Bacterial metabolism of side chain fluorinated aromatics: cometabolism of 4-trifluoromethyl(TFM)-benzoate by 4-isopropylbenzoate grown Pseudomonas putida JT strains.
Enzymes of the p-cymene pathway in Pseudomonas putida strains cometabolized the intermediate analogue 4-trifluoromethyl(TFM)benzoate. Three products, 4-TFM-2,3-dihydro-2,3-dihydroxybenzoate, 4-TFM-2,3-dihydroxybenzoate and 2-hydroxy-6-oxo-7,7,7-trifluorohepta-2,4-dienoate (7-TFHOD) were identified chemically and by spectroscopic properties. Certain TFM-substituted analogue metabolites of the p-cymene pathway were transformed at drastically reduced rates. Hammett type analysis of ring cleavage reactions of 4-substituted 2,3-dihydroxybenzoates revealed the negative inductive and especially mesomeric effect of substituents to be rate determining. Whereas decarboxylation of 3-carboxy-7-TFHOD was not affected by fluorine substitution the subsequent hydrolysis of 7-TFHOD proceeded very slowly. The negative inductive effect of the TFM-group probably inhibited heterolysis of the carbon bond between C5 and C6 of 7-TFHOD.
Engesser
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KH
Institut für Mikrobiologie der Universität Stuttgart, Federal Republic of Germany.
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Ribbons
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D001565:Benzoates / Q000378:metabolism*; D001673:Biodegradation, Environmental; D002262:Carboxy-Lyases / Q000378:metabolism; D055598:Chemical Phenomena; D002621:Chemistry; D002851:Chromatography, High Pressure Liquid; D002855:Chromatography, Thin Layer; D008401:Gas Chromatography-Mass Spectrometry; D006868:Hydrolysis; D007700:Kinetics; D010088:Oxidoreductases / Q000378:metabolism; D010105:Oxygenases / Q000378:metabolism; D011549:Pseudomonas / Q000201:enzymology* / Q000254:growth & development; D014050:Toluene / Q000031:analogs & derivatives* / Q000378:metabolism
D001565:Benzoates; D014050:Toluene; C028383:4-(trifluoromethyl)benzoic acid; C055607:cumic acid; D010088:Oxidoreductases; D010105:Oxygenases; D002262:Carboxy-Lyases