EP0504563B1 - Perfuming ingredient with a spiranic structure - Google Patents

Perfuming ingredient with a spiranic structure Download PDF

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Publication number
EP0504563B1
EP0504563B1 EP92101748A EP92101748A EP0504563B1 EP 0504563 B1 EP0504563 B1 EP 0504563B1 EP 92101748 A EP92101748 A EP 92101748A EP 92101748 A EP92101748 A EP 92101748A EP 0504563 B1 EP0504563 B1 EP 0504563B1
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EP
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Prior art keywords
spiro
perfuming
ene
tridec
ingredient
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EP92101748A
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German (de)
French (fr)
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EP0504563A1 (en
Inventor
Wolfgang Klaus Giersch
Pierre-Alain Blanc
Karl-Heinrich Schulte-Elte
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Firmenich SA
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Firmenich SA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • 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
    • C11B9/0046—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings
    • C11B9/0049—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings the condensed rings sharing two common C atoms

Definitions

  • the present invention relates to the field of perfumery. It relates more particularly to the use of a spiranic ketone compound of formula or spiro [5.7] tridéc-1-ene-3-one, as a perfuming ingredient for the preparation of perfumes and perfumed products.
  • Spiro [5.7] tridec-1-ene-3-one is a known chemical entity. Kane Vinayak described its preparation from enamines of cycloaliphatic aldehydes by reaction with methyl vinyl ketone [Synth. Common. 6 , 237-42 (1976)].
  • a similar synthesis has been proposed by NR Natale et al. [Org. Prep. Proced. Int.
  • triconvergec-1-ene-3-one is used to develop iridescent notes recalling by some of its aspects 5-ethyl-2-nonanol or p-tert-amylcyclohexanone [Orivone: IFF; see S. Arctander, Perfume and Flavor Chemicals, sec. 166, Montclair, N.J. USA (1969)].
  • the spiro-ketone of the invention also has a costus, animal and leather appearance, its base notes recalling flax and coumarin. With excellent olfactory power, spiro-ketone (I) has very good substantivity on linen, particularly on cotton fabrics.
  • spiro-ketone (I) The proportions in which spiro-ketone (I) is used to develop the desired odorous effects can vary within a fairly wide range of values. Given its power, concentrations of the order of 0.5-1% may, in many cases, be sufficient. Lower concentration values can be used when perfuming functional or maintenance products, for example in soaps or detergents, where concentrations of 0.1% can already promote the desired effects. Of course, these concentration values should not be interpreted restrictively, those skilled in the art know from experience that in any practical use, the determination of such values depends on the nature of the products which it is desired to flavor as well as that of the co-ingredients in a given composition.
  • triconvergec-1-ene-3-one can be used in an isolated state, but more generally it will be used in admixture with usual diluents, carriers or excipients, as well as with other perfuming ingredients currents. Many examples of such co-ingredients and additives are provided in the prior art [see for example S. Arctander, op. cit.].
  • the present invention therefore relates, in addition to the use as defined above, a perfuming composition and products fragrances containing spiro [5.7] tridec-1-ene-3-one as an active fragrance ingredient.
  • spiro [5.7] tridec-1-ene-3-one is a known compound which can be obtained by following one of the preparation methods described in the cited documents, for example from cyclooctanecarboxaldehyde by reaction with methyl vinyl ketone in the presence of p-toluenesulfonic acid.
  • the product obtained was identical in all respects to the indications provided by the literature.
  • a basic perfuming composition for powdered detergents was prepared by mixing the following ingredients: Ingredients Parts by weight Benzyl acetate 250 Phenylethyl acetate 100 Styrallyl acetate 125 Aldehyde C9 10% * 50 Aldehyde C10 10% * 50 Allyl amyl glycolate 50 Methyl anthranilate 10% * 50 Citronellol 50 Verdyl acetate 25 Diphenyloxide 10% * 200 P-tert-butylcyclohexyl acetate 250 Clove essence from Madagascar 100 Galaxolide 50 MIP 1) 200 Galione 2) 50 Raw Geraniol (Glidden) 465 100 Lilial ® 3) 100 Linalol 1000 Purified menthone 10% * 250 Essence of patchouli 125 Phenylethyl phenylacetate 50 Brazilian orange essence 125 Amyl salicylate 100 Benzyl salicylate 150 Hexyl salicylate 3500 Terpineol ord.
  • a basic perfume composition of the vetyver type was prepared by mixing the following ingredients: Ingredients Parts by weight Essence of vetyver Haiti 500 Rhubofix 1) 20 Vertofix heart 2) 260 Cedroxide 3) 100 Cedrol 100 Total 980 1) epoxyethyl-methyltricycloundecene; origin: Firmenich SA, Geneva, Switzerland 2) origin: International Flavors and Fragrances Inc., USA 3) epoxy trimethylcyclododecatriene; origin: Firmenich SA, Geneva, Switzerland The addition, at a rate of 2% of spiro [5.7] tridéc-1-ene-3-one to the perfume base thus prepared reinforces the woody-vetyver aspect of the composition while giving it a natural character.

Description

La présente invention a trait au domaine de la parfumerie. Elle concerne plus particulièrement l'utilisation d'un composé cétonique spirannique de formule

Figure imgb0001

ou spiro[5.7]tridéc-1-ène-3-one, à titre d'ingrédient parfumant pour la préparation de parfums et produits parfumés. La spiro[5.7]tridéc-1-ène-3-one est une entité chimique connue. Kane Vinayak en a décrit la préparation à partir d'énamines d'aldéhydes cycloaliphatiques par réaction avec la méthyl-vinyle cétone [Synth. Commun. 6, 237-42 (1976)]. Une synthèse analogue a été proposée par N. R. Natale et al. [Org. Prep. Proced. Int. 9, 103-8 (1977)], tandis que R. E. Zipkin et al. [Synthesis 1035-7 (1980)] ont décrit un procédé qui avait recours au chlorure de phényl-sélénium et eau oxygénée. Enfin Kane Vinayak et al. ont pu préparer la spiro-cétone (I) par condensation du cyclcoctanecarboxaldéhyde avec la pipéridine, suivie d'une cyclisation avec la méthyl-vinyle cétone [Org. Synth. 61, 129-133 (1983)].The present invention relates to the field of perfumery. It relates more particularly to the use of a spiranic ketone compound of formula
Figure imgb0001
or spiro [5.7] tridéc-1-ene-3-one, as a perfuming ingredient for the preparation of perfumes and perfumed products. Spiro [5.7] tridec-1-ene-3-one is a known chemical entity. Kane Vinayak described its preparation from enamines of cycloaliphatic aldehydes by reaction with methyl vinyl ketone [Synth. Common. 6 , 237-42 (1976)]. A similar synthesis has been proposed by NR Natale et al. [Org. Prep. Proced. Int. 9 , 103-8 (1977)], while RE Zipkin et al. [Synthesis 1035-7 (1980)] described a process which used phenyl-selenium chloride and hydrogen peroxide. Finally Kane Vinayak et al. were able to prepare spiro-ketone (I) by condensation of cyclcoctanecarboxaldehyde with piperidine, followed by cyclization with methyl vinyl ketone [Org. Synth. 61 , 129-133 (1983)].

Utilisée en tant qu'intermédiaire pour la préparation de dérivés du cyclophare, la spiro[5.7]tridéc-1-ène-3-one n'a pas été reconnue dans l'art antérieur comme pouvant présenter des propriétés odorantes utiles. En effet, aucun des documents cités ne mentionne ni ne suggère la possibilité d'un emploi de ce composé en parfumerie. C'est donc de façon surprenante que nous avons découvert qu'il présentait des caractères odorants avantageux et que par conséquent il pouvait être employé pour la manufacture de parfums et de bases parfumées concentrées et servir pour conférer, améliorer ou modifier l'odeur de produits de consommation variés, tels les savons, les détergents liquides et solides, les adoucissants textiles, les produits de toilette tels les cosmétiques, les shampoings, les crèmes, les produits de traitement capillaire, ou encore les produits d'entretien et les désodorisants d'air ambiant.Used as an intermediate for the preparation of cyclophare derivatives, spiro [5.7] tridec-1-ene-3-one has not been recognized in the prior art as being capable of exhibiting useful odorous properties. Indeed, none of the documents cited mentions or suggests the possibility of using this compound in perfumery. It was therefore surprisingly that we discovered that it had advantageous odorous characteristics and that consequently it could be used for the manufacture of perfumes and concentrated perfumed bases and serve for impart, improve or modify the odor of various consumer products, such as soaps, liquid and solid detergents, fabric softeners, toiletries such as cosmetics, shampoos, creams, hair treatment products, or cleaning products and air fresheners.

La spiro[5.7]tridéc-1-ène-3-one sert à développer des notes irisées rappelant par certains de ses aspects le 5-éthyl-2-nonanol ou la p-tert-amylcyclohexanone [Orivone : IFF; voir S. Arctander, Perfume and Flavor Chemicals, sec. 166, Montclair, N.J. USA (1969)]. La spiro-cétone de l'invention possède en outre un aspect costus, animal et cuir, ses notes de fond rappellant le lin et la coumarine. Dotée d'une excellente puissance olfactive, la spiro-cétone (I) possède une très bonne substantivité sur le linge, particulièrement sur des tissus en coton. Des tissus lavés à l'aide de détergents parfumés avec la spiro-cétone (I) ont montré, après séchage, posséder une odeur plaisante poudrée et irisée, très prononcée. Ils développaient en outre une douceur presque coumarinée, ce qui confère à cet ingrédient une grande valeur, notamment pour toute utilisation en parfumerie fonctionnelle.Spiro [5.7] tridéc-1-ene-3-one is used to develop iridescent notes recalling by some of its aspects 5-ethyl-2-nonanol or p-tert-amylcyclohexanone [Orivone: IFF; see S. Arctander, Perfume and Flavor Chemicals, sec. 166, Montclair, N.J. USA (1969)]. The spiro-ketone of the invention also has a costus, animal and leather appearance, its base notes recalling flax and coumarin. With excellent olfactory power, spiro-ketone (I) has very good substantivity on linen, particularly on cotton fabrics. Fabrics washed with detergents scented with spiro-ketone (I) showed, after drying, to have a pleasant powdery and iridescent odor, very pronounced. They also developed an almost coumarinée sweetness, which gives this ingredient great value, especially for any use in functional perfumery.

Les proportions dans lesquelles la spiro-cétone (I) sert à développer les effets odorants recherchés peuvent varier dans une gamme de valeurs assez étendue. Compte tenu de sa puissance, des concentrations de l'ordre de 0,5-1% peuvent, dans bien des cas, être suffisantes. Des valeurs de concentration inférieures peuvent être employées lors du parfumage de produits fonctionnels ou d'entretien, par exemple dans des savons ou des détergents, où des concentrations de 0,1% peuvent déjà promouvoir les effets recherchés. Bien entendu, ces valeurs de concentration ne doivent pas être interprétées de manière restrictive, l'homme du métier sait par expérience que dans toute utilisation pratique, la détermination de telles valeurs dépend de la nature des produits que l'on désire parfumer ainsi que de celle des co-ingrédients dans une composition donnée. La spiro[5.7]tridéc-1-ène-3-one peut être utilisée en l'état isolé, mais plus généralement elle sera employée en mélange avec des diluants, des supports ou excipients usuels, ainsi qu'avec d'autres ingrédients parfumants courants. De multiples exemples de tels co-ingrédients et additifs sont fournis dans l'art antérieur [voir par exemple S. Arctander, op. cit.].The proportions in which spiro-ketone (I) is used to develop the desired odorous effects can vary within a fairly wide range of values. Given its power, concentrations of the order of 0.5-1% may, in many cases, be sufficient. Lower concentration values can be used when perfuming functional or maintenance products, for example in soaps or detergents, where concentrations of 0.1% can already promote the desired effects. Of course, these concentration values should not be interpreted restrictively, those skilled in the art know from experience that in any practical use, the determination of such values depends on the nature of the products which it is desired to flavor as well as that of the co-ingredients in a given composition. Spiro [5.7] tridéc-1-ene-3-one can be used in an isolated state, but more generally it will be used in admixture with usual diluents, carriers or excipients, as well as with other perfuming ingredients currents. Many examples of such co-ingredients and additives are provided in the prior art [see for example S. Arctander, op. cit.].

La présente invention a donc pour objet, outre l'utilisation telle que définie plus haut, une composition parfumante ainsi que des produits parfumés contenant la spiro[5.7]tridéc-1-ène-3-one à titre d'ingrédient parfumant actif.The present invention therefore relates, in addition to the use as defined above, a perfuming composition and products fragrances containing spiro [5.7] tridec-1-ene-3-one as an active fragrance ingredient.

Comme indiqué plus haut, la spiro[5.7]tridéc-1-ène-3-one est un composé connu qui peut être obtenu en suivant l'un des procédés de préparation décrits dans les documents cités, par exemple à partir de cyclooctanecarboxaldéhyde par réaction avec la méthyl-vinyle cétone en présence d'acide p-toluénesulfonique. Le produit obtenu était en tous points identique aux indications fournies par la littérature.As indicated above, spiro [5.7] tridec-1-ene-3-one is a known compound which can be obtained by following one of the preparation methods described in the cited documents, for example from cyclooctanecarboxaldehyde by reaction with methyl vinyl ketone in the presence of p-toluenesulfonic acid. The product obtained was identical in all respects to the indications provided by the literature.

L'invention est illustrée de manière plus détaillée par les exemples d'application suivants.The invention is illustrated in more detail by the following application examples.

Exemple 1Example 1

On a préparé une composition parfumante de base pour détergents en poudre en mélangeant les ingrédients suivants : Ingrédients Parties en poids Acétate de benzyle 250 Acétate de phényléthyle 100 Acétate de styrallyle 125 Aldéhyde C9 10% * 50 Aldéhyde C10 10% * 50 Allyl amyle glycolate 50 Anthranilate de méthyle 10% * 50 Citronellol 50 Acétate de verdyle 25 Diphényloxyde 10% * 200 Acétate de p-tert-butylcyclohexyle 250 Essence de girofle de Madagascar 100 Galaxolide 50 MIP 1) 200 Galione 2) 50 Geraniol brut (Glidden) 465 100 Lilial ® 3) 100 Linalol 1000 Menthone purifiée 10% * 250 Essence de patchouli 125 Phénylacétate de phényléthyle 50 Essence d'orange du Brésil 125 Salicylate d'amyle 100 Salicylate de benzyle 150 Salicylate d'hexyle 3500 Terpinéol ord. 2000 Tetrahydromuguol 1) 600 Polywood ® 4) 50 Ylang synthétique 50 Coumarine 100 Total 9850 * dans le dipropylèneglycol (DIPG) 1) origine : International Flavors and Fragrances Inc., USA 2) méthylionone; origine : Firmenich SA, Genève, Suisse 3) origine : L. Givaudan, Vernier, Suisse 4) acétate de 1,7,7,-triméthylbicyclo[4.4.0]décyle; origine : Firmenich SA, Genève, Suisse
L'adjonction de 15 parties en poids de spiro[5.7]tridéc-1-ène-3-one à 985 parties de la composition de base a fourni une nouvelle composition possédant un caractère marqué de type irisé et violette. La spiro[5.7]tridéc-1-ène-3-one ajoutée confère à la composition un aspect odorant de propreté dont la note se marie agréablement avec la douceur des notes poudrées de type coumariné, méthylionone ou de type salicylate.A basic perfuming composition for powdered detergents was prepared by mixing the following ingredients: Ingredients Parts by weight Benzyl acetate 250 Phenylethyl acetate 100 Styrallyl acetate 125 Aldehyde C9 10% * 50 Aldehyde C10 10% * 50 Allyl amyl glycolate 50 Methyl anthranilate 10% * 50 Citronellol 50 Verdyl acetate 25 Diphenyloxide 10% * 200 P-tert-butylcyclohexyl acetate 250 Clove essence from Madagascar 100 Galaxolide 50 MIP 1) 200 Galione 2) 50 Raw Geraniol (Glidden) 465 100 Lilial ® 3) 100 Linalol 1000 Purified menthone 10% * 250 Essence of patchouli 125 Phenylethyl phenylacetate 50 Brazilian orange essence 125 Amyl salicylate 100 Benzyl salicylate 150 Hexyl salicylate 3500 Terpineol ord. 2000 Tetrahydromuguol 1) 600 Polywood ® 4) 50 Synthetic ylang 50 Coumarin 100 Total 9850 * in dipropylene glycol (DIPG) 1) origin: International Flavors and Fragrances Inc., USA 2) methylionone; origin: Firmenich SA, Geneva, Switzerland 3) origin: L. Givaudan, Vernier, Switzerland 4) 1,7,7 acetate, trimethylbicyclo [4.4.0] decyl; origin: Firmenich SA, Geneva, Switzerland
The addition of 15 parts by weight of spiro [5.7] tridec-1-ene-3-one to 985 parts of the basic composition provided a new composition having a marked character of iridescent and violet type. The added spiro [5.7] tridéc-1-ene-3-one gives the composition an odorous, clean appearance, the note of which blends pleasantly with the soft powdery notes of coumarin, methylionone or salicylate type.

Exemple 2Example 2

On a préparé une composition parfumante de base de type vetyver en mélangeant les ingrédients suivants : Ingrédients Parties en poids Essence de vetyver Haïti 500 Rhubofix 1) 20 Vertofix coeur 2) 260 Cedroxyde 3) 100 Cedrol 100 Total 980 1) époxyéthyl-méthyltricycloundécène; origine : Firmenich SA, Genève, Suisse 2) origine : International Flavors and Fragrances Inc., USA 3) triméthylcyclododécatriène époxyde; origine : Firmenich SA, Genève, Suisse
L'adjonction, à raison de 2% de spiro[5.7]tridéc-1-ène-3-one à la base parfumante ainsi préparée renforce l'aspect boisé-vetyver de la composition tout en lui conférant un caractère naturel.A basic perfume composition of the vetyver type was prepared by mixing the following ingredients: Ingredients Parts by weight Essence of vetyver Haiti 500 Rhubofix 1) 20 Vertofix heart 2) 260 Cedroxide 3) 100 Cedrol 100 Total 980 1) epoxyethyl-methyltricycloundecene; origin: Firmenich SA, Geneva, Switzerland 2) origin: International Flavors and Fragrances Inc., USA 3) epoxy trimethylcyclododecatriene; origin: Firmenich SA, Geneva, Switzerland
The addition, at a rate of 2% of spiro [5.7] tridéc-1-ene-3-one to the perfume base thus prepared reinforces the woody-vetyver aspect of the composition while giving it a natural character.

Claims (5)

  1. Use of spiro[5.7]tridec-1-ene-3-one as a perfuming ingredient.
  2. Perfuming composition characterized in that it contains as an active perfuming ingredient spiro[5.7]tridec-1-ene-3-one in combination with current solvents, carriers or excipients, as well as other perfuming ingredients of current use.
  3. Perfumed article characterized in that it contains as an active perfuming ingredient spiro[5.7]tridec-1-ene-3-one.
  4. As a perfumed article according to claim 3, a soap, a detergent, a fabric softener, a cosmetic preparation, a cream, a shampoo, a hair care product, a household product or an ambient air deodorant.
  5. A method to confer, improve or modify the odour properties of a perfuming composition or a perfumed consumer article, characterized in that there is added to a perfuming base or a consumer product spiro[5.7]tridec-1-ene-3-one in an olfactively perceptible amount.
EP92101748A 1991-03-15 1992-02-03 Perfuming ingredient with a spiranic structure Expired - Lifetime EP0504563B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH79691 1991-03-15
CH796/91 1991-03-15

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EP0504563A1 EP0504563A1 (en) 1992-09-23
EP0504563B1 true EP0504563B1 (en) 1994-12-28

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JP (1) JPH0570792A (en)
DE (1) DE69200982T2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100337692C (en) * 2005-03-16 2007-09-19 周娉 Chinese medicine perfume and its preparing method

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4261866A (en) * 1979-11-02 1981-04-14 Fritzsche Dodge & Olcott Inc. Spirodienones and spirocyclic ketones
NL8104271A (en) * 1981-09-16 1983-04-18 Naarden International Nv PERFUME COMPOSITIONS AND PERFUMED PRODUCTS CONTAINING SPIROUNDECANONES AND -UNDECENONES AS PERFUME RAW.

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DE69200982D1 (en) 1995-02-09
EP0504563A1 (en) 1992-09-23
US5151410A (en) 1992-09-29
DE69200982T2 (en) 1995-05-11
JPH0570792A (en) 1993-03-23

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