Benziodoxoles structure

Esters of 2-iodoxybenzoic acid (IBX-esters) 242 were obtained by the hypochlorite oxidation of appropriate 2-iodobenzoate esters 241 (Scheme 55) and isolated in the form of stable microcrystalline solids (2004CC106,2005JOC6484). This procedure has been used for the synthesis of various IBX—esters 242 derived from primary, secondary, and tertiary alcohols, adamantanols, as well as from the optically active menthols and bomeol. A single-crystal X-ray analysis of products 242 has revealed a pseudo-benziodoxole structure in which the intramolecular I 0 secondary bonds partially replace the intermolecular I 0 secondary bonds... 

Methyl-2-iodoxybenzoate can be further converted to the diacetate 243 or a similar bis(trifluoroacetate) by treatment with acetic anhydride or trifluoroacetic anhydride, respectively (2005JOC6484). A single-crystal X-ray diffraction analysis of methyl-2-[(diacetoxy)(oxo)iodo]benzoate 243 revealed a pseudo-benziodoxole structure with three relatively weak intramolecular I 0 interactions. Esters of 2-iodoxyisophthalic acid (e.g., 244) were prepared by the oxidation of the respective iodoarenes with dimethyl-dioxirane. An X-ray structural analysis of diisopropyl 2-iodoxyisophthalate 244 has demonstrated strong intramolecular interaction with the... 

Several cyclic A3-iodanes of diverse structure have been reported over the years since Victor Meyer s o-iodosobenzoic acid, IBA, whose systematic name is 1 -hydroxy-1,2-benziodoxol-3(lH)-one. A recent review on benziodoxoles presents in detail their preparation and interconversions [51]. In Scheme 13 appears a collection of the main types of A3-iodanes which contain either a benziodox-ole ring or a 5-membered-ring with iodine, oxygen and another atom. 

A similar reaction occurred with Me3SiCN to afford 1-cyanobenziodoxoles or their analogs in which the CO group of benziodoxole was CMe2 or C(CF3)2 [169, 170]. Another heterocycle coming from an o-iodobenzenesulfonic acid gave with terminal alkynes 1-alkynyl derivatives as shown in Scheme 56 [171]. The cyclic structure of these iodanes was established by single-crystal X-ray analysis [76,169,170,171]. 

Halobenziodoxoles l-Chloro-l,2-benziodoxol-3-(l//)-one (88, 2X = O, Y = Cl) can be easily prepared by direct chlorination of 2-iodobenzoic acid [233], or by the oxidation of 2-iodobenzoic acid with sodium chlorite (NaC102) in aqueous hydrochloric acid media [267]. The original X-ray single-crystal analysis of l-chloro-l,2-benziodoxol-3-(l//)-one reported in 1976 was relatively imprecise [268]. More recently, Koser and coworkers reported the single-crystal X-ray structure of a 1 1 complex of l-chloro-1,2-benziodoxol-3-(l/7)-one and tetra-n-butylammonium chloride [262], The primary bond distances at iodine in this compound are consistent with expectations for a X -iodane. In particular, the I—Cl and I—O bond distances of 2.454 and 2.145 A, respectively, are greater than the sums of the appropriate covalent radii and reflect the... 

Fig. 12 Crystal structure of l-(phenylethynyl)-l,2-benziodoxol-3(l//)-one where two different I-O bonds are present. One is 2.309 A long (i.e., it is similar to a covalent I-O bond), is depicted as a solid red-violet line, and forms the planar 1-substituted-1,2-beniodoxolone moiety left). The other I - O bond is 2.933 A long (i.e., 0.84 the sum of oxygen and iodine van der Waals radii) and forms infinite and supramolecular chains right). It can be considered as a halogen bond, is depicted as a blue dotted line, and is produced by the entrance of a lone pair of the carbonyl oxygen in the o-hole of iodine. Color codes as in Fig. 2...

Zhdankin VV, Krasutsky AP, Kuehl CJ, Simonsen AJ, Woodward JK, Mismash B, Bolz JT (1996) Preparation, X-ray crystal structure, and chemistry of stable azidoiodinanes derivatives of benziodoxole. J Am Chem Soc 118(22) 5192-5197... 

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