benzylation cascade of 2-morpholinoanilines on water ... · supporting information...

36
S1 Supporting Information Palladium-catalyzed dehydrative N-benzylation/C-H benzylation cascade of 2-morpholinoanilines on water Hidemasa Hikawa*, Risa Ichinose, Shoko Kikkawa and Isao Azumaya* Faculty of Pharmaceutical Sciences, Toho University, Funabashi, Chiba 274-8510, Japan [email protected] and [email protected] 1. Table of contents S1 2. Effects of catalysts and solvents S2 3. Competitive deuterium labeling experiment S3 4. Hammett study S4 5. Scale-up experiment S5 6. Copies of 1 H and 13 C NMR spectra of the all compounds S6-S36 Electronic Supplementary Material (ESI) for Green Chemistry. This journal is © The Royal Society of Chemistry 2018

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S1

Supporting Information

Palladium-catalyzed dehydrative N-benzylation/C-H

benzylation cascade of 2-morpholinoanilines on water

Hidemasa Hikawa*, Risa Ichinose, Shoko Kikkawa and Isao Azumaya*

Faculty of Pharmaceutical Sciences, Toho University, Funabashi, Chiba 274-8510, Japan

[email protected] and [email protected]

1. Table of contents S12. Effects of catalysts and solvents S23. Competitive deuterium labeling experiment S34. Hammett study S45. Scale-up experiment S56. Copies of 1H and 13C NMR spectra of the all compounds S6-S36

Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2018

S2

Effects of catalysts and solvents (see Table 1, entry 8).

A mixture of 2-morpholinoaniline 1a (178 mg, 1 mmol), palladium(II) acetate (11 mg, 0.05 mmol),

sodium diphenylphosphinobenzene-3-sulfonate (TPPMS, 36 mg, 0.1 mmol) and benzyl alcohol 2a (515

L, 5 mmol) in H2O (4 mL) was heated at 100 oC for 20 h in a sealed tube under Ar. After the reaction

mixture was cooled, 1,3,5-trimethoxybenzene (168.2 mg, 1 mmol, internal standard) was added to the

reaction mixture, which was extracted with CDCl3 (8 mL), then the organic layer was analyzed by 1H-

NMR spectroscopy.

abun

danc

e0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

0.18

X : parts per Million : Proton

7.06.9 6.8 6.7 6.6 6.5 6.4 6.3 6.2 6.1 6.0 5.9 5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1

6.

926

6.

922

6.

808

6.

805

6.

789

6.

615

6.

612

6.

596

6.

592

6.

286

6.

283

6.

264

6.

089

6.

049

5.

289

5.

099

4.

699

4.

558

4.

548

4.

535

4.

365

4.

209

3.00

0.95

0.95

91.4

2m

abun

danc

e0

0.1

0.2

X : parts per Million : Proton

7.06.9 6.8 6.7 6.6 6.5 6.4 6.3 6.2 6.1 6.0 5.9 5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4 4.3 4.2 4.1

6.

947

6.

944

6.

928

6.

924

6.

810

6.

616

6.

613

6.

598

6.

595

6.

285

6.

282

6.

266

6.

262

5.

298

4.

552

11.4

2 5.01

3.93

1.00

1.00

1.00

0.99

0.98

0.96

Filename = M-HH7-81_Proton-1-7.jdfAuthor = deltaExperiment = proton.jxpSample_Id = M-HH7-81Solvent = CHLOROFORM-DCreation_Time = 5-OCT-2017 09:47:35Revision_Time = 21-NOV-2017 14:01:44Current_Time = 21-NOV-2017 14:23:55

Comment = single_pulseData_Format = 1D COMPLEXDim_Size = 13107Dim_Title = ProtonDim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 2.18365952[s]X_Domain = 1HX_Freq = 399.78219838[MHz]X_Offset = 5[ppm]X_Points = 16384X_Prescans = 1X_Resolution = 0.45794685[Hz]X_Sweep = 7.5030012[kHz]X_Sweep_Clipped = 6.00240096[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Tri_Domain = ProtonTri_Freq = 399.78219838[MHz]Tri_Offset = 5[ppm]Clipped = FALSEScans = 8Total_Scans = 8

Relaxation_Delay = 5[s]Recvr_Gain = 36Temp_Get = 21.7[dC]X_90_Width = 13.67[us]X_Acq_Time = 2.18365952[s]X_Angle = 45[deg]X_Atn = 2.2[dB]X_Pulse = 6.835[us]Irr_Mode = OffTri_Mode = OffDante_Presat = FALSEInitial_Wait = 1[s]Repetition_Time = 7.18365952[s]

NH2

N

O

1a3a

Ph OH 2a (5 equiv)Pd catalyst (5 mol%)TPPMS (10 mol%)

100 oC, 20 h, Ar NH

N

O

PhPh

N

N

O

Ph

5not detected Ph

NH

PhPh

NO

3a

authentic sample

OMe

MeO OMe

S3

Competitive deuterium labeling experiment (see Scheme 4A).

H2O/D2O (1:1)100 oC, 16 h

2a (1 mmol)

NH

N

O

4a (0.25 mmol)

Ph OH

Pd(OAc)2 (5 mol%)TPPMS (10 mol%)

PhH

H

NH

N

O

D5-PhD

D4a-d (0.25 mmol)

D5-Ph OH

D D

2a-d (1 mmol)

NH

N

O

PhPh

H/D3a (kH/kD = 2.7)

A mixture of 4a (67.1 mg, 0.25 mmol), 4a-d (68.9 mg, 0.25 mmol), Pd(OAc)2 (6 mg, 0.025 mmol),

sodium diphenylphosphinobenzene-3-sulfonate (TPPMS, 18 mg, 0.05 mmol), benzyl alcohol 2a (108 mg,

1.0 mmol), and 2a-d (115 mg, 1.0 mmol) in H2O (1 mL) and D2O (1 mL) was heated at 100 oC for 16 h in

a sealed tube under air. After cooling, the reaction mixture was poured into water and extracted with

EtOAc. The organic layer was washed with brine, dried over MgSO4 and concentrated in vacuo. The

residue was washed with hexanes, then purified by flash column chromatography (silica gel,

hexanes/EtOAc) to give desired product 3a.

Signal 6.27 (Ar-H) 4.55 (methine-H)

Integral value 1.00 (1H) 0.73 (1H): kH/kD = 0.73/0.27 = 2.7

abun

danc

e0

0.1

0.2

X : parts per Million : Proton

6.3 6.2 6.1 6.0 5.9 5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4

6.

285

6.

266

5.

289

5.

154

4.

564

4.

540

9.06

1.02

1.00

0.93

0.85

0.73

0.56

0.52

76.1

3m

57.5

6m

21.5

9m

16.1

5m

5.93

m

abun

danc

e0

0.1

0.2

X : parts per Million : Proton

6.3 6.2 6.1 6.0 5.9 5.8 5.7 5.6 5.5 5.4 5.3 5.2 5.1 5.0 4.9 4.8 4.7 4.6 4.5 4.4

6.

285

6.

282

6.

266

6.

262

5.

298

4.

552

11.4

2

5.01

3.93

1.03

1.00

1.00

1.00

0.99

0.98

0.96

Filename = M-HH7-81_Proton-1-6.jdfAuthor = deltaExperiment = proton.jxpSample_Id = M-HH7-81Solvent = CHLOROFORM-DCreation_Time = 5-OCT-2017 09:47:35Revision_Time = 21-NOV-2017 12:59:10Current_Time = 21-NOV-2017 12:59:19

Comment = single_pulseData_Format = 1D COMPLEXDim_Size = 13107Dim_Title = ProtonDim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 2.18365952[s]X_Domain = 1HX_Freq = 399.78219838[MHz]X_Offset = 5[ppm]X_Points = 16384X_Prescans = 1X_Resolution = 0.45794685[Hz]X_Sweep = 7.5030012[kHz]X_Sweep_Clipped = 6.00240096[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Tri_Domain = ProtonTri_Freq = 399.78219838[MHz]Tri_Offset = 5[ppm]Clipped = FALSEScans = 8Total_Scans = 8

Relaxation_Delay = 5[s]Recvr_Gain = 36Temp_Get = 21.7[dC]X_90_Width = 13.67[us]X_Acq_Time = 2.18365952[s]X_Angle = 45[deg]X_Atn = 2.2[dB]X_Pulse = 6.835[us]Irr_Mode = OffTri_Mode = OffDante_Presat = FALSEInitial_Wait = 1[s]Repetition_Time = 7.18365952[s]NH

PhPh

NO

3a

authentic sample

S4

Hammett study (see Figure 4).

A mixture of 3- or 5-substituted 2-morpholinoanilines 1 (X = Me, Cl and CF3 groups) (0.25 mmol),

Pd(OAc)2 (6 mg, 0.025 mmol), sodium diphenylphosphinobenzene-3-sulfonate (TPPMS, 18 mg, 0.05

mmol) and benzylic alcohol 2a (258 L, 2.5 mmol) in H2O (2 mL) was heated at 120 oC in a sealed tube

under air. After cooling, the reaction mixture was poured into water and extracted with EtOAc. The

organic layer was washed with brine, dried over MgSO4 and concentrated in vacuo. The residue was

analyzed by 1H-NMR spectroscopy.

X = CF3: log(kX/kH) = log(1/9) = -0.95

abun

danc

e0

0.1

X : parts per Million : Proton

6.8 6.7 6.6 6.5 6.4 6.3 6.2 6.1 6.0

6.

826

6.

821

6.

816

6.

811

6.

803

6.

787

6.

784

6.

731

6.

711

6.

708

6.

693

6.

614

6.

611

6.

595

6.

591

6.

575

6.

572

6.

490

6.

290

6.

269

26.5

7 12.3

4

10.1

5

9.00

1.00

abun

danc

e0

0.1

0.2

0.3

X : parts per Million : Proton

6.9 6.8 6.7 6.6 6.5 6.4 6.3 6.2 6.1 6.0

6.

829

6.

826

6.

810

6.

807

6.

790

6.

787

6.

616

6.

613

6.

598

6.

595

6.

579

6.

575

6.

285

6.

282

6.

266

6.

262

11.4

2

5.01

3.93

1.00

1.00

1.00

0.99

0.98

0.96

abun

danc

e0

0.1

0.2

0.3

X : parts per Million : Proton

6.9 6.8 6.7 6.6 6.5 6.4 6.3 6.2 6.1 6.0

6.

855

6.

851

6.

835

6.

832

6.

485

6.

480

9.81

4.29

2.31

2.27

1.94

1.09

1.08

1.07

1.06

1.05

1.05

1.00

Filename = M-HH7-22-1-F1-CD_Proton-1-Author = deltaExperiment = proton.jxpSample_Id = M-HH7-22-1-F1-CDSolvent = CHLOROFORM-DCreation_Time = 15-SEP-2017 13:20:31Revision_Time = 21-NOV-2017 14:06:00Current_Time = 21-NOV-2017 14:06:06

Comment = single_pulseData_Format = 1D COMPLEXDim_Size = 13107Dim_Title = ProtonDim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 2.18365952[s]X_Domain = 1HX_Freq = 399.78219838[MHz]X_Offset = 5[ppm]X_Points = 16384X_Prescans = 1X_Resolution = 0.45794685[Hz]X_Sweep = 7.5030012[kHz]X_Sweep_Clipped = 6.00240096[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Tri_Domain = ProtonTri_Freq = 399.78219838[MHz]Tri_Offset = 5[ppm]Clipped = FALSEScans = 8Total_Scans = 8

Relaxation_Delay = 5[s]Recvr_Gain = 36Temp_Get = 22[dC]X_90_Width = 13.5[us]X_Acq_Time = 2.18365952[s]X_Angle = 45[deg]X_Atn = 2.2[dB]X_Pulse = 6.75[us]Irr_Mode = OffTri_Mode = OffDante_Presat = FALSEInitial_Wait = 1[s]Repetition_Time = 7.18365952[s]

    log(kX/kH)

5-Me (m) -0.07 0.17

H 0 0

3-Cl (m) 0.37 -0.6

5-Cl (m) 0.37 -1.02

5-CF3 (m) 0.43 -0.954

2a (2.5 mol)Ph OH

1X(0.25 mmol)

H2O, 120 oC

3X

Pd(OAc)2 (5 mol%)TPPMS (10 mol%)

NH2

NO

X

NH

NO

X

PhPh1a

(0.25 mmol)

NH2

NO

+

3a

NH

NO

PhPh

+

NH

PhPh

NO

3a

authentic sample

authentic sample

NH

PhPh

NO

3e

F3C

S5

Scale-up experiment (see Scheme 9).

2a(5 equiv)

NH2

N

O

100 oC, 16 h1a1.1 g

Ph OH

Pd(OAc)2 (5 mol%)TPPMS (10 mol%)

NH

N

O

PhPh

3a: 1.6 g (76%)

+

A mixture of 2-morpholinoaniline (1.07 g, 6 mmol), palladium(II) acetate (67.4 mg, 0.3 mmol),

TPPMS (218.6 mg, 0.6 mmol), and benzyl alcohol (2a, 3.09 mL, 30 mmol) in H2O (24 mL) was heated at

100 oC for 16 h under Ar. After cooling, the reaction mixture was poured into water and extracted with

EtOAc. The organic layer was washed with brine, dried over MgSO4 and concentrated in vacuo. The

residue was recrystallized from hexane/AcOEt to give desired product 3a (1.63 g, 4.55 mmol, 76%) as a

pale yellow solid.

After 10 min After 16 h

S6

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

X : parts per Million : Proton

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

7.

351

7.

346

7.

328

7.

269

7.

256

7.

198

6.

928

6.

924

6.

598

6.

285

6.

282

6.

266

6.

262

5.

298

4.

552

3.

771

3.

227

3.

215

2.

993

2.

935

2.

638

0.

008

-0.

000

-0.

008

11.1

5

4.89

3.84

1.00

1.00

0.99

0.98

0.96

0.96

0.93

Filename = M-HH7-81_Proton-1-5.jdfAuthor = deltaExperiment = proton.jxpSample_Id = M-HH7-81Solvent = CHLOROFORM-DCreation_Time = 5-OCT-2017 09:47:35Revision_Time = 21-NOV-2017 12:56:10Current_Time = 21-NOV-2017 12:56:17

Comment = single_pulseData_Format = 1D COMPLEXDim_Size = 13107Dim_Title = ProtonDim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 2.18365952[s]X_Domain = 1HX_Freq = 399.78219838[MHz]X_Offset = 5[ppm]X_Points = 16384X_Prescans = 1X_Resolution = 0.45794685[Hz]X_Sweep = 7.5030012[kHz]X_Sweep_Clipped = 6.00240096[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Tri_Domain = ProtonTri_Freq = 399.78219838[MHz]Tri_Offset = 5[ppm]Clipped = FALSEScans = 8Total_Scans = 8

Relaxation_Delay = 5[s]Recvr_Gain = 36Temp_Get = 21.7[dC]X_90_Width = 13.67[us]X_Acq_Time = 2.18365952[s]X_Angle = 45[deg]X_Atn = 2.2[dB]X_Pulse = 6.835[us]Irr_Mode = OffTri_Mode = OffDante_Presat = FALSEInitial_Wait = 1[s]Repetition_Time = 7.18365952[s]

3a

NH

PhPh

NO

S7

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

X : parts per Million : Carbon13

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0

143

.934

142

.389

138

.547

137

.927

129

.318

128

.621

128

.526

127

.001

126

.753

126

.228

125

.141

119

.564

116

.760

111

.564

77.

335

77.

011

76.

696

67.

772

59.

219

51.

735

45.

661

0.

000

Filename = M-HH7-81-C_Carbon-1-3.jdfAuthor = deltaExperiment = carbon.jxpSample_Id = M-HH7-81-CSolvent = CHLOROFORM-DCreation_Time = 22-NOV-2017 14:03:40Revision_Time = 22-NOV-2017 14:17:14Current_Time = 22-NOV-2017 14:17:42

Comment = single pulse decoupled gatData_Format = 1D COMPLEXDim_Size = 26214Dim_Title = Carbon13Dim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 1.04333312[s]X_Domain = 13CX_Freq = 100.52530333[MHz]X_Offset = 100[ppm]X_Points = 32768X_Prescans = 4X_Resolution = 0.95846665[Hz]X_Sweep = 31.40703518[kHz]X_Sweep_Clipped = 25.12562814[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Clipped = FALSEScans = 512Total_Scans = 512

Relaxation_Delay = 2[s]Recvr_Gain = 60Temp_Get = 21.9[dC]X_90_Width = 9.74[us]X_Acq_Time = 1.04333312[s]X_Angle = 30[deg]X_Atn = 3.3[dB]X_Pulse = 3.24666667[us]Irr_Atn_Dec = 20.699[dB]Irr_Atn_Noe = 20.699[dB]Irr_Noise = WALTZIrr_Pwidth = 0.115[ms]Decoupling = TRUEInitial_Wait = 1[s]Noe = TRUENoe_Time = 2[s]Repetition_Time = 3.04333312[s]

3a

NH

PhPh

NO

S8

abun

danc

e0

0.1

0.2

0.3

0.4

X : parts per Million : Proton

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

7.

351

7.

346

7.

327

7.

276

7.

258

7.

186

6.

845

6.

825

6.

417

6.

414

6.

103

6.

099

5.

310

5.

300

4.

572

4.

561

4.

549

4.

538

4.

527

3.

785

3.

757

3.

215

3.

203

2.

986

2.

963

2.

852

2.

843

2.

079

0.

008

0.

000

-0.

008

13.4

1

5.08

4.01

3.20

1.11

1.07

1.04

1.02

1.01

1.00

Filename = M-HH7-70-4_Proton-1-7.jdfAuthor = deltaExperiment = proton.jxpSample_Id = M-HH7-70-4Solvent = CHLOROFORM-DCreation_Time = 21-OCT-2017 13:06:41Revision_Time = 21-NOV-2017 15:19:35Current_Time = 21-NOV-2017 15:19:49

Comment = single_pulseData_Format = 1D COMPLEXDim_Size = 52429Dim_Title = ProtonDim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 8.73463808[s]X_Domain = 1HX_Freq = 399.78219838[MHz]X_Offset = 5[ppm]X_Points = 65536X_Prescans = 1X_Resolution = 0.11448671[Hz]X_Sweep = 7.5030012[kHz]X_Sweep_Clipped = 6.00240096[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Tri_Domain = ProtonTri_Freq = 399.78219838[MHz]Tri_Offset = 5[ppm]Clipped = FALSEScans = 8Total_Scans = 8

Relaxation_Delay = 5[s]Recvr_Gain = 36Temp_Get = 21.6[dC]X_90_Width = 13.67[us]X_Acq_Time = 8.73463808[s]X_Angle = 45[deg]X_Atn = 2.2[dB]X_Pulse = 6.835[us]Irr_Mode = OffTri_Mode = OffDante_Presat = FALSEInitial_Wait = 1[s]Repetition_Time = 13.73463808[s]

3b

NH

PhPh

NO

Me

S9

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

X : parts per Million : Carbon13

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0

144

.010

142

.294

137

.975

136

.211

134

.848

129

.318

128

.583

128

.478

126

.934

126

.705

126

.228

119

.554

117

.170

112

.260

77.

335

77.

221

77.

011

76.

696

67.

819

59.

076

51.

983

45.

623

21.

424

0.

000

Filename = M-HH7-70-4-C_Carbon-1-5.jdAuthor = deltaExperiment = carbon.jxpSample_Id = M-HH7-70-4-CSolvent = CHLOROFORM-DCreation_Time = 22-OCT-2017 09:20:15Revision_Time = 21-NOV-2017 15:23:55Current_Time = 21-NOV-2017 15:24:06

Comment = single pulse decoupled gatData_Format = 1D COMPLEXDim_Size = 26214Dim_Title = Carbon13Dim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 1.04333312[s]X_Domain = 13CX_Freq = 100.52530333[MHz]X_Offset = 100[ppm]X_Points = 32768X_Prescans = 4X_Resolution = 0.95846665[Hz]X_Sweep = 31.40703518[kHz]X_Sweep_Clipped = 25.12562814[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Clipped = FALSEScans = 12000Total_Scans = 12000

Relaxation_Delay = 2[s]Recvr_Gain = 60Temp_Get = 22.2[dC]X_90_Width = 9.74[us]X_Acq_Time = 1.04333312[s]X_Angle = 30[deg]X_Atn = 3.3[dB]X_Pulse = 3.24666667[us]Irr_Atn_Dec = 20.699[dB]Irr_Atn_Noe = 20.699[dB]Irr_Noise = WALTZIrr_Pwidth = 0.115[ms]Decoupling = TRUEInitial_Wait = 1[s]Noe = TRUENoe_Time = 2[s]Repetition_Time = 3.04333312[s]

3b

NH

PhPh

NO

Me

S10

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

X : parts per Million : Proton

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

7.

311

7.

303

7.

288

7.

268

7.

258

7.

256

6.

755

6.

735

6.

496

6.

166

6.

002

5.

991

4.

636

4.

623

4.

612

4.

600

4.

589

3.

919

3.

896

3.

701

3.

685

3.

325

3.

318

3.

025

3.

002

2.

590

2.

562

2.

254

2.

226

-0.

000

-0.

008

11.6

3

3.02

2.02

1.03

1.03

1.02

1.01

1.01

1.01

1.00

1.00

1.00

0.97

Filename = M-HH7-70-2_Proton-1-6.jdfAuthor = deltaExperiment = proton.jxpSample_Id = M-HH7-70-2Solvent = CHLOROFORM-DCreation_Time = 11-SEP-2017 12:37:55Revision_Time = 21-NOV-2017 15:47:58Current_Time = 21-NOV-2017 15:48:17

Comment = single_pulseData_Format = 1D COMPLEXDim_Size = 13107Dim_Title = ProtonDim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 2.18365952[s]X_Domain = 1HX_Freq = 399.78219838[MHz]X_Offset = 5[ppm]X_Points = 16384X_Prescans = 1X_Resolution = 0.45794685[Hz]X_Sweep = 7.5030012[kHz]X_Sweep_Clipped = 6.00240096[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Tri_Domain = ProtonTri_Freq = 399.78219838[MHz]Tri_Offset = 5[ppm]Clipped = FALSEScans = 8Total_Scans = 8

Relaxation_Delay = 5[s]Recvr_Gain = 36Temp_Get = 22[dC]X_90_Width = 13.5[us]X_Acq_Time = 2.18365952[s]X_Angle = 45[deg]X_Atn = 2.2[dB]X_Pulse = 6.75[us]Irr_Mode = OffTri_Mode = OffDante_Presat = FALSEInitial_Wait = 1[s]Repetition_Time = 7.18365952[s]

3c

NH

PhPh

NOCl

S11

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

X : parts per Million : Carbon13

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0

146

.823

143

.391

137

.632

133

.541

132

.206

129

.203

128

.669

128

.583

127

.592

127

.144

126

.858

126

.171

117

.971

109

.705

77.

335

77.

020

76.

696

68.

382

68.

086

58.

514

48.

703

48.

674

45.

203

-0.

000

Filename = M-HH7-70-2-C_Carbon-1-3.jdAuthor = deltaExperiment = carbon.jxpSample_Id = M-HH7-70-2-CSolvent = CHLOROFORM-DCreation_Time = 30-SEP-2017 18:46:40Revision_Time = 2-OCT-2017 13:08:16Current_Time = 21-NOV-2017 15:49:46

Comment = single pulse decoupled gatData_Format = 1D COMPLEXDim_Size = 26214Dim_Title = Carbon13Dim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 1.04333312[s]X_Domain = 13CX_Freq = 100.52530333[MHz]X_Offset = 100[ppm]X_Points = 32768X_Prescans = 4X_Resolution = 0.95846665[Hz]X_Sweep = 31.40703518[kHz]X_Sweep_Clipped = 25.12562814[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Clipped = TRUEScans = 1024Total_Scans = 1024

Relaxation_Delay = 2[s]Recvr_Gain = 60Temp_Get = 22.3[dC]X_90_Width = 9.74[us]X_Acq_Time = 1.04333312[s]X_Angle = 30[deg]X_Atn = 3.3[dB]X_Pulse = 3.24666667[us]Irr_Atn_Dec = 20.699[dB]Irr_Atn_Noe = 20.699[dB]Irr_Noise = WALTZIrr_Pwidth = 0.115[ms]Decoupling = TRUEInitial_Wait = 1[s]Noe = TRUENoe_Time = 2[s]Repetition_Time = 3.04333312[s]

3c

NH

PhPh

NOCl

S12

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

1.4

1.5

1.6

1.7

1.8

X : parts per Million : Proton

7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

7.

331

7.

327

7.

289

7.

270

7.

257

7.

174

6.

810

6.

550

6.

544

6.

233

6.

227

5.

360

5.

349

4.

556

4.

544

4.

533

4.

521

4.

510

3.

747

3.

230

3.

219

2.

983

2.

960

2.

593

-0.

000

9.79

3.99

3.54

2.06

1.06

1.04

1.01

1.00

1.00

0.99

0.97

Filename = M-HH7-70-3-F2-2_Proton-1-9Author = deltaExperiment = proton.jxpSample_Id = M-HH7-70-3-F2-2Solvent = CHLOROFORM-DCreation_Time = 11-OCT-2017 09:14:24Revision_Time = 21-NOV-2017 15:54:50Current_Time = 21-NOV-2017 15:55:09

Comment = single_pulseData_Format = 1D COMPLEXDim_Size = 13107Dim_Title = ProtonDim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 2.18365952[s]X_Domain = 1HX_Freq = 399.78219838[MHz]X_Offset = 5[ppm]X_Points = 16384X_Prescans = 1X_Resolution = 0.45794685[Hz]X_Sweep = 7.5030012[kHz]X_Sweep_Clipped = 6.00240096[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Tri_Domain = ProtonTri_Freq = 399.78219838[MHz]Tri_Offset = 5[ppm]Clipped = FALSEScans = 8Total_Scans = 8

Relaxation_Delay = 5[s]Recvr_Gain = 36Temp_Get = 22.1[dC]X_90_Width = 13.67[us]X_Acq_Time = 2.18365952[s]X_Angle = 45[deg]X_Atn = 2.2[dB]X_Pulse = 6.835[us]Irr_Mode = OffTri_Mode = OffDante_Presat = FALSEInitial_Wait = 1[s]Repetition_Time = 7.18365952[s]

3d

NH

PhPh

NO

Cl

S13

abun

danc

e0

0.1

0.2

0.3

X : parts per Million : Carbon13

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0

143

.486

143

.057

137

.632

137

.060

130

.719

129

.260

128

.765

128

.583

127

.277

126

.858

126

.142

120

.708

116

.312

111

.326

77.

335

77.

221

77.

020

76.

696

67.

667

58.

933

51.

811

45.

442

0.

000

Filename = M-HH7-70-3-F2-C_Carbon-1-4Author = deltaExperiment = carbon.jxpSample_Id = M-HH7-70-3-F2-CSolvent = CHLOROFORM-DCreation_Time = 14-OCT-2017 14:54:59Revision_Time = 16-OCT-2017 09:49:08Current_Time = 21-NOV-2017 15:56:34

Comment = single pulse decoupled gatData_Format = 1D COMPLEXDim_Size = 26214Dim_Title = Carbon13Dim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 1.04333312[s]X_Domain = 13CX_Freq = 100.52530333[MHz]X_Offset = 100[ppm]X_Points = 32768X_Prescans = 4X_Resolution = 0.95846665[Hz]X_Sweep = 31.40703518[kHz]X_Sweep_Clipped = 25.12562814[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Clipped = FALSEScans = 35000Total_Scans = 35000

Relaxation_Delay = 2[s]Recvr_Gain = 60Temp_Get = 21.9[dC]X_90_Width = 9.74[us]X_Acq_Time = 1.04333312[s]X_Angle = 30[deg]X_Atn = 3.3[dB]X_Pulse = 3.24666667[us]Irr_Atn_Dec = 20.699[dB]Irr_Atn_Noe = 20.699[dB]Irr_Noise = WALTZIrr_Pwidth = 0.115[ms]Decoupling = TRUEInitial_Wait = 1[s]Noe = TRUENoe_Time = 2[s]Repetition_Time = 3.04333312[s]

3d

NH

PhPh

NO

Cl

S14

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

1.4

1.5

1.6

1.7

1.8

1.9

2.0

2.1

2.2

2.3

X : parts per Million : Proton

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

7.

345

7.

339

7.

331

7.

300

7.

282

7.

257

6.

963

6.

944

6.

485

6.

480

5.

302

5.

292

4.

600

4.

589

4.

577

4.

566

4.

553

3.

772

3.

253

3.

241

3.

015

2.

992

2.

662

-0.

000

9.23

4.03

2.18

2.14

1.83

1.03

1.01

1.01

1.00

1.00

0.99

0.99

Filename = M-HH7-22-1-F1-CD_Proton-1-Author = deltaExperiment = proton.jxpSample_Id = M-HH7-22-1-F1-CDSolvent = CHLOROFORM-DCreation_Time = 15-SEP-2017 13:20:31Revision_Time = 21-NOV-2017 16:00:49Current_Time = 21-NOV-2017 16:01:05

Comment = single_pulseData_Format = 1D COMPLEXDim_Size = 13107Dim_Title = ProtonDim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 2.18365952[s]X_Domain = 1HX_Freq = 399.78219838[MHz]X_Offset = 5[ppm]X_Points = 16384X_Prescans = 1X_Resolution = 0.45794685[Hz]X_Sweep = 7.5030012[kHz]X_Sweep_Clipped = 6.00240096[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Tri_Domain = ProtonTri_Freq = 399.78219838[MHz]Tri_Offset = 5[ppm]Clipped = FALSEScans = 8Total_Scans = 8

Relaxation_Delay = 5[s]Recvr_Gain = 36Temp_Get = 22[dC]X_90_Width = 13.5[us]X_Acq_Time = 2.18365952[s]X_Angle = 45[deg]X_Atn = 2.2[dB]X_Pulse = 6.75[us]Irr_Mode = OffTri_Mode = OffDante_Presat = FALSEInitial_Wait = 1[s]Repetition_Time = 7.18365952[s]

3e

NH

PhPh

NO

F3C

S15

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

X : parts per Million : Carbon13

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0

150

.953

143

.878

129

.824

129

.033

128

.852

127

.574

127

.069

126

.764

113

.539

107

.094

107

.056

107

.017

67.

096

58.

792

51.

250

44.

661

40.

533

40.

323

40.

113

39.

904

39.

694

39.

484

39.

274

Filename = M-HH7-22-1-F1_Carbon-1-3.jAuthor = deltaExperiment = carbon.jxpSample_Id = M-HH7-22-1-F1Solvent = DMSO-D6Creation_Time = 26-SEP-2017 23:33:13Revision_Time = 21-NOV-2017 16:03:01Current_Time = 21-NOV-2017 16:03:26

Comment = single pulse decoupled gatData_Format = 1D COMPLEXDim_Size = 26214Dim_Title = Carbon13Dim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 1.04333312[s]X_Domain = 13CX_Freq = 100.52530333[MHz]X_Offset = 100[ppm]X_Points = 32768X_Prescans = 4X_Resolution = 0.95846665[Hz]X_Sweep = 31.40703518[kHz]X_Sweep_Clipped = 25.12562814[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Clipped = FALSEScans = 8000Total_Scans = 8000

Relaxation_Delay = 2[s]Recvr_Gain = 60Temp_Get = 22.4[dC]X_90_Width = 9.74[us]X_Acq_Time = 1.04333312[s]X_Angle = 30[deg]X_Atn = 3.3[dB]X_Pulse = 3.24666667[us]Irr_Atn_Dec = 20.699[dB]Irr_Atn_Noe = 20.699[dB]Irr_Noise = WALTZIrr_Pwidth = 0.115[ms]Decoupling = TRUEInitial_Wait = 1[s]Noe = TRUENoe_Time = 2[s]Repetition_Time = 3.04333312[s]

3e

NH

PhPh

NO

F3C

S16

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

1.4

1.5

1.6

1.7

X : parts per Million : Proton

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

7.

299

7.

277

7.

191

7.

170

6.

852

6.

850

6.

466

6.

204

6.

200

6.

183

5.

212

5.

198

4.

475

4.

463

4.

451

4.

440

4.

427

3.

708

3.

689

3.

338

3.

263

3.

011

2.

904

2.

879

2.

567

2.

537

9.97

5.12

2.03

2.01

1.98

1.71

1.04

1.02

1.02

1.00

0.99

0.98

0.96

Filename = M-HH7-21-1-F2_Proton-1-4.jAuthor = deltaExperiment = proton.jxpSample_Id = M-HH6-21-1-F2Solvent = DMSO-D6Creation_Time = 11-NOV-2016 13:59:50Revision_Time = 21-NOV-2017 16:08:01Current_Time = 21-NOV-2017 16:08:20

Comment = single_pulseData_Format = 1D COMPLEXDim_Size = 13107Dim_Title = ProtonDim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 2.18365952[s]X_Domain = 1HX_Freq = 399.78219838[MHz]X_Offset = 5[ppm]X_Points = 16384X_Prescans = 1X_Resolution = 0.45794685[Hz]X_Sweep = 7.5030012[kHz]X_Sweep_Clipped = 6.00240096[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Tri_Domain = ProtonTri_Freq = 399.78219838[MHz]Tri_Offset = 5[ppm]Clipped = FALSEScans = 8Total_Scans = 8

Relaxation_Delay = 5[s]Recvr_Gain = 34Temp_Get = 20.2[dC]X_90_Width = 13.1[us]X_Acq_Time = 2.18365952[s]X_Angle = 45[deg]X_Atn = 2.2[dB]X_Pulse = 6.55[us]Irr_Mode = OffTri_Mode = OffDante_Presat = FALSEInitial_Wait = 1[s]Repetition_Time = 7.18365952[s]

3f

NH

NO

MeO

OMe

S17

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

X : parts per Million : Carbon13

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0

158

.542

158

.409

142

.286

138

.825

136

.537

130

.816

130

.787

127

.822

125

.066

119

.756

116

.714

114

.264

114

.187

111

.413

67.

363

58.

420

55.

521

55.

483

51.

841

44.

328

40.

571

40.

361

40.

151

39.

942

39.

732

39.

532

39.

322

Filename = M-HH7-21-1-F2-C_Carbon-1-4Author = deltaExperiment = carbon.jxpSample_Id = M-HH7-21-1-F2-CSolvent = DMSO-D6Creation_Time = 2-OCT-2017 02:44:43Revision_Time = 2-OCT-2017 12:59:03Current_Time = 21-NOV-2017 16:09:19

Comment = single pulse decoupled gatData_Format = 1D COMPLEXDim_Size = 26214Dim_Title = Carbon13Dim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 1.04333312[s]X_Domain = 13CX_Freq = 100.52530333[MHz]X_Offset = 100[ppm]X_Points = 32768X_Prescans = 4X_Resolution = 0.95846665[Hz]X_Sweep = 31.40703518[kHz]X_Sweep_Clipped = 25.12562814[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Clipped = FALSEScans = 4000Total_Scans = 4000

Relaxation_Delay = 2[s]Recvr_Gain = 60Temp_Get = 22.2[dC]X_90_Width = 9.74[us]X_Acq_Time = 1.04333312[s]X_Angle = 30[deg]X_Atn = 3.3[dB]X_Pulse = 3.24666667[us]Irr_Atn_Dec = 20.699[dB]Irr_Atn_Noe = 20.699[dB]Irr_Noise = WALTZIrr_Pwidth = 0.115[ms]Decoupling = TRUEInitial_Wait = 1[s]Noe = TRUENoe_Time = 2[s]Repetition_Time = 3.04333312[s]

3f

NH

NO

MeO

OMe

S18

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

X : parts per Million : Proton

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

7.

226

7.

204

7.

064

7.

042

6.

852

6.

831

6.

811

6.

789

6.

591

6.

306

6.

304

6.

283

5.

252

5.

243

4.

454

4.

443

4.

432

4.

420

4.

000

3.

982

3.

784

3.

110

3.

097

2.

915

2.

668

1.

423

1.

411

1.

406

1.

394

1.

387

1.

376

-0.

000

6.45

5.28

4.18

3.61

3.09

2.14

1.93

1.84

1.06

1.05

1.04

1.03

1.02

1.00

Filename = M-HH7-21-5_Proton-1-6.jdfAuthor = deltaExperiment = proton.jxpSample_Id = M-HH7-21-5Solvent = CHLOROFORM-DCreation_Time = 30-SEP-2017 11:24:41Revision_Time = 21-NOV-2017 16:12:55Current_Time = 21-NOV-2017 16:13:07

Comment = single_pulseData_Format = 1D COMPLEXDim_Size = 13107Dim_Title = ProtonDim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 2.18365952[s]X_Domain = 1HX_Freq = 399.78219838[MHz]X_Offset = 5[ppm]X_Points = 16384X_Prescans = 1X_Resolution = 0.45794685[Hz]X_Sweep = 7.5030012[kHz]X_Sweep_Clipped = 6.00240096[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Tri_Domain = ProtonTri_Freq = 399.78219838[MHz]Tri_Offset = 5[ppm]Clipped = FALSEScans = 8Total_Scans = 8

Relaxation_Delay = 5[s]Recvr_Gain = 34Temp_Get = 22[dC]X_90_Width = 13.67[us]X_Acq_Time = 2.18365952[s]X_Angle = 45[deg]X_Atn = 2.2[dB]X_Pulse = 6.835[us]Irr_Mode = OffTri_Mode = OffDante_Presat = FALSEInitial_Wait = 1[s]Repetition_Time = 7.18365952[s]

3g

NH

NO

EtO

OEt

S19

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

X : parts per Million : Carbon13

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0

157

.874

157

.750

142

.504

138

.518

135

.811

130

.300

129

.842

127

.258

125

.132

119

.468

116

.627

114

.463

114

.434

111

.631

77.

335

77.

020

76.

706

67.

781

63.

434

63.

367

58.

733

51.

744

44.

870

14.

903

14.

845

-0.

000

Filename = M-HH7-21-5-C_Carbon-1-3.jdAuthor = deltaExperiment = carbon.jxpSample_Id = M-HH7-21-5-CSolvent = CHLOROFORM-DCreation_Time = 1-OCT-2017 09:32:34Revision_Time = 2-OCT-2017 13:02:49Current_Time = 21-NOV-2017 16:13:57

Comment = single pulse decoupled gatData_Format = 1D COMPLEXDim_Size = 26214Dim_Title = Carbon13Dim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 1.04333312[s]X_Domain = 13CX_Freq = 100.52530333[MHz]X_Offset = 100[ppm]X_Points = 32768X_Prescans = 4X_Resolution = 0.95846665[Hz]X_Sweep = 31.40703518[kHz]X_Sweep_Clipped = 25.12562814[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Clipped = FALSEScans = 3551Total_Scans = 3551

Relaxation_Delay = 2[s]Recvr_Gain = 60Temp_Get = 22.1[dC]X_90_Width = 9.74[us]X_Acq_Time = 1.04333312[s]X_Angle = 30[deg]X_Atn = 3.3[dB]X_Pulse = 3.24666667[us]Irr_Atn_Dec = 20.699[dB]Irr_Atn_Noe = 20.699[dB]Irr_Noise = WALTZIrr_Pwidth = 0.115[ms]Decoupling = TRUEInitial_Wait = 1[s]Noe = TRUENoe_Time = 2[s]Repetition_Time = 3.04333312[s]

3g

NH

NO

EtO

OEt

S20

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

X : parts per Million : Proton

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

7.

257

7.

228

7.

206

6.

813

6.

792

6.

591

6.

306

6.

302

6.

285

6.

283

5.

246

5.

237

4.

448

4.

436

4.

426

4.

416

3.

938

3.

918

3.

780

3.

719

3.

110

3.

099

2.

906

2.

663

1.

761

1.

743

1.

738

1.

724

1.

548

1.

485

0.

990

0.

981

0.

971

0.

962

-0.

000

6.54

5.23

5.15

4.92

4.25

4.12

3.24

1.90

1.70

1.07

1.06

1.03

1.01

1.00

0.93

Filename = M-HH7-89-5-nBu-di_Proton-1Author = deltaExperiment = proton.jxpSample_Id = M-HH7-nBu-diSolvent = CHLOROFORM-DCreation_Time = 5-OCT-2017 09:30:32Revision_Time = 21-NOV-2017 16:16:22Current_Time = 21-NOV-2017 16:16:38

Comment = single_pulseData_Format = 1D COMPLEXDim_Size = 13107Dim_Title = ProtonDim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 2.18365952[s]X_Domain = 1HX_Freq = 399.78219838[MHz]X_Offset = 5[ppm]X_Points = 16384X_Prescans = 1X_Resolution = 0.45794685[Hz]X_Sweep = 7.5030012[kHz]X_Sweep_Clipped = 6.00240096[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Tri_Domain = ProtonTri_Freq = 399.78219838[MHz]Tri_Offset = 5[ppm]Clipped = FALSEScans = 8Total_Scans = 8

Relaxation_Delay = 5[s]Recvr_Gain = 34Temp_Get = 21.6[dC]X_90_Width = 13.67[us]X_Acq_Time = 2.18365952[s]X_Angle = 45[deg]X_Atn = 2.2[dB]X_Pulse = 6.835[us]Irr_Mode = OffTri_Mode = OffDante_Presat = FALSEInitial_Wait = 1[s]Repetition_Time = 7.18365952[s]

3h

NH

NO

nBuO

OnBu

S21

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

X : parts per Million : Carbon13

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0

158

.083

157

.969

142

.532

138

.518

135

.763

130

.261

129

.785

127

.220

125

.122

119

.459

116

.608

114

.472

111

.640

77.

335

77.

221

77.

020

76.

706

67.

781

67.

715

58.

762

51.

735

44.

908

31.

407

31.

312

19.

288

19.

231

13.

892

13.

854

-0.

000

Filename = M-HH7-89-5-C_Carbon-1-3.jdAuthor = deltaExperiment = carbon.jxpSample_Id = M-HH7-89-5-CSolvent = CHLOROFORM-DCreation_Time = 24-NOV-2017 09:19:18Revision_Time = 24-NOV-2017 10:51:25Current_Time = 24-NOV-2017 10:52:00

Comment = single pulse decoupled gatData_Format = 1D COMPLEXDim_Size = 26214Dim_Title = Carbon13Dim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 1.04333312[s]X_Domain = 13CX_Freq = 100.52530333[MHz]X_Offset = 100[ppm]X_Points = 32768X_Prescans = 4X_Resolution = 0.95846665[Hz]X_Sweep = 31.40703518[kHz]X_Sweep_Clipped = 25.12562814[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Clipped = FALSEScans = 1220Total_Scans = 1220

Relaxation_Delay = 2[s]Recvr_Gain = 60Temp_Get = 21.8[dC]X_90_Width = 9.74[us]X_Acq_Time = 1.04333312[s]X_Angle = 30[deg]X_Atn = 3.3[dB]X_Pulse = 3.24666667[us]Irr_Atn_Dec = 20.699[dB]Irr_Atn_Noe = 20.699[dB]Irr_Noise = WALTZIrr_Pwidth = 0.115[ms]Decoupling = TRUEInitial_Wait = 1[s]Noe = TRUENoe_Time = 2[s]Repetition_Time = 3.04333312[s]

3h

NH

NO

nBuO

OnBu

S22

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

X : parts per Million : Proton

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

7.

290

7.

270

7.

185

7.

164

7.

128

7.

104

6.

872

6.

868

6.

474

6.

194

6.

173

5.

231

5.

219

4.

513

4.

501

4.

489

4.

478

4.

465

3.

713

3.

335

3.

312

3.

053

2.

930

2.

907

2.

502

2.

267

1.

990

1.

174

-0.

000

6.50

6.42

4.40

4.07

2.20

2.16

2.12

1.39

1.13

1.10

1.10

1.09

1.09

1.08

1.03

1.00

Filename = M-HH7-21-3-F1_Proton-1-8.jAuthor = deltaExperiment = proton.jxpSample_Id = M-HH6-21-3-F1Solvent = DMSO-D6Creation_Time = 11-NOV-2016 14:05:39Revision_Time = 22-NOV-2017 10:30:51Current_Time = 22-NOV-2017 10:31:00

Comment = single_pulseData_Format = 1D COMPLEXDim_Size = 13107Dim_Title = ProtonDim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 2.18365952[s]X_Domain = 1HX_Freq = 399.78219838[MHz]X_Offset = 5[ppm]X_Points = 16384X_Prescans = 1X_Resolution = 0.45794685[Hz]X_Sweep = 7.5030012[kHz]X_Sweep_Clipped = 6.00240096[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Tri_Domain = ProtonTri_Freq = 399.78219838[MHz]Tri_Offset = 5[ppm]Clipped = FALSEScans = 8Total_Scans = 8

Relaxation_Delay = 5[s]Recvr_Gain = 36Temp_Get = 20.2[dC]X_90_Width = 13.1[us]X_Acq_Time = 2.18365952[s]X_Angle = 45[deg]X_Atn = 2.2[dB]X_Pulse = 6.55[us]Irr_Mode = OffTri_Mode = OffDante_Presat = FALSEInitial_Wait = 1[s]Repetition_Time = 7.18365952[s]

3i

NH

NO

Me

Me

S23

abun

danc

e-0

.01

00.

010.

020.

030.

040.

050.

060.

070.

080.

090.

10.

110.

120.

130.

140.

150.

16

X : parts per Million : Carbon13

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0

142

.267

141

.704

138

.815

136

.241

135

.955

135

.821

129

.710

129

.500

129

.367

126

.687

125

.066

119

.765

116

.724

111

.375

67.

335

40.

609

40.

399

40.

199

39.

989

39.

780

39.

570

39.

360

21.

197

21.

168

Filename = M-HH7-21-3-F1_Carbon-1-4.jAuthor = deltaExperiment = carbon.jxpSample_Id = M-HH7-21-3-F1Solvent = DMSO-D6Creation_Time = 1-OCT-2017 00:57:50Revision_Time = 22-NOV-2017 10:32:32Current_Time = 22-NOV-2017 10:32:43

Comment = single pulse decoupled gatData_Format = 1D COMPLEXDim_Size = 26214Dim_Title = Carbon13Dim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 1.04333312[s]X_Domain = 13CX_Freq = 100.52530333[MHz]X_Offset = 100[ppm]X_Points = 32768X_Prescans = 4X_Resolution = 0.95846665[Hz]X_Sweep = 31.40703518[kHz]X_Sweep_Clipped = 25.12562814[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Clipped = FALSEScans = 6000Total_Scans = 6000

Relaxation_Delay = 2[s]Recvr_Gain = 60Temp_Get = 22.1[dC]X_90_Width = 9.74[us]X_Acq_Time = 1.04333312[s]X_Angle = 30[deg]X_Atn = 3.3[dB]X_Pulse = 3.24666667[us]Irr_Atn_Dec = 20.699[dB]Irr_Atn_Noe = 20.699[dB]Irr_Noise = WALTZIrr_Pwidth = 0.115[ms]Decoupling = TRUEInitial_Wait = 1[s]Noe = TRUENoe_Time = 2[s]Repetition_Time = 3.04333312[s]

3i

NH

NO

Me

Me

S24

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

1.4

1.5

1.6

1.7

1.8

1.9

2.0

2.1

2.2

2.3

X : parts per Million : Proton

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

7.

317

7.

297

7.

257

7.

199

7.

179

7.

152

6.

922

6.

904

6.

579

6.

294

6.

277

6.

275

5.

252

5.

243

4.

513

4.

503

4.

488

4.

478

4.

467

3.

751

3.

198

3.

187

2.

902

2.

866

2.

589

1.

260

1.

257

1.

243

1.

239

1.

222

1.

205

-0.

000

12.4

3

6.34

5.02

4.05

2.17

1.34

1.04

1.03

1.03

1.01

1.01

1.00

0.96

Filename = M-HH7-28-2-iso_Proton-1-8.Author = deltaExperiment = proton.jxpSample_Id = M-HH7-28-2-isoSolvent = CHLOROFORM-DCreation_Time = 22-SEP-2017 09:30:51Revision_Time = 22-NOV-2017 10:36:04Current_Time = 22-NOV-2017 10:36:14

Comment = single_pulseData_Format = 1D COMPLEXDim_Size = 13107Dim_Title = ProtonDim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 2.18365952[s]X_Domain = 1HX_Freq = 399.78219838[MHz]X_Offset = 5[ppm]X_Points = 16384X_Prescans = 1X_Resolution = 0.45794685[Hz]X_Sweep = 7.5030012[kHz]X_Sweep_Clipped = 6.00240096[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Tri_Domain = ProtonTri_Freq = 399.78219838[MHz]Tri_Offset = 5[ppm]Clipped = FALSEScans = 8Total_Scans = 8

Relaxation_Delay = 5[s]Recvr_Gain = 36Temp_Get = 21.9[dC]X_90_Width = 13.67[us]X_Acq_Time = 2.18365952[s]X_Angle = 45[deg]X_Atn = 2.2[dB]X_Pulse = 6.835[us]Irr_Mode = OffTri_Mode = OffDante_Presat = FALSEInitial_Wait = 1[s]Repetition_Time = 7.18365952[s]

3j

NH

NO

iPr

iPr

S25

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

X : parts per Million : Carbon13

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0

147

.433

147

.328

142

.685

141

.589

138

.509

135

.525

129

.174

126

.657

126

.591

126

.019

125

.132

119

.487

116

.532

111

.545

77.

335

77.

020

76.

696

67.

781

58.

981

51.

687

45.

461

33.

743

33.

714

24.

065

24.

008

-0.

000

Filename = M-HH7-28-2-C_Carbon-1-4.jdAuthor = deltaExperiment = carbon.jxpSample_Id = M-HH7-28-2-CSolvent = CHLOROFORM-DCreation_Time = 30-SEP-2017 16:55:08Revision_Time = 2-OCT-2017 13:04:46Current_Time = 22-NOV-2017 10:38:14

Comment = single pulse decoupled gatData_Format = 1D COMPLEXDim_Size = 26214Dim_Title = Carbon13Dim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 1.04333312[s]X_Domain = 13CX_Freq = 100.52530333[MHz]X_Offset = 100[ppm]X_Points = 32768X_Prescans = 4X_Resolution = 0.95846665[Hz]X_Sweep = 31.40703518[kHz]X_Sweep_Clipped = 25.12562814[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Clipped = FALSEScans = 2048Total_Scans = 2048

Relaxation_Delay = 2[s]Recvr_Gain = 60Temp_Get = 22.3[dC]X_90_Width = 9.74[us]X_Acq_Time = 1.04333312[s]X_Angle = 30[deg]X_Atn = 3.3[dB]X_Pulse = 3.24666667[us]Irr_Atn_Dec = 20.699[dB]Irr_Atn_Noe = 20.699[dB]Irr_Noise = WALTZIrr_Pwidth = 0.115[ms]Decoupling = TRUEInitial_Wait = 1[s]Noe = TRUENoe_Time = 2[s]Repetition_Time = 3.04333312[s]

3j

NH

NO

iPr

iPr

S26

abun

danc

e0

1.0

2.0

3.0

4.0

X : parts per Million : Proton

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

7.

259

7.

234

7.

214

7.

174

7.

154

7.

109

6.

837

6.

818

6.

552

6.

327

6.

324

6.

306

5.

382

5.

038

5.

026

5.

016

3.

913

3.

810

3.

160

3.

149

3.

080

3.

058

2.

729

-0.

000

10.0

4

7.07

4.06

3.84

2.09

1.03

1.01

1.00

1.00

1.00

0.90

Filename = M-HH7-28-4-F3-re_Proton-1-Author = deltaExperiment = proton.jxpSample_Id = M-HH7-28-4-F3-reSolvent = CHLOROFORM-DCreation_Time = 29-NOV-2017 11:43:15Revision_Time = 29-NOV-2017 12:28:20Current_Time = 29-NOV-2017 12:28:42

Comment = single_pulseData_Format = 1D COMPLEXDim_Size = 13107Dim_Title = ProtonDim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 2.18365952[s]X_Domain = 1HX_Freq = 399.78219838[MHz]X_Offset = 5[ppm]X_Points = 16384X_Prescans = 1X_Resolution = 0.45794685[Hz]X_Sweep = 7.5030012[kHz]X_Sweep_Clipped = 6.00240096[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Tri_Domain = ProtonTri_Freq = 399.78219838[MHz]Tri_Offset = 5[ppm]Clipped = FALSEScans = 8Total_Scans = 8

Relaxation_Delay = 5[s]Recvr_Gain = 46Temp_Get = 21.5[dC]X_90_Width = 11.69[us]X_Acq_Time = 2.18365952[s]X_Angle = 45[deg]X_Atn = 1.5[dB]X_Pulse = 5.845[us]Irr_Mode = OffTri_Mode = OffDante_Presat = FALSEInitial_Wait = 1[s]Repetition_Time = 7.18365952[s]

3k

NH

NO

OMeOMe

S27

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

X : parts per Million : Carbon13

220.0210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0

157

.931

156

.872

131

.987

130

.843

127

.620

127

.554

126

.858

125

.065

120

.660

120

.345

119

.220

116

.026

111

.154

110

.563

110

.401

77.

335

77.

221

77.

020

76.

696

67.

791

55.

634

55.

434

52.

602

51.

696

36.

708

0.

000

Filename = M-HH7-28-4-F3-C_Carbon-1-4Author = deltaExperiment = carbon.jxpSample_Id = M-HH7-28-4-F3-CSolvent = CHLOROFORM-DCreation_Time = 29-NOV-2017 14:10:13Revision_Time = 29-NOV-2017 15:48:11Current_Time = 29-NOV-2017 15:48:44

Comment = single pulse decoupled gatData_Format = 1D COMPLEXDim_Size = 26214Dim_Title = Carbon13Dim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 1.04333312[s]X_Domain = 13CX_Freq = 100.52530333[MHz]X_Offset = 100[ppm]X_Points = 32768X_Prescans = 4X_Resolution = 0.95846665[Hz]X_Sweep = 31.40703518[kHz]X_Sweep_Clipped = 25.12562814[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Clipped = FALSEScans = 1024Total_Scans = 1024

Relaxation_Delay = 2[s]Recvr_Gain = 60Temp_Get = 22[dC]X_90_Width = 9.36[us]X_Acq_Time = 1.04333312[s]X_Angle = 30[deg]X_Atn = 3.3[dB]X_Pulse = 3.12[us]Irr_Atn_Dec = 20.394[dB]Irr_Atn_Noe = 20.394[dB]Irr_Noise = WALTZIrr_Pwidth = 0.115[ms]Decoupling = TRUEInitial_Wait = 1[s]Noe = TRUENoe_Time = 2[s]Repetition_Time = 3.04333312[s]

3k

NH

NO

OMeOMe

S28

abun

danc

e0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

2.2

2.4

2.6

2.8

3.0

3.2

X : parts per Million : Proton

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

7.

332

7.

322

7.

276

7.

259

7.

179

7.

162

6.

941

6.

920

6.

466

5.

386

5.

375

4.

567

4.

554

4.

544

4.

533

4.

521

3.

244

3.

231

3.

209

3.

196

3.

039

3.

017

3.

005

2.

983

2.

855

2.

640

1.

668

-0.

000

11.5

8

6.50

4.46

1.01

1.00

0.99

0.98

0.97

0.93

Filename = M-HH7-47-1-F1-CDCl3_ProtonAuthor = deltaExperiment = proton.jxpSample_Id = M-HH7-47-1-F1-CDCl3Solvent = CHLOROFORM-DCreation_Time = 21-JAN-2017 13:23:29Revision_Time = 22-NOV-2017 11:22:46Current_Time = 22-NOV-2017 11:22:59

Comment = single_pulseData_Format = 1D COMPLEXDim_Size = 13107Dim_Title = ProtonDim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 2.18365952[s]X_Domain = 1HX_Freq = 399.78219838[MHz]X_Offset = 5[ppm]X_Points = 16384X_Prescans = 1X_Resolution = 0.45794685[Hz]X_Sweep = 7.5030012[kHz]X_Sweep_Clipped = 6.00240096[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Tri_Domain = ProtonTri_Freq = 399.78219838[MHz]Tri_Offset = 5[ppm]Clipped = FALSEScans = 8Total_Scans = 8

Relaxation_Delay = 5[s]Recvr_Gain = 44Temp_Get = 20.6[dC]X_90_Width = 11.55[us]X_Acq_Time = 2.18365952[s]X_Angle = 45[deg]X_Atn = 1.5[dB]X_Pulse = 5.775[us]Irr_Mode = OffTri_Mode = OffDante_Presat = FALSEInitial_Wait = 1[s]Repetition_Time = 7.18365952[s]

3l

NH

PhPh

N

F3C

S29

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

X : parts per Million : Carbon13

220.0210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0

143

.152

142

.256

137

.727

129

.346

128

.679

128

.478

127

.220

126

.228

107

.340

107

.302

107

.264

107

.226

77.

631

77.

335

77.

221

77.

011

76.

696

59.

353

52.

555

45.

413

26.

830

24.

275

0.

000

Filename = M-HH7-47-1-F1_Carbon-1-5.jAuthor = deltaExperiment = carbon.jxpSample_Id = M-HH7-47-1-F1Solvent = CHLOROFORM-DCreation_Time = 26-SEP-2017 16:40:19Revision_Time = 22-NOV-2017 11:24:51Current_Time = 22-NOV-2017 11:25:22

Comment = single pulse decoupled gatData_Format = 1D COMPLEXDim_Size = 26214Dim_Title = Carbon13Dim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 1.04333312[s]X_Domain = 13CX_Freq = 100.52530333[MHz]X_Offset = 100[ppm]X_Points = 32768X_Prescans = 4X_Resolution = 0.95846665[Hz]X_Sweep = 31.40703518[kHz]X_Sweep_Clipped = 25.12562814[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Clipped = FALSEScans = 8000Total_Scans = 8000

Relaxation_Delay = 2[s]Recvr_Gain = 60Temp_Get = 22.4[dC]X_90_Width = 9.74[us]X_Acq_Time = 1.04333312[s]X_Angle = 30[deg]X_Atn = 3.3[dB]X_Pulse = 3.24666667[us]Irr_Atn_Dec = 20.699[dB]Irr_Atn_Noe = 20.699[dB]Irr_Noise = WALTZIrr_Pwidth = 0.115[ms]Decoupling = TRUEInitial_Wait = 1[s]Noe = TRUENoe_Time = 2[s]Repetition_Time = 3.04333312[s]

3l

NH

PhPh

N

F3C

S30

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

1.4

1.5

1.6

1.7

X : parts per Million : Proton

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

7.

356

7.

348

7.

344

7.

269

7.

257

7.

026

6.

714

6.

711

6.

614

6.

611

6.

595

6.

591

5.

159

4.

375

4.

361

3.

829

2.

944

2.

932

2.

921

1.

561

0.

008

0.

000

-0.

008

4.08

3.92

3.92

2.07

2.04

1.84

1.01

1.00

0.95

Filename = M-HH7-30_Proton-1-5.jdfAuthor = deltaExperiment = proton.jxpSample_Id = M-HH7-30Solvent = CHLOROFORM-DCreation_Time = 22-NOV-2016 13:20:51Revision_Time = 1-DEC-2017 12:58:12Current_Time = 1-DEC-2017 12:58:18

Comment = single_pulseData_Format = 1D COMPLEXDim_Size = 13107Dim_Title = ProtonDim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 2.18365952[s]X_Domain = 1HX_Freq = 399.78219838[MHz]X_Offset = 5[ppm]X_Points = 16384X_Prescans = 1X_Resolution = 0.45794685[Hz]X_Sweep = 7.5030012[kHz]X_Sweep_Clipped = 6.00240096[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Tri_Domain = ProtonTri_Freq = 399.78219838[MHz]Tri_Offset = 5[ppm]Clipped = FALSEScans = 8Total_Scans = 8

Relaxation_Delay = 5[s]Recvr_Gain = 36Temp_Get = 21.6[dC]X_90_Width = 13.1[us]X_Acq_Time = 2.18365952[s]X_Angle = 45[deg]X_Atn = 2.2[dB]X_Pulse = 6.55[us]Irr_Mode = OffTri_Mode = OffDante_Presat = FALSEInitial_Wait = 1[s]Repetition_Time = 7.18365952[s]

4aNH

NO

Ph

S31

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

X : parts per Million : Carbon13

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0

143

.154

139

.931

138

.606

128

.718

127

.145

127

.107

125

.438

119

.641

117

.134

110

.622

77.

441

77.

127

76.

802

67.

821

51.

889

48.

189

Filename = M-HH7-30-C_Carbon-1-2.jdfAuthor = deltaExperiment = carbon.jxpSample_Id = M-HH7-30-CSolvent = CHLOROFORM-DCreation_Time = 24-NOV-2017 10:28:32Revision_Time = 24-NOV-2017 10:49:51Current_Time = 24-NOV-2017 10:50:13

Comment = single pulse decoupled gatData_Format = 1D COMPLEXDim_Size = 26214Dim_Title = Carbon13Dim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 1.04333312[s]X_Domain = 13CX_Freq = 100.52530333[MHz]X_Offset = 100[ppm]X_Points = 32768X_Prescans = 4X_Resolution = 0.95846665[Hz]X_Sweep = 31.40703518[kHz]X_Sweep_Clipped = 25.12562814[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Clipped = FALSEScans = 352Total_Scans = 352

Relaxation_Delay = 2[s]Recvr_Gain = 60Temp_Get = 21.9[dC]X_90_Width = 9.74[us]X_Acq_Time = 1.04333312[s]X_Angle = 30[deg]X_Atn = 3.3[dB]X_Pulse = 3.24666667[us]Irr_Atn_Dec = 20.699[dB]Irr_Atn_Noe = 20.699[dB]Irr_Noise = WALTZIrr_Pwidth = 0.115[ms]Decoupling = TRUEInitial_Wait = 1[s]Noe = TRUENoe_Time = 2[s]Repetition_Time = 3.04333312[s]

4aNH

NO

Ph

S32

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

1.4

X : parts per Million : Proton

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

7.

307

7.

254

7.

047

7.

032

7.

025

7.

004

6.

996

6.

722

6.

718

6.

574

6.

571

6.

554

6.

551

5.

144

4.

330

3.

828

2.

936

2.

924

2.

913

-0.

000

4.23

4.23

4.09

2.07

2.01

1.00

1.00

0.95

Filename = M-HH7-28-1_Proton-1-5.jdfAuthor = deltaExperiment = proton.jxpSample_Id = M-HH7-28-1Solvent = CHLOROFORM-DCreation_Time = 27-SEP-2017 06:26:53Revision_Time = 22-NOV-2017 11:33:52Current_Time = 22-NOV-2017 11:34:12

Comment = single_pulseData_Format = 1D COMPLEXDim_Size = 13107Dim_Title = ProtonDim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 2.18365952[s]X_Domain = 1HX_Freq = 399.78219838[MHz]X_Offset = 5[ppm]X_Points = 16384X_Prescans = 1X_Resolution = 0.45794685[Hz]X_Sweep = 7.5030012[kHz]X_Sweep_Clipped = 6.00240096[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Tri_Domain = ProtonTri_Freq = 399.78219838[MHz]Tri_Offset = 5[ppm]Clipped = FALSEScans = 8Total_Scans = 8

Relaxation_Delay = 5[s]Recvr_Gain = 34Temp_Get = 22[dC]X_90_Width = 13.67[us]X_Acq_Time = 2.18365952[s]X_Angle = 45[deg]X_Atn = 2.2[dB]X_Pulse = 6.835[us]Irr_Mode = OffTri_Mode = OffDante_Presat = FALSEInitial_Wait = 1[s]Repetition_Time = 7.18365952[s]

4b

NH

NO

F

S33

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

1.4

1.5

1.6

1.7

1.8

1.9

2.0

2.1

2.2

2.3

2.4

2.5

2.6

X : parts per Million : Carbon13

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0

163

.137

160

.705

142

.857

138

.547

135

.477

135

.439

128

.555

128

.478

125

.332

119

.621

117

.228

115

.521

115

.311

110

.525

77.

354

77.

240

77.

039

76.

725

67.

696

51.

792

47.

444

-0.

000

Filename = M-HH7-28-1-C_Carbon-1-7.jdAuthor = deltaExperiment = carbon.jxpSample_Id = M-HH7-28-1-CSolvent = CHLOROFORM-DCreation_Time = 1-OCT-2017 12:41:38Revision_Time = 22-NOV-2017 11:36:04Current_Time = 22-NOV-2017 11:36:19

Comment = single pulse decoupled gatData_Format = 1D COMPLEXDim_Size = 26214Dim_Title = Carbon13Dim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 1.04333312[s]X_Domain = 13CX_Freq = 100.52530333[MHz]X_Offset = 100[ppm]X_Points = 32768X_Prescans = 4X_Resolution = 0.95846665[Hz]X_Sweep = 31.40703518[kHz]X_Sweep_Clipped = 25.12562814[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Clipped = FALSEScans = 4000Total_Scans = 4000

Relaxation_Delay = 2[s]Recvr_Gain = 60Temp_Get = 22.2[dC]X_90_Width = 9.74[us]X_Acq_Time = 1.04333312[s]X_Angle = 30[deg]X_Atn = 3.3[dB]X_Pulse = 3.24666667[us]Irr_Atn_Dec = 20.699[dB]Irr_Atn_Noe = 20.699[dB]Irr_Noise = WALTZIrr_Pwidth = 0.115[ms]Decoupling = TRUEInitial_Wait = 1[s]Noe = TRUENoe_Time = 2[s]Repetition_Time = 3.04333312[s]

4b

NH

NO

F

S34

abun

danc

e0

0.1

0.2

0.3

0.4

0.5

0.6

X : parts per Million : Proton

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

7.

258

7.

252

7.

046

7.

026

7.

021

7.

017

6.

997

6.

978

6.

729

6.

710

6.

705

6.

692

6.

613

6.

593

5.

138

3.

828

2.

944

2.

938

2.

932

2.

921

-0.

000

4.38

4.32

2.12

1.10

1.04

1.00

0.95

Filename = M-HH7-33-D_Proton-1-4.jdfAuthor = deltaExperiment = proton.jxpSample_Id = M-HH7-33-DSolvent = CHLOROFORM-DCreation_Time = 22-NOV-2016 13:29:40Revision_Time = 22-NOV-2017 11:43:34Current_Time = 22-NOV-2017 11:44:33

Comment = single_pulseData_Format = 1D COMPLEXDim_Size = 13107Dim_Title = ProtonDim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 2.18365952[s]X_Domain = 1HX_Freq = 399.78219838[MHz]X_Offset = 5[ppm]X_Points = 16384X_Prescans = 1X_Resolution = 0.45794685[Hz]X_Sweep = 7.5030012[kHz]X_Sweep_Clipped = 6.00240096[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Tri_Domain = ProtonTri_Freq = 399.78219838[MHz]Tri_Offset = 5[ppm]Clipped = FALSEScans = 8Total_Scans = 8

Relaxation_Delay = 5[s]Recvr_Gain = 36Temp_Get = 21.6[dC]X_90_Width = 13.1[us]X_Acq_Time = 2.18365952[s]X_Angle = 45[deg]X_Atn = 2.2[dB]X_Pulse = 6.55[us]Irr_Mode = OffTri_Mode = OffDante_Presat = FALSEInitial_Wait = 1[s]Repetition_Time = 7.18365952[s]

4b-d

NO

NHDD

D

D

DD

D

S35

abun

danc

e0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

2.2

2.4

2.6

2.8

3.0

3.2

X : parts per Million : Proton

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

7.

266

7.

261

7.

251

7.

248

7.

238

7.

235

7.

221

7.

095

7.

091

7.

075

7.

001

6.

999

6.

990

6.

986

4.

352

3.

875

3.

864

3.

852

3.

281

3.

270

3.

259

0.

000

6.96

4.53

4.34

4.22

4.02

1.91

1.00

0.97

Filename = ric-013-Ndi_Proton-1-6.jdfAuthor = deltaExperiment = proton.jxpSample_Id = ric-013-NdiSolvent = CHLOROFORM-DCreation_Time = 18-NOV-2017 09:49:39Revision_Time = 22-NOV-2017 11:39:06Current_Time = 22-NOV-2017 11:39:17

Comment = single_pulseData_Format = 1D COMPLEXDim_Size = 13107Dim_Title = ProtonDim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 2.18365952[s]X_Domain = 1HX_Freq = 399.78219838[MHz]X_Offset = 5[ppm]X_Points = 16384X_Prescans = 1X_Resolution = 0.45794685[Hz]X_Sweep = 7.5030012[kHz]X_Sweep_Clipped = 6.00240096[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Tri_Domain = ProtonTri_Freq = 399.78219838[MHz]Tri_Offset = 5[ppm]Clipped = FALSEScans = 8Total_Scans = 8

Relaxation_Delay = 5[s]Recvr_Gain = 34Temp_Get = 21.6[dC]X_90_Width = 13.67[us]X_Acq_Time = 2.18365952[s]X_Angle = 45[deg]X_Atn = 2.2[dB]X_Pulse = 6.835[us]Irr_Mode = OffTri_Mode = OffDante_Presat = FALSEInitial_Wait = 1[s]Repetition_Time = 7.18365952[s]

N

NO

Ph

Ph5

S36

abun

danc

e0

1.0

2.0

3.0

4.0

X : parts per Million : Carbon13

220.0 210.0 200.0 190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0

144

.364

143

.668

138

.367

129

.004

128

.270

126

.992

123

.112

122

.702

121

.891

118

.821

77.

489

77.

174

76.

860

67.

659

53.

576

50.

592

Filename = M-ric-013-C_Carbon-1-4.jdfAuthor = deltaExperiment = carbon.jxpSample_Id = M-ric-013-CSolvent = CHLOROFORM-DCreation_Time = 22-NOV-2017 10:23:28Revision_Time = 22-NOV-2017 12:24:00Current_Time = 22-NOV-2017 12:24:17

Comment = single pulse decoupled gatData_Format = 1D COMPLEXDim_Size = 26214Dim_Title = Carbon13Dim_Units = [ppm]Dimensions = XSite = JNM-ECS400Spectrometer = DELTA2_NMR

Field_Strength = 9.389766[T] (400[MHz])X_Acq_Duration = 1.04333312[s]X_Domain = 13CX_Freq = 100.52530333[MHz]X_Offset = 100[ppm]X_Points = 32768X_Prescans = 4X_Resolution = 0.95846665[Hz]X_Sweep = 31.40703518[kHz]X_Sweep_Clipped = 25.12562814[kHz]Irr_Domain = ProtonIrr_Freq = 399.78219838[MHz]Irr_Offset = 5[ppm]Clipped = FALSEScans = 160Total_Scans = 160

Relaxation_Delay = 2[s]Recvr_Gain = 60Temp_Get = 21.8[dC]X_90_Width = 9.74[us]X_Acq_Time = 1.04333312[s]X_Angle = 30[deg]X_Atn = 3.3[dB]X_Pulse = 3.24666667[us]Irr_Atn_Dec = 20.699[dB]Irr_Atn_Noe = 20.699[dB]Irr_Noise = WALTZIrr_Pwidth = 0.115[ms]Decoupling = TRUEInitial_Wait = 1[s]Noe = TRUENoe_Time = 2[s]Repetition_Time = 3.04333312[s]

N

NO

Ph

Ph5