Acylated dihydrochalcones, methods of manufacture and uses thereof

Abstract

The present invention relates to the use of a compound of formula (I) or a mixture of two or more compounds of formula (I) for providing sweetness and / or modulating the sweetness of one or more sweet substances, and to a method for producing such a compound. Furthermore, the present invention relates to a compound of formula (I), a composition comprising such a compound, and a method for modulating the sweetness of one or more sweet substances.

Description

TECHNICAL FIELD

[0001] The present invention relates to the use of a compound of formula (I) or a mixture of two or more compounds of formula (I) for providing a sweet taste and / or modulating the sweet taste of one or more sweet-tasting substances, and a process for manufacturing such a compound. Furthermore, the present invention relates to a compound of formula (I), a composition comprising such a compound, and a method for modulating the sweet taste of one or more sweet-tasting substances. BACKGROUND

[0002] The sweet taste of foods and beverages containing high amounts of sugar is generally considered desirable by consumers. However, it is increasingly recognized that when high amounts of sugars, such as sucrose, glucose and fructose, are consumed, they have adverse effects on the health of the consumer. Potential negative effects of a high sugar diet include weight gain and associated cardiovascular problems, insulin resistance and type 2 diabetes, and oral health problems.

[0003] Sweet taste modulating taste solutions are an important tool to reduce the sugar content in sweet tasting foods by maintaining the overall taste profile. Existing solutions used in the flavor industry such as Advantame®, neohesperidin dihydrochalcone, rebaudioside, rubusoside, mogroside and erythritol have their own drawbacks such as bad aftertaste, bitter taste profile, low sweet taste modulation potency, and the fact that some compounds are provided as synthetic, non-natural compounds.

[0004] Stevia based extracts and isolates in sweet tea and monk fruit are widely used to improve the sweetness. Such natural sweet taste modulating systems are the preferred solution for today’s product developers. However, sweet taste modulating terpene glycosides such as rebaudioside, rubusoside and mogroside have inherent non-sugar like taste attributes as described above (such as bad aftertaste and bitterness). Dihydrochalcones are another class of sweet taste compounds such as neohesperidin dihydrochalcone, however, neohesperidin dihydrochalcone is an artificial compound.

[0005] In contrast, the hesperetin dihydrochalcone-4’-O-β-d-glucoside (HG) in its rhamnose-eliminated form represents a natural dihydrochalcone as it has been identified in a natural source material (Red mangrove) (Prakash et al., 2020).

[0006]

[0007] HG, compound 1

[0008] HG has been described as a sweetener compound in US 10,463,063 B2, which discloses that a 5 mg / kg aqueous solution of HG has no sweetness, 10 mg / kg HG is iso-sweet compared to 0.5% sucrose, and 20 mg / kg HG is iso-sweet compared to a 1% sucrose solution. Furthermore, the use of HG in sweetener formulations is also described in documents such as US 2022 / 0295833 A1.

[0009] HG can be obtained from the artificial compound neohesperidin dihydrochalcone via fermentation as described in CN 114181987 A, or via enzymatic derhamnization as described in CN 101787062 A, or from hesperidin via derhamnization and hydrogenation using a metal catalyst as described in CN 108220366 A.

[0010] However, as mentioned above, there is a significant demand for novel and improved sweetness and / or sweetness-modifying compounds. Summary of the Invention

[0011] Therefore, the main objective of this invention is to provide compounds that: provide sweetness, preferably improved sweetness; and / or regulate the sweetness of one or more sweeteners comprising a sweetener. Thus, the objective of this invention is to facilitate the reduction of the amount of sugar, sweeteners, or sweeteners in food or beverages while maintaining overall sweetness.

[0012] The main objective of this invention is to provide and / or adjust the sweetness of one or more sweeteners by means of a compound of formula (I) or a mixture of two or more compounds of formula (I).

[0013]

[0014] R1, R2, R3, and R4 are independently selected from the group consisting of: hydrogen, acetyl residue, propionyl residue, butyryl residue, valeryl residue, hexanoyl residue, heptayl residue, octanoyl residue, nonanoyl residue, and decanoyl residue.

[0015] At least one of R1, R2, R3, and R4 is not hydrogen.

[0016] Surprisingly, acylation of dihydrochalcone hesperidin dihydrochalcone-4'-O-β-d-glucoside (HG) was found to increase its sweetness and its sweetness-modifying properties. Therefore, compounds according to formula (I) exhibit both improved inherent sweetness and improved sweetness-modifying properties.

[0017] Surprisingly, the compound according to formula (I) provided a sweetness similar to HG or similar sweetness-modulating properties, however at much lower concentrations.

[0018] The term "where at least one of R1, R2, R3, and R4 is not hydrogen" should be understood as follows:

[0019] - Only one of R1, R2, R3, and R4 is hydrogen.

[0020] - Only two of R1, R2, R3, and R4 are hydrogen, or

[0021] Only three of R1, R2, R3, and R4 are hydrogen.

[0022] The non-hydrogen residues in R1, R2, R3, and R4 are selected from the following groups: acetyl residues, propionyl residues, butyryl residues, valeryl residues, hexanoyl residues, heptanyl residues, octanoyl residues, nonanoyl residues, and decanoyl residues.

[0023] Preferably, the use for providing sweetness describes its use as a sweetener.

[0024] The terms “sweetness adjustment,” “sweetness adjustment,” or “sweetness adjustment property” preferably refer to one or more of the following effects: increasing sweetness, increasing initial sweetness, improving mouthfeel, and altering (such as prolonging or reducing) the persistence of sweetness.

[0025] Depending on the specific application of the compounds or mixtures of compounds described herein, it may be desirable to prolong or reduce the duration of sweetness. Therefore, for example, it may be desirable to provide a particularly persistent sweetness. Surprisingly, it has been found that compounds or mixtures of compounds described herein can alter the duration of sweetness.

[0026] The term "adjusting the sweetness of one or more sweet substances" preferably refers to the sweetness of one or more sweet substances in a composition containing one or more sweet substances and / or the sweetness of a composition containing one or more sweet substances.

[0027] Preferably, the compound of formula (I), one, two, three or more, or all of them, is selected from the following:

[0028]

[0029]

[0030]

[0031]

[0032]

[0033] .

[0034] Preferably, R2, R3 and R4 are each hydrogen.

[0035] More preferably, the compound of formula (I), one, two, three or more, or all of them, is selected from the following:

[0036]

[0037]

[0038] .

[0039] If a compound is described by its chemical name and chemical structure, and there is any discrepancy between the name and the structure, then the compound shall be described by the provided chemical structure.

[0040] The term "sweetening substance" refers to any substance that has a sweet taste, especially sweeteners, but also to substances that cannot provide a sufficiently strong sweetness to qualify as sweeteners.

[0041] Surprisingly, it was found that compounds according to formula (I) can advantageously modulate the sweetness of one or more sweet substances.

[0042] More preferably, the sweeteners, one, two, three or more, or all of them, are selected from the group consisting of:

[0043] This includes natural sweeteners derived from plant extracts, preferably naturally occurring sweeteners such as sweet carbohydrates (e.g., sucrose, D-(+)-trehalose, lactose, maltose, D-(+)-melinotriose, melibiose, D-(+)-raffinose, paraginose, lactulose, D-fructose, D-(+)-allulose, D-glucose, D-galactose, D-(+)-allose, D-(+)-atrolose, D-(-)-gulose, D-(+)-mannose, D-(-)-iduroose, D-(+)-taroose, L-(+)-rhamnose, L-(-)-fucose, D-sorbose, D-mannose, D-(-)-tagatose, D-arabinose, L-arabinose, etc.). D-(+)-xylose, D-lythose, D-ribose, D-ribulose, D-(-)-erythritol, D-(+)-threoose, D-glyceraldehyde, maltodextrin), sugar alcohols (such as erythritol, threitol, arabinitol, ribitol, xylitol, sorbitol, mannitol, maltitol, isomaltitol, eugenol, lactitol), proteins (such as mirabilite, pentadine, indigofera oleifera, kiwifruit oleifera, curculigofera oleifera, carbapenem, areca catechin), D-amino acids (such as D-phenylalanine, D-tryptophan), or containing these amino acids and / or proteins, and physiologically acceptable salts of these amino acids and / or proteins.In particular, extracts or fractions of its sodium, potassium, calcium, or ammonium salts obtained from natural sources, steviol glycosides, steviosides, mono-, di-, tri-, or tetra-α-saccharified steviol glycosides or lebodiin, steviol disaccharides, lebodiin, lebodiin A, lebodiin B, lebodiin C, lebodiin D, lebodiin E, lebodiin F, lebodiin G, lebodiin H, lebodiin M, lebodiin N, lebodiin X, durqueside, suavioside, mono-, di-, tri-, or tetra-α-saccharified suavioside, suavioside A, suavioside B, suavioside G, suavioside H, suavioside I, suavioside J, Ginsenoside 1, Ginsenoside 2, Gentiana macrophylla 1, Gentiana macrophylla 2, Gentiana macrophylla 3, Gentiana macrophylla 4, Abrusoside A, Abrusoside B, Abrusoside C, Abrusoside D, Cyclocarioside A, Cyclocarioside I, Osladin, Pteridoside A, Strogin 1, Strogin 2, Strogin 4, Pteridoside A, Dihydroquercetin-3-acetate, Perilla frutescens, Telosmoside A15, Glycyrrhizin IV, Decacoside Glycosides, including pterocaryoside, qingqianliu glycoside, soapberry sesquiterpene glycoside, trans-anestigmoside, bryonodulcoside, carnosifloside, scandenoside, gypenosides, hematoxylin, anthocyanins, chlorogenic acid, albizia saponins, night-blooming jasmine glycoside, gaudichaudioside, and balansin. A. balansin; B. mogrosides, such as mogroside V, hernandulcin, monadine, glycyrrhetinic acid and its derivatives, especially glycyrrhizin, preferably glycyrrhizin ammonium salt; extracts or enriched fractions of such extracts, such as Maranta or Stevia subspecies extracts, especially Stevia rebaudiana, Stevia leaf extract, Swingle extract, especially Momordica charantia or Siratia grosvenorii / Luo-Han-Guo, Glycyrrhiza subspecies extracts, especially Glycyrrhiza glabra or Glycyrrhiza uracilii, Rubus subspecies extracts, especially extracts of sweet tea or raspberry containing balshinone, Mycetia balansae, preferably containing balansin A and / or balansin B;

[0044] The synthetic sweetener is preferably selected from the group consisting of: magap, sodium cyclohexylsulfamate or other physiologically acceptable salts of cyclohexylsulfamate, acesulfame K, saccharin, sodium saccharin, aspartame, superaspartame, neotame, alitame, adventitia, perilla stigma, sucralose, lugduname, carrelame, sucrononate and sucrooctate.

[0045] Particularly preferred is that the one, two, three or more or all of the sweet substances are selected from the group consisting of: sucrose, fructose, glucose, steviol glycoside, rebaudioside, rebaudioside A, rebaudioside M, mono-, di-, tri- or tetra-α-saccharified steviol glycoside or rebaudioside, stevia glycoside, mono-, di-, tri- or tetra-α-saccharified stevia glycoside.

[0046] The term "mixture of two or more compounds of formula (I)" refers to a compound containing two or more of formula (I) or a mixture composed of two or more compounds of formula (I).

[0047] Preferably, a compound of formula (I) or a mixture of two or more compounds of formula (I) is used, said compound or said mixture being preferably used to adjust the sweetness of one or more sweeteners, said compound or said mixture being used in an amount that is perceived as having the same sweetness as or lower than that of a 5%, preferably 2.5%, preferably 1.5% aqueous sucrose solution.

[0048] Compounds of formula (I) can be prepared by chemical acylation and enzymatic acylation. HG, hesperidin dihydrochalcone, hesperidin dihydrochalcone, or mixtures thereof can be used as starting materials. Acylation can be synthetic or enzymatic, as described in the examples below.

[0049] The present invention further relates to a method for manufacturing a compound of formula (I), the method comprising the following steps:

[0050] i) Provide one or two or all of the compounds selected from the group consisting of hesperidin dihydrochalcone, hesperidin dihydrochalcone and hesperidin dihydrochalcone-4'-O-β-d-glucoside (HG);

[0051] ii) Provide one or more acyl donors;

[0052] iii) Mix the compound provided in step i) and the acyl donor provided in step ii) to subject the compound provided in step i) to chemical acylation or enzymatic acylation.

[0053] HG, hesperidin dihydrochalcone, hesperidin dihydrochalcone, or mixtures thereof can be provided as plant extracts, such as red winter jasmine extract.

[0054] Therefore, preferably, in step i) of the method according to the invention, a plant extract comprising one, two or all of the compounds selected from the group consisting of hesperidin dihydrochalcone, hesperidin dihydrochalcone and hesperidin dihydrochalcone-4'-O-β-d-glucoside (HG) is provided, preferably wherein the plant extract is a red wintersnake extract.

[0055] As an example of providing such an extract, plant material, particularly leaves of *Hemiberlesia lingua*, can be subjected to solvent extraction at temperatures ranging from 0°C to the boiling points of the solvents. For extraction, the ratio of plant material to solvent can be between 1:10 and 1:30, preferably between 1:5 and 1:25. Preferably, the solvent is selected from the group consisting of water, subcritical or supercritical water, methanol, ethanol, and mixtures thereof. The solvent can be removed, and the extract can be purified by solid-phase adsorption. The adsorbent can be, for example, polystyrene or a mixture of polystyrene and other components. Preferably, water and ethanol are used as solvents, wherein the weight ratio of water to ethanol is at least 1:3, and the extraction temperature is between 30°C and 50°C, preferably between 35°C and 45°C. Alternatively, extracts of plant material such as *Hemiberlesia lingua* are commercially available.

[0056] Preferably, the acylation in step iii) of the method according to the invention is chemical acylation. This acylation can be performed according to the following scheme.

[0057]

[0058] Preferably, the acylation in step iii) of the method according to the invention is enzymatic acylation. In this case, a compound selected from the group consisting of hesperidin dihydrochalcone, hesperidin dihydrochalcone, and hesperidin dihydrochalcone-4'-O-β-d-glucoside (HG) is incubated with an acyl donor and an enzyme, preferably a lipase.

[0059] Therefore, preferably, the acylation in step iii) is enzymatic acylation, and wherein the enzyme is an esterase, preferably a lipase, and preferably wherein the lipase is a lipase obtained from a microorganism selected from the group consisting of: Candida antarctica A, Candida antarctica B, Candida pleuropsus, Burkholderia cepacia, Rhizopus, Rhizopus spp., Rhizopus javanica, Yersinia lipolytica, Geotrichum candida, Aspergillus niger, Aspergillus oryzae, Pseudomonas alcaligenes, Pseudomonas mendoza, Thermophilus spp., and Chromobacterium spp.

[0060] Preferably, the one, two, three or more, or all acyl donors are selected from the group consisting of: acetyl donors, propionyl donors, butyryl donors, valeryl donors, hexanoyl donors, heptanyl donors, octanoyl donors, nonanoyl donors, and decanoyl donors.

[0061] Typically, in order to produce compounds as described herein, the acyl donor is an ester having the corresponding acyl residue. For example, if a compound having propionyl residues at R1, R2, R3 and / or R4 is to be produced, the acyl donor is an ester having propionyl residues.

[0062] Preferably, the acetyl donor as described herein is selected from the group consisting of: triacetylglycerol, acetic acid, methyl acetate, ethyl acetate, acetic anhydride, and mixtures thereof.

[0063] Preferably, the propionyl donor as described herein is selected from the group consisting of: tripropionyl ester, propionic acid, methyl propionate, ethyl propionate, and mixtures thereof.

[0064] Preferably, the butyryl donor as described herein is selected from the group consisting of glyceryl tributyrate, butyric acid, methyl butyrate, ethyl butyrate, and mixtures thereof.

[0065] Preferably, the valeryl donor as described herein is selected from the group consisting of: glyceryl trivalerate, valeric acid, methyl valerate, ethyl valerate, and mixtures thereof.

[0066] Preferably, the hexanoyl donor as described herein is selected from the group consisting of: trihexanoic acid glyceride, hexanoic acid, methyl hexanoate, ethyl hexanoate, and mixtures thereof.

[0067] Preferably, the heptanyl donor as described herein is selected from the group consisting of: triheptanyl glycerol, heptanic acid, methyl heptanate, ethyl heptanate, and mixtures thereof.

[0068] Preferably, the octanoyl donor as described herein is selected from the group consisting of: trioctanoic acid glyceride, octanoic acid, methyl octanoate, ethyl octanoate, and mixtures thereof.

[0069] Preferably, the nonanoyl donor as described herein is selected from the group consisting of: glyceryl trinonanoate, nonanoic acid, methyl nonanoate, ethyl nonanoate, and mixtures thereof.

[0070] Preferably, the decyl donor as described herein is selected from the group consisting of: tridecanoic acid glyceride, decanoic acid, methyl decanoate, ethyl decanoate, and mixtures thereof.

[0071] Preferably, the acyl donors, or one, two, three or more, or all of them, are selected from the group consisting of: triacetin, acetic acid, methyl acetate, ethyl acetate, acetic anhydride, tripropionyl glycerol, propionic acid, methyl propionate, ethyl propionate, tributyric acid, butyric acid, methyl butyrate, ethyl butyrate, trivalerate, valerate, methyl valerate, ethyl valerate, trihexanoate, hexanoate, methyl hexanoate, ethyl hexanoate, triheptanoate, heptanoate, methyl heptanoate, ethyl heptanoate, tricaprylic acid, caprylic acid, methyl caprylic acid, ethyl caprylic acid, trinonanoate, nonanoic acid, methyl nonanoate, ethyl nonanoate, tridecanoate, decanoic acid, methyl decanoate, and ethyl decanoate.

[0072] The present invention further relates to a compound according to formula (I),

[0073]

[0074] The compounds mentioned therein are selected from the following:

[0075]

[0076]

[0077]

[0078]

[0079]

[0080] .

[0081] As described herein, it was surprisingly found that acylation of dihydrochalcone hesperidin dihydrochalcone-4'-O-β-d-glucoside (HG) increased its sweetness and its sweetness-modifying properties. Therefore, compounds according to formula (I) exhibit both improved inherent sweetness and improved sweetness-modifying properties.

[0082] Surprisingly, the compound according to formula (I) provided a sweetness similar to HG or similar sweetness-modulating properties, however at much lower concentrations.

[0083] Preferably, R2, R3, and R4 of the compound according to the invention are each hydrogen. Therefore, R1 is selected from the group consisting of acetyl residues, propionyl residues, butyryl residues, valeryl residues, hexanoyl residues, and heptanyl residues.

[0084] More preferably, the compounds according to the present invention are selected from the following:

[0085]

[0086]

[0087] .

[0088] The present invention further relates to a composition comprising a compound according to the invention.

[0089] Preferably, the composition further comprises one or more sweeteners selected from the group consisting of:

[0090] Including natural sweeteners derived from plant extracts, preferably naturally occurring sweeteners such as sweet carbohydrates (e.g., sucrose, D-(+)-trehalose, lactose, maltose, D-(+)-melinotriose, melibiose, D-(+)-raffinose, paraginose, lactulose, D-fructose, D-(+)-allulose, D-glucose, D-galactose, D-(+)-allose, D-(+)-atrolose, D-(-)-gulose, D-(+)-mannose, D-(-)-iduroose, D-(+)-taroose, L-(+)-rhamnose, L-(-)-fucose, D-sorbose, D-mannose, D-(-)-tagatose, D-arabinose, L-arabinose, etc.). D-(+)-xylose, D-lythose, D-ribose, D-ribulose, D-(-)-erythritol, D-(+)-threoose, D-glyceraldehyde, maltodextrin), sugar alcohols (such as erythritol, threitol, arabinitol, ribitol, xylitol, sorbitol, mannitol, maltitol, isomaltitol, eugenol, lactitol), proteins (such as mirabilite, pentadine, indigofera oleifera, kiwifruit oleifera, curculigofera oleifera, carbapenem, areca catechin), D-amino acids (such as D-phenylalanine, D-tryptophan), or containing these amino acids and / or proteins, and physiologically acceptable salts of these amino acids and / or proteins.In particular, extracts or fractions of its sodium, potassium, calcium, or ammonium salts obtained from natural sources, steviol glycosides, steviosides, mono-, di-, tri-, or tetra-α-saccharified steviol glycosides or lebodiin, steviol disaccharides, lebodiin, lebodiin A, lebodiin B, lebodiin C, lebodiin D, lebodiin E, lebodiin F, lebodiin G, lebodiin H, lebodiin M, lebodiin N, lebodiin X, durqueside, suavioside, mono-, di-, tri-, or tetra-α-saccharified suavioside, suavioside A, suavioside B, suavioside G, suavioside H, suavioside I, suavioside J, Ginsenoside 1, Ginsenoside 2, Gentiana macrophylla 1, Gentiana macrophylla 2, Gentiana macrophylla 3, Gentiana macrophylla 4, Abrusoside A, Abrusoside B, Abrusoside C, Abrusoside D, Cyclocarioside A, Cyclocarioside I, Osladin, Pteridoside A, Strogin 1, Strogin 2, Strogin 4, Pteridoside A, Dihydroquercetin-3-acetate, Perilla frutescens, Telosmoside A15, Glycyrrhizin IV, Decacoside Glycosides, including pterocaryoside, qingqianliu glycoside, soapberry sesquiterpene glycoside, trans-anestigmoside, bryonodulcoside, carnosifloside, scandenoside, gypenosides, hematoxylin, anthocyanins, chlorogenic acid, albizia saponins, night-blooming jasmine glycoside, gaudichaudioside, and balansin. A. balansin; B. mogrosides, such as mogroside V, hernandulcin, monadine, glycyrrhetinic acid and its derivatives, especially glycyrrhizin, preferably glycyrrhizin ammonium salt; extracts or enriched fractions of such extracts, such as Maranta or Stevia subspecies extracts, especially Stevia rebaudiana, Stevia leaf extract, Swingle extract, especially Momordica charantia or Siratia grosvenorii / Luo-Han-Guo, Glycyrrhiza subspecies extracts, especially Glycyrrhiza glabra or Glycyrrhiza uracilii, Rubus subspecies extracts, especially extracts of sweet tea or raspberry containing balshinone, Mycetia balansae, preferably containing balansin A and / or balansin B;

[0091] The synthetic sweetener is preferably selected from the group consisting of: magap, sodium cyclohexylsulfamate or other physiologically acceptable salts of cyclohexylsulfamate, acesulfame K, saccharin, sodium saccharin, aspartame, superaspartame, neotame, alitame, adventitia, perilla stigma, sucralose, lugduname, carrelame, sucrononate and sucrooctate.

[0092] Particularly preferred is that the composition comprises one or more sweeteners selected from the group consisting of: sucrose, fructose, glucose, steviol glycoside, rebaudioside, rebaudioside A, rebaudioside M, mono-, di-, tri- or tetra-α-saccharified steviol glycoside or rebaudioside, stevia glycoside, mono-, di-, tri- or tetra-α-saccharified stevia glycoside.

[0093] Particularly preferred is that the composition comprises one or more sweetening substances selected from the group consisting of: hesperidin, hesperidin dihydrochalcone, naringenin, phloroglucinol, sennaol, hypersennaol, foetin, neohesperidin dihydrochalcone, naringin dihydrochalcone, phloroglucinol, extracts of Hydrangea macrophylla containing an active amount of foetin, particularly extracts of Oamacha, Amacha, or Amagi amacha varieties.

[0094] Further surprising findings revealed that combining two or more compounds of formula (I) provides synergistic effects.

[0095] Therefore, it is preferred that the composition according to the invention comprises two or more compounds of formula (I).

[0096] Therefore, it is preferred that the composition according to the invention comprises two or more compounds of formula (I), wherein at least two of R1, R2, R3 and R4 are acetyl residues, preferably wherein R1 and at least one of R2, R3 and R4 are acetyl residues.

[0097] Therefore, it is preferred that the composition according to the invention comprises two or more compounds of formula (I), wherein at least two of R1, R2, R3 and R4 are propionyl residues, preferably wherein R1 and at least one of R2, R3 and R4 are propionyl residues.

[0098] Therefore, it is preferred that the composition according to the invention comprises two or more compounds of formula (I), wherein at least two of R1, R2, R3 and R4 are butyryl residues, preferably wherein R1 and at least one of R2, R3 and R4 are butyryl residues.

[0099] Therefore, it is preferred that the composition according to the invention comprises two or more compounds of formula (I), wherein at least two of R1, R2, R3 and R4 are valeryl residues, preferably wherein R1 and at least one of R2, R3 and R4 are valeryl residues.

[0100] Therefore, it is preferred that the composition according to the invention comprises two or more compounds of formula (I), wherein at least two of R1, R2, R3 and R4 are hexanoyl residues, preferably wherein R1 and at least one of R2, R3 and R4 are hexanoyl residues.

[0101] Therefore, it is preferred that the composition according to the invention comprises two or more compounds of formula (I), wherein at least two of R1, R2, R3 and R4 are heptanoyl residues, preferably wherein R1 and at least one of R2, R3 and R4 are heptanoyl residues.

[0102] Therefore, it is preferred that the composition according to the invention comprises two or more compounds of formula (I), wherein at least two of R1, R2, R3 and R4 are octanoyl residues, preferably wherein R1 and at least one of R2, R3 and R4 are octanoyl residues.

[0103] Therefore, it is preferred that the composition according to the invention comprises two or more compounds of formula (I), wherein at least two of R1, R2, R3 and R4 are nonanoyl residues, preferably wherein R1 and at least one of R2, R3 and R4 are nonanoyl residues.

[0104] Therefore, it is preferred that the composition according to the invention comprises two or more compounds of formula (I), wherein at least two of R1, R2, R3 and R4 are decyl residues, preferably wherein R1 and at least one of R2, R3 and R4 are decyl residues.

[0105] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 9 and compound 25.

[0106] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 9 and compound 41.

[0107] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 9 and compound 57.

[0108] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 9 and compound 73.

[0109] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 9 and compound 89.

[0110] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 9 and compound 105.

[0111] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 9 and compound 121.

[0112] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 9 and compound 137.

[0113] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 25 and compound 41.

[0114] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 25 and compound 57.

[0115] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 25 and compound 73.

[0116] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 25 and compound 89.

[0117] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 25 and compound 105.

[0118] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 25 and compound 121.

[0119] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 25 and compound 137.

[0120] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 41 and compound 57.

[0121] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 41 and compound 73.

[0122] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 41 and compound 89.

[0123] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 41 and compound 105.

[0124] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 41 and compound 121.

[0125] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 41 and compound 137.

[0126] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 57 and compound 73.

[0127] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 57 and compound 89.

[0128] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 57 and compound 105.

[0129] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 57 and compound 121.

[0130] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 57 and compound 137.

[0131] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 73 and compound 89.

[0132] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 73 and compound 105.

[0133] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 73 and compound 121.

[0134] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 73 and compound 137.

[0135] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 89 and compound 105.

[0136] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 89 and compound 121.

[0137] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 89 and compound 137.

[0138] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 105 and compound 121.

[0139] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 105 and compound 137.

[0140] More preferably, the composition according to the invention comprises two or more compounds of formula (I), wherein the composition comprises compound 121 and compound 137.

[0141] Preferably, based on the total weight of the composition, the amount of the compound according to formula (I) in the composition is in the range of 0.0001 wt.-% to 75 wt.-%; more preferably in the range of 0.0002 wt.-% to 50 wt.-%; more preferably in the range of 0.0003 wt.-% to 25 wt.-%; more preferably in the range of 0.0005 wt.-% to 10 wt.-%; more preferably in the range of 0.00075 wt.-% to 5 wt.-%; more preferably in the range of 0.001 wt.-% to 1 wt.-%

[0142] Preferably, the term "amount of the compound according to formula (I) in the composition" refers to the total amount of all compounds according to formula (I) present in the composition.

[0143] The present invention further relates to a product comprising a composition according to the present invention.

[0144] Preferably, based on the total weight of the product, the amount of the compound according to formula (I) in the product is in the range of 0.0001 wt.-% to 1 wt.-%; more preferably in the range of 0.0002 wt.-% to 0.1 wt.-%; more preferably in the range of 0.0003 wt.-% to 0.01 wt.-%; and more preferably in the range of 0.0005 wt.-% to 0.005 wt.-%

[0145] Preferably, the amount of the compound according to formula (I) in the product relative to the total product is at most 50 ppm, preferably at most 25 ppm, particularly preferably at most 20 ppm, especially preferably at most 10 ppm, further preferably at most 7.5 ppm, and even more preferably at most 5 ppm.

[0146] Preferably, the amount of the compound according to formula (I) in the product is at least 3 ppm, preferably at least 5 ppm, particularly preferably at least 10 ppm, especially preferably at least 15 ppm, further preferably at least 20 ppm, more preferably at least 25 ppm, and even more preferably at least 50 ppm, relative to the total product.

[0147] Preferably, the term "amount of the compound according to formula (I) in the product" refers to the total amount of all compounds according to formula (I) present in the product.

[0148] The products according to the invention can be selected from the group consisting of: pharmaceutical products for oral administration, oral care products, liquid and solid nutritional or recreational products, and semi-finished products.

[0149] Preferably, semi-finished products refer to substances, products, or commodities that have not yet completed the production or manufacturing process and have not been sold to or provided for use or consumption by consumers and / or customers in the food service or catering industry. Therefore, semi-finished products preferably refer to products, commodities, or articles intended for further industrial processing and / or use in industrial processing.

[0150] Preferably, the semi-finished product should be understood as a product unsuitable for use as a ready-to-eat food. The semi-finished product is transformed into a ready-to-eat food simply by mixing it with at least one other ingredient (e.g., to reduce the concentration of a flavoring agent) and optionally by further processing steps (e.g., heating, freezing).

[0151] Preferably, the semi-finished product is selected from substances, products or commodities to be used in food, such as aromatic compositions, extracts made from vegetables or fruits, pastes, powders, oils or grouts, flavorings, toppings, seasoning mixtures, granular or pulverized foods.

[0152] Preferably, based on the total weight of the semi-finished product, the amount of the compound according to formula (I) in the semi-finished product is in the range of 0.0001 wt.-% to 75 wt.-%; more preferably in the range of 0.0002 wt.-% to 50 wt.-%; more preferably in the range of 0.0003 wt.-% to 25 wt.-%; more preferably in the range of 0.0005 wt.-% to 10 wt.-%; more preferably in the range of 0.00075 wt.-% to 5 wt.-%; more preferably in the range of 0.001 wt.-% to 1 wt.-%

[0153] Preferably, the nutritional or recreational product may be selected from the group consisting of: (low-calorie) baked goods (e.g., bread, biscuits, cakes, other baked goods), confectionery (e.g., cereal bars, chocolate, chocolate bars, other bar products, fruit gummies, sugar-coated pills, hard and soft caramel, chewing gum), non-alcoholic beverages (e.g., cocoa, coffee, green tea, black tea, (green, black) tea beverages rich in (green, black) tea extracts, rooibos tea, other herbal teas, fruit-containing soft drinks, isotonic beverages, refreshing beverages, nectar, fruit and vegetable juices, fruit or vegetable juice preparations), and instant beverages (e.g., instant...). Instant cocoa beverages, instant tea beverages, instant coffee beverages), meat products (such as ham, fresh sausages or raw sausage products, flavored or cured fresh or salted meat products), eggs or egg products (dried eggs, egg whites, egg yolks), cereal products (such as breakfast cereals, cereal bars, pre-cooked rice products), dairy products (such as whole or low-fat or skim milk beverages, rice pudding, yogurt, kefir, cream cheese, soft cheese, hard cheese, milk powder, whey, butter, buttermilk, ice cream, products containing partially or completely hydrolyzed milk proteins), and products made from soy protein or other soy fractions (such as...). Soy milk and products made from it, beverages containing isolated or enzymatically treated soy protein, beverages containing soy flour, preparations containing soy lecithin, fermented products such as tofu or tempeh or products made from them, and mixtures with fruit preparations and optionally flavorings), dairy-like preparations (milk-type, yogurt-type, dessert-type, ice cream) derived from protein-rich plant materials (e.g., from seeds of oats, almonds, peas, lupins, lentils, broad beans, chickpeas, rice, rapeseed), non-dairy beverages rich in plant protein, and fruit preparations (e.g., jams, sorbets, fruit sauces, fruit fillings). Vegetable preparations (e.g., tomato sauce, sauces, dried vegetables, frozen vegetables, pre-cooked vegetables, boiled vegetables), snacks (e.g., baked or fried potato chips or potato dough products, corn or peanut extrusions), fats and oils or their emulsions (e.g., mayonnaise, remoulade, seasonings, in each case full-fat or low-fat), other ready-made dishes and soups (e.g., soup powders, instant soups, pre-cooked soups), flavorings, flavoring mixtures and especially seasonings used in the snack sector, sweetener preparations, tablets or sachets, and other preparations used to sweeten or whiten beverages.

[0154] The product may be a dietary supplement or pharmaceutical product in the form of capsules, tablets (uncoated and coated tablets, such as antacid-coated tablets), sugar-coated pills, granules, pellets, solid mixtures, dispersions in the liquid phase, as an emulsion, as a powder, as a solution, as a paste, or as other swallowable or chewable formulations.

[0155] Oral care products are formulations commonly used by those skilled in the art for cleaning and caring for the mouth and throat and for freshening breath. Known and common oral care products are in the form of creams, gels, pastes, foams, emulsions, suspensions, aerosols, sprays, as well as capsules, granules, lozenges, tablets, candies, or chewing gum; this list of dosage forms is not limiting in terms of possible applications. Such formulations are used for cleaning and caring for the structure of teeth and the oral cavity and for freshening breath. In particular, oral care products according to the invention are preferably selected from the group consisting of: toothpaste, tooth gel, mouthwash, oral cleanser, gargle liquid, oral or pharyngeal spray (pump or aerosol spray), lozenges, tablets, candies, chewing gum, chewable candies, and dental care chewing gum.

[0156] Preferably, the unit "ppm" refers to weight and describes a unit corresponding to, for example, mg / kg.

[0157] Furthermore, the present invention relates to a method for adjusting the sweetness of one or more sweet substances, the method comprising the following steps:

[0158] a) Provide one or more compounds according to the invention;

[0159] b) Provide one or more sweeteners; and

[0160] c) Mix the compound provided in step a) with one or more sweeteners provided in step b).

[0161] Preferably, the one, two, three or more, or all of the sweet substances are selected from the group consisting of:

[0162] Including natural sweeteners derived from plant extracts, preferably naturally occurring sweeteners such as sweet carbohydrates (e.g., sucrose, D-(+)-trehalose, lactose, maltose, D-(+)-melinotriose, melibiose, D-(+)-raffinose, paraginose, lactulose, D-fructose, D-(+)-allulose, D-glucose, D-galactose, D-(+)-allose, D-(+)-atrolose, D-(-)-gulose, D-(+)-mannose, D-(-)-iduroose, D-(+)-taroose, L-(+)-rhamnose, L-(-)-fucose, D-sorbose, D-mannose, D-(-)-tagatose, D-arabinose, L-arabinose, etc.). D-(+)-xylose, D-lythose, D-ribose, D-ribulose, D-(-)-erythritol, D-(+)-threoose, D-glyceraldehyde, maltodextrin), sugar alcohols (such as erythritol, threitol, arabinitol, ribitol, xylitol, sorbitol, mannitol, maltitol, isomaltitol, eugenol, lactitol), proteins (such as mirabilite, pentadine, indigofera oleifera, kiwifruit oleifera, curculigofera oleifera, carbapenem, areca catechin), D-amino acids (such as D-phenylalanine, D-tryptophan), or containing these amino acids and / or proteins, and physiologically acceptable salts of these amino acids and / or proteins.In particular, extracts or fractions of its sodium, potassium, calcium, or ammonium salts obtained from natural sources, steviol glycosides, steviosides, mono-, di-, tri-, or tetra-α-saccharified steviol glycosides or lebodiin, steviol disaccharides, lebodiin, lebodiin A, lebodiin B, lebodiin C, lebodiin D, lebodiin E, lebodiin F, lebodiin G, lebodiin H, lebodiin M, lebodiin N, lebodiin X, durqueside, suavioside, mono-, di-, tri-, or tetra-α-saccharified suavioside, suavioside A, suavioside B, suavioside G, suavioside H, suavioside I, suavioside J, Ginsenoside 1, Ginsenoside 2, Gentiana macrophylla 1, Gentiana macrophylla 2, Gentiana macrophylla 3, Gentiana macrophylla 4, Abrusoside A, Abrusoside B, Abrusoside C, Abrusoside D, Cyclocarioside A, Cyclocarioside I, Osladin, Pteridoside A, Strogin 1, Strogin 2, Strogin 4, Pteridoside A, Dihydroquercetin-3-acetate, Perilla frutescens, Telosmoside A15, Glycyrrhizin IV, Decacoside Glycosides, including pterocaryoside, qingqianliu glycoside, soapberry sesquiterpene glycoside, trans-anestigmoside, bryonodulcoside, carnosifloside, scandenoside, gypenosides, hematoxylin, anthocyanins, chlorogenic acid, albizia saponins, night-blooming jasmine glycoside, gaudichaudioside, and balansin. A. balansin; B. mogrosides, such as mogroside V, hernandulcin, monadine, glycyrrhetinic acid and its derivatives, especially glycyrrhizin, preferably glycyrrhizin ammonium salt; extracts or enriched fractions of such extracts, such as Maranta or Stevia subspecies extracts, especially Stevia rebaudiana, Stevia leaf extract, Swingle extract, especially Momordica charantia or Siratia grosvenorii / Luo-Han-Guo, Glycyrrhiza subspecies extracts, especially Glycyrrhiza glabra or Glycyrrhiza uracilii, Rubus subspecies extracts, especially extracts of sweet tea or raspberry containing balshinone, Mycetia balansae, preferably containing balansin A and / or balansin B;

[0163] The synthetic sweetener is preferably selected from the group consisting of: magap, sodium cyclohexylsulfamate or other physiologically acceptable salts of cyclohexylsulfamate, acesulfame K, saccharin, sodium saccharin, aspartame, superaspartame, neotame, alitame, adventitia, perilla stigma, sucralose, lugduname, carrelame, sucrononate and sucrooctate.

[0164] Particularly preferred is that the one, two, three or more or all of the sweet substances are selected from the group consisting of: sucrose, fructose, glucose, steviol glycoside, rebaudioside, rebaudioside A, rebaudioside M, mono-, di-, tri- or tetra-α-saccharified steviol glycoside or rebaudioside, stevia glycoside, mono-, di-, tri- or tetra-α-saccharified stevia glycoside.

[0165] Preferably, the method according to the present invention further includes the following steps:

[0166] b.2) Provide one or more sweeteners selected from the group consisting of: hesperidin, hesperidin dihydrochalcone, naringenin, phloroglucinol, sennaol, hypersennaol, floridin, neohesperidin dihydrochalcone, naringin dihydrochalcone, phloroglucinol, extracts of Hydrangea macrophylla containing active amounts of floridin, particularly extracts of Oamacha, Amacha, or Amagi amacha varieties.

[0167] In step c), the compound provided in step a), one or more sweeteners provided in step b), and one or more sweetness-modifying substances provided in step b.2) are mixed. In this case, the provided components can be mixed simultaneously or subsequently. For example, the compound provided in step a) and the sweetener provided in step b) can be mixed first, and then mixed with the sweetness-modifying substance provided in step b.2). Furthermore, in subsequent mixing, as described herein, the provided components can be mixed in any order. Attached Figure Description

[0168] Figure 1 The LC-HRMS chromatogram of the acetylated product of HG obtained in Example 1 is described. The signal from the electro-fogging detector is shown.

[0169] Figure 2 The LC-HRMS chromatogram of the acetylated product of HG obtained in Example 2 is described. The signal from the electrosmosis detector is shown. Peak 3 corresponds to compound 9.

[0170] Figure 3 The LC-HRMS chromatogram of the acetylated product of HG obtained in Example 3 is described. The signal from the electrosmosis detector is shown. Peak 3 corresponds to compound 25.

[0171] Figure 4 The LC-HRMS chromatogram of the acetylated product of HG obtained in Example 3 is described. The signal from the electrosmosis detector is shown. Peak 3 corresponds to compound 41.

[0172] Figure 5 The LC-HRMS chromatogram of the acetylated product of HG obtained in Example 3 is described. The signal from the electrosmosis detector is shown. Peak 3 corresponds to compound 57.

[0173] Figure 6 The LC-HRMS chromatogram of the acetylated product of HG obtained in Example 3 is described. The signal from the electrosmosis detector is shown. Peak 3 corresponds to compound 73.

[0174] Figure 7 The LC-HRMS chromatogram of the acetylated product of HG obtained in Example 3 is described. The signal from the electrosmosis detector is shown. Peak 3 corresponds to compound 89.

[0175] Figure 8 The LC-HRMS chromatogram of the acetylated product of HG obtained in Example 3 is described. The signal from the electro-vapor detector is shown. Peak 3 corresponds to compound 105.

[0176] Figure 9 The LC-HRMS chromatogram of the acetylated product of HG obtained in Example 3 is described. The signal from the electro-vapor detector is shown. Peak 3 corresponds to compound 137.

[0177] Other aspects and advantages of the invention will be apparent from the following description of preferred embodiments. Detailed Implementation

[0178] Examples

[0179] Example 1 : Chemical acylation of HG

[0180] 500 mg of hesperidin dihydrochalcone-4'-O-β-d-glucoside (HG) was dissolved in 10 mL of tetrahydrofuran, followed by the addition of 100 μL of acetyl acetate and 0.15 μL of triethylamine at room temperature. The solution was stirred at room temperature for 18 hours. The reaction mixture was quenched with 15 mL of H₂O and the aqueous layer was extracted with ethyl acetate (3 × 10⁻⁶ mL). The combined organic layers were dried over Na₂SO₄ and the solvent was removed under reduced pressure.

[0181]

[0182] The compounds obtained by LC-HRMS analysis (results shown in...) Figure 1 middle).

[0183] Example 2: Enzymatic acylation of HG

[0184] Hesperidin dihydrochalcone-4'-O-β-d-glucoside (HG) was resuspended at a concentration of 5 g / L in triacetin, ethyl acetate, acetone, or acetonitrile and dissolved by incubation at 70 °C. Lipase Novozym 435 (Novozymes, Lyngby, Denmark) was added to the solution at a concentration of 10 g / L, and ethyl acetate was added at a concentration of 3 g / L in the presence of acetonitrile or acetone. The solution was incubated at 70 °C with stirring for 4.5 h. After incubation, the lipase was removed by filtration. The sample was analyzed by HPLC-MS (results shown in...). Figure 2 (in Chinese), the analysis includes the following results:

[0185]

[0186] Example 3: Enzymatic acylation of HG

[0187] Hesperidin dihydrochalcone-4'-O-β-d-glucoside (HG) was resuspended in acetone or acetonitrile at a concentration of 5 g / L and dissolved by incubation at 70 °C. Lipase Novozym 435 (Novozymes, Lyngby, Denmark) was added to the solution at a concentration of 10 g / L, and acyl donors of the group consisting of ethyl acetate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl hexanoate, ethyl heptaate, ethyl octanoate, ethyl nonanoate, or ethyl decanoate were added at concentrations of 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, or 7 g / L, respectively.

[0188] The solution was incubated at 70°C with stirring for 4.5 hours. After incubation, lipase was removed by filtration. The sample was analyzed by HPLC-MS (results shown in...). Figures 3 to 9 (In the middle), the analysis included the following results (peaks classified as nd were below the threshold and could not be determined):

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196] Example 4: Sweetness of compounds of formula (I)

[0197] Compounds 9, 41, 57, 73, and 89 were provided as described in Example 3 and purified to >95% using preparative chromatography. Sensory evaluation was performed using the obtained compounds.

[0198] The intrinsic sweetness of the compounds was determined by a panel of 20 trained members. The intrinsic sweetness was determined by evaluating the sweetness of aqueous solutions of different concentrations of the compounds relative to a 1.5% sucrose solution. Then, the concentrations that did not provide a statistically significant difference (p < 0.05) between the samples and the 1.5% sucrose control (in both directions: higher or lower sweetness) were determined, i.e., the concentrations of each compound that provided the same sweetness as the 1.5% sucrose solution.

[0199] As shown in the table below, the concentration of the acylated compound exhibiting the same sweetness as a 1.5% sucrose solution is approximately 1 / 3 to 1 / 17 of the required concentration of HG (non-acylated). Therefore, acylation of HG provides a significant increase in intrinsic sweetness.

[0200]

[0201] Example 5: Sweetness of mixtures of compounds of formula (I)

[0202] As described in Example 3, a mixture of butyrylated HG and a mixture of pentanoylated HG are provided.

[0203] The intrinsic sweetness was determined as described in Example 4. The results are shown in the table below. As shown in the table, the concentration of the acylated compound exhibiting the same sweetness as a 1.5% sucrose solution was approximately 1 / 5 to 1 / 8 of the desired concentration of HG (non-acylated). Therefore, acylation of HG provided a significant increase in intrinsic sweetness.

[0204]

[0205] Example 6: Modulation of the sweetness of a sweetening substance (sucrose)

[0206] Prepare a 5% sucrose solution. Compounds 9, 41, 57, 73, and 89 were provided as described in Example 3 and purified to >95% by preparative chromatography.

[0207] Sensory characteristics of sucrose solution (control) and sucrose solution including HG (control), compound 9, compound 41, compound 57, compound 73 or compound 89 were determined by comparing effects, intensity and mouthfeel by a trained panel of flavorists.

[0208] The addition of HG was found to increase impact, strength, and mouthfeel. Furthermore, it was found that lower concentrations of acylated HG were required to provide comparable results.

[0209]

[0210] Example 7: Modulation of the sweetness of a sweetening substance (sucrose)

[0211] The sensory effects of compounds 9, 41, 57, 73, and 89 on a 5% sucrose aqueous solution were analyzed by a series of paired comparative tests (Duo tests) conducted by a trained sensory panel (n=20). Samples were coded and randomly assigned.

[0212] The compound tested was found to increase the sweetness of sucrose solution. Surprisingly, the observed effect was similar to that observed for HG, however, in which the compound according to formula (I) was applied at a lower concentration.

[0213]

[0214] Example 8: Modulation of the sweetness of a sweetening substance

[0215] A sugar matrix (5% sucrose + 0.1% citric acid) is provided. Additionally, sweeteners RS (20% steviol glycosides), SG (90% steviol oligoglucosides), HC (8% hesperidin dihydrochalcone), LHG (52% mogroside V), and sweetness modifiers PD (>95% fosetyl-Aldrich), HT (>85% hesperidin), and PH (>98% phlorizin) are provided and added to the sugar matrix to create different samples (A).

[0216] Compound 41 at a dose of 2 mg / kg or compound 57 at a dose of 1.2 mg / kg was added to the sample to obtain sample (B).

[0217] A panel of five flavorists (n=5) used a 0-9 scale to compare the different flavor descriptors between samples (A) and (B).

[0218] Panel members were instructed to neutralize each sample with tap water between tastings and to define the strength of the descriptor for each sample before tasting the next. After tasting each of RS, SG, HC, LHG, PD, HT, or PH (sample (A)), samples with added RS, SG, HC, LHG, PD, HT, or PH+ compounds (41 or 57) were tasted (sample (B)), and the strength of each sample was compared to the matrix.

[0219] Example 8.1 : Compound 41

[0220] Descriptor "Initial Sweetness":

[0221]

[0222] Descriptor "Overall Sweetness":

[0223]

[0224] Descriptor "texture":

[0225]

[0226] Descriptor "persistent sweetness":

[0227]

[0228] Example 8.2: Compound 57

[0229] Descriptor "Initial Sweetness":

[0230]

[0231] Descriptor "Overall Sweetness":

[0232]

[0233] Descriptor "texture":

[0234]

[0235] Descriptor "persistent sweetness":

[0236]

[0237] Example 9: Sweetness modulation properties of compounds in a lemonade base with low sugar content

[0238] Compound 41 at a dose of 5 mg / kg or compound 57 at a dose of 3 mg / kg were applied to different low-sugar lemonade bases to restore the overall flavor and sweetness of the low-sugar bases. A panel of five flavorists (n=5) determined different descriptors and assigned strengths from 0 to 9.

[0239] The lemonade base is available in "full sugar", "low sugar", "stevioside mixture", "sugar-free base Suc / Ace K" and "sugar-free base Asp / Ace K", as follows:

[0240]

[0241] Lemonade base is "low sugar":

[0242]

[0243] Lemonade base "stevioside blend":

[0244]

[0245] Lemonade base "Sugar-free base Suc / Ace K":

[0246]

[0247] Lemonade base "Sugar-free base Asp / Ace K":

[0248]

[0249] Application Examples

[0250] Application Example 1

[0251] Spray-dried formulations used in flavored finished products and as semi-finished products.

[0252]

[0253] Place drinking water in a container and dissolve maltodextrin and gum arabic in it. Then, emulsify the flavoring agent in the carrier solution using Turrax. The temperature of the spray solution should not exceed 30°C. The mixture is then spray-dried (inlet nominal temperature: 185°C-195°C, outlet nominal temperature: 70°C-75°C).

[0254] Application Example 2

[0255] Combination with sweeteners

[0256] Add 90g of sucrose and 10g of tagatose to 0.5g of spray-dried semi-finished product from Application Example 1 (according to Formulation A, Formulation D, or Formulation G) and mix. The product can be used, for example, as a sweetener.

[0257] Application Example 3

[0258] chewing gum

[0259]

[0260] Mix and knead portions A through D thoroughly. The raw material can be processed, for example, into ready-to-eat chewing gum in the form of thin strips.

[0261] Application Example 4

[0262] toothpaste

[0263]

[0264] In each case, premix components A and B separately and stir thoroughly under vacuum at 25°C–30°C for 30 minutes. Premix component C and add it to A and B; add D and stir the mixture thoroughly under vacuum at 25°C–30°C for 30 minutes. After decompression, the toothpaste is complete and ready for filling.

[0265] Application Example 5

[0266] Sugar-free hard candy

[0267]

[0268] Palatinite is mixed with water and melted at 165°C, then cooled to 115°C. Other ingredients are added, and the mixture is poured into molds after mixing. After hardening, the mixture is removed from the molds and individually packaged.

[0269] Application Example 6

[0270] Low-sugar tomato sauce

[0271] A: Comparative formulations containing sugar

[0272] B: A comparative formulation with a low sugar content (compared to A).

[0273] CH: The formulation according to the invention having a low sugar content (compared to A) and 6''-O-butyryl-HG, i.e., compound (41).

[0274]

[0275] Mix the ingredients in the order described, homogenize the finished tomato sauce using a mixer, pour it into a bottle, and sterilize it.

[0276] Low-sugar tomato sauce

[0277] A: Comparative formulations containing sugar

[0278] B: A comparative formulation with a low sugar content (compared to A).

[0279] CH: A formulation according to the invention having a low sugar content (compared to A) and 6''-O-pentanoyl-HG, i.e., compound (73).

[0280]

[0281] Mix the ingredients in the order described, homogenize the finished tomato sauce using a mixer, pour it into a bottle, and sterilize it.

[0282] Application Example 7

[0283] Low-sugar fruit gummies

[0284]

[0285] Note: Polydextrose itself is a low-calorie, non-sweet polysaccharide.

[0286] Application Example 8

[0287] Carbonated beverages (flavor profile: cola)

[0288] A: Sugary (comparative) beverages

[0289] B: Low-calorie beverages

[0290] C: Low-calorie beverages

[0291] D: Low-calorie beverages

[0292] E: Low-calorie beverages

[0293]

[0294] Each solid component or ingredient is individually mixed with water to form 100g. The resulting concentrate is then allowed to mature overnight at ambient temperature. Finally, 1 part concentrate is mixed with 5 parts carbonated water, filled into a bottle, and sealed.

[0295] Application Example 9

[0296] Drinkable chocolate instant powder

[0297] Formulation A: Standard Formulation

[0298] Formulation BD: Formulation according to the present invention

[0299]

[0300] Standard dosage in milk for use in preparing chocolate beverages: 6.9 g / L.

[0301] Application Example 10

[0302] Instant peachy iced tea

[0303] Formulation A: Standard Formulation

[0304] Formulation BD: Formulation according to the present invention

[0305]

[0306] The standard dosage of water used in the preparation of peach iced tea beverage is 7.5% by weight.

[0307] Application Example 11

[0308] iced tea

[0309] Comparative example containing sucrose (A)

[0310]

[0311] Mix the ingredients into the bottle in the listed order and sterilize.

Claims

1. Use of a compound of formula (I) or a mixture of two or more compounds of formula (I) for providing sweetness and / or modulating the sweetness of one or more sweeteners. R1, R2, R3, and R4 are independently selected from the group consisting of: hydrogen, acetyl residue, propionyl residue, butyryl residue, valeryl residue, hexanoyl residue, heptayl residue, octanoyl residue, nonanoyl residue, and decanoyl residue. At least one of R1, R2, R3, and R4 is not hydrogen.

2. The use according to claim 1, wherein the compound of formula (I) is selected from the following: 。 3. The use according to claim 1 or 2, wherein R2, R3 and R4 are each hydrogen.

4. The use according to any one of the preceding claims, wherein the compound of formula (I) is selected from the following: 。 5. The use according to any one of the preceding claims, wherein the one, two, three or more, or all of the sweeteners are selected from the group consisting of: Including natural sweeteners derived from plant extracts, preferably naturally occurring sweeteners such as sweet carbohydrates (e.g., sucrose, D-(+)-trehalose, lactose, maltose, D-(+)-melinotriose, melibiose, D-(+)-raffinose, paraginose, lactulose, D-fructose, D-(+)-allulose, D-glucose, D-galactose, D-(+)-allose, D-(+)-atrolose, D-(-)-gulose, D-(+)-mannose, D-(-)-iduroose, D-(+)-taroose, L-(+)-rhamnose, L-(-)-fucose, D-sorbose, D-mannose, D-(-)-tagatose, D-arabinose, L-arabinose, etc.). D-(+)-xylose, D-lythose, D-ribose, D-ribulose, D-(-)-erythritol, D-(+)-threoose, D-glyceraldehyde, maltodextrin), sugar alcohols (such as erythritol, threitol, arabinitol, ribitol, xylitol, sorbitol, mannitol, maltitol, isomaltitol, eugenol, lactitol), proteins (such as mirabilite, pentadine, indigofera oleifera, kiwifruit oleifera, curculigofera oleifera, carbapenem, areca catechin), D-amino acids (such as D-phenylalanine, D-tryptophan), or containing these amino acids and / or proteins, and physiologically acceptable salts of these amino acids and / or proteins.In particular, extracts or fractions of its sodium, potassium, calcium, or ammonium salts obtained from natural sources, steviol glycosides, steviosides, mono-, di-, tri-, or tetra-α-saccharified steviol glycosides or lebodiin, steviol disaccharides, lebodiin, lebodiin A, lebodiin B, lebodiin C, lebodiin D, lebodiin E, lebodiin F, lebodiin G, lebodiin H, lebodiin M, lebodiin N, lebodiin X, durqueside, suavioside, mono-, di-, tri-, or tetra-α-saccharified suavioside, suavioside A, suavioside B, suavioside G, suavioside H, suavioside I, suavioside J, Ginsenoside 1, Ginsenoside 2, Gentiana macrophylla 1, Gentiana macrophylla 2, Gentiana macrophylla 3, Gentiana macrophylla 4, Abrusoside A, Abrusoside B, Abrusoside C, Abrusoside D, Cyclocarioside A, Cyclocarioside I, Osladin, Pteridoside A, Strogin 1, Strogin 2, Strogin 4, Pteridoside A, Dihydroquercetin-3-acetate, Perilla frutescens, Telosmoside A15, Glycyrrhizin IV, Decacoside Glycosides, including pterocaryoside, qingqianliu glycoside, soapberry sesquiterpene glycoside, trans-anestigmoside, bryonodulcoside, carnosifloside, scandenoside, gypenosides, hematoxylin, anthocyanins, chlorogenic acid, albizia saponins, night-blooming jasmine glycoside, gaudichaudioside, and balansin. A. balansin; B. mogrosides, such as mogroside V, hernandulcin, monadine, glycyrrhetinic acid and its derivatives, especially glycyrrhizin, preferably glycyrrhizin ammonium salt; extracts or enriched fractions of such extracts, such as Maranta or Stevia subspecies extracts, especially Stevia rebaudiana, Stevia leaf extract, Swingle extract, especially Momordica charantia or Siratia grosvenorii / Luo-Han-Guo, Glycyrrhiza subspecies extracts, especially Glycyrrhiza glabra or Glycyrrhiza uracilii, Rubus subspecies extracts, especially extracts of sweet tea or raspberry containing balshinone, Mycetia balansae, preferably containing balansin A and / or balansin B; The synthetic sweetener is preferably selected from the group consisting of: magap, sodium cyclohexylsulfamate or other physiologically acceptable salts of cyclohexylsulfamate, acesulfame K, saccharin, sodium saccharin, aspartame, superaspartame, neotame, alitame, adventitia, perilla stigma, sucralose, lugduname, carrelame, sucrononate and sucrooctate.

6. A method for manufacturing a compound of formula (I), the method comprising the steps of: i) Provide one or two or all of the compounds selected from the group consisting of hesperidin dihydrochalcone, hesperidin dihydrochalcone and hesperidin dihydrochalcone-4'-O-β-d-glucoside (HG); ii) Provide one or more acyl donors; iii) Mix the compound provided in step i) and the acyl donor provided in step ii) to subject the compound provided in step i) to chemical acylation or enzymatic acylation.

7. The method of claim 6, wherein the one, two, three or more, or all of the acyl donors are selected from the group consisting of: acetyl donors, propionyl donors, butyryl donors, valeryl donors, hexanoyl donors, heptanyl donors, octanoyl donors, nonanoyl donors, and decanoyl donors. Preferably, the one, two, three or more, or all of the acyl donors are selected from the group consisting of: triacetin, acetic acid, methyl acetate, ethyl acetate, acetic anhydride, tripropionyl glycerol, propionic acid, methyl propionate, ethyl propionate, tributyric acid, butyric acid, methyl butyrate, ethyl butyrate, trivalerate, valerate, methyl valerate, ethyl valerate, trihexanoate, hexanoate, methyl hexanoate, ethyl hexanoate, triheptanoate, heptanoate, methyl heptanoate, ethyl heptanoate, tricaprylic acid, caprylic acid, methyl caprylic acid, ethyl caprylic acid, trinonanoate, nonanoic acid, methyl nonanoate, ethyl nonanoate, tridecanoate, decanoic acid, methyl decanoate, and ethyl decanoate.

8. The method according to claim 6 or 7, wherein the acylation in step iii) is enzymatic acylation, and wherein the enzyme is a lipase. Preferably, the lipase is obtained from microorganisms selected from the group consisting of: Candida antarctica A, Candida antarctica B, Candida pleuropsis, Burkholderia cepacia, Rhizopus, Rhizopus mirifica, Rhizopus javanica, Yersinia lipophila, Geotrichum candida, Aspergillus niger, Aspergillus oryzae, Pseudomonas alcaligenes, Pseudomonas mendoza, Thermophilus spp., and Chromobacterium viscous.

9. The method according to any one of claims 6 to 8, wherein step i) provides a plant extract comprising one or two or all of the compounds selected from the group consisting of hesperidin dihydrochalcone, hesperidin dihydrochalcone, and hesperidin dihydrochalcone-4'-O-β-d-glucoside (HG). Preferably, the plant extract is red winter snake mushroom extract.

10. A compound according to formula (I), The compounds mentioned therein are selected from the following: 。 11. The compound according to claim 10, wherein R2, R3 and R4 are each hydrogen.

12. The compound according to claim 10 or 11, wherein the compound is selected from the group consisting of: 。 13. A composition comprising the compound according to any one of claims 10 to 12 and one or more sweeteners selected from the group consisting of: Including natural sweeteners derived from plant extracts, preferably naturally occurring sweeteners such as sweet carbohydrates (e.g., sucrose, D-(+)-trehalose, lactose, maltose, D-(+)-melinotriose, melibiose, D-(+)-raffinose, paraginose, lactulose, D-fructose, D-(+)-allulose, D-glucose, D-galactose, D-(+)-allose, D-(+)-atrolose, D-(-)-gulose, D-(+)-mannose, D-(-)-iduroose, D-(+)-taroose, L-(+)-rhamnose, L-(-)-fucose, D-sorbose, D-mannose, D-(-)-tagatose, D-arabinose, L-arabinose, etc.). D-(+)-xylose, D-lythose, D-ribose, D-ribulose, D-(-)-erythritol, D-(+)-threoose, D-glyceraldehyde, maltodextrin), sugar alcohols (such as erythritol, threitol, arabinitol, ribitol, xylitol, sorbitol, mannitol, maltitol, isomaltitol, eugenol, lactitol), proteins (such as mirabilite, pentadine, indigofera oleifera, kiwifruit oleifera, curculigofera oleifera, carbapenem, areca catechin), D-amino acids (such as D-phenylalanine, D-tryptophan), or containing these amino acids and / or proteins, and physiologically acceptable salts of these amino acids and / or proteins.In particular, extracts or fractions of its sodium, potassium, calcium, or ammonium salts obtained from natural sources, steviol glycosides, steviosides, mono-, di-, tri-, or tetra-α-saccharified steviol glycosides or lebodiin, steviol disaccharides, lebodiin, lebodiin A, lebodiin B, lebodiin C, lebodiin D, lebodiin E, lebodiin F, lebodiin G, lebodiin H, lebodiin M, lebodiin N, lebodiin X, durqueside, suavioside, mono-, di-, tri-, or tetra-α-saccharified suavioside, suavioside A, suavioside B, suavioside G, suavioside H, suavioside I, suavioside J, Ginsenoside 1, Ginsenoside 2, Gentiana macrophylla 1, Gentiana macrophylla 2, Gentiana macrophylla 3, Gentiana macrophylla 4, Abrusoside A, Abrusoside B, Abrusoside C, Abrusoside D, Cyclocarioside A, Cyclocarioside I, Osladin, Pteridoside A, Strogin 1, Strogin 2, Strogin 4, Pteridoside A, Dihydroquercetin-3-acetate, Perilla frutescens, Telosmoside A15, Glycyrrhizin IV, Decacoside Glycosides, including pterocaryoside, qingqianliu glycoside, soapberry sesquiterpene glycoside, trans-anestigmoside, bryonodulcoside, carnosifloside, scandenoside, gypenosides, hematoxylin, anthocyanins, chlorogenic acid, albizia saponins, night-blooming jasmine glycoside, gaudichaudioside, and balansin. A. balansin; B. mogrosides, such as mogroside V, hernandulcin, monadine, glycyrrhetinic acid and its derivatives, especially glycyrrhizin, preferably glycyrrhizin ammonium salt; extracts or enriched fractions of such extracts, such as Maranta or Stevia subspecies extracts, especially Stevia rebaudiana, Stevia leaf extract, Swingle extract, especially Momordica charantia or Siratia grosvenorii / Luo-Han-Guo, Glycyrrhiza subspecies extracts, especially Glycyrrhiza glabra or Glycyrrhiza uracilii, Rubus subspecies extracts, especially extracts of sweet tea or raspberry containing balshinone, Mycetia balansae, preferably containing balansin A and / or balansin B; The synthetic sweetener is preferably selected from the group consisting of: magap, sodium cyclohexylsulfamate or other physiologically acceptable salts of cyclohexylsulfamate, acesulfame K, saccharin, sodium saccharin, aspartame, superaspartame, neotame, alitame, adventitia, perilla stigma, sucralose, lugduname, carrelame, sucrononate and sucrooctate.

14. A method for adjusting the sweetness of one or more sweeteners, the method comprising the steps of: a) Providing one or more compounds according to any one of claims 10 to 12; b) Provide one or more sweeteners; and c) Mix the compound provided in step a) with one or more sweeteners provided in step b). Preferably, the one, two, three or more, or all of the sweet substances are selected from the group consisting of: Including natural sweeteners derived from plant extracts, preferably naturally occurring sweeteners such as sweet carbohydrates (e.g., sucrose, D-(+)-trehalose, lactose, maltose, D-(+)-melinotriose, melibiose, D-(+)-raffinose, paraginose, lactulose, D-fructose, D-(+)-allulose, D-glucose, D-galactose, D-(+)-allose, D-(+)-atrolose, D-(-)-gulose, D-(+)-mannose, D-(-)-iduroose, D-(+)-taroose, L-(+)-rhamnose, L-(-)-fucose, D-sorbose, D-mannose, D-(-)-tagatose, D-arabinose, L-arabinose, etc.). D-(+)-xylose, D-lythose, D-ribose, D-ribulose, D-(-)-erythritol, D-(+)-threoose, D-glyceraldehyde, maltodextrin), sugar alcohols (such as erythritol, threitol, arabinitol, ribitol, xylitol, sorbitol, mannitol, maltitol, isomaltitol, eugenol, lactitol), proteins (such as mirabilite, pentadine, indigofera oleifera, kiwifruit oleifera, curculigofera oleifera, carbapenem, areca catechin), D-amino acids (such as D-phenylalanine, D-tryptophan), or containing these amino acids and / or proteins, and physiologically acceptable salts of these amino acids and / or proteins.In particular, extracts or fractions of its sodium, potassium, calcium, or ammonium salts obtained from natural sources, steviol glycosides, steviosides, mono-, di-, tri-, or tetra-α-saccharified steviol glycosides or lebodiin, steviol disaccharides, lebodiin, lebodiin A, lebodiin B, lebodiin C, lebodiin D, lebodiin E, lebodiin F, lebodiin G, lebodiin H, lebodiin M, lebodiin N, lebodiin X, durqueside, suavioside, mono-, di-, tri-, or tetra-α-saccharified suavioside, suavioside A, suavioside B, suavioside G, suavioside H, suavioside I, suavioside J, Ginsenoside 1, Ginsenoside 2, Gentiana macrophylla 1, Gentiana macrophylla 2, Gentiana macrophylla 3, Gentiana macrophylla 4, Abrusoside A, Abrusoside B, Abrusoside C, Abrusoside D, Cyclocarioside A, Cyclocarioside I, Osladin, Pteridoside A, Strogin 1, Strogin 2, Strogin 4, Pteridoside A, Dihydroquercetin-3-acetate, Perilla frutescens, Telosmoside A15, Glycyrrhizin IV, Decacoside Glycosides, including pterocaryoside, qingqianliu glycoside, soapberry sesquiterpene glycoside, trans-anestigmoside, bryonodulcoside, carnosifloside, scandenoside, gypenosides, hematoxylin, anthocyanins, chlorogenic acid, albizia saponins, night-blooming jasmine glycoside, gaudichaudioside, and balansin. A. balansin; B. mogrosides, such as mogroside V, hernandulcin, monadine, glycyrrhetinic acid and its derivatives, especially glycyrrhizin, preferably glycyrrhizin ammonium salt; extracts or enriched fractions of such extracts, such as Maranta or Stevia subspecies extracts, especially Stevia rebaudiana, Stevia leaf extract, Swingle extract, especially Momordica charantia or Siratia grosvenorii / Luo-Han-Guo, Glycyrrhiza subspecies extracts, especially Glycyrrhiza glabra or Glycyrrhiza uracilii, Rubus subspecies extracts, especially extracts of sweet tea or raspberry containing balshinone, Mycetia balansae, preferably containing balansin A and / or balansin B; The synthetic sweetener is preferably selected from the group consisting of: magap, sodium cyclohexylsulfamate or other physiologically acceptable salts of cyclohexylsulfamate, acesulfame K, saccharin, sodium saccharin, aspartame, superaspartame, neotame, alitame, adventitia, perilla stigma, sucralose, lugduname, carrelame, sucrononate and sucrooctate.

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