SUPPLEMENTARY DATA
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2
3
A facile, highly efficient and novel method for the synthesis of 5-substituted 1H-
4
tetrazoles catalysed by copper(I) chloride
5
aİbrahim
6
Esirden, aErhan Başar, bMuharrem Kaya
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a
Chemistry Department, bBiochemistry Department, Faculty of Arts and Science,
Dumlupınar University, Evliya Çelebi Campus 43100 Kütahya, Turkey.
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Received 18 December 2014; Revised 15 March 2015; Accepted 17 March 2015
Corresponding
authors, e-mail: muharrem.kaya@dpu.edu.tr
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Product number
III
Spectral data
As a white powder, M.p.: 214-216 oC (lit. 215-216 oC) (Rama et al., 2011)
FT–IR (cm-1): 3053, 2979, 2906, 2833, 2682, 2601, 2536, 1607, 1561, 1285,
1254
1
H NMR (300 MHz, DMSO-d6): δ = 7.60-7.65 (m, 3H, Ar-H), 8.03-
8.07 (m, 2H, Ar-H), 16.85 (br, 1H, -NH) ppm
C NMR (75 MHz, DMSO-d6): δ = 124.60, 127.40, 129.79, 131.62, 155.77
13
ppm
HRMS (QTOF-ESI): m/z [M-H]- calculated for C7H6N4: 145.0514; found [MH]-: 145.0517
IV
As a white powder, M.p.: 254 oC (lit. 254-255 oC) (Rama et al., 2011)
FT–IR (cm-1): 3055, 2969, 2885, 2410, 1627, 1526, 1291, 1237, 1041
1
H NMR (300 MHz, DMSO-d6): δ = 8.05 (s, 2H, Ar-H), 8.90 (s, 2H, Ar-H),
15.60 (br, 1H, -NH) ppm
C NMR (75 MHz, DMSO-d6): δ = 121.60, 133.91, 150.51, 155.20, 155.64
13
ppm
HRMS (QTOF-ESI): m/z [M-H]- calculated for C6H5N5: 146.0467; found [MH]-: 146.0468
As an orange powder, M.p.: 220 oC (lit. 219-221 oC) (Rama et al., 2011)
V
FT–IR (cm-1): 3078, 2913, 2845, 2770, 1605, 1551, 1512, 1291, 1222
1
H NMR (300 MHz, DMSO-d6): δ = 8.31 (d, J= 9.01 Hz, 2H, Ar-H), 8.46 (d,
J= 9.00 Hz, 2H, Ar-H) ppm
C NMR (75 MHz, DMSO-d6): δ = 125.03, 128.63, 131.10, 149.16, 155.92
13
ppm HRMS (QTOF-ESI): m/z [M-H]- calculated for C7H5N5O2: 190.0365;
found [M-H]-: 190.0367
As a white powder, M.p.: 183-185 oC (lit. 183-185 oC) (Chermahini et al.,
VI
2011)
FT–IR (cm-1): 3065, 2978, 2912, 2817, 2686, 2542, 1698, 1565, 1557, 1289,
1255 1H NMR (300 MHz, DMSO-d6): δ = 8.13 (d, J= 8.42 Hz, 2H, Ar-H),
8.27 (d, J= 8.22 Hz, 2H, Ar-H), 10.10 (s, 1H, -CHO), 17.15 (br, 1H, -NH)
3
ppm
C NMR (75 MHz, DMSO-d6): δ = 128.07, 130.00, 130.82, 138.07, 155.90,
13
193.13 ppm
HRMS (QTOF-ESI): m/z [M-H]- calculated for C8H6N4O: 173.0463; found
[M-H]-: 173.0461
As a white powder, M.p.: 196-198 oC (lit. 196-198 oC) (Zhu et al., 2009)
VII
FT–IR (cm-1): 3045, 2987, 2958, 2835, 2758, 2606, 1676, 1611, 1558, 1283,
1249
1
H NMR (300 MHz, DMSO-d6): δ = 7.86 (t, J= 7.71 Hz, 1H, Ar-H),
8.14 (d, J= 7.66 Hz, 1H, Ar-H), 8.36 (d, J= 7.78 Hz, 2H, Ar-H), 8.58 (s, 1H,
Ar-H), 10.15 (s, 1H, -CHO) 17.15 (br, 1H, -NH) ppm
C NMR (75 MHz, DMSO-d6): δ = 125.78, 127.75, 130.84, 132.57, 132.85,
13
137.37, 155.64, 193.07 ppm
HRMS (QTOF-ESI): m/z [M-H]- calculated for C8H6N4O: 173.0463; found
[M-H]- : 173.0465
As a white powder, M.p.: 249-250 oC (lit. 250-252 oC) (Sreedhar et al., 2011)
VIII
FT–IR (cm-1): 3063, 2973, 2902, 2680, 2540, 1606, 1561, 1484, 1276, 1255
1097 1H NMR (300 MHz, DMSO-d6): δ = 7.70 (d, J= 8.56 Hz, 2H, Ar-H),
8.06 (d, J= 8.57 Hz, 2H, Ar-H), 16.95 (br, 1H, -NH) ppm
C NMR (75 MHz, DMSO-d6): δ = 123.67, 129.18, 130.03, 136.37, 156.00
13
ppm HRMS (QTOF-ESI): m/z [M-H]- calculated for C7H5ClN4: 179.0124;
found [M-H]-: 179.0123
IX
As a brown powder, M.p.: 260 oC (lit. 260.6-261 oC) (Cristiano et al., 2005)
FT–IR (cm-1): 3061, 2969, 2720, 2613, 1599, 1556, 1480, 1276, 1251 1074
1
H NMR (300 MHz, DMSO-d6): δ = 7.84 (d, J= 8.48 Hz, 2H, Ar-H), 7.99 (d,
J= 8.46 Hz, 2H, Ar-H), 16.95 (br, 1H, -NH) ppm
C NMR (75 MHz, DMSO-d6): δ = 124.02, 125.17, 129.33, 132.93, 155.53
13
ppm HRMS (QTOF-ESI): m/z [M-H]- calculated for C7H5BrN4: 222.9619;
found [M-H]-: 222.9627
X
As a white powder, M.p.: 248-250 oC (lit. 248-249 oC) (Jin et al., 2008)
4
FT–IR (cm-1): 3044, 2979, 2916, 2846, 2767, 2679, 2608, 2541, 1612, 1569,
1285, 1256, 1162, 1085
1
H NMR (300 MHz, DMSO-d6): δ = 7.42 (d, J= 8.09 Hz, 2H, Ar-H), 7.93 (d,
J= 8.17 Hz, 2H, Ar-H), 16.75 (br, 1H, -NH) ppm
C NMR (75 MHz, DMSO-d6): δ = 21.47, 121.71, 127.34, 130.40, 141.69,
13
155.53 ppm
HRMS (QTOF-ESI): m/z [M-H]- calculated for C8H8N4: 159.0671; found [MH]-: 159.0674
XI
As a white powder, M.p.: 288 oC (lit. 287 oC) (Chand et al., 1997)
FT–IR (cm-1): 3264, 3132, 3078, 2201, 2151, 1600, 1544, 1322, 1290, 1263
1
H NMR (300 MHz, DMSO-d6): δ = 2.07 (s, 3H, -CH3), 7.58 (d, J= 8.21 Hz,
2H, Ar-H), 7.88 (d, J= 8.26 Hz, 2H, Ar-H), 9.95 (s, 1H, -NH) ppm
C NMR (75 MHz, DMSO-d6): δ = 24.45, 119.40, 126.59, 127.91, 138.74,
13
156.50, 168.73 ppm
HRMS (QTOF-ESI): m/z [M-H]- calculated.for C9H9N5O: 202.0729; found
[M-H]-: 202.0732
XII
As a white powder, M.p.: 253-254 oC decomposition (lit. 254-255 oC
decomposition) (McManus & Herbst, 1959)
FT–IR (cm-1): 3389, 3280, 3064, 2199, 2142, 1673, 1619, 1595, 1567, 1321,
1291, 1263
1
H NMR (300 MHz, DMSO-d6): δ = 2.08 (s, 3H, -CH3), 7.28 (s, 1H, Ar-H),
7.60 (d, J= 7.98 Hz, 2H, Ar-H), 8.15 (s, 1H, Ar-H) 9.98 (s, 1H, -NH) ppm
C NMR (75 MHz, DMSO-d6): δ = 24.47, 117.21, 118.21, 121.21, 129.05,
13
133.52, 139.86, 156.00, 168.77 ppm
HRMS (QTOF-ESI): m/z [M-H]- calculated for C9H9N5O: 202.0729; found
[M-H]-: 202.0734
13
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17
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5
19
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5-Phenyl 1H-tetrazole (III)
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a)
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b)
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c)
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CU24CN
2500
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Wavenumber cm-1
Instrument type and / or accessory
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1500
1285.82
1254.92
1161.32
1101.12
1081.65
1054.51
1032.60
1012.96
1607.14
1561.76
1483.32
1463.21
1407.83
1852.87
2452.05
2601.57
2536.47
2682.82
3127.75
3053.98
2979.22
2906.48
2833.79
70
75
80
85
90
Transmittance [%]
95
100
6
1000
500
9/13/2014
7
63
64
65
d)
66
67
68
Fig. 1. a) FT-IR, b) 1H NMR, c)
69
tetrazole
70
13
C NMR (APT), d) Q-TOF LC/HRMS of 5-Phenyl 1H-
4-(1H-tetrazol-5-yl)pyridine (IV)
3500
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72
73
74
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b)
75
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c)
3000
CU24N
Instrument type and / or accessory
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2500
2000
Wavenumber cm-1
1627.91
1526.66
1438.86
1386.39
1353.10
1291.39
1237.16
1200.27
1185.66
1145.28
1119.65
1094.08
1041.73
1017.87
988.08
968.52
869.34
841.84
748.24
713.26
648.69
526.29
458.47
1715.86
1806.17
1905.54
2015.39
2105.83
50
60
70
80
90
100
71
2410.65
3098.14
3055.84
3035.71
2969.22
2885.21
40
8
a)
1500
1000
500
9/13/2014
9
78
79
d)
80
81
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Fig. 2. a) FT-IR, b) 1H NMR, c) 13C NMR (APT), d) Q-TOF LC/HRMS of 4-(1H-tetrazol-5-
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yl)pyridine
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5-(4-nitrophenyl)-1H-tetrazole (V)
3500
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87
90
b)
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c)
CU24NO2
3000
1605.20
1551.29
1512.31
1437.38
1386.38
1362.19
1337.03
1317.35
1291.87
1222.69
1145.59
1119.90
1108.86
1076.14
1064.01
2913.55
2845.51
2770.22
70
75
80
85
90
95
100
85
3101.16
3078.28
3206.83
65
Transmittance [%]
10
a)
2500
2000
Wavenumber cm-1
Instrument type and / or accessory
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1500
1000
500
9/13/2014
11
91
92
d)
93
94
Fig. 3. a) FT-IR, b) 1H NMR, c) 13C NMR (APT), d) Q-TOF LC/HRMS of 5-(4-nitrophenyl)-
95
1H-tetrazole
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97
98
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b)
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CU24CN
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Instrument type and / or accessory
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1698.99
1665.87
1613.93
1577.57
1565.28
1499.40
1441.60
1404.44
1387.14
1353.40
1303.51
1289.76
1255.92
1207.31
1174.45
1161.31
1120.64
1086.15
1048.88
1021.03
1009.91
1866.32
2161.55
2457.82
2542.68
2686.51
70
75
80
85
90
99
2817.57
65
100
3190.12
3140.09
3090.63
3065.57
2978.17
2912.32
3391.57
3353.68
3297.22
60
Transmittance [%]
12
a)
4-(1H-tetrazol-5-yl)benzaldehyde (VI)
1500
1000
500
9/13/2014
13
105
c)
106
107
d)
108
109
Fig. 4. a) FT-IR, b) 1H NMR, c) 13C NMR (APT), d) Q-TOF LC/HRMS of 4-(1H-tetrazol-5-
110
yl)benzaldehyde
111
112
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60
70
80
90
100
114
115
3500
C:\OPUS_7.0.129\MEAS\.145
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117
118
119
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b)
3000
CU23CN
1676.67
1611.42
1558.58
1479.25
1459.70
1446.97
1401.97
1383.50
1370.46
1323.14
1283.40
1249.43
1224.98
1205.87
1088.46
1071.56
1027.01
1003.55
3176.34
3135.73
3080.48
3060.06
3045.75
2987.28
2958.98
2916.69
2835.29
2780.87
2758.64
2606.73
50
Transmittance [%]
14
a)
3-(1H-tetrazol-5-yl)benzaldehyde (VII)
2500
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Wavenumber cm-1
Instrument type and / or accessory
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1500
1000
500
9/13/2014
15
121
c)
122
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d)
124
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Fig. 5. a) FT-IR, b) 1H NMR, c) 13C NMR (APT), d) Q-TOF LC/HRMS of 3-(1H-tetrazol-5-
126
yl)benzaldehyde
127
128
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131
132
133
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b)
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CU24CL
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1606.41
1561.79
1484.81
1457.99
1435.29
1407.04
1297.32
1276.81
1255.37
1225.04
1202.13
1163.14
1119.55
1097.30
1052.58
1022.91
1007.54
1707.45
2163.90
2134.70
2031.50
1993.27
1905.73
2453.48
2540.10
75
80
85
90
95
100
130
2680.27
70
129
2973.82
2902.40
2825.76
3063.40
65
Transmittance [%]
16
a)
5-(4-chlorophenyl)-1H-tetrazole (VIII)
1500
1000
500
9/13/2014
17
135
c)
136
137
d)
138
139
Fig. 6. a) FT-IR, b) 1H NMR, c)
140
chlorophenyl)-1H-tetrazole
141
142
143
13
C NMR (APT), d) Q-TOF LC/HRMS of 5-(4-
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b)
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CU24BR
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2500
2000
Wavenumber cm-1
1703.12
1599.92
1556.49
1480.09
1453.76
1428.68
1401.00
1298.79
1276.38
1251.91
1190.83
1155.91
1119.22
1074.83
1051.52
1017.45
986.54
862.66
826.40
741.30
724.55
707.70
691.16
626.35
500.21
460.75
450.03
1907.90
2123.71
70
75
80
85
90
95
100
145
2613.88
65
144
2720.74
3117.08
3088.30
3061.44
2969.22
2897.16
2843.76
60
Transmittance [%]
18
a)
5-(4-bromophenyl)-1H-tetrazole (IX)
1500
1000
500
9/13/2014
19
150
c)
151
152
d)
153
154
Fig. 7. a) FT-IR, b) 1H NMR, c)
155
bromophenyl)-1H-tetrazole
156
13
C NMR (APT), d) Q-TOF LC/HRMS of 5-(4-
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159
160
161
162
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b)
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CU24CH3
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2500
2000
Wavenumber cm-1
1612.17
1569.02
1503.61
1432.52
1402.87
1373.76
1285.00
1256.87
1215.00
1187.02
1162.30
1125.25
1085.01
1052.36
1025.65
1014.03
1711.71
1884.95
1993.98
2166.08
2119.03
80
90
100
158
2455.83
70
157
2679.76
2608.02
2541.80
3082.42
3044.98
2979.19
2916.11
2846.39
2767.13
60
Transmittance [%]
20
a)
5-(p-tolyl)-1H-tetrazole (X)
1500
1000
500
9/13/2014
21
164
c)
165
166
d)
167
168
Fig. 8. a) FT-IR, b) 1H NMR, c)
169
tetrazole
170
171
13
C NMR (APT), d) Q-TOF LC/HRMS of 5-(p-tolyl)-1H-
C:\OPUS_7.0.129\MEAS\.143
174
175
176
177
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b)
3500
3000
CU24ABN
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Instrument type and / or accessory
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1500
1000
573.09
523.42
463.54
423.96
1446.87
1419.45
1369.98
1322.13
1290.79
1263.37
1178.02
1119.30
1037.22
1008.84
962.84
838.86
790.56
759.25
671.24
1645.70
1600.02
1544.64
2201.41
2151.11
2325.50
3132.05
3078.71
75
80
85
90
95
100
172
3264.79
70
173
3590.78
3744.36
65
Transmittance [%]
22
a)
N-(4-(1H-tetrazol-5-yl)phenyl)acetamide (XI)
500
9/13/2014
23
179
c)
180
181
d)
182
183
Fig. 9. a) FT-IR, b) 1H NMR, c) 13C NMR (APT), d) Q-TOF LC/HRMS of N-(4-(1H-tetrazol-
184
5-yl)phenyl)acetamide
185
186
3500
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189
190
191
192
193
b)
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CU23ABN
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Instrument type and / or accessory
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1673.63
1649.86
1619.52
1595.10
1567.91
1502.95
1471.73
1420.65
1372.29
1321.13
1291.53
1263.43
1200.51
1171.23
1138.42
1084.72
1041.91
1015.90
70
75
80
85
90
95
100
188
2199.39
2142.04
65
187
3280.44
3230.79
3211.13
3178.21
3105.54
3064.89
3389.66
60
Transmittance [%]
24
a)
N-(3-(1H-tetrazol-5-yl)phenyl)acetamide (XII)
1500
1000
500
9/13/2014
25
194
c)
195
196
d)
197
198
Fig. 10. a) FT-IR, b) 1H NMR, c)
199
tetrazol-5-yl)phenyl)acetamide
200
13
C NMR (APT), d) Q-TOF LC/HRMS of N-(3-(1H-
References
26
201
Chand, P., Babu, Y. S., Bantia, S., Chu, N., Cole, L. B., Kotian, P. L., Laver, W. G.,
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206
Chermahini, A. N., Teimouri, A., & Moaddeli, A. (2011). Simple and efficient synthesis of 5–
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Cristiano, R., Ely, F., & Gallardo, H. (2005). Light–emitting bent–shape liquid crystals.
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Jin, T., Kitahara, F., Kamijo, S., & Yamamoto, Y. (2008). Copper–catalyzed synthesis of 5–
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substituted 1H-tetrazoles via the [3+2] cycloaddition of nitriles and trimethylsilyl azide.
213
Tetrahedron Letters, 49, 2824–2827. DOI: 10.1016/j.tetlet.2008.02.115.
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McManus, J. M., & Herbst, R. M. (1959). Tetrazole analogs of aminobenzoic acid
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Rama, V., Kanagaraj, K., & Pitchumani, K. (2011). Syntheses of 5-substituted 1H-tetrazoles
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catalyzed by reusable CoY zeolite. Journal of Organic Chemistry, 76, 9090–9095. DOI:
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10.1021/jo201261w.
219
Sreedhar, B., Suresh Kumar, A., & Yada, D. (2011). CuFe2O4 nanoparticles: a magnetically
220
recoverable and reusable catalyst for the synthesis of 5-substituted 1H-tetrazoles.
221
Tetrahedron Letters, 52, 3565–3569. DOI: 10.1016/j.tetlet.2011.04.094.
222
Zhu, Y., Ren, Y., & Cai, C. (2009). One-pot synthesis of 5-substituted 1H-tetrazoles from aryl
223
bromides with potassium hexakis(cyano–kC)ferrate(4–) (K4[Fe(CN)6]) as cyanide source.
224
Helvetica Chimica Acta, 92, 171–175. DOI: 10.1002/hlca.200800254.
225