DK142041B - Means to provide food chicken flavor and aroma. - Google Patents

Description

(11) PRESENTATION 11 + 2041 (S)

Vp.bl / DENMARK lrt C | a A 23 L 1/231 «(21) Note no. 813/71 (22) Filed on 2J. February 1971 (23) Live day 23 · Feb. 1971 (44) The application presented and the writ of publication published on 1 8th August. 1 980 THE DIRECTORATE OF _. . _. .

PATENT AND TRADEMARKET SYSTEM (30), 0 "1® * k®0®1 **" 8 «η

Feb 24 1970, 60396, LU

(7i) UNILEVER N.V., Museum Park 1, Rotterdam, NL.

(72) Inventor: Willem Johan Begemann, 20 Van Tedingerbrouckstraat, The Hague, NL: Pieter Daniel Harkes, 50 Willem Frederikstraat, Vlaardingen, NL.

(74) Plenipotentiary in the proceedings:

The engineering company Budde, Schou & Co.

(54) Means for providing food chicken meat Butuag and flavor.

The present invention relates to a means for giving foods an aroma or flavor reminiscent of chicken meat or to enhance such flavor.

It is known to impart chicken flavor and flavor to foods using poultry meat, but although the quality of such products is intolerable, the aroma or flavor is often considered too flat or too weak. To counter this objection, products have been marketed under the term "chicken meat flavor", the composition of which has mostly not been revealed, but among these products no one has solved the above-mentioned problem. According to Danish Patent No. 112,420, foods of improved taste, especially chicken meat flavor or flavor, are obtained by an agent comprising aliphatic aldehydes having 11-17 carbon atoms and 2-4 double bonds and / or a precursor for such compounds. but this solution has not been entirely satisfactory either.

It has now been found that the aldehyde 4cis decenal has the remarkable property of increasing a chicken meat flavor or aroma present in foods, especially when added with certain of the ages referred to in Danish Patent No. 112,420, and it applies, whether this aldehyde is used as such or is formed in situ.

Accordingly, the present invention relates to a means for providing chicken meat flavor and flavor and containing 2,4,7-tridecatrienal and / or 2,6-dodecadienal and / or a precursor thereof, which agent of the invention is characterized by that it additionally contains 4cis decenal and / or a precursor therefor.

By a "precursor" for a flavoring and flavoring agent is meant a compound which, after incorporation into the food, is converted into the flavoring and flavor enhancing compound itself under the conditions encountered during the preparation, storage or preparation of the food for consumption. A precursor is used to overcome problems that will occur using the desired compound itself.

From Swedish Patent Specification No. 302,075, it is known in foods to incorporate cis and / or trans-hepten-4-al to obtain a cream or butter-like aroma, but it has not previously been recognized that incorporation of 4cis decenal would lead to increase or communication of chicken meat flavor and aroma.

Precursors for 4cis decenal are e.g. functional derivatives of the aldehyde such as the acetals, especially diethyl acetal, the acylates, especially the diacetate, enol ethers, enol esters and bisulfite compounds of 4cis decenal, and thiazolidine derivatives are derived from the reaction of the aldehyde with organic compounds containing NH group and an SH group at adjacent carbon atoms, especially those formed by reaction of the aldehyde with cysteine, (3-lactoglobulin and glutathione. In reaction with cysteine, for example, the new compound 2- (3cis) is formed -nonenyl} - thiazolidine-4-carboxylic acid which can be converted to its salts or esters by known methods.

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According to the invention, as the precursor of 4cis .-- decenal, preferably 2- (3cis-nonenyl) -thiazolidine-4-carboxylic acid or 1,1-diethoxy-4cis-decene is used, since these two compounds are particularly easily hydrolyzed to 4cis-decenal.

The foods whose flavor and aroma can be enhanced through the composition of the invention are, in particular, soups, preferably dry soups, ready-made meat dishes, chicken meats and broth cubes, as well as pies, ragout, snacks, croquettes, meatballs, salads and sauces with chicken meat, and vegetable protein products, which it is desired to give chicken flavor and where desired chicken meat provides part of the taste and aroma.

The compositions of the invention may also be incorporated into a flavor enhancement blend which may be used for the preparation or preparation of the food, such flavor enhancement comprising the flavoring and flavor enhancers incorporated in an edible carrier or edible diluent. Such carriers or diluents may be a constituent or mixture of constituents of the food which is then made to contain a quantity of 4cis decenal suitable for the particular food or a precursor therefor.

The composition of the invention may also be in the form of a concentrated liquid or solid flavoring agent, e.g. a spreading powder used by the user to enhance the aroma or taste, either in the kitchen or at the table.

The amount of 4cis decenal to be found in the ready-to-eat food can range from 0.003 to 0.03 mg / kg and is preferably between 0.006 and 0.015 mg / kg, and precursors for 4c ± s - decenal can be used in such amount that the amount of aldehyde formed in the finished food is within said range.

The amounts of 2trans, 4cis, 7cis-tridecatrlenal and 2trans, 6cis-dodecadienal, calculated on the amount of 4cis-decenal, may vary between 1 and 6 parts by weight of the tridecatrienal and 0.1 and 0.5 parts by weight of the dodecadienal for each part of the decanal. , preferably between 2 and 5 and between 0.2 and 0.4 parts by weight, respectively. In special cases, larger or smaller quantities can also be used.

The amount of flavor or flavor in a concentrated flavoring and flavor enhancer, such as a powder, may also vary within wide limits, which also depends on other substances incorporated into the agent. An appropriate amount is e.g. 22.5 mg per day kg of powdered powder.

The problem of the durability of the aldehyde can be solved not only by using precursors, but also by bringing the aldehyde in a stabilized form such as by encapsulation or coating, e.g. with grease, gelatin or gum arabic. A very satisfactory form is the product obtained by appropriate dehydration of a solution of the agent of the invention in a concentrated solution of maltose / dextrin, preferably by freeze-drying or spray-drying. The stabilized forms thus obtained, especially those in maltose / dextrin, are very well suited for dosing the flavoring agent of the invention, and the amount of the agent therein is, of course, not bound to certain limits. An appropriate amount is e.g. 0.1-10 mg / g, but it is also possible to use larger or smaller amounts.

The stabilized forms described above may also be mixed with one of the ingredients to be used in the preparation of the food, or with a portion of such ingredients or with a mixture of several ingredients.

The composition of the invention can be used with other substances which serve the desired purpose. Thus, is it possible to use one or more of the compounds belonging to one or more of the following groups? (a) Amino acids that can be obtained in any conventional manner from vegetable or animal proteins such as e.g. gluten, casein, zein and soy protein.

(b) Peptides of similar origin as well as such peptides as alanylalanine, alanyl phenylalanine, alanylasparagin, carnosine and anserin.

(c) Nucleotides such as adenosine, guanosine, inosine, xanthosine, uridine and cytidine S * monophosphates, as well as e.g. amides, deoxide derivatives and their salts.

(d) Monocarboxylic acids such as saturated or unsaturated fatty acids, e.g. those with 2-12 carbon atoms, lactic acid, glycolic acid and β-hydroxybutyric acid, as well as dicarboxylic acids such as e.g. succinic and glutaric acid.

(e). Pyrrolidone carboxylic acid and its precursors.

(f) Natural sweeteners such as mono- and disaccharides, as well as artificial sweeteners such as saccharin and cyclamates.

(G) 4-Hydroxy-5-methyl-2,2-dihydrofuran-3-one and 4-hydroxy-2,5 '-dimethyl-2,3-dihydrofuran -> - one.

(h) The products of the reaction of sulfur-containing amino acids or hydrogen sulfide with reducing sugars or ascorbic acid or the compounds mentioned in (g) or lower aliphatic aldehydes and ketones.

(i) Sulfur compounds such as hydrogen sulfide, thiols, sulfides and disulfides, e.g. dimethyl sulfide and diallylsulfide, as well as 2-acetyl-thiazole and 2-acetyl-2-thiazoline.

(j) Guanidines such as creatine and creatinine.

(k) Salts such as sodium chloride and mono- and disodium and ammonium phosphates.

(l) Organic phosphates such as phosphorus-containing amino acids.

(m) Nitrogen compounds not mentioned above, such as ammonia, amines, urea, indole and skatole.

(n) 4- and 5-Alkhnolides as well as the esters and salts of the corresponding hydroxy acids such as 5-decanolide, 5-dodecanolide, sodium 5-hydroxydecanoate and the glycerides of 5-hydroxy-alkanoic acids such as the reaction product of 5-alkanolides and glycerol .

(o) Aldehydes such as ethanal, propanal and 4-heptenal.

(p) Ketones such as methyl ketones with e.g. 5-15 carbon atoms and biacetyl.

(q) Esters of 5-oxoalkanoic acids such as the glycerol esters.

(r) Tricholomic and ibotenic acid and its salts.

(s) Flavoring and flavoring agents, e.g. o-aminoacetophenone, N-acetonylpyrrole, maltol, isomaltol, ethylmaltol, vanillin, ethyl-vanillin, cycloene (2-hydroxy-3-methyl-2-cyclopenten-1-one), ethone / T- (p-methoxyphenyl) -1 -penten-3-acid, coumarin and ethoxymethyicumarin.

(t) Alcohols such as ethanol and octanol.

(u) Dyes such as turmeric and caramel.

(v) Thickeners such as gelatin and starch.

(w) Emulsifiers such as the monoglycerides of diethyl tartaric acid.

The amount of the substances used above depends on the nature of the food and the other ingredients added, such as herbs and spices, as well as on the smell or taste desired.

The agent of the invention may be incorporated together with the above-mentioned flavorings in maltose / dextrin or another stabilized form or in one of the ingredients for the preparation of the food as mentioned above.

142041 6

The 4-egg component of the invention according to the invention can be prepared by. partial catalytic reduction of 4-decynal or by hydrolysis of diethyl acetal obtainable by conversion of jjcis-nonenyl-magnesium bromide with triethoxymethane. The compound 1,1-diethoxy-4cis-decene is a novel compound. The derivatives of the aldehyde can also be prepared by methods known in the literature.

The following examples are intended to further illustrate the invention.

Example 1.

Chicken fat in an amount of 298.6 g was melted and to this melt was added 1.25 g of peanut oil containing 5.4 mg of 2trans, 4cis, -7cis-trideeatrienal and 0.345 mg of 2trans, 6cis dodecadienal. To one half of this chicken fat was added 0.15 g of peanut oil, in which was dissolved 0.9 mg of 4cis-deeenal, while to the other half an equal amount of peanut oil was added without any additive. Of both portions of chicken fat, a dry mix of the following composition was prepared:

Chopped chicken fat 3.0

Chopped chicken meat 4.0

Salt 8.0

Monosodium glutamate 6.0

Dextrose 3.0 Onion powder 0.7

Enzymatic hydrolyzed yeast 0.5

Curcuma 0.12

Parsley 0.04

Sage 0.01

Noodles 32.0

From both mixtures, a soup was prepared by boiling 57 g with 800 ml of water for 7 min. Both soups were then compared by a triangle test by an expert panel of 23 people, 16 of whom made a correct taste assessment (significance p = 0.001). Of these 16 people, the 9 preferred the soup containing 4cis decenal (0.0225 mg / kg) (significance p = 0.05). Significance was determined according to the table in K. Bengtsson, Wallerstein Laboratories Comm. 16, 231 (1953).

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Example 2.

The compound 4cis-decenal was synthesized as follows: From the magnesium compound of 1-heptyne (kgp 99.5-100.5 ° C, n + = 1.4084, purity according to GLC 96%, prepared by Jenny and Meyer, Angew Chem.

71, 245-246 (19591 from 1-bromopentane and sodium acetylide in dimethylformamide 1, 3-nonyn-1-ol was prepared by reaction with ethylene oxide following Knight and Diamond, J. Org. Chem. 24, 400-403 (1959), which, after conversion to the tetrahydro-pyranyl ether, was purified by distillation. The nonyole, which after decomposition of the ether, was recovered by boiling with methanol and pr-boluenesulfonic acid by Van der Steen et al., Rec. Trav., Chim. 82, 1015-1025 ( 1963), had a purity (GLC) of 99%, and kgp 108-109 ° C / 16 mm Hg and n 2 = = 1.4559. By partial hydrogenation with 10% Lindlar catalyst and 4% quinoline was obtained containing 3 cis-nonen-1-ol with kgp 103-1Q4 ° C / 15 mm Hg, n + + = 1.4488 and purity (GLC) 95%. This compound was converted according to Hunsdiecker, Ber. 75, 460- 468 (1942) with FBr ^ to the 1-bromo-3cis nonene with kgp 78-81 ° C / 5 mm Hg and n ^ = 1.4707.

Of this 1-bromo-3cis non-15.6 g (0.076 mol) was dissolved in 50 ml of ether and converted in the usual manner with 1.82 g (0.076 mol), magnesium to the magnesium compound. The solution was cooled to + 5 ° C and 12.4 g (0.084 mole) of triethoxymethane was rapidly added and then the reaction mixture was heated to boiling for 6 hours, then 50 ml of water was added followed by such a 10% hydrochloric acid to pH -quora of 6.5-7.

The ether layer was separated and the aqueous layer was extracted with 50 ml of ether. After drying the ethereal solution with anhydrous

The solvent of MgSO4 was evaporated and the residue consisting of 1,1-diethoxy-4cis-decene was distilled. Bp. 57.5-67 ° C / 0.02 mm Hg, 70 n + = 1.4344, yield 60%.

The diethyl acetal was hydrolyzed to red oxalic acid in an aqueous acetone solution according to the method of Winter, Helv. Chem. Acta 46, 1792-1797 (19631. Yield was 82% 4cis decenal with kgp 51-52.5 ° C / -20 0.9 mm Hg, ηβ = 1.4429, purity (GLC) 94%. absorption band for the cis double bond was clearly present, whereas the bands for a trans double bond were not found. The usual 2,4-dinitrophenyl-hydrazone prepared from the aldehyde melted at 73.8-74.4 ° C. micro-elemental analysis corresponding to the assembly formula.

8 142041

Example 3 In 500 ml of a 50 µl solution of maltose / dextrin in water, 0.0675 g of 4eis decenal, 0.27 g of 2trans, 4cis, 7cis-tridecatrienal and 0.0173 g of 2trans, 6eis dodecadienal and were thoroughly mixed and the solution lyophilized. The powder obtained contained 0.27 mg of 4c in s-dec e-nal, 1.08 mg of 2trans, 4cis, 7cis-tridecatrienal and 0.069 mg of 2trans, 6cis-dodecadienal per ml. g.

Example 4

A solution of 180 mg of 4cis decenal in 1 ml of 100% 1s of ethanol was added to a solution of 134.2 mg of cysteine in 1 ml of distilled water, and after thorough mixing, the mixture was allowed to stand overnight at 0-4 ° C.

The resulting mass was triturated and stirred with 2 ml of 100% ethanol, then the precipitate was centrifuged and the supernatant was carefully removed by pipette. After drying the solid over calcium chloride, 132 mg (51 $ of theory) of 2- (3cis-nonenyl) -thiazolidine-4-carboxylic acid melting at 133-137 ° C were obtained. during decomposition. NMR (solvent deuterated pyridine, internal standard tetramethylsilane) showed signals at δ = 0.87 (distorted triplet), 1.03-1.62 (complex), 1.68-2.56 (complex), 2.99-3 , 59 (complex), 4.05-4.33 (double doublet), 4.69-4.96 (double triplet) and 5.44 ppm (complex).

By means of an ethereal diazomethane solution, the methyl ester was prepared, which showed in the infrared spectrum absorption peaks at 3320, 3020, 1705, 1658, 1442, 1345, 1230, 1205, 1182, 1030, 825, 795 and 725 about the the methyl ester had a molecular peak for m / e 271 and additional peaks for m / e 224 (20), 212 (23) and 149 (100), the brackets indicating the relative intensities relative to the intensity of the peak of m / e 149.

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Example 5 »

A chicken regout is composed of the following components:

Flour 54 g

Margarine 54 g Chicken Soup Meat (with bone) 90 g

Mushrooms 94 g

Salt 2.25 g

Pepper 0.0575 g

Protein hydrolyzate 0.0375 g

Maltose / dextrin powder of Example 3 0.075 g

Water 300 g

Of the chicken meat and water, a broth was cooked in a pressure cooker over 1 hour, after which the cooked meat was removed from the soup and boned, yielding ea. 56 g of meat. The soup was filtered and filled up to 300 ml. The margarine was melted and the flour and soup were alternately added in small portions with thorough stirring to prevent burning. After all the flour and soup had been added, the other ingredients were added and the whole was allowed to simmer for 5 minutes.

Similarly, a control ragout was prepared with non-aromatized maltose / dextrin powder and compared with the aromatized ragout. The latter had a fuller aroma and taste, which more closely resembled the aroma and taste of cooked chicken,

Example 6

A dough was prepared from the following ingredients: Weight portions

Pig liver. 25 Chicken meat 150

Flour 40 Cured fat (m.p. about 37 ° C) 25

Thyme 0.5

Nutmeg 0.5

Monosodium glutamate 0.5 Onion powder 0.5

Pepper 0.5

Salt 5

Maltose / dextrin powder according to Example 3 0.05

Water 250 10 142041

The pork liver was boiled with 150 parts by weight of water for 50 minutes, after which it was taken up and after draining was finely ground in a mincer.

The chicken, thyme and nutmeg are cooked for 45 minutes with 500 parts by weight of water, then the meat is taken up and after draining is also comminuted in a meat chopper.

The chopped liver and minced chicken were thoroughly mixed for 8 minutes in a mixer with 100 parts by weight of water and with the salt, the monosodium glutamate, the onion powder, the pepper and the fat. Then the flour was stirred with 150 parts by weight of water, the flavored maltose / dextrin powder was added and the whole was mixed with the meat mixture. The whole mixture was then heated to boiling until it was of appropriate thickness.

The pastry thus produced had a pleasant aroma and taste like chicken liver pastry.

Example J.

A powder soup was prepared by thoroughly mixing the following: Weight parts Chicken meat, lyophilized 9.75 Cured fat (m.p. about 57 ° C) 59

Sugar 17

Mix of dehydrated chicken meat - 0.25 soup and salt (1: 1)

Oxidized potato starch 7

Vermicelli 560

Salt 86

Pepper essence 0.52

Thyme Essence 0.02

Spices 0.28

Curcuma 0.55

Celery salt (1: 2) 2.25

Monosodium Glutamate 22 Onion Powder 4

Parsley, freeze-dried 0.8

Maltose / dextrin powder according to Example 5 0.55

From 55 S of this mixture, after stirring in 1 liter of water and boiling for 10 minutes, a soup was obtained which had a pleasant taste and aroma as chicken meat soup.

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Example 8.

A powdered powder was prepared in the usual manner from the following: · ..η · .. · Weight parts

Monosodium Glutamate 4

Salt 7

Pr otein hydrolyzate, powdered 4 '

Pepper 0.02

Laurel leaves, powdered 0.02

Cloves, powdered 0.02 Onion, powdered 1 Yeast extract 1.5

Maltose / dextrin powder according to Ex. 3. 2.44

By adding 100 mg of this powder to 1 liter of chicken meat a soup was obtained with a richer and more pronounced aroma and sinag ^

Example 9

To 598 g of melted chicken fat was added a solution of 4 mg of 2trans, 4eis, 7cis-tridecatrienal and 0.26 mg of 2trans, 6cis-dodecadienal in 2 g of peanut oil, and all mixed thoroughly.

Also 15 g of potato starch and 150 mg of 2- (3cis-nonenyl) -thiazolidine-4-carboxylic acid were thoroughly mixed.

A powder blend was then prepared with these two ingredients by admixing the following:

Flavored chicken fat 4

Flavored potato starch 0.0015 Chicken meat, minced 3.1

Salt 8.5

Pepper o, 032

Thyme 0.0025

Carnations 0.0l8

Celery salt (1: 2) 0.226 Onion powder 0.42

Sugar 1.7

Vermicelli 52.0 12 142041

By boiling 50 g of this powder soup with 1 liter of water for 7 minutes, a soup was obtained with an aroma and taste that was more reminiscent of cooked chicken meat.

Example 10.

A flavoring and flavoring product was prepared by mixing the following: Weight portions

Salt 0.5

Pepper 0.2

Monosodium Glutamate 1.5

Protein hydrolyzate 2.3

Maltose / dextrin powder according to Ex. 3 3.0

This product can be used in place of the flavored maltose / dextrin powder used in Examples 5-7 in the following amounts:

Ex. Amount 5 200 mg 6 150-250 parts by weight 7 100 parts by weight