CH628217A5 - Process for altering organoleptic properties of products - Google Patents

Description

The invention also relates to an agent for carrying out the method, which agent is characterized in that it contains at least one compound of the formula (1) as a component, preferably together with at least one auxiliary (adjuvant) and / or a carrier.

As auxiliary substances or carriers e.g. among others, the stabilizers, thickeners, surfactants, conditioning agents, flavoring agents, flavoring agents, etc. known from food technology, cosmetics and tobacco processing. The excipient can be solid or liquid and can preferably give a homogeneous product with the compound (1) or the mixture of such compounds when dispersing or mixing. The expedient auxiliary substance can essentially depend on the desired end product.

The amount of the compound (1) used according to the invention can be varied within wide limits, and even small amounts, for example from 0.10 to about 50 parts per million (ppm), based on the weight of the entire food, are sufficient for foods. Higher concentrations are usually unnecessary. For flavoring or flavoring agents, the compounds (1) are expediently used in higher proportions, for example in concentrations of about 0.015 to about 10%, based on the total weight of the flavoring or flavoring agents.

Appropriate agents can be added or prepared using customary methods, such as those described in e.g. are known for processing dough masses or vegetable juices by simply mixing them to the desired consistency and equilibrium. Preparations in the form of particulate solids can e.g. by mixing compound of formula (1) with adjuvants such as arabic gum, gum gum and the like, and then spray drying the mixture to form a particulate solid. Finished powdered flavor mixtures, e.g. a strawberry or raspberry flavored powder mix can be made by mixing with solid components e.g. Starch, sugar and the like can be obtained.

Examples of preferred auxiliaries for combination with compounds of the formula (1) are the following: p-hydroxy-benzylacetone, vanillin, maltol, ethyl-3-methyl-3-phenyl-glvcidate, benzyl acetate, ethyl butyrate, methyl cinnamate, methyl etherhranilate, a -Jonon, y-undecalactone, diacetyl, anethole, cis-3-hexenoI, 2 (4-hydroxy-4-methylpentyl) -nörb0tnadiene, ß-Jonon, isobutyl acetate, dimethyl sulfide, acetic acid, acetal dehyde, 4 (2,6, 6-trimethyl-l, 3-cyclohexadien-l-yl) -2-butanone, 4 (6,6-dimethyl-2-methylene-3-cyclohexen-l-yl) -2-butanone, Geranio !, ethyl pelargonate, isoamyl acetate , Naphthyl ethyl ether, ethyl acetate, isoamyl butyrate, 2-methyl-2-pentenoic acid, 2-methyl-3-pentenoic acid, «elemecin» (4-allyl-l, 2,6-tri-methoxybenzene) and «isoelemecin» [4 ( l-propenyl) -l, 2,6-tri-methoxybenzene].

The invention is also applicable to smokers' goods and enables products with the desired sweet, fruity and woody aroma properties of Turkish tobacco, whether to produce this aroma, to intensify it or to keep it at a certain uniform value when the tobacco components change. You can do that

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Smoke tobacco or a substitute therefor (e.g. dried lettuce leaves) or parts of smokers' goods, such as filters (e.g. cellulose acetate filters), are provided with a flavoring agent which contains at least one compound of the formula (1) as active component. The following are suitable as additional flavor and aroma additives:

(I) Synthetic substances

β-ethyl cinnamaldehyde, eugenol, dipentene, damascenone, maltol, ethyl maltol, A-undecalactone, A-decalactone, benzaldehyde, amyl acetate, ethyl butyrate, ethyl valerate, ethyl acetate, 2-hexenol-l, 2-methyl-5-isopropyl l, 3-nonadien-8-one, 2,6-dimethyl-2,6-undecadien-10-one, 2-methyl-5-isopropyl-aceto-phenone, 2-hydroxy-2,5,5, 8a-tetramethyl-l (2-hydroxyethyl) decahydronaphthalene, dodecahydro-3a, 6,6,9a-tetramethyl-naphtho (2, lb) furan, 4-hydroxyhexanoic acid, y-lactone and polyisoprenoid hydrocarbons according to US Pat. No. 3,589 372.

(II) Natural oils

Celery seed oil, coffee extract, bergamot oil, cocoa extract, nutmeg oil and oregano oil.

The flavoring agent with compound (1) can be added to smoking tobacco, to the filter or to the sheet or paper wrapping material. The tobacco can be treated in all processing and blending stages and reconstituted tobacco or tobacco substitutes (e.g. lettuce leaves) can also be treated. The levels of flavor additive can be changed as needed, with good results e.g. with total proportions between 5 and 500 ppm (0.005% to 0.05%) of the active component (1), based on the tobacco weight, or if the proportion by weight of compound (1) 0.02 to 5% of the tobacco flavoring agent (Sauce) makes up. The compounds (1) can be introduced into the tobacco product or its components in any manner, e.g. alone or together with other flavor additives or in suitable solvents such as ethanol, pentane or diethyl ether.

For example, stored fermented and shredded North American "Buriey" tobacco can be sprayed with a 20% ethanol solution of compound (43) in an amount to provide the tobacco mixture with 20 ppm compound (43), based on dry weight. Then the alcohol can be removed by evaporation and the tobacco can be processed into cigarettes in the usual way. The cigarettes treated in this way show a desired and pleasantly sweet, fruity and woody aroma, which is recognizable when smoking in the main stream and the side streams. The aroma can be described as sweet, rich, less spicy and tobacco-like with woody and fruity notes.

In an analogous manner, a 20% ethanol solution of a mixture of 50% compound (31) and 50% compound (33) can be sprayed onto the tobacco in such an amount that it contains 100 ppm (weight) of compound (31) and 100 ppm (Weight) of compound (33) on a dry basis. These cigarettes also have a desirable, pleasant aroma, which is noticeable when the cigarette is smoked in the main stream and in the side streams and can be described as a “Turkish / Orient” tobacco flavor.

For the production of fragrance mixtures, one or more compounds (1) can optionally be used with auxiliary perfume components, such as alcohols, aldehydes, nitriles, esters, cyclic esters or natural aromatic oils, or with the additives customary in perfumery, the Total amount of compound (1) in the perfumed article or the perfume composition of, for example 0.3% or less (e.g. 0.05%) for soaps, detergents or less fragrant cosmetic preparations can make up to 100% of the odor-causing components. In addition to detergents and soap, many other products such as room fragrances and deodorants, perfume, colognes, toilet water, bath additives, e.g. Bath oils and solid bath additives, hair treatment agents such as hair varnish, brilliants, pommade and shampoo, cosmetic preparations such as creams, deodorants, hand lotions and sunscreens, powders such as talcum powder, e.g. Body or face powder, flavored with compounds (1), whereby amounts of only 100 ppm compound (1) are sufficient to produce a fruity, green strawberry note with camomile nuances or fruity, herbal-like notes or fruity, peppery-camomile-like floral notes , which are basic smell characteristics of strawberry and / or raspberry perfume preparations. In general, no more than 2.0% of compound (1), based on the end product, is required in perfume preparations.

The perfumed articles or perfume preparations mentioned may contain customary vehicles for the compound (1), e.g. cosmetically permissible liquid substances, such as alcohols, glycols or the like. Solids having an absorptive or adsorptive action, e.g. Natural rubbers (plant mucilages), such as arabic gum, or encapsulating agents, such as gelatin, are suitable.

According to one embodiment of the invention, solid or liquid foods, chewing gum and flavoring or flavoring agents for the products mentioned can have sweet, vinous, peach, strawberry-tagetesoil-like and / or apple aromas and sweet, vinous, strawberry, pear, days-tesoil, Apple-like and / or creamy notes, as well as new perfume preparations with berry, pungent, apple, wermuth, chamomile and / or pineapple notes and tobacco flavoring agents are obtained that contain tobacco or tobacco items, e.g. Cigarettes can give a fruity and woody character with aromatic, sweet and woody notes by using isomer mixtures as the compound (1) which contain at least one 2-methyl 1-3,4 - pentadienoic acid alkyl ester (the alkyl radical contains 1-6 C- Atoms) contain and by reacting propargyl alcohol (6) and a trialkyl orthopropionate (7) (whose alkyl groups contain 1-6 carbon atoms) in the presence of a lower alkanoic acid according to the scheme

Alkanoic acid (6) + (7) ^ (4)

are available. R in formulas (4) and (7) means alkyl radicals, such as e.g. Methyl, ethyl, isobutyl or n-hexyl residues. The reaction can be carried out at 2-10 atmospheres and 140 to 180 ° C. The molar ratio values of the compounds (7): (6) can be between 1: 2 and 2: 1, a weak molar excess of compound (6) being preferred. Suitable lower alkanoic acids for this reaction are acetic acid, propionic acid, butyric acid, valeric acid or isovaleric acid.

According to a further embodiment, it was found that solid or liquid foods, chewing gum and flavoring agents for these products with sweet, fruity, fresh, berry, pineapple, green, herbal, strawberry and peach-like aromas and fruity, berry, woody, green pear flavors, as well as new ones Perfume preparations with fruity, peppery, woody, green, herbal, strawberry and chamomile notes, as well as new tobacco flavoring agents which give tobacco the character of Turkish tobacco with aromatic, sweet and bitter notes can be obtained if compounds (1) are alkyl esters of 2-methyl-cis-3-pentene acids (compounds of the formula 2) or isomer mixtures which contain more than 50% cis isomers of the formula (2)

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hold, wherein R in formula (2) is an alkyl radical having up to 6 carbon atoms, in particular 2-6 carbon atoms. These connections are available through:

(I) Preparation of 2-halogen-3-pentene and reaction with magnesium to form 2-halogeno-3-pentene; the 2-magnesium-halogen-3-pentene compound thus obtained can be reacted with carbon dioxide to form the magnesium halogen salt of 2-methyl-3-pentenoic acid, which can then be hydrolyzed in the presence of acid to form an isomer mixture which is approximately 60%

Contains 2-methyl-cis-3-pentenoic acid (formula 21) and 40% of the corresponding trans form of this acid. This mixture of "ice" and "trans" isomers of 2-methyl-3-pentenoic acid can then be reacted with alkyl halide in a basic medium to form an isomer mixture of the corresponding lower alkyl esters (22).

(II) Reaction of methyl acetylene with a methyl magnesium halide to form methylacetylene magnesium halide Grignard reagent, which with acetaldehyde to

3-Pentin-2-ol-magnesium halide salt implemented and so to

3-Pentin-2-ol is hydrolyzed. The hydrolyzate obtained can be halogenated to produce 4-halo-2-pentine and then with magnesium to a corresponding one

4-Magnesium-halogen-2-pentin-Grignard compound can be implemented. This Grignard compound can in turn be reacted with carbon dioxide to form a mixture of magnesium halocarboxylate salts of the formulas (10) and (12), in which X denotes halogen. The mixture thus obtained can finally be hydrolyzed to form a mixture of carboxylic acids which correspond to the formulas (10) and (11) but carry hydrogen atoms instead of the MgX group. The resulting mixture of carboxylic acids can be hydrogenated to form a mixture containing 80% compound of formula (21) and 20% 2-methyl-2-pentenoic acid. Then this mixture of pentenoic acids with alkyl halide in the presence of alkali metal hydroxide in a solvent, e.g. Esterify hexamethylphosphoramide, di-lower alkylformamide or dimethyl sulfoxide. If desired, the esters obtained can be worked up to obtain practically pure compound of the formula (22).

(III) Furthermore, at least one compound of the formula (4) in the presence of hydrogenation catalyst, in particular Raney nickel, palladium-on-carbon or palladium-on-calcium carbonate (“LindIar” catalyst), at 10 to 100 ° C. under Hydrogen pressures of about 0.35 to 5.6 atü hydrogen, the concentration of the catalyst, based on the weight of compound (4), for example is between about 0.1 and about 10%. A product which contains at least 60% by weight of at least one compound of the formula (22) can be obtained from the reaction mass. If necessary, the product can be worked up to obtain high-purity compound (22) (up to 100% purity). However, the corresponding carboxylic acid (21) can also be prepared by hydrolyzing the optionally isolated or the unprocessed hydrogenation product with a basic hydrolysis agent which is an aqueous or an alcoholic alkali metal hydroxide solution and then esterified, e.g. by reaction with an esterifying agent such as alkanol in the presence of protonic acid as a catalyst.

According to a further embodiment of the invention, it has been found that solid or liquid foods, chewing gum and flavoring or flavoring agents for this purpose have sweet, fruity, strawberry-like, wine / cognac-like, pineapple-like, pear-like, green and apple-like aromas or taste types with aroma or taste nuances of cooked strawberries, as well as new perfume preparations with fruity, strawberry-like,

sweet, cheesy, animal, berry, green, pear and banana-like notes, and new tobacco flavoring agents that give tobacco the character of Turkish tobacco with aromatic, sweet, sour, bitter, fruity, green and strawberry-like notes, through the use of compounds (1 ) in the form of compounds of the formula (3), in which R represents the hydrogen atom or alkyl having up to 6 C atoms, in particular having 1-6 C atoms, in foods, perfume preparations, perfumed articles, colognes and tobacco or Tobacco substitutes can be obtained.

The compounds of formula (3) in the form of acids

(31) or ester (32) can be obtained by one of the following processes:

(A) reaction of a 1,1,1-trialkoxypropane with 2-propenol-1 to give the ester (32), which according to one process form (i) is used directly because of its organoleptic properties, or (ii) saponification of the ester (32 ) with base to form a salt of acid (31) and then acidifying the salt of (31) with acid to form acid (31) and using this acid for its organoleptic properties.

(B) reaction of 1,1,1-trialkoxypropane with 2-propynol-l to form ester (42), then according to one embodiment either (i) hydrogenation of the ester (42) thus formed with hydrogen in the presence of Palladium-on-carbon or palladium on calcium carbonate catalyst to form a mixture, the compounds of the formula

(32), which mixture can be used directly because of its organoleptic properties, or (ii) can be worked up to isolate the ester (32), which is then used for its organoleptic properties, or finally (iii) saponification of the ester (32) with base to form a salt of acid (31), then acidifying the salt of acid (31) to obtain free acid (31), which is then used for its organoleptic properties.

New isomer mixtures of 2-methyl-3-pentenoic acid alkyl esters which have a cis: trans isomer ratio of approximately 60:40 can be prepared as follows:

(a-1) Preparation of 2-halo-3-pentene by intimately mixing hydrogen chloride or hydrogen bromide with 1,3-pentadiene at -20 to + 30 ° C, preferably at 0-10 ° C, and preferably atmospheric pressure. The 1,3-pentadiene obtained in this way, also referred to as “piperylene”, preferably has a purity of 90%, but 5Q% piperylene can also be used. The resulting 2-halogeno-3-pentene can be used in its crude form for the following reactions without further purification.

(b-1) The 2-halogen-3-pentene is then reacted with magnesium to give Grignard's reagent, which can also be referred to as 2-magnesium-halogen-3-pentene. The reaction with magnesium is preferably carried out in the presence of tetra-hydrofuran, but other solvents, such as diethyl ether, can also be used. The molar ratio of magnesium to halogen pentene is preferably 1-10 mol of magnesium per mol of halogen pentene, in particular 3-5 mol of magnesium per mol of halogen pentene. The reaction temperature can be 10-50 ° C, preferably 10-20 ° C. Temperatures below 10 ° C lead to a slow and therefore uneconomical implementation. Temperatures above 50 ° C usually cause side reactions, which reduces the yield.

(c-1) The Grignard reagent produced in step (b-1) is reacted with carbon dioxide (preferably in the form of crushed dry ice). This conversion can also be achieved by adding carbon dioxide to the Grignard

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Bubbling in reagent at atmospheric pressure between -20 to + 40 ° C, preferably 0-20 ° C, or the Grignard reagent at higher pressures of, for example, 2.70 to 7.0 kg / cm 2 absolutely at temperatures up to 50 ° C reacted gaseous C02. If the reaction is carried out with crushed dry ice, this determines the reaction temperature. The carbonation forms the magnesium salt of 2-methyl-3-pentenoic acid, Mg-halogen salt of the formula (12), in which X denotes a chlorine or bromine atom.

(d-1) Hydrolysis of the magnesium salt thus obtained in acid at a pH of 2-3, with mineral acids such as hydrochloric acid or sulfuric acid being preferred.

(e-1) esterifying the 2-methyl-3-pentenoic acid obtained with alkyl halide of the formula RX, in which R is an alkyl radical having 1-6, preferably 2-6 C atoms and X is the chlorine, bromine or iodine atom, in the presence of an equivalent amount of base (e.g. 50% aqueous sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate or lithium hydroxide) and in the presence of solvents, e.g. Hexamethylphosphoramide, di-lower alkylformamide, such as dimethylformamide and dimethyl sulfoxide, at 0-50 ° C, at room temperature, i.e. 20-30 ° C, is preferred. The solvent ratio is in the range of 300 to 900 g of solvent per mole of 2-methyl-3-pentenoic acid, with a ratio of 600 g of solvent per mole of the acid being preferred. The reaction rate is inversely proportional to the reaction temperature. However, temperatures that are too high usually lead to isomerization of the reaction product. The reaction time can be 2-50 hours.

(f-1) If desired, the resulting 60:40 cis-trans mixture of 2-methyl-3-pentenoic acid alkyl esters can be separated chromatographically (GLC systems).

New isomer mixtures which contain a high proportion of 2-methyl-cis-3-pentenoic acid alkyl ester of the formula (22), namely 80% of compound (22) and 20% of 2-methyl-2-pentene acid alkyl ester, are according to the following procedure available:

(a-2) Preparation of a methyl acetylene magnesium halide Grignard reagent by mixing methyl magnesium halide (the chloride, bromide or iodide) with a weak molar excess of methyl acetylene (preferably "Mapp" gas, see Example 15) at temperatures of 40 -60, preferably 40-50 ° C, in an inert solvent such as tetrahydrofuran or diethyl ether. The reaction time is preferably between 4 and 12 hours.

(b-2) Preparation of 3-pentyn-2-ol by mixing the above product (a-2), preferably in its original reaction solvent, with a slight molar excess of acetaldehyde to form a magnesium halide salt of 3-pentyn-2-ol at temperatures from 20 to 30 ° C. and subsequent hydrolysis of the magnesium halide of 3-pentyn-2-ol, preferably with cold concentrated mineral acid, such as hydrochloric acid in ice, and cleaning of the 3-pentyn-2-ol formed by customary processes, e.g. Extraction and distillation.

(c-2) Preparation of 4-halo-2-pentyne (e.g. 4-chloro-2-pentyne or 4-bromo-2-pentyne) by halogenating the 3-pentyn-2-ol with a slight molar excess of halo generating agents, e.g. Phosphorus trichloride, phosphorus tribromide or SOCl2, at 20-80 ° C. PC13 is preferred at 20-25 ° C.

(d-2) Preparation of 4-magnesium-halo-2-pentin - Grignard reagent by reacting the 4-halo-2-pentene with magnesium in a solvent, e.g. Tetrahydrofuran or diethyl ether, at 25-50 ° C depending on the solvent used.

(e-2) preparation of a magnesium-halogen-carboxylate-salt mixture of compounds of the formulas (10) and (11),

in which X halogen, e.g. Chlorine or bromine means by reaction with carbon dioxide in the gaseous or solid phase, as described in (c-1).

(f-2) hydrolyzing the mixture with aqueous mineral acid, for example hydrochloric acid, at 20-30 ° C. to form a crude mixture of (i) 2-methyl-3-pentic acid and (ii) 2-methyl-2,3- pentadienoic acid in an (i): (ii) ratio of 3: 1.

(g-2) Preparation of a mixture containing about 80% compound of formula (21) and 20% 2-methyl-2-pentenoic acid by hydrogenating the mixed product obtained in step (f-2) in the presence of palladium / calcium sulfate Catalyst containing 3% palladium at a pressure of 0.7 to 7.0 atü, preferably at 1.4 to 2.8 atü, preferably in lower alkanol as a solvent, for example Methanol or ethanol, at temperatures of 20-40, especially 20-25 ° C. The percentage of catalyst is e.g. 0.05 to 1.5%, with a range of 0.1 to 1% being preferred. The resulting acid can be purified in a conventional manner, e.g. by extraction or distillation.

(h-2) Esterifying the resulting mixture containing 80% compound of formula (21) and 20% 2-methyl-2-pentenoic acid as described in (e-1) above.

(i-2) If desired, the ester mixture obtained can be separated by chromatography (GLC).

You can also work according to the invention as follows:

(a-3) Reaction of 1,1,1-triethoxypropane with 2-propenol-1 in the presence of a phosphoric acid catalyst to give ethyl 2-methyl-4-pentenoate. The temperature can be 100-225 ° C, preferably 140-180 ° C. The preferred molar ratio of the reaction components is 1: 1, a large excess of 2-propenol-1 being undesirable and a large excess of triethoxypropane being uneconomical. The rate of conversion is inversely proportional to the reaction temperature. At reaction temperatures of 165-185 ° C, the reaction time is about 3 hours. The reaction product, 2-methyl-4-pentenoic acid ethyl ester, can be used as such or further implemented as in steps (b-3) and (c-3) below will. In any case, the reaction product is worked up by combining the phosphoric acid used as catalyst with base, e.g. Sodium bicarbonate, neutralized and the reaction product is then fractionally distilled.

(b-3) If desired, the compound (32) obtained, in which alk denotes alkyl having 1-6 C atoms, can be converted into the acid (31) in the customary manner by saponification and acidification. The saponification is preferably carried out with a strong aqueous base, e.g. 50% aqueous sodium hydroxide solution or 50% sodium hydroxide solution mixed with methanol. After acidifying the resulting salt of compound (31), i.e. the sodium or potassium salt, using mineral acid, e.g. 6 molar aqueous hydrochloric acid, the compound (31) is extracted from the aqueous phase with organic solvent, such as toluene. The organic solvent is then separated from the acid and this is fractionally distilled. The resulting solution can be used as such or, if desired, esterified with a C3-C6 alkanol to give an ester of the formula (32).

(c-3) If desired, the ester (32) obtained according to (a-3) can be converted into another ester, a C3, C4, C5 or C6 ester of 2-methyl-4-pentenoic acid by reaction with alkanol, which contains 3-6 C atoms, can be converted in the presence of protonic acid as a catalyst at 100-170 ° C. The preferred temperature depends on the alkanol. When using isobutanol, it is e.g. about 110 ° C, when using n-hexanol e.g. 140-150 ° C. p-toluenesulfonic acid is the preferred catalyst.

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The above reactions can be represented by the following scheme:

h3po4

(7), R = C2H5, + (8) - * (32), R = C2H5,

Transesterification R'OH

(32), R = C2H5,

-> (32), R - R ',

hydrolysis

-> - (31)

(R '= C3-C6 lower alkyl)

Another method according to the invention is based on the following steps:

(a-4) reaction of compound (7), e.g. 1,1,1-tri-ethoxypropane or 1,1,1-trihexyloxypropane, with compound

(6) in the presence of propionic acid as a catalyst to form the starting compound of formula (42). This reaction can take place at 120-180, preferably 145-150 ° C. The preferred molar ratio is 1: 1, with a slight excess of each component being allowed. A large excess of compound (6) is undesirable, a large excess of compound (7) is uneconomical. The proportion of propionic acid can be 1-3%, preferably 2%. Because of the reaction temperature at 120-180 ° C, work is carried out under increased pressure, e.g. 2.10 to 7 atm, which requires the use of an autoclave. The reaction time is inversely proportional to the reaction temperature. At temperatures of 150-160 ° C it takes about 3 hours. The reaction time can vary between 2 and 6 hours, preferably 3-4 hours. The reaction product of formula (42) can then be worked up, for example by destroying the excess compound

(7) by washing with 5% hydrochloric acid solution. After neutralization, e.g. with sodium bicarbonate solution, the reaction mixture can be fractionated.

(b-4) The compound (42) can be used as such or hydrogenated in the presence of a catalyst such as Raney nickel, palladium-on-carbon or “Lindlar” catalyst. The palladium content of the catalysts can be between about 2 and 7%, preferably 5%. The hydrogenation can be carried out at about 10 to about 100 ° C, preferably at 25-35 ° C. Since the implementation is exothermic, cooling is usually required from the outside. The hydrogen pressure can be between about 0.35 and 7.0 atm, preferably about 1.4 atm. Pressures of over 10.5 atü lead to larger proportions of saturated ester. The hydrogenation can be carried out with or without a solvent. Conventional inert solvents such as isopropanol, hexane or ethanol can be used as solvents, the alkyl group of the alcohol being the same as the alkyl group of the alkoxy group of the hydrogenated ester. With solvent, a molar ratio of solvent: ester of approximately 1: 1 is preferred. With a palladium-containing catalyst, the catalyst content of the reaction mixture can be between 0.125 and 2.0%, preferably about 0.25%. With Raney nickel as the catalyst, the catalyst content is usually about 3 to about 10%, preferably about 5%. The hydrogenation yields a mixture of compounds of the formulas (22), (32) and (52), all mixtures containing at least 60% of compound (22). Compound (22) can be separated and purified by fractional distillation, especially if the only other hydrogenation product is a compound of formula (52). If the hydrogenation product contains compounds of the formula (32), the proportion of compound (22) can be enriched by fractional distillation or as such for perfume preparations or tobacco.

Flavoring agents or as a flavor adjuvant or flavor enhancer for food or chewing gum can be used. When using «Lindlar» * catalyst, a mixture of compounds (22) and 5 (32) is formed. A mixture of (22), (32) and (52) is formed with palladium-on-carbon as a catalyst, but not always with a «Lindlar» catalyst, which in turn is also used as a flavor additive or enhancer for food, tobacco products , Chewing gum or for perfume preparations io or as an additive for perfumed articles. With Raney nickel as a catalyst, a mixture of (22), (32) and (52) is first formed, the percentage of (22) being over 50% by weight of the total product. As the hydrogenation progresses, however, the percentage of (32) falls to zero, while the percentage of (52) increases, the percentage of (22) remaining approximately the same. The mixture obtained after the hydrogenation is generally filtered to remove the catalyst and the filtrate is fractionally distilled under reduced pressure. 20 (c-4) If desired, the compounds (32) obtained and, if desired, other esters present which have not been separated off after the hydrogenation can be converted into the corresponding carboxylic acids by conventional saponification and acidification as in (b-3). 25 (d-4) If desired, the 2-methylpentensic acid alkyl esters obtained according to (b-4) can be transesterified according to (c-3).

Implementations (a-4) to (d-4) correspond to the following scheme:

30th

(6) + (7)

Propionic acid

(42)

35 (42)

(1)

Hydrogenate

[(22), (32), (52)]

[Oh-]

^ [(21), (31), (51)]

(2) [H +]

40

Examples of compounds (1) obtainable after the reactions described above and the organoleptic properties of these substances are described individually below.

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Connection (23):

Fresh, fruity, pineapple-like strawberry aroma and sweet, fruity, pineapple-like, strawberry-like, melon-green taste at 1 ppm, also a fruity, green strawberry-50 fragrance with camomile nuance.

Compound (22), Alk = isopropyl:

Fruity, characteristic strawberry flavor and sweet 55 astringent aftertaste at 5 ppm and a fruity herbal fragrance.

Compound (22), alk - isobutyl:

Characteristic sweet strawberry flavor with persistent-60 aftertaste of strawberry at 5 ppm; characteristic sweet strawberry flavor at 10 ppm with persistent strawberry aftertaste; also a fruity, woody fragrance.

65 compound (22), alk = n-hexyl:

Pear-like, fruity strawberry aroma and sweet fruity, pear-like strawberry flavor at 2 ppm; also fruity, peppery notes of camomile and flowers.

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Connection (33):

(i) Flavor - at 0.05 ppm fresh, sweet, fruity; very pleasant at 0.1 ppm, strawberry-like, wine-like; at 0.2 ppm wine-like, pineapple-like; at 0.5 ppm strawberry-like, apple-like, fruity; at 1 ppm green, fruity; at 2 ppm green, apple-like; (ii) fragrance - green, sweet notes; Fruit and strawberry notes; (iii) tobacco taste - sweet, fruity, strawberry-like and slightly green aroma; at 100 ppm and 200 ppm smoking more aromatic, less biting, similar to Turkish tobacco.

Connection (31):

(i) Flavor - Aroma and taste of cooked strawberries at 10 ppm; (ii) fragrance - cheesy, slightly animal, sweet, berry-like notes; (iii) tobacco taste - acrid, sweet, fruity, sour and green notes; at 100 ppm and 200 ppm when smoking sweeter and more like oriental Turkish tobacco.

Compound (32), Alk = isobutyl:

(i) Flavor - at 5 ppm fruity, pineapple and strawberry-like aroma and fruity, pineapple-like, strawberry-like, sweet taste; (ii) Fragrance - green, sweet, fruity and berry notes.

Compound (32), Alk = n-hexyl:

(i) Flavor - at 5 ppm pear-like green aromas and flavors; (ii) Fragrance - a green, floral, slightly fruity, apple-like pear and banana note.

Connection (43):

(i) Flavor - at 0.2 ppm fruity, strawberry-like, creamy aroma with berry, apple and pineapple notes and a sweet, fruity strawberry flavor with woody and creamy nuances; (ii) tobacco taste - the aroma of cigarettes with this compound in the tobacco or filter is sweeter and fruity; the smoke of such cigarettes is more aromatic, sweeter, fruity and less acrid in the mouth and throat and gives a woody nuance when smoking.

Compound (42), alk - n-hexyl:

(i) Flavor - sweet, fruity, strawberry-like and tagetes oil-like aroma as well as flavors with berry, pear and wine-like nuances; (ii) Scent - green, floral pear aroma with wormwood notes.

Compound (42), Alk = i-butyl:

Food taste - at 1 ppm wine and ester-like aroma and taste; at 2 ppm fruity and sweet aroma; at 5 ppm fruity and pineapple-like; at 10 ppm liquorice-like notes, wine-like.

In the following examples for the preparation or use of compounds (1), all parts and percentages are by weight, unless stated otherwise. The structure analysis is carried out by IR, chromatographic, NMR analysis, mass spectrography and the like. Detailed analytical values are given in the priority documents.

example 1

To prepare ethyl 2-methyl-3,4-pentadienoate (formula 43), a compound (6) is reacted with a compound (7), R = ethyl, to give the compound (43). For this purpose, 495 g of triethyl orthopropionate, 90 g of 2-propyne-l-oil and 12 g of propionic acid are heated in an autoclave at 150 ° C. for 50 minutes. The reaction mass is then 3 hours at 135-160 ° C below 1.5 to

Held 4.2 atm. The autoclave is then opened and the reaction mixture is allowed to cool to room temperature. Now 12.6 g sodium bicarbonate for the neutralization of propionic acid and 30 g "Primol" (registered trademark 5 ke for a hydrocarbon mineral oil from Exxon Corp.) and 0.1 g "Ionol" (registered trademark for 2.6 -Di - t-butyl-4-methylphenol) added. It is then distilled only at atmospheric pressure and a flask temperature of 129 ° C, a mixture of ethanol and ethyl propionate passing over. Then distillation is continued under vacuum, a total of about 220 g of compound (43) passing over at a steam temperature of 65-69 ° C. under a pressure of 24-33 mm Hg, the structure of which is confirmed by IR, NMR and mass spectrography.

15 At a concentration of 0.5 ppm, the compound (43) obtained has a fruity, strawberry-like, creamy aroma with berry, apple-like or pineapple-like notes and a sweet, fruity strawberry taste with woody and creamy nuances.

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Example 2

25 g of the compound (43) obtained according to Example 1 are placed with 0.025 g of a 5% palladium-on-carbon hydrogenation catalyst in a pressurized hydrogenation system (“Parr” -25 bomb) and with hydrogen at 1.75 to 3.5 kg / cm2 hydrogenated. The reaction temperature is kept at room temperature by external cooling. After 3.5 hours, the reaction mixture is filtered. According to chromatography, the conversion is then complete.

30 The product obtained is a mixture of 65.7% ethyl 2-methyl cis 3-pentenoate (formula 23), 14.3% ethyl 2-methyl 4-pentenoate (formula 33) and 19.9 % Ethyl 2-methyl pentenoate (Formula 53).

35 Example 3

577.8 g of the compound (43) obtained according to Example 1 and 1.4 g of 5% “Lindlar” catalyst are hydrogenated in an autoclave for 19 hours at a hydrogen pressure of 4.2 kg / cm 2 and the reaction mass is cooled by external cooling 40 kept at room temperature. Then another 1.4 g of “Lindlar” catalyst are added and the mixture is hydrogenated with stirring for a further 10 hours. The reaction mixture is then filtered off, a further 2.8 g of “Lindlar” catalyst are added, and the mixture is then hydrogenated further in an autoclave with hydrogen and a pressure 45 of 4.2 atm. After 105 minutes, the implementation, according to the chromatographic test, is complete. The reaction mixture is filtered off and with the addition of 10 g "Primol" and 0.1 g "Ionol" under about 200-205 mm Hg at a reflux ratio decreasing from 19: 1 to 9: 1 and decreasing to 4: 1. While the temperature of the distilled steam rose from 31 to 112 ° C, eleven fractions with a total of 138 g were removed. The following fractions 12-31, which passed at a steam temperato of 113-116 ° C, were pooled after analysis. The chromatographic examination of selected fractions gives the following values:

Fraction No.

Group weight

Share (23) in%

Share (33) in%

12th

6.2 g

57.6%

41.6%

13

7.0 g

59.2%

38.9%

21st

10.0 g

70.9%

28.7%

23

20.8 g

75.6%

24.1 g

31

13.5 g

93.8%

4.9%

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The structures of compounds (23) and (33) were confirmed by mass spectroscopy, nuclear magnetic resonance and IR analysis.

Example 4

283.3 g of the compound (43) obtained according to Example 1 are hydrogenated with 14 g of Raney nickel in an autoclave at 1.4 atm hydrogen pressure. The temperature is kept at 20 ° C. for 3 hours, which was sufficient for a complete reaction. The reaction mixture is then filtered off and chromatographed. Evidence from chromatography, nuclear magnetic resonance, IR and mass spectrometric analysis shows that the reaction mixture contains 65% of compound (23) and 35% of compound (53).

After adding 5.0 g "Primol" and 0.1 g "Ionol", the reaction mixture is fractionated at an absolute pressure of 20.0 mm Hg under a reflux ratio of 19: 1. When the steam temperature rises from 50 to 52 ° C, 15 fractions with a total of 180 g are removed. Then further fractions with a total of 62.3 g are taken at steam temperatures of 52-53 ° C. Chromatography, nuclear magnetic resonance and IR analysis show that the second group of fractions consisted of 5.7% compound (53) (ethyl 2-methylpentanoate) and 93.8% compound (23). This material has a fresh strawberry taste with slight gummy side notes. When this fraction is distilled again to remove the saturated ester, which counteracts the fine strawberry taste of the unsaturated cis ester, the material obtained is an excellent flavor with the taste of fresh strawberries. The material, which is made from 100% ice, has a fruity strawberry and pineapple aroma with rum and honey-like undertones and is suitable for flavoring foods, cosmetic articles and as a flavor additive for tobacco. The IR, NMR and mass spectroscopy data for the unsaturated cis ester of the formula (23) are identical to those determined in connection with Example 3.

Example 5

187 g of compound (43) and 7 g of Raney nickel are hydrogenated with stirring in an autoclave at 20-30 ° C. (external cooling) at 3.5 atm with hydrogen gas. The pressure is kept at the stated value by feeding in hydrogen and the temperature is kept at 20-30 ° C. for 5.5 hours. After 2.5 hours, 1 mol of hydrogen is absorbed by the reaction mass and the chromatographic analysis shows the following proportions: 2% compound (53), 25.7% compound (33), 62.5% compound (23) and 8.9 % Compound (43), the starting material. The reaction is continued by first bringing the pressure back to 3.5 kg / cm 2 with hydrogen. After 3.5 hours the reaction mass had absorbed 1.19 g-mole of hydrogen. Chromatographic analysis of this material showed that the mixture contained 11% of compound (53), 19.7% of compound (33) and 68% of compound (23). The reaction mixture was hydrogenated at 3.5 atm hydrogen for a further 2 hours, after which 1.5 g-mole of hydrogen (total) had been taken up by the reaction mass. After this period, gas chromatographic analysis showed that the product consisted of 35% compound (53) and 65% compound (23). It is noteworthy that after a total reaction time of 5.5 hours, the reaction mixture no longer contains any compound (33).

The reaction mixture is filtered off and fractionated with 5.0 g "Primol" and 0.1 g "Ionol" at a reflux ratio of 19: 1. At 20.0 mm Hg, a total of about 220 g of material (fractions 1-21) pass over at a steam temperature of 50-53 ° C. Then four more fractions are taken at 53 ° C, each weighing 5.5, 6.0, 7.5 and 3.8 g. Analysis of fraction No. 22 by nuclear magnetic resonance, chromatography and mass spectroscopy reveals 95% compound (23) and 5% compound (53). The statements made in Example 4 apply to further processing or use. When the hydrogenation is run for 5.5 hours without sampling, 1.48 g-mole of hydrogen is absorbed by the reaction mixture and the analysis shows 38% of compound (53) and 61.4% of compound (23). If the hydrogenation is repeated with sampling at 3.5 and 4 hours, the following results are obtained: after 3.5 hours, the hydrogen uptake is 1.4 g-mol and the product contains 27% of compound (53), 4 % of compound (33) and 68% of compound (23). After 4 hours the hydrogen uptake is 1.5 g-mol and the mixture contains 36% compound (53) and 63.6% compound (23).

Example 6

To prepare compound (7), R = n-hexyl, as starting material for the preparation of compound (46), 528 g (3 mol) of triethyl orthopropionate, 1530 g (15 mol) of n-hexyl alcohol, 3.4 g (0 , 02 mol) of p-toluenesulfonic acid and 20 g of "Primol" heated to 150 ° C. under atmospheric pressure. 398.9 g of “light” fractions, mainly ethanol, distill. The reaction mass was then further distilled under vacuum, a total of 930.7 g (87.6%) colorless liquid, namely trihexyl orthopropionate [formula (7), R = n-hexyl] at 1.3 mm Hg and 140-171 ° C. distilled over.

1240 g (3.5 mol) of the n-hexyl orthopropionate thus obtained, 196 g (3.5 mol) of 2-propyn-1-ol and 30 g of propionic acid are heated in an autoclave to 120-130 ° C. in 50 minutes. The mixture is kept at this temperature for 5 hours. The autoclave is then cooled to room temperature, the mixture is poured off and 35 g of sodium bicarbonate are added to re-neutralize the propionic acid. Then 40 g of "Primol" are added and the mixture obtained is distilled to form 10 fractions. Fractions Nos. 6, 7 and 8 distill at 95-101 ° C / 2.2-2.5 mm Hg (yield of 481.3 g of crude product), are combined and fractionated with the addition of 10 g of "Primol" and 0 , 1 g of "Ionol" distilled. At 3.2 to 3.5 mm Hg, a reflux ratio of 9: 1 and a steam temperature of 44-89 ° C initially 260 g (fractions No. 1-8) pass over. Fractions Nos. 9 and 10 are taken at steam temperatures of 89-90 ° C, 3.1 / 3.2 mm Hg at a reflux ratio of 3: 1 and weigh 84.1 g and 83.6 g, respectively. The remaining four fractions are taken at steam temperatures of 86-110 ° C and a reflux ratio of 9: 1 to 3: 1. IR, nuclear magnetic resonance and mass spectroscopy show a product of more than 99% purity and confirm the structure of the formula (46). The compound has an apple taste or aroma similar to tagetes oil with pear-like or greasy nuances.

Example 7

98 g (0.5 mol) of the compound (46) obtained according to Example 6 and 1.0 g of “Lmdlar” catalyst are hydrogenated in an autoclave at 3.5 atm with stirring for 40 min. Then the autoclave was opened and the reaction mixture was filtered off. ' Chromatographic analysis shows complete conversion to n-hexyl-2-methyl-cis-3-pentenoate (formula 26) and n-hexyl-2-methyl-4-pentenoate (formula 36).

Example 8

696.9 g of triisobutyl orthopropionate (compound 7, R = isobutyl), 151 g of 2-propyn-l-ol (compound 6) and 17 g of propionic acid are heated in an autoclave to 140 ° C. in 50 minutes. The mixture is kept at this temperature for 4 hours.

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The autoclave is then cooled to room temperature and 20 g of sodium bicarbonate are added to the reaction mixture to neutralize the propionic acid. After adding 30 g «Primol», the reaction mixture is fractionated again, at steam temperatures of 41-72 ° C and 7.3 to 7.8 mm Hg. First, three fractions with a total of 43.4 g at a reflux ratio of 19 : 1 taken. Fractions 4-10 are then taken at a reflux ratio of first 9: 1 and then 4: 1 with a total yield of 278 g. The further distillation still gives a small amount of product. Fractions Nos. 4-10 consisted of nuclear magnetic resonance and IR analysis from 99% pure product, whereby the structure of formula (45) was confirmed.

Example 9

168 g of the isobutyl-2-methyl-3,4-pentadienoate (formula 45) obtained according to Example 8 and 2.0 g of “Lindlar” catalyst are in the autoclave at 3.15 to 3.5 atm with hydrogen gas Stir hydrogenated. During 60 min of the hydrogenation time, the reaction mixture is kept at 50-82 ° C. by external cooling. The reaction mixture is then removed and filtered off. Chromatographic analysis shows that the entire material has been converted into a mixture of iso-butyl-2-methyl-4-pentenoate (formula 35) and isobutyl-2-methyl-cis-3-pentenoate (formula 25). The formulas given are confirmed by nuclear magnetic resonance, IR and mass spectroscopy.

Example 10

To produce 2-methyl-cis-3-pentenoic acid (formula 21), 60 g of 50% aqueous sodium hydroxide solution and 50 g of methanol are first mixed in a flask provided with a heating jacket. The reaction mixture heats up to 55 ° C and is kept at 20 ° C by external cooling. Then the compound (23) prepared according to Example 5 is added dropwise with stirring at 20 ° C. The addition takes place in 30 min. After completion, the reaction mixture is stirred for a further 30 min and then 22 g of concentrated sulfuric acid are added dropwise with stirring. To adjust the pH of the reaction mixture to 4, 150 ml of 5% hydrochloric acid are added. Then the reaction mixture is stirred for 15 min and extracted three times with 150 ml of diethyl ether. The extracts are combined and evaporated, the concentrated material is distilled. At steam temperatures of 80-90 ° C and 7.5 to 8.2 mm Hg, a total of 28.4 g of product pass over, with the first two fractions of 0.7 g and 3.0 g being at least 90% product (23 ), the two following fractions each consisted of more than 99% of product (23). Purity and structure are confirmed by NMR, IR and mass spectroscopy.

Example 11

To produce a cis-trans mixture of 2-methyl-3-pentenoic acid, 4-chloro-2-pentene is first prepared from 1000 g (14.8 mol) of piperylene (97.7% pure). For this purpose, the piperylene is cooled to 10 ° C. and the reaction vessel is flushed with dry nitrogen. With the introduction of hydrogen chloride, the reaction mixture is stirred vigorously and the temperature is kept at 10-15 ° C. by external cooling. The hydrogen chloride feed is carried out for 7 hours. The reaction mixture is then flushed with nitrogen at room temperature for 10-20 minutes to remove excess HCl. 1435 g of crude 4-chloro-2-pentene are obtained, which can be further processed directly into a 2-methyl-3-pentenoic acid / isomer mixture without purification.

600 g of magnesium shavings and 3 liters of tetrahydrofuran are mixed with 70 ml of a solution prepared by mixing 750 g of 4-chloro-2-pentene and 2 liters of tetrahydrofuran under stirring at 50 ° C. under nitrogen. The temperature rise shows the start of the Grignard reaction. Then, with continued stirring, the remaining part of the solution of 4-chloro-2-pentene is added, specifically over a period of 5 hours. After the first 30 minutes of addition, the reaction mixture is slowly cooled to 25-30 ° C. and then to this temperature held. After the addition is complete, the mixture is stirred at this temperature for 1 hour.

7.2 kg of finely ground dry ice are placed in a correspondingly large flask. The Grignard reagent prepared according to the above information is poured onto the dry ice 15, the excess magnesium chips being retained in the batch flask. A nitrogen stream is used to avoid premature reaction with carbon dioxide at the inlet. The mixture of dry ice and Grignard reagent is then slowly stirred until the excess carbon dioxide has evaporated. The mixture is stirred for a total of 8 hours. Then 2.5 liters of water are added to dissolve the magnesium salt and the tetrahydrofuran is recovered by distillation at normal pressure and a pot temperature of 80 ° C. 25 1.25 liters of toluene and 750 ml of concentrated hydrochloric acid are then added over the course of 30 minutes, the temperature being kept at 30-40 ° C. The reaction mixture is stirred for a further 30 min without further heating or cooling. The organic phase is removed and the aqueous layer is extracted with 1.5 liters of toluene, whereupon the organic layers are combined. The organic solutions are freed from solvent and the crude 2-methyl-2-pentenoic acid is rapidly distilled over at 180 ° C./2 mm Hg. The crude distillate is fractionated at 3 mm Hg and a steam temperature of 62-63 ° C with the addition of «Primol» 35 and «Ionol». NMR, IR and Raman spectral analyzes show that the product is a 60:40 cis: trans mixture of isomers of 2-methyl-3-pentenoic acid.

Example 12

40 To prepare a mixture of ice and trans isomers of ethyl 2-methyl-3-pentenoate, 38 g (0.33 mol) of the isomer mixture obtained according to Example 9, 40 g (0.37 mol) of ethyl bromide, 32 g (0.40 mol) of sodium hydroxide (50% aqueous solution) and 200 g of hexamethyl-45 phosphoramide were stirred for 15 hours at room temperature. Then 300 ml of water are added and the solution extracted with 200 ml of diethyl ether. The extract is washed with 20 ml of 20% saline and then concentrated on the rotary evaporator. The residue obtained (32 g) is thus distilled at 50 mm Hg, which gives 23 g of ethyl 2-methyl-3-pen-tenoate (chemical yield: 50%), bp 75 ° C./50 mm Hg. The ratio of cis isomer to trans isomer is 3: 2.

The cis-ethyl-2-methyl-3-pentenoate is separated chromatographically from this mixture of isomers.

Example 13

17.1 g (0.15 mol) of the 2-methyl-3-pentenoic acid obtained according to Example 11, 4.26 g (0.03 mol) of iodomethane, 3.6 g (0.03 60 mol) of isopropyl bromide, 4.11 g (0.03 mol) of isobutyl bromide, 4.53 g (0.03 mol) of isoamyl bromide, 16.0 g (0.2 mol) of sodium hydroxide (50% solution) and 180 g of hexamethylphosphoramide are used for 72 hours stirred at 20-25 ° C. After this time, the reaction mixture is diluted with 100 ml of water and extracted twice with 100 ml of diethyl ether. The extracts are evaporated and the residue distilled at 0.3 mm Hg, giving 6 g of oil. Chromatography shows that this mass consists of at least two main components and

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there are three secondary components. The main components are chromatographically intercepted and are shown to be mass spectrometry and nuclear magnetic resonance as iso-propyl-2-methyl-3-pentenoate and isobutyl-2-methyl-3-pen-tenoate.

Example 14

To prepare n-hexyl-2-methyl-3-pentenoate as a 3: 2 ice: trans isomer mixture, 1.1 g (0.01 mol) of the isomer mixture obtained according to Example 11, 2.0 g (0.012 mol) 1 -Bromhexane, 20 g hexamethylphosphoramide and 1.0 g (0.012 mol) sodium hydroxide (50% aqueous solution) stirred for 3 hours at room temperature. Then it is diluted with 100 ml of water and extracted with 50 ml of diethyl ether. The extract is washed three times with 10 ml of 20% saline. The ether is evaporated, giving 2.0 g of an oil. The chromatographic analysis shows 67% n-hexyl - 2-methyl-3-pentenoate. The mixture of the esters is separated by chromatography.

Example 15

To prepare a mixture containing 80% cis-2-methyl-3-pentenoic acid and 20% 2-methyl-2-pentenoic acid, 3-pentyn-2-ol is first prepared as follows: A technical mixture of methyl acetylene and allen ("Mapp gas") is introduced in a total amount of 600 g via a sodium hydroxide drying tube into a methyl magnesium chloride solution at 40-50 ° C. This takes 5 hours. The mixture is heated to 50 ° C. for a further 2 hours and then cooled. The cooled solution is mixed at 20-30 ° C. for 2 hours with 264 g acetaldehyde with cooling. The mixture is stirred for a further 1 hour at 25 ° C. and 800 ml of concentrated hydrochloric acid and 5 kg of ice are then added. The resulting lower layer is extracted with 1 liter of benzene and the combined organic liquids are washed with two 200 ml portions of 20% aqueous sodium chloride solution, heated to 92 ° C. at atmospheric pressure and then distilled under vacuum. The rapidly distilled material is distilled again at 45-50 mm Hg and a pot temperature of 72 ° C and then used to produce 4-chloro-2-pentine without further purification.

84 g (1 mol) of that obtained according to the above information

3-Pentin-2-ols and 69 g (0.5 mol) of phosphorus trichloride are combined at 20-25 ° C with cooling. The mixture will

Stirred at 20-25 ° C for 12 hours and then held at 72 ° C for 5 hours. The IR analysis indicates that the reaction is complete. Then the material is quickly distilled under vacuum. The 4-chloro-2-pentyne obtained is used for the following Grignard reaction.

46 g (0.5 mol) of that obtained as described above

4-Chloro-2-pentins are dissolved in 200 ml of tetrahydrofuran and added to 60 g of magnesium shavings in 300 ml of tetrahydrofuran within 4.5 hours (after initiation of the reaction with iodine crystals). At the start of implementation, the temperature rises to 44-50 ° C and is kept at 28-30 ° C by external cooling. After the addition is finished

Stirred for 1 hour. The resulting Grignard reagent is poured onto 620 g of powdered dry ice with stirring. After evaporation of the CO 2, 300 ml of water are added and the solution is extracted three times with 200 ml of toluene. After cooling and acidifying, the aqueous solution is processed further with 50 ml of concentrated hydrochloric acid by first being extracted twice with 200 ml of toluene. These toluene extracts are freed from solvent after washing three times with 50 ml of 20% sodium chloride solution and distilled crude. 22 g of crude acids are obtained. This crude product is then fractionated in a semi-microdistillation unit and gives 6.2 g of an acid mixture which is a 3: 1 mixture of 2-methyl, 3-pentynoic acid and 2-methyl-2,3-pentadienoic acid.

4 g of the mixture thus obtained are hydrogenated at room temperature in methanol in the presence of 0.1 g of 3% palladium-on-calcium sulfate catalyst at 2.8 atm hydrogen pressure. The implementation is complete in 5 minutes. After removal of the methanol, the oil remaining as a residue is analyzed. The chromatographic analysis shows only one peak, the nuclear magnetic resonance analysis, on the other hand, points to two products, namely cis-2-methyl-3-pentenoic acid and 2-methyl-2-pentenoic acid as a 4: 1 mixture.

Example 16

38 g (0.33 mol) of the acid mixture obtained according to Example 15, 40 g (0.37 mol) of ethyl bromide, 32 g (0.40 mol) of sodium hydroxide (as a 50% aqueous solution) and 200 g of hexamethylphosphoramide are 25 ° C. mixed with stirring and cooling. The mixture is stirred for 15 hours at room temperature and then mixed with 300 ml of water. The solution is extracted with 200 ml of diethyl ether, the extract is washed with 20 ml of 20% sodium chloride solution and then concentrated on a rotary evaporator. The resulting residue (32 g) is worked up at 55 mm Hg in a semi-microdistillation unit, which is 23 g of a mixture of 80% cis-ethyl-2-methyl-3-pentenoate and 20% ethyl-2-methyl-2-pentenoate results. The mixture is separated into its components by chromatography.

Example 17

1.1 g (0.01 mol) of the acid mixture obtained according to Example 15, 2.0 g (0.012 mol) of 1-bromohexane, 20 g of hexamethylphosphoramide and 1.0 g (0.012 mol) of sodium hydroxide as a 50% aqueous solution are 3 hours stirred at room temperature, then diluted with 100 ml of water and extracted with 50 ml of diethyl ether. The extract is washed three times with 10 ml of 20% aqueous saline and then evaporated to give 2.0 g of an oil as a product. Chromatographic separation gives cis-n-hexyl-2-methyl-3-pentenoate.

Example 18

495 g (2.4 mol) of triethyl orthopropionate (1,1,1-triethoxy propane), 140 g of allyl alcohol (2.4 mol) and 12 g of 85% phosphoric acid are stirred for 3 hours at 165-185 ° in an autoclave C warmed. The reaction mixture removed from the autoclave is mixed with 12.6 g of sodium bicarbonate to neutralize the phopsoric acid. Then 30 g «Primol» are added and the mixture is first fractionated at atmospheric pressure and 129 ° C, resulting in a mixture of ethanol and ethyl propionate (245 g). Then at 40 mm Hg and 75 ° C 264 g of ethyl 2-methyl-4 - pentenoate are distilled off as a product. The yield, based on the triethyl orthopropionate used, was 73.5%.

Example 19

To produce 2-methyl-4-pentenoic acid, 80 g of the ethyl 2-methyl-4-pen-tenoate obtained according to Example 18, 70 g of 50% sodium hydroxide and 100 ml of methanol are stirred at 30-50 ° C. for 4 hours and then mixed with 200 ml of water. The mixture is extracted three times with 200 ml of toluene and, after acidification, the aqueous layer is extracted with twice 100 ml of toluene. The combined toluene extracts are washed three times with 50 ml of 20% aqueous sodium chloride solution and then once with 40 ml of 10% sodium acetate. The reaction product treated in this way is evaporated to remove the toluene. The target product is obtained by fractional distillation at 72-74 ° C / 5 mm Hg.

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Example 20

56 g (0.4 mol) of the product obtained according to Example 18, 112 g of isobutyl alcohol, 0.5 g of p-toluenesulfonic acid, 10 g of “Primol” and 0.1 g are used to produce isobutyl 2-methyl-4-pentenoate "Ionol" heated to 110 ° C for 10 hours under atmospheric pressure, the lighter fractions distilling off at pot temperatures of 45-83 ° C. After 10 hours, 72.4 g of light fractions have been distilled off. Then the remaining isobutyl alcohol is distilled off under vacuum and the remaining product is roughly distilled, which gives a mixture of isobutyl 2-methyl-4 ~ pentenoate and ethyl 2-methyl-4-pen-tenoate. The mixture is fractionated on a Vigreaux column with twelve plates at 95-96 ° C and 40 mm Hg to isolate isobutyl-2-methyl-4-pentenoate.

Example 21

To prepare n-hexyl-2-methyl-4-pentenoate, 56 g (0.4 mol) of the ethyl 2-me-thyI-4-pentenoate obtained according to Example 18, 60 g of n-hexyl alcohol, 0.4 g p-Toluenesulphonic acid, 10 g "Primol" and 0.1 g "Ionol" were kept under atmospheric pressure at 140-150 ° C for 18 hours, the light fractions being distilled off. After this period, 11.7 g of low-boiling fractions are distilled off. The remaining product is then rapidly distilled and fractionated on a column of the type described in Example 20 at 88 ° C. and 3.9 to 4.1 mm Hg.

Quantity offset by 4%. Another sixth of the basic taste is mixed with ethyl 2-methyl-4-pentenoate (prepared according to Example 18) in an amount corresponding to 1%. A further sixth of the basic taste is mixed with 5 2-methyl-4-pentenoic acid (prepared according to Example 19) in an amount corresponding to 8%. The last sixth of the basic taste is used for comparison. The taste mixtures produced in this way are evaluated in concentrations of 0.005% (50 ppm) in water by a group of testers.

The samples of the basic taste mixed with the compounds used according to the invention were consistently rated better than the basic mixture with regard to the freshness and naturalness of the strawberry aroma.

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Example 23

A concentrate of the following composition is produced:

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Example 22

A basic strawberry flavor is produced from the following components: 30

Components

Parts by weight of p-hydroxybenzyl acetone

Vanillin

Maltol

Ethyl methylphenyl glycidate

Benzyl acetate

Ethyl butyrate

Methyl cinnamate

Methylanthranilate a-ionone

Y-undecalactone

Diacetyl

Anethole cis-3-hexenol

Ethanol (95% aqueous)

Propylene glycol

35

Component%

Geraniol 1.00

Ethyl methylphenyl glycidate 3.50

Isobutyl 2-methyl pentenoate mixture

(made according to one of the examples

8, 9, 13, 20) 5.00

Vanillin 5.50

Ethyl pelargonate 13.00

Isoamyl acetate 14.00

Ethyl butyrate 58.00

100.00

15 20 15 20 10 5 5

1

2 2 1

17 385 500

Example 24

Another concentrate is made from the following components:

40

45

50

55

component

Naphthyl ethyl ether

Vanillin

Ethyl methylphenyl glycidate

Isobutyl-2-methyl pentenoate mixture (produced according to one of Examples 8, 9, 13 or 20)

Ethyl acetate

Isoamyl acetate

Ethyl butyrate

Isoamyl butyrate

1.0 2.5 3.0

5.0 9.5 12.0 26.0 41.0

100.0

One sixth of this basic taste is mixed with ethyl 2-60-methyl-pentenoate (prepared according to Example 3 - fractions No. 12-31 - or according to Examples 2, 4, 5, 12 or 16) in an amount corresponding to 1% transferred. Another sixth of this basic taste is mixed with the 2-methylpentenic acid mixture (prepared according to Examples 10, 65 11 or 15) in an amount corresponding to 8%. Another sixth of the basic taste is with ethyl 3,4-. pentandienoate, which is prepared according to Example 1, in one

Example 25

The concentrate prepared in Example 23 is dissolved in four volumes of propylene glycol and the mixture is added to a hard candy melt in a concentration of 42 g of concentrate solution per 45 kg of melt. The finished sweets show an excellent strawberry taste.

Example 26

The propylene glycol solution of the concentrate according to Example 23 or 24 becomes a simple syrup in one

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Amount of 1 g per liter of syrup added. The syrup is acidified by adding 11g of 50% aqueous citric acid solution per liter of syrup and then processed by mixing 1 liter of the flavored acidified syrup with 5 liters of carbonated water to a carbonated drink that has an excellent taste of fresh strawberries .

Example 27

The flavor concentrate prepared according to Example 23 is mixed with arabic gum in a ratio of 3.17 kg concentrate to 12.6 kg arabic gum in 29.5 liters of water and the aqueous mixture is processed by spray drying. The flavor concentrate-carrier combination thus obtained is added to a gelatin-dessert mixture in an amount of 1 g of the spray-dried material per 1.6 kg of the powdery dessert mixture. The gelatin dessert made from the mixture has an excellent strawberry taste.

Example 28

A strawberry flavor mix is made as follows:

Component parts by weight

Ethyl pelargonate 5

Ethyl laurate 20

Cinnamyl isobutyrate 10

Diacetyl (10%) 5

Cumin acetate 10

Peach aldehyde (“coeur”) 50 •

Ethyl isobutyrate 100

Ethyl isovalerate 50

Ethylheptoate 10

p-hydroxyphenylbutanone 3

Ethyl acetate 2

ß-ionon 10

Palaton 2

Vanillin 5

Ethyl vanillin 2

Ethyl methylphenyl glycidate 75

Isobutyl 2-methyl pentenoate mixture

(made according to one of the examples

8, 9, 13 or 20) 10

Ethyl 2-methyl pentenoate mixture

(prepared according to Example 3 - fractions

Nos. 12-31 - or one of the examples

1, 2, 4, 5, 12, 16 or 18) 3

The ethyl 2-methyl pentenoate mixture gives this strawberry taste an extraordinarily pleasant green, sweet taste. The isobutyl-2-methylpentenoate mixture gives the strawberry aroma a green, tart, acidic note.

Example 29

It is a tobacco blend of 40.1 parts "Bright", 24.9 parts "Burley", 1.1 parts "Maryland", 11.6 parts Turkish tobacco, 14.2 parts quickly dried stems, 2.8 parts glycerin and 5.3 parts of water produced and processed into cigarettes. Furthermore, a flavoring agent is made from 0.05 parts of ethyl butyrate, 0.05 parts of ethyl valerate, 2.0 parts of maltol, 26.0 parts of cocoa extract, 10.0 parts of coffee extract, 20.0 parts of ethyl alcohol and 41.9 Parts of water made.

This flavoring agent ("sauce") for tobacco is applied in an amount of 0.1% to all cigarettes from the above mixture. Half of the cigarettes serve as experimental cigarettes and are treated with 100 or 200 ppm of 2-methyl-cis-3-pentenoic acid (produced according to Example 10), the other half serves as a comparison and remains untreated. The cigarettes are rated by tester groups and it can be seen that the trial cigarettes are compared to the comparative cigarettes as aromatic, sweeter, bitter and less biting in the mouth and throat and produce a slightly sweet, chemical mouth coating effect similar to Turkish tobacco. All cigarettes are rated with a 20 mm cellulose acetate filter. The compound (21) according to the invention thus enhances the tobacco-like taste and aroma of the cigarettes made from tobacco mixture and gives them the character of Turkish cigarettes. In an analogous manner, ethyl 2-methyl-4-pentenoate according to Examples 3 (fractions Nos. 12 and 13), 5 and 18 or with 2-methyl-4-pentenoic acid according to Example 2 is used and the Evaluation of treated cigarettes achieved similar results.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

15

628217

TABLE

example

Addition of

Addition to

Result

30th

Mixture of Example 28 (1 g)

Soap flakes (100 g)

scented soap with strawberry flavor; green, sweet, tart and seed-like nuances

31

Mixture of Example 28 (0.15 g)

Washing powder with an excellent strawberry scent

32

Ethyl 2-methylpentene mixture according to one of Examples 1, 2, 3, 4, 5, 10, 16 or 18 (0.25 g)

Cosmetic powder (talc powder, 100 g)

excellent sweet, green strawberry aroma

33

Isobutyl-2-methylpentenoate mixture according to one of Examples 8, 9, 13 or 20 (0.1%; 0.15%; 0.20%)

liquid washing concentrate green, tart strawberry aroma; Intensity increases with concentration

34

Ethyl 2-methyl pentenoate according to one of Examples 1, 2, 3, 4, 5, 10, 14 or 18 (2.5% or 20%)

Colognes (85% ethanol) or perfume (95% ethanol)

clear sweet, green strawberry scent

Example 35 The following mixture is produced:

Component parts by weight.

Ethyl acetoacetate 3

Ethyl laurate 10

Cinnamyl isobutyrate 3

Cinnamyl isovalerate 5

Diacetyl 2

Heliotropylacetate 20

Peach aldehyde (“oeur”) 100

Ethyl butyrate 200

Ethyl isovalerate 20

Ethyl heptanoate 1

Dulcinyl 5

2 (p-hydroxyphenyl) -3-butanone 2

Ethyl acetate 1

ß-ionon 10

Palaton 2

Ethyl vanillin 1

Ethyl 3-methyl-3-phenylglycidate 150

n-Hexyl-2-methyl pentenoate mixture (according to one of the examples

6, 7, 14, 17 or 21) 5

30th

of Examples 6, 7, 14, 17 or 21) a toilet powder is produced. This has an excellent fruity chamomile aroma.

Example 37

A basic mix with pear flavor is made from the following components:

35

40

45

50

55

The component used according to the invention, the n-hexyl-2-methyl pentenoate mixture, gives this strawberry taste a fruity, camomile-like, peppery, floral note.

Example 36

By mixing 100 g talcum powder with 0.25 g n - hexyl-2-methyl pentenoate mixture (prepared according to a

60

component

Vanillin

Ethyl hexanoate

Ethyl decanoate

Benzyl acetate

Ethyl octanoate

X- undecalactone 10% (in 95% ethanol)

a-ionone 0.1% (in 95% ethanol)

Hexyl acetate

Lemon oil, cold pressed

Ethyl butyrate

Ethyl acetate

Butyl acetate

Amylvalerate

Amyl acetate

Ethyl alcohol

Parts by weight 2.0 0.5 1.0 0.5 2.0

2.0 5.0 25.0 5.0 7.0 40.0 20.0 65.0 640.0 185.0

n-Hexyl-2-methyl pentenoate, prepared according to one of Examples 6, 7, 14, 17 or 21, is added in an amount corresponding to 6% to a part of the above basic pear flavor mixture. The other part is left without comparison for comparison. Both samples are compared in water in amounts of 50 ppm and evaluated by test groups. This rating shows that the addition of

628217

16

n-Hexyl-2-methyl pentenoate gives a fresh, pumice-like, vinous, tagetes oil-like aroma and a full ripe pear taste or a winey, slightly spicy taste. The pear taste with one of the n-hexyl-2-methyl pentenoates is preferred because it provides the taste notes missing in the basic preparation.

Example 38

(A) Aroma powder

In each case 20 g of one of the taste preparations of Examples 22 or 37, which contain an alkyl 2-methyl pentenoate in a taste-enhancing or taste-enhancing amount, are emulsified in a solution which contains 300 g of acacia gum and 700 g of water. The emulsion is processed into a powder by spray drying

(B) mixed paste

48.4 g each of the preparation of Example 22 or 37 with alkyl 2-methyl pentenoate in an effective amount are mixed with 3.2 g of SiO 2 airgel (200 m 2 / g surface area, particle size 0.012 micrometer) with vigorous stirring, whereby one each viscous liquid is formed. 48.4 parts of the powdery taste preparation prepared according to (A) are then incorporated into the viscous liquid with stirring at 25 ° C. for 30 minutes, which gives a thixotropic paste with a lasting taste release.

This paste can be mixed, for example, in an amount of 4 parts with 100 parts of chewing mass, 300 parts of sucrose and 100 parts of starch syrup. The mass is kneaded in the usual way for the production of chewing gum and processed into strips. The chewing gum thus obtained has a persistent fruit taste.

The flavor paste prepared according to the above information can also be incorporated in a conventional toothpaste paste in an amount of, for example, 1.2%. With normal use, this paste shows a pleasant fruity taste with constant strong intensity during use (1 to 1.5 min).

Formula sheets or

(la)

(lb)

(Ig)

o or ch.

A

H

(2)

v

0

(2a)

Ndr ch h

i

0

c

RO ^ (2b)

or

(3)

17th

628217

(3a)

CH.

.H

O.

"V

OR

/

(3b)

(6)

(8th)

CH3 O ■ ^

CH -CH = C = C-C-

^ OMgX

(11)

CH3 O '

CH -C = -C-CH-C

^ OMgX

(10)

? H3 O

CH -CH = CH-CH-07

vOMgX

(12)

c /. V-C ^ °

OH \ = / ^ -OAlk

(21) (22)

628217

18th

N_>

\

0

(26)

X

0

OH

(31)

S \

O

OAlk

(32)

O

(33)

• ° C2H5

'CM)

(35)

S

O

•O'

(36)

O

"Oalkyl

(42)

(43)

.0

OC2H5

.0

O

(45)

(46)

\

0

\

, 0 OH

(51)

, 0

OAlk

(52)

(53)

■ ° C2H5

V

Claims (2)

628217 2 PATENT CLAIMS (1) - see formula sheet - in which R denotes the hydrogen atom or alkyl groups with up to 6 C atoms and at least one of the broken lines is a carbon-carbon-rc bond, with the proviso that (A) if at least the broken line in the cut-off is a carbon-carbon-Tc bond, R only represents alkyl radicals with up to 6 C atoms but not the hydrogen atom, and (B) if only the broken line in the A3.4 position denotes a carbon-carbon n bond, the substituent at the 4 position of the A3.4 double bond in the cis orientation to the substituent at the 3 position of the corresponding one A3.4 double bond is are suitable for changing organoleptic properties of products of the type explained below. The formula (1) comprises the corresponding isomers of the formulas (la), (lb) and (lc) and compounds of the formulas 1. Method for changing organoleptic properties of food or consumer products, characterized by using at least one compound of the formula (1) . /O (5) \ (2) (1) Cv (1) (4) "" (3) OR in which R represents the hydrogen atom or an alkyl group with up to 6 C atoms and at least one of the broken lines is a carbon-carbon u bond, with the proviso that (A) if at least the broken line in the cut-off is a carbon-carbon 7r bond, R only represents an alkyl radical with up to 6 C atoms, and (B) if only the broken line in the A3'4 position means a carbon-carbon rc bond, the substituent at the 4-position of the A3.4 double bond in the cis orientation to the substituent at the 3-position of the corresponding A3'4 double bond. 2. The method according to claim 1, characterized in that the compound (1) is one of the formula (22) 4 '\ c ^ ° V / C \ (22) \ = / XOAlk is used in which «Alk» is an alkyl group with up to 6 C-atoms, e.g. the ethyl, n-hexyl or isobutyl group. 3. The method according to claim 2, characterized in that the compound (22) is used in a mixture with the corresponding trans isomer, preferably in a ratio of 3: 2. 4. The method according to claim 2, characterized in that the compound (22) is used in a mixture with a 2-methyl-2-pentenoate, preferably in a ratio of 80% compound (22) to 20% of the 2-methyl 2-pentenoate. 5. The method according to claim 2, characterized in that the compound (22) is used as a mixture containing more than 60% compound (22) and also 2-methyl-4-pentenoate lower alkyl ester and / or 2-methylpenetic acid lower alkyl ester . 6. The method according to claim 1, characterized in that the compound (1) is one of the formula (3) is used. 7. The method according to claim 1, characterized in that as the compound (1) a 2-methyl-3,4-pentadiene acid alkyl ester according to the formula (4) is used. 8. The method according to any one of claims 2-7, characterized in that the compound (1) is used for flavoring foods together with at least one of the following auxiliaries: hydroxybenzyl acetone, vanillin, maltol, ethyl 3-methyl-3-phenylglycidate, Benzyl acetate, ethyl butyrate, methyl cinnamate, methyl anthranilate, 1-ionone, y-undecalactone, diacetyl, anethole, cis-3-hexenol, 2 (4-hydroxy-4-methylpentyl) norbornadiene, β-ionone, isobutyl sulfide, dimethyl sulfate , Acetic acid, acetaldehyde, 4- (2,6,6 - trimethyl-1,3-cyclohexadien-1-yl) -2-butanone, 4- (6,6-dimethyl-2-methylene-3-cyclohexene -l-yl) -2-butanone, geraniol, ethyl pelargonate, isoamyl acetate, naphthyl ethyl ether, ethyl acetate, isoamyl butyrate, 2-methyl-2-pentenoic acid, 2-methyl-3-pentenoic acid, 4-allyl-l, 2.6 -trimethoxybenzene, 4-propenyl-1,2,6-trimethoxybenzoI. 9. The method according to any one of claims 2-7, characterized in that the compound (1) for fragrances or fragrance-containing preparations, e.g. a cosmetic or detergent, together with auxiliary perfume, e.g. natural or artificial perfume oil, alcohols, aldehydes, ketones, esters, lactones or / and in a mixture with aqueous alcohol, in particular ethanol. 10. The method according to any one of claims 2-7, characterized in that the connection (1) for the. Flavoring tobacco containing goods is used together with at least one of the following excipients: ethyl butyrate, ethyl valerate and maltol. 11. Means for changing organoleptic properties of food or consumer products, characterized in that it contains at least one compound of the formula (1) as active ingredient (5) OR in which R represents the hydrogen atom or an alkyl group with up to 6 C atoms and at least one of the broken lines is a carbon-carbon-rc bond, with the proviso that (A) if at least the broken line in the cut-off is a carbon-carbon 7t bond, R only represents an alkyl radical with up to 6 C atoms, and (B) if only the broken line in the A3'4 position means a carbon-carbon Tt bond, the substituent at the 4 position of the A3'4 double bond in the cis orientation to the substituent at the 3 position of the corresponding A3'4 double bond. 12. Composition according to claim 11, characterized in that it is a compound of formula (22) as compound (1) V) he; (22) \ = / XOAlk, in which «Alk» is an alkyl group with up to 6 C atoms, e.g. the ethyl, n-hexyl or isobutyl group. 13. Composition according to claim 12, characterized in that it contains the compound (22) in a mixture with the corresponding trans-isomer, preferably in a ratio of 3: 2. 14. Composition according to claim 12, characterized in that it contains the compound (22) in a mixture with a 2-methyl-2-pentenoate, preferably in a ratio of 80% compound (22) to 20% of the 2-methylene - 2 -pentenic acid ester. 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 3rd 628217 15. Composition according to claim 12, characterized in that the compound (22) is present in a mixture which contains more than 60% compound (22) and moreover 2-methyl-4-pentenoic acid lower alkyl ester and / or 2-methylpentanoic acid lower alkyl ester. 16. Composition according to claim 11, characterized in that it is a compound of formula (3) as compound (1) Ndr contains. 17. Composition according to claim 11, characterized in that it as the compound (1) 2-methyl-3,4-pentadienoic acid or its lower alkyl ester according to formula (4) xor contains. 18. Composition according to one of the claims 12-17, characterized in that it is a preparation for flavoring food and the compound (1) preferably contains together with at least one of the following auxiliaries: hydroxybenzyl acetone, vanillin, maltol, ethyl-3-methyl -3-phenylglycidate, benzyl acetate, ethyl butyrate, methyl cinnamate, methyl anthranilate, a-ionone, y-undeca-lactone, diacetyl, anethole, cis-3-hexenol, 2- (4-hydroxy-4-methy] pentyl) norbornadiene, β-ionone, isobutyl acetate, dimethyl sulfide, acetic acid, acetaldehyde, 4- (2,6,6-trimethyl-l, 3-cyclohexadien-l-yl) -2-butanone, 4- (6,6-dimethyl-I- 2-me-thyIen-3-cyclohexen-l-yl) -2-butanone, Geranio !, ethyl pelargonate, isoamyl acetate, naphthyl ethyl ether, ethyl acetate, iso-amyl butyrate, 2-methyl-2-pentenoic acid, 2-methyl-3- pentene acid, 4-allyl-l, 2,6-trimethoxybenzene or 4-propenyl-l, 2,6-trimethoxybenzene. 19. Composition according to one of claims 12-17, characterized in that it is a fragrance preparation or a preparation containing fragrances, e.g. is a cosmetic or detergent, and the compound (1) is preferably used together with auxiliary perfume, e.g. natural or artificial perfume oil, alcohols, aldehydes, ketones, Contains esters, lactones and / or in a mixture with aqueous alcohol, especially ethanol. 20. Composition according to one of claims 12-17, characterized in that it is a preparation for flavoring tobacco-containing goods and the compound (1) preferably contains together with at least one of the auxiliaries ethyl butyrate, ethyl valerate and maltol. 21. Process for the preparation of compounds of formula (1) (5) \ (2) (Dc ^ ° \ - / ^ OR (1) (4) (3) in which R represents the hydrogen atom or an alkyl group with up to 6 C atoms and one of the broken lines is a carbon-carbon-u bond, with the proviso that (A) if the broken line in A3'4 position is a is a carbon-to-carbon rc bond, R represents only an alkyl radical with up to 6 C atoms, and (B) the substituent at the 4-position of the A3'4 double bond in the cis orientation to the substituent at the 3-position the corresponding A3'4 double bond, characterized in that compounds of the formula (4) ^ OR hydrated. 22. The method according to claim 21, for the preparation of the 2-methylpentenoic acid compounds of the formula (1), characterized in that hydrogenation is carried out in the presence of Raney nickel, palladium-on-carbon or palladium-on-calcium carbonate as a catalyst, e.g. at a temperature of 10-100 ° C, a hydrogen pressure of 0.35 to 5.6 atü and a catalyst concentration of 0.1 to 10%, based on the weight of the compound (4). 23. The method according to claim 21 or 22, characterized in that a reaction mixture is isolated as the product which contains at least 60% by weight of at least one compound of the formula (22) (22) ^ OAlk contains, in which «Alk» means an alkyl radical with 1-6 C atoms. 24. The method according to any one of claims 21-23, characterized in that the reaction mixture obtained by hydrogenation, optionally after isolating a reaction mass consisting of at least 60% by weight of compound of the formula (22), is hydrolyzed, preferably with an aqueous or alcoholic solution of alkali metal hydroxide. 25. The method according to claim 24, characterized in that after the hydrolysis, a reaction mixture is obtained which contains at least 60% by weight of the compound of the formula (21) consists. 26. The method according to any one of claims 21-25, characterized in that the hydrogenation catalyst is Raney nickel and the reaction mixture obtained and optionally isolated is at least 60% by weight of compounds of the formulas (21) or (22) and less than 40% consists of 2-methylpentanoic acid or a lower alkyl ester of this acid. 27. The method according to any one of claims 21-25, characterized in that the hydrogenation catalyst is palladium on carbon and the mixture obtained and optionally isolated at least 60% by weight of compounds of the formulas (21) or (22) and less contains as 40% by weight 2-methyl-4-pentenoic acid or its lower alkyl ester or / and 2-methylpentanoic acid or its lower alkyl ester. 28. The method according to any one of claims 21-25, characterized in that the hydrogenation catalyst Palladium5 10th 15 20th 25th 30th 35 40 45 50 55 60 65 628217 4th is calcium carbonate and the isolated mixture contains at least 60% by weight of compounds of the formulas (21) or / and (22) and less than 40% by weight of 2-methyl-4-pentenoic acid or / and their lower alkyl esters. 29. The method according to any one of claims 21-28, characterized in that R in the formulas (1), (4), (21) and (22) means the ethyl group. 30. The method according to claim 26, characterized in that the concentration of the hydrogenation catalyst is 3-10%, based on the weight of compound (4). 31. The method according to claim 30, characterized in that the concentration of the hydrogenation catalyst is about 5% of the weight of the compound (4) and the hydrogenation at 25-35 ° C in an organic solvent, e.g. n-hexane, isopropanol or ethanol is carried out. 32. The method according to any one of claims 27 or 28, characterized in that the concentration of the hydrogenation catalyst is 0.125 to 2.0% of the weight of the compound (4). 33. The method according to claim 32, characterized in that the concentration of the hydrogenation catalyst is about 0.25% of the weight of the compound (4) and that hydrogenates at 25-35 ° C in organic solvent such as n-hexane, isopropanol or ethanol becomes. It has been found that new compounds of the formula (2), (3) and (4) including the isomers corresponding to them, e.g. Compounds of the formulas (2a), (2b), (3a) and (3b), further isomers being possible, depending on the nature of the alkyl radicals R present. According to the invention, the compounds (1) are used to change the organoleptic properties of food or consumer products. For this purpose, the compounds (1) can be used individually, in a mixture with one another or in a mixture with other components in order to give products of the type mentioned which have no or only a weak taste or little or no aroma with a certain taste or To provide aroma character, or to reinforce or supplement such products with given taste or aroma properties, for example if a natural or artificial flavor mixture needs to be supplemented in any way. The change in organoleptic properties can also consist in the fact that a given taste * or aroma impression is supplemented in order to modify its quality, its character or its fragrance. Both solid and liquid foods or additives with or without nutritional value can be considered as food products, e.g. Soups, finished food preparations, Beverages, dairy products, confectionery, vegetables, cereals, non-alcoholic beverages, snacks and the like. Utility products that can be treated according to the invention are e.g. Chewing gum, cosmetics including perfumes, and tobacco or tobacco products. Spice, flavor or flavoring or perfuming compositions are also to be understood here as food or consumer products and can be treated according to the invention.