Synthesis of Stable Cyclic Sulfinamides with a Hydroperoxy Function by Oxidation of Isothiazolium Salts

Abstract

The oxidation of isothiazolium salts 4 to stable 2‐aryl‐2,3,4,5,6,7‐hexahydro‐3‐hydroperoxy‐1,2‐benzisothiazole 1‐oxides rac‐cis‐6 (sultims) as a new class of cyclic sulfinamides is described. The formations of the oxidation products rac‐cis‐6 as well as 3‐hydroperoxy and 3‐hydroxy sultams, 8 and 9, respectively, and isothiazol‐3(2H)‐one 1,1‐dioxides 10 are presented.

Synthesis of Monocyclic Hydroperoxy- and Hydroxy-Substituted Sulfin- and Sulfonamides by Oxidation of 4,5-Dimethylisothiazolium Salts

“…In the first step, nucleophilic attack of H 2 O 2 at C(3) of 10 probably occurs in analogy to the mechanism proposed for bicyclic sultams [22]. A second attack of the oxidant at the Satom then results in the formation of the rac-cis-and rac-trans-3-hydroperoxy compounds 13.…”

Crystal structure of rac-cis-N-(2,4-dinitrophenyl)-3,4-diphenyl-5H-1,2-oxathiol- 5-amine 2-oxide, C21H15N3O6S, sultim and sultam structures – part 4

“…Atfirst, the salts can be oxidized with H 2 O 2 in acetic acid to yield 3-hydroperoxysultims rac-cis/ trans,s ultams and 3-oxosultams [1][2][3][4][5]. Furthermore, the isothiazolium salts reacted with magnesium monoperoxyphthalate (MMPP)inwater or alcohol to obtain the 3-hydroxysultims rac-cis/ trans,sultams or 3-alkoxysultams [6,7].…”

“…The oxidation of monocyclic and bicyclic isothiazolium salts has been research intensively since the last years [1][2][3][4][5][6][7] and can be classified in two principle oxidation methods. Atfirst, the salts can be oxidized with H 2 O 2 in acetic acid to yield 3-hydroperoxysultims rac-cis/ trans,s ultams and 3-oxosultams [1][2][3][4][5].…”

Five‐Membered Heterocycles: 1,2‐Azoles. Part 2. Isoxazoles and Isothiazoles

“…Cycloalka [c]isothiazoles 122 can be prepared by a similar method [216]. 2-Thiocyanatocyclohex-1-ene carbaldehyde (123) reacts with anilines to afford isothiazolium salts 124 [217]. Methacrylonitrile reacts with trithiazyl trichloride (NSCl) 3 in the presence of excess SO 2 Cl 2 , in refluxing chloroform, to give 4-cyanoisothiazole in 78% yield [218].…”