Monoterpenes are a class of

terpene Terpenes () are a class of natural products consisting of compounds with the formula (C5H8)n for n > 1. Comprising more than 30,000 compounds, these unsaturated hydrocarbons are produced predominantly by plants, particularly conifers. Terpenes ar ...

s that consist of two

isoprene Isoprene, or 2-methyl-1,3-butadiene, is a common volatile organic compound with the formula CH2=C(CH3)−CH=CH2. In its pure form it is a colorless volatile liquid. Isoprene is an unsaturated hydrocarbon. It is produced by many plants and animals ...

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.

Biosynthesis

Monoterpenes are derived biosynthetically from units of isopentenyl pyrophosphate, which is formed from

acetyl-CoA Acetyl-CoA (acetyl coenzyme A) is a molecule that participates in many biochemical reactions in protein, carbohydrate and lipid metabolism. Its main function is to deliver the acetyl group to the citric acid cycle (Krebs cycle) to be oxidized fo ...

via the intermediacy of mevalonic acid in the

HMG-CoA reductase pathway The mevalonate pathway, also known as the isoprenoid pathway or HMG-CoA reductase pathway is an essential metabolic pathway present in eukaryotes, archaea, and some bacteria. The pathway produces two five-carbon building blocks called isopenten ...

. 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). 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 Geraniol is a monoterpenoid and an alcohol. It is the primary component of citronella oil and is a primary component of rose oil, palmarosa oil. It is a colorless oil, although commercial samples can appear yellow. It has low solubility in w ...

. Additional rearrangements and oxidations provide compounds such as citral,

citronellal Citronellal or rhodinal ( C10 H18 O) is a mono terpenoid aldehyde, the main component in the mixture of terpenoid chemical compounds that give citronella oil its distinctive lemon scent. Citronellal is a main isolate in distilled oils from the ...

, citronellol,

linalool Linalool () refers to two enantiomers of a naturally occurring terpene alcohol found in many flowers and spice plants. Linalool has multiple commercial applications, the majority of which are based on its pleasant scent (floral, with a touch o ...

, and many others. Many monoterpenes found in marine organisms are halogenated, such as

halomon Halomon is a polyhalogenated monoterpene first isolated from the marine red algae ''Portieria hornemannii''. Halomon has attracted research interest because of its promising profile of selective cytotoxicity that suggests its potential use as a ...

Main examples

Myrcen.png, Myrcene is an acyclic monoterpene, an

alkene In organic chemistry, an alkene is a hydrocarbon containing a carbon–carbon double bond. Alkene is often used as synonym of olefin, that is, any hydrocarbon containing one or more double bonds.H. Stephen Stoker (2015): General, Organic, an ...

hydrocarbon In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic, and their odors are usually weak or ...

Menthol_skeletal.svg,

Menthol Menthol is an organic compound, more specifically a monoterpenoid, made synthetically or obtained from the oils of corn mint, peppermint, or other mints. It is a waxy, clear or white crystalline substance, which is solid at room temperature and ...

is a monocyclic monoterpenoid Limonene-2D-skeletal.svg,

Limonene Limonene is a colorless liquid aliphatic hydrocarbon classified as a cyclic monoterpene, and is the major component in the oil of citrus fruit peels. The -isomer, occurring more commonly in nature as the fragrance of oranges, is a flavoring ...

is a monocyclic monoterpene Carvone.svg, Carvone is a monoterpenoid Beta-thujaplicin.png, Hinokitiol is a monoterpenoid, a tropolone derivative Linalool_skeletal.svg,

Linalool Linalool () refers to two enantiomers of a naturally occurring terpene alcohol found in many flowers and spice plants. Linalool has multiple commercial applications, the majority of which are based on its pleasant scent (floral, with a touch o ...

is an acyclic monoterpenoid Bicyclic monoterpenes include carene, sabinene, camphene, and thujene.

Camphor Camphor () is a waxy, colorless solid with a strong aroma. It is classified as a terpenoid and a cyclic ketone. It is found in the wood of the camphor laurel ('' Cinnamomum camphora''), a large evergreen tree found in East Asia; and in the k ...

borneol Borneol is a bicyclic organic compound and a terpene derivative. The hydroxyl group in this compound is placed in an '' endo'' position. The exo diastereomer is called isoborneol. Being chiral, borneol exists as enantiomers, both of which are foun ...

eucalyptol Eucalyptol is a monoterpenoid. A colorless liquid, it is a bicyclic ether. Eucalyptol has a fresh mint-like smell and a spicy, cooling taste. It is insoluble in water, but miscible with organic solvents. Eucalyptol makes up ~70% - 90% of euc ...

and ascaridole are examples of bicyclic monoterpenoids containing ketone, alcohol, ether, and bridging

peroxide In chemistry, peroxides are a group of compounds with the structure , where R = any element. The group in a peroxide is called the peroxide group or peroxo group. The nomenclature is somewhat variable. The most common peroxide is hydrogen ...

functional groups, respectively. Umbellulone is another example of bicyclic monoterpene ketone.

Natural roles

Monoterpenes are found in many parts of different plants, such as barks,

heartwood Wood is a porous and fibrous structural tissue found in the stems and roots of trees and other woody plants. It is an organic materiala natural composite of cellulose fibers that are strong in tension and embedded in a matrix of lignin t ...

, bark and leaves of coniferous trees, in

vegetable Vegetables are parts of plants that are consumed by humans or other animals as food. The original meaning is still commonly used and is applied to plants collectively to refer to all edible plant matter, including the flowers, fruits, stems ...

fruit In botany, a fruit is the seed-bearing structure in flowering plants that is formed from the ovary after flowering. Fruits are the means by which flowering plants (also known as angiosperms) disseminate their seeds. Edible fruits in partic ...

s and

herb In general use, herbs are a widely distributed and widespread group of plants, excluding vegetables and other plants consumed for macronutrients, with savory or aromatic properties that are used for flavoring and garnishing food, for medicina ...

s. Essential oils are very rich in monoterpenes. Several monoterpenes produced by trees, such as

, hinokitiol, and ocimene have

fungicidal Fungicides are biocidal chemical compounds or biological organisms used to kill parasitic fungi or their spores. A fungistatic inhibits their growth. Fungi can cause serious damage in agriculture, resulting in critical losses of yield, quality ...

and

antibacterial An antibiotic is a type of antimicrobial substance active against bacteria. It is the most important type of antibacterial agent for fighting bacterial infections, and antibiotic medications are widely used in the treatment and prevention ...

activities and participate in wound healing. Some of these compounds are produced to protect the trees from

insect Insects (from Latin ') are pancrustacean hexapod invertebrates of the class Insecta. They are the largest group within the arthropod phylum. Insects have a chitinous exoskeleton, a three-part body (head, thorax and abdomen), three pairs ...

attacks. Monoterpenes are emitted by

forest A forest is an area of land dominated by trees. Hundreds of definitions of forest are used throughout the world, incorporating factors such as tree density, tree height, land use, legal standing, and ecological function. The United Nations' ...

s and form

aerosol An aerosol is a suspension of fine solid particles or liquid droplets in air or another gas. Aerosols can be natural or anthropogenic. Examples of natural aerosols are fog or mist, dust, forest exudates, and geyser steam. Examples of ant ...

s that are proposed to serve as

cloud condensation nuclei Cloud condensation nuclei (CCNs), also known as cloud seeds, are small particles typically 0.2 µm, or one hundredth the size of a cloud droplet. CCNs are a unique subset of aerosols in the atmosphere on which water vapour condenses. This c ...

(CCN). Such aerosols can increase the brightness of clouds and cool the climate. Many monoterpenes have unique smell and flavor. For example, sabinene contributes to the spicy taste of

black pepper Black pepper (''Piper nigrum'') is a flowering vine in the family Piperaceae, cultivated for its fruit, known as a peppercorn, which is usually dried and used as a spice and seasoning. The fruit is a drupe (stonefruit) which is about in di ...

, 3-carene gives

cannabis ''Cannabis'' () is a genus of flowering plants in the family Cannabaceae. The number of species within the genus is disputed. Three species may be recognized: '' Cannabis sativa'', '' C. indica'', and '' C. ruderalis''. Alternativel ...

an earthy taste and smell, citral has a lemon-like pleasant odor and contributes to the distinctive smell of

citrus ''Citrus'' is a genus of flowering trees and shrubs in the rue family, Rutaceae. Plants in the genus produce citrus fruits, including important crops such as oranges, lemons, grapefruits, pomelos, and limes. The genus ''Citrus'' is nati ...

fruits, and thujene and carvacrol are responsible for the pungent flavors of

summer savory Summer savory (''Satureja hortensis'') is among the best known of the savory genus. It is an annual, but otherwise is similar in use and flavor to the perennial winter savory. It is used more often than winter savory, which has a slightly more ...

and oregano, respectively. Monoterpenes are considered allelochemicals.

Uses

Many monoterpenes are volatile compounds and some of them are well-known fragrants found in the essential oils of many plants. For example,

camphor Camphor () is a waxy, colorless solid with a strong aroma. It is classified as a terpenoid and a cyclic ketone. It is found in the wood of the camphor laurel ('' Cinnamomum camphora''), a large evergreen tree found in East Asia; and in the k ...

, citral, citronellol,

grapefruit mercaptan Grapefruit mercaptan is the common name for a natural organic compound found in grapefruit. It is a monoterpenoid that contains a thiol (also known as a mercaptan) functional group. Structurally a hydroxy group of terpineol is replaced by the thi ...

, ocimene, myrcene,

limonene Limonene is a colorless liquid aliphatic hydrocarbon classified as a cyclic monoterpene, and is the major component in the oil of citrus fruit peels. The -isomer, occurring more commonly in nature as the fragrance of oranges, is a flavoring ...

menthol Menthol is an organic compound, more specifically a monoterpenoid, made synthetically or obtained from the oils of corn mint, peppermint, or other mints. It is a waxy, clear or white crystalline substance, which is solid at room temperature and ...

, camphene and

pinene 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 co ...

s are used in

perfume Perfume (, ; french: parfum) is a mixture of fragrant essential oils or aroma compounds (fragrances), fixatives and solvents, usually in liquid form, used to give the human body, animals, food, objects, and living-spaces an agreeable scent. ...

s and

cosmetic Cosmetic may refer to: * Cosmetics, or make-up, substances to enhance the beauty of the human body, apart from simple cleaning *Cosmetic, an adjective describing beauty, aesthetics, or appearance, especially concerning the human body *Cosmetic, ...

products.

and perillyl alcohol are used in

cleaning Cleaning is the process of removing unwanted substances, such as dirt, infectious agents, and other impurities, from an object or environment. Cleaning is often performed for aesthetic, hygienic, functional, environmental, or safety purposes. ...

products. Many monoterpenes are used as food flavors and

food additive Food additives are substances added to food to preserve flavor or enhance taste, appearance, or other sensory qualities. Some additives have been used for centuries as part of an effort to preserve food, for example vinegar (pickling), salt (sal ...

s, such as

bornyl acetate Bornyl acetate is a chemical compound. Its molecular formula is C12H20O2 and its molecular weight is 196.29 g/mol. It is the acetate ester of borneol. It is used as a food additive, flavouring agent, and odour agent. It is a component of the ess ...

, citral,

, hinokitiol, camphene and

, hinokitiol and

thymol Thymol (also known as 2-isopropyl-5-methylphenol, IPMP), , is a natural monoterpenoid phenol derivative of ''p''-Cymene, isomeric with carvacrol, found in oil of thyme, and extracted from '' Thymus vulgaris'' (common thyme), ajwain, and va ...

are also used in

oral hygiene Oral hygiene is the practice of keeping one's mouth clean and free of disease and other problems (e.g. bad breath) by regular brushing of the teeth (dental hygiene) and cleaning between the teeth. It is important that oral hygiene be carried out ...

products.

Thymol Thymol (also known as 2-isopropyl-5-methylphenol, IPMP), , is a natural monoterpenoid phenol derivative of ''p''-Cymene, isomeric with carvacrol, found in oil of thyme, and extracted from '' Thymus vulgaris'' (common thyme), ajwain, and va ...

also has

antiseptic An antiseptic (from Greek ἀντί ''anti'', "against" and σηπτικός ''sēptikos'', "putrefactive") is an antimicrobial substance or compound that is applied to living tissue/skin to reduce the possibility of infection, sepsis, or putre ...

and

disinfectant A disinfectant is a chemical substance or compound used to inactivate or destroy microorganisms on inert surfaces. Disinfection does not necessarily kill all microorganisms, especially resistant bacterial spores; it is less effective than s ...

properties. Volatile monoterpenes produced by plants can attract or repel insects, thus some of them are used in

insect repellent An insect repellent (also commonly called "bug spray") is a substance applied to skin, clothing, or other surfaces to discourage insects (and arthropods in general) from landing or climbing on that surface. Insect repellents help prevent and co ...

s, such as citronellol,

, hinokitiol,

and

Ascaridole Ascaridole is a natural organic compound classified as a bicyclic monoterpenoid that has an unusual bridging peroxide functional group. It is a colorless liquid with a pungent smell and taste that is soluble in most organic solvents. Like other ...

and

are monoterpenes that have pharmaceutical use.

Health effects

A study suggests that a range of floor cleaners with certain monoterpenes may cause indoor

air pollution Air pollution is the contamination of air due to the presence of substances in the atmosphere that are harmful to the health of humans and other living beings, or cause damage to the climate or to materials. There are many different type ...

equivalent or exceeding the harm to respiratory tracts when the time is spent near a busy road. This is due to

ozonolysis In organic chemistry, ozonolysis is an organic reaction where the unsaturated bonds of alkenes (), alkynes (), or azo compounds () are cleaved with ozone (). Alkenes and alkynes form organic compounds in which the multiple carbon–carbon bon ...

of monoterpenes like

leading to the production of atmospheric SOA. Another study suggests monoterpenes substantially affect ambient organic aerosol with uncertainties regarding environmental impacts. In a review, scientists concluded that they hope that these "substances will be extensively studied and used in more and more in medicine". 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." 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.

References