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EP1329443B1 - Cyclohexénylcyclopropylcétone - Google Patents

Cyclohexénylcyclopropylcétone Download PDF

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Publication number
EP1329443B1
EP1329443B1 EP20020250378 EP02250378A EP1329443B1 EP 1329443 B1 EP1329443 B1 EP 1329443B1 EP 20020250378 EP20020250378 EP 20020250378 EP 02250378 A EP02250378 A EP 02250378A EP 1329443 B1 EP1329443 B1 EP 1329443B1
Authority
EP
European Patent Office
Prior art keywords
damascone
compound
trimethylcyclohex
cyclopropyl
damasconene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP20020250378
Other languages
German (de)
English (en)
Other versions
EP1329443A1 (fr
Inventor
William L. Schreiber
Richard M. Boden
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
International Flavors and Fragrances Inc
Original Assignee
International Flavors and Fragrances Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by International Flavors and Fragrances Inc filed Critical International Flavors and Fragrances Inc
Priority to EP20020250378 priority Critical patent/EP1329443B1/fr
Priority to DE2002607974 priority patent/DE60207974T2/de
Publication of EP1329443A1 publication Critical patent/EP1329443A1/fr
Application granted granted Critical
Publication of EP1329443B1 publication Critical patent/EP1329443B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
    • C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms

Definitions

  • the present invention relates to new chemical entities and the incorporation and use of the new chemical entities as fragrance chemicals.
  • the present invention provides a novel compound, incorporation of the compound to provide a fragrance to perfumes, toilet water, colognes, personal products and the like.
  • the present invention is directed to the use of related compounds as a fragrance in perfumes, toilet water, colognes, personal products and the like.
  • the present invention is directed to cyclopropyl-2,6,6-trimethylcyclohex-3-enyl ketone, which is set forth below.
  • in another embodiment of the invention is a method for enhancing, modifying or augmenting a product by incorporating an olfactory acceptable amount of the compound into a fragrance formulation.
  • a method for making the claimed compound is also described.
  • the present invention is directed to the compound cyclopropyl-2,6,6-trimethylcyclohex-3-enyl ketone and the use of the compound in fragrance.
  • the compound is prepared by a two-step reaction sequence that is preferably conducted in a single pot. Generically, the reaction is described as the reaction of 4-acetyl-3,5,5-trimethylcyclohexene with a (C 1 -C 6 )alkyl magnesium chloride, preferably butyl magnesium chloride and bromochloroethane.
  • the odor characteristic of the compound is described as more floral, less minty and less fruity than the analog compounds set forth in U.S. Patents 6,025,527 and 6,051,548.
  • the cyclopropyl-2,6,6-trimethylcyclohex-3-enyl ketone compound was also found to possess a desirable cooling characteristic that the other cyclohexenyl cyclopropyl compounds in U.S. Patents 6,025,527 and 6,051,548 did not possess.
  • this compound is widely applicable in current perfumery products, including the preparation of perfumes and colognes, the perfuming of personal care products, such as soaps, shower gels and hair care products, as well as air fresheners and cosmetic preparations.
  • the present invention can also be used to perfume cleaning agents, such as, but not limited to, detergents, dishwashing materials, scrubbing compositions, window cleaners and the like.
  • the compounds of the present invention can be used alone or in combination with other perfuming compositions, solvents, adjuvants and the like.
  • the nature and variety of the other ingredients that can be additionally used in the various preparations are known to those with skill in the art.
  • fragrances can be employed in the present invention, the only limitation being the compatibility with the other components being employed.
  • Suitable fragrances include, but are not limited to, fruits such as almond, apple, cherry, grape, pear, pineapple, orange, strawberry, raspberry; musk; flower scents such as lavender-like, rose-like, iris-like and carnation-like.
  • Other pleasant scents include herbal scents, such as rosemary, thyme, basil and lavender, and woodland scents derived from pine, spruce and other forest smells.
  • Fragrances may also be derived from various oils, such as essential oils, or from plant materials, such as peppermint, spearmint and the like.
  • fragrances A list of suitable fragrances is provided in U.S. Patent 4,534,891. Another source of suitable fragrances is found in Perfumes Cosmetics and Soaps, Second Edition, edited by W. A. Poucher. 1959.
  • the fragrances provided in this treatise are acacia, cassie, chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle, hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cut hay, orange blossom, orchids, reseda, sweet pea, trefle, tuberose, vanilla, violet, wallflower and the like.
  • Olfactory effective amount is understood to mean the amount of compound in perfume compositions the individual component will contribute its particular olfactory characteristics, but the olfactory effect of the perfume composition will be the sum of the effects of each of the perfume or fragrance ingredients.
  • the compound of the invention can be used to alter the aroma characteristics of the perfume composition, or by modifying the olfactory reaction contributed by another ingredient in the composition. The amount will vary depending on many factors, including other ingredients, their relative amounts and the effect that is desired.
  • the level of compound of the invention employed in the perfumed article varies from about 0.005 to about 10 weight percent, preferably from about 0.5 to about 8 and most preferably from about 1 to about 7 weight percent.
  • other agents can be used, such as surfactants, emulsifiers and polymers to encapsulate the fragrance, without departing from the scope of the present invention.
  • Another method of reporting the level of the compound of the invention in the perfumed composition i.e., the compound as a weight percentage of the materials, is added to impart the desired fragrance.
  • the compound of the invention can range widely from 0.005 to about 70 weight percent of the perfumed composition, preferably from about 0.1 to about 50 and most preferably from about 0.2 to about 25 weight percent. Those with skill in the art will be able to employ the desired level of the compound of the invention to provide the desired fragrance and intensity.
  • Another advantage of the present compound is that its fragrance has been found to be complimentary to ⁇ -damascone, ⁇ -damascone and ß-damascone. This allows the cyclopropyl-2,6,6-trimethylcyclohex-3-enyl ketone to be used in combination with these commercially available fragrance materials.
  • a fragrance mixture contains multiple compounds including (a) first compound cyclopropyl-2,6,6-trimethylcyclohex-3-enyl ketone and (b) at least one compound selected from the group: ⁇ -damascone, ⁇ -damascone and ⁇ -damascone; wherein the weight of the first compound cyclopropyl-2,6,6-trimethylcyclohex-3-enyl ketone provided in said fragrance mixture is greater than the weight of the second material selected from the group consisting of ⁇ -damascone, ⁇ -damascone, ⁇ -damascone and mixtures of ⁇ -damasconene, ⁇ -damascone and ⁇ -damascone.
  • the weight ratio of cyclopropyl-2,6,6-trimethylcyclohex-3-enyl ketone to the damascone materials is generally from about 1.5:1 to about 10:1, preferably from 2:1 to about 8:1, most preferably from about 3:1 to about 5:1.
  • Butyl magnesium chloride provided in ether (1050 milliliters) was charged to a reaction vessel equipped with a stirrer, heating unit and equipment suitable for conducting vacuum distillation.
  • 4-acetyl-3,3,5-trimethylcyclohexene which is described and prepared in the literature, see K.S. Ayyar, R.C.Cookston, and A. Kagi, Journal Chemical Society Perkin, 1725 (1975); step 1 (250 grams) was added at room temperature, with the constant release of butane gas.
  • Bromochloroethane (228 grams) was added at 25°C over one hour. 250 Milliliters of 1-methyl-2-pyrrolidinone was then added to the reaction mixture, and the temperature of the reaction mixture was increased to about 42°C for about one hour.
  • the temperature was then raised to 60°C while distilling off ether.
  • the pot temperature was raised to 70°C and maintained at that temperature for about 24 hours.
  • Aqueous acetic acid 200 grams,10 weight percent was then added to the reaction mass.
  • the aqueous layer was separated and discarded.
  • the organic layer was washed a single time with 500 milliliters of 10% salt solution. Distillation provided approximately 249 grams of product.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Fats And Perfumes (AREA)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (13)

  1. Le composé cyclopropyl-2,6,6-triméthylcyclohex-3-ényl cétone.
  2. Le composé de la revendication 1 incorporé à des parfums, des eaux de Cologne, des eaux de toilette et des produits d'hygiène.
  3. Le composé de la revendication 2, dans lequel le produit d'hygiène est choisi dans le groupe consistant en des détergents, des compositions de lavage de la vaisselle, des composés à récurer et des produits de lavage des vitres.
  4. Procédé pour parfumer un produit en incorporant une quantité acceptable du point de vue olfactif du composé de la revendication 1.
  5. Procédé suivant la revendication 4, dans lequel le produit est incorporé à des parfums, à des eaux de Cologne, à de l'eau de toilette, à des produits de nettoyage et à des produits d'hygiène.
  6. Procédé suivant la revendication 5, dans lequel le produit de nettoyage est choisi dans le groupe consistant en des détergents, des compositions de lavage de la vaisselle, des composés à récurer et des produits de lavage des vitres.
  7. Mélange de senteurs qui contient de multiples composés, y compris (a) comme premier composé de la cyclopropyl-2,6,6-triméthylcyclohex-3-ényl cétone et (b) un deuxième composé choisi dans le groupe : α-damascone et γ-damascone.
  8. Mélange de senteurs suivant la revendication 7, dans lequel le poids de la cyclopropyl-2,6,6-triméthylcyclohex-3-ényl cétone servant de premier composé prévu dans le mélange de senteurs est supérieur au poids de la deuxième substance choisie dans le groupe consistant en la δ-damascone, la β-damascone, l'α-damascone et les mélanges de δ-damasconène, de β-damascone et d'α-damascone.
  9. Mélange de senteurs suivant la revendication 8, dans lequel le rapport en poids de la cyclopropyl-2,6,6-triméthylcyclohex-3-ényl cétone en tant que premier composé et de la deuxième substance choisie dans le groupe consistant en le δ-damasconène, le β-damasconène, l'α-damasconène et les mélanges de δ-damasconène, de β-damasconène et d'α-damasconène est compris entre 1,5:1 et environ 10:1.
  10. Mélange de senteurs suivant la revendication 8, dans lequel le rapport en poids de la cyclopropyl-2,6,6-triméthylcyclohex-3-ényl cétone servant de première substance et de la deuxième substance choisie dans le groupe consistant en la δ-damascone, la β-damascone, l'α-damascone et les mélanges de δ-damascone, de β-damascone et d'α-damascone est compris entre 2:1 et environ 8:1.
  11. Mélange de senteurs suivant la revendication 8, dans lequel le rapport en poids de la cyclopropyl-2,6,6-triméthylcyclohex-3-ényl cétone servant de première substance et de la deuxième substance choisie dans le groupe consistant en la δ-damascone, la β-damascone, l'α-damascone et les mélanges de δ-damascone, de β-damascone et d'α-damascone est compris entre environ 3:1 et environ 5:1.
  12. Procédé de préparation de la cyclopropyl-2,6,6-triméthylcyclohex-3-ényl cétone comprenant la réaction du 4-acétyl-3,5,5-triméthylcyclohexène, d'un chlorure d'alcoylmagnésium ayant de 1 à 6 atomes de carbone et du bromochloroéthane.
  13. Procédé suivant la revendication 12, dans lequel le chlorure d'alcoyl magnésium ayant de 1 à 6 atomes de carbone est le chlorure de butyl magnésium.
EP20020250378 2002-01-21 2002-01-21 Cyclohexénylcyclopropylcétone Expired - Lifetime EP1329443B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP20020250378 EP1329443B1 (fr) 2002-01-21 2002-01-21 Cyclohexénylcyclopropylcétone
DE2002607974 DE60207974T2 (de) 2002-01-21 2002-01-21 Cyclohexenylcyclopropylketon

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20020250378 EP1329443B1 (fr) 2002-01-21 2002-01-21 Cyclohexénylcyclopropylcétone

Publications (2)

Publication Number Publication Date
EP1329443A1 EP1329443A1 (fr) 2003-07-23
EP1329443B1 true EP1329443B1 (fr) 2005-12-14

Family

ID=8185653

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20020250378 Expired - Lifetime EP1329443B1 (fr) 2002-01-21 2002-01-21 Cyclohexénylcyclopropylcétone

Country Status (2)

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EP (1) EP1329443B1 (fr)
DE (1) DE60207974T2 (fr)

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6051548A (en) * 1998-11-05 2000-04-18 International Flavors & Fragrances Inc. Trimethylcyclohexenylcyclopropyl ketones perfume composition

Also Published As

Publication number Publication date
DE60207974T2 (de) 2006-08-17
EP1329443A1 (fr) 2003-07-23
DE60207974D1 (de) 2006-01-19

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