JPH03220153A - Benzoyl pinacolone derivative, uv ray absorbent containing the same and cosmetic containing the same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

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

[Conventional technology]

Ultraviolet rays are known to cause various changes in the skin. Dermatologically, the wavelength of action is 400 to 320.
Ultraviolet rays are divided into long wavelength ultraviolet rays (320 to 290 nm), medium wavelength ultraviolet rays (320 to 290 nm), and short wavelength ultraviolet rays (290 nm or less), and are called IIV-A, tlV-8, and UV-C, respectively. The ultraviolet rays in sunlight are IIV-A and UV-8, and UV-C is absorbed in the ozone layer and hardly reaches the ground.

When the skin is irradiated with a certain amount of light, tlV-8 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-A causes a blackening effect on the skin (immediate blackening) immediately after irradiation, and since the energy reaches the dermis, it causes changes in blood vessel walls and elastic fibers in connective tissue. It is believed that the effects of both UV-A and UV-8 accelerate skin aging and are 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 and UV-8 have been developed. It is said that it is desirable that such ultraviolet absorbers satisfy all of the following conditions.

■ Absorb UV-B or UV-A light as completely as possible.

■ Stable against light and heat.

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

■　Effects should last.

■ Excellent compatibility with cosmetic bases.

Conventionally, as UV-^ absorbers, for example, dibenzoylmethane derivatives have been used, and as tlV-8111 collectors, for example, derivatives of cinnamic acid ester, benzophenone, p-aminobenzoic acid, salicylic acid, etc. have been used.

[Problem to be solved by the invention]

However, these conventional ultraviolet absorbers do not necessarily fully satisfy the above-mentioned conditions, and in particular, their stability against light is insufficient, and it is known that they decompose or react with ultraviolet light [Int, J.

Cosmetic 5science, 10.53(1
98B)) o Strict decomposition of UV 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 the formulation cannot be ignored [Fragrance Journal, 84.34
(1987)].

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.

[Means to solve the problem]

In view of these circumstances, the present inventors have synthesized a number of benzoyl ketone derivatives and studied their properties, and found that
The benzoylbinacolone derivative represented by the general formula (I) below has excellent UV-8 and UV-8 absorbing properties and is extremely stable against light, and furthermore, when it is blended, excellent sun tanning properties can be obtained. discovered that a cosmetic having a preventive effect could be obtained and completed the present invention.

That is, the present invention relates to the following general formula (1) () [wherein R represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, an alkenyloxy group having 1 to 8 carbon atoms, or a (polyoxyalkylene)oxy group] , or two R may form an α-methylenedioxy group, and n represents an integer of 1 to 3]; The present invention provides a cosmetic containing an ultraviolet absorber.

Furthermore, among the compounds of general formula (I), the following general formula (I)
The compound represented by ' is new. Therefore, the present invention relates to the following general formula (I)' (R).

[In the formula, R represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, an alkenyloxy group having 1 to 8 carbon atoms, or a (polyoxyalkylene)oxy group, or two R represents an α-methylenedioxy group. may be formed, and n represents an integer of 1 to 3 (however, when n = 1, the group CH30- is 2 on the benzene nucleus.
The present invention also provides benzoylbinacolone derivatives represented by <)] except when the hydroxyl group is bonded to the benzene nucleus or the 3-position, and when the hydroxyl group is bonded to the 2-position on the benzene nucleus with port=1.

In the above general formulas (I) and (I)', examples of the alkoxy group having 1 to 8 carbon atoms represented by R include methoxy group, ethoxy group, n-propyloxy group, n-butoxy group, t
Examples of the alkenyloxy group having 1 to 8 carbon atoms include allyloxy group, butenyloxy group, pentenyloxy group, and hexenyloxy group; Examples of the (polyoxyalkylene)oxy group include, for example, Examples include methoxymethoxy group and methoxyethoxymethoxy group.

Further, two Rs can also form an α-methylenedioxy group.

Among these R, an alkoxy group or an alkenyloxy group having 1 to 3 carbon atoms is particularly preferable, and specific examples thereof include:
Examples include methoxy group, ethoxy group, n-propyloxy group, and allyloxy group.

Moreover, although n is an integer of 1-3, 2 or 3 is preferable.

The benzoylbinacolon derivative (1) of the present invention can be prepared, for example, by a known method (J, Am, [:hem, Soc, .
80°4891 (1958); J, Chroma
togr,, 312.109 (1984>: J, P
al)m, Sci, Polym, Chem, Bd
9.20.3079 (1982)], and can be produced by the following method (a) or (b).

[In the formula, R1 represents a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, and R and n represent the same as described above.] That is, benzoate (II) and binacolon (I[l
) to form a benzobina colon derivative (
I) is produced. The reaction in method (a) is preferably carried out in a solvent such as anhydrous tetrahydrofuran, toluene, or xylene at 20 to 150°C for several tens of minutes to 10 hours using a base as a catalyst. Examples of bases 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; and metal alkoxide compounds such as sodium methoxide. It will be done.

[In the formula, R, R, and n are the same as above] That is, an acetylbenzene derivative (rV) and an ester (V
) to produce benzoylbinacolone derivative (I). Examples of the ester (V) used in this reaction include methyl pivalate, ethyl pivalate, propyl pivalate, butyl pivalate, and the like. The reaction in method (b) is carried out under the same conditions as in method (a) above.

The ultraviolet absorber of the present invention containing the benzoylbinacolon derivative (1) obtained in this way may be prepared by using one or more of these benzoylbinacolon derivatives (1) as is, or by adding it to a carrier and mixing it. Preferably, it is in a compacted form. The carrier may be any carrier as long as it is inert to the benzoylbinacolone derivative (I), and may be solid, liquid, emulsion, foam, gel, or the like. Typical examples include water, alcohol, fats and oils (e.g. hydrocarbon oil, fatty acid ester alcohol, silicone oil), fine powders such as starch or talc, low-boiling hydrocarbons used as aerosol propellants, or Examples include halogenated carbon hydrogen. The ultraviolet absorber of the present invention further includes the benzoylbinacolon derivative (1) 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 benzoylbina cologne derivative (1) (
The benzoylvina cologne derivative (hereinafter referred to as the "cosmetic composition of the present invention") 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 benzoylvina cologne derivative (1) according to the cosmetic base, oil-based cosmetic oils, oil-based creams and emulsions containing a large amount of oil, and weak oil-based cosmetics containing a large amount of water can be produced. cream or weak oily emulsion,
Cosmetics of all types with UV absorbing properties can be produced, 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 hydrocarbons such as solid or liquid paraffin, crystal oil, ceresin, osichelite 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, glyceryl thinostearate, glyceryl distearate, glycerine monooleate, isopropyl myristate, isopropyl stearate or butyl stearate; Its esters include alcohols such as ethyl alcohol, isopropyl alcohol, heptyl alcohol, stearyl alcohol, valmityl 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 benzoylbinacolon 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, as long as it is present in an effective amount, but generally from 0.1 to 0.1 in the total composition. 20% by weight, preferably 0.5-1O
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 contain only benzoylbinacolon derivative (I), but may also contain other [I].
In combination with V-8 absorber or UV-A absorber,
It is more preferable to use it as a regular sunscreen cosmetic. Examples of such UV-e absorbers include 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, 4-phenylbenzophenone-27-carboxylic acid isooctyl ester, p-methoxycinnamate ester, 2-phenyl-5-methyl benzoxazole or p
-dimethylaminobenzoic acid esters and the like. As a UV-A absorber, 4-methoxy-2'-carboxydibenzoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 4-isopropyldibenzoylmethane, 2-hydroxy-4-methoxybenzophenone or dibenzoylmethane is used. 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, W2
Examples include O-type and 0/W-type emulsifiers. As the emulsifier, commercially available emulsifiers can be used. Also methylcellulose, ethylcellulose or carboxymethylcellulose,
Thickening agents such as 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 described in more detail with reference to Examples and Test Examples.

Example 1 3.4-dimethoxypivaloylacetylbenzene [according to general formula (I), R=OCH3, n=2 (D)]
Synthesis of I a): In a 200-length three-meter flask equipped with a stirring device, dropping funnel, reflux condenser, and nitrogen inlet tube, 2.45 g (61 mmol) of 60% sodium hydride, 3゜4-dimethoxy Methyl benzoate 10 g (51 mmall)
and 100 ml of anhydrous tetrahydrofuran under a nitrogen stream,
Stir and mix, heat and reflux 6.1 g (61 mm) of Vinacolon.
ol) was added dropwise. After heating under reflux for 7 hours, let cool and add 30mj of 2N hydrochloric acid! was added, and extracted twice with chloroform. After drying the extract over anhydrous sodium sulfate, the solvent was distilled off.
A crude product was obtained. Bexane was added to this, and after filtering out insoluble matter, the filtrate was concentrated and recrystallized to obtain 8.9 g of colorless needle-like crystals of the target compound (yield: 65%).

Melting point: 52.3-53.3°C IR (1'Klr, Cl1l-'): 1602.
1521.1470.1446°1365, 1299.
1266, 121B.

1188, 1131.885.786°29' H-NMR (CDC13, δ): 1.26 (
9H, s, t-CJs).

3, 95 (3) 1. s, OCH,).

3,96 (3H,s, 0CHs).

6, 24 (IH, s).

6, 90 (IH, d, J = 8.4Hz).

7.49 (IH,s).

7, 51 (lft, d, J=8.4Hz) Elemental analysis calculation value (%) C; 68.16. H: 7.63 Actual value (%) C: 68.23. H; 7.60 Example 2 3.4.5-) Dimethoxypivaloylacetylbenzene [according to general formula (1), R=OCH3, n=2 (7)
(1) Synthesis of (Ib): 200wd! equipped with a stirrer, dropping funnel, reflux condenser and nitrogen inlet tube! In a Mitsuro flask, 3.0 g (? 5 mmol) of 60% sodium hydride, 3°4
．． 5-) Methyl dimethoxybenzoate 10g (44.3m
molt) and anhydrous tetrahydrofuran 80rrf.

were stirred and mixed under a nitrogen atmosphere, and heated under reflux with Vinacolon 5 and 3.
g (53.2 mmof) was added dropwise. After heating under reflux for 5 hours, the mixture was allowed to cool, and 2N hydrochloric acid (45-) was added thereto, followed by extraction twice with chloroporm. After drying the extract over anhydrous sodium sulfate, the solvent was distilled off to obtain a crude product. Hexane was added thereto, and after filtering out insoluble matter, the filtrate was concentrated and recrystallized to obtain 9.6 g of colorless needle-like crystals of the target compound (yield: 74%).

Melting point: 67.3-68.4°C IR (cm-'): 2968.159
3.1560.1509゜1473, 1434.133
5.1233゜121g, 1176, 1131.99
3゜01'H-NMR (CDCj! 5.δ): 1.26 (
91 (, s, t-C4L).

3,91 (3H,s, 0CH3).

3, 93 (6H, s, QC) 1. ).

6, 21 (IH, s).

7, 13 (2)1. s) Elemental analysis calculated value (%') C; 65.29. H; 7.53 actual value (%) C; 65J8. H; 7.51 Test Example 1 Ultraviolet absorption effect of the compound of the present invention: 3,4- obtained in Examples and 2 as the compound of the present invention
Using dimethoxypivaloylacetylbenzene (I a) and 3.4.5-)dimethoxypivaloylacetylbenzene (I b), 2-hydroxy-
4-Methoxybenzotuunone (UV-^ absorber) and 2
-Ethylhexyl-p-methoxycinnamate (UV-
The ultraviolet absorption effect (absorbance) was measured using the following method. The results are shown in Table 1.

(Measurement method) 2.5X l O-'m of the present invention compound and comparative compound
ail/j! A concentrated ethanol (99.5% reagent grade) solution was prepared, placed in a quartz cell (1 cm x 1 cm), and then measured using a Hitachi U-3410 self-recording spectrophotometer.

The following margin indicates that the compound of the present invention was exposed to UV-A ultraviolet light and U
For V-8 ultraviolet light, the comparative compound 2-hydroxy-4
-methoxybenzophenone or 2-ethylhexyl-p
-It has a stronger absorption effect than methoxycinnamate, indicating that it has a high sun protection effect.

Test Example 2 Stability of the compound of the present invention against ultraviolet light: (Experimental method) The compound of the present invention and the comparative compound were mixed at 2 mtnoi! in a solvent of 99.5% ethanol/M distilled water (3/2). /12 and irradiated with ultraviolet rays for 14 hours using a xenon light resistance tester having a wavelength and intensity very similar to sunlight. After distilling off the solvent, quantitative analysis was performed and stability was evaluated from the residual rate. The results are shown in Table 2.

Margin below Table 2 Photostability evaluation Ia: 3.4-dimethoxypivaloylacetylbenzene Ib: 3,4.5-)dimethoxypivaloylacetylbenzene 1: 4-methoxy-4'-t-butyldibenzoylmethane 2:2-Ethylhexyl-p-methoxycinnamate From the results in Table 2, 4-methoxy-4'-t-butyldibenzoylmethane, which is commonly used as a UV-A absorber, or [as an IV-B absorber] It is clear that the compound of the present invention has significantly better stability against ultraviolet light than the commonly used 2-ethylhexyl-p-methoxycinnamate.

Example 3 O/W type cream: The following composition was blended according to a conventional method to prepare an O/W type cream.

[Composition] (% by weight) Stearic acid lipophilic monostearic acid glyceride 1.0 2.0 Cetyl alcohol Stearyl alcohol Squalane Liquid paraffin Vaseline Butyl paraben Methyl paraben Triethanolamine 1.0 1.0 10.0 20.0 5 .0 0.1 0.1 1.0 Glycerin flavored water 10.0 Proper amount balance 100.0 Example 4 W10 type cream: A W10 type cream was prepared by blending the lower composition according to a conventional method.

[Composition] (% by weight) Sorbitan sesquioleate Aluminum stearate Heptyl alcohol Liquid paraffin Squalane Isopropyl myristate Sodium benzoate Glycerin Flavored water 4.0 0.5 4.0 16.0 10.0 5.0 0.3 10.0 Proper amount balance 100.0 Example 5 0/W type emulsion: The following composition was blended according to a conventional method to prepare a 0/W type emulsion.

[Composition] (% by weight) Sorbitan stearate monostearate 2.0 1.5 Caustic potash flavored water Example 6 Lotion: The following composition was blended according to a conventional method.

〔composition〕

0.4 Appropriate amount balance ioo,.

Preparation of lotion (wt%) Cetyl alcohol Stearyl alcohol Isopropyl squalane myristate Liquid paraffin Solid paraffin Ethyl paraben Methyl paraben Carpopol 0.4 0.3 7.0 5.0 5.0 2.0 0.1 0.1 0 .2 Ether ethanol Glycerin Dipropylene glycol Lactate Sodium lactate Methyl paraben Flavor pigment 10.0 3.0 7.0 0.05 0.12 0.1 Appropriate amount of water Balance procedure amendment letter) 100, 0 [Effect of the invention] Book Since the benzoylvina cologne derivative <1) of the invention has excellent ultraviolet absorbing action and outstanding stability, ultraviolet absorbers or cosmetics containing it have excellent sunburn prevention effects.

that's all

Claims (1)

[Claims] 1. The following formula (I)' ▲ Numerical formula, chemical formula, table, etc. ▼ (I)' [In the formula, R is a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or a carbon number 1 to 8 represents an alkenyloxy group or (polyoxyalkylene)oxy group, or two R's may form an α-methylenedioxy group, and n represents an integer of 1 to 3 (however, n = 1 Benzoylpinacolon derivatives represented by . 2. The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R is a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, an alkenyloxy group having 1 to 8 carbon atoms, or ( (polyoxyalkylene)oxy group, or two R may form an α-methylenedioxy group, and n is an integer of 1 to 3. UV absorber. 3. A cosmetic containing the benzoylpinacolon derivative according to claim 2.