Page 1
1
Supporting Information
Reusable, Homogeneous Water Soluble Photoredox Catalyzed Oxidative Dehydrogenation of N-heterocycles in Biphasic System: Applications to
Synthesis of Biologically Active Natural Products
S. Srinatha, R. Abinayaa, Arun Prasanthb, M. Mariappanb, R. Sridharc, B. Baskara*aLaboratory of Sustainable Chemistry, Department of Chemistry, SRM Institute of Science and Technology, Kattankulatur, 603 203, Kancheepuram (Dt), Tamilnadu, India. bBioiorganic laboratory, Department of Chemistry, SRM Institute of Science and Technology, Kattankulatur, 603 203, Kancheepuram (Dt), Tamilnadu, India. cCancer Science Institute of Singapore, National University of Singapore, Singapore - 117599
Table of Contents
1. General information and mechanistic investigation S2-S62. Copy of 1H and 13C Spectra S7-S47
Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2020
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a) b)
Figure 1.a) Photochemical reaction set up b) Biphasic layer of the reaction mixture
Figure 2 IR spectra of CoPc (3a) and different water soluble MPc(SO3Na)4 [M = Co (3b), Fe (3c), Ni (3d) and Cu (3e)] photoredox catalysts measured using KBr pellet.
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3
Figure 3 UV-Visible spectral absorbance of CoPc (3a) photoredox catalyst measured in
DMSO.
Cyclic Voltammetric Experiment:The Voltammetric experiments are analyzed in Biologic SP-300 electrochemical workstation
using Glassy carbon as working electrode, Standard calomel electrode as reference electrode,
Pt wire as counter electrode and 0.1 M TBAPF6 as supporting electrolyte in DMF with 2.0
mM solution of the sample. Ferrocene was used as an internal standard (Fig. 4). All the
experiments are performed using argon purged solutions at room temperature. High purity
dimethylformamide (DMF) was purchased from SRL. The supporting electrolyte,
tetrabutylammoniumhexafluoro phosphate (TBAPF6), was purchased from Sigma Aldrich.
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4
Figure 4. Cyclic Voltammogram of Ferrocene
Figure 5. Cyclic Voltammogram of CoPc(SO3Na)4 [CoPcTs]
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5
Figure 6. Cyclic voltammogram of substrate 1a measured in DMF
Calculation of the Excited State Potential of the Catalyst:The excited state potential of the catalyst can be calculated using the Rehm–Weller
formalism by employing the following equation.
(E(I*/I·‾) = E(I/I·‾) + E0,0(I*/I))
E(I/I.-) is the ground state reduction potential of the catalyst. E0-0(I*/I) is the excited state
energy of catalyst which was estimated spectroscopically. E0-0(I*/I) was calculated to be 2.74
eV.
Thereby,
E(I*/I·‾ ) = -1.01+2.74 = +1.73V (vs SCE)
Page 6
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Figure 7 Detection of superoxide anion radical through KI experiment
The produced H2O2 can be detected in the photocatalyzed dehydrogenation of tetrahydro--carboline using the procedure reported in the literature1. The color of the dehydrogenation reaction after using KI solution denotes the presence of H2O2 which can be compared to non-illuminated reactions.
The experimental steps are:
1) Four of ethanol:water (2:1) solutions (3 mL) each containing tetrahydro--carboline (10
mM) and Co catalyst (500 µM, catalyst) were prepared. Then two of them were illuminated
under standard conditions in white LED. The remaining samples are placed as such without
illumination.
2) Each of the four solutions (0.04 ml) above was diluted with water (0.9 ml).
3) 0.06 ml of KI aqueous solution (0.6M) was added into one of the diluted irradiated (IV)
and non-irradiated (I) samples respectively. The other two samples are diluted with 0.06 ml
water (II and III). It can be clearly observed that the solution in sample IV gets deeper
yellow colour than the other samples which is due to the presence of H2O2 produced in the
reaction. The sample irradiated under light without KI doesn’t produce any colour change due
to the absence of the reaction between KI and H2O2.
References:
1. S. Chen, Q. Wan, A. K. Badu-Tawiah, Angew. Chem. Int. Ed., 2016, 55, 9345-9349.
I- (Without Irradiation) Photocatalyst + Substrate + KI
II-(Without Irradiation) Photocatalyst + Substrate
III-(Irradiation) Photocatalyst + Substrate
IV-(Irradiation) Photocatalyst + Substrate + KI
Page 7
7
1-Phenyl-9H-pyrido[3,4-b]indole (2a):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-10000
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
1E+05
1E+05
1E+05
1E+05
1.34
1.15
1.10
2.06
1.00
2.05
1.00
1.03
1.00
2.51
2.51
2.53
2.53
7.23
7.25
7.26
7.48
7.50
7.51
7.53
7.54
7.56
7.58
7.59
7.61
7.65
7.66
7.97
7.99
8.08
8.09
8.21
8.22
8.42
8.43
7.27.47.67.88.08.28.48.6f1 (ppm)
0102030405060708090100110120130140150160170180190f1 (ppm)
-2000
-1000
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
11000
12000
13000
14000
15000
16000
17000
18000
19000
2000039.5
039
.67
39.8
340
.00
40.1
740
.33
40.5
0
112.
9511
4.38
120.
0112
1.35
122.
0812
8.66
128.
9112
9.01
129.
23
138.
8713
8.93
141.
6414
2.70
NH
N
HN
N
Page 8
8
1-(Naphthalen-1-yl)-9H-pyrido[3,4-b]indole (2b):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
1.04
1.04
3.17
1.04
1.88
0.98
1.01
1.01
1.03
1.00
2.51
7.24
7.25
7.27
7.39
7.40
7.42
7.49
7.51
7.52
7.54
7.55
7.69
7.71
7.72
8.03
8.05
8.08
8.09
8.19
8.20
8.26
8.28
8.48
8.49
7.27.47.67.88.08.28.48.68.8f1 (ppm)
0102030405060708090100110120130140150160170180190200f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
39.1
339
.30
39.4
739
.55
39.6
439
.72
39.8
0
112.
6211
4.57
120.
0612
1.17
122.
2012
5.77
126.
1812
6.59
126.
8812
7.94
128.
8212
9.02
129.
2813
1.51
134.
0413
4.94
135.
6513
8.42
141.
1914
3.02
NH
N
NH
N
Page 9
9
1-(4-Methoxyphenyl)-9H-pyrido[3,4-b]indole (2c):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)
-10000
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
1E+05
1E+05
1E+05
1E+05
1E+05
2E+05
2E+05
2E+05
3.19
2.17
1.06
1.07
1.03
2.07
1.02
1.02
1.00
2.51
2.51
2.51
2.53
2.53
3.84
7.14
7.15
7.23
7.25
7.26
7.52
7.54
7.55
7.65
7.66
7.93
7.95
8.04
8.05
8.20
8.38
8.39
0102030405060708090100110120130140150160170180190f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
6000
6500
39.1
339
.29
39.4
639
.54
39.6
339
.71
39.8
0
55.7
0
112.
7911
3.86
114.
6812
0.10
121.
1812
2.01
128.
7012
9.50
130.
0813
0.95
138.
6414
1.31
142.
49
160.
05
NH
N
OMe
NH
N
OMe
Page 10
10
1-(p-tolyl)-9H-pyrido[3,4-b]indole (2d)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.5f1 (ppm)
-5000
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
55000
60000
65000
70000
75000
80000
85000
3.17
1.07
2.18
1.13
1.08
2.15
1.08
1.06
1.00
1.10
2.43
2.50
7.24
7.26
7.27
7.41
7.42
7.53
7.55
7.56
7.65
7.67
7.93
7.95
8.08
8.09
8.24
8.25
8.44
8.45
11.5
0
0102030405060708090100110120130140150160170180190200f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
6000
21.3
9
39.5
839
.75
39.9
140
.08
40.1
740
.25
40.4
1
112.
9011
4.12
119.
9612
1.30
122.
0312
8.60
128.
7412
9.57
129.
7813
3.39
136.
0013
8.46
138.
7014
1.56
142.
72
NH
N
Me
NH
N
Me
Page 11
11
1-(4-Isopropylphenyl)-9H-pyrido[3,4-b]indole (2e):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)
-20000
-10000
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
1E+05
1E+05
1E+05
1E+05
1E+05
2E+05
2E+05
2E+05
2E+05
2E+05
2E+05
2E+05
2E+05
6.34
1.03
1.02
2.07
1.04
1.00
2.04
1.03
1.02
1.00
1.22
1.24
2.51
2.51
2.51
2.92
2.94
2.95
7.23
7.24
7.26
7.42
7.43
7.52
7.54
7.55
7.64
7.66
7.89
7.90
8.06
8.07
8.20
8.22
8.39
8.40
7.07.27.47.67.88.08.28.48.6f1 (ppm)
0102030405060708090100110120130140150160170180190200f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
6000
650024.2
1
33.7
539
.13
39.3
039
.46
39.5
539
.63
39.7
239
.80
112.
8111
4.16
120.
1112
1.15
122.
0112
7.22
128.
7112
8.74
129.
5913
3.20
136.
0613
8.67
141.
3714
2.64
149.
47
NH
N
NH
N
Page 12
12
6-Methoxy-1-phenyl-9H-pyrido[3,4-b]indole (2f):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-10000
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
1E+05
1E+05
1E+05
1E+05
3.10
1.09
1.10
3.16
1.03
2.06
1.01
1.00
2.51
3.85
7.18
7.19
7.20
7.20
7.56
7.57
7.59
7.97
7.98
8.09
8.37
8.38
0102030405060708090100110120130140150160170180190200f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
6000
650039.1
239
.29
39.4
639
.54
39.6
339
.71
39.7
9
56.0
5
103.
67
113.
7411
4.48
118.
8712
1.48
128.
6612
9.11
129.
3012
9.55
133.
7813
6.27
138.
1613
8.48
142.
59
153.
99
HN
NMeO
HN
NMeO
Page 13
13
1-(4-Nitrophenyl)-9H-pyrido[3,4-b]indole (2g):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-10000
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
1E+05
1E+05
0.94
0.96
0.95
3.86
1.87
1.00
2.51
7.27
7.29
7.30
7.56
7.58
7.59
7.65
7.66
8.19
8.20
8.22
8.24
8.27
8.40
8.42
8.48
8.49
0102030405060708090100110120130140150160170180190200f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
38.9
639
.13
39.2
939
.46
39.6
339
.79
39.9
6
112.
7511
5.63
120.
4612
0.97
122.
1912
4.34
129.
2112
9.89
130.
3713
3.61
139.
0514
1.49
144.
6914
7.54
HN
N
NO2
HN
N
NO2
Page 14
14
1-(4-Bromophenyl)-9H-pyrido[3,4-b]indole (2h):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
0
50000
1E+05
2E+05
2E+05
2E+05
Srinath-SRM-CHE-SS-EX-Br-AROMATIZEDSrinath-SRM-CHE-SS-EX-Br-AROMATIZED
1.02
1.02
1.07
2.10
2.11
1.00
1.05
1.00
2.49
2.50
2.50
2.51
2.51
2.52
3.82
7.23
7.25
7.26
7.53
7.54
7.56
7.62
7.64
7.74
7.76
7.90
7.92
8.10
8.11
8.21
8.23
8.40
8.41
NH
N
Br
0102030405060708090100110120130140150160170180190f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
6000
6500
7000
39.1
339
.30
39.4
739
.55
39.6
339
.72
39.8
0
112.
7611
4.76
120.
2712
2.12
122.
50
128.
9712
9.89
130.
8013
2.20
133.
2113
7.61
138.
8514
1.27
141.
39
NH
N
Br
Page 15
15
6-Methoxy-1-(4-nitrophenyl)-9H-pyrido[3,4-b]indole (2i)
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-2000
0
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
22000
24000
26000
28000
30000
32000
34000
3.30
1.00
1.12
0.99
3.17
3.05
2.50
3.67
7.21
7.22
7.55
7.57
7.80
8.18
8.19
8.22
8.24
8.40
8.42
8.44
8.45
7.58.08.5f1 (ppm)
0102030405060708090100110120130140150160170180190200f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
39.1
339
.30
39.4
739
.55
39.6
439
.72
39.8
0
56.0
7
103.
84
113.
7111
5.75
119.
2612
1.38
124.
37
129.
8613
0.27
134.
1313
6.37
138.
5013
9.84
144.
7614
7.56
154.
19
100110120130140150160f1 (ppm)
HN
NMeO
NO2
HN
NMeO
NO2
Page 16
16
1-(Thiophen-2-yl)-9H-pyrido[3,4-b]indole (2j):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
1.11
1.22
1.06
0.96
1.09
1.98
0.98
1.00
2.50
7.25
7.26
7.27
7.29
7.30
7.31
7.55
7.56
7.58
7.66
7.67
7.71
7.73
8.03
8.05
8.19
8.21
8.31
8.32
0102030405060708090100110120130140150160170180190f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
39.1
339
.29
39.4
639
.55
39.6
339
.71
39.8
0
112.
9711
4.39
120.
5312
1.08
122.
0312
6.16
128.
4612
9.04
129.
08
136.
8313
8.53
141.
4814
3.69
HN
N
S
HN
N
S
Page 17
17
Methyl 1-phenyl-9H-pyrido[3,4-b]indole-3-carboxylate (2k):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)
-20000
0
20000
40000
60000
80000
1E+05
1E+05
1E+05
2E+05
2E+05
2E+05
2E+05
2E+05
3E+05
3E+05
3E+05
3.12
1.01
1.11
3.15
1.12
2.03
1.00
0.93
2.51
2.51
2.51
2.52
2.53
2.53
3.91
7.31
7.32
7.34
7.53
7.55
7.56
7.59
7.60
7.60
7.61
7.61
7.61
7.62
7.63
7.68
7.70
7.96
7.98
8.34
8.36
8.86
7.58.08.59.0f1 (ppm)
0102030405060708090100110120130140150160170180190200f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
39.1
239
.29
39.4
639
.54
39.6
339
.71
39.7
9
52.6
2
113.
1611
7.05
121.
0512
1.42
122.
3112
8.94
129.
3312
9.57
134.
8313
7.06
137.
7214
1.68
142.
60
166.
63
HN
N
OO
HN
N
OO
Page 18
18
Methyl 1-(4-isopropylphenyl)-9H-pyrido[3,4-b]indole-3-carboxylate (2l):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
-2000
0
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
22000
24000
26000
28000
30000
6.36
1.18
3.32
1.13
2.22
1.22
1.15
2.24
1.01
1.00
1.22
1.23
2.50
2.91
2.92
2.94
2.95
2.96
3.89
7.28
7.30
7.31
7.40
7.42
7.55
7.57
7.58
7.66
7.67
7.84
7.85
8.31
8.32
8.80
0102030405060708090100110120130140150160170180190f1 (ppm)
0
100
200
300
400
500
600
700
800
900
1000
24.8
6
34.4
539
.75
39.9
240
.09
40.2
540
.33
40.4
2
53.2
6
113.
8211
7.50
121.
6812
2.09
122.
9412
7.87
129.
6012
9.87
135.
4213
6.02
137.
6614
2.31
143.
37
150.
64
167.
33
HN
N
CO2Me
HN
N
CO2Me
Page 19
19
Methyl 1-(thiophen-2-yl)-9H-pyrido[3,4-b]indole-3-carboxylate (2m):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-5000
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
55000
60000
65000
70000
75000
80000
3.11
2.22
1.09
2.12
1.04
1.05
1.00
2.59
3.99
7.40
7.42
7.43
7.68
7.70
7.71
7.82
7.83
7.85
8.16
8.16
8.41
8.43
8.88
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
39.1
239
.29
39.4
639
.54
39.6
339
.71
39.7
9
52.7
1
113.
3211
6.85
121.
3812
2.29
127.
0812
9.07
129.
2812
9.49
130.
1413
2.71
136.
7213
6.78
141.
7514
2.54
166.
20
110120130140150160170f1 (ppm)
HN
N
COOMe
S
HN
N
COOMe
S
Page 20
20
Methyl 1-methyl-9H-pyrido[3,4-b]indole-3-carboxylate (2n):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-10000
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
1E+05
1E+05
1E+05
1E+05
3.17
3.31
1.14
1.13
1.11
1.06
1.00
2.50
2.51
2.51
2.52
2.53
2.53
2.78
3.87
7.27
7.28
7.30
7.56
7.57
7.58
7.63
7.64
8.26
8.27
8.70
0102030405060708090100110120130140150160170180190200f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
6000
6500
700021.0
839
.50
39.6
639
.83
39.9
240
.00
40.0
840
.17
40.2
540
.33
40.4
240
.50
53.0
0
113.
2911
6.90
121.
3612
2.15
122.
9612
7.74
129.
54
136.
7013
7.01
141.
5714
3.31
167.
20
NH
NMeO2C
HN
N
CO2Me
Page 21
21
Quinoline (5a) :
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-10000
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
1E+05
1E+05
1E+05
1E+05
1.04
1.04
1.03
1.03
2.02
1.00
7.31
7.32
7.32
7.32
7.33
7.33
7.48
7.50
7.51
7.67
7.68
7.70
7.75
7.76
8.07
8.09
8.11
8.13
8.89
8.90
0102030405060708090100110120130140150160170180190200f1 (ppm)
-2000
0
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
22000
24000
26000
28000
30000
32000
34000
36000
38000
40000
77.0
377
.28
77.5
4
121.
0112
6.47
127.
7612
9.38
129.
40
135.
97
148.
2115
0.33
N
N
7.07.17.27.37.47.57.67.77.87.98.08.18.28.38.48.58.68.78.88.99.09.1f1 (ppm)
-10000
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
1E+05
1E+05
1E+05
1E+05
1.04
1.04
1.03
1.03
2.02
1.00
7.31
7.32
7.32
7.32
7.33
7.33
7.48
7.50
7.51
7.67
7.68
7.70
7.75
7.76
8.07
8.09
8.11
8.13
8.89
8.90
Page 22
22
6-Methoxyquinoline (5b):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
0
50000
1E+05
2E+05
2E+05
2E+05
3E+05
4E+05
4E+05
4E+05
3.30
1.04
2.06
0.99
1.10
1.00
3.44
6.57
6.58
6.86
6.87
6.87
6.89
7.50
7.52
7.55
7.56
8.27
8.27
8.27
8.28
0102030405060708090100110120130140150160170180190200f1 (ppm)
-200
0
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
2400
2600
2800
3000
55.5
4
76.7
977
.05
77.3
0
105.
13
121.
3712
2.28
129.
3113
0.87
134.
79
144.
45
147.
95
157.
74
N
H3CO
N
H3CO
Page 23
23
6-Bromoquinoline (5c):
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-10000
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
1E+05
1E+05
1E+05
1E+05
1E+05
2E+05
2E+05
2E+05
2E+05
1.07
1.03
1.02
0.97
1.11
1.00
7.26
7.39
7.39
7.40
7.41
7.75
7.75
7.76
7.77
7.95
7.96
7.97
8.89
8.90
8.90
8.90
0102030405060708090100110120130140150160170180190200f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
6000
6500
76.8
477
.09
77.3
4
120.
4812
1.90
129.
3412
9.81
131.
1813
2.97
135.
10
146.
78
150.
71
N
Br
N
Br
Page 24
24
2-Methylquinoline (5d):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-20000
0
20000
40000
60000
80000
1E+05
1E+05
1E+05
2E+05
2E+05
2E+05
2E+05
2E+05
3E+05
3E+05
3E+05
3.18
1.00
0.98
0.97
0.98
1.91
2.75
7.27
7.28
7.47
7.48
7.50
7.67
7.68
7.70
7.76
7.77
8.03
8.04
0102030405060708090100110120130140150160170180190f1 (ppm)
0
500
1000
1500
2000
2500
3000
3500
4000
4500
Srinath-2-Methyl QuinolineSrinath-2-Methyl Quinoline 25
.36
76.8
477
.10
77.3
5
122.
0012
5.66
126.
4812
7.49
128.
6112
9.42
136.
17
147.
86
158.
98
N
N
Page 25
25
7-Chloro-2-methylquinoline (5e):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
-10000
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
1E+05
1E+05
3.23
1.18
1.03
1.05
2.00
2.75
7.29
7.30
7.44
7.44
7.46
7.46
7.71
7.72
8.02
8.03
8.04
8.04
0102030405060708090100110120130140150160170180190f1 (ppm)
0
500
1000
1500
2000
2500
3000
25.3
8
76.8
077
.05
77.3
1
122.
2512
4.85
126.
7412
7.71
128.
72
135.
2313
5.99
148.
20
160.
24
NCl
NCl
Page 26
26
6,7-dimethoxyisoquinoline (5f):
N
MeO
MeO
N
MeO
MeO
Page 27
27
6,7-Dimethoxy-1-phenylisoquinoline (5g):
N
MeO
MeO
N
MeO
MeO
Page 28
28
6,7-Dimethoxy-1-(4-methoxyphenyl)isoquinoline (5h):
-1.0-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
-20000
-10000
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
1E+05
1E+05
1E+05
1E+05
1E+05
2E+05
2E+05
2E+05
2E+05
2E+05
2E+05
2E+05
2E+05
2E+05Srinath-SRM-CHE-SS-EX-DIMETHOXY-ANISASrinath-SRM-CHE-SS-EX-DIMETHOXY-ANISA
3.23
3.02
3.14
2.03
1.03
1.35
1.02
1.02
2.03
1.00
-0.0
0
3.81
3.83
3.97
6.98
7.00
7.04
7.19
7.34
7.39
7.40
7.59
7.60
8.38
8.39
0102030405060708090100110120130140150160170180190200f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
6000
6500
7000
7500
8000
8500
Srinath-SRM-CHE-SS-EX-DIMETHOXY-ANISASrinath-SRM-CHE-SS-EX-DIMETHOXY-ANISA 55
.38
55.9
356
.09
76.8
177
.06
77.3
1
105.
0110
5.71
113.
8711
8.45
122.
55
130.
9313
2.54
133.
81
141.
33
149.
9115
2.58
158.
0015
9.83
N
MeO
MeO
OMe
N
MeO
MeO
OMe
Page 29
29
1-(4-Isopropylphenyl)-6,7-dimethoxyisoquinoline (5i):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-20000
0
20000
40000
60000
80000
1E+05
1E+05
1E+05
2E+05
2E+05
2E+05
2E+05
2E+05
3E+05
3E+05
3E+05Srinath-SRM-CHE-SS-EX-DIMETHOXY IPASrinath-SRM-CHE-SS-EX-DIMETHOXY IPA
6.25
1.14
3.34
3.17
1.14
2.10
2.06
2.07
1.00
1.21
1.22
2.87
2.88
2.90
2.91
2.93
3.76
3.90
6.98
7.27
7.29
7.33
7.34
7.53
7.55
8.34
8.35
0102030405060708090100110120130140150160170180190f1 (ppm)
-5000
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
55000
60000
65000
70000
75000Srinath-SRM-CHE-SS-EX-DIMETHOXY IPASrinath-SRM-CHE-SS-EX-DIMETHOXY IPA 23
.98
34.0
0
55.9
056
.00
76.9
577
.21
77.4
6
104.
9910
5.73
118.
5412
2.44
126.
5312
9.59
133.
7613
7.51
141.
31
149.
1614
9.89
152.
55
158.
27
N
MeO
MeO
N
MeO
MeO
Page 30
30
1-(4-Chlorophenyl)-6,7-dimethoxyisoquinoline (5j):
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
0
50000
1E+05
2E+05
2E+05
2E+05
Srinath-SRM-CHE-SS-EX-DIMETHOXY CHLOROSrinath-SRM-CHE-SS-EX-DIMETHOXY CHLORO
3.17
3.13
1.03
1.04
3.05
2.05
1.00
3.70
3.85
6.92
7.12
7.31
7.32
7.34
7.36
7.49
7.50
8.29
8.30
-100102030405060708090100110120130140150160170180190200210f1 (ppm)
-10000
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
1E+05
1E+05
Srinath-SRM-CHE-SS-EX-DIMETHOXY CHLOROSrinath-SRM-CHE-SS-EX-DIMETHOXY CHLORO 55
.76
55.9
3
77.0
877
.34
77.5
9
104.
9010
4.98
118.
9612
2.25
128.
5613
0.94
133.
6913
4.37
138.
4614
1.23
150.
0915
2.61
156.
72
N
MeO
MeO
Cl
N
MeO
MeO
Cl
Page 31
31
6,7-Dimethoxy-1-(4-nitrophenyl)isoquinoline (5k):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
0
50000
1E+05
2E+05
2E+05
2E+05
3E+05
4E+05
4E+05
4E+05
5E+05
Srinath-SRM-CHE-SS-EX-DIMETHOXY NITRO-FASrinath-SRM-CHE-SS-EX-DIMETHOXY NITRO-FA
3.13
3.17
1.02
1.03
1.02
2.03
1.99
1.00
3.80
3.99
7.09
7.14
7.50
7.51
7.82
7.83
8.32
8.33
8.42
8.43
0102030405060708090100110120130140150160170180190200f1 (ppm)
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
Srinath-SRM-CHE-SS-EX-DIMETHOXY NITRO-FASrinath-SRM-CHE-SS-EX-DIMETHOXY NITRO-FA 55
.99
56.2
1
76.8
177
.07
77.3
2
104.
3210
5.21
119.
8312
2.35
123.
74
130.
65
133.
95
141.
4614
6.51
147.
8115
0.65
153.
0015
5.56
N
MeO
MeO
NO2
N
MeO
MeO
NO2
Page 32
32
6,7-Dimethoxy-1-(thiophen-2-yl)isoquinoline (5l):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
1E+05
Srinath-Dimethoxy ThiopheneSrinath-Dimethoxy Thiophene
3.24
3.24
1.06
1.01
1.06
0.95
1.04
1.10
1.00
3.90
3.95
7.01
7.02
7.12
7.36
7.43
7.44
7.52
7.52
7.72
8.33
8.35
0102030405060708090100110120130140150160170180190f1 (ppm)
-200
-100
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
56.0
056
.08
76.8
377
.08
77.3
4
105.
0710
5.17
118.
80
122.
0812
7.41
127.
5112
7.61
134.
02
141.
2914
3.45
150.
5115
1.10
152.
69
MeO
MeON
S
MeO
MeON
S
Page 33
33
Indole (7a):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-5000
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
55000
60000
65000
70000
75000
80000
85000
90000Srinath-SRM-CHE-SS-EX-INDOLESrinath-SRM-CHE-SS-EX-INDOLE
0.99
0.99
0.98
1.07
1.01
1.00
0.98
1.62
6.63
6.63
6.63
7.20
7.24
7.28
7.44
7.45
7.72
7.74
8.13
0102030405060708090100110120130140150160170180190200f1 (ppm)
-1000
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
Srinath-SRM-CHE-SS-EX-INDOLESrinath-SRM-CHE-SS-EX-INDOLE 77
.02
77.2
877
.53
102.
57
111.
32
119.
9912
0.90
122.
1212
4.49
127.
96
135.
88
NH
NH
Page 34
34
2-Methylindole (7b):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
3.31
0.94
1.98
1.15
1.11
1.00
2.46
6.27
7.11
7.15
7.18
7.30
7.31
7.56
7.58
7.83
0102030405060708090100110120130140150160170180190f1 (ppm)
-200
0
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
2400
2600
2800
300013
.72
76.8
477
.10
77.3
5
100.
39
110.
28
119.
6612
0.95
129.
09
135.
1313
6.08
NH
NH
Page 35
35
5-Methoxyindole (7c):
3.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.28.48.6f1 (ppm)
0
50000
1E+05
2E+05
2E+05
2E+05
3E+05
4E+05
4E+05
4E+05
5E+05
3.29
1.00
1.01
0.98
1.01
0.97
1.02
3.87
6.49
6.50
6.50
6.87
6.87
6.89
6.89
7.12
7.13
7.18
7.18
7.19
7.26
7.28
7.29
8.07
0102030405060708090100110120130140150160170180190200f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
6000
55.9
5
76.9
277
.17
77.4
3
102.
3310
2.40
111.
9011
2.37
125.
0912
8.34
131.
07
154.
20
NH
MeO
NH
MeO
Page 36
36
5-Nitroindole (7d):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-10000
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
1E+05
1E+05
0.98
0.98
1.01
0.99
1.00
0.83
1.67
6.73
6.74
6.74
7.26
7.38
7.39
7.39
7.44
7.46
8.10
8.11
8.12
8.13
8.61
8.62
8.71
0102030405060708090100110120130140150160170180190200f1 (ppm)
-200
0
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
2400
2600
2800
3000
3200Srinath-SRM-CHE-SS-EX-NO2 INDOLESrinath-SRM-CHE-SS-EX-NO2 INDOLE 76
.80
77.0
577
.31
105.
09
111.
08
117.
7211
8.05
127.
2612
7.42
138.
8314
1.95
NH
O2N
NH
O2N
Page 37
37
5-Cyanoindole (7e):
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)
-10000
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
1E+05
1E+05
1E+05
1E+05
1E+05
2E+05
2E+05
2E+05
2E+05
1.04
0.10
1.02
1.02
1.03
1.00
1.01
1.80
6.63
6.63
6.63
6.63
6.64
7.35
7.35
7.36
7.42
7.47
7.48
7.99
7.99
8.78
0102030405060708090100110120130140150160170180190200f1 (ppm)
-200
0
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
2400
2600
2800
3000
76.8
577
.10
77.3
6
102.
6010
3.37
112.
12
121.
0112
4.82
126.
4312
6.63
127.
69
137.
60
NH
NC
NH
NC
Page 38
38
5- Bromoindole (7f):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-10000
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
1E+05
1E+05
1E+05
1E+05
1E+05
2E+05
2E+05
2E+05
2E+05
1.03
0.96
1.80
1.00
0.89
1.58
6.50
6.50
6.51
7.21
7.21
7.22
7.26
7.27
7.78
8.20
0102030405060708090100110120130140150160170180190f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
600076.7
577
.00
77.2
5
102.
19
112.
4311
2.92
123.
1212
4.74
125.
3712
9.54
134.
31
NH
Br
NH
Br
Page 39
39
5-Bromo-7-nitro indole (7g):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-5000
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
55000
60000
65000
70000
1.04
1.05
1.02
1.00
1.05
-0.0
0
6.60
6.61
6.61
7.35
7.36
7.36
8.02
8.03
8.03
8.21
8.21
9.87
0102030405060708090100110120130140150160170180190200f1 (ppm)
-200
-100
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
76.7
777
.02
77.2
8
103.
60
111.
35
121.
64
127.
9212
8.14
131.
1113
3.16
NH
Br
NO2
NH
Br
NO2
Page 40
40
7-Azaindole (7h):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.5f1 (ppm)
-5000
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
0.98
1.01
1.01
1.00
1.00
0.93
2.37
6.52
6.53
7.11
7.11
7.12
7.40
7.41
7.98
7.98
8.35
8.35
8.36
8.36
11.4
9
0102030405060708090100110120130140150160170180190200f1 (ppm)
-200
0
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
240076.8
277
.07
77.3
3
100.
57
115.
7512
0.59
125.
4012
9.10
142.
31
148.
86
HNN
HNN
Page 41
41
Ethyl indole-2-carboxylate (7i):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
1E+05
3.29
2.14
1.03
1.03
1.03
1.02
1.00
0.99
1.44
1.45
1.47
4.44
4.45
4.47
4.48
7.17
7.18
7.20
7.27
7.34
7.35
7.37
7.45
7.47
7.72
7.73
9.17
0102030405060708090100110120130140150160170180190f1 (ppm)
-200
-100
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
210014.4
2
61.0
9
76.8
177
.06
77.3
2
108.
68
111.
93
120.
7912
2.61
125.
3512
7.51
136.
93
162.
21
NH
O
O
NH
O
O
Page 42
42
Eudistomin U (9a)
NH
N
HN
NH
N
HNH
Page 43
43
9H-pyrido[3,4-b]indole (11a):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
1.06
1.07
0.96
1.07
1.05
1.06
1.00
2.51
7.22
7.23
7.54
7.55
7.59
7.61
8.09
8.19
8.20
8.31
8.89
0102030405060708090100110120130140150160170180190f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
6000
39.1
239
.29
39.4
639
.54
39.6
239
.71
39.7
9
112.
3611
5.29
119.
9512
0.87
122.
27
128.
1612
8.86
134.
0913
6.21
138.
2914
0.90
HN
N
HN
N
Page 44
44
1-Methyl-9H-pyrido[3,4-b]indole (13a):
0102030405060708090100110120130140150160170180190f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
6000
6500
20.3
8
39.1
339
.30
39.4
739
.55
39.6
339
.72
39.8
0
112.
3911
3.34
119.
9412
1.30
122.
2512
7.62
128.
61
134.
7313
7.51
140.
7714
2.37
105110115120125130135140145f1 (ppm)
NH
N
CH3
NH
N
CH3
Page 45
45
1-(Furan-2-yl)-9H-pyrido[3,4-b]indole (15a):
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-20000
-10000
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
1E+05
1E+05
1E+05
1E+05
1E+05
2E+05
2E+05
2E+05
2E+05
2E+05
2E+05
2E+05
2E+05
2E+05
2E+05
0.98
1.99
1.04
1.00
0.93
1.04
1.02
1.00
2.50
6.75
7.24
7.26
7.26
7.54
7.56
7.57
7.74
7.76
7.95
8.03
8.04
8.19
8.20
8.32
8.33
6.87.07.27.47.67.88.08.28.4f1 (ppm)
0102030405060708090100110120130140150160170180190200f1 (ppm)
-200
0
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
2400
2600
2800
3000
3200
3400
39.1
239
.29
39.4
639
.54
39.6
239
.71
39.7
9
109.
4111
2.74
112.
9711
4.36
120.
2912
0.78
122.
03
129.
0313
0.02
130.
8813
3.35
138.
4314
1.43
144.
35
153.
25
NH
N
O
NH
N
O
Page 46
46
Methyl 1-(furan-2-yl)-9H-pyrido[3,4-b]indole-3-carboxylate (18a):
.
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-20000
0
20000
40000
60000
80000
1E+05
1E+05
1E+05
2E+05
2E+05
2E+05
2E+05
2E+05
3E+05
3E+05
3E+05
3E+05
3E+05
3.08
1.04
1.10
1.03
1.10
1.08
1.02
1.09
1.00
2.49
2.50
2.50
2.50
2.51
3.89
6.74
6.75
7.26
7.31
7.32
7.75
7.76
7.95
7.95
7.95
7.95
8.23
8.25
8.70
0102030405060708090100110120130140150160170180190f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
6000
6500
7000Srinath-SRM-CHE-SS-EX-TRY ESTFLSrinath-SRM-CHE-SS-EX-TRY ESTFL 39
.67
39.8
340
.00
40.0
840
.17
40.2
540
.34
53.1
7
111.
0011
3.33
113.
8311
7.21
121.
5912
1.62
122.
68
129.
8713
0.37
132.
8713
3.76
137.
1814
2.22
145.
24
153.
00
166.
83
NH
N
CO2Me
O
NH
N
CO2Me
O
Page 47
47
1-(3,4-Dihydroquinolin-1(2H)-yl)ethanone (20)
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
-5000
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000
55000
60000
65000
70000
75000
80000
85000Srinath-1-Acetyl quinolineSrinath-1-Acetyl quinoline
2.12
3.30
2.01
2.00
3.90
1.85
1.86
1.88
1.89
1.90
2.15
2.62
2.64
2.65
3.70
3.71
7.02
7.04
7.06
7.08
7.09
7.10
7.12
0102030405060708090100110120130140150160170180190200f1 (ppm)
0
1000
2000
3000
4000
5000
6000
7000
8000
900023.1
424
.05
26.8
8
76.9
177
.17
77.4
2
124.
5812
5.15
126.
0712
8.42
170.
06
N
OH3C
N
OH3C
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