Muconic Acids Research Articles

Subcritical Aqueous-Phase Oxidation Kinetics of Acrylic, Maleic, Fumaric, and Muconic Acids

Unsaturated carboxylic acids such as acrylic, maleic, fumaric, and muconic acids have been observed as intermediate products in wet oxidation reactions of phenols. Oxidation kinetics of these compounds dissolved in water were studied in a titanium autoclave at a temperature range of 180 and 280 °C and oxygen partial pressures between 10 and 55 bar. The acid-decay data are well-represented by a three-half power-law kinetics for all acids. The disappearance rate of acrylic and fumaric acids is proportional to a square root of the oxygen partial pressure; for maleic acid the order takes a very low value (0.12). Thermal decomposition of acrylic acid can be neglected at temperatures employed, but it was found highly significant for maleic, fumaric, and muconic acids. These three acids completely decomposed at 280 °C with formic acid as a major intermediate product, whereas acetic acid was formed only in the presence of oxygen. The conversion of acrylic acid into CO2 and other acid intermediates at 290 °C was found to be about 72%. The lumped TOC (total organic carbon) concentration in solutions reduced by a first-order process for all acids investigated, but the order with respect to oxygen was between 0.3 and 1.0. The activation energy for the thermal decomposition of maleic and fumaric acids was 56.6 and 71 kJ/mol, respectively, whereas for the total decomposition (oxidative and thermal) of acrylic, maleic, and fumaric acids it was 94.3, 99.2, and 83.6 kJ/mol, respectively. The data for TOC reduction of acrylic and muconic acids gave the activation energy of 102 and 87.4 kJ/mol, respectively, whereas for maleic and fumaric acids its values were found to be 104.7 and 84.2 kJ/mol for the first step and 83.4 and 54.4 kJ/mol for the second step, respectively.

ChemInform Abstract: Synthesis of Muconic Acids by Peracetic Acid Oxidation of Catechols.

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Synthesis Of Muconic Acids By Peracetic Acid Oxidation Of Catechols

Monomeric and dimeric muconic acids were prepared in 30-83% yield by oxidation of catechols with peracetic acid in acetic acid.

γ-radiolysis and pulse radiolysis of aqueous 4-chloroanisole

Using pulse radiolysis and steady state γ-radiolysis in combination with product analysis by HPLC the radiolytic degradation mechanism of 4-chloroanisole (4-ClAn) has been elucidated. Pulse radiolysis experiments show that OH radicals react in neutral aqueous N 2O saturated solutions with 4-ClAn by addition to all aromatic ring positions to yield hydroxycyclohexadienyl radicals (OH-adducts), k(OH + 4-ClAn) = 6.5 × 10 9dm 3mol −1s −1. Those OH-adducts formed on ipso positions of the molecule subsequently undergo HCl or CH 3OH elimination forming methoxyphenoxyl- and chlorophenoxyl radicals. Their yield corresponds to ∼ 20% of the OH-radicals, whereby the distribution is roughly 3:1 in favor of the methoxyphenoxyl radicals, which reflects the stronger ortho-, para-directing activity of the methoxy group. The OH-adducts decay second order, 2 k = 1 × 10 9dm 3mol −1s −1. The presence of oxygen leads to its addition on the hydroxycyclohexadienyl radicals, k(OH-adduct + O 2) = 3.2 × 10 8dm 3mol −1s −1. In airfree solution the reaction of H-atom with the substrate, k(H + 4-ClAn) = 1.2 × 10 9dm 3mol −1s −1, results in H-adducts which decay in bimolecular reactions, 2 k = 8.2 × 10 8dm 3mol −1s −1. The rate constant for the reaction of the solvated electrons has been determined to k(e aq − + 4-ClAn) = 2 × 10 9dm 3mol −1s −1. The absorption spectra of H- and OH-adducts were measured in the range of 280–450 nm. The products analysed by HPLC after γ-radiolysis in dependence of dose (100–600 Gy) are given for N 2O-, air-, oxygen- and argon saturated neutral aqueous solutions. In conditions favoring the OH radical oxidation 4-chlorophenol, 4-methoxyphenol, 5-chloro-2-methoxyphenol and 2-chloro-5-methoxyphenol were determined as final products. In the presence of Ar, where about equal amounts of OH and e aq − are present, additionally anisole could be detected. Under both reaction conditions the amount of identified products is about 20% of decomposed 4-ClAn. The reaction of e aq − leads to reductive dechlorination which corresponds quantitatively to the degradation of the substrate. In the presence of air or solutions saturated with pure oxygen predominantly hydroquinone, 4-chlorophenol and muconic acids are formed and the material balance is ∼50%. The efficient dechlorination (∼60% of the decomposed 4-ClAn) as well as ring fragmentation products as intermediates en route to complete mineralization in oxygenated solution indicate that high energy radiation is a promising method for degradation of halogenated aromatic compounds in water. Variation of dose rates from 79 Gy min −1 to 266 Gy min −1 did not show any influence on the product distribution.

Identification of Muconic Acids in Bleach Plant Effluent

Muconic acids derived from guaiacol (4) were identified in ethyl acetate extracts of samples of effluents from 100% chlorine dioxide bleaching. Concentrations were estimated to be in the range 7.5-26 g/tonne. Chlorinated muconic acids derived from guaiacol were not found, but other muconic acids are likely present, both in the low molecular mass fraction and as moieties in the high molecular mass material. The isomers 5a and 5b were also obtained in the reaction of guaiacol (4) with chlorine dioxide but were not found in the effluent samples.

Production of catechols and muconic acids from various aromatics by the styrene-degraderRhodococcus rhodochrous NCIMB 13259

Intact cells ofRhodococcus rhodochrous NCIMB 13259 which had been grown in the presence of styrene were used to produce metabolic intermediates from other aromatic substrates in the presence of 3-fluorocatechol as an inhibitor of catechol oxygenase. Toluene and ethylbenzene gave 3-methylcatechol and 3-ethylcatechol respectively. The enol form of 3-acetylcatechol was produced from acetophenone and 1-phenylethanol. Benzoic acid was produced from cinnamic acid. This organism cannot metabolise muconic acids, and methylmuconic acid and ethylmuconic acid accumulated under appropriate conditions. 2-Fluoromuconic acid was also produced from the added 3-fluorocatechol. This organism provides a convenient tool for producing catechols and muconic acids from a variety of substrates without need for gentic manipulation.

Degradation of Phenolic Compounds and Ring Cleavage of Catechol by Phanerochaete chrysosporium

POL-88, a mutant of the white-rot fungus Phanerochaete chrysosporium, was selected for diminished phenol-oxidizing enzyme activity. A wide variety of phenolic compounds were degraded by ligninolytic cultures of this mutant. With several o-diphenolic substrates, degradation intermediates were produced that had UV spectra consistent with muconic acids. Extensive spectrophotometric and polarographic assays failed to detect classical ring-cleaving dioxygenases in cell homogenates or in extracts from ligninolytic cultures. Even so, a sensitive carrier-trapping assay showed that intact cultures degraded [U-C]catechol to [C]muconic acid, establishing the presence of a system capable of 1,2-intradiol fission. Significant accumulation of [C]muconic acid into carrier occurred only when evolution of CO(2) from [C]catechol was inhibited by treating cultures with excess nutrient nitrogen (e.g., l-glutamic acid) or with cycloheximide. l-Glutamic acid is known from past work to repress the ligninolytic system in P. chrysosporium and to mimic the effect of cycloheximide. The results here indicate, therefore, that the enzyme system responsible for degrading ring-cleavage products to CO(2) turns over faster than does the system responsible for ring cleavage.

Chemical structure and biodegradability of halogenated aromatic compounds. Conversion of chlorinated muconic acids into maleoylacetic acid.

1. An enzyme for the cycloisomerization of 2- and 3-chloro-cis,cis-muconic acid was isolated from 3-chlorobenzoate-grown cells of Pseudomonas sp. B13. It was named muconate cycloisomerase II, because it could it clearly be differentiated by its Km and Vmax. values from an ordinary muconate cycloisomerase, which functioned in benzoate catabolism and exhibited low activity with the chlorinated substrates. 2-Chloro-cis,cis-muconic acid was converted into trans- and 3-chloro-cis,cis--muconic acid into cis-4-carboxymethylenebut-2-en-4-olide together with dehalogenation. 2. An enzyme was isolated from chlorobenzoate-grown cells, which converted the 4-carboxymethylenebut-2-en-4-olides into maleoylacetic acid.

Chemical structure and biodegradability of halogenated aromatic compounds. Halogenated muconic acids as intermediates.

Substituted muconic acids were prepared from the corresponding catechols by pyrocatechase II from Pseudomonas sp. B13. The stabilities of substituted muconic acids were compared under different pH conditions. 3-Substituted cis, cis-muconic acids cycloisomerized readily in slightly acidic solutions, whereas 2-chloro- and 2-fluoro-cis,cis-muconic acids were stable under these conditions and could be isolated as crystalline compounds. They were isomerized to the cis, trans-form in highly acidic solution (pH 1), particularly when heated to 80 degrees C. Cycloisomerization of 2-chloro-cis,cis-muconic acid in 75% (v/v) H2SO4 yields 4-carboxymethyl-2-chloro-but-2-en-4-olide (4-chloro-2,5-dihydro-5-oxo-3H-furan-2-ylacetic acid). THe cis,cis-configuration of 2-chloromuconic acid was certified by 1H n.m.r. spectroscopy and by enzymic cycloisomerization. Although the cis,cis-configuration of 2-fluoromuconic acid was confirmed by corresponding spectroscopic data, it was not cycloisomerized by crude extracts or cycloisomerase II preparations from Pseudomonas sp. B13.

Copper(II)-induced cleavage of carbon-carbon bonds. Mononitriles of muconic acids from o-benzoquinones, catechols, and phenols by reaction with copper(II) in the presence of ammonia

Copper(II)-induced cleavage of carbon-carbon bonds. Mononitriles of muconic acids from o-benzoquinones, catechols, and phenols by reaction with copper(II) in the presence of ammonia

Preparation and properties of 1,2,2,2‐tetrachloroethyl esters of β‐vinylacrylic, fumaric, and muconic acids and their homopolymers or copolymers

Abstract1,2,2,2‐Tetrachloroethyl esters of β‐vinylacrylic, muconic, and fumaric acids were prepared by the addition reaction of chloral with pentadienoyl chloride, hexadienedioyl chloride, and fumaroyl chloride in the presence of FeCl3. The homopolymer of the first and copolymers of the other esters with styrene were obtained by radical polymerization. The basic chemical and physical characteristics of the compounds prepared were determined, and the assumed structure was confirmed by the infrared, NMR, and mass spectra.

New heterocyclic compounds containing two pyrazolidone rings

1. Five heterocyclic compounds have been obtained for the first time and characterized: diethylenebis-(1-pyrazolinium-3-oxide) (III); p-phenylene-bis-(5-pyrazolidone-3) (IV); 1,2-dimethylene-bis-(1-pyrazolidone-3) (Va); 1,6-hexamethylene-bis-(1-pyrazolidone-3) (Vb); methyl ester of 1,6-methylene-bis-(1-pyrazolidone-3)-5-p-phenyleneacrylic acid (VI), and also the dimethylhydrazides of p-phenylenediacrylic and muconic acids.

The function of the beta-ketoadipate pathway in Pseudomonas acidovorans.

SUMMARY Aerobic enrichment at 30° in a medium containing either cis, cis- or cis, trans-muconic acid as the sole source of carbon and energy is a highly specific method for the isolation of Pseudomonas acidovorans from soil. Nutritional studies with previously isolated strains of P. acidovorans and P. testosteroni, none of which was selected for the ability to utilize muconates, show that nearly all strains of both these species grow readily and promptly with both cis isomers of muconic acid. This ability is absent from all fluorescent pseudomonads examined, despite the fact that they possess the requisite enzymic machinery. The fluorescent pseudomonads appear to be impermeable to the muconic acids, and can use them as substrates for growth only through a mutation that alters the permeability of the cell. Studies with one strain of Pseudomonas acidovorans show that it synthesizes inducibly all the enzymes responsible for the conversion of catechol to β-ketoadipate, their synthesis being elicited by growth with either cis, cis- or cis, trans-muconate. Mutants of P. acidovorans defective in the synthesis of either β-ketoadipate enol-lactone hydrolase or β-ketoadipate succinyl-CoA transferase are unable to grow at the expense of cis, cis-or cis, trans-muconate; this confirms the role of the β-ketoadipate pathway in the dissimilation of these two substrates by P. acidovorans.

The alkaline peroxide oxidation of 1′,2′-dihydroxy-3,4-benzotropolones

The alkaline peroxide oxidation of 1′,2′-dihydroxy-3,4-benzotropolones proceeds via the corresponding 1′,2′-quinone anions, which undergo two types of peroxide decomposition. (a) At low temperature and alkali concentration, peroxide attack on the 3′- and 4′-positions of the cyclohexadiene ring predominates, and results in the formation of unstable hydroperoxides which decompose to hydroxyquinones, also formed directly by solvolysis. The greater reactivity of the 3′-position is ascribed to its conjugation with both quinonoid and tropolone carbonyl groups. The 2′-hydroxy-1′,4′-quinones formed from 3′-substituted substrates are further oxidised to tropolone-3,4-dicarboxylic anhydride. (b) At high temperature and alkali concentration, muconic acids are formed via tetrahydroxybenzotropolones and dihydroxy-2′,6′-quinones arising from peroxide attack on the 5- and 6- and 7-positions of the tropolone ring. These tetrahydroxybenzotroplones (also obtained by hydrolysis of the abnormal Thiele penta-acetates of the 1′,2′-quinones) are not formed when the substrate bears a carboxy-group at the 6-position; in this case peroxide attack on the 1′- and 2′-positions of the cyclohexadiene ring predominates.

Microanalysis of catechols as lead salts by infrared spectroscopy

A method is described for qualitative determination of various catechols in the microgram range based on the infrared spectra of their lead salts. Neutral Pb(OAc) 2 precipitated catechols as their lead salts from aqueous and from ether solutions. From 5 ml aqueous solution, 25 μg catechol was easily recovered and identified by IR as lead catecholate. The salts could be reconverted to free catechols by treatment with (NH 4) 2S, H 2S, or H 2SO 4 and this solution analyzed directly by gas chromatography. Two muconic acids were also precipitated by Pb(OAc) 2 and characterized by their IR spectra.

Polyene acids. Part VIII. The isomeric muconic diamides and mucononitriles

The three geometrically isomeric muconic acids have been converted via their dimethyl esters to the corresponding diamides and thence dinitriles. Light absorption data and other evidence for the constitutions of these products are given.

Enzymatic conversion of two geometrical isomers into enantiomorphs.

MUCONIC acid is an intermediate in the oxidation of certain aromatic compounds by bacteria. It is formed enzymatically by an oxidative ring cleavage from catechol1, and is then rearranged to β-ketoadipic acid, which cannot be further degraded by the cell-free extracts. Evans, Smith, Linstead and Elvidge2 studied the action of crude cell-free bacterial extracts on the three isomers of muconic acid, and found that only the cis-cis isomer could be converted to β-ketoadipic acid. They also tested the ability of extracts to attack certain lactones related to the muconic acids, and demonstrated that γ-carboxymethyl-Δa-butenolide could be rapidly converted to β-ketoadipic acid. On the basis of these findings they postulated the reaction sequence shown in Fig. 1.

369. Polyene acids. Part VII. Half methyl esters and amides of the muconic acids

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143. Polyene acids. Part V. Catalytic semi-hydrogenation of the three isomeric muconic acids and comfirmation of their configurations

143. Polyene acids. Part V. Catalytic semi-hydrogenation of the three isomeric muconic acids and comfirmation of their configurations

Studies in detoxication. 44. The metabolism of benzene; the muconic acid excreted by rabbits receiving benzene; determination of the isomeric muconic acids.

Studies in detoxication. 44. The metabolism of benzene; the muconic acid excreted by rabbits receiving benzene; determination of the isomeric muconic acids.