Mechanism of hydroxylation of aromatic compounds: II. Evidence for the involvement of superoxide anions in enzymatic hydroxylations

The mechanism of hydroxylation reactions catalyzed by m-hydroxybenzoate-4-hydroxylase and anthranilate hydroxylase from Aspergillus niger was investigated using superoxide dismutase from ovine erythrocytes. Inclusion of superoxide dismutase in the assay mixtures of the two enzymes resulted in complete inhibition of the hydroxylation reaction, indicating the possible involvement of superoxide anions (O2−) in these reactions.

Mechanism of hydroxylation of aromatic compounds: Evidence for the involvement of superoxide anion in a model system

Hydroxylation of aromatic compounds was observed in NADH-phenazine methosulfate-O2 model system known to generate superoxide anions (Image ). Addition of superoxide dismutase prepared from ovine erythrocytes to this hydroxylating system resulted in complete inhibition, suggesting an involvement of Image in aromatic hydroxylations.

Synthesis of ethyl arylacetates by means of Friedel-Crafts reactions of aromatic compounds with ethyl alpha-chloro-alpha-(ethylthio)acetate catalysed by ytterbium triflate

An efficient Friedel-Crafts alkylation of aromatic compounds with ethyl alpha -chloro-alpha-(ethylthio)acetate catalysed by ytterbium triflate, followed by desulfurisation of the product provides a convenient methodology for the synthesis of ethyl arylacetates of aromatic and heteroaromatic compounds. (C) 2000 Elsevier Science Ltd. All rights reserved.

1,2-Shift in the anodic oxidation of aromatic compounds

The 1,2-shift observed during oxidation of organic substrates can arise by involvement of cation radicals.

A new general method for the introduction of the aldehyde function in aromatic compounds

Side chain bromination of aromatic amidomethylated compounds yields aldehydes.

CHEMICAL-IONIZATION MASS-SPECTROMETRY OF SOME NITRO-CONTAINING BIFUNCTIONAL AROMATIC-COMPOUNDS - LOCATION OF PROTONATION SITE

It is found that the nitro substituent of some aromatic bifunctional compounds shows unusual reactivity towards protonation. In the chemical ionization mass spectra of nitrobenzoic acids and their esters and amides, and of nitrophenols and their ethers, protonations on the carboxyl, ester, amide, hydroxyl or alkoxyl groups are highly suppressed by that on the nitro group. As a result, fragmentations based on protonation on these groups unexpectedly become negligible. Ortho effects were observed for all the ortho isomers where the initial protonation on the nitro group is followed by an intramolecular proton transfer reaction, which leads to the expected 'normal' fragmentations. Protonation on the nitro substituent is much more favourable in energy than on any of the other substituents. The interaction of the two substituents through the conjugating benzene ring is found to be responsible for this 'unfair' competitive protonation. The electron-attracting nitro group strongly destabilizes the MH+ ions formed through protonation on the other substituent; although the COR (R = OH, OMe, OEt, NH2) groups are also electron-withdrawing, their effects are weaker than that of NO2; thus protonation on the latter group produces more-stable MH+ ions. On the other hand, an electron-releasing group OR (R = H, Me, Et) stabilizes the nitro-protonated species; the stronger the electron-donating effect of this group the more stable the nitro-protonated ions.

Column switching-back flushing technique for the analysis of aromatic compounds in gasoline

A simple method, based on the technique of capillary column switching-back flushing, has been developed for the detailed analysis of aromatic compounds in gasoline. The sample was first separated on a 30-m long OV-2330 polar precolumn and then backflushed onto a nonpolar analytical column. The early eluting components from the precolumn and the components of interest (aromatic compounds plus heavier compounds) eluting from the analytical column are all directed to the same flame ionization detection system through a T piece, which permits the quantitative analysis of aromatic hydrocarbons in gasoline by a normalization method using correcting factors. The switching time window of the method is +/-5 s, resulting in easier operation and higher reliability. The reproducibility of the quantitative analysis was less than or equal to3% RSD for real gasoline samples. (C) 2002 Elsevier Science B.V. All rights reserved.

Biotransformation of polycylic aromatic compounds by fungi and an investigation into the oxidation of alkylbenzenes by Mortierella isabellina NRRL 1757

Incubations of several polycyclic heteroaromatic compounds and two polycyclic aromatic hydrocarbons with a series of common fungi have been performed. The fungi Cunninghamella elegans ATCC 26269, Rhizopus arrhizus ATCC 11145, and Mortierella isabellina NRRL 1757 were studied in this regard. Of the aza heteroaromatics, only dibenzopyrrole gave a ring hydroxylated product following the incubation with C. elegans. From the thio heteroaromatics studied, dibenzothiophene was metabolized by all the three fungi and thioxanthone by C. elegans and M. isabellina giving sulfones and sulphoxides. Thiochromanone was metabolized stereoselectively to the corresponding sulphoxide by C. elegans. Methyl substituted thioxanthones on incubation with C. elegans produced oxidative products, arising from S -oxidation and hydroxylation at the methyl group. Of the cyclic ketones studied, only fluorenone was reduced to hydroxyfluorene and this metabolism is compared with that reported with cytochrome P-450 monooxygenases of hepatic microsomes. A series of para-substituted ethylbenzenes has been transformed stereoselectively to the 1-phenylethanols by incubation with M. isabellina. Comparisons of the enantiomeric purities obtained from products with their respective para substituent of the same steric size but different electronic properties indicate that the stereoselectivity of hydroxylation at benzylic carbon may be susceptible to electron donating or withdrawing factors in some cases, but that observation is not va lid in all the comparisons. The stereochemistry of the reaction is discussed in terms of three possible steps, ethylbenzene ---) 1-phenylethanol ---) acetophenone ---) 1-phenylethanol. This metabolic pathway could account for the inconsistencies observed in the comparisons of optical purities and electronic character of para substituents. Furthermore, formation of 2-phenylethanol (in some cases), l-(p-acetylphenyl)ethanol from p-diethylbenzene, and N-acetylation of p-ethylaniline was observed. n-Propylbenzene was also converted to optically active 1-phenylpropanol. Acetophenone, p-ethylacetophenone, and o(,~,~-trifluoroacetophenone were transformed to 1-phenylethanol, l-(p-ethylphenyl)ethanol, and 1-phenyl-2,2,2-trifluoroethanol, respectively, with high chemical and excellent optical yields. The 13 C NMR spectra of several substrates and metabolic products have been reported and assigned for the first time.

Reactions of polyhalogenated aromatic compounds and related ethers with metal/ammonia solutions

This work contains the results of a series of reduction studies on polyhalogenated aromatic compounds and related ethers using alkali metals in liquid ammonia. In general, polychlorobenzenes were reduced to t he parent aromatic hydrocarbon or to 1 ,4-cyc1ohexadiene, and dipheny1ethers were cleaved to the aroma tic hydrocarbon and a phenol. Chlorinated dipheny1ethers were r eductive1y dechlorinated in the process. For example, 4-chlorodipheny1- ether gave benzene and phenol. Pentach1orobenzene and certain tetrachlorobenzenes disproportionated to a fair degree during the reduction process if no added proton source was present. The disproportionation was attributed to a build-up of amide ion. Addition of ethanol completely suppressed the formation of any disproportionation products. In the reductions of certain dipheny1ethers , the reduction of one or both of the dipheny1ether rings occurred, along with the normal cleavage. This was more prevalent when lithium was the metal used . As a Sidelight, certain chloropheno1s were readily dechlorinated. In light of these results, the reductive detoxification of the chlorinated dibenzo-1,4-dioxins seems possible with alkali metals in l iquid ammonia.

Optical and electrical diagnostics measurements of plasmas generated in aromatic compounds

Plasmas generated in de discharges in aromatic compounds have been used for several years in polymerization processes. The chemical kinetics developed in such a plasma environment are extremely complicated. Therefore it is extremely important to set up optical and electrical diagnostics in order to establish the kinetics of the film growth, In this work we studied de plasmas generated ill low-pressure atmospheres of benzene for different values of gas pressure and power coupled to the discharge. The pressure range varied from 0.2 to 1.0 mbar for electric power running from 4 to 25 W, the main chemical species observed within the discharge were CH, H and C. It was observed that the CH relative concentration increases continuously with the power in the range investigated. The electron temperature varied from 0.5 to 2.0 eV with the increase of the power, for a fixed value of gas pressure. The relative dielectric constant of the plasma polymerized benzene was kept around 4.8 from 100 Hz to 10 kHz, presenting a resonance near 25 kHz. This electric behaviour of the film was the same fur different conditions of polymeric film deposition, (C) 1997 Elsevier B.V. S.A.

Aromatic compounds from three Brazilian Lauraceae species

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Aromatic compounds produced by Periconia atropurpurea, an endophytic fungus associated with Xylopia aromatica

6,8-Dimethoxy-3-(2'-oxo-propyl)-coumarin (1) and 2,4-dihydroxy-6-[(1'E,3'E)-penta-1', 3'-dienyl]-benzaldehyde (2), in addition to the known compound periconicin B (3), were isolated from the ethyl acetate extract of Periconia atropurpurea, an endophytic fungus obtained from the leaves of Xylopia aromatica, a native plant of the Brazilian Cerrado. Their chemical structures were assigned based on analyses of MS, 1D and 2D-NMR spectroscopic experiments. Biological analyses were performed using two mammalian cell lines, human cervix carcinoma (HeLa) and Chinese hamster ovary (CHO). The results showed that compound I had no effect when compared to the control group, which was treated with the vehicle (DMSO). Compound 2 was able to induce a slight increase in cell proliferation of HeLa (37% of increase) and CHO (38% of increase) cell lines. Analysis of compound 3 showed that it has potent cytotoxic activity against both cell lines, with an IC50 of 8.0 mu M. Biological analyses using the phytopathogenic fungi Cladosporium sphaerospermum and C. cladosporioides revealed that also 2 showed potent antifungal activity compared to nystatin. (c) 2006 Elsevier Ltd. All rights reserved.