Convenient Synthesis of Symmetrical Diketosulfides from Enolizable Ketones 175
NMR (400 MHz, CDCl3, δ): 37.58, 126.80, 128.75,
2-(1-Benzoyl-propylsulfanyl)-1-phenyl-butan-1-
one (2l). mp 133–135◦C; IR (KBr) ν: 3061, 2960,
2926, 2008, 1682, 1597, 1579, 1449, 1340, 1221,
1076, 1030, 905, 685 cm−1; 1H NMR (400 MHz,
CDCl3, δ): 0.89 (t, 6H, J = 7.32 Hz, 2CH3), 1.73–1.82
(m, 4H, 2CH2), 4.09 (t, 2H, J = 8.2 Hz, 2SCH), 7.26
(t, 2H, J = 8.0 Hz, ArH), 7.39 (t, 3H, J = 7.84 Hz,
ArH), 7.48 (t, 1H, J = 7.4 Hz, ArH), 7.71 (d, 2H,
J = 7.2 Hz, ArH), 7.92 (d, 2H, J = 7.08 Hz, ArH);
13C NMR (400 MHz, CDCl3, δ): 12.09, 25.94, 48.69,
128.45, 128.75, 133.06, 135.97, 197.12; LCMS m/z:
327 (M + 1).
130.16, 133.64, 135.20, 136.84, 192.78; LCMS m/z:
339 (M + 1), 341 (M + 3).
1-(4-Chlorophenyl)-2-[2-(4-chlorophenyl)-2-oxo-
ethylsulfanyl]-ethanone (2g). mp 123–125◦C (lit.
[7a] 122–123◦C); IR (KBr) ν: 2918, 1701, 1671, 1591,
1400, 1361, 1288, 1174, 1093, 968, 819, 777 cm−1;
1H NMR (400 MHz, CDCl3, δ): 3.93 (s, 4H, CH2),
7.45 (d, 4H, J = 8.6 Hz, ArH), 7.91 (d, 4H, J = 8.6
Hz, ArH); 13C NMR (400 MHz, CDCl3, δ): 37.52,
129.16, 130.11, 133.61, 140.84, 192.94; LCMS m/z:
339 (M + 1), 341 (M + 3).
2-(1-Benzoyl-butylsulfanyl)-1-phenyl-pentan-1-one
(2m). mp 154–157◦C; IR (KBr) ν: 3061, 2959, 2924,
2980, 2342, 1813, 1682, 1598, 1580, 1447, 1368,
1-(2-Bromophenyl)-2-[2-(2-bromophenyl)-2-oxo-
ethylsulfanyl]-ethanone (2h). mp 94–96◦C; 1H NMR
(400 MHz, CDCl3, δ): 3.94 (s, 4H, CH2), 7.34 (t, 2H,
J = 7.84 Hz, ArH), 7.40 (t, 2H, J = 7.56 Hz, ArH),
7.51 (d, 2H, J = 7.64 Hz, ArH), 7.63 (d, 2H, J = 7.92
Hz, ArH); 13C NMR (400 MHz, CDCl3, δ): 40.58,
127.56, 129.50, 132.19, 133.75, 139.90, 197.54;
LCMS (M + 1) m/z: 339 (M + 1), 341 (M + 3).
1
1339, 1202, 1105, 1001, 899, 812, 746, 689 cm−1; H
NMR (400 MHz, CDCl3, δ): 0.91 (t, 6H, J = 2.72 Hz,
2CH3), 1.24–1.28 (m, 4H, 2CH2), 1.82–1.85 (m, 2H,
2CH2), 4.25–4.29 (m, 2H, 2SCH), 7.35 (t, 2H, J = 8.0
Hz, ArH), 7.48 (t, 3H, J = 7.88 Hz, ArH), 7.57 (t, 1H,
J = 7.4 Hz, ArH), 7.79 (d, 2H, J = 8.2 Hz, ArH), 8.0
(d, 2H, J = 7.2 Hz, ArH); 13C NMR (400 MHz, CDCl3,
δ): 13.65, 20.50, 34.17, 46.57, 128.44, 128.74, 133.05,
135.94, 197.19; LCMS m/z: 355 (M + 1).
1-(4-Bromophenyl)-2-[2-(4-bromophenyl)-2-oxo-
ethylsulfanyl]-ethanone (2i). mp 141–143◦C (lit.
[7a] 142–143◦C); IR (KBr) ν: 2922, 1671, 1583, 1402,
1204, 1071, 814, 769 cm−1; 1H NMR (400 MHz,
CDCl3, δ): 3.92 (s, 4H, CH2), 7.62 (d, 4H, J = 8.56
Hz, ArH), 7.82 (d, 4H, J = 8.64 Hz, ArH); 13C NMR
(400 MHz, CDCl3, δ): 37.51, 129.04, 130.22, 132.19,
134.05, 193.16; LCMS m/z: 427 (M + 1), 429 (M + 3),
449 (M + 23).
2-(2-Oxo-1,2-diphenyl-ethylsulfanyl)-1,2-diphenyl-
ethanone (2n). mp 69–71◦C; IR (KBr) ν: 3061,
2928, 1804, 1676, 1595, 1571, 1493, 1449, 1273,
1207, 1001, 841, 760, 694 cm−1; 1H NMR (400 MHz,
CDCl3, δ): 5.28 (3, 2H, 2ArCH), 7.18–7.45 (m, 12H,
ArH), 7.48–7.51 (m, 3H, ArH), 7.76–7.79 (m, 5H,
ArH); 13C NMR (400 MHz, CDCl3, δ): 62.31, 127.87,
128.07, 128.42, 128.43, 133.46, 133.56, 135.61,
136.32, 195.57; LCMS m/z: 377 (M + 1).
1-(3-Nitrophenyl)-2-[2-(3-nitrophenyl)-2-oxo-
ethylsulfanyl]-ethanone (2j). mp 129–131◦C; IR
(KBr) ν: 2924, 1678, 1526, 1405, 1348, 1262, 1022,
1
810, 764, 679 cm−1; H NMR (400 MHz, CDCl3, δ):
4.03 (s, 4H, CH2), 7.72 (t, 2H, J = 8.0 Hz, ArH), 8.30
(d, 2H, J = 7.8 Hz, ArH), 8.46 (d, 2H, J = 8.24 Hz,
ArH), 8.78 (s, 2H, ArH); 13C NMR (400 MHz, CDCl3,
δ): 37.58, 123.59, 127.99, 130.22, 134.22, 136.53,
148.57, 191.69; LCMS m/z: 361 (M + 1).
SUPPORTING INFORMATION
Supporting Information related to the structure and
spectral data of different compounds is available
from the corresponding author (e-mail: nnkarade@
gmail.com).
2-(1-Methyl-2-oxo-2-phenylethylsulfanyl)-1-phe-
nyl-propan-1-one (2k). mp 146–148◦C; IR (KBr)
ν: 3061, 2974, 2928, 2866, 1994, 1682, 1595, 1578,
1512, 1442, 1374, 1340, 1234, 1204, 1078, 1001, 951,
REFERENCES
[1] (a) Koser, G. F.; Wettach, R. H. J Org Chem 1976,
41, 3609; (b) Koser, G. F.; Wettach, R. H. J Org
Chem 1976, 42, 176; (c) Koser, G. F.; Wettach, R.
H. J.; Smith, C. S. J Org Chem 1980, 45, 1542;
(d) Koser, G. F.; Relenyi, A. G.; Kalos, A. N.; Rebrovic,
L.; Wettach, R. H. J Org Chem 1982, 47, 2487;
(e) Moriarty, R. M.; Vaid, R. K.; Koser, G. F. Synlett
1990, 365; (f) Varvoglis, A. Hypervalent Iodine in
Organic Synthesis; Academic Press: London, 1997;
Chap. 7, p. 115.
1
797, 716, 687 cm−1; H NMR (400 MHz, CDCl3, δ):
1.44 (d, 6H, J = 5.12 Hz, 2CH3), 4.45 (q, 2H, J = 5.36
Hz, 2CH), 7.37 (t, 2H, J = 8.2 Hz, ArH), 7.48 (t, 3H,
J = 7.64 Hz, ArH), 7.56 (t, 1H, J = 8.08 Hz, ArH),
7.81 (d, 2H, J = 7.04 Hz, ArH), 7.99 (d, 2H, J = 7.04
Hz, ArH); 13C NMR (400 MHz, CDCl3, δ): 18.60,
41.95, 128.67, 128.88, 133.56, 135.20, 196.97; LCMS
m/z: 299 (M + 1).
Heteroatom Chemistry DOI 10.1002/hc