JPH0873490A - Strogin compound, its production, taste modifier and blend - Google Patents

Abstract

PURPOSE: To obtain the subject new compound which is a specific strogin compound available by separation and purification from a plant belonging to the family Acanthaceae and having taste modifying activities and excellent in stability due to a nonprotein and useful as a taste modifier, etc. CONSTITUTION: This new strogin compound of the formula [A is a hexapyranose residue in which OH groups may optionally be etherified or acylated; B is a hexapyranose residue and pentopyranose residue in which OH groups may optionally be etherified or acylated and a uronic acid residue in which the primary alcohol group in the pyranose residue is converted into carboxyl group; (n) is 1-3; R1 to R3 are each H, a 1-4C alkyl or a 2-4C acyl]. The compound has taste modifying activities and is excellent in stability due to a nonprotein and useful as a taste modifier, etc. The compound is obtained by extracting a plant belonging to the family Acanthaceae (e.g. Strobilanthes dyerianus) with a solvent and then purifying the resultant extract by the column chromatography.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel strogin compound, a method for producing the same, a taste modifier comprising the novel strogin compound, and a taste modifying composition containing the novel strogin compound as a taste modifier.

[0002]

2. Description of the Related Art As terpenoid taste modifiers,
Up to now, gymnemic acid and didifin are known. However, although they have the effect of eliminating sweetness,
It has no effect of changing tasteless to sweet. As a substance having such an action, a protein-based taste-modifying substance called curculin is known (for example, JP-A-2-1042).
63 publication). However, since curculin is a protein, it has a drawback that it is inferior in stability against heat and organic solvents.

[0003]

DISCLOSURE OF THE INVENTION The present inventor has searched for a compound which is a non-protein compound and has the action of changing tastelessness to sweetness. It was found that glycosides / strodin are excellent compounds in the above points. The present invention is based on these findings.

[0004]

Accordingly, the present invention provides a compound represented by the general formula (I):

Embedded image (In the formula, A is a hexapyranose residue whose hydroxyl group is optionally etherified or acylated, and B is a hexapyranose residue whose hydroxyl group is optionally etherified or acylated. Group, a hydroxyl group is a pentopyranose residue which may be etherified or acylated in some cases, or a uronic acid residue in which the primary alcohol group of these pyranose residues is a carboxyl group, and n is 1 Is an integer from 3 to 3, and when n is 2 or 3, B can be the same or different groups, and R ₁ , R ₂
And R ₃ are the same or different and each is a hydrogen atom or a carbon number of 1-4
Alkyl groups or acyl groups having 2 to 4 carbon atoms)
And a salt thereof.

The present invention also relates to the family Acanthaceae (Acanth).
aceae) from a plant belonging to the general formula (I) or a salt thereof.
The present invention also relates to a method for producing the above-mentioned strozin compound or a salt thereof. Furthermore, the present invention relates to a taste-modifying agent, characterized in that the taste-modifying agent comprises a strogin compound represented by the general formula (I) or a salt thereof. Furthermore, the present invention relates to a taste-modifying formulation, characterized in that it comprises a strogin compound represented by the general formula (I) or a salt thereof as a taste-modifying agent.

The present invention will be described in detail below. In the general formula (I), the group A is a hexapyranose residue, for example, D-glucose, D-galactose, L-galactose or D-mannose, or preferably 6-deoxyhexose (for example, L-rhamnose or L- Fucose), the hydroxyl groups of which may optionally be acylated or etherified. Also,
The group A can be bonded to the ring carbon atom of the pentacyclic compound moiety via any hydroxyl group, but can be bonded to the ring carbon atom of the pentacyclic compound moiety via the 1-position hydroxyl group. Is preferred. Therefore, the preferred group A
Is, for example, the general formula (II):

[Chemical 3] (In the formula, R ₄ , R ₅ and R ₆ are the same or different and each is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an acyl group having 2 to 4 carbon atoms). It is a base.

The group B is a pentopyranose residue, for example
L-arabinose, D-xylose or D-ribose residues, hexapyranose residues such as D-glucose,
It is a residue of D-galactose, L-galactose, D-mannose, L-rhamnose, L-fucose, or a uronic acid residue, especially a residue of uronic acid derived from 6-carbon sugar, for example, glucuronic acid. , Residues of mannuronic acid, iduronic acid or galacturonic acid, the hydroxyl groups of which may optionally be acylated or etherified. Also, when two or more groups B are present, those 5-carbon sugars, 6-carbon sugars or uronic acids may be the same or different 5-carbon sugars, 6-carbon sugars or uronic acid residues, The hydroxyl groups of can also be substituted with the same or different substituents. Furthermore, the two or three groups B may each be linked by a 1,3-bond, a 1,4-bond or preferably a 1,2-bond.
For example, a preferred BB- is represented by the general formula (III):

[Chemical 4] (In the formula, R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an acyl group having 2 to 4 carbon atoms. There is) a group represented by.

In the present specification, the alkyl group having 1 to 4 carbon atoms is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, or It is a tert-butyl group. Further, the acyl group having 2 to 4 carbon atoms is, for example,
It is an acetyl group, a propionyl group or a butyryl group.

The salt of the trozine compound represented by the general formula (I) is a compound in which the group R ₁₂ of the COOR ₁₂ group is a hydrogen atom, and the group R ₁₂ is substituted with various metal atoms. Those metal atoms are, for example, alkali metals (eg sodium, potassium or lithium), alkaline earth metals (eg magnesium, calcium or barium), aluminum, iron, zinc, copper,
Nickel or cobalt with a metal having a valence (n) of 2 or more forms a 1 / n salt.

In the pentacyclic compound portion of the stromdine compound represented by the above general formula (I), as a substituent, a 5-carbon sugar,
6-carbon sugar or uronic acid substituent (B-, BB- or BB
-B-) 1, 6-carbon sugar substituent (A) 1, methyl group 6
Exist, _one —CH ₂ OR ₁ group, one —CH ₂ OR ₃ group, and one OR ₂ group. The configuration of these substituents is not particularly limited, but it is preferably, for example, the same configuration as that of strozine represented by the formula (IV) described later.

The compound represented by the general formula (I) according to the present invention can be isolated by, for example, extracting from a plant belonging to the genus Amblyceae. That is, from a plant of a family belonging to the genus Amblyceae, a component containing stromin is extracted, and then the extract is subjected to adsorption column chromatography using a synthetic adsorbent, silica gel column chromatography, and / or a reversed-phase silica gel column. It is possible to obtain a purified product of trodin by separating it by chromatography.

The plant from which the compound represented by the general formula (I) according to the present invention can be extracted is a plant belonging to the genus Lepidoptera.
bilanthes) plants, for example, Uramurasaki (dy
erianus), Ryukyuai (cusia), Isehanabi (japonica), Suzushisou (oligantha) or Maingai (maingayi); Plants belonging to the genus Justicia, for example, foxgroom (procumbens) or Lisnosipia (betonica); )
Plants belonging to, for example, sardine vine (alata), Kodachi sardine vine (erecta), Bengal sardine vine (gr)
andiflora), laurel vine (laurifolia), purple vine (affinis), odor vine (fr)
agrans), Scutellaria japonicum (kirkii) or Fogella yazazuzura (vogeliana);
ne) plants such as, for example, guttat; Staurorogyne plants, for example, merguensis, setiger, kingiana, elongata; Hygrophila. Plants to which they belong, for example, Phlomoides; Ruellia
Plant belonging to, for example, repens. Staurogyne melgensis
merguensis) is particularly preferred.

A part (leaves, stems, roots, etc.) or the whole of the above-mentioned plant is used as it is or after it is dried, and then preferably, it is crushed to a slightly finer size before use. Preference is given to using dried leaves. Water can be used for extraction. The temperature of water is not limited, and extraction with water of 0 to 100 ° C is possible, but water of 40 to 60 ° C is preferably used. Also,
Instead of pure water, extraction can be performed with alcohol-added water or alcohol. The alcohol concentration of alcohol-water is not particularly limited, but is 1% (v / v%) to 4
0% (v / v%) is preferred. The amount of alcohol added is 4
Extraction is possible even with 0% (v / v%) to 100% (v / v%), but the alcohol concentration of the extract must be 40% (v / v%) or less after the extraction operation. There is. As the alcohol that can be used for extraction, a lower alcohol, particularly methanol or ethanol is preferable.

In the extraction operation, 5 volumes or more of water (normal temperature water, warm water or hot water) or lower alcohol added water is added to the plant raw material and stirred. The stirring time is 5 minutes or more. After stirring, filtration is performed to obtain an extract. This extraction operation is preferably repeated until the presence of strodin in the extract is no longer confirmed. The presence of strogin is confirmed by, for example, a sensory test.

Next, the obtained extract is purified by various chromatographic treatments. Specifically, it is first treated by adsorption chromatography using a synthetic adsorbent, followed by silica gel chromatography, and finally by reversed-phase silica gel chromatography, or first, adsorption using a synthetic adsorbent as described above. High-purity strogin can be obtained by subjecting it to chromatography, followed by silica gel chromatography, and preferably repeating twice or more.

In adsorption chromatography using a synthetic adsorbent, for example, a support of a high porous polymer obtained by polymerizing styrene and divinylbenzene is used. Add the above extract to the column of synthetic adsorbent. in this case,
The alcohol concentration of the extract is preferably 40% (v / v%) or less. The pH of the extract when added to the column may be 7 or less, but it is preferable to lower the pH of the extract to 4 or less in order to strongly adsorb strogin to the gel. An organic acid or an inorganic acid can be used to adjust the pH, but hydrochloric acid, sulfuric acid, nitric acid, acetic acid or the like is preferable.

Elution of the adsorbed strogin is performed, for example, with a mixed solution of organic solvent / water. As the organic solvent, a lower alcohol (for example, methanol or ethanol),
Alternatively, acetone or the like can be used. The concentration of lower alcohol in the mixed eluate is 60% (v / v%) to 90%
It is preferably (v / v%). When acetone is used as the organic solvent, 40% (v / v%) to 60% (v
/ V%) is preferred. A crude extract of strogin can be obtained by flowing the mixed eluate in an amount equal to or more than 1 time the gel volume.

The crude extract is then further processed by silica gel chromatography. As for the method of addition, the crude extract is adsorbed on a small amount of silica gel in advance (elution separation method), or a solution dissolved in a small amount of eluent is added. As the eluent, for example, the lower layer of a mixed solution composed of three components of alcohol / non-alcoholic organic solvent / water is used. Alcohols that can be used are, for example, methanol or ethanol. As the non-alcoholic organic solvent, methylene chloride, chloroform or the like can be used. The mixing ratio of them is, for example, 30% (v / v%) or more for alcohol and 50% (v / v%) or more for non-alcoholic organic solvent. When methanol is used as the alcohol and methylene chloride is used as the non-alcoholic organic solvent, the methanol content is 30%.
(V / v%) to 35% (v / v%), and methylene chloride is preferably 52% (v / v%) to 57% (v / v%).

The detection of strogin can be performed using thin layer chromatography (hereinafter, TLC) or high performance liquid chromatography (hereinafter, HPLC). TL
In C, a normal phase silica gel plate can be used, and a mixed solution having the same composition as the eluate of silica gel chromatography can be used as a developing solvent. The composition ratio of the mixed solution used as the developing solvent is, for example, 30% alcohol.
(V / v%) or more, and the non-alcoholic organic solvent is 5
It is 0% (v / v%) or more. When methanol is used as the alcohol and chloroform is used as the non-alcoholic organic solvent, the methanol content is 35% (v / v%) to 38%.
% (V / v%), 53% chloroform (v / v%)
It is preferably ˜56% (v / v%).

When strogin is detected by HPLC, a reverse phase HPLC column can be used for separation and detection. For detection, ultraviolet absorption or differential refraction is measured. The ultraviolet absorption preferably has a wavelength of 200 nm to 240 nm, and particularly preferably 205 nm to 215 nm. Further, as the eluent, for example, a mixed liquid containing two components of alcohol and water is used. The alcohol used is, for example, methanol, ethanol, n-propanol, iso-propanol or the like. The mixing ratio is, for example, 40% (v / v%) to 80% alcohol.
(V / v%). Further, as the alcohol, two kinds of alcohol can be mixed. In this case, the mixing ratio of highly polar alcohol is 50% (v / v%) to 70%.
% (V / v%), alcohol with low polarity is 1% (v / v%)
v%) to 10% (v / v%) is preferable. Preferably, highly polar alcohol is 50% (v / v%)
~ 60% (v / v%), low polar alcohol 5%
It is preferably (v / v%) to 10% (v / v%). It is particularly preferable to add 0.1% (v / v%) to 1% (v / v%) acetic acid.

When purification is carried out by reversed-phase silica gel column chromatography after the separation operation by silica gel chromatography, a mixed solution of a water-soluble organic solvent and water can be used as a solution and an eluent. Examples of the water-soluble organic solvent include acetonitrile, methanol, ethanol, isopropanol, acetone and the like. The concentration of the water-soluble organic solvent is, for example, 10%
(V / v%) to 50% (v / v%). Furthermore, 0.
It is preferred to include from 01% (v / v%) to 1.0% (v / v%) acetic acid. 35% for acetonitrile
(V / v%) to 40% (v / v%) acetonitrile aqueous solution, acetic acid 0.05% (v / v%) to 0.2% (v / v
%) Is preferable.

Various substituents can be converted into other substituents in the novel strozine compound represented by the above general formula (I) obtained by the above extraction method. For example, the corresponding acyl group can be introduced by treating a strozine compound having a free hydroxyl group on the sugar substituent with a carboxylic acid, an acid anhydride or an acid halide. In addition, a strozine compound having an acylated hydroxyl group can be converted to a strozine compound having a corresponding free hydroxyl group by treating with an alkali.

Strodin compounds having a free hydroxyl group on the saccharide substituent group should be converted to the corresponding alcoholate by the action of an alkali metal and then treated with an alkyl halide to introduce the corresponding alkoxy group. You can Alternatively, the rosin compound having an etherified hydroxyl group can be converted to a corresponding strodin compound having a free hydroxyl group by treating with a hot mineral acid.

The ester group can be introduced by treating a strozine compound having a free carboxyl group (R ₁ = H) with an alcohol to which any strong acid is added. On the contrary, the esterified carboxyl group (R ₁ =
By treating a strozine compound having an alkyl group) with a carboxylic acid, it can be converted into a strozine compound having a corresponding free carboxyl group (R ₁ = H). Furthermore, a strozine compound having a free carboxyl group (R ₁ = H) can be converted into a corresponding salt by treating it with an alkaline solution containing a salt or a chloride solution containing a salt, and vice versa. Can also be converted to the corresponding free carboxylic acid by treatment with acid. The strogin compound represented by the general formula (I) according to the present invention can also be prepared by a chemical synthesis method.

The stromdine compound represented by the general formula (I) according to the present invention can be used as a taste modifier. For example, the strogin compound of the present invention or a salt thereof,
When tasteless substances or water are consumed as they are or after being contained in the mouth in the form of a solution or the like, they have an effect of making those tasteless substances or water feel sweet. Furthermore, when a strogin compound or a salt thereof is contained in the mouth, it has an effect of making even the air breathing thereafter feel sweet.

The taste-modifying agent of the present invention comprises a strozine compound represented by the above general formula (I) or a salt thereof, and depending on the case, a suitable solvent (for example, an aqueous alcohol solvent, water, a weak acid solution or a weak alkali). Solution) or a suitable dispersion medium (eg, methyl cellulose,
Dispersed form dispersed in starch, lactose, carboxymethyl cellulose, sugar, sugar alcohol, sodium alginate, calcium hydrogen phosphate, synthetic aluminum silicate, microcrystalline cellulose, polyvinylpyrrolidone, or colloidal silica gel, and further, film form, tablet It can be in the form of powder, emulsion or spray. Furthermore, the taste-modifying agent of the present invention may contain any substance that does not impair the taste-modifying effect of strogin and that has edible properties.

By eating the taste-modifying agent of the present invention in advance, sweetness can be felt when eating or drinking a non-taste substance (for example, water or air) or green tea. In this case, the single dose (drinking amount) of the taste-modifying agent of the present invention is
0.001-0.5 mg in terms of strodin compound,
It is preferably 0.01 to 0.2 mg.

Further, since the strogin compound of the present invention or its salt itself exhibits a weak sweetness, it can be added to food or beverage to maintain the sweetness and further modify the taste. The food or beverage to which the taste modifier of the present invention can be added is not particularly limited, but it is particularly preferable to add it to a food or beverage that is not kept warm (cooled to room temperature or lower) during eating and drinking.

Further, the above-mentioned strozine compound or a salt thereof can be blended in a plastic material for molding a container for food or beverage. In particular, when foods and beverages are stored in a plastic container, a bitterness component or the like exudes from the container material and is transferred to foods or beverages, which can improve the phenomenon of impairing the taste of the contents of the container. That is,
When a food or beverage is stored in a container molded from a plastic material containing the taste modifier according to the present invention, not only the bitterness component described above exudes, but also the strozine compound according to the present invention or a salt thereof exudes. The activity of the above-mentioned bitterness components is suppressed by the strogin compound or its salt.

In the case where the above-mentioned strozine compound represented by the general formula (I) or a salt thereof according to the present invention is blended with food as a taste modifier, it can be taken per one intake (for example, one can juice). , 0.001 to 1 mg, preferably 0.01 to 0.5 mg, and when blended with a plastic material (for example, a plastic material for molding a container),
The amount is 0.001 to 1% by weight, preferably 0.05 to 0.2% by weight.

[0031]

The present invention will be described in more detail with reference to the following examples, which do not limit the scope of the present invention. Example 1 (1) Extraction Staurogyne melgensis kuntsue (Staurogyne m
erguensis Kuntze (Malaysia) leaves were dried and finely crushed to obtain 20 g of crushed product, and 600 ml of water was added to the crushed product to give 5
The mixture was kept warm at 0 ° C, stirred, and filtered with a cotton plug. This filtrate was dark brown and had taste-modifying activity. The taste-modifying activity was also confirmed in the crushed leaves that had been filtered. Further, 500 ml of water was added to the crushed leaves separated by filtration, the temperature was kept at 50 ° C., and the mixture was stirred, and then filtered again with a cotton plug. The filtrate was dark brown and had a taste-modifying activity, but leaves separated by filtration had no taste-modifying activity. The filtrates obtained from the two times were combined to obtain an extract containing strogin. The taste-modifying activity was confirmed by a sensory test.

(2) Separation by Adsorption Chromatography To the extract obtained in Example 1 (1), hydrochloric acid was added to adjust the pH to 3. Next, the extract was treated with a synthetic adsorbent-packed column chromatography (Diaion HP-21 column: diameter 2.7 cm × 14 cm; bed volume 120 m).
1; manufactured by Mitsubishi Kasei Co., Ltd.) to adsorb strogin. Then, 40% (v / v%) aqueous acetone solution was flowed in an amount 5 times the gel volume to elute impurities. Further, the strogin active fraction was eluted with a 60% (v / v%) acetone aqueous solution which was 5 times the gel volume and dried under reduced pressure. As a result, 230 mg of dark brown crystals were obtained.

(3) Silica gel column chromatography
Separation by means of 230 mg of the brownish brown crystals of Example 1 (2) / methylene chloride as a solvent for silica gel column chromatography /
Methanol / water (60:38:14) mixture (lower layer) 1
It was dissolved in 0 ml. A silica gel (Silica gel 60 No. 7734; manufactured by Merck & Co.) column (diameter 2.
2 cm x 33 cm; dry gel weight 60 g).
A methylene chloride / methanol / water (60:38:14) mixture (lower layer) was poured, and the eluate was collected in 200 ml portions. The collected fractions were confirmed by thin layer chromatography (Merck). The developing solvent used was chloroform / methanol / water (6: 4: 1). The eluate fractions of strogin confirmed by thin layer chromatography were combined and dried under reduced pressure to give 90 mg of a crudely purified product.

(4) Reversed phase silica gel column chromatograph
Purification by Fee 90 mg of the crude product of Example 1 (3) was added in a small amount of 0.1%.
It was dissolved in a 38% aqueous acetonitrile solution containing acetic acid. This solution was pre-filled with the same solution as the solution of Example 1 (3) above, reverse phase silica gel RP-2 (silica gel 60
Silanized; Merck) column (diameter 1.7 cm
X 40 cm; dry gel weight 45 g) and place on top of 0.
It was developed with a 38% acetonitrile aqueous solution containing 1% acetic acid. The active fractions were collected and dried under reduced pressure to obtain 30 mg of white highly pure strogin.

Various physicochemical data of strogin obtained by the above method are shown below. (A) color and shape; white powder (b) Elemental analysis; C = 57.56%; H = 7.96% (c) molecular _{formula; C 53 H 82 O 22 ·} 2H 2 O (d) Mass spectrum ( FAB-MS); m / z 10
70 (FIG. 1) (e) Melting point; 252 to 253 ° C. (f) Ultraviolet and visible absorption spectrum (FIG. 2)

(G) Infrared absorption spectrum (FIG. 3) (K
Br cm ^-1 ): 3404, 2978, 2926, 17
45, 1612, 1416, 1373, 1230, 11
75,1132,1045,797,602 (h) ¹ H-NMR spectrum (400 MHz, CD ₃
OD) (Fig. 4) δ (ppm) 0.70 (3H, s), 0.95 (3
H, s), 0.96 (3H, s), 0.98 (3H,
s), 1.01 (3H, s), 0.89 to 1.09 (4
H, m), 1.16 (3H, d), 1.23 (3H,
s), 1.29 (2H, m), 1.40 (1H, br
m), 1.50 (1H, br m), 1.56-1.7.
7 (4H, m), 1.89 (5H, m), 1.96 (3
H, s), 2.04 (3H, s), 2.13 (3H,
s), 2.30 (2H, br s), 2.92 (1H,
d), 3.13 (1H, dd), 3.22 (2H,
m), 3.31 (1H, dd), 3.39 (1H,
d), 3.42 to 3.54 (4H, m), 3.59 (2
H, m), 3.75 (1H, br s), 3.79 (2
H, dd), 3.98 (1H, br d), 4.14.
(1H, m), 4.54 (2H, dd), 4.91 (1
H, br s), 5.01 (1H, dd), 5.23
(1H, brs), 5.31 (1H, dd), 5.41
(1H, dd)

(I) ¹³ C-NMR spectrum (100M
Hz, CD ₃ OD) (FIG. 5) δ (ppm) 13.1q, 16.6q, 17.6q,
17.7q, 17.7q, 18.8t, 20.6q, 2
0.7q, 20.7q, 22.1q, 24.7t, 2
6.5t, 27.3t, 27.3q, 27.9t, 3
3.1t, 37.5s, 39.6t, 40.1s, 4
1.2s, 41.2t, 41.7s, 42.9s, 4
3.6d, 44.0s, 47.8d, 48.9d, 6
4.1t, 67.1t, 67.9d, 69.2t, 7
0.9d, 71.1d, 72.3d, 73.0d, 7
6.2d, 76.3d, 77.7d, 77.8d, 7
8.1d, 79.4d, 79.9d, 82.9d, 8
3.3d, 100.7d, 104.5d, 106.2
d, 123.6d, 145.1s, 171.7s, 17
1.7s, 171.8s, 173.2s

(J) Color reaction: 10% sulfuric acid, positive for sulfuric acid-orcinol reaction (k) Solubility: Soluble in methanol and pyridine, difficult to dissolve in water and acetone, and insoluble in chloroform and ethyl acetate. (L) Thin layer chromatography; carrier silica gel plate (manufactured by Merck Ltd.) Developing solvent system [chloroform / methanol / water (6:
4: 1)]: Rf value = 0.6 Developing solvent system [methylene chloride / methanol / water (60:
38:12, lower layer): Rf value = 0.68 (m) distinction between basic, acidic and neutral; weakly acidic substance

(5) Acid Hydrolysis of Strogin About 2 mg of high-purity strodin obtained in Example 1 (4) was accurately weighed in a sealed tube and dissolved in 1 ml of 4N sulfuric acid. After sealing the tube, it was heated at 100 ° C. for 4 hours. The reaction solution was returned to room temperature and added to an anion exchange resin (Amberlite IRA-400) (carbonate type) for neutralization. Filter this,
A hydrolyzed solution was obtained. (6) Trimethylsilylation of free sugar After hydrolyzing the hydrolyzed solution of Example 1 (5) under reduced pressure, 2 m of water was added.
It was dissolved in 1. 5 ml of chloroform was added to this aqueous solution, and water-insoluble substances other than monosaccharides were extracted into the chloroform layer. After repeating this extraction operation 5 times, the aqueous layer was dried under reduced pressure. The obtained dried product under reduced pressure was subjected to trimethylsilyl (TMS) conversion. A pyridine / hexamethyldisilazane / trimethylchlorosilane (10: 2: 1) mixture was used as the TMS agent. 0.24 ml of TMS agent was added to the dried product under reduced pressure and stirred for 30 seconds,
Let stand for 30 minutes at room temperature. Next, 0.6 ml each of chloroform and water were added and stirred. After standing still, the aqueous layer was discarded, 0.6 ml of water was newly added, and the mixture was stirred. After repeating this operation 5 times, the chloroform layer was dried to remove pyridine. This was redissolved in about 1 ml of chloroform. L-rhamnose, D (+)-xylose and glucuronic acid as standard sugars were subjected to acid hydrolysis and TMS in the same manner.
Turned into These are analyzed by gas chromatography mass spectrometry (G
It was analyzed by the C-MS) method.

(7) Gas chromatography mass spectrometry
Monosaccharide composition analysis by (GC-MS) method The sample of Example 1 (6) was analyzed under the following conditions. Apparatus: JMS-DX303HF (JEOL) Column: DBI-3000 Initial temperature: 100 ° C Final temperature: 220 ° C Temperature increase: 10 ° C / min Injection temperature: 200 ° C Carrier gas; He gas flow rate: 10.5 ml / min The above conditions The elution time of each sugar was compared as a result of the analysis in (FIG. 6).

The above analysis results and Correlation Sp
ectroscopy (COSY), HomonuclearHartmann-Hahn (HOH
AHA), Nuclear Overhauser and Exchange Spectrosco
py (NOESY), ¹ H-Detected Multiple Quantum Coherre
nce Spectrum (HMQC), ¹ H-Detected Multiple-bond
Heteronuclear Multiple Quantum Coherrence Spectrum
From the analysis results of (HMBC) and Relayed COSY Spectrum, it was found that the structure of strogin obtained in Example 1 (4) above is represented by the following formula (IV).

[Chemical 5] (In the formula, Me is a methyl group and Ac is an acetyl group.)

Example 2 Sweetness of Strogin The high-purity strogin powder obtained in Example 1 (4) was dissolved in water to prepare 0.2%, 0.1%, 0.05%, 0.025.
%, 0.0125%, 0.00625% and 0.003
A 125% aqueous solution was prepared. This strogin aqueous solution 0.
The sweetness intensity when 5 ml was contained in the mouth was compared with the sucrose aqueous solution of each concentration. As a result, when the 0.1% strogin aqueous solution was contained in the mouth, the sweetness became maximum, and the sweetness at this time corresponded to the sweetness of the 0.4 M sucrose aqueous solution.

Example 3 Induced Sweetness of Strogin The high-purity strogin powder obtained in Example 1 (4) was dissolved in water to give 0.43%, 0.215%, 0.1075%,
0.05375% and 0.026875% aqueous solutions were prepared. After 0.5 ml of this aqueous solution of strogin was contained in the mouth for 2 minutes and then spit out, cold water at 1 ° C. was consumed. At this time, the intensity of sweetness induced by strogin was compared with the sucrose aqueous solution of each concentration. As a result, when 0.215% strogin aqueous solution was contained in the mouth, the sweetness-inducing activity by strogin became maximum, and the sweetness at this time corresponded to the sweetness of the 6% sucrose aqueous solution.

Example 4: Strogin compounded tablets Tablets were prepared using the crudely purified trodin powder obtained in Example 1 (3). The composition is described below. Gum arabic; 8% by weight Crude purified strogin powder; 0.015% by weight mannitol; 91.985% by weight 1.3 g of tablets prepared by the above formulation was eaten. as a result,
The sweetness of mannitol was enhanced. Also, tablets 1.3g
After eating, water, green tea and air were felt sweet.

Example 5 One commercially available chewing gum (about 3 g) and Example 1
About 0.5 mg of the crudely purified strogin powder of (3) was simultaneously included in the mouth and ate. As a result, the time during which sweetness was felt lasted for about 2 minutes longer than when only chewing gum was eaten.

Example 6 To a commercially available fresh cream, 0.0002% by weight of high-purity strodin of Example 1 (4) was added to prepare a fresh strogin-containing cream. On the other hand, coffee jelly with sugar and coffee jelly without sugar were created. A commercially available fresh cream was placed on the sugar-containing coffee jelly, and a strogin-containing fresh cream was placed on the sugar-free coffee jelly (the ratio of each fresh cream and the coffee jelly was the same), and they were tasted. As a result, the sugar-free coffee jelly had the same sweetness as the sugar-containing coffee jelly.

Example 7 To 340 g of commercially available cold canned oolong tea, 1 mg of the highly pure strogin of Example 1 (4) was added and consumed. As a result, mellow sweetness was felt in the oolong tea. In addition, the astringency on the tongue felt after eating and drinking commercially available oolong tea was suppressed.

Example 8 A plastic test piece was prepared according to the formulation shown in Table 1 below.

[Table 1] Ingredients by weight Polypropylene random copolymer 100 Tetrakis [methylene-β- (3,5-ditertiary butyl 0.1-4-hydroxyphenyl) propionate] methane Tris (2,4-ditertiary) Butylphenyl ) phosphite 0.1 Calcium stearate 0.05 Crude strogin powder [Example 1 (3)] 0.1

After blending each of the above ingredients, 25
Extrusion processing was performed at 0 ° C. to prepare pellets. next,
The pellets were injection-molded at 250 ° C. and then rapidly cooled to 60 ° C. to prepare test pieces with a thickness of 1 mm. This test piece 10g
200 ml of water was placed in a glass container and kept at 60 ° C. for 24 hours, and the odor (bitterness) of the test piece transferred to water was examined. A test piece containing no crudely purified strogin powder [product of Example 1 (3)] as a blank was prepared, and the same test was performed. As a result, the water contacted with the test piece containing no crude purified strogin powder was slightly bitter, with the odor oozing out from the test piece, while the water was contacted with the test piece containing the crude strogin powder. The water had no bitterness or odor.

Example 9 After smoking a cigarette, 0.5 ml of a 0.05% aqueous solution of strogin described in Example 2 was included in the mouth. For about 10 seconds,
By including a 0.05% aqueous solution of strogin in the mouth, the bitterness remaining in the mouth after smoking the cigarette disappeared, and a slight sweetness was felt in the mouth. This sweetness lasted for about 15 minutes. Further, when the cigarette was smoked during these 15 minutes, the taste of cigarette was felt sweet.

Example 10 0.2 m of a 0.05% aqueous solution of strogin as described in Example 2
l was allowed to soak into the filter portion of a commercially available cigarette (one). Then, it was dried overnight in a dryer at 40 ° C. When I smoked this cigarette, I felt a slight sweetness. Also, the bitterness that usually remains in the mouth after smoking is sweet and faint.

[0052]

INDUSTRIAL APPLICABILITY The novel substance strogin and its salt according to the present invention are excellent in stability because they are not proteins, unlike the already known taste-modifying substance curculin, and curculin is used from the viewpoint of stability. It can be used in fields that cannot. In addition, since it has a peculiar effect of making the air to be breathed sweet, it can be widely used for foods and beverages, etc. that need to maintain sweetness.

[Brief description of drawings]

FIG. 1 is a graph showing a mass spectrum of strogin according to the present invention.

FIG. 2 is a graph showing ultraviolet and visible absorption spectra of strogin according to the present invention.

FIG. 3 is a graph showing an infrared absorption spectrum of strogin according to the present invention.

FIG. 4 is a graph showing a ¹ H-NMR spectrum of strogin according to the present invention.

FIG. 5 is a graph showing a ¹³ C-NMR spectrum of strogin according to the present invention.

FIG. 6 is a graph showing the results of gas chromatography-mass spectrometry (GC-MS) on the decomposition products of strogin according to the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Haruyuki Yamashita 7-35 Higashiohisa, Arakawa-ku, Tokyo Asahi Denka Kogyo Co., Ltd.

Claims (4)

[Claims] 1. A compound represented by the general formula (I): (In the formula, A is a hexapyranose residue whose hydroxyl group is optionally etherified or acylated, and B is a hexapyranose residue whose hydroxyl group is optionally etherified or acylated. Group, a hydroxyl group is a pentopyranose residue which may be etherified or acylated in some cases, or a uronic acid residue in which the primary alcohol group of these pyranose residues is a carboxyl group, and n is 1 Is an integer from 3 to 3, and when n is 2 or 3, B can be the same or different groups, and R ₁ , R ₂
And R ₃ are the same or different and each is a hydrogen atom or a carbon number of 1-4
Alkyl groups or acyl groups having 2 to 4 carbon atoms)
The strogin compound represented by or its salt. 2. A method for producing the above-mentioned strozin compound or a salt thereof, which comprises obtaining a stroszin compound represented by the general formula (I) or a salt thereof from a plant belonging to the family Amblyceae. 3. A strogin compound represented by the general formula (I) according to claim 1 or a salt thereof,
Taste modifier. 4. A taste-modifying composition comprising the strogin compound represented by the general formula (I) according to claim 1 or a salt thereof as a taste-modifying agent.