Mesaconic Acid Research Articles

Asymmetric synthesis by chiral ruthenium complexes : III. Regioselectivity and asymmetric induction in catalytic hydrogenation of α,β-unsaturated dicarboxylic acids

The homogeneous catalytic hydrogenation of citraconic and mesaconic acids in the presence of H 4Ru 4(CO) 8[(—)-DIOP] 2 gives, in addition to (—)( S)-methylsuccinic acid, a mixture of λ-lactones in ratios which depend on the substrate and the reaction temperature. An exceptionally high regioselectivity is obtained in the hydrogenation at 120°C of the more hindered carboxyl group of mesaconic acid.

Mechanism of the permanganate oxidation of unsaturated compounds. Part VI. Kinetic investigation of the oxidation of methylmaleic acid, methylfumaric acid, and dimethylmaleic acid

The kinetics of the permanganate oxidation of methylmaleic (MMA), methylfumaric (MFA), and dimethylmaleic (DMA) acids have been studied by the stopped-flow technique in aqueous solution between pH 0.0 and 5.0. Manganese(III) has been detected as a short-lived intermediate in all cases. The reactions are first order with respect to both MnO4– and the substrate. The second-order rate constant depends strongly on the pH. The rate of interconversions of the acid, the mono-, and the di-anion is much higher than the rate of oxidation. The rate constants are, in the above order (at 25°C, in dm3 mol–1 s–1) : 150, 660, and 310 (MMA); 1 240, 370, and 98 (MFA); 240, 90, and 54 (DMA). Low activation enthalpies and high negative activation entropies are observed in all cases. The rate-determining step is the cis-attack of permanganate on the double bond, resulting in the formation of a short-lived, undetectable cyclic hypomanganate (MnO43–) ester. The relative reactivities reflect the influence of steric factors.

Studies of the Isomerization of Unsaturated Carboxylic Acids. II. The Thermal Rearrangement of Citraconic Acid to Itaconic Acid in Aqueous Solutions

Abstract The thermal reaction of citraconic acid (2) in water gives a mixture of products similar to that obtained from itaconic acid (1) in water. After 22 h at 170 °C, the equilibrium composition about 74%, 18%, and 8% 1, 2, and mesaconic acid respectively. At the optimum conditions (170 °C for 3 h), the yield of 1 is 65%. The mechanism of the reaction is discussed.

The mass spectra of carboxylic acids—I: Fragmentation mechanisms in maleic and fumaric acids and related compounds

AbstractThe mass spectra of maleic acid, maleic acid‐2,3‐d, fumaric acid and fumaric acid‐2,3‐d have been examined and fragmentation mechanisms are proposed for these compounds. The molecular ion of the cis‐acid fragments via H atom transfer from one carboxyl group to the other followed by loss of CO2. The trans acid does not fragment significantly by this route and the former effect may be characteristic of molecules containing two carboxyl groups cis‐oriented to each other. This hypothesis was successfully tested by examining the mass spectra of citraconic, itaconic and phthalic acids. Itaconic and mesaconic acids show some of the fragmentation characteristics of fumaric acid.

Studies in α-peptide formation by hydrogen migration polymerization I—Oligomers from maleamide, mesaconic acid α-methylester β-amide and mesaconamide

The possibility of preparing polymers containing α amino acid residues by the hydrogen migration polymerization of simple olefinic monomers has been explored. Three monomers, viz. maleamide, mesaconic acid α-methyl ester β-amide and mesaconamide, have been subjected to the action of the anionic initiators n-butyl lithium and sodium t-butoxide. In each case oligomers were formed which were shown by hydrolysis and paper chromatography to contain peptide linkages; only with mesaconic acid α-methyl ester β-amide was distinction possible between α- and β-residues present in the polymer; the results showed that both types of residue were incorporated. An α-peptide residue is considered to arise from addition of the anion to the carbon atom of the monomer carrying the amide group [equation (2)], and the structural features favouring this mode of addition are discussed together with the mechanism of chain growth and the conditions necessary for obtaining high molecular weight products. Addition to both carbon atoms of mesaconamide was shown to occur.

Radiation Yield of Citraconic and Mesaconic Acids in Aqueous Solution

EXPERIMENTS have been carried out in order to ascertain whether the double-bound radiolability of citraconic acid is different from that of its isomer mesaconic acid in aqueous solution. Mesaconic and citraconic acids were purchased from Fluka and were used without further purification. The water was prepared by distillation of de-ionized water from potassium permanganate. The solutions were irradiated with a cobalt-60 source at (4.20±0.12) × 1015 eV/(ml. × min). The source calibration was made with the Fricke dosimeter1. The determinations of mesaconic and citraconic acids were carried out spectrophotometrically at 220 mµ by a Beckman spectrophotometer model DU. When carboxylic group is conjugated with C=C, its absorption band in the ultra-violet regions is shifted to longer wave-lengths and the molecular extinction coefficient is increased at the same time by a factor of about 102 (ref. 2).

Fermentation of Glutamic Acid by Rumen Bacteria

Washed suspension of rumen bacteria fermented glutamic acid forming ammonia, carbon dioxide, butyric, propionic and acetic acids as end products. Fermentation of glutamic acid by acetone dried cells gave rise to several dicarboxylic acids, namely: α-ketoglutaric acid, succinic acid, mesaconic acid and possibly citramalic acid. Carbon dioxide, butyric, propionic and acetic acid were found after fermentation of α-ketoglutarate by washed suspension of rumen bacteria, and only succinic acid after fermentation of α-ketoglutarate by acetone dried cells. After dissimilation of glutamate-1-14C 75 per cent of the labelled carbon was recovered in the carbon dioxide, acetic, butyric and propionic acid fractions. The interpretation of the results is discussed in the light of recognized fermentation pathways.

PATHWAY FOR THE DISSIMILATION OF ITACONIC AND MESACONIC ACIDS

Brightman, Vernon (The University of Chicago, Chicago), and William R. Martin. Pathway for the dissimilation of itaconic and mesaconic acids. J. Bacteriol. 82:376-382. 1961.-Studies on the oxidation of itaconic and mesaconic acids by a Pseudomonas sp., adapted to utilize either of these acids as a sole carbon source, have provided evidence for a pathway converting both itaconate and mesaconate to succinate. A metabolic interconversion of itaconate, mesaconate, and citramalate has also been demonstrated by whole cell and cell-free enzyme studies. Succinate derived from methylene-labeled itaconate was found to be labeled in the inside carbon atoms, a fact which indicates that the branched chain compound was converted into a straight chain molecule by a shift of the methylene carbon (C-5) from the side chain of itaconate to a position between C-2 and C-3 in an, as yet, unknown straight chain intermediate prior to its conversion to succinate.

Chromatographic Fractionation of Non‐Nitrogenous Organic Acids in Taiwan Sugar Cane by Silica Gel Column

AbstractPartition chromatography on silica gel columns has been applied to isolate and identify some of the hitherto undetected non‐nitrogenous organic acids present in sugar cane juice. In this experiment, nine organic acids were identified from Taiwan sugar cane, F 127 and N:CO 310, and eight of them from F 126. They are mesaconic, syringic, fumaric, succinic, aconitic, glycolic, malic, citric and oxalic acid. Among these, mesaconic acid was not identified by comparing with the authentic acid, but was indirectly identified from the position of its peak effluent volume. Though the crystal of syringic acid could not be obtained, the position of its peak was definitely identified by that of the authentic acid‐Other acids were identified by the mesurement of their respective Rf values, the microphotographs of the crystal shape, and the determination of the melting points.According to the results, the recovery of all the non‐nitrogenous organic acids present in the sugar cane was almost quantitative with the exception of oxalic acid, the result of which was obviously erratic. Other acids were recovered with excellent rates ranging from 96.9% to 102% In three varieties of sugar cane, F 126, F 127 and N:CO 310, the aconitic acid was the highest content, those of citric, glycolic, malic and oxalic acid came next. The contents of the other acids were comparatively low.

Conjugate Additions of Grignard Reagents to alpha,beta-Unsaturated Esters. V. Addition of n-Butylmagnesium Bromide to sec-Butyl Esters of Maleic, Fumaric, Citraconic, and Mesaconic Acids.

Conjugate Additions of Grignard Reagents to alpha,beta-Unsaturated Esters. V. Addition of n-Butylmagnesium Bromide to sec-Butyl Esters of Maleic, Fumaric, Citraconic, and Mesaconic Acids.

Studies on Synthetic Pyrethroid

Methyl αδ-dimethylsorbate, when submitted to the selective oxidation sequence by the actions of perbenzoic acid, mineral acid, lead tetraacetate and peracetic acid in this order, finally gives β-monomethyl mesaconate, which is converted after hydrolysis to mesaconic acid of the well-defined trans-configuration. The reaction sequence involves no process likely to invert the configuration, and thus another cogent chemical evidence for the trans-configuration of αδ-dimethylsorbic acid is obtained in agreement with the physico-chemical conclusion, previously reported.

Studies on Synthetic Pyrethroid

Methyl αδ-dimethylsorbate, when submitted to the selective oxidation sequence by the actions of perbenzoic acid, mineral acid, lead tetraacetate and peracetic acid in this order, finally gives β-monomethyl mesaconate, which is converted after hydrolysis to mesaconic acid of the well-defined trans-configuration. The reaction sequence involves no process likely to invert the configuration, and thus another cogent chemical evidence for the trans-configuration of αδ-dimethylsorbic acid is obtained in agreement with the physico-chemical conclusion, previously reported.

Stereochemistry of cyclic compounds Communication 15. Condensation of 2-methoxy-1, 3-butadiene with maleic and citraconic anhydrides and with the methyl esters of fumaric and mesaconic acids

1. A study was made of the condensations of 2-methoxy-l, 3-butadiene with maleic and citraconic anhydrides and with fumaric and mesaconic esters. The corresponding cis- and trans-4-oxo-1, 2-cyclohexanedicarboxylic acids, their anhydrides, and their methyl esters are described. 2. It was shown that, in the condensation of 2-methoxy-1, 3-butadiene with citraconic anhydride and mesaconic ester, mainly para-adducts are formed, and these were characterized by their derivatives.

Aconic acid and related compounds: I. Discussion of the structure of aconic acid

AbstractTo aconic acid, first described in literature by Kekulé, the structure of a β,γ‐butenolide was given by Fittig and Beer. In 1947 Campbell and Hunt put forward arguments for an α,β‐butenolide structure. These arguments were based on a new synthesis of the acid and a comparison of the U.V. absorption spectrum of aconic acid with those of mesaconic acid and itaconic acid. Close inspection of the properties of aconic acid shows however that Campbell and Hunt's synthesis of aconic acid is not proving for its structure.Moreover these authors drew their spectral conclusions only from curveshapes, so we found it necessary to repeat the U.V. measurements at lower wave lengths. The rightness of the structure proposed by Campbell and Hunt could be proved.

Synthesis of polycyclic compounds related to the steroids, XI.

1. Condensation of divinyl with citraconic anhydride, citraconic acid, mesaconic acid, and their dimethyl esters gives the cis- and trans-1-methyl-cyclohexane-1,2-dicarboxylic acids (VI), (VII), (X) and (XI), their anhydrides (V), (VIII), (XII), and (XIII), and their dimethyl esters (XV), (XVI), (XVII), and (XVIII). 2. Condensation of divinyl with dimethyl mesaconate gives dimethyl trans-1-methylcyclohex-1-ene-1,2-dicarboxylate (XV) in good yields; the trans-acids (X), and (XI) are readily hence derived. 3. The dimethyl esters of teh cis-acids (XVII) and (XVIII) are converted by the action of sodium methoxide into the corresponding trans-cis (X) and (XI), in good yield. 4. The trans-acids (X) and (XI), and their anhydrides (XII) and (XIII) isomerize when heated at 200°, to afford the corresponding cis-compounds.

The Reaction of Anthracene with Maleic and Fumaric Acid and their Derivatives and with Citraconic Anhydride and Mesaconic Acid

The Reaction of Anthracene with Maleic and Fumaric Acid and their Derivatives and with Citraconic Anhydride and Mesaconic Acid

Studies on Unsaturated 1,4-Dicarbonyl Compounds. VII. Aryl Unsaturated 1,4-Diketones and Ketonic Acids Derived from Citraconic and Mesaconic Acids, with Particular Reference to the β-[p-Bromobenzoyl]-methylacrylic Acids

Studies on Unsaturated 1,4-Dicarbonyl Compounds. VII. Aryl Unsaturated 1,4-Diketones and Ketonic Acids Derived from Citraconic and Mesaconic Acids, with Particular Reference to the β-[p-Bromobenzoyl]-methylacrylic Acids

Note on the Serological Differentiation of Steric Isomers

A relationship between spatial configuration and serological specificity has been established in several instances.1, 2, 3, 4 In recent studies it has been found that the cis-trans isomerism of maleic and fumaric acid can be detected serologically. The immune serum used was obtained by injection of an antigen consisting of protein to which was coupled diazotized p-aminosuccinanilic acid. The reaction of this immune serum with the corresponding antigen was inhibited by succinic acid (as sodium salt) and moreover by maleic, but not by fumaric acid. This differentiation of the cis and transforms extended to the monoesters of the two acids and furthermore to the methyl substituted compounds (citraconic and mesaconic acid).On the basis of our former results the suggestion was made5 that in certain cases serological reactions could be used for determining spatial configuration, in a way similar to that in which enzymes have been applied to this purpose. At the same time a first example was cited dealing with th...

Note on the isolation of mesaconic acid from cabbage leaves

Note on the isolation of mesaconic acid from cabbage leaves

Societies and Academies

LONDON Chemical Society, November 3.—Dr. Gilbert in the chair.—The following papers were read:—On citraconic and mesaconic ethers arid malic and fumaric acids, by W. H. Perkin. The author has carefully investigated the physical properties of the methylic and ethylic ethers of citra- and metaconic acids. Dr. Gladstone has also measured their refractive indices. The citraconic ethers boil at a higher temperature than the mesaconic ethers, but their specific gravities, magnetic rotatory power, and refractive indices are lower. Only one anhydride can be obtained from maleic and fumaric acids, one from citra- and mesaconic acids, and one from α and β coumaric acids. Maleic anhydride can be obtained directly from malic acid by heating with an excess of acetylie chloride.—On the action of potassium cyanide on bismuthous nitrate, by M. M. P. Muir. A puce-coloured body is formed, Bi7(CN)6O15; by heating with strong potash Bi4O7 is obtained.—On the atomic weight, of bismuth, by M. M. P. Muir. The author has analysed bismuthous chloride, and obtained as a mean atmospheric weight 210.46, but he is not satisfied with the results, and hopes to obtain better numbers by the synthesis of bismuthous iodide.—Additional observations on the halogen salts of bismuth, by M. M. P. Mnir.—Note on the action of sulphuric acid on zinc and tin, by M. M. P. Muir and C. E. Robbs.—On the volumetric estimation of bismuth in the form of oxalate, by M. M. P. Muir and C. E. Robbs.—Note on the influence of water on the reaction between potassium iodide and chlorine, by M. M. P. Muir and R. Threlfall.—Laboratory notes, by M. M. P. Muir. I. Lecture experiment showing the effect of “a” time, “b” temperature, “c” mass. This consists in adding a solution of bismuth iodide in hydriodic acid to-each of three beakers, one containing 100 cc. of cold water, 100 cc. of hot water, and 500 cc. of eoM water. 2. The solution of manganese dioxide and manganese ores in hydrochloric acid is much hastened by potassium iodide. 3. A new method of detecting tin in the presence of antimony: by boiling with metallic copper and testing for stannous salt with mercuric chloride. 4. To detect the haloid acids in presence of nitrous and nitric acids.—On suberone, by R. S. Dale and C. Schorlemmer.—On sulphonic acids derived from isodinaphthyl, by Watson Smith and T. Takamatsu.—On phenyl aphthalene, by Watson Smith and T. Takamatsu.—On dimethylmalonic acid and dimethylbarbituric acid, by L. T. Thome. The author confirms the conclusions arrived at by Conrad and Guthzeit.