US3679749A - Perhydro 1,4,9,9-tetramethyl-4,7-methandazulenones - Google Patents

Abstract

Novel perhydro 1,4,9,9-tetramethyl-4,7-methano-azulenones useful as olfactory agents; perfume compositions containing such azulenones; and methods for preparing such azulenones and such compositions.

Description

United States Patent Grossman et al.

[ 51 July 25, 1972 PERHYDRO l,4,9,9-TETRAMETHYL- 4,7-METHANDAZULENONES Inventors: James D. Grosman, Old Bridge; Braja D. Mookherjee, Matawan; Robert De Simone, Madison Township, Middlesex County; Ernst T. Theimer, Rumson, all of NJ.

Assignee: International Flavors & Fragrances Inc.,

New York, NY.

Filed: June 10, 1968 Appl. No.: 735,544

US. Cl. ..260/586 R, 252/DlG. 5, 252/DlG. l3,

252/DIG. l4, 252/l32, 252/522, 260/462 A,

260/586 B, 260/606.5 B, 260/617 F, 260/666 PY, 424/59, 424/65, 424/69, 424/70, 424/76 Int. Cl ..C07c 49/27 Field of Search ..260/586 Chiurdoglu et al. Chem Abstracts" Vol. 51, pp. 4292f 4293a (1957).

Treibs Chem Abstracts" Vol. 44, pp. 3945c- 3947b, (1950).

Brown l-lydroboration" pp. 214- 215, 1962).

Primary Examiner-Leon Zitver Assistant Examiner-Norman Morgenstern Attorney-Brooks, l-laidt & Hafiner [5 7] ABSTRACT Novel perhydro l,4,9,9-tetramethyl-4,7-methano-azulenones useful as olfactory agents; perfume compositions containing such azulenones; and methods for preparing such azulenones and such compositions.

4 Claims, No Drawings PERHYDRO l,4,9,9-TETRAMETHYI'.-4,7- METHANDAZULENONES BACKGROUND OF THE INVENTION Materials which can provide amber and woody fragrance notes are known in the art of perfumery. Many of the natural materials which provide such fragrances and contribute desired nuances to perfume compositions are high in cost, variable in quality from one batch or crop to another, and/or are generally subject to the vagaries of natural products.

There is accordingly a continuing effort to find synthetic materials which will replace the essential fragrance notes of perfume compositions, but many of these synthetic materials either have the desired nuance only to a relatively small degree or else contribute undesirable or unwanted odors to compositions. Buchi et al., 83 J.A.C.S. 927 (1961), shows the production of a material called patchoulione which is stated to be octahydro-l,4,9,9-tetramethyl-3a,7-methanoazulen- 5(4H)-one.

THE INVENTION mula Ha I

wherein one of R,, R and R is oxygen and each of the other two represents two hydrogen atoms. It also relates to the use of these ketones as olfactory agents and in perfume compositions. The novel azulenones of the present invention provide a superior amber, precious wood, camphoraceous fragrance note and are much more intense than those previously known. Accordingly, smaller quantities can be used to impart a woody amber fragrance to perfume compositions and to perfumed articles, such as soap, face powder and other articles as disclosed hereinafter.

The novel materials according to the present invention can be considered as perhydro derivatives of methanoazulene and are octahydrol ,4,9,9-tetramethyl-4,7-methanoazulen-3( 2H)- one, I; octahydrol,4,9,9-tetramethyl-4,7-methanoazulen-Z (3H )-one, I]; octahydrol ,4,9,9-tetramethyl-4,7-methanoazulen-8( 7H)-one, Ill; and mixtures thereof.

I II III It will be appreciated that the foregoing structures include the various stereoisomeric forms.

I and ll can be used individually or in admixture with each other or with lll. Generally, III is utilized in admixture with the other two novel materials, and in many aspects of the present invention a mixture of the three ketones is preferred.

The ketones of this invention are useful as olfactory agents and fragrances. They have a camphoraceous woody amber LII fragrance in their own right and can impart this fragrance note to perfume compositions and perfumed articles according to the present invention. They can either be formulated into, or used as components of, perfume compositions.

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) topnotes which are usually low-boiling 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 mixtures or compounds of this 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 by weight of mixtures or compounds of this invention, or even less, may be used to impart a fine 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 azulene ketones described herein 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, bath salts; hair preparations such as lacquers, brilliantines, pomades, and shampoos; cosmetic preparations such as creams, deodorants, hand lotions, 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 0.011 percent of the novel ketone will suffice to impart an amber, camphoraceous woody odor.

in addition, the perfume composition can contain a vehicle or carrier for other ingredients. The vehicle can be a liquid such as alcohol, glycol, or the like. The carrier can be an absorbent or adsorbent solid such as a gum or components for encapsulating the composition.

The examples which appear hereinbelow illustrate perfume mixtures, soap and other formulations within the scope of this invention. It is to be understood that these compositions are preferred examples, and the invention is not to be considered as restricted thereto except as indicated in the appended claims.

The ketones of this invention can be prepared by a novel process which comprises treating a saturated alcohol having the structure or mixtures of such alcohols wherein one of R R and R is OH and the other two are H with an agent which will oxidize a secondary hydroxyl to a carbonyl and provide the novel ketones having the structure wherein R,, R and R are as disclosed above.

More specifically, the perhydro alcohol or alcohols are oxidized to a ketone by a strong oxidizing agent such as chromium trioxide, an alkali-metal dichromate such as potassium dichromate, sodium dichromate and the like, or an alkalimetal permanganate such as potassium permanganate and the like. It will be understood that the oxidizing agent and conditions used are such as to convert the secondary hydroxyl group to the carbonyl group without further oxidizing the hydrocarbon.

This secondary hydroxy-to-carbonyl reaction is preferably carried out in the presence of a chromium trioxide catalyst because of its relative mildness and specificity.

The reaction is carried out under acidic conditions. Thus, inorganic acids such as sulfuric acid and the like or organic acids such as lower aliphatic acids like acetic acid can be used to provide the acidic reaction milieu. There is also preferably a reaction vehicle such as an aqueous vehicle present to permit moderation and control of the reaction and to facilitate contact of the oxidizing agent with the secondary alcohol.

A temperature is maintained sufficient to provide a satisfactory rate of oxidation while avoiding further oxidation beyond the alcohol. It has been found that the reaction can be carried out at temperatures of from 5 C to the reflux temperature of the aqueous reaction system. It is generally preferred to carry out the oxidation at temperatures on the order of 20 30 C since this provides an acceptable reaction rate and minimizes side reactions.

The reaction can be carried out under atmospheric or subor superatmospheric pressures. However, because of the moderate temperature requirement of the reaction, atmospheric pressure is suitably used.

The novel ketones of this invention are conveniently prepared from beta-patchoulene having the structure octahydro-4,7-methanoazulene) octahydro-4,7-methanoazulene) by converting these materials to the saturated alcohols and then oxidizing the alcohol to the ketones as disclosed above. One method of obtaining the alcohol is by a direct oxidation of the patchoulene to provide the unsaturated ketones, as described in the copending application of Braja D. Mookherjee, entitled Novel Process and Product", Ser. No. 735,545 filed on even date herewith, and then hydrogenating the unsaturated ketones to produce the saturated alcohols. A novel method for preparation of the alcohols according to the present invention comprises treatment of the patchoulene with a diborane source to form a boron addition compound and then oxidizing and hydrolyzing the rearranged addition compounds to provide the secondary alcohols.

The novel ketones of the present invention can also be produced from patchouli alcohol, stated by Buchi et al., 86 J.A.C.S. 4438 et seq. 1964) to have the structure This alcohol is dehydrated under acid conditions to deltaf wherein one of the dashed lines is a double bond and the other two dashed lines are single bonds, and one of R, and R is oxygen and the other represents two hydrogen atoms.

The double bond of the methanoazulenone is hydrogenated and the keto group is simultaneously converted to a secondary alcohol group. The hydrogenation to obtain the secondary alcohol can be carried out with gaseous hydrogen in the presence of a hydrogenation catalyst such as Raney nickel, palladium on carbon, and the like. The reduction can also be perfonned using an alkali-meta] reduction process which utilizes sodium or other alkali-metal amide. It will be understood that the alkali-metal amide reduction can also be carried out alkali-metal such as sodium and a lower alkanol such as ethanol and the like.

The hydrogenation of the monounsaturated methanoazulenone is carried out at a temperature sufficient to afford a reasonable reaction rate. For the alkali-metal amide reduction, substantial molar excesses of alcohol, alkali-metal and ammonium hydroxide are used, based on the quantity of methanoazulenone. Thus, ten or more moles of ammonium hydroxide and two to four moles of alkali-metal are used. It will be understood that sodium amide in alcohol can also be used in the same relative proportions as set forth above. The amide reduction process is preferably carried out at temperatures ranging from 0 to about 30C.

According to a novel process the perhydro secondary alcohol can also be prepared directly from beta-patchoulene, described above, by treatment with a diborane source to form the boron addition compound and oxidation and hydrolysis to form the aforesaid rearranged secondary alcohol having the formula in an acidic reaction medium to form a methano bridge. Bulnesol is conveniently obtained from guaiacwood oil. The cyclization is carried out by treating the bulnesol or bulnesol fraction of guaiacwood oil with p-toluene-sulfonic acid and formic acid in a vehicle such as toluene. The mixture is heated at reflux until evolution of water ceases. The reaction mixture is then neutralized with alkali such as an alkali-metal hydroxide and distilled to obtain the beta-patchoulene.

Beta-Patchoulene is treated with a diborane source such as diborane itself, an alkali-metal borohydride-aluminum chloride mixture, an alkali-metal borohydride-boron trifluoride mixture, and the like. The alkali metal borohydride sources of diborane which can be used include lithium borohydride-aluminum chloride, sodium borohydride-boron trifluoride, and the like. The reaction is desirably carried out in an inert vehicle in which diborane is soluble to facilitate control of the reactants, lower the reaction pressure, and permit moderation and control of the reaction. It will be understood by those skilled in the art that the formation of the boron adduct is to be carried out in a substantially water-free environment. Suitable reaction vehicles for use in the hydroboration reaction include high-boiling ethers such as tetrahydrofuran, dimethoxyethane, diglyme, and the like.

As noted above, the diborane can be supplied to the reaction either directly in the gaseous form or as a diboraneproducing mixture such as alkali-metal borohydride-boron trifluoride. A preferred mixture is sodium borohydride-boron trifluoride.

ln carrying out the reaction, it has been found that the proportions of beta-patchoulene and diborane can be varied over a range. Thus, equivalent quantities of patchoulene and diborane can be used in carrying out the process. It will be understood that, when a complex furnishing diborane to the reaction is used, the quantity of the complex which can be used is that required to provide the desired proportion of diborane in the reaction. Generally, it is preferred than an excess of the diborane be present in the reaction mixture to assure complete reaction of the patchoulene and isomerization of the initially formed tertiary adduct. The formation of the boron adduct from patchoulene is preferably carried out at temperatures of 65C to 100C.

After the boron adduct has been prepared, it is oxidized and hydrolyzed to the perhydro secondary alcohol shown above. Those skilled in the art will appreciate from the present description that the oxidation and hydrolysis can be carried out sequentially or substantially simultaneously in a single reaction mixture. The oxidation of the boron adduct is carried out through the use of a relatively strong oxidizing agent. Suitable oxidizing agents for this step of the process include hydrogen peroxide and acid-dichromate media. Hydrogen peroxide strengths of from about to about 60 percent are preferred. When an acid-dichromate medium is utilized, the acid is preferably a strong inorganic acid such as sulfuric and the chromate is provided by chromic trioxide or an alkalimetal dichromate such as potassium dichromate and the like. All percentages, parts, proportions and ratios herein are by weight, unless otherwise indicated.

The oxidation reaction is carried out at temperatures which afford a good reaction rate while minimizing undesirable side reactions. Thus, when hydrogen peroxide is used as an oxidizing agent to form the perhydro secondary alcohol, temperatures on the order of from 20 to 40C are used. When an aciddichromate medium is used, the temperatures can range from 15C to 40C. The time for carrying out the reaction can vary, and it has been found that good yields are obtained in one-half to 2 hours.

The hydrolysis to provide secondary alcohols is preferably carried out with a strong base. Examples of preferred strong bases are the alkali-metal hydroxides such as sodium hydroxide, potassium hydroxide, and the like. When hydrogen peroxide is the oxidizing agent, the base can be added to the boron adduct before the treatment with peroxide.

For convenience, the perhydro alcohol obtained when R, is hydroxyl will be referred to as 3-01"; when R is hydroxyl, 2-ol"; and when R is hydroxyl, 8-ol". The proportion of each of these isomers obtained by hydroboration and oxidation-hydrolysis of beta-patchoulene varies according to the concentration of the reactants, the temperature of the hydroboration reaction, and to a lesser extent the time of reaction and whether the reaction is performed by adding oxidation agents directly to the hydroboration reaction mixture or whether a separation is first performed. It has been found in carrying out the process of this invention that the 2-ol is generally the major product, the 15-01 is obtained in lesser amounts, and the 8-01 is obtained in relatively small quantities. It will be appreciated that the oxidation of the secondary alcohol to provide the perhydro ketone will generally provide the keto-isomer corresponding to the secondary alcohol isomer. For instance, oxidation of the 2-0] provides the corresponding 2 -one (ll).

Depending upon the particular isomer or isomer mixture of ketones prepared according to this invention, the intermediate products, e.g., the boron adduct, the monounsaturated methanoazulenone, the perhydro secondary alcohol, can be purified and/or isolated as desired. Alternatively, purification and/or isolation can be carried out on the final perhydro ketone product. At least the final perhydro ketone is desirably purified to remove unreacted materials, by-products, color bodies, foreign odor bodies, and the like. The purification and/or isolation of the intermediates and the final ketonic products can be carried out by conventional techniques. Thus, the intermediate and final products can be purified, separated, and/or isolated by distillation, extraction, preparative chromatographic techniques, and the like.

The ketones obtained according to this invention have an amber, precious wood fragrance note. This fragrance note is quite intense, and relatively small quantities of the ketones according to this invention confer such a fragrance note on perfumed articles, perfume compositions and other olfactory I agents. Moreover, the novel ketones herein disclosed maintain substantially the same fragrance note over a period of time on a blotter, so that formulation of olfactory agents is facilitated and simplified.

The following Examples are given to illustrate embodiments of the invention as it is presently preferred to practice it. It will be understood that these Examples are illustrative and the invention is not to be considered as restricted thereto except as indicated in the appended claims.

EXAMPLE I HYDROBORATION OF BETA-PATCHOULENE FOLLOWED BY OXlDATlVE HYDROLYSIS TO PRODUCE SECONDARY ALCOHOL MIXTURE A 20-liter reaction vessel is charged with 2,500 ml. of tetrahydrofuran and 640 g. of sodium borohydride, and 2,800 g. of boron trifiuoride etherate is added dropwise to the mixture. Eighteen hundred and fifty grams of l,4,9,9-tetramethyl- A -octahydro-4,7-methanoazulene (beta-patchoulene) is added to the reaction mass, and the mass is refluxed at atmospheric pressure for 8 hours.

After cooling to 25C, 300 ml. of water is added over a 30- minute period while the mass is maintained at 25C. Six and three tenths grams of 3.0 M aqueous sodium hydroxide is then added with stirring during 45 minutes. Fifteen hundred ml. of a 50 percent solution of H 0 is added at 25C over 75 minutes. After the addition is complete, the organic layer is separated, the aqueous phase is extracted twice with equal volumes of diethyl ether, and the ether extracts and the organic layer are combined, washed twice with equal volumes of 5 percent sodium chloride solutions, dried over anhydrous magnesium sulfate, filtered and concentrated on a flash evaporator. The yield of crude secondary alcohol mixture, containing secondary alcohols of the structure wherein R R and R are defined as above, is 2364 g. Gasliquid phase chromatography (GLC) (8 X 1/4 feet 20 percent Carbowax 20M polyethylene glycol coated on "Anakron ABS" silanized acid-washed calcined diatomaceous earth made by Analab, Inc., Hamden, Conn. column; flow rate 100 ml./min.; chart speed, 15 inches/hr) indicates 82.2 percent of the 2ol; 12.7 percent 3-01; and 5.1 percent 8-ol.

EXAMPLE II OXIDATION OF THE SECONDARY ALCOHOL TO THE KETONE A l-liter reaction vessel is charged with 888 g. of chromium trioxide, 3.8 liters of glacial acetic acid and 1,600 ml. of water. A solution of 2,254 g. of the alcohol mixture prepared in Example I in 2.2 liters of acetic acid is added dropwise to the mixture, while the temperature is kept at 25-30C. The mixture is stirred until the exotherm ceases.

A solution of 250 g. of chromium trioxide in 600 ml. of glacial acetic acid and 100 ml. of water is then added to the reaction mass. The mass is maintained at 25-30C with stirring for 12 hours. At this point the reaction is 95 percent complete as indicated by GLC, and the acetic acid is distilled off and the resulting crude oil washed twice with equal volumes of percent sodium chloride-5% NaI'ICO solution, dried over anhydrous magnesium sulfate, and filtered. The filtered material is rushed over (flash distilled) to yield 1,338 g. of a crude mixture. This crude mixture is then distilled at 103-l44C at 0.8 mm Hg pressure.

GLC (conditions set forth above) shows three peaks which are identified as three ketones having the generic structure:

wherein R R and R are as defined above, the ratio of II I 111 being 70:21:5. The structures are confirmed by nuclear magnetic resonance (NMR) and infrared (IR) analyses. The mixture is separated and isolated (via GLC-conditions set forth above). Each of the three isomers possesses strong amber and patchouli fragrance notes, with additional camphoraceous notes. IR analysis of the three mixtures yields the following data:

I 11 I III S-Membered ring carbonyl 1735 cm 1730 cm Methylene alpha 1412 cm 1410 cm" 1410 cmgem-Dimethyl I365, I363, I364,

1388 cmv 1388 cm' 1387 cm- Methyl 1375 cm 1375 cm 1375 cm -Membered ring I735 cm carbonyl EXAMPLE Ill HYDROBORATION OF BETA-PATCHOULENE FOLLOWED BY OXIDATION IN SITU A 5-liter reaction vessel is charged with 1000 ml. of tetrahydrofuran, 80 g. of sodium borohydride, and 250 g.

beta-patchoulene, and 183 g. of boron tetrafluoride-diethyl etherate is added (this being one-half of the amount required to convert all the sodium borohydride to diborane). The reaction mass is refluxed at atmospheric pressure for four hours and an additional 30 g. of boron trifluoride-diethyl etherate is then added to the mass. The mixture is refluxed again for a period of four hours.

The resulting mixture containing boron addition compounds is subjected to oxidative hydrolysis and final oxidation to the desired ketone in the same reaction vessel as follows: A mixture of 1000 g. 93 percent Sulfuric acid 1000 g. Water 150 g. Sodium dichromate is then added to the reaction mass with stirring, while the mass is maintained at 25 C. Stirring at 25 C is continued until GLC (using the parameters set forth in Example II) shows the reac tion to be complete.

The phases are separated and the aqueous phase is extracted twice with equal volumes of diethyl ether. The ether extracts and organic layer are combined and washed three times with equal volumes of saturated sodium chloride solution, dried over anhydrous magnesium sulfate and treated in a flash evaporator to remove the diethyl ether. The crude ketone is then rushed over under good vacuum, and subsequently distilled at l03l44 C at 0.8 mm Hg pressure.

GLC (conditions set forth in Example 11) indicates three ketones. The structures are confirmed by IR and NMR analysis to be the 2-one, 3-one, and 8-one. The ratio of II I III according to the GLC analysis is 30:24:15. The mixture produced has a strong amber, patchouli, camphoraceous odor with an additional fine woody cigar box fragrance note. The 2-one and 3-0ne when separated by GLC have the same fragrance notes as those compounds obtained in Example II. IR analysis of the mixtures yields data identical to those obtained for the mixtures of Example II.

EXAMPLE IV PERHYDRO KETONES FROM PATCHOULI ALCOHOL Three and seven-tenths grams of patchouli alcohol is dissolved in 3.5 ml. of distilled hexane, and 1.0 g. of cation exchange resin [Amberlite IRC 120(H)CP, a chemically pure sulfonated styrene 8 percent divinyl benzene copolymer having an exchange capacity of 1.7 meq/ml (wet), manufactured by Rohm & Haas Co. of Philadelphia, Pa.] is added to the solution. The mixture is refluxed for 5 hours at atmospheric pressure. The ion exchange resin is then removed from the reaction mass by filtration and the mass is separated into three components using GLC (procedure of Example II): betapatchoulene, delta-patchoulene, and the patchouli alcohol starting material.

Into a ml. three-necked flask equipped with a condenser, nitrogen feed means, pressure-equilibrated dropping funnel, and magnetic stirring bar are placed the following materials:

123 mg. delta-Patchoulene trace Zinc Chloride 5 ml. Anhydrous diethyl ether 1.0 g. Sodium borohydride.

The reaction mass is cooled to 5 C and, maintaining this temperature, the mass is stirred for one hour. Boron trifluon'de-etherate, 10 ml., diluted with 10 ml. of diethyl ether is added to the reaction mass over a period of 1% hours, still maintaining the mass at 5 C. After stirring for 1 hour at 5 C, 2 ml. of water is added to destroy any remaining unreacted hydride. To the boron adduct mixture, 5 ml. of 3M aqueous sodium hydroxide solution is added. Immediately thereafter, 7 ml. of a 30 percent H 0 solution is added to the reaction mass during 1 hour while maintaining the temperature at 5 C. The reaction mass is then stirred at 5 C for an additional 2 hours.

The organic phase is separated, and the aqueous phase is successively extracted with three 10 ml. volumes of diethyl ether. The ether extract is combined with the organic phase and the combination is then washed successively with three 10 ml. volumes of water, dried over anhydrous sodium sulfate, and stripped of diethyl ether. The crude material chromatographed over silicic acid 15 percent deactivated, 3 g.) is found to be the perhydro secondary alcohol.

To 40 mg. of this secondary alcohol dissolved in 2 ml. glacial acetic acid is added 50 mg. of CrO dissolved in 1.5 ml. of glacial acetic acid. The mixture is maintained at C for 1 hour, diluted with 10 ml. of water, and extracted with two successive 10 ml. portions of diethyl ether. The combined ether extracts are then washed with three ml. portions of 2N Na CO and three 5 ml. portions of water. The washed ether extracts are dried over anhydrous sodium sulfate, and the solvent is removed to furnish crude ketone which is purified using the GLC procedure of Example I].

The purified ketone mixture has an amber, patchouli, camphoraceous odor. IR analysis of the mixture of ketones shows a 5-membered ring moiety at 1,735 cm". Mass spectral analysis shows a molecular ion at m/e of 220. The mass spectra, IR and MMR analyses confirm I and II.

EXAMPLE V PERHYDRO KETONE FROM DIRECT OXIDATION OF BETA-PATCI-IOULENE A: Oxidizing Agent Preparation Into a 3-liter reaction flask equipped with a reflux condenser, Y-tube, stirrer and nitrogen purge means is placed 1.2 liters of t-butyl alcohol. With nitrogen purging, 400 g. of anhydrous chromium trioxide is added over 1 hour. The mass is then dissolved in 2 liters of carbon tetrachloride, washed with three 500 cc. portions of water and dried over anhydrous sodium sulfate.

B: Direct Oxidation Into a l2-liter reaction flask equipped with a reflux condenser, stirrer, Y-tube, thermometer and addition funnel, are introduced the following materials:

200 g. beta-Patchoulene 2 liters Carbon tetrachloride 160 cc. Acetic Anhydride 600 cc. Acetic acid.

The mass is stirred and heated to 50 C.

A solution consisting of 3% liters of the chromium trioxidet-butyl alcohol complex prepared as in A, 160 cc. acetic anhydride, and 600 cc. of acetic acid is prepared. This solution is added dropwise to the beta-patchoulene solution over a 2% hour period, while the reaction mass is maintained at 50 C. The reaction mass is stirred for a period of 20 hours at 50 C and washed with a solution of 1,500 g. oxalic acid dissolved in 12 liters of water.

The organic layer is separated from the aqueous phase and washed with two 500 cc. portions of water, neutralized with a saturated sodium carbonate solution, and washed twice again with two successive 500 cc. portions of water. The washed material is dried over anhydrous sodium sulfate and concentrated under vacuum.

The crude concentrated material is distilled at 113l48C at 1.8-0.8 mm Hg pressure.

C. Reduction The distilled product, 2.5 g., produced by the foregoing direct oxidation is dissolved in 3 cc. of benzene and 3 cc. of aqueous saturated NH OI-I in a 50 cc. three-neck reaction flask equipped with a reflux condenser, thermometer, and magnetic stirring bar. The reaction mixture is cooled to 5 C. To the cooled mass, 08 g. of sodium particles are added over 1 hour. The temperature of the reaction mass is maintained between 10 and C. After a 1 hour period, 3 cc. of benzene and 5 cc. of aqueous saturated NI-LOI-I are added to the reaction flask. Then 0.8 g. of sodium particles are added over a 56 hour period. The reaction mass is then stirred for 2 hours at 25C and stored at 0C for a period of 13 hours. Two phases thereupon exist in the reaction mass: an organic phase and an aqueous phase.

The organic phase is washed with 5 cc. of a 3.7 percent solution of HC1 and washed twice with 5 cc. portions of distilled water. The washed organic phase is dried over anhydrous sodium sulfate, and the benzene solvent is removed with nitrogen. IR analysis indicates that a substantial portion of the ketone is reduced to perhydro secondary alcohol.

D. Oxidation The secondary alcohol formed in the immediately preceding section is dissolved in 9 cc. of glacial acetic acid and cooled to 0C. To this solution is added a solution consisting of 350 mg. chromium trioxide dissolved in 12 cc. of glacial acetic acid and 0.3 ml of distilled water. The reaction mass is stirred and maintained at 0C during the addition. The mass is then stirred at 24-25C for a period of 1 hour.

The reaction mass so obtained is poured into 30 cc. of distilled water in a 250 cc. separatory funnel and extracted four times with 25 cc. portions of diethyl ether. The ether extracts are combined and washed with 10% Na CO solution until basic. They are then washed with distilled water until neutral, dried over anhydrous sodium sulfate, and concentrated under vacuum. The resulting crude ketone mixture is distilled at l10-140C under 0.8 mm. pressure. IR, NMR and mass spectral analyses show the presence of I, II and Ill. The purified ketone mixture has an amber, patchouli, camphoraceous odor with a woody-cigar box note.

EXAMPLE VI PERFUME COMPOSITION A perfume composition is prepared with the following ingredients:

Ingredient Parts Vetivert Oil 40 Ketone Mixture of Example ll 60 Sandalwood Oil Rose Geranium Oil 200 Musk Extract (3%) 25 Civet Extract (3%) 25 Benzyl-iso-Eugenol 100 Coumarin 100 Heliotropin 50 Bois de Rose Oil 200 Benzoin Resin 100 Total: 1000 The perfume composition exhibits an excellent woody fragrance. When the ketone mixture is omitted, the composition lacks the woody, amber fullness of the complete perfume composition of this Example.

It will be understood from the present description that I, II and Ill produced according to the present invention can be used separately or in combination with each other to provide a good intense amber, woody fragrance note.

EXAMPLE VII The Example 11 mixture is evaluated against the known material patchoulione by preparing a solution of each in diethyl phthalate and comparing blotter strips containing samples of the solutions. The patchoulione" has a rooty earthy fragrance character, while the Example II material according to the present invention has an amber precious wood fragrance. The Example ll material is much more intense, being at least twice as strong as patchoulione, and maintains its strength and aroma pattern after several days dryout on the blotter strips.

In the following Examples, the soap base and soap chips used are unperfumed sodium-based toilet soaps made from tallow and coconut oil. The detergent powder is a material obtained from Lever Bros. Co. and sold under the trademark Rinso". The liquid detergent is a product manufactured by Ultra Chemical Co., and is known as P-87 liquid detergent.

EXAMPLE VIII PREPARATION OF SOAP COMPOSITION One hundred grams of soap chips are mixed with one gram of the perfume composition of Example VI until a substantially homogeneous composition is obtained. The perfumed soap composition manifests an excellent woody, amber, patchouli odor character.

EXAMPLE IX PREPARATION OF A DETERGENT COMPOSITION A total of 100 grams of a detergent powder is mixed with 0.l5 grams of the perfume composition of Example VI until a substantially homogeneous composition is obtained. This composition has an excellent woody, amber odor.

EXAMPLE X PREPARATION OF A COSMETIC POWDER COMPOSITION A cosmetic powder is prepared by mixing in a ball mill 100 grains of talcum powder with 0.25 grams of the mixture ob tained from the process of Example III. A second cosmetic powder is similarly prepared except that the mixture of Example II is used. Both have excellent woody, amber, patchoulilike odors.

EXAMPLE XI PERFUMED LIQUID DETERGENT Concentrated liquid detergents with a woody, amber, patchouli-like odor are prepared containing 0.10 percent 0. l 5 percent and 0.20 percent of the 3-one of this invention. They are prepared by adding and homogeneously mixing the appropriate quantity of the compound in the liquid detergent. The detergents all possess a woody amber fragrance, the intensity increasing with greater concentration of the ketone of this invention.

What is claimed is:

l. A ketone having the formula

Claims (3)

1. 2. The ketone of claim 1 wherein R1 is oxygen and R2 and R3 each represents two hydrogen atoms.
2. 3. The ketone of claim 1 wherein R2 is oxygen and R1 and R3 each represents two hydrogen atoms.
3. 4. The ketone of claim 1 wherein R3 is oxygen and R1 and R2 each represents two hydrogen atoms.