A Photochemical Amplifier Based on Self-Immolative Dendritic
Spacers
Agonist Kastrati and Christian G. Bochet*
Department of chemistry, University of Fribourg,
9 Chemin du Musée, CH-1700 Fribourg, Switzerland
[email protected]
Supplementary Information
Table of contents:
(4)
1H-NMR
S2
1G3OH (5)
1H-NMR,
13C-NMR, HR-MS, IR
S3
1G3Br (6)
1H-NMR,
13C-NMR, MALDI-TOF, IR, MP
S7
1G3PNP (1)
1H-NMR,
13C-NMR, MALDI-TOF, IR, MP
S11
(8)
1H-NMR
S15
(9)
1H-NMR,
13C-NMR, HR-MS, IR, MP
S16
(10)
1H-NMR
S20
2G9TBS (11)
1H-NMR,
13C-NMR, MALDI-TOF, IR
S21
2G9OH (12)
1H-NMR,
13C-NMR, MALDI-TOF, IR, MP
S25
2G9Cl (13)
1H-NMR,
13C-NMR, MALDI-TOF, IR, MP
S29
2G9PNP (2)
1H-NMR,
13C-NMR, MALDI-TOF, IR, MP
S33
(14)
1H-NMR
S37
(15)
1H-NMR,
13C-NMR, HR-MS, IR, MP
S38
3G27dioxolane (16)
1H-NMR,
13C-NMR, MALDI-TOF, IR, MP
S42
(17)
1H-NMR,
13C-NMR, HR-MS, IR
S49
(18)
1H-NMR,
13C-NMR, HR-MS, IR
S53
3G18THP9OH (19)
1H-NMR,
13C-NMR, MALDI-TOF, IR
S57
3G27OH (20)
1H-NMR,
13C-NMR, MALDI-TOF, IR
S61
3G27Cl (21)
1H-NMR,
13C-NMR, MALDI-TOF, IR, MP
S66
3G27PNP (3)
1H-NMR,
13C-NMR, MALDI-TOF, IR, MP
S72
18.12.2016 10:45:33 AK-PHD-012, PURIFIED_001001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 Normalized Intensity 2.12 2.00 DEUTERIUM OXIDE 4.51 4.67 4.75 7.16
ONa
OH
O
H
OH
18.12.2016 11:11:53 AK-PHD-013, CD3CN_001001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 Normalized Intensity 2.99 6.55 2.00 1.92 1.12 0.98 1.90 ACETONITRILE-d3 1.27 1.92 1.93 1.94 1.95 1.96 1.96 2.13 3.08 4.59 4.88 5.30 7.35 7.37 7.59 7.82 7.82 8.08 8.10 8.11 8.11 8.14 8.14
O
OH
O
H
OH
O
2N
18.12.2016 11:00:54 AK-PHD-013, MELTING POINT_005001r
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 Chemical Shift (ppm) 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10 0.11 0.12 0.13 0.14 0.15 0.16 0.17 0.18 0.19 Normalized Intensity ACETONITRILE-d3 0.57 0.84 1.11 1.39 1.67 1.94 2.21 60.10 62.40 64.54 73.59 118.39 125.71 127.87 129.76 135.02 135.16 135.81 139.47 148.15 154.08 O OH O H OH O2N
18.12.2016 11:21:35 AK-PHD-015, PURE CRYSTALS_002001r
9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 Normalized Intensity 1.99 2.00 1.98 1.01 1.97 CHLOROFORM-d 1.55 4.47 4.50 5.60 7.27 7.46 7.58 7.79 7.81 8.17 8.17 8.19 8.21 8.21 8.23 8.23 O Br Br Br O2N
18.12.2016 11:25:27 AK-PHD-015, 13C NMR_001001r 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 Normalized Intensity CHLOROFORM-d 26.88 29.68 31.79 72.66 76.69 77.00 77.32 125.06 128.68 132.70 132.84 134.25 135.29 146.69 154.95 O Br Br Br O2N
AK-PHD-018_001001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 5.949 3.996 1.034 1.999 1.022 DMSO-d6 DMSO Water 5.30 5.31 5.41 7.12 7.13 7.16 7.24 7.26 7.49 7.63 7.63 7.74 8.00 8.01 8.03 8.14 8.17 8.19 8.22
O
O
O
O
NO
2NO
2O
2N
NO
202.06.2017 08:09:57 AK-PHD-018_002001r 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 Chemical Shift (ppm) 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10 0.11 0.12 0.13 0.14 0.15 0.16 Normalized Intensity DMSO-d6 38.88 39.09 39.30 39.51 39.72 39.93 40.14 65.78 69.40 73.38 115.08 115.33 124.57 125.75 125.83 128.13 129.92 130.85 132.80 134.11 140.97 146.29 155.56 163.28 163.43 O O O O NO2 NO2 NO2 O2N
27.12.2017 14:00:35 AK-PHD-052-1_001001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5 -1.0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 Normalized Intensity 6.158 9.257 2.000 1.986 1.958 CHLOROFORM-d 0.09 0.10 0.11 0.93 0.94 0.95 1.25 1.27 1.30 2.06 4.13 4.15 4.67 6.78 6.81 7.18 7.21 7.27
OH
OTBS
19.12.2016 09:52:58 AK-PHD-052-2 NP,P_001001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00 Normalized Intensity 5.89 9.02 1.99 2.00 ACETONITRILE-d3 0.09 0.91 0.92 0.93 1.93 1.94 1.95 4.62 4.68 7.05 OH OTBS OH O H
19.12.2016 09:55:55 AK-PHD052-2_002001r 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 Normalized Intensity ACETONITRILE-d3 -4.94 0.57 0.84 1.11 1.39 1.67 1.94 2.21 19.06 26.17 26.39 62.41 65.66 118.37 126.32 127.58 133.36 153.94 OH OTBS OH O H
27.12.2017 13:34:43 AK-PHD-033, TBS_001001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5 -1.0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 Normalized Intensity 7.561 31.140 2.178 2.126 1.000 CHLOROFORM-d 0.07 0.08 0.09 0.13 0.14 0.86 0.93 0.94 0.95 0.95 0.96 4.65 4.85 7.08 7.27 8.18
OH
OTBS
SBTO
OTBS
27.12.2017 13:55:05 AK-PHD-033, PURE 9TBS_001001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5 Chemical Shift (ppm) 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10 0.11 0.12 0.13 0.14 0.15 0.16 Normalized Intensity 1.032 85.027 12.018 1.964 4.093 1.056 1.026 CHLOROFORM-d TMS -0.01 0.01 0.07 0.10 0.12 0.13 0.65 0.84 0.85 0.86 0.91 0.94 0.96 0.97 1.07 1.22 1.56 2.18 4.71 4.85 4.98 5.28 7.27 7.34 7.40 7.46 7.67 7.80 8.15 8.15 8.18 8.18 O O O NO2 SBTO OTBS OTBS O SBTO SBTO OTBS OTBS OTBS SBTO
19.12.2016 09:43:37 AK-PHD-033, PURE 9TBS_002001r 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 Normalized Intensity CHLOROFORM-d -5.24 -5.21 -4.87 18.32 18.44 25.92 25.97 60.27 60.36 64.95 65.01 70.65 75.39 76.58 77.00 77.43 124.74 124.85 128.12 131.72 133.80 133.99 137.26 145.92 152.09 152.88 O O O NO2 SBTO OTBS OTBS O SBTO SBTO OTBS OTBS OTBS SBTO
18.12.2016 12:54:41 AK-PHD-020_001001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 Normalized Intensity 11.64 2.02 1.96 3.96 2.99 1.01 METHANOL-d4 Methanol 4.59 4.71 5.02 5.06 5.43 7.37 7.43 7.56 7.78 8.02 8.12 8.13 8.15 O O O NO2 OH OH O O H OH OH OH O H O H O H
18.12.2016 12:31:54 AK-PHD-020, H-NMR, 13C-NMR_003001r 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 Chemical Shift (ppm) 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10 0.11 0.12 0.13 0.14 0.15 0.16 Normalized Intensity DMSO-d6 14.08 20.75 38.88 39.09 39.30 39.51 39.72 39.93 40.14 48.60 58.05 59.76 62.88 70.40 72.86 75.02 124.72 125.45 128.65 131.32 133.42 134.62 137.87 146.12 151.93 152.04 153.16 170.35 O O O NO2 OH OH O O H OH OH OH O H O H O H
11.02.2018 12:20:31 1 HNMR_000001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00 Normalized Intensity 4.894 5.918 4.135 1.061 2.078 CHLOROFORM-d 4.56 4.59 4.60 4.73 5.24 5.26 5.47 7.27 7.42 7.44 7.52 7.54 7.76 7.79 7.98 8.14 8.17 8.20 8.21
O
O
O
NO
2Cl
Cl
Cl
O
Cl
Cl
Cl
Cl
Cl
Cl
19.02.2018 08:01:10 2G9CL_002001r 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00 Normalized Intensity CHLOROFORM-d 13.98 14.12 20.95 22.23 40.46 40.59 44.96 45.05 60.27 71.98 73.56 76.44 76.68 77.00 77.32 124.88 127.59 128.29 129.90 130.98 131.92 132.03 132.13 134.56 145.92 154.47 155.08 155.11 170.99 O O O NO2 Cl Cl Cl O Cl Cl Cl Cl Cl Cl
18.12.2016 13:23:14 AK-PHD-022, ACETONE_004001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00 Normalized Intensity 1.82 2.02 7.68 2.91 2.00 13.20 ACETONE-d6 1.18 1.20 1.21 1.96 2.04 2.04 2.05 2.06 2.06 2.78 2.78 2.81 3.23 4.04 4.93 5.09 5.12 5.24 5.27 5.29 5.35 6.94 6.95 6.98 6.99 7.14 7.15 7.17 7.18 7.20 7.21 7.24 7.52 7.54 7.67 7.78 7.99 8.00 8.02 8.07 8.17 8.19 8.21 O O O NO2 O O O O O O O O O O O2N O2N O2N NO2 NO2 NO2 NO2 NO2 NO2
18.12.2016 13:26:20 AK-PHD-022, ACETONE_005001r 216 208 200 192 184 176 168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 Chemical Shift (ppm) 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10 0.11 0.12 0.13 0.14 0.15 0.16 0.17 0.18 0.19 Normalized Intensity ACETONE-d6 29.34 29.53 29.73 29.92 30.11 30.31 30.50 66.87 67.09 70.66 73.27 73.91 77.93 115.73 116.08 116.12 125.73 126.56 126.65 130.52 131.00 131.48 134.05 134.35 135.31 142.51 142.59 147.20 154.79 157.12 164.37 164.56 164.72 164.77 206.03 206.23 206.42 O O O NO2 O O O O O O O O O O O2N O2N O2N NO2 NO2 NO2 NO2 NO2 NO2
09.12.2016 18:20:49 AK-PHD-068, PURE ALDEHYDE_001001r
16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2 -3 -4 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00 Normalized Intensity 1.99 0.99 ACETONE-d6 2.04 2.05 2.06 2.06 8.63 10.08 10.38
OH
H
O
H
O
H
O
19.04.2017 14:47:41 AK-PHD-075,1,2DIOL PROTECTION_001001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00 Normalized Intensity 12.38 1.00 2.00 2.00 0.99 CHLOROFORM-d 1.68 3.97 3.99 4.04 4.05 4.05 4.06 4.10 4.11 4.13 4.13 4.15 5.75 6.07 7.27 7.50 8.35
O
O
O
OH
O
O
O
20.04.2017 07:53:22 AK-PHD-075,1,2DIOL PROTECTION_002001r 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00 Normalized Intensity CHLOROFORM-d 64.95 65.10 76.58 77.00 77.42 101.60 103.32 123.22 126.74 129.09 154.49
O
O
O
OH
O
O
O
27.12.2017 14:19:43 AK-PHD-076_001001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00 Normalized Intensity 109.030 5.949 1.811 3.835 0.945 8.200 1.842 ACETONE-d6 1.17 1.20 1.22 1.97 2.05 2.06 2.06 2.80 2.83 3.67 3.70 3.72 3.82 3.90 3.96 3.97 3.98 4.07 4.10 4.15 4.18 5.13 5.18 5.24 5.32 5.69 5.72 5.75 5.77 5.95 6.10 6.14 6.21 7.05 7.08 7.10 7.14 7.17 7.19 7.64 7.72 7.82 7.94 7.96 O O O O NO2 O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
26.04.2017 07:58:13 AK-PHD-076_001001r 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 Normalized Intensity ACETONE-d6 14.58 20.90 29.34 29.53 29.73 29.92 30.11 30.31 30.50 30.55 60.61 65.99 66.12 66.17 72.69 74.03 74.30 74.43 79.10 79.23 99.61 99.69 103.82 103.89 125.35 127.72 127.83 130.24 132.76 132.86 135.42 135.55 146.72 154.71 155.17 155.33 157.92 158.08 170.98 206.01 206.22 206.42 O O O O NO2 O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
17.01.2018 13:15:58 AK-PHD-093_001001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5 -1.0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 Normalized Intensity 5.943 9.144 9.753 2.110 2.067 2.036 3.983 2.003 0.926 CHLOROFORM-d 0.09 0.10 0.10 0.93 0.93 0.94 0.95 0.95 1.25 1.27 1.29 1.56 1.57 1.58 1.59 1.60 1.62 2.05 3.57 3.58 3.59 3.60 3.93 3.95 3.96 3.98 4.12 4.14 4.16 4.63 4.64 4.65 4.66 4.67 4.74 4.86 4.87 4.89 7.16 7.27 7.74
OH
O
O
OTBS
O
O
18.01.2018 08:44:55 AK-PHD-093_002001r 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 Normalized Intensity CHLOROFORM-d -5.18 14.19 18.44 19.56 21.03 25.31 25.99 30.52 60.37 62.71 64.70 65.95 76.68 77.00 77.31 98.23 98.27 123.78 126.97 132.42 152.95
OH
O
O
OTBS
O
O
26.01.2018 13:08:18 AK-PHD-BB9_001001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00 Normalized Intensity 9.920 2.080 2.068 1.985 1.221 2.041 1.000 CHLOROFORM-d 1.24 1.27 1.29 1.29 1.57 1.58 1.60 1.63 1.64 1.66 1.77 1.81 1.87 1.88 1.91 2.05 3.55 3.57 3.59 3.60 3.93 3.95 3.96 3.99 4.11 4.12 4.14 4.16 4.60 4.66 4.67 4.75 4.86 4.87 4.91 7.22 7.27 7.27 7.87
OH
O
O
OH
O
O
20.02.2018 17:07:35 AK-PHD-BB9_002001r 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 Normalized Intensity CHLOROFORM-d 19.61 25.25 30.49 62.85 65.11 65.83 76.58 77.00 77.42 98.40 124.18 128.16 132.01 153.61
OH
OTHP
PHTO
OH
01.03.2018 13:12:49 AK-PHD-3G18THP9OH_001001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 Normalized Intensity 110.706 18.015 18.047 105.141 30.000 ACETONE-d6 0.82 0.82 0.83 0.84 0.85 0.87 0.88 0.90 1.06 1.17 1.20 1.22 1.34 1.41 1.43 1.44 1.47 1.51 1.62 1.66 1.69 1.74 1.75 1.95 1.96 2.05 2.06 2.06 2.86 3.28 3.31 3.48 3.50 3.63 3.64 3.66 3.66 3.70 3.80 3.84 4.01 4.04 4.06 4.09 4.21 4.22 4.24 4.26 4.40 4.44 4.48 4.55 4.56 4.60 4.61 4.63 4.67 4.79 4.83 4.98 5.00 5.10 5.22 5.35 7.17 7.29 7.33 7.41 7.47 7.79 7.91 7.94 8.00 O O O O NO2 O O O O O O O O O OH OTHP OTHP OH PHTO PHTO PHTO O H PHTO PHTO O H PHTO O H OH OTHP PHTO OH PHTO PHTO O H OTHP OTHP OTHP OTHP OH OTHP OTHP
01.03.2018 13:15:57 AK-PHD-3G18THP9OH_002001r 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 Chemical Shift (ppm) 0 0.005 0.010 0.015 0.020 0.025 0.030 0.035 0.040 0.045 0.050 0.055 0.060 0.065 Normalized Intensity ACETONE-d6 14.57 20.08 20.14 20.90 26.26 26.30 29.15 29.41 29.66 29.92 30.18 30.44 30.69 31.29 31.44 31.51 60.61 62.27 64.74 64.90 72.18 72.34 72.50 77.27 98.45 98.63 98.77 125.43 127.80 128.59 129.32 132.51 132.62 132.70 135.11 135.31 139.06 139.17 146.48 154.08 154.49 155.03 155.68 170.98 205.99 206.26 206.52 O O O O NO2 O O O O O O O O O OH OTHP OTHP OH PHTO PHTO PHTO O H PHTO PHTO O H PHTO O H OH OTHP PHTO OH PHTO PHTO O H OTHP OTHP OTHP OTHP OH OTHP OTHP
30.01.2018 11:23:01 3G27OH-DMSO_001001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00 Normalized Intensity 106.561 30.000 DMSO-d6 DMSO 1.07 1.09 1.11 3.35 3.37 3.39 4.40 4.42 4.49 4.59 4.61 4.66 4.85 4.98 4.99 5.13 5.14 5.16 5.18 5.18 7.20 7.32 7.36 7.67 7.79 O O O O NO2 O O O O O O O O O OH OH OH OH O H O H O H O H O H O H O H O H O H OH OH O H OH O H O H O H OH OH OH OH OH OH OH
29.01.2018 10:16:57 AK-3G27OH FROM PURE 3G18THP9TBS TEST_001001r
9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10 0.11 0.12 0.13 Normalized Intensity 58.318 15.697 29.999 METHANOL-d4 Methanol Methanol 1.16 1.18 1.20 3.35 3.48 3.50 3.52 4.47 4.48 4.61 4.65 4.70 4.85 4.95 4.98 5.01 5.14 5.22 7.24 7.27 7.39 7.42 7.61 7.74 7.81
AK-3G27OH FROM PURE 3G18THP9TBS TEST_001001r
8.00 7.75 7.50 7.25 Chemical Shift (ppm) 0 0.01 0.02 0.03 0.04 0.05 0.06 Normalized Intensity 29.999 7.81 7.74 7.61 7.42 7.39 7.36 7.33 7.32 7.30 7.27 7.24
03.02.2018 11:20:25 AK-PHD--3G27OH_002001r 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 Chemical Shift (ppm) 0 0.005 0.010 0.015 0.020 0.025 0.030 0.035 0.040 0.045 Normalized Intensity DMSO-d6 15.20 38.68 38.96 39.23 39.51 39.79 40.07 40.35 58.04 58.17 62.90 64.95 70.23 70.41 75.04 75.16 125.44 125.56 128.19 130.77 131.14 134.42 134.65 137.71 137.87 145.41 151.79 151.84 152.04 153.30 153.58 O O O O NO2 O O O O O O O O O OH OH OH OH OH O H OH OH OH OH OH O H O H O H O H O H OH O H O H O H O H O H O H OH O H O H OH
31.01.2018 13:06:40 3G27CL NOT DRY IN CDCL3_001001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 Normalized Intensity 53.471 25.567 29.992 CHLOROFORM-d 0.87 0.89 0.91 1.25 1.27 1.29 1.30 1.56 2.06 2.18 4.44 4.47 4.51 4.60 4.65 4.71 5.11 5.12 5.15 5.29 7.27 7.36 7.47 7.51 7.80 7.92 O O O O NO2 O O O O O O O O O Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl
03.02.2018 10:01:31 3G27CL_001001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00 Normalized Intensity 54.411 25.468 30.000 ACETONE-d6 0.86 0.88 0.89 1.20 1.28 1.30 1.30 1.97 2.04 2.05 2.06 2.06 2.78 2.81 4.57 4.59 4.63 4.66 4.75 4.81 4.86 5.21 5.24 5.29 5.37 7.39 7.40 7.41 7.47 7.50 7.62 7.66 7.91 7.94 8.06 O O O O NO2 O O O O O O O O O Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl
03.02.2018 10:01:31 3G27CL_001001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00 Normalized Intensity 54.411 25.468 30.000 ACETONE-d6 0.86 0.88 0.89 1.20 1.28 1.30 1.30 1.97 2.04 2.05 2.06 2.06 2.78 2.81 4.57 4.59 4.63 4.66 4.75 4.81 4.86 5.21 5.24 5.29 5.37 7.39 7.40 7.41 7.47 7.50 7.62 7.66 7.91 7.94 8.06 O O O O NO2 O O O O O O O O O Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl
05.02.2018 07:48:58 3G27CL_001001r 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 Chemical Shift (ppm) 0 0.005 0.010 0.015 0.020 0.025 0.030 0.035 0.040 0.045 0.050 0.055 0.060 0.065 0.070 0.075 Normalized Intensity ACETONE-d6 14.36 23.02 29.15 29.41 29.66 29.92 30.18 30.44 30.69 34.87 41.59 41.64 41.77 45.92 73.07 73.23 74.00 77.32 77.41 77.59 125.47 128.41 129.23 129.76 130.82 132.07 133.07 133.20 133.36 135.81 135.95 146.93 154.59 156.08 156.23 205.96 206.23 206.50 O O O O NO2 O O O O O O O O O Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl
07.02.2018 15:55:26 3G27PNP_001001r 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 Chemical Shift (ppm) 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10 0.11 0.12 0.13 0.14 0.15 0.16 Normalized Intensity 80.000 138.089 ACETONE-d6 1.20 1.29 1.96 2.04 2.04 2.05 2.06 2.06 2.09 2.79 4.81 4.88 4.91 4.96 5.05 5.15 5.19 5.31 5.36 6.78 6.80 6.81 7.05 7.08 7.09 7.11 7.22 7.25 7.41 7.54 7.72 7.81 7.82 7.84 7.94 8.08 8.10 8.12 8.19 8.21 8.22 8.24 O O O O NO2 O O O O O O O O O O O O O O O O O O O O O O2N NO2 NO2 NO2 O O O O O O O O O O O O NO2 NO2 O2N O2N NO2 NO2 NO2 O2N O2N O2N NO2 O2N O O O O2N O2N O2N O2N O2N NO2 NO2 NO2 O2N NO2 NO2
11.02.2018 12:00:53 3G27PNP-13C NMR_001001r 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20 Chemical Shift (ppm) 0 0.001 0.002 0.003 0.004 0.005 0.006 0.007 0.008 0.009 0.010 0.011 0.012 0.013 0.014 0.015 0.016 0.017 0.018 0.019 0.020 0.021 0.022 Normalized Intensity DMSO-d6 38.88 39.09 39.31 39.51 39.72 39.93 40.14 65.23 65.52 69.25 71.38 76.06 114.34 114.98 115.28 119.32 125.24 125.62 125.76 127.48 129.21 129.52 132.34 132.54 133.27 140.59 140.72 140.86 140.95 153.00 154.63 155.21 162.69 163.01 163.20 163.36 163.41 O O O O NO2 O O O O O O O O O O O O O O O O O O O O O O2N NO2 NO2 NO2 O O O O O O O O O O O O NO2 NO2 O2N O2N NO2 NO2 NO2 O2N O2N O2N NO2 O2N O O O O2N O2N O2N O2N O2N NO2 NO2 NO2 O2N NO2 NO2
