JP2006519289A - Amino acid derivatives of dicarboxylic acids as flavor components - Google Patents

Abstract

The present invention relates to the use of amino acids and derivatives from diacids as flavoring components, wherein one of the carboxyl groups of the diacid is bonded to the α-amino group of the amino acid to form an amide group. In particular, this compound is particularly useful as an oral flavor and / or umami agent and / or as a partial or complete replacement for monosodium glutamate (MSG).

Description

TECHNICAL FIELD The present invention relates to the field of flavors, and in particular to flavoring of products where it is desired to impart or enhance its taste or aroma, ie the fullness and harmony of the oral flavor.

Along with this problem, the present invention more specifically relates to the formula (a)

［式中、Ｇは直鎖のＣ_１〜Ｃ_６−アルキル基またはＥまたはＺ立体配置を有する炭素−炭素二重結合を有するＨＣ＝ＣＨ基を表し；および
Ａは蛋白質形成性α−アミノ酸残基を表し、この残基はα−窒素原子を介してカルボニル基に結合している］の酸；および
（ｂ）式（Ｉ）の化合物の食用のアルカリ金属塩またはアルカリ土類金属塩、およびその水和物
からなる群から選択された少なくとも１種の化合物のフレーバリング成分としての使用に関する。

[Wherein G represents a linear C ₁ -C ₆ -alkyl group or an HC═CH group having a carbon-carbon double bond having an E or Z configuration; and A represents a protein-forming α-amino acid residue. And the residue is bonded to the carbonyl group via the α-nitrogen atom; and (b) an edible alkali metal salt or alkaline earth metal salt of the compound of formula (I), and It relates to the use of at least one compound selected from the group consisting of its hydrates as a flavoring component.

  Similarly, the invention relates to flavoring compositions and flavoring products containing at least one compound of the invention as a flavoring component.

Prior art Almost all of the compounds of the present invention are known. The compounds have been described for their presence in many contexts, for example in plant fruiting or in some microbial catabolism.

  However, according to our knowledge, none of these compounds is described as a flavoring ingredient, nor is it described as an umami and / or mouthfeel flavoring agent.

Detailed Description of the Invention Surprisingly,
(A) Formula

［式中、Ｇは直鎖のＣ_１〜Ｃ_６−アルキル基またはＥまたはＺ立体配置を有する炭素−炭素二重結合を有するＨＣ＝ＣＨ基を表し；および
Ａは蛋白質形成性α−アミノ酸残基を表し、この残基はα−窒素原子を介してカルボニル基に結合している］の酸；および
（ｂ）式（Ｉ）の化合物の食用のアルカリ金属塩またはアルカリ土類金属塩、およびその水和物
からなる群から選択された少なくとも１種の化合物のフレーバリング成分としての使用が特にフレーバー産業に有用であることが立証された。特に、口腔内風味および／またはうま味剤としておよび／またはグルタミン酸モノナトリウム（ＭＳＧ）の部分的または完全代替品としての使用は特に魅力的である。

[Wherein G represents a linear C ₁ -C ₆ -alkyl group or an HC═CH group having a carbon-carbon double bond having an E or Z configuration; and A represents a protein-forming α-amino acid residue. And the residue is bonded to the carbonyl group via the α-nitrogen atom; and (b) an edible alkali metal salt or alkaline earth metal salt of the compound of formula (I), and The use as a flavoring component of at least one compound selected from the group consisting of its hydrates has proved particularly useful in the flavor industry. In particular, the use as an oral flavor and / or umami agent and / or as a partial or complete replacement for monosodium glutamate (MSG) is particularly attractive.

  This use is, for example, a method for imparting, improving or enhancing the umami character and / or oral flavor of a flavoring composition or flavored product, the method comprising at least one kind of said composition or flavored product. It consists in adding an amount effective for the umami and / or oral flavor of the compounds of the present invention.

  By “oral flavoring agent” is meant here a flavoring ingredient that can change, impart, improve or enhance the taste characteristics of the flavoring composition or food to which it is added, and this is said flavoring Regarding the oral impact of the fragrance of the composition or food. In other words, the “oral flavor” according to the present invention provides an effect on the aroma or taste roundness and spread sensation of the product to which it is added.

  By “umami agent” we mean a flavoring ingredient that can impart what is usually defined by those skilled in the art as umami.

  The term “α-amino acid residue” has its usual meaning in the art, which is an α-amino acid without the hydrogen atom of the α-amino group, ie the group — (— HN—CHR—COOH. ). Hereafter, this residue will be represented by the three letter abbreviation shown below in parentheses, which is currently used to present the structure of the polypeptide chain (see, eg, Eur. J. Bioch. 1984, 138, 9-37). For clarity, it should also be mentioned that “protein-forming α-amino acid” here means any of the 12 amino acids naturally used in the synthesis of proteins. These amino acids are: L-glycine (Gly), L-alanine (Ala), L-valine (Val), L-leucine (Leu), L-isoleucine (Ile), L-proline (Pro), L-serine ( Ser), L-threonine (Thr), L-phenylalanine (Phe), L-tyrosine (Tyr), L-tryptophan (Trp), L-lysine (Lys), L-arginine (Arg), L-histidine (His) ), L-aspartic acid (Asp), L-glutamic acid (Glu), L-asparagine (Asn), L-glutamine (Gln), L-cysteine (Cys) and L-methionine (Met).

Accordingly, the present invention is C ₃ -C 8 _- about dicarboxylic acid moieties and compounds including residues of the protein-forming amino acids. Thus, to give a specific example, the derivative N- (3-carboxypropionyl) -glutamic acid, or succinoyl-Glu of the present invention has the following structure:

を有する。

Have

  The most interesting sensory characteristic of the present invention is the possibility of imparting highly appreciated umami and / or oral flavor characteristics to the composition or food to which it is added. More particularly, the oral flavor or oral impact provided by the presence of the compounds of the invention occurs in a very obvious roundness, spread and harmony of the overall taste of the flavoring composition or flavored product. . The overall sensory effect consists of a simple salt between free diacids and free amino acids that has a sharper taste associated with sourness and cannot impart umami and oral flavor characteristics to foods to which it is added It is different from what can be obtained with compounds.

  Such behavior makes the compounds of the present invention a useful partial or complete replacement for MSG, an oral flavoring agent known in the food industry. However, the overall sensory effect provided by the compounds of the present invention is less sweet than that provided by MSG and thus provides another means for flavor production.

According to a particular embodiment of the invention, in formula (I), G represents a CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ or HC═CH group and A is a residue of the amino acids Ala, Leu or Glu And the corresponding hydrates or edible alkali metal salts or alkaline earth metal salts have proved to be clearly useful for use according to the invention. In particular, succinoyl derivatives of Glu, Ala or Leu, ie N- (3-carboxypropionyl) -glutamic acid (succinoyl-Glu), N- (3-carboxypropionyl) -alanine (succinoyl-Ala), N- (3-carboxy Propionyl) -leucine (succinoyl-Leu) or its hydrate or its edible salt shows very good performance as a MSG substitute and / or as an oral flavor and / or umami agent and is highly evaluated Flavoring compositions and flavored products can be provided having the following sensory characteristics.

  For example, succinoyl-Glu has a slightly sour note with characteristics that have a sufficiently perceptible umami or bouillon connotation, and the overall sensory characteristics are good with long lasting roundness and spread. The compounds succinoyl-Leu and succinoyl-Ala have a slightly stronger acidity and slightly less umami than that of succinoyl-Glu, providing a similar sensory effect. Furthermore, the sensory effect of these compounds has been found to be slightly sweeter than that provided by MSG, thus the compounds of the present invention offer advantages for use in savory applications where sweet notes are not desired.

  Compound (Z) -N- (3-carboxy-2-propenoyl) -L-glutamic acid, N- (4-carboxybutanoyl) -L capable of imparting umami and oral flavor effects similar to those of succinoyl-Glu -Glutamic acid and N- (4-carboxybutanoyl) -L-leucine (maleyl-Glu, glutaryl-Glu, glutaryl-Leu, respectively) can also be cited. However, in meat-type applications, maleyl-Glu imparts a slightly strong juicy flavor, while glutaryl-Glu and glutaryl-Leu likewise impart a slightly strong fat-like flavor.

  It is pointed out that the compounds of formula (I) and said salts or hydrates thereof can also be used in the form of flavoring compositions that can be advantageously applied in the flavor industry, consistent with the purpose of the present invention. It is also important to do.

Accordingly, another subject of the invention is i) at least one compound of the invention as described above;
ii) at least one component selected from the group consisting of a flavor carrier and a flavor base; and iii) optionally at least one flavor adjuvant;
Is a flavoring composition containing

  The composition of the present invention comprising at least one compound of the present invention and at least one flavor carrier comprises at least one compound of the present invention, at least one flavor carrier, at least one flavor base, and optionally As with flavoring compositions containing at least one adjuvant, it represents a special embodiment of the present invention.

  By “flavor carrier” is meant a material that is substantially neutral from a flavor standpoint, ie, that does not significantly alter the sensory properties of the flavoring component. This carrier may be liquid or solid.

  Examples of the liquid carrier include, but are not limited to, an emulsifier system or a solvent usually used in flavors. A detailed description of the nature and type of solvents commonly used in flavor bases is not complete. One skilled in the art can select these based on the nature of the product to be flavored. However, examples of solvents commonly used in flavors may include propylene glycol, triacetin, triethyl citrate, benzyl alcohol, ethanol, vegetable oils or terpenes.

  As solid carriers, for example, absorbent gums or polymers, or encapsulating materials described in more detail below, can be cited, but are not limited thereto.

  In general, “flavored base” refers herein to a composition containing at least one flavoring co-component.

  This flavoring co-component is not of formula (I). Furthermore, “flavoring co-component” means herein a compound used in a flavoring product or composition for imparting a taste effect. In other words, co-components to be recognized as such flavorings not only have a taste but can also impart or modify the taste of the composition in a positive or pleasant direction by those skilled in the art. Must be accepted as.

  The nature and type of flavoring co-components present in the base are based on their general knowledge and can be selected by the intended use or application and the desired sensory effect, where any In some cases, no further details will be given. In general terms, this perfume co-component belongs to a diverse group of compounds such as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpene hydrocarbons, nitrogen or sulfur heterocyclic compounds and essential oils. The perfume co-component may be of natural or synthetic origin. Many of these co-components are often found in S. Arctander's book, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or more recent references, or in the flavor field. It has been described in other similar studies such as patent literature.

  Flavoring compositions containing at least one compound of formula (I) such as succinoyl-Glu, succinoyl-Ala and succinoyl-Leu and / or derivatives thereof are particularly useful from a functional standpoint.

  In a special embodiment of the invention, the flavor base contains at least one flavoring co-component selected from the group consisting of extracts derived from unicellular organisms, protein hydrolysates and fat hydrolysates. The flavoring composition has proven particularly useful as a MSG replacement.

  By “extract derived from a unicellular organism” is meant an extract obtained by degradation of a unicellular organism, eg autolysis, eg yeast. Examples of unicellular organisms are Saccharomyces cerevisiae and Torulla cells.

  As used herein, “protein hydrolysis” means a residue obtained by protein degradation, for example, hydrolysis. Examples of such materials are products obtained by hydrolysis of proteins currently used in the flavor industry such as casein, soy protein and pea protein. In particular, casein hydrolyzate is very interesting.

  By “fat hydrolyzate” is meant here the residue obtained by the breakdown of fat, for example by enzymatic hydrolysis. An example of such a material is hydrolyzed butter oil.

  An advantageous composition of an embodiment of the invention is a flavoring composition wherein the flavor base contains at least one yeast extract, at least one protein hydrolyzate and at least one fat hydrolysate. Indeed, in such an embodiment, an unexpected synergistic effect between the co-components can be very advantageous for the intended use of the flavoring composition, e.g. clearly rich and balanced. It has been found to impart additional sensory effects such as flavor spread, volume and perception, which are similar or even more suitable as obtained with MSG.

  The flavoring composition according to the invention may be in the form of a simple mixture of flavoring ingredients, or the encapsulated form, for example the flavoring composition may be encapsulated in a solid matrix. Encapsulation methods that can protect the fragrance may consist of techniques such as spray drying, agglomeration or further extrusion; or may consist of coating encapsulation including coacervation and complex coacervation techniques. Good. The carrier materials used for the matrix are wall-forming and plasticizing materials such as monosaccharides, disaccharides, trisaccharides, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetate, polyvinyl alcohol, proteins or Pectin. Examples particularly useful as matrix materials are sucrose, glucose, lactose, levulose, fructose, maltose, ribose, dextrose, isomalt, sorbitol, mannitol, xylitol, lactitol, maltitol, pentatol, arabinose, pentose, xylose, Galactose, maltodextrin, dextrin, chemically modified starch, hydrogenated starch hydrolyzate, succinylated or hydrolyzed starch, agar, carrageenan, gum arabic, acacia gum, tragacanth, alginate, methyl celcose, carboxymethylcellulose, hydroxy Ethyl cellulose, hydroxypropyl methyl cellulose, derivatives and mixtures thereof. Coaching encapsulation is typically based on a thin xerogel carrier system that includes gelatin, agar and alginate. Other suitable carrier components are cited in references such as H. Scherz, Hydrocolloids: Stabilisatoren, Dickungs- und Giehermittel in Lebensmittel, Band 2 der Schriftenreihe Lebensmittelchemie, Lebensmittelqualitaet, Behr's Verlag GmbH & Co., Hamburg, 1996. . The cited materials are given by way of example and should not be understood as limiting the invention.

  In the above composition, more particularly one or more compounds of formula (I) or derivatives thereof have the flavor tones or properties of the various compounds of the present invention, thereby providing new means for the work. It is useful to mention here that it has the potential to be important as it allows the flavor list to produce the flavors that it creates.

  Unless otherwise suggested or described, any mixture resulting directly from chemical synthesis may contain, for example, without suitable purification, the compounds of the invention as starting materials, intermediates or final products therein. It should also be understood here that it cannot be recognized as a composition according to the invention.

  In general, “flavor adjuvant” means here an ingredient capable of imparting additional added benefits such as color, in particular lightfastness, chemical stability and the like. Although a detailed description of the nature and type of adjuvants commonly used in flavoring bases cannot be completed, it should be noted that this component is well known to those skilled in the art.

The compounds or compositions of the present invention that are advantageously described are useful flavoring ingredients that can be advantageously incorporated into flavored products or foods to improve or enhance their taste. Therefore:
i) at least one compound selected from the group consisting of a compound of formula (I) and its edible alkali metal or alkaline earth metal salt, and hydrates thereof, or a composition of the present invention; and ii) Flavored products consisting of a food base are likewise the subject of the present invention.

  For the sake of clarity, “food-based” here specifies that it is an edible product, for example food or beverage. Accordingly, flavored products according to the invention are usually added to functional formulations and optionally edible products, for example additional advantageous agents corresponding to stock, and flavor effective amounts and optionally flavors of at least one compound of the invention. Contains one or more solvents used.

  The nature and type of ingredients of the food or beverage will not be described in more detail here, but this cannot be fully described in any case, and the person skilled in the art is familiar with the general knowledge and the nature of the product. This can be selected based on.

  Suitable food bases such as food or beverages may be low fat or classic, ie non-fat reduced type. "Low fat" here means that the fat content is 30%, preferably 50% lower than in the classic product. Indeed, low fat and classic food products, and especially low fat products, can be improved in terms of umami and / or oral flavor characteristics using the compounds or flavoring compositions according to the invention. I found it.

  Suitable food bases include, for example, all savory foods such as meat, poultry meat, fish, vegetables, cheese, dairy types.

  The proportion at which the compounds according to the invention can be mixed into the various products or compositions described above varies within a wide range of values. These values depend on the nature of the product or product to be flavored and are determined when the compounds according to the invention are mixed with flavoring co-components, solvents or additives normally used in the field. It depends on the desired effect as well as the nature of the co-components in the composition.

  For example, typical concentrations of 0.05% to 0.25%, and preferably 0.1% to 0.2% by weight of these compounds relative to the food product in which these compounds are mixed are typically Can be used. Of course, higher concentrations can be used when this compound is mixed into the flavoring composition.

  The compounds of the invention can be prepared from commercially available products and using methods that employ conventional reactions. For example, one of the methods that can be used to prepare the compounds of the present invention is the starting diacid of formula HOOC-G-COOH, where G is as defined in formula (I) And approximately 1 molar equivalent of a protein-forming α-amino acid in the presence of a carboxylic acid activator such as DCC (N, N-dicyclohexylcarbodiimide) and N-hydroxysuccinimide. Optionally, if appropriate, approximately 1 molar equivalent of a suitable acid in water / dioxane or an aqueous solution buffered at a pH between 7.0-11 with a protein-forming α-amino acid without heating. It is possible to react together with the anhydride. Of course, it is also possible to produce the compound of formula (I) by reacting an amino acid with an acid chloride derivative.

Details of this production method will be described further. Temperatures are given in degrees Celsius (° C.); unless otherwise noted, ¹ H-NMR spectral data were recorded at 400 MHz, ¹³ C-NMR at 100 MHz, and recorded in D ₂ O. The chemical shift is δ, shown in ppm relative to TMS as standard, the coupling constant J is shown in Hz, and all abbreviations have their usual meaning in the field.

General method A) Reaction of amino acids with acid anhydrides A pH of 9.3 (adjusted using an aqueous solution of concentrated NaOH) to a solution of α-amino acids (1.5 mol) in 800 ml of demineralized water. An equimolar amount of powdered acid anhydride was added to a small amount. During the addition of the anhydride and the reaction, the pH value of the reaction medium is continuously monitored and, if necessary, adjusted to a pH value of 8.7 to 9.5 by controlled addition of a portion of concentrated aqueous NaOH solution. Retained. After stirring overnight, the addition of a sufficient amount of an acid type cation exchange resin (e.g. Dowex ^(R) 50WX8) to lower the pH value to about 2 to 3 in the reaction medium. The resulting mixture was filtered and the solution was evaporated to dryness to give the compound of the invention in its acid form. Optionally, if an edible salt is desired, an appropriate amount of a suitable base can be added prior to evaporation to dryness. The product thus obtained has a purity of at least 90% and often exceeds 95%, the remainder being the dicarboxylic acid obtained by hydrolysis of the starting acid anhydride.
B) Reaction of amino acids with diacids DCC (16 mmoles) was added over 5 minutes to a 15 ° C solution of dicarboxylic acid (15 mmoles) and N-hydroxysuccinimide (16 mmoles) in 22.5 ml of dioxane. The mixture thus obtained was stirred for 4 hours and then the white precipitate was filtered off. The solution thus obtained was added into a solution of amino acid (17 mmol), NaHCO ₃ (17 mmol) in 24 ml of demineralized water. After stirring for 18 hours at room temperature, the organic solvent was evaporated and the resulting aqueous solution was washed three times with ethyl acetate. The pH value of the resulting aqueous phase thus adjusted to 2 by addition of Dowex ^(R) 50WX8 resin. After filtration of the resin, the pH value of the aqueous solution was adjusted to 5.5-6 by adding 1 M aqueous NaOH solution, and then the crude solution was lyophilized to obtain the crude product. The crude product was purified by preparative HPLC (conditions: Column Microsorb C18, 250 · 10 mm, Rainin, eluted with 4 ml / min of isocratic mixture of water and acetonitrile 8/2 containing 0.2% formic acid, Detection: UV @ 214nm).
C) Reaction with amino acids and acid chlorides A solution of an acid dichloride, such as fumaryl dichloride (0.25 mol) in 100 ml of dioxane, over 2 minutes, an amino acid, such as glutamic acid, in 150 ml of a 1/2 mixture of water and dioxane. A solution of (0.25 mole) and NaOH (4 mole equivalent) was added. The pH value of the resulting mixture was adjusted to 9.5 by adding a portion of 1M aqueous NaOH. After stirring for 90 minutes, the reaction mixture was washed with ethyl acetate, the aqueous phase cation exchange resin (e.g., Dowex ^(R) 50WX8) and filtered through a column containing. The aqueous solution thus obtained was freeze-dried to obtain a crude product. The crude product was purified by preparative HPLC (conditions: Column Microsorb C18, 250 · 10 mm, Rainin, eluted with 4 ml / min of isocratic mixture of water and acetonitrile 8/2 containing 0.2% formic acid, Detection: UV @ 214nm).

  The invention is illustrated in more detail by the following examples, whose omissions have their ordinary meaning in the art. These examples represent representative methods for practicing the present invention and are not described separately, and are not specifically described with respect to the relative or absolute proportions of the components recited.

Example 1
Flavors containing the compounds of the invention Beef-type flavors, A), B) and C) were prepared by mixing the following ingredients:

  Beef stock base, A '), B') and C ') were prepared by mixing the following ingredients:

  Three different bouillons were obtained using the above three different stock bases in an amount of 10 g per 500 g of hot water. According to a panel of five familiar flavorists, the tastes of the three bouillons are listed below:

  In conclusion, bouillons containing B ') and C') showed similar profiles with regard to taste roundness and persistence. However, the latter is slightly different, i.e. B ') provided a sweeter bouillon, where C') resulted in a bouillon with enhanced meat-like characteristics.

Claims (10)

(A) Formula

[Wherein G represents a linear C ₁ -C ₆ -alkyl group or an HC═CH group having a carbon-carbon double bond having an E or Z configuration; and A represents a protein-forming α-amino acid residue. And the residue is bonded to the carbonyl group via the α-nitrogen atom; and (b) an edible alkali metal salt or alkaline earth metal salt of the compound of formula (I), and Use as a flavoring component of at least one compound selected from the group consisting of its hydrates.   Use according to claim 1, wherein the compound is an oral flavor and / or umami and / or as a partial or complete replacement for monosodium glutamate. i) Equation (a)

[Wherein G represents a linear C ₁ -C ₆ -alkyl group or an HC═CH group having a carbon-carbon double bond having an E or Z configuration; and A represents a protein-forming α-amino acid residue. And the residue is bonded to the carbonyl group via the α-nitrogen atom; and (b) an edible alkali metal salt or alkaline earth metal salt of the compound of formula (I), and At least one compound selected from the group consisting of its hydrates;
ii) at least one component selected from the group consisting of a flavor carrier and a flavor base; and iii) optionally at least one flavor adjuvant;
Flavoring ingredients in the form of a composition comprising   4. A flavoring component according to claim 3, wherein the flavor base has at least one flavoring co-component selected from the group consisting of extracts derived from unicellular organisms, protein hydrolysates and fat hydrolysates.   The flavoring component according to claim 4, wherein the extract derived from a unicellular organism is a yeast extract.   The flavoring component according to claim 4, wherein the protein hydrolyzate is a casein hydrolyzate, a soy protein hydrolyzate or a pea protein hydrolysate.   The flavoring component according to claim 4, wherein the fat hydrolyzate is hydrolyzed butter oil.   5. A flavoring component according to claim 4, wherein the flavor base comprises at least one yeast extract, at least one protein hydrolysate and at least one fat hydrolysate. i) Equation (a)

[Wherein G represents a linear C ₁ -C ₆ -alkyl group or an HC═CH group having a carbon-carbon double bond having an E or Z configuration; and A represents a protein-forming α-amino acid residue. And the residue is bonded to the carbonyl group via the α-nitrogen atom; and (b) an edible alkali metal salt or alkaline earth metal salt of the compound of formula (I), and At least one compound selected from the group consisting of its hydrates;
Or a composition according to claim 4; and ii) a flavored product containing a food base.   10. A flavored product according to claim 9, wherein the food base is in the form of a savory food.