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Supporting InformationA Simple and Efficient in situ Generated Ruthenium Catalyst for Chemoselective Transfer Hydrogenation of Nitroarenes: Kinetic and Mechanistic Studies and Comparison with Iridium SystemsBhaskar Paul, Kaushik Chakrabarti, Sujan Shee, Milan Maji, Anju Mishra and Sabuj Kundu*
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2016
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ContentsTextS1:General Procedure for Optimization of Amount of NaOiPr 3
Text S2:General Procedure for Only NaOiPr Catalysed TH of Nitrobenzene 3
Text S3:Performance Comparison of Ruthenium and Iridium Catalyst in the TH 3
Experiment of Nitrobenzene
Text S4:General Procedure for Influence of External Amine on TH of Nitrobenzene 3 With Ru- catalyst
Characterisation of Product 4-8
Copies of 1H and 13C NMR Spectra of Amines 9-34
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3
Text S1: General Procedure for Optimization of Amount of NaOiPr:Eightidentical TH experiments of nitroarenes were conducted in parallel following the outlined procedurewith varying amount of NaOiPr (0, 10, 20, 30, 40, 50, 60, 70 and 80 mol% with respect to catalyst). All the reactions were carried out at 110°C (oil bath Temp) and the progress was monitored after 5 hours by gas chromatography. All the reactions were repeated three times and the average data were plotted as yield of aniline (%) vs amount of NaOiPr (mol%) (Fig. 1).
Text S2: General Procedure for Only NaOiPr Catalysed TH of Nitrobenzene:In a screw cap tube nitrobenzene (123 mg, 1 mmol), NaOiPr (32.8 mg, 0.4 mmol), toluene (as internal standard) and 10 mL dry isopropanol were taken under argon atmosphere. The mixture was heated to reflux at 110°C(oil bath Temp). The conversion and product selectivity were determined by gas chromatographyat different time interval. The reaction was repeated three times and an average data were plotted as conversion (%) vs time (minute) (Fig. 5).
Text S3: Performance Comparison of Ruthenium and Iridium Catalyst in the TH Experiment of Nitrobenzene:Two identical TH experiments of nitroarenes were conducted in parallel following the outlined procedure, one with Ru-catalyst and other with Ir-catalyst. Both the reaction tubes were heated at 110°C (oil bath Temp) and the progress of the reaction was monitored at different time interval by gas chromatography. The reactions was repeated three times and an average data for both catalyst were plotted as yield of aniline (%) vs time (minute) (Fig. 7).
Text S4: General Procedure for Influence of External Amine on TH of Nitrobenzene with Ru-catalyst:Two identical TH experiments of nitrobenzene were conducted in parallel following the outlined procedure, one acted as a control reaction. Under argon atmosphere 4-methoxy aniline (1 eq.) was added to one of the reaction tube whereas the other one keep in same argon condition. Both the tubes were heated at 110 °C in the oil bath and the progress of the reaction was monitored after 1 hour and 5 hours by gas chromatography. The yield of aniline with and without externally added 4-methoxy aniline were shown in Scheme 3.
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Characterisation of products:
NH2
1H NMR (500 MHz, CDCl3): δ = 7.17 (t, JH,H = 7.75 Hz, 2H), 6.77 (t, JH,H = 7.45 Hz, 1H), 6.69 (d, JH,H = 7.51 Hz, 2H), 3.95 (br s, 2H). 13C NMR (125 MHz, CDCl3): δ = 146.42, 129.38, 118.68, 115.23
NH2
Me
1H NMR (500 MHz, CDCl3): δ = 7.04 (t, JH,H = 7.63 Hz, 1H), 6.59 (d, JH,H = 7.54 Hz, 1H), 6.53-6.48 (m, 2H), 3.47 (br s, 2H), 2.26 (s, 2H). 13C NMR (125 MHz, CDCl3): δ = 141, 129.25, 123.45, 119.72, 116.13, 112.46, 21.49
NH2
Me
1H NMR (400 MHz, DMSO-D6): δ = 6.83 (t, JH,H = 7.64 Hz 1H), 6.33-6.25 (m, 3H), 4.86(br s, 2H), 2.10 (s, 3H). 13C NMR (125 MHz, DMSO-D6): δ = 149.02, 138.22, 129.20, 117.07, 115.05, 111.68, 21.74
NH2
Me
1H NMR (400 MHz, CDCl3): δ = 6.96 (d, JH,H = 7.88 Hz,2H), 6.61 (d,JH,H = 8.36 Hz, 2H), 3.35(br s, 2H), 2.20(s, 3H). 13C NMR (125 MHz, CDCl3): δ = 143.81, 129.83, 127.92, 115.37, 20.68
NH2
MeO
1H NMR (400 MHz, DMSO-D6): δ = 6.74(d, JH,H = 8.84 Hz, 2H), 6.65 (d, JH,H = 9.0 Hz, 2H), 3.73(s, 3H), 3.31(br s, 2H). 13C NMR (125 MHz, DMSO-D6): δ =152.90, 139.77, 116.62, 115.02, 55.82
NH2
MeS
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5
1H NMR (400 MHz, CDCl3): δ = 7.17(d, JH,H = 8.48 Hz, 2H), 6.62 (d, JH,H = 8.63 Hz, 2H), 3.59(br s, 2H), 2.40(s, 2H). 13C NMR (125 MHz, CDCl3): δ =145.15, 131.16, 125.93, 115.83, 18.88
NH2Me
Me
1H NMR (400MHz, CDCl3): δ = 6.98 (d, JH,H = 7.42 Hz,2H), 6.68 (t, JH,H = 7.68 Hz 1H), 3.57 (br s, 2H), 2.21(s, 6H). 13C NMR (125 MHz, CDCl3): δ = 142.81, 128.36, 121.82, 118.12, 17.73
NH2
F
1H NMR (500 MHz, CDCl3): δ = 7.76 (d, JH,H = 7.25 Hz,1H), 7.47 (t, JH,H = 7.47 Hz, 1H), 7.06(d, JH,H = 8.35Hz, 1H), 6.98(t, JH,H = 7.65 Hz, 1H). 13C NMR (125 MHz, CDCl3): δ = 151.34, 136.99, 133.63, 125.51, 120.16, 116.21
NH2
Cl
1H NMR (400 MHz, CDCl3): δ = 7.05 (t, JH,H = 7.92 Hz,1H), 6.71 (d, JH,H = 7.86 Hz, 1H), 6.66(t, JH,H = 2.21 Hz, 1H), 6.54-6.51(m, 1H) 3.67(br s, 2H). 13C NMR (125 MHz, CDCl3): δ = 147.74, 134.92, 130.42, 118.53, 115.01, 113.29
F
NH2
1H NMR (500 MHz, CDCl3): δ = 8.17 (d, JH,H = 9.30 Hz,2H), 6.9 (m, JH,H = 9.20 Hz, 2H). 13C NMR (125 MHz, CDCl3): δ = 158.76, 121.58, 110.88, 66.51
NH2
Cl
1H NMR (400 MHz, CDCl3): δ = 7.08 (d, JHH = 8.72 Hz,2H), 6.59 (d, JHH = 8.68 Hz, 2H), 3.64(br s, 2H). 13C NMR (125 MHz, CDCl3): δ = 145.0, 129.19, 123.27, 116.30
NH2
Br
Page 6
6
1H NMR (400 MHz, CDCl3): δ = 7.22 (d, JH,H = 8.28 Hz,2H), 6.54 (d, JH,H = 8.28 Hz, 2H), 3.58(br s, 2H). 13C NMR (125 MHz, CDCl3): δ = 145.53, 132.09, 116.81, 110.25
NH2
1H NMR (500 MHz, CDCl3): δ = 7.83-7.78 (m, 2H), 7.47-7.45 (m 2H), 7.33-7.25(m, 2H), 6.78(dd, JH,H = 6.95 Hz, JH,H = 1.2 Hz, 1H) 4.14(br, 2H). 13C NMR (125 MHz, CDCl3): δ = 139.60, 131.98, 126.08, 123.85, 123.35, 122.37, 121.24, 118.30, 116.53, 107.23
NH2
COMe
1H NMR (400 MHz, CDCl3): δ = 7.69 (dd, JH,H = 8.32 Hz, JH,H = 1.48 Hz, 2H), 7.26-7.22 (m, 1H), 6.65-6.60(m, 2H), 6.26(br s, 2H), 2.55 (s, 3H). 13C NMR (125 MHz, CDCl3): δ =200.84, 150.37, 134.46, 132.12, 118.32, 117.29, 115.81, 27.94
NH2
COMe
1H NMR (500 MHz, CDCl3): δ = 7.32 (d, JH,H = 7.65 Hz, 1H), 7.26-7.21(m, 2H), 6.87(dd, JH,H = 8.05 Hz, JH,H = 1.95 Hz, 1H), 2.03 (s, 3H). 13C NMR (125 MHz, CDCl3): δ = 198.46, 146.69, 139.58, 129.50, 119.75, 119.02, 114.15, 29.76
NH2
MeOC
1H NMR (500 MHz, CDCl3): δ = 7.80(d, JH,H = 8.6 Hz, 2H), 6.64 (d, JH,H = 8.5 Hz, 2H), 4.11(br s, 2H), 2.49 (s, 3H). 13C NMR (125 MHz, CDCl3): δ =191.78, 146.40, 126.12, 123.27, 109.05, 21.40
NH2
CN
1H NMR (500 MHz, CDCl3): δ = 7.10 (t, JH,H = 7.9 Hz, 1H), 6.90 (d, JH,H = 7.55 Hz, 1H), 6.78 (s, 1H), 6.75(m, 1H). 13C NMR (125 MHz, CDCl3): δ = 146.97, 130.13, 122.12, 119.27, 117.54, 113.04
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7
NH2
1H NMR (500 MHz, CDCl3): δ = 7.13(t, JH,H = 7.70 Hz, 1H), 6.84 (d, JH,H = 7.61 Hz, 1H), 6.75 (t, JH,H = 1.95 Hz, 1H), 6.67-6.59(m, 2H), 5.72-5.69(d, JH,H = 17.3 Hz 1H), 5.22(d, JH,H = 10.95 Hz, 1H), 3.52(br s, 2H). 13C NMR (125 MHz, CDCl3): δ = 146.52, 138.83, 137.13, 129.49, 117.10, 114.92, 113.65, 112.90
NH2
CONH2
1H NMR (500 MHz, DMSO-d6): δ = 7.68 (s, 1H), 7.07-7.00 (m, 3H), 6.94 (d, JH,H = 7.75 Hz, 1H), 6.65(d, JH,H = 9.15 Hz, 1H), 5.13(br s, 2H). 13C NMR (125 MHz, DMSO-d6): δ = 169.34, 149.06, 135.66, 129.09, 117.08, 115.27, 113.62
NH2
H2NOC
1H NMR (400 MHz, DMSO-d6): δ = 7.54 (d, JH,H = 8.60 Hz, 2H), 6.78 (br s, 4H), 6.48 (d, JH,H = 8.64 Hz, 2H). 13C NMR (125 MHz, DMSO-d6): δ = 168.64, 152.23, 129.64, 121.31, 112.96
HO
NH2
1H NMR (500 MHz, CDCl3): δ = 7.15 (d, JH,H = 8.15 Hz, 2H), 6.67 (d, JH,H = 8.25 Hz, 2H), 4.55 (s, 2H). 13C NMR (125 MHz, CDCl3): δ = 146.13, 131.10, 128.88, 115.20, 65.43
NH2
NH2
1H NMR (400 MHz, CDCl3): δ = 6.73-6.68 (m, 4H), 3.32(br s, 4H). 13C NMR (125 MHz, CDCl3): δ = 130.10, 115.62, 112.12
Page 8
8
NH2
NO2
1H NMR (500 MHz, CDCl3): δ = 7.57 (dd, JH,H = 8.05 Hz, JH,H = 2.1 Hz, 1H), 7.48 (t, JH,H = 2.15 Hz, 1H), 7.26 (t, JH,H = 8.12 Hz, 1H), 6.94(dd, JH,H = 8.05 Hz, JH,H = 2.25 Hz, 1H), 2.40 (br s, 2H). 13C NMR (125 MHz, CDCl3): δ = 158.14, 147.49, 130.0, 120.68, 113.26, 109.12
NH2
NO2F
F
1H NMR (500 MHz, CDCl3): δ = 8.72 (d, JH,H = 7.95 Hz, 1H), 6.93 (d, JH,H = 12.4 Hz ,1H). 13C NMR (125 MHz, CDCl3): δ = 160.01, 157.84, 157.18, 135.67, 124.91, 104.62
N
NH2
1H NMR (400 MHz, CDCl3): δ = 8.08 (d, JH,H = 2.64 Hz, 1H), 7.99 (dd, JH,H = 4.6 Hz , JHH = 1.22 Hz, 1H), 7.06-7.02 (m, 1H), 6.96-6.93(m,1H), 3.60(br s, 2H). 13C NMR (125 MHz, CDCl3): δ = 142.57, 140.08, 137.55, 123.79, 121.54
N
H2N
1H NMR (500 MHz, CDCl3): δ = 8.64(d, JH,H = 4.01 Hz, 1H), 7.89 (t, JH,H = 9.65 Hz, 2H), 7.25(t, JH,H = 4.80 Hz, 1H), 7.14(dd, JH,H = 9.07 Hz, JH,H = 2.65 Hz, 1H), 6.88 (d, JH,H = 2.5Hz, 1H), 3.84 (br s, 2H). 13C NMR (125 MHz, CDCl3): δ =146.83, 144.72, 143.48, 133.90, 130.58, 129.89, 121.67, 121.46, 107.49
Page 9
9
Copies of 1H and 13C NMR Spectra of Amines
NH2
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
-2
0
2
4
6
8
10
12
14
16
18
20
22
24
26
28
30
32
34
36
38
40
1.06
0.99
0.50
1.00
3.34
68
6.68
376.
6855
6.70
056.
7024
6.75
366.
7553
6.76
836.
7701
6.78
326.
7849
7.14
947.
1653
7.18
087.
2526
0102030405060708090100110120130140150160170180f1 (ppm)
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
76.8
877
.13
77.3
9
115.
2311
8.68
129.
38
146.
73
Page 10
10
NH2
Me
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
0
1
2
3
4
5
6
7
8
9
3.15
2.39
1.98
0.96
1.00
2.25
94
3.46
61
6.47
736.
5041
6.52
006.
5318
6.58
186.
5968
7.02
427.
0395
7.05
477.
2524
0102030405060708090100110120130140150160f1 (ppm)
-0.03
-0.02
-0.01
0.00
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
0.20
0.21
0.22
0.23
21.4
9
76.8
377
.08
77.3
4
112.
4611
6.13
119.
7212
3.45
129.
25
141.
00
Page 11
11
NH2
Me
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
-1
0
1
2
3
4
5
6
7
8
9
10
11
3.15
2.01
3.00
1.00
2.09
59
3.33
72
4.85
53
6.25
286.
2713
6.29
396.
3134
6.32
626.
8133
6.83
236.
8514
0102030405060708090100110120130140150160170180190f1 (ppm)
-0.05
0.00
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
21.7
4
39.3
439
.55
39.7
539
.96
40.1
740
.38
40.5
9
111.
6811
5.05
117.
07
129.
20
138.
22
149.
02
Page 12
12
NH2
Me
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
-1
0
1
2
3
4
5
6
7
8
9
10
11
12
13
1.58
1.00
1.00
1.00
2.19
53
3.34
83
6.59
596.
6168
6.94
886.
9685
7.24
69
0102030405060708090100110120130140150160170180190f1 (ppm)
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
20.6
8
76.7
877
.10
77.4
2
115.
37
127.
9212
9.83
143.
81
Page 13
13
NH2
MeO
1.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
-2
0
2
4
6
8
10
12
14
16
18
20
22
24
0.90
1.59
0.98
1.00
3.31
25
3.73
31
6.63
636.
6588
6.72
586.
7479
7.24
71
0102030405060708090100110120130140150160170180190f1 (ppm)
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.0
2.1
2.2
2.3
55.8
2
76.7
877
.10
77.4
1
115.
0211
6.62
139.
77
152.
90
Page 14
14
NH2
MeS
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
-1
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
1.52
1.03
1.00
1.00
2.39
76
3.58
86
6.60
986.
6313
7.15
657.
1777
7.24
58
-100102030405060708090100110120130140150160170180f1 (ppm)
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
18.8
8
76.7
877
.10
77.4
2
115.
83
125.
93
131.
16
145.
15
Page 15
15
NH2Me
Me
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
0
5
10
15
20
25
30
35
40
45
6.44
2.03
1.00
1.99
2.21
17
3.56
92
6.65
966.
6779
6.69
716.
9678
6.98
637.
2453
0102030405060708090100110120130140150160170180f1 (ppm)
-0.2
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
2.0
2.1
2.2
17.7
3
76.8
777
.19
77.5
0
118.
1212
1.82
128.
36
142.
81
Page 16
16
NH2
F
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
-1
0
1
2
3
4
5
6
7
8
9
10
11
1.04
1.06
1.09
1.00
6.96
056.
9758
6.99
127.
0568
7.07
357.
2521
7.45
637.
4711
7.48
687.
7492
7.76
37
0102030405060708090100110120130140150160170180190f1 (ppm)
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
76.8
377
.09
77.3
4
116.
2112
0.16
125.
51
133.
6313
6.99
151.
34
Page 17
17
NH2
Cl
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
-5
0
5
10
15
20
25
30
35
40
45
50
55
60
2.07
0.99
0.97
0.98
1.00
3.67
27
6.51
456.
5166
6.52
026.
5223
6.53
516.
5371
6.54
086.
5428
6.65
006.
6553
6.66
066.
7044
6.72
397.
0314
7.05
157.
0713
7.24
60
0102030405060708090100110120130140150160170180190f1 (ppm)
-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
76.8
477
.16
77.4
8
113.
2911
5.01
118.
53
130.
4213
4.92
147.
74
Page 18
18
F
NH2
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
-5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
1.12
1.00
6.89
426.
9126
7.25
25
8.15
928.
1778
0102030405060708090100110120130140150160170180f1 (ppm)
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
66.5
172
.33
72.5
872
.84
110.
88
121.
58
158.
76
Page 19
19
NH2
Cl
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
-2
0
2
4
6
8
10
12
14
16
18
20
22
24
26
28
30
32
34
0.97
1.00
1.00
3.64
21
6.58
196.
6036
7.07
337.
0951
7.24
62
0102030405060708090100110120130140150160170180190f1 (ppm)
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
76.7
777
.09
77.4
1
116.
3012
3.27
129.
19
145.
00
Page 20
20
NH2
Br
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
-5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
1.04
1.00
0.99
3.57
78
6.52
976.
5504
7.20
767.
2283
0102030405060708090100110120130140150160170180190f1 (ppm)
-1
0
1
2
3
4
5
6
7
8
9
10
1176.8
577
.17
77.4
8
110.
25
116.
81
132.
09
145.
53
Page 21
21
NH2
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
-1
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
0.47
0.95
0.97
1.00
1.26
02
4.14
23
6.77
606.
7784
6.78
996.
7923
7.25
267.
2882
7.30
227.
3130
7.44
557.
4498
7.45
407.
4564
7.46
007.
4646
7.81
10
0102030405060708090100110120130140150160170180190f1 (ppm)
-0.04
-0.02
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
0.20
0.22
0.24
0.26
0.28
0.30
0.32
0.34
0.36
0.38
74.2
874
.53
74.7
9
107.
23
116.
5311
8.30
121.
2412
2.37
123.
3512
3.85
126.
0813
1.98
139.
60
Page 22
22
NH2
COMe
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
0
5
10
15
20
25
30
35
40
45
3.24
1.85
2.00
1.04
1.00
2.55
32
6.25
846.
6050
6.60
746.
6130
6.61
606.
6223
6.62
546.
6336
6.63
676.
6429
6.64
597.
2373
7.24
06
7.67
757.
6812
7.69
837.
7020
0102030405060708090100110120130140150160170180190200f1 (ppm)
0.0
0.5
1.0
1.5
2.0
2.5
27.9
4
76.8
477
.16
77.4
8
115.
8111
7.29
118.
32
132.
1213
4.46
150.
37
200.
84
Page 23
23
NH2
COMe
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
-2
-1
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
1.00
2.41
0.93
2.03
17
6.85
606.
8599
6.87
216.
8760
7.21
267.
2281
7.24
377.
2526
7.25
897.
2629
7.31
437.
3296
0102030405060708090100110120130140150160170180190200f1 (ppm)
-0.02
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
0.20
0.22
0.2429.7
6
76.8
277
.08
77.3
3
114.
1511
9.02
119.
75
129.
50
139.
58
146.
69
198.
46
Page 24
24
NH2
MeOC
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
-2
0
2
4
6
8
10
12
14
16
18
20
22
24
26
28
1.57
0.92
1.04
1.00
2.49
33
4.11
47
6.62
746.
6444
7.25
32
7.78
797.
8051
-100102030405060708090100110120130140150160170180190200f1 (ppm)
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
21.4
0
72.0
872
.34
72.5
9
109.
05
123.
2712
6.12
146.
40
191.
78
Page 25
25
NH2
CN
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
-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
0.92
0.84
0.84
1.00
6.73
886.
7432
6.75
476.
7592
6.78
396.
8951
6.91
027.
0885
7.10
417.
1199
7.15
05
0102030405060708090100110120130140150160170180f1 (ppm)
-0.02
-0.01
0.00
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
0.20
0.21
0.22
76.8
477
.09
77.3
4
113.
0411
7.54
119.
2712
2.12
130.
13
146.
97
Page 26
26
NH2
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
-2
0
2
4
6
8
10
12
14
16
18
20
22
24
26
2.41
1.18
1.21
2.00
1.04
1.01
1.00
3.52
01
5.20
335.
2252
5.68
745.
7220
6.59
346.
5979
6.59
946.
6097
6.61
396.
6356
6.64
916.
6708
6.74
446.
7481
6.75
206.
8319
6.84
717.
1096
7.12
537.
1407
0102030405060708090100110120130140150160170180190f1 (ppm)
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
76.8
577
.10
77.3
6
112.
9011
3.65
114.
9211
7.10
129.
4913
7.13
138.
8314
6.52
Page 27
27
NH2
CONH2
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
0
1
2
3
4
5
6
7
8
9
10
1.90
1.00
1.09
3.04
1.10
3.39
62
5.12
72
6.63
776.
6560
6.93
316.
9486
7.00
317.
0081
7.01
687.
0324
7.07
047.
6756
0102030405060708090100110120130140150160170180190f1 (ppm)
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.039.4
639
.63
39.8
039
.96
40.1
340
.30
40.4
6
113.
6211
5.27
117.
08
129.
09
135.
66
149.
06
169.
34
Page 28
28
NH2
H2NOC
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
-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
0.81
0.93
0.57
1.00
3.37
84
5.58
35
6.46
586.
4873
6.77
56
7.52
607.
5475
0102030405060708090100110120130140150160170180f1 (ppm)
-0.05
0.00
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
39.3
439
.55
39.7
639
.97
40.1
840
.39
40.5
9
112.
96
121.
31
129.
64
152.
23
168.
64
Page 29
29
HO
NH2
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
-2
0
2
4
6
8
10
12
14
16
18
20
22
24
26
0.96
0.95
1.00
4.54
59
6.65
806.
6745
7.14
567.
1619
7.25
26
0102030405060708090100110120130140150160170180190f1 (ppm)
-0.02
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
0.20
0.22
0.24
0.26
0.28
0.30
0.32
65.4
3
76.8
377
.09
77.3
4
115.
20
128.
8813
1.10
146.
13
Page 30
30
NH2
NH2
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
-5
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
1.00
0.90
3.32
16
6.68
026.
6855
6.68
976.
6932
6.69
906.
7033
6.70
706.
7171
6.72
046.
7251
6.73
067.
2460
0102030405060708090100110120130140150160170f1 (ppm)
-1
0
1
2
3
4
5
6
7
8
9
10
11
12
13
72.2
272
.47
72.7
3
112.
1211
5.62
130.
10
Page 31
31
NH2
NO2
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
-2
0
2
4
6
8
10
12
14
16
18
20
22
24
26
28
30
2.40
1.00
1.31
0.98
0.96
3.99
10
6.92
466.
9291
6.94
076.
9452
7.24
827.
2528
7.26
447.
2806
7.47
347.
4778
7.48
217.
5559
7.56
017.
5720
7.57
627.
7237
0102030405060708090100110120130140150160170180190f1 (ppm)
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.4076.8
477
.10
77.3
5
109.
1211
3.26
120.
68
130.
00
147.
49
158.
14
Page 32
32
NH2
NO2F
F
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
0
5
10
15
20
25
30
35
40
1.25
1.00
6.91
506.
9398
8.71
268.
7285
0102030405060708090100110120130140150160170180f1 (ppm)
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
76.8
577
.10
77.3
6
104.
62
124.
91
135.
67
157.
1815
7.84
160.
01
Page 33
33
N
NH2
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
-1
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
2.06
1.05
1.00
1.01
1.00
3.60
38
6.92
996.
9335
6.93
696.
9402
6.94
996.
9535
6.95
716.
9599
7.02
427.
0356
7.03
757.
0447
7.05
627.
2462
7.98
547.
9883
7.99
687.
9998
8.06
918.
0757
0102030405060708090100110120130140150160170180f1 (ppm)
-0.1
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
76.7
977
.11
77.4
3
121.
5412
3.79
137.
5514
0.08
142.
57
Page 34
34
N
H2N
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
-1
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
2.07
1.00
1.07
1.21
2.12
1.00
3.84
32
6.87
686.
8818
7.12
777.
1326
7.14
537.
1506
7.23
817.
2467
7.25
357.
2631
7.87
027.
8895
7.90
81
8.63
498.
6429
0102030405060708090100110120130140150160170180f1 (ppm)
-0.05
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
76.8
577
.10
77.3
5
107.
49
121.
4612
1.67
129.
8913
0.57
133.
90
143.
4814
4.72
146.
83
