JPH0925290A - New compound included in sugar beet, medical composition and function food - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound included in sugar beets, a sugar beet saponin obtained from an extract of sugar beets, having blood glucose-reducing activities, low toxicity and no limitation in doses and useful as a blood glucose- reducing agent, functional food, etc. SOLUTION: This new compound comprises sugar beet saponin compound expressed by formula I (R<1> is H or -D-Glu; R<3> and R<4> are each H or CH3 ) or formula II (R<2> is H or -D-Glu). The new compound has blood glucose-reducing activities, low toxicity and no limitation in doses and is useful as a blood glucose-reducing agent, functional food, etc. The compound can be obtained by adding 50% aqueous methanol to sugar beets cut in small sizes, heat- extracting under reflux for 3 hours, filtrating the extracted solution, removing methanol under reduced pressure, lyophilizing the resulting material to obtain a water-containing methanol extract which is treated with a reverse-phase silica gel column, eluted with water to remove sucrose, eluted with methanol and purified the obtained fraction by a high speed liquid chromatography, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to novel compounds contained in sugar beet, hypoglycemic agents and functional foods containing these compounds.

Sugar beet ( Beta vulgaris ) is a plant of the family Rhinoceros family, improved from a wild species native to Europe, and is a perennial plant cultivated in northern Honshu, Hokkaido and the like.
At a height of 60 to 90 cm, the roots are fleshy and have a spindle-shaped enlargement, and the meat is white-yellow or crimson. From the roots, long-oval leaves with a long handle are clustered and the quality is high. In the summer, the stem, which is about 1 m high, is extended and many yellow-green florets are attached to the spikes. The leaves are edible. The root contains 15 to 18% sucrose and is a raw material for sugar beet (beet sugar). Pour roots, add lime to squeezed juice and boil to remove floating impurities, boil down to produce white sucrose, and purify.

It is known that roots show sedative and menstrual action in Chinese medicine. The presence of saponins, betacyanins and phenolic compounds are known as the chemical constituents of sugar beet, and recently several kinds of oleanolic acid glycosides have been identified from the leaves of this plant.

[0004]

[Means for Solving the Problems] In studies of biologically active substances in edible plants, saponin fractions derived from roots and leaves of sugar beet inhibit the increase in plasma glucose level in an oral glucose tolerance test in rats. Was found to show. This time, as a continuation of the research on the hypoglycemic saponin component, we conducted a chemical study on the active components of the root and leaf of sugar beet to find out that beta bulgaroside I (1), II
Separating (2), III (3), IV (4) and V (5),
Purified. Furthermore, it was also confirmed that these components have a hypoglycemic effect.

The present invention provides the formula A:

Embedded image [Wherein R ¹ is H or β-D-Glu, and R ³ and R ⁴ are H or CH ₃ ], more specifically beta bulgaroside I and II And is represented by the formula B:

[Chemical 6] [Wherein R ¹ , R ³ and R ⁴ have the same meanings as described above,
R ² is H or β-D-Glu], more specifically compounds represented by beta bulgaroside III, IV and V.

The present invention further comprises an extract of sugar beet containing at least one of the above compounds, and a pharmaceutical composition for lowering blood glucose activity and functional foods containing at least one of the above compounds or an extract containing the same as an active ingredient. Is provided.

The present invention also provides the formula A:

Embedded image [Wherein R ¹ is H or β-D-Glu, and R ³ and R ⁴ are H or lower alkyl], and a compound of formula B:

Embedded image [Wherein R ¹ , R ³ and R ⁴ have the same meanings as described above,
R ² is H or β-D-Glu], which provides a hypoglycemic active pharmaceutical composition containing at least one compound represented by the formula [2] as an active ingredient.

In the above, β-D-Glu is an abbreviation for β-D-glucose. Lower alkyl is a saturated straight-chain or branched chain having 1 to 6 carbon atoms, preferably 1
~ 5, more preferably 1 to 4 hydrocarbon residues. For example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl and the like are included.

The pharmaceutical composition is preferably orally administered, and its form includes powders, granules, fine granules, capsules, tablets, pills, liquids and the like. The above-mentioned compounds and extracted extracts are components of beet sugar, and since they can be used for food production, functional foods that can be expected to lower blood glucose levels are included. Examples of the form of the functional food include drinks, candy, gums, cookies, and the like.

Generally, sugar beet (cultivated in Hokkaido)
Aqueous extracts of fresh roots of S. cerevisiae were subjected to reverse phase SiO ₂ column chromatography (ODS Cosmozil, H ₂ O-MeOH) and conventional SiO ₂ column chromatography (CHCl ₃ −).
MeOH-H ₂ O) and finally subjected to HPLC (YMC-Pack ODS, MeOH-1% trifluoroacetic acid),
Beta bulgaroside I (1: 0.0061 from fresh root
%), II (2: 0.0004%), III (3: 0.0029)
%) And IV (4: 0.0005%), and further, Chixetusaponin IVa (8: 0.0002%) was separated. On the other hand, beta bulgaroside V (5: 0.0011
%) Is separated from sugar beet leaves by the same separation method. In addition, a methyl ester derivative can be obtained using a commonly used treatment method with MeOH or diazomethane (Heterocycles No. 41).
See Volume 8 (posting)).

Pharmacological Experiments Hypoglycemic Activity Test in Rats Male Wistar rats weighing 125-155 g were inoculated with water ad libitum, but they were fasted for 20-24 hours. The test compound was dissolved in water and orally administered at the prescribed doses (5 ml / k
g). After 30 minutes D-glucose (5 g / kg)
Oral administration of sucrose (1.0 g / kg is acceptable) (5 ml / k
g). Blood was collected from the carotid artery under unanesthetized restraint at 0.5, 1.0 and 2.0 hours after administration of D-glucose (0.4 m
l), after cooling with ice water, separating serum by centrifugation,
The glucose concentration in plasma was measured by the glucose oxidase method.

Beta bulgaroside I (1), II (2),
Table 1 summarizes the inhibitory effects of III (3), IV (4) and V (5), and prosapogenol (6) on elevated blood glucose levels in the oral glucose tolerance test in rats.

[Table 1] Administration of beta-bulgaroside I (1), II (2), III (3), IV (4) and V (5), and prosapogenol (6) in blood glucose tolerance test in oral glucose tolerance test Amount Rat blood glucose level (mg / dl) (mg / kg, number 0.5 hours 1 hour 2 hours Oral) Normal group 10 72.4 ± 3.3 ** 95.8 ± 5.0 ** 90.6 ± 4.8 * Control group 9 148.6 ± 4.7 138.3 ± 4.6 107.9 ± 4.1 (76.2 ± 4.7) (42.5 ± 4.6) (17.3 ± 4.1) 1 100 5 153.5 ± 5.9 144.7 ± 4.7 114.0 ± 5.3 (81.1 ± 5.9) (48.9 ± 4.7) (23.4 ± 5.3) 2 100 5 108.5 ± 9.1 ** 137.7 ± 5.4 121.8 ± 4.9 (36.1 ± 9.1 **) (41.9 ± 5.4) (31.2 ± 4.9) 3 100 5 139.3 ± 3.3 135.1 ± 4.9 103.0 ± 1.9 (66.9 ± 3.3) (39.3 ± 4.9) (12.4 ± 1.9) 4 100 3 111.5 ± 5.7 ** 125.8 ± 5.9 114.0 ± 0.6 (39.1 ± 5.7 **) (30.0 ± 5.9) (23.4 ± 0.6) 5 100 5 147.0 ± 3.4 138.5 ± 3.1 108.3 ± 5.7 (74.6 ± 3.4) (42.7 ± 3.1) (17.7 ± 5.7) 6 100 6 124.1 ± 5.9 ** 139.3 ± 4.8 119.3 ± 3.0 (51.7 ± 5.9 **) (43.5 ± 4.8) (28.7 ± 3.0) * p <0.05, ** p <0.01 Each test compound was orally administered to rats 30 minutes before the oral administration of D-glucose (0.5 g / kg). Numbers in parentheses indicate the difference in blood glucose level (plasma glucose concentration) between normal control and each test compound treatment.

In the glucose tolerance test, beta bulgaroside II (2), III (3) and IV (4), prosapogenol (6) showed hypoglycemic activity. It is noteworthy that 3-O-monodesmoside (2,4,6) showed even more potent activity than 3,28-O-bisdesmoside (3). This may suggest characterization of structure and hypoglycemic activity.

The beta-bulgaroside compounds represented by the formulas A and B of the present invention and the extract of sugar beet exhibit hypoglycemic activity and are useful as hypoglycemic agents. In addition, those that exhibit substantially the same physiological activity or pharmacological activity as the free form in vivo, for example, derivatives of the compound of the present invention and pharmaceutically acceptable salts, addition salts, hydrates, etc. It is within the technical scope of the invention.

The method of administration may be oral or parenteral, but oral administration is preferred. In preparing an orally administered pharmaceutical composition, a commonly used pharmaceutically acceptable additive (carrier, excipient, disintegrant, lubricant, binder,
Surfactants, preservatives, suspending agents, flavoring agents, etc.) can be used. The beta bulgaroside compound has low toxicity and therefore the dose is not particularly limited.

[0016]

【Example】

Example 1 Isolation of beta bulgaroside IV from sugar beet Shredded sugar beet [fresh roots from Hokkaido (1994),
12 kg] is added with 50% water-containing methanol (or ethanol) (10 liters), and the mixture is extracted with heating under reflux for 3 hours. After the extract is filtered off, 50% hydrous methanol (10 liters) is added to the residue and the same extraction operation is performed three times in total.
The extracts were combined, the methanol was distilled off under reduced pressure, and the extract was freeze-dried to obtain a hydrous methanol extract (2 kg).
Extract the hydrous methanol extract with a reversed-phase silica gel column [C
hromatorex ODS (Fuji Silysia Chemical LT
D.), 2 kg], and eluted with water to remove sucrose, and then eluted with methanol (or ethanol) to obtain a methanol elution portion (crude saponin fraction, 15 g).

The elution part of methanol was subjected to silica gel column chromatography [silica gel 60 (Merck)],
Elute with chloroform-methanol water mixture, then eluate chloroform-methanol water mixture [7: 3: 1 (lower layer)] elution part (Fr. 2.05g) with chloroform-methanol water mixture (6: 4: 1). Part (Fr. 4, 0.6 g) was obtained. Fr. 2 and Fr. 4 is silica gel column chromatography [silicagel 60 Fr. 220 to 2
g, Fr. After separating with 4 to 70 g, mixed solution of chloroform-methanol water, high performance liquid chromatography [apparatus: Shimadzu LC-10AS (manufactured by Shimadzu), column:
YMC-Pack ODS-A (YMC Co., Ltd.), elution solvent: 75% methanol-1% trifluoroacetic acid] and purified to obtain beta bulgaroside I (0.0061%), II (0.006%).
0004%), III (0.0029%), IV (0.000)
5%) and chikusetsusaponin IVa (0.0002%).

On the other hand, freshly chopped sugar beet leaves (2.6k
g) was extracted with hydrous methanol (5 liters x 3 times) as in the case of fresh roots, and the hydrous methanol extract (115
g) was obtained. The extract containing water-containing methanol was subjected to reverse phase silica gel column chromatography to obtain a methanol eluate (crude saponin fraction, 8.6 g). The methanol eluate was separated and purified by silica gel column chromatography and then high performance liquid chromatography (all under the same conditions as the root) to obtain beta bulgaroside V (0.0011%).

Beta bulgaroside I (1) is represented by Formula A where R ¹ is β-D-Glu and R ³ and R ⁴ are H. Colorless fine crystals, mp215-21
7 ° C. [α] _D + 44.9 ° (MeOH) Positive mode FAB-MS: m / z 977 (M + Na) ⁺
C ₄₇ H ₇₀ O ₂₀ Na, negative mode FAB-MS: 953 (M- H) - C 47 H 69
O ₂₀ ¹ H NMR (pyridine _{-d 5) IR (KBr):} 3453,1740,1736,10
78 cm ^-1 methanol decomposition (9% HCl-MeOH, reflux)
Oleanolic acid, methyl-D-glucoside and methyl-D-glucuronide were separated.

Beta bulgaroside I-1 "'-methyl ester (1a) Formula A wherein R ¹ is β-D-Glu, R ³ is H,
R ⁴ is represented by CH ₃ a is). Colorless fine crystals mp 200 to 202 ° C. [α] _D + 57.3 ° (MeOH) Positive mode FAB-MS: m / z 991 (M + Na) ⁺ C ₄₈
H ₇₂ O ₂₀ Na IR (KBr): 3474, 1743, 1736, 10
76cm ^{-1 1} H NMR (pyridine _{-d 5): δ3.28 (dd-} like, 3
-H), 5.00 (d, J = 7.6, 1'-H), 4.72
(m, 3'-H), 5.38 (m, 4'-H), 5.82 (s, 3 "
-H), 4.63 (s, 2 "'- H 2), 6.33 (d, J = 7.
9,1 ""-H) 1 "'-OCH ₃ and 1"' in HMBC data of (1a)
Remote spin coupling was observed between -C, 1 "'-of (1a)
The methylated structure was confirmed. Finally, methylation of 1 with an excess of diazomethane in MeOH produced the 6 ', 1 ", 2", 1 "'-tetra-O-methyl derivative (1b), which was the achillanthoside A (achyranthoside A) methyl ester. (Ida et al., Tetrahedron Letters, Vol. 35, page 6887 (19
1994)). The structures of beta bulgaroside I (1) and II (2) were determined based on the above results.

Beta bulgaroside II (2) is represented by the formula A (wherein R ¹ , R ³ and R ⁴ are H). Alkaline hydrolysis of (1) (5% aq. NaOH, reflux) gave beta bulgaroside II (2). Colorless microcrystals _{mp173~174 ℃ [α] D + 98.0} ° (MeOH) negative mode FAB-MS: m / z791 ( M-H) - C
₄₁ H ₅₉ O ₁₅ IR (KBr): 3432, 1741, 1731, 10
80 cm ^-1 ) ¹ H NMR (pyridine-d ₅ ): δ3.30 (dd-like, 3
-H), 4.99 (d, J = 7.3, 1'-H), 4.85 (m,
3'-H), 5.38 (dd-like, 4'-H), 5.99 (s,
3 "-H), 4.80 (m , 2"'- H 2) 1 H NMR ( pyridine -d ₅₎ and (1) and (2) of ¹³ C NMR (see Table 2) COZY ⁽¹ H − ¹
H, ¹ H- ¹³ C), HOHAHA and ROESY experiments, and showed the presence of a bis-acetal glucuronide moiety consisting of 3-oxopyruvic acid and glycolic acid [(1): δ 5.00 (d, J = 7.3, 1'-
H), 4.75 (m, 3'-H), 5.38 (dd-like, 4'-
H), 5.99 (s, 3 "-H), 4.80 (m, 2"'-
H ₂ )]. C of the 3-O-glucuronide moiety in (1)
The bis-acetal structures at the 3'and 4'positions were confirmed by HMBC experiments. That is, there is a remote spin bond between the following carbon and proton of (1) (1'-H and 3-C; 3'-H and 3 "-C;3" -H and 3 '.
-C, 2 "'-C;4'-H and 2"-C; 2. "' - H 2 and 3" -C, 1 "'- by C) treating at reflux MeOH, (1) Is easily converted into 1 "'-methyl ester (1
a), weak alkaline hydrolysis [2% aq. K ₂ CO _{3
-CH 3 CN (1: 1)} , and returned to at rt] (1).

Beta bulgaroside III (3) is represented by Formula B, where R ¹ is β-D-Glu and R ₂ , R ³ and R ⁴ are H. Colorless fine crystals mp212-214 ° C [α] _D + 11.0 ° (MeOH) Positive mode FAB-MS: m / z 979 (M + Na) ⁺
C ₄₇ H ₇₂ O ₂₀ Na negative mode FAB-MS: m / z955 ( M-H) - C
^{_{47 H 71 O 20 1 H NMR}} ( pyridine _{-d 5): δ3.55 (dd-} like, 3
-H), 4.98 (d, J = 7.6, 1'-H), 4.51 (m,
3'-H), 4.65 (m, 4'-H), 5.34 (brs, 2 "-
H), 6.31 (brs, 3 "-H), 5.06, 5.35 (AB
q, J = 16.5, ₂ "'-H2) IR (KBr): 3429, 1742, 1736, 10
76 cm ^-1 )

Treatment of (3) with MeOH produced 1 "'-methyl ester (3a) which was hydrolyzed back to (3). The 1"'-methyl ester structure (3a) was converted to (3a). ) HMBC between 1 "'-OCH ₃ and 1"'-C
This was confirmed by the observed correlation. Of (3)
¹ H NMR and ¹³ C NMR and (3a) and (4)
By detailed ¹ H and ¹³ C NMR comparisons (see Table 2) of beta bulgaroside III (3) and IV
The structural formula of (4) was determined.

Beta bulgaroside III-1 "'-methyl ester (3a) Formula B wherein R ¹ is β-D-Glu, R ² and R ³ are H, R ⁴ is CH ₃ . represented by a is) colorless microcrystals _{mp191~192 ℃ [α] D + 13.5} ° (MeOH) negative mode FAB-MS: m / z969 ( M-H) - C 48
H ₇₃ O ₂₀ IR (KBr): 3410, 1740, 1736, 10
76cm ^{-1 1} H NMR (pyridine _{-d 5): δ3.34 (dd-} like, 3
-H), 4.97 (d, J = 7.6, 1'-H), 4.46 (m,
3'-H), 4.46 (m, 3'-H), 4.60 (m, 4'-
H), 5.40 (br s, 2 "-H), 6.25 (br s, 3"-
H), 4.92, 5.33 (ABq, J = 16.5, 2 "'-H
₂ ), 6.33 (d, J = 7.6, 1 ""-H) data valgologide III is a compound O (I.
Yoshioka, M. Fujio, M. Osamura, I. Kitagawa, Tetra
hedron Lett., 1966 , 6303). On the other hand, beta-bulgaroside IV (4) was produced by alkaline hydrolysis of (3).

Beta bulgaroside IV (4) is represented by Formula B (wherein R ¹ , R ₂ , R ³ and R ⁴ are H). Colorless microcrystals _{mp186~187 ℃ [α] D + 10.4} ° (MeOH) negative mode FAB-MS: m / z793 ( M-H) - C
^{_{41 H 61 O 15 1 H NMR}} ( pyridine _{-d 5): δ3.37 (dd-} like, 3
-H), 5.00 (d, J = 5.9, 1'-H), 4.52 (m,
3'-H), 4.68 (m, 4'-H), 5.34 (brs, 2 "-
H), 6.34 (brs, 3 "-H), 5.07, 5.38 (AB
q, J = 16.7, ₂ "'-H2) IR (KBr): 30, 34, 1740, 1736, 1
076 cm ^-1 )

The ¹ H NMR ¹²⁾ and ¹³ C NMR (see Table 2) spectra of (3) and (4) are the same as those of (3).
The presence of an acetal substituent consisting of tartronaldehyde acid and glycolic acid was shown at the 3'-hydroxyl group of the -O-glucuronide moiety (HMBC relationship: 1'-H.
And 3-C; 3 "-H and 3'-C;2"'-C; 2 "
-H and 1 "-C, 3"-C; 2 "'- H 2 and 3" -
C, 1 "'-C). The results and (3) and Chixetusaponin IVa (I. Yoshioka, M. Fujio, M. Osamura, I.
Kitagawa, Tetrahedron Lett., 1966 , 6303) ¹³ C NM
The structure of (3) was determined based on comparison of R data.

Beta bulgaroside V (5) is represented by Formula B where R ¹ and R ² are β-D-Glu and R ³ and R ⁴ are H. Colorless fine crystals mp 205 to 206 ° C. [α] _D + 23.8 ° (MeOH) Positive mode FAB-MS: m / z 1141 (M + Na) ⁺
C ₅₃ H ₈₂ O ₂₅ Na Negative mode FAB-MS: m / z 1117 (M−H) ⁻
C ₅₃ H ₈₁ O ₂₅ IR (KBr): 3432, 1740, 1736, 10
¹ H NMR and ¹³ C NMR (see Table 2) data of 76 cm ⁻¹ 5 are obtained by 2′-O-β-D-glucopyranosyl [δ5.69.
(d, J = 7.3, 1 ""'-H)] and 3'-O-acetal substituents [δ4.40 (m, 3'-H), 4.63 (m, 4'-).
H)] having a 3-O-glucuronide moiety [δ4.97
(d, J = 8.9, 1'-H)], and tartraldehyde acid [δ5.38 (brs, 2 "-H), (brs, 3"-).
H)] and glycolic acid [δ 4.92, 5.17 (AB
q, J = 16.1,2 "'- .HMB constructed from H _2)]
The C correlation was determined by the following proton and carbon (1'-H and 3-C; 1 ""'-H and 2'-C; 3 "-H and 3'-
C; 2 "-C;2"'-C; 2 "-H and 1" -C, 2 "'
-H and 1 "'-C). This evidence and 5 and Chixetusaponin V (T.D. Lin, N. Kndo, J.S.
hoji, Chem, Pharm.Bull., 24 , 253 (1976)) 5
Guessed the structure of.

Treatment of (5) with MeOH provided 1 "'-methyl ester (5a) which was hydrolyzed back to (5). 1"'-methyl ester structure (5a).
Was confirmed by the HMBC experiment. On the other hand, the methylation of (5) with diazomethane gives the tetramethyl derivative (5
b) was obtained, and prosapogenol (6) was obtained by alkaline hydrolysis of (5). These results and the ¹ H NMR and ¹³ C NMR data of (5) and (5
a), (5b) and (6) ¹ H NMR and ¹³ C NM
Beta Bulgaroside V based on comparison of R data
The structure of (5) was determined.

Beta bulgaroside V-1 "'-methyl ester (5a) Formula B (wherein R ¹ and R ² are β-D-Glu, R ³ is H, R ⁴ is CH ₃ Colorless fine crystals, mp 211-213 ° C. [α] _D + 26.6 ° (MeOH) Positive mode FAB-MS: m / z 1155 (M + Na) ⁺
C ₅₄ H ₈₄ O ₂₅ Na IR (KBr): 3473, 1742, 1736, 107
6cm ^{-1 1} H NMR (pyridine _{-d 5): δ3.26 (dd-} like, 3-
H), 4.99 (d, J = 6.9, 1'-H), 4.43 (m, 3 '
-H), 4.60 (m, 4'-H), 5.41 (br s, 2 "-
H), 6.36 (brs, 3 "-H), 4.77, 5.69 (AB
q, J = 16.5, ₂ "'-H2), 6.33 (d, J = 7.9,
1 ""-H), 5.69 (d, J = 7.3, 1 ""-H)

Beta bulgaroside V-tetramethyl ester (5b) is represented by Formula B, where R ¹ and R ² are β-D-Glu and R ³ and R ⁴ are CH ₃ . Colorless fine crystals mp155-157 ° C. [α] _D + 38.2 ° (MeOH) Positive mode FAB-MS: m / z 1197 (M + Na) ⁺ C
₅₇ H ₉₀ O ₂₅ Na IR (KBr): 3432, 1747, 1736, 107
6cm ^{-1 1} H NMR (pyridine _{-d 5): δ3.21 (dd-} like, 3-
H), 5.00 (d-like, 1'-H), 4.42 (m, 3'-
H), 4.38 (m, 4'-H), 4.80 (brs, 2 "-H),
6.10 (br s, 3 "-H), 4.76, 5.08 (ABq, J
_{= 16.3,2 "'- H 2)} , 6.35 (d, J = 7.6,1""
-H), 5.42 (d, J = 7.2, 1 ""'-H)

Prosapogenol (6) Formula B (wherein R ¹ is H, R ² is β-D-Glu,
R ³ and R ⁴ are H). Colorless fine _{crystals, mp174~176 ℃ [α] D +} 30.0 ° (MeOH) negative mode FAB-MS: m / z955 ( M-H) - C 47
H ₇₁ O ₂₀ IR (KBr): 3432, 1748, 1736, 10
78cm ^{-1 1} H NMR (pyridine _{-d 5): δ3.38 (dd-} like, 3
-H), 4.99 (d, J = 7.0, 1'-H), 4.48 (m,
3'-H), 4.52 (m, 4'-H), 5.41 (brs, 2 "-
H), 6.35 (brs, 3 "-H), 4.94, 5.21 (AB
q, J = 16.2, ₂ "'-H2), 5.72 (d, J = 7.6.
1 ""'-H)

[0032]

TABLE 2 beta Bull astragaloside I (1), II (2 ), III (3), IV (4) and V (5) and related compounds (1a, 3a, 5a, 5b , 6) * for ¹³ C NMR data 1 1a 2 3 3a 4 5 5a 5b 6 C-1 38.4 38.5 38.5 38.6 38.6 38.6 38.6 38.6 38.6 38.5 C-2 26.4 26.5 26.5 26.6 26.6 26.6 26.4 26.5 26.5 26.5 C-3 89.2 89.4 89.3 89.2 89.2 89.2 89.5 89.5 89.6 89.3 C-4 39.3 39.5 39.5 39.5 39.5 39.5 39.5 39.5 39.5 39.5 C-5 55.5 55.6 55.7 55.7 55.7 55.7 55.8 55.8 55.6 55.7 C-6 18.3 18.5 18.4 18.5 18.5 18.4 18.5 18.5 18.5 18.4 C-7 33.0 33.0 33.3 33.1 33.1 33.1 33.1 33.1 33.2 33.3 C-8 39.7 39.9 39.7 39.9 39.9 39.7 39.9 39.9 39.9 39.7 C-9 47.8 47.9 47.9 48.0 48.0 48.0 48.0 48.0 48.0 47.9 C-10 36.7 36.9 36.9 36.9 36.9 36.9 36.9 36.9 36.9 36.9 C-11 23.2 23.4 23.8 23.4 23.4 23.4 23.4 23.4 23.2 23.8 C-12 122.7 122.9 122.5 122.8 122.8 122.5 122.8 122.8 122.9 122.5 C-13 144.0 144.1 144.8 144.1 144.1 144.8 144.1 144.1 144.2 144.8 C-14 42.0 42.1 42.1 42.1 42 .1 42.2 42.1 42.1 42.2 42.1 C-15 28.1 28.2 28.3 28.2 28.2 28.3 28.2 28.2 28.3 28.3 C-16 23.6 23.7 23.8 23.7 23.7 23.8 23.6 23.7 23.7 23.8 C-17 46.8 47.0 46.6 47.0 47.0 46.7 47.0 47.0 47.0 46.6 C-18 41.6 41.8 42.0 41.7 41.7 42.0 41.7 41.7 41.8 42.0 C-19 46.0 46.0 46.4 46.4 46.2 46.4 46.2 46.1 46.0 46.4 C-20 30.6 30.8 31.0 30.7 30.8 31.0 30.7 30.8 30.8 31.0 C-21 33.8 34.0 34.2 34.0 34.0 34.2 34.0 34.0 34.0 34.2 C- 22 32.4 32.5 33.2 32.5 32.5 32.1 32.5 32.5 32.6 33.2 C-23 27.9 28.0 28.1 28.1 28.1 28.2 28.0 28.0 28.0 28.1 C-24 16.7 16.9 16.9 16.9 16.9 16.9 16.7 16.7 16.8 16.9 C-25 15.3 15.5 15.4 15.5 15.5 15.4 15.5 15.5 15.5 15.4 C-26 17.3 17.4 17.3 17.4 17.4 17.4 17.4 17.4 17.6 17.3 C-27 26.0 26.1 26.2 26.1 26.1 26.2 26.1 26.1 26.1 26.2 C-28 176.3 176.4 180.1 176.4 176.4 180.2 176.4 176.4 176.4 180.1 C-29 33.0 33.0 33.3 32.1 33.1 33.1 33.1 33.1 33.2 33.3 C-30 23.5 23.6 23.8 23.6 23.6 23.8 23.4 23.6 23.4 23.8 3-O-Gluc.A C-1 '107.4 107.6 107.6 106.7 106.8 106.8 105.1 105.2 104.8 105.3 C-2' 7 1.9 72.0 72.1 74.8 74.7 74.8 78.3 78.2 79.1 78.3 C-3 '72.4 72.5 72.5 85.4 85.1 85.5 83.9 82.9 84.0 83.9 C-4' 70.0 70.1 70.1 72.3 72.3 72.4 72.9 73.2 71.1 72.9 C-5 '75.1 75.3 75.3 77.5 77.5 77.6 77.2 77.2 76.5 77.3 C-6 '171.4 171.4 171.6 172.4 172.4 172.4 172.2 172.3 170.3 172.2 6'-OMe 51.9 C-1 "171.0 171.1 171.2 174.8 174.6 174.6 174.5 177.4 170.3 174.5 1" -OMe 52.1 C-2 "93.8 93.8 94.0 74.2 74.2 74.2 73.0 72.6 82.8 72.8 2 "-OMe 58.9 C-3" 97.9 98.2 98.1 105.4 104.9 105.4 105.2 104.6 102.3 105.2 C-1 "'172.2 170.0 172.3 173.9 171.3 173.9 173.7 171.0 170.3 173.7 1"'-OMe 51.5 51.3 51.2 51.4 C-2 "'64.7 64.5 64.9 65.1 64.2 64.3 65.7 64.8 64.1 65.7 28-O-Glu. C-1""95.7 95.7 95.7 95.7 95.7 95.7 95.8 C-2""74.0 74.1 74.1 74.1 74.1 74.1 74.2 C-3""78.7 78.9 78.8 78.9 78.8 78.9 79.0 C-4 "" 70.9 71.1 71.1 71.1 71.1 71.1 71.1 C-5 "" 79.1 79.3 79.3 79.3 79.2 79.3 79.4 C-6 "" 62.0 62.2 62.2 62.2 62.2 62.2 62.2 2'-O-Glu. C-1 ""'103.6 103.6 103.6 103.7 C-2 ""' 76.3 76.4 76.1 76.4 C-3 ""'78.1 78.2 78.3 78.2 C- 4 ""'72.4 72.3 72.4 72.5 C-5 ""' 77.8 78.0 78.4 77.8 C-6 "" '63.2 63.1 63.1 63.3 * (68MHz, pyridine-d ₅ , δc)

Example 2 Preparation of soft extract of sugar beet Extracting step of sugar beet root 12 kg of sugar beet root as a raw material was weighed, 10 l of 50% ethanol was added, and heat extraction was performed at 90 ° C. for 3 hours, and after cooling,
After passing through a 150 mesh sieve, filter paper (Toyo Filter Paper N
o.2) for filter paper separation and solid-liquid separation, and heated extract (A)
Get. 50% ethanol was added to the heat extraction residue collected by filtration.
1 was added, the same operation was performed twice, and the heated extract (B),
(C) is obtained. Discard the residue collected by filtration. The heated extracts (A), (B), and (C) are concentrated under reduced pressure at about 60 ° C. to obtain a concentrated liquid (about 4.5 kg). The concentrated solution is sterilized by heating at 90 ° C. for 1 hour, and then sterilized purified water is used to adjust the product to Brix 40.0, which is the product standard as a soft extract of sugar beet. About 5.0 kg of the product as a sugar beet extract soft extract was obtained.

Example 3 Production of dried extract of sugar beet (powder) Brix of 5.0 kg of soft extract of sugar beet was adjusted to Brix 50 with sterile purified water and sterilized at 90 ° C. for 30 minutes. This is fog-dried to obtain 2.0 kg of dried extract of sugar beet.

Example 4 Production of sugar beet extract fine granules 30 kg of lactose was weighed, put in a flow coater and granulated for 1 minute, and 1 kg of starch and 10 kg of sugar beet extract soft extract were added and mixed in advance. While adding, atomize and granulate for 60 minutes with a flow coater and further dry for 10 minutes in a flow coater. The particles were sized using a 40-80 mesh sieve to obtain sugar beet extract fine particles.

Example 5 Production of Granules Containing Sugar Beet Extract Extract 10 kg of dried sugar beet extract, 64.38 kg of lactose, 7.37 kg of dried starch, 0.8 kg of Zein DP (trade name) (corn protein) were mixed in a mixer for about 20 minutes. To do. 22 kg of anhydrous ethanol was further added to this, and the mixture was kneaded with a high speed mixer for about 10 minutes. Transfer to a cylindrical granulator, granulate at 30 rpm, and dry for 5 hours in a tray dryer. The particles are sized using a 16 mesh sieve.

Example 6 Production of Tablets Containing Sugar Beet Extract Extract To about 80 kg of the granules obtained in Example 5, 3 kg of sucrose fatty acid ester was added as a lubricant, and the mixture was mixed for 15 minutes with a mixer, and then a rotary type (wet type) was used. Each tablet was compressed into tablets of about 400 mg with a tableting machine.

Example 7 Preparation of drink containing sugar beet extract Extract 300 liters of purified water is heated to 70 ° C. To this, 3 kg of sugar beet extracted soft extract and a small amount of other extracts for the final product are added and stirred and mixed, and further a small amount of vitamins and acids are added and stirred and mixed again.
About 300 kg of saccharides and 1500 liters of purified water are added to this and stirred and dissolved. Filter through a 1μ filter and add an appropriate amount of purified water to obtain the final product of about 3000
Adjust the liquid volume to 1 and add a small amount of fragrance and stir. Adjust the brix and acidity in the intermediate tank, heat until reaching 85 ° C, and fill at 80 ° C to make a product in cans or bottles.

Example 8 Production of candy containing sugar beet extract (candy) 77.48 kg of starch syrup, 66.71 kg of granulated sugar, 0.94 kg of soft sugar beet extract and 14.84 k of brown sugar
g is melted at 102-109 ° C. using a compounding heater. Stir at 60 ° C. for 30 minutes and concentrate with a vacuum cooker until the water content is 2%. A small amount of fragrance is added to this, mixed in a pan, cooled using a cooler, and mixed. Roll with batch rolls and sizing rollers,
Mold using a stamping machine and cool to room temperature on a cooling conveyor. Visual inspection after metal detector. To this, 22.2 kg of granulated sugar, a small amount of pigment, 0.18 kg of gum arabic and others are added, and a syrup is adjusted to apply sugar. Let stand at room temperature for 1 hour to dry and polish, then let stand at room temperature overnight to dry and inspect visually. About 160 kg of candy (candy) containing sugar beet extracted soft extract was obtained.

Example 9 Preparation of cookie containing sugar beet extract 20 kg of trio sugar and 10 kg of shortening are weighed, stirred and mixed. 1kg of sugar beet soft extract
And 0.2 kg of sweetener and liquid raw materials such as a proper amount of flavor and the like, stirred and mixed, soybean protein 16k
20 kg of other raw materials such as g and 4 kg of soybean fiber are added, and the mixture is stirred and mixed again. 20 kg of eggs and 30 kg of flour are added to this and kneaded to prepare a dough.
Die the dough on a roller with a thickness of 4 mm with a molding machine. Put the die-cut into a band oven and leave it at 180 ° C for 15
Bake for minutes. After cooling, about 100 kg of sugar beet extracted soft extract-containing cookies 100 kg were obtained.

Example 10 Production of chewing gum containing soft beet extract: 60 kg of gum base, 168 kg of sugar, 39 kg of starch syrup,
To 30 kg of glucose and 3 kg of a softening agent, 3 kg of a sugar beet extract soft extract aqueous solution obtained by previously diluting a sugar beet extract soft extract with twice the amount of water was added to prepare a chewing gum containing the sugar beet extract according to a conventional method. .

Claims (7)

[Claims] 1. Formula A: ## STR1 ## [Wherein R ¹ is H or β-D-Glu, and R ³ and R ⁴ are H or CH ₃ ], or a compound of the formula B: [Wherein R ¹ , R ³ and R ⁴ have the same meanings as described above, and R ² is H or β-D-Glu]. 2. At least one of the compounds according to claim 1.
Extract of sugar beet including seeds. 3. At least one of the compounds according to claim 1.
A hypoglycemic active pharmaceutical composition comprising a seed as an active ingredient. 4. A hypoglycemic active pharmaceutical composition containing the extract according to claim 2 as an active ingredient. 5. Formula A: [Wherein R ¹ is H or β-D-Glu, and R ³ and R ⁴ are H or lower alkyl], and a compound of the formula B: [In the formula, R ¹ , R ³ and R ⁴ have the same meaning as described above, and R ² is H or β-D-Glu] A hypoglycemic activity containing at least one compound represented by the formula Pharmaceutical composition. 6. At least one of the compounds according to claim 1.
Functional food containing seed as an active ingredient. 7. A functional food containing the extract according to claim 2 as an active ingredient.