Mild hydrolysis of 2-trifluoromethylphenol: kinetics, mechanism and environmental relevance.
2-Trifluoromethylphenol was hydrolysed in a phosphate buffer at neutral pH. At mild temperatures ranging from 34 degrees C to 69 degrees C this compound liberates consecutively fluorine anions to form salicylic acid. This process is energetically driven by the hydration of the fluorine anions. No intermediates have been detected by HPLC and (19)F-NMR and this was confirmed by computer calculations which favor the first step in the whole reaction sequence being rate-limiting. Accordingly, the reaction energy of the first dehalogenation of the trifluoromethyl anion is 28.4 kcal mol(-1) higher than for the second dehalogenation. The pseudo-first-order kinetic was determined and from an Arrhenius diagram an activation energy of E(a)=25.1 kcal mol(-1) has been estimated. At 37 degrees C and a pH of 7.4 the half-life was 6.9 h. The rate of hydrolysis was favored at higher pH and it was not influenced by oxygen, sunlight or trace elements found in natural water. The latter was shown by incubations with lake water instead of distilled water.
Reinscheid
Uwe M
UM
Max Planck Institute for Biophysical Chemistry, NMR II, Am Fassberg 11, 37 077 Göttingen, Germany. urei@nmr.mpibpc.mpg.de
Vervoort
Jacques
J
Zuilhof
Han
H
D000838:Anions; D002851:Chromatography, High Pressure Liquid; D005461:Fluorine / Q000032:analysis / Q000737:chemistry; D005618:Fresh Water; D006845:Hydrocarbons, Fluorinated / Q000032:analysis* / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D007700:Kinetics; D009682:Magnetic Resonance Spectroscopy; D010100:Oxygen / Q000737:chemistry; D010636:Phenols / Q000032:analysis* / Q000737:chemistry; D020156:Salicylic Acid / Q000032:analysis / Q000737:chemistry; D013472:Sunlight; D013696:Temperature; D014131:Trace Elements / Q000737:chemistry
C113796:2-trifluoromethylphenol; D000838:Anions; D006845:Hydrocarbons, Fluorinated; D010636:Phenols; D014131:Trace Elements; D005461:Fluorine; D020156:Salicylic Acid; D010100:Oxygen