JPH04134042A - Styryl ketone derivative, ultraviolet absorber containing said derivative and cosmetic containing said absorber - Google Patents

Abstract

NEW MATERIAL:A styryl ketone derivative expressed by formula I [R is -COC(CH3)3 or formula V; n is integer of 1-3]. EXAMPLE:3,4-Dimethoxystyryl-tert.-butylketone. USE:An ultraviolet absorber and cosmetic having excellent sunburn preventing effect. The styryl keton derivative expressed by formula I has excellent light stability. PREPARATION:For example, a pinacolone expressed by formula II or isophorone expressed by formula III is condensed with a benzaldehyde derivative expressed by formula IV in the presence of a base catalyst to provide the styryl ketone derivative expressed by formula I.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a novel styryl ketone derivative that has an ultraviolet absorbing effect and excellent photostability, and a novel styryl ketone derivative containing the same that has a sunburn prevention effect. This invention relates to excellent ultraviolet absorbers and cosmetics.

[Prior Art] It is known that ultraviolet rays cause various changes in the skin. Dermatologically, the working wavelength is 400 to 320n.
Divided into long wavelength ultraviolet rays (m), medium wavelength ultraviolet rays (320 to 290 nm), and short wavelength ultraviolet rays (290 nm or less),
They are called IV-A, UV-8 and UV-C. The ultraviolet rays in sunlight are UV-A and [IV-8;
-C is absorbed in the ozone layer and hardly 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 the formation of erythema and chickenpox, as well as accelerated melanin formation and pigmentation.

On the other hand, UV-8 causes a blackening effect on the skin immediately after irradiation (immediate blackening), and since its energy reaches the dermis, it causes changes in the elastic fibers in blood vessel walls and connective tissues. Such UV-A effects are thought to accelerate skin aging and cause age spots, wrinkles, and freckles.

As the effects of ultraviolet rays on human skin r1'rf have become clearer, compounds that absorb IIV-8 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, dibenzoylmethane derivatives, for example, have been used as the IIV-A absorbent.

[Issues that Hathu tries to solve]

However, these conventional ultraviolet absorbers do not necessarily fully satisfy the above conditions, and in particular, they have insufficient stability against light, and are known to cause decomposition and reactions due to ultraviolet light.

Cosmetic 5science, 10.53(1
988):] o Such decomposition of ultraviolet absorbers not only leads to a reduction in the duration of their effects, but also the effects on the skin of the decomposed products themselves or products generated by reactions with formulations cannot be ignored [Fragrance Journal, 84.3
4 (1987) 3° Therefore, there has been a desire for an ultraviolet absorber that satisfies the above conditions, especially an ultraviolet absorber that has excellent stability against light.

[Indispensable means to solve problems]

In view of these circumstances, the present inventors have synthesized a number of styryl ketone derivatives and studied their properties, and have found that a new styryl ketone derivative represented by the following - Shipman CI> has excellent Uv-Δ absorption action. The present invention has been completed based on the discovery that the present invention has the following properties: and is extremely stable against light, and that by blending the same, a cosmetic having an excellent sunburn prevention effect can be obtained.

That is, the present invention provides a styryl ketone derivative represented by the following general formula (I), where ``input represents an integer from 1 to 3'', and ultraviolet absorbers and cosmetics containing the styryl ketone derivative.

The styryl ketone derivative (■) (M1) of the present invention can be easily produced according to the formula shown below.

(II) (III) (■) [In the formula, R and 0 are the same as above] That is,
The styryl ketone derivative (1) can be produced by condensing binacolone (n) or vinophorone (I) with a benzaldehyde derivative (IV) in the presence of a base catalyst.The solvent used at this time is methanol. Alcohols such as , ethanol, and isopropanol are preferred, and the reaction is preferably carried out at 20 to 150°C for several tens of minutes to several tens of hours.The bases used here include sodium hydroxide, potassium hydroxide, etc. Alkali metal hydroxides such as soot and lithium methoxide; metal alcoholades such as sodium ethoxide and potassium t-butoxide.

The ultraviolet absorber of the present invention containing the styryl ketone derivative (I) obtained in this way may use one or more of these styryl ketone derivatives (I) as is, but it may be added to a carrier and mixed. Preferably, it is in the form of The carrier may be any carrier as long as it is inert to the styryl ketone derivative (1), and may be solid, liquid, emulsion, foam,
It may be any 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 may further contain other ingredients, such as preservatives, fragrances, colorants, surfactants, etc., as long as they do not impair the ultraviolet absorbing effect of the styryl ketone derivative (1) of the present invention. be able to.

Cosmetics containing styryl ketone derivative (1) (hereinafter referred to as
The "cosmetic composition of the present invention") is prepared by appropriately selecting one or more styryl ketone derivatives (1) that have an affinity for the cosmetic base, and applying the styryl ketone derivatives (1) to a known cosmetic composition by a conventional method. It is prepared by blending it into a base and making it into a dosage form such as a cream, solution, oil, spray, stick, emulsion, foundation, or ointment.

That is, by selectively using the styryl ketone derivative (I) according to the cosmetic base, oil-based cosmetic oils, oil-based creams and emulsions containing a large amount of oil, and moisturizing oil-based creams containing a large amount of water can be produced. We can manufacture all types of cosmetics with UV absorption properties, from base θ cosmetics such as oil-based emulsions, water-based lotions, and oil-based makeup cosmetics such as foundations and lipsticks. can. 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 waxes 1 Furthermore, fatty acids and their Esters: alcohols such as ethyl alcohol, isopropyl alcohol, cetyl alcohol, stearyl alcohol, palmityl alcohol, or hexyldodecyl alcohol, and the like. Also,
Polyhydric alcohols with moisturizing properties such as glycol, glycerin or sorbitol can also be used.

The amount of the styryl 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 the styryl ketone derivative is present in an effective amount, but generally 0.1 to 20 % by weight, preferably 0.5-10% by weight
It is best to mix them so that

The ultraviolet absorber and cosmetics of the present invention may contain only the styryl ketone derivative, but it is more preferable to combine them with other LIVB absorbers or UV-absorbers and use them as ordinary sunscreen cosmetics. preferable. Such UV-E absorbers include, for example, p-methylbenzylidene-D, L-camphor or its sulfonic acid sodium salt; 2-phenylbenzimidazole-5-sulfonic acid sodium salt, 34-dimethylphenylglyoxylic acid sodium salt. , 4-phenylbenzophenone, 4-phenylbenzophenone-2'-carboxylic acid isooctyl ester, p-methoxycinnamic acid ester, 2-phenyl-5
-Methylbenzoxazole or p-dimethylaminobenzoic acid esters. IIV-A absorbers include 4-methoxy-2'carboxydibenzoylmethane, 4-methoxy4'-t-butyldibenzoylmethane, 4-isopropyldibenzoylmethane, 2-hydroxy-4=methoxybenzophenone or dibenzoylmethane. Examples include benzylidene camphors.

In addition to the above-mentioned components, various additives can be added to the cosmetic composition of the present invention. Suitable additives include, for example, Wl
Examples include emulsifiers of the o and O/IQ type.

As the emulsifier, commercially available emulsifiers can be used. Thickeners such as methylcellulose, ethylcellulose or hacarboxymethylcellulose, polyacrylic acid, tragacanth, 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 with reference to test examples and examples.

Example 1 3.4-Dimethoxystyryl-t-butylketone [-Funenin (I), R=-C0C(Clls)3,
Compound represented by n = 2] Synthesis of (Ia) 34-dimethoxybenzaldehyde 2 in a 100 ml three-tube flask equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube.
．． 0g (12,0mmoj2) and Vinacolon 4.3
Dissolve 42.9 mmof (42.9 mmof) in 20 ml of ethanol, add 0.2 g (1.03 mmof!) of 28% sodium methylate methanol solution, and react by heating under reflux for 20 hours under a nitrogen stream. After cooling, the solvent was distilled off and recrystallized from methanol to obtain 1.6 g of the target product in the form of colorless scales. Yield: 53.7% If-NMR: δ
(CDCA3) 1.24 (9H, s), 3.92
(31Ls).

394 (3H, s), 6.87 (ltl, d, 8.3
Hz>, 7.00 (IH, d15.6Hz), 7.
08(If(, d, 1.811z>, 7.18(if
t, dd, 8J1.8flz), 7.64(ltl,
d, 15.6 Hz) Example 2 2.3.4-) Dimethoxystyryl-t-butylketone [-R=-COC(CH3) in Shipin (1) 3. n
= Compound represented by 3] Synthesis of (Ib).

2.3.4-) Dimethoxybenzaldehyde 2.0g
<10.2 mmoA), Vinacolon 2.0g (2
0.0 mmop), 02 g of 28% sodium methylate/methanol solution (1.03 mmoA) and 20 d of ethanol, and reacted for 20 hours in the same manner as in Example 1 to obtain the desired product in the form of pale yellow scale-like crystals. .27
I got g. Yield 9.5% 'H-NMR: δ(CDCβ3) 1.23 (9H
, s) , 3.88 (3H, s) 3.90 (3H,
s), 3.9H311,s), 6.69(Ill,
d, 8.811z) 7.17 (Iff, d, 15.7H
z), 7.30 (IH, d, 8.8Hz), 7.8
4 (IH, d, 15.7 Hz) Example 3 2.4.5-) Dimethoxystyryl-t-butylketone [-R=-COC(CH3) in Shipin (1) 3. n
= Compound represented by 3] Synthesis of (Ic) 2.
4.5-) IJ methoxybenzaldehye F3. Og(
15.3 mmoj2>, Vinacolon 3. Og (30
, 0 mmo, I2), 0.3 g of 28% sodium methylate/methanol solution (1,55 mmo, R), and 50 d of ethanol, and reacted for 20 hours in the same manner as in Example 1 to obtain the objective of yellow needle crystals. 2.3 g of product was obtained. Yield 54.0% Example 4 34.5-) dimethoxystyryl-t-butyl ketone [
-Sailor (1) and R--CQ [: (CH3)3, n
= 3] Synthesis of (16) 3.4.5-) Dimethoxybenzaldehyde 30g (
15.3mmoffl), Vinacolon 3.0g (
30,0 mmo! '), 20 g of 28% sodium methylate methanol solution (1.03 mmoA) and 20 g of ethanol in the same manner as in Example 1.
By reacting for a period of time, the desired product is obtained as colorless scaly crystals.
7 g was obtained. Yield 13.4%) 1-NMR: δ(CDCβ3>1.24 (9i
L s), 3.89 (31-1, s) 391 (6
ft, s), 6.79 (2H, s), 7.00 (1
1-1, d, 15.5 Hz) 760 (LH, [1, 1
5,5H2) Example 5 3-(4-methoxystyryl)-55-dimethylcyclohex-2-enone [-Synthesis of (I e) with Funato (I) p-methoxybenzaldehyde 2.0 g (14,
7 mmoA, isoborone 2.0 g (14.5 mmoA
), potassium hydroxide 1.05g (15.9mmol)
By using 30 ml of ethanol and reacting for 20 hours in the same manner as in Example 1, 0.5 g of the target product in the form of yellow flaky crystals was obtained. Yield 13.5% 'H-NMR: δ (CDCA3) 1.10 (611
, s), 2.30(2)1. s) 2.46(21(,
brs), 3.82(31-1,s), 6.04(
IH,brS)6.77(ill,d,16.2tlz
), 6.89 (2H, d, 8.911z), 6.9
6 (LH, d, 16.2 tlz>, 7.44 (2 tl
, d, 8.9 Hz) Example 6 3-(3,4-dimethoxystyryl)-5,5-dimethylcyclohex-2-enone [-Shipin (I > (I f
) Synthesis of 3.4-dimethoxybenzaldehyde 2.0g (12
, Ommoj? ), isophorone 1.66 g (1
2, Qmmofl), 0.8 g of 28% sodium methylate/methanol solution (4.15 mmol and 30 g of ethanol), and reacted for 20 hours in the same manner as in Example 1 to obtain the desired product as yellow granular crystals. Yield: 11.6% 'H-NMR: δ(CDCj!s) 1.11(6f
l, s), 2.31 (2H, s) 2.48 (2t (,
brs), 3.92 (3H, s), 3.94 (3H
,s), 6.06(Iff,brs), 6.79(
LH, d, 16.1tlz), 6.87 (IH, d.

8.1Hz>, 6.96(lfl, d, 16.1Hz
), 7.0 to 7.1 (2H, m) Test Example 1 Ultraviolet absorption effect of styryl ketone derivative (I) of the present invention: As the styryl ketone derivative of the present invention, (I a) to ( Using the compound of If) and using 2-hydroxy-4-methoxybenzophenone, which is a UV-A absorber, as a comparison compound, the ultraviolet absorption effect (absorbance) was measured.
was measured by the method below.

The results are shown in Table 1.

(Measurement method) 2.5x 10-5 mo of the present invention compound and comparative compound
! ! .

An ethanol (99.5% reagent special grade) solution having a concentration of /β was prepared and placed in a quartz cell (1 cm x 1 cm), and then measured using a U-3410 self-recording spectrophotometer manufactured by Hitachi.

The results shown in Margin-1 below show that the styryl ketone derivative of the present invention has UV-A
It has a stronger absorption effect against ultraviolet rays than the comparative compound 2-hydroxy-4-methoxybenzophenone, indicating that it has a high sunburn prevention effect.

Test Example 2 Stability of the styryl ketone derivative of the present invention against ultraviolet rays: Using the compounds (Ia) to (If) obtained in the above examples,
Using 4-methoxy-4't-butyldibenzoylmethane as a comparative compound, 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 the comparative compound were dissolved in 99.5% ethanol/distilled water (3/2> solvent to a concentration of 2 mmoA/A, and had a wavelength and intensity very close to sunlight. Ultraviolet rays were irradiated for 14 hours using a xenon needle tip 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 A sample was prepared.

〔composition〕

Compound of the present invention (la) Stearic acid lipophilic monostearate glyceridoylmethane From the results in Table 2, compared with 4-methoxy-4'-t-butyldibenzoylmethane, which is commonly used as a Uv-Δ absorber, It is clear that the compounds of the present invention have excellent stability against ultraviolet light.

Example 7 0/W type Norm: The following composition was blended according to a conventional method, and O/W type Crytyl Alcohol Stearyl Alcohol Squalane Liquid Paraffin Vaseline Butyl Paraben Methyl Paraben Triethanolamine Glycerin Fragrance Water Example 8 W10 Type Cream : 1.0 20.0 5.0 0.1 OO Appropriate balance 100.0 The following composition was blended according to a conventional method to prepare a mulch.

〔composition〕

Compound of the present invention (lb) sorbitan sesquioleate aluminum stearate cetyl alcohol liquid paraffin Squalane Isopropyl myristate sodium benzoate glycerin fragrance water Example 9 0/W type emulsion: Mix the following composition according to the usual method, was prepared.

〔composition〕

W10 type Li (weight%) 10.0 10.0 Appropriate amount balance 100, 0 0/W type emulsion (weight%) Compound of the present invention (1e) stearic acid Sorbitan monostearate Heptyl alcohol stearyl alcohol Isopropyl myristate Squalane liquid paraffin solid paraffin ethylparaben Methylparaben carbopol caustic potash fragrance water 2.0 Example 10 Lotion; A lotion was prepared by blending the following composition according to a conventional method.

〔composition〕

Compound of the present invention (If) (% by weight) 2.0 Ethanol 10.0 Glycerin 3.0 Dipropylene glycol 70 Lactic acid 0.
05 Sodium lactate 0.12 Methylparaben 0.1 Fragrance
Appropriate amount of dye
trace water
Balance [Effect of the Invention] The styryl ketone derivative (I) of the present invention has an excellent ultraviolet absorbing effect and outstanding stability, so the ultraviolet absorber or cosmetic containing it has an excellent sunburn prevention effect. It is.

that's all

Claims (1)

[Claims] 1. The following general formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, R is a group -COC(CH_3)_3 or ▲ Numerical formula,
A styryl ketone derivative represented by ▼, where n is an integer from 1 to 3. 2. An ultraviolet absorber containing the styryl ketone derivative according to claim 1. 3. A cosmetic containing the styryl ketone derivative according to claim 1.