S1

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

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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

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