CH528470A - Unsaturated cycloaliphatic ketones - Google Patents

Unsaturated cycloaliphatic ketones

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Publication number
CH528470A
CH528470A CH555970A CH555970A CH528470A CH 528470 A CH528470 A CH 528470A CH 555970 A CH555970 A CH 555970A CH 555970 A CH555970 A CH 555970A CH 528470 A CH528470 A CH 528470A
Authority
CH
Switzerland
Prior art keywords
acidic
formula
lower alkyl
alkyl radical
trimethyl
Prior art date
Application number
CH555970A
Other languages
French (fr)
Inventor
Ervin Dr Kovats
Edouard Dr Demole
Guenther Dr Ohloff
Max Dr Stoll
Original Assignee
Firmenich & Cie
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CH697669A external-priority patent/CH520767A/en
Priority to CH555970A priority Critical patent/CH528470A/en
Priority to CH1236372A priority patent/CH539682A/en
Priority to CH1236272A priority patent/CH536834A/en
Application filed by Firmenich & Cie filed Critical Firmenich & Cie
Priority to DE2065324A priority patent/DE2065324C3/en
Priority to FR7016523A priority patent/FR2042452A1/fr
Priority to DE2065322A priority patent/DE2065322C3/en
Priority to DE19702022216 priority patent/DE2022216C3/en
Priority to DE2065323*A priority patent/DE2065323A1/en
Priority to NL7006649.A priority patent/NL163211C/en
Priority to GB2221570A priority patent/GB1305621A/en
Priority to JP3858770A priority patent/JPS553328B1/ja
Priority to DD153631A priority patent/DD96077A6/xx
Priority to IT24347/70A priority patent/IT1047883B/en
Publication of CH528470A publication Critical patent/CH528470A/en
Priority to US05/503,738 priority patent/US3975310A/en
Priority to US503794A priority patent/US3928456A/en
Priority to US05/523,743 priority patent/US3931326A/en
Priority to US05/782,536 priority patent/US4187863A/en
Priority to US05/900,522 priority patent/US4226892A/en

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    • C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
    • C07C403/16—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms not being part of —CHO groups
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/20—Synthetic spices, flavouring agents or condiments
    • A23L27/203—Alicyclic compounds
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
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    • A24B15/34—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a carbocyclic ring other than a six-membered aromatic ring
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
    • A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
    • A24B15/36—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring
    • A24B15/40—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring having only oxygen or sulfur as hetero atoms
    • A24B15/403—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a heterocyclic ring having only oxygen or sulfur as hetero atoms having only oxygen as hetero atoms
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    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
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    • 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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    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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    • C07C33/04—Acyclic alcohols with carbon-to-carbon triple bonds
    • C07C33/048—Acyclic alcohols with carbon-to-carbon triple bonds with double and triple bonds
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
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    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/32—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by aldehydo- or ketonic radicals
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
    • C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms
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    • C11B9/00—Essential oils; Perfumes
    • C11B9/0069—Heterocyclic compounds
    • C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
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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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  • Epoxy Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

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

Description

  

  
 



  Procédé de préparation de cétones insaturées
 La présente invention concerne un procédé de préparation de composés odoriférants et aromatisants, lesdits composés pouvant être utilisés pour la préparation de parfums et de produits parfumés et comme agents aromatisants pour modifier les propriétés organoleptiques d'aliments pour l'homme et les animaux, de boissons, de préparations pharmaceutiques et du tabac.



   L'invention concerne un procédé pour la préparation de composés de formule:
EMI1.1     
 dans laquelle les symboles R1, R2 et   R3    représentent l'hy   drogène    ou   l'un    d'eux un radical alcoyle inférieur, par exemple méthyle ou éthyle, et les autres l'hydrogène et
R4, R5,   R6    et R7 représentent l'hydrogène ou   l'un    d'eux un radical alcoyle inférieur, par exemple méthyle ou éthyle, et les autres l'hydrogène, caractérisé en ce qu'on traite par un agent acide un composé de formule:

  :
EMI1.2     
 contenant une double liaison dans la position 2'- ou 3'de la chaîne latérale, la double liaison étant indiquée par les pointillés, dans laquelle n vaut zéro ou 1, les symboles
R ayant le même sens que ci-dessus, et dans laquelle l'oxygène de la fonction époxyde est relié aux positions 1- et 2- ou 2- et 3- du cycle, comme indiqué par les pointillés.



   Comme agent acide on peut utiliser des produits acides, minéraux ou organiques, tels les acides chlorhydrique, phosphorique ou sulfurique, les terres argileuses acides ou encore les acides tosylique et trifluoracétique.



   On peut effectuer la réaction dans un solvant organique, de préférence inerte, comme par exemple le ben  zène, le dioxanne, le tétrahydrofuranne ou l'acétate d'éthyle, et de préférence à la température d'ébullition dudit solvant.



   On a trouvé que les composés de formule IIa, comme par exemple le cis- et   trans-2,6,6-triméthyl-l-crotonoyl-      1,2-époxycyclohexane,    le   2,6,6-triméthyl- 1 -vinylacétyl- 1,2-    époxycyclohexane ou le   2,6, 6-triméthyl- 1 -crotonoyl-2,3 -    cyclohexane, et IIb, comme par exemple le 2,6,6-tri   méthyl- 1 -(1    -hydroxy-2-butényl)- 1,2-époxycyclohexane ou le   2,6,6-triméthyl-1-(1    -hydroxy-3-butényl)-   1,2 - époxy -    cyclohexane, qui sont des composés nouveaux, possèdent d'intéressantes propriétés   organoleptiques.   



   Les cétones de formule IIa peuvent être préparées à partir des composés hydroxylés de formule:
EMI2.1     
 dans laquelle les substituants R et l'indice n ont le même sens qu'indiqué plus haut, suivant un procédé selon lequel on oxyde les composés IIb au moyen d'un agent oxydant. Comme agent oxydant on peut employer les agents connus en général pour transformer les fonctions hydroxylées secondaires en fonctions cétoniques. En particulier on peut employer des dérivés oxygénés de l'argent ou d'un élément de transition comme le chrome, le manganèse ou le nickel.   I1    est avantageux d'utiliser un bichromate alcalin, par exemple le bichromate de sodium, en solution acide, par exemple sulfurique.



   Les composés IIb utilisés comme produit de départ pour la préparation mentionnée ci-dessus peuvent être obtenus par époxydation, au moyen d'un peracide comme par exemple l'acide peracétique, l'acide perbenzoique, l'acide performique, l'acide monoperphtalique ou m-chloroperbenzoïque dans un solvant organique tamponné, d'un composé de formule
EMI2.2     
 dans laquelle les substituants R, l'indice n et les pointillés ont le même sens que celui indiqué pour la formule IIa.



   Le processus indiqué ci-dessus ainsi que la préparation des composés IIIb sont illustrés par le schéma suivant
EMI2.3     
  
 Les exemples qui suivent illustrent l'invention d'une manière plus détaillée. Dans lesdits exemples les températures sont indiquées en degrés centigrades.



   Exemple   1   
 Trans-2,6,6-triméthyl-1-crotonoyl   -1,3-cyclohexadiène   
 Un mélange constitué par les isomères cis- et transde   2,6,6-triméthyl-1-crotonoyl-1,2-époxycyclohexane    (10 g), obtenu suivant la méthode décrite ci-après, et 2g de terre silicieuse acide dans 50 ml de dioxanne a été maintenu à   100-105     sous atmosphère d'azote jusqu'à transformation complète des dérivés époxydés en 2,6,6-triméthyl-1-crotonoyl-1,3-cyclohexadiène, le cours de la réaction étant suivi par chromatographie en phase gazeuse. Après filtration, la solution est soumise à distillation. On obtient un produit à Eb.   60-850/0,5    Torr (g.



  8,0) qui d'après son analyse spectrométrique révèle un contenu de 7,5 g   (82 /o)    en   2,6,6-triméthyl-1 -crotonoyl-    1,3-cyclohexadiène.



   IR: 1670, 1635,   1610,970cm-1   
 RMN: 1,01 (6 H, s), 1,62 (3 H, s), 1,93 (3 H, d.d.,
 J = 6,5 et 1,5   cps),    2,07 (2 H, d, J = 2,3 cps),
 5,77 (2 H, t, J = 2,3 cps), 6,06 (1 H, d.q., J =
 16 et 1,5 cps), 6,75 (1 H, d.q., J = 16 et 6,5 cps);
 SM: m/e 69-121, 105, 41, 190.



   La réaction ci-dessus procède avec formation d'un intermédiaire hydroxylé qui a été défini par chromatographie en phase gazeuse; ses données analytiques sont les suivantes:    n2D0 = 1,5049; d4  = 1,018;   
   CisHioOo    Calculé : C 74,96 H 9,68
 Trouvé : C 74,68 H 9,69 %
 IR: 3090 (OH), 1675 (CO), 1620 (C = C), 970   cm-t;   
 RMN: 0,72 (3 H, s), 0,97 (3 H, s), 1,45 (3 H, m),
 1,92 (d, J = 7,5 cps), 4,07 (1 H, m), 5,7 (1 H, m),
 6,35-7,2 (2 H, m),   â    ppm;
 SM: M+ = 208 (0,1), m/e = 190 (0,1), 175 (0,1), 165
 (0,1), 152 (0,1), 139 (49), 121 (3), 109 (2), 95 (33),
 82 (3), 69 (28), 55 (7), 43 (100), 27 (5).



   Le mélange d'isomères cis- et trans- de 2,6,6-triméthyl-   l-crotonoyl-    1,2-époxycyclohexane, utilisé comme produit de départ dans la préparation donnée ci-dessus, a été obtenu ainsi:
 a) 2,6,6-triméthyl-1-(1-hydroxy-3-butényl)-
 I-cyclohexène
 5 g de chlorure d'allyle sont ajoutés sous atmosphère d'azote à une suspension de magnésium   (28,8 g)    dans 50   ml    d'éther sec. Suivant les conditions habituelles d'une réaction de Grignard, on ajoute goutte à goutte au mélange ci-dessus, 85 g de chlorure d'allyle et 152 g de   p-    cyclocitral dans   350ml    d'éther sec à une vitesse telle qu'elle maintienne le mélange à reflux.

  A cette température, le mélange est laissé pendant 3 h et versé ensuite dans une solution aqueuse de   NHLC1.    Après séparation, la phase éthérée donne, à la suite des traitements habituels et distillation, 178,1 g   (900/o)    de produit hydroxylé (97   0/o    de pureté).   Eb.    500/0,01 Torr.



      = = 1,4958; d20 = 0,9390;   
 b)   2,6,6-triméthyl-l-(l-hydroxy-3-butényl)-       I ,2-époxycyclohexane   
 Un mélange d'acide peracétique   40 oxo    (105 g) et   acér    tate de sodium anhydre (3,0 g) est ajouté à 250 avec agitation à une suspension de 2,6,6-triméthyl-1-(1-hydroxy3-butényl)-1-cyclohexène (97 g) et acétate de sodium anhydre (60 g) dans 175   ml    de   CH2C12    (1,5 h).



   On laisse le mélange de réaction avec agitation pendant une nuit, ensuite on y ajoute   500 ml    d'eau et   l'on    sépare la phase organique. Après les traitements habituels de lavage et séchage on obtient par distillation 98 g (83    /o)    des deux diastéréoisomères du produit époxydé.



  Les deux isomères peuvent être séparés par chromatographie en phase gazeuse (Carbowax,   1700,    3 m).



   Pic 1: (80   0/o),      Eb.    88-90/0,5 Torr;    n2D0 = 1,4790; d24  = 0,9772;   
 IR: 3450, 1820,   1640,990,    900   cm-1   
 RMN: 1,0 et 1,03 (6 H, 2 s), 1,42 (3 H, s), 2,52    (1 H, m), 3,92 (1 H, t), 4,7-6,4 (3 H), 6 ppm;   
 SM: M+ = 210 (0,1), m/e: 192 (0,1), 177 (0,1), 169
 (2), 149 (5), 140 (3), 125 (22), 109 (28), 95 (12),
 83 (23), 69 (46), 55 (36), 43 (100), 27 (12);
 Pic 2:   (2O0/o),      Eb.    93-40/0,5 Torr;
   n2D0    =   1,4839;      d4     = 0,9945;
 IR: 3095, 3060, 1635, 990, 910   cm-1   
 RMN: 1,00 et 1,16 (6 H, 2 s), 1,33 (3 H, s), 3,92    (1 H, m), 4,68-6,2 (3 H), ppm;   
 SM:

  M+ = 210 (0,1), m/e: 192 (0,1), 177 (0,1) 169
 (2), 149 (5), 140 (2), 119 (59), 109 (34), 95 (13),
 83 (25), 69 (47), 55 (42), 43 (100), 27 (13).



   c)   2,6,6-triméthyl-1-vinylacétyl-   
 1,2-époxycyclohexane
 Une solution de 2,6,6-triméthyl-1-(1-hydroxy-3-butényl)-1,2-époxycyclohexane (178,5 g), préparé suivant b), dans 265   ml    de toluène est ajoutée goutte à goutte, avec vigoureuse agitation et à une température de 0-50, à une solution de   Na2Cr207    (620 g) dans 500   ml    d'acide sulfurique concentré et 1220   ml    d'eau. On laisse le mélange de réaction à   0-50    pendant 3 h; on l'extrait à l'éther et après les traitements habituels on obtient par évaporation 114,7 g   (67 0/o)    de produit brut qui, après distillation,   Eb.    780/0,4 Torr, donne 100 g (59 O/o) d'un produit huileux.

  L'analyse par chromatographie en phase gazeuse montre que ce dernier a une pureté de 95 % en 2,6,6triméthyl- 1   -vinylacétyl- 1 ,2-époxycyclohexane.   



     n2nO=    1,4721;   d24 = 0,9781;   
   C15H20O2 Calculé :    C 74,96 H 9,68
 Trouvé : C 74,66 H 9,72 %
 IR: 3080, 1700, 1820, 1640, 915,   910 cm-t;   
 RMN: 1,02 et 1,05 (6 H, 2 s),   1,1(3    H, s), 3,2 (2 H,
 m),   4,8-6,2(3    H),   3    ppm;
 SM: M+ = 208 (0,1), m/e: 193 (1), 177 (1), 165
 (0,1), 151 (15), 135 (2), 123 (8), 111(4), 95 (3),
 81 (2), 69 (100), 55 (18), 41 (29).

 

   d) cis- et trans-2,6,6-triméthyl-1-crotonoyl-    I ,2-époxycyclohexane   
   2,6,6 -      triméthyl - 1 -    vinylacétyl - 1,2 - époxycyclohexane (10 g, pureté 95 %) et 1 g d'acétate de sodium dans 50   ml    de dioxanne sont chauffés à 1000 jusqu'à transformation complète du produit de départ en dérivé crotonoyl, le cours de la réaction étant suivi par chromatographie en phase gazeuse (Carbowax ou Silicone,   1800,    3 m). 2h sont généralement requises pour opérer une telle transformation. Après refroidissement et filtration les pro  duits époxydés sont obtenus par distillation (9,8 g; 10 % de dérivé trans- et   90 oxo    de dérivé cis-).



   La séparation des deux isomères peut être effectuée par chromatographie en phase gazeuse:    trans-2,6,6-triméthyl-1-crotonoyl-1,2-époxycyclo-   
 hexane
   Eb.    80 /0,5 Torr;    nz,o = 1,4861; d24  = 0,9849;   
   Cl3H2002    Calculé: C 74,96 H 9,68
 Trouvé : C 75,02 H   9,640/o   
 IR: 1700-1620, 968   cm-t;   
 RMN: 1,0 et 1,06 (6 H, 2 s), 1,08   (3 H, s),      1,92 (3 H,   
 d, J   = 7 cps), 6,1-7,2 (2 H, m), 6 ppm ;   
SM:   M+    = 208 (0,1), m/e: 193 (0,1), 180 (0,1), 165
 (0,1), 151 (5), 139 (12), 125 (14), 111(64), 95 (5),
 82 (12), 69 (100), 55 (80), 41(62), 29 (8).

 

      cis-2,6,6-triméthyl-l -crotonoyl-1,2-époxycyc70hexane   
Eb. 790/0,5 Torr;   n20    = 1,4803; d420 = 0,9833;   C10H20O2    Calculé: C 74,96 H 9,68
 Trouvé : C 75,11 H   9,60 /o   
IR:   1680,1615,748cm-1;   
RMN:   1,00 et 1,07 (6H, 2 s),    1,1(3 H, s), 2,12 (3 H,
 d, J = 7 cps), 6,0-6,57 (2 H, m),   ô   ppm;
SM: M+ = 208 (0,1), m/e: 193 (1), 175 (0,1), 165
 (0,1), 151 (15), 135 (2), 123 (9), 111(6), 95 (4),
   81(2),    69 (100), 55 (18),   41(26),    29 (3). 



  
 



  Process for preparing unsaturated ketones
 The present invention relates to a process for the preparation of odoriferous and flavoring compounds, said compounds being able to be used for the preparation of perfumes and perfumed products and as flavoring agents for modifying the organoleptic properties of foodstuffs for humans and animals, of beverages. , pharmaceutical preparations and tobacco.



   The invention relates to a process for the preparation of compounds of the formula:
EMI1.1
 in which the symbols R1, R2 and R3 represent hydrogen or one of them a lower alkyl radical, for example methyl or ethyl, and the others hydrogen and
R4, R5, R6 and R7 represent hydrogen or one of them a lower alkyl radical, for example methyl or ethyl, and the others hydrogen, characterized in that a compound of formula:

  :
EMI1.2
 containing a double bond in the 2'- or 3'-position of the side chain, the double bond being indicated by the dotted lines, where n is zero or 1, the symbols
R having the same meaning as above, and in which the oxygen of the epoxide function is linked to positions 1- and 2- or 2- and 3- of the ring, as indicated by the dotted lines.



   As acidic agent, it is possible to use acidic, inorganic or organic products, such as hydrochloric, phosphoric or sulfuric acids, acidic clay soils or also tosylic and trifluoroacetic acids.



   The reaction can be carried out in an organic solvent, which is preferably inert, such as, for example, ben zene, dioxane, tetrahydrofuran or ethyl acetate, and preferably at the boiling point of said solvent.



   It has been found that compounds of formula IIa, such as, for example, cis- and trans-2,6,6-trimethyl-1-crotonoyl-1,2-epoxycyclohexane, 2,6,6-trimethyl-1-vinylacetyl- 1,2-epoxycyclohexane or 2,6,6-trimethyl-1 -crotonoyl-2,3-cyclohexane, and IIb, such as 2,6,6-tri methyl-1 - (1-hydroxy-2- butenyl) - 1,2-epoxycyclohexane or 2,6,6-trimethyl-1- (1 -hydroxy-3-butenyl) - 1,2 - epoxy - cyclohexane, which are new compounds, have interesting organoleptic properties .



   Ketones of formula IIa can be prepared from hydroxy compounds of formula:
EMI2.1
 in which the substituents R and the index n have the same meaning as indicated above, according to a process according to which the compounds IIb are oxidized by means of an oxidizing agent. As oxidizing agent, it is possible to use agents known in general for converting secondary hydroxyl functions into ketone functions. In particular, oxygenated derivatives of silver or of a transition element such as chromium, manganese or nickel can be used. It is advantageous to use an alkaline dichromate, for example sodium dichromate, in acidic solution, for example sulfuric solution.



   The compounds IIb used as starting material for the preparation mentioned above can be obtained by epoxidation, using a peracid such as for example peracetic acid, perbenzoic acid, performic acid, monoperphthalic acid or m-chloroperbenzoic acid in a buffered organic solvent, of a compound of the formula
EMI2.2
 in which the substituents R, the index n and the dotted lines have the same meaning as that indicated for formula IIa.



   The above process as well as the preparation of compounds IIIb are illustrated by the following scheme
EMI2.3
  
 The examples which follow illustrate the invention in more detail. In said examples, temperatures are indicated in degrees centigrade.



   Example 1
 Trans-2,6,6-trimethyl-1-crotonoyl -1,3-cyclohexadiene
 A mixture consisting of the cis- and trans isomers 2,6,6-trimethyl-1-crotonoyl-1,2-epoxycyclohexane (10 g), obtained according to the method described below, and 2 g of acidic siliceous earth in 50 ml of dioxane was maintained at 100-105 under a nitrogen atmosphere until complete transformation of the epoxidized derivatives into 2,6,6-trimethyl-1-crotonoyl-1,3-cyclohexadiene, the course of the reaction being followed by chromatography in the gas phase. After filtration, the solution is subjected to distillation. This gives a product at Eb. 60-850 / 0.5 Torr (g.



  8.0) which according to its spectrometric analysis reveals a content of 7.5 g (82 / o) of 2,6,6-trimethyl-1 -crotonoyl-1,3-cyclohexadiene.



   IR: 1670, 1635, 1610,970cm-1
 NMR: 1.01 (6H, s), 1.62 (3H, s), 1.93 (3H, d.d.,
 J = 6.5 and 1.5 cps), 2.07 (2H, d, J = 2.3 cps),
 5.77 (2H, t, J = 2.3 cps), 6.06 (1H, d.q., J =
 16 and 1.5 cps), 6.75 (1H, d.q., J = 16 and 6.5 cps);
 SM: m / e 69-121, 105, 41, 190.



   The above reaction proceeds with the formation of a hydroxylated intermediate which has been defined by gas chromatography; its analytical data are as follows: n2D0 = 1.5049; d4 = 1.018;
   CisHioOo Calculated: C 74.96 H 9.68
 Found: C 74.68 H 9.69%
 IR: 3090 (OH), 1675 (CO), 1620 (C = C), 970 cm-t;
 NMR: 0.72 (3H, s), 0.97 (3H, s), 1.45 (3H, m),
 1.92 (d, J = 7.5 cps), 4.07 (1H, m), 5.7 (1H, m),
 6.35-7.2 (2H, m), ppm;
 MS: M + = 208 (0.1), m / e = 190 (0.1), 175 (0.1), 165
 (0.1), 152 (0.1), 139 (49), 121 (3), 109 (2), 95 (33),
 82 (3), 69 (28), 55 (7), 43 (100), 27 (5).



   The mixture of cis- and trans- isomers of 2,6,6-trimethyl-1-crotonoyl-1,2-epoxycyclohexane, used as starting material in the preparation given above, was obtained as follows:
 a) 2,6,6-trimethyl-1- (1-hydroxy-3-butenyl) -
 I-cyclohexene
 5 g of allyl chloride are added under a nitrogen atmosphere to a suspension of magnesium (28.8 g) in 50 ml of dry ether. According to the usual conditions of a Grignard reaction, are added dropwise to the above mixture, 85 g of allyl chloride and 152 g of p-cyclocitral in 350 ml of dry ether at a rate such as to maintain the mixture at reflux.

  At this temperature, the mixture is left for 3 h and then poured into an aqueous solution of NHLC1. After separation, the ethereal phase gives, following the usual treatments and distillation, 178.1 g (900 / o) of hydroxylated product (97 0 / o purity). Eb. 500 / 0.01 Torr.



      = = 1.4958; d20 = 0.9390;
 b) 2,6,6-trimethyl-1- (1-hydroxy-3-butenyl) - I, 2-epoxycyclohexane
 A mixture of 40 oxo peracetic acid (105 g) and anhydrous sodium acetate (3.0 g) is added to 250 with stirring to a suspension of 2,6,6-trimethyl-1- (1-hydroxy3-butenyl). ) -1-Cyclohexene (97 g) and anhydrous sodium acetate (60 g) in 175 ml of CH2C12 (1.5 h).



   The reaction mixture is left with stirring overnight, then 500 ml of water are added thereto and the organic phase is separated. After the usual washing and drying treatments, 98 g (83%) of the two diastereoisomers of the epoxidized product are obtained by distillation.



  The two isomers can be separated by gas chromatography (Carbowax, 1700, 3m).



   Pic 1: (80 0 / o), Eb. 88-90 / 0.5 Torr; n2D0 = 1.4790; d24 = 0.9772;
 IR: 3450, 1820, 1640,990, 900 cm-1
 NMR: 1.0 and 1.03 (6H, 2 s), 1.42 (3H, s), 2.52 (1H, m), 3.92 (1H, t), 4.7 -6.4 (3H), 6 ppm;
 MS: M + = 210 (0.1), m / e: 192 (0.1), 177 (0.1), 169
 (2), 149 (5), 140 (3), 125 (22), 109 (28), 95 (12),
 83 (23), 69 (46), 55 (36), 43 (100), 27 (12);
 Peak 2: (2O0 / o), Eb. 93-40 / 0.5 Torr;
   n2D0 = 1.4839; d4 = 0.9945;
 IR: 3095, 3060, 1635, 990, 910 cm-1
 NMR: 1.00 and 1.16 (6H, 2 s), 1.33 (3H, s), 3.92 (1H, m), 4.68-6.2 (3H), ppm ;
 SM:

  M + = 210 (0.1), m / e: 192 (0.1), 177 (0.1) 169
 (2), 149 (5), 140 (2), 119 (59), 109 (34), 95 (13),
 83 (25), 69 (47), 55 (42), 43 (100), 27 (13).



   c) 2,6,6-trimethyl-1-vinylacetyl-
 1,2-epoxycyclohexane
 A solution of 2,6,6-trimethyl-1- (1-hydroxy-3-butenyl) -1,2-epoxycyclohexane (178.5 g), prepared according to b), in 265 ml of toluene is added dropwise , with vigorous stirring and at a temperature of 0-50, to a solution of Na2Cr207 (620 g) in 500 ml of concentrated sulfuric acid and 1220 ml of water. The reaction mixture is left at 0-50 for 3 h; it is extracted with ether and after the usual treatments one obtains by evaporation 114.7 g (67 0 / o) of crude product which, after distillation, Eb. 780 / 0.4 Torr, gives 100 g (59 O / o) of an oily product.

  Analysis by gas chromatography shows that the latter has a purity of 95% of 2,6,6trimethyl-1 -vinylacetyl-1, 2-epoxycyclohexane.



     n2nO = 1.4721; d24 = 0.9781;
   C15H20O2 Calculated: C 74.96 H 9.68
 Found: C 74.66 H 9.72%
 IR: 3080, 1700, 1820, 1640, 915, 910 cm-t;
 NMR: 1.02 and 1.05 (6H, 2 s), 1.1 (3H, s), 3.2 (2H,
 m), 4.8-6.2 (3H), 3 ppm;
 MS: M + = 208 (0.1), m / e: 193 (1), 177 (1), 165
 (0.1), 151 (15), 135 (2), 123 (8), 111 (4), 95 (3),
 81 (2), 69 (100), 55 (18), 41 (29).

 

   d) cis- and trans-2,6,6-trimethyl-1-crotonoyl- I, 2-epoxycyclohexane
   2,6,6 - trimethyl - 1 - vinylacetyl - 1,2 - epoxycyclohexane (10 g, purity 95%) and 1 g of sodium acetate in 50 ml of dioxane are heated to 1000 until complete transformation of the product of starting in crotonoyl derivative, the course of the reaction being followed by gas phase chromatography (Carbowax or Silicone, 1800, 3 m). 2 hours are generally required to make such a transformation. After cooling and filtration, the epoxidized products are obtained by distillation (9.8 g; 10% of trans- derivative and 90 oxo of cis- derivative).



   The separation of the two isomers can be carried out by gas chromatography: trans-2,6,6-trimethyl-1-crotonoyl-1,2-epoxycyclo-
 hexane
   Eb. 80 / 0.5 Torr; nz, o = 1.4861; d24 = 0.9849;
   Cl3H2002 Calculated: C 74.96 H 9.68
 Found: C 75.02 H 9.640 / o
 IR: 1700-1620, 968 cm-t;
 NMR: 1.0 and 1.06 (6H, 2 s), 1.08 (3H, s), 1.92 (3H,
 d, J = 7 cps), 6.1-7.2 (2H, m), 6 ppm;
MS: M + = 208 (0.1), m / e: 193 (0.1), 180 (0.1), 165
 (0.1), 151 (5), 139 (12), 125 (14), 111 (64), 95 (5),
 82 (12), 69 (100), 55 (80), 41 (62), 29 (8).

 

      cis-2,6,6-trimethyl-1 -crotonoyl-1,2-epoxycyc70hexane
Eb. 790 / 0.5 Torr; n20 = 1.4803; d420 = 0.9833; C10H20O2 Calculated: C 74.96 H 9.68
 Found: C 75.11 H 9.60 / o
IR: 1680,1615,748cm-1;
NMR: 1.00 and 1.07 (6H, 2 s), 1.1 (3H, s), 2.12 (3H,
 d, J = 7 cps), 6.0-6.57 (2H, m), ppm ppm;
MS: M + = 208 (0.1), m / e: 193 (1), 175 (0.1), 165
 (0.1), 151 (15), 135 (2), 123 (9), 111 (6), 95 (4),
   81 (2), 69 (100), 55 (18), 41 (26), 29 (3).

Claims (1)

REVENDICATION CLAIM Procédé pour la préparation de composés de formule: EMI4.1 dans laquelle les symboles R1, R2 et R3 représentent l'hydrogène ou l'un d'eux un radical alcoyle inférieur, et les autres l'hydrogène et R4, R5, R6 et R7 représentent l'hydrogène ou l'un d'eux un radical alcoyle inférieur, et les autres l'hydrogène, caractérisé en ce qu'on traite par un agent acide un composé de formule: EMI4.2 contenant une double liaison dans la position 2'- ou 3'de la chaîne latérale, la double liaison étant indiquée par les pointillés, dans laquelle n vaut zéro ou 1, les symboles R ayant le même sens que ci-dessus, et dans laquelle l'oxygène de la fonction époxyde est relié aux positions 1- et 2- ou 2- et 3- du cycle, comme indiqué par les pointillés. Process for the preparation of compounds of the formula: EMI4.1 in which the symbols R1, R2 and R3 represent hydrogen or one of them a lower alkyl radical, and the others hydrogen and R4, R5, R6 and R7 represent hydrogen or one of them a lower alkyl radical, and the others hydrogen, characterized in that a compound of formula is treated with an acidic agent: EMI4.2 containing a double bond in the 2'- or 3'-position of the side chain, the double bond being indicated by the dotted lines, where n is zero or 1, the symbols R having the same meaning as above, and in which the oxygen of the epoxide function is linked to positions 1- and 2- or 2- and 3- of the ring, as indicated by the dotted lines. SOUS-REVENDICATIONS 1. Procédé suivant la revendication, caractérisé en ce qu'on utilise comme agents acides des produits acides, minéraux ou organiques, tels les acides chlorhydrique, phosphorique, sulfurique, les terres argileuses acides ou encore les acides tosylique et trifluoracétique. SUB-CLAIMS 1. Process according to claim, characterized in that acidic, inorganic or organic products such as hydrochloric, phosphoric or sulfuric acids, acidic clay or alternatively tosylic and trifluoroacetic acids are used as acidic agents. 2. Procédé suivant la revendication et la sous-revendication 1, caractérisé en ce qu'on utilise comme agent acide l'acide phosphorique ou les terres argileuses acides et qu'on opère dans un solvant organique inerte comme par exemple le dioxanne ou le tétrahydrofuranne. 2. Method according to claim and sub-claim 1, characterized in that phosphoric acid or acidic clay soils are used as the acid agent and that the operation is carried out in an inert organic solvent such as, for example, dioxane or tetrahydrofuran. .
CH555970A 1967-11-09 1970-04-14 Unsaturated cycloaliphatic ketones CH528470A (en)

Priority Applications (18)

Application Number Priority Date Filing Date Title
CH555970A CH528470A (en) 1969-05-07 1970-04-14 Unsaturated cycloaliphatic ketones
CH1236372A CH539682A (en) 1970-04-14 1970-04-14 Unsaturated cycloaliphatic ketones
CH1236272A CH536834A (en) 1970-04-14 1970-04-14 Unsaturated cycloaliphatic ketones
DE2065324A DE2065324C3 (en) 1969-05-07 1970-05-06 2,6,6-Trimethyl-Miydroxy-lcrotonoyl-cyclohexene-Q), its use as a fragrance and flavor and process for its production
FR7016523A FR2042452A1 (en) 1969-05-07 1970-05-06
DE2065322A DE2065322C3 (en) 1969-05-07 1970-05-06 Cycloaliphatically unsaturated epoxy compounds and processes for their preparation
DE19702022216 DE2022216C3 (en) 1969-05-07 1970-05-06 04/17/70 Switzerland 5725-70 Cycloaliphatic unsaturated ketones, process for their production and their use as fragrances and flavorings
DE2065323*A DE2065323A1 (en) 1969-05-07 1970-05-06 CYCLOALIPHATIC UNSATURATED ALCOHOLS
NL7006649.A NL163211C (en) 1969-05-07 1970-05-06 Process for the preparation of unsaturated cycloaliphatic ketones containing preparations, the formed preparations, and process for the preparation of unsaturated cycloaliphatic ketones with organic properties.
GB2221570A GB1305621A (en) 1969-05-07 1970-05-07
DD153631A DD96077A6 (en) 1969-05-07 1970-05-07
JP3858770A JPS553328B1 (en) 1969-05-07 1970-05-07
IT24347/70A IT1047883B (en) 1969-05-07 1970-05-08 PROCEDURES FOR PREPARING UNSATURATED CYCLOALIPHATIC KETONES
US05/503,738 US3975310A (en) 1967-11-09 1974-09-06 Cycloaliphatic unsaturated ketones as odor- and taste-modifying agents
US503794A US3928456A (en) 1967-11-09 1974-09-06 Cycloaliphatic unsaturated ketones as odour- and taste-modifying agents
US05/523,743 US3931326A (en) 1967-11-09 1974-11-14 Alkenoyl-cyclohexadienes
US05/782,536 US4187863A (en) 1967-11-09 1977-03-29 Cycloaliphatic unsaturated ketones as odor and taste modifying agents in tobacco products
US05/900,522 US4226892A (en) 1967-11-09 1978-04-27 Flavoring with cycloaliphatic unsaturated ketones

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH697669A CH520767A (en) 1969-05-07 1969-05-07 Unsaturated cycloaliphatic ketones
CH555970A CH528470A (en) 1969-05-07 1970-04-14 Unsaturated cycloaliphatic ketones

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CH528470A true CH528470A (en) 1972-09-30

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