Phellandrene

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Phellandrenes
a-Phellandrene Phellandrene alpha.svg
α-Phellandrene
α-Phellandrene
b-Phellandrene Phellandrene beta.svg
β-Phellandrene
β-Phellandrene
Names
IUPAC names
(α): 2-Methyl-5-(propan-2-yl)cyclohexa-1,3-diene
(β): 3-Methylidene-6-(propan-2-yl)cyclohex-1-ene
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.014.121 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • (α):202-792-5
  • (β):209-081-9
  • (−)-(α):224-167-6
KEGG
PubChem CID
UNII
  • (α):InChI=1S/C10H16/c1-8(2)10-6-4-9(3)5-7-10/h4-6,8,10H,7H2,1-3H3
    Key: OGLDWXZKYODSOB-UHFFFAOYSA-N
  • (β):InChI=1S/C10H16/c1-8(2)10-6-4-9(3)5-7-10/h4,6,8,10H,3,5,7H2,1-2H3
    Key: LFJQCDVYDGGFCH-UHFFFAOYSA-N
  • (−)-(α):InChI=1S/C10H16/c1-8(2)10-6-4-9(3)5-7-10/h4-6,8,10H,7H2,1-3H3/t10-/m1/s1
    Key: OGLDWXZKYODSOB-SNVBAGLBSA-N
  • (+)-(α):InChI=1S/C10H16/c1-8(2)10-6-4-9(3)5-7-10/h4-6,8,10H,7H2,1-3H3/t10-/m0/s1
    Key: OGLDWXZKYODSOB-JTQLQIEISA-N
  • (α):CC1=CCC(C=C1)C(C)C
  • (β):CC(C)C1CCC(=C)C=C1
  • (−)-(α):CC1=CC[C@@H](C=C1)C(C)C
  • (+)-(α):CC1=CC[C@H](C=C1)C(C)C
Properties [1]
C10H16
Molar mass 136.24 g/mol
AppearanceColorless oil (α and β)
Density α: 0.846 g/cm3
β: 0.85 g/cm3
Boiling point α: 171-172 °C
β: 171-172 °C
Insoluble (α and β)
Hazards
GHS labelling:
GHS-pictogram-flamme.svg GHS-pictogram-silhouette.svg
Danger
H226, H304
P210, P233, P240, P241, P242, P243, P280, P301+P310, P303+P361+P353, P331, P370+P378, P403+P235, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Phellandrenes are organic compounds with the formula C10H20. have a similar molecular structure and similar chemical properties. α-Phellandrene and β-phellandrene are cyclic monoterpenes and are double-bond isomers. In α-phellandrene, both double bonds are endocyclic, and in β-phellandrene, one of them is exocyclic. Both are insoluble in water, but miscible with organic solvents.

Contents

Etymology and occurrence

α-Phellandrene was named after Eucalyptus phellandra, now called Eucalyptus radiata , from which it can be isolated. [2] It is also a constituent of the essential oil of Eucalyptus dives . [3] β-Phellandrene has been isolated from the oil of water fennel and Canada balsam oil. The main source of β-phellandrene is terpentine. [4]

β-pinene is a source of β-phellandrene. [4]


Reactions and uses

α-Phellandrene undergoes hydrochlorination to give phellandrene hydrochloride (a cyclohexenyl chloride). Base hydrolysis of this hydrochloride gives piperitol. [4]

The phellandrenes are used in fragrances because of their pleasing aromas. The odor of β-phellandrene has been described as peppery-minty and slightly citrusy.

Like other cyclohexadienes, α-phellandrene reacts with ruthenium trichloride to give (cymene)ruthenium chloride dimer.

Biosynthesis

The biosynthesis of phellandrene begins with dimethylallyl pyrophosphate and isopentenyl pyrophosphate condensing in an SN1 reaction to form geranyl pyrophosphate. The resultant monoterpene undergoes cyclization to form a menthyl cationic species. A hydride shift then forms an allylic carbocation. Finally, an elimination reaction occurs at one of two positions, yielding either α-phellandrene or β-phellandrene. [5]

Phellandrene mechanism.jpg

Safety

The α-phellandrene isomer can form hazardous and explosive peroxides on contact with air at elevated temperatures. [6]

Related Research Articles

<span class="mw-page-title-main">Alkene</span> Hydrocarbon compound containing one or more C=C bonds

In organic chemistry, an alkene, or olefin, is a hydrocarbon containing a carbon–carbon double bond. The double bond may be internal or in the terminal position. Terminal alkenes are also known as α-olefins.

<span class="mw-page-title-main">Carotene</span> Class of compounds

The term carotene (also carotin, from the Latin carota, "carrot") is used for many related unsaturated hydrocarbon substances having the formula C40Hx, which are synthesized by plants but in general cannot be made by animals (with the exception of some aphids and spider mites which acquired the synthesizing genes from fungi). Carotenes are photosynthetic pigments important for photosynthesis. Carotenes contain no oxygen atoms. They absorb ultraviolet, violet, and blue light and scatter orange or red light, and (in low concentrations) yellow light.

<span class="mw-page-title-main">Ester</span> Compound derived from an acid

In chemistry, an ester is a functional group derived from an acid in which the hydrogen atom (H) of at least one acidic hydroxyl group of that acid is replaced by an organyl group. Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well, but not according to the IUPAC.

<span class="mw-page-title-main">Thujone</span> Group of four possible stereoisomers found in various plants: a.o., absinthe and mint

Thujone is a ketone and a monoterpene that occurs predominantly in two diastereomeric (epimeric) forms: (−)-α-thujone and (+)-β-thujone.

<span class="mw-page-title-main">Terpene</span> Class of oily organic compounds found in plants

Terpenes are a class of natural products consisting of compounds with the formula (C5H8)n for n ≥ 2. Terpenes are major biosynthetic building blocks. Comprising more than 30,000 compounds, these unsaturated hydrocarbons are produced predominantly by plants, particularly conifers. In plants, terpenes and terpenoids are important mediators of ecological interactions, while some insects use some terpenes as a form of defense. Other functions of terpenoids include cell growth modulation and plant elongation, light harvesting and photoprotection, and membrane permeability and fluidity control.

<span class="mw-page-title-main">Geraniol</span> Monoterpenoid and alcohol that is the primary component of citronella oil

Geraniol is a monoterpenoid and an alcohol. It is the primary component of citronella oil and is a primary component of rose oil and palmarosa oil. It is a colorless oil, although commercial samples can appear yellow. It has low solubility in water, but it is soluble in common organic solvents. The functional group derived from geraniol is called geranyl.

<span class="mw-page-title-main">Linalool</span> Chemical compound with a floral aroma

Linalool refers to two enantiomers of a naturally occurring terpene alcohol found in many flowers and spice plants. Together with geraniol, nerol, citronellol, linalool is one of the rose alcohols. Linalool has multiple commercial applications, the majority of which are based on its pleasant scent.

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

Isoquinoline is an individual chemical specimen - a heterocyclic aromatic organic compound - as well as the name of a family of many thousands of natural plant alkaloids, any one of which might be referred to as "an isoquinoline". It is a structural isomer of quinoline. Isoquinoline and quinoline are benzopyridines, which are composed of a benzene ring fused to a pyridine ring. In a broader sense, the term isoquinoline is used to make reference to isoquinoline derivatives. 1-Benzylisoquinoline is the structural backbone in many naturally occurring alkaloids such as papaverine. The isoquinoline ring in these natural compound derives from the aromatic amino acid tyrosine.

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

Carvone is a member of a family of chemicals called terpenoids. Carvone is found naturally in many essential oils, but is most abundant in the oils from seeds of caraway, spearmint, and dill.

<span class="mw-page-title-main">Limonene</span> Liquid terpene hydrocarbon fragrance and flavor, extract of citrus peel

Limonene is a colorless liquid aliphatic hydrocarbon classified as a cyclic monoterpene, and is the major component in the essential oil of citrus fruit peels. The (+)-isomer, occurring more commonly in nature as the fragrance of oranges, is a flavoring agent in food manufacturing. It is also used in chemical synthesis as a precursor to carvone and as a renewables-based solvent in cleaning products. The less common (-)-isomer has a piny, turpentine-like odor, and is found in the edible parts of such plants as caraway, dill, and bergamot orange plants.

<span class="mw-page-title-main">Pinene</span> Oily organic chemical found in plants

Pinene is a collection of unsaturated bicyclic monoterpenes. Two geometric isomers of pinene are found in nature, α-pinene and β-pinene. Both are chiral. As the name suggests, pinenes are found in pines. Specifically, pinene is the major component of the liquid extracts of conifers. Pinenes are also found in many non-coniferous plants such as camphorweed (Heterotheca) and big sagebrush.

<span class="mw-page-title-main">Ruthenium(III) chloride</span> Chemical compound

Ruthenium(III) chloride is the chemical compound with the formula RuCl3. "Ruthenium(III) chloride" more commonly refers to the hydrate RuCl3·xH2O. Both the anhydrous and hydrated species are dark brown or black solids. The hydrate, with a varying proportion of water of crystallization, often approximating to a trihydrate, is a commonly used starting material in ruthenium chemistry.

p-Cymene is a naturally occurring aromatic organic compound. It is classified as an alkylbenzene related to monocyclic monoterpenes. Its structure consists of a benzene ring para-substituted with a methyl group and an isopropyl group. p-Cymene is insoluble in water, but miscible with organic solvents.

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

Caryophyllene, more formally (−)-β-caryophyllene (BCP), is a natural bicyclic sesquiterpene that occurs widely in nature. Caryophyllene is notable for having a cyclobutane ring, as well as a trans-double bond in a 9-membered ring, both rarities in nature.

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

Humulene, also known as α-humulene or α-caryophyllene, is a naturally occurring monocyclic sesquiterpene (C15H24), containing an 11-membered ring and consisting of 3 isoprene units containing three nonconjugated C=C double bonds, two of them being triply substituted and one being doubly substituted. It was first found in the essential oils of Humulus lupulus (hops), from which it derives its name. Humulene is an isomer of β-caryophyllene, and the two are often found together as a mixture in many aromatic plants.

The terpinenes are a group of isomeric hydrocarbons that are classified as monoterpenes. They each have the same molecular formula and carbon framework, but they differ in the position of carbon-carbon double bonds. α-Terpinene has been isolated from cardamom and marjoram oils, and from other natural sources. β-Terpinene has no known natural source but has been prepared from sabinene. γ-Terpinene and δ-terpinene have been isolated from a variety of plant sources. They are all colorless liquids with a turpentine-like odor.

α-Pinene Chemical compound

α-Pinene is an organic compound of the terpene class. It is one of the two isomers of pinene, the other being β-pinene. An alkene, it contains a reactive four-membered ring. It is found in the oils of many species of coniferous trees, notably Pinus and Picea species. It is also found in the essential oil of rosemary and Satureja myrtifolia. Both enantiomers are known in nature; (1S,5S)- or (−)-α-pinene is more common in European pines, whereas the (1R,5R)- or (+)-α-isomer is more common in North America. The enantiomers' racemic mixture is present in some oils such as eucalyptus oil and orange peel oil.

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

Succinic anhydride, is an organic compound with the molecular formula (CH2CO)2O. This colorless solid is the acid anhydride of succinic acid.

<span class="mw-page-title-main">Sesquiterpene</span> Class of terpenes

Sesquiterpenes are a class of terpenes that consist of three isoprene units and often have the molecular formula C15H24. Like monoterpenes, sesquiterpenes may be cyclic or contain rings, including many combinations. Biochemical modifications such as oxidation or rearrangement produce the related sesquiterpenoids. It is estimated (2006) that 3000 sesquiterpenes have been identified.

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

Terpineol is any of four isomeric monoterpenoids. Terpenoids are terpene that are modified by the addition of a functional group, in this case, an alcohol. Terpineols have been isolated from a variety of sources such as cardamom, cajuput oil, pine oil, and petitgrain oil. Four isomers exist: α-, β-, γ-terpineol, and terpinen-4-ol. β- and γ-terpineol differ only by the location of the double bond. Terpineol is usually a mixture of these isomers with α-terpineol as the major constituent.

References

  1. The Merck Index , 12th Edition, 7340, 7341
  2. Jacobs, S.W.L., Pickard, J., Plants of New South Wales, 1981, ISBN   0-7240-1978-2.
  3. Boland, D. J., Brophy, J. J., and A. P. N. House, Eucalyptus Leaf Oils, 1991, ISBN   0-909605-69-6.
  4. 1 2 3 Sell, Charles S. (2006). "Terpenoids". Kirk-Othmer Encyclopedia of Chemical Technology. doi:10.1002/0471238961.2005181602120504.a01.pub2. ISBN   0471238961.
  5. Dewick, Paul M. (9 March 2009). Medicinal natural products : a biosynthetic approach (3rd ed.). Chichester, West Sussex, United Kingdom. ISBN   9780470741689. OCLC   259265604.{{cite book}}: CS1 maint: location missing publisher (link)
  6. Urben, Peter (2007). Bretherick's Handobook of Reactive Chemical Hazards. Vol. 1 (7 ed.). Butterworth-Heinemann. p. 1154.