JP2000095961A - Ylidoid compound, preparation thereof and dyeing method using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for easily preparing ylidoid compounds from gardenia without being disturbed by crocin in fruit, chlorophyll in leaves or the like. SOLUTION: Ylidoid compounds contained in white flowers of gardenia, particularly in white flowers of a double flower species of gardenia are extracted with a solvent composed of at least one of a lower alcohol and water. For example, white flowers of gardenia are cut off, ground in a solvent composed of at least one of a lower alcohol and water and filtered, and the filtrate is condensed and purified by chromatography to obtain crude crystals of ylidoid compounds. Further, the filtrate (extract) can be used in dyeing silk cloth and the like by directly adding an amine thereto to be allowed to develop color in the presence of a β-glycosidase, and silk cloth and the like can be dyed in various colors of blue series.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an iridoid compound useful for plant dyeing, a method for producing the compound, and a dyeing method using the compound.

[0002]

BACKGROUND OF THE INVENTION Gardenia, a plant belonging to the family Rubiaceae, has been used for plant dyeing for a long time, but it uses fruits for yellow dyeing of clothing, and the yellow source is a pigment called crocin. It is known. In addition, the gardenia fruit contains an iridoid compound, which is colored by red-purple-blue by the action of β-glucosidase, and by allowing β-glucosidase and a primary amino group-containing substance to act. It is described in JP-B-61-19234 that a blue dye can be produced.

[0003] In recent years, it has been pointed out that such iridoid compounds are not only useful for producing colorants by condensation with amines, but also have antitumor medicinal effects, and the production of drugs in this area is expected. Demand is expected to increase in the future.

However, the method for producing an iridoid compound from a gardenia has heretofore been carried out only by a complicated method of purifying a gardenia fruit while removing yellow crocin [“Pharmaceutical Magazine” 94 (5) 577-586 (1974)
And JP-B-61-19234].

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing an iridoid compound from a gardenia extremely easily without being hindered by crocin in fruits or chlorophyll in leaves.

[0006]

Means for Solving the Problems The present inventor has paid attention to the double-flowered gardenia, which has recently increased large white flowers,
The present invention was completed by discovering that the large white gardenia flower contained a large amount of an iridoid compound.

The iridoid compound of the present invention is obtained by extracting an iridoid compound contained in a white flower of a gardenia with a solvent composed of at least one of lower alcohol and water. Is ground in a solvent consisting of one or more lower alcohols and water,
It can be produced by filtering, concentrating the filtrate, and purifying by a chromatographic method to obtain crude iridoid crystals.

The use of a double-flowered gardenia flower without fruit is particularly effective as follows. (1) Gardenia fruits used in the usual iridoid compound production process only bear fruit in single-flowered gardenia, but single-flowered gardenia trees are generally small and have few flowers, making them suitable for viewing in a corner of a Japanese garden. It is not easy to obtain a large amount of gardenia fruit, and it is necessary to remove yellow crocin from gardenia fruit to obtain an iridoid compound as described above. (2) In contrast, double-flowered gardenia, which has recently been planted for park and street greening, has many large flowers of about 10 g per grain, so it is easy to use and because it is a flower, It does not contain contaminants such as tannins, and it does not bear fruit, so it does not contain the main yellow pigment crocin in fruits. Therefore,
Extraction of iridoid compounds is extremely easy. (3) Gardenia double-flowered species can be planted very easily by cutting method for the purpose of white flower production.

In order to obtain an extract from the double flower of gardenia gardenia, a mixer is used, for example, methanol, ethanol,
Grind with water or an arbitrary mixture thereof to produce a juice, which is filtered with a filter cloth or filter paper, and the filtrate is used as an extract. In addition, the filtrate may have a slight yellow color, but may be said to be almost colorless. (1) The solvent is distilled off from the extract using a rotary distillation apparatus, and the concentrated liquid is cooled in a refrigerator to obtain a crude iridoid liquid. Further, it is appropriately purified by a chromatographic method to obtain crude iridoid crystals. (2) The extract is diluted appropriately, amines (primary amines) are added, and the temperature is maintained at 30 to 50 ° C. and pH around 6 to 7 for several hours in the presence of a small amount of β-glucosidase. Upon reaction, different colors are obtained depending on the type of amines added. An object to be dyed such as a cloth is put into this liquid,
It can be dyed in various colors.

The amines used in the dyeing method (2) are as follows:
For example, urea, methylamine, tetramethylenediamine,
It may be selected from the group consisting of hexamethylenediamine, γ-aminobutyric acid, 2-aminoethanesulfonic acid, p-aminobenzoic acid, aminobenzenesulfonic acid, glycine, glutamic acid, glucosamine, chitin and chitosan.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, the present invention will be described with reference to embodiments. Example 1 50 double-flowered gardenia white flowers (fresh weight: about 500 g) of Yaesaki were ground using a household juicer in 500 ml of ethanol to obtain a juice. This juice was filtered, ethanol was distilled off by a rotary distillation apparatus, and 2 g of activated carbon was added to the concentrated liquid to adsorb iridoid. Then, about 40 ml of methanol was dropped into the activated carbon, and the mixture was appropriately purified by a chromatographic method to obtain 0.75 g of crude iridoid crystals.

Example 2 100 g of double-flowered gardenia white flowers were collected, 150 ml of shochu containing 35% alcohol was added to the white flowers, and the mixture was mixed with a mixer to obtain a pale yellow juice. The juice is filtered through a cloth, and glucosamine and the enzyme glucosidase are added using the amount of juice corresponding to one white flower to 30 ° C to 40 ° C.
The color was developed at ℃ to obtain a dark blue dyeing liquor. This coloring is similar to the case where one commercially available gardenia fruit is used for coloring, and one white flower contains iridoids that are almost equivalent to one gardenia fruit (branch). Understand.

Example 3 The method of Example 2 was repeated except that urea, methylamine, γ-aminobutyric acid, tetramethylenediamine, hexamethylenediane, 2-aminoethanesulfonic acid, p-aminobenzoic acid were used instead of glucosamine as amines. The test was carried out using an acid and p-aminobenzenesulfonic acid, and silk cloth was put into the resulting eight dyeing liquors and dyed. As a result, the silk cloth was beautifully dyed in a gray, blue-violet, mauve, navy bellflower, bellflower, natural forget-me-not, celadon porcelain, and water onion color corresponding to each amine.

Example 4 Sixty white flowers (250 g) of double-flowered gardenia were immersed in 600 ml of methanol and ground with a juicer, and the juice was used as a stock solution of iridoid. Separately, 0.1 g of chitosan, pH 5.0
~ 6.0 solution was prepared, 2 ml of chitosan solution and 2 ml of iridoid stock solution were mixed, and about 10 mg of β-glucosidase was added thereto. The mixture was shaken well, adjusted to pH 5-6 and 30-40 ° C, and reacted overnight. I let it. As a result, a dark blue viscous liquid was obtained, which could be used as a paint.

[0015]

According to the present invention, gardenia white flowers (especially double-flowered gardenia flowers), which were not considered to be usable for plant dyeing or drug production, are used in the present invention, and the operability is very good.
Production of iridoid compounds has been made possible. In addition, it was possible to easily carry out a staining with a bluish change using gardenia white flowers.

Claims (5)

[Claims] 1. An iridoid compound obtained by extracting an iridoid compound contained in a white flower of a gardenia with a solvent comprising at least one of lower alcohol and water. 2. A white flower of gardenia is ground in a solvent comprising one or more of lower alcohol and water, filtered, concentrated, and purified by a chromatographic method to obtain crude iridoid crystals. A method for producing an iridoid compound. 3. The method according to claim 2, wherein the gardenia is a double-flowered gardenia. 4. An amine is added to a liquid containing an iridoid compound extracted from a white flower of a gardenia with a solvent comprising at least one of lower alcohol and water, and a temperature of 30 to 50 ° C.
Keep pH 6-7, add β-glucosidase to react,
A dyeing method using an iridoid compound, which comprises adding a material to be dyed to a liquid having a desired color tone. 5. The method according to claim 1, wherein the amines are urea, methylamine,
Tetramethylenediamine, hexamethylenediamine, γ
5. The composition according to claim 4, which is selected from the group consisting of -aminobutyric acid, 2-aminoethanesulfonic acid, p-aminobenzoic acid, aminobenzenesulfonic acid, glycine, glutamic acid, glucosamine, chitin and chitosan.
the method of.