GB1591342A - Carbonyl compounds processes for preparing same and uses of such carbonyl compounds in affecting the aroma and taste of foodstuffs robaccos beverages perfumes and perfumed articles - Google Patents

Description

(54) CARBONYL COMPOUNDS, PROCESSES FOR PREPARING SAME AND USES OF SUCH CARBONYL COMPOUNDS IN AFFECTING THE AROMA AND TASTE OF FOODSTUFFS, TOBACCOS, BEVERAGES, PERFUMES AND PERFUMED ARTICLES (71) We, INTERNATIONAL FLAVORS & FRAGRANCES INC., a corporation of the State of New York in the United States of America of 521, West 57th Street, New York, N.Y. 10019, United States of America, do hereby declare the invention for which we pray that a patent may be granted to us and the method by which it is to be performed to be particularly described in and by the following statement:- The present invention relates to novel chemical compounds of the genus:

wherein the moiety: C=F3 represents a cycloalkyl group or a cycloalkenyl group having six carbon atoms which may be substituted or unsubstituted and either (i) R2, is hydrogen and R22 represents a methyl group substituted by one or two of the structures:

(wherein R24 is saturated alkyl containing 2 or more carbon atoms or alkenyl or (ii) R22 represents methyl or hydrogen and R21 represents allyl or methallyl having one of the structures:

The present invention also relates to processes for preparing the compounds, 1 - acetyl - I(methallyl or allyl) - 3,3 - dimethylcyclohexane and 1 - (2 - (methallyl or allyl) - 5 - methyl - 4 - pentenoyl) - 3,3 - dimethylcyclohexane having the generic structure:

wherein one of Rl or one or both of R2 and/or R3 is allyl or methallyl and the other of R1 or R2 and/or R3 is hydrogen, a process for producing same and perfumes, perfumed articles, foodstuffs, foodstuff flavorings, medicinal products, tobaccos and tobacco flavorings containing I - acetyl - 3,3- dimethylcyclohexane derivatives having the above generic structure.

The compounds having the structure: (E)

are capable of augmenting or enhancing orange flavors by providing thereto pineapple, allyl caproate-like, galbanum, woody, fatty, sweet, fruity, citrus, green aromas with rosy, ionone, oriental-like, woody, sweet, fruity, citrus flavor characteristics in conjunction with foodstuffs, chewing gums and medicinal products.

The compounds having the generic structure: (E)

are also capable of modifying or enhancing the aroma characteristics of perfumed compositions and perfumed articles by imparting thereto or augmenting or enhancing sweet, earthy, animal, green, herbaceous, melony and fruity aromas with pineapple, ambery, galbanum-like, ginger and citrus nuances and tobacco/animal notes thus fulfilling a need in the field of perfumery.

The compounds having the generic structure: (E)

wherein one of R, or one or both of R2 and/or R3 is methallyl or allyl, and the other of Rl or R2 is hydrogen, are produced by reacting acetyl - 3,3 dimethylcyclohexane with a methallyl halide or an allyl halide in the presence of base such as an alkali metal hydroxide or potassium-t-butoxide and, further, in the presence of a third compound which may be either a tertiary amine, toluene, tbutanol or a crown ether (or various mixtures of same) (hereinafter referred to as a "reaction promoter") according to the following general reaction:

wherein R is ally or methallyl and X is chloro or bromo. The nature of the reaction product is primarily dependent upon the particular reaction promoter used, insofar as the isomer ratios of the reaction products are concerned. Thus, when crown ethers having the generic- structure:

wherein Z is C1-C4 lower alkylene, e.g., methylene or ethylene, n and m are from 2 up to 7, P and Q are the same or different and represent C1-C4 lower alkylene or ortho phenylene, such as compounds having the structure:

(dibenzo-18-crown 6) are used as reaction promoters, the reaction product consists essentially of those products where the methallyl or ally substituent is at the "1" position on the ring, thus:

R4 Xc + ss CROWN ETHER X x MOH (A6) (G) (H) Rq wherein R4 is methyl or hydrogen X is chlorine or bromine and M is an alkali metal.

However, if a phase transfer agent is used as a reaction promoter several byproducts are created, thus:

+ } PthaQnSseer 0 agent (H) (A6) 0 (G) (H) R4 X J\RA RI XRl+ h, h; R4 wherein R4 is methyl or hydrogen, M is an alkali metal and X is chloro or bromo.

When a tertiary amine is used as a reaction promoter, or when toluene or tbutanol is used as a reaction promoter, the reaction that takes place is as follows:

wherein R4 is methyl or hydrogen and X is chloro or bromo. Examples of tertiary amines which can be used in our invention are trimethyl amines, triethyl amines, dimethylaminoethyl-dimethyl amine.

The process of this aspect of our invention is carried out in an inexpensive solvent which is (a) inert to the reaction system and (b) may also serve as a reaction promoter. Among such solvents are toluene, benzene, o-xylene, m-xylene, pxylene, ethyl benzene, n-hexane, cyclohexane, methylene chloride, odichlorobenzene, t-butanol and crown ethers such as dibenzo-18-crown-6.

The particular base used in the reaction is critical and, preferred are, sodium hydroxide, potassium hydroxide and potassium-t-butoxide.

Another aspect of our invention concerns the discovery that novel solid and liquid foodstuff, chewing gum, medicinal product and toothpaste compositions and flavoring compositions therefore having sweet, fruity, raspberrry, woody, lemon, piney, ionone-like, blueberry and floral aroma characteristics and sweet, raspberry, lemony, sweet fruity, red berry, piney, floral, ionone-like and nut meat flavor characteristics and novel perfume compositions, colognes and perfumed articles having fruity, woody, piney aromas with armoise and floral nuances and slight chocolate undertones, may be provided by the utilization of one or more l-acetyl- 3,3-dimethylcyclohexane derivatives having the formula:

wherein R is hydrogen or methyl, in foodstuffs, chewing gums, toothpastes and medicinal product flavors.

The 1 - acetyl - 3,3 - dimethylcyclohexane derivatives useful as indicated supra may be produced preferably by a process which comprises reaction of I acetyl - 3,3 - dimethylcyclohexane with an aldehyde having the structure:

thereby producing a compound having the structure: (L)

wherein the dotted line is a carbon-carbon double bond in the presence of an inorganic base or a mixture of boron oxide (B2O3) and boric acid and reducing the resulting product with hydrogen thereby producing a compound having the structure:

wherein R is hydrogen or methyl.

The first reaction with aldehyde having the structure:

is carried out at a temperature of from about 20"C up to 1600C, when using a catalyst which is an inorganic base, such as an alkali metal hydroxide, for example, potassium hydroxide, sodium hydroxide and lithium hydroxide or an alkaline earth metal hydroxide such as barium hydroxide or lithium hydroxide; or at a temperature in the range of from about 100"C up to 2000C when using a catalyst which is a mixture of boric acid (HBO3) and boron oxide.

The time of reaction is inversely proportional to the temperature of reaction.

Thus, when using a mixture of boric acid and boron oxide the time of reaction varies between 2 and 10 hours and when using a higher temperature the time of reaction varies from between 1 and 8 hours.

When using an inorganic base, the mole ratio of inorganic base: I - acetyle 3,3 - dimethylcyclohexane may vary from 0.1:1 up to 2:1 with a mole ration of 1:1 being preferred. When using the mixture of boric acid and boron oxide the mole ratio of boron oxide: I - acetyl - 3,3 - dimethylcyclohexane varies from 0.5:1 up to 1.5:1 with a mole ratio of 1:1 being preferred. The concentration of boric acid in the reaction mass may vary from I up to 80 grams per mole of aldehyde having the structure (4).

In all cases, the mole ratio of the aldehyde:l - acetyle - 3,3 dimethylcylcohexane may vary from 1:1 up to about 3:1 with a mole ratio of 2:1 being preferred.

Both reactions take place preferably in the presence of an inert solvent.

The reduction reaction to form the genus having the structure:

is carried out preferably in the presence of inert solvents such as isopropyl alcohol; at hydrogenation pressures of between 50 and 150 psig; at temperatures of between 25 and 150"C; and using hydrogenation catalysts such as 5% palladium-on-carbon, rhodium, platinum and Raney nickel. The time of reaction varies inversely with the temperature and pressure of reaction. Thus, lower pressures and temperatures give rise to a need for greater times of reaction. Thus, the time of reaction may vary from I hour up to 5 hours.

The previous reaction:sequence is illustrated as follows:

Examples and organoleptic properties of materials which can be produced according to the aforementioned process are as follows: TABLE I Organoleptic Properties

Name Structure Flavor Fragrance 3,3-dimethyl-l- Sweet, piney, Low-keyed, (4-methylvaleryl)- < fruity, blue- sweet, woody, cyclohexane z > berry, woody somewhat aroma, char- chocolate acter with like.

sweet, piney fruity, nut O (M1) meat char fruity, nut meat char acteristics.

Another aspect of our invention involves the discovery that novel perfume compositions, colognes and perfumed articles having fruity, berry, herbaceous aromas with green and tobacco nuances may be provided by the utilization of 1butanoyl - 3,3 - dimethylcyclohexane having the formula:

The 1 - butanoyl - 3,3 - dimethylcyclohexane useful as indicated supra may be produced preferably by a process which comprises the reaction of 1 - acetyl 3,3 - dimethylcyclohexane (A6) with acetaldehyde in the presence of an inorganic base or a mixture of boron oxide (B2O3) and boric acid, thereby producing a compound having the structure:

(mixture of "cis" and "trans" isomers) and a compound having the structure:

and then reducing the resulting product with hydrogen thereby producing a compound having the structure:

The first reaction with acetaldehyde is carried out at a temperature of from about 20"C up to 1600C, when using a catalyst which is an inorganic base, such as an alkali metal hydroxide, for example, potassium hydroxide, sodium hydroxide and lithium hydroxide or an alkaline earth metal hydroxide such as barium hydroxide or lithium hydroxide; or at a temperature in the range of from about 100"C up to 2000C when using a catalyst which is a mixture of boric acid (HBO3) and boron oxide.

The time of reaction is inversely proportional to the temperature of reaction.

Thus, when using a mixture of boric acid and boron oxide the time of reaction varies between 2 and 10 hours and when using a higher temperature, the time of reaction varies from between I and 8 hours.

When using an inorganic base, the mole ratio of inorganic base:l - acetyl 3,3 - dimethylcyclohexane may vary from 0.1:1 up to 2:1 with a mole ratio of 1:1 being preferred. When-using the mixture of boric acid and boron oxide, the mole ratio of boron oxide: I - acetyl - 3,3 - dimethylcyclohexane varies from 0.5:1 up to 1.5:1 with a mole ratio of 1:1 being preferred. The concentration of boric acid in the reaction mass may vary from I up to 80 grams per mole of acetaldehyde.

In all cases the mole ratio of acetaldehyde: I -. acetyl - 3,3 dimethylcyclohexane may vary from 1:1 up to about 3:1 with a mole ratio of 2:1 being preferred.

The reactions may take place in the presence or in the absence of an inert solvent. When using boric acid or boric oxide, the reaction preferably is carried out without solvent. When using an inorganic base catalyst, the reaction preferably takes place using a solvent, for example methanol, ethanol or isopropanol.

The reduction reaction to form the compound having the structure:

is carried out preferably in the presence of inert solvents for example, isopropyl alcohol; at hydrogenation pressures of between 50 and 15 psig; at temperatures of between 25 and 150"C; and using hydrogenation catalysts such as 5% palladiumon-carbon, rhodium, platinum and Raney nickel. The time of reaction varies inversely with the temperature and pressure of reaction. Thus, lower pressures and temperatures give rise to a need for greater times of reaction. Thus, the time of reaction may vary fron I hour up to 5 hours.

The previous reaction sequence is illustrated as follows:

+ ", CH3 - (A6) (B9/10) reducing 0 1 agent t agent (B9/10) 0 (B8) 0 wherein one of the dashed lines represents a carbon-carbon double bond and the other of the dashed lines represents a carbon-carbon single bond.

Yet another aspect of our invention concerns the discovery of the compounds - - (2 - propenyl) - 3 - (4 - methyl - 3 - pentenyl) - A3 - cyclohexane - 1 - carboxaldehydes and I - (2 - propenyl) - 4 - (4 - methyl - 3 - pentenyl) - A3 cyclohexene - I - carboxaldehydes having the generic structure:

wherein the carboxaldehyde and 2 - propenyl moieties are both bonded either at the alpha-carbon atom or the beta-carbon atom of the cyclohexenyl moiety; their organoleptic uses and processes for producing same.

The compounds having the structures:

as well as the mixtures produced by the structure:

are each capable of augmenting or enhancing cocoa butter-like flavors, apricot flavors, peach flavors, dairy flavors and coconut flavors by providing therein or imparting thereto, sweet, fatty, cocoa butter-like, green/grassy, dairy, diacetyl-like, apricot-like and carrot-like aroma characteristics with fatty, cocoa butter-like, green/grassy, dairy-like, diacetyl-like, peach and coconut flavor characteristics.

The compounds I - (2 - propenyl) - 3 - (4 - methyl - 3 - pentenyl) - A3 cyclohexene - 1 - carboxaldehyde and 1 - (2 - propenyl) - 4 - (4 - methyl - 3 pentenyl) - A3 - cyclohexene - I - carboxaldehyde are also capable of modifying or enhancing the odor characteristics of perfume compositions and perfumed articles by imparting thereto sweet, fruity, lavender-like notes with citrus, floral and balsam nuances, thus fulfilling a need in the field of perfumery.

In tobacco and tobacco flavoring compositions the compounds 1 - (2 propenyl) - 3 - (4- methyl - 3 - pentenyl) - b3 - cyclohexene - I carboxaldehyde and I - (2 - propenyl) - 4 - (4 - methyl - 3 - pentenyl) - A3 cyclohexene - 1 - carboxaldehyde impart cocoa liquor-like, sweet-rich and creamy oily notes.

The compounds 1 - (2 - propenyl) - 3 - (4 - methyl - 3 - pentenyl) - A3 cyclohexene - I - carboxaldehyde and 1 - (2 - propenyl) - 4 - (4 - methyl - 3 pentenyl) - A3 - cyclohexene - I - carboxaldehyde are produced by reacting myrac aldehyde having the structure:

with an allylic halide in the presence of an inert solvent and an alkali metal hydroxide and in the presence of a "phase transfer agent". The reaction is carried out in a two phase system. Thus, one aspect of our invention is illustrated in the following reaction:

wherein the carboxaldehyde and 2 - propenyl moieties are both bonded to the alphacarbon atom or the beta-carbon atom, X is chloro or bromo and M is alkali metal.

One aspect of our invention involves the aforementioned process comprising the step of placing the reactants for the process and the base, respectively, in two immiscible phases, an organic phase and either (i) an aqueous base phase or (ii) a solid base phase with the reactants being located substantially entirely in the first mentioned organic phase and the base being located substantially entirely in the second mentioned phase; and adding to this two phase system a "phase transfer agent" which may be one or more of several organic quaternary ammonium salts.

Specific examples of phase transfer agents useful in our invention are as follows: Quaternary Ammonium Salts Tricapryl methyl ammonium chloride; Cetyl trimethyl ammonium chloride; Cetyl trimethyl ammonium bromide; and Benzyl trimethyl ammonium hydroxide.

Tertiary Amines Trimethylamine; Triethylamine; and Dimethyl (dimethyl amino ethyl) amine.

Crown Ethers 18-crown-6 having the structure:

Dibenzo-18-crown-6 having the structure:

In general, the phase transfer agents most preferred have the generic formula:

wherein at least one of R4l, R42, R43 and R44 is C6~l4 aryl, C6-C10 aralkyl, C6-C20 alkyl, C6-C14 alkaryl and C6-C20 alkenyl and the other of R43, R43 and R44 is alkyl such as methyl, ethyl n-propyl, i-propyl, butyl, 2-butyl, l-methyl-2-propyl, 1pentyl and l-octyl and Z- is an anion such as chloride, bromide and hydroxide.

The process of this aspect of our invention is carried out in an inexpensive solvent which is inert to the reaction system such as toluene, benzene, o-xylene, mxylene, p-xylene, ethyl benzene, n-hexane, cyclohexane, methylene chloride and odichlorobenzene.

The process of this aspect of our invention is carried out at a temperature in the range of from about 10"C up to about 1500C with a temperature range of 50- 120"C being preferred. The reaction time is inversely proportional to the reaction temperature, with lower reaction temperatures giving rise to greater reaction times; and, accordingly, the reaction time ranges from about 30 minutes up to about 10 hours.

In the reaction of this aspect of our invention the mole ratio of myrac aldehyde to the allyl halide reactant is in the range of from 0.5:1.5 up to 1.5 to 0.5 with a preferred ratio being from 1:1 up to 1.2:1.

The mole ratio of base to allylic halide in the reaction mass may be in the range of from about 0.75:1 up to about 1.5:1 with a preferred ratio of base:allylic halide being from 1:1 up to 1.2:1.

The quantity of "phase transfer agent" in the reaction mass, based on the amount of myrac aldehyde in the reaction mass, may vary from 0.5 grams per mole of the myrac aldehyde up to 25 grams per mole, with a preferred concentration of "phase-transfer agent" being in the range of from about 2.5 up to about 7.5 grams of "phase transfer agent" per mole of myrac aldehyde.

The reaction of our invention is preferably carried out at atmospheric pressure since that is the most convenient condition, however, lower or higher pressures can be used without detrimentally affecting the ultimate yield of desired reaction product.

The particular base used in the reaction is critical and, preferred are, sodium hydroxide and potassium hydroxide.

The terms "alter" and "modify" in their various forms will be understood herein to mean the supplying or imparting of a flavor character or note to an otherwise bland, relatively tasteless substance, or augmenting an existing flavor characteristic where the natural flavor is deficient in sdme regard, or supplementing the existing flavor or aroma impression to modify the organoleptic character. The materials which are so altered are generally referred to herein as consumable materials.

The term "enhance" in its various forms will be understood herein to mean the intensification of a given flavor and/or aroma "nuance" or "note" in a food flavor composition and/or in a foodstuff without changing the type or quality of said flavor or aroma nuance or note.

The term "foodstuff" as used herein includes both solid and liquid ingestible materials for man or animals, which materials usually do, but need not, have nutritional value. Thus, foodstuffs includes fruit juices, meats, gravies, soups and convenience foods, vegetables, snack foods, dog and cat foods and other veterinary products, and the like.

When the compounds having the generic structure: (E)

wherein one of R1 or both of R3 and/or R3 is methallyl or allyl and the other of R, or R2 and/or R3 is hydrogen (hereinafter referred to as "the 1 - acetyl - 3,3 dimethylcyclohexane derivative of our invention") are used as food flavor adjuvants, the nature of the co-ingredients included with the 1 - acetyl - 3,3 dimethylcyclohexane derivatives of our invention in formulating the product composition will also serve to alter, modify, augment or enhance the organoleptic characteristics of the ultimate foodstuff treated therewith.

As used herein, the term "medicinal product" includes both solids and liquids which are ingestible non-toxic materials which have medicinal value such as cough syrups, cough drops, aspirin and chewable medicinal tablets.

The term "chewing gum" is intended to mean a composition which comprises a substantially water-insoluble, chewable plastic gum base such as chicle, or substitutes therefor, including jelutong, guttakay, rubber or certain comestible natural or synthetic resins or waxes. Incorporated with the gum base in admixture therewith may be plasticizers or softening agents, e.g., glycerine; and a flavoring composition which incorporates the I - acetyl - 3,3 - dimethylcyclohexane derivatives of our invention, and in addition, sweetening agents which may be sugars, including sucrose or dextrose and/or artificial sweeteners such as cyclamates or saccharin. Other optional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoring adjuvants are well known in the art for such use, being extensively described in the relevant literature. It is a requirement that any such material be "ingestibly" acceptable and thus non-toxic and otherwise non-deleterious particularly from an organoleptic standpoint whereby the ultimate flavor and/or aroma of the consumable material used is not caused to have unacceptable aroma and taste nuances. Such materials may in general be characterized as flavoring adiuvants or vehicles comprising broadly stabilizers, thickeners, surface active agents, conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride; antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid, butylated hydroxyanisole (mixture of 2- and 3 - tertiary - butyl -- 4 - hydroxy - anisole), butylated hydroxy toluene (2,6 - di - tertiary - butyl - 4 - methyl phenol) and propyl gallate and sequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids, suspending agents and emulsifiers, e.g., agar agar, carrageenan; cellulose and cellulose derivatives such as carboxymethyl cellulose and methyl cellulose; natural and synthetic gums such as gum arabic, gum tragacanth; gelatin, proteinaceous materials; lipids; carbohydrates; starches, pectins and emulsifiers, e.g., mono and diglycerides of fatty acids, skim milk powder, hexoses, pentoses, disaccharides, e.g., sucrose corn syrup.

Surface active agents include emulsifying agents, e.g., fatty acids such as capric acid, caprylic acid, palmitic acid and myristic acid, mono- and diglycerides of fatty acids, lecithin, defoaming and flavor-dispersing agents such as sorbitan monostearate, potassium stearate and hydrogenated tallow alcohol.

Conditioners include compounds such as bleaching and maturing agents, e.g., benzoyl peroxide, calcium peroxide and hydrogen peroxide; starch modifiers such as peracetic acid, sodium chlorite, sodium hypochlorite, propylene oxide and succinic anhydride, buffers and neutralizing agents, e.g., sodium acetate, ammonium bicarbonate, ammonium phosphate, citric acid, lactic acid and vinegar; colorants, e.g., carminic acid, cochineal, tumeric and curcuma; firming agents such as aluminum sodium sulfate, calcium chloride and calcium gluconate; texturizers, anti-caking agents, e.g., aluminum calcium sulfate and tribasic calcium phosphate; enzymes; yeast foods, e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g., iron salts such as ferric phosphate and ferrous gluconate, riboflavin, vitamins, zinc sources such as zinc chloride and zinc sulfate.

Other flavorants and flavor intensifiers include organic acids, e.g., acetic acid, formic acid, 2 - hexenoic acid, benzoic acid, n-butyric acid, caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovaleric acid, alpha-methyl-butyric acid, propionic acid, valeric acid, 2-methyl-2-pentenoic acid, and 2-methyl-3-pentenoic acid, ketones and aldehydes, and ketals and acetals thereof, e.g., acetaldehyde, acetophenone, acetone, acetyl methyl carbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methyl butanal, beta, beta-dimethylacrolein, methyl-n-amyl ketone, nhexenal, 2-hexenal, isopentanal, hydrocinnamic aldehyde, cis-3-hexenal, 2heptanal, nonyl aldehyde, 4-(p-hydroxyphenyl) - 2 - butanone, alpha-ionone, betaionone, methyl - 3 - butanone, benzaldehyde, damascone, damasenone, acetophenone, 2 - heptanone, o-hydroxy-acetophenone, 2 - methyl - 2 - hepten 6 - one, 2 - octanone, 2 - undecanone, 3 - phenyl - 4 - pentenal, 2 - phenyl - 2 hexenal, 2 - phenyl - 2 - pentenal, furfural, 5 - methyl furfural, cinnamaldehyde, cis - ethylidene - cis - 3 - hexenal, cis - ethylidene - trans - 3 - hexenal, cis ethylidene - trans - 3 - heptenal, cis - ethylidene - trans - 3 - heptenal diethylacetal, cis - 3 - ethylidene - 4 - octenal, beta - cyclohomocitral, 2pentanone, 2 - pentenal and propanal; alcohols such as I - butanol, benzyl alcohol, I - borneol, trans - 2 - buten - I - ol, ethanol, geraniol, I - hexanal, 2 heptanol, trans - 2 - hexenol - 1, cis - 3 - hexen - I - ol, 3 - methyl - 3 - buten - - ol, I - pentanol, I - penten - 3 - ol, p - hydroxyphenyl - 2 - ethanol, isoamyl alcohol, isofenchyl alcohol, phenyl - 2 - ethanol, alpha - terpineol, cis - terpineol hydrate, eugenol, linalool, 2 - heptanol, acetoin; esters, such as butyl acetate, ethyl acetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethyl caprate, ethyl caproate, ethyl caprylate, ethyl cinnamate, ethyl crotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyl laurate, ethyl myristate, ethyl alpha methylbutyrate, ethyl propionate, ethyl salicylate, trans - 2 - hexenyl acetate, hexyl acetate, 2 - hexenyl butyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, methyl acetate, methyl butyrate, methyl caproate, methyl isobutyrate, alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate, cinnamyl formate, methyl cinnamate and terpenyl acetate; hydrocarbons such as dimethyl naphthalene, dodecane, methyl diphenyl, methyl napthalene, myrcene, naphthalene, octadecane, tetradecane, tetramethyl napthalene, tridecane, trimethyl napththalene, undecane, caryophyllene, 1 - phellandrene, p-cymene, 1 - alphapinene; pyrazines such as 2,3 - dimethylpyrazine, 2,5 - dimethylpyrazine, 2,6 - dimethylpyrazine, 3 - ethyl - 2,5 - dimethylpyrazine, 2 - ethyl - 3,5,6 trimethylpyrazine, 3 - isoamyl - 2,5 - dimethylpyrazine, 5 - isoamyl - 2,3 dimethylpyrazine, 2 - isoamyl - 3,5,6 - trimethylpyrazine, isopropyl dimethylpyrazine, methyl ethylpyrazine, tetramethylpyrazine, trimethylpyrazine; essential oils such as jasmine absolute, cassia oil, cinnamon bark oil, rose absolute, orris absolute, lemon essential oil, Bulgarian rose, yara yara and vanilla; lactones such as 6 -- nonalactone; sulfides, e.g., methyl sulfide and other materials such as maltol, acetoin and other acetals (e.g., 1,1 - diethoxyethane, 1,1 dimethoxyethane and dimethoxymethane).

The specific flavoring adjuvant selected for use may be either solid or liquid depending upon the desired physical form of the ultimate product, i.e., foodstuff, whether simulated or natural, and should, in any event, (i) be organoleptically compatible with the I - acetyl - 3,3 - dimethylcyclohe derivatives of our invention are added to the foodstuff as an integral component of a flavoring composition, it is, of course, essential that the total quantity of flavoring composition employed be sufficient to yield an effective 1 - acetyl - 3,3 dimethylcyclohexane derivative concentration in the foodstuff product.

Food flavoring compositions prepared in accordance with the present invention preferably contain the 1 - acetyl - 3,3 - dimethylcyclohexane derivative of our invention in concentrations ranging from about 0.1 /n up to about 15% by weight based on the total weight of the said flavoring composition.

The composition described herein can be prepared according to conventional techniques well known as typified by cake batters and fruit drinks and can be formulated by merely admixing the involved ingredients within the proportions stated in a suitable blender to obtain the desired consistency and homogeneity of dispersion. Alternatively, flavoring compositions in the form of particulate solids can be conveniently prepared by mixing the 1 - acetyl - 3,3 - dimethylcyclohexane derivatives of our invention with, for example, gum arabic, gum tragacanth and carrageenan, and thereafter spray-drying the resultant mixture whereby to obtain the particular solid product. Pre-prepared flavor mixes in powder form, e.g., a fruitflavored powder mix, are obtained by mixing the dried solid components, e.g., starch and sugar and the 1 - acetyl - 3,3 - dimethylcyclohexane derivatives of our invention in a dry blender until the requisite degree of uniformity is achieved.

It is presently preferred to combine with the 1 - acetyl - 3,3 dimethylcyclohexane derivatives of our invention, the following adjuvants; phydroxybenzyl acetone, geraniol, cassia oil, acetaldehyde, maltol, ethyl methyl phenyl glycidate, benzyl acetate, dimethyl sulfide, eugenol, vanillin, caryophyllene, methyl cinnamate, guiacol, ethyl pelargonate, cinnamaldehyde, methyl anthranilate, 5-methyl furfural, isoamyl acetate, cis-ethylidene - cis - 3 - hexenal, cis - ethylidene - trans - 3 - hexenal, cis - ethylidene - trans - 3 - heptenal, cis ethylidene - trans - 3 - heptenal - diethylacetal, cis - 3 - ethylidene - 4 - octenal, isobutyl acetate, cuminaldehyde, alpha ionone, cinnamyl formate, ethyl butyrate, methyl cinnamate, acetic acid, gamma-undecalactone, naphthyl ethyl ether, diacetyl, furfural, ethyl acetate, anethole, 2,3 - dimethyl pyrazine, 2 - ethyl - 3 methyl pyrazine, 3 - phenyl - 4 - pentenal, 2 - phenyl - 2 - hexanal, 2 - phenyl 2 - pentenal, 3 - phenyl - 4 - pentenal diethyl acetal, damascone (I - crotonyl 2,2,6 - trimethylcyclohex - I - one), damascenone (1 - crotonyl - 2,2,6 trimethylcyclohexa - 1,5 - diene), beta - cyclohomocitral (2,2,6 trimethylcyclohex - I - ene carboxaldehyde), isoamyl butyrate, cis - 3 - hexenol 1, 2- methyl - 2 - pentenoic acid, elemecine (4 - allyl - 1,2,6 - trimethoxy benzene), isoelemecine (4 - propenyl - 1,2,6 - trimethoxy benzene) and 2 - (4 hydroxy - 4 - methylpentyl) norbornadiene.

The I - acetyl - 3,3 - dimethylcyclohexane derivatives of our invention and one or more auxiliary perfume ingredients, including, for example, alcohols, aldehydes, ketones, terpinic hydrocarbons, nitriles, esters, lactones, natural essential oils and synthetic essential oils, may be admixed so that the combined odors of the individual components produce a pleasant and desired fragrance, particularly and preferably in petitgrain fragrances. Such perfume compositions usually contain (a) the main note or the "bouquet" or foundation stone of the composition; (b) modifiers which round off and accompany the main note; (c) fixatives which include odorous substances which lend a particular note to the perfume throughout all stages of evaporation and substances which retard evaporation; and (d) topnotes which are usually low boiling fresh smelling materials.

In perfume compositions, it is the individual components which contribute their particular olfactory characteristics, however, the over-all sensory effect of the perfume composition will be at least the sum total of the effects of each of the ingredients. Thus, the I - acetyl - 3,3 - dimethylcyclohexane derivatives of our invention can be used to alter, modify or enhance the aroma characteristics of a perfume composition, for example, by utilizing or moderating the olfactory reaction contributed by another ingredient in the composition.

The amount of 1 - acetyl - 3,3 - dimethylcyclohexane derivatives of our invention which will be effective in perfume compositions as well as in perfumed articles and colognes 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 0.01 M, of I - acetyl - 3,3 dimethylcyclohexane derivatives of our invention or even less (e.g., 0.005 /") can be used to impart green, fruity, aldehydic notes with galbanum, ginger and citrus-like nuances to soaps, cosmetics or other products. The amount employed can range up to 70% of the fragrance components 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 1 - acetyl - 3,3 - dimethylcyclohexane derivatives of our invention are useful [taken alone or together with other ingredients in perfume compositions] as (an) olfactory component(s) in detergents and soaps, space odorants and deodorants; perfumes; colognes; toilet water; bath preparations such as bubble bath or bath salts; hair preparations such as lacquers, brilliantines, pomades and shampoos; cosmetic preparations, such as creams, deodorants, hand lotions and sun screens; powders, such as talcs, dusting powders and face powders. When used as (an) olfactory component(s), as little as 1% of 1 - acetyl - 3,3 dimethylcyclohexane derivatives of our invention will suffice to impart ginger, citrus and galbanum nuances to petitgrain aromas. Generally, no more than 3% of 1 - acetyl - 3,3 - dimethylcyclohexane derivatives of our invention, based on the ultimate end product, is required in the perfume composition.

In addition, the perfume composition or fragrance composition of our invention can contain a vehicle, or carrier for the 1 - acetyl - 3,3dimethylcyclohexane derivatives of our invention. The vehicle can be a liquid such as a non-toxic alcohol or a non-toxic glycol. The carrier can also be an absorbent solid, such as a gum (e.-g., gum arabic) or components for encapsulating the composition (such as gelatin).

Furthermore, 1 - acetyl - -3,3 - dimethylcyclohexane derivatives of our invention are capable of supplying and/or potentiating certain flavor and aroma notes usually lacking in many tobacco flavors heretofore provided.

As used herein in regard to tobacco flavors, the terms "alter" and "modify" in their various forms means "supplying or imparting flavor character or note to otherwise bland tobacco, tobacco substitutes, or tobacco flavor formulations or augmenting the existing flavor characteristic where a natural flavor is deficient in some regard or supplementing the existing flavor impression to modify its quality, character or taste".

As used herein, the term "enhance" is intended to mean the intensification (without change in kind or quality of aroma or taste) of one or more taste and/or aroma nuances present in the organoleptic impression of tobacco or a tobacco substitute or a tobacco flavor.

Our invention thus provides an organoleptically improved smoking tobacco product and additives therefor, as well as methods of making the same which overcome specific problems heretofore encountered in which specific desired green, sweet, fruity, floral and Virginia tobacco-like nuances prior to smoking and in the main and sidestreams on smoking, are created or enhanced and may be readily controlled and maintained at the desired uniform level regardless of variations in the tobacco components of the blend.

This invention further provides improved tobacco additives and methods whereby green, sweet, fruity, floral and Virginia tobacco-like nuances prior to smoking and in the main and sidestreams on smoking may be imparted to smoking tobacco products and may be readily varied and controlled to produce the desired uniform flavor characteristics.

In carrying out this aspect of our invention, we add to smoking tobacco materials or a suitable substitute therefor (e.g., dried lettuce leaves) an aroma and flavor additive containing as an active ingredient I - acetyl - 3,3dimethylcyclohexane derivatives of our invention.

In addition to the 1 - acetyl - 3,3 - dimethylcyclohexane derivatives of our invention other flavoring and aroma additives may be added to the smoking tobacco materials or substitute therefor either separately or in mixture with the I acetyl - 3,3 - dimethylcyclohexane derivatives of our invention as follows; 1.

Synthetic Materials: beta-ethyl-cinnamaldehyde, eugenol, dipentene, damascenone, maltol, ethyl maltol, delta undecalactone, delta decalactone, benzaldehyde, amyl acetate, ethyl butyrate, ethyl valerate, ethyl acetate, beta-cyclohomocitral, 2hexenol - 1,2 - methyl - 5 - isopropyl - 1,3 - nonadiene - 8 - one, 2,6 dimethyl - 2,6 - undecadiene - 10 - one, 2 - methyl - 5 - isopropyl acetophenone, 2 - hydroxy - 2,5,5,8a - tetramethyl - 1 - (2 - hydroxyethyl) - decahydronaphthalene, dodecahydro - 3a,6,6,9a - tetramethylnaphtho - (2,1 - b) - furan, 4 hydroxy hexanoic acid, gamma lactone and polyisoprenoid hydrocarbons defined in Example V of U.S. Patent 3,589,372 issued on June 29, 1971 and II. Natural Oils: celery seed oil, coffee extract, bergamot oil, cocoa extract, nutmeg oil and origanum oil.

An aroma and flavoring concentrate containing I - acetyl - 3,3 - dimethylcyclohexane derivatives of our invention and, if desired, one or more of the above indicated additional flavoring additives may be added to the smoking tobacco material, to the filter or to the leaf or paper wrapper. The smoking tobacco material may be shredded, cured, cased and blended tobacco material or reconstituted tobacco material or tobacco substitutes (e.g., lettuce leaves) or mixtures thereof. The proportions of flavoring additives may be varied in accordance with taste but insofar as enhancement or the imparting of natural and/or sweet notes, we have found that satisfactory results are obtained if the proportion by weight of the sum total of 1 - acetyl - 3,3 - dimethylcyclohexane derivatives of our invention to smoking tobacco material is between 250 ppm and 1,500 ppm (between 0.025% and .15 /n) of the active ingredients to the smoking tobacco material. We have further found that satisfactory results are obtained if the proportion by weight of the sum total of I - acetyl - 3,3 - dimethylcyclohexane derivatives of our invention used to flavoring material is between 2,500 and 10,000 ppm (between 0.25 and 1.0 /n).

Any convenient method for incorporating the I - acetyl - 3,3 dimethylcyclohexane derivatives of our invention in the tobacco product may be employed. Thus, the 1 - acetyl - 3,3 - dimethylcyclohexane derivatives of our invention taken alone or along with other flavoring additives may be dissolved in a suitable solvent such as ethanol, pentane, diethyl ether and/or other volatile organic solvents and the resulting solution may either be sprayed on the cured, cased and blended tobacco material or the tobacco material may be dipped into such solution. Under certain circumstances, a solution of the I - acetyl - 3,3 dimethylcyclohexane derivatives of our invention taken alone or taken further together with other flavoring additives as set forth above, may be applied by means of a suitable applicator such as a brush or roller on the paper or leaf wrapper for the smoking product, or it may be applied to the filter by either spraying, or dipping, or coating.

Furthermore, it will be apparent that only a portion of the tobacco or substitute therefor need be treated and the thus treated tobacco may be blended with other tobaccos before the ultimate tobacco product is formed. In such cases, the tobacco treated may have the 1 - acetyl - 3,3 - dimethylcyclohexane derivatives of our invention in excess of the amounts or concentrations above indicated so that when blended with other tobaccos, the final product will have the percentage within the indicated range.

In accordance with one specific example of our invention an aged, cured and shredded domestic burley tobacco is sprayed with a 20% ethyl alcohol solution of 1 - acetyl - 3,3 - dimethylcyclohexane derivatives of our invention in an amount to provide a tobacco composition containing 800 ppm by weight of I - acetyl - 3,3 .dimethylcyclohexane derivatives of our invention on a dry basis. Thereafter, the alcohol is removed by evaporation and the tobacco is manufactured into cigarettes by the usual techniques. The cigarette when treated as indicated has a desired and pleasing aroma (increased smoke body sensation in the mouth with enhanced tobacco-like notes and pleasant aromatic nuances) which is detectable in the main and sidestreams when the cigarette is smoked. This aroma is described as having green, sweet, fruity, floral and Virginia tobacco-like nuances prior to smoking and in the main and sidestreams on smoking.

While our invention is particularly useful in the manufature of smoking tobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco, other tobacco products formed from sheeted tobacco dust or fines may also be used. Likewise, the I - acetyl - 3,3 - dimethylcyclohexane derivatives of our invention can be incorporated with materials such as filter tip materials, seam paste and packaging materials which are used along the tobacco to form a product adapted for smoking.

Furthermore, the I - acetyl - 3,3 - dimethylcyclohexane derivatives of our invention can be added to certain tobacco substitutes of natural or synthetic origin (e.g., dried lettuce leaves) and, accordingly, by the term "tobacco" as used throughout this specification is meant any composition intended for human consumption by smoking or otherwise, whether composed of tobacco plant parts or substitute materials or both.

It will thus be apparent that the 1 - acetyl - 3,3 - dimethylcyclohexane derivatives of our invention can be utilized to alter, modify or enhance sensory properties, such as flavor(s) and/or fragrance(s) of a wide variety of consumable materials.

It will thus be apparent that the 1 - butanoyl - 3,3 - dimethylcyclohexane of our invention can be utilized to alter, modify or enhance fragrances of a wide variety of consumable materials.

When the compound(s) 1 - (2 - propenyl) - (4 - methyl - 3 - pentenyl) - A3 cyclohexene - I - carboxaldehydes of our invention are used as a food flavor adjuvant, the nature of the co-ingredients included with the compound(s) I - (2 propenyl) - (4 - methyl - 3 - pentenyl) - A3 - cyclohexene - I - carboxaldehydes in formulating the product composition will also serve to alter, modify, augment or enhance the organoleptic characteristics of the ultimate foodstuff treated therewith.

The specific flavoring adjuvant selected for use may be either solid or liquid depending upon the desired physical form of the ultimate product, i.e., foodstuff, whether simulated or natural, and should, in any event, (i) be organoleptically compatible with the compound(s) 1 - (2 - propenyl) - (4 - methyl - 3 - pentenyl) A3 - cyclohexene - 1 - carboxaldehydes of our invention by not covering or spoiling the organoleptic properties (aroma and/or taste) thereof; (ii) be nonreactive with the compound(s) 1 - (2 - propenyl) - (4 - methyl - 3 pentenyl) - A3 - cyclohexene - 1 - carboxaldehydes of our invention and (iii) be capable of providing an environment in -which the compound(s) 1 - (2 propenyl) - (4 - methyl - 3 - pentenyl) - A3 - cyclohexane - 1 - carboxaldehydes can be dispersed or admixed to provide a homogeneous medium. In addition, selection of one or more flavoring adjuvants, as well as the quantities thereof will depend upon the precise organoleptic character desired in the finished product.

Thus, in the case of flavoring compositions, ingredient selection will vary in accordance with the foodstuff, chewing gum, medicinal product or toothpaste to which the flavor and/or aroma are t9 be imparted, modified, altered or enhanced.

In contradistinction, in the preparation of solid products, e.g., simulated foodstuffs, ingredients capable of providing normally solid compositions should be selected such as various cellulose derivatives.

Our invention thus provides an organoleptically improved smoking tobacco product and additives therefor, as well as methods of making the same which overcome speeific problems heretofore encountered in which specific desired woody cocoa and cocoa liquer-like flavor characteristics of natural Burley tobacco as well as the sweet-rich and creamy oily nuances thereof, are created or enhanced and may be readily controlled and maintained at the desired uniform level regardless of variations in the tobacco components of the blend.

This invention further provides improved tobacco additives and methods whereby various cocoa, cocoa liquor-like, sweet-rich and creamy oily notes may be imparted to smoking tobacco products and may be readily varied and controlled to produce the desired uniform flavor characteristics.

In carrying out this aspect of our invention, we add to smoking tobacco materials or a suitable substitute therefor (e.g., dried lettuce leaves) an aroma and flavor additive containing as an active ingredient the 1 - (2 - propenyl) - (4 methyl - 3 - pentenyl) - 3 - cyclohexene - I - carboxaldehyde(s).

In addition to the I - (2 - propenyl) - (4 - methyl - 3 - pentyl) - A3 cyclohexene - I - carboxaldehyde(s) of our invention other flavoring and aroma additives may be added to the smoking tobacco materials or substitute therefor either separately or in mixture with the I - (2 - propenyl) - (4 - methyl - 3 pentenyl) - A3 - cyclohexene - 1 - carboxaldehyde(s).

An aroma and flavoring concentrate containing the 1 - (2 - propenyl) - (4 methyl - 3 - pentenyl) - A3 - cyclohexene - I - carboxaldehyde(s) and, if desired, one or more of the above indicated additional flavoring additives may be added to the smoking tobacco material, to the filter or to the leaf or paper wrapper. The smoking tobacco material may be shredded, cured, cased and blended tobacco material or reconstituted tobacco material or tobacco substitutes (e.g., lettuce leaves) or mixtures thereof. The proportions of flavoring additives may be varied in accordance with taste but insofar as enhancement or the imparting of natural and/or sweet notes, we have found that satisfactory results are obtained if the proportion by weight of the sum total of the 1 - (2 - propenyl) - (4 - methyl - 3 pentenyl) - A3 - cyclohexene - 1 - carboxaldehyde(s) to smoking tobacco material is between 250 ppm and 1,500 ppm (0.025 /n. I 5 /n) of the active ingredients to the smoking tobacco material. We have further found that satisfactory results are obtained if the proportion by weight of the sum total of the 1 - (2 - propenyl) - (4 methyl - 3 - pentenyl) - A3 - cyclohexene - 1 - carboxaldehyde(s) used to flavoring material is between 2,500 and 10,000 ppm (between 0.25 and 1).

Any convenient method for incorporating the I - (2 - propenyl) - (4 methyl - 3 - pentenyl) - A3 - cyclohexene - 1 - carboxaldehyde(s) in the tobacco product may be employed. Thus, the I - (2 - propenyl) - (4 - methyl - 3 pentenyl) - A3 - cyclohexene - I - carboxaldehyde(s) taken alone or along with other flavoring additives may be dissolved in a suitable solvent such as ethanol, pentane, diethyl ether and/or other volatile organic solvents and the resulting solution may either by sprayed on the cured, cased and blended tobacco material or the tobacco material may be dipped into such solution. Under certain circumstances, a solution of the I - (2 - propenyl) - (4 - methyl - 3 - pentenyl) A3 - cyclohexene - I - carboxaldehyde(s) taken alone or taken further together with other flavoring additives as set forth above, may be applied by means of a suitable applicator such as a brush or roller on the paper or leaf wrapper for the smoking product, or it may be applied to the filter by either spraying, or dipping, or coating.

Furthermore, it will be apparent that only a portion of the tobacco or substitute therefor need be treated and the thus treated tobacco may be blended with other tobaccos before the ultimate tobacco product is formed. In such cases, the tobacco treated may have the I - (2 - propenyl) - (4 - methyl - 3 - pentenyl) A3 - cyclohexene - I - carboxaldehyde(s) in excess of the amount or concentrations above indicated so that when blended with other tobaccos, the final product will have the percentage within the indicated range.

In accordance with one specific example of our invention, an aged, cured and shredded domestic burley tobacco is sprayed with a 20% ethyl alcohol solution of the 1 - (2 - propenyl) - (4 - methyl - 3 - pentenyl) - A3 - cyclohexene - I carboxaldehyde(s) in an amount to provide a tobacco composition containing 800 ppm by weight of the 1 - (2 - propenyl) - (4 - methyl - 3 - pentenyl) - A3 cyclohexene - 1 - carboxaldehyde(s) on a dry basis. Thereafter, the alcohol is removed by evaporation and the tobacco is manufactured into cigarettes by the usual techniques. The cigarette when treated as indicated has a desired and pleasing aroma (increased smoke body sensation in the mouth with enhanced tobacco-like notes and pleasant aromatic nuances) which is detectable in the main and side streams when the cigarette is smoked. This aroma is described as having increased body, more tobacco-like, more aromatic, slightly oily and slightly cocoalike with cocoa liquor-like, creamy oily and sweet rich notes.

While our invention is particularly useful in the manufacture of smoking tobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco, other tobacco products formed from sheeted tobacco dust or fines may also be used. Likewise.

the i - (2 - prnpeny!) - (4 - methyl - 3 - - pentenyl) - 3 - cyclohexene - I carboxaldehyde(s) ot our invention can be incorporated with materials such as filter tip materials, seam paste, packaging materials and the like which are used along with tobacco to form a product adapted for smoking. Furthermore, the I (2 - propenyl) - (4 - methyl - 3 - pentenyl) - A3 - cyclohexene - I carboxaldehyde(s) can be added to certain tobacco substitutes of natural or synthetic origin (e.g., dried lettuce leaves) and, accordingly, by the term "tobacco" as used throughout this specification is meant any composition intended for human consumption by smoking or otherwise, whether composed of tobacco plant parts or substitute materials or both.

The following Examples generally serve to illustrate our invention and the invention is to be considered restricted thereto only as indicated in the appended claims. Examples XIV to XLII, XLVI, LXXII to LXXXIX specifically illustrate the present invention as claimed.

All parts and percentages given herein are by weight unless otherwise specified. The words "Aliquat", "Primol", "Ionox" and "Carbowax" are Trade Marks, as is the word "Rocoat".

Examples I to IX are described and claimed in our Application No. 7935258 (Serial No. 1,591,343) and Examples X to XIII are described and claimed in our Application No. 7935259 (Serial No. 1,591,344), being retained herein solely to provide a better understanding of the present invention.

EXAMPLE I Preparation of 2,5-dimethyl-2-propenyl hex-4-enal (B 1) Into a I liter reaction flask equipped with stirrer, thermometer, reflux condenser and addition funnel are added a solution of 72 grams of sodium hydroxide in 72 grams of water. 80 Grams of toluene and 5 grams of tricapryl methyl ammonium chloride (Aliquat 336, produced by General Mills Chemicals Inc.) are then added to the mixture. The mixture is heated to a temperature in the range of 75-800C with stirring. Over a period of 6 hours, a solution of 200 grams of 2-methyl-pent-2-enal (Al) and 210 grams of prenyl chloride is added to the reaction mass. At the end of the 6 hour period, the reaction mass is stirred at 75 80"C for another 4 hours. At the end of the 4 hour period the organic layer is separated, washed neutral, and the solvent stripped off.

The residual oil is then distilled on a 12" Vigreaux column after adding 10 grams Primol and 1 gram Ionox. The fractions taken off the column are as follows: Vapor Liquid Fraction Temperature Temperature Vac. Weight No. ( C) ( C) mm Hg (g) 1 6" 75 93-110 4494 24.4 2 115 123 44 23.9 3 118 131 44 52.3 4 119 139 44 52.8 5 121 168 44 39.7 6 138 190 44 17.2 Fractions 2-5 are bulked and re-distilled on a 12 plate Vigreaux column at a reflux ratio of 12:1 after adding thereto 8 grams of Primol and 0.4 grams of Ionox.

The Fractional Distillation Data is as follows: Vapor Liquid Fraction Temperature Temperature Vac. Weight No. ( C) ( C) mm Hg (g) 55-58 106 4444 1.1 2 68 108 44 3.3 3 94 109 32 4.2 4 108 111 .38 3.0 5 112 112.5 38 5.2 6 112 113 38 6.6 7 115 115 38 7.3 8 114 115 38 8.3 9 114 116 38 8.6 10 115 118 38 11.3 11 115 118 38 8.5 12 115 118 38 9.1 13 115 120 38 8.0 14 115 120 38 8.1 15 116 120 38 11.0 16 117 120 38 10.4 17 117 120 38 9.2 18 118 120 38 4.7 19 112-114 122-123 38-38 4.7 20 114 131 38 10.5 21 120 151 38 9.0 22 123 230 38 5.5 Fractions 119 are analyzed using GLC, NMR and IR analyses which confirm that the major component is the compound, 2,5-dimethyl - 2 - propenyl hex - 4 - enal. This material has a tart, green, citrus, cumin, sweet, carvone-like note with a lavandulol-like nuance.

EXAMPLE II Preparation of 2-methyl-2-benzyl-pent-3-enal (B2) Into a I liter reaction flask equipped with stirrer, thermometer, reflux condenser and addition funnel are placed a solution of 72 grams of sodium hydroxide in 72 grams of water. 80 Grams of toluene and 5 grams of tricapryl methyl ammonium chloride are then added to the NaOH solution. The resulting mixture is heated to a temperature in the range of 75-800C. While maintaining the temperature at 75-800C and over a 6 hour period, a solution of 200 g of 2 - methyl pent - 2 - enal (Al) and 253 grams ofbenzyl chloride is added to the reaction mass.

The reaction mass is then stirred for another 6 hours while maintaining the temperature in the range of 75-80"C. The reaction mass is then refluxed for a period of 2.5 hours in order to cause the remaining benzyl chloride to be reacted.

The organic layer is separated, washed neutral and the solvent stripped off.

The residual oil is then distilled on a 3" Splash column after adding thereto 14 grams of Primol and I gram of lonox. The distillation data is as follows: Vapor Liquid Fraction Temperature Temperature Vac. Weight No. ( C) ( C) mm Hg (g) I 79-100 <RT mass is refluxed for an additional 1 hour. At this point, 200 ml water is added, the reaction mass is stirred for 15 minutes and then transferred into a separatory funnel. The organic layer is separated, washed neutral and the solvent stripped off.

The residual oil is then distilled at 2.5 mm Hg through a 6" Vigreaux column, after adding thereto 10.9 grams of Primol and 1 gram of Ionox. The Fractional Distillation data is as follows: Vapor Liquid Fraction Temperature Temperature Weight No. ( C) ( C) (g) 1 51 106 8.0 2 64 134 11.1 3 102 133 10.1 4 118 138 13.1 5 122 141 15.1 6 125 148 32.8 7 127 154 23.7 8 127 159 24.0 9 135 176 19.9 10 142 184 15.4 11 164 195 24.2 Fractions 5-9 are bulked and distilled on an 8 plate Vigreaux column after adding thereto 3 grams of Primol and 0.5 grams of Ionox. The Fractional Distillation Data is as follows: Vapor Liquid Fraction Temperature Temperature Vac. Weight No. ( C) ( C) mm Hg (g) 1 107-139 150--156 3.1 2 141 155 3.0 4.8 3 143 155 3.0 5.8 4 144 156 3.0 8.1 5 144 157 2.6 7.5 6 144 160 2.6 11.1 7 7 140 162 2.5 7.0 8 144 176 2.4 8.7 9 146 214 2.4 7.3 10 138 250 2.4 6.1 Fractions 3-8 are bulked and analyzed using NMR, IR and GLC analyses which confirm that the resulting product is 2-prenyl citral. This material has a sweet, creamy, orangy note with woody, citrusy and resinous nuances.

EXAMPLE IV Production of 2-butenyl-2-ethyl-5-methyl hex-4-enal (B3) Into a I liter reaction flask equipped with stirrer, thermometer, condenser, addition funnel, heating mantle and Thermo-watch are placed a solution of 72 grams of sodium hydroxide and 72 grams of water. 81 grams of toluene and 5 grams of tricapryl methyl ammonium chloride is then added and the mixture is heated with stirring to a temperature in the range of 75-900C. Over a period of 6 hours, a solution of 252 grams of 2-ethyl hex-2-enal (A2) and 215 grams prenyl chloride is added to the reaction mass while maintaining the temperature at 75--800C. After addition is complete the reaction mass is stirred for a period of 4 hours at 75 80"C. The organic layer is separated, washed neutral and the solvent stripped off.

13 Grams of Primol is then added to the residual oil and the residual oil is distilled at 2.5 mm Hg on a rush-over column yielding the following fractions: Vapor Liquid Fraction Temperature Temperature Weight No. ( C) ( C) (g) 40 57 14.8 2 47 62 22.9 3 51 58 15.4 4 54 71 18.0 5 58 73 23.4 6 67 83 17.9 7 80 89 13.4 8 83 92 26.6 9 85 92 22.3 10 85 94 19.0 II 85 99 18.5 12 87 98 16.8 13 94 119 26.9 14 130 -160 19.5 15 195 250 22.8 Fractions 5-14 are bulked and re-distilled at 2.5 mm Hg at a reflux ratio of 9:1 on a 12 plate Vigreaux column after adding thereto 5.1 grams of Primol and 0.5 gram lonox. The following fractions are recovered: Vapor Liquid Fraction Temperature Temperature Weight No. ( C) ( C) (g) 44 -88 8.1 2 50 95 6.9 3 93 117 13.7 4 96 119 9.2 5 97 116 10.4 6 95 114 10.4 7 92 110 11.5 8 96 110 16.9 9 88 105 10.1 10 89 105 10.9 11 83 105 9.9 12 85 106 9.3 13 85 112 11.2 14 85 115 11.1 15 85 132 6.6 16 85 143 4.3 17 93 171 3.4 18 96 250 3.8 Fractions 3-16 are bulked and analyzed using GLC, NMR and IR analyses confirming that the resulting material is 2 - butenyl - 2 - ethyl - 5 - methyl - hex 4 - enal having the structure: (B3)

This material has a green, sweet, tomato aroma with a citrus character and a floral, rosey note becoming more rosey on dry out.

EXAMPLE V Preparation of 2-benzyl-2-ethyl-hex-3-enal (B4) Into a 1 liter reaction flask equipped with condenser, stirrer, thermometer, addition funnel, heating mantle and Thermo-watch is placed a solution of 85 grams sodium hydroxide in 100 grams of water. 100 Grams of toluene and 5 grams of tricapryl methyl ammonium chloride is then added and the reaction mass is heated to 700C with stirring. While maintaining the reaction mass at 700 C, over a 5 hour period a mixture of 252 grams 2-ethyl hexenal (A2) and 235 grams benzyl chloride is added to the reaction mass. After addition is complete the reaction mass is maintained with stirring at 700C for a period of 4 hours. At the end of this period of time the reaction mass is cooled down to 250C and 300 ml of water is added. The organic layer is separated, and washed neutral.

After adding 15.7 grams of Primol and 2 grams of Ionox, to the residual oil, toluene is stripped off and the resulting product is then rushed over at 2.5 mm Hg to yield the following fractions: Vapor Liquid Fraction Temperature Temperature Weight No. ( C) ( C) (g) 1 47--48 110--80 106.9-30.6 2 113 117 31.5 3 120 127 55.7 4 121 123 49.4 5 122 123 49.2 6 122 123 39.0 7 125 125 33.9 8 126 133 50.8 9 138 164 25.3 10 225 205 15.8 Fractions 2-9 are bulked and after adding thereto 9.6 grams Primol and 0.8 grams Ionox, the resulting material is redistilled at a vacuum of 2.5 mm Hg at 9:1 reflux ratio on a 12 plate Vigreaux column yielding the following fractions: Vapor Liquid Fraction Temperature Temperature Weight No. ( C) ( C) (g) I 38 107 7.2 2 38 124 6.5 3 86 150 9.2 4 117 141 7.1 5 117 141 12.8 6 117 141 13.8 7 117 141 13.5 8 117 142 13.6 9 117 142 14.9 10 117 142 11.2 11 117 138 13.0 12 118 139 12.9 13 118 146 13.5 14 118 148 14.1 15 120 150 15.8 16 121 151 14.8 17 121 154 14.7 18 121 154 14.2 19 121 154 14.8 20 121 154 15.3 21 121 154 13.9 22 123 163 6.6 23 125 175 11.4 24 118 188 7.0 25 132 250 7.7 Fractions 7-19 are bulked and analyzed using GLC, IR and Mass Spectral analyses which confirm that the resulting product is 2 - benzyl - 2 - ethyl - hex 3 - enal. This material has a sweet, floral, rosey note.

EXAMPLE VI Preparation of 2-prenyl nonenal (B6) Into a 500 ml reaction flask equipped with cooling bath, thermometer, condenser, stirrer, addition funnel and Thermo-watch are placed a solution of 30.5 grams of sodium hydroxide in 30.5 grams of water. 30.5 Grams of toluene and 6 grams of tricapryl methyl ammonium chloride is then added and the mixture is cooled to 300C. Over a 1-1/2 hour period, a solution of 110 grams of 2-nonenal (A4) and 45 grams of prenyl chloride is added to the reaction mass. The reaction mass is then stirred for another hour at 270C after which time 100 ml water is added. The organic layer is separated and washed neutral and the solvent stripped off.

The residual oil is then distilled through a 12" Vigreaux column, after adding thereto 3.5 grams of Primol and 1 gram of lonox. The distillation data is as follows: Vapor Liquid Fraction Temperature Temperature Vac. Weight No. ( C) ( C) mm Hg (g) 139 163 0.8 8.6 2 151 180 0.8 10.3 3 175 193 0.8 8.0 4 192 210 0.7 10.4 5 200 225 1.9 12.1 NMR, IR and Mass Spectral analyses confirm that this material is 2-prenyl nonenal having the structure:

mixture of isomers) EXAMPLE VII Orange Terpeneless Perfume Formulation The following mixture is prepared: Parts by Ingredient Weight Alcohol C5 (n-nonanol) 2 Alcohol C,0 (n-decanol) Alcohol C12 (n-dodecanol) 4 Aldehyde C5 (n-nonanal) 2 Aldehyde C10 (n-decanal) 3 Aldehyde C12 (n-dodecanal) Citral 2 Methyl Anthranilate Neryl Acetate 3 Geranyl Acetate 4 Terpenyl Acetate 5 Nerol 10 Terpineol 5 Geraniol 20 Linalool 40 Lenalyl Acetate 15 In the alternative one of Parts by Weight (i) 2,5-dimethyl-2-propenyl-hex-4-enal; (B 1) (ii) 2-methyl-2-benzyl-pent-3-enal; (B2) (iii) 2-prenyl citral; (B5) 10 (iv) 2-butenyl-2-ethyl-5-methyl hex-4-enal; (B3) (v) 2-benzyl-2-ethyl-hex-3-enal; (B4) (vi) 2-prenyl nonenal (B6) 2,5 - Dimethyl - 2 - propenyl hex - 4 - enal; 2 - methyl - 2 - benzyl - pent 3 - enal; 2 - prenal citral; 2 - butenyl - 2 - ethyl - 5 - methyl hex - 4 - enal; 2 benzyl - 2 - ethyl - hex - 3 - enal; and 2 - prenyl non - 2 - enal imparts a decided green, citrus, fruity, floral note, enhancing the orange note of this orange terpeneless perfume formulation.

EXAMPLE VIII Preparation of 2,4,7-trimethyl-2,6-octadienal (I) Reaction:

Into a 12 liter reaction flask equipped with stirrer, thermometer, reflux condenser and addition funnel is placed a solution of 720 grams of sodium hydroxide and 720 grams of water. 800 Grams of cyclohexane and 50 grams of tricapryl methyl ammonium chloride are then added to the mixture. The mixture is heated to a temperature in the range of 75-80"C with stirring; over a period of 6 hours, a solution of 2000 grams of 2-methyl-pent-2-enal (Al) and 2100 grams of prenyl chloride is added to the reaction mass. At the end of the 6 hour period, the reaction mass is stirred at 75-800C for another 4 hours. At the end of the 4 hour period, the organic layer is separated, washed neutral and the solvent stripped off.

The residual oil is then distilled on a rushover column after adding 82.0 grams of Primol and 6 grams of Ionox. The fractions taken off the column are as follows: Vapor Liquid Fraction Temperature Temperature Vacuum Weight No. ( C) ( C) mm Hg 1 42-65 100100 12095 24.7 2 75 100 87 34.8 3 80 102 87 41.7 4 87 102 75 82.7 5 90 102 64 94.9 6 88 105 59 121.1 7 94 114 58 133.8 8 108 125 58 179.4 9 120 130 56 165.2 10 122 132 57 161.5 11 124 134 57 199.5 12 125 136 57 197.4 13 127 139 57 182.3 14 129 145 57 198.5 15 133 157 57 173.1 16 144 185 57 165.8 17 172 212 57 99.0 18 179 215 55 35.1 Fractions 4-17 of the rushed over material are then bulked and re-distilled on an 18" Goodloe column after adding thereto 5 grams of Ionox and 63 grams of Primo. The distillation is carried out using a reflux ratio of 9:1. The fractions distilled are as follows: Vapor Liquid Fraction Temperature Temperature Vacuum Weight No. ( C) ( C) mm Hg (g) 1 49-55 96-97 50 14.2 2 59 100 50 27.9 3 60 104 50 40.6 4 60 109 50 45.5 5 66 120 50 85.6 6 100 124 50 56.5 7 113 125 50 27.0 8 118 125 50 27.5 9 118 125 50 89.4 10 95-100 1l(wl10 25-27 22.0 11 108 113 30 51.8 12 100 109 26 74.9 13 99 109 26 79.0 14 99 109 26 73.0 15 104 110 26 63.1 16 108 113 26 83.8 17 106 113 26 73.4 18 105 111 26 82.3 19 105 112 25 82.4 20 105 112 25 83.5 21 105 112 25 89.7 22 105 116 25 98.4 23 105 119 25 92.0 24 107 124 25 91.1 25 112 131 25 92.8 26 114 145 25 91.5 27 116 170 20 48.6 28 124 192 20 36.5 29 140 216 15 31.8 30 147 250 15 22.7 Fractiona 24-27 are then bulked and combined with 10 grams of Primol and 0.3 grams of Ionox. The resulting material is distilled on a 12" Vigreaux column equipped with heating mantle and fraction cutter. The fractionation data is as follows: Vapor Liquid Fraction Temperature Temperature Vacuum Weight Reflux No. ( C) ( C) mm Hg (g) Ratio 83-85 98-98 15-14 2.0 14:1 2 86 99 14 9.0 14:1 3 86 99 12 10.5 14:1 4 86 99 12 8.1 14:1 5 86 99 12 8.5 14:1 6 88 99 12 14.4 14:1 7 85 99 12 7.3 14:1 8 85 99 12 6.2 14:1 9 85 99 12 11.3 14:1 10 85 99 12 11.3 14:1 11 85 99 12 14.1 14:1 12 85 99 12 15.4 14:1 13 85 102 12 14.5 14:1 14 83-85 99-101 10-10 4.8 12:1 15 90 104 12 8.3 12:1 16 89 104 13 9.9 12:1 17 82 104 12 7.0 12:1 18 87 105 12 12.8 12:1 Vapor Liquid Fraction Temperature Temperature Vacuum Weight Reflux No. ("C) ( C) mm Hg (g) Ratio 19 90 105 11 11.2 12:1 20 92 105 11 9.6 12:1 21 94 105 11 8.6 12:1 22 94 105 11 11.9 12:1 23 94 105 11 15.8 12:1 24 94 105 11 16.9 12:1 25 94 105 11 14.6 12:1 26 94 105 11 15.8 12:1 27 94 105 11 14.4 12:1 28 94 119 11 8.4 12:1 29 100 140 11 5.7 12:1 30 108 220 11 5.7 12:1 Fraction 26 of the resulting distillate is then chromatographed on a GLC column (conditions: 1/4"x10'; 5% Carbowax 20M [adsorbed on Chromasorb G] column programmed at 100 C/minute from 80--2200C) indicating a major component of 90 purity. NMR, Mass Spectral and IR analyses yield the information that this major component is 2,4,7 - trimethyl - 2,6 - octadienal.

The NMR spectrum for fraction 26, major peak, is set forth in Figure 2. The IR spectrum for fraction 26, major peak, is set forth in Figure 3.

EXAMPLE IX Mandarin Orange Flavor Formulation An orange flavor formulation is prepared by admixing: Ingredients Parts Natural orange oil 13.00 Acetaldehyde 1.50 Ethyl acetate 0.10 Ethyl butyrate 0.50 Propanal 0.10 Trans-2-hexenal 0.10 Ethyl alcohol (95%) 60.00 Fusel oil 0.05 Propylene glycol 24.65 This is denominated Flavor "A". A second formulation, Flavor "B" is prepared by adding 2,4,7 - trimethyl - 2,6 - octadienal produced according to Example VIII (one percent in ethanol) to a portion of Flavor "A".

Each of Flavors "A" and "B" is added in the amount of two ounces per gallon of 32 Baume sugar syrup to produce a syrup for combination with water to form a drink. The beverage prepared using Flavor "A" is a passable orange beverage of good character, flavor and intensity.

The beverage prepared using Flavor "B" has a much improved mandarin orange flavor with new mandarin orange and lemony nuances.

EXAMPLE X Preparation of Cis-jasmone (B7) Into a 250 ml reaction flask equipped with heating mantle, condenser, stirrer, thermometer and addition funnel is placed a solution of 21.3 grams of sodium hydroxide and 21.3 grams of water. Twenty grams of toluene and 1.5 grams of tricapryl methyl ammonium chloride (Aliquat 336, produced by the General Mills Chemicals, Inc.) are then added to the mixture. The reaction mass is then heated to reflux (102"C) and, over a one hour period, a mixture of 35 grams of cis-pent-2enyl-l-chloride and 24.5 grams of 3-methyl cyclopentenone-2 (A5) is added to the reaction mass while refluxing. The reaction mass is then refluxed for an additional 4 hour period, after which time it is mixed with 100 ml cold water and transferred to a separatory funnel.

The organic layer is separated, washed neutral and the solvent stripped off.

The residual oil is then retained for admixture with the reaction product of Example II prior to distillation.

EXAMPLE XI Preparation of Cis-jasmone (B7) Into a 1 liter reaction flask equipped with heating mantle, condenser, thermometer, addition funnel and stirrer is placed a solution of 106.5 grams of sodium hydroxide in 106.5 grams of water. 100 Grams of toluene and 7.5 grams of tricapryl methylammonium chloride are then added to the mixture. The mixture is heated to reflux and over a one hour period, a mixture of 122.5 grams of 3-methyl cyclopentenone-2 (A5) and 175 grams of cis-pent-2-enyl-l-chloride is added to the reaction mass. The reaction mass is then refluxed for a period of two hours, after which time 250 ml water is added thereto and the resulting mixture is transferred to a separatory funnel.

The organic layer is separated, washed neutral and the solvent is stripped off.

The residual oil is then bulked with the product of Example I and the resulting product is combined with 17 grams of Primol, 7 grams of triethanolamine and rushed over to yield the following fractions: Vapor Liquid Fraction Temperature Temperature Vacuum Weight No. ( C) ( C) mm (g) I 43-120 91-159 2.6 27.3 2 125 162 2.6 19.0 3 167 185 2.6 18.3 4 184 201 2.5 19.4 5 203 217 2.5 16.4 6 220 240 2.5 26.9 Fractions 1, 2 and 3 of the rushed over material, are then bulked and the bulked material is combined with 2 grams of Primol and lonox. The resulting material is then fractionally distilled on a 12 plate Vigreaux column yielding the following fractions: Vapor Liquid Fraction Temperature Temperature Vacuum Weight No. ( C) ( C) mm (g) 1 53 107 3.5 4.8 2 36 100 1.0 4.5 3 72 120 0.8 3.1 4 80 121 0.8 4.0 5 80 123 1.0 4.9 6 78 122 1.2 4.2 7 79 128 1.2 3.8 8 79 137 1.2 4.6 9 79 144 1.2 3.9 10 87 151 1.2 2.3 11 97 159 1.2 4.1 12 98 174 1.2 3.8 13 112 182 1.2 2.4 14 120 204 1.2 1.9 15 125 250 1.2 2.6 Fractions 6-9 are bulked, analyzed and evaluated NMR, IR and Mass Spectral analyses yield the result that the product is 94 / < cis-jasmone having the structure:

and the remainder, trans jasmone. The NMR spectrum is set forth in Figure 4. The IR spectrum is set forth in Figure 5.

(There is no Example XII).

EXAMPLE XIII Jasmine Perfume The following mixture is prepared: Parts by Ingredient Weight Para Cresol I Acetyl Methyl Anthranilate 20 Farnesol 4 Cis-3-hexenyl benzoate 30 Nerolidol 30 Indol 15 Eugenol 20 Benzyl Alcohol 40 Methyl Linoleate 40 Jasmin Lactone 20 Dihydromethyl Jasmonate 10 Linalool 150 Benzyl Acetate 400 Abietyl Alcohol 150 Cis Jasmone (Produced according to Example XI; bulked fractions 6-9) 50 The cis-jasmone, produced according to Example XI, imparts to this jasmine formulation the green, sweet, celery-like note so important to the jasmine perfume formulation.

EXAMPLE XIV Preparation of l-acetyl-3,3-dimethyl-(2-propenyl)cyclohexane (H 1) Reaction:

0+ c Totuene Toluene < (A6) (Hl) or (minor product) (JI) Allyl chloride (222 grams, 3.8 moles) are added over a period of 15 minutes to a stirred slurry of l-acetyl-3,3-dimethylcyclohexane (A6) (462 grams, 3 moles), granular sodium hydroxide (180 grams, 4.5 moles), Aliquat 336 (tricapryl methyl ammonium chloride) (24 grams) and toluene (200 grams) at 700C. The slurry is heated to reflux for 7.5 hours at the end of which period of time the temperature rises to 830C. The slurry is then cooled and 1 liter of water is added to the reaction mass with stirring. The organic phase of the reaction mass is washed twice with water and distilled through a 12"x1/2" packed Goodloe column fixed with an automatic reflux head set at a 19:1 reflux take-off ratio (85"C, 2.7 mm Hg pressure) yielding 275 grams of product having the structure:

(56 /n conversion), 40 grams of the compound having the structure:

(8 yield) and 147 grams of 1 - acetyl - 3,3 - dimethycyclohexane.

When sodium hydride instead of sodium hydroxide a compound having the structure:

is produced.

The NMR spectrum for the compound having the structure:

is set forth in Figure 6. The Infrared spectrum for this compound is set forth in Figure 7.

The NMR analysis is as follows:

, ppm Interpretation 0.74 (s,3) 0.90 (s, 3) methyl groups "A" 2.14 (s, 3) CH3 Group "B" 4.8e5.1 (m, 2) CH2GroupC 5 4e5.8 (m, 1) H The infrared analysis is as follows: C=O; 1690 cm-' C=C; 1660 The Mass Spectral analysis is as follows: m/e= 95, 94, 69, 41, 109, 55, 194 (parent peak).

The NMR spectrum for the compound having the structure:

is set forth in Figure 8. The NMR analysis is as follows:

, ppm Interpretation 0.90 (s,3) 0.93 (s,3) Methyl Groups "A" 2.22.65 (m, 5) CH2,s "B" and Hc 4.60-5.12 (m, 2) CH2 "D" 5.50-5.95 (m, 1) HE The Mass Spectral analysis is as follows: m/e=69, 111, 55, 41, 83, 139, 194 (parent peak).

The NMR spectrum for the compound having the structure:

H < 0 (B12) (stereochemistry unknown) (produced when using sodium hydride) is set forth in Figure 9. The Infrared spectrum is set forth in Figure 10.

The NMR analysis is as follows:

A c D (stereochemistry unknown) 03C CH3 B CH3 A 8, ppm Interpretation 0.83-0.93 Methyl Groups "A" 2.08 (d, 1) small coupling J=(Hz) CH3 "B" scattered allylic H resonances H, The Infrared analysis is as follows: 1600 cm-'; C=C 1700; C=O The Mass Spectral analysis is as follows: m/e=l 11, 69, 55, 41, 43, 57, 290 (parent peak).

EXAMPLE XV A perfume composition is prepared by admixing the following ingredients in the indicated proportions: Amount Ingredient (Grams) n-Decyl Aldehyde n-Dodecyl Aldehyde 2 Methyl Nonyl Acetaldehyde 0.5 Linalool 50 Linalyl Acetate 70 Phenyl Ethyl Alcohol 100 Petigrain SA 20 Bergamot Oil 30 Alpha Methyl lonone 25 1 - Acetyl - 3,3 - dimethyl - (2 - propenyl)cyclo- hexane produced according to the process of Example XIV 10 Cyclized Bicyclo C-12 material produced according to the process of Example IV of Canadian Patent 854,225, issued on October 20, 1970 5 Isobornyl cyclohexyl alcohol 10 Benzyl Acetate 25 2 - n - Heptyl cyclopentanone 5 353.3 (Total) 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 note.

The base composition can also be used to scent soap or other toilet goods such as lotion, aerosol and sprays.

EXAMPLE XVI Preparation of a Cosmetic Powder Composition A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcum powder with 0.25 g of I - acetyl - 3,3 - dimethyl - (2 - propenyl)cyclohexane produced according to Example XIV. It has an excellent woody, earthy, amber aroma.

EXAMPLE XVII Perfumed Liquid Detergent Concentrated liquid detergents with woody, earthy and amber aromas (which detergents are produced from Lysine salt of n-dodecyl benzene sulfonic acid as more specifically described in U.S. Patent No. 3,948,818, issued on April 6, 1976) are prepared containing 1 - acetyl - 3,3 - dimethyl - (2 - propenyl) cyclohexane prepared according to Example XIV. They are prepared by adding and homogeneously mixing the appropriate quantity of I - acetyl - 3,3 - dimethyl (2 - propenyl)cyclohexane in the liquid detergent. The detergents all possess a woody, earthy, amber aroma, the intensity increasing with greater concentrations of I - acetyl - 3,3 - dimethyl - (2 - propenyl)cyclohexane.

EXAMPLE XVII I Preparation of a Cologne and Handkerchief Perfume I - Acetyl - 3,3 - dimethyl - (2 - propenyl)cyclohexane, prepared according to the process of Example XIV is incorporated in a cologne at a concentration of 2.5 /n in 85 /n aqueous ethanol; and into a handkerchief perfume at a concentration of 20% (in 95 /n aqueous ethanol). A distinct and definite woody, earthy, amber aroma is imparted to the cologne and to the handkerchief perfume.

EXAMPLE XIX Preparation of a Cologne and Handkerchief Perfume The composition of Example XV is incorporated in a cologne at a concentration of 2.5 in 85 /n aqueous ethanol; and into a handkerchief perfume at a concentration of 20% (in 95 /n aqueous ethanol). The use of the I - acetyl - 3,3 dimethyl - (2 - propenyl)cyclohexane in the composition of Example XV affords a distinct and definite strong woody, earthy, amber aroma to the handkerchief perfume and cologne.

EXAMPLE XX Preparation of Soap Composition One hundred grams of soap chips are mixed with two grams of the composition of Example XV until a substantially homogeneous composition is obtained. The perfumed soap composition manifests an excellent amber aroma with intense woody and earthy nuances.

EXAMPLE XXI Preparation of a Detergent Composition A total of 100 grams of a detergent (Lysine salt of n-dodecylbenzene sulfonic acid as more specifically described in U.S. Patent No. 3,948,818, issued on April 6, 1976) powder is mixed with 0.70 grams of the composition of Example XV until a substantially homogeneous composition is obtained. This composition has an excellent amber aroma with intense earthy and sweet woody nuances.

EXAMPLE XXII Raspberry Flavor Formulation The following basic raspberry flavor formulation is produced: Parts by Ingredient Weight Vanillin 2.0 Maltol 5.0 Parahydroxybenzylacetone 5.0 Alpha-ionone (10 /n in propylene glycol) 2.0 Ethyl butyrate 6.0 Ethyl acetate 16.0 Dimethyl sulfide 1.0 Isobutyl acetate 13.0 Acetic acid 10.0 Acetaldehyde 10.0 Propylene glycol 930.0 1 - Acetyl - 3,3 - dimethyl - (2 - propenyl)cyclohexane is added to half of the above formulation at the rate of 2.0. The formulation with the 1 - acetyl - 3,3 dimethyl - (2 - propenyl)cyclohexane is compared with the formulation without the I - acetyl - 3,3 - dimethyl - (2 - propenyl)cyclohexane at the rate of 0.01 percent (100 ppm) in water and evaluated by a bench panel.

The flavor containing the 1 - acetyl - 3,3 - dimethyl - (2 propenyl)cyclohexane is found to have substantially sweeter aroma notes and a sweet raspberry, raspberry kernel-like and sweet aftertaste and mouthfeel missing in the basic raspberry formulation. It is the unanimous opinion of the bench panel that the chemical, 1 - acetyl - 3,3 - dimethyl - (2 - propenyl)cyclohexane rounds the flavor out and contributes to a very natural fresh aroma and taste as found in full ripe raspberries. Accordingly, the flavor with the addition of the 1 - acetyl3,3 dimethyl - (2 - propenyl)cyclohexane is considered as substantially better than the flavor without 1 - acetyl - 3,3 - dimethyl - (2 - propenyl)cyclohexane.

EXAMPLE XXIII A. Powder Flavor Composition 20 Grams of the flavor composition of Example XXII emulsified in a solution containing 300 gm gum acacia and 700 gm water. The emulsion is spray-dried with a Bowen Lab Model Drier utilizing 260 c.f.m. of air with an inlet temperature of 500OF., an outlet temperature of 200OF., and a wheel speed of 50,000 r.p.m.

B. Sustained Release Flavor The following mixture is prepared: Parts by Ingredient Weight Liquid Raspberry Flavor Composition of Example XXII 20 Propylene glycol 9 Cab-O-Sil M-5 (Brand of Silica produced by the Cabot Corporation of 125 High Street, Boston, Mass. 02110; Physical Properties: Surface Area: 200 m2/gm Nominal particle size: 0.012 microns Density: 2.3 Ibs/cu.ft.) 5.00 The Cab-O-Sil is dispersed in the liquid raspberry flavor composition of Example XXII with vigorous stirring, thereby resulting in a viscous liquid. 71 Parts by weight of the p

EXAMPLE XXVII Toothpaste Formulation The following separate groups of ingredients are prepared: Parts by Weight Ingredient Group "A" 30.200 Glycerin 15.325 Distilled Water .100 Sodium Benzoate .125 Saccharin Sodium .400 Stannous Fluoride Group "B" 12.500 Calcium Carbonate 37.200 Dicalcium Phosphate (Dihydrate) Group "C" 2.000 Sodium N-Lauroyl Sarcosinate (foaming agent) Group "D" 1.200 Flavor Material of Example XXIII 100.00(Total) Procedure: 1. The ingredients in Group "A" are stirred and heated in a steam jacketed kettle to 1600 F.

2. Stirring is continued for an additional three to five minutes to form a homogenous gel.

3. The powders of Group "B" are added to the gel, while mixing until a homogenous paste is formed.

4. With stirring, the flavor of "D" is added and lastly the sodium n-lauroyl sarcosinate.

5. The resultant slurry is then blended for one hour. The completed paste is then transferred to a three roller mill and then homogenized, and finally tubed.

The resulting toothpaste when used in a normal toothbrushing procedure yields a pleasant raspberry flavor, of constant strong intensity throughout said procedure (1--1.5 minutes).

EXAMPLE NXVIII Chewable Vitamin Tablets The flavor material produced according to the process of Example XXIV is added to a Chewable Vitamin Tablet formulation at a rate of 10 gm/Kg which Chewable Vitamin Tablet formulation is prepared as follows: In a Hobart Mixer, the following materials are blended to homogeneity: Gms/1000 Tablets Vitamin C (ascorbic acid) as ascorbic acid-sodium ascorbate mixture 1:1 70.0 Vitamin B1 (thiamine mononitrate) as Rocoat thiamine mononitrate 33 1/3 /n (Hoffman La Roche) 4.0 Vitamin B2 (riboflavin) as Rocoat riboflavin 331/3% 5.0 Vitamin B6 (pyridoxine hydrochloride) as Rocoat pyridoxine hydrochloride 331/3% 4.0 Niacinamide as Rocoat niacinamide 33 1/3 /n 33.0 Calcium pantothenate 11.5 Vitamin B,2 (cyanocobalamin) As Merck 0.1 /" in gelatin 3.5 Vitamin E (dl-alpha tocopheryl acetate) as dry Vitamin E acetate 33 1/3 /"Roche 6.6 d-Biotin 0.044 Certified lake color 5.0 Flavor of Example XXIV (as indicated above) Gums11000 Tablets Sweetener-sodium saccharin 1.0 Magnesium stearate lubricant 20.0 Mannitol q.s. to make 500.0 Preliminary tablets are prepared by slugging with flat-faced punches and grinding the slugs to 14 mesh. 13.5 Grams dry Vitamin A acetate and 0.6 grams Vitamin D are then added as beadlets. The entire blend is then compressed using concave punches at 0.5 grams each.

Chewing of the resultant tablets yields a pleasant, long-lasting, consistently strong raspberry flavor for a period of 12 minutes.

EXAMPLE XXIX Preparation of l-acetyl-l-methallyl-3,3-dimethylcyclohexane and l-(2)methallyl-4-methyl-4-pentenoyl)-3,3-dimethylcyclohexane Reaction:

p + ss ALlaUOT036 OLUENE (A6) 0 (G2) CI (G2)Cl 0 + 0 (major (minor (minor (H2) t Product) (K2)1 product) (J2) product) A slurry of l-acetyl-3,3-dimethylcyclohexane (A6) (624 grams, 4 moles), ganular sodium hydroxide (240 grams, 6 moles), Aliquat 336 (tricaprylmethylammonium chloride [35 grams]), methallyl chloride (G2) (432 grams, 4.8 moles), and 400 ml of toluene is heated at reflux for 4 1/4 hours. At the end of this time, one liter of water is added to the cooled reaction mass. The aqueous layer is discarded, and the organic layer is distilled rapidly through a short column to afford 203 grams of recovered 1-acetyl-3,3 - dimethylcyclohexane, 500 grams of I - acetyl - 3,3 - dimethyl - 1 - methallylcyclohexane (H2), and 73 grams of 3,3 - dimethyl - I - (2 - methallyl - 4 - methyl - 4 - pentenoyl)cyclohexane (K2) (14", 3.0 mm Hg) containing 5% of 3,3 - dimethyl - I - (4 - methyl - 4 pentenoyl)cyclohexane (J2). A portion of the latter compound is isolated by GLC chromatography (I'xl/4" 80 /n SE-30 packed column; 200"C isothermal) and exhibits the following odor and flavor properties: Odor Properties: Flavor Properties: Green; Fatty; Herbaceous; Sweet; Melony; Fruity; Fruity; Citrus; Galbanum-like; Green; Ginger-like; and Vegetable-like; and Citrusy. Waxy.

The NMR analysis for the compounds set forth below is as follows:

ppm Interpretation 0.92 (s, 3) 0.94 (s, 3) methyl groups "A" 1.70 (s,6) methyl groups "C" 3.02 (quintet, I, J=6H) HD 4.76 (d, 4, J=8H) methyl groups "B" The Infrared analysis is as follows: C=O 1695 cm-' C=CH2 1635 cm- The Mass Spectral analysis is as follows: MW-262 (confirmed by GC-MS) The NMR spectrum is set forth in Figure 11 for I - acetyl - 3,3 - dimethyl 1 - methallylcyclohexane. The Infrared spectrum is set forth in Figure 12 for 1 acetyl - 3,3 - dimethyl - I - methallylcyclohexane.

The NMR spectrum for 3,3-dimethyl - 1 - (2 - methallyl - 5 - methyl - 4 pentenoyl)cyclohexane is set forth in Figure 13. The Infrared spectrum is set forth in Figure 14.

EXAMPLE XXX Reaction:

C toluene X KOH Cl (G2) (H2) 0 (A6) (G2) (H2) (J2) A slurry of I - acetyl - 3,3 - dimethylcyclohexane (A6) (156 grams, 1 mole), potassium hydroxide (86 grams, 1.5 moles), and toluene (300 ml) is heated to reflux.

Methallyl chloride (G2) (135 grams, 1.5 moles) is added to the thickened reaction mass whereupon the mass becomes more fluid. The mixture is heated at reflux for 6 1/2 hours. At the end of this period, the reaction mass is cooled to room temperature, and 500 ml of water are added thereto. The aqueous layer is discarded, and the organic layer is distilled to afford recovered I - acetyl - 3,3 dimethylcyclohexane (86 gm), I - acetyl - 3,3 - dimethyl - 1 - methallylcyclohexane (H2) (76 gm, containing 2% 3,3 - dimethyl - 1 - (4 - methallylcyclohexane. (H2) (67 gm, containing 2% 3,3 - dimethyl - 1 - (4 - methyl4 - pentenoyl)cyclohexane) (J2). (NMR Spectrum Fig. 11 IR spectrum, Fig. 12, and 3,3 - dimethyl - I - (4 - methyl - 4 - pentenoyl)cyclohexane (52) (12 gm).

EXAMPLE XXXI Reaction:

A mixture of l-acetyl-3,3 - dimethylcyclohexane (A6) (156 grams, 1 mole) sodium hydroxide (60 grams, 1.5 moles), methallyl chloride (G2) (135 grams, 1.5 moles) and triethylamine (10 grams) is stirred and heated at 8840C for 12 hours.

The reaction mass is cooled to room temperature. Water is added with stirring, and the aqueous layer is discarded. The organic layer is distilled to afford 1 - acetyl 3,3 - dimethylcyclohexane (62.4 gm), I - acetyl - 3,3 - dimethyl - I - (2 methyl - 2 - propenyl)cyclohexane (80 gm) (H2), (NMR spectrum, Fig. ll; IR spectrum, (Fig. 12), and 3,3 - dimethyl - 1 - (4 - methyl - 4pentenoyl)cyclohexane (J2) (8 gm).

EXAMPLE XXXII Reaction:

A fresh solution of potassium - t - butoxide is prepared by adding potassium metal (28 grams, 0.72 moles) to 500 ml of anhydrous t - butanol under a nitrogen blanket. I - Acetyl - 3,3 - dimethylcyclohexane (A6) is added thereto, and the resulting mixture is stirred at room temperature for I hour. Methallyl chloride (74.4 grams, 0.8 moles) is added, and the reaction mass is allowed to stir for an additional hour. The mixture is filtered to remove potassium chloride, and the t-butanol is removed by evaporation on a rotary evaporator. The residual oil is distilled to afford a mixture of I - acetyl - 3,3 - dimethylcyclohexane, 1 - acetyl - 3,3 dimethyl - I - (2 - methyl - 2 - propenyl)cyclohexane, (NMR spectrum, Fig. l l; IR spectrum, Fig. 12) and 3,3 - dimethyl - 1 - (4 - methyl - 4pentenoyl)cyclohexane.

EXAMPLE XXXIII Preparation of l-acetyl-3,3-dimethyl (2-methyl-2-propenyl)cyclohexane (H2) Reaction:

18-crown-6 0 KO-t-Bu Ct( Diben zo derivative (A6) (G2) (H2) A slurry of potassium hydroxide (84 grams, 1.5 moles), 1 - acetyl - 3,3 dimethylcyclohexane (156 grams, 1 mole), dibenzo - 18 - crown - 6 (3 grams) having the structure:

produced by the Aldrich Chemical Company of Metuchen, New Jersey, and toluene (150 ml) is heated to reflux whereupon the reaction mass thickens. The mass is cooled to 700C, and methallyl chloride (135 grams, 1.5 moles) is added thereto rendering the reaction mixture more fluid. The reaction mixture is heated at reflux for an additional 9 hours whereupon the mass is cooled, and water is added. The aqueous layer is decanted and the organic layer is distilled to afford I acetyl - 3,3 - dimethylcyclohexane (62 gm) and 1 - acetyl - 3,3 - dimethyl - I (2 - methyl - 2 - propenyl)cyclohexane (83 gm, NMR spectrum, Fig. 11; TR spectrum, Fig. 12).

EXAMPLE XXXIV A tobacco blend is made up by mixing the following materials: Parts by Ingredient Weight Bright 40.1 Burley 24.9 Maryland 1.1 Turkish 11.6 Stem (flue cured) 14.2 Glycerine 2.8 Water 5.3 The above tobacco is used in producing cigarettes and the following formulatidn is compounded and incorporated into each of these cigarettes.

Parts by Ingredient Weight Ethyl butyrate .05 Ethyl valerate .05 Maltol 2.00 Cocoa extract 26.00 Coffee extract 10.00 Ethyl alcohol 41.90 Water 20.00 The above flavor is incorporated into model "filter" cigarettes at the rate of 0.1if. One-third of these model cigarettes are treated in the tobacco section with the mixture of 1 - acetyl - I - methallyl - 3,3 - dimethylcyclohexane and 1 - (2 methallyl - 5 - methyl - 4 - pentenoyl) - 3,3 - dimethylcyclohexane produced according to Example XXIX at 100 ppm per cigarette. Another third of these model cigarettes are treated in the filter with the mixture of 1 - acetyl - 1 methallyl - 3,3 - dimethylcyclohexane and 1 - (2 - methallyl - 5 - methyl - 4 pentenoyl) - 3,3 - dimethylcyclohexane at the rate of 2xl0-5 gm and 3x10-5 gm.

When evaluated by paired comparison the cigarettes treated both in the tobacco and in the filter with the mixture of 1 - acetyl - I - methallyl - 3,3 dimethylcyclohexane and 1 - (2 - methallyl - 5 - methyl - 4 - pentenoyl - 3,3 dimethylcyclohexane are found, in smoke flavor, to have a green, sweet, fruity, floral and Virginia tobacco-like flavor and aroma nuance in the mainstream and in the sidestream on smoking and, in addition, prior to smoking.

EXAMPLE XXXV A tobacco blend is made up by mixing the materials as in Example XXXIV.

The tobacco blend is used in producing cigarettes and the formulation as described in Example XXXIV is compounded and incorporated into model "filter" cigarettes at the rate of 0.1%. One-third of these model cigarettes are treated in the tobacco section with 1 - acetyl - 1 - 3,3 - dimethylcyclohexane produced according to Example XXXIII at 100 ppm per cigarette. Another third of these model cigarettes are treated in the filter with I - acetyl - I - methallyl - 3,3 dimethylcyclohexane at the rate of 2x 10-5 gm. and 3x 10-5 gm. When evaluated by paired comparison, the cigarettes treated both in the tobacco and in the filter with 1 - acetyl - 1 - methallyl - 3,3 - dimethylcyclohexane are found, in smoke flavour, to have a green, sweet, fruity, floral and Virginia tobacco-like flavour and aroma nuance in the mainstream and in the sidestream on smoking and, in addition, prior to smoking.

EXAMPLE XXXVI A tobacco blend is made up by mixing the materials as in Example XXXIV.

The tobacco blend is used in producing cigarettes and the formulation as described in Example XXXIV is compounded and incorporated into model "filter" cigarettes at the rate of 0.1%. One-third of these model cigarettes are treated in the tobacco section with the I - acetyl - I - methallyl - 3,3 - dimethylcyclohexane produced according to one of Examples XXX, XXI, or XXII at 100 ppm per cigarette. Another third of these model cigarettes are treated in the filter with the 1 - acetyl - I - methallyl - 3,3 - dimethylcyclohexane at the rate of 2x 10-5 gm.

and 3x 10-5 gm. When evaluated by paired comparison, the cigarettes treated both in the tobacco and in the filter with the I - acetyl - I - methallyl - 3,3 dimethylcyclohexane are found, in smoke flavour, to have a green, sweet, fruity, floral and Virginia tobacco-like flavour and aroma nuance in the mainstream and in the sidestream on smoking and, in addition, prior to smoking.

EXAMPLE XXXVII Orange Flavour Formulation An orange flavour formulation is prepared as in Example IX.

This is denominated Flavour "A". A second formulation, Flavour "B" is prepared by adding l-acetyl - 1 - methallyl - 3,3 - dimethylcyclohexane (one percent in ethanol) to a portion of Flavour "A" in the ratio of 2 parts to 100 parts of Flavour "A".

Each of Flavours "A" and "B" is added in the amount of two ounces per gallon of 32 Baume sugar syrup to produce a syrup for combination with water to form a drink. The beverage prepared using Flavour "A" is a passable orange beverage of good character, flavour and intensity.

The beverage prepared using Flavour "B" has a much improved flavour. The improvement contributed by the I - acetyl - I - methallyl - 3,3 dimethylcyclohexane is due to: 1. a greater degree of the natural character of freshly squeezed orange juice.

2. greater orange juice flavour depth.

* EXAMPLE XXXVI II Perfume Formulation A perfume formulation is prepared by admixing: Ingredients Parts Linalool 30 Linalyl acetate 10 Terpineol coeur 5 Nerol coeur 10 Terpinyl acetate 2 Geranyl acetate 2 Neryl acetate 2 Methyl anthranilate I Citral 10 n-Decyl alcohol n-Dodecyl alcohol 5 n-Dodecanal 15 n-Decanal 30 n-Nonanol 3 n-Nonanal 5 n-Decyl acetate 5 n-Dodecyl acetate 3 I - acetyl - I - methallyl - 3,3 - dimethylcyclohexane (Produced by Example XXIX) 5 The I - acetyl - I - methallyl - 3,3 - dimethylcyclohexane imparts a natural, tart, orange character to this terpeneless orange perfume formulation.

EXAMPLE XXXIX Reaction:

toluene 0+ lr ? c-i cl (A6) 0 (G1) (HI) (JI) A slurry of I - acetyl - 3,3 - dimethylcyclohexane (156 grams, I mole), potassium hydroxide (86 grams, 1.5 moles), and toluene (300 ml) is heated to reflux.

Allyl chloride (114 grams, 1.5 moles) is added to the thickened reaction mass whereupon the mass becomes more fluid. The mixture is heated at reflux for 6 1/2 hours. At the end of this period, the reaction mass is cooled to room temperature, and 500 ml of water is added thereto. The aqueous layer is discarded, and the organic layer is distilled to afford 74 grams of recovered I - acetyl - 3,3 dimethylhexane, 53 grams of 1 - acetyl - 3,3 - dimethyl - 1 - (2 - propenyl)cyclohexane, and 35 grams of 3,3 - dimethyl - I - (4 - pentenoyl)cyclohexane.

The NMR spectrum for the I - acetyl - 3,3 - dimethyl - 1 - (2 - propenyl)cyclohexane is set forth in Fig. 15. The Infrared spectrum is set forth in Fig. 16.

The NMR analysis is as follows:

8. ppm Interpretation 0.74 (s,3) 0.90 (s, 3) methyl groups "A" 2.14(s, 3) CH3Group"B" 4.8o5.1 (m,2) CH3 Group "C" 5.4o5.8 (m,l) HD The Infrared analysis is as follows: C=O; 1690 cm- C=C; 1660 The Mass Spectral analysis is as follows: m/e= 95, 94, 69, 41, 109, 55, 194 (parent peak).

The NMR analysis for 3,3 - dimethyl - I - (4 - pentenoyl)cyclohexane is set forth in Fig. 17 and is as follows:

Us, ppm Interpretation 0.90 (s,3) Methyl Groups 'A" 0.93 (s,3) 2.2 < 2.65 (m,5) CH2,s "B" and Hc 4.605.12 (m, 2) CH2 "D" .5.55.95(m, 1) HE The Mass Spectral analysis is as follows: m/e=69, 111, 55, 41, 83, 139, 194 (parent peak).

EXAMPLE XL Reaction:

A mixture of I - acetyl - 3,3 - dimethylcyclohexane (156 grams, 1 mole), sodium hydroxide (60 grams, 1.5 moles), allyl chloride (114 grams, 1.5 moles) and triethylamine (10 grams) is stirred and heated at 8O840C for 12 hours. The reaction mass is cooled to room temperature. Water is added with stirring, and the aqueous layer is discarded. The organic layer is distilled to afford 119 grams of 1 acetyl - 3,3 - dimethylcyclohexane, 31 grams of I - acetyl - 3,3 - dimethyl - 1 (2 - pentenyl)cyclohexane, and 5 grams of 3,3 - dimethyl - 1 - (4 - pentenoyl)cyclohexane.

The NMR spectrum for I - acetyl - 3,3 - dimethyl - I - (2 propenyl)cyclohexane is set forth in Fig. 15. The Infrared spectrum is set forth in Fig. 16. The NMR spectrum for 3,3 - dimethyl - 1 - (4 - pentenoyl)cyclohexane is set forth in Fig. 17.

EXAMPLE XLI Reaction:

A fresh solution of potassium-t-butoxide is prepared by adding potassium metal (28 grams, 0.72 moles) to 500 ml of anhydrous t-butanol under a nitrogen blanket. I - Acetyl - 3,3 - dimethylcyclohexane is added thereto, and the resulting mixture is stirred at room temperature for 1 hour. Allyl chloride (63.2 grams, 0.8 moles) is added, and the reaction mass is allowed to stir for an additional hour. The mixture is filtered to remove potassium chloride, and the t-butanol is removed by evaporation on a rotary evaporator. The residual oil is distilled to afford 78 grams of a 13:1 mixture of 1 - acetyl - 3,3 - dimethyl - I - (2 - propenyl)cyclohexane and 3,3 - dimethyl - I - (4 - pentenoyl)cyclohexane (ratio determined by integration of GLC chromatogram. GLC conditions: 10'x 1/4" 10% SE-30 packed column, 200"C isothermal), and 41 grams of nonvolatile material.

The NMR spectrum for I - acetyl - 3,3 - dimethyl - 1 - (2 - propenyl)cyclohexane is set forth in Fig. 15. The Infrared spectrum is set forth in Fig. 16. The NMR spectrum for 3,3 - dimethyl - I - (4 - pentenoyl)cyclohexane is set forth in Fig. 17.

EXAMPLE XLII Preparation of l-acetyl-3,3-dimethyl-(2-propenyl)cyclohexane (Hl) Reaction:

+ 1'O-t-Bu 0 a- crown-6 derivative) (A6) (Gl) (Hl) A slurry of potassium hydroxide (84 grams, 1.5 moles), 1 - acetyl - 3,3 dimethyl)cyclohexane (156 grams, 1 mole), dibenzo - 18 - crown - 6 (3 grams) having the structure:

produced by the Aldrich Chemical Company of Metuchen, New Jersey, and toluene (150 ml) is heated to reflux whereupon the reaction mass thickens. The mass is cooled to 700C, and allyl chloride (114 grams, 1.5 moles) is added thereto rendering the reaction mixture more fluid. The reaction mixture is heated at reflux for an additional 9 hours whereupon the mass is cooled, and water is added. The aqueous layer is added, and the organic layer is distilled to afford 24 grams of 3,3 dimethylcyclohexane, 48 grams of I - acetyl- 3,3 - dimethyl - 1 - (2 - propenyl)cyclohexane, and 90 grams of nonvolatile material.

The NMR spectrum for 1-acetyl - 3,3 - dimethyl - I - (2 propenyl)cyclohexane is set forth in Fig. 15. The Infrared spectrum is set forth in Fig. 16.

EXAMPLE XLIII Preparation of 1-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2 and 3)-penten-l-one (LI) Reaction:

A solution of 474 grams of I - acetyl - 3,3 - dimethylcyclohexane, 500 ml methanol, 40 grams NaOH and 50 ml toluene is heated to reflux. Isobutyraldehyde (240 grams), is added dropwise over a 45 minute period. The reaction mixture is heated to reflux for a further 90 minutes, at which time, the solution is cooled to room temperature and neutralized with hydrochloric acid. The methanol is removed by distillation, and the aqueous layer is removed from the resulting two phase mixture. The organic layer is washed once with water and distilled rapidly through a short column to afford a mixture of 1 - (3,3 - dimethylcyclohexyl) - 4 methyl - cis and trans --(2 and 3) - penten - I - one (360 grams, 58 /,) [112--117"C, 2.8 mm] and higher boiling products identified as:

Redistillation of this material through a I 1/2"x 12" Goodloe column gave the following fractions: Vapor Liquid Fraction Temperature Temperature Vacuum Weight Reflux No. ( C) ( C) mm Hg (g) Ratio 85-101 128 2.8 6.6 9:1 2 112 128 2.8 10.6 9:1 3 112 128 2.8 16.6 9:1 4 112 132 2.8 12.9 9:1 5 112 128 2.8 28.3 9:1 6 112 128 2.8 12.0 9:1 7 112 128 2.8 24.2 9:1 8 112 128 2.8 27.3 9:1 9 114 134 2.8 27.1 4:1 10 115 135 2.8 22.7 4:1 11 115 137 2.8 26.9 4:1 12 115 140 2.8 25.7 4:1 13 116 149 2.8 25.0 4:1 14 116 149 2.8 26.9 4:1 15 117 155 2.8 16.9 4:1 16 122 160 2.8 16.9 4:1 17 128 165 2.8 23.9 4:1 18 128 176 2.8 26.9 4:1 19 130 205 2.8 24.3 4:1 20 130 214 2.8 23.1 4:1 21 130 219 2.8 25.5 4:1 22 138 241 2.8 25.5 4:1 23 149 250 2.8 11.7 4:1 Fractions 5-13 contain greater than 99 /" desired product having the formulae:

The following fractions contain the following percentages of this mixture: Percent Fraction No. Desired Product 3 60 4 90 5-13 > 99 14 98 15 96 16 90 17 60 18 20 Fractions 5-13, from a fragrance standpoint, have fruity, woody, piney aromas with armoise, floral nuances and a slight chocolate undertone.

From a flavor standpoint, this material has a sweet, fruity, raspberry, woody, lemon, piney aroma with a sweet, raspberry and lemon flavor character.

EXAMPLE XLIV Preparation of 1-(3,3-dimethylcyclohexyl)-4-methyl cis and trans-(2 and 3)-penten-1-one (ill) Reaction:

A mixture of I - acetyl - 3,3 - dimethylcyclohexane (462 grams), isobutyraldehyde (108 grams), boric acid (6.2 grams) and boron oxide (52 grams) is heated and stirred in an autoclave at 1500C for 5 hours. The solution is filtered from inorganic salts and washed three times with 10% HCI. Distillation affords 319 grams of I - acetyl - 3,3 - dimethylcyclohexane and 138 grams of I - (3,3 dimethylcyclohexyl) - 4 - methyl - cis - and trans - (2 and 3) - penten - 1 - one (22%, based on charged 1 - acetyl - 3,3 - dimethylcyclohexane.

The 1 - (3,3 - dimethylcyclohexyl) - 4 - methyl - cis and trans - (2 and 3) penten - 1 - one is determined by NMR and Infrared analyses to be a mixture of:

(cis and trans)

The NMR spectrum for this mixture is set forth in Figure 18. The Infrared spectrum for this mixture is set forth in Fig. 19.

The NMR analysis is as follows: ppm Interpretation 1.85 (s) 1.87 (s) Methyl Groups "A" 2.62(d,j=1 Hz) 2.76 (d,J=l Hz) Methyl Groups "C" 2.03(s) Methyl Groups "B" 2.1(s) 2.3-2.8 (broad multiplet) HD 3.14 (d, J=7Hz) CH3Group"E" 5.28 (broad t, J=7HZ) HF 6.0 and 6.28 (two multiplets) HG 6.685.92 (two multiplets) HH The Infrared analysis is as follows:

1665 cm 1710 1690 (sh) C=O 1720 (sh) 1620 cm-' C=C EXAMPLE XLV Synthesis of 1-(3,3-dimethylcyclohexyl)-cis and trans-(2 and 3)-penten-1-one (L2) Reaction:

A mixture of 462 grams of 1 - acetic - 3,3 - dimethylcyclohexane, 87 grams of propionaldehyde, 52 grams boron oxide and 6.2 grams of boric acid is heated at 1500C in an autoclave for 8 hours. After cooling to room temperature, the solution is filtered from inorganic salts, washed once with aqueous sodium carbonate and twice with saturated salt solution. Distillation through a short column afforded a mixture containing 367 grams of 1 - acetyl - 3,3 - dimethylcyclohexane and 60 grams of 1 - (3,3 - dimethylcyclohexyl) - cis and trans - (2 and 3) - penten - 1 one (20 based on charged propionaldehyde).

A portion of the distillate rich in the desired product(s) was distilled through a 1.5"x12" Goodloe column giving the following fractions: Vapor Liquid Fraction Temperature Temperature Vacuum Weight Reflux No. ( C) ( C) mm Hg (g) Ratio 55-52 105-103 2.5 10.2 9:1 2 52 109 2.2 11.1 9:1 3 60 126 2.0 5.5 9:1 4 82 138 2.0 6.6 4:1 5 88 138 2.0 3.0 4:1 6 90 140 2.0 5.3 4:1 7 90 140 2.0 6.7 4:1 8 90 144 2.0 6.7 4:1 9 90 154 2.0 6.5 4:1 10 95 181 2.0 7.0 4:1 11 93 220 2.0 2.6 4:1 Fraction &num;7, at 2 ppm, has a sweet, raspberry, fruity, piney, floral, ionone aroma and a sweet, sweet fruity, redberry, raspberry, piney, floral, ionone-like flavor. The mixture 1 - (3,3 - dimethylcyclohexyl) - cis and trans - (2 and 3 penten - 1 - one is trapped out via preparative GLC and has the structure:

(cis and trans) The GC-MS profile for this mixture is set forth in Fig. 20. The NMR spectrum is set forth in Fig. 21. The Infrared spectrum is set forth in Fig. 22.

The NMR analysis is as follows: S, ppm Interpretation 1.95 (s, 6H) CH3 Groups "A" 2.08 (t, 3, J=8Hz CH3 Groups "B" 2.25 (quintet, 2H, J=8Hz) CH2 Groups "C" 2.7-2.9 (broad multiplet, 1H) HG 6.05 and 6.22 (two multiplets) HE 6.75-7.05 (m, 1H) HF The Infrared analysis is as follows: C=O 1665 and 1685 cm-' C=C 1620 EXAMPLE XLVI Hydrogenation of l-(3,3-dimethylcyclohexyl)-4-methyl-cis and trans-(2 and 3)-penten-1-one Reaction:

Into a 250 cc Parr shaker is placed 107 grams of 1 - (3,3 - dimethylcyclohexyl) - 4 - methyl - cis and trans - (2 and 3) - penten - I - one prepared according to Example XLIII, 1 gram of 5% Palladium-on-carbon catalyst and 125 grams of isopropyl alcohol. The Parr shaker is sealed and heated to a temperature of 125"C at a pressure of 5150 psig of hydrogen and maintained at that pressure range and temperature range for a period of 1.5 hours. At the end of the 1.5 hour period, the reaction product is filtered and distilled in a 48" Vigreaux column. The distillation data is as follows: Vapor Liquid Fraction Temperature Temperature Vacuum Weight Reflux No. (0C) ( C) mm Hg (g) Ratio 67-89 118-126 2.2 3.8 9:1 2 91 137 2.2 3.7 9:1 3 91 129 2.2 7.4 4:1 4 91 129 2.2 8.6 4:1 5 91 129 2.2 13.4 4:1 6 91 129 2.2 14.0 4:1 7 91 131 2.2 15.2 4:1 8 91 156 2.2 14.7 4:1 9 94 187 2.2 8.2 4:1 10 98 240 2.2 3.5 4:1 From a food flavor standpoint, fraction &num;6, resulting from the distillation, has a sweet, piney, fruity, blueberry,

From a perfumery standpoint, bulked fractions #29, at 10% in food grade alcohol, have a low-keyed, sweet woody aroma with chocolate-like nuances.

Fraction &num;7 is determined by NMR, Infrared and Mass Spectral analyses to have the structure:

The NMR analysis is as follows: Sppm Interpretation 0.82-0.98 (m, 12H) CH3 Groups 2.43 (t, 2H, J=8Hz) Methylene "A" The Infrared analysis is as follows: 2950 cam~' 2870 1700 1560 (C=O) 1390 1360 The Mass Spectral analysis is as follows: 111, 41, 43, 69, 55 and 27 The NMR spectrum for this compound is set forth in Fig. 23. The Infrared spectrum for this compound is set forth in Fig. 24.

EXAMPLE XLVII Raspberry Flavor Formulation The basic raspberry flavor formulation is produced as in Example XXII.

1 - (3,3 - Dimethylcyclohexyl) - 4 - methyl - cis and trans - (2 and 3) - penten - I - one prepared according to Example XLIII is added to half of the basic formulation at the rate of 2.0 /n. The formulation with the 1 - (3,3 - dimethylcyclohexyl) - 4 - methyl - cis and trans - (2 and 3 - penten - I - one is compared with the formulation without the 1 - (3,3 - dimethylcyclohexyl) - 4 methyl - cis and trans - (2 and 3) - penten - 1 - one at the rate of 0.01 percent (100 ppm) in water and evaluated by a bench panel.

The flavor containing the I - (3,3 - dimethylcyclohexyl) - 4 - methyl - cis and trans(2 and 3) - penten - I - one is found to have substantially sweeter aroma notes and a sweet raspberry, raspberry kernel-like and sweet aftertaste and mouthfeel missing in the basic raspberry formulation. It is the unanimous opinion of the bench panel that the chemical, I - (3,3 - dimethylcyclohexyl) - 4 - methyl - cis and trans - (2 and 3) - penten - 1 - one rounds the flavor out and contributes to a very natural fresh aroma and taste as found in full ripe raspberries. Accordingly, the flavor with the addition of the 1 - (3,3 - dimethylcyclohexyl) - 4 - methyl - cis and trans - (2 and 3) - penten - I - one is considered as substantially better than the flavor without I - (3,3 - dimethylcyclohexyl) - 4 - methyl - cis and trans - (2 and 3) - penten - I - one.

EXAMPLE XLVIII Raspberry Flavor Formulation The following basic raspberry flavor formulation is produced as in Example XXII.

1 - (3,3 - Dimethylcyclohexyl) - cis and trans - (2 and 3) - penten - 1 - one prepared according to Example XLV is added to half of the basic formulation at the rate of 2.0. The formulation with the I - (3,3 - dimethylcyclohexyl) - cis and trans - (2 and 3) - penten - I - one is compared with the formulation without the 1 - (3,3 - dimethylcyclohexyl) - cis and trans - (2 and 3) - penten - 1 - one at the rate of 0.01 percent (100 ppm) in water and evaluated by a bench panel.

The flavor containing the 1 - (3,3 - dimethylcyclohexyl) - cis and trans - (2 and 3) - penten - 1 - one is found to have substantially sweeter aroma notes and a sweet raspberry, raspberry kernel-like and sweet aftertaste and mouthfeel missing in the basic raspberry formulation. It is the unanimous opinion of the bench panel that the chemical, I - (3,3 - dimethylcyclohexyl) - cis and trans - (2 and 3) penten - 1 - one rounds the flavor out and contributes to a very natural fresh aroma and taste as found in full ripe raspberries. Accordingly, the flavor with the addition of the 1 - (3,3 - dimethylcyclohexyl) - cis and trans - (2 and 3) - penten 1 - one is considered as substantially better than the flavor without I - (3,3 dimethylcyclohexyl) - cis and trans - (2 and 3) - penten - I - one.

EXAMPLE XLIX A. Powder Flavor Composition 20 Grams of the flavor composition of Example XLVII is emulsified in a solution containing 300 grams gum acacia and 700 grams water. The emulsion is spray-dried with a Bowen Lab Model Drier utilizing 260 c.f.m. of air with an inlet temperature of 500OF., an outlet temperature of 200OF., and a wheel speed of 50,000 r.p.m.

B. Sustained Release Flavor The process of Example XXIIIB is repeated using instead of the liquid raspberry flavor composition of Example XXII that of Example XLVII, to produce a dry, free flowing sustained release flavor powder.

EXAMPLE L Example XXIV is repeated using the liquid flavor composition of Example XLVIII instead of that of Example XXII to produce a similar cake.

EXAMPLE LI Chewing Gum 100 Parts by weight of chicle are mixed with 4 parts by weight of the flavor prepared in accordance with Example XLIX. 300 Parts of sucrose and 100 parts of corn syrup are added. Mixing is effected in a ribbon blender with jacketed side walls of the type manufactured by the Baker Perkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inch in width and 0.1 inches in thickness. The strips are cut into lengths of 3 inches each.

On chewing, the chewing gum has a pleasant long lasting raspberry flavor.

EXAMPLE LII Chewing Gum 100 Parts by weight of chicle are mixed with 18 parts by weight of the flavor prepared in accordance with Example L. 300 Parts of sucrose and 100 parts of corn syrup are then added. Mixing is effected in a ribbon blender with jacketed side walls of the type manufactured by the Baker Perkins Co.

The resultant chewing gum blend is then manufactured into strips I inch in width and 0.1 inches in thickness. The strips are cut into lengths of 3 inches each.

On chewing, the chewing gum has a pleasant long lasting raspberry flavor EXAMPLE LIII Toothpaste Formulation The groups of ingredients as in Example XXVII are prepared substituting the flavor material with Example XLIX for that of Example XXIII in Group D.

Procedure: The procedure of Example XXVII is followed to prepare a toothpaste and the resulting toothpaste when used in a normal toothbrushing procedure yields a pleasant raspberry flavor, of constant strong intensity throughout said procedure (1--1.5 minutes).

EXAMPLE LIV Chewable Vitamin Tablets The flavor material produced according to the process of Example L is added to a Chewable Vitamin Tablet Formulation at a rate of 10 gm/Kg which Chewable Vitamin Tablet Formulation is prepared as in Example XXVIII by substituting the product of Example L for that of Example XXIV.

Chewing of the resultant tablets yields a pleasant, long-lasting, consistently strong raspberry flavor for a period of 12 minutes.

EXAMPLE LV Blueberry Fondant Formulation The following blueberry fondant formulation is prepared: Parts by Ingredient Weight Oil of Cardamom 0.25 Oil of Cloves 0.50 Oil of Galanga 1.00 Oil of Cinnamon 1.25 Oil of Coriander 2.50 Oil of Fennel 2.50 Amyl Acetate 22.00 Benzyl Benzoate 33.00 1 - (3,3 - dimethylcyclohexyl) - 4 - methyl - cis and 37.00 trans - (2 and 3) - penten - 1 - one, fraction #6 produced according to Example XLV 0.1 The 1 - (3,3 - dimethylcyclohexyl) - 4 - methyl - cis and trans - (2 and 3) penten - I - one produced according to Example XLV adds sweet, piney, fruity and woody nuances to the blueberry fondant formulation thereby causing it to be more natural-like in taste and aroma.

EXAMPLE LVI A perfume composition is prepared by admixing the ingredients as in Example XV substituting I - (3,3 - dimethylcyclohexyl) - 4 - methyl - cis and trans - (2 and 3) - penten - 1 - one produced according to Example XLIV for the product of Example XIV.

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 cologned so prepared has an amber aroma leaning towards a woody amber note with an excellent armoise nuance. The base composition can also be used to scent soap or other toilet goods such as lotion, aerosol and sprays.

EXAMPLE LVII Preparation of a Cosmetic-Powder Composition A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcum powder with 0.25 g of I - (3,3 - dimethylcyclohexyl) - 4 - methyl - cis and trans - (2 and 3) - penten - 1 - one prepared according to Example XLIV. It has an excellent piney, woody, floral and fruity aroma.

EXAMPLE LVII I Perfumed Liquid Detergent Concentrated liquid detergents (Lysine salt of n-dodecylbenzene sulfonic acid as more specifically described in U.S. Patent No. 3,948,818, issued on April 6, 1976) with a piney, woody odor are prepared containing 0.10%, 0.15 /n and 0.20 /X) of 1 - (3,3 - dimethylcyclohexyl) - 4 - methyl - cis and trans - (2 and 3) - penten 1 - one prepared according to Example XLIV. They are prepared by adding and homogeneously mixing the appropriate quantity of 1 - (3,3 - dimethylcyclohexyl) 4 - methyl - cis - and trans - (2 and 3) - penten - I - one in the liquid detergent. The detergents all possess a piney, woody fragrance, the intensity increasing with greater concentrations of I - (3,3 - dimethylcyclohexyl) - 4 - methyl - cis and trans - (2 and 3) - penten - 1 - one.

EXAMPLE LIX Preparation of a Cologne and Handkerchief Perfume 1 - (3,3 - Dimethylcyclohexyl) - 4 - methyl - cis and trans - (2 and 3) - penten - 1 - one prepared according to the process of Example XLIV is incorporated in a cologne at a concentration of 2.5% in 85 aqueous ethanol; and into a handkerchief perfume at a concentration of 20% (in 95 aqueous ethanol). A distinct and definite piney, woody fragrance is imparted to the cologne and to the handkerchief perfume.

EXAMPLE LX Preparation of a Cologne and Handkerchief Perfume The composition of Example LVI is incorporated in a cologne at a concentration of 2.5 in 85 /n aqueous ethanol; and into a handkerchief perfume at a concentration of 20% (in 95 /n aqueous ethanol). The use of I - (3,3 dimethylcyclohexyl) - 4 - methyl - cis and trans - (2 and 3) - penten - I - one in the composition of Example XLIV affords a distinct and definite strong amber aroma with piney, woody notes to the handkerchief perfume and cologne.

EXAMPLE LXI Preparation of Soap Composition One hundred grams of soap chips are mixed with one gram of I - (3,3 dimethylcyclohexyl) - 4 - methyl - cis and trans - (2 and 3) - penten - 1 - one of Example XLIV until a substantially homogeneous composition is obtained. The perfumed soap composition manifests an excellent woody, piney aroma.

EXAMPLE LXII Preparation of a Detergent Composition A total of 100 g of a detergent powder (Lysine salt of n-dodecyl benzene sulfonic acid as more specifically described in U.S. Patent No. 3,948,818, issued on April 6, 1976) is mixed with 0.15 g of the I - (3,3 - dimethylcyclohexyl) - 4 methyl - cis and trans - (2 and 3) - penten - 1 - one of Example XLIV until a substantially homogeneous composition is obtained. This composition has an excellent woody, piney aroma.

EXAMPLE LXIII Synthesis of I (3,3-dimethylcyclohexyl)-cis and trans-(2 and 3)-buten-l-one Reaction:

A mixture of 616 grams of I - acetyl - 3,3 - dimethylcyclohexane (4 moles), 132 grams of acetaldehyde (3 moles), 105 grams boron oxide (1.5 moles) and 12 grams of boric acid (0.2 moles) is heated at 1500C in an autoclave for 3 hours. After cooling to room temperature the solution is filtered from inorganic salts, washed once with aqueous sodium carbonate and twice with saturated salt solution.

Distillation through a short column afforded 127.2 grams of 1 - acetyl - 3,3 dimethylcyclohexane and 127.2 grams of a mixture of 1 - (3,3 - dimethylcyclohexyl) - cis and trans - 2 - buten - 1 - one and I - (3,3 dimethylcyclohexyl) - 3 - buten - 1 - one.

A portion of the distillate rich in the desired product(s) was distilled through a l"x 12" Goodloe column giving the following fractions: Vapor Liquid Fraction Temperature Temperature Vacuum Weight Reflux No. ( C) ( C) mm Hg (g) Ratio 67-70 89-91 4.44.7 37.9 2:1 2 70 95 4.9 40.9 2:1 3 70 103 5.0 40.1 2:1 4 74 113 5.0 29.9 2:1 5 100 116 5.4 16.7 9:1 6 102 123 4.8 17.1 9:1 7 102 125 5.0 29.2 9:1 8 112 131 8.2 20.7 9:1 9 106 139 5.7 22.8 9:1 10 104 154 5.2 13.3 9:1 II 104 179 5.3 11.3 9:1 12 100 202 5.2 6.7 6:1 Bulked fractions 6-10 at 2 ppm, have a cedarwood aroma and a sweet, rootbeer-like, cedarwood flavor.

The mass spectral analysis is as follows: 180/69, 41, 39, .55, 165, 27.

The NMR spectrum (for fraction 9) is set forth in Fig. 25. The infrared spectrum (for fraction 9) is set forth in Figure 26.

The NMR analysis is as follows: 0.94 ppm (s) gem dimethyl protons 6 H 1.74-1.08(m) H2- 8H

0 1.90 (doublet with allylic coupling) CH3-C=C-C- 3 H 0 I II 2.74(m) HC-C- IH I 0 H 6.18 (broad doublet) -C-C=C- 1 H 0 I H 7.046.70 (m) -C-C=C- I H The IR analysis is as follows: 960 cm-1, 1290, 1360, 1380, 1440, 1625, 1670, 1690, 2860, 2940.

EXAMPLE LXIV Hydrogenation of 1 -(3,3-dimethylcyclohexyl)-cis and trans-(2 and 3)-buten-1-one Reaction:

Into a 250 cc Parr shaker is placed 107 grams (6 moles) of I - (3,3 dimethylcyclohexyl) - cis and trans - (2 and 3) - buten - 1 - one prepared according to Example LXIII 1 gram of 5% Palladium-on-carbon catalyst and 125 grams of isopropyl alcohol. The Parr shaker is sealed and heated to a temperature of 125"C at a pressure of 50--150 psig of hydrogen and maintained at that pressure range and temperature range for a period of 1.5 hours. At the end of the 1.5 hour period the reaction product is filtered, the solvent is removed in vacuo, and the residual oil is distilled on a 8 plate Vigreaux column. The distillation data follows: Vapor Liquid Fraction Temperature Temperature Vacuum Weight Reflux No. ( C) ( C) mm Hg (g) Ratio 86-89 100 4.6 9.0 11:1 2 90 102 4.7 12.0 11:1 3 90 102 4.6 8.8 11:1 4 90 102 4.7 11.5 11:1 5 90 105 4.6 14.0 11:1 6 90 110 4.6 13.5 11:1 7 90 113 4.6 8.4 11:1 8 90 141 4.6 11.1 11:1 9 90 205 4.6 4.4 11:1 From a perfumery standpoint fraction 7 at 100/, in food grade alcohol has a fruity, berry, herbaceous aroma with green, tobacco nuances.

The mass spectral analysis is as follows: 182/111, 69, 43, 41, 71, 55, 27.

The NMR analysis is as follows (fraction 8): 0.90 ppm (t) CH3-CH2- 3 H 0.91 ppm (s) dimethyl protons 6 H 1.95--1.16(m) -CH2- 10H

0 2.49 (t) -CH2-CH2-C- 2 H 0 2.69-2.31(m) HC-C- I H The IR analysis (fraction 8) is as follows: 1020 cm-1, 1120, 1175, 1290, 1360, 1375, 1400, 1455, 1705, 2860, 2930.

The NMR spectrum for this compound (fraction 8) is set forth in Fig. 27. The infrared spectrum for this compound (fraction 8) is set forth in Fig. 28.

EXAMPLE LXV A perfume composition is prepared by admixing the ingredients as in Example XV substituting I - (3,3 - dimethylcyclohexyl) - butan - 1- one produced according to Example LXIV for the product of Example XIV.

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 note with excellent fruity and herbacenous nuances. The base composition can also be used to scent soap or other toilet goods such as lotion, aerosol and sprays.

EXAMPLE LXVI Preparation of a Cosmetic-powder Composition A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcum powder with 0.25 g of 1 - (3,3 - dimethylcyclohexyl) - butan - I - one prepared according to Example LXIV. It has an excellent fruity, berry, herbaceous aroma with green and tobacco nuances.

EXAMPLE LXVII Perfumed Liquid Detergent Concentrated liquid detergents (lysine salt of n-dodecyl-benzene sulfonic acid as more specifically described in U.S. Patent No. 3,948,818 issued on April 6, 1976) with a herbaceous odor are prepared containing 0.10 /^, 0.150/, and 0.20% of I (3,3 - dimethylcyclohexyl) - butan - 1 - one prepared according to Example LXIV. They are prepared by adding and homogeneously mixing the appropriate quantity of 1 - (3,3 - dimethylcyclohexyl) - butan - 1 - one in the liquid detergent.

The detergents all possess a herbaceous fragrance with green and tobacco nuances, the intensity increasing with greater concentrations of I - (3,3 dimethylcyclohexyl) - butan - 1 - one.

EXAMPLE LXVIII Preparation of a Cologne and Handkerchief Perfume 1 - (3,3 - Dimethylcyclohexyl) - butan - I - one prepared according to the process of Example LXIV is incorporated in a cologne at a concentration of 2.5" in 85 /n aqueous ethanol; and into a handkerchief perfume at a concentration of 20,; (in 95 aqueous ethanol). A distinct and definite herbaceous fragrance is imparted to the cologne and to the handkerchief perfume.

EXAMPLE LXIX Preparation of a Cologne and Handkerchief Perfume The composition of Example LXV is incorporated in a cologne at a concentration of2.5% in 85% aqueous ethanol; and into a handkerchief perfume at a concentration of 20% (in 95 /n aqueous ethanol). The use of I - (3,3 dimethylcyclohexyl) - butan - I - one in the composition of Example III affords a distinct and definite strong amber aroma with herbaceous and tobacco notes to the handkerchief perfume and cologne.

EXAMPLE LXX Preparation of Soap Composition One hundred grams of soap chips are mixed with one gram of I - (3,3 dimethylcyclohexyl) - butan - I - one of Example LXIV until a substantially homogeneous composition is obtained. The perfumed soap composition manifests an excellent fruity, berry, tobacco aroma with green and tobacco nuances.

EXAMPLE LXXI Preparation of a Detergent Composition A total of 100 g of a detergent powder (Lysine salt of n-dodecyl benzene sulfonic acid as more specifically described in U.S. Patent No. 3,948,818 issued April 6, 1976) is mixed with 0.15 g of the 1 - (3,3 - dimethylcyclohexyl) - butan I - one of Example LXIV until a substantially homogeneous composition is obtained. This composition has an excellent fruity, berry, herbaceous aroma with green and tobacco nuances.

EXAMPLE LXXII Preparation of l-allyl-4-(4-methyl-3-pentenyl)-3-cyclohexene- I-carboxaldehyde and l-allyl-3-(4-methyl-3-pentenyl)-3-cyclohexene-1- carboxaldehyde Reaction:

Procedure: A slurry containing 289 grams of allyl chloride; 180 grams of granular sodium hydroxide; 400 ml of toluene; 25 grams of Aliquat 336; and 576 grams of a mixture of 4 - (4 - methyl - 3 - pentenyl) - 3 - cyclohexene - 1 - carboxaldehyde and 3 (4 - methyl - 3 - pentenyl) - 3 - cyclohexene - I - carboxaldehyde is heated at reflux for 7 hours. Water is added to the cooled reaction mass and the resulting organic phase is separated and washed twice with water. Distillation through a short column affords an oil which contained 381 grams (55 /n) of product (b.p. 140- 144", 1.5 mm). The product is purified by steam vacuum fractional distillation through a l"x12" Goodloe-packed column (b.p. 113120 , 1.5 mm at a steam rate of 1.6 ml liq. H2O/min.).

The NMR data for the mixture produced above is as follows: , ppm Interpretation 1.08 (3, s) methyl groups "a" 1.02 (3, s) 1.79 (2, d, J=Hz) methylene groups "b"

9.05(1,s) o -C-H The Infrared data for the mixture produced above is as follows:

1712 cm-' C=O / 1630 cm-' C=C 1630 cm C=C The Mass Spectral data is as follows: 41, 69, 93, 39, 91, 79 The NMR spectrum for the reaction product produced herein is set forth in Figure 29.

The Infrared spectrum is set forth in Figure 30.

EXAMPLE LXXIII A perfume composition is prepared by admixing the ingredients as in Example XV substituting a mixture of the I - (2 - propenyl) - (4 - methyl - 3 - pentenyl) A3 - cyclohexene - I - carboxaldehyde(s), produced according to Example LXXII for the product of Example XIV.

The foregoing blend is evaluated and found to have a high degree of richness and persistence in its novel natural fruity quality. This base composition can be admixed with aqueous ethanol, chilled and filtered to produce a finished cologne.

The cologne so prepared has a fruity aroma leaning towards a lavender-like note.

The base composition can also be used to scent soap or other toilet goods such as lotion, aerosol and sprays.

EXAMPLE LXXIV Preparation of a Cosmetic Powder Composition A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcum powder with 0.25 g of the 1 - (2 - propenyl) - (4 - methyl - 3 - pentenyl) - A3 cyclohexene - I - carboxaldehyde(s) produced according to Example LXXII. It has an excellent fruity, lavender-like note with citrus and balsam nuances.

EXAMPLE LXXV Perfumed Liquid Detergent Concentrated liquid detergents with fruity, lavender-like notes and citrus and balsam nuances (which detergents are produced from Lysine salt of n-dodecyl benzene sulfonic acid as more specifically described in U.S. Patent No. 3,948,818, issued on April 6, 1976) are prepared containing the 1 - (2 - propenyl) - (4 methyl - 3 - pentenyl) - A3 - cyclohexene - 1 - carboxaldehyde(s) prepared according to Example LXXII. They are prepared by adding and homogeneously mixing the appropriate quantity of the 1 - (2 - propenyl) - (4 - methyl - 3 pentenyl) - A3 - cyclohexene - I - carboxaldehyde(s) in the liquid detergent. The detergents all possess a fruity, lavender-like note with citrus and balsam nuances, the intensity increasing with greater concentrations of the I - (2 - propenyl) - (4 methyl - 3 - pentenyl) - A3 - cyclohexene - I - carboxaldehyde(s).

EXAMPLE LXXVI Preparation of a Cologne and Handkerchief Perfume The 1 - (2 - propenyl) - (4 - methyl - 3 - pentenyl) - A3 - cyciohexene - I carboxaldehyde(s), prepared according to the process of Example LXXII is incorporated in a cologne at a concentration of 2.5 in 85 aqueous ethanol; and into a handkerchief perfume at a concentration of 20% (in 95% aqueous ethanol). A distinct and definite fruity, lavender-like note with citrus and balsam nuances is imparted to the cologne and to the handkerchief perfume.

EXAMPLE LXXVII Preparation of a Cologne and Handkerchief Perfume The composition of Example LXXIII is incorporated in a cologne at a concentration of 2.5% in 85 /n aqueous ethanol; and into a handkerchief perfume at a concentration of 20% (in 85% aqueous ethanol). The use of the I - (2 propenyl) - (4 - methyl - 3 - pentenyl) - A3 - cyclohexene - I - carboxaldehyde(s) in the composition of Example LXXII I affords a distinct and definite fruity, lavender-like note with citrus and balsam nuances to the handkerchief perfume and cologne.

EXAMPLE LXXVII I Preparation of Soap Composition One hundred grams of soap chips are mixed with two grams of the composition of Example LXXIII until a substantially homogeneous composition is obtained.

The perfumed soap composition manifests an excellent fruity, lavender-like note with citrus and balsam nuances.

EXAMPLE LXXIX Preparation of a Detergent Composition A total of 100 grams of a detergent powder (Lysine salt of n-dodecyl benzene sulfonic acid as more specifically described in U.S. Patent No. 3,948,818, issued on April 6, 1976) is mixed with 0.70 grams of the composition of Example LXXIII until a substantially homogeneous composition is obtained. This composition has an excellent fruity, lavender-like note with citrus and balsam nuances.

EXAMPLE LXXX Basic Chocolate Flavor Formulation The following basic chocolate flavor formulation is produced: Parts by Ingredient Weight Dimethyl Sulfide 1.0 Isobutyl Acetate 1.0 Isoamyl Acetate 1.0 Phenylethyl Acetate 0.5 Diacetyl (10 /n in ethanol) 0.5 Furfural (50 /n in propylene) 0.5 Isoamyl Alcohol 1.0 Gamma-butyrolactone 5.0 Acetophenone 0.5 Benzaldehyde 1.0 Phenyl Acetic Acid 2.0 Maltol 3.0 Acetaldehyde 2.0 Isobutyraldehyde 8.0 Isovaleraldehyde 15.0 Phenylethyl Alcohol 8.0 Vanillin 15.0 Propylene Glycol 40.0 100.0 Total To the above chocolate formulation 15% by weight of the mixture of I - allyl 4 - (4 - methyl - 3 - pentenyl) - 3 - cyclohexene - 1 - carboxaldehyde and 1 allyi - 3 - (3 - methyl - 3 - pentenyl) - 3 - cyclohexene - I - carboxaldehyde produced according to Example LXXII is added. A portion of the formulation contains no such additive. The formulation with the I - allyl - (4 - methyl - 3 pentenyl) - 3 - cyclohexene - 1 - carboxaldehydes is compared to the formulation without the I - allyl - (4 - methyl - 3 - pentenyl) - 3 - cyclohexene - I - carboxaldehydes in water at the rate of 5 ppm and submitted for evaluation to a bench panel. The opinion of the panel is unanimous; that the flavor with the compound(s) 1 - allyl - (4 - methyl - 3 - pentenyl) - 3 - cyclohexene - I - carboxaldehyde(s), at the level of 15%, has the characteristics cocoa butter-like aroma and taste characteristics.

When the compound(s) I - allyl - (4 - methyl - 3 - pentenyl) - 3 cyclohexene - 1 - carboxaldehyde is added at the rate of 5% to the same basic chocolate formulation, fuller, more cocoa powder-like notes in aroma and taste are created as compared to the same formulation without the compound(s) 1 - allyl (4 - methyl - 3 - pentenyl) - 3 - cyclohexene - 1 - carboxaldehyde at the level of 5 ppm in water.

In conclusion, the compound(s) 1 - allyl - (4 - methyl - 3 - pentenyl) - 3 cyclohexene - 1 - carboxaldehyde(s) surprisingly, unexpectedly and advantageously improves cocoa and chocolate notes as well as cocoa butter characteristics in chocolate.

EXAMPLE LXXXI A. Powder Flavor Composition 20 Grams of the flavor composition of Example LXXX is emulsified in a solution containing 300 gm gum acacia and 700 gm water. The emulsion is spraydried with a Bowen Lab Model Drier utilizing 260 c.f.m. of air with an inlet temperature of 500OF., an outlet temperature of 200OF., and a wheel speed of 50,000 r.p.m.

B. Sustained Release Flavor The process of Example XXIIIB is repeated using the liquid chocolate flavor composition of Example LXXX instead of the flavor composit

EXAMPLE LXXXIII 100 Parts by weight of chicle are mixed with 4 parts by weight of the flavor prepared in accordance with Example LXXXI. 300 Parts of sucrose and 100 parts of cornr syrup are added. Mixing is effected in a ribbon blender with racketed side walls of the type manufactured by the Baker Perkins & Co.

The resultant chewing gum blend is then manufactured into strips I inch in width and 0.1 inches in thickness. The strips are cut into lengths of 3 inches each.

On chewing, the chewing gum has a pleasant long lasting chocolate flavor.

EXAMPLE LXXXIV Chewing Gum 100 Parts by weight of chicle are mixed with 18 parts by weight of the flavor prepared in accordance with Example LXXXlI. 300 Parts of sucrose and 100 parts of corn syrup are then added. Mixing is effected in a ribbon blender with racketed side walls of the type manufactured by the Baker Perkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inch in width and 0.1 inches in thickness. The strips are cut into lengths of 3 inches each.

On chewing, the chewing gum has a pleasant long lasting chocolate flavor.

EXAMPLE LXXXV Toothpaste Formulation The groups of ingredients as in Example XXVII are prepared substituting the flavor material of Example LXXXI for that of Example XXIII in Group D.

The procedure of Example XXVII is followed to prepare a toothpaste and the resulting toothpaste when used in a normal toothbrushing procedure yields a pleasant chocolate flavor, of constant strong intensity throughout said procedure (1--1.5 minutes).

EXAMPLE LXXXVI Chewable Vitamin Tablets The flavor material produced according to the process of Example LXXXII is added to a Chewable Vitamin Tablet Formulation at a rate of 10 gm/Kg which Chewable Vitamin Table Formulation is prepared as in Example XXVIII by utilising the product of Example LXXXII for that of Example XXIV.

Chewing of the resultant tablets yields a pleasant, long lasting, consistently strong chocolate flavor for a period of 12 minutes.

EXAMPLE LXXXVII Tobacco Formulation A tobacco mixture is produced as in Example XXXIV. Cigarettes are prepared from this tobacco and the flavor formulation as described in Example XXX IV is prepared.

The above-stated tobacco flavor formulation is applied at the rate of 1.0 /O to all of the cigarettes produced using the above tobacco formulation. Half of the cigarettes are then treated with 500 or 1,000 ppm of the mixture produced according to Example I of 1 - allyl - 3 and 4 - (4 - methyl - 3 - pentenyl) - A3 cyclohexene - 1 - carboxaldehyde(s). The control cigarettes not containing the mixture of I - allyl - 3 or 4 - (4 - methyl - 3 - pentenyl) - A3 - cyclohexene - 1 carboxaldehyde(s) produced according to the process of Example I and the experimental cigarettes which contain the mixture of I - allyl - 3 or 4 - (4 methyl - 3 - pentenyl) - A3 - cyclohexene - 1 - carboxaldehyde(s) produced according to the process of Example LXXII are evaluated by paired comparison and the results are as follows: The experimental cigarettes are found to have more smoke body and a fuller smoke body sensation in the mouth on smoking. The tobacco-like notes are enhanced and the flavor of the tobacco on smoking is more aromatic with cocoa liquer-like, sweet-rich and creamy oily notes.

The tobacco of the experimental cigarettes, prior to smoking, has cocoa liquer-like, sweet-rich and creamy oily notes. All cigarettes are evaluated for smoke flavor with a 20 mm cellulose acetate filter.

EXAMPLE LXXVIII A slurry containing 289 grams of ally chloride; 252 grams of flaked potassium hydroxide; 400 ml of toluene; 40 grams of 18-crown-6 having the structure:

and 576 grams of myrac aldehyde is heated at reflux for three hours. The reaction mass is treated as in Example LXXII to afford 287 grams of product, a mixture of compounds having the structures:

EXAMPLE LXXXIX A slurry containing 289 grams of ally chloride; 180 grams of granular sodium hydroxide; 400 ml of toluene; 40 grams of triethylamine; and 576 grams of a mixture of myrac aldehyde is heated at reflux for 8 hours. The reaction mass is treated as in Example LXXII to afford 240 grams of product, a mixture of compounds having the structures:

WHAT WE CLAIM IS:- 1. A compound having the generic structure:

wherein the moiety C=F3 represents a cycloalkyl group or a cycloalkenyl group having six carbon atoms which may be substituted or unsubstituted and either (i) R21is hydrogen and R22 represents a methyl group substituted by one or two of the structures -CH2-R24; -CH2-CH=CH3; -CH2-C(CH3)=CH2 (wherein R24 is saturated ethyl containing 2 or more carbon atoms or alkenyl) or (ii) R22 represents methyl or hydrogen and R2, represents allyl (-CH2-CH--CH2) or methallyl (-CH2-C(CH3)=CH2).

2. The use in perfumery, food flavorings or tobacco flavorings of one or more of the compounds according to Claim 1.

3. A compound according to Claim 1, which has the structure

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (44)

1. **WARNING** start of CLMS field may overlap end of DESC **.

   and 576 grams of myrac aldehyde is heated at reflux for three hours. The reaction mass is treated as in Example LXXII to afford 287 grams of product, a mixture of compounds having the structures:

   EXAMPLE LXXXIX A slurry containing 289 grams of ally chloride; 180 grams of granular sodium hydroxide; 400 ml of toluene; 40 grams of triethylamine; and 576 grams of a mixture of myrac aldehyde is heated at reflux for 8 hours. The reaction mass is treated as in Example LXXII to afford 240 grams of product, a mixture of compounds having the structures:

   WHAT WE CLAIM IS:- 1. A compound having the generic structure:

   wherein the moiety C=F3 represents a cycloalkyl group or a cycloalkenyl group having six carbon atoms which may be substituted or unsubstituted and either (i) R21is hydrogen and R22 represents a methyl group substituted by one or two of the structures -CH2-R24; -CH2-CH=CH3; -CH2-C(CH3)=CH2 (wherein R24 is saturated ethyl containing 2 or more carbon atoms or alkenyl) or (ii) R22 represents methyl or hydrogen and R2, represents allyl (-CH2-CH--CH2) or methallyl (-CH2-C(CH3)=CH2).
2. 2. The use in perfumery, food flavorings or tobacco flavorings of one or more of the compounds according to Claim 1.
3. 3. A compound according to Claim 1, which has the structure

   wherein R, or one or both of R2 and/or R3 is allyl or methallyl, and the other of R, and K2 and/or K3 is hydrogen, and further characterized in the step of intimately admixing an allylic halide or a methallylic halide with I - acetyl - 3,3 dimethylcyclohexane.
4. 4. A compound according to Claim I which is a derivative of I - acetyl - 3,3 dimethylcyclohexane having the structure:

   wherein R is hydrogen or methyl.
5. 5. A compound according to Claim I, which is the compound I - acetyl - 3,3 dimethyl - (2 - propenyl)cyclohexane having the structure:
6. 6. A compound or a mixture of compounds according to Claim I, wherein the compounds are either I - (2 - propenyl) - 3 - (4 - methyl - 3 - pentenyl) - A3 cyclohexene - I - carboxaldehyde or I - (2 - propenyl) - 4 - (4 - methyl - 3 pentenyl) - A3 - cyclohexene - I - carboxaldehyde defined by the structure:

   wherein the carboxaldehyde and 2 - propenyl moieties are both bonded either at the alpha-carbon atom or the beta-carbon atom of the cyclohexenyl moiety.
7. 7. A process for producing a compound in accordance with Claim 5, which comprises the step of intimately admixing an allylic halide with I - acetyl - 3,3 dimethylcyclohexane in the presence of a phase transfer agent and an alkali metal hydroxide.
8. 8. A process for preparing a compound in accordance with Claim 4, which comprises the step of intimately admixing an aldehyde having the structure:

   with I - acetyl - 3,3 - dimethylcyclohexane in the presence of a material selected from (i) a mixture of boron oxide and boric acid; or (ii) an inorganic base.
9. 9. A process for producing a compound in accordance with Claim 6, which comprises the step of intimately admixing an allylic halide with myrac aldehyde in the presence of a phase transfer agent and an alkali metal hydroxide.
10. 10. A perfume composition comprising the compound of Claim 5 and at least one adjuvant selected from natural perfume oils, sythetic perfume oils, alcohols, aldehydes, ketones, nitriles, esters and lactones.
11. II. A perfumed article comprising the compound of Claim 5 and a detergent, soap, cosmetic preparation or powder.
12. 12. A cologne composition comprising ethanol, water and the compound of Claim 5.
13. 13. A flavoring composition comprising the compound of claim 5 and a flavor adjuvant.
14. 14. A composition according to Claim 13, wherein the flavoring adjuvant is selected from p-hydroxy-benzyl acetone, maltol, benzyl acetate, methyl cinnamate, geraniol, ethyl methyl phenyl glycidate, vanillin, methyl anthranilate, alpha-ionone, gamma undecalactone, ethyl pelargonate, isoamyl acetate, acetaldehyde, dimethyl sulfide, isobutyl acetate, acetic acid, ethyl butyrate, diacetyl, anethole, cis - 3 hexenol - 1, naphthyl ethyl ether, ethyl acetate, isoamyl butyrate, 2 - methyl - 2 pentenoic acid, 2(4 - hydroxy - 4 - methylphenyl) norbornadiene, 4 - allyl 1,2,6 - trimethoxy benzene, cassia oil, eugenol, caryophyllene, guiacol, cinnamaldehyde, 5 - methyl furfural, cuminaldehyde, cinnamyl formate, methyl cinnamate, furfural, 2,3 - dimethyl pyrazine, 2 - ethyl - 3 - methyl pyrazine, 3 phenyl - 4 - pentenal, 2 - phenyl - 2 - hexenal, 2 - phenyl - 2 - pentenal, 3 phenyl - 4 - pentenal diethyl acetal, 1 - crotonyl - 2,2,6 - trimethylcyclohex - 1 ene, 1 - crotonyl - 2,2,6 - trimethylcyclohexa - 1,5 - diene, 2,2,6 - trimethyl cyclohex - 1 - ene carboxaldehyde and 4 - propenyl - 1,2,6 - trimethoxv benzene.
15. 15. A process for augmenting or enhancing the fruit flavor of a foodstuff, which process comprises the step of adding to a foodstuff from 0.5 ppm up to about 100 ppm of the compound of Claim 5.
16. 16. A flavor composition according to Claim 14, wherein the quantity of the compound I - acetyl - 3,3 - dimethyl - (2 - propenyl)cyclohexane is from 0.1 /O up to 15 /O by weight based on the total weight of the flavoring composition.
17. 17. A compound according to Claim 4 having the structure:
18. 18. A process for augmenting or enhancing the organoleptic properties of a consumable material selected from perfume compositions, perfumed articles, food flavoring compositions, foodstuffs, chewing gums, chewing gum flavoring compositions, medicinal products, medicinal product flavoring compositions, toothpastes and toothpaste flavoring compositions, which comprises adding thereto a small but effective amount of a composition comprising a compound in accordance with Claim 4.
19. 19. A process according to Claim 18, wherein the consumable material is a perfume composition.
20. 20. A process according to Claim 18 wherein the consumable material is a foodstuff.
21. 21. A flavor modifying composition comprising a compound in accordance with Claim 4 and as a flavor adjuvant a compound selected from p-hydroxybenzyl acetone, maltol, benzyl acetate, methyl cinnamate, geraniol, ethyl methyl phenyl glycidate, vanillin, methyl anthranilate, alpha-ionone, gamma undecalactone, ethyl pelargonate, isoamyl acetate, acetaldehyde, dimethyl sulfide, isobutyl acetate, acetic acid, ethyl butyrate, diacetyl, anethole, cis - 3 - hexenol - 1, naphthyl ethyl ether, ethyl acetate, isoamyl butyrate, 2-methyl - 2 - pentenoic acid, 2 - (4 hydroxy - 4 - methylpentyl) - norbornadiene, 4 - allyl - 1,2,6 trimethoxybenzene, cassia oil, eugenol, caryophyllene, guiacol, cinnamaldehyde, 5 - methylfurfural, cuminaldehyde, cinnamyl formate, methyl cinnamate, furfural, 2,3 - dimethylpyrazine, 2 - ethyl - 3 - methylpyrazine, 3 - phenyl - 4 - pentenal 2 - phenyl - 2 - hexenal, 2 - phenyl - 2 - pentenal, 3 - phenyl - 4 - pentenal diethyl acetal, 1 - crotonyl - 2,2,6 - trimethylcyclohex - I - ene, I - crotonyl 2,2,6 - trimethylcyclohexa - 1,5 - diene, 2,2,6 - trimethyl - cyclohex - I - ene carboxaldehyde and 4 - propenyl - 1,2,6 - trimethoxybenzene.
22. 22. A fragrance modifying composition comprising a compound in accordance with Claim 4 and one or more auxiliary perfume ingredients compatible with said compound.
23. 23. A perfumed article comprising one or more compounds in accordance with Claim 4 and a detergent, soap, cosmetic preparation or powder.
24. 24. A cologne composition comprising ethanol, water and one or more compounds in accordance with Claim 4.
25. 25. 1 - Butanoyl - 3,3 - dimethylcyclohexane in accordance with Claim I, represented by the structure:
26. 26. A process for augmenting or enhancing the organoleptic properties of a consumable material selected from perfume compositions, colognes and perfumed articles which comprises adding thereto a small but effective amount of a composition comprising the compound of Claim 25.
27. 27. A process according to Claim 26, wherein the consumable material is a perfume conposition.
28. 28. A fragrance modifying composition comprising the compound of Claim 25 and one or more auxiliary perfume ingredients compatible with said compound.
29. 29. A perfumed article comprising the compound of Claim 25 and a detergent, soap, cosmetic preparation or powder.
30. 30. A cologne composition comprising ethanol, water and the compound of Claim 25.
31. 31. A perfume composition comprising a compound in accordance with Claim 6 and at least one adjuvant selected from natural perfume oils, synthetic perfume oils, alcohols, aldehydes, ketones, nitriles, esters and lactones.
32. 32. A perfumed article comprising a compound in accordance with Claim 6 and a detergent, soap, cosmetic preparation or powder.
33. 33. A cologne composition comprising ethanol, water and a compound in accordance with Claim 6.
34. 34. A flavoring composition comprising a compound in accordance with Claim 6 and a flavor adjuvant.
35. 35. A composition according to Claim 34, wherein the flavoring adjuvant is selected from p-hydroxy - benzyl acetone, maltol, benzyl acetate, methyl cinnamate, geraniol, ethyl methyl phenyl glycidate, vanillin, methyl anthranilate, alpha-ionone, gamma undecalactone, ethyl pelargonate, isoamyl acetate, acetaldehyde, dimethyl sulfide, isobutyl acetate, acetic acid, ethyl butyrate, diacetyl, anethole, cis - 3 - hexenol - 1, napthyl ethyl ether, ethyl acetate, isoamyl butyrate, 2 - methyl - 2 - pentenoic acid, 2(4 - hydroxy - 4 methylphenyl)norbornadiene, 4 - allyl - 1,2,6 - trimethoxy benzene, cassia oil, eugenol, caryophyllene, guiacol, cinnamaldehyde, 5 - methyl furfural, cuminaldehyde, cinnamyl formate, methyl cinnamate, furfural, 2,3 - dimethyl pyrazine, 2 - ethyl - 3 - methyl pyrazine, 3 - phenyl - 4 - pentenal, 2 - phenyl 2 - hexenal, 2 - phenyl - 2 - pentenal, 3 - phenyl - 4 - pentenal diethyl acetal, 1 - crotonyl - 2,2,6 - - trimethylcyclohex - 1 - ene, 1 - crotonyl - 2,2,6 trimethylcyclohexa - 1,5 - diene, 2,2,6 - trimethyl - cyclohex - 1 - ene carboxaldehyde and 4 - propenyl - 1,2,6 - trimethoxy benzene.
36. 36. A process for augmenting or enhancing the fruit flavor of a foodstuff comprising the step of adding to a foodstuff from 0.5 ppm up to 100 ppm of a compound in accordance with Claim 6.
37. 37. A composition according to Claim 34, wherein the quantity of the compounds 1 - (2 - propenyl) - 3 - (4 - methyl - 3 - pentenyl) - A3 - cyclohexene I - carboxaldehyde and I - (2 - propeny1) - 4 - (4 - methyl - 3 - pentenyl) - A3 cyclohexene - I - carboxaldehyde is from 0.1 /n to 15 /" by weight based on the total weight of the flavoring composition.
38. 38. A compound according to Claim 1, having the structure:
39. 39. A compound according to Claim I having the structure:
40. 40. A compound in accordance with Claim 1 and substantially as hereinbefore described in any one of foregoing Examples XIV, XXIX, XXX, XXXI, XXXII, XXXIII, XXXIX, XLI, XLII, XLVI, LXXII, LXXXVIII or LXXXIX.
41. 41. A process of organoleptically using a compound in accordance with Claim 1, substantially as hereinbefore described in any one of foregoing Examples XV, XVI, XVII, XVIII XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII, XXXIV, XXXV, XXXVI, XXXVII, XXXVIII, LXXIII, LXXIV, LXXV, LXXVI, LXXVII, LXXVIII, LXXIX, LXXX, LXXXI, LXXXII, LXXXIII, LXXXIV, LXXXV, LXXXVI or LXXXVII.
42. 42. A process in accordance with Claim 7 and substantially as hereinbefore described in foregoing Example XIV.
43. 43. A compound in accordance with Claim 3, substantially as hereinbefore described in any one of foregoing Examples XIV, XXIX, XXXIX, XL or XLII.
44. 44. A process in accordance with Claim 9, substantially as herein described with reference to any one of Examples LXXII, LXXXVIII or LXXXIX.