Preparation and X-ray structure of 2-iodoxybenzenesulfonic acid (IBS) – a powerful hypervalent iodine(V) oxidant

Abstract

The selective preparation of 2-iodoxybenzenesulfonic acid (IBS, as potassium or sodium salts) by oxidation of sodium 2-iodobenzenesulfonate with Oxone or sodium periodate in water is reported. The single crystal X-ray diffraction analysis reveals a complex polymeric structure consisting of three units of IBS as potassium salt and one unit of 2-iodoxybenzenesulfonic acid linked together by relatively strong I=O···I intermolecular interactions. Furthermore, a new method for the preparation of the reduced form of IBS, 2-iodosylbenzenesulfonic acid, by using periodic acid as an oxidant, has been developed. It has been demonstrated that the oxidation of free 2-iodobenzenesulfonic acid under acidic conditions affords an iodine(III) heterocycle (2-iodosylbenzenesulfonic acid), while the oxidation of sodium 2-iodobenzenesulfonate in neutral aqueous solution gives the iodine(V) products.

A new hypervalent iodine(iii/v) oxidant and its application to the synthesis of 2H-azirines

“…3A ). The crystal structure of 1 is uncommon among the known hypervalent iodine structures that have been characterized to date, with a pentavalent I(2) atom and a trivalent I(1) atom coexisting in one molecule via connection of an O(3) atom 17,28 ( Fig. 3B ).…”

“…The existing hypervalent iodine( iii ) reagents include phenyliodine diacetate (PIDA), phenyliodine bis(trifloroacetate) (PIFA), iodosylbenzene (PhIO), [hydroxyl(tosyloxy)iodo]benzene (HTIB, Koser reagent), 4 PhICl 2 , 5 TolIF 2 , 6 diaryl iodonium salts, 7 Togni's reagents, 8 μ-oxobis(trifluoroacetoxyiodobenzene) (μ-oxo BTI), 9 cyano(trifluoromethylsulfonyloxy)iodobenzene (Stang's reagent), 10 1-phenyl-2-(phenyl-λ 3 -iodaneylidene)-2-((trifluoromethyl)sulfon-yl)ethan-1-one (Shibata reagent II), 11 iodosodilactone, 1 e etc. 12 The more widely studied hypervalent iodine( v ) regents mainly include 2-iodoxybenzoic acid (IBX), 13 Dess–Martin periodinane (DMP), 14 Hara reagent, 15 pentafluorophenyliodine tetrafluoride (PFITF), 16 2-iodoxybenzenesulfonic acid (IBS), 17 iodine pentafluoride, 18 iodoxybenzene, 19 and diaryliodosyl salts 20 ( Fig. 1 ).…”

2-Iodoxybenzoic acid ditriflate: the most powerful hypervalent iodine(v) oxidant

“…According to elemental analysis, a sample of product 4 prepared by recrystallization in open air is a complex of IBX with two molecules of trifluoromethanesulfonic acid. 1 H NMR spectrum of triflate 4 displayed signals in the aromatic region corresponding to the benziodoxole unit, while 13 C NMR displayed the signal of C-I(V) at about 147 ppm, which is typical of organoiodine(V) derivatives. X-ray crystallographic study of a single crystal 4 revealed a complex structure characterized by numerous intramolecular and intermolecular secondary contacts in a solid state ( Fig.…”

“…In a search for the more powerful iodine(V) oxidants, several IBX modifications have been synthesized and investigated. [12][13][14][15][16] The most notable powerful iodine(V) oxidants are represented by the highly electrophilic IBX-tosylate and IBX-OTs diacetate 3, 16 which show high reactivity in the oxidation of structurally complex primary and secondary alcohols. 17 In the present communication, we want to report the preparation, structure and reactivity of IBX-ditriflate 4, the most powerful oxidant in the series of structurally similar IBX derivatives ( Fig.…”

Carbon-Electrode-Mediated Electrochemical Synthesis of Hypervalent Iodine Reagents Using Water as the O-Atom Source

“… 1 H NMR aromatic region of 20 mM PhI-sulfonic acid, 100 mM LiClO 4 supporting electrolyte with 10% added water (v/v%) showing peaks before electrolysis and after 19, 59, and 120 C of charge passed and the same 120 C solution aged 2 days. 1 H NMR peaks for IBA- and IBX-sulfonic acid match the literature. ,, † The theoretical yield for IBX-sulfonic acid was determined assuming full conversion to IBX-sulfonic acid (i.e., 4e – /molecule). See the Supporting Information for a sample calculation of the Faradaic efficiency and additional discussion.…”