Pyruvic acid, reaction with

Sulfuryl chloride, reaction with pyruvic acid to yield chloropyruvic acid, 40,54... 

Hydralazine 219 is a good precursor for that ring system. Its reactions with pyruvic acid (75JOC2901), arylidene pyruvic acids (81AP1030), and 4-aryl-2-oxo-butanoic acids (87JHC63) gave the respective hydrazones... 

This reaction makes the wrong ring size But another interesting reaction with pyruvic acid makes the required quinoline 50, esterified without isolation.6... 

Figure 6.3. Structures of C4 substituted anthocyanins identified in aged red wines formed by reaction with pyruvic acid, vinylphenol, vinylcatechol, vinylguaiacol, vinyl(epi)catechin (Fulcrand et al., 1998 Hayasaka and Asenstorfer, 2002 Alcade-Eon et al., 2004 Gomez-Ariza et al., 2006.)...

The initial syntheses of Cypridina luciferin and its analogues were performed in low yields by reaction of appropriate 2-aminopyrazines with a-keto acids, followed by reduction with aluminum amalgam or catalytic hydrogenation, and treatment of the product with dicyclohexyl-carbodiimide. For example, 2-amino-5-phenylpyrazine (36) on reaction with pyruvic acid gave the product 37, which was reduced to give an intermediate formulated as 38, which was then cyclized to give the 0x0 compound 39 in 7% yield. It was later discovered that these products could be obtained in high yield in one step by reaction of aminopyrazines such as 36 with a-keto aldehydes such as pyruvaldehyde (MeCOCHO). Condensation of the appropriate aminopyrazine with... 

A synthesis of the neuraminidase inhibitor 4-deoxy-4-guanidino-neuraminic acid derivative 28 from neuraminic acid has been effected and a number of N-substituted guanidines were also prepared,while further chain-shortened analogues of 28 have been prepared without C-9 then C-8 and then C-7. Other analogues 29 have been prepared from Kdn and the 5-deoxy-derivative 30 has been synthesized from 2-deoxy-D-arafewio-hexose by way of an aldolase-catalysed reaction with pyruvic acid. Neuraminic acid has also been converted into the 3,4-dideoxy-4-guanidino derivative 31. ... 

This is an example of the Doebner synthesis of quinoline-4-carboxylic acids (cinchoninic acids) the reaction consists in the condensation of an aromatic amine with pyruvic acid and an aldehj de. The mechanism is probably similar to that given for the Doebner-Miller sj nthesis of quinaldiiie (Section V,2), involving the intermediate formation of a dihydroquinoline derivative, which is subsequently dehydrogenated by the Schiff s base derived from the aromatic amine and aldehyde. 

The scope of this reaction was investigated by Djerassi, °° who showed that 4-bromo ketones in the series and 2-bromo ketones in the 5a series give unsaturated 2,4-dinitrophenylhydrazones in 80-90% yield on warming under nitrogen with 1.1 moles of 2,4-dinitrophenylhydrazine in acetic acid. Cleavage with pyruvic acid affords the pure unsaturated ketones in 60-70 % yield. 

Doebner showed that certain aldehydes, citral, for example, form condensation products with pyruvic acid and )8-naphthylamine, known as naphthocinchoninic acids. The reaction takes place as follows —... 

Nef prepared acetol in several ways, the more important of which depended upon the reaction between bromoacetone and potassium or sodium formate or acetate, and the subsequent hydrolysis of the ester by methyl alcohol.1 2 Acetol is also formed, together with pyruvic acid, by the direct oxidation of acetone by Baeyer and Villiger s acetone-peroxide reagent.3... 

Some derivatives of pyrimidof 1,6-6][ 1,2,4]triazines 245 have been prepared (88SC805) as potential anticancer agents by reaction of the triamino-pyrimidinethione 244 with pyruvic acid, followed by alkylation. 

The thiadiazolo[3,4-g] indole 100 was prepared from 4-amino-5-chlorobenzothiadiazole 99 by treatment with pyruvic acid in the presence of [Pd(But3P)2] (Equation 14) <2004AGE4526>. The Herz reaction of 4-aminoben-zothiadiazole 101 with disulfur dichloride gave the fused 1,2,3-dithiazolium chloride 102, which was condensed with malononitrile to give the ylidene 103 (Scheme 15) <2002J(P1)315>. 

Knoevenagel adduct 239 of oxohomophthalimide 240 with malononitrile 27a in reactions with CH-acids behaves ambiguously (82CPB1215). Reactions of 239 with acetylacetone, ethyl esters of acetoacetic and ben-zoylacetic acids, as well as methyl pyruvate led to the formation of the desired spiropyrans 241. However, benzoylacetone, dibenzoylmethane, cyanacetamide, and oxindole always gave the same 242. Authors explain this feature in terms of a retro-cleavage of adducts of Michael product 239... 

If the total reaction is a simple decarboxylation of malic acid to lactic acid, it is difficult to understand how the utilization of malic acid can influence cell growth. Carbon dioxide also has been shown to stimulate growth of L. oenos ML 34 (84), yet it would seem the carbon dioxide formed from the reaction would be superfluous in new wine already saturated with it. In the original conception of the pathway, the reaction was considered as two stages with pyruvic acid and reduced NAD (NADH) as intermediates (72). Morenzoni (71) discussed the research and thinking (4, 85, 86, 87) which lead to the belief that there was only one step in the reaction and no formation of NADH or pyruvic acid as intermediates. However, any evidence to show a real formation of pyruvic acid would help explain the stimulatory effect of the reaction on cellular metabolism. 

Further developments are shown in Figure 4. On the basis that glucosamine reacted with pyruvic acid in the presence of alkali to yield pyrrole-2-carboxylic acid, in 1% yield, Gottschalk (21) proposed that sialic acid was formed by an aldol condensation reaction between N-ace-tylglucosamine and pyruvic acid. Kuhn and Brossmer (15) and Zilliken and Glick (22) showed that the reverse reaction also took place under alkaline conditions. Cornforth, Firth, and Gottschalk (23) synthesized crystalline N-acetylneuraminic acid (NANA) from N-acetylglucosamine and oxaloacetic acid (pH 11, 20°C). Under conditions less subject to misinterpretation, Heimer and Meyer (24) found that Vibrio cholerae enzymes cleaved NANA into an N-acetylhexosamine and pyruvic acid. 

Reaction of benzo[6]thiophene-2-carboxaldehyde with pyruvic acid yields the keto acid (321), the oxime of which gives a-amino-y-(2-benzo[6]thienyl)butyric acid (322) on catalytic hydrogenation, and j9-(2-benzo[6]thienyl)acrylonitrile on treatment with acetic anhydride the latter yields 8-(2-benzo[6]thienyl)acrylic acid on hydro-... 

The solvent deuterium isotope effect in the reaction of 359 with glyoxylate decreases from ( H2o/ D2o) °f 1-66 to ( H2o/ D2o) °f 1-12 with increasing pH from 1.25 to 6.43, respectively. 361 probably decarboxylates via a cyclic transition state. Transfer of the carboxylic proton takes place simultaneously with heavy-atom reorganization as indicated by small solvent DIE in the acid-catalysed reaction. The solvent DIE h2o/ D20 °f 1-20 at 1. M H+, observed in the reaction of 359 with pyruvic acid, is similar to the reaction of pyruvic acid with nitrosobenzene for which nucleophilic attack of nitroso nitrogen has been proposed395. 

Reaction of pyruvic acid with H2NNHC(S)NHNH2 gave the cyclic Schiff bases possessing the 1,2,4,5-tetrazepine fragment (Equation 13) <1996MI67>. 

Fig. 5. Study of the equilibria in the reaction of histidine with pyruvic acid. 9x10 Sodium pyruvate, histidine buffer pH 9.17, concentration of histidine is given in the polarogram. Ionic strength kept constant. Curves starting at —0.8 V, S.C.E., 200 mV/absc., t = 2.8 sec, m= 1.8 mg/sec, full scale sensitivity 6.5 p.A...

EC 1.11.1.7) (68) and diphenol oxidase (EC 1.10.3.1) (69) have been identified. The potential role of pyruvic decarboxylase (EC 4.1.1.1) catalyzed reaction as a source of acetaldehyde and other aldehydes in juice was discussed (70). Raymond et al. (71) isolated the decarboxylase from orange juice sections and demonstrated that only 10 to 15% of the enzyme was in an active form. Since the purified enzyme was only active with pyruvic acid and 2-ketobutyric acid of the series of 2-ketoacids examined, they (71) concluded that the direct contribution of orange pyruvic decarboxylase to the orange volatile profile was limited to acetaldehyde and possibly propionaldehyde. 

However, the key disadvantage of the reaction described in [199] is observed in the first step—synthesis of unsaturated ketoacids 236 with very low yields (20-30%) [200]. The same authors [201] proposed a multicomponent approach to azolopyr-imidinecarboxylic acids. The reactions of pyruvic acid 239 and aromatic aldehydes 240 with 2-aminobenzimidazole, 5-aminotetrazole 156 and 3-amino-1,2,4-triazole 147 in alcohols, DMF and acetic acid were studied (Scheme 3.67). 

Chebanov et al. [202] noted that condensation of the unsaturated acids 236 with 5-aminopyrazoles 220-222 never yielded isomers with opposite location of the aryl and carboxyl groups on the pyridine or pyrimidine rings, respectively. In the case of the multicomponent reaction of aminopyrazoles 220-222 with pyruvic acid 239 and aromatic aldehydes a different direction was observed. Refluxing of the starting materials in acetic acid led exclusively to pyrazolo[3,4-Z ]pyridine-4-carboxylic acids 249-251 instead of the anticipated carboxylic acids 243-248 (Scheme 3.69). The three-component procedures led only to the formation of heteroaromatized compounds even under a nitrogen atmosphere [202]. 

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). 

The three-component reaction of amines 220-222 with pyruvic acid 239 and aromatic aldehydes has as the first step the formation of the appropriate azomethine intermediate D (Scheme 3.72). This hypothesis was proved by Chebanov et al. [202] through the synthesis of compounds 249-251 by the reaction of azomethine D with pyruvic acid. 

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