BRPI0719989B1 - taste modulating substances, flavoring compositions and products comprising them, product taste enhancing method, and taste preparation production process - Google Patents

Description

DESCRIPTION OF THE INVENTION PATTERN FOR "FLAVOR MODULATION SUBSTANCES, FLAVOR COMPOSITIONS AND PRODUCTS UNDERSTANDING THE PRODUCTS, FLAVOR PRODUCT IMPROVEMENT METHOD, AND FLAVOR PREPARATION PRODUCTION PROCESS".

Field of the Invention The present invention relates to the field of taste enhancement of foodstuffs, beverages, tobacco products, pharmaceuticals and oral care products. More particularly, the present invention provides taste modulating substances and compositions comprising them which may be used to enhance and complement the impression of other flavoring substances. The present invention also encompasses the use of the above taste modulating substances as well as foodstuffs, beverages, tobacco products, pharmaceuticals and oral care products containing these substances.

Background of the Invention The taste of food and beverages consists of two parts: the aroma and the taste. In general what is perceived through the olfactory epithelium in the nasal cavity is referred to as' aroma ', whereas the term' flavor * is generally used to describe the sensory impression that is perceived through the mouth, especially the tongue. The taste sensation experienced in consumption, especially taste, provides the final analysis of the food prior to ingestion. Visual and olfactory signals (smell) already give a first indication but only after the food enters the mouth is the final decision made to either ingest or reject the food. Sweet flavor is usually a sign that food is safe (appetizing) leading to food intake. The 'reactions' for salt and umami are really dependent on signal strength. Bitter and sour are generally repulsive taste sensations, leading to rejection. Temperature is another measure by which food is judged, just as are painful sensations like capsaicin (hot pepper) and certain chemicals (like carbon dioxide).

In short, this means that flavor is a very important and very complex system. Until recently more flavor research has been focused on aroma. Especially in recent years, a number of publications referring to molecules with a (positive) contribution to the taste of food have emerged.

Such research has been significantly stimulated by the fact that indeed some receptors that are involved in different taste sensations have so far been characterized (J. Chandrashekar et al., Nature 444, 288 (2006)).

Another interesting aspect of flavor is that it can have an impression on aroma. People with artificially sweetened water in their mouths have been reported to be significantly more sensitive to the smell of benzaldehyde than people with ordinary water in their mouth (P. Dalton et al., Nature Neurosci. 3, 431-432 (2000)).

Several analysis systems have been described which make it possible to analyze in a short time large series of molecules for their effect (modulation) on taste response (cf. WO 04/055048, GB 2396414, WO 01/77292 and US 2004/0072254).

More research on flavor modulation has so far been devoted to flavor enhancement in tasty products. Several publications, mainly Japanese, describe umami molecules, that is, alternatives to mono sodium glutamate (MSG) (H Suzuki et al., J Agric Food Chem 50, 313-318 (2002); K Shima et al., J Agric Food Chem 46, 1465-1468 (1998); Ueda et al., Biosc Biotech Biochem 61, 1977 (1997)).

In EP 1291342, a 'general flavor enhancer' is described where it has been reported to be suitable for sweetness enhancement as well.

WO 97/04667 and WO 04/075633 tripeptides and amino acid condensates with lactic acid and succinic acid are described having both their own taste as well as some enhancing properties. Alpha-keto acids are reported to produce body and mouth sensation in the foodstuffs to which they are added (US 6,287,620). Chlorogenic acids are claimed to enhance sweetness and reduce bitterness (WO 02/100192).

Truly a lot of work has been devoted to finding bitter taste suppressants (ANPronin et al., Chemical Senes 29, 583-593 (2004); EP 1401500; PA Breslin, Trends in Food Science & Technology 7, 390-399 ( 1996)).

In candy and beverage products, additional examples of the importance of the taste dimension of flavorings have been reported. These examples include flavor attributes such as bitterness, tingling and cooling-freshness.

Bitterness is an essential aspect of some food flavors, including chocolate flavor. Purine alkaloids such as theobromine and caffeine as well as amino acids and peptides have long been recognized as bitter substances. British Patent No. GB 1420909 discloses that the bitter cocoa taste can be reproduced using a combination of a purine alkaloid and an amino acid or oligopeptide which produces a surprisingly more natural bitter and astringent taste note than or the same kinds of substances alone. '

Menthol, a major constituent of peppermint oil, has a strong impression on flavored products not only because of its mint smell, but also because it gives it a cooling and fresh flavor. Following mint flavored products, it has been suggested to employ menthol in other flavor types to impart a freshness flavor. United States Patent Application No. US 2005/013846, for example, describes how menthol and derivatives thereof that can be used as a flavoring in water-dispersible acidic flavored products to obtain table dispersions exhibiting a refreshing freshness taste impression .

Similarly cinnamic aldehyde and eugenol, constituents of cinnamon oil, are used in flavoring composition for confectionery, not only because of their smell but also because they impart a warm and tingling taste. The oral pungency of cinnamic aldehyde has been described as burning and tingling by Cliff M and Heymann H (Journal of Sensory Studies 7, 279-290 (1992)). According to the same authors, euge-nol exhibits a long lasting numbing effect. Cinnamon oil has been proposed as a flavor enhancing flavoring. International Patent Application No. WO 90/06689 discloses that cinnamon oil, among other spice extracts, added to a menthol flavor formulation, can be used to enhance the long lasting taste of chewing gum.

Vanillyl alcohol derivatives (for example, vani-lila or ethyl methyl ether) are described in US Patent 2002/0013235 as having a strong pungent taste and effect giving a heated sensation. The same substances are described in JP 57082308 to be effective in enhancing the effect conferring menthol refreshment sensation. Vanylyl ethyl ether is more specifically described as beer flavor enhancing agent in JP 20044229562. Substances of the same group such as vanillyl n-propyl ether are also described in JP 57009729 as useful ingredients for salty taste.

Six carbamic amides other than vanillylamine, being structurally analogous to the cayenne pepper principle, were tested for their pungency properties (Lange et al; J. Am. Chem. Soc., Vol. 51, No. 6,1911-1914 (1929) Vanillylurea, vanillylthiourea and phenylvanylylthiourea were however reported to be tasteless both as a dry powder and as an alcoholic or aqueous solution Phenylvanylthiourea, p-tolylvanylthiourea and o-tolylvanylthiourea were found to have the property of pungency but in a less than capsaicin.

Vanillyl amine and vanillyl acyl amides are also reported (US Patent 1,329,272) to be spicy molecules and may be used as substitutes or to fortify cayenne pepper for use in food and drink to produce a hot or spicy taste.

N- (3-Acyloxy-2-benzylpropyl) -N- (4-hydroxy-3-methoxy-benzyl) thiourea derivatives are described as potent vanilloid receptor agonists and analgesics (Lee et al; Bioorganic and medicinal chemistry 9, 9 -12 (2001)). According to WO 2005/006881, these thiourea derivatives are also TRP V1 receptor binders, so that they would exhibit salty taste characteristics.

Derivatives of α-hydroxy and purine carboxylic acids or pyrimidines such as GMP, AMP, CMP and IMP are described in WO 2005/096843. According to said international patent application, these substances are capable of modification and complementation of the sensory impression of flavoring substances. Thus, the present flavor enhancing substances are advantageously applied to flavor compositions, foodstuffs, pharmaceuticals, tobacco products, pharmaceuticals and oral care products. There is still a need for new substances having a positive contribution to the taste, especially taste, of foodstuffs, beverages, tobacco products, pharmaceuticals and / or oral care products in which they are incorporated within. An object of the present invention is the provision of novel substances and compositions that can complement and enhance the printing of other flavoring substances, in particular substances having the ability to improve the impression of other flavoring substances in very low concentrations.

Summary of the Invention The present inventors have surprisingly found that substances selected from the group represented by formula (I): (i) and edible salts thereof and edible esters thereof can advantageously be used for taste modulation of foodstuffs, beverages, tobacco products. , pharmaceuticals and o-ral care products.

The present flavor modulating substances may be used to impart desirable flavor attributes in a wide variety of applications and products. Further, the present taste modulating substances are capable of modulating the taste and / or aroma impression of other flavoring substances contained within the same products, thereby improving the overall taste quality of the same products. Despite the above-mentioned prior art description teaching the use of purine or pyrimidine taste modulation derivatives with α-hydroxy carboxylic acids, it has now been found that purine or pyrimidine derivatives with carboxylic acids not containing an α-hydroxyl group constitute substances. very powerful flavor modulation Furthermore, as will be explained and illustrated below, the present invention provides taste modulating substances which can achieve the desired effects at remarkably low dosages, as compared to said prior art taste modulating substances.

Therefore, the present invention relates to these taste modulating substances and compositions comprising one or more of these substances. In addition, methods of flavor enhancement of a product selected from foodstuffs, beverages, tobacco products, pharmaceuticals and oral care products, as well as products comprising the present taste modulating substances are provided by the invention.

Detailed Description of the Invention In one aspect of the invention, taste modulating substances according to formula (I) are provided as well as edible salts and esters thereof: d) wherein X represents. hydrogen; . C 1 -C 12 alkyl or C 2 -C 12 branched or unbranched aliphatic or cyclic alkenyl, each optionally substituted with one or more substituents selected from the group of oxo, hydroxyl, amine, thiol, lower thioalkyl, lower alkoxy, guanidine and heterocyclic moieties. saturated or unsaturated clinics; . a moiety represented by the formula -Z-Phe, wherein Z represents a covalent bond or a branched or unbranched saturated or unsaturated C1-C6 alkylene optionally substituted with one or more substituents selected from the group of oxo, hydroxyl, amine, and alkoxy lower and wherein Phe represents phenyl, optionally substituted with one or more substituents selected from hydroxyl, amine and lower alkoxy; . a moiety represented by the formula -Y-CO-NHR, wherein Y represents branched or unbranched saturated or unsaturated C1-C12 alkylene, optionally substituted with one or more substituents selected from the group of oxo, hydroxyl, amine, thiol, lower thioalkyl lower alkoxy and lower carboxyl; provided that X does not represent a moiety wherein the carbon atom of α is substituted with a hydroxyl group; and wherein R represents (i) a moiety comprising a six membered heterocyclic ring comprising at least two nitrogen atoms, whose heterocyclic ring is also optionally substituted with one or more substituents selected from the amino group; hydroxyl; oxo; alkyl; ribose and deoxyribose and ribose and deoxyribose phosphate esters; or (ii) a portion comprising a bicyclic fused ring system comprising a five membered heterocyclic ring and a six membered heterocyclic ring, each ring comprising at least two nitrogen atoms, and each ring optionally also being substituted with one or more substituents. selected from the amino group; hydroxyl; oxo; alkyl; ribose and deoxyribose and ribose and deoxyribose phosphate esters. The term "lower" as used herein in connection with the terms "alkoxy" and "thioalkyl" means that the related moiety comprises a carbon chain moiety of no more than six carbon atoms, preferably no more than four carbon atoms, more preferably no more than three carbon atoms.

The present inventors have found that the above-mentioned taste modulating substances are very useful taste ingredients which, particularly in the presence of other flavoring substances, are capable of imparting highly appreciated taste sensations to the products in which they are incorporated, specifically "cooling", "spicy", "sour", "tingling" "hot", "sharp", "burning", "heated", "alcohol" type, "continuity", "complexity", "spreading" "," salty "," umami "and / or" long term ". Because of this, the present substances may be employed to improve the taste, especially taste (including "mouthfeel"), of foodstuffs, beverages, tobacco products, pharmaceuticals and oral care products.

The taste modulating substances of the present invention as such are capable of imparting highly desirable taste attributes. In addition, it has been found that the taste modulating substances according to the invention are capable of complementing and modifying the sensory impression of other flavoring substances contained in the aforementioned products including "feeling alcohol" complementation and modulation. , "bitterness", "warm taste sensation", "cold taste sensation", "carbonation effects", and / or "salt taste impression". Without wishing to be bound by any theory, the findings of the present invention seem to suggest that the presence of sodium chloride and / or mono sodium glutamate greatly affects the aforementioned properties, since the aforementioned effects are achieved at much lower concentrations. of taste modulating substances in the presence of NaCI and / or MSG.

Throughout this document, the term "taste" is used to describe the sensory impression that is perceived through the mouth, especially the tongue, and the olfactory epithelium in the nasal cavity. The term "sensory impression complementation and modification" as used herein refers to the ability of the present compositions or substances to alter the taste and / or aroma impression of other flavoring substances present within the same product, provided that this change in taste impression is not caused by the taste contribution of said composition or substance per se, but rather that it mainly results from the combined effect of the present taste modulation composition or substance and on the other hand, the other flavoring substance (s). The present flavor modulating substances combine the ability to modulate the taste and / or aroma of others, flavoring substances and a taste contribution of their own. The favorable impression of the present taste modulating substances is believed to be the result of the combination of the same two effects. Because the taste modulating substances according to the invention are not particularly volatile, they do not produce a strong aroma impression, even though they may affect the aroma impression of other flavoring substances. At this point, the term "aroma" refers to the taste aspect that is perceived through the olfactory epithelium. Because of the low volatility of the present flavor modulating substances, it is believed that the advantageous properties of these substances are somewhat associated with the impression these substances have on sensory receptors located within the mouth.

In one embodiment of the invention, X represents hydrogen, so that the X-CO- portion represents the formic acid residue.

In another equally preferred embodiment of the invention, X represents C 1 -C 12 alkyl or C 2 -C 12 aliphatic or branched or unbranched cyclic alkenyl, each optionally substituted with one or more substituents selected from the group of oxo, hydroxyl, amine, thiol , lower thioalkyl, lower alkoxy, guanidine and saturated or unsaturated heterocyclic moieties.

Particularly satisfactory results are obtained with taste modulating substances as defined hereinbefore wherein X represents C1-C8 alkyl or C2-C8 branched or unbranched alkenyl each optionally substituted with one or more substituents selected from the oxo, hydroxyl group , amine, thiol, lower thioalkyl, lower alkoxy, guanidine, imidazole, indole and pyrrolidine. Even more preferably, X represents C1 -C4 alkyl, preferably C1 -C4, more preferably branched or unbranched C1 -C2; X represents C1-C5 α-amino branched or unbranched alkyl, optionally substituted with one or more substituents selected from oxo, hydroxyl, amine, thiol, lower thioalkyl, lower alkoxy, guanidine, imidazole, indole and pyrrolidine; X represents C1 -C2 alkyl substituted with an oxo substituent; or X represents C 2 -C 6 saturated or unsaturated carboxyl, optionally substituted with a substituent selected from the lower oxo and carboxyl group, or C 2 -C 4 α-amino carboxyl. More preferably, the X-CO- moiety represents the residue of acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, pyruvic acid, oxalic acid, succinic acid, glutamic acid, fumaric acid, maleic acid, adipic acid, citric acid, oxalacetic acid, aspartic acid, glutamic acid, glycine, alanine, arginine, asparagine, cysteine, glutamine, histidine, isoleucine, leucine, lysine, methionine, proline, serine, threonine , tryptophan, or valine.

In another preferred embodiment, substances as defined hereinbefore are provided wherein X represents C1 -C12 alkyl or branched or unbranched C2 -C12 alkenyl, preferably C1 -C6 alkyl or C2 -C6 alkenyl, each optionally substituted with one or more. substituents selected from the group of oxo, hydroxyl, amine, thiol, lower thioalkyl and lower alkoxy. Even more preferably, X represents branched or unbranched C1 -C6 alkyl, more preferably C1 -C4, more preferably C1 -C2 alkyl; X represents C1 -C2 substituted with an oxo substituent; or X represents C 2 -C 6 saturated or unsaturated carboxyl, optionally substituted with a substituent selected from the lower oxo and carboxyl group, or C 2 -C 4 α-amino carboxyl. More preferably, the X-CO- moiety represents the residue of acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, pyruvic acid, oxalic acid, succinic acid, glutaric acid, fumaric acid, maleic, adipic acid, citric acid and oxalacetic acid.

In another equally preferred embodiment of the invention, X represents -Phe, that is, Z represents a covalent bond. Particularly satisfactory results are obtained with taste modulating substances as defined hereinbefore, wherein -Phe represents phenyl substituted with 1 to 3 substituents selected from hydroxyl, amino and methoxy. More preferably, the X-CO- moiety represents the residue of benzoic acid, gallic acid, vanillic acid or anthranilic acid.

In yet another, equally preferred embodiment of the invention, Z represents saturated or unsaturated C1 -C4 alkylene optionally substituted with one or more substituents selected from the group of oxo, hydroxyl, amine, and lower alkoxy. Particularly satisfactory results are obtained with taste modulating substances as defined hereinbefore, wherein Z represents C 2 -C 4 unsaturated alkylene and -Phe represents phenyl optionally substituted with 1 to 3 substituents selected from hydroxyl and methoxy, or wherein Z represents a C1 -C2 α-amino alkylene, optionally substituted with 1 to 3 hydroxyl groups. More preferably, the X-CO- moiety represents the residue of cinnamic acid, caffeic acid, ferulic acid, phenylalanine or tyrosine.

In yet another, equally preferred embodiment of the invention, X represents a moiety represented by the formula -Y-CO-NHR, wherein Y represents branched or unbranched saturated or unsaturated C1 -C12 alkylene, optionally substituted with one or more substituents selected from the group of oxo, hydroxyl, amine, thiol, lower thioalkyl, lower alkoxy and lower carboxyl. Particularly satisfactory results are obtained with taste modulating substances as defined hereinbefore, wherein X represents a moiety represented by the formula -Y-CO-NHR, wherein Y represents saturated or unsaturated C1 -C6 alkylene, optionally substituted with a or more substituents selected from the group of oxo, hydroxyl, amine and lower carboxyl. According to said embodiment, the taste modulating substance is preferably a derivative of a di or tri carboxylic acid having two moieties represented by the formula -NHR, said dicarboxylic acid being more preferably selected from the group of oxalic acid, succinic acid. , glutaric acid, fumaric acid, maleic acid, adipic acid, citric acid, oxalacetic acid, aspartic acid or glutamic acid.

In one embodiment of the invention, it is preferred that the R moiety represents a purine or a pyrimidine moiety that is substituted with a pentose monosaccharide moiety, preferably ribose or deoxyribose, or a phosphate ester thereof, such that the -NRH moiety represents the residue of a nucleoside or nucleotide.

In a particularly preferred embodiment, the -NRH moiety represents the residue of a purine radical, a pyrimidine radical, a nucleotide or nucleoside selected from the group of cytosine, guanine, adenine, guanosine, adenosine, cytidine, 5'-monophosphate guanosine (GMP), adenosine 5'-monophosphate (AMP), or cytidine 5-monophosphate (CMP), more preferably the GMP residue.

In an even more preferred embodiment, the invention relates to taste modulating substances selected from the group of N-acetyl GMP, N-formyl GMP, N-propanoyl GMP, N-butanoyl GMP, N-acetyl GMP. pentanoyl, N-hexanoyl GMP, N-heptanoyl GMP, N-octanoyl GMP, N-oxalyl GMP, N-sucinyl GMP, N-glutaryl GMP, N-fumaryl GMP, N-maleyl GMP, N-adipyl GMP, N-citryl GMP, N-galloyl GMP, N-oxalacetyl-GMP, N-feruloyl GMP, N-pyruvyl GMP, N-benzoyl GMP, N-vanilloy GMP, N-anthranoyl, N-caffeoyl GMP, N-cinnamoyl GMP, N-acetyl AMP, N-formyl AMP, N-propanoyl AMP, N-Butanoyl AMP, N-Pentanoyl AMP, N- hexanoyl, N-heptanoyl AMP, N-octanoyl AMP, N-oxalyl AMP, N-sucinyl AMP, N-glutaryl AMP, N-fumaryl AMP, N-adipile AMP, N-Citryl AMP, N-Galloyl AMP, N-Oxalacetyl-AMP, N-Feruloyl AMP, N-Pyruvyl AMP, N-Benzoyl AMP, AMP N-vanyloyl NMP, N-anthranoyl AMP, N-Caffeoyl AMP, N-Cinnamoyl AMP, N-Acetyl CMP, N-Formyl CMP, N-Propanoyl CMP, N-Butanoyl CMP, N CMP -pentanoyl, N-hexanoyl CMP, N-heptanoyl CMP, N-octanoyl CMP, N-oxalyl CMP, N-sucinyl CMP, N-glutaryl CMP, N-fumaryl CMP, N-maleyl CMP , N-adipyl CMP, N-citryl CMP, N-galloyl CMP, N-oxalacetyl-CMP, N-feruloyl CMP, N-pyruvyl CMP, N-benzoyl CMP, N-vanilloyl CMP, CMP N-anthranoyl, N-caffeoyl CMP, N-cinnamoyl CMP, edible salts thereof and edible esters thereof. Even more preferably, the invention relates to taste modulating substances selected from the group of N-acetyl GMP, N-formyl GMP, N-propanoyl GMP, N-butanoyl GMP, N-pentanoyl GMP, GMP N-hexanoyl GMP, N-heptanoyl GMP, N-octanoyl GMP, N-oxalyl GMP, N-sucinyl GMP, N-glutaryl GMP, N-fumaryl GMP, N-maleyl GMP, N GMP -adipyl, N-citryl GMP, N-galloyl GMP, N-oxalacetyl-GMP, N-feruloyl GMP, N-pyruvyl GMP, N-benzoyl GMP, N-vanyloyl GMP, N-anthranoyl GMP , N-caffeoyl GMP, N-cinnamoyl GMP, edible salts thereof and edible esters thereof. More preferably, the invention relates to taste modulating substances selected from the group of N-acetyl GMP, edible salts thereof and edible esters thereof.

As used herein, the term "edible esters thereof" refers to a derivative of a taste modulating substance of the invention and an acid or alcohol formed by reaction of said acid or alcohol with a hydroxyl group or carboxyl group respectively, which is present in said taste modulating substance, said derivative being suitable for human consumption, that is, being non-toxic, and having taste modulating properties as explained hereinbefore. The term "edible salt" as used herein refers to a salt that is generally considered suitable for human consumption, particularly a non-toxic salt. Acceptable salts include base addition salts and acid addition salts of the corresponding free acid. These salts typically can be prepared by conventional acid free mechanisms of the present taste modulating substances. Illustrative base addition salts include metal salts and organic salts. Metal salts include alkali metal salts such as sodium and potassium salts, alkaline earth metal salts such as calcium and magnesium salts. Organic salts include salts made of secondary, tertiary and quaternary amines such as diethylamine, triethylamine, ethanolamine, diethanolamine, and salts made of cationic amino acids such as arginine, lysine and histidine. Examples of suitable acid addition salts include hydrochloride, phosphate, hydrogen phosphates, acetate, aspartate, ascorbate, citrate, glyconate, lactate, succinate, rat rat.

A second aspect of the invention relates to flavoring compositions comprising at least 60 ppt of one or more of the present flavor modulating substances selected from the group of substances represented by formula (I), edible salts thereof and edible esters thereof, as well as as at least 0.1% by weight of one or more flavoring substances. Particularly preferred examples of the taste modulating substances according to the invention are as defined hereinbefore. Typically, the taste compositions of the present invention comprise one or more taste modulating substances in an amount of less than 10,000 ppm. The term "comprising" whenever used herein is intended to indicate the presence of specified aspects, integers, steps, components, but not to prevent the presence or addition of one or more other aspects, integers, steps, components or groups thereof.

As used herein the term "flavoring substance" is intended to encompass any food grade substance that is capable of imparting a detectable taste impression, typically at concentrations below 1% by weight, more preferably below 0.1% by weight. Weight. Suitable examples of one or more flavoring substances include alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpene hydrocarbons, nitrogenous or sulfurous heterocyclic compounds and essential oils, and said one or more flavoring substances may be of natural or synthetic origin. Many of these are listed in reference texts such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or later versions, or other works of a similar nature, as well as in the literature. patent patent in the field of flavors. It will be clear to the skilled person that the type of flavoring substance added entirely would depend on the type of product to which the composition is added.

The terms "ppt", "ppb" and "ppm" as used herein refer to amounts expressed in parts per trillion respectively, 1 ppt corresponding to 1 ng / kg; parts per billion, 1 ppb corresponding to 1 pg / kg; and parts per million, 1 ppm corresponding to 1 mg / kg. These expressions are common terms in the taste and fragrance technique and are understood by the skilled person to have the meaning given herein.

Preferably, the taste composition contains at least 120 ppt, more preferably at least 300 ppt, even more preferably at least 1.2 ppb, more preferably at least 6 ppb of the present taste modulating substances. In another preferred embodiment, the composition contains less than 1,000 ppm, preferably less than 200 ppm, more preferably less than 50 ppm and more preferably less than 10 ppm of the present taste modulating substances.

In a preferred embodiment, the taste composition according to the invention comprises a flavoring substance in an amount of at least 0.5 wt%, preferably at least 1 wt%, based on the total weight of the composition.

Typically, in the present taste composition, taste modulating substances and one or more flavoring substances as defined hereinbefore are employed in a weight ratio of less than 1:50, preferably less than 1: 100. more preferably less than 1: 1,000 and more preferably in a weight ratio of less than 1: 10,000. The taste composition according to the present invention may suitably be prepared as a liquid, paste or powder. In a particularly preferred embodiment, the taste composition is a free flowing powder. Typically the present flavoring compositions also comprise a flavoring material. As used herein, the term "taste carrier material" encompasses a filler material that is substantially neutral from a taste standpoint, that is, that does not significantly alter the organoleptic properties of flavoring ingredients. Said carrier may be a liquid or a solid. Suitable examples of liquid carriers include emulsifier systems, that is, a solvent system and a surfactant system, or a solvent commonly used in perfumery or flavors. Suitable limiting examples of solvents commonly used in flavors may include compounds such as propylene glycol, triacetin, triethyl citrate, benzyl alcohol, ethanol, vegetable oils or terpenes. Examples of solid carriers include absorbent gums or polymers or encapsulation materials. Examples of such materials, for example, may comprise wall forming and plasticizing materials such as mono, di- or trisaccharides, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetates, polyvinyl alcohols, proteins or pectins, or the like. materials cited in reference texts such as H. Scherz, hydrokolloids: Stabilisatoren, Dickungs- und Gehermittel in Lebensmittel, Band 2 der Schriftenreihe Lebensmittelchemie, Lebensmittelqualitat, Behr's VerlagGmbH & Co., Hamburg, 1996.

Typical examples of flavor compositions according to the present invention include flavoring flavorings, dairy flavoring, sour flavoring, sweet flavoring and mint flavoring, flavoring and dairy flavoring being particularly preferred. The present flavor composition advantageously contains at least 0.5% by weight of a processed flavor, in particular a processed flavor containing cysteine derived from Maillard reaction products.

The present flavor compositions defined hereinbefore are typically prepared by composition of one or more of the flavoring substances with a solution containing at least 10 ppb, preferably at least 50 ppb of the present flavor modulating substances or edible salt thereof. The preparation of taste compositions containing said taste modulating substances at extremely low concentrations is facilitated by the composition of a solution of these taste modulating substances with one or more of the flavoring substances. In particular, this method offers the advantage that it allows accurate dosing of taste modulating substances. Typically, the solution containing the taste modulating substances and / or edible salts thereof is composed with the remainder of the taste composition in a weight ratio of less than 1: 1, preferably less than 1: 5 and more. preferably less than 1:10. It is noted that the solution may suitably contain one or more flavoring substances, especially highly potent flavoring substances. The solvent employed in the solution may be any food grade solvent that is permitted for use in flavor compositions. Examples of suitable solvents include ethanol, water, triglyceride oil and propylene glycol.

A third aspect of the invention relates to a product selected from the group of foodstuffs, beverages, pharmaceuticals, oral care products and tobacco products, preferably from the group of foodstuffs and beverages, said product comprising an amount of modulation of flavor of one or more of the present flavor modulating substances selected from the group of substances represented by formula (I), edible salts thereof and edible esters thereof as defined hereinbefore.

Typically, the present product comprises at least 0.3 ppt of one or more of the taste modulating substances present. More preferably, products of the invention comprise at least 0.6 ppt, more preferably at least 1.5 ppt, more preferably at least 30 ppt of one or more of the taste modulating substances according to formula (I) or edible salts. of these. Typically, the above-mentioned products preferably contain the taste modulating substances at a concentration of no more than 5 ppm, preferably no more than 2.5 ppm, more preferably no more than 1 ppm, even more. preferably no more than 250 ppb, more preferably no more than 50 ppb. The precise level at which the present substances are incorporated depends on the nature (s) of the taste modulation substance (s) and the nature of the product, as will be clear to the skilled person, and as will be illustrated in the examples.

Preferred examples of foodstuffs according to the present invention include soups, sauces, assortments, broths, light meals, cheese products, salad dressings, seasonings, margarines, cake, bread, pastry and pasta noodles.

A preferred example of a beverage according to the present invention includes a dairy drink. The term 'tobacco products' as used herein refers to any type of tobacco product for smoking as well as non-smoking applications. It is further noted that tobacco products are available for both smoke and non-smoke applications. The use of flavor modulating substances present in tobacco substitutes is also encompassed by the present invention.

Suitable examples of oral care products according to the present invention include toothpastes, mouthwashes, dental floss, antiplaque compositions, and anti-gingivitis.

More preferably, according to the invention, the product is selected from the group of foodstuffs and beverages.

Still, according to another preferred embodiment of the invention, the food or drink contains sodium chloride and / or monosodium glutamate. As explained hereinbefore, the presence of NaCI and MSG greatly increases the taste modulation potency of the substances of the invention. More preferably, the food or beverage contains at least 0.01 wt% NaCl and / or 0.001 wt% MSG.

A fourth aspect of the invention relates to a taste enhancing method of a product selected from the group of foodstuffs, beverages, pharmaceuticals, oral care products and tobacco products, said method comprising incorporating into said product an amount of taste modulation of one or more of the present taste modulation substances selected from the group of substances represented by formula (I), edible salts thereof and edible esters thereof as defined hereinbefore.

Particularly preferred examples of taste modulating substances, products and amounts according to the invention are as described hereinabove.

A fifth aspect of the invention relates to the use of one or more flavor modulating substances selected from the group of substances represented by formula (I), edible salts thereof and edible esters thereof for flavor enhancement of a product selected from the group. of foodstuffs, beverages, pharmaceuticals, oral care products and tobacco products.

Preferred examples of taste modulating substances, products and amounts according to the invention are as described hereinbefore.

As mentioned hereinabove, the taste modulating substances present are particularly suitable for modulation, especially enhancement and / or complementation of salty taste printing, umami printing, sweet taste printing, complexity and continuity. Accordingly, a preferred embodiment of the invention relates to the above defined use for enhancing and / or complementing salt flavor printing, umami printing, sweet taste printing, flavor complexity and flavor continuity. Complexity and continuity are terms commonly used in the flavoring technique to denote flavor qualities also referred to as "integrity and taste" and "long lasting and expanding" respectively.

A sixth aspect of the invention relates to a process for producing a taste modulating substance represented by formula (I), an edible salt thereof or an edible ester thereof, said process comprising reacting a suitably protected amine represented by the formula NH 2 R, wherein R has the same meaning as hereinbefore defined with respect to formula (I) with an activated carboxylate derivative represented by formula (III): (ii) wherein X has the same meaning as as defined hereinbefore with respect to formula (I), typically by heating combinations of such starting materials. As will be appreciated by the skilled person, suitably protected as used herein, it means that all reactive groups of the molecule are protected by protecting groups which are known in the art except the primary amine which must be derived with carboxylic acid. . The term activated carboxylic acid typically embraces (mixed) anhydrides, esters, acid chlorides or carboxylic acid bromides as will be recognized by the skilled person. It has been found that in order to obtain the carboxylic acid derivative and a nucleotide according to formula (I), it is typically preferred to first prepare the corresponding nucleoside derivative and prepare the phosphate ester thereof in a second step, as will be shown. in the attached examples. The present method of preparing taste modulating substances comprises processes that make use of conventional reactions. Preferably said reaction is performed by refluxing the reactants in an organic solvent or a mixture of organic solvents, for example DMF / pyridine, for a period of from 0.1 to 10 hours. In accordance with the present processes, reaction products are typically obtained as a precipitate and may be isolated by evaporation of the solvent and optionally also purified using any of the techniques known to the skilled person, such as chromatography and crystallization.

According to another particularly preferred embodiment of the present process, a reaction of the purine, pyrimidine, nucleotide and / or nucleoside with a carboxylate is performed in the presence of a carbohydrate source. Typically, the reaction is performed by first preparing a mixture of (i) one or more amines represented by the formula NH 2 R; (ii) one or more of the carboxylates; and the carbohydrate source, followed by heating said mixture. Preferably, the carbohydrate source is incorporated into the mixture at a concentration of at least 0.5 wt%, more preferably at least 1 wt%.

In a particularly preferred embodiment of the present process, a process flavor preparation, preferably a Maillard flavor preparation, is produced by heating a mixture of (i) a carbohydrate source; (ii) a nitrogen source, said nitrogen source comprising 0.5 to 100 wt%, preferably 1 to 50 wt%, more preferably 2 to 25 wt%, of one or more purines, pyrimidines , nucleotides and / or nucleosides and (iii) one or more of the carboxylates represented by formula (II) above. The combination of nitrogen source and carbohydrate source preferably represents at least 1% by weight of the mixture before it is heated. More preferably, said mixture represents at least 5 wt% and more preferably at least 15 wt% of the mixture. Maillard flavor preparations obtained by said process will typically comprise one or more of the flavor modulating substances present. Thus, the above process preferably yields a Maillard flavor preparation comprising effective amounts of one or more substances according to formula (I) or salts thereof. The term "Maillard flavor preparation" as used herein refers to a flavor preparation which is obtained by heating a mixture of ingredients including a nitrogen source, preferably amino nitrogen, and a carbohydrate source, of preferably a reducing sugar. The terms "process flavor" or "reaction taste" which are used interchangeably herein refer to compositions or products obtained by thermal processing together with a protein nitrogen source and a carbohydrate source at a temperature, preferably, not exceeding 180 ° C. In the present process it is particularly preferred to heat the combination of carbohydrate source, nitrogen source and liquid phase to a temperature of from 60 to 180 ° C, more preferably from 100 to 140 ° C. According to a preferred embodiment, heating is performed over a period of 0.1 to 8 hours, preferably 0.5 to 7 hours.

According to a particularly preferred embodiment, the carboxylates are present in the mixture as a continuous liquid phase. The term "liquid" as used herein in relation to the continuous liquid phase refers to the fact that, especially under the heating conditions employed, the continuous phase exhibits fluid or flow behavior. In addition, it should be understood that the term liquid encompasses emulsions and suspensions.

According to a preferred embodiment of the present invention, the process is performed in a continuous liquid phase containing at least 40 wt%, more preferably at least 45 wt%, more preferably at least 50 wt% of the carboxylate. The present continuous liquid phase advantageously comprises water in an amount sufficient to liquefy the carboxylate, for example in an amount of at least 2 wt.%, More preferably at least 5 wt.%. It is preferred that the amount of water does not exceed 70 wt%, based on the total weight of the continuous liquid phase, preferably it does not exceed 60 wt%, more preferably it does not exceed 45 wt%.

Preferably, said continuous liquid phase comprises a carboxylic acid such as formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanic acid, oxalic acid, succinic acid, glutaric acid, fumaric acid, maleic acid, adipic acid, citric acid, pyruvic acid, oxalacetic acid, cinnamic acid, caffeic acid, benzoic acid, gallic acid, vanillic acid, anthranilic acid, ferulic acid or a salt thereof. In a particularly preferred embodiment, the carboxylic acid component is acetic acid. The carbohydrate source may be any type conventionally used in the field of process flavors and Maillard flavor preparations. Preferably the carbohydrate source comprises a reducing sugar. Non-limiting examples include ribose, xylose, glucose, fructose, ranose, lactose, maltose and sucrose. The present "nitrogen source", in addition to the substances represented by the above-mentioned formula NH-R, may further comprise a protein nitrogen source, autolysed yeasts, peptides, amino acids and / or their salts, decarboxylated amino acids, salts of the same and mixtures thereof. In a particularly preferred embodiment of the invention, the nitrogen source comprises a yeast extract, in particular a yeast extract comprising GMP in amounts ranging from 1 to 25 wt%, preferably from 2 to 20 wt%. Suitable examples of such yeast extracts include Aromild, containing approximately 10 wt% GMP, Umamex I, containing approximately 15 wt% GMP, Umamex II, containing approximately 4.4 wt% GMP and / or YEP 99, containing approximately 2.5% by weight of GMP. Aromild is a commercially available yeast extract sold by Kohjin. Umamex I and II and YEP 99 are commercially available from Kerry Biosciences. In a preferred embodiment of the present process, the nitrogen source and the carbohydrate source are employed in a weight ratio within the range of 1:20 to 20: 1. In another preferred embodiment, the weight ratio employed of carboxylates and / or salts thereof relative to the combination of carbohydrate source and nitrogen source is within the range 1: 1 to 20: 1, more preferably within the range 2: 1 to 10: 1. The present invention will now also be illustrated by the following examples, which are not intended to limit the scope of the invention as described hereinbefore and / or as defined in the claims.

Examples Example 1: Preparation of N-Acetyl Quanosine A solution of 11.3 g of guanosine in DMF / pyridine / acetic anhydride (50 ml each) was heated at reflux (116 ° C) for 3 hours. All liquids were distilled off (100 ° C / 3 kPa (30 mbar)), and the residue was dissolved in 80 ml methylene chloride. The methylene chloride solution was washed twice with 1M hydrochloric acid solution and twice with saturated sodium bicarbonate solution. The solvent was evaporated and the residue was taken up in a mixture of 50 ml THF, 40 ml methanol and 35 ml water. This solution was treated with a solution of 1.6 g of sodium hydroxide in 4 ml of water. The mixture was allowed to stand at room temperature for 20 minutes. 5 ml of acetic acid was added and the solution was concentrated to approximately 80 ml. A little isopropanol was added and the solution was cooled to -20 ° C. N-acetyl guanosine was filtered and dried in a vacuum oven at 50 ° C / 1 kPa (10 mbar) to yield 4 g of light brown powder. Using 1 H NMR spectroscopy, the product was shown to be N-acetyl guanosine.

Example 2: Preparation of N-acetyl-GMP 1.8 g of phosphoryl chloride were mixed with 7 ml of trimethyl phosphate and cooled to -10 ° C under a nitrogen atmosphere. To this solution, 1.6 g of acetyl guanosine (example 1) was added in small portions and under stirring keeping the temperature below -10 ° C. The mixture was stirred for 3 hours keeping the temperature below -5 ° C. The reaction mixture was dissipated by pouring the solution into 300 ml ice / water and subsequently the pH was adjusted to 2 with 33% sodium hydroxide. The solution was percolated on a column (diameter = 3 cm) containing 30 g of activated charcoal, washed with water to remove salts and eluted with a 28% ethanol / water / NH4OH (50/48/2) mixture consisting of 100 ml ethanol, 100 ml water and 4 ml 28% ammonia. The eluate was evaporated to dryness. The semisolid residue was taken up in ethanol / tert ether. methyl butyl and solids were filtered and dried in a vacuum oven at 60 ° C / 1 kPa (10 mbar) to yield 0.8 g of N-acetyl-GMP. Using 1 H NMR spectroscopy, it was confirmed that the product was N-acetyl-GMP.

Example 3: Six aqueous solutions were prepared: A. 0.5% salt and 0.05% MSG Β. 1 ppm GMP dissolved in solution A

C. 0.2 ppm of a process flavor containing 0.3% lactoil-GMP dissolved in solution A

D. 0.6 ppb lactoil-GMP dissolved in solution A

E. 1 ppb of acetyl-GMP in solution A

F. 30 ppb of acetyl-GMP in solution A

The solutions were tested by a professional sensory panel. Solution A was described as: "salty" Solution B was described as: "sweet", "prolonged umami" Solution C was described as: "sweet", "prolonged umami", "stronger than B" Solution D was described as : "sweet", "prolonged umami", "more salivating", "stronger than C" Solution E was described as: "salivating", "salty", "stronger than D" Solution F was described as: " salivant "," salty "," stronger than E "Example 4: Three aqueous solutions were prepared: A. 0.5% salt and 0.05% MSG B. 0.6 ppb lactoil-GMP dissolved in solution A

C. 0.1 ppt of acetyl-GMP in solution A

D. 10 ppt of acetyl-GMP in solution A

The solutions have been proven by a professional sensory panel. Solution A was described as: "salty" Solution B was described as: "sweet", "prolonged umami", "most salivating" Solution C was described as: "sweet", "umami". 40% of the panel found this detectable.

Solution D was described as: "sweet", "umami '. 100% of the panel found this detectable.

The taste intensities of solutions B and D are comparable.

Example 5: Four different tomato soup powder compositions were prepared by dry mixing the ingredients as shown in table 1.

Grams of each composition were mixed with 100 ml of hot water to obtain tomato soups. The different soups were tested and evaluated by a sensory panel. Product C, comprising α-cetyl-GMP as prepared in example 2, was clearly preferred over product B (50% salt reduction). Product D comprising lac-toyl-GMP was clearly preferred over product B (50% salt reduction). Despite the reduced salt content of products C and D, the perceived lack of salt in the products was comparable to that of product A. In addition, the taste of products C and D was described as having "more flavor", "more impression" , "more kokumr," long lasting "and" salivating ".

Example 6: Three yogurts were prepared according to the recipe in table 2.

Table 2 All products were tested and evaluated by a sensory panel. Products B and C were clearly preferred over product A. Product A was described as sweet, fruity, berry-like, tasteless and slightly bitter, while products B and C were described as sweet, fuller, berry-like flavor. natural, fruitful and more balanced. The intensity of products B and C was comparable.

Example 7: Preparation of a Process Flavor In a container, 90 g acetic acid, 10 g water, 2.5 g dextrose and 5 g salt are combined and mixed by stirring. To this mixture is added 22.5 g GMP of disodium salt. The mixture is stirred and heated at 100 ° C for 4 hours. The mixture is cooled to room temperature and 25 g of water is added resulting in a total of 155 g of product. 120 g of water is added to 37.2 g of this product. The pH of this mixture is adjusted to 6 using 50% NaOH solution. 88.8 g of Maltodextrin are dissolved in this mixture and the resulting solution is spray dried resulting in a final powder product.

Example 8: Process Flavor Evaluation Three aqueous solutions were prepared: A. 0.5% salt and 0.05% MSG B. 0.2 ppm product as prepared in example 7 dissolved in solution A C. 1 ppt of product as prepared in example 2 dissolved in solution A.

The solutions were tested by a professional sensory panel. Solution A has been described as: "salty". Solution B has been described as: "sweet", "umami". Solution C was described as: "sweet", "umamí '. The sensory effects of solutions B and C were comparable. The intensity of solution B was slightly weaker than solution C.

Example 9: Preparation of a N-Sucinyl GMP Process Flavor In a vessel 50 g succinic acid, 50 g water, 2.5 g dextrose and 5 g salt are combined and mixed by stirring. To this mixture, 22.5 g of disodium GMP is added. The mixture is stirred and heated at 100 ° C for 4 hours. The mixture is cooled to room temperature and 25 g of water is added resulting in a total of 155 g of product. 120 g of water is added to 37.2 g of this product. The pH of this mixture is adjusted to 6 using 50% NaOH solution. 88.8 g of Maltodextrin is dissolved in this mixture and the resulting solution is spray dried resulting in a final powder product.

Example 10: Taste Evaluation of N-Sucinyl GMP Process Three aqueous solutions were prepared: A. 0.5% salt and 0.05% MSG B. 10 ppm product as prepared in Example 9 dissolved in solution THE

C. 50 ppm product as prepared in example 9 dissolved in solution A

The solutions were tested by a professional sensory panel. Solution A was described as: "salty" and "umamí '. Solution B has been described as: "salivant", "umami", "salty", "long term" and "broth type". The perception of lack of salt and umami in solution B was stronger than in solution A. Solution C was described as stronger than solution B but still pleasant, especially the lack of salt was perceived to be sharper and more severe. strong.

Claims (8)

1. Flavor modulating substances, characterized in that they have the formula (I): (i) as well as edible salts and esters thereof; wherein X represents methyl; R represents a portion comprising a bicyclic fused ring system comprising a five membered heterocyclic ring and a six membered heterocyclic ring, each ring comprising at least two nitrogen atoms, and said five membered heterocyclic ring is still substituted with a ribose phosphate ester, and the -NRH moiety represents the guanosine 5'-monophosphate (GMP) residue. Taste modulating substances according to claim 1, characterized in that the - NHR moiety represents the N-acetyl GMP compound, edible salts thereof and edible esters thereof. Flavoring compositions, characterized in that they comprise at least 60 ppt of one or more flavor modulating substances as defined in claim 1 or 2, as well as at least 0.1% by weight of one or more flavoring substances. 4. Product selected from the group consisting of foodstuffs, beverages, pharmaceuticals, oral care products and tobacco products, characterized in that it comprises a taste modulation amount of one or more taste modulation substances as defined herein. in claim 1 or 2. Product according to Claim 4, characterized in that said amount of taste modulation is an amount of at least 0.3 ppt. 6. Method for improving the taste of a product selected from the group consisting of foodstuffs, beverages, pharmaceuticals, oral care products and tobacco products, characterized in that it comprises incorporating in said product an amount of modulation of flavor of one or more taste modulating substances as defined in claim 1 or 2. Method according to claim 6, characterized in that said amount of taste modulation is an amount of at least 0.3 ppt. Process for producing a flavor preparation, characterized in that it comprises heating a mixture of (i) a carbohydrate source; (ii) a nitrogen source, said nitrogen source comprising 0.5 to 100% by weight of one or more amines represented by the formula NhfeR, wherein R is as defined in claim 1; and (iii) one or more of carboxylic acids represented by formula (II) and / or salts thereof: wherein X is as defined in claim 1.