US3929677A

US3929677A - Perfume compositions and perfurme articles containing one isomer of an octahydrotetramethyl acetonaphthone

Info

Publication number: US3929677A
Application number: US529086A
Authority: US
Inventors: John B Hall; James Milton Sanders
Original assignee: International Flavors and Fragrances Inc
Current assignee: International Flavors and Fragrances Inc
Priority date: 1974-01-21
Filing date: 1974-12-03
Publication date: 1975-12-30
Anticipated expiration: 1992-12-30

Abstract

(WHEREIN THE DASHED LINES REPRESENT METHYL GROUPS ''''CIS'''' TO ONE ANOTHER) HAVE BEEN DISCOVERED TO BE USEFUL AS AMBER AND FRUITY AMBER FRAGRANCE INGREDIENTS.

Products produced by the process comprising reacting myrcene with 3-methyl-3-pentene-2-one to form a substituted acyl cyclohexene Diels-Alder adduct and then cyclizing said DielsAlder adduct with an acid cyclizing agent, in particular, the isomer having the structure;

Description

United States Patent [191 Hall et al.

[451 Dec. 30, 1975 [75] Inventors: John B. Hall, Rumson; James Milton Sanders, Eatontown, both of NJ.

[73] Assignee: International Flavors & Fragrances Inc., New York, NY.

22 Filed: Dec. 3, 1974 21 Appl. No.: 529,086

Related U.S. Application Data [60] Division of Ser. No. 434,948, Jan. 21, 1974, which is a continuation-in-part of Ser. No. 336,172, Feb. 27, 1973, abandoned.

[52] U.S. Cl 252/522; 260/586 R; 260/586 C;

260/675.5 [51] Int. Cl. A61K 2/46; C1 13 9/00 [58] Field of Search 252/522; 260/675.5, 506

[56] References Cited UNITED STATES PATENTS 4/1960 Ohloff et al 260/343.2 1/1963 Kitchens 260/488 OTHER PUBLlCATlONS R. Gould, Mechanism and Structure in Organic Chemistry," p 537, (1959).

Primary Examiner-Hetbert Levine Assistant ExaminerG. E. Schmitkons Attorney, Agent, or FirmArthur L. Liberman, Esq.; Harold Haidt, Esq.

57 ABSTRACT Products produced by the process comprising reacting myrcene with 3-methyl-3-pentene-2-one to form a substituted acyl cyclohexene Diels-Alder adduct and then cyclizing said Diels-Alder adduct with an acid cyclizing agent, in particular, the isomer having the structure;

(wherein the dashed lines represent methyl groups cis" to one another) have been discovered to be useful as amber and fruity amber fragrance ingredients.

8 Claims, 6 Drawing Figures 2mm m6 A 618 4365 ...zw om Gm N.

Ewan? mmm m aonmdwv 'IVNQIS 9 onm one om n 03 02 3w 8 0 9 1 p 1 .rr PL. a 1. P11. 2fi m E9; mu E 009 A 61 Sheet 2 0f 6 Dec. 30, 1975 US. Patent MAJOR PEAK FROM EXAMPLE IE1 INTENSITY I800 I700 I600 I500 I400 US. Patent Dec. 30, 1975 Sheei4 on 3,929,677-

A 200 0ZmDOmmm 00% 00mm 000m 00mm 000m w m w m PERFUME COMPOSITIONS AND PERFUME ARTICLES CONTAINING ONE ISOMER OF AN OCTAHYDROTETRAMETHYL ACETONAPHTHONE This application is a Division of copending application for U.S. Letters Patent Ser. No. 434,948 tiled on Jan. 21, 1974 which is, in turn, a continuation-in-part of application for U.S. Letters Pat. Ser. No. 336,172 filed on Feb. 27, 1973, now abandoned.

BACKGROUND OF THE INVENTION Materials which can provide amber fragrance notes are known in the art of perfumery. Manyof the natural materials which provide such amber fragrances and contribute desired nuances to perfumery compositions such as ambergris can no longer be obtained or are high in cost or vary in quality from one batch to another and/or generally subject to the usual variations of natural products. v

There is accordingly a continuing effort to find synthetic materials which will replace the essential fragrance notes provided by natural essential oils or compositions thereof having an amber aroma. Unfortunately, many of these synthetic materials either have the desired nuances only to a relatively small degree or else contribute undesirable or unwanted odors to the compositions. The search for materials which can provide a more refined amber fragrance has been difficult and relatively costly in the areas of both natural products and synthetic products.

The present invention provides a solution to the aforementioned problem by providing perfume compositions and perfumed articles which include isomer mixtures and a specific isomer which give rise to unexpectedly intense and persistent natural amber or fruity amber fragrance notes heretofore unknown in the'acetonaphthone class of fragrance materials. Indeed, in the perfumers art, there is considerable need today for substituents having amber or fruity amber fragrance notes which are persistent. Especially desirable are materials which have an amber or fruity amber fragrance note which do not discolor with age. Such amber or fruity amber fragrance materials as stated above have a wide utilization in the preparation of finished perfume compounds. The materials when they are available from natural sources are subject to wide variations in quality, are expensive and are limited or often in critically short supply.

The prior art contains several disclosures of fragrance uses of compounds having structures similar to the compounds contained in the isomer mixtures useful in the practice of our invention and to the specific isomer useful in the practice of our invention.

British Pat. No. 896,039 entitled Method of Producing Derivatives of the l,l-Dimethyl-Octahydronaphthalene Series" discloses the generic process:

c

cu R2 compound

1,1,6,6 Tetramethyl-7-Ketomethyl-Octalin produced by (l) reacting myrcene and mesityl oxide thermally followed by (2) subsequent cyclization, has a pleasant woody ambergris smell. However, a repetition of the teachings of this British patent gives rise to the following results:

STRUCTURE -OF COMPOUND:

PERFUME PROPERTIES: Green, fruity STRUCTURE OF COMPOUND:

3 4 NAME: l,2,3',4,,6',7',8'-octuhydro-2',8',8(zmd -Continued 2', 5'5 )-trimetHyl2-naphthuldehyde PERFUME PROPERTIES: Green floral. fruity CH STRUCTURE OF COMPOUND:

. CHQ CHO 3 NAME: l',2,3',5',6,7',8'octahydro-3',3',8,8 (and 3 ,3 ,5 ,5 )-tetramethyl-2 '-acetonaphthone PERFUME PROPERTIES: Yeasty, Valerian-like.

. STRUCTURE OF COMPOUND:

CHO

PERFUME PROPERTIES: Green, buttery, woody 4 CH3 H STRUCTURE OF COMPOUND:

NAME: l,2,3,4,5,6',7,8-octahydro-2,8',8' (and 2', 5',5)-trimethyl-2'-acctonaphthone PERFUME PROPERTIES: Fruity, woody, pineapple- 40 like.

STRUCTURE OF COMPOUND:

8')-dimethyl-2"acetonaphthone PERFUME PROPERTIES: Ionone-like STRUCTURE OF COMPOUND:

Q 1 8. a. lnukai and M. Kasai,j.()rg.C/zem., 30,3567

(1965). v A b. T. lnukaiand T. Kojima,.J.Org.Chem., 31,1121

1966). 5 Lewis acid catalyzed reaction of isoprene with various acrylic acid derivatives.

9. Br. 1,076,304 (1965); CA, 68,49177f(l968 AlCl catalyzed reaction of methyl acrylatc, methyl methylacrylatc, or acrylonitrile with isoprene, pi-

perylene, chloroprcne, cyclopentadiene, or 1,3-

butadiene. (cf. U.S. Pat. No. 3,390,169).

10. G. P. Kugatova-Shemyakina, L. l. Rozhkova, V.

N. Gramenitskaya and V. M. Andreev, J.0rg.- Chem. USSR, 6,2459 (.1970).

Catalysis of the reaction of acrolein or crotonaldehyde with isoprene or piperylene.

11. S. R. Wallis J.Amer.Chem.S0c., 92,3218 (1970').

AlCl catalyzed Diels-Alder reaction of butadiene.

with 2-phenyl-2-cyclohexenone. v In addition, Lewis acid catalyzed Diels-Alder reactions wherein the dienophile is a,B-disubstituted with alkyl groups are disclosed in our copending U.S. patent aplI,2!,3l4ls!,6!,7I,8l octahydro 3l,sI,5I (and plication Set. NO. on June 7, 0W 3', 8, 8)-trimethyl-2-acetonaphthone PERFUME PROPERTIES, Low keyed woody, fruity. Further, cycl1zat1on react1ons of D1els-Alder adducts In addition to the above-mentioned British patent, of myrcene and a fhenophlle, are Set forth the above stated Sequence of: No. 3,076,022. Th1s patent d1scloses mteraha, preparal. Diels-Alder Reaction to form Diels-Alder adducts tion of thermal DielstAlder adduct of myrc,ene

methyl 1sopropenyl ketone and subsequent ac1d cycl1- f ll 2 gyzgfi gz of the DielS Alder.adduCtS zat1on to a product sa1d to possess an mtense amberis disclosed in detail y Ohlofi. Ann. 606,100 (1957) gr1s-l1ke note Repet1t1on of the process as d1sclosed The prior art is replete with disclosures of Dielsgave rise toaproduct possessing fruity'woody'pineap Alder reactions wherein Lewis acids are used as catapie notes rather.than an ambergrisdike note l 6 Ohloff [Chem1stry ofOdorlferous and Flavormg Subysts, as follows:

. I 1. H. o. Oddy, J.Amer.Chem.S0c., 45,2156 1923 stances 240 (dtpdge Fortschmteg def aluminum chloride catalyzed Dicls-Alder reaction of anthracene and maleic anhydride. 2. A. N. Johnson. U.S. Pat. No. 2.724,730 (1955);

a compound having the structure:

CA,51,74()9b(I9 57). 40 I t O AlCl catalyzed reaction of hexachlorocyclopentadiene with cyclopentene and hexachlorocyclopentene. 3. P.Yates and P.Eaton, J.Amer.Chem.S0c., 82,4436

(1960). AlCL, catalyzed reaction ofvanthrac enc and maleic anhydridc- 1 Ohloff indicates that materials of this nature have y and R Robmson, "rcsiny odors like olibanum, with amber type under- 83,249 1961 U.S. Pat. N0. 3,067,244 (1962). meg Lewis acid catalyzed Diels-Alder reaction of but-a.- diene, cyclopentadicnc, or anthracene with various THE INVENTION dlellophiles acroleln, methacrolein acrylic This invention relates to the use of synthetic amberacld, methyl Vinyl ketone)- dlenophllcs like fragrance ingredients for perfumes and cosmetics. ing a terminal Vinyl P are claimcd- More particularly, the invention has to do with amberwillbofskyt Banish and Davis, like fragrance compositions for use in p'erfumery comg- 26,4778 Tefrahedmn, posed of octahydro-2',3f,8,8'-tetramethyl-(2' or 3')- l9,2333 (I963). acetonaphthones in which a majority of said aceto- AlCl catalyzed reaction of butadiene d naphthones contains the double bond in the 9' l0 dimenthyl fumarate. position.

6. l. A. Favorskaya and E. M- Au inen, Zh. O s 16h. This invention also covers the use in perfumcry of a Khim., 33,2795 (1963); CA, 59,15191 d. novel isomer ofoctahydro-tetramethyl acetonaphthone BF catalyzed reaction of isoprene or 2,3-dimcthylhaving the structure:

butadicne-l,3 with methyl vinyl ketone, 2-hexen- 4-one, l-propionylcyclopentene, and l-propionylcyclohexene. 7. E. F. Lutz and G. M. Bailey, J.Amer.Chem.S0c.,

86,3899 (1964). Comparison of isomer ratio of thermal and SnCl4 catalyzed reaction of isoprene with acrolcin or methyl vinyl ketone.

Chemischen Forschung Vol. 12, Part2, l969,discloses wherein the dashed lines represent methyl groups cis" to one another. The materials useful in our invention include isomer mixtures of octahydro-2.3,8,8'-tetramethyl-(Z' or 3')- acetonaphthone having the generlc structure:

Such a generic structure includes individually compounds having an acetyl group at the 2' position, compounds having an acetyl group at the 3'-position and mixtures of such compounds. The generic structures set forth above are also intended to include geometric isomers wherein the acetyl group is cis" to the methyl group on the carbon atom adjacent to that bonded to the acetyl moiety and where the acetyl group is trans" to the methyl group on the carbon atom adjacent to that bonded to the acetyl moiety. The processes of our invention give rise to isomer mixtures containing the above-named isomers as well as the isomer having the structure:

b. Reacting myrcene with 3-methyl-3-penten-2-one without using a catalyst at temperatures in the range of 120 up to l80C forming a mixture of isomers (including geometric isomers) of alkenyl acetyl dimethyl substituted cyclohexenes having the generic structure:

tion as set forth in Example X1) or they can themselves be incorporated into a wide variety of finished perfume compounds. It has been found that the materials useful for practicing this invention have persistent fragrances more fully described below which adapts them for incorporation into perfume compounds where a distinct amber of fruity amber fragrance note is required.

In the first of the two reactions of the process for preparing the materials useful in practicing our invention, myrcene and 3-methyl-3-penten-2-one are the reactants. Myrcenc is generally available at purities of and upwards and it can be used in this form. It is generally preferred in the practice of this invention to use commercial myrcene (approximately 77% purity) although, obviously, purified myrcene may be used. Such a purification is readily accomplished by fractional distillation. The initial reaction may be a thermal Dicls-Alder reaction without the use of a Lewis acid catalyst at a temperature in the range of l2()l80C. Preferably. but not necessarily. an antioxidant and polymerization inhibitor such as the mixture of betanaphthylamine and pyrogallol may be utilized. as set forth in Example V of British Pat. No. 896.039. Upon performing the first step of the process of our invention by carrying out a thermal Diels Alder reaction without the use of a Lewis-acid catalyst. the resulting material will be a mixture of approximately 70 weight percent:

and 30 weight percent:

with unknown ratios of geometric cis-trans isomers of each. Where the initial Diels-Alder reaction is carried out using a Lewis acid catalyst, primarily geometric isomers having one basic structure are obtained, to wit:

Suitable Lewis acid catalysts are aluminum chloride, stannic chloride, titanium tetrachloride, boron trifluoride, and boron trifluoride complexes such as boron trifluoride etherates. The Lewis acid catalyst concentration workable in our process is from 0.5 up to 100 mole percent based on 3-methyl-3-penten-2-one with the preferred range being 3-8 mole percent. When using the Lewis acid catalyst, it is preferred that a solvent be used and suitable solvents are toluene, benzene and inert chlorinated hydrocarbon solvents such as chloroform and methylene chloride since they do not take part in the reaction. When using a Lewis acid catalyst, the first reaction is operated at a temperature in the range of up to 509C, preferably 35 -50C. In both the thermal and catalytic Diels-Alder reactions, the mole ratio of myrcene to 3-methyl-3-penten-2-one may be varied from 1:3 to 3:1 or even higher, since the excess reagent may be recovered substantially quantitatively. However, for efficiency and economy as to time, the preferred mole ratio is from 1.1:1 up to 1.211. The reagents and catalyst may be mixed in any order, however. it is preferred to sequentially add 3-methyl-3- pentcn-2-one and myrcene to a premix of the catalyst and solvent, the use of solvent in this reaction being preferred also.

The next reaction, following the Diels-Alder reaction, namely cyclization of the acetyl cyclohexene derivative (the Diels-Alder adduct), is accomplished by heating the cyclohexene derivative preferably with a mixture of an acid such as phosphoric acid, dilute sulfuric acid, boron trifluoride or boron trifluoride etherate in the presence of a solvent. The amount of acid cyclization agent may vary from up to 100 weight percent based on the weight of the cyclohexene derivative to he cyclized. Preferably, the weight percent of acid should be between 40 and 50 weight percent. Preferably, an inert solvent having a boiling point at or about the desired reaction temperature is used in the eyclization reaction. The reaction temperature may be anywhere between 25C and the reflux temperature of the reaction mixture. The preferred reaction temperature range is between 95 and 1 C and accordingly toluene is the preferred solvent since its boiling point at atmospheric pressure is 1 10C. The quantity of solvent used in the eyclization reaction may vary from 0 weight percent up to 100 weight percent based on the amount of cyclohexene derivative being cyclized. It is preferred to use approximately 50 weight percent of solvent. in the eyclization reaction, the order of mixing reagents and solvents is not critical.

The length of time and temperature of the eyclization reaction will determine the percentage of the geometric isomers having the basic structure:

as compared with the geometric isomers having the other possible basic structures, namely:

and

Periods of time of the order of -7 hours at temperatures of 7080C. will yield a mixture wherein isomers having the basic structure (I) will be produced in a quantity of about 80 85%, the remaining isomers having the basic structures (II)..(III) and (IV). However, if the cyclization reaction is run for a period of time of approximately hours, and, at 80C., greater, than 96% of the reaction product has a geometric isomer mixture having the basic structure (I). A temperature of reaction of l ISfC coupled with a time of reaction of 4 hours will also yield a geometric isomer mixture more than 96% of the compounds of which have the basic structure (I). A time of reaction of 6 hours coupled with a reaction temperature of l C will give rise to a reaction product wherein more than 99% of the geometric isomers have" the basic structure (I).

In the event that the first reaction, the Diels-Alder reaction, is carried out using a Lewis-acid catalyst, the mixture of isomers produced as a result of carrying out the second cyclization reaction on the resulting Diels- Alder reaction product has been found to contain a predominant quantity of an isomer having the structure:

Chromatographic techniques can then be effectively utilized to separate this novel isomer from the cyclization reaction mixture and such a technique is illustrated in Example XIV, infra. This isomer useful in carrying out our invention has a characteristic intense fruityamber note. The above isomers are distinguishable from one another by examination of their respective NMR, infrared, and Raman spectra. The fact that the isomers indicated by formulae 1 and V have a tetrasubstituted double bond, and the isomers indicated by formulae II, III and- IV have a double bond which is only trisubstituted and not tetrasubstituted is apparent from a study of FIGS. 1-6.

The two foregoing reactions may be performed in separate reaction vessels or, more preferably, they may be performed in the same reaction vessel whereby the Diels-Aldcr reaction and subsequent cyclization steps are carried out without isolating the intermediate Diels- Alder adduclt', the cyclohexene derivative. Accordingly, when the Diels-Alder reaction is complete, the desired amount of acid is added without any additional solvents, and the reaction mixture is then stirred at the desired temperature until cyclization is complete.

When the cyclization reaction is substantially complete, the reaction mass is then washed and the organic layer is separated and distilled.

The distilled product may be used as is or it may be further purified by using gas chromatography tech- 12 niques and/or oximation (see Example XI) followed by recovery of the purified reaction product from the oximc.

The reaction product mixtures as well as the specific isomer of our invention are clear liquids with intense and persistent unique amber and fruity-amber odors. The isomer mixtures as well as the novel specific iso mer of our invention are particularly suited to use as perfume materials in the preparation of perfume compositions. They are very well adapted to perfumery where an amber or fruity-amber aroma is required. The specific isomer useful in practicing our invention as well as the octahydro-tetramethyl-acetonaphthone isomer mixtures are particularly remarkable for their persistent'fruity amber and amber odors. To make an amber or fruity amber type of perfume, the materials useful in practicing this invention can be combined with auxiliary perfume adjuvants including one or more of many types of odor materials such as bergamot oil, vetiver oil, patchouli oil, sandalwood oil, oakmoss and floral musk. The novel materials of this invention can also be combined with the customary perfume auxiliary adjuvants, such as natural oils, synthetic oils, aldehydes, ketones, carboxylic acid esters, aryl alcohols, alkanols, lactones, saturated hydrocarbons, unsaturated hydrocarbons, fixatives, solvents, dispersants, surfact active agents, aerosol propellants, and the like.

In the accompanying drawings forming part of this application, the figures which represent charts referred to in the examples are listed as follows:

FIG. 1 is a chart showing the nuclear magnetic resonance spectrum of peak No. l trapped by gas chromatography techniques from the product produced by the process of Example II, or the major peak trapped by gas chromatography techniques from the product of Example VII.

FIG. 2 is a chart showing the nuclear magnetic resonance spectrum of peak Nos 2 trapped by gas chromatographic techniques from the material produced by the process of Example II.

FIG. 3 is a portion of the Raman spectrum of the major peak trapped by gas chromatographic techniques from the material produced according to the process of Example VII.

FIG. 4 is an infrared analysis spectrum of the material which is the major peak trapped by gas chromatographic techniques from the material produced according to the process of Example VII.

FIG. 5 is a nuclear magnetic resonance spectrum of the material produced according to the process of Example XIV.

FIG. 6 is the nuclear magnetic resonance spectrum of the product produced according to the process of Example XI.

The following examples serve to illustrate embodiments of our 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 1 toluene 3-Methyl-3-pentenone (2060 g, 95%) is added in minutes to a suspension of aluminum chloride (90 g) in toluene (2 kg). The initial exotherm dies out after approximately 5% of the 3-methyl-3-pentenone is added. The mass is warmed to C, and myrcene (3530 g, 77%) was added over a period of 2 hours with external cooling as needed to maintain the reaction mixture at 3540C. The mixture is stirred at 3540C for 2 hours, 27 g aluminum chloride is added, and the mass is stirred an additional 9 hours at 3 5-40C.

After standing overnight at room temperature, the mixture is washed at C with 10% sodium chloride 1430l380.1373,1351,l222,ll95,llll38,l098,

1090, I080 cm.

NMR analysis MH CDCl l.772.50 6(9H. mult.)

2.06 5( 3H. sing.)

.62 5(3H. sing.) .54 5(3H. sing.)

0.92 5(3H. sing.)

0.76 8( 3H. doublet) Note l:

All nuclear magnetic resonance chemical shifts are reported in parts per million relative to tctramethylsilane.

Mass Spectral Analysis: m/e 234 (M l9 l 123, l2l,106.69.43,4l. y

EXAMPLE Ir H PO The product of Example I (3 kg, 98.7%) is added over a period of 45 minutes to a well-stirred mixture of. 1.5 kg of toluene and 1.5 kg of 85% phosphoric acid maintained at 70-80C. The mixture is stirred vigorously at 7080C for 5.5 hours and then is cooled and mixed with 3 kg of crushed ice. The organic phase is subsequently washed with 10% sodium chloride solution. 10% sodium carbonate solution and saturated sodium chloride solution. The washed organic solution is mixed with triethanolamine (lOO g), Primol (50 g) and lonol (3 g) and is rapidly distilled under reduced pressure using a short column.

Fractionation of the crude product gives 2604 g of a mixture of geometric isomers (bp l34l 35C/2.8 mm Hg) having an intense amber aroma.

Using GLC analysis, this material shows two major peaks (Varian Aerograph model 200. 10' X A", 5% Carbowax K 20 M on chromosorb G, helium flow rate 80 cc per minute, temperature programmed l()0-200C at l0C/min.), Peak 1 93%, Peak 2 7%. Peaks 1 and 2 are trapped from the above column. The NMR spectra of the two peaks are quite different. The NMR analysis for Peak 1 is set forth in Table l and is as follows:

Table l Chemical Shifts Interpretation 2.!6 5(3H, singlet) /T\ [.00 5( 3H. singlet) 0.98 5(6H. singlet) 5 c c 1 c 4 O and 0.8] 8(3H, doublet. o

J=6cps) Table lcontinuecl Chemical Shifts lnterpretation 0.6l2.566( l lH.multiplct) The NMR analysis for Peak 2 is set forth in Table 2 and is as follows: 20

Table 2 Chemical Shifts Interpretation i 2.ll 5(3H. singlet) 1.08 8( 3H, singlet) Clj o 0.89 8(3H singlet) 5 C ().76 5(3H. singlet) 0470 8( 3H. doublet,

.l=4cps) Table 2-continued Chemical Shifts I I Interpretation U.652.I08( lUH. multiplet) and/or IR analysis for Peak 1: 2950, 2922, 1702, I455,

1440, 1382, 1359, 1235, 1196, 1178, 1159, I120, continued 1 103, 1092, 1083, 956cm". Ingredient Amount (Grams) Mass spectral analysis for Peak 1: m/e 234 (M 4',5'.6',7',8'- h d -2'. 2 9.191. 188.186.161. 149.147. 135.133.12 .11 3.8.8'-tetram :ihyl 2 :1ceto 109,107,105, 95, 93, 92, 83, 8] 79, 77, 69, 67, 55, 43, ph h nc produced by the process 41 of Example ll (prlor to GLC separation) 10 Generic structure of lsomers of mixture of Peak 1: Cyclizcd Bicyclo C-12 material produced according to the process of Example IV of 0 Canadian Patent 854.225 issued October 20, I970 5 lso Bornyl Cyclohexyl Alcohol 10 Benzyl Acetate 25 2n-Heptyl Cyclopentanonc 5 (TOTAL) 353.3

The foregoing blend is evaluated and found to have a high degree of richness and persistence in its novel natural amber quality. This base composition can be admixed with aqueous ethanol, chilled and filtered to produce a finished cologne. The cologne so prepared has an amber aroma leaning towards a woody amber EXAMPLE note. The base composition can also be used to scent soap or other toilet goods such as lotion, aerosol, sprays and the like.

Peak 1 has a slight buttery note with a strong woody amber character. Peak 2 is weak, low keyed with a green vegetable character.

A perfume composition is prepared by admixing the following ingredients in the indicated proportions:

(,0 EXAMPLE [V d 1 Amount(Grams) lnto a 2 liter reactlon vessel equipped w1th stirrer, xggg fi i sgfi thermometer and reflux condenser, the following ingre- M ethyl Nonyl Acetaldehyde 0.5 dients are Placed: F F I 400 grams Myrcene (77%) au if I00 228 grams 86.1% 3-Methyl-3-penten'e-2-one Petitgrain gA 1 gram lonol" (Registered trademark of the Shell Ber amot il Alp a Methyl mom 25 Chemical Co.) (Butylated Hydroxy Toluene) Mixture of isomers of l'.2',3' 50 grams Toluene The reaction vessel is operated at atmospheric pressure and the reaction mass is refluxed over a period of'28 hours at temperatures varying between 1 18 and 147C. At the end of the 28-hour reaction period. the reaction mass is distilled through a fractionation column after initially being stripped of toluene. The fractionation reflux ratio is 4:1 and the distillation range is 1121l4C vapor temperature at 0.8 mm. Hg. pressure. Yield 168 grams (55.7% of theory based on 3- methyl-3-pentene-2-one) of a mixture of Diels-Alder adducts having the generic structure:

EXAMPLE V The Diels-Alder product of Example 1V is added over a period of 45 minutes to a'well-stirred mixture of 100 grams toluene and 100 grams 62% sulfuric acid maintained at 7080C. The mixture is stirred vigorously at 70-80C for 6 hours and is then cooled and mixed with 1 kilogram of crushed ice. The organic phase is subse-' quently washed with 10% sodium chloride solution, 10% sodium carbonate solution and saturated sodium chloride solution. The washed organic solution is then mixed with triethanolamine g), Primol (5 g) and lonol (1 g) and is rapidly distilled under reduced pressure using a short column. In this way, a product is obtained containing only traces of uncyclized starting material and containing geometric isomers having the basic generic structure: A

EXAMPLE V1 Into a 2 liter reaction flask equipped with reflux condenser, stirrer and thermometer, the following ingredients are placed:

500 grams Diels-Alder adduct mixture prepared according to the process of Example IV 250 grams 85% phosphoric acid 250 grams toluene The reaction mass is heated to reflux at atmospheric pressure (1 18C) and maintained at reflux for a period of 3% hours after which time the reaction mass was cooled down. The reaction mass is then washed with one 1 liter portion of water; then two 500 cc portions of water; then one 500 cc portion of 5% sodium carbonate and finally one 500 cc portion of saturated sodium chloride. The washed reaction mass is then stripped of solvent thereby giving rise to 445 grams of crude product. The crude product is then rushed over and distilled through a fractionation column after adding to it 2 grams of calcium carbonate, grams of Primol and l 22 gram of lonol at a vapor temperature of 124126C and 2.1-2.8 mm. Hg. pressure.

1R, NMR and mass spectral analyses yield the information that the resultant product is a mixture of geometric isomers having chemical structures, of which have the generic structure:

and 30% of which have the generic structure:

wherein one of the wavy lines in each of the above structures is a carbon-carbon double bond and the other of the wavy lines in each of the above structures represents a carbon-carbon single bond.

EXAMPLE Vll In Situ Preparation of 1', 2, 3, 4', 5', 6', 7, 8'-Octahydro-2', 3', 8', 8'-Tetramethyl-2'-Acetonaphthone isomer Mixture From Myrcene and 3-Methyl-3-Pentene-2-One Into a 5 liter reaction flask equipped with stirrer, reflux condenser, addition funnel and thermometer, the following ingredients are placed:

53 grams aluminum chloride 500 grams toluene 545 Grams of 3-methyl-3'pentene-2-one is then added through the addition funnel into the 5 liter reaction flask over a period of 5 minutes, the temperature of the mass rising to 41C. Immediately thereafter, 975 grams of 77% myrcene is added, with stirring, to the reaction vessel over a period of 1 hour while maintaining the temperature of the mass at 4050C. The A reaction mass is then maintained at 4()50C for a period of 4V2 hours after which period 300 grams of phosphoric acid is added through the addition funnel. The reaction mass is then heated to lO0-l 15C and maintained at that temperature for a period of 8 hours. At the end of the reaction, the reaction mass is washed with two 1 kilo portions of 50C water; then one 250 cc portion of 50C 10% sodium carbonate solution; and finally one 500 gram portion of 50C 15% sodium sulfate solution. After separation of the organic phase from the aqueous phase, 215 grams of triethanolamine is added to the reaction mass. The 5 liter reaction vessel is then equipped with stirrer, reflux condenser, thermometer and Bidwell trap and the mass is then heated to reflux (128C) while removing solvent thereby gradually increasing the pot temperature to C. After 8 hours, sampling of the reaction mass and analysis thereof yielded the information that no labile organic halide is present in the reaction mass. The reaction mass is then stripped of solvent, the. crude mass weighing 1410 23 grams. The crude product is rushed over and then fractionated after adding 40 grams Primol, 1 grams lonol and 10 grams calcium carbonate and purging with nitrogen, at a 1:1 reflux ratio at vapor temperature of 129131C and 2.6-2.9 mm. Hg. pressure. Yield 845 grams.

The major peak is separated out by GLC analysis in accordance with the same procedure as is set forth in Example 11. The Raman spectrum for the major peak (using a Raman spectrometer manufactured by Spex Incorporated of Plainfield, New Jersey) is, in part, set forth in FIG. 3. The Raman spectrum indicates a tetrasubstituted double bond at 1679 cm and a carbonyl group at 1711 cm.

The infrared analysis for the major peak is set forth in FIG. 4.

The NMR analysis for the major peak is set forth in FIG 1.

IR, NMR and Raman spectral analyses yield the information that the resulting product is a mixture of isomers having the generic structure:

EXAMPLE VIII A perfume composition is prepared exactly as in Example 111 except that the mixture ofisomers of l', 2, 3', 4, 5, 6, 7', 8'-0ctahydro-2, 3', 8', 8'-tetramethyl- 2'-acetonaphthonesproduced by the process of Example VII is applied in lieu of the mixture of Example 11 (prior to GLC separation).

This blend is evaluated and found to have a high degree of richness and persistence in its novel natural amber quality. This composition can be admixed with aqueous 95% ethanol (ratio: 95 parts ethanol:5 parts composition) chilled and filtered to produce a finished cologne. The cologne so prepared has an amber aroma leaning towards a woody amber note. The composition can also be used to scent soap or other toilet goods such as lotion, aerosol. sprays and the like.

EXAMPLE IX Autoclave Reaction of Myrcene-and 3-Methyl-3-Pentene-2-OneThermal Reaction (Non-Catalytic) Into a 1 liter stirred autoclave, the following ingredients are placed:

Myrcene (77%) 400 grams 3 Mcthyl-3-Pentene- 2One (90%) 220 grams lonol 1 gram Toluene 20 grams The autoclave is operated for a period of hours at a temperature of 175C and at a pressure of 2-3 atmospheres. At the end of the reaction period, the auto- 24 (reflux ratio 9:1). The resulting product is a mixture of isomers having the generic structure:

EXAMPLE X Cyclization of Diels-Alder Adduct Mixture of Example IX Into a 2 liter reaction flask, the following materials are charged:

150 grams Phosphoric Acid 275 grams Toluene pressure and a vapor temperature of l l0l 17C. The

rushedover material is then distilled at a vapor temperature of 128132C and a pressure of 2.5 mm. Hg. (reflux ratio 9:1). GLC, NMR, IR and mass spectral analyses yield the information that the resulting product is a mixture of isomers having the generic structure:

EXAMPLE Xl Preparation of Oxime of l, 2', 3, 4', 5', 6, 7', 8'-Octahydro-2', 3', 8, 8-Tetramethyl-2-Acetonaphthone and Regeneration of l, 2', 3', 4, 5', 6, 7, 8-Octahydro-2', 3', 8, 8-Tetramethyl-2'-Acetonaphth0ne A. PREPARATION OF OXIME In a 2 liter flask is placed 1000 ml of aqueous ethanol and 61 gms. of hydroxylamine sulfate. The reaction mass is stirred while a solution of 30 gms. of sodium hydroxide in 30 gms. of water is added slowly. After an additional 35 minutes of stirring, the reaction mass is filtered to remove the suspended sodium sulfate.

The resulting alcoholic solution of hydroxylamine is charged to a 2 liter three neck flask and gms. of material prepared as in Example VII (prior to GLC separation) is added. The resultant mixture is stirred vigorously at reflux for approximately 8.5 hours. The

solution is cooled to room temperature and the resulting crystals are filtered and air dried to give 70 gms. of oxime. The oxime is crystalized twice from toluene (2-3 ml toluene per gram oxime) to get 50 gms. purified oxime.

B. REGENERATION OF 1, 2', 3, 4', 5, 6', 7', 8- OCTAHYDRO-Z', 3, 8', 8-TETRAMETHYL-2- ACETONAPHTHONE A mixture of 50 gms. of the recrystalized oxime produced in Part A herein. 250 gms. of 20% weight/weight sulfuric acid, and 500 gms. of 95% aqueous ethanol is stirred at reflux for 4.5 hours. The mixture is washed with 2500 ml of 10% sodium hydroxide solution and then with water. Toluene (100 ml) is added to the organic layer and the material is stripped under reduced pressure (10-20 ml Hg pressure) to remove traces of water. The washed and dried product is then distilled to give 30 gms. of product which is essentially identical to the product of Example XlV by comparison of NMR spectra and GLC elution times. The NMR analysis of this material is set forth in FIG. 6.

This material is evaluated as being a very clean version of the material prepared in accordance with the process of Example Vll, significantly better than the material which contains other isomers.

EXAMPLE Xll A perfume composition is prepared exactly as in ished cologne. The cologne so prepared has a citrus aroma leaning towards an amber note. The composition can also be used to scent soap or other toilet goods such as lotion, aerosol, sprays and the like.

Chemical Shifts EXAMPLE Xlll The Dials-Alder reaction product of Example IV (250 gms. thereof) is added over a period of minutes to a well stirred mixture of 1000 gms. of toluene and 145 gms. of boron trifluoride diethyl ether complex in a 3 liter reaction vessel equipped with stirrer, reflux condenser, thermometer, and addition funnel. The reaction mass is then maintained at 485lC over a period of 13 hours and is then cooled to less than 25C with stirring. While being maintained at 25C, 600 gms. of 10 aqueous sodium hydroxide is added to the reaction mass. The resulting organic layer is then washed with 10% sodium hydroxide and water. The reaction mass is then stripped of solvent thereby yielding 332 gms. of crude product. The crude product is fractionated at a vapor temperature of l25-l 28C and a pressure of 2.2 mm. Hg. after 30 gms. of Primol, 1 gm. of

,lonol and 5 gms. of calcium carbonate is added thereto.

In this way, a product is obtained containing geometric isomers having the basic generic structure:

EXAMPLE XlV The major GLC peak of the product of Example Vll is trapped from a 500' X 0.03, SE96 (a non-polar silicone polymer manufactured by Analabs Inc. of PO. Drawer 5397, Hamden, Connecticut 065 18) column at l85C isothermal. This peak is 86.l% of the total material produced (according to GLC on a similar column). The trapped peak is 99.9% one peak when rechromatographed on a 500' X 0.03", SF96 column programmed l C at 4C/min.

The trapped material is submitted for NMR analysis and the results are as follows:

Interpretation 82.09.3H, sharp singlet 82.404 .20. l lH. complex multiplct 81.01. 3H, sharp singlet 50.90, 6H, broadened singlet and

Claims

1. A PROCESS FOR ALTERING THE AROMA PROPERTIES OF CONSUMABLE MATERIAL SELECTED FROM THE GROUP CONSISTING OF PERFUME COMPOSITIONS AND PERFUMED ARTICLES WHICH COMPRISES ADDING THERETO A SMALL BUT EFFECTIVE AMOUNT OF AN AMBER-LIKE FRAGRANCE COMPOSITION CONTAINING A MAJOR PROPORTION OF 1'',2'',3'',4'',5z,6'',7'',8''-OCTAHYDRO-1'',3'',8''-TETRAMETHYL ACETONAPHTHONE ISOMERS PRODUCTED BY A SYNTHESIS COMPRISING THE STEPS OF; I. ADMIXING AT A TEMPERATURE OF FROM ABOUT 0*C UP TO ABOUT 50*C MYRCENE AND 3-METHYL-3-PENTENE-2-ONE IN THE PRESENCE OF A LEWIS ACID CATALYST THEREBY FORMING AN ACETYL SUBSTITUTED CYCLOHEXANE MIXTUE, AND II. CYCLIZING THE RESULTING ACETYL SUBSTITUTED CYCOHEXANE MIXTURE WITH A CYCLIZING AGENT SELECTED FROM THE GROUP CONSISTING OF CONCENTRATED PHOSPHORIC ACID, SULFURIC ACID, BORON TRIFLUORIDE AND COMPLEXES OF BORON TRIFLUORIDE.

2. A process for altering the aroma properties of consumable material selected from the group consisting of perfume compositions and perfumed articles which comprises adding thereto a small but effective amount of an amber-like fragrance composition containing a major proportion of 1'',2'',3'',4'',5'',6'', 7'',8''-octahydro-2'',3'',8'',8''-tetramethylacetonaphthone isomers produced by a synthesis comprising the steps of: i. Admixing at a temperature of from about 120* up to 180*C, myrcene and 3-methyl-3-pentene-2-one thereby forming a mixture of acetyl cyclohexene isomers, and ii. Cyclizing the resulting acetyl cyclohexene isomers with a cyclizing agent selected from the group consisting of concentrated phosphoric acid, sulfuric acid, boron trifluoride and complexes of boron trifluoride.

3. The process of claim 1 wherein the first step of the synthesis and the second step of the synthesis are carried out in the same reaction vessel, without isolating the acetyl substituted cyclohexene isomer mixture.

4. The process of claim 2 wherein the first step of the synthesis and the second step of the synthesis are carried out in the same reaction vessel, without isolating the acetyl substituted cyclohexene isomer mixture.

5. The process of claim 1 wherein the first reaction step of the synthesis is carried out at a temperature in the range of from 35* up to 50*C and the second reaction is carried out in the presence of toluene as solvent at a temperature of from 95* up to 115*C.

6. A perfume composition comprising an effective perfuming amount of an amber-like fragrance composition containing a major proportion of 1'',2'',3'',4'',5'',6'',7'',8''-octahydro-2'',3'',8'',8''-tetramethyl acetonaphthone isomers produced by a synthesis comprising the steps of: i. Admixing at a temperature of from about 0* up to about 50*C myrcene and 3-methyl-3-pentene-2-one in the presence of a Lewis acid catalyst thereby forming an acetyl substituted cyclohexene mixture, and ii. Cyclizing the resulting acetyl substituted cyclohexene mixture with a cyclizing agent selected from the group consisting of concentrated phosphoric acid, sulfuric acid, boron trifluoride and complexes of boron trifluoride, and an auxiliary perfume adjuvant.

7. A perfume composition comprising an effective perfuming amount of an amber-like fragrance composition containing a major proportion of 1'',2'',3'',4'',5'',6'',7'',8''-octahydro-2'',3'',8'',8''-tetramethyl acetonaphthone isomers produced by a synthesis comprising the steps of: i. Admixing at a temperature of from about 120* up to 180*C, myrcene and 3-methyl-3-pentene-2-one thereby forming a mixture of acetyl cyclohexene isomers, and ii. Cyclizing the resulting acetyl cyclohexene isomers with a cyclizing agent selected from the group consisting of concentrated phosphoric acid, sulfuric acid, boron trifluoride and complexes of boron trifluoride, and an auxiliary perfume adjuvant.

8. A perfume composition comprising an effective prefuming amount of a compound having the structure: