S. Ayuba et al.
Bull. Chem. Soc. Jpn., 75, No. 7 (2002) 1601
Calcd for C12H14ClFO2S: (M+) 276.0387. Found: m/z 276.0405.
Calcd for C12H14ClFO2S: C, 52.08; H, 5.10; Cl, 12.81; F, 6.86; S,
11.59%. Found: C, 51.93; H, 5.11; Cl, 12.85; F, 6.86; S, 11.78%.
Methyl 2-(p-Chlorophenylthio)-2-fluoropropanoate (2e).
A clear liquid; 1H NMR (400 MHz) δ 1.91 (3H, d, J = 18.3 Hz),
3.60 (3H, s), 7.33 (2H, d, J = 8.5 Hz), 7.47 (2H, d, J = 8.5 Hz);
19F NMR (376 MHz) δ −127.24 (1F, q, J = 18.3 Hz); IR (neat)
2953, 1759, 1573, 1476, 1442, 1390, 1283, 1128, 1091, 1014,
979, 911, 824, 747, 699 cm−1; MS m/z (rel intensity) 250 (M+
+ 2, 19), 248 (M+, 50), 189 (100), 108 (19), 40 (20); HRMS (EI)
Calcd for C10H10ClFO2S: (M+) 248.0074. Found: m/z 248.0089.
Calcd for C10H10ClFO2S: C, 48.29; H, 4.05; Cl, 14.26; F, 7.64; S,
12.89%. Found: C, 48.29; H, 4.04; Cl, 14.28; F, 7.88; S, 13.10%.
4.23; Cl, 11.44; F, 6.13; N, 4.52; S, 10.30%. Found: C, 58.20; H,
4.37; Cl, 11.67; F, 6.31; N, 4.63; S, 10.50%.
N,N-Diisopropyl-2-(p-chlorophenylthio)-2,2-difluoroacet-
amide (3i). A white solid, Mp 62–63 °C; 1H NMR (400 MHz) δ
1.22 (6H, d, J = 6.59 Hz), 1.43 (6H, d, J = 6.83 Hz), 3.47–3.55
(1H, m), 4.40–4.46 (1H, m), 7.37 (2H, d, J = 8.5 Hz), 7.56 (2H, d,
J = 8.5 Hz); 19F NMR (376 MHz) δ −73.46 (2F, s); IR (KBr)
2974, 1653, 1573, 1444, 1376, 1347, 1146, 1093, 999, 897, 818,
787, 747, 608, 531, 504 cm−1; MS m/z (rel intensity) 321 (M+,
20), 193 (18), 128 (72), 108 (10), 86 (100), 43 (68); HRMS (EI)
Calcd for C14H18ClF2NOS: (M+) 321.0765. Found: m/z 321.0774.
Calcd for C14H18ClF2NOS: C, 52.25; H, 5.64; Cl, 11.02; F, 11.81;
N, 4.35; S, 9.96%. Found: C, 52.31; H, 5.60; Cl, 10.94; F, 11.78;
N, 4.37; S, 9.99%.
2-(p-Chlorophenylthio)-2-fluoro-4-butanolide (2f).
A
white solid; Mp 71 °C; 1H NMR (400 MHz) δ 2.55–2.60 (1H, m),
2.74–2.86 (1H, m), 4.32–4.45 (2H, m), 7.36 (2H, d, J = 8.5 Hz),
7.51 (2H, d, J = 8.5 Hz); 19F NMR (376 MHz) δ −135.76 (1F, d,
J = 15.9 Hz); IR (KBr) 1793, 1574, 1474, 1374, 1305, 1223,
1180, 1049, 1011, 947, 891, 822, 742, 675, 607, 495 cm−1; MS
m/z (rel intensity) 248 (M+ + 2, 15), 246 (M+, 40), 226 (100), 169
(74), 163 (55), 155 (20), 139 (47), 134 (65), 125 (60), 108 (49), 89
(14), 75 (41), 71 (32), 59 (22), 50 (20), 45 (18); HRMS (EI) Calcd
for C10H8ClFO2S: (M+) 245.9917. Found: m/z 245.9914.
N,N-Diisopropyl-2-(p-chlorophenylthio)-2-fluoroacetamide
(2i). A white solid, Mp 85 °C; 1H NMR (400 MHz) δ 1.24 (3H,
d, J = 6.3 Hz), 1.25 (3H, d, J = 6.3 Hz), 1.35 (3H, d, J = 6.8 Hz),
1.42 (3H, d, J = 6.8 Hz), 3.42–3.49 (1H, m), 4.16–4.22 (1H, m),
6.16 (1H, d, J = 55.9 Hz), 7.33 (2H, d, J = 8.3 Hz), 7.50 (2H, d, J
= 8.3 Hz); 19F NMR (376 MHz) δ −152.36 (1F, d, J = 55.9 Hz);
IR (KBr) 2993, 1646, 1475, 1338, 1208, 1133, 1092, 1046, 1011,
933, 824, 788, 741, 635, 605 cm−1; MS m/z (rel intensity) 303
(M+, 3), 143 (37), 128 (45), 108 (41), 99 (10), 86 (59), 75 (12), 43
(100); HRMS (EI) Calcd for C14H19ClFNOS: (M+) 303.0860.
Found: m/z 303.0858. Calcd for C14H19ClFNOS: C, 55.34; H,
6.30; Cl, 11.67; F, 6.25; N, 4.61; S, 10.55%. Found: C, 55.47; H,
6.21; Cl, 11.63; F, 6.23; N, 4.71; S, 10.49%.
2-(p-Chlorophenylthio)-2-buten-4-olide (6f). A white solid,
1
Mp 79–80 °C; H NMR (400 MHz) δ 4.82–4.83 (2H, m), 6.72–
6.73 (1H, m), 7.40 (2H, d, J = 8.5 Hz), 7.49 (2H, d, J = 8.5 Hz);
IR (KBr) 3087, 1758, 1477, 1438, 1390, 1343, 1280, 1156, 1093,
1050, 1008, 834, 821, 763, 727, 498 cm−1; MS m/z (rel intensity)
228 (M+ + 2, 37), 226 (M+, 100), 169 (63), 139 (33), 134 (57),
125 (44), 108 (24), 75 (34), 71 (33); HRMS (EI) Calcd for
C10H7ClO2S: (M+) 225. 9855. Found: m/z 225.9843.
N-Butyl-2-(p-chlorophenylthio)-2-fluoroacetamide (2j).
A
white solid, Mp 53 °C; 1H NMR (400 MHz) δ 0.87 (3H, t, J = 7.3
Hz), 1.12–1.32 (4H, m), 3.05–3.24 (2H, m), 6.05 (1H, bs), 6.06
(1H, d, J = 52.2 Hz), 7.33 (2H, d, J = 8.5 Hz), 7.51 (2H, d, J =
8.3 Hz); 19F NMR (376 MHz) δ −156.82 (1F, d, d J = 4.3, 52.2
Hz); IR (KBr) 3331, 2956, 2870, 1662, 1542, 1475, 1304, 1261,
1093, 1002, 977, 831, 805, 729, 701cm−1; MS m/z (rel intensity)
275 (M+, 22), 176 (20), 143 (56), 108 (53), 100 (55), 75 (15), 57
(100), 43 (49); HRMS (EI) Calcd for C12H15ClFNOS: (M+)
275.0547. Found: m/z 275.0550. Calcd for C12H15ClFNOS: C,
52.26; H, 5.48; Cl, 12.86; F, 6.89; N, 5.08; S, 11.63%. Found: C,
52.18; H, 5.41; Cl, 12.83; F, 6.88; N, 5.18; S, 11.62%.
2-(p-Chlorophenylthio)-2-fluoroacetamide (2g).
A white
solid, Mp 119 °C; 1H NMR (400 MHz) δ 5.58 (1H, bs), 6.03 (1H,
bs), 6.07 (1H, d, J = 52.7 Hz), 7.35 (2H, d, J = 8.3 Hz), 7.53 (2H,
d, J = 8.3 Hz); 19F NMR (376 MHz) δ −155.46 (1F, d, J = 52.7
Hz); IR (KBr) 3415, 3177, 2946, 1671, 1474, 1408, 1241, 1092,
1001, 921, 824, 798, 657, 572, 511 cm−1; MS m/z (rel intensity)
219 (M+, 28), 175 (32), 143 (91), 108 (100), 75 (36), 63 (33), 44
(92); HRMS (EI) Calcd for C8H7ClFNOS: (M+) 218.9921.
Found: m/z 218.9913. Calcd for C8H7ClFNOS: C, 43.74; H, 3.21;
Cl, 16.14; F, 8.65; N, 6.38; S, 14.60%. Found: C, 44.01; H, 3.38;
Cl, 16.05; F, 8.56; N, 6.38; S, 14.81%.
N-Butyl-2-(p-chlorophenylthio)-2,2-difluoroacetamide (3j).
A white solid, Mp 44 °C; 1H NMR (400 MHz) δ 0.92 (3H, t, J =
7.3 Hz), 1.25–1.34 (2H, m), 1.43–1.50 (2H, m), 3.28 (2H, q, J =
6.8 Hz), 6.12 (1H, bs), 7.38 (2H, d, J = 8.8 Hz), 7.57 (2H, d, J =
8.5 Hz); 19F NMR (376 MHz) δ −82.8 (2F, s); IR (KBr) 3311,
2957, 1678, 1544, 1475, 1308, 1092, 1035, 1014, 987, 930, 822
cm−1; MS m/z (rel intensity) 293 (M+, 49), 193 (18), 144 (30),
111 (13), 100 (55), 57 (100), 41 (19); HRMS (EI) Calcd for
C12H14ClF2NOS: (M+) 293.0426. Found: m/z 293.0439. Calcd
for C12H14ClF2NOS: C, 49.06; H, 4.80; Cl, 12.07; F, 12.93; N,
4.77; S, 10.92%. Found: C, 48.94; H, 4.69; Cl, 12.21; F, 13.07; N,
4.87; S, 10.93%.
2-(p-Chlorophenylthio)-2,2-difluoroacetamide (3g).
A
white solid, Mp 125–126 °C; 1H NMR (400 MHz) δ 5.65 (1H, bs),
6.09 (1H, bs), 7.39 (2H, d, J = 8.5 Hz), 7.58 (2H, d, J = 8.5 Hz);
19F NMR (376 MHz) δ −155.46 (2F, d, J = 52.7 Hz); IR (KBr)
3473, 3403, 3180, 1717, 1685, 1611, 1476, 1415, 1122, 1078,
1015, 983, 827, 795, 625, 505 cm−1; MS m/z (rel intensity) 239
(M+ + 2, 37), 237 (M+, 100), 193 (76), 144 (80), 108 (56), 75
(22), 44 (55); HRMS (EI) Calcd for C8H6ClF2NOS: (M+)
236.9826. Found: m/z 236.9837.
N-Benzyl-2-(p-chlorophenylthio)-2-fluoroacetamide (2h).
A white solid, Mp 85 °C; 1H NMR (400 MHz) δ 4.24 (1H, dd, J =
4.9, 14.6 Hz), 4.40 (1H, dd, J = 6.3, 14.6 Hz), 6.11 (1H, d, J =
52.0 Hz), 6.29 (1H, bs), 6.99–7.01 (2H, m), 7.26–7.33 (5H, m),
7.49 (2H, d, J = 8.5 Hz); 19F NMR (376 MHz) δ −157.47 (1F, dd,
J = 4.3, 52.0 Hz); IR (KBr) 3389, 1672, 1517, 1475, 1455, 1096,
1023, 984, 823, 799, 757, 720, 696, 614, 511, 472 cm−1; MS m/z
(rel intensity) 309 (M+, 4), 166 (24), 143 (18), 108 (20), 91 (100),
65 (14); HRMS (EI) Calcd for C15H13ClFNOS: (M+) 309.0390.
Found: m/z 309.0393. Calcd for C15H13ClFNOS: C, 58.16; H,
(p-Chlorophenylthio)fluoromethane (2k).15 A clear liquid;
1H NMR (400 MHz) δ 5.69 (2H, d, J = 52.7 Hz), 7.32 (2H, d, J =
8.5 Hz), 7.43 (2H, d, J = 8.5 Hz); 19F NMR (376 MHz) δ
−182.84 (1F, t, J = 52.7 Hz); IR (neat) 2943, 1895, 1637, 1574,
1478, 1429, 1390, 1322, 1232, 1096, 1013, 965, 818, 747,
731cm−1; MS m/z (rel intensity) 176 (M+, 100), 143 (65), 108
(76).
1
(Phenylthio)fluoromethane (2l).9f A clear liquid; H NMR
(400 MHz) δ 5.37 (2H, d, J = 52.9 Hz), 7.29–7.51 (5H, m); 19F
NMR (376 MHz) δ −182.25 (1F, t, J = 52.9 Hz); IR (neat) 3061,