EP0021100B1 - Cyclohexènes seuls ou en mélange avec (IV), procédé (II) pour la préparation de (I), utilisation de (I) resp. (I+IV) comme substances aromatisantes et/ou parfumantes et compositions de substances aromatisantes et/ou parfumantes contenant (I) resp. (I+IV) - Google Patents

Cyclohexènes seuls ou en mélange avec (IV), procédé (II) pour la préparation de (I), utilisation de (I) resp. (I+IV) comme substances aromatisantes et/ou parfumantes et compositions de substances aromatisantes et/ou parfumantes contenant (I) resp. (I+IV) Download PDF

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Publication number
EP0021100B1
EP0021100B1 EP80102995A EP80102995A EP0021100B1 EP 0021100 B1 EP0021100 B1 EP 0021100B1 EP 80102995 A EP80102995 A EP 80102995A EP 80102995 A EP80102995 A EP 80102995A EP 0021100 B1 EP0021100 B1 EP 0021100B1
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Prior art keywords
mixture
ester
methyl
ethyl
formula
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Expired
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EP80102995A
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German (de)
English (en)
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EP0021100A1 (fr
Inventor
Hanspeter Dr. Schenk
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Givaudan SA
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L Givaudan and Co SA
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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 invention relates to new fragrances and / or flavors. These are the compounds of the formula wherein R is C 1-4 alkyl or C 2 - 4 alkenyl means and one of the three dashed lines represents an additional bond.
  • the radicals R can be straight-chain or branched. Ethyl, isobutyl and allyl are preferred.
  • the invention further relates to a process for the preparation of the compounds of formula I.
  • This process is characterized in that an ester of the formula wherein RC 1-4 alkyl or C 2-4 alkenyl, cyclized.
  • esters I can be prepared by the known methods of preparing cyclogeranoyl derivatives.
  • Suitable cyclizing agents are inorganic and organic protonic acids, such as sulfuric acid, phosphoric acid, methanesulfonic acid, formic acid, acetic acid, etc., or Lewis acids, such as BF 3 , SnC1 4 , ZnCl 2 , etc.
  • the cyclization can be carried out with or without a solvent.
  • Suitable solvents are inert solvents such as hexane, benzene, nitromethane, etc.
  • the temperature is not critical (room temperature, or higher or lower temperatures).
  • the new organoleptically active esters II which are also the subject of the present application, are expediently prepared from the known 3,6-dimethyl-5-hepten-2-one.
  • reaction temperature is not critical. The temperature range of approximately 40-60 ° is preferred, but it is also possible to work at a lower or higher temperature.
  • a resulting methyl or ethyl ester of formula II can optionally be transesterified in a conventional manner, for. B. by heating with a higher alcohol, e.g. B. isobutanol, advantageously under alkaline conditions, the methanol or ethanol formed from the Reaction mixture can be distilled off continuously.
  • a higher alcohol e.g. B. isobutanol
  • the separation of the isomer mixtures can, if desired, in the usual way, e.g. B. by means of preparative gas chromatography.
  • the isomers of I do not differ fundamentally in their organoleptic properties, so that the isomer mixture in particular can be used for economic reasons.
  • the compounds I have particular organoleptic properties which make them particularly suitable as fragrances and / or flavors.
  • the invention accordingly also relates to the use of the compounds I as fragrances and / or flavorings.
  • the compounds of formula I are particularly suitable due to their natural odor notes for modifying known compositions in which, for. B. the citrus notes should be expressed more (e.g. for Cologne types and the like, 0.0s), but also of floral, especially rose compositions, where u. a. the use of compounds of the formula I leads to a clarification of the musk effect (ry types, composition of the feminine direction) and of wood compositions, where the addition of the new compounds 1 underlines the sought-after, expensive sandal notes (did types of general direction).
  • Fruit bases e.g. B. of the type apricot containing I appear fuller, sweeter and have a pronounced jam note.
  • the 2,3,6,6-tetramethyl-2-cyclohexene-1-carboxylic acid ethyl ester z. B. is characterized by strong, floral-spicy and woody notes of great radiance. The fruity-sweet, slightly powdery side notes of this compound are also worth mentioning.
  • This preferred compound differs organoleptically in a clear and surprising manner from the structurally obvious known compound, the 2,5,6,6-tetramethyl-cyclohex-2-ene-1-carboxylic acid ethyl ester (H. Favre and H. Schinz, Helv 35, 1627 (1952), which ester has only musty and earthy odor notes.
  • the compounds I can be used, for example, to produce or improve, reinforce, increase or modify a wide variety of fruit flavors, e.g. B. raspberry or apricot flavors can be used.
  • fruit flavors e.g. B. raspberry or apricot flavors
  • the characteristic characteristic of fresh grapes are advantageously emphasized.
  • Food yogurt, confectionery, etc.
  • luxury foods tea, tobacco, etc.
  • beverages lemonade, etc.
  • DT-OS see, eg. 2644762
  • 2-ethyl-6,6-dimethyl-2-cyclohexene-1-carboxylate surprising odor qualities namely those of great naturalness and radiance.
  • the new mixtures are also excellently suitable for use in fruit flavors of all kinds, but in particular also for flavoring tobacco.
  • the ratio of I to IV can be varied within a wide range, e.g. B. 90:10 to 10:90. The range from 10:90 to 30:70 is preferred.
  • the compounds of the formula (or the mixtures I + IV) can be used within wide limits, which can range, for example, from 0.1 (detergents) to 30% (alcoholic solutions) in compositions, without these values, however, being intended to represent limit values, since the experienced perfumer can achieve effects with even lower concentrations or build up new complexes with even higher doses.
  • the preferred concentrations are between 0.5 and 25%.
  • the compositions produced with I can be used for all types of perfumed consumer goods (Eaux de Cologne, Eaux de Toilette, extras, lotions, creams, shampoos, soaps, ointments, powder, toothpaste, mouthwashes, deodorants, detergents, tobacco, etc.).
  • the compounds 1 can accordingly be used in the preparation of compositions and - as the above compilation shows - using a wide range of known odorants or odorant mixtures.
  • the above-mentioned known fragrances or mixtures of fragrances can be used in a manner known to the perfumer, such as, for example, B. from W. A. Poucher, Perfumes, Cosmetics, Soaps 2, 7th edition, Chapman and Hall, London 1974.
  • a suitable dosage includes, for example, the range of 0.01 ppm-100 ppm, preferably the range of 0.01 ppm-20 ppm in the finished product, i. i.e. the flavored food, stimulant or beverage.
  • the dosage can, however, also be higher and cover a larger range, for example the range from 1 to 1000 ppm, preferably 50-500 ppm.
  • the compounds can be mixed in a conventional manner with the constituents used for flavoring compositions or added to such flavors.
  • the aromas used according to the invention are understood to mean flavoring compositions which can be diluted in a manner known per se or distributed in edible materials. They contain, for example, about 0.1-10, in particular 0.5-3,% by weight. They can be converted into the usual forms of use, such as solutions, pastes or powders, using methods known per se.
  • the products can be spray dried, vacuum dried or lyophilized.
  • carrier materials thickeners, flavor enhancers, spices and auxiliary ingredients etc. are suitable for the production of the usual forms of use: gum arabic, tragacanth, salts or brewer's yeast, alginates, carrageenan or similar absorbents; Indoles, maltol, dienals, spice oleoresins, smoke flavors; Cloves, diacetyl, sodium citrate; Monosodium glutamate, disodium aminosin 5'-monophosphate (IMP), disodium guanosine 5-phosphate (GMP); or special flavorings, water, ethanol, propylene glycol, glycerin.
  • gum arabic tragacanth, salts or brewer's yeast, alginates, carrageenan or similar absorbents
  • Indoles maltol, dienals, spice oleoresins, smoke flavors
  • Cloves diacetyl, sodium citrate
  • Example 1 According to the procedure of Example 1, 90 g of an ester mixture consisting of 75% c, t-3-ethyl-7-methyl-2,6-octadienoic acid ethyl ester and 25% c, t-3,4,7- Trimethyl-2,6-octadienklareäthylester 88.7 g of crude product.
  • Example 2 According to the procedure of Example 1, 71 g of an ester mixture consisting of 80% c, t-3,4,7-trimethyl-2,6-octadienoic acid ethyl ester and 20% c, t-3-ethyl-7- Methyl methyl 2,6-octadienoate 66.5 g of crude product.
  • the ketone mixture consisting of 23.9% 3,6-dimethyl-5-hepten-2-one and 76.1% 7-methyl-6-octen-3-one, can be prepared in a manner known per se (see e.g. Belgian patent 634 738 from 10.1.1964) can be obtained from 3-methyl-1-buten-3-ol, methylbutenyl ether and phosphoric acid as a catalyst in an autoclave at 180 ° C. in 54.4% yield.
  • the mixture consists of 71.6% c, t-3-ethyl-7-methyl-2,6-octadienoic acid isobutyl ester and 20.1% c, t-3,4,7-trimethyl-2,6-octadienoic acid isobutyl ester.
  • the suitable dosage is, for example, 100 g / 100 kg tobacco.
  • the tobacco note is significantly increased.
  • Smoking the flavored tobacco creates a typical smell and taste impression that is strongly pronounced of bright Virginia tobacco.
  • the suitable dosage is e.g. B. 40 g per 100 liters of syrup.
  • Suitable dosage e.g. B. 40 g per 100 liters of syrup.
  • the addition of the mixture I '+ IV' (in a ratio of 25:75) to composition A results in a clearly noticeable change in smell and taste.
  • the original sweet note is advantageously weakened, a fruity-fresh note appears that is characteristic of fresh grapes.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (14)

1. Composés de formule:
Figure imgb0030
où R représente un alcoyle en C1 à C4 ou un alcényle en C2 à C4 et où l'une des trois lignes dessinées en pointillé représente une liaison supplémentaire.
2. Composés de formule 1 selon la revendication 1, où R = éthyle.
3. Ester éthylique de l'acide 2,3,6,6-tétraméthyl-2-cyclohexène-1-carboxylique.
4. Mélanges de composés de formules:
Figure imgb0031
où R représente un alcoyle en Ci à C4 ou un alcényle en C2 à C4 et où dans les formules I et IV l'une des lignes dessinées en pointillé représente une liaison supplémentaire.
5. Mélanges selon la revendication 4, caractérisés en ce que I et IV se présentent surtout sous forme α.
6. Mélanges selon l'une des revendications 4 ou 5, caractérisés en ce que R est un éthyle.
7. Mélanges selon l'une des revendications 4 ou 5, caractérisés en ce que R est un méthyle, un isobutyle ou un allyle.
8. Composés de formule:
Figure imgb0032
où R représente un alcoyle en Ci à C4 ou un alcényle en C2 à C4 et où l'une des trois lignes dessinées en pointillé représente une liaison supplémentaire, comme agents odorants et/ou aromatisants.
9. Mélanges selon l'une des revendications 4 à 7 comme agents odorants et/ou aromatisants.
10. Compositions odorantes et/ou aromatisantes, caractérisées en ce qu'elles contiennent un composé de formule:
Figure imgb0033
où R représente un alcoyle en Ci à C4 ou un alcényle en C2 à C4 et où l'une des trois lignes dessinées en pointillé représente une liaison supplémentaire.
11. Compositions odorantes et/ou aromatisantes, caractérisées en ce qu'elles contiennent un mélange selon l'une des revendications 4 à 7.
12. Procédé de préparation de composés de formule:
Figure imgb0034
où R représente un alcoyle en C1 à C4 et où l'une des trois lignes dessinées en pointillé représente une liaision supplémentaire, caractérisé en ce qu'on cyclise un ester de formule:
Figure imgb0035
où R représente un alcoyle en C1 à C4 ou un alcényle en C2 à C4.
13. Application de composés de formule:
Figure imgb0036
où représente un alcoyle en C1 à C4 ou un alcényle en C2 à C4 et où l'une des trois lignes dessinées en pointillé représente une liaison supplémentaire, comme agents odorants et/ou aromatisants.
14. Application de mélanges selon l'une des revendications 4 à 7 comme agents odorants et/ou aromatisants.
EP80102995A 1979-06-13 1980-05-29 Cyclohexènes seuls ou en mélange avec (IV), procédé (II) pour la préparation de (I), utilisation de (I) resp. (I+IV) comme substances aromatisantes et/ou parfumantes et compositions de substances aromatisantes et/ou parfumantes contenant (I) resp. (I+IV) Expired EP0021100B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH5527/79 1979-06-13
CH552779 1979-06-13
CH316380 1980-04-24
CH3163/80 1980-04-24

Publications (2)

Publication Number Publication Date
EP0021100A1 EP0021100A1 (fr) 1981-01-07
EP0021100B1 true EP0021100B1 (fr) 1982-11-17

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EP80102995A Expired EP0021100B1 (fr) 1979-06-13 1980-05-29 Cyclohexènes seuls ou en mélange avec (IV), procédé (II) pour la préparation de (I), utilisation de (I) resp. (I+IV) comme substances aromatisantes et/ou parfumantes et compositions de substances aromatisantes et/ou parfumantes contenant (I) resp. (I+IV)

Country Status (6)

Country Link
US (3) US4375001A (fr)
EP (1) EP0021100B1 (fr)
BR (1) BR8003579A (fr)
CA (1) CA1142955A (fr)
DE (1) DE3061098D1 (fr)
ES (1) ES492367A0 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3514665A1 (de) * 1985-04-23 1986-10-30 Consortium für elektrochemische Industrie GmbH, 8000 München Trimethylcyclohexen-derivate, ihre herstellung und deren verwendung als duftstoffe
US4832059A (en) * 1987-12-08 1989-05-23 Lorillard, Inc. Citrus-flavored tobacco articles
EP0378825B1 (fr) * 1989-01-18 1994-07-06 Firmenich Sa Esters alicycliques et leur utilisation à titre d'ingrédients parfumants
JP2840899B2 (ja) * 1991-03-26 1998-12-24 高砂香料工業株式会社 光学活性な（１ｒ，６ｓ）−２，２，６−トリメチルシクロヘキサンカルボン酸エチルを含有する香料組成物及びその有効成分の製造法
WO1994013766A2 (fr) * 1992-12-11 1994-06-23 Quest International B.V. Esters d'acide dimethyl-cyclohexanecarboxylique en parfumerie
US5451401A (en) * 1993-09-29 1995-09-19 The Procter & Gamble Company Diphosphonic acid esters as tartar control agents
EP1182190A1 (fr) * 2000-08-25 2002-02-27 Givaudan SA Esters insaturés
JP4177002B2 (ja) * 2002-02-22 2008-11-05 高砂香料工業株式会社 香料組成物

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3931326A (en) * 1967-11-09 1976-01-06 Firmenich Sa Alkenoyl-cyclohexadienes
US4028278A (en) * 1971-08-17 1977-06-07 Firmenich S.A. Cycloaliphatic unsaturated ketones as fragrance modifying agents
CH586551A5 (fr) * 1974-01-29 1977-04-15 Firmenich & Cie
IT1034605B (it) * 1974-04-19 1979-10-10 Givaudan & Cie Sa Profumi
US4018718A (en) * 1974-04-19 1977-04-19 Givaudan Corporation 2-Ethyl-3,6,6-trimethyl-1-crotonyl-2-cyclohexene-type compounds and perfume compositions
CH615827A5 (en) * 1975-10-09 1980-02-29 Givaudan & Cie Sa Use of ethyl 2-ethyl-6,6-dimethyl-2-cyclohexene-1-carboxylate as perfume
US4113663A (en) * 1975-10-09 1978-09-12 Givaudan Corporation 2-Ethyl-6,6-dimethyl-2-cyclohexene-1-carboxylic acid ethyl ester perfume compositions
DE2849642A1 (de) * 1978-11-16 1980-06-04 Henkel Kgaa Neue aldehyde und deren verwendung als riechstoffe
US4313842A (en) * 1978-12-15 1982-02-02 International Flavors & Fragrances Inc. Process for hydrogenation of 2,6,6-trimethyl cyclohexene derivatves, products produced thereby and organoleptic uses of said products
US4283576A (en) * 1979-06-27 1981-08-11 International Flavors & Fragrances Inc. Cyclohexenemethanols
US4260527A (en) * 1980-06-05 1981-04-07 International Flavors & Fragrances Inc. Use of 1-acetyl-22,6-trimethyl cyclohexene-1 in augmenting or enhancing the aroma of perfumes and cologne

Also Published As

Publication number Publication date
US4474687A (en) 1984-10-02
US4570648A (en) 1986-02-18
EP0021100A1 (fr) 1981-01-07
ES8105256A1 (es) 1981-06-01
BR8003579A (pt) 1981-01-05
US4375001A (en) 1983-02-22
ES492367A0 (es) 1981-06-01
DE3061098D1 (en) 1982-12-23
CA1142955A (fr) 1983-03-15

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