CH575362A5 - Tricyclic undecane derivs - useful as perfume ingredients and organoleptic modifiers to replace natural etherial oils - Google Patents
Tricyclic undecane derivs - useful as perfume ingredients and organoleptic modifiers to replace natural etherial oilsInfo
- Publication number
- CH575362A5 CH575362A5 CH355974A CH355974A CH575362A5 CH 575362 A5 CH575362 A5 CH 575362A5 CH 355974 A CH355974 A CH 355974A CH 355974 A CH355974 A CH 355974A CH 575362 A5 CH575362 A5 CH 575362A5
- Authority
- CH
- Switzerland
- Prior art keywords
- tricyclic
- undecane
- derivs
- useful
- formula
- Prior art date
Links
- 239000002304 perfume Substances 0.000 title abstract description 6
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 title 2
- 239000004615 ingredient Substances 0.000 title 1
- 239000003921 oil Substances 0.000 title 1
- 239000003720 organoleptic modifier Substances 0.000 title 1
- 238000000034 method Methods 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 150000001844 chromium Chemical class 0.000 claims 1
- 238000006213 oxygenation reaction Methods 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- 241000208125 Nicotiana Species 0.000 abstract 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 abstract 1
- 125000002252 acyl group Chemical group 0.000 abstract 1
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 239000012437 perfumed product Substances 0.000 abstract 1
- 239000000825 pharmaceutical preparation Substances 0.000 abstract 1
- 239000000344 soap Substances 0.000 abstract 1
- 239000000341 volatile oil Substances 0.000 description 9
- 150000002576 ketones Chemical class 0.000 description 8
- IJGMVUXEZUEDJR-UHFFFAOYSA-N 7,7-dimethyl-8-methylideneoctahydro-1h-3a,6-methanoazulene-3-carboxylic acid Chemical compound C=C1C(C)(C)C(C2)CCC32C(C(O)=O)CCC31 IJGMVUXEZUEDJR-UHFFFAOYSA-N 0.000 description 7
- KYWIYKKSMDLRDC-UHFFFAOYSA-N undecan-2-one Chemical compound CCCCCCCCCC(C)=O KYWIYKKSMDLRDC-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000000746 purification Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 235000007769 Vetiveria zizanioides Nutrition 0.000 description 4
- 244000284012 Vetiveria zizanioides Species 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- XMUJIPOFTAHSOK-UHFFFAOYSA-N undecan-2-ol Natural products CCCCCCCCCC(C)O XMUJIPOFTAHSOK-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- -1 potassium aluminum hydride Chemical compound 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- PFFITEZSYJIHHR-UHFFFAOYSA-N 2-methyl-undecanoic acid Chemical compound CCCCCCCCCC(C)C(O)=O PFFITEZSYJIHHR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- IJGMVUXEZUEDJR-RTWAVKEYSA-N Zizanoic acid Chemical compound C=C1C(C)(C)[C@@H](C2)CC[C@]32[C@@H](C(O)=O)CC[C@@H]31 IJGMVUXEZUEDJR-RTWAVKEYSA-N 0.000 description 1
- IJGMVUXEZUEDJR-BLTAXRJOSA-N Zizanoic acid Natural products O=C(O)[C@@H]1[C@]23[C@@H](C(=C)C(C)(C)[C@@H](C2)CC3)CC1 IJGMVUXEZUEDJR-BLTAXRJOSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 235000019568 aromas Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000012729 immediate-release (IR) formulation Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- HABRKYMFOVMIBP-UHFFFAOYSA-N undecan-2-yl acetate Chemical compound CCCCCCCCCC(C)OC(C)=O HABRKYMFOVMIBP-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/16—Unsaturated compounds
- C07C61/35—Unsaturated compounds having unsaturation outside the rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/647—Unsaturated compounds containing a keto groups being part of a ring having unsaturation outside the ring
- C07C49/653—Unsaturated compounds containing a keto groups being part of a ring having unsaturation outside the ring polycyclic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Abstract
Cpds. of formula: (in which the double bond is opt. m, n and p=0 or 1, X, if taken together, =O or, if taken separately, one X=acyl-, hydroxyl O-acyl, CH2OH-, CH2-O-acyl, or COO-alkyl gp. and the other X=H, and (i) R= low alkyl if m=p=0 and n=1; (ii) R=low alkylene if m=n=1 and p=0; or (iii) one of R and R1=low alkyl and the other =H if m=n=p=1). are added in small amts. to improve or modify the organoleptic props of perfumes, perfumed products, drinks, foodstuffs, pharmaceutical preparations, soap animal feeds, tobacco drinks, etc.
Description
Le composé carbonylé tricyclique de formule
EMI1.1
est un composé d'origine naturelle. La 7,7-diméthyl-6-méthylène tricyclo[6.2.1.01-5]undécane-2-one a été en effet identifiée dans l'huile essentielle de vétiver, s'y trouvant à raison de 0,1 à 0,5%, selon la provenance de ladite huile essentielle [voir à ce sujet: The Flavour Industry 1, 623 (1970) et Perfume and Essential
Oil Records 60, 307 (1969)].
On a récemment découvert que la 7,7-dimèthyl-6-méthylène- tricyclo[6.2. 1.01 '5]undécane-2-one possède, à l'état pur, une odeur à caractère boisé originale, très franche et très intense. Cette odeur est en outre très stable et parfaitement reproductible, alors que celle de l'huile essentielle naturelle, résultant de la combinaison des notes olfactives d'un très grand nombre de constituants odoriférants, varie selon la provenance, les méthodes d'extraction ou la pureté de ladite huile essentielle.
Grâce à ses qualités olfactives originales, la cétone tricyclique susmentionnée possède en parfumerie un champ d'application très vaste, nettement plus diversifié que celui de l'huile essentielle de vétiver, permettant notamment de créer des notes olfactives à caractère boisé totalement inédites. Ladite cétone tricyclique possède également un effet olfactif renforçateur et fixateur particulièrement apprécié.
Isolée au moyen d'un procédé fort coûteux et extrêmement complexe, comprenant notamment plusieurs distillations successives sur colonne à pouvoir séparateur élevé, ainsi que de nombreuses chromatographies sur colonne, ladite cétone est actuellement hors de prix pour l'industrie des parfums, comme pour celle des arômes.
La présente invention apporte précisément une solution au problème posé par l'obtention rationnelle de la cétone tricyclique mentionnée ci-dessus.
Au moyen du procédé objet de la présente invention, procédé de synthèse original, industriellement et économiquement plus avantageux que l'isolation de la cétone susmentionnée à partir de l'huile essentielle de vétiver, il est désormais possible de mettre à la disposition de l'industrie des parfums ou des arômes, une 7,7diméthyl-6-méthylène-tricyclo[6.2. 1.01 '5]undécane-2-one pratiquement pure, supprimant ainsi les difficultés d'approvisionnement, de stockage et de purification inhérentes à l'huile essentielle d'origine naturelle.
La présente invention a en effet pour objet un procédé pour la préparation d'un composé carbonylé tricyclique de formule
EMI1.2
caractérisé en ce qu'on traite un composé de formule
EMI1.3
dans laquelle l'un des symboles X représente un groupe COOH et l'autre un atome d'hydrogène au moyen de tétracétate de plomb dans l'acide acétique pour obtenir un composé de formule
EMI1.4
dans laquelle l'un des symboles X représente un groupe O-acétyle et l'autre un atome d'hydrogène, on hydrolyse ensuite l'ester lla ainsi préparé pour en obtenir l'alcool correspondant et finalement oxyde l'alcool ainsi obtenu.
Ledit procédé consiste en fait à préparer la cétone tricyclique susmentionnée à partir d'un produit de départ relativement bon marché, l'acide 7,7-diméthyl-6-mèthylène-tricyclo[6.2. 1.01 .S] undécane-2-ylcarboxylique, également connu sous le nom d'acide vétivénique ou zizanoïque. Ce composé peut être en effet obtenu en très grandes quantités et à un prix de revient extrêmement bas, en tant que sous-produit résultant de la purification de l'huile essentielle de vétiver.
Comme indiqué ci-dessus, la première étape réactionnelle du procédé consiste à traiter l'acide vétivénique II au moyen de tétracétate de plomb. Ce traitement s'effectue selon les méthodes usuelles, comme indiqué par exemple dans J. Amer,Chem. Soc.
83, 927 (1961).
L'ester ainsi obtenu peut être ensuite converti en alcool correspondant par hydrolyse en milieu acide ou alcalin. On peut également obtenir ledit alcool par réduction de l'ester lia au moyen d'un hydrure ou aluminohydrure de métal alcalin, tel l'hydrure de sodium ou l'aluminohydrure de sodium ou potassium par exemple.
L'oxydation subséquente de l'alcool ainsi préparé peut s'effectuer au moyen des réactifs communément utilisés, pour transformer un alcool secondaire en cétone correspondante. On peut utiliser à cet effet un dérivé oxygéné d'un métal de transition comme le chrome, le nickel ou le manganèse, opérant le cas échéant en présence d'un acide minéral, tel l'acide sulfurique ou phosphorique par exemple, ou en présence d'une base organique, telle la pyridine par exemple. On utilise de préférence le trioxyde de chrome ou un bichromate de métal alcalin, en présence d'acide sulfurique.
L'exemple ci-après illustrera la présente invention de façon plus détaillée. Dans ledit exemple, les températures sont indiquées en degrés centigrades.
Exemple
Préparation de la 7,7-diméthyl-6-méthylène- tricyclof6.2. J .01,5]undécane-2-one.
a) acétate de 7,7-diméthyl-6-métllylène-tricyclo- [6.2.J.01.5]undécane-2-yle:
4,68 g (20 mmole) d'acide 7,7-diméthyl-6-méthylène-tri- cyclo[6.2. 1.01 '5]undécane-2-ylcarboxylique (acide vétivénique) et 16,4 g d'acétate de sodium anhydre, dissous dans 45 ml d'acide acétique, ont été chauffés à 75". On a ensuite ajouté au mélange ci-dessus 12,0 g de tétracétate de plomb en une seule portion, provoquant un dégagement immédiat de CO2. La décarboxylation s'est poursuivie durant 60 mn, le mélange réactionnel étant maintenu à 75". Après refroidissement, on a ajouté 300 ml d'eau et extrait le mélange au moyen de 6 portions de 200 ml de n-pentane.
Après les traitements usuels de lavage, séchage et concentration de la phase organique, on a isolé 4,61 g (92%) d'un produit brut contenant environ 80% d'ester désiré selon l'analyse par chromatographie en phase gazeuse (Carbowax 20M/250 ). Ce produit a été utilisé sans purification ultérieure pour l'étape réactionnelle suivante.
Un échantillon pour analyse a été obtenu après purification par chromatographie sur colonne (gel de silice 0,05-0,2 mm éluant: hexane/acétate d'éthyle 98:2).
[a]2D= = + 16,30 (c= 1,2% dans CHCl3)
IR (CC4): 3085, 1730, 1633, 1240, 1030, 890 cm-l
RMN (CC4): 1,07 (3H, s); 1,10 (3H, s); 1,96 (3H, s); 2,70 (1H, m); 4,60 (1H, large s); 4,78 (1H, large s); 4,95 (1H, d,
J= 5 cps) 6 ppm
SM: m/e= 188 (100), 173 (80), 145 (93), 43 (71).
b) 7,7-diméthyl-6-méthylène-tricyclo[6.2. 1.015]-
undécane-2-ol:
9,7 g (39 mmole) de l'acétate préparé sous lettre a (pureté 80%) ont été chauffés durant 2 h à reflux, en présence de 50 ml
HCI 2N. Après extraction à l'éther, la phase organique finalement lavée, séchée et concentrée selon les méthodes usuelles a donné un résidu de 8,4 g contenant 80% de 7,7-diméthyl-6-méthylène- tricyclo[6.2.1.0.1.5] '5]undécane-2-ol selon l'analyse effectuée par chromatographie en phase gazeuse (Carbowax 20M/250 ).
[2D0= = + 39,3 (e= 0,7% dans CHCI3)
c) oxydation du 7,7-diméthyl-6-méthylène-tricyclo-
[6.2. 51undécane-2-ol:
Une solution d'acide chromique a été préparée comme suit: 100 g (330 mmole) de Na2Cr207.2H2O ont été dissous dans 300 ml d'eau, additionnés ensuite de 135 ml de H2SO4 jonc. et finalement portés à 500 ml avec H2O.
A 5,2 g d'alcool obtenu selon la méthode décrite sous lettre b, dissous dans 120 ml d'éther et maintenus à 0 , on a ajouté, goutte à goutte et sous forte agitation, 52 ml de la solution d'acide chromique préparée ci-dessus. 15 mn après addition, le mélange réactionnel a été versé sur glace, extrait à l'éther, la phase organique étant successivement lavée au moyen d'une solution de
NaHCO3 à 10% dans H2O et d'une solution saturée de NaCI, finalement séchée et concentrée selon les techniques usuelles. On a ainsi obtenu 3,8 g (74%) d'un résidu contenant environ 80% de cétone tricyclique désirée.
Après purification par chromatographie sur colonne (gel de silice - éluant: hexane/aeétate d'méthyle 90:10), on a obtenu une 7,7-diméthyl-6-méthylène-tricyelo[6.2. 1.01 S]undéeane-2-one en tous points identique au produit décrit dans la littérature.
L'acide vétivénique utilisé comme produit de départ dans le procédé ci-dessus peut être utilisé tel qu'obtenu dans le commerce (pureté env. 90%) ou après avoir été purifié comme suit:
50,0 g d'acide vétivénique brut ( Bonga I - commercialisé par K. von Ahlefeldt, Angola) dissous dans 250 ml d'acétone, ont été mélangés à 25 g de cyclohexylamine. Le produit solide ainsi obtenu a ensuite été recristallisé 3 fois dans un mélange acétone/méthanol 10:1 et finalement hydrolysé au moyen d'acide chlorhydrique 2N. On a ainsi obtenu 41,5 g d'acide vétivénique pur (83% - rendement basé sur le produit brut).
F. 76-78 [a]2D0= et 25,9 (c = 1,5% dans CHCl3)
IR (CCl4): 3100, 2800-2400, 1700, 1640, 1462, 1420, 1380, 1365, 1230, 895 cm-l
RMN (CCl4): 1,08 et 1,11 (6H, 2s); 4,66 (1H, m); 4,82 (1H, m);
11,03 (1H, s) 6 ppm
SM: M + = 234; m/e = 219, 164,119.
The tricyclic carbonyl compound of formula
EMI1.1
is a compound of natural origin. The 7,7-dimethyl-6-methylene tricyclo [6.2.1.01-5] undecan-2-one has indeed been identified in the essential oil of vetiver, being there in an amount of 0.1 to 0.5 %, according to the origin of said essential oil [see on this subject: The Flavor Industry 1, 623 (1970) and Perfume and Essential
Oil Records 60, 307 (1969)].
It was recently discovered that 7,7-dimethyl-6-methylene-tricyclo [6.2. 1.01 '5] undecane-2-one has, in its pure state, an original, very frank and very intense woody odor. This odor is also very stable and perfectly reproducible, whereas that of natural essential oil, resulting from the combination of the olfactory notes of a very large number of odoriferous constituents, varies according to the origin, the extraction methods or the purity of said essential oil.
Thanks to its original olfactory qualities, the aforementioned tricyclic ketone has in perfumery a very wide field of application, clearly more diversified than that of the essential oil of vetiver, making it possible in particular to create completely new olfactory notes with a woody character. Said tricyclic ketone also has a particularly appreciated strengthening and fixing olfactory effect.
Isolated by means of a very expensive and extremely complex process, comprising in particular several successive distillations on a column with a high separating power, as well as numerous column chromatographies, said ketone is currently out of price for the perfume industry, as for that of the perfume industry. aromas.
The present invention precisely provides a solution to the problem posed by rationally obtaining the tricyclic ketone mentioned above.
By means of the process which is the subject of the present invention, an original synthetic process, industrially and economically more advantageous than the isolation of the aforementioned ketone from the essential oil of vetiver, it is now possible to make available to the perfume or flavoring industry, a 7,7dimethyl-6-methylene-tricyclo [6.2. 1.01 '5] practically pure undecan-2-one, thus eliminating the difficulties of supply, storage and purification inherent in essential oil of natural origin.
A subject of the present invention is in fact a process for the preparation of a tricyclic carbonyl compound of formula
EMI1.2
characterized in that a compound of formula
EMI1.3
in which one of the symbols X represents a COOH group and the other a hydrogen atom by means of lead tetracetate in acetic acid to obtain a compound of formula
EMI1.4
wherein one of the symbols X represents an O-acetyl group and the other a hydrogen atom, the ester 11a thus prepared is then hydrolyzed to obtain the corresponding alcohol and finally the alcohol thus obtained is oxidized.
Said process consists in fact of preparing the aforementioned tricyclic ketone from a relatively inexpensive starting material, 7,7-dimethyl-6-methylene-tricyclo acid [6.2. 1.01 .S] undecan-2-ylcarboxylic acid, also known as vetivenic or zizanoic acid. This compound can in fact be obtained in very large quantities and at an extremely low cost price, as a by-product resulting from the purification of the essential oil of vetiver.
As indicated above, the first reaction step of the process consists in treating vetivenic acid II with lead tetracetate. This treatment is carried out according to the usual methods, as indicated for example in J. Amer, Chem. Soc.
83, 927 (1961).
The ester thus obtained can then be converted into the corresponding alcohol by hydrolysis in an acidic or alkaline medium. Said alcohol can also be obtained by reducing the ester IIa by means of an alkali metal hydride or aluminum hydride, such as sodium hydride or sodium or potassium aluminum hydride, for example.
The subsequent oxidation of the alcohol thus prepared can be carried out by means of the reagents commonly used, to convert a secondary alcohol into the corresponding ketone. For this purpose, an oxygenated derivative of a transition metal such as chromium, nickel or manganese can be used, where appropriate operating in the presence of a mineral acid, such as sulfuric or phosphoric acid for example, or in the presence of an organic base, such as pyridine for example. Chromium trioxide or an alkali metal dichromate is preferably used in the presence of sulfuric acid.
The following example will illustrate the present invention in more detail. In said example, temperatures are given in degrees centigrade.
Example
Preparation of 7,7-dimethyl-6-methylene-tricyclof6.2. J .01,5] undecan-2-one.
a) 7,7-dimethyl-6-metllylene-tricyclo- [6.2.J.01.5] undecan-2-yl acetate:
4.68 g (20 mmol) of 7,7-dimethyl-6-methylene-tri-cyclo acid [6.2. 1.01 '5] undecan-2-ylcarboxylic (vetivenic acid) and 16.4 g of anhydrous sodium acetate, dissolved in 45 ml of acetic acid, were heated to 75 ". Then added to the above mixture. 12.0 g of lead tetracetate in a single portion, causing immediate release of CO 2. The decarboxylation continued for 60 min, the reaction mixture being maintained at 75 ". After cooling, 300 ml of water was added and the mixture was extracted with 6 x 200 ml portions of n-pentane.
After the usual treatments of washing, drying and concentration of the organic phase, 4.61 g (92%) of a crude product containing approximately 80% of the desired ester were isolated according to the analysis by gas chromatography (Carbowax 20M / 250). This product was used without further purification for the next reaction step.
A sample for analysis was obtained after purification by column chromatography (silica gel 0.05-0.2 mm eluent: hexane / ethyl acetate 98: 2).
[a] 2D = = + 16.30 (c = 1.2% in CHCl3)
IR (CC4): 3085, 1730, 1633, 1240, 1030, 890 cm-l
NMR (CC4): 1.07 (3H, s); 1.10 (3H, s); 1.96 (3H, s); 2.70 (1H, m); 4.60 (1H, broad s); 4.78 (1H, broad s); 4.95 (1H, d,
J = 5 cps) 6 ppm
MS: m / e = 188 (100), 173 (80), 145 (93), 43 (71).
b) 7,7-dimethyl-6-methylene-tricyclo [6.2. 1.015] -
undecan-2-ol:
9.7 g (39 mmol) of the acetate prepared under letter a (80% purity) were heated for 2 h at reflux, in the presence of 50 ml
2N HCI. After extraction with ether, the organic phase finally washed, dried and concentrated according to the usual methods gave a residue of 8.4 g containing 80% of 7,7-dimethyl-6-methylene-tricyclo [6.2.1.0.1.5 ] '5] undecan-2-ol according to the analysis carried out by gas chromatography (Carbowax 20M / 250).
[2D0 = = + 39.3 (e = 0.7% in CHCl3)
c) oxidation of 7,7-dimethyl-6-methylene-tricyclo-
[6.2. 51undecan-2-ol:
A solution of chromic acid was prepared as follows: 100 g (330 mmol) of Na2Cr207.2H2O were dissolved in 300 ml of water, then added with 135 ml of rushed H2SO4. and finally brought to 500 ml with H2O.
To 5.2 g of alcohol obtained by the method described under letter b, dissolved in 120 ml of ether and maintained at 0, was added, dropwise and with vigorous stirring, 52 ml of the chromic acid solution prepared above. 15 min after addition, the reaction mixture was poured onto ice, extracted with ether, the organic phase being successively washed with a solution of
10% NaHCO3 in H2O and a saturated NaCl solution, finally dried and concentrated according to the usual techniques. There was thus obtained 3.8 g (74%) of a residue containing about 80% of the desired tricyclic ketone.
After purification by column chromatography (silica gel - eluent: hexane / methyl acetate 90:10), a 7,7-dimethyl-6-methylene-tricyelo was obtained [6.2. 1.01 S] undéeane-2-one in all points identical to the product described in the literature.
The vetivenic acid used as the starting material in the above process can be used as obtained commercially (purity approx. 90%) or after having been purified as follows:
50.0 g of crude vetivenic acid (Bonga I - marketed by K. von Ahlefeldt, Angola) dissolved in 250 ml of acetone, were mixed with 25 g of cyclohexylamine. The solid product thus obtained was then recrystallized 3 times from a 10: 1 acetone / methanol mixture and finally hydrolyzed with 2N hydrochloric acid. There was thus obtained 41.5 g of pure vetivenic acid (83% - yield based on the crude product).
F. 76-78 [a] 2D0 = and 25.9 (c = 1.5% in CHCl3)
IR (CCl4): 3100, 2800-2400, 1700, 1640, 1462, 1420, 1380, 1365, 1230, 895 cm-l
NMR (CCl4): 1.08 and 1.11 (6H, 2s); 4.66 (1H, m); 4.82 (1H, m);
11.03 (1H, s) 6 ppm
MS: M + = 234; m / e = 219,164,119.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH355974A CH575362A5 (en) | 1972-10-10 | 1972-10-10 | Tricyclic undecane derivs - useful as perfume ingredients and organoleptic modifiers to replace natural etherial oils |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH355974A CH575362A5 (en) | 1972-10-10 | 1972-10-10 | Tricyclic undecane derivs - useful as perfume ingredients and organoleptic modifiers to replace natural etherial oils |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH575362A5 true CH575362A5 (en) | 1976-05-14 |
Family
ID=4258596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH355974A CH575362A5 (en) | 1972-10-10 | 1972-10-10 | Tricyclic undecane derivs - useful as perfume ingredients and organoleptic modifiers to replace natural etherial oils |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH575362A5 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0029259A1 (en) * | 1979-10-09 | 1981-05-27 | Pfw (Nederland) B.V. | A method of preparing tricycloundecane derivatives, these compounds and a perfume composition containing at least one of them |
-
1972
- 1972-10-10 CH CH355974A patent/CH575362A5/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0029259A1 (en) * | 1979-10-09 | 1981-05-27 | Pfw (Nederland) B.V. | A method of preparing tricycloundecane derivatives, these compounds and a perfume composition containing at least one of them |
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