JP2001081092A - Acridine derivative and ultraviolet light absorber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new acridine derivative which has excellent chemical stability, has a function for absorbing light in the medium wavelength ultraviolet light (UV-B) region, and is useful as an inexpensive ultraviolet light absorber. SOLUTION: An acridine derivative of formula I (R1 to R4 are each H, a1 to 6C alkyl, a 1 to 6C alkoxy or the like), for example, a compound of formula II. The compound of formula I can be obtained, for example, by condensing m-aminophenol with an excessive amount of a substituted cyclohexanone (for example, 4-methylcyclohexanone) preferably at 20 to 250 deg.C, removing the non- reacted substituted cyclohexanone outside the system by a concentration operation, and subjecting the concentrated solution to a dehydrogenation reaction in the presence of a hydrogen acceptor (for example, p-cresol) and a dehydrogenation catalyst (for example, Pd/C). The product may be isolated by an operation such as distillation, crystallization, filtration or extraction, and may further be purified using a silica gel column, or the like.

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] Among these, all UV-B absorbers are expensive. Moreover, in order to obtain a higher ultraviolet absorption effect, it becomes necessary to mix a large amount of an ultraviolet absorber.
If they are used, the cost becomes enormous and the prescription is restricted.

[0006]

Recently, the influence of ultraviolet rays in daily life has also become a problem, and there has been a strong demand for an inexpensive UV-B absorber having a higher ultraviolet absorbing effect. However, most of the conventional UV-B absorbers are expensive as described above, and when attempting to use a large amount to obtain a high UV-B absorption effect,
There was a problem that the prescription was restricted from the viewpoint of cost.

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 ultraviolet absorber having excellent UV-B absorption.

[0008]

Means for Solving the Problems As a result of intensive studies by the present inventors to achieve the above object, the present inventors have found that a novel acridine derivative synthesized from an inexpensive raw material has excellent UV-B absorption. The invention has been completed.

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

Embedded image (Wherein R ₁ to R ₄ independently represent 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, Represents a linear or branched acyl group, a halogen atom, a hydroxyl group, a nitro group, or a substituted or unsubstituted amino group.) An acridine derivative represented by the following general 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, in the formula, R ₁ to R ₄ represent a hydrogen atom, a carbon number of 1 to 6;
Linear or branched alkyl group, linear or branched alkoxyl group having 1 to 6 carbon atoms, linear or branched acyl group having 1 to 6 carbon atoms, halogen atom, hydroxyl group, nitro group, substituted or unsubstituted Represents an amino group, and specific examples include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, and a hexyl group. -C6 straight-chain or branched alkyl, methoxy, ethoxy, propoxy, butoxy and other straight-chain or branched alkoxyl groups having 1 to 6 carbon atoms, formyl group, acetyl group, propionyl group, butyryl group, etc. A linear or branched acyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, a hydroxyl group,
Examples thereof include a nitro group, an amino group, a dimethylamino group, and a diethylamino group. The functional groups R ₁ to R _{4 in} the general formula (1) according to the present invention may be all the same functional groups or 2 to 4 different functional groups. R ₁ to R ₄
Is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a methoxy group, an ethoxy group, or a propoxy group.

As a method for producing the acridine derivative of the general formula (1), for example, after condensing m-aminophenol and an excessively substituted cyclohexanone, the unreacted substituted cyclohexanone is removed from the system by a concentration operation. The concentrate is produced by performing a dehydrogenation reaction in the presence of a hydrogen acceptor and a dehydrogenation 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 the m-aminophenol and the substituted cyclohexanone of the present invention, the reaction solvent may be used with or without a solvent. When a solvent is used, for example, toluene, xylene, ter-butanol, phenol And nitrobenzene, but are not particularly limited.

In the synthesis of 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 reaction 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 increased pressure, normal pressure or reduced pressure, and is preferably performed under normal pressure.

The hydrogen acceptor used in synthesizing the acridine derivative of the present invention includes, but is not particularly limited to, phenols, nitrobenzenes, styrenes, etc., and one or more of these may be used simultaneously. Is also good.

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
Etc., but it is preferable to use Pd / carbon.

The acridine derivative according to the present invention is UV-B
When used as an absorbent, 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 the UV-B region. 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]

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[0026]

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

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

[0028]

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,
336.51 g of 4-methylcyclohexanone (3.0 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 mixed with p-cresol, a hydrogen acceptor, for 32 hours.
4.42 g (3.0 mol), 5% P as dehydrogenation catalyst
5.46 g of d / C (= dry conversion amount) was charged, and 195
The mixture was heated to 200 ° C. to perform a dehydrogenation reaction for 8 hours. After filtering the dehydrogenation reaction solution to remove 5% Pd / C, unreacted p-cresol and produced 4-methylcyclohexanone were removed by distillation under reduced pressure. 300 parts of toluene were added to the obtained residue.
Then, 300 g of MeOH was added, and the mixture was heated with stirring to form a uniform solution, and then cooled to recrystallize. The recrystallization slurry was filtered and dried to obtain 168.9 g of crystals. Analysis by HPLC revealed a purity of 99.5%. MS (FIG. 1), IR (FIG. 2), ¹ H-NMR to determine the structure of the crystal
(FIG. 3), The spectrum was measured by ¹³ C-NMR (FIG. 4). As a result, the acridine derivative was found to have the structure shown below.

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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 of 80 nm (FIG. 5).

[0030]

The acridine derivative and ultraviolet absorber according to the present invention have excellent chemical stability and can efficiently absorb ultraviolet rays in the UV-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 chart in Example 2.

Claims (3)

[Claims] 1. An acridine derivative represented by the following general formula (1). Embedded image (Wherein R ₁ to R ₄ independently represent 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, Represents a linear or branched acyl group, 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.