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Chemicals >> Oxidizing Agents

1,3-Diiodo-5,5-Dimethylhydantoin, DIH

DIH has a comparable reactivity to molecular iodine, but DIH is more convenient to handle, because the solid reagent does not sublimate. DIH is also an alternative to NIS (N-iodosuccinimide) for the iodination of arenes or enols.

Recent Literature

Various primary alcohols, and primary, secondary, and tertiary amines were efficiently converted into the corresponding nitriles in good yields by oxidation with 1,3-diiodo-5,5-dimethylhydantoin (DIH) in aqueous ammonia at 60 C.
S. Iida, H. Togo, Synlett, 2007, 407-410.

S. Iida, H. Togo, Synlett, 2007, 407-410.

Various alcohols were efficiently converted into the corresponding nitriles at room temperature by treatment with tert-butyl hypochlorite, diiodine, or 1,3-diiodo-5,5-dimethylhydantoin (DIH) in the presence of TEMPO, followed by treatment with diiodine and aqueous ammonia. The nitriles were obtained in good yields and high purities by a simple extraction of the reaction mixture with chloroform and subsequent removal of the solvent.
H. Shimojo, K. Moriyama, H. Togo, Synthesis, 2013, 45, 2155-2156.

An efficient and robust method enables a general conversion of aliphatic and aromatic carboxylic acids to organic iodides without the use of heavy metals or strong oxidizing agents. Commercially available N-iodoamides were used for both initiation and halogen donation under irradiative conditions. Isolation of the product is extremely simple and the major co-product is water-soluble.
K. Kulbitski, G. Nisnevich, M. Gandelman, Adv. Synth. Catal., 2011, 353, 1438-1442.

In a disulfide-catalyzed electrophilic iodination of electron-rich aromatic compounds using 1,3-diiodo-5,5-dimethylhydantoin (DIH), the disulfide activates DIH as a Lewis base to promote the iodination reaction in acetonitrile under mild conditions. This system is applicable to a wide range of substrates, including anisoles, acetanilides, imidazoles, and pyrazoles.
K. Iida, S. Ishida, T. Watanabe, T. Arai, J. Org. Chem., 2019, 84, 7411-7417.

An organocatalytic iodination of activated aromatic compounds using 1,3-diiodo-5,5-dimethylhydantoin (DIH) as the iodine source with thiourea catalysts in acetonitrile is applicable to a number of aromatic substrates with significantly different steric and electronic properties. The iodination is generally highly regioselective and provides high yields of isolated products.
G. Jakab, A. Hosseini, H. Hausmann, P. R. Schreiner, Synthesis, 2013, 45, 1635-1640.

The use of 1,3-diiodo-5,5,-dimethylhydantoin and HF-based reagents enables a regio- and stereoselective iodofluorination of internal and terminal alkynes. A facile method for a controlled regioselective double iodofluorination of terminal alkynes is also presented.
L. Pfeifer, V. Gouverneur, Org. Lett., 2018, 20, 1576-1579.

Various aromatic and aliphatic aldehydes were converted into the corresponding 2-aryl and 2-alkyl-2-oxazolines, respectively, in good yields by reaction with 2-aminoethanol and 1,3-diiodo-5,5-dimethylhydantoin.
S. Takahashi, H. Togo, Synthesis, 2009, 2329-2332.