US3911018A - Novel process and products produced by said process - Google Patents

Novel process and products produced by said process Download PDF

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US3911018A
US3911018A US434948A US43494874A US3911018A US 3911018 A US3911018 A US 3911018A US 434948 A US434948 A US 434948A US 43494874 A US43494874 A US 43494874A US 3911018 A US3911018 A US 3911018A
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reaction
amber
mixture
isomer
isomers
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John B Hall
James Milton Sanders
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International Flavors and Fragrances Inc
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International Flavors and Fragrances Inc
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Priority to US434948A priority Critical patent/US3911018A/en
Priority to NLAANVRAGE7401583,A priority patent/NL182075C/xx
Priority to AU65443/74A priority patent/AU476465B2/en
Priority to GB723274A priority patent/GB1436991A/en
Priority to MX704974U priority patent/MX5067E/es
Priority to DE2408689A priority patent/DE2408689C3/de
Priority to MX705074U priority patent/MX5607E/es
Priority to CA193,242A priority patent/CA1029036A/fr
Priority to IT48758/74A priority patent/IT1049269B/it
Priority to FR7406687A priority patent/FR2219140B1/fr
Priority to CH277174A priority patent/CH605539A5/xx
Priority to JP49023215A priority patent/JPS6055484B2/ja
Priority to US529086A priority patent/US3929677A/en
Priority to US529087A priority patent/US3907321A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/02—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains containing only carbon and hydrogen atoms
    • 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
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/527—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings
    • C07C49/553—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings polycyclic
    • 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
    • C11B9/0046—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings
    • C11B9/0049—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings the condensed rings sharing two common C atoms
    • C11B9/0053—Essential oils; Perfumes compounds containing condensed hydrocarbon rings containing only two condensed rings the condensed rings sharing two common C atoms both rings being six-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • ABSTRACT A process for the preparation of mixtures of isomers of octahydro-tetramethyl acetonaphthones comprising reacting myrcene with 3mcthyl3-pentene2 -one to form a substituted acyl cyclohexene Diels-Alder adduct and then cyclizing said Diels-Alder adduct with an acid cyclizing agent.
  • the present invention provides a solution to the aforementioned problem by providing isomer mixtures and a specific isomer and processes for producing same which give rise to unexpectedly intense and persistent natural amber or fruity amber fragrance notes heretofore unknown in the acetonaphthone class of fragrance materials.
  • isomer mixtures and a specific isomer and processes for producing same which give rise to unexpectedly intense and persistent natural amber or fruity amber fragrance notes heretofore unknown in the acetonaphthone class of fragrance materials.
  • materials which have an amber or fruity amber fragrance note which do not discolor with age Such amber or fruity amber fragrance materials as stated above have a wide utilization in the preparation of finished perfume compounds. The materials when they are available from natural sources are subject to wide variations in quality, are expensive and are limited or often in critically short supply.
  • the isomer mixtures and specific isomer of our invention have also been found to modify the smoke side stream and main stream of smoking articles by imparting a sweet, spicey. cedarwood-like aroma to such side streams and main streams.
  • Materials having such properties have been widely sought after in the past but not such materials which are easily available and have relatively low cost have heretofore been discovered.
  • the prior art contains several disclosures of fragrance uses of compounds having structures similar to the compounds contained in the isomer mixtures of our invention and to the specific isomer of our invention.
  • NAME Perfume Properties: Fruity. woody. pineapple-like l', 2'. 3'. 4" 5', 6', 7', X'mctahydro-fl'. 8, t4'( and 3', and iummumkc 5', 5 )-trimethyl-Z'-naphthaldchydc S'lRLI'lURl: OF COMPOUND Perfume Propertiesi 5 O (ireen. huttery. woody STRUCTURE OF COMPOUND NAM 1 1'. 2'. 5'. 4. 5, 6. 7'. 8'-octahydro-3. 5', 5'-(and K 3, 8'. 8'] trimethylfl acetonaphthone Perfume Properties; l.o ⁇ v keyed woody. fruity.
  • This invention relates to the preparation of synthetic amber-like fragrance ingredients for perfumes and cosmetics and for fragrancing the side streams and main streams of smoking articles containing tobacco. More particularly, the invention has to do with a process for the preparation of amber-like fragrance compositions for use in perfumery and in tobacco composed of octahydro-Z', 3', 8', 8'-tetramethyl-(2'or 3' acetonaphthones in which a majority of said acetonaphthones contains the double bond in the 9'-10' position.
  • This invention also covers a novel isomer of octahydrotetramethyl acetonaphthone having the structure:
  • the invention also covers processes for producing isomer mixtures of octahydro-Z', 3', 8', 8'-
  • mixtures produced by the processes of our invention contain from mole percent up to 99 mole percent of compounds having the generic structure:
  • Such a generic structue includes individually compounds having an acetyl group at the 2' position. compounds having an acetyl group at the 3'position and mixtures of such compounds.
  • the generic structures set forth above are also intended to include geometric isomers wherein the acetyl group is eis to the methyl group on the carbon atom adjacent to that bonded to the acetyl moiety and where the acetyl group is "trans to the methyl group on the carbon atom adjacent to that bonded to the acetyl moiety.
  • the processes of our invention give rise to isomer mixtures containing the above-named isomers as well as the isomer having the structure:
  • novel mixtures of our invention are produced by means of a two step reaction:
  • novel isomer mixtures produced thusly can be further separated by standard physical separation techniques (e.g., chromatographic techniques as set forth in Example XIV) or standard chemical techniques (eg. oximation as set forth in Example Xl) or they can themselves be incorporated into tobacco or tabacco flavors or into a wide variety of finished perfume compounds.
  • standard physical separation techniques e.g., chromatographic techniques as set forth in Example XIV
  • standard chemical techniques eg. oximation as set forth in Example Xl
  • they can themselves be incorporated into tobacco or tabacco flavors or into a wide variety of finished perfume compounds.
  • the novel materials of this invention have persistent fragrances more fully described below which adapts them for incorporation into perfume compounds where a distinct amber or fruity amber fragrance note is required. or into tobacco or tobacco flavors where it is desired to modify aromas of the main stream and side stream of a smoking article on smoking by imparting to the aroma of such main stream and side stream. sweet. spicey. cedarwood-like notes.
  • myrcene and 3-methyl3-penten-Z-one are the reactants.
  • Myrcene is generally available at purities of 70'; and upwards and it can be used in this form. It is generally preferred in the practice of this invention to use commercial myrcene [approximately 77% parity) although. obviously. purified myrcene may be used. Such a purification is readily accomplished by fractional distillation
  • the initial reaction may be a thermal Diels-Alder reaction without the use ofa Lewis acid catalyst at a temperature in the range of lZt "lt t)"Cv Preferably. but not necessarily.
  • an antioxidam and polymerization inhibitor such as the mixture of fi-naphthylamine and pyrogallol may be utilized, as set forth in Example of British Pat, No. 896.039 Upon performing the first step of the process of our invention by carrying out a thermal Diels-Alder reaction without the use of a Lewis-acid catalyst. the resulting material will be a mixture of approximately 70 weight percent:
  • Suitable Lewis acid catalysts are aluminum chloride, stannic chloride. titanium tetrachloride. boron trifluoride. and boron trifluoridc complexes such as boron trifluoride etherates.
  • the Lewis acid catalyst concentra tion workable in our process is from 0.5 up to I00 mole percent based on 3-methyl-3'penten-Z-one with the preferred range being 3-8 mole percent.
  • a solvent be used and suitable solvents are toluene. benzene and inert chlorinated hydrocarbon solvents such as chloroform and methylene chloride since they do not take part in the reaction. when using a Lewis acid catalyst.
  • the first reaction is operated at a temperature in the range ofll C up to 50C. preferably C5()C
  • the mole ratio of myrcene to 3-methyI-B-penten-Lonc may be varied from 1:3 to 3:l or even higher. since the excess reagent may be recovered substantially quantitatively. However. for efficiency and economy as to time. the preferred mole ratio is from 1.1:1 up to l.2:l.
  • the reagents and catalyst may be mixed in any order. however. it is preferred to sequentially add 3methyl-3- pentenJ-one and myrcene to a premix of the catalyst and solvent. the use of solvent in this reaction being preferred also.
  • the amount of acid cyelization agent may vary from It) up to 100 weight percent based on the weight of the cyclohexene derivative to be cyclired.
  • the weight percent of acid should be between and weight percent. preferably.
  • reaction temperature may be anywhere between 25% and the reflux temperature of the reaction mixture.
  • the preferred reaction temperature range is between C and l IS C and accordingly toluene is the preferred solvent since its boiling point at atmospheric pressure is l lU C.
  • 'lhe quantity of solvent used in the cyclization reaction may vary from weight percent up to lUtJ weight percent based on the amount ofcyclohexene derivative being cyclized. lt is preferred to use approximately 50 weight percent of solvent.
  • the order of mixing reagents and solvents is not critical.
  • Periods of time of the order of 5-7 hours at temperatures of 7()8()C will yield a mixture wherein isomers having the basic structure(l) will be produced in a quantity of about 8()857z, the remaining isomers having the basic structures (II), (III) and (IV).
  • the cyclization reaction is run for a period of time of approximately l hours, and at 80C greater than 96% of the reaction product has a geometric isomer mixture having the basic structure (I).
  • a temperature of reaction of l lC coupled with a time of reaction of4 hours will also yield a geometric isomer mixture more than 96% of the compounds of which have the basic struc ture (l).
  • a time of reaction of 6 hours coupled with a reaction temperature of l 15C will give rise to a reaction product wherein more than 9992 of the geometric isomers have the basic structure (I ln the event that the first reaction.
  • the Diels-Alder reaction is carried out using a Lewis acid catalyst.
  • the mixture of isomers produced as a result of carrying out the second cyelization reaction on the resulting Diels Alder reaction product has been found to contain a predominant quantity of an isomer having the structure:
  • Example XIV. infra This novel isomer has a characteristic intense fruity-amber note.
  • the above isomers are distinguishable from one another by examination of their respective NMR, infrared, and Raman spectra.
  • the fact that the isomers indicated by formulae l and V have a tetrasubstituted double bond, and the isomers indicated by formulae II, III and IV have a double bond which is only trisubstituted and not tetrasubstituted is apparent from a study of FIGS. 1-6.
  • the two foregoing reactions may be performed in separate reaction vessels or, more preferably, they may be performed in the same reaction vessel whereby the Diels-Alder reaction and subsequent cyclization steps are carried out without isolating the intermediate Diels- Alder adduct, the cyclohexene derivative. Accordingly, when the Diels-Alder reaction is complete, the desired amount of acid is added without any additional solvents, and the reaction mixture is then stirred at the desired temperature until cyclization is complete.
  • the distilled product may be used as is" or it may be further purified by using gas chromatography techniques and/or oximation (see Example XI) followed by recovery of the purified reaction product from the oxime.
  • the reaction product mixtures as well as the specific isomer of our invention are clear liquids with intense and persistent unique amber and fruity-amber odors.
  • the isomer mixtures as well as the novel specific isomer of our invention are particularly suited to use as perfume materials in the preparation of perfume compositions and in tobacco and tobacco flavors as modifers of the aromas of the main stream and side stream of the smoke created on smoking smoking articles containing said tobacco. They are very well adapted to perfumery where an amber or fruity-amber aroma is required. They are adapted to modifying tobacco smoke aromas where sweet. spicey, cedarwood aromas are required in the smoke main stream and side stream.
  • novel isomer of our invention as well as the oetahydrotetramethyl-acetonaphthone isomer mixtures are par ticularly remarkable for their persistent fruity amber and amber odors.
  • auxiliary perfume adjuvants including one or more of many types of odor materials such as hergamot oil vetivert oil, patchouli oil. sandalwood oil. oalt'moss and floral musk
  • the novel materials of this invention can also be combined with the customary perfume auxiliary adjuvants such as natural oils synthetic oils. aldehydes, ketones, earboxylic acid esters. aryl alcohols. alkanols, lactones, saturated hydrocarbons. unsaturated hydrocarbons, fixatives, solvents. dispersants surface active agents, aerosol propellants, and the like.
  • toluene 3-methyl-3-pentenone (2060 g. 959?) is added in 15 minutes to a suspension of aluminum chloride (90 g) in toluene (2 kg). The initial exotherm dies out after ap proximately '7? of the 3methyl-3-pentenone is added. The mass is warmed to 35C. and myrcene (3530 g, 77% was added over a period of 2 hours with external cooling as needed to maintain the reaction mixture at 35 40C. The mixture is stirred at 35 40C for 2 hours 27 g aluminum chloride is added, and the mass is stirred an additional 9 hours at 35 40C.
  • Example 13 EXAMPLE n
  • the product of Example 1 (3 kg, 98.7%) is added over a period of 45 minutes to a well-stirred mixture of 1.5 kg of toluene and 1.5 kg of 85% phosphoric acid maintained at 70 80C.
  • the mixture is stirred vigorously at 70 80C for 5.5 hours and then is cooled and mixed with 3 kg of crushed ice.
  • the organic phase is subsequently washed with sodium chloride solution 10% sodium carbonate solution and saturated sodium chloride solution.
  • the washed organic solution is mixed with triethanolamine (100 g), Primol (50 g) and lonol (3 g) and is rapidly distilled under reduced pressure using a short column.
  • this material shows two major peaks (Varian Aerograph model 200, 10 feet X Ainch, 5% Carbowax K 20 M on chromosorb G, helium flow rate 80 cc per minute, temperature programmed 3S l00200C at l0C/min.), Peak 1 93%. Peak 2 7%. Peaks 1 and 2 are trapped from the above column. The NMR spectra of the two peaks are quite different.
  • the NMR analysis for Peak 1 is set forth in Table l and is as follows:
  • Peak 1 has a slight buttery note with a strong woody amher character Peak 2 is weak, low keyed with a green ⁇ egetahle character
  • EXAMPLE 111 A perfume composition is prepared by admixing the following ingredients in the indicated proportions:
  • Lintt1 ⁇ l Acetate Phen ⁇ l lth ⁇ l Alcohol Pclitgrani 5A (Ill (ontinued Ingredient Amount ((jrantsl Bergamot Oil Alpha Mclhxl lonone 3'rtihh' tetraniethylI'stcclo naphlhones produced h the process separatlultl (ycli/etl HIL' ⁇ L'1U l 1 material produced according to the (anadizln Patent -1115 Issued October 111 197(1 lso Horn (" ⁇ clohex tl Alcohol Ben/ 1 Acetate I'n'Heptfl clopentanonc 5 (TOTAL!
  • This base composition can be admixed with aqueous ethanol. chilled and filtered to produce a finished cologne
  • the cologne so prepared has an amber aroma leaning towards a woody amber note.
  • the base composition can also be used to scent soap or other toilet goods such as lotion aerosol. sprays and the like.
  • EXAMPLE VI Diels-Alder adduct mixture prepared according to the process of Example IV 85% phosphoric acid toluene 250 grams 25H grams The reaction mass is heated to reflux at atmospheric pressure l l8C) and maintained at reflux for a period of 3 A; hours after which time the reaction mass was cooled down. The reaction mass is then washed with one liter portion of water; then two 500 cc portions of water; then one 500 cc portion of 5% sodium carbonate and finally one 500 cc portion of saturated sodium chloride.
  • one of the wavy lines in each of the above structures is a carbon-carbon double bond and the other of the wavy lines in each of the above structures represents a carbon-carbon single bond.
  • reaction mass is washed with two 1 kilo portions of 50C water; then one 250 cc portion of 50C I071 sodium carbonate solution; and finally one 500 gram portion of 50C 15% sodium sulfate solution.
  • 2l5 grams of triethanolamine is added to the reaction mass.
  • the 5 liter reaction vessel is then equipped with stirrer, reflux condenser, ther mometer and Bidwell trap and the mass is then heated to reflux 128C) while removing solvent thereby gradually increasing the pot temperature to C.
  • sampling of the reaction mass and analysis thereof yielded the information that no labile organic halide is present in the reaction mass.
  • the reaction mass is then stripped of solvent, the crude mass weighing [410 grams.
  • the crude product is rushed over and then fractionated after adding 40 grams Primol 1 gram lonol and 10 grams calcium carbonate and purging with nitrogen, at a l l reflux ratio at vapor temperature of l29l3lC and 2.6-2.9 mm. Hg. pressure. Yield 845 grams.
  • the major peak is separated out by GLC analysis in accordance with the same procedure as is set forth in Example II.
  • the Raman spectrum for the major peak (using a Raman spectrometer manufactured by Spex Incorporated of Plainficld. NJ.) is. in part. set forth in FIG. 3.
  • the Raman spectrum indicates a tetrasuhstituted double bond at I679 cm" and a carbonyl group at l7l 1 cm".
  • EXAMPLE 'lll A perfume composition is prepared exactly as in Example [ll except that the mixture ofisomers of 1,2',3,- 4'5'.h',7'.8-octahydro-2',3',8'.8-tetramethyl-2'- aeetonaphthones produced by the process of Example Vll is applied in lieu of the mixture of Example 11 (prior to GLC separation I.
  • This blend is evaluated and found to have a high degree of richness and persistence in its novel natural amber quality.
  • This composition can he admixed with aqueous 95" ethanol (ratio: 95 parts ethanol: parts composition] chilled and filtered to produce a finished cologne.
  • the cologne so prepared has an amber aroma leaning towards a woody amber note.
  • the composition can also he used to scent soap or other toilet goods such as lotion, aerosol, sprays and the like.
  • reaction mass is then stripped off and reaction mass is rushed over at 1-1.5 mm. Hg. pressure and a vapor temperature of ll0l 17C.
  • the rushed over material is then distilled at a vapor temperature of 128 1 32C and a pressure of 2.5 mm. Hg. (reflux ratio 9:1).
  • GLC. NMR. IR and mass spectral analysis yield the information that the resulting product is a mixture of isomers having the generic structure:
  • EXAMPLE Xl A Preparation of Oxime
  • 957 aqueous ethanol and 61 gms. of hydroxylamine sulfate.
  • the re action mass is stirred while a solution of 30 gms. of sodium hydroxide in 30 gms. of water is added slowly. After an additional 35 minutes of stirring, the reaction mass is filtered to remove the suspended sodium sulfate.
  • the resulting alcoholic solution of hydroxylamine is charged to a two liter three neck flask and l 15 gms. of material prepared as in Example Vll (prior to GLC separation] is added. The resultant mixture is stirred vigorously at reflux for approximately 8.5 hours. The solution is cooled to room temperature and the resulting crystals are filtered and air dried to give 70 gms of oxime. The oxime is crystalized twice from toluene (23 ml toluene per gram oxime) to get 50 gms. purified ox- B.
  • This material is evaluated as being a very clean version of the material prepared in accordance with the process of Example VII, significantly better than the material which contains other isomers.
  • Example XII A perfume composition is prepared exactly as in Example lll except that the mixture of isomers of l ',2',3',- 4,5,6,7,8'-octahydro-2,3',8',8'-tetramethyl-2- acetonaphthones produced by the process of Example X is employed in lieu of the mixture of Example ll.
  • This blend is evaluated and found to have a high degree of richness and persistence in its novel natural amber quality.
  • This composition can be admixed with aqueous ethanol, chilled and filtered to produce a fin ished cologne.
  • the cologne so prepared has a citrus aroma leaning towards an amber note.
  • the composition can also be used to scent soap or other toilet goods such as lotion, aerosol, sprays and the like.
  • EXAMPLE Xlll The Diels-Alder reaction product of Example IV (250 gms. thereof) is added over a period of 50 minutes to a well stirred mixture of l000 gms. of toluene and 145 gms. of boron trifluoride diethyl ether complex in a 3 liter reaction vessel equipped with stirrer, reflux condenser. thermometer, and addition funnel. The reaction mass is then maintained at 485 lC over a period of 13 hours and is then cooled to less than C with stirring. While being maintained at 25C, 600 gms. of IO aqueous sodium hydroxide is added to the reaction mass. The resulting organic layer is then washed with 10% sodium hydroxide and water.
  • the reaction mass is then stripped of solvent thereby yielding 332 gms. of crude product.
  • the crude product is fractionated at a vapor temperature of l25l 28C and a pressure of 2.2 mm. Hg. after 30 gms. of Primol, 1 gm. of lonol and 5 gms. of calcium carbonate is added thereto. In this way, a product is obtained containing geometric isomers having the basic generic structure:
  • EXAMPLE XIV The major GLC peak of the product of Example VlI is trapped from a 500 foot X 0.03 inch, SF96 (a nonpolar silicone polymer manufactured by Analabs Inc. of R0, Drawer 5397, Hamden Conn. 06518) column (L at 185C isothermal. This peak is 86.171 of the total material produced (according to GLC on a similar column). The trapped peak is 99.992 one peak when rechromatographed on a 500 foot X 0.03 inch, SF96 column programmed -l C at 4C/min.
  • Example XI or Example XIV produced by the process of Example XI or Example XIV is employed in lieu of the mixture of Example II.
  • the foregoing blend is evaluated and found to have a high degree of richness and persistence in its novel natural amber quality.
  • This composition can be admixed with aqueous 957: ethanol (ratio: parts ethanol:5 parts composition) chilled and filtered to produce a finished cologne.
  • the cologne so prepared has an amber aroma leaning towards a woody amber note.
  • the composition can also be used to scent soap or other toilet goods such as lotion, aerosol, sprays and the like.
  • EXAMPLE XVIII Preparation of a Detergent Composition A total of I00 gms. ofa detergent powder sold under the trademark RINSO are mixed with 0.15 gms. of a perfume composition containing the mixture obtained in Example XV until a substantially homogeneous com position having an amber fragrance is obtained.
  • EXAMPLE XIX Preparation of a Cosmetic Base
  • a cosmetic powder is prepared by mixing 100 gms. of talcum powder with (1.25 gms. of the perfume com position of Example XV in a ball mill.
  • a second cosmetic powder is similarly prepared except that the mixture produced in Example XV is replaced with the product produced in Example XI or Example XIV.
  • the cosmetic powder containing the material of Example XV has an amber fragrance.
  • the cosmetic powder produced using the material produced in Example XI or Example XIV has a fruity amber character.
  • EXAMPLE XX Liquid Detergent Concentrated liquid detergents with fruity amber odor containing (1.2%. 0.57: and LEW of the product produced in accordance with Example XI or Example XIV are prepared by adding the appropriate quantity of the specific isomer so produced to liquid detergent known as P-B'l. The fruity amber aroma of the liquid detergent increases with increasing concentration of the isomer of Example XI or Example XIV.
  • Example XXI Preparation of Cologne and Handkerchief Perfume
  • the composition of Example XV is incorporated in a cologne having a concentration of 2.55% in 85% aqueous ethanol; and into a handkerchief perfume in a concentration of (in 95% ethanol).
  • the use of the composition of Example XV affords a distinct and definite amber aroma to the handkerchief perfume and to the cologne.
  • Example XI or Example XIV affords a distinct and definite fruity amber aroma to the handkerchief perfume and to the cologne.
  • the abovementioned tobacco blend is divided into four portions: Portion A; Portion B; Portion C; and Portion D.
  • Portion C and D are each combined separately with the abovemcntioned tobacco flavor formulation. at the rate of(l.27(.
  • Each of Portions A. B, C and D are then manufactured into cigarettes.
  • the cigarettes containing tobacco Portions A and C are left as is.
  • To the cigarettes manufactured from tobacco Portions B and D are added at the rates of 200 and 2000 ppm the mixture of isomers of l',2',3',4',5',6',7',8'-octahydro- 2,3,8',8'tetramethyI-2'-acetonaphthone produced by the process of Example VII.
  • the cigarettes are then evaluated by paired comparison and the results are as follows.
  • the aroma on smoking of cigarettes produced from tobacco Portions B and D are found to be more sweet aromatic. more woody, more green and more spicey (sandalwood. cedarwood-like) than the aroma of those cigarettes produced from Portions A and C.
  • the cigarettes produced from Portion D are found to be more sweet. aromatic. more woody and more spicey. i.e.. having an oriental. balsamic, sandalwood, cedarwoodlike character.
  • the mixture of isomers of l',2',3',4',5',6',7'.8'- octah vdro2',3,8'.8'-tetramethyl-2'-acetonaphthones produced by the process of Example VII modifies the side stream and main stream smoke aromas by imparting thereto a pleasant, spicey. sandalwood. cedarwoodlike character.
  • FIG. I is a chart showing the nuclear magnetic resonance spectrum of peak No. I trapped by gas chromatography techniques from the product produced by the process of Example II or the major peak trapped by gas chromatography techniques from the product of Example VII.
  • FIG. 2 is a chart showing the nuclear magnetic resonance spectrum of peak No. 2 trapped by gas chromatographic techniques from the material produced by the process of Example II.
  • FIG. 3 is a portion of the Raman spectrum of the major peak trapped by gas chromatographic techniques from the material produced according to the process of Example VII.
  • FIG. 4 is an infrared analysis spectrum of the material which is the major peak trapped by gas chromatographic techniques from the material produced according to the process of Example VII.
  • FIG. 5 is a nuclear magnetic resonance spectrum of the material produced according to the process of Example XIV.
  • FIG. 6 is the nuclear magnetic resonance spectrum of the product produced according to the process of Example XI.
  • composition consisting essentially of a compound having the structure:

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US434948A 1973-02-27 1974-01-21 Novel process and products produced by said process Expired - Lifetime US3911018A (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
US434948A US3911018A (en) 1973-02-27 1974-01-21 Novel process and products produced by said process
NLAANVRAGE7401583,A NL182075C (nl) 1973-02-27 1974-02-05 Werkwijze ter bereiding van een reukstofpreparaat dat een 1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethylacetonaftonisomeer bevat, alsmede werkwijze ter bereiding van een tabaksmengsel.
AU65443/74A AU476465B2 (en) 1973-02-27 1974-02-11 PROCESS FOR PREPARING ISOMER MIXTURES OF OCTAHYDRO-2'3' 8' 8'TETRAMETHYL-(2' or 3 ACETONAPHTONE AND FRAGRANCE USE OF SAME
GB723274A GB1436991A (en) 1973-02-27 1974-02-18 Octahydro-tetramethyl-acetonaphthones their preparation and their use in perfume and tobacco compositions
MX705074U MX5607E (es) 1973-02-27 1974-02-22 Procedimiento para producir una composicion de fragancia semejante a ambar
DE2408689A DE2408689C3 (de) 1973-02-27 1974-02-22 Hydroacetonaphthonderivate, deren geometrische Isomere, Verfahren zu ihrer Herstellung und diese enthaltende Parfümzusammensetzungen und Tabakmassen
MX704974U MX5067E (es) 1973-02-27 1974-02-22 El nuevo uso de caracter industrial de isomero cis de acetonaftona de 1',2',3',4',5',6',7',8'-octahidro-2',3',8',8'-tetrametilo,como agente de fragancia de ambar en perfumeria
CA193,242A CA1029036A (fr) 1973-02-27 1974-02-22 Derives d'octahydro-acetonaphtone
IT48758/74A IT1049269B (it) 1973-02-27 1974-02-26 Procedimento per produrre composizioni con fragranza di tipo ambra e prodotti ottenuti
CH277174A CH605539A5 (fr) 1973-02-27 1974-02-27
FR7406687A FR2219140B1 (fr) 1973-02-27 1974-02-27
JP49023215A JPS6055484B2 (ja) 1973-02-27 1974-02-27 オクタヒドロ−テトウメチルアセトナフトンの有効な芳香量を必須成分として含有している香料組成物
US529086A US3929677A (en) 1974-01-21 1974-12-03 Perfume compositions and perfurme articles containing one isomer of an octahydrotetramethyl acetonaphthone
US529087A US3907321A (en) 1974-01-21 1974-12-03 Novel tobacco product comprising one or more isomers of an octahydrotetramethyl acetonaphthone

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US434948A US3911018A (en) 1973-02-27 1974-01-21 Novel process and products produced by said process

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CA (1) CA1029036A (fr)
CH (1) CH605539A5 (fr)
DE (1) DE2408689C3 (fr)
FR (1) FR2219140B1 (fr)
GB (1) GB1436991A (fr)
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Cited By (13)

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US4083373A (en) * 1976-10-07 1978-04-11 International Flavors & Fragrances Inc. Novel tobacco product comprising one or more sulfides and process
JPS5368761A (en) * 1976-11-11 1978-06-19 Int Flavors & Fragrances Inc Substituted acetonaphtone process for preparing same ferfume using same and intermediate for preparing same
US4156695A (en) * 1977-07-28 1979-05-29 International Flavors & Fragrances Inc. Preparing substituted acetonaphthones
US4162266A (en) * 1975-06-25 1979-07-24 Givaudan Corporation Trimethyl-acetyl octalins, process for making and fragrance compositions containing same
US4406828A (en) * 1979-08-10 1983-09-27 Givaudan Corporation Odorant and/or flavorant substances
US5077273A (en) * 1991-05-16 1991-12-31 International Flavors & Fragrances Inc. Epoxyoctahydrodimethylacetonaphthones, and perfumery uses thereof
EP0855378A1 (fr) * 1997-01-28 1998-07-29 INTERNATIONAL FLAVORS & FRAGRANCES INC. Dérivés de 1(4'-methylpentyl)ethylcyclohexane subsitué en position 4 et son usge comme organoleptique
EP0985651A1 (fr) * 1998-08-19 2000-03-15 Millennium Specialty Chemicals, Inc. Procédé de préparation de mélanges d'isomères d'acyloctahydronaphtalènes
US6114565A (en) * 1999-09-03 2000-09-05 Millennium Specialty Chemicals Process for obtaining nitriles
EP1925607A1 (fr) * 2006-11-06 2008-05-28 INTERNATIONAL FLAVORS & FRAGRANCES, INC. Dérivés de naphtalène hydrogénés substitués et leur utilisation dans des compositions parfumées
CN103058843A (zh) * 2012-12-26 2013-04-24 淮安万邦香料工业有限公司 提高龙涎酮中γ-异构体含量的制备方法
US11225629B2 (en) 2017-04-04 2022-01-18 Firmenich Sa Vetiver odorant
CN116217365A (zh) * 2023-03-23 2023-06-06 福州大学 一种改进的龙涎酮合成方法

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EP0405427B1 (fr) * 1989-06-30 1995-03-29 Firmenich Sa Nouveaux composés aromatiques, leur procédé de préparation et leur utilisation à titre d'ingrédients parfumants
US5185318A (en) * 1989-06-30 1993-02-09 Firmenich S.A. Aromatic compounds, a process for preparation thereof and use of same as perfuming ingredients
CA2042673C (fr) * 1990-06-02 2001-10-16 Franz Etzweiler Acetyle-tri et tetramethyle-octahydronaphtalenes et compositions de fragrances les contenant
US5214160A (en) * 1990-06-02 1993-05-25 Givaudan Corporation Acetyl-tri-and-tetramethyl-octahydronaphthalenes and fragrance compositions containing same
GB0503528D0 (en) * 2005-02-21 2005-03-30 Givaudan Sa Process
EP2794538B1 (fr) * 2011-12-21 2016-10-12 Firmenich SA Matières odorantes boisées
US10787627B2 (en) * 2015-10-01 2020-09-29 Firmenich Sa Vetiver odorant
JP2020515661A (ja) * 2017-04-04 2020-05-28 フイルメニツヒ ソシエテ アノニムＦｉｒｍｅｎｉｃｈ Ｓａ ベチバーの匂い物質

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US2933506A (en) * 1956-05-04 1960-04-19 Dragoco Gerberding Co Gmbh 1, 1-dimethyldecaline lactones and their 6-and 7-pyridyl, thienyl and furyl substituted derivatives
US3076022A (en) * 1959-04-15 1963-01-29 Givaudan Corp Myrcene-methyl isopropenyl ketone adducts, derivatives thereof

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US2933506A (en) * 1956-05-04 1960-04-19 Dragoco Gerberding Co Gmbh 1, 1-dimethyldecaline lactones and their 6-and 7-pyridyl, thienyl and furyl substituted derivatives
US3076022A (en) * 1959-04-15 1963-01-29 Givaudan Corp Myrcene-methyl isopropenyl ketone adducts, derivatives thereof

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4162266A (en) * 1975-06-25 1979-07-24 Givaudan Corporation Trimethyl-acetyl octalins, process for making and fragrance compositions containing same
US4083373A (en) * 1976-10-07 1978-04-11 International Flavors & Fragrances Inc. Novel tobacco product comprising one or more sulfides and process
JPS5368761A (en) * 1976-11-11 1978-06-19 Int Flavors & Fragrances Inc Substituted acetonaphtone process for preparing same ferfume using same and intermediate for preparing same
US4107208A (en) * 1976-11-11 1978-08-15 International Flavors & Fragrances Inc. Tetramethyl-hexahydroacetonaphthones
US4108799A (en) * 1976-11-11 1978-08-22 International Flavors & Fragrances Inc. Substituted acetonaphthone perfume compositions
US4108899A (en) * 1976-11-11 1978-08-22 International Flavors & Fragrances Inc. Process for preparing mixtures of substituted-hexahydro-acetonaphthones
US4156695A (en) * 1977-07-28 1979-05-29 International Flavors & Fragrances Inc. Preparing substituted acetonaphthones
US4406828A (en) * 1979-08-10 1983-09-27 Givaudan Corporation Odorant and/or flavorant substances
US5077273A (en) * 1991-05-16 1991-12-31 International Flavors & Fragrances Inc. Epoxyoctahydrodimethylacetonaphthones, and perfumery uses thereof
EP0855378A1 (fr) * 1997-01-28 1998-07-29 INTERNATIONAL FLAVORS & FRAGRANCES INC. Dérivés de 1(4'-methylpentyl)ethylcyclohexane subsitué en position 4 et son usge comme organoleptique
EP0985651A1 (fr) * 1998-08-19 2000-03-15 Millennium Specialty Chemicals, Inc. Procédé de préparation de mélanges d'isomères d'acyloctahydronaphtalènes
US6160182A (en) * 1998-08-19 2000-12-12 Millennium Specialty Chemicals Process for obtaining mixtures of isomeric acyloctahydronaphthalenes
US6114565A (en) * 1999-09-03 2000-09-05 Millennium Specialty Chemicals Process for obtaining nitriles
EP1925607A1 (fr) * 2006-11-06 2008-05-28 INTERNATIONAL FLAVORS & FRAGRANCES, INC. Dérivés de naphtalène hydrogénés substitués et leur utilisation dans des compositions parfumées
CN103058843A (zh) * 2012-12-26 2013-04-24 淮安万邦香料工业有限公司 提高龙涎酮中γ-异构体含量的制备方法
US11225629B2 (en) 2017-04-04 2022-01-18 Firmenich Sa Vetiver odorant
CN116217365A (zh) * 2023-03-23 2023-06-06 福州大学 一种改进的龙涎酮合成方法
CN116217365B (zh) * 2023-03-23 2024-05-31 福州大学 一种改进的龙涎酮合成方法

Also Published As

Publication number Publication date
IT1049269B (it) 1981-01-20
FR2219140B1 (fr) 1977-09-16
CA1029036A (fr) 1978-04-04
AU476465B2 (en) 1976-09-23
FR2219140A1 (fr) 1974-09-20
NL182075C (nl) 1988-01-04
JPS6055484B2 (ja) 1985-12-05
DE2408689C3 (de) 1980-10-16
NL182075B (nl) 1987-08-03
CH605539A5 (fr) 1978-09-29
NL7401583A (fr) 1974-08-29
DE2408689B2 (de) 1980-02-07
GB1436991A (en) 1976-05-26
DE2408689A1 (de) 1974-09-05
AU6544374A (en) 1975-08-14
JPS5035148A (fr) 1975-04-03

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