Cinnamaldehyde

Cinnamaldehyde
Skeletal formula of cinnamaldehyde
Ball-and-stick model of the cinnamaldehyde molecule
Names
IUPAC name
(2E)-3-phenylprop-2-enal
Other names
Cinnamic aldehyde; trans-cinnamaldehyde
Identifiers
14371-10-9 N
3D model (Jmol) Interactive image
ChEBI CHEBI:16731 YesY
ChEMBL ChEMBL293492 YesY
ChemSpider 553117 YesY
ECHA InfoCard 100.002.922
EC Number 203-213-9
2423
KEGG C00903 YesY
PubChem 637511
RTECS number GD6475000
UNII SR60A3XG0F YesY
Properties
C9H8O
Molar mass 132.16 g/mol
Appearance Yellow oil
Odor pungent, cinnamon-like
Density 1.0497 g/mL
Melting point −7.5 °C (18.5 °F; 265.6 K)
Boiling point 248 °C (478 °F; 521 K)
Slightly Soluble
Solubility soluble in ether, chloroform
insoluble in petroleum ether
miscible with alcohol, oils
1.6195
Hazards
R-phrases R36 R37 R38
S-phrases S26 S36
NFPA 704
Flammability code 2: Must be moderately heated or exposed to relatively high ambient temperature before ignition can occur. Flash point between 38 and 93 °C (100 and 200 °F). E.g., diesel fuel Health code 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g., chloroform Reactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g., liquid nitrogen Special hazards (white): no codeNFPA 704 four-colored diamond
2
2
0
Flash point 71 °C (160 °F; 344 K)
Lethal dose or concentration (LD, LC):
3400 mg/kg (rat, oral)
Related compounds
Related compounds
 Cinnamic acid
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YesYN ?)
Infobox references

Cinnamaldehyde is an organic compound with the formula C6H5CH=CHCHO. Occurs naturally as predominately the trans (E) isomer, it gives cinnamon its flavor and odor.[1] It is a flavonoid that is naturally synthesized by the shikimate pathway.[2] This pale yellow, viscous liquid occurs in the bark of cinnamon trees and other species of the genus Cinnamomum. The essential oil of cinnamon bark is about 50% cinnamaldehyde.[3]

Structure and synthesis

Cinnamaldehyde was isolated from cinnamon essential oil in 1834 by Dumas and Péligot[4] and synthesized in the laboratory by the Italian chemist Luigi Chiozza (1828-1889) in 1854.[5]

The natural product is trans-cinnamaldehyde. The molecule consists of a benzene ring attached to an unsaturated aldehyde. As such, the molecule can be viewed as a derivative of acrolein. Its color is due to the π → π* transition: increased conjugation in comparison with acrolein shifts this band towards the visible.[6]

Biosynthesis

Pathway for the biosynthesis of cis-cinnamaldehyde.

The biosynthesis of cinnamaldehyde begins with deamination of L-phenylalalanine into cinnamic acid by the action of phenylalanine ammonia lyase (PAL).[7][8] PAL catalyzes this reaction by a non-oxidative deamination. This deamination relies on the MIO prosthetic group of PAL.[9] PAL gives rise to trans-cinnamic acid.

In the second step, 4-coumarate: CoA ligase (4CL) converts cinnamic acid to cinnamoyl-CoA by an acid-thiol ligation.[7] 4CL uses ATP to catalyze the formation of cinnamoyl-CoA.[10] 4CL effects this reaction in two steps.[11] 4CL forms a hydroxycinnamate-AMP anhydride, followed by a nucleophile attack on the carbonyl of the acyl adenylate.[12]

Cinnamoyl-CoA is reduced by NADPH catalyzed by CCR (cinnamoyl-CoA reductase) to form cinnamaldehyde.[7][13]

Synthesis

Several methods of laboratory synthesis exist, but cinnamaldehyde is most economically obtained from the steam distillation of the oil of cinnamon bark. The compound can be prepared from related compounds such as cinnamyl alcohol, (the alcohol form of cinnamaldehyde), but the first synthesis from unrelated compounds was the aldol condensation of benzaldehyde and acetaldehyde.

Metabolism

Cinnamaldehyde occurs widely, and closely related compounds give rise to lignin. All such compounds are biosynthesized starting from phenylalanine, which undergoes conversion.[14]

Cinnamoyl-CoA reductase is an enzyme responsible for the production of cinnamoyl-CoA from cinnamaldehyde.

Applications

As a flavorant

The most obvious application for cinnamaldehyde is as flavoring in chewing gum, ice cream, candy, and beverages; use levels range from 9 to 4900 parts per million (ppm) (that is, less than 0.5%). It is also used in some perfumes of natural, sweet, or fruity scents. Almond, apricot, butterscotch, and other aromas may partially employ the compound for their pleasant smells. Cinnamaldehyde can be used as a food adulterant; powdered beechnut husk aromatized with cinnamaldehyde can be marketed as powdered cinnamon.[15] Some breakfast cereals contain as much as 187 ppm cinnamaldehyde.[16]

As an agrichemical

Cinnamaldehyde is also used as a fungicide.[17] Proven effective on over 40 different crops, cinnamaldehyde is typically applied to the root systems of plants. Its low toxicity and well-known properties make it ideal for agriculture. Cinnamaldehyde is an effective insecticide, and its scent is also known to repel animals, such as cats and dogs.[17] It has been tested as a safe and effective insecticide against mosquito larvae.[18] A concentration of 29 ppm of cinnamaldehyde kills half of Aedes aegypti mosquito larvae in 24 hours.[19] Trans-cinnamaldehyde works as a potent fumigant and practical repellant for adult mosquitos.[20]

Miscellaneous uses

Cinnamaldehyde is also known as a corrosion inhibitor for steel and other ferrous alloys in corrosive fluids such as hydrochloric acid. It is believed that this is achieved by polymerization to form a protective film on the metal surface.[21][22] It can be used in combination with additional components such as dispersing agents, solvents and other surfactants. Cinnamaldehyde is also a potent inducer of apoptosis via ROS-mediated mitochondrial permeability transition in human promyelocytic leukemia HL-60 cells.[23] Cinnamaldehyde also has antimicrobial properties.[24] Cinnamaldehyde is also a TRPA1 activator, and can excite a subset of sensory neurons that are mainly cold-sensitive neurons, to cause nociceptive behavior in mice.[25]

Derivatives of cinnamaldehyde

Numerous derivatives of cinnamaldehyde are commercially useful. Dihydrocinnamyl alcohol, which occurs naturally but is produced by double hydrogenation of cinnamaldehyde, is used to confer the fragrances of hyacinth and lilac. Cinnamyl alcohol similarly occurs naturally and has the odor of lilac, but can be also produced starting from cinnamaldehyde.[26] Dihydrocinnamaldehyde is produced by the selective hydrogenation of the alkene subunit. α-Amyl- and α-hexylcinnamaldehyde are important commercial fragrances, but they are not prepared from cinnamaldehyde.[15]

Toxicology

Cinnamaldehyde is used in agriculture because of its low toxicity, but it is a skin irritant.[27]

References

  1. ↑ "Cinnamon". Transport Information Service. Gesamtverband der Deutschen Versicherungswirtschaft e.V. Retrieved 2007-10-23.
  2. ↑ Gutzeit, Herwig (2014). Plant Natural Products: Synthesis, Biological Functions and Practical Applications. Wiley. pp. 19–21. ISBN 978-3-527-33230-4.
  3. ↑ Singh, Gurdip; Maurya, Sumitra; deLampasona, M.P.; Catalan, Cesar A.N. (2007). "A comparison of chemical, antioxidant and antimicrobial studies of cinnamon leaf and bark volatile oils, oleoresins and their constituents". Food and Chemical Toxicology. 45 (9): 1650–1661. doi:10.1016/j.fct.2007.02.031. ISSN 0278-6915.
  4. ↑ Dumas, J.; Péligot, E. (1834). "Recherches de Chimie organique. — Sur l'Huile de Cannelle, l' Acide hippurique et l' Acide sébacique" [Organic chemistry research – On cinnamon oil, the hippuric acid and sebacic acid]. Annales de chimie et de physique (in French). 57: 305–34.
  5. ↑ L. Chiozza (1856). "Sur la production artificielle de l´essence de cannelle" [On the artificial production of cinnamon oil]. Comptes rendus (in French). 42: 222–227.
  6. ↑ Inuzuka, Kozo (1961). "Π Electronic structure of cinnamaldehyde". Bulletin of the Chemical Society of Japan. 34 (11): 1557–60. doi:10.1246/bcsj.34.1557.
  7. 1 2 3 Bang, Hyun Bae; Lee, Yoon Hyeok; Kim, Sun Chang; Sung, Chang Keun; Jeong, Ki Jun (2016-01-19). "Metabolic engineering of Escherichia coli for the production of cinnamaldehyde". Microbial Cell Factories. 15 (1). doi:10.1186/s12934-016-0415-9. ISSN 1475-2859. PMC 4719340Freely accessible. PMID 26785776.
  8. ↑ Koukol, J.; Conn, E. E. (1961-10-01). "The metabolism of aromatic compounds in higher plants. IV. Purification and properties of the phenylalanine deaminase of Hordeum vulgare". The Journal of Biological Chemistry. 236: 2692–2698. ISSN 0021-9258. PMID 14458851.
  9. ↑ Kong, Jian-Qiang (2015-07-20). "Phenylalanine ammonia-lyase, a key component used for phenylpropanoids production by metabolic engineering". RSC Advances. 5 (77): 62587–62603. doi:10.1039/C5RA08196C. ISSN 2046-2069.
  10. ↑ Beuerle, Till; Pichersky, Eran (2002-03-15). "Enzymatic Synthesis and Purification of Aromatic Coenzyme A Esters". Analytical Biochemistry. 302 (2): 305–312. doi:10.1006/abio.2001.5574.
  11. ↑ Allina, Sandra M.; Pri-Hadash, Aviva; Theilmann, David A.; Ellis, Brian E.; Douglas, Carl J. (1998-02-01). "4-Coumarate:Coenzyme A Ligase in Hybrid Poplar". Plant Physiology. 116 (2): 743–754. doi:10.1104/pp.116.2.743. ISSN 0032-0889. PMC 35134Freely accessible. PMID 9489021.
  12. ↑ Li, Zhi; Nair, Satish K. (2015-11-03). "Structural Basis for Specificity and Flexibility in a Plant 4-Coumarate:CoA Ligase". Structure (London, England: 1993). 23 (11): 2032–2042. doi:10.1016/j.str.2015.08.012. ISSN 1878-4186. PMID 26412334.
  13. ↑ WENGENMAYER, Herta; EBEL, Jurgen; GRISEBACH, Hans (1976). "Enzymic Synthesis of Lignin Precursors. Purification and Properties of a Cinnamoyl-CoA: NADPH Reductase from Cell Suspension Cultures of Soybean (Glycine max)". European Journal of Biochemistry. 65 (2): 529–536. doi:10.1111/j.1432-1033.1976.tb10370.x. ISSN 0014-2956.
  14. ↑ Boerjan, Wout; Ralph, John; Baucher, Marie (2003). "Ligninbiosynthesis". Annual Review of Plant Biology. 54: 519–46. doi:10.1146/annurev.arplant.54.031902.134938. PMID 14503002.
  15. 1 2 Fahlbusch, Karl-Georg; Hammerschmidt, Franz-Josef; Panten, Johannes; Pickenhagen, Wilhelm; Schatkowski, Dietmar; Bauer, Kurt; Garbe, Dorothea; Surburg, Horst (2003). "Flavors and Fragrances". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a11_141. ISBN 3-527-30673-0.
  16. ↑ Friedman, M; Kozuekue, N; Harden, L.A (2000). "Cinnamaldehyde content in foods determined by gas chromatography-mass spectrometry". Journal of Agricultural and Food Chemistry. 48: 5702–5709. doi:10.1021/jf000585g.
  17. 1 2 "Cinnamaldehyde Use". PAN Pesticides Database. Retrieved 2007-10-23.
  18. ↑ Dick-Pfaff, Cornelia (July 19, 2004). "Wohlriechender Mückentod" (in German).
  19. ↑ Cheng, Sen-Sung; Liu, Ju-Yun; Tsai, Kun-Hsien; Chen, Wei-June; Chang, Shang-Tzen (2004). "Chemical Composition and Mosquito Larvicidal Activity of Essential Oils from Leaves of Different Cinnamomum osmophloeum Provenances". Journal of Agricultural and Food Chemistry. 52 (14): 4395–400. doi:10.1021/jf0497152. PMID 15237942. Lay summary – Science Daily (July 16, 2004).
  20. ↑ Ma WB, Feng JT, Jiang ZL, Zhang X (2014). "Fumigant Activity of 6 Selected Essential Oil Compounds and Combined Effect of Methyl Salicylate And Trans-Cinnamaldehyde Against Culex pipiens pallens". Journal of the American Mosquito Control Association. 30 (3): 199–203. doi:10.2987/14-6412R.1. PMID 25843095.
  21. ↑ Growcock, F. B. (December 1989). "Inhibition of Steel Corrosion in HCl by Derivatives of Cinnamaldehyde:". Corrosion. 45 (12): 1003–1007. doi:10.5006/1.3585007.
  22. ↑ Growcock, F. B.; Frenier, W. W.; Andreozzi, P. A. (December 1989). "Inhibition of Steel Corrosion in HCl by Derivatives of Cinnamaldehyde:". Corrosion. 45 (12): 1007–1015. doi:10.5006/1.3585008.
  23. ↑ Ka, Hyeon; Park, Hee-Juhn; Jung, Hyun-Ju; Choi, Jong-Won; Cho, Kyu-Seok; Ha, Joohun; Lee, Kyung-Tae (2003). "Cinnamaldehyde induces apoptosis by ROS-mediated mitochondrial permeability transition in human promyelocytic leukemia HL-60 cells". Cancer Letters. 196: 143–152.
  24. ↑ López, P.; Sánchez, C.; Batlle, R.; Nerín, C. (2007). "Vapor-Phase Activities of Cinnamon, Thyme, and Oregano Essential Oils and Key Constituents against Foodborne Microorganisms". J. Agric. Food Chem. 55: 4348–4356.
  25. ↑ Bandell, M; Story, GM; Hwang, SW; Viswanath, V; Eid, SR; Petrus, MJ; Earley, TJ; Patapoutian, A. "Noxious cold ion channel TRPA1 is activated by pungent compounds and bradykinin". Neuron. 41: 849–857.
  26. ↑ Zucca P, Littarru M, Rescigno A, Sanjust E (2009). "Cofactor recycling for selective enzymatic biotransformation of cinnamaldehyde to cinnamyl alcohol". Bioscience, Biotechnology, and Biochemistry. 73 (5): 1224–6. doi:10.1271/bbb.90025. PMID 19420690.
  27. ↑ Olsen, R. V.; Andersen, H. H.; Møller, H. G.; Eskelund, P. W.; Arendt-Nielsen, L (2014). "Somatosensory and vasomotor manifestations of individual and combined stimulation of TRPM8 and TRPA1 using topical L-menthol and trans-cinnamaldehyde in healthy volunteers". European Journal of Pain. 18 (9): 1333–42. doi:10.1002/j.1532-2149.2014.494.x. PMID 24664788.

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