The Journal of Organic Chemistry
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Hz, 9.1 Hz, 1H), 4.80 (q, J = 6.4 Hz, 1H), 6.96−7.02 (m, 3H), 7.42−
7.46 (m, 2H); 13C NMR (100 MHz, CDCl3, ppm) δ 13.8, 19.4, 22.4,
31.5, 67.9, 84.6, 115.7 (d, JC−F = 22.0 Hz), 127.6 (d, JC−F = 3.8 Hz),
136.2 (d, JC−F = 8.6 Hz), 162.7 (d, JC−F = 247.3 Hz); 19F NMR (376
MHz, CDCl3, ppm) δ −113.9; IR (NaCl) 2959, 2932, 2870, 1894,
1740, 1589, 1489, 1462, 1396, 1369, 1265, 1227, 1157, 1107, 1088,
1034, 972, 907, 829, 760 cm−1; Anal. Calcd for C12H17FOS: C, 63.12;
H, 7.50. Found: C, 62.98; H, 7.56.
1-[(p-Chlorophenyl)thio]ethyl Butyl Ether (3ae). This compound
was prepared from n-butyl vinyl ether (64.7 μL, 0.5 mmol) and 4-
chlorobenzenethiol (72.3 μL, 0.5 mmol) following the general
procedure for hydrothiolation of vinyl ethers. Isolated as a colorless
oil (118.6 mg, 97%); 1H NMR (400 MHz, CDCl3, ppm) δ 0.92 (t, J =
7.3 Hz, 3H), 1.38 (sext, J = 7.3 Hz, 2H), 1.47 (d, J = 6.4 Hz, 3H),
1.53−1.64 (m, 2H), 3.42 (td, J = 6.9 Hz, 9.0 Hz, 1H), 3.85 (td, J = 6.9
Hz, 9.0 Hz, 1H), 4.85 (q, J = 6.4 Hz, 1H), 7.25 (d, J = 8.2 Hz, 2H),
7.39 (d, J = 8.2 Hz, 2H); 13C NMR (100 MHz, CDCl3, ppm) δ 13.8,
19.4, 22.4, 31.4, 67.7, 84.5, 128.7, 131.5, 133.6, 134.9; IR (NaCl) 2959,
2932, 2870, 1570, 1474, 1389, 1373, 1315, 1269, 1111, 1092, 1015,
972, 907, 822, 741, 625 cm−1; Anal. Calcd for C12H17ClOS: C, 58.88;
H, 7.00. Found: C, 58.65; H, 6.88.
1-(Phenylmethylthio)ethyl Butyl Ether (3af). This compound was
prepared from n-butyl vinyl ether (64.7 μL, 0.5 mmol) and
phenylmethylthiol (58.6 μL, 0.5 mmol) following the general
procedure for hydrothiolation of vinyl ethers. Isolated as a colorless
oil (39.2 mg, 35%); 1H NMR (400 MHz, CDCl3, ppm) δ 0.93 (t, J =
7.3 Hz, 3H), 1.39 (sext, J = 7.3 Hz, 2H), 1.52 (d, J = 6.3 Hz, 3H),
1.51−1.59 (m, 2H), 3.41 (td, J = 6.3 Hz, 9.1 Hz, 1H), 3.61 (td, J = 6.4
Hz, 9.1 Hz, 1H), 3.45 (d, J = 13.1 Hz, 1H), 3.79 (d, J = 13.1 Hz), 4.64
(q, J = 6.3 Hz, 1H), 7.19−7.34 (m, 5H); 13C NMR (100 MHz, CDCl3,
ppm) δ 13.9, 19.5, 22.1, 31.7, 32.6, 66.4, 80.6, 126.8, 128.4, 128.9,
138.8; IR (NaCl) 3028, 2959, 2932, 2866, 1597, 1489, 1454, 1369,
1265, 1231, 1103, 1030, 972, 907, 764, 702, 629 cm−1.
1-(Cyclohexylthio)ethyl Butyl Ether (3ag). This compound was
prepared from n-butyl vinyl ether (64.7 μL, 0.5 mmol) and 4-
methylbenzenethiol (61.2 μL, 0.5 mmol) following the general
procedure for hydrothiolation of vinyl ethers. Isolated as a pale yellow
oil (42.7 mg, 39%); 1H NMR (400 MHz, CDCl3, ppm) δ 0.93 (t, J =
7.3 Hz, 3H), 1.21−1.43 (m, 8H), 1.51−1.63 (m, 5H), 1.72−1.75 (m,
2H), 1.93−2.02 (m, 2H), 2.81−2.89 (m, 1H), 3.44 (td, J = 6.4 Hz, 9.2
Hz, 1H), 3.63 (td, J = 6.4 Hz, 9.2 Hz, 1H), 4.78 (q, J = 6.4 Hz, 1H);
13C NMR (100 MHz, CDCl3, ppm) δ 13.9, 19.4, 22.6, 25.7, 31.7, 34.5,
35.0, 41.4, 66.1, 80.6; IR (NaCl) 2928, 2855, 1447, 1369, 1312, 1265,
1204, 1103, 1034, 999, 973, 907, 887, 772, 741, 637 cm−1; HRMS (EI)
Calcd for C12H24OS: 216.1548. Found: 216.1549.
1186, 1091, 1025, 928, 745, 692 cm−1; HRMS (FAB) Calcd for
C15H22NOS [M + H]+: 264.1422. Found: 264.1425.
1-[3-Phenyl-(1-Phenylthio)propyl]-2-pyrrolidinone (5ca). This
compound was prepared from 1-(3-Phenyl-1-propenyl)-2-pyrrolidi-
none (112 mg, 0.5 mmol) and benzenethiol (51.1 μL, 0.5 mmol)
following the general procedure for hydrothiolation of a N-vinyl
lactam. Isolated as a yellow oil (107.0 mg, 69%); 1H NMR (400 MHz,
CDCl3, ppm) δ 1.66−1.84 (m, 2H), 2.00−2.26 (m, 4H), 2.59−2.66
(m, 1H), 2.74−2.81 (m, 1H), 3.14−3.20 (m, 1H), 3.50−3.56 (m, 1H),
5.80 (dd, J = 6.0 Hz, 9.2 Hz, 1H), 7.17−7.30 (m, 8H), 7.38−7.40 (d, J
= 6.9 Hz, 2H); 13C NMR (100 MHz, CDCl3, ppm) δ 17.6, 31.0, 33.0,
34.3, 41.4, 58.9, 126.1, 127.4, 128.2, 128.4, 128.8, 132.2, 132.6, 140.5,
174.9; IR (NaCl) 3500, 3061, 3024, 2942, 1685, 1585, 1501, 1489,
1411, 1359, 1283, 1265, 1082, 1027, 908, 838, 745, 693 cm−1; HRMS
(FAB) Calcd for C19H22NOS [M + H]+: 312.1422. Found: 312.1417.
1-[3,3-Dimethyl-(1-Phenylthio)butyl]-2-pyrrolidinone (5da). This
compound was prepared from 1-(3,3-dimethyl-1-butenyl)-2-pyrrolidi-
none (83.6 mg, 0.5 mmol) and benzenethiol (51.1 μL, 0.5 mmol)
following the general procedure for hydrothiolation of a N-vinyl
1
lactam. Isolated as a yellow oil (98.3 mg, 71%); H NMR (400 MHz,
CDCl3, ppm) δ 0.97 (s, 9H), 1.57 (dd, J = 3.2 Hz, 14.7 Hz, 1H),
1.61−1.70 (m, 1H), 1.74−1.87 (m, 2H), 1.90−1.99 (m, 1H), 2.09−
2.20 (m, 1H), 3.26−3.32 (m, 1H), 3.50−3.56 (m, 1H), 5.94 (dd, J =
3.2 Hz, 9.6 Hz, 1H), 7.20−7.28 (m, 3H), 7.40−7.42 (m, 2H); 13C
NMR (100 MHz, CDCl3, ppm) δ 17.7, 29.3, 31.3, 31.3, 41.2, 44.7,
56.3, 127.5, 128.6, 132.3, 132.6, 174.4; IR (NaCl) 3492, 3057, 2953,
2878, 1691, 1582, 1476, 1411, 1362, 1283, 1266, 1153, 1020, 933, 895,
843, 744, 692 cm−1; Anal. Calcd for C16H23NOS: C, 69.27; H, 8.36; N,
5.05. Found: C, 69.00; H, 8.38; N, 5.13.
1-[2-Phenyl-(1-phenylthio)ethyl]-2-pyrrolidinone (5ea). This
compound was prepared from 1-styryl-2-pyrrolidinone (93.5 mg, 0.5
mmol) and benzenethiol (51.1 μL, 0.5 mmol) following the general
procedure for hydrothiolation of a N-vinyl lactam. Isolated as a yellow
1
oil (70.9 mg, 48%); H NMR (400 MHz, CDCl3, ppm) δ 1.65−1.81
(m, 2H), 1.95−2.12 (m, 2H), 2.99−3.05 (m, 1H), 3.16−3.29 (m, 2H),
3.53−3.59 (m, 1H), 6.05 (dd, J = 6.9 Hz, J = 9.2 Hz, 1H), 7.21−7.31
(m, 8H), 7.39−7.41 (m, 2H); 13C NMR (100 MHz, CDCl3, ppm) δ
17.7, 30.9, 38.9, 41.7, 59.4, 126.9, 127.5, 128.4, 128.7, 128.8, 132.2,
132.6, 136.4; IR (NaCl) 3491, 3068, 3024, 2969, 1690, 1646, 1583,
1482, 1456, 1438, 1410, 1265, 1157, 1078, 1025, 993, 929, 926, 746,
697 cm−1; HRMS (FAB) Calcd for C18H20NOS [M + H]+: 298.1266.
Found: 298.1261.
1-(1-Phenylthio)ethyl-2-caprolactam (5fa). This compound was
prepared from 1-vinyl-2-caprolactam (69.6 mg, 0.5 mmol) and
benzenethiol (51.1 μL, 0.5 mmol) following the general procedure
for hydrothiolation of a N-vinyl lactam. Isolated as a yellow oil (108.0
1
1-[(1-Phenylthio)ethyl]-2-pyrrolidinone (5aa). This compound
was prepared from 1-vinyl-2-pyrrolidinone (53.2 μL, 0.5 mmol) and
benzenethiol (51.1 μL, 0.5 mmol) following the general procedure for
hydrothiolation of a N-vinyl lactam. Isolated as a pale yellow oil (104.4
mg, 87%); H NMR (400 MHz, CDCl3, ppm) δ 1.38−1.66 (m, 6H),
1.42 (d, J = 6.9 Hz, 3H), 2.32−2.43 (m, 2H), 3.27−3.33 (m, 1H),
3.41−3.47 (m, 1H), 6.05 (q, J = 6.9 Hz, 1H), 7.15−7.19 (m, 1H),
7.23−7.27 (m, 2H), 7.33−7.35 (m, 2H); 13C NMR (100 MHz,
CDCl3, ppm) δ 19.0, 23.1, 28.9, 29.7, 37.3, 42.5, 55.7, 126.4, 128.6,
130.0, 133.9, 175.5; IR (NaCl) 3512, 3050, 2929, 2854, 1640, 1477,
1438, 1412, 1366, 1310, 1183, 1147, 1094, 1059, 923, 888, 846, 743,
691 cm−1; Anal. Calcd for C14H19NOS: C, 67.43; H, 7.68; N, 5.62.
Found: C, 67.17; H, 7.87; N, 5.68.
1
mg, 94%); H NMR (400 MHz, CDCl3, ppm) δ 1.48 (d, J = 6.9 Hz,
3H), 1.76−1.83 (m, 1H), 1.86−1.96 (m, 1H), 2.04−2.12 (m, 1H),
2.22−2.30 (m, 1H), 3.28−3.34 (m, 1H), 3.52−3.58 (m, 1H), 5.89 (q, J
= 6.9 Hz, 1H), 7.20−7.30 (m, 3H), 7.39−7.41 (m, 2H); 13C NMR
(100 MHz, CDCl3, ppm) δ 17.5, 18.7, 31.0, 41.1, 54.2, 127.3, 128.6,
132.0, 132.8, 174.3; IR (NaCl) 3495, 3071, 2986, 2881, 1686, 1585,
1481, 1458, 1416, 1350, 1269, 1200, 1092, 1065, 1018, 953, 926, 837,
748, 694 cm−1; HRMS (EI) Calcd for C12H15NOS: 221.0874. Found:
221.0875.
1-[(1-Phenylthio)pentyl]-2-pyrrolidinone (5ba). This compound
was prepared from 1-(1-pentenyl)-2-pyrrolidinone (76.6 mg, 0.5
mmol) and benzenethiol (51.1 μL, 0.5 mmol) following the general
procedure for hydrothiolation of N-vinyl lactam. Isolated as a yellow
oil (96.3 mg, 73%); 1H NMR (400 MHz, CDCl3, ppm) δ 0.90 (t, J =
6.9 Hz, 3H), 1.25−1.42 (m, 4H), 1.68−1.97 (m, 4H), 2.04−2.12 (m,
1H), 2.24−2.32 (m, 1H), 3.20−3.26 (m, 1H), 3.52−3.58 (m, 1H),
5.73 (dd, J = 5.7 Hz, 9.4 Hz, 1H), 7.19−7.29 (m, 3H), 7.38−7.40 (m,
2H); 13C NMR (100 MHz, CDCl3, ppm) δ 13.8, 17.7, 22.0, 28.5, 31.1,
32.2, 41.3, 58.8, 127.2, 128.7, 132.0, 132.9, 174.8; IR (NaCl) 3441,
3049, 2931, 2861, 1685, 1583, 1486, 1458, 1412, 1348, 1281, 1265,
1-{[1-(p-Methylphenyl)thio]ethyl}-2-pyrrolidinone (5ab). This
compound was prepared from 1-vinyl-2-pyrrolidinone (53.2 μL, 0.5
mmol) and 4-methylbenzenethiol (62.1 μL, 0.5 mmol) following the
general procedure for hydrothiolation of a N-vinyl lactam. Isolated as a
pale yellow oil (100.6 mg, 85%); 1H NMR (400 MHz, CDCl3, ppm) δ
1.47 (d, J = 6.8 Hz, 3H), 1.75−1.98 (m, 2H), 2.05−2.13 (m, 1H),
2.22−2.30 (m, 1H), 2.30 (s, 3H), 3.28−3.34 (m, 1H), 3.56−3.62 (m,
1H), 5.82 (q, J = 6.8 Hz, 1H), 7.08 (d, J = 7.7 Hz, 2H), 7.28−7.31 (m,
2H); 13C NMR (100 MHz, CDCl3, ppm) δ 17.6, 18.7, 21.0, 31.1, 41.1,
54.7, 129.0, 129.5, 132.7, 137.7, 174.3; IR (NaCl) 3499, 2974, 2951,
1928, 2885, 1693, 1493, 1458, 1412, 1350, 1265, 1200, 1099, 1088,
1061, 957, 810, 691 cm−1; HRMS (FAB) Calcd for C13H18NOS [M +
H]+: 236.1109. Found: 236.1123.
1-{[1-(p-Methoxylphenyl)thio]ethyl}-2-pyrrolidinone (5ac). This
compound was prepared from 1-vinyl-2-pyrrolidinone (53.2 μL, 0.5
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dx.doi.org/10.1021/jo500586a | J. Org. Chem. 2014, 79, 5028−5035