Oxidation of a thiol to a sulfonyl chloride; Dodecane-1-sulfonyl chloride
Submitted Jun 02, 2013, published Jun 06, 2013
Nenad Maraš (firstname.lastname@example.org
A contribution from
M. Kocevar's group
dodecane-1-thiol, ≥98% (Sigma-Aldrich)
trichloroisocyanuric acid, ≥95% (Fluka)
sodium sulfate, anhydrous
petroleum ether (bp 40–60 °C)
To a stirring solution of dodecane-1-thiol (1.74 g, 86 mmol) in a mixture of acetonitrile and water (4 : 1 vol., 40 mL) on an ice-bath was added portion-wise trichloroisocyanuric acid (2.90 g, 125 mmol) at such a rate to maintain the temperature at no more than 5 °C. The mixture was left stirring for 30 min in the ice-bath. The precipitated cyanuric acid was then removed by filtration and washed with ethyl acetate (30 mL). The combined filtrate was evaporated under reduced pressure at the bath temperature not higher than 30 °C (to minimize the losses from hydrolysis). The so obtained crude product was dissolved in petroleum ether (50 mL), washed with cold 1% HCl(aq) (50 mL), dried over Na2SO4 and again evaporated under reduced pressure to give the product as a white powder (1.40 g, 61%).
mp 38–39 °C (lit. 42–43 °C, Sprague and Johnson).
1H NMR (300 MHz, 302 K, CDCl3) δ 0.883 (t, J = 6.8, 3H), 1.20–1.40 (m, 16H), 1.49 (m, 2H), 2.07 (m, 2H), 3.66 (m, 2H).
IR (KBr) 1618, 1467, 1416, 1356, 1153 cm-1.
Ed.: A. R. Katritzky, S. V. Ley, O. Meth-Cohn, C. W. Rees: Comprehensive organic functional group transformations, vol. 2., 1995, Elsevier, Oxford, 177–180.
J. M. Sprague, T. B. Johnson: Preparation of alkylsulfonyl chlorides from isothioureas. II. J. Am. Chem. Soc. 1937, 59, 1837–1840.
Dodecane-1-sulfonyl chloride 1H NMR.pdf
Keywords: chlorination, electrophilic, halogenation, mercaptans, oxidation, sulphides