Limonene
| Limonene | |
|---|---|
| Skeletal structure of the R-isomer | Ball-and-stick model of the R-isomer |
| 1-methyl-4-(1-methylethenyl)-cyclohexene | |
| Other names 4-isopropenyl-1-methylcyclohexene | |
| Identifiers | |
| CAS number | 5989-27-5 7px |
| PubChem | 22311, 439250 (S-isomer) |
| ChemSpider | 20939 (Racemic) 7px, 388386 (S-isomer), 389747 (R-isomer) |
| UNII | GFD7C86Q1W 7px |
| KEGG | D00194 7px |
| ChEBI | CHEBI:15384 7px |
| ChEMBL | CHEMBL449062 7px |
| Jmol-3D images | Image 1 |
| |
| Molecular formula | C10H16 |
| Molar mass | 136.24 g/mol |
| Density | 0.8411 g/cm³ |
| Melting point |
-74.35 °C, 199 K, -102 °F |
| Boiling point |
176 °C, 449 K, 349 °F |
| Hazards | |
| R-phrases | R10 R38 R43 R50/53 |
| S-phrases | (S2) S24 S37 S60 S61 |
| NFPA 704 | |
| Flash point | 50 °C |
| 14px (verify) (what is: 10px/10px?) Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) | |
| Infobox references | |
Limonene is a colourless liquid hydrocarbon classified as a cyclic terpene. The more common D isomer possesses a strong smell of oranges.[1] It is used in chemical synthesis as a precursor to carvone and as a renewably based solvent in cleaning products.
Limonene takes its name from the lemon, as the rind of the lemon, like other citrus fruits, contains considerable amounts of this compound, which contributes to their odor. Limonene is a chiral molecule, and biological sources produce one enantiomer: the principal industrial source, citrus fruit, contains D-limonene ((+)-limonene), which is the (R)-enantiomer (CAS number 5989-27-5, EINECS number 227-813-5). Racemic limonene is known as dipentene.[2] D-Limonene is obtained commercially from citrus fruits through two primary methods: centrifugal separation or steam distillation.
Contents
Chemical reactions
Limonene is a relatively stable terpene and can be distilled without decomposition, although at elevated temperatures it cracks to form isoprene.[3] It oxidizes easily in moist air to produce carveol, carvone, and limonene oxide.[4] With sulfur, it undergoes dehydrogenation to p-cymene.[citation needed]
Limonene occurs naturally as the (R)-enantiomer, but racemizes to dipentene at 300 °C. When warmed with mineral acid, limonene isomerizes to the conjugated diene α-terpinene (which can also easily be converted to p-cymene). Evidence for this isomerization includes the formation of Diels-Alder adducts between α-terpinene adducts and maleic anhydride.
It is possible to effect reaction at one of the double bonds selectively. Anhydrous hydrogen chloride reacts preferentially at the disubstituted alkene, whereas epoxidation with MCPBA occurs at the trisubstituted alkene.
In another synthetic method Markovnikov addition of trifluoroacetic acid followed by hydrolysis of the acetate gives terpineol.
Biosynthesis
Limonene is formed from geranyl pyrophosphate, via cyclization of a neryl carbocation or its equivalent as shown.[5] The final step involves loss of a proton from the cation to form the alkene.
Uses
The most widely practiced conversion of limonene is to carvone. The three step reaction begins with the regioselective addition of nitrosyl chloride across the trisubstituted double bond. This species is then converted to the oxime with base, and the hydroxylamine is removed to give the ketone-containing carvone.[1]
Limonene is common in cosmetic products. As the main odor constituent of citrus (plant family Rutaceae), D-limonene is used in food manufacturing and some medicines, e.g. as a flavoring to mask the bitter taste of alkaloids, and as a fragrant in perfumery; it is also used as botanical insecticide,[6] particularly the (R)-(+)-enantiomer is most active as an insecticide. It is added to cleaning products such as hand cleansers to give a lemon-orange fragrance (see orange oil). In contrast, L-limonene has a piney, turpentine-like odor.
In natural and alternative medicine, D-limonene is marketed to relieve gastroesophageal reflux disease and heartburn.[7]
Limonene is increasingly being used as a solvent for cleaning purposes, such as the removal of oil from machine parts, as it is produced from a renewable source (citrus oil, as a byproduct of orange juice manufacture). It also serves as a paint stripper when applied to painted wood and is also useful as a fragrant alternative to turpentine. Limonene is also used as a solvent in some model airplane glues. All-natural commercial air fresheners, with air propellants, containing limonene are used by philatelists to remove self-adhesive postage stamps from envelope paper.[8]
As it is combustible, limonene has also been considered as a biofuel.[9]
Limonene can be used to dissolve polystyrene, and is a more ecologically friendly substitute for acetone.[citation needed]
In preparing tissues for histology or histopathology, D-limonene is often used as a less toxic substitute for xylene when clearing dehydrated specimens. Clearing agents are liquids miscible with alcohols (such as ethanol or isopropanol) and with melted paraffin wax, in which specimens are embedded to facilitate cutting of thin sections for microscopy.[10][11][12]
Safety
Limonene and its oxidation products are skin and respiratory irritants, and limonene-1,2-oxide (formed by aerial oxidation) is a known skin sensitizer. Most reported cases of irritation have involved long-term industrial exposure to the pure compound, e.g. during degreasing or the preparation of paints. However, a study of patients presenting dermatitis showed that 3% were sensitized to limonene.[13]
Although high doses have been shown to cause renal cancer in male rats,[14] limonene is considered by some researchers to be a potential chemopreventive agent [15] with value as a dietary anti-cancer tool in humans.[16] There is no evidence for carcinogenicity or genotoxicity in humans. The IARC classifies D-limonene as a Group 3 carcinogen: not classifiable as to its carcinogenicity to humans.[13][17]
No information is available on the health effects of inhalation exposure to D-limonene in humans,[dubious ] and no long-term inhalation studies have been conducted in laboratory animals.[citation needed]
D-Limonene is biodegradable, but due to its low flash point, it must be treated as hazardous waste for disposal.[citation needed]
Compendial status
See also
References
- ↑ 1.0 1.1 Script error
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- ↑ EPA R.E.D. Fact Sheet on Limonene, September 1994
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- ↑ Cyclone Power to Showcase External Combustion Engine at SAE Event, Green Car Congress, 20 September 2007
- ↑ Script error
- ↑ Carson F 1997 Histotechnology. A Self-Instructional Text. Chicago: ASCP Press, pp.28-31. ISBN 089189411.
- ↑ Kiernan JA 2008 Histological and Histochemical Methods. 4th ed. Bloxham, UK, pp.54,57. ISBN 978-1-904842-42-2.
- ↑ 13.0 13.1 Script error
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- ↑ "Ranking Possible Cancer Hazards on the HERP Index". http://potency.lbl.gov/pdfs/herp.pdf. Retrieved 19 March 2007.
- ↑ The British Pharmacopoeia Secretariat (2009). "Index, BP 2009". http://www.pharmacopoeia.co.uk/pdf/2009_index.pdf. Retrieved 31 March 2010.
Further reading
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- "Limonene". Workplace Hazardous Materials Information System. Commission de la santé et de la sécurité du travail. 3 November 2005. http://www.reptox.csst.qc.ca/DetailSimdut.asp?no_produit=6783&langue=A.
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External links
- Detailed description of d-limonene from Biochem Corp.
- d-limonene information from the United States Environmental Protection Agencyar:ليمونين
bg:Лимонен ca:Limonè cs:Limonen da:Limonen de:Limonen es:Limoneno fa:لیمونن fr:Limonène it:Limonene hu:Limonén nl:Limoneen ja:リモネン pl:Limonen pt:Limoneno ru:Лимонен sl:Limonen fi:Limoneeni sv:Limonen zh:柠烯
