Glyoxal
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| Names | |||
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| Preferred IUPAC name
Oxaldehyde[1] | |||
| Systematic IUPAC name
Ethanedial[1] | |||
| Other names | |||
| Identifiers | |||
3D model (JSmol)
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| ChEBI | |||
| ChemSpider | |||
| ECHA InfoCard | 100.003.160 | ||
| KEGG | |||
PubChem CID
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| UNII | |||
CompTox Dashboard (EPA)
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| Properties | |||
| C2H2O2 | |||
| Molar mass | 58.036 g·mol−1 | ||
| Melting point | 15 °C (59 °F; 288 K) | ||
| Boiling point | 51 °C (124 °F; 324 K) | ||
| Thermochemistry | |||
Heat capacity (C)
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1.044 J/(K·g) | ||
| Hazards | |||
| NFPA 704 (fire diamond) | |||
| Flash point | −4 °C (25 °F; 269 K) | ||
| 285 °C (545 °F; 558 K) | |||
| Related compounds | |||
Related aldehydes
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acetaldehyde glycolaldehyde propanedial methylglyoxal | ||
Related compounds
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glyoxylic acid glycolic acid oxalic acid pyruvic acid diacetyl acetylacetone | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Glyoxal is an organic compound with the chemical formula OCHCHO. It is the smallest dialdehyde (a compound with two aldehyde groups). It is a crystalline solid, white at low temperatures and yellow near the melting point (15 °C). The liquid is yellow, and the vapor is green.[2]
Pure glyoxal is not commonly encountered because glyoxal is usually handled as a 40% aqueous solution (density near 1.24 g/mL). It forms a series of hydrates, including oligomers. For many purposes, these hydrated oligomers behave equivalently to glyoxal. Glyoxal is produced industrially as a precursor to many products.[3]
Production
[edit]Glyoxal was first prepared and named by the German-British chemist Heinrich Debus (1824–1915) by reacting ethanol with nitric acid.[4][5]
Commercial glyoxal is prepared either by the gas-phase oxidation of ethylene glycol in the presence of a silver or copper catalyst (the Laporte process) or by the liquid-phase oxidation of acetaldehyde with nitric acid.[3]
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The first commercial glyoxal source was in Lamotte, France, started in 1960. The single largest commercial source is BASF in Ludwigshafen, Germany, at around 60,000 tons per year. Other production sites exist also in the US and China. Commercial bulk glyoxal is made and reported as a 40% solution in water by weight[3] (approx. 1:5 molar ratio of glyoxal to water).
Laboratory methods
[edit]Glyoxal may be synthesized in the laboratory by oxidation of acetaldehyde with selenious acid[6] or by ozonolysis of benzene.[7]
Anhydrous glyoxal is prepared by heating solid glyoxal hydrate(s) with phosphorus pentoxide and condensing the vapors in a cold trap.[8]
Properties
[edit]The experimentally determined Henry's law constant of glyoxal is:
![{\displaystyle K_{\text{H}}=4.19\times 10^{5}\times \exp \left[{\frac {6.22\times 10^{4}\,{\text{J}}\,{\text{mol}}^{-1}}{R}}\times \left({\frac {1}{T}}-{\frac {1}{298\,{\text{K}}}}\right)\right]\,{\text{M}}\,{\text{atm}}^{-1}.}](https://wikimedia.org/api/rest_v1/media/math/render/svg/b0b2a288b5770ef350f3249431764b3c2d799d45)
Biochemistry
[edit]
Advanced glycation end-products (AGEs) are proteins or lipids that become glycated as the result of a high-sugar diet.[10] They are a bio-marker implicated in aging and the development, or worsening, of many degenerative diseases, such as diabetes, atherosclerosis, chronic kidney disease, and Alzheimer's disease.[11]
Guanine bases in DNA can undergo non-enzymatic glycation by glyoxal to form glyoxal-guanine adducts.[12] These adducts may then produce DNA crosslinks. Glycation of DNA may also lead to mutation, breaks in DNA and cytotoxicity.[13] In humans, glyoxal-glycated nucleotides can be repaired by the protein DJ-1 also known as Park7.[13]
Applications
[edit]Coated paper and textile finishes use large amounts of glyoxal as a crosslinker for starch-based formulations. It condenses with urea to afford 4,5-dihydroxy-2-imidazolidinone, which further reacts with formaldehyde to give the bis(hydroxymethyl) derivative dimethylol ethylene urea, which is used for wrinkle-resistant chemical treatments of clothing, i.e. permanent press.[3]
Glyoxal is used as a solubilizer and cross-linking agent in polymer chemistry.
Glyoxal is a valuable building block in organic synthesis, especially in the synthesis of heterocycles such as imidazoles.[14] A convenient form of the reagent for use in the laboratory is its bis(hemiacetal) with ethylene glycol, 1,4-dioxane-2,3-diol. This compound is commercially available.
Glyoxal solutions can also be used as a fixative for histology, that is, a method of preserving cells for examining them under a microscope.
Speciation in solution
[edit]
Glyoxal is supplied typically as a 40% aqueous solution.[3] Like other small aldehydes, glyoxal forms hydrates. Furthermore, the hydrates condense to give a series of oligomers, some of which remain of uncertain structure. For most applications, the exact nature of the species in solution is inconsequential. At least one hydrate of glyoxal is sold commercially, glyoxal trimer dihydrate: [(CHO)2]3(H2O)2 (CAS 4405-13-4). Other glyoxal equivalents are available, such as the ethylene glycol hemiacetal 1,4-dioxane-trans-2,3-diol (CAS 4845-50-5, m.p. 91–95 °C).
It is estimated that, at concentrations less than 1 M, glyoxal exists predominantly as the monomer or hydrates thereof, i.e., OCHCHO, OCHCH(OH)2, or (HO)2CHCH(OH)2. At concentrations above 1 M, dimers predominate. These dimers are probably dioxolanes, with the formula [(HO)CH]2O2CHCHO. Dimer and trimers precipitate as solids from cold solutions.[15]
Other occurrences
[edit]Glyoxal has been observed as a trace gas in the atmosphere, e.g. as an oxidation product of hydrocarbons.[16] Tropospheric concentrations of 0–200 ppt by volume have been reported, in polluted regions up to 1 ppb by volume.[17]
Safety
[edit]The LD50 (oral, rats) is 3300 mg/kg,[3] when LD50 of common salt is 3000 mg/kg.[18]
References
[edit]- ^ a b c "Characteristic (Functional) and Substituent Groups". Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book). Cambridge: The Royal Society of Chemistry. 2014. pp. 415, 417. doi:10.1039/9781849733069-00372. ISBN 978-0-85404-182-4.
- ^ O'Neil, M.J. (2001): The Merck Index, 13th Edition, page 803.
- ^ a b c d e f Mattioda, Georges; Blanc, Alain. "Glyoxal". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a12_491.pub2. ISBN 978-3527306732.
- ^ See:
- H. Debus (1857) "On the action of nitric acid on alcohol at common temperatures," Philosophical Magazine, 4th series, 13 : 39–49. From p. 40 : "This residue consisted almost entirely of the aldehyde of glyoxylic acid; I proposed to call it Glyoxal, C2H4O3."
- H. Debus (1857) "On glyoxal," Philosophical Magazine, 4th series, 13 : 66.
- ^ Henry Enfield Roscoe and Carl Schorlemmer, A Treatise on Chemistry, vol. 3 (New York, New York: D. Appleton and Co., 1890), pp. 101-102.
- ^ Ronzio, A. R.; Waugh, T. D. (1944). "Glyoxal Bisulfite". Organic Syntheses. 24: 61. doi:10.15227/orgsyn.024.0061.
- ^ US3637860A, Keaveney, William P. & Pappas, James J., "Process of preparing glyoxal", issued 1972-01-25
- ^ Harries, C.; Temme, F. (1907). "Über monomolekulares und trimolekulares Glyoxal" [On monomoleular and trimoecular glyoxal]. Berichte. 40 (1): 165–172. doi:10.1002/cber.19070400124.
Man erhitzt nun das Glyoxal-Phosphorpentoxyd-Gemisch mit freier Flamme und beobachtet bald, dass sich unter Schwarzfärbung des Kolbeninhalte ein flüchtiges grünes Gas bildet, welches sich in der gekühlten Vorlage zu schönen Krystallen von gelber Farbe kondensiert. [One heats the mixture of (crude) glyoxal and P4O10 with an open flame and soon observes, upon blackening of the contents, a mobile green gas which condenses in the cooled flask as beautiful yellow crystals.]
- ^ Ip, H. S.; Huang, X. H.; Yu, J. Z. (2009). "Effective Henry's law constants of glyoxal, glyoxylic acid, and glycolic acid" (PDF). Geophys. Res. Lett. 36 (1): L01802. Bibcode:2009GeoRL..36.1802I. doi:10.1029/2008GL036212. S2CID 129747490.
- ^ Goldin, Alison; Beckman, Joshua A.; Schmidt, Ann Marie; Creager, Mark A. (2006). "American Heart Association". Circulation. 114 (6): 597–605. doi:10.1161/CIRCULATIONAHA.106.621854. PMID 16894049.
- ^ Vistoli, G; De Maddis, D; Cipak, A; Zarkovic, N; Carini, M; Aldini, G (Aug 2013). "Advanced glycoxidation and lipoxidation end products (AGEs and ALEs): an overview of their mechanisms of formation" (PDF). Free Radic. Res. 47: Suppl 1:3–27. doi:10.3109/10715762.2013.815348. PMID 23767955. S2CID 207517855.
- ^ Vilanova B, Fernández D, Casasnovas R, Pomar AM, Alvarez-Idaboy JR, Hernández-Haro N, Grand A, Adrover M, Donoso J, Frau J, Muñoz F, Ortega-Castro J. Formation mechanism of glyoxal-DNA adduct, a DNA cross-link precursor. Int J Biol Macromol. 2017 May;98:664-675. doi: 10.1016/j.ijbiomac.2017.01.140. Epub 2017 Feb 10. PMID 28192135
- ^ a b Richarme G, Liu C, Mihoub M, Abdallah J, Leger T, Joly N, Liebart JC, Jurkunas UV, Nadal M, Bouloc P, Dairou J, Lamouri A. Guanine glycation repair by DJ-1/Park7 and its bacterial homologs. Science. 2017 Jul 14;357(6347):208-211. doi: 10.1126/science.aag1095. Epub 2017 Jun 8. PMID 28596309
- ^ Snyder, H. R.; Handrick, R. G.; Brooks, L. A. (1942). "Imidazole". Organic Syntheses. 22: 65; Collected Volumes, vol. 3, p. 471.
- ^ Whipple, E. B. (1970). "Structure of Glyoxal in Water". J. Am. Chem. Soc. 92 (24): 7183–7186. doi:10.1021/ja00727a027.
- ^ Vrekoussis, M.; Wittrock, F.; Richter, A.; Burrows, J. P. (2009). "Temporal and spatial variability of glyoxal as observed from space". Atmos. Chem. Phys. 9 (13): 4485–4504. Bibcode:2009ACP.....9.4485V. doi:10.5194/acp-9-4485-2009.
- ^ Volkamer, Rainer; et al. (2007). "A missing sink for gas‐phase glyoxal in Mexico City: Formation of secondary organic aerosol". Geophys. Res. Lett. 34 (19): 19. Bibcode:2007GeoRL..3419807V. doi:10.1029/2007gl030752. S2CID 17490842.
- ^ "Safety (MSDS) data for sodium chloride". ox.ac.uk. Archived from the original on 2011-06-07.