The Journal of Organic Chemistry
Article
1-(Nitro(tosyl)methyl)-3-(trifluoromethyl)benzene 3g. Analytical
TLC on silica gel, 1:4 ethyl acetate/hexane Rf = 0.29; yellow liquid
(183 mg, 51%); H NMR (600 MHz, CDCl3) δ 7.78 (d, J = 7.8 Hz,
2H), 7.60−7.58 (m, 4H), 7.34 (d, J = 8.4 Hz, 2H), 6.51 (s, 1H), 2.47
(s, 3H); 13C {1H}NMR (150 MHz, CDCl3) δ 147.6, 133.5, 133.3,
130.7, 130.2, 129.8, 129.4, 128.6, 127.3, 126.6, 126.3, 103.1, 22.0; FT-
IR (neat) 2926, 1596, 1566, 1452, 1384, 1332, 1261, 1159, 1133, 1101,
1081, 814, 703, 659 cm−1; HRMS (APCI) m/z [M − H]− calcd for
C15H12F3NO4S, 358.0361; found, 358.0367.
(s, 3H), 2.48 (s, 3H); 13C {1H}NMR (150 MHz, CDCl3) δ 157.0,
147.0, 136.0, 132.9, 131.8, 130.5, 130.0, 115.7, 113.3, 112.9, 95.1, 56.5,
22.0; FT-IR (KBr) 2981, 1595, 1556, 1487, 1462, 1441, 1403, 1352,
1329, 1305, 1282, 1260, 1213, 1186, 1155, 1116, 1085, 1019, 820, 647
cm−1; HRMS (APCI) m/z [M − H]− calcd for C15H14BrNO5S,
397.9703; found, 397.9710.
1,2,4-Trimethoxy-5-(nitro(tosyl)methyl)benzene 3o. Analytical
TLC on silica gel, 1:2 ethyl acetate/hexane Rf = 0.64; yellow solid
(274 mg, 72%); mp 148−149 °C; 1H NMR (600 MHz, CDCl3) δ 7.69
(d, J = 8.4 Hz, 2H), 7.34 (d, J = 8.4 Hz, 2H), 7.15 (s, 1H), 7.11 (s,
1H), 6.46 (s, 1H), 3.91 (s, 3H), 3.74 (s, 3H), 3.73 (s, 3H), 2.46 (s,
3H); 13C {1H}NMR (150 MHz, CDCl3) δ 153.5, 153.0, 146.5, 143.4,
132.4, 130.5, 129.9, 112.1, 104.4, 96.6, 95.9, 56.9, 56.4, 56.2, 21.9; FT-
IR (KBr) 2977, 1599, 1525, 1406, 1384, 1332, 1305, 1232, 1214, 1153,
1112, 1083, 1039, 1027 cm−1; HRMS (APCI) m/z [M − H]− calcd
for C17H19NO7S, 380.0809; found, 380.0807.
1,2,3-Trimethoxy-5-(nitro(tosyl)methyl)benzene 3p. Analytical
TLC on silica gel, 1:2 ethyl acetate/hexane Rf = 0.59; yellow solid
(267 mg, 70%); mp 150−151 °C; 1H NMR (600 MHz, CDCl3) δ 7.64
(d, J = 8.4 Hz, 2H), 7.34 (d, J = 7.8 Hz, 2H), 6.63 (s, 2H), 6.37 (s,
1H), 3.86 (s, 3H), 3.75 (s, 6H), 2.46 (s, 3H); 13C {1H}NMR (150
MHz, CDCl3) δ 153.4, 147.0, 140.9, 131.1, 130.8, 129.9, 120.1, 107.0,
103.8, 61.1, 56.3, 21.9; FT-IR (KBr) 2945, 1593, 1557, 1509, 1465,
1424, 1336, 1277, 1244, 1230, 1155, 1129, 1079, 1018 cm−1; HRMS
(APCI) m/z [M − H]− calcd for C17H19NO7S, 380.0809; found,
380.0815.
2-(Nitro(tosyl)methyl)naphthalene 3q. Analytical TLC on silica
gel, 1:4 ethyl acetate/hexane Rf = 0.71; white solid (249 mg, 73%); mp
175−176 °C; 1H NMR (600 MHz, CDCl3) δ 7.95 (s, 1H), 7.86 (t, J =
9.0 Hz, 2H), 7.82 (d, J = 7.8 Hz, 1H), 7.61−7.52 (m, 5H), 7.29 (d, J =
8.4 Hz, 2H), 6.63 (s, 1H), 2.45 (s, 3H); 13C {1H}NMR (150 MHz,
CDCl3) δ 147.0, 134.6, 132.7, 131.3, 130.9, 130.7, 130.0, 129.0, 128.8,
128.4, 127.9, 127.3, 125.3, 122.5, 104.2, 22.0; FT-IR (KBr) 2987, 1593,
1559, 1507, 1338, 1306, 1211, 1156, 1125, 1083, 1018, 818, 665 cm−1;
HRMS (APCI) m/z [M − H]− calcd for C18H15NO4S, 340.0649;
found, 340.0653.
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1-Bromo-4-(nitro(tosyl)methyl)benzene 3h. Analytical TLC on
silica gel, 1:4 ethyl acetate/hexane Rf = 0.40; white solid (222 mg,
1
60%); mp 129−130 °C; H NMR (600 MHz, CDCl3) δ 7.62 (d, J =
8.4 Hz, 2H), 7.55 (d, J = 8.4 Hz, 2H), 7.37−7.33 (m, 4H), 6.41 (s,
1H), 2.47 (s, 3H); 13C {1H}NMR (150 MHz, CDCl3) δ 147.3, 132.5,
131.3, 131.0, 130.7, 130.2, 126.8, 124.2, 103.2, 22.0; FT-IR (KBr)
2923, 1626, 1562, 1488, 1408, 1384, 1340, 1155, 1075, 1012, 707, 658
cm−1; HRMS (APCI) m/z [M − H]− calcd for C14H12BrNO4S,
367.9598; found, 367.9591.
1-Chloro-4-(nitro(tosyl)methyl)benzene 3i. Analytical TLC on
silica gel, 1:3 ethyl acetate/hexane Rf = 0.50; white solid (201 mg,
1
62%); mp 128−129 °C; H NMR (600 MHz, CDCl3) δ 7.62 (d, J =
7.8 Hz, 2H), 7.44 (d, J = 8.4 Hz, 2H), 7.39 (d, J = 8.4 Hz, 2H), 7.34
(d, J = 8.4 Hz, 2H), 6.43 (s, 1H), 2.47 (s, 3H); 13C {1H}NMR (150
MHz, CDCl3) δ 147.3, 138.5, 131.2, 131.0, 130.6, 130.2, 129.5, 123.7,
103.1, 22.0; FT-IR (KBr) 2979, 1665, 1594, 1568, 1494, 1413, 1340,
1310, 1291, 1177, 1152, 1082, 1018, 818, 662 cm−1; HRMS (APCI)
m/z [M − H]− calcd for C14H12ClNO4S, 324.0103; found, 324.0108.
4-(Nitro(tosyl)methyl)benzonitrile 3j. Analytical TLC on silica gel,
1:2 ethyl acetate/hexane Rf = 0.40; white solid (164 mg, 52%); mp
125−126 °C; 1H NMR (600 MHz, CDCl3) δ 7.72 (d, J = 8.4 Hz, 2H),
7.66 (d, J = 8.4 Hz, 2H), 7.63 (d, J = 7.8 Hz, 2H), 7.36 (d, J = 7.8 Hz,
2 H), 6.49 (s, 1H), 2.48 (s, 3H); 13C {1H}NMR (150 MHz, CDCl3) δ
147.8, 132.8, 130.8, 130.7, 130.4, 129.7, 117.7, 115.9, 102.9, 22.1; FT-
IR (KBr) 2924, 2853, 2231, 1741, 1628, 1563, 1462, 1338, 1152, 1081,
1017, 812 cm−1; HRMS (APCI) m/z [M − H]− calcd for
C15H12N2O4S, 315.0445; found, 315.0451.
1-Fluoro-4-(nitro(tosyl)methyl)benzene 3k. Analytical TLC on
1-Chloro-4-(nitro(phenylsulfonyl)methyl)benzene 3s. Analytical
silica gel, 1:2 ethyl acetate/hexane Rf = 0.56; yellow solid (182 mg,
TLC on silica gel, 1:6 ethyl acetate/hexane Rf = 0.29; white solid
1
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59%); mp 107−108 °C; H NMR (600 MHz, CDCl3) δ 7.62 (d, J =
(205 mg, 66%); mp 117−118 °C; H NMR (400 MHz, CDCl3) δ
7.8 Hz, 2H), 7.52−7.49 (m, 2H), 7.34 (d, J = 8.4 Hz, 2H), 7.10 (t, J =
8.4 Hz, 2H), 6.44 (s, 1H), 2.47 (s, 3H); 13C {1H}NMR (100 MHz,
CDCl3) δ 166.1 (JC−F = 251.7 Hz), 147.2, 132.2 (JC−F = 9.2 Hz),
131.0, 130.6, 130.1, 121.2 (JC−F =3.8 Hz), 116.5 (JC−F = 22.1 Hz),
103.0, 22.0; FT-IR (KBr) 2979, 1605, 1566, 1512, 1406, 1384, 1339,
1233, 1154, 1083, 1016, 820, 665 cm−1; HRMS (APCI) m/z [M −
H]− calcd for C14H12FNO4S, 308.0398; found, 308.0396.
7.76−7.74 (m, 3H), 7.56 (t, J = 7.6 Hz, 2H), 7.44−7.38 (m, 4H), 6.46
(s, 1H); 13C {1H}NMR (100 MHz, CDCl3) δ 138.6, 135.7, 134.0,
131.1, 130.6, 129.6, 129.5, 123.5, 103.0; FT-IR (KBr) 2979, 1565,
1488, 1448, 1411, 1355, 1337, 1289, 1180, 1154, 1080, 1012, 770, 728
cm−1; HRMS (APCI) m/z [M − H]− calcd for C13H10ClNO4S,
309.9941; found, 309.9943
1-Methoxy-4-(nitro(phenylsulfonyl)methyl)benzene 3t. Analytical
TLC on silica gel, 1:6 ethyl acetate/hexane Rf = 0.31; white solid (209
mg, 68%); mp 143−144 °C; 1H NMR (600 MHz, CDCl3) δ 7.73 (d, J
= 8.4 Hz, 2H), 7.70 (d, J = 8.4 Hz, 1H), 7.52 (t, J = 7.8 Hz, 2H), 7.39
(d, J = 8.4 Hz, 2H), 6.89 (d, J = 9.0 Hz, 2H), 6.43 (s, 1H), 3.82 (s,
3H); 13C {1H}NMR (150 MHz, CDCl3) δ 162.4, 135.4, 134.4, 131.4,
130.6, 129.3, 116.8, 114.5, 103.5, 55.6; FT-IR (KBr) 2990, 1607, 1578,
1554, 1513, 1460, 1445, 1338, 1309, 1276, 1262, 1181, 1160, 1113,
1084, 1018 cm−1; HRMS (APCI) m/z [M − H]− calcd for
C14H13NO5S, 306.0442; found, 306.0448.
1-Chloro-4-(((4-chlorophenyl)(nitro)methyl)sulfonyl)benzene 3u.
Analytical TLC on silica gel, 1:4 ethyl acetate/hexane Rf = 0.45; white
solid (197 mg, 57%); mp 117−118 °C; 1H NMR (600 MHz, CDCl3)
δ 7.67 (d, J = 9.0 Hz, 2H), 7.53 (d, J = 8.4 Hz, 2H), 7.41 (s, 4H), 6.44
(s, 1H); 13C {1H}NMR (150 MHz, CDCl3) δ 143.0, 138.8, 132.4,
132.1, 131.0, 129.9, 129.7, 123.3, 103.1; FT-IR (KBr) 2901, 2072,
1639, 1430, 1372, 1339, 1319, 1282, 1205, 1163, 1059, 1032, 896, 707
cm−1; HRMS (APCI) jkm/z [M − H]− calcd for C13H9Cl2NO4S,
343.9557; found, 343.9550.
1-Methoxy-4-(nitro(tosyl)methyl)benzene 3l. Analytical TLC on
silica gel, 1:4 ethyl acetate/hexane Rf = 0.51; yellow solid (221 mg,
1
69%); mp 126−127 °C; H NMR (600 MHz, CDCl3) δ 7.61 (d, J =
8.4 Hz, 2H), 7.41 (d, J = 8.4 Hz, 2H), 7.32 (d, J = 7.8 Hz, 2H), 6.89
(d, J = 9.0 Hz, 2H), 6.40 (s, 1H), 3.83 (s, 3H), 2.46 (s, 3H); 13C
{1H}NMR (150 MHz, CDCl3) δ 162.4, 146.9, 131.5, 131.4, 130.7,
130.0, 117.0, 114.5, 103.6, 55.6, 22.0; FT-IR (KBr) 2995, 1609, 1596,
1552, 1515, 1460, 1341, 1309, 1278, 1263, 1182, 1157, 1085, 1019
cm−1; HRMS (APCI) m/z [M − H]− calcd for C15H15NO5S,
320.0598; found, 320.0599.
Methyl-4-(nitro(tosyl)methyl)benzoate 3m. Analytical TLC on
silica gel, 1:4 ethyl acetate/hexane Rf = 0.22; white solid (202 mg,
1
58%); mp 110−111 °C; H NMR (600 MHz, CDCl3) δ 8.05 (d, J =
8.4 Hz, 2H), 7.59−7.54 (m, 4H), 7.32 (d, J = 8.4 Hz, 2H), 6.52 (s,
1H), 3.94 (s, 3H), 2.46 (s, 3H); 13C {1H}NMR (150 MHz, CDCl3) δ
166.1, 147.4, 133.2, 130.9, 130.7, 130.2, 130.1, 129.8, 129.5, 103.4,
52.7, 22.0; FT-IR (KBr) 2995, 1714, 1593, 1555, 1432, 1341, 1291,
1187, 1154, 1114, 1083, 1018 cm−1; HRMS (APCI) m/z [M − H]−
calcd for C16H15NO6S, 348.0547; found, 348.0541.
1-Chloro-4-(((4-methoxyphenyl)(nitro)methyl)sulfonyl)benzene
1-Bromo-2-methoxy-3-(nitro(tosyl)methyl)benzene 3n. Analytical
TLC on silica gel, 1:3 ethyl acetate/hexane Rf = 0.35; white solid (260
mg, 65%); mp 153−154 °C; 1H NMR (600 MHz, CDCl3) δ 7.76 (d, J
= 2.4 Hz, 1H); 7.69 (d, J = 7.8 Hz, 2H), 7.56 (dd, J = 9.0, 2.4 Hz, 1H),
7.37 (d, J = 8.4 Hz, 2H), 7.12 (s, 1H), 6.80 (d, J = 9.0 Hz, 1H), 3.76
3v. Analytical TLC on silica gel, 1:4 ethyl acetate/hexane Rf = 0.40;
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yellow solid (208 mg, 61%); mp 113−114 °C; H NMR (400 MHz,
CDCl3) δ 7.63 (d, J = 8.4 Hz, 2H), 7.49 (d, J = 8.4 Hz, 2H), 7.35 (d, J
= 8.4 Hz, 2H), 6.89 (d, J = 8.4 Hz, 2H), 6.39 (s, 1H), 3.82 (s, 3H); 13C
{1H}NMR (100 MHz, CDCl3) δ 162.5, 142.5, 132.7, 132.1, 131.3,
F
J. Org. Chem. XXXX, XXX, XXX−XXX