Halogens electrophilic fluorinating agents

Pyridines react easily with halogens and inter-halogens to give crystalline compounds, largely undissociated when dissolved in solvents such as carbon tetrachloride. Structurally they are best formulated as resonance hybrids related to trihalide anions. 1-Fluoropyridinium triflate is also crystalline and serves as an electrophilic fluorinating agent (31.1). ... 

Fluorinated olefins, 77 866 Fluorinated organics, production of, 77 847 Fluorinated polyimides, 20 278 Fluorinated thermoplastics, 10 8 Fluorinated titanocycle, 25 118 Fluorinating agents, electrophilic, 77 847 Fluorination, 9 281, 678-679 aromatic ring, 77 866 chlorocarbons, 6 235 direct, 77 864, 882 electrochemical, 77 864—865, 882 of germanium, 72 552 halogen exchange, 77 861-864 selective, 77 831... 

Fluorine has been used for the generation of extremely strong electrophilic halogenating agents in electrophilic iodination and bromination of deactivated aromatic substrates in highly acidic reacton media. Polyhalogenation of more activated aromatic substrates is also possible (Fig. 90) [231-233]. 

The general concept is that sulfur is introduced into the organic substrate as a direct synthetic precursor of fluorine. Tlte sulfur compound is then treated with a thiophilic, soft electrophilic oxidant, for example electrophilic halogenation agents (NBS, NIS, DBH, Br2, SO2CI2 [148], Fj [149], IF5 [150], BrFj [151], 4-MePhIF2 [152], or nitrosyl cations (NO BF., ) [146] in the presence of a fluoride source (50% or 70% HF-pyridine [143], HF-melamine [144], NEt3 3HF) [147]. 

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