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.
Elemental sulfur (S8) mediates aromatic halogenations using N-halosuccinimides
for bromination and chlorination or 1,3-diiodo-5,5-dimethylhydantoin for
iodination. The reaction effectively halogenated also less-reactive aromatic
compounds, such as ester-, cyano-, and nitro-substituted anisole derivatives.
J. Matsuoka, Y. Yano, Y. Hirose, K. Mashiba, N. Sawada, A. Nakamura, T.
Maegawa, J. Org. Chem., 2024, 89,
770-777.
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.