CH537452A - Unsaturated cycloaliphatic ketones - Google Patents

Unsaturated cycloaliphatic ketones

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Publication number
CH537452A
CH537452A CH537452DA CH537452A CH 537452 A CH537452 A CH 537452A CH 537452D A CH537452D A CH 537452DA CH 537452 A CH537452 A CH 537452A
Authority
CH
Switzerland
Prior art keywords
trimethyl
formula
cyclohexene
ketones
methyl
Prior art date
Application number
Other languages
French (fr)
Inventor
Ervin Dr Kovats
Guenther Dr Ohloff
Edouard Dr Demole
Max Dr Stoll
Original Assignee
Firmenich & Cie
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
Priority claimed from CH697669A external-priority patent/CH520767A/en
Application filed by Firmenich & Cie filed Critical Firmenich & Cie
Publication of CH537452A publication Critical patent/CH537452A/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
    • C07C403/16—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms not being part of —CHO groups
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/20—Synthetic spices, flavouring agents or condiments
    • A23L27/203—Alicyclic compounds
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
    • A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
    • A24B15/34—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a carbocyclic ring other than a six-membered aromatic ring
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
    • A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
    • A24B15/36—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring
    • A24B15/40—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring having only oxygen or sulfur as hetero atoms
    • A24B15/403—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring having only oxygen or sulfur as hetero atoms having only oxygen as hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/04—Acyclic alcohols with carbon-to-carbon triple bonds
    • C07C33/048—Acyclic alcohols with carbon-to-carbon triple bonds with double and triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
    • C07C403/08—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/14—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by free hydroxyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/32—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by aldehydo- or ketonic radicals
    • 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
    • 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
    • C11B9/0069—Heterocyclic compounds
    • C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
    • C11B9/0076—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing less than six atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

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  • General Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nutrition Science (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Fats And Perfumes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The ketones have organoleptic properties and can be used in the perfumery industry, as ingredients in artificial essences and as additives for human and animal food, drinks, pharmaceuticals and tobacco. They have the formula : (where R1, R2 and R3 are H or one of them is a lower alkyl radical; R4, R5, R6 and R7 are H or one of them is a lower alkyl radical and n is 0 or 1). Prepn. is by oxidation of the corresponding alcohols (in posn.11) which also possess similar properties and are themselves prepd. by the addition of an organometallic cpd. of formula : Me CHn(R3) = C(R2) - CH2-nR1 (where Me is Li or BrMg) to alpha-, beta- or gamma-cyclocitral derivs. followed by hydrolysis of the resulting addn. product.

Description

  

  
 



   La présente invention a pour objet l'utilisation comme agent parfumant d'au moins une des cétones insaturées de formule
EMI1.1     
 contenant une double liaison dans l'une des positions indiquées par les pointillés et dans laquelle les substituants R représentent l'hydrogène ou   l'un    d'entre-eux un groupe méthyle et les autres l'hydrogène.



   On a découvert que les composés de formule I sont doués de propriétés organoleptiques particulièrement intéressantes et de ce fait sont utilisables comme agents parfumants dans l'industrie des parfums.



   Les composés de l'invention peuvent   etre    utilisés comme ingrédients odoriférants dans les parfums dilués ou concentrés et dans les produits parfumés tels les savons, les détergents. les produits cosmétiques. les cires et autres produits pouvant être parfumés et susceptibles de devenir ainsi plus intéressants du point de vue commercial. De plus. les composés de cette invention sont très prisés en tant qu'ingrédients entrant dans la préparation d'huiles essentielles artificielles. telles par exemple les essences de jasmin. de géranium Bourbon, de rose etc..



  Les cétones de formule I augmentent souvent la puissance et le pouvoir de diffusion des compositions de parfums et leur confèrent dans bien des cas une richesse très naturelle.



   Les proportions dans lesquelles les cétones insaturées de formule I peuvent être employées pour produire un effet odoriférant intéressant varient de façon étendue. Par exemple.



  dans la préparation de compositions de parfums. des effets intéressants peuvent déjà être obtenus par la présence desdites cétones en proportions de   100    ppm à   5%    du total de la composition. Suivant les buts odoriférants spécifiques recherchés.



  ces proportions peuvent être portées jusqu'à   10%    et même plus.



   Il est bien   entende    que les limites de proportions données ci-dessus ne représentent pas des limites absolues: dans certains cas où on désire obtenir des effets spéciaux, les nouvelles cétones peuvent être employées en concentrations supérieures ou inférieures à celles indiquées plus haut.



   Pour la préparation des cétones de formule I, on peut   oxvder    des alcools de formule
EMI1.2     
    55    dans laquelle les pontillés et les R ont le même sens que pour
I, au moyen d'un agent oxydant.



   Comme agents oxydants on peut utiliser la plupart des agents généralement connus pour oxyder les alcools en cétones ou en aldéhydes. On peut employer comme agents oxydants le carbonate d'argent en présence de terre d'infusoires, des sels et dérivés oxygénés de certains éléments de transition comme le chrome, le nickel et le manganèse, et l'oxygène sous forme de gaz (pur ou atmosphérique) en présence d'activateurs comme par exemple des initiateurs de la formation de radicaux libres.



  Des sels et dérivés du chrome et du manganèse utilisables dans le procédé d'oxydation ci-dessus comprennent par exemple   CrO    ou l'acide chromique. le   MnO    ou des permanganates.



  De préférence on emploie le trioxyde de chrome ou les chromates alcalins [voir par exemple J. Org. Chem. 26. 4814   (1961)j.   



   On peut préparer les alcools de formule II, qui sont nouveaux, par une réaction de Grignard entre   1'(e-    ou le   5-cycloci-    tral et un dérivé halogéné allylique de formule
 X-CHR-CR=CHR dans laquelle X désigne un halogène et les R ont le même sens que ci-dessus.



   L'une des cétones insaturées de formule I, plus précisément le   2.6.6-triméthyl-1-vinylacétyl-1-cyclohexène,    peut être préparée comme suit [voir J. Am. Chem. Soc. 75. 422   (1953)l.   



   On a refroidi 450   ml    de pyridine anhydre à   04C    et, sous vive agitation, on a introduit par portions. 41 g d'anhydride chromique pur, la température étant maintenue à   0 > C.    On a ensuite ajouté goutte à goutte à   0nC    une solution de 25,4 g de 2,6,6   triméthyl- 1-11    -hydroxybutén-3-yl-   1l-cyclohexène- 1    dans 80   ml    de pyridine. On a maintenu 30 minutes à   0OC,    puis 10 heures à   200C.    On a versé le mélange sur 1 litre d'eau. On a extrait le mélange à l'éther et lavé l'extrait à l'acide chlorhydrique aqueux à   10etc,    puis au   Ma2CO3    aqueux à   5Cc.    puis à l'eau.

  Après le traitement usuel et purification par distillation.



  on a obtenu le 2,6,6-triméthyl-1-vinylacétylcyclohexène-1 avec un rendement de   60C c.   



     n     = 1,4897;   d420    = 0,9361.



   En remplaçant ci-dessus le   2.6.6-triméthyl i      1-[1 -hydroxybutén-3-vllcyclohexène-    1 par le    2,6.6-triméthyl- 1 -[1 -hydroxy-3-méthylbutén-3-yl]-cyclo- hexène-l   
   (n20    = 1,4939;   d42o    = 0,9270) on a obtenu le   2,6,6-triméthyl- l-[3-méthyl-butén-.?-oyli-    cyclohexène- 1,
   nDo    = 1,4862; d420 = 0,9307.



   Les composés hydroxylés utilisés comme produits de départ ci-dessus ont été préparés, suivant les conditions usuelles. par
 une réaction de Grignard, entre le   5-cyclocitral    et le chlorure ou le bromure d'allyle, ou le chlorure de méthallyle. Ainsi, à
 10,7 g de Mg en copeaux, on a ajouté une solution de 5 g de bromure d'allyle dans 70   ml    d'éther sec. Le solvant s'est mis à bouillir. On a introduit alors goutte à goutte en agitant, une solution de 46 g de bromure d'allyle, 61 g de   5-cyclocitral    et
 160   ml    d'éther à une vitesse suffisante pour maintenir l'éther en ébullition. On a ensuite chauffé 6 h à reflux. 

  Après refroidissement, on a traité le mélange par une solution aqueuse concentrée glacée de   NH4Cl    puis on a traité la couche éthérée comme d'habitude; on a obtenu 44,5 g   (57Czc)    de 2,6,6-trimé   thyl-l-[l -hydroxybutén-3-yl] -cyclohexène-l. éb. 60-62^C,    0,001 Torr;
   n20    = 1,4964;   d420    = 0,9398; 0,9398; spectre RMN   (CCl4):    0,98 (3H, s); 1,10 (3H, s); 1,82
 (3H, s); 1,20-2,80 (9H, m);   4,22    (1H, m); 5,04 (2H, d.   J= 15    cps); 5,88 (1H, m)   b    ppm.



   En remplaçant dans la réaction ci-dessus le bromure d'allyle par un équivalent de chlorure de méthallyle, on a obtenu le carbinol correspondant avec des rendements similaires.  



   On peut également procéder comme suit:
Entre - 5 et   - 10 >     on a ajouté goutte à goutte une solution de 15 g de   2,6,6-triméthyl- 1-[ 1 -hydroxybutén-3-yl] -cyclohexène- 1    dans 100 ml d'acétone à un mélange de 800 ml d'acétone purifiée et de 100 ml d'une solution aqueuse contenant 26 g de   CrO3    et 23 ml de   H2S04    concentré (réactif de Jones). Après virage de la couleur initiale, on a dilué à l'eau, concentré sous vide et extrait à l'éther. Le traitement habituel a fourni 9 g de distillat lequel, après purification par distillation au moyen d'un appareil à bande tournante ou par chromatographie en phase gazeuse, a donné   384    de 3,6,6-triméthyl-1-vinylacétyl   cyclohexène- 1    pur.



   En remplaçant dans la réaction ci-dessus le carbinol susmenntionné par son homologue, le 2,6,6-triméthyl-1-[1- hydroxy3-méthyl-butén-3-yl]-cyclohexène-1, on a obtenu le 2,6,6triméthyl-1-[3-méthylbutén-3-oyll-cyclohexène-1 avec un rendement de   424.   



   On peut aussi procéder comme suit: A   0O,    on a ajouté goutte à goutte une solution de 15 g de 2,6,6-triméthyl-1-[1   hydroxybutén-3-yl]-cyclohexène-t    dans 50 ml de benzène à une solution en agitation de 160 ml d'H20, 20 ml d'AcOH, 60 ml de benzène, 40 g de   Na2CrO4,    64 g de   H2S04.    Après 3 h d'agitation, on a dilué à l'eau, extrait à l'éther et traité l'extrait comme de coutume. On a ainsi obtenu 8,8 g de cétone brute qui, purifiée comme décrit à l'Exemple précédent, a fourni   44%    de   2,6,6-triméthyl-1-vinyl-acétylcyclohexène- t    pur.



   Finalement, on peut encore procéder comme suit:
Entre   O    et   -50C,    à l'abri de la lumière, on a ajouté goutte à goutte une solution de   11 g    de 2,6,6-triméthyl-1-[1-hydroxy   butén-3-yll-cyclohexène-1    dans 50 ml de benzène à une solution en agitation de 18 g de   CrO    dans 130 g de tert.-butanol et 60 ml de benzène. On a agité encore 12 h dans l'obscurité, puis on a dilué à l'eau et séparé la couche benzénique. Celle-ci, traitée comme d'habitude, a fourni après distillation 8,5 g de produit brut qui, après purification, a fourni 35   %    de cétone pure.



   L'Exemple suivant illustre l'invention de manière plus détaillée.



   Exemple
 Composition de parfum de type Chypre
 On prépare une composition de type Chypre en mélangeant les ingrédients suivants:
Ingrédients Parties en poids
Bergamote 21
Portugal 0,5
Néroli synthétique 1
Rose synthétique 9
Jasmin synthétique 9
Ylang extra 6
Méthylionone 6
Hydroxycitronellal 6
Santal oriental 3
Patchouli 1,5
Acétate de vétivéryle 4,5
Civette naturelle dégraissée à 10%*) 3
Labdanum ciste absolu à 10%*) 2
Musc cétone 4   1,1-Diméthyl-6-(tert.)butyl-4-acétylindane    0,5
Coumarine 3
Acétate de trichlorméthyl-phénylcarbinyle 1,5
Estragon à 10%*) 3
Mousse de chêne absolue à 50%*) 6
Benjoin larmes à 10%*) 1,5
Alcool cinnamique du Styrax 1,5
Jasmin absolu 1,5
Rose absolue 1
Cyclopentadécanolide   à 10%*)    2
Aldéhyde méthylnonylacétique 1,5
Total 99,5
 En ajoutant à 99,5 g de ce mélange 0,5 g d'une solution à  <RTI   

    ID=2.22> jonc*)    de   2,6,6-triméthyl-l -vinylacétylcyclohexène- 1,    on obtient une composition plus puissante que la composition de base dont la diffusion est améliorée et qui présente une richesse très naturelle. 



  
 



   The present invention relates to the use as a perfuming agent of at least one of the unsaturated ketones of formula
EMI1.1
 containing a double bond in one of the positions indicated by the dotted lines and in which the substituents R represent hydrogen or one of them a methyl group and the others hydrogen.



   It has been discovered that the compounds of formula I are endowed with particularly advantageous organoleptic properties and therefore can be used as perfuming agents in the perfume industry.



   The compounds of the invention can be used as odoriferous ingredients in diluted or concentrated perfumes and in perfumed products such as soaps and detergents. cosmetic products. waxes and other products which can be perfumed and thus likely to become more interesting from a commercial point of view. Furthermore. the compounds of this invention are highly valued as ingredients for the preparation of artificial essential oils. such, for example, essences of jasmine. Bourbon geranium, rose, etc.



  The ketones of formula I often increase the potency and the diffusing power of the perfume compositions and in many cases give them a very natural richness.



   The proportions in which the unsaturated ketones of formula I can be employed to produce a desirable odoriferous effect vary widely. For example.



  in the preparation of perfume compositions. interesting effects can already be obtained by the presence of said ketones in proportions of 100 ppm to 5% of the total of the composition. According to the specific odoriferous goals sought.



  these proportions can be increased up to 10% and even more.



   It is understood that the limits of proportions given above do not represent absolute limits: in certain cases where it is desired to obtain special effects, the new ketones can be used in concentrations higher or lower than those indicated above.



   For the preparation of the ketones of formula I, it is possible to oxidize alcohols of formula
EMI1.2
    55 in which the pontillates and the R have the same meaning as for
I, by means of an oxidizing agent.



   As oxidizing agents, most of the agents generally known for oxidizing alcohols to ketones or to aldehydes can be used. As oxidizing agents can be used silver carbonate in the presence of diatomaceous earth, salts and oxygenated derivatives of certain transition elements such as chromium, nickel and manganese, and oxygen in the form of gas (pure or atmospheric) in the presence of activators such as for example initiators of the formation of free radicals.



  Salts and derivatives of chromium and manganese which can be used in the above oxidation process include, for example, CrO or chromic acid. MnO or permanganates.



  Preferably, chromium trioxide or alkali metal chromates are used [see for example J. Org. Chem. 26. 4814 (1961) j.



   The alcohols of formula II, which are novel, can be prepared by a Grignard reaction between 1 '(e- or 5-cycloctral and a halogenated allylic derivative of formula
 X-CHR-CR = CHR in which X denotes a halogen and the Rs have the same meaning as above.



   One of the unsaturated ketones of formula I, more precisely 2,6.6-trimethyl-1-vinylacetyl-1-cyclohexene, can be prepared as follows [see J. Am. Chem. Soc. 75. 422 (1953) l.



   450 ml of anhydrous pyridine was cooled to 04C and, with vigorous stirring, was introduced in portions. 41 g of pure chromic anhydride, the temperature being maintained at 0> C. A solution of 25.4 g of 2,6,6 trimethyl-1-11 -hydroxybuten-3-yl was then added dropwise at 0 nC. - 11-cyclohexene-1 in 80 ml of pyridine. Was maintained 30 minutes at 0OC, then 10 hours at 200C. The mixture was poured onto 1 liter of water. The mixture was extracted with ether and the extract washed with aqueous hydrochloric acid at 10 ° C., then with aqueous Ma2CO3 at 5 ° C. then to water.

  After the usual treatment and purification by distillation.



  2,6,6-trimethyl-1-vinylacetylcyclohexene-1 was obtained with a yield of 60C c.



     n = 1.4897; d420 = 0.9361.



   By replacing above 2.6.6-trimethyl i 1- [1 -hydroxybuten-3-vllcyclohexene- 1 by 2,6.6-trimethyl- 1 - [1 -hydroxy-3-methylbuten-3-yl] -cyclo- hexene-l
   (n20 = 1.4939; d42o = 0.9270) was obtained 2,6,6-trimethyl- 1- [3-methyl-buten -.?- oyli- cyclohexene- 1,
   nDo = 1.4862; d420 = 0.9307.



   The hydroxylated compounds used as starting products above were prepared, according to the usual conditions. by
 a Grignard reaction, between 5-cyclocitral and allyl chloride or bromide, or methallyl chloride. So at
 10.7 g of Mg shavings, a solution of 5 g of allyl bromide in 70 ml of dry ether was added. The solvent started to boil. Was then introduced dropwise with stirring, a solution of 46 g of allyl bromide, 61 g of 5-cyclocitral and
 160 ml of ether at a speed sufficient to keep the ether boiling. Then heated for 6 h at reflux.

  After cooling, the mixture was treated with an ice-cold concentrated aqueous NH4Cl solution and then the ethereal layer was treated as usual; 44.5 g (57Czc) of 2,6,6-trimer thyl-1- [1 -hydroxybuten-3-yl] -cyclohexene-1 were obtained. eb. 60-62 ° C, 0.001 Torr;
   n20 = 1.4964; d420 = 0.9398; 0.9398; NMR spectrum (CCl4): 0.98 (3H, s); 1.10 (3H, s); 1.82
 (3H, s); 1.20-2.80 (9H, m); 4.22 (1H, m); 5.04 (2H, d. J = 15 cps); 5.88 (1H, m) b ppm.



   By replacing in the above reaction allyl bromide with one equivalent of methallyl chloride, the corresponding carbinol was obtained with similar yields.



   You can also proceed as follows:
Between -5 and -10> a solution of 15 g of 2,6,6-trimethyl- 1- [1-hydroxybuten-3-yl] -cyclohexene-1 in 100 ml of acetone was added dropwise to a mixture of 800 ml of purified acetone and 100 ml of an aqueous solution containing 26 g of CrO3 and 23 ml of concentrated H2SO4 (Jones reagent). After changing to the initial color, it was diluted with water, concentrated in vacuo and extracted with ether. The usual work-up gave 9 g of distillate which, after purification by distillation using a rotary band apparatus or by gas chromatography, gave 384 of pure 3,6,6-trimethyl-1-vinylacetyl cyclohexene-1. .



   By replacing in the above reaction the above-mentioned carbinol by its homologue, 2,6,6-trimethyl-1- [1-hydroxy3-methyl-buten-3-yl] -cyclohexene-1, we obtained 2, 6,6trimethyl-1- [3-methylbuten-3-oyll-cyclohexene-1 with a yield of 424.



   It is also possible to proceed as follows: At 0O, a solution of 15 g of 2,6,6-trimethyl-1- [1 hydroxybuten-3-yl] -cyclohexene-t in 50 ml of benzene was added dropwise. a stirring solution of 160 ml of H2O, 20 ml of AcOH, 60 ml of benzene, 40 g of Na2CrO4, 64 g of H2SO4. After 3 h of stirring, it was diluted with water, extracted with ether and the extract treated as usual. There was thus obtained 8.8 g of crude ketone which, purified as described in the preceding Example, provided 44% of pure 2,6,6-trimethyl-1-vinyl-acetylcyclohexene-t.



   Finally, we can still proceed as follows:
Between 0 and -50C, protected from light, was added dropwise a solution of 11 g of 2,6,6-trimethyl-1- [1-hydroxy buten-3-yll-cyclohexene-1 in 50 ml of benzene to a stirring solution of 18 g of CrO in 130 g of tert.-butanol and 60 ml of benzene. Stirred a further 12 h in the dark, then diluted with water and separated the benzene layer. This, treated as usual, gave after distillation 8.5 g of crude product which, after purification, gave 35% pure ketone.



   The following Example illustrates the invention in more detail.



   Example
 Cyprus type perfume composition
 A Cyprus-type composition is prepared by mixing the following ingredients:
Ingredients Parts by weight
Bergamot 21
Portugal 0.5
Synthetic neroli 1
Synthetic pink 9
Synthetic jasmine 9
Ylang extra 6
Methylionone 6
Hydroxycitronellal 6
Eastern sandalwood 3
Patchouli 1.5
Vetiveryl acetate 4.5
Natural civet defatted to 10% *) 3
Labdanum cistus absolute 10% *) 2
Musk ketone 4 1,1-Dimethyl-6- (tert.) Butyl-4-acetylindane 0.5
Coumarin 3
1.5 Trichlormethyl-phenylcarbinyl acetate
Tarragon 10% *) 3
Oakmoss 50% absolute *) 6
Benzoin tears at 10% *) 1.5
Cinnamic alcohol from Styrax 1.5
Absolute jasmine 1.5
Absolute rose 1
10% cyclopentadecanolide *) 2
Methyl nonylacetic aldehyde 1.5
Total 99.5
 By adding to 99.5 g of this mixture 0.5 g of a solution at <RTI

    ID = 2.22> rod *) of 2,6,6-trimethyl-1-vinylacetylcyclohexene-1, a more potent composition is obtained than the base composition, the diffusion of which is improved and which exhibits a very natural richness.

Claims (1)

REVENDICATION CLAIM Utilisation d'au moins une des cétones synthétiques insaturées de formule EMI2.1 contenant une double liaison dans l'une des positions indiquée par les pointillés et dans laquelle les substituants R représentent l'hydrogène ou l'un d'entre-eux un groupe méthyle et les autres l'hydrogène, comme agent parfumant. Use of at least one of the unsaturated synthetic ketones of formula EMI2.1 containing a double bond in one of the positions indicated by the dotted lines and in which the substituents R represent hydrogen or one of them a methyl group and the others hydrogen, as a perfuming agent. SOUS-REVENDICATION Utilisation suivant la revendication d'au moins un des composés suivants: ¯ 2,6,6-triméthyl-l-vinylacéty]-cyclohexèn 2,6,6-triméthyl- 1-[3-méthyl-butén-3-oyl)- t j-cyclohexène- 1, 2,6,6-triméthyl- 1-vinylacétyl-cyclohexène-2, 2.6,6-triméthyl- 1-[3-méthyl-butén-3-oyl- t j-cyclohexène-2. SUB-CLAIM Use according to claim of at least one of the following compounds: ¯ 2,6,6-trimethyl-1-vinylacety] -cyclohexen 2,6,6-trimethyl- 1- [3-methyl-buten-3-oyl) - t j-Cyclohexene-1, 2,6,6-trimethyl-1-vinylacetyl-cyclohexene-2, 2.6,6-trimethyl-1- [3-methyl-buten-3-oyl-t-j-cyclohexene-2.
CH537452D 1969-05-07 1969-08-08 Unsaturated cycloaliphatic ketones CH537452A (en)

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CH697669A CH520767A (en) 1969-05-07 1969-05-07 Unsaturated cycloaliphatic ketones
CH1206569 1969-08-08

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CH537452A true CH537452A (en) 1973-07-13

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5069047A (en) * 1973-10-22 1975-06-09

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5069047A (en) * 1973-10-22 1975-06-09

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