Chemistry:Chrysanthemic acid

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Chrysanthemic acid
(1R,3R)- or (+)-trans-chrysanthemic acid
Names
IUPAC name
2,2-Dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylic acid
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
  • 16747 (1R,3R) or (+)-trans
  • 33607 (1S,3S) or (−)-trans
  • 33606 (1R,3S) or (+)-cis
  • 20755 (1S,3R) or (−)-cis
UNII
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

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]

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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]

Chrysanthemic ester synthesis

Many pyrethroids are accessible by re-esterification of chrysanthemic acid ethyl ester - a perfume ingredient.

References

  1. ↑ 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. 
  2. ↑ H. Staudinger, L. Ružička: "Insektentotende Stoffe H. Zur Konstitution der Chrysanthemummonocarbonsiiure und -dicarbonsiiure", Helv. Chem. Acta 7 (1924) 201
  3. ↑ 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. et al. (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. PMID 11287653. PMC 31842. https://www.pnas.org/doi/full/10.1073/pnas.071543598. 
  4. ↑ Yang, Ting; Stoopen, Geert; Yalpani, Nasser; Vervoort, Jacques; de Vos, Ric; Voster, Alessandra; Verstappen, Francel W. A.; Bouwmeester, Harro J. et al. (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. https://www.sciencedirect.com/science/article/pii/S1096717611000127. 
  5. ↑ Xu, Haiyang; Moghe, Gaurav D.; Wiegert-Rininger, Krystle; Schilmiller, Anthony L.; Barry, Cornelius S.; Last, Robert L.; Pichersky, Eran (January 2018). "Coexpression Analysis Identifies Two Oxidoreductases Involved in the Biosynthesis of the Monoterpene Acid Moiety of Natural Pyrethrin Insecticides in Tanacetum cinerariifolium" (in en). Plant Physiology 176 (1): 524–537. doi:10.1104/pp.17.01330. ISSN 0032-0889. PMID 29122986. PMC 5761793. https://academic.oup.com/plphys/article/176/1/524-537/6117124. 
  6. ↑ 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. PMID 29649589. PMC 6659395. https://www.sciencedirect.com/science/article/pii/S1096717617304585. 
  7. ↑ Kelly Lawrence F (1987). "A synthesis of chrysanthemic ester: An undergraduate experiment". J. Chem. Educ. 64 (12): 1061. doi:10.1021/ed064p1061. Bibcode: 1987JChEd..64.1061K. 



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