JPH0510069B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for imparting sweetness by adding aminoacylated sugar or a salt thereof as a sweetening agent. Sucrose is a typical sweet-tasting substance, but intake or excessive intake of sucrose is often restricted for medical reasons. In particular, in patients with diabetes and the like, in order to actively limit sugar intake, the amount of sugar used for sweetening may be reduced or eliminated altogether. In recent years, there has been a strong tendency to reduce the intake of sucrose, even if it is not intended for treatment, in order to prevent adult diseases such as those mentioned above, to prevent dental caries, and to prevent obesity. So-called substitute sweeteners or dietary sweeteners used to compensate for the lack of sweetness due to reduction or elimination of sucrose inoculation include sugar alcohols such as sorbitol and maltitol, dipeptide sweeteners typified by aspartame, There are stevioside, glycyrrhizin, acesulfam, saccharin, etc., but unless sugar alcohols, aspartame, etc. are excluded, the quality of sweetness is not necessarily satisfactory. Therefore, there is still a need for a sweetener that has good sweetness and can replace sucrose. The present inventors conducted research on the synthesis and usefulness of peptides, and while conducting research on the synthesis and usefulness of aminoacylated sugars in which amino acids and sugars, which are widely present in living organisms, are ester-bonded, The present invention was completed by discovering that high-fructose sugar has a sweet taste, and furthermore, the existence of aminoacylated sugar that is of good quality and has a strong sweet taste. Regarding the taste of amino acids and peptides,
There have been reports on many amino acids and peptides that exhibit a bitter taste, including hydrophobic amino acids, arginine, and proline, and amino acids that exhibit a sweet taste, such as glycine and alanine, and sweet peptides, such as aspartame, are also known. On the other hand, there are no reports regarding the sweetness of aminoacylated sugars, except for those regarding the taste functions of aminoacylated sugars such as glycine, alanine, valine, isoleucine, and proline, and their salts (Japanese Patent Application No. 46093/1982). The aminoacylated sugar of the present invention is
It may be obtained by any method such as chemical synthesis or microbial fermentation, and there are no particular limitations on the manufacturing method. Specifically, for example, ethyl-4,6-blocked with benzylidene at the 4 and 6 positions.
Boc-amino acids were introduced into the 2nd and 3rd positions of O-benzylidene-α-D-glucopyranoside by the DCC method in the presence of DMAP (dimethylaminopyridine),
After that, Boc was treated with HC/dioxane.
(t-butoxycarbonyl) and benzylidene are removed to obtain the desired aminoacylated sugar. When the above-mentioned aminoacylated sugar is added as a sweetening agent, there is no change in its sweetness-producing function whether it is added by itself or in the form of a salt such as hydrochloride, and it can be used in any form.For example, it can be added by chemical synthesis method. Obtained final target product (aminoacylated sugar)
If the physical properties of
It is preferable to use it in the form of a maleate salt, a fumarate salt, etc., and the use of a hydrochloride salt is particularly preferable in terms of imparting sweetness. Examples of the aminoacylated sugar of the present invention include, in the following formula, R ₁ is an aminobutyryl group or a seryl group, R ₂ is an alkyl group having 1 to 6 carbon atoms,
Specifically, methyl-2,3-di-O-(L-α
-aminobutyryl)-α-D-glycopyranoside, methyl-2,3-di-O-(L-seryl)-α
-D-glucopyranoside, ethyl-2,3-di-
Examples include O-(L-α-aminobutyryl)-α-D-gracopyranoside, ethyl 2,3-di-O-(L-seryl)-α-D-gracopyranoside, and hydrochlorides thereof. formula The above aminoacylated sugar may be any of L-form, D-form, and DL-form. Moreover, each aminoacylated sugar or its salt may be used alone, or two or more types may be used in combination. Experiments on taste: Methyl-2,
3-di-O-(L-α-aminobutyryl)-α-
D-glucopyranoside and methyl-2,3-di-
O-(L-seryl)-α-D-gracopyranoside was evaluated for taste. The result is methyl-2,
3-di-O-(L-α-aminobutyryl)-α-
D-glucopyranoside is 53 times sweeter than sucrose, and methyl-2,3-di-O-(L-seryl)
-α-D-gracopyranoside was 3.4 times sweeter than sucrose.

[Table] Luceril Sweetness 1.46 3.4
In the sweetening method of the present invention, one or more components selected from aminoacylated sugars or salts thereof are added alone or in combination with other components to an edible material. Other ingredients used in combination include sucrose, glucose, lactose, sorbitol, maltitol, aspartame, stevioside,
Glycyrrhizin and other sweetening ingredients, sodium chloride, potassium chloride and other salty flavoring ingredients, amino acids, their salts, 5' nucleotides such as L-glutamic acid, L-glutamic acid salts, 5'-inosinic acid and 5'-guanylate Salts, succinates, animal protein hydrolysates, plant protein hydrolysates, extracts such as yeast extract, and other flavor-imparting ingredients, acidity-imparting ingredients such as glutamic acid, fumaric acid, citric acid, malic acid, tartaric acid, ascorbic acid, etc. Combinations of any other ingredients are also possible. For example, methyl-2,3-di-O-(L-α-
When adding aminobutyryl)-α-D-glucopyranoside (hydrochloride) alone, a sweetness equivalent to that of sucrose can be obtained at a molar concentration ratio of 1/50 to 1/55, but other taste components that coexist, The preferred amount to be added varies depending on the edible material, the desired intensity of sweetness, etc. The sweetening method of the present invention can be applied to various foods, beverages,
It can be applied to all kinds of edible materials that require sweetening, such as pharmaceuticals, and its usefulness as a method for imparting sweetness using a sweetener composed of amino acids and sugars is clear. The edible materials covered by the present invention include beverages such as juice and cola, fruit products, frozen desserts such as ice cream and sherbett, foods such as jelly, pudding, yogurt, chocolate, chewing gum, yellowtail, cakes, and Japanese sweets. It may be any edible material, such as beverages, sweeteners (powders, granules, cubes, syrups, etc.), toothpastes, other oral preparations, sugar-coated tablets, powder preparations, granule preparations, syrup preparations, and other pharmaceuticals. Next, the present invention will be further explained with reference to production examples and examples. In addition, the abbreviations in the manufacturing examples are as follows. Boc- t-butoxycarbonyl group Boc-ON 2-t-butoxycarbonylimino-2-phenylacetonitrile DCC dicyclohexylcarbodiimide DCU _rea N,N'-dicyclohexylurea TEA triethylamine THF tetrahydrofuran DMAP 4-dimethylaminopyridine GM chloroform-methanol ( 5:1) Production Example 1 Synthesis of sugar raw material - methyl-4,6-O-benzylidene-α-D-glucopyranoside (1) 200 g of anhydrous glucose was dehumidified with 500 ml of methanol containing 25% hydrochloric acid and heated on an oil bath for 18 hours. Boil at reflux for an hour. After the reaction, the mixture was left in an ice chamber and a mother nucleus was added to precipitate crystals. The crystals were filtered, washed with methanol, and the mother liquor was concentrated again to precipitate more crystals. The obtained crystals were combined and recrystallized from methanol to give methyl-α-
Crystals of D-glucopyranoside were obtained. Yield 97g (45%) mp 166℃ [α] ²⁵ _D +159° (c1.0, H ₂ O) R _f 0.02 (developing solvent CM) Calculated value as C ₇ H ₁₄ O ₆ C, 43.29%, H, 7.27%, O, 49.44
% Actual value C, 43.11%, H, 7.41%, O, 49.48
% (2) Suspend 28 g of methyl-α-D-glucopyranoside in 70 ml of benzaldehyde and add 21 g of zinc chloride.
g and stirred at room temperature. After 3 hours, the reaction solution was dissolved in ethyl acetate and washed with water. The organic layer was dried over anhydrous sodium sulfate, concentrated, and crystallized from ether. Yield 30g (74%) mp 161-167℃ [α] ²⁵ _D (c1.0, CHC ₃ ) R _f 0.58 (CM) Calculated value as C ₁₄ H ₁₈ O ₆ C, 59.56%, H, 6.43%, O, 34.01
% Actual value C, 59.48%, H, 6.39%, O, 34.13
% 2 Synthesis of methyl-2,3-di-O-(L-α-aminobutyryl)-α-D-glucopyranoside (1) Methyl=4,6-O-benzylidene-2,
3-di-O-[N-(t-butoxycarbonyl)-L-α-aminobutyryl]-α-D-
Synthesis of glucopyranoside N-(T-t-butoxycarbonyl)-L-α-
Aminobutyric acid dicyclohexylammonium salt (2.54 g, 6 mmol) was suspended in ethyl acetate, and 2N-
Stir vigorously _{with H2SO4} . Dilute the organic layer with anhydrous Na ₂ SO ₄
After drying and concentrating, an oily substance was obtained. This oily substance
Dicyclohexylcarbodiimide (DCC) (1.24 g,
6 mmol) was added thereto, and the mixture was stirred at 0°C for 20 min. followed by methyl 4,6-O-benzylidene-
α-D-glucopyranoside (0.57g, 2mmol) and 2,2-dimethylaminopyridine (65mg)
A solution dissolved in 5 ml of THF was added. After stirring overnight,
Remove N,N′-dicyclohexylurea,
The liquid was concentrated and dissolved in ethyl acetate. The organic layer was washed sequentially with water, 4% citric acid, water, 4% sodium bicarbonate, and water, and dried over anhydrous Na ₂ SO ₄ .
After vacuum concentration and concentration, the residue was subjected to silica gel column chromatography (solvent: hexane-ethyl acetate =
4:1) to give 0.56 g (1.28 mmol,
64%). mp 135−136℃ [α] ²⁵ _D +37° (c1, CHC ₃ ) R _f 0.42 (hexane/ethyl acetate = 2/1) Calculated value as C ₃₂ H ₄₈ O ₁₂ N ₂ C, 58.88%, H, 7.39%, O, 4.28% Actual value C, 59.01%, H, 7.35%, O, 4.30% (2) Methyl = 2,3-di-O-(L-α-aminobutyryl)-α-D- Synthesis of glucopyranosides. Methyl=4,6-O-benzylidene-2,3-
di-O-[N-(t-butoxycarbonyl)-L-
To α-aminobutyryl]-α-D-glucopyranoside (391 mg, 0.6 mmol) was added a solution of 4.3N HC in dioxane (10 ml). After the reaction was completed, it was concentrated and solidified by adding ether. Yield 96
% mp 110℃ [α] ²⁵ _D +88° (c1, MeOH) R _f 0.41 (1-BuOH/AcOH/Py/H ₂ O=
4/1/1/2) C ₁₄ H ₃₀ O ₈ N ₂ Calculated value as C ₂ C, 39.44%, H, 7.09%, N, 6.57% Actual value C, 39.38%, H, 7.15%, N, 6.51% 3 Methyl = 2,3-di-O-(L-α-seryl)
-Synthesis of α-D-glucopyranoside. (1) Methyl = 4,6-O-benzylidene-2,
Synthesis of 3-di-O-[N-(t-butoxycarbonyl)-O-benzylseryl]-α-D-glucopyranoside N-(t-butoxycarbonyl)-O-benzyl-L-serine (1.78 g, 6 mmol ), DCC (1.24g,
6mmol), methyl 4,6-O-benzylidene-α
-D-glucopyranoside (0.57g, 2mmol), 2,
2-dimethylaminopyridine (65mg) to methyl =
4,6-O-benzylidene-2,3-di-O-
Hygroscopic crystals were obtained in the same manner as the synthesis of [N-(t-butoxycarbonyl)-L-α-aminobutyryl]-α-D-glucopyranoside. Yield 63
% mp (hygroscopic) [α] ²⁵ _D +8° (c1, CHC ₃ ) Calculated value as C ₄₄ H ₅₆ O ₁₄ N ₂ C, 63.14%, H, 6.74%, N, 3.34% Actual value C, 63.09% , H, 6.71%, N, 3.37% (2) Methyl=2,3-di-O-(L-seryl)-
Synthesis of α-D-glucopyranoside. Methyl=4,6-O-benzylidene-2,3-
di-O-[N-(t-butoxycarbonyl)-O-
α-Benzyl-L-seryl]-α-D-glucopyranoside (502 mg, 0.6 mmol) was treated with 4.3 N HC/dioxane (10 ml) to remove the Boc and benzylidene groups. After concentration under reduced pressure, AcOH-MeOH (1:
1) (10 ml) and subjected to catalytic reduction using palladium black to remove the benzyl group. After removing the palladium black, it was concentrated, and acetone was added to the resulting residue to obtain hygroscopic crystals. Yield 78% mp (hygroscopic) [α] ²⁵ _D +69° (c1, MeOH) Calculated value as C ₁₃ H ₂₆ N ₂ O ₁₀ C ₂ C, 35.38%, H, 5.93%, N, 6.35% Actual value C, 35.29%, H, 5.97%, N, 6.31% Example 1 A coffee liquid was prepared by dissolving 2 g of one serving of instant coffee in 150 ml of each serving of hot water. In this coffee liquid, methyl-2,3-di-
O-(L-α-aminobutyryl)-α-D-glucopyranoside dihydrochloride (sample A) or methyl-2,3-di-O-(L-seryl)-α-D-glucopyranoside dihydrochloride A solution of salt (sample B) (test group) and a solution of sucrose (control group) were prepared, and sensory evaluation was conducted using a two-point comparison method using 20 well-trained taste panels. carried out. The results are shown in Table 2.
(Samples A to B and sucrose concentration) Sample A 0.15g/dl B 1.4″ Sucrose 6″

【table】

【table】

[Table] After preparing sweet chocolate in advance (the product of the present invention contains bitter chocolate, the compound of the present invention, dextrin, and cocoa butter; the control product contains bitter chocolate, sugar, and cocoa butter),
Chiyocolate mousse was prepared by a conventional method using eggs and fresh cream. The two types of thiokolate mousses obtained were stored in a refrigerator for one day to cool and solidify, and then sensory evaluation was performed by 20 taste panels. The results are shown in Table 3. Based on the evaluation results and comments, the product of the present invention exhibited refreshing sweetness and bitterness similar to the sucrose-added product, and was evaluated as having good palatability.

【table】

Claims (1)

[Claims] 1 Formula: (In the formula, R ₁ is an aminobutyryl group or a seryl group, and R ₂ is a lower alkyl group.) A method for imparting sweetness, which comprises adding an aminoacylated sugar or a salt thereof to an edible material.