Oxidation of tartronic acid and dihydroxyacetone to sodium mesoxalate mediated by TEMPO

Tetrahedron Letters

Volumn 45, Issue 34, 2004, Pages 6381-6383

  Ciriminna, Rosaria ^a   Pagliaro, Mario ^a  

^a CNR   (Italy)

Author keywords

DHA; Mesoxalic; Oxidation; Tartronic acid; TEMPO

Indexed keywords

ANTIDIABETIC AGENT; DIHYDROXYACETONE; SODIUM MESOXALATE; TARTRONIC ACID; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL REACTION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OXIDATION;

EID: 4143058026     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2004.07.021     Document Type: Article

References (13)

1. To find practical applications and replace current commercial conversions, however, such processes will need to be economic (low capital investment) or afford high value-added products. For a recent account on recent important advancements in the field, see: P.L. Bragd, H. van Bekkum, and A.C. Besemer Top. Catal. 27 2004 49 66
2. R. Ciriminna, and M. Pagliaro Adv. Synth. Catal. 345 2003 383 388 A vast 10% w/w surplus of glycerine is obtained in biodiesel production and with a UE directive requiring 5.75% of the entire fuel consumption coming from biodiesel by 2005, 400,000 t of glycerine are expected to reach the market: a 7-fold increase from the 60,000 t produced in 2001
3. (a) Trademark of ICN Pharmaceuticals (now Valeant)
4. W.R. Davis, J. Tomsho, S. Nikam, E.M. Cook, D. Somand, and J.A. Peliska Biochemistry 39 2000 14279 14291
5. (a) The starting material of tartronic acid is malonic acid and the price of TA is currently 30 times higher that that of ketomalonic acid monohydrate
6. (b) Currently the bioprocess affords a yearly worldwide production of 2000 t of DHA mainly for use in cosmetics due to the skin-binding properties of the molecule
7. Despite notable recent improvements such as the syntheses of mesoxalic acid from tartronic reported in Kimura, H. Japanese Patent Laid Open 1,51,346, 1996 and
8. P. Fordham, M. Besson, and P. Gallezot Catal. Lett. 46 1997 195 199 heterogeneous aerobic catalytic processes have not yet found commercial applications mainly due to the low stability of supported metals in the oxidative environment, which requires high metal/substrate ratios and a thorough control of the reaction conditions to minimize the formation of undesired byproducts, which, nonetheless, are always present in the reaction mixture and high selectivities becoming more difficult as the compounds become more oxidized
9. A.E.J. de Nooy, A.C. Besemer, and H. van Bekkum Synthesis 1996 1153 1174
10. 2 catalyst affords high molecular weight poly(ketomalonate): (a) H. Kimura Polym. Adv. Technol. 12 2001 697 710
11. 13C NMR shows that the reaction product is sodium mesoxalate (hydrate) with the NMR signal of the carboxyls and the gem-diol carbons resonating at 175 and at 165 ppm
12. S. Carrettin, P. McMorn, P. Johnston, K. Griffin, C.J. Kiely, G.A. Attard, and G.J. Hutchings Top. Catal. 27 2004 131 136
13. 2O were recorded on a Bruker spectrometer working at a proton resonating frequency of 250 MHz