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Synlett 2012(2): 208-214
DOI: 10.1055/s-0031-1290118
DOI: 10.1055/s-0031-1290118
LETTER
© Georg Thieme Verlag
Stuttgart ˙ New York
Remarkable Switch in the Regiochemistry of the Iodination of Anilines by N-Iodosuccinimide: Synthesis of 1,2-Dichloro-3,4-diiodobenzene
Weitere Informationen
Received
2 November 2011
Publikationsdatum:
22. Dezember 2011 (online)
Publikationsverlauf
Publikationsdatum:
22. Dezember 2011 (online)
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Abstract
Direct iodination of anilines by NIS in polar solvents (such as DMSO) affords p-iodinated products with up to >99% regioselectivity. Switching to less polar solvents (such as benzene) in the presence of AcOH inverts this outcome toward dramatically increased or preferential generation of the o-isomers, also with up to >99% regioselectivity. This finding was exploited in the synthesis of 1,2-dichloro-3,4-diiodobenzene.
Key words
aromatic amine - electrophilic substitution - halogenation - regioselectivity - solvent effects
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References and Notes
The structures of all new compounds (Scifinder) were in accord with their analytical and/or spectroscopic properties; see Supporting Information.