JPS61177963A - Sweetness imparter - Google Patents

Abstract

PURPOSE:A sweetness imparter, consisting of an aminoacylated saccharide (salt) such as methyl 2, 3-di-O-(L-norvalyl)-alpha-D-gluocopyranoside, etc., having good sweetness, and substitutive for sucrose. CONSTITUTION:A sweetness imparter obtained by reacting an N-(tert- butoxycarbonyl)-L-norvaline dicyclohexylammonium salt with dicyclohexylcarbodiimide and methyl 4,6,O-benzylidene-alpha-D-gluocopyranoside, filtering the resulting N,N'-dicyclohexylurea, treating the oily residue, dissolving the resultant product in dioxane, adding HCl to the solution allowing the solu tion to stand, to give methyl, 2,3-di-O-(L-norvalyl)-alpha-D-glucopyranoside (A), and preparing the aimed sweetness imparter consisting of one or more aminoacylated saccharides (salts) selected from the component (A), (B) methyl 2,3,4,6-tetra-O-(L-alanyl)-alpha-D-glucopyranoside, etc., obtained by the operation similar to the operation described above.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a sweetening agent comprising aminoacylated wMs or salts thereof.

[Conventional technology]

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 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 sugars such as sorbitol and maltitol, and dipeptides typified by Ltcol and aspartame. Sweeteners include stevioside, glycyrrhizin, acesulfame, saccharin, etc.
If 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 sweet taste and can replace sucrose.

[Problem that the invention seeks to solve]

An object of the present invention is to improve the problems of conventional sweeteners, such as calories and sweet taste quality, and to provide a sweetener that is low in calories and has good sweet taste quality.

[Means for solving problems]

The present inventors have conducted research on the synthesis and utility of peptides, as well as 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. Aminoacylated sugar has a sweet taste, and furthermore, to discover the existence of aminoacylated sugars that are of good quality and have a strong sweetness.Patent application 1986-46093)
After further research, they completed the present invention.

Regarding the taste of amino acids and peptides, there have been reports on many bitter-tasting amino acids and peptides, including hydrophobic amino acids, arginine, and proline;
Amino acids that exhibit a sweet taste, such as alanine, and sweet peptides, such as aspartame, are also known.

On the other hand, there are no reports regarding the taste of aminoacylated sugars, and methyl 2.3-diO-(L-norvalyl)-α-D-glucopyranoside, methyl 2.3.
4.6-Chitler 0-(L-alanyl)-α-D-glucopyranoside, methyl 2,3-di0-(L-aspartyl-thi-phenylalanyl)-α-D-glucopyranoside These substances, whose taste function is completely unknown, may be obtained by any method such as chemical synthesis or microbial fermentation, and there are no particular limitations on the production method.

When the above-mentioned aminoacylated class II is added as a sweetening 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, for example, by chemical synthesis method. The final target product obtained by It is preferable to use it in the form of a salt, etc., and in particular, use in the form of a hydrochloride is preferable in terms of imparting sweetness.

Aminoacylated IF of the above norvaline, alanine or aspartyl-phenylalanine! Classes are L body, 0 body, D
Any L-form may be used. Moreover, each aminoacylated saccharide or its salt may be used alone, or two or more types may be used in combination.

Experiments on Taste Taste was evaluated using a sensory test method using multiple dilutions. The results showed that methyl 2.3.4.6-chitler 0- (L-alanyl)-α-D-glucopyranoside and methyl 2.3
-Di0-(L-aspartyl-phenylalanyl)-α-D-glucopyranoside imparts sweetness, methyl 2.3
-G0-(L-norbaryl)-α-D-glucopyranoside exhibited sweetness and bitterness, and the taste power was about 2 to 14 times that of sucrose (molar concentration ratio).

(In addition, when a taste experiment was simultaneously conducted on lower alkyls other than methyl in the aminoacylated W group, it was found that all of them had a sweet taste.) Table 1 Production Example 1. (Methyl 2,3-di0-(L-norvalyl)-α-D-glucopyranoside) (1) Methyl 4.6-0-benzylidene-2,3-
Synthesis of di○-(N-(t-butoxycarbonyl)-L-norvalyl)-α-D-glucopyranoside
-butoxycarbonyl)-L-norvaline dicyclohexylammonium salt 1.99 g.

15 gmol was dissolved in 100 ml of ethyl acetate, and 50 IIll of 1M sulfuric acid was added to this mixture and stirred.

The organic layer was washed with water and dried over anhydrous sulfuric acid.

Vacuum dry the transfer and remove the oily residue with chloroform, 25ml
dissolved in. 3.09 g of dicyclohexylcarbodiimide was added to this solution at a temperature of 0°C, and the mixture was stirred for 20 minutes. To the mixture, add methyl 4,6-0-benzylidene-
A solution of 1.41 g of α-D-glucopyranoside and 0.15 g of 4-dimethylaminopyridine dissolved in 25 ml of chloroform was added, and stirring was continued at room temperature for 25 hours. The produced N,N'-dicyclohexylurea was filtered off, and the filtrate was evaporated to dryness. The oily residue was dissolved in ethyl acetate and washed successively with 4% sodium bicarbonate-4% citric acid-water. The organic layer was dried and evaporated over anhydrous sodium sulfate, and the oily residue was treated with a silica gel column using hexane-ethyl acetate (8:1 v/v) as an eluent to obtain powdered methyl 4.6-0-benzylidene- 2,
3-di0-(N-(t-butoxycarbonyl)-L
-Norbaryl]-α-D-glucopyranoside 2.45g
was obtained (yield 72%).

m, p, 143-144℃ [α]! D'52° (C+, CHCIt 5) Rf
O,56(benzene-acetone 9:1v/v)C
Calculated value as 2211%201□N2 C59,98X 117.69X N 4
．． 11% actual value C60,03χ H7,66χ N
4.13χ(2) Synthesis of methyl 2,3-di0-(L-norvalyl)-α-D-glucopyranoside: Methyl 4,6-〇-benzylidene-2,3-diO-(
N-(t-butoxycarbonyl)-L-norbaryl]-
1.36 g of α-D-glucopyranoside.

2111+01 was dissolved in 2 ml of dioxane and 10 ml of 4N-HCI dissolved in dioxane was added to the solution. This mixture was left at room temperature for 1.5 hours to obtain 0.82 g of methyl 2,3-di-0-(L-norvalyl)-α-D-glucopyranoside crystals (yield: 88%).

m, p, 163-165℃ (decomposition) [α)'','
+101° (C+, MeO)1) Rf O,1
1 (CHCII s-MeOH5:1v/v)C+t
l13aoaNzc II 2 and teno calculated value C43
, 87X l (7,362N 6.022 actual value C
43,82$ H6,02χ N 6.05X Production Example 2. (Methyl 2,3,4.6-Citler 0- (L-alanyl)-α-D-glucopyranoside) (1) Methyl 4,6-0-benzylidene-2,3-diO-(N-
(benzyloxycarbonyl)-L-alanyl]-α-
Synthesis of D-glucopyranoside: Chloroform 25mj!
3.35 g of N-(bendi/L/oxycarbonyl)-L-alanine, 15m+++ol and 3.0 g of dicyclohexylcarbodiimide were dissolved in the solution and stirred at 0°C for 20 minutes. To this mixture, 1.41 g of methyl 4,6-0-henzylidene-α-D-glucopyranoside and 0.15 g of 4-dimethylaminopyridine were added to 25 m# of chloroform.
A solution of g was added thereto, and stirring was continued at room temperature for 24 hours. The produced N,N'-dicyclohexylurea was filtered off, and the filtrate was evaporated to dryness. The oily residue was dissolved in ethyl acetate and thoroughly washed with 4% sodium bicarbonate-2% hydrochloric acid-water. The organic layer was dried with anhydrous sulfuric acid) and evaporated with IJum, crystallized with ether-petroleum ether, and methyl 4.6
-0-benzylidene-2,3-diO-(N-(benzyloxycarbonyl)-L-alanyl)-α-D-glucopyranoside was obtained.

Yield 80% m, p, 62-63℃ [α)” +23@(cl, chloroform) I”
1'1650.1550 cm-' (7 mido) ax 750.690 (phenyl) 1690, 1980 (ester) 3300 cm (NH) Teno calculated value as C3hHaoNzOIt C62,42χ, H5,82χ, N4
．． 05χ actual value C62,39χ, H5,80
X, N4.06X(2) Methyl 2,3,4.6-
Chitler 0- (N-(benzyloxycarbonyl)-
Synthesis of L-alanyl]-α-D-glucopyranoside: Methyl 4,6-〇-benzylidene-2,3-diO-(
N-(benzyloxycarbonyl)-L-alanyl]-
2.77 g of α-D-glucopyranoside.

4 mmol was dissolved in 5 ml of dioxane, and 100 mj of 90% acetic acid was added to the solution. was added and held at 75°C for 2.5 hours. The solvent was evaporated and the residue was azeotropically distilled several times to obtain an oily residue of methyl 2,3-di0-(N-(benzyloxycarbonyl)-L-alanyl)-α-D-glucopyranoside (uncrystallized). 1.93g (yield: 8)
0%). 1.34 g of N-(benzyloxycarbonyl)-L-alanine in 15 ml of chloroform, 6III
llol and dicyclohex'/)Lp, /J JL
t 1.24 g of fodiimide was dissolved and stirred at 0° C. for 20 minutes. Methyl 2,3-di0'''' [N-(benzyloxycarbonyl)-L-7 in 15mf of chloroform
Ranil]-α-D-glucopyranoside 1.21g, 21
1111101 and 4-dimethylaminopyrodine 0.0
6 g was dissolved and stirring was continued for 24 hours at room temperature. The produced N,N'-dicumehexylurea was filtered off, and the filtrate was evaporated to dryness. The oily residue was dissolved in ethyl acetate and washed successively with 4% sodium bicarbonate-2% hydrochloric acid-water. The organic layer was dried over anhydrous sodium sulfate and evaporated, using benzene-acetone (9:1 v/v) as the eluent.
After treatment with a silica gel column and ether-petroleum ether, 1.66 g of methyl 2.3.4.6-Chittler-(N-(benzyloxycarbonyl)-L-alanyl)-α-D-glucopyranoside was obtained (yield 82%).

m, p, 102-104℃ [α)”+34° (C+, CHC13)Cs+1
Calculated value as IssN40+a C60,34χ 115.76χ N 5.5
2χ actual value C60, 31χ )l 5.74χ N
S, 54χ(3) Synthesis of methyl 2,3,4,6-chitler 0-(L-alanyl)-α-D-glucopyranoside: methyl 2,3,4,6-chitler 0-(N-(benzyloxy Carbonyl) L-7 Rani) Lt] = α
- Riichi glucopyranoside 1.01 g, 1 mmol
methanol-II' aft (1; 1) 4 ml
Dissolved in l. Add palladium black (ca, 2g) to this solution.
was added, and hydrogen gas was gently blown in while stirring. After 4 hours, the catalyst was filtered off and the filtrate was evaporated. Dissolve the residue in a small amount of acetone and dioxane 18.3++1
4N-HC dissolved in 1/! Add 2, 3.4.
0.56 g of 6-Chitler 0-(L-alanyl)-α-D-glucopyranoside was obtained (yield 90%).

m, p, 128 131℃ [α)”+85° (C+ Meal) C+ Calculated value as J13aNaO+ oC1a C
36,55X If 6.13Z N 8.97!
Actual value C36,60χ H6,07χ N 8.92
χ Production Example 3. (Methyl 2,3-di0-(L-aspartyl-L-phenylalanyl)-α-D-glucopyranoside) (11methyl4.6-0-benzylidene-2,3-diO-2,3-di Synthesis of 0-(β,N-bis(benzyloxycarbonyl)-L-alanyl-L-phenylalanyl]-α-D-glucopyranoside: Chloroform 1
β,N-bis(benzyloxycarbonyl)-
L-alanyl-shi-phenylalanine (Z-Asp(
OBzl) -Phe-〇H) 3.03 g, 6m
mol and dicyclohexylalbodiimide 1.24
g was dissolved and stirred at 0°C for 20 minutes. Add 15nj of chloroform to the mixture. Methyl 4.6-0-benzylidene-α-D-glucopyranoside 0.56 g, 2 mm
A solution of 0.06 g of ol and 4-dimethylaminopyridine was added, and stirring was continued at room temperature for 24 hours. The N,N'-dicyclohexylurea formed was filtered off, the filtrate was evaporated to dryness, and the oily residue was dissolved in ethyl acetate.
% sodium bicarbonate-2% hydrochloric acid-water.

The organic layer was dried over anhydrous sodium sulfate, evaporated, and crystallized from ether-petroleum ether to obtain 2.00 g of the desired product (yield: 80%).

m, p, 87-88℃ [”) %' +19 (CI, Cl1tl,)R
f O,3H benzene-acetone 9:1)C7°+1. . Calculated value as 0IIIN4 C66,97X H5,62X N 4.
46g actual value C66,93Z I! 5.60X
N 4.49χ+2) 2.3-G0- (L
Synthesis of -7'

-[β,N-bis(benzyloxycarbonyl)-L-
Alanyl-L-phenylalanyl]-α-D-glucopyranoside was dissolved in methanol-acetic acid (1:1) and hydrogenated overnight at room temperature using palladium black as a catalyst.

The catalyst was filtered off, the filtrate was evaporated, and powdered methyl 2.3
-G. 0.55 g of -(L-aspartyl-d-phenylalanyl)-α-D-glucopyranoside was obtained (yield 76%).

m, p, 94 97℃ [α)”D'+35° (C+1MeOH)Rf
O,5(n-BuOH-acetone-pyridine-water 4
:1:1:2) Calculated value as Casl14JLaO+ 4C1z C
50,06χ H5,60χ N 7.07χ Actual value
C50, 11
mj! to prepare a coffee liquid.

The methyl 2,3-di0- obtained in the production example was added to this coffee liquid.
(L-norvalyl)-α-D-glucopyranoside (sample A), methyl 2,3,4.6-chitler 0- (
L-alanyl)-α-D-glucopyranoside (sample B) or methyl 2,3-di-0-(L-aspartyl-phenylalanyl)-α-D-glucopyranoside (sample C), respectively. A sample (test group) and a sample in which RvM was dissolved (control group) were prepared, and a sensory evaluation was performed using a two-point comparison method using 20 well-trained taste panels. The results are shown in Table 2.

Table 2 (Samples A-C and sucrose concentration) Sample A
O05νdl B 4 〃 C1, 5〃 蔗 IJ! 6. Example 2 Preparation of chocolate mousse Sweet chocolate (products of the present invention include bitter chiccolate, methyl-2,3-di-0-(L-aspartyl-phenylalanyl)-α-D-glucopyranoside, dextrin, After preparing a chocolate mousse (with cocoa butter and a control (currently with bitter chocolate, sugar, and cocoa butter)), a chocolate mousse was prepared using eggs and fresh cream in a conventional manner.

The resulting two types of chocolate mousse 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. From the evaluation results and comments, the product of the present invention exhibits a mild sweetness and bitterness similar to sucrose-added products,
The taste also received good reviews.

Table 3

Claims (1)

[Claims] Methyl 2,3-di-O-(L-norvalyl)-α-D-
Glucopyranoside, methyl 2,3,4,6-tetra-O
-(L-alanyl)-α-D-glucopyranoside and methyl 2,3-di-O-(L-aspartyl-L-phenylalanyl)-α-D-glucopyranoside at least one aminoacylation A sweetening agent characterized by comprising a sugar or a salt thereof.