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Towards Greener Fluorine Organic Chemistry: Direct Electrophilic Fluorination of Carbonyl Compounds in Water and Under Solvent‐Free Reaction Conditions
Author(s) -
Stavber Gaj,
Stavber Stojan
Publication year - 2010
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201000477
Subject(s) - chemistry , selectfluor , reactivity (psychology) , octane , trifluoromethyl , reagent , electrophile , tetrafluoroborate , organic chemistry , electrophilic fluorination , solvent , fluorine , ionic liquid , catalysis , alkyl , medicine , pathology , alternative medicine
Selective and efficient fluorination of organic 1,3‐dicarbonyl compounds was achieved using the electrophilic fluorinating reagents Selectfluor TM F‐TEDA‐BF 4 (1‐chloromethyl‐4‐fluoro‐1,4‐diazoniabicyclo[2.2.2]octane bis‐tetrafluoroborate) in aqueous medium or Accufluor TM NFSi ( N ‐fluorobenzenesulfonimide) under solvent‐free reaction conditions (SFRC). Under both reaction conditions cyclic 1,3‐dicarbonyl compounds were transformed into 2‐fluoro‐substituted derivatives and acyclic analogues into 2,2‐difluoro‐substituted compounds, while the reactions of 1‐trifluoromethyl‐substituted 1,3‐dicarbonyls in water resulted in the formation of 2,2‐difluoro‐3,3‐dihydroxy‐1‐one derivatives. The reactivity of the starting material in water was found to be dependent on its enolizability, hydrophobic interactions and aggregate state at the reaction temperature. Reactions under SFRC proceeded in the molten eutectic phase of the reactants. The technique of competitive reactivity was used in order to evaluate and better understand the effects of reaction conditions on the course of these reactions.