Figure 2 Molecular structure of cyclopropane derivative D2 in the … · 2008. 1. 18. · College...

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Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2008 1 One-step synthesis of polysubstituted benzenes by multi-component cyclization of α-bromoacetate, malononitrile and aromatic aldehydes Chao Guo Yan,* Xiao Kai Song, Qi Fang Wang, Jing Sun College of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou 225002, China Ulrich Siemeling,* Clemens Bruhn Institute of Chemistry, University of Kassel, Heinrich-Plett-Strasse 40, D-34132 Kassel, Germany Supporting Information Figures Figure 1 2 Figure 2 2 Figure 3 3 Figure 4 3 Scheme1-2 4 General Experimental Methods and Characterization of compounds 5-21 X-Ray Crystallographic Data CIF in separate file. Crystallographic data (1a: CCDC 663309; 1b: CCDC 663310; 1c: CCDC 663311; 1h CCDC 663312. D1: CCDC 663313; D2: CCDC 663314. F CCDC 663315. ) have been deposited vat the Cambridge Crystallographic Database Centre and is available on request from the Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (Fax: +44-1223-336033; e-mail: [email protected] or www:http//www.ccdc.cam.ac.uk).

Transcript of Figure 2 Molecular structure of cyclopropane derivative D2 in the … · 2008. 1. 18. · College...

Page 1: Figure 2 Molecular structure of cyclopropane derivative D2 in the … · 2008. 1. 18. · College of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou 225002, China

Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2008

1

One-step synthesis of polysubstituted benzenes by multi-component cyclization

of α-bromoacetate, malononitrile and aromatic aldehydes

Chao Guo Yan,* Xiao Kai Song, Qi Fang Wang, Jing Sun

College of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou 225002, China

Ulrich Siemeling,* Clemens Bruhn

Institute of Chemistry, University of Kassel, Heinrich-Plett-Strasse 40, D-34132 Kassel, Germany

Supporting Information

Figures

Figure 1 2

Figure 2 2

Figure 3 3

Figure 4 3

Scheme1-2 4

General Experimental Methods and

Characterization of compounds 5-21

X-Ray Crystallographic Data CIF in separate file.

Crystallographic data (1a: CCDC 663309; 1b: CCDC 663310; 1c: CCDC 663311; 1h CCDC 663312. D1:

CCDC 663313; D2: CCDC 663314. F CCDC 663315. ) have been deposited vat the Cambridge

Crystallographic Database Centre and is available on request from the Director, CCDC, 12 Union

Road, Cambridge, CB2 1EZ, UK (Fax: +44-1223-336033; e-mail: [email protected] or

www:http//www.ccdc.cam.ac.uk).

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Figure 1 Molecular structure of 1c in the crystal

Figure 2 Molecular structure of cyclopropane derivative D2 in the crystal

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Figure 3 Molecular structure of intermediate F in the crystal

Figure 4 Molecular structure of 1h in the crystal

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2ArCHO +CN

CNBrCH2CO2Et+ +

N

CO2EtAr

ArCN

NH2

CN2

Scheme 1 One-pot four-component reaction affording polysubstituted benzene derivatives

N

+ Py

N

+ BrCH2CO2Et

ArCH=C(CN)2

-Py + Py

CO2Et

CN

CN

Ar

ArCH=C(CN)2

CO2Et

Ar

NC

NC

CO2Et

Ar

Ar

CN

CN

CN

C N

CO2Et

CN

N

NC CN

Ar

Ar

CO2Et

CN

NH2

NC CN

Ar

Ar

CO2Et

CN

NH2Ar

Ar

CN

CH2CO2EtNCHCO2Et

NCHCO2Et

CO2Et

CN

CN

ArC(CN)2ArCH

- HPy

- HPy- Br

+ Py

- HCN- HPy

A

B

C

D

E

F 1

+ H

Scheme 2 Proposed mechanism for the formation of polysubstituted benzenes 1

Page 5: Figure 2 Molecular structure of cyclopropane derivative D2 in the … · 2008. 1. 18. · College of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou 225002, China

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General procedure for the synthesis of polysubstituted Benzenes

A mixture of pyridine (20.0mmol, 1.58g), ethyl α-bromoacetate (4.0mmol, 0.668g),

aromatic aldehyde (4.0mmol, 0.562g) and malononitrile (4.0mmol, 0.264g) in

acetonitrile (20mL) was refluxed for 12 hours. The solvent was removed by

evaporation and the residue was titrated with ethanol (10mL) to give the crude

product, which is recrystallized in ethanol to give light yellow solid

1a: mp151~152�. 1H NMR (CDCl3, 600 MHz) δ(ppm) 7.273 (m, J = 8.4Hz, 3H,

C6H5), 7.132 (m, J = 7.2 Hz, 3H, C6H5), 7.054 (d, J = 8.4 Hz, 2H, C6H5), 6.921 (d, J =

8.4 Hz, 2H, C6H5), 5.380 (s, 2H, NH2), 4.082 (q, J = 7.2 Hz, 2H, CH2), 0.972 (t, J =

7.2 Hz, 3H, CH3); 13C NMR (CDCl3, 600 MHz) δ(ppm) 147.81, 147.48, 146.97,

131.34, 131.14, 128.82, 127.86, 127.24, 126.55, 124.80, 124.52, 124.23, 109.93,

38.44, 34.54, 34.13, 27.43, 27.05, 19.78; IR(KBr)ν3432, 3355, 3254, 2220, 1727,

1648, 1565, 1568, 1454, 1374, 1267, 1231, 1034, 754, 703; Found: C,75.15; H,4.47;

N,11.39. C23H17N3O2 requires C,75.19; H,4.66; N,11.44. The structure of 1a was

further proved by X-ray crystallographic analysis (Figure 1).

ppm (t1)1.02.03.04.05.06.07.0

0

10000

20000

30000

40000

500007.25

87.

244

7.23

17.

154

7.13

87.

126

7.11

5

7.06

17.

047

6.92

86.

917

6.91

5

5.38

0

4.10

04.

088

4.07

64.

064

0.97

2

2.00

2.00

2.002.003.003.00

3.00

O

O CNNH2

CN

5a

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ppm (t1)050100150

0

50000

10000

15000

20000

25000

30000

35000164.

433

149.

821

140.

599

134.

997

134.

870

129.

094

128.

869

128.

294

127.

819

127.

163

126.

846

126.

647

113.

913

113.

160

98.8

57

93.5

07

61.5

07

12.4

54

CN

NH2CN

O

O

5a

Figure 1 X-ray crystallographic structure of 1a

1b mp190~191�. 1H NMR (CDCl3, 600 MHz) δ 7.049 (d, J = 7.8 Hz, 2H,

p-CH3C6H4), 6.942 (d, J = 7.8 Hz, 4H, p-CH3C6H4), 6.801 (d, J = 7.8 Hz, 2H,

p-CH3C6H4) 5.342 (s, 2H, NH2), 4.103 (q, J = 7.2 Hz, 2H, CH2), 2.292 (s, 3H, CH3),

2.251 (s, 3H, CH3), 0.972 (t, J = 7.2 Hz, 3H, CH3); 13C NMR (CDCl3, 600 MHz)

δ(ppm) 164.23, 150.18, 148.60, 140.93, 134.66, 133.42, 133.29, 133.25, 130.57,

129.80, 128.02, 127.59, 113.79, 113.04, 96.97, 94.24, 61.57, 12.74; IR(KBr)ν3467,

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3356, 3256, 2225, 1741, 1640, 1588, 1560, 1449, 1376, 1266, 1232, 1031, 795, 762;

Found: C,76.12; H,5.11; N,10.60. C25H21N3O2 requires C,75.93; H,5.35; N,10.63.

The structure of 5b was further proved by X-ray crystallographic analysis (Figure 2).

ppm (t1)0.01.02.03.04.05.06.07.0

0

10000

20000

30000

40000

50000

60000

7.26

27.

050

7.03

76.

949

6.93

6

6.80

86.

795

5.34

2

4.10

94.

097

2.29

22.

251

1.02

41.

012

1.00

0

3.00

3.003.00

2.00

2.00

2.004.002.00

O

O CNNH2

CN

CH3

H3C

5b

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CNNH2

CN

CH3

H3C

O

O

ppm (t1)050100150

0

50000

10000

15000

20000

164.

227

150.

178

148.

596

140.

932

134.

662

133.

420

133.

294

133.

253

130.

570

129.

795

128.

017

127.

590

113.

792

113.

046

98.9

59

94.2

43

61.9

85

12.7

44

5b

Figure 2 X-ray crystallographic structure of 1b

1c mp231~232�. 1H NMR (CDCl3, 600 MHz) δ 7.257 (d, J = 7.8 Hz, 2H,

p-ClC6H4), 7.156 (d, J = 8.4 Hz, 2H, p-ClC6H4), 6.990 (d, J = 7.8 Hz, 2H, p-ClC6H4),

6.860 (d, J = 8.4 Hz, 2H, p-ClC6H4), 5.423 (s, 2H, NH2), 4.129 (q, J = 7.2 Hz, 2H,

CH2), 1.051 (t, J = 7.2 Hz, 3H, CH3); 13C NMR (CDCl3, 600 MHz) δ(ppm) 162.84,

148.82, 147.13, 139.53, 132.40, 132.36, 129.63, 129.49, 129.21, 126.67, 125.19,

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121.60, 120.25, 112.42, 111.67, 97.54, 92.93, 60.66, 11.37; IR(KBr)ν3469, 3351,

3244, 2221, 1743, 1642, 1557, 1493, 1447, 1375, 1276, 1218, 1016, 789, 743;Found:

C,63.09; H,3.22; N,9.54. C23H15Cl2N3O2 requires C,63.32; H,3.47; N,9.63. The

structure of 5c was further proved by X-ray crystallographic analysis (Figure 3).

ppm (t1)1.02.03.04.05.06.07.0

0

10000

20000

30000

40000

7.26

47.

260

7.25

17.

163

7.14

96.

996

6.98

36.

867

6.85

3

5.42

3

4.14

64.

134

4.12

34.

111

1.05

1

3.00

2.00

2.00

2.002.002.00

2.00

OO CN

NH2

CN

Cl

Cl

5c

Page 10: Figure 2 Molecular structure of cyclopropane derivative D2 in the … · 2008. 1. 18. · College of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou 225002, China

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CNNH2

CN

Cl

Cl

O

O

5c

ppm (t1)050100150

0

50000

10000

15000

162.

842

148.

821

147.

134

139.

538

132.

386

132.

362

129.

632

129.

487

129.

212

128.

659

126.

187

121.

604

120.

251

112.

415

111.

671

97.5

36

92.9

32

60.6

50

11.3

86

Figure 3 X-ray crystallographic structure of 1c

1d mp201~202℃ . 1H NMR (600MHz, CDCl3) δ(ppm) 7.27~7.25 (m, 1H,

m-ClC6H4), 7.22~7.16 (m, 2H, m-ClC6H4), 7.10~7.04 (m, 2H, m-ClC6H4), 6.95 (s, 2H,

m-ClC6H4), 6.78 (s, 1H, m-ClC6H4), 5.44 (s, 2H, NH2), 4.13 (q, J = 8.4Hz, 2H, CH2),

1.03 (t, J = 8.4Hz, 3H, CH3). 13C NMR (600MHz, CDCl3) δ(ppm) 150.9, 148.9, 137.1,

137.1, 134.4, 134.4, 129.9, 129.7, 129.3, 129.2, 128.3, 128.2, 127.4, 114.4, 113.8,

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99.6, 62.8, 16.5.

ppm (t1)0.01.02.03.04.05.06.07.08.0

0

50

100

150

200

250

7.27

07.

256

7.24

07.

220

7.20

57.

189

7.17

37.

156

7.10

07.

084

7.06

97.

037

6.94

56.

783

5.43

8

4.15

04.

135

4.12

14.

107

1.04

01.

026

1.01

2

3.00

2.00

1.002.002.002.011.00

2.00

ppm (t1)050100150

0

500

150.

935

148.

909

137.

146

137.

116

134.

386

134.

354

129.

940

129.

711

129.

310

129.

181

128.

276

128.

146

127.

355

114.

399

113.

790

99.6

02

77.2

4676

.992

76.7

38

62.8

07

13.5

13

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1e mp252~253�. 1H NMR (CDCl3, 600 MHz) δ 7.419 (d, J = 8.4 Hz, 2H,

p-BrC6H4), 7.315 (d, J = 8.4 Hz, 2H, p-BrC6H4), 6.926 (d, J = 8.4 Hz, 2H, p-BrC6H4),

6.797 (d, J = 8.4 Hz, 2H, p-BrC6H4), 5.423 (s, 2H, NH2), 4.129 (q, J = 7.2 Hz, 2H,

CH2), 1.052 (t, J = 7.2 Hz, 3H, CH3); 13C NMR (CDCl3, 600 MHz) δ(ppm) 163.31,

149.48, 147.33, 140.08, 135.93, 131.43, 130.72, 129.57, 128.39, 127.97, 127.26,

125.61, 125.30, 120.85, 120.50, 112.85, 112.25, 96.16, 93.67, 61.30, 12.03; IR(KBr)

ν3469, 3352, 3243, 2221, 1742, 1639, 1558, 1445, 1376, 1305, 1262, 1219, 1025,

785, 734;Found: C,52.49; H,2.68; N,7.87. C23H15Br2N3O2 requires C,52.60; H,2.88;

N,8.00.

ppm (t1)0.01.02.03.04.05.06.07.0

0

10000

20000

30000

40000

50000

60000

7.42

97.

415

7.32

57.

311

6.93

66.

923

6.80

56.

792

5.44

8

4.13

64.

124

1.04

6

2.00

2.002.00

3.00

2.00

2.00

2.00

O

O CNNH2

CN

Br

Br

5d

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CNNH2

CN

Br

Br

O

O5d

ppm (t1)050100150

0

50000

10000

15000

163.

306

149.

476

147.

332

140.

077

135.

926

131.

431

130.

719

129.

571

128.

391

127.

970

127.

259

126.

609

126.

295

120.

850

120.

501

112.

854

112.

254

98.1

63

93.6

73

61.3

04

12.0

36

1f mp187~188�. 1H NMR (CDCl3, 600 MHz) δ 7.437 (d, J = 8.4 Hz, 1H,

m-BrC6H4), 7.340 (d, J = 7.2 Hz, 1H, m-BrC6H4), 7.214 (s, 1H, m-BrC6H4), 7.163

(q, J = 7.8 Hz, 2H, m-BrC6H4), 7.028 (q, J = 7.8 Hz, 2H, m-BrC6H4), 6.846 (s, 1H,

m-BrC6H4), 5.450 (s, 2H, NH2),4.154(q, J = 7.2 Hz, 2H, CH2), 1.060 (t, J = 7.2 Hz,

3H, CH3); 13C NMR (CDCl3, 600 MHz) δ(ppm) 165.05, 150.55, 150.15, 141.18,

138.22, 136.81, 132.53, 132.40, 129.40, 126.69, 126.36, 126.06, 114.63, 113.73,

99.42, 93.70, 61.91, 20.75, 20.61, 12.97; IR(KBr)ν3464, 3348, 3238, 2223, 1728,

1636, 1563, 1448, 1384, 1275, 1232, 1029, 775, 682; Found: C,52.47; H,2.68; N,7.87.

C23H15Br2N3O2 requires C,52.60; H,2.88; N,8.00.

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ppm (t1)0.01.02.03.04.05.06.07.08.0

0

10000

20000

30000

40000

500007.44

47.

430

7.34

67.

334

7.26

07.

214

7.17

67.

163

7.15

07.

139

7.05

37.

041

7.02

87.

014

6.84

2

5.45

0

4.17

24.

160

4.14

84.

136

1.07

21.

060

1.04

8

3.00

1.001.001.002.002.001.00

2.00

2.00

O

O CNNH2

CN

BrBr

5e

CNNH2

CN

O

O

BrBr

ppm (t1)050100150

0

50000

10000

15000

20000

165.

065

150.

554

150.

156

141.

184

138.

219

136.

809

132.

632

132.

403

129.

389

128.

693

128.

368

128.

057

114.

628

113.

734

99.4

18

93.6

95

61.9

12

20.7

5720

.610

12.9

74

5e

1g mp171~172℃. 1H NMR (600MHz, CDCl3) δ(ppm) 7.52 (d, J = 9.6Hz, 1H,

o-BrC6H4), 7.39 (d, J = 8.4Hz, 1H, o-BrC6H4), 7.16~7.10 (m, 3H, o-BrC6H4),

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7.06~6.99 (m, 3H, o-BrC6H4), 5.48 (s, 2H, NH2), 4.10 (q, J = 8.4Hz, 2H, CH2), 0.99 (t,

J = 8.4Hz, 3H, CH3).13CNMR (600MHz,CDCl3) δ(ppm) 164.4, 150.9, 149.2, 140.9,

136.0, 135.8, 133.4, 133.1, 132.6, 131.6, 130.5, 129.5, 129.4, 126.5, 126.1, 124.5,

123.0, 114.4, 114.2, 101.2, 95.9, 62.6, 13.3 . C23H15Br2N3O2 (Mw= 525.19, M+ =

525.95)

ppm (t1)1.02.03.04.05.06.07.08.0

0

50

100

150

200

250

300

7.52

87.

511

7.39

57.

380

7.24

07.

160

7.14

57.

126

7.11

07.

095

7.05

87.

045

7.02

37.

006

6.98

8

5.48

3

4.14

04.

133

4.12

64.

119

4.10

44.

101

4.08

74.

079

4.07

24.

065

1.00

60.

992

0.97

8

3.00

1.001.00

3.003.00

2.00

2.00

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ppm (t1)50100150

-500

0

500

1000

1500

2000

2500

3000

3500164.

373

150.

944

149.

157

140.

962

135.

991

135.

825

133.

398

133.

057

132.

624

131.

642

130.

459

129.

485

129.

384

126.

513

126.

116

124.

547

123.

039

114.

367

114.

173

101.

189

95.9

65

77.2

4876

.993

76.7

39

62.5

95

13.3

38

1h mp187-188℃.1H NMR (600MHz, CDCl3) δ(ppm) 7.25 (d, J = 9.6Hz, 2H,

p-(CH3)3CC6H4), 7.16 (d, J = 8.4Hz, 2H, p-(CH3)3CC6H4), 6.99 (d, J = 9.6Hz, 2H,

p-(CH3)3CC6H4), 6.84 (d, J = 9.6Hz, 2H, p-(CH3)3CC6H4), 5.44 (s, 2H, NH2), 4.13 (q,

J = 8.4Hz, 2H, CH2), 1.28 (s, 9H, (CH3)3C), 1.25 (s, 9H, (CH3)3C), 0.95 (t, J = 8.4Hz,

3H, CH3). 13C NMR (600MHz, CDCl3) δ(ppm) 165.7, 151.7, 151.2, 150.5, 141.3,

132.9, 129.6, 129.0, 124.3, 124.5, 115.2, 114.3, 99.5, 93.9, 62.3, 34.5, 34.4, 31.1, 31.1,

13.3. C31H33N3O2 (Mw = 479.26, M+ = 479.61)

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17

ppm (t1)1.02.03.04.05.06.07.0

0

500

7.31

1

7.25

77.

240

7.16

37.

149

7.00

06.

984

6.84

86.

831

5.43

9

4.15

14.

137

4.12

24.

108

1.27

91.

253

0.96

00.

946

0.93

2

3.00

2.002.00

2.002.00

2.00

2.00

9.009.00

ppm (t1)050100150

0

5000

165.

656

151.

698

151.

184

150.

445

141.

302

132.

902

129.

627

129.

033

124.

769

124.

477

115.

180

114.

327

99.5

04

93.9

1493

.908

77.2

4776

.994

76.7

39

62.3

34

34.5

2434

.359

31.1

0731

.054

13.3

03

F (Ar = p-(CH3)3CC6H4) Yield: 22%; Mp: 180-182. 1H NMR (600MHz, CDCl3) δ(ppm)

7.39 (d, J = 9.6Hz, 2H, p-(CH3)3CC6H4), 7.26 (t, J = 8.4Hz, 4H, p-(CH3)3CC6H4), 6.97

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Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2008

18

(d, J = 9.6Hz, 2H, p-(CH3)3CC6H4), 5.47 (s, 2H, NH2), 4.31 (s, 1H, CH), 4.07 (q, J =

7.2Hz, 2H, CH2), 1.29 (s, 9H, (CH3)3C), 1.24 (s, 9H, (CH3)3C), 0.91 (t, J = 8.4Hz, 3H,

CH3). 13C NMR (600MHz, CDCl3) δ(ppm) 165.1, 153.4, 151.9, 142.3, 134.7, 133.5,

129.1, 126.9, 126.5, 125.7, 125.3, 124.9, 115.0, 111.9, 110.7, 80.2, 61.8, 53.1, 42.4,

34.7, 31.1, 13.3.C32H34N4O2 (Mw = 506.65, M+ = 507.27)

ppm (f1)0.01.02.03.04.05.06.07.0

0

100

200

300

400

500

6007.39

67.

379

7.27

47.

257

7.24

47.

240

6.98

16.

964

5.47

3

4.31

04.

089

4.07

74.

063

4.06

04.

048

1.29

2

1.24

10.

921

0.90

70.

893

3.00

9.009.00

2.00

2.004.00

2.00

2.00

1.00

Page 19: Figure 2 Molecular structure of cyclopropane derivative D2 in the … · 2008. 1. 18. · College of Chemistry & Chemical Engineering, Yangzhou University, Yangzhou 225002, China

Supplementary Material (ESI) for Chemical Communications This journal is (c) The Royal Society of Chemistry 2008

19

ppm (t1)050100150

-1000

0

1000

2000

3000

4000

5000

600016

5.07

8

153.

357

151.

869

142.

303

134.

742

133.

482

129.

097

126.

913

126.

491

125.

656

125.

340

124.

881

115.

011

111.

919

110.

656

80.1

51

77.2

4776

.993

76.7

38

61.7

63

53.1

22

42.3

56

34.7

1834

.602

31.1

30

13.3

36

General procedure for the synthesis of cyclopropane derivatives

A mixture of pyridine (20.0mmol, 1.58g), ethyl α-bromoacetate (5.0mmol,

0.835g), aromatic aldehyde (5.0mmol), malononitrile (5.mmol, 0.330g) and

triethylamine (1.0mL) in acetonitrile (20mL) was refluxed for 12 hours. The solvent

was removed by evaporation and the residue was titrated with ethanol (10mL) to give

the crude product, which is recrystallized in ethanol to give light yellow solid D

D1 (Ar = p-ClC6H4): yield 84.8%,mp: 175~176�。1H NMR (600MHz, CDCl3) δ

(ppm) 7.43 (d, J = 8.4Hz, 2H, C6H4), 7.26 (d, J = 8.4Hz, 2H, C6H4), 4.71 (q, J =

7.2Hz, 2H, CH2), 3.66 (d, J = 7.2Hz,1H, CH), 3.11 (d, J = 7.2Hz, 1H, CH), 1.39 (t, J

= 7.2Hz,3H, CH3).

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D2 (Ar = o-BrC6H4): yield: 75.2% mp: 191-193�. 1H NMR (600MHz, CDCl3) δ(ppm)

7.77 (d, J = 9.6Hz, 1H, o-BrC6H4), 7.44~7.36 (m, 2H, o-BrC6H4), 7.23 (d, J = 8.4Hz,

1H, o-BrC6H4), 4.43 (q, J = 8.4Hz, 2H, CH2), 3.74 (d, J = 7.2Hz, 1H, CH), 3.17 (d, J

= 9.6Hz, 1H, CH), 1.44 (t, J = 8.4Hz, 3H, CH3). 13C NMR (600MHz, CDCl3) δ(ppm)

164.5, 133.5, 133.5, 131.3, 131.3, 129.6, 129.6, 129.3, 129.3, 127.9, 127.9, 126.2,

126.207, 111.5, 111.3, 63.4, 39.2, 34.5, 14.0. C14H11BrN2O2 (M+ 318.93, 320.93)

ppm (t1)0.01.02.03.04.05.06.07.0

0

10000

20000

30000

40000

7.43

37.

419

7.26

47.

250

4.38

84.

377

4.36

54.

354

3.66

83.

655

3.11

83.

105

1.39

91.

388

1.37

6

3.00

1.00

2.002.00

2.00

1.00

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ppm (t1)0.01.02.03.04.05.06.07.08.0

0

100

200

300

400

500

7.77

37.

757

7.43

87.

423

7.40

87.

386

7.37

17.

356

7.30

4

7.24

07.

225

4.45

14.

437

4.42

34.

409

3.75

23.

736

3.17

93.

163

1.45

61.

442

1.42

8

3.00

1.00

2.001.00

2.00

1.00

0.95

ppm (t1)050100150

0

5000

164.

545

133.

498

133.

486

131.

326

131.

314

129.

604

129.

591

129.

348

129.

335

127.

951

127.

939

126.

219

126.

207

111.

481

111.

336

77.2

5276

.998

76.7

44

63.4

14

39.1

86

34.4

64

14.0

47