JPH07109294A - Stigmastanol glycoside and hair producing and growing agent containing the same - Google Patents

Abstract

PURPOSE:To obtain the glycoside, expressed by a specific formula, having excellent hair producing and growing effects and safety capable of sufficiently withstanding the use for a long period and useful as a hair producing and growing agent. CONSTITUTION:This glycoside is expressed by the formula [(n) is 1-4], specifically stigmastanol maltoside, etc. Furthermore, the glycoside is preferably obtained by adding stigmastanol as a starting substance and an acylated maltooligosaccharide having 2-5 number of saccharides to a solvent of dichloromethane, reacting both in the presence of a catalyst such as a BF3 etherate complex in an N2 gas stream, fractionating and isolating the reactional product according to the silica gel chromatography, deacylating the resultant purified substance, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to stigmasteranol glycosides and a hair-growth / hair-growth material containing the same as an active ingredient.

[0002]

2. Description of the Related Art Generally, as an active ingredient of a hair growth and hair-growth agent, an ingredient that improves blood circulation in the scalp and enhances skin function to activate the metabolic function of hair follicles and hair bulbs, or Examples include dandruff, itching prevention, nutritional supplementation, moisturizing, and other ingredients that maintain normal physiological functions of the scalp. Many herbal medicines, plant extracts and synthetic compounds have been reported as hair growth and hair growth ingredients.

As such herbal medicine and plant extract, for example, extract of Yokuinin, Ginkgo, Kashi, etc. (Japanese Patent Publication No. 1-13451, JP-A-2-48).
512, JP-A-2-48514) and the like, and synthetic compounds include vitamin E, alloxazine, pyridine N-oxide, adenosine-3 ′,
5'-cyclic monophosphate, etc. (JP-A-64-
56608, JP-A-1-261321, JP-A-2-204406) and the like.

However, most of the hair-growth and hair-growth agents containing the above-mentioned hair-growth and hair-growth ingredients show no remarkable effect, and even those having a certain degree of effect are strongly irritating and cause dermatitis, or However, there were problems such as continuous use being difficult due to side effects.

[0005] By the way, among such hair-growth and hair-growth ingredients, there have been many reports especially paying attention to saponins (glycosides whose non-sugar portion is a steroid or triterpenoid) contained in herbal medicines and plant extracts (special characteristics). Kaisho 60-38314
Japanese Patent Publication No. 62-93217, Japanese Patent Publication No. 3-6
1642), and more recently, reports on steroid glycosides and triterpenoid glycosides as active ingredients (JP-A-4-5219 and JP-A-5-25023) have come to be reported.

[0006] Thus, saponins and steroid glycosides,
Triterpenoid glycosides are expected to have hair-growth and hair-growth effects and various attempts have been made, but so far, those having sufficient hair-growth and hair-growth effects have not been obtained.

[0007]

SUMMARY OF THE INVENTION The present invention has been made from the above point of view, and is of a steroid glycoside-containing content which is excellent in hair growth and hair-growth effects and which is sufficiently safe for long-term use. The challenge is to provide hair growth and hair restoration materials.

[0008]

In order to solve the above-mentioned problems, the present inventors have synthesized various steroid glycosides,
As a result of screening these with hair growth and hair growth effects as indexes, a stigmasteranol glycoside having excellent hair growth and hair growth effects and safety was found, and the present invention was completed.

That is, the present invention is a stigmasteranol glycoside represented by the following general formula (I) and a hair-growth / hair-growth material containing the same.

[0010]

[Chemical 2]

However, in chemical formula 2, n represents an integer of 1 to 4. Hereinafter, the present invention will be described in detail.

<1> Stigmasteranol Glycosides of the Present Invention The stigmasteranol glycosides of the present invention are compounds represented by the general formula (I), and can be used in soybean oil, coconut oil, cotton seeds and the like. It can be synthesized from stigmasteranol, which is one of the contained sterols, by the following method.
A commercially available product may be used as the starting material stigmasteranol.

Stigmasteranol and an acylated maltooligosaccharide having a sugar number of 2 to 5 are added to a dichloromethane solvent and reacted in the presence of a catalyst of a BF ₃ ether complex under a nitrogen stream. After the reaction was completed, the dichloromethane layer was evaporated to dryness,
Fractionation by silica gel column chromatography, deacylation after isolation, yields the stigmasteranol glycoside represented by the general formula (I).

If acylated maltose (number of sugars 2) is used as the acylated maltooligosaccharide to be reacted with stigmasteranol, the obtained stigmasteranol glycoside is n in the compound of the general formula (I). Is Stigmasteranol maltoside of 1. Similarly, if acylated maltotriose (3 sugars) is used, n = 2 stigmasteranol maltotrioside, and if acylated maltotetraose (4 sugars) is used, n = 3 stigmasteranol is used. If maltotetraoside and acylated maltopentose (having 5 sugars) are used, stigmasteranol maltopentaoside with n = 4 can be obtained.

<2> Hair growth / hair-growth agent of the present invention The hair growth / hair-growth agent of the present invention contains the above-mentioned stigmasteranol glycoside. The blending amount is 0.
It is preferably 0005 to 5% by weight. Furthermore, it is more preferable in the present invention that the blending amount is 0.001 to 5% by weight based on the total amount. Compounding amount 0.0
If the amount is less than 005% by weight, sufficient hair growth and hair growth effects cannot be expected, and if the amount is more than 5% by weight, the effect reaches a ceiling and is not economical.

The dosage form of the hair-growth / hair-growth material of the present invention is not particularly limited, but, for example, hair tonic, shampoo, conditioner, pomade, hair lotion, hair cream, hair treatment and the like are generally used. -The thing used as a hair growth material is mentioned. These hair-growth / hair-growth agents can be produced by the same method as that for a normal hair-growth / hair-growth agent, except that a stigmasteranol glycoside is added.

Further, the hair-growth / hair-growth material of the present invention is usually
Hydrocarbons, waxes, oils and fats, esters, higher fatty acids, higher alcohols, surfactants, fragrances, pigments, preservatives, antioxidants, UV protection agents, which are applied to hair growth and hair restoration agents,
Alcohols, pH adjusters, and various medicinal components suitable for various purposes are appropriately selected and prepared. Furthermore, hair growth of the present invention, hair growth and hair growth components other than stigmasteranol glycoside which is a hair growth component, for example, estrogen, peripheral vascular blood flow promoter, local stimulant, keratolytic agent, antiseborrheic agent , Bactericide, metabolism enhancer, oxygen activity inhibitor, antiphlogistic, nutritional supplement,
A moisturizer or the like can also be used in combination with stigmasteranol glycoside.

[0018]

EXAMPLES Examples of the present invention will be described below. First, examples of stigmasteranol glycosides, which are the hair-growth and hair-growth components of the present invention, will be shown.

[0019]

Example 1 Stigmasteranol Maltoside 1.25 g of stigmasteranol and 6.1 g of acetylmaltose were added to 10 ml of a dichloromethane solvent, 1.0 g of a BF ₃ ether complex as a catalyst was added thereto, and the mixture was added under a nitrogen stream. The reaction was carried out for 12 hours. Then, the dichloromethane layer was evaporated to dryness from the reaction solution, and fractionated and isolated by silica gel column chromatography to give a purified product,
This was deacetylated to obtain 0.75 g of stigmasteranol maltoside. The NMR measurement results of the obtained stigmasteranol maltoside are shown in FIG.

[0020]

Example 2 Stigmasteranol Maltotrioside Using 8.7 g of acetylmaltotriose instead of acetylmaltose of Example 1, the same reaction as in Example 1 was carried out to give 0.65 g of stigma. Stanol maltotrioside was obtained. The NMR measurement results of the obtained stigmasteranol maltotrioside are shown in FIG.

[0021]

Example 3 Stigmasteranol Maltotetraoside Instead of the acetylmaltose of Example 1, 11.3 g
The same reaction as in Example 1 was carried out using acetyl maltotetraose of to obtain 0.28 g of stigmasteranol maltotetraoside. The NMR measurement results of the obtained stigmasteranol maltotetraoside are shown in FIG.

[0022]

Example 4 Stigmasteranol Maltopentaoside Instead of the acetylmaltose of Example 1, 13.9 g was used.
The same reaction as in Example 1 was carried out using acetyl maltopentaose of Example 1 to obtain 0.44 g of stigmasteranol maltopentaoside. The NMR measurement results of the obtained stigmasteranol maltopentaoside are shown in FIG.

Similarly, acetylmaltohexaose was used in place of acetylmaltose of Example 1 to give stigmasteranol hexaoside of Comparative Example 1,
The stigmastanol maltoheptaoside of Comparative Example 2 was produced using acetylmaltoheptaose.

<Evaluation of stigmasteranol glycosides> Using the stigmasteranol glycosides obtained in each of the above Examples and Comparative Examples, a hair growth test was conducted on mice to evaluate hair growth and hair growth effects. . For further comparison, hair growth, stigmasteranol as a raw material for the hair-growth ingredient stigmasteranol glycoside, stigmasteranol glucoside having a sugar number of 1 among stigmasteranol glycosides, Vitamin E, which has hitherto been known as a substance having hair growth and hair growth effects, was evaluated in the same manner.

The backs of 9-week-old C3H mice in 12 groups of 10 mice each were hair-removed to a size of 2.0 × 2.0 cm, and the L value of the color difference at that site was measured using a color difference meter. . From the next day, for 16 days, 70% ethanol aqueous dispersion containing 1% by weight of each of the samples shown in Table 1 was applied to the dorsal hair removal site of 11 groups of the mice at 0.04 per day.
The remaining 1 group was applied as a control group, and only the 70% ethanol aqueous solution was similarly applied to the dorsal part of the back of the group. After the application is completed, the color difference L of the hair removal site is again set to L.
The value was measured using a color difference meter and compared with the result immediately after hair removal. Here, the smaller the L value of the color difference meter, the stronger the black color, that is, the higher the hair density. The results are shown in Table 1.
Shown in.

[0026]

[Table 1]

As is apparent from these results, the L value on the 16th day after application of the sample containing the stigmasteranol glycosides, which is a hair growth and hair-growth component of the present invention, was the same as that of the comparative products of vitamin E and suture. The L value on the 16th day after application of the samples containing the samples containing tigmasteranol, stigmasteranol glucoside, stigmasteranol maltohexaoside, and stigmasteranol maltoheptaoside was L of the control group.
Although it is almost the same as the value, it is significantly smaller, indicating that the rate of increase in hair density is faster. In this experiment, the skin color of the mouse did not change at all, and it can be said that the change in the L value of the color difference was related to the hair density.

Next, examples of the hair-growth / hair-growth material of the present invention using the stigmasteranol glycosides obtained in the above examples will be described. In addition, all compounding amounts used below are parts by weight.

[0029]

Examples 5 to 15 Hair Tonic Each of the components shown in Table 2 was dissolved by heating and solubilized to produce a hair tonic. Similarly, hair tonics of Comparative Examples 3 to 6 containing stigmasteranol glucoside instead of the stigmasteranol glycoside of the present invention shown in Table 3 and Comparative Example 7 not containing stigmasteranol glycoside were also produced. did.

[0030]

[Table 2]

[0031]

[Table 3]

<Evaluation of Hair Growth and Hair Growth Agent of the Present Invention> Regarding the hair tonics of Examples 5 to 15 and Comparative Examples 3 to 7,
Human hair growth and hair growth tests were carried out.

160 panelists who complain of thinning hair and alopecia were divided into 16 groups of 10 people each, and the hair tonics obtained in Examples 5 to 15 and Comparative Examples 3 to 7 were used in a usual tonic method. I applied it twice a day to the head evenly, and I had it used for 6 consecutive months. The evaluation was performed by conducting a questionnaire survey on hair growth and hair growth after 3 months and 6 months. The results are shown in the bottom columns of Tables 2 and 3.

As shown in the table, in the group using the hair tonic of the present invention, particularly the hair tonic containing the stigmasteranol glycoside in a preferable amount, stigmasteranol glucoside was used instead of the stigmasteranol glycoside. Compared to the group using the hair tonic of the comparative example and the hair tonic of the comparative example that did not contain the stigmasteranol glycoside, the number of people who had downy hairs and the number of hairs that had bristles was greater. At the end of the test, the condition of the scalp was improved, and many people declared that hair loss was reduced. From this, it is clear that the hair-growth / hair-growth material of the present invention has excellent hair growth and hair-growth effects.

Furthermore, during the use test period, no skin damage such as deterioration of the scalp or inflammation was observed in any panelist, so that the hair growth and hair restoration agent of the present invention is highly safe. Was confirmed.

[0036]

Example 16 Hair Tonic Component A in Table 4 was mixed and mixed well with component B and C.
The ingredients were added to make a hair tonic.

[0037]

[Table 4]

[0038]

Example 17 Hair Treatment Each of the components A and B in Table 5 was heated to 80 ° C.,
Both were mixed and emulsified. After that, it was cooled to around 40 ° C., and at that time, the component C was added and the component D was further added to obtain a product.

[0039]

[Table 5]

[0040]

Example 18 Hair Shampoo The components A in Table 6 were mixed at 80 ° C., then cooled to around 40 ° C., the components B were added, and the components C were further added to obtain a product.

[0041]

[Table 6]

[0042]

Example 19 Hair Rinse Components A and B of Table 7 were each heated to 80 ° C.,
At that time, they were mixed and emulsified. After that, the product was cooled to around 40 ° C., the C component was added, and the D component was further added to obtain a product.

[0043]

[Table 7]

[0044]

Example 20 Hair Cream The component A in Table 8 was mixed and dissolved at 80 ° C., and the component B preheated to 80 ° C. was gradually added to form a cream. Then, it cooled to 40 degreeC and added the C component, and it was set as the product.

[0045]

[Table 8]

[0046]

EFFECTS OF THE INVENTION The hair growth and hair growth product of the present invention contains the newly synthesized stigmasteranol glycoside, so that it has excellent hair growth and hair growth effects and is sufficiently resistant to long-term use. It has good safety.

[Brief description of drawings]

FIG. 1 is a diagram showing NMR measurement results of stigmasteranol maltoside obtained in Example 1.

FIG. 2 shows NMR measurement results of stigmasteranol maltotrioside obtained in Example 2.

FIG. 3 shows NMR measurement results of stigmasteranol maltotetraoside obtained in Example 3.

FIG. 4 shows NMR measurement results of stigmasteranol maltopentaoside obtained in Example 4.

Claims (3)

[Claims] 1. A stigmasteranol glycoside represented by the following general formula (I). [Chemical 1] However, n in Chemical formula 1 shows the integer of 1-4. 2. A hair-growth / hair-growth material containing the stigmasteranol glycoside according to claim 1. 3. The hair-growth / hair-growth agent according to claim 2, wherein the content of the stigmasteranol glycoside is 0.0005 to 5% by weight based on the total amount.