Chrysanthemic acid
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| IUPAC name
2,2-Dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylic acid
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3D model (JSmol)
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| ECHA InfoCard | 100.022.788 |
PubChem CID
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CompTox Dashboard (EPA)
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| Properties | |
| C10H16O2 | |
| Molar mass | 168.236 g·mol−1 |
| Melting point | 17 °C (63 °F; 290 K) (1R,3R) or (+)-trans |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references
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Chrysanthemic acid is an organic compound that is related to a variety of natural and synthetic insecticides. It is a terpenoic acid related to the pyrethrin I and II, as well as the pyrethroids. One of the four stereoisomers, (1R,3R)- or (+)-trans-chrysanthemic acid (pictured), is the acid part of the ester pyrethrin I, which occurs naturally in the seed cases of Chrysanthemum cinerariaefolium. Many synthetic pyrethroids, for example the allethrins, are esters of all four stereoisomers.[1] Staudinger and Ružička named chrysanthemic acid in 1924.[2]
Biosynthesis
Chrysanthemic acid is derived from two dimethylallyl diphosphate (DMAPP) isoprene units in several steps. First, the enzyme chrysanthemyl diphosphate synthase (CDS) catalyses the head-to-head coupling of the isoprene units to produce trans-chrysanthemyl diphosphate (CDP).[3] In the second step, CDP is converted into trans-chrysanthemol, catalysed by either CDS or one or more phosphatases.[4] Two subsequent oxidation reactions, catalysed sequentially by an alcohol dehydrogenase (ADH) and an aldehyde dehydrogenase (ALDH), convert trans-chrysanthemol to trans-chrysanthemic acid.[5][6]
Industrial synthesis
Chrysanthemic acid is produced industrially in a cyclopropanation reaction of a diene as a mixture of cis- and trans isomers, followed by hydrolysis of the ester:[7]
Many pyrethroids are accessible by re-esterification of chrysanthemic acid ethyl ester - a perfume ingredient.
References
- ^ Faust, Rüdiger (2001). "Fascinating Natural and Artificial Cyclopropane Architectures". Angewandte Chemie International Edition. 40 (12): 2251–2253. doi:10.1002/1521-3773(20010618)40:12<2251::AID-ANIE2251>3.0.CO;2-R. PMID 11433485.
- ^ H. Staudinger, L. Ružička: "Insektentotende Stoffe H. Zur Konstitution der Chrysanthemummonocarbonsiiure und -dicarbonsiiure", Helv. Chem. Acta 7 (1924) 201
- ^ Rivera, Susan B.; Swedlund, Bradley D.; King, Gretchen J.; Bell, Russell N.; Hussey, Charles E.; Shattuck-Eidens, Donna M.; Wrobel, Wislawa M.; Peiser, Galen D.; Poulter, C. Dale (2001-04-10). "Chrysanthemyl diphosphate synthase: Isolation of the gene and characterization of the recombinant non-head-to-tail monoterpene synthase from Chrysanthemum cinerariaefolium". Proceedings of the National Academy of Sciences. 98 (8): 4373–4378. doi:10.1073/pnas.071543598. PMC 31842. PMID 11287653.
- ^ Yang, Ting; Stoopen, Geert; Yalpani, Nasser; Vervoort, Jacques; de Vos, Ric; Voster, Alessandra; Verstappen, Francel W. A.; Bouwmeester, Harro J.; Jongsma, Maarten A. (2011-07-01). "Metabolic engineering of geranic acid in maize to achieve fungal resistance is compromised by novel glycosylation patterns". Metabolic Engineering. 13 (4): 414–425. doi:10.1016/j.ymben.2011.01.011. ISSN 1096-7176.
- ^ Xu, Haiyang; Moghe, Gaurav D.; Wiegert-Rininger, Krystle; Schilmiller, Anthony L.; Barry, Cornelius S.; Last, Robert L.; Pichersky, Eran (2018-01). "Coexpression Analysis Identifies Two Oxidoreductases Involved in the Biosynthesis of the Monoterpene Acid Moiety of Natural Pyrethrin Insecticides in Tanacetum cinerariifolium". Plant Physiology. 176 (1): 524–537. doi:10.1104/pp.17.01330. ISSN 0032-0889. PMC 5761793. PMID 29122986.
{{cite journal}}: Check date values in:|date=(help) - ^ Xu, Haiyang; Lybrand, Daniel; Bennewitz, Stefan; Tissier, Alain; Last, Robert L.; Pichersky, Eran (2018-05-01). "Production of trans-chrysanthemic acid, the monoterpene acid moiety of natural pyrethrin insecticides, in tomato fruit". Metabolic Engineering. 47: 271–278. doi:10.1016/j.ymben.2018.04.004. ISSN 1096-7176. PMC 6659395. PMID 29649589.
- ^ Kelly Lawrence F (1987). "A synthesis of chrysanthemic ester: An undergraduate experiment". J. Chem. Educ. 64 (12): 1061. Bibcode:1987JChEd..64.1061K. doi:10.1021/ed064p1061.