Methyl dihydrojasmonate

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Structural formula
Structural formula of methyl dihydrojasmonate
Simplified structural formula without stereochemistry
General
Surname Methyl dihydrojasmonate
other names
  • Methyl 3-oxo-2-pentylcyclopentane acetate
  • Hedion
  • Kharismal
  • Cepionat
Molecular formula C 13 H 22 O 3
Brief description

colorless liquid with a floral, citrus-like, jasmine-like odor

External identifiers / databases
CAS number
  • 24851-98-7
  • 2630-39-9 [(-) - (1 R , 2 R ) -isomer]
  • 39647-11-5 [(+) - (1 R , 2 S ) -isomer]
  • 151716-36-8 [(+) - (1 S , 2 S ) -isomer]
PubChem 102861
Wikidata Q3144605
properties
Molar mass 226.31 g mol −1
Physical state

liquid

density

1.0 g cm −3

Melting point

<−20 ° C

boiling point

302-303 ° C

Vapor pressure

0.2 Pa (25 ° C)

solubility
  • very sparingly soluble in water (approx. 0.55 g l −1 at 20 ° C)
  • soluble in paraffin and propylene glycol
  • soluble in ethanol and oils
Refractive index

1.459 (20 ° C, cis-trans mixture)

safety instructions
GHS labeling of hazardous substances
no GHS pictograms
H and P phrases H: no H-phrases
P: no P-phrases
Toxicological data

> 5 g kg −1 ( LD 50 ,  rat ,  oral )

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

Methyl dihydrojasmonate is a chemical compound from the group of substituted carboxylic acid esters .

history

Methyl dihydrojasmonate was first synthesized in 1958 by Edouard Demole , who was commissioned by Roger Firmenich from the Firmenich company of the same name to study the olfactory compounds in jasmine.

Occurrence

Jasmine ( Jasminum grandiflorum )

Methyl dihydrojasmonate occurs naturally in jasmine oil ( Jasminum grandiflorum L.) and black tea, as well as in tobacco and tobacco smoke.

Extraction and presentation

Methyl jasmonate is contained in jasmine oil. The hydrogenation of the double bond in it produces methyl dihydrojasmonate and (+) - methyl dihydrojasmonate (Paradison).

Methyl dihydrojasmonate can be obtained by condensation of 2-pentyl-2-cyclopenten-1-one with methylmalonate , followed by hydrolysis , decarboxylation and methylation . This creates a 9: 1 mixture of the trans and cis isomers, which is marketed as a hedione.

Several thousand tons are produced or imported in Europe every year.

properties

Methyl dihydrojasmonate is a non-toxic, flammable, hardly inflammable, colorless liquid with a flowery, citrus-like, jasmine-like odor, which is very sparingly soluble in water.

Methyl dihydrojasmonate was identified as the first fragrance to stimulate the human pheromone receptor ( VN1R1 ). This causes an activation of a brain region that is involved in hormone control. In women, the effect is ten times stronger than in men. In laboratory studies by researchers from the Universities of Bern, Bochum and Cologne, Hedion reinforced reciprocal behaviors according to the motto "Like you me, like you me".

use

Methyl dihydrojasmonate is mainly used as an odorant for perfume , but also as an aroma and fragrance in various foods, air care products, biocides (e.g. disinfectants, pest control products), polishes and waxes, detergents and cleaning agents, cosmetics and personal care products, fillers, putties, Plasters, modeling clay, finger paints, fuels, inks and toners, and leather treatment products. The cis isomers have a much stronger odor than the trans isomers and have a 20 times lower odor threshold . Of all possible isomers, the (+) - (1 R ) - cis isomer has the most characteristic and intense jasmine odor, which is why special manufacturing processes have been developed for it.

Methyl dihydrojasmonate, for example, formed the basis for Edmond Roudnitska's Eau Sauvage by Dior (1966), Calandre and Metal by Paco Rabanne (1969 and 1977) and Yves Saint Laurent's Rive Gauche (1971). Chanel Nº 19 (1971) already contains 13% Hedion and First by Van Cleef & Arpels (1976) and Beautiful by Estée Lauder (1986) even 22%. Jasmine notes combined in equal parts (25% each) with sandalwood can be found in Samsara by Jean-Paul Guerlain (1990).

Individual evidence

  1. ↑ a b c d e f g h i j Entry on methyl dihydrojasmonate in the GESTIS substance database of the IFA , accessed on June 7, 2017(JavaScript required) .
  2. ↑ a b Datasheet Methyl dihydrojasmonate, mixture of cis and trans, ≥96%, FG from Sigma-Aldrich , accessed on June 7, 2017 ( PDF ).
  3. ↑ a b c d George A. Burdock: Fenaroli's Handbook of Flavor Ingredients, Fifth Edition . CRC Press, 2004, ISBN 978-1-4200-3787-6 , pp. 1985 ( limited preview in Google Book Search).
  4. ↑ methyl dihydrojasmonate . In: Food and Chemical Toxicology . tape 30 , 1992, pp. 85-86 , doi : 10.1016 / 0278-6915 (92) 90250-o (supplement).
  5. ^ Christian Chapuis: The Jubilee of Methyl Jasmonate and Hedione. In: Helvetica Chimica Acta . 95, 2012, pp. 1479–1511, doi : 10.1002 / hlca.201200070 .
  6. ↑ Alan Rodgman, Thomas A. Perfetti: The Chemical Components of Tobacco and Tobacco Smoke, Second Edition . CRC Press, 2016, ISBN 978-1-4665-1552-9 , pp. 443 ( limited preview in Google Book search).
  7. ↑ Wolfgang Legrum: Fragrances, between stench and fragrance occurrence, properties and use of fragrances and their mixtures . Springer-Verlag, 2011, ISBN 978-3-8348-8276-9 , pp. 128 ( limited preview in Google Book search).
  8. ↑ Christian Chapuis, George H. Büchi, Hans Wüest: Synthesis ofcis-Hedione and Methyl Jasmonate via Cascade Baylis-Hillman Reaction and Claisen Ortho Ester Rearrangement . In: Helvetica Chimica Acta . tape 88 , no. December 12 , 2005, pp. 3069 , doi : 10.1002 / hlca.200590248 .
  9. ↑ a b Wiley-VCH: Ullmann's Food and Feed, 3 Volume Set . John Wiley & Sons, 2017, ISBN 978-3-527-33990-7 , pp. 1106 ( limited preview in Google Book search).
  10. ^ Günther Ohloff : Fragrances . John Wiley & Sons, 2004, ISBN 3-906390-30-6 , pp. 53 ( limited preview in Google Book search).
  11. ↑ a b InfoCard for methyl 3-oxo-2-pentylcyclopentaneacetate from the European Chemicals Agency (ECHA), accessed on June 10, 2017.
  12. ^ Valerie T. Politano, Elise M. Lewis, Alan M. Hoberman, Mildred S. Christian, Robert M. Diener, Anne Marie Api: Evaluation of the Developmental Toxicity of Methyl Dihydrojasmonate (MDJ) in Rats. In: International Journal of Toxicology. 27, 2008, pp. 295-300, doi : 10.1080 / 10915810802210158 .
  13. ^ I. Wallrabenstein, J. Gerber, S. Rasche, I. Croy, S. Kurtenbach, T. Hummel, H. Hatt: The smelling of Hedione results in sex-differentiated human brain activity. In: NeuroImage. 113, 2015, p. 365, doi : 10.1016 / j.neuroimage.2015.03.029 .
  14. ^ Sebastian Berger, Hanns Hatt, Axel Ockenfels: Exposure to Hedione Increases Reciprocity in Humans. In: Frontiers in Behavioral Neuroscience. 11, 2017, doi : 10.3389 / fnbeh.2017.00079 .
  15. ↑ The fragrance Hedion influences human behavior , Laborpraxis , accessed on June 7, 2017.
  16. ^ John Buckingham: Dictionary of Natural Products, Supplement 2 . CRC Press, 1995, ISBN 978-0-412-60420-1 , pp. 271 ( limited preview in Google Book search).
  17. ↑ Jian Zhou: Multi Catalyst system in Asymmetric Catalysis . John Wiley & Sons, 2014, ISBN 978-1-118-07186-1 , pp. 5 ( limited preview in Google Book search).
  18. ^ Robert R. Calkin, J. Stephan Jellinek: Perfumery Practice and Principles . John Wiley & Sons, 1994, ISBN 0-471-58934-9 , pp. 129 ( limited preview in Google Book search).
  19. ^ Günther Ohloff: Earthly Scents - Heavenly Lust . A cultural history of fragrances. Springer, Basel 1992, ISBN 978-3-0348-6160-1 , pp. 224 ( limited preview in Google Book search).