Hydrangine
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Umbelliferone, also known as 7-hydroxycoumarin, hydrangine, skimmetine, and ''beta''-umbelliferone, is a natural product of the
coumarin Coumarin () or 2''H''-chromen-2-one is an aromatic organic chemical compound with formula . Its molecule can be described as a benzene molecule with two adjacent hydrogen atoms replaced by an unsaturated lactone ring , forming a second six-me ...
family. It absorbs
ultraviolet Ultraviolet radiation, also known as simply UV, is electromagnetic radiation of wavelengths of 10–400 nanometers, shorter than that of visible light, but longer than X-rays. UV radiation is present in sunlight and constitutes about 10% of ...
light strongly at several wavelengths. There are some indications that this chemical is
antimutagenic Antimutagens are the agents that interfere with the mutagenicity of a substance. The interference can be in the form of prevention of the transformation of a promutagenic compound into actual active mutagen, inactivation, or otherwise the preventio ...
, it is used in
sunscreen Sunscreen, also known as sunblock, sun lotion or sun cream, is a photoprotection, photoprotective topical product for the Human skin, skin that helps protect against sunburn and prevent skin cancer. Sunscreens come as lotions, sprays, gels, fo ...
s. Umbelliferone has been reported to have antioxidant properties. It is a yellowish-white crystalline solid that has a slight solubility in hot water, but high solubility in
ethanol Ethanol (also called ethyl alcohol, grain alcohol, drinking alcohol, or simply alcohol) is an organic compound with the chemical formula . It is an Alcohol (chemistry), alcohol, with its formula also written as , or EtOH, where Et is the ps ...
.


Natural occurrences and name

Umbelliferone's name is from the
umbelliferae Apiaceae () or Umbelliferae is a family of mostly aromatic flowering plants named after the type genus '' Apium,'' and commonly known as the celery, carrot, or parsley family, or simply as umbellifers. It is the 16th-largest family of flowering ...
family of plants, and the plant family in turn was named for their
umbrella An umbrella or parasol is a folding canopy supported by wooden or metal ribs that is mounted on a wooden, metal, or plastic pole. It is usually designed to protect a person against rain. The term ''umbrella'' is traditionally used when protec ...
-shaped
inflorescence In botany, an inflorescence is a group or cluster of flowers arranged on a plant's Plant stem, stem that is composed of a main branch or a system of branches. An inflorescence is categorized on the basis of the arrangement of flowers on a mai ...
s, each called an
umbel UMBEL (Upper Mapping and Binding Exchange Layer) is a logically organized knowledge graph of 34,000 concepts and entity types that can be used in information science for relating information from disparate sources to one another. It was retired ...
. Umbelliferone occurs in many familiar plants from the
Apiaceae Apiaceae () or Umbelliferae is a family of mostly aromatic flowering plants named after the type genus ''Apium,'' and commonly known as the celery, carrot, or parsley family, or simply as umbellifers. It is the 16th-largest family of flowering p ...
(Umbelliferae) family such as
carrot The carrot ('' Daucus carota'' subsp. ''sativus'') is a root vegetable, typically orange in colour, though heirloom variants including purple, black, red, white, and yellow cultivars exist, all of which are domesticated forms of the wild ...
,
coriander Coriander (), whose leaves are known as cilantro () in the U.S. and parts of Canada, and dhania in parts of South Asia and Africa, is an annual plant, annual herb (''Coriandrum sativum'') in the family Apiaceae. Most people perceive the ...
and
garden angelica ''Angelica archangelica'', commonly known as angelica, garden angelica, wild celery, and Norwegian angelica, is a biennial plant from the family Apiaceae, a subspecies of which is cultivated for its sweetly scented edible stems and roots. Like s ...
, as well as in plants from other families, such as the mouse-ear hawkweed (''
Hieracium pilosella ''Pilosella officinarum'' (synonym ''Hieracium pilosella''), known as mouse-ear hawkweed, is a yellow-flowered species of flowering plant in the daisy family Compositae (= Asteraceae), native to Europe and northern Asia. It produces single, lemon ...
'', Asteraceae) or the bigleaf hydrangea (''
Hydrangea macrophylla ''Hydrangea macrophylla'' is a species of flowering plant in the family (biology), family Hydrangeaceae, native plant, native and endemism, endemic to Japan. It is a deciduous shrub growing to tall by or more broad with large heads of pink or ...
'', Hydrangeaceae, under the name hydrangine). It is one of the components of
asafoetida Asafoetida (; also spelled asafetida) is the dried latex (Natural gum, gum oleoresin) exuded from the rhizome or tap root of several species of ''Ferula'', perennial herbs of the carrot family. It is produced in Iran, Afghanistan, Central As ...
, the dried latex from the giant fennel (''
Ferula communis ''Ferula communis'', the giant fennel, is a species of flowering plant in the carrot family Apiaceae. It is related to the common fennel (''Foeniculum vulgare''), which belongs to the same family. ''Ferula communis'' is a tall herbaceous peren ...
''). It is also found in ''
Justicia pectoralis ''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 fr ...
'' (Acanthaceae).


Biosynthesis

Umbelliferone is a
phenylpropanoid 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 ...
and as such is synthesized from
L-phenylalanine Phenylalanine (symbol Phe or F) is an essential α-amino acid with the formula . It can be viewed as a benzyl group substituted for the methyl group of alanine, or a phenyl group in place of a terminal hydrogen of alanine. This essential amin ...
, which in turn is produced via the
shikimate pathway The shikimate pathway (shikimic acid pathway) is a seven-step metabolic pathway used by bacteria, archaea, fungi, algae, some protozoans, and plants for the biosynthesis of folates and aromatic amino acids (tryptophan, phenylalanine, and tyrosine) ...
. Phenylalanine is lyased into
cinnamic acid Cinnamic acid is an organic compound with the formula phenyl, C6H5-CH=CH-Carboxylic acid, COOH. It is a white crystalline compound that is slightly soluble in water, and freely soluble in many organic solvents. Classified as an unsaturated carboxy ...
, followed by
hydroxylation In chemistry, hydroxylation refers to the installation of a hydroxyl group () into an organic compound. Hydroxylations generate alcohols and phenols, which are very common functional groups. Hydroxylation confers some degree of water-solubility ...
by
cinnamate 4-hydroxylase In enzymology, a trans-cinnamate 4-monooxygenase () is an enzyme that catalyzes the chemical reaction :trans-cinnamate + NADPH + H+ + O2 \rightleftharpoons 4-hydroxycinnamate + NADP+ + H2O The 4 substrates of this enzyme are trans-cinnamate, N ...
to yield
4-coumaric acid ''p''-Coumaric acid is an organic compound with the formula HOC6H4CH=CHCO2H. It is one of the three isomers of coumaric acid. It is a white solid that is only slightly soluble in water but very soluble in ethanol and diethyl ether. Natural occur ...
. The 4-coumaric acid is again hydroxylated by cinnamate/coumarate 2-hydroxylase to yield 2,4-dihydroxy-cinnamic acid (
umbellic acid Umbellic acid (2,4-dihydroxycinnamic acid) is a hydroxycinnamic acid. It is an isomer of caffeic acid. It is a precursor in the umbelliferone biosynthesis pathway. Umbelliferone is a phenylpropanoid and as such is synthesized from L-phenylalanin ...
) followed by a bond rotation of the unsaturated bond adjacent to the
carboxylic acid In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group () attached to an Substituent, R-group. The general formula of a carboxylic acid is often written as or , sometimes as with R referring to an organyl ...
group. Finally an intramolecular attack from the hydroxyl group of C2' to the carboxylic acid group closes the ring and forms the
lactone Lactones are cyclic carboxylic esters. They are derived from the corresponding hydroxycarboxylic acids by esterification. They can be saturated or unsaturated. Lactones are formed by lactonization, the intramolecular esterification of the corresp ...
umbelliferone.
 \begin\\\xrightarrow\mathrm\\\end  \begin\\\xrightarrow\mathrm\\\end  \begin\\\xrightarrow\mathrm\\\end  \longrightarrow 


Chemical synthesis

Umbelliferone is traditionally synthesized using the
Pechmann condensation The Pechmann condensation is a synthesis of Coumarin derivatives, coumarins, starting from a phenol and a carboxylic acid or ester containing a β-carbonyl group. The condensation is performed under acidic conditions. The mechanism involves an e ...
, from
resorcinol Resorcinol (or resorcin) is a phenolic compound. It is an organic compound with the formula C6H4(OH)2. It is one of three isomeric benzenediols, the 1,3-isomer (or ''meta- (chemistry), meta''-isomer). Resorcinol crystallizes from benzene as co ...
and formylacetic acid (generated from
malic acid Malic acid is an organic compound with the molecular formula . It is a dicarboxylic acid that is made by all living organisms, contributes to the sour taste of fruits, and is used as a food additive. Malic acid has two stereoisomeric forms ( ...
''in situ''). : A newer synthesis uses
methyl propionate Methyl propionate, also known as methyl propanoate, is an organic compound with the molecular formula . It is a colorless liquid with a fruity, rum-like odor. Preparation Methyl propionate can be prepared by esterification of propionic acid with ...
and a
palladium Palladium is a chemical element; it has symbol Pd and atomic number 46. It is a rare and lustrous silvery-white metal discovered in 1802 by the English chemist William Hyde Wollaston. He named it after the asteroid Pallas (formally 2 Pallas), ...
catalyst Catalysis () is the increase in rate of a chemical reaction due to an added substance known as a catalyst (). Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quick ...
.


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
alkali In chemistry, an alkali (; from the Arabic word , ) is a basic salt of an alkali metal or an alkaline earth metal. An alkali can also be defined as a base that dissolves in water. A solution of a soluble base has a pH greater than 7.0. The a ...
ne solution, since the phenolic
hydroxyl In chemistry, a hydroxy or hydroxyl group is a functional group with the chemical formula and composed of one oxygen atom covalently bonded to one hydrogen atom. In organic chemistry, alcohols and carboxylic acids contain one or more hydroxy ...
group is
deprotonated Deprotonation (or dehydronation) is the removal (transfer) of a proton (or hydron, or hydrogen cation), (H+) from a Brønsted–Lowry acid in an acid–base reaction.Henry Jakubowski, Biochemistry Online Chapter 2A3, https://employees.csbsju.ed ...
( pKa = 7.7).


Uses

The ultraviolet activity of umbelliferone led to its use as a
sunscreen Sunscreen, also known as sunblock, sun lotion or sun cream, is a photoprotection, photoprotective topical product for the Human skin, skin that helps protect against sunburn and prevent skin cancer. Sunscreens come as lotions, sprays, gels, fo ...
agent, and an
optical brightener Optical brighteners, optical brightening agents (OBAs), fluorescent brightening agents (FBAs), or fluorescent whitening agents (FWAs), are chemical compounds that absorb light in the ultraviolet and violet region (usually 340-370 nm) of the ...
for
textiles Textile is an Hyponymy and hypernymy, umbrella term that includes various Fiber, fiber-based materials, including fibers, yarns, Staple (textiles)#Filament fiber, filaments, Thread (yarn), threads, and different types of #Fabric, fabric. ...
. It has also been used as a
gain medium The active laser medium (also called a gain medium or lasing medium) is the source of optical gain within a laser. The gain results from the stimulated emission of photons through electronic or molecular transitions to a lower energy state from ...
for
dye laser A dye laser is a laser that uses an organic dye as the lasing medium, usually as a liquid solution. Compared to gases and most solid state lasing media, a dye can usually be used for a much wider range of wavelengths, often spanning 50 to 100 n ...
s. Umbelliferone can be used as a
fluorescence Fluorescence is one of two kinds of photoluminescence, the emission of light by a substance that has absorbed light or other electromagnetic radiation. When exposed to ultraviolet radiation, many substances will glow (fluoresce) with colore ...
indicator for metal ions such as
copper Copper is a chemical element; it has symbol Cu (from Latin ) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkish-orang ...
and
calcium Calcium is a chemical element; it has symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar to it ...
. It acts as a pH indicator in the range 6.5-8.9. Umbelliferone is a potent inhibitor of type 3
17β-hydroxysteroid dehydrogenase A hydroxysteroid is a molecule derived from a steroid with a hydrogen replaced with a hydroxy group. When the hydroxy group is specifically at the C3 position, hydroxysteroids are referred to as sterols, with an example being cholesterol ...
, the primary enzyme responsible for the conversion of 4-androstene-3,17-dione to testosterone, with IC50 of 1.4 μM.


Derivatives

Umbelliferone is the parent compound for a large number of natural products.
Herniarin Herniarin is a natural chemical compound. Chemically, it can be considered a methoxy derivative of coumarin or a methyl derivative of umbelliferone. Herniarin is found in ''Herniaria glabra'', ''Ayapana triplinervis ''Ayapana triplinervis'' ( ...
(7-''O''-methylumbelliferone or 7-methoxycoumarin) occurs in the leaves of water hemp ('' Eupatorium ayapana'') and rupturewort (''
Herniaria ''Herniaria'' is a genus of flowering plants in the family Caryophyllaceae known generally as ruptureworts. They are native to Eurasia and Africa but several species have been widely introduced to other continents. These are flat, mat-forming ann ...
''). ''O''-Glycosylated derivatives such as skimmin (7-''O''-β-D-glucopyranosylumbelliferone) occur naturally and are used for the fluorimetric determination of
glycoside hydrolase In biochemistry, glycoside hydrolases (also called glycosidases or glycosyl hydrolases) are a class of enzymes which catalysis, catalyze the hydrolysis of glycosidic bonds in polysaccharide, complex sugars. They are extremely common enzymes, wi ...
enzyme An enzyme () is a protein that acts as a biological catalyst by accelerating chemical reactions. The molecules upon which enzymes may act are called substrate (chemistry), substrates, and the enzyme converts the substrates into different mol ...
s. Isoprenylated derivatives are also widespread, such as marmin (found in
grapefruit The grapefruit (''Citrus'' × ''paradisi'') is a subtropical citrus tree known for its relatively large, sour to semi-sweet, somewhat bitter fruit. The flesh of the fruit is segmented and varies in color from pale yellow to dark red. Grapefru ...
skin and in the bark of the Bael tree) and
furocoumarins The furanocoumarins, or furocoumarins, are a class of organic chemical compounds produced by a variety of plants. Most of the plant species found to contain furanocoumarins belong to a handful of plant families. The families Apiaceae and Rutacea ...
such as
marmesin Marmesin (nodakenetin) is a chemical compound precursor in psoralen and linear furanocoumarins biosynthesis. Marmesin plays a central role in the biosynthesis of furocoumarins in the plant ruta graveolens, more commonly known as rue. It acts as ...
,
angelicin 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 ...
, and
psoralen Psoralen (also called psoralene) is the parent compound in a family of naturally occurring organic compounds known as the linear furanocoumarins. It is structurally related to coumarin by the addition of a fused furan ring, and may be considered a ...
. :
Umbelliferone 7-apiosylglucoside Umbelliferone, also known as 7-hydroxycoumarin, hydrangine, skimmetine, and ''beta''-umbelliferone, is a natural product of the coumarin family. It absorbs ultraviolet light strongly at several wavelengths. There are some indications that this c ...
can be isolated from the root of ''
Gmelina arborea ''Gmelina arborea'', (in English beechwood, gmelina, goomar teak, Kashmir tree, Malay beechwood, white teak, yamane ), locally known as gamhar, is a fast-growing deciduous tree in the family Lamiaceae. Distribution and habitat ''Gmelina arborea ...
''.


See also

*
Aesculetin Aesculetin (also known as esculetin, 6,7-dihydroxycoumarin and cichorigenin) is a derivative of coumarin. It is a natural lactone that derives from the intramolecular cyclization of a cinnamic acid derivative. It is present in chicory and in many ...
*
Laser dye file:Coherent 899 dye laser.jpg, Close-up of a table-top dye laser using Rhodamine 6G as active medium. file:rhodamine 6G.svg, Molecular structure of Rhodamine 6G, perhaps the best known laser dye. A Laser dye is a dye used as laser medium in a dy ...
s


References


Further reading

* * *


External links


USDA ARS info on uses
{{coumarin Coumarins Fluorescent dyes Laser gain media Sunscreening agents