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Supporting InformationNitrogen rich graphitic-carbon stabilized cobalt nanoparticles for
chemoselective hydrogenation of nitroarenes at milder
conditions
CONTENTS
Page NoA. General Information 2
B. Synthesis of glycoluril 3
C. Synthesis of CB[6] 3
D. Particle distribution of the catalyst 4
E. TEM elemental mapping of catalyst 4
F. Thermogravimetric analysis of the catalyst 5
G. Recyclability of the catalyst 5
H. TEM images of the recycled catalyst 6
I. Filtration method procedure and its results 6
J. Procedure for preparation of ICP samples 7
K. Comparison chart 7
L. Analytical data and NMR spectra of the products 8
M. References 46
Electronic Supplementary Material (ESI) for Inorganic Chemistry Frontiers.This journal is © the Partner Organisations 2018
2
(A) General Information
All the chemicals were purchased from commercial grade and used without further any
treatment. The hydrogen gas used was from Hydro Gas India Pvt. Ltd., India.
All the hydrogenation reactions were performed in a 100 mL stainless steel autoclave high-
pressure reactor (Autoclave Engineers, EZE-Seal Reactor, USA). 1H and 13C NMR spectra of
compounds were measured in CDCl3 and CD3OD as a solvent by using TMS as an internal
standard, on a Bruker Avance 500 MHz FT-NMR. Infrared Spectra were recorded using KBr
pellet on a Perkin-Elmer, G-FTIR. The catalyst was activated overnight at 120 oC prior to use.
Transmission Electron Microscopy images of glycoluril, Co catalyst was carried out on a JEOL
JEM-2100 microscope with an acceleration voltage of 200 kV using carbon coated 200 mesh
copper grids. The samples were ultrasonically dispersed in acetone for 10 min and deposited on
the copper grid using capillary and left to dry overnight in air. Thermogravimetric analysis
(TGA) was carried out by using a Mettler TGA/SDTA 851e equipment in flowing N2 (flow rate
= 50 ml/min), at a heating rate of 10 oC/min and data were processed by Stare software. XRD
pattern of the samples were analyzed on a Philips X’pert X-ray powder diffractometer by using
Cu Kα (λ= 1.54178Å) radiation. Samples were grounded to make fine powder before XRD
analysis. XPS analysis of the catalyst was done on Omicron Nanotechnology. Inductive
Coupled Plasma (ICP) of the cobalt catalyst was carried out on Perkin Elmer, Optima 2000. Gas
Chromatography of the samples was carried out on a Shimadzu GC-2010 with a capillary
column, column oven temperature of 110 oC, FID of 200 oC, Pressure was 110 kPa. Samples
were prepared by using DCM as a solvent.
3
(B) Synthesis of glycoluril1
In a single necked 500 mL RB flask, 40% glyoxal (40 mL; 0.35 mol) and urea (53.4 g, 0.89 mol,
2 eqv.) were taken, and the resulting solution was stirred for 15-20 min. Subsequently, water (80
mL) was added to the reaction mixture and further stirred for 15 min followed by the addition of
8.5 mL conc. HCl in 20 mL of water very slowly. After complete addition of acid (pH= 1.5-2),
the reaction mixture was refluxed on a steam bath that triggered precipitation of white solid. The
heating and stirring were continued for about 45 min, cooled to room temperature, poured into
ice water, filtered, and the solid was washed with cold water (2 x 50 mL) and finally with
acetone (2 x 50 mL). The resulting white solid was allowed to dry overnight at 80-85 oC. (Yield:
32.69 g, 65%).
(C) Synthesis of CB[6]2
In a single necked 250 mL RB flask which is equipped with dean-stark apparatus and a
condenser, glycoluril (15 g, 106 mmol) and 37% aqueous formaldehyde were taken to which
conc. H2SO4 (14.3 mL) and water (100 mL) were added, and the resulting mass was heated for
12 h. During that time water was removed completely from the reaction mixture, after that the
reaction mixture was stirred at 160 oC for 24 h. Then the reaction mixture was cooled down to
RT and poured into water (250 mL). A yellowish precipitate was formed, which was filtered off,
and the solid mass was dissolved in Conc. HCl. The clear brown solution was diluted with water
to get a white precipitate that was washed thoroughly with water and dried at 130-140oC (Yield:
80.9%).
4
(D) Particle distribution of the catalyst
(E) TEM elemental mapping of catalyst
Co N
CO
5
(F) Thermogravimetric analysis of the catalyst
(G) Recyclability of the catalyst
1 2 3 4 5
100 100 100 99 96
100 100 100 100 100
Conversion
Selectivity
No. of cycles
6
(H) TEM images of the recycled catalyst
a b
a b
(I) Filtration method procedure and its results
To verify the cobalt leaching in the reaction mixture, the filtration test was carried out at room
temperature. A 100 mg of catalyst was stirred with 5 mL of nitrobenzene in 20 mL of water-THF
mixture under typical reaction conditions, i.e. bubbling hydrogen gas at 50 oC. After 1.5 h, the
reaction showed 56% of conversion of nitrobenzene without affecting selectivity of aniline. At
this point the catalyst was removed from the liquid phase by filtration through Whatman filter
paper and the reaction mixture was allowed to further react under reaction conditions. It was
observed that in the absence of a catalyst, no further change in nitrobenzene conversion was
observed even after 3 h which confirms zero Co leaching.
(J) Procedure for preparation of ICP samples
Catalyst sample was mixed with pure conc. HNO3 acid solution (20% v/v) in 50 mL PFA beaker.
The sample was heated in a Parr bomb at 100 oC in an oven for 3 h. After cooling the sample, the
solution was taken out in a volumetric flask. The solution was then diluted to 100 mL using milli
7
Q water by using calibrated volumetric flask which was further subjected to ICP analysis. Metal
leaching was studied by ICP-AES analysis of the catalyst before, after first and third reaction
cycles. The Co concentration was found to be negligible before and after the reaction, which
confirmed negligible Co leaching; this is due to strong metal support interaction.
(K) Table 1. Comparison chart
No. Catalyst Reaction Conditions
Hydrogen Source
Reaction Scale
Time Yield Ref.
1 Co(Phen)2(OAc)2adsorbed on Vulcan XC72R
110 oC, 50 bar, THF:H2O
0.5mmol 4h 98 3
2 Co3O4/NGr@C 43 CoOx@NCNTs 110 °C, EtOH, 30
bar1mmol 2.5h 98 5
4 Co nanocomposite 110 °C, EtOH: H2O, 50 bar
1.5mmol 15h >99 6
5 Co/CoO@Carbon 120 °C, THF/H2O, 30 bar
1mmol 4-24h >80 7
6 Co-Co3O4/NGr@C or Fe2O3/NGr@C
70-120 °C, EtOH: H2O, 20 bar, Et3N
H2 0.5mmol 20-28h >99 8
7 Nanolayered Co-Mo-S
150 oC, 11 bar, Toluene
0.25 7h >99 9
8 Zr12-TPDC-Co 110 oC, 40 bar, Toluene
0.4 42h 100 10
9 Co@NMC 80 °C, 10 bar, EtOH 1 1.5h 99 1110 CoPd@CNT RT, H2O:MeOH NaBH4 1 3-5 min >99 1211 Co-
Co3O4@carbon-700
110 oC, 40 bar, EtOH/H2O
0.5 6 >99 13
12 Co@g-C/N-800 50 °C, H2O:THF, 10 bar
H2 48mmol 12h >99 This Work
8
(L) Analytical data and NMR spectra of the products
1H NMR of aniline14
1H NMR (CDCl3, 500MHz, TMS) δ = 7.15-7.13(m, 2H), 6.76-6.73(m, 1H), 6.66-6.65(d, 2H, J=
7.5Hz), 3.60 (s, 2H).
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1 (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
2.00
1.96
1.00
2.01
-0.0
0
3.60
6.65
6.66
6.73
6.74
6.76
7.13
7.14
7.15
9
13C NMR of aniline13C NMR (CDCl3, 125MHz) δ = 115.02, 118.44, 129.20, 146.30.
7580859095100105110115120125130135140145150f1 (ppm)
-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
76.7
977
.00
77.2
1
115.
02
118.
44
129.
20
146.
30
10
1H NMR of 1-naphthylamine14
1H NMR (CDCl3, 500MHz, TMS) δ = 7.73-7.71(m, 2H), 7.38-7.23 (m, 4H), 6.70-6.69 (d,
1H, J= 7), 4.05 (s, 2H).
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
2.07
1.00
4.11
2.02
-0.0
0
4.05
6.69
6.70
7.23
7.36
7.37
7.38
7.71
7.72
7.73
11
13C NMR of 1-naphthylamine
13C NMR (CDCl3, 125MHz) δ = 142.02, 134.35, 128.51, 126.29, 125.81, 124.82, 123.61,
120.75, 118.94, 109.65.
7580859095100105110115120125130135140145f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
6E+08
7E+08
76.7
477
.00
77.2
5
109.
65
118.
94
120.
75
123.
6112
4.82
125.
8112
6.29
128.
51
134.
35
142.
02
12
1H NMR of 1,2-diaminobenzene14
1H NMR (CDCl3, 500MHz, TMS) δ = 6.72-6.68 (m, 4H), 3.38 (s, 4H).
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1 (ppm)
0
1
2
3
4
5
6
7
8
9
10
4.00
4.03
-0.0
0
3.38
6.68
6.69
6.69
6.69
6.70
6.71
6.71
6.72
13
13C NMR of 1,2-diaminobenzene
13C NMR (CDCl3, 125MHz) δ = 134.66, 120.20, 116.68.
74767880828486889092949698102106110114118122126130134f1 (ppm)
-0.005
0.000
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
0.080
0.08576.7
977
.00
77.2
1
116.
68
120.
20
134.
66
14
1H NMR of 1,4-diaminobenzene14
1H NMR (CDCl3, 500MHz, TMS) δ = 6.56 (s, 4H), 3.32 (bs, 4H).
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1 (ppm)
-1
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
4.00
3.95
-0.0
0
3.32
6.56
15
13C NMR of 1,4-diaminobenzene
13C NMR (CDCl3, 125MHz) δ = 116.65, 138.53.
707580859095100105110115120125130135140f1 (ppm)
-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
76.7
977
.00
77.2
1
116.
65
138.
53
16
1H NMR of 1,3-diaminobenzene14
1H NMR (MeOD, 500MHz, TMS) δ = 6.81(m, 1H), 6.14-6.10 (m, 2H), 4.84 (s, 8H), 3.29 (s,
1H).
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1 (ppm)
-1
0
1
2
3
4
5
6
7
8
9
10
11
0.97
8.00
2.32
0.92
0.00
3.29
4.84
6.10
6.14
6.81
17
13C NMR of 1,3-diaminobenzene
13C NMR (MeOD, 125MHz) δ = 149.34, 130.83, 107.90, 104.55.
4550556065707580859095100105110115120125130135140145150f1 (ppm)
-0.005
0.000
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
0.08048.7
248
.86
49.0
149
.15
49.2
949
.43
49.5
7
104.
55
107.
90
130.
83
149.
34
18
1H NMR of 2-chloroaniline14
1H NMR (CDCl3, 500MHz, TMS) δ = 7.23-7.03 (m, 2H), 6.74-6.66 (m, 2H), 4.01 (s, 2H).
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (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
2.00
1.91
1.94
0.00
4.01
6.66
6.67
6.69
6.73
6.74
7.03
7.05
7.06
7.22
7.23
19
13C NMR of 2-chloroaniline
13C NMR (CDCl3, 125MHz) δ = 142.85, 129.34, 127.56, 119.21, 118.95, 115.81.
7580859095100105110115120125130135140145150f1 (ppm)
-0.005
0.000
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
76.7
977
.00
77.2
1
115.
81
118.
9511
9.21
127.
56
129.
34
142.
85
20
1H NMR of 2-chloro-1,4-diaminobenzene16
1H NMR (CDCl3, 500MHz, TMS) δ = 8.32-8.26 (m, 2H), 8.10-8.07 (m, 1H), 4.38 (s, 4H).
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
4.33
1.00
1.01
0.94
-0.0
0
4.38
8.07
8.10
8.26
8.27
8.32
21
13C NMR of 2-chloro-1,4-diaminobenzene
13C NMR (CDCl3, 125MHz) δ = 154.50, 149.61, 131.12, 127.35, 126.19, 125.08.
7580859095100105110115120125130135140145150155f1 (ppm)
-0.005
0.000
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
0.080
0.085
0.090
76.7
477
.00
77.2
6
125.
0812
6.19
127.
35
131.
12
149.
61
154.
50
22
1H NMR of 4-bromoaniline5
1H NMR (CDCl3, 500MHz, TMS) δ = 7.24-7.22 (d, 2H, J= 9), 6.57-6.55 (d, 2H, J= 9), 3.65
(s, 2H).
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
1E+09
1E+09
1.94
2.00
1.94
-0.0
0
3.65
6.55
6.57
7.22
7.24
23
13C NMR of 4-bromoaniline
13C NMR (CDCl3, 125MHz) δ = 145.39, 131.99, 116.67, 110.18.
7580859095100105110115120125130135140145150f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+0876.7
477
.00
77.2
5
110.
18
116.
67
131.
99
145.
39
24
1H NMR of 4-chloroaniline5
1H NMR (CDCl3, 500MHz, TMS) δ = 7.10-7.09 (d, 2H, J= 8.5), 6.61-6.59 (d, 2H, J= 8.5), 3.64
(s, 2H).
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1 (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
2.00
1.88
1.84
0.00
3.64
6.59
6.61
7.09
7.10
25
13C NMR of 4-chloroaniline
13C NMR (CDCl3, 125MHz) δ = 144.91, 129.08, 123.12, 116.19.
7580859095100105110115120125130135140145f1 (ppm)
-0.005
0.000
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
0.080
0.085
76.7
977
.00
77.2
1
116.
19
123.
12
129.
08
144.
91
26
1H NMR of 2,3,4-fluoroaniline14
1H NMR (CDCl3, 500MHz, TMS) δ = 8.47-8.43 (m, 1H), 8.07-8.03 (m, 1H), 4.69 (s, 2H).
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
0
1
2
3
4
5
6
7
8
9
10
11
2.00
0.89
0.91
0.00
4.69
8.03
8.05
8.07
8.43
8.45
8.47
27
13C NMR of 2,3,4-fluoroaniline
13C NMR (CDCl3, 150MHz) δ = 144.81-144.74 (d, 0.5C), 143.22-143.15 (d, 0.5, C), 141.46-
141.21 (m, 1C), 139.85-139.47 (m, 1C), 132.03-131.96 (m, 1C), 111.36-111.22 (m, 1C), 109.54
(s, 1C)
7580859095100105110115120125130135140145f1 (ppm)
-0.005
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0.045
0.050
76.7
977
.00
77.2
1
109.
5411
1.22
111.
2411
1.34
111.
36
131.
9613
2.03
139.
4713
9.56
139.
6713
9.85
141.
2114
1.38
141.
4614
3.15
143.
2214
4.74
144.
81
28
19F NMR of 2,3,4-fluoroaniline
19F NMR (CDCl3, 564.72MHz) δ = (-)148.76- (-)148.86 (m, 1F), (-)155.48- (-)155.56 (m,
1F), (-)160.69- (-)160.82 (m, 1F).
-165-164-163-162-161-160-159-158-157-156-155-154-153-152-151-150-149-148-147f1 (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
-160
.82
-160
.81
-160
.79
-160
.78
-160
.76
-160
.74
-160
.73
-160
.70
-160
.69
-155
.56
-155
.54
-155
.52
-155
.51
-155
.49
-155
.48
-148
.86
-148
.85
-148
.84
-148
.83
-148
.81
-148
.80
-148
.79
-148
.78
-148
.77
-148
.76
-148
.76
29
1H NMR of 4-bromo-1,2-diaminobenzene16
1H NMR (CDCl3, 500MHz, TMS) δ = 8.51-8.18 (m, 3H), 4.20 (bs, 4H).
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
0
1
2
3
4
5
6
7
8
9
10
11
12
3.85
3.42
-0.0
0
4.20
8.18
8.20
8.38
8.48
8.50
8.51
30
13C NMR of 4-bromo-1,2-diaminobenzene
13C NMR (CDCl3, 125MHz) δ = 134.69, 122.60, 120.27, 119.03, 117.88, 116.73.
7880828486889092949698102106110114118122126130134f1 (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
76.7
977
.00
77.2
1
116.
7311
7.88
119.
0312
0.27
122.
60
134.
69
31
1H NMR of 4-methylaniline14
1H NMR (CDCl3, 500MHz, TMS) δ = 6.96-6.95 (d, 2H, J= 6.5), 6.60-6.59 (d, 2H, J= 7), 3.51
(bs, 2H), 2.23 (s, 3H).
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1 (ppm)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
3.21
2.00
2.00
1.99
0.00
2.23
3.51
6.59
6.60
6.95
6.96
32
13C NMR of 4-methylaniline
13C NMR (CDCl3, 125MHz) δ = 160.41, 142.83, 140.35, 124.73, 6.25.
102030405060708090100110120130140150160f1 (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
6.25
76.7
477
.00
77.2
7
124.
73
140.
3514
2.83
160.
41
33
1H NMR of 4-aminobenzenesulfonamide14
1H NMR (MeOD, 500MHz, TMS) δ = 7.72-7.57 (m, 2H), 6.99-6.97 (d, 2H, J= 9), 6.69-6.68 (d,
1H, J= 8.5), 4.85 (s, 6H), 3.30 (s, 1H).
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (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
8.5
9.0
0.70
6.00
0.73
1.49
0.72
1.50
-0.0
0
3.30
4.85
6.68
6.69
6.97
6.99
7.57
7.58
7.71
7.72
34
13C NMR of 4-aminobenzenesulfonamide
13C NMR (MeOD, 125MHz) δ = 156.72, 135.16, 129.13, 128.50, 114.55, 113.37.
4550556065707580859095100105110115120125130135140145150155160f1 (ppm)
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
48.6
448
.81
48.9
849
.15
49.3
249
.49
49.6
6
113.
3711
4.55
128.
5012
9.13
135.
16
156.
72
35
1H NMR of 3-aminobenzonitrile14
1H NMR (CDCl3, 500MHz, TMS) δ = 7.23-7.20 (m, 1H), 7.01-7.00 (m, 1H), 6.90-6.86 (m, 2H),
3.91 (bs, 2H).
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
2.00
0.97
0.95
0.98
0.98
0.00
3.91
6.86
6.86
6.87
6.87
6.90
6.90
7.00
7.01
7.20
7.22
7.23
36
13C NMR of 3-aminobenzonitrile
13C NMR (CDCl3, 125MHz) δ = 146.92, 129.99, 121.86, 119.29, 117.35, 112.80.
7580859095100105110115120125130135140145150f1 (ppm)
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
76.7
977
.00
77.2
1
112.
80
117.
35
119.
29
121.
86
129.
99
146.
92
37
1H NMR of 4-aminobenzonitrile5
1H NMR (CDCl3, 500MHz, TMS) δ = 9.24-9.22 (d, 2H, J= 9), 8.31-8.29 (d, 2H, J=9), 5.32 (bs,
2H).
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (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
2.00
2.01
1.94
0.00
5.32
8.29
8.31
9.22
9.24
38
13C NMR of 4-aminobenzonitrile
13C NMR (CDCl3, 125MHz) δ = 150.50, 133.67, 123.64, 120.15, 114.32, 99.73.
7580859095100105110115120125130135140145150f1 (ppm)
-0.002
-0.001
0.000
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
0.023
76.7
977
.00
77.2
1
99.7
3
114.
32
120.
15
123.
64
133.
67
150.
50
39
1H NMR of 2-aminophenol14
1H NMR (MeOD, 500MHz, TMS) δ = 6.74-6.56 (m, 6H), 4.88 (s, 6H), 3.30 (s, 1H).
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1 (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
0.72
6.20
6.00
-0.0
0
3.30
4.88
6.56
6.58
6.59
6.62
6.63
6.65
6.68
6.69
6.72
6.74
40
13C NMR of 2-aminophenol
1H NMR (MeOD, 125MHz) δ = 146.70, 136.13, 121.19, 120.43, 117.71, 115.71.
4550556065707580859095100105110115120125130135140145f1 (ppm)
-0.005
0.000
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
0.080
48.7
348
.87
49.0
149
.15
49.2
949
.44
49.5
8
115.
7111
7.71
120.
4312
1.19
136.
13
146.
70
41
1H NMR of 3-aminophenol17
1H NMR (MeOD, 500MHz, TMS) δ = 6.91-6.88 (t, 1H, J=8), 6.23-6.15 (m, 4H), 4.87 (s, 5H),
3.31 (s, 1H).
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1 (ppm)
-5E+07
0
5E+07
1E+08
2E+08
2E+08
2E+08
3E+08
4E+08
4E+08
4E+08
5E+08
6E+08
6E+08
6E+08
7E+08
8E+08
0.48
4.96
3.90
1.31
-0.0
0
3.31
4.87
6.15
6.16
6.17
6.21
6.21
6.23
6.88
6.89
6.91
42
13C NMR of 3-aminophenol
1H NMR (MeOD, 125MHz) δ = 159.16, 149.84, 130.86, 108.61, 106.62, 103.79.
404550556065707580859095100105110115120125130135140145150155160f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
1E+09
1E+09
2E+09
2E+09
2E+09
48.5
348
.70
48.8
749
.04
49.2
249
.38
49.5
6
103.
7910
6.62
108.
61
130.
86
149.
84
159.
16
43
1H NMR of 4-aminophenol5
1H NMR (MeOD, 500MHz, TMS) δ = 6.65-6.59 (m, 4H), 4.88 (s, 6H), 3.31 (s, 1H).
0.00.51.01.52.02.53.03.54.04.55.05.56.06.5f1 (ppm)
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
1E+09
1E+09
2E+09
0.63
5.00
4.22
-0.0
0
3.31
4.88
6.59
6.60
6.63
6.65
44
13C NMR of 4-aminophenol
13C NMR (MeOD, 125MHz) δ = 151.44, 140.34, 118.69, 116.88.
4550556065707580859095100105110115120125130135140145150f1 (ppm)
-1E+08
0
1E+08
2E+08
3E+08
4E+08
5E+08
6E+08
7E+08
8E+08
9E+08
1E+09
1E+09
1E+09
1E+09
1E+09
48.6
448
.81
48.9
849
.15
49.3
249
.49
49.6
6
116.
8811
8.69
140.
34
151.
44
45
1H NMR of 4-aminobenzoic acid14
1H NMR (DMSO, 500MHz, TMS) δ = 11.96 (bs, 1H), 7.63-7.62 (d, 2H, J= 8.5), 6.56-6.55 (d,
2H, J= 8.5), 5.87 (s, 2H), 3.39 (s, 3H), 2.51 (s, 1H).
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.5f1 (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
0.36
1.30
1.95
2.00
1.98
0.87
0.00
2.51
3.39
5.87
6.55
6.56
7.62
7.63
11.9
6
46
13C NMR of 4-aminobenzoic acid
1H NMR (DMSO-D6, 125MHz) δ = 167.55, 153.18, 131.26, 116.91, 112.60.
35404550556065707580859095100105110115120125130135140145150155160165170f1 (ppm)
-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
39.0
939
.23
39.3
739
.51
39.6
539
.79
39.9
3
112.
60
116.
91
131.
26
153.
18
167.
55
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