185. Stereochemistry of metabolic diols from naphthalene and anthracene

Cook, J. W.; Loudon, J. D.; Williamson, W. F.

doi:10.1039/jr9500000911

Cited by 11 publications

(4 citation statements)

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“…After 30 min, rra/is-l,2-dihydroxycyclohexa-3,5-diene (rram-benzene glycol) caused the appearance of a purple color. A similar observation was reported for fra«j-l ,2-dihydroxytetrahydronaphthalene (Cook et al, 1950). The results obtained indicate that the isolated glycol is either cis (ae) II or IV, or possibly trans (ee) III. Nuclear Magnetic Resonance Spectrum.…”

Section: Resultssupporting

confidence: 87%

Oxidative degradation of aromatic hydrocarbons by microorganisms. II. Metabolism of halogenated aromatic hydrocarbons

Gibson¹,

Koch²,

Schuld³

et al. 1968

Biochemistry

226

129

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Pseudomonas putida, grown with toluene as sole source of carbon, oxidized chloro-, bromo-, iodo-, and fluorobenzenes to their respective 3-halogenated catechol derivatives. The dihydroxy compounds from the first three substrates above were identified by isolation and comparison with synthetic compounds. The investigation of the metabolism of ^-chlorotoluene resulted in the isolation of two compounds which have Our continued interest in the mechanism of oxygen fixation into the aromatic nucleus led us to try to isolate the early intermediates in the degradation of several aromatic compounds. Since both toluene and benzene are metabolized at an extremely rapid rate by Pseudomonas putida (Gibson et al., 1968), with little accumulation of reaction products, it seemed probable that cooxidation (Leadbetter and Foster, 1960; Davis and Raymond, 1961) might be of use in our studies. Halogenated aromatic derivatives were chosen as potential partially metabolizable intermediates. The presence of a halogen atom seems to greatly reduce the biodegradability of many aromatic compounds (Alexander and Lustigman, 1966;Ichihara et al., 1962).This paper describes the isolation and identification of the products formed from chloro-, bromo-, iodo-, and fluorobenzenes and also p-chlorotoluene when these substrates are incubated with cells of P. putida, grown with toluene as the sole source of carbon. Materials and Methods1Organism and Growth Conditions. P. putida was grown in media whose composition has been described previously (Gibson et al., 1968).

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Section: Resultssupporting

confidence: 87%

Oxidative degradation of aromatic hydrocarbons by microorganisms. II. Metabolism of halogenated aromatic hydrocarbons

Gibson¹,

Koch²,

Schuld³

et al. 1968

Biochemistry

226

129

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“…trans -1,2-Dihydroxy-1,2,3,4-tetrahydronaphthalene (11) ,,, was prepared in accord with a previously published method . The crude product was purified by recrystallization from chloroform, mp 110−111 °C.…”

Section: Methodsmentioning

confidence: 99%

Kinetic and Thermodynamic Stability of Naphthalene Oxide and Related Compounds. A Comparative Microcalorimetric and Computational (DFT) Study

2002

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The kinetics of the acid-catalyzed ring opening of naphthalene 1,2-oxide (5) in highly aqueous media to give naphthols has been measured by heat-flow microcalorimetry. The reaction enthalpy of this aromatization reaction was measured as DeltaH = -51.3 +/- 1.7 kcal mol(-)(1). The unexpectedly low reactivity of naphthalene oxide is suggested to be due to an unusually large thermodynamic stability. A crude estimate of the stabilization effect, approximately 1 kcal mol(-)(1)(not a significant stabilization), is obtained by using the measured reaction enthalpies of structurally related substrates as references. A larger value (2.7 kcal mol(-)(1)) was obtained by calculation using the B3LYP hybrid functional corrected with solvation energies derived from semiempirical AM1/SM2 calculations. The origin of this effect is discussed in terms of homoconjugative stabilization and homoaromaticity. There is a good linear correlation (with slope = 0.63) between the experimentally measured free energy of activation and the calculated enthalpy of carbocation formation in water.

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“…The trans-[3H]diols (ca. 0.1 µ%) formed metabolically from BP and nonradioactive synthetic (±)-irani-diols (50 µ%) in 0.1 mL of pyridine were reacted with (-)-menthoxyacetyl chloride (10 mg) for 16 h at room temperature similarly as reported by Cook et al (1950). One milliliter of water was added to the reaction mixture and was extracted twice with 2 mL of diethyl ether/benzene (1:1, v/v).…”

Section: Methodsmentioning

confidence: 99%

Enzymic mechanism of benzo[a]pyrene conversion to phenols and diols and an improved high-pressure liquid chromatographic separation of benzo[a]pyrene derivatives

Yang¹,

Roller²,

Gelboin³

1977

Biochemistry

102

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Benzofajpyrene is stereospecifically converted in two enzymatic steps by rat liver microsomal mixed-function oxidases and epoxide hydratase to the (-) enantiomers of the trans-4,5-, /rani-7,8-, and /rans-9,10-diols. The initial mixed-function epoxidation at the 4,5, 7,8, and 9,10 positions occurs at one side of the planar benzo[a]pyrene molecule to form epoxide intermediates, and this is followed by a substrate-stereoselective and a product-stereospecific hydration of the epoxide intermediates by epoxide hydratase to the (-)-rrans-diols. The identification of the diols as optically pure (-)-trans enantiomers was accomplished by high-pressure liquid chromatographic separation of the cis and trans isomers, and of the di-(-)-menthoxyacetates of the (+)and (-)-trans enantiomers. Incubation of benzofajpyrene with rat liver Benzofajpyrene (BP)* 1 is the most commonly studied polycyclic aromatic hydrocarbon of the environment and exerts several biological effects (Particulate Polycyclic Organic Matter, National Academy of Sciences, 1972). The biological activities included toxicity, mutagenicity, tumorigenicity, and covalent binding to DNA (

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185. Stereochemistry of metabolic diols from naphthalene and anthracene

Cited by 11 publications

References 0 publications

Oxidative degradation of aromatic hydrocarbons by microorganisms. II. Metabolism of halogenated aromatic hydrocarbons

Oxidative degradation of aromatic hydrocarbons by microorganisms. II. Metabolism of halogenated aromatic hydrocarbons

Kinetic and Thermodynamic Stability of Naphthalene Oxide and Related Compounds. A Comparative Microcalorimetric and Computational (DFT) Study

Enzymic mechanism of benzo[a]pyrene conversion to phenols and diols and an improved high-pressure liquid chromatographic separation of benzo[a]pyrene derivatives

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