Chrysanthemic acid

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Chrysanthemic acid
(R,R)-(+)-trans-chrysanthemic acid.svg
Names
IUPAC name
2,2-Dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylic acid
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.022.788 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
  • 16747  (1R,3R) or (+)-trans
  • 33607  (1S,3S) or (−)-trans
  • 33606  (1R,3S) or (+)-cis
  • 20755  (1S,3R) or (−)-cis
UNII
  • InChI=1S/C10H16O2/c1-6(2)5-7-8(9(11)12)10(7,3)4/h5,7-8H,1-4H3,(H,11,12)/t7-,8+/m0/s1
    Key: XLOPRKKSAJMMEW-JGVFFNPUSA-N
  • CC(=CC1C(C1(C)C)C(=O)O)C
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).

Chrysanthemic acid is an organic compound that is related to a variety of natural and synthetic insecticides. It is 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]

Contents

Biosynthesis

Chrysanthemic acid is derived from its pyrophosphate ester, which in turn is produced naturally from two molecules of dimethylallyl diphosphate. [3]

CCPaseRxn'.png

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: [4]

ChrysanthemicAcidSynthesis.png

Many pyrethroids are accessible by re-esterification of chrysanthemic acid ethylester.

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Pyrethrin II Chemical compound

Pyrethrin II is an organic compound that is a potent insecticide. It is one of the two pyrethrins, the other being pyrethrin I. Thousands of tons this mixture are produced annually from chrysanthemum plants, which are cultivated in warm climates. Whereas pyrethrin I is a derivative of (+)-trans-chrysanthemic acid, in pyrethrin II one methyl group is oxidized to a carboxymethyl group, the resulting core being called pyrethric acid. Knowledge of their chemical structures opened the way for the production of synthetic analogues, which are called pyrethroids. In terms of their biosynthesis, pyrethrins are classified as terpenoids, being derived from dimethylallyl pyrophosphate.

Pyrethrin I Chemical compound

Pyrethrin I is one of the two pyrethrins, natural organic compounds with potent insecticidal activity. It is an ester of (+)-trans-chrysanthemic acid with (S)-(Z)-pyrethrolone.

Jasmolone Chemical compound

Jasmolone is an irregular monoterpene. Irregular monoterpenes are derived from two isoprene C5 units, but do not follow the usual head-to-tail coupling mechanism. Jasmolins are found in pyrethrum flowers. They can specifically be found in the flower heads of Chrysanthemum cinerariaefolium. Jasmolins act as an insecticide for the flower. It is found in the cytoplasm of plants.

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. Shattuck-Eidens DM, Wrobel WM, Peiser GD, Poulter CD (2001). "Chrysanthemyl diphosphate synthase: isolation of the gene and characterization of the recombinant non-head-to-tail monoterpene synthase from Chrysanthemum cinerariaefolium". Proc. Natl. Acad. Sci. U.S.A. 98 (8): 4373–8. Bibcode:2001PNAS...98.4373R. doi: 10.1073/pnas.071543598 . PMC   31842 . PMID   11287653.
  4. 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.