EP0021100A1 - 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
EP0021100A1
EP0021100A1 EP80102995A EP80102995A EP0021100A1 EP 0021100 A1 EP0021100 A1 EP 0021100A1 EP 80102995 A EP80102995 A EP 80102995A EP 80102995 A EP80102995 A EP 80102995A EP 0021100 A1 EP0021100 A1 EP 0021100A1
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EP
European Patent Office
Prior art keywords
compounds
ester
mixture
formula
methyl
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.)
Granted
Application number
EP80102995A
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German (de)
English (en)
Other versions
EP0021100B1 (fr
Inventor
Hanspeter Dr. Schenk
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.)
Givaudan SA
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L Givaudan and Co SA
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Publication date
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Publication of EP0021100A1 publication Critical patent/EP0021100A1/fr
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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
  • 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 means 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 , SnCl 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 ester II which is also the subject of the present application, is expediently prepared from the known 3,6-dimethyl-5-hepten-2-one.
  • reaction temperature is not critical. The temperature range is from about 40 to 60 0, but can also be carried out at lower or higher temperature.
  • a resulting methyl or ethyl ester of the formula II can optionally be transesterified in a conventional manner, e.g. by heating with a higher alcohol, e.g. Isobutanol, expediently under alkaline conditions, where the methanol or ethanol formed can be continuously distilled off from the reaction mixture.
  • a higher alcohol e.g. Isobutanol
  • I 1 is obtained as a mixture of isomers of Ia, Ib and Ic.
  • the separation of the isomer mixtures can, if desired, be carried out in the usual way, e.g. 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 special 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 for modifying known compositions in which e.g. the citrus notes should be increasingly expressed (e.g. for Cologne types and the like, tincts), but also of floral, especially rose compositions, where, among other things, the use of compounds of formula I leads to a clarification of the musk effect (pos types, composition of the feminine direction) and of wood compositions, where the addition of the new compounds I underlines the sought-after, expensive sand notes (general types of tincts) ).
  • the 2,3,6,6-tetramethyl-2-cyclohexene-1-carbonate e.g. is characterized by strong, floral-spicy and woody notes of great radiance. Also worth mentioning are the fruity sweet, slightly powdery side notes of this compound.
  • This preferred compound accordingly differs organoleptically in a clear and surprising manner from the structurally obvious known compound, the 2,5,6,6-tetramethyl-cyclohex-2-en-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. Raspberry or apricot flavors can be used.
  • fruit flavors e.g. Raspberry or apricot flavors
  • the characteristic characteristic of fresh grapes is advantageously emphasized.
  • Food yogurt, confectionery, etc.
  • luxury foods tea, tobacco, etc.
  • drinks lemonade, etc.
  • 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. 90:10 to 10:90. The range from 10:90 to 30:70 is preferred.
  • the compounds of the formula I can be used within wide limits, which can range, for example, from 0.1 (detergents) -30% (alcoholic solutions) in compositions, without these values, however, being intended to represent limit values , because the experienced perfumer can achieve effects with even lower concentrations or build new types of 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 (eau de cologne, eau de toilette, extras, lotions, creams, shampoos, soaps, ointments, powder, toothpaste, mouthwashes, deodorants, detergents, tobacco , Etc.).
  • the compounds I can accordingly be used in the production of compositions and - as the above composition 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 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.e. the flavored food, luxury food or drink.
  • the dosage can, however, also be higher and comprise 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, by methods known per se.
  • the products can be spray dried, vacuum dried or lyophilized.
  • yeast alginates, carrageenan or similar absorbents
  • Cloves diacetyl, sodium citrate
  • IMP disodium iso
  • the ethyl c, t-3,4,7, -trimethyl-2,6-octadienate can be obtained as follows:
  • Example 1 According to the procedure of Example 1, 71 g of an ester mixture consisting of 80 0 / oc, t-3,4,7-trimethyl-2,6-octadienoic acid ethyl ester and 200 / oc, t-3-ethyl- 7-methyl-2,6-octadienoic acid ethyl ester 66.5 g of crude product.
  • the ester mixture used as starting material consisting of 77.1% c, t-3-ethyl-7-methyl-2,6-octadienoic acid methyl ester and 22.4% c, t-3,4,7-trimethyl-2 , 6-octadienoic acid methyl ester can be obtained as follows:
  • a solution of 85 g (0.467 mol) of trimethyl phosphonoacetate and 50 g (0.357 mol) of a ketone mixture is added to a solution of 9.7 g (0.422 mol) of sodium in 220 ml of absolute methanol, cooled to 5 ° C., at this temperature for 1 hour. consisting of 23.9% 3,6-dimethyl-5-hepten-2-one and 76.1% 7-methyl-6-octen-3-one added dropwise in 220 ml of absolute toluene.
  • the reaction mixture is then allowed to assume room temperature and react overnight.
  • the reaction mixture is poured onto ice and extracted three times with hexane.
  • the combined hexane solutions are washed neutral with saline, dried over sodium sulfate and evaporated.
  • the crude product (81.8 g) is fractionally distilled in a high vacuum over a 15 cm Widmer column. 44.8 g (64.0%) of a mixture of b.p. 58-61 ° C / 0.02 mmHg are obtained; n: 1.4708.
  • the mixture consists of 77.1% c, t-3-ethyl-7-methyl-2,6-octadienoic acid methyl ester and 22.4% c, t-3,4,7-trimethyl-2,6-octadienoic acid methyl ester.
  • 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, for example, Belgian patent 634738 of 10.1.1964) from 3-methyl-l-buten-3-ol, methylbutenyl ether and phosphoric acid as catalyst in an autoclave at 180 ° C in 54.4% yield).
  • the reaction mixture is poured onto ice and extracted twice with hexane.
  • the combined hexane solutions are washed with water (lx), with sat. Bicarbonate solution (2x) and finally washed neutral with water (2x), dried over sodium sulfate and evaporated.
  • the crude product (21.2 g) is fractionally distilled in a high vacuum on a 15 cm Widmer column liert. 16.9 g (69.0%) of a mixture of b.p. 64-66 ° C./0.04 mmHg are obtained; : 1.4608.
  • ester mixture used as the starting material consisting of 71.6% c, t-3-acetyl-7-methyl-2,6-octadienoic acid isobutyl ester and (20.1%) c, t-3,4,7-trimethyl-2 , Isobutyl 6-octa-diene can be obtained as follows:
  • the mixture consists of 71.6% of c, t-3-ethyl-7-methyl-2,6-octadienoic acid isobutyl ester and 20.1% of c, t-3,4,7-tri methyl isobutyl 2,6-octadienate.
  • ester mixture used as starting material consisting of 83.8% c, t-3-ethyl-7-methyl-2,6-octadienic acid allyl ester and 9.1% c, t-3,4,7-trimethyl-2, 6-octadienic acid allyl ester can be obtained as follows:
  • the mixture consists of 83.8% c, t-3-ethyl-7-methyl-2,6-octadienoic acid allyl ester and 9.1% c, t-3,4,7-trimethyl-2,6-octadienoic acid allyl ester.
  • composition (chypre)
  • the base appears brighter overall and thus provides a composition with a new direction for the well-known chypre range by adding the new ester.
  • composition woody type
  • composition (cologne type)
  • Tobacco flavor top flavor, e.g. for cigarettes
  • the suitable dosage is, for example, 100 g / 100 kg tobacco.
  • the tobacco note is significantly increased.
  • smoking the aro-. flavored tobacco creates a typical smell and taste impression that strongly reminds of bright Virginia tobacco.
  • the suitable dosage is e.g. 40 g per 100 liters of syrup.
  • Suitable dosage e.g. 40 g per 100 liters of syrup.
  • the addition of the mixture I '+ IV (in a ratio of 25:75) to composition A leads to a noticeable change in smell and taste.
  • the original sweet note is advantageously weakened, a fresh, fruity note appears, which 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)
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
CH3163/80 1980-04-24
CH316380 1980-04-24

Publications (2)

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

Family

ID=25692349

Family Applications (1)

Application Number Title Priority Date Filing Date
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) ES8105256A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0378825A2 (fr) * 1989-01-18 1990-07-25 Firmenich Sa Esters alicycliques et leur utilisation à titre d'ingrédients parfumants
WO1994013766A2 (fr) * 1992-12-11 1994-06-23 Quest International B.V. Esters d'acide dimethyl-cyclohexanecarboxylique en parfumerie

Families Citing this family (6)

* 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
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
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4006108A (en) * 1974-04-19 1977-02-01 Givaudan Corporation Z-ethyl-3,6,6-trimethyl-2-cyclohexene-1-carboxylic acid esters
DE2644762A1 (de) * 1975-10-09 1977-04-21 Givaudan & Cie Sa Neuer riechstoff
US4028278A (en) * 1971-08-17 1977-06-07 Firmenich S.A. Cycloaliphatic unsaturated ketones as fragrance modifying agents
US4147672A (en) * 1974-01-29 1979-04-03 Firmenich Sa Cyclic C6 ketones in perfumes

Family Cites Families (7)

* 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
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
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4028278A (en) * 1971-08-17 1977-06-07 Firmenich S.A. Cycloaliphatic unsaturated ketones as fragrance modifying agents
US4147672A (en) * 1974-01-29 1979-04-03 Firmenich Sa Cyclic C6 ketones in perfumes
US4006108A (en) * 1974-04-19 1977-02-01 Givaudan Corporation Z-ethyl-3,6,6-trimethyl-2-cyclohexene-1-carboxylic acid esters
DE2559957B1 (de) * 1974-04-19 1980-02-07 Givaudan & Cie Sa 3,6,6-Trimethylcyclohexen-1-carbonsaeureester,Verfahren zu deren Herstellung und diese enthaltende Riechstoffkompositionen
DE2644762A1 (de) * 1975-10-09 1977-04-21 Givaudan & Cie Sa Neuer riechstoff

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0378825A2 (fr) * 1989-01-18 1990-07-25 Firmenich Sa Esters alicycliques et leur utilisation à titre d'ingrédients parfumants
EP0378825A3 (fr) * 1989-01-18 1992-01-15 Firmenich Sa Esters alicycliques et leur utilisation à titre d'ingrédients parfumants
WO1994013766A2 (fr) * 1992-12-11 1994-06-23 Quest International B.V. Esters d'acide dimethyl-cyclohexanecarboxylique en parfumerie
WO1994013766A3 (fr) * 1992-12-11 1996-02-01 Quest Int Esters d'acide dimethyl-cyclohexanecarboxylique en parfumerie

Also Published As

Publication number Publication date
CA1142955A (fr) 1983-03-15
DE3061098D1 (en) 1982-12-23
US4570648A (en) 1986-02-18
EP0021100B1 (fr) 1982-11-17
US4375001A (en) 1983-02-22
ES492367A0 (es) 1981-06-01
US4474687A (en) 1984-10-02
ES8105256A1 (es) 1981-06-01
BR8003579A (pt) 1981-01-05

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