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Gallic acid

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Gallic acid (also known as 3,4,5-trihydroxybenzoic acid) is a trihydroxybenzoic acid with the formula C6H2(OH)3CO2H. It is classified as a phenolic acid. It is found in gallnuts, sumac, witch hazel, tea leaves, oak bark, and other plants.[1] It is a white solid, although samples are typically brown owing to partial oxidation. Salts and esters of gallic acid are termed "gallates".

Gallic acid
Skeletal formula
Space-filling model of gallic acid
Names
Preferred IUPAC name
3,4,5-Trihydroxybenzoic acid
Other names
Gallic acid
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.005.228 Edit this at Wikidata
EC Number
  • 205-749-9
KEGG
RTECS number
  • LW7525000
UNII
  • InChI=1S/C7H6O5/c8-4-1-3(7(11)12)2-5(9)6(4)10/h1-2,8-10H,(H,11,12) checkY
    Key: LNTHITQWFMADLM-UHFFFAOYSA-N checkY
  • InChI=1/C7H6O5/c8-4-1-3(7(11)12)2-5(9)6(4)10/h1-2,8-10H,(H,11,12)
    Key: LNTHITQWFMADLM-UHFFFAOYAN
  • O=C(O)c1cc(O)c(O)c(O)c1
Properties
C7H6O5
Molar mass 170.12 g/mol
Appearance White, yellowish-white, or
pale fawn-colored crystals.
Density 1.694 g/cm3 (anhydrous)
Melting point 260 °C (500 °F; 533 K)
1.19 g/100 mL, 20°C (anhydrous)
1.5 g/100 mL, 20 °C (monohydrate)
Solubility soluble in alcohol, ether, glycerol, acetone
negligible in benzene, chloroform, petroleum ether
log P 0.70
Acidity (pKa) COOH: 4.5, OH: 10.
-90.0·10−6 cm3/mol
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Irritant
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineFlammability 0: Will not burn. E.g. waterInstability (yellow): no hazard codeSpecial hazards (white): no code
1
0
Lethal dose or concentration (LD, LC):
5000 mg/kg (rabbit, oral)
Safety data sheet (SDS) External MSDS
Related compounds
Related
phenols,
carboxylic acids
Related compounds
 Benzoic acid, Phenol, Pyrogallol
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Its name is derived from oak galls, which were historically used to prepare tannic acid. Despite the name, gallic acid does not contain gallium.

Isolation and derivatives

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Electrostatic potential map of surface of gallic acid molecule
 
Ellagic acid molecule structure resembles that of two gallic acid molecules assembled in head to tail position and linked together by a C–C bond (as in biphenyl) and two cyclic ester links (lactones) forming two additional 6-piece cycles.

Gallic acid is easily freed from gallotannins by acidic or alkaline hydrolysis. When heated with concentrated sulfuric acid, gallic acid converts to rufigallol. Hydrolyzable tannins break down on hydrolysis to give gallic acid and glucose or ellagic acid and glucose, known as gallotannins and ellagitannins, respectively.[2]

Biosynthesis

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Chemical structure of 3,5-didehydroshikimate

Gallic acid is formed from 3-dehydroshikimate by the action of the enzyme shikimate dehydrogenase to produce 3,5-didehydroshikimate. This latter compound aromatizes.[3][4]

Reactions

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Oxidation and oxidative coupling

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Alkaline solutions of gallic acid are readily oxidized by air. The oxidation is catalyzed by the enzyme gallate dioxygenase, an enzyme found in Pseudomonas putida.

Oxidative coupling of gallic acid with arsenic acid, permanganate, persulfate, or iodine yields ellagic acid, as does reaction of methyl gallate with iron(III) chloride.[5] Gallic acid forms intermolecular esters (depsides) such as digallic and cyclic ether-esters (depsidones).[5]

Hydrogenation

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Hydrogenation of gallic acid gives the cyclohexane derivative hexahydrogallic acid.[6]

Decarboxylation

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Heating gallic acid gives pyrogallol (1,2,3-trihydroxybenzene). This conversion is catalyzed by gallate decarboxylase.

Esterification

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Many esters of gallic acid are known, both synthetic and natural. Gallate 1-beta-glucosyltransferase catalyzes the glycosylation (attachment of glucose) of gallic acid.

Historical context and uses

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Gallic acid is an important component of iron gall ink, the standard European writing and drawing ink from the 12th to 19th centuries, with a history extending to the Roman empire and the Dead Sea Scrolls. Pliny the Elder (23–79 AD) describes the use of gallic acid as a means of detecting an adulteration of verdigris[7] and writes that it was used to produce dyes. Galls (also known as oak apples) from oak trees were crushed and mixed with water, producing tannic acid. It could then be mixed with green vitriol (ferrous sulfate)—obtained by allowing sulfate-saturated water from a spring or mine drainage to evaporate[citation needed]—and gum arabic from acacia trees; this combination of ingredients produced the ink.[8]

Gallic acid was one of the substances used by Angelo Mai (1782–1854), among other early investigators of palimpsests, to clear the top layer of text off and reveal hidden manuscripts underneath. Mai was the first to employ it, but did so "with a heavy hand", often rendering manuscripts too damaged for subsequent study by other researchers.[9]

Gallic acid was first studied by the Swedish chemist Carl Wilhelm Scheele in 1786.[10] In 1818, French chemist and pharmacist Henri Braconnot (1780–1855) devised a simpler method of purifying gallic acid from galls;[11] gallic acid was also studied by the French chemist Théophile-Jules Pelouze (1807–1867),[12] among others.

When mixed with acetic acid, gallic acid had uses in early types of photography, like the calotype to make the silver more sensitive to light; it was also used in developing photographs.[13]

Occurrence

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Gallic acid is found in a number of land plants, such as the parasitic plant Cynomorium coccineum,[14] the aquatic plant Myriophyllum spicatum, and the blue-green alga Microcystis aeruginosa.[15] Gallic acid is also found in various oak species,[16] Caesalpinia mimosoides,[17] and in the stem bark of Boswellia dalzielii,[18] among others. Many foodstuffs contain various amounts of gallic acid, especially fruits (including strawberries, grapes, bananas),[19][20] as well as teas,[19][21] cloves,[22] and vinegars.[23][clarification needed] Carob fruit is a rich source of gallic acid (24–165 mg per 100 g).[24]

Esters

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Also known as galloylated esters:

Gallate esters are antioxidants useful in food preservation, with propyl gallate being the most commonly used. Their use in human health is scantly supported by evidence.

Spectral data

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UV-Vis
Lambda-max: 220, 271 nm (ethanol)
 
Spectrum of gallic acid
Extinction coefficient (log ε)
IR
Major absorption bands ν : 3491, 3377, 1703, 1617, 1539, 1453, 1254 cm−1 (KBr)
NMR
Proton NMR


(acetone-d6):
d : doublet, dd : doublet of doublets,
m : multiplet, s : singlet

δ :

7.15 (2H, s, H-3 and H-7)

Carbon-13 NMR


(acetone-d6):

δ :

167.39 (C-1),
144.94 (C-4 and C-6),
137.77 (C-5),
120.81 (C-2),
109.14 (C-3 and C-7)

Other NMR data
MS
Masses of
main fragments 		ESI-MS [M-H]- m/z : 169.0137 ms/ms (iontrap)@35 CE m/z product 125(100), 81(<1)

[17]

See also

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References

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  1. ^ Haslam, E.; Cai, Y. (1994). "Plant polyphenols (vegetable tannins): Gallic acid metabolism". Natural Product Reports. 11 (1): 41–66. doi:10.1039/NP9941100041. PMID 15206456.
  2. ^ Andrew Pengelly (2004), The Constituents of Medicinal Plants (2nd ed.), Allen & Unwin, pp. 29–30
  3. ^ Gallic acid pathway on metacyc.org
  4. ^ Dewick, PM; Haslam, E (1969). "Phenol Biosynthesis in Higher Plants. Gallic Acid". Biochemical Journal. 113 (3): 537–542. doi:10.1042/bj1130537. PMC 1184696. PMID 5807212.
  5. ^ a b Edwin Ritzer; Rudolf Sundermann (2007), "Hydroxycarboxylic Acids, Aromatic", Ullmann's Encyclopedia of Industrial Chemistry (7th ed.), Wiley, p. 6
  6. ^ Albert W. Burgstahler and Zoe J. Bithos (1962). "Hexahydrogallic Acid and Hexahydrogallic Acid Triacetate". Organic Syntheses. 42: 62. doi:10.15227/orgsyn.042.0062.
  7. ^ Pliny the Elder with John Bostock and H.T. Riley, trans., The Natural History of Pliny (London, England: Henry G. Bohn, 1857), vol. 6, p. 196. In Book 34, Chapter 26 of his Natural History, Pliny states that verdigris (a form of copper acetate (Cu(CH3COO)2·2Cu(OH)2), which was used to process leather, was sometimes adulterated with copperas (a form of iron(II) sulfate (FeSO4·7H2O)). He presented a simple test for determining the purity of verdigris. From p. 196: "The adulteration [of verdigris], however, which is most difficult to detect, is made with copperas; ... The fraud may also be detected by using a leaf of papyrus, which has been steeped in an infusion of nut-galls; for it becomes black immediately upon the genuine verdigris being applied."
  8. ^ Fruen, Lois. "Iron Gall Ink". Archived from the original on 2011-10-02.
  9. ^ L.D. Reynolds and N.G. Wilson, "Scribes and Scholars" 3rd Ed. Oxford: 1991, pp 193–4.
  10. ^ Carl Wilhelm Scheele (1786) "Om Sal essentiale Gallarum eller Gallåple-salt" (On the essential salt of galls or gall-salt), Kongliga Vetenskaps Academiens nya Handlingar (Proceedings of the Royal [Swedish] Academy of Science), 7: 30–34.
  11. ^ Braconnot Henri (1818). "Observations sur la préparation et la purification de l'acide gallique, et sur l'existence d'un acide nouveau dans la noix de galle" [Observations on the preparation and purification of gallic acid, and on the existence of a new acid in galls]. Annales de Chimie et de Physique. 9: 181–184.
  12. ^ J. Pelouze (1833) "Mémoire sur le tannin et les acides gallique, pyrogallique, ellagique et métagallique," Annales de chimie et de physique, 54: 337–365 [presented February 17, 1834].
  13. ^ Taylor, Roger; Schaaf, Larry John (2007). Impressed by Light: British Photographs from Paper Negatives, 1840-1860. Metropolitan Museum of Art. ISBN 978-1-58839-225-1.
  14. ^ Zucca, Paolo; Rosa, Antonella; Tuberoso, Carlo; Piras, Alessandra; Rinaldi, Andrea; Sanjust, Enrico; Dessì, Maria; Rescigno, Antonio (11 January 2013). "Evaluation of Antioxidant Potential of "Maltese Mushroom" (Cynomorium coccineum) by Means of Multiple Chemical and Biological Assays". Nutrients. 5 (1): 149–161. doi:10.3390/nu5010149. PMC 3571642. PMID 23344249.
  15. ^ Nakai, S (2000). "Myriophyllum spicatum-released allelopathic polyphenols inhibiting growth of blue-green algae Microcystis aeruginosa". Water Research. 34 (11): 3026–3032. Bibcode:2000WatRe..34.3026N. doi:10.1016/S0043-1354(00)00039-7.
  16. ^ Mämmelä, Pirjo; Savolainen, Heikki; Lindroos, Lasse; Kangas, Juhani; Vartiainen, Terttu (2000). "Analysis of oak tannins by liquid chromatography-electrospray ionisation mass spectrometry". Journal of Chromatography A. 891 (1): 75–83. doi:10.1016/S0021-9673(00)00624-5. PMID 10999626.
  17. ^ a b Chanwitheesuk, Anchana; Teerawutgulrag, Aphiwat; Kilburn, Jeremy D.; Rakariyatham, Nuansri (2007). "Antimicrobial gallic acid from Caesalpinia mimosoides Lamk". Food Chemistry. 100 (3): 1044–1048. doi:10.1016/j.foodchem.2005.11.008.
  18. ^ Alemika, Taiwo E.; Onawunmi, Grace O.; Olugbade, Tiwalade A. (2007). "Antibacterial phenolics from Boswellia dalzielii". Nigerian Journal of Natural Products and Medicine. 10 (1): 108–10.
  19. ^ a b Pandurangan AK, Mohebali N, Norhaizan ME, Looi CY (2015). "Gallic acid attenuates dextran sulfate sodium-induced experimental colitis in BALB/c mice". Drug Design, Development and Therapy. 9: 3923–34. doi:10.2147/DDDT.S86345. PMC 4524530. PMID 26251571.
  20. ^ Koyama, K; Goto-Yamamoto, N; Hashizume, K (2007). "Influence of maceration temperature in red wine vinification on extraction of phenolics from berry skins and seeds of grape (Vitis vinifera)". Bioscience, Biotechnology, and Biochemistry. 71 (4): 958–65. doi:10.1271/bbb.60628. PMID 17420579.
  21. ^ Hodgson JM, Morton LW, Puddey IB, Beilin LJ, Croft KD (2000). "Gallic acid metabolites are markers of black tea intake in humans". Journal of Agricultural and Food Chemistry. 48 (6): 2276–80. doi:10.1021/jf000089s. PMID 10888536.
  22. ^ Pathak, S. B.; Niranjan, K.; Padh, H.; Rajani, M.; et al. (2004). "TLC Densitometric Method for the Quantification of Eugenol and Gallic Acid in Clove". Chromatographia. 60 (3–4): 241–244. doi:10.1365/s10337-004-0373-y. S2CID 95396304.
  23. ^ Gálvez, Miguel Carrero; Barroso, Carmelo García; Pérez-Bustamante, Juan Antonio (1994). "Analysis of polyphenolic compounds of different vinegar samples". Zeitschrift für Lebensmittel-Untersuchung und -Forschung. 199: 29–31. doi:10.1007/BF01192948. S2CID 91784893.
  24. ^ Goulas, Vlasios; Stylos, Evgenios; Chatziathanasiadou, Maria; Mavromoustakos, Thomas; Tzakos, Andreas (10 November 2016). "Functional Components of Carob Fruit: Linking the Chemical and Biological Space". International Journal of Molecular Sciences. 17 (11): 1875. doi:10.3390/ijms17111875. ISSN 1422-0067. PMC 5133875. PMID 27834921.
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