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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