JPH0262542B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel perfumes and/or flavoring substances. The novel fragrance and/or flavoring substance of the present invention has the formula K0147 (wherein R ¹ represents C _1-4 -alkyl, R ² and R ³ represent hydrogen or methyl, provided that both simultaneously represent hydrogen). ). The formula includes all possible stereoisomers of substituents at the relative positions of the _C1- , _C2- and _C3- atoms in the formula. The group represented by R ¹ is linear or branched. Methyl and isobutyl are preferred, and ethyl is particularly preferred. A mixture of compounds of the formula in which R ² represents hydrogen and R ³ represents methyl and compounds of the formula in which R ² represents methyl and R ³ represents hydrogen are preferred. Furthermore R ² and
Compounds of the formula in which both R ³ represent methyl are preferred. The present invention also relates to a method for preparing compounds of formula. This process is characterized by the catalytic hydrogenation of an ester having the formula K0148, in which R ¹ , R ² and R ³ are as defined above, and one of the dotted lines indicates an additional bond. do. Catalysts suitable for this process are, for example, noble metal catalysts containing platinum, palladium, ruthenium or rhodium. Hydrogenation may be carried out with or without the addition of a solvent (preferably inert solvents such as ethyl alcohol, methyl alcohol, cyclohexane, etc.). Hydrogenation for example from 0℃ to 100℃, especially from 15℃
At a temperature of 30°C, normal pressure or higher pressure (e.g. 5
-20 atm) (HOHouse, Modern
Synthetic Reactions, NABenjamin Inc.
New York 1972). The products of the formula are obtained by the process of the invention as stereoisomeric mixtures. If necessary, separation of the isomer mixture can be carried out in a conventional manner, for example by preparative gas chromatography.
The isomers of the compounds of the formula do not differ fundamentally in their organoleptic properties, so that for economic reasons it is possible to use isomer mixtures. The ester starting material of the formula can be prepared by known methods for the preparation of cyclozeranoyl derivatives, for example by cyclizing an ester having the formula K0149, where R ¹ , R ² and R ³ are as defined above. It can be implemented by Suitable cyclizing agents are inorganic and organic protic acids such as sulfuric acid, phosphoric acid, methanesulfonic acid, formic acid, acetic acid, or Lewis acids such as boron trifluoride, tin tetrachloride, zinc chloride and the like. Cyclization can be carried out in the presence or absence of a solvent. Suitable solvents are inert solvents such as hexane, benzene, nitromethane, and the like. temperature is not important,
Crystallization can be carried out at room temperature or at higher or lower temperatures. In the ester of the formula, for example, R ² represents hydrogen and R ³
When represents methyl, the known 3,6-dimethyl-
Prepared from 5-hepten-2-one. Horner−Witting〔Wadsworth／Emmos
modification, J.Amer.Chem.Soc. 83 , 1733
[1961], for example, this ketone can be reacted with C _1-4 -carbalkoxy-methylene-diethylphosphonate in the presence of an alkali hydride or alkali alcoholate as base. The reaction is preferably carried out in an aprotic solvent such as benzene, toluene, dimethoxyethane and the like. Temperature is not important. A temperature range of about 40-60°C is preferred, but lower or higher temperatures can also be carried out. The following reaction scheme, in which R ¹ , R ² , R ³ and the dotted lines are as defined above, illustrates the preparation of compounds of formula. K0150 Highly saturated esters of the formula (e.g. esters in which R ¹ represents propyl or isobutyl) can be obtained from the methyl or ethyl esters of the formula by transesterification, i.e. by heating with a higher alcohol (e.g. propanol or isobutanol). is conveniently prepared in a conventional manner, preferably under alkaline conditions, so that the methanol or ethanol produced can be continuously distilled off from the reaction mixture. The compounds have special organoleptic properties which make them highly suitable as perfumes and/or flavoring agents. The invention therefore relates to the use of compounds of the formula as perfumes and/or flavoring substances. Due to their natural aroma notes, compounds of the formula, especially those in which R ² represents hydrogen and R ³ represents methyl, and compounds where R ² represents methyl and R ³ represents hydrogen or R ² and R ³ Mixtures of compounds in which both represent methyl are particularly suitable for improving known compositions. Said mixture of compounds of the formula (wherein R ¹ represents ethyl) may be a spice-like, fruit-like,
Displays a strong, diffusible and very natural warm top note with woody tendencies. Furthermore, it is worth mentioning the olfactory characteristics, such as powdery flowers. The compounds of the formula may be combined with a large number of known natural or synthetic fragrance composition ingredients, and the range of natural ingredients can include not just readily volatile substances, but also semi-volatile and exvolatile substances. The range of possible and synthetic components can include analogues of almost any type of material, as will be apparent from the following description. Trimos absolute, mebuki oil, bergamot oil, mandarin oil, frankincense absolute, silver plum blossom oil, palmarosa oil, patch lily oil,
Natural products such as petitgrain oil (balaguay) and bittern wormwood oil Alcohols such as geraniol, linalool, nerol, phenylethyl alcohol, rhodinol and cinnamic alcohol Citral, Helional, α-hexylcinnamaldehyde, hydroxycitroloneral,
Aldehydes, such as Lilial (p-tert-butyl-α-methyl, hydrocinnamaldehyde), (p-tert-butyl-α-methyl-dihydrocinnamaldehyde) and methylnonylacetaldehyde, allylionone, α-ionone, Ketones such as β-ionone and methylionone, allyl phenoxyacetate, benzyl salicylate,
Cinnamyl propionate, dimethylbenzylcarbinyl butyrate, ethyl acetoacetate, linalyl acetate,
Esters like methyl dihydrodiasmonate, styralyl acetate and vetiberyl acetate, lactones like coumarin, musk ambrette, Celestolid,
Galaxolid, indole, p-menthane-8-
Various ingredients often used in perfumery such as thiol-3-ones and methyleugenol. The compounds of the formula round out and harmonize the aroma notes of known compositions without dominating.
worth it. Thus, for example, a compound of the formula may emphasize spice-like and herbal notes in a perfume base with tea and green properties, and in the case of a rose base, it may be somewhat "synapse" (apple brandy).
It emphasizes the desirable characteristics of a deep, sweet Bulgarian rose, reminiscent of a rose. In fruit bases (such as the apricot type), the mixtures described above can be effectively used to produce a rounding effect with a velvety, natural aroma. A compound of the formula (or a mixture thereof) can be used for example from 0.1% in detergents to 30% in alcoholic solutions.
It can be used in a wide range of areas. These numbers are not limiting, as a skilled perfumer can synthesize novel complexes that are effective at low concentrations and even at high concentrations. Preferred concentrations are 0.5 to 25%. Compositions prepared from compounds of the formula can be used in all kinds of aromatic consumer products (colognes, toiletries, essences, lotions, creams, shampoos, soaps, ointments, powders, toothpastes, mouthwashes, deodorants) , cleaning agents, cigarettes, etc.). Therefore, a compound (or mixture thereof) of formula
As is clear from the foregoing description, it can be used to prepare compositions using a wide variety of known flavoring substances or mixtures of flavoring substances. In the production of such compositions, the above-mentioned known flavoring substances or mixtures of flavoring substances are added by methods well known to perfumers (e.g. WAPoucher, Perfumes, Cosmetics,
Soaps 2 , 7th Edition, Champan and Hall,
London1974) can be used. Compounds of the formula or mixtures thereof are likewise very suitable for use as flavoring agents in various fruit flavors, but especially in tobacco. As flavoring substances, the compounds of the formula can be used, for example, for producing or improving, enhancing, enhancing or modifying various fruit flavours, such as strawberry or apricot flavours. These flavors can be used, for example, in foods (yogurt, confectionery, etc.), luxury goods (tea, cigarettes, etc.), and beverages (lemonade, etc.). The compounds of the formula (or mixtures thereof) can be used as flavoring substances in low concentrations due to their significant flavor properties. Suitable concentration ranges include, for example, 0.01ppm-100ppm in the final product (i.e. flavored food, luxury item or beverage);
Preferably it is 0.01ppm-20ppm. However, for example in the flavoring of cigarettes, the concentration can be even higher and within a wider range, for example from 1 ppm to 1000 ppm, preferably 50 ppm.
Can be used at concentrations in the range -500ppm. The compounds of the formula can be mixed with ingredients used in flavoring compositions or ingredients conventionally added to such flavoring agents. Among the flavoring agents contemplated by the invention are flavoring substance compositions which can be diluted or dispersed in edible substances in a manner known per se. For example, they are about 0.1
-10% by weight, especially 0.5-3% by weight. These flavoring agents can be converted into conventional usage forms such as solutions, pastes or powders by known methods. The product can be spray dried, vacuum dried or freeze dried. Known flavoring agents which are advantageously used for the production of such flavoring agents are mentioned in the above description or can be cited from the relevant literature (for example, J.
Merory，Food Flavorings，Ccmposition，
Manufacture and Use，Second Edition，the
Avi Publishing Company, Inc., Westport,
Conn.1968, or G.Fenaroli, Fenaroli′s
Handbook of Flavor Ingredients，Second
Edition, Volume 2, CRC Press, Inc.
(See Cleveland, Ohio, 1975). For the preparation of the usual usage forms, the following carrier substances, thickeners, flavor enhancers, spices, auxiliaries, etc. can be used, for example. Gum arabic, tragaganth, salt or baker's yeast, alginate, carrageenan or similar absorbents; indole, manthol, dienal, spiced oleoresin, smoked sleba, T-shaped, diacetyl, sodium citrate, ionosodium glutamate, inosine-5 Disodium '-monophosphate (IMP), disodium guanosy-5-phosphate (GMP), or special flavoring substances, aqueous ethanol, propylene glycol, glycerin. The following examples illustrate the invention. Example 1 Approximately 20% 2,3,6,6-tetramethyl-2-
Cyclohexene-1-carboxylic acid ethyl ester, approximately 14% C,t-2-ethylidene-6,6-
dimethyl, cyclohexane-1-carboxylic acid ethyl ester and about 65% 2-ethyl-6,6-
30 g of an ester mixture consisting of dimethyl-2-cyclohexene-1-carboxylic acid ethyl ester,
600 mg of palladium (10
% on carbon) and hydrogenate. 96.9% of the theoretical amount of hydrogen is absorbed after 24 hours. The catalyst is filtered through Celite, backwashed with a small amount of ethanol, and the solvent is distilled off on a rotary evaporator. The crude product (29.8 g) was transferred to a 10 cm high vacuum tube.
Fractional distillation is performed using a Widmer column. boiling point 42−55
28g of mixture with °C/0.05mmHg (theoretical value of 92.4
%) is obtained. Gas chromatography [Glass capillary column (50 m x 0.3 mm i.d.) with Ucon HB5100 as stationary phase, 140 °C isothermal, helium flow rate
2.5 ml/min], the product has essentially the following composition: 41.8% cis-2-ethyl-6,6
-dimethylcyclohexane-1-carboxylic acid ethyl ester, 34.6% trans-2-ethyl-
6,6-dimethylcyclohexane-1-carboxylic acid ethyl ester and 19.6% of 2,3,6,6
-tetra-methylcyclohexane-1-carboxylic acid ethyl ester (various stereoisomers, especially about
4.1% 1,2cis-2,3-trans-2,3,
6,6-tetramethyl-1-cyclohexanecarboxylic acid ethyl ester and about 9.1% of 1,2-
trans-2,3-trans-2,3,6,6-
Tetramethyl-1-cyclohexane-1-cyclohexanecarboxylic acid ethyl ester). The isomer mixture was separated by preparative gas chromatography. The main peak showed the following spectroscopic data.

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【table】

【table】

【table】

[Table] The starting material is prepared as follows. 5.8g (0.252g atoms) in 130ml absolute ethanol
of sodium at a temperature of 5-10°C, 20
30 g (0.214 mol) of a ketone mixture consisting of % 3:6-dimethyl-5-hepten-2-one and 80% 7-methyl-6-octen-3-one and 62.4 g in 130 ml anhydrous toluene. (0.278 mol) of phosphonoacetic acid triethyl ester solution is added dropwise. The mixture is then allowed to reach room temperature,
Let react overnight. The mixture is poured into ice water and extracted three times with hexane. The combined hexane solutions are washed with sodium chloride solution until neutral, dried over sodium sulfate and evaporated. Crude product (43
g) is fractionally distilled in high vacuum on a 10 cm Widmer column. Boiling point 58−61℃/0.02mmHg, n ²⁰ _D = 1.4708
28.9g (64.3%) of the mixture was obtained. The mixture is
20% C,t-3,4,7-trimethyl-2,6
-octadienoic acid ethyl ester and 80% C,t-3-ethyl-7-methyl-2,6-octadienoic acid ethyl ester. Cool 228 ml of formic acid to 0-5°C. At this temperature 12 ml of concentrated sulfuric acid are added and the mixture is then stirred for 1 hour. The resulting acid mixture contains 20% C,t-
24 g of the above ester mixture consisting of 3,4,7-trimethyl-2,6-octadienoic acid ethyl ester and 80% C,t-3-ethyl-7-methyl-2,6-octadienoic acid ethyl ester,
Add carefully dropwise at 5°C. After the addition is complete, the mixture is allowed to reach room temperature and stirred for a further hour at this temperature. Pour the mixture onto ice and extract three times with hexane. The combined hexane solutions are washed neutral once with water, twice with sodium bicarbonate solution and finally twice with water, dried over sodium sulfate and evaporated. The crude product (22.5 g) is fractionally distilled in high vacuum on a 10 cm Widmer column. Approximately 20% 2,
3,6,6-tetramethyl 2-cyclohexene-1-carboxylic acid ethyl ester, 14% C,t
-2-ethylidene-6,6-dimethyl-cyclohexane-1-carboxylic acid ethyl ester and 65% of 2-ethyl-6,6-dimethyl-2-cyclohexene- with a boiling point of 102°C/6 mmHg, n ²⁰ _D = 1.4626
17 g (70.8%) of an ester mixture consisting of 1-carboxylic acid ethyl ester are obtained. Example 2 Consisting of about 80% 2-ethyl-3,6,6-trimethyl-2-cyclohexene-1-carboxylic acid ethyl ester (residue, double bond isomer),
22.4 g (0.1 mol) of the ester mixture was dissolved in 250 ml of anhydrous ethyl alcohol and 800 mg
of palladium (10% on carbon) and hydrogenated in an autoclave at 10 bar and 60° C. for 24 hours. The catalyst is filtered through Celite, backwashed with a small amount of ethyl alcohol, and the solvent is distilled off on a rotary evaporator. The crude product (21.8 g) is fractionally distilled on a 5 cm Widmer column under high vacuum. Boiling point 80−81°/0.15mmHg,
18.0 g (79.6% of theory) of a mixture with n ²⁰ _D =1.4527 are obtained. Capillary gas chromatogram (50m x 0.31
mm inner diameter. , Ucon HB5100, 140° C. isothermal, helium flow rate 2.5 ml/min, separation 1:30), there are four distinct peaks in the total mixture (indicated by increasing retention time) at the following percentages: P ₁ 42.4% P ₂ 34.9% P ₃ 16.5% P ₄ 6.2% Peaks 1, 2, 3 and 4 are 2-ethyl-3,
The four possible isomers of 6,6-trimethyl-cyclohexane-1-carboxylic acid ethyl ester are shown. The product of peak-1 was separated by preparative gas chromatography and showed the following spectral characteristics.

[Table] Aroma: Woody, fruity, aromatic, reminiscent of strawberry, camphor, and eucalyptus seeds. Example 3 Approximately 90% 2-ethyl-6,6-dimethyl-2-
5 g of the ester mixture consisting of cyclohexane-1-carboxylic acid ethyl ester (residue: double bond isomer) are dissolved in 50 ml of absolute ethyl alcohol and treated with 100 mg of palladium (10% on carbon) at normal pressure and room temperature. Hydrogenate with vigorous stirring for 24 hours. The catalyst is removed on Celite, backwashed with a little ethyl alcohol and the solvent is distilled off on a rotary evaporator. The crude product (4.9 g) is distilled in a bulb-tube. 4.3g (85.2% of theory), boiling point 65
A mixture having a temperature of 0.degree. C./0.08 mmHg is obtained. Capillary gas chromatogram (50m x 0.31mm inner diameter, Ucon
HB5100, with 140℃ isothermal, helium flow rate 2.5
ml/min, separation ratio 1:30), the following composition is obtained.
Approximately 47% cis-2-ethyl-6,6-dimethyl-
1-Cyclohexanecarboxylic acid ethyl ester and about 50% trans-2-ethyl-6,6-dimethyl-1-cyclohexanecarboxylic acid ethyl ester (spectroscopic data: see Example 1). Aroma: bites and tagetes
Very natural in direction. Example 4 About 21% of 2,3,6,6-tetra-2-cyclohexene-1-carboxylic acid isobutyl ester,
About 12% C,t-2-ethylidene-6,6-dimethyl-cyclohexane-1-carboxylic acid isobutyl ester and about 61% 2-ethyl-6,6-
10 g of ester mixture consisting of dimethyl-2-cyclohexene-1-carboxylic acid isobutyl ester
was dissolved in 75 ml of absolute ethyl alcohol and 300 mg of palladium (5% on carbon) was added,
Hydrogenate for 15 hours in an autoclave at 10 bar and 50 °C. The catalyst is separated off through Celite, backwashed with a small amount of ethyl alcohol, and the solvent is distilled off on a rotary evaporator. The crude product (9.9 g) is fractionally distilled on a 5 cm Vigreux column under high vacuum. 8.2g (theoretical amount)
85.4%), boiling point 67-68℃/0.09mmHg, n ²⁰ _D =
A mixture having 1.4510 is obtained. According to gas chromatography (glass capillary column (50 m x 0.3 mm internal diameter) with Ucon HB5100 as stationary phase, 140° C. isothermal helium flow rate 2.5 ml/min), the product has essentially the following composition: 55.1% cis-2-ethyl-6,6-dimethyl-cyclohexane-1-
carboxylic acid isobutyl ester, 31.2% trans-2-ethyl-6,6-dimethyl-cyclohexane 1-carboxylic acid isobutyl ester and
13.7% of 2,3,6,6-tetramethyl-1-cyclohexanecarboxylic acid isobutyl ester (various stereoisomers). Aroma: floral, somewhat fatty, grassy. The starting materials are prepared as follows. A solution of 140 mg of sodium in 101.3 g of isobutyl alcohol contains about 20% C,t-3,4,7-trimethyl-2,6-octadienoic acid ethyl ester and about 80% C,t-3-ethyl-7. - 27 g of a mixture consisting of methyl-2,6-octadienoic acid ethyl ester (prepared as described in Example 1)
A solution of 135 g of cyclohexane is added dropwise. The mixture is heated to boiling point, whereby the cyclohexane is distilled off and the distilled volume is replenished continuously from the dropping funnel (approximately 250 ml in 4 hours). The mixture is washed to neutrality with water (3 times), dried over sodium sulfate and evaporated. The crude product (29.4 g) is fractionally distilled on a 15 cm Widmer column under high vacuum. Boiling point 80-82℃/
27.5 g of a mixture with 0.04 mmHg, n ²⁰ _D = 1.4660
(70.9% of the theoretical value) obtained. The mixture is about 20
% C,t-3,4,7-trimethyl-2,6-
Octadienoic acid isobutyl ester and about 80%
C,t-3-ethyl-7-methyl-2,6-octadienoic acid isobutyl ester. This mixture is cyclized in a manner analogous to Example 1. In this way, boiling point 64−66℃/0.04mmHg, n ²⁰ _D =
A mixture of 1.4608 is obtained with a yield of 68.9%. The mixture contains about 21% 2,3,6,6-tetramethyl-2-cyclohexane-1-carboxylic acid isobutyl ester, about 12% C,t-2-ethylidene-6,6-dimethyl-cyclohexane-1 -carboxylic acid isobutyl ester and about 61% of 2-ethyl-6,6-dimethyl-2-cyclohexene-
Consists of 1-carboxylic acid isobutyl ester. In the following examples, "mixture" refers to the product of Example 1. Example 5 Fragrance base with tea characteristics Parts by weight Dipropylene glycol 500 Linalool Extra 70 Methyleugenol 50 p-methane-8-thiol-3-one [10% in dipropylene glycol (DPG)] 50 Mandarin oil 50 Silver plum blossom oil 50 Petitgrain oil 40 β-ionone 30 Mebuki oil 20 Helional (α-methyl-3,4-methylenedioxy-hydro-cinnamaldehyde) 20 Allyl phenoxyacetate 10 Indole (10% in DPG) 10 900 100 parts by weight By adding the mixture
The composition substantially spreads and becomes more potent. It's also fresher, spicier, sweeter, and has a rose-like, subtly floral character. When the composition was dissolved in ethyl alcohol and sensory tested in the concentration range of normal lotions, i.e. 5-10% by weight, the composition containing the mixture showed remarkable diffusibility and dispersibility on scented paper after a few hours. At the same time it exhibits a very warm glow. Although this effect is highly desirable, it is actually rather unusual for substances that volatilize relatively easily. Example 6 Green base Parts by weight Citral 10 Wormwood oil 10 Mastix Absolute 20 Amethyst oil 80 Methyl dihydrodiasmonate 100 Linalyl acetate 200 α-hexylcinnamaldehyde 200 Benzyl salicylate 200 Ethyl alcohol (95°) 130 950 Above Addition of 50 parts by weight of the mixture to the green base considerably enhances the herbaceous, fresh and spicy character of the composition (particularly confirmed by the freshly infused scent paper). The average morphological impression, combined with floral-saltylate-like notes, is very strongly reminiscent of anthranilate perfume substances when smelling on the stored gradient paper. The composition is more potent both fresh as well as stored and has a greatly increased spreading effect. Example 7 Composition with rose character Parts by weight Phenylethyl alcohol 465 Synthetic geraniol 80 Cinnamyl alcohol (substituted) 70 Nerol 65 Cinnamyl propionate 55 Celetolid (4-acetyl-6-tert-butyl-1,1- By adding a mixture of 155 900 100 parts by weight of dipropylene glycol 10 dimethyl indane)
The rose character of the first composition increases in warmth and softness, and the diffusivity increases. Produces a more pronounced damascone note. At the bottom, the pronounced jazz character softens slightly, creating a pleasant roundness. Example 8 Composition with apricot character Parts by weight α-ionone 160 Dimethylbenzylcarbinyl butyrate 100 Ethyl acetyl acetate 60 Galaxolid (1,3,4,6,7,8-hexahydro-4,6,6,7,8 , 8-hexamethyl-cyclopenta-γ-2-benzopyran)
50 Undecalactone 30 Palmarosa Oil 40 Allyl Ionone 40 Dipropylene Glycol 500 980 By adding a mixture of 20 parts by weight, the apple-like weak green note of the first composition and its pear note are modified to the desired apricot note. Can be changed often. Compositions containing the mixture are clearly more natural, harmonious and less harsh. The influence of the addition is clearly significant, especially in the bottom, in that the elements of the composition that were previously unharmonized match each other very harmoniously, and at the same time suppress the less desirable jacquard characteristics. Example 9 Composition (Chypre) Part by weight Styraryl acetate 20 Methylnonylacetaldehyde [aldehyde
C ₁₂ -MNA] (10% in diethyl phthalate) 20 Vetiveryl acetate 50 Rhodinol (citronellol-geraniol mixture) 50 Pachyuli oil 50 Tri-Mos absolute (50% in diethyl phthalate) 50 p-tertiary butyl-α-methyl Hydrocinnamaldehyde 100 Hydroxycitronellal 100 Methyl Ionone 100 Musk Ambrette 100 Coumarin 100 Bergamot Oil 100 The addition of 900 100 parts by weight of the mixture gives the freshly soaked gradient paper a very pleasant fruity note,
As a result, the new composition is substantially warmer, softer, and less intrusive. At the bottom, unpleasant soapy and irritating notes, especially those of aldehyde _C12 -MNA, are conveniently hidden. Example 10

【table】

Table: By adding the mixture to the apricot composition, its fruity notes are quite clearly enhanced. The fruity notes become richer, more rounded, and a velvety smooth note reminiscent of fully ripened apricots develops.

Claims (1)

Claims: 1. A compound having the formula K0143, in which R ¹ represents C _1-4 -alkyl and R ² and R ³ represent hydrogen or methyl, provided that both do not represent hydrogen at the same time. 2. A compound of the formula according to claim 1, wherein both R ² and R ³ represent methyl. 3. The compound according to claim 1, which is 2-ethyl-3,6,6-trimethyl-cyclohexane-1-carboxylic acid ethyl ester. 4. The compound according to claim 1, which is 2,3,6,6-tetramethyl-cyclohexane-1-carboxylic acid ethyl ester. 5. The compound according to claim 1, which is 2-ethyl-6,6-dimethyl-cyclohexane-1-carboxylic acid ethyl ester. 6 Perfume and/or containing a compound having the formula K0144 (wherein R ¹ is C _1-4 -alkyl, R ² and R ³ are hydrogen or methyl, but not both at the same time) Flavoring composition. 7 Process for producing a compound having the formula K0145 (wherein R ¹ represents C _1-4 -alkyl and R ² and R ³ represent hydrogen or methyl, provided that both do not represent hydrogen at the same time) In catalytic hydrogenation of the ester of a compound having the formula K0146, where R ¹ , R ² and R ³ are as defined above and one of the three dotted lines indicates an additional bond. The above manufacturing method is characterized in that: