JPH04290887A - 4,4-dimethyl-1-phenylpentane-1,3-dione derivative, ultraviolet ray absorber and cosmetic containing the same - Google Patents

Abstract

PURPOSE:To obtain the subject derivative, excellent in ultraviolet ray absorbing action and light stability, etc., and capable of imparting excellent anti-suntan effects to ultraviolet ray absorbers arid cosmetics. CONSTITUTION:A derivative expressed by formula I [R<1> is 1-8C alkoxy, 1-8C alkyl, etc.; two groups R<1> may form methylenedioxy; R<2> is 2-3C alkylene or 2-11C alkyleneoxy; R<3> is 1-6C alkyl or phenyl; (n) is 0-3], e.g. 1-(4-(3,3- diethylmethylsilyl)-propoxy-3-methoxyphenyl)-4,4-dimethylpentane-1,3-d ione. For example, the derivative expressed by formula I is obtained by reacting a silane derivative expressed by formula II with a benzoylpinacolone derivative expressed by formula III (R<4> is 2-3C omega-alkenyl or 2-11C omega-alkenyloxy), preferably in the presence of a catalyst of chloroplatinic acid, as necessary, in a solvent such as pentane, preferably at 0-100 deg.C for 0.5-24hr.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention is directed to a novel 4,4-
The present invention relates to a dimethyl-1-phenylpentane-1,3-dione derivative, and ultraviolet absorbers and cosmetics containing the same and having excellent sun protection effects. BACKGROUND OF THE INVENTION It is known that ultraviolet rays cause various changes in the skin. Dermatologically, the action wavelength is divided into long wavelength ultraviolet rays from 400 to 320 nm, medium wavelength ultraviolet rays from 320 to 290 nm, and short wavelength ultraviolet rays below 290 nm.
They are called A, UV-B, and UV-C. Ultraviolet rays in sunlight are UV-A and UV-B, and UV-C is absorbed in the ozone layer and hardly reaches the ground. [0003] When UV-B is irradiated onto the skin in an amount exceeding a certain level, it causes changes in the skin, such as forming erythema and blisters, promoting melanin formation, and causing pigmentation. The destruction of the ozone layer in the sky due to air pollution in recent years has become a serious problem because it causes an increase in UV-B. 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 UV-A and UV
- Both effects of B accelerate skin aging, causing age spots, wrinkles, and
It is thought to cause freckles, etc., and in the long term, to cause skin cancer. [0004] As the effects of ultraviolet rays on human skin become clearer, compounds that absorb UV-A and UV-B have been developed. Such ultraviolet absorbers include (1) UV-B or UV
- absorb the light of A as completely as possible; (2) be stable to light and heat; (3) have no toxic, irritating or other toxic effects on the skin; (4)
It is said that it is desirable that all conditions such as (5) long-lasting effects and (5) excellent compatibility with the cosmetic base be satisfied. Conventionally, as UV-A absorbers, for example,
Dibenzoylmethane derivatives are used as UV-B absorbers, and derivatives such as cinnamic acid ester, benzophenone, p-aminobenzoic acid, and salicylic acid are used. However, these conventional ultraviolet absorbers do not necessarily fully satisfy the above conditions, and are known to be absorbed through the skin, have insufficient stability particularly against light, and cause decomposition and reactions due to ultraviolet light. [I
nt. J. Cosmetic Science,
10, 53 (1988)]. There is a problem in that transdermal absorption and decomposition of such ultraviolet absorbers leads to a decrease in the duration of their effects. [0007]Therefore, there has been a desire for a compound that satisfies the above conditions, is hardly absorbed into the skin, and has particularly excellent stability against light, as well as ultraviolet absorbers and cosmetics that have excellent sun protection effects. [Means for Solving the Problems] Under these circumstances, the present inventors conducted intensive research and found that 4,4-dimethyl-1-phenylpentane-1 represented by the general formula (1) below
,3-dione derivative exhibits excellent ultraviolet absorption effect,
The present invention was completed based on the discovery that it is difficult to absorb into the skin, is extremely stable against light, and exhibits excellent oil solubility. That is, the present invention provides the following general formula (1):
[0010] [In the formula, R1 is the same or different and represents an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. It represents 2 to 10 acyl groups or hydroxyl groups, and two R1's may form a methylenedioxy group. n represents an integer of 0 to 3, R2
represents an alkylene group having 2 to 3 carbon atoms or an alkyleneoxy group having 2 to 11 carbon atoms, and R3 is the same or different and represents an alkyl group having 1 to 6 carbon atoms or a phenyl group]
4,4-dimethyl-1-phenylpentane-
The present invention provides a 1,3-dione derivative, and ultraviolet absorbers and cosmetics containing the same. In the present invention, in general formula (1), R1
Among them, examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, n-propoxy group, iso-
Examples include propoxy group, butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, etc., and examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n -propyl group, iso-propyl group, n-butyl group, t-butyl group,
Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, tolyl group, xylyl group, and naphthyl group. Examples of the acyl group include an acetyl group, a propionyl group, a butanoyl group, a benzoyl group, and two R1's may form a methylenedioxy group. Among these, a lower alkoxy group having 1 to 4 carbon atoms is preferred as R1. Examples of the alkylene group having 2 to 3 carbon atoms represented by R2 include ethylene group and propylene group, and examples of the alkylene group having 2 to 11 carbon atoms include ethyleneoxy group, propyleneoxy group, undecyleneoxy group, etc. etc., among which propyleneoxy group is particularly preferred. Furthermore, the alkyl group having 1 to 6 carbon atoms represented by R3 includes, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc. Among these, lower alkyl groups having 1 to 5 carbon atoms Particularly preferred are groups. The 4,4-dimethyl-1-phenylpentane-1,3-dione derivative (1) of the present invention can be produced, for example, according to the following reaction formula. [0014] [In the formula, R4 represents an ω-alkenyl group having 2 to 3 carbon atoms or an ω-alkenyloxy group having 2 to 11 carbon atoms, and R1, R3 and n are the same as above. In other words, the 4,4-dimethyl-1-phenylpentane-1,3-dione derivative of the present invention can be obtained by subjecting the silane derivative (2) and the benzoylpinacolon derivative (3) to a hydrosilylation reaction. can. The silane derivative (2) used as a raw material can be easily obtained as a commercial product, and the benzoylpinacolone derivative (3) can be obtained by, for example, a known method [J.
Am. Chem. Soc. , 80, 4891
(1958); J. Chromatogr. , 312
, 109 (1984); J. Polym. Sc
i. Polym. Chem. Ed. , 20, 3
079 (1982)], the following method (a) or (b)
). Method (a) [Formula 4] [In the formula, R5 is a methyl group, an ethyl group, n
- represents a propyl group or n-butyl group, R1, R4
and n have the same meanings as above] That is, benzoylpinacolon derivative (3) can be produced by condensing benzoate (4) and pinacolon (5). The reaction involves anhydrous tetrahydrofuran, toluene,
In a solvent such as xylene, using a base as a catalyst, 20 to 1
It is preferable to carry out the reaction at 50° C. for several tens of minutes to 10 hours. Examples of the base used here include metal hydrides such as sodium hydride; metal alkylated compounds such as butyllithium; amines such as triethylamine; metal amides such as sodium amide; metal alkoxide compounds such as sodium methoxide, etc. Can be mentioned. Method (b) ##STR5## [In the formula, R1, R4, R5 and n have the same meanings as above] That is, acetylbenzene derivative (6) and ethyl ester (7) By condensing the benzoylpinacolon derivative (3), the benzoylpinacolone derivative (3) can be produced. Examples of the ester (7) used in this reaction include methyl pivalate, ethyl pivalate,
Examples include propyl pivalate and butyl pivalate. The reaction is also carried out under similar conditions to method (a). The reaction between the silane derivative (2) and the benzoylpinacolone derivative (3) is carried out in the presence of a catalyst, such as those commonly used for hydrosilylation, such as free radical initiators; photoinitiators; ruthenium. , rhodium, palladium, osmium, iridium, platinum, and other metal complex compounds; examples include those supported on silica gel or alumina. Among these, chloroplatinic acid, Speier's reagent (isopropyl alcohol solution of chloroplatinic acid), and the like are particularly preferred. The amount of the catalyst used is not particularly limited as long as it is sufficient to promote the reaction, but it is preferably in the range of 10-6 to 10-1 mol per 1 mol of the benzoylpinacolon derivative used. Although the reaction solvent is not essential, the reaction may be carried out in a suitable solvent if necessary. The reaction solvent is not particularly limited as long as it does not inhibit the reaction, and includes, for example, hydrocarbon solvents such as pentane, hexane, and cyclohexane; benzene solvents such as benzene, toluene, and xylene; diethyl ether, diisopropyl ether, and tetrahydrofuran. Ether solvents; alcoholic solvents such as methanol, ethanol, isopropyl alcohol, and butanol; and the like. When using an alcohol solvent, a pH adjuster such as potassium acetate (Japanese Patent Laid-Open No. 149290/1982) is used to prevent or suppress the dehydrogenation reaction between Si-H and -OH. is preferable. [0025] The reaction proceeds at a temperature of 0 to 200°C, but it is preferably carried out at a temperature of 0 to 100°C in consideration of reaction rate and coloring of the product. Further, the reaction time is preferably about 0.5 to 24 hours. The ultraviolet absorber of the present invention comprises 4,4-dimethyl-1-phenylpentane-1 obtained as described above.
, 3-dione derivatives (1) may be used as they are, but it is preferable to mix them with a carrier. As the carrier, the above 4,4-dimethyl-1-phenylpentane-1,3-dione derivative (1)
There is no particular restriction as long as it is inert to solids,
It may be a 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, etc.), fine powders (e.g. starch, talc, etc.), and low-carbon compounds used as aerosol propellants. Examples include boiling point hydrocarbons and halogenated hydrocarbons. Furthermore, the ultraviolet absorber of the present invention includes a 4,4-dimethyl-1-phenylpentane-1,3-dione derivative (1).
Other components such as preservatives, fragrances, colorants, surfactants, etc. may be appropriately added within a range that does not impair the ultraviolet absorbing effect of the composition. The cosmetic of the present invention contains 4,4-dimethyl-1
-4,4-dimethyl-1-phenylpentane-1,3, which contains phenylpentane-1,3-dione derivative (1) and has an affinity for the cosmetic base.
- Manufactured by blending one or more dione derivatives (1) into a known cosmetic base by a conventional method, such as creams, solutions, oils, sprays, sticks, milky lotions, foundations, ointments, etc. It can be made into a type. That is, 4,4-dimethyl-1-phenylpentane-1
, 3-dione derivative (1) selected according to the cosmetic base, oil-based cosmetic oils, oil-based creams and emulsions containing a large amount of oil, and weak oil-based creams containing a large amount of water can be produced. We manufacture all types of cosmetics that have UV absorption properties, from basic cosmetics such as oil-based emulsions, water-based lotions, and oil-based makeup products such as foundations and lipsticks. be able to. Suitable bases and solvents include hydrocarbons such as solid or liquid paraffin, crystal oil, ceresin, ozokerite, montan wax; vegetable oils or animal oils such as olive oil, earth wax, carnauba wax, lanolin, spermaceti. Fats and oils; stearic acid, palmitic acid, oleic acid, glycerin monostearate, glycerin distearate, glycerin monooleate, isopropyl myristate, isopropyl stearate,
Fatty acids and their esters such as butyl stearate; ethyl alcohol, isopropyl alcohol,
Examples include alcohols such as cetyl alcohol, stearyl alcohol, palmityl alcohol, and hexyldodecyl alcohol. Further, polyhydric alcohols having a moisturizing effect such as glycol, glycerin, and sorbitol can also be used. In the ultraviolet absorber and cosmetic of the present invention, 4,4-dimethyl-1-phenylpentane-1,3-
The amount of the dione derivative (1) varies depending on the form of use and is not particularly limited as long as it is present in an effective amount, but it is generally 0.1 to 20% by weight, preferably 0.1 to 20% by weight in the total composition.
It is blended in an amount of 0.5 to 10% by weight. [0029] The ultraviolet absorber and cosmetic of the present invention contain 4.
In addition to the 4-dimethyl-1-phenylpentane-1,3-dione derivative (1), other UV-B absorbers or UV
-It is more preferable to use it in combination with an absorbent as an ordinary sunscreen cosmetic. As such a UV-B absorber, for example, p-methylbenzylidene-D(L)
-camphor or its sulfonic acid sodium salt, 2-phenylbenzimidazole-5-sulfonic acid sodium salt, 3,4-dimethylphenylglyoxylic acid sodium salt, 4-phenylbenzophenone, isooctyl 4-phenylbenzophenone-2'-carboxylate ester,
Examples include p-methoxycinnamic acid ester, 2-phenyl-5-methylbenzoxazole, p-dimethylaminobenzoic acid ester, and examples of UV-A absorbers include 4-methoxy-2'-carboxydibenzoylmethane. , 4-methoxy-4'-t-butyldibenzoylmethane, 4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxybenzophenone, dibenzylidene camphor, and the like. In addition to the above-mentioned components, the cosmetic of the present invention contains various additives, such as the commonly used W/O type and O/W type.
Type emulsifiers; thickeners such as methylcellulose, ethylcellulose, carboxymethylcellulose, polyacrylic acid, tragacanth, agar, gelatin; other fragrances, preservatives, humectants, emulsion stabilizers, medicinal ingredients, physiologically acceptable colorants etc. may be appropriately blended within a range that does not impair the effects of the present invention. [Examples] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 1-(4-(3,3-diethylmethylsilyl)-propoxy-3-methoxyphenyl)-4,4-dimethylpentane-1,3-dione (Compound 1 of the present invention; general formula (
1), R1 = OCH3, R2 = CH2CH2C
H2O, R3 = CH3, C2H5, C2H5,
Synthesis of n=1): (1) 1-(4-allyloxy-3
-methoxyphenyl)-4,4-dimethylpentane-1
, 3-dione; 200 ml of tetrahydrofuran was placed in a 1000 ml three-neck flask equipped with a stirrer, a dropping funnel, a reflux condenser, and a nitrogen inlet tube, and 24 g (0.6 mol) of 60% sodium hydride was dispersed therein. The mixture was heated to reflux. To this, a solution of 61.9 g (0.3 mol) of 4-allyloxy-3-methoxyacetophenone and 39.1 g (0.3 mol) of ethyl pivalate dissolved in 200 ml of tetrahydrofuran was carefully added dropwise over about 3.5 hours. Further, heating and stirring was continued overnight. After cooling on ice, 300 ml of 2N hydrochloric acid was carefully added, and the mixture was further washed twice with 100 ml of saturated saline. After drying the organic layer over anhydrous magnesium sulfate, the solvent was distilled off to obtain a brown oil. This oil was mixed with hexane/ethyl acetate (2:
Perform silica gel column chromatography using 1) as a developing solvent to obtain the desired title compound as a pale red oil.
4.6 g (yield 86%) was obtained. Melting point: 40.0°C IR (ν KBr, cm-1): 3090, 296
0, 2930, 2870, 2620, 1710
, 1680, 1600, 1520, 1470,
1430, 1370, 1340, 1280,
1210, 1180, 1150, 1140, 1
080, 1020, 1000, 930, 880
, 730, 640, 620, 570, 480
1H-NMR (CCl4, δ): 1.23 (s, 9H
, t-Bu), 3.83(s,3H,O-CH3),
4.43-4.60 (m, 2H, O-CH2), 5.
06-5.50 (m, 2H, Allylic-CH2)
, 5.70 ~ 6.10 (m, 1H, Allylic-
CH), 6.05 (s, 1H), 6.67 (d, 1H
, J=9.0Hz, Aromatic), 7.17
~7.32 (m, 2H, Aromatic), 16.7
6(bs,1H) (2) 1-(4-(3,3-diethylmethylsilyl)
-Synthesis of propoxy-3-methoxyphenyl)-4,4-dimethylpentane-1,3-dione; magnetic stirring device,
30ml with dropping funnel, reflux condenser and nitrogen inlet tube
1-(4-allyloxy-3-methoxyphenyl)-4,4-dimethylpentane-1,3-
Put 3.0 g (10 mmol) of dione and 3.2 g (31 mmol) of diethylmethylsilane, add about 0.1 ml of 10% potassium acetate ethanol solution and about 0.2 ml of 2% chloroplatinic acid hexahydrate isopropanol solution, The mixture was stirred at room temperature for 3 hours. After the reaction was completed, the solvent was distilled off to obtain a pale yellow oil. This oil was subjected to silica gel column chromatography using hexane/ethyl acetate (20:1) as a developing solvent to obtain 3.37 g (yield: 83%) of the target title compound as a colorless oil. IR (ν neat, cm −1): 2960, 2
880, 1600, 1510, 1470, 12
80, 1210, 1180, 1150, 114
0, 1040, 880, 790, 750 1H-NMR (CDCl3, δ): -0.04 (s, 3
H, Si-CH3), 0.49-0.70 (m, 6H
,Si-CH2-),0.93(s,6H,Si-CH
2-CH3), 1.24(s,9H,t-Bu),
1.80-2.02 (m, 2H, -CH2-), 3.9
4(s, 3H, O-CH3), 4.02(t, 2H,
J=7.3Hz, O-CH2), 6.23(s, 1H
), 6.94 (d, 1H, J=8.9Hz, Aroma
tic), 7.43-7.60 (m, 2H, Arom
atic), 16.72 (bs, 1H) Test Example 1 Ultraviolet absorption effect: Compound 1 of the present invention obtained in Example 1, 2-hydroxy-4-methoxybenzophenone (
The ultraviolet absorption effect (absorbance) was investigated using a UV-A absorber; comparative compound 1) and 2-ethylhexyl-p-methoxycinnamic acid (UV-B absorber; comparative compound 2). The results are shown in Table 1. (Measurement method) Dissolve the test compound in ethanol (99.5% reagent grade) to prepare a solution with a concentration of 2.5 x 10-5 mol/l, put it in a quartz cell (1 cm x 1 cm), and then perform self-recording spectroscopy. Absorbance was measured using a photometer (model U-3410, manufactured by Hitachi). [Table 1] As is clear from Table 1, the compound of the present invention has a stronger absorption effect on UV-A ultraviolet rays and UV-B ultraviolet rays than the comparative compound, indicating that it has a high sunscreen effect. . Test Example 2 Stability against ultraviolet light: Compound 1 of the present invention obtained in Example 1, 4-methoxy-4'-t-butyldibenzoylmethane (comparative compound 3) and 2-ethylhexyl-
Stability against ultraviolet light was investigated using p-methoxycinnamate (comparative compound 4). The results are shown in Table 2. (Experimental method) The test compound was dissolved in a 99.5% ethanol/distilled water (3/2) solvent at a concentration of 2 mmol/l, and a xenon light fastness tester having a wavelength and intensity very similar to sunlight was used. Ultraviolet rays were irradiated for 14 hours or 65 hours. After distilling off the solvent, quantitative analysis was performed and stability was evaluated from the residual rate. [0036] As is clear from Table 2, it can be seen that the compounds of the present invention have significantly better stability against ultraviolet rays than the comparative compounds. Example 2 W/O type cream: A W/O type cream having the following composition was produced by a conventional method. (composition)

(% by weight) 1-(4-(3,3-diethylmethylsilyl)-propoxy-3-methoxyphenyl)-4
,4-dimethylpentane-1,3-dione
2.0
sorbitan sesquioleate
4.0
aluminum stearate
0.5
cetyl alcohol
4
．． 0 liquid paraffin

16.0 Squalane

10.0 Isopropyl myristate
5.0 Sodium Benzoate
0.3 Glycerin

10.0
fragrance

Appropriate amount of water

balance

10
Example 3 Lotion: A lotion having the following composition was produced by a conventional method. (composition)

(% by weight) 1-(4-(3,3-diethylmethylsilyl)-propoxy-3-methoxyphenyl)-4
,4-dimethylpentane-1,3-dione
2.0
Polyoxyethylene (23) lauryl ether
4.0 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 pigment

Very small amount
water

balance

100.0 0040
Example 4 O/W type emulsion: An O/W type emulsion having the following composition was produced by a conventional method. (composition)

(% by weight) 1-(4-(3,3-diethylmethylsilyl)-propoxy-3-methoxyphenyl)-4
,4-dimethylpentane-1,3-dione
3.0
stearic acid

2.0 Sorbitan monostearate

1.5 Polyoxyethylene (23) Sorbitan Monostearate 1.0 Cetyl Alcohol
0.4
stearyl alcohol
0.3
Isopropyl myristate
7.0
Squalane

5.0 Liquid paraffin

5.0 Solid paraffin

2.0 Ethylparaben
0.1 Methylparaben
0
．． 1 Carboxyvinyl polymer (Carbopol, manufactured by Goodrich)
0.2 Potassium hydroxide
0.4
fragrance

Appropriate amount of water

balance


100.0 [0041] Example 5
O/W type cream: O/W type cream with the following composition by a conventional method.
A W-type cream was produced. (composition)

(% by weight) 1-(4-(3,3-diethylmethylsilyl)-propoxy-3-methoxyphenyl)-4
,4-dimethylpentane-1,3-dione
2.0
stearic acid

1.0 Lipophilic monostearic acid glyceride
2.
0 Polyoxyethylene (23) Sorbitan Monostearate 1.0 Cetyl Alcohol
1.0 Stearyl alcohol
1.0 Squalane

10.0 Liquid paraffin

20.0 Vaseline

5.0 Butylparaben
0.
1 Methylparaben

0.1 Triethanolamine

1.0 Glycerin

10.0 Fragrance

Appropriate amount of water

balance

100.0 004
2] [Effect of the invention] The 4,4-dimethyl-1-phenylpentane-1,3-dione derivative (1) of the present invention has an excellent ultraviolet absorption effect and excellent photostability,
The ultraviolet absorber and cosmetics of the present invention containing this have excellent sun protection effects.

Claims (3)

[Claims] Claim 1: General formula (1) [Formula 1] [In the formula, R1 is the same or different and represents an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 6 to 8 carbon atoms.
It represents 10 aryl groups, acyl groups having 2 to 10 carbon atoms, or hydroxyl groups, and two R1's may form a methylenedioxy group. n represents an integer of 0 to 3, R2 has 2 carbon atoms
-3 alkylene group or an alkyleneoxy group having 2 to 11 carbon atoms, R3 is the same or different and represents an alkylene group having 1 to 11 carbon atoms.
~6 alkyl group or phenyl group] represented by 4
, 4-dimethyl-1-phenylpentane-1,3-dione derivative. [Claim 2] 4,4-dimethyl-1 according to Claim 1
- An ultraviolet absorber containing a phenylpentane-1,3-dione derivative. [Claim 3] 4,4-dimethyl-1 according to Claim 1
- A cosmetic comprising a phenylpentane-1,3-dione derivative.