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Author: Subject: Glyoxylic Acid via Glycolic Acid Oxidation (Questions)
enima
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[*] posted on 9-12-2004 at 02:07
Glyoxylic Acid via Glycolic Acid Oxidation (Questions)


I recently found an interested article were catechol is converted to vanillin via the condensation of glyoxylic acid followed by the oxidation using a CuO NaOH system.

The paper is found in:
Organic Process Research & Development, 2000, 4, 534-543.

The synthesis seems very easy it is a base catalyzed reaction, NaOH is used as the base.

The only problem arises from the aquisition of the glyoxylic acid. There are two problems associated with it.

1. Glyoxylic acid is expensive.
2. Glyoxylic acid is used for illegal chemistry (not sure what) and for this reason is a watched chemical.

Since I neither have a deep pocket or the time to deal with law enforcement, (chemistry is a hobby of mine), i've been looking into ways of synthezing glyoxylic acid.

Two methods come up.

1. Oxidation of glyoxal or glycolic acid.
2. Reduction of oxalic acid.


Both methods can be done electrolytically, however the task does not provide high yields. (Nor do I have the know how to build an electrolytic cell for electrolysis.)


DuPont claims that their glycolic acid can be oxidized to glyoxylic acid with H2o2 in the presence of an Iron salt.

DuPont also claims that at a neutral pH the same reagents result in the production of oxalic, an formic acid.

I'm curious to if anyone has a proceedure for the production of glyoxylic acid via the H2O2 oxidation.

(http://www.dupont.com.br/adm/port/ upload_produto_pdf/Think%20Glycolic!.pdf )
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chemoleo
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[*] posted on 9-12-2004 at 12:39


If you check the patent servers (such as espace.net, and the US one), there are a variety of methods available.
The ones that are doable are described in the following two patents:
http://l2.espacenet.com/espacenet/viewer?PN=CA1295967&CY...
http://l2.espacenet.com/espacenet/viewer?PN=GB437649&CY=...

Indeed, electrolysis can done, of oxalic acid with a lead dioxide electrode - whereby a different thread deals with making lead dioxide electrodes.

Alternatively, if you can generate dichloro acetic acid, then it's a simple matter to just boil the salt of it with sodium acetate.

Or, you can partiallly oxidise glyoxal with nitric acid, according to the procedure described in German Pat. No. 932,369 and in French Pat. No. 1,326,605.

There are many more methods, but this might get you started.




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aliced25
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[*] posted on 21-3-2012 at 06:30


There is also the oxidative cleavage of tartaric acid (or esters thereof) by either lead tetraacetate or periodate. Orgsyn has a Lead based procedure (http://www.orgsyn.org/orgsyn/prep.asp?prep=cv4p0124).



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[*] posted on 21-3-2012 at 06:45


Why would glyoxylic acid be used for illegal chemistry any more then things like sulfuric acid and solvents? You could make piperonal with it, but that's the hard way

You could oxidize glyoxal, a photography chemical, with nitric acid. I believe there is a thread about this. I also have a few papers and patents stored away somewhere.




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Waffles SS
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[*] posted on 16-10-2013 at 09:47




What about Sommelet reaction?
I think maybe this is possible to convert Chloroacetic acid to Glyoxylic acid by Sommelet reaction.
Some body has experience or suggestion about this?
Does Sommelet reaction only covert Aromatic halide to aldehyde?what about aliphatic halide?


[Edited on 16-10-2013 by Waffles SS]
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WGTR
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[*] posted on 16-10-2013 at 11:08


Glyoxilic acid from creatine by the action of H2O2 and ferrous sulfate:

http://www.jbc.org/content/1/4/271.full.pdf

Creatine monohydrate is a popular health supplement, and fairly cheap.

Calcium glyoxylate has limited solubility in water, calcium formate is considerably more soluble.

"Calcium Glyoxylate.

This salt, like calcium acetate, exists in two forms, one stable and crystallised, the other gelatinous and unstable. If a. concentrated solution of ammonium glyoxylate is mixed with one of calcium nitrate, the mixture turns into a jelly, so that the vessel may be inverted without any loss. In the course of a few hours, white particles become visible in the mass ; these particles increase gradually in number and magnitude, and develop finally into fine crystals having the form of the original calcium glyoxylate.

The crystals dissolve at 8° in 177 parts of water, and at 100° in about 40 parts. The hot saturated solution remains supersaturated for some time when allowed to cool down to the ordinary temperature, the excess of the dissolved salt crystallising out very slowly. Tufts of fine needles appear at first on the sides of the beaker, and as they grow larger they change in the course of a day or two into single prisms. The crystals thus obtained are very hard. The formula of the crystalline salt is Ca(C2HOB)2,2H.L,O. When a solution of pure calcium glyoxylate is concentrated on the water-bath, the salt will, as the water evaporates, separate as a crust round the sides of the dish ; if, however, calcium glycollate is present, the solution may be concentrated to a considerable extent without the separation of any salt."

Journal of the Chemical Society, 1904, pg. 1391


Quote: Originally posted by enima  
DuPont claims that their glycolic acid can be oxidized to glyoxylic acid with H2o2 in the presence of an Iron salt.


This method is referenced in the JBC article, but only small amounts were obtained.


[Edited on 16-10-2013 by WGTR]
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