JPH04134041A - P-xylidene ketone derivative, ultraviolet absorber containing said derivative and cosmetic containing said absorber - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R<1> is saturated hydrocarbon group or cyclic hydrocarbon group; R<2> and R<3> are H or form a divalent hydrocarbon group which may have a substituent group together with R<1>; n is 0 or 1). EXAMPLE:1,4-Bis(4,4-dimethyl-3-oxopenta-1-enyl)benzene. USE:An ultraviolet absorber and cosmetic having excellent stability to light. PREPARATION:A compound expressed by formula II or formula III is reacted with a compound expressed by formula IV in an alcohol based solvent using a base as a catalyst at 20-150 deg.C to produce the compound expressed by formula I.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides a novel p-xylidene ketone derivative that has an ultraviolet absorbing effect and excellent photostability, and a novel p-xylidene ketone derivative containing the same that has an ultraviolet absorption effect and excellent photostability. relates to ultraviolet absorbers and cosmetics with excellent UV protection effects.

[Conventional technology]

Ultraviolet rays are known to cause various changes in the skin. Dermatologically, the working wavelength is 400 to 320n.
It is divided into long wavelength ultraviolet rays of m, medium wavelength ultraviolet rays of 320 to 290 nm, and short wavelength ultraviolet rays of 290 nm or less.
They are called V-AXIIV-8 and UV-C. The ultraviolet rays in sunlight are UV-A and IIV-B, and UV-
C is absorbed in the ozone layer and almost never reaches the ground.

When UV-8 is irradiated to the skin with a certain amount of light, it causes changes in the skin, such as erythema and water damage, as well as accelerating melanin formation and pigmentation.

On the other hand, UV-A causes a blackening effect on the skin (immediate blackening) immediately after irradiation, and since its energy reaches the dermis, it causes changes in blood vessel walls and elastic fibers in connective tissues. Such action on IIV- accelerates skin aging and is thought to be a factor in the appearance of age spots, wrinkles, and freckles.

As the effects of ultraviolet rays on human skin become clearer, compounds that absorb IIV-A have been developed. It is said that it is desirable that such ultraviolet absorbers satisfy all of the following conditions.

■ [Absorb IV-A light as completely as possible.

■ Stable against light and heat.

■ No toxicity, irritation or other harmful effects on the skin.

■　Effects should last.

■ Excellent compatibility with cosmetic bases.

Conventionally, for example, dibenzoylmethane derivatives have been used as +1 V -A absorbers.

[Problem to be solved by the invention]

However, these conventional ultraviolet absorbers do not necessarily fully satisfy the above conditions, and are particularly unstable against light, and are known to cause decomposition and reactions due to ultraviolet light [: Int, J .

Cosmet, ic 5science, 10.53 (
I988)] o Such decomposition of ultraviolet absorbers not only leads to a decrease in the duration of their effects, but also the effects on the skin of the decomposed products themselves or products generated by reaction with the formulation cannot be ignored [Fragrance Journal, 84 .3
4 (I9B?)).

Therefore, there has been a desire for an ultraviolet absorber that satisfies the above conditions, particularly an ultraviolet absorber that has excellent stability against light.

[A means of saving to solve problems]

In view of these circumstances, the present inventors have synthesized a number of p-xylidene ketone derivatives and studied their properties, and found that the novel p-xylidene ketone derivative represented by the general formula (I) below is an excellent IIV. -He discovered that it had an A-absorbing effect and was extremely stable against light, and that by incorporating it, a cosmetic with excellent sunburn prevention effects could be obtained, and he completed the invention of wood. .

That is, the present invention relates to the following general formula (I) [wherein R1 represents a saturated hydrocarbon group or a cyclic hydrocarbon group, and R2 and R3 represent a hydrogen atom or have a substituent together with R1] A divalent hydrocarbon group may also be formed. n is an integer of O or 1]
The present invention provides xylidene ketone derivatives and ultraviolet absorbers and cosmetics containing the same.

In the above general formula (I), the saturated hydrocarbon group represented by R1 includes methyl group, ethyl group, n-propyl group, isopropyl group, η-butyl group, isobutyl group, t-butyl group, pentyl group, and hexyl group. Examples include alkyl groups such as
Examples of the cyclic hydrocarbon group include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. The divalent hydrocarbon group formed by R2 and R3 together with R1 is:
For example, methylene, ethylene, which may have substituents,
Examples include trimethylene and tetramethylene groups, and examples of substituents here include methyl, ethyl, n-propyl, isopropyl, n-butyl, isophthyl, and t-butyl groups.

The p-xylidene ketone derivative (T) of the present invention can be produced, for example, according to the reaction formula shown below.

(n) (II') (III) [In the formula, R1, R2, R3 and n are the same as above] That is, by condensing the ketone derivative (n) or (■') with terephthalaldehyde. , p-xylidene ketone derivative (I) can be produced.

Ketone derivative (II), (■') used in this reaction
Examples include methyl isopropyl ketone, binacolon, methyl cyclopropyl ketone, methyl cyclobutyl ketone,
Examples include methylcyclopentylketone, methylcyclohexylketone, adamantylmethylketone, 2-methylcyclohexanone, 2-t-butylcyclohexanone, and isophorone.

This reaction is carried out using a base as a catalyst in an alcoholic solvent such as methanol, ethanol, ifpropanol, etc.
It is preferable to carry out the heating at ~150°C for several tens of minutes to several tens of hours. Examples of the base used here include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; metal alcoholades such as sodium methoxide, sodium ethoxide, and potassium t-butoxide.

The ultraviolet absorbent of the present invention containing the p-xylidene ketone derivative (I) thus obtained may use one or more of these p-xylidene ketone derivatives (I) as is, but a carrier Preferably, it is in the form of a mixture. The carrier may be any carrier as long as it is inert to the p-xylidene ketone derivative (I), and may be solid, liquid, emulsion, foam, gel, or the like. Typical examples include water, alcohol, fats and oils (e.g. hydrocarbon oils, fatty acid esters, long-chain alcohols, silicone oils), fine powders such as starch or talc, and low-boiling hydrocarbons used as aerosol propellants. or halogenated hydrocarbons. The ultraviolet absorber of the present invention further includes the p-xylidene ketone derivative (I) of the present invention.
Other ingredients, as long as they do not impair the ultraviolet absorption effect of
For example, preservatives, fragrances, colorants, surfactants, etc. can be added and blended.

Cosmetics containing p-xylidene ketone derivative (I) (
Hereinafter, the cosmetic composition of the present invention) is a p-xylidene ketone derivative (hereinafter referred to as the "cosmetic composition of the present invention") that has an affinity for the cosmetic base.
One or more of I) are appropriately selected and blended into a known cosmetic base by a conventional method to create creams, solutions, oils,
It is prepared in the form of a spray, stick, emulsion, foundation, ointment, etc.

That is, by selectively using the p-xylidene ketone derivative (I) according to the cosmetic base, oil-based cosmetic oils, oil-based creams or oil-based emulsions containing a large amount of oil, and large amounts of water can be blended. Weakly oily creams and emulsions,
It is possible to produce all types of cosmetics that have a mouth-absorbing effect, from basic cosmetics such as water-based lotions to makeup cosmetics such as oil-based foundations and lipsticks. Suitable bases and solvents for this include solid or liquid paraffin, crystal oil, hydrocarbons such as ceresin, osikerite or montan wax; vegetable oils or animal oils such as olive, earth wax, carnauba wax, lanolin or spermaceti. fats and oils; and fatty acids such as stearic acid, palmitic acid, oleic acid, glycerin monostearate, glycerin distearate, chrycerin thinooleate, isopropyl myristate, isopropyl stearate, or butyl stearate; Esters: Examples include alcohols such as ethyl alcohol, isopropyl alcohol, heptyl alcohol, stearyl alcohol, palmityl alcohol, and hexyldodecyl alcohol.

Further, polyhydric alcohols having a moisturizing effect such as glycol, glycerin or sorbitol can also be used.

The amount of the p-xylidene ketone derivative in the ultraviolet absorber and cosmetics of the present invention is not particularly limited as it may vary depending on the form of use, and it is sufficient that it is present in an effective amount, but generally 0. 1-20% by weight, preferably 0.5-10
It is preferable to mix them in such a manner that the weight percentage is the same.

The ultraviolet absorbers and cosmetics of the present invention may be formulated with only p-xylidene ketone derivatives, but they can also be used in combination with other ULB absorbers or UV-Δ absorbers as ordinary sunscreen cosmetics. It is more preferable to do so. Such [IV-B absorbers include, for example, p-methylbenzylidene-〇, L-camphor or its sulfonic acid sodium salt; 2-phenylbenzimidazole-5-sulfonic acid sodium salt, 3.4-dimethylphenylglyoxyl. acid sodium salt, 4-phenylbenzophenone, 4-phenylbenzophenone-2'-carboxylic acid isooctyl ester, p-methoxycinnamic acid ester, 2
Examples include -phenyl-5-methylbenzoxazole and p-dimethylaminobenzoic acid esters. U
As a VA absorbent, 4-methoxy-2'-carboxydibenzoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 4isopropyldibenzoylmethane, 2-hydroxy-4-methoxybenzophenone or dibenzylidene is used. Examples include camphor.

In addition to the above-mentioned components, various additives can be added to the present cosmetics. Suitable additives include, for example,
Emulsifiers of type 110 and type O/III may be mentioned. As the emulsifier, commercially available emulsifiers can be used.

Also methylcellulose, ethylcellulose or carboxymethylcellulose, polyacrylic acid, tragacanth,
Thickening agents such as agar or gelatin can also be added as additives. Furthermore, fragrances, preservatives, humectants, emulsion stabilizers, medicinal ingredients, and/or physiologically acceptable colorants may be added as necessary.

〔Example〕

The present invention will be explained in more detail by giving test examples and examples.

Example 1 1,4-bis(4,4-dimethyl-3-year-old xopene 1-
enyl) benzene [-Sailor (I), (Clls) 3C
-, R2=R3=H, n=O compound] (I a
) Synthesis: 100 m equipped with stirrer, reflux condenser and nitrogen inlet tube
1. Terephthalaldehyde 2, Og in a three-turn flask
(I3,4mmo, i!) and Vinacolon 3.0g (
30,0mmoA) to ethanol 40mf! Add 0.3 g (4.54 mmol) of potassium hydroxide, stir and react under a nitrogen stream at room temperature for 5 hours. The precipitated crystals are collected by filtration, washed with methanol, and then recrystallized from methanol. 3.2 g of the target product in the form of pale yellow flaky crystals was obtained. Yield 80.0% H-NMR: δ(CDCfl 3) 1.24 (I
8H, s), 7.15 (2) I, d.

15.6Hz), 7.59 (4H, s), 7.67
(21Ld, 15.6Hz) Example 2 Synthesis of 1,4-bis[3-(I-adamantyl)-3oxuburo-1-enyl]benzene [-Funato% formula% n=0 compound (Ib) : Terephthalaldehyde 0.5g (3.35mmof!
, ), ■-adamantyl methyl ketone 1.25 g (
7,01 mmofl) and potassium hydroxide 0.2 g (
2.3,03 mmoA) in the same manner as in Example 1.
By reacting for a period of time, 135 g of the target product in pale yellow fine needle-like crystals was obtained. Yield 89.4% 'H-NMR: δ(CDCβ3) 1.7-1.8(
61 (, m), 1.8-2.0 (6H, m), 2.
10 (3H, brs), 7.18 (2H, +j, 15
．． 6Hz).

7.58 (4H, s), 7.65 (2H, d, 15.
6Hz) Example 3 14-bisC2-(3-methyl-2-oxocyclohexylidene)vinyl]benzene [-Sailor's compound] (
Synthesis of Ic): Terephthalaldehyde 1. Og (6,71 mmoj2
>, 2-methylcyclohexanone2. Og (I7,
8 mmo, i'), potassium hydroxide 0.3 g (4,5
4mmoA) and ethanol 30rnf! By reacting for 8 hours in the same manner as in Example 1, 0.17 g of the target product as a yellow powder was obtained. Yield 7.9% 'H-NMR: δ (CDCj!3) 1.211fl
, d, 7.5 flz), 1.5-3, H14H, m)
, 7.39 (6H, m) Example 4 Synthesis of 1.4-bis[2-(3-,t-butyl-2-oxocyclohexylidene)vinyl]benzene[-1[compound] (Id): Terephthalaldehyde 1.0g (6,71mmoj
2Jg of 2-t-butylcyclohexanone (I4,
9 mmoj? ), potassium hydroxide 0.3g (4,54
mmoj! ) and ethanol 20-, Example 1
Stir at room temperature for 24 hours in the same manner as above, and then stir at 50°C for 24 hours.
Heat and react for a period of time. After cooling the reaction mixture, 2N hydrochloric acid was added to neutralize it and the mixture was left to stand. The precipitated crystals were collected by filtration, washed with ethanol, and then recrystallized from ethanol to obtain 0.5 g of the target product in the form of pale yellow needle crystals.

Yield 18.3% 'H-NMR: δ(CDCj! 3) 1.03
(I8H,s), 1.4~3.1(I4N,m
), 7.2H2fl, r), 7.42(4H,
s) Example 5 1.4-bis[2-(5,5-dimethyl-3-oxocyclohex-1-enyl)vinyl]benzene[-Sailor (
I) CH.

Synthesis of (Ie): 2.0 g of terephthalaldehyde (I3,4mmoA
), 4.2 g of isophorone (Ho, 4 mmoβ), 0.5 g of potassium hydroxide (7,57 mmoj), and 50 ml of ethanol were reacted for 24 hours in the same manner as in Example 1 to obtain 4.5 g of the desired product as a yellow powder. Yield: 89.7% IR Niji K11r 2B88.2865.
1652.1616.1581.1380°1307,
1285.1247cm −''l(-NMR:δ(C
DCA3) 1.12(I2H,s), 2.33(
4H,s).

2.49 (48, brs), 6.10 (2H, brs
), 6.93 (2fl, d.

16.9Hz), 7.01(2H,d, 16.91
1z), 7.5H4H,s) Test Example 1 Ultraviolet absorption effect of p-xylidene ketone derivative (I) of the present invention: As the p-xylidene ketone derivative (I) of the present invention, (I Using the compounds of a) to (Ie),
As a comparison compound, 2-hydroxy-4-methoxybenzophenone, which is a UV absorber, was used, and its ultraviolet absorption effect (absorbance) was measured by the method described below. The results are shown in Table 1.

(Measurement method) 2.5x 10-5 mo of the present invention compound and comparative compound
j! An ethanol (99.5% reagent special grade) solution with a concentration of /l was prepared, placed in a quartz cell (I cm x 1 cm), and then measured using a U-3410 self-recording spectrophotometer manufactured by Hitachi.

These results show that the p-xylidene ketone derivative of the present invention has a higher resistance to UV-A ultraviolet light than the comparative compound 2-hydroxy-
It has a stronger absorption effect than 4-methoxybenzophenone, indicating that it is highly effective in preventing sunburn.

Test Example 2 Stability of the p-xylidene ketone derivative of the present invention against ultraviolet light: Using the compounds (Ia) to (Ie) obtained in the above examples, 4-methoxy-4't- Using butyldibenzoylmethane, its stability against ultraviolet light was tested by the following experimental method.

The results are shown in Table 2.

(Experimental method) The present invention compound and comparative compound were dissolved in 99.5% ethanol/distilled water (3/2> solvent to a concentration of 2 mmoA/p, and a xenon needle having a wavelength and intensity extremely similar to sunlight) was used. Ultraviolet rays were irradiated for 14 hours using an original tester. After the solvent was distilled off, quantitative analysis was performed and stability was evaluated from the residual rate. The results are shown in Table 2.

Table 2 Photostability Evaluation From the results in Table 2, the compounds of the present invention are more stable against ultraviolet light than 4-methoxy-4'-t-butyldibenzoylmethane, which is commonly used as a UV-A absorber. It is clear that it is superior.

Example 6 0/W type cream The following composition was blended according to a conventional method to prepare a 0/W type cream.

C1vA formation] Compound of the present invention (lb) stearic acid Lipophilic glyceryl monostearate Heptyl alcohol stearyl alcohol Squalane liquid paraffin Vaseline butylparaben Methylparaben triethanolamine glycerin fragrance water Example 7 W10 type creamy de 1.0 1.0 10.0 20.0 0.1 0.1 1.0 10.0 Appropriate amount balance Mix the following composition according to the usual method, - A sample was prepared.

〔composition〕

Compound of the present invention (lc) sorbitan sesquioleate aluminum stearate Heptyl alcohol liquid paraffin Squalane Isopropyl myristate sodium benzoate glycerin fragrance water Example 8 0/W type emulsion: Mix the following composition according to the usual method, was prepared.

〔composition〕

W10 type Li (weight%) 4.0 0.5 10.0 Appropriate amount balance 0/W type emulsion (weight%) Compound of the present invention (Id) stearic acid Sorbitan monostearate Heptyl alcohol stearyl alcohol Isoprovil myristate Squalane liquid paraffin solid paraffin ethylparaben Methylparaben carbopol caustic potash fragrance water 1.5 Example 9 Lotion: A lotion was prepared by blending the following composition according to a conventional method.

〔composition〕

Compound of the present invention (I e) (% by weight) 2.0 Polyoxyethylene (23) lauryl 4.0 Ether ethanol 10.0 Glycerin 3.0 Dipropylene glycol 7.0 Lactic acid 0
．． 05 Sodium lactate 0.12 Methylparaben 0.1 Fragrance
Appropriate amount of dye
trace water
Balance: 100, 0 [Effects of the Invention] Since the p-xylidene ketone derivative (I) of the present invention has an excellent ultraviolet absorbing effect and excellent stability, ultraviolet absorbers or cosmetics containing it are resistant to sunburn. It has an excellent preventive effect.

that's all October 24, 1990

Claims (1)

[Claims] 1. The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1 represents a saturated hydrocarbon group or a cyclic hydrocarbon group, and R^ 2 and R^3 represent a hydrogen atom, or R^
Together with 1, a divalent hydrocarbon group which may have a substituent may be formed. n represents an integer of 0 or 1] A p-xylidene ketone derivative represented by: 2. An ultraviolet absorber containing the p-xylidene ketone derivative according to claim 1. 3. A cosmetic containing the p-xylidene ketone derivative according to claim 1.