electronic supplementary information - royal … 1 electronic supplementary information ligand-free...
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S 1
Electronic Supplementary Information
Ligand-Free Suzuki–Miyaura Coupling Using Ruthenium(0) Nanoparticles
and a Continuously Irradiating Microwave System
Toshiki Akiyama†, Takahisa Taniguchi
‡, Nozomi Saito
⊥
, Ryohei Doi‡, Tetsuo Honma
§, Yusuke Tamenori
§, Yuuta
Ohki#, Naoyuki Takahashi
#, Hiromichi Fujioka
†, Yoshihiro Sato,*
‡ and Mitsuhiro Arisawa*
†
†Graduate School of Pharmaceutical Sciences, Osaka University, Yamada-oka 1-6, Suita, Osaka 565-0871, Japan
‡Faculty of Pharmaceutical Sciences, Hokkaido University, Kita-12, Nishi-6, Kita-ku, Sapporo 060-0812, Japan
⊥
Meiji Pharmaceutical University, 2-522-1 Noshio, Kiyose, Tokyo 204-8588, Japan
§Japan Synchrotron Radiation Research Institute, 1-1-1 Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5198, Japan
#Tokyo Rikakikai Co., Ltd. (Brand: EYELA), TN Koishikawa Bldg. 1-15-17 Koishikawa Bunkyo-ku, Tokyo
112-0002 Japan
*Corresponding Author. Phone: +81-6-6879-8226, Fax: +81-6-6879-8229, E-mail: [email protected]
Contents • NMR charts of 3a – 3u S2-S22
Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2017
S 2
PPM
8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
DFILE 150314_proton- 1- 1.alsCOMNT single_pulseDATIM 2016- 10- 06 11:57:22OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 16384FREQU 7503.00 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 20.4 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 50
E:\ 1. NMR\ NMR Date\ 150314_proton- 1- 1.als
4.08
4.07
2.00
7.61
067.
6072
7.59
007.
4640
7.44
577.
4262
7.37
017.
3678
7.36
447.
3541
7.34
957.
3437
7.33
347.
3311
7.32
777.
2544
0.00
00
PPM
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 0.0
DFILE 150314_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2016- 10- 06 18:53:19OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .0000 secPW1 3.05 usecIRNUC 1HCTEMP 20.9 cSLVNT CDCL3EXREF 77.00 ppmBF 0.12 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150314_carbon- 1- 1.als
141.
2068
128.
7354
127.
2289
127.
1527
77.
3146
77.
0000
76.
6854
S 3
PPM
8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
DFILE 150316_proton- 1- 1.alsCOMNT single_pulseDATIM 2016- 10- 07 12:34:08OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 460.0 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 50
E:\ 1. NMR\ NMR Date\ 150316_proton- 1- 1.als3.
961.
950.
97
1.95
3.00
7.57
187.
5684
7.56
387.
5489
7.54
327.
5329
7.52
717.
5191
7.44
127.
4366
7.42
297.
4034
7.33
017.
3278
7.32
447.
3141
7.30
957.
3038
7.29
357.
2900
7.28
777.
2637
7.00
596.
9979
6.99
336.
9819
6.97
616.
9693
3.86
04
0.04
240.
0137
0.00
57-0
.003
4
PPM
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 0.0
DFILE 150316_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2017- 04- 05 11:53:40OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .0000 secPW1 3.05 usecIRNUC 1HCTEMP 19.7 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150316_carbon- 1- 1.als
159.
1060
140.
7993
133.
7531
128.
7188
128.
1467
126.
7356
126.
6498
114.
1688
77.
3362
77.
0120
76.
6973
55.
3395
0.
0000
S 4
PPM
8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
DFILE 150318_proton- 1- 1.alsCOMNT single_pulseDATIM 2016- 10- 11 11:59:07OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 20.6 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 50
E:\ 1. NMR\ NMR Date\ 150318_proton- 1- 1.als2.
05
2.02
2.02
1.99
0.95
3.00
8.05
528.
0506
8.04
618.
0346
8.02
898.
0243
7.70
937.
7035
7.69
907.
6875
7.68
297.
6783
7.64
747.
6440
7.63
827.
6256
7.61
767.
4974
7.49
287.
4790
7.47
567.
4596
7.42
867.
4252
7.42
177.
4126
7.40
697.
4011
7.38
857.
3851
7.26
14
2.64
73
0.00
800.
0000
-0.0
080
PPM
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 0.0
DFILE 150318_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2016- 10- 11 12:04:20OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .0000 secPW1 3.05 usecIRNUC 1HCTEMP 20.8 cSLVNT CDCL3EXREF 77.00 ppmBF 0.12 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150318_carbon- 1- 1.als
197.
8050
145.
7740
139.
8529
135.
8102
128.
9452
128.
9070
128.
2205
127.
2671
127.
2194
77.
3146
77.
0000
76.
6854
26.
6853
-0.
0215
S 5
PPM
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 0.0
DFILE 150320_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2016- 10- 13 12:05:43OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .0000 secPW1 3.05 usecIRNUC 1HCTEMP 20.3 cSLVNT CDCL3EXREF 77.00 ppmBF 0.12 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150320_carbon- 1- 1.als
147.
6237
147.
0516
138.
7564
129.
1454
128.
9070
127.
8010
127.
3815
124.
1015
77.
3146
77.
2002
77.
0000
76.
6854
-0.
0215
PPM
8 7 6 5 4 3 2 1 0
DFILE 150320_proton- 1- 1.alsCOMNT single_pulseDATIM 2016- 10- 13 11:58:53OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 19.9 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 50
E:\ 1. NMR\ NMR Date\ 150320_proton- 1- 1.als
2.00
2.02
2.00
3.02
8.32
448.
3187
8.31
308.
3015
8.29
588.
2900
7.76
207.
7562
7.75
057.
7391
7.73
337.
7276
7.64
407.
6405
7.63
487.
6234
7.61
997.
6142
7.52
717.
5237
7.51
917.
5065
7.50
197.
4905
7.48
707.
4813
7.47
227.
4687
7.46
537.
4573
7.45
047.
4435
7.43
557.
4321
7.26
14
0.00
800.
0000
-0.0
080
S 6
PPM
8 7 6 5 4 3 2 1 0
DFILE 150322_proton- 1- 1.alsCOMNT single_pulseDATIM 2016- 10- 14 13:10:18OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 20.4 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 50
E:\ 1. NMR\ NMR Date\ 150322_proton- 1- 1.als4.
005.
02
7.56
727.
5638
7.55
817.
5489
7.54
557.
5432
7.53
747.
5306
7.52
607.
5145
7.50
887.
5031
7.46
187.
4573
7.44
477.
4401
7.42
867.
4252
7.41
837.
4137
7.40
237.
3965
7.39
087.
3828
7.37
947.
3759
7.36
567.
3610
7.35
537.
3461
7.34
277.
3393
7.25
79
0.00
00
PPM
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 0.0
DFILE 150322_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2016- 10- 14 13:51:58OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .0000 secPW1 3.05 usecIRNUC 1HCTEMP 20.2 cSLVNT CDCL3EXREF 77.00 ppmBF 0.12 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150322_carbon- 1- 1.als
139.
9673
139.
6336
133.
3407
128.
8880
128.
8689
128.
3731
127.
5722
126.
9715
77.
3146
77.
2002
77.
0000
76.
6854
-0.
0120
S 7
PPM
8 7 6 5 4 3 2 1 0
DFILE 150324_proton- 1- 1.alsCOMNT single_pulseDATIM 2016- 10- 17 12:14:11OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 20.0 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 50
E:\ 1. NMR\ NMR Date\ 150324_proton- 1- 1.als1.
971.
982.
000.
942.
73
3.00
7.58
787.
5695
7.50
657.
4859
7.44
587.
4263
7.40
697.
3416
7.32
327.
3049
7.26
257.
2556
7.24
30
2.39
75
0.00
690.
0000
-0.0
092
PPM
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
DFILE 150324_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2016- 10- 17 12:19:25OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .0000 secPW1 3.05 usecIRNUC 1HCTEMP 20.8 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150324_carbon- 1- 1.als
141.
1426
138.
3393
137.
0235
129.
4720
128.
7474
128.
6997
127.
1646
126.
9644
77.
3266
77.
2122
77.
0120
76.
6973
21.
1003
0.
0000
S 8
PPM
8 7 6 5 4 3 2 1 0
DFILE 150326_proton- 1- 1.alsCOMNT single_pulseDATIM 2016- 10- 27 12:08:20OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 20.1 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 42
E:\ 1. NMR\ NMR Date\ 150326_proton- 1- 1.als1.
972.
904.
05
3.00
7.43
327.
4298
7.42
637.
4172
7.41
147.
3977
7.39
437.
3920
7.35
877.
3553
7.35
197.
3358
7.33
137.
3187
7.31
527.
3118
7.27
747.
2694
7.26
717.
2637
7.25
687.
2453
7.24
087.
2373
7.23
397.
2270
7.22
47
2.27
50
0.00
920.
0000
-0.0
080
PPM
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 0.0
DFILE 150326_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2016- 10- 27 12:13:33OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .0000 secPW1 3.05 usecIRNUC 1HCTEMP 20.2 cSLVNT CDCL3EXREF 77.00 ppmBF 0.12 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150326_carbon- 1- 1.als
141.
9219
141.
8933
135.
3239
130.
2800
129.
7747
129.
1645
128.
0394
127.
2194
126.
7331
125.
7320
77.
3242
77.
2098
77.
0000
76.
6854
20.
4591
-0.
0120
S 9
PPM
8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
DFILE 150328_proton- 1- 1.alsCOMNT single_pulseDATIM 2016- 11- 03 16:47:21OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 19.4 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 44
E:\ 1. NMR\ NMR Date\ 150328_proton- 1- 1.als2.
001.
02
9.00
7.91
667.
8960
7.87
427.
8536
7.55
587.
5466
7.52
947.
5088
7.50
317.
4916
7.47
567.
4722
7.46
187.
4492
7.44
477.
4378
7.43
437.
4286
7.42
407.
4206
7.41
727.
4080
7.25
11
0.00
00
PPM
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 0.0
DFILE 150328_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2016- 11- 03 16:52:32OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .0000 secPW1 3.05 usecIRNUC 1HCTEMP 19.8 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150328_carbon- 1- 1.als
140.
7326
140.
2272
137.
4240
133.
7531
132.
1227
131.
5792
130.
0632
128.
2421
127.
6128
127.
2218
126.
9167
126.
0109
125.
7535
125.
3721
77.
3266
77.
2122
77.
0120
76.
6973
0.
0000
S 10
PPM
9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
DFILE 150592_proton- 1- 1.alsCOMNT single_pulseDATIM 2016- 11- 22 12:51:18OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 19.8 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 50
E:\ 1. NMR\ NMR Date\ 150592_proton- 1- 1.als
1.96
0.97
1.97 2.
011.
00
8.01
637.
8582
7.62
797.
6234
7.61
887.
6062
7.60
397.
5374
7.53
407.
5283
7.51
577.
5122
7.50
087.
4974
7.49
167.
4802
7.47
677.
4733
7.46
417.
4584
7.45
157.
4435
7.44
017.
4366
7.26
14
0.00
00
PPM
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 0.0
DFILE 150592_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2017- 04- 12 13:48:52OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .0000 secPW1 3.05 usecIRNUC 1HCTEMP 19.9 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 60
F:\ 1. NMR\ NMR Date\ 150592_carbon- 1- 1.als
143.
3260
138.
2535
132.
5994
132.
2753
131.
9415
131.
6078
129.
3004
128.
9000
127.
2600
124.
7524
122.
0445
120.
9194
77.
2313
77.
0311
76.
7164
0.
0000
S 11
PPM
8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
DFILE 150493_proton- 1- 1.alsCOMNT single_pulseDATIM 2017- 01- 06 11:50:03OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 460.0 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 34
E:\ 1. NMR\ NMR Date\ 150493_proton- 1- 1.als
4.00
4.00
2.13
2.00
7.51
577.
4974
7.36
687.
3484
7.33
017.
3152
7.26
717.
2488
7.23
167.
2052
7.10
227.
0861
0.00
00
PPM
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 0.0
DFILE 150493_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2017- 01- 06 11:55:19OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .5000 secPW1 3.05 usecIRNUC 1HCTEMP 460.0 cSLVNT CDCL3EXREF 77.00 ppmBF 0.12 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150493_carbon- 1- 1.als
137.
2881
128.
6782
128.
6591
127.
6199
126.
5043
77.
3528
77.
3242
77.
0286
77.
0000
76.
7140
76.
6854
-0.
0215
S 12
PPM
9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
DFILE 150462_proton- 1- 1.alsCOMNT single_pulseDATIM 2016- 11- 16 18:55:04OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 19.5 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 44
E:\ 1. NMR\ NMR Date\ 150462_proton- 1- 1.als1.
01
1.00
1.00
2.11
2.09
2.04
8.86
178.
8559
8.60
628.
6028
8.59
478.
5902
7.89
487.
8903
7.88
457.
8754
7.87
087.
8651
7.60
277.
5993
7.59
367.
5810
7.57
307.
5088
7.50
657.
5019
7.48
937.
4848
7.47
337.
4699
7.46
417.
4343
7.43
097.
4275
7.41
837.
4137
7.40
697.
3977
7.39
437.
3874
7.38
517.
3759
7.36
797.
3656
7.35
537.
2625
0.00
00
PPM
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 0.0
DFILE 150462_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2016- 11- 16 19:23:53OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .0000 secPW1 3.05 usecIRNUC 1HCTEMP 19.5 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150462_carbon- 1- 1.als
148.
4843
148.
3508
137.
8435
136.
6326
134.
3729
129.
0811
128.
0990
127.
1646
123.
5510
77.
3457
77.
2313
77.
0215
76.
7069
0.
0000
S 13
PPM
8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
DFILE 150470_proton- 1- 1.alsCOMNT single_pulseDATIM 2016- 12- 06 12:15:14OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 18.6 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 44
E:\ 1. NMR\ NMR Date\ 150470_proton- 1- 1.als2.
00
2.02
3.00
1.00
7.62
567.
6062
7.39
777.
3794
7.35
997.
3187
7.30
957.
2980
7.28
667.
2843
7.27
867.
2740
7.27
057.
2614
7.25
117.
0930
7.08
387.
0804
7.07
12
0.00
00
PPM
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 0.0
DFILE 150470_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2016- 12- 06 12:20:29OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .0000 secPW1 3.05 usecIRNUC 1HCTEMP 19.1 cSLVNT CDCL3EXREF 77.00 ppmBF 1.20 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150470_carbon- 1- 1.als
144.
4010
134.
3609
128.
8594
127.
9822
127.
4387
125.
9227
124.
7880
123.
0527
77.
3242
77.
2098
77.
0000
76.
6854
-0.
0120
S 14
PPM
8 7 6 5 4 3 2 1 0
DFILE 150492_proton- 1- 1.alsCOMNT single_pulseDATIM 2016- 12- 15 12:09:09OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 18.4 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 50
E:\ 1. NMR\ NMR Date\ 150492_proton- 1- 1.als1.
99
1.00
1.00
2.01
1.01
2.97
0.99
7.88
807.
8845
7.87
887.
8662
7.85
827.
6004
7.58
217.
5798
7.54
097.
5191
7.47
447.
4699
7.45
617.
4527
7.44
017.
4366
7.37
827.
3759
7.37
257.
3622
7.35
767.
3519
7.34
167.
3381
7.33
587.
3095
7.30
617.
2912
7.28
777.
2717
7.26
837.
2579
7.25
347.
2499
7.23
397.
2316
7.21
567.
2133
7.03
57
0.00
00
PPM
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 0.0
DFILE 150492_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2016- 12- 15 12:14:25OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .5000 secPW1 3.05 usecIRNUC 1HCTEMP 18.4 cSLVNT CDCL3EXREF 77.00 ppmBF 0.12 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150492_carbon- 1- 1.als
155.
8713
154.
8320
130.
4326
129.
1740
128.
7736
128.
5257
124.
8929
124.
2350
122.
9002
120.
8788
111.
1534
101.
2659
77.
3146
77.
2002
77.
0000
76.
6758
0.
0071
S 15
PPM
9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
DFILE 150467_proton- 1- 1.alsCOMNT single_pulseDATIM 2016- 11- 17 12:05:41OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 19.4 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 42
E:\ 1. NMR\ NMR Date\ 150467_proton- 1- 1.als
0.99
2.00 2.05
3.09
0.99
8.70
478.
6933
8.00
378.
0002
7.99
567.
9819
7.97
397.
7734
7.77
007.
7539
7.74
947.
7368
7.73
337.
7184
7.71
617.
5019
7.49
857.
4939
7.48
137.
4767
7.46
187.
4561
7.43
787.
4343
7.43
097.
4217
7.41
607.
4091
7.40
117.
3977
7.39
437.
2568
7.24
657.
2408
7.23
397.
2293
7.22
477.
2178
7.21
21
0.00
800.
0000
-0.0
092
PPM
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 0.0
DFILE 150467_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2016- 11- 17 12:10:55OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .0000 secPW1 3.05 usecIRNUC 1HCTEMP 19.6 cSLVNT CDCL3EXREF 77.00 ppmBF 0.12 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150467_carbon- 1- 1.als
157.
4445
149.
6546
139.
3762
136.
7255
128.
9166
128.
7259
126.
8762
122.
0706
120.
5451
77.
3146
77.
0000
76.
6854
-0.
0215
S 16
PPM
8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
DFILE 150476_proton- 1- 1.alsCOMNT single_pulseDATIM 2016- 11- 21 12:17:04OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 19.4 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 52
E:\ 1. NMR\ NMR Date\ 150476_proton- 1- 1.als2.
000.
963.
971.
01
7.61
537.
6119
7.60
737.
5947
7.59
247.
5867
7.46
187.
4561
7.45
157.
4206
7.40
237.
3977
7.39
437.
3908
7.38
287.
3129
7.30
957.
2992
7.29
357.
2763
7.25
91
1.52
12
0.00
800.
0000
PPM
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 0.0
DFILE 150476_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2016- 11- 21 12:22:16OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .0000 secPW1 3.05 usecIRNUC 1HCTEMP 19.9 cSLVNT CDCL3EXREF 77.00 ppmBF 0.12 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150476_carbon- 1- 1.als
142.
3415
135.
8293
128.
7831
127.
1145
126.
4376
126.
3327
126.
1897
120.
2591
77.
3909
77.
3146
77.
0000
76.
6854
-0.
0120
S 17
PPM
8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
DFILE 150478_proton- 1- 1.alsCOMNT single_pulseDATIM 2017- 01- 12 00:14:24OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 460.0 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 44
E:\ 1. NMR\ NMR Date\ 150478_proton- 1- 1.als
5.19
1.00
1.05
2.98
7.46
187.
4435
7.42
407.
4057
7.40
117.
3977
7.39
317.
3794
7.36
567.
3633
7.24
767.
1972
7.18
817.
0265
7.02
437.
0185
7.01
62
2.27
04
0.00
00
PPM
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 0.0
DFILE 150478_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2017- 01- 12 00:19:36OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .0000 secPW1 3.05 usecIRNUC 1HCTEMP 460.0 cSLVNT CDCL3EXREF 77.00 ppmBF 0.12 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150478_carbon- 1- 1.als
143.
0852
137.
0306
136.
1344
128.
5924
128.
2873
127.
1431
122.
9383
121.
9562
77.
3146
77.
2002
77.
0000
76.
6758
15.
5296
-0.
0597
S 18
PPM
8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
DFILE 150477_proton- 1- 1.alsCOMNT single_pulseDATIM 2017- 02- 07 19:34:44OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 460.0 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 42
E:\ 1. NMR\ NMR Date\ 150477_proton- 1- 1.als
0.99
3.01
2.10
1.31
1.00
7.73
337.
5008
7.47
907.
3943
7.37
597.
3565
7.28
207.
2637
7.24
99
6.70
70
0.00
00
PPM
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 0.0
DFILE 150477_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2017- 02- 07 19:39:57OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .0000 secPW1 3.05 usecIRNUC 1HCTEMP 19.6 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150477_carbon- 1- 1.als
143.
6597
138.
4538
132.
3897
128.
8046
126.
9930
126.
4400
125.
8584
108.
8389
77.
3362
77.
0120
76.
6973
0.
0000
S 19
PPM
9 8 7 6 5 4 3 2 1 0
DFILE 150483_proton- 1- 1.alsCOMNT single_pulseDATIM 2017- 01- 20 22:24:20OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 18.2 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 44
E:\ 1. NMR\ NMR Date\ 150483_proton- 1- 1.als
1.00
1.03
2.06
3.91
1.08
1.62
1.00
8.16
297.
8651
7.66
697.
6635
7.64
637.
6428
7.45
847.
4550
7.44
017.
4206
7.33
017.
3267
7.31
187.
3072
7.29
577.
2935
7.29
007.
2476
7.23
967.
2327
6.61
876.
6130
6.60
61
0.00
00
PPM
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
DFILE 150483_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2017- 01- 20 22:29:34OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .0000 secPW1 3.05 usecIRNUC 1HCTEMP 18.8 cSLVNT CDCL3EXREF 77.00 ppmBF 0.12 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150483_carbon- 1- 1.als
142.
5036
135.
2381
133.
3884
128.
6115
128.
3254
127.
3720
126.
2850
124.
8071
121.
8990
119.
2293
111.
1915
103.
0012
77.
3146
77.
2002
77.
0000
76.
6854
0.
0071
S 20
PPM
8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
DFILE 150604_proton- 1- 1.alsCOMNT single_pulseDATIM 2017- 03- 23 15:31:29OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 18.4 cSLVNT ACETNEXREF 0.00 ppmBF 0.12 HzRGAIN 46
E:\ 1. NMR\ NMR Date\ 150604_proton- 1- 1.als2.
01
2.00 2.
151.
08
8.01
057.
6234
7.60
397.
3725
7.35
307.
3335
7.21
337.
1938
7.17
55
2.06
762.
0619
2.05
622.
0505
2.04
59
0.00
00
PPM
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 0.0 - 10.0
DFILE 150604_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2017- 03- 23 17:36:05OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 32767FREQU 31407.04 HzSCANS 2000ACQTM 1 .0433 secPD 2 .0000 secPW1 3.05 usecIRNUC 1HCTEMP 19.0 cSLVNT ACETNEXREF 0.00 ppmBF 0.12 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150604_carbon- 1- 1.als
136.
4972
134.
1612
129.
5846
126.
7624
126.
1617
125.
9519
122.
7864
79.
3087
78.
9845
78.
6604
30.
4344
30.
2342
30.
0435
29.
8528
29.
6621
29.
4714
29.
2712
0.
0000
S 21
PPM
8 7 6 5 4 3 2 1 0
DFILE 150605_proton- 1- 1.alsCOMNT single_pulseDATIM 2017- 01- 21 13:56:14OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 460.0 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 44
E:\ 1. NMR\ NMR Date\ 150605_proton- 1- 1.als2.
010.
99
3.08
1.00
7.99
797.
9876
7.98
197.
9773
7.97
167.
9670
7.96
367.
8788
7.87
087.
4790
7.47
447.
4699
7.46
537.
4561
7.45
277.
4435
7.43
897.
4263
7.42
297.
4103
7.40
577.
4023
7.34
047.
3324
7.26
02
0.00
00
PPM
180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 - 10
DFILE 150605_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2017- 01- 21 14:01:26OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .0000 secPW1 3.05 usecIRNUC 1HCTEMP 460.0 cSLVNT CDCL3EXREF 77.00 ppmBF 0.12 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150605_carbon- 1- 1.als
168.
4190
143.
6191
133.
5028
130.
0035
128.
9547
126.
5615
118.
8193
77.
3146
77.
2002
77.
0000
76.
6854
-0.
0215
S 22
PPM
8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
DFILE 150485_proton- 1- 1.alsCOMNT single_pulseDATIM 2017- 01- 26 12:27:35OBNUC 1HEXMOD proton.jxp OBFRQ 399.78 MHzOBSET 4.19 KHzOBFIN 7.29 HzPOINT 13107FREQU 6002.40 HzSCANS 16ACQTM 2 .1837 secPD 5 .0000 secPW1 5.64 usecIRNUC 1HCTEMP 460.0 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 42
E:\ 1. NMR\ NMR Date\ 150485_proton- 1- 1.als0.
97
4.04
1.09
0.98
1.84
3.00
7.91
327.
4790
7.45
847.
4527
7.44
477.
4355
7.43
097.
3931
7.38
517.
3805
7.37
827.
3725
7.36
457.
3576
7.35
077.
2625
7.22
597.
2213
4.53
16
2.23
95
0.00
00
PPM
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 0.0
DFILE 150485_carbon- 1- 1.alsCOMNT single pulse decouple d gated NOEDATIM 2017- 01- 26 12:32:49OBNUC 13CEXMOD carbon.jxp OBFRQ 100.53 MHzOBSET 5.35 KHzOBFIN 5.86 HzPOINT 26214FREQU 25125.63 HzSCANS 1000ACQTM 1 .0433 secPD 2 .0000 secPW1 3.05 usecIRNUC 1HCTEMP 460.0 cSLVNT CDCL3EXREF 0.00 ppmBF 0.12 HzRGAIN 60
E:\ 1. NMR\ NMR Date\ 150485_carbon- 1- 1.als
153.
6902
146.
3866
139.
1117
138.
0247
129.
0525
128.
6807
127.
7558
127.
5174
123.
4175
77.
3457
77.
0215
76.
7069
17.
4009
0.
0000