US3929675A

US3929675A - Novel products and processes

Info

Publication number: US3929675A
Application number: US446141A
Authority: US
Inventors: Seymour Lemberg
Original assignee: International Flavors and Fragrances Inc
Current assignee: International Flavors and Fragrances Inc
Priority date: 1967-05-15
Filing date: 1974-02-27
Publication date: 1975-12-30
Anticipated expiration: 1992-12-30

Abstract

Novel cyclic materials produced by cyclizing and/or epoxidizing trimethyl cyclododecatriene, and, optionally, converting the products to alcohols or ketones and/or hydrogenating the products to provide a lower degree of unsaturation; processes for producing such materials; and perfume and fragrance-imparting compositions containing such materials.

Description

4 United States Patent [191 1111 3,929,675

Lemberg 5] Dec. 30, 1975 [54] NOVEL PRODUCTS AND PROCESSES 2,656,390 10/1953 Stoll 260/586 3,l28,304 4/1964 Lafont 260/487 [751 Invent: Lemberg, Elzabem 3,235,60l 2/1966 Parsons....- 260/586 [73] Assignee; International flavors & Fragrances 3,723,478 3/1973 Ohloff 61 al 260/348 c lnc., New York, N.Y. [g2] pu d; F 27 1974 Primary ExaminerC. Davis Attorney, Agent, or Firm-Biooks Haidt Haffner & [2i] Appl. No.. 446,141 Delahumy Related U.S. Application Data [60] I Division of Ser. No. 638,429, May I5, 1967, Pat. No.

3,845,078, which is a continuation-in-part of Ser. No. ABSTRACT 551,675, May 20, l966, abandoned.

Novel cyclic materials produced by cyclizing and/or 52 U.S. c1. 252/522 epoxidiling Irimethyl cyclododecatriene, and, Option- 511 1111. (:1. A61K 7/46; c1113 9/00 y. converting the Products-t9 alcohols of ketones [58] Field 6: Search 260/348 0, 586, 487; and/or hydrogenating the Products to Provide a lower 252 522 degree of unsaturation; processes for producing such materials; and perfume and fragrance-imparting com- [5 R f r Cited positions containing such materials.

UNITED STATES PATENTS 1,702,847 2 1929 Ruzicka 260/586 4 Draw'ng US. Patent Dec. 30, 1975 Sheet 2 of4 3,929,675

Q m m n 09 QQQ QR Gm gwgag QQGQQQQW NOVEL PRODUCTS AND PROCESSES This application is a division of application Ser. No. 638,429 filed May 15, 1967, now US. Pat. No. 3,845,078; and said application Ser. No. 638,429 in turn is a continuation-in-part of application Ser. No. 551,675 filed May 20, 1966 now abandoned.

BACKGROUND OF THE INVENTION In the perfumers art there is a considerable need for substances having a woody fragrance note which is at least moderately persistent. Especially desirable are materials which combine a woody fragrance with a camphoraceous fragrance note. Such woody, camphoraceous fragrance materials have a wide utility in the preparation of fragrance-modifying and finished perfume compositions. A limited amount of such materials is available from natural sources, but the natural materials are subject to wide variation in quality, are expensive, and are in limited (and often critically short) supply.

TI-IE INVENTION This invention provides novel compositions and components together with novel processes and steps of processes, specific embodiments of which are described hereinafter by way of example and in accordance with which it is now preferred to practice the invention.

Briefly, the novel cyclic materials of this invention are l ,5 ,9-trimethyl-l 3-oxabicyclo[ 10.1.0] trideca-4,8- diene and hydrogenated, cyclized and reduced derivatives thereof, including l,5,9-trimethylcyclododeca- 5,9-dien-2-one, and cyclized trimethylcyclododecatriene and epoxy derivatives of the cyclized trimethylcyclododecatriene. The processes of this invention broadly involve the reaction of 1,5,9-trimethylcyclododecatriene with an epoxidizing agent and if desired a cyclizing agent, in which case either of these agents can be used. Under some conditions the treatment provides a preponderance of an epoxy derivative, and under other conditions a ketonic material is obtained as the main product. The substances thus produced can be further treated, as by hydrogenation or reduction, to produce other useful new materials. These novel cyclic materials are:

l,5,9-Cyclododecatriene-l ,5,9 derivatives of the formula H %-cn,

2 and the dashed lines represent single or double bonds; the cyclized derivatives when and the epoxy products of said cyclized derivatives when -tion is l,5,9-trimethyl-l3-oxabicyclo[10.1.0] trideca- 4,8-diene (hereinafter generally referred to as bicyclo C-l2). The bicyclo C-l2 is prepared by treating l,5,9-trimethylcyclododecatriene (hereinafter also referred to as cyclo C-12) with an organic percarboxylic acid in the presence of an alkaline reagent. This reaction should be conducted under anhydrous conditions since any substantial amount of water is deleterious to the reaction.

Another primary material provided by carrying out the process of this invention is cyclized trimethylcyclododecatriene (hereinafter also referred to as cyclized cyclo C-l2). A cyclized bicyclo C-l2 can also be obtained according to the present invention. It will be understood from the following description that the cyclized materials are useful perfume and fragrancemodifying substances and intermediates in preparing other perfume and fragrance-modifying substances.

The cyclized materials according to this invention can be obtained by treating the cyclo C-l 2 or the bicyclo material with a proton donor or an electron acceptor. While the reaction mechanism may not be entirely elucidated, it is presently believed that the proton donor forms andintermediate material in which one of the double bonds contains a proton or a positive charge and that such charge renders it reactive. Exemplary of such proton donor materials are sulfuric acid, and various phosphoric acids including dilute orthophosphoric acid, concentrated phosphoric acid, and higher phosphoric acids such as pyroand polyphosphoric acids. A preferred cyclizing agent is phosphoric acid. Boron trifiuoride is also a useful cyclizing agent. Unless otherwise indicated, all parts, proportions, percentages, and ratios herein are by weight.

The present invention is further illustrated in the accompanying drawings, wherein FIGS. 1 and 2 are, respectively, infrared absorption and NMR spectra of cyclized bicyclo C-l2;

FIG. 3 is an infrared absorption spectrum of cyclized cyclo C-l2; and

FIG. 4 is an infrared absorption spectrum of epoxy cyclized cyclo C-l2.

Cyclo C-l2 is generally available atpurities of and upwards, and it can be used in this form. It is generally preferred however in the practice of this invention 3 to refine the material to substantially 100% purity. Such purification is readily accomplished by fractional distillation.

An epoxidizing agent used in carrying out the process of this invention is an organic percarboxylic acid. Generally, any organic aliphatic or aromatic percarboxylic acid having from 1 to about carbon atoms can be successfully used in this invention. Aromatic percarboxylic acids such as perbenzoic, perphthalic, and chloroperbenzoic acids, and aliphatic percarboxylic acids such as performic acid are desirably used in the process of this invention. A preferred organic carboxylic acid for use herein is peracetic acid. It is generally preferred to use substantially one mole of the organic peracid for each mole of the cyclo C12 to be treated.

ln-order to secure good yields of bicyclo C12 an alkaline reagent should be present. While the reaction mixture of this invention should be substantially anhydrous, the term alkaline reagent as used herein means a material which would make the reaction mixture alkaline in aqueous media. A wide variety of salts of a strong base and a weaker acid can be used for this purpose. A preferred pH-controlling material is anhydrous sodium acetate.

The treatment of cyclo C12 with epoxidizing agent is preferably carried out in an inert reaction vehicle. Such a reaction vehicle is desirably a solvent for the components of the reaction mixture or a liquid in which the components of the reaction mixture readily disperse. The vehicle serves to insure more intimate contact of the ingredients of the reaction mixture and to assist in temperature control, as well as to moderate the reaction. Suitable vehicles for use in the process include chlorinated hydrocarbons such as chloroform and carbon tetrachloride, aromatic materials such as benzene and toluene, and oxygen-containing solvents such as diethylether. A preferred vehicle in the practice of this aspect of the invention is methylene chloride. The epoxidation can be carried out over a fairly wide range of temperatures, depending upon the particular concentration of reactants, the size of the reaction vessel and other equipment available, and the like. At too low a temperature, the reaction requires an inordinately long period of time, while at too high a temperature the reaction becomes unduly rapid. In fact, at unduly high temperatures the reaction rate may become so vigorous as to be explosive. Accordingly, it is desirable to carry out the epoxidation reaction at temperatures in the range of from about -l5C to about 30C.

The time required. for the epoxidation reaction varies inversely with the temperature and should be sufficient to provide a high completeness for the reaction. The reaction is conveniently controlled by introducing the cyclo C12 and vehicle, if any, into a reaction vessel fitted with mixing means and heat transfer means and then slowly adding the requisite amount of epoxidation agent. The reaction mass can, if necessary, be maintained in the desired temperature range after all the agent is added until the reaction is complete.

Generally, a temperature range of from about -l5 to about 30C over a period of about 2-5 hours is required for the percarboxylic acid addition. The reaction can be carried out at subor superatmospheric pressure, but if a subatmospheric pressure is used it should not be so low as to cause ebullition or substantial evaporation of the vehicle or any of the reactants. The reaction is preferably carried out at atmospheric 4 pressure. Since this reaction is sensitive to the presence of water, it should not be conducted in a very humid atmosphere, although there is no need to exclude air. If desired, the reaction can be carried out under an inert atmosphere such as nitrogen, argon, and the like.

When the epoxidation reaction is substantially complete, it is terminated by the addition of water. The water is mixed into the organic material and is subsequently removed therefrom, being most readily removed by decantation of the organic layer from the aqueous layer.

The reaction product mixture can be further purified by the addition of a reducing agent to inactivate any traces of the epoxidation agent. For example, the organic layer can be treated with an aqueous solution of a reagent such as ferrous ammonium sulfate. The reaction product is generally further deacidified, for example with aqueous sodium bicarbonate solution, to remove all traces of acidic materials. The bicyclo C1 2 is obtained from the reaction mixture by distillation after the washing and decantation of the organic layer.

The reaction product is a clear liquid with an intense and persistent woody-amber odor. It has a boiling point of l06-l08C. at 1.0 mm. Hg and an n of 15046-15053. The IR, NMR, and mass spectra are consistent with several possible geometric isomers, including one having the structure:

Bicyclo C12 derivatives are produced by treatment with hydrogen in the presence of a hydrogenation catalyst such as nickel, palladium, platinum, rhodium, or salts thereof. Preferred hydrogenation catalysts are palladium and it salts such as palladium chloride.

Where the dihydro bicyclo C12 derivative is desired, the material is treated with 1 mole of hydrogen. The tetrahydro material can be obtained by utilizing 2 or more moles of hydrogen. It will be understood that mixtures of the bicyclo C-1 2 and dihydro material or of the dihydro and tetrahydro derivatives can be made by varying the quantity of hydrogen up to two moles. The hydrogenation can be carried out at pressures from atmospheric up to about 200 psig. Superatmospheric pressures on the order of 100 psig are preferred because the reaction proceeds more rapidly and completely under such pressure conditions.

To carry out the hydrogenation, the catalyst can be directly introduced into the bicyclo C12 and the mixture can then be treated with hydrogen. It is preferred that an inert reaction vehicle be admixed with the bicyclo C12 in the hydrogenation process. For example; lower alkanols are desirable reaction vehicles, and ethanol is a preferred reaction vehicle.

The temperature used can range from room temperature to over 100C, and is preferably maintained at -100C. At low temperatures the hydrogen is only slowly absorbed, whereasat temperatures greatly in excess of 100C, the reaction proceeds so rapidly as to present problems in controlling it.

The hydrogenated bicyclo C-l2 is recovered from the reaction mixture by filtration to remove the catalyst solids and by a subsequent distillation to remove any reaction vehicle which has been used. It is preferred that such distillation to remove the vehicle be carried out under a vacuum. If desired, the hydrogenated material can be further purified by fractional distillation.

Hydrogenation of the bicyclo C-l2 with one mole of hydrogen produces dihydro compounds including 1,5 ,9-trimethyl-l 3-oxabicyclo[ l 0. l .O]-tridec-4-ene. This is a colorless oil having a woody-amber odor, a boiling point of 72C at 0.2 mm Hg, and an n of 1.5021. Spectral tests indicate a molecular weight of 222 and that the structure of the compound is as follows:

The cyclization of the cyclo C-l2 or bicyclo C-l2 is preferably carried out in the presence of a reaction vehicle, desirably one in which the reactants are soluble or readily dispersed. Examples of desirable solvents are aromatic solvents and substituted aromatic solvents such as benzene, toluene, xylene, and chlorobenzene, aliphatic solvents such as hexane, and chlorinated aliphatic hydrocarbons. Benzene and toluene are preferred vehicles.

The cyclization of cyclo.C-l2 is carried out by admixing in any order the vehicle, the cyclizing agent, and the cyclo C-l2. The cyclization temperature can range from room temperature or somewhat below, e.g. C, up to 300C, although upper temperatures of 200C or below are desirable in many instancesQThelower temperatures result in very long reaction times, so that it is preferable to use higher temperatures,depending upon the cyclizing agent and the reaction vehicle used. Tem- 6 peratures at the upper end of the range may cause side reactions to proceed more rapidly than the desired cyclization and thus lower the yield.

A further factor determining the cyclization temperature is the boiling or melting point of the reaction vehicle. The reaction can be carried out at subor superatmospheric temperatures, and atmospheric pressure is usually the most convenient and desirable. Accordingly, it is generally preferred to carry out the cyclization reaction at temperatures at or below the boiling point of the vehicle, and use of a vehicle at reflux temperatures provides ready temperature control. Thus, for cyclizing cyclo C-1 2, temperatures of 25 to 300C, can be used, although an upper temperature limit of 200 is desirable. This cyclization reaction is most usefully carried out at temperatures of to C. At these temperatures the reaction can be carried out for from about 15 minutes to about ten hours, the actual time depending upon the cyclizing agent, vehicle, pressure, and type of cyclized product desired.

To cyclize bicyclo C-l2 a mixture of vehicles and cyclizing agent is prepared, and the bicyclo C-l2 is then added over a period of from about 2 to about 8 hours while the temperature is desirably maintained in the range of from 30C. to 40C. A preferred temperature range for carrying out the cyclization reaction is from about 32-35C. The time required varies inversely with temperature. If the addition is carried out too rapidly and the temperature is very high, some breakdown of the bicyclo C-l2 may occur, but very low reaction temperatures require inordinately long times to complete the reaction. Accordingly, it is preferred to perform this reaction under conditions such that 4-8 hours are required substantially to complete the reaction.

After the cyclization reaction is complete water is added to wash the organicmaterial which is then decanted. The reaction'product' can be subjected to one or more further washings and is then treated with an alkalizing agent, such as a strongalkali like sodium hydroxide or the salt'of a strongbase and a weak acid like sodium bicarbonate, to removeall further traces of acidity.

After the cyclization reaction is complete and the reaction-mixture has been neutralized and washed, the product is preferably further purified, for example, by distillation or extraction. Fractional distillation has been found to be especially satisfactory for purifying the product. When even greater purity is desirable, the product can be purified by preparative chromatographic techniques.

Cyclized cyclo C-12 produced according to this invention can further be treated with an epoxidation agent to form the epoxy derivatives. The epoxy derivatives of cyclized cyclo C-12are prepared in substantially the same manner as is the bicyclo C-l2 prepared from the cyclo C-12. r

For the distilled cyclized bicyclo C-l2, it has been found preferable for perfumery to utilize the cyclized material which forms a constant-boiling mixture as determined by gas-liquid chromatographic analyses. By this method cyclized l,5,9-trimethyl-l3-oxabicyclo[l0.1 .O]trideca-4,8-diene is obtained as a clear liquid with a boiling point of 95-100C. at 0.4 mm. Hg, an n,, of 1.5040-1.510l, the infrared (IR) absorption spectrum shown in FIG. 1, and the nuclear magnetic resonance (NMR) spectrum shown in FIG. 2. This material has a pleasant, woody, camphoraceous odor.

In the FIG. 2 spectrum, the inflection peaking at about 5.3 ppm on the chart is presented in amplified form just above the complete presentation. The IR spectrum is obtained on a Beckman spectrophotometer Mode IR 4 under the indicated conditions and the NMR spectrum is obtained on a Varian Model A 60 at the indicated parameters.

The cyclized cyclo C-l 2, in a liquid having for example, fractions boiling at 106C to 128C at 1.0-1.5 mm. Hg with the lower boiling fractions showing an n,, of 1.5045 and ranging up to 1.5104 for the higher boiling fractions. After further treatment to epoxidize the cyclized material, the epoxy cyclized cyclo C-12 is a liquid having fractions boiling at temperatures of 120.134C at 1.6-1.3 mm Hg. The n ranges from 1.4948 for lower boilers to 1.4982 for the higher boilers. The cyclized cyclo C-12 has the infrared absorption spectrum shown in FIG. 3, and the epoxy cyclized cyclo C-12 has the infrared absorption spectrum shown in FIG. 4. The IR spectra of FIGS. 3 and 4 are obtained under the indicated conditions. The epoxy cyclized cyclo C-l2 has an intense pleasant woody, camphoraceous odor which is persistent. It is noted that the combination of cyclized bicyclo C-12 and epoxy cyclized cyclo C-12 gives a fragrance material having an intense initial odor note with excellent persistence.

The alcohol derivative of bicyclo C-l2 is prepared by treating the bicyclo material with a reducing agent to form the alcohol. Water and oxygen should be excluded from this reaction, and it is preferred that the reaction be conducted in an inert atmosphere, such as. nitrogen, argon, and the like. It is especially preferred that the reaction be carried out under a blanket of dry nitrogen.

of the alcohol is lithium aluminum hydride. The reaction is preferably carried out in the presence of a vehicle which is a solvent for the reducing agent. When lithium aluminum hydride is used as the reducing agent, materials such as Diglyme" (diethyleneglycol dimethyl ether) can be used as solvents, and tetrahydrofuran is particularly suited to the process. Tetrahydrofuran is also valuable in controlling the reaction because the mass can be held at the reflux temperature of the solvent.

The reduction is desirably carried out at temperatures of from 60 to 200C. The solvents for the reducing agents generally determine the upper temperatures at which the reaction can be carried out. At temperatures below the desired range the reduction is unduly slow. Superatmospheric pressures can be used to raise the ebullition temperature of the solvent or dispersing agent and permit operation at slightly higher temperatures. The time required for the reduction desirably ranges from 2 to hours.

After the alcohol has been formed by the reduction, water is slowly added to the reaction mass and the alkaline materials are then neutralized by the addition of a suitable acid such as acetic acid. The alcohol formed is removed from the reaction mass with a suitable solvent such as diethylether.

The mixture of

geometric isomers

1,5,9-trimethylcyclododeca-4,8-dien-l-ol so prepared is a clear liquid having a boiling point of 1l31l8C at 0.1 mm. Hg and an u of 1.5134-1.5143. This alcohol has a persistent woody, vetivert odor. One component of this mixture can be represented by the structural formula:

The ketone isomer mixture of this invention can be prepared by a reaction similar to that used to form the epoxide, except that the alkalizing or pH-controlling agent is omitted from the percarboxylic acid. The same times, temperatures, pressures, and inert vehicles are used for the ketone production as are set forth above in connection with the bicyclo C-l2. The ketonic reaction product mixture is washed with water and an aqueous reducing agent to decompose any unreacted percarboxylic acid. The organic layer after washing until it is neutral to litmus is vacuum-distilled to remove any inert reaction vehicle. Treatment of the product with an alkalizing agent such as aqueous sodium bicarbonate can be used to assure removal of any residual acid.

The product is then fractionally distilled to obtain 1,5,9-trimethylcyclododeca-5,9-dien-2-one as a clear liquid with a boiling point of 128131C, at 2.6 mm. Hg and an n of l.5050-1.5057. The material can be represented by the structural formula:

The novel cyclododecadiene derivatives of this invention are particularly suited for use as perfume materials, as fragrance-modifying materials, and in the preparation of perfume compositions. They are very well adapted to perfumery where a woody aroma is required. The cyclized bicyclo C-12 is particularly remarkable for its persistent woody, camphoraceous odor, and the epoxy cyclized cyclo C-12 for its intense woody odor. The bicyclo C-l2 and the alcohol also possess a persistent woody amber odor with camphoraceous overtones. To make a woody amber type of perfume the materials of this invention can be combined with many types of odor materials such as floral, musk, spice, aldehydic, oak-moss, oriental, and fougere. The novel materials of this invention can also be combined with customary perfume additives such as natural oils,

synthetic oils, esters, aldehydes, ketones, alcohols, lactones, fixatives, solvents, dispersants, emulsifiers, surface-active agents, aerosol propellants, and the like.

It will be understood that the cyclized materials, the alcohol, and the ketone can be hydrogenated if desired to produce the dihydro or tetrahydro derivatives as described above in connection with the production of the dihydro and tetrahydro derivatives of bicyclo C-12 itself. I

The following examples serve to illustrate embodiments of the invention as it is now preferred to practice it. It will be understood that these examples are illustrative and the invention is to be considered restricted thereto only as indicated in the appended claims.

EXAMPLE I Preparation of the Bicyclo C-12 A mixture of 3 liters of anhydrous methylene chloride, 820 g. (10 moles) anhydrous sodium acetate and 1020 g. (5 moles) of l ,5,9-trimethylcyclododeca-l ,5,9- triene is introduced into a reaction vessel fitted with a stirrer, thermometer, and dropping funnel. The stirred reaction mass is brought to C and maintained at that temperature during a 3-hour period while 1005 g. (5.5 moles) of 40% peracetic acid is added. The reaction mass is maintained at 0-5C for an additional hour.

The organic layer is then washed with 2 liters of water to stop the reaction and decanted. The organic layer is washed with an equal volume of a aqueous solution of ferrous ammonium sulfate to remove any residual peracetic acid. The organic layer is then decanted, treated with a saturated aqueous solution of sodium bicarbonate and distilled to obtain 944 g. of 1,5 ,9-trimethyl-l 3-oxabicyclo[ 10. 1 .0]trideca-4,8- diene.

This material is a clear liquid with an intense woody amber odor. It has a B.P. of 106-108C. at 1.0 mm. Hg and an n of 1.5046-1 .5033. The NMR, IR, and mass spectrographic data are entirely consistent with the described structure.

Similar results are obtained when perbenzoic, chloroperbenzoic, performic, and perphthalic acids are utilized in lieu of the peracetic acid in the foregoing procedure.

EXAMPLE ll Partial Hydrogenation of the Bicyclo C-12 A mixture of 500 g. of the bicyclo C-l2 of Example I and 25 g. of palladium chloride is diluted with 500 g. of anhydrous ethanol, and one mole of hydrogen is introduced into the reaction mixture and absorbed at 100C, and 100 psig. The solid catalyst material is removed by filtration, and the resulting liquid is vacuum distilled to remove the ethanol.

1 ,5 ,9-Trimethyl-1 3-oxabicyclo[ 10. l .0]trideca-4-ene in the amount of 475 g. is obtained. This colorless oil has a molecular weight of 222, a boiling point of 72C, at 0.2 mm. Hg, and an n of 1.5021.

EXAMPLE-Ill The bicyclo C-l2,of. Example 1 is hydrogenated according to the method of Example ll over a 4-hour period to completely hydrogenate it. After filtration to remove the catalyst and removal of the ethanol as in Example 11, fractionation yields 480 g. of 1,5,9-trimethyl-13-oxabicyclo[10.l .0]tridecane, a colorless oil having a boiling point of 72C, at 0.2 mm, Hg and an n of 1,4975. NMR spectroscopy shows no unsaturation, and mass spectrometry shows a molecular weight of 224.

EXAMPLE 1V Cyclized Bicyclo C-12 A mixture of 960 g. of 85% phosphoric acid and 480 g. of benzene is introduced into a flask fitted with a stirre'r, reflux condenser, thermometer, and dropping funnel. The mixture is brought to a temperature of about 34C, and is then maintained at 3235C, while 957 g. of the bicyclo C-l2 prepared in Example I is added over a 1-2 hour time.

After six hours of continuous agitation at 3235C, the reaction mass is added to an equal volume of water. The organic layer is decanted and washed until it is neutral to litmus with a saturated aqueous solution of sodium bicarbonate and then distilled on a 24-inch Podbielniak column.

Approximately 750 g. of a constant boiling mixture of the cyclized material, as determined by gasliquid chromatographic analysis, is obtained. This material has a pleasant woody, camphoraceous odor, a boiling point of 32-36C, at 1.1 mm, Hg, an n of l.50401.5l0l, the infrared absorption

spectrum EXAMPLE V

1,5 ,9-Trimethylcyclododeca-4,8-dien-1-ol A mixture of 19 g. of lithium aluminum hydride and 500 ml. of tetrahydrofuran is introduced into a reaction flask fitted with a stirrer, reflux condenser, and dropping funnel after the flask is purged with dry nitrogen. A mixture of 51 g. of l,5,9-trimethyl-l3-oxabicyclo[10.1.0]-trideca-4,8-diene and ml. of tetrahydrofuran is added to the flask from the dropping funnel during a 2-hour period while the mixture is maintained at a gentle reflux. The heating is then continued for an additional 6 hours to maintain the mixture at reflux.

The reaction mixture is then cooled to roorri temperature and 32 g. of water is slowly added. Thirty ml. of 52% acetic acid is then added to the water and reaction mixture, and the mixture is extracted with an equal volume of diethylether.

The diethylether is distilled off toobtain 15 g. of 1,5,9-trimethylcyclododeca-4,8-dien-l-ol as a clear liquid with a boiling point of 1l3118C, at 0.1 mm. Hg and an n of l.5134-1.5143. Nuclear magnetic resonance data show that the material is a tertiary alcohol.

EXAMPLE V1

1 ,5 ,9-Trimethylcyclododeca-S ,9-dien-2-one A mixture o612 g. of 1,5,9-trimethylcyclododeca- 1,5,9-triene and 1800 ml. of methylene chloride are introduced into a flask fitted with a stirrer, thermometer, reflux condenser, and dropping funnel. The mixture is brought to a temperature of about 0C, and 605 g. of 40% peracetic acid is added during a 3-hour period while the mixture is maintained at 0-5C, with stirring. The agitation is continued for 3 hours after completion of the peracetic acid addition.

The reaction mass is then'washed with an equal volume of a 5% aqueous ferrous ammonium sulfate solution to destroy any unreacted peracetic acid. The organic layer is then washed to neutrality by test with litmus and the solvent is removed by vacuum distilla- 11 tion. The final product is distilled by means of a 3-foot tantalum wire column.

This produces I06 g. of I,5,9-trimethylcyclododeca- 5,9-dien-2-one as a water-white liquid having a boiling point of l28l3lC, at 2.6 mm, Hg and an n of l.5050-I.5057.

EXAMPLE VII Cyclized Cyclo C-l2 Into a one liter reaction flask equipped with a stirrer, thermometer, reflux condenser and heating mantle is placed 250 g. benzene, 250 g. polyphosphoric acid, and 250 g. trimethylcyclododecatriene. The mass is stirred and refluxed for 8 hours. The reaction mass thereupon separates into two phases: an organic phase and an aqueous acid phase. The organic phase is decanted, and the aqueous acid phase is washed with I volume of benzene.

The benzene layer is washed with three volumes of saturated sodium chloride solution and dried over magnesium sulfate and filtered. The benzene is recovered and the product is distilled. The resulting product is a mixture of isomers having a boiling range of I06l28C, at 1.0-1.5 mm, Hg and an n range of I.5045-l. 5 104. The infrared spectrum of this material is as shown in FIG. 3.

EXAMPLE VIII Epoxy Cyclized Cyclo C-l2 Into a 3 liter reaction flask equipped with a stirrer, a thermometer, reflux condenser and dropping funnel are placed 1000 ml. methylene chloride (Cl-l cl I80 g. anhydrous sodium acetate, and 238 g. cyclized cyclo C-l2 produced in Example VII. The reaction mass is cooled to C and stirred for a period of 3 hours during which time 248 g. of 40% peracetic acid is added dropwise.

When the addition of the peracetic acid is completed, stirring is continued for a period of 3 hours at a temperature range of 0C. up to C. The reaction mass is then left to stand overnight. After a period of approximately 12 hours the reaction mass is tested for peroxide content. One liter of water is added to the reaction mass, and the mass is' then stirred and transferred to a separatory funnel.

The organic layer is separated and washed with l volume of aqueous sodium chloride, 2 volumes of ferric ammonium sulfate [FeNl-I (SO two times 2 volumes of saturated sodium bicarbonate, and two volumes of saturated sodium chloride. The reaction mass .is then dried over magnesium sulfate and filtered, and the solvent is recovered at 50C at l0 mm Hg. The crude weight of the epoxidized product is 256 g.

The product is then distilled to obtain epoxy cyclized cyclo C-l2 as a liquid having a boiling range of l-l34C, at 1.6-1.3 mm,I-Ig and an n range of l.4948-l.4922. The IR spectrum is shown in FIG. 4. The material has an intense pleasant woody, camphoraceous odor.

EXAMPLE IX Perfume Composition A perfume composition is prepared by admixing the following ingredients in the indicated proportions:

Ingredient 1 Parts Bergamot oil I50 Orange oil (Florida) Lemon oil (California), C.P. l5 IMGA" (Gamma methyl ionone) 20 Cyclized bicyclo C-l 2 prepared in Example IV 50 Eugenol, U.S.P. l0 Lyral" (hydroxymethylpentyl cyclohexenecarboxaldehyde) 30 Styrallyl acetate 5 Ylang extra 4 Petitgrain SA 25 Patchouli dark 5 Camomile Oil, bulked 1 EXAMPLE X A second perfume composition is prepared by admixing the following ingredients in the indicated proportions:

Ingredient Parts Perfume composition prepared in Example IX' 390 Alcohol of bicyclo C-l2 prepared in Example V 50 Each of these two perfume base compositions is then admixed with aqueous ethanol, chilled, and filtered to produce a finished cologne. The two colognes so prepared have a citrus aroma leaning toward a woody, amber, camphoraceous fragrance note.

These base compositions can also be used to scent soap or other toilet goods such as lotion, aerosol sprays,

and the like. The other derivatives prepared according to this invention are similarly used, as further illustrated in the following Example.

EXAMPLE XI The following perfume composition is prepared:

The foregoing blend is evaluated and found to have a high degree of richness and persistence in its novel woody, amber-like quality.

What is claimed is:

1. A perfume composition containing as an essential fragrance ingredient a l,5,9-trimethylcyclododecatriene.-l,5 ,9 derivative of the formula v |:icH3 ..1 l

wherein CH 3 Let...

and the dashed lines represent double bonds; or

and the dashed lines represent single or double bonds, and at least one perfume additive selected from the group consisting of natural oils, synthetic oils, and fixatives.

2. A perfume composition as defined in claim 1, wherein said derivative is 1,5,9-trimethy1-l3-oxabicyclo [10.1.0] tridec-4-en.

3. A perfume composition as defined in claim 1, wherein said derivative is l,5,9-trimethyl-13-oxabicyclo [10.1.0] tridecane.

4. A perfume composition as defined in claim 1, wherein said derivative is 1,5,9-trimethylcyclododeca- 5,9-dierie-2-one.

5. A method for altering the fragrance of a perfume composition which comprises adding thereto a fragrance effective amount of a 1,5,9-trimethylcy- 14 clododecatriene-l,5,9-derivative selected from the group consisting of 1,5 ,9-trimethy1cycl0dodeca-4,8- dien-lo1; 1,5,9-trimethyl-13-oxabicyclo [10.1.0] tridec-4-ene; l,5,9-trimethyl-l3-oxabicyclo [10.1.0] tridecane; 1,5,9-trimethylcyclododeca-5,9-diene-2-one; cyclized l,5,9-trimethyl-l3-oxabicyclo [10.1.0] trideca-4,8 diene having a boiling point of -100% at 0.4 mmHg, and n of 1.5040-1.5101, the infrared spectrum shown in FIG. 1 and the NMR spectrum shown in FIG. 2; cyclized 1,5,9-trimethylcyclod0decatriene having a boiling range of 106 to 128C at 1.0-1.5 mmI-lg, an m of l.50451.5104 and the infrared absorption spectrum shown in FIG. 3; and an epoxycyclized 1,5,9- trimethylcyclododecatriene-1,5,9 having a boiling range of to 134C at 1.6-1.3 mmI-lg, an n of 1.4948 1.4922, and the infrared absorption spectrum shown in FIG. 4.

6. A method as defined in claim 5 wherein said derivative is 1,5,9-trimethyl-13-oxabicycl0 [10.1.0] tridec- 4-en.

7. A method as defined in claim 5 wherein said derivative is 1,5,9-trimethyl-l3-oxabicyclo [10.1.0] tridecane.

8. A method as defined in claim 5 wherein said derivative is 1,5,9-trimethylcyclododeca-5,9-diene-2-one.

9. A method as defined in claim 5 wherein said derivative is a cyclized 1,5,9-trimethyl-13-oxabicyclo [10.1.0]-trideca-4,8-diene having a boiling point of 95-100C at 0.4 mmI-Ig, an u of 1.5040-1.5101, the infrared absorption spectrum shown in FIG. 1 and the NMR spectrum shown in FIG. 2.

10. A method as defined in claim 5 wherein said derivative is a cyclized l,5,9-trimethylcyclododecatriene-1,5,9 having a boiling range 106 to 128C at l.0-1.5 mmI-Ig, an m of l.50451.51004, and the infrared absorption spectrum shown in FIG. 3.

11. A method as defined in claim 5 wherein said derivative is an

epoxy cyclized

1,5,9-trimethylcyclododecatriene-l ,5 ,9 having a boiling range of 120 to 134C at 1.6 1.3 mmI-Ig, an n of'1.4948-l.4922, and the infrared absorption spectrum shown in FIG. 4.

12. A method as defined in claim 5 wherein said derivative is 1,5,9-trimethyl-cyclododeca-4,8-dien-1- 0L =1 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATEHFNO. 3,929,675

DATED December 30 1975 INVENTOR(S) EYMOUR LEMBERG it is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 7, line 4, insert an "1" after "Mode" line 35, after "nitrogen" insert the following:

The desirable reducing agent for use in preparation-- Signed and Sealed this Twenty-seventh Day Of July 1976 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN 41 X ff (mnmissr'uner of Patents and Trademarks

Claims

1. A PERFUME COMPOSITION CONTAINING AS AN ESSENTIAL FRAGRANCE INGREDIENT A 1,5,9-TRIMETHYLCYCLODODECATRIENE-1,5,9 DERIVATIVE OF THE FORMULA

2. A perfume composition as defined in claim 1, wherein said derivative is 1,5,9-trimethyl-13-oxabicyclo (10.1.0) tridec-4-en.

3. A perfume composition as defined in claim 1, wherein said derivative is 1,5,9-trimethyl-13-oxabicyclo (10.1.0) tridecane.

4. A perfume composition as defined in claim 1, wherein said derivative is 1,5,9-trimethylcyclododeca-5,9-diene-2-one.

5. A method for altering the fragrance of a perfume composition which comprises adding thereto a fragrance effective amount of a 1,5,9-trimethylcyclododecatriene-1,5,9-derivative selected from the group consisting of 1,5,9-trimethylcyclododeca-4,8-dien-1-ol; 1,5,9-trimethyl-13-oxabicyclo (10.1.0) tridec-4-ene; 1,5,9-trimethyl-13-oxabicyclo (10.1.0) tridecane; 1,5,9-trimethylcyclododeca-5,9-diene-2-one; cyclized 1,5,9-trimethyl-13-oxabicyclo (10.1.0) trideca-4,8 diene having a boiling point of 95-100% at 0.4 mmHg, and nD20 of 1.5040-1.5101, the infrared spectrum shown in FIG. 1 and the NMR spectrum shown in FIG. 2; cyclized 1,5,9-trimethylcyclododecatriene having a boiling range of 106* to 128*C at 1.0-1.5 mmHg, an nD20 of 1.5045-1.5104 and the infrared absorption spectrum shown in FIG. 3; and an epoxycyclized 1,5,9-trimethylcyclododecatriene-1,5,9 having a boiling range of 120* to 134*C at 1.6-1.3 mmHg, an nD20 of 1.4948 - 1.4922, and the infrared absorption spectrum shown in FIG. 4.

6. A method as defined in claim 5 wherein said derivative is 1, 5,9-trimethyl-13-oxabicyclo (10.1.0) tridec-4-en.

7. A method as defined in claim 5 wherein said derivative is 1, 5,9-trimethyl-13-oxabicyclo (10.1.0) tridecane.

8. A method as defined in claim 5 wherein said derivative is 1, 5,9-trimethylcyclododeca-5,9-diene-2-one.

9. A method as defined in claim 5 wherein said derivative is a cyclized 1,5,9-trimethyl-13-oxabicyclo (10.1.0)-trideca-4,8-diene having a boiling point of 95*-100*C at 0.4 mmHg, an nD20 of 1.5040-1.5101, the infrared absorption spectrum shown in FIG. 1 and the NMR spectrum shown in FIG. 2.

10. A method as defined in claim 5 wherein said derivative is a cyclized 1,5,9-trimethylcyclododecatriene-1,5,9 having a boiling range 106* to 128*C at 1.0-1.5 mmHg, an nD20 of 1.5045-1.51004, and the infrared absorption spectrum shown in FIG. 3.

11. A method as defined in claim 5 wherein said derivative is an epoxy cyclized 1,5,9-trimethylcyclododecatriene-1,5,9 having a boiling range of 120* to 134*C at 1.6 - 1.3 mmHg, an nD20 of 1.4948-1.4922, and the infrared absorption spectrum shown in FIG. 4.

12. A method as defined in claim 5 wherein said derivative is 1, 5,9-trimethyl-cyclododeca-4,8-dien-1-ol.