Glyoxylates reactions

Shortly before Hopkins and Cole isolated tryptophane, they studied the Adamkiewicz reaction—the production of a violet colour when concentrated sulphuric acid is added to a protein dissolved in glacial acetic acid—and found that it was caused by the presence of glyoxylic acid in the glacial acetic acid, from which it arose by the action of sunlight. On applying the glyoxylic reaction to tryptophane a very intense colour was produced, and hence the presence of tryptophane in the protein molecule is the cause of this reaction. 

Downie, I. M., Earle, M. J., Heaney, H., Shuhaibar, K. F. Vilsmeier formylation and glyoxylation reactions of nucleophilic aromatic compounds using pyrophosphoryl chloride. Tefra/jedrorr 1993,49,4015-4034. 

Figure 30. The Nitroso-Glyoxylate Reaction. Initial observations and earliest proposed mechanism.

Kinetic studies showed the reaction to follow a second order rate equation. An unusual observation at the time, but which later proved to be a key point in mechanistic considerations, was the strong solvent dependency of the reaction rate. The nitroso-glyoxylate reaction appears to be restricted to aqueous solvents. The reaction rate is largely independent of pH above 5 and the rate decreased markedly as the pH was decreased from 5 to about 2. 

Corbett, M. D. and B. R. Corbett. 1993. Studies on the nitroso-glyoxylate reaction. Relative hydroxamic acid production by glyoxylate, pyruvate, and formaldehyde in reactions with 4-nitrosobiphenyl. Chem. Res. Toxicol. 6 82-90. 

A combination of the promoting effects of Lewis acids and water is a logical next step. However, to say the least, water has not been a very popular medium for Lewis-acid catalysed Diels-Alder reactions, which is not surprising since water molecules interact strongly with Lewis-acidic and the Lewis-basic atoms of the reacting system. In 1994, when the research described in this thesis was initiated, only one example of Lewis-acid catalysis of a Diels-Alder reaction in water was published Lubineau and co-workers employed lanthanide triflates as a catalyst for the Diels-Alder reaction of glyoxylate to a relatively unreactive diene . No comparison was made between the process in water and in organic solvents. 

Glycohc acid also undergoes reduction or hydrogenation with certain metals to form acetic acid, and oxidation by hydrogen peroxide ia the presence of ferrous salts to form glyoxylic acid [298-12A], HCOCOOH, and ia the presence of ferric salts ia neutral solution to form oxaHc acid, HOOCCOOH formic acid, HCOOH and Hberate CO2 and H2O. These reduction and oxidation reactions are not commercially significant. 

This process has the advantage that, under the reaction conditions, the glyoxyl radical enters the aromatic guaiacol ring almost exclusively para to the phenoHc hydroxyl group. Tedious separation procedures are thus avoided. 

Isothiazole-4,5-dicarboxylic acid, 3-phenyl-dimethyl ester synthesis, S, 150 Isothiazole-5-glyoxylic acid ethyl ester reduction, 6, 156 Isothiazole-4-mercurioacetate reactions, 6, 164 Isothiazole-5-mercurioacetate reactions, 6, 164 Isothiazoles, 6, I3I-I75 acidity, 6, 141 alkylation, 6, 148 aromaticity, S, 32 6, 144-145 basicity, 6, I4I biological activity, 6, 175 boiling points, 6, I43-I44, 144 bond fixation, 6, 145 bond orders, 6, I32-I34 calculated, 6, 133 bromination, S, 58 6, 147 charge densities, 6, 132-134 cycloaddition reactions, 6, 152 desulfurization, S, 75 6, 152 deuteration, S, 70... 

A weak cation-exchange resin is obtained by reaction of glyoxylic acid and a cross-linked polyvinyl alcohol. The polyvinyl alcohol is cross-linked with glutaraldehyde in the presence of hydrochloric acid. The cation-exchange resin has an exchange capacity of 3 meq/g or greater and a swelling volume of 10 ml/g or smaller (37-38). 

FIGURE 20.28 The glyoxylate cycle. The first two steps are identical to TCA cycle reactions. The third step bypasses the C09-evolving steps of the TCA cycle to produce snc-cinate and glyoxylate. The malate synthase reaction forms malate from glyoxylate and another acetyl-CoA. The result is that one torn of the cycle consumes one oxaloacetate and two acetyl-CoA molecnles bnt produces two molecnles of oxaloacetate. The net for this cycle is one oxaloacetate from two acetyl-CoA molecnles. 

With semicarbazones of lower a-keto acids the reaction proceeds with some difficulty or not at all. Thus, the semicarbazones of pyruvic acid cannot be cyclized and that of glyoxylic acid is predominantly hydrolyzed so that the yield of the cyclization product is only 20-25%. ° This reaction was used in work with a different object, for preparing 6-azauracil, for the first time. 

In a further synthesis, Gut ° used the cyclization of the thiosemi-carbazone of glyoxylic acid (56) the 2-thioxo-5-oxo-2,3,4,6-tetra-hydro-l,2,4-triazine (57) formed was converted to 6-azauracil by applying aqueous solution of chloroacetic acid. (This reaction will be discussed later, e.g.. Section II,B,4,b.) The same procedure was used... 

In a study of the nitrosation of camphor-3-glyoxylic acid (89), Chorley and Lapworth isolated a compound whose structure (90) has recently been clarified by Hatfield and Huntsman. Decarboxylation and ring expansion occur and the reaction is rationalized in the sequence 89 90. The buttressing effect of a methyl group on... 

Metal-catalyzed asymmetric hetero Diels-Alder reactions of unactivated dienes with glyoxylates 98PAC1117. 

Reaction of o-phenylenediamine and n-butyl glyoxylate gives quinoxalin-2-onc in excellent yield with 4-nitro-o-phcnylcncdiaminc (5) a mixture of 6- and 7-nitro-quinoxaIin-2-ones, (6) and (7), is obtained. ... 

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