NMR study on the structure and stability of 4‐substituted aromatic iodosyl compounds

Abstract

Two 4-substituted aromatic iodosyl compounds were investigated with regard to their solubility, stability and chromatographic behaviour. 1-Iodosyl-4-methoxy- and 1-iodosyl-4-nitro-benzene are soluble in methanol and provide acceptable 1H and 13C NMR spectra; however, gradual oxidation of the solvent was observed. LC-MS analyses suggest that unlike the parent substance, iodosylbenzene, which has a polymeric structure, both compounds rather exist in the monomeric form.

Advances in Synthetic Applications of Hypervalent Iodine Compounds

“…Under these conditions, various substituted iodosylarenes 7 can be prepared from the corresponding (diacetoxyiodo)­arenes (Scheme ). ,− This procedure can also be used for the synthesis of 4 - methoxyiodosylbenzene, 4 - nitroiodosylbenzene, and the pseudocyclic iodosylarenes 8 – 11 bearing 2- tert -butylsulfonyl, ,, or 2-diphenylphosphoryl groups ­(Figure ). …”

Chemistry of Polyvalent Iodine

“…Several important spectroscopic structural studies of polyvalent iodine compounds in the solution have been published 108–112. Hiller and co-workers reported NMR and LC-MS study on the structure and stability of 1-iodosyl-4-methoxybenzene and 1-iodosyl-4-nitrobenzene in methanol solution 108.…”

“…Several important spectroscopic structural studies of polyvalent iodine compounds in the solution have been published. − Hiller and co-workers reported NMR and LC-MS studies on the structure and stability of 1-iodosyl-4-methoxybenzene and 1-iodosyl-4-nitrobenzene in methanol solution . Interestingly, LC-MS analyses provided evidence that unlike the parent iodosylbenzene, which has a polymeric structure, the 4-substituted iodosylarenes exist in the monomeric form.…”

“…Both iodosylarenes are soluble in methanol and provide acceptable 1 H and 13 C NMR spectra; however, gradual oxidation of the solvent was observed after several hours. Unlike iodosylbenzene, the two compounds did not react with methanol to give the dimethoxy derivative ArI(OMe) 2 …”

“…The most important representative of iodosylarenes, iodosylbenzene, is best prepared by alkaline hydrolysis of (diacetoxy)iodobenzene . The same procedure can be used for the preparation of a variety of ortho -, meta -, and para -substituted iodosylbenzenes from the respective (diacetoxy)iodoarenes (Scheme ). − ,, This procedure, for example, was recently used for the preparation of 4-methoxyiodosylbenzene, 4-nitroiodosylbenzene, and pseudocyclic iodosylarenes bearing tert -butylsulfonyl or diphenylphosphoryl groups in the ortho -position.…”