CH603071A5 - Di:methyl-cyclohexene-alkenone cpds. - Google Patents

Di:methyl-cyclohexene-alkenone cpds.

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Publication number
CH603071A5
CH603071A5 CH120975A CH120975A CH603071A5 CH 603071 A5 CH603071 A5 CH 603071A5 CH 120975 A CH120975 A CH 120975A CH 120975 A CH120975 A CH 120975A CH 603071 A5 CH603071 A5 CH 603071A5
Authority
CH
Switzerland
Prior art keywords
dimethylcyclohex
pent
ene
mixture
nmr
Prior art date
Application number
CH120975A
Other languages
French (fr)
Inventor
Karl-Heinrich Dr Schulte-Elte
Bruno Dr Willhalm
Fritz Dr Gautschi
Original Assignee
Firmenich & Cie
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Publication date
Application filed by Firmenich & Cie filed Critical Firmenich & Cie
Priority to CH120975A priority Critical patent/CH603071A5/en
Publication of CH603071A5 publication Critical patent/CH603071A5/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
    • C11B9/0026—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
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    • 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
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    • 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
    • C07C403/02—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 containing only carbon and hydrogen atoms
    • 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
    • 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
    • C07C403/12—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 esterified hydroxy groups
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    • 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
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    • C07—ORGANIC CHEMISTRY
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
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    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
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    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/515—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an acetalised, ketalised hemi-acetalised, or hemi-ketalised hydroxyl group
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    • C07—ORGANIC CHEMISTRY
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    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
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    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
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    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
    • C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
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    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/385—Saturated compounds containing a keto group being part of a ring
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    • 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)
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  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Perfuming and aromatising compsns. are claimed contg. as active ingredient a cpd. of formula (I) in which the ring may be satd., or have a double bond in posns. 1,4 or 6. or two double bonds in posns. 1 and 4, 1 and 5 or 4 and 6, n is 0, 1 or 2; Z may be bound to posns. 1 or 6 and is a gp. CO, COR8 or C(OR9)2, in which R8 is 1-6C acyl gp. and R9 is 1-6C alkyl or 2-6C alkylene gp.; Y is O or CH2; R1-5 are H or one of R1-5 is CH3 and the remainder are H; and R6 and R7 are 1-3C alkyl.In an exceptional case, cpd. (I) has a double bond in posn. 1 or 6, Z is O and is bound to posn. 1, Y is CH2, n is 1, R1-5 are H and R6 and R7 are CH3.(I) impart a green, fruity, woody, note to perfume and aromatising compsns. and are used e.g. at 0.01-5%, esp. 0.01-2% in compsns. used to impart or to build the fragrance of food, drinks, tobacco, cosmetics, detergents, soap, etc.

Description

  

  
 



   Le brevet suisse   N"    586551 a pour objet une composition parfumante contenant en tant qu'ingrédient actif un composé oxygéné alicyclique de formule:
EMI1.1     
 possédant une double liaison cyclique dans l'une des positions indiquées par les pointillés.



   La formule ci-dessus englobe plus précisément la 1-(3,3-di   méthylcyclohex-l-ène- l-yl)pent-4-ène-l -one    et la l-(3,3-diméthyl   cyclohex-6-ène-1-yl)pent-4-ène-1-one.      I1    a été trouvé que de nombreux composés homologues ou analogues à ceux décrits plus haut possédaient également d'intéressantes propriétés organoleptiques et qu'ils pouvaient être de ce fait tout aussi avantageusement utilisés à titre d'ingrédients parfumants et/ou aromatisants.



   La présente invention a par conséquent pour objet une composition parfumante ou aromatisante contenant en tant qu'ingrédient actif au moins un des composés oxygénés alicycliques de formule:
EMI1.2     
 possédant un cycle à six membres saturé, ou possédant une double liaison en position 1, 4 ou 6, ou encore deux doubles liaisons en positions 1 et 4, 1 et 5, ou 4 et 6 du cycle comme indiqué par les pointillés, et dans laquelle:

  :
   - Pindice    n vaut 0, 1 ou 2;
 - le symbole Z, fixé en position I ou 6 comme indiqué par les pointillés, représente un groupe CO, COR8 ou C(OR9)2 dans lesquels le symbole R8 représente un reste acyle contenant de 1 à 6 atomes de carbone et R9 représente un reste alkyle ou alkylène contenant de 1, respectivement 2, à 6 atomes de carbone;
 - le symbole Y représente un atome d'oxygène ou un groupe
CH2;

  ;
 - chacun des symboles   Rl,    R2, R3, R4 et R5 représente un atome d'hydrogène ou run d'entre eux représente un groupe CH3 et les autres un atome d'hydrogène, et chacun des symboles R6 et   R'    représente un reste alkyle contenant de 1 à 3 atomes de carbone, exception faite du cas où ledit composé I possède une double liaison en position 1 ou 6, le symbole Z, relié en position 1, représente un atome d'oxygène, Y représente un groupe   CH2,rindice    n vaut 1, chacun des symboles   Rl,    R2, R3,
R4 et R5 représente un atome d'hydrogène et chacun des symboles
R6 et   R'    représente un groupe méthyle.



   La présente invention a en outre pour objet rutilisation de ladite composition parfumante ou aromatisante pour la préparation de parfums et produits parfumés ou, respectivement, pour raromatisation d'aliments, boissons ou tabac.



   Dans le domaine des arômes par exemple, les composés I se distinguent par leur note fruitée et tout à la fois boisée, verte et huileuse, ce dernier caractère rappelant par certains côtés la note verte et huileuse du galbanum ou du genièvre par exemple.



   Il a été découvert en outre que les composés I présentaient également d'intéressantes propriétés olfactives et qu'ils trouvaient de ce fait un emploi fort avantageux dans   l'art    de la parfumerie.



  Les composés I se caractérisent en effet par leur odeur originale, puissante, dont la note verte, herbacée rappelle notamment celle de l'essence ou du   résinoîde    de galbanum par exemple. Cette odeur particulière se marie fort bien avec celle de nombreuses compositions de type floral, boisé, vert, herbacé, chypre ou même animal.



  Les composés I ont en outre pour effet, dans la plupart des cas, de renforcer ou développer, au sein des compositions auxquelles ils sont incorporés, une note verte, montante, d'une grande distinction.



   Les composés I sont également très appréciés pour la reconstitution d'huiles essentielles diverses et pour la préparation de produits parfumés tels que savons, détergents, produits d'entretien ou produits cosmétiques par exemple.



   Les proportions utilisées afin d'obtenir un effet odoriférant tel que celui décrit ci-dessus, peuvent varier de façon étendue.



   Lors de la préparation de compositions parfumantes par exemple, des effets intéressants peuvent être obtenus par l'emploi de proportions comprises entre 0,01 et 5% du poids de ladite composition. Les composés I s'utilisent de préférence à raison de 0,01 à 2% environ. Etant donné leur odeur particulièrement puissante, lesdits composés exercent déjà un effet significatif à des concentrations relativement faibles, voisines de la limite inférieure donnée ci-dessus.



   Il demeure entendu que des quantités supérieures ou inférieures à celles mentionnées plus haut peuvent être également envisagées, notamment lorsque   l'on    désire obtenir un effet organoleptique particulier.



   Parmi les composés de formule I que   l'on    peut utiliser selon la présente invention, il convient de citer les composés ci-après: 1-(3,3-diméthylcyclohexyl)pent-4-ène-1-one; 1-(3,3-diméthylcyclohexa-4,6-diène-1-yl)pent-4-ène-1-one; 1-(3,3-diméthylcyclohexa-1,5-diène-1-yl)pent-4-ène-1-one; 1-(3,3-diméthylcyclohex-4-ène-1-yl)pent-4-ène-1-one :

   acétate de   l-(3,3-diméthylcyclohex- l-ène-l -yl)pent-4-ène- 1 -yle;    formiate de 1 -(3,3-diméthylcyclohex-   1 -éne-l    -yl)pent-4-ène- l-yle;    l-(3,3-diméthylcyclohex-l-ène-l-yl)-l ,l-éthylènedioxypent-4-ène;    acétate de   I -(3,3-diméthylcyclohex-6-ène- 1 -yl)pent-4-ène- I-yle;    formiate de 1   -(3,3-diméthylcyclohex-6-ène-      i -yl)pent-4-ène-    l-yle;   I -(3,3-diméthylcyclohex-6-ène-1    -yl)-   1,1 -éthylènedioxypent-4-êne;      l-(3,3-diméthylcyclohexa-l ,4-diène- 1 -yl)pent-4-ène- 1 -one;    1-(3,3-diméthylcyclohex-6-ène-1-yl)hex-5-ène-1-one; 1-(3,3-diméthylcyclohex-1-ène-1-yl)hex-4-ène-1-one;

   1-(3,3-diméthylcyclohex-6-ène-1-yl)hex-4-ène-1-one;   
I -(3,3-diméthylcyclohex-6-ène- 1 -yl)-3-méthylpent-4-ene- 1 -one; 1-(3,3-diméthylcyclohex- 1 -ène-l -yl)-3-méthylpent-4-ène-l-one;      1-(4,4-diméthylcyclohex-      I-éne-      l-yl)pent-4-ène-    I-one; 1-(3,3,4-triméthylcyclohex-6-ène-1-yl)pent-4-ène-1-one;

   1-(3,3,5-triméthylcyclohex-6-ène-1-yl)pent-4-ène-1-one;   I -(3,3,5-triméthylcyclohex- 1 -ène- I -yl)pent-4-ène- 1 -one;      I -(3,3,5-triméthylcyclohexa-4,6-diène- 1 -yl)pent-4-ène- 1    -one:   l-(3,3-diméthylcyclohex-6-ène-l -yl)but-3-ène-l-one;      l-(3,3-dimèthylcyclohex-6-ène-i-yl)-3-méthylbut-3-ène-    1-one;   I -(3,3-diméthylcyclohex-6-ène- 1 -yl)-2-méthylbut-3-ène- 1 -one;    3,3-diméthylcyclohex-6-ène- 1 -ylcarboxylate de prop-2-ène- 1 -yle;   I -(3,5-diméthylcyclohex-6-ène- 1 -yl)pent-4-ène- 1 -one;    1-(cis-3,4-diméthylcyclohex-6-ène-1-yl)pent-4-ène-1-one; 

   1   -(trans-3,4-diméthylcyclohex-6-ène-      1 -yl)pent-4-ène- 1    -one, et 1   -(trans-3,4-diméthylcyclohex-1    -ène- 1 -yl)pent-4-ène- 1 -one.  



   Les composés ci-dessus, de même que la 1-(3,3-diméthylcyclohex-6-ène-1-yl)pent-4-ène-1-one et la   1-(3,3-diméthylcyclohex-1-ène-      1-yl)pent-4-ène-1-one,    ont été obtenus au moyen de   l'un    des procédés décrits ci-après:
Schéma   1:   
EMI2.1     
 et ss-déhydrolinalol
EMI2.2     
  
Schéma II
EMI3.1     
  
Schéma III:
EMI4.1     

On a ainsi préparé la 1-(3,3-diméthylcyclohex-1-ène-1-yl)-pent-4-ène-1-one et la 1-(3,3-diméthylcyclohex-6-ène-1-yl)pent-4-ène-1-one  
Schéma IV:
EMI5.1     

 Les composés suivants ont été préparés selon le procédé ci-dessus: 1-(3,3-diméthylcyclohexyl)pent-4-ène-1-one; 1-(3,3-diméthylcyclohex-4-ène-1-yl)pent-4-ène-1-ène; 1 -(3,3-diméthylcyclohex-6-ène   1-yl)pent-4ène 1    -one, et 1-(3,3-diméthylcyclohex-1-ène-1-yl)pent-4-ène-1-one.  



  Schéma V:
EMI6.1     

 On a ainsi préparé les composés suivants: 1-(3,3-diméthylcyclohexa-1,4-diène-1-yl)pent-4-ène-1-one; 1   -(3,3-diméthylcyclohexa-4,6-diène-1    -yl)pent-4-ène- 1 -one, et
I -(3,3-diméthylcyclohexa- 1 ,5-diène- 1   -yl)pent-4-ène. 1    -one.  



  Schéma VI:
EMI7.1     

EMI7.2     

 On a ainsi préparé les composés ci-après:   3,3-diméthylcyclohex-6-ène-1-ylcarboxylate    de   prop-2-ène- 1-yle;    1-(3,3-diméthylcyclohex-6-ène-1-yl)hex-5-ène-1-one;    1-(3,3-diméthyleyclohex-6-ène-1 -yl)-3-méthylbut-3-ène-1-one;      1-(3,3-diméthylcyclohex-6-ène-1-yl)-2-méthylbut-3-ène-1-one,    et 1-(3,3-diméthylcyclohex-6-ène-1-yl)but-3-ène-1-one.
EMI7.3     




   Les composés suivants ont été préparés selon le procédé ci-dessus: acétate de 1-(3,3-diméthylcyclohex-1-ène-1-yl)pent-4-ène-1-yle; formiate de 1-(3,3-diméthylcyclohex-1-ène-1-yl)pent-4-ène-1-yle;   1-(3,3-diméthylcyclohex- 1 -ène-1 -yl)- 1,1 -éthylènedioxypent-4-ène;    acétate de   1-(3,3-diméthylcyclohex-6.    ène-l -yl)pent-4-ène- 1 -yle; formiate de 1-(3,3-diméthylcyclohex-6-ène-1-yl)pent-4-ène-1-yle, et 1-(3,3-diméthylcyclohex-6-ène-1-yl)-1,1-éthylènedioxypent-4-ène.  



  Schéma VIII:
EMI8.1     

EMI8.2     

   1 voir     J. Org. Chem. , 23, 1507 (1958).



    J. Org. Chem. , 37, 1020 (1972).



   C'est ainsi qu'on a préparé la 1-(4,4-diméthylcyclohex-1-ène-   1 -yl)pent-4-ène- 1 -one.   



  Schéma IX:
EMI8.3     
  
Schéma   X:   
EMI9.1     

 (coir schéma IV)
 Les composés suivants ont été ainsi obtenus: 1-(3,3-diméthylcyclohex-6-ène-1-yl)hex-4-ène-1-one; 1-(3,3-diméthylcyclohex-1-ène-1-yl)hex-4-ène-1-one; 1-(3,3-diméthylcyclohex-6-ène-1-yl)-3-méthylpent-4-ène-1-one, et 1-(3,3-diméthylcyclohex-   1 -ène-l      -yl)-3-méthylpent-4-ène-1    -one.



   Le produit de départ utilisé ci-dessus peut être obtenu comme suit:
EMI9.2     

 déhydrolinalol
Schéma XI:
EMI9.3     
  
EMI10.1     

Les composés suivants ont été obtenus selon le procédé ci-après:
 1-(3,3,5-triméthylcyclohexa-1,5-diène-1-yl)pent-ène-1-one, et
 1-(3,3,5-triméthylcyclohexa-4,6-diène-1-yl)pent-4-ène-1-one.
EMI10.2     




   On a préparé ainsi les composés suivants: 1-(3,5-diméthylcyclohex-6-ène-1-yl)pent-4-ène-1-one; 1-(cis-3,4-diméthylcyclohex-6-ène-1-yl)pent-4-ène-1-one; 1 -(trans-3,4-diméthylcyclohex-6-ène- 1 -yl)pent-4-ène-1 -one, et 1   -(trans-3,4-diméthylcyclohex-      1-éne- 1    -yl)pent-4-ène-1-one.



   La synthèse des composés I susnommés est décrite ci-après de façon plus détaillée. Dans le texte ci-dessous, les températures sont indiquées en degrés centigrades et les abréviations possèdent le sens usuel dans l'art.



      1-(3,3-Diméthylcyclohex-6-ène-1-yl)pent4-ène-1-one et   
 1-(3,3-diméthylcyclohex-1-ène-1-yl)pent-4-ène-1-one
 (schéma I).



   a) 100 g   d'α-déhydrolinalol   ont été chauffés à   70-75     sous 12 torrs, en présence de 30 g d'acide borique, jusqu'à la disparition de la formation de H2O. La température du bain a ensuite été lentement portée à   160-170     et on a ainsi recueilli, avec un rendement de 47%, un mélange de 3-méthylène-7-méthyloct   I-yne-7-ène    et de 3,7   diméthyloct-1-yne-3,7-diène.    En utilisant par contre le   P-déhydrolinalol,    on isole ledit mélange avec un rendement de 66%. Le mélange ci-dessus peut être séparé en ses constituants par distillation fractionnée ou par chromatographie en phase gazeuse (c.p.g.) préparative (Carbowax - 5 m -   130 ).   



   b) 2 g du mélange ci-dessus dissous dans 5 ml d'isopropanol ont été ajoutés goutte à goutte à un mélange refroidi de 1,1 g de
KOH, 0,15 g de K2CO3 et 0,1 g de CuCI dans 5   ml    de méthanol.



  30 mn après addition des réactifs, on a encore ajouté 1,5 g de chlorure d'allyle, puis on a laissé reposer le mélange durant la nuit.



  Le mélange réactionnel, dilué avec H2O. a ensuite été extrait à l'éther de pétrole et la phase organique lavée, séchée et évaporée  selon les techniques usuelles, et le résidu finalement distillé dans un tube à boules. On a ainsi recueilli un produit contenant environ 80% d'un mélange de 6-méthylène-10-mèthylundéca-1,10-   diène-4-yne    et 6-méthylène-10-méthylundéca-1,9-diène-4-yne et environ 20% d'un mélange de 6,10-diméthylundéca-1,6,10-triène- 4-yne et 6,10-diméthylundéca-1,6,9-triène-4-yne.



   c) 100 g du mélange obtenu ci-dessus ont été chauffés à   90-100     en présence de 200   ml    d'acide formique à 80%. Après la disparition des deux tiers du produit de départ (environ 90 mn), le mélange réactionnel, dilué avec H20, a été extrait à   éther    de pétrole et traité comme indiqué précédemment. La distillation du résidu a donné 77 g d'un mélange de   1-(3,3-diméthylcyclohex-1-    ène-1-yl)pent-4-ène-1-yne et 1-(3,3-diméthylcyclohex-6-ène-1-yl)   pent-4éne-1-yne.    Les deux composés ont été isolés à rétat pur par c.p.g. préparative.



   d) 3 g du mélange oléfinique obtenu ci-dessus ont été chauffés durant 150 mn à   90 ,    en présence d'acide formique à 80%. Après refroidissement, le mélange réactionnel, dilué avec H20, a été traité comme précédemment pour donner finalement 2,8 g d'un produit ayant Eb.   65-75V2    torrs et contenant 75% d'un mélange 2:3 de 1 -(3,3-diméthylcyclohex-1 -ène-1 -yl)pent-4-ène-1 -one (A) et   1-(3,3-diméthylcyclohex-6-ène-1-yl)pent-4-ène-1-one    (B) respectivement.



  (A) :n20 = 1,4891; d20 = 0,9247;
IR :3080, 1820,1675,1640,990,910cm-Ú;
RMN: 1,06 (6H, 2s); 4,73-6,00 (3H, m); 6,40 (1H, m)   #    ppm;
SM:   M+=192 (13);    m/e: 177 (6), 137 (100), 109 (85), 93 (12),
 81 (32), 67 (55), 55 (58), 41 (45).



  (B):   nD0=      1,4879;    d20 = 0,9262;
IR : 3080,1680,1640,990,910,820 cm-Ú;
RMN: 0,88 (6H, 2s); 1,32 (2H, t,   J=7    Hz); 4,75-6,20 (3H, m);
 6,73 (1H, m) 6 ppm;
SM:   M+=192 (7); m/e:    177(5), 164(3), 149 (2), 137 (100),
 121(6), 109 (45), 93 (6), 81(13), 67 (33), 55 (28), 41(16).



     1-(3,3-Diméthylcyclohex-6-ène-1-yl)pent-4-ène-1-one    et
 1-(3,3-diméthylcyclohex-1-ène-1-yl)pent-4-ène-1-one
 (schéma   II).   



   a) 27 g de triphénylphosphine et 15 g de 5-bromopent-1-ène dans 100   ml    de xylène ont été chauffés à reflux pendant 40 h.



  Après refroidissement à 0.5  et filtration, on a isolé 33 g (100%) du bromure de phosphonium désiré, F. = 188-190 .



   b) 8 g d'une solution à 14% de butyllithium dans   éther    ont été ajoutés en 15 mn, sous azote, à 7 g du sel de phosphonium en suspension dans 80   ml    d'éther. Au mélange réactionnel refroidi à   5-10 ,    on a ensuite ajouté 2,1 g de 3,3-diméthylcyclohex-5-ène-1one dans 10   ml    d'éther. Le mélange ci-dessus a encore été agité durant 3 h, puis filtré, lavé avec H2O jusqu'à neutralité, évaporé et finalement distillé pour donner 1,5 g (50%) de 1-(3,3-diméthylcyclohex-5-éne-1-ylidène)pent-4-ène.



   c) 1,5 g du composé ci-dessus ont été époxydés au moyen de 2 g d'acide peracétique à 40%, en présence de 1 g d'acétate de sodium et 20   ml    de   CH2Cl2.    3 h après addition des réactifs, le mélange dilué avec H2O a été traité comme ci-dessus pour donner, après distillation, 1,3 g d'un composé époxydé de formule
EMI11.1     

 Le composé ci-dessus a ensuite été chauffé durant 8 h à   1000,    en présence de 0,5 g de terre de diatomées acide dans 10   ml    de dioxanne, pour donner, après distillation fractionnée du mélange réactionnel, 1,1 g d'un produit contenant 30% de 1-(3,3-diméthylchclohex-6-ène-1-yl)pent-4-ène-1-one selon l'analyse par c.p.g.



   a') On a premièrement procédé à l'hydrogénation de la 3,3-diméthylcyclohex-5-ène-1-one en présence de palladium sur charbon.



  La 3,3-diméthylcyclohexanone ainsi obtenue a ensuite été traitée au moyen d'acétylène en milieu basique pour donner, avec un rendement de 50%, le 1-éthynyl-1-bydroxy-3,3-diméthylcyclohexune.



   b') 4,2 g de chlorure d'allyle dans 5 mi de méthanol ont été ajoutés, à 0-10 , à un mélange de 3,2 g de KOH, 0,5 g de
K2CO3 et 0,3 g de Cu2Cl2 dans 20 ml de méthanol. Le mélange réactionnel a ensuite été porté à 40-50  et agité durant une nuit.



  Après dilution avec H20, extraction à   éther    de pétrole et traitement de la phase organique comme indiqué précédemment, on a isolé 7,5 g (90%) de 1-(1-hydroxy-3,3-diméthylcyclohexyl)pent-4- ène-l-yne.



  n = 1.4899; d20 = 0.9354;
IR : 3450,3080,2235,1640,990,910 cm-Ú
 c') 7 g du produit ci-dessus ont été chauffés dans un appareil à distiller sous 12 torrs, en présence de 2 g d'acide borique, jusqu'à disparition de formation de H2O. La température a ensuite été portée à 120-1300 et   l'on    a recueilli 5,3 g (70%) d'un mélange 2:3 de   1-(3,3-diméthylcyclohex-      1-ène-1-yl)pent-4-ène-1    -yne et 1-(3,3-diméthylcyclohex-6-ène-   i -yi)pent-4-ène-1    -yne. La conversion desdits composés en cétones correspondantes s'est effectuée comme indiqué plus haut - schéma I; lettre d.



   d') L'alcool insaturé obtenu sous lettre b' a été transformé en cétone correspondante par traitement de 3 g dudit carbinol au moyen de 30   ml    d'acide formique à 80%, durant 2 h à reflux.



  Après les traitements usuels d'extraction, lavage et distillation, on a obtenu 1,8 g d'un mélange 1:2 de 1-(3,3-diméthylcyclohex-1ène-1-yl)pent-4-ène-1-one et 1-(3,3-diméthylcyclohex-6-ène-1-yl)pent-4-ène-1-one. La   3,3-diméthylcyclohex-5-ène-1-one    utilisée cidessus comme produit de départ peut être obtenue selon la méthode décrite dans  J. Org. Chem. , 38, 3637 (1973).



     1-(3,3-Diméthylcyclohex-6-ène-1-yl)pent-4-ène-1-one    et
 1-(3,3-diméthylcyclohex-1-ène-1-yl)pent-4-ène-1-one
 (schéma III).



   a) 467 g de méthylvinylcétone et 480 g   d'isobutyraldéhyde    dissous dans un mélange de 700   ml    d'eau et 350   ml    de méthanol ont été ajoutés en 3 h, sous azote, à un mélange maintenu à 60-70  de 25 g de KOH, 150   ml    de méthanol et 1000   ml    d'eau.



  Après avoir été chauffé durant   I    h à 70  et refroidi à   25 ,    le mélange, dilué avec H2O, a été extrait à l'éther de pétrole et finalement traité comme indiqué précédemment pour donner 325 g (40%) de 4,4-diméthylcyclohex-2-ène-1-one, Eb. 73-76 /15 torrs.



   b) 124 g du composé ci-dessus ont été hydrogénés en présence de 2 g de nickel de Raney dans 300   ml    d'isopropanol pour donner finalement 120 g de 4,4-diméthylcyclohexanone.



   c) 26 g du composé ci-dessus, dissous dans 200   ml    d'éther, ont été ajoutés en 45 mn, à   0 ,    à un mélange de 22 g de méthylate de sodium, 30 g de formiate d'éthyle et 100   ml    d'éther. Le mélange réactionnel a ensuite été agité durant une nuit à température ambiante, puis additionné de 600   ml    d'eau maintenue à   0     et finalement acidifié au moyen de   HCl à    30%. Après extraction à   éther    de pétrole et traitement de la phase organique comme indiqué plus haut, on a isolé 26 g d'un composé de formule:
EMI11.2     

Eb.   29-33 /0,01    torr, rendement 75%. 

  Après traitement à 68  durant 3-5 mn de 15 g dudit composé au moyen de 10,5 g d'orthoformiate d'éthyle, en présence de 0,1 g d'acide p-toluènesulfonique dans 20   ml    de méthanol, et extraction du mélange  réactionnel à   éther    de pétrole, on a isolé 17 g d'un mélange de composés de formules:
EMI12.1     

EMI12.2     

 Le mélange ci-dessus a été utilisé pour l'étape réactionnelle suivante sans autre purification.



   d) 6,0 g du mélange ci-dessus, dissous dans 20   ml    d'éther, ont été ajoutés sous azote à 0,8 g de LiAIII4 en suspension dans 30   ml    d'éther et finalement agités durant une nuit. Après addition de H2O, extraction à l'éther de pétrole, lavage, séchage et distillation comme indiqué plus haut, on a isolé 6,8 g de matériel impur. Après chauffage à reflux durant 90 mn en présence de 0,3 g d'acide p-toluènesulfonique et distillation, on a finalement obtenu 4,8 g d'un produit contenant 78% de 1-formyl-3,3-diméthylcyclohex-6-   ène.   



   e) 1,5 g du composé ci-dessus dans 20   ml    d'éther ont été ajoutés à une solution préparée à partir de 1,3 g de CH3I, 1,25 g de
Mg en tournures et 50   ml    d'éther. Après avoir été agité durant 2 h, le mélange a été versé sur glace, puis extrait et finalement distillé pour donner 1,43 g de 1-(3,3-diméthylcyclohex-6-ène-1-yl)-1- hydroxyéthane.



  IR : 34000 cm-Ú;
RMN: 0,91 (6H, 2s); 1,18 (3H, J=6Hz); 4,06 (1H, m); 5,53 (1H, m)   
 Gppm;
SM: M+ = 154 (21), m/e: 139(6), 121(16), 85 (26),69 (20),43 (100).   



   f) 1,2 g du composé ci-dessus ont été traités, sous azote et à   25 ,    au moyen de 20 g de MnO2 dans 50   ml    d'éther de pétrole.



  36 h après addition des réactifs, filtration et distillation fractionnée du mélange réactionnel, on a isolé 1,08 g (85%) de (3,3-diméthylcyclohex-6-ène-1 -yl)méthylcétone.



  nD= 1,4809;   d420=0,9309;   
IR: 1670,   1640cm1.   



   g) 10 g du composé ci-dessus ont été ajoutés à 0  à un mélange obtenu à partir de 5 g d'une solution de butyllithium à 12% dans
Phexame, 7,3 g d'isopropylamine et 70   mi d'éther.    1 h après addition des réactifs, on a encore ajouté 8,8 g de bromure d'allyle et laissé reposer durant la nuit. Après addition de H2O et traitement du mélange réactionnel comme indiqué plus haut, on a isolé 6 g d'un produit contenant 20% de 1-(3,3-diméthylcyclohex-6-ène-1-yl)-   pent-4-éne-t-one.    Ce composé a été obtenu à rétat pur par c.p.g.



  préparative.



   g') 5 g d'une solution de butyllithium à 12% dans l'hexane et 100   ml    d'éther ont été ajoutés, à 00, à 73 g d'isopropylamine dissous dans 70   ml    d'éther. 10 g de (3,3-diméthylcyclohex-1-ène-1-yl)- méthylcétone ont ensuite été ajoutés, en 1 h et à   0 ,    au mélange ci-dessus et finalement 8,8 g de bromure d'allyle. Après les traitements décrits ci-dessus, on a recueilli 5,9 g d'un mélange contenant 40% de   1-(3,3-diméthylcyclohex- 1-éne- 1.yl)pent.4.ène. 1 -one,    finalement isolée à   l'état    pur par c.p.g. préparative.



   La (3,3-diméthylcyclohex-1-ène-1-yl)méthylcétone, utilisée ci-dessus comme produit de départ, a été obtenue selon la méthode donnée dans  Z. Chem. , 9, 64 (1969).



     1 -(3 ,3-Diméthylcyclohex-6-ène-1 -yl)pent-4-ène-1    -one;
 1-(3,3-diméthyljcycllohex-1-ène-1-yl)pent-4-ène-1-one;
 1-(3,3-diméthyljcyclohex-4-ène-1-yl)pent-4-ène-1-one, et
 1-(3,3-diméthylcyclohexyl)pent-4-ène-1-one (schéma IV).



   a) On a premièrement procédé à l'ozonolyse du   A3-carène    dans le méthanol, selon la méthode décrite dans  Ber. , 60, 1591 (1927), pour obtenir un composé de formule:
EMI12.3     

 Le composé obtenu ci-dessus, dilué dans 10 fois son volume de méthanol, a ensuite été chauffé à reflux en présence de quelques gouttes de KOH à 25%. Après 90 mn de chauffage, dilution avec
H2O, extraction à l'éther et traitement comme indiqué plus haut, on a isolé la (3,3-diméthylcyclohexa-1,4-diène-1-yl)méthylcétone avec un rendement de 65%. Eb. 27-30 .



  nD = 1,4886 ; d20 = 0,9493 ;
IR : 1670,1630,1560,720 cm-Ú;
UV (EtOH):   # :    220, 240 et 310 nm.



   b) 15 g du composé ci-dessus ont été hydrogénés en présence de palladium sur charbon pour donner un mélange   31:35:17:17    des composés ci-après:
EMI12.4     
 respectivement. Ces quatre composés cétoniques ont été isolés à l'état pur par c.p.g. préparative.



   c) Par traitement du mélange ci-dessus au moyen de bromure d'allyle et d'isopropylamine - voir schéma   II;    lettre h - et séparation du mélange réactionnel par c.p.g. préparative, on a isolé les composés ci-après:
 1-(3,3-diméthylcyclohexyl)pent-4-ène-1-one.



  nD= 1,4749;   d20=0,9226;   
IR : 3080,1706,1640,990 et 910 cm-Ú;
RMN: 0,9 (6H, 2s); 4,72-6,1 (3H,   m) 6    ppm;
SM: M+=194(3);m/e: 179(2), 139(27), 117(60), 111(100),
 69 (92), 55 (85), 41(40).



   1-(3,3-diméthylcyclohex-4-ène-1-yl)pent-4-ène-1-one.



  nD= 1,4788; d20 = 0,9212:
IR : 3080,1710,1645,990,910 et 722 cm-1;
RMN: 1,02 (6H, 2s); 4,76-6,1 (3H, m); 5,41 (2H,   m) 6    ppm;
SM : M+ = 192 (5) :m/e : 177 (7), 109 (45), 83(82), 67 (44), 55 (100),
 41(55); ainsi que la 1-(3,3)diméthylcyclohex-1-ène-1-yl)pent-4-éne-1-one et la 1-(3,3-diméthylcyclohex-6-ène-1-yl)pent-4-ène-1-one.



   1-(3,3-Diméthylcyclohexa-1,4-diène-1-yl)pent-4-ène-1-one;
   1-(3,3-Diméthylcyclohexa-4,6-diène-1-yl)pent-4-ène-1-one,    et
 1-(3,3-diméthylcyclohexa-1,5-diène-1-yl)pent-4-ène-1-one
 (schéma V).



   a) 52 g de méthylate de sodium ont été ajoutés à   0-5     à 71 g de formiate d'éthyle dans 700   ml    d'éther. 20 mn après addition des réactifs, on a ensuite ajouté 60 g de 4,4-diméthylcyclohex-2ène-l-one et finalement maintenu le mélange réactionnel durant une nuit à 250, avant de le verser sur glace. Après les traitements usuels d'extraction, lavage, séchage et distillation on a recueilli 63,1 g d'un composé de formule:
EMI12.5     
 ayant Eb. 40.45 /0,1 torr rendement 87%).



  nD= 1.5231 ; d20 = 1,036.  



   b) le composé ci-dessus a ensuite été converti en dérivés monoet diméthoxylés respectivement, selon le procédé du schéma III lettre c.



  Monométhoxycétone : nD= 1,5167; d20 = 1,035:
IR : 1680, 1625,1590 cm-Ú.



  Diméthoxycétone: nD= 1,4821 ; d20 = 1,033 :
IR:   1680,770, 710cm1.   



   c) 26 g d'un mélange 7:3 des composés respectivement monoet   diméthoxylés    obtenus ci-dessus, dissous dans 50   ml    d'éther, ont été ajoutés sous azote à 5,5 g de LiAiH4 en suspension dans 200   ml    d'éther, pour donner finalement 18,3 g d'un mélange des carbinols correspondants.



  IR : 3400, 725 cm-Ú.



   Ledit mélange traité au moyen de 0,5 g d'acide p-toluènesulfonique dans 250   ml    de toluène à l'ébullition et distillé, a finalement donné 14 g d'un produit contenant 50% de 3,3-diméthyl-1formylcyclohexa-4,6-diène. Après purification via le réactif de
Girard T, on a isolé 7,8 g (35%) du composé ci-dessus: nD= = 1,5089 et   d4 =0,9672;   
IR : 3060,2620,1675,1575,704 cmÚ.



   d) 1,5 g du composé ci-dessus, dissous dans 50   ml    d'éther, ont été ajoutés sous azote à la solution obtenue à partir de 0,3 g de tournures de Mg, 1,7 g de 1-bromobut-3-ène et 20 ml d'éther.



  Après avoir été chauffé durant 1 h à reflux et refroidi à 25 .



  le mélange réactionnel a donné, après les traitements usuels de lavage, séchage et distillation, 100 /0,01 torr, 1,5 g (76%) de   I      -(3,3-diméthylcyclohexa-4,6-diène-    1   -yî)-1-hydroxypent-4-ène.   



  nD= 1,4999;   d20=0,9754;   
IR: 3450, 3080, 1640, 990, 910 et 725   cm¯l;   
 e) 1 g du composé ci-dessus a été oxydé au moyen de 12 g de
MnO2 dans 200   ml    d'éther de pétrole, sous azote, pour donner finalement 0,85 g de 1-(3,3-diméthylcyclohexa-4,6-diène-1-yl)- pent-4-éne-1-one.



  nD = 1,5009 : d20 = 0,9309:
IR : 3080,1670,1640,1580,990 et 910 cm-Ú :
RMN: 1,01 (6H, 2s); 4,75-6,1 (3H, m); 5,88 (2H, m) et 6,76 (1H, m)    Gppm;   
SM: M+=190 (20); m/e: 175 (30), 148 (16), 135 (90), 119 (100),
 109 (80),   91(80),    55 (90), 41 (40).



   f) 237 g de 1-méthylène-3,3-diméthylcyclohex-5-ène obtenu selon  Bull. Soc. Chim. France , 1972, 4170, dissous dans 300   ml    de   CH2C12.    ont été traités par 400 g d'acide   peracétique    à 40%, en présence de 260 g d'acétate de sodium anhydre et 10 g de
Na2CO3, et à   200.    Après addition de H2O, extraction, lavage et séchage de la phase organique comme indiqué plus haut, l'acétate de 1-hydroxy-3,3-diméthylcyclohex-5-éne-1-ylméthyle a été isolé à   l'état    pur par c.p.g. préparative.



  nD = 1,4741 : d20 = 1,031 :
IR : 3450, 1740, 732 cm-Ú.



   g) Le composé ci-dessus a ensuite été chauffé dans un réacteur muni d'un séparateur d'eau, en présence de 3 g d'acide p-toluènesulfonique et 1000   ml    de toluène pour donner, après 1 h, un mélange 1:1 d'acétate de 3,3-diméthylcyclohexa-1,5-diène-1-ylméthyl et d'acétate de 3,3-diméthylcyclohexa-4,6-diène-1-ylméthyle respectivement. Après hydrolyse, et subséquemment oxydation au moyen de MnO2, du mélange ci-dessus, on a isolé un mélange 1:2 de 1-formyl-3,3-diméthylcyclohexa-4,6-diène et 1-formyl-3,3-diméthylcyclohexa-1,5-diène respectivement.



  nD= = 1,5022 et d20 = 0,9705.



   h) Le mélange ci-dessus a ensuite été traité dans les conditions d'une réaction de Grignard, avec le chlorure de butylmagnésium, pour donner finalement, après oxydation du produit résultant au moyen de MnO2, la 1-(3,3-diméthylcyclohexa-1,5-diène-1-yl).



     pent-4-ène-1-one.   



  RMN: 1,1 (6H, 2s); 2,3 (2H, m): 4,8-6,1 (3H, m); 5,65 (2H, m) et
 6,32 (1H,   m) 6    ppm.



   La 1-(3,3-diméthylcyclohexa-1,4-diène-1-yl)pent-4-ène-1-one a été obtenue à partir de (3,3-diméthylcyclohexa-1,4-diène-1-yl)- méthylcétone selon le procédé du schéma III, lettre h.



  nD=   1,4981;    d20=0,9759;
IR: 3070, 1675, 1625 et 722 cm-Ú;
RMN: 1,11 (6H, 2s); 4,8-6,1 (3H, m); 5,5 (2H, m);   6,47 (1H,    m);
 6 ppm;
SM: M+ = 190 (1): m/e: 175 (60), 135 (20), 119 (100), 107 (40),
 91(55), 55 (65), 43 (25).



   3,3-Diméthylcyclohex-6-ène-1-ylcarboxylate de prop-2-ène-1-yle;
 1-(3,3-diméthylcyclohex-6-ène-1-yl)hex-5-éne-1-one:
   I    -(3,3-diméthylcyclohex-6-ène-1   -yl)-3-méthylbut-3-ène-1    -one;
 1-(3,3-diméthylcyclohex-6-ène-1-yl)-2-méthylbut-3-ène-1-one, et
 1-(3,3-diméthylcyclohex-6-ène-1-yl)but-3-ène-1-one
 (schéma VI).



   a) Le 1-formyl-3,3-diméthylcyclohex-6-ène, voir schéma III, a été converti par la méthode dite de Grignard en dérivés hydroxylés correspondants, de formule:
EMI13.1     

R=(CH2)3-CH=CH2 a)
   =CH2-C(CH3)=CH2    b)
   =CH(CH3)-CH=CH2    c)
   =CH2-CH=CH2    d) et dont les caractères analytiques sont donnés ci-après:
Dérivé a): nD = 1,4832; d20 = 0,9143
IR: 3450, 3075, 1640,990 et 910 cm-Ú.



  Dérivé b): nD=   1,4858; d20=0,9198;   
IR : 3450,3075,1645,885 cm-Ú.



  Dérivé c): nD= 1,4845; d20=0,9198;
IR : 3400, 3075,1645,990 et 910 cm-Ú.



  Dérivé d):   nD= 1,4853; d20=0,9243;   
IR: 3450, 3075,   1640,990 et 910 cm3.   



   b) Chacun des alcools ci-dessus a ensuite été oxydé en cétone correspondante comme indiqué ci-après:1 partie de carbinol, diluée dans 10 parties de toluène, a été traitée à   10-15     et sous azote avec un mélange de 15 parties de Na2Cr2O,, 4 parties de
H2SO4 concentré et 5 parties de H2O. Après l'agitation du mélange réactionnel poursuivie pendant 12 h et les traitements usuels de lavage, séchage et distillation, on a isolé à   l'état    pur chacun des composés carbonylés suivants:
 1-(3,3-Diméthylcyclohex-6-ène-1-yl)hex-5-ène-1-one.

 

     nD=    1,4868; d20=0,9226;
IR : 3075, 1665, 1640, 990 et 910 cm-Ú;
RMN: 0,91 (6H, 2s); 4,75-6,0 (3H, m) 6 ppm;
SM: M+ = 206 (15) : m/e: 152 (72), 137 (90), 109 (100), 67 (60),
 53 (40), 41 (70).



      1 -(3,3-Diméthylcyclohex-6-ène-1 -yl)-3-méthylbut-3-ène-1 -one.   



  nD= 1,4883;   d20=0,9461;   
IR: 3080, 1665, 1640, 885   cm';   
RMN: 0,91   (6H, 2s);    132 (2H, t,   J=5Hz);    1,72 (3H, s); 3,26 (2H, m);
 4,66 et 4,8 (2H, 2m); 6,78 (1H, m) 6 ppm;
SM: M+=192 (1); m/e: 177 (3), 137 (100), 121(10), 109 (40),
 81(12), 87 (36), 55 (28), 41 (18).  



   1-(3,3-Diméthylcyclohex-6-ène-1-yl)-2-méthylbut-3-ène-1-one.



  nD= 1,4822 ; d20 = 0,9358;
IR : 3075, 1655, 1640, 990 et 910 cm-Ú;
RMN: 0,91 (6H, 2s); 1,16 (3H, d, J=7Hz); 3,78 (1H, m);
 4,76-6,1 (3H, m); 6,79 (1H,   m) Ï    ppm;
SM:   M+=192 (i); m/e:    177(2); 137(100), 124 (3), 109 (30),
 81 (12), 67 (30), 31(15).



      1-(3 ,3-Diméthylcyclohex-6-ène-1 -yl)but-3-ène-1 -one.   



  nD= 1,4828;   d20=0,9387;   
IR : 3080, 1668, 1640, 990 et 910 cm-Ú;
RMN: 0,92 (6H, 2s); 1,36 (2H, t, J =6Hz); 3,32 (2H, d, J = 5Hz);
 4,8-6,1 (3H, m); 6,78 (1H,   m) 6    ppm;
SM:   M+=178 (3);    m/e: 165 (12), 137 (100), 109 (40), 67 (44),
 41(26).



   Ce dernier composé peut être également obtenu à partir de 1-formyl-3,3-diméthylcyclohex-6-ène, via le 3,3-diméthylcyclohex6-ène-1-ylcarboxylate d'éthyle, comme indiqué ci-après. 1,8 g de
Prster ci-dessus, voir  J. Am. Chem. Soc. , 90, 5616 (1968), a été traité au moyen de bromure d'allylmagnésium, dans les conditions d'une réaction dite de Grignard, pour l'alcool tertiaire de formule:
EMI14.1     
 5 g du composé ci-dessus, pyrolysés à 440  sous 12 torrs, ont finalement donné 3,5 g d'un mélange contenant 65% de 1-(3,3diméthylcyclohex-6-ène-   i -yi)but-3-ène- 1    -one.



   Le 3,3-diméthylcyclohex-6-ène-1-ylcarboxylate de   prop-2-éne-i -    yle a été obtenu comme suit: 3,8 g de 3,3-diméthylcyclohex-6ène-l-ylcarboxylate d'éthyle ont été chauffés à reflux, durant 12 h, en présence de 44   ml    d'un mélange 1:1 de méthanol et d'une solution 0,5N de KOH dans H20. Après extraction à Péther de pétrole et évaporation à sec de la phase aqueuse, on a obtenu un résidu solide, finalement chauffé à reflux pendant 2 h, sous azote et en présence de 3,1 g de bromure d'allyle dans 50   ml    d'acétone. Après filtration du mélange réactionnel, évaporation et finalement distillation du résidu, on a recueilli 3,1 g (80%) d'ester désiré. Eb. 70-75"/0,1 torr.



  nD= 1,4789; d20=0,9811;
IR: 3080, 1715, 1640, 990 et 915 cm-Ú;
RMN: 0,9 (6H, 2s); 1,32 (2H, t,   J=5Hz);    2,1 (2H, m); 4,45-6,2
 (3H, m); 6,86 (1H, m) 6 ppm;
SM:   M+=194 (20);    m/e: 179 (10), 153 (40), 137 (60), 167 (48),
 93 (52), 67 (40), 41 (100).



   Acétate de   1-(3,3-diméthylcyclohex-1-ène-1-yl)pent-4-ene-1-yle;   
 formiate de   I -(3,3-diméthylcyclohex-l -ène-l -yl)pent-4-ène-l -yle;   
 1-(3,3-diméthylcyclohex-1-ène-1-yl)-1,1-éthylènedioxypent-4    ène;   
 acétate de   1 -(3,3-diméthylcyclohex-6-éne-l -yl)pent-4-ène-l -yle;   
 formiate de 1-(3,3-diméthylcyclohex-6-ène-1-yl)pent-4-ène-1-yle,
 et
 1-(3,3-diméthylcyclohex-6-ène-1-yl)-1,1-éthylénedioxy
 pent-4-éne (schéma VII).



   a) 15 g de   1-(3,3-diméthylcyclohex-1-ène-1-yl)pent-4-ène-1-    one, respectivement 1-(3,3-diméthylcyclohex-6-ène-1-yl)pent-4ène-l-one, ont été réduits au moyen de 2,2 g de LiAiH4 dans 50   ml    d'éther pour donner les carbinols correspondants.



   b) Les alcools ci-dessus ont ensuite été convertis en acétates correspondants, au moyen d'anhydride acétique, selon les techniques usuelles.



   Acétate de   1-(3,3-diméthylcyclohex-1-ène-1-yl)pent-4-ène-1-yle.   



  nD= 1,4648; d20=0,9374;
IR : 3080, 1730, 1635, 1230, 990 et 910 cm-;
RMN: 0,99 (6H, 2s); 1,98 (3H, s); 4,8-6,1 (3H, m); 5,32 (1H, m);    Gppm;   
SM:   M+=236    (0,7); m/e: 194 (10), 176 (6), 161 (15), 135 (30),
 107 (40), 93 (25), 81(32), 55 (35), 43 (100).



   Acétate de 1-(3,3-diméthylcyclohex-6-ène-1-yl)pent-4-ène-1-yle.



  nD = 1,4681; d20 = 0,9592;
IR : 3080, 1740,1640, 990 et 910 cmÚ;
RMN: 0,91 et 0,92 (6H, 2s); 1,32 (2H, t,   J=5Hz);    1,75 (2H, Im);
 1,98 (3H, s); 2,01 (2H, m); 4,8-6,1 (3H, m); 5,56 (1H, m)    Gppm;   
SM: M+ =236 (0,1); m/e: 194(14), 176 (12), 135 (40), 107 (26),
 93 (30), 79 (32), 43 (100).



   c) Les carbinols obtenus sous lettre a) ont été convertis en formiates correspondants, après traitement d'une partie d'alcool avec 5 parties d'acide formique à 100%, en présence de 2 parties de tamis moléculaire et 5 parties de toluène, et à température ambiante. La purification des esters désirés a été effectuée par chromatographie sur colonne (Silicagel-hexane/éther 9/1).



   Formiate de   1-(3,3-diméthylcyclohex-1-ène-1-yl)pent-4-ène-1-yle.   



  nD= 1,4704; d20 = 0,9486;
IR : 3075,1725,1645,1175,990 et 910 cm-Ú;
RMN: 0,98 (6H, 2s); 4,8-6,1 (3H, m); 5,4 (H, m); 7,9 (1H,   s) 6    ppm;
SM: M+ =222 (0,1); m/e: 208 (1), 177 (15), 161 (35), 135 (60),
 109 (70), 93 (45),   81(55),    69 (65), 55 (90), 41(100).



   Formiate de 1-(3,3-diméthylcyclohex-6-ène-1-yl)pent-4-ène-1-yle.



  nD= 1,4759; d20=0,9515;
IR : 3080, 1730, 1640, 1180, 990 et 910 cm-Ú;
RMN: 0,92 et 0,94 (6H, 2s); 4,8-6,1 (3H, m); 5,66 (1H, m);
 7,92 (1H,   s) Ï    ppm;
SM: M+ =222 (1); m/e: 207 (1), 192 (2), 176 (24), 161 (24),
 135 (98), 107 (60), 79 (75), 69 (50), 41 (100).



   d) Les éthylènecétals mentionnés ci-après ont été préparés à partir des cétones correspondantes, par traitement au moyen   d'éthylèneglycol,    en présence d'acide p-toluènesulfonique dans le benzène, temps de réaction 3-4 h:
 1-(3,3-Diméthylcyclohex-1-ène-1-yl)-1,1-éthylènedioxypent-4-ène.



     nD= 1,4761; d20=0,9607;   
IR : 3080, 1640, 1190, 1040, 990 et 910 cm-Ú;
RMN: 1,0 (6H, 2s); 3,78 (4H, m); 4,72-6,1 (3H, m): 5,5   (1H    m)    Gppm;   
SM: M+ =236 (0,1); m/e: 181 (100), 166 (1), 137 (2), 127 (20),
 109 (10), 73 (10), 55 (12).



   1-(3,3-Diméthylcyclohex-6-ène-1-yl)-1,1-éthylènedioxy
 pent-4-ène.

 

  nD = 1,4810 ; d20 = 0,9677;
IR: 3080, 1640, 1190, 1040, 990 et 910   cm8;   
RMN: 0,9 (6H,   2s):    3,8 (4H, m); 4,75-6,1 (3H, m): 5,75 (1H, m)    Gppm;   
SM: M+   =236(0,1);    m/e: 221 (1), 207 (1), 181 (100), 137 (15),
 127 (20), 109 (10), 91(7), 55 (20), 41(10).



      1-(4 ,4-Diméthylcyclohex-1 -ène-l -yl)pent-4-ène-1 -one   
 (schéma VIII).



   a) Le l-éthynyl-4,4-diméthylcyclohexanol a été préparé selon la méthode décrite dans  J. Chem. Soc. , 79, 5886 (1957).



   b) Le carbinol ci-dessus a ensuite été converti en ène-yne correspondante, selon la méthode décrite dans le schéma I, lettre b, avec un rendement de 78%.



  nD= 1,4919;   d20=0,9378;   
IR: 3400, 3080, 2290, 1640, 990 et 910   cm1;     
RMN: 0,96 (6H, 2s); 3,0 (2H, m); 4,95-6,1 (3H,   m) 6    ppm;
SM:   M+=192 (3);      m/e:    177 (7), 159 (8),   122(100),    121(90),
 71(65), 43 (55).



   c) Le composé ci-dessus a été finalement transformé en cétone correspondante, par traitement au moyen d'acide formique à 80%, dans les conditions d'une réaction dite de Rupe, rendement 68%.



  nD = 1,4881: d20 = 0,9298:
IR : 3080, 1670, 1640,990 et 910 cm-Ú;
RMN: 0,92 (6H, 2s); 1,4 (3H, t, J=6Hz); 4,75-6,1 (3H, m);
 6,69 (1H, m) 6 ppm;
SM:   M+=192 (3);    m/e: 177 (2), 137 (100), 109 (20), 81(50),
 69 (25), 55 (36), 41 (30).



   1-(3,3,4-Triméthylcyclohex-6-ène-1-yl)pent-4-ène-1-one ;
   1-(3,3,5-triméthylcyclohex-6-ène-1-yl)pent-4-ène-1-one,    et
 1-(3,3,5-triméthylcyclohex-1-ène-1-yl)pent-4-ène-1-one,
   (schéma    IX).



   a) 109 g de CuCI ont été ajoutés par petites portions à la solution obtenue à partir de 26,4 g de magnésium en tournures, 156,2 g de CH3I et 200   ml    d'éther, sous azote, 124 g de 4,4-diméthyl- cyclohex-2-ène-1-one dans l'éther ont ensuite été ajoutés au mélange réactionnel et le tout a été chauffé durant 2 h à reflux. Après hydrolyse au moyen d'une solution de NH4CI dans H20 et les traitements usuels de lavage, séchage et évaporation, on a recueilli 88 g (63%) de 3,4,4-triméthylcyclohexanone, Eb.   80-85V12    torrs.



   b) 43 g du composé ci-dessus et 34 g de méthylate de sodium dans 100   ml    d'éther ont été ajoutés sous azote, à un mélange refroidi de 46 g de formiate de méthyle et 200   ml    d'éther. Après avoir été agité durant 12 h à température ambiante, le mélange réactionnel a été versé sur glace, extrait à   éther    et finalement traité comme indiqué précédemment pour donner 30 g (65%) d'un composé de formule:
EMI15.1     

 c) Le cétoéther correspondant a été obtenu après traitement au moyen d'orthoformiate de méthyle selon la méthode figurant au schéma IV.



   d) 7,7 g du composé ci-dessus ont été réduits au moyen de
LiA1H4 dans   éther,    à 0-5  pour donner 6,6 g d'hydroxyéther correspondant.



   e) 4 g du composé ci-dessus ont été chauffés à reflux en présence de 0,2 g d'acide p-toluènesulfonique dans 75   ml    de toluène pour donner 2,7 g de   I-formyl-3,3Ptriméthylcyclohex-6-ène.   



  nD = 1,4849; d20 = 0,9484.



   f) Après conversion du composé ci-dessus en 1-(3,3,4-tri- méthylcyclohex-6-ène-1-yl)pent-4-ène-1-ol au moyen de chlorure d'allylmagnésium et oxydation subséquente au moyen de MnO2, voir schéma V, lettre e, on a isolé le composé suivant:
 1-(3,3,4-triméthylcyclohex-6-ène-1-yl)pent-4-ène-1-one.



  nD= 1,4896 ; d30 = 0,9311 ;
IR : 3080 , 1670, 1640, 990 et 910 cm-Ú ;   RMN:0,9    (3H, d,   3=6Hz);    0,78 et 0,99 (6H, 2s); 4,76-6,1 (3H, m);
 6,7 (1H, m) 6 ppm;
SM:   M+=206    (10); m/e: 191(5), 151(100), 123 (22), 95 (12),
   81(35),    70 (20), 55 (35), 41(20).



   En appliquant le procédé ci-dessus à la 2,4,4-triméthylcyclohexanone, on a obtenu la 1-(3,3,5-triméthylcyclohex-6-ène-1-yl)- pent-4-ène-1-one.



  nD= 1,4853; d20=0,9170;
IR : 3080, 1670, 1645, 990 et 910 cm-Ú;
RMN: 1,11 (3H, d, J = 7Hz); 0,82 et 1,03 (6H, 1s); 4,75-6,1 (3H, m);
 6,5 (1H,   m) 6    ppm;
 SM: M+=206 (45); m/e: 191(10), 165 (25), 151(100), 123 (95),
   81(60),    67 (60), 55 (65), 41(55).



     L'hydroxyéthynyl-3,3,5-triméthylcyclohexane    utilisé ci-dessus
 comme produit de départ a été préparé selon W. Ziegenstein,
  Athinylierung und Alkylnylierung , Verlag Chemie 1963, p. 9.



   Sa conversion en 1-(3,3,5-triméthylcyclohex-1-ène-1-yl)pent-4-ène-
 I-one a été effectuée selon le procédé du schéma I, lettre d.



   nD = 1,4838; d20 = 0,9107;
 IR : 3080, 1670, 1645, 990 et 910 cm-Ú.



  RMN: 1,02 (3H, d,   3=6Hz);    1,08 et 1,1 (6H, 2s); 4,78-6,1 (3H, m);
 6,4(1H,m)6ppm;
 SM: M+=206 (20); m/e: 191(7), 177 (6), 151(90), 123 (100),
   81(55),    55 (44), 41 (30).



     1-(3,3-Diméthylcyclohex-6-ène-1-yl)hex-4-ène-1-one    (i);
 1-(3,3-diméthylcyclohex-1-ène-1-yl)hex-4-ène-1-one (ii) ;
 1-(3,3-diméthylcyclohex-6-ène-1-yl)-3-méthylpent-4-ène-1-one
 (iii), et
 -(3,3-diméthylcyclohex-1-ène-1-yl)-3-méthylpent-4-ène-1-one
 (iv). (schéma X).



   Les composés ci-dessus ont été préparés conformément au pro
 cédé du schéma I, à partir de   7,1 l-diméthyl-7-hydroxydodéca-   
 2,10-diène-5-yne. Les caractères analytiques des composés obtenus
 sont donnés ci-après:
 (i)
 nD= 1,4921; d20=0,9296;
 IR : 1670, 1640, 965 cm-Ú;
 RMN:0,9 (6H, 2s); 1,6 (3H, d, J¯4Hz); 5,3 (2H, m); 6,68 (1H, m)    Gppm;   
 SM: M+ =206 (15); m/e: 191 (8), 177 (7), 137 (100), 109 (58),
 81(22), 67 (40), 41 (45).



   (ii)
 nD = 1,500; d20 = 0,9378 ;
 IR : 1670, 1645,965 cm-Ú ;
 RMN: 1,02 (6H, 2s); 1,6 (3H, d,   J5Hz);    5,3 (2H, m), 6,62 (1H, s)    Gppm;   
 SM: M+=206 (15); m/e: 188 (12), 146 (90), 137 (100), 131(55),
 109 (75), 83 (48), 55 (60), 41 (65).



   (iii)
 nD = 1,4873 ; d20 = 0,9202;
 IR: 3080, 1670, 1645, 990 et 910 cm-Ú ;
 RMN: 1,01 (3H, d, J¯6Hz); 0,92 (6H, 2s); 4,7-6,1 (3H, m);
 6,74 (1H,   m) 6    ppm;
 (iv)
 nD= 1,4889; d20=0,9311;
 IR: 3080, 1665, 1635, 985 et 910   cm-';   
 RMN: 1,02 (3H, d,   J#7Hz);    1,11 (6H, 2s); 4,72-6,1 (3H, m);    6,4 (1H,m) # ppm ;   
 SM:   M+=206 (8);    m/e: 191(3), 137 (100), 109 (65), 67 (30),
 41 (32).

 

   1-(3,3,5-Triméthylcyclohexa-1,5-diène-1-yl)pent-4-ène-1-one , et
 1-(3,3,5-triméthylcyclohexa-4,6-diène-1-yl)pent-4-ène-1-one
 (schéma XI).



   Les composés ci-dessus ont été préparés à partir de 2,2,4-tri-
   méthylcyclohex-2-ène-1-one,    selon le procédé du schéma V.



   1   -(3,3,5-Triméthylcyclohexa-1    ,5-diène-1 -yl)pent-4-ène-1-one.



   nD = 1,5132 ; d4 = 0,9612 ;
 IR : 3080, 1650, 1640, 1570, 990 et 910 cm-Ú;
 SM:   M+=204 (8); m/e:    109(14).



   1-(3,3,5-Triméthylcyclohexa-4,6-diène-1-yl)pent-4-ène-1-one.



   IR : 3080, 1660, 1645, 1575, 990 et 910 cm-Ú;
 RMN: 0,94 (6H, 2s); 1,8 (3H, d, J¯2Hz); 2,22 (2H, d, J¯2Hz);
 4,7-6,1 (3H, m); 5,53 et 6,61 (2H, 2s) 6 ppm;
 SM:   M+=204(15);m/e:    189(25).  



   1-(3,5-Diméthylcyclohex-6-ène-1-yl)pent-4-ène-1-one (i);
 1-(cis-3,4-diméthylcyclohex-6-ène-1-yl)pent-4-ène-1-one (ii);    1 -( trans-3,4-diméthylcyclohex-6-ène-1-yl)pent-4-ène-1-one   
 (iii), et
 1-(trans-3,4-diméthylcyclohex-1-éne-1-yl)pent-4-ène-1-one
 (iv), (schéma XII)
 Les composés ci-dessus ont été préparés conformément au procédé du schéma VIII. Les données analytiques des composés obtenus sont les suivantes: (i) nD = 1,4881 ; d20 = 0,9249 ;
 IR : 3075, 1665, 1640, 990 et 910 cm-Ú;
 RMN: 1,04 et 1,12 (6H, 2d, J   #   7Hz); 2,2-2,9 (4H, m); 4,75-6,2
 (3H, m); 6,55 (1H,   m) 6    ppm;
 SM:   M+=192 (1);    m/e: 191(25), 177 (2), 137 (100), 109 (98),
 67 (55), 55 (50), 41(35).



  (ii) nD= 1,4929;   d20=0,9410;   
IR : 3080, 1665, 1640, 990 et 910 cm-Ú ;
RMN: (90MHz): 0,85 et 0,87 (6H, 2d, J   ¯   7Hz); 2,75 (4H, m);
 4,9-6,1 (3H, m); 6,8 (1H,   m) 8    ppm;
SM:   M+=192 (6):    m/e:   177(4),      163(2),    137 (100), 109 (40),
   81(15),    67 (43), 55 (38), 41(36).



  (iii)   nD=    1,4899;   d20=0,9292;   
IR : 3080, 1665, 1645, 995 et 910 cm-Ú;   RMN:0,98    (6H,   2d, J@7Hz);   2,75 (4H, m); 4,88-6,1 (3H, m);
 6,85 (1H, m) 6 ppm;
SM:   M+=192 (7);    m/e: 177 (4), 137 (100),   109(40),81    (18),
 67 (38), 55 (30), 41(25).



  (iv)   nD=    1,4888; d20=0,9290;
IR: 3080, 1665,   1645,992et910cm5;   
RMN: 1,04 (3H, d,   J 6Hz);    1,12 (3H, d,   18Hz);    2,75 (4H, m);
 4,9-6,1 (3H, m); 6,65 (1H, m) 6 ppm;
SM:   M+=192    (15); m/e:   177(6),    151(14), 137 (100), 121 (6),
 109 (55), 85 (11), 81(16), 67 (48), 55 (44), 41 (38).



   Les exemples suivants illustreront la présente invention de façon plus détaillée.



  Exemple 1:
 On a préparé une composition parfumante de base pour eau de toilette en mélangeant les ingrédients suivants (parties en poids):
 Essence de patchouli . 30
 Acétate de vétivéryle......................... 50
 Jasmin synthétique . . 50
 Rose synthétique. 100
 Essence de galbanum . . 20
 Bergamote synthétique....................... 80
 Essence de racines d'angélique à 10% *   .   . 20
 a-Isométhylionone . 100
 Hydroxycitroncllal............ 80
 Cyclopentadécanolide à 10% *...................50
   "-Undécalactone à    10% * . ...... 20
 Aldéhyde undécylénique ............... 70
 Méthylnonylaldéhyde à 10% * . 10
 Dodécanal à 1%*................... 20
 Phénylacétaldéhyde à 10% * . . 20
 ss-Damascone à 10% *   .    ... 20
 Phénylméthylcarbinol . 20
 Civette synthétique .. 5
 Essence d'ylang .

  . 25
 Santal de   Misore..    20
 Coumarine. . 20
 Musc cétone .............. 30
 Mousse de chêne à 50% * . 20
   Eugénol      ..    . 40
 Essence de citron .. 20
 Phtalate de diéthyle . 60
 Total. . ... 1000
 * Dans le phtalate de diéthyle.



   En ajoutant à 90 g de la base ci-dessus 10 g de   1-(3,3-diméthyl-    cycohexa-1,5-diène-1-yl)pent-4-ène-1-one, on a obtenu une nouvelle composition parfumante possédant une note verte plus plaisante et plus intense que celle de ladite base. Un effet olfactif analogue a également été observé lors de Pemploi du composé ci-dessus à raison de 1 g pour 99 g de base.



   On a ensuite introduit séparément les composés ci-après dans la base susmentionnée, à des concentrations variant de 0,01 à 2% du poids de ladite base: formiate de   I -(3,3-diméthylcyclohex-6-ène- 1 -yl)pent-4-ène-1-yle;      I -(3,3-diméthylcyclohex-6-ène- 1-yl)hex-5-ène-1 -one;    3,3-diméthylcyclohex-6-ène- I-ylcarboxylate de prop-2-ène-1-yle ; 1-(3,3-diméthylcyclohexa-1,4-diène-1-yl)pent-4-ène-1-one, et 1 -(4,4-diméthylcyclohex-1-ène-1 -yl)pent-4-ène-1 -one.



   Les nouvelles compositions ainsi obtenues présentaient une note verte et fruitée plus intense que celle de la base préparée plus haut.



  Exemple 2:
 On a préparé une composition parfumante de base pour savon de toilette en mélangeant les ingrédients suivants (parties en poids):
 Aldéhyde undécylénique à 10% * ... ... 50
 Aldéhyde méthylnonylacétique à 10%* ... ........ 20
 3-Oxo-2-pentylcyclopentylacétate de méthyle 10% * 20
 Acétate de   trichiorométhyiphénylcarbinyle    . 20
 Ambre synthétique à 10%*................. 20    Méthylphénylglycidate d'éthyle à 10% * . @ 20
 Coumarine. .

  . @ 30   
 Héliotropine 20
 1,1-Diméthyl-4-acétyl-6-t-butylindane. 30
 Acétylcédrène ..................... 60
 Acétate de phényléthylcarbinyle . 10
 Salicylate de benzyle . 30
   α -Isométhyliononc    ... 60   
 Essence de patchouli @ 10
 Aldéhyde hexylcinnamique . @ 50   
   Alcool phenyléthylique    . 100
 Géranium synthétique .. ..... 50
 Mousse d'arbre concrète à 50% * . 40
 Essence de galbanum .. . 5
 Ylang synthétique . . 65
 Aldéhyde   cyclamen . .    40
 Acétate de benzyle . . 50
 Bergamote synthétique . 200
 Total . .. 1000
 * Dans le phtalate de diéthyle.

 

   En ajoutant à la base ci-dessus les composés mentionnés à l'exemple 1, soit aux concentrations indiquées, soit à raison de deux fois plus, on a obtenu de nouvelles compositions parfumantes possédant une plus grande diffusion que celle de la base ci-dessus. 



  
 



   Swiss patent N "586551 relates to a perfuming composition containing as active ingredient an alicyclic oxygenated compound of formula:
EMI1.1
 having a cyclic double bond in one of the positions indicated by the dotted lines.



   The above formula more specifically encompasses 1- (3,3-dimethylcyclohex-1-ene-1-yl) pent-4-en-1 -one and 1- (3,3-dimethyl cyclohex-6- ene-1-yl) pent-4-en-1-one. It has been found that many compounds homologous or analogous to those described above also possessed interesting organoleptic properties and that they could therefore be equally advantageously used as perfuming and / or flavoring ingredients.



   A subject of the present invention is therefore a perfuming or flavoring composition containing as active ingredient at least one of the alicyclic oxygenated compounds of formula:
EMI1.2
 having a saturated six-membered ring, or having one double bond in position 1, 4 or 6, or two double bonds in positions 1 and 4, 1 and 5, or 4 and 6 of the ring as indicated by the dotted lines, and in which:

  :
   - the index n is 0, 1 or 2;
 - the symbol Z, fixed in position I or 6 as indicated by the dotted lines, represents a CO, COR8 or C (OR9) 2 group in which the symbol R8 represents an acyl residue containing from 1 to 6 carbon atoms and R9 represents a an alkyl or alkylene residue containing from 1, respectively 2, to 6 carbon atoms;
 - the symbol Y represents an oxygen atom or a group
CH2;

  ;
 - each of the symbols Rl, R2, R3, R4 and R5 represents a hydrogen atom or one of them represents a CH3 group and the others a hydrogen atom, and each of the symbols R6 and R 'represents an alkyl residue containing from 1 to 3 carbon atoms, except for the case where said compound I has a double bond in position 1 or 6, the symbol Z, linked in position 1, represents an oxygen atom, Y represents a CH2 group, the index n is 1, each of the symbols R1, R2, R3,
R4 and R5 represents a hydrogen atom and each of the symbols
R6 and R 'represents a methyl group.



   A further subject of the present invention is the reuse of said perfuming or flavoring composition for the preparation of perfumes and perfumed products or, respectively, for raromatization of foods, drinks or tobacco.



   In the field of aromas, for example, compounds I are distinguished by their fruity note which is at the same time woody, green and oily, the latter character recalling in certain ways the green and oily note of galbanum or juniper for example.



   It was further discovered that the compounds I also exhibited interesting olfactory properties and that they therefore found a very advantageous use in the art of perfumery.



  Compounds I are in fact characterized by their original, powerful odor, the green, herbaceous note of which recalls in particular that of gasoline or galbanum resinoid, for example. This particular scent goes very well with that of many floral, woody, green, herbaceous, chypre or even animal compositions.



  The compounds I also have the effect, in most cases, of strengthening or developing, within the compositions in which they are incorporated, a green, rising note of great distinction.



   The compounds I are also very appreciated for the reconstitution of various essential oils and for the preparation of perfumed products such as soaps, detergents, cleaning products or cosmetic products for example.



   The proportions used in order to obtain an odoriferous effect such as that described above can vary widely.



   During the preparation of perfuming compositions, for example, interesting effects can be obtained by the use of proportions of between 0.01 and 5% of the weight of said composition. The compounds I are preferably used in an amount of approximately 0.01 to 2%. Given their particularly powerful odor, said compounds already exert a significant effect at relatively low concentrations, close to the lower limit given above.



   It remains understood that quantities greater or less than those mentioned above can also be envisaged, in particular when it is desired to obtain a particular organoleptic effect.



   Among the compounds of formula I which can be used according to the present invention, mention should be made of the compounds below: 1- (3,3-dimethylcyclohexyl) pent-4-en-1-one; 1- (3,3-dimethylcyclohexa-4,6-diene-1-yl) pent-4-en-1-one; 1- (3,3-dimethylcyclohexa-1,5-diene-1-yl) pent-4-en-1-one; 1- (3,3-dimethylcyclohex-4-en-1-yl) pent-4-en-1-one:

   1- (3,3-Dimethylcyclohex-1-en-1 -yl) pent-4-en-1 -yl acetate; 1 - (3,3-Dimethylcyclohex-1 -ene-1 -yl) pent-4-en-1-yl formate; 1- (3,3-dimethylcyclohex-1-ene-1-yl) -l, 1-ethylenedioxypent-4-ene; I - (3,3-Dimethylcyclohex-6-en-1 -yl) pent-4-en-I-yl acetate; 1 - (3,3-dimethylcyclohex-6-en-i-yl) pent-4-en-1-yl formate; I - (3,3-dimethylcyclohex-6-en-1 -yl) - 1,1-ethylenedioxypent-4-en; 1- (3,3-dimethylcyclohexa-1,4-diene-1 -yl) pent-4-ene-1 -one; 1- (3,3-dimethylcyclohex-6-en-1-yl) hex-5-en-1-one; 1- (3,3-dimethylcyclohex-1-en-1-yl) hex-4-en-1-one;

   1- (3,3-dimethylcyclohex-6-en-1-yl) hex-4-en-1-one;
I - (3,3-dimethylcyclohex-6-ene-1 -yl) -3-methylpent-4-ene-1 -one; 1- (3,3-dimethylcyclohex-1 -ene-1 -yl) -3-methylpent-4-en-1-one; 1- (4,4-dimethylcyclohex-I-en-1-yl) pent-4-en-I-one; 1- (3,3,4-trimethylcyclohex-6-en-1-yl) pent-4-en-1-one;

   1- (3,3,5-trimethylcyclohex-6-en-1-yl) pent-4-en-1-one; I - (3,3,5-trimethylcyclohex-1 -ene-I -yl) pent-4-ene-1 -one; I - (3,3,5-trimethylcyclohexa-4,6-diene- 1 -yl) pent-4-ene- 1 -one: l- (3,3-dimethylcyclohex-6-en-1 -yl) but- 3-en-1-one; 1- (3,3-dimethylcyclohex-6-en-i-yl) -3-methylbut-3-en-1-one; I - (3,3-dimethylcyclohex-6-ene-1 -yl) -2-methylbut-3-ene-1 -one; Prop-2-en-1-yl 3,3-dimethylcyclohex-6-en-1 -ylcarboxylate; I - (3,5-dimethylcyclohex-6-ene-1 -yl) pent-4-en-1 -one; 1- (cis-3,4-dimethylcyclohex-6-en-1-yl) pent-4-en-1-one;

   1 - (trans-3,4-dimethylcyclohex-6-ene- 1 -yl) pent-4-ene- 1 -one, and 1 - (trans-3,4-dimethylcyclohex-1 -ene- 1 -yl) pent -4-ene-1 -one.



   The above compounds, as well as 1- (3,3-dimethylcyclohex-6-ene-1-yl) pent-4-en-1-one and 1- (3,3-dimethylcyclohex-1-ene - 1-yl) pent-4-en-1-one, were obtained by means of one of the processes described below:
Diagram 1:
EMI2.1
 and ss-dehydrolinalol
EMI2.2
  
Diagram II
EMI3.1
  
Diagram III:
EMI4.1

1- (3,3-dimethylcyclohex-1-en-1-yl) -pent-4-en-1-one and 1- (3,3-dimethylcyclohex-6-en-1-yl) were thus prepared. ) pent-4-en-1-one
Diagram IV:
EMI5.1

 The following compounds were prepared according to the above method: 1- (3,3-dimethylcyclohexyl) pent-4-en-1-one; 1- (3,3-dimethylcyclohex-4-en-1-yl) pent-4-en-1-ene; 1 - (3,3-dimethylcyclohex-6-ene 1-yl) pent-4ene 1 -one, and 1- (3,3-dimethylcyclohex-1-en-1-yl) pent-4-en-1-one .



  Diagram V:
EMI6.1

 The following compounds were thus prepared: 1- (3,3-dimethylcyclohexa-1,4-dien-1-yl) pent-4-en-1-one; 1 - (3,3-dimethylcyclohexa-4,6-diene-1 -yl) pent-4-ene-1 -one, and
I - (3,3-dimethylcyclohexa-1,5-diene-1 -yl) pent-4-ene. 1 -one.



  Diagram VI:
EMI7.1

EMI7.2

 The following compounds were thus prepared: prop-2-en-1-yl 3,3-dimethylcyclohex-6-en-1-ylcarboxylate; 1- (3,3-dimethylcyclohex-6-en-1-yl) hex-5-en-1-one; 1- (3,3-dimethylyclohex-6-en-1 -yl) -3-methylbut-3-en-1-one; 1- (3,3-dimethylcyclohex-6-en-1-yl) -2-methylbut-3-en-1-one, and 1- (3,3-dimethylcyclohex-6-en-1-yl) but- 3-en-1-one.
EMI7.3




   The following compounds were prepared according to the above method: 1- (3,3-dimethylcyclohex-1-en-1-yl) pent-4-en-1-yl acetate; 1- (3,3-dimethylcyclohex-1-en-1-yl) pent-4-en-1-yl formate; 1- (3,3-dimethylcyclohex-1 -ene-1 -yl) - 1,1-ethylenedioxypent-4-ene; 1- (3,3-dimethylcyclohex-6. ene-1 -yl) pent-4-en-1 -yl acetate; 1- (3,3-dimethylcyclohex-6-en-1-yl) pent-4-en-1-yl, and 1- (3,3-dimethylcyclohex-6-en-1-yl) -1 formate, 1-ethylenedioxypent-4-ene.



  Diagram VIII:
EMI8.1

EMI8.2

   1 see J. Org. Chem. , 23, 1507 (1958).



    J. Org. Chem. , 37, 1020 (1972).



   Thus, 1- (4,4-dimethylcyclohex-1-ene-1 -yl) pent-4-en-1 -one was prepared.



  Diagram IX:
EMI8.3
  
Diagram X:
EMI9.1

 (see diagram IV)
 The following compounds were thus obtained: 1- (3,3-dimethylcyclohex-6-ene-1-yl) hex-4-en-1-one; 1- (3,3-dimethylcyclohex-1-en-1-yl) hex-4-en-1-one; 1- (3,3-dimethylcyclohex-6-en-1-yl) -3-methylpent-4-en-1-one, and 1- (3,3-dimethylcyclohex-1 -ene-1 -yl) -3 -methylpent-4-en-1 -one.



   The starting material used above can be obtained as follows:
EMI9.2

 dehydrolinalool
Diagram XI:
EMI9.3
  
EMI10.1

The following compounds were obtained according to the process below:
 1- (3,3,5-trimethylcyclohexa-1,5-diene-1-yl) pent-en-1-one, and
 1- (3,3,5-trimethylcyclohexa-4,6-diene-1-yl) pent-4-en-1-one.
EMI10.2




   The following compounds were thus prepared: 1- (3,5-dimethylcyclohex-6-en-1-yl) pent-4-en-1-one; 1- (cis-3,4-dimethylcyclohex-6-en-1-yl) pent-4-en-1-one; 1 - (trans-3,4-dimethylcyclohex-6-ene- 1 -yl) pent-4-en-1 -one, and 1 - (trans-3,4-dimethylcyclohex-1-en-1 -yl) pent -4-en-1-one.



   The synthesis of the above-named compounds I is described in more detail below. In the text below, temperatures are indicated in degrees centigrade and the abbreviations have the usual meaning in the art.



      1- (3,3-Dimethylcyclohex-6-en-1-yl) pent4-en-1-one and
 1- (3,3-dimethylcyclohex-1-en-1-yl) pent-4-en-1-one
 (diagram I).



   a) 100 g of α-dehydrolinalool were heated to 70-75 under 12 torr, in the presence of 30 g of boric acid, until the formation of H2O disappeared. The temperature of the bath was then slowly increased to 160-170 and there was thus collected, with a yield of 47%, a mixture of 3-methylene-7-methyloct I-yne-7-ene and 3.7 dimethyloct- 1-yne-3,7-diene. By using P-dehydrolinalol on the other hand, said mixture is isolated with a yield of 66%. The above mixture can be separated into its constituents by fractional distillation or by preparative gas chromatography (c.p.g.) (Carbowax - 5 m - 130).



   b) 2 g of the above mixture dissolved in 5 ml of isopropanol was added dropwise to a cooled mixture of 1.1 g of
KOH, 0.15 g of K2CO3 and 0.1 g of CuCl in 5 ml of methanol.



  30 min after addition of the reagents, another 1.5 g of allyl chloride was added, then the mixture was left to stand overnight.



  The reaction mixture, diluted with H2O. was then extracted with petroleum ether and the organic phase washed, dried and evaporated according to the usual techniques, and the residue finally distilled in a ball tube. A product was thus collected containing about 80% of a mixture of 6-methylene-10-methylundeca-1,10-diene-4-yne and 6-methylene-10-methylundeca-1,9-diene-4-yne. and about 20% of a mixture of 6,10-dimethylundeca-1,6,10-triene-4-yne and 6,10-dimethylundeca-1,6,9-triene-4-yne.



   c) 100 g of the mixture obtained above were heated to 90-100 in the presence of 200 ml of 80% formic acid. After two thirds of the starting product had disappeared (about 90 min), the reaction mixture, diluted with H20, was extracted with petroleum ether and treated as indicated above. Distillation of the residue gave 77 g of a mixture of 1- (3,3-dimethylcyclohex-1-en-1-yl) pent-4-en-1-yne and 1- (3,3-dimethylcyclohex-6 -ene-1-yl) pent-4ene-1-yne. The two compounds were isolated in pure state by c.p.g. preparatory.



   d) 3 g of the olefinic mixture obtained above were heated for 150 min at 90 minutes, in the presence of 80% formic acid. After cooling, the reaction mixture, diluted with H2O, was treated as before to finally give 2.8 g of a product having Eb. 65-75V2 torr and containing 75% of a 2: 3 mixture of 1 - (3,3-dimethylcyclohex-1 -ene-1 -yl) pent-4-ene-1 -one (A) and 1- (3 , 3-dimethylcyclohex-6-en-1-yl) pent-4-en-1-one (B) respectively.



  (A): n20 = 1.4891; d20 = 0.9247;
IR: 3080,1820,1675,1640,990,910cm-Ú;
NMR: 1.06 (6H, 2s); 4.73-6.00 (3H, m); 6.40 (1H, m) # ppm;
MS: M + = 192 (13); m / e: 177 (6), 137 (100), 109 (85), 93 (12),
 81 (32), 67 (55), 55 (58), 41 (45).



  (B): nD0 = 1.4879; d20 = 0.9262;
IR: 3080,1680,1640,990,910,820 cm-Ú;
NMR: 0.88 (6H, 2s); 1.32 (2H, t, J = 7Hz); 4.75-6.20 (3H, m);
 6.73 (1H, m) 6 ppm;
MS: M + = 192 (7); m / e: 177 (5), 164 (3), 149 (2), 137 (100),
 121 (6), 109 (45), 93 (6), 81 (13), 67 (33), 55 (28), 41 (16).



     1- (3,3-Dimethylcyclohex-6-en-1-yl) pent-4-en-1-one and
 1- (3,3-dimethylcyclohex-1-en-1-yl) pent-4-en-1-one
 (scheme II).



   a) 27 g of triphenylphosphine and 15 g of 5-bromopent-1-ene in 100 ml of xylene were heated under reflux for 40 h.



  After cooling to 0.5 and filtration, 33 g (100%) of the desired phosphonium bromide were isolated, mp = 188-190.



   b) 8 g of a 14% solution of butyllithium in ether were added over 15 min, under nitrogen, to 7 g of the phosphonium salt suspended in 80 ml of ether. To the reaction mixture cooled to 5-10 was then added 2.1 g of 3,3-dimethylcyclohex-5-ene-1one in 10 ml of ether. The above mixture was further stirred for 3 h, then filtered, washed with H2O until neutral, evaporated and finally distilled to give 1.5 g (50%) of 1- (3,3-dimethylcyclohex-5- en-1-ylidene) pent-4-ene.



   c) 1.5 g of the above compound were epoxidized with 2 g of 40% peracetic acid, in the presence of 1 g of sodium acetate and 20 ml of CH2Cl2. 3 h after addition of the reagents, the mixture diluted with H2O was treated as above to give, after distillation, 1.3 g of an epoxy compound of formula
EMI11.1

 The above compound was then heated for 8 h at 1000, in the presence of 0.5 g of acidic diatomaceous earth in 10 ml of dioxane, to give, after fractional distillation of the reaction mixture, 1.1 g of a product containing 30% 1- (3,3-dimethylchclohex-6-en-1-yl) pent-4-en-1-one according to analysis by cpg



   a ') The hydrogenation of 3,3-dimethylcyclohex-5-en-1-one was first carried out in the presence of palladium on carbon.



  The 3,3-dimethylcyclohexanone thus obtained was then treated with acetylene in a basic medium to give, with a yield of 50%, 1-ethynyl-1-bydroxy-3,3-dimethylcyclohexune.



   b ') 4.2 g of allyl chloride in 5 ml of methanol were added, at 0-10, to a mixture of 3.2 g of KOH, 0.5 g of
K2CO3 and 0.3 g of Cu2Cl2 in 20 ml of methanol. The reaction mixture was then brought to 40-50 and stirred overnight.



  After dilution with H2O, extraction with petroleum ether and treatment of the organic phase as indicated above, 7.5 g (90%) of 1- (1-hydroxy-3,3-dimethylcyclohexyl) pent-4-ene were isolated. -l-yne.



  n = 1.4899; d20 = 0.9354;
IR: 3450,3080,2235,1640,990,910 cm-Ú
 c ') 7 g of the above product were heated in a distillation apparatus under 12 torr, in the presence of 2 g of boric acid, until the formation of H2O disappeared. The temperature was then raised to 120-1300 and 5.3 g (70%) of a 2: 3 mixture of 1- (3,3-dimethylcyclohex-1-en-1-yl) pent was collected. -4-ene-1 -yne and 1- (3,3-dimethylcyclohex-6-ene-i -yi) pent-4-en-1 -yne. The conversion of said compounds into corresponding ketones was carried out as indicated above - scheme I; letter d.



   d ') The unsaturated alcohol obtained under letter b' was converted into the corresponding ketone by treating 3 g of said carbinol with 30 ml of 80% formic acid for 2 h at reflux.



  After the usual extraction, washing and distillation treatments, 1.8 g of a 1: 2 mixture of 1- (3,3-dimethylcyclohex-1ene-1-yl) pent-4-en-1- was obtained. one and 1- (3,3-dimethylcyclohex-6-en-1-yl) pent-4-en-1-one. The 3,3-dimethylcyclohex-5-en-1-one used above as starting material can be obtained according to the method described in J. Org. Chem. , 38, 3637 (1973).



     1- (3,3-Dimethylcyclohex-6-en-1-yl) pent-4-en-1-one and
 1- (3,3-dimethylcyclohex-1-en-1-yl) pent-4-en-1-one
 (scheme III).



   a) 467 g of methyl vinyl ketone and 480 g of isobutyraldehyde dissolved in a mixture of 700 ml of water and 350 ml of methanol were added over 3 h, under nitrogen, to a mixture maintained at 60-70 of 25 g of KOH , 150 ml of methanol and 1000 ml of water.



  After being heated for 1 h at 70 and cooled to 25, the mixture, diluted with H2O, was extracted with petroleum ether and finally treated as indicated above to give 325 g (40%) of 4,4-dimethylcyclohex -2-ene-1-one, Eb. 73-76 / 15 torr.



   b) 124 g of the above compound were hydrogenated in the presence of 2 g of Raney nickel in 300 ml of isopropanol to finally give 120 g of 4,4-dimethylcyclohexanone.



   c) 26 g of the above compound, dissolved in 200 ml of ether, were added over 45 min, at 0, to a mixture of 22 g of sodium methoxide, 30 g of ethyl formate and 100 ml of 'ether. The reaction mixture was then stirred overnight at room temperature, followed by the addition of 600 ml of water maintained at 0 and finally acidified with 30% HCl. After extraction with petroleum ether and treatment of the organic phase as indicated above, 26 g of a compound of formula were isolated:
EMI11.2

Eb. 29-33 / 0.01 torr, yield 75%.

  After treatment at 68 for 3-5 minutes of 15 g of said compound by means of 10.5 g of ethyl orthoformate, in the presence of 0.1 g of p-toluenesulfonic acid in 20 ml of methanol, and extraction of the reaction mixture with petroleum ether, 17 g of a mixture of compounds of formulas were isolated:
EMI12.1

EMI12.2

 The above mixture was used for the next reaction step without further purification.



   d) 6.0 g of the above mixture, dissolved in 20 ml of ether, was added under nitrogen to 0.8 g of LiAIII4 suspended in 30 ml of ether and finally stirred overnight. After addition of H2O, extraction with petroleum ether, washing, drying and distillation as indicated above, 6.8 g of impure material was isolated. After heating at reflux for 90 min in the presence of 0.3 g of p-toluenesulfonic acid and distillation, 4.8 g of a product containing 78% of 1-formyl-3,3-dimethylcyclohex-6 was finally obtained. - ene.



   e) 1.5 g of the above compound in 20 ml of ether was added to a solution prepared from 1.3 g of CH3I, 1.25 g of
Mg in turnings and 50 ml of ether. After being stirred for 2 h, the mixture was poured onto ice, then extracted and finally distilled to give 1.43 g of 1- (3,3-dimethylcyclohex-6-en-1-yl) -1-hydroxyethane.



  IR: 34000 cm-Ú;
NMR: 0.91 (6H, 2s); 1.18 (3H, J = 6Hz); 4.06 (1H, m); 5.53 (1H, m)
 Gppm;
MS: M + = 154 (21), m / e: 139 (6), 121 (16), 85 (26), 69 (20), 43 (100).



   f) 1.2 g of the above compound were treated, under nitrogen and at 25, with 20 g of MnO2 in 50 ml of petroleum ether.



  36 h after addition of the reagents, filtration and fractional distillation of the reaction mixture, 1.08 g (85%) of (3,3-dimethylcyclohex-6-en-1 -yl) methyl ketone was isolated.



  nD = 1.4809; d420 = 0.9309;
IR: 1670, 1640cm1.



   g) 10 g of the above compound were added at 0 to a mixture obtained from 5 g of a 12% solution of butyllithium in
Phexame, 7.3 g of isopropylamine and 70 ml of ether. 1 hour after addition of the reagents, a further 8.8 g of allyl bromide was added and left to stand overnight. After addition of H2O and treatment of the reaction mixture as indicated above, 6 g of a product containing 20% of 1- (3,3-dimethylcyclohex-6-en-1-yl) - pent-4-ene was isolated. -t-one. This compound was obtained in pure state by c.p.g.



  preparatory.



   g ') 5 g of a 12% solution of butyllithium in hexane and 100 ml of ether were added, at 00, to 73 g of isopropylamine dissolved in 70 ml of ether. 10 g of (3,3-dimethylcyclohex-1-en-1-yl) -methyl ketone were then added, over 1 h and at 0, to the above mixture and finally 8.8 g of allyl bromide. After the treatments described above, 5.9 g of a mixture containing 40% of 1- (3,3-dimethylcyclohex-1-en-1.yl) pent.4.ene was collected. 1 -one, finally isolated in the pure state by c.p.g. preparatory.



   (3,3-Dimethylcyclohex-1-en-1-yl) methyl ketone, used above as a starting material, was obtained according to the method given in Z. Chem. , 9, 64 (1969).



     1 - (3, 3-Dimethylcyclohex-6-ene-1 -yl) pent-4-en-1 -one;
 1- (3,3-dimethyljcycllohex-1-en-1-yl) pent-4-en-1-one;
 1- (3,3-dimethyljcyclohex-4-en-1-yl) pent-4-en-1-one, and
 1- (3,3-dimethylcyclohexyl) pent-4-en-1-one (scheme IV).



   a) The ozonolysis of the A3-carene in methanol was first carried out, according to the method described in Ber. , 60, 1591 (1927), to obtain a compound of formula:
EMI12.3

 The compound obtained above, diluted in 10 times its volume of methanol, was then heated to reflux in the presence of a few drops of 25% KOH. After 90 minutes of heating, dilution with
H2O, extraction with ether and treatment as indicated above, (3,3-dimethylcyclohexa-1,4-diene-1-yl) methyl ketone was isolated in a yield of 65%. Eb. 27-30.



  nD = 1.4886; d20 = 0.9493;
IR: 1670,1630,1560,720 cm-Ú;
UV (EtOH): #: 220, 240 and 310 nm.



   b) 15 g of the above compound were hydrogenated in the presence of palladium on charcoal to give a 31: 35: 17: 17 mixture of the following compounds:
EMI12.4
 respectively. These four ketone compounds were isolated in their pure state by c.p.g. preparatory.



   c) By treating the above mixture with allyl bromide and isopropylamine - see scheme II; letter h - and separation of the reaction mixture by c.p.g. Preparatively, the following compounds were isolated:
 1- (3,3-dimethylcyclohexyl) pent-4-en-1-one.



  nD = 1.4749; d20 = 0.9226;
IR: 3080,1706,1640,990 and 910 cm-Ú;
NMR: 0.9 (6H, 2s); 4.72-6.1 (3H, m) 6 ppm;
MS: M + = 194 (3); m / e: 179 (2), 139 (27), 117 (60), 111 (100),
 69 (92), 55 (85), 41 (40).



   1- (3,3-dimethylcyclohex-4-en-1-yl) pent-4-en-1-one.



  nD = 1.4788; d20 = 0.9212:
IR: 3080,1710,1645,990,910 and 722 cm-1;
NMR: 1.02 (6H, 2s); 4.76-6.1 (3H, m); 5.41 (2H, m) 6 ppm;
MS: M + = 192 (5): m / e: 177 (7), 109 (45), 83 (82), 67 (44), 55 (100),
 41 (55); as well as 1- (3,3) dimethylcyclohex-1-en-1-yl) pent-4-en-1-one and 1- (3,3-dimethylcyclohex-6-en-1-yl) pent- 4-en-1-one.



   1- (3,3-Dimethylcyclohexa-1,4-diene-1-yl) pent-4-en-1-one;
   1- (3,3-Dimethylcyclohexa-4,6-diene-1-yl) pent-4-en-1-one, and
 1- (3,3-dimethylcyclohexa-1,5-diene-1-yl) pent-4-en-1-one
 (diagram V).



   a) 52 g of sodium methoxide was added to 0-5 to 71 g of ethyl formate in 700 ml of ether. 20 min after addition of the reagents, 60 g of 4,4-dimethylcyclohex-2ene-1-one were then added and the reaction mixture was finally maintained overnight at 250, before pouring it on ice. After the usual extraction, washing, drying and distillation treatments, 63.1 g of a compound of formula were collected:
EMI12.5
 having Eb. 40.45 / 0.1 torr yield 87%).



  nD = 1.5231; d20 = 1.036.



   b) the above compound was then converted into mono and dimethoxylated derivatives respectively, according to the process of scheme III letter c.



  Monomethoxyketone: nD = 1.5167; d20 = 1.035:
IR: 1680, 1625.1590 cm-Ú.



  Dimethoxyketone: nD = 1.4821; d20 = 1.033:
IR: 1680,770, 710cm1.



   c) 26 g of a 7: 3 mixture of the respectively mono and dimethoxylated compounds obtained above, dissolved in 50 ml of ether, were added under nitrogen to 5.5 g of LiAiH4 suspended in 200 ml of ether, to finally give 18.3 g of a mixture of the corresponding carbinols.



  IR: 3400, 725 cm-Ú.



   Said mixture, treated with 0.5 g of p-toluenesulfonic acid in 250 ml of boiling and distilled toluene, finally gave 14 g of a product containing 50% of 3,3-dimethyl-1formylcyclohexa-4 , 6-diene. After purification using the reagent of
Girard T, 7.8 g (35%) of the above compound were isolated: nD = = 1.5089 and d4 = 0.9672;
IR: 3060,2620,1675,1575,704 cmÚ.



   d) 1.5 g of the above compound, dissolved in 50 ml of ether, were added under nitrogen to the solution obtained from 0.3 g of Mg turnings, 1.7 g of 1-bromobut- 3-ene and 20 ml of ether.



  After being heated for 1 h at reflux and cooled to 25.



  the reaction mixture gave, after the usual washing, drying and distillation treatments, 100 / 0.01 torr, 1.5 g (76%) of I - (3,3-dimethylcyclohexa-4,6-diene- 1 - yî) -1-hydroxypent-4-ene.



  nD = 1.4999; d20 = 0.9754;
IR: 3450, 3080, 1640, 990, 910 and 725 cm 1;
 e) 1 g of the above compound was oxidized using 12 g of
MnO2 in 200 ml of petroleum ether, under nitrogen, to finally give 0.85 g of 1- (3,3-dimethylcyclohexa-4,6-diene-1-yl) - pent-4-en-1-one .



  nD = 1.5009: d20 = 0.9309:
IR: 3080,1670,1640,1580,990 and 910 cm-Ú:
NMR: 1.01 (6H, 2s); 4.75-6.1 (3H, m); 5.88 (2H, m) and 6.76 (1H, m) Gppm;
MS: M + = 190 (20); m / e: 175 (30), 148 (16), 135 (90), 119 (100),
 109 (80), 91 (80), 55 (90), 41 (40).



   f) 237 g of 1-methylene-3,3-dimethylcyclohex-5-ene obtained according to Bull. Soc. Chim. France, 1972, 4170, dissolved in 300 ml of CH2C12. were treated with 400 g of 40% peracetic acid, in the presence of 260 g of anhydrous sodium acetate and 10 g of
Na2CO3, and at 200. After addition of H2O, extraction, washing and drying of the organic phase as indicated above, 1-hydroxy-3,3-dimethylcyclohex-5-en-1-ylmethyl acetate was isolated from pure state by cpg preparatory.



  nD = 1.4741: d20 = 1.031:
IR: 3450, 1740, 732 cm-Ú.



   g) The above compound was then heated in a reactor equipped with a water separator, in the presence of 3 g of p-toluenesulfonic acid and 1000 ml of toluene to give, after 1 h, a mixture 1: 1 of 3,3-dimethylcyclohexa-1,5-diene-1-ylmethyl acetate and 3,3-dimethylcyclohexa-4,6-diene-1-ylmethyl acetate respectively. After hydrolysis, and subsequent oxidation using MnO2, of the above mixture, a 1: 2 mixture of 1-formyl-3,3-dimethylcyclohexa-4,6-diene and 1-formyl-3,3- was isolated. dimethylcyclohexa-1,5-diene respectively.



  nD = = 1.5022 and d20 = 0.9705.



   h) The above mixture was then treated under the conditions of a Grignard reaction, with butylmagnesium chloride, to finally give, after oxidation of the resulting product by means of MnO2, 1- (3,3-dimethylcyclohexa -1,5-diene-1-yl).



     pent-4-en-1-one.



  NMR: 1.1 (6H, 2s); 2.3 (2H, m): 4.8-6.1 (3H, m); 5.65 (2H, m) and
 6.32 (1H, m) 6 ppm.



   1- (3,3-Dimethylcyclohexa-1,4-diene-1-yl) pent-4-en-1-one was obtained from (3,3-dimethylcyclohexa-1,4-diene-1- yl) - methyl ketone according to the process of scheme III, letter h.



  nD = 1.4981; d20 = 0.9759;
IR: 3070, 1675, 1625 and 722 cm-Ú;
NMR: 1.11 (6H, 2s); 4.8-6.1 (3H, m); 5.5 (2H, m); 6.47 (1H, m);
 6 ppm;
MS: M + = 190 (1): m / e: 175 (60), 135 (20), 119 (100), 107 (40),
 91 (55), 55 (65), 43 (25).



   Prop-2-en-1-yl 3,3-Dimethylcyclohex-6-en-1-ylcarboxylate;
 1- (3,3-dimethylcyclohex-6-en-1-yl) hex-5-en-1-one:
   I - (3,3-dimethylcyclohex-6-ene-1 -yl) -3-methylbut-3-en-1 -one;
 1- (3,3-dimethylcyclohex-6-en-1-yl) -2-methylbut-3-en-1-one, and
 1- (3,3-dimethylcyclohex-6-en-1-yl) but-3-en-1-one
 (diagram VI).



   a) 1-formyl-3,3-dimethylcyclohex-6-ene, see scheme III, was converted by the so-called Grignard method into corresponding hydroxylated derivatives, of formula:
EMI13.1

R = (CH2) 3-CH = CH2 a)
   = CH2-C (CH3) = CH2 b)
   = CH (CH3) -CH = CH2 c)
   = CH2-CH = CH2 d) and the analytical characteristics of which are given below:
Derivative a): nD = 1.4832; d20 = 0.9143
IR: 3450, 3075, 1640,990 and 910 cm-Ú.



  Derivative b): nD = 1.4858; d20 = 0.9198;
IR: 3450,3075,1645.885 cm-Ú.



  Derivative c): nD = 1.4845; d20 = 0.9198;
IR: 3400, 3075,1645,990 and 910 cm-Ú.



  Derivative d): nD = 1.4853; d20 = 0.9243;
IR: 3450, 3075, 1640,990 and 910 cm3.



   b) Each of the above alcohols was then oxidized to the corresponding ketone as indicated below: 1 part of carbinol, diluted in 10 parts of toluene, was treated at 10-15 and under nitrogen with a mixture of 15 parts of Na2Cr2O ,, 4 parts of
H2SO4 concentrate and 5 parts of H2O. After stirring the reaction mixture continued for 12 h and the usual washing, drying and distillation treatments, each of the following carbonyl compounds was isolated in the pure state:
 1- (3,3-Dimethylcyclohex-6-en-1-yl) hex-5-en-1-one.

 

     nD = 1.4868; d20 = 0.9226;
IR: 3075, 1665, 1640, 990 and 910 cm-Ú;
NMR: 0.91 (6H, 2s); 4.75-6.0 (3H, m) 6 ppm;
MS: M + = 206 (15): m / e: 152 (72), 137 (90), 109 (100), 67 (60),
 53 (40), 41 (70).



      1 - (3,3-Dimethylcyclohex-6-ene-1 -yl) -3-methylbut-3-en-1 -one.



  nD = 1.4883; d20 = 0.9461;
IR: 3080, 1665, 1640, 885 cm ';
NMR: 0.91 (6H, 2s); 132 (2H, t, J = 5Hz); 1.72 (3H, s); 3.26 (2H, m);
 4.66 and 4.8 (2H, 2m); 6.78 (1H, m) 6 ppm;
MS: M + = 192 (1); m / e: 177 (3), 137 (100), 121 (10), 109 (40),
 81 (12), 87 (36), 55 (28), 41 (18).



   1- (3,3-Dimethylcyclohex-6-en-1-yl) -2-methylbut-3-en-1-one.



  nD = 1.4822; d20 = 0.9358;
IR: 3075, 1655, 1640, 990 and 910 cm-Ú;
NMR: 0.91 (6H, 2s); 1.16 (3H, d, J = 7Hz); 3.78 (1H, m);
 4.76-6.1 (3H, m); 6.79 (1H, m) Ï ppm;
MS: M + = 192 (i); m / e: 177 (2); 137 (100), 124 (3), 109 (30),
 81 (12), 67 (30), 31 (15).



      1- (3, 3-Dimethylcyclohex-6-ene-1 -yl) but-3-en-1 -one.



  nD = 1.4828; d20 = 0.9387;
IR: 3080, 1668, 1640, 990 and 910 cm-Ú;
NMR: 0.92 (6H, 2s); 1.36 (2H, t, J = 6Hz); 3.32 (2H, d, J = 5Hz);
 4.8-6.1 (3H, m); 6.78 (1H, m) 6 ppm;
MS: M + = 178 (3); m / e: 165 (12), 137 (100), 109 (40), 67 (44),
 41 (26).



   The latter compound can also be obtained from 1-formyl-3,3-dimethylcyclohex-6-ene, via ethyl 3,3-dimethylcyclohex6-ene-1-ylcarboxylate, as indicated below. 1.8 g of
Prster above, see J. Am. Chem. Soc. , 90, 5616 (1968), was treated with allylmagnesium bromide, under the conditions of a so-called Grignard reaction, for the tertiary alcohol of formula:
EMI14.1
 5 g of the above compound, pyrolyzed at 440 under 12 torr, finally gave 3.5 g of a mixture containing 65% of 1- (3,3dimethylcyclohex-6-ene-i -yi) but-3-ene - 1 -one.



   Prop-2-en-i-yl 3,3-dimethylcyclohex-6-en-1-ylcarboxylate was obtained as follows: 3.8 g of ethyl 3,3-dimethylcyclohex-6ene-1-ylcarboxylate have was heated at reflux for 12 h in the presence of 44 ml of a 1: 1 mixture of methanol and a 0.5N solution of KOH in H2O. After extraction with petroleum ether and evaporation of the aqueous phase to dryness, a solid residue was obtained, finally heated under reflux for 2 h, under nitrogen and in the presence of 3.1 g of allyl bromide in 50 ml of acetone. After filtration of the reaction mixture, evaporation and finally distillation of the residue, 3.1 g (80%) of the desired ester was collected. Eb. 70-75 "/ 0.1 torr.



  nD = 1.4789; d20 = 0.9811;
IR: 3080, 1715, 1640, 990 and 915 cm-Ú;
NMR: 0.9 (6H, 2s); 1.32 (2H, t, J = 5Hz); 2.1 (2H, m); 4.45-6.2
 (3H, m); 6.86 (1H, m) 6 ppm;
MS: M + = 194 (20); m / e: 179 (10), 153 (40), 137 (60), 167 (48),
 93 (52), 67 (40), 41 (100).



   1- (3,3-Dimethylcyclohex-1-en-1-yl) pent-4-ene-1-yl acetate;
 I - (3,3-Dimethylcyclohex-1 -ene-1 -yl) pent-4-en-1 -yl formate;
 1- (3,3-dimethylcyclohex-1-en-1-yl) -1,1-ethylenedioxypent-4 ene;
 1 - (3,3-Dimethylcyclohex-6-en-1 -yl) pent-4-en-1 -yl acetate;
 1- (3,3-dimethylcyclohex-6-en-1-yl) pent-4-en-1-yl formate,
 and
 1- (3,3-dimethylcyclohex-6-en-1-yl) -1,1-ethylenedioxy
 pent-4-en (scheme VII).



   a) 15 g of 1- (3,3-dimethylcyclohex-1-en-1-yl) pent-4-en-1-one, respectively 1- (3,3-dimethylcyclohex-6-en-1-yl) pent-4ene-1-one, were reduced with 2.2 g of LiAiH4 in 50 ml of ether to give the corresponding carbinols.



   b) The above alcohols were then converted into the corresponding acetates, using acetic anhydride, according to the usual techniques.



   1- (3,3-Dimethylcyclohex-1-en-1-yl) pent-4-en-1-yl acetate.



  nD = 1.4648; d20 = 0.9374;
IR: 3080, 1730, 1635, 1230, 990 and 910 cm-;
NMR: 0.99 (6H, 2s); 1.98 (3H, s); 4.8-6.1 (3H, m); 5.32 (1H, m); Gppm;
MS: M + = 236 (0.7); m / e: 194 (10), 176 (6), 161 (15), 135 (30),
 107 (40), 93 (25), 81 (32), 55 (35), 43 (100).



   1- (3,3-Dimethylcyclohex-6-en-1-yl) pent-4-en-1-yl acetate.



  nD = 1.4681; d20 = 0.9592;
IR: 3080, 1740,1640, 990 and 910 cmÚ;
NMR: 0.91 and 0.92 (6H, 2s); 1.32 (2H, t, J = 5Hz); 1.75 (2H, Im);
 1.98 (3H, s); 2.01 (2H, m); 4.8-6.1 (3H, m); 5.56 (1H, m) Gppm;
MS: M + = 236 (0.1); m / e: 194 (14), 176 (12), 135 (40), 107 (26),
 93 (30), 79 (32), 43 (100).



   c) The carbinols obtained under letter a) were converted into corresponding formates, after treatment of one part of alcohol with 5 parts of 100% formic acid, in the presence of 2 parts of molecular sieve and 5 parts of toluene, and at room temperature. The purification of the desired esters was carried out by column chromatography (silica gel-hexane / ether 9/1).



   1- (3,3-Dimethylcyclohex-1-en-1-yl) pent-4-en-1-yl formate.



  nD = 1.4704; d20 = 0.9486;
IR: 3075,1725,1645,1175,990 and 910 cm-Ú;
NMR: 0.98 (6H, 2s); 4.8-6.1 (3H, m); 5.4 (H, m); 7.9 (1H, s) 6 ppm;
MS: M + = 222 (0.1); m / e: 208 (1), 177 (15), 161 (35), 135 (60),
 109 (70), 93 (45), 81 (55), 69 (65), 55 (90), 41 (100).



   1- (3,3-Dimethylcyclohex-6-en-1-yl) pent-4-en-1-yl formate.



  nD = 1.4759; d20 = 0.9515;
IR: 3080, 1730, 1640, 1180, 990 and 910 cm-Ú;
NMR: 0.92 & 0.94 (6H, 2s); 4.8-6.1 (3H, m); 5.66 (1H, m);
 7.92 (1H, s) Ï ppm;
MS: M + = 222 (1); m / e: 207 (1), 192 (2), 176 (24), 161 (24),
 135 (98), 107 (60), 79 (75), 69 (50), 41 (100).



   d) The ethylenecetals mentioned below were prepared from the corresponding ketones, by treatment with ethylene glycol, in the presence of p-toluenesulfonic acid in benzene, reaction time 3-4 h:
 1- (3,3-Dimethylcyclohex-1-en-1-yl) -1,1-ethylenedioxypent-4-ene.



     nD = 1.4761; d20 = 0.9607;
IR: 3080, 1640, 1190, 1040, 990 and 910 cm-Ú;
NMR: 1.0 (6H, 2s); 3.78 (4H, m); 4.72-6.1 (3H, m): 5.5 (1H m) Gppm;
MS: M + = 236 (0.1); m / e: 181 (100), 166 (1), 137 (2), 127 (20),
 109 (10), 73 (10), 55 (12).



   1- (3,3-Dimethylcyclohex-6-en-1-yl) -1,1-ethylenedioxy
 pent-4-ene.

 

  nD = 1.4810; d20 = 0.9677;
IR: 3080, 1640, 1190, 1040, 990 and 910 cm8;
NMR: 0.9 (6H, 2s): 3.8 (4H, m); 4.75-6.1 (3H, m): 5.75 (1H, m) Gppm;
MS: M + = 236 (0.1); m / e: 221 (1), 207 (1), 181 (100), 137 (15),
 127 (20), 109 (10), 91 (7), 55 (20), 41 (10).



      1- (4, 4-Dimethylcyclohex-1 -ene-1 -yl) pent-4-en-1 -one
 (scheme VIII).



   a) 1-ethynyl-4,4-dimethylcyclohexanol was prepared according to the method described in J. Chem. Soc. , 79, 5886 (1957).



   b) The above carbinol was then converted into the corresponding ene-yne, according to the method described in scheme I, letter b, with a yield of 78%.



  nD = 1.4919; d20 = 0.9378;
IR: 3400, 3080, 2290, 1640, 990 and 910 cm1;
NMR: 0.96 (6H, 2s); 3.0 (2H, m); 4.95-6.1 (3H, m) 6 ppm;
MS: M + = 192 (3); m / e: 177 (7), 159 (8), 122 (100), 121 (90),
 71 (65), 43 (55).



   c) The above compound was finally converted into the corresponding ketone, by treatment with 80% formic acid, under the conditions of a so-called Rupe reaction, yield 68%.



  nD = 1.4881: d20 = 0.9298:
IR: 3080, 1670, 1640,990 and 910 cm-Ú;
NMR: 0.92 (6H, 2s); 1.4 (3H, t, J = 6Hz); 4.75-6.1 (3H, m);
 6.69 (1H, m) 6 ppm;
MS: M + = 192 (3); m / e: 177 (2), 137 (100), 109 (20), 81 (50),
 69 (25), 55 (36), 41 (30).



   1- (3,3,4-Trimethylcyclohex-6-en-1-yl) pent-4-en-1-one;
   1- (3,3,5-trimethylcyclohex-6-en-1-yl) pent-4-en-1-one, and
 1- (3,3,5-trimethylcyclohex-1-ene-1-yl) pent-4-en-1-one,
   (diagram IX).



   a) 109 g of CuCl were added in small portions to the solution obtained from 26.4 g of magnesium turnings, 156.2 g of CH3I and 200 ml of ether, under nitrogen, 124 g of 4.4 -dimethyl-cyclohex-2-en-1-one in ether were then added to the reaction mixture and the whole was heated for 2 h at reflux. After hydrolysis using a solution of NH4Cl in H20 and the usual washing, drying and evaporation treatments, 88 g (63%) of 3,4,4-trimethylcyclohexanone, Eb. 80-85V12 torr.



   b) 43 g of the above compound and 34 g of sodium methoxide in 100 ml of ether were added under nitrogen, to a cooled mixture of 46 g of methyl formate and 200 ml of ether. After having been stirred for 12 h at room temperature, the reaction mixture was poured onto ice, extracted with ether and finally treated as indicated above to give 30 g (65%) of a compound of formula:
EMI15.1

 c) The corresponding ketoether was obtained after treatment with methyl orthoformate according to the method shown in scheme IV.



   d) 7.7 g of the above compound was reduced by means of
LiA1H4 in ether, at 0-5 to give 6.6 g of the corresponding hydroxyether.



   e) 4 g of the above compound were heated to reflux in the presence of 0.2 g of p-toluenesulfonic acid in 75 ml of toluene to give 2.7 g of I-formyl-3,3Ptrimethylcyclohex-6-ene .



  nD = 1.4849; d20 = 0.9484.



   f) After conversion of the above compound to 1- (3,3,4-tri-methylcyclohex-6-en-1-yl) pent-4-en-1-ol by means of allylmagnesium chloride and subsequent oxidation using MnO2, see diagram V, letter e, the following compound was isolated:
 1- (3,3,4-trimethylcyclohex-6-en-1-yl) pent-4-en-1-one.



  nD = 1.4896; d30 = 0.9311;
IR: 3080, 1670, 1640, 990 and 910 cm-Ú; NMR: 0.9 (3H, d, 3 = 6Hz); 0.78 and 0.99 (6H, 2s); 4.76-6.1 (3H, m);
 6.7 (1H, m) 6 ppm;
MS: M + = 206 (10); m / e: 191 (5), 151 (100), 123 (22), 95 (12),
   81 (35), 70 (20), 55 (35), 41 (20).



   Applying the above method to 2,4,4-trimethylcyclohexanone, 1- (3,3,5-trimethylcyclohex-6-ene-1-yl) - pent-4-en-1-one was obtained .



  nD = 1.4853; d20 = 0.9170;
IR: 3080, 1670, 1645, 990 and 910 cm-Ú;
NMR: 1.11 (3H, d, J = 7Hz); 0.82 and 1.03 (6H, 1s); 4.75-6.1 (3H, m);
 6.5 (1H, m) 6 ppm;
 MS: M + = 206 (45); m / e: 191 (10), 165 (25), 151 (100), 123 (95),
   81 (60), 67 (60), 55 (65), 41 (55).



     Hydroxyethynyl-3,3,5-trimethylcyclohexane used above
 as starting material was prepared according to W. Ziegenstein,
  Athinylierung und Alkylnylierung, Verlag Chemie 1963, p. 9.



   Its conversion to 1- (3,3,5-trimethylcyclohex-1-en-1-yl) pent-4-ene-
 I-one was carried out according to the method of scheme I, letter d.



   nD = 1.4838; d20 = 0.9107;
 IR: 3080, 1670, 1645, 990 and 910 cm-Ú.



  NMR: 1.02 (3H, d, 3 = 6Hz); 1.08 and 1.1 (6H, 2s); 4.78-6.1 (3H, m);
 6.4 (1H, m) 6ppm;
 MS: M + = 206 (20); m / e: 191 (7), 177 (6), 151 (90), 123 (100),
   81 (55), 55 (44), 41 (30).



     1- (3,3-Dimethylcyclohex-6-en-1-yl) hex-4-en-1-one (i);
 1- (3,3-dimethylcyclohex-1-en-1-yl) hex-4-en-1-one (ii);
 1- (3,3-dimethylcyclohex-6-en-1-yl) -3-methylpent-4-en-1-one
 (iii), and
 - (3,3-dimethylcyclohex-1-en-1-yl) -3-methylpent-4-en-1-one
 (iv). (diagram X).



   The above compounds were prepared in accordance with pro
 assigned from Scheme I, from 7.1 1-dimethyl-7-hydroxydodeca-
 2,10-diene-5-yne. The analytical characteristics of the compounds obtained
 are given below:
 (i)
 nD = 1.4921; d20 = 0.9296;
 IR: 1670, 1640, 965 cm-Ú;
 NMR: 0.9 (6H, 2s); 1.6 (3H, d, J¯4Hz); 5.3 (2H, m); 6.68 (1H, m) Gppm;
 MS: M + = 206 (15); m / e: 191 (8), 177 (7), 137 (100), 109 (58),
 81 (22), 67 (40), 41 (45).



   (ii)
 nD = 1.500; d20 = 0.9378;
 IR: 1670,1645.965 cm-Ú;
 NMR: 1.02 (6H, 2s); 1.6 (3H, d, J5Hz); 5.3 (2H, m), 6.62 (1H, s) Gppm;
 MS: M + = 206 (15); m / e: 188 (12), 146 (90), 137 (100), 131 (55),
 109 (75), 83 (48), 55 (60), 41 (65).



   (iii)
 nD = 1.4873; d20 = 0.9202;
 IR: 3080, 1670, 1645, 990 and 910 cm-Ú;
 NMR: 1.01 (3H, d, J¯6Hz); 0.92 (6H, 2s); 4.7-6.1 (3H, m);
 6.74 (1H, m) 6 ppm;
 (iv)
 nD = 1.4889; d20 = 0.9311;
 IR: 3080, 1665, 1635, 985 and 910 cm- ';
 NMR: 1.02 (3H, d, J # 7Hz); 1.11 (6H, 2s); 4.72-6.1 (3H, m); 6.4 (1H, m) # ppm;
 MS: M + = 206 (8); m / e: 191 (3), 137 (100), 109 (65), 67 (30),
 41 (32).

 

   1- (3,3,5-Trimethylcyclohexa-1,5-diene-1-yl) pent-4-en-1-one, and
 1- (3,3,5-trimethylcyclohexa-4,6-diene-1-yl) pent-4-en-1-one
 (diagram XI).



   The above compounds were prepared from 2,2,4-tri-
   methylcyclohex-2-en-1-one, according to the process of scheme V.



   1 - (3,3,5-Trimethylcyclohexa-1, 5-diene-1 -yl) pent-4-en-1-one.



   nD = 1.5132; d4 = 0.9612;
 IR: 3080, 1650, 1640, 1570, 990 and 910 cm-Ú;
 MS: M + = 204 (8); m / e: 109 (14).



   1- (3,3,5-Trimethylcyclohexa-4,6-diene-1-yl) pent-4-en-1-one.



   IR: 3080, 1660, 1645, 1575, 990 and 910 cm-Ú;
 NMR: 0.94 (6H, 2s); 1.8 (3H, d, J¯2Hz); 2.22 (2H, d, J¯2Hz);
 4.7-6.1 (3H, m); 5.53 and 6.61 (2H, 2s) 6 ppm;
 MS: M + = 204 (15); m / e: 189 (25).



   1- (3,5-Dimethylcyclohex-6-en-1-yl) pent-4-en-1-one (i);
 1- (cis-3,4-dimethylcyclohex-6-en-1-yl) pent-4-en-1-one (ii); 1 - (trans-3,4-dimethylcyclohex-6-en-1-yl) pent-4-en-1-one
 (iii), and
 1- (trans-3,4-dimethylcyclohex-1-en-1-yl) pent-4-en-1-one
 (iv), (scheme XII)
 The above compounds were prepared according to the method of Scheme VIII. The analytical data of the compounds obtained are as follows: (i) nD = 1.4881; d20 = 0.9249;
 IR: 3075, 1665, 1640, 990 and 910 cm-Ú;
 NMR: 1.04 and 1.12 (6H, 2d, J # 7Hz); 2.2-2.9 (4H, m); 4.75-6.2
 (3H, m); 6.55 (1H, m) 6 ppm;
 MS: M + = 192 (1); m / e: 191 (25), 177 (2), 137 (100), 109 (98),
 67 (55), 55 (50), 41 (35).



  (ii) nD = 1.4929; d20 = 0.9410;
IR: 3080, 1665, 1640, 990 and 910 cm-Ú;
NMR: (90MHz): 0.85 and 0.87 (6H, 2d, J ¯ 7Hz); 2.75 (4H, m);
 4.9-6.1 (3H, m); 6.8 (1H, m) 8 ppm;
MS: M + = 192 (6): m / e: 177 (4), 163 (2), 137 (100), 109 (40),
   81 (15), 67 (43), 55 (38), 41 (36).



  (iii) nD = 1.4899; d20 = 0.9292;
IR: 3080, 1665, 1645, 995 and 910 cm-Ú; NMR: 0.98 (6H, 2d, J @ 7Hz); 2.75 (4H, m); 4.88-6.1 (3H, m);
 6.85 (1H, m) 6 ppm;
MS: M + = 192 (7); m / e: 177 (4), 137 (100), 109 (40), 81 (18),
 67 (38), 55 (30), 41 (25).



  (iv) nD = 1.4888; d20 = 0.9290;
IR: 3080, 1665, 1645.992and910cm5;
NMR: 1.04 (3H, d, J 6Hz); 1.12 (3H, d, 18Hz); 2.75 (4H, m);
 4.9-6.1 (3H, m); 6.65 (1H, m) 6 ppm;
MS: M + = 192 (15); m / e: 177 (6), 151 (14), 137 (100), 121 (6),
 109 (55), 85 (11), 81 (16), 67 (48), 55 (44), 41 (38).



   The following examples will illustrate the present invention in more detail.



  Example 1:
 A basic perfume composition for eau de toilette was prepared by mixing the following ingredients (parts by weight):
 Patchouli essence. 30
 Vetiveryl acetate ......................... 50
 Synthetic jasmine. . 50
 Synthetic pink. 100
 Essence of galbanum. . 20
 Synthetic bergamot ....................... 80
 10% angelica root essence *. . 20
 a-Isomethylionone. 100
 Hydroxycitroncllal ............ 80
 10% Cyclopentadecanolide * ................... 50
   "-Undecalactone 10% *. ...... 20
 Undecylenic aldehyde ............... 70
 10% methylnonylaldehyde *. 10
 Dodecanal at 1% * ................... 20
 10% phenylacetaldehyde *. . 20
 10% ss-Damascone *. ... 20
 Phenylmethylcarbinol. 20
 Synthetic civet .. 5
 Essence of ylang.

  . 25
 Sandalwood from Misore .. 20
 Coumarin. . 20
 Musk ketone .............. 30
 50% oak moss *. 20
   Eugenol ... 40
 Lemon essence .. 20
 Diethyl phthalate. 60
 Total. . ... 1000
 * In diethyl phthalate.



   By adding to 90 g of the above base 10 g of 1- (3,3-dimethyl-cycohexa-1,5-dien-1-yl) pent-4-en-1-one, a new perfuming composition having a more pleasant and more intense green note than that of said base. A similar olfactory effect was also observed when using the above compound at a rate of 1 g per 99 g of base.



   The compounds below were then introduced separately into the aforementioned base, at concentrations varying from 0.01 to 2% of the weight of said base: formate of I - (3,3-dimethylcyclohex-6-ene-1 -yl ) pent-4-en-1-yl; I - (3,3-dimethylcyclohex-6-ene-1-yl) hex-5-en-1 -one; Prop-2-en-1-yl 3,3-dimethylcyclohex-6-en-I-ylcarboxylate; 1- (3,3-dimethylcyclohexa-1,4-diene-1-yl) pent-4-ene-1-one, and 1 - (4,4-dimethylcyclohex-1-en-1 -yl) pent-4 -ene-1 -one.



   The new compositions thus obtained presented a more intense green and fruity note than that of the base prepared above.



  Example 2:
 A basic fragrance composition for toilet soap was prepared by mixing the following ingredients (parts by weight):
 10% undecylenic aldehyde * ... ... 50
 10% methyl nonylacetic aldehyde * ... ........ 20
 Methyl 3-Oxo-2-pentylcyclopentylacetate 10% * 20
 Trichioromethyiphenylcarbinyl acetate. 20
 10% synthetic amber * ................. 20 10% ethyl methylphenylglycidate *. @ 20
 Coumarin. .

  . @ 30
 Heliotropin 20
 1,1-Dimethyl-4-acetyl-6-t-butylindane. 30
 Acetylcedrene ..................... 60
 Phenylethylcarbinyl acetate. 10
 Benzyl salicylate. 30
   α -Isomethyliononc ... 60
 Patchouli essence @ 10
 Hexylcinnamic aldehyde. @ 50
   Phenylethyl alcohol. 100
 Synthetic geranium .. ..... 50
 50% concrete tree moss *. 40
 Essence of galbanum ... 5
 Synthetic ylang. . 65
 Cyclamen aldehyde. . 40
 Benzyl acetate. . 50
 Synthetic bergamot. 200
 Total. .. 1000
 * In diethyl phthalate.

 

   By adding to the above base the compounds mentioned in Example 1, either at the concentrations indicated, or at a rate of twice as much, new perfuming compositions were obtained having a greater diffusion than that of the above base. .

Claims (1)

REVENDICATION CLAIM Composition parfumante ou aromatisante contenant en tant qu'ingrédient actif au moins un des composés oxygénés alicycliques de formule: EMI17.1 possédant un cycle à six membres saturé, ou possédant une double liaison en position 1,4 ou 6, ou encore deux doubles liaisons en positions I et 4, 1 et 5, ou 4 et 6 du cycle comme indiqué par les pointillés, et dans laquelle: Perfuming or flavoring composition containing as active ingredient at least one of the alicyclic oxygenates of formula: EMI17.1 possessing a saturated six-membered ring, or having a double bond in position 1,4 or 6, or two double bonds in positions I and 4, 1 and 5, or 4 and 6 of the ring as indicated by the dotted lines, and in which: : - I'indice n vaut 0, 1 ou 2; - le symbole Z, fixé en position I ou 6 comme indiqué par les pointillés, représente un groupe CO, COR8 ou C(OR9)2 dans lesquels le symbole R8 représente un reste acyle contenant de I à 6 atomes de carbone et R9 représente un reste alkyle ou alkylène contenant de 1, respectivement 2, à 6 atomes de carbone; - le symbole Y représente un atome d'oxygène ou un groupe CH2; : - the index n is 0, 1 or 2; - the symbol Z, fixed in position I or 6 as indicated by the dotted lines, represents a CO, COR8 or C (OR9) 2 group in which the symbol R8 represents an acyl residue containing from I to 6 carbon atoms and R9 represents a an alkyl or alkylene residue containing from 1, respectively 2, to 6 carbon atoms; - the symbol Y represents an oxygen atom or a CH2 group; ; - chacun des symboles Rl, R2, R3, R4 et R5 représente un atome d'hydrogène ou l'un d'entre eux représente un groupe CH3 et les autres un atome d'hydrogène, et chacun des symboles R6 et R7 représente un reste alkyle contenant de 1 à 3 atomes de carbone, exception faite du cas ou ledit composé I possède une double liaison en position I ou 6, le symbole Z, relié en position 1, représente un atome d'oxygène, Y représente un groupe CH2, indice n vaut 1, chacun des symboles Rl, R2, R3, R4 et R5 représente un atome d'hydrogène et chacun des symboles R6 et R7 représente un groupe méthyle. ; - each of the symbols Rl, R2, R3, R4 and R5 represents a hydrogen atom or one of them represents a CH3 group and the others a hydrogen atom, and each of the symbols R6 and R7 represents a residue alkyl containing 1 to 3 carbon atoms, except for the case where said compound I has a double bond in position I or 6, the symbol Z, linked in position 1, represents an oxygen atom, Y represents a CH2 group, subscript n is 1, each of the symbols R1, R2, R3, R4 and R5 represents a hydrogen atom and each of the symbols R6 and R7 represents a methyl group.
CH120975A 1975-01-31 1975-01-31 Di:methyl-cyclohexene-alkenone cpds. CH603071A5 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CH120975A CH603071A5 (en) 1975-01-31 1975-01-31 Di:methyl-cyclohexene-alkenone cpds.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
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Publication Number Publication Date
CH603071A5 true CH603071A5 (en) 1978-08-15

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7914793B2 (en) 1997-01-29 2011-03-29 Shozo Koyama Method for producing an antigenic substance and antibody
EP2687586A1 (en) 2012-07-17 2014-01-22 Symrise AG Use of defined cyclohexenones as a means for the additive reinforcement of a smell impression and composition of aromas and/or tastes
JP2017514794A (en) * 2014-03-28 2017-06-08 ディーエスエム アイピー アセッツ ビー．ブイ． Process for the production of 1- (5,5-dimethylcyclohex-1-en-1-yl) ethanone and 1- (5,5-dimethylcyclohex-6-en-1-yl) ethanone

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7914793B2 (en) 1997-01-29 2011-03-29 Shozo Koyama Method for producing an antigenic substance and antibody
EP2687586A1 (en) 2012-07-17 2014-01-22 Symrise AG Use of defined cyclohexenones as a means for the additive reinforcement of a smell impression and composition of aromas and/or tastes
JP2017514794A (en) * 2014-03-28 2017-06-08 ディーエスエム アイピー アセッツ ビー．ブイ． Process for the production of 1- (5,5-dimethylcyclohex-1-en-1-yl) ethanone and 1- (5,5-dimethylcyclohex-6-en-1-yl) ethanone

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