US3681464A - Saturated indane derivatives and processes for producing same - Google Patents

Saturated indane derivatives and processes for producing same Download PDF

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US3681464A
US3681464A US851048A US3681464DA US3681464A US 3681464 A US3681464 A US 3681464A US 851048 A US851048 A US 851048A US 3681464D A US3681464D A US 3681464DA US 3681464 A US3681464 A US 3681464A
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saturated
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indane derivatives
ketone
producing same
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Ernst T Theimer
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International Flavors and Fragrances Inc
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    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C07C35/22—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system
    • C07C35/23—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings
    • C07C35/32—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring polycyclic, at least one hydroxy group bound to a condensed ring system with hydroxy on a condensed ring system having two rings the condensed ring system being a (4.3.0) system, e.g. indenols
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    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C07C37/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of SO3H groups or a derivative thereof
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    • 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
    • C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
    • C—CHEMISTRY; METALLURGY
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    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/385—Saturated compounds containing a keto group being part of a ring
    • C07C49/417—Saturated compounds containing a keto group being part of a ring polycyclic
    • C07C49/423—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system
    • C07C49/427—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system having two rings
    • C07C49/443—Saturated compounds containing a keto group being part of a ring polycyclic a keto group being part of a condensed ring system having two rings the condensed ring system containing eight or nine carbon atoms
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    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/613—Unsaturated compounds containing a keto groups being part of a ring polycyclic
    • C07C49/617—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system
    • C07C49/623—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system having two rings
    • C07C49/633—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system having two rings the condensed ring system containing eight or nine carbon atoms
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    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
    • C07C5/11—Partial hydrogenation
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
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    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/32—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by aldehydo- or ketonic radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B9/00—Esters or ester-salts of leuco compounds of vat dyestuffs
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
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    • C11B9/00—Essential oils; Perfumes
    • C11B9/0069—Heterocyclic compounds
    • C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
    • C11B9/0076—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing less than six atoms
    • 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
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    • 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
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/44—Perfumes; Colouring materials; Brightening agents ; Bleaching agents
    • C11D9/442—Perfumes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
    • 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
    • Y10S424/00—Drug, bio-affecting and body treating compositions
    • Y10S424/01—Aerosol hair preparation
    • 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
    • Y10S424/00—Drug, bio-affecting and body treating compositions
    • Y10S424/02—Resin hair settings

Definitions

  • R is a carbonyl oxygen, a hydroxy group, an acyloxy group, or an alkyloxy group; perfume compositions containing such indane derivatives; and process for producing same.
  • the present invention provides novel saturated indane derivatives having the formula having the formula
  • the indanols and derivatives contemplated according to this disclosure include l,l,2,3,3-pentamethylhexahydroindan-4-ol having the formula l l ,2,3,3-pentamethylhexahydroindan-S-ol having the formula the corresponding indanyl alkyl ethers according to the formulas j@ o m and the corresponding indanyl esters according to the and formulas ;/ ⁇ O OR2 and ln the foregoing formulas R is a lower alkyl group,
  • the alcohols can be prepared directly from the corresponding pentamethylindane by sulfonation, alkali fusion, and hydrolysis to provide pentamethylindanol and then hydrogenation to the hexahydropentamethylindanol.
  • the saturated 3a,7aepoxypentamethylindane can be treated with an aluminum trialkoxide to form the monounsaturated alcoho].
  • the alcohols can also be produced directly from pentamethylindane by treatment with an acyl halide such as acetyl chloride or the like in the presence of a Friedel-Crafts catalyst followed by oxidation of the indane-alkyl ketone with a peroxygen material such as peracetic acid and the like to provide the indanyl ester. Hydrolysis of the ester provides the indanol which is then hydrogenated as set forth below to afford the saturated indanol.
  • a tetrahydroindanol can also be obtained by Birch reduction of S-indanol as shown in J. Am. Chem. Soc., 89, 1044. The tetrahydroindanols so prepared are then hydrogenated and oxidized to the ketone, as taught hereinafter.
  • the ketones of this invention can be produced by a number of routes.
  • One preferred route is the oxidation of a saturated or unsaturated 4-indanol or S-indanol under conditions providing the corresponding ketone.
  • any reagent which will convert a secondary hydroxyl to a carbonyl oxygen can be used.
  • oxidizing agents are Jones reagent (a chromium trioxide-sulfuric acid mixture) and oxygen-metal systems.
  • the oxidation of the hydroxyl group is carried out on a hydrogenated indanol.
  • a catalyst under conditions which will not reduce the carbonyl group.
  • Suitable catalysts for this reaction include metallic catalysts such as Raney nickel, or noble metals such as platinum, palladium, and the like utilized at substantially superatmospheric pressures on the order of 50 to 125 atmospheres. it is preferred to carry out the hydrogenation at from 1,000 to about 1,500 psig at l50 to 250 C.
  • the oxidation is carried out by treating the secondary alcohol with hexavalent chromium or oxygen-metallic catalyst oxidizing systems. It is desirable in carrying out such a reaction that the alcohol be dissolved or dispersed in a reaction vehicle which serves to moderate the reaction and provide better control. Suitable vehicles include oxygenated solvents such as acetone or lower carboxylic acids such as acetic acid. It will be understood that mutual solubility of the indanyl alcohol and oxidizing agent in the reaction vehicle is preferred.
  • the Jones reagent is prepared by dissolving chromium trioxide or alkali metal dichromate in aqueous sulfuric acid, e.g., 30 to 50 percent H S)O preferably 40 percent H2804. At least an equimolar quantity of the oxidizing agent is mixed with the indanol in, the reaction vehicle for best results. It is preferred to use an excess of oxidizing agent up to about 50 molar percent based upon the weight of the indanol, and a molar excess of 25 to 40 percent is preferred.
  • the oxidation is carried out at mild temperatures on the order of l30 C. In a preferred embodiment of the invention, the reaction is carried out at l520 C.
  • the oxidation to provide the ketones can also be carried out with the oxygen-metallic catalyst system disclosed above.
  • the oxygen caneither be pure or in admixture with an inert diluent such as nitrogen or the like.
  • the catalyst is preferably a metal such as silver. Copper can also be used.
  • the product can be separated from the vehicle and any unreacted materials or unwanted byproducts removed by conventional means including washing, distillation, crystallization, extraction, preparative chromatography, and the like. It is preferred to fractionally distill the washed reaction product under relatively high vacuum so as to obtain a pure product. Product purities of 80 percent are readily obtained, and much higher purities can also be provided by suitable treatment. All parts, proportions, percentages and ratios herein are by weight unless otherwise indicated.
  • the pentamethylhexahydroindanones of this invention are useful as fragrances. They can be used singly or in combination to contribute a woody amber fragrance.
  • the indanones of this 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, 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 or 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.
  • perfume compositions containing as little as 2 percent by weight of mixtures or compounds of this invention, or even less, may be used to impart a woody amber odor to soaps, cosmetics, and other products.
  • the amount employed can range up to 7 percent or higher and will depend on considerations of cost, nature of the end product, the effect desired on the finished product and the particular fragrance sought.
  • the indanones of this invention can be used alone or in a perfume composition as olfactory components in detergents and soaps; space deodorants; perfumes; colognes; bath preparations such as bath oil and bath salts; hair preparations such as lacquers, brilliantines, pomades and shampoos; cosmetic preparations such as creams, deodorants, hand lotions and sun screens; powders such as talcs, dusting powders, face powder, and the like.
  • olfactory component of a perfumed article as little as 0.01 percent of the novel ketones will suffice to impart a woody amber odor.
  • the perfume composition can contain a vehicle or carrier for the other ingredients.
  • vehicle can be a liquid such as alcohol, glycol, or the like.
  • carrier can be an absorbent solid such as a gum or components for encapsulating the composition.
  • the pentamethylhexahydroindanones according to this invention can be used to enhance, modify, or supplement the fragrance properties of natural or synthetic fragrance compositions.
  • the indanones can be used in fragrance compositions for addition to perfume compositions or directly to products such as soap, detergents, cosmetics, and the like.
  • the fragrance compositions so prepared do not entirely provide the olfactory properties to the finished perfume or other article, but they do EXAMPLE I a.
  • a 5-liter flask is se up with a thermometer and stirrer and immersed in a dry ice-isopropanol bath, and 1 liter of water is charged to the flask. After the water is cooled to C the foregoing reaction mixture is added dropwise to the water while the 10 temperature is maintained. The addition of reaction mixture to the water is completed and the stirring is continued for 30 minutes before filtering the flask contents through a Buchner funnel under vacuum. The solids so obtained are pressed to remove water.
  • the solids are rinsed in 100 ml of 1 percent hydrochloric acid at 0 C and pressed to obtain 822.2 g of crude crystals. After overnight drying in a vacuum desiccator, the 773.9 g of crude solids are placed in 3 liters ofbenzene and refluxed to remove further water. The benzene mixture is cooled to 40 C and filtered, and the benzene is distilled off under 50 mm Hg to recover l,1,2,3 ,3-pentamethylindanesulfonic acid.
  • reaction mass is cooled and extracted with water.
  • product is then neutralized with dilute hydrochloric acid, and the indanol so produced is extracted with benzene.
  • the benzene is stripped to provide 1, l ,2,3,3-pentamethylindanol.
  • reaction mass After 18 hours of hydrogenation at 1,500 psi and 178 C, the crude reaction mass is stripped free of solvent. Infrared and NMR analysis indicate that the reaction mass contains l,l,2,3,3-pentamethylindan-5-ol having the structure Similar reactions are run with a Raney nickel catalyst at 1,500 psig and 200 C and with a palladium on carbon catalyst at 150 psig and 200 C to provide substantially identical results.
  • a substantially identical reaction is carried out with l,l,2,3,3-pentamethylindan-4-ol to produce l,l,2,3,3- hexahydroindan-4-ol having the formula
  • a 500 ml reaction flask is charged with 50 g of crude hexahydropentamethylindan-S-ol obtained by hydrogenating the indan-S-ol produced in Example 1.
  • Jones reagent is produced by dissolving chromium trioxide in 20percent aqueous sulfuric acid.
  • the flask contents are maintained at l5-20 C while ml (0.33 mole) of the Jones reagent is added.
  • the reaction flask contents are then stirred for one-half hour beyond the thirty minutes required for addition of the Jones reagent.
  • the ketone is recovered by adding 25 cc of methanol and 50 cc of toluene.
  • the organic layer is separated, and the remaining aqueous layer is extracted with toluene.
  • the toluene extract is added to the original extract, and the organic material is washed to neutrality with water and then stripped and distilled.
  • the 33 g of distilled material is admixed with 2 g of Primol mineral oil and antioxidant and distilled at a vapor temperature of 96-l20 C at l-2 mm Hg to obtain 23.5 g of the pentamethylhexahydro-S-indanone.
  • the purified material is a clear liquid boiling at 9699 C at 2.0 mm Hg.
  • the IR spectrum shows significant peaks as follows: at 5.8 microns, at 7.1 microns, and at 7.2 and 7.3 microns. These peaks are attributable to a cyclohexanyl ketone, a methylene adjacent to a carbonyl, and to gem-dimethyl and methyl respectively. Raman spectrometry does not show the presence of any carbon-to-carbon unsaturation.
  • the ketone so obtained has an unmistakeable woody amber odor with a musk quality.
  • This material is compared with a ketone called Ketone BD9, a 3,5,5,7,7-pentamethyldecahydro-2-naphthalenone, and it is found that the indanone is a product having a much better woody amber character, whereas said napthalenone has a simple woody aroma.
  • the fragrance characteristics are considered to be quite different.
  • Example II The process set forth in Example II can be carried out with the corresponding pentamethylhexahydroim dan-4-ol to obtain a fragrance product similar to that obtained in Example II.
  • Enough hydrogen is fed into the autoclave to raise the pressure to 1,000 psig.
  • the hydrogen feed is then continued at 3 ml/min, and the autoclave is heated up to a temperature in the range of l50-185 C over a period of 8 hours. During this time the pressure in the autoclave is maintained at 1,500 psig.
  • Fraction 1 Distills at a temperature of 788 2 C and 4.0 mm Hg to provide 401 g of 4,5,6,7-tetrahydrol,1,2,3 ,3-pentamethylindane.
  • Fraction II Distills at a temperature of 868 8 C and 3.53.8 mm Hg to provide 729 g of hexahydrol, l ,2,3 ,3-pentamethylindane.
  • Fraction 1 is further refined on a 6-foot by inch gas liquid chromatographic (GLC) column containing 20 percent Carbowax polyethylene glycol and operated at 1 10 C. Analysis by infrared (IR) and proton magnetic resonance (PMR) confirms the structure:
  • the solvent is stripped off leaving a crude produce weighing 208 g.
  • the crude epoxy product is distilled on a 12-inch Goodloe column after addition of 4.0 g of triethanolamine at 7274 C and 1.0-1 .4 mm Hg.
  • the cooled reaction mass is poured into a mixture of 500 g ice and 200 cc of ISpercent sulfuric acid, stirred for 15 minutes, and separated into an aqueous phase and an organic phase.
  • the aqueous phase is extracted with 200 cc toluene, and the toluene extract is combined with the organic layer.
  • the bulked material is washed with saturated aqueous sodium bicarbonate and twice with 100 cc of water.
  • the solvent is stripped from the washed organic phase to provide a crude product weighing 71 g.
  • the crude product is distilled on a 4-inch micro- Vigreux column at a vapor temperature of l05l07 C and 2.1-2.3 mm Hg to obtain 4,5,6,7-tetrahydro- 1,l,2,3, 3-pentamethyl-4-indanol.
  • the solvent is stripped ofi and the remaining organic material is distilled to provide l,l,2,3,3-pentamethylhexahydro-4-(5l-l)-indanone having a woody amber odor with a fruit-like musk quality.
  • the perfume composition consists of the following ingredients:
  • EXAMPLE VI Preparation of a Detergent Composition A total of 100 g of a detergent powder is mixed with 0.15 g of the perfume composition set forth in Example V until a substantially homogeneous composition having a woody amber or amber-musk like odor is obtained.
  • EXAMPLE VII Preparation of a Cosmetic Powder Composition
  • a cosmetic powder is prepared by mixing 100 g of talcum powder with 0.25 g of the ketone obtained from the process of Example II in a ball mill.
  • a second cosmetic powder is similarly prepared except that the ketone prepared by Example II is replaced by the compound prepared by Example IV. All have woody amber, musk-like odors.
  • R is a carbonyl oxygen

Abstract

Saturated indane derivatives having the formula WHEREIN R is a carbonyl oxygen, a hydroxy group, an acyloxy group, or an alkyloxy group; perfume compositions containing such indane derivatives; and process for producing same.

Description

Unite States Patent Theimer [451 Aug. 1, 1972.
[54] SATURATED INDANE DERIVATIVES AND PROCESSES FOR PRODUCING SAME [72] Inventor: Ernst T. Theimer, Rumson, N1.
[73] Assignee: International Flavors & Fragrances Inc., New York, NY.
[22] Filed: Aug. 18, 1969 [21] App1.No.: 851,048
[5 6] References Cited OTHER PUBLICATIONS Moller, Chemistry of Organic Compounds 3rd Edition, pp. 150- 152, (1965) Appel et a1. J. Chem. Soc. Vol. 1959 pp. 3322 Moun, Chem. Abstracts" Vol. 57 pp. 7317- 7319, (1962) Dutta et al., Chem. Abstracts Vol. 59, p. 468C, (1963) Primary Examinerl ,eon Zitver Assistant Examiner-Norman Morgenstern Attorney-Ward, McElhannon, Brooks & Fitzpatrick [57] ABSTRACT Saturated indane derivatives having the formula &
wherein R is a carbonyl oxygen, a hydroxy group, an acyloxy group, or an alkyloxy group; perfume compositions containing such indane derivatives; and process for producing same.
3 Claims, No Drawings SATURATED INDANE DERIVATIVES AND PROCESSES FOR PRODUCING SAME BACKGROUND OF THE INVENTION There is a continuing need for fragrance materials having desirable woody amber odors with satisfactory olfactory overtones or qualities. Many natural products have such woody amber fragrances, but the more desirable of these are frequently in short supply, and
hence difficult to obtain and expensive. Further, while both natural and some synthetic materials can provide woody amber fragrance qualities, many of these are fleeting and unsuitable for use in quality perfumes or other olfactory compositions. Moreover, it is desirable to have such fragrance materials with musk, fruit-like, or similar overtones which can be blended with other materials.
THE INVENTION Briefly, the present invention provides novel saturated indane derivatives having the formula having the formula The indanols and derivatives contemplated according to this disclosure include l,l,2,3,3-pentamethylhexahydroindan-4-ol having the formula l l ,2,3,3-pentamethylhexahydroindan-S-ol having the formula the corresponding indanyl alkyl ethers according to the formulas j@ o m and the corresponding indanyl esters according to the and formulas ;/\O OR2 and ln the foregoing formulas R is a lower alkyl group,
desirably one having from one to five carbon atoms, with methyl being a preferred lower alkyl group; and R is a lower alkyl acyl group having from one to five carbon atoms, with the acetyl group being preferred. It will be appreciated from the present disclosure that the foregoing materials can exist in several stereoisomeric forms, and it is contemplated that the formulas given above include the several isomeric forms.
The alcohols can be prepared directly from the corresponding pentamethylindane by sulfonation, alkali fusion, and hydrolysis to provide pentamethylindanol and then hydrogenation to the hexahydropentamethylindanol. Alternatively, the saturated 3a,7aepoxypentamethylindane can be treated with an aluminum trialkoxide to form the monounsaturated alcoho].
The alcohols can also be produced directly from pentamethylindane by treatment with an acyl halide such as acetyl chloride or the like in the presence of a Friedel-Crafts catalyst followed by oxidation of the indane-alkyl ketone with a peroxygen material such as peracetic acid and the like to provide the indanyl ester. Hydrolysis of the ester provides the indanol which is then hydrogenated as set forth below to afford the saturated indanol. A tetrahydroindanol can also be obtained by Birch reduction of S-indanol as shown in J. Am. Chem. Soc., 89, 1044. The tetrahydroindanols so prepared are then hydrogenated and oxidized to the ketone, as taught hereinafter.
The ketones of this invention can be produced by a number of routes. One preferred route is the oxidation of a saturated or unsaturated 4-indanol or S-indanol under conditions providing the corresponding ketone. According to this preferred route, any reagent which will convert a secondary hydroxyl to a carbonyl oxygen can be used. Exemplary of such oxidizing agents are Jones reagent (a chromium trioxide-sulfuric acid mixture) and oxygen-metal systems.
The oxidation of the hydroxyl group is carried out on a hydrogenated indanol. In the event that the ketone is not saturated the six-membered ring is subsequently hydrogenated with a catalyst under conditions which will not reduce the carbonyl group. Suitable catalysts for this reaction include metallic catalysts such as Raney nickel, or noble metals such as platinum, palladium, and the like utilized at substantially superatmospheric pressures on the order of 50 to 125 atmospheres. it is preferred to carry out the hydrogenation at from 1,000 to about 1,500 psig at l50 to 250 C.
The oxidation is carried out by treating the secondary alcohol with hexavalent chromium or oxygen-metallic catalyst oxidizing systems. It is desirable in carrying out such a reaction that the alcohol be dissolved or dispersed in a reaction vehicle which serves to moderate the reaction and provide better control. Suitable vehicles include oxygenated solvents such as acetone or lower carboxylic acids such as acetic acid. It will be understood that mutual solubility of the indanyl alcohol and oxidizing agent in the reaction vehicle is preferred.
The Jones reagent is prepared by dissolving chromium trioxide or alkali metal dichromate in aqueous sulfuric acid, e.g., 30 to 50 percent H S)O preferably 40 percent H2804. At least an equimolar quantity of the oxidizing agent is mixed with the indanol in, the reaction vehicle for best results. it is preferred to use an excess of oxidizing agent up to about 50 molar percent based upon the weight of the indanol, and a molar excess of 25 to 40 percent is preferred The oxidation is carried out at mild temperatures on the order of l30 C. In a preferred embodiment of the invention, the reaction is carried out at l520 C.
The oxidation to provide the ketones can also be carried out with the oxygen-metallic catalyst system disclosed above. In this case the oxygen caneither be pure or in admixture with an inert diluent such as nitrogen or the like. The catalyst is preferably a metal such as silver. Copper can also be used.
After the reaction to produce the ketone is completed, the product can be separated from the vehicle and any unreacted materials or unwanted byproducts removed by conventional means including washing, distillation, crystallization, extraction, preparative chromatography, and the like. it is preferred to fractionally distill the washed reaction product under relatively high vacuum so as to obtain a pure product. Product purities of 80 percent are readily obtained, and much higher purities can also be provided by suitable treatment. All parts, proportions, percentages and ratios herein are by weight unless otherwise indicated.
The pentamethylhexahydroindanones of this invention are useful as fragrances. They can be used singly or in combination to contribute a woody amber fragrance.
As olfactory agents the indanones of this invention can be formulated into or used as components of a perfume composition.
The term perfume composition is used herein to mean a mixture of organic compounds, including, for example, alcohols, aldehydes, ketones, esters and frequently hydrocarbons which are admixed so that the combined odors of the individual components produce a pleasant or desired fragrance. Such perfume compositions usually contain: (a) the main note or 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.
In perfume compositions 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. Thus, 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 compounds of this invention which will be eflective 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 by weight of mixtures or compounds of this invention, or even less, may be used to impart a woody amber odor to soaps, cosmetics, and other products. The amount employed can range up to 7 percent or higher and will depend on considerations of cost, nature of the end product, the effect desired on the finished product and the particular fragrance sought.
The indanones of this invention can be used alone or in a perfume composition as olfactory components in detergents and soaps; space deodorants; perfumes; colognes; bath preparations such as bath oil and bath salts; hair preparations such as lacquers, brilliantines, pomades and shampoos; cosmetic preparations such as creams, deodorants, hand lotions and sun screens; powders such as talcs, dusting powders, face powder, and the like. When used as an olfactory component of a perfumed article, as little as 0.01 percent of the novel ketones will suffice to impart a woody amber odor.
In addition, the perfume composition can contain a vehicle or carrier for the other ingredients. The vehicle can be a liquid such as alcohol, glycol, or the like. The carrier can be an absorbent solid such as a gum or components for encapsulating the composition.
It will also be appreciated that the pentamethylhexahydroindanones according to this invention can be used to enhance, modify, or supplement the fragrance properties of natural or synthetic fragrance compositions. Thus, the indanones can be used in fragrance compositions for addition to perfume compositions or directly to products such as soap, detergents, cosmetics, and the like. The fragrance compositions so prepared do not entirely provide the olfactory properties to the finished perfume or other article, but they do EXAMPLE I a. Preparation of Pentarnethylindanesulfonic Acid A 5-liter flask equipped with a stirrer, condenser, and dropping funnel is charged with 1,500 g of concentrated sulfuric acid, and 400 g of l,l,2,3,3-pentamethylindane is added dropwise while the temperature is maintained at 3035 C. After addition is completed stirring is continued for an additional hour.
A 5-liter flask is se up with a thermometer and stirrer and immersed in a dry ice-isopropanol bath, and 1 liter of water is charged to the flask. After the water is cooled to C the foregoing reaction mixture is added dropwise to the water while the 10 temperature is maintained. The addition of reaction mixture to the water is completed and the stirring is continued for 30 minutes before filtering the flask contents through a Buchner funnel under vacuum. The solids so obtained are pressed to remove water.
The solids are rinsed in 100 ml of 1 percent hydrochloric acid at 0 C and pressed to obtain 822.2 g of crude crystals. After overnight drying in a vacuum desiccator, the 773.9 g of crude solids are placed in 3 liters ofbenzene and refluxed to remove further water. The benzene mixture is cooled to 40 C and filtered, and the benzene is distilled off under 50 mm Hg to recover l,1,2,3 ,3-pentamethylindanesulfonic acid.
b. Preparation of Pentamethylindanol One mole of the indanesulfonic acid so produced is thoroughly admixed with 2 moles of sodium hydroxide, and the mixture is heated to the fusion temperature of 360 C and maintained at that temperature for 2 hours. During the fusion the reaction mass is mechanically agitated.
After the heating is completed, the reaction mass is cooled and extracted with water. The product is then neutralized with dilute hydrochloric acid, and the indanol so produced is extracted with benzene. The benzene is stripped to provide 1, l ,2,3,3-pentamethylindanol.
c. Production of Pentamethylhexahydroindanol Into a 200 ml stainless steel autoclave are introduced 70 g of 1,l,2,3,3-pentamethylindan-5-ol, 5 g of 5 percent rhodium on carbon catalyst, and 150 ml of isopropyl alcohol. While maintaining the temperature within the autoclave at C, hydrogen gas is fed in until a pressure of 1,025 psi is reached. While the hydrogen pressure is maintained at about 1,025 psi, the temperature of the reaction mass is raised over a period of 3 hours to 178 C (at which point the pressure rises to 1,500 psi).
After 18 hours of hydrogenation at 1,500 psi and 178 C, the crude reaction mass is stripped free of solvent. Infrared and NMR analysis indicate that the reaction mass contains l,l,2,3,3-pentamethylindan-5-ol having the structure Similar reactions are run with a Raney nickel catalyst at 1,500 psig and 200 C and with a palladium on carbon catalyst at 150 psig and 200 C to provide substantially identical results.
A substantially identical reaction is carried out with l,l,2,3,3-pentamethylindan-4-ol to produce l,l,2,3,3- hexahydroindan-4-ol having the formula A 500 ml reaction flask is charged with 50 g of crude hexahydropentamethylindan-S-ol obtained by hydrogenating the indan-S-ol produced in Example 1. Jones reagent is produced by dissolving chromium trioxide in 20percent aqueous sulfuric acid. The flask contents are maintained at l5-20 C while ml (0.33 mole) of the Jones reagent is added. The reaction flask contents are then stirred for one-half hour beyond the thirty minutes required for addition of the Jones reagent.
The ketone is recovered by adding 25 cc of methanol and 50 cc of toluene. The organic layer is separated, and the remaining aqueous layer is extracted with toluene. The toluene extract is added to the original extract, and the organic material is washed to neutrality with water and then stripped and distilled.
The 33 g of distilled material is admixed with 2 g of Primol mineral oil and antioxidant and distilled at a vapor temperature of 96-l20 C at l-2 mm Hg to obtain 23.5 g of the pentamethylhexahydro-S-indanone.
The purified material is a clear liquid boiling at 9699 C at 2.0 mm Hg. The IR spectrum shows significant peaks as follows: at 5.8 microns, at 7.1 microns, and at 7.2 and 7.3 microns. These peaks are attributable to a cyclohexanyl ketone, a methylene adjacent to a carbonyl, and to gem-dimethyl and methyl respectively. Raman spectrometry does not show the presence of any carbon-to-carbon unsaturation.
The ketone so obtained has an unmistakeable woody amber odor with a musk quality. This material is compared with a ketone called Ketone BD9, a 3,5,5,7,7-pentamethyldecahydro-2-naphthalenone, and it is found that the indanone is a product having a much better woody amber character, whereas said napthalenone has a simple woody aroma. The fragrance characteristics are considered to be quite different.
The process set forth in Example II can be carried out with the corresponding pentamethylhexahydroim dan-4-ol to obtain a fragrance product similar to that obtained in Example II.
EXAMPLE III Preparation of 1,1 ,2,3,3-Pentamethylhexahydroindan- 4-ol The following ingredients are charged into a stainless steel five-liter autoclave equipped with a hydrogen gas feed:
1,800 g (8.14 moles) of l, 1 ,2,3,3-pentamethylindane (85 percent pure) 90 g of Raney nickel.
Enough hydrogen is fed into the autoclave to raise the pressure to 1,000 psig. The hydrogen feed is then continued at 3 ml/min, and the autoclave is heated up to a temperature in the range of l50-185 C over a period of 8 hours. During this time the pressure in the autoclave is maintained at 1,500 psig.
The 1,641 g of crude product removed from the autoclave is distilled on a 12-inch Goodloe column after being mixed with 10.0 g of Primol mineral oil. The distillate is recovered in two fractions:
Fraction 1: Distills at a temperature of 788 2 C and 4.0 mm Hg to provide 401 g of 4,5,6,7-tetrahydrol,1,2,3 ,3-pentamethylindane.
Fraction II: Distills at a temperature of 868 8 C and 3.53.8 mm Hg to provide 729 g of hexahydrol, l ,2,3 ,3-pentamethylindane.
A sample of Fraction 1 is further refined on a 6-foot by inch gas liquid chromatographic (GLC) column containing 20 percent Carbowax polyethylene glycol and operated at 1 10 C. Analysis by infrared (IR) and proton magnetic resonance (PMR) confirms the structure:
Into a 250 ml flask equipped with thermometer, stirrer, reflux condenser and ice bath are introduced 195 g of the 'tetrahydroindane produced above and g of sodium acetate. At 25t0 30C 124g of 40percent peracetic acid (0.65 mole) is added during 4 hours. After addition is completed an equal volume of water is added to the reaction mass. The aqueous phase is separated from the organic phase and extracted with 150 ml of toluene. The toluene extract is combined with the organic phase and washed with 1 volume of Spercent aqueous sodium hydroxide solution and then with 1 volume of water.
The solvent is stripped off leaving a crude produce weighing 208 g. The crude epoxy product is distilled on a 12-inch Goodloe column after addition of 4.0 g of triethanolamine at 7274 C and 1.0-1 .4 mm Hg.
Into a 500 ml flask equipped with reflux condenser, stirrer thermometer and addition funnel are introduced 250 cc toluene and 80 g aluminum triisopropoxide. The mixture is heated to reflux and 90 g of the epoxyhexahydroidane as produced above is added drop-wise over 1 A hours at reflux. The reaction mass is further refluxed for 10 hours whereupon it is cooled at 25 C.
The cooled reaction mass is poured into a mixture of 500 g ice and 200 cc of ISpercent sulfuric acid, stirred for 15 minutes, and separated into an aqueous phase and an organic phase. The aqueous phase is extracted with 200 cc toluene, and the toluene extract is combined with the organic layer. The bulked material is washed with saturated aqueous sodium bicarbonate and twice with 100 cc of water. The solvent is stripped from the washed organic phase to provide a crude product weighing 71 g.
The crude product is distilled on a 4-inch micro- Vigreux column at a vapor temperature of l05l07 C and 2.1-2.3 mm Hg to obtain 4,5,6,7-tetrahydro- 1,l,2,3, 3-pentamethyl-4-indanol.
Into a 200 mi stainless steel autoclave are introduced 60 g of the tetrahydropentamethyl-4-indanol so produced, 5g of Spercent rhodium on carbon catalyst, and 150 ml of isopropanol. The temperature of the autoclave is maintained at 20 C while hydrogen gas is fed in to obtain a pressure of 1,025 psig. The temperature is then raised to 180 C whereupon the temperature rises to 1,500 psig.
After 18 hours of hydrogenation under these conditions, the hydrogen is vented and the autoclave is clave is cooled to room temperature. The solvent is stripped ofi to yield a crude product weighing 35 g. The product is washed and distilled to obtain 1 l ,2,3,3-pentamethylhexahydroindan-4-ol.
EXAMPLE IV Preparation of 1 ,1 ,2,3 ,3-Pentamethylhexahydro 4( 5 H)-indanone Into a 500 ml flask fitted with cooling means, stirrer, thermometer and reflux condenser are introduced 50 g of the hexahydroindan-4-ol produced in Example 111 and 300 ml of acetone. The mixture is stirred while ml of Jones reagent is added. The reaction mixture is then stirred for 1 hour, after which 25 ml of ethanol and 50 ml of toluene are added. The aqueous phase is removed and the organic phase is washed and neutralized with sodium bicarbonate.
The solvent is stripped ofi and the remaining organic material is distilled to provide l,l,2,3,3-pentamethylhexahydro-4-(5l-l)-indanone having a woody amber odor with a fruit-like musk quality.
EXAMPLE V Preparation of Soap Compositions A total of g of soap chips is mixed with 1 g of the perfume composition given below until a substantially homogeneous composition is obtained. The soap composition manifests a characteristic woody amber, musklike odor.
The perfume composition consists of the following ingredients:
ingredient Parts Vetivert Oil 40 Ketone Produced in Example 11 60 Sandalwood Oil 100 Rose Geranium Oil 200 Musk Extract (3%) 25 Civet Extract (3%) 25 Benyl-iso-Eugenol 100 Coumarin 100 Heliotropin 50 Bois de Rose Oil 200 Benzoin Resin 100 1.000
Similar results are obtained when the ketone of Example 1V is used to replace the ketone of Example 11.
EXAMPLE VI Preparation of a Detergent Composition A total of 100 g of a detergent powder is mixed with 0.15 g of the perfume composition set forth in Example V until a substantially homogeneous composition having a woody amber or amber-musk like odor is obtained.
EXAMPLE VII Preparation of a Cosmetic Powder Composition A cosmetic powder is prepared by mixing 100 g of talcum powder with 0.25 g of the ketone obtained from the process of Example II in a ball mill. A second cosmetic powder is similarly prepared except that the ketone prepared by Example II is replaced by the compound prepared by Example IV. All have woody amber, musk-like odors.
EXAMPLE VIIl compound to P87 liquid detergent produced by Ultra Chemical Co.
What is claimed is:
1. Saturated indane derivatives having the formula &
wherein R is a carbonyl oxygen.
2. 1,1,2,3,3-Pentamethylhexahydro-4(5l-l)-indanone.
3. l, l ,2,3,3-Pentamethy1hexahydro-5(4H)-indanone.

Claims (2)

  1. 2. 1,1,2,3,3-Pentamethylhexahydro-4(5H)-indanone.
  2. 3. 1,1,2,3,3-Pentamethylhexahydro-5(4H)-indanone.
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US85104969A 1969-08-18 1969-08-18
US11583471A 1971-02-16 1971-02-16
US18464071A 1971-09-28 1971-09-28
US00286994A US3806472A (en) 1969-08-18 1972-09-07 Perfume composition containing hydrogenated indane derivative
US00325676A US3839368A (en) 1969-08-18 1973-01-22 7,7a-epoxy-5,6,7,7a-tetrahydro-1,1,2,3,3-pentamethyl-4(3ah)-indanone
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US4634547A (en) * 1985-08-08 1987-01-06 International Flavors & Fragrances Inc. Organoleptic uses of bicyclononenyl alcohols
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US10570086B2 (en) 2016-03-17 2020-02-25 Fmc Corporation Process for converting S-enantiomer to its racemic form
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US11208374B2 (en) 2016-03-17 2021-12-28 Fmc Corporation N-(7-fluoro-1,1,3-trimethyl -1 H-inden-4yl) amides and a process for preparing same
US11319277B2 (en) 2016-03-17 2022-05-03 Fmc Corporation Process for converting S-enantiomer to its racemic form

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US3636165A (en) 1972-01-18
US3647826A (en) 1972-03-07
US3773836A (en) 1973-11-20
US3806472A (en) 1974-04-23
US3636176A (en) 1972-01-18

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