JPH11116556A - Aminomethylenepyrimidine derivative, its production and use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new derivative having excellent UV light- absorbing ability and high photostability and useful for UV absorbers, cosmetics, organic polymer compositions, and the like. SOLUTION: A compound of formula I (R<1> ,R<2> are each H, an alkyl or the like; R<3> is an alkyl, an aralkyl or the like). For example, 1,3-dimethyl-5-(4- ethoxyphenylaminomethylene)pyrimidine-2,4,6-(1H,3H,5H)-trione. The compound of the formula I is obtained by reacting a 1,3-disubstituted barbituric acid derivative of formula II (e.g. barbituric acid) with an N-(o-, m- or p-substituted phenyl) formamide derivative of formula III [e.g. N-(4-hydroxyphenyl)formamide] in the presence of an acid catalyst (e.g. phosphorus oxychloride) at 10-60 deg.C, preferably 30-50 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an aminomethylene pyrimidine derivative having excellent ultraviolet absorbing ability and high light stability, an ultraviolet absorbent containing the same, a cosmetic, an organic polymer composition, and an aminomethylene pyrimidine derivative. It relates to a manufacturing method.

[0002]

2. Description of the Related Art It is a well-known fact that organic substances, especially high molecular compounds, are yellowed, discolored, cracked or embrittled by the action of ultraviolet rays. On the other hand, ultraviolet rays that reach the surface
V-B (280-320 nm) and UV-A (320-320 nm)
400 nm). Among these, ultraviolet rays in the UV-A region are considered to cause erythema of the skin when irradiated with a certain amount or more of light to the skin, and to promote a decrease in elasticity and a browning of the skin. So-called sunscreen cosmetics containing an ultraviolet absorber have been known for the purpose of preventing skin changes due to ultraviolet rays in the UV-A region. Known UV absorbing compounds include benzophenone derivatives, for example, 4-phenylbenzophenone,
Dibenzoylmethane derivatives such as -hydroxy-4-methoxybenzophenone-5-sulfonic acid and the like, benzotriazole derivatives such as 4-tert-butyl-4'-methoxydibenzoylmethane and the like and 2-hydroxy-5-methoxyphenyl Benzotriazole and the like have been used.

[0003] As the above-mentioned conventionally known UV absorber in the UV-A region, for example, a dibenzoylmethane-based synthetic compound has a disadvantage of causing a coloring reaction with metal ions. On the other hand, known synthetic compounds used as UV absorbers in the UV-A region are usually compounded in cosmetics and the like, but due to the problem of irritation to the skin, the amount of use is limited. The amount required for sunscreening of the skin, which is the purpose of the above, could not be used, and therefore, the ultraviolet shielding effect in the UV-A region was small. Therefore, UV-
It has been desired to develop a compound that absorbs ultraviolet light in the A region and has a very large absorption capacity, in other words, a synthetic compound having a large molecular extinction coefficient.

[0004]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a novel compound having an extremely large ultraviolet absorption capacity in the UV-A region, that is, a molecular absorption coefficient, and a method for producing the same. A second object of the present invention is to provide a novel ultraviolet absorber utilizing the above ultraviolet absorbing ability, a cosmetic containing the same, and a weather-resistant organic polymer composition.

[0005]

Means for Solving the Problems A first aspect of the present invention is that the general formula (1)

Embedded image [Wherein, R ¹ and R ² is a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aralkyl group and independently selected groups from the group consisting of aryl group, R ³ is a linear or It represents a group selected from the group consisting of a branched alkyl group, an aralkyl group, an aryl group, a cycloalkyl group, an alkyl group containing a hydroxyl group, an alkoxycarbonylalkylene group, and an alkyl group containing an oxygen atom. And the aminomethylene pyrimidine derivative represented by the formula:

A second aspect of the present invention relates to an ultraviolet absorber containing the aminomethylenepyrimidine derivative according to claim 1.

A third aspect of the present invention relates to a cosmetic containing the aminomethylpyrimidine derivative according to claim 1.

A fourth aspect of the present invention relates to a weather-resistant organic polymer composition containing the aminomethylenepyrimidine derivative according to the first aspect.

A fifth aspect of the present invention is the following general formula (2):

Embedded image [Wherein, R ¹ and R ² each independently represent a group selected from the group consisting of a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aralkyl group, and an aryl group. A 1,3-disubstituted barbituric acid derivative represented by the following general formula (3):

Embedded image [Wherein, R ³ is selected from the group consisting of a linear or branched alkyl group, an aralkyl group, an aryl group, a cycloalkyl group, an alkyl group containing a hydroxy group, an alkoxycarbonylalkylene group, and an alkyl group containing an oxygen atom. Represents a group. N- (o-, m- or p
-Substituted phenyl) formamide derivative reacted in the presence of an acid catalyst in an organic solvent, represented by the following general formula (1):

Embedded image Wherein R ¹ , R ² and R ³ are the same as above. And a method for producing the aminomethylenepyrimidine derivative represented by the formula:

The linear or branched alkyl group for R ¹ and R ² includes, for example, methyl group, ethyl group, n
-Propyl group, iso-propyl group, n-butyl group, i
Although a so-butyl group etc. can be mentioned, the carbon number is preferably 1-8. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the aralkyl group include a phenylethyl group and a phenylpropyl group.Examples of the aryl group include unsubstituted or methyl, methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, halogen, acetyl, and cyano. And the like. Alternatively, R ¹ and R ² may together form a tetramethylene group, a pentamethylene group, or a hexamethylene group.

The straight-chain or branched alkyl group for R ³ includes, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-
Examples thereof include a hexadecyl group, an n-heptadecyl group, and an n-octadecyl group.
Is preferred. Examples of the aralkyl group include a benzyl group and a phenylethyl group.
Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the aryl group include, for example, unsubstituted or methyl,
Examples include a phenyl group substituted with ethyl, methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, halogen, acetyl, cyano and the like. Examples of the alkyl group containing a hydroxyl group include a methylol group and an ethylol group. Examples of the alkoxycarbonylalkylene group include a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, and a 2-ethylhexyloxycarbonylmethyl group. Examples of the alkyl group containing an oxygen atom include a methoxyethyl group, an ethoxyethyl group, and a methoxyethyloxy group.

The above reaction is carried out usually at 10 to 60 ° C, preferably at 30 to 50 ° C.

The organic solvent used in this reaction includes
There is no particular limitation as long as it dissolves the general formulas (2) and (3), and aromatic hydrocarbons, alkyl halides and the like, for example, toluene, xylene, dichloroethylene,
Chloroform and the like can be mentioned.

Examples of the acid catalyst include phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, thionyl chloride, sulfuryl chloride and the like.

Specific examples of the aminomethylenepyrimidine derivative represented by the general formula (1) used in the present invention include the following compounds. However, “-T” at the end of the compound name is “−2, 4,
6- (1H, 3H, 5H) -trione ".
1,3-dimethyl-5- (4-ethoxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5-
(4-i-propoxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-i-butoxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-sec-butoxy) Phenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4
-T-butoxyphenylaminomethylene) pyrimidine-
T, 1,3-dimethyl-5- (4-n-pentyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-n-hexyloxyphenylaminomethylene) pyrimidine-T, 3-dimethyl-5-
(4-n-heptyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-n-nonyloxyphenylaminomethylene) pyrimidine-T,
1,3-dimethyl-5- (4-n-decyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-n-undecyloxyphenylaminomethylene) pyrimidine-T, 1,3 -Dimethyl-5- (4-
n-dodecyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-n-tridecyloxyphenylaminomethylene) pyrimidine-T,
3-dimethyl-5- (4-n-tetradecyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-n-pentadecyloxyphenylaminomethylene) pyrimidine-T, 1,3- Dimethyl-5-
(4-n-hexadecyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-n
-Heptadecyloxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5- (4-methoxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5- (4-ethoxyphenylaminomethylene) pyrimidine- T, 1,3-diethyl-5- (4-n-propoxyphenylaminomethylene) pyrimidine-T, 1,3
-Diethyl-5- (4-i-propoxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5-
(4-n-butoxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5- (4-n-pentyloxyphenylaminomethylene) pyrimidine-T, 1,3
-Diethyl-5- (4-n-hexyloxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5
-(4-n-heptyloxyphenylaminomethylene)
Pyrimidine-T, 1,3-diethyl-5- [4- (2-
Ethylhexyloxyphenylaminomethylene)] pyrimidine-T, 1,3-diethyl-5- (4-n-octadecyloxyphenylaminomethylene) pyrimidine-
T, 1,3-dimethyl-5- (4-methoxyethylphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-ethoxyethyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl −5- (4
-Methoxycarbonylmethyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-
Ethoxycarbonylmethyloxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5- (4-methoxyethyloxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5- (4-ethoxyethyloxyphenylamino Methylene) pyrimidine-T, 1,
3-diethyl-5- (4-methoxycarbonylmethyloxyphenylaminomethylene) pyrimidine-T, 1,3
-Diethyl-5- (4-ethoxycarbonylmethyloxyphenylaminomethylene) pyrimidine-T, 1,3-
Dimethyl-5- (2-ethoxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (2-i
-Propoxyphenylaminomethylene) pyrimidine-
T, 1,3-dimethyl-5- (2-i-butoxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (2-sec-butoxyphenylaminomethylene) pyrimidine-T, 1,3- Dimethyl-5- (2-t
-Butoxyphenylaminomethylene) pyrimidine-T,
1,3-dimethyl-5- (2-n-pentyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (2-n-hexyloxyphenylaminomethylene) pyrimidine-T, 1,3- Dimethyl-5- (2-
n-heptyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (2-n-octyloxyphenylaminomethylene) pyrimidine-T, 1,3
-Diethyl-5- (2-methoxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5- (2-ethoxyphenylaminomethylene) pyrimidine-T,
3-diethyl-5- (2-n-propoxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5-
(2-i-propoxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5- (2-n-butoxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5- (2-n-pentyl (Oxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5-
(2-n-hexyloxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5- (2-n-heptyloxyphenylaminomethylene) pyrimidine-T,
1,3-diethyl-5- [2- (2-ethylhexyloxyphenylaminomethylene)] pyrimidine-T,
3-diethyl-5- (2-n-octyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-
5- (3-ethoxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (3-i-propoxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (3-i-butoxy Phenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (3-s
ec-butoxyphenylaminomethylene) pyrimidine-
T, 1,3-dimethyl-5- (3-t-butoxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (3-n-pentyloxyphenylaminomethylene) pyrimidine-T, 1,3 -Dimethyl-5- (3-n
-Hexyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (3-n-heptyloxyphenylaminomethylene) pyrimidine-T, 1,3-
Dimethyl-5- (3-n-nonyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5-
(3-n-decyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (3-n-undecyloxyphenylaminomethylene) pyrimidine-T,
1,3-dimethyl-5- (3-n-dodecyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (3-n-tridecyloxyphenylaminomethylene) pyrimidine-T, 1,3 -Diethyl-5- (3
-Methoxyphenylaminomethylene) pyrimidine-T,
1,3-diethyl-5- (3-ethoxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5-
(3-n-propoxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5- (3-i-propoxyphenylaminomethylene) pyrimidine-T, 1,3-
Diethyl-5- (3-n-butoxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5- (3-
n-pentyloxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5- (3-n-hexyloxyphenylaminomethylene) pyrimidine-T, 1,3
-Diethyl-5- (3-n-heptyloxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5
-[3- (2-ethylhexyloxyphenylaminomethylene)] pyrimidine-T, 1,3-diethyl-5-
(3-n-octadecyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (3-methoxyethyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (3-ethoxyethyl Oxyphenylaminomethylene) pyrimidine-T, 1,
3-dimethyl-5- (3-methoxycarbonylmethyloxyphenylaminomethylene) pyrimidine-T, 1,3
-Dimethyl-5- (3-ethoxycarbonylmethyloxyphenylaminomethylene) pyrimidine-T, 1,3-
Diethyl-5- (3-methoxyethyloxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5
-(3-ethoxyethyloxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5- (3-methoxycarbonylmethyloxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5- (3-ethoxy Carbonylmethyloxyphenylaminomethylene) pyrimidine-T and the like.

The following general formula (2)

Embedded image Wherein R ¹ and R ² are the same as above. Specific examples of the compound of the formula (1) include barbituric acid, 1,3-dimethyl-
Barbituric acid, 1,3-diethyl-barbituric acid, 1,
3-di-n-propyl-barbituric acid, 1,3-di-i
-Propyl-barbituric acid, 1,3-di-n-butyl-
Barbituric acid, 1,3-di-i-butyl-barbituric acid, 1,3-di-sec-butyl-barbituric acid, 1,
3-di-n-pentyl-barbituric acid, 1,3-di-n
-Hexyl-barbituric acid, 1,3-di-n-heptyl-barbituric acid, 1,3-di-n-octyl-barbituric acid, 1,3-diphenyl-barbituric acid, 1,3-dibenzyl-barbituric acid, 1,3-dicyclohexyl-
Barbituric acid, 1,3-di-o-tolyl-barbituric acid, 1,3-di-m-tolyl-barbituric acid, 1,3-
Di-p-tolyl-barbituric acid, 1,3-di-o-anisyl-barbituric acid, 1,3-di-m-anisyl-barbituric acid, 1,3-di-p-anisyl-barbituric acid,
1,3-di-o-chlorophenyl-barbituric acid, 1,
3-di-m-chlorophenyl-barbituric acid, 1,3-
Di-p-chlorophenyl-barbituric acid, 1,3-di-
o-bromophenyl-barbituric acid, 1,3-di-m-
Bromophenyl-barbituric acid, 1,3-diallyl-barbituric acid, 1,3-di- (2-methylcyclohexyl) -barbituric acid, 1,3-di- (3-methylcyclohexyl) -barbituric acid, 1,3 -Di- (4-methylcyclohexyl) -barbituric acid;

The following general formula (3)

Embedded image Wherein R ³ is the same as defined above. Specific examples of the compound of the formula: N- (4-hydroxyphenyl) formamide, N- (4-methoxyphenyl) formamide, N-
(4-ethoxyphenyl) formamide, N- (4-n
-Butoxyphenyl) formamide, N- (4-i-butoxyphenyl) formamide, N- (4-sec-butoxyphenyl) formamide, N- (4-n-pentyloxyphenyl) formamide, N- (4-n- Hexyloxyphenyl) formamide, N- (4-n-heptyloxyphenyl) formamide, N- (4-n-
Octyloxyphenyl) formamide, N- [4-
(2-ethylhexyloxyphenyl)] formamide, N- (4-n-nonyloxyphenyl) formamide, N- (4-n-decyloxyphenyl) formamide, N- (4-n-undecyloxyphenyl) formamide, N- (4-n-tridecyloxyphenyl) formamide, N- (4-n-tetradecyloxyphenyl) formamide, N- (4-n-pentadecyloxyphenyl) formamide, N- (4-n-hexa Decyloxyphenyl) formamide, N- (4-n-heptadecyloxyphenyl) formamide, N- (4-n-
Octadecyloxyphenyl) formamide, N- (4
-N-nonadecyloxyphenyl) formamide, N-
(4-methoxyethyloxyphenyl) formamide,
N- (4-ethoxyethyloxyphenyl) formamide, N- (4-n-propoxyethyloxyphenyl)
Formamide, N- (4-methoxycarbonylmethyloxyphenyl) formamide, N- (4-ethoxycarbonylmethyloxyphenyl) formamide, N- (4
-N-propoxycarbonylmethyloxyphenyl) formamide, N- (4-cyclopentyloxyphenyl) formamide, N- (4-cyclohexyloxyphenyl) formamide, N- (4-phenyloxyphenyl) formamide, N- (4-benzyl Oxyphenyl) formamide, N- (4-phenylethyloxyphenyl) formamide, N- (4-phenylpropyloxyphenyl) formamide, N- (4-phenylbutyloxyphenyl) formamide, N- (2- or 3
-Hydroxyphenyl) formamide, N- (2- or 3-methoxyphenyl) formamide, N- (2- or 3-ethoxyphenyl) formamide, N- (2-
Or 3-n-butoxyphenyl) formamide, N-
(2- or 3-i-butoxyphenyl) formamide, N- (2- or 3-sec-butoxyphenyl)
Formamide, N- (2- or 3-n-pentyloxyphenyl) formamide, N- (2- or 3-n-
Hexyloxyphenyl) formamide, N- (2- or 3-n-heptyloxyphenyl) formamide,
N- (2- or 3-n-octyloxyphenyl) formamide, N- (2- or 3-methoxyethyloxyphenyl) formamide, N- (2- or 3-ethoxyethyloxyphenyl) formamide, N- (2 −
Or 3-n-propoxyethyloxyphenyl) formamide, N- (2- or 3-methoxycarbonylmethyloxyphenyl) formamide, N- (2- or 3-ethoxycarbonylmethyloxyphenyl) formamide and the like.

The organic substance stabilized by the compound represented by the general formula (1), for example, a cosmetic or a polymer material, may further contain conventional additives, for example, an antioxidant, a light stabilizer and the like. , A metal deactivator and a peroxide scavenger.

The organic polymer substance may be a natural or synthetic polymer substance, such as cellulose, CM
C, natural rubber, synthetic rubber such as SBR and NBR, polyolefin such as polyethylene and polypropylene, and synthetic resin such as polyester, polyamide, polyurethane and polyvinyl chloride.

Antioxidants which may be added in addition to the compounds according to the invention include, for example, 2,6-di-tert-
Butyl-4-methylphenol, 2-tert-4,6
-Dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert
-Butyl-4-isobutylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol,
2,6-dioctadecyl-4-methylphenol, 2,
4,6-tricyclohexylphenol, 2,6-dinonyl-4-methylphenol, 2,6-di-tert-
Butyl-4-methoxymethylphenol, 2,4-dimethyl-6- (1'-methyl-undec-1'-yl)-
Phenol, 2,4-dimethyl-6- (1'-methyl-
Heptadec-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyl-trideca-1'-yl)-
Phenol and mixtures thereof, 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,
4-di-octylthiomethyl-6-methylphenol,
2,4-di-octylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol and mixtures thereof, 2,6-di-tert-
Butyl-4-methoxyphenol, 2,5-di-ter
t-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4
-Hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert
-Butyl-4-hydroxyphenylstearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate and mixtures thereof, 2,4-bis-octylmercapto-6- (3,5-diphenyl -Tert-
Butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3
5-di-tert-butyl-4-hydroxyanilino)
-1,3,5-triazine, 2-octylmercapto-
4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,
4,6-tris (3,5-di-tert-butyl-4-
Hydroxyphenoxy) -1,2,3-triazine,
1,3,5-tris (3,5-di-tert-butyl-
4-hydroxybenzyl) -isocyanurate, 1,
3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -isocyanurate,
2,4,6-tris (3,5-di-tert-butyl-
4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) -isocyanurate and the like and 2,2′-methylenebis (6-tert-butyl-4-methylphenol),
2,2'-methylenebis (6-tert-butyl-4-
Ethylphenol), 2,2'-ethylidenebis (4,
6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 4,4'-methylenebis (2,6-di-
tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol),
1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, ethylene glycol bis [3,3'-bis (3'-tert-butyl-4'-)
Hydroxyphenyl) butyrate] and 1,3,
5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene,
1,4-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-
4-hydroxybenzyl) -phenol and the like.

Light stabilizers which may be added in addition to the compounds according to the invention include, for example, 2- (2'-hydroxy-
5'-methylphenyl) benzotriazole, 2-
(3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-ter
t-butyl-2'-hydroxyphenyl) benzotriazole, 2- [2'-hydroxy-5 '-(1,1,
3,3-tetramethylbutyl) phenyl] benzotriazole, 2- (3 ', 5'-di-tert-butyl-
2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-4 '-Octoxyphenyl) benzotriazole, 2- (3', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- [3'-tert-butyl-2 '
-Hydroxy-5 '-(2'-octyloxycarbonylethylphenyl) -5-chlorobenzotriazole and the like: 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4
-Benzyloxy-, 4,2 ', 4'-trihydroxy-, 2'-hydroxy-4,4'-dimethoxy- or 4- (2-ethylhexyloxy) -2-hydroxybenzophenone derivative, etc .: 4-tert- Butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol,
Bis (4-tert-butylbenzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate Etc .: ethyl α-cyano-β, β-diphenylacrylate, isooctyl α-cyano-
β, β-diphenyl acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, etc .: bis (2,2,6,
6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) adipate and the like: 4,4′- Jee
Octyloxyoxanilide, 2,2'-diethoxyoxyoxanilide, 2,2'-di-octyloxy-
5,5'-di-tert-butyl oxanilide, 2,
2'-di-dodecyloxy-5,5'-di-tert-
Butyl oxanilide, 2-ethoxy-2'-ethyl oxanilide, N, N'-bis (3-dimethylaminopropyl) oxanilide, 2-ethoxy-5-tert-butyl-2'-ethoxy oxanilide and the like : 2,4,6-tris (2-hydroxy-4-octyloxyphenyl)-
1,3,5-triazine, 2- (2-hydroxy-4-
(Octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2-
(2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6 (2,4-dimethylphenyl)-
1,3,5-triazine, 2- (2-hydroxy-4-
Dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like.

Metal deactivators which may be added in addition to the compounds according to the invention include, for example, N, N'-diphenyloxalic acid diamide, N-sartilal-N'-salicyloylhydrazine, N, N ' -Bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,3-triazole, bis (benzylidene) ) Oxalic acid hydrazide, isophthalic acid dihydrazide, N, N'-diacetal-adipic dihydrazide, N, N'-bis-salicyloyloxalic acid dihydrazide, N, N'-bis-salicyloyl-thiopropionic acid dihydrazide and the like. Can be

Peroxide scavengers which may be added in addition to the compounds according to the invention include, for example, dilauryl-thiodipropionate, distearyl-thiodipropionate, dimyristyl-thiodipropionate or ditridecyl-thiodipropionate. And thiodipropionate, 2-mercaptobenzimidazole, and pentaerythritol tetrakis (dodecylmercapto) propionate.

The maximum absorption range of the aminomethylenepyrimidine derivative of the general formula (1) of the present invention is in the range of 330 to 360 nm, and has an excellent ultraviolet absorbing ability as compared with the conventionally known UV-B ultraviolet absorber. It has favorable characteristics such as being irritating to the skin, having no other harmful effects, being excellent in compatibility with a cosmetic base, and being difficult to be percutaneously absorbed.

The cosmetic having the aminomethylene pyrimidine derivative (1) of the present invention is blended with the above-mentioned known cosmetic base by a conventional method, and is used as a cream, a solution, an oil, a spray,
Manufactured by dispensing into sticks, emulsions, foundations, and ointments.

The amount of the aminomethylenepyrimidine derivative (1) in the cosmetic composition of the present invention can be varied depending on the form of use, and is not particularly limited, and may be mixed in an effective amount. 1 to 20% by weight, preferably 0.
It is preferable that the content is 5 to 5% by weight. Further, the aminomethylene pyrimidine derivative (1) of the present invention comprises:
It may be a mixture of only itself, but also other UV-
A favorable effect is exhibited by using it as a normal sunscreen cosmetic in combination with the B absorbent.

The base of the external preparation for skin, which is a cosmetic according to the present invention, may be any one which is inert to the aminomethylenepyrimidine derivative, and may be any of solid, liquid, emulsion, foamy liquid, gel and the like. There may be. Examples of the cosmetic base of the present invention include, for example, olive oil, camellia oil, cottonseed oil, castor oil, soybean oil, coconut oil, cocoa butter, lanolin, beeswax, carnauba wax, hardened oil, stearic acid, palmitic acid, myristic acid, ascorbin Examples include acids, behenic acid, or esters thereof, or metal salts thereof, and higher alcohols such as decylethyl, oleyl, lauryl, cetyl, or stearyl alcohol. As synthetic oils, for example, squalane monostearate glyceride, synthetic polyether oils, sorbitan monooleate,
Lanolin and its hydrogenated product or squalane. Examples of the mineral oil include paraffin, petrolatum, liquid paraffin, microcrystal wax and the like. Furthermore, silicone oil, polyethers,
Examples thereof include dialkylsiloxanes, fine powders such as starch and talc, and low-boiling hydrocarbons or halogen-containing hydrocarbons used as switchesbout type propellants.

The aminomethylenepyrimidine derivative (1) of the present invention can be used by blending it in cosmetics together with various additives. Suitable additives include, for example, W / O type and O / W Emulsifiers. As the emulsifier, a commercially available emulsifier may be used, and a thickener such as ethyl cellulose, polyacrylic acid, gelatin, and agar may be added as necessary. Further, a fragrance, a humectant, an emulsion stabilizer, a medicinal ingredient and the like may be added as necessary.

Examples of the humectant include glycerin, propylene glycol, sorbite, polyethylene glycol, sodium pyrrolidonecarboxylate and the like. Examples of the adhesive include polyvinyl alcohol, sodium carboxylmethyl cellulose, sodium alginate, propylene glycol ester and the like. Examples of the preservative include benzoic acid, sorbic acid, dehydroacetic acid, p-oxybenzoic esters and the like. Examples of the solvent include ethanol, acetone, acetic ester, isopropanol and the like. Examples of the emulsifier include polyglycerin fatty acid ester, polyoxyethylene lanolin derivative, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene sorbitol fatty acid ester, sucrose fatty acid ester, propylene glycol fatty acid ester and the like. Is mentioned.

[0030]

EXAMPLES The present invention will be specifically described below with reference to synthesis examples of the compounds of the present invention. However, these are merely examples of preferred embodiments, and the present invention is not limited to these examples. .

Example 1 1,3-dimethyl-5- (4-methoxyphenylaminomethylene) -2,4,6- (1H, 3H, 5H) -trione [In the general formula (1), R ¹ = R ² = methyl, R ³
= 4-methoxy] To a stirred suspension of 0.20 mol of barbituric acid, 0.50 mol of N- (4-methoxyphenyl) formamide and 25 ml of toluene, 0.50 mol of phosphorus oxychloride is added.
Add over minutes. During this addition, the temperature is kept below 45 ° C. Stirring is continued for 10 minutes, then 250 ml
Of a 0.30 mol solution of barbituric acid in toluene
Add at 0-65 ° C over 45 minutes. The reaction mixture was allowed to cool to room temperature with stirring and then
The reaction is stopped by dropwise addition into 600 ml of a 5% sodium hydroxide solution. This organic layer is washed with 200 ml of a saturated saline solution. Separate the organic layer, dry over anhydrous sodium sulfate, filter, and concentrate to give the crude product. Recrystallized from dioxane, melting point 19
A purified product at 0-191 ° C is obtained. The physical properties of this purified product are as follows.

Ultraviolet absorption spectrum (chloroform): λ
max (nm) 356.5 εmax 29,100 Infrared absorption spectrum: cm ^-1 (KBr) 1722 (lactone C = O), 1652, 1236 (heterocyclic absorption),
1480 (*), 1260 (C-O-C)

Embedded image

Example 2 1,3-dimethyl-5- (4-ethoxyphenylaminomethylene) -2,4,6- (1H, 3H, 5H) -trione [In the general formula (1), R ¹ = R ² = methyl, R ³
= Ethyl] N- (4-methoxyphenyl) formamide is converted to N- (4
A procedure similar to that of Example 1 was repeated, except that -ethoxyphenyl) formamide was used. The melting point of the purified product is 198 to 198.5 ° C, and its physical properties are as follows.

Ultraviolet absorption spectrum (chloroform): λ
max (nm) 357.5 εmax 31,600 Infrared spectrum: cm ^-1 (KBr) 1718 (lactone C = O), 1660, 1636 (heterocyclic absorption), 15
20 (*), 1258 (C-O-C)

Embedded image

Example 3 1,3-dimethyl-5- (4-i-propoxyphenylaminomethylene) -2,4,6- (1H, 3H, 5H)
Synthesis of -trione [in the general formula (1), R ¹ = R ² = methyl, R ³ = i-propyl] N- (4-methoxyphenyl) formamide is converted to N- (4
A procedure similar to that of Example 1 was repeated, except that -ethoxyphenyl) formamide was used. The melting point of the purified product is 144.5 to 145.5 ° C, and its physical properties are as follows.

Ultraviolet absorption spectrum (chloroform): λ
max (nm) 358 εmax 32,900 Infrared spectrum: cm ^-1 (KBr) 1718 (lactone C = O), 1660, 1650 (heterocyclic absorption), 14
78 (*), 1258 (C-O-C)

Embedded image

Example 4 1,3-Dimethyl-5- (4-n-butoxyphenylaminomethylene) -2,4,6- (1H, 3H, 5H)-
Trione [in the general formula (1), R ¹ = R ² = methyl,
R ³ = n-butyl] N- (4-methoxyphenyl) formamide is converted to N- (4
The same procedure as in Example 1 was repeated, except that -n-butoxyphenyl) formamide was used. The melting point of the purified product is 127 to 128.5 ° C, and its physical properties are as follows.

Ultraviolet absorption spectrum (chloroform): λ
max (nm) 357.5 εmax 29,100 Infrared absorption spectrum: (KBr) cm ^-1 1720 (lactone C = O), 1662, 1632 (heterocyclic absorption), 1480 (*), 1258 (CO- C)

Embedded image

Example 5 N- [4- (2-ethylhexyloxy) phenylaminomethylene] -2,4,6- (1H, 3H, 5H) -trione [In the general formula (1), R ¹ = R ² = Methyl, R
Synthesis of ³ = 2-ethylhexyl] N- (4-methoxyphenyl) formamide was converted to N- [4
A procedure similar to that of Example 1 was repeated, except that-(2-ethylhexyloxy) phenyl] formamide was used. The melting point of the purified product is 88.5 to 90 ° C,
Its physical properties are as follows.

Ultraviolet absorption spectrum (chloroform): λ
max 358.5 εmax 50,500 Infrared absorption spectrum: (KBr) cm ^-1 1720 (lactone C = O), 1660, 1632 (heterocyclic absorption), 1482 (*), 1258 (COC)

Embedded image

Example 6 Hereinafter, specific examples of the formulation of the skin external preparation according to the present invention will be described. According to the formulation as shown in Table 1, the compound of Example 4, "1,3-dimethyl-5- (4-n-butoxyphenylaminomethylene) -2,4,6- (1H, 3H, 5
H) -trione ”, a serum containing control compound 1 of“ 2,2 ′, 4,4′-tetrahydroxybenzophenone ”and a control example 2 compound“ p-methoxycinnamic acid 2- A serum containing "ethylhexyl" was manufactured.

[0042]

[Table 1] Comparative Example 1 exhibited a pale yellow color and no cosmetic liquid was obtained.

Confirmation of Sunscreen Effect Each of the cosmetics prepared in Example 5 and the serum of Comparative Example 2 was applied to the skin, and the effect of actual use on the beach was tested. The sample solution was applied to the left and right halves of 10 males and 10 females each, and the degree of sunburn was examined.
Shown in The evaluation criteria were the following evaluation criteria according to the degree of sunburn. Evaluation criteria No erythema was observed 〇 Slight erythema was observed △ Strong erythema was observed ×

[0044]

[Table 2]

Light Stabilizing Effect on Polymeric Substance The samples prepared in Example 1 were mixed with 100 parts by weight of polyethylene powder and polypropylene powder, respectively, for 0.05%.
Parts, 0.2 parts by weight, and 0.5 parts by weight, and sufficiently mixed with a mixer.
The mixture was melt-kneaded by a 5 mm diameter extruder and granulated. The obtained pellet was compression molded at 210 ° C. into a sheet having a thickness of 0.25 mm to prepare a test piece. The obtained test piece was punched out into a dumbbell type corresponding to a tensile test. In the same manner as described above, a test piece for comparison and control without addition of a light stabilizer was prepared and evaluated.

These test pieces were prepared by using W
Using a EL-75XS-HS-BEC type xenon sunshine long life weatherometer, light irradiation was performed at a black panel temperature of 80 ° C., and changes in tensile strength of each test piece over time were compared. The tensile test was performed using a DSS-5000 type tensile tester manufactured by Shimadzu Corporation at a temperature of 2
3 ± 2 ° C, relative humidity 50 ± 5%, test speed 50 ± per minute
The measurement was performed at 5.0 mm. The tensile strength was determined by the following method.

(Equation 1) Ts = tensile strength (kgf / mm ² ) T = thickness of sample (mm) W = width of sample (mm) S = maximum strength of sample (kgf)

The results obtained are as shown in Table 3.
As is evident from the results shown in Table 3, the aminomethylene pyrimidine derivative according to the present invention shows an excellent stabilizing effect (ie, prolonged deterioration time).

[0048]

[Table 3]

[0049]

【effect】

(1) According to the present invention, a novel aminomethylenepyrimidine derivative having a use as an ultraviolet absorber or the like and a method for producing the same can be provided. (2) According to the present invention, for ultraviolet rays in the UV-A region,
It exhibits better absorption ability than conventional UV absorbers, and cosmetics using the same have the property that they are less likely to damage the skin and that the compound is less likely to be transdermally absorbed. (3) It is also useful as a stabilizer for polymer compounds.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09K 15/30 C09K 15/30

Claims (5)

[Claims] 1. A compound of the general formula (1) [Wherein, R ¹ and R ² is a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aralkyl group and independently selected groups from the group consisting of aryl group, R ³ is a linear or It represents a group selected from the group consisting of a branched alkyl group, an aralkyl group, an aryl group, a cycloalkyl group, an alkyl group containing a hydroxyl group, an alkoxycarbonylalkylene group, and an alkyl group containing an oxygen atom. ] The aminomethylene pyrimidine derivative represented by these. 2. An ultraviolet absorber containing the aminomethylene pyrimidine derivative according to claim 1. 3. A cosmetic comprising the aminomethylene pyrimidine derivative according to claim 1. 4. A weather-resistant organic polymer composition containing the aminomethylene pyrimidine derivative according to claim 1. 5. The following general formula (2): [Wherein, R ¹ and R ² each independently represent a group selected from the group consisting of a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aralkyl group, and an aryl group. And a 1,3-disubstituted barbituric acid derivative represented by the following general formula (3): [Wherein, R ³ is selected from the group consisting of a linear or branched alkyl group, an aralkyl group, an aryl group, a cycloalkyl group, an alkyl group containing a hydroxy group, an alkoxycarbonylalkylene group, and an alkyl group containing an oxygen atom. Represents a group. N- (o-, m- or p
-Substituted phenyl) formamide derivative is reacted in an organic solvent in the presence of an acid catalyst, characterized by the following general formula (1): Wherein R ¹ , R ² and R ³ are the same as above. ] The method for producing an aminomethylenepyrimidine derivative represented by the formula: