JPH0798808B2 - Novel dimethoxybenzal hydantoin derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Industrial Field The compound of the present invention can be used as an ultraviolet absorber, is effective in preventing sunscreen, spots, freckles and the like, and can be applied to the cosmetic field.

2. Description of the Related Art Ultraviolet rays are known to cause various changes in skin. In dermatology, ultraviolet rays are
0-320 nm), medium-wavelength ultraviolet light (320-290 nm), and short-wavelength ultraviolet light, which are called UV-A, UV-B, and UV-C, respectively. Of these, UV-C is absorbed in the ozone layer and hardly reaches the ground. Further, it is known that when a certain amount or more of UV-B is irradiated on the skin, erythema, blisters are formed, and pigmentation is caused. On the other hand, UV-A
Conventionally, it has been said that it does not cause much change to the skin. However, recently it has been found from electron microscopy and histological evaluation that UV-A causes changes in elastic fibers in the blood vessel wall and connective tissue. In addition, sensitive skin,
Causes damage to the skin which is constantly exposed to sunlight. It has also been reported that UV-A promotes the action of UV-B (J. Willis, A. Kligman, and J. Epstein.
“Photo-enhancement” The Journal of Investigative D
ermatology 59 Vol. 6, No. 6, 416, 1973), it is important to block UV-A.

For UV-B, many have been developed so far, such as benzophenone-based UV absorbers, para-aminobenzoic acid-based UV absorbers, cinnamic acid-based UV absorbers, and salicylic acid-based UV absorbers. However, the history of research on UV-A is short, and there are few known substances that effectively absorb UV-A when applied to the skin. Currently, only a few dibenzoylmethane derivatives, cinnamic acid derivatives and chalcone derivatives are known. (West German Patent Publication No. 2728241
No. 2,728,243, JP-A-51-61641, JP-A-52-46056,
No. 57-59840, No. 57-197209, No. 60-109544) Problems to be solved by the present invention UV-absorbing ability, safety, solubility in solvent or resin, and stability UV- A UV absorber is desired.

Means for Solving Problems As a result of intensive studies in view of such circumstances, the present inventors have found that a novel dimethoxybenzal hydantoin derivative represented by the following general formula (I) has a long wavelength as shown in Table 1. These novel dimethoxybenzal hydantoin derivatives have a great absorption effect in the ultraviolet region (320 to 400 nm) and are easily soluble in various animal and vegetable oils, fats and organic solvents. They have found that it is an absorbent and have completed the present invention.

(However, in Formula 1, X is a hydrogen atom or —CH ₂ —CH ₂ CO ₂ R. R is an alkyl group having 1 to 18 carbon atoms, a cyclohexyl group, or a trimethylcyclohexyl group.) General according to the present invention The dimethoxybenzal hydantoin derivatives represented by the formula (1) are all novel compounds, but they can be produced by a known method. That is, it is obtained by Michael-adding an acrylate ester to dimethoxybenzal hydantoin produced by condensation of dimethoxybenzaldehyde and hydantoin by a base catalyst (formula 1). (However, in Formula 1, X is a hydrogen atom or —CH ₂ —CH ₂ CO ₂ R. R is an alkyl group having 1 to 18 carbon atoms, a cyclohexyl group, or a trimethylcyclohexyl group.) The general formula of the present invention (1) To exemplify the indicated compounds,
4- (3,4-dimethoxyphenyl) methylene-2,5
-Dioxo-1,3-imidazolidine dipropionic acid dimethyl ester, 4- (3,4-dimethoxyphenyl)
Methylene-2,5-dioxo-1,3-imidazolidine dipropynoic acid diethyl ester, 4- (3,4-dimethoxyphenyl) methylene-2,5-dioxo-1,3-
Imidazolidine dipropionic acid diisopropyl ester, 4- (3,4-dimethoxyphenyl) methylene-
2,5-Dioxo-1,3-imidazolidine dipropionic acid di-n-butyl ester, 4- (3,4-dimethoxyphenyl) methylene-2,5-dioxo-1,3-imidazolidine dipropionic acid diisobutyl ester Four
-(3,4-dimethoxyphenyl) methylene-2,5-
Dioxo-1,3-imidazolidinedipropionic acid bis (2-ethylhexyl ester), 4- (3,4-dimethoxyphenyl) methylene-2,5-dioxo-1-imidazolidinepropionic acid isopropyl ester, 4-
(3,4-dimethoxyphenyl) methylene-2,5-dioxo-1-imidazolidinepropionic acid methyl ester, 4- (3,4-dimethoxyphenyl) methylene-
2,5-Dioxo-1-imidazolidinepropionic acid ethyl ester, 4- (3,4-dimethoxyphenyl) methylene-2,5-dioxo-1-imidazolidinepropionic acid n-butyl ester, 4- (3,4 -Dimethoxyphenyl) methylene-2,5-dioxo-1-imidazolidinepropionic acid isobutyl ester, 4-
(3,4-dimethoxyphenyl) methylene-2,5-dioxo-1-imidazolidinepropionic acid 2-ethylhexyl ester and the like can be mentioned.

EFFECTS OF THE INVENTION The novel dimethoxybenzal hydantoin derivative represented by the general formula (1) used in the present invention has a high molecular absorption coefficient of 10 ⁴ or more at 320 to 400 nm as shown in Table 1. In addition, these novel dimethoxybenzal hydantoin derivatives are the existing compounds due to the effect of R in the molecule.
For example, compared with 5- (3,4-dimethoxyphenyl) methylenehydantoin and the like, the solubility in various animal and vegetable oils, oils and fats, and organic solvents was significantly improved.

Therefore, the novel dimethoxybenzal hydantoin derivative represented by the general formula (1) is added to a cosmetic base by a conventional method to prepare a base such as cream, solution, oil, spray, stick, emulsion, foundation, ointment. A type of effective UV-A absorber can be prepared.

That is, by mixing the compound of the present invention with an ointment base or cream base (an emulsifier may be added), a sunscreen oil, lotion or skin care agent can be produced. At this time, it is applied. As a base, solid or liquid paraffin, crystal oil, ceresin,
Hydrocarbons such as ozokerite or montan wax; vegetable or animal oils and waxes such as olive, ground wax, carnauba wax, lanolin or whale wax; stearic acid,
Fatty acids such as palmitic acid, oleic acid, and isopropyl myristate ester, or esters thereof; alcohols such as ethyl alcohol, isopropyl alcohol, cetyl alcohol, stearyl alcohol, and palmityl alcohol. Further, polyhydric alcohols having a moisturizing action such as glycerin or sorbitol can also be used.

The content of the dimethoxybenzal hydantoin derivative of the present invention is generally 0.1 to 20% by weight, preferably 0.5 to 10% by weight of the composition.

Further, the novel dimethoxybenzal hydantoin derivative of the present invention can be further blended with other ultraviolet absorbers and used as a sunscreen cosmetic. Suitable ultraviolet absorbers include, 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, 4-
Phenylbenzophenone-2-carboxylic acid isooctyl ester, p-methoxycinnamic acid ester, 2-phenyl-
Examples thereof include 5-methylbenzoxazole and p-dimethylaminobenzoic acid esters.

Further, various additives such as w / o type and o / w type emulsifiers can be added to the cosmetic composition containing the novel dimethylbenzalhydantoin derivative of the present invention.

Next, the maximum absorption wavelength and other physical properties of the representative compounds according to the present invention are summarized in Table 1 and shown in Table 1. A typical manufacturing method is shown in Example 2,
The invention is not limited by these examples.

Example 1 Example 2 Synthesis Example 1 4- (3,4-dimethoxyphenylmethylene) -2,5
-Synthesis of dioxo-1-imidazolidinepropionic acid n-butyl ester To 150 ml of dimethylformamide, 20 g (80.6 mmol) of 5- (3,4-dimethoxybenzylidene) hydantoin, 12.4 g (96 mmol) of acrylic acid n-butyl ester and water. 0.90 g (1.6 mmol) of potassium oxide was added, and the mixture was stirred at 110 ° C for 2 hours. After cooling, add 200 ml of water to the reaction mixture,
It was extracted with 500 ml of ethyl acetate. After the extract was dried over sodium sulfate, the solvent was distilled off under reduced pressure. Triene was added, and the precipitated crystals were dried, and 4- (3,4-dimethoxyphenylmethylene) -2,5-dioxo-1-imidazolidinepropionic acid n-butyl ester 24.7 g (81.
5%).

Synthesis Example 2 4- (3,4-dimethoxyphenylmethylene) -2,5
Synthesis of 2-dioxo-1-imidazolidinepropionic acid 2-ethylhexyl ester To 150 ml of dimethylformamide, 20 g (80.6 mmol) of 5- (3,4-dimethoxybenzylidene) hydantoin, 17.8 g (96 mmol) of 2-ethylhexyl acrylate and hydroxylation were added. 0.90 g (1.6 mmol) of potassium was added, and the mixture was stirred at 110 ° C for 2 hours. After cooling, add 200 ml of water to the reaction mixture,
It was extracted with 500 ml of ethyl acetate. After the extract was dried over sodium sulfate, the solvent was distilled off under reduced pressure. The residue was recrystallized from toluene-n-hexane (1: 1), and the precipitated crystals were dried and then 4- (3,4-dimethoxyphenylmethylene) -2,5-dioxo-1-imidazolidinepropionic acid. 27.1 g (77.8%) of 2-ethylhexyl ester was obtained. Synthesis Example 3 4- (3,4-dimethoxyphenylmethylene) -2,5
-Synthesis of dioxo-1,3-imidazolidinepropionic acid diethyl ester To 150 ml of dimethylformamide, 20 g (80.6 mmol) of 5- (3,4-dimethoxybenzylidene) hydantoin, 17.7 g (177 mmol) of ethyl acrylate and potassium hydroxide were added.
0.90 g (1.6 mmol) was added, and the mixture was stirred at 110 ° C for 2 hours.
After cooling, add 200 ml of water to the reaction mixture and add 500 ml of ethyl acetate.
It was extracted with. After drying the extract with sodium sulfate,
The solvent was distilled off under reduced pressure. The residue is subjected to silica gel column chromatography (eluent: toluene: ethyl acetate = 3: 1).
The product was separated and purified with 4 to give 4- (3,4-dimethoxyphenylmethylene) -2,5-dioxo-1,3-imidazolidinepropionic acid diethyl ester 22.5 g (62.3%).

Claims (1)

[Claims] 1. A novel dimethoxybenzal hydantoin derivative represented by the following general formula (1). (However, in the formula 1, X is a hydrogen atom or —CH ₂ —CH ₂ CO ₂ R. R is an alkyl group having 1 to 18 carbon atoms, a cyclohexyl group or a trimethylcyclohexyl group.)