Synthesis of mesoxalic acid

[Carnepan]

Hello

For further research I need mesoxalate (as acid or salt). It is quite expensive in stores, so I decided to synthesize it in the lab. I tried to hydrolyze alloxan with alkali (NaOH or Ba(OH)2), but I only got alloxanate of the corresponding salt. I also tried to oxidize diethyl malonate with NO2 and NaClO2, but the oxidation did not work at all.

Does anyone have a working synthesis method? Or can anyone help me figure out what went wrong?

[chenbeier]

Mesoxalic acid can be obtained synthetically by hydrolysis of alloxan with baryta water,^[2] by warming caffuric acid^[3] with lead acetate solution,^[2] or from glyceryl diacetate and concentrated nitric acid in ice-cold water. The product can be obtained also by oxidation of tartronic acid^[4] or glycerol.^[5] Since they are carried out in water, these procedures generally give the dihydroxy derivative.

It is also prepared by the oxidation of glycerol with the help of bismuth(III) nitrate.

References

1.  

• Merck Index (12th ed.). p. 5971.
•  
• Henry Enfield Roscoe (1888), A Treatise on Chemistry, volume 3, part2 Organic Chemistry, p. 161. D. Appleton and Co., New York
•  
• The chemical structure of caffuric acid was given in Allen, W. F. (1932). The preparation and pyrolytic molecular rearrangment [sic] of the 8-ethers of caffeine: And their conversion to 8-methyl and 8-ethylcaffeine. Ann Arbor, Mich.: Edwards Brothers.
•  
• Rosaria Ciriminna and Mario Pagliaro (2004), Oxidation of tartronic acid and dihydroxyacetone to sodium mesoxalate mediated by TEMPO. Tetrahedron Letters, volume 45, issue 34, pp. 6381–6383 doi:10.1016/j.tetlet.2004.07.021
•  
• Rosaria Ciriminna and Mario Pagliaro (2003), One-Pot Homogeneous and Heterogeneous Oxidation of Glycerol to Ketomalonic Acid Mediated by TEMPO. Advanced Synthesis & Catalysis, volume 345, issue 3, Pages 383–388. doi:10.1002/adsc.200390043

[Carnepan]

12 hours ago, chenbeier said:

Mesoxalic acid can be obtained synthetically by hydrolysis of alloxan with baryta water,^[2] by warming caffuric acid^[3] with lead acetate solution,^[2] or from glyceryl diacetate and concentrated nitric acid in ice-cold water. The product can be obtained also by oxidation of tartronic acid^[4] or glycerol.^[5] Since they are carried out in water, these procedures generally give the dihydroxy derivative.

It is also prepared by the oxidation of glycerol with the help of bismuth(III) nitrate.

References

1.  

• Merck Index (12th ed.). p. 5971.
•  
• Henry Enfield Roscoe (1888), A Treatise on Chemistry, volume 3, part2 Organic Chemistry, p. 161. D. Appleton and Co., New York
•  
• The chemical structure of caffuric acid was given in Allen, W. F. (1932). The preparation and pyrolytic molecular rearrangment [sic] of the 8-ethers of caffeine: And their conversion to 8-methyl and 8-ethylcaffeine. Ann Arbor, Mich.: Edwards Brothers.
•  
• Rosaria Ciriminna and Mario Pagliaro (2004), Oxidation of tartronic acid and dihydroxyacetone to sodium mesoxalate mediated by TEMPO. Tetrahedron Letters, volume 45, issue 34, pp. 6381–6383 doi:10.1016/j.tetlet.2004.07.021
•  
• Rosaria Ciriminna and Mario Pagliaro (2003), One-Pot Homogeneous and Heterogeneous Oxidation of Glycerol to Ketomalonic Acid Mediated by TEMPO. Advanced Synthesis & Catalysis, volume 345, issue 3, Pages 383–388. doi:10.1002/adsc.200390043

Yes, I tried to synthesize this compound based on these considerations. Not a single reaction worked, since there is no exact description of the synthesis. If you have one, please share it.

[KJW]

 

34 minutes ago, Carnepan said:

Not a single reaction worked, since there is no exact description of the synthesis.

Did you actually look up the references?

 

[Carnepan]

1 hour ago, KJW said:

 

Did you actually look up the references?

 

Yes, I looked at the original articles and did as described in them, but the syntheses do not work. According to NMR data, there is only the initial substance in the solution, and no product was observed

I understand that I could be wrong about them, so I need someone who could tell me about the intricacies of organic synthesis.

I am just a specialist in inorganic synthesis, and I encountered organic synthesis for the first time

[KJW]

8 hours ago, Carnepan said:

I need someone who could tell me about the intricacies of organic synthesis.

Perhaps you could post the full procedure here.