N-Halosuccinimides (NXS, 1) are efficiently activated in trifluoromethanesulfonic acid and BF(3)-H(2)O, allowing the halogenations of deactivated aromatics. Because BF(3)-H(2)O is more economic, easy to prepare, nonoxidizing, and offers sufficiently high acidity (-H(0) approximately 12, only slightly lower than that of trifluoromethanesulfonic acid), an efficient new electrophilic reagent combination of NXS/BF(3)-H(2)O has been developed. DFT calculations at the B3LYP/6-311++G//B3LYP/6-31G level suggest that protonated N-halosuccinimides undergo further protosolvation at higher acidities to reactive superelectrophilic species capable either in the transfer of X(+) from the protonated forms of NXS to the aromatic substrate or in forming a highly reactive and solvated X(+) which would readily react with the aromatic substrates. Structural aspects of the BF(3)-H(2)O complex have also been investigated.
Aromatics. -N-halosuccinimide/BF3·H2O mixtures are found to be efficient reagents for halogenation of deactivated arenes. DFT theoretical calculations show that superelectrophilic reagents are generated by multiple protonation of the N-halosuccinimides under the present conditions. -(PRAKASH*, G. K. S.; MATHEW, T.; HOOLE, D.; ESTEVES, P. M.; WANG, Q.; RASUL, G.; OLAH, G. A.; J. Am. Chem.
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