EP0053704A1 - Esters cycliques, procédé de préparation et leur utilisation comme agents parfumants et aromatisants, compositions parfumantes et aromatisantes les contenant - Google Patents

Esters cycliques, procédé de préparation et leur utilisation comme agents parfumants et aromatisants, compositions parfumantes et aromatisantes les contenant Download PDF

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Publication number
EP0053704A1
EP0053704A1 EP81108921A EP81108921A EP0053704A1 EP 0053704 A1 EP0053704 A1 EP 0053704A1 EP 81108921 A EP81108921 A EP 81108921A EP 81108921 A EP81108921 A EP 81108921A EP 0053704 A1 EP0053704 A1 EP 0053704A1
Authority
EP
European Patent Office
Prior art keywords
ethyl
hydrogen
methyl
compounds
formula
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
EP81108921A
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German (de)
English (en)
Other versions
EP0053704B1 (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
Original Assignee
L Givaudan and Co SA
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 L Givaudan and Co SA filed Critical L Givaudan and Co SA
Publication of EP0053704A1 publication Critical patent/EP0053704A1/fr
Application granted granted Critical
Publication of EP0053704B1 publication Critical patent/EP0053704B1/fr
Expired legal-status Critical Current

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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 1 is C 1-4 alkyl and R 2 and R 3 are hydrogen or methyl, but not both are hydrogen at the same time.
  • the formula I is intended to encompass all possible stereoisomers, defined by the relative position of the substituents on the C 1 - are possible and C 3 atom of I -, C. 2
  • the radicals R 1 can be straight-chain or branched. Methyl and isobutyl are preferred, and ethyl is particularly preferred.
  • the invention further relates to a process for the preparation of compounds of formula H I.
  • Suitable catalysts for this process are noble metal catalysts which e.g. Contain platinum, palladium, ruthenium or rhodium.
  • the hydrogenation can be carried out with or without the addition of solvents; inert solvents such as ethyl alcohol, methyl alcohol, cyclohexane etc. are preferred
  • the hydrogenation can be carried out at temperatures between e.g. 0 ° -100 ° C, especially between 15-30 ° C, as well as normal pressure or higher pressures, e.g. 5-20 atm. (H.O. House, Modern Synthetic Reactions, N.A. Benjamin Inc., New York 1972).
  • the separation of the isomers may, if desired, effected in a customary manner, for example by preparative chromatography as- G.
  • 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.
  • esters I I can be prepared by the known methods of preparing cyclogeranoyl derivatives, for example by cyclization of esters of the formula
  • 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).
  • R 2 H
  • reaction temperature is not critical. The temperature range of approximately 40-60 ° C. is preferred, but it is also possible to work at a lower or higher temperature.
  • R 1 for example propyl, isobutyl
  • esters of the formula I are expediently converted from a methyl or ethyl ester of the formula III by transesterification, in the usual way by heating with a higher alcohol, for example propanol or isobutanol, preferably under alkaline conditions, prepared, the methanol or ethanol formed can be continuously distilled off from the reaction mixture.
  • a higher alcohol for example propanol or isobutanol
  • the compounds I have special organoleptic properties which make them particularly suitable as fragrances and / or flavors.
  • the invention accordingly also relates to the uses du n g of the compounds I as fragrances and / or flavors.
  • the compounds I round off and harmonize the olfactory notes of known compositions, but without dominating. For example, they underline in fragrance bases with tea and green character the spicy and herbaceous notes, and in rose bases the sought-after character of the heavy, sweet and somewhat Bulgarian rose is underlined.
  • 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, since 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 (Eaux de Cologne, Eaux de Toilette, extras, lotions, creams, shampoos, soaps, ointments, powder, toothpastes, 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.
  • the new compounds of formula I or their mixtures are also excellently suitable for use in fruit flavors of all kinds, but in particular also for flavoring tobacco.
  • 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.
  • Foods yogurt, confectionery, etc.
  • luxury foods tea, tobacco, etc.
  • drinks lemonade, etc.
  • 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 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 the usual way with the esch mack substance compositions for G components used or added to such flavorings.
  • 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.
  • the crude product (29.8 g) is fractionally distilled in a high vacuum using a 10 cm Widmer column. 28 g (92.4% of theory) of a mixture with a boiling point of 42-55 ° C./0.05 mm Hg are obtained.
  • the reaction mixture is poured onto ice and extracted 3 times with hexane.
  • the combined hexane solutions are washed neutral with water (1 time), with sodium bicarbonate solution (2 times) and finally with water (2 times), dried over sodium sulfate and evaporated.
  • the crude product (22.5 g) is fractionally distilled in a high vacuum on a 10 cm Widmer column.
  • the crude product (21.8 g) is fractionally distilled in a high vacuum using a 5 cm Widmer column. There is obtained (79.6% d. Th.) 18.0 g g of a mixture of boiling point 80-81 ° / 0.15 mm H. : 1.4527.
  • capillary gas chromatography 50m x 0.31 mm i. D. Ucon HB 5100.14 0 ° C isothermal, helium flow 2.5 ml / min. Split ratio 1:30) are visible, arranged 4 peaks with the following percentages of the total mixture ( after increasing retention time):
  • Peaks 1, 2, 3 4 represent the 4 possible stereoisomers of the 2-ethyl-3,6,6-trimethyl-cyclohexane-1-carboxylic acid ethyl ester.
  • Smell woody, fruity-berry-like, camp-like, reminiscent of eucalyptus seeds, aromatic.
  • Smell very natural, in the direction of chamomile and tagetes.
  • the crude product (29.4 g) is fractionally distilled in a high vacuum using a 15 cm Widmer column. 27.5 g (70.9% of theory) of a mixture having a boiling point of 80-82 ° C./0.04 mm Hg are obtained; : 1.4660.
  • the mixture consists of around 20% c, t-3,4,7-trimethyl-2,6-octadienoic acid isobutyl ester and around 80% c, t-3-ethyl-7-methyl-2,6-octadienoic acid isobutyl ester. This mixture is cyclized analogously to that described in Example 1.
  • the composition receives significantly more diffusion and it becomes stronger. It also looks fresher, more spicy and sweeter and, subliminally, gets a floral character in the direction of the rose.
  • the composition with the addition of the new mixture I shows an extraordinary diffusion even after several hours on the smell strip very warm look at the same time. This effect is very desirable, but rather unusual for a substance that is relatively volatile.
  • the rose character of the original composition becomes significantly warmer and softer, and the diffusion increases. There is also a clear Damascon note. In the rear, the dominant musk character is slightly weakened and pleasantly rounded off.
  • the apple-like, weak green note of the basic composition and its musky note are advantageously changed to the desired apricot note.
  • the composition becomes much more natural, harmonious, less rough.
  • the influence of the addition is particularly noticeable in the rear, as elements of the composition that previously did not harmonize are now combined very harmoniously and at the same time the musk character, which is not desired here, is suppressed.

Landscapes

  • 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)
  • Cosmetics (AREA)
EP81108921A 1980-12-10 1981-10-26 Esters cycliques, procédé de préparation et leur utilisation comme agents parfumants et aromatisants, compositions parfumantes et aromatisantes les contenant Expired EP0053704B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH910380 1980-12-10
CH9103/80 1980-12-10
CH657381 1981-10-14
CH6573/81 1981-10-14

Publications (2)

Publication Number Publication Date
EP0053704A1 true EP0053704A1 (fr) 1982-06-16
EP0053704B1 EP0053704B1 (fr) 1984-01-04

Family

ID=25699808

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81108921A Expired EP0053704B1 (fr) 1980-12-10 1981-10-26 Esters cycliques, procédé de préparation et leur utilisation comme agents parfumants et aromatisants, compositions parfumantes et aromatisantes les contenant

Country Status (3)

Country Link
US (1) US4439353A (fr)
EP (1) EP0053704B1 (fr)
DE (1) DE3161847D1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994013766A2 (fr) * 1992-12-11 1994-06-23 Quest International B.V. Esters d'acide dimethyl-cyclohexanecarboxylique en parfumerie

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE68916634T2 (de) * 1989-01-18 1994-11-03 Firmenich & Cie Alicyclische Ester und ihre Anwendung als Riechstoffkomponenten.
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
EP1347035B1 (fr) * 2002-03-22 2008-07-23 Takasago International Corporation Composition d'isomères contenant un trans-2,2,6-trimethylcyclohexylcarboxylate d'ethyle optiquement actif et une composition parfumante incluant cette composition d'isomères
EP3024427B1 (fr) 2013-07-22 2019-10-09 Takasago International Corporation Dérivés de 2,2,6-triméthylcyclohexane-carboxylate

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2329655A1 (fr) * 1973-07-26 1977-05-27 Firmenich & Cie Nouveaux alcools, utilisables comme intermediaires pour la synthese de cetones alicycliques insaturees

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH563951A5 (fr) * 1972-02-03 1975-07-15 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
US4113663A (en) * 1975-10-09 1978-09-12 Givaudan Corporation 2-Ethyl-6,6-dimethyl-2-cyclohexene-1-carboxylic acid ethyl ester perfume compositions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2329655A1 (fr) * 1973-07-26 1977-05-27 Firmenich & Cie Nouveaux alcools, utilisables comme intermediaires pour la synthese de cetones alicycliques insaturees

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
EP0053704B1 (fr) 1984-01-04
US4439353A (en) 1984-03-27
DE3161847D1 (en) 1984-02-09

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