Pyruvic acid structure

In spite of the number of different structural types lipids share a common biosyn thetic origin m that they are ultimately derived from glucose During one stage of car bohydrate metabolism called glycolysis glucose is converted to lactic acid Pyruvic acid IS an intermediate... 

The sodium or potassium salt of 6-azauracil in aqueous ethanol, anhydrous ethanol, or ethylene glycol reacted with methyl iodide practically exclusively to give the 3-methyl derivative (63). In toluene the sodium, potassium, and mercuric salts produced no methylated derivatives whereas the silver salt also yielded the 3-methyl derivative, Similarly, the 3-methyl derivative was prepared from the mercuric salt of 6-azathymine, and its structure was established by hydrolysis to pyruvic acid 4-methylthiosemicarbazone. ... 

Only in the case of the pyruvic acid condensation product was it possible to isolate the corresponding ethyl ester under these conditions. This, on mild hydrolysis, reverted to 1-methyl-1,2,3,4-tetrahydro-j8-carbohne-1-carboxylic acid, identical with the starting material, which therefore had the assigned structure 26 (R = CH3) and was not the SchiflF s base 25 (R = CH3). Alkaline hydrolysis of the ester was accompanied by decarboxylation. ... 

Most coenzymes have aromatic heterocycles as major constituents. While enzymes possess purely protein structures, coenzymes incorporate non-amino acid moieties, most of them aromatic nitrogen het-erocycles. Coenzymes are essential for the redox biochemical transformations, e.g., nicotinamide adenine dinucleotide (NAD, 13) and flavin adenine dinucleotide (FAD, 14) (Scheme 5). Both are hydrogen transporters through their tautomeric forms that allow hydrogen uptake at the termini of the quinon-oid chain. Thiamine pyrophosphate (15) is a coenzyme that assists the decarboxylation of pyruvic acid, a very important biologic reaction (Scheme 6). 

Structure 12 was originally proposed for the product, with the composition CjHgOfiP, obtained by passing a mixture of phosphine and HCl into an ether solution of pyruvic acid, an a-keto acid However, the infra-red... 

An interesting synthetic approach to thietanes is the selective desulfurization of cyclic disulfides.The treatment of dithiolanes with a diethyl-aminophosphine results in a ring contraction to thietanes, (Eq. 19). This has been demonstrated with a-lipoic acid, a coenzyme with a dithiolane structure involved in the biological oxidation of pyruvic acid. The reaction is proposed to be initiated by the electrophilic attack of the phosphorus on the ring sulfur atom, resulting in the formation of an acyclic internal phosphonium salt, which by subsequent elimination of a phosphine sulfide, closes to the four-membered ring. °... 

In the majority of dehydration reactions, heterocyclic compounds are formed, rather than carbocyclic compounds. Many possibilities for formation of carbocyclic compounds exist, but these are important only if (a) the heterocyclic or acyclic tautomers cannot undergo further elimination reactions, or (b) the conditions of reaction greatly favor the formation of an acyclic tautomer capable of affording only the carbocyclic compound. Both five- and six-membered carbocyclic compounds have been isolated, with reductic acid being the compound most frequently reported. Ring closure occurs by an inter-molecular, aldol reaction that involves the carbonyl group and an enolic structure. Many examples of these aldol reactions that lead to formation of carbocyclic rings have been studied.47 As both elimination and addition of a proton are involved, the reaction occurs in both acidic and basic solutions. As examples of the facility of this reaction, pyruvic acid condenses spontaneously to a dibasic acid at room temperature in dilute solution, and such 8-diketones as 29 readily cyclize to form cyclohexenones, presumably by way of 30, either in acid or base. 

The oscillatory behavior of product-inhibited cultures cannot simply be described by a common inhibition term in the equation for the biomass growth. A better description must include an indirect or delayed effect of the product ethanol on the biomass growth rate as indicated in experiments. The decay rate pmaa was introduced to account for the accumulation of the inhibitory product pyruvic acid. Other more mechanistic, structured models can be formed that relate to the internal key-compound e. In these, the inhibitory action of ethanol is accounted for in the inhibition of the key-compound e formation. Mathematically, however, these two model descriptions are equivalent, except that the key-compound e is washed out as a part of the biomass in continuous cultures and the rate constant //ma55 does not vary. Our proposed indirect inhibition model provides a good qualitative description of the experimental results shown in Figure 7.25. 

Decarboxylation of pyruvic acid and its isomers, including the enol tautomers and enantiomeric lactone structures, has been investigated at the B3LYP/6-311+- -G(3df, 3pd) level.18 It has been found that a keto form with trans CmethyiCketoCacidOhydroxyi and cis CketoCacidOH, and with one methyl hydrogen in a synperiplanar position with respect to the keto oxygen, is the most stable. 

Thus, it is clear that in the case of 3-amino-1,2,4-triazole and 5-aminotetra-zole, reactions with arylidenepyruvic acids and their synthetic precursors lead to identical reaction products [199, 201], while applying sequential or multi-component procedures for interaction with 3-substituted 5-aminopyrazoles allows for the isolation of heterocycles of different structures [202]. However, it is interesting to note that, according to publication [202], reactions of 5-amino-7V-arylpyrazolo-4-carboxamides 213 with arylidenepyruvic acids 236 or with pyruvic acid 239 and aldehydes 240 also yielded identical reaction products—pyrimidine heterocycles 255 (Scheme 3.70). 

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