Mandelic acid

Summary

Mandelic acid[1]
Structural formula of mandelic acid
Ball-and-stick model of the mandelic acid molecule
Names
Preferred IUPAC name
Hydroxy(phenyl)acetic acid
Other names
2-Hydroxy-2-phenylacetic acid
Mandelic acid
Phenylglycolic acid
α-Hydroxyphenylacetic acid
Identifiers
  • 90-64-2 checkY
  • 611-71-2 (R) checkY
  • 17199-29-0 (S) checkY
3D model (JSmol)
  • Interactive image
ChEBI
  • CHEBI:35825 checkY
ChEMBL
  • ChEMBL1609 checkY
ChemSpider
  • 1253 checkY
ECHA InfoCard 100.001.825 Edit this at Wikidata
EC Number
  • 202-007-6
  • 1292
RTECS number
  • OO6300000
UNII
  • NH496X0UJX checkY
  • PPL7YW1M9W (R) checkY
  • L0UMW58G3T (S) checkY
  • DTXSID6023234 Edit this at Wikidata
  • InChI=1S/C8H8O3/c9-7(8(10)11)6-4-2-1-3-5-6/h1-5,7,9H,(H,10,11) checkY
    Key: IWYDHOAUDWTVEP-UHFFFAOYSA-N checkY
  • InChI=1/C8H8O3/c9-7(8(10)11)6-4-2-1-3-5-6/h1-5,7,9H,(H,10,11)
    Key: IWYDHOAUDWTVEP-UHFFFAOYAD
  • O=C(O)C(O)c1ccccc1
Properties
C8H8O3
Molar mass 152.149 g·mol−1
Appearance White crystalline powder
Density 1.30 g/cm3
Melting point 119 °C (246 °F; 392 K) optically pure: 132 to 135 °C (270 to 275 °F; 405 to 408 K)
Boiling point 321.8 °C (611.2 °F; 595.0 K)
15.87 g/100 mL
Solubility soluble in diethyl ether, ethanol, isopropanol
Acidity (pKa) 3.41[2]
1.5204
Thermochemistry
0.1761 kJ/g
Pharmacology
B05CA06 (WHO) J01XX06 (WHO)
Hazards
Flash point 162.6 °C (324.7 °F; 435.8 K)
Related compounds
Related compounds
mandelonitrile, phenylacetic acid, vanillylmandelic acid
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)
Infobox references

Mandelic acid is an aromatic alpha hydroxy acid with the molecular formula C6H5CH(OH)CO2H. It is a white crystalline solid that is soluble in water and polar organic solvents. It is a useful precursor to various drugs. The molecule is chiral. The racemic mixture is known as paramandelic acid.

Isolation, synthesis, occurrence

Mandelic acid was discovered in 1831 by the German pharmacist Ferdinand Ludwig Winckler (1801–1868) while heating amygdalin, an extract of bitter almonds, with diluted hydrochloric acid. The name is derived from the German "Mandel" for "almond".[3]

Mandelic acid is usually prepared by the acid-catalysed hydrolysis of mandelonitrile,[4] which is the cyanohydrin of benzaldehyde. Mandelonitrile can also be prepared by reacting benzaldehyde with sodium bisulfite to give the corresponding adduct, forming mandelonitrile with sodium cyanide, which is hydrolyzed:[5]

Preparation of mandelic acid.png

Alternatively, it can be prepared by base hydrolysis of phenylchloroacetic acid as well as dibromacetophenone.[6] It also arises by heating phenylglyoxal with alkalis.[7][8]

Biosynthesis

Mandelic acid is a substrate or product of several biochemical processes called the mandelate pathway. Mandelate racemase interconverts the two enantiomers via a pathway that involves cleavage of the alpha-CH bond. Mandelate dehydrogenase is yet another enzyme on this pathway.[9] Mandelate also arises from trans-cinnamate via phenylacetic acid, which is hydroxylated.[10] Phenylpyruvic acid is another precursor to mendalic acid.

Derivatives of mandelic acid are formed as a result of metabolism of adrenaline and noradrenaline by monoamine oxidase and catechol-O-methyl transferase. The biotechnological production of 4-hydroxy-mandelic acid and mandelic acid on the basis of glucose was demonstrated with a genetically modified yeast Saccharomyces cerevisiae, in which the hydroxymandelate synthase naturally occurring in the bacterium Amycolatopsis was incorporated into a wild-type strain of yeast, partially altered by the exchange of a gene sequence and expressed.[11]

It also arises from the biodegradation of styrene, as detected in urine.[12]

Uses

Mandelic acid has a long history of use in the medical community as an antibacterial, particularly in the treatment of urinary tract infections.[13] It has also been used as an oral antibiotic, and as a component of chemical face peels analogous to other alpha hydroxy acids.[14]

The drugs cyclandelate and homatropine are esters of mandelic acid.

References

  1. ^ Merck Index, 11th Edition, 5599.
  2. ^ Bjerrum, J., et al. Stability Constants, Chemical Society, London, 1958.
  3. ^ See:
    • Winckler, F. L. (1831) "Ueber die Zersetzung des Calomels durch Bittermandelwasser, und einige Beiträge zur genaueren Kenntniss der chemischen Zusammensetzung des Bittermandelwassers" (On the decomposition of calomel [i.e., mercury(I) chloride] by bitter almond water, and some contributions to a more precise knowledge of the chemical composition of bitter almond water), Repertorium für die Pharmacie, 37 : 388–418; mandelic acid is named on p. 415.
    • Winckler, F. L. (1831) "Ueber die chemische Zusammensetzung des Bittermandelwassers; als Fortsetzung der im 37sten Band S. 388 u.s.w. des Repertoriums enthaltenen Mittheilungen" [On the chemical composition of bitter almond water; as a continuation of the report contained in the 37th volume, pp. 388 ff. of the Repertorium], Repertorium für die Pharmacie, 38 : 169–196. On p. 193, Winckler describes the preparation of mandelic acid from bitter almond water and hydrochloric acid (Salzsäure).
    • (Editor) (1832) "Ueber einige Bestandtheile der Bittermandeln" (On some components of bitter almonds), Annalen der Chemie und Pharmacie, 4 : 242–247.
    • Winckler, F. L. (1836) "Ueber die Mandelsäure und einige Salze derselben" (On mandelic acid and some salts of the same), Annalen der Chemie und Pharmacie, 18 (3) : 310–319.
    • Hermann Schelenz, Geschichte der Pharmazie [The History of Pharmacy] (Berlin, German: Julius Springer, 1904), p. 675.
  4. ^ Ritzer, Edwin; Sundermann, Rudolf (2000). Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a13_519.
  5. ^ Corson, B. B.; Dodge, R. A.; Harris, S. A.; Yeaw, J. S. (1926). "Mandelic Acid". Org. Synth. 6: 58. doi:10.15227/orgsyn.006.0058.
  6. ^ J. G. Aston; J. D. Newkirk; D. M. Jenkins & Julian Dorsky (1952). "Mandelic Acid". Organic Syntheses.; Collective Volume, vol. 3, p. 538
  7. ^ Pechmann, H. von (1887). "Zur Spaltung der Isonitrosoverbindungen". Berichte der Deutschen Chemischen Gesellschaft. 20 (2): 2904–2906. doi:10.1002/cber.188702002156.
  8. ^ Pechmann, H. von; Muller, Hermann (1889). "Ueber α-Ketoaldehyde". Berichte der Deutschen Chemischen Gesellschaft. 22 (2): 2556–2561. doi:10.1002/cber.188902202145.
  9. ^ Kenyon, George L.; Gerlt, John A.; Petsko, Gregory A.; Kozarich, John W. (1995). "Mandelate Racemase: Structure-Function Studies of a Pseudosymmetric Enzyme". Accounts of Chemical Research. 28 (4): 178–186. doi:10.1021/ar00052a003.
  10. ^ Lapadatescu, Carmen; Giniès, Christian; Le QuéRé, Jean-Luc; Bonnarme, Pascal (2000). "Novel Scheme for Biosynthesis of Aryl Metabolites from l-Phenylalanine in the Fungus Bjerkandera adusta". Applied and Environmental Microbiology. 66 (4): 1517–1522. doi:10.1128/AEM.66.4.1517-1522.2000. PMC 92016. PMID 10742235.
  11. ^ Mara Reifenrath, Eckhard Boles: Engineering of hydroxymandelate synthases and the aromatic amino acid pathway enables de novo biosynthesis of mandelic and 4-hydroxymandelic acid with Saccharomyces cerevisiae. Metabolic Engineering 45, Januar 2018; S. 246-254. doi:10.1016/j.ymben.2018.01.001.
  12. ^ Engström K, Härkönen H, Kalliokoski P, Rantanen J. "Urinary mandelic acid concentration after occupational exposure to styrene and its use as a biological exposure test" Scand. J. Work Environ. Health. 1976, volume 2, pp. 21-6.
  13. ^ Putten, P. L. (1979). "Mandelic acid and urinary tract infections". Antonie van Leeuwenhoek. 45 (4): 622–623. doi:10.1007/BF00403669.
  14. ^ Taylor, MB. (1999). "Summary of mandelic acid for the improvement of skin conditions". Cosmetic Dermatology. 21: 26–28.
  •  This article incorporates text from a publication now in the public domainChisholm, Hugh, ed. (1911). "Mandelic Acid". Encyclopædia Britannica. Vol. 17 (11th ed.). Cambridge University Press. p. 559.