319-92-6Relevant academic research and scientific papers
Fluorination of aromatic compounds with N-fluorobenzenesulfonimide under solvent-free conditions
Andreev,Borodkin,Shubin
scheme or table, p. 1468 - 1473 (2010/03/24)
Reactions of N-fluorobenzenesulfonimide with methylbenzenes, phenols, and phenol ethers were studied under solvent-free conditions. The rate constant ratio for the reactions with mesitylene and durene indicates polar mechanism of the process. Solvent-free fluorination of aromatic compounds with N-fluorobenzenesulfonimide in some cases is more selective than reactions with other N-F reagents in a solvent.
First application of ionic liquids in electrophilic fluorination of arenes; Selectfluor (F-TEDA-BF4) for "green" fluorination
Laali, Kenneth K.,Borodkin, Gennady I.
, p. 953 - 957 (2007/10/03)
The NF fluorinating agent F-TEDA-BF4 dication salt (Selectfluor) 1 dissolves in imidazolium-based ionic liquids [emim][OTf] 7, [emim][BF4] 8, [bmim][PF6] 9 and [bmim][BF4] 10 (assisted by sonication), providing a convenient medium for fluorination of arenes under essentially acid-free conditions in a simple set-up (no volatile solvent; simple extraction of the aromatics without aqueous work-up), from which the ionic liquid can be easily recycled and reused. Comparative studies in [emim][OTf] 7 with anisole as substrate show that 1 is superior to NFTh-BF4 (Accufluor) 2 and that the N-fluoropyridinium salt NFPy-B2F7 4 is least effective. The scope of the reaction has been surveyed. Substrate selectivity (k mesitylene: k durene = 10) measured in competitive experiments in 7 is clearly indicative of a conventional polar mechanism. Substrate selectivity measured without the ionic liquid in MeCN solvent is also indicative of a polar mechanism but exhibits lower magnitude (k mesitylene: kdurene = 6). Addition of dicyclohexano-24-crown-8 to the fluorination reaction mixture (1 and anisole) in 7 reduced the conversion but did not change the isomer distribution. AM1 minimization was used to model the complexation of 1 with this crown. With reactive aromatics optimal fluorination yields in ionic liquids (using 1 equivalent of the NF reagent) are around 50% (higher for naphthalene). A key control experiment suggests that the free base (produced upon transfer-fluorination) could complex to unreacted 1 (generating a bulky dimer complex which may be ineffective for fluorine transfer) in competition to N-protonation.
Time-resolved Spectroscopy and Charge-transfer Photochemistry of Aromatic EDA Complexes with X-Pyridinium Cations
Bockman, T. M.,Lee, K. Y.,Kochi, J. K.
, p. 1581 - 1594 (2007/10/02)
Direct photoexcitation of 1: 1 aromatic EDA complexes with various N-substituted X-pyridinium cations (X = nitro, fluoro, methoxy and acetoxy) is achieved by the specific irradiation of their charge-transfer (CT) absorption bands.Time-resolved picosecond spectroscopy refers to charge-transfer activation by the identification of the aromatic cation radical as the initial transient (T1) formed in a photoinduced electron-transfer together with the X-pyridinyl radical.The homolytic fragmentation of the latter varies with the X-substituent in the order X = NO2 > F > AcO >CH3O, and the addition of X. to the aromatic donors leads to a series of cyclohexadienyl adducts that are identified as longer-lived transients (T2) by time-resolved (nanosecond/microsecond) spectroscopy.The phototransients T1 and T2 together account for the different types of aromatic product (resulting from ring substitution, side-chain substitution and dimerization) that are generated by steady-state CT photochemistry of the aromatic EDA complexes with X-pyridinium cations.
Effect of Catalyst on the Fluorination of Methyl-Substituted Benzenes with Xenon Difluoride
Stavber, Stojan,Zupan, Marko
, p. 2223 - 2226 (2007/10/02)
The course of acid-catalyzed liquid-phase fluorination of methyl-substituted benzene derivatives with xenon difluoride depends strongly on the structure and concentration of the substrate, its molar ratio to xenon difuoride, and the catalyst.HF-catalyzed
