Abstract
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-dihydroxy-benzoate and 2-hydroxy-6-oxo-7,7,7-trifluorohepta-2,4-dienoate (7-TFHOD) were identified chemically and by spectroscopic proterties.
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.
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Abbreviations
- DHB:
-
1,2-Dihydroxy-2-hydrobenzoate
- DHC:
-
2,3-Dihydro-2,3-dihydroxybenzoate, this compound was termed DHC simply to distinguish it from the similar 1,2-dihydroxy-2-hydrobenzoate (DHB) as described in the preceeding paper (Engesser et al. 1988)
- HMS:
-
2-Hydroxymuconic semialdehyde
- HOD:
-
2-Hydroxy-6-oxohepta-2,4-dienoate
- 7-TFHOD:
-
2-Hydroxy-6-oxo-7,7,7-trifluorohepta-2,4-dienoate
- TFM:
-
Trifluoromethyl
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This work was supported, in part, by the Gesellschaft für Strahlen- und Umweltforschung, Neuherberg/München, FRG
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Engesser, K.H., Rubio, M.A. & Ribbons, D.W. Bacterial metabolism of side chain fluorinated aromatics: cometabolism of 4-trifluoromethyl(TFM)-benzoate by 4-isopropylbenzoate grown Pseudomonas putida JT strains. Arch. Microbiol. 149, 198–206 (1988). https://doi.org/10.1007/BF00422005
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DOI: https://doi.org/10.1007/BF00422005