N-Halosuccinimide/BF3−H2O, Efficient Electrophilic Halogenating Systems for Aromatics
Citations Over TimeTop 10% of 2004 papers
Abstract
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.
Related Papers
- → Exotic Electrophiles in Chlorinated and Chloraminated Water: When Conventional Kinetic Models and Reaction Pathways Fall Short(2020)54 cited
- → Rh-Catalyzed Reactions of 1,4-Benzoquinones with Electrophiles: C–H Iodination, Bromination, and Phenylselenation(2016)60 cited
- → Dioxoiodane Compounds as Versatile Sources for Iodine(I) Chemistry(2016)49 cited
- → Sulfoxylic Acid Derivatives as Novel Sulfenylating Reagents(1994)
- → A Versatile, Electrophilic Reagent for Monofluoromethylthiola-tion(2023)