DE202004021058U1 - Use of N-alkyl alkenoamides as sharp-tasting substances, for inducing a temperature-independent feeling of warmth, for enhancing or imitating the flavor of ethanol or for inducing salivation - Google Patents

Abstract

N-alkyl alkenamides (I) are used as sharp-tasting substances, for inducing a temperature-independent feeling of warmth, for enhancing or imitating the flavor of ethanol or for inducing salivation. N-alkyl alkenamides of formula (I) are used as sharp-tasting substances, for inducing a temperature-independent feeling of warmth, for reinforcing or imitating the flavor of ethanol or for inducing salivation. R-CO-NHR 2>(I) R : R 1>CH 2CH 2CH 2CH=CH- or R 1>CH 2CH 2CH=CHCH 2-; R 1>alkyl; R 2>lower alkyl. An independent claim is also included for a nutritional, oral hygiene, semiluxury, cosmetic or dermatological product comprising (I).

Description

The Invention describes the use of alkenecarboxylic acid N-alkylamides and their Stereoisomers as intense pungent and flavoring agents, preferred in the diet, Oral hygiene or pleasure preparations. Further concerns the invention of nutrition, oral hygiene or pleasure-containing preparations containing the alkenecarboxylic acid N-alkylamides according to the invention.

Capsaicin [N- (4-hydroxy-3-methoxybenzyl) -8-methyl- (6E) -nonoic acid amide, formula (1)] and other capsaicinoids have been available as pungent-tasting and heat-generating flavorings of various Capsicum species, especially chilli Known in 1871. Heat-producing substances or substances with a heat-generating effect are understood as meaning those which cause sensation of heat. With a correspondingly low dosage of capsaicinoids (the threshold is at a dilution of about 1:10 ⁵ ) only a pleasant, neutral sharpness and a warm sensation in the mouth is perceived. The problem with capsaicin is the high acute toxicity (LD ₅₀ (mouse oral) 47 mg), which makes the preparation more difficult to prepare, as well as the chronic effects of 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 minerals. The piperine (1-piperoylpiperidine, formula (2),), which occurs in white pepper, also gives 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 that is reminiscent of pepper, so that the application can be limited in many preparations.

task The present invention was to provide fabrics with a sharp, tingling, mouthwashing and / or heat-generating Effect as well as an otherwise relatively neutral flavor profile, which as flavorings in the diet or benefit preparations.

oder einer Mischung aus zwei oder mehr Verbindungen der Formel (3a) und/oder (3b)
wobei jeweils
R¹ einen Alkylrest darstellt,
und
R² einen Niederalkylrest darstellt,
als (i) Scharfstoff und/oder (ii) zur Erzeugung eines Gefühls von Wärme beim Verzehr unabhängig von der Temperatur des Alkencarbonsäure-N-alkylamids und/oder (iii) zur Verstärkung des Geschmacks von Ethanol und/oder (iv) zur Imitierung des Geschmacks von Ethanol und/oder (v) zur Induzierung des Speichelflusses insbesondere zur Verwendung in der Ernährung, der Mundhygiene oder dem Genuss dienenden Zubereitung.The invention solves this problem by the use of an alkenecarboxylic acid N-alkylamide of the formula

or a mixture of two or more compounds of the formula (3a) and / or (3b)
each one
R ^{1 represents} an alkyl radical,
and
R ^{2 represents} a lower alkyl radical,
as (i) pungent and / or (ii) to produce a sensation of heat on consumption regardless of the temperature of the alkenecarboxylic acid N-alkylamide and / or (iii) to enhance the taste of ethanol and / or (iv) to mimic the Flavor of ethanol and / or (v) to induce salivation, particularly for use in nutrition, oral hygiene or pleasure preparation.

The wavy Line in the formulas (3a) and (3b) means that the associated double bond E- or Z-configured. The compounds of the formulas (3a) and (3b) in the case of the presence of asymmetric carbon atoms as pure Enantiomers and / or diastereomers or as mixtures thereof available. An alkyl radical in the context of the invention are linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms, wherein the following groups are preferred: ethyl, propyl, butyl, pentyl and hexyl.

One Lower alkyl in the context of the invention are linear, branched or cyclic alkyl groups having 1 to 5 carbon atoms, wherein the following groups are preferred: methyl, ethyl, propyl, 2-propyl, cyclopropyl, butyl, 2-butyl; 3-methylpropyl (i.e. Isobutyl), cyclobutyl, 1- or 2-methylcyclopropyl, 2-methylpropyl, pentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, cyclopentyl and 1-, 2- or 3-methylcyclobutyl, but especially Isobutyl or 2-methylbutyl.

Though It is already known that some fatty acid isobutylamides ("alkamides") trigeminal stimuli like local anesthesia, sharpness or tingling in the oral cavity or on the skin and mucous membranes can cause. Structurally similar to the compounds of formula (3a) and (3b) Pellitorin (2E, 4E-decadienoic acid N-isobutylamide) shows, however, mainly a numbing Effect (see H. C. F. Su and R. Horvat, J. Agric., Food Chem., Jhrg. 1981, Vol. 29, pages 115-118), which also delays entry. For the also known 2E, 4Z-decadienoic acid N-isobutylamide have not been sensory Data described. In an unspecified study (B. Bryant and I. Mezine, in ACS Symposium Series, Vol. 825, Chemistry of Taste, P. Given and D. Paredes, Eds., Vol. 825, American Chemical Society 2002, pp. 202-212) was shown to be 2E-decenoic acid N-isobutylamide in contrast to the 2,4-alkadienoic acid amides gave no good impression (further sensory data were not published). In a study of 2E-tetradecenoic acid N-isobutylamide was also no sharpness at the concentrations tested (H. Shibuya et al., Chem. Pharm. Bull., Jhrg. 1992, Vol. 40, 2325-2330).

Surprised and for The person skilled in the art was therefore unable to foresee that the invention to be used Alkene carboxylic acid N-alkylamides in the sensory examination a somewhat delayed onset, flock, but especially warm, sometimes slightly numbing, sometimes tingling or as described by (English) Tingling taste impression as well as partially salivary are the sensory impressions at higher Use concentrations are relatively strong and persist for a relatively long time. There are further sensory impressions to be seen, the profile so that the compounds of the formula (3a) and (3b) (and their mixtures) are excellent as flavorings (for the mentioned Purposes) can be used.

Some the compounds of formula 3a are known: so was 2E-decenoic acid N-isobutylamide found in Piper guineense, a plant used in Nigeria as a spice (S.K. Adesina, A.S. Adebayo, S.K. O. Adesina and R. Groening, Pharmacy 2002, 57 (9), 622-627).

3E-decenoic acid N-isobutylamide was earlier ever produced and characterized (see Journal of the Indian Chemical Society, vol. 14, jhr. 1937, pages 421 and 424 or Beilstein reference no. 1778318).

Particularly preferred are the following alkenecarboxylic acid N-alkylamides:
2E-decenoic acid N-isobutylamide
2Z-decenoic acid N-isobutylamide
2E-decenoic acid-N- (2-methylbutyl) amide
3E-decenoic acid N-isobutylamide
3E-None acid N-isobutylamide
as well as their mixtures. Another object of the present invention are preparations, semi-finished goods and fragrance, flavor and Geschmackstoffkompositionen containing the Alkencarbonsäure-N-alkylamides invention. See below.

The alkenecarboxylic acid N-alkylamides (or mixtures thereof) to be used according to the invention can also be used in cosmetic or dermatological preparations for producing a sensation of heat the skin can be used.

In a particularly preferred embodiment The invention relates to the alkenecarboxylic acid N-alkylamides according to the invention (or their mixtures) in combination with other pungent-tasting and / or a feeling of heat generating and / or salivation inducing substances or (in particular) sharp-tasting and / or salivary-inducing used herbal extracts. This way can be a special rounded sensory profile can be achieved. especially the Combination of the invention to be used Alkene carboxylic acid N-alkylamides with a pungent-tasting and / or salivary-inducing vegetable 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, combination suitable for aart-tasting and / or a feeling of heat-generating substances are hereby, for example: capsaicin, dihydrocapsaicin, gingerols, paradole, Shogaole, piperine, carboxylic acid N-vanillylamide, in particular Nonanoic-N-vanillylamide, Pellitorin or spilanthol, 2-nonenoic acid N-4-hydroxy-3-methoxyphenylamide, Alkyl ethers of 4-hydroxy-3-methoxybenzyl alcohol, in particular 4-hydroxy-3-methoxybenzyl n-butyl ether, Alkyl ethers of 4-acyloxy-3-methoxybenzyl alcohol, in particular 4-acetyloxy-3-methoxybenzyl n-butyl ether and 4-acetyloxy-3-methoxybenzyl n-hexyl ether, Alkyl ethers of 3-hydroxy-4-methoxybenzyl alcohol, Alkyl ethers of 3,4-dimethoxybenzyl alcohol, Alkyl ethers of 3-ethoxy-4-hydroxybenzyl alcohol, alkyl ethers of 3,4-methylenedioxybenzyl alcohol, (4-hydroxy-3-methoxyphenyl) essigsäureamide, in particular (4-hydroxy-3-methoxyphenyl) acetic acid N-n-octylamide, vanillomandelic acid alkylamides, Ferulic acid phenethylamides, Nicotinaldehyde, methyl nicotinate, propyl nicotinate, 2-butoxyethyl nicotinate, Benzyl nicotinate, 1-acetoxychavicol, polygodial and isodrimeninol.

to Combination are suitable pungent-tasting herbal extracts all for food suitable herbal extracts that have a sharp and / or warm cause sensory impression. Preferred as herbal extracts are in this respect, for example, pepper extract (Piper ssp., in particular Piper nigrum), water pepper extract (Polygonum ssp., In particular Polygonum hydropiper), extracts of Allium ssp. (especially onion and garlic extracts), extracts of radish (Raphanus ssp.), horseradish extracts (Cochlearia armoracia), extracts of black (Brassica nigra), wild or yellow mustard (Sinapis ssp., especially Sinapis arvensis and Sinapis alba), Bertram root extracts (Ancyclus ssp., especially Anacylcus pyrethrum L.), extracts of the sun-hawk (Echinaceae ssp.), extracts Szechuan pepper (Zanthoxylum ssp., Especially Zanthoxylum piperitum), Spilanthate extract (Spilanthes spp., In particular Spilanthes acmella), chile extract (Capsicum ssp., Especially Capsicum frutescens), grains of paradise extract (Aframomum ssp., Especially Aframomum melegueta [Rose] K. Schum.), Ginger extract (Zingiber ssp., Especially Zingiber officinale), Galanga extract (Kaempferia galanga or Alpinia galanga) and Jaborandi extract (Pilocarpus species, in particular Pilocarpus jaborandi).

The Salivary flux inducing substances may, for example, be certain ungesätttigte Alkamides (e.g., Pellitorine, Spilanthole, Shogaoole), alkaloids (e.g. Pilocarpine), salivary Peptides (e.g., substance P, tachykinins, physalaemin), but also simple ones fruit acids (e.g., citric acid, Tartaric acid).

The For example, salivary flow-inducing plant extracts may the aforementioned salivary flux-inducing substances containing plants or plant extracts.

The pungent and / or salivary-inducing plant Extracts can frequently the corresponding fresh or dried plants or parts of plants, but especially white, green or black peppercorns, Water peppercorns, Onions and garlic, radish root, horseradish, mustard seeds, sun hat roots, Bertram root, plant parts of Zanthoxylum species, parts of plants spilanthes species, chili peppers, grains of paradise or ginger or galanga roots be won. The dried parts of the plant, which are preferably crushed beforehand, usually with a food-grade and stimulants suitable solvents, at a temperature in the range of 0 ° C to the boiling point of the respective solvent extracted, then filtered and the filtrate concentrated completely or partially, preferably by distillation, freeze or spray drying. The thus obtained Crude extract can then be worked up even further, for example with steam at pressures from 0.01 mbar to normal pressure and / or in a food-grade and stimulants suitable solvent become. For Food and beverage suitable solvents 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 Another particularly preferred embodiment of the invention the invention to be used Alkene carboxylic acid N-alkylamides (or mixtures thereof) in combination with one or more of them physiological cooling effect used causing substances.

When physiological cooling effect causing substances For example, menthol and menthol derivatives (e.g., L-menthol, rac. Menthol) menthyl ether (e.g., (1-menthoxy) -1,2-propanediol, (1-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 carbonates (e.g., menthyl propylene glycol carbonate, Menthyl ethylene glycol carbonate, menthyl glycerol carbonate), the half esters of menthol with dicarboxylic acid (e.g., menthyl succinate, menthyl glutarate), menthane carboxylic acid amides (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 (I - (-) - isopulegol, I - (-) - isopulegol acetate), menthane derivatives (e.g., p-menthane-3,8-diol), Cubebol, pyrrolidone derivatives of cycloalkyldione derivatives (e.g., 3-methyl-2 (1-pyrrolidinyl) -2-cyclopenten-1-one) or Icilin serve.

Of course, the physiological cooling effect causative substances, as far as they occur in nature, too in the form of an extract, a distillate, a crystallization or otherwise processed and / or purified preparation from natural Sources, preferably from natural occurring or bred Plants or parts of plants and / or plant Callus or Cell cultures or derived from fermentative processes. For example can suitable menthol, menthone or isopulegol-containing preparations and their derivatives from a variety of Mentha ssp. by steam distillation or other distillation processes are obtained.

Another object of the invention are nutritional or pleasure preparations containing an effective amount of an alkenecarboxylic acid N-alkylamide (to provide a sensation of sharpness or heat, or to enhance or mimic the taste of ethanol, or to induce salivary) Formula (3a) or (3b) or a mixture of two or more compounds of the formula (3a) and / or (3b)
each one
R ¹
and
R ^{2 have} the meanings given above,
and optionally other common basic, auxiliary and additives for food and beverage. These preparations generally contain 0.0000001% by weight to 10% by weight, preferably 0.00001 to 1% by weight, but more preferably 0.00001% by weight to 0.1% by weight, based on the total weight of the preparation, of one or more alkenecarboxylic acid N-alkylamides of the formula (3a) or (3b). Further customary bases, auxiliaries and additives for foodstuffs or semi-luxury foods 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 may 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 pungent-tasting and / or heat-generating and / or salivation-inducing substance or at least one hard-tasting and / or salivation-inducing vegetable extract. For the purposes of the invention, nutrition or pleasure-serving preparations are, for example, baked goods (eg bread, dry biscuits, cakes, other pastries), confectionery (for example chocolates, chocolate bar products, other bar products, fruit gums, hard and soft caramels, chewing gum), alcoholic or non-alcoholic beverages. alcoholic beverages (eg coffee, tea, wine, wine-based drinks, beer, beer-based drinks, liqueurs, brandies, brandies, fruit-based sodas, isotonic drinks, soft drinks, nectars, fruit and vegetable juices, fruit or vegetable juice preparations), instant drinks (eg instant drinks) Cocoa drinks, instant tea drinks, instant coffee drinks), meat products (eg ham, fresh sausage or raw sausage preparations, spiced or marinated fresh or salted meat products), eggs or egg products (dry egg, egg white, egg yolks), cereal products (eg breakfast cereals, Muesli bars, pre-cooked finished rice products), dairy products (eg milk drinks, milk ice cream, yoghurt , Kefir, cream cheese, soft cheese, hard cheese, dried milk powder, whey, butter, buttermilk), fruit preparations (eg jams, fruit, fruit sauces, fruit fillings), vegetable preparations (eg ketchup, sauces, dried vegetables, frozen vegetables, pre-cooked vegetables, cooked vegetables), snacks (Eg baked or fried potato chips or potato dough products, extrusions based on corn or peanut), products based on fat and oil or emulsions thereof (eg mayonnaise, remoulade, dressings), other ready meals and soups (eg dry soups, instant soups, pre-cooked Soups), spices, spice mixtures and in particular seasoning seasonings, which are used, for example, in the snack area. The preparations according to the invention can also serve as semi-finished goods for the production of further preparations serving for nutrition or enjoyment. The preparations according to the invention may also be in the form of capsules, tablets (non-coated and coated tablets, eg gastric juice-resistant coatings), dragees, granules, pellets, solid mixtures, dispersions in liquid phases, as emulsions, as powders, as solutions, as pastes or as other swallowable or chewable preparations are available as a dietary supplement.

oder einer Mischung aus zwei oder mehr Verbindungen der Formel (3a) und/oder (3b),
wobei jeweils
R¹ einen Alkylrest darstellt,
und
R² einen Niederalkylrest darstellt,
als (i) Scharfstoff und/oder (ii) zur Erzeugung eines Gefühls von Wärme beim Verzehr unabhängig von der Temperatur des Alkencarbonsäure-N-alkylamids und/oder (iii) zur Verstärkung des Geschmacks von Ethanol und/oder (iv) zur Imitierung des Geschmacks von Ethanol sowie gegebenenfalls eine wirksame Menge (i) einer weiteren scharf schmeckenden und/oder wärmeerzeugenden Substanz und/oder (ii) eines scharf schmeckenden pflanzlichen Extrakts.It has also been found to be particularly advantageous that the alkenecarboxylic acid N-alkylamides to be used according to the invention, in particular in the preferred combination with pungent-tasting plant extracts, can mimic the pungent taste of alcohol in alcoholic beverages or preparations with alcoholic beverages, making it possible to use the To lower or completely replace alcoholic strength in alcoholic beverages or in preparations containing alcoholic beverages with the same sensory evaluation. A corresponding preparation according to the invention therefore comprises an effective amount of alkenecarboxylic acid N-alkylamide of the formula

or a mixture of two or more compounds of the formula (3a) and / or (3b),
each one
R ^{1 represents} an alkyl radical,
and
R ^{2 represents} a lower alkyl radical,
as (i) pungent and / or (ii) to produce a sensation of heat on consumption regardless of the temperature of the alkenecarboxylic acid N-alkylamide and / or (iii) to enhance the taste of ethanol and / or (iv) to mimic the Flavor of ethanol and optionally an effective amount of (i) another pungent-tasting and / or heat-generating substance and / or (ii) a pungent-tasting vegetable extract.

Preferably The taste reminiscent of the taste of ethanol is there essentially determined by the amount of alkenecarboxylic acid N-alkylamide (s) determined. ethanol is in such preparations according to the invention at most in an amount of 0.5% by weight when an alcohol reduction across from a desired tasting comparable product is sought. Preferably contains such a preparation less than 0.1 wt .-% ethanol.

Especially Advantageously, it has also been found that the alkenecarboxylic acid N-alkylamides according to the invention the great taste of capsaicin, dihydrocapsaicin and nonivamide can imitate and it makes it possible is the capsaicin content in those diet or pleasure serving Preparations with constant sensory evaluation essential lower.

The invention further provides oral hygiene preparations, in particular dentifrices such as toothpastes, tooth gels, tooth powders, mouthwashes, chewing gums and other oral hygiene products containing an effective (see above) amount 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),
each one
R ¹
and
R ^{2 have} the meaning given above
and optionally other common bases, excipients and additives for such preparations. They preferably contain 0.0000001 wt .-% to 10 wt .-%, preferably 0.00001 to 1 wt .-%, but in particular 0.00001 wt .-% to 0.1 wt .-%, based on the total weight the preparation, to Alkencarbonsäure N-alkylamides of the formula (3a) or (3b). Other customary bases, auxiliaries and additives for oral hygiene preparations may 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 may 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 pungent-tasting and / or heat-generating and / or salivation-inducing substance or at least one hard-tasting and / or salivation-inducing vegetable extract. Dentifrices containing the alkenecarboxylic acid N-alkylamides according to the invention generally consist of an abrasive system (grinding or polishing agents), such as, for example, silicic acids, calcium carbonates, calcium phosphates, aluminum oxides and / or hydroxyapatites, surface-active substances, such as sodium lauryl sulfate, sodium lauryl sarcosinate and or cocamidopropylbetaine, from humectants, such as glycerol and / or sorbitol, from thickeners, such as carboxymethylcellulose, polyethylene glycols, carrageenans and / or Laponites ^® , sweeteners, such as saccharin, stabilizers and active ingredients, such as sodium fluoride, sodium monofluorophosphate , Tin difluoride, 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 carbonate.

chewing gum, which the invention to be used Alkene carboxylic acid N-alkylamides generally consist of a chewing gum base, i. a chewing gum that becomes plastic during chewing, different kinds of sugars Species, sugar substitutes, sweeteners, Sugar alcohols, humectants, thickeners, emulsifiers, flavors and stabilizers.

Prefers can the alkenecarboxylic acid N-alkylamides of the formulas (3a) and / or (3b) or preparations according to the invention in Aufstreuwürzungen, so-called (English) Seasonings, are used to dry Mouthfeel when eating corn, potato or rice flour chips and snacks arises, to avoid and to improve the overall sensory impression.

preferred Aufstreuwürzungen contain e.g. synthetic, natural or nature-identical flavorings as well as carriers such as e.g. maltodextrin, Salts, e.g. Table salt, spices such as. Peppers and peppers, sugar sweeteners, e.g. Saccharin and flavor enhancer such as. Monosodium glutamate and / or inosine monophosphate.

The preparations according to the invention, which one or more alkenecarboxylic acid N-alkylamides of the formula (3a) or (3b) by preparing 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 into one of the diet, the oral hygiene or the benefit serving base preparation incorporated will be). Advantageously, compositions according to the invention which are present as a solution also by spray drying be converted into a solid preparation.

For the preparation of preparations according to the invention, according to a further preferred embodiment, the alkenecarboxylic acid N-alkylamides and optionally other constituents of the preparation according to the invention also previously in emulsions, in liposomes, for example starting from phosphatidylcholine, in microspheres, in nanospheres or in capsules, granules or extrudates a suitable for food and luxury food matrix, for example from starch, starch derivatives, cellulose or cellulose derivatives (eg hydroxypropyl cellulose), other polysaccharides (eg alginate), natural fats, natural waxes (eg Bie nenwachs, carnauba wax) or from proteins, such as gelatin, are incorporated. In a further preferred preparation process, the alkenecarboxylic acid N-alkyl-amides are previously complexed with one or more suitable complexing agents, for example with cyclodextrins or cyclodextrin derivatives, preferably β-cyclodextrin, and used in this complexed form.

Especially preferred is a preparation according to the invention, where the matrix is chosen is that the alkenecarboxylic acid N-alkylamides delayed be released from the matrix, giving you a long-lasting sharp or heat-producing Receives effect.

As other constituents for the preparations according to the invention, which serve nutrition or pleasure, it is possible to use further customary bases, auxiliaries and additives for foods or luxury foods, for example water, mixtures of fresh or processed, vegetable or animal raw materials or raw materials (eg crude fried, dried, fermented, smoked and / or cooked meat, egg, bone, cartilage, fish, crustacean and shellfish, vegetables, fruits, herbs, nuts, vegetable or fruit juices or pastes or their mixtures), digestible or not digestible carbohydrates (eg, sucrose, maltose, fructose, glucose, dextrins, amylose, amylopectin, inulin, xylans, cellulose), sugar alcohols (eg, sorbitol, mannitol, xylitol), natural or hydrogenated fats (eg, tallow, lard, palm fat, coconut fat, hardened Vegetable fat), fatty oils (eg sunflower oil, peanut oil, corn oil, thistle 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 (eg gelatin), enzymes (eg peptidases, glucosidases, lipases), nucleic acids , Nucleotides (inositol phosphate), taste modulating substances (eg sodium glutamate, 2-phenoxypropionic acid, hydroxyflavanones according to EP 1,258,200 ), Emulsifiers (eg lecithins, diacylglycerols), stabilizers (eg carageenan, alginate, locust bean gum, guar gum), preservatives (eg benzoic acid, sorbic acid), antioxidants (eg tocopherol or its derivatives, ascorbic acid or derivatives thereof), chelators (eg citric acid), organic or inorganic acidulants (eg malic acid, acetic acid, citric acid, tartaric acid, phosphoric acid), bitter substances (eg quinine, caffeine, limonin), sweeteners (eg saccharin, cyclamate, aspartame, neotame, neohesperidin-hydrochalcone, tagatose, sucralose), mineral salts ( For example, sodium chloride, potassium chloride, magnesium chloride, sodium phosphates), the enzymatic browning-preventing substances (eg sulfite, ascorbic acid), essential oils, plant extracts, natural or synthetic dyes or color pigments (eg carotenoids, flavonoids, anthocyanins, chlorophyll and their derivatives), spices, and Fragrances, synthetic, natural or nature-identical aroma and Geschm ackstoffe.

Prefers contain preparations according to the invention also a flavoring composition to the taste and / or smell to round off and refine the preparation. Suitable flavor compositions included e.g. synthetic, natural or nature-identical flavorings and fragrances, in particular but also other pungent-tasting and / or heat-producing substances or Plant extracts.

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

The preparations according to the invention, which serve as semi-finished goods, usually contain 0.0001 wt .-% to 95 wt .-%, preferably 0.001 to 80 wt .-%, but in particular From 0.01% by weight to 50% by weight, based on the total weight of the preparation, the invention to be used alkylamides alkenoic N and optionally one or more other flavoring and flavoring agents, if necessary, also different carrier and Auxiliaries or various solvents.

Especially semi-finished goods are preferred for the flavoring of finished goods, those to be used according to the invention using alkenoic acid N-alkylamides (or mixtures thereof) in combination with one or several pungent tasting and / or a feeling of heat generating substances or (especially) pungent-tasting plant extracts, containing these substances and / or in combination with others Saline-inducing substances or plant extracts containing these substances, the semi-finished goods also different carrier and May include adjuvants and / or various solvents.

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

Examples

Preparation of alkenoic acid N-alkylamides

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

56 g 2E-decenoic acid were dissolved in 82 ml of toluene and at 20-23 ° C with 44 g thionyl chloride added. The mixture was stirred overnight at 20-23 ° C, then 1 h at 40 ° C heated and then distilled off the toluene in a water-jet vacuum at 40 ° C. From the crude 2E-decenoic acid chloride (61 g) 40 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 and recrystallized from petroleum ether, where 20 g of product are obtained in the form of slightly yellowish crystal needles (purity GC: 96.5%).

¹ H-NMR (CDCl _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 (CDCl _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 Presentation of 2E-decenoic acid N- (2-methylbutyl) amide

Analogous to Example 1, starting from 2E-decenoic acid and 2-methylbutylamine was the 2E-decenoic acid N- (2-methylbutyl) amide prepared (purity GC: 94.2%).

¹ H-NMR (CDCl ₃ , 400 MHz, δ): 6.83 (1H, dt, 15.2 Hz, 6.9 Hz, H-3), 5.76 (1H, dt, 15.3 Hz, 1, 5Hz, H-2), 5.45 (1H, bs, NH), 3.27 (1H, dt, 13.4Hz, 6.1Hz, H-1 '), 3.13 (1H, 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 (1H, m, 6.7Hz, H-2 '), 1.48-1.35 (2H, m), 1.35-1.23 (8H, m), 1.16 (1H , m, H-3 '), 0.91 (3H, t, 7.4Hz, H-4'), 0.906 (3H, d, 6.8Hz, H-5 '), 0.88 (3H , t, 6.8 Hz, H-10) ppm.
¹³ C-NMR (CDCl 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 , C 10), 11.28 (CH ₃ , C-4 ') ppm.

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

2.5 g 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 added. The cloudy Expecting mixture will be at 20-23 ° C overnight touched 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. The reaction mixture becomes 4 at 20-23 ° C h stirred, acidified with 25 ml of 10% HCl, with 25 ml of 10% sodium carbonate solution washed over Dried sodium sulfate, filtered and the filtrate concentrated in vacuo. You get 3.33 g of a yellowish oil (Purity GC: 96.2% major product, 2E isomer 2.5%).

¹ N-NMR (CDCl ₃ , 400 MHz, δ): 6.02 (1H, bs), 5.63 (1H, dtt, J = 15.24 Hz, J = 6.5 Hz, J = 1.10 Hz, H-4), 5.53 (1H, 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 (1H, m, J = 6.73 Hz, H-2 '), 1.43-1, 23 (6H, m, H-6, H-7, H-8), 0.90 (6H, d, J = 6.7Hz, H-3 '), 0.88 (3H, t, J = 6.95 Hz, H-9) ppm.

Example 4 Presentation of 3E-decenoic acid N-isobutylamide

2.72 g 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 added. The cloudy Expecting mixture will be at 20-23 ° C overnight touched 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. The reaction mixture becomes 4 at 20-23 ° C h stirred, acidified with 25 ml of 10% HCl, with 25 ml of 10% sodium carbonate solution washed over Dried sodium sulfate, filtered and the filtrate concentrated in vacuo. You get about 3 g of a yellowish oil, by chromatography on silica gel 60 with the eluent n.-hexane / ethyl acetate was purified.

¹ H-NMR (CDCl ₃ ; 400 MHz, δ): 5.70 (1H, bs), 5.64 (1H, dtt, J = 15.2 Hz, J = 6.6 Hz, J = 1 Hz, H-4), 5.52 (1H, dtt, J = 15.2Hz, J = 7Hz, J = 1Hz, H-3), 3.07 (2H, dd, J = 6.9Hz, 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, J = 1 Hz, H-5), 1.72 (1H, 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 = 6.7Hz, H-3 '), 0.85 (3H, t, J = 7Hz, H-10) ppm.
¹³ C-NMR (CDCl 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 rating

• a) Profil 2E-Decensäure-N-isobutylamid (Beispiel 1): c = 10 ppm: leicht scharf, betäubend, Wärmegefühl, speichelfördernd; leicht krautig, Citrus-artig, kribbelnd, Ingwer-artig
• b) Profil 2E-Decensäure-N-(2-methylbutyl)amid (Beispiel 2): c = 10 ppm: leicht scharf, speichelfördernd, kribbelnd, leichtes Wärmegefühl
• c) Profil 3E-Nonensäure-N-isobutylamid (Beispiel 3): c = 10 ppm: anästhesierend, Schärfe baut sich auf, Eindruck nach süßer Mandel, leicht bitter
• d) Profil 3E-Decensäure-N-isobutylamid (Beispiel 4): c = 10 ppm: kratzende Schärfe, baut sich langsam im Rachen auf, leicht bitter

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). For tasting, approximately 5 ml of the sugar solution were swallowed in each case. When the threshold value 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 hot, numbing, sensation of warmth, salivary; slightly herbaceous, citrus-like, tingling, ginger-like
• b) Profile 2E-Decenoic acid N- (2-methylbutyl) amide (Example 2): c = 10 ppm: slightly spicy, salivary, tingling, slight heat sensation
• c) Profile 3E-nonenoic acid N-isobutylamide (Example 3): c = 10 ppm: anesthetizing, sharpness builds up, impression of sweet almond, slightly bitter
• d) Profile 3E-decenoic acid N-isobutylamide (Example 4): c = 10 ppm: scratching sharpness, builds up slowly in the throat, slightly bitter

Comparative Examples

• e) profile dihydrocapsaicin: c = 100 ppb: slightly delayed onset of action in the pharynx, aggressive, burning sharpness (chili, slight heat development)
• f) Profile 2E, 4E-decadienoic acid N-isobutylamide (Trans-pellitorin) c = 10 ppm: salivary, greasy, fruity, light tingling, weakly sharp

Example 6 Application in an apple schnapps as an alcohol flavor enhancer

Standard preparation with 20% by volume ethanol: 20 l Ethanol 96 vol.% 5.2 l Aroma (Natural Apple Fruit Juice Liqueur Flavor, 15% Vol.) 27 kg sugar syrup 1 kg Citric acid monohydrate

Fill up with Water, demineralized to 100 l; Total quantity 100 l

Reduced preparation with alcohol flavor enhancer 14.90 l Ethanol 96 vol.% 5.2 l Aroma (Natural Apple Fruit Juice Liqueur Flavor, 15% by volume, contains 0.01% by weight of 2E-decenoic acid N-isobutylamide) 27 kg sugar syrup 1 kg Citric acid monohydrate

Fill up with Water, demineralized to 100 l; Total quantity 100 l

The Both preparations are almost identical in sensory terms.

Example 7 Application in Combination with a sharp plant extract as alcohol flavor enhancer

Standard preparation with 20% by volume ethanol: 20 l Ethanol 96 vol.% 5.2 l Aroma (Natural Apple Fruit Juice Liqueur Flavor, 15% Vol.) 27 kg sugar syrup 1 kg Citric acid monohydrate

Fill up with Water, demineralized to 100 l; Total quantity 100 l

Reduced preparation with alcohol flavor enhancer 14.90 l Ethanol 96 vol.% 5.2 l Aroma (Natural Apple Fruit Juice Liqueur Flavor, 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 Citric acid monohydrate

Fill up with Water, demineralized to 100 l; Total quantity 100 l

The Both preparations are almost identical in sensory terms.

example 8 Application in an alcohol-free preparation as alcohol-imitation

Standard preparation with alcohol (5.5% vol. Alcohol): 4.06 g Absolute ethanol, pA 20 g Invert sugar syrup 66.5% dry matter 75.94 g tap water

Preparation without alcohol: 20 g Invert sugar syrup 66.5% dry matter 80 g tap water

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

For the individual Preparations are mixed all the ingredients and the aroma last dosed.

tasting notes: the preparation without alcohol has a character of alcoholic character which agrees well with the standard preparation (5.5% by volume).

Example 9 Application in an alcohol-free preparation as alcohol-imitation together with a sharp plant extract

Standard preparation with alcohol (5.5% vol. Alcohol): 4.06 g Absolute ethanol, pA 20 g Invert sugar syrup 66.5% dry matter 75.94 g tap water

Preparation without alcohol: 20 g Invert sugar syrup 66.5% dry matter 80 g tap water

20 ppm bez. to total preparation of 2E-decenoic acid N-isobutylamide from Example 1 0.3 g Grains of paradise extract

For the individual Preparations are mixed all the ingredients and the aroma last dosed.

tasting notes: Again, the preparation without ethanol shows a character of alcohol sharpness which agrees very well with the standard preparation (5.5% by volume).

Example 10 Use in a toothpaste as a flavoring agent

The Ingredients of Parts A and B are each premixed and together under vacuum at 25-30 ° C for 30 min well mulled. Part C is premixed and added to A and B; D is added and the mixture under vacuum. 25-30 ° C 30 min well mulled. After relaxation, the toothpaste is ready and can be bottled.

Example 11 Use in a Sugarless Chewing Gum as a Flavoring Agent

parts A to D are mixed and kneaded intensively. The raw mass can e.g. in the form of thin strips be processed into ready to eat chewing gum.

Example 12 Use in a mouthwash as a flavoring agent

The Ingredients of Parts A and B are mixed individually. Part B becomes slowly stirred into Part A, until the mixture is homogeneous.

Example 13 Application in a sprinkling wort for fried breadsticks

100 g not spiced Tortilla chips are made with a mixture of 7 g cheese dry flavor for snacks and 0.07 g of 2E-decenoic acid N-isobutylamide is scattered.

Example 14 Application in a biscuit cream filling

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

Example 15 Use in a hard caramel as a flavoring agent

sucrose is in water at 115 ° C solved. The glucose syrup is added and the mixture is brought to 140 ° C. The aroma and the ethanolic solution are added and after mixing with a temperature from 130-135 ° C in molds poured and allowed to solidify.

Claims (16)

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

or a mixture of two or more compounds of the formula (3b), wherein each R ^{1 represents} an alkyl radical, and R ² represents a lower alkyl radical. A preparation according to claim 1, comprising at least another pungent-tasting and / or a feeling of heat-producing and / or drooling inducing substance. A preparation according to claim 1 or 2, comprising at least a pungent and / or salivary-inducing plant Extract. A preparation according to any one of the preceding claims comprising at least one substance which causes a physiological cooling effect. As a semi-finished product present preparation after a of the preceding claims. As fragrance, flavor or flavor compositions or seasoning mix present preparation according to at least one of claims 1 to 5th A composition having a taste reminiscent of the taste of ethanol, comprising an effective amount of alkenecarboxylic acid N-alkylamide of the formula

or a mixture of two or more compounds of formula (3b), wherein each R ^{1 represents} an alkyl radical, and R ² represents a lower alkyl radical, as (i) pungent and / or (ii) for producing a sensation of heat when consumed independently the temperature of the alkenecarboxylic acid N-alkylamide and / or (iii) to enhance the taste of ethanol and / or (iv) to mimic the taste of ethanol and / or (v) to induce salivation and optionally an effective amount (i) another hard-tasting and / or heat-generating and / or salivation-inducing substance and / or (ii) a pungent-tasting and / or salivation-inducing plant extract. A preparation according to claim 7, wherein the flavor taste reminiscent of ethanol substantially by the amount of alkenecarboxylic acid N-alkylamide (s) is determined. A preparation according to claim 7 or 8, wherein ethanol is present in a maximum amount of 0.5 wt .-%, based on the total mass of the preparation. A preparation according to any one of claims 1 to 9, wherein in the compound of formula (3b) or at least one compound of formula (3b) in the mixture R ^{1 is} ethyl, propyl, butyl, pentyl or hexyl and R ² Methyl, ethyl, propyl, 2-propyl, cyclopropyl, butyl, 2-butyl, 3-methylpropyl, cyclobutyl, 1- or 2-methylcyclopropyl, 2-methylpropyl, pentyl, 2-pentyl , 3-pentyl, 2-methylbutyl, 3-methylbutyl, cyclopentyl or 1-, 2- or 3-methylcyclobutyl. A preparation according to claim 10, wherein in the compound of the formula (3b) or at least one compound of the formula (3b) in the mixture R ^{1 is} propyl and R ^{2 is} methyl, ethyl, propyl, 2-propyl, cyclopropyl, Butyl, 2-butyl, 3-methylpropyl, cyclobutyl, 1- or 2-methylcyclopropyl, 2-methylpropyl, pentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, cyclopentyl or 1-, 2- or 3-methylcyclobutyl- or R ^{1 is} ethyl, propyl, butyl, pentyl or hexyl and R ^{2 is} ethyl or cyclopropyl. Use or preparation according to claim 11, wherein in the compound of the formula (3b) or at least one compound of the formula (3b) in the mixture R ^{1 is} propyl and R ^{2 is} ethyl or R ^{1 is} propyl and R ^{2 is} cyclopropyl. Compound of the formula (3b)

wherein R ^{1 represents} an alkyl radical and R ^{2 represents} a lower alkyl radical, with the exception of 3E-decenoic acid N-isobutylamide. A compound according to claim 13, wherein R ^{1 is} ethyl, propyl, butyl, pentyl or hexyl and R ^{2 is} methyl, ethyl, propyl, 2-propyl, cyclopropyl, butyl, 2-butyl , 3-methylpropyl, cyclobutyl, 1- or 2-methylcyclopropyl, 2-methylpropyl, pentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, cyclopentyl or 1-, 2- or 3-methylcyclobutyl means. A compound according to claim 13 or 14, wherein R ^{1 is} propyl and R ^{2 is} methyl, ethyl, propyl, 2-propyl, cyclopropyl, butyl, 2-butyl, 3-methylpropyl, cyclobutyl, 1- or 2-methylcyclopropyl, 2-methylpropyl, pentyl, 2-pentyl, 3-pentyl, 2-methylbutyl, 3-methylbutyl, cyclopentyl or 1, 2 or 3-methylcyclobutyl or R ^{1 is} ethyl, propyl, butyl, pentyl or hexyl and R ^{2 is} ethyl or cyclopropyl. A compound according to any one of claims 13 to 15 wherein R ^{1 is} propyl and R ^{2 is} ethyl or R ^{1 is} propyl and R ^{2 is} cyclopropyl.