chungws tetrahedron-supporting information …...p. s-12. figure s19. 1h nmr (300 mhz, cdcl 3)...

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

[email protected]

[email protected]

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-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


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




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





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


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


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





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


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


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





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


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


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




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


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


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




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


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


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




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


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


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





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


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


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




7.77.87.98.0 ppm

7.614

7.625

7.635

7.646

7.912

7.923

7.933

7.944


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


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




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


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


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


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


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





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


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


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

chungws tetrahedron-supporting information …...p. s-12. figure s19. 1h nmr (300 mhz, cdcl 3)...

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