SHORT PAPER
Chemoselective Preparation of Arylthiols
3213
Synthesis of Arylthiols; General Procedure14
(3) (a) Takikawa, Y. Kogyo Kagaku Zasshi 1967, 70, 1384;
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To a solution of arylsulfonyl chloride (5 mmol) in anhyd toluene (30
mL) in a three-neck round-bottom flask with a nitrogen inlet, reflux
condenser, and calcium chloride guard tube, was added Ph3P (15
mmol) in portions (CAUTION: reaction is highly exothermic and
may start refluxing). The reaction was stirred for 10 min and al-
lowed to cool to below 50 °C. H2O (5 mL) was added and the mix-
ture was stirred for 10 min. The aqueous layer was discarded and the
organic layer was extracted with 10% NaOH (2 × 15 mL). The al-
kaline aqueous extract was washed with toluene (2 × 10 mL), acid-
ified with dilute HCl and extracted with CH2Cl2 (2 × 15 mL). The
organic layer was dried over Na2SO4 and the solvent was evaporat-
ed under reduced pressure to give practically pure arylthiol.
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1985. (b) Sugita, S.; Masuda, K.; Nakagawa, S. JP 6207063,
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5140086, 1992.
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H. A. J. Org. Chem. 1966, 31, 3981. (c) Kwart, H.; Evans,
E. R. J. Org. Chem. 1966, 31, 410.
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H. F.; Tarbell, D. S. J. Am. Chem. Soc. 1950, 72, 5200.
(11) Sainsbury, M.; Theobald, R. S. In Rodd’s Chemistry of
Carbon Compounds, Vol. 3A; Coffey S., Ansell M. F.,
Elsevier: Amsterdam, 1986, 447–448.
4-Methyl-3-nitrobenzenethiol (Entry 12)
Oil.
IR (CHCl3): 2576, 1514, 1335 cm–1.
1H NMR (300 MHz, CDCl3): d = 8.08 (s, 1 H), 7.66–7.22 (m, 2 H),
3.48 (s, 1 H), 2.56 (s, 3 H).
MS (EI): m/z = 169 [M+], 152, 121, 97, 77.
Anal. Calcd for C7H7NO2S: C, 49.69; H, 4.17; N, 8.28. Found: C,
49.70; H, 4.07; N, 8.32.
(12) (a) Hudlicky, M. In Reductions in Organic Chemistry, ACS
Monograph 188; American Chemical Society: Washington
DC, 1996, 119–127; and references cited therein.
(b) Marvel, C. S.; Caser, P. D. J. Am. Chem. Soc. 1951, 73,
1097. (c) Marvel, C. S.; Caser, P. D. J. Am. Chem. Soc. 1950,
72, 1033. (d) Wagner, A. W. Chem. Ber. 1966, 99, 375.
(e) Buckler, S. A.; Doll, L.; Lind, F. K.; Epstein, M. J. Am.
Chem. Soc. 1962, 95, 794. (f) Overberger, C. G.; Biletech,
H.; Orttung, F. W. J. Org. Chem. 1959, 24, 289. (g) Thies,
H.; Von Kaenel, F. EP 2755, 1978. (h) Brown, H. C.;
Subba Rao, B. C. J. Am. Chem. Soc. 1956, 78, 2582.
(i) Itabashi, K. Yuki Gosei Kagaku Kyokaishi 1961, 19, 601;
Chem. Abstr. 1961, 55, 23412.
(13) Scott, P. H.; Smith, C. P.; Kober, E.; Churchill, J. W.
Tetrahedron Lett. 1970, 14, 1153.
(14) For reference data of known compounds, see:
(a) Dictionary of Organic Compounds, 6th ed.; Bukiyahan,
J.; Macdonald, F., Eds.; Chapman and Hall Electric
Publishing House: London, 1996. (b) Wang, W.; Hu, G. H.
J. Appl. Polym. Sci. 1993, 47, 1665.
4-Chloro-3-nitrobenzenethiol (Entry 13)
Yellow solid; mp 53–55 °C (Lit.15 yellow solid).
IR (KBr): 2559, 1509, 1335 cm–1.
1H NMR (300 MHz, CDCl3): d = 7.20 (m, 3 H), 3.44 (s, 1 H).
Anal. Calcd for C6H4ClNO2S: C, 38.00; H, 2.13; N, 7.39. Found: C,
37.89; H, 2.30; N, 7.32.
Acknowledgment
E.V.B. thanks the World Bank for financial assistance under the
Technical Education Quality Improvement Program (TEQIP). The
authors wish to thank the University Grants Commission (UGC)
and All India Council for Technical Education (AICTE) for finan-
cial support.
References
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Synthesis 2009, No. 19, 3211–3213 © Thieme Stuttgart · New York