Iodo(trisyl)sulfane: Reactivity of a Stable Alkanesulfenyl Iodide towards Antithyroid Drugs

• Published in: European journal of inorganic chemistry Vol. 2014; no. 8; pp. 1399 - 1406
• Main Authors: Wismach, Cathleen, Jones, Peter G., du Mont, Wolf-Walther, Mugesh, Govindasamy, Papke, Ulrich, Linden, H. Bernhard, Arca, Massimiliano, Lippolis, Vito
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.03.2014; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Density functional calculations; Iodine; Medicinal chemistry; Physical Sciences; Science & Technology; Solids; Spectrum analysis; Sulfanes; Medicinal chemistry; SULFUR HALIDES; Sulfanes; IODOTHYRONINE DEIODINASE; STABILIZATION; CHEMISTRY; THYROXINE; Density functional calculations; BIS(THIOCARBONYL) DONORS; Iodine; SELENENYL IODIDE
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201301576

Iodination of tris(trimethylsilyl)methanethiol (trisylthiol, TsiSH) in tetrahydrofuran provides the new thermally stable alkanesulfenyl iodide [iodo(trisyl)sulfane, TsiSI] as a violet solid. Iodo(trisyl)sulfane exhibits iodine–iodine contacts between pairs of TsiSI molecules in the solid state. Properties of TsiSI were studied by vibrational spectroscopy and with the help of density functional calculations. TsiSI reacts in the presence of triethylamine with the antithyroid drugs 6‐n‐propyl‐ and 6‐methylthiouracil (PTU, MTU) and with N‐methylmethimazole (MMI) to form unsymmetric disulfides that were investigated by means of X‐ray crystallography. In the solid state, the PTU and MTU derivatives exist as hydrogen‐bonded centrosymmetric dimers, whereas the MMI‐derived disulfide is an unsymmetric monomer. Iodination of tris(trimethylsilyl)methanethiol (TsiSH) in tetrahydrofuran provides stable violet iodo(trisyl)sulfane (TsiSI) 3, which exhibits iodine–iodine contacts between pairs of TsiSI molecules in the solid state. TsiSI reacts with the antithyroid drugs 6‐n‐propyl‐ and 6‐methylthiouracil (PTU, MTU) and with methylmethimazole (MMI) to deliver unsymmetric disulfides like Tsi‐S‐S‐PTU.