Succinic acid, oxidation with

Nitric acid oxidation of coal, with or without oxygen, leads to the formation of complex mixtures of the benzenoid or aromatic type of organic acida Nitric acid oxidation of carbohydrates yfelds oxalic acid. Nitric acid of 50-76 per cent concentration at temperatures of 20-40 C oxidizes tetra-hydrofuran to good yields of succinic acid. Oxidation with nitric acid of a secondary aliphatic alcohol or an aliphatic ketone results in fistion of the aliphatic chain at the point of attachment of the functional group accom-... 

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. 

Oxidation. Succinic acid reacts with hydrogen peroxide, giving different products that depend on the experimental conditions peroxysuccinic acid [2279-96-1] (CH2COOOH)2, oxosuccinic acid [328-42-7] (oxaloacetic acid) malonic acid [141-82-2] or a mixture of acetaldehyde, malonic acid, and make acid [6915-15-7]. Succinic anhydride in dimethylformamide (DMF) with H2O2 gives monoperoxysuccinic acid [3504-13-0], HOOCCH2CH2COOOH, mp 107°C (70). 

Succinic Yeasts Oxidation with Acetic acid... 

U.S. 4,486,338 (1984) Ootani et al. (Kao) Succinic acid derivative with anionic and tertiary amine oxide Superior foaming, detergency, and stability... 

Very recently, a simple oxidation of furfural to produce succinic acid (SA) with a combination of a heterogeneous acid catalyst and hydrogen peroxide has been achieved (Scheme 6.3) [75]. Maleic acid (MA) was formed as a by-product (11%). 

The oxidation of cyctopentanone (Section 111,73) with dilute nitric acid gives glutaric acid accompanied by some succinic acid the latter is removed as the sparingly-soluble barium salt ... 

Vapor-phase oxidation over a promoted vanadium pentoxide catalyst gives a 90% yield of maleic anhydride [108-31-6] (139). Liquid-phase oxidation with a supported palladium catalyst gives 55% of succinic acid [110-15-6] (140). 

Although many variations of the cyclohexane oxidation step have been developed or evaluated, technology for conversion of the intermediate ketone—alcohol mixture to adipic acid is fundamentally the same as originally developed by Du Pont in the early 1940s (98,99). This step is accomplished by oxidation with 40—60% nitric acid in the presence of copper and vanadium catalysts. The reaction proceeds at high rate, and is quite exothermic. Yield of adipic acid is 92—96%, the major by-products being the shorter chain dicarboxytic acids, glutaric and succinic acids,and CO2. Nitric acid is reduced to a combination of NO2, NO, N2O, and N2. Since essentially all commercial adipic acid production arises from nitric acid oxidation, the trace impurities patterns ate similar in the products of most manufacturers. 

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). 

Potassium permanganate oxidizes succinic acid to a mixture of malic and tartaric acid [133-37-9]. 3-Hydroxypropionic acid [503-66-2] is obtained with sodium perchlorate. Cerium(IV) sulfate in sulfuric acid medium oxidizes succinic acid to oxaloacetic acid (71). 

Various methods can be used to analy2e succinic acid and succinic anhydride, depending on the characteristics of the material. Methods generally used to control specifications of pure products include acidimetric titration for total acidity or purity comparison with Pt—Co standard calibrated solutions for color oxidation with potassium permanganate for unsaturated compounds subtracting from the total acidity the anhydride content measured by titration with morpholine for content of free acid in the anhydride atomic absorption or plasma spectroscopy for metals titration with AgNO or BaCl2 for chlorides and sulfates, respectively and comparison of the color of the sulfide solution of the metals with that of a solution with a known Pb content for heavy metals. 

Several procedures for making glutaric acid have been described in Organic Syntheses starting with trimethylene cyanide (28), methylene bis (malonic acid) (29), y-butyrolactone (30), and dihydropyran (31). Oxidation of cyclopentane with air at 140° and 2.7 MPa (400 psi) gives cyclopentanone and cyclopentanol, which when oxidized further with nitric acid at 65—75° gives mixtures of glutaric acid and succinic acid (32). 

In a 2-1. round-bottomed, 3-necked flask fitted with a stirrer and two large-bore condensers are placed 200 cc. of 50 per cent nitric acid and 0.25 g. of vanadium pentoxide. The flask is heated to 65-70° in a water bath (thermometer in water), and I cc. of cyclopentanone added. Oxidation is indicated by the production of brown fumes. The water bath is removed, and 42 g. (less the i cc.) of the cyclic ketone added from a dropping funnel through the condenser at the rate of a drop every three seconds. The heat of the reaction keeps the flask at about 70°. If the temperature drops, oxidation ceases until the ketone has accumulated, when it may proceed almost explosively. In such a case, or if the temperature is higher, much succinic acid is formed. After addition has been completed, the water bath... 

The space inside the inner mitochondrial membrane is called the matrix, and it contains most of the enzymes of the TCA cycle and fatty acid oxidation. (An important exception, succinate dehydrogenase of the TCA cycle, is located in the inner membrane itself.) In addition, mitochondria contain circular DNA molecules, along with ribosomes and the enzymes required to synthesize proteins coded within the mitochondrial genome. Although some of the mitochondrial proteins are made this way, most are encoded by nuclear DNA and synthesized by cytosolic ribosomes. 

This is a crucial point because (as we will see) proton transport is coupled with ATP synthesis. Oxidation of one FADHg in the electron transport chain results in synthesis of approximately two molecules of ATP, compared with the approximately three ATPs produced by the oxidation of one NADH. Other enzymes can also supply electrons to UQ, including mitochondrial 5w-glyc-erophosphate dehydrogenase, an inner membrane-bound shuttle enzyme, and the fatty acyl-CoA dehydrogenases, three soluble matrix enzymes involved in fatty acid oxidation (Figure 21.7 also see Chapter 24). The path of electrons from succinate to UQ is shown in Figure 21.8. 

Formal oxidation of pyrrolidine to the succinimide stage affords a series of compounds used as anticonvulsant agents for treatment of seizures in petit mal epilepsy. Knoevnagel condensation of benzaldehyde with ethyl cyanoacetate affords the unsaturated ester, 9. Conjugate addition of cyanide ion leads to the di-nitrile ester (10). Hydrolysis in mineral acid affords the succinic acid (11), presumably by decarboxylation of the intermediate tricarboxyllie acid. Lactamization with methylamine gives phensuximide (12). ... 

This complex consists of four subunits, all of which are encoded on nuclear DNA, synthesized on cytosolic ribosomes, and transported into mitochondria. The succinate dehydrogenase (SDH) component of the complex oxidizes succinate to fumarate with transfer of electrons via its prosthetic group, FAD, to ubiquinone. It is unique in that it participates both in the respiratory chain and in the tricarboxylic acid (TC A) cycle. Defects of complex II are rare and only about 10 cases have been reported to date. Clinical syndromes include myopathy, but the major presenting features are often encephalopathy, with seizures and psychomotor retardation. Succinate oxidation is severely impaired (Figure 11). 

L-dihydroxy-succinic acid (L(dexiro)-tartaric acid, CXIII). This result establishes the position of the double bond between C4 and C5 and demonstrates that C4 carries only one hydrogen atom while C5 has attached to it the enolic hydroxyl group. Treatment of the enol CXI with ethereal diazomethane gives 5-methyl-A4-D-glucosaccharo-3,6-lactone methyl ester (CXIY) which upon further methylation with silver oxide and methyl iodide yields 2,5-dimethyl-A4-D-glucosaccharo-3,6-lactone methyl ester (CXV). When the latter is subjected to ozonolysis there is formed oxalic acid and 3-methyl-L-threuronic acid (CXVI). Oxidation of this aldehydic acid (CXYI) with bromine gives rise to a monomethyl derivative (CXVII) of L-ilireo-dihydroxy-succinic acid. 

In the hydroxycyclopropanation of alkenes, esters may be more reactive than N,N-dialkylcarboxamides, as is illustrated by the exclusive formation of the disubstituted cyclopropanol 75 from the succinic acid monoester monoamide 73 (Scheme 11.21) [91]. However, the reactivities of both ester- as well as amide-carbonyl groups can be significantly influenced by the steric bulk around them [81,91]. Thus, in intermolecular competitions for reaction with the titanacydopropane intermediate derived from an alkylmagnesium halide and titanium tetraisopropoxide or methyltitanium triisoprop-oxide, between N,N-dibenzylformamide (48) and tert-butyl acetate (76) as well as between N,N-dibenzylacetamide (78) and tert-butyl acetate (76), the amide won in both cases and only the corresponding cyclopropylamines 77 and 79, respectively, were obtained (Scheme 11.21) [62,119]. 

Wet oxidation of phenol at elevated pressure and temperature gave the following products acetone, acetaldehyde, formic, acetic, maleic, oxalic, and succinic acids (Keen and Baillod, 1985). Chlorine dioxide reacted with phenol in an aqueous solution forming p-benzoquinone and hypochlorous acid (Wajon et al., 1982). 

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