JPH06298753A - New cromanol derivative and its use - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as an antioxidant for food and drink, medicines, cosmetics and chemical raw materials. CONSTITUTION:A compound of the formula (R is H or acyl), e.g. 2,8-dimethyl-5- iodine-2-(1'-isobutyl-10'-methylundecyl)-6-cromanol. This compound is obtained by extracting a see weed which is a raw material for producing sodium alginate, e.g. Laminaria japonica, Eisenia bicyclis Setchell, Ecklonia cava Kjellman, Eckloniopsis radicosa or a seaweed belonging to the genus Macrocystis, the genus Ascophyllum, etc., with an organic solvent (e.g. diethyl ether) and purifying the extract with chromatography. The compound is an antioxidant substance derived from a natural product and usable in place of tocopherol.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel chromanol derivative and its use. More specifically, the present invention relates to a novel chromanol derivative having antioxidant activity, which is useful for foods and drinks, pharmaceuticals and the like.

[0002]

2. Description of the Related Art Conventionally, various antioxidants have been developed and used for various purposes. However, many of these antioxidants are industrially produced by chemical synthesis, and the number of substances having natural antioxidant activity is extremely small. For example, there are only tocopherols that have been put into practical use as substances having antioxidant activity obtained by extracting from natural products.

In recent years, the relationship between the phenomena such as cancer, arteriosclerosis, and further aging and the oxidative reaction in the body has been attracting attention.
There is an increasing expectation for antioxidants as drugs capable of suppressing the oxidation mechanism in the living body. For this reason, natural antioxidants that can be used in foods and drinks, pharmaceuticals, etc. are being searched for, and developments for their practical use are in progress, but so far promising ones have been realized. It has not been.

[0004]

The present invention has been made based on the background described above, and is useful as a natural antioxidant that replaces tocopherol, and is expected to be applied to foods and drinks, pharmaceuticals and the like. It is intended to provide antioxidants extracted from natural products.

[0005]

In order to solve the above problems, the present invention provides the following formula (1):

[0006]

[Chemical 3]

There is provided a novel chromanol derivative represented by the formula (wherein R represents a hydrogen atom or an acyl group). The compound represented by the above formula (1) of the present invention is a novel substance derived from a natural product, has antioxidant activity, and can be applied as an antioxidant for foods and drinks, pharmaceuticals, cosmetics, and chemical raw materials.

The novel chromanol derivative represented by the above formula (1) is obtained by separating it from seaweed powder which is a raw material for producing sodium alginate. Typical sodium alginate raw materials include, for example, kelp, sea bream, swordfish, antcum, Macrocystis , Ascophyllum , Durville.
Seaweeds belonging to the genus a, the genus Lessonia, etc. are mentioned. Seaweed, which is a raw material for the production of these sodium alginates, is extracted with an organic solvent such as acetone, diethyl ether, methanol and hexane, and then purified by chromatography such as high performance liquid chromatography to obtain the above formula (1) of the present invention. ) To obtain a novel chromanol derivative.

[0009]

【Example】

[Example 1] To 1930 g of dry powder of Ascophylum nodosum was added 5 times amount of acetone, and the mixture was stirred at room temperature for 1 hour and then filtered. The solvent was distilled off from the obtained filtrate under reduced pressure to obtain 113.0 g of extract. Partition the extract with diethyl ether / water (1: 1),
The diethyl ether layer was allowed to stand until it became transparent, then the diethyl ether layer was separated and the solvent was distilled off under reduced pressure.
7.4 g of extract was obtained.

Further, 57.2 g of this extract was added to hexane 3
It was dissolved in 00 ml, 300 ml of 50% methanol containing 3.6 g of sodium hydroxide was added, and the mixture was vigorously stirred and allowed to stand. The separated hexane layer was separated and the solvent was distilled off under reduced pressure to obtain an extract. 36.5 g of the obtained extract was saponified in accordance with the standard oil and fat analysis test method (2.4.10-71) to obtain 3.91 g of an unsaponifiable matter. After adding hot methanol to 3.91 g of this unsaponifiable matter and stirring,
The mixture was left overnight at 5 ° C to obtain 2.12 g of a methanol-soluble fraction. 2.12 g of this methanol-soluble fraction was loaded onto a silica gel column (silica gel 60, manufactured by Nacalai Tesque, Inc.) and developed with hexane / diethyl ether (90:10) to give 45.6 mg of an elution fraction showing an antioxidant effect. Got Furthermore, this was applied to an ODS column (MSGELC ₁₈ ,
Asahi Glass Co., Ltd.), and when developed with methanol, 34.2 mg of a fraction showing an antioxidant action which was eluted first was obtained. This was dissolved in ethanol to a concentration of about 5 mg / ml, 20 μl of each was injected into a high performance liquid chromatograph column (Cosmo Seal 5C ₁₈ , manufactured by Nacalai Tesque, Inc.), and a peak of 7.4 mg for a retention time of 9.05 minutes was obtained. A purified product of

The operating conditions of the high performance liquid chromatography were as follows. Eluent: Methanol Flow rate: 4 ml / min Detection: UV 283 nm The maximum value λ _MAX of UV absorption spectrum of the above purified product is 2
51.7 nm, and ¹ H-NMR is 500 MH.
_The obtained chart is shown in FIG. 1 for _Z and CDCl ₃ . The ¹³ C-NMR was performed 125MH _Z, in CDCl _3, resulting peaks, 16.041, 19.650, 19.765,
20.980, 22.629, 22.720, 23.649, 24.454, 2
4.811, 27.990, 29.563, 32.237, 32.699,
32.812, 37.302, 37.415, 37.455, 39.393, 3
9.487, 75.531, 88.980, 114.393, 122.864, 12
It was 8.189, 146.420, and 147.538.

The above UV absorption spectrum, ¹ H-NM
By R, ¹³ C-NMR, etc., the substance obtained in the present invention is
The following formula (1),

[0013]

[Chemical 4]

(In the formula, R represents a hydrogen atom or an acyl group.) A chromanol derivative represented by 2,8
-Dimethyl-5-iodo-2- (1'-isobutyl-1)
It was determined to be 0'-methylundecyl) -6-chromanol. As a result of searching this compound, it was found to be a novel compound.

Example 2 With respect to the chromanol derivative obtained in Example 1 above, the rate of lipid peroxidation inhibition was measured for each concentration, using α-tocopherol as a control. The results are shown in Table 1 below.

[0016]

[Table 1]

FIG. 2 is a correlation diagram of the lipid peroxidation inhibition rate with respect to the concentration of the chromanol derivative of the present invention.
-Shows a comparison of antioxidant activity with tocopherol. Figure 2
Inside, the black circles indicate the chromanol derivative of the present invention, and the white circles indicate α-tocopherol.

[0018]

INDUSTRIAL APPLICABILITY In the present invention, a novel chromanol derivative is obtained from seaweed, which is a raw material for alginic acid. The novel chromanol derivative of the present invention has an antioxidant effect,
Expected as an antioxidant for food and drink, pharmaceuticals, cosmetics, chemical products, etc.

[Brief description of drawings]

FIG. 1 ¹ H of a chromanol derivative of Example 1 of the present invention
-Shows an NMR spectrum.

FIG. 2 is a correlation diagram of the lipid peroxidation inhibition rate with respect to each concentration of the chromanol derivative of the present invention, showing the antioxidant activity of the compound.

Claims (2)

[Claims] 1. The following formula (1): (R in the formula represents a hydrogen atom or an acyl group.) A new chromanol derivative. 2. The following formula (1): (An R in the formula represents a hydrogen atom or an acyl group.) An antioxidant containing a novel chromanol derivative as an active ingredient.