Post on 24-Jul-2020
S-1
Supporting Information
Photochemistry of benzene and quinoxaline fused ∆2-1,2,3-triazolines and their
trapping products
Yu-Jen Chen,a Hao-Chih Hung,a Chin-Kang Sha,b, * and Wen-Sheng Chung*, a
(a) Department of Applied Chemistry, National Chiao Tung University, Hsinchu,
30050, Taiwan, Republic of China
(b) Department of Chemistry, National Tsing Hua University, Hsinchu,
300, Taiwan, Republic of China
wschung@cc.nctu.edu.tw
cksha@mx.nthu.edu.tw
Contents
P. S-3. Figure S1. 1H NMR (300 MHz, CDCl3) spectrum of 1a and Figure S2.
13C NMR (75 MHz, CDCl3) spectrum of 1a
P. S-4. Figure S3. 1H NMR (300 MHz, CDCl3) spectrum of 1b and Figure S4.
13C NMR (75 MHz, CDCl3) spectrum of 1b
P. S-5. Figure S5. 1H NMR (300 MHz, CDCl3) spectrum of 3 and Figure S6. 13C
NMR (75 MHz, CDCl3) spectrum of 3
P. S-6. Figure S7. 1H NMR (300 MHz, CDCl3) spectrum of 4 and Figure S8. 13C
NMR (75 MHz, CDCl3) spectrum of 4
P. S-7. Figure S9. 1H NMR (300 MHz, CDCl3) spectrum of 5 and Figure S10.
13C NMR (75 MHz, CDCl3) spectrum of 5
P. S-8. Figure S11. 1H NMR (300 MHz, CDCl3) spectrum of 6 and Figure S12.
13C NMR (75 MHz, CDCl3) spectrum of 6
S-2
P. S-9. Figure S13. 1H NMR (300 MHz, CDCl3) spectrum of 9b and Figure S14.
13C NMR (75 MHz, CDCl3) spectrum of 9b
P. S-10. Figure S15. 1H NMR (300 MHz, CDCl3) spectrum of 10b and Figure S16.
13C NMR (75 MHz, CDCl3) spectrum of 10b
P. S-11. Figure S17. 1H NMR (300 MHz, CDCl3) spectrum of 11a and Figure S18.
13C NMR (75 MHz, CDCl3) spectrum of 11a
P. S-12. Figure S19. 1H NMR (300 MHz, CDCl3) spectrum of 12b and Figure S20.
13C NMR (75 MHz, CDCl3) spectrum of 12b
P. S-13. Figure S21. 1H NMR (300 MHz, CDCl3) spectrum of 13a and Figure S22.
13C NMR (75 MHz, CDCl3) spectrum of 13a
P. S-14. Figure S23. 1H NMR (300 MHz, CDCl3) spectrum of 14a and Figure S24.
13C NMR (75 MHz, CDCl3) spectrum of 14a
P. S-5. Figure S25. 1H NMR (600 MHz, CDCl3) spectrum of 15b and Figure S26.
13C NMR (150 MHz, CDCl3) spectrum of 15b
P. S-6. Figure S27. 1H NMR (300 MHz, CDCl3) spectrum of 16a and Figure S28.
13C NMR (75 MHz, CDCl3) spectrum of 16a
P. S-17. Figure S29. Expand 1H NMR spectra for photolysis of 1a in CD3CN
P. S-18. Figure S30. Expand 1H NMR spectra for photolysis of 1b in CD3CN
P. S-19. Figure S31. 1H NMR spectra for photolysis of 1a in d8-THF
P. S-20. Figure S32. 1H NMR spectra for photolysis of 1b in d8-THF and
P. S-21. Figure S33. EPR spectrum for photolysis of 1a in MTHF matrix at 77 K and
Figure S34. EPR spectrum for photolysis of 1b in MTHF matrix at 77
K
S-3
9 8 7 6 5 4 3 2 1 0 ppm
0.0002
1.1171
1.1413
1.1655
1.3448
1.3683
1.3925
1.6307
4.1674
4.1796
4.1916
4.2038
4.2156
4.2274
4.2387
4.2941
4.3181
4.3292
4.3528
4.4136
4.4377
4.4494
4.4724
4.6499
4.7015
5.3114
5.3630
5.7152
7.0925
7.1174
7.2210
7.2276
7.2530
7.2666
7.2900
7.3113
3.340
3.429
2.194
2.298
1.044
1.065
1.000
1.029
3.805
Current Data ParametersNAME cyj060411-PhN3EXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20060422Time 17.32INSTRUM spectPROBHD 5 mm BBO 1H-BPULPROG zg30TD 16384SOLVENT CDCl3NS 16DS 0SWH 5995.204 HzFIDRES 0.365918 HzAQ 1.3664756 secRG 1625.5DW 83.400 usecDE 6.50 usecTE 300.0 KD1 3.00000000 secP1 9.90 usecSFO1 300.1319508 MHzNUC1 1HPL1 -3.00 dB
F2 - Processing parametersSI 8192SF 300.1300042 MHzWDW EMSSB 0LB 0.10 HzGB 0PC 1.00
7.27.4 ppm
7.093
7.117
7.221
7.228
7.253
7.267
7.290
7.311
4.24.34.44.5 ppm
4.192
4.204
4.216
4.227
4.239
4.294
4.318
4.329
4.353
4.414
4.438
4.449
4.472
Figure S1. 1H NMR (300 MHz, CDCl3) spectrum of 1a
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
13.712
13.901
54.990
62.422
63.325
68.061
76.581
77.004
77.428
94.963
123.036
123.271
127.732
129.096
135.914
137.524
164.409
164.866
Figure S2. 13C NMR (75 MHz, CDCl3) spectrum of 1a
125130135 ppm
123.036
123.271
127.732
129.096
135.914
137.524
N
NN
EtO2CCO2Et
1a
N
NN
EtO2CCO2Et
1a
S-4
9 8 7 6 5 4 3 2 1 0 ppm
-0.0002
1.2070
1.2309
1.2546
1.3751
1.3987
1.4226
4.2914
4.3042
4.3148
4.3207
4.3280
4.3324
4.3388
4.3445
4.3515
4.3564
4.3625
4.3802
4.4767
4.5005
4.5124
4.5361
4.8974
4.9551
5.5241
5.5818
5.8611
7.2709
7.7467
7.7530
7.7593
7.7694
7.7792
7.7859
7.7926
7.9842
7.9925
8.0113
8.0167
8.0581
8.0632
8.0828
8.0907
3.178
3.253
4.129
0.992
1.000
0.895
2.035
1.968
Current Data ParametersNAME cyj070523EXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20070525Time 4.14INSTRUM spectPROBHD 5 mm MultinuPULPROG zg30TD 16384SOLVENT CDCl3NS 16DS 0SWH 4789.272 HzFIDRES 0.292314 HzAQ 1.7105396 secRG 57DW 104.400 usecDE 6.50 usecTE 300.0 KD1 2.00000000 sec
============ CHANNEL f1 =============NUC1 1HP1 9.70 usecPL1 -3.00 dBSFO1 300.1319508 MHz
F2 - Processing parametersSI 16384SF 300.1300032 MHzWDW EMSSB 0LB 0.10 HzGB 0PC 1.00
1D NMR plot parametersCX 23.00 cmF1P 10.000 ppmF1 3001.30 HzF2P -0.500 ppmF2 -150.07 HzPPMCM 0.45652 ppm/cmHZCM 137.01587 Hz/cm
7.87.98.08.1 ppm
7.747
7.753
7.759
7.769
7.779
7.786
7.793
7.984
7.992
8.011
8.017
8.058
8.063
8.083
8.091
4.34.44.5 ppm
4.291
4.304
4.315
4.321
4.328
4.332
4.339
4.345
4.351
4.356
4.362
4.380
4.477
4.500
4.512
4.536
Figure S3. 1H NMR (300 MHz, CDCl3) spectrum of 1b
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
13.839
13.932
53.776
62.730
63.605
65.558
76.574
76.998
77.421
95.925
129.222
129.269
130.207
130.560
141.982
142.441
152.431
153.298
163.568
164.181
Figure S4. 13C NMR (75 MHz, CDCl3) spectrum of 1b
ppm
141.982
142.441
130 ppm
129.222
129.269
130.207
130.560
13.839
13.932
N
NN
NN
EtO2CCO2Et
1b
N
NN
NN
EtO2CCO2Et
1b
S-5
9 8 7 6 5 4 3 2 1 0 ppm
0.0000
1.7155
2.8881
4.7577
7.2680
7.6936
7.7000
7.7167
7.7238
7.7274
7.7385
7.7493
7.7537
7.7607
7.7772
7.7839
8.0065
8.0111
8.0212
8.0286
8.0321
8.0392
8.0488
8.0539
3.170
2.145
2.084
2.000
Current Data ParametersNAME cyj060627-PhN2N3-paper-2EXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20060708Time 19.58INSTRUM spectPROBHD 5 mm MultinuPULPROG zg30TD 16384SOLVENT CDCl3NS 16DS 0SWH 4789.272 HzFIDRES 0.292314 HzAQ 1.7105396 secRG 32DW 104.400 usecDE 6.50 usecTE 300.0 KD1 2.00000000 sec
============ CHANNEL f1 =============NUC1 1HP1 9.90 usecPL1 -3.00 dBSFO1 300.1319508 MHz
F2 - Processing parametersSI 16384SF 300.1300040 MHzWDW EMSSB 0LB 0.10 HzGB 0PC 1.00
7.77.87.98.08.1 ppm
7.694
7.700
7.717
7.724
7.727
7.739
7.749
7.754
7.761
7.777
7.784
8.007
8.011
8.021
8.029
8.032
8.039
8.049
8.054
Figure S5. 1H NMR (300 MHz, CDCl3) spectrum of 3
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
22.415
31.790
76.575
76.999
77.201
77.422
128.358
128.967
129.439
130.407
140.766
141.912
150.801
153.062
Figure S6. 13C NMR (75 MHz, CDCl3) spectrum of 3
128.358
128.967
129.439
130.407
N
N
3
Br
N
N
3
Br
S-6
11 10 9 8 7 6 5 4 3 2 1 ppm
0.0001
0.0065
0.0088
0.0108
3.0539
7.2650
7.7915
7.7962
7.8146
7.8191
7.8237
7.8421
7.8470
7.8789
7.8841
7.9020
7.9069
7.9118
7.9299
7.9349
8.0851
8.0884
8.1127
8.1165
8.1942
8.1987
8.2214
8.2229
8.2262
10.3268
3.326
2.181
2.142
1.000
Current Data ParametersNAME cyj060806-PhN2N3-paper-3EXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20060825Time 15.05INSTRUM spectPROBHD 5 mm MultinuPULPROG zg30TD 16384SOLVENT CDCl3NS 16DS 0SWH 4789.272 HzFIDRES 0.292314 HzAQ 1.7105396 secRG 32DW 104.400 usecDE 6.50 usecTE 300.0 KD1 2.00000000 sec
============ CHANNEL f1 =============NUC1 1HP1 9.90 usecPL1 -3.00 dBSFO1 300.1319508 MHz
F2 - Processing parametersSI 16384SF 300.1300046 MHzWDW EMSSB 0LB 0.10 HzGB 0PC 1.00
7.87.98.08.18.2 ppm
7.792
7.796
7.815
7.819
7.824
7.842
7.847
7.879
7.884
7.902
7.907
7.912
7.930
7.935
8.085
8.088
8.113
8.117
8.194
8.199
8.221
8.223
8.226
Figure S7. 1H NMR (300 MHz, CDCl3) spectrum of 4
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
-0.025
23.215
76.573
76.996
77.419
128.553
129.982
130.021
133.018
140.788
142.728
145.243
153.540
193.959
Figure S8. 13C NMR (75 MHz, CDCl3) spectrum of 4
130132 ppm
128.553
129.982
130.021
133.018
N
N
4
H
O
N
N
4
H
O
S-7
9 8 7 6 5 4 3 2 1 0 ppm
-0.0004
1.2959
1.3197
1.3437
1.3540
1.3779
1.4015
2.8933
4.3396
4.3633
4.3871
4.4116
4.4155
4.4403
4.4642
4.4879
7.6979
7.7271
7.7550
7.9212
7.9494
7.9831
8.0098
8.0137
8.0283
6.019
3.108
4.000
2.069
2.990
Current Data ParametersNAME cyj060808EXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20060901Time 21.59INSTRUM spectPROBHD 5 mm MultinuPULPROG zg30TD 16384SOLVENT CDCl3NS 16DS 0SWH 4789.272 HzFIDRES 0.292314 HzAQ 1.7105396 secRG 32DW 104.400 usecDE 6.50 usecTE 300.0 KD1 2.00000000 sec
============ CHANNEL f1 =============NUC1 1HP1 9.90 usecPL1 -3.00 dBSFO1 300.1319508 MHz
F2 - Processing parametersSI 16384SF 300.1299999 MHzWDW EMSSB 0LB 0.10 HzGB 0PC 1.00
1D NMR plot parametersCX 23.00 cmF1P 10.000 ppmF1 3001.30 HzF2P -0.500 ppmF2 -150.07 HzPPMCM 0.45652 ppm/cmHZCM 137.01587 Hz/cm
7.87.98.0 ppm
7.698
7.727
7.755
7.921
7.949
7.983
8.010
8.014
8.028
4.44.5 ppm4.363
4.387
4.412
4.415
4.440
4.464
4.488
1.4 ppm
1.296
1.320
1.344
1.354
1.378
1.402
Figure S9. 1H NMR (300 MHz, CDCl3) spectrum of 5
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
14.050
22.611
61.374
62.053
76.573
76.996
77.420
128.358
129.275
129.613
131.106
132.377
134.758
140.658
141.903
145.828
153.103
163.497
165.958
Figure S10. 13C NMR (75 MHz, CDCl3) spectrum of 5
135 ppm
128.358
129.275
129.613
131.106
132.377
134.758
N
N
5
CO2Et
CO2Et
N
N
5
CO2Et
CO2Et
S-8
9 8 7 6 5 4 3 2 1 0 ppm
-0.0002
1.3027
1.3264
1.3503
1.3638
1.3876
1.4112
4.3527
4.3766
4.4002
4.4196
4.4234
4.4431
4.4671
4.4907
4.8469
7.7630
7.7707
7.7840
7.7959
7.8057
7.9476
7.9566
7.9804
8.0185
8.0229
8.0240
8.0424
8.0510
8.1227
6.414
4.021
1.999
2.180
2.004
1.104
Current Data ParametersNAME cyj060812-PhN2N3-paper-5EXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20060909Time 19.59INSTRUM spectPROBHD 5 mm MultinuPULPROG zg30TD 16384SOLVENT CDCl3NS 16DS 0SWH 4789.272 HzFIDRES 0.292314 HzAQ 1.7105396 secRG 32DW 104.400 usecDE 6.50 usecTE 300.0 KD1 2.00000000 sec
============ CHANNEL f1 =============NUC1 1HP1 9.70 usecPL1 -3.00 dBSFO1 300.1319508 MHz
F2 - Processing parametersSI 16384SF 300.1299964 MHzWDW EMSSB 0LB 0.10 HzGB 0PC 1.00
7.87.98.0 ppm
7.763
7.771
7.784
7.796
7.806
7.948
7.957
7.980
8.018
8.023
8.024
8.042
8.051
4.44.5 ppm
4.353
4.377
4.400
4.420
4.423
4.443
4.467
4.491
1.4 ppm
1.303
1.326
1.350
1.364
1.388
1.411
Figure S11. 1H NMR (300 MHz, CDCl3) spectrum of 6
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
14.000
14.018
30.271
61.382
62.121
76.576
77.000
77.425
128.975
129.174
131.001
131.520
132.600
133.687
141.305
141.388
145.374
150.711
163.300
165.758
Figure S12. 13C NMR (75 MHz, CDCl3) spectrum of 6
132134 ppm
128.975
129.174
131.001
131.520
132.600
133.687
N
N
6
CO2Et
CO2Et
Br
N
N
6
CO2Et
CO2Et
Br
S-9
9 8 7 6 5 4 3 2 1 0 ppm
0.0001
0.0705
1.2542
1.3211
1.3448
1.3576
1.3684
1.3815
1.4054
1.4204
1.6793
4.2525
4.2762
4.2999
4.3236
4.4715
4.4954
4.5192
4.5431
4.8764
7.2639
7.8235
7.8287
7.8444
7.8493
7.8555
7.8717
7.8768
8.1220
8.1295
8.1473
8.1548
9.0032
6.084
2.017
1.967
1.612
2.000
1.780
0.757
Current Data ParametersNAME cyj070529-PhN2N3-diesterEXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20070531Time 18.06INSTRUM spectPROBHD 5 mm MultinuPULPROG zg30TD 16384SOLVENT CDCl3NS 64DS 0SWH 4789.272 HzFIDRES 0.292314 HzAQ 1.7105396 secRG 57DW 104.400 usecDE 6.50 usecTE 300.0 KD1 2.00000000 sec
============ CHANNEL f1 =============NUC1 1HP1 9.70 usecPL1 -3.00 dBSFO1 300.1319508 MHz
F2 - Processing parametersSI 16384SF 300.1300049 MHzWDW EMSSB 0LB 0.10 HzGB 0PC 1.00
8.08.2 ppm
7.829
7.844
7.849
7.856
7.872
7.877
8.122
8.130
8.147
8.155
4.44.5 ppm
4.253
4.276
4.300
4.324
4.471
4.495
4.519
4.543
1.31.4 ppm
1.254
1.321
1.345
1.358
1.368
1.382
1.405
1.420
Figure S13. 1H NMR (300 MHz, CDCl3) spectrum of 9b
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
-0.018
14.113
14.393
29.691
49.271
60.315
61.337
76.580
77.003
77.206
77.427
129.073
130.346
130.392
131.546
142.270
142.479
147.276
154.723
154.965
166.871
167.876
Figure S14. 13C NMR (75 MHz, CDCl3) spectrum of 9b
14
14.113
14.393
130131 ppm
129.073
130.346
130.392
131.546
ppm
142.270
142.479
ppm
154.723
154.965
NH
EtO2CCO2Et
9b
N
N
NH
EtO2CCO2Et
9b
N
N
S-10
9 8 7 6 5 4 3 2 1 0 ppm
0.0001
1.2556
1.6120
3.0558
3.2613
5.1135
7.2632
7.3329
7.3575
7.4217
7.4452
7.4747
7.5000
7.5235
7.7568
7.7683
7.7770
7.7886
8.0380
8.0494
8.0580
8.0698
0.967
2.100
2.000
2.053
3.169
2.204
2.170
Current Data ParametersNAME cyj070717-PhN2N3-NH-NPM-CDCl3EXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20070720Time 18.44INSTRUM spectPROBHD 5 mm MultinuPULPROG zg30TD 16384SOLVENT CDCl3NS 128DS 0SWH 4789.272 HzFIDRES 0.292314 HzAQ 1.7105396 secRG 57DW 104.400 usecDE 6.50 usecTE 300.0 KD1 2.00000000 sec
============ CHANNEL f1 =============NUC1 1HP1 9.70 usecPL1 -3.00 dBSFO1 300.1319508 MHz
F2 - Processing parametersSI 16384SF 300.1300052 MHzWDW EMSSB 0LB 0.10 HzGB 0PC 1.00
7.27.47.67.88.08.2 ppm7.263
7.333
7.357
7.422
7.445
7.475
7.500
7.524
7.757
7.768
7.777
7.789
8.038
8.049
8.058
8.070
Figure S15. 1H NMR (300 MHz, CDCl3) spectrum of 10b
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
46.880
63.650
76.575
76.998
77.200
77.421
126.469
128.902
129.211
129.287
129.963
131.954
140.570
160.833
174.657
Figure S16. 13C NMR (75 MHz, CDCl3) spectrum of 10b
130 ppm
128.902
129.211
129.287
129.963
HN
10b
N
N
NPh
O
O
HH
HN
10b
N
N
NPh
O
O
HH
S-11
9 8 7 6 5 4 3 2 1 0 ppm
1.2438
1.2676
1.2913
3.5833
4.0216
4.0276
4.0334
4.0394
4.2015
4.2145
4.2251
4.2385
4.2493
4.9744
4.9805
4.9863
4.9922
6.3817
6.3907
6.4020
6.4138
7.2385
7.2485
7.2600
7.3267
7.3348
7.3402
7.3469
7.3521
7.3604
7.3670
6.735
1.085
2.142
4.096
1.773
2.000
3.169
4.451
Current Data ParametersNAME cyj060705-PhN3-NPM-diesterEXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20060722Time 20.12INSTRUM spectPROBHD 5 mm MultinuPULPROG zg30TD 16384SOLVENT CDCl3NS 16DS 0SWH 4789.272 HzFIDRES 0.292314 HzAQ 1.7105396 secRG 32DW 104.400 usecDE 6.50 usecTE 300.0 KD1 2.00000000 sec
============ CHANNEL f1 =============NUC1 1HP1 9.90 usecPL1 -3.00 dBSFO1 300.1319508 MHz
F2 - Processing parametersSI 16384SF 300.1300020 MHzWDW EMSSB 0LB 0.10 HzGB 0PC 1.00
1.3 ppm
1.244
1.268
1.291
7.37.4 ppm
7.239
7.248
7.260
7.327
7.335
7.340
7.347
7.352
7.360
7.367
ppm6.382
6.391
6.402
6.414
5.0 ppm
4.974
4.981
4.986
4.992
4.14.24.3 ppm
4.022
4.028
4.033
4.039
4.202
4.215
4.225
4.239
4.249
Figure S17. 1H NMR (300 MHz, CDCl3) spectrum of 11a
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
13.900
46.932
62.111
64.178
66.613
76.577
77.001
77.426
123.978
126.185
126.272
128.500
128.647
128.869
130.878
138.987
166.239
174.196
Figure S18. 13C NMR (75 MHz, CDCl3) spectrum of 11a
126128130 ppm
123.978
126.185
126.272
128.500
128.647
128.869
130.878
11a
N
N
O
OPh
CH(CO2Et)2
HH
11a
N
N
O
OPh
CH(CO2Et)2
HH
S-12
9 8 7 6 5 4 3 2 1 0 ppm
-0.0002
1.1870
1.2106
1.2344
1.2562
1.3793
1.4032
1.4269
3.3032
3.3271
3.7364
3.7602
4.1275
4.1514
4.1775
4.4122
4.4361
4.4584
4.4701
4.4939
5.0699
7.2640
7.3284
7.3315
7.3551
7.3601
7.4136
7.4332
7.4377
7.4682
7.4883
7.4935
7.5169
7.7051
7.7118
7.7174
7.7276
7.7375
7.7434
7.7503
8.0160
8.0222
8.0325
8.0368
4.128
3.319
1.000
1.072
2.362
3.095
0.927
4.817
2.132
2.251
Current Data ParametersNAME cyj071001EXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20071013Time 0.40INSTRUM spectPROBHD 5 mm MultinuPULPROG zg30TD 16384SOLVENT CDCl3NS 16DS 0SWH 4789.272 HzFIDRES 0.292314 HzAQ 1.7105396 secRG 57DW 104.400 usecDE 6.50 usecTE 300.0 KD1 2.00000000 sec
============ CHANNEL f1 =============NUC1 1HP1 9.70 usecPL1 -3.00 dBSFO1 300.1319508 MHz
F2 - Processing parametersSI 16384SF 300.1300046 MHzWDW EMSSB 0LB 0.10 HzGB 0PC 1.00
1D NMR plot parametersCX 23.00 cmF1P 6.000 ppmF1 1800.78 HzF2P 0.000 ppmF2 0.00 HzPPMCM 0.26087 ppm/cmHZCM 78.29478 Hz/cm
7.47.67.88.0 ppm7.264
7.328
7.332
7.355
7.360
7.414
7.433
7.438
7.468
7.488
7.494
7.517
7.705
7.712
7.717
7.728
7.737
7.743
7.750
8.016
8.022
8.033
8.037
8.047
3.54.04.5 ppm
3.303
3.327
3.736
3.760
4.128
4.151
4.178
4.412
4.436
4.458
4.470
4.494
ppm
1.187
1.211
1.234
1.256
Figure S19. 1H NMR (300 MHz, CDCl3) spectrum of 12b
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
-0.041
13.909
14.073
29.658
47.761
48.305
51.306
61.934
62.105
62.447
70.943
76.574
76.998
77.201
77.422
126.513
128.889
129.030
129.172
129.564
129.743
129.854
131.778
140.325
140.550
160.127
160.251
166.550
168.007
173.889
174.429
Figure S20. 13C NMR (75 MHz, CDCl3) spectrum of 12b
p
61.934
62.105
62.447
14
13.909
14.073
ppm
140.325
140.550
pp
160.127
160.251
ppm
128.889
129.030
129.172
129.564
129.743
129.854
12b
N
NN
O
O
Ph
HNCH(CO2Et)2
12b
N
NN
O
O
Ph
HNCH(CO2Et)2
S-13
9 8 7 6 5 4 3 2 1 0 ppm
-0.0001
1.6246
3.7138
3.9617
7.2638
7.6143
7.6251
7.6350
7.6459
7.9119
7.9231
7.9326
7.9436
8.2602
1.197
6.209
2.145
2.122
2.000
Current Data ParametersNAME cyj060729-PhN3-NH-DMADEXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20060809Time 20.07INSTRUM spectPROBHD 5 mm MultinuPULPROG zg30TD 16384SOLVENT CDCl3NS 32DS 0SWH 4789.272 HzFIDRES 0.292314 HzAQ 1.7105396 secRG 362DW 104.400 usecDE 6.50 usecTE 300.0 KD1 2.00000000 sec
============ CHANNEL f1 =============NUC1 1HP1 9.90 usecPL1 -3.00 dBSFO1 300.1319508 MHz
F2 - Processing parametersSI 16384SF 300.1300052 MHzWDW EMSSB 0LB 0.10 HzGB 0PC 1.00
7.77.87.98.0 ppm
7.614
7.625
7.635
7.646
7.912
7.923
7.933
7.944
Figure S21. 1H NMR (300 MHz, CDCl3) spectrum of 13a
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
52.680
76.576
77.000
77.424
128.411
128.578
128.655
130.137
133.370
168.164
Figure S22. 13C NMR (75 MHz, CDCl3) spectrum of 13a
129130 ppm
128.411
128.578
128.655
130.137
HN
13aCO2Me
CO2Me
HN
13aCO2Me
CO2Me
S-14
9 8 7 6 5 4 3 2 1 0 ppm
1.1535
1.1773
1.2009
1.2513
1.2607
1.2641
1.2750
1.2988
1.7464
3.3617
3.7332
3.7743
3.7888
3.8037
3.8101
3.8179
3.8340
3.8705
3.8759
3.9115
3.9285
4.2112
4.2353
4.2441
4.2590
4.2826
5.2607
7.0619
7.0719
7.0792
7.0892
7.2811
7.3975
7.4076
7.4147
7.4248
6.255
1.336
5.802
5.235
1.676
2.000
2.184
Current Data ParametersNAME cyj060801-PhN3-DMAD-diesterEXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20060814Time 17.08INSTRUM spectPROBHD 5 mm MultinuPULPROG zg30TD 16384SOLVENT CDCl3NS 16DS 0SWH 4789.272 HzFIDRES 0.292314 HzAQ 1.7105396 secRG 32DW 104.400 usecDE 6.50 usecTE 300.0 KD1 2.00000000 sec
============ CHANNEL f1 =============NUC1 1HP1 9.90 usecPL1 -3.00 dBSFO1 300.1319508 MHz
F2 - Processing parametersSI 16384SF 300.1300000 MHzWDW EMSSB 0LB 0.10 HzGB 0PC 1.00
7.27.37.4 ppm
7.062
7.072
7.079
7.089
7.281
7.398
7.408
7.415
7.425
ppm
4.211
4.235
4.244
4.259
4.283
1.3 ppm
1.251
1.261
1.264
1.275
1.299
Figure S23. 1H NMR (300 MHz, CDCl3) spectrum of 14a
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
13.898
52.294
62.031
64.834
72.265
76.578
77.001
77.426
123.319
126.205
144.686
149.435
163.275
166.176
Figure S24. 13C NMR (75 MHz, CDCl3) spectrum of 14a
N
14aCO2Me
CO2Me
CH(CO2Et)2
N
14aCO2Me
CO2Me
CH(CO2Et)2
S-15
9 8 7 6 5 4 3 2 1 0 ppm
0.0000
1.1604
1.1660
1.1723
1.1796
1.1841
1.2552
3.7166
3.7217
3.9027
3.9581
4.1874
4.1940
4.1992
4.2059
4.2111
4.2179
4.2231
4.2236
4.2298
5.0624
7.2627
7.8142
7.8167
7.8196
7.8278
7.8308
7.8335
7.8384
7.8415
7.8446
7.8472
7.8492
7.8521
7.8556
7.8583
8.1196
8.1210
8.1227
8.1332
8.1354
8.1362
8.1805
5.933
1.293
1.648
0.856
3.308
3.276
3.810
0.583
0.137
4.322
2.000
Current Data ParametersNAME CYJ-071005EXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20090511Time 18.56INSTRUM spectPROBHD 5 mm QNP 1H/1PULPROG zgTD 32768SOLVENT CDCl3NS 16DS 0SWH 7183.908 HzFIDRES 0.219235 HzAQ 2.2807028 secRG 128DW 69.600 usecDE 6.50 usecTE 301.4 KD1 1.50000000 secMCREST 0.00000000 secMCWRK 0.01500000 sec
======== CHANNEL f1 ========NUC1 1HP1 10.50 usecPL1 0.00 dBSFO1 599.2029960 MHz
F2 - Processing parametersSI 32768SF 599.2000115 MHzWDW noSSB 0LB 0.00 HzGB 0PC 1.00
1D NMR plot parametersCX 20.00 cmCY 6.00 cmF1P 10.000 ppmF1 5992.00 HzF2P -0.500 ppmF2 -299.60 HzPPMCM 0.52500 ppm/cmHZCM 314.58002 Hz/cm
7.87.98.08.18.2 ppm7.814
7.817
7.820
7.828
7.831
7.833
7.838
7.841
7.845
7.847
7.849
7.852
7.856
7.858
8.120
8.121
8.123
8.133
8.135
8.136
8.181
8.183
8.193
4.204.25 ppm
4.187
4.194
4.199
4.206
4.211
4.218
4.223
4.224
4.230
ppm
1.160
1.166
1.172
1.180
1.184
Figure S25. 1H NMR (600 MHz, CDCl3) spectrum of 15b
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
-0.029
14.056
29.683
51.657
51.957
52.145
52.513
61.428
76.787
76.999
77.211
99.996
117.050
129.487
130.755
131.759
134.804
136.798
140.994
142.759
143.834
150.202
167.288
168.265
169.014
Figure S26. 13C NMR (150 MHz, CDCl3) spectrum of 15b
52 ppm
51.657
51.957
52.145
52.513
H2O grease
X
X
X
grease X
15b
N
N
HNCH(CO2Et)2
CO2Me
CO2Me
15b
N
N
HNCH(CO2Et)2
CO2Me
CO2Me
S-16
9 8 7 6 5 4 3 2 1 0 ppm
-0.0002
1.1943
1.2181
1.2421
1.2476
1.2613
1.2715
1.6567
2.6432
2.6576
3.6280
3.6800
3.6946
3.7091
4.0544
4.0668
4.0795
4.0904
4.1038
4.1139
4.1276
4.1394
4.1464
4.1637
4.1702
4.1822
4.9313
5.0469
5.0614
7.2672
7.3455
7.3562
7.3647
7.3743
7.3907
7.4629
7.4801
7.4865
6.602
0.931
0.912
0.971
4.400
1.010
0.968
4.000
Current Data ParametersNAME cyj071006EXPNO 1PROCNO 1
F2 - Acquisition ParametersDate_ 20071101Time 0.47INSTRUM spectPROBHD 5 mm MultinuPULPROG zg30TD 16384SOLVENT CDCl3NS 16DS 0SWH 4789.272 HzFIDRES 0.292314 HzAQ 1.7105396 secRG 57DW 104.400 usecDE 6.50 usecTE 300.0 KD1 2.00000000 sec
============ CHANNEL f1 =============NUC1 1HP1 9.70 usecPL1 -3.00 dBSFO1 300.1319508 MHz
F2 - Processing parametersSI 16384SF 300.1300037 MHzWDW EMSSB 0LB 0.10 HzGB 0PC 1.00
1D NMR plot parametersCX 23.00 cmF1P 5.301 ppmF1 1590.90 HzF2P 2.393 ppmF2 718.21 HzPPMCM 0.12642 ppm/cmHZCM 37.94286 Hz/cm
7.47.5 ppm
7.346
7.356
7.365
7.374
7.391
7.463
7.480
7.487
3.84.04.24.44.64.85.05.2 ppm
3.680
3.695
3.709
4.054
4.067
4.080
4.090
4.104
4.114
4.128
4.139
4.146
4.164
4.170
4.182
4.931
5.047
5.061
ppm
2.643
2.658
1.3 ppm
1.194
1.218
1.242
1.248
1.261
1.272
Figure S27. 1H NMR (300 MHz, CDCl3) spectrum of 16a
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
13.861
35.426
36.301
62.035
62.126
63.374
66.326
68.351
76.578
77.001
77.425
116.958
118.326
122.499
124.429
129.160
129.207
138.320
140.124
165.985
166.041
Figure S28. 13C NMR (75 MHz, CDCl3) spectrum of 16a
ppm
165.985
166.041
pp
129.160
129.207
63 ppm
62.035
62.126
63.374
N
16aCN
CN
CH(CO2Et)2
N
16aCN
CN
CH(CO2Et)2
S-17
3.94.04.14.24.34.44.54.64.74.8 ppm 0.81.01.21.4 ppm
Figure S29. Expand 1H NMR spectra of (a) triazoline 1a (0.025 M in CD3CN), and (b)
1a after irradiated (254 nm) for 15 min, (c) 9a (in CD3CN), and (d) 7 (in CD3CN); the
signals around 0.7 ppm were from aziridines 8a.
≈ ≈
≈ ≈
(a)
(b)
(c)
(d)
S-18
3.94.04.14.24.34.44.54.64.74.84.9 ppm 0.81.01.21.4 ppm
Figure S30. Expand 1H NMR spectra of (a) triazoline 1b (0.025 M in CD3CN), and (b)
1a after irradiated (254 nm) for 15 min, (c) 9b (in CD3CN), and (d) 7 (in CD3CN); the
signals around 0.7 ppm were from aziridines 8b.
≈ ≈
≈ ≈
(a)
(b)
(c)
(d)
S-19
789 ppm 1.01.5 ppm4.04.55.05.5 ppm
Figure S31. 1H NMR spectra of (a) triazoline 1a (0.025 M in d8-THF), and (b) 1a
after irradiated (254 nm) for 15 min, (c) 9a (in d8-THF), and (d) 7 (in d8-THF); where
* denotes an internal standard 1,4-dioxane or the signal of residual THF, and the
signals around 0.6 ppm were from aziridines 8a.
≈ ≈
≈ ≈
≈ ≈
≈ ≈
(a)
(b)
(c)
(d)
*
S-20
8.08.59.0 ppm 1.01.5 ppm4.04.55.05.5 ppm
Figure S32. 1H NMR spectra of (a) triazoline 1b (0.025 M in d8-THF), and (b) 1b
after irradiated (254 nm) for 15 min, (c) 9b (in d8-THF), and (d) 7 (in d8-THF); where
* denotes an internal standard 1,4-dioxane or the signal of residual THF, and the
signals around 0.6 ppm were from aziridines 8b.
*
≈ ≈
≈ ≈
≈ ≈
≈ ≈
(a)
(b)
(c)
(d)
S-21
3000 3200 3400 3600 3800-4
-2
0
2
4
3423
G(g
= 2
.004
5)
EP
R In
tens
ity
Magnetic Field / G
Figure S33. The EPR spectrum in 3000−3800 guess region by the photolysis
(230−325 nm) of a glassy matrix of 1a in MTHF at 77 K for 5 min.
3000 3200 3400 3600 3800-4
-2
0
2
4
3435
G(g
= 2
.004
5)
EP
R In
tens
ity
Magnetic Field / G
Figure S34. The EPR spectrum in 3000−3800 guess region by the photolysis
(230−325 nm) of a glassy matrix of 1b in MTHF at 77 K for 5 min.
N
NN
EtO2CCO2Et
1a
N
NN
NN
EtO2CCO2Et
1b