2- -/?ketocarboxylic acid

In another procedure, D-amino acid oxidase (52) is usehil to produce L-amino acids from DL-amino acids. a-Ketocarboxylic acids which are formed by the action of enzymes on D-amino acids, are aminated to form L-amino acids by coupling through the action of amino acid aminotransferases (53). 

We detenuined the influence of oxy- and ketocarboxylic acids (succinate, fumarate, adipinate, a-ketoglutarate, isocitrate, tartrate, E-malate) on the luminescence intensity of the Eu-OxTc complex. These substances interact as polydentate ligands similarly to citrate with the formation of ternary complexes with Eu-OxTc. As to succinate, fumarate, adipinate and a-ketoglutarate this they cannot effectively coordinate with EiT+ and significant fluorescence enhancement was not observed. 

Other contributions to this discussion have been made by Harvey, Miller and Robson, and by Dewar and King, and important additional experimental evidence for the location of the. CHOH group at has been provided by Witkop, who explains the improvement in the yield of yohimbone, which occurs when the decarboxylation of yohimbic acid takes place under oxidising conditions, as due to the primary formation of a j8-ketocarboxylic acid, which is readily decarboxylated. This may be represented, using part of the yohimbine formula fXIV), as follows MeO. OC. CH. 1 CHOH. ->HO. OC. CH. CHOH. ... 

Whilst ketocarboxylic acids can be dimerized satisfactorily (Table 2, No. 9, 10), the corresponding aldehydes couple poorly. Good yields can be obtained in these cases when the acetals, e.g. 17 [133], 18 [134], are electrolyred instead. 

Thermolytic processes are so far known to play only a minor role in the generation of the PO ion. An isolated case is the thermolysis of the monosodium salt of acetonylphosphonic acid at 150 °C, which leads to acetone and sodium polymetaphosphate 107). A cyclic fragmentation mechanism, as known for P-ketocarboxylic acids, could lead to PO in this case. 

The nickel hydroxide electrode resembles in its applications and selectivity the chemical oxidant nickel peroxide. The nickel hydroxide electrode is, however, cheaper, easy to use and in scale-up, and produces no second streams/ waste- and by-products [196], Nickelhydroxide electrode has been applied to the oxidation of primary alcohols to acids or aldehydes, of secondary alcohols to ketones, as well as in the selective oxidation of steroid alcohols, cleavage of vicinal diols, in the oxidation of y-ketocarboxylic acids, of primary amines to nitriles, of 2,6-di-tert-butylphenol to 2,2, 6,6 -tetra-rert-butyldiphenoquinone, of 2-(benzylideneamino)-phenols to 2-phenyloxazols, of 1,1-dialkylhydrazines to tetraalkyltetrazenes. For details the reader is referred to Ref. [195]. 

Constitution of the Esters of the (3-Ketocarboxylic Acids and of the P-Diketones.—Ethyl acetoacetate is taken as example. It reacts like a ketone with phenylhydrazine, bisulphite, and other ketone reagents on the other hand it shows an acid reaction, it dissolves in alkalis, and gives the colour reaction with ferric chloride characteristic of ends and also of phenols. From this double behaviour it was formerly concluded that it was either purely ketonic or purely enolic and that the reactions in the other form were to be attributed to a rearrangement caused by the reagents used. The true state of affairs was first disclosed by... 

Isatin is the inner anhydride (lactam) of a y-amino-a-ketocarboxylic acid, isatinic acid (A), and is converted into a salt of this acid by the action of alkali. The keto-group in position 3 can condense with many other substances, and for this reason isatin is manufactured on a technical scale and converted into valuable indigoid vat dyes. The magnificent thioindigo scarlet, which is obtained from isatin and a sulphur analogue of indoxyl (the so-called hydroxythionaphthene), may be taken as example qq... 

Thermal degradation prior to ionization can cause decarbonylation or decarboxylation of the analyte. Decarbonylation, for example, is observed from a-ketocarboxylic acids and a-ketocarboxylic acid esters, whereas decarboxylation is typical behavior of P-oxocarboxylic acids such as malonic acid and its derivatives and di-, tri-, or polycarboxylic acids. 

Likewise, aromatic ketocarboxylic acids with the carbonyl and the carboxyl groups attached in the 1,2 position react as lactols (7 ) ... 

Another example of Ugi/Pictet-Spengler two-step procedure was employed by El Kaim et al. to prepare polycyclic 1,4-diketopiperazines 228 [69]. The four-component Ugi reaction of homoveratryl isocyanide 229 and a-ketocarboxylic acids 230 allows the formation of Ugi products, which were treated with trifluor-oactic acid to afford tricychc 2,5-diketopiperazines 228 in a Pictet-Spengler-type cyclization (Scheme 42). 

Complex mixtures of oxidized products are produced in the ozonolysis of BaP on solid substrates. For example, BaP deposited on a glass fiber filter and exposed to 1 ppm 03 in air primarily formed products characteristic of the ring-opening mechanism, e.g., dialdehydes and dicarboxylic and ketocarboxylic acids. However, some quinones and phenols, were also formed. For details on the mechanisms and O-PAH products of these BaP-Ov gas-solid substrate reactions, see Van Cauwenberghe et al. (1979) and Van Cauwenberghe and Van Vaeck (1983 and references therein). 

Photolysis of JV-aryl amides of /3-ketocarboxylic acids 135 proceeds in a different way.93 Thus, phenylisocyanate 136 is formed in 60% yield when in 135 R = phenyl. When R = methyl or propyl, the yield decreases to 18%. Consequently, this reaction belongs only formally to the scope of the discussed rearrangements. It seems that this is a special example of Norrish Type II reaction.324 This assumption is supported by the yield dependence of... 

Use of a /3-ketocarboxylic acid derivative may circumvent this problem (8-ketocarboxylic acid derivatives react with esters of a-amino carboxylic acids to give (Y) a-aminonitriles afford (Z) in a condensation step. 

The considerations that (Z), as a vinylogous amide, may undergo hydrolysis to (Y) whereas (Y) and (Z), being derivatives of /3-ketocarboxylic acids, can be subjected to acid cleavage suggest starting with (Z) itself as a general synthetic approach (Scheme 2). 

Retrosynthetic Scheme 1 shows the general synthetic approach. Under certain conditions, the preparation of the /3-ketocarboxylic acids R4—CO—CH2—COOH or their esters might become the largest chal-... 

Tertiary amine salts of ketocarboxylic acids were used initially. Newer systems based on peptide chemistry have been described and used in microlithography. 

Furthermore these reagents can attack ethers, double bonds and aromatic rings in more functionalized compounds. The nickel hydroxide electrode is a suitable reagent to overcome these difficulties The necessary alkaline electrolyte opens the lactone ring to the oxidizable hydroxycarboxylate. The nickel hydroxide electrode tolerates double bonds, ethers and aromatic rings and leads in good to excellent yields to ketocarboxylic acids (Eq. (6), Table 11). 

Table 11. Oxidation of lactones to ketocarboxylic acids at the nickel hydroxide electrode...

Other carboxylate-dye interactions have been reported. Ethylenediamine tetracarboxylic acid (EDTA) and its salts are well known reductants for a variety of dyes (54,55). The amino-acid N-phenylglycine can be photooxidized and induce polymer formation (26,56,57). Studies of the efficiency of photopolymerization of acrylate monomers by MB/N-phenylglycine combinations as a function of the pH of the medium suggest that either the amino group or the free carboxylate can act as an electron donor for the dye excited state, but that the amine functional-lity is the more efficient coinitiator (10). Davidson and coworkers (58) have shown that ketocarboxylic acids are photode-carboxylated by electron transfer quenching of dye triplet states under anaerobic conditions. Superoxide formation can occur when oxygen is present. 

Gas-phase decarboxylation of /i-ketocarboxylic acids XCOCH2COOH (X = H, OH, and CH3) has also been the subject of theoretical studies.42 Ah initio calculations reveal that decarboxylation via a six-membered (rather than four-membered) ring transition state is favoured. Activation barriers of 23.8, 23.3 and 28.5 kcal mol-1 have been calculated for decarboxylation of 3-oxopropanoic acid, acetoacetic acid, and malonic acid, respectively. Only marginal effects of solvent on the energy barriers and on the geometries of the reactants and transition structures are predicted. The activation energy predicted for reaction of malonic acid agrees well with the experimental value and rate constants have been predicted for decarboxylation of 3-oxopropanoic acid and acetoacetic acid in the gas phase. 

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