S1
Highly Selective Direct Azidation of Alcohols over Heterogeneous Povidone – Phosphotungstic Solid Acid Catalyst
Sumit B. Kamble, Sagar B. More, Chandrashekhar V. Rode*
Chemical Engineering and Process Development Division,
CSIR-National Chemical Laboratory, India, Pune-411008.
Email: [email protected]
Supporting Information for New Journal OF Chemistry
Contents
Experimental procedure for synthesis of alcohols, S1
XRD of fresh and recovered PVP-PWA (3:1), S2
Spectroscopic data of all the compounds, S3-S7
1H and 13C-NMR spectra of the products, S8-S25
Experimental procedure for the synthesis of alcohols
To the ice cold solution of ketone (10 mmol) in methanol (20 mL), sodium borohydride (5
mmol) was slowly added under stirring. Then, the mixture was further stirred for 1 h at 0 oC
followed by 1 h at room temperature. After completion of the reaction monitored by TLC,
mixture was extracted with ethyl acetate and washed with water. Evaporation of the ethyl
acetate gave alcohol up to 95-99% yields.
Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2016
S2
XRD of fresh and recovered PVP-PWA (3:1)
10 20 30 40 50 60 70 80
800
1000
1200
1400
1600
B
A
A. PVP-PWA (Fresh) B. PVP-PWA (Recovered)
2Degree
Inte
nsity
(au)
Fig. S1 XRD of A. Fresh and B. Recovered PVP-PWA (3:1)
S3
Spectroscopic data of all the compounds
All the compounds were confirmed using reported literature.11-15, 21-24
N3
(1-azidoethyl)benzene, Table 3, Entry 1.
FT-IR (max): 2926, 2103, 1727, 1601, 1494, 1452, 1372, 1243, 1066, 1066, 762, 737, 700 cm-1. 1H NMR (CHLOROFORM-d, 200MHz): = 7.28 - 7.44 (m, 5 H), 5.89 (q, J=6.6 Hz, 1 H), 1.55 ppm (d, J=6.6 Hz, 3 H).13C NMR (CHLOROFORM-d, 50MHz): = 141.6, 128.5, 127.8, 126.1, 72.3, 22.2 ppm.
N3
O
1-(1-azidoethyl)-4-methoxybenzene, Table 3, Entry 2.
FT-IR (max): 2978, 2935, 2837, 2098, 1611, 1585, 1513, 1463, 1376, 1340, 1304, 1285, 1243, 1176, 1120, 1061, 1032, 991, 830, 810, 747, 650, 628 cm-1. 1H NMR (CHLOROFORM-d, 200MHz): = 7.27 (d, J=8.7 Hz, 2 H), 6.92 (d, J=8.8 Hz, 2 H), 4.58 (q, J=6.9 Hz, 1 H), 3.83 (s, 3 H), 1.52 ppm (d, J=6.8 Hz, 3 H). 13C NMR (CHLOROFORM-d, 50MHz): = 159.4, 132.9, 127.7, 114.1, 77.7, 76.4, 60.7, 55.3, 21.5 ppm.
N3
O
1-(1-azidoethyl)-2-methoxybenzene, Table 3, Entry 3.
FT-IR (max): 2092, 1492, 1463, 1438, 1286, 1242, 1061, 1047, 1028, 751 cm-1. 1HNMR (CHLOROFORM-d, 200MHz): = 7.24 - 7.41 (m, 2 H), 6.88 - 7.06 (m, 2 H), 5.08 (q, J=6.8 Hz, 1 H), 3.87 (s, 3 H), 1.51 ppm (d, J=6.8 Hz, 3 H). 13C NMR (CHLOROFORM-d, 50MHz): = 156.4, 129.1, 128.9, 126.5, 120.7, 110.5, 55.3, 54.9, 20.1 ppm.
N3
OO
1-(1-azidoethyl)-2,4-dimethoxybenzene, Table 3, Entry 4.
S4
FT-IR (max): 2930, 2790, 2089, 1589, 1512, 1461, 1420, 1350, 1299, 1245, 1220, 1159, 1135, 1100, 1050, 1012, 920, 860, 802, 699 cm-1. 1H NMR (CHLOROFORM-d, 200MHz): = 6.86 (s, 3 H), 4.57 (q, J=6.8 Hz, 1 H), 3.88 (s, 3 H), 3.91 (s, 3 H), 1.52 ppm (d, J=6.8 Hz, 3 H).13C NMR (CHLOROFORM-d, 50MHz): = 149.1, 148.8, 133.2, 118.6, 110.9, 109.3, 60.9, 55.8, 21.5 ppm.
N3
OO
4-(1-azidoethyl)-1,2-dimethoxybenzene, Table 3, Entry 5.
FT-IR (max): 2936, 2836, 2105, 1605, 1592, 1515, 1463, 1419, 1375, 1353, 1310, 1256, 1235, 1162, 1141, 1102, 1065, 1025, 914, 855, 808, 765 cm-1. 1H NMR (CHLOROFORM-d, 200MHz): = 6.87 (s, 3 H), 4.58 (d, J=6.8 Hz, 1 H), 3.89 (s, 3 H), 3.92 (s, 3 H), 1.53 ppm (d, J=6.8 Hz, 3 H). 13C NMR (CHLOROFORM-d, 50MHz): = 149.1, 148.8, 133.2, 118.6, 110.9, 109.3, 60.9, 55.8, 21.5 ppm.
N3
Cl
1-(1-azidoethyl)-4-chlorobenzene, Table 3, Entry 6.
IR (max): 2946, 2099, 1497, 1451, 1369, 1230, 1045, 1059, 752 cm-1. .1H NMR (CHLOROFORM-d, 200MHz): = 7.45 - 7.58 (m, J=8.5 Hz, 2 H), 7.12 - 7.26 (m, J=8.5 Hz, 2 H), 4.60 (q, J=6.9 Hz, 1 H), 1.52 ppm (d, J=6.8 Hz, 3 H).13C NMR (CHLOROFORM-d, 50MHz): = 139.4, 133.8, 128.9, 127.7, 60.3, 21.6 ppm.
N3
Br
1-(1-azidoethyl)-4-bromobenzene, Table 3, Entry 7.
IR (max): 2936, 2101, 1605, 1489, 1377, 1222, 1052, 761, 730 cm-1. 1H NMR (CHLOROFORM-d, 200MHz): = 7.23 - 7.41 (m, 5 H), 4.61 (q, J=6.7 Hz, 1 H), 1.52 ppm (d, J=6.8 Hz, 3 H).13C NMR (CHLOROFORM-d, 50MHz): = 139.6, 134.1, 129.2, 128.0, 77.9, 76.6, 60.6, 21.8 ppm.
S
N3
2-(1-azidoethyl)thiophene, Table 3, Entry 8.
S5
IR (max): 2977, 2104, 1453, 1377, 1264, 1235, 1044, 895, 850, 808, 734, 702 cm-1. 1H NMR (CHLOROFORM-d, 200MHz): = 7.30 (dd, J=4.9, 1.5 Hz, 1 H), 6.98 - 7.07 (m, 2 H), 4.84 (q, J=6.8 Hz, 1 H), 1.64 ppm (d, J=6.8 Hz, 3 H). 13C NMR (CHLOROFORM-d, 50MHz): = 143.8, 126.7, 125.2, 124.8, 56.4, 21.7 ppm.
N3
1-(1-azidoethyl)naphthalene, Table 3, Entry 9.
FT-IR (max): 3056, 2978, 2097, 1601, 1508, 1449, 1377, 1305, 1242, 1176, 1143, 1127, 1058, 1018, 988, 950, 894, 817, 770, 672, 619 cm-1. 1H NMR (CHLOROFORM-d, 200MHz): = 7.73 - 8.00 (m, 4 H), 7.40 - 7.60 (m, 3 H), 4.81 (q, J=6.8 Hz, 1 H), 1.64 ppm (d, J=6.8 Hz, 3 H). 13C NMR (CHLOROFORM-d, 50MHz): = 138.2, 133.2, 133.1, 128.7, 128.0, 127.7, 126.4, 126.2, 125.3, 124.2, 61.3, 21.5 ppm.
N3
(Azidomethylene) dibenzene, Table 3, Entry 10.
FT-IR (max): 3063, 3030, 2094, 1953, 1809, 1601, 1493, 1452, 1237, 1181, 1157, 1078, 1030, 1002, 940, 909, 870, 758, 741, 695, 673, 640, 617 cm-1.1H NMR (200 MHz, CHLOROFORM-d) ppm 5.73 (s, 1 H) 7.28 - 7.40 (m, 10 H). 13C NMR (CHLOROFORM-d, 50MHz): = 139.5, 128.7, 128.0, 127.4, 68.5 ppm.
N3
O
1-(azido (phenyl) methyl)-4-methoxybenzene, Table 3, Entry 11.
FT-IR (max): 2976, 2838, 2091, 1601, 1588, 1492, 1464, 1438, 1372, 1346, 1286, 1242, 1194, 1173, 1162, 1121, 1062, 1047, 1028, 993, 935, 842, 803, 751, 691, 647 cm-1.1H NMR (CHLOROFORM-d, 200MHz): = 7.34 (d, J=2.4 Hz, 5 H), 7.24 (d, J=8.8 Hz, 2 H), 6.90 (d, J=8.7 Hz, 2 H), 5.69 (s, 1 H), 3.82 ppm (s, 3 H).13C NMR (CHLOROFORM-d, 50MHz): = 128.8, 128.7, 128.0, 127.3, 114.1, 68.1, 55.3 ppm.
N3
O O
S6
4,4'-(azidomethylene)bis(methoxybenzene, Table 3, Entry12.
FT-IR (max): 3001, 2956, 2836, 2094, 1609, 1584, 1509, 1462, 1441, 1421, 1303, 1242, 1172, 1111, 1031, 943, 881, 826, 810, 778, 729, 706, 664, 625 cm-1. 1H NMR (CHLOROFORM-d, 200MHz): = 7.23 (d, J=8.6 Hz, 4 H), 6.86 - 6.94 (m, 4 H), 5.65 (s, 1 H), 3.81 ppm (s, 6 H).13C NMR (CHLOROFORM-d, 50MHz): = 159.2, 131.9, 128.5, 113.9, 67.5, 55.2 ppm.
N3
1-(azido(phenyl)methyl)-4-methylbenzene, Table 3, Entry 13.
FT-IR (max): 3027, 2922, 2096, 1512, 1493, 1451, 1241, 1176, 1111, 1079, 1057, 1029, 1020, 915, 875, 842, 797, 779, 731, 719, 696, 667, 640, 622 cm-1. 1H NMR (CHLOROFORM-d, 200MHz): = 7.28 - 7.45 (m, 5 H), 7.12 - 7.26 (m, 4 H), 5.70 (s, 1 H), 2.36 ppm (s, 3 H). 13C NMR (CHLOROFORM-d, 50MHz): = 142.5, 139.8, 139.3, 129.4, 129.0, 128.6, 128.3, 127.9, 127.3, 127.3, 68.3, 21.1 ppm.
N3
Cl1-(azido(phenyl)methyl)-4-chlorobenzene, Table 3, Entry14.
FT-IR (max): 3030, 2096, 1599, 1490, 1453, 1407, 1239, 1179, 1090, 1030, 1015, 949, 913, 872, 794, 752, 717, 698, 657, 630 cm-11H NMR (CHLOROFORM-d, 400MHz): = 7.27 - 7.41 (m, 8 H), 7.24 - 7.27 (m, 1 H), 5.70 ppm (s, 1 H).13C NMR (CHLOROFORM-d, 50MHz): = 165.0, 160.1, 139.6, 135.7, 129.4, 129.2, 129.0, 128.7, 128.4, 127.5, 116.0, 115.6, 68.0 ppm
N3
F
1-(azido(phenyl)methyl)-4-fluorobenzene, Table 3, Entry 15.
FT-IR (max): 2096, 1603, 1507, 1494, 1453, 1280, 1223, 1181, 1157, 1097, 1077, 1057, 1028, 1015, 876, 849, 813, 792, 737, 720, 696, 669, 638, 616 cm-1.1H NMR (CHLOROFORM-d, 200MHz): = 7.28 - 7.44 (m, 6 H), 7.23 - 7.26 (m, 1 H), 7.04 (t, J=8.7 Hz, 2 H), 5.70 ppm (s, 1 H).13C NMR (CHLOROFORM-d, 50MHz): = 164.8, 159.9, 139.4, 129.2, 129.0, 128.8, 128.2, 127.3, 115.8, 115.4, 67.8 ppm.
N3
S7
1-(1-azido-3-phenylpropyl)-4-methylbenzene, Table 3, Entry 16.
FT-IR (max): 3026, 2923, 2092, 1603, 1514, 1496, 1454, 1306, 1242, 1182, 1113, 1082, 1030, 1019, 908, 882, 815, 772, 748, 721, 698, 637 cm-1. 1H NMR (CHLOROFORM-d, 200MHz): = 7.14 - 7.36 (m, 9 H), 4.37 (t, J=7.2 Hz, 1 H), 2.61 - 2.76 (m, 2 H), 2.37 (s, 3 H), 2.00 - 2.27 ppm (m, 3 H).13C NMR (CHLOROFORM-d, 50MHz): = 140.9, 138.1, 136.3, 129.5, 128.4, 126.9, 126.0, 65.2, 37.5, 32.3, 21.1 ppm.
O
ON3
1-azido-5,6-dimethoxy-2,3-dihydro-1H-indene, Table 3, Entry 17.
FT-IR (max): 2937, 2086, 1606, 1503, 1464, 1454, 1413, 1338, 1308, 1257, 1220, 1187, 1167, 1089, 1036, 1008, 980, 923, 890, 850, 801, 773, 759, 654 cm-1. 1H NMR (CHLOROFORM-d, 200MHz): = 6.90 (s, 1 H), 6.80 (s, 1 H), 4.82 (dd, J=7.1, 4.3 Hz, 1 H), 3.89 (s, 3 H), 3.90 (s, 3 H), 2.72 - 3.16 (m, 2 H), 2.38 - 2.61 (m, 1 H), 2.06 - 2.28 ppm (m, 1 H).13C NMR (CHLOROFORM-d, 50MHz): = 150.0, 148.5, 135.8, 132.2, 107.5, 107.2, 77.8, 77.1, 76.5, 66.5, 56.1, 56.0, 32.9, 30.5 ppm.
N3
O
1-(allyloxy)-4-(1-azidoethyl)benzene, Table 3, Entry 18.
FT-IR (max): 2967, 2925, 2102, 1609, 1510, 1455, 1373, 1237, 1175, 1104, 1022, 996, 928, 831, 732, 700 cm-1. 1H NMR (CHLOROFORM-d, 200MHz): = 7.21 - 7.30 (m, 2 H), 6.85 - 6.99 (m, 2 H), 5.96 - 6.18 (m, 1 H), 5.23 - 5.51 (m, 2 H), 4.47 - 4.65 (m, 3 H), 1.52 ppm (d, J=6.8 Hz, 3 H). 13C NMR (CHLOROFORM-d, 50MHz): = 158.4, 133.1, 133.0, 127.6, 117.7, 114.8, 68.8, 60.6, 21.4 ppm.
S8
1H and 13 C NMR data of the compounds
N3
(1-azidoethyl)benzene, Table3, Entry 1.
1H NMR
9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5Chemical Shift (ppm)
3.000.855.05
CHLOROFORM-d
1.53
1.56
5.84
5.88
5.91
5.94
7.27
7.29
7.32
7.33
7.36
7.37
7.38
13C NMR
152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
22.1
6
72.2
9
126.
0512
7.83
128.
45
141.
64
S9
N3
O
1-(1-azidoethyl)-4-methoxybenzene Table 3, Entry 2.
1H NMR
FRI4AV2#139.001.001.1R.esp
11.5 11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5Chemical Shift (ppm)
3.082.980.951.972.20
CHLOROFORM-d
TMS
1.50
1.54
3.83
4.53
4.57
4.60
4.63
6.90
6.94
7.25
7.29
13C NMR
13 C.002.001.1R.esp
168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
159.
43
132.
87
127.
70
114.
10
77.7
177
.07
76.4
4
60.7
1
55.3
1
21.4
9
S10
N3
O
1-(1-azidoethyl)-2-methoxybenzene, Table 3, Entry 3.
1H NMR
WED2AV2#125.001.001.1R.esp
10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
3.093.000.982.022.17
CHLOROFORM-d
1.50
1.53
3.87
5.03
5.06
5.10
5.13
6.90
6.94
7.00
7.00
7.27
7.30
7.31
7.34
7.38
7.39
13C NMR
Fri4av2#205.002.001.1r.esp
168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
156.
52
129.
1712
9.04
126.
59
120.
80
110.
62
77.7
377
.10
76.4
6
55.4
254
.98
20.1
6
S11
N3
OO
1-(1-azidoethyl)-2,4-dimethoxybenzene, Table 3, Entry 4.
1H NMR
THU5AV2#126.001.001.1R.esp
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0Chemical Shift (ppm)
3.006.010.942.87
CHLOROFORM-d
1.50
1.54
3.88
3.91
4.55
4.59
6.86
13 C NMR
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20Chemical Shift (ppm)
CHLOROFORM-d
149.
0814
8.77
133.
24
118.
64
110.
9110
9.34
77.0
0
60.9
255
.81
21.4
5
S12
N3
OO
4-(1-azidoethyl)-1,2-dimethoxybenzene, Table 3, Entry 5.
1H NMR
FRI4AV2#140.001.001.1R.esp
11.5 11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
3.005.930.952.92
CHLOROFORM-d
1.51
1.54
3.89
3.92
4.56
4.60
6.87
7.27
13C NMR
13 C.002.001.1R.esp
168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
149.
0814
8.77
133.
24
118.
64
110.
9110
9.34
77.6
377
.00
76.3
6
60.9
2
55.8
1
21.4
5
S13
N3
Cl
1-(1-azidoethyl)-4-chlorobenzene, Table 3, Entry 6.
1H NMR
Fri4av2#135.001.001.1r.esp
11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
3.001.022.061.99
CHLOROFORM-d
7.54
7.50
7.27
7.24
7.19
4.65
4.62
4.58
4.55
1.53
1.50
13C NMR
160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
CHLOROFORM-d
139.
36
133.
85
128.
9112
7.72
60.3
3
21.5
6
S14
N3
Br
1-(1-azidoethyl)-4-bromobenzene, Table 3, Entry 7.
1H NMR
10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5Chemical Shift (ppm)
3.000.944.15
CHLOROFORM-d
7.39
7.36
7.34
7.33
7.29
7.28
7.27
7.25
4.66
4.63
4.60
4.56
1.54
1.50
13C NMR
220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 -10 -20Chemical Shift (ppm)
CHLOROFORM-d
CHLOROFORM-d
139.
6113
4.10
129.
1612
7.97
77.8
877
.25
76.6
2
60.5
8
21.8
1
S15
S
N3
2-(1-azidoethyl)thiophene, Table 3, Entry 8.
1H NMR
10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5Chemical Shift (ppm)
3.231.001.960.91
CHLOROFORM-d
1.62
1.66
4.79
4.82
4.86
4.89
7.01
7.01
7.03
7.04
7.27
7.29
7.30
7.31
7.32
13C NMR
168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
21.6
9
56.3
7
124.
8312
5.20
126.
69
143.
79
S16
N3
1-(1-azidoethyl)naphthalene, Table 3, Entry 9.
1H NMR
10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
3.000.972.953.97
CHLOROFORM-d
1.62
1.66
4.76
4.79
4.83
4.86
7.27
7.46
7.50
7.52
7.53
7.53
7.55
7.80
7.85
7.87
7.89
7.92
13C NMR
152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
138.
2113
3.18
133.
0612
8.71
127.
9812
7.67
126.
3712
6.19
125.
2512
4.18
77.0
0
61.2
5
21.5
4
S17
N3
(Azidomethylene) dibenzene, Table 3, Entry 10.
1H NMR
FRI4AV2#138.001.001.1R.esp
11.5 11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
1.0010.35
CHLOROFORM-d
7.38
7.35
7.34
7.33
7.32
7.31
7.27
5.73
13C NMR
13 C.002.001.1R.esp
160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
68.4
8
77.0
0
127.
3512
8.02
128.
67
139.
53
S18
N3
O
1-(azido (phenyl) methyl)-4-methoxybenzene, Table 3, Entry 11.
1H NMR
FRI2AV2#004.001.001.1R.esp
10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0 -0.5Chemical Shift (ppm)
3.010.962.042.054.95
CHLOROFORM-d
7.35
7.34
7.26
7.22
6.92
6.88
5.69
3.82
13C NMR
SAT2AV2#149.001.001.1R.esp
160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
128.
8512
8.72
127.
9912
7.31
114.
12
68.1
4
55.3
3
S19
N3
O O
4,4'-(azidomethylene)bis(methoxybenzene , Table 3, Entry12.
1H NMR
Fri2av2#003.001.001.1r.esp
9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
6.000.964.254.12
CHLOROFORM-d
7.27
7.25
7.21
6.92
6.90
6.88
6.87
5.65
3.81
13C NMR
168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
159.
15
131.
9112
8.50
113.
89
67.5
5
55.1
6
S20
N3
1-(azido(phenyl)methyl)-4-methylbenzene, Table 3, Entry 13.
1H NMR
10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
3.000.934.044.89
CHLOROFORM-d
2.36
5.70
7.20
7.24
7.27
7.30
7.32
7.34
7.35
7.36
7.37
13C NMR
152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
21.0
9
68.3
4
76.3
777
.00
77.6
4
127.
2712
7.34
127.
9012
8.29
128.
6112
9.05
129.
3513
9.33
139.
7714
2.46
S21
N3
Cl
1-(azido(phenyl)methyl)-4-chlorobenzene, Table 3, Entry14.
1H NMR
TUE4ECX400#128_PROTON-3.ESP
11.5 11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
1.021.118.02
CHLOROFORM-d
7.41
7.38
7.37
7.35
7.33
7.31
7.30
7.27
7.25
5.70
0.02
13C NMR
168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
165.
01
160.
09
139.
5513
5.67
129.
3712
9.21
128.
9712
8.74
128.
3812
7.49
116.
0011
5.57
77.8
477
.20
76.5
7
67.9
8
S22
N3
F
1-(azido(phenyl)methyl)-4-fluorobenzene, Table 3, Entry 15.
1H NMR
FRI2AV2#002.001.001.1R.esp
11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
0.812.001.016.18
CHLOROFORM-d
7.34
7.33
7.31
7.30
7.29
7.27
7.24
7.08
7.04
5.70
13C NMR
168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
164.
81
159.
89
139.
35
129.
1712
9.01
128.
7712
8.18
127.
29
115.
8011
5.37
77.0
0
67.7
8
S23
N3
1-(1-azido-3-phenylpropyl)-4-methylbenzene, Table 3, Entry 16.
1H NMR
WED2AV2#127.001.001.1R.esp
10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
2.413.191.990.949.47
CHLOROFORM-d
1.98
2.06
2.10
2.11
2.13
2.15
2.37
2.63
2.65
2.67
2.71
2.73
4.34
4.38
4.41
7.16
7.20
7.23
7.24
7.26
7.27
7.31
7.34
13C NMR
Fri4av2#203.002.001.1r.esp
152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
141.
0313
8.17
136.
45
129.
5712
8.55
126.
9912
6.15
77.7
477
.10
76.4
7
65.3
1
37.6
2
32.4
4
21.2
2
S24
O
ON3
1-azido-5,6-dimethoxy-2,3-dihydro-1H-indene, Table 3, Entry 17.
1H NMR
WED2AV2#128.001.001.1R.esp
9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
1.021.071.986.000.931.020.96
CHLOROFORM-d
2.15
2.17
2.19
2.21
2.44
2.47
2.50
2.83
2.85
2.87
2.90
3.02
3.05
3.09
3.89
3.90
4.79
4.81
4.83
4.85
6.80
6.90
7.27
13C NMR
Fri4av2#204.002.001.1r.esp
160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
150.
0414
8.48
135.
7613
2.17
107.
5210
7.17
77.7
677
.12
76.4
9
66.4
7
56.1
055
.99
32.9
130
.50
S25
N3
O
1-(allyloxy)-4-(1-azidoethyl)benzene, Table 3, Entry 18.
1H NMR
10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
3.002.882.040.901.952.02
CHLOROFORM-d
7.28
7.27
7.25
7.24
6.95
6.94
6.92
6.91
6.11
6.09
6.05
6.03
6.00
5.47
5.47
5.34
5.33
5.31
5.28
4.60
4.57
4.57
4.56
4.55
4.54
4.53
1.54
1.50
13C NMR
168 160 152 144 136 128 120 112 104 96 88 80 72 64 56 48 40 32 24 16 8 0Chemical Shift (ppm)
CHLOROFORM-d
21.3
8
60.6
1
68.7
8
77.0
0
114.
8211
7.69
127.
5913
2.97
133.
09
158.
37