Chrysanthemum acid

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Structural formula
Structural formula of chrysantemic acid
(1 R , 3 R ) - (+) - chrysanthemum acid
General
Surname Chrysanthemum acid
other names
  • (1 R , 3 R ) -2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanoic acid
  • (+) - trans -Chrysanthemum acid
Molecular formula C 10 H 16 O 2
Brief description

colorless to light yellow liquid

External identifiers / databases
CAS number
  • 10453-89-1 (undefined stereochemistry)
  • 4638-92-0 (1 R , 3 R )
  • 26771-06-2 (1 S , 3 R )
  • 2259-14-5 (1 S , 3 S )
  • 15259-78-6 (1 RS , 3 SR )
EC number 225-067-5
ECHA InfoCard 100,022,788
PubChem 16747
ChemSpider 15876
Wikidata Q5114537
properties
Molar mass 168.23 g mol −1
Physical state

liquid

Melting point

17-21 ° C

Refractive index

1.477

safety instructions
GHS labeling of hazardous substances
05 - Corrosive

Caution

H and P phrases H: 315-319
P: 305 + 351 + 338
Toxicological data

98 mg kg −1 ( LD 50 ,  mouse ,  intraperitoneal )

As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions . Refractive index: Na-D line , 20 ° C

Chrysanthemum acid is a chemical compound from the group of carboxylic acids . It is one of the monocyclic monoterpenes with a cyclopropane structure. The (+) - trans isomer is the naturally occurring acid component of pyrethrin I, an insecticide from the group of pyrethrins .

properties

Chrysanthemum acid is a colorless to light yellow liquid.

Occurrence

Chrysanthemum acid can be obtained from the flower heads of the daisy family of the genus Chrysanthemum .

Tanacetum cinerariifolium ( Syn . : Chrysanthemum cinerariifolium )

In some related species of wild flowers such as the Dalmatian insect flower ( Tanacetum cinerariifolium ), the monoterpenes formed are intermediates for the synthesis of pyrethrins.

Besides Chrysanthemylester were also called pheromones of species of mealybugs found, for example as sex pheromone of zitrophilen Wolllaus Pseudococcus calceolariae.

Synthetic routes

In plants, the first steps in the biosynthesis of chrysanthemum acid starting from dimethylallyl pyrophosphate (DMAPP) are catalyzed by chrysanthemyl diphosphate synthase (CDS), an enzyme related to farnesyl diphosphate synthase . First of all, the chrysanthemyl diphosphate (CPP) is produced by two molecules of DMAPP reacting with each other to split off pyrophosphate (PP i ):

synthesis

Under the conditions prevailing in plant cells, the enzyme also catalyzes the next step, in which CPP becomes chrysanthemol by splitting off the diphosphate residue . With this enzymatic hydrolysis , CDS is bifunctional and develops chrysanthemol synthase activity. The subsequent oxidation of the monocyclic monoterpene alcohol then leads to chrysanthemum acid.

Using this synthetic route, enantiomerically pure (+) - trans -chrysanthemum acid can be obtained with cloned E. coli strains .

In the laboratory, the ethyl ester of chrysanthemum acid can be obtained by reacting 2,5-dimethyl-hexa-2,4-diene with diazoacetic acid ethyl ester using transition metal catalysts , followed by hydrolysis to obtain chrysanthemum acid.

Individual evidence

  1. ↑ a b c d e f g data sheet (+) - trans-Chrysanthemic acid from Sigma-Aldrich , accessed on February 6, 2016 ( PDF ).
  2. ↑ A. Townshend, DT Burns, Ryszard Lobinski, EJ Newman, G. Guilbault, Z. Marczenko, H. Onishi: Dictionary of Analytical Reagents . CRC Press, 1993, ISBN 978-0-412-35150-1 , pp. 253 ( limited preview in Google Book search).
  3. ↑ Entry on pyrethrum. In: Römpp Online . Georg Thieme Verlag, accessed on April 6, 2016.
  4. ↑ Jonathan Clayden, Nick Greeves, Stuart G. Warren: Organic Chemistry . 2nd Edition. Springer Spectrum, Berlin, Heidelberg 2013, ISBN 978-3-642-34715-3 .
  5. ↑ EuroMed PlantBase , accessed on February 2, 2017.
  6. ↑ Susan B. Rivera, Bradley D. Swedlund, Gretchen J. King, Russell N. Bell, Charles E. Hussey, Donna M. Shattuck-Eidens, Wislawa M. Wrobel, Galen D. Peiser, C. Dale Poulter: Chrysanthemyl diphosphate synthase: Isolation of the gene and characterization of the recombinant non-head-to-tail monoterpene synthase from Chrysanthemum cinerariaefolium . In: Proceedings of the National Academy of Sciences of the United States of America . tape 98 , no. 8 , 2001, ISSN  0027-8424 , p. 4373–4378 , doi : 10.1073 / pnas.071543598 , PMC 31842 (free full text).
  7. ↑ Yunfan Zou and Jocelyn G. Millar: Chemistry of the pheromones of mealybug and scale insects . In: Natural Product Reports . tape 32 , no. 7 , 2015, p. 1067-1113 , doi : 10.1039 / C4NP00143E . free access
  8. ↑ Ting Yang, Liping Gao, Hao Hu, Geert Stoopen, Caiyun Wang, Maarten A. Jongsma: Chrysanthemyl Diphosphate Synthase Operates in Planta as a Bifunctional Enzyme with Chrysanthemol Synthase Activity . In: The Journal of Biological Chemistry . tape 289 , no. 52 , December 26, 2014, p. 36325-36335 , doi : 10.1074 / jbc.M114.623348 , PMC 4276892 (free full text).
  9. ↑ M. Nishizawa, M. Shimizu, H. Ohkawa, M. Kanaoka: Stereoselective production of (+) - trans-chrysanthemic acid by a microbial esterase: cloning, nucleotide sequence, and overexpression of the esterase gene of Arthrobacter globiformis in Escherichia coli . In: Applied and Environmental Microbiology . tape 61 , no. 9 , September 1995, p. 3208-3215 , PMC 167599 (free full text).
  10. ^ Klaus Schwetlick: Organikum . Ed .: Heinz GO Becker. 21st edition. Wiley-VCH, Weinheim 2001, ISBN 3-527-29985-8 .