|Title of Invention||
"PREPARATIONS USED IN NUTRITION OR IN ORAL HYGIENE OR CONSUMED FOR PLEASURE COMPRISING TRANS-PELLITORIN"
|Abstract||The invention relates to the use of 2E,4E-decadienoic acid-N-isobutylamide (trans-peUitorin) as an aroma substance, in particular as a saliva-inducing aroma substance, preferably in preparations used in nutrition or in oral hygiene or consumed for pleasure. The invention further relates to preparations and semi-finished products as well as odour, aroma and flavour substance compositions comprising trans-peUitorin, as well as to a process for the preparation of trans-peUitorin.|
|Full Text||PREPARATIONS USED IN NUTRITION OR IN ORAL HYGIENE OR CONSUMED FOR PLEASURE COMPRISING TRANS-PELLITORIN
The invention relates to preparations and semi-finished products as well as odour, aroma and flavour substance compositions comprising tran-pellitorin, as well as to a process for the preparation of tran-pellitorin.
Saliva-inducing substances are employed, for example, in order to combat clinical dry mouth, to stimulate the appetite or also to improve oral hygiene, in that harmful substances or germs are rinsed from the oral cavity owing to the increased flow of saliva. Edible acids, for example citric, tartaric or malic acid, are usually employed for this purpose in food preparations. Specific substances which stimulate the salivary glands, such as, for example, pilocarpine extracted from the jaborandi tree, are employed in clinical dry mouth (Acta Med. Croatica 2000, 54, 65-67). However, such highly potent cholinergic parasympathomimetics generally have serious side-effects and some are highly toxic.
Of the long-chain fatty acid alkyl amides, 2E,6Z,8E-decatrienoic acid-N-isobutylamide (spilanthol) has been described as strongly saliva-inducing and tingling. However, spilanthol is at the same time above all fiery and highly
anaesthetising as well as astringent (Lebensm.-Wiss. u. -Technol. 1992, 25, 417-421). While other, longer-chain polyenoic acid-N-isobutylamides or polyyne acid-N-isobutylamides appear to be more strongly saliva-inducing, they additionally give a bitter flavour perception (c.f. above citation).
The object of the present invention was to develop a substance having a saliva-inducing and/or a tingling effect as well as having an otherwise largely neutral aroma profile, which can be incorporated as an aroma substance into preparations, in particular preparations used in nutrition or in oral hygiene or consumed for pleasure
The invention therefore relates to the use of 2E,4E-decadienoic acid isobutylamide (trans-pellitorin) as an aroma substance, preferably as an aroma substance having a saliva-inducing and/or tingling effect, in particular preferably as an aroma substance having a saliva-inducing and/or tingling effect in preparations used in nutrition or in oral hygiene or consumed for pleasure.
The present invention also provides preparations, semi-finished products and odour, aroma and flavour substance compositions, comprising 2E,4E-decadienoic acid-N-isobutylamide, preferably comprising synthetic 2E,4E-decadienoic acid-N-isobutylamide.
Organoleptic investigation of the trans-pellitorin according to the invention has shown that it provides a relatively persistent pleasant saliva-inducing and weakly tingling sensory perception. Surprisingly, only a saliva-stimulating effect is observable if the concentration in the final product, for example in a finished preparation, is below 20 ppm, in particular below 10 ppm. In this case no additional sensory perceptions are detectable, so that the flavour profile is very neutral. The largely neutral flavour profile constitutes a substantial advantage in terms of incorporation into preparations, since the trans-pellitorin brings about no change in or corruption of the flavour profile of the preparation.
This is in particular surprising because a marked burning effect on the tongue during tasting of trans-pellitorin in the pure state is described in J. Am. Chem. Soc. 1953, Volume 75, 2584-2586, in addition to an elevated flow of saliva. Its organoleptic perception was also described as predominantly anaesthetising (J. Agric. Food Chem., 1981, Volume 29, pages 115 et seq., or Fitoterapia, 2001, Volume 72, pages 197 et seq.).
The natural occurrence of pure 2E,4E-decadienoic acid-N-isobutylamide has been widely described in the literature; for example, it occurs in pepper (review by G.M. Strunz, Stud. Nat. Prod. Chem. 2000, Volume 24 (Bioactive Natural Products (Part E)), 683-738).
Natural products such as, for example, natural extracts, which comprise trans-pellitorin have additional aroma effects and thus do not have a neutral flavour profile. This is a frequently undesirable characteristic of natural products when incorporated into preparations. For this reason the use of synthesised, that is to say synthetic, trans-pellitorin is preferred in the present invention.
In a particularly preferred embodiment of the invention 2E,4E-decadienoic acid-N-isobutylamide is used in combination with other saliva-inducing, tingling, fiery and/or hot-tasting substances or plant extracts. In this way it is possible to achieve a particularly well-rounded organoleptic profile in a targeted manner.
Other saliva-inducing, tingling, fiery and/or hot-tasting substances may, for example, be edible acids (for example citric acid, malic acid, tartaric acid), capsaicin, dihydrocapsaicin, gingerol, paradol, shogaol, piperin, carboxylic acid-N-vanillylamides, in particular nonanoic acid-N-vanillylamide, 2-alkenoic acid amides, in particular 2-nonenoic acid-N-isobutylamide, spilanthol, 2-nonenoic acid-N-4-hydroxy-3-methoxyphenylamide, alkylethers of 4-hydroxy-3-methoxybenzyl alcohol, in particular 4-hydroxy-3-methoxybenzyl-n-butylether, alkylethers of 4-acyloxy-3-methoxybenzyl alcohol, in particular 4-acetyloxy-3-methoxybenzyl-n-butylether and 4-acetyloxy-3-methoxybenzyl-n-hexylether, alkylethers of 3-hydroxy-4-methoxybenzyl alcohol, alkylethers of 3,4-dimethoxybenzyl alcohol, alkylethers of 3-ethoxy-4-hydroxybenzyl alcohol, alkylethers of 3,4-methylenedi-oxybenzyl alcohol, (4-hydroxy-3-methoxyphenyl) acetic acid amides, in particular (4-hydroxy-3-methoxyphenyl) acetic acid-N-n-octylamide, ferulic acid phenethylamides, nicotinaldehyde, methylnicotinate, propylnicotinate, 2-butoxyethylnicotinate, benzylnicotinate, 1-acetoxychavicol, polygodial, isodrimeninol or pilocarpine.
The trans-pellitorin may advantageously be used with at least one additional N-iso-butylamide selected from the group comprising decanoic acid, 2E-decenoic acid, 2E,4Z-decadienoic acid, 2Z,4E-decadienoic acid, 2Z,4Z-decadienoic acid,
2E,4Z,7Z-decatrienoic acid, 3Z,5E-decadienoic acid or 3Z,5E,7Z-decatrienoic acid. A mixture of at least 80 wt. % 2E,4E-decadienoic acid-N-isobutylamide and at most 20 wt. % 2E,4Z-decadienoic acid-N-isobutylamide is preferred.
Saliva-inducing, tingling, fiery and/or hot-tasting plant extracts may be any of those plant extracts suitable for nutrition or oral hygiene which bring about a saliva-inducing, tingling, fiery and/or hot organoleptic perception. For example, pepper extract (Piper ssp., in particular Piper nigrum), water pepper extract (Polygonum ssp., in particular Polygonum hydropiper), extracts of Allium ssp. (in particular onion and garlic extracts), extracts of radish (Raphanus ssp.), horseradish extracts (Cochlearia armoracia), extracts of black mustard (Brassica nigra), wild or yellow mustard (Sinapis ssp., in particular Sinapis arvensis and Sinapis alba), pellitory root extracts (Anacyclus ssp., in particular Anacyclus pyrethrum L.), purple coneflower extracts (Echinaceae ssp.), extracts of Szechuan pepper (Zanthoxylum ssp., in particular Zanthoxylum piperitum), spilanthes extract (Spilanthes ssp., in particular Spilanthes acmella), chilli extract (Capsicum ssp., in particular Capsicum frutescens), paradise-seed extract (Aframomum ssp., in particular Aframomum melegueta [Rose] K. Schum.), ginger extract (Zingiber ssp., in particular Zingiber officinale), galangal extract (Kaempferia galanga or Alpinia galanga) and jaborandi extract (Pilocarpus species, in particular Pilocarpus jaborandi) are preferred as plant extracts.
The plant extracts according to the invention can be obtained from the corresponding fresh or dried plants or plant parts, in particular, however, from white, green or black peppercorns, water pepper seeds, onions and garlic, radish roots, horseradish, mustard seeds, purple coneflower roots, pellitory roots, plant parts from Zanthoxylum varieties, plant parts from spilanthes varieties, chilli pods, paradise seeds or ginger root or galangal root, as well as jaborandi. The dried plant parts, preferably previously comminuted, are conventionally extracted with a solvent suitable for foods and products consumed for pleasure, preferably ethanol, water, hexane or heptane or ethanol/water mixtures, at from 0°C up to the boiling point of the respective solvent or solvent mixture, and then filtered, and the filtrate is wholly
or partially concentrated, preferably by distillation, freeze-drying or spray-drying. The raw extract thus obtained can then be worked up further, for example treated with steam, generally at pressures of from 0.01 mbar to standard pressure, and/or dissolved in a solvent suitable for foods and products consumed for pleasure.
A solvent suitable for foods and products consumed for pleasure may, for example, be water, ethanol, methanol, propylene glycol, glycerol, acetone, dichloromethane, ethyl acetate, diethylether, hexane, heptane, triacetin, vegetable oils or fats, as well as supercritical carbon dioxide or mixtures of the aforementioned solvents.
The trans-pellitorin synthesis methods hitherto described in the literature are of a multi-stage type and give moderate to poor yields (J. Am. Chem. Soc. 1953, Volume 75, 2584-2586) or use toxic reagents such as, for example, the toxic selenium dioxide (Bull. Chem. Soc. Jpn., 1984, Volume 57, pages 3013 et seq.).
The invention therefore also relates to a process for the preparation of 2E,4E-decadienoic acid-N-isobutylamide, characterised in that
a) a 2E,4E- or 2E,4Z-decadienoic acid ester or a mixture of these esters is reacted with isobutylamine in the presence of a catalyst, and
b) the product formed in step a), optionally following purification steps, is isomerised to 2E,4E-decadienoic acid-N-isobutylamide;
i) a 2E,4Z-decadienoic acid ester or a mixture of 2E,4E- and 2E,4Z-
decadienoic acid ester is isomerised to 2E,4E-decadienoic acid ester, and
ii) the product formed in step i), optionally following purification steps, is reacted with isobutylamine in the presence of a catalyst.
Step i) may naturally be omitted and a 2E,4E-decadienoic acid ester be fed directly into the reaction with isobutylamine.
A process is advantageous which is characterised in that the reaction with isobutylamine takes place in the presence of a catalyst, preferably an enzyme, in particular an enzyme having lipase activity, in which the enzyme may be present as free protein or in association with a carrier,
the resulting reaction mixture optionally undergoes saponification with unreacted 2,4-decadienoic acid ester, preferably with an enzyme in an aqueous medium or a base diluted with water, in particular preferably an aqueous solution of inorganic basic salts,
the 2,4-decadienoic acid formed is separated, preferably in extractive manner,
the purified or unpurified raw product is isomerised to 2E,4E-decadienoic acid-N-isobutylamide, and
the mixture is then purified by physico-chemical methods, preferably by crystallisation, chromatography, distillation or co-distillation.
The process can be explained with reference to the following graphic formula:
It has surprisingly been ascertained that the process according to the invention gives very simple access to high yields of the desired 2E,4E-decadienoic acid-N-isobutylamide which can be readily purified. Furthermore, in this way when natural reagents within the meaning of the regulations governing aroma substances are employed, natural trans-pellitorin can be obtained.
The 2E,4E- or 2E,4Z-decadienoic acid esters are advantageously esters of the 2E,4E- or 2E,4Z-decadienoic acid with aliphatic monohydric alcohols having 1 to 20carbon atoms, in particular, however, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1-octanol, 2-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 1-nonadecanol, 1-eicosanol
or with polyhydric alcohols having 2 to 18 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, glycerol, pentaerythritol, sugar alcohols such as erythritol, sorbitol, glucitol, mannitol, monosaccharides such as tetroses, for example erythrose or threose, pentoses, for example arabinose, ribose, lyxose, xylose, hexoses such as allose, altrose, galactose, mannose, gulose, idose, glucose, talose, fructose, oligosaccharides such as maltose, raffmose, sucrose, maltooligosaccharides or lactose, wherein the further OH groups of the polyhydric alcohols can be esterified with aliphatic saturated or unsaturated carboxylic acids, as well as mixtures thereof or of saturated or unsaturated hydroxycarboxylic acids having 4 to 20 carbon atoms, which can for their part be esterified with the aforementioned alcohols.
Advantageous aliphatic saturated or unsaturated carboxylic acids within the meaning of the invention are saturated or mono- or polyunsaturated linear carboxylic acids having 2 to 26 carbon atoms, in particular, however, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, 2E- nonenoic acid, decanoic acid, 2E-decenoic acid, the various isomers of decadienoic or decatrienoic acid, for example 2E,4E-decadienoic acid, 2E,4Z-decadienoic acid, 2E,4Z,7Z-decatrienoic acid, 3Z,5E-decadienoic acid, 3Z,5E,7Z-decatrienoic acid, deca-2,8-dien-4,6-diynoic acid, deca-2-en-4,6,8-triynoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, 9E- or 9Z-hexadecenoic acid, heptadecanoic acid, octadecanoic acid, 9E- or 9Z- or HE- or 1 lZ-octadecenoic acid, the various geometric isomers of 9,12-octadecadienoic acid, of 6,9,12-octadecatrienoic acid, of 9,12,15-octadecatrienoic acid, of 6,9,12,15-octadecatetraenoic acid, nonadecanoic
acid, eicosanoic acid, the various geometric isomers of eicosaenoic acid, of 11,14-eicosadienoic acid, of 8,11,14-eicosatrienoic acid, of 5,8,11,14-eicosatetraenoic acid, of 5,8,11,14,17-eicosapentaenoic acid, of 10,13,16-docosatrienoic acid, of 7,10,13,16-docosatetraenoic acid, of 4,7,10,13,16-docosapentaenoic acid and of 4,7,10,13,16,19-docosahexaenoic acid.
The 2,4-decadienoic acid esters within the meaning of the invention can be present preferably in the form of natural or concentrated processed triglycerides, for example from stillingia oil or as methyl or ethyl esters. A fraction obtained by enzymatic transesterification of stillingia oil in ethanol followed by distillation, which is characterised in that it comprises at least 80 wt. % ethyl-2E,4Z-decadienoate, is particularly preferred.
Isomerisation within the meaning of the invention means that the other possible geometric isomers of the 2,4-decadienoic acid radical (2E,4Z-, 2Z,4Z- or 2Z,4E-) not corresponding to trans-pellitorin are converted to the 2E,4E- isomer by methods which are known per se. The 2E,4Z- isomer is preferably converted to the 2E,4E-isomer by treatment with iodine or by irradiation with UV-light (wavelength between 250 and 320 nm). The isomerisation can be carried out on the 2,4-decadienoic acid-N-isobutylarnides or the 2,4-decadienoic acid esters.
The invention also provides the preparations used in nutrition or consumed for pleasure comprising 2E,4E-decadienoic acid-N-isobutylamide in an active amount and optionally other conventional base materials, aids and additives for foods and products consumed for pleasure. These preparations generally comprise from 0.000001 wt. % (0.01 ppm) to 0.05 wt. % (500 ppm), preferably 0.00001 wt. % (0.1 ppm) to 0.005 wt. % (50 ppm), particularly preferably 0.00001 wt. % (0.1 ppm) to 0.0015 wt. % (15 ppm), of 2E,4E-decadienoic acid-N-isobutylamide, with reference to the total weight of the preparation. Further conventional base materials, aids and additives for foods or products consumed for pleasure may be comprised in amounts of from 0.000001 to 99.999999 wt. %, preferably 10 to 80 wt. %, with reference to the total weight of the preparation. The preparations may furthermore exhibit water
in an amount of up to 99.999999 wt. %, preferably 5 to 80 wt. %, with reference to the total weight of the preparation.
The preparations used in nutrition or consumed for pleasure within the meaning of the invention are, for example, bakery products (for example bread, dry biscuits, cake, other baked goods), confectionery (for example chocolate, fruit gum, hard and soft toffee, chewing gum), alcoholic or non-alcoholic beverages (for example coffee, tea, wine, wine-containing beverages, beer, beer-containing beverages, liqueurs, spirits, brandies, fruit-containing carbonated beverages, isotonic beverages, refreshment beverages, nectars, fruit and vegetable juices, fruit or vegetable juice preparations), instant beverages, meat products (for example ham, fresh sausage or uncooked sausage preparations), eggs or egg products (dried egg, egg white, egg yolk), cereal products (for example breakfast cereals, muesli bars), milk products (for example milk beverages, ice milk, yoghurt, kefir, non-matured cheese, soft cheese, hard cheese, dried milk powder, whey, butter, buttermilk), fruit preparations (for example jams, fruit ices, fruit sauces), vegetable preparations (for example ketchup, sauces, dried vegetables), snack articles (for example baked or fried potato crisps or potato dough products, extrudates based on maize or peanuts), products based on fat and oil or emulsions thereof (for example mayonnaise, remoulade sauce, dressings), prepared dishes and soups, spices, condiment mixtures as well as in particular condiments for sprinkling (seasonings), which are used in the snacks sector. The preparations within the meaning of the invention can also serve as semifinished products for the preparation of further preparations used in nutrition or consumed for pleasure. The preparations within the meaning of the invention can also be present as nutritional supplements in the form of capsules, tablets (non-coated as well as coated tablets, for example coatings resistant to gastric juices), dragees, granules, pellets, solid mixtures, dispersions in liquid phases, as emulsions, as powders, as solutions, as pastes or as other preparations able to be swallowed or chewed.
Oral hygiene preparations, in particular dental care products such as toothpastes, tooth gels, tooth powders, mouthwashes, chewing gums and other oral care products,
which comprise 2E,4E-decadienoic acid-N-isobutylamide in an active amount and optionally other conventional base materials, aids and additives for such preparations, are a particularly preferred embodiment of the invention. They generally comprise from 0.000001 wt. % (0.01 ppm) to 0.05 wt. % (500 ppm), preferably 0.00001 wt. % (0.1 ppm) to 0.005 wt. % (50 ppm), particularly preferably 0.00001 wt. % (0.1 ppm) to 0.0015 wt. % (15 ppm), with reference to the total weight of the preparation, of 2E,4E-decadienoic acid-N-isobutylamide. Further conventional base materials, aids and additives for the oral hygiene preparations can be comprised in amounts of from 0.000001 to 99.999999 wt. %, preferably 10 to 80 wt. %, with reference to the total weight of the preparation. The preparations can furthermore comprise water in an amount of up to 99.999999 wt. %, preferably 5 to 80 wt. %, with reference to the total weight of the preparation.
Dental care products comprising 2E,4E-decadienoic acid-N-isobutylamide generally consist of an abrasive system (scouring or polishing agent) such as, for example, silicic acids, calcium carbonates, calcium phosphates, aluminium oxides and/or hydroxylapatites, of surface active agents such as, for example, sodium lauryl sulfate, sodium lauryl sarcosinate and/or cocamidopropylbetaine, of humectants such as, for example, glycerol and/or sorbite, of thickeners such as, for example, carboxymethyl cellulose, polyethylene glycols, carragheens and/or Laponites®, of sweeteners such as saccharin, of stabilisers and of active ingredients such as, for example, sodium fluoride, sodium monofluorophosphate, tin(II) fluoride, quaternary ammonium fluorides, zinc citrate, zinc sulfate, tin pyrophosphate, tin(II) chloride, mixtures of various pyrophosphates, triclosan, cetylpyridinium chloride, aluminium lactate, potassium citrate, potassium nitrate, potassium chloride, strontium chloride, hydrogen peroxide, aromas and/or sodium bicarbonate.
Chewing gums comprising 2E,4E-decadienoic acid-N-isobutylamide generally consist of a chewing gum base, that is to say a chewing mass which becomes plastic when chewed, sugars of various types, sugar substitutes, sweeteners, sugar alcohols, humectants, thickeners, emulsifiers, aromas and stabilisers.
Preparations according to the invention can also preferably be employed in condiments for sprinkling, so-called seasonings, in order to avoid the dry mouth feel which occurs when eating maize-flour, potato-flour or rice-flour crisps and snacks, and to improve the overall organoleptic perception.
Suitable condiments for sprinkling include, for example, synthetic, natural or nature-identical aroma substances as well as carrier substances such as, for example, maltodextrin, salts such as, for example, common salt, spices such as, for example, paprika and pepper, sweeteners such as, for example, saccharin, and flavour enhancers such as, for example, monosodium glutamate and/or inosine monophosphate.
The preparations according to the invention which comprise 2E,4E-decadienoic acid-N-isobutylamide can be prepared such that 2E,4E-decadienoic acid-N-isobutylamide is incorporated without a solvent, as a solution or in the form of a mixture with a solid or liquid carrier substance, into the preparations used in nutrition or in oral hygiene or consumed for pleasure. Advantageously, the preparations according to the invention which are present as solutions, comprising 2E,4E-decadienoic acid-N-isobutylamide can also be converted into a solid preparation by spray-drying.
In order to prepare the preparations, it is also possible in a further preferred embodiment first to incorporate the 2E,4E-decadienoic acid-N-isobutylamide and optionally other constituents of the preparation according to the invention into emulsions, into liposomes, for example beginning with phosphatidylcholine, into microspheres, into nanospheres or also into capsules made of a matrix suitable for foods and products consumed for pleasure, for example of starch, starch derivatives, other polysaccharides, natural fats, natural waxes, or of proteins, for example gelatine. A further embodiment consists in first complexing 2E,4E-decadienoic acid-N-isobutylamide with suitable complexing agents, for example with cyclodextrins or cyclodextrin derivatives, preferably -cyclodextrin, and employing it in this form.
As other constituents of the preparations used in nutrition or consumed for pleasure according to the invention, further conventional base materials, aids and additives for foods or products consumed for pleasure can be used, for example water, mixtures of fresh or processed plant- or animal-based base or raw materials (for example raw, fried, dried, fermented, smoked and/or boiled meat, egg, bone, cartilage, fish, crustaceans and shell fish, vegetables, fruits, herbs, nuts, vegetable or fruit juices or pastes, or mixtures thereof), digestible or also non-digestible carbohydrates (for example saccharose, maltose, fructose, glucose, dextrins, amylose, amylopectin, inulin, xylans, cellulose), sugar alcohols (for example sorbite, mannitol, xylitol), natural or hydrogenated fats (for example tallow, lard, palm oil, coconut oil, hydrogenated vegetable oil), fatty oils (for example sunflower oil, groundnut oil, maize oil, thistle oil, olive oil, walnut oil, fish oil, soybean oil, sesame seed oil), fatty acids or salts thereof (for example potassium stearate, potassium palmitate), proteinogenic or non-proteinogenic amino acids and related compounds (for example taurine, creatine, creatinine), peptides, native or processed proteins (for example gelatine), enzymes (for example peptidases, glucosidases, lipases), nucleic acids, nucleotides (inositol phosphate), flavour-modulating substances (for example monosodium glutamate, 2-phenoxypropionic acid), emulsifiers (for example lecithins, diacyl glycerols), stabilisers (for example carragheen, alginate, carob flour, guar gum), preservatives (for example benzoic acid, sorbic acid), antioxidants (for example tocopherol, ascorbic acid), chelating agents (for example citric acid), organic or inorganic acidifying agents (for example malic acid, ethanoic acid, citric acid, tartaric acid, phosphoric acid), bitter substances (for example quinine, caffeine, limonin), sweeteners (for example saccharin, cyclamate, aspartam, neotame, neohesperidin dihydrochalcone), mineral salts (for example sodium chloride, potassium chloride, magnesium chloride, sodium phosphates), substances for preventing enzymatic browning (for example sulfite, ascorbic acid), essential oils, plant extracts, natural or synthetic colourings or coloured pigments (for example carotinoids, flavonoids, anthocyans, chlorophyll and derivatives thereof), spices as well as odour substances, synthetic, natural or nature-identical aroma and flavour substances.
The preparations according to the invention can preferably also comprise an aroma composition in order to round out or refine the flavour and/or odour of the preparation. Suitable aroma compositions comprise, for example, synthetic, natural or nature-identical aroma substances as well as odour substances, however in particular also other saliva-inducing, tingling, fiery or hot-tasting substances or plant extracts.
The invention also provides the use of the preparations according to the invention as semi-finished products, for aromatising preparations prepared as finished products therefrom.
The invention also provides odour, aroma and flavour substance compositions comprising 2E,4E-decadienoic acid-N-isobutylamide. These compositions generally comprise from 0.001 wt. % to 5 wt. %, preferably 0.01 wt. % to 2 wt. %, particularly preferably 0.05 wt. % to 1 wt. % of 2E,4E-decadienoic acid-N-isobutylamide, with reference to the total weight of the composition.
The invention can be illustrated by reference to the Examples which follow.
2E,4E-decadienoic acid-N-isobutylamide (trans-pellitorin) by enzymatic reaction
with ethyl-2E,4Z-decadienoate followed by isomerisation
Reaction with isobutylamine:
10 g ethyl-2E,4Z-decadienoate, 4.7 g Chirazym L-2 (c.-f., C2, lyo., Catalogue No. 1859242, Roche Diagnostics, Basle, Switzerland) and 4 g isobutylamine were stirred for 4 days at 55°C. 100 ml diethylether were added to the batch which was then filtered; the filtrate was evaporated under vacuum (raw yield 15.2 g). The product was stirred in a 10% KOH/methanol (1:1-mixture) for 45 min at room temperature, and extracted with ether, the etheric phase was dried over sodium sulfate, and filtered, and the filtrate was evaporated. The raw intermediate product was chromatrographed on silica gel 60 (eluent hexane/ethyl acetate 10:1 (v/v)). Yield 9.1 g(GC: 99.4%).
1H-NMR (CDC13; 200 MHz): = 7.56 (1H, ddd, 11.5 Hz, 14.9 Hz, 1.0 Hz), 6.08 (1H, dddd 11.5 Hz, 10.8 Hz, 1.4 Hz, 0.6 Hz), 5.82 (1H, d, 14.9 Hz), 5.79 (1H, dtd 10.8 Hz, 7.8 Hz, 0.9 Hz), 5.50 (1H, bs), 3.18 (2H, dd, 6.8 Hz, 6.1 Hz), 2.36-2.22 (2H, m), 1.81 (1H, m, 6.7 Hz), 1.50 - 1.22 (6H,m), 0.93 (6H, d, 6.7 Hz), 0.88 (3H, m) ppm.
13C-NMR (CDCI3; 50 MHz): = 166.34 (C), 140.07 (CH), 135.76 (CH), 126.28 (CH), 123.78 (CH), 46.96 (CH2), 31.41 (CH2), 29.14 (CH2), 28.63 (CH), 28.15 (CH2), 22.52 (CH2), 20.15 (CH3), 14.02 (CH3) ppm.
277 mg of the purified 2E,4Z-decadienoic acid-N-isobutylamide were stirred with
29 mg iodine in 10 ml toluene for one hour at room temperature. The mixture was
chromatographed on silica gel 60 with hexane/ethyl acetate 5:1 (v/v) as eluents.
Yield: 61 mg (purity > 95 %, NMR).
1H-NMR (CDCI3; 200 MHz): = 7.19 (1H, dd, 14.9 Hz, 9.7 Hz), 6.13 (1H, dd 15.1
Hz, 9.6 Hz), 6.07 (1H, dd, 15.1 Hz, 6.4 Hz), 5.75 (1H, d, 14.9 Hz), 5.50 (1H, bs),
3.17 (2H, dd, 6.9 Hz, 6.1 Hz), 2.14 (2H, dd, 7Hz, 6.4 Hz), 1.80 (1H, m, 6.7 Hz), 1.42 (2H, m, 7.1 Hz), 1.37 - 1.22 (4H, m), 0.93 (6H, d, 6.7 Hz), 0.89 (3H, m) ppm.
Isomerisation Variant 1:
60 mg iodine were added to 3.1 g of the raw intermediate product from the reaction with isobutylamine in 20 ml toluene, and the mixture was stirred for 26 h at room temperature. 30 ml n-hexane were added, and the mixture was stored at approximately 18°C for 1 h. The crystalline product was filtered off (GC: 86% 2E,4E- isomer, 10.5 % 2E,4Z- isomer). A 95%-pure product could be obtained by recrystallisation out of approximately 30 ml n-hexane (yield 1.6 g).
Isomerisation Variant 2:
3.1 g of the raw intermediate product from the reaction with isobutylamine were dissolved in 100 ml ethanol and, with cooling, were irradiated for 8 hours with a mercury vapour high-pressure lamp having a quartz glass tube. The solution was evaporated, and the oily residue (GC: 22 % 2E,4E- isomer, 62% 2E,4Z- isomer) was purified chromatographically (yield approximately 400 mg).
Example 2: Tasting
The trans-pellitorin was dissolved in ethanol and the ethanolic solution was then diluted with an 11 wt. % sugar solution (final concentration: c). For tasting, approximately 5 ml of the sugar solution was in each case swallowed. A group of 6 to 8 testers tasted the solution:
c = 10 ppm: saliva-inducing, slightly tingling, and not fiery
c = 20 ppm: saliva-inducing, slightly anaesthetising, slightly fatty, weakly
fruity, tingling, persistent, and not fiery
Example 3: Use in a toothpaste
The ingredients of Parts A and B are respectively premixed and then stirred together thoroughly under vacuum at 25 - 30°C for 30 min. Part C is premixed and added to A and B; D is added to this and the mixture is stirred thoroughly under vacuum at 25 - 30°C for 30 min. After relaxing, the toothpaste is finished and can be filled.
Example 4: Use in a sugar-free chewing gum
Parts A to D are mixed and kneaded intensively. The raw mass can be processed into ready-to-use chewing gum, for example in the shape of thin strips.
Example 5: Use in a mouthwash
The ingredients of Parts A and B are respectively individually mixed. Part B is introduced slowly into Part A until the mixture is homogenous.
Example 6: Use in a condiment for sprinkling on deep-fried snack food
100 g of unseasoned tortilla chips are sprinkled with a mixture of 7 g cheese dry aroma for snacks and 0.07 g 2E,4E-decadienoic acid-N-isobutylamide.
Example 7: Use in a cream filling for biscuits
100 g standard cream filling are mixed intensively with 0.4 g strawberry aroma and 0.1 g 2E,4E-decadienoic acid-N-isobutylamide.
Preparations used in nutrition or in oral hygiene or consumed for pleasure comprising trans-pellitorin in an amount below 20 ppm with reference to the finished preparation and conventional base materials, aids and additives for foods or products for pleasure in amounts from 10 to 80 wt.-% with reference to the finished preparation.
2. Preparations as claimed in Claim 1, wherein these comprise trans-pellitorin in an amount below 10 ppm with reference to the finished preparation.
3. Preparations as claimed in Claim 1, wherein these comprise at least one optionally saliva-inducing, tingling, fiery or hot-tasting substance and plant extract.
4. Preparations as claimed in any one of Claims 1 to 3, wherein the trans-pellitorin is synthetic.
|Indian Patent Application Number||1759/DELNP/2005|
|PG Journal Number||02/2011|
|Date of Filing||29-Apr-2005|
|Name of Patentee||SYMRISE GMBH & CO.KG|
|Applicant Address||MUHLENFELDSTR.1, 37603 HOLZMINDEN, GERMANY.|
|PCT International Classification Number||C07C 231/00|
|PCT International Application Number||PCT/EP2003/012686|
|PCT International Filing date||2003-11-13|