Monoterpene

Monoterpenes are a class of terpenes that consist of two isoprene units and have the molecular formula C10H16. Monoterpenes may be linear (acyclic) or contain rings (monocyclic and bicyclic). Modified terpenes, such as those containing oxygen functionality or missing a methyl group, are called monoterpenoids. Monoterpenes and monoterpenoids are diverse. They have relevance to the pharmaceutical, cosmetic, agricultural, and food industries.[1]

## Contents

* 1 Biosynthesis
* 2 Main examples
* 3 Natural roles
* 4 Uses
* 5 Health effects
* 6 See also
* 7 References

## Biosynthesis

Monoterpenes are derived biosynthetically from units of isopentenyl pyrophosphate, which is formed from acetyl-CoA via the intermediacy of mevalonic acid in the HMG-CoA reductase pathway. An alternative, unrelated biosynthesis pathway of IPP is known in some bacterial groups and the plastids of plants, the so-called MEP-(2-methyl-D-erythritol-4-phosphate) pathway, which is initiated from C5 sugars. In both pathways, IPP is isomerized to DMAPP by the enzyme isopentenyl pyrophosphate isomerase.

Geranyl pyrophosphate is the precursor to monoterpenes (and hence monoterpenoids).[2] Elimination of the pyrophosphate group from geranyl pyrophosphate leads to the formation of acyclic monoterpenes such as ocimene and the myrcenes. Hydrolysis of the phosphate groups leads to the prototypical acyclic monoterpenoid geraniol. Additional rearrangements and oxidations provide compounds such as citral, citronellal, citronellol, linalool, and many others. Many monoterpenes found in marine organisms are halogenated, such as halomon.

## Main examples

* Selected Monoterpenes and Monoterpenoids[lower-alpha 1]
* Myrcene is an acyclic monoterpene, an alkene hydrocarbon.[lower-alpha 2]

* Menthol is a monocyclic monoterpenoid.

* Limonene is a monocyclic monoterpene.

* Carvone is a monoterpenoid.

* Hinokitiol is a monoterpenoid, a tropolone derivative.

* Linalool is an acyclic monoterpenoid.

Bicyclic monoterpenes include carene, sabinene, camphene, and thujene. Camphor, borneol, eucalyptol and ascaridole are examples of bicyclic monoterpenoids containing ketone, alcohol, ether, and bridging peroxide functional groups, respectively.[3][4] Umbellulone is another example of bicyclic monoterpene ketone.

1. ↑ Notation is discussed at Stereochemistry
2. ↑ CH2 and CH3 side chains are drawn explicitly in this diagram rather than being implied by omission, as is commonly seen.

## Natural roles

Monoterpenes are found in many parts of different plants, such as barks, heartwood, bark and leaves of coniferous trees, in vegetables, fruits and herbs.[5] Essential oils are very rich in monoterpenes. Several monoterpenes produced by trees, such as linalool, hinokitiol, and ocimene have fungicidal and antibacterial activities and participate in wound healing.[6] Some of these compounds are produced to protect the trees from insect attacks.

Monoterpenes are emitted by forests and form aerosols that are proposed to serve as cloud condensation nuclei (CCN). Such aerosols can increase the brightness of clouds and cool the climate.[7]

Many monoterpenes have unique smell and flavor. For example, sabinene contributes to the spicy taste of black pepper, 3-carene gives cannabis an earthy taste and smell, citral has a lemon-like pleasant odor and contributes to the distinctive smell of citrus fruits, and thujene and carvacrol are responsible for the pungent flavors of summer savory and oregano, respectively.[8][9][10]

Monoterpenes are considered allelochemicals.[11]

## Uses

Many monoterpenes are volatile compounds and some of them are well-known fragrants found in the essential oils of many plants.[12] For example, camphor, citral, citronellol, geraniol, grapefruit mercaptan, eucalyptol, ocimene, myrcene, limonene, linalool, menthol, camphene and pinenes are used in perfumes and cosmetic products. Limonene and perillyl alcohol are used in cleaning products.[13][14]

Many monoterpenes are used as food flavors and food additives, such as bornyl acetate, citral, eucalyptol, menthol, hinokitiol, camphene and limonene.[15][16] Menthol, hinokitiol and thymol are also used in oral hygiene products. Thymol also has antiseptic and disinfectant properties.[17]

Volatile monoterpenes produced by plants can attract or repel insects, thus some of them are used in insect repellents, such as citronellol, eucalyptol, limonene, linalool, hinokitiol, menthol and thymol.[16]

Ascaridole, camphor and eucalyptol are monoterpenes that have pharmaceutical use.[18][19]

## Health effects

A study suggests that a range of floor cleaners with certain monoterpenes may cause indoor air pollution equivalent or exceeding the harm to respiratory tracts when the time is spent near a busy road. This is due to ozonolysis of monoterpenes like limonene leading to the production of atmospheric SOA.[20][21] Another study suggests monoterpenes substantially affect ambient organic aerosol with uncertainties regarding environmental impacts.[22] In a review, scientists concluded that they hope that these "substances will be extensively studied and used in more and more in medicine".[23] A 2013 study found that "Based on adverse effects and risk assessments, d-limonene may be regarded as a safe ingredient. However, the potential occurrence of skin irritation necessitates regulation of this chemical as an ingredient in cosmetics."[24][better source needed] According to a review, several studies showed "that some monoterpenes (e.g., pulegone, menthofuran, camphor, and limonene) and sesquiterpenes (e.g., zederone, germacrone) exhibited liver toxicity" and that i.a. intensive research on terpenes toxicity is needed.[25]

## See also

* Terpene
* Terpenoid
* Diterpene
* Sesquiterpene

## References

1. ↑ Eberhard Breitmaier (2006). "Hemi- and Monoterpenes". Terpenes: Flavors, Fragrances, Pharmaca, Pheromones. pp. 10–23. doi:10.1002/9783527609949.ch2. ISBN 978-3-527-60994-9.
2. ↑ Davis, Edward M.; Croteau, Rodney (2000). "Cyclization enzymes in the biosynthesis of monoterpenes, sesquiterpenes, and diterpenes". Topics in Current Chemistry 209: 53–95. doi:10.1007/3-540-48146-X_2. ISBN 978-3-540-66573-1.
3. ↑ Brown, R.T. (1975). "Bicyclic Monoterpenoids". Supplements to the 2nd Edition of Rodd's Chemistry of Carbon Compounds: 53–93. doi:10.1016/B978-044453346-3.50098-6. ISBN 978-0-444-53346-3.
4. ↑ Vil', Vera; Yaremenko, Ivan; Ilovaisky, Alexey; Terent'ev, Alexander (2 November 2017). "Peroxides with Anthelmintic, Antiprotozoal, Fungicidal and Antiviral Bioactivity: Properties, Synthesis and Reactions". Molecules 22 (11): 1881. doi:10.3390/molecules22111881. PMID 29099089.
5. ↑ Sjöström, Eero (22 October 2013). "Chapter 5: Extractives". Wood Chemistry: Fundamentals and Applications (Second ed.). San Diego. ISBN 978-0-08-092589-9.
6. ↑ Rowell, Roger M. (2013). "Chater 3: Cell Wall Chemistry". Handbook of Wood Chemistry and Wood Composites (2nd ed.). Boca Raton: Taylor & Francis. ISBN 978-1-4398-5380-1.
7. ↑ D. V. Spracklen; B. Bonn; K. S. Carslaw (2008). "Boreal forests, aerosols and the impacts on clouds and climate". Philosophical Transactions of the Royal Society A 366 (1885): 4613–26. doi:10.1098/rsta.2008.0201. PMID 18826917. Bibcode: 2008RSPTA.366.4613S. http://homepages.see.leeds.ac.uk/~eardvs/papers/spracklen08c.pdf.
8. ↑ Tamer, Canan Ece; Suna, Senem; Özcan-Sinir, Gülşah (2019). "14 - Toxicological Aspects of Ingredients Used in Nonalcoholic Beverages". Non-alcoholic beverages. Volume 6: The Science of Beverages. Duxford, United Kingdom: Woodhead Publishing. pp. 441–481. doi:10.1016/B978-0-12-815270-6.00014-1. ISBN 978-0-12-815270-6. https://www.sciencedirect.com/science/article/pii/B9780128152706000141.
9. ↑ PDR for herbal medicines. (4th ed.). Montvale, NJ: Thomson. 2007. p. 802. ISBN 978-1-56363-512-0.
10. ↑ "Herbs of the Labiatae". Encyclopedia of food sciences and nutrition (2nd ed.). Amsterdam: Academic Press. 2003. pp. 3082–3090. doi:10.1016/B0-12-227055-X/00593-9. ISBN 978-0-12-227055-0. https://www.sciencedirect.com/science/article/pii/B012227055X005939.
11. ↑ Saeidnia, Soodabeh; Gohari, Ahmad Reza (2012). "Trypanocidal Monoterpenes". Studies in Natural Products Chemistry 37: 173–190. doi:10.1016/B978-0-444-59514-0.00006-7. ISBN 978-0-444-59514-0.
12. ↑ Loza-Tavera, Herminia (1999). "Monoterpenes in Essential Oils". Chemicals via Higher Plant Bioengineering. Advances in Experimental Medicine and Biology. 464. pp. 49–62. doi:10.1007/978-1-4615-4729-7_5. ISBN 978-1-4613-7143-4.
13. ↑ "Limonene" (in en). https://pubchem.ncbi.nlm.nih.gov/compound/___-Limonene#section=Use-and-Manufacturing.
14. ↑ Laszlo, Pierre (2007). Citrus: A history. Chicago: University of Chicago Press. ISBN 978-0-226-47028-3.
15. ↑ Caputi, Lorenzo; Aprea, Eugenio (1 January 2011). "Use of Terpenoids as Natural Flavouring Compounds in Food Industry". Recent Patents on Food, Nutrition & Agriculture 3 (1): 9–16. doi:10.2174/2212798411103010009. PMID 21114471.
16. ↑ 16.0 16.1 Comprehensive natural products chemistry (1st ed.). Amsterdam: Elsevier. 1999. p. 306. ISBN 978-0-08-091283-7.
17. ↑ "R.E.D. FACTS: Thymol". https://archive.epa.gov/pesticides/reregistration/web/pdf/3143fact.pdf.
18. ↑ "Camphor Cream and Ointment Information" (in en). https://www.drugs.com/cdi/camphor-cream-and-ointment.html.
19. ↑ Tisserand, Robert (2014). "Chapter 13: Essential oil profiles". Essential oil safety: a guide for health care professionals (Second ed.). Edinburgh: Churchill Livingstone. ISBN 978-0-443-06241-4. https://www.sciencedirect.com/science/article/pii/B9780443062414000138.
20. ↑ "Cleaning products cause indoor pollution levels similar to a busy road". New Scientist. https://www.newscientist.com/article/2309721-cleaning-products-cause-indoor-pollution-levels-similar-to-a-busy-road/.
21. ↑ Rosales, Colleen Marciel F.; Jiang, Jinglin; Lahib, Ahmad; Bottorff, Brandon P.; Reidy, Emily K.; Kumar, Vinay; Tasoglou, Antonios; Huber, Heinz et al. (25 February 2022). "Chemistry and human exposure implications of secondary organic aerosol production from indoor terpene ozonolysis". Science Advances 8 (8). doi:10.1126/sciadv.abj9156. ISSN 2375-2548. PMID 35213219. Bibcode: 2022SciA....8J9156R.
22. ↑ Zhang, Haofei; Yee, Lindsay D.; Lee, Ben H.; Curtis, Michael P.; Worton, David R.; Isaacman-VanWertz, Gabriel; Offenberg, John H.; Lewandowski, Michael et al. (12 February 2018). "Monoterpenes are the largest source of summertime organic aerosol in the southeastern United States". Proceedings of the National Academy of Sciences 115 (9): 2038–2043. doi:10.1073/pnas.1717513115. ISSN 0027-8424. PMID 29440409. Bibcode: 2018PNAS..115.2038Z.
23. ↑ Wojtunik-Kulesza, Karolina A.; Kasprzak, Kamila; Oniszczuk, Tomasz; Oniszczuk, Anna (8 November 2019). "Natural Monoterpenes: Much More than Only a Scent". Chemistry & Biodiversity 16 (12). doi:10.1002/cbdv.201900434. ISSN 1612-1872. PMID 31587473.
24. ↑ Kim, Young Woo; Kim, Min Ji; Chung, Bu Young; Bang, Du Yeon; Lim, Seong Kwang; Choi, Seul Min; Lim, Duck Soo; Cho, Myung Chan et al. (1 January 2013). "Safety Evaluation And Risk Assessment Of d-Limonene". Journal of Toxicology and Environmental Health, Part B 16 (1): 17–38. doi:10.1080/10937404.2013.769418. ISSN 1093-7404. PMID 23573938. Bibcode: 2013JTEHB..16...17K.
25. ↑ Zárybnický, Tomáš; Boušová, Iva; Ambrož, Martin; Skálová, Lenka (1 January 2018). "Hepatotoxicity of monoterpenes and sesquiterpenes" (in en). Archives of Toxicology 92 (1): 1–13. doi:10.1007/s00204-017-2062-2. ISSN 1432-0738. PMID 28905185. Bibcode: 2018ArTox..92....1Z.

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Types of terpenes and terpenoids (# of isoprene units)

Basic forms:|

* Acyclic (linear, cis and trans forms)
* Monocyclic (single ring)
* Bicyclic (2 rings)
* Iridoids (cyclopentane ring)
* Iridoid glycosides (iridoids bound to a sugar)
* Steroids (4 rings)

Hemiterpenoids (1)|

* Isoprene (C5H8)
* Prenol
* Isovaleric acid

Monoterpene (C10H16)(2)|

| Acyclic|

* Ocimene
* Myrcenes

|

Monocyclic|

* Limonene
* Terpinene
* Phellandrene
* Umbellulone

Bicyclic|

* Pinene (β and α)
* Camphene
* Thujene
* Sabinene
* Carene

Monoterpenoids (2,modified)|

| Acyclic|

* Linalool
* Citronellal
* Citral
* Citronellol
* Geraniol
* Geranyl pyrophosphate

|

Monocyclic|

* Grapefruit mercaptan
* menthol
* p-Cymene
* thymol
* Perillyl alcohol
* Carvacrol

Bicyclic|

* Camphor
* Borneol
* Eucalyptol
* Halomon
* Pinene
* Ascaridole

Sesquiterpenoids (3)|

* Farnesyl pyrophosphate
* Artemisinin
* Bisabolol

Diterpenoids (4)|

* Geranylgeranyl pyrophosphate
* Gibberellin
* Retinol
* Retinal
* Phytol
* Taxol
* Forskolin
* Aphidicolin
* Salvinorin A

Sesterterpenoids (5)|

* geranylfarnesol

Triterpenoids (6)|

| Steroids|

* Phytosterols
* Campesterol
* beta Sitosterol
* gamma sitosterol
* Stigmasterol
* Tocopherols
* Cholesterol
* Testosterone
* Cholecalciferol (Vit D)
* Ecdysones

|

Other|

* Saponins
* Squalane
* Lanosterol
* Acids
* Oleanolic acid
* Ursolic acid
* Betulinic acid
* Moronic acid

Sesquarterpenes/oids (7)|

* ferrugicadiol
* tetraprenylcurcumene

Tetraterpenoids
(Carotenoids) (8)|

| Carotenes|

* Alpha-Carotene
* Beta-Carotene
* Gamma-Carotene
* Delta-Carotene
* Lycopene
* Neurosporene
* Phytofluene
* Phytoene

|

Xanthophylls:|

* Canthaxanthin
* Cryptoxanthin
* Zeaxanthin
* Astaxanthin
* Lutein
* Rubixanthin

Polyterpenoids (many)|

* sap, resins, latex of many plants, e.g. rubber

Norisoprenoids (modified)|

* 3-oxo-α-ionol
* 7,8-dihydroionone

Synthesis|

* Terpene synthase enzymes (many), having in common a Terpene synthase N terminal domain (protein domain)

Activated isoprene forms|

* Isopentenyl pyrophosphate (IPP)
* Dimethylallyl pyrophosphate (DMAPP)

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