EP1682489A1

EP1682489A1 - Use of alkene carboxlic acid n alkylamides as flavouring agents

Info

Publication number: EP1682489A1
Application number: EP04818140A
Authority: EP
Inventors: Jakob Ley; Günter Kindel; Gerhard Krammer
Original assignee: Symrise AG
Current assignee: Symrise AG
Priority date: 2003-11-04
Filing date: 2004-10-28
Publication date: 2006-07-26
Also published as: CN1878745A; JP2007510634A; US20070202188A1; DE10351422A1; WO2005044778A1

Abstract

Disclosed is the use of an alkene carboxylic acid N alkylamide of formula (3a) or (3b) or a mixture of two or several compounds of formula (3a) and/or (3b), wherein R<1> respectively represents an alkyl radical, and R<2> represents a low alkyl radical (I), as an acrid agent and/or (ii) in order to produce a feeling of warmth upon consumption and/or (iii) in order to intensify the taste of ethanol and/or (iv) in order to imitate the taste of ethanol.

Description

Use of alkenecarboxylic acid-N-alkylamides as flavorings

The invention describes the use of alkenecarboxylic acid Λ / - alkylamides and their stereoisomers as intense pungent and aromatic substances, preferably in nutritional, oral hygiene or pleasure-making preparations. The invention further relates to nutritional, oral hygiene or pleasure-making preparations containing the alkenecarboxylic acid / V-alkylamides according to the invention.

Capsaicin [Λ / - (4-hydroxy-3-methoxybenzyl) -8-methyl- (6E) - nonenoic acid amide, formula (1)] and other capsaicinoids are already tasty and heat-generating aroma substances from various types of Capsicum, especially chilli known since 1871. Heat-generating substances or substances with a heat-generating effect are understood to mean those which cause a sensation of heat by sensors. With a correspondingly low dosage of the capsaicinoids (the threshold value is a dilution of approximately 1:10 ⁵ ), only a pleasant, neutral sharpness and a feeling of warmth in the mouth is perceived. The high acute toxicity is a problem with capsaicin (LD ₅ o (mouse oral) 47 mg), which complicates the applicability in the preparation, as well as the chronic occurring with frequent use and overdose. Gastritis, kidney and liver damage (Römpp Lexikon Naturstoffchemie, Thieme 1997, p. 109). Thus, despite the good sensory properties, there is a need for less problematic sharp substances. The piperine (1-piperoylpiperidine, formula (2),) found in white pepper also causes a sharp impression (Römpp Lexikon Naturstoffchemie, Thieme 1997, p. 500), but shows a relative sharpness of only about 1 compared to capsaicin %. In addition, piperine has an intense taste of its own, reminiscent of pepper, so that it can only be used to a limited extent in many preparations.

The object of the present invention was to identify substances with a pungent, tingling, mouthwashing and / or heat-generating effect and an otherwise relatively neutral aroma profile which can be used as aroma substances in the diet or for pleasure-making preparations.

The invention solves this problem by using an alkenecarboxylic acid / V-alkylamide of the formula

or

(3b)

or a mixture of two or more compounds of the formula (3a) and / or (3b)

where each

R ^{1 represents} an alkyl radical,

and

R represents a lower alkyl radical,

as (i) pungent and / or (ii) to produce a feeling of warmth when consumed regardless of the temperature of the alkenecarboxylic acid-N-alkylamide and / or (iii) to enhance the taste of ethanol and / or (iv) to imitate the Taste of ethanol and / or (v) for Induction of the flow of saliva, in particular for use in nutrition, oral hygiene or in the preparation of food.

The meandering line in the formulas (3a) and (3b) means that the associated double bond is E- or Z-configured. If asymmetric carbon atoms are present, the compounds of the formulas (3a) and (3b) can be present as pure enantiomers and / or diastereomers or as mixtures thereof. For the purposes of the invention, an alkyl radical is linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms, the following groups being preferred: ethyl, propyl, butyl, pentyl and hexy

A lower alkyl radical for the purposes of the invention are linear, branched or cyclic alkyl groups having 1 to 5 carbon atoms, the following groups being preferred: methyl, ethyl, propyl, 2-propyl, cyclopropyl, butyl, 2-butyl , 3-methylpropyl (ie isobutyl), cyclobutyl, 1- or 2-methylcylopropyl, 2-methylpropyl, pentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, cyclopentyl and 1 -, 2- or 3-methylcyclobutyl, but especially isobutyl or 2-methyl butyl.

It is already known that some fatty acid isobutylamides (“Al amide”) can cause trigeminal stimuli such as local anesthetic, sharpness or tingling in the oral cavity or on the skin and mucous membranes. This is structurally quite right for the compounds of the formulas (3a) and (3b) Similar pellitor (2E, 4E-decadienoic acid / V-isobutylamide), however, mainly shows an anesthetic effect (cf. HCF Su and R. Horvat, J. Agric. Food Chem. Jhrg. 1981, Vol. 29, pages 115-118) So far, no sensory data have been described for the also known 2E, 4Z-decadienoic acid / V-isobutylamide. In a study which was not carried out in more detail (B. Bryant and I. Mezine, in ACS Symposium Series, Vol. 825 , Chemistry of Taste, P. Given and D. Paredes, ed., Vol. 825, American Chemical Society 2002, pp. 202-212), it was shown that 2E-decenoic acid Λ / -isobutylamide in contrast to the 2.4 - Alkadienamides did not give a sharp impression (no further sensory data were published). In a study of 2E-tetradecenoic acid-N-isobutylamide, no sharpness was also found in the concentrations tested (H. Shibuya et al., Chem. Pharm. Bull., Jhrg. 1992, volume 40, 2325-2330).

It was therefore surprising and unforeseeable for the person skilled in the art that the alkenecarboxylic acid Λ / alkylamides to be used according to the invention have a somewhat delayed, sharp, but above all warm, sometimes slightly anesthetic, sometimes also tingling or as (English) tingling cause the described taste impression and are partially salivatory, the sensory impressions are relatively strong at higher use concentrations and last relatively long. Further sensory impressions can be seen that round off the profile, so that the compounds of the formulas (3a) and (3b) (and their mixtures) can be used excellently as flavorings (for the purposes mentioned).

Some of the compounds of formula 3a are known: for example, 2E-decenoic acid / V-isobutylamide was found in Piper guineense, a plant used as a spice in Nigeria (SK Adesina, AS Adebayo, SKO Adesina and R. Groening, Pharmazie 2002, 57 ( 9), 622-627).

3E-decenoic acid-N-isobutylamide has previously been prepared and characterized (see Journal of the Indian Chemical Society, vol. 14, year 1937, pages 421 and 424 or Beilstein reference no. 1778318).

The following alkenecarboxylic acid Λ / alkylamides are particularly preferred:

2E-decenoic acid Λ / -isobutylamide 2Z-decenoic acid / V-isobutylamide 2E-decenoic acid Λ / - (2-methylbutyl) amide 3E-decenoic acid Λ / -isobutylamide 3E-Nonensäure- / V-isobutylamide

as well as their mixtures. The present invention further provides preparations, semi-finished goods and fragrance, aroma and flavor compositions, containing the alkenecarboxylic / V-alkylamides according to the invention. See below.

The alkenecarboxylic acid / V-alkylamides to be used according to the invention (or mixtures thereof) can also be used in cosmetic or dermatological preparations to produce a feeling of warmth on the skin.

In a particularly preferred embodiment of the invention, the alkenecarboxylic acid Λ / alkylamides (or mixtures thereof) according to the invention are used in combination with other substances which taste hot and / or induce a feeling of heat and / or salivation or (in particular) taste and / or Saliva-inducing herbal extracts used. In this way, a particularly rounded sensory profile can be achieved. In particular, the combination of the alkenecarboxylic acid Λ / alkylamides to be used according to the invention with a pungent taste and / or saliva-inducing plant extract in a ratio of 0.01 to 1 to 100 to 1, preferably 0.1 to 1 to 10 to 1, produces a pleasant sensory profile.

Other substances with a sharp taste and / or a feeling of heat which are suitable for combination are, for example: capsaicin, dihydrocapsaicin, gingerols, paradoles, shogaols, piperine, carboxylic acid-N-vanillylamides, in particular nonanoic acid-N-vanillylamide, pellitorin or spilanthol, -Nenenoic acid-N-4-hydroxy-3-methoxyphenylamide, alkyl ether of 4-hydroxy-3-methoxybenzyl alcohol, in particular 4-hydroxy-3-methoxybenzyl-n-butyl ether, alkyl ether of 4-acyloxy-3-methoxybenzyl alcohol, especially 4-acetyloxy -3-methoxybenzyl-n-butyl ether and 4-acetyloxy-3-methoxybenzyl-n-hexyl ether, alkyl ether of 3-hydroxy-4-methoxybenzyl alcohol, alkyl ether of 3,4-dimethoxybenzyl alcohol, alkyl ether of 3-ethoxy-4-hydroxybenzyl alcohol, alkyl ether of 3,4-methylenedioxybenzyl alcohol, (4-hydroxy-3-methoxyphenyl) acetic acid amides, especially (4-hydroxy-3-methoxyphenyl) acetic acid-Nn-octylamide, vanillomandelic acid alkylamides,

Ferulic acid phenethylamide, nicotinaldehyde, methyl nicotinate,

Propyl nicotinate, 2-butoxyethyl nicotinate, benzyl nicotinate, 1-acetoxychavicol, polygodial and isodrimeninol.

Herbal extracts that are suitable for combination are all herbal extracts that are suitable for nutrition and produce a sharp and / or warm sensory impression. In this respect, preferred plant extracts are, for example, pepper extract (Piper ssp., In particular Piper nigrum), water pepper extract (Polygonum ssp., In particular Polygonum hydropipeή, extracts from Allium sp. (In particular onion and garlic extracts), extracts from radish (Raphanus ssp.), Horseradish extracts (Cochlearia armoracia), extracts from black (Brassica nigra), wild or yellow mustard (Sinapis ssp., Especially Sinapis arvensis and Sinapis alba), bertram root extracts (Ancyclus ssp., Especially Anacylcus pyrethrum L.), coneflower extracts (Echinaceae ssp. ), Extracts from Szechuan pepper (Zanthoxylum ssp., Especially Zanthoxylum piperitum), Spilanthes extract (Spilanthes ssp., Especially Spilanthes acmella), chilli extract (Capsicum ssp., Especially Capsicum frutescens), paradise grain extract (Aframetaamum ssp., Especially [Rose] K. Schum.), Ginger extract (Zingiber ssp., Especially Zingiber officinale), galanga extract (Kaempferia gala nga or Alpinia galanga) and Jaborandi extract (Pilocarpus spec \ es, especially Pilocarpus jaborandi).

The substances that induce salivation can, for example, certain unsaturated alkamides (e.g. pellitorins, spilanthols, Shogaoole),

Alkaloids (e.g. pilocarpine), salivary peptides (e.g. substance P, tachykinins, physalaemine), but also simple fruit acids (e.g. citric acid, tartaric acid).

The salivary flow-inducing plant extracts can, for example, be plants or plant extracts containing the aforementioned salivary flow-inducing substances.

The pungent-tasting and / or saliva-inducing plant extracts can often be obtained from the corresponding fresh or dried plants or parts of plants, but especially from white, green or black peppercorns, water peppercorns, onions and garlic, radish root, horseradish, mustard seeds, coneflower roots, bertram roots, parts of plants Zanthoxylum seeds, parts of plants from the Spilanthes species, chili peppers, grains of paradise or ginger or galanga roots are obtained. The dried parts of the plant, which have preferably been ground beforehand, are usually extracted with a solvent suitable for foodstuffs and luxury foods, at a temperature in the range from 0 ° C. to the boiling point of the particular solvent, then filtered and the filtrate is partially or completely concentrated. preferably by distillation, freeze or spray drying. The crude extract obtained in this way can then be worked up further, for example treated with steam at pressures from 0.01 mbar to normal pressure and / or taken up in a solvent suitable for foodstuffs and luxury foods. Solvents suitable for foodstuffs and luxury foods are, for example: water, ethanol, methanol, propylene glycol, glycerol, acetone, dichloromethane, diethyl ether, hexane, heptane, triacetin, a vegetable oil or fat, supercritical carbon dioxide or a mixture of the aforementioned solvents.

In a further particularly preferred embodiment of the invention, the alkenecarboxylic acid Λ / alkylamides to be used according to the invention are (or mixtures thereof) are used in combination with one or more substances which cause a physiological cooling effect.

Examples of substances which cause physiological cooling effects are menthol and menthol derivatives (for example L-menthol, rac.Menthol) menthyl ether (for example (l-menthoxy) -1, 2-propanediol, (l-menthoxy) -2-methyl-1,2-propanediol , Menthyl methyl ether), menthyl esters (e.g. menthyl acetate, menthyl isobutyrate, menthyl lactate, menthyl (2-methoxy) acetate, menthyl (2-methoxyethoxy) acetate, menthyl pyroglutamate), menthyl carbonate (e.g. menthyl propylene glycol carbonate, menthyl glycol carbonate, menthyl methylene glycol, menthyl glycol carbonate, menthyl methylene glycol, menthyl glycol carbonate, menthyl glycol carbonate, menthyl glycol carbonate, menthyl glycol carbonate, menthyl glycol carbonate, menthyl glycol carbonate, menthyl methylene glycol carbonate, menthyl methylene glycol carbonate, methyl carbonate, methylbenzene glycol, (e.g. menthyl succinate, menthyl glutarate), menthane carboxamides (e.g. menthane carboxylic acid-N-ethylamide), menthone and menthone derivatives (e.g. menthone glycerol ketal), 2,3-dimethyl-2- (2-propyl) butanoic acid derivatives (e.g. 2,3-dimethyl-2- (2-propyl) butanoic acid-N-methylamide), isopulegol or its esters (l - (-) - isopulegol, l - (-) - isopulegol acetate), menth derivatives (e.g. p-menthane-3,8-diol), cubebol , Pyrrolidone derivatives of cycloalkyldione derivatives (e.g. B. 3-methyl-2 (1-pyrrolidinyl) -2-cyclopenten-1-one) or Icilin.

Of course, the substances that cause the physiological cooling effect, as far as they occur in nature, can also be in the form of an extract, a distillate, a crystallization or other processed and / or purified preparation from natural sources, preferably from naturally occurring or cultivated plants or parts of plants and / or vegetable callus or cell cultures or from fermentative processes. For example, suitable menthol-, menthone- or isopulegol-containing preparations and their derivatives can be obtained from a large number of Mentha ssp. be obtained by steam distillation or other distillation processes.

The invention furthermore relates to preparations for nutrition or pleasure, containing a (to achieve a feeling of Hotness or warmth, or to enhance or imitate the taste of ethanol, or to induce the saliva foot) effective amount of an alkenecarboxylic acid Λ / alkylamide of the formula (3a) or (3b) or a mixture of two or more compounds of the formula (3a ) and / or (3b)

where each

R ¹

and

R ^{2 have} the meanings given above,

and, if necessary, other usual basic, auxiliary and additive substances for food and beverages. These preparations generally contain 0.0000001% by weight to 10% by weight, preferably 0.00001 to 1% by weight, but particularly preferably 0.00001% by weight to 0.1% by weight, based on the total weight of the preparation, on one or more alkenecarboxylic acid Λ / alkylamides of the formula (3a) or (3b). Other common basic substances, auxiliaries and additives for foodstuffs or luxury foods can be contained in amounts of 0.0000001 to 99.9999999% by weight, preferably 10 to 80% by weight, based on the total weight of the preparation. Furthermore, the preparations can contain water in an amount of up to 99.9999999% by weight, preferably 5 to 80% by weight, based on the total weight of the preparation.

The preparation according to the invention preferably comprises at least one further sharp-tasting and / or sensation of heat-generating and / or salivating flow-inducing substance or at least one sharp-tasting and / or salivating flow-inducing plant extract. For the purposes of the invention, nutritional or pleasure-making preparations are, for example, baked goods (for example bread, dry biscuits, Cakes, other pastries), confectionery (e.g. chocolates, chocolate bar products, other bar products, fruit gums, hard and soft caramels, chewing gum), alcoholic or non-alcoholic drinks (e.g. coffee, tea, wine, wine-based drinks, beer, beer-based drinks, liqueurs, Schnapps, brandies, fruit-containing lemonades, isotonic drinks, soft drinks, nectars, fruit and vegetable juices, fruit or vegetable juice preparations), instant drinks (e.g. instant cocoa drinks, instant tea drinks, instant drinks)

Coffee beverages), meat products (e.g. ham, fresh sausage or raw sausage preparations, seasoned or marinated fresh or pickled meat products), eggs or egg products (dry egg, egg white, egg yolk), cereal products (e.g. breakfast cereals, cereal bars, pre-cooked ready-rice products), milk products (e.g. milk drinks) , Milk ice cream, yogurt, kefir, cream cheese, soft cheese, hard cheese, dry milk powder, whey, butter, buttermilk), fruit preparations (e.g. jams, fruit ice cream, fruit sauces, fruit fillings), vegetable preparations (e.g. ketchup, sauces, dried vegetables, frozen vegetables, pre-cooked vegetables, cooked vegetables ), Snack foods (e.g. baked or fried potato chips or potato dough products, extrudates based on corn or peanuts), products based on fat and oil or emulsions thereof (e.g. mayonnaise, tartar sauce, dressings), other ready meals and soups (e.g. dry soups, instant soups, pre-cooked soups), spices, seasoning mixes and especially Au litter seasonings, which are used, for example, in the snack area. The preparations within the meaning of the invention can also serve as semi-finished goods for the production of further preparations serving for nutrition or pleasure. The preparations according to the invention can also be in the form of capsules, tablets (non-coated and coated tablets, for example enteric coatings), dragées, granules, pellets, solid mixtures, dispersions in liquid phases, as emulsions, as powders, as solutions, as pastes or as other swallowable or chewable preparations as dietary supplements. It has also proven to be particularly advantageous that the alkenecarboxylic acid Λ / alkylamides to be used according to the invention, in particular in the preferred combination with pungent-tasting plant extracts, can imitate the pungent taste of alcohol in alcoholic beverages or preparations with alcoholic beverages and it is thus possible to to lower or replace the alcohol content in alcoholic beverages or in preparations with alcoholic beverages with the same sensory assessment. A corresponding preparation according to the invention therefore comprises an effective amount of alkenecarboxylic acid N-alkylamide of the formula

(3a)

or

(3b)

or a mixture of two or more compounds of the formula (3a) and / or (3b),

where each R ^{1 represents} an alkyl radical,

and

R ^{2 represents} a lower alkyl radical,

as (i) pungent and / or (ii) to produce a feeling of warmth when consumed regardless of the temperature of the alkenecarboxylic acid-N-alkylamide and / or (iii) to enhance the taste of ethanol and / or (iv) to imitate the Taste of ethanol and optionally an effective amount (i) of another hot-tasting and / or heat-generating substance and / or (ii) of a hot-tasting vegetable extract.

The taste reminiscent of the taste of ethanol is preferably determined essentially by the amount of alkenecarboxylic acid-N-alkylamide (s). Ethanol is present in such preparations according to the invention in a maximum amount of 0.5% by weight if the aim is to reduce alcohol compared to a comparably tasting comparative product. Such a preparation preferably contains less than 0.1% by weight of ethanol.

It has also proven to be particularly advantageous that the alkenecarboxylic acid Λ / alkylamides according to the invention can imitate the pungent taste of capsaicin, dihydrocapsaicin and nonivamide and it is thus possible to reduce the capsaicin content in the preparations used for nutrition or enjoyment with a constant sensory assessment adjust.

The invention further provides preparations for oral hygiene, in particular dental care products such as toothpastes, tooth gels,

Tooth powder, mouthwashes, chewing gums and other oral care products, containing an effective (see above) amount of an alkenecarboxylic acid Λ / alkyl amide of the formula (3a) or (3b)

or a mixture of two or more compounds of the formula (3a) and / or (3b),

where each

R

and

R ^{2 have} the meaning given above

and, if appropriate, other customary basic substances, auxiliaries and additives for such preparations. They preferably contain 0.0000001% by weight to 10% by weight, preferably 0.00001 to 1% by weight, but in particular 0.00001% by weight to 0.1% by weight, based on the total weight of the preparation, on alkenecarboxylic acid Λ / alkylamides of the formula (3a) or (3b). Other conventional basic substances, auxiliaries and additives for the preparations used for oral hygiene can be present in amounts of 0.0000001 to 99.9999999% by weight, preferably 10 to 80% by weight, based on the total weight of the preparation. Furthermore, the preparations can contain water in an amount of up to 99.9999999% by weight, preferably 5 to 80% by weight, based on the total weight of the preparation.

The preparation according to the invention preferably comprises at least one further sharp-tasting and / or sensation of heat-generating and / or salivating flow-inducing substance or at least one sharp-tasting and / or salivating flow-inducing plant extract. Dental care products which contain the alkenecarboxylic acid / V-alkylamides according to the invention generally consist of an abrasive system (abrasive or polishing agents), such as, for example, silicas, Calcium carbonates, calcium phosphates, aluminum oxides and / or hydroxyapatites, from surface-active substances, such as sodium lauryl sulfate, sodium lauryl sarcosinate and / or

Cocamidopropyl betaine, from humectants such as glycerol and / or sorbitol, from thickeners such as carboxymethyl cellulose, polyethylene glycols, carrageenans and / or Laponiten ^® , from sweeteners such as saccharin, from stabilizers and from active ingredients such as sodium fluoride, sodium monofluorophosphoride, zin , quaternary ammonium fluorides, zinc citrate, zinc sulfate, tin pyrophosphate, tin dichloride, mixtures of various pyrophosphates, triclosan,

Cetylpyridinium chloride, aluminum lactate, potassium citrate, potassium nitrate, potassium chloride, strontium chloride, hydrogen peroxide, flavors and / or sodium bicarbonate.

Chewing gums which contain the alkenecarboxylic acid Λ / alkylamides to be used according to the invention generally consist of a chewing gum base, i.e. a chewing mass that becomes plastic when chewing, from sugars of various types, sugar substitutes, sweeteners, sugar alcohols, humectants, thickeners, emulsifiers, flavors and stabilizers.

The alkenecarboxylic acid N-alkylamides of the formulas (3a) and / or (3b) or preparations according to the invention can preferably be used in sprinkling seasonings, in order to reduce the dry mouthfeel that occurs when eating corn, potato or rice flour -Chips and snacks are avoided and the overall sensory impression is improved.

Preferred sprinkling seasonings contain, for example, synthetic, natural or nature-identical flavorings and carriers such as maltodextrin, salts such as table salt, spices such as bell pepper and pepper, sugar substances such as saccharin and flavor enhancers such as monosodium glutamate and / or inosine monophosphate. The preparations according to the invention, which comprise one or more alkenecarboxylic acid N-alkylamides of the formula (3a) or (3b), can be prepared by using the alkenecarboxylic acid (N) alkylamide (s) as a substance, as a solution or in the form of a Mixture with a solid or liquid carrier is (are) incorporated into a basic preparation for nutrition, oral hygiene or pleasure. Preparations according to the invention which are present as a solution can advantageously also be converted into a solid preparation by spray drying.

To prepare preparations according to the invention, the alkenecarboxylic acid N-alkylamides and, if appropriate, other constituents of the preparation according to the invention can also be prepared beforehand in emulsions, in liposomes, e.g. starting from phosphatidylcholine, in microspheres, in nanospheres or also in capsules, granules or extrudates from a matrix suitable for food and beverages, e.g. from starch, starch derivatives, cellulose or cellulose derivatives (e.g. hydroxypropyl cellulose), other polysaccharides (e.g. alginate), natural fats, natural waxes (e.g. beeswax, carnauba wax) or from proteins, e.g. Gelatin. In a further preferred production process, the alkenecarboxylic acid N-alkyl amides are complexed beforehand with one or more suitable complexing agents, for example with cyclodextrins or cyclodextrin derivatives, preferably β-cyclodextrin, and used in this complexed form.

A preparation according to the invention is particularly preferred in which the matrix is selected such that the alkenecarboxylic acid N-alkylamides are released from the matrix with a delay, so that a long-lasting sharp or heat-generating effect is obtained.

Other customary basic ingredients can be used as other constituents for the preparations according to the invention, serving for nutrition or pleasure. Auxiliaries and additives for food or luxury foods are used, e.g. water, mixtures of fresh or processed, vegetable or animal base or raw materials (e.g. raw, roasted, dried, fermented, smoked and / or cooked meat, egg, bones, Cartilage, fish, crustaceans and shellfish, vegetables, fruits, herbs, nuts, vegetable or fruit juices or pastes or their mixtures), digestible or non-digestible carbohydrates (e.g. sucrose, maltose, fructose, glucose, dextrins, amylose, amylopectin, Inulin, xylans, cellulose), sugar alcohols (e.g. sorbitol, mannitol, xylitol), natural or hardened fats (e.g. tallow, lard, palm fat, coconut fat, hardened vegetable fat), fatty oils (e.g. sunflower oil, peanut oil, corn oil, safflower oil, olive oil, walnut oil , Fish oil, soybean oil, sesame oil), fatty acids or their salts (eg potassium stearate, potassium palmitate), proteinogenic or non-proteinogenic amino acids and related compounds (eg taurine , Creatine, creatinine), peptides, native or processed proteins (e.g. gelatin), enzymes (e.g. peptidases, glucosidases, lipases), nucleic acids, nucleotides (inositol phosphate), taste-modulating substances (e.g. sodium glutamate, 2-phenoxypropionic acid, hydroxyflavanones according to EP 1, 258,200 ), Emulators (e.g. lecithins, diacylglycerols), stabilizers (e.g. carageenan, alginate, locust bean gum, guar gum), preservatives (e.g. benzoic acid, sorbic acid), antioxidants (e.g. tocopherol or its derivatives, ascorbic acid or its derivatives), chelators (e.g. citric acid) organic or inorganic acidulants (e.g. malic acid, acetic acid, citric acid, tartaric acid, phosphoric acid), bitter substances (e.g. quinine, caffeine, limonin), sweeteners (e.g. saccharin, cyclamate, aspartame, neotame, neohesperidine hydrochalcon, tagatose, sucralose), mineral salts ( e.g. sodium chloride, potassium chloride, magnesium chloride, sodium phosphates), substances that prevent enzymatic browning (e.g. Sulfite, ascorbic acid), essential oils, plant extracts, natural or synthetic colors or pigments (e.g. carotenoids, flavonoids, anthocyanins, chlorophyll and their derivatives), spices, as well as fragrances, synthetic, natural or nature-identical aromas and flavors. Preparations according to the invention preferably also contain an aroma composition in order to round off and refine the taste and / or smell of the preparation. Suitable aroma compositions contain, for example, synthetic, natural or nature-identical aroma substances and fragrances, but in particular also other pungent tasting and / or heat-generating substances or plant extracts.

Another aspect of the invention relates to the use of the preparations according to the invention as semi-finished products, in particular with the aim of flavoring finished products made from the semi-finished products.

The preparations according to the invention, which serve as semi-finished products, generally contain 0.0001% by weight to 95% by weight, preferably 0.001 to 80% by weight, but in particular 0.01% by weight to 50% by weight. %, based on the total weight of the preparation, of the alkenoic acid-N-alkylamides to be used according to the invention and, if appropriate, one or more other flavoring and flavoring substances, if appropriate also various carriers and auxiliaries or different solvents.

In particular, semi-finished goods for flavoring finished goods are preferred which contain the alkenoic acid-N-alkylamides (or mixtures thereof) to be used according to the invention in combination with one or more hot-tasting and / or a feeling of heat-generating substances or (in particular) hot-tasting vegetable Extracts containing these substances and / or in combination with other substances which induce salivation or plant extracts containing these substances, the semi-finished products also being able to contain various carriers and auxiliaries and / or different solvents.

Another object of the invention is the use of 2E-decenoic acid-N-isobutylamide and / or 2E-decenoic acid-N- (2-methylbutyl) amide as an agent for promoting saliva.

Examples

Representation of alkenoic acid-N-alkylamides

Example 1 Preparation of 2E-decenoic acid-N-isobutylamide

56 g of 2E-decenoic acid were dissolved in 82 ml of toluene and 44 g of thionyl chloride were added at 20-23 ° C. The mixture was stirred at 20-23 ° C. overnight, then heated to 40 ° C. for 1 h and then the toluene was distilled off at 40 ° C. in a water jet vacuum. 40 g of the crude 2E-decenoic acid chloride (61 g) were dissolved in 40 ml of acetone and added to a solution of 17 g of isobutylamine in 40 ml of acetone and 100 ml of sodium hydroxide solution (9.7 g of NaOH in water). The oily product is separated off and recrystallized from petroleum ether, giving 20 g of product in the form of slightly yellowish crystal needles (purity GC: 96.5%).

¹ H NMR (CDCI ₃ ; 400 MHz, δ): 6.82 (1H, dt, J = 15.2 Hz, J = 7.0 Hz, H-3), 5.78 (1H, dt, J = 15.2 Hz, J = 1.5 Hz, H-2), 5.65 (1H, bs, NH), 3.14 (2H, dd, J = 6.85 Hz, J = 6.17 Hz , H-1 '), 2.16 (2H, m, J = 7 Hz, J = 1.5 Hz, H-4), 1.80 (1H, m, J = 6.75 Hz, H-2 '), 1.44 (2H, m, J = 7.19 Hz, H-5), 1.34-1.23 (8H, m, H-6, H-7, H-8, H-9 ), 0.92 (6H, d, J = 6.78 Hz, H-3 '), 0.88 (3H, t, J = 6.82 Hz, H-10) ppm.

¹³ C NMR (CDCI ₃ ; 100 MHz, δ): 165.80 (C, C-1), 144.38 (CH, C-3), 123.32 (CH, C-2), 46.75 (CH ₂ , C-1 '), 31, 98 (CH ₂ , C-4), 31, 70 (CH ₂ , C-8), 29.11 (CH ₂ ), 29.04 (CH ₂ ), 28.54 (CH, C-2 '), 28.25 (CH ₂ ), 22.59 (CH ₂ ), 20.10 (2 CH ₃ , C-3'), 14.05 (CH ₃ , C -10) ppm.

Example 2 Preparation of 2E-decenoic acid N- (2-methylbutvOamide

Analogously to Example 1, the 2E-decenoic acid N- (2-methylbutyl) amide was prepared from 2E-decenoic acid and 2-methylbutylamine (purity GC: 94.2%). ¹ H-NMR (CDCI ₃ ; 400 MHz, δ): 6.83 (1 H, dt, 15.2 Hz, 6.9 Hz, H-3), 5.76 (1 H, dt, 15.3 Hz, 1.5 Hz, H-2), 5.45 (1 H, bs, NH), 3.27 (1 H, dt, 13.4 Hz, 6.1 Hz, H-1 '), 3.13 (1 H, ddd, 13.4 Hz, 7.2 Hz, 6.1 Hz, H-1 '), 2.17 (2H, ddd, 7.1 Hz, 7.1 Hz, 1, 6 Hz, H-4), 1, 58 (1 H, m, 6.7 Hz, H-2 '), 1, 48 - 1, 35 (2H, m), 1, 35 - 1, 23 (8H, m) , 1, 16 (1 H, m, H-3 '), 0.91 (3H, t, 7.4 Hz, H-4'), 0.906 (3H, d, 6.8 Hz, H-5 ' ), 0.88 (3H, t, 6.8 Hz, H-10) ppm.

¹³ C NMR (CDCI ₃ ; 100 MHz, δ): 166.17 (C, C-1), 144.80 (CH, C-3), 123.57 (CH, C-2), 45.11 (CH ₂ , C-1 '), 35.02 (CH ₂ , C-2'), 32.04 (CH ₂ , C-4), 31, 77 (CH ₂ , C-8), 29.16 (CH ₂ , C-5,6 or 7), 29,10 (CH ₂ , C-5,6 or 7), 28,29 (CH ₂ , C-5,6 or 7), 27,03 (CH ₂ , C-3 '), 22.64 (CH ₂ , C-9), 17.19 (CH ₃ , C-5'), 14.08 (CH ₃ , C10), 11, 28 (CH ₃ , C-4 ") ppm.

Example 3 Preparation of 3E-nonenoic acid-N-isobutylamide

2.5 g of 3E-nonenoic acid and 1.84 g of N-hydroxysuccinimide were dissolved in 20 ml of 1,4-dioxane and a solution of 3.30 g of N, N'-dicyclohexylcarbodiimide was metered in. The mixture, which becomes cloudy, is stirred at 20-23 ° C. overnight and filtered. The filtrate is evaporated to dryness in vacuo (4.2 g, yellow oil). The crude product is dissolved in 50 chloroform and a mixture of 1.8 ml of isobutylamine and 5 ml of triethylamine is added. The reaction mixture is stirred at 20-23 ° C. for a further 4 h, acidified with 25 ml of 10% HCl, washed with 25 ml of 10% sodium carbonate solution, dried over sodium sulfate, filtered and the filtrate is concentrated in vacuo. 3.33 g of a yellowish oil are obtained (purity GC: 96.2% main product, 2E isomer 2.5%).

¹ H NMR (CDCI ₃ ; 400 MHz, δ): 6.02 (1 H, bs), 5.63 (1 H, dtt, J = 15.24 Hz, J = 6.5 Hz, J = 1 , 10 Hz, H-4), 5.53 (1 H, dtt, J = 15.27 Hz, J = 6.83 Hz, J = 1, 15 Hz, H-3), 3.07 (2H, dd, J = 6.82 Hz, J = 5.98 Hz, H-1 '), 2.94 (2H, dd, J = 6.8 Hz, J = 1, 10 Hz, H-2), 2 , 05 (2H, td, J = 7.05 Hz, J = 0.97 Hz, H-5), 1.77 (1 H, m, J = 6.73 Hz, H-2 '), 1, 43 -1, 23 (6H, m, H-6, H-7, H-8), 0.90 (6H, d, J = 6.7 Hz, H-3 '), 0.88 (3H, t, J = 6.95 Hz, H-9) ppm. Example 4 Preparation of 3E-decenoic acid-N-isobutylamide

2.72 g of 3E-decenoic acid and 1.84 g of N-hydroxysuccinimide were dissolved in 20 ml of 1,4-dioxane and a solution of 3.30 g of N, N'-dicyclohexylcarbodiimide was metered in. The mixture, which becomes cloudy, is stirred at 20-23 ° C. overnight and filtered. The filtrate is evaporated to dryness in vacuo (yellow oil). The crude product is dissolved in 50 chloroform and a mixture of 1.8 ml of isobutylamine and 5 ml of triethylamine is added. The reaction mixture is stirred at 20-23 ° C. for a further 4 h, acidified with 25 ml of 10% HCl, washed with 25 ml of 10% sodium carbonate solution, dried over sodium sulfate, filtered and the filtrate is concentrated in vacuo. About 3 g of a yellowish oil are obtained, which was purified by chromatography on silica gel 60 using the eluent n-hexane / ethyl acetate.

¹ H-NMR (CDCI ₃ ; 400 MHz, δ): 5.70 (1H, bs), 5.64 (1 H, dtt, J = 15.2 Hz, = 6.6 Hz, J = 1 Hz, H-4), 5.52 (1 H, dtt, J = 15.2 Hz, J = 7 Hz, J = 1 Hz, H-3), 3.07 (2H, dd, J = 6.9 Hz , J = 6.1 Hz, H-1 '), 2.95 (2H, dd, J = 7 Hz, J = 1 Hz, H-2), 2.02 (2H, td, J = 7 Hz, = 1 Hz, H-5), 1.72 (1 H, m, J = 6.7 Hz, H-2 '), 1.43-1.23 (8H, m, H-6, H-7 , H-8, H-9), 0.86 (6H, d, J = 6.7 Hz, H-3 "), 0.85 (3H, t, J = 7 z, H-10) ppm.

¹³ C NMR (CDCI ₃ ; 100 MHz, δ): 171, 32 (C, C-1), 136.85 (CH, C-4), 122.70 (CH, C-3), 46.83 (CH ₂ , C-1 '), 40.65 (CH ₂ , C-2), 32.57 (CH ₂ , C-5), 31, 70 (CH ₂ , C-8), 29.20 ( CH ₂ , C-6), 28.87 (CH ₂ , C-7), 28.46 (CH, C-2 '), 20.04 (2 CH ₃ , C-3'), 14.09 ( CH ₃ , C-10) ppm.

Example 5 Sensory evaluation

The substance to be tasted (see below) was dissolved in ethanol and the ethanolic solution was then diluted with 11% sugar solution (final concentration: c). About 5 ml of the sugar solution were swallowed for tasting. If the threshold of the substance was known, a value just above the threshold was chosen for the tasting. A group of 6 - 8 examiners tasted the solutions.

a) Profile 2E-decenoic acid-N-isobutylamide (Example 1):

c = 10 ppm: slightly sharp, anesthetic, feeling warm, promoting saliva; slightly herbaceous, citrus-like, tingling, ginger-like

b) Profile 2E-decenoic acid N- (2-methylbutyl) amide (example 2):

c = 10 ppm: slightly sharp, salivating, tingling, slight feeling of warmth

c) Profile 3E-nonenoic acid-N-isobutylamide (Example 3):

c = 10 ppm: anesthetic, sharpness builds up, impression of sweet almond, slightly bitter

d) Profile 3E-decenoic acid-N-isobutylamide (Example 4):

c = 10 ppm: scratchy sharpness, builds up slowly in the throat, slightly bitter

Comparative Examples

e) Dihydrocapsaicin profile:

c = 100 ppb: slightly delayed effect in the throat, aggressive, burning sharpness (chilli, slight heat)

f) Profile 2E, 4E-decadienoic acid-N-isobutylamide (trans-pellitorin) c = 10 ppm: salivating, greasy, fruity, slightly tingling, slightly spicy

Example 6 Use in an apple brandy as an alcohol flavor enhancer

Standard preparation with 20 vol% ethanol:

20 l ethanol 96 vol.%

5.2 I aroma (natural apple fruit juice liqueur aroma, 15% vol.)

27 kg sugar syrup

1 kg of citric acid monohydrate

Fill up with water, demineralized to 100 l; Total amount 100 I.

Reduced preparation with alcohol flavor enhancer

14.90 1 ethanol 96 vol.%

5.2 I aroma (natural apple-fruit juice-liqueur aroma, 15% vol., Contains 0.01% by weight 2E-decenoic acid-N-isobutylamide)

27 kg sugar syrup

1 kg of citric acid monohydrate

Fill up with water, demineralized to 100 l; Total amount 100 I.

The two preparations are almost identical in terms of sensors. Example 7 Use in combination with a spicy plant extract as an alcohol flavor enhancer

Standard preparation with 20 vol% ethanol:

20 l ethanol 96 vol.%

5.2 I aroma (natural apple fruit juice liqueur aroma, 15% vol.)

27 kg sugar syrup

1 kg of citric acid monohydrate

Fill up with water, demineralized to 100 l; Total amount 100 I.

Reduced preparation with alcohol flavor enhancer

14.90 1 ethanol 96 vol.%

5.2 I aroma (natural apple fruit juice liqueur aroma, 15% vol., Contains 0.0025% by weight of 2E-decenoic acid-N-isobutylamide and 0.0075% by weight of paradise grain extract)

27 kg sugar syrup

1 kg of citric acid monohydrate

Fill up with water, demineralized to 100 l; Total amount 100 I.

The two preparations are almost identical in terms of sensors. Example 8 Use in an alcohol-free preparation as an imitation alcohol

Standard preparation with alcohol (5.5% alcohol by volume):

4.06 g absolute ethanol, p.A.

20 g invert sugar syrup 66.5% dry matter

75.94 g of tap water

Preparation without alcohol:

20 g invert sugar syrup 66.5% dry matter

80 g tap water

20 ppm on total preparation 2E-decenoic acid-N-isobutylamide from Example 1

For the individual preparations, all ingredients are mixed and the aroma is dosed last.

Tasting notes: the preparation without alcohol has an alcoholic sharpness character, which is in good agreement with the standard preparation (5.5% by volume). Example 9 Use in a non-alcoholic preparation as an imitation alcohol together with a spicy plant extract

Standard preparation with alcohol (5.5% alcohol by volume):

4.06 g absolute ethanol, p.A.

20 g invert sugar syrup 66.5% dry matter

75.94 g of tap water

Preparation without alcohol:

20 g invert sugar syrup 66.5% dry matter

80 g tap water

20 ppm on total preparation 2E-decenoic acid-N-isobutylamide from Example 1

0.3 g grain of paradise extract

Tasting: Here too, the preparation without ethanol shows an alcoholic sharpness character, which corresponds very well with the standard preparation (5.5% by volume). Example 10 Use in a toothpaste as a flavoring

The ingredients of parts A and B are each premixed separately and thoroughly stirred together under vacuum at 25-30 ° C. for 30 minutes. Part C is premixed and added to A and B; D is added and the mixture is stirred well under vacuum at 25-30 ° C. for 30 minutes. After relaxation, the toothpaste is ready and can be filled.

Example 11 Use in a sugar-free chewing gum as a flavoring

Parts A to D are mixed and kneaded intensively. The raw material can be processed into ready-to-eat chewing gum, for example in the form of thin strips.

Example 12 Use in a mouthwash as a flavoring

The ingredients of parts A and B are mixed individually. Part B is slowly stirred into Part A until the mixture is homogeneous.

Example 13 Use in a sprinkling wort for fried nibbles 100 g of non-seasoned tortilla chips are sprinkled with a mixture of 7 g of dry cheese flavor for snacks and 0.07 g of 2E-decenoic acid-N-isobutylamide. Example 14 Use in a biscuit cream filling

100 g of standard cream filling are mixed intensively with 0.4 g of strawberry flavor and 0.1 g of 2E-decenoic acid-N-isobutylamide.

Example 15 Use in a hard caramel as a flavoring

Sucrose is dissolved in water at 115 ° C. The glucose syrup is added and the mixture is brought to 140.degree. The aroma and the ethanolic solution are added and, after mixing, poured into molds at a temperature of 130 - 135 ° C and allowed to solidify.

Claims

Expectations

1. Use of an alkenecarboxylic acid N-alkylamide of the formula

(3a)

or

(3b)

or a mixture of two or more compounds of the formula (3a) and / or (3b), where in each case

R ^{1 represents} an alkyl radical, and

R ^{2 represents} a lower alkyl radical, as (i) pungent and / or (ii) to produce a feeling of warmth when consumed regardless of the temperature of the alkenecarboxylic acid N-alkylamide and / or (iii) to enhance the taste of ethanol and / or (iv) to imitate the Taste of ethanol and / or (v) to induce salivation.

2. Use according to claim 1 in a nutritional or pleasure preparation.

3. Use according to claim 1 or 2 in an oral hygiene preparation.

4. Nutritional, oral hygiene or pleasure or cosmetic or dermatological preparation comprising an effective amount of alkenecarboxylic acid N-alkylamide of the formula

(3a)

or

(3b) or a mixture of two or more compounds of the formula (3a) and / or (3b), where in each case

R ^{1 represents} an alkyl radical, and

R ^{2 represents} a lower alkyl radical.

5. A preparation according to claim 4, comprising at least one other substance which tastes pungent and / or induces a feeling of heat and / or induces salivation.

6. Preparation according to claim 4 or 5, comprising at least one sharp-tasting and / or salivary-inducing plant extract.

7. Preparation according to one of claims 4 to 6, comprising at least one substance causing a physiological cooling effect.

8. A semi-finished product according to one of claims 4 to 7.

9. Preparation as a fragrance, aroma or flavor composition or seasoning mixture according to at least one of claims 4 to 8.

10. Preparation with a taste reminiscent of the taste of ethanol, comprising an effective amount of alkenecarboxylic acid-N-alkylamide of the formula

(3a)

or

(3b)

or a mixture of two or more compounds of the formula (3a) and / or (3b),

where each

R ^{1 represents} an alkyl radical,

and

R ^{2 represents} a lower alkyl radical,

as (i) pungent and / or (ii) to produce a feeling of warmth when consumed regardless of the temperature of the alkenecarboxylic acid N-alkylamide and / or (iii) to enhance the taste of ethanol and / or (iv) to imitate the

Taste of ethanol and / or (v) for inducing Salivation and optionally an effective amount of (i) a further pungent and / or heat-generating and / or salivating substance and / or (ii) a pungent and / or salivating plant extract.

11. The preparation according to claim 10, wherein the taste reminiscent of the taste of ethanol is essentially determined by the amount of alkenecarboxylic acid-N-alkylamide (s).

12. Preparation according to claim 10 or 11, wherein ethanol is present in a maximum amount of 0.5 wt .-%, based on the total mass of the preparation.

13. Use of 2E-decenoic acid-N-isobutylamide and / or 2E-decenoic acid-N- (2-methylbutyl) amide as an agent for promoting saliva.