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CH513098A - Unsaturated cycloaliphatic ketones - Google Patents

Unsaturated cycloaliphatic ketones

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Publication number
CH513098A
CH513098A CH1805570A CH1805570A CH513098A CH 513098 A CH513098 A CH 513098A CH 1805570 A CH1805570 A CH 1805570A CH 1805570 A CH1805570 A CH 1805570A CH 513098 A CH513098 A CH 513098A
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Switzerland
Prior art keywords
sep
formula
symbols
derivatives
double bond
Prior art date
Application number
CH1805570A
Other languages
French (fr)
Inventor
Ervin Dr Kovats
Edouard Dr Demole
Guenther Dr Ohloff
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
Application filed by Firmenich & Cie filed Critical Firmenich & Cie
Priority to CH1805570A priority Critical patent/CH513098A/en
Publication of CH513098A publication Critical patent/CH513098A/en

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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
    • C11B9/0069—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
    • 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
    • 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
    • A23L27/70—Fixation, conservation, or encapsulation of flavouring agents
    • 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
    • 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
    • C07C29/74—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
    • C07C403/14—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
    • 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
    • C11B9/0007—Aliphatic compounds
    • C11B9/0015—Aliphatic compounds containing oxygen as the only heteroatom
    • 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
    • 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
    • C07C2601/14—The ring being saturated
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Polymers & Plastics (AREA)
  • Nutrition Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Food Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)
  • Epoxy Compounds (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Seasonings (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

  

  
 



  Procédé pour   a    préparation de composés   cycloolefiniques    carbonylés
La présente invention concerne un procédé pour la préparation de cétones cyclooléfiniques de formule:
EMI1.1     
 dans laquelle les pointillés représentent soit une double liaison endocyclique en position 1- (structure   )    ou 2 (structure a) soit une double liaison en position exocyclique (structure   dry),    soit deux doubles liaisons conjuguées et dans laquelle les symboles R et R' constituent deux classes de substituants dans chacune desquelles lesdits substituants représentent soit l'hydrogène, soit   l'un    d'entre eux un alcoyle et les autres l'hydrogène.

  Lesdits substituants ne peuvent cependant représenter simultanément tous l'hydrogène que lorsque le cycle ne contient qu'une double liaison exocyclique.



   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, comme ingrédients dans la préparation d'arômes artificiels et comme agents aromatisants pour l'aromatisation d'aliments, d'aliments pour animaux, de boissons, de préparations pharmaceutiques et du tabac.



   Les nouvelles cétones peuvent être utilisées comme ingrédients odoriférants dans les parfums dilués ou con centrés et dans les produits parfumés tels les savons, les    I-a,=    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, ces composés 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 cétones I possèdent également des propriétés aromatisantes très intéressantes. Selon la nature des produits auxquels on les ajoute elles développent des notes aromatiques fruitées, vineuses, boisées, florales, cireuses ou de plantes aromatiques, ou toute combinaison desdites notes.



   Le procédé de préparation des composés I suivant l'invention est caractérisé en ce qu'on acyle un dérivé organo-métallique du propène de formule:    ME-CR= CR-CH2R     dans laquelle les symboles R ont le sens défini plus haut et ME représente une fonction métallique réactive au moyen d'un dérivé de formule:
EMI2.1     
 dans laquelle les pointillés et les symboles R' ont le sens défini plus haut et dans laquelle X représente un groupe scindable dans les conditions de la réaction.



  Comme fonction métallique on peut utiliser, par exemple, le lithium, le zinc, le cadmium ou le groupe Mg-halogène et comme réactif acylant un composé de formule   II    dans laquelle X représente, par exemple, un reste halogène, un groupe O-alcoyle, O-aryle, O-CO-alcoyle ou
O-CO-aryle.



   Dans le procédé défini ci-dessus on utilise de préférence comme dérivés cyclogéranylés des halogénures de géranoyle (par exemple les chlorures et bromures) ou des géraniates (par exemple de méthyle, d'éthyle ou de lithium).



   Les dérivés cyclogéraniques et safraniques utilisables dans le procédé ci-dessus peuvent être préparés suivant des méthodes dont quelques exemples sont donnés ciaprès. Ainsi,   1)    les dérivés cyclogéraniques de structure   IIa-    et   p-    peuvent être obtenus à partir des acides cy   clogéraniques    correspondants   (a-    ou   ,8-)    par les moyens habituels.

  Les acides   Q-    et   f;-cyclogéraniques    eux-mêmes peuvent être obtenus à partir des dérivés correspondants du citral III suivant des méthodes connues, par exemple par oxydation desdits dérivés du citral en acides géraniques [voir à ce sujet   Gildmeister     & Hoffmann, Die   Àtherischen      Ôle,    IIId, pp. 137-138, Akademie-Verlag,
Berlin (1966)].



   La méthode de préparation des dérivés   II    de structure   Q-    et p- peut être illustrée par le schéma A suivant dans lequel les symboles R' et les pointillés ont le sens déjà expliqué plus haut.



  Schéma A
EMI2.2     


<tb>  <SEP> R' <SEP> R' <SEP> R'
<tb> R <SEP> t <SEP> W <SEP> CHO <SEP> R <SEP> W <SEP> COOH <SEP> R <SEP> t <SEP> C <SEP> COOH
<tb>  <SEP> OXYdtIO$,·Ç <SEP> cyclisation
<tb>  <SEP> R'
<tb>  <SEP> R' <SEP> R' <SEP> R'
<tb>  <SEP> III
<tb>  <SEP> halogénation
<tb>  <SEP> ou <SEP> esterifidérivés <SEP> du <SEP> dérivés <SEP> de <SEP> ou <SEP> estérìfi
<tb>  <SEP> citral <SEP> l'acide <SEP> géranique
<tb>  <SEP> R'
<tb>  <SEP> R'J <SEP> COX
<tb>  <SEP> Cox
<tb>  <SEP> II-a, 
 2) Les dérivés cyclogéraniques   II    de structure   Q-,      p-    et y- peuvent être aussi obtenus à partir des dérivés correspondants du citral (III) par cyclisation en cyclocitrals a- et   p-    correspondants [voir par exemple Bedoukian,

   Perfumery and
Flavoring   Synthetics,    Elsevier, New York (1967)]. Pour obtenir la structure y-, on procède à l'isomérisation des cyclocitrale   p-.    Puis on oxyde le groupe aldéhyde des cyclocitrals en groupe -COOH et finalement on transforme le groupe -COOH en groupe -COX par les moyens habituels. Le schéma B ci-dessous dans lequel les R' et les pointillés ont le sens expliqué plus haut illustre cette méthode.  



  Schéma B
EMI3.1     


<tb>  <SEP> R' <SEP> 1
<tb>  <SEP> R <SEP> ' <SEP> RN
<tb> R <SEP> cyclisation <SEP> R' <SEP> CHO <SEP> CHO
<tb>  <SEP> R' <SEP> t
<tb>  <SEP> IV- <SEP>  2 <SEP> lV
 <SEP> III
<tb>  <SEP> o(-cyclocitrals <SEP> j-cyclocitrals
<tb>  <SEP> isomérisation
<tb>  <SEP> R'
<tb>  <SEP> I
<tb>  <SEP> Rus
<tb>  <SEP> IV-Y
<tb>  <SEP> IV
<tb>  <SEP> -cyc1oc <SEP> itral <SEP> s
<tb>  <SEP> R'
<tb>  <SEP> R <SEP> CHO <SEP> oxydation <SEP> R <SEP> ' <SEP> tY <SEP> COOH
<tb>  <SEP> R'
<tb>  <SEP> R'
<tb>  <SEP> R'
<tb>  <SEP> IV
<tb>  <SEP> ci-,(s- <SEP> et <SEP> t-cycloeitrals
<tb> 
 Les méthodes pouvant servir à préparer les dérivés du citral III seront évoquées ultérieurement.

 

   3) Les dérivés cyclogéraniques   II    de structure y- (avec X   =    O-alcoyle) peuvent être préparés par analogie avec
Helv. Chim. Acta 41, 1359 (1958) à partir des dérivés d'un a-carboxylate d'alcoyle de la cyclohexanone. Ces dérivés peuvent être condensés avec un halogénoacétate d'éthyle en présence de zinc pour donner un diester hydroxylé.



  Ce dernier peut alors être déshydraté, partiellement saponifié et mono-décarboxylé suivant le schéma C ci-dessous où les R' et les pointillés ont le sens expliqué plus haut.



  Schéma C
EMI3.2     


<tb>  <SEP> R'
<tb>  <SEP> R <SEP> Ha1C2-COOt <SEP> R <SEP> AX <SEP> COX
<tb>  <SEP> 2 <SEP>  >  <SEP> I <SEP> ISH
<tb> Ru <SEP> xi <SEP> Zn
<tb> R' <SEP> Zn
<tb>  <SEP> R' <SEP> R'
<tb>  <SEP> -H2O
<tb>  <SEP> 1) <SEP> -H20
<tb>  <SEP> 2 <SEP> ) <SEP> saponi <SEP> fi <SEP> c <SEP> at <SEP> ion
<tb>   
EMI4.1     


<tb>  <SEP> R' <SEP> R'
<tb> Rt <SEP> --- <SEP> COX <SEP> décarboxylation <SEP> R'
<tb> R' <SEP> Cox <SEP> décarboxylation
<tb> R'/
<tb>  <SEP> R' <SEP> R' <SEP> COOH
<tb>  <SEP> II- <SEP> r
<tb> 
 Les dérivés   cr-alcoxycarbonylés    de la cyclohexanone peuvent être préparés par exemple à partir de dérivés de la méthylheptanone V (voir schéma E ci-après, suivant Helv. Chim.

  Acta 35, 1753 (1952), et D) dans lesquels les R' ont le sens déjà décrit, ME représente une fonction métallique réactive et r désigne une réaction d'addition d'un réactif or   gano-métallique    sur une cétone [voir par exemple   D.J.    Cram et G.S. Hammond, Organic Chemistry, McGraw-Hill,
New York (1959) p.   294].    Ces schémas illustrent aussi une méthode de préparation des dérivés du citral III.



  Schéma D
EMI4.2     
  
Schéma E b: Réaction de Carroll (voir par exemple J. Chem. Soc. pp. 704, 1266 (1940), p. 507 (1941)).



  c: Diverses réactions de conversion des méthylhepténones en citrals correspondants (voir par exemple Bedoukian,
Perfumery and Flavoring Synthetics, Elsevier, New York (1967) p. 102-103).
EMI5.1     


<tb>



   <SEP> R <SEP> ' <SEP> R'
<tb> R' <SEP> OIi <SEP> R <SEP> Q <SEP> P- <SEP> *r"
<tb> CO <SEP> OE <SEP> t
<tb>  <SEP> COQEt <SEP> R'
<tb>  <SEP> R'
<tb>  <SEP> dérivés <SEP> de <SEP> la <SEP> méthyl
<tb>  <SEP> hepténone
<tb>  <SEP> 1C
<tb>  <SEP> fl <SEP> /
<tb>  <SEP> R'
<tb>  <SEP> R' <SEP> CITO
<tb>  <SEP> If <SEP> III
<tb>  <SEP> R <SEP> Iii
<tb> 
 4) Les dérivés safranylés utilisables dans le procédé de l'invention peuvent être obtenus simplement par une déshydrogénation des dérivés cyclogéranylés p-correspondants. ainsi:
Schéma F
EMI5.2     

 La déshydrogénation peut être effectuée suivant les méthodes destinées habituellement à former une double liaison conjuguée cyclique supplémentaire. Ainsi, la déshydrogénation peut être obtenue par une halogénation en position allylique, suivie d'une déshydrohalogénation.

 

  Comme agent d'halogénation on peut employer des composés halogénés connus pour leur action halogénante en position allylique. Parmi de tels agents on peut citer les amides halogénées, par exemple la N-bromosuccinimide, la N-bromoacétamide, la   N-diméthyldibromohydantoïne    et leurs analogues chlorés. Selon la pratique usuelle, on préfère employer la N-bromosuccinimide comme agent d'halogénation en position allylique (voir à ce sujet
Chem. Rev. 63, 21 (1963)). 



  
 



  Process for the preparation of carbonyl cycloolefinic compounds
The present invention relates to a process for the preparation of cycloolefinic ketones of formula:
EMI1.1
 in which the dotted lines represent either an endocyclic double bond in position 1- (structure) or 2 (structure a) or a double bond in exocyclic position (dry structure), or two conjugated double bonds and in which the symbols R and R 'constitute two classes of substituents in each of which said substituents represent either hydrogen, or one of them an alkyl and the others hydrogen.

  However, said substituents can not simultaneously represent all of the hydrogen unless the ring contains only one exocyclic double bond.



   It has been found that the compounds of formula I are endowed with particularly advantageous organoleptic properties and therefore are useful as perfuming agents in the perfume industry, as ingredients in the preparation of artificial flavors and as flavoring agents for flavoring. 'food, feed, drink, pharmaceutical preparations and tobacco.



   The new ketones can be used as scent ingredients in diluted or concentrated perfumes and in scented products such as soaps, Ia, = detergents, cosmetics, waxes and other products which can be scented and thus likely to become more interesting. from a business point of view.



  In addition, these compounds are very popular as ingredients used in the preparation of artificial essential oils, such as for example the 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.



   Ketones I also have very interesting flavoring properties. Depending on the nature of the products to which they are added, they develop fruity, vinous, woody, floral, waxy or aromatic plant aromatic notes, or any combination of said notes.



   The process for preparing the compounds I according to the invention is characterized in that an organometallic derivative of propene of the formula is acylated: ME-CR = CR-CH2R in which the symbols R have the meaning defined above and ME represents a reactive metallic function by means of a derivative of formula:
EMI2.1
 in which the dotted lines and the symbols R 'have the meaning defined above and in which X represents a group which can be cleaved under the conditions of the reaction.



  As metal function, it is possible to use, for example, lithium, zinc, cadmium or the Mg-halogen group and as acylating reagent a compound of formula II in which X represents, for example, a halogen residue, an O-alkyl group. , O-aryl, O-CO-alkyl or
O-CO-aryl.



   In the process defined above, use is preferably made as cyclogeranyl derivatives of geranoyl halides (for example chlorides and bromides) or geraniates (for example of methyl, ethyl or lithium).



   The cyclogeranic and saffron derivatives which can be used in the above process can be prepared according to methods, some examples of which are given below. Thus, 1) the cyclogeranic derivatives of structure IIa- and p- can be obtained from the corresponding cyclogeranic acids (a- or, 8-) by the usual means.

  The Q- and f; -cyclogéranic acids themselves can be obtained from the corresponding citral III derivatives according to known methods, for example by oxidation of said citral derivatives to geranic acids [see on this subject Gildmeister & Hoffmann, Die Àtherischen Ôle, IIId, pp. 137-138, Akademie-Verlag,
Berlin (1966)].



   The method of preparing derivatives II of structure Q- and p- can be illustrated by the following diagram A in which the symbols R ′ and the dotted lines have the meaning already explained above.



  Diagram A
EMI2.2


<tb> <SEP> R '<SEP> R' <SEP> R '
<tb> R <SEP> t <SEP> W <SEP> CHO <SEP> R <SEP> W <SEP> COOH <SEP> R <SEP> t <SEP> C <SEP> COOH
<tb> <SEP> OXYdtIO $, · Ç <SEP> cyclization
<tb> <SEP> R '
<tb> <SEP> R '<SEP> R' <SEP> R '
<tb> <SEP> III
<tb> <SEP> halogenation
<tb> <SEP> or <SEP> esterifidérives <SEP> from <SEP> derived <SEP> from <SEP> or <SEP> estérìfi
<tb> <SEP> citral <SEP> geranic acid <SEP>
<tb> <SEP> R '
<tb> <SEP> R'J <SEP> COX
<tb> <SEP> Cox
<tb> <SEP> II-a,
 2) The cyclogeranic derivatives II of structure Q-, p- and y- can also be obtained from the corresponding derivatives of citral (III) by cyclization into the corresponding a- and p- cyclocitrals [see for example Bedoukian,

   Perfumery and
Flavoring Synthetics, Elsevier, New York (1967)]. To obtain the y- structure, the isomerization of the p- cyclocitral is carried out. Then the aldehyde group of the cyclocitrals is oxidized to the -COOH group and finally the -COOH group is converted to the -COX group by the usual means. Diagram B below in which the R 'and the dotted lines have the meaning explained above illustrates this method.



  Diagram B
EMI3.1


<tb> <SEP> R '<SEP> 1
<tb> <SEP> R <SEP> '<SEP> RN
<tb> R <SEP> cyclization <SEP> R '<SEP> CHO <SEP> CHO
<tb> <SEP> R '<SEP> t
<tb> <SEP> IV- <SEP> 2 <SEP> lV
 <SEP> III
<tb> <SEP> o (-cyclocitrals <SEP> j-cyclocitrals
<tb> <SEP> isomerization
<tb> <SEP> R '
<tb> <SEP> I
<tb> <SEP> Rus
<tb> <SEP> IV-Y
<tb> <SEP> IV
<tb> <SEP> -cyc1oc <SEP> itral <SEP> s
<tb> <SEP> R '
<tb> <SEP> R <SEP> CHO <SEP> oxidation <SEP> R <SEP> '<SEP> tY <SEP> COOH
<tb> <SEP> R '
<tb> <SEP> R '
<tb> <SEP> R '
<tb> <SEP> IV
<tb> <SEP> ci -, (s- <SEP> and <SEP> t-cycloeitrals
<tb>
 The methods that can be used to prepare the citral III derivatives will be discussed later.

 

   3) Cyclogeranic derivatives II of structure y- (with X = O-alkyl) can be prepared by analogy with
Helv. Chim. Acta 41, 1359 (1958) from derivatives of an alkyl α-carboxylate of cyclohexanone. These derivatives can be condensed with an ethyl haloacetate in the presence of zinc to give a hydroxylated diester.



  The latter can then be dehydrated, partially saponified and mono-decarboxylated according to scheme C below where the R ′ and the dotted lines have the meaning explained above.



  Diagram C
EMI3.2


<tb> <SEP> R '
<tb> <SEP> R <SEP> Ha1C2-COOt <SEP> R <SEP> AX <SEP> COX
<tb> <SEP> 2 <SEP>> <SEP> I <SEP> ISH
<tb> Ru <SEP> xi <SEP> Zn
<tb> R '<SEP> Zn
<tb> <SEP> R '<SEP> R'
<tb> <SEP> -H2O
<tb> <SEP> 1) <SEP> -H20
<tb> <SEP> 2 <SEP>) <SEP> saponi <SEP> fi <SEP> c <SEP> at <SEP> ion
<tb>
EMI4.1


<tb> <SEP> R '<SEP> R'
<tb> Rt <SEP> --- <SEP> COX <SEP> decarboxylation <SEP> R '
<tb> R '<SEP> Cox <SEP> decarboxylation
<tb> R '/
<tb> <SEP> R '<SEP> R' <SEP> COOH
<tb> <SEP> II- <SEP> r
<tb>
 The cr-alkoxycarbonyl derivatives of cyclohexanone can be prepared for example from derivatives of methylheptanone V (see scheme E below, according to Helv. Chim.

  Acta 35, 1753 (1952), and D) in which the R 'have the meaning already described, ME represents a reactive metallic function and r denotes an addition reaction of an or gano-metallic reagent on a ketone [see by example DJ Cram and GS Hammond, Organic Chemistry, McGraw-Hill,
New York (1959) p. 294]. These schemes also illustrate a method of preparing the citral III derivatives.



  Diagram D
EMI4.2
  
Scheme E b: Carroll reaction (see for example J. Chem. Soc. Pp. 704, 1266 (1940), p. 507 (1941)).



  c: Various reactions for converting methylheptenones into corresponding citrals (see for example Bedoukian,
Perfumery and Flavoring Synthetics, Elsevier, New York (1967) p. 102-103).
EMI5.1


<tb>



   <SEP> R <SEP> '<SEP> R'
<tb> R '<SEP> OIi <SEP> R <SEP> Q <SEP> P- <SEP> * r "
<tb> CO <SEP> OE <SEP> t
<tb> <SEP> COQEt <SEP> R '
<tb> <SEP> R '
<tb> <SEP> derived <SEP> from <SEP> the <SEP> methyl
<tb> <SEP> heptenone
<tb> <SEP> 1C
<tb> <SEP> fl <SEP> /
<tb> <SEP> R '
<tb> <SEP> R '<SEP> CITO
<tb> <SEP> If <SEP> III
<tb> <SEP> R <SEP> Iii
<tb>
 4) The safranyl derivatives which can be used in the process of the invention can be obtained simply by dehydrogenation of the p-corresponding cyclogeranyl derivatives. so:
Diagram F
EMI5.2

 The dehydrogenation can be carried out according to the methods usually intended to form an additional conjugated cyclic double bond. Thus, dehydrogenation can be obtained by halogenation in the allylic position, followed by dehydrohalogenation.

 

  As halogenating agent, halogenated compounds known for their halogenating action in the allylic position can be employed. Among such agents, mention may be made of halogenated amides, for example N-bromosuccinimide, N-bromoacetamide, N-dimethyldibromohydantoin and their chlorinated analogues. According to usual practice, it is preferred to use N-bromosuccinimide as a halogenating agent in the allylic position (see on this subject
Chem. Rev. 63, 21 (1963)).

Claims (1)

REVENDICATION CLAIM Procédé pour la préparation de composés de formule: EMI5.3 dans laquelle les pointillés représentent soit une double liaison endocyclique en position 1- (structure ,8-) ou 2 (structure a-) soit une double liaison exocyclique (structure &gamma;-) soit deux doubles liaisons conjuguées, et dans laquelle les symboles R et R' constituent deux classes de substituants dans chacune desquelles lesdits substituants représentent soit l'hydrogène soit l'un d'entre eux un alcoyle et les autres l'hydrogène, étant cependant donné que lesdits substituants ne peuvent simultanément tous représenter l'hydrogène que lorsque le cycle contient une double liaison en position exocyclique, caractérisé en ce qu'on acyle un dérivé organo-métallique du propène de formule: Process for the preparation of compounds of the formula: EMI5.3 in which the dotted lines represent either an endocyclic double bond in position 1- (structure, 8-) or 2 (structure a-) or an exocyclic double bond (structure &gamma;-) or two conjugated double bonds, and in which the symbols R and R 'constitute two classes of substituents in each of which said substituents represent either hydrogen or one of them an alkyl and the others hydrogen, however since said substituents can not simultaneously all represent hydrogen only when the ring contains a double bond in the exocyclic position, characterized in that an organometallic derivative of propene of formula is acylated: : ME-CR=CR-CH2R dans laquelle les symboles R ont le sens défini ci-dessus et ME représente une fonction métallique réactive au moyen d'un dérivé de formule: EMI6.1 Il-Q > -ss,-&gamma; - > -# dans laquelle les pointillés et les symboles R' ont le sens défini ci-dessus et dans laquelle X représente un groupe scindable dans les conditions de la réaction. : ME-CR = CR-CH2R in which the symbols R have the meaning defined above and ME represents a reactive metallic function by means of a derivative of formula: EMI6.1 Il-Q> -ss, - &gamma; -> - # in which the dotted lines and the symbols R 'have the meaning defined above and in which X represents a group which can be cleaved under the conditions of the reaction. SOUS-REVENDICATION Procédé suivant la revendication, caractérisé en ce qu'on utilise comme composé organo-métallique le dérivé lithié du propène ou du propène méthylé en 1-, 2- ou 3- et comme composé acylant II un composé dans lequel X représente Cl > Br, I, O-éthyle ou O-méthyle. SUB-CLAIM Process according to claim, characterized in that the organometallic compound used is the lithiated derivative of propene or propene methylated in 1-, 2- or 3- and as acylating compound II a compound in which X represents Cl> Br, I, O-ethyl or O-methyl.
CH1805570A 1969-05-07 1969-05-07 Unsaturated cycloaliphatic ketones CH513098A (en)

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CH1805570A CH513098A (en) 1969-05-07 1969-05-07 Unsaturated cycloaliphatic ketones
CH697669A CH520767A (en) 1969-05-07 1969-05-07 Unsaturated cycloaliphatic ketones

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CH1804970A CH528225A (en) 1969-05-07 1969-05-07 Unsaturated cycloaliphatic ketones
CH1805070A CH521099A (en) 1969-05-07 1969-05-07 Unsaturated cycloaliphatic ketones
CH1805370A CH513094A (en) 1969-05-07 1969-05-07 Unsaturated cycloaliphatic ketones
CH1805470A CH521298A (en) 1969-05-07 1969-05-07 Unsaturated cycloaliphatic ketones
CH697669A CH520767A (en) 1967-11-09 1969-05-07 Unsaturated cycloaliphatic ketones
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CH1805070A CH521099A (en) 1969-05-07 1969-05-07 Unsaturated cycloaliphatic ketones
CH1805370A CH513094A (en) 1969-05-07 1969-05-07 Unsaturated cycloaliphatic ketones
CH1805470A CH521298A (en) 1969-05-07 1969-05-07 Unsaturated cycloaliphatic ketones
CH697669A CH520767A (en) 1967-11-09 1969-05-07 Unsaturated cycloaliphatic ketones
CH1805270A CH513097A (en) 1969-05-07 1969-05-07 Unsaturated cycloaliphatic ketones

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CH521099A (en) 1972-04-15
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