N-Halosuccinimide/BF3−H2O, Efficient Electrophilic Halogenating Systems for Aromatics
Top Cited Papers
- 12 November 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 126 (48) , 15770-15776
- https://doi.org/10.1021/ja0465247
Abstract
N-Halosuccinimides (NXS, 1) are efficiently activated in trifluoromethanesulfonic acid and BF3−H2O, allowing the halogenations of deactivated aromatics. Because BF3−H2O is more economic, easy to prepare, nonoxidizing, and offers sufficiently high acidity (−H0 ≈ 12, only slightly lower than that of trifluoromethanesulfonic acid), an efficient new electrophilic reagent combination of NXS/BF3−H2O 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 BF3−H2O complex have also been investigated.This publication has 32 references indexed in Scilit:
- t-Butyl Hypochlorite: A Powerful Electrophilic Aromatic Ring Chlorinating AgentSynthetic Communications, 1998
- Regioselective A-Ring Chlorination of Benzodiazepine Analogues Usingtert-Butyl HypochloriteSynthetic Communications, 1994
- Friedel-Crafts-Type Cyclodehydration of 1,3-Diphenyl-1-propanones. Kinetic Evidence for the Involvement of DicationJournal of the American Chemical Society, 1994
- Convenient Preparation of Alkyl Nitrates Free of Nitrites with Potassium Nitrate and Boron Trifluoride HydrateSynthesis, 1993
- Evaluation of acidity of strong acid catalysts I. The strength of boron trifluoride-water systemsJournal of Catalysis, 1992
- Aromatic Nitration with Potassium Nitrate or Nitric Acid and Boron Trifluoride MonohydrateSynthesis, 1992
- Boron Trifluoride Monohydrate Catalyzed One-Flask Preparation of Sulfides from Carbonyl Compounds with Thiols and TriethylsilaneSynthesis, 1992
- The Chlorination of Anilines. Proof of the Existence of an N-Chloro IntermediateJournal of the American Chemical Society, 1965
- Reactions of Peroxides with Halide Salts. Electrophilic and Homolytic HalogenationsJournal of the American Chemical Society, 1964
- The Action of t-Butyl Hypochlorite on Organic Compounds. II. Aromatic Aldehydes1Journal of the American Chemical Society, 1951