Experimental Supporting Information Organic Dye Catalyzed, Visible-Light Photoredox Bromination of Arenes and Heteroarenes using NBromosuccinimide David A. Rogers, Roxanne G. Brown, Zachary C. Brandeburg, Eric Y. Ko, Megan D. Hopkins, Gabriel LeBlanc and Angus A. Lamar* Department of Chemistry and Biochemistry, The University of Tulsa, 800 S. Tucker Dr., Tulsa, OK 74104, USA.
[email protected]
Index General information - LED chamber
S-1
Electrochemistry Information
S-2
Characterization of Compounds 3 and 5
S-3
1
S-5
H and 13C NMR Spectra
Figure S1. On the left – A red LED strip (620 nm) light bath reaction vessel On the right – A white LED strip (cool white) light bath reaction vessel Photocatalytic reactions were performed in a light bath which was constructed in our laboratory similar to our previous reports as follows.1-3 Waterproof 5050 LED strips (12V with power adapter, 18 LEDs/foot, approximately 0.24 Watt per LED – 72 Watt per strip) are coiled around the interior of evaporating dish (170mm x 90mm) using the adhesive backing of the LED strip. A Petri dish (150 x 20 mm) is placed upside down at the bottom of the dish to serve as an elevated glass “floor” to ensure that a round-bottom flask receives maximum light exposure. The temperature inside the dish is monitored and is generally maintained (air-cooled) between 19-22 oC (the temperature has not been observed above 25 o C).
S-1
Methods for electrochemical experiments Electrochemical experiments were performed using a BioLogic SP-200 Potentiostat using a platinum disk working electrode, a platinum mesh counter electrode, and a silver wire as the quasi-reference electrode. The electrolyte consisted of 0.25 mM erythrosine B and 100 mM tetrabutylammonium hexafluorophosphate in acetonitrile. In some experiments, 1 mM ferrocene was used as an internal standard, as well as for calibration of the quasi-reference electrode. The ferrocene formal potential was found to be 0.477 V vs the silver wire quasi-reference electrode. Cyclic voltammetry was performed using a scan rate of 500 mV/s.
Figure S2. Cyclic voltammograms of (A) ferrocene, (B) NBS with ferrocene, (C) Ery B with (black) and without (red) ferrocene, and (D) Ery B with ferrocene using a platinum disk working electrode. Major redox peaks have been labeled as oxidation (O) or reduction (R) along with an abbreviation for the chemical entity. Formal potentials for irreversible electrochemical behavior were estimated using the half-wave potential. Note that the oxidation peak observed in (D), labeled EryBO2, only appears after a reducing potential (below -1V vs Fc/Fc+) has been reached and is therefore not an oxidation of the ground state Ery B.
S-2
1-Bromonaphthalene (3) The title compound was quantified using gas chromatography with adamantane as an internal standard. A standard curve of 1-bromonaphthalene (Figure S3) was prepared in 5 separate reaction vessels by adding varying amounts of 1bromonaphthalene (between 0 and 0.25 mmol) to 3 mL of acetonitrile. To each of the 3 mL acetonitrile solutions was added 8 mL of hexanes and 0.156 mmol (20 mg) of adamantane. The acetonitrile solution was extracted with the hexanes, and 1 mL of the hexanes portion was removed for gas chromatography injection. Gas chromatography was performed using a Shimadzu GC-2010 Plus with GCMS-QP2010 with a Restek Rtx-5MS capillary column (30m; 0.25 mmID; 0.25 um df; Crossbond – 5% diphenyl/95% dimethyl pilosiloxane). The GC method was as follows: 40 °C for 5 minutes, then increase at 10 °C/minute for 16 minutes (up to 200 °C). 200 °C is maintained for 10 additional minutes. As seen in Figure S4, 1Bromonaphthalene is observed at 16.8 minutes, and confirmed by MS (EI) m/z 206 and 208 (M+ 1:1 ratio; 50% rel. intensity) 127 (100% rel. intensity) 63 (90% rel. intensity).
Theoretical % Yield 1-Bromonaphthalene
1-Bromonaphthalene/Adamantane after Extraction 120 110 100 90 80 70 60 50 40 30 20 10 0
y = 80.155x R² = 0.9948
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
1.1
1.2
1.3
1.4
1.5
Integration Ratio 1-Br-Naphth/Adamantane
Figure S3. Standard curve of 1-bromonaphthalene versus internal standard (adamantane)
Figure S4. Expanded view of a typical GCMS chromatogram.
S-3
1-Bromo-4-methoxybenzene (5) The title compound was observed by 1H NMR and compared to a reported spectrum.4 One equivalent of nitrobenzene was added as internal standard at the conclusion of the reaction time period. The 1H NMR spectrum is included within this supporting information document (Figure S10).
References: 1. Brueckner, A. C.; Hancock, E. N.; Anders, E. J.; Tierney, M. M.; Morgan, H. R.; Scott, K. A.; Lamar, A. A., Visible-light-mediated, nitrogen-centered radical amination of tertiary alkyl halides under metal-free conditions to form []-tertiary amines. Organic & biomolecular chemistry 2016, 14 (19), 4387-4392.
2. Hopkins, M. D.; Scott, K. A.; DeMier, B. C.; Morgan, H. R.; Macgruder, J. A.; Lamar, A. A., Formation of N-sulfonyl imines from iminoiodinanes by iodine-promoted, N-centered radical sulfonamidation of aldehydes. Organic & biomolecular chemistry 2017, 15 (43), 9209-9216.
3. Hopkins, M.; Brandeburg, Z.; Hanson, A.; Lamar, A., Visible-Light, Iodine-Promoted Formation of N-Sulfonyl Imines and NAlkylsulfonamides from Aldehydes and Hypervalent Iodine Reagents. Molecules 2018, 23 (8), 1838.
4. Braddock, D. C.; Cansell, G.; Hermitage, S. A., (Diacetoxyiodo)benzene-Lithium Bromide as a Convenient Electrophilic Br+ Source. Synlett 2004, 461-464.
S-4
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.21 ZB-11-1H 0.20
Figure S5 - Product 4
0.19 0.18 0.17 0.16 0.15 0.14 0.13
Normalized Intensity
0.12 0.11 0.10 0.09 0.08 0.07 0.06 0.05 0.04 0.03 0.02 0.01 0 0.97 1.01 1.04 1.06 1.00 0.98 11
10
9
8
7
3.01 6 5 Chemical Shift (ppm)
4
3
2
1
0
S-5
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ AL-2-127-B-10min
Figure S6 - 2-methylnaphthalene (uncatalyzed reaction - 10 min) 0.025
Normalized Intensity
0.020
0.015
0.010
0.005
0 1.01 1.99 0.94 2.13 1.00 9.5
9.0
8.5
8.0
7.5
7.0
6.5 6.0 Chemical Shift (ppm)
5.5
5.0
4.5
4.0
3.5
S-6
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ AL-2-127-B-2hr 0.013
0.012
Figure S7 - 2-methylnaphthalene (uncatalyzed reaction - 120 min)
0.011
0.010
0.009
Normalized Intensity
0.008
0.007
0.006
0.005
0.004
0.003
0.002
0.001
0 0.38 1.01 3.79 1.44 0.66 1.72 2.47 1.31 9.5
9.0
8.5
8.0
7.5
0.75 0.89 7.0
6.5 6.0 Chemical Shift (ppm)
5.5
5.0
4.5
4.0
3.5
S-7
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ AL-2-127-A-10min 0.019 0.018
Figure S8 - 2-methylnaphthalene (catalyzed reaction - 10 min)
0.017 0.016 0.015 0.014 0.013
Normalized Intensity
0.012 0.011 0.010 0.009 0.008 0.007 0.006 0.005 0.004 0.003 0.002 0.001 0 0.94 9.5
9.0
8.5
0.97 1.07 1.01 1.00 1.11 8.0
7.5
7.0
6.5 6.0 Chemical Shift (ppm)
5.5
5.0
4.5
4.0
3.5
S-8
127.25
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ ZB-11-13C 0.30 128.67
Figure S9 - Product 4
77.00 76.68
125.61 124.00
0.15
0.10 135.97 132.97
Normalized Intensity
77.32
0.20
24.15
0.25
0.05
0
220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-9
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.100
RB-Anisole-nitrobenzene25min
0.095 0.090
Figure S10 - anisole reaction (with nitrobenzene internal standard) 0.085 0.080 0.075 0.070 0.065
Normalized Intensity
0.060 0.055 0.050 0.045 0.040 0.035 0.030 0.025 0.020 0.015 0.010 0.005 0 1.94 1.00 1.98 1.94 1.99 11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
2.98 6.5 6.0 5.5 5.0 Chemical Shift (ppm)
4.5
4.0
4.36 3.19 3.5
3.0
2.5
2.0
1.5
1.0
0.5
0
-0.5
S-10
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.21 RB-89-pure 0.20 0.19
Figure S11 - Product 6
0.18 0.17 0.16 0.15 0.14 0.13
Normalized Intensity
0.12 0.11 0.10 0.09 0.08 0.07 0.06 0.05 0.04 0.03 0.02 0.01 0 0.961.02 11
10
9
8
1.09 7
3.37 6 5 Chemical Shift (ppm)
4
3.21 3
2
1
0
S-11
77.30 76.99 76.67
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ RB89-4000scans-13C
0.25
Figure S12 - Product 6
133.84
0.15
159.56
56.47
26.30
0.05
111.83 111.04
131.21 129.46
0.10
195.62
Normalized Intensity
0.20
0
220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-12
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.30
EK-64pureaftervacuum-5hrs
0.25
Figure S13 - Product 7
Normalized Intensity
0.20
0.15
0.10
0.05
0 1.00 0.23 1.17 0.26 2.69 1.48 1.23 1.55 11
10
9
8
7
6 5 Chemical Shift (ppm)
4
3
2
1
0
S-13
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.30
EK-64pureaftervacuum-5hrs
Figure S14 - Product 7 aromatic region 0.25
Normalized Intensity
0.20
0.15
0.10
0.05
0 1.00 8.2
8.1
8.0
0.23 7.9
1.17 7.8
0.26
2.69
7.7 7.6 Chemical Shift (ppm)
7.5
1.48
1.23 7.4
1.55 7.3
7.2
7.1
7.0
S-14
76.30 75.98 75.66
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ EK-64-13C-10000scans 0.30
Figure S15 - Product 7
0.25
0.05
112.15 110.84
122.49 119.80
125.22
126.89
128.85
0.10
0.00
0.15
129.70
155.57 153.87
Normalized Intensity
0.20
0
220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-15
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.30
DR-6-41-f23-29-1H
Figure S16 - Product 8 0.25
Normalized Intensity
0.20
0.15
0.10
0.05
0 2.00 1.04 11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
2.00
6.5 6.0 5.5 5.0 Chemical Shift (ppm)
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0
-0.5
S-16
101.57
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ DR-6-41-F23-29-13C 0.30
Figure S17 - Product 8
146.96
124.28
113.00
0.15
0.10
109.55
148.55
Normalized Intensity
112.26
0.20
77.31 76.99 76.67
0.25
0.05
0
-0.05
220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-17
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.30
ZB-1-NBS-7-pure-1H
Figure S18 - Product 9 0.25
Normalized Intensity
0.20
0.15
0.10
0.05
0 0.92 2.04 1.03 1.00 1.18 11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
0.92 6.5 6.0 5.5 5.0 Chemical Shift (ppm)
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0
-0.5
S-18
117.12
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 128.19
ZB-1-NBS-5-pure-13C 0.30
127.82
Figure S19 - Product 9
77.31 77.00 76.68
124.12
0.25
132.26 129.65
0.10
106.12
0.15 150.54
Normalized Intensity
129.31
0.20
0.05
0
220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-19
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ DR-5-152-F40-54-1H 0.14
0.13
Figure S20 - Product 10 0.12
0.11
0.10
Normalized Intensity
0.09
0.08
0.07
0.06
0.05
0.04
0.03
0.02
0.01
0 1.01 1.050.98 11
10
9
8
7
0.97 6 5 Chemical Shift (ppm)
9.03 4
3
2
1
0
S-20
128.74
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ DR-5-152-13C 0.30
Figure S21 - Product 10
115.48
31.36
76.67
126.21
0.20
0.10
109.83
145.07
0.15
0.05
34.20
149.83
Normalized Intensity
77.30 76.98
0.25
0
220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-21
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.30
DR-5-189-1H-pure
Figure S22 - Product 11 0.25
Normalized Intensity
0.20
0.15
0.10
0.05
0 0.99 1.04 0.99 11
10
9
8
7
0.94 6 5 Chemical Shift (ppm)
1.11 4
3
6.72 2
1
0
S-22
24.04
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ DR-5-189-13C-pure-FEB16 0.30
Figure S23 - Product 11
0.25
76.99 76.67
115.78
33.15
127.22
77.30
0.15
150.10 0.05
109.93
0.10
142.66
Normalized Intensity
129.59
0.20
0
220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-23
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.30
DR-6-122-F15-18-1H
Figure S24 - Product 12 0.25
Normalized Intensity
0.20
0.15
0.10
0.05
0 1.01 1.07 1.01 11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
0.98 6.5 6.0 5.5 5.0 Chemical Shift (ppm)
1.13 4.5
4.0
3.5
3.0
2.5
4.93 2.0
5.06 1.5
1.0
0.5
0
-0.5
S-24
26.83
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ DR-6-122-13C 0.30 34.59
Figure S25 - Product 12
0.25
26.07 43.49
115.82
130.03 127.59
0.15
77.41 77.09 76.77
109.99
0.05
141.97
0.10
150.15
Normalized Intensity
0.20
0 220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-25
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.30
DR-5-140
Figure S26 Product 13 0.25
Normalized Intensity
0.20
0.15
0.10
0.05
0 1.99 11
10
9
8
1.00 7
6 5 Chemical Shift (ppm)
4
3
2
1
0
S-26
131.54
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ DR-5-140-13C-5000scans 0.30
Figure S27 - Product 13
77.31 76.68
0.25
0.15
126.17
0.05
109.90
0.10
148.48
Normalized Intensity
0.20
0
-0.05
220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-27
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.30
DR-6-69
Figure S28 - Product 14 0.25
Normalized Intensity
0.20
0.15
0.10
0.05
0 1.00 1.01 11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
1.00 7.0
6.5 6.0 5.5 5.0 Chemical Shift (ppm)
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0
S-28
131.38
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ DR-6-69-13C 0.30
Figure S29 - Product 14
133.55
0.25
77.34 77.02 76.70
0.15
121.47
0.05
110.78
112.22
0.10
148.13
Normalized Intensity
0.20
0
220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-29
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.30
DR-5-160-F26-41-1H
Figure S30 - Product 15 0.25
Normalized Intensity
0.20
0.15
0.10
0.05
0
0.89 11.5
11.0
10.5
10.0
9.5
9.0
8.5
1.00 8.0
7.5
1.05 7.0
2.04
6.5 6.0 5.5 5.0 Chemical Shift (ppm)
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0
-0.5
S-30
128.27
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ DR-5-160-13C 0.30
Figure S31 - Product 15
138.44
120.30
0.25
107.80
77.33 77.01 76.70
0.15
0.10
143.54
Normalized Intensity
0.20
0.05
0 220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-31
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.30
DR-6-65-1h
Figure S32 - Product 16 0.25
Normalized Intensity
0.20
0.15
0.10
0.05
0 2.00 11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
2.06 7.0
6.5 6.0 5.5 5.0 Chemical Shift (ppm)
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0
-0.5
S-32
131.19
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ DR-6-65-5000scans-13C 0.30
Figure S33 - Product 16
108.37
0.25
76.69
77.33 77.01 0.15
122.56
0.10
140.91
Normalized Intensity
0.20
0.05
0
220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-33
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.30
DR-6-58-F15-27-1H
Figure S34 - Product 17 0.25
Normalized Intensity
0.20
0.15
0.10
0.05
0 4.02 0.83 11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
3.08 6.5 6.0 5.5 5.0 Chemical Shift (ppm)
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0
S-34
76.68
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ DR-6-58-13C-6000scans 77.31
0.30
Figure S35 - Product 17
0.25
131.92 121.34
0.15
24.59
0.10
116.84
136.89
0.05 168.28
Normalized Intensity
0.20
0 220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-35
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.30
DR-6-29-1H-F7-18
Figure S36 - Product 18
0.25
Normalized Intensity
0.20
0.15
0.10
0.05
0 1.02 11.5
11.0
10.5
10.0
9.5
9.0
2.02 8.5
8.0
7.5
7.0
1.95 6.5 6.0 5.5 5.0 Chemical Shift (ppm)
4.5
4.0
3.5
3.0
4.01 2.5
5.90 2.0
5.95 1.5
1.0
0.5
0
-0.5
S-36
12.64
48.93
128.17
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ DR-6-29-F7-16-13C-pure
18.56
Figure S37 - Product 18 127.01
0.17
57.49
0.16 0.15 0.14 0.13
135.04
0.11 0.10 0.09 0.08 0.07 0.06
133.96
0.04 0.03
77.48 77.16 76.84
0.05
170.23
Normalized Intensity
0.12
0.02 0.01 0 220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-37
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.30
DR-5-178-F6-18-1H
Figure S38 - Product 19 0.25
Normalized Intensity
0.20
0.15
0.10
0.05
0 1.00 0.95 2.11 2.19 1.02 11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
6.5 6.0 5.5 5.0 Chemical Shift (ppm)
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0
S-38
-0.5
118.99
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ DR-5-178-5000scans-13C 0.30
Figure S39 - Product 19
0.25
129.52
0.15
77.35 77.03 76.71 95.61
0.05
126.99
141.49
127.02
0.10
139.60
Normalized Intensity
0.20
0
220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-39
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.30
DR-5-128
Figure S40 - Product 20 0.25
Normalized Intensity
0.20
0.15
0.10
0.05
0 1.00 12
1.97 1.00 1.03 11
10
9
8
7 6 Chemical Shift (ppm)
5
4
3
2
1
0
S-40
121.83
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ DR-5-128-13C 0.30
120.11
Figure S41 - Product 20
110.53
0.25
77.00 76.68 77.32
128.14
0.15
141.21
0.10
122.96
Normalized Intensity
0.20
0.05
0 220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-41
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.30
DR-6-60-F52-57-1H
Figure S42 - Product 21 0.25
Normalized Intensity
0.20
0.15
0.10
0.05
0 2.21 2.17 1.14 11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
0.22 6.5 6.0 5.5 5.0 Chemical Shift (ppm)
4.5
0.33 3.00 4.0
3.5
3.0
2.92 2.5
2.0
1.5
1.0
0.5
0
S-42
-0.5
129.20 127.00 124.13
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/
0.100
36.43
DR-6-60-13C
Figure S43 - Product 21
0.095 0.090 0.085 0.080 0.075 12.46
0.070
154.02
0.060 0.055 0.050
129.37
0.045 0.040
134.78
77.47 77.15 76.83
0.035 0.030
36.83
0.020 0.015
19.18
90.45
0.025 162.12
Normalized Intensity
0.065
0.010 0.005 0 -0.005 220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-43
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.25
DR-6-56-NaOHwash
0.24 0.23
Figure S44 - Product 22
0.22 0.21 0.20 0.19 0.18 0.17 0.16
Normalized Intensity
0.15 0.14 0.13 0.12 0.11 0.10 0.09 0.08 0.07 0.06 0.05 0.04 0.03 0.02 0.01 0 3.00 3.00 3.02 11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
7.5
7.0
6.5 6.0 5.5 5.0 Chemical Shift (ppm)
4.5
4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0
-0.5
S-44
29.79
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ DR-6-56-4500scans-13C 0.30
33.92
Figure S45 - Product 22
76.71 128.09
0.15
147.95
0.10
0.05
109.29
154.36 151.19
Normalized Intensity
0.20
27.97
77.35 77.03
0.25
0 220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-45
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.30
DR-6-137-1H
Figure S46 - Product 23 0.25
Normalized Intensity
0.20
0.15
0.10
0.05
0 0.93 11.5
11.0
10.5
10.0
9.5
9.0
0.97 2.00 1.02 8.5
8.0
7.5
7.0
2.20 6.5 6.0 5.5 5.0 Chemical Shift (ppm)
4.5
3.33 4.0
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0
-0.5
S-46
77.31 76.99
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ DR-6-132-3900scans-sep6-13C
76.68
0.30
Figure S47 - Product 23
121.45 121.31
0.25
111.95
14.33
0.15
98.29
135.27
0.05
124.07
127.97 126.56
61.45
0.10
160.95
Normalized Intensity
0.20
0
220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-47
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ 0.30
DR-6-139-JUL24-2
Figure S48 - Product 24 0.25
Normalized Intensity
0.20
0.15
0.10
0.05
0 2.04 11
10
9
8
2.16 1.01 0.96 7
0.95 6 5 Chemical Shift (ppm)
3.22 4
3
2
1
0
S-48
77.30 76.67
This report was created by ACD/NMR Processor Academic Edition. For more information go to www.acdlabs.com/nmrproc/ DR-6-139A-F38-53-13C 0.30
Figure S49 - Product 24
0.25
124.85
0.10
134.66
0.05
21.74
58.07
128.82
129.62
0.15
148.84 145.80
Normalized Intensity
0.20
0
220
200
180
160
140
120 100 Chemical Shift (ppm)
80
60
40
20
0
-20
S-49