1
Supplementary Information
Fast synthesis of amides from ethyl salicylate under microwave radiation and solvent-free system
Rafaely N. Limaa, Valdenizia R. Silvab, Luciano de S. Santosb, Daniel P. Bezerrab, Milena
B. P. Soaresb, André L. M. Portoa*
aLaboratório de Química Orgânica e Biocatálise, Instituto de Química de São Carlos, Universidade de São Paulo, Av. João Dagnone, 1100, Ed. Química Ambiental, Santa Angelina, 13563-120, São Carlos-SP, Brazil. Tel.: +55 16 33738103; Fax: + 55 16 33739952; e-mail: [email protected]*.bFundação Oswaldo Cruz, Centro de Pesquisas Gonçalo Moniz, R. Waldemar Falcão, 121, 40296-710, Candeal, Salvador-BA, Brazil.
Summary
1. Chromatograms, GC-MS, FTIR and NMR data for the amides S-Aa to S-Aj ..........1
2. Analytical curve of ethyl salicylate ES ....................................................................22
3. References ................................................................................................................22
1. Chromatograms, GC-MS, FTIR and NMR data for the amides S-Aa to S-Aj
5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0(x1,000,000)
TIC
Figure S1. Chromatogram obtained by GC-MS (EI, 70 eV) of 2-hydroxy-N-(2-hydroxyethyl)benzamide (S-Aa).
NH
OH
OOH
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2017
2
50.0 75.0 100.0 125.0 150.0 175.00
25
50
75
100
%
121
18165 93 163138 150
14844 53 77 107 180132 165116
Figure S2. Mass spectrum (EI, 70 eV) of 2-hydroxy-N-(2-hydroxyethyl)benzamide (S-Aa).
3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 400Wavenumber (cm-1)
56
64
72
80
88
96
%Tr
ansm
ittan
ce 33873298
29342874
16341589
15491493
1358 1227
1053 752
Figure S3. FTIR spectrum (silicon plate) of 2-hydroxy-N-(2-hydroxyethyl)benzamide (S-Aa).
NH
OH
OOH
NH
OH
OOH
3
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
1.811.720.85
TMS
7.79
7.77
7.36
7.36
6.90
6.88
6.88
6.86
3.73
3.71
3.70
3.53
3.52
3.51
0.00
3.7 3.6 3.5Chemical Shift (ppm)
1.81 1.773.
733.
713.
70
3.53
3.52
3.51
6.900 6.875Chemical Shift (ppm)
1.72
6.90
6.90
6.89
6.89
6.88
6.88
6.88
6.88 7.375 7.350
Chemical Shift (ppm)
0.92
7.38
7.37
7.36
7.36
7.36
7.36
7.79 7.77Chemical Shift (p...
0.85
7.79
7.79
7.77
7.77
Figure S4. 1H NMR spectrum (400 MHz, CD3OD) of 2-hydroxy-N-(2-hydroxyethyl)benzamide (S-Aa).
220 200 180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
Methanol-d4
171.
0
161.
0
134.
712
9.1
120.
111
8.3
117.
1
61.5
49.0
43.0
Figure S5. 13C NMR spectrum (126 MHz, CD3OD) of 2-hydroxy-N-(2-hydroxyethyl)benzamide (S-Aa).
NH
OH
OOH
NH
OH
OOH
4
5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5
0.25
0.50
0.75
1.00
1.25
(x1,000,000)MIC1
Figure S6. Chromatogram obtained by GC-MS (EI, 70 eV) of 2-hydroxy-N-(3-hydroxypropyl)benzamide (S-Ab).
50.0 75.0 100.0 125.0 150.0 175.0 200.00
25
50
75
100
%
121
12065 92 19515057 17744 18816474 133 14794 105 174
Figure S7. Mass spectrum (EI, 70 eV) of 2-hydroxy-N-(3-hydroxypropyl)benzamide (S-Ab).
3500 3000 2500 2000 1500 1000 500Wavenumber (cm-1)
40
60
80
100
%Tr
ansm
ittan
ce
3362
3084 29342882
16381597
15491493
1452 13661344130812521234
1065
756696 665
625611
Figure S8. FTIR spectrum (silicon plate) of 2-hydroxy-N-(3-hydroxypropyl)benzamide (S-Ab).
NH
OH
O
OH
NH
OH
O
OH
NH
OH
O
OH
5
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
2.012.001.900.98
TMS
7.74
7.72
7.72
7.38
7.36
7.36
7.34
6.90
6.88
6.86
3.67
3.65
3.64
3.50
3.49
3.48
3.32
3.31
1.86
1.85
1.83
1.81
0.00
3.65 3.60 3.55 3.503.45Chemical Shift (ppm)
2.001.99
3.67
3.65
3.64
3.50
3.49
3.48
1.8501.825Chemical Sh...
2.01
1.86
1.85
1.83
1.82
6.875 6.850Chemical Shift (p...
1.90
6.90
6.89
6.89
6.88
6.87
6.86
7.375 7.350Chemical Shift ...
0.97
7.37
7.36
7.36
7.36
7.35
7.74 7.72Chemical S...
0.98
7.74
7.74
7.72
7.72
Figure S9. 1H NMR spectrum (400 MHz, CD3OD) of 2-hydroxy-N-(3-hydroxypropyl)benzamide (S-Ab).
220 200 180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
Methanol-d4
171.
0
161.
1
134.
712
8.7
120.
011
8.4
117.
0
60.6
49.0
37.7
33.2
Figure S10. 13C NMR spectrum (400 MHz, CD3OD) of 2-hydroxy-N-(3-hydroxypropyl)benzamide (S-Ab).
NH
OH
O
OH
NH
OH
O
OH
6
5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5
1.0
2.0
3.0
4.0
5.0
6.0
7.0
(x1,000,000)TIC
Figure S11. Chromatogram obtained by GC-MS (EI, 70 eV) of 2-hydroxy-N-(5-hydroxypentyl)benzamide (S-Ac).
50.0 75.0 100.0 125.0 150.0 175.0 200.0 225.00
25
50
75
100
%
121
120 150 22365 93164 178102 1388541 69 192 205 216 231
Figure S12. Mass spectrum (EI, 70 eV) of 2-hydroxy-N-(5-hydroxypentyl)benzamide (S-Ac).
4000 3500 3000 2500 2000 1500 1000 500Wavenumber (cm-1)
20
40
60
80
100
%Tr
ansm
ittan
ce
3358
3080
29382864
16381597
15491493
1364130812521233
1049
756664
Figure S13. FTIR spectrum (silicon plate) of 2-hydroxy-N-(5-hydroxypentyl)benzamide (S-Ac).
NH
OH
O
HO
NH
OH
O
HO
NH
OH
O
HO
7
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
4.071.981.911.00
TMS
7.75
7.73
7.36
7.36
7.34
6.89
6.88
6.86
3.58
3.57
3.55
3.41
3.39
3.38
3.31
1.65
1.63
1.59
1.57
1.46
1.45
0.00
1.6 1.5 1.4Chemical Shift (ppm)
4.07 2.04
1.66
1.65
1.63
1.62
1.60
1.59
1.57
1.46
1.45
3.573.54Chemic...
1.98
3.58
3.57
3.55
3.40 3.37Chemic...
1.97
3.41
3.39
3.38
6.89 6.88 6.87 6.86Chemical Shift (ppm)
1.91
6.89
6.89
6.88
6.88
6.87
6.86
7.37 7.35 7.33Chemical Shift (ppm)
1.02
7.37
7.36
7.36
7.35
7.34
7.34
7.74 7.72Chemical Shif...
1.00
7.75
7.75
7.73
7.73
Figure S14. 1H NMR spectrum (400 MHz, CD3OD) of 2-hydroxy-N-(5-hydroxypentyl)benzamide (S-Ac).
220 200 180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
Methanol-d4
170.
9
161.
2
134.
612
8.7
120.
011
8.4
117.
0
62.8
49.0
40.5
33.3
30.3
24.4
Figure S15. 13C NMR spectrum (127 MHz, CD3OD) of 2-hydroxy-N-(5-hydroxypentyl)benzamide (S-Ac).
NH
OH
O
HO
NH
OH
O
HO
8
5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5
1.0
2.0
3.0
4.0
(x1,000,000)TIC
Figure S16. Chromatogram obtained by GC-MS (EI, 70 eV) of 2-hydroxy-N-(2-hydroxypropyl)benzamide (S-Ad).
50.0 75.0 100.0 125.0 150.0 175.0 200.00
25
50
75
100
%
121
15065 19593
138 1775745 19677 164132107
Figure S17. Mass spectrum (EI, 70 eV) of 2-hydroxy-N-(2-hydroxypropyl)benzamide (S-Ad).
3500 3000 2500 2000 1500 1000 500Wavenumber (cm-1)
40
50
60
70
80
90
100
%Tr
ansm
ittan
ce
3364
3084 29742930
2880
16391597
154914931368
13421306
12501236
1146945926 841
754696 664
569532
Figure S18. FTIR spectrum (Silicon plate) of 2-hydroxy-N-(2-hydroxypropyl)benzamide (S-Ad).
NH
OH
O
OH
NH
OH
O
OH
NH
OH
O
OH
9
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
3.001.96 1.050.99
TMS
7.81
7.79
7.38
7.36
7.35
6.90
6.89
6.87
3.96
3.48
3.47
3.45
3.44
3.34
3.32
3.31
3.29
1.20
0.00
7.81 7.79Chemical Sh...
0.99
7.79
7.80
7.81
7.37 7.35Chemical Shift...
1.007.
357.
367.
367.
367.
38
6.900 6.875Chemical Shift ...
1.96
6.87
6.88
6.89
6.90
6.90
3.975 3.925Chemical S...
1.01
3.95
3.96
3.97
3.97 3.475 3.425
Chemical Shift ...
1.05
3.44
3.45
3.47
3.48
3.350 3.325 3.300Chemical Shift (ppm)
1.27
3.31
3.31
3.31
3.32
3.32
3.34
1.21 1.18Chemica...
3.001.
201.
21
Figure S19. 1H NMR spectrum (400 MHz, CD3OD) of 2-hydroxy-N-(2-hydroxypropyl)benzamide (S-Ad).
220 200 180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
Methanol-d4
170.
8
160.
8
134.
712
9.3
120.
111
8.3
117.
3
67.4
49.0
47.8
21.0
Figure S20. 13C NMR spectrum (127 MHz, CD3OD) of 2-hydroxy-N-(2-hydroxypropyl)benzamide (S-Ad).
NH
OH
O
OH
NH
OH
O
OH
10
5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5
1.0
2.0
3.0
4.0
5.0
6.0
7.0(x1,000,000)
TIC
Figure S21. Chromatogram obtained by GC-MS (EI, 70 eV) of N-butyl-2-hydroxybenzamide (S-Ae).
50.0 75.0 100.0 125.0 150.0 175.0 200.0 225.00
25
50
75
100
%
121
193
15065 93164 17511972 13344 53 80 107 147 213
Figure S22. Mass spectrum (EI, 70 eV) of N-butyl-2-hydroxybenzamide (S-Ae).
3500 3000 2500 2000 1500 1000 500Wavenumber (cm-1)
0
20
40
60
80
100
%Tr
ansm
ittan
ce
3375
30672961
29342870
16411595
15451493
1452 136413061233
11501038
947 860 820754
664
534
Figure S23. FTIR spectrum (Silicon plate) of N-butyl-2-hydroxybenzamide (S-Ae).
NH
OH
O
NH
OH
O
NH
OH
O
11
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
3.072.142.092.001.01
TMS
7.75
7.73
7.37
7.35
7.34
6.89
6.88
6.85
3.40
3.38
3.31
1.62
1.60
1.59
1.43
1.42
1.40
0.98
0.97
0.95
0.00
7.73Chemical ...
1.01
7.73
7.73
7.75
7.75
7.350Chemical Shift (p...
1.027.
347.
347.
357.
357.
367.
37
6.875Chemical Shift (...
2.00
6.85
6.87
6.88
6.88
6.89
3.375Chemical...
2.09
3.37
3.38
3.40
1.6251.6001.575Chemical Shift (p...
2.14
1.57
1.59
1.60
1.60
1.62
1.63
1.450 1.400Chemical Shift ...
2.16
1.39
1.40
1.42
1.43
1.45
Chemi...
3.070.
970.
98
Figure S24. 1H NMR spectrum (400 MHz, CD3OD) of N-butyl-2-hydroxybenzamide (S-Ae).
220 200 180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
Methanol-d4
170.
9
161.
2
134.
612
8.7
120.
011
8.4
117.
0
49.0
40.2
32.6
21.2
14.1
Figure S25. 13C NMR spectrum (127 MHz, CD3OD) of N-butyl-2-hydroxybenzamide (S-Ae).
NH
OH
O
NH
OH
O
12
5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5
1.0
2.0
3.0
4.0
5.0
6.0
7.0(x1,000,000)
TIC
Figure S26. Chromatogram obtained by GC-MS (EI, 70 eV) of 2-hydroxy-N-pentylbenzamide (S-Af).
50.0 75.0 100.0 125.0 150.0 175.0 200.0 225.00
25
50
75
100
%
121
20715065 93 178164 18941 13358 86 17977 147107 209118 221
Figure S27. Mass spectrum (EI, 70 eV) of 2-hydroxy-N-pentylbenzamide (S-Af).
3500 3000 2500 2000 1500 1000 500Wavenumber (cm-1)
40
60
80
100
%Tr
ansm
ittan
ce
3375
306529592932
2864
1641 15951545
14931452 1364
130612521231
11501038
754664
Figure S28. FTIR spectrum (Silicon plate) of 2-hydroxy-N-pentylbenzamide (S-Af).
NH
OH
O
NH
OH
O
NH
OH
O
13
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
4.142.132.021.05
TMS
7.75
7.73
7.37
7.36
7.34
6.89
6.88
6.85
3.38
3.37
3.36
3.32
3.31
1.63
1.62
1.59
1.39
1.38
1.37
1.36
0.94
0.93
0.00
Chemical...
3.00
0.94
0.93
1.4001.3751.350Chemical Shift (p...
4.14
1.39
1.38
1.38
1.37
1.36
1.36
1.625 1.575Chemical Shift (p...
2.13
1.65
1.63
1.63
1.62
1.61
1.59
3.3753.350Chemical S...
2.13
3.38
3.37
3.36
6.875 6.850Chemical Shift (ppm)
2.02
6.89
6.88
6.88
6.88
6.87
6.85
6.85 7.375 7.350
Chemical Shift (ppm)
1.03
7.37
7.37
7.36
7.36
7.35
7.34
7.75 7.73Chemical Shift...
1.05
7.75
7.75
7.73
7.73
Figure S29. 1H NMR spectrum (400 MHz, CD3OD) of 2-hydroxy-N-pentylbenzamide (S-Af).
220 200 180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
Methanol-d4
170.
9
161.
2
134.
612
8.7
120.
011
8.4
117.
0
49.0
40.5
30.1
23.4
14.4
Figure S30. 13C NMR spectrum (127 MHz, CD3OD) of 2-hydroxy-N-pentylbenzamide (S-Af).
NH
OH
O
NH
OH
O
14
5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5
1.0
2.0
3.0
4.0
5.0
6.0
7.0(x1,000,000)
TIC
Figure S31. Chromatogram obtained by GC-MS (EI, 70 eV) of N-heptyl-2-hydroxybenzamide (S-Ag).
50 100 150 200 2500
25
50
75
100
%
121
235151
16465 93 178 19241 20613355 86 217100 249
Figure S32. Mass spectrum (EI, 70 eV) of N-heptyl-2-hydroxybenzamide (S-Ag).
3500 3000 2500 2000 1500 1000 500Wavenumber (cm-1)
60
70
80
90
100
%Tr
ansm
ittan
ce
3329
31053013
2957 29282859
2816
16391601
15121460
13811248
11611101 826
Figure S33. FTIR spectrum (Silicon plate) of N-heptyl-2-hydroxybenzamide (S-Ag).
NH
O
OH
NH
O
OH
NH
O
OH
15
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
8.001.991.900.97
TMS
7.75
7.73
7.37
7.35
7.34
6.89
6.88
6.85
3.38
3.37
3.36
1.63
1.61
1.60
1.37
1.36
1.33
1.31
1.30
0.90
0.89
0.00
0.925 0.875Chemical ...
2.81
0.91
0.90
0.89
1.40 1.30Chemical Shift (pp...
8.001.
371.
371.
361.
321.
311.
31
1.625Chemic...
2.01
1.63
1.61
1.58
3.375 3.350Chemical Sh...
1.99
3.38
3.37
3.36
6.875 6.850Chemical Shift (ppm)
1.90
6.89
6.88
6.88
6.88
6.87
6.85
7.350Chemical Shift (ppm)
0.97
7.37
7.37
7.36
7.35
7.35
7.34
7.34
7.750 7.725Chemical Shift (...
0.97
7.75
7.75
7.73
7.73
Figure S34. 1H NMR spectrum (400 MHz, CD3OD) of N-heptyl-2-hydroxybenzamide (S-Ag).
220 200 180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
Methanol-d4
170.
8
161.
2
134.
612
8.7
120.
011
8.4
117.
1
49.0
40.5
32.9
30.4
30.1
28.1
23.7
14.4
Figure S35. 13C NMR spectrum (127 MHz, CD3OD) of N-heptyl-2-hydroxybenzamide (S-Ag).
NH
O
OH
NH
O
OH
16
5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5(x1,000,000)
TIC
Figure S36. Chromatogram obtained by GC-MS (EI, 70 eV) of N-dodecyl-2-hydroxybenzamide (S-Ah).
50 100 150 200 250 3000
25
50
75
100
%
121
151305150
120 178 1929365 20641 262248220 234 28755 27686 319
Figure S37. Mass spectrum (70 eV) of N-dodecyl-2-hydroxybenzamide (S-Ah).
3500 3000 2500 2000 1500 1000 500Wavenumber (cm-1)
60
80
100
%Tr
ansm
ittan
ce
3302
29552920
2853
17261636
15491516
14621371 1256
1101 826719
523
Figure S38. FTIR spectrum (Silicon plate) of N-dodecyl-2-hydroxybenzamide (S-Ah).
NH
O
OH
NH
O
OH
NH
O
OH
17
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
18.041.951.930.96
TMS
7.4
7.4
7.4
7.3
7.3
7.0
7.0
6.9
6.8
3.5
3.4
3.4
1.6
1.6
1.6
1.3
1.3
1.3
1.2
0.9
0.9
0.9
0.0
0.875Chemical Sh...
2.780.
890.
880.
87
1.35 1.25Chemical Shift ...
18.04
1.31
1.30
1.28
1.26
1.23
1.650 1.600Chemical Sh...
2.08
1.63
1.62
1.61
3.450 3.400Chemical Shift (ppm)
1.95
3.46
3.45
3.44
3.43
3.43
3.42
6.85 6.84 6.83 6.82Chemical Shift (ppm)
0.96
6.85
6.85
6.84
6.84
6.83
6.82
6.99 6.97Chemical Shift...
0.87
6.99
6.99
6.97
6.97
7.400 7.375 7.3507.325Chemical Shift (ppm)
1.93
7.40
7.38
7.38
7.36
7.36
7.34
7.34
Figure S39. 1H NMR spectrum (400 MHz, CDCl3) of N-dodecyl-2-hydroxybenzamide (S-Ah).
220 200 180 160 140 120 100 80 60 40 20 0 -20Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
Chloroform-d
169.
916
1.5
134.
012
5.2
118.
611
4.4
77.0
39.7
31.9
29.5
29.3
26.9
22.7
14.1
Figure S40. 13C NMR spectrum (127 MHz, CDCl3) of N-dodecyl-2-hydroxybenzamide (S-Ah).
NH
O
OH
NH
O
OH
18
5.0 10.0 15.0 20.0 25.0 30.0
0.5
1.0
1.5
(x1,000,000)MIC1
Figure S41. Chromatogram obtained by GC-MS (EI, 70 eV) of N-allyl-2-hydroxybenzamide (S-Ai).
50.0 75.0 100.0 125.0 150.0 175.00
25
50
75
100
%
121
57177
65 9341 148 16253 9177 105 131117 191185
Figure S42. Mass spectrum (EI, 70 eV) of N-allyl-2-hydroxybenzamide (S-Ai).
3500 3000 2500 2000 1500 1000 500Wavenumber (cm-1)
40
60
80
100
%Tr
ansm
ittan
ce
3364
3078
29262855
16391597
15431493
137113081256
12331152
754
Figure S43. FTIR spectrum (Silicon plate) of N-allyl-2-hydroxybenzamide (S-Ai).
NH
OH
O
NH
OH
O
NH
OH
O
19
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
1.751.660.83 0.810.78
TMS
7.78
7.76
7.38
7.37
7.35
6.91
6.89
6.88
6.87
5.93
5.25
5.22
5.15
5.13
4.03
4.01
4.00
0.00
7.78 7.76Chemical ...
0.83
7.76
7.77
7.78
7.78
7.375 7.350Chemical Shift...
1.00
7.35
7.36
7.37
7.37
7.38
6.900Chemical Shift...
1.66
6.88
6.89
6.90
6.91 5.950
Chemical Shift (...
0.78
5.91
5.93
5.95
5.96
5.97
5.250 5.225Chemical Shift (ppm)
0.81
5.22
5.22
5.23
5.25
5.25
5.26
5.26
5.150 5.125Chemical Shift...
0.77
5.13
5.13
5.15
5.15
5.16
4.02 4.00Chemical Shift ...
1.75
4.00
4.00
4.01
4.01
4.01
Figure S44. 1H NMR spectrum (400 MHz, CD3OD) of N-allyl-2-hydroxybenzamide (S-Ai).
220 200 180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
Methanol-d4
170.
7
161.
1
135.
413
4.7
128.
912
0.1
118.
411
7.0
116.
2
49.0
42.7
Figure S45. 13C NMR spectrum (127 MHz, CD3OD) of N-allyl-2-hydroxybenzamide (S-Ai).
NH
OH
O
NH
OH
O
20
5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5
2.5
5.0
7.5(x1,000,000)
TIC
Figure S46. Chromatogram obtained by GC-MS (EI, 70 eV) of N-benzyl-2-hydroxybenzamide (S-Aj).
50 100 150 200 2500
25
50
75
100
%
91
227
12110665120 2107951 22918141 152 165 196133 251
Figure S47. Mass spectrum (EI, 70 eV) of N-benzyl-2-hydroxybenzamide (S-Aj).
3500 3000 2500 2000 1500 1000 500Wavenumber (cm-1)
64
72
80
88
96
%Tr
ansm
ittan
ce
3356
30262938
16391589
149513681348 1248
1076
748 698658604
Figure S48. FTIR spectrum (Silicon plate) of N-benzyl-2-hydroxybenzamide (S-Aj).
NH
OH
O
NH
OH
O
NH
OH
O
21
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0 -1 -2Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
4.58 2.00
TMS
7.79
7.78
7.37
7.35
7.34
7.31
7.30
6.91
6.89
6.88
4.58
0.00
7.375 7.350 7.325 7.300Chemical Shift (ppm)
4.58
7.38
7.37
7.37
7.36
7.35
7.35
7.34
7.33
7.31
7.30
7.80 7.79 7.78 7.77Chemical Shift (ppm)
0.95
7.80
7.79
7.78
7.78
7.25 7.23Chemical Shift (...
0.90
7.25
7.25
7.25
7.24
7.22
6.900 6.875Chemical Shift (ppm)
1.906.
91
6.89
6.89
6.88
6.86
Figure S49. 1H NMR spectrum (400 MHz, CD3OD) of N-benzyl-2-hydroxybenzamide (S-Aj).
220 200 180 160 140 120 100 80 60 40 20 0Chemical Shift (ppm)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Inte
nsity
Methanol-d4
170.
9
161.
2
140.
013
4.8
129.
512
8.9
128.
512
8.2
120.
111
8.4
117.
0
49.0
44.0
Figure S50. 13C NMR spectrum (127 MHz, CD3OD) of N-benzyl-2-hydroxybenzamide (S-Aj).
NH
OH
O
NH
OH
O
22
2. Analytical curve of ethyl salicylate ES used to calculate the conversion of amide
Figura S51. Analytical curve of ethyl salicylate used to calculate the conversion of amide.