Mesaconate

Itaconic acid (1) is isomeric with citraconic [498-23-7] (2) and mesaconic [498-24-8] (3) acids. Under acidic, neutral, or mildly basic conditions and at moderate temperatures, itaconic acid is stable. At elevated temperatures or under strongly basic conditions, the isomers are interconvertible. 

Methylsuccinic acid has been prepared by the pyrolysis of tartaric acid from 1,2-dibromopropane or allyl halides by the action of potassium cyanide followed by hydrolysis by reduction of itaconic, citraconic, and mesaconic acids by hydrolysis of ketovalerolactonecarboxylic acid by decarboxylation of 1,1,2-propane tricarboxylic acid by oxidation of /3-methylcyclo-hexanone by fusion of gamboge with alkali by hydrog. nation and condensation of sodium lactate over nickel oxide from acetoacetic ester by successive alkylation with a methyl halide and a monohaloacetic ester by hydrolysis of oi-methyl-o -oxalosuccinic ester or a-methyl-a -acetosuccinic ester by action of hot, concentrated potassium hydroxide upon methyl-succinaldehyde dioxime from the ammonium salt of a-methyl-butyric acid by oxidation with. hydrogen peroxide from /9-methyllevulinic acid by oxidation with dilute nitric acid or hypobromite from /J-methyladipic acid and from the decomposition products of glyceric acid and pyruvic acid. The method described above is a modification of that of Higginbotham and Lapworth. ... 

Mesaconic acid (methylfumaric acid) [498-24-8] M 130.1, m 204-205°, pK 4.82. Crystd from water or EtOH [Katakis et al. J Chem Soc, Dalton Trans 1491 79S6]. 

Maleic, fumaric, glutaconic, citraconic, mesaconic and itaconic acid... 

Karrer and Matter have confirmed the presence of succinic acid as recorded by Boehm, and of protoeatechuic acid as found by Wieland, Konz and Sonderhoff and have added thereto, mesaconic acid as a constituent of calabash curare. 

MES.A.CONIC Acid.—To a saturated solution of citraconic acid in ether (4 parts citraconic acid require about 5 parts of anhydrous ether), about i part of chloroform is added, and a few drops of a moderately strong solution of bromine in chloroforna-The mixture is placed in strong sunlight, when mesaconic acid, which is insoluble in ether and chloroform, begins at once to deposit on the side of the vessel nearest the light. Drops of bromine are added from time to time until no further precipitation occurs. The pasty mass is then filtered, washed with ethei, and dried on a porous plate. Yield 73 per cent, of the citraconic acid m. p. 203°. See Appejidix, p. 265. 

These compounds were not stuicturally but stereo-isomeric, the relation being similar to that which exists between fumaric, maleic or mesaconic and citraconic acids (p. 265), or again between the tw O diazotates of potassium (p. 283), and wdiich may be represented as follow s ... 

C. Itaconic Acid, Citraconic Acid, and Mesaconic Acid... 

The TBDMS derivative has been used for low molecular weight acids such as formic and for acids such as itaconic, citraconic, and mesaconic where a 30-m DB-210 column programmed from 60 to 210° at 107min separates the latter acids as the TBDMS derivatives. 

GC separation of derivatized carboxylic acids, 46-52 bacterial fatty acids, 51-52 bile acids, 50-51 C6-C24 monocarboxylic acids and dicarboxylic acids, 51 cyano acids, 52 higher-boiling acids, 49 itaconic acid, citraconic acid, and mesaconic acid, 49... 

Mercaptoethanol reagent 380 Mercury cations 144,311 Mercury lamps 20, 22 ff emission lines 23, 24 -, high pressure 22 ff -, technical data 23 Mercury(I) nitrate reagent 337 Mercury(II) salt reagent 340 Mesaconic acid 61 Mesoporphyrin 101, 102 Metal cations 310—312,398 Metal complexes 248, 398 Methanol, dipole moment 97 Methine dyestuffs 360 4-Methoxyaniline see Anisidine 4-Methoxybenzaldehyde see Anisaldehyde Methoxybenzaldehyde derivatives 72 Methoxycinnamic acid 277... 

Citric acid yields itaconic, citraconic, and mesaconic acids during coffee roasting.3... 

On similar reasonings the configuration of citraconic acid is cis because it forms the anhydride while its isomer mesaconic acid is trans. 

S. Except for oxido-reductases, transferases, and hydrolases, most ligases (enzymes that catalyze bond formation) are entirely substrate specific. Thus, fumarate hydratase (or fumarase) reversibly and stereospecifically adds water to fumaric acid to produce (S)-( — )-malic acid only (8) (Figure 1), and another enzyme, mesaconase, adds water to mesaconic acid to form (+ )-citramalic acid (9) (Figure 2). Although no extensive studies are available, it appears that neither fumarase nor mesaconase will add water stereospecifically to any other a,(3-unsaturated acid. 

This cobalamin-dependent enzyme [EC 4.3.1.2], also known as /3-methylaspartase, catalyzes the conversion of L-r/ireo-3-methylaspartate to mesaconate and ammonia. 

This enzyme [EC 4.2.1.34], also known as mesaconase and mesaconate hydratase, catalyzes the conversion of (5 )-2-methylmalate to 2-methylfumarate and water. The enzyme will also catalyze the hydration of fumarate to (5 )-malate. 

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