Carvone

Chembox new
Name = Carvone
ImageFile = Carvone.png ImageName = Carvone
ImageFile1 = S-carvone-stickModel.png ImageSize1 = 180px
IUPACName = 2-methyl-5-(prop-1-en-2-yl)
cyclohex-2-enone
OtherNames = Δ^6:8(9)-"p"-menthadien-2-one
1-methyl-4-isopropenyl-
Δ⁶-cyclohexen-2-one
carvol (obsolete)
Section1 = Chembox Identifiers
SMILES = O=C1C [C@@H] (CC=C1C)C(C)=C ("R")
O=C1C [C@H] (CC=C1C)C(C)=C ("S")
CASOther = [6485-40-1] (("R")-Carvone)
[2244-16-8] (("S")-Carvone)
RTECS = OS8650000 ("R")
OS8670000 ("S")
Section2 = Chembox Properties
Formula = C₁₀H₁₄O
MolarMass = 150.22
Appearance = Clear, colorless liquid
Density = 0.958 g/cm³ ()
Solubility = Insoluble (cold)
Slightly soluble (hot)
SolubilityOther = soluble
Solvent = Ethanol
SolubilityOther = soluble
Solvent = Diethyl ether
SolubilityOther = soluble
Solvent = Chloroform
MeltingPt = 89 °C
BoilingPt = 231 °C
pKa =
SpecRotation = -61° ("R")-Carvone
61° ("S")-Carvone

Section7 = Chembox Hazards
ExternalMSDS = [http://physchem.ox.ac.uk/MSDS/ME/(S)-2-methyl-5-(1-methylethenyl)-2-cyclohexene-1-one.html External MSDS]
MainHazards = inflammable
EUClass =
NFPA-H = 1
NFPA-F = 2
NFPA-R = 0
RPhrases = 22
SPhrases = 36
Section8 = Chembox Related
Function = ketone
OtherFunctn = menthone
dihydrocarvone
carvomenthone
OtherCmpds = limonene, menthol,
"p"-cymene, carveol

Carvone is a member of a family of chemicals called terpenoids.cite book | author = Simonsen, J. L. | year = 1953 | title = The Terpenes | edition = 2nd edition | volume = 1 | location = Cambridge | publisher = Cambridge University Press | pages = 394-408] Carvone is found naturally in many essential oils, but is most abundant in the oils from seeds of caraway ("Carum carvi") and dill.De Carvalho, C. C. C. R; Da Fonseca, M. M. R. "Carvone: Why and how should one bother to produce this terpene" "Food Chemistry" 2006, 95, 413-422.]

tereoisomerism and odor

Carvone forms two mirror image forms or enantiomers: "S"-(+)-carvone smells like caraway. Its mirror image, "R"-(–)-carvone, smells like spearmint. [cite journal | doi = 10.1021/jf60176a035 | title=Chemical and sensory data supporting the difference between the odors of the enantiomeric carvones | author= Theodore J. Leitereg, Dante G. Guadagni, Jean Harris, Thomas R. Mon, and Roy Teranishi | journal=J. Agric. Food Chem. | volume=19 | issue=4 | year=1971 | pages=785] The fact that the two enantiomers are perceived as smelling differently is proof that olfactory receptors must contain chiral groups, allowing them to respond more strongly to one enantiomer than to the other. Not all enantiomers have distinguishable odors. Squirrel monkeys have also been found to be able to discriminate between carvone enantiomers. [Laska, M.; Liesen, A.; Teubner, P. "American Journal of Physiology- Regulatory Integrative and Comparative Physiology", 1999, "277", R1098-R1103.]

The two forms are also referred to by older names, with "dextro"-, "d"- referring to "S"-carvone, and "laevo"-, "l"- referring to "R"-carvone.

Occurrence

"S"-(+)-Carvone is the principal constituent (50-70%) of the oil from caraway seeds ("Carum carvi"), [Hornok, L. "Cultivation and Processing of Medicinal Plants", John Wiley & Sons, Chichester, UK, 1992.] , which is produced on a scale of about 10 tonnes per year. It also occurs to the extent of about 40-60% in dill seed oil (from "Anethum graveolens"), and also in mandarin orange peel oil. "R"-(–)-Carvone is present at levels greater than 51% in spearmint oil ("Mentha spicata"), which is produced on a scale of around 1500 tonnes annually. This isomer also occurs in kuromoji oil. Some oils, like gingergrass oil, contain a mixture of both enantiomers. Many other natural oils, for example peppermint oil, contain lower concentrations of carvones.

History

Caraway was used for medicinal purposes by the ancient Romans, but carvone was probably not isolated as a pure compound until Varrentrapp obtained it in 1841. It was originally called "carvol" by Schweizer. Goldschmidt and Zűrrer identified it as a ketone related to limonene, and the structure was finally elucidated by Wagner in 1894. [Wagner, G. "Chemische Berichte" 1894, "27", 2270.]

Preparation

The dextro-form is obtained practically pure by the fractional distillation of caraway oil; the laevo-form from the oils containing it, by first forming its addition compound with hydrogen sulfide, decomposing this by potassium hydroxide in ethanol, and distilling the product in a current of steam. It may be synthetically prepared from limonene nitrosochloride, alcoholic converting this compound into 1-carvoxime, which on boiling with dilute sulfuric acid yields l-carvone. The major use of d-limonene is as a precursor to carvone. The large scale availability of orange rinds, a byproduct in the production of orange juice, has made limonene cheaply available, and synthetic carvone correspondingly inexpensively prepared.Karl-Georg Fahlbusch, Franz-Josef Hammerschmidt, Johannes Panten, Wilhelm Pickenhagen, Dietmar Schatkowski, Kurt Bauer, Dorothea Garbe, Horst Surburg “Flavors and Fragrances“ in Ullmann's Encyclopedia of Industrial Chemistry, 2002, Wiley-VCH, Weinheim. DOI|10.1002/14356007.a11_141}.]

The biosynthesis of carvone is by oxidation of limonene.

Chemical properties

Reduction

There are three double bonds in carvone capable of reduction; the product of reduction depends on the reagents and conditions used.cite book | author = Simonsen, J. L. | year = 1953 | title = The Terpenes | edition = 2nd edition | volume = 1 | location = Cambridge | publisher = Cambridge University Press | pages = 394-408] Catalytic hydrogenation of carvone (1) can give either carvomenthol (2) or carvomenthone (3). Zinc and acetic acid reduce carvone to give dihydrocarvone (4). MPV reduction using propan-2-ol and aluminium isopropoxide effects reduction of the carbonyl group only to provide carveol (5); a combination of sodium borohydride and CeCl₃ (Luche reduction) is also effective. Hydrazine and potassium hydroxide give limonene (6) via a Wolff-Kishner reduction.

Oxidation

Oxidation of carvone can also lead to a variety of products.cite book | author = Simonsen, J. L. | year = 1953 | title = The Terpenes | edition = 2nd edition | volume = 1 | location = Cambridge | publisher = Cambridge University Press | pages = 394-408] In the presence of an alkali such as Ba(OH)₂, carvone is oxidised by air or oxygen to give the diketone 7. With hydrogen peroxide the epoxide 8 is formed. Carvone may be cleaved using ozone followed by steam, giving dilactone 9, while KMnO₄ gives 10.

Conjugate additions

As an α,beta;-unsaturated ketone, carvone undergoes conjugate additions of nucleophiles. For example, carvone reacts with lithium dimethylcuprate to place a methyl group "trans" to the isopropenyl group with good stereoselectivity. The resulting enolate can then be allylated using allyl bromide to give ketone 11.cite journal
author = Srikrishna, A.
coauthors = Jagadeeswar Reddy, T.
year = 1998
title = Enantiospecific synthesis of (+)-(1S, 2R, 6S)-1, 2-dimethylbicyclo [4.3. 0] nonan-8-one and (-)-7-epibakkenolide-A
journal = Tetrahedron
volume = 54
issue = 38
pages = 11517–11524
url = http://linkinghub.elsevier.com/retrieve/pii/S0040402098006723
accessdate = 2008-01-22
doi = 10.1016/S0040-4020(98)00672-3]

Uses

Both carvones are used in the food and flavor industry.De Carvalho, C. C. C. R; Da Fonseca, M. M. R. "Carvone: Why and how should one bother to produce this terpene" "Food Chemistry" 2006, 95, 413-422.] "R"-(-)-Carvone is also used for air freshening products and, like many essential oils, oils containing carvones are used in aromatherapy and alternative medicine.

Food applications

As the compound most responsible for the flavor of caraway, dill and spearmint, carvone has been used for millennia in food.De Carvalho, C. C. C. R; Da Fonseca, M. M. R. "Carvone: Why and how should one bother to produce this terpene" "Food Chemistry" 2006, 95, 413-422.] Wrigley's Spearmint Gum is gum soaked in "R"-(–)-carvone and powdered with sugar.

Agriculture

"S"-(+)-Carvone is also used to prevent premature sprouting of potatoes during storage, being marketed in the Netherlands for this purpose under the name "Talent".De Carvalho, C. C. C. R; Da Fonseca, M. M. R. "Carvone: Why and how should one bother to produce this terpene" "Food Chemistry" 2006, 95, 413-422.]

Organic synthesis

Carvone is available inexpensively in both enantiomerically pure forms, making it an attractive starting material for the asymmetric total synthesis of natural products. For example, ("S")-(+)-carvone was used to begin a 1998 synthesis of the terpenoid quassin [(a) Shing, T. K. M.; Jiang, Q; Mak, T. C. W. "J. Org. Chem." 1998, "63", 2056-2057. (b) Shing, T. K. M.; Tang, Y. "J. Chem. Soc. Perkin Trans. 1 1994, 1625.] :

Metabolism

In the body, "in vivo" studies indicate that both enantiomers of carvone are mainly metabolized into dihydrocarvonic acid, carvonic acid and uroterpenolone. [Engel, W. "J. Agric. Food Chem.", 2001, "49" (8), 4069-4075.] (4"R",6"S")-(–)-carveol is also formed as a minor product via reduction by NADPH. (4"S")-(+)-carvone is likewise converted to (4"S",6"S")-(+)-carveol. [Jager, W.; Mayer, M.; Platzer, P.; Reznicek, G.; Dietrich, H.; Buchbauer, G.; "Journal of Pharmacy and Pharmacology" 2000, "52", 191-197.] This mainly occurs in the liver and involves cytochrome P450 oxidase and (+)-trans-carveol dehydrogenase.

References