JP2001089456A - Acridine derivative and ultraviolet absorber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an excellent ultraviolet absorber less expensive, and having ability capable of efficiently absorbing ultraviolet rays in an UV-A region and an UV-B region at the same time. SOLUTION: An acridine derivative of formula (1) [R1 is H, a 1-6C normal or branched alkyl or acyl; and R2 to R4 are each independently H, a 1-6C normal or branched alkyl, a 1-6C normal or branched alkoxy, a 1-6C normal or branched acyl, a halogen, OH, nitro or a (substituted) amino], and an ultraviolet absorber comprising the compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel acridine derivative. In particular, the present invention relates to an acridine derivative having an ultraviolet absorbing ability and an ultraviolet absorbent using the same.

[0002]

2. Description of the Related Art Ultraviolet rays contained in sunlight are 400 n.
m to 320 nm long wavelength ultraviolet (hereinafter abbreviated as UV-A),
It is classified into a medium wavelength ultraviolet ray (hereinafter abbreviated as UV-B) of 320 to 280 nm and a short wavelength ultraviolet ray (hereinafter abbreviated as UV-C) of 280 nm or less. Among them, short-wavelength ultraviolet rays of 290 nm or less are absorbed by the ozone layer and do not reach the surface of the earth.

[0003] Ultraviolet rays that reach the surface of the earth strongly induce a chemical reaction. Therefore, blending of an ultraviolet absorber into various paints and coating agents has been tried. On the other hand, ultraviolet rays also have various effects on human skin. UV-A also causes a problem of primary blackening, but the effect of UV-B is particularly great, and when a certain amount or more of light is irradiated on human skin, red spots or blisters are formed. It causes problems such as increased melanin formation and pigmentation, and further promotes skin aging in the long term, causing skin cancer and the like.

[0004] Therefore, in order to remove the influence of ultraviolet rays, various ultraviolet absorbers have been developed. As existing ultraviolet absorbers, cinnamic acid derivatives, salicylic acid derivatives, benzophenone derivatives, urocanine derivatives, camphor derivatives, and heterocyclic derivatives are known.

[0005] These UV-A and UV-B absorbers are:
Both were expensive. In addition, in order to obtain a higher ultraviolet absorbing effect, it is necessary to add a large amount of an ultraviolet absorber. However, when these are used, the cost becomes enormous and the formulation is limited. UV-A and UV
In order to simultaneously remove -B, it was necessary to formulate two or more ultraviolet absorbers.

[0006]

Recently, the influence of ultraviolet rays in daily life has become a problem, and there is a strong demand for UV-A and UV-B absorbers having a higher ultraviolet ray absorbing effect and inexpensive UV-A and UV-B absorbers. It had been. However, most of the conventional UV-A and UV-B absorbers are expensive as described above, and have a high UV-A absorption effect and UV-A absorption.
When using a large amount to obtain the B-absorbing effect, there is a problem that the formulation is limited from the viewpoint of cost. Also, when trying to simultaneously obtain UV-A and UV-B absorption capabilities, it was necessary to use two or more ultraviolet absorbers.

The present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is to provide an inexpensive and excellent ultraviolet absorber capable of simultaneously and efficiently absorbing ultraviolet rays in the UV-A and UV-B regions. To provide.

[0008]

Means for Solving the Problems As a result of intensive studies by the present inventors to achieve the above object, the novel UV-A and U-Acridine derivatives synthesized from inexpensive raw materials are excellent.
The present inventors have found that it is an ultraviolet absorber that efficiently absorbs ultraviolet rays in the VB region, and have completed the present invention.

That is, the present invention is as follows. 1. An acridine derivative represented by the following general formula (1).

Embedded image (Wherein R ₁ represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched acyl group having 1 to 6 carbon atoms, and R _{2 to} R ₄ are each independently A hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, a linear or branched acyl group having 1 to 6 carbon atoms, a halogen atom,
It represents a hydroxyl group, a nitro group, or a substituted or unsubstituted amino group. ) 2. An acridine derivative represented by the following formula (2).

Embedded image An ultraviolet absorber comprising the acridine derivative according to 3.1.
Consisting of

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In the compound represented by the general formula (1) according to the present invention, R ₁ is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkyl group having 1 to 6 carbon atoms. Represents a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl,
A linear or branched alkyl group having 1 to 6 carbon atoms such as a pentyl group and a hexyl group; a linear or branched acyl group having 1 to 6 carbon atoms such as a formyl group, an acetyl group, a propionyl group and a butyryl group; Can be R _{2 to} R ₄ are a hydrogen atom,
A linear or branched alkyl group having 1 to 6 carbon atoms, 1 carbon atom
Represents a straight-chain or branched alkoxyl group having 1 to 6 carbon atoms, a straight-chain or branched acyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, a nitro group, a substituted or unsubstituted amino group, and specific examples include a hydrogen atom, Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec
Straight-chain or branched alkyl groups having 1 to 6 carbon atoms, such as -butyl group, t-butyl group, pentyl group, hexyl group, etc., methoxy group, ethoxy group, propoxy group, butoxy group, etc .; A chain or branched alkoxyl group, a formyl group, an acetyl group, a propionyl group, a linear or branched acyl group having 1 to 6 carbon atoms such as a butyryl group, a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, Hydroxyl group, nitro group, amino group, dimethylamino group,
Examples thereof include a diethylamino group.

According to the present invention, R _{2 to} R _{4 in the} general formula (1)
May be the same functional group or different functional groups. R _{2 to} R ₄ are preferably a methyl group, an ethyl group,
Propyl, isopropyl, methoxy, ethoxy, and propoxy.

The acridine derivative of the general formula (1) is
For example, after condensing m-aminophenol and 2-fold mol of substituted cyclohexanone with respect to m-aminophenol, unreacted substituted cyclohexanone is removed from the system by a concentration operation, and the concentrated solution is subjected to a hydrogen acceptor and dehydrogenation. It is produced by performing a dehydrogenation reaction in the presence of a catalyst. Thereafter, it can be isolated by operations such as distillation, crystallization, filtration, and extraction. Further, purification may be performed using a silica gel column or the like.

In the condensation reaction of m-aminophenol and substituted cyclohexanone of the present invention, a reaction solvent may be used or may be used without a solvent. When a solvent is used, for example, toluene, xylene, ter-butanol, phenol And nitrobenzene, but are not particularly limited.

When synthesizing an acridine derivative in the present invention, the form of the condensation reaction may be a reaction in which m-aminophenol and a substituted cyclohexanone are charged in a lump, the reaction is performed while charging either of them in a divided manner, or The reaction may be carried out while charging both parts separately in the solvent.

The condensation temperature of the present invention is not particularly limited, but is in the range of 20 ° C. to 250 ° C., preferably in the range of 80 ° C. to 180 ° C., more preferably 120 ° C. to 160 ° C. Temperature range.

In the present invention, the water produced by the condensation reaction may or may not be removed, but is preferably removed outside the system. When removing the generated water out of the system, the water may be removed by azeotropic dehydration using an azeotropic agent, or only the generated water may be distilled off without using the azeotropic agent. In the case of using an azeotropic agent, the azeotropic agent is not particularly limited,
Examples include toluene, xylene, mesitylene, cumene, ter-butanol and the like.

The condensation reaction of the present invention can be carried out under pressure, under normal pressure, or under reduced pressure, preferably under normal pressure.

The hydrogen acceptor used for synthesizing the acridine derivative according to the present invention is not particularly limited, but includes phenols, nitrobenzenes, styrenes and the like. These may be used simultaneously.

The dehydrogenation catalyst used in synthesizing the acridine derivative according to the present invention is not particularly limited, but Pd / carbon, Pd / alumina, Pt / carbon, Pt / carbon,
t / alumina, Ru / carbon, Ru / alumina, Ni
And the like, preferably Pd / carbon.
When used as an ultraviolet absorber that simultaneously and efficiently absorbs ultraviolet rays in the UV-A and UV-B regions, it may be purified or used without purification.

The acridine derivative thus obtained is a compound having excellent chemical stability and an excellent function of absorbing UV-A and UV-B regions. Specific examples of the compound are shown below.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

Embedded image Although the above compounds are mentioned, the present invention is not limited to the compounds of these specific examples.

In the present invention, in addition to the acridine derivative, other commonly used paints, coatings, cosmetics and pharmaceutical ingredients can be appropriately compounded from below. For example,
Liquid hydrocarbons such as liquid paraffin, squalane, petrolatum, cetyl alcohol, isostearyl alcohol, cetyl 2-ethylhexanoate, 2-octyldodecyl alcohol, glyceryl triisostearate, macadamian nut oil, lanolin, oils and fats, and waxes Oil components such as silicones, surfactants, thickeners, neutralizers, preservatives, bactericides, antioxidants, powder components, pigments, fragrances, other ultraviolet absorbers, medicinal agents, sequestering agents , PH adjusters and the like.

[0027]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to only the examples. Example 1 54.57 g (0.5 mol) of m-aminophenol,
168.26 g of 4-methylcyclohexanone (1.5 m
ol) in a four-necked flask, and heated to 140-1
At 50 ° C., toluene as an azeotropic agent was charged, and azeotropic dehydration was performed at 140 to 150 ° C. while adjusting the amount of toluene so that the azeotropic agent and water circulated. A condensation reaction is carried out for about 10 hours while keeping the temperature at 140 to 150 ° C. until no water is distilled off by azeotropic dehydration, and then cooled to room temperature. It was concentrated using an evaporator. The concentrated solution was added with p-cresol as a hydrogen acceptor for 27 days.
0.35 g (2.5 mol), 5% P as dehydrogenation catalyst
5.46 g of d / carbon (= dry conversion amount) was charged,
The mixture was heated to 195 to 200 ° C. to perform a dehydrogenation reaction for 8 hours. After filtering the dehydrogenation solution to remove 5% Pd / carbon, unreacted p-cresol and the product 4-
Methylcyclohexanone was removed. 300 g of toluene was added to the obtained residue, and then 300 g of methanol was added. The mixture was heated with stirring to form a uniform solution, and then cooled to recrystallize. The recrystallized slurry was filtered and dried to obtain 115.1 g of crystals. HP
Analysis by LC showed a purity of 93.0%. The crystals were further purified using a silica gel column to obtain purified crystals having a purity of 98.8%. In order to determine the structure of the crystal, a spectrum was measured by MS (FIG. 1), IR (FIG. 2), ¹ H-NMR (FIG. 3), and ¹³ C-NMR (FIG. 4). As a result, the acridine derivative was found to have the structure shown below.

Embedded image

Example 2 The acridine derivative synthesized in Example 1 was adjusted to a concentration of 20 ppm with a MeOH solution, and the ultraviolet absorption spectrum was measured.
The compound was found to be a compound that absorbs ultraviolet light having a wavelength of 00 nm and a UV-B region of 280 to 320 nm (FIG. 5).

[0029]

The acridine derivative and the ultraviolet absorber according to the present invention are excellent in chemical stability, and can be used for UV-A and UV.
-It is possible to simultaneously and efficiently absorb ultraviolet light in the B region.

[Brief description of the drawings]

FIG. 1 is a mass spectrum diagram of the compound shown in Example 1.

FIG. 2 is an infrared absorption spectrum of the compound shown in Example 1.

FIG. 3 is a ¹ H-NMR spectrum of the compound shown in Example 1.

FIG. 4 shows the results of the compound shown in Example 1.¹³ C-NMR spec
FIG.

FIG. 5 is an ultraviolet absorption spectrum diagram in Example 2.

Continued on the front page (72) Inventor Akinori Nagatomo 30 Asamuta-cho, Omuta-shi, Fukuoka Mitsui Chemicals, Inc. F-term (reference) 4C034 CK06 4C083 AC851 EE17 4C086 AA01 AA03 BC27 ZA89

Claims (3)

[Claims] 1. An acridine derivative represented by the following general formula (1). Embedded image (Wherein R ₁ represents a hydrogen atom, a linear or branched alkyl group or an acyl group having 1 to 6 carbon atoms, and R _{2 to} R ₄ each independently represent a hydrogen atom, a straight-chain having 1 to 6 carbon atoms. A chain or branched alkyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, a linear or branched acyl group having 1 to 6 carbon atoms,
It represents a halogen atom, a hydroxyl group, a nitro group, or a substituted or unsubstituted amino group. ) 2. An acridine derivative represented by the following general formula (2). Embedded image 3. An ultraviolet absorber comprising the acridine derivative according to claim 1.