Oxidation glycerate

Methylsuccinic acid has been prepared by the pyrolysis of tartaric acid from 1,2-dibromopropane or allyl halides by the action of potassium cyanide followed by hydrolysis by reduction of itaconic, citraconic, and mesaconic acids by hydrolysis of ketovalerolactonecarboxylic acid by decarboxylation of 1,1,2-propane tricarboxylic acid by oxidation of /3-methylcyclo-hexanone by fusion of gamboge with alkali by hydrog. nation and condensation of sodium lactate over nickel oxide from acetoacetic ester by successive alkylation with a methyl halide and a monohaloacetic ester by hydrolysis of oi-methyl-o -oxalosuccinic ester or a-methyl-a -acetosuccinic ester by action of hot, concentrated potassium hydroxide upon methyl-succinaldehyde dioxime from the ammonium salt of a-methyl-butyric acid by oxidation with. hydrogen peroxide from /9-methyllevulinic acid by oxidation with dilute nitric acid or hypobromite from /J-methyladipic acid and from the decomposition products of glyceric acid and pyruvic acid. The method described above is a modification of that of Higginbotham and Lapworth. ... 

Figure 17-3. Mechanism of oxidation of giyceraldehyde 3-phosphate. (Enz, glycer-aldehyde-3-phosphate dehydrogenase.) The enzyme is inhibited by the— 5H poison iodoacetate, which is thus abie to inhibit glycolysis. The NADH produced on the enzyme is not as firmly bound to the enzyme as is NAD. Consequently, NADH is easily displaced by another molecule of NAD". ...

Figure 8. Product composition vs. time for glyceric acid oxidation at pH=10-ll on 5%Pt2%Bi/C.

Scheme 2. Proposed mechanism for oxidation of the secondary alcohol function of glyceric acid.

The liquid-phase oxidation of glycerol was carried out by using carbon-supported gold particles of different sizes (2.7 2 nm) which were prepared by a colloidal route [120]. Indeed, a particle-size effect was observed because the selectivity to glyceric acid was increased to 75% with smaller particle sizes (4)ptmimn = 3.7 nm). 

From product distribution analysis it could be concluded that larger particles present higher selectivity to glycerate due to the reduction of consecutive reaction, i.e. oxidation of glycerate to tartronate, remaining glycolate amount being almost stable. 

The importance of size control has been depicted for the selective oxidation of glycerol it was shown that by increasing particle size a high selectivity to glycerate has been reached at the expense of the consecutive oxidation of glycerate to tartronate. 

This curious phenomenon of inversion of groups about the asymmetric carbon atom, first studied by Walden (1893, 1985) is called Walden Inversion. In a number of other reactions, the inversion was so quantitative that the yield of the opitcal isomer was 100% while in others the product was a mixture of the (+) and (-) forms in unequal amounts signifying that the inversion was partial. The above conversion has been shown to occur in two steps. The step in which the actual inversion occurs constitutes a Walden inversion. Change in the sign of rotation does not necessarily mean that an inversion of configuration has occurred as is clear from the oxidation of D(+) glyceraldehyde to D(-) glyceric acid. 

The Pt/C catalyst, compared with Pd/C, showed not only enhanced activity (vide supra) but also reduced selectivity for glyceric acid (only 55% at 90% conversion), favoring dihydroxyacetone formation up to 12%, compared with 8% for the Pd case [48]. The Pt/C catalyst promoted with Bi showed superior yields of dihydroxyacetone (up to 33%), at lower pHs. Glyceric and hydroxypyruvic acids, apparently, are formed as by-product and secondary product, respectively [48], The addition of Bi seems to switch the susceptibility of glycerol oxidation from the primary towards the secondary carbon atoms. 

In a second wave of activity in the area of glycerol oxidation with Pt or Pd-on-carbon catalysts, the high yields for glyceric add at 60 °C and atmospheric pressure described earlier, were initially no longer obtained by other authors. It seems that there is appreciable formation of compounds other than C3 and C2 oxidized... 

At 0.3 MPa of oxygen, the sum of the observed C2 and C3 oxidation products amounted to correct mass balances, with glyceraldehyde, glyceric acid and oxalic acid being the dominant products in absence of added NaOH [81]. NaOH addition resulted in the disappearance of oxalic acid formation. 

Furthermore, a base-catalyzed transformation by OH from the reaction medium between glycerate and hydroxypyruvate aldehyde (or hydroxypyruvic acid) could be excluded, while hydroxyacetone and glyceraldehyde interconversion was possible (Scheme 11.11). The existence of two major routes, of which hydroxyacetone and glyceric aldehyde are the primary oxidation products and glycolic and oxalic acid are the end-members, respectively, is now firmly established. Clearly, rapid oxidation of glyceraldehydes favors glyceric acid rather than hydroxyacetone formation. 

The Ru(m)-catalyzed oxidation of glycerol by an acidified solution of bromate (BrCfi ) at 45 °C consumes the required amount of 2 moles of bromate to obtain pure glyceric acid. Traces of Hg(OAc)2 were used as scavenger for potentially formed bromide, thereby eliminating the formation of bromine (formed by reaction of bromide and bromate) as an alternative oxidant [96]. The reaction is first order in Ru(m) (0.58 ms-1 at 45 °C) and zero order in substrate and protons. The addition of RuC163 to protonated bromate is assumed to be rate limiting. Similar catalytic chemistry is obtained with Rh(m)Cl3 [97]. 

Now for the glycerates. 1,3 bis-phosphoglycerate [compound (iii)] is the only molecule with two attached P groups. When we number the carbon atoms in an aliphatic organic compound we invariably start at the most oxidized carbon (drawn at the top of the chain), so carbon 2 of the glyceric acid derivatives must be the middle... 

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