US3679750A - Hexahydro-1,4,9,9-tetramethyl-4,7-methano-azulenones - Google Patents

Abstract

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

Description

I United States Patent 11 1 ,679,750

Mookherjee July 25, 1972 HEXAHYDRO-l,4,9,9-TETRAMETHYL- [56] References Cited 4,7-METHANO-AZULENONES UNITED STATES PATENTS [721 Mwkheflu, Matawan, 3,407,225 10/1968 Dunkle .l ..260/586 A x [73] Assignee: International Flavors 8t Fragrances lnc., OTHER PUBLICATIONS New York, NY.

Treibs, Chem Abstracts," Vol. 44, pp. 3945i- 3947a, 1950 1 F11ed= June 10, 1968 Brown at al. Chem Abstracts," Vol. 66., p. 648471), (1967).

[21] Appl' 735545 Primary Examiner-Leon Zitver Assistant ExaminerNorman Morgenstern 52 U.S. c1. .260/586 A, 252/89, 252/108, y Haidt & Haffner 252/522, 252/DlG. 5, 252/DIG. l3, 252/DIG. 14, 260/617 F, 260/617 M, 260/6755, 424/59, 424/65, [57] ABSTRACT /70, 424/76 Novel hexahydro-l,4,9,9-tetramethyl-4,7-methanoazulenones [51] Int. Cl ..C07c 49/54 useful as olfactory agents; perfume compositions containing [58] Field of Search ....260/586,' 586 A, 586 R such azulenones; and methods for preparing such azulenones and such compositions.

3 Claims, No Drawings HEXAHYDRO-l ,4,9,9-TETRAMETHYL4,7-METHANO- AZULENONES BACKGROUND OF THE INVENTION fragrances to compositions. For example, Buchi et al., 84

J.A.C.S. 3205 (I962), show the production of hexahydro- 4,9,9-trimethyl-A --4,7-methanoazulenel 2H )-one. The odor of this ketone was not stated. It is found to have a weak woody odor.

THE INVENTION R1 1 ll wherein one of R and R is oxygen and the other represents two hydrogen atoms, R is methyl, or when R is oxygen, methyl or methylene, and one of the dashed lines represents a double bond. It also relates to the use of these unsaturated ketones as olfactory agents and in perfume compositions, as well as in the preparation of such compositions. The novel azulenones of the present invention providea superior intense, camphoraceous woody amber fragrance note. Accordingly, smaller quantities can be used to impart a camphoraceous, 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 hexahydro derivatives of methanoazulene and are hexahydrol ,4,9,9-tetramethyl-A -4,7- methanoazulen-3(2H)-one O l l hexahydro-l ,4,9,9-tetramethyl-A" -4,7-methanoazulen-3( hexahydrol -methylene-4,9,9-trimethyl-A -4,7- mcthanoazulen-3 2H )-one hexahydro-l ,4,9,9-tetramethyl-A --4,7-methanoazulen-8( (Ill) and mixtures thereof. It will be appreciated that the foregoing structures include the various stereoisomeric forms.

The unsaturated ketones can be used individually or in admixture. Generally, the ketones are utilized in admixture, and

in many aspects of the present invention a mixture of the four cyclic ketones is preferred.

The unsaturated ketones of this invention are useful as olfactory agents and fragrances. They have a camphoraceous woody amber 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 proportioned 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; (0) 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 low-boiling freshsmelling 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 effects of all ingredients. 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 other ingredients 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 5-7 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 0.01 percent of the novel ketones will suffice to impart an amber, camphoraceous woody odor. Generally it is'preferred not to use more than 0.5 percent because no additional benefit is obtained and the fragrance may become unbalanced.

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

The novel unsaturated ketones of this invention are prepared by oxidizing l,4,9,9-tetramethyl-A --octahydrowherein the dashed lines, R R and R, are as set forth above. As further disclosed hereinafter, the oxidation is to provide the keto form as indicated without change in the hydrocarbon skeleton.

beta-Patchoulene is readily prepared according to the method of Bates and Slagel, 84 J.A.C.S. 1307 (1962). The beta-patchoulene utilized herein as starting material is obtained by treating bulnesol treating the patchoulene with an agent which will oxidize a methylene group in the position alpha to a carbon-carbon double bond. Suitable agents are metal oxides such as chromium trioxide, selenium dioxide, and the like and alkali-metal dichromates such as sodium dichromate, potassium dichromate, and the like. It will be understood by those skilled in the art that materials furnishing these oxidizing agents under the reaction conditions can be used in the practice of this process.

It is frequently desirable to carry out the reaction in an acidic milieu, and acids suitable for this purpose include both strong mineral acids such as sulfuric acid and the like and organic acids such'as acetic acid, acetic anhydride, and other lower alkanoic acids and their anhydrides. Thus, the combination of sulfuric acid with alkali-metal dichromates and of acetic acid and/or acetic anhydride with chromium trioxide is used. Chromiumtrioxide-acetic acid is the preferred oxidizing agent because of its specificity in oxidizing a methylene to a carbonyl.

The time and temperature at which the reaction is carried out are interrelated. It has been found that temperatures of from about C to about 80 C can be used in carrying out the process of the present invention. The reaction time is chosen to obtain the desired yields of the unsaturated ketones. Thus, it has been found that the reaction can be carried out for to days at 2030 C or for 20 to 22 hours at 50-60 C with good results.

The reaction is preferably carried out in an inert vehicle which will not be attacked by the reactants under the reaction conditions and which will serve to promote contact between the reactants and to moderate'the reaction. The vehicle can be a solvent for reactants. It is preferred to have t-butanol present.

The amount of oxidizing agent can be varied over a range depending upon the desired reaction rate, the particular oxidizing agent, the reaction vehicle employed, and the time and temperature of the reaction. It is generally preferred that an equimolar or greater quantity of oxidizing agent, based on the amount of patchoulene, be present. The quantity of acid present should be from 10 to 20 equivalents, based on the beta-patchoulene.

The reaction can be carried out over a wide range of pressure from subto superatmospheric. It is generally preferred to carry out the reaction under atmospheric pressure.

Depending upon the particular isomer or isomer mixture of ketones prepared according to this invention, the ketones can be purified and/or isolated as desired. Any unreacted chromic oxidizing agent can be decomposed with a suitable agent, such as oxalic acid. The final unsaturated 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 products can be carried out by conventional techniques. Thus, the products can be purified, separated, and/or isolated by distillation, extraction, preparative chromatographic techniques, and the like. It is frequently desirable to wash and dry the mixture of ketones prior to final purification and/or isolation.

As disclosed above, the novel unsaturated methanoazulene ketones of this invention can be utilized as olfactory agents and in perfume and perfumed articles. They can also be further treated to obtain other useful materials. Thus, copending application Ser. No. 735,544 filed June 10, 1968, in the name of James D. Grossman et al., entitled Novel Process and Product," discloses methods for the production of per hydro alcohols from the novel unsaturated ketones of this invention. Such alcohols can be further treated to provide saturated ketones having great utility as olfactory agents.

All parts, proportions, percentages, and'ratios herein are by weight, unless otherwise stated.

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 DIRECT OXIDATION OF BETA-PATCHOULENE TO FORM UNSATURATED KETONES A: Oxidizing Agent Into a 3-liter reaction flask equipped with a reflux condenser, Y-tube, stirrer and nitrogen purge means, 1.2 liters of t-butyl alcohol is introduced. During nitrogen purging, 400 g. of anhydrous chromium trioxide is added to the t-butyl alcohol over a l-hour period. The reaction mass is then dissolved in carbon tetrachloride (2 liters) and washed with three 500 cc. portions of water and dried over anhydrous sodium sulfate. B: Direct Oxidation Reaction Into a l2-liter reaction flask equipped with a reflux condenser, stirrer, Y-tube, thermometer and addition funnel, are placed:

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

The mass is stirred and heated to 50 C.

A solution is obtained by admixing 3% liters of the chromium oxide/t-butyl alcohol complex prepared as in A above, 160 cc. of acetic anhydride, and 600 cc. of acetic acid. This solution is added dropwise to the beta-patchoulene solution over a 2 k hour period, while maintaining the reaction mass at 50 C. The reaction mass is then stirred for hours at 50 C.

The reaction mixture is then washed with a solution of 1,500 g. of oxalic acid in 12 liters of water, twice with 500 cc. of water, neutralized with saturated Na CO solution and then again twice with water. The washed material is dried over anhydrous sodium sulfate and concentrated under vacuum.

The crude concentrated material (195 g.) is distilled at ll3l48 C and 1.8-0.8 mm Hg to yield a mixture ofl. 11, 111, and IV. This mixture has a pleasant woody-amber camphoraceous patchouli-like odor. The individual compounds are separated by gas-liquid chromatography (GLC) (20 feet X 7 4 feet column containing 5 percent Carbowax 20M" polyethylene glycol coated on Anakrom ABS" silanized acid-washed calcined diatomaceous earth made by Analab, Inc., Hamden, Conn.; flow rate, 100 microliters/minute; column temperature, 220 C; chart speed, 15 in./hour).

I has a strong patchouli camphor aroma.

I] has an excellent minty-camphory -woody odor, and a patchouli note as well as a peppery fragrance note. ll is obtained by means offractional distillation.

lll has an ambery-cedar woody aroma and a desirable incense quality.

IV has a woody-camphory odor.

According to GLC analysis, the ratio of lzlllzlV is approximately 17.7 percent: 65.0 percent: l7.2 percent.

lnfrared analysis of the four materials yields the following data:

Table 1 shows the absorption bands (in cm") of various structural features of the four compounds.

Mass spectra of the four materials show peaks (in order of decreasing intensity) on a Consolidated Electrodynamics Corp. Model 21-103C instrument:

Material Parent Peaks Other Peaks I 218 l75,41,133,69

11 218 41,39.190,109,9l,45 III 218 l2l,l22,4l,39,9l.

1V 2.16 173,4l,2l6,31,45,69

Nuclear magnetic resonance (NMR) analysis confirms the structures of compounds I-IV as given above. NMR analyses for specific stereo isomers of each of compounds I-IV are as follows, wherein the number and H in parentheses indicates the number of hydrogen atoms attributable to the band:

lsonur (n) of Formuln l 11' em Singlet time. an). .n

Il :u-.ing ()j olupounil ll U I 'lwo singlets nl. 50

1\ n|ul5Hll7,(till). ll (I! llu & Singlet nt (18 H7, (3H). I F (llh- (ll Il-uciug (1 ()1 llrolul singlet at 106 I llz. (lll; (3'

lsonur (n) 01 Formula 111 'lwo singlets tit 51 I :nulM llz (fill). (illn (Z- Ulla Doublets nt 58 and ti l I llz. Ulla-"(#43 11 ISOl ltl (h) of Formula 111 Singlet nth 1 ll7. (till). I (lllzrtll (lllzi Singlet nt 65 111.5. I

out 0 "(1.41 ll Ella I H Doublct at 63 and 70 (1:

Hz. CII -|-O C- Compound IV 0 Two singlets at 60 CII3CC H l 1\ and 55 Hz (611). I Singlet at 78 Hz (3H). OH3-CC=C l [Facing 0:0]

Broad singlet at Hz (2H). C=C-CI-I Broad doublet at 298 C CH; I17, (211).

The presence of conjugated carbonyl in compounds I and IV is indicated by X m at 274 and 242 mg, respectively, in the ultraviolet. spectra.

EXAMPLE II The ketone mixture prepared in Example I is dissolved in alcohol to obtain a 10 percent solution, and a second 10 percent solution is prepared by dissolving hexahydro-4,9,9-trimethyl- A--4,7-methanoazulen-l(2I-I)-one (the trialkyl azulene material produced by Buchi et al., supra, hereinafter called the trialkyl azulene" material) in alcohol. A 10 percent solution of ketones prepared according to Example I has a strong camphoraceous woody amber fragrance, whereas the other solution is almost odorless. A I percent solution of the ketones prepared in Example I displays a distinct, recognizable patchouli-like odor and is still considerably stronger than the 10 percent solution of the trialkyl azulene material.

Similar results are obtained with the individual ketones I, II, III and IV prepared according to the present invention.

EXAMPLE III PERFUME COMPOSITION A further comparison is carried out utilizing the following perfume base compositions:

Ingredient Benzyl Acetate Petitgrain Absolute Phenyl Ethyl Alcohol Bergamot Cananga Oil Java Opoponax Oil Geraniol Citronellol Myrrh Oil Tincture Castoreum 20% Musk Xylol Sandalwood Oil Vanillin Coumarin Amount (Parts) To separate samples of the foregoing base are added (A) 5 parts of the trialkyl azulene material, (B) 5 parts of the ketone mixture of Example I, and (C) 5 parts of patchouli oil.

Sample A shows substantially no change in aroma from the base composition, while sample B shows the woody, oriental fragrance effect resembling that obtained by the use of genuine patchouli oil (Sample C).

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

Ingredient Parts Vetivert Oil 40 Ketone Mixture of Example I 60 Sandalwood Oil I00 Rose Geranium Oil 200 Musk Extract (3%) 25 Civet Extract (3%) 25 Benzyl-iso-Eugenol I00 Coumarin I00 Heliotropin 50 Bois de Rose Oil 200 Benzoin Resin I00 I000 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 the individual ketones of the present invention can be used separately or in combination with each other to provide a good intense camphoraceous woody fragrance note.

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 v PREPARATION OF SOAP COMPOSITION One hundred grams of soap chips are mixed with 1 gram of the perfume composition of Example IV until a substantially homogeneous composition is obtained. The perfumed soap composition manifests an excellent woody, amber, patchouli odor character.

EXAMPLE VI PREPARATION OF A DETERGENT COMPOSITION A total of grams of detergent powder is mixed with 0.15 grams of the perfume composition of Example IV until a substantially homogeneous composition is obtained. This composition has an excellent woody, amber odor.

EXAMPLE VII PREPARATION OF A COSMETIC POWDER COMPOSITION A cosmetic powder is prepared by mixing in a ball mill 100 grams of talcum powder with 0.25 grams of the mixture obtained from the process of Example I. The powder has an excellent camphoraceous, woody, patchouli-like odor.

EXAMPLE VIII PERFUMED LIQUID DETERGENT wherein R is methyl or methylene, and one of the dashed lines represents a double bond. I I

2. An unsaturated ketone according to claim 1, wherein R is methyl.

3. An unsaturated ketone according to claim I, wherein R is methylene, and the dashed line which is beta to R is a double bond.

CERTIFICATE OF CORRECTION Patent NO. 3,679,750 Dated July 25, 1972 lnvento D.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 1, lines 35-55 correct Table 1 to read as .follows:

TABLE I Compound I I I 111 I 7 5-Membered 1625,1695 1740 5 None 1700 ring carbonyl (conjugated) (non-conjugated) (conjugated) Methylene 1425 1425 None 1432 Alpha to carbonyl gem-Dimethyl 1370-90 1370-90 1370-90 1390, and l or 2 (2 Me (2 Me (2 Me (1 Me Group) methyl group Groups) Groups) Groups) 6-Membered None None 1625 None conjugated 1670 ring ketone Conjugated None None None 1570,1630 C=C bonds exo-Vinylidene None None None 885,3080

in 5-m'embered ring (Continued) USC OMM-DC 60376-969 h u s covcnrmzm PRINYING OFFICE I969 0-166-131 UNITED STATES PATENT OJQIC 1 F. e A. IFF 2028B CbRTlr IQATQL 0F LDRRECTEON Patent No. 3, 679 750 1 Dated July 25 1972 Inventor(s) BRAJA M OKHERJEE It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Page 2 Col. 6, Lines 5-10, correct Formula I to read:

Col. 6, line 40, correct Formula III to read:

Claim 1, col. 8, line 55, correct the formula to read:

Signed and sealed this 6th day of February 1973.

(SEAL) Attest:

ROBERT GOITSCHALK Commissioner of Patents EDWARD MQFLETCHER R. Attesting Officer

Claims (2)

1. 2. An unsaturated ketone according to claim 1, wherein R3 is methyl.
2. 3. An unsaturated ketone according to claim 1, wherein R3 is methylene, and the dashed line which is beta to R3 is a double bond.