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M. A. Rahim et al. / Tetrahedron 56 (2000) 763–770
92%). 3g: 1H NMR 1.69–1.82 (m, 4H), 1.87–1.95 (m, 2H),
4.27 (t, J6.1 Hz, 2H), 4.40 (t, J6.5 Hz, 1H), 7.22–7.31
(m, 6H), 7.40–7.47 (m, 6H), 7.51–7.56 (m, 1H), 8.00–8.05
(m, 2H); 13C NMR 23.60, 28.17, 35.35, 58.27, 64.57,
127.74, 128.32, 128.89, 129.52, 130.34, 132.78, 132.85,
134.05, 166.54; IR (neat) 3058, 2947, 1716, 1583, 1479,
1438, 1274, 1117, 1025, 748, 713, 690. Anal. Calcd
for C24H24S2O2: C, 70.55; H, 5.92. Found: C, 70.63;
H, 6.05.
Anal. Calcd for C26H28S2O2: C, 71.52; H, 6.46. Found: C,
71.51; H, 6.55.
5,5-Bis(phenylthio)pentyl octanoate (3f). 1H NMR 0.87 (t,
J7.0 Hz, 3H), 1.22–1.34 (m, 8H), 1.55–1.72 (m, 6H), 1.87
(dt, J6.7, 8.2 Hz, 2H), 2.28 (t, J7.6 Hz, 2H), 4.03 (t,
J6.4 Hz, 2H), 4.39 (t, J6.7 Hz, 1H), 7.24–7.33 (m,
6H), 7.42–7.48 (m, 4 H); 13C NMR 14.03, 22.56, 23.52,
24.97, 28.09, 28.90, 29.09, 31.63, 34.32, 35.38, 58.27,
63.86, 127.71, 128.87, 132.75, 134.10, 173.86; IR (neat)
3059, 2933, 2858, 1739, 1439, 1169, 748, 692. Anal.
Calcd for C25H34S2O2: C, 69.72; H, 7.96. Found C, 69.68;
H, 8.11.
In a similar manner, the following v,v-bis(phenylthio)alkyl
alkanoates 3 were obtained.
1
3,3-Bis(phenylthio)propyl 3-phenylpropanoate (3a). H
NMR 2.11 (dt, J6.1, 7.0 Hz, 2H), 2.56 (t, J7.8 Hz,
2H), 2.88 (t, J7.8 Hz, 2H), 4.31 (t, J6.1 Hz, 2H), 4.43
(t, J7.0 Hz, 1H), 7.14–7.33 (m, 11H), 7.42–7.48 (m, 4H);
13C NMR 30.81, 34.83, 35.72, 55.02, 61.54, 126.25, 127.93,
128.17, 128.47, 128.92, 132.96, 133.54, 140.33, 172.50; IR
(neat) 3060, 3028, 2958, 1732, 1583, 1439, 1248, 1161, 748,
692. Anal. Calcd for C24H24S2O2: C, 70.55; H, 5.92. Found:
C, 70.75; H, 6.09.
6,6-Bis(phenylthio)hexyl octanoate (3h). 1H NMR 0.86 (t,
J6.9 Hz, 3H), 1.20–1.40 (m, 10H), 1.52–1.72 (m, 6H),
1.80–1.90 (m, 2H), 2.26 (t, J7.5 Hz, 2H), 4.01 (t,
J6.6 Hz, 2H), 4.39 (t, J6.6 Hz, 1H), 7.22–7.38 (m,
6H), 7.40–7.52 (m, 4H); 13C NMR 14.04, 22.56, 24.97,
25.44, 26.63, 28.41, 28.89, 29.08, 31.63, 34.33, 35.66,
58.30, 64.05, 127.64, 128.85, 132.67, 134.23, 173.91; IR
(neat) 3059, 2929, 2856, 1734, 1583, 1439, 1169, 748,
692. Anal. Calcd for C26H36S2O2: C, 70.23; H, 8.16.
Found: C, 70.31; H, 8.21.
3,3-Bis(phenylthio)propyl 4-propylbenzoate (3b). 1H
NMR 0.94 (t, J7.3 Hz, 3H), 1.66 (tq, J7.3, 7.6 Hz,
2H), 2.28 (dt, J6.1, 7.0 Hz, 2H), 2.64 (t, J7.5 Hz, 2H),
4.55 (t, J6.1 Hz, 2H), 4.59 (t, J7.0 Hz, 1H), 7.20–7.32
(m, 8H), 7.45–7.52 (m, 4H), 7.85–7.90 (m, 2H); 13C NMR
13.70, 24.22, 35.09, 37.99, 55.15, 61.88, 127.48, 127.89,
128.45, 128.95, 129.57, 132.88, 133.69, 148.33, 166.31;
IR (neat) 3059, 2962, 1720, 1439, 1275, 1109, 748, 690.
Anal. Calcd for C25H26S2O2: C, 71.05; H, 6.20. Found: C,
71.30; H, 6.34.
6,6-Bis(phenylthio)hexyl 3-phenylpropanoate (3i). 1H
NMR 1.22–1.31 (m, 2H), 1.52–1.64 (m, 4H), 1.83 (dt,
J6.7, 8.9 Hz, 2H), 2.61 (t, J7.8 Hz, 2H), 2.94 (t,
J7.9 Hz, 2H), 4.03 (t, J6.6 Hz, 2H), 4.39 (t, J6.7 Hz,
1H), 7.15–7.21 (m, 3H), 7.23–7.33 (m, 8H), 7.42–7.48 (m,
4H); 13C NMR 25.38, 26.61, 28.35, 30.94, 35.63, 35.85,
58.28, 64.29, 126.20, 127.64, 128.23, 128.43, 128.85,
132.65, 134.21, 140.46, 172.89; IR (neat) 3060, 3028,
2939, 2860, 1732, 1583, 1479, 1161, 748, 690. Anal.
Calcd for C27H30S2O2: C, 71.96; H, 6.71. Found: C, 72.05;
H, 6.78.
4,4-Bis(phenylthio)butyl 4-phenylbutanoate (3c). 1H
NMR 1.86–1.98 (m, 6H), 2.24 (t, J7.5 Hz, 2H), 2.62 (t,
J 7.6 Hz, 2H), 4.04 (t, J6.1 Hz, 2H), 4.40 (t, J6.3 Hz,
1H), 7.14–7.32 (m, 11H), 7.43–7.48 (m, 4H); 13C NMR
26.09, 26.39, 32.15, 33.50, 35.10, 57.88, 63.46, 125.96,
127.81, 128.36, 128.45, 128.90, 132.82, 133.86, 141.28,
173.36; IR (neat) 3060, 2954, 1732, 1583, 1439, 1146,
748, 692. Anal. Calcd for C26H28S2O2: C, 71.52; H, 6.46.
Found: C, 71.67; H, 6.64.
1
6,6-Bis(phenylthio)hexyl benzoate (3j). H NMR 1.38–
1.47 (m, 2H), 1.64–1.78 (m, 4H), 1.88 (dt, J6.7, 8.5 Hz,
2H), 4.37 (t, J6.6 Hz, 2H), 4.40 (t, J6.7 Hz, 1H), 7.22–
7.31 (m, 6H), 7.39–7.48 (m, 6H), 7.52–7.56 (m, 1H), 8.00–
8.05 (m, 2H); 13C NMR 25.52, 26.64, 28.48, 35.64, 58.29,
64.77, 127.64, 128.29, 128.85, 129.49, 130.37, 132.67,
132.79, 134.19, 166.56; IR (neat) 3059, 2939, 2858, 1716,
1583, 1275, 1117, 1026, 748, 714, 690. Anal. Calcd for
C25H26S2O2: C, 71.05; H, 6.20. Found: C, 71.26; H, 6.44.
4,4-Bis(phenylthio)butyl 4-propylbenzoate (3d). 1H NMR
0.95 (t, J7.3 Hz, 3H), 1.66 (tq, J7.3, 7.6 Hz, 2H), 1.97–
2.04 (m, 2H), 2.04–2.13 (m, 2H), 2.64 (t, J7.6 Hz, 2H),
4.29 (t, J6.3 Hz, 2H), 4.46 (t, J6.6 Hz, 1H), 7.19–7.23
(m, 2H), 7.23–7.31 (m, 6H), 7.43–7.50 (m, 4H), 7.84–7.88
(m, 2H); 13C NMR 13.71, 24.25, 26.22, 32.21, 38.02, 57.84,
63.91, 127.64, 127.79, 128.44, 128.92, 129.57, 132.83,
133.88, 148.22, 166.56; IR (neat) 3059, 2962, 1716, 1439,
1282, 1178, 1113, 748, 692. Anal. Calcd for C26H28S2O2: C,
71.52; H, 6.46. Found: C, 71.62, H; 6.61.
4,4-Bis(phenylthio)butyl 4-methylbenzoate (3k). 1H NMR
1.95–2.02 (m, 2 H), 2.04–2.11 (m, 2H), 2.40 (s, 3 H), 4.27
(t, J6.1 Hz, 2H), 4.44 (t, J6.4 Hz, 1H), 7.20 (d,
J7.9 Hz, 2H), 7.22–7.30 (m, 6H), 7.42–7.49 (m, 4H),
7.82 (d, J7.9 Hz, 2H); 13C NMR 21.66, 26.22, 32.22,
57.87, 63.94, 127.42, 127.81, 128.94, 129.02, 129.57,
132.84, 133.88, 143.54, 166.55; IR (neat) 3060, 2958,
1716, 1614, 1481, 1275, 1109, 841, 752, 690. Anal. Calcd
for C24H24S2O2: C, 70.27; H, 11.01. Found: C, 70.33, H;
11.19.
5,5-Bis(phenylthio)pentyl 3-phenylpropanoate (3e). 1H
NMR 1.53–1.68 (m, 4H), 1.81–1.90 (m, 2H), 2.61 (t,
J7.8 Hz, 2H), 2.94 (t, J7.8 Hz, 2H), 4.03 (t, J6.4 Hz,
2H), 4.37 (t, J6.6 Hz, 1H), 7.16–7.21 (m, 3H), 7.23–7.33
(m, 8H), 7.42–7.47 (m, 4H); 13C NMR 23.43, 27.97, 30.88,
35.30, 35.77, 58.16, 64.05, 126.16, 127.66, 128.19, 128.39,
128.83, 132.67, 134.04, 140.40, 172.76; IR (neat) 3060,
3030, 2949, 2866, 1732, 1583, 1439, 1161, 748, 692.
Carbonyl olefination of v,v-bis(phenylthio)alkyl
alkanoates 3 followed by hydrolysis
Preparation of 6-hydroxy-1-phenylhexan-1-one (2g).
Magnesium turnings (58 mg, 2.4 mmol), finely powdered