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EP0008103B1 - Application of esters of the mixture tricyclo-(5.2.1.0)decane-3- and tricyclo(5.2.1.0)decane-4-carboxylic acids as perfumes; perfuming compositions containing them - Google Patents

Application of esters of the mixture tricyclo-(5.2.1.0)decane-3- and tricyclo(5.2.1.0)decane-4-carboxylic acids as perfumes; perfuming compositions containing them Download PDF

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Publication number
EP0008103B1
EP0008103B1 EP79102824A EP79102824A EP0008103B1 EP 0008103 B1 EP0008103 B1 EP 0008103B1 EP 79102824 A EP79102824 A EP 79102824A EP 79102824 A EP79102824 A EP 79102824A EP 0008103 B1 EP0008103 B1 EP 0008103B1
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EP
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Prior art keywords
tricyclo
decane
esters
mixture
carboxylic acids
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Expired
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EP79102824A
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German (de)
French (fr)
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EP0008103A1 (en
Inventor
Ulf-Armin Dr. Schaper
Klaus Dr. Bruns
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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
    • C11B9/0042—Essential oils; Perfumes compounds containing condensed hydrocarbon rings

Definitions

  • esters of the mixture of tricyclo [5.2.1.0 2.6 ] decane-3 (4) -carboxylic acids of the general formulas in which R represents a saturated or unsaturated, straight-chain or branched aliphatic hydrocarbon radical with 1-5 carbon atoms, can advantageously be used as fragrances in compositions for perfuming technical and cosmetic preparations.
  • esters to be used according to the invention can be prepared by generally known methods by reacting the tricyclo [5.2.1.0 2.6 ] decane-3 (4) carboxylic acids or their acid chlorides with the corresponding alcohols.
  • the mixture of acids is obtained by hydroformylation of tricyclo [5.2.1.0 2.6 ] dec-3-ene with subsequent oxidation, according to the following scheme:
  • esters are obtained directly.
  • the acids or esters also obtained here are a mixture of different stereoisomers of tricyclo [5.2.1.0 2.6 ] decane-3 (4) -carboxylic acids or their esters. This mixture is not separated, but as such forms the interesting fragrance to be used according to the invention.
  • esters covered by the general formula mentioned above the methyl ester and ethyl ester are known from the literature as such, but their suitability as a fragrance was not recognized.
  • the much more interesting esters of unsaturated alcohols are new compounds.
  • the mixtures of the esters of tricyclo [5.2.1.0 2.6 ] decane-3 (4) -carboxylic acids to be used according to the invention are valuable fragrances with characteristic odor notes. They can be combined very well to create new and interesting smells. Among the products, the allyl and propargyl ester mixtures are of the greatest importance due to their special smell notes.
  • the Propargylester have an interesting Maggi-Walnut note, while the Allylestern can be attributed an Ocimen, Styrolyl note. Such olfactory notes are particularly suitable for the development of novel fragrance compositions.
  • the esters of the mixture of tricyclo [5.2.1.O 2.6 ] decane-3 (4) -carboxylic acids to be used according to the invention as fragrances can be mixed with other fragrances in various proportions to give new fragrance compositions.
  • the proportion of the esters of the mixture of tricyclo [5.2.1.0 2.6 ] decane-3 (4) -carboxylic acids in the fragrance compositions will range from 1-50 percent by weight, based on the overall composition.
  • Such compositions can be used to perfume cosmetics such as creams, lotions, aerosols, toilet soaps, technical articles such as washing and cleaning agents, disinfectants and textile treatment agents.
  • esters were prepared by generally known Ahren f Verest fürsver from the available as a commercial product TCD-carboxylic acid S, which is as stated above, is to mixtures.

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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)
  • Cosmetics (AREA)
  • Detergent Compositions (AREA)

Description

Es wurde gefunden, daß Ester des Gemisches der Tricyclo[5.2.1.02.6]decan-3(4)-carbonsäuren der allgemeinen Formeln

Figure imgb0001
in denen R einen gesättigten oder ungesättigten, geradkettigen oder verzweigten aliphatischen Kohlenwasserstoffrest mit 1-5 Kohlenstoffatomen darstellt, in vorteilhafter Weise als Riechstoffe in Kompositionen zur Parfümierung technischer und kosmetischer Präparate verwendet werden können.It was found that esters of the mixture of tricyclo [5.2.1.0 2.6 ] decane-3 (4) -carboxylic acids of the general formulas
Figure imgb0001
 in which R represents a saturated or unsaturated, straight-chain or branched aliphatic hydrocarbon radical with 1-5 carbon atoms, can advantageously be used as fragrances in compositions for perfuming technical and cosmetic preparations.

Von besonderem Interesse ist dabei das Gemisch der Ester, in denen R den Allylrest -CH2-CH=CH2 oder den Propargylrest -CH2-C≡CH darstellt.Of particular interest is the mixture of esters in which R represents the allyl radical -CH 2 -CH = CH 2 or the propargyl radical -CH 2 -C≡CH.

Die Herstellung der erfindungsgemäß zu verwendenden Ester kann nach allgemein bekannten Methoden durch Umsetzung der Tricyclo[5.2.1.02.6]decan-3(4)carbonsäuren oder deren Säurechloriden mit den entsprechenden Alkoholen erfolgen.The esters to be used according to the invention can be prepared by generally known methods by reacting the tricyclo [5.2.1.0 2.6 ] decane-3 (4) carboxylic acids or their acid chlorides with the corresponding alcohols.

Das Gemisch der Säuren wird durch Hydroformylierung von Tricyclo[5.2.1.02.6]dec-3-en mit nachfolgender Oxidation erhalten, entsprechend folgendem Schema:

Figure imgb0002
The mixture of acids is obtained by hydroformylation of tricyclo [5.2.1.0 2.6 ] dec-3-ene with subsequent oxidation, according to the following scheme:
Figure imgb0002

Das auf diesem Wege gewonnene Gemisch der Tricyclo[5.2.1.02.6]-decan-3(4)-carbonsäuren ist unter dem Namen TCD-Carbonsäure S Handelsprodukt.The mixture of tricyclo [5.2.1.0 2.6 ] -decane-3 (4) -carboxylic acids obtained in this way is a commercial product under the name TCD-carboxylic acid S.

Eine andere Möglichkeit zu den erfindungsgemäß zu verwendenden Estern bzw. den ihnen zugrundeliegenden Säuren zu gelangen, bieten die Carbonylierungsreaktionen nach Reppe oder Koch. Die Reaktion verläuft dabei nach folgendem Schema:

Figure imgb0003
Another way to get to the esters to be used according to the invention or the acids on which they are based is provided by the carbonylation reactions according to Reppe or Koch. The reaction proceeds as follows:
Figure imgb0003

Führt man die Reaktion in Alkohol anstatt in wäßrigem Milieu durch, so gelangt man direkt zu den entsprechenden Estern. Die auch hierbei erhaltenen Säuren bzw. Ester sind ein Gemisch verschiedener Stereoisomerer der Tricyclo[5.2.1.02.6]decan-3(4)-carbonsäuren bzw. deren Estern. Dieses Gemisch wird nicht aufgetrennt, sondern bildet als solches den erfindungsgemäß zu verwendenden interessanten Riechstoff.If the reaction is carried out in alcohol instead of in an aqueous medium, the corresponding esters are obtained directly. The acids or esters also obtained here are a mixture of different stereoisomers of tricyclo [5.2.1.0 2.6 ] decane-3 (4) -carboxylic acids or their esters. This mixture is not separated, but as such forms the interesting fragrance to be used according to the invention.

Von den unter vorgenannte allgemeine Formel fallenden Estern sind bisher der Methylester und Äthylester als solche literaturbekannt, ohne daß jedoch ihre Eignung als Riechstoff erkannt worden wäre. Die wesentlich interessanteren Ester ungesättigter Alkohole stellen neue Verbindungen dar.Of the esters covered by the general formula mentioned above, the methyl ester and ethyl ester are known from the literature as such, but their suitability as a fragrance was not recognized. The much more interesting esters of unsaturated alcohols are new compounds.

Die erfindungsgemäß zu verwendenden Gemische der Ester der Tricyclo[5.2.1.02.6]decan-3(4)-carbonsäuren sind wertvolle Riechstoffe mit charakteristischen Geruchsnoten. Sie lassen sich sehr gut zu neuartigen und interessanten Geruchsnuancen kombinieren. Unter den Produkten kommt den Allyl-und Propargylestergemischen aufgrund ihrer besonderen Geruchsnoten die größte Bedeutung zu. Die Propargylester besitzen eine interessante Maggi-Walnuß-Note, während den Allylestern eine Ocimen-, Styrolyl-Note zuzuschreiben ist. Derartige Geruchsnoten sind für die Entwicklung neuartiger Riechstoffkompositionen besonders geeignet.The mixtures of the esters of tricyclo [5.2.1.0 2.6 ] decane-3 (4) -carboxylic acids to be used according to the invention are valuable fragrances with characteristic odor notes. They can be combined very well to create new and interesting smells. Among the products, the allyl and propargyl ester mixtures are of the greatest importance due to their special smell notes. The Propargylester have an interesting Maggi-Walnut note, while the Allylestern can be attributed an Ocimen, Styrolyl note. Such olfactory notes are particularly suitable for the development of novel fragrance compositions.

Die erfindungsgemäß als Riechstoffe zu verwendenden Ester des Gemisches der Tricyclo[5.2.1.O2.6]decan-3(4)-carbonsäuren können mit anderen Riechstoffen in den verschiedensten Mengenverhältnissen zu neuen Riechstoffkompositionen gemischt werden. Im allgemeinen wird sich der Anteil der Ester des Gemisches der Tricyclo[5.2.1.02.6]decan-3(4)-carbonsäuren in den Riechstoffkompositionen in den Mengen von 1-50 Gewichtsprozent, bezogen auf die gesamte Komposition, bewegen. Derartige Kompositionen können zur Parfümierung von Kosmetika wie Cremes, Lotionen, Aerosolen, Toiletteseifen, technischen Artikeln wie Wasch- und Reinigungsmitteln, Desinfektionsmitteln und Textilbehandlungsmitteln dienen.The esters of the mixture of tricyclo [5.2.1.O 2.6 ] decane-3 (4) -carboxylic acids to be used according to the invention as fragrances can be mixed with other fragrances in various proportions to give new fragrance compositions. In general, the proportion of the esters of the mixture of tricyclo [5.2.1.0 2.6 ] decane-3 (4) -carboxylic acids in the fragrance compositions will range from 1-50 percent by weight, based on the overall composition. Such compositions can be used to perfume cosmetics such as creams, lotions, aerosols, toilet soaps, technical articles such as washing and cleaning agents, disinfectants and textile treatment agents.

Die nachfolgenden Beispiele sollen die Gegenstand der Erfindung näher erläutern, ohne ihn jedoch hierauf zu beschränken.The following examples are intended to explain the subject matter of the invention in more detail, but without restricting it thereto.

BeispieleExamples

Nach allgemein bekannten Veresterungsverfahren wurden aus der als Handelsprodukt erhältlichen TCD-Carbonsäure S folgende Ester hergestellt, wobei es sich, wie vorstehend ausgeführt, um Gemische handelt.

Figure imgb0004
The following esters were prepared by generally known Ahren f Veresterungsver from the available as a commercial product TCD-carboxylic acid S, which is as stated above, is to mixtures.
Figure imgb0004

Beispiel 1example 1

Figure imgb0005
Figure imgb0005

Beispiel 2Example 2

Figure imgb0006
Figure imgb0006

Claims (4)

1. The use of esters of a mixture of tricyclo[5.2.1.02.6]decane-3(4)-carboxylic acids corresponding to the following general formulae
Figure imgb0008
in which R is a saturated or unsaturated, straight-chain or branched aliphatic hydrocarbon radical containing from 1 to 5 carbon atoms, as fragrances.
2. The use claimed in claim 1, characterised in that allyl and/or propargyl esters of the mixture of tricyclo[5.2.1.02.6]decane-3(4)-carboxylic acids are used.
3. Fragrance compositions, characterized by a content of esters of the mixture of tricyclo-[5.2.1.02.6]decane-3(4)-carboxylic acids according to claims 1 and 2.
4. Fragrance compositions as claimed in claim 3, characterised in that they contain the esters of the mixture of tricyclo-[5.2.1.02.6]decane-3(4)-carboxylic acids in a quantity of from 1 to 50% by weight, based on the composition as a whole.
EP79102824A 1978-08-12 1979-08-06 Application of esters of the mixture tricyclo-(5.2.1.0)decane-3- and tricyclo(5.2.1.0)decane-4-carboxylic acids as perfumes; perfuming compositions containing them Expired EP0008103B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2835445 1978-08-12
DE2835445A DE2835445C2 (en) 1978-08-12 1978-08-12 Use of esters of the mixture of tricyclo- [5.2.1.0 → 2 → →. → → 6 →] decane-3 and tricyclo [5.2.1.0 → 2 → →. → → 6 →] decane-4-carboxylic acid as fragrances, and fragrance compositions containing them

Publications (2)

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EP0008103A1 EP0008103A1 (en) 1980-02-20
EP0008103B1 true EP0008103B1 (en) 1981-05-20

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US (2) US4311616A (en)
EP (1) EP0008103B1 (en)
JP (1) JPS5527188A (en)
BR (1) BR7905147A (en)
CA (1) CA1126165A (en)
DE (1) DE2835445C2 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4311852A (en) * 1978-07-05 1982-01-19 Firmenich Sa Oxygen containing derivatives of tricyclo[6.2.1.02,7 ]undecane
CH654204A5 (en) * 1980-03-14 1986-02-14 Kao Corp PERFUME COMPOSITIONS AND PROCEDURE FOR THEIR PREPARATION.
US4411828A (en) * 1980-03-14 1983-10-25 Kao Corporation Fragrant tricyclic carboxylates
JPS56128710A (en) * 1980-03-14 1981-10-08 Kao Corp Perfume composition
US4529599A (en) * 1982-12-16 1985-07-16 Kao Corporation Tricyclic carboxylate ester and insecticide containing the same
JP6283416B2 (en) * 2013-07-22 2018-02-21 高砂香料工業株式会社 Derivatives of 2,2,6-trimethylcyclohexanecarboxylic acid
EP3098216B1 (en) * 2014-01-20 2019-11-06 Kokyu Alcohol Kogyo Co., Ltd. Novel ester compound, and cosmetic component and cosmetic product each containing same
JP5580947B1 (en) * 2014-01-20 2014-08-27 高級アルコール工業株式会社 Novel ester compound and cosmetics and cosmetics containing the same
JP5663111B1 (en) * 2014-07-08 2015-02-04 高級アルコール工業株式会社 Novel ester compound and cosmetics and cosmetics containing the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2688627A (en) * 1952-05-08 1954-09-07 Standard Oil Dev Co Dicyclopentadiene carboxylic acids
US3679749A (en) * 1968-06-10 1972-07-25 Int Flavors & Fragrances Inc Perhydro 1,4,9,9-tetramethyl-4,7-methandazulenones
US3598745A (en) * 1968-10-31 1971-08-10 Universal Oil Prod Co Substituted 4,7-methanoindenes perfume compositions
CH529214A (en) * 1970-04-06 1972-10-15 Roure Bertrand Dupont Sa Fragrance compositions
CH602111A5 (en) * 1975-12-08 1978-07-31 Firmenich & Cie

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JPS5527188A (en) 1980-02-27
EP0008103A1 (en) 1980-02-20
BR7905147A (en) 1980-05-06
JPS622564B2 (en) 1987-01-20
US4289660A (en) 1981-09-15
DE2835445A1 (en) 1980-02-28
DE2835445C2 (en) 1986-12-11
US4311616A (en) 1982-01-19
CA1126165A (en) 1982-06-22

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