Caryophyllene

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Caryophyllene
Beta-Caryophyllen.svg
Names
Preferred IUPAC name
(1R,4E,9S)-4,11,11-Trimethyl-8-methylidenebicyclo[7.2.0]undec-4-ene
Other names
β-Caryophyllene
trans-(1R,9S)-8-Methylene-4,11,11-trimethylbicyclo[7.2.0]undec-4-ene
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.001.588
UNII
Properties
C15H24
Molar mass 204.357 g·mol−1
Density 0.9052 g/cm3 (17 °C)[1]
Boiling point 262–264 °C (504–507 °F; 535–537 K)[2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Caryophyllene /ˌkæriˈfɪln/, more formally (−)-β-caryophyllene, is a natural bicyclic sesquiterpene that is a constituent of many essential oils, especially clove oil, the oil from the stems and flowers of Syzygium aromaticum (cloves),[3] the essential oil of Cannabis sativa, rosemary,[4] and hops.[5] It is usually found as a mixture with isocaryophyllene (the cis double bond isomer) and α-humulene (obsolete name: α-caryophyllene), a ring-opened isomer. Caryophyllene is notable for having a cyclobutane ring, as well as a trans-double bond in a 9-membered ring, both rarities in nature.

The first total synthesis of caryophyllene in 1964 by E. J. Corey was considered one of the classic demonstrations of the possibilities of synthetic organic chemistry at the time.[6]

Caryophyllene is one of the chemical compounds that contributes to the aroma of black pepper.[7]

Metabolism and derivatives[edit]

14-Hydroxycaryophyllene oxide (C15H24O2) was isolated from the urine of rabbits treated with (−)-caryophyllene (C15H24). The X-ray crystal structure of 14-hydroxycaryophyllene (as its acetate derivative) has been reported.[citation needed]

The metabolism of caryophyllene progresses through (−)-caryophyllene oxide (C15H24O) since the latter compound also afforded 14-hydroxycaryophyllene (C15H24O) as a metabolite.[8]

Caryophyllene (C15H24) → caryophyllene oxide (C15H24O) → 14-hydroxycaryophyllene (C15H24O) → 14-hydroxycaryophyllene oxide (C15H24O2).

Caryophyllene oxide,[9] in which the alkene group of caryophyllene has become an epoxide, is the component responsible for cannabis identification by drug-sniffing dogs[10][11] and is also an approved food flavoring.[clarification needed][citation needed]

Natural sources[edit]

The approximate quantity of caryophyllene in the essential oil of each source is given in square brackets ([ ]):

Biosynthesis[edit]

Caryophyllene is a common sesquiterpene among plant species. It is biosynthesized from the common terpene precursors dimethylallyl pyrophosphate (DMAPP) and isopentenyl pyrophosphate (IPP). First, single units of DMAPP and IPP are reacted via an SN1-type reaction with the loss of pyrophosphate, catalyzed by the enzyme GPPS2, to form geranyl pyrophosphate (GPP). This further reacts with a second unit of IPP, also via an SN1-type reaction catalyzed by the enzyme IspA, to form farnesyl pyrophosphate (FPP). Finally, FPP undergoes QHS1 enzyme-catalyzed intramolecular cyclization to form caryophyllene.[28]

Biosynthesis of caryophyllene

Compendial status[edit]

Notes and references[edit]

  1. ^ SciFinder Record, CAS Registry Number 87-44-5
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  4. ^ a b Ormeño, E.; Baldy, V.; Ballini, C.; Fernández, C. (September 2008). "Production and diversity of volatile terpenes from plants on calcareous and siliceous soils: effect of soil nutrients". Journal of Chemical Ecology. 34 (9): 1219–1229. doi:10.1007/s10886-008-9515-2. PMID 18670820.
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  7. ^ a b Jirovetz, L.; Buchbauer, G.; Ngassoum, M. B.; Geissler, M. (November 2002). "Aroma compound analysis of Piper nigrum and Piper guineense essential oils from Cameroon using solid-phase microextraction–gas chromatography, solid-phase microextraction–gas chromatography–mass spectrometry and olfactometry". Journal of Chromatography A. 976 (1–2): 265–275. doi:10.1016/S0021-9673(02)00376-X. PMID 12462618.
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  18. ^ Vasconcelos Silva, M. G.; Abreu Matos, F. J.; Oliveira Lopes, P. R.; Oliveira Silva, F.; Tavares Holanda, M. (August 2, 2004). Cragg, G. M.; Bolzani, V. S.; Rao, G. S. R. S. (eds.). "Composition of essential oils from three Ocimum species obtained by steam and microwave distillation and supercritical CO2 extraction" (PDF). Arkivoc. 2004 (6): 66–71. doi:10.3998/ark.5550190.0005.609. ISSN 1424-6376. Retrieved September 6, 2010.
  19. ^ Harvala C, Menounos P, Argyriadou N (February 1987). "Essential oil from Origanum dictamnus". Planta Medica. 53 (1): 107–109. doi:10.1055/s-2006-962640. PMID 17268981.
  20. ^ Calvo Irabién, L. M.; Yam-Puc, J. A.; Dzib, G.; Escalante Erosa, F.; Peña Rodríguez, L. M. (July 2009). "Effect of postharvest drying on the composition of Mexican oregano (Lippia graveolens) essential oil". Journal of Herbs, Spices & Medicinal Plants. 15 (3): 281–287. doi:10.1080/10496470903379001. ISSN 1540-3580.
  21. ^ Mockutė, D.; Bernotienė, G.; Judžentienė, A. (May 2001). "The essential oil of Origanum vulgare L. ssp. vulgare growing wild in Vilnius district (Lithuania)". Phytochemistry. 57 (1): 65–69. doi:10.1016/s0031-9422(00)00474-x. PMID 11336262.
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  24. ^ Kaul, P. N.; Bhattacharya, A. K.; Rao, B. R.; et al. (2003). "Volatile constituents of essential oils isolated from different parts of cinnamon (Cinnamomum zeylanicum Blume)". Journal of the Science of Food and Agriculture. 83 (1): 53–55. doi:10.1002/jsfa.1277.
  25. ^ Ahmed, A.; Choudhary, M. I.; Farooq, A.; et al. (2000). "Essential oil constituents of the spice Cinnamomum tamala (Ham.) Nees & Eberm". Flavour and Fragrance Journal. 15 (6): 388–390. doi:10.1002/1099-1026(200011/12)15:6<388::AID-FFJ928>3.0.CO;2-F.
  26. ^ Leandro, L. M.; Vargas, F. S.; Barbosa, P. C.; Oliveira Neves, J. K.; Da Silva, J. A.; Da Veiga Junior, V. F. (2012). "Chemistry and biological activities of terpenoids from copaiba (Copaifera spp.) oleoresins". Molecules. 17 (4): 3866–3889. doi:10.3390/molecules17043866. PMC 6269112. PMID 22466849.
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  28. ^ Yang, J.; Li, Z.; Guo, L.; Du, J.; Bae, H.-J. (2016-12-01). "Biosynthesis of β-caryophyllene, a novel terpene-based high-density biofuel precursor, using engineered Escherichia coli". Renewable Energy. 99: 216–223. doi:10.1016/j.renene.2016.06.061. ISSN 0960-1481.
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