An Efficient and Odorless Synthesis of Thioethers
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ture was neutralized with aq. HCl (0.1 mol•L , 10 mL),
and extracted with Et2O (15 mL×3). The combined
organic extracts were washed with H2O (15 mL×3),
dried over MgSO4, filtered and concentrated in vacco.
Separation was carried out over silica gel chromatogra-
phy (eluent: Et2O-petroleum ether, V∶V=1∶30) to
give a pure product 4. 4a—4e,[12] 4g and 4k,[16] 4m,[17]
4n, 4g, 4o, 4h and B[18] are known compounds, and their
spectroscopic data (NMR) and elemental analyses are in
good agreement with those reported in literatures.
Acknowledgment
This work was supported by the National Natural
Science Foundation of China (No. 20572013) and the
Doctoral Foundation of Anshan Normal University.
References
[1] Trost, B. M. Acc. Chem. Res. 1978, 11, 453.
[2] Cremlyn, R. J. An Introduction to Organo-Sulfur Chemistry, Wiley
& Sons, New York, 1996.
[3] McReynolds, M. D.; Doughtery, J. M.; Hanson, P. R. Chem. Rev.
2004, 104, 2239.
[4] (a) Trost, B. M. Chem. Rev. 1978, 78, 363; (b) Kondo, T.; Mitsudo,
T. Chem. Rev. 2000, 100, 3205; (c) Ley, S. V.; Thomas, A. W.
Angew. Chem., Int. Ed. 2003, 42, 5400; (d) Ranu, B. C.; Mandal, T.
J. Org. Chem. 2004, 69, 5793; (e) Taniguchi, N. J. Org. Chem. 2004,
69, 6904; (f) Wang, W.; Li, H.; Wang, J.; Liao, L. X. Tetrahedron
Lett. 2004, 45, 8229; (g) Salvatore, R. N.; Smith, R. A.; Nischwitza,
A. K.; Gavin, T. Tetrahedron Lett. 2005, 46, 8931; (h) Ranu, B. C.;
Jana, R. Adv. Synth. Catal. 2005, 347, 1811.
2-(Benzylthio)-1-p-tolylethanone (4f): White solid,
m.p. 61—63 ℃; 1H NMR (CDCl3, 500 MHz) δ: 2.42 (s,
3H), 3.66 (s, 2H), 3.76 (s, 2H), 7.25—7.26 (m, 3H),
7.30—7.35 (m, 4H), 7.83—7.84 (d, J=8 Hz, 2H); 13C
NMR (CDCl3, 125 MHz) δ: 23.5, 37.5, 40.2, 126.8,
128.3 (2C), 128.6 (2C), 129.1 (2C), 129.6 (2C), 133.1,
137.2, 140.3, 193.0; IR (KBr) ν: 3051, 2926, 1665, 1603,
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1
1558, 1279 cm . Anal. calcd for C16H16OS: C 74.96, H
6.29; found C 74.83, H 6.37.
[5] Nishide, K.; Miyamoto, T.; Kumar, K.; Ohsugi, S. I.; Node, M.
Tetrahedron Lett. 2002, 43, 8569.
[6] Zhan, Z. P.; Lang, K. Chem. Lett. 2004, 33, 1370.
2-(Benzylthio)-1-(4-phenylphenyl)ethanone
(4h):
1
White solid, m.p. 108—110 ℃; H NMR (CDCl3, 500
MHz) δ: 3.70 (s, 2H), 3.78 (s, 2H), 7.27 (m, 1H), 7.33 (t,
J=7.5 Hz, 2H), 7.37—7.41 (m, 3H), 7.47—7.50 (t, J=
7.5 Hz, 2H), 7.63 (d, J=8 Hz, 2H), 7.68 (d, J=8 Hz,
2H), 8.01 (d, J=8 Hz, 2H); 13C NMR (CDCl3, 125
MHz) δ: 35.58, 35.85, 127.00, 127.03 (2C), 127.06 (2C),
128.05, 128.30 (2C), 128.72 (2C), 129.05 (2C), 129.07
(2C), 133.78, 137.03, 139.54, 145.78, 198.76; IR (KBr)
[7] Wang, W.; Li, H.; Wang, J.; Liao, L. X. Tetrahedron Lett. 2004, 45,
8229.
[8] (a) Liu, Q.; Che, G. B.; Yu, H. F.; Liu, Y. C.; Zhang, J. P.; Zhang,
Q.; Dong, D. W. J. Org. Chem. 2003, 68, 9148; (b) Yu, H. F.; Liu,
Q.; Yin, Y. B.; Fang, Q. X.; Zhang, J. P.; Dong, D. W. Synlett 2004,
999; (c) Liu, J.; Liu, Q.; Yu, H. F.; Ouyang, Y.; Dong, D. W. Synth.
Commun. 2004, 34, 4545; (d) Sun, R.; Liu, Q.; Yu, H. F.; Zhao, Y.
L.; Liu, J.; Ouyang, Y.; Dong, D. W. Chin. J. Chem. 2005, 23, 1060;
(e) Yu, H. F.; Ouyang, Y.; Dong, D. W.; Liu, Q. Can. J. Chem. 2005,
83, 1741; (f) Ouyang, Y.; Yu, H. F.; Dong, D. W.; Liu, J.; Wang, M.;
Liu, Q. Chem. J. Chin. Univ. 2005, 26, 2237 (in Chinese); (g) Lin,
C.; Yu, H. F.; Liu, Q.; Hou, D. Y. Chin. J. Org. Chem. 2005, 25, 819
(in Chinese); (h) Yu, H. F.; Wang, Y. R.; Ouyang, Y.; Wang, Y.; Liu,
Q. Chem. J. Chin. Univ. 2006, 27, 2300 (in Chinese); (i) Zhao, H.;
Hou, D. Y.; Yu, H. F.; Liu, Q. Chin. J. Appl. Chem. 2009, 26, 667
(in Chinese); (j) Dong, D. W.; Ouyang, Y.; Yu, H. F.; Liu, Q.; Liu,
J.; Zhu, J. J. Org. Chem. 2005, 70, 4535; (k) Ouyang, Y.; Dong, D.
W.; Zheng, C. B.; Yu, H. F.; Liu, Q.; Fu, Z. Q. Synthesis 2006, 22,
3801; (l) Zhao, H.; Yu, H. F.; Lin, C. J. Beihua Univ. (Nat. Sci. Ed.)
2008, 9, 210 (in Chinese).
[9] (a) Yu, H. F.; Dong, D. W.; Ouyang, Y.; Liu, Q.; Wang, Y. Lett. Org.
Chem. 2005, 2, 755; (b) Chai, Y. Y.; Dong, D. W.; Ouyang, Y.; Li-
ang, Y. J.; Wang, Y.; Li, M. H.; Liu, Q. Lett. Org. Chem. 2007, 4,
281; (c) Ouyang, Y.; Yu, H. F.; Dong, D. W.; Liu, Q. J. Northeast
Normal Univ. (Nat. Sci. Ed.) 2006, 38, 67 (in Chinese); (d) Lin, C.;
Zhang, X. L.; Ouyang, Y.; Yu, H. F.; Dong, D. W. Chin. J. Chem.
2008, 26, 1431.
[10] Dong, D. W.; Sun, R.; Yu, H. F.; Ouyang, Y.; Zhang, Q.; Liu, Q.
Tetrahedron Lett. 2005, 46, 7331.
[11] Dong, D. W.; Yu, H. F.; Ouyang, Y.; Liu, Q.; Bi, X. H.; Lu, Y. M.
Synlett 2006, 283.
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ν: 3065, 2921, 1672, 1604,1559, 1450, 1194 cm . Anal.
calcd for C21H18OS: C 79.21, H 5.70; found C 79.35, H
5.61.
1-(4-Phenylphenyl)-2-(ethylthio)ethanone
(4i):
1
White solid, m.p. 75—77 ℃; H NMR (CDCl3, 500
MHz) δ: 1.29 (t, J=14.5 Hz, 3H), 2.62 (q, J=14.5 Hz,
2H), 3.83 (s, 2H), 7.39—7.42 (m, 1H), 7.46—7.49 (m,
2H), 7.63 (dd, J=8.5, 3.5 Hz, 2H), 7.70 (d, J=8 Hz,
2H), 8.06 (d, J=8 Hz, 2H); 13C NMR (CDCl3, 125
MHz) δ: 13.9, 26.1, 36.5, 127.0 (4C), 128.0, 128.7 (2C),
129.2 (2C), 133.6, 139.6, 145.8, 193.9; IR (KBr) ν:
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1
3055, 2926, 1665, 1604, 1420, 1283 cm . Anal. calcd
for C16H16OS: C 74.96, H 6.29; found C 74.85, H 6.31.
2-(Benzylthio)-1-(4-chlorophenyl)ethanone
(4j):
1
White solid, m.p. 85—87 ℃; H NMR (CDCl3, 500
MHz) δ: 3.60 (s, 2H), 3.74 (s, 2H), 7.26—7.27 (m, 1H),
7.32—7.34 (m, 4H), 7.43 (d, J=8 Hz, 2H), 7.86 (d, J=
8 Hz, 2H); 13C NMR (CDCl3, 125 MHz) δ: 35.5, 35.8,
127.1, 128.3 (2C), 128.7 (2C), 129.0 (2C), 129.9 (2C),
133.4, 136.8, 139.5, 192.9; IR (KBr) ν: 3067, 2923,
1672, 1584, 1453, 1271 cm - 1. Anal. calcd for
C15H13ClOS: C 65.09, H 4.73; found C 65.21, H 4.64.
(4-tert-Butylbenzyl)(benzyl)sulfane (4l): Colorless
oil; 1H NMR (CDCl3, 500 MHz) δ: 1.36 (s, 9H), 3.61 (s,
2H), 3.65 (s, 2H), 7.25—7.27 (m, 1H), 7.34—7.39 (m,
8H); 13C NMR (CDCl3, 125 MHz) δ: 31.7 (3C), 34.8,
35.5, 35.9, 125.7 (2C), 127.3, 128.8 (2C), 129.0 (2C),
129.4 (2C), 135.4, 138.6, 150.1; IR (KBr) ν: 3060, 2962,
[12] Yu, H. F.; Dong, D. W.; Ouyang, Y.; Wang, Y.; Liu, Q. Synlett 2007,
151.
[13] (a) Choi, E. B.; Youn, I. K.; Pak, C. S. Synthesis 1988, 792; (b)
Ouyang, Y.; Dong, D. W.; Yu, H. F.; Liang, Y. J.; Liu, Q. Adv.
Synth. Catal. 2006, 348, 206; (b) Padmavathi, V.; Balaiah, A.;
Reddy, M. M.; Reddy, D. B. Indian J. Chem., Sect. B: Org. Chem.
Incl. Med. Chem. 2003, 42, 1519.
[14] Wang, M.; Xu, X.; Sun, S.; Liu, Q. Synth. Commun. 2004, 34, 287.
[15] Boeykens, M.; Kimpe, N. D. Tetrahedron 1994, 50, 12349.
[16] Batigalhia, F.; Zaldini-Hernandes, M.; Ferreira, A. G.; Malvestiti, I.;
Cass, Q. B. Tetrahedron 2001, 57, 9669.
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[17] Ukrainets, I. V.; Bezugly, P. A.; Treskach, V. I.; Taran, S. G.;
Gorokhova, O. V. Tetrahedron 1994, 50, 10331.
1683, 1540, 1419, 1235 cm . Anal. calcd for C18H22S:
C 79.94, H 8.20; found C 79.81, H 8.27.
(Zhao, C.)
Chin. J. Chem. 2012, 30, 367—371
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