Acylated dihydrochalcone, its manufacturing method and use

Abstract

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

Background Art

[0002] The sweetness of foods and beverages containing a significant amount of sugar is often recognized as desirable by consumers. However, there is a growing awareness that sugars such as sucrose, glucose, and fructose have harmful effects on the health of consumers when consumed in large amounts. Weight gain and related cardiovascular problems, insulin resistance and type 2 diabetes, and oral hygiene problems are some of the potential adverse effects of a high-sugar diet.

[0003] Sweetness-modulating taste solutions are an important tool for reducing the sugar content in sweetened foods by maintaining the overall taste profile. Existing solutions used in the flavor industry, such as advantame, neohesperedine dihydrochalcone, rebaudioside, rubusoside, mogroside, and erythritol, have their own drawbacks, such as a negative aftertaste, a bitter aspect, low sweetness-modulating efficacy, and some of the compounds being provided as synthetic non-natural compounds.

[0004] Extracts and isolates based on Stevia rebaudiana are widely used to enhance sweetness between Rubus suavissimus and Siraitia grosvenorii. These natural sweetness modifiers are a preferred solution for product developers today. However, sweetness modifier terpene glycosides such as rebaudioside, rubusoside, and mogroside possess inherent non-sugar-like taste attributes (negative aftertaste, bitterness, etc.), as mentioned above. Dihydrochalcones, such as neohesperidin dihydrochalcone, are another class of sweetening compounds, but these are artificial compounds.

[0005] In contrast, the rhamnosyl-de-rhamnosyl hesperetine dihydrochalcone-4'-O-β-d-glucoside (HG) is a natural dihydrochalcone, as identified in the natural source material (Balanophora harlandii) (Prakash et al., 2020).

[0006] [ka]

[0007] HG is described as a sweetness-modifying compound in Patent Document 1. According to that disclosure, 5 mg / kg of HG in water has no sweetness, 10 mg / kg of HG has the same sweetness as 0.5% sucrose, and 20 mg / kg of HG has the same sweetness as a 1% sucrose solution. Furthermore, the application of HG is also described in sweetener blends in Patent Document 2, etc.

[0008] HG can be obtained from the artificial compound neohesperidin dihydrochalcone via fermentation as described in Patent Document 3, via enzymatic derhamnosylation as described in Patent Document 4, or from hesperidin via derhamnosylation and hydrogenation using a metal catalyst as described in Patent Document 5.

[0009] However, as mentioned above, there is a great need for novel and improved sweetening and / or sweetening-modifying compounds. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] US Patent No. 10,463,063(B2) [Patent Document 2] U.S. Patent Application Publication No. 2022 / 0295833(A1) [Patent Document 3] Chinese Patent Application Publication No. 114181987(A) Specification [Patent Document 4] Chinese Patent Application Publication No. 101787062(A) Specification [Patent Document 5] Chinese Patent Application Publication No. 108220366(A) Specification [Overview of the project] [Problems that the invention aims to solve]

[0011] Therefore, a primary objective of the present invention was to provide compounds that produce sweetness, preferably improved sweetness, and / or modulate the sweetness of one or more sweetening substances, including sweeteners. Thus, one objective of the present invention was to facilitate the reduction of the amount of sugar, sweetening substances, or sweeteners in food or beverages while maintaining overall sweetness. [Means for solving the problem]

[0012] The main objective of the present invention is to be achieved by using a compound of the following formula (I) or a mixture of two or more compounds for providing sweetness and / or adjusting the sweetness of one or more sweetening substances.

[0013] [ka]

[0014] In the formula, R1, R2, R3, and R4 are independently selected from the group consisting of hydrogen, an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, and a decanoyl group, At least one of R1, R2, R3, and R4 is not hydrogen.

[0015] Surprisingly, the acylation of dihydrochalcone glucoside hesperetin dihydrochalcone-4'-O-β-d-glucoside (HG) has been found to increase its sweetness and its sweetness-modulating properties. Therefore, the compound of formula (I) exhibits improved sweetness and improved sweetness-modulating properties per se.

[0016] Surprisingly, the compound of formula (I) has been found to bring about a sweetness similar to HG or similar sweetness-modulating properties, but already at a much lower concentration.

[0017] The term "at least one of R1, R2, R3, and R4 is not hydrogen" should be understood as follows.

[0018] - Only one of R1, R2, R3, and R4 is hydrogen, - Only two of R1, R2, R3, and R4 are hydrogen, or - Only three of R1, R2, R3, and R4 are hydrogen,

[0019] Here, those among R1, R2, R3, and R4 that are not hydrogen are selected from the group consisting of an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, and a decanoyl group.

[0020] Preferably, the use for providing sweetness indicates use as a sweetener.

[0021] Terms such as "adjusting sweetness," "sweetness adjustment," and "sweetness adjustment characteristics" preferably refer to one or more effects selected from increasing sweetness, increasing the occurrence of sweetness, enhancing texture, and altering the lingering sweetness (e.g., extending or reducing it).

[0022] Depending on the specific application of the compounds or mixtures of compounds described herein, a long-lasting or subdued sweetness may be desirable. For example, it may be desirable to provide a particularly long-lasting sweetness. Surprisingly, it has been found that the compounds or mixtures of compounds described herein can alter the long-lasting sweetness.

[0023] The term "adjusting the sweetness of one or more sweetening substances" preferably refers to the sweetness of one or more sweetening substances in a composition containing one or more sweetening substances and / or the sweetness of a composition containing one or more sweetening substances.

[0024] Preferably, one, two, three or more, or all of the compounds of formula (I) are selected from the following compounds.

[0025] [Table 1]

[0026] [Table 2]

[0027] [Table 3]

[0028] [Table 4]

[0029] Particularly preferably, R2, R3, and R4 are hydrogen.

[0030] More preferably, one, two, three or more, or all of the compounds of formula (I) above are selected from the following compounds.

[0031] [Table 5]

[0032] [Table 6]

[0033] [Table 7]

[0034] If a compound is described by its chemical name and chemical structure, and there is a deviation between the name and the structure, the compound shall be described by the shown chemical structure.

[0035] The term "sweet substance" refers to any substance that has a sweet taste, especially sweeteners, but also includes substances that do not, on their own, produce enough sweetness to be considered a sweetener.

[0036] Surprisingly, it was found that the compound of formula (I) can favorably regulate the sweetness of one or more sweetening substances.

[0037] More preferably, the one, two, three or more, or all of the sweetening substances are selected from the group consisting of the following:

[0038] Natural sweeteners (one or more), preferably natural sweeteners including plant extracts, for example sweet carbohydrates (sucrose, D-(+)-trehalose, lactose, maltose, D-(+)-melizitose, melibiose, D-(+)-raffinose, palatinose, lactulose, D-fructose, D-(+)-allulose, D-glucose, D-galactose, D-(+)-allose, D-(+)-altrose, D-(-)-glucose, D-(+)-mannose, D-(-)-idos, D-(+)-talose, L-(+)- Rhamnose, L-(-)-fucose, D-sorbose, D-mannose, D-(-)-tagatose, D-arabinose, L-arabinose, D-(+)-xylose, D-lyxose, D-ribose, D-ribulose, D-(-)-erythrose, D-(+)-threose, D-glyceraldehyde, maltodextrin, etc., sugar alcohols (erythritol, threitol, arabitol, ribitol, xylitol, sorbitol, mannitol, maltitol, isomaltitol, dulcitol, lactitol, etc.), tan Proteins (such as miraculin, pentadin, monellin, thaumatin, curculin, blazein, mavinlin, etc.), D-amino acids (such as D-phenylalanine, D-tryptophan, etc.), or extracts or fractions obtained from natural sources containing these amino acids and / or proteins, and physiologically acceptable salts of these amino acids and / or proteins, in particular their sodium, potassium, calcium or ammonium salts, steviol glycoside, stevioside, mono-, di-, tri- or tetra-al Alpha-glycosylated stevioside or rebaudioside, steviolbiosid, rebaudioside, rebaudioside A, rebaudioside B, rebaudioside C, rebaudioside D, rebaudioside E, rebaudioside F, rebaudioside G, rebaudioside H, rebaudioside M, rebaudioside N, rebaudioside X, dulcoside, rubusoside, mono-, di-, tri- or tetra-alpha-glycosylated rubusoside, suavioside A, suavioside B, suavioside G, suavioside H, suavioside I, suavioside J,Bayunoside 1, Bayunoside 2, Florisoside 1, Florisoside 2, Florisoside 3, Florisoside 4, Abulsoside A, Abulsoside B, Abulsoside C, Abulsoside D, Cyclocarioside A, Cyclocarioside I, Oslandin, Polypodoside A, Strogin 1, Strogin 2, Strogin 4, Selligueanin A, Dihydroquercetin-3-acetate, Perillartin, Telosmoside A15, Periandrin IV, Pterocarioside, Cyclocarioside, Muclodioside, Trans-Anethole, Brioside, Brionoside, Brionodorcoside, Ca Runosifloside, candenoside, gypenoside, hematoxylin, cyanine, chlorogenic acid, albidiasaponin, telosmoside, goudichooside, balancin A, balancin B, mogrosides such as mogroside V, hernandulcin, monatin, glycyrrhetinic acid and its derivatives, especially glycyrrhizin, preferably glycyrrhizinammonium salt; extracts of Thaumatococcus or Stevia subspecies, especially Stevia japonica, Stevia leaf extract, Swingle extract, especially Momordica or Luo Han Guo or Luo Han Guo; subspecies of Glyceridium, especially Glyceridium Extracts such as extracts of Glycerrhyzia glabra or Glycerrhyzia uralensis, extracts of Rubus subspecies, especially Rubus suavissimus or Rubus chingii containing rubusoside, and extracts of Mycetia balansae, preferably containing balancin A and / or balancin B, or concentrated fractions of such extracts. Preferably, a synthetic sweetener selected from the group consisting of magap, sodium cyclamate or other physiologically acceptable salts of cyclamate, acesulfame K, saccharin, sodium saccharin salt, aspartame, super aspartame, neotame, alitarm, advantame, perillartin, sucralose, ruguznam, carrelame, sucrononate, and sucrooctate.

[0039] Particularly preferably, the one, two, three or more, or all of the sweetening substances are selected from the group consisting of sucrose, fructose, glucose, stevioside, rebaudioside, rebaudioside A, rebaudioside M, mono-, di-, tri- or tetra-alpha-glycosylated stevioside or rebaudioside, rubusoside, mono-, di-, tri- or tetra-alpha-glycosylated rubusoside.

[0040] The term "mixture of two or more compounds of formula (I)" refers to a mixture containing or consisting of two or more compounds of formula (I).

[0041] Preferably, the compound of formula (I) or a mixture of two or more compounds is used in an amount that is perceived as sweeter or less sweet than a 5%, preferably 2.5%, preferably 1.5% aqueous solution of sucrose, to adjust the sweetness of one or more sweetening substances.

[0042] Compounds of formula (I) can be prepared by chemical and enzymatic acylation. HG, hesperetine dihydrochalcone, hesperidin dihydrochalcone, or mixtures thereof can be used as starting materials. Acylation may be synthetic or enzymatic, as described in the following examples.

[0043] The present invention further provides a method for producing a compound of formula (I), i) A step of preparing one, two, or all of the compounds selected from the group consisting of hesperetin dihydrochalcone, hesperidin dihydrochalcone, and hesperetin dihydrochalcone-4'-O-β-d-glucoside (HG), ii) A step of preparing one or more acyl donors, iii) Mixing the compound(s) provided in step i) with the acyl donor(s) provided in step ii) and subjecting the compound(s) prepared in step i) to chemical or enzymatic acylation. This also relates to methods that include this.

[0044] HG, hesperetin dihydrochalcone, hesperidin dihydrochalcone, or mixtures thereof may be provided as plant extracts, such as an extract of Balanophora harlandii.

[0045] Therefore, in step i) of the method according to the present invention, a plant extract is prepared containing one, two, or all of the compounds selected from the group consisting of hesperetin dihydrochalcone, hesperidin dihydrochalcone, and hesperetin dihydrochalcone-4'-O-β-d-glucoside (HG), and preferably the plant extract is an extract of Balanophora harlandii.

[0046] As an example of providing such extracts, plant material, particularly the leaves of Balanophora harlandii, can be subjected to solvent extraction at temperatures ranging from 0°C to the boiling point of each solvent. For extraction, the ratio of plant material to solvent may be 1:10 to 1:30, preferably 1:5 to 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 may be, for example, polystyrene, or a mixture of polystyrene and other components. Preferably, water and ethanol are used as solvents in a weight ratio of at least 1:3 water:ethanol, and the extraction temperature is 30°C to 50°C, preferably 35°C to 45°C. Alternatively, extracts from plant material, for example, Balanophora harlandii, are commercially available.

[0047] Preferably, the acylation in step iii) of the method according to the present invention is a chemical acylation. Such acylation can be carried out according to the following scheme.

[0048] [ka]

[0049] Preferably, the acylation in step iii) of the method according to the present invention is enzymatic acylation. In this case, one or more prepared compounds selected from the group consisting of hesperetin dihydrochalcone, hesperidin dihydrochalcone, and hesperetin dihydrochalcone-4'-O-β-d-glucoside (HG) are incubated together with an acyl donor and an enzyme, preferably a lipase.

[0050] Therefore, preferably, the acylation in step iii) is enzymatic acylation, and the enzyme is an esterase, preferably a lipase, and preferably the lipase is Candida antarctica A, Candida antarctica B, Candida rugosa, Burkholderia cepacia, Rhizopus species, Rhizomucor miehei, Mucor javanicus, Yarrowia lypolytica, Geotrichum candidum, Aspergillus niger, Aspergillus oryzae, Pseudomonas alcaligenes, Pseudomonas This lipase is obtained from microorganisms selected from the group consisting of Pseudomonas mendocina, Thermomyces lanuginosus, and Chromobacterium viscosum.

[0051] Preferably, the above-mentioned acyl donors, or one, two, three or more, or all of them, are selected from the group consisting of ethanol donors, propanoyl donors, butanoyl donors, pentanoyl donors, hexanoyl donors, heptanyl donors, octanoyl donors, nonanoyl donors, and decanoyl donors.

[0052] Typically, to produce the compounds described herein, the aforementioned or one acyl donor(s) is an ester having the corresponding acyl residue. For example, when a compound having propionyl residues at R1, R2, R3, and / or R4 is produced, the aforementioned or one acyl donor(s) is an ester having propionyl residues.

[0053] Preferably, the ethanol donor described herein is selected from the group consisting of triacetin, acetic acid, methyl acetate, ethyl acetate, acetic anhydride, and mixtures thereof.

[0054] Preferably, the propanoyl donor described herein is selected from the group consisting of trippropionine, propionic acid, methyl propanoate, ethyl propanoate, and mixtures thereof.

[0055] Preferably, the butanoyl donor described herein is selected from the group consisting of triptyline, butanoic acid, methyl butanoate, ethyl butanoate, and mixtures thereof.

[0056] Preferably, the pentanoyl donor described herein is selected from the group consisting of tripentanoin, pentanoic acid, methyl pentanoate, ethyl pentanoate, and mixtures thereof.

[0057] Preferably, the hexanoyl donor described herein is selected from the group consisting of trihexanoin, hexanoic acid, methyl hexanoate, ethyl hexanoate, and mixtures thereof.

[0058] Preferably, the heptanoyl donor described herein is selected from the group consisting of triheptanoin, heptanoic acid, methyl heptanoate, ethyl heptanoate, and mixtures thereof.

[0059] Preferably, the octanoyl donor described herein is selected from the group consisting of trioctanoin, octanoic acid, methyl octanoate, ethyl octanoate, and mixtures thereof.

[0060] Preferably, the nonanoyl donor described herein is selected from the group consisting of trinonanoin, nonanoic acid, methyl nonanoate, ethyl nonanoate, and mixtures thereof.

[0061] Preferably, the decanoyl donor described herein is selected from the group consisting of tricaprine, decanoic acid, methyl decanoate, ethyl decanoate, and mixtures thereof.

[0062] Preferably, the above-mentioned 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, trippropionine, propionic acid, methyl propanoate, ethyl propanoate, triptyline, butanoic acid, methyl butanoate, ethyl butanoate, tripentanoin, pentanoic acid, methyl pentanoate, ethyl pentanoate, trihexanoin, hexanoic acid, methyl hexanoate, ethyl hexanoate, triheptanoin, heptanoic acid, methyl heptanoate, ethyl heptanoate, trioctanoin, octanoic acid, methyl octanoate, ethyl octanoate, trinonanoin, nonanoic acid, methyl nonanoate, ethyl nonanoate, tricaprine, decanoic acid, methyl decanoate, and ethyl decanoate.

[0063] The present invention further includes the following formula (I): [ka] Regarding the compound, The ingredients will be selected from the following:

[0064] [Table 8]

[0065] [Table 9]

[0066] [Table 10]

[0067] [Table 11]

[0068] As described herein, surprisingly, acylation of dihydrochalcone glycoside hesperetine dihydrochalcone-4'-O-β-d-glucoside (HG) has been found to increase its sweetness and sweetness-modulating properties. Therefore, the compound of formula (I) itself exhibits improved sweetness and improved sweetness-modulating properties.

[0069] Surprisingly, the compound of formula (I) was found to provide a similar sweetness or similar sweetness-modifying properties to HG, but at a much lower concentration.

[0070] Preferably, R2, R3, and R4 of the compound according to the present invention are each hydrogen. Therefore, R1 is selected from the group consisting of an acetyl group, a propionyl group, a butanoyl group, a pentanoyl group, a hexanoyl group, and a heptanol group.

[0071] More preferably, the compound according to the present invention is selected from the following compounds.

[0072] [Table 12]

[0073] [Table 13]

[0074] [Table 14]

[0075] The present invention also relates to compositions comprising the compounds according to the present invention.

[0076] Preferably, the composition further comprises one or more sweetening substances selected from the group consisting of the following:

[0077] Natural sweeteners (one or more), preferably natural sweeteners including plant extracts, for example sweet carbohydrates (sucrose, D-(+)-trehalose, lactose, maltose, D-(+)-melizitose, melibiose, D-(+)-raffinose, palatinose, lactulose, D-fructose, D-(+)-allulose, D-glucose, D-galactose, D-(+)-allose, D-(+)-altrose, D-(-)-glucose, D-(+)-mannose, D-(-)-idos, D-(+)-talose, L-(+)- Rhamnose, L-(-)-fucose, D-sorbose, D-mannose, D-(-)-tagatose, D-arabinose, L-arabinose, D-(+)-xylose, D-lyxose, D-ribose, D-ribulose, D-(-)-erythrose, D-(+)-threose, D-glyceraldehyde, maltodextrin, etc., sugar alcohols (erythritol, threitol, arabitol, ribitol, xylitol, sorbitol, mannitol, maltitol, isomaltitol, dulcitol, lactitol, etc.), tan Proteins (such as miraculin, pentadin, monellin, thaumatin, curculin, blazein, mavinlin, etc.), D-amino acids (such as D-phenylalanine, D-tryptophan, etc.), or extracts or fractions obtained from natural sources containing these amino acids and / or proteins, and physiologically acceptable salts of these amino acids and / or proteins, in particular their sodium, potassium, calcium or ammonium salts, steviol glycoside, stevioside, mono-, di-, tri- or tetra-al Alpha-glycosylated stevioside or rebaudioside, steviolbiosid, rebaudioside, rebaudioside A, rebaudioside B, rebaudioside C, rebaudioside D, rebaudioside E, rebaudioside F, rebaudioside G, rebaudioside H, rebaudioside M, rebaudioside N, rebaudioside X, dulcoside, rubusoside, mono-, di-, tri- or tetra-alpha-glycosylated rubusoside, suavioside A, suavioside B, suavioside G, suavioside H, suavioside I, suavioside J,Bayunoside 1, Bayunoside 2, Florisoside 1, Florisoside 2, Florisoside 3, Florisoside 4, Abulsoside A, Abulsoside B, Abulsoside C, Abulsoside D, Cyclocarioside A, Cyclocarioside I, Oslandin, Polypodoside A, Strogin 1, Strogin 2, Strogin 4, Selligueanin A, Dihydroquercetin-3-acetate, Perillartin, Telosmoside A15, Periandrin IV, Pterocarioside, Cyclocarioside, Muclodioside, Trans-Anethole, Brioside, Brionoside, Brionodorcoside, Ca Runosifloside, candenoside, gypenoside, hematoxylin, cyanine, chlorogenic acid, albidiasaponin, telosmoside, goudichooside, balancin A, balancin B, mogrosides such as mogroside V, hernandulcin, monatin, glycyrrhetinic acid and its derivatives, especially glycyrrhizin, preferably glycyrrhizinammonium salt; extracts of Thaumatococcus or Stevia subspecies, especially Stevia japonica, Stevia leaf extract, Swingle extract, especially Momordica or Luo Han Guo or Luo Han Guo; subspecies of Glyceridium, especially Glyceridium Extracts such as extracts of Glycerrhyzia glabra or Glycerrhyzia uralensis, extracts of Rubus subspecies, especially Rubus suavissimus or Rubus chingii containing rubusoside, and extracts of Mycetia balansae, preferably containing balancin A and / or balancin B, or concentrated fractions of such extracts. Preferably, a synthetic sweetener selected from the group consisting of magap, sodium cyclamate or other physiologically acceptable salts of cyclamate, acesulfame K, saccharin, sodium saccharin salt, aspartame, super aspartame, neotame, alitarm, advantame, perillartin, sucralose, ruguznam, carrelame, sucrononate, and sucrooctate.

[0078] Particularly preferably, the composition contains one or more sweetening substances selected from the group consisting of sucrose, fructose, glucose, stevioside, rebaudioside, rebaudioside A, rebaudioside M, mono-, di-, tri- or tetra-alpha-glycosylated stevioside or rebaudioside, rubusoside, mono-, di-, tri- or tetra-alpha-glycosylated rubusoside.

[0079] Particularly preferably, the composition includes hesperetin, hesperetin dihydrochalcone, naringenin, phloretin, eriodictiol, homoeriodictiol, phyllodulcin, neohesperidin dihydrochalcone, naringin dihydrochalcone, phloretin, an extract of the hydrangea subspecies Hydrangea macrophylla, particularly containing an effective amount of phyllodulcin, and one or more sweeteners selected from the group consisting of Hydrangea macrophylla var. japonica, Hydrangea macrophylla or Hydrangea macrophylla var. japonica.

[0080] Even more surprisingly, it was discovered that a synergistic effect can be obtained by combining two or more compounds of formula (I).

[0081] Therefore, the composition according to the present invention preferably contains two or more compounds of formula (I).

[0082] Therefore, the composition according to the present invention comprises two or more compounds of formula (I), wherein at least two of R1, R2, R3, and R4 are acetyl groups, and preferably R1 and at least one of R2, R3, and R4 are acetyl groups.

[0083] Therefore, the composition according to the present invention comprises two or more compounds of formula (I), wherein at least two of R1, R2, R3, and R4 are propionyl groups, and preferably R1 and at least one of R2, R3, and R4 are propionyl groups.

[0084] Therefore, the composition according to the present invention comprises two or more compounds of formula (I), wherein at least two of R1, R2, R3, and R4 are butanoyl groups, and preferably R1 and at least one of R2, R3, and R4 are butanoyl groups.

[0085] Therefore, the composition according to the present invention comprises two or more compounds of formula (I), wherein at least two of R1, R2, R3, and R4 are pentanoyl groups, and preferably R1 and at least one of R2, R3, and R4 are pentanoyl groups.

[0086] Therefore, the composition according to the present invention comprises two or more compounds of formula (I), wherein at least two of R1, R2, R3, and R4 are hexanoyl groups, and preferably R1 and at least one of R2, R3, and R4 are hexanoyl groups.

[0087] Therefore, the composition according to the present invention comprises two or more compounds of formula (I), wherein at least two of R1, R2, R3, and R4 are heptanoyl groups, and preferably R1 and at least one of R2, R3, and R4 are heptanoyl groups.

[0088] Therefore, the composition according to the present invention comprises two or more compounds of formula (I), wherein at least two of R1, R2, R3, and R4 are octanoyl groups, and preferably R1 and at least one of R2, R3, and R4 are octanoyl groups.

[0089] Therefore, the composition according to the present invention comprises two or more compounds of formula (I), wherein at least two of R1, R2, R3, and R4 are nonanoyl groups, and preferably R1 and at least one of R2, R3, and R4 are nonanoyl groups.

[0090] Therefore, the composition according to the present invention comprises two or more compounds of formula (I), wherein at least two of R1, R2, R3, and R4 are decanoyl groups, and preferably R1 and at least one of R2, R3, and R4 are decanoyl groups.

[0091] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 9 and compound 25.

[0092] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 9 and compound 41.

[0093] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 9 and compound 57.

[0094] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 9 and compound 73.

[0095] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 9 and compound 89.

[0096] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 9 and compound 105.

[0097] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 9 and compound 121.

[0098] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 9 and compound 137.

[0099] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 25 and compound 41.

[0100] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 25 and compound 57.

[0101] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 25 and compound 73.

[0102] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 25 and compound 89.

[0103] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 25 and compound 105.

[0104] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 25 and compound 121.

[0105] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 25 and compound 137.

[0106] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 41 and compound 57.

[0107] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 41 and compound 73.

[0108] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 41 and compound 89.

[0109] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 41 and compound 105.

[0110] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 41 and compound 121.

[0111] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 41 and compound 137.

[0112] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 57 and compound 73.

[0113] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 57 and compound 89.

[0114] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 57 and compound 105.

[0115] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 57 and compound 121.

[0116] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 57 and compound 137.

[0117] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 73 and compound 89.

[0118] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 73 and compound 105.

[0119] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 73 and compound 121.

[0120] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 73 and compound 137.

[0121] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 89 and compound 105.

[0122] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 89 and compound 121.

[0123] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 89 and compound 137.

[0124] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 105 and compound 121.

[0125] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 105 and compound 137.

[0126] The composition according to the present invention comprises two or more compounds of formula (I), and it is more preferable that the composition comprises compound 121 and compound 137.

[0127] Preferably, the amount of one or more compounds of formula (I) in the composition is in the range of 0.0001 to 75% by weight, preferably 0.0002 to 50% by weight, preferably 0.0003 to 25% by weight, preferably 0.0005 to 10% by weight, preferably 0.00075 to 5% by weight, and preferably 0.001 to 1% by weight, based on the total weight of the composition.

[0128] Preferably, the term "amount of compound(s) of formula(I) in the composition" refers to the total amount of all compounds(s) of formula(I) present in the composition.

[0129] The present invention also relates to products comprising the composition according to the present invention.

[0130] Preferably, the amount of one or more compounds of formula (I) in the product is in the range of 0.0001 to 1% by weight, preferably 0.0002 to 0.1% by weight, preferably 0.0003 to 0.01% by weight, and preferably 0.0005 to 0.005% by weight, based on the total weight of the product.

[0131] Preferably, the amount of one or more compounds of formula (I) in the product is a maximum of 50 ppm, preferably a maximum of 25 ppm, particularly preferably a maximum of 20 ppm, particularly preferably a maximum of 10 ppm, even more preferably a maximum of 7.5 ppm, and even more preferably a maximum of 5 ppm, relative to the total product.

[0132] Preferably, the amount of one or more compounds of formula (I) in the product is at least 3 ppm, preferably at least 5 ppm, particularly preferably at least 10 ppm, particularly preferably at least 15 ppm, even more preferably at least 20 ppm, more preferably at least 25 ppm, and even more preferably at least 50 ppm relative to the total product.

[0133] Preferably, the term "amount of compound(s) of formula(I) in the product" refers to the total amount of all compounds(s) of formula(I) present in the product.

[0134] The products according to the present invention can be selected from the group consisting of pharmaceuticals for oral administration, oral care products, liquid and solid products for nutrition or palatability, and semi-finished products.

[0135] Preferably, semi-finished products refer to substances, products, or goods that have not completed their manufacturing or production process and are not ready for sale to consumers and / or clients in the food service or catering industry, or for use or consumption by consumers and / or clients. Therefore, semi-finished products preferably refer to products, goods, or articles that are intended for further industrial processing and / or use in industrial processing.

[0136] Preferably, the semi-finished product should be understood as a product unsuitable for use as instant food. The semi-finished product is converted into instant food only by mixing it with at least one other ingredient (for example, to reduce the concentration of flavor), and possibly by further processing steps (e.g., heating, freezing).

[0137] Preferably, the semi-finished product is selected from substances, products, or goods intended for use in food, such as aromatic compositions, extracts, mashes, powders, oils or pastes made from vegetables or fruits, spices, toppings, seasoning mixtures, granules or finely ground foods.

[0138] Preferably, the amount of one or more compounds of formula (I) in the semi-finished product is in the range of 0.0001 to 75% by weight, preferably 0.0002 to 50% by weight, preferably 0.0003 to 25% by weight, preferably 0.0005 to 10% by weight, preferably 0.00075 to 5% by weight, and preferably 0.001 to 1% by weight, based on the total weight of the semi-finished product.

[0139] Preferably, the nutritional or flavorful product can be selected from the group consisting of: (low-calorie) baked goods (e.g., bread, dry biscuits, cakes, other baked goods), confectionery (e.g., muesli bar products, chocolate, chocolate bars, other bar products, fruit gummies, dragees, hard and soft caramels, chewing gum), non-alcoholic beverages (e.g., cocoa, coffee, green tea, black tea, (green tea, black tea) extract-fortified (green tea, black tea) beverages, rooibos tea, other herbal teas, fruit-flavored soft drinks, iso). Tonic drinks, soft drinks, nectars, fruit and vegetable juices, fruit or vegetable juice preparations), instant beverages (e.g., instant cocoa drinks, instant tea drinks, instant coffee drinks), meat products (e.g., ham, fresh sausages or raw sausage preparations, spiced or marinated fresh or salted meat products), eggs or egg products (dried eggs, egg whites, egg yolks), cereal products (e.g., breakfast cereals, muesli bars, cooked instant rice products), dairy products (e.g., full-fat, low-fat or non-fat milk beverages, rice puddings) (Soy products, yogurt, kefir, cream cheese, soft cheese, hard cheese, dried milk powder, whey, butter, buttermilk, ice cream, products containing partially or completely hydrolyzed milk protein), products made from soy protein or other soy fractions (e.g., soy milk and products made therefrom, beverages containing isolated or enzymatically treated soy protein, beverages containing soy flour, preparations containing soy lecithin, fermented products such as tofu and tempeh or products made therefrom, and fruit preparations and mixtures with flavorings), Dairy-like preparations (milk type, yogurt type, dessert type, ice cream), plant protein-enriched non-dairy beverages, fruit preparations (e.g., jams, sherbets, fruit sauces, fruit fillings), vegetable preparations (e.g., ketchup, sauces, dried vegetables, frozen vegetables, cooked vegetables, boiled vegetables), snacks (e.g., baked or fried potato crisps or potato dough products),Extruded products based on corn or ground potatoes), fats and oils-based products or their emulsions (e.g., mayonnaise, remoulade, dressings, in either full-fat or reduced-fat varieties), other ready-made dishes and soups (e.g., dried soups, instant soups, prepared soups), spices, spice mixtures, and especially seasonings, sweetener preparations, tablets or packets, and other preparations for sweetening or whitening beverages, used, for example, in the snack sector.

[0140] The product may be a nutritional supplement or pharmaceutical product in the form of capsules, tablets (uncoated tablets and coated tablets, e.g., gastric-resistant coatings), sugar-coated tablets, granules, pellets, solid mixtures, dispersions in a liquid phase, emulsions, powders, solutions, pastes, or other swallowable or chewable formulations.

[0141] Oral care products are formulations commonly used by those skilled in the art to cleanse and care for the oral cavity and pharynx, and to freshen breath. Known common oral care products are in the form of creams, gels, pastes, foams, emulsions, suspensions, aerosols, sprays, and capsules, granules, lozenges, tablets, sweets, or chewing gum, but this list of dosage forms is not limited to possible uses. Such formulations are used to cleanse and care for tooth structure and oral cavity, and to freshen breath. In particular, oral care products according to the present invention are preferably selected from the group consisting of: toothpaste, toothpaste gel, mouthwash, mouth rinse, gargle liquid, oral or pharyngeal spray (pump or aerosol spray), lozenges, candy, chewing gum, chewing candy, and dental care chewing gum.

[0142] Preferably, the unit "ppm" refers to weight, and for example, the unit corresponding to mg / kg is described.

[0143] Furthermore, the present invention relates to a method for adjusting the sweetness of one or more sweetening substances, comprising the following steps. a) A step of preparing one or more compounds according to the present invention, b) A step of preparing one or more sweetening substances, c) A step of mixing one or more compounds prepared in step a) with one or more sweetening substances prepared in step b), Preferably, the one, two, three or more, or all of the sweetening substances mentioned above are selected from the group consisting of the following: Natural sweeteners (one or more), preferably natural sweeteners including plant extracts, for example sweet carbohydrates (sucrose, D-(+)-trehalose, lactose, maltose, D-(+)-melizitose, melibiose, D-(+)-raffinose, palatinose, lactulose, D-fructose, D-(+)-allulose, D-glucose, D-galactose, D-(+)-allose, D-(+)-altrose, D-(-)-glucose, D-(+)-mannose, D-(-)-idos, D-(+)-talose, L-(+)- Rhamnose, L-(-)-fucose, D-sorbose, D-mannose, D-(-)-tagatose, D-arabinose, L-arabinose, D-(+)-xylose, D-lyxose, D-ribose, D-ribulose, D-(-)-erythrose, D-(+)-threose, D-glyceraldehyde, maltodextrin, etc., sugar alcohols (erythritol, threitol, arabitol, ribitol, xylitol, sorbitol, mannitol, maltitol, isomaltitol, dulcitol, lactitol, etc.), tan Proteins (such as miraculin, pentadin, monellin, thaumatin, curculin, blazein, mavinlin, etc.), D-amino acids (such as D-phenylalanine, D-tryptophan, etc.), or extracts or fractions obtained from natural sources containing these amino acids and / or proteins, and physiologically acceptable salts of these amino acids and / or proteins, in particular their sodium, potassium, calcium or ammonium salts, steviol glycoside, stevioside, mono-, di-, tri- or tetra-al Alpha-glycosylated stevioside or rebaudioside, steviolbiosid, rebaudioside, rebaudioside A, rebaudioside B, rebaudioside C, rebaudioside D, rebaudioside E, rebaudioside F, rebaudioside G, rebaudioside H, rebaudioside M, rebaudioside N, rebaudioside X, dulcoside, rubusoside, mono-, di-, tri- or tetra-alpha-glycosylated rubusoside, suavioside A, suavioside B, suavioside G, suavioside H, suavioside I, suavioside J,Bayunoside 1, Bayunoside 2, Florisoside 1, Florisoside 2, Florisoside 3, Florisoside 4, Abulsoside A, Abulsoside B, Abulsoside C, Abulsoside D, Cyclocarioside A, Cyclocarioside I, Oslandin, Polypodoside A, Strogin 1, Strogin 2, Strogin 4, Selligueanin A, Dihydroquercetin-3-acetate, Perillartin, Telosmoside A15, Periandrin IV, Pterocarioside, Cyclocarioside, Muclodioside, Trans-Anethole, Brioside, Brionoside, Brionodorcoside, Ca Runosifloside, candenoside, gypenoside, hematoxylin, cyanine, chlorogenic acid, albidiasaponin, telosmoside, goudichooside, balancin A, balancin B, mogrosides such as mogroside V, hernandulcin, monatin, glycyrrhetinic acid and its derivatives, especially glycyrrhizin, preferably glycyrrhizinammonium salt; extracts of Thaumatococcus or Stevia subspecies, especially Stevia japonica, Stevia leaf extract, Swingle extract, especially Momordica or Luo Han Guo or Luo Han Guo; subspecies of Glyceridium, especially Glyceridium Extracts such as extracts of Glycerrhyzia glabra or Glycerrhyzia uralensis, extracts of Rubus subspecies, especially Rubus suavissimus or Rubus chingii containing rubusoside, and extracts of Mycetia balansae, preferably containing balancin A and / or balancin B, or concentrated fractions of such extracts. Preferably, a synthetic sweetener selected from the group consisting of magap, sodium cyclamate or other physiologically acceptable salts of cyclamate, acesulfame K, saccharin, sodium saccharin salt, aspartame, super aspartame, neotame, alitarm, advantame, perillartin, sucralose, ruguznam, carrelame, sucrononate, and sucrooctate.

[0144] Particularly preferably, the one, two, three or more, or all of the sweetening substances mentioned above are selected from the group consisting of sucrose, fructose, glucose, stevioside, rebaudioside, rebaudioside A, rebaudioside M, mono-, di-, tri- or tetra-alpha-glycosylated stevioside or rebaudioside, rubusoside, mono-, di-, tri- or tetra-alpha-glycosylated rubusoside.

[0145] Preferably, the method according to the present invention further, b.2) A step of preparing one or more sweetening agents selected from the group consisting of hesperetin, hesperetin dihydrochalcone, naringenin, phloretin, eriodictiol, homoeriodictiol, phyllodulcin, neohesperidin dihydrochalcone, naringin dihydrochalcone, phloretin, and an extract of the hydrangea subspecies Hydrangea macrophylla, particularly containing an effective amount of phyllodulcin, Hydrangea macrophylla var. japonica, Hydrangea macrophylla var. japonica or Hydrangea macrophylla var. japonica. Includes, In step c), the compound(s) prepared in step a), one or more sweeteners prepared in step b), and one or more sweeteners prepared in step b.2) are mixed. In this case, the prepared components may be mixed simultaneously or sequentially. For example, the compound(s) prepared in step a) and the sweetener(s) prepared in step b) may be mixed first, and then mixed with the sweeteners(s) prepared in step b.2). Furthermore, in the subsequent mixing, the mixing of the prepared components may be in any order as described herein. [Brief explanation of the drawing]

[0146] [Figure 1] Figure 1 shows the LC-HRMS chromatogram of the acetylation product of HG obtained in Example 1. The charged aerosol detector signal is shown. [Figure 2] Figure 2 shows the LC-HRMS chromatogram of the acetylation product of HG obtained in Example 2. The charged aerosol detector signal is shown. Peak 3 corresponds to compound number 9. [Figure 3] Figure 3 shows the LC-HRMS chromatogram of the acetylation product of HG obtained in Example 3. The charged aerosol detector signal is shown. Peak 3 corresponds to compound number 25. [Figure 4] Figure 4 shows the LC-HRMS chromatogram of the acetylation product of HG obtained in Example 3. The charged aerosol detector signal is shown. Peak 3 corresponds to compound number 41. [Figure 5] Figure 5 shows the LC-HRMS chromatogram of the acetylation product of HG obtained in Example 3. The charged aerosol detector signal is shown. Peak 3 corresponds to compound number 57. [Figure 6] Figure 6 shows the LC-HRMS chromatogram of the acetylation product of HG obtained in Example 3. The charged aerosol detector signal is shown. Peak 3 corresponds to compound number 73. [Figure 7]Figure 7 shows the LC-HRMS chromatogram of the acetylation product of HG obtained in Example 3. The charged aerosol detector signal is shown. Peak 3 corresponds to compound number 89. [Figure 8] Figure 8 shows the LC-HRMS chromatogram of the acetylation product of HG obtained in Example 3. The charged aerosol detector signal is shown. Peak 3 corresponds to compound number 105. [Figure 9] Figure 9 shows the LC-HRMS chromatogram of the acetylation product of HG obtained in Example 3. The charged aerosol detector signal is shown. Peak 3 corresponds to compound number 137. [Modes for carrying out the invention]

[0147] Further aspects and effects of the present invention can be obtained from the following description of preferred embodiments. [Examples]

[0148] Example 1: Chemical acylation of HG 500 mg of hesperetine dihydrochalcone-4'-O-β-d-glucoside (HG) was dissolved in 10 mL of tetrahydrofuran, and then 100 μL of acetyl acetate and 0.15 μL of triethylamine were added at room temperature. The solution was stirred at room temperature for 18 hours. The reaction was quenched with 15 mL of H2O, and the aqueous layer was extracted with ethyl acetate (3 × 10 mL). The mixed organic layer was dehydrated with Na2SO4, and the solvent was removed under reduced pressure.

[0149] [ka]

[0150] The obtained compounds were analyzed by LC-HRMS (the results are shown in Figure 1).

[0151] Example 2: Enzymatic acylation of HG Hesperetine 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, or ethyl acetate at a concentration of 3 g / L if using acetonitrile or acetone solvent. The solution was incubated at 70°C for 4.5 hours with stirring. After incubation, the lipase was removed by filtration. The sample was analyzed by HPLC-MS (results are shown in Figure 2), and the following results were obtained.

[0152] [Table 15]

[0153] Example 3: Enzymatic acylation of HG Hesperetine 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 from the group consisting of ethyl acetate, ethyl propionate, ethyl butyrate, ethyl pentanoate, ethyl hexanoate, ethyl heptanoate, 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.

[0154] The solution was incubated at 70°C for 4.5 hours while stirring. After incubation, lipase was removed by filtration. The sample was analyzed by HPLC-MS (results are shown in Figures 3 to 9), and the following results were obtained (peaks classified as nd were below the threshold and could not be measured).

[0155] [Table 16]

[0156] [Table 17]

[0157] [Table 18]

[0158] [Table 19]

[0159] [Table 20]

[0160] [Table 21]

[0161] [Table 22]

[0162] Example 4: Sweetness of the compound of formula (I) Compounds 9, 41, 57, 73, and 89 were prepared as described in Example 3 and purified to a purity of more than 95% by preparative chromatography. The obtained compounds were used for sensory evaluation.

[0163] The intrinsic sweetness of each compound was determined by a panel of 20 trained panelists. The intrinsic sweetness was determined by evaluating the sweetness of the compound at different concentrations in water relative to a 1.5% sucrose solution. Then, the concentration at which the sample did not yield a statistically significant difference (p<0.05) (bidirectional: sweeter or less sweet) between the sample and the 1.5% sucrose control was determined, i.e., the concentration of each compound that yielded the same sweetness as the 1.5% sucrose solution.

[0164] As shown in the table below, the concentration of the acylated compound that exhibits 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 results in a significant increase in its inherent sweetness.

[0165] [Table 23]

[0166] Example 5: Sweetness of a mixture of compounds of formula (I) A mixture of butanoylated HG and a mixture of pentanoylated HG were prepared as described in Example 3.

[0167] 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 that exhibits sweetness equivalent to a 1.5% sucrose solution is approximately 1 / 5 to 1 / 8 of the required concentration of HG (non-acylated). Therefore, acylation of HG results in a significant increase in intrinsic sweetness.

[0168] [Table 24]

[0169] Example 6: Adjustment of the sweetness of a sweetening substance (sucrose) A 5% sucrose solution was prepared. Compounds 9, 41, 57, 73, and 89 were prepared as described in Example 3 and purified to a purity of more than 95% by preparative chromatography.

[0170] The sensory profiles of sucrose solution (control) and sucrose solution containing HG (control), compounds 9, 41, 57, 73, or 89 were determined by a trained flavorist panel comparing influence, intensity, and texture.

[0171] The addition of HG was found to increase the effect, strength, and texture. Furthermore, it was found that much lower concentrations of acylated HG were required to produce a similar effect.

[0172] [Table 25]

[0173] Example 7: Adjustment of the sweetness of a sweetening substance (sucrose) The sensory effects of compounds 9, 41, 57, 73, and 89 on a 5% sucrose aqueous solution were analyzed using a series of paired comparative tests (Duo tests) with a trained sensory panel (n=20). Samples were coded and randomized.

[0174] The test compound was found to increase the sweetness of the sucrose solution. Surprisingly, the observed effect was similar to that observed for HG, but the compound of formula (I) was applied at a much lower concentration.

[0175] [Table 26]

[0176] Example 8: Adjustment of sweetness of sweetening substances A sugar base (5% sucrose + 0.1% citric acid) was prepared. In addition, the sweetening substances RS (20% rubusoside), SG (90% steviol oligoglucoside), HC (8% hesperetin dihydrochalcone), LHG (52% mogroside V), and the sweetening modifiers PD (>95% phyllodulcin), HT (>85% hesperetin), and PH (>98% phloretin) were prepared and added to the sugar base to produce different samples (A).

[0177] Sample (B) was obtained by adding compound 41 at a dose of 2 mg / kg or compound 57 at a dose of 1.2 mg / kg to the sample.

[0178] Different taste descriptors were compared between samples (A) and (B) using a scale from 0 to 9 by a panel of five flavorists (n=5).

[0179] Panelists were asked to neutralize each sample with tap water between tastings, and the strength of the descriptor in each sample was defined before tasting the next sample. Following the tasting of each RS, SG, HC, LHG, PD, HT, or PH (Sample (A)), the samples to which RS, SG, HC, LHG, PD, HT, or PH+ compound (41 or 57) was added (Sample (B)) were compared to the strength of the base.

[0180] Example 8.1: Compound 41 Descriptor "Sweetness at start": [Table 27]

[0181] Descriptor "Overall sweetness": [Table 28]

[0182] Descriptor "texture" [Table 29]

[0183] Descriptor "Lingering sweetness": [Table 30]

[0184] Example 8.2: Compound 57 Descriptor "Sweetness at start": [Table 31]

[0185] Descriptor "Overall sweetness": [Table 32]

[0186] Descriptor "texture": [Table 33]

[0187] Descriptor "Lingering sweetness": [Table 34]

[0188] Example 9: Sweetness-modifying properties of compounds in lemonade base with reduced sugar content Compound 41 at a dose of 5 mg / kg or compound 57 at 3 mg / kg each was applied to different sugar-reduced lemonade bases to restore the overall sweetness and flavor of each matrix with reduced sugar content. Different descriptors were determined by a panel of five flavorists (n=5) and expressed as an intensity from 0 to 9.

[0189] The lemonade bases included "Full Sugar," "Reduced Sugar," "Stevia Hybrid," "Sugar-Free Base Suc / Ace K," and "Sugar-Free Base Asp / Ace K," all with the following recipes.

[0190] [Table 35]

[0191] Lemonade base "reduced sugar": [Table 36]

[0192] Lemonade base "Stevia Hybrid": [Table 37]

[0193] Lemonade base "Sugar-free base Suc / Ace K": [Table 38]

[0194] Lemonade base "Sugar-free base Asp / Ace K": [Table 39]

[0195] Application examples Application Example 1 Spray-dried preparation as a semi-finished product for flavoring the final product [Table 40] Pour drinking water into a container and dissolve maltodextrin and gum arabic in it. Then, emulsify the flavoring in the carrier solution using Turrax. The temperature of the spray solution must not exceed 30°C. Then, spray-dry the mixture (nominal inlet temperature: 185 to 195°C, nominal outlet temperature: 70 to 75°C).

[0196] Application Example 2 Combination with sweeteners Add 90 g of sucrose and 10 g of tagatose to 0.5 g of the spray-dried semi-finished product from Application Example 1 (preparation A, D, or G) and mix. The product can be used, for example, as a sweetener.

[0197] Application Example 3 Chewing gum [Table 41] Parts A through D are mixed and kneaded vigorously. The raw material mass can be processed, for example, into ready-to-consume chewing gum in the form of thin strips.

[0198] Application Example 4 toothpaste [Table 42] Pre-mix the components of parts A and B separately in each case, and stir well for 30 minutes at 25 to 30 °C under reduced pressure. Pre-mix part C and add it to A and B. Add D and stir the mixture well for 30 minutes at 25 to 30 °C under reduced pressure. After releasing the pressure, the chewing toothpaste is completed and can be filled.

[0199] Application Example 5 Sugar-free hard-boiled candy

Table 43

[0200] Application Example 6 Low-sugar tomato ketchup A: Comparative preparation using sugar B: Comparative preparation with reduced sugar content (compared to A) C~H: Preparations according to the present invention with reduced sugar content (compared to A), 6”-O-butanoyl-HG, compound (41)

[0201]

Table 44

[0202] Mix the components in the order described, homogenize the completed ketchup using a stirrer, pour it into bottles, and sterilize it.

[0203] Low-sugar tomato ketchup A: Comparative preparation using sugar B: Comparative preparation with reduced sugar content (compared to A) C~H: Preparations according to the present invention with reduced sugar content (compared to A), 6”-O-pentanoyl-HG, compound (73)

[0204]

Table 45

[0205] Mix the ingredients in the order described, homogenize the finished ketchup using a stirrer, pour it into bottles, and sterilize.

[0206] Application Example 7 Low-sugar fruit gum [Table 46] Note: Polydextrose is a non-sweet polysaccharide with a low calorie value by itself.

[0207] Application Example 8 Carbonated beverage (flavor direction: cola) A: Sugar-containing beverage (comparison) B: Low-calorie beverage C: Low-calorie beverage D: Low-calorie beverage E: Low-calorie beverage

[0208] [Table 47]

[0209] Mix the solid components or materials individually with water, combine them, and make up to 100 g with water. Then, let the resulting concentrate age overnight at ambient temperature. Finally, mix 1 part of the concentrate with 5 parts of carbonated water, fill into bottles, and seal.

[0210] Application Example 9 Instant Chocolate Powder Preparation A: Standard preparation Preparations B - D: Preparations according to the present invention

[0211] [Table 48] ​​​​​​​​ Instant Iced Tea (Peach Flavor) Preparation A: Standard preparation Preparations B-D: Preparations according to the present invention

[0214] [Table 49]

[0215] Standard amount of water for preparing peach iced tea beverage: 7.5% by weight.

[0216] Application Example 11 Iced tea Comparative example using sucrose (A)

[0217] [Table 50]

[0218] The ingredients were mixed in the order listed, placed in a bottle, and sterilized.

Claims

1. The use of a compound of formula (I) or a mixture of two or more compounds for providing sweetness and / or adjusting the sweetness of one or more sweetening substances, 【Chemistry 1】 In the formula, R1, R2, R3, and R4 are independently selected from the group consisting of hydrogen, acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanolyl group, octanoyl group, nonanoyl group, and decanoyl group. At least one of R1, R2, R3, and R4 is not hydrogen. use.

2. The use according to claim 1, wherein one, two, three or more, or all of the compounds of formula (I) are selected from the following compounds. Table 1 Table 2 Table 3 Table 4

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 claims 1 to 3, wherein one, two, three or more, or all of the compounds of formula (I) are selected from the following compounds. Table 5 Table 6 Table 7

5. The use according to any one of claims 1 to 4, wherein the one, two, three or more, or all of the sweetening substances are Natural sweeteners (one or more), preferably natural sweeteners including plant extracts, for example sweet carbohydrates (sucrose, D-(+)-trehalose, lactose, maltose, D-(+)-melizitose, melibiose, D-(+)-raffinose, palatinose, lactulose, D-fructose, D-(+)-allulose, D-glucose, D-galactose, D-(+)-allose, D-(+)-altrose, D-(-)-glucose, D-(+)-mannose, D-(-)-idos, D-(+)-talose, L-(+)- Rhamnose, L-(-)-fucose, D-sorbose, D-mannose, D-(-)-tagatose, D-arabinose, L-arabinose, D-(+)-xylose, D-lyxose, D-ribose, D-ribulose, D-(-)-erythrose, D-(+)-threose, D-glyceraldehyde, maltodextrin, etc.), sugar alcohols (erythritol, threitol, arabitol, ribitol, xylitol, sorbitol, mannitol, maltitol, isomaltitol, dulcitol, lactitol, etc.), tannins Proteins (such as miraculin, pentadine, monellin, thaumatin, curculin, blazein, mavinrin, etc.), D-amino acids (such as D-phenylalanine, D-tryptophan, etc.), or extracts or fractions obtained from natural sources containing these amino acids and / or proteins, and physiologically acceptable salts of these amino acids and / or proteins, in particular their sodium, potassium, calcium or ammonium salts, steviol glycosides, steviosides, mono-, di-, tri- or tetra-al Alpha-glycosylated stevioside or rebaudioside, steviolbioside, rebaudioside, rebaudioside A, rebaudioside B, rebaudioside C, rebaudioside D, rebaudioside E, rebaudioside F, rebaudioside G, rebaudioside H, rebaudioside M, rebaudioside N, rebaudioside X, dulcoside, rubusoside, mono-, di-, tri- or tetra-alpha-glycosylated rubusoside, suavioside A, suavioside B, suavioside G, suavioside H, suavioside I, suavioside J,Bayunoside 1, Bayunoside 2, Florisoside 1, Florisoside 2, Florisoside 3, Florisoside 4, Abulsoside A, Abulsoside B, Abulsoside C, Abulsoside D, Cyclocarioside A, Cyclocarioside I, Oslandin, Polypodoside A, Strogin 1, Strogin 2, Strogin 4, Selligueanin A, Dihydroquercetin-3-acetate, Perillartin, Telosmoside A15, Periandrin I-V, Pterocarioside, Cyclocarioside, Muclodioside, Trans-Anethole, Brioside, Brionoside, Brionodorcoside, Ca Runosifloside, candenoside, gypenoside, hematoxylin, cyanine, chlorogenic acid, albidiasaponin, telosmoside, goudichooside, balancin A, balancin B, mogrosides such as mogroside V, hernandulcin, monatin, glycyrrhetinic acid and its derivatives, especially glycyrrhizin, preferably glycyrrhizinammonium salt; extracts of Thaumatococcus or Stevia subspecies, especially Stevia japonica, Stevia leaf extract, Swingle extract, especially Momordica or Luo Han Guo or Luo Han Guo, subspecies of Glyceridium, especially Glyceridium Extracts such as extracts of Glycerrhizia glabra or Glycerrhizia uralensis, extracts of Rubus subspecies, especially Rubus suavissimus or Rubus chingii containing rubusoside, and extracts of Mycetia balansae, preferably containing balansin A and / or balansin B, or concentrated fractions of such extracts. Preferably, synthetic sweeteners selected from the group consisting of Magap, sodium cyclamate or other physiologically acceptable salts of cyclamate, acesulfame K, saccharin, sodium saccharin salts, aspartame, super aspartame, neotame, alitarm, advantame, perillartin, sucralose, ruguznam, carrelame, sucrononate, and scrooctate. Selected from the group consisting of, for use.

6. A method for producing the compound of formula (I), comprising the following steps: i) A step of preparing one, two, or all of the compounds selected from the group consisting of hesperetin dihydrochalcone, hesperidin dihydrochalcone, and hesperetin dihydrochalcone-4'-O-β-d-glucoside (HG), ii) A step of preparing one or more acyl donors, iii) Mixing the compound(s) prepared in step i) with the acyl donor(s) prepared in step ii) and subjecting the compound(s) prepared in step i) to chemical or enzymatic acylation. Methods that include...

7. The method according to claim 6, wherein the acyl donor, or one, two, three or more, or all of the acyl donors, is selected from the group consisting of ethanolyl donors, propanoyl donors, butanoyl donors, pentanoyl donors, hexanoyl donors, heptanyl donors, octanoyl donors, nonanoyl donors, and decanoyl donors. Preferably, the acyl donor, or one, two, three or more, or all of the acyl donors, is selected from the group consisting of triacetin, acetic acid, methyl acetate, ethyl acetate, acetic anhydride, trippropionine, propionic acid, methyl propanoate, ethyl propanoate, triptyline, butanoic acid, methyl butanoate, ethyl butanoate, tripentanoin, pentanoic acid, methyl pentanoate, ethyl pentanoate, trihexanoin, hexanoic acid, methyl hexanoate, ethyl hexanoate, triheptanoin, heptanoic acid, methyl heptanoate, ethyl heptanoate, trioctanoin, octanoic acid, methyl octanoate, ethyl octanoate, trinonanoin, nonanoic acid, methyl nonanoate, ethyl nonanoate, tricaprin, decanoic acid, methyl decanoate, and ethyl decanoate. method.

8. The method according to claim 6 or 7, wherein the acylation in step iii) is enzymatic acylation, and the enzyme is a lipase, Preferably, the lipase is Candida antarctica A, Candida antarctica B, Candida rugosa, Burkholderia cepacia, Rhizopus species, Rhizomucor miehei, Mucor javanicus, Yarrowia lipolytica, Geotrichum candidam, Aspergillus niger, Aspergillus oryzae This lipase is obtained from microorganisms selected from the group consisting of *Oryzae*, *Pseudomonas alcaligenes*, *Pseudomonas mendocina*, *Thermomyces lanuginosus*, and *Chromobacterium viscosum*. method.

9. A method according to any one of claims 6 to 8, wherein in step i), a plant extract is prepared comprising one, two, or all compounds selected from the group consisting of hesperetin dihydrochalcone, hesperidin dihydrochalcone, and hesperetin dihydrochalcone-4'-O-β-d-glucoside (HG), Preferably, the plant extract is an extract of Balanophora harlandii. method.

10. Formula (I) below: 【Chemistry 2】 A compound wherein the compound is selected from the following compounds. Table 8 Table 9 Table 10 Table 11

11. The compound according to claim 10, wherein R2, R3, and R4 are each hydrogen.

12. A compound according to claim 10 or 11, selected from the following compounds. Table 12 Table 13 Table 14

13. A compound according to any one of claims 10 to 12, Natural sweeteners (one or more), preferably natural sweeteners including plant extracts, for example sweet carbohydrates (sucrose, D-(+)-trehalose, lactose, maltose, D-(+)-melizitose, melibiose, D-(+)-raffinose, palatinose, lactulose, D-fructose, D-(+)-allulose, D-glucose, D-galactose, D-(+)-allose, D-(+)-altrose, D-(-)-glucose, D-(+)-mannose, D-(-)-idos, D-(+)-talose, L-(+)- Rhamnose, L-(-)-fucose, D-sorbose, D-mannose, D-(-)-tagatose, D-arabinose, L-arabinose, D-(+)-xylose, D-lyxose, D-ribose, D-ribulose, D-(-)-erythrose, D-(+)-threose, D-glyceraldehyde, maltodextrin, etc.), sugar alcohols (erythritol, threitol, arabitol, ribitol, xylitol, sorbitol, mannitol, maltitol, isomaltitol, dulcitol, lactitol, etc.), tannins Proteins (such as miraculin, pentadine, monellin, thaumatin, curculin, blazein, mavinrin, etc.), D-amino acids (such as D-phenylalanine, D-tryptophan, etc.), or extracts or fractions obtained from natural sources containing these amino acids and / or proteins, and physiologically acceptable salts of these amino acids and / or proteins, in particular their sodium, potassium, calcium or ammonium salts, steviol glycosides, steviosides, mono-, di-, tri- or tetra-al Alpha-glycosylated stevioside or rebaudioside, steviolbioside, rebaudioside, rebaudioside A, rebaudioside B, rebaudioside C, rebaudioside D, rebaudioside E, rebaudioside F, rebaudioside G, rebaudioside H, rebaudioside M, rebaudioside N, rebaudioside X, dulcoside, rubusoside, mono-, di-, tri- or tetra-alpha-glycosylated rubusoside, suavioside A, suavioside B, suavioside G, suavioside H, suavioside I, suavioside J,Bayunoside 1, Bayunoside 2, Florisoside 1, Florisoside 2, Florisoside 3, Florisoside 4, Abulsoside A, Abulsoside B, Abulsoside C, Abulsoside D, Cyclocarioside A, Cyclocarioside I, Oslandin, Polypodoside A, Strogin 1, Strogin 2, Strogin 4, Selligueanin A, Dihydroquercetin-3-acetate, Perillartin, Telosmoside A15, Periandrin I-V, Pterocarioside, Cyclocarioside, Muclodioside, Trans-Anethole, Brioside, Brionoside, Brionodorcoside, Ca Runosifloside, candenoside, gypenoside, hematoxylin, cyanine, chlorogenic acid, albidiasaponin, telosmoside, goudichooside, balancin A, balancin B, mogrosides such as mogroside V, hernandulcin, monatin, glycyrrhetinic acid and its derivatives, especially glycyrrhizin, preferably glycyrrhizinammonium salt; extracts of Thaumatococcus or Stevia subspecies, especially Stevia japonica, Stevia leaf extract, Swingle extract, especially Momordica or Luo Han Guo or Luo Han Guo, subspecies of Glyceridium, especially Glyceridium Extracts such as extracts of Glycerrhizia glabra or Glycerrhizia uralensis, extracts of Rubus subspecies, especially Rubus suavissimus or Rubus chingii containing rubusoside, and extracts of Mycetia balansae, preferably containing balansin A and / or balansin B, or concentrated fractions of such extracts. Preferably, synthetic sweeteners selected from the group consisting of Magap, sodium cyclamate or other physiologically acceptable salts of cyclamate, acesulfame K, saccharin, sodium saccharin salts, aspartame, super aspartame, neotame, alitarm, advantame, perillartin, sucralose, ruguznam, carrelame, sucrononate, and scrooctate. A composition comprising one or more sweetening substances selected from the group consisting of the following.

14. A method for adjusting the sweetness of one or more sweetening substances, comprising the following steps: a) A step of preparing one or more compounds according to any one of claims 10 to 12, b) A step of preparing one or more sweetening substances, c) Mixing the compound(s) prepared in step a) with the one or more sweetening substances prepared in step b). Includes, Preferably, the above-mentioned one, two, three or more, or all of the sweetening substances are Natural sweeteners (one or more), preferably natural sweeteners including plant extracts, for example sweet carbohydrates (sucrose, D-(+)-trehalose, lactose, maltose, D-(+)-melizitose, melibiose, D-(+)-raffinose, palatinose, lactulose, D-fructose, D-(+)-allulose, D-glucose, D-galactose, D-(+)-allose, D-(+)-altrose, D-(-)-glucose, D-(+)-mannose, D-(-)-idos, D-(+)-talose, L-(+)- Rhamnose, L-(-)-fucose, D-sorbose, D-mannose, D-(-)-tagatose, D-arabinose, L-arabinose, D-(+)-xylose, D-lyxose, D-ribose, D-ribulose, D-(-)-erythrose, D-(+)-threose, D-glyceraldehyde, maltodextrin, etc.), sugar alcohols (erythritol, threitol, arabitol, ribitol, xylitol, sorbitol, mannitol, maltitol, isomaltitol, dulcitol, lactitol, etc.), tannins Proteins (such as miraculin, pentadine, monellin, thaumatin, curculin, blazein, mavinrin, etc.), D-amino acids (such as D-phenylalanine, D-tryptophan, etc.), or extracts or fractions obtained from natural sources containing these amino acids and / or proteins, and physiologically acceptable salts of these amino acids and / or proteins, in particular their sodium, potassium, calcium or ammonium salts, steviol glycosides, steviosides, mono-, di-, tri- or tetra-al Alpha-glycosylated stevioside or rebaudioside, steviolbioside, rebaudioside, rebaudioside A, rebaudioside B, rebaudioside C, rebaudioside D, rebaudioside E, rebaudioside F, rebaudioside G, rebaudioside H, rebaudioside M, rebaudioside N, rebaudioside X, dulcoside, rubusoside, mono-, di-, tri- or tetra-alpha-glycosylated rubusoside, suavioside A, suavioside B, suavioside G, suavioside H, suavioside I, suavioside J,Bayunoside 1, Bayunoside 2, Florisoside 1, Florisoside 2, Florisoside 3, Florisoside 4, Abulsoside A, Abulsoside B, Abulsoside C, Abulsoside D, Cyclocarioside A, Cyclocarioside I, Oslandin, Polypodoside A, Strogin 1, Strogin 2, Strogin 4, Selligueanin A, Dihydroquercetin-3-acetate, Perillartin, Telosmoside A15, Periandrin I-V, Pterocarioside, Cyclocarioside, Muclodioside, Trans-Anethole, Brioside, Brionoside, Brionodorcoside, Ca Runosifloside, candenoside, gypenoside, hematoxylin, cyanine, chlorogenic acid, albidiasaponin, telosmoside, goudichooside, balancin A, balancin B, mogrosides such as mogroside V, hernandulcin, monatin, glycyrrhetinic acid and its derivatives, especially glycyrrhizin, preferably glycyrrhizinammonium salt; extracts of Thaumatococcus or Stevia subspecies, especially Stevia japonica, Stevia leaf extract, Swingle extract, especially Momordica or Luo Han Guo or Luo Han Guo, subspecies of Glyceridium, especially Glyceridium Extracts such as extracts of Glycerrhizia glabra or Glycerrhizia uralensis, extracts of Rubus subspecies, especially Rubus suavissimus or Rubus chingii containing rubusoside, and extracts of Mycetia balansae, preferably containing balansin A and / or balansin B, or concentrated fractions of such extracts. Preferably, synthetic sweeteners selected from the group consisting of Magap, sodium cyclamate or other physiologically acceptable salts of cyclamate, acesulfame K, saccharin, sodium saccharin salts, aspartame, super aspartame, neotame, alitarm, advantame, perillartin, sucralose, ruguznam, carrelame, sucrononate, and scrooctate. A method selected from the group consisting of the following.

Images