electronic supplementary information · s1 electronic supplementary information nucleophilic...

S1

Electronic Supplementary Information

Nucleophilic Ring-Opening Reactions of trans-2-Aroyl-3-Aryl-Cyclopropane-1,1-Dicarboxylates with Hydrazines

Gopal Sathishkannan, V. John Tamilarasan and Kannupal Srinivasan*

School of Chemistry, Bharathidasan University, Tiruchirappalli-620 024, Tamil Nadu, India

Copies of 1H NMR and 13C NMR spectra …..………………………….……………….S2-S51

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2017

S2

COPIES OF 1H NMR AND 13C NMR SPECTRA

10 9 8 7 6 5 4 3 2 1 0 ppm

-0.000

0.978

0.996

1.014

1.119

1.137

1.155

3.732

3.743

3.805

3.823

3.832

3.841

3.850

3.859

3.933

3.941

3.950

3.960

3.967

3.972

3.977

3.986

3.995

4.003

4.092

4.110

4.119

4.137

5.507

5.513

6.665

6.683

6.702

6.958

6.977

7.071

7.090

7.111

7.143

7.161

7.175

7.185

7.205

7.222

7.227

7.246

7.265

7.277

7.281

7.296

7.314

7.590

7.608

3.17

3.07

1.01

1.31

3.03

1.03

1.00

1.02

2.00

3.29

3.29

4.97

2.04

NN

EtO2CEtO2C

7a

S3

200 180 160 140 120 100 80 60 40 20 0 ppm

1.16

13.92

14.07

51.98

54.08

62.02

62.13

66.59

76.84

77.16

77.48

113.06

119.22

126.13

126.41

127.79

128.72

128.88

129.06

129.12

131.96

140.02

143.45

145.98

167.23

168.27

NN

EtO2CEtO2C

7a

S4

11 10 9 8 7 6 5 4 3 2 1 0 ppm

1.036

1.054

1.071

1.174

1.192

1.210

2.257

3.794

3.806

3.865

3.875

3.883

3.892

3.901

3.910

3.928

3.976

3.994

4.012

4.020

4.026

4.029

4.038

4.056

4.074

4.132

4.150

4.159

4.168

4.177

4.185

4.194

5.553

6.718

6.736

6.754

7.035

7.055

7.056

7.079

7.130

7.148

7.169

7.195

7.218

7.238

7.253

7.271

7.289

7.325

7.344

7.362

7.649

7.668

3.00

3.05

3.01

1.01

1.06

3.04

1.03

1.00

1.01

4.06

2.11

2.27

0.95

2.03

1.99

NN

EtO2CEtO2C

Me

7b

S5

200 180 160 140 120 100 80 60 40 20 0 ppm

13.86

14.01

21.16

51.92

54.07

61.92

62.03

66.37

76.84

77.16

77.48

113.00

119.10

126.03

126.25

128.61

128.80

129.04

129.67

131.95

137.00

137.35

143.43

145.93

167.18

168.20

NN

EtO2CEtO2C

Me

7b

S6

NN

EtO2CEtO2C

MeO

7c

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

1.052

1.070

1.087

1.190

1.208

1.226

1.572

3.738

3.789

3.801

3.878

3.887

3.896

3.905

3.923

3.941

3.986

4.004

4.008

4.014

4.020

4.029

4.031

4.037

4.046

4.049

4.064

4.156

4.173

4.182

4.191

4.200

5.527

5.532

6.739

6.757

6.776

6.794

6.816

7.031

7.051

7.148

7.166

7.188

7.244

7.257

7.266

7.303

7.321

7.353

7.372

7.390

7.663

7.681

3.03

3.00

3.05

1.03

1.07

3.07

1.03

1.00

1.04

2.00

2.02

2.05

1.93

1.08

2.04

2.05

S7

200 180 160 140 120 100 80 60 40 20 0 ppm

13.92

14.07

51.95

54.11

55.34

62.01

62.13

66.15

76.84

77.16

77.48

113.07

114.41

119.16

126.09

127.58

128.68

128.87

129.10

132.02

143.44

145.98

159.17

167.29

168.32

NN

EtO2CEtO2C

MeO

7c

S8

10 9 8 7 6 5 4 3 2 1 0 ppm

1.047

1.065

1.083

1.200

1.217

1.235

3.793

3.804

3.865

3.874

3.883

3.892

3.901

3.910

3.982

3.987

3.993

3.999

4.008

4.017

4.026

4.037

4.044

4.056

4.064

4.082

4.153

4.170

4.180

4.188

4.197

4.215

5.572

5.577

6.759

6.777

6.795

7.003

7.023

7.156

7.174

7.196

7.234

7.238

7.249

7.290

7.295

7.312

7.333

7.359

7.378

7.396

7.654

7.672

2.94

3.00

0.92

1.15

3.17

0.97

1.11

0.97

1.98

3.98

4.95

1.92

NN

EtO2CEtO2C

Cl

7d

S9

200 180 160 140 120 100 80 60 40 20 0 ppm

13.79

13.95

51.63

53.85

62.00

62.11

65.75

76.73

77.05

77.36

112.90

119.33

125.98

127.83

128.77

128.82

129.09

129.12

131.59

133.48

138.34

143.05

145.90

167.06

168.21

NN

EtO2CEtO2C

Cl

7d

S10

10 9 8 7 6 5 4 3 2 1 0 ppm

0.978

0.996

1.014

1.118

1.136

1.153

2.206

3.720

3.732

3.815

3.824

3.833

3.851

3.868

3.950

3.958

3.967

3.976

4.086

4.089

4.093

4.104

4.112

4.120

4.130

4.148

5.476

6.664

6.681

6.699

6.981

7.000

7.019

7.074

7.091

7.109

7.146

7.161

7.177

7.225

7.243

7.245

7.277

7.294

7.311

7.313

7.589

7.607

3.06

3.25

3.00

1.00

1.00

2.98

1.03

1.00

1.00

3.90

2.19

2.24

0.97

2.10

2.00

NN

EtO2CEtO2C

7e

Me

S11

200 180 160 140 120 100 80 60 40 20 0 ppm

1.16

13.91

14.06

21.22

51.98

54.11

61.99

62.10

66.42

76.84

77.16

77.48

113.05

119.14

126.10

126.29

128.66

128.85

129.10

129.72

132.01

137.02

137.42

143.47

145.98

167.25

168.27

NN

EtO2CEtO2C

7e

Me

S12

10 9 8 7 6 5 4 3 2 1 0 ppm

1.054

1.072

1.090

1.199

1.217

1.235

3.784

3.795

3.821

3.869

3.878

3.883

3.887

3.896

3.914

3.994

4.000

4.003

4.005

4.011

4.021

4.030

4.044

4.047

4.062

4.071

4.088

4.170

4.188

4.197

4.215

5.542

5.547

6.716

6.734

6.752

6.892

6.914

7.002

7.021

7.135

7.153

7.175

7.214

7.220

7.228

7.232

7.235

7.253

7.276

7.293

7.336

7.354

7.600

7.623

3.06

3.06

1.09

3.00

1.20

3.27

1.08

1.02

1.02

2.03

2.10

2.08

1.14

2.81

2.05

2.03

NN

EtO2CEtO2C

7f

OMe

S13

200 180 160 140 120 100 80 60 40 20 0 ppm

13.92

14.08

52.00

54.28

55.50

62.01

62.13

66.38

76.84

77.16

77.48

112.83

114.35

118.83

124.61

126.42

127.61

127.71

129.01

129.09

140.12

143.64

146.06

160.22

167.24

168.32

NN

EtO2CEtO2C

7f

OMe

S14

10 9 8 7 6 5 4 3 2 1 0 ppm

1.046

1.064

1.082

1.207

1.224

1.242

3.757

3.768

3.873

3.882

3.891

3.900

3.918

3.936

3.986

3.992

3.998

4.004

4.022

4.031

4.040

4.043

4.049

4.061

4.070

4.079

4.088

4.106

4.124

4.184

4.202

4.210

4.219

4.228

5.592

5.598

6.753

6.771

6.789

7.019

7.038

7.147

7.165

7.187

7.225

7.242

7.250

7.265

7.284

7.301

7.326

7.348

7.591

7.612

3.06

3.17

0.98

1.05

1.29

0.77

1.06

1.08

1.00

1.01

2.00

2.07

1.16

2.20

4.07

2.09

NN

EtO2CEtO2C

7g

Cl

S15

200 180 160 140 120 100 80 60 40 20 0 ppm

0.14

13.92

14.08

51.85

53.93

62.12

62.21

66.72

76.85

77.16

77.48

113.11

119.50

126.33

127.24

127.89

129.11

129.17

130.50

134.41

139.73

143.17

144.74

167.09

168.15

NN

EtO2CEtO2C

7g

Cl

S16

10 9 8 7 6 5 4 3 2 1 0 ppm

1.050

1.068

1.086

1.194

1.211

1.229

3.732

3.769

3.780

3.817

3.877

3.888

3.897

3.915

3.966

3.971

3.978

3.998

4.015

4.028

4.042

4.058

4.075

4.140

4.158

4.176

4.185

4.194

4.203

5.492

6.711

6.729

6.747

6.789

6.809

6.889

6.910

7.003

7.023

7.133

7.152

7.171

7.242

7.263

7.597

7.618

3.00

3.02

3.09

1.32

3.00

1.55

3.38

1.24

1.01

1.04

1.98

2.01

1.94

2.07

2.38

2.01

NN

EtO2CEtO2C

7h

OMe

MeO

S17

200 180 160 140 120 100 80 60 40 20 0 ppm

13.91

14.07

52.06

54.41

55.33

55.49

61.96

62.08

66.03

76.84

77.16

77.48

112.90

114.36

114.40

118.79

124.76

127.60

129.06

132.23

143.71

146.09

159.16

160.23

167.26

168.34

NN

EtO2CEtO2C

7h

OMe

MeO

S18

10 9 8 7 6 5 4 3 2 1 0 ppm

1.064

1.082

1.099

1.208

1.225

1.243

3.804

3.814

3.878

3.901

3.913

3.921

3.928

3.945

3.963

3.995

4.013

4.034

4.042

4.069

4.078

4.088

4.094

4.111

4.129

4.149

4.168

4.186

4.205

4.213

4.224

4.230

5.562

6.901

6.923

7.233

7.255

7.285

7.301

7.319

7.340

7.360

7.378

7.652

7.670

3.08

3.07

1.02

1.23

3.65

1.07

1.01

2.00

4.30

4.15

2.49

2.09

NN

EtO2CEtO2C

7iBr

S19

200 180 160 140 120 100 80 60 40 20 0 ppm

13.97

14.08

51.87

54.31

62.10

62.15

66.48

76.84

77.15

77.47

111.34

114.66

126.21

126.37

128.00

128.95

129.02

129.16

131.65

131.95

139.60

142.52

146.86

167.14

168.18

NN

EtO2CEtO2C

7iBr

S20

1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5 ppm

1.066

1.083

1.101

1.214

1.231

1.249

1.536

3.782

3.792

3.828

3.876

3.894

3.920

3.938

3.955

3.996

4.002

4.007

4.027

4.055

4.076

4.104

4.122

4.139

4.172

4.191

4.209

4.235

5.524

6.872

6.894

6.916

7.220

7.240

7.258

7.281

7.298

7.315

7.589

7.609

3.02

3.04

1.03

3.03

1.17

2.09

1.07

1.04

1.00

4.04

7.39

2.04

NN

EtO2CEtO2C

7jBr

OMe

S21

200 180 160 140 120 100 80 60 40 20 0 ppm

13.85

13.96

51.75

54.36

55.38

61.95

62.01

66.12

76.70

77.02

77.34

110.74

114.31

124.15

126.25

127.57

127.78

128.97

131.76

139.55

142.54

146.77

160.33

167.02

168.10

NN

EtO2CEtO2C

7jBr

OMe

S22

10 9 8 7 6 5 4 3 2 1 0 ppm

1.116

1.133

1.151

1.237

1.254

1.272

3.897

3.906

4.071

4.114

4.133

4.151

4.176

4.194

4.217

4.234

4.252

4.278

4.297

5.880

6.747

6.771

7.258

7.307

7.336

7.427

7.591

7.601

8.022

8.045

8.385

3.13

3.24

1.06

4.31

1.12

1.09

1.08

5.64

3.30

2.21

1.08

1.00

NN

EtO2CEtO2C

7kNO2

NO2

S23

200 180 160 140 120 100 80 60 40 20 0 ppm

13.88

14.08

51.70

54.37

62.51

62.66

67.44

76.84

77.16

77.48

115.26

122.14

126.09

127.00

127.12

128.91

129.29

129.69

129.82

130.86

137.36

138.02

138.11

138.99

153.56

166.94

167.80

NN

EtO2CEtO2C

7kNO2

NO2

S24

10 9 8 7 6 5 4 3 2 1 0 ppm

1.113

1.131

1.149

1.234

1.252

1.269

2.309

3.883

3.893

4.090

4.112

4.130

4.148

4.166

4.209

4.227

4.245

4.253

4.262

4.271

4.289

5.831

6.764

6.788

7.132

7.151

7.192

7.212

7.258

7.413

7.425

7.577

7.585

7.595

8.021

8.044

8.381

3.00

3.06

3.01

1.01

4.05

1.03

1.05

1.18

4.55

3.15

2.12

1.00

0.93

NN

EtO2CEtO2C

7lNO2

NO2

Me

S25

200 180 160 140 120 100 80 60 40 20 0 ppm

13.88

14.09

21.26

51.74

54.44

62.48

62.63

67.36

76.84

77.16

77.48

115.35

122.14

126.01

126.99

127.11

129.28

129.90

130.33

130.82

135.06

137.33

138.05

138.83

139.07

153.63

166.95

167.79

NN

EtO2CEtO2C

7lNO2

NO2

Me

S26

10 9 8 7 6 5 4 3 2 1 0 ppm

1.121

1.138

1.156

1.245

1.263

1.281

1.548

3.839

3.849

4.054

4.062

4.070

4.092

4.102

4.112

4.119

4.131

4.137

4.149

4.157

4.167

4.176

4.184

4.193

4.211

4.226

4.244

4.253

4.262

4.271

4.280

4.289

5.881

5.886

6.733

6.757

7.259

7.309

7.315

7.328

7.341

7.356

7.386

7.407

7.509

7.530

8.026

8.033

8.050

8.056

8.381

8.387

3.15

3.24

1.08

1.12

3.35

1.13

1.08

1.08

5.07

2.20

2.25

1.07

1.00

NN

EtO2CEtO2C

7mNO2

NO2

Cl

S27

200 180 160 140 120 100 80 60 40 20 0 ppm

13.91

14.10

51.62

54.29

62.61

62.76

67.60

76.84

77.16

77.48

115.34

122.10

126.05

127.03

128.29

128.38

129.02

129.63

129.76

136.94

137.82

138.37

138.81

152.31

166.82

167.68

NN

EtO2CEtO2C

7mNO2

NO2

Cl

S28

10 9 8 7 6 5 4 3 2 1 0 ppm

1.109

1.127

1.145

1.252

1.270

1.287

2.395

3.889

3.899

4.088

4.097

4.103

4.115

4.121

4.132

4.139

4.148

4.160

4.166

4.184

4.189

4.194

4.200

4.205

4.224

4.243

4.261

4.270

4.288

6.122

6.127

6.907

6.916

6.919

6.928

6.964

6.988

7.004

7.011

7.229

7.248

7.261

7.494

7.514

8.094

8.100

8.117

8.124

8.412

8.418

3.02

3.01

3.00

1.01

5.17

1.01

1.01

2.03

3.04

2.05

0.99

0.91

NN

EtO2CEtO2C

7nNO2

NO2

Me

S

S29

200 180 160 140 120 100 80 60 40 20 0 ppm

13.75

13.97

21.56

51.35

54.68

62.44

62.57

63.32

115.68

122.05

125.93

126.22

126.83

126.89

126.96

127.28

129.88

137.22

138.19

139.10

140.57

141.32

153.48

166.72

167.66

NN

EtO2CEtO2C

7nNO2

NO2

Me

S

S30

10 9 8 7 6 5 4 3 2 1 0 ppm

6.819

7.293

7.311

7.328

7.348

7.367

7.384

7.698

7.715

0.99

6.22

4.00

NH

N

10a

S31

200 180 160 140 120 100 80 60 40 20 0 ppm

100.11

125.66

128.24

128.87

131.28

148.77

NH

N

10a

S32

10 9 8 7 6 5 4 3 2 1 0 ppm

3.852

6.574

7.247

7.266

7.284

7.354

7.372

7.375

7.387

7.391

7.397

7.404

7.408

7.824

7.838

7.842

3.00

0.98

0.99

6.87

1.96

NN

10b

Me

S33

200 180 160 140 120 100 80 60 40 20 0 ppm

37.63

103.30

125.62

127.71

128.61

128.74

128.80

130.72

133.56

145.13

150.53

NN

10b

Me

S34

10 9 8 7 6 5 4 3 2 1 0 ppm

0.887

0.905

0.923

2.809

2.825

3.520

3.677

3.692

3.946

3.964

3.982

4.000

7.297

7.316

7.330

7.348

7.360

7.365

7.383

7.443

7.449

7.458

7.825

7.831

7.840

7.849

3.12

1.00

3.00

1.03

2.04

5.16

2.99

2.00

NN

O

H

EtO2C Me

11

S35

200 180 160 140 120 100 80 60 40 20 0 ppm

13.65

28.62

32.03

38.57

39.91

62.03

126.33

127.97

128.62

128.75

130.08

132.52

135.16

145.85

159.83

164.56

NN

O

H

EtO2C Me

11

S36

10 9 8 7 6 5 4 3 2 1 0 ppm

0.877

0.895

0.912

2.990

3.006

3.720

3.736

3.970

3.988

3.995

4.013

7.353

7.360

7.374

7.454

7.460

7.467

7.832

7.841

8.758

3.00

1.05

0.90

1.99

5.19

2.96

2.01

1.10

NNH

O

H

EtO2C

12a

S37

200 180 160 140 120 100 80 60 40 20 0 ppm

13.67

28.22

32.43

38.99

62.19

126.35

128.19

128.28

128.69

128.82

130.23

131.96

135.04

146.91

160.90

164.06

NNH

O

H

EtO2C

8a

NNH

O

H

EtO2C

12a

S38

10 9 8 7 6 5 4 3 2 1 0 ppm

0.872

0.889

0.907

2.957

2.973

3.686

3.702

3.856

3.941

3.950

3.959

3.968

3.978

3.986

3.996

4.003

4.014

4.023

4.032

4.040

6.960

6.982

7.305

7.311

7.322

7.327

7.330

7.343

7.354

7.367

7.373

7.385

7.390

7.771

7.793

8.785

3.00

1.01

0.96

3.00

1.97

2.11

4.90

1.94

0.95

NNH

O

H

EtO2C

12b

MeO

S39

200 180 160 140 120 100 80 60 40 20 0 ppm

13.66

28.20

32.53

39.00

55.42

62.12

114.18

127.75

127.89

128.18

128.65

132.14

146.60

160.90

161.27

164.19

NNH

O

H

EtO2C

12b

MeO

S40

10 9 8 7 6 5 4 3 2 1 0 ppm

0.873

0.891

0.909

2.963

2.979

3.656

3.672

3.972

3.990

3.998

4.016

7.311

7.330

7.343

7.347

7.358

7.369

7.374

7.404

7.426

7.753

7.774

9.121

3.00

1.00

1.03

2.05

4.94

2.09

2.07

1.02

NNH

O

H

EtO2C

12c Cl

S41

200 180 160 140 120 100 80 60 40 20 0 ppm

13.66

27.92

32.29

39.06

62.27

76.76

77.08

77.40

127.61

128.13

128.34

128.73

129.03

131.80

133.53

136.30

145.72

160.94

164.01

NNH

O

H

EtO2C

12c Cl

S42

10 9 8 7 6 5 4 3 2 1 0 ppm

0.896

0.914

0.932

3.040

3.056

3.878

3.894

3.971

3.980

3.989

3.998

4.007

4.016

4.025

4.034

4.043

4.052

4.061

4.070

7.338

7.344

7.350

7.360

7.363

7.372

7.397

7.409

7.522

7.526

7.536

7.545

7.550

7.562

7.851

7.867

7.878

7.900

7.923

7.985

7.990

8.007

8.011

8.233

8.870

3.06

1.00

0.99

2.08

5.40

2.10

3.23

1.07

1.07

1.10

NNH

O

H

EtO2C

12d

S43

200 180 160 140 120 100 80 60 40 20 0 ppm

13.70

28.10

32.57

39.02

62.25

123.07

126.65

126.77

127.33

127.81

128.24

128.31

128.67

128.74

132.05

132.50

132.96

134.04

146.73

160.95

164.16

NNH

O

H

EtO2C

12d

S44

10 9 8 7 6 5 4 3 2 1 0 ppm

0.948

0.966

0.984

2.391

2.899

2.916

3.636

3.652

4.008

4.022

4.026

4.039

7.235

7.257

7.280

7.327

7.348

7.687

7.707

9.217

3.05

3.00

0.99

1.01

1.94

4.18

2.08

2.05

0.94

NNH

O

H

EtO2C

12eMe

Cl

S45

200 180 160 140 120 100 80 60 40 20 0 ppm

13.78

21.41

28.37

31.76

38.73

62.29

126.23

128.82

129.54

129.60

130.81

132.23

134.19

140.56

146.49

160.85

164.13

NNH

O

H

EtO2C

12eMe

Cl

S46

10 9 8 7 6 5 4 3 2 1 0 ppm

0.961

0.978

0.996

2.371

3.015

3.031

3.724

3.740

3.998

4.007

4.016

4.025

4.042

4.060

4.069

4.077

4.087

7.135

7.144

7.148

7.157

7.175

7.196

7.229

7.249

7.456

7.468

7.532

7.539

8.300

3.03

3.00

0.90

1.01

2.02

5.02

0.93

1.02

0.94

NNH

O

H

EtO2C

12f

Me

S

S47

200 180 160 140 120 100 80 60 40 20 0 ppm

13.71

21.11

28.44

32.52

38.48

62.17

127.73

128.22

128.72

128.79

129.31

138.16

139.95

143.05

160.86

164.02

NNH

O

H

EtO2C

12f

Me

S

S48

10 9 8 7 6 5 4 3 2 1 0 ppm

1.090

1.108

1.125

2.344

3.904

3.922

3.939

3.957

4.698

7.122

7.141

7.197

7.216

7.234

7.253

7.271

7.303

7.323

7.359

7.374

7.377

7.398

7.417

7.435

7.702

7.721

6.19

3.08

4.19

1.00

2.18

3.22

2.41

2.20

1.08

2.26

2.10

NN

EtO2CEtO2C

8

Me

S49

200 180 160 140 120 100 80 60 40 20 0 ppm

13.94

21.45

49.63

61.72

76.84

77.16

77.48

111.61

125.02

126.79

127.11

128.22

128.37

128.74

129.01

129.21

130.53

133.25

138.94

140.04

143.15

152.24

168.51

NN

EtO2CEtO2C

8

Me

S50

11 10 9 8 7 6 5 4 3 2 1 0 ppm

2.340

6.781

7.098

7.118

7.150

7.170

7.232

7.266

7.283

7.300

7.317

7.336

7.364

7.384

7.396

7.415

7.433

7.906

7.924

3.04

1.00

4.08

8.09

2.02

NN

9

Me

S51

200 180 160 140 120 100 80 60 40 20 0 ppm

21.39

76.84

77.16

77.47

105.10

125.46

125.96

127.46

127.86

128.06

128.75

129.00

129.32

133.31

138.36

140.44

144.62

152.06

NN

9

Me