Of malic acid

Colourless prisms m.p. 130 C. Manufactured by treating maleic anhydride with water. It is converted to the anhydride by heating at By prolonged heating at 150 "C or by heating with water under pressure at 200 C, it is converted to the isomeric (trans) fumaric acid. Reduced by hydrogen to succinic acid. Oxidized by alkaline solutions of potassium permanganate to mesotartaric acid. When heated with solutions of sodium hydroxide at 100 C, sodium( )-malate is formed. Used in the preparation of ( )-malic acid and in some polymer formulations. 

Optically inactive starting materials can give optically active products only if they are treated with an optically active reagent or if the reaction is catalyzed by an optically active substance The best examples are found m biochemical processes Most bio chemical reactions are catalyzed by enzymes Enzymes are chiral and enantiomerically homogeneous they provide an asymmetric environment m which chemical reaction can take place Ordinarily enzyme catalyzed reactions occur with such a high level of stereo selectivity that one enantiomer of a substance is formed exclusively even when the sub strate is achiral The enzyme fumarase for example catalyzes hydration of the double bond of fumaric acid to malic acid m apples and other fruits Only the S enantiomer of malic acid is formed m this reaction... 

The reaction is reversible and its stereochemical requirements are so pronounced that neither the cis isomer of fumaric acid (maleic acid) nor the R enantiomer of malic acid can serve as a substrate for the fumarase catalyzed hydration-dehydration equilibrium... 

The optical activity of malic acid changes with dilution (8). The naturally occurring, levorotatory acid shows a most peculiar behavior in this respect a 34% solution at 20°C is optically inactive. Dilution results in increasing levo rotation, whereas more concentrated solutions show dextro rotation. The effects of dilution are explained by the postulation that an additional form, the epoxide (3), occurs in solution and that the direction of rotation of the normal (open-chain) and epoxide forms is reversed (8). Synthetic (racemic) R,.9-ma1ic acid can be resolved into the two enantiomers by crystallisation of its cinchonine salts. 

Alkyl hahdes in the presence of silver oxide react with alkyl malates to yield alkoxy derivatives of succinic acid, eg, 2-ethoxysuccinic acid, H00CCH2CH(0C2H )C00H (12,13). A synthetic approach to produce ethers of malic acid is the reaction of malic esters and sodium alkoxides which affords 2-alkoxysuccinic esters (14). 

Make acid yields coumaUc acid when treated with fuming sulfuric acid (19). Similar treatment of malic acid in the presence of phenol and substituted phenols is a facile method of synthesi2ing coumarins that are substituted in the aromatic nucleus (20,21) (see Coumarin). Similar reactions take place with thiophenol and substituted thiophenols, yielding, among other compounds, a red dye (22) (see Dyes and dye intermediates). Oxidation of an aqueous solution of malic acid with hydrogen peroxide (qv) cataly2ed by ferrous ions yields oxalacetic acid (23). If this oxidation is performed in the presence of chromium, ferric, or titanium ions, or mixtures of these, the product is tartaric acid (24). Chlorals react with malic acid in the presence of sulfuric acid or other acidic catalysts to produce 4-ketodioxolones (25,26). 

The production is primarily used for food (26.6%) and beverages (54.7%) however, some industrial appHcations (18.7%) exist, eg, coatings, polymers, and resins. (Historical patterns of use in the United States have been stable and are as noted in parentheses.) Over the past few years, the Hst price of malic acid has been stable. In the United States, the current Hst price for malic acid is 1.79/kg, deHvered and packaged in 50-lb (22.7-kg) bags (39). 

Thiomahc acid [70-49-5] (mercaptosuccinic acid), C H O S, mol wt = 150.2, is a sulfur analogue of malic acid. The properties of the crystalline, soHd thiomalic acids ate given in Table 6. The racemic acid has the following acid dissociation constants at 25°C pTf i — 3.30 pffc2 — 4.94. 

Physical Properties. Malonic acid, HOOC—CH2—COOH (1), was discovered and isolated in 1858 as a product of malic acid oxidation. The physical properties of malonic acid are Hsted in Table 1. 

The amount of malic acid theoretically is sufficient to convert half of the amine to the acid salt and the remaining half to the neutral salt. 

In 1896, the German chemist Paul Walden made a remarkable discovery. He found that the pure enantiomeric (+)- and (-)-malic acids could be intercon-veited through a series of simple substitution reactions. When Walden treated (-)-malic acid with PCl5, he isolated (4-)-chlorosuccinic acid. This, on treatment with wet Ag20, gave (+)-malic acid. Similarly, reaction of (+)-malic acid with... 

E. P. Delhaize, P. R. Ryan, and P. J. Randall, Aluminium tolerance in wheat Triti-cum aestirum L.). II. Aluminium-stimulated excretion of malic acid from root apices. Plant Physiol. 103 695 (1993). 

Ethyl fumarate has been prepared from fumaric acid and ethyl alcohol, with or without sulfuric acid as catalyst,4 from silver fumarate and ethyl iodide,5 from silver maleate and ethyl iodide plus a trace of iodine,6 from ethyl maleate by the action of iodine,6 from ethyl maleate and phosphorus pentachloride,7 and by passing hydrogen chloride into a boiling absolute alcohol solution of malic acid.8... 

Figure 4.22 Slurry reactor synthesis of malic acid from fumaric acid applying a batch process followed by precipitation and crystallization...

Addition of salts, adds and bases tend to make the laevo-rotary acid more dextro-rotary. With rising temperature, the pure add and also the solutions become more laevo-rotary. These changes cannot be due to dectrolytic dissociation, because the effect of hydrochloric acid is quite marked up to rdatively high concentrations and it would take relatively little acid to force back the dissociation of malic acid to a negligible value. Another reason is that we get a similar change with the concentration with malic ester in alcoholic solution. 

We have thus eliminated ionization, polymerization, hydrate formation, 0-lactone formation and formation of d-malic acid from /-malic acid as playing important parts in the change of optical rotation of malic acid with concentration, though some or most of these may play a minor part. 

The changes in optical rotation and the anomalous dispersion of solutions of /-malic acid in solution are due to the presence of two tautomeric forms in dynamic equilibrium. 

Thus Pasteur noted that the amide of (-) malic acid forms molecular compounds of different properties with the enantiomeric amides of tartaric acid. With amide of (+) tartaric acid large transparent crystals are formed whose solubility is 18% at 20°C, while with the amide of (-) tartaric acid, thin needles are formed with solubility almost two times higher. Free malic and tartaric acids also form diastereomeric molecular compounds. 

Step 1 Conversion of malic acid to an equivalent amount of calcium salt,... 

The major portion of malic acid currently produced at an approximate 10,000 t/y is racemic, because it originates from petrochemically produced fumaric acid. The L-form can also be generated from fumaric acid by its hydration with immobilized cells of Brevibacterium or Corynebacterium. 

Figure 6. Concentration of malic acid (mg ml"l) exuded to growing medium as influenced by species and exposure time to in concentration of 45 ppm.

The name, maleic anhydride, came about in the same fashion. as any number of compounds early in the petrochemical Business Many organic acids and their derivatives were given common names based on some early observations, their special source in nature, or on some special feature of their structure. MA was first isolated in the 1850—75 era by dehydration of malic acid, a sugar acid found in apple juice. The Latin word for apple is malum. Hence, malum, malic, maleic. The suffix, anhydride, which follows each alias of MA, has a simple definition a compound derived by the loss of a molecule of water from two carboxyl groups (-COOH). 

Some other methods of resolution include the use of /-malic acid [(+)-form], /- and d/-malic acids [(+)- and (—)-forms], /-malic acid and d-tartaric acids [(+)- and (—)-forms], d-a-bro-mocamphor-TT-sulfonic acid [(—)-form], /-quinic and d-tartaric acids [(+)- and (—)-forms], 2,3,4,6-tetraacetyl-D-glucose [(+)-form], " and barium (—)-bornyl sulfate [(+)- and (—)-forms]."... 

The absolute configuration of the major isomers of spirolactone 102 and amide 103 was ISySRyl R, based on the known configuration of malic acid and determination of the relative configuration by an X-ray structure analysis of amide 103 [62]. 

The synthesis of 9-(l,4-dihydroxybut-2-oxy)purines commenced with 2-butene-l,4-diol (1004) and via 1005 to 1006, which upon reaction with 1007 gave 1011 and then, upon hydrolysis, the racemic alkoxyamine 1012. The chiral derivatives commenced with the enantiomers of malic acid (1009) through 1010 to 1008, as shown in the scheme. Treatment of 1012 with 996 and further transformations followed almost the same sequence as before to give 1013. 

Its composition, C H7N04, was established in 1833 by Boutron-Charlard and Pelouze, and confirmed by Liebig. In 1848 Piria showed that aspartic acid was converted into malic acid by the action of nitrous acid, and he regarded aspartic acid and asparagine as the two amides of malic acid... 

This idea of their constitution was proved to be erroneous by Kolbe in 1862, who showed that aspartic acid did not give off ammonia when boiled with dilute caustic alkali, and that asparagine only lost half of its nitrogen when thus treated. Aspartic acid was therefore not the amide of malic acid, but amino-succinic acid, and asparagine the amide of this compound. 

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