Post on 03-Feb-2018
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Supporting Information
Polymer based heterogeneous reusable catalyst for the synthesis of
benzoyl fumerate from aldehyde and acetylenedicarboxylate
BishwapranKashyap and ProdeepPhukan
Department of Chemistry, GauhatiUniversity, Guwahati-781014, Assam, India
Typical experimental procedure for polymer catalyzed synthesis of benzoyl
fumarate: A solution of DMAD (0.142 g, 1 mmol) and 4-nitrobenzaldehyde (0.045 g, 1
mmol) in anhydrous DME (5 mL) was cooled to 0 °C under N2. PVPEVB (15 wt%) was
then added and the reaction was stirred at room temperature for 8 hour. After the
completion of the reaction the mixture was filtered and the residue was washed with
DCM. The combined filtrate was concentrated and purified using column
chromatography to get the pure product 1e with 80% yield.
Experimental Data
Dimethyl (2E)-2-benzoylbut-2-enedioate (1a)2, 3,6,7: Colorless crystalline solid. mp: 79-81
°C. IR (KBr, cm-1): ν 1207, 1261, 1423, 1681, 1728, 2306, 2985, 3055. 1H NMR
(300MHz, CDCl3, TMS): δ 3.64 (s, 3H), 3.79 (s, 3H), 7.11 (s, 1H), 7.3-7.55 (m, 2H),
7.56-7.65 (m, 1H), 7.7-7.98 (m, 2H). 13C NMR (75 MHz, CDCl3, TMS): δ 52.49, 53.29,
128.66, 128.82, 130.47, 133.91, 135.47, 145.21, 163.58, 164.18, 192.20.
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Dimethyl (2E)-2-(4-bromobenzoyl)but-2-enedioate (1b)1-5: white crystalline solid.mp: 88-
90 °C. IR (KBr, cm-1): ν 1192, 1271, 1425, 1576, 1725, 2951 1H NMR (300MHz,
CDCl3, TMS): δ 3.63 (s, 3H), 3.76 (s, 3H), 7.08 (s, 1H), 7.61 (d, J = 6 Hz, 2H), 7.73 (d, J
= 6Hz, 2H). 13C NMR (75 MHz, CDCl3, TMS): δ 52.48, 53.23, 129.09, 129.95, 130.63,
132.08, 134.20, 144.64, 163.20, 164.02, 191.14.
Dimethyl (2E)-2-(4-chlorobenzoyl)but-2-enedioate (1c)2a, 3-5: Colorless crystalline solid.
mp: 78-80°C . IR (KBr, cm-1): ν 1207, 1273, 1423, 1589, 1685, 2985. 1H NMR (300MHz,
CDCl3, TMS): δ 3.66 (s, 3H), 3.79 (s, 3H), 7.10 (s, 1H), 7.465 (d, J = 9 Hz, 2H),
7.825(d, J = 9 Hz, 2H). 13C NMR (75 MHz, CDCl3, TMS): δ 52.58, 53.35, 129.22,
129.97, 130.72, 133.90, 140.41, 144.79, 163.34, 164.14, 191.04.
Dimethyl (2E)-2-(4-fluorobenzoyl)but-2-enedioate (1d)4-6: Yellow oil. IR (KBr, cm-1): ν
1397, 1422, 1674, 1729, 2955.1H NMR (300MHz, CDCl3, TMS): δ 3.66 (s, 3H), 3.79 (s,
3H), 7.10 (s, 1H), 7.11-7.22 (m, 2H), 7.86-7.97 (m, 2H). 13C NMR (75 MHz, CDCl3,
TMS): δ 52.54, 53.31, 115.95, 116.24, 130.55, 131.26, 131.39, 144.91, 163.43, 164.15,
190.64.
Dimethyl (2E)-2-(4-nitrobenzoyl)but-2-enedioate (1e)2-5: Yellow crystalline solid. ). mp:
115-117 °C. IR (KBr, cm-1): ν 1194, 1359, 1453, 1665, 1721, 2943.1H NMR (300MHz,
CDCl3, TMS): δ 3.65 (s, 3H), 3.78 (s, 3H), 7.12 (s, 1H), 8.025 (d, J = 9 Hz, 2H), 8.305
(d, J = 9 Hz, 2H). 13C NMR (75 MHz, CDCl3, TMS): δ 52.66, 53.36, 123.96, 129.46,
131.24, 139.67, 144.25, 150.46, 162.84, 164.07, 190.69.
Dimethyl (2E)-2-(4-methoxybenzoyl)but-2-enedioate (1f)3-6: Yellow oil. IR (KBr, cm-1): ν
1120, 1270, 1425, 1724, 2945. 1H NMR (300MHz, CDCl3, TMS): δ 3.64 (s, 3H), 3.78
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(s,3H), 3.88 (s, 3H), 6.955 (d, J = 9 Hz, 2H), 7.08 (s, 1H), 7.855 (d, J = 9Hz, 2H). 13C
NMR (75 MHz, CDCl3, TMS): δ 52.28, 52.69, 53.46, 129.33, 130.08, 130.83, 134.01,
140.52, 144.90, 163.45, 164.25, 191.15.
Dimethyl (2E)-2-(4-methylbenzoyl)but-2-enedioate (1g)2-5: Colorless crystalline solid.
mp: 85-87 °C. IR (KBr, cm-1): ν 1169, 1278, 1433, 1609, 1721, 2956. 1H NMR
(300MHz, CDCl3, TMS): δ 2.42 (s, 3H), 3.64 (s, 3H), 3.78 (s, 3H), 7.09 (s, 1H), 7.285 (d,
J = 9 Hz, 2H), 7.785 (d, J = 9 Hz, 2H). 13C NMR (75 MHz, CDCl3, TMS): δ 30.28, 53.05,
53.85, 129.39, 130.15, 130.84, 133.69, 145.57, 145.92, 164.28, 164.80, 192.41.
Dimethyl (2E)-2-(naphthalen-2-ylcaronyl)but-2-enedioate (1h)5-6: Yellow oil. IR (KBr, cm-
1): ν1265, 1422, 1571, 1672, 1731, 2956.1H NMR (300MHz, CDCl3, TMS): δ 3.61 (s,
3H), 3.79 (s, 3H), 7.19 (s, 1H), 7.51-7.69 (m, 2H), 7.85-7.98 (m, 3H), 8.01-8.11 (m, 1H),
8.30 (s, 1H). 13C NMR (75 MHz, CDCl3, TMS): 52.47, 53.30, 123.53, 126.89, 127.87,
128.88, 129.69, 130.61, 131.12, 132.44, 133.01, 136.02, 145.27, 163.69, 164.17,
192.09.
Dimethyl (2E)-2-(3-bromobenzoyl)but-2-enedioate (1i)4-5: Yellow oil.IR (KBr, cm-1): ν
1186, 121254, 1430, 1577, 1732, 1941. 1H NMR (300MHz, CDCl3, TMS): δ 3.66 (s,
3H), 3.79 (s, 3H), 7.11 (s, 1H), 7.30-7.45 (m, 1H), 7.65-7.86 (m, 2H), 8.01 (s, 1H). 13C
NMR (75 MHz, CDCl3, TMS): δ 52.60, 53.36, 123.13, 127.22, 130.38, 130.90, 131.34,
136.69, 137.15, 144.59, 163.18, 164.09, 190.88.
Dimethyl (2E)-2-(3-chlorobenzoyl)but-2-enedioate (1j)2a,4,5: Colorless crystalline
solid.mp: 76-77 °C IR (KBr, cm-1): ν 774, 1072, 1253, 1424, 1580, 1731, 2976. 1H NMR
(300MHz, CDCl3, TMS): δ 3.65 (s, 3H), 3.78 (s, 3H), 7.10 (s, 1H), 7.37-7.48 (m, 1H),
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7.555 (d, J = 9 Hz, 1H), 7.725 (d, J = 9Hz, 1H), 7.85 (s, 1H). 13C NMR (75 MHz, CDCl3,
TMS): δ 52.53, 53.29, 126.72, 128.36, 130.11, 130.82, 133.73, 135.06, 136.92, 144.58,
163.14, 164.04, 190.92.
References:
1. (a) Iesce MR,Cermola F, Piazza A,Graziano ML,Scarpati R (1995) Synthesis 439; (b)
Iesce MR,Cermola F,Graziano ML,Scarpati R (1994) Synthesis944.
2.(a)Li C-Q, Shi M (2003)Org Lett 5:4273; (b) Nair A,Sreekanth AR,Abhilash N,Biju AT,
Devi BR,Menon RS, Rath NP,Srinivas R (2003)Synthesis 1895.
3. Bayat M,Imanieh H,Hassanzadeh F (2010)Tetrahedron Lett 51:1873.
4. Kashyap B,Phukan P (2013) RSC Advances 3:15327.
5. Singh RSK,Kashyap B,Phukan P (2013) Tetrahedron Lett 54:6687.
6. Wang Y,Luo Y-C, Hu X-Q,Xu P-F (2011) Org Lett 13:5346.
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10 9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)
3.193.061.002.070.912.07
7.90
7.87
7.64
7.61
7.59
7.52
7.49
7.47
7.27
7.11
3.79
3.64
0.00
180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)
192.
20
164.
1816
3.58
145.
21
135.
4713
3.91
130.
4712
8.82
128.
66
77.4
377
.00
76.5
8
53.2
952
.49
O
H
COOMe
COOMe1a
O
H
COOMe
COOMe1a
S6
10 9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)
3.463.491.002.292.17
7.74
7.72
7.62
7.60
7.27
7.08
3.76
3.63
180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)
191.
14
164.
0216
3.20
144.
64
134.
2013
2.08
130.
6312
9.95
129.
09
77.4
377
.00
76.5
7
53.2
352
.48
O
H
COOMe
COOMe1bBr
O
H
COOMe
COOMe1bBr
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10 9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)
3.262.791.002.012.01
7.84
7.81
7.48
7.45
7.27
7.10
3.79
3.66
0.00
180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)
191.
04
164.
1416
3.34
144.
7914
0.41
133.
9013
0.72
129.
9712
9.22
77.4
377
.00
76.5
7
53.3
552
.58
O
H
COOMe
COOMe1cCl
O
H
COOMe
COOMe1cCl
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10 9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)
3.403.290.992.472.08
7.93
7.93
7.91
7.91
7.90
7.89
7.27
7.19
7.18
7.16
7.13
7.10
3.79
3.66
0.00
180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)
190.
64
164.
1516
3.43
144.
91
131.
3913
1.26
130.
55
116.
2411
5.95
77.4
277
.00
76.5
8
53.3
152
.54
O
H
COOMe
COOMe1dF
O
H
COOMe
COOMe1dF
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10 9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)
3.143.311.002.082.15
8.32
8.29
8.04
8.01
7.12
3.78
3.65
180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)
190.
69
164.
0716
2.84
150.
46
144.
2513
9.67
131.
2412
9.46
123.
96
77.4
277
.00
76.5
8
53.3
652
.66
O
H
COOMe
COOMe1eO2N
O
H
COOMe
COOMe1eO2N
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10 9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)
2.842.872.932.001.001.93
7.87
7.84
7.27
7.08
6.97
6.94
3.88
3.78
3.64
0.00
220 200 180 160 140 120 100 80 60 40 20 0 -20Chemical Shift (ppm)
191.
15
164.
2516
3.45
144.
9014
0.52
134.
0113
0.83
130.
0812
9.33
77.5
477
.11
76.6
8
53.4
652
.69
52.2
8
O
H
COOMe
COOMe1fMeO
O
H
COOMe
COOMe1fMeO
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9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)
3.053.063.021.002.751.94
7.80
7.77
7.30
7.27
7.09
3.78
3.64
2.42
200 180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)
185.
41
157.
8015
7.28
138.
9213
8.57
126.
6912
3.84
123.
1512
2.39
71.0
170
.59
70.1
7
46.8
546
.05
23.2
8
O
H
COOMe
COOMe1g
O
H
COOMe
COOMe1g
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9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)
3.213.331.002.073.041.021.03
8.30
8.03
8.03
7.95
7.93
7.90
7.88
7.62
7.59
7.58
7.55
7.27
7.19
3.79
3.61
0.00
180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)
192.
09
164.
1716
3.69
145.
2713
6.02
133.
0113
2.44
131.
1213
0.61
129.
6912
8.88
127.
8712
6.89
123.
53
77.4
277
.00
76.5
8
53.3
052
.47
O
H
COOMe
COOMe1h
O
H
COOMe
COOMe1h
S13
10 9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)
3.153.241.001.192.191.07
8.01
7.79
7.77
7.73
7.71
7.39
7.36
7.34
7.27
7.11
3.79
3.66
180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)
190.
88
164.
0916
3.18
144.
5913
7.15
136.
6913
1.34
130.
9013
0.38
127.
2212
3.13
77.4
377
.00
76.5
8
53.3
652
.60
O
H
COOMe
COOMe1i
Br
O
H
COOMe
COOMe1i
Br
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10 9 8 7 6 5 4 3 2 1 0Chemical Shift (ppm)
3.293.191.001.131.121.041.04
7.85
7.74
7.71
7.57
7.54
7.44
7.41
7.39
7.27
7.10
3.78
3.65
180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)
190.
92
164.
0416
3.14
144.
5813
6.92
135.
0613
3.73
130.
8213
0.11
128.
3612
6.72
77.4
277
.00
76.5
8
53.2
952
.53
O
H
COOMe
COOMe1j
Cl
O
H
COOMe
COOMe1j
Cl
S15