NL8304147A - PROCESS FOR PREPARING CYCLOHEXAN DERIVATIVES AND FOR AROMATIZING FOODSTUFFS USING THESE CYCLOHEXAN DERIVATIVES. - Google Patents

Description

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Process for preparing cyclohexane derivatives and for flavoring foodstuffs using these cyclohexane derivatives.

The invention relates to a process for preparing at least one of the substances: (a) a mixture of 1- (3,3-dimethylcyclohexyl) -4-methyl-cis-2-penten-1-one, 1- ( 3,3-dimethylcyclohexyl) -4-5 methyl-trans-2-penten-1-one and 1- (3,3-dimethylcyclohexyl) -4-methyl-3-penten-1-one, (b) a mixture of 1- (3,3-dimethylcyclohexyl) - cis-2-pentene-1-one, 1- (3,3-dimethylcyclohexyl) -trans-2-pentene-10 1-one and 1- (3,3-dimethylcyclohexyl) -3-penten-1-one, (c) a mixture of 1-butenoyl-3,3-dimethyl-cyclohexanes of the formula 1, which mixture consists of compounds of the formulas 2, 3 and 4, wherein one of the dots - 15 peeling lines a single and the other dotted line representing a carbon-carbon double bond, (d) 1-butanoyl-3,3-dimethylcyclohexane of the formula 5, 20 (e) a compound of the formula 6, (f) the compound 1 -acetyl-3,3-dimethyl- (2-propenyl) -cyclohexane of the formula 7 (g) compounds of the formula 8, wherein methallyl, R 2 represents hydrogen and R 2 represents r represents hydrogen, or R 1 represents hydrogen and R 2 and represents methyllyl 8304147 - - ^ * - 2 -% * (h) a mixture of the compounds 3 1- (2-propenyl) -3- (4-methyl-3- pentenyl) -Δ-cyclohexene-1-3 carboxaldehyde and 1- (2-propenyl) -4- (4-methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehyde of the formula 9, in which the 5-carboxaldehyde residue is bonded to either the α-carbon or the β-carbon atom of the cyclohexenyl radical, whereby a suitably substituted halide or aldehyde is reacted with a suitable carbonyl compound in the presence of a reaction catalyst, base or boron compound, characterized in that one in 3 -place dimethyl-substituted cyclohexyl group or an acyclic hydrocarbon group to react with an aldehyde or allyl chloride or bromide or a methallyl chloride or bromide in the presence of a tertiary amine, toluene, t-butanol or a crown ether, as well as in the presence of base or a mixture of boron oxide and boric acid and that me n optionally hydrogenate the resulting compound or mixture.

The compounds of formula 13 can enhance or enhance orange flavors by providing them with. 20 pineapple-allyl-caproate, mother resin, woody, fatty, sweet, fruity, citrus, green flavor with rosy, ionone, oriental, woody, sweet, fruity citrus flavor properties in connection with food, chewing gum and medicinal products.

The compounds of the general formula 13 are also capable of modifying or enhancing the aroma properties of perfumed articles and perfumed compositions by providing them or by enhancing sweet, earthy, animal, green, spicy, melon and fruity aromas with pineapple, "ambery", mother resinous, ginger and citrus nuances and tobacco / animal notes, fulfilling a need in the perfume industry.

The compounds of the general formula 13, 35 in which one of the groups or one or both groups and / or 8304147 <r - 3 - represent methallyl or allyl and the other represents group or hydrogen, are obtained by acetyl-3, Reacting 3-dimethyl-cyclohexane with a methallyl or allyl halide in the presence of a 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, t-butanol or a crown ether (or various mixtures thereof) (hereinafter referred to as "reaction promoter") according to the general reaction scheme J, wherein R represents allyl 10 or methallyl and X represents chlorine or bromine. The nature of the reaction product depends primarily on the particular reaction promoter used, as far as the isomer ratios of the reaction products are concerned. Thus, when using crown ethers of the general formula 15, wherein 15 represents Z, a lower alkylene of 1-4 carbon atoms, for example methylene or ethylene, N is equal to 3-8 P and Q is the same or different and a lower alkylene with 1-4 carbon atoms or orthophenylene, for example compounds of the formula 16 (dibenzo-18-crown 6) as reaction promoters, the reaction product mainly from products whose methallyl or allyl substituent is in the "1-" position of the ring, therefore according to scheme K, wherein R 1 is methyl or hydrogen and M represents an alkali metal.

However, if a phase transfer agent is used as the reaction promoter, various by-products are formed, and the reaction scheme L is obtained, wherein methyl represents hydrogen or X equals chlorine or bromine.

When a tertiary amine is used as the reaction promoter 30, or when toluene or t-butanol is used as the reaction promoter, the reaction proceeds according to the scheme M, wherein R 1 represents methyl or hydrogen and X is chlorine or bromine. Examples of tertiary amines which can be used in the invention are trimethylamines, triethylamine, dimethylaminoethyl dimethylamine.

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The process of this aspect of the invention is carried out in an inexpensive solvent, which (a) is inert to the reaction system and (b) can also serve as a reaction promoter.

These solvents include toluene, benzene, o-xylene, m-xylene, p-xylene, ethylbenzene, n-hexane, cyclohexane, methylene chloride-o-dichlorobenzene, t-butanol and crown ethers, for example dibenzo-18-crown-6.

The process of this aspect of the invention is carried out at a temperature from about 10 to about 150 ° C, with a temperature range of from 50 to 120 ° C being preferred. The reaction time is inversely proportional to the reaction temperature, with lower reaction temperatures giving rise to longer reaction times and therefore the reaction time can vary from about 30 minutes to about 10 hours.

In any of the reactions of this aspect of the invention, regardless of which reaction promoter is used, the molar ratio of 1-acetyl-3,3-dimethyl-20-cyclohexane to allyl halide or methallyl halide reagent is in the range of 0, 5: 1.5 to about 1.5: 0.5, with a ratio of about 1: 1 to about 1: 1.2 being preferred.

The molar ratio of base: allyl halide or base: methallyl halide reagent in the reaction mass may range from about 0.75: 1 to about 1.5: 1, with a ratio of base: methallyl halide or base: allyl halide of about 1: 1 to about 1.2: 1 is preferred.

The reaction of the invention is preferably carried out at atmospheric pressure, since it is most effective. However, lower or higher pressures can be used without adversely affecting the final yield of desired reaction product.

The base used in the reaction, 8304147-5, is critical, and sodium hydroxide, potassium hydroxide and potassium t-butoxide are preferred.

According to a fourth aspect of the invention, novel solid and liquid foods, chewing gum, medicinal products and toothpaste compositions and aroma compositions containing sweet, fruity, raspberry, woody, lime, pain-like, ionic, blueberry and blossom flavor and sweet , raspberry, lime, sweet fruity, red currant, painful, blossom, ionic and nut flesh flavor-10 properties and new perfume compositions, waters of fragrance and perfumed products with fruity, woody, painful aromas with "armoise" and floral notes and weak chocolate undertones are provided using one or more 1-acetyl-3,3-dimethylcyclohexane derivatives of formula 17, wherein one of the dotted lines represents a single carbon-carbon bond or a double carbon-carbon bond and the other dotted line is a single carbon-carbon bond , while R is hydrogen or methyl, in food, chewing gum, tooth pastes and flavorings for '20 medical products.

The above-mentioned 1-acetyl-3,3-dimethyl-cyclohexane derivatives can preferably be obtained by a process whereby 1-acetyl-3,3-dimethylcyclohexane is reacted with an aldehyde of the formula 18, whereby a compound is obtained with the formula 17, wherein one of the dotted lines represents a double carbon-carbon bond and the other dotted line is a single carbon-carbon bond. This takes place in the presence of an inorganic base or a mixture of boron oxide (B2O3) and boric acid and by using the product obtained on account of its organoleptic properties or by further reducing the product obtained with hydrogen, whereby a compound is obtained with the formula 20, wherein R represents hydrogen or methyl.

The first reaction with the aldehyde of the 8304147 i - δ - formula 18 is carried out at a temperature of about 20 to about 160 ° C, using a catalyst consisting of an inorganic base, such as an alkali metal hydroxide, for example potassium hydroxide, sodium hydroxide or lithium-5 hydroxide or an alkali earth metal hydroxide, for example barium hydroxide or lithium hydroxide, or at a temperature in the range of about 100 to 200 ° C using a catalyst consisting of a mixture of boric acid (HBO4) and boron oxide. The reaction time is inversely proportional to the reaction temperature. For example, when using a mixture of boric acid and boron oxide, the reaction time varies between 2 and 10 hours, and at higher temperatures, the reaction time varies between 1 and 8 hours.

When using an inorganic base, the 15 molar ratio of inorganic base: 1-acetyl-3,3-dimethylcyclohexane can range from 0.1: 1 to 2: 1, with a 1: 1 molar ratio being preferred. When using a mixture of boric acid and boron oxide, the molar ratio of boron oxide: 1-acetyl-3,3-dimethyl-cyclohexane ranges from 0.5: 1 to 1.5: 1, with a 1: 1 molar ratio being preferred. The concentration of boric acid in the reaction mass can vary from 1 to 80 g per mole of aldehyde of the formula 18.

In all cases, the molar ratio of aldehyde of the formula 18 (1-acetyl-3,3-dimethylcyclohexane) can range from 1: 1 to about 3: 1, with a molar ratio of 2: 1 being preferred.

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

The reduction reaction to prepare the genus of formula 20 is preferably carried out in the presence of inert solvents, such as isopropanol, at 2 hydrogenation pressures between 3.5 and 10.5 kg per cm of overpressure, at temperatures between 25 and 150 ° C and using hydrogenation catalyst such as 5% palladium on carbon, rhodium, 1 '35 platinum and Raney nickel. The reaction time varies inversely with 8304147 t & - 7 - the temperature and the reaction pressure. For example, lower pressures and temperatures lead to longer reaction times. The reaction time can therefore vary from 1 hour to 5 hours.

The preceding reaction sequence is explained by scheme N.

Examples of organoleptic properties of materials obtained by the aforementioned method are summarized in Table A.

10 TABLE A

Structure name Organoleptic properties _ Aroma_ Fragrance_

Mixture of 1- (3.3- formula 21 sweet, woody, fruity, 15 dimethylcyclohexyl) - raspberry, lime, woody, 4-methyl-cis-2-pentene-pain-aroma-pain-aroma 1-one, 1- (3.3 -dimethyl character with cyclohexyl) -4-methyl-sweet, raspberry "armoise" trans-2-penten-1-one and lime aroma blossom- 20 and 1- (3,3-dimethyl character with nuances and cyclohexyl) -4 -mehyl- 1.0 ppm a light 3-pentene-1-one chocolate, undertone 25

Mixture of 1- (3.3- formula 22 sweet, raspberry, sweet, dimethylcyclohexyl) - fruity, pine, cis-2-pentene-l-one, like, blossom woody l- (3,3-dimethylionone-like ( pain) with 30 cyclohexyl) -trans-2 flavor with sweet, pineapple pentene-l-one and fruity, galbanum, 1- (3,3-dimethyl raspberry, red hexalone cyclohexyl) -3 berries, pine nuts pentene -l-on like blossom 35 and ionic aroma properties 40 3.3-dimethyl-l-formula 23 sweet, painful, weak under- (4-methylvaleryl) - fruity, blueberry, tone, sweet, cyclohexane woody aroma - woody character slightly choco-sweet, pain, drawer, 45 fruity, nut flesh properties 8304147

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A fifth aspect of the invention involves the preparation of new perfume composition, waters of fragrance and perfumed products with fruity, berry and spicy aromas with green and tobacco nuances, using 1-butanoyl-5-3,3-dimethylcyclohexane of the formula 24.

The 1-butanoyl-3,3-dimethylcyclohexane, which can be used in the manner indicated above, is preferably prepared by a process of reacting 1-acetyl-3,3-dimethylcyclohexane with acetaldehyde in the presence of an inorganic base or a mixture of boron oxide (B203) and boric acid to give a compound of the formula 25 (mixture of cis and trans isomers) and a compound of the formula 39, after which the product obtained is reduced with hydrogen to obtain a compound 15 with the formula 24.

The first reaction with acetaldehyde is carried out at a temperature of about 20 to 100 ° C using a catalyst consisting of an inorganic base, such as an alkali metal hydroxide, for example, potassium hydroxide, sodium hydroxide or lithium hydroxide, or an alkaline earth metal hydroxide, such as barium hydroxide or lithium hydroxide, or at a temperature between about 100 and 200 ° C, using a catalyst consisting of a mixture of boric acid (HB03) and boron oxide.

The reaction time is inversely proportional to the reaction temperature. When using a mixture of boric acid and boron oxide, the reaction time therefore varies between 2 and 10 hours and when using a higher temperature, the reaction time varies between 1 and 8 hours.

When using an inorganic base, the inorganic base: 1-acetyl-3,3-dimethylcyclohexane molar ratio may range from 0.1: 1 to 2: 1, with a 1: 1 molar ratio being preferred. When using the mixture of boric acid and boron oxide, the molar ratio of boron oxide: 1-acetyl-3,3-dimethylcyclohexane ranges from 0.5: 1 to 8304147 - 9 - 1.5: 1, with a 1: 1 molar ratio being preferred.

The concentration of boric acid in the reaction mass can vary from 1 - 80 g per mole of acetaldehyde.

In all cases, the acetal-5-aldehyde: 1-acetyl-3,3-dimethylcyclohexane molar ratio may range from 1: 1 to about 3: 1, with a molar ratio of 2: 1 being preferred.

The reactions can take place in the presence or absence of an inert solvent. When using boric acid or boron oxide, the reaction is preferably conducted without a solvent. When an inorganic base is used as a catalyst, the reaction preferably takes place with a solvent, such as methanol, ethanol or isopropanol.

The reduction reaction to prepare a compound of formula 24 is preferably carried out in the presence of inert solvents, such as isopropanol; at 2 hydrogenation pressures between 3.5 and 1.0 kg per cm of overpressure; at temperatures between 25 and 150 ° C and with hydrogenation catalysts such as 5% palladium on carbon, rhodium, platinum and Raney nickel. The reaction time is inversely proportional to the temperature and the reaction pressure. For example, longer reaction times are required at lower temperatures and pressures. The reaction time can vary from 1 hour to 5 hours.

The aforementioned reaction is illustrated by reaction scheme 0, wherein one of the dotted lines represents a double carbon-carbon bond and the other dotted line is a single carbon-carbon bond.

A sixth aspect of the invention relates to the use of the compounds 1- (2-propenyl) -3- (4-methyl-3-pentenyl) -Δ- cyclohexene-1-carboxaldehydes and 1- (2-propenyl) - 3 4- (4-methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehydes of the general formula 38, wherein the carboxaldehyde moiety is bonded to either the α-carbon or the β-carbon atom of the cyclohexenyl moiety of their 35 organoleptic properties, this part also concerns the 8304147 - 10 -

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preparation of these compounds.

The compounds of formulas 26 and 27, as well as mixtures obtained by the structure 38, are all capable of enhancing or enhancing cocoa buttery flavors, apricot flavors, peach flavors, milk product flavors and coconut flavors by providing sweet, fatty cocoa buttery flavors thereto. green / grassy, milk-like, diacety-like, apricot-like, and carrot-like aroma properties with fat-like, cocoa-buttery, green / grassy, milk-like, diacety-like, peach, and coconut flavor properties.

The compounds 1- (2-propenyl) -3- (4-methyl-3-3-pentenyl) -Δ-cyclohexene-1-carboxaldehyde and 1- (2-propenyl) -3 4- (4-methyl-3-pentenyl) ) -Δ-cyclohexene-1-carboxaldehyde can also modify or enhance the fragrance properties of perfume compositions and perfumed products by providing sweet, fruity, lavender notes with citrus, blossom or balm nuances, thus satisfying a perfume industry need. .

.20 In tobacco and tobacco aroma compositions, the compounds provide 1- (2-propenyl) -3- (4-methyl-3-pentenyl) - 3 Δ-cyclohexene-1-carboxaldehyde and 1- (2-propenyl) - 4- (4-methyl-3 3-pentenyl) -Δ-cyclohexene-l-carboxaldehyde cocoa, liqueur-like, sweet-rich and creamy oily notes.

The compounds 1- (2-propenyl) -3- (4-methyl-3 3-pentenyl) -Δ-cyclohexene-1-carboxaldehyde and 1- (2-propenyl) - 4- (4-methyl-3-pentenyl C-cyclohexene-1-carboxaldehyde is obtained by reacting myracaldehyde of the formula 14 with an allyl halide in the presence of an inert solvent, an alkali metal hydroxide and a phase transfer agent. The reaction is carried out in a two-phase system.

An aspect of the invention is therefore illustrated by the reaction scheme P, wherein the carboxaldehyde moiety is bonded to the α-carbon or β-carbon atom, while X represents chlorine or bromine and m is an alkali metal.

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An aspect of the invention includes the above-mentioned process, wherein the reagent for the process and the base are applied in two immiscible phase, an organic phase and either (1) an aqueous base phase or (2) a solid base phase, respectively. wherein the reagents are substantially entirely in the first-mentioned organic phase and the base is substantially entirely in the second phase.

A phase transfer agent, which may consist of one or more of several organic quaternary ammonium salts, is added to the 2-phase system.

Specific examples of phase transfer agents useful according to the invention are the following:

Quaternary ammonium salts 15 Tricaprymethylammonium chloride,

Cetyl trimethyl ammonium chloride, Cetyl trimethyl ammonium bromide and Benzyl trimethyl ammonium hydroxide "20 Tertiary amines

Trimethylamine,

Triethylamine and

Dimethyl (dimethylaminoethyl) amine.

25 Crown ethers 18-crown-6 with the formula 19 and dibenzo-18-crown-6 with the formula 16.

In general, it is most preferred that the phase transfer agents of the general formula II, wherein at least one of the groups R 1, R 1 / and R 1, an aryl group having 6-14 carbon atoms, an aralkyl group having 6-10 carbon atoms, an alkyl group of 6-20 carbon atoms, an alkaryl group of 6-14 carbon atoms, and an alkenyl group of 6-20 carbon atoms, and the other groups R14 and 8304147-1-12-R44 are alkyl groups, for example methyl, ethyl , n-propyl, i-propyl, 1-butyl, 2-butyl, 1-methyl-2-propyl, 1-pentyl and 1-octyl, while Z is an anion, for example chloride, bromide or hydroxide.

The process of this aspect of the invention is carried out in an inexpensive solvent which is inert to the reaction system, for example toluene, benzene, o-xylene, m-xylene, p-xylene, ethylbenzene, n-hexane, cyclohexane, methylene chloride or o-dichlorobenzene.

The process of this aspect of the invention is conducted at a temperature range from about 10 to about 150 ° C, with a temperature range from 50 to 120 ° C being preferred. The reaction time is inversely proportional to the reaction temperature, with lower reaction temperatures leading to longer reaction times and this reaction time ranging from about 30 minutes to about 10 hours.

In the reaction of this aspect of the invention, the molar ratio of myracaldehyde to allyl halide reagent is in the range of 0.5: 1 to 1.5: 0.5, with -20 being a ratio of 1: 1 to 1: 1, 2 is preferred.

The molar ratio of base to allylic aldehyde in the reaction mass may range from about 0.75: 1 to about 1.5: 1, with a base allylic aldehyde ratio of 1: 1 to 1.2: 1 being preferred. deserves.

The amount of "phase transfer agent" in the reaction mass, based on the amount of myracaldehyde in the reaction mass, may range from 0.5 g per mole of myracaldehyde to 25 g per mole, with a concentration of "phase transfer agent" in the a range of from about 2.5 to about 7.5 "phase transfer agent" per mole of myracaldehyde is preferred.

The reaction according to the invention is preferably carried out at atmospheric pressure, since it is most effective, but it is possible to operate at higher or lower pressures 3304147 m * V * - 13 - without adversely affecting the final yield of the desired reaction product. affects.

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

The terms "change" and "modify" in their various forms here mean that an aroma character or note is provided or imparted to an otherwise relatively soft, tasteless substance or that an existing aroma character is enhanced when the natural aroma is determined falls short or that an existing aroma or an existing aroma impression is supplemented to modify the organoleptic character The materials thus changed are herein referred to as consumable materials.

The term "enhancing" in its various forms means that a particular aroma, a particular flavor "nuance" or "nut" is enhanced in a food flavor composition and / or in a foodstuff without the nature or quality of the aroma, the taste, nuance or note.

The term "food" includes both solid and liquid digestible materials for humans and animals, which materials usually, but not necessarily, have nutritional values. Foods therefore include fruit juices, meats, meat juices, soups and packaged foods, vegetables, snack foods, dog and cat foods, other animal products and the like.

When the 2,4,7-trimethyl-2,6-octadienal prepared according to the invention is used in a food flavor composition, it can be combined with the usual flavor ingredients or additives. Such co-used ingredients or flavor additives are well known for this use and have been widely described in the literature. Apart from the requirement that such an added material must be acceptable with regard to the digestion and must therefore be non-toxic and also otherwise non-harmful, the usual materials can be applied and on wide widely, these include other flavorings, vehicles, stabilizers, thickeners, surfactants, preservatives and flavor enhancers.

Examples of preferred aromatizing additives are: natural orange oil; acetaldehyde; ethyl acetate; Ethyl butyrate; propanal; trans-2-hexenal; trans-2-ethylidene-cis-3-hexenal? 2-ethylidene-6-methyl-cis-3-heptenal and 15 cis-2-ethylidene-cis-3-hexenal.

The 2,4,7-trimethyl-2,6-octadienal or compositions containing it may be combined with one or more vehicles or carriers to add it to the particular product. Vehicles can be an edible or other suitable material such as ethyl alcohol, propylene glycol, water and the like. Carriers include materials such as gum arabic, carrageenans, other gums and the like. The 2,4,7-trimethyl-2,5-octadienal according to the invention can be incorporated in the carriers in the usual manner, for example by spray drying, drum drying and the like. Such carriers may also contain materials to process the 2,4,7-trimethyl-2,6-octadienal (and any other flavoring ingredients) into encapsulated products.

When the carrier is an emulsion, the aroma composition may also contain emulsifiers, such as mono- and diglycerides of fatty acids and the like. With these carriers or vehicles, the desired physical shape of the composition can be prepared.

The amount of 2,4,7-trimethyl-2.6-35 octadienal used should be sufficient to give the product the desired 83 0 4 1 4 7 mtf - 15 aroma properties, but otherwise the use of an excessive amount of the derivative not only wasteful and uneconomical, but in certain cases too great an amount can balance the aroma or other organoleptic properties of the consumed product.

The amount used will vary depending on the final nutrient, depending on the amount and nature of the flavor originally present in the food, on the further processing steps, to which food will be subjected, on local or other preferred factors, on the mode of storage, if this is done, and the treatment before consumption, for example baking, cooking, etc., which the product undergoes to the final consumer. Thus, the terms "effective amount" and "sufficient amount" are, in connection with the present invention, to be considered quantitatively suitable for altering, modifying or enhancing the flavor of the food.

It is therefore preferred that the final composition contain from about 0.08 parts per million (ppm) to about 250 ppm 2,4,7-trimethyl-2,6-octadienal. More particularly, in nutritional compositions it is desirable to use from about 0.15 ppm to 50 ppm to enhance or modify flavor, and in certain preferred embodiments of the invention, about 0.2 to 10 ppm 2,4,7-trimethyl-2,6-octadienal incorporated to provide the finished product with positive citrus aromas. All parts, amounts, percentages and ratios are by weight unless otherwise stated.

The amount of 2,4,7-trimethyl-2,6-octadienal of the invention used in flavor compositions may vary over a wide range depending upon the particular property desired to be imparted to the food. For example, amounts of 2,4,7-trimethyl-2,6-octadienal of the invention of from about 1 to 80 or 90% of the total aroma composition can be included in such compositions. Generally, it is desirable from about 2 to about 20% of 2,4,7-trimethyl-2,6-octadienal in such compositions.

As far as the perfume properties are concerned, this compound has an excellent lime-citrus character, which is useful for providing lime nuances to perfume compositions and citrus-type essential oils.

As the compounds of the general formula 13, wherein one of the groups R ^ or both of R2 and / or R ^ consists of methallyl or allyl and the other group R ^ or R2 and / or R ^ consists of hydrogen (hereinafter referred to as as the "1-acetyl-3,3-dimethyl-cyclohexane derivative of the invention") are used as additives for food flavorings, which are the nature of the other ingredients, containing the 1-acetyl-3,3-dimethylcyclohexane derivative of the invention are used to formulate the product composition, including to change, modify, enhance or enhance the organoleptic properties of the final food which is treated therewith.

The term "medicinal product" includes both solids and liquids, which are digestible, non-toxic materials of medical value, such as cough syrups, cough tablets, aspirin, and chewable medicinal tablets.

The term "chewing gum" includes a composition consisting of a substantially water-insoluble chewable gum plastic base, such as "chicle" or substitutes therefor, including jelutong, guttakay, rubber or certain digestible natural or synthetic resins or waxes. The gum base and mixed therewith may include plasticizers or softeners, for example glycerol as well as an aroma composition containing the 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention and in addition sweeteners such as sugars, including sucrose or dextrose and / or Artificial sweeteners, such as cyclamates or saccharin.

Substances suitable for co-processing or flavor additives are well known and extensively described in the art for such applications. It is a requirement that such a material be digestible and therefore non-toxic and otherwise non-harmful, in particular from an organoleptic point of view, so that the final taste and / or aroma of the consumable material does not have unacceptable aroma and taste nuances. Such materials are generally characterized as flavor additives or vehicles and broadly include stabilizers, thickeners, surfactants, preservatives, other flavor ingredients and flavor enhancers.

Stabilizers include preservatives, eg sodium chloride, anti-oxidants, eg calcium and sodium ascorbate, ascorbic acid, butylated hydroxyanisole (mixture of 2- and 3-tertiary-butyl-4-hydroxyanisole), butylated hydroxytoluene (2,6-ditertiary-butyl-4-methylphenol) propyl gallate and the like, as well as sequestrants, e.g. citric acid.

Thickening agents include carriers, binders, shaking cololds, suspending agents, emulsifiers and the like, for example 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, starch products, pectins and emulsifiers, for example mono- and diglycerides of fatty acids, skimmed milk powder, hexoses, pentoses, disaccharide, for example sucrose corn syrup and the like.

Surface active agents include emulsifying agents, eg fatty acids, such as capric acid, caprylic acid, palimitic acid, myristic acid and the like, mono and diglycerides of fatty acids, lecithin, defoaming and dispersing agents such as sorbitan monostearate, potassium stearate, hydrogenated tall 3304147-18 alcohol and the like.

Conditioning agents include bleaching and maturing agents, for example, benzoyl peroxide, calcium peroxide, hydrogen peroxide and the like; setting modifying agents, such as peracetic acid, sodium chlorite, sodium hypochlorite, propylene oxide, succinic anhydride and the like, buffers and neutralizing agents, eg sodium acetate, ammonium bicarbonate, ammonium phosphate, citric acid, lactic acid, vinegar and the like; coloring agents, for example, carmonic acid, cochineal, "tumeric" and turmeric and the like; reinforcing agents such as aluminum sodium sulfate, calcium chloride and calcium gluconate, texturizing agents, anti-caking agents, for example, aluminum calcium sulfate and tribasic calcium phosphate, enzymes, yeast foods, for example, calcium lactate and calcium sulfate, nutritional supplements, for example, iron salts, such as ferrous phosphate, ferrous gluconate and the like riboflavonate zinc sources, such as zinc chloride, zinc sulfate and the like.

Other flavor ingredients and flavor enhancers include organic acids, for example, acetic acid, formic acid, 2-hexene carboxylic acid, benzoic acid, n-butyric acid, caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovaleric acid, α-methylbutyric acid, propionic acid , valeric acid, 2-methyl-2-pentene carboxylic acid and 2-methyl-3-pentene carboxylic acid, ketones 25 and aldehydes and ketals and acetals thereof, for example acetaldehyde, acetophenone, acetone, acetylmethylcarbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methylbutanal , beta, beta-dimethylacrolein, methyl-n-amylketone, n-hexenal, 2-hexenal, isopentanal, hydro-cinnamaldehyde, cis-3-hexenal, 2-heptanal, nonylaldehyde, 4- (p-hydroxyphenyl) -2-butanone, alpha ionone, beta ionone, methyl 3-butanone, benzaldehyde, damascon, damascenone, acetophenone, 2-heptanone, o-hydroxyacetophenone, 2-methyl-2-hepten-6-one, 2-octanone, 2-undecanone, 3-phenyl-4-pentenal, 2-phenyl-2-hexenal, 2-phenyl-2-pentenal, furfural, 5-methylfurfural, cinnamaldehyde, cis-ethylidene cis-3-hexenal, 83 0 4 1 4 7 • * - 19 - * cis-ethylidene-trans-3-hexenal, cis-ethylidene-trans-3-heptenal, cis-ethylidene-trans-3-heptenal-diethyl acetal, cis-3-ethylidene-4-octenal, faeta-cyclohomocitral / 2-pentanone, 2-pentenal and propanal; alcohols, such as 1-butanol, benzyl alcohol, 5-bomole, trans-2-buten-1-ol, ethanol, geraniol, 1-hexanal, 2-heptanol, trans-2-hexenol-1, cis-3-hexene- 1-ol, 3-methyl-3-buten-1-ol, 1-pentanol, l-pentene-3-ol, p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isophenchyl alcohol, phenyl 1-2-ethanol, alpha-terpineol hyrate , eugenol, linalool, 2-heptanol, 10 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-methyl butyrate, ethyl ethyl ethyl butyrate, hexyl acetate, 2-hexenyl butyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, methyl acetate, methyl butyrate, methyl caproate, methyl isobutyrate, alpha methyl phenyl glycidate, ethyl succinate, isobutyl cinnamate, cinnyl acetate, methyl pentyl acetate; Hydrocarbons such as dimethylnaphthalene, dodecane, methyl diphenyl, methylnaphthalene, myrcene, naphthalene, octadecane, tetradecane, tetramethyl, naphthalene, tridecane, trimethyl-naphthalene, undecane, caryophyllene, 1-fellandrene, p-cymene, 1-alpha-phenylene; pyrazines such as 2,3-dimethylpyrazine, 2,5-di-methylpyrazine, 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, isopropyldimethylpyrazine, methyl ethylpyrazine, tetramethylpyrazine, trimethylpyrazine; 30 essential oils such as jasmine absolute, cassia oil, cinnamon bark oil, rose absolute, Florentine iris absolute, lime essential oil, Bulgarian rose, yara yara and vanilla; lactones such as 6-nonalactone; sulfides, for example, methyl sulfide and other products, such as maltol, acetoin and other acetals (for example, 1,1-diethoxyethane, 1,1-dimethoxyethane Λ-r λ f * i 3 ^ 0 ^ 74 /. *

V

- 20 - and dimethoxymethane).

The specific additive selected may be either solid or liquid depending on the desired physical shape of the final product, ie the food, either synthetic or natural and must in any case be (1) organoleptically compatible with the 1-acetyl 3,3-dimethylcyclohexane derivatives according to the invention because the organoleptic properties thereof (aroma and / or taste) are not suppressed, (2) do not react with the 10 l-acetyl-3,3-dimethylcyclohexane derivatives according to the invention and (3) can provide a medium in which the 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention can be dispersed or mixed to obtain a homogeneous medium. In addition, the choice of one or more flavoring additives, as well as the amounts thereof, depends on the nature of the organoleptic character desired in the final product. For example, in the case of flavor compositions, the choice of the ingredient will vary with the food, chewing gum, medicinal product or toothpaste to which the taste and / or the aroma must be imparted, or which must be modified, changed or enhanced. In contrast, in the preparation of solid products, for example, synthetic foods, ingredients must be selected which can normally give solid compositions, such as various cellulose derivatives.

As will be appreciated by one skilled in the art, the amount of 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention used in any one case may vary over a relatively wide range depending upon the desired organoleptic effects to be achieved. Thus, correspondingly larger amounts will be needed in those cases where the final nutritional composition to be flavored is relatively neutral in taste, while relatively small amounts will be sufficient crowning in 35 cases where a composition is to be reinforced, which is 83 0 4 1 4 7 - 21 -> it only falls short in natural aroma and / or taste.

The first requirement is that the selected amount is effective, ie sufficient to change, modify or enhance the organoleptic properties of the basic composition, whether food as such, chewing gum as such, medicinal product as such, toothpaste as such or flavor composition .

The use of insufficient amounts of the 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention will, of course, significantly diminish the ability to achieve the desired results, while excessive amounts are unnecessarily expensive and, in extreme cases, the distort flavor aroma balance, causing them to miss their target. Thus, the terms "effective amount" and "sufficient amount" are to be attributed in the present description a meaning consistent with obtaining the desired flavor effects.

Therefore, and in connection with the final nutritional compositions, chewing gum compositions, medicinal product compositions and toothpaste compositions, it has been found that amounts of the 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention vary from a small but effective amount, e.g. , 5 parts per million to about 100 parts per million, based on the total composition, are suitable. Concentrations above the stated maximum amount are normally not recommended as they are generally not suitable for enhancing the organoleptic properties. In those cases where the 30-acetyl-3,3-dimethylcyclohexane derivatives of the invention are added to the food as an integral component of an aroma composition, it is of course essential that the total amount of the aroma composition used is sufficient to be contained in the food an effective concentration of the 1-acetyl-3,3-dimethylcyclohexane derivatives 8304147

4 V.

- 22 - to be provided.

Food flavor compositions prepared according to the invention preferably contain the 1-acetyl-3,3-dimethylcyclohexane derivative of the invention in concentrations from 0.1 to about 15% by weight, based on the total weight of the flavor composition concerned.

The composition described here can be prepared in the usual manner, for example, as it is done in the beating of dough and in the preparation of fruit drinks, and they can be formulated by mixing the respective ingredients in the indicated amount in a suitable mixing device, so that the desired consistency, homogeneity of the dispersion, etc. are achieved. Alternatively, flavor compositions in the form of particulate solids can be conveniently prepared by mixing the 1-acetyl-3,3-dimethylcyclohexane derivative of the invention with, for example, gum arabic, gum tragacanth, carrageenan and the like, and then spray spraying the resulting mixture drying to yield the 20-part solid product. Pre-prepared powdered flavor blends, for example a fruit flavored powder blend, may be obtained by mixing the dried solid components, for example starch, sugar and the like, and the 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention in a dry mixer to the desired degree. of uniformity has been achieved.

Preference is given to combining the 1-acetyl-3,3-dimethylcyclohexane derivatives according to the invention with the following additives: p-hydroxybenzyl acetone, geraniol, cassia oil, acetaldehyde, maltol, ethylmethyl phenyl glycidate, benzyl acetate, dimethyl sulfide, eugenol, vanillin, caryphenylene, methyl cinnamate, guajacol, ethyl pelargonate, cinnamaldehyde, methyl anthranilate, 5-methyl furfural, isoamyl acetate, cis-ethylidene-cis-3-hexenal, 35 cis-ethylidene-trans-3-hexenal, cis-ethylidene-trans -3-heptenal, 8304147 - 4 - 23 - * cis-ethylidene-trans-3-heptenal-diethyl acetal, cis-3-ethylidene-4-octenal, isobutyl acetate, cuminaldehyde, alpha ionone, cinnamyl formate, ethyl butyrate, methyl cinnamate gamma-undecalactone, naphthyl ethyl ether, diacetyl, furfural, ethyl acetate, anethole, 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, daxnascon (1-crotonyl-2,2,6-trimethylcycl ohex-1-one), damascenone (1-crotonyl-2,2,6-trimethylcyclohexa-1,5-diene), beta-cyclo-10 homocitral (2,2,6-trimethylcyclohex-1-a carboxaldehyde), isoanyl butyrate , cis-3-hexenol-1,2-methyl-2-pentene carboxylic acid, elemecine (4-allyl-1,2,6-trimethoxybenzene), isoelemecine (4-propenyl-1,2,6-trimethoxybenzene) and 2- ( 4-hydroxy-4-methyl-pentyl) norbomadiene prepared according to United States Patent Application 461,703 of April 17, 1974.

The 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention and one or more auxiliary perfume ingredients, such as, for example, alcohols, aldehydes, ketones, terpene hydrocarbons, nitriles, esters, lactones, natural essential oils and synthetic essential oils, can be mixed so that the combined fragrances of the individual components provide a pleasant and desirable fragrance, especially and preferably with "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, containing fragrant substances, which contain a special note to the perfume during all stages of evaporation and substances that slow evaporation and 30 (d) top notes, which usually consist of low-boiling, fresh-smelling materials.

Λ

In perfume compositions, it is separate components that contribute their particular scent properties, but the total sensory effect of the perfume compositions 8304147 v - 24 -> is at least equal to the sum total of the effects of each of the individual ingredients. For example, the 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention can be used to alter, modify, or enhance the aroma properties of a perfume composition, for example, by using or moderating the odor reaction provided by another component of the perfume composition. composition.

The amount of 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention, which will act in perfume compositions and in perfumed products and perfumed waters, depends on many factors, including the other ingredients, their amounts and the effects sought.

It has been found that perfume compositions containing only 0.01% 1-acetyl-3,3-dimethylcyclohexane derivative of the invention 15 or even less (e.g. 0.005%) can be used to provide green, fruity, aldehyde nuts with mother resin, ginger and citrus-like nuances to soaps, cosmetics and other products. The amount used can be up to 70% of the fragrance components and depends on considerations of cost, the nature of the final product, the effect desired in the final product and the desired fragrance.

The 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention are useful (either alone or together with other ingredients in perfume compositions) as fragrance components in detergents and soaps, odorants and deodorants for space, perfumes, fragrance waters, toilet water, bath preparations such as bubble baths or bath salts, hair preparations such as lacquers, brilliantines, pomades and shampoos, cosmetic preparations, such as ointments, deodorants, hand lotions and suntan oils, powders such as talcum powder, dusting powders, face powders and the like. When used as a fragrance component, an amount of only 1% 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention is sufficient to impart ginger, citrus and mother resin nuances to "petitgrain" flavors.

83 04 1 4 7

* JT

- 25 -

Generally, no more than 3% is 1-acetyl-3,3-dimethyl-cyclohexane derivative. according to the invention, calculated on the final end product, required in the paffrum composition.

In addition, a perfume or fragrance composition according to the invention may contain a vehicle or carrier for the 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention. The vehicle can be a liquid, for example 1 a non-toxic alcohol, a non-toxic glycol or the like.

The carrier can also be an absorbent solid, eg a gum (eg gum arabic) or components for encapsulating the composition (eg gelatin).

In addition, the 1-acetyl-3,3-dimethyl-cyclohexane derivatives of the invention are capable of supplementing and / or energizing certain fragrance and aroma notes, which are usually lacking in many previously available tobacco flavors.

In connection with tobacco flavors, the terms "change" and "modify" in their various forms mean "supplementing or providing flavor characters or notes to otherwise soft tobacco or tobacco substitutes or tobacco flavor composition or enhancing existing flavors". properties, if a natural aroma falls short in some respect or to supplement the existing aroma impression to modify its quality, character or taste. "

The term "enhancement" means intensifying "without change in the nature or the quality of the aroma or taste" one or more flavor and / or aroma nuances present in the organoleptic impression of tobacco or a tobacco substitute or a tobacco flavor.

The invention provides an organoleptically improved smoking tobacco product and additives therefor, as well as methods for their preparation, which overcome specific problems encountered so far and which include specific desirable grains, sweet, fruity, and blossom 8304147.

Tobacco-like nuances for smoking and in the main and side streams of smoking are developed or reinforced and can be easily controlled and maintained at the desired uniform level, independent of variations in the tobacco components of the mixture.

The invention further provides improved tobacco additives and methods whereby green, sweet, fruity, blossom and virginia tobacco-like nuances for smoking and in the main and side streams when smoking can be imparted to smoking tobacco products and easily varied and controlled to obtain the desired uniform aroma properties.

In carrying out this aspect of the invention, a flavoring or flavoring additive is added to smoking tobacco materials or a suitable substitute "for example, dried lettuce leaves", the main ingredient of which is an active 1-acetyl-3,3-dimethylcyclohexane derivative of the invention contains.

In addition to the 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention, other flavoring and / or flavoring additives may be added to the smoking tobacco materials or the substitutes therefor, either separately or mixed with the 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention in the following manner: 25 I. Synthetic materials: beta-ethyl-cinnamaldehyde, eugenol, dipentene, damascenone, maltol, ethyl maltol, delta undecalactone, each decalactone, benzaldehyde, amyl acetate, ethyl butyrate, ethyl valerate, ethyl acetate , beta-cyclohomocitral, 2-hexenol-1,2-methyl-5-isopropyl-1,3-nonadiene-8-one, 2,6-dimethyl-2,6-30 undecadiene-10-one, 2-methyl-5-isopropyl acetophenone, 2 -hydroxy-2.5.5.8a-tetramethyl-1- (2-hydroxyethyl) -decahydro-naphthalene, dodecahydro-3a.6.6.9a-tetramethylnaphtho (2.1-b) -furan, 4-hydroxy hexanecarboxylic acid, gamma lactone and polyisoprenoid hydrocarbons, defined in Example V of U.S. Pat. Nos. 3,589,372 and 830 4147 - 27 - *> II. Natural oil; celery seed oil, coffee extract, mountain moth oil, cocoa extract, nutmeg oil and marjoram oil.

A flavoring and flavoring concentrate containing 1-acetyl-3,3-dimethylcyclohexane derivatives according to the invention and optionally one or more of the additional flavoring additives mentioned above may be added to the smoking tobacco material, the filter or the wrapper consisting of leaves or paper. The smoking tobacco material may consist of crushed, dried, wrapped and mixed tobacco materials or reconstituted tobacco materials or tobacco substitutes (eg lettuce leaves) or mixtures thereof.

The amounts of the flavoring additives can be varied according to the taste, but as far as the enhancement or provision of natural and / or sweet notes has been found, satisfactory results have been achieved as the weight amount of the total sum of 1-Acetyl-3,3-dimethylcyclohexane derivatives of the present invention to smoking tobacco material is between 250 ppm and 1500 ppm (0.025-0.15%) of the active ingredients to the smoking tobacco material. Further, satisfactory results have been found to be obtained when the weight amount of the sum total of 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention used for the flavoring material is between 2500 and 10,000 ppm (0.25-1.5%) .

Any suitable method for incorporating the 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention into the tobacco product can be used. For example, the 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention, either alone or together with other flavor additives, can be dissolved in a suitable solvent, for example ethanol, pentene, diethyl ether and / or other volatile organic solvents, after which the resulting solution can be sprayed on the dried, wrapped and mixed tobacco materials or after which the tobacco material can be dipped in this solution. Under certain conditions, a solution of # 30 * 147 v * - 28 - the 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention, either alone or in conjunction with other flavoring additives, may be applied using a suitable device, e.g. a brush or roller , on the paper or sheet 5 wrapper for the smoking product, or it may be applied to the filter by spraying, dipping or coating.

Moreover, it will be appreciated that only part of the tobacco or tobacco substitute needs to be treated and the tobacco thus treated can be mixed with other tobaccos before the final tobacco product is formed. In such cases, the treated tobacco may contain the 1-acetyl-3,3-dimethylcyclohexane derivative of the invention in excess of the amount or concentration mentioned above, so that when mixed with other tobaccos, the final product will be the percentage within the specified range contains.

According to a specific example of the invention, an aged, dried and crushed domestic burley tobacco is sprayed with a 20% ethyl alcohol solution of 1-acetyl-3,3-dimethylcyclohexane derivatives according to the invention in such an amount that a tobacco composition containing 800 ppm by weight of 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention on a dry basis is obtained. The alcohol is then removed by evaporation and the tobacco is processed into cigarettes in the usual manner. The cigarette thus treated has a desirable and pleasant aroma (enhances smoke "body" sensation in the mouth with enhanced tobacco-like notes and pleasant aromatic nuance) which can be detected in the main and side streams when smoking the cigarette. This aroma has been described as possessing green, sweet, fruity, blossom and Virginia tobacco-like nuances for smoking and in the main and side stream when smoking.

Although the invention is particularly useful for the manufacture of smoking tobacco, for example cigarette tobacco, 8304147

a

Cigarette tobacco and pipe tobacco, other tobacco products formed from sheeted tobacco dust or fine particles may also be used. Likewise, the 1-acety1-3,3-dimethyl-cyclohexane derivatives of the invention may be incorporated into materials, such as nozzles, suture adhesives, packaging materials and the like, which are used in conjunction with the tobacco to make a smoking product. to gain. In addition, the 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention may be added to certain tobacco substitutes for natural or synthetic origin (eg dried lettuce leaves) and therefore, the term "tobacco" in this specification means any composition, which is intended to be smoked or consumed in such a manner, regardless of whether it is composed of parts of tobacco plants or replacement materials therefor.

It will be appreciated that the 1-acetyl-3,3-dimethylcyclohexane derivatives of the invention can be used to alter, modify or enhance the sensory properties, such as the taste and / or the smell of a number of consumable materials.

The 1-butanoyl-3,3-dimethylcyclohexane derivatives of the invention and one or more auxiliary perfume ingredients, including, for example, alcohols, aldehydes, nitriles, esters, cyclic esters (or lactones) and natural essential oils, can be mixed so that the mixed odors of the individual components give a pleasant and desired odor impression, in particular and preferably in "amber" scents. Such perfume compositions usually contain (a) the main note or the "bouguet" or foundation stone of the composition, (b) modifiers that round off and accompany the main note, (c) fixatives, containing fragrant substances, which give a special note to the perfume during all stages of the evaporation, as well as substances that delay evaporation, and (d) top notes, usually consisting of low boiling, 8304147. > t.

- 30 - freshly scented materials.

In perfume compositions they are separate components, which contribute to the special fragrance properties; however, the total sensory effect of the perfume composition will be at least equal to the sum total of the effects of each of the ingredients. For example, 1-butanoyl-3,3-dimethyl-cyclohexane can be used to alter, modify, or enhance the aroma properties of a perfume composition, for example, by using or moderating the odor reaction, which is produced by another component in the composition provided.

The amount of 1-butanoyl-3,3-dimethylcyclohexane of the invention, which will act in perfume compositions and in perfumed articles and waters of odor, depends on many factors, including the other ingredients, the amounts thereof and the desired effects. It has been found that pafrum compositions containing only 0.01% 1-butanoyl-3,3-dimethylcyclohexane or even less (for example 0.005%) can be used to provide a. fruity, berry-like, spicy aroma with green and tobacco nuances to soaps, cosmetics and other products. The amount used can be up to 70% of the fragrance components and depends on considerations of cost, the nature of the final product, the effect desired in the finished product, and the desired fragrance. The 1-butanoyl-3,3-dimethylcyclohexane of the invention is useful (either alone or together with other ingredients in perfume compositions) as a fragrance component in detergents and soaps, odorants and deodorants for space, perfumes, perfumes, toilet water, bath preparations, such as 30 lacquers, brilliantines, pomades and shampoos, cosmetic preparations such as ointments, deodorants, hand lotions and suntan oils, powders such as talc, pollinating powders, face powders and the like. When used as a fragrance component, only 1% l-butanoyl-3,3-dimethylcyclohexane is sufficient to provide an intense spicy note to "amber" compositions.

8304147 »'X" - 31 -

Generally no more than 3% 1-butanoyl-3,3-dimethyl-cyclohexane, based on the final product, is required in the perfume composition.

In addition, the perfume composition or fragrance composition of the invention may contain a vehicle or carrier for the 1-butanoyl-3,3-dimethylcyclohexane. The cell can be a liquid, for example a non-toxic alcohol, a non-toxic glycol or the like. The carrier can also be an absorbent solid, such as a gum "eg gum arabic" or components for encapsulating the composition (eg gelatin).

It will be understood that the 1-butanoyl-3,3-dimethylcyclohexane of the invention can be used to alter, modify or enhance odor of a variety of consumable materials.

When the 1- (2-propenyl) - (4-methyl-3-pentenyl) - 3Δ-cyclohexene-1-carboxaldehydes of the invention are used as food additives, the nature of the ingredients added together with these compounds will be Also contribute to altering, modifying, improving or enhancing the organoleptic properties of the food finally treated therewith.

The specific additive selected may be either solid or liquid depending on the desired physical shape of the final product, ie the food, either synthetic or natural and in any case (1) must be organoleptically compatible with the 3 1 - (2-propenyl) - (- methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehydes according to the invention by not covering or spoiling the organoleptic properties thereof (aroma and / or taste) (2) are not reactive to the 3 1- (2-propenyl) - (4-methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehydes and (3) are capable of providing an environment in which 3 the compound 1 - (2-propenyl) - (4-methyl-3-pentenyl) -Δ-cyclo-35 hexene-1-carboxaldehyde can be dispersed or mixed to 8304147

* V

4 - 32 - obtain a homogeneous medium. In addition, the choice of one or more flavor additives, as well as the amount thereof, will depend on the precise organoleptic character ultimately desired in the final product. For example, in aroma compositions, the choice will vary with regard to the food, chewing gum, medicinal product or toothpaste, in which the aroma and / or the flavor must be communicated, modified, changed or enhanced. In contrast, in the preparation of solid products, for example, synthetic foods, the ingredients must be selected so that normally solid compositions are obtained. For example different cellulose derivatives.

It will be apparent to one skilled in the art that the amount of 1- (2-propenyl) - (4-methyl-3-pentenyl) -Δ-15 cyclohexene-1-carboxaldehyde used in a given case covers a wide range can vary depending on the desired organoleptic properties. Accordingly, correspondingly larger amounts are needed in those cases where the final flavor composition to be flavored is relatively soft in taste, while relatively small amounts may be sufficient in cases where the composition serves only to enhance the one or more otherwise inadequate natural aroma or taste. The first requirement is that the amount selected is effective, ie sufficient to alter, modify or enhance the organoleptic properties of the base composition, whether food as such, chewing gum as such, medical product as such, toothpaste as such or flavor composition .

The use of an insufficient amount of 3 1- (2-propenyl) - (4-methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehyde will, of course, impair the ability to achieve the desired results, while excessive amounts are unnecessarily expensive and in excessive cases may disrupt the aroma-taste balance and thereby nullify an inherent 8304147 * - 33 - * effect. Thus, the terms "effective amount" and "sufficient amount" are to be attributed in the present application a meaning consistent with achieving the desired aroma effects.

5 With regard to the final nutritional compositions, chewing gum composition, medicinal product compositions and toothpaste compositions, amounts of 1- (2-propenyl) -3 (4-methy1-3-pentenyl) -Δ-cyclohexene-1-carboxaldehydes from a small, but effective amount, for example, 0.5 parts per million, to about 100 parts per million, based on the total composition, are suitable. Concentrations above the maximum amount are normally not recommended as they do not give rise to a proportional enhancement of the organoleptic properties. In those cases where the 3 15 1- (2-propenyl) - (4-methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehydes are added to the food as an integral component of an aroma composition essential that the total amount of flavor composition used is sufficient to provide an effective concentration of 1- (2-propenyl) - (4-methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehyde in the food product to provide.

Food compositions prepared according to the invention preferably contain 1- (2-propenyl) - (4-methyl-3-3-pentenyl) -Δ-cyclohexene-1-carboxaldehydes in concentrations from about 0.1 to about 15 wt. %, based on the total weight of the said aroma composition.

The composition described herein can be prepared in the usual manner, as is also the case, for example, in the beating of dough and in the preparation of fruit drinks, and they can be obtained by mixing the respective constituents in the indicated amount in a suitable mixing device, to achieve the desired consistency, homogeneity of the dispersion, etc.

Alternatively, flavor compositions in the form of 35-particle solids can be conveniently prepared, for example, by using the 8304147 - 34 - 3 1- (2-propenyl) - (4-methy1-3-penteny1) -Δ-cyclohexene-1-carboxaldehydes mixing with gum arabic, gum tragacanth, carrageenan and the like and then drying the resulting mixture by spraying to give the 5-part solid product. Pre-prepared powdered flavor blends, for example a fruit flavored powder blend, can be obtained by mixing the dried solids, for example, sugar, starch 3 and the like and the 1- (2-propenyl) - (4-methyl-3-penteny1) - Mix Δ -10 cyclohexene-l-carboxaldehydes in a dry mixer until the desired level of uniformity is achieved.

It is preferable to combine the 1- (2-propenyl) - 3 (4-methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehydes according to the invention with the following additives 15 p-hydroxybenzylacetone, geranio, cassia oil , acetaldehyde, maltol, ethylmethylphenylglycidate, benzyl acetate, dimethyl sulfide, eugenol, vanillin, caryophyllene, methyl cinnamate, guajacol, ethyl pelargonate, cinnamaldehyde, methylanthhranilate, 5-methylfurfural, isoamyl acetate, alpha ethyl butyrate, methyl cinnamate, acetic acid, gamma undecalactone, naphthylethyl ether, diacetyl, furfural, ethyl acetate, anethole, 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, damascone (1-crotonyl-2,2,6-trimethylcyclohex-1-one), damascenone (1-crotonyl-2,2,6 trimethylcyclohexa-1,5-diene), beta-cyclohomocitral (2,2,6-trimethylcyclohex-1-a carboxaldehyde), isoamylbutyrate, cis-3-hex enol-1,2-methyl-2-pentene-carboxylic acid, elemecine (4-allyl-1,2,6-trimethoxybenzene), 30 isoelemecine (4-propenyl-1,2,6-trimethoxybenzene) and 2- (4- hydroxy-4-methylpentyl) norbornadiene prepared according to U.S. Patent Application 461,703 of April 17, 1974.

The 1- (2-propenyl) - (4-methyl-3-pentenyl) -Δ3-cyclohexene-1-carboxaldehydes and one or more auxiliary perfume constituents, such as, for example, alcohols, aldehydes, ketones, terps. n 4 1 4 7 -> - 35 - * 'hydrocarbons, nitriles, esters, lactones, natural essential oils and synthetic essential oils, and synthetic essential oils, can be mixed so that the combined odors of the individual components are pleasant and give the desired fragrance effect, especially in roses. Such perfume compositions usually contain (a) the main note or the "bouquet" or keynote of the compositions, (b) modifiers which round off and accompany the main note; (C) fixatives, containing fragrant substances, which give the perfume a special note during all stages of evaporation and substances that delay evaporation and (d) top notes, which usually consist of low-boiling, freshly-scented material.

In perfume compositions, it is the individual components that contribute to the particular fragrance characteristic, but the total sensory effect of the perfume composition is at least equal to the sum total of the effects of each of the ingredients. For example, compounds 1- (2-propenyl) - 20 (4-methy1-3-penteny1) -Δ-cyclohexene-1-carboxaldehydes can be used to alter, modify, or enhance the aroma properties of a pafrum composition, for example by using or moderating the odor reaction provided by another ingredient in the composition.

The amount of the 1- (2-propenyl) - (4-3 methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehyde according to the invention, which will act in perfume compositions and in perfumed products and waters of smell, depends on of many factors, including the other components, their amounts and the desired effects. Perfume compositions have been found to contain only 0.01% of the 1- (2-propenyl) - (4-methyl-3-3-pentenyD-Δ-cyclohexene-1-carboxaldehydes or even less (e.g. 0.005%) can be used to provide a sweet, fruity, lavender nut with citrus-35 and balsam nuances to soaps, cosmetida or other products.

Ö "Z ·> 7 ö V>" J ï t. - 36 -

The amount used can vary up to 70% of the fragrance components and depends on considerations regarding the cost, the nature of the end product, the effect sought with the finished product and the desired odor.

The 1- (2-propenyl) - (4-methyl-3-pentenyl) -Δ- cyclohexene-1-carboxaldehyde of the invention, either alone or together with other ingredients in perfume compositions, are useful as fragrance components in detergents and soaps , space odorants and deodorants, perfumes, scents, toilet water, bath preparations such as lacquers, brilliantines, pomades and shampoos, cosmetic preparations such as ointments, deodorants, hand lotions and suntan oils, powders such as talc, pollinating powders, face powders and the like. When used as fragrance component 3, only 1% 1- (2-propenyl) - (4-methyl-3-pentenyl) -Δ-cyclohexene-15-1-carboxaldehyde is sufficient to impart an intense blossom note to rose compositions. Generally no more than 3% of the 1- (2-propenyl) - (4-methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehyde, based on the final product, is required in the perfume composition .

In addition, the perfume composition or fragrance composition of the invention may contain a vehicle or carrier for the 3 1- (2-propenyl) - (4-methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehydes. The vehicle can be a liquid, for example an alcohol, a non-toxic alcohol, a non-toxic glycol or the like. The carrier may also be an absorbent solid such as a gum (e.g. gum arabic) or composition encapsulation ingredients (e.g. gelatin).

It is clear that the 1- (2-propenyl) - (4-3 methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehyde of the invention can be used to alter, modify or enhance sensory properties, in particular organoleptic properties, such as the aroma and / or odor and / or taste of a wide range of consumable materials.

8304147. i r - 37 -

In addition, the 1- (2-propenyl) - (4-3 methyl-3-penteny1) -Δ-cyclohexene-1-carboxaldehydes of the invention may complement certain fragrance and aroma notes, which are usually lacking in many previously known tobacco flavors, and / or 5 confirm.

With regard to tobacco flavors, the terms "change" and "modify" in their various forms mean the "provision or communication of flavor characters or nuts to otherwise soft tobacco, tobacco substitutes or tobacco flavor compositions or to improve the existing flavor properties as a natural aroma in some respects falls short or supplementing the existing aroma impression for modifying the quality, character or taste ".

The term "enhancing" means intensifying (without change in the nature or quality of the aroma or taste) one or more flavor and / or aroma nuances present in the organoleptic impression of tobacco or a tobacco substitute or a tobacco flavor.

The invention provides an organoleptically improved smoking tobacco product and additives therefor, as well as a method for preparing it, which overcome specific problems encountered hitherto with specific desired woody cocoa and cocoa liqueur-like flavor properties of natural burley tobacco, as well as the sweet-rich and Creamy-oily nuances thereof, which are enhanced or developed and can be easily controlled and maintained at the desired uniform level, regardless of variations in the tobacco components of the mixture.

The invention further provides improved tobacco additives and method by which various cocoa-like, cocoa-liqueur-like sweet-rich and creamy oily nuts can be provided to smoking tobacco products and these can be easily varied and controlled to obtain the desired even flavoring properties .

When carrying out the method according to the ft λ ·· /, v - 38 - *> invention, a flavoring or flavoring additive is added to smoking tobacco materials or a suitable substitute therefor (for instance dried lettuce leaves), which active ingredient l - (2-propenyl) - (4-methyl-3-pentenyl) -Δ-cyclohexene-5-1-carboxaldehydes.

In addition to 1- (2-propenyl) - (4-methyl-3-pentenyl) cyclohexene-1-carboxaldehyde of the invention, other flavor and fragrance additives may be added to smoking tobacco materials or substitutes therefor, either singly or in admixture with the 1- (2-propenyl) - (4-methyl-3-pentenyl) - 3 Δ-cyclohexene-1-carboxaldehydes in the following manner: I. 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, 2-hexenol-1,2-methyl-5-isopropyl-1,3-nonadiene-8-one, 2,6-dimethyl-2,6-undecadien-10-one, 2-methyl-5-isopropyl acetophenone, 2-hydro-2,5,5,8a-tetramethyl-1- (2-hydroxyethyl) decahydronaphthalene, dodecahydro- 3a, 6,6,9a-tetramethylnaphtho (2,1b) -furan, 4-hydroxy hexanecarboxylic acid, gamma lactone, polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No. 3,589,372 and II. Natural oils: celery seed oil, coffee extract, bergamot oil, cocoa extract, nutmeg oil and marjoram oil.

A flavor and aroma concentrate containing the 1- (2-propenyl) - (4-methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehyde from one or more of the additional flavoring additives if desired added to the smoking tobacco material, filter or sheet or paper wrapper. The smoking tobacco material may be crushed, dried, wrapped and mixed tobacco material or reconstituted tobacco material or tobacco substitution products (eg lettuce leaves) or mixtures thereof. The amount of flavoring additives can be varied according to taste, but as far as it contains the enhancement or provision of natural and / or sweet nuts, it has been found to be beneficial. ; . Results can be obtained if the weight amount of the sum total of the 1- (2-propenyl) - (4-methyl-3-pentenyl) -3Δ-cyclohexene-1-carboxaldehydes to smoke material is between 250 ppm and 1500 ppm (0.025 - 0.15%) of the active ingredients 5 to the smoking tobacco material. Furthermore, it has been found that favorable results are obtained when the weight amount of the 3 sum total of the 1- (2-propenyl) - (4-methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehydes to flavor material is between 2500 and 10,000 ppm (0.25 to 1.5%).

Any suitable method for incorporating the 1- (2-propenyl) - (4-methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehydes into the tobacco product can be used. Thus, the 1- (2-propenyl) - (4-methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehydes, either alone or together with other flavor additives, can be dissolved in a suitable solvent, such as ethanol, pentane, diethyl ether and / or other volatile solvents, and the resulting solution can be sprayed on the dried, wrapped and mixed tobacco materials or the tobacco material can be dipped in this solution.

Under certain circumstances, a solution of the 1- (2-3-propenyl) - (4-methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehyde, either alone or in combination with other flavoring additives, can be applied using a suitable device, for example a brush or roller, on the paper or on the wrapper for the smoking product, which can be applied to the filter by spraying, dipping or coating.

In addition, it will be appreciated that only part of the tobacco or the tobacco substitute needs to be treated and the tobacco thus treated can be mixed with other tobaccos before the final tobacco product is formed. In such cases, the treated tobacco may contain 1- (2-propenyl) - (4-methyl-3-Λ pentenyD-Δ-cyclohexene-1-carboxaldehydes) in an amount greater than the above concentration, so that when mixed of other tobaccos, the final product contains a 8304147% -40% percentage within the specified range.

According to a specific example, an aged, dried and crushed rural burley tobacco is sprayed with a 20% ethyl alcohol solution of the 1- (2- 3 propenyl) - (4-methyl-3-pentenyl) -Δ-cyclohexene-1 -carboxaldehyde in an amount such that a tobacco composition is obtained on a dry basis 800 ppm by weight of the 3 1- (2-propenyl) - (4-methyl-3-pentenyl) -Δ-cyclohexene-1-carboxal -dehyde. The alcohol is then removed by evaporation and the tobacco is processed into cigarettes in the usual manner. The cigarette thus treated has a pleasant and desirable aroma (increased smoky "body" sensation in the mouth with enhanced tobacco-like notes and pleasant aroma nuances), which can be seen in the main and side streams when smoking the cigarette. This aroma is described as having a more body, more tobacco-like, more aromatic, slightly oily and slightly cocoa-like aroma with cocoa liqueur-like, creamy, oily and sweet-rich notes.

Although the invention is particularly useful in the manufacture of smoking tobacco, such as cigarette tobacco, cigarette tobacco and pipe tobacco, other tobacco products formed from sheeted powder or fine products can also be used. Also, the 1- (2-propenyl) - (4-methyl-3-3-pentenyl) -Δ-cyclohexene-1-carboxaldehyde according to the invention can be incorporated into materials such as nozzles, seam adhesives, packaging materials and the like which are used in conjunction with tobacco to obtain a smoking product. In addition, the 1- (2-propenyl) -3 (4-methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehydes can be added to certain tobacco substitutes of natural or synthetic origin (eg dried lettuce leaves) and therefore description by the term "tobacco" meant any composition consumed by smoking or otherwise consumed by man regardless of whether it is composed of parts of tobacco plants, substitute * p T p! 4 1 V 'J - * ·, Jf' t f - 41 - means for that or both.

The following examples further illustrate the invention and all parts and percentages therein are by weight unless otherwise stated.

5

Example I

Preparation of 1-Acetyl-3,3-dimethyl- (2-propenyl) cyclohexane

The reaction proceeds according to scheme R.

222 g allyl chloride (3.8 mol) was added over 15 min to a stirred slurry of 462 g (3 mol) 1-acetyl-3,3-dimethyl-cyclohexane, 180 g (4.5 mol) granular sodium hydroxide, 24 g Aliquat 336 (tricapryl methyl ammonium chloride) and 200 g toluene at 70 ° C. The slurry was refluxed for 7 hours, after which the temperature rose to 83 ° C. The slurry was then cooled and 1 L of water was added to the reaction mass with stirring. The organic phase of the reaction mass was washed twice with water and distilled through a 30 x 1.3 cm packed Goodloe column equipped with an automatic reflux 8304147 * 42

Tb Λ setup, set to a 19: 1 reflux discharge ratio (85 ° C, 2.7 mm Hg pressure), yielding 275 g of product of formula 31 (conversion%) as well as high of a compound of formula 32 ( yield 8% and 1 ^ 7 g of 1-acetyl-3,3-dimethylydohexane.

When using sodium hydride instead of sodium hydroxide, a compound of the formula 33 was obtained.

The µMR spectrum for the compound of formula 31 is shown in Figure 6. The infrared spectrum for this compound is shown in Figure 7 * g. HMR analysis leads to the formula 3¾5. Pro interpretation 0.7¾ (s, 3) (0.90 Cs, 3) methyl groups "A" 2.1¾ (s, 3) CH3 group "B" ^ U, 8 - »5 * 1 (m, 2) CHg group C.

5, ¾— »5.8 (m.1) Ηρ

The infrared analysis is as follows: O 1690 cm1 20 C * C; 1660

The mass spectral analysis is as follows: m / es 95, 9¾. 69, Ui, 109, 55, 19¾ (main peak).

The NMR spectrum for the compound of the formula 32 C is shown in Figure 8. The NMR analysis leads to the formula 35.

25 5, ppm interpretation 0.90 (s, 3) • 0.93 (s, 3) methyl groups "A" 2,2- »2,65 (m, 5) CHg's" B "and Hc U, 60 - 5 , 12 (m, 2) CH2 "D” 30 5.50 - 5.95 (m, 1) Hg ______ - - -------- ------ -------- ------ - - ..... '...... -' 8 3 0 4 1 4? '* «43 f * Γ t

The mass spectral analysis is as follows: m / e * 69, 111, 55, fcl, 83, 139, 19¾ (main peak).

The HMR spectrum for a compound of formula 33 (stereochemistry unknown), which is formed when using sodium hydride, is shown in Fig. 9. The infrared spectrum is shown in Fig. 10.

The NMR analysis leads to the formula 36 (stereochemistry unknown) S. ram interpretation 0.83-0.93 methyl groups "A" 2.08 (d, 1) small coupling J = (Hz) CH ^ "B" (-; - scattered allylic H resonances

The infrared analysis is as follows: 1600 cm "% C * C 1700; C * 0

The mass spectral analysis is as follows: m / e * 111, 69, 55, Ui, h3t 57, 290 (main peak).

Example II

A perfume composition prepared by mixing the following ingredients in stated amounts: ingredients amount (grams) n-decylaldehyde 1 n-dodecylaldehyde 2 methylnonylacetaldehyde 0.5 linalool · 50 linalyl acetate 70 * phenylethyl alcohol 100 petigrain SA 20 bergamot oil 30 alpha methyl ionone 25 1 - acetyl-3,3-dimethyl- (2-propenyl) cyclohexane obtained according to the procedure of example i 10 t 'Sj: - · ..

# *, 44

/ V

Constituents amount (grams) of cyclized bicyclo C-12 material obtained by the method of. Example IV of Canadian Patent 85-2255 isobornylcyclohexyl alcohol 10 benzyl acetate 2-n-heptyl cyclopentanone 5.

353.3 (total) 10 The preceding mixture is evaluated and appears to have a high degree of richness and persistence with regard to the new natural "amber" quality. This base composition can be mixed with aqueous ethanol, cooled and filtered to obtain a ready-to-use fragrance. The fragrance water thus prepared has an amber aroma, which abuts against a woody amber nut. The base composition can also be used to scent soap or other toiletries such as lotions, aerosol, pollinators and the like.

Example III.

Preparation of a cosmetic powder composition. A cosmetic powder is prepared by mixing in a ball mill 100 g talcum powder with 0.25 g 1-acetyl-3,3-dimethyl- (2-propenyl) cyclohexane, obtained according to example I. It has an excellent woody, earthy, amber aroma.

Example IV

25 Perfumed liquid detergent

Concentrated liquid detergents with woody, earthy and amber flavors (which detergents are prepared from the lysine salt of n-dodecylbenzenesulfonic acid, as described in U.S. Patent 3,98,818,118), which prepare 1-acetyl-3.3-30 dimethyl- (2- propenyl) cyclohexane prepared according to Example 1. They are prepared by adding the appropriate amount of 1-acetyl-3,3-dimethyl- (2-propenyl) cyclohexane and mixing homogeneously in the liquid detergent. The detergents all have a woody, earthy amber aroma, the intensity increasing with higher concentrations of 1-acetyl-3,3-dimethyl- (2-propenyl) cyclohexane.

83 0 4 1 4 7. ♦

λ t 4S

*

Example y

Preparation of a fragrance water and a handkerchief perfume 1-acetyl-3,3-dimethyl- (2-propenyl) cyclohexane, prepared according to example I:, is taken up in a fragrance water at a concentration of 2.5% in 85 l of aqueous ethanol and in a handkerchief perfume at a concentration of 20 Jf in 95 l of aqueous ethanol. A clear and defined woody, earthy, amber aroma is imparted to the perfume and to the handkerchief perfume.

Example VX-TO Preparation of a perfume and a handkerchief perfume {*: ·

The use of the 1-acetyl-3,3-dimethyl- (2-propenyl) cyclohexane 15 in the composition of Example n gives a clear and defined strong woody, earthy amber aroma to the handkerchief perfume and the fragrance water.

Preparation of a soap composition 100 g of soap flakes are mixed with 2 g of the composition of Example IX until a substantially homogeneous whole is obtained. The scented soap composition exhibits an excellent amber aroma with powerful woody and earthy nuances.

Example fin

Preparation of a detergent composition A total of 100 g of a detergent (lysine salt of t n-dodecylbenzenesulfonic acid, as described in U.S. Patent 3 9½ 818) in powder form is mixed with 0.70 g of the composition of Example II to a substantially completely homogeneous product is obtained. This composition has an excellent amber aroma with powerful earthy 30 and sweet woody nuances.

Example IX

Raspberry flavor composition

The following basic raspberry flavor composition was prepared: 35 8304147 r Λ f 46 ',

V

ingredients parts by weight vanillin 2.0 maltol 3.0 parahydroxybenzylacetone 5.0 5 alpha ionone (10% in propylene glycol) 2.0 ethyl butyrate 6.0 ethyl acetate 16.0 dimethyl sulfide 1.0 isobutyl acetate 13.0 10 acetic acid 10.0 acetaldehyde 10 .0 propylene glycol 930.0 (2.0% of 1-acetyl-3,3-dimethyl- (2-propenyl) cyclohexane is added to half of the above composition. The composition with the 1-acetyl-3.3-dimethyl - (2-propenyl) cyclohexane is compared to the composition without the 1-acetyl-3,3-dimethyl- (2-propenyl) cyclohexane in an amount of 0.01% (100 ppm) in water and judged by a group of experts.

The aroma, containing the 1-acetyl-3,3-dimethyl- (2-propenyl) cyclohexane, appears to exhibit significantly sweeter aroma notes and a sweet raspberry, raspberry kernel and sweet aftertaste and a mouthfeel lacking in the base raspberry composition. It is the unanimous opinion of the experts that the 1-acetyl-3,3-dimethyl- (2-propenyl) cyclohexane rounds off the aroma and contributes to a very natural. Fresh aroma and taste, as is found with whole ripe raspberries. Therefore, the flavor to which the 1-acetyl-3,3-dimethyl- (2-propenyl) cyclohexane has been added is judged to be significantly better than the flavor without the 1-acetyl-3,3-dimethyl (2-propenyl) cyclohexane.

Example T

30 A, Powder Flavor Composition 20 g of the aroma composition of Example IX was emulsified in a solution of 300 g of acacia gum and 700 g of water. The emulsion was spray dried with a Bowen Lab Model Drier, 2 ° c.f.m. air was used with an inlet temperature of 500 ° F, an outlet temperature of 200 ° F and a wheel speed of $ 0,000 revolutions 3304147 *. 47 - * ι * * per minute.

B. Persistent release of aroma ». -

The following mixture is prepared: component parts by weight 5-: liquid raspberry flavor composition of example IX 20 propylene glycol 9

Cab-O-sil® M-5 (silica oxide blend, manufactured 10 'by Cabot Corporation 125 High

Street, Boston, Mass. 02110; physical properties: _ specific, area: 200 m / g nominal particle size 0.012 micron 15 density 2.3 lbs / cu ft 5.00

The Cab-O-sil is dispersed in the liquid raspberry flavor composition of Example IX with vigorous stirring to obtain a viscous liquid. 71 parts by weight of the powder aroma composition of Part A above are then added to the viscous 20. " liquid mixed with stirring at 25 ° C for 30 minutes to obtain a dry, loose, sustained-release flavor powder.

Example '-XI

10 parts by weight of 50 Bloom pigskin gelatin are added to 90 parts by weight of water at a temperature of 150 ° P. The mixture is stirred until the gelatin is completely dissolved and the solution is cooled to 120 ° F. 20 parts by weight of the liquid aroma composition of Example IX is added to the solution and it is homogenized to give a to form an emulsion with a particle size typically between 2 and 5 microns. The material is kept at 120 ° F, including 3p; circumstances the gelatin will not gel.

The confluence is initiated by the slow and steady addition of 40 parts by weight of the 20 µS aqueous sodium sulfate solution. During the confluence, the gelatin molecules are evenly deposited around each oil droplet as the core.

Gelling is effected by pouring the heated confluent mixture into 1000 parts by weight of a J% aqueous sodium sulfate solution at 65 ° F. The resulting gelled and co-annealed product can be filtered and washed with water at temperatures 8304147

Tw * 48 / Λ .Λ below the melting point of gelatin to remove the salt.

The filtered cake is set in this example by washing with 200 parts by weight of a 37% solution of formaldehyde in water. The cake is then washed to remove any remaining 5 grams of aldehyde.

Example xn.

100 parts by weight of "chicle" are mixed with 1+ parts by weight of the flavoring prepared according to Example xi. 300 parts of sucrose and 100 parts of corn syrup are added. The mixing is done in a belt mixer with side walls provided with a jacket, such as these in is marketed by the Baker Perkins Co.

The resulting chewing gum mixture is then processed into (strips with a width of 2.5 cm and a thickness of 2.5 mm. The strips are cut into pieces with a length of 7 »5 cm each. When chewing, this chewing gum has a pleasant and long-lasting raspberry flavor Example xtii

Chewing gum 100 parts by weight of "chicle" are mixed with 18 parts by weight of the flavor, prepared according to Example xn. 300 parts of sucrose and 100 parts of corn syrup are added, mixing is performed in a sidewall belt mixer with a jacket, as sold by the Baker Perkins Co.

The resulting chewing gum mixture is then made into strips 2.5 cm wide and 2.5 mm thick. The 25 strips are cut into pieces with a length of 7.5 cm. When chewed, the chewing gum has a pleasant and long-lasting raspberry flavor Example xiv

Toothpaste comuosition

The following separate groups of ingredients are prepared: 8 3 0 * 1 A 7 l .........

Fri "'49 9 * *% of the components

Group "A" 30,200 glycerol 15,325 distilled water 5 0.100 sodium benzoate 0.125 sodium ac charine 0.005 stannous fluoride

Group "B" 12,500 * calcium carbonate 10 37 * 200 dicalcium phosphate (dihydrate)

Group "C" (* 2,000 sodium H-lauroyl sarcosinate (foaming agent)

Group "D" 1,200 arco material of Example χ 100.00 (total) Method: 1. The ingredients in group "A" are stirred and heated in a boiler with a steam jacket to a temperature of 160 ° F.

2. Stirring is continued for another 3 to 5 minutes to form a homogeneous gel.

3. The powders of group nB "are added to the gel while mixing to form a hamogen paste.

U. While stirring, the arcana of "fD" is added and finally the sodium n-lauroyl sarcosinate.

5. The resulting slurry is then mixed for one hour. The finished pasta is transferred to a three-roller and then homogenized and finally packed in tubes.

The toothpaste obtained gives a pleasant raspberry aroma with a regular and strong intensity during normal treatment during the entire treatment (1 - 1.5 minutes).

___4 8304147, 50. 'ï

Example χν

Chewable vitamin tablets

The arama product obtained by the procedure of Example xi is added to a chewable vitamin tablet composition in an amount of 10 g / kg, which chewable vitamin tablet composition was prepared in the following manner;

In a Hobart mixture, the following materials were mixed to homogeneous g / 1000 tablets

Vitamin C (ascorbic acid) as ascorbic acid-sodium ascorbate mixture 1: 1 70.0

Vitamin (Thiamine Mononitrate) as Rocoat® Thiamine Mononitrate 33 1/3% (Hoffman La Roche) ^ »0

Vitamin B_ (riboflavin) as Rocoat © riboflavin 33 1/3% 5> 0

Vitamin Bg (Luyridoxine Hydrochloride) as Rocoat Pyridoxine Hydrochloride 33 1/3% ^, 0

Niacinamide as Rocoat® Niacinamide 33 1/3 # 33.0

Calcium pantothenate 11.5

Vitamin B ^ (cyanocobalamin) - as a trademark ^ 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 0.0UU

approved paint dye 5.0 (~ Flavor of Example XX (as stated above)

Sweetener (sodium saccharin) 1.0

Magnesium stearate lubricant 20.0

Mannitol q, .s. make up to 500.0

Pre-tablets are prepared by beating together with flat surface punching and milling the products into 1U mesh.

Then 13.5g of dry vitamin A acetate and 0.6g of vitamin D are added in the form of granules. The entire mixture is then compressed with hollow punches in amounts of 0.5 g each.

Chewing the obtained tablets gives a pleasant, long-lasting and strong raspberry flavor for 12 minutes.

8304147 51 O v Λ

Example, χνι

Preparation of 1-acetyl-1-methallyl-3,3-dimethylcyclohexane and 1- (2-methallyl-5-methyl-1 + -pentenoyl) -3,3-dimethyl-cyclohexane

5 The reaction proceeds according to scheme S

A slurry of 62b g of 1-acetyl-3,3-dimethylcyclohexane d (0 + 1 mole), 2b0 g (6 mole) of granular sodium hydroxide 35 g of Aliquot ^ 335 (tricaprylmethyl ammonium chloride) 1 + 32 g (1 +, 8 mole of methallyl chloride and 1 +00 ml of toluene are refluxed for 1 + hour, then 10 liters of water are added to the cooled reaction mass, the aqueous layer is discarded and the organic layer is quickly distilled through a short column to recover 203 g of 1-acetyl 3,3-dimethylcyclohexane, 500 g of 1-acetyl-3,3-dimethyl-1-methallylcyclohexane and 73 g of 3,3-dimethyl-1- (2-methallyl-5-methyl-1 + -pentenoyl) cyclohexane (1-1 + °, 3 .0 mm Hg) to obtain, 15 containing 5% 3,3-dimethyl-1 - (1 + -methyl-U-pentenoyl). Part of the latter compound is isolated by GLC chromatography (1 'x 1 / bn 80% SE-30 packed column, 200 ° C isothermal) and exhibits the following odor and aroma properties

Fragrance properties 20 green, spicy, melon-like, fruity, mother-resinous, 25 ginger-like and citrus-like

Aroma properties fat-like, sweet, 3 ° fruity, citrus, green, vegetable-like and waxy. 35 MR analysis for the compounds indicates the formula 37.

t 8304147 52 • pom interpretation 0.92 (s, 3) 0.9Ms, 3) methyl groups "A" 1.70 (s, 6) methyl groups "C" 5 3.02 (quintet, 1, J = 6h) Hp h, 16 (d, J = 8h) methyl groups ”B, f

The infrared analysis is as follows: \ C * 0 ΐβ95 cm "1 10 C = CH2 1635 cm" 1 C The mass spectral analysis is as follows:

Mtf-262 (confirmed by GC-MS)

The HMR spectrum is shown in FIG. 1 for 1-acetyl-3,3-dimethyl-1-methallyl cyclohexane. The infrared spectrum is shown in Figure 12 for 1-acetyl-3,3-dimethyl-1-methallyl cyclohexane.

The HMR spectrum for 3,3-dimethyl-1- (2-methallyl-5-methyl-H-pentenoyl) cyclohexane is shown in Figure 13. The infrared spectrum is shown in Figure 11.

Example xvn

2o The reaction proceeds according to scheme T.

A slurry of 158 g (1 mol) of 1-acetyl-3,3-dimethylcydo-hexane, 86 g (1.5 mol of potassium hydroxide and 300 ml of toluene is heated to reflux. 135 g (1.5 mol) of C are added to the thickened reaction mass methallyl chloride is added and the mass becomes more liquid The mixture is heated under reflux for 61 hours, then 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 obtain of 86 g of recovered 1-acetyl-3,3-dimethylcyclohexane, 67 g, containing 2% 3,3-dimethyl-1 - (1-methyl-gentenoyl) cyclohexane) 1-acetyl-3,3-dimethyl-1-methallylcyclohexane (HMR spectrum Fig. 11, IR spectrum Fig. 12) and 12 g of 3,3-dimethyl-1 - (1 - methyl - 1 - pentenoyl) cyclohexane.

§ t η ί 1 r? <* 'Y 1}' 53 * ** iv *

Example χντττ

The reaction proceeds according to scheme U.

A mixture of 156 g of 1-acetyl-3,3-dimethylcyclohexane (1 mol), 60 g of sodium hydroxide (1.5 mol), 135 g of methallyl chloride 5 (1.5 mol) and 10 g of triethylanine is stirred and heated at 80-8H for 12 hours ° C

heated. The reaction mass is cooled to room temperature. Vater is added with stirring and the vater layer is deposited.

The organic layer is distilled to give 1-acetyl-3,3-dimethylcyclohexane (62, ¼ g), 1-acetyl-3,3-dimethyl-1 (2-methyl-2-10 propenyl) cyclohexane (80 g), (MR spectrum Fig. 11, IR spectrum Fig. 12) and 3,3-dimethyl-1 - (1 - methyl - 1 - pentenoyl) cy clohexane (8 g).

Example XIX

The reaction proceeds according to scheme V.

A fresh solution of potassium t-butoxide 15 is prepared by adding potassium metal (28 g, 0.72 mol) to 500 ml of free t-butanol under a nitrogen blanket. To this 1-acetyl-3,3-dimethyl-cyclohexane is added and the resulting mixture is stirred at room temperature for 1 hour. 7¼ S (0.8 mol) of methallyl chloride is added and the reaction mass is stirred 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 obtain a mixture of 1-acetyl-3,3-dimethyl-cyclohexane, 1-acetyl-3,3-dimethyl-1 - (2-methyl-2-propenyl) cyclohexane, (HMR spectrum Fig. 11, IR spectrum (Fig. 12) and 3,3-dimethyl-1- (k-methyl-25-pentenqyl) cyclohexane.

V Example xx

Preparation of 1-acetyl-3,3-dimethyl- (2-methyl-2-propenyl) cyclohexane

The reaction proceeds according to scheme W.

30 A slurry of potassium hydroxide (8¼ g, 1.5 mol) 1-acetyl-3,3-dimethylcyclohexane (156 g, 1 mol), dibenzo-18-crown-6 (3 g) of the formula 16 prepared by the Aldrich Chemical Company of Metuchen, Jersey and 150 ml of toluene is heated to reflux, thickening the reaction mass. The mass is cooled to 70 ° C and 135 g (1.5 mole) of methallyl chloride are added, due to the reaction mixture more 3? f); 7 ^ - J j Λ Χ- <· 54 * 'becomes liquid. The reaction mixture is heated to reflux for a further 9 hours, after which the mass is cooled and water is added. The aqueous layer is decanted and the organic layer is distilled to give 1-acetyl-3,3-dimethylcyclohexane (62 g) and 5 1-acetyl-3,3-dimethyl-1- (2-methyl-2-propenyl) cyclohexane (83 g , HMR spectrum Fig. 11, IR spectrum Fig. 12).

Example xxi

A tobacco mixture is prepared by mixing the following ingredients: 10 ingredients, parts by weight light k0.1

Burley 2U, 9 (Maryland 1.1

Turkish 11.6 15 stem (smoke-dried) 1U, 2 glycerol 2.8 water 5.3

The above-mentioned tobacco is used for the preparation of cigarettes and the following composition is formulated and included in each of these cigarettes.

ingredients parts by weight ethyl butyrate 0.05 ethyl valerate 0.05 maltol 2.00 ^ 25 caeao extract 26.00 coffee extract 10.00 ethyl alcohol 20.00 water U1.90

The above aroma is incorporated into model "filter" 20 cigarettes in an amount of 0.1% · 1/3 of these model cigarettes are treated in the tobacco section with the mixture of 1-acetyl-1-methallyl-3,3-dimethylcyclohexane and 1 - (2-methallyl-5-methyl-1-pentenoyl) -3,3-dimethylcyclohexane, obtained according to Example XV, in an amount of 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-1-pentenoyl) -3,3-dimethyl-8304147 * * 55.

5 ’5 cyclohexane in an amount of 2 x 10; g and 3 x 10 g.

Evaluation by paired comparison reveals that the cigarettes treated as much in the tobacco as in the filter are treated with the mixture of 1-acetyl-1-methallyl-3,3-dimethylcyclohexane and 1- (2-methallyl-5-methyl-1 *). -pentenoyl) -3,3-dimethylcyclohexane in the smoke aroma have a green, sweet, fruity, blossom-like and virginia tobacco-like aroma and aroma nuance in the main stream and in the side stream when smoking and, moreover, before smoking.

Example xxn j A tobacco mixture is prepared by mixing the following materials: ingredient by weight; Light 1 * 0.1

Burley 2U, 9 ^ Maryland 1.1

Turkish 11.6 stem (smoke-dried) 11 *, 2 glycerol 2.8 water 5.3 * This tobacco is used for the manufacture of cigarettes and the following composition is composed and component contained in each of these cigarettes parts by weight of ethyl butyrate 0, 05 ethyl valerate .0.05 maltol 2.00 cocoa extract 26.00 coffee extract 10.00 ethyl alcohol 20.00 2q water 1 * 1.90

The above aroma is incorporated into model "filter" cigarettes in an amount of 0.1%. One third of these model siga rettes are treated in the tobacco section with 1-acetyl-1-methallyl-3,3-dimethylcyclohexane, obtained according to example χχ , in an amount of 100 ppm per cigarette. Another third of these model cigarettes, jP * in the filter is treated with 1-acetyl-1-methallyl-3,3-dimethylcyclo- • 3304347 _____ ^ 56 ·

' · A

hexane in an amount of 2 x 10 7 g and 3 x 10 g. Judgment by paired comparison reveals the cigarettes which have been treated both in the tobacco and in the filter with 1-acetyl-1-methallyl-3.3- dimethylcyclohexane, with respect to smoke aroma, has a green, sweet, fruity, blossom-like and virginia tobacco-like aroma to have an aroma nuance in the main stream and in the side stream when smoking and in addition for smoking.

Example xxm

A tobacco mixture is prepared from the following ingredients: 10 parts by weight

Light U0.1 3urley 2.19 I. Maryland 1.1

Turkish 11.6 15 stem (smoke-dried) 1U, 2 glycerol 2.8 water 5.3

This tobacco is used in the manufacture of cigarettes and the following composition is formulated and incorporated into each of these cigarettes.

ingredient parts by weight ethyl butyrate 0.05 ethyl valerate 0.05 maltol 2.00 25 cocoa extract 26.00 coffee extract 10.00 ethyl alcohol 20.00 water U1.90

The above aroma is included in model "filter" 30 cigarettes in an amount of 0.1%. One third of these model cigarettes are treated in the tobacco section with 1-acetyl-1-methallyl-3β-dimethylcyclohexane, obtained according to a of Examples XVII, VEII or IX, in an amount of 100 ppm per cigarette Another third of these model cigarettes are treated in the filter with the 1-acetyl-1-methallyl-3,3-dimethylcyclohexane in an amount of O '7 A = ¾ * '57 ♦ * -5-5 of 2 ς 10 and 3 x 10 g When paired comparison evaluates the cigarettes treated blow as much into the tobacco as into the filter with 1-acetyl-1-methallyl-3.3 -dimethylcyclohexane in the smoke aroma has a green, sweet, fruity, blossom-like and virginia tobacco-like aroma and aroma nuance in the main stream and in the side stream when smoking and, moreover, before smoking.

Example XXIV

Orange pulp aroma composition

An orange flavor composition is prepared by mixing: components parts of natural orange oil 13.00 C 'acetaldehyde 1.50 ethyl acetate 0.10. You ethyl butyrate 0.50 propanal 0.10 trans-2-hexenal 0.10 ethyl alcohol (95%) 60 0.00 Fusel Oil 0.05-20 Propylene Glycol 2U, 65 - This is referred to as aroma "A". A second composition, aroma "B, t is prepared by adding 1-acetyl-1-methallyl-3,3-dimethylcyclohexane (1% in ethanol) to one part of flavor" A "in an amount of 2 parts to 100 parts aroma "A".

Each of the flavors "A" and "B" is added at a rate of 25 2 ounces per gallon of 32 ° Baumê sugar syrup to obtain a syrup which can be combined with water to make a beverage. The drink, which is prepared with aroma MA, f, is a reasonable orange drink with good character, aroma and intensity.

2Q The beverage prepared with aroma "B" has a much improved aroma. The improvement by the 1-acetyl-1-methallyl-3,3-dimethylcyclohexane is due to: 1. A greater degree of natural character of freshly squeezed orange juice and 2 ^ 2. Greater depth of the orange juice flavor.

8? Ή 1 4 7 «58 •

Example XXV

Perfume composition

A perfume composition is prepared by mixing ingredients parts 5 Linalool 30

Linalyl acetate 10

Terpineol coeur 5

Nerol coeur 10

Terpinylacetate 2 10 Geranyl acetate 2

Uryl acetate 2

Methyl anthranilate 1 'Citral 10 n-decyl alcohol 1 15 n-dodecyl alcohol 5 n-dodecanal 15 n-decanal 30 n-nonanol 3 n-nonanal 5 20 n-decyl acetate 5 n-dodecyl acetate 3 1-acetyl-1-methallyl-3,3-dimethyl cyclohexane (obtained according to example 'xvi) 5

The 1-acetyi-1-methallyl-3,3-dimethylcyclohexane provides -25 (a natural, tart, bland apple character to this orange perfume composition without terpenes.

Example χνττ

The reaction proceeds according to scheme X.

A slurry of 156 g (1 mole 1-acetyl-3,3-dimethylcyclohexane, 5 Λ J 86 g (1.5 mole) potassium hydroxide and 300 ml toluene is heated to reflux. 11U g (1.5 mole) allyl chloride is added added to the thickened reaction mass, after which the mass becomes more liquid, the mixture is heated under reflux for 62 hours, after which the reaction mass is cooled to room temperature and 500 ml of water are added, the aqueous layer is discarded and the organic layer is distilled, 8304147 * '59 * j- -r>, to obtain 7U g of recovered 1-acetyl-3,3-dimethylcyclohexane, 53 g of 1-acetyl-3,3-dimethyl-1 - (2-propenyl) cyclohexane and 35 g of 3,3-dimethyl-1- (U-pentenoyl} cyclohexane.

The HMR spectrum for the 1-acetyl-3,3-dimethyl-1-5 (2-propenyl) cyclohexane is shown in FIG. 15. The infrared spectrum is shown in Figure 16.

The HMR analysis leads to the formula 3U

8.pom interpretation 0.7U (s, 3)

1090 (s> 3) methyl groups V

2.1U (s, 3) CH group "B" / '____ 8.ppm interpretation M -> 5.1 (m, 2) CH2 group "C" 5, U—> 5.8 (m, 1) Ηρ The infrared analysis is as follows: C = 0; 1690 cm ”* C = C; 1660

The mass spectral analysis is as follows: m / e * 95, 9 ^, 69, Ui, 109, 55, 191 * (main peak).

The HMR analysis for 3,3-dimethyl-1 - (U-pentenoyl) cyclohexane is shown in Figure 17 and leads to the formula 35 θ, -ppm interpretation 0.90 (s, 3) 0.93 (s, -3 ) methyl groups "A" 25 2.2 -> 2.65 (m, 5) CH2's "B” βηΗβ MO - 5.12 (m, 2) CH2 "D" 5.50 - 5.95 Cm, 1) Hg ___ »____ ______

The mass spectral analysis is as follows: 30 m / e = 69, 111, 55, Ui, 83, 139, 19U (main peak).

r 33 C '* 60 Λ

Example χχνιι

The reaction proceeds according to schedule Y. «

A mixture of 156 g of 1-acetyl-3,3-dimethylcyclohexane (1 mol), 60 g of sodium hydroxide (1.5 mol), 11U g of allyl chloride (1.5 mol) and 10 g of triethylamine was stirred and at 80-8U for 12 hours. ° C heated. The reaction mass was cooled to room temperature. Water was added with stirring and the aqueous layer was discarded. The organic layer was distilled to give 119 g of 1-acetyl-3,3-dimethylcyclohexane, 31 g of 1-acetyl-3,3-dimethyl-1- (2-pentenyl) cyclo-10 hexane and 5 g of 3-dimethyl-1 - (1 + -pentenyl) cyclohexane.

The HMR spectrum for 1-acetyl-3,3-dimethyl-1- (2-propenyl) cyclohexane is shown in fig. 15 · The infrared spectrum is shown in C in fig. 16. The HMR spectrum for 3,3-dimethyl-1 - (^ - pentenoyl) cyclohexane is shown in Fig. 17-15

The reaction proceeds according to scheme Z.

A fresh solution of potassium t-butoxide is prepared by adding 28 g of potassium metal (0.72 mol) under a nitrogen blanket to 500 ml of anhydrous t-butanol. To this is added 1-acetyl-3,3-dimethylcyclo-20 hexane and the resulting mixture is stirred at room temperature for 1 hour. 63.2 g (0.8 mol of allyl chloride are added and the reaction mixture is stirred 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 obtain 8 g of a 13: 1 mixture of 1-acetyl-3,3-dimethyl-1- (2-propenyl) cyclohexane and 3,3-dimethyl-1- (U-pentenoyl) cyclohexane (ratio determined by integration of GLC chromatogram. GLC conditions: 10 'x 1 / V 10% SE packed column, 200 ° C isothermal) and 1 * 1 g non-volatile material.

The HMR spectrum for 1-acetyl-3,3-dimethyl-1- (2-propenyl) cyclohexane is shown in Fig. 15. The infrared spectrum is shown in Fig. 16. The HMR spectrum for 3,3-dimethyl-1- (U- pentenoyl) cyclohexane is shown in Figure 17.

35 8304147 · »61 λ *

Example xxix

Preparation of 1-acetyl-3,3- & imethyl- (2-propenyl) cyclohexane

The reaction proceeds according to scheme AA, 5 units of 8¾ g of potassium hydroxide (1.5 moles, 156 g of 1-acetyl-3,3-dimethylcyclohexane (1 mol) and 3 g of dibenzo-18-crown-6 of the formula 16 prepared by the Aldrich Chemical Company of Metuchen, TTev Jersey and 150 ml of toluene is heated to reflux, the reaction mass thickening The mass is cooled by 70 ° C and 10 µl + g (1.5 mole) of allyl chloride is added to give the reaction - mixture becomes more liquid The reaction mixture is heated to reflux for an additional 9 hours, after which the mass is cooled and water is added F. The aqueous layer is discarded and the organic layer is distilled to obtain 2h g of 3,3-dimethylcyclo-hexane. 1 + 8 g of 1-acetyl-3,3-dimethyl-1- (2-propenyl) cyclohexane and 90 g of non-volatile material.

The spectrum for 1-acetyl-3, 3-dimethyl-1 - (2-propenyl) cyelohexane is shown in Fig. 15. The infrared spectrum is shown in Fig. 16.

20 Example xxx

Preparation of 1- (3,3-dimethylcyclohexyl) -1 + -methyl-cis and trans- (2 and 3) -entene-1-one. The reaction proceeds according to scheme SB.

A solution of 1 + 7 g of 1-acetyl-3,3-dimethylcyclohexane, 500 ml of methanol, 1 + 0 g of HaOH and 50 ml of toluene is heated to reflux. 2L + 0g of isobutyr aldehyde are added dropwise over 1 + 5 minutes. The reaction mixture is heated to reflux for an additional 90 minutes, after which 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 two phase mixture.

The organic layer is washed once with water and quickly distilled through a short column to give a mixture of 1 - (3,3-dimethylcylohexyl) -1 + -methyl-cis and trans- (2 and 3) penten-1-one ( 3 & 0 g, 58%) (112-117 ° C, 2.8 mm) and higher boiling products, which are identified as compounds of formulas 1 + 0 and 1 + 1.

8304147 Μ * 62 + 1 *

j V

Redistillate this material by a 1g, T x 12 ”

Goodloe column gave the following fraction

Fraction vapor temperature liquid temperature Vacuum weight reflux temperature (° C) temperature (° C) mm Hg (g) ratio 5 1 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 10 6 112 128 2.8 12.0 9: 1 T 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 15 11 115 137 2.8 26.9 4: 1 12 115 140 2.8 25.7 4: 1 13 116 1119 2.8 25.0 4: 1 14 116 149 2.8 26.9 Us 1 15 117 155 2.8 16.9 4: 1 20 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 25 21 130 219 2.8 25.5 4: 1 V 22 138 241 2.8 25.5 4: 1 23 149 250 2.8 11.7 4: 1

Fraction 5-13 contains more than 99% of the desired product of formulas 42 and 43.

The following fractions contain the following percentages of this mixture.

t 8304147 i 4ft * · »63

-V

Fraction no, -percentage desired -product 3 60 4 90 5-13> 99 5 1¾ 98 15 96 16 90 IT 6θ 18 20 10 The fractions 5-13 have a fruity, woody and slightly nighty aroma with armoise, nuances of hints, from an odor point of view and a weak chocolate undertone.

From an aroma point of view, this material has a sweet, fruity, raspberry, woody, lime, painful aroma with a sweet, raspberry and lime-aroma flavor.

Example XXXI

Preparation of 1- (3,3-dimethylcyclohexyl) -V-methyl-cis and trans (2 and 3) -nenten-1-one

The reaction proceeds according to scheme CC.

A mixture of h62 g of 1-acetyl-3,3-dimethylcyclohexane, 108 g of isobutyraldehyde, 6.2 g of boric acid and 52 g of boron oxide is heated and stirred in an autoclave at 150 ° C for 5 hours. The solution is filtered from inorganic salts and washed three times with 10% HCl.

Distillation gives 319 g of 1-acetyl-3,3-cimethyl-cyclohexane and 138 g of 1- (3,3-dimethylcyclohexyl) -U-methyl-cis and trans- (2 and 3) -pentene-1-one (22 J, calculated to the starting 1-acetyl-3,3-dimethylcyclohexane).

The 1- (3,3-dimethylcyclohexyl) -U-methyl-cis and trans- (2 and 3) -pentene-1-one is examined by ΒΙ-JR and infrared analysis and then appears to be a mixture of compounds of the formulas UU (cis and trans) and ^ 5

The NMR spectrum for this mixture is shown in Figure 18.

The infrared spectrum is shown in fig. 19 ·

The HMR analysis is as follows: 1 8304147 64 ♦ mL. interpretation 1.85 (s) ^ βγ methyl groups "A" 2.62 (d, J 1 Hz) 5 2.76 (a, J - 1 H ") methyl groups" 0 "L · 2.03 (s) methyl groups" B "2.1 (s) 2.3-2.8 (wide multiplet) 3.1¾ (d, J = 7HZ) CH2 group" E "10 5.28 (broad t, J = 7HZ) '6.0 and 6.28 (two multiplets) H_ (i 6.68-6.92 (two multiplets)

The infrared analysis is as follows: 1665 cm "1"

15. 1710 I.

1690 (sch) I ^ ^ 1720 (sch))

1620 cm -1 C = C

Example xxkii v 20 Synthesis of 1- (3,3-dimethylcyclohexyl) -cis and trans- (2 and 3) nenten-1-one

The reaction proceeds according to scheme DD.

A mixture of 62 g of 1-acetyl-3,3-dimethylcyclohexane, 87 g of propionaldehyde, 52 g of boron oxide and 6.2 g of boric acid is heated in an autoclave for 8 hours at 150 ° C. After cooling to room temperature, the solution of the inorganic salts is filtered off, washed once with aqueous sodium bicarbonate and twice with saturated saline. Distillation through a short column gave a mixture of 367 g of 1-acetyl-3,3-dimethyl-cyclohexane and 60 g of 1- (3,3-dimethylcyclo-30-hexyl) -cis and trans- (2 and 3) -pentene-1-one ( 20 calculated on the basis of propion-8304147 - 65% aldehyde (which was used).

A portion of the distillate, which was rich in the desired products, was distilled through a 1.5 "x 12" Goodloe column to give the following fractions: 5 Fraction vapor temperature liquid temperature Vacuum weight reflux temperature (° C) rature (° C) mm Hg (g) ratio 1 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 10 U 82 138 2.0 6.6 U: 1 5 88 138 2.0 3.0 lf: 1 6 90 1U0 2.0 5.3 ^: 1 7 '90 140 2.0 6.7 1 » : 1 8 90 1¾¾ 2.0 6.7 '1 15 9 90 15U 2.0 6.5 U: 1 10 95 181 2.0 7.0 Ui 1 11 93 220 2.0 2.6 U: 1

Fraction 7, at a dosage of 2 ppm, has a sweet, raspberry, fruity, painful, floral, ionic aroma and a sweet, sweet-fruity, red currant, raspberry, painful, floral, ionic fragrance. The mixture of 1- (3,3-dimethylcyclohexyl) -cis and trans (2 and 3) -pentene-1-one is separated by preparative GLC and then corresponds to formula h6 (cis and trans).

The GC-MS profile for this mixture is shown in Figure 20. The HMR spectrum is shown in Figure 21. The infrared v spectrum is shown in Figure 22.

The HMR analysis is as follows: S3 G 4 1 4 7 66 \ δ, npm interpretation 1.95 (s, 6h) CH ^ groups "A" * 2.08 (t, 3, J ^ H ^) CH ^ groups "B" 2.25 (quintet, 2H, J = 8HZ) CH 2 groups "C" 5 2.7-2.9 (step multiplet, 1H) 6.05 and 6.22 (two multiplets) 6.75- 7.05 (η, 1H) Hp (. The infrared analysis is as follows: C = 0 1665 and 1685 cm "1 10 OC 1620.

Example XXXlli

Hydrogenation of 1- (3-3-dimethylcyclohexyl) -U-methyl-cis and trans- (2 and 3) -tentene-1-one.

The reaction proceeds according to scheme EE.

15 "To a 250 cm Parr shaker, 107 g of 1- (3,3-dimethylcyclohexyl) -U-methyl-cis and trans- (2 and 3) -pentene-1-one are prepared, prepared according to Example 1, 1 g of 5 % palladium on charcoal catalyst and 125 g of isopropyl alcohol The Parr shaker is closed and heated to a temperature of 125 ° C at a hydrogen overpressure of 2 to 3.5 kg to 10.5 kg / cm and at that pressure and temperature held for 1§ hour.

v At the end of this 1 hour period, the reaction product is filtered and distilled in a U8 "Vigreaux column. The details of the distillation are as follows: 83 0 4 1 4 7 i ief · 67 •> * f * *

Fraction vapors enroof liquid empe- Vacuum compound reflux no. Rature (° C) rature (° C) mm Hg (g) ratio »_ _ 1 67-89 118-126 2.2 3.8 9: 1 2 91 137 2.2 3.7 9: 1 5 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 10 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 the standpoint of a nutritional flavor, Fraction 6 obtained by distillation has a sweet, painful, fruity, boshes, woody aroma with a sweet, painful, fruity, nut-meat flavor.

From a perfume standpoint, the combined fractions 2-9, in an amount of 10% in food grade alcohol, have developed a weakness; sweet woody aroma with chocolate-like nuances.

Fraction 7 appears to correspond to formula 47 in HMR, infrared and mass spectral analysis.

The HHR analysis gives the following result: S ppm interpretation 0.82-0.98 (m, 12H) groepen ^ groups ... 25. 2.43 (t, 2H, J * 8h ^) methylene "A"

The infrared analysis is as follows: 2950 cm "1 2870 1700.

30 1560 (C = 0) 1390 1360

The mass spectral analysis is as follows: 111, 41, 43, 69, 55 and 27 8304147 * 68 '* *' <„s

The HMR spectrum for this compound is shown in Figure 23. The infrared spectrum for this compound is shown in Figure 2k.

• Example xxxiv 5 Raspberry flavor composition

The following basic raspberry flavor composition is prepared: ingredients by weight vanillin 2.0 maltol 5.0 IQ parahydroxybenzylacetone 5.0 alpha ionone (10% in propylene glycol) 2.0 ethyl butyrate 6.0 ethyl acetate 16.0 dimethyl sulfide 1.0 T5 isobutyl acetate 13.0 acetic acid 10.0 acetaldehyde 10.0 propylene glycol 930.0 1 - (3,3-dinethylcyclohexyl) -U-methyl-cis and trans- (2 and 3) -2o penten-1-one, prepared according to example χχχ , is added to half of the above composition in an amount of 2.0%. The composition with the 1- (3,3-dimethylcyclohexyl) -U-methyl-cis and trans- (2 and 3) -pentene-1-one is compared to the composition without the 1- (3,3-dimethylcyclohexyl) -1 + - methyl cis and trans- (2 and 3) -pentene-1-one in an amount of 0.01% (100 ppm) in water and judged by a group of experts.

The aroma, containing the 1 - (3,3-dimethylcyclohexyl) -U-methyl-cis and trans- (2 and 3) -pentene-1-one, appears to have significantly sweeter aroma notes and a sweet raspberry, raspberry kernel-like 3q and sweet aftertaste and a mouthfeel that is missing from the basic raspberry composition. It is the unanimous opinion of the experts that the substance 1- (3,3-dimethylcyclohexyl) -1 + -methyl-cis and trans- (2 and 3) -. pentene-1-on rounds off the aroma and contributes to a very natural fresh aroma and taste, as is found with fully ripe raspberries.

Therefore, the flavor is evaluated significantly hotter than the 1- (3,3-dimethylcyclo-8304147 * * 69 * hexyl) -k-aethyl-cis and trans- (2 and 3) -pentene-1-one than the flavor without addition of this product.

Example xxxv

Raspberry Flavor Composition 5 The following basic raspberry flavor composition is prepared: components weight parts vanillin 2.0 maltol 5 * 0 parahydroxybenzylacetone 5.0 10 alpha ionone (10% in propylene glycol) 2.0 ethyl butyrate 6.0 ethyl acetate 16.0 (* dimethyl sulfide 1.0 isobutyl acetate 13.0 15 acetic acid 10.0 acetaldehyde 10.0 propylene glycol 930.0

1- (3,3-dimethylcyclohexyl) requirement and trans- (2 and 3) -pentene-XXXXXI

1-one prepared according to Example 1 is added to half of the above composition in an amount of 2.0%. The composition with the 1- (3,3-dimethylcyclohexyl) -cis and trans- (2 and 3) -pentene-1-one is compared to the composition without this product in an amount of 0.01% (100 ppm) in water and assessed by a group of experts.

The flavor, containing the 1- (3,3-dimethylcyclohexyl) -cis and 25 trans- (2 and 3) -pentene-1-one, appears to have a significantly sweeter aroma and furthermore a sweet raspberry, raspberry kernel-like and sweet aftertaste and a mouthfeel that is missing from the basic raspberry composition. It is the unanimous opinion of the experts that the product rounds off the aroma of 1- (3,3-dimethylcyclohexyl) -cis and trans- (2 and 3) -pentene-1-30 and contributes to a very natural fresh aroma and taste, such as found in fully ripe raspberries. Therefore, the flavor with the addition of 1- (3,3-dimethylcyclohexyl) -cis and trans- (2 and 3) -pentene-1-one is rated as significantly better than the flavor without this product.

358304147 70 (a 9 * *>

Example XXXVI

A. Powder Flavor Composition *> 20 g of the flavor composition of Example XXXIV is emulsified in a solution of 300 g of acacia gum in TOO g of water. The emulsion is spray dried with a Bowen Lab Model Drier using 260 c.f.m. air with an inlet temperature of 500 ° F, an outlet temperature of 200 ° F, and a wheel speed of 50,000 revolutions per minute.

B. Persistent released aroma 10 The following mixture is prepared: components parts by weight

Liquid raspberry flavor position of example xxxiv '20 propylene glycol 9

Cab-0-Sil® M-5? (silica blend sold by the Cabot Corporation 125 High Street, Boston, Mass.

Physical properties: 2 20 specific surface area: 200 ia / g nominal particle size 0.012 micron density: 2.3 Lbs / cu.ft 5 »00

The Cab-O-Sil is dispersed in the liquid raspberry flavor composition of Example 1 with vigorous stirring to give a viscous liquid. 71 parts by weight of the powder flavor composition of Part A above are then mixed with the viscous liquid with stirring at 25 ° C and for 30 minutes to obtain a dry, free flowing powder with sustained release flavor.

Example XXXVII

^ 10 parts by weight of 50 Bloom pigskin gelatin are added to 90 parts by weight of water at a temperature of 150 ° C. The mixture is stirred until the gelatin is completely dissolved and the solution is cooled to 120 ° F. Parts of the liquid aroma composition of Example xxxv are added to the solution and it is then homogenized to obtain an emulsion. particle size is typically between 2 and 5 microns. This material is kept at a temperature of 120 ° C, under which conditions the gelatin does not gel. The confluence is induced by slowly and steadily adding parts by weight of the 20% aqueous sodium sulfate solution. 8304147 * "71 * ν ·» ν * ». During the confluence, the gelatin molecules are evenly deposited to every oil droplet at its core.

Gelling is done by pouring the heated confluent mixture into 1000 parts by weight of a T% 1s aqueous sodium sulfate solution at 65 ° F. The resulting gelled, fluxed material can be filtered and washed with water at a temperature below the melting point of gelatin to remove the salt.

In this example, the filtered cake is cured by washing with 200 parts by weight of 37% aqueous solution of formaldehyde. The cake is then washed to remove excess formaldehyde.

Example. xxxvm

Chewing gum 100 parts by weight of "chide" are mixed with U parts by weight of the aroma prepared according to example. 300 parts of sucrose and 100 parts of corn syrup are added. Mixing is done in a sidewall belt mixer with a jacket, of the type manufactured by Baker Perkins Co.

The chewing gum mixture obtained is then processed into 20 strips with a width of 2.5 cm and a thickness of 2.5 mm. The strips were cut into pieces with a length of 7.5 cm each. When chewed, the chewing gum has a pleasant and long-lasting raspberry flavor.

Example, ΧΧΧΙΧ

Chewing gum 100 parts by weight of chicle are mixed with 18 parts by weight of the flavor, prepared according to example L. Then 300 parts of sucrose and 100 parts of corn syrup are added. The mixing is done in a jacketed mixer of the type , which is manufactured by Baker Perkins Co.

The chewing gum mixture obtained is then processed into strips with a width of 2.5 cm and a thickness of 2.5 mm. These strips are cut into pieces just 7.5 cm long each. Chewing gum has a pleasant and long-lasting raspberry flavor.

t 83041 ^ / 35 * 72 * * »

t * «F

* Λ

Example xl

Toothpaste composition

The following separate groups of ingredients are prepared: 5 parts by weight of ingredients group "A" 30,200 glycerol 15,325 distilled water 0,100 sodium benzoate 10 0,125 saccharin sodium 0,1 * 00 stannous fluoride group "B" \ 12,500 'calcium carbonate 37,200 dicalcium phosphate ^ (dihydrate) group "C" 2,000 sodium N-lauroyl sarcosinate (blowing agent) group "D" 20 1,200 aroma material of

example XXXVI

100.00 (total)

Method: 1. The ingredients in group "A, f are stirred and heated to 160 ° F in a steam jacketed kettle.

2. Stirring is continued for an additional 3-5 minutes to form a homogeneous gel.

3. Group "B" powders are added to the gel and mixed until a homogeneous paste is formed.

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

5. The resulting slurry is then mixed for one hour. The. finished pasta is transferred to a three-roll and then homogenized and finally placed in tubes.

When the obtained toothpaste is used in normal toothbrushing, a pleasant raspberry flavor is obtained with a constant, strong intensity throughout the treatment (1 to 1.5 minutes). v Example XL ·!

Chewable vitamin tablets

The flavoring material obtained according to the method of Example L is added to a pourable vitamin tablet composition in an amount of 10 g per kg, which pourable vitamin tablet composition is prepared as follows:

The following materials are mixed in a Hobart mixer until a homogeneous whole is obtained: 10 g / 1000 tablets

Vitamin C (ascorbic acid) as ascorbic acid sodium ascorbate mixture 1: 1 70.0 r Vitamin B .-. (Thiamine nononitrate) as Rocoat1® thiamine nononitrate 33 1/3%

15r (Hofflnan La Hoche) U, Q

Vitamin B (iriboflavin) as Rocoat © riboflavin 33 1/3% 5.0

Vitamin B (pyridoxine hydrochloride) as Rociat pyridoxine hydrochloride 33 1/3% U, 0 20 Eiacinamide as Rocoat'S niacinamide 33 1/3% 33.0 calcium pantothenate 11.5

Vitamin 3 ^. (cyanocobalamin) as Merck ü, 1% in gelatin 3.5 25 Vitamin E (dl-alpha tocopheryl acetate) as dry Vitamin E acetate 33 1/3% Roche 6.6 d-Biotin 0.0Uk 'approved colorant 5.0 flavor of example xxxviï (as mentioned above) 30 sweetener - sodium saccharin 1.0 magnesium stearate lubricant 20.0 mannitol gs make up to 500.0

Pre-tablets are prepared by beating with flat surface punching and grinding the obtained products to 1 nesh. Then, 13.5 g of dry vitamin A acetate and 0.6 g of vitamin D are added in a form of granules. The whole mixture is then compressed with concave punches into products of 0.5 g each.

Chewing the obtained tablets gives a pleasant, long-lasting and always strong raspberry flavor over a period of 12 minutes.

A 1 '7 * - 74 - r

Example XLII

A perfume composition is prepared by mixing the following ingredients in the amounts indicated. 5 Ingredients Amount (g) n-decylaldehyde 1 n-dodecylaldehyde 2 methylnonylacetaldehyde 0.5 10 linalool 50 linalyl acetate 70 phenylethyl alcohol 100

Petigrain SA 20

Bergamot oil 30 15 alfamethyl ionone 25 t 3304147 »Ύ 75 y / component quantity (g):. 1- (3,3-dimethylcyclohexyl) -U-methyl-cis and trans- (2 and 3) -pentene-1-one obtained according to Example XXII-10 cyclic bicyclo C-12 material obtained according to Example IV of the Canadian Patent 85½,225 5 isobornylcyclohexyl alcohol 10 10 benzyl acetate 25 2-n-heptyl cyclopentanone 5 353.3 (total)

The mixture in question is assessed and appears to have a high degree of richness and persistence with regard to the new natural amber quality. This base composition can be mixed with aqueous ethanol, cooled and filtered to obtain a ready fragrance water. The fragrance water thus prepared has an amber aroma, which rests against a woody amber nut with an excellent armoise nuance. The base composition can also be used to make soap or other toiletries fragrant, such as lotions, aerosols, pollinators and the like.

Example XDIII

Preparation of a cosmetic parent composition A cosmetic powder is prepared by mixing 100 g talcum powder with 0.25 g 1- (3,3-dimethylcyclohexyl) -U-methyl-cis and trans- (2 and 3) -pentene-1 in a ball mill. -on, prepared according to example χχχι It has an excellent painful, woody, blossomy and fruity aroma.

Example xliv 30 Scented liquid detergent

Concentrated liquid detergents (lysine salt of n-dodecylbenzene sulfonic acid, as described in U.S. Patent 3,98,818) with a painful, woody odor are prepared * by 0.10 lb, 0.15% and 0.20% 1- ( Add 3,3-dimethylcyclohexyl) -U-methyl-cis and trans- (2 and 3) -pentene-1-one, prepared according to example xxxi.

They are prepared by the appropriate amount of 1- (3,3-dimethylcyclohexyl) - ^ 3 3 C "v 1 4? 76 • add methyl-cis and trans- (2 and 3) -pentene-1-one and mix homogeneously in the liquid detergent. The detergents all have a painful, woody odor, the intensity of which increases with higher concentrations of 1- (3,3-dimethylcyclohexyl) -1-methyl-cis and 5 trans- (2 and 3) -pentene-1-one.

Example yt.v

Preparation of an odor water and a handkerchief perfume 1 (3,3-dimethylcyclohexyl) -U-methyl-cis and trans- (2 and 3) -pentene-1-one, prepared according to the procedure of example wordtι, is added in an odor water incorporated at a concentration of 2.5% in 85% aqueous ethanol and in a handkerchief perfume at a concentration of 20% in 95% aqueous ethanol. A clear and certain painful, ". woody scent is provided to the fragrance water and to the handkerchief perfume.

Example xlvi Preparation of a fragrance water and a handkerchief perfume.

The composition of Example xlh is taken up in a fragrance water at a concentration of 2.5% in 85% aqueous ethanol and in a handkerchief perfume at a concentration of 20% in 95% aqueous. ethanol. The use of 1- (3,3-dimethylcyclohexyl) -U-methyl-cis and 20 trans- (2 and 3) -pentene-1-one in the composition of Example verschaftι provides a clear and definite powerful anber aroma with painful, woody notes to the handkerchief perfume and the perfume.

Example xlvii

Preparation of a sea composition. " 100 g of soap flakes are mixed with 1 g of 1- (3.3-dimethyl)

^ cyclohexyl) -U-methyl-cis and trans- (2 and 3) -pentene-1-one of Example XXXI

until an almost homogeneous composition is obtained. The perfumed soap composition exhibits an excellent woody, pain-like aroma Example xlviii 30 Preparation of a detergent composition

A total of 100 g of detergent powder (lysine salt of n-dodecyl-benzenesulfonic acid, as described in U.S. Pat. No. 3,9½ 818) is mixed with 0.15 g of the 1- (3,3-dimethylcvclohexyl) -h-methyl-cis and trans ( 2 and 3) -pentene-1-one from Example 1 until a substantially homogeneous composition is obtained. This composition has an 8304147 f * 77. * * $ / · Excellent woody, onion-like aroma.

Example XLix

.V

Preparation of 1- (3,3-dimethylcyclohexyl) -cis and trans- (2 and 3) -butene-1-one. The reaction proceeds according to scheme FF.

A mixture of 616 g of 1-acetyl-3.3- <umethylcyclohexane (k mole), 132 g of acetaldehyde (3 moles), 105 g of boron oxide (1.5 moles) and 12 g of boric acid (0.2 moles) is placed in a autoclave heated at 150 ° C. After cooling to room temperature, the solution is filtered off from inorganic salts, washed once with aqueous sodium carbonate and twice with saturated saline. Short column distillation gives 127.2 g of 1-acetyl-3,3-dimethylcyclohexane and 127.2 g of a mixture of 1— (3,3-dimethylcyclohexyl) -cis and trans-2-buten-1-one and 1- ( 3,3-dimethylcyclohexyl) -3-buten-1-one.

Part of the distillate, which was rich in the desired products, was distilled through 1 "x 12" Goodloe column to give the following fractions.

Fraction vapor temperature - liquid temperature - Vacuum weight reflux-no. rature (° C) rature (° C) (mm Hg) (g) ratio 20 i 67-70 89-91 MU, 7 37.9 2: 1 2 70 95 4.9 ^ 0.9 2: 1 3 70 103 5.0 1 + 0.1 2: 1 k 7¼ 113 5.0 29.9 2: 1 5 100 116 5, ¾ 16.7 9: 1 25 6 102 123 M 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 10Ï4. 15¾ 5.2 13.3 9: 1 30 11 10k 179 5.3 11.3 9: 1 12 100 202 5.2 6.7 9: 1 The combined fractions 6-10 at 2 ppm have a cedar wood aroma and a sweet , plant root beer-like cedar wood scent.

The mass spectral analysis is as follows: 35 180/69, It1, 39, 55, 165, 27.

3304147 '♦ * * * *

The NMR spectrum (for fraction 9) is shown in FIG. 25.

The infrared spectrum for fraction 9 'is shown in Fig. 26.

The NMR analysis is as follows:

0.9 ^ pn (s) gem dimethyl protons ÖH

5.1, TU - 1.08 (m) - CHg - 8H

1.90 (doublet with ^ \ allylic „

coupling) CH ^ - C = C - C - 3 H

10 (m), 2

HC-C-1H

f '6.18 (broad doublet) 0.

ti ii t

-0-0 = 0-1 H

7.0U6.70 (m) 0H

15 - C -C = C - 1H

The IR analysis is as follows: 960 cm -1, 1290, 1360, 1380, 1UU0, 1625, 1670, 1690, 2860, 29 ^ 0.

Example L

Hydrogenation of 1 - (3,3-dimethylcyclohexyl) -cis and trans- (2 and 3) -butene-1-one_

The reaction proceeds according to schedule GG.

O

(In a 250 cm Parr shaker, 107 g (6 mol) of 1- (3,3-dimethylcyclohexyl) -cis and trans- (2 and 3) -butene-1-one are prepared according to Example 1.1). g 5% palladium-on-charcoal catalyst and 125 g isopropyl alcohol The Parr shaker is closed and heated to a temperature of 125 ° C at a material pressure of 3.5 - 2 10.5 kg / cm and at that temperature and pressure held for 1.5 hours.

After the end of the 1.5 hour period, the reaction product is filtered off, the solvent is removed in vacuo and the residual oil is distilled on an 8-dish Vigreaux column. The distillation gives the following result: t 8304147 _ ___________________ * * 79. sr ^ *

Fraction vapor temperature liquid temperature Vacuum weight reflux no. Temperature (° C) temperature (° C) (mm Hg) (g) ratio 1 86-89 100 h, 6 9.0 11: 1 2 90 102 bfT 12.0 11.1 53 90 102 k, 6 8.8 11: 1 U 90 102 U, 7 11.5 11 *, 1 5 90 105 M 1 ^, 0 11: 1 6 90 110 U, 6 13.5 11: 1 7 90 113, bt6 8, ¾ 11: 1 10 8 90 1M U, 6 11.1 11: 1 9 90 205 h, 6 M 11: 1

From a perfume standpoint, Fraction 7 at a concentration of 10% in food grade alcohol has a fruity, berry-like, spicy aroma with green, tobacco nuances.

The mass spectral analysis is as follows: 182/111, 69, U3, ^ 1, 71, 55, 27.

The NMR analysis is as follows (fraction 8):

0.90 ppm (t) CH2 -CH2-3H

1.91 npm (s) dimethyl protons 6 H

20

T, 95-1.16 (m) - GH2 - 10H

2, k9 (t) 0

- CH2 - C12 - C - 2 H

0 f * »

2.69-2.31 (m) HC-C-1H

The IR analysis (fraction 8) is as follows: 1020 cm -1, 1120, 1175, 1290, 1360, 1375, 1U00, 1U55, 1705, 2860, 2930.

. The HMR spectrum for this compound (fraction 8 is shown in Figure 27) and the infrared spectrum for this compound 30 (fraction 8) is shown in Figure 28f * 83041 * 7 '♦ 80

Example Li

A perfume composition is prepared by mixing the following ingredients in the amounts indicated: ingredients amount (g) 5 n-decylaldehyde 1 n-dodecylaldehyde 2 methylnonylacetaldehyde 0.5 linalool 50 linalyl acetate 70 ΊΟ phenylethyl alcohol 100

Petigrain SA 20

Bergamot oil 30 alpha methyl ionone 25 1- (3,3-dimethylcyclohexyl) -JU butan-1-one, obtained according to Example 10 / cyclized bicyclo C-12 material, obtained according to Example IV of Canadian patent 85U 225 5, Obornylcyclohexyl alcohol 10 2-benzyl acetate 25 2- n-heptylcyclopentanone 5 353.3 (total)

The said mixture is evaluated and appears to have a high degree of richness and persistence with regard to the new natural amber quality. This base composition can be mixed with aqueous ethanol, cooled and filtered to obtain a ready fragrance water. The odor water thus obtained has an amber aroma, which leans against a woody amber nut with excellent fruity and spicy nuances. The base composition can also be used to flavor soap or other toiletries such as lotions, aerosols, spray formulations and the like.

Example Lil

Preparation of a cosmetic powder conosition. A cosmetic powder is prepared by mixing in a ball mill 2 ^ 100 g talc powder with 0.25 g 1- (3,3-dimethylcyclohexyl) -butane-1-one, prepared according to example L. It has an excellent fruity, 8304147 81 * t "berry-like, spicy aroma with green and tobacco nuances.

* Example lazy

Scented liquid detergent

Concentrated liquid detergents (lysine salt of n-dodecylbenzene sulfonic acid according to U.S. Patent 3,98,818) with a spicy fragrance are prepared containing 0.10, 0.15 and 0.20% 1 - (3,3-dimethylcyclohexyl) butane -1 -on. prepared according to Example L. This is done by adding the appropriate amount of 1- (3,3-dimethylcylohexyl) -butan-1-one to the liquid detergent and mixing it homogeneously. The detergents all have a spicy fragrance with green and tobacco nuances, the intensity increasing with higher concentrations of 1- (3,3-dimethylcylohexyl) -but-1-one.

f «i. Example. liv.

Preparation of a fragrance water and a handkerchief perfume ^ 1- (3,3-dimethylcyclohexyl) -butan-1-one, prepared according to Example L, is taken up in a fragrance water at a concentration of 2.5% in 85% aqueous ethanol and in a handkerchief perfume at a concentration of 20% in 95% aqueous ethanol. A clear and defined spicy aroma is provided to the fragrance water and to the handkerchief perfume.

Example lv

Preparation of a perfume and a handkerchief perfume

The composition of Example LI is taken up in a fragrance water at a concentration of 2.5% in 85% aqueous ethanol and in a handkerchief perfume at a concentration of 20% in 95% aqueous ethanol.

%

EXAMPLE IV 20 Preparation of a soap composition 100 g of soap flakes are mixed with 1 g of 1- (3,3-dimethyl-cyclohexyl) -butan-1-one according to Example L until a substantially hamene composition is obtained. The perfumed soap composition shows a clearly fruity, berry-like, tobacco aroma with green and tobacco nuances.

3 ^ * Λ i 4 7 35 82, * m • 'fi

Example LVII

Preparation of a detergent composition

A total of 100 g of detergent powder (lysine salt of n-dodecyl-benzenesulfonic acid, as described in U.S. Patent No. 3,9 ^ 8.818) is mixed with 0.15 g of the 1- (3,3-dimethylcyclohexyl) -butan-1-one of Example L until an almost homogeneous composition is obtained. The composition has an excellent fruity, berry-like, spicy aroma with green and tobacco nuances.

Example tVIII

IQ Preparation of 1-allyl-U- (U-methyl-3-pentenyl) -3-cyclohexene-1-carboxaldehyde and 1-allyl-3- (3-methyl-3-pentenyl) -3-cyclohexene-1- carboxaldehyde The reaction proceeds according to scheme HH.

A slurry containing 289 g of allyl chloride, 180 g of granular jou sodium hydroxide, UOO ml of toluene, 25 g of aliquat 336® and 576 g of a mixture of U- (U-methyl-3-pentenyl) -3-cyclohexene-1-carboxaldehyde and 3 - (- - methyl-3-pentenyl-3-cyclohexene-1-carboxaldehyde is heated under reflux for 7 hours. To the cooled reaction mass, water is added and the resulting organic phase is separated and washed twice with water. Distillation by short column gives an oil containing 381 g (55%) of product with a boiling point of 11 DEG-100 DEG C. at 1.5 mm. The product is purified by fractional steam distillation in vacuo through a 1 "x 12" filled Goodloe column ( boiling point 113-120 °, 1.5 mm at a steam speed of 1.6 mm liquid HgO / min.).

^ 22 (see Schedule II).

The HMR data for the obtained mixture are the following i 6, ppm interpretation 1.08 (3, s) j 02 s methyl groups "a" 1.79 (2, d, J = Hz) methylene groups "b" 0

9.05 (1, s) -C-H

8304147 e 83 * »ƒ · *

The infrared data for the mixture are as follows: 1712 ca-1 \> 0 1630 cm ”" * ~ * C = Cy / >>

The mass spec data are as follows: fcl, 69, 93, 39, 91, 79

The NMR spectrum for the reaction product is shown in Figure 29 and the infrared spectrum is shown in Figure 30.

Example t.tt

A perfume composition is prepared by mixing the following ingredients in the indicated amounts of ingredients amount (g) r n-decalvaldehyde 1 ^ n-dodecylaldehyde 2 methylnonylacetaldehyde 0.5 linalool 50 linalyl acetate 70 f enylethyl alcohol 100

Petigrain SA 20

Bergamot oil 30 alpha methyl ionone 25 a mixture of the 1 - (2-propenyl) - (- - methyl-3-pentenyl) -A 2 -cyclohexene-1-carboxaldehyde, prepared according to Example VIII 10 cyclic bicyclo C-12 material obtained according to example IV of Canadian patent 85 ^ 225 5 isobornylcyclohexyl alcohol 10 benzyl acetate 25 2-n-heptyl cyclopentanone 5 353.3 (total)

This mixture is assessed and appears to have a high degree of richness and persistence with regard to the new natural fruity quality. This base composition can be "mixed with aqueous ethanol, chilled egg filtered to obtain a ready fragrance water. The fragrance water thus prepared has a fruity aroma, leaning against a lavender-like note. The base composition can also be 5 H 0 k 1 4 7 i * £ ____ 84 are used to make soap or other toiletries such as lotions, aerosols, pollinators and the like.

Example JLX

Preparation of a cosmetic powder composition 5 A cosmetic powder is prepared by mixing 100 g talcum powder in a ball mill with 0.15 g of the (1- (2-propenyl) - (U-methyl-3-)

O

pent enyl) -Δ-cyclohexene-1-carboxaldehyde (s) obtained according to example LVIII, It has an excellent fruity, lavender note with citrus and balm nuances.

10 Example LXI

Scented liquid detergent

Concentrated liquid detergents with fruity, lavender-like nuts and citrus and balsam nuances (which detergents are prepared from the lysine salt of n-dodecylbenzenesulfonic acid, as described in U.S. Pat. No. 3,98,818) which are prepared 1 - (2-propenyl) - (U-methyl-3-pentenyl) -ΔΔ-cyclohexene-1-carboxaldehydes prepared according to example lviii. This is done by adding the respective carboxaldehydes to and mixing homogeneously in the appropriate amount with the liquid detergent. The detergents 2q all have a fruity, lavender-like note with citrus and balm nuances, the intensity increasing with higher concentrations of 1- (2-propenyl) - (U-methyl-3-pentenyl) -Δ-cyclohexene- 1-carboxaldehydes.

Example lxii.

Preparation of a fragrance water and a handkerchief perfume The 1- (2-propenyl) - (^ - methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehydes, prepared according to the method of Example LVIII, are taken up in a fragrance water in a concentration of 2.5% in 85% aqueous ethanol and in a handkerchief perfume in a concentration of 20% in 95% aqueous ethanol. A clear and defined fruity, lavender-2q like note with citrus and balm nuances is provided with the fragrance and handkerchief perfume.

Example LXIII

Preparation of a perfume and a handkerchief perfume 35 r) - λ * ί * - * 85. r · + ƒ *

The use of the 1 - (2-propenyl) - (4-methyl-3-pentertyl) -Δ-cyclohexene-1-carboxaldehydes in the composition of example lix provides a clear and defined fruity, lavender note with 5 citrus and balsam nuanese on the handkerchief perfume and the perfume.

Example 1xiv

Preparation; from a sea composition 100 g of soap flakes are mixed with 2 g of the composition of Example 1 xix until a substantially homogeneous whole is obtained. The perfumed soap composition shows a clear fruity, lavender-like note with citrus and balsam nuuan.

Example LXV.

Preparation of a detergent composition

A total of 100 g of detergent powder (lysine salt of n-dodecyl-15 benzenesulfonic acid, as described in U.S. Pat.

3, 8, 8, 818) is mixed with 0.70 g of the composition of Example LIX until a substantially homogeneous whole is obtained. This composition has an excellent fruity, lavender-like note with citrus and balsam nuuan. Example LXVI

20 Bas is chocolate flavor composition

The following basic chocolate flavor composition is prepared. Components by weight parts of dimethyl sulfi 1.0 isobutyl acetate 1.0. 25 isoamyl acetate 1.0 \ phenylethyl acetate 0.5 diacetyl (10% in ethanol) 0.5 furfural (50% in propylene) 0.5 isoamyl alcohol 1.0 30 gamma-butyrolactone 5 »0 acetophenone 0.5 benzaldehyde 1.0 phenylacetic acid 2.0 maltol 3.0 35 acetaldehyde 2.0 8 ^ 04 147 86.

v ¥

* 'V

ingredients parts by weight isobutyraldehyde 8.0 i sovaleraldehyde 15 »0 phenylethyl alcohol 8.0 ^ vanillin 15» 0 propylene glycol ^ 0.0 100.0 (total)

To the above chocolate composition, 15 wt.% Of the mixture of 1-allyl- (- - methyl-3-pentenyl) -3-1q cyclohexene-1-carboxaldehyde and 1-allyl-1-3- (3-methyl) is added -3-pentenyl) -3-cyclohexene-1-carboxaldehyde, which is formed according to example "LVIII. Part of the composition does not contain such an additive. The composition with the 1-allyl- (H-methyl-3-pentenyl) 3-cyclohexene-1-carboxaldehyde is compared to the composition without these compounds Ij in water at 5 ppm and by group of experts judged The opinion of this group was unanimous that the flavor with the compounds 1-allyl- (1-methyl-3-pentenyl) -3-cyclohexene-1-carboxaldehydes, in an amount of 15% t, is the characteristic cocoa butter-like aroma and the characteristic taste.

When the compound 1-allyl- (U-methyl-3-pentenyl) -3-eyclohexene-1-carboxaldehyde is added to the same base chocolate composition in an amount of 5%, fuller, stronger cocoa powdery notes are produced in aroma and taste compared to the same composition without the compound 1-allyl- (H-methyl-3-pentenyl) -3-25 cyclohexene-1-carboxaldehyde in an amount of 5 ppm in water.

In conclusion, it can be said that the compound 1-allyl- (U-methyl-3-pentenyl) -3-cyclohexene-1-carboxaldehyde surprisingly and unexpectedly and efficiently improves the cocoa and chocolate nuts as well as the cocoa butter properties in chocolate.

Example 1xvii A. Powder aroma composition 20 g of the aroma composition of example LXVI are emulsified in a solution of 300 g of acacia gum in 700 g of water.

The emulsion is spray dried with a Bowen Lab Model Drier, 35, 2β0 c.f.m. air is used with an inlet temperature of §504 I 4 /. V. 87> A.

500 ° F, an exhaust temperature of 200 ° F and a wheel speed of .50,000 revolutions per minute.

B. Persistent release of aroma

The following mixture is prepared: 5 parts by weight parts of liquid chocolate flavor composition of example LXVI 20 propylene glycol 9

Cab-O-sil R M-5 (silica mixture, prepared by 10 de Cabot Corporation 125 High Street,

Boston, Mass.

physical properties _ specific surface area: 200 m / g nominal particle size: 0.012 micron 15 density: 2.3 lbs / cu.ft.) 5.00

The Cab-O-Sil is dispersed in the liquid chocolate flavor composition of Example LXVI with vigorous stirring to obtain a viscous liquid. 71 parts by weight of the powder flavor composition of Part A above are then mixed in said viscous liquid with stirring at 25 ° C and for 30 minutes, thereby obtaining a dry, free flowing powder which gives sustained aroma.

Example LXVIII

10 parts by weight of 50 Bloom pigskin gelatin are added to 80 parts by weight of water at a temperature of 150 ° F. The mixture is stirred until the gelatin is completely dissolved and the solution (cooled to 120 ° F. 20 parts by weight of the liquid aroma composition of Example LXVI is added to the solution, which is then homogenized to form an emulsion with a dssLtj ash size, typically in the range of 2-5 microns, This material is maintained at 120 ° F, under which conditions the gelatin does not gel.

The flow-in is initiated by the slow and uniform addition of 50 parts by weight of a 20% aqueous solution of sodium sulfate. During the confluence, the. gelatin-35 molecules evenly deposited around each oil droplet as a core.

Gelling is effected by pouring the heated confluent mixture into 1000 parts by weight of a 7% aqueous sodium 8304147 88-sulfate solution at 65 ° F. The resulting gelled confluent can be filtered and washed with water at temperatures below the gelatin gel point to remove the salt.

The filtered cake is cured in this example by washing with 200 parts by weight of a 37% formaldehyde solution in water. The cake is then washed to remove residual formaldehyde.

Example LXIX

100 parts by weight of "chicle" are mixed with k parts by weight of the flavor prepared according to Example LXVII. 300 parts of sucrose and 100 parts of corn syrup are added. Mixing takes place in a belt mixer with sidewall jackets, as it is sold (, by Baker Perkins Co.

The resulting chewing gum mixture is then processed into strips 2.5 cm wide and 2.5 mm thick. These strips are cut into pieces with a length of 7.5 cm. When chewed, the chewing gum has a pleasant long-lasting chocolate taste.

Example lxx '

Chewing gum 100 parts by weight of "chicle" are mixed with 18 parts by weight of the flavor, prepared according to example LXVIII. Then 300 parts of sucrose and 100 parts of corn syrup are added. Mixing is done in a belt mixer with sidewall jackets as sold by the Baker Perkins Co.

^. The chewing gum mixture obtained is then processed into strips with a width of 2.5 cm and a thickness of 2.5 mm. These strips are cut into pieces with a length of 7 »5 cm each.

When chewed, the gum has a pleasant and long-lasting chocolate taste.

Example LXXI

30 Toothpaste composition

The following individual groups of ingredients are prepared: 83 0 4.i47 $ 35 * c ** 89 * r * J * * parts by weight of ingredients.

group "A" <* 30,200 glycerol 15,325 distilled water tj parts by weight of ingredients 0,100 sodium benzoate 0,125 saccharin sodium ΟΛΟΟ stannous fluoride group "B" -] q 12,500 calcium carbonate 37,200 dicalcium phosphate (dihydrate) group c.

2,000 sodium H-lauroyl sarcosinate (foaming agent) 15 group "Dw 1,200 aroma material of

example LXVII

100.00 (total)

Method: 1. The constituents in group "A" are stirred and heated to 160 ° P in a steam jacketed kettle.

2. Stirring is continued for an additional 3-5 minutes to form a homogeneous gel.

3. The "Group B" powders are added to the gel 25 ζ with mixing until a homogeneous paste is formed.

k. While stirring, the flavor of "D" is added and finally the sodium n-lauryl sarcosinate.

The slurry obtained is then mixed for one hour. The finished pasta is transferred to a three-roll and then homogenized and finally m tubes processed.

When used with normal toothbrushing, this toothpaste gives a pleasant chocolate taste with constant strong intensity throughout the treatment (1 - 1.5 min.).

8304147 ψ,> '90 η

Example LXXII

Kauvbare vitamin tablets'

The flavor material of Example LXXXII is added to a chewable vitamin tablet composition in an amount of 10 g / kg, which chewable vitamin tablet composition is prepared as follows:

The following materials are mixed in a Hobart mixer until a homogeneous whole is obtained.

g / 1000 tablets

Vitamin C (ascorbic acid) ^ as ascorbic acid-sodium ascorbate mixture 1: 1 70.0

Vitamin - (Thiamine Mononitrate) as Rocoat 0 / Thiamine Mononitrate 33 1/3% (Hoffman La Roche) ^. 0

Vitamin B_ (riboflavin)

Ij as Rocoat® riboflavin 33 1/3% 5.0

Vitamin Br - (pyridoxine hydrochloride) as Rocoat OP pyridoxine hydrochloride 33 1/3% H, 0 niacinamide ^ as Rocoat ® niacinamide 33 1/3% 33.0 20 Calcium pantothenate 11.5

Vitamin B _ (cyanocobalamin) as Merck * 0.1% in 3.5 gelatin

Vitamin E (dl-alpha tocopheryl acetate) as dry vitamin E acetate 33 1/3% Roche 6.6 25 d-biotin 0.0¼ approved lacquer liquid 5 »0 flavor of example LXVIII (as indicated above), sweetener - sodium saccharin 1 Magnesium stearate lubricant 20.0 mannitol q, s. make up to 500.0

Pre-tablets are prepared by beating together with flat-surface punching and comminuting the products to 1U mesh.

Then 13.5 g of dry vitamin A acetate and 0.6 g of vitamin D in granular form are added. The whole mixture is compressed with concave punches to produce products of 0.5 g each.

Chewing the obtained tablets gives a pleasant long lasting, cohesive strong chocolate taste for 12 minutes.

8304147, *. - 91 - * ^ *

Example LXXIII

Tobacco congestion i

A tobacco mixture is prepared by mixing the following ingredients: 5 ingredients by weight - light 1 * 0.1 y Burley 2fc, 9 (; I Maryland 1.1; Turkish 11.6 ^. Stem (just smoke-dried) 1U, 2 y glycerol 2.8 • water 5 * 3 y Cigarettes are made from this tobacco.

i The following flavor composition is prepared: ^ components parts by weight

S

ethyl butyrate 0.05 i; ethyl valerate 0.05 maltol 2.00 cocoa extract 26.00 20 | coffee extract 10.00 | ethyl alcohol 20.00 j water 1 * 1.90 i; The above tobacco arona composition is applied in an amount of 1.0% to all cigarettes manufactured; from the above tobacco composition. Half of the cigarettes are then treated with 500 or 1000 ppm of the mixture

[O

Example 1 consisting of 1-allyl-3 and 1 * - (1 * -methyl-3-pentenyl) -A -: cyclohexene-1-carboxaldehyde. The blank cigarettes containing this mixture 'i! not contain and the test cigarettes containing the mixture, i t ^; are assessed by paired comparison and the results are as follows: i

i I

I The test cigarettes have more smoke "body" and a fuller f * i! smoke "body, f-sensation in the mouth when smoking. The tobacco-like notes i. i 'are enhanced and the aroma of the tobacco when smoking is more aromatic 35 ·. · i; with cocoa liqueur-like, sweet-rich and creamy oily notes.!

| I

! _________________ (8304147 ν '- 92 - ψ Λ

The tobacco from the test cigarettes for smoking has cocoa liqueur-like, salt-rich and creamy oily notes. All cigarettes were evaluated for the smoke aroma with a 20 mm cellulose acetate filter.

5

Example LXXIV

A slurry of 289 g of allyl chloride, 252 g of flaked potassium hydroxide, 400 ml of toluene and 400 g of 18-crown-6-of formula 19 and 576 g of myrac aldehyde is heated to reflux for 3 hours. The reaction mass is treated as in Example 1 to give 287 g of a product consisting of a mixture of compounds of formulas 26 and 27.

Example LXXV

A slurry of 289 g of allyl chloride, 180 g of granular sodium hydroxide, 400 ml of toluene, 40 g of triethylamine and 576 g of a mixture of myracaldehyde is heated under reflux for 8 hours. The reaction mass is treated as in Example 1 to obtain 240 g of a product consisting of a mixture of compounds of formulas 26 and 27.

83 04 1 4 7

Claims (2)

A process for preparing at least one of the substances: (a) a mixture of 1- (3,3-dimethylcyclohexyl) -4-methyl-cis-2-penten-1-one, 1- (3, 3-dimethylcyclohexyl) - 5 4-methyl-trans-2-penten-1-one and 1- (3,3-dimethylcyclohexy1) - 4-methyl-3-penten-1-one, (b) a mixture of 1- (3,3-dimethylcyclohexyl) -cis-2-penten-1-one, 1- (3,3-dimethylcyclohexy1) -trans-2-pentenene-1-one and 1- (3,3-dimethylcyclohexyl) - 3-penten-1-one, 10 (c) a mixture of 1-butenoyl-1,3,3-dimethyl cyclohexanes of the formula 1, which mixture consists of compounds of the formulas 2, 3 and 4, one of the dotted lines being a single and the other dotted line represents a carbon-to-carbon double bond, 15 (d) 1-butanoyl-3,3-dimethylcyclohexane of the formula 5, (e) a compound of the formula 6, (f) the compound 1-acetyl-3 3-dimethyl- (2-propenyl) -cyclohexane of the formula 7 (g) compounds of the formula 8, wherein R 1 represents methallyl, R 1 represents hydrogen and R 1 represents hydrogen, or R 1 represents hydrogen, or hydrogen and R 2 and R 2 represent methallyl (h) a mixture of the compounds 1- (2-propenyl) -3- (4-methyl-3-pentenyl) -Δ-cyclohexene-1-carboxaldehyde and 1- ( 2-propenyl) -4- (4-methyl-3-pentenyl) -Δ ^ -cyclohexene-1-carboxaldehyde of the formula 9, wherein the carboxaldehyde moiety is bonded to either the α-carbon atom or the β-carbon atom of the cyclohexenyl moiety, wherein a suitably substituted halide or aldehyde is reacted with a suitable carbonyl compound in the presence of a reaction catalyst, base or boron compound, 8304147 κ κ 1 - 94 - ί characterized in that a 3-position dimethyl-substituted cyclohexyl group or an acyclic hydrocarbon group reacts with an aldehyde or allyl chloride or bromide or a methallyl chloride or bromide in the presence of a tertiary amine, toluene, t-butanol or a crown ether, as well as in the presence of base or a mixture of boron oxide and boric acid and possibly the procurement and compound or hydrogenating the resulting mixture. 10 A method for flavoring food, drinks, tobacco materials, perfume articles and the like, characterized in that one or more products are used here, which can be prepared according to the method of claim 1. 15 8304147 4 / / /