JPS60188039A - Method of enhancing sweetness - Google Patents

Abstract

PURPOSE:A specific aminoacylated saccharide or its salt is added a sweetness enhancer to give food products sweetness of good quality. CONSTITUTION:At least one of aminoacrylated saccharides of the formula (R1 is an aminoalkyl group of branched or straight 1-5C chain, imidazolidinyl group; R2 is lower alkyl) or its salt is used, when necessary, in combination with other components in a variety of food products, beverages and medicines.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a sweetening method in which aminoacylated sugar or a salt thereof is added as a sweetening agent.

Sucrose is a typical substance that gives a sweet taste.
Sucrose intake or excessive intake is often restricted for medical reasons. In particular, in patients with diabetes, etc., in order to actively limit sugar intake, the amount of sugar used to provide sweetness may be reduced or completely eliminated. 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, and dibenotide sweeteners such as asnoeltame. There are many sweeteners, such as stevioside, glycyrrhizin, acesulfame, and saccharin, but unless sugar alcohols, as-altame, etc. are excluded, the quality of sweetness is not necessarily satisfactory. Therefore, there is still a need for a sweetener that has good sweet taste and can replace sucrose.

The present inventors conducted research on the synthesis and usefulness of bezotide, and while conducting ω1 research on the synthesis and usefulness of aminoafurated sugars in which amino acids and sugars are ester-bonded, which are widely present in living organisms. The present invention was completed by discovering that aminoacylated sugars have a sweet taste, and furthermore, that aminoacylated sugars have a high quality and strong sweetness.

Regarding the taste of amino acids and zotides, there have been reports on zezotide, a hydrophobic amino acid, arginine, many bitter amino acids including noroline, glycine,
Amino acids that exhibit a sweet taste, such as alanine, and sweet zotides, such as aspartame, are also known.

On the other hand, there are no reports regarding the taste of aminoacylated sugars, and nothing is known about the taste functions of glycine, alanine, valine, inleucine, Zorori A aminoacylated sugars and their salts in the present invention. These substances are
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, methyl-4,6-0-pennolidene-α-D in which the 4 and 6 positions are blocked with benzylidene
- D BoC-amino acid at position 2.3 of glucopyranoside
In the presence of MAP (dimethylaminobilinone), the aminoacylated sugar of the target product is removed by introducing it by the DCC method, and then removing Boc (t-butoxycarbonyl) and hypennolidene by HC1/dioxane treatment.
It will be done. When the above-mentioned aminoacylated sugar is added as a flavor imparting agent, there is no change in its sweetness-producing function whether it is used by itself or in the form of a salt such as hydrochloride, and it can be used in any form. If the physical properties of the final target product (aminoacylated saccharide) obtained by a synthetic method are unstable or difficult to handle, use hydrochloride, sulfate, citrate, tartrate, or maleate. , fumarate, etc. are important, and hydrochloride is particularly preferred for imparting sweetness.

R2 is an alkyl group having 1 to 6 carbon atoms, specifically,
Methyl-2,3-no〇-L-glycyl-α-D-glucopyranoside, Methyl-2,3-no〇-L-alanyl-α-D-glucopyranoside, Methyl-2,3-di〇-L-paryl-α- D-glucobylanondo, methyl-2
, 3-no〇-L-isoleucyl-α-D-glucopyranoside, methyl-2,3-no゛-0-L-norolyl-α
-D-glucopyranoside, ethyl-2,3-no〇-L
-Grituru-α-D-glucopyranoside, ethyl-2,
3-C0-L-77niluα-D-glucopyranoside, ethyl-2,3-di〇-L-noglyl-α-D-
Glucopyrano7-do, ethyl-2,3-no〇-L! Inleucyl-α-D-glucopyranoside, ethyl-2,3
-No〇-L-zorolyl-α-D-glucopyranoside and their hydrochlorides, and the like.

Formula above glycine, alanine, marine, 470470 bodies,
Any DL body may be used. The aminoacylated sugars or salts thereof may be used alone or in combination of two or more.

Experiments on Taste Taste was evaluated using a sensory test method using multiple dilutions. The results show that the aminoacylated sugars of glycine, alanine, ・guri/, and proline produce sweetness, while the aminoacylated sugars of isoloinone and threonine produce sweetness and bitterness, and the aminoacylated sugars of aspartic acid produce sweetness. It exhibits sweetness and sourness respectively,
In particular, the aminoacylated sugar of Arani/ was of good quality and had a strong sweet taste. Their taste power was approximately 2.5 to 25 times (molar concentration ratio) that of sucrose.0 (According to a taste experiment conducted at the same time, aminoacylated sugars of lysine and ornithine exhibit umami (simple It was found that the taste threshold in an aqueous solution system was -0.2-0.5mM).

) JP-A-188039 (3) In the sweetening method of the present invention, one or more components selected from aminoacylated sugars or salts thereof are added alone, or they are used in combination with other components. and then added to edible materials.

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, L- Salts of 5' nucleotides such as glutamic acid, L-glutamic acid salts, 5'-inosinic acid and 5'-guanylate, succinates, dynamic protein hydrolysates, plant protein hydrolysates, extracts such as yeast extract, etc. It is also possible to combine other flavor-imparting ingredients, acidity-imparting ingredients such as glutamic acid, fumaric acid, citric acid, malic acid, tartaric acid, ascorbic acid, and any other ingredients.

To impart a preferable sweetness to foods (or medicines), for example, methyl-2,3-・no-0-L-alanyl-α-D-
When glucopyranoside (hydrochloride) is added alone, 1/1
A sweetness equivalent to sucrose can be obtained at a molar concentration ratio of 0 to 1/15, but the exact amount added will vary depending on other coexisting flavor components, edible materials, and the desired intensity of sweetness. do.

The sweetening method of the present invention can be applied to various foods, drinks, medicines, etc.
It can be applied to all kinds of edible materials that require sweetening, and its usefulness as a method for imparting sweetness using a sweetener composed of naturally occurring amino acids and sugars is clear.

The edible materials covered by the present invention include foods such as citrus, chocolate, chewing gum, candy cakes, and Japanese sweets, beverages, sweeteners (powder, granules, kiev, cilantro, etc.), toothpaste, and other oral preparations. It may be any edible material, such as drugs such as sugar-coated tablets, powder preparations, granule preparations, and white horn preparations.

Next, the present invention will be further explained with reference to production examples and examples. In addition, the abbreviations in "¥LJ Haku" are as follows.

Boc-t-butoxy7carbonyl group Boc-ON 2-t-butquine carbonylimino-
2-phenylacetonitrile DCC nocyclohexylcarpodiimide DCU rea
N + N'-dicyclohexylurea TEA Triethylamine DMAP 4-Tmethylaminopyrinone CM Chloroform-methanol (5:1) Production Example 1 Sugar raw material - methyl-4,6-0-pentulytin-α-
Synthesis of D-glucopyranoside (1) 200 g of anhydrous glucose was dehumidified with 500 ml of methanol containing 25% hydrochloric acid, and the mixture was boiled and refluxed on an oil bath for 18 hours. When the reaction mixture was left in a water drainage chamber and mother nuclei were added, crystals precipitated. 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-D-
Crystals of glucopyranoside were obtained.

Yield tF: 97 g (4.5%) m, p, 166°C [α几”' +1.59° (c 1.0, H2O) R
f O,02 (Developing solvent CM) Calculated value as C7H1406 C, 43,29%, H, 7,27%, 0,4
9.4.4 Actual measurement value C, 43, 11%, H, 7, 41
%, 0.49.48 (2) 28 methyl-α-D-glucopyranoside was suspended in 70 ml of benzaldehyde, 11 g of zinc chloride was added, and the mixture was stirred at room temperature. After 3 hours, the reaction solution was dissolved in ethyl acetate and washed with water. The organic layer was dried with anhydrous sulfuric acid (l) ram, concentrated, and crystallized with ether.

Storage and hanging 30 g (74%) m, p-161-167℃ [α几5 (C1,0, CHCl3j) Rf O,58 (CM) Calculated value as C14H1806 C, 59,56%, H, 6, 43%, 0.34
．． 01% actual value C, 59,48%, H, 6,39%
, 0,34.13%2 Synthesis of methyl-2,3-no-glycyl-α-D-glucopyranoside (1) Suspend 75 g of glycine and Boc-ON 279 in 200 ml of water-Nooxa 7 (1:1), TEA '2
1ml! was added and stirred at room temperature for 3 hours. After concentrating the reaction solution to about half the volume, remove impurities with ether, and add 10% to the aqueous layer.
Citric acid was added to adjust the pH to 4. After extracting the aqueous layer with ethyl acetate, the organic layer was dried over sodium sulfate and concentrated. Add ether-petroleum ether to the oily residue and Boc・Gly
-OH was obtained.

Yield 1. 5 2,? (Part 87) mp' 8
4-95℃ Rf 0.33 (CM) Calculated value as C7111304N C, 47, 99th, H, 7, 48th, 0,36
．． 53%N, 8.00chi Actual value C, 48,06%H, 7, /13chi, 0.3
6. /17CHN, 8.04% (2) Dissolve Boc-Gly-OH2,63fj in 20 me of chloroform and add DCC3,0 while cooling on ice.
9,! i'e was added and stirred. Methyl after 10 minutes - 4.6
-0-pennolidene-α-D-glucopyranoside 1.4
1g and DMAI) 0. :33g to chloroform5
ml of the solution was added, and the mixture was stirred at room temperature overnight. Precipitated DCUrea ff: After filtering off, it was concentrated and dissolved in ethyl acetate. The organic layer was dissolved in water-4% citric acid-water-4% Na.
After thoroughly washing with HCO3 water, it was dried over anhydrous sodium sulfate and concentrated. Ether-petroleum ether was added to the oily residue, and methyl-4,6-〇-pennolidene-2,3-
Crystals of No〇-[:N-(1-ptoxy/carbonyl)glycyl]-α-D-glucopyranoside were obtained.

Collection Ji-2189 (73%) mp 8 8 - 8 9 ℃ [α] Otsu” +21° (c 1.0, CHCt3)
Rf O,75(CM) Calculated value as C28H4oO12N2 C,56,36chi H,6,76chi 0,3
2.18%N, 4.7% Actual value C, 56,4,1% H, 6,76% 0,3
2.20% N, 4.63% (3) Methyl-4,6-0-pennoligan-2,3-no-0-(N-(j-butoxycarbonyl)g') 7/
179 g of :)-α-D-glucopyra/cyto was dissolved in 5 ml of nooxane, 30 ml of a 4.2 M HCl dioxane solution was added, and the mixture was left at room temperature for 2.5 hours. After concentration under reduced pressure, the residue was crystallized from acetone to obtain the desired methyl-2,3-no-gly/ru-α-D-glucopyranoside dihydrochloride.

Yield t, 1y (ioochi) m-1), 120-135°C [α], +149' (c 1.0, MeOH)
Rf O,06(CM) C', , Calculated value as H2208N2C12 C
, 34,66chi H, 5,82% 0, 33.58chi N, 7.35chi actual measurement value C, 34,58chi H, 5,7g% 0, 3
3.59 Section N, 7.37 Section 3 Methyl-2,3-no〇-L-alanyl-α-D-
Synthesis of glucopyranoside (1) 891 g of L-alanine and Boc-ON 279 were suspended in 200 ml of water-soxane (1:1), and T
EA 21 me 1. H was added thereto, and the mixture was stirred at room temperature for 3 hours.

After concentrating the reaction solution to about half its volume, it was washed with ether and added to the aqueous layer for 10 minutes.
Citric acid was added to make p+-14. After extraction with ethyl acetate and drying over anhydrous sodium sulfate, the extract was concentrated and crystallized from ether-petroleum ether to obtain Boc-Aha-OH.

Yield 15.89g (84%) m, p, 83-84 °C [α]-5-22 (cl, o, Ac0H) Rf O,3
9 (CM) Calculated value as C8■■1504N C, 50,78chi H, 7,99% o,
33.82 coefficient N, 7.41 coefficient actual measurement value C, 50.71% H, 8.0:3 attack 0.3
3.84 ChiN, 7.42% (2) Boc-Ala-OH2,84g, DCC3
,09g, methyl-4,6-0-penturitin-α-D
- Glucobylanondo, DMAP 0.339 2-
Treat in the same manner as in (2) to obtain crystals of methyl-4,6-0-pentulytin-2,3-no〇-(N-(t-butylcarbonyl)-L-7ranyl)-α-D-glucopyranoside. It's a good deal.

Acquisition 252 g, (81 section) m, p, 85-87℃ [α) 2D5 + 24° (c 1-0-CHCt3)R
f O, 88 (CM) C5oH4401□ Division value as N2 C, 57, 68 H, 7, 161) 0, 30
．． 74 Chi N, 4.48 coefficient Actual measurement value C, 57, 61 coefficient H, 7, 14% 0, 3
0.78 coefficient N, 4.47% (3) Methyl-4,6-0-pennolithene-2,3-diO-[N-(t-butoxycarbonyl)-L-alanyl]-α-D-glucopyranoside 1. 87 gf,
2-(3) and treated in the same manner as methyl~2.3-no0-
L-alanyl-α-D-glucopyranoside was obtained.

Yield 1.23 g (100 parts) m-p, 58.62°C [αlfi” +88 (c 1.Q, MeOH)Rf
0.07 (CM) Calculated value as C13H2608N2C42 C, 38, 15% Old 6.4 Chi 0, 31.
28% N, 6.85 Chi 1 clay C, 38,08 Chi H, 6,36 Chi 0,3134
ChiN, 6.87Chi4, Methyl-2,3-No〇-L-
Synthesis of paryl α-ri-gluco-lanoside (1) L-barrier 11.711/, Boc-ON
27,! Process i' in the same way as 2-(1) and obtain Boc-
Van-OH was obtained.

Yield 21.73g (83%) rn, p, 77-79°C [α]D-58° (cl, 0.Ac0H) Rf 045
(CM) Calculated value as C1oH1904N C, 55, 28% H, 8, 82 Chi 0, 2
9.46 coefficient N, 6.44% Actual value C, 55, 24 CH H, 8, 78 coefficient 0,29
．． 51 ChiN, Section 6.4.7 (2) BoC-Val-OH3,26&, DCC
3,09,9, methyl-4,6-0-benzylidene-α
-D-glucopyranoside 1.41,! / , DMA
P O,331/ was treated in the same manner as 2-(2) to give methyl-4,6-0-pennolithene-2,3-di-1:N
-(t-butquine carbinyl)-L-valyl]-α-D
- Glucogiranoside was obtained.

Yield Ko, 31g (68chi) m, p, 160-162℃ [α), +: 31° (C1,0ICHC63)Rf
O,89(CM) Calculated value as C34H52012N2 C,59,98chi Fertilizer 7.8chi 0,28
．． 2nd coefficient N, 4.02% Actual value C, 59,92nd coefficient H, 7,82% 0,28
．． 27%N, 3.99% (3) Methyl-4,6-0-pennolyan-2,3-no-CN-(t-butoxylic acid)
2.04 g of methyl-2-valyl]-α-D-glucopyranone was treated in the same manner as in 2-(3).
, 3-No 07 L-valyl-α-D-glucohyranozod dihydrochloride was obtained.

Yield 1.08 g (77%) m, p, 120-1.25°C [α), +90° (c 1.O, MeOH) Rf O
,13(CM) Calculated value as C17H6408N2Ct2 C, 43,87chi H,7,36 section 0,2
7.51 coefficient N, 6.02 coefficient actual measurement value C, 4,3,'l 1% H, 7,33 coefficient 0
, 27.56%N, 6.08% 5 Methyl-2,3-no〇-isoloin-α-D-
Synthesis of glucopyrano7d (1) 13.12g of L-inroinone and Boc-ON2
7 g was suspended in 200 +++ l of water-nooxane (1:1), 21 ml of TEA was added, and the mixture was stirred at room temperature for 4 hours. The reaction solution was concentrated to about half its volume, washed with ether, and the aqueous layer was added with 10% citric acid. When the pH was adjusted to 4 by adding Boc-41e-O, crystals precipitated.The crystals were collected by filtration and washed thoroughly with water.
H4H20f was obtained.

Yield 18.26g (76%) m, p, 49-57°C [α]. +3° (c 1.0, Ac0H) C11H
2104N-1/! Calculated value as H20 C, 54,
98% H, 923% 0, 29.96% N, 5.83
% Actual value C, 55,07chi H, 9,20% 0,3
0.0chiN, 5.73chi(2) Boc-I Ie-OI('/2H203,6
0 g was dissolved in ethyl acetate, anhydrous sodium sulfate was added, and the mixture was left overnight. Concentrate the filtrate, and pour the resulting residue into 70 ml of ooform! Dissolved in DCC3,09g'! r added.

After 10 minutes, methyl-4.6-0-pensolidene-α-D-
Glucopyranoside 1.41',! ? , DMAPQ
, 33 g dissolved in 5 rnl of chloroform was added, and in the same manner as 2-(2), methyl-4,6-O-pennolithene-2,3-di-1:N-(t-)l- +
7carbonyl)-L-isoroy/l]-α-D-glucopyranoside was obtained.

Yield 2.26&(64chi) m, p, 135-137℃ [α], +31° (c 1 , O, CHC1=, )
Rf, 0.91 (CM) Calculated value as C36H56012N2 C,6],,00% H,7,96% 0,2
7.09 Chi N, 3.95% Actual value C, 6]-,08% H, 7,94% 0.2
7.11 thiN, 3.87% (3) Methyl-4,,6-0-pennolian-2,3-
213 g of No0-(N-(t-butoxycarbonyl)-L-isoleutur)-α-D-glucopyranoside was added to 2-
Processing was carried out in the same manner as in (3) to obtain methyl-2,3-no-o-leucyl-α-D-glucopyranoside.

Yield 1.05.9 (71%) m・p・88-9.0℃ [α]9 +10° (c O, 5, MeOH) Rf O
,08(CM) Calculated value as C1,H5808N2Ct2 C,46,25% H,7,76chi 0,25
．． 94 inches N, 5.68% Actual value C, 46,29 inches H, 7,77% 0,25
．． 91 N, 5.70% 6 Methyl-2,:3-no〇-L-zorolyru α-D
-Synthesis of glucopyrano7d (1) L-proline 11.5.9. Boc-ON 2
7,9 f, 12- Treated in the same manner as (1), Boc-
Pro-OHfc was obtained.

Calculated value as simple seal C,,H,qOOH C155・30%)l, 8.76chi Q
, 29.49 people N, 6.45θ Actual value C, 55,32% H, 8,80% 0.29
．． 47%N, 6.41 turtles (2) Boc-Pro-OH3, 26g, DCC3
', OLg, methyl-4,6-0-pe/noridene-α-
D-Glukogi 2 Noshito'-0.33g, DMAP 1
・41g was treated in the same manner as 2-(2) to obtain methyl-4,6
-0-benzylidene-2,3-no-[N-(t-butoquinocarbonyl)-L-prolyl]-α-p-glucopyranodone was obtained.

Yield 2.67q +79 too) m-p・150-154°C [α)25 -15°(C1,CHCl3)Rf O,
87 C14H (calculated value as to012N) C26Q, 36% H, 7, 10% Q, 28
．． 40&N* 4.14 Tortoise actual measurement C, 60, 31J H, 7, 13% 0. 2
8.43@N, 4.13 (3) Methyl-4,6-0-pennolidan-2,3-no-O-[:N-(t-butoxycarginyl)-L-zorolyl]-α-D -Darkopyranoside 204g total 2- (
31 to obtain methyl-2,3-no-0-L-zorolyl-α-D-glucopyrano/do dihydrochloride, yield: 1.39 g (100%). (C1, MeOH) Rf O, 11 C, lH), 0) Calculated value as N to C1a C, 44, 26% H, 6', 5] J 0.2
7.77&N, 6.08% Actual value C, 44, 31%)l, 6.48% Q,
27.82&N, 6.11 Turtle Example 1 1 serving of instant coffee 2J and 1 serving of boiling water 150 each
A coffee liquid was prepared by dissolving the mixture in 100ml and 100ml. This coffee liquid was added to methyl-2,3-no-glycyl-α-D-glucolanondo dihydrochloride (sample A) obtained in the production example.
), methyl-2,3-no〇-alanyl~α-D-glucobyranone dihydrochloride (sample B), methyl-2,
3-no-paryl-alpha-D-glucopyranoside dihydrochloride (samp/l/c), methyl-2,3-no-0-ino-inoleucyl-alpha-ri-glucopyrano/do-dihydrochloride (sump/l/c) D), or methyl ~2.3-)-0-f loliru α-D-glucopyranoside dihydrochloride (sample E), respectively dissolved in each (test group) and dissolved in sucrose (control group), respectively. Sensory evaluation was performed using a two-point comparison method using 20 well-trained taste panels. The results are shown in Table 2.

(Samples A-E and concentration of sucrose added) Sample A 3
g/dt B O, 5' CO, 5〃 D 0.3 ff E 2〃 Sucrose 6〃 Example 2 Mixing of chocolate mousse Sweet chocolate (the product of the present invention contains bitter chocolate, acylaminated sugar of alanine, dextrin, cacao) After preparing a chocolate mousse (with butter, and a control product with bitter chocolate, sugar, and cocoa butter) using eggs and fresh cream, a chocolate mousse was prepared in a conventional manner using eggs and fresh cream.

The resulting two types of chocolate mousse were stored in a refrigerator for several days to cool and harden, and then sensory evaluation was performed by 20 taste panels.

The results are shown in Table 3. From the evaluation results and comments, the product of the present invention exhibited a mild 1" taste and bitterness similar to the sucrose-added product, and was evaluated as having good palatability.

Claims (1)

[Scope of Claims] An edible aminoacylated sugar having the formula: (wherein R1 is a branched or unbranched C1-C5 aminoalkyl group or imidazolidinyl group, and R2 is a lower alkyl group) or a salt thereof. A sweetening method characterized by adding sweetness to ingredients.