JPH03157344A - New substances fr-12 and fr-14-a, production thereof and antioxidant containing the same as active ingredient - Google Patents

Abstract

NEW MATERIAL:Fr-12 expressed by formula I and Fr14-A expressed by formula II. USE:An antioxidant. PREPARATION:A turmeric (curcumae rhizoma), as necessary, is pulverized to 30-60 mesh particle size and then extracted with an organic solvent such as methanol, ethanol, acetone, ethyl acetate or chloroform to provide an extract. For further purification, the resultant extract may be dissolved in a water- immisicble solvent such as ethyl acetate and partitioned with water and the aforementioned solvent to remove the aqueous layer. Furthermore, adsorption methods, gel filtration methods, etc., as necessary, may be combined to carry out the purification.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel substance having antioxidant properties, a method for producing the same, and an antioxidant containing the same as an active ingredient. [Background of the Invention] When preserving food, in addition to spoilage caused by microorganisms, deterioration caused by oxygen in the air is a major problem. This change manifests itself as off-taste, off-odor, discoloration and oxidative fading of pigments due to rancidity of fats and oils. To prevent this oxidative deterioration phenomenon, there are two methods: placing the product in a packaging container such as a bottle or canned food to cut off contact with air, and adding an antioxidant. Antioxidants include water-soluble ones such as ascorbic acid and erythorbic acid, and oil-soluble phenolic compounds such as gallic acid esters. The former is mainly used to prevent the oxidation of pigments. The latter is mainly used to prevent oxidation of fats and oils. Fats and oils are easily oxidized in the presence of enzymes, water, metal salts, heat, light, etc., and oxidation progresses gradually at first, but rapidly after this period. Oxidation is thought to occur when oxygen acts on the double bond carbons of unsaturated fatty acids in fats and oils, producing free radicals or peroxides, which progress in a chain reaction and decompose into aldehydes, ketones, acids, etc. There is. At this time, the enzyme
Metal salts act as catalysts, and heat and light supply energy. Oils and fats with a high degree of unsaturation have faster reaction rates. Antioxidants act on this free radical or peroxide,
It interrupts the chain reaction and oxidizes itself. On the other hand, antioxidants have traditionally been used to treat various diseases caused by platelet aggregation, inflammation, liver damage, heart and liver damage caused by certain drugs, ischemic vascular disease, stroke, myocardial infarction, cerebral hemorrhage, cerebral infarction, and cerebral thrombosis. has been proposed and widely used as a preventive and therapeutic agent for cataracts, etc.
-145871, JP-A-57-188586, JP-A-60-142919, JP-A-63-30415,
JP-A-63-117090, JP-A-63-21864
No. 9, JP-A-63-130548, JP-A-63130
No. 590). [Problems to be Solved by the Invention] An object of the present invention is to provide a novel substance having antioxidant properties, a method for producing the same, and an antioxidant containing the same as an active ingredient. [Means for Solving the Problems] The present invention provides a novel substance Fr-12 represented by general formula (I),
The present invention provides a method for producing the same, an antioxidant containing the same as an active ingredient, a novel substance Fr14-A represented by general formula (II), a method for producing the same, and an antioxidant containing the same as an active ingredient. . H3 (I) Hereinafter, the present invention will be explained in detail. The novel substances Fr-12 and Fr14-A of the present invention can be advantageously produced by extracting turmeric with an organic solvent. Turmeric is a perennial herb of the Zingiberaceae family or its rhizome, and the rhizome can be used as it is or with appropriate treatment for 1) aromatic bitter stomachic medicine, diuretic, liver disease treatment, 2) food coloring. , 3) Raw material for manufacturing curcuma paper, 4
) is known to be used as a dye. Curcumin, curcumene, etc. are known components, but the new substance of the present invention was completely unknown. Turmeric used in the production method of the present invention is not particularly limited, and can be from any country of origin, such as India, Indonesia, China, Bangladesh, Taiwan, Jamaica, Haiti, Peru, etc. can also be used. First, turmeric is crushed into, for example, 30 to 60 meshes if necessary, and then extracted with an organic solvent such as methanol, acetone, ethyl acetate, or chloroform.
Obtain the extract. When using a water-immiscible solvent such as ethyl acetate or chloroform as a solvent, it is preferable to dry the turmeric in advance. This results in
Extraction efficiency can be improved. In order to further purify the extract (crude sample) obtained in this way, the crude sample is dissolved in a water-immiscible solvent such as ethyl acetate, and partitioned between the water and the solvent. After removing the aqueous layer, adsorption methods, gel filtration methods, etc. may be performed as many times as necessary in combination as necessary. For example, column chromatography using an adsorbent such as silica gel or a gel filtration agent such as Toyopearl HW-40J (manufactured by SO Corporation) can be carried out in appropriate combination. A has the following physicochemical properties, and as a result of examining these, it was found that each has the chemical structure shown in (1) (I[>) above. <Fr12> (1) Appearance Colorless oil (2) Molecular formula C,,H,.02 (3) High resolution El mass spectrum m/z232.
1476 (Ma actual value 232.1463 Theoretical value (4) Solubility Soluble in methanol, ethanol, ethyl acetate, chloroform, insoluble in water (5) Rf value (using Merck's "Siligel 60Fzs<J") n-hexane- Ethyl acetate (5:1) 0.39
Chloroform-methanol (100:1) 0.60 (6
) Ultraviolet absorption spectrum λ□xnm (ε) shown in FIG. 201 (23500), 232 <9900),
277 (2600) (in methanol) (7) Infrared absorption spectrum (film method) shown in Figure 2. (cm=)3350.2950.2900.1670.
1610.1440.1420.1370, 280 (8) Proton nuclear magnetic resonance spectrum (500 MHz, in deuterated chloroform) 1°28 (3H), 1.84 (3H), 2.11 (3
H), 2.25 (3H), 2.78 (IH), 2.79
(IH), 3.56 (IH), 5.99 (IH), 6.
70 (IH), 6.73 (LH>, 7.01 (IH),
8.04 (LH)

[9] Carbon-13 nuclear magnetic resonance spectrum (125 MHz, in deuterated chloroform) shown in FIG. 201.9(S), 157.8(S), 153.7(S)
), 137.1 (S) 130, 2 (S), 126°0
(d), 123.1(d), 121.6(6) 118.
4(d), 54.1(t), 27.8(q),
25.7 (d) 21, 4 (Q), 21.1 (
Q), 20.9 (Q) αQ light intensity [α) - (C0,
1, CHCβ3)+79<Fr14-A> (1) Appearance Colorless oil (2) Molecular formula C, SH,, O. (3) High resolution EIl mass spectrum m/z232.
1499 (M+) Actual value 232.1463 Theoretical value (4) Solubility Soluble in methanol, ethanol, ethyl acetate, chloroform, insoluble in water (5) Rf value (Merck & Co., Ltd. "Silica Gel 60F 2si
J) n-hexane-ethyl acetate (5:1) 0.
23 Chloroform-methanol (100:1) 0.2
7 (6) Ultraviolet absorption spectrum λsaw nu (ε) 4th
As shown in the figure. 201 (33200), 238 (12100>
, 275 (2700) (in methanol) (7)
The infrared absorption spectrum (film method) is shown in Figure 5. (am”)3450,3000.2950.1690°1630S1460,1440.1390°270 (8) Proton nuclear magnetic resonance spectrum (500 MHz, in deuterochloroform) 1.21 (3H), 1.85 (3H), 2 .10 (3H
. 2.19 (3H), 2.58 (IH), 2.69 (LH
. 3.23 (LH), 5.18 (LH), 6.02 (IH
. 6.65 (LH), 6°69 (l H), 7.01 (
LH(9) carbon-13 nuclear magnetic resonance spectrum (125 mechahertz, in deuterated chloroform) is shown in FIG. 200.1 (S), 155.4 (S), 153.9 (
S), 146.0 (S) 130, 9 (d), 124
゜■(d), 121.4(S), 118.8(d)11
3.5(d), 52.6(t), 35°3(d)
, 27.6 (Q)21, 9 (q), 2.0.7
(q), 15.3 (C1) αQ light intensity [αE(C
O, l, CH(J!3)+68 Compound of the present invention Fr12
and Fr14-A were found to have excellent antioxidant activity. Therefore, Fr12 and Fr1 of the present invention
4-A can be used as an antioxidant. The antioxidants of the present invention can be used to stabilize biological membranes, foods, edible oils, fats, waxes, vitamins, fragrances, and the like. In that case, the antioxidant is present in the substance to be stabilized by approximately 1.0 to 1.
Concentration of 1000pp, preferably about 2.5-200pp
m (based on the weight of the substance to be stabilized). [Example] In the following, "%" means "r w / v %". (Example 1) 28 g of Chinese turmeric powder (root) was extracted with 120-methanol to obtain an extract (crude sample). Next, the obtained extract (crude sample) was filtered and concentrated, and then partitioned between water and ethyl acetate. Next, the ethyl acetate layer was washed with 5% aqueous sodium bicarbonate, then dehydrated and concentrated. After that, silica gel (manufactured by Wako Pure Chemical Industries, Ltd. [Wako Gel C-3]
00J) column (φ3cm x 55cm>),
Elution was performed with n-hexane-ethyl acetate (15:1). Next, it was applied to a Toyobar HW-40J (manufactured by SO Corporation) column (φ2 cm x 80 cm), the active fraction was eluted with methanol, concentrated and solidified, and 5.4 mg of Fr12
and 7.9 mg of pure Fr14-A was obtained. (Comparative Experiment 1) First, Fr12 and Fr14 obtained in the same manner as in Example 1
-A, 2000 μg/rn1. 0.5 ml of ethanol solution was prepared. Next, add 0.5 mj of linoleic acid solution to 0.5 mf of each of the above ethanol solutions! (0.14g of linoleic acid in 5m
(prepared by dissolving in 1 liter of ethanol), 13uff
er1, OmJ' (1/10M phosphate BufferS
pH 7, O), water 0.5rn1. The mixed solution prepared by adding Rhodan iron (
Sample liquid 0.1ml1. 75% ethanol 4.7rd, 3
Add 0.1 ml of 0% rhodan ammonium, and measure the absorbance at 500 mμ after exactly 3 minutes (see "Nutrition and Food" Vol. 19, No. 3, p. 61) if necessary. The results are shown in FIG. As a control, 0.5 d of ethanol was added instead of 0.5 d of ethanol solution. (Comparative Experiment 2) First, F'12, Fr14 obtained in the same manner as in Example 1
For each of -A, 2rnl of 2000 μg/ml ethanol solution was prepared. Next, add 20 d of each of the above ethanol solutions to 20 d of beef tallow.
Large test tube containing rtt' (φ25mm x 200mm
) was added to prepare the sample. After that, each test tube was heated to 97.
Maintained in an oil bath at 8℃ and aeration rate 2.33 with an air pump.
rnI! Ventilation was carried out under the condition of /second. Thereafter, the change in PV value of each sample over time was measured. The PV value was measured according to the standard oil and fat analysis test method. The results are shown in Table 1. In addition, as a control, a solution in which ethanol 2- was added instead of ethanol solution 2d was used. Table 1 (note) - indicates unmeasurable. (Comparative experiment 3) 0.1rd Tween 20 in 0.1ml linoleic acid
After adding 0.3 ml of IN-KOH and dissolving well, distilled water is added to obtain a substrate solution of 25-. 0.06 methanol and 0.27 m67 m of the above substrate solution
73 ml of M phosphate buffer pH 1, O2 and 0.01 ml of soybean lipoxygenase (manufactured by Sigma) solution were added as a control. The amount of enzyme added was such that the increase in absorbance of the control at 234 nm was 1.0 per 5 minutes. Methanol solutions of Fr-12 and Fr14-A at various concentrations were prepared, and 0.06 ml of this was added in place of the methanol in the control above, and the increase in absorbance at 234 nm per 5 minutes was measured. . The inhibition rate was calculated based on the following formula from the increase in absorbance at 234 nm per 5 minutes of methanol solutions of Fr-12 and Fr14-A at various concentrations. The results are shown in Table 2. 8A... Control absorbance increase per 5 minutes B...
・Table 2 of increase in absorbance per 5 minutes of sample reaction solution

[Brief explanation of the drawing]

FIG. 1 is an ultraviolet absorption spectrum of Fr12 in methanol. FIG. 2 is an infrared absorption spectrum of Fr12 obtained by the film method. Figure 3 shows 125 of Fr12 in deuterated chloroform.
Megahertz carbon-13 nuclear magnetic resonance spectrum. FIG. 4 is an ultraviolet absorption spectrum of Fr14-A in methanol. FIG. 5 is an infrared absorption spectrum of Fr14-A measured by the film method. No. 6 rllJ is a 125 MHz carbon-13 nuclear magnetic resonance spectrum of Fr14-A in deuterated chloroform. FIG. 7 is a graph showing the results of Comparative Experiment 1. Figure 1 Wavelength (nm) Figure 4 Wavelength (nm) Figure Elapsed time (hours)

Claims (6)

[Claims] (1) A new substance Fr-12 represented by the following formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (2) An antioxidant containing the compound Fr-12 represented by formula (I) as an active ingredient. (3) A method for producing Fr-12, which comprises separating and collecting the Fr-12 from an extract obtained by extracting turmeric with an organic solvent. (4) A novel substance Fr14-A represented by the following formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (5) An antioxidant containing the compound Fr14-A represented by formula (II) as an active ingredient. (6) A method for producing Fr14-A, which comprises separating and collecting the above-mentioned Fr14-A from an extract obtained by extracting turmeric with an organic solvent.