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M. Shimizu et al. / Tetrahedron 62 (2006) 2175–2182
7.67 (1H, s), 8.07 (1H, dd, JZ7.6, 1.2 Hz); 13C NMR
(125 MHz, CDCl3): d 14.2, 62.0, 121.6, 123.6, 125.0, 125.4,
130.6, 131.1, 133.9, 143.2, 145.5, 167.1; IR (KBr): nmax
2983, 1688, 1463, 1280, 1156, 1057, 743 cmK1; HRMS:
Calcd for C12H12N2O2S: 248.0619. Found: 248.0597.
(2H, m), 7.48 (1H, dd, JZ7.6, 1.5 Hz), 8.10 (1H, dd, JZ7.9,
1.5 Hz); 13C NMR (125 MHz, CDCl3): d 14.3, 62.1, 113.3,
121.7, 122.8, 123.0, 124.7, 125.0, 125.4, 126.9, 131.3,
133.7, 137.9, 141.9, 167.2, 171.4; IR (KBr): nmax 1701,
1458, 1281, 1138, 747 cmK1
.
Anal. Calcd for
C16H13NO3S2: C, 57.99; H, 3.95; N, 4.23. Found: C,
57.99; H, 3.85; N, 4.15.
4.2.2. N-[(2-Ethoxycarbonylbenzene)sulfenyl]benzimida-
zole (2b). Mp 136.8–138.0 8C (from ethyl acetate–hexane);
RfZ0.3 (CH2Cl2/ethyl acetateZ20:1); 1H NMR (500 MHz,
CDCl3): d 1.48 (3H, t, JZ7.3 Hz), 4.50 (2H, q, JZ7.3 Hz),
6.10 (1H, d, JZ7.9 Hz), 7.20–7.27 (2H, m), 7.34 (1H, t, JZ
7.6 Hz), 7.37 (1H, t, JZ7.6 Hz), 7.51 (1H, d, JZ7.9 Hz),
7.90 (1H, d, JZ7.6 Hz), 8.03 (1H, s), 8.11 (1H, d, JZ
7.6 Hz); 13C NMR (125 MHz, CDCl3): d 14.3, 62.1, 111.0,
120.8, 121.8, 123.5, 124.2, 124.5, 125.5, 131.0, 133.8,
136.2, 143.9, 144.3, 148.3, 167.2; IR (KBr): nmax 1692,
1146, 748 cmK1. Anal. Calcd for C16H14N2O2S: C, 64.41;
H, 4.73; N, 9.39. Found: C, 64.55; H, 4.67; N, 9.15.
4.2.7. N-[(2-Ethoxycarbonylbenzene)sulfenyl]-2,1-benz-
isothiazoline-3-one (2g). Mp 160.8–161.8 8C (from ethyl
acetate–hexane); RfZ0.6 (CH2Cl2/ethyl acetateZ100:1);
1H NMR (500 MHz, CDCl3): d 1.45 (3H, t, JZ7.3 Hz), 4.46
(2H, q, JZ7.3 Hz), 6.84 (1H, dd, JZ8.2, 0.6 Hz), 7.16 (1H,
ddd, JZ7.9, 6.7, 1.2 Hz), 7.26 (1H, ddd, JZ7.9, 7.3,
0.6 Hz), 7.42 (1H, ddd, JZ8.2, 7.3, 1.2 Hz), 7.54 (1H, dd,
JZ6.7, 1.5 Hz), 7.57 (1H, ddd, JZ7.9, 7.3, 1.5 Hz), 7.89
(1H, dd, JZ7.3, 1.2 Hz), 8.10 (1H, dd, JZ7.9, 1.2 Hz); 13C
NMR (125 MHz, CDCl3): d 14.3, 62.0, 113.6, 121.5, 121.9,
122.9, 123.8, 124.6, 125.5, 131.2, 133.6, 134.6, 144.6,
155.3, 167.0, 190.0; IR (KBr): nmax 1682, 1601, 1468, 1312,
1154, 941, 897, 743 cmK1. Anal. Calcd for C16H13NO3S2:
C, 57.99; H, 3.95; N, 4.23. Found: C, 58.32; H, 3.78;
N, 4.11.
4.2.3. N-[(2-Methoxycarbonylbenzene)sulfenyl]benz-
imidazole (2c). Mp 167.2–169.2 8C (from ethyl acetate–
1
hexane); RfZ0.5 (CH2Cl2/ethyl acetateZ10:1); H NMR
(500 MHz, CDCl3): d 4.04 (3H, s), 6.11 (1H, dd, JZ8.2,
1.2 Hz), 7.21–7.29 (2H, m), 7.33–7.40 (2H, m), 7.51 (1H,
dd, JZ7.2, 0.9 Hz), 7.90 (1H, dt, JZ7.9, 0.9 Hz), 8.04 (1H,
s), 8.09 (1H, dd, JZ7.9, 1.5 Hz); 13C NMR (125 MHz,
CDCl3): d 52.9, 111.0, 120.8, 121.9, 123.5, 123.8, 124.5,
125.5, 131.0, 133.9, 136.2, 143.9, 144.3, 148.3, 167.6; IR
(KBr): nmax 1698, 1433, 1300, 1142, 748 cmK1. Anal. Calcd
for C15H12N2O2S: C, 63.36; H, 4.25; N, 9.85. Found: C,
63.26; H, 4.15; N, 9.66.
4.2.8. N-[(2-Ethoxycarbonylbenzene)sulfenyl]phthal-
imide (2h). Mp 228.0–229.0 8C (from ethyl acetate); RfZ
0.6 (CH2Cl2/ethyl acetateZ10:1); 1H NMR (500 MHz,
CDCl3): d 1.44 (3H, t, JZ7.3 Hz), 4.46 (2H, q, JZ7.3 Hz),
6.87 (1H, dd, JZ8.2, 0.9 Hz), 7.22 (1H, td, JZ7.9, 1.2 Hz),
7.39 (1H, ddd, JZ8.2, 7.3, 1.5 Hz), 7.85–7.86 (2H, m),
8.02–8.02 (2H, m), 8.08 (1H, dd, JZ7.9, 1.5 Hz); 13C NMR
(125 MHz, CDCl3): d 14.3, 61.9, 121.5, 124.2, 125.1, 125.2,
131.2, 132.2, 133.3, 134.9, 142.6, 166.9, 168.1; IR (KBr):
nmax 1740, 1688, 1273, 1046, 748, 711 cmK1. Anal. Calcd
for C17H13NO4S: C, 62.37; H, 4.00; N, 4.28. Found: C,
62.41; H, 3.84; N, 4.28.
4.2.4. N-[(2-Ethoxycarbonylbenzene)sulfenyl]benzotria-
zole (2d). Mp 152.0–154.0 8C (from ethyl acetate–hexane);
RfZ0.5 (CH2Cl2/ethyl acetateZ100:1); 1H NMR
(500 MHz, CDCl3): d 1.49 (3H, t, JZ7.3 Hz), 4.50 (2H,
q, JZ7.3 Hz), 5.85–5.87 (1H, m), 7.21–7.26 (2H, m), 7.47
(1H, ddd, JZ8.2, 7.0, 0.9 Hz), 7.55 (1H, ddd, JZ7.9, 7.0,
0.9 Hz), 7.63 (1H, dt, JZ8.2, 0.9 Hz), 8.09–8.11 (1H, m),
8.19 (1H, dt, JZ8.2, 0.9 Hz); 13C NMR (125 MHz, CDCl3):
d 14.4, 62.3, 110.5, 120.5, 122.1, 124.2, 124.8, 125.7, 128.9,
130.8, 133.8, 137.2, 143.6, 145.9, 167.4; IR (KBr): nmax
4.2.9.
N-[(2-Ethoxycarbonylbenzene)sulfenyl]-3,5-
dimethylpyrazole (2i). Mp 95.2–96.2 8C (from hexane);
RfZ0.6 (CH2Cl2); 1H NMR (500 MHz, CDCl3): d 1.43 (3H,
t, JZ7.2 Hz), 2.26 (3H, s), 2.30 (3H, s), 4.44 (2H, q, JZ
7.2 Hz), 6.04 (1H, dd, JZ8.2, 0.9 Hz), 6.06 (1H, s), 7.19
(1H, td, JZ7.9, 0.9 Hz), 7.36 (1H, ddd, JZ8.2, 7.3, 1.4 Hz),
8.04 (1H, dd, JZ7.9, 1.4 Hz); 13C NMR (125 MHz,
CDCl3): d 11.7, 14.0, 14.3, 61.8, 107.5, 122.4, 123.9,
125.0, 130.7, 133.6, 146.4, 147.6, 152.4, 166.8; IR (KBr):
nmax 1686, 1562, 1462, 1294, 743 cmK1. Anal. Calcd for
C14H16N2O2S: C, 60.85; H, 5.84; N, 10.14. Found: C, 60.95;
H, 5.79; 10.10.
1687, 1300, 1007, 748 cmK1
.
Anal. Calcd for
C15H13N3O2S: C, 60.18; H, 4.38; N, 14.04. Found: C,
60.18; H, 4.28; N, 13.82.
4.2.5. N-[(2-Ethoxycarbonylbenzene)sulfenyl]benz-
oxazol-2-one (2e). Mp 166.5–168.3 8C (from ethyl acet-
ate–hexane); RfZ0.5 (CH2Cl2/ethyl acetateZ100:1); 1H
NMR (500 MHz, CDCl3): d 1.45 (3H, t, JZ7.2 Hz), 4.47
(2H, q, JZ7.2 Hz), 6.82 (1H, dd, JZ8.2, 0.6 Hz), 7.17–7.25
(5H, m), 7.40–7.43 (1H, m), 8.10 (1H, dd, JZ7.8, 1.4 Hz);
13C NMR (125 MHz, CDCl3): d 14.2, 62.1, 110.4, 110.5,
121.4, 123.9, 124.4, 124.8, 125.5, 131.2, 132.3, 133.6,
141.8, 143.2, 155.2, 167.1; IR (KBr): nmax 1793, 1684,
1474, 1274, 750 cmK1. Anal. Calcd for C16H13NO4S: C,
60.94, H, 4.16, N, 4.44. Found: C, 60.89; H, 4.13; N, 4.32.
4.2.10. N-[(2-Methoxycarbonylbenzene)sulfenyl]-3,5-
dimethylpyrazole (2j). Mp 91.8–93.2 8C (from hexane);
RfZ0.5 (CH2Cl2/ethyl acetateZ10:1); 1H NMR (500 MHz,
CDCl3): d 2.26 (3H, s), 2.30 (3H, s), 3.98 (3H, s), 6.04 (1H,
dd, JZ8.2, 0.9 Hz), 6.07 (1H, s), 7.19 (1H, ddd, JZ7.8, 7.3,
0.9 Hz), 7.37 (1H, ddd, JZ8.2, 7.3, 1.5 Hz), 8.02 (1H, dd,
JZ7.8, 1.5 Hz); 13C NMR (125 MHz, CDCl3): d 11.7, 14.0,
52.6, 103.2, 107.6, 122.4, 123.5, 125.0, 130.7, 133.7, 146.5,
147.5, 152.4, 161.1, 167.2; IR (KBr): nmax 1695, 1564,
1462, 1437, 1278, 790, 752 cmK1. Anal. Calcd for
C13H14N2O2S: C, 59.52; H, 5.38; N, 10.68. Found: C,
59.61; H, 5.30; N, 10.34.
4.2.6. N-[(2-Ethoxycarbonylbenzene)sulfenyl]benz-
othiazol-2-one (2f). Mp 138.8–139.5 8C (from ethyl
1
acetate–hexane); RfZ0.7 (CH2Cl2); H NMR (500 MHz,
CDCl3): d 1.45 (3H, t, JZ7.0 Hz), 4.47 (2H, q, JZ7.0 Hz),
6.70 (1H, dd, JZ8.2, 0.6 Hz), 7.21–7.29 (3H, m), 7.35–7.40