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Regioselective radical arylation of anilines with arylhydrazines.

The Journal of organic chemistry (2012-11-08)
Hannelore Jasch, Julia Scheumann, Markus R Heinrich
ABSTRACT

Substituted 2-aminobiphenyls have been prepared from arylhydrazines and anilines via radical arylation reactions under simple oxidative conditions. The strong directing effect of the free and unprotonated amino functionality leads to high regioselectivities, and anilines have been shown to be significantly better aryl radical acceptors than nitrobenzenes or phenyl ethers. The methodology is also applicable to phenols, which react best as phenolates under strongly basic conditions. Finally, radical arylation reactions of anilines and anilinium salts under various conditions have for the first time demonstrated that regioselectivity can also be controlled through the rearomatization step and that the addition of an aryl radical to a substituted benzene might even be reversible.

MATERIALS
Product Number
Brand
Product Description

Sigma-Aldrich
Aniline-15N, 98 atom % 15N
Sigma-Aldrich
Aniline, ACS reagent, ≥99.5%
Supelco
Aniline, analytical standard
Sigma-Aldrich
Aniline, ReagentPlus®, 99%
Sigma-Aldrich
Aniline hydrochloride, ≥99%
Supelco
Aniline solution, certified reference material, 5000 μg/mL in methanol