US3879466A - Bicyclo-{8 2.2.2{9 octa-5,7-dien-2-ones and a process for their preparation - Google Patents

Bicyclo-{8 2.2.2{9 octa-5,7-dien-2-ones and a process for their preparation Download PDF

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US3879466A
US3879466A US436847A US43684774A US3879466A US 3879466 A US3879466 A US 3879466A US 436847 A US436847 A US 436847A US 43684774 A US43684774 A US 43684774A US 3879466 A US3879466 A US 3879466A
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methyl
bicyclo
compounds
sodium
reaction
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Kenneth K Light
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International Flavors and Fragrances Inc
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International Flavors and Fragrances Inc
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Priority to US436847A priority patent/US3879466A/en
Priority to DE19752500772 priority patent/DE2500772A1/de
Priority to NL7500948A priority patent/NL7500948A/xx
Priority to JP50011037A priority patent/JPS50106949A/ja
Priority to FR7502622A priority patent/FR2259079A1/fr
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Priority to FR7519271A priority patent/FR2279709A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • 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
    • C07C45/69—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
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/20—Synthetic spices, flavouring agents or condiments
    • A23L27/203—Alicyclic compounds
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18—Treatment of tobacco products or tobacco substitutes
    • A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
    • A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
    • A24B15/34—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a carbocyclic ring other than a six-membered aromatic ring
    • A24B15/345—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances containing a carbocyclic ring other than a six-membered aromatic ring containing condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/15—Unsaturated ethers containing only non-aromatic carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/164—Unsaturated ethers containing six-membered aromatic rings
    • C07C43/166—Unsaturated ethers containing six-membered aromatic rings having unsaturation outside the aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • 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
    • C07C45/63—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 introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • 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
    • C07C49/457—Saturated compounds containing a keto group being part of a ring containing halogen
    • C07C49/467—Saturated compounds containing a keto group being part of a ring containing halogen polycyclic
    • C07C49/473—Saturated compounds containing a keto group being part of a ring containing halogen polycyclic a keto group being part of a condensed ring system
    • C07C49/477—Saturated compounds containing a keto group being part of a ring containing halogen polycyclic a keto group being part of a condensed ring system having two rings
    • 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
    • C07C49/487—Saturated compounds containing a keto group being part of a ring containing hydroxy groups
    • C07C49/507—Saturated compounds containing a keto group being part of a ring containing hydroxy groups polycyclic
    • C07C49/513—Saturated compounds containing a keto group being part of a ring containing hydroxy groups polycyclic a keto group being part of a condensed ring system
    • 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
    • C07C49/687—Unsaturated compounds containing a keto groups being part of a ring containing halogen
    • C07C49/693—Unsaturated compounds containing a keto groups being part of a ring containing halogen polycyclic
    • 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
    • C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
    • C07C49/723—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups polycyclic
    • C07C49/727—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups polycyclic a keto group being part of a condensed ring system
    • C07C49/733—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups polycyclic a keto group being part of a condensed ring system having two rings
    • 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
    • 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
    • C11B9/0042—Essential oils; Perfumes compounds containing condensed hydrocarbon rings
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D9/00—Compositions of detergents based essentially on soap
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S426/00—Food or edible material: processes, compositions, and products
    • Y10S426/805—Pet food for dog, cat, bird, or fish

Definitions

  • Z is a moiety selected from the group consisting of:
  • R R R R R R R R R R R R and R are the same or different and each is selected from the group consisting of methyl and hydrogen and wherein R is selected fromthe group consisting of methyl, ethyl and hydrogen; and wherein X is selected from the group consisting of bromo, chloro, hydroxyl, benzyloxyl and alkoxyl and a process for preparing such compounds involving intimately admixing a methyl substituted cyclohexadienone having the structure:
  • the compounds thus produced are valuable intermediates used in producing chemical compounds having valuable organoleptic properties; particularly in perfumery, in flavoring foodstuffs and in flavoring tobacco.
  • artifical flavoring agents for foodstuffs have received increasing attention in recent years.
  • such food flavoring agents have been preferred over natural flavoring agents at least in part due to their diminished cost and their reproducible flavor qualities.
  • natural food flavoring agents such as extracts, concentrates, and the like are often subject to wide variations clue to changes in the quality, type and treatment of the raw materials. Such variations can be reflected in the end product and result in unfavorable flavor characteristics in said end product.
  • the presence of the natural product in the ultimate food may be undesirable because of increase tendency to spoil. This is particularly troublesome in food and food uses where such products as dips, soups, chips, sausages, gravies and the like are apt to be stored prior to use.
  • Patchouli alcohol is shown to be prepared via the reaction sequence:
  • dotted line can be a carbon-carbon single bond or a carbon-carbon double bond; and each of R R R R R R R R R and R is the same or different and each represents hydrogen or methyl and wherein R is hydrogen, methyl or ethyl with the proviso that the dashed line is a carbon-carbon single bond when one of R or R is hydrogen.
  • tricyclic alcohols produced using, interalia, the process of my invention are actually reacemic mixture rather than individual steroisomers, such as the case concerning isomers of patchoulic alcohol which are so obtained from patchouli oil.
  • This compound has a warmm patchouli-like fragrance aroma and a woody-balsamic, walnut-kernel and walnut-skin like taste in food flavors.
  • This compound has a warn patchouli fragrance and a wherein X may be either hydroxyl, bromo, chloro, benzyloxyl, and alkoxyl thereby forming a diene compound having the structure:
  • reaction it is best to proceed at a temperature in the range of 200-260C with the most preferred temperature being 220C.
  • the reaction may be carried out in the presence of an inert solvent such as benzene, hexane or cyclohexane (or any other inert solvent) or the reaction may be carried out in the absence of solvent.
  • an inert solvent such as benzene, hexane or cyclohexane (or any other inert solvent) or the reaction may be carried out in the absence of solvent.
  • the acetylenic compound or the cyclohexadienone may be used in excess, it is preferred to use equimolar quantities of each reactant.
  • novel diene compound which is also within the scope of my invention may then be hydrogenated with hydrogen in the presence of a catalyst such as palladium, platinum, nickel or other suitable hydrogenation catalyst.
  • the reaction temperature may be from 20-220C with a temperature range of l00-200being preferred.
  • the reaction is preferably carried out at superatmospheric pressures and pressures in the range of 1-150 atomspheres are suitable. Preferred pressures range from 5-150 atmospheres.
  • the compound produced is one where the dashed line is a carbon-carbon single bond if one of R or R is hydrogen and the compound primarily produced is one where the dashed line is a carbon-carbon double bond if R and R are both methyl.
  • R is methyl or ethyl
  • a reaction pressure of greater than 130 atmospheres is preferred.
  • the ketone thus produced may then be immediately cyclized by treating same with an alkali metal selected from the group consisting of sodium, potassium or lithium.
  • the cyclization may be carried out in diethyl ether, tetrahydrofuran or benzene,
  • the reaction temperature preferred is the reflux temperature of the reaction mass at atmospheric pressure and is a function of the solvent used.
  • the cyclization reaction temperature is approximately 65C.
  • the reaction can be carried out at temperatures ranging from C up to 100C.
  • the mole ratio of ketone to metal is preferably 7:1 although mole ratio of ketone to metal is from 1:1 up to 10:1 may be used.
  • the ketone Prior to cyclization, in the event that X is OH, the ketone must be halogenated with thionyl chloride or any other suitable halogenating agent, for example, thionyl ch1oride-pyridine complex, phosphorous trichloride, phosphorous tribromide, aqueous HCl or aqueous l-lBr.
  • the halogenation reaction may be carried out in the presence or in the absence of an inert solvent such as benzene, toluene, cyclohexane or pyridine.
  • the reaction temperature may range from 20C up to 100C with a reaction temperature of 80C being preferred.
  • the mole ratio of halogenating agent2ketone of 3:1 is preferred when using thionyl chloride and a ratio of 5 :1 is preferred when using aqueous HC1 and l-lBr.
  • cleavage of the ether may be carried out using refluxing hydriodic acid or refluxing hydrobromic acid in acetic acid.
  • alkyl ethers and benzyl ethers are preferably produced by means of one of three techniques, all using the Williamson synethesis, J. Chem.
  • the initial reaction may utilize, for example, the following reactants:
  • reaction mixture is worked-up using routine purification procedures including the unit operations of extraction, crystallization, drying and/or distillation.
  • the individual tricyclic compounds produced using, interalia, the process of my invention can be obtained in puruer form or in substantially pure form by conventional purification techniques.
  • the products can be purified and/or isolated by distillation, extraction, crystallization, preparative chromatographic techniques, and the like. It has been found desirable to purify the tricyclic compounds by fractional distillation under vacuum.
  • tricyclic compounds and mixtures thereof produced using, interalia, the process of my invention can be used alter, vary, fortify, modify, enhance or otherwise improve the flavor of a wide variety of materials which are ingested, consumed, or otherwise organoleptically sensed.
  • alter in its various forms will be understood herein to mean the supplying or imparting of a flavor character or note to an otherwise bland, relatively tasteless substance, or augmenting an existing flavor characteristic where the natural flavor is deficient in some regard or supplementing the existing flavor impression to modify the organoleptic character.
  • a flavoring composition is taken to mean one which contributes a part of the overall flavor impression by supplementing or fortifying a natural or artificial flavor in a material or one which supplies substantially all the flavor and/or aroma character to a consumable article.
  • foodstuff as used herein includes both solid and liquid ingestible materials for man or animals, which materials usually do, but need not, have nutritional value.
  • foodstuffs includes meats, gravies, soups, convenience foods, malt, alcoholic, and other beverages, mile and dairy products, seafoods including fish, crustaceans, mollusks, and the like, candies, vegetables, cereals, soft drinks, snacks, dog and cat food, other veterinary products, and the like.
  • tobacco will be understood herein to mean natural products such as, for example, burley, Vietnamese tobacco, Maryland tobacco, flue-cured tobacco and the like including tobacco-like or tobaccobased products such as reconstituted or homogenized leaf and the like, as well as tobacco substitutes intended to replace natural tobacco, such as lettuce and cabbage leaves and the like.
  • tobaccos and tobacco products include those designed or used for smoking such as in cigarette, cigar, and pipe tobacco, as well as products such as snuff, chewing tobacco and the like.
  • the tricyclic compounds produced using, interalia, the process of my invention are used in a flavoring composition, they can be combined with conventional flavoring materials or adjuvants.
  • conventional flavoring materials or adjuvants are well known in the art for such use and have been extensively described in the literature.
  • conventional materials can be used and broadly include other flavor materials, vehicles, stabilizers, thickeners, surface active agents, conditioners and flavor intensifiers.
  • Such conventional flavoring materials include satuacids; alcohols, including primary and secondary alcohols; esters; carbonyl compounds including ketones and aldehydes; lactones; other cyclic organic materials including benzene derivatives, alicyclic compounds, heterocyclics such as furans, pyridines, pyrazines and the like; sulfur-containing materials including thiols, sulfides, disulfides and the like; proteins; lipids carbohydrates; so-called flavor potentiators such as monosodium glutamate, guanylates, and inosinates; natural flavoring materials such as cocoa, vanilla, and caramel; essential oils and extracts such as anise oil; clove oil; and the like; and artificial flavoring materials such as vanillin; and the like.
  • Propylene glycol The tricyclic compounds produced using interalia, the process of my invention can be used to contribute warm, patchouli-like aromas.
  • the tricyclic compounds of my invention can be formulated into or used as components of a perfume composition.
  • perfume composition is used herein to mean a mixture of organic compounds, including, for example, alcohols, aldehydes, ketones, nitriles, esters, and frequently hydrocarbons which are admixed so that the combined odors of the individual components produce a pleasant or desired fragrance.
  • perfume compositions usually contain: (a) the main note of the bouquet or foundation-stone of the composition; (b) modifiers which round-off and accompany the main note; (c) fixatives which include odorous substances which lend a particular note to the perfume throughout all stages of evaporation, and substances which retard evaporation; and (d) top-notes which are usually lowboiling fresh smelling materials.
  • the individual component will contribute its particular olfactory characteristics, but the overall effect of the perfume composition will be the sum of the effect of each ingredient.
  • the individual compounds of this invention, or mixtures thereof can be used to alter the aroma characteristics of a perfume composition, for example, by highlighting or moderating the olfactory reaction contributed by another ingredient in the composition.
  • the amount of the tricyclic compounds produced using, interalia, the process of my invention which will be effective in perfume compositions depends on many factors, including the other ingredients, their amounts and the effects which are desired. It has been found that perfume compositions containing as little as 2 percent of the tricyclic compounds produced used, interalia, the process of my invention, or even less, can be used to impart a patchouli scent to soaps, cosmetics, and the other products.
  • the amount employed can range up to 50% or higher and will depend on considerations of cost, nature of the end product, the effect de-.
  • the tricyclic compounds produced using, interalia, the process of my invention can be used alone or in a perfume composition as an olfactory component in detergents and soaps, space odorants and deodorants; perfumes; colognes; toilet waters; bath salts; hair preparations such as lacquers, brilliantines, pomades, and
  • odorants such as hand lotions, and sun screens; powders such as talcs, dusting powders, face powder, and the like.
  • powders such as talcs, dusting powders, face powder, and the like.
  • the perfume composition can contain a vehicle or carrier for the tricyclic compounds alone or with other ingredients.
  • vehicle can be a liquid such as an alcohol such as ethanol, 21 glycol such as propylene glycol, or the like.
  • carrier can be an absorbent solid such as a gum or components for encapsulating the composition.
  • reaction mass is then removed from the autoclave and the resultant product is stripped of benzene and distilled at a vapor temperature of l36-138C and 3.03.2 mm. Hg. pres- 40 sure.
  • the structure of the resultant product is confirmed by NMR, IR and mass spectral analyses to be 3,- 3-dimethyl-6-(3-chloropropyl)-bicyclo-[2.2.2]-octa- 5,7-diene-2-one.
  • the reaction mass is stirred for a period of 5 hours at a temperature of 100-115C during which period the pressure in the autoclave varies from 240 up to 260 pounds per square inch.
  • the autoclave is then cooled and the product is removed and distilled. Two products are obtained.
  • the first has a boiling point of 90100C at 1.5 mm. Hg. pressure and is shown by IR, MS and NMR to be 3,3-dimethyl-6-propy1-bicyclo- [2.2.2]-octane-5-one.
  • the second is the desired material, 3,3-dimethy1-6-(3-ch1oropropy1)-bicyc1o-[2.2.2]- oc'tan-Z-one with a boiling point of 131C at 1.5 mm. Hg. pressure weighing 8.2 grns.
  • Tetrahydrofuran 50.0 ml 3,3-dimethyl-6-(3-ch1oropropy1)- 1.4 gm.
  • the reaction mass is refluxed for a period of 4 hours and allowed to stand overnight.
  • the liquid phase is separated from the sodium spheres.
  • the liquid phase is then washed with 100 ml water and acidified with dilute hydrochloric acid.
  • the resultant material is extracted twice with diethyl ether.
  • the combined ether phases are washed with saturated aqueous NaHCO and then dried over anhydrous magnesium sulfate.
  • the solution is stripped of solvent and the remaining residue is separated on a GLC column:
  • Mass Spectral Analysis is as follows: 41, 55, 84, 97, 133, and l 10.
  • GLC shows no trimethylcyclohexadien-l-one remaining and the solvent is removed under vacuum and the residue is distilled to yield about 37 gm. of the product, 1,3,- 3-trimethy1-6-( l-methyl-3-hydroxypropyl)-bicyc1o- [2.2.21-octa-5,7-dien-2-one.
  • the mixture is filtered, stripped of solvent and vacuum distilled, yielding about 27 gm. of the product, 1,3,3-trimethyl-6-(l-methy1-3- hydroxypropyl)-bicyclo-[2.2.2]-octan-2-one.
  • the solution is decanted from the excess sodium and is acidified with 5% I-ICI.
  • the excess acid is neutralized by a single wash with saturated sodium bicarbonate solution.
  • the solution is dried over magnesium sulfate, filtered and stripped, yielding a residue which is recrystallized from hexane to yield about 10 gm. (50%) of racemic patchouli alcohol, mp 39-40 having the structure:
  • EXAMPLE IX preparation of a Soap Composition A total of 100 gm. of soap chips produced from unperfumed sodium base toilet soap made from tallow and coconut oil are mixed with 1 gm. of the perfume composition set forth in Exampel VIII until a substantially homogeneous composition is obtained.
  • the soap composition manifests a characteristic woody cologne perfumed sodium base toilet soap made from tallow and coconut oil is mixed with 1 gm. of octahydro-9,9- dimethyll -methanonaphthalene-l-(2H )-ol until a substantially homogeneous composition is obtained.
  • the soap composition manifests a warm patchouli-like character.
  • EXAMPLE x11 Preparation of a Cosmetic Base EXAMPLE XIII Liquid Detergent Containing octahydro-9,9-dimethyl-l ,6-methanonaphthalenel (2H )-ol
  • Concentrated liquid detergents with a patchouli-like odor containing 0.2%, 0.5% and l.2%-of the product produced in accordance with the process of Example III, octahydro-9,9-dimethyl-l,6-methanonaphthalenel-(2l-I)-ol are prepared by adding the appropriate quantity of octahydro-9,9-dimethyl-l ,6- methanonaphthalene-l-(2I-I)-ol to the liquid detergent known as P-87.
  • the patchouli aroma of the liquid detergent increases with increasing concentration of the octahydro-9,9-dimethyl-l ,6-methanonaphthalene- I (2H)
  • Example XIV Preparation of Cologne and Handkerchief Perfume
  • the composition of Example VIII is incorporated in a cologne having a concentration of 2.5% in aque- 5 ous ethanol; and into a handkerchief perfume in a concentration of 20% (in ethanol).
  • the use of the composition of Example VIII affords a distinct and definite woody cologne aroma having a warm patchouli- Propylene Glycol like character to the handkerchief perfume and to the cologne.
  • EXAMPLE XV Cologne and Handkerchief Perfume
  • the octahydro-9,9-dimethyl-l .6-methanonaphthalene-l-(2l-I)-ol produced by the process of Example 111 is incorporated into a cologne having a concentration of 2.5% in 85% ethanol; and into a handkerchief perfume in a concentration of (in 95% ethanol).
  • the octahydro-9,9-dimethyl-l ,6-methanonaphthalenel (2H)-ol produced in Example III affords a distinct and definite warm patchouli-like aroma to the handkerchief perfume and to the cologne.
  • This formulation is compared to a formulation which does not have octahydro-9,9-dimethyl-l ,6- methanonaphthalene-l-(2H)-ol added to it, at the rate of 20 ppm in water.
  • the formulation containing octahydro-9,9-dimethyl-l ,6-methanonaphthalenel -(2I-I )-ol has a woody-balsamic, fresh walnut kernel and walnut skin-like taste and, in addition, has a fuller mouthfeel and longer lasting tast.
  • the flavor that has added to it octahydro-9,9-dimethyl-l,-methanonaphthalene-l-(2H)-ol, is preferred by a group of flavor panelists, and they consider it to be a substantially improved walnut flavor.
  • EXAMPLE XVII Beverage The addition of octahydro-9,9-dimethyl-l ,6- methanonaphthalene-l-(2H)-ol prepared by the process of Example III at the rate of 0.3 ppm to a commercial Cola beverage gives the beverage a fuller woodybalsamic long lasting taste and adds to the pleasant top notes of the beverage.
  • Cigarettes are produced using the following tobacco formulation:
  • the following tobacco flavor formulation is applied to all of the cigarettes produced with the above tobacco formulation.
  • the experimental cigarettes are found to be more aromatic, more sweet, more bitter, more green, richer and slightly less harsh in the mouth and more cigarette tobacco-like than the control cigarettes.
  • reaction mass is stirred at reflux for a period of 30 minutes. After the 30 minute period, the sodium sand coagulates into one lump. Stirring is continued at reflux for a period of 3 additional hours. The mixture is then cooled and the liquid is decanted from the sodium. The reaction product is then added to ml of water and the mixture is acidified to a pH of 3 with 5% hydrochloric acid. 50 ml of diethyl ether is then added and the layers are then separated. The aqueous layer is extracted once with 50 ml of diethyl ether.
  • Mass spectral analysis is as follows: m/e 70, 105, 106, 42, 117, 91.
  • Infra-red analysis shows a characteristic peak at 1709 cm.
  • Mass spectral analysis is as follows: m/e 82, 170, 171, 41, 242 (Parent peak).
  • the mixture is heated to C while stirring vigorously.
  • the stirring is ceased and the heat source is removed after which time the mixture is cooled using an ice bath.
  • the sodium dispersion temperature reaches 30C, the xylene isdecanted and replaced with 50 gms. of tetrahydrofuran.
  • the resulting mixture is refluxed and 11 gm. of 1,3,3-trimethyl-6-(3- chloropropy1)-bicyclo-[2.2.2]-octan-2-one are added.
  • the reaction mass is then maintained at reflux for a period of 3 hours with moderate stirring.
  • the sodium remains disperseduntil 5 minutes before reflux is discontinued where upon it coagulates into a large ball.
  • the heat source is then removed and stirring is ceased.
  • the reaction mass is decanted from the sodium, acidified to a pH of 3 with 5% of hydrochloric acid and then neutralized to a pH 7 with a sodium bicarbonate solution.
  • the organic layer is separated from the aqueous layer,
  • EXAMPLE XXVIII Diels Alder Reaction Product of 3-hexyn-l-ol and 2,2-dimethyl cyclohexa-3,5-dien-l-one Ingredients Parts by Weight 2.2-Dimethylcyclohexa-3 ,S-dienl-one 3-Hexyn-1-ol Benzene 12.2 grns. (0.10 moles) 19.6 gms. (0.20 moles) 300 mil
  • the ingredients in the autoclave are stirred at a temperature of from 210C up to 230C for a period of 7 hours while the pressure within the autoclave is maintained at 245 pounds per square inch gauge.
  • the autoclave is sealed and the reaction mass is stirred for a period of hours at 220C.
  • the reaction mass is then removed from the autoclave and stripped of solvent on a rotary evaporator.
  • a GLC sample of the material shows no 2,2,6-trimethyl-cyclohexadienone remaining 41 inch X 10 feet, 10% carbowax; 80C-220C at 8C/min.). The residue (55 gms.) is
  • Mass spectral analysis is as follows: m/e 82, 170,-
  • NMR analysis is as follows: 0.91(s,3H), l.07'(s,3H), 1.1l(s,3H-), 1.4-2.1 (signal for 12H), 3.47 (t,2l-l) ppm.
  • the mixture is heated to 90C while stirring vigorously.
  • the stirring is ceased and the heat source is removed after which time the mixture is cooled using an ice bath.
  • the sodium dispersion temperature reaches 30C, the xylene is decanted and replaced with 50 gms. of tetrahydrofuran.
  • the resulting mixture is refluxed 'and l 1 gms. of 1,3,3-trimethyl-6-(3- chloropropyl)-bicyclo-[2.2.2]-octan-2-one are added.
  • the reaction mass is then maintained at reflux for a period of 3 hours with moderate stirring.
  • the sodium remains dispersed until 5 minutes before reflux is discontinued where upon it coagulates into a large ball.
  • the heat source is then removed and stirring is ceased.
  • the reaction mass is decanted from the sodium, acidified to a pH of 3 with 5% of hydrochloric acid and then neutralized to a pH 7 with a sodium bicarbonate solution.
  • the organic layer is separated from the aqueous layer, and the aqueous layer is extracted four times with 100 ml portions of diethyl ether and vacuum distilled at a temperature of 120 and a pressure of 0.6 mm.
  • Mass spectral, IR and NMR analyses yield the data that the major product, obtained in 64% yield, is the title compound having the structure:
  • Mass spectral anaylsis is as follows: m/e 208 (Parent Peak), 41, 84,124, 81.
  • EXAMPLE XXXV A Preparation of 4-pentyn-l-yl-benzyl ether from potassium-4-pentyn-1-oxide An alcoholic solution of potassium-4-pentyn-l-oxide is prepared by adding 4-pentyn-1-ol 170 gms.) to a solution of 47 gms. of potassium in 500 cc of 1,2-
  • the autoclave is sealed and pressurized to pounds per square inch with hydrogen.
  • the reaction mass is heated to C and the pressure rises to 220 pounds per square inch. Heating and stirring is continued until GLC or mass spectral analyses indicates reaction is complete (about 20 hours).
  • the autoclave is vented and the reaction mass is filtered and stripped of solvent, yielding 21 gms. of residue. Distillation under vacuum gives the title material.
  • Mass spectral analysis is as follows: m/e 82, 170, 171, 41, 242 (Parent Peak).
  • the sodium remains dispersed until 5 minutes before reflux is discontinued where upon it coagulates into a large ball.
  • the heat source is then removed and stirring is ceased.
  • the reaction mass is decanted from the sodium, acidified to a pH of 3 with 5% of hydrochloric acid and then neutralized to a pH 7 with a sodium bicarbonate solution.
  • the organic layer is separated from the aqueous layer, and the aqueous layer is extracted four times with ml portions of diethyl ether and vacuum distilled at a temperature of C and a pressure of 0.6 mm.
  • Mass spectral, IR and NMR analyses yield the data that the major product, obtained in 64% yield, is the title compound having the structure:
  • Mass spectral analysis is as follows: m/e 208 (Parent Peak),4l,84, 124,81.
  • NMR analysis is as follows: 0.83(s,3H), 1.07(s,3l-I), l.10(s,3H), 1.0-2.0 (Complex signals), 14H) ppm.
  • Z is a moiety selected from the group consisting of R T Ra wherein each of R R R R R R R R R R and R is the same or different and each represents a moiety selected from the group consisting of methyl and hydrogen; wherein R is selected from the group consisting of hydrogen, methyl and ethyl and wherein X is selected from the group consisting of bromo, chloro, hydroxyl, benzloxyl and alkoxyl.
  • each of R R R R and R is methyl and each of R R R R R and R is hydrogen 4.
  • each of R R R R and R is methyl; wherein each of R R R R R and R is hydrogen and wherein X is hydroxyl.
  • Z is a moiety selected from the group consisting of and wherein each of R R R R R R R R R R R R R R 3 with an acetylenic compound having the structure: and R is the same or different and each represents a moiety selected from the group consisting of methyl and hydrogen, wherein R is selected from the group consisting of hydrogen, methyl and ethyl and wherein X is selected from the group consisting of bromo, chloro, hydroxyl, benzyloxyl and alkoxyl.
  • each of R R R R and R is methyl and each of R R R R R and R is hydrogen.
  • each of R R R R and R is methyl; wherein each of R R R R R and R is hydrogen and wherein X is hydroxyl.
  • R R R R R R R R R R R R and R is the same or different and each represents a moiety selected from the group consisting of methyl and hydrogen; wherein R, is selected from the group consisting of hydrogen, methyl and ethyl; and wherein X is selected from the group consisting of bromo, chloro, hydroxyl, benzyloxyl and alkoxyl.

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US436847A 1974-01-28 1974-01-28 Bicyclo-{8 2.2.2{9 octa-5,7-dien-2-ones and a process for their preparation Expired - Lifetime US3879466A (en)

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US436848A US3907908A (en) 1974-01-28 1974-01-28 Novel tricyclic alcohols, novel uses of tricyclic alcohols and processes for preparing same
US436847A US3879466A (en) 1974-01-28 1974-01-28 Bicyclo-{8 2.2.2{9 octa-5,7-dien-2-ones and a process for their preparation
DE19752500772 DE2500772A1 (de) 1974-01-28 1975-01-10 Neue verbindungen, verfahren zu deren herstellung und deren verwendung
NL7500948A NL7500948A (nl) 1974-01-28 1975-01-27 Werkwijze voor het bereiden van cyclische verbindingen, werkwijze voor het veranderen van de smaak en/of geur van verbruiksmateri- alen en werkwijze voor het bereiden van smaak- en/of geurpreparaten.
JP50011037A JPS50106949A (cs) 1974-01-28 1975-01-28
FR7502622A FR2259079A1 (cs) 1974-01-28 1975-01-28
FR7519271A FR2279709A1 (fr) 1974-01-28 1975-06-19 Nouveaux bicyclooctadienes et leur procede de preparation
US05/614,078 US3996169A (en) 1974-01-28 1975-09-17 Perfume uses of tricyclic alcohols and processes

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2282419A1 (fr) * 1974-08-23 1976-03-19 Firmenich & Cie Composes sesquiterpeniques, leur utilisation a titre d'ingredients parfumants et procede pour la preparation desdits composes
US3989760A (en) * 1974-07-03 1976-11-02 International Flavors & Fragrances Inc. Tricyclic alcohols and lithium salts thereof
US4041084A (en) * 1974-07-03 1977-08-09 International Flavors & Fragrances Inc. Tricyclic alcohols
US4064184A (en) * 1976-11-11 1977-12-20 International Flavors & Fragrances Inc. Norbornanol derivatives
US4064181A (en) * 1973-02-28 1977-12-20 Societe Anonyme Roure Bertrand Dupont Preparation of novel ethers
US4076853A (en) * 1977-02-04 1978-02-28 International Flavors & Fragrances Inc. Flavoring with substituted norbornane derivatives
US4128729A (en) * 1977-03-23 1978-12-05 International Flavors & Fragrances Inc. Bicyclo[2.2.2]-octene derivatives and mixtures thereof
US4139650A (en) * 1974-07-03 1979-02-13 International Flavors & Fragrances Inc. Flavoring with a tricyclic alcohol
US4166916A (en) * 1977-03-23 1979-09-04 International Flavors & Fragrances Inc. Substituted bicyclooctenemethanols
US4167947A (en) * 1977-03-23 1979-09-18 International Flavors & Fragrances Inc. Substituted bicyclooctenemethanols, process for producing same and uses of same for augmenting or enhancing the organoleptic properties of smoking compositions
US4339467A (en) * 1980-08-29 1982-07-13 International Flavors & Fragrances Inc. Flavoring with methyl substituted oxobicyclo-4,4,0-decane derivatives
US4439354A (en) * 1980-11-13 1984-03-27 International Flavors & Fragrances Inc. Tricyclic alcohols, ethers and esters, process for preparing same and use thereof in augmenting or enhancing the organoleptic properites of consumable materials
US4909854A (en) * 1980-11-13 1990-03-20 International Flavors & Fragrances Inc. Process for augmenting or enhancing the aroma or taste of smoking tobacco or smoking tobacco articles using tricyclic alcohols, ethers and/or esters and smoking tobacco compositions and articles so modified

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Publication number Priority date Publication date Assignee Title
US4002691A (en) * 1973-09-27 1977-01-11 Ethyl Corporation Polycyclic compounds
JPS5111751A (en) * 1974-07-16 1976-01-30 Kao Corp 44 homoisotsuisuchirukarubinooruno seizoho
US4371461A (en) * 1980-10-02 1983-02-01 The Procter & Gamble Company Liquid detergent compositions with tertiary alcohol skin feel additives
US4549971A (en) * 1982-03-26 1985-10-29 International Flavors & Fragrances, Inc. Methyl substituted pinyl oxopentenes, organoleptic uses thereof and process for preparing same
US4424378A (en) 1982-03-26 1984-01-03 International Flavors & Fragrances Inc. Methyl substituted pinyl oxopentenes, organoleptic uses thereof and process for preparing same
US4510340A (en) * 1982-07-08 1985-04-09 International Flavors & Fragrances, Inc. Methyl substituted pinyl oxopentenes, organoleptic uses thereof and process for preparing same

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US3173942A (en) * 1958-07-23 1965-03-16 Polaroid Corp Dienoic acid amides
US3711553A (en) * 1968-03-15 1973-01-16 Hoffmann La Roche Tricyclic ketones

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BE788301A (fr) * 1971-09-01 1973-03-01 Roure Bertrand Fils & Justin S Alcool tricyclique

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US3173942A (en) * 1958-07-23 1965-03-16 Polaroid Corp Dienoic acid amides
US3711553A (en) * 1968-03-15 1973-01-16 Hoffmann La Roche Tricyclic ketones

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4064181A (en) * 1973-02-28 1977-12-20 Societe Anonyme Roure Bertrand Dupont Preparation of novel ethers
US3989760A (en) * 1974-07-03 1976-11-02 International Flavors & Fragrances Inc. Tricyclic alcohols and lithium salts thereof
US4041084A (en) * 1974-07-03 1977-08-09 International Flavors & Fragrances Inc. Tricyclic alcohols
US4139650A (en) * 1974-07-03 1979-02-13 International Flavors & Fragrances Inc. Flavoring with a tricyclic alcohol
FR2282419A1 (fr) * 1974-08-23 1976-03-19 Firmenich & Cie Composes sesquiterpeniques, leur utilisation a titre d'ingredients parfumants et procede pour la preparation desdits composes
US4011269A (en) * 1974-08-23 1977-03-08 Firmenich S.A. Process for the preparation of sesquiterpenic derivatives
US4107094A (en) * 1976-11-11 1978-08-15 International Flavors & Fragrances Inc. 3,3-Dimethyl 2(3-butenyl) norbornanol-2 perfume compositions
US4089986A (en) * 1976-11-11 1978-05-16 International Flavors & Fragrances Inc. Flavoring with norbornanol derivatives
US4064184A (en) * 1976-11-11 1977-12-20 International Flavors & Fragrances Inc. Norbornanol derivatives
US4076853A (en) * 1977-02-04 1978-02-28 International Flavors & Fragrances Inc. Flavoring with substituted norbornane derivatives
US4128729A (en) * 1977-03-23 1978-12-05 International Flavors & Fragrances Inc. Bicyclo[2.2.2]-octene derivatives and mixtures thereof
US4166916A (en) * 1977-03-23 1979-09-04 International Flavors & Fragrances Inc. Substituted bicyclooctenemethanols
US4167947A (en) * 1977-03-23 1979-09-18 International Flavors & Fragrances Inc. Substituted bicyclooctenemethanols, process for producing same and uses of same for augmenting or enhancing the organoleptic properties of smoking compositions
US4339467A (en) * 1980-08-29 1982-07-13 International Flavors & Fragrances Inc. Flavoring with methyl substituted oxobicyclo-4,4,0-decane derivatives
US4439354A (en) * 1980-11-13 1984-03-27 International Flavors & Fragrances Inc. Tricyclic alcohols, ethers and esters, process for preparing same and use thereof in augmenting or enhancing the organoleptic properites of consumable materials
US4909854A (en) * 1980-11-13 1990-03-20 International Flavors & Fragrances Inc. Process for augmenting or enhancing the aroma or taste of smoking tobacco or smoking tobacco articles using tricyclic alcohols, ethers and/or esters and smoking tobacco compositions and articles so modified

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FR2259079A1 (cs) 1975-08-22

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