Appendix II-D:
NMR spectra chapter 5
1.07
4.04
1.01
0.990.99
1.00
0.52 2.05 Acetone-d6
7.017.027.027.037.047.047.047.067.067.077.197.207.227.227.257.267.267.277.277.297.297.597.597.607.967.977.978.018.02
8.688.688.688.698.708.70
9.19
N-phenylpyridine-2-sulfonamide (1)
1H NMR (acetone-d6, 300 MHz)
N-(4-Methoxyphenyl)pyridine-2-sulfonamide (2)
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 75 MHz)
N-(p-Tolyl)pyridine-2-sulfonamide (9)
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 75 MHz)
20.7
29.8 Acetone-d6
122.6123.5127.8130.3135.0135.9139.0
150.9
158.1
N-(4-Iodophenyl)pyridine-2-sulfonamide (10)
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 75 MHz)
N-(4-Bromophenyl)pyridine-2-sulfonamide (11)
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 75 MHz)
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0
f1 (ppm)
4.13
1.02
1.031.02
1.00
0.77 2.05 Acetone-d6
7.247.267.277.287.287.297.307.317.327.617.61
7.987.998.018.048.04
8.688.688.708.70
9.33
N-(4-Chlorophenyl)pyridine-2-sulfonamide (12)
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 75 MHz)
N-(4-Fluorophenyl)pyridine-2-sulfonamide (13)
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 75 MHz)
19F NMR (acetone-d6, 282 MHz)
N-(4-(Trifluoromethyl)phenyl)pyridine-2-sulfonamide (3)
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 75 MHz)
19F NMR (acetone-d6, 282 MHz)
Methyl 4-[N-(2-pyridyl)sulfonylamino]benzoate (14).
1H NMR (acetone-d6, 300 MHz)
N-(3-fluorophenyl)pyridine-2-sulfonamide (15)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
19F NMR (acetone-d6, 471 MHz)
-200 -190 -180 -170 -160 -150 -140 -130 -120 -110 -100 -90 -80 -70 -60 -50 -40 -30 -20 -10 0
f1 (ppm)
N-(3-isopropylphenyl)pyridine-2-sulfonamide (16)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0
f1 (ppm)
N-[3-(trifluoromethyl)phenyl]pyridine-2-sulfonamide (17)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 75 MHz)
29.8 Acetone-d6
117.7117.8117.8117.9121.5121.5121.6121.6123.4124.9124.9126.7128.3131.0131.4131.8139.4139.7
151.1
157.7
19F NMR (acetone-d6, 471 MHz)
-200 -190 -180 -170 -160 -150 -140 -130 -120 -110 -100 -90 -80 -70 -60 -50 -40 -30 -20 -10 0
f1 (ppm)
1.06
1.001.021.04
1.021.04
1.00
0.93 2.05 Acetone-d6
7.057.057.067.077.527.537.797.808.048.048.048.088.09
8.698.698.708.708.708.708.718.71
9.54
N-(3-chloro-4-iodophenyl)pyridine-2-sulfonamide (18)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
29.8 Acetone-d6
91.6
121.2121.6123.4128.3
139.2139.4140.6141.5
151.1
157.6
1.07
1.001.061.03
1.031.03
1.00
0.67 2.05 Acetone-d6
7.207.217.227.227.537.537.587.598.048.048.088.08
8.698.708.708.708.708.718.718.71
9.54
N-(4-Bromo-3-chlorophenyl)pyridine-2-sulfonamide (19)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
29.8 Acetone-d6
117.2121.3122.7123.4128.3
134.9135.0139.4139.6
151.1
157.6
1.071.021.001.02
1.041.02
1.00
0.80 2.05 Acetone-d6
7.277.287.297.307.437.457.527.537.637.637.647.647.657.657.667.668.038.038.088.08
8.708.708.708.708.718.718.718.71
9.54
N-(3,4-Dichlorophenyl)pyridine-2-sulfonamide (20)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
29.8 Acetone-d6
121.3122.9123.4127.9128.3131.7132.9
139.0139.4
151.1
157.6
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0
f1 (ppm)
4-Methyl-N-phenylbenzenesulfonamide (4)
1H NMR (acetone-d6, 300 MHz)
13C NMR (CDCl3, 75 MHz)
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0
f1 (ppm)
N-Methyl-N-phenylpyridine-2-sulfonamide (8)
1H NMR (acetone-d6, 300 MHz)
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0
f1 (ppm)
N-(4-Chloro-2-fluorophenyl)pyrimidine-2-sulfonamide (21-Cl)
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 75 MHz)
NHSO2Pyr Cl
F
19F NMR (acetone-d6, 282 MHz)
-40 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190
f1 (ppm)
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0
f1 (ppm)
N-(2-Bromo-4-methylphenyl)pyrimidine-2-sulfonamide (22)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220
f1 (ppm)
120 125 130 135 140 145 150 155 160 165
f1 (ppm)
N-(4-Fluorophenyl)pyrimidine-2-sulfonamide (21)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 75 MHz)
19F NMR (acetone-d6, 282 MHz)
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0
f1 (ppm)
N-(p-Tolyl)pyrimidine-2-sulfonamide (23)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220
f1 (ppm)
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0
f1 (ppm)
N-phenyl-2-pyridinecarboxamide (7)
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 75 MHz)
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220
f1 (ppm)
1.021.030.98
1.99
0.991.00
0.671.00 2.05 Acetone-d67.137.137.147.157.157.167.167.167.167.177.187.187.197.247.257.257.267.277.287.287.287.287.297.307.317.317.357.367.367.377.387.387.397.397.617.617.627.627.627.637.637.647.647.647.657.657.667.677.67
7.967.968.058.06
8.598.698.698.698.708.708.718.718.71
N-(2-Chlorophenyl)pyridine-2-sulfonamide (1-Cl)
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 75 MHz)
29.8 Acetone-d6
123.2125.9127.5127.9128.2128.5130.5135.0139.2
151.1
158.2 123.2125.9127.5127.9128.2128.5130.5
135.0
139.2
151.1
158.2
N-(2-Chloro-4-methoxyphenyl)pyridine-2-sulfonamide (2-Cl)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
N-(2-Chloro-4-(trifluoromethyl)phenyl)pyridine-2-sulfonamide (3-Cl)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
19F NMR (acetone-d6,282 MHz)
-40 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190
f1 (ppm)
N-(4-chlorophenyl)-4-methylbenzenesulfonamide (4-Cl)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
N-(4-chlorophenyl)-2-pyridinecarboxamide (7-Cl).
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 75 MHz)
N-Methyl-N-(4-chlorophenyl)pyridine-2-sulfonamide (8-Cl)
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 75 MHz)
N-(2-Chloro-4-methylphenyl)pyridine-2-sulfonamide (9-Cl)
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 125 MHz)
N-(2-Chloro-4-iodophenyl)pyridine-2-sulfonamide (10-Cl)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
N-(4-Bromo-2-chlorophenyl)pyridine-2-sulfonamide (11-Cl)
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 125 MHz)
1.040.932.07
1.021.05
1.000.69 2.05 Acetone-d6
7.347.357.367.367.467.477.667.667.667.677.677.677.677.687.687.687.957.977.978.078.08
8.708.708.708.708.718.718.718.718.79
N-(2,4-dichlorophenyl)pyridine-2-sulfonamide (12-Cl)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
29.8 Acetone-d6
123.2127.5128.3128.7129.2130.0131.8134.3139.4
151.1
158.1 123.2
127.5128.3128.7129.2130.0131.8134.3
139.4
151.1
158.1
N-(2-Chloro-4-fluorophenyl)pyridine-2-sulfonamide (13-Cl)
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 125 MHz)
19F NMR (acetone-d6, 471 MHz)
Methyl 3-chloro-4-(pyridine-2-sulfonamido)benzoate (14-Cl)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
N-(2-chloro-3-fluorophenyl)pyridine-2-sulfonamide (15-Cl)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
19F NMR (acetone-d6, 471 MHz)
N-(2-chloro-5-isopropylphenyl)pyridine-2-sulfonamide (16-Cl)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
-1.0 -0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0
f1 (ppm)
N-(2-chloro-3-(trifluoromethyl)phenyl)pyridine-2-sulfonamide and N-(2-chloro-5- (trifluoromethyl)phenyl)pyridine-2-sulfonamide (17-Cl).
1H NMR (acetone-d6, 300 MHz)
NHSO2Py F3C
Cl
NHSO2Py F3C
Cl +
N-(2,3-dichloro-4-iodophenyl)pyridine-2-sulfonamide (18-Cl).
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
N-(4-bromo-2,3-dichlorophenyl)pyridine-2-sulfonamide (19-Cl).
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
0.95
2.06
1.041.05
1.00
0.58 2.05 Acetone-d6
7.547.577.667.667.667.677.687.687.697.707.707.728.008.018.098.10
8.698.698.718.71
8.97
N-(2,3,4-trichlorophenyl)pyridine-2-sulfonamide (20-Cl)
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 125 MHz)
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220
f1 (ppm) 125 130 135 140 145 150 155
f1 (ppm)
N-(2-Bromo-4-methoxyphenyl)pyridine-2-sulfonamide (2-Br)
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 125 MHz)
N-(2-Bromo-4-methylphenyl)pyridine-2-sulfonamide (9-Br)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0
f1 (ppm)
7.4 7.6 7.8 8.0 8.2 8.4 8.6
f1 (ppm)
N-(2-Bromo-4-iodophenyl)pyridine-2-sulfonamide (10-Br)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
N-(2,4-dibromophenyl)pyridine-2-sulfonamide (11-Br)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
N-(2-bromo-4-chlorophenyl)pyridine-2-sulfonamide (12-Br)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
N-(2-Bromo-4-fluorophenyl)pyridine-2-sulfonamide (13-Br)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
19F NMR (acetone-d6, 471 MHz)
N-(2-Bromo-4-(trifluoromethyl)phenyl)pyridine-2-sulfonamide (3-Br)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
19F NMR (acetone-d6, 471 MHz)
Methyl 3-bromo-4-(pyridine-2-sulfonamido)benzoate (14-Br)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
N-(2-Bromo-3-fluorophenyl)pyridine-2-sulfonamide (15-Br)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
19F NMR (acetone-d6, 471 MHz)
N-(2-bromo-3,4-dichlorophenyl)pyridine-2-sulfonamide (20-Br)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
N-(2-Iodo-4-(trifluoromethyl)phenyl)pyridine-2-sulfonamide (3-I)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
19F NMR (acetone-d6, 471 MHz)
Methyl 3-iodo-4-(pyridine-2-sulfonamido)benzoate (14-I).
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5
f1 (ppm)
N-(2,6-dichloro-4-fluorophenyl)pyrimidine-2-sulfonamide (21-Cl2)
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 125 MHz)
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220
f1 (ppm) 120 130 140 150 160
f1 (ppm)
19F NMR (acetone-d6, 282 MHz)
-40 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190
f1 (ppm)
N-(2-Bromo-6-chloro-4-methylphenyl)pyrimidine-2-sulfonamide (22-Cl)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
N-(2,6-Dichloro-4-methylphenyl)pyrimidine-2-sulfonamide (23-Cl2)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
N-(2,6-Dichloro-4-methylphenyl)pyrimidine-2-sulfonamide (26)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
19F NMR (acetone-d6, 471 MHz)
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0
f1 (ppm)
2-Phenyl-5-(trifluoromethyl)-1H-indole (27)
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 75 MHz)
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220
f1 (ppm)
100 105 110 115 120 125 130 135 140
f1 (ppm)
N-phenylpyridine-2-sulfonamide-d1 (29)
1H NMR (acetone-d6, 300 MHz)
13C NMR (acetone-d6, 75 MHz)
1.021.030.98
1.99
0.991.00
0.671.00 2.05 Acetone-d67.137.137.147.157.157.167.167.167.167.177.187.187.197.247.257.257.267.277.287.287.287.287.297.307.317.317.357.367.367.377.387.387.397.397.617.617.627.627.627.637.637.647.647.647.657.657.667.677.67
7.967.968.058.06
8.598.698.698.698.708.708.718.718.71
INTRAMOLECULAR ISOTOPIC KINETIC EFFECT
NHSO2Py
Cl +
NHSO2Py Cl
H D
1:1
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0
f1 (ppm)
7.5 8.0
8.5
f1 (ppm)
REGIOSELECTIVITY
N-(2-Chloro-4-iodophenyl)pyridine-2-sulfonamide (10-Cl)
1H NMR (acetone-d6, 500 MHz)
N-(2-Chloro-4-iodophenyl)pyridine-2-sulfonamide (30)
1H NMR (acetone-d6, 500 MHz)
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5
f1 (ppm)
N-(2-Chloro-4-fluorophenyl)pyridine-2-sulfonamide (13-Cl):
1H NMR (acetone-d6, 500 MHz)
N-(2-Chloro-4-fluorophenyl)pyridine-2-sulfonamide (31)
1H NMR (acetone-d6, 500 MHz)
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0
f1 (ppm)
Methyl 3-chloro-4-(pyridine-2-sulfonamido)benzoate (14-Cl)
1H NMR (acetone-d6, 500 MHz)
Methyl 3-chloro-4-(pyridine-2-sulfonamido)benzoate (32)
1H NMR (acetone-d6, 500 MHz)
1.06
1.001.021.04
1.021.04
1.00
0.93 2.05 Acetone-d6
7.057.057.067.077.527.537.797.808.048.048.048.088.09
8.698.698.708.708.708.708.718.71
9.54
N-(2-Chloro-4-iodophenyl)pyridine-2-sulfonamide (10-Cl)
1H NMR (acetone-d6, 500 MHz)
N-(3-chloro-4-iodophenyl)pyridine-2-sulfonamide (18)
1H NMR (acetone-d6, 500 MHz)
1.07
1.001.061.03
1.031.03
1.00
0.67 2.05 Acetone-d6
7.207.217.227.227.537.537.587.598.048.048.088.08
8.698.708.708.708.708.718.718.71
9.54
N-(4-Bromo-2-chlorophenyl)pyridine-2-sulfonamide (11-Cl)
1H NMR (acetone-d6, 300 MHz)
N-(4-Bromo-3-chlorophenyl)pyridine-2-sulfonamide (19)
1H NMR (acetone-d6, 500 MHz)
1.071.021.001.02
1.041.02
1.00
0.80 2.05 Acetone-d6
7.277.287.297.307.437.457.527.537.637.637.647.647.657.657.667.668.038.038.088.08
8.708.708.708.708.718.718.718.71
9.54 1.040.932.07
1.021.05
1.000.69 2.05 Acetone-d6
7.347.357.367.367.467.477.667.667.667.677.677.677.677.687.687.687.957.977.978.078.08
8.708.708.708.708.718.718.718.718.79
N-(2,4-dichlorophenyl)pyridine-2-sulfonamide (12-Cl)
1H NMR (acetone-d6, 500 MHz)
N-(3,4-Dichlorophenyl)pyridine-2-sulfonamide (20)
1H NMR (acetone-d6, 500 MHz)
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0
f1 (ppm) 7.0 7.2 7.4 7.6 7.8 8.0 8.2 8.4 8.6 8.8
f1 (ppm)
N-(2-Chloro-4-methoxyphenyl)pyridine-2-sulfonamide (2-Cl)
1H NMR (acetone-d6, 500 MHz)
N-(3-chloro-4-methoxyphenyl)pyridine-2-sulfonamide (33)
1H NMR (acetone-d6, 500 MHz)
13C NMR (acetone-d6, 125 MHz)
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220
f1 (ppm)
115 120 125 130 135 140 145 150 155
f1 (ppm)