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. 2021 Mar 27;26(7):1897.
doi: 10.3390/molecules26071897.

Practical Synthesis of 2-Iodosobenzoic Acid (IBA) without Contamination by Hazardous 2-Iodoxybenzoic Acid (IBX) under Mild Conditions

Hideyasu China  1   2 , Nami Kageyama  2 , Hotaka Yatabe  2 , Naoko Takenaga  3 , Toshifumi Dohi  2
Affiliations

Practical Synthesis of 2-Iodosobenzoic Acid (IBA) without Contamination by Hazardous 2-Iodoxybenzoic Acid (IBX) under Mild Conditions

Hideyasu China et al. Molecules. .

Abstract

We report a convenient and practical method for the preparation of nonexplosive cyclic hypervalent iodine(III) oxidants as efficient organocatalysts and reagents for various reactions using Oxone® in aqueous solution under mild conditions at room temperature. The thus obtained 2-iodosobenzoic acids (IBAs) could be used as precursors of other cyclic organoiodine(III) derivatives by the solvolytic derivatization of the hydroxy group under mild conditions of 80 °C or lower temperature. These sequential procedures are highly reliable to selectively afford cyclic hypervalent iodine compounds in excellent yields without contamination by hazardous pentavalent iodine(III) compound.

Keywords: Oxone®; cyclic organoiodine(III) compounds; water, solvolytic functionalization, mild condition, metal-free, 2-iodosobenzoic acid.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
2-Iodosobenzoic acid (IBA) and its precursor 2-iodobenzoic acid (2-IB).
Figure 2
Figure 2
Synthesis of 2-iodosobenzoic acids (IBAs) and 2-iodoxybenzoic acids (IBXs) from 2-iodobenzoic acids (2-IBs).
Figure 3
Figure 3
Solvent effect on the selective synthesis of IBA 2a from 2-IB 1a using Oxone®.
Figure 4
Figure 4
Substrate scope of the selective preparation of IBAs 2b–v using Oxone® under aqueous conditions. (a) This reaction was performed at 30 °C in the presence of 1.2 equivalents of Oxone®. (b) Performed using 5 equivalents of Oxone® at 40 °C.
Scheme 1
Scheme 1
Synthesis of tricyclic hypervalent iodine compound 4.
Scheme 2
Scheme 2
Effect of a ferric salt on the selective synthesis of IBA 2a.
Figure 5
Figure 5
Optimization of (a) temperature using 1.0 equivalent of Oxone® and (b) amount of Oxone® at 60 °C for the synthesis of IBA 2a from 2-IB 1a in the presence of 2.5 mol% FeCl3 (MeCN/DW (1/1)).
Scheme 3
Scheme 3
Short-time selective synthesis of IBAs 2a–j in the presence of ferric salt.
Figure 6
Figure 6
Benziodoxole alkoxides 6a–h by solvolytic functionalization of IBA 2a.
Scheme 4
Scheme 4
Transformation of IBAs 2a–i to benziodoxole acetates 7a–i.
See this image and copyright information in PMC

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