Verbenone

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Verbenone
Verbenone structure.png
Verbenone Verbenone3D.png
Verbenone
Names
IUPAC name
rel-(1R,5R)-Pin-2-en-4-one
Systematic IUPAC name
rel-(1R,5R)-4,6,6-Trimethylbicyclo[3.1.1]hept-3-en-2-one
Other names
Verbenone
2-Pinen-4-one
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.001.176 OOjs UI icon edit-ltr-progressive.svg
KEGG
PubChem CID
UNII
  • InChI=1S/C10H14O/c1-6-4-9(11)8-5-7(6)10(8,2)3/h4,7-8H,5H2,1-3H3/t7-,8+/m1/s1 Yes check.svgY
    Key: DCSCXTJOXBUFGB-SFYZADRCSA-N Yes check.svgY
  • InChI=1/C10H14O/c1-6-4-9(11)8-5-7(6)10(8,2)3/h4,7-8H,5H2,1-3H3/t7-,8+/m1/s1
    Key: DCSCXTJOXBUFGB-SFYZADRCBG
  • CC1=CC(=O)[C@@H]2C[C@H]1C2(C)C
Properties
C10H14O
Molar mass 150.221 g·mol−1
Density 0.978 g/cm3
Melting point 6.5 °C (43.7 °F; 279.6 K)
Boiling point 227 to 228 °C (441 to 442 °F; 500 to 501 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Verbenone is a natural organic compound classified as a terpene that is found naturally in a variety of plants. The chemical has a pleasant characteristic odor. Besides being a natural constituent of plants, it and its analogs are insect pheromones. In particular, verbenone when formulated in a long-lasting matrix has an important role in the control of bark beetles such as the mountain pine beetle and the Southern pine bark beetle.

Contents

Chemistry

Verbenone is a monoterpene, to be specific a bicyclic ketone terpene. It is the primary constituent of the oil of Spanish verbena, hence its name; it is also found in the oil of rosemary. It is nearly insoluble in water, but miscible with most organic solvents. [1]

Verbenone can be readily prepared synthetically by the oxidation of the more common terpene α-pinene: [2]

Verbenone by oxidation of pinene.png

Verbenone can then be converted into chrysanthenone through a photochemical rearrangement reaction: [3]

Chrysanthenone synthesis.png

Use for insect control

The southern pine beetle ( Dendroctonus frontalis ), a bark beetle, is a major threat to pine trees in the southeastern United States. Its reproductive cycle is controlled by varying ratios of certain natural chemicals, including verbenone. To reproduce, pine bark beetles aggregate in large numbers in their host pine trees. At the beginning of an attack, various chemicals produced by infested trees and by the beetles attract additional beetles of the same species. When the numbers of adults and larvae approach the maximum that the tree can support, antiaggregation signal chemicals, i.e., verbenone, are produced, reducing the likelihood that additional beetles will land and attack the tree. Forest managers frequently try to control infestations of the Southern pine bark beetle by cutting down and sometimes burning infested trees and nearby healthy trees. They then place verbenone formulations on nearby susceptible healthy trees to repel and confuse the beetles. [4]

Verbenone is also used to manage mountain pine beetle (Dendroctonus ponderosae) infestations. [5] Verbenone is recognized by the mountain pine beetle, Dendroctonus ponderosae Hopkins, a notable forest insect capable of causing extensive levels of tree mortality in western North America. Several formulations of verbenone have been registered with the U.S. Environmental Protection Agency [6] for tree protection. Failures in tree protection efficacy can be seen in situations where there is an excessive population of infesting insects, for example an area which contains more than 50 percent infested trees. [7] Loss of response to verbenone as a repellent is not due to any particular failure of the verbenone devices but is instead a response innate to the biology of the beetles which allows populations to continue flourishing even in situations of extreme environmental stress.

Verbenone is also used to manage redbay ambrosia beetle (Xyleborus glabratus) the vector of the fungus that causes laurel wilt. A 9-month trial in forest demonstrated a reduction in the number of beetles landing on redbay and a reduction in redbay mortality [8]

Other uses

Because of its pleasant aroma, verbenone (or essential oils high in verbenone content) are used in perfumery, aromatherapy, herbal teas, spices, and herbal remedies. The L-isomer is used as a cough suppressant under the name levoverbenone. Verbenone may also have antimicrobial properties. [9]

Related Research Articles

<span class="mw-page-title-main">Bark beetle</span> Subfamily of beetles

A bark beetle is the common name for the subfamily of beetles Scolytinae. Previously, this was considered a distinct family (Scolytidae), but is now understood to be a specialized clade of the "true weevil" family (Curculionidae). Although the term "bark beetle" refers to the fact that many species feed in the inner bark (phloem) layer of trees, the subfamily also has many species with other lifestyles, including some that bore into wood, feed in fruit and seeds, or tunnel into herbaceous plants. Well-known species are members of the type genus Scolytus, namely the European elm bark beetle S. multistriatus and the large elm bark beetle S. scolytus, which like the American elm bark beetle Hylurgopinus rufipes, transmit Dutch elm disease fungi (Ophiostoma). The mountain pine beetle Dendroctonus ponderosae, southern pine beetle Dendroctonus frontalis, and their near relatives are major pests of conifer forests in North America. A similarly aggressive species in Europe is the spruce ips Ips typographus. A tiny bark beetle, the coffee berry borer, Hypothenemus hampei is a major pest on coffee plantations around the world.

<span class="mw-page-title-main">Mountain pine beetle</span> Species of beetle

The mountain pine beetle is a species of bark beetle native to the forests of western North America from Mexico to central British Columbia. It has a hard black exoskeleton, and measures approximately 5 millimetres, about the size of a grain of rice.

<span class="mw-page-title-main">Disturbance (ecology)</span> Temporary change in environmental conditions that causes a pronounced change in an ecosystem

In ecology, a disturbance is a temporary change in environmental conditions that causes a pronounced change in an ecosystem. Disturbances often act quickly and with great effect, to alter the physical structure or arrangement of biotic and abiotic elements. A disturbance can also occur over a long period of time and can impact the biodiversity within an ecosystem.

<i>Thanasimus formicarius</i> Species of beetle

The ant beetle, also known as the European red-bellied clerid, is a medium size insect, rather soft-bodied, with strong mandibles that can tear between the hard sclerotized integument of bark beetles. Larvae and adults are common predators of bark beetles in Europe.

Mating disruption (MD) is a pest management technique designed to control certain insect pests by introducing artificial stimuli that confuse the individuals and disrupt mate localization and/or courtship, thus preventing mating and blocking the reproductive cycle. It usually involves the use of synthetic sex pheromones, although other approaches, such as interfering with vibrational communication, are also being developed.

<span class="mw-page-title-main">Boggs Mountain Demonstration State Forest</span> State forest in California

Boggs Mountain Demonstration State Forest is a state forest in Lake County, California that covers the northwest of Boggs Mountain. It was founded in 1949, and came into operation in 1950 when most of the site had been clear cut. The purpose was to demonstrate good practices in restoring and managing a forest. The state forest was open for recreational use, including camping, hiking, mountain biking etc. The 2015 Valley Fire destroyed 80% of the trees. The state forest as of 2021 was replanting saplings.

<i>Dendroctonus</i> Genus of beetles

Dendroctonus is a genus of bark beetles. It includes several species notorious for destroying trees in the forests of North America. The genus has a symbiotic relationship with many different yeasts, particularly those in the genera Candida and Pichia that aid in digestion and pheromone production.

<span class="mw-page-title-main">Laurel wilt</span> Plant disease

Laurel wilt, also called laurel wilt disease, is a vascular disease that is caused by the fungus Raffaelea lauricola, which is transmitted by the invasive redbay ambrosia beetle, Xyleborus glabratus. The disease affects and kills members of the laurel family. The avocado is perhaps the most commercially valuable plant affected by laurel wilt.

<i>Xyleborus glabratus</i> Species of beetle

Xyleborus glabratus, the redbay ambrosia beetle, is a type of ambrosia beetle invasive in the United States. It has been documented as the primary vector of Raffaelea lauricola, the fungus that causes laurel wilt, a disease that can kill several North American tree species in the family Lauraceae, including redbay, sassafras, and avocado.

Blue stain fungi is a vague term including various fungi that cause dark staining in sapwood. The staining is most often blue, but could also be grey or black. Because the grouping is based solely on symptomatics, it is not a monophyletic grouping.

<i>Dendroctonus rufipennis</i> Species of beetle

Dendroctonus rufipennis, the spruce beetle, is a species of bark beetle native to British Columbia, Newfoundland and Labrador, Nova Scotia, Ontario, Quebec, Northern Manitoba, the Yukon, Colorado, Wyoming, Montana, and Maine. They are known to destroy forests of spruce trees including Engelmann, White, Sitka, and Colorado blue spruce. Adults average 4 to 7 mm in length.

<span class="mw-page-title-main">European spruce bark beetle</span> Species of beetle

The European spruce bark beetle, is a species of beetle in the weevil subfamily Scolytinae, the bark beetles, and is found from Europe to Asia Minor and some parts of Africa.

<i>Dendroctonus frontalis</i> Species of beetle

Dendroctonus frontalis, the southern pine beetle, often shortened to simply SPB, is a species of bark beetle native to the forests of the southern United States, Mexico and Central America. It has recently expanded its range to the northeastern United States, where it is considered an invasive species and has destroyed massive amounts of pine forest.

<i>Ips</i> (beetle) Genus of beetles

Ips is a genus of beetles in the family Curculionidae, the true weevils. They are bark beetles, members of the subfamily Scolytinae. Species are distributed throughout the Northern Hemisphere. Some are known as introduced species in Australia and Africa. Many species are pests of forest trees, especially pines and spruces. They are known commonly as engraver beetles, ips engraver beetles, and pine engravers.

<i>Dendroctonus valens</i> Species of beetle

Dendroctonus valens, the red turpentine beetle, is a species of bark beetle native to the forests of North America, Mexico, Guatemala and Honduras. It has been introduced to China where it has become invasive. In its native range it causes little damage, but in China it is a destructive pest and has killed more than six million pine trees.

<i>Rhizophagus grandis</i> Species of beetle

Rhizophagus grandis is a species of predatory beetle in the family Monotomidae. R. grandis is a specialist predator on the larvae of the great spruce bark beetle, a pest of spruce trees (Picea), and is found in Eurasian forests where its prey is found.

<i>Dendroctonus terebrans</i> Species of beetle

Dendroctonus terebrans, the black turpentine beetle, is a species of bark beetle native to the eastern United States. Its larvae tunnel under the bark of pine trees, weakening and sometimes killing the trees.

<span class="mw-page-title-main">Forest disturbance by invasive insects and diseases in the United States</span>

Species which are not native to a forest ecosystem can act as an agent of disturbance, changing forest dynamics as they invade and spread. Invasive insects and pathogens (diseases) are introduced to the United States through international trade, and spread through means of natural and human-dispersal. Invasive insects and pathogens are a serious threat to many forests in the United States and have decimated populations of several tree species, including American chestnut, American elm, eastern hemlock, whitebark pine, and the native ash species. The loss of these tree species is typically rapid with both short and long-term impacts to the forest ecosystem.

Verbenol (2-pine-4-ol) is a group of stereoisomeric bicyclic monoterpene alcohols. These compounds have been found to be active components of insect pheromones and essential oils.

Dendroctonus adjunctus, the roundheaded pine beetle, is a species of bark beetle in the family Curculionidae found in North America. A parasite, the roundheaded pine beetle feeds on and eventually kills pine trees of several species in Guatemala, Mexico, and the Southern United States.

References

  1. Merck Index, 11th Edition, 9862
  2. Glidden, U.S. Patent 2,911,442 (1959)
  3. Erman, William F. (1967). "Photochemical transformations of unsaturated bicyclic ketones. Verbenone and its photodynamic products of ultraviolet irradiation". Journal of the American Chemical Society. 89 (15): 3828–3841. doi:10.1021/ja00991a026.
  4. U.S. Environmental Protection Agency Pesticide Fact Sheet #128986.
  5. Mafra-Neto, Agenor; de Lame, Frédérique M.; Fettig, Christopher J.; Perring, Thomas M.; Stelinski, Lukasz L.; Stoltman, Lyndsie L.; Mafra, Leandro E. J.; Borges, Rafael; Vargas, Roger I. (2013). "Manipulation of Insect Behavior with Specialized Pheromone and Lure Application Technology (SPLAT®)". In John Beck; Joel Coats; Stephen Duke; Marja Koivunen (eds.). Natural Products for Pest Management. Vol. 1141. American Chemical Society. pp. 31–58.
  6. U.S. Environmental Protection Agency Pesticide Fact Sheet #128986.
  7. Progar, R. A. 2005. Five-year operational trial of verbenone to deter mountain pine beetle (Dendroctonus ponderosae ; Coleoptera: Scolytidae) attack of lodgepole pine (Pinus contorta). Environmental Entomology 34: 1402 – 1407
  8. Martini, X., Sobel, L., Conover, D., Mafra‐Neto, A., & Smith, J. (2020). Verbenone reduces landing of the redbay ambrosia beetle, vector of the laurel wilt pathogen, on live standing redbay trees. Agricultural and Forest Entomology, 22(1), 83-91.
  9. Santoyo, S; Cavero, S; Jaime, L; Ibañez, E; Señoráns, FJ; Reglero, G (2005). "Chemical composition and antimicrobial activity of Rosmarinus officinalis L. Essential oil obtained via supercritical fluid extraction". Journal of Food Protection. 68 (4): 790–5. doi:10.4315/0362-028x-68.4.790. PMID   15830672.