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Synlett 2005(19): 2935-2938  
DOI: 10.1055/s-2005-921906
LETTER
© Georg Thieme Verlag Stuttgart · New York

Rapid Method for the Ring Expansion of 1,3-Dithiolanes and 1,3-Dithianes with tert-Butyl Hypochlorite

Nitin D. Arote, Vikas N. Telvekar, K. G. Akamanchi*
Department of Pharmaceutical Sciences and Technology, University Institute of Chemical Technology, Matunga, Mumbai-400019, India
Fax: 91(22)24145614; e-Mail: kgap@rediffmail.com;
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Publikationsverlauf

Received 23 August 2005
Publikationsdatum:
04. November 2005 (online)

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Abstract

A new method for the ring expansion of 1,3-dithiolanes and 1,3-dithianes to dihydro-1,4-dithiins and dihydro-1,4-dithiepines, respectively, using tert-butyl hypochlorite at room temperature is described. The salient features of the protocol include mild reaction conditions, very short reaction time, and high yield.

Key words

tert-butyl hypochlorite - 1,3-dithiolanes - 1,3-dithianes - sulfur-containing rings - ring expansion

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18

General Experimental Procedure: To a stirred solution of 1,3-dithiolane/1,3-dithiane (1.0 equiv) in CCl4 (10 mL) was added tert-butyl hypochlorite (1.05 equiv) dropwise at r.t. under a stream of nitrogen. The reaction mixture was stirred at r.t. until the starting material had been completely consumed (TLC). The reaction mixture was diluted with CH2Cl2. The organic layer was washed successively with a 5% solution of sodium thiosulfate (2 × 15 mL), H2O (2 × 15 mL), and brine (15 mL). The organic layer was dried over Na2SO4 and concentrated in vacuo. Purification by silica gel column chromatography (10% EtOAc-hexane) afforded the pure dihydro-1,4-dithiins and dihydro-1,4-dithianes.

19

2-Phenyl-5,6-dihydro-1,4-dithiin (Table [2] , entry 1): white solid; mp 54-55 °C. 1H NMR (CCl4, 60 MHz): δ = 3.25-3.34 (m, 4 H), 6.27 (s, 1 H), 7.38-7.53 (m, 5 H). 13C NMR (CDCl3, 125 MHz): δ = 30.29, 32.26, 113.54, 126.36, 127.97, 128.47, 128.62, 129.81. Anal. Calcd for C10H10S2: C, 61.86; H, 5.15; S, 32.98. Found: C, 61.83; H, 5.12.
3-Methyl-2-phenyl-5,6-dihydro-1,4-dithiin (Table [2] , entry 3): viscous oil. 1H NMR (CCl4, 60 MHz): δ = 2.22 (s, 3 H), 3.64 (m, 4 H), 7.68 (m, 5 H). 13C NMR (CDCl3, 125 MHz): δ = 22.49, 29.83, 30.21, 121.14, 124.65, 127.93, 128.27, 129.71, 139.78. MS (70 eV): m/z = 208, 180, 147, 121. Anal. Calcd for C11H12S2: C, 63.46; H, 5.77; S, 30.77. Found: C, 63.34; H, 5.72.
2-(4-Chlorophenyl)-5,6-dihydro-1,4-dithiin (Table [2] , entry 6): off-white soild; mp 64-65 °C. 1H NMR (CDCl3, 60 MHz): δ = 3.18-3.30 (m, 4 H), 6.31 (s, 1 H), 7.14-7.25 (m, 4 H). 13C NMR (CDCl3, 125 MHz): δ = 32.82, 33.65, 121.31, 128.76, 129.84, 131.45, 133.24, 134.79. Anal. Calcd for C10H9ClS2: C, 52.50; H, 3.94; Cl, 5.54; S, 28.01. Found: C, 52.43; H, 3.89; Cl, 15.61.
2-(4-Nitrophenyl)-5,6-dihydro-1,4-dithiin (Table [2] , entry 9): yellow solid; mp 139-140 °C. 1H NMR (CDCl3, 60 MHz): δ = 3.28-3.57 (m, 4 H), 6.54 (s, 1 H), 7.46-7.61 (d, J = 8.88 Hz, 2 H), 8.09-8.24 (d, J = 8.88 Hz, 2 H). 13C NMR (CDCl3, 125 MHz): δ = 30.79, 32.96, 121.28, 122.79, 123.45, 127.63, 127.68, 144.36. Anal. Calcd for C10H9NO2S2: C, 50.20; H, 3.77; N, 5.86; S, 26.78. Found: C, 50.15; H, 3.71; N, 5.78.
2-(4-Allyloxyphenyl)-5,6-dihydro-1,4-dithiin (Table [2] , entry 10): viscous oil. 1H NMR (CDCl3, 60 MHz): δ = 3.13-3.33 (m, 4 H), 4.44-4.52 (m, 2 H), 5.15-5.45 (m, 2 H), 5.72-6.15 (m, 2 H), 6.68-6.82 (d, J = 8.4 Hz, 2 H), 7.19-7.36 (d, J = 8.4 Hz, 2 H). Anal. Calcd for C13H14OS2: C, 62.40; H, 5.60; S, 25.60. Found: C, 62.32; H, 5.58.