JPH0761905A - Beautifully whitening cosmetic - Google Patents

Abstract

PURPOSE:To provide a beautifully whitening cosmetic containing a karahanaenone derivative obtained from the oil of Humulus lupulus L., having a strong beautifully whitening action, and safe for skins. CONSTITUTION:A beautifully whitening cosmetic contains a Karahanaenone derivative [karahanaenone derivatives of formulas I and II (R is alkyl) are especially effective]. The karahanaenone derivative can be compounded with other cosmetic raw materials, e.g. a liquid oil such as squalane or jojoba oil, a solid oil such as beewax or cetyl alcohol, various activators, a humectant such as glycerol or 1,3-butylene glycol, and various medicinal agents, and subsequently be prepared into various shape cosmetics, such as lotions, creams, milky lotions or packs.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cosmetic having a high whitening effect.

[0002]

Kalahana enone is a monoterpene compound obtained from hop oil and the like, and is one of the important compounds in perfume. The chemical structural formula of Kalahana enone is shown in Chemical Formula 3 below. Kalahana Enon itself has no whitening effect.

[Chemical 3]

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a cosmetic which is safe when applied to the skin and has a large whitening effect.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have prepared various derivatives of karahanaenone obtained from hop oil and conducted experiments to find the following structures. The present inventors have completed the present invention by detecting that the derivative substance of (1) has a strong whitening effect and is very effective as a raw material for cosmetics. A known method may be used to prepare these derivatives.

As a method of utilizing this derivative substance, other cosmetic materials such as liquid oils such as squalane and jojoba oil, solid oils such as beeswax and cetyl alcohol, various active agents,
Moisturizers such as glycerin and 1,3 butylene glycol,
Cosmetics of various dosage forms can be prepared by adding various drugs and the like. For example, a lotion, a cream, a milky lotion, a pack, or the like may be used depending on the purpose.

Among the derivatives of karahanaenanone, which is the active ingredient for whitening cosmetics of the whitening cosmetic composition of the present invention, those having the following structures are particularly effective.

[Chemical 4]

[Chemical 5]

[0007]

[Manufacturing Example] The following describes a manufacturing example which is a method for manufacturing an actual derivative, but the present invention is not limited to this manufacturing example.

(Production Example 1) N-p-hydroxyphenyl-3,3,6-trimethyl-5-cycloheptan-2-one-1-carboxamide Under a nitrogen stream, 200 ml equipped with a magnetic stirrer and a septum cap. While cooling the four-necked flask of 1. in a dry ice-acetone bath, 1.64 mol / liter-
23.4 ml of n-butyllithium and a hexane solution were injected, and 20 ml of dry ether was further added. A solution of 4.2 g of diisopropylamine and 10 ml of dry ether was added dropwise thereto over 50 minutes, and the mixture was stirred for 1 hour after the addition. After stirring, a solution of 5.0 g of kalahananone and 10 ml of dry ether was added dropwise over 40 minutes, and after the addition, the mixture was stirred for 1 hour and 30 minutes. After stirring, after replacing the reaction system with carbon dioxide,
3 while stirring dry frost-free pieces of dry ice
It took 0 minutes and was charged. Then, the cooling bath was removed, and the mixture was stirred for 30 minutes while gradually returning to room temperature. After completion of the reaction, the mixture was acidified by adding 100 ml of 1N hydrochloric acid, extracted with 500 ml of ethyl acetate, and washed with saturated saline until the aqueous layer became neutral. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain a crude product.

Further, the crude product was washed with hexane while sucking on the Nutsche, and dried under reduced pressure to obtain 3,
3,6-Trimethyl-5-cyclohepten-2-one-
1-carboxylic acid was obtained. The yield was 5.57g. In a 50 ml four-necked flask equipped with a stirrer, a calcium chloride tube and a dropping funnel, 3,3,6-trimethyl-
5-Cyclohepten-2-one-1-carboxylic acid 2.5
g and hexamethylphosphoric triamide in catalytic amounts, and while vigorously stirring under ice cooling, 1 ml of thionyl chloride (3.5 ml) was added.
The mixture was added dropwise over 0 minutes and stirred for 40 minutes after the addition. Then, the mixture was stirred under reduced pressure for 20 minutes to remove excess thionyl chloride. After completion of the reaction, the reaction product was extracted with ethyl acetate and operated in a usual manner to obtain a crude product of β-ketocarboxylic acid chloride.

Next, 10.2 ml of acetic acid and 1.5 g of p-aminophenol were placed in a 50 ml four-necked flask equipped with a stirrer and a dropping funnel, and the prepared β-ketocarboxylic acid chloride was stirred at room temperature. It dripped over 20 minutes. After completion of dropping, aqueous sodium acetate solution (3.0 g / 1
2.5 ml) was added in one portion and the mixture was further stirred for 1 hour and 30 minutes. After completion of the reaction, the reaction product was extracted with ethyl acetate and operated in a usual manner to obtain a crude product. Further, it was purified by silica gel column chromatography (200 mesh, solvent hexane: ethyl acetate = 7: 3), and Np-hydroxyphenyl-3,3,6-trimethyl-5-cycloheptene-2-
On-1-carboxamide was obtained in a yield of 2.8 g.

(Production Example 2) 2-hydroxy-Np-hydroxyphenyl-3,
3,6-trimethyl-5-cycloheptene-1-carboxamide 50ml with stirrer, calcium chloride tube, dropping funnel
Sodium borohydride (0.2 g) and anhydrous ethanol (2.0 ml) were placed in the four-necked flask described above and stirred under ice-cooling, and N-p-hydroxyphenyl-3,3,3 of Production Example 1 was stirred.
6-trimethyl-5-cyclohepten-2-one-1-
Carboxamide (1.0 g) was dissolved in the minimum amount of absolute ethanol and added dropwise over 30 minutes. After completion of dropping, the mixture was stirred at room temperature for 1 hour.

After completion of the reaction, the reaction product was extracted with ethyl acetate and operated in a conventional manner to obtain a crude product. Further purified by silica gel column chromatography (200 mesh, solvent hexane: ethyl acetate = 9: 1) to give 2-hydroxy-N.
-P-hydroxyphenyl-3,3,6-trimethyl-
Yield of 5-cycloheptene-1-carboxamide 2.
Obtained in 0 g.

[0013]

Example 1 Lotion (parts by weight) Olive oil 0.5 Np-hydroxyphenyl-3,3,6-trimethyl-5-cyclohepten-2-one-1-carboxamide 0.5 polyoxy of Production Example 1 Ethylene (20E.O.) sorbitan monostearate 2.0 Polyoxyethylene (60E.O.) Hydrogenated castor oil 2.0 Ethanol 10.0 1.0% sodium hyaluronate aqueous solution 5.0 Purified water 80.0

[0014]

Example 2 Cream A Squalane 20.5 Olive Oil 2.0 Mink Oil 1.0 Jojoba Oil 5.0 Beeswax 5.0 Cetostearyl Alcohol 2.0 Glycerin Monostearate 1.0 Sorbitan Monostearate 2.0 Production 2-Hydroxy-N-p-hydroxyphenyl-3,3,6-trimethyl-5-cycloheptene-1-carboxamide of Example 2 0.5

B Purified water 47.9 Polyoxyethylene (20 E.O.) sorbitan monostearate 2.0 Polyoxyethylene (60 E.O.) hydrogenated castor oil 1.0 glycerin 5.0 1.0% hyaluronic acid Aqueous sodium solution 5.0 Methyl paraoxybenzoate 0.1 A and B were weighed and heated to 70 ° C., A was slowly added to B with stirring, and then 30 with slow stirring.
Cooled to ° C.

(Tyrosinase activity inhibition test) (Test method) 30 mM sodium phosphate buffer (pH
6.8) 1.8 ml, 1.66 mM tyrosine aqueous solution 1.0
After incubating ml at 37 ° C, 0.1 ml of a 15 mM dimethylsulfoxide solution of the sample was added and stirred, and then 0.1 ml of an aqueous tyrosinase solution (about 900 unit / ml) was added, and the mixture was stirred and kept at 37 ° C at 475 nm. After the addition of the aqueous tyrosinase solution, the wavelength was measured 1 minute and 11 minutes later. As a control, 0.1 ml of dimethyl sulfoxide was added instead of the above test solution, and the same measurement was performed. In this test, the final concentration of the sample is 0.5 mM. (Calculation formula) Tyrosinase activity inhibition rate (%) = ((B11-B1)-(A11-A1))
/ (B11-B1) × 100 However, A1: Absorbance of sample specimen after 1 minute A11: Absorbance of sample specimen after 11 minutes B1: Absorbance after 1 minute of control B11: Absorbance after 11 minutes of control It shows in Table 1.

[0017]

[Table 1]

(Usage test) The faces of seven women were divided into left and right, the left side was used with the lotions and creams of Examples 1 and 2, and the right side was used with the lotions and creams of Comparative Examples 1 and 2. After three months, the sensory test results were surveyed according to the following criteria to obtain the total score. Comparative Example 1 is a lotion obtained by removing the compound of Production Example 1 from Example 1, and Comparative Example 2 is a cream obtained by removing the compound of Production Example 2 from Example 2. That is, the experiment No1 is shown in Table 2
become that way.

[0019]

[Table 2]

The judgment criteria are as follows, and Table 3 below shows the total values of the questionnaire results. Example is very good 3 Example is considerably good 2 Example is slightly good 1 No difference 0 Comparative example is good −1 Comparative example is good −2 Comparative example Is very good -3

[0021]

[Table 3]

[0022]

[Effect of the invention] From the tyrosinase activity inhibition test,
Also, the results of the usage test revealed that the Kalahana enone derivative of the present invention has an excellent whitening effect. An excellent whitening cosmetic product can be obtained by blending with cosmetics.

Claims (2)

[Claims] 1. A whitening cosmetic containing a derivative of kalahana enone. 2. A whitening cosmetic composition containing a Kalahana enone derivative according to claim 1, wherein the Kalahana enone derivative has a structure shown below. [Chemical 1] [Chemical 2]