JPS6225135B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel flavoring and/or flavoring materials. More specifically, the present invention relates to the general formula (wherein R represents _C1-4 -alkyl or _C2-4 -alkenyl and one of the three dashed lines represents an additional bond). Therefore, the above formula is

【formula】

【formula】

It is intended to include esters having the formula: ##STR1## where R has the meaning given above. Alkyl and alkenyl groups denoted by the symbol R may be straight-chain or branched. Particularly good are ethyl, isobutyl and allyl. The invention also relates to a process for preparing esters of the above formula. This method is a general formula (wherein R has the above-mentioned meaning) is cyclized. The preparation of esters of the formula can be carried out according to methods known for the preparation of cyclogeranoyl derivatives. Suitable cyclizing agents are inorganic and organic protic acids, such as sulfuric acid, phosphoric acid, methanesulfonic acid, formic acid, acetic acid, etc., or Lewis acids, such as boron trifluoride, tin tetrachloride, zinc chloride, etc. Cyclization is carried out in the presence or absence of a solvent. Suitable solvents are inert solvents such as hexane-benzene, nitromethane, and the like. There is no particular restriction on the temperature, and the cyclization can be carried out at room temperature or at higher or lower temperatures. The ester starting materials of formula are new and form part of this invention. These esters have organoleptic properties and the known 3,6-dimethyl-5-heptene-2
- Conveniently made from the on. For example, this ketone is called Horner-Wittig.
[Wadsworth/Emmows]
83 , 1733 (1961)] with C _1-4 -carboalkoxy-methylene-diethyl phosphate in the presence of an alkali hydride or alkali alcoholate as base. I can do it. This reaction is carried out using aprotic solvents such as benzene,
Conveniently carried out in toluene, dimethoxyethane, etc. There is no particular restriction on the temperature at which the reaction is carried out.
A temperature range of about 40 DEG -60 DEG C. is particularly preferred, although the reaction can also be carried out at lower or higher temperatures. If desired, the resulting methyl or ethyl ester of the formula is heated in a customary manner, for example with a higher alcohol (e.g. isobutanol), conveniently under alkaline conditions, and the resulting methanol or ethanol is constantly removed from the reaction mixture. Transesterification can be carried out by distillation. According to the process of the invention, the product obtained is an isomeric mixture of esters having the formulas a, b and c. If desired, separation of the isomer mixture (with a significant preponderance of esters of formula a) can be carried out by customary methods, for example by preparative gas chromatography. Since the abovementioned isomers do not fundamentally differ in their organoleptic properties, it is therefore possible, especially from an economic point of view, to use isomer mixtures. The esters of the formula have special organoleptic properties, on the basis of which they are used as flavoring agents and/or
Very well suited as a flavoring agent. The invention therefore also relates to the use of esters of the formula as flavoring and/or flavoring substances. Based on these natural fragrance notes, the esters of the formula can be used in the modification of known compositions, for example when trying to intensify the cytrus notes (e.g. cologne type, extracts), and also in floral, especially rose compositions. In the modification of formulas, the use of esters in particular can lead to a clear musk effect (extract type, compositions for women), as well as in depressing compositions (addition of esters in formulas can lead to a sort-after, expensive, dull tone). Especially suitable for strengthening (extract type for general use). Fruit bases containing esters of the formula (eg, apricot-type ones) are fuller, sweeter, and have a pronounced confectionery note. For example, 2,3,6,6-tetramethyl-2-
Cyclohexene-1-carboxylic acid ethyl ester has a bright, strong, floral spice note and a daytime note. Additionally, the fruit-sweet, somewhat powdery side-notes of this ester are also worth mentioning. This particularly suitable ester is a structurally closely related known ester, 2,5,6,6-tetramethyl-cyclohex-2-ene-1-carboxylic acid ethyl ester [H. .Favre and H.Sching), Helv.
35 , 1627 (1952)], the latter ester having only a moldy, earthy note. The esters of the formula are combined with a number of known natural or synthetic ingredients of fragrance compositions. In this case, the range of natural ingredients can include not only readily volatile substances, but also semi-volatile and refractory substances, and the range of synthetic ingredients can include almost any kind of substances, as is clear from the following collected materials: may include representative ones from. Natural products such as Trimos absolute, Mebuki oil, Bengamoto oil, Acetylated Cedar
Wood oil [e.g. VertofixIFF or
Cadartcne Givaudan], oakmoss, galbanul oil, geranium oil, diasmine absolute and its substitutes, lavender oil, lavandin oil, masticus absolute, neroli oil, pachy lily oil, petitgrain oil, Paraguay, violet oil, vetiver oils, ylang-ylang oil, lemon oil, and wormwood oil. Alcohols such as linalool, citronellol, geraniol, natural rhodinol, alpha-terpineol, phenylethyl alcohol, phenylpropyl alcohol, and cinnamyl alcohol. Aldehydes such as 3,5-dimethyl-cyclohex-3-ene-carboxaldehyde,
decanal, methylnonylacetaldehyde,
Hydroxycitronellal, α-hexylcinnamaldehyde, cyclamenaldehyde, p-
tert.Butyl-α-methyl-dihydro-cinnamaldehyde (e.g. Lilial Givaudan)
and citral. Ketones such as α-ionone, acetylcedrene, p-methylacetophenone and methylionone. Esters For example, cedryl acetate, Cis
-3-hexenyl acetate, Cis-3-hexenylbenzoate, ethyl acetoacetate, linalyl acetate, geranyl acetate, terpenyl acetate, phenylethyl acetate, styralyl acetate, p-tert.
Butyl cyclohexyl acetate, 4-[4-
Methyl-3-pentenyl]-cyclohexa-3
-en-1-yl-carbinyl acetate (Myraldyl acetate givaudan), cinnamyl formate, benzyl acetate, benzyl salicylate, amyl salicylate and methyl dihydrodiasmonate. Lactones such as γ-undecalactone and coumarin. Various additional substances often used in perfumery, e.g.
Musk compounds [musk ambulette, musk ketone, 12-oxa-hexadecanolide (e.g. Musk 174 nadene), 1,1-dimethyl-4-acetyl-6-tert.butylindane, indole], p-menthane-8-thiol- 3-one, eugenol, acetaldehyde-propylphenyl-ethyl acetal and methyl 1-methylcyclododecyl ether (e.g. Madrox Givaudan). As flavoring substances, the esters of the formula can be used, for example, to produce, improve, enhance, enhance or modify various types of fruit flavours, such as strawberry or apricot flavours. Surprisingly, for example in the grape flavor, the characteristic notes of fresh grapes are advantageously emphasized. Application areas for these flavors include foods (yogurt, sweet products, etc.), luxury goods (tea, tobacco, etc.) and beverages (lemonade, etc.). Finally, a particularly surprising and valuable discovery according to the present invention is the general formula (wherein R has the meaning given above and one of the three dashed lines represents an additional bond) or in combination with a mixture of esters of the formula, especially R is ethyl (esters') and 2-ethyl-6,6-dimethyl-2-cyclohexene-1-
Carboxylic acid ethyl ester (e.g. DT-
(see OS2644.762) has surprising olfactory qualities, ie great naturalness and brilliance. These mixtures therefore represent another aspect of the invention. The importance of the new mixtures lies above all in their wide range of applications. In particular, interesting effects can be achieved in compositions of floral bases (especially of the rose type), immature bases and fruit bases, and of the cologne type. The novel mixtures are likewise particularly suitable for use in various types of fruit flavours, in particular for tobacco flavoring. The ratio of ester of formula' to ester of formula can vary within a wide range, for example from 90:10 to 10:90.
A range of 10:90 to 30:70 is particularly good. Its (extreme) values can be easily adjusted, in particular by appropriate selection of the synthesis of starting materials, as can be easily seen from the schematic below. 3,6-dimethyl-5- depicted in the above schematic formula
Both routes for the preparation of hepten-2-one/7-methyl-6-octen-3-one mixtures are known from the literature [e.g. Belgian Patent No. 634,738 for route A and also for route B. HOHouse,
“Medern Synthetic Reaetions”, by
WABenjamin Inc.,
New York 1972. and JUNef, Ann. 310 , 318 (1900)]. According to the above schematic, the esters of formula and occur as a mixture of isomers with a significant predominance of the α-form. Esters of the formula (or ester mixtures with the formula) can be used within a wide range, extending for example from 0.1% in detergents to 30% in alcoholic solutions. These values are not limiting, since an experienced perfumer can achieve effects at lower concentrations or synthesize new compounds at higher concentrations. Particularly suitable concentrations vary from 0.5% to 25%. Compositions made with esters of the formula can be used in all kinds of perfumed articles (colognes, lotions, extracts, lotions, creams, soaps, shampoos, liniments, powders, toothpastes, mouthwashes, deodorants, cleaning products, cigarettes, etc.). Therefore, esters of the formula (or mixtures of esters with the formula) can be used in the preparation of compositions by using a wide range of known flavoring substances or mixtures of flavoring substances, as is clear from the above collection. . In the production of such compositions, known flavoring substances or flavoring substance mixtures, such as those mentioned above, are added according to methods known to perfumers, for example by W.
A.Poucher), Perfumes, Cosmetics, Soaps.
2 , 7th edition, Chapman and Hall, London (1974). The remarkable flavor qualities of the esters of the formula (or mixtures of esters of the formula and) enable them to be used as flavoring substances at low concentrations. Suitable ranges include, for example, in finished products (i.e. flavored foods, snacks or beverages):
0.01ppm−100ppm, preferably 0.01ppm−
It is 20ppm. However, for example, in the flavor of cigarettes,
The concentration may be high and may range over a wide range, for example from 1 ppm to 1000 ppm, preferably from 50 to 500 ppm. Esters can be mixed with ingredients used in flavoring compositions or added to such flavoring agents in the usual manner. Flavoring agents contemplated by this invention include flavoring compositions that can be diluted or dispersed in edible materials by known methods. These contain, for example, about 0.1-10% by weight, especially 0.5-3% by weight. These can be converted by known methods into customary forms for use such as solutions, pastes or powders. Spray dry the product,
Can be vacuum dried or freeze dried. Known flavoring substances conveniently used in the production of such flavoring agents are cited in the above collection or in related literature [e.g., J. Melory, Food
Flavorings, Composition, Manufacturing and
'Use', 2nd edition, The Avi Publishers
Publishing Company, Inc.), Westport,
Connecticatuto (1968), or G.Fenaroli, “Fenaroli´s Handbook of
Flauov Ingredients”, 2nd edition, CRC Press,
Cleveland, Ohio (1975)]. For the production of the customary use forms, the following carrier substances, thickeners, flavor enhancers, spices and auxiliary ingredients can be used, for example. Beer gum arabic, tragacanth, salts or alginates, carrageenan or similar absorbents, indole, maltol, dienals, spiced oleoresins, smoked flavors, chives, diacetyl, sodium citrate, monosodium glutamate, inosine-5'-monophosphate. disodium (IMP), disodium guanosine-5-phosphate (GMP), or special flavoring substances, water, ethanol, propylene glycol, glycerin. The following examples illustrate the method of the invention. Example 1 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. c・t−3・4・7− to the resulting acid mixture
24 g (0.114 mol) of trimethyl-2,6-octadienoic acid ethyl ester are carefully added dropwise at +5°C. After the addition is complete, the mixture is allowed to reach room temperature and stirred at this temperature for a further 1 hour. Pour the mixture onto ice and extract three times with hexane. The combined hexane solutions are neutralized by washing 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 using a 10 cm Widmer column under high vacuum. Boiling _point 55℃/0.07mmHg, ^n20D
=1.4640 of 2,3,6,6-tetramethyl-2-
Cyclohexene-1-carboxylic acid ethyl ester
17g (70.8%) is obtained. According to gas chromatography (glass capillary column 50m, UCON
HB5100, 110℃, isothermal, carrier gas helium
2.0 ml/min), this product has the following composition:
2,3,6,6-tetramethyl-2-cyclohexene-1-carboxylic acid ethyl ester (relative retention
1.00) approximately 91.5%, 2-methylene-3,6,6-trimethylcyclohexane-1-carboxylic acid ethyl ester (cis/trans-isomers, relative retention
1.01 and 1.06) approximately 9%, and 2, 3, 6, 6
-tetramethyl-1-cyclohexene-1-carboxylic acid ethyl ester (relative retention 1.12) approx. 0.5
%. Spectral data of main products: IR (liquid): 1735 cm ^-1 band (C=0, ester) NMR (CHCl ₃ ): 0.9 s (6H)

【formula】 1.26t/7 (3H)

【formula】 1.60 m (6H)

[expression] and

【formula】 1.95 m (2H)

【formula】 2.57 s (1H)

【formula】 4.15 q/7 (2H)

[Formula] MS: 210 (M, 11), 137 (100), 136 (42), 95
(24), 121(22) and 81(10). The c·t-3·4·7-trimethyl-2·6-octadienoic acid ethyl ester used as starting material can be prepared as follows: 5.8 g of sodium in 130 ml of absolute ethanol.
(0.252 g atoms) in 130 ml of dry toluene at a temperature of 5°-10°C.
30 g (0.214 mol) of 5-hepten-2-one and 62.4 g of phosphonoacetic acid triethyl ester
(0.278 mol) is added dropwise. The mixture is then brought to room temperature and allowed to react overnight. Pour the mixture onto ice/water and extract three times with hexane. The combined hexane solutions are washed with sodium chloride solution until neutral, dried over sodium sulfate and evaporated.
The crude product (43 g) is fractionally distilled on a 10 cm Widmer column under high vacuum. Boiling point 67°-72°C/0.035
c·t-3·4·7-trimethyl-2·6-octadienoic acid ethyl ester with mmHg, n ²⁰ _D =1.4690
28.9g (64.3%) is obtained. Example 2 Following the procedure described in Example 1, c·t-3-ethyl-7-methyl-2·6-octadienoic acid ethyl ester 75% and c·t-3·4·7-trimethyl-2·6- Octadienoic acid ethyl ester
88.7 g of crude product are obtained in a similar manner from 90 g of a 25% ester mixture. Boiling point 102 after fractional distillation with 10cm Widmer column top water flow pump vacuum
2-ethyl-6.6 at °C/6 mmHg, n ²⁰ _D = 1.4626
-74.4 g of a mixture consisting of 75% dimethyl-2-cyclohexene-1-carboxylic acid ethyl ester and 25% 2,3,6,6-tetramethyl-2-cyclohexene-1-carboxylic acid ethyl ester (82.7% of theory) ). Example 3 According to the method described in Example 1, c/t-3/4/7
66.5 g of crude product are obtained in the same way from 71 g of an ester mixture consisting of 80% -trimethyl-2,6-octadienoic acid ethyl ester and 20% c.t-3-ethyl-7-methyl-octadienoic acid ethyl ester. After fractional distillation in high vacuum on a 20 cm Widmer column, boiling point 64°-66°C/0.01 mmHg, n ²⁰ _D
80% of 2,3,6,6-tetramethyl-2-cyclohexene-1-carboxylic acid ethyl ester and 20% of 2-ethyl-6,6-dimethyl-2-cyclohexene-1-carboxylic acid ethyl ester with =1.4610 59.6 g of a mixture consisting of (theoretical value 83.9
%). Example 4 Cool 204 ml of formic acid to 0°-5°C. At this temperature, 11 ml of concentrated sulfuric acid are added and the mixture is stirred for 1 hour. At the same temperature c・t-3-ethyl-7-methyl-
2,6-octadienoic acid methyl ester 77.1% and c·t-3·4·7-trimethyl-2·6-
20 g (0.102 mol) of a mixture consisting of 22.4% octadienoic acid methyl ester are added dropwise. The mixture is brought to room temperature and allowed to react for 1 hour. Pour the mixture onto ice and extract three times with hexane. The combined hexane solution was washed once with water, twice with saturated sodium bicarbonate solution, and finally twice with water to neutralize it.
Dry over sodium sulfate and evaporate. The crude product is fractionally distilled on a 15 cm Widmer column under high vacuum. Boiling point 38°-41°C/ _0.05mmHg , ^n20D =
15.5 g (77.5%) of a mixture having a concentration of 1.4650 are obtained. Gas chromatography [Glass capillary column 50 m x 0.3 mm (inner diameter), Ucon HB5100 packed, 70
゜-185℃ (temperature increase 3℃/min), helium flow rate 2.5
ml/min], the product has the following composition: 2,3,6,6-tetramethyl-2-cyclohexene-1-carboxylic acid methyl ester 20.2
%, 2-ethyl-6,6-dimethyl-2-cyclohexene-1-carboxylic acid methyl ester 73.4
%, as well as a small amount of c·t-2-ethylidene-
6,6-dimethyl-cyclohexane-1-carboxylic acid methyl ester. c・t-3-ethyl-7 used as starting material
-Methyl-2,6-octadienoic acid methyl ester 77.1% and c.t-3.4.7-trimethyl-2,6-octadienoic acid methyl ester 22.4%
An ester mixture consisting of can be prepared as follows: 9.7 g of sodium in 220 ml of absolute methanol
85 g (0.467 mol) of phosphonoacetic acid trimethyl ester and 23.9% of 3,6-dimethyl-5-hepten-2-one and 7-methyl-
A solution of 50 g (0.357 mol) of a ketone mixture consisting of 76.1% of 6-octen-3-one in 220 ml of anhydrous toluene is added dropwise. Then let the mixture come to room temperature,
Let react overnight. Pour the mixture onto ice and extract three times with hexane. The combined hexane solutions are washed neutral with sodium chloride solution, dried over sodium sulfate and evaporated. Crude product (81.8
g) is fractionally distilled on a 15 cm Widmer column under high vacuum. Boiling point 58°-61°C/ _0.02mmHg , ^n20D =
44.8 g (64.0%) of a mixture of 1.4708 is obtained. This mixture is c.t-3-ethyl-7-methyl-
It consists of 77.1% of 2,6-octadienoic acid methyl ester and 22.4% of c.t-3.4.7-trimethyl-2,6-octadienoic acid methyl ester. 3,6-dimethyl-5-hepten-2-one
A ketone mixture consisting of 23.9% and 76.1% of 7-methyl-6-octen-3-one was prepared in known manner (e.g. Belgian Patent No. 634,738, 1964).
10.1), 3-methyl-1-butene-3-
It is obtained in a yield of 54.4% from ol, methyl butenyl ether and phosphoric acid as a catalyst at 180° C. in an autoclave. Example 5 Cool 155 ml of formic acid to 0°-5°C. At this temperature 15.5 ml of concentrated sulfuric acid are added and the mixture is then stirred for 1 hour. At the same temperature, c.t-3-ethyl-7-methyl-2.6-octadienoic acid isobutyl ester 71.6% and c.t-3.4.7 in 50 ml of hexane.
A solution of 24.5 g (0.103 mol) of a mixture consisting of 20.1% -trimethyl-2,6-octadienoic acid isobutyl ester is added dropwise. Bring the mixture to room temperature,
Let react for 1 hour. Pour the mixture onto ice and extract three times with hexane. The combined hexane solution is neutralized by washing once with water, twice with saturated sodium bicarbonate solution and finally twice with water, dried over sodium sulfate and evaporated. Crude product (21.2g) 15
Fractionally distill at high vacuum on a cm Widmer column.
16.9 g (69.0%) of a mixture with a boiling point of 64°-66°C/0.04 mmHg and n ²⁰ _D =1.4608 are obtained. Gas chromatography [glass capillary column
50m x 0.3mm (inner diameter), filled with Ucon HB5100, 3.0
Temperature increase: 70°-185°C, helium flow rate: 2.5ml/min
According to [minute], this product has the following composition:
c・t-2-ethylidene-6,6-dimethyl-cyclohexene-1-carboxylic acid isobutyl ester 12.7%, 2,3,6,6-tetramethyl-2-
19.9% cyclohexene-1-carboxylic acid isobutyl ester, and 60.1% 2-ethyl-6,6-dimethyl-2-cyclohexene-1-carboxylic acid isobutyl ester. c・t-3-ethyl-7 used as starting material
An ester mixture consisting of 71.6% -methyl-2,6-octadienoic acid isobutyl ester and c.t-3.4,7-trimethyl-2,6-octadienoic acid isobutyl ester can be prepared as follows: Sodium 140 mg (6.1 mmol) is dissolved in 100 g of isobutanol with heating under a nitrogen atmosphere. c.t-3- in 200 ml of cyclohexane at room temperature.
Ethyl-7-methyl-2,6-octadienoic acid methyl ester 77.1% and c.t-3.4.7-trimethyl-2,6-octadienoic acid methyl ester
A solution of 27 g (0.138 mol) of a mixture consisting of 22.4% is added dropwise. Approximately 150 ml of cyclohexane is then continuously distilled off over a 15 cm Vigreux column for approximately 4 hours. At the same time, the distillate amount of cyclohexane is constantly replenished from the dropping funnel. Then pour the solution into water,
Wash once with saturated sodium bicarbonate solution and twice with water to neutralize. After drying over sodium sulfate and concentration on a rotary evaporator, 29.4 g of crude product remain.
Fractional distillation under high vacuum on a 15 cm Widmer column gives 23.3 g (71.0%) of a mixture with boiling point 77°-80° C./0.04 mm Hg, n ²⁰ _D =1.4660. This mixture was composed of 71.6% c.t-3-ethyl-7-methyl-2.6-octadienoic acid isobutyl ester and c.t.
-3,4,7-trimethyl-2,6-octadienoic acid isobutyl ester 20.1%. Example 6 35 ml of formic acid are cooled to 0-5°C. At this temperature, 3.5 ml of concentrated sulfuric acid are added, after which the mixture is stirred for 1 hour. c in 15 ml of hexane at the same temperature.
t-3-ethyl-7-methyl-2,6-octadienoic acid allyl ester 83.8% and c.t-3.4.
A solution of 5.2 g (23.4 mmol) of a mixture consisting of 9.1% allyl 7-trimethyl-2,6-octadienoic acid is added dropwise. Allow the mixture to come to room temperature and stir for 1.5 hours. Pour the mixture onto ice and extract twice with hexane. The combined hexane solutions are neutralized by washing once with water, twice with saturated sodium bicarbonate solution and finally twice with water, dried over sodium sulfate and evaporated. The crude product (3.9 g) is distilled in a bulb-tube. boiling point
110℃/0.05mmHg, n ²⁰ _D = 1.4720 mixture 3.7g
(71.2%). Gas chromatography (glass capillary column)
50m x 0.3mm inner diameter, filled with Ucon HB5100, heated at 3°C/min to 70°-185°C, helium flow rate 2.5ml/min), c・t-2-ethylidene-6,6-dimethyl-cyclohexane-1 -Carboxylic acid allyl ester 12.3%, 2,3,6,6-tetramethyl-
2-cyclohexene-1-carboxylic acid allyl ester 7.2% and 2-ethyl-6,6-dimethyl-2-cyclohexene-1-carboxylic acid allyl ester 67.4%. c・t-3-ethyl-7 used as starting material
-Methyl-2,6-octadienoic acid allyl ester 83.8% and c.t-3.4.7-trimethyl-
An ester mixture consisting of 9.1% of allyl 2,6-octadienoic acid ester is prepared as follows: 250 mg (10.8 mmol) of sodium are dissolved in 145 g of allyl alcohol with heating under a nitrogen atmosphere. c.t-3 in 250 ml of cyclohexane at room temperature.
-ethyl-7-methyl-2,6-octadienoic acid methyl ester 86.5% and c.t.3.4.7
A solution of 49 g (0.25 mol) of a mixture consisting of 9.5% -trimethyl-2,6-octadienoic acid methyl ester is added dropwise. 200 ml of cyclohexane are continuously distilled off over a period of 3 hours on a 15 cm Vigreux column at a bath temperature of 90 DEG C., and the distilled amount of cyclohexane is constantly replenished from the dropping funnel. Then pour the mixture onto ice and
Wash once with saturated sodium bicarbonate solution and twice with water to neutralize. After drying over sodium sulfate and concentration on a rotary evaporator, 53.8 g of crude product remain. Fractional distillation in high vacuum over a 20 cm Widmer column gives 38.7 g (69.7%) of a mixture with a boiling point of 92°-94° C./0.08 mm Hg, n ²⁰ _D =1.4768. This mixture contains 83.8% c.t-3-ethyl-7-methyl-2.6-octadienoic acid allyl ester and c.t-3.
Consists of 9.1% 4,7-trimethyl-2,6-octadienoic acid allyl ester. Example 7 Composition (Chypre) Parts by weight Styralyl acetate 20 Methylnonyl acetaldehyde (10% in diethyl phthalate) 20 Vetiveryl acetate 50 Rosinol 50 Pachyuli oil 50 Trimos absolute (50% in diethyl phthalate) 50 p-tert .Butyl-alpha-methylhydrocinnamaldehyde 100 Hydroxycitronellal 100 Methylionone 100 Musk Amblets 100 Coumarin 100 Bergamot oil 100 840 By the addition of 16% of the ethyl ester of formula ('), the methylnonylacetaldehyde in the composition is highly Pleasantly strengthened, the base is lighter overall and in this way, with the addition of new esters, compositions with new directions in the well-known chypre range are prepared. Example 8 Composition (Utsuday type) Parts by weight Mebuki oil 30 Methyl ionone 50 p-tert.butyl cyclohexyl acetate 50 Methyl dihydrdiasmonate 70 Cedryl acetate (crystalline) 100 Beyakudan oil 200 Pachu lily oil 200 Bergamotu oil 200 900 The addition of 1'100 parts of ester clearly intensifies the bright notes. Ester mixture ′ and ′ (ratio 10:90 to
30:70) gives truly surprising results. This addition gives a very elegant note to the generally mushy composition, and this, in the manufacture of simple compositions, virtually stamps the finished composition "Men's Lines". Example 9 Composition (colon type) Parts by weight indole (10%) 10 Coumarin 10 Ylang-ylang oil 20 Neroli oil 40 Lavandin oil 40 Benzyl acetate 40 Eugenol (extra) 40 Citral 60 Methyl dihydrodiasmonate 100 α-hexylcinnamaldehyde 100 Lemon Oil (Italian) 100 Bergamotu Oil 360 920 The addition of '80 parts of esters gives this generally cologne type a strong perceptible lemon effect, which is particularly distinguished by its freshness. A better effect can be achieved by adding the ester mixture ' and (15:85). This is because it not only gives freshness but also character, and at the same time is a very pleasant improvement over the original "simple" working cologne type. Example 10 Parts by weight of Green Base Citral 10 Wormwood oil 10 Masticus absolute 20 Amethyst oil 80 Methyl dihydrodiasmonate 100 Alcohol (95°C) 130 Linalyl acetate 200 α-hexylcinnamaldehyde 200 Benzyl salicylate 200 950 The addition of 50 parts of ester 'intensifies the influence of wormwood oil in this composition in a remarkable manner, whereas ester ', in contrast, Highlight notes. But ester mixtures ′ and ′ (15:85)
The merger effect of shows surprising results. Neither one somewhat bitter character nor the other character is accentuated, whereas on the other hand the composition leaves behind a very harmonious overall impression with fruity notes and a considerably increased diffusivity. . The judges found the last composition to be more effective than the others. Example 11 Perfume composition with floral character Parts by weight Lauryl (Hydroxycitronellal Extra) 760 Linalool 70 N-hexyl salicylate 30 Cyclamenaldehyde 20 Galbanum oil 20 900 This simply prepared floral complex undergoes a change in that the effect of cyclamenaldehyde is suppressed by the addition of 100 parts of ester. This composite appears to be substantially fresher and lighter than without this addition. On the other hand, ester' strengthens linalool. On the other hand, if equal amounts of ester mixtures ' and ' (10:90 to 30:70) are added, the hydroxycitronellal notes are surprisingly intensified. This composition was the most potent and most diffusive to date, and was therefore rated well by the reviewers. Example 12 Composition of bulk character Parts by weight of 3,5-dimethyl-cyclohex-3-ene-carboxaldehyde (10% in propylene glycol)
%) 2 n-decanal (10% in propylene glycol)
3 Geranyl acetate 5 α-ionone 10 1,1-dimethyl-4-acetyl-6-tert.butyl-indane 10 Cinnamyl alcohol (synthetic) 50 Citronellol (extra) 100 Geranyl (extra) 200 Phenylethyl alcohol (extra) 500 880 The addition of 12% ester' gives this base a very pronounced musky character. In its floral nature this one reminds me of pale roses. Muskiness cannot be created by adding 12% ester'. On the other hand, the olfactory quality of a dark rose (damask rose) occurs. With the addition of 12% of the ester mixture 'and' (15:85), the olfactory properties of the original base were very substantially improved, and the addition of the ester mixture 'and' alone resulted in a somewhat fruity, pleasant taste. It will be improved in the direction of fresh dotu growth. Example 13 Tobacco flavor (e.g. top flavor for cigarettes)

【table】

[Table] A suitable concentration would be, for example, 100g of flavor per 100kg of tobacco. Composition A contains ester mixture'
By adding and ′ (in a ratio of 25:75), the tobacco note is significantly emphasized. Smoking this flavored tobacco produces a typical olfactory flavor impression that is strongly reminiscent of blonde Virginia tobacco. Example 14

【table】

[Table] A suitable concentration is, for example, 40 g in 100 syrup. Ester mixture ′ and ′ (in a ratio of 25:75)
By adding to composition A, the original fruity notes in terms of aroma and taste are sharply intensified. In both cases, new notes reminiscent of fresh yellow strawberries can be detected. Example 15

【table】

[Table] A suitable concentration is, for example, 40 grams of flavor in 100 grams of syrup. Ester mixture ′ and ′ (25:75
) to composition A, a perceptible change in aroma and flavor occurs. As for the flavor, the sweet notes that were originally present are advantageously softened and new notes of fruity freshness typical of fresh grapes appear.

Claims (1)

[Claims] 1. General formula (wherein R represents _C1-4 -alkyl or _C2-4 -alkenyl and one of the three dashed lines represents an additional bond). 2. Ester according to claim 1, wherein R is ethyl. 3 General formula Perfuming or flavoring compositions containing an ester having the formula: wherein R represents _C1-4 -alkyl or _C2-4 -alkenyl and one of the three dashed lines represents an addition bond. 4 General formula (In the formula, R represents C _1-4 -alkyl or C _2-4 -alkenyl, and one of the three broken lines represents an addition bond.) In the method for producing an ester having the general formula A process as described above, characterized in that the ester of C _1-4 -alkyl or C _2-4 -alkenyl is cyclized.