October 2010
1351
8.0 Hz), 7.44 (2H, t, Jϭ7.2 Hz), 7.55 (1H, t, Jϭ7.2 Hz), 7.94 (2H, d, Jϭ
6.4 Hz). 13C-NMR (100 MHz, CDCl3) d: 17.3, 46.4, 55.3, 114.4, 119.0,
126.1, 128.4, 128.5, 129.6, 133.0, 133.1, 135.5, 159.4, 196.2. IR (neat):
2930, 1681, 1589, 1479, 1231, 1040 cmϪ1. MS (EI) m/z: 272 (Mϩ, 47%),
167 (MϩϪC7H5O, 100%). HR-MS Calcd for C16H16O2S: 272.0871. Found:
272.0862.
7.2 Hz), 1.63—1.73 (1H,m),1.77—1.87 (1H, m), 2.56 (2H, t, Jϭ7.2 Hz),
3.62 (1H, t, Jϭ7.2 Hz), 7.23—7.31 (3H, m), 7.35 (2H, dd, Jϭ8.0, 1.6 Hz).
13C-NMR (100 MHz, CDCl3) d: 13.8, 13.9, 22.4, 23.5, 29.4, 30.1, 31.3,
39.2, 56.9, 127.7, 129.0, 132.3, 133.3, 207.6. IR (neat): 2956, 1709, 744,
691 cmϪ1. MS (EI) m/z: 278 (Mϩ, 25%), 179 (MϩϪC6H11O, 100%). HR-MS
Calcd for C17H26OS: 278.1704. Found: 278.1711.
a-(m-Methoxyphenylthio)ethyl p-Methylphenyl Ketone 1H-NMR (400
MHz, CDCl3) d: 1.54 (3H, d, Jϭ6.8 Hz), 2.41 (3H, s), 3.74 (3H, s), 4.64
(1H, q, Jϭ6.8 Hz), 6.82 (1H, dd, Jϭ8.0, 2.0 Hz), 6.86 (1H, d, Jϭ1.6 Hz),
6.94 (1H, d, Jϭ8.0 Hz), 7.17 (1H, t, Jϭ7.6 Hz), 7.23 (2H, d, Jϭ8.0 Hz), 7.84
(2H, d, Jϭ8.8 Hz). 13C-NMR (100 MHz, CDCl3) d: 17.4, 21.8, 46.4, 55.3,
114.3, 118.8, 125.9, 128.6, 129.1, 129.5, 132.9, 141.2, 143.8, 159.4, 195.9.
IR (neat): 2929, 1675, 1589, 1478, 1245, 1040, 949 cmϪ1. MS (EI) m/z: 286
(Mϩ, 77%), 119 (Mϩ– C9H11OS, 100%). HR-MS Calcd for C17H18SO2:
286.1028. Found: 286.1018.
2-(Phenylthio)cyclohexanone18) 1H-NMR (400 MHz, CDCl3) d: 1.64—
1.72 (1H, m), 1.78—1.86 (1H, m), 1.88—1.98 (2H, m), 2.03—2.10 (1H, m),
2.19—2.24 (1H, m), 2.26—2.32 (1H, m), 2.90 (1H, ddd, Jϭ14.0, 9.2, 6.0
Hz), 3.83 (1H, t, Jϭ6.0 Hz), 7.23 (1H, t, Jϭ7.6 Hz), 7.28 (2H, t, Jϭ8.0 Hz),
7.40 (2H, d, Jϭ8.0 Hz). 13C-NMR (100 MHz, CDCl3) d: 22.6, 27.2, 33.9,
39.0, 56.2, 127.3, 128.9, 131.8, 133.7, 207.6. IR (neat): 3060, 2939, 2860,
1708, 1482, 1438, 1123, 1023, 744, 691 cmϪ1. MS (EI) m/z: 206 (Mϩ, 90%),
110 (MϩϪC6H8O, 100%). HR-MS Calcd for C12H14OS: 206.0765. Found:
206.0765.
a-(m-Methoxyphenylthio)butyrophenone 1H-NMR (400 MHz, CDCl3)
d: 1.06 (3H, t, Jϭ7.2 Hz), 1.89 (1H, ddq, Jϭ14.4, 7.2, 7.2 Hz), 2.07 (1H,
ddq, Jϭ14.4, 7.2, 7.2 Hz), 3.72 (3H, s), 4.40 (1H, t, Jϭ7.2 Hz), 6.81 (1H, dd,
Jϭ8.4, 2.4 Hz), 6.84 (1H, bs), 6.92 (1H, d, Jϭ7.6 Hz), 7.17 (1H, t, Jϭ7.6
Hz), 7.42 (2H, t, Jϭ7.6 Hz), 7.54 (1H, t, Jϭ7.2 Hz), 7.91 (2H, d, Jϭ7.2 Hz).
13C-NMR (100 MHz, CDCl3) d: 12.1, 24.5, 53.4, 55.3, 114.3, 118.9, 126.0,
128.4, 128.4, 129.5, 132.9, 133.4, 136.1, 159.3, 195.9. IR (neat): 2965,
1680, 1589, 1477, 1247, 1040 cmϪ1. MS (EI) m/z: 286 (Mϩ, 47%), 181
(MϩϪC7H5O, 100%). HR-MS Calcd for C17H18O2S: 286.1028. Found:
p-Methoxyphenyl a-(Phenylthio)methyl Ketone19) mp 87—88 °C
(hexane). Lit. 85—85.5 °C. 1H-NMR (400 MHz, CDCl3) d: 3.88 (3H, s),
4.24 (2H, s), 6.93 (2H, ddd, Jϭ9.2, 2.8, 2.0 Hz), 7.22 (1H, t, Jϭ7.6 Hz), 7.28
(2H, t, Jϭ6.8 Hz), 7.39 (2H, d, Jϭ7.2 Hz), 7.93 (2H, ddd, Jϭ8.8, 2.8, 2.0
Hz). 13C-NMR (100 MHz, CDCl3) d: 41.0, 55.5, 113.9, 127.0, 128.4, 129.0,
130.4, 131.1, 135.1, 163.8, 192.7. IR (KBr): 3060, 2925, 2846, 1670, 1599,
1575, 1509, 1260, 1172, 1024, 831, 740, 690 cmϪ1. MS (EI) m/z: 258 (Mϩ,
7%), 135 (MϩϪC7H7S, 100%). HR-MS Calcd for C15H14O2S: 258.0714.
Found: 258.0700.
a-(Octylthio)propiophenone 1H-NMR (400 MHz, CDCl3) d: 0.86 (3H, 286.1018.
a-(3-Methoxypropylthio)butyrophenone 1H-NMR (400 MHz, CDCl3)
t, Jϭ7.2 Hz), 1.21—1.30 (10H, m), 1.48 (2H, quint, Jϭ7.2 Hz), 1.56 (3H, d,
Jϭ6.4 Hz), 2.37 (1H, dt, Jϭ11.6, 7.2 Hz), 2.53 (1H, dt, Jϭ12.4, 7.2 Hz),
4.32 (1H, q, Jϭ6.4 Hz), 7.46 (2H, td, Jϭ7.2, 1.6 Hz), 7.56 (1H, tt, Jϭ7.2,
1.6 Hz), 8.01 (2H, dd, Jϭ7.2, 1.6 Hz). 13C-NMR (100 MHz, CDCl3) d: 14.1,
16.4, 22.6, 28.7, 28.9, 29.1, 29.1, 29.2, 31.7, 41.5, 128.5, 128.5, 132.9,
135.7, 196.1. IR (neat): 2926, 1678, 716, 688 cmϪ1. MS (EI) m/z: 278 (Mϩ,
4%), 173 (MϩϪC7H5O, 100%). HR-MS Calcd for C17H26OS: 278.1680.
Found: 278.1704.
Typical Procedures for Organothio Exchange Reaction of Phenylthio
Aryl Ketones, a-(m-Methoxyphenylthio)acetophenone In a two-necked
flask equipped with a reflux condenser were placed RhH(PPh3)4 (1 mol%,
2.9 mg), dppe (2 mol%, 2.0 mg), and a-(phenylthio)acetophenone (0.25
mmol, 57 mg) under an argon atmosphere. After THF (2 ml) and bis(m-
methoxyphenyl) disulfide (0.75 mmol, 208 mg) were added, the solution was
heated at reflux for 1 h. The solvent was removed under reduced pressure,
and flash chromatography (hexane/ethyl acetateϭ15/1) over silica gel gave
a-(m-methoxyphenylthio)acetophenone (53.9 mg, 84%). 1H-NMR (400
MHz, CDCl3) d: 3.76 (3H, s), 4.29 (2H, s), 6.75 (1H, dd, Jϭ8.0, 2.0 Hz),
6.92 (1H, t, Jϭ2.4 Hz), 6.95 (1H, d, Jϭ8.0 Hz), 7.18 (1H, t, Jϭ8.0 Hz), 7.45
(2H, t, Jϭ7.6 Hz), 7.57 (1H, t, Jϭ8.0 Hz), 7.94 (2H, d, Jϭ8.0 Hz). 13C-NMR
(100 MHz, CDCl3) d: 41.1, 55.3, 112.8, 115.3, 122.2, 128.5, 128.5, 129.7,
133.3, 135.2, 135.9, 159.6, 193.8. IR (neat): 2937, 2834, 1681, 1590, 1277,
1040 cmϪ1. MS (EI) m/z: 258 (Mϩ, 65%), 105 (MϩϪC8H9OS, 100%). HR-
MS Calcd for C15H14O2S: 258.0714. Found: 258.0711.
d: 1.03 (3H, t, Jϭ7.2 Hz), 1.74 (2H, quint, Jϭ6.4 Hz), 1.86 (1H, ddq, Jϭ
14.0, 7.2, 7.2 Hz), 2.10 (1H, ddq, Jϭ14.0, 7.2, 7.2 Hz), 2.45 (1H, dt, Jϭ
14.0, 7.2 Hz), 2.58 (1H, dt, Jϭ14.0, 7.2 Hz), 3.27 (3H, s), 3.35 (2H, td, Jϭ
6.0, 2.0 Hz), 4.05 (1H, t, Jϭ7.2 Hz), 7.45 (2H, t, Jϭ7.6 Hz), 7.55 (1H, t, Jϭ
7.2 Hz), 7.98 (2H, dd, Jϭ8.0, 1.2 Hz). 13C-NMR (100 MHz, CDCl3) d: 12.2,
23.6, 25.8, 29.5, 48.8, 58.6, 71.2, 128.3, 129.4, 132.8, 136.0, 195.5. IR
(neat): 2929, 2873, 1675, 1447, 1223, 1118 cmϪ1. MS (EI) m/z: 252 (Mϩ,
26%), 89 (MϩϪC10H11S, 100%). HR-MS Calcd for C14H20O3S: 252.1184.
Found: 252.1183.
a-(Cyclopentylthio)butyrophenone 1H-NMR (400 MHz, CDCl3) d:
1.02 (3H, t, Jϭ7.2 Hz), 1.32—1.54 (4H, m), 1.59—1.70 (2H, m), 1.84—
1.92 (2H, m), 1.94—2.04 (1H, m), 2.13 (1H, ddq, Jϭ15.2, 7.6, 7.6 Hz), 3.02
(1H, quint, Jϭ7.6 Hz), 4.08 (1H, t, Jϭ7.6 Hz), 7.46 (2H, t, Jϭ7.6 Hz), 7.55
(1H, t, Jϭ7.6 Hz), 7.99 (2H, d, Jϭ7.6 Hz). 13C-NMR (100 MHz, CDCl3) d:
12.4, 24.8, 24.9, 25.0, 34.3, 35.1, 42.4, 50.0, 128.4, 128.4, 132.8, 136.3,
196.8. IR (neat): 2962, 2871, 1677, 1447, 1262, 1224 cmϪ1. MS (EI) m/z:
248 (Mϩ, 4%), 143 (MϩϪC7H5O, 100%). HR-MS Calcd for C15H20OS:
248.1235. Found: 248.1232.
a-(Cyclohexylthio)butyrophenone 1H-NMR (400 MHz, CDCl3) d: 1.01
(3H, t, Jϭ7.6 Hz), 1.15—1.34 (5H, m), 1.52—1.55 (1H, m), 1.65—1.70
(2H, m), 1.81—1.91 (3H, m), 2.12 (1H, ddq, Jϭ15.2, 7.6, 7.6 Hz), 2.64—
2.73 (1H, m), 4.07 (1H, t, Jϭ7.6 Hz), 7.45 (2H, t, Jϭ8.0 Hz), 7.55 (1H, t,
Jϭ8.0 Hz), 7.99 (2H, d, Jϭ8.0 Hz). 13C-NMR (100 MHz, CDCl3) d: 12.4,
a-(p-Methylphenylthio)acetophenone20) 1H-NMR (400 MHz, CDCl3) 25.1, 25.6, 34.4, 34.9, 42.7, 49.3, 128.36, 128.40, 132.7, 136.2, 196.9. IR
(neat): 2930, 2852, 1677, 1578, 1262, 1224, 999 cmϪ1. MS (EI) m/z: 262
d: 2.31 (3H, s), 4.20 (2H, s), 7.08 (2H, d, Jϭ8.0 Hz), 7.28 (2H, d, Jϭ8.0
(Mϩ, 6%), 157 (MϩϪC7H5O, 100%). HR-MS Calcd for C16H22SO:
Hz), 7.45 (2H, t, Jϭ7.6 Hz), 7.56 (1H, t, Jϭ7.2 Hz), 7.92 (2H, d, Jϭ7.6 Hz).
13C-NMR (100 MHz, CDCl3) d: 21.2, 41.9, 128.5, 128.6, 129.7, 130.7,
262.1391. Found: 262.1373.
Typical Procedures for Organothio Exchange Reaction of Alkylthio
131.4, 133.2, 137.4, 141.4, 193.9. IR (neat): 2938, 2835, 1680, 1277 cmϪ1
.
MS (EI) m/z: 242 (Mϩ, 65%), 105 (MϩϪC8H9S, 100%). HR-MS Calcd for
C15H14OS: 242.0765. Found: 242.0756.
Ketone, a-(m-Methoxyphenylthio)propiophenone In a two-necked flask
equipped with a reflux condenser were place a-(octylthio)propiophenone
(139.2 mg, 0.5 mmol), bis(m-methoxyphenyl) disulfide (315.5 mg, 1.5 mmol),
RhH(PPh3)4 (11.6 mg, 2.0 mol%) and dppe (8.0 mg, 4.0 mol%) in THF
(2 ml) under an argon atmosphere, and the solution was heated at reflux
for 3 h. The solvent was removed under reduced pressure, and the residue
was purified by flash column chromatography on silica gel giving a-(m-
methoxyphenylthio)propiophenone (109.2 mg, 80%), and m-methoxyphenyl
octyl disulfide (110.4 mg, 78%).
a-(3-Methoxypropylthio)acetophenone 1H-NMR (400 MHz, CDCl3)
d: 1.87 (2H, quint, Jϭ7.2 Hz), 2.65 (2H, t, Jϭ7.2 Hz), 3.31 (3H, s), 3.43
(2H, t, Jϭ6.8 Hz), 3.80 (2H, s), 7.46 (2H, t, Jϭ7.2 Hz), 7.57 (1H, t, Jϭ7.2
Hz), 7.97 (2H, d, Jϭ7.2 Hz). 13C-NMR (100 MHz, CDCl3) d: 29.1, 29.2,
37.2, 58.6, 70.9, 128.5, 128.6, 133.2, 135.1, 194.2. IR (neat): 3060, 2926,
1673, 1277, 1116 cmϪ1. MS (EI) m/z: 224 (Mϩ, 42%), 105 (MϩϪC5H11OS,
100%). HR-MS Calcd for C12H16O2S: 224.0871. Found: 224.0879.
p-Methoxyphenyl a-(m-Methoxyphenylthio)methyl Ketone 1H-NMR
(400 MHz, CDCl3) d: 3.76 (3H, s), 3.87 (3H, s), 4.25 (2H, s), 6.74 (1H, dd,
Jϭ8.0, 2.0 Hz), 6.91—6.96 (4H, m), 7.18 (1H, t, Jϭ8.0 Hz), 7.92 (2H, d, Jϭ
8.8 Hz). 13C-NMR (100 MHz, CDCl3) d: 40.8, 55.3, 55.5, 112.6, 113.7,
115.1, 121.9, 128.2, 129.7, 130.9, 136.2, 159.6, 163.6, 192.4. IR (neat):
2936, 2837, 1670, 1597, 1479, 1260, 1173, 1036 cmϪ1. MS (EI) m/z: 288
(Mϩ, 27%), 135 (Mϩ–C8H9OS, 100%). HR-MS Calcd for C16H16O3S:
288.0820. Found: 288.0826.
1
a-(p-Methoxyphenylthio)propiophenone mp 85—87 °C (hexane). H-
NMR (400 MHz, CDCl3) d: 1.46 (3H, d, Jϭ7.2 Hz), 3.76 (3H, s), 4.49 (1H,
q, Jϭ6.8 Hz), 6.79 (2H, d, Jϭ8.8 Hz), 7.25 (2H, d, Jϭ8.8 Hz), 7.43 (2H, t,
Jϭ8.0 Hz), 7.54 (1H, t, Jϭ8.0 Hz), 7.96 (2H, d, Jϭ7.2 Hz). 13C-NMR (100
MHz, CDCl3) d: 16.4, 46.0, 55.1, 114.3, 121.2, 128.4, 128.5, 132.8, 135.7,
137.4, 160.2, 195.9. IR (KBr): 2966, 1677, 1593, 1494, 1249, 1030, 828,
708, 688 cmϪ1. MS (EI) m/z: 272 (Mϩ, 53%), 167 (MϩϪC7H5O, 100%).
HR-MS Calcd for C16H16O2S: 272.0853. Found: 272.0871.
a-(3-Methyloxypropylthio)propiophenone 1H-NMR (400 MHz, CDCl3)
d: 1.57 (3H, d, Jϭ6.8 Hz), 1.75 (2H, m, Jϭ7.6 Hz), 2.47 (1H, dt, Jϭ12.4,
7.2 Hz), 2.62 (1H, dt, Jϭ12.4, 7.2 Hz), 3.27 (3H, s), 3.36 (2H, td, Jϭ6.8,
a-(m-Methoxyphenylthio)propiophenone 1H-NMR (400 MHz, CDCl3)
d: 1.56 (3H, d, Jϭ6.4 Hz), 3.74 (3H, s), 4.65 (1H, q, Jϭ6.8 Hz), 6.83 (1H,
dd, Jϭ8.0, 2.4 Hz), 6.86 (1H, s), 6.93 (1H, d, Jϭ7.2 Hz), 7.18 (1H, t, Jϭ