ([M－1] , 100). Anal. calcd
for C17H18N4O4S: C 54.53, H 4.85, N 14.96; found C
54.40, H 5.17, N 14.62.
1
1h: White solid, yield 34%, m.p.＞250 ℃; H NMR
＋
－1
(DMSO-d6, 600 MHz) δ: 8.01 (s, 2H, NH2), 7.88 (brs,
1H, NH), 7.36 (d, J＝7.2 Hz, 2H, ArH), 7.28 (d, J＝7.2
Hz, 2H, ArH), 6.95 (s, 1H, CONH2), 4.68 (s, 1H,
CONH2), 3.39 (s, 4H, CH2), 2.92 (s, 4H, CH2), 2.38 (s,
3H, CH3); 13C NMR (DMSO-d6, 150 MHz) δ: 166.9,
164.7, 161.2, 151.3, 142.2, 138.9, 131.9, 129.9, 129.3,
113.5, 109.3, 65.6, 44.0, 20.8; IR (KBr) v: 3481, 3390,
3308, 1707, 1632, 1573, 1483, 1413, 1301, 1219, 1169,
897, 861, 787, 757 cm ; MS m/z (%): 391.83 ([M－1] ,
＋
100), 393.88 ([M ＋ 1] , 38). Anal. calcd for
C17H17ClN4O3S: C 51.97, H 4.36, N 14.26; found C
51.80, H 4.76, N 13.89.
1
1d: White solid, 34%, m.p. 248—249 ℃; H NMR
(DMSO-d6, 600 MHz) δ: 8.33 (brs, 1H, NH), 7.69 (s,
2H, NH2), 7.66 (d, J＝7.8 Hz, 2H, ArH), 7.25 (d, J＝7.8
Hz, 2H, ArH), 6.96 (brs, 1H, CONH2), 5.05 (brs, 1H,
Chin. J. Chem. 2011, 29, 2461— 2464
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
2463

Yao et al.
FULL PAPER
－1
1119, 934, 846, 789, 756 cm ; MS m/z (%): 387.82
([M－1]＋, 100). Anal. calcd for C18H20N4O4S: C 55.66,
H 5.19, N 14.42; found C 55.29, H 5.47, N 14.35.
References
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1
1i: White solid, yield 32%, m.p.＞250 ℃; H NMR
(DMSO-d6, 600 MHz) δ: 8.55 (s, 1H, NH), 7.81 (s, 2H,
NH2), 7.36 (brs, 2H, ArH), 7.33—7.31 (m, 2H, ArH),
6.97 (s, 1H, CONH2), 4.93 (s, 1H, CONH2), 3.42 (s, 4H,
CH2), 3.01 (s, 4H, CH2); 13C NMR (DMSO-d6, 150
MHz) δ: 166.7, 163.7, 163.0, 162.1, 161.4, 151.9, 151.5,
141.6, 131.7, 131.6, 131.3, 115.7, 115.5, 114.3, 113.4,
110.0, 65.8, 65.6, 63.9, 47.1, 44.2, 43.3; IR (KBr) v:
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1410, 1366, 1301, 1271, 1227, 1171, 1113, 1024, 933,
2
3
4
5
6
7
8
9
＋
－1
896, 864, 801, 756 cm ; MS m/z (%): 391.87 ([M－1] ,
100). Anal. calcd for C17H17FN4O4S: C 52.03, H 4.37, N
14.28; found C 51.84, H 4.77, N 13.89.
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1
1j: White solid, yield 42%, m.p.＞250 ℃; H NMR
(DMSO-d6, 600 MHz) δ: 8.45 (brs, 1H, NH), 7.72 (s,
2H, NH2), 7.52 (d, J＝8.4 Hz, 2H, ArH), 7.31 (d, J＝8.4
Hz, 2H, ArH), 6.98 (brs, 1H, CONH2), 5.07 (brs, 1H,
CONH2), 3.42—3.41 (m, 4H, CH2), 3.00 (s, 4H, CH2);
13C NMR (DMSO-d6, 150 MHz) δ: 166.6, 163.3, 162.4,
152.0, 141.4, 134.0, 133.4, 131.4, 131.0, 129.4, 128.5,
113.4, 110.2, 65.6, 65.4, 44.5, 44.1; IR (KBr) v: 3491,
3385, 3294, 2968, 2856, 1717, 1632, 1574, 1479, 1418,
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＋
1
895, 856, 785, 753 cm ; MS m/z (%): 407.40 ([M－1] ,
100). Anal. calcd for C17H17ClN4O4S: C 49.94, H 4.19,
N 13.70; found C 50.15, H 4.66, N 13.42.
1
1k: White solid, yield 40%, m.p.＞250 ℃; H NMR
(DMSO-d6, 600 MHz) δ: 8.49 (brs, 1H, NH), 7.71 (s,
2H, NH2), 7.65 (d, J＝6.6 Hz, 2H, ArH), 7.24 (d, J＝7.2
Hz, 2H, ArH), 6.98 (brs, 1H, CONH2), 5.09 (brs, 1H,
CONH2), 3.42 (s, 4H, CH2), 2.99 (s, 4H, CH2); 13C
NMR (DMSO-d6, 150 MHz) δ: 166.6, 163.3, 162.4,
151.9, 141.4, 134.4, 132.3, 131.7, 131.5, 131.4, 131.3,
131.2, 122.1, 113.4, 110.2, 65.6, 65.1, 44.4, 44.1; IR
(KBr) v: 3496, 3408, 3391, 3299, 1777, 1721, 1633,
1569, 1481, 1418, 1299, 1214, 1171, 1119, 1015, 972,
－1
932, 896, 850, 787, 756 cm ; MS m/z (%): 452.15
([M－1]＋, 100). Anal. calcd for C17H17BrN4O4S: C
45.04, H 3.78, N 12.36; found C 44.77, H 4.24, N 12.37.
Supporting information
Crystallographic data of 3j (CCDC 753689) has
been deposited at the Cambridge Crystallographic Da-
tabase Centre and is available on request from
http://www.ccdc.cam.ac.uk.
25 Sun, J.; Xia, E. Y.; Wu, Q.; Yan, C. G. Tetrahedron 2010, 66,
7794.
(E1104064 Lu, Y.; Fan, Y.)
2464
www.cjc.wiley-vch.de
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2011, 29, 2461— 2464