JPH11263778A - Aminomethylenepyrimidine derivative, its production and use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound with high ability to absorb ultraviolet light corresponding to UV-A region, and useful as an ultraviolet light absorber, and for cosmetics and weathering organic polymer compositions. SOLUTION: This new compound is shown by formula I (R<1> and R<2> are each an alkyl or the like; R<3> is H or the like; R<4> is an acyloxy or the like), e.g. 1,3-dimethyl-5-(4pivaloyloxyphenylaminomethylene)pyrimidine-2,4,6-(1H, 3H,5H)- trione. The compound of formula I is obtained by reaction of 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- pivaloyloxyphenyl) formamide] in an organic solvent such as toluene in the presence of an acid catalyst such as phosphorus oxychloride pref. at 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
４００400 nm) in most cases. Of these, ultraviolet rays in the UV-A region are irradiated with a certain amount of light to the skin,
It causes erythema of the skin, and is considered to be a cause of promoting a decrease in skin elasticity and browning. Such UV-
So-called sunscreen cosmetics containing an ultraviolet absorber have been known for the purpose of preventing skin changes due to ultraviolet rays in the A region. Known UV absorbing compounds include benzophenone derivatives such as 4-phenylbenzophenone and 2-hydroxy-4-methoxybenzophenone-5.
-Dibenzoylmethane derivatives such as sulfonic acid, for example,
Benzotriazole derivatives such as 4-tert-butyl-4'-methoxydibenzoylmethane and the like, for example, 2-hydroxy-5-methoxyphenylbenzotriazole 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 [In the formula, R ¹ and R ² are linear or branched, alkyl group, aralkyl group, cycloalkyl group and independently selected groups from the group consisting of aryl group,, R ³ is
A group selected from the group consisting of a hydrogen atom, a linear or 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. , R ⁴ is an acyloxy group or an aroyloxy group. 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 are linear or branched groups independently selected from the group consisting of alkyl groups, aralkyl groups, cycloalkyl groups, and aryl groups. A 1,3-disubstituted barbituric acid derivative represented by the following general formula (3):

Embedded image [Wherein, R ³ represents a hydrogen atom, a linear or branched alkyl group, an aralkyl group, an aryl group, a cycloalkyl group,
It is a group selected from the group consisting of an alkyl group containing a hydroxyl group, an alkoxycarbonylalkylene group and an alkyl group containing an oxygen atom, and R ⁴ is an acyloxy group or an aroyloxy group. N- (o-,
An m- or p-substituted phenyl) formamide derivative is
Reacting in an organic solvent in the presence of an acid catalyst;

Embedded image Wherein R ¹ , R ² , R ³ and R ⁴ are the same as described above. And a method for producing the aminomethylenepyrimidine derivative represented by the formula:

[0010] The reaction is usually carried out at 10 to 60 ° C, preferably 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.

The linear or branched alkyl group for R ¹ and R ² includes, for example, a methyl group, an ethyl group,
n-propyl group, iso-propyl group, n-butyl group,
Although an iso-butyl group and the like can be mentioned, the number of carbon atoms is preferably 1 to 8. As the aralkyl group,
For example, a phenylethyl group, a phenylpropyl group and the like can be mentioned. Examples of the cycloalkyl group include, for example, cyclopentyl group and cyclohexyl group, and examples of the aryl group include unsubstituted or methyl, methoxy, ethoxy, methoxycarbonyl, ethoxycarbonyl, halogen, acetyl, cyano, and the like. Examples include a substituted phenyl group.
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 acyloxy group for R ⁴ includes, for example, acetyloxy group, n-propionyloxy group, i
so-propionyloxy group, pivaloyloxy group, n
-Butyryloxy group, iso-butyryloxy group, n-
Valeroyloxy group, iso-valeroyloxy group, n
-Caproyloxy group, n-caprylyloxy group, n-
Heptanoyloxy group, 2-ethylhexanoyloxy group, 2-methylcaproyloxy group, 5-methylcaproyloxy group, methoxyacetyloxy group, ethoxyacetyloxy group, n-propoxyacetyloxy group, i
so-propoxyacetyloxy group, 3,3-dimethyl-n-butyryloxy group, 2,2-dimethyl-n-valeroyloxy group, 2,2-dimethylpropionyloxy group, 3,5,5-trimethylhexanoyloxy And the like. The carbon number is preferably 1 to 8. Examples of the aroyloxy group for R ⁴ include a benzoyloxy group, a phenylacetyloxy group, a phenylpropionyloxy group, a p-toluoyloxy group, m
-Toluoyloxy group, o-toluoyloxy group, p-
Tolylacetyloxy group, m-tolylacetyloxy group, o-tolylacetyloxy group, p-anisoyloxy group, m-anisoyloxy group, o-anisoyloxy group, 4-ethoxybenzoyloxy group, 3-ethoxy Benzoyloxy group, 2-ethoxybenzoyloxy group,
4-ethylbenzoyloxy group, 4-n-propylbenzoyloxy group, 4-iso-propylbenzoyloxy group, 4-n-butylbenzoyloxy group, 4-iso
-Butylbenzoyloxy group, 4-tert-butylbenzoyloxy group, 4-n-pentylbenzoyloxy group, 4-n-hexylbenzoyloxy group, 4-n-heptylbenzoyloxy group, 1-naphthoyloxy group,
Examples thereof include a 2-naphthoyloxy group.

Specific examples of the aminomethylene pyrimidine derivative represented by the above general formula (1) used in the present invention include the following compounds. In addition, “-T” at the end of the compound name is “−2, 4,
6- (1H, 3H, 5H) -trione ".

1,3-dimethyl-5- (4-acetyloxyphenylaminomethylene) pyrimidine-T, 1,3
-Dimethyl-5- (4-n-propionyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-iso-propionyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5 −
(4-pivaloyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (2-methyl-4
-Pivaloyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-n-butyryloxyphenylaminomethylene) pyrimidine-T, 1,3
-Dimethyl-5- (4-iso-butyryloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-n-valeroyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl −5- (4-
iso-valeroyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-n-caproyloxyphenylaminomethylene) pyrimidine-
T, 1,3-dimethyl-5- (4-n-heptanoyloxyphenylaminomethylene) pyrimidine-T, 1,3
-Dimethyl-5- (4-n-caprylyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-
5- [4- (2-ethylhexanoyloxyphenylaminomethylene)] pyrimidine-T, 1,3-dimethyl-
5- [4- (2-methylcaproyloxyphenylaminomethylene)] pyrimidine-T, 1,3-dimethyl-5
-[4- (5-methylcaproyloxyphenyloxyphenylaminomethylene)] pyrimidine-T, 1,3-
Dimethyl-5- (4-methoxyacetyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-
5- (4-ethoxyacetyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-
n-propoxyacetyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-i
so-propoxyacetyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- [4-
(3,3-dimethyl-n-butyryloxyphenylaminomethylene)] pyrimidine-T, 1,3-dimethyl-5
-[4- (2,2-dimethyl-n-valeroyloxyphenylaminomethylene)] pyrimidine-T, 1,3-dimethyl-5- [4- (2,2-dimethylpropionyloxyphenylaminomethylene)] pyrimidine −T, 1,
3-dimethyl-4- (3,5,5-trimethylhexanoyloxyphenylamino) pyrimidine-T, 1,3-
Dimethyl-5- (4-benzoyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5-
(4-phenylacetyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-phenylpropionyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (p-toluoyloxy Phenylaminomethylene) pyrimidine-T,
1,3-dimethyl-5- (p-anisoyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-ethoxybenzoyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl- 5-
(4-ethylbenzoyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-n
-Propylbenzoyloxyphenylaminomethylene)
Pyrimidine-T, 1,3-dimethyl-5- (4-iso
-Propylbenzoyloxyphenylaminomethylene)
Pyrimidine-T, 1,3-dimethyl-5- (4-n-butylbenzoyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-iso-butylphenylbenzoyloxyphenylaminomethylene)
Pyrimidine-T, 1,3-dimethyl-5- (4-ter
t-butylbenzoyloxyphenylaminomethylene)
Pyrimidine-T, 1,3-dimethyl-5- (4-pentylbenzoyloxyphenylaminomethylene) pyrimidine-T, 1,3-dimethyl-5- (4-n-hexylbenzoyloxyphenylaminomethylene) pyrimidine-
T, 1,3-dimethyl-5- (4-n-heptylbenzoyloxyphenylaminomethylene) pyrimidine-T,
1,3-dimethyl-5- [4- (1-naphthoyloxyphenylaminomethylene)] pyrimidine-T, 1,3-
Dimethyl-5- [4- (2-naphthoyloxyphenylaminomethylene)] pyrimidine-T, 1,3-diethyl-5- (4-iso-propionyloxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl −5-
(4-iso-butyryloxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5- (4-pivaloyloxyphenylaminomethylene) pyrimidine-
T, 1,3-diethyl-5- (4-acetyloxyphenylaminomethylene) pyrimidine-T, 1,3-diethyl-5- (4-iso-valeroyloxyphenylaminomethylene) pyrimidine-T, 1,3 -Diethyl-5-
[4- (2-methylcaproyloxyphenylaminomethylene)] pyrimidine-T, 1,3-diethyl-5-
[4- (2-ethylhexanoyloxyphenylaminomethylene)] pyrimidine-T, 1,3-diethyl-5-
[4- (3,3-dimethyl-n-butyryloxyphenylaminomethylene)] pyrimidine-T, 1,3-diethyl-5- [4- (2,2-dimethyl-n-valeroyloxyphenylaminomethylene) )] Pyrimidine-T, 1,
3-diethyl-5- (4-iso-propylbenzoyloxyphenylaminomethylene) pyrimidine-T, 1,
3-diethyl-5- (4-tert-butylbenzoyloxyphenylaminomethylene) pyrimidine-T, 1,
3-diethyl-5- [4- (1-naphthoyloxyphenylaminomethylene)] pyrimidine-T, 1,3-diethyl-5- [4- (2-naphthoyloxyphenylaminomethylene)] 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-5-barbituric acid, 1,3-di-i-propyl-5-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,
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 and R ⁴ are the same as above. Specific examples of the compound of the formula: N- (4-acetyloxyphenyl) formamide, N- (4-n-propionyloxyphenyl) formamide, N- (4-iso-propionyloxyphenyl) formamide, N- (4 -Pivaloyloxyphenyl) formamide, N- (2-methyl-4-pivaloyloxyphenyl) formamide, N-
(4-n-butyryloxyphenyl) formamide, N
-(4-iso-butyryloxyphenyl) formamide, N- (4-n-valeroyloxyphenyl) formamide, N- (4-iso-valeroyloxyphenyl) formamide, N- (4-n-caproyl Oxyphenyl) formamide, N- (4-n-caprylyloxyphenyl) formamide, N- (4-n-heptanoyloxyphenyl) formamide, N- [4- (2-ethylhexanoyloxyphenyl)] formamide, N
-[4- (2-methylcaproyloxyphenyl)] formamide, N- (4-n-undecyloxyphenyl) formamide, N- [4- (5-methylcaproyloxyphenyl)] formamide, N- ( 4-methoxyacetyloxyphenyl) formamide, N- [4-
(3,5,5-trimethylhexanoyloxyphenyl)] formamide, N- (4-ethoxyacetyloxyphenyl) formamide, N- (4-n-propoxyacetyloxyphenyl) formamide, N- (4-i
so-propoxyacetyloxyphenyl) formamide, N- [4- (3,3-dimethyl-n-butyryloxyphenyl)] formamide, N- [4- (2,2-dimethyl-n-valeroyloxyphenyl) Formamide, N- [4- (2,2-dimethylpropionyloxyphenyl)] formamide, N- (benzoyloxyphenyl) formamide, N- (phenylacetyloxyphenyl) formamide, N- (phenylpropionyloxyphenyl) formamide, N- (p-toluoyloxyphenyl) formamide, N- (m-toluoyloxyphenyl) formamide, N- (o-toluoyloxyphenyl) formamide, N- (p-tolylacetyloxyphenyl) formamide, N- (p-toluoyloxyphenyl) formamide (M-tolylacetyloxyf Yl) formamide, N-(o-tolyl acetyloxy phenyl) formamide, N-(p
-Anisoyloxyphenyl) formamide, N- (m
-Anisoyloxyphenyl) formamide, N- (o
-Anisoyloxyphenyl) formamide, N- (4
-Ethoxybenzoyloxyphenyl) formamide,
N- (3-ethoxybenzoyloxyphenyl) formamide, N- (4-ethylbenzoyloxyphenyl)
Formamide, N- (4-n-propylbenzoyloxyphenyl) formamide, N- (4-iso-propylbenzoyloxyphenyl) formamide, N- (4
-N-butylbenzoyloxyphenyl) formamide, N- (4-iso-butylbenzoyloxyphenyl) formamide, N- (4-tert-butylbenzoyloxyphenyl) formamide, N- (4-n-pentylbenzoyloxyphenyl) Formamide, N-
(4-n-hexylbenzoyloxyphenyl) formamide, N- (4-n-heptyloxyphenyl) formamide, N- [4- (2-naphthoyloxyphenyl)] formamide, N- [4- (1-naphtho) Yloxyphenyl)] formamide.

The organic substance stabilized by the compound represented by the general formula (1), for example, a cosmetic or a polymer material may further contain a conventional additive such as 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-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-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyl Oxyphenol, 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-
Hydroxyphenyl stearate, bis (3,5-di-
tert-butyl-4-hydroxyphenyl) adipate and mixtures thereof, 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5- Triazine, 2-octylmercapto-4,6-bis (3,5-di-ter
t-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, 1,3,3 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-ter
t-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-ethylidenebis (4,6-di-ter
t-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 can be mentioned.

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-saltyl-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 aminomethylene pyrimidine derivative of the general formula (1) of the present invention is in the range of 330 to 350 nm, and has an ultraviolet absorption capacity comparable to that of a 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 aminomethylenepyrimidine 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. An effective amount may be mixed. 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 products or squalanes. Examples of the mineral oil include paraffin, petrolatum, liquid paraffin, microcrystal wax and the like. Further examples include fine powders such as silicone oil, polyethers, dialkylsiloxanes, starch and talc, and low-boiling hydrocarbons or halogen-containing hydrocarbons used as switchesbout type propellants.

The aminomethylene pyrimidine 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, acetate, isopropanol and the like. As the emulsifier, for example, 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 can be mentioned.

[0032]

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-pivaloyloxyphenylaminomethylene) pyrimidine-2,4,6- (1H,
3H, 5H) -trione [in the general formula (1), R ¹
= R ² = methyl, R ³ = hydrogen atom, R ⁴ = 4-pivaloyloxy]. Phosphorus oxychloride was added to a stirred suspension of barbituric acid 0.020 mol, N- (4-pivaloyloxyphenyl) formamide 0.050 mol and toluene 25 ml.
050 mol is added over 15 minutes. During this addition,
The temperature is kept below 45 ° C. Stirring is continued for 10 minutes, after which 0.030 barbituric acid in 25 ml of toluene is added.
The solution containing the moles is added at 60-65 ° C. over 45 minutes. The reaction mixture is allowed to cool to room temperature with stirring and then added dropwise to 60 ml of 15% sodium hydroxide solution and the reaction is stopped. The organic layer is washed with 20 ml of a saturated saline solution. Separate the organic layer, dry over anhydrous sodium sulfate, filter, and concentrate to give the crude product. Recrystallization from isopropanol gives a purified product with a melting point of 171-172 ° C. Yield 94
%Met.

Ultraviolet absorption spectrum (chloroform): λmax (nm) 347 εmax 34,300 Infrared absorption spectrum: cm ^-1 (KBr) 1722 (lactone C = O), 1708 (ester C = O), 16
58, 1630 (heterocyclic absorption), 1480 (*), 12
00 (C-O-C).

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Example 2 1,3-dimethyl-5- (2-methyl-4-pivaloyloxyphenylaminomethylene) pyrimidine-2,4
6- (1H, 3H, 5H) -trione [In the general formula (1), R ¹ = R ² = methyl, R ³ = 2-methyl, R ⁴ = 4
-Pivaloyloxy]. The same procedure as in Example 1 was repeated except that N- (4-pivaloyloxyphenyl) formamide was replaced with N- (2-methyl-4-pivaloyloxyphenyl) formamide. The purified product has a melting point of 190-191 ° C.
The yield was 93%.

Ultraviolet absorption spectrum: (chloroform) λmax (nm) 350 εmax 27,800 Infrared absorption spectrum: cm ^-1 (KBr) 1728 (lactone C = O), 1708 (ester C = O), 16
60, 1636 (heterocyclic absorption), 1472 (*), 12
48 (C-O-C).

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Example 3 1,3-Dimethyl-5- (4-iso-propionyloxyphenylaminomethylene) pyrimidine-2,4,6
-(1H, 3H, 5H) -trione [in the general formula (1), R ¹ = R ² = methyl, R ³ = hydrogen atom, R ⁴ = iso
-Propionyloxy]. The same procedure as in Example 1 was repeated, except that N- (4-pivaloyloxyphenyl) formamide was replaced with N- (4-iso-propionyloxyphenyl) formamide. The purified product has a melting point of 145.5-147.
The yield was 5 ° C and the yield was 85%.

Ultraviolet absorption spectrum: (chloroform) λmax (nm) 347 εmax 31,800 Infrared absorption spectrum: cm ⁻¹ (KBr) 1728 (lactone C = O), 1708 (ester C = O), 16
60, 1640 (heterocyclic absorption), 1480 (*), 13
08 (C-O-C).

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Example 4 1,3-Dimethyl-5- (4-iso-butyryloxyphenylaminomethylene) pyrimidine-2,4,6-
(1H, 3H, 5H) -trione [in the general formula (1), R ¹ = R ² = methyl, R ³ = hydrogen atom, R ⁴ = iso-
Butyryloxy]. The same procedure as in Example 1 was repeated, except that N- (4-pivaloyloxyphenyl) formamide was replaced with N- (4-iso-butyryloxyphenyl) formamide. The purified product had a melting point of 137 to 138.5 ° C and a yield of 85%.

Ultraviolet absorption spectrum: (chloroform) λmax (nm) 347 εmax 30,000 Infrared absorption spectrum: (KBr) cm ⁻¹ 1760 (lactone C = O), 1708 (ester C = O), 16
60, 1630 (heterocyclic absorption), 1488 (*), 1
265 (C-O-C).

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Example 5 1,3-Dimethyl-5- [4- (3,5,5-trimethylhexanoyloxyphenylaminomethylene)] pyrimidine-2,4,6- (1H, 3H, 5H) -trione Synthesis of [R ¹ = R ² = methyl, R ³ = hydrogen atom, R ⁴ = 3,5,5-trimethylhexanoyloxy in the general formula (1)]. A procedure similar to that of Example 1 was performed, except that N- (4-pivaloyloxyphenyl) formamide was replaced with N- [4- (3,5,5-trimethylhexanoyloxyphenyl)]-formamide. Repeated. The purified product had a melting point of 141.5 to 142.5 ° C and a yield of 75%.

UV absorption spectrum: (chloroform) λmax (nm) 347 εmax 34,100 Infrared absorption spectrum: (KBr) cm ⁻¹ 1760 (lactone C = O), 1708 (ester C = O), 1
660, 1630 (heterocyclic absorption), 1470 (*), 1
308 (C-O-C).

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Example 6 1,3-Dimethyl-5- [4- (2-ethylhexanoyloxyphenylaminomethylene)] pyrimidine-2,
4,6- (1H, 3H, 5H) -trione [In the general formula (1), R ¹ = R ² = methyl, R ³ = hydrogen atom,
R ⁴ = 2-ethylhexanoyloxy]. The same procedure as in Example 1 was repeated except that N- (4-valeroyloxyphenyl) formamide was replaced with N- [4- (2-ethylhexanoyloxyphenyl)] formamide. Purified product has a melting point of 103-1
04 ° C., yield 86%.

UV absorption spectrum: (chloroform) λmax (nm) 347 εmax 36,000 Infrared absorption spectrum: cm ⁻¹ (KBr) 1758 (lactone C = O), 1706 (ester C = O), 16
62, 1636 (heterocyclic absorption), 1480 (*), 13
00 (C-O-C).

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Example 7 1,3-Dimethyl-5- (4-tert-butylbenzoyloxyphenylaminomethylene) pyrimidine-2,
4,6- (1H, 3H, 5H) -trione [In the general formula (1), R ¹ = R ² = methyl, R ³ = hydrogen atom,
R ⁴ = 4-tert-butylbenzoyloxy]. Example 1 except that N- (4-pivaloyloxyphenyl) formamide was replaced with N- (4-tert-butylbenzoyloxyphenyl) formamide.
The same method as described above was repeated. The purified product has a melting point of 196-19.
The yield was 86% at 7 ° C.

UV absorption spectrum: (chloroform) λmax (nm) 347.5 εmax 30,200 Infrared spectrum: cm ⁻¹ (KBr) 1718 (lactone C = O), 1660, 1630 (heterocyclic absorption), 14
78 (*), 1265 (C-O-C).

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Example 8 1,3-Dimethyl-5- [4- (1-naphthoyloxyphenylaminomethylene)] pyrimidine-2,4,6-
Synthesis of (1H, 3H, 5H) -trione [in the general formula (1), R ¹ = R ² = methyl, R ³ = hydrogen atom, R ⁴ = 1-naphthoyloxy]. The same procedure as in Example 1 was repeated, except that N- (4-pivaloyloxyphenyl) formamide was replaced with N- [4- (1-naphthoyloxyphenyl)] formamide. The purified product has a melting point of 208.5 to 209.5.
° C and the yield was 93%.

UV absorption spectrum: (chloroform) λmax (nm) 346.5 εmax 39,900 Infrared absorption spectrum: (KBr) cm ⁻¹ 1720 (lactone C = O and ester C = O), 1680,
1630 (heterocyclic absorption), 1480 (*), 1258
(C-O-C).

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Example 9 1,3-dimethyl-5- [4- (2-naphthoyloxyphenylaminomethylene)] pyrimidine-2,4,6-
Synthesis of (1H, 3H, 5H) -trione [in the general formula (1), R ¹ = R ² = methyl, R ³ = hydrogen atom, R ⁴ = 2-naphthoyloxy]. The same procedure as in Example 1 was repeated except that N- (4-pivaloyloxyphenyl) formamide was replaced with N- (2-naphthoyloxyphenyl) formamide. The purified product has a melting point of 228.5 to 229 ° C and a yield of 91.
%Met.

UV absorption spectrum: (chloroform) λmax (nm) 345.5 εmax 42,700 Infrared absorption spectrum: (KBr) cm ⁻¹ 1730 (lactone C = O and ester C = O), 1678,
1630 (heterocyclic absorption), 1478 (*), 1268
(C-O-C).

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Example 10 Hereinafter, specific examples of the formulation of the external preparation for skin according to the present invention will be described. The compound of Example 6 "1,3-dimethyl-5- [4- (2-ethylhexanoyloxyphenylaminomethylene)] pyrimidine-
2,4,6- (1H, 3H, 5H) -trione "and a serum, as a control, compound" 2,2 ', 4,4'-tetrahydroxybenzophenone "of control example 1, control example A serum containing the compound No. 2 “2-ethylhexyl p-methoxycinnamate” was prepared.

[0052]

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

Confirmation of Sunscreen Effect The serums of the formulation prepared in Example 10 and two comparative examples were respectively applied to the skin, and an effect test of actual use on the beach was conducted. The left and right halves of the sample solution were applied to the backs of 10 men and women, respectively, and the degree of sunburn was examined. The results are shown in Table 2. 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 ×

[0054]

[Table 2]

Example 11 (Light stabilizing effect on polymer substance) Polyethylene powder and polypropylene powder were each 1
After mixing 0.05 parts by weight, 0.2 parts by weight, and 0.5 parts by weight of the sample produced in Example 1 with 00 parts by weight, and thoroughly mixing with a mixer, the cylinder temperature was 200 ° C., and 25 mm The mixture was melt-kneaded with a diameter extruder and granulated. The obtained pellets were heated at 210 ° C. and had a thickness of 0.25 m.
A test piece was prepared by compression molding into a sheet of m. The obtained test piece was punched out into a dumbbell type corresponding to a tensile test. In addition, a test piece for comparison without light stabilizer was prepared and evaluated in the same manner as above.

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 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).

[0058]

[Table 3]

[0059]

(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 3/00 104 C09K 3/00 104B

Claims (5)

[Claims] 1. A compound of the general formula (1) [In the formula, R ¹ and R ² are linear or branched, alkyl group, aralkyl group, cycloalkyl group and independently selected groups from the group consisting of aryl group,, R ³ is
A group selected from the group consisting of a hydrogen atom, a linear or 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. , R ⁴ is an acyloxy group or an aroyloxy group. ] 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 are linear or branched groups independently selected from the group consisting of alkyl groups, aralkyl groups, cycloalkyl groups, and aryl groups. And a 1,3-disubstituted barbituric acid derivative represented by the following general formula (3): [Wherein, R ³ comprises a hydrogen atom, a linear or 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 R ⁴ is an acyloxy group or an aroyloxy group. Wherein the N- (o-, m- or p-substituted phenyl) formamide derivative of the formula (1) is reacted in an organic solvent in the presence of an acid catalyst. Wherein R ¹ , R ² , R ³ and R ⁴ are the same as described above. ] The method for producing an aminomethylenepyrimidine derivative represented by the formula: