Umbelliferone

Umbelliferone
Names
	Preferred IUPAC name 7-Hydroxy-2H-1-benzopyran-2-one
	Other names 7-hydroxycoumarin, hydrangine, skimmetine, beta-umbelliferone
Identifiers
CAS Number	93-35-6 ;
3D model (JSmol)	Interactive image ;
ChEBI	CHEBI:27510 ;
ChEMBL	ChEMBL51628 ;
ChemSpider	4444774 ;
ECHA InfoCard	100.002.038
PubChem CID	5281426 ;
UNII	60Z60NTL4G ;
CompTox Dashboard (EPA)	DTXSID5052626 ;
	InChI InChI=1S/C9H6O3/c10-7-3-1-6-2-4-9(11)12-8(6)5-7/h1-5,10H Key: ORHBXUUXSCNDEV-UHFFFAOYSA-N ; InChI=1/C9H6O3/c10-7-3-1-6-2-4-9(11)12-8(6)5-7/h1-5,10H Key: ORHBXUUXSCNDEV-UHFFFAOYAL;
	SMILES c1cc(cc2c1ccc(=O)o2)O;
Properties
Chemical formula	C9H6O3
Molar mass	162.14 g/mol
Appearance	yellowish-white crystalline odorless powder
Melting point	230 °C (446 °F; 503 K) (decomposes)
Magnetic susceptibility (χ)	-88.22·10−6 cm3/mol
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). verify (what is ?) Infobox references

Last updated March 03, 2024

Umbelliferone, also known as 7-hydroxycoumarin, hydrangine, skimmetine, and beta-umbelliferone, is a natural product of the coumarin family.

Natural occurrences and name

Umbelliferone's name is from the umbelliferae family of plants, and the plant family in turn was named for their umbrella-shaped inflorescences, each called an umbel.

Umbelliferone occurs in many familiar plants from the Apiaceae (Umbelliferae) family such as carrot, coriander and garden angelica, as well as in plants from other families, such as the mouse-ear hawkweed ( Hieracium pilosella , Asteraceae) or the bigleaf hydrangea ( Hydrangea macrophylla , Hydrangeaceae, under the name hydrangine).

It is one of the components of asafoetida, the dried latex from the giant fennel ( Ferula communis ).

It is also found in Justicia pectoralis (Acanthaceae).^[5]^[6]

Biosynthesis

Umbelliferone is a phenylpropanoid and as such is synthesized from L-phenylalanine, which in turn is produced via the shikimate pathway. Phenylalanine is lyased into cinnamic acid, followed by hydroxylation by cinnamate 4-hydroxylase to yield 4-coumaric acid. The 4-coumaric acid is again hydroxylated by cinnamate/coumarate 2-hydroxylase to yield 2,4-dihydroxy-cinnamic acid (umbellic acid) followed by a bond rotation of the unsaturated bond adjacent to the carboxylic acid group. Finally an intramolecular attack from the hydroxyl group of C2' to the carboxylic acid group closes the ring and forms the lactone umbelliferone.

${\begin{matrix}{}\\{\xrightarrow {\mathrm {PAL} }}\\{}\end{matrix}}$ ${\begin{matrix}{}\\{\xrightarrow {\mathrm {C4H} }}\\{}\end{matrix}}$ ${\begin{matrix}{}\\{\xrightarrow {\mathrm {C2H} }}\\{}\end{matrix}}$ $\longrightarrow$

Chemical synthesis

Umbelliferone is traditionally synthesized using the Pechmann condensation, from resorcinol and formylacetic acid (generated from malic acid in situ).^[7]

A newer synthesis uses methyl propionate and a palladium catalyst.

Ultraviolet fluorescence

Umbelliferone absorbs strongly at 300, 305 and 325 nm, with log ε values of 3.9, 3.95 and 4.15 respectively, and it fluoresces blue in both ultraviolet and visible light. The powerful absorption at three different wavelengths, coupled with the fact that the energy is dissipated safely as visible light, make umbelliferone a useful sunscreen agent. The absorption changes in alkaline solution, since the phenolic hydroxyl group is deprotonated (pK_a = 7.7).

Uses

The ultraviolet activity of umbelliferone led to its use as a sunscreen agent, and an optical brightener for textiles. It has also been used as a gain medium for dye lasers. Umbelliferone can be used as a fluorescence indicator for metal ions such as copper and calcium. It acts as a pH indicator in the range 6.5-8.9.^{[ citation needed ]}

Umbelliferone is a potent inhibitor of type 3 17β-hydroxysteroid dehydrogenase, the primary enzyme responsible for the conversion of 4-androstene-3,17-dione to testosterone, with IC50 of 1.4 μM.^[8]

Derivatives

Umbelliferone is the parent compound for a large number of natural products. Herniarin (7-O-methylumbelliferone or 7-methoxycoumarin) occurs in the leaves of water hemp ( Eupatorium ayapana ) and rupturewort ( Herniaria ). O-Glycosylated derivatives such as skimmin (7-O-β-D-glucopyranosylumbelliferone) occur naturally and are used for the fluorimetric determination of glycoside hydrolase enzymes. Isoprenylated derivatives are also widespread, such as marmin (found in grapefruit skin and in the bark of the Bael tree) and furocoumarins such as marmesin, angelicin, and psoralen.

Umbelliferone 7-apiosylglucoside can be isolated from the root of Gmelina arborea .^[9]

Related Research Articles

Cinnamic acid is an organic compound with the formula C₆H₅-CH=CH-COOH. It is a white crystalline compound that is slightly soluble in water, and freely soluble in many organic solvents. Classified as an unsaturated carboxylic acid, it occurs naturally in a number of plants. It exists as both a cis and a trans isomer, although the latter is more common.

Coumarin or 2H-chromen-2-one is an aromatic organic chemical compound with formula C₉H₆O₂. Its molecule can be described as a benzene molecule with two adjacent hydrogen atoms replaced by an unsaturated lactone ring −(CH)=(CH)−(C=O)−O−, forming a second six-membered heterocycle that shares two carbons with the benzene ring. It belongs to the benzopyrone chemical class and considered as a lactone.

<i>Gmelina arborea</i> Species of flowering plant

Gmelina arborea,, locally known as gamhar, is a fast-growing deciduous tree in the family Lamiaceae.

<span class="mw-page-title-main">Methoxsalen</span> Chemical compound

Methoxsalen, sold under the brand name Oxsoralen among others, is a medication used to treat psoriasis, eczema, vitiligo, and some cutaneous lymphomas in conjunction with exposing the skin to ultraviolet (UVA) light from lamps or sunlight. Methoxsalen modifies the way skin cells receive the UVA radiation, allegedly clearing up the disease. Levels of individual patient PUVA exposure were originally determined using the Fitzpatrick scale. The scale was developed after patients demonstrated symptoms of phototoxicity after oral ingestion of methoxsalen followed by PUVA therapy. Chemically, methoxsalen belongs to a class of organic natural molecules known as furanocoumarins. They consist of coumarin annulated with furan. It can also be injected and used topically.

<span class="mw-page-title-main">Chlorogenic acid</span> Chemical compound

Chlorogenic acid (CGA) is the ester of caffeic acid and (−)-quinic acid, functioning as an intermediate in lignin biosynthesis. The term "chlorogenic acids" refers to a related polyphenol family of esters, including hydroxycinnamic acids with quinic acid.

p-Coumaric acid is an organic compound with the formula HOC₆H₄CH=CHCO₂H. It is one of the three isomers of hydroxycinnamic acid. It is a white solid that is only slightly soluble in water but very soluble in ethanol and diethyl ether.

The phenylpropanoids are a diverse family of organic compounds that are biosynthesized by plants from the amino acids phenylalanine and tyrosine in the shikimic acid pathway. Their name is derived from the six-carbon, aromatic phenyl group and the three-carbon propene tail of coumaric acid, which is the central intermediate in phenylpropanoid biosynthesis. From 4-coumaroyl-CoA emanates the biosynthesis of myriad natural products including lignols, flavonoids, isoflavonoids, coumarins, aurones, stilbenes, catechin, and phenylpropanoids. The coumaroyl component is produced from cinnamic acid.

<span class="mw-page-title-main">Daidzein</span> Chemical compound

Daidzein is a naturally occurring compound found exclusively in soybeans and other legumes and structurally belongs to a class of compounds known as isoflavones. Daidzein and other isoflavones are produced in plants through the phenylpropanoid pathway of secondary metabolism and are used as signal carriers, and defense responses to pathogenic attacks. In humans, recent research has shown the viability of using daidzein in medicine for menopausal relief, osteoporosis, blood cholesterol, and lowering the risk of some hormone-related cancers, and heart disease. Despite the known health benefits, the use of both puerarin and daidzein is limited by their poor bioavailability and low water solubility.

In enzymology, a trans-cinnamate 2-monooxygenase (EC 1.14.13.14) is an enzyme that catalyzes the chemical reaction

In enzymology, a trans-cinnamate 4-monooxygenase (EC 1.14.14.91) is an enzyme that catalyzes the chemical reaction

The enzyme phenylalanine ammonia lyase (EC 4.3.1.24) catalyzes the conversion of L-phenylalanine to ammonia and trans-cinnamic acid.:

In enzymology, a 2-coumarate O-beta-glucosyltransferase is an enzyme that catalyzes the chemical reaction

Dianthera pectoralis is an herb in the family Acanthaceae. This water-willow is widely known as tilo in Latin America and in Cuba. In Haiti, it is called chapantye and zeb chapantyè on Dominica and Martinique. Other folk names are freshcut, chambácarpintero ("carpenter"), té criollo, curia, death-angel, masha-hari, or "piri piri". This species was described by Nikolaus Joseph von Jacquin in 1760, who provided additional data in 1763. A well-marked variety, var. stenophylla, was described by Emery Clarence Leonard in 1958.

Indirect DNA damage occurs when a UV-photon is absorbed in the human skin by a chromophore that does not have the ability to convert the energy into harmless heat very quickly. Molecules that do not have this ability have a long-lived excited state. This long lifetime leads to a high probability for reactions with other molecules—so-called bimolecular reactions. Melanin and DNA have extremely short excited state lifetimes in the range of a few femtoseconds (10⁻¹⁵s). The excited state lifetime of compounds used in sunscreens such as menthyl anthranilate, avobenzone or padimate O is 1,000 to 1,000,000 times longer than that of melanin, and therefore they may cause damage to living cells that come in contact with them.

<span class="mw-page-title-main">Aesculetin</span> Chemical compound

Aesculetin is a derivative of coumarin. It is a natural lactone that derives from the intramolecular cyclization of a cinnamic acid derivative.

Coumaroyl-coenzyme A is the thioester of coenzyme-A and coumaric acid. Coumaroyl-coenzyme A is a central intermediate in the biosynthesis of myriad natural products found in plants. These products include lignols, flavonoids, isoflavonoids, coumarins, aurones, stilbenes, catechin, and other phenylpropanoids.

Angelicin is the parent compound in a family of naturally occurring organic compounds known as the angular furanocoumarins. Structurally, it can be considered as benzapyra-2-one fused with a furan moiety in the 7,8-position. Angelicin is commonly found in certain Apiaceae and Fabaceae plant species such as Bituminaria bituminosa. It has a skin permeability coefficient (LogK_p) of -2.46. The maximum absorption is observed at 300 nm. The ¹HNMR spectrum is available; the infrared and mass spectra of angelicin can be found in this database. The sublimation of angelicin occurs at 120 °C and the pressure of 0.13 Pa. Angelicin is a coumarin.

The biosynthesis of phenylpropanoids involves a number of enzymes.

o-Coumaric acid is a hydroxycinnamic acid, an organic compound that is a hydroxy derivative of cinnamic acid. There are three isomers of coumaric acids — o-coumaric acid, m-coumaric acid, and p-coumaric acid — that differ by the position of the hydroxy substitution of the phenyl group.

Umbellic acid is a hydroxycinnamic acid. It is an isomer of caffeic acid.

References

↑ Ohta T, Watanabe K, Moriya M, Shirasu Y, Kada T (1983). "Anti-mutagenic effects of coumarin and umbelliferone on mutagenesis induced by 4-nitroquinoline 1-oxide or UV irradiation in e. Coli". Mutation Research. 117 (1–2): 135–138. doi:10.1016/0165-1218(83)90160-x. PMID 6403855.
↑ Du L (2008). "Rational design of a fluorescent hydrogen peroxide probe based on the umbelliferone fluorophore". Tetrahedron Letters. 49 (19): 3045–3048. doi:10.1016/j.tetlet.2008.03.063. PMC 2490821 . PMID 19081820.
↑ "UMBELLIFERONE". www.chemicalland21.com. Retrieved 21 November 2011.
↑ Sim MO, Lee HI, Ham JR, Seo KI, Kim MJ, Lee MK (2015). "Anti-inflammatory and antioxidant effects of umbelliferone in chronic alcohol-fed rats". Nutr Res Pract. 9 (4): 364–369. doi:10.4162/nrp.2015.9.4.364. PMC 4523479 . PMID 26244074.
↑ Leal LK, A. A. G. Ferreira, G. A. Bezerra, F. J. A.Matos, G. S. B. Viana (May 2000). "Antinociceptive, anti-inflammatory and bronchodilator activities of Brazilian medicinal plants containing coumarin: a comparative study". Journal of Ethnopharmacology. 70 (2): 151–159. doi:10.1016/S0378-8741(99)00165-8. ISSN 0378-8741. PMID 10771205.
↑ Lino CS, M. L. Taveira, G. S. B. Viana, F. J. A. Matos (1997). "Analgesic and antiinflammatory activities of Justicia pectoralis Jacq and its main constituents: coumarin and umbelliferone". Phytotherapy Research. 11 (3): 211–215. doi:10.1002/(SICI)1099-1573(199705)11:3<211::AID-PTR72>3.0.CO;2-W. S2CID 84525194. Archived from the original on 2013-01-05. Retrieved 2010-06-26.
↑ Ahluwalia VK (2010-09-30). Intermediates for Organic Synthesis. I. K. International. p. 211. ISBN 978-81-88237-33-3.
↑ Poirier D (Mar 2003). "Inhibitors of 17 beta-hydroxysteroid dehydrogenases". Curr Med Chem. 10 (6): 453–477. doi:10.2174/0929867033368222. PMID 12570693.
↑ P. Satyanarayana, P. Subrahmanyam, R. Kasai, O. Tanaka (1985). "An apiose-containing coumarin glycoside from gmelina arborea root". Phytochemistry. 24 (8): 1862–1863. Bibcode:1985PChem..24.1862S. doi:10.1016/S0031-9422(00)82575-3.

External links

USDA ARS info on uses

This page is based on this Wikipedia article
Text is available under the CC BY-SA 4.0 license; additional terms may apply.
Images, videos and audio are available under their respective licenses.

[1] Ohta T, Watanabe K, Moriya M, Shirasu Y, Kada T (1983). "Anti-mutagenic effects of coumarin and umbelliferone on mutagenesis induced by 4-nitroquinoline 1-oxide or UV irradiation in e. Coli". Mutation Research. 117 (1–2): 135–138. doi:10.1016/0165-1218(83)90160-x. PMID 6403855.

[2] Du L (2008). "Rational design of a fluorescent hydrogen peroxide probe based on the umbelliferone fluorophore". Tetrahedron Letters. 49 (19): 3045–3048. doi:10.1016/j.tetlet.2008.03.063. PMC 2490821 . PMID 19081820.

[3] "UMBELLIFERONE". www.chemicalland21.com. Retrieved 21 November 2011.

[pmc-4] Sim MO, Lee HI, Ham JR, Seo KI, Kim MJ, Lee MK (2015). "Anti-inflammatory and antioxidant effects of umbelliferone in chronic alcohol-fed rats". Nutr Res Pract. 9 (4): 364–369. doi:10.4162/nrp.2015.9.4.364. PMC 4523479 . PMID 26244074.

[Leal_et_al-5] Leal LK, A. A. G. Ferreira, G. A. Bezerra, F. J. A.Matos, G. S. B. Viana (May 2000). "Antinociceptive, anti-inflammatory and bronchodilator activities of Brazilian medicinal plants containing coumarin: a comparative study". Journal of Ethnopharmacology. 70 (2): 151–159. doi:10.1016/S0378-8741(99)00165-8. ISSN 0378-8741. PMID 10771205.

[Lino_et_al-6] Lino CS, M. L. Taveira, G. S. B. Viana, F. J. A. Matos (1997). "Analgesic and antiinflammatory activities of Justicia pectoralis Jacq and its main constituents: coumarin and umbelliferone". Phytotherapy Research. 11 (3): 211–215. doi:10.1002/(SICI)1099-1573(199705)11:3<211::AID-PTR72>3.0.CO;2-W. S2CID 84525194. Archived from the original on 2013-01-05. Retrieved 2010-06-26.

[7] Ahluwalia VK (2010-09-30). Intermediates for Organic Synthesis. I. K. International. p. 211. ISBN 978-81-88237-33-3.

[Poirier-8] Poirier D (Mar 2003). "Inhibitors of 17 beta-hydroxysteroid dehydrogenases". Curr Med Chem. 10 (6): 453–477. doi:10.2174/0929867033368222. PMID 12570693.

[9] P. Satyanarayana, P. Subrahmanyam, R. Kasai, O. Tanaka (1985). "An apiose-containing coumarin glycoside from gmelina arborea root". Phytochemistry. 24 (8): 1862–1863. Bibcode:1985PChem..24.1862S. doi:10.1016/S0031-9422(00)82575-3.

[1]

[2]

[3]

[4]

[5]

[6]

[7]

[8]

[9]