JP2001089457A - Acridine derivative and ultraviolet ray absorbent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet absorber less expensive and having excellent UV-B absorbing ability. SOLUTION: An acridine derivative of formula (1) [R1 and R2 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 R3 is H, a 1-6C normal or branched alkyl or a 1-6C normal or branched acyl], 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] 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.
When they are used, the cost is enormous and the prescription is limited.

[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. Thus, the present 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 and R ₂ independently represent a hydrogen atom and a carbon atom of 1
To 6 linear or branched alkyl groups, 1 to 6 carbon atoms
Linear or branched alkoxy group, linear or branched acyl group having from 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, a nitro group and a substituted or unsubstituted amino group, R ₃ is a hydrogen atom and a carbon number 1 A straight-chain or branched alkyl group having 1 to 6 carbon atoms; and a straight-chain or branched acyl group having 1 to 6 carbon atoms. ) 2. An acridine derivative represented by the following general formula (2).

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

[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 and R ₂ represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a straight-chain or branched alkyl group having 1 to 6 carbon atoms. A chain or branched alkoxyl group, a linear or branched acyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, a nitro group,
Represents a substituted or unsubstituted 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, and t.
A straight-chain or branched alkyl group having 1 to 6 carbon atoms such as butyl group, pentyl group, hexyl group and cyclohexyl group, a straight-chain or branched alkyl group having 1 to 6 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group; A branched or 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, a hydroxyl group, Nitro group, amino group, dimethylamino group,
Examples thereof include a diethylamino group.

R ₃ 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 specific examples thereof include a hydrogen atom, a methyl group and an ethyl group. , Propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group,
Examples thereof include a linear or branched alkyl group having 1 to 6 carbon atoms such as a pentyl group and a hexyl group, and 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. . The functional groups of R ₁ and R _{2 in} the general formula (1) according to the present invention may be the same functional groups,
Different functional groups may be used. R ₁ and R ₂ are preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a methoxy group, an ethoxy group, and a propoxy group.

As a method for producing the acridine derivative of the general formula (1), for example, 3-condensed aniline and 2-fold mol of the substituted cyclohexanone with respect to the 3-substituted aniline are condensed, and then the unreacted substituted cyclohexanone is concentrated. It is produced by removing the concentrated solution out of the system by operation and 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 3-substituted aniline and the 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 the 3-substituted aniline and the substituted cyclohexanone are charged in a lump, the reaction is carried out by dropping either, or the reaction may be carried out in a solvent. The reaction may be carried out while dropping both.

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 in synthesizing the acridine derivative of the present invention is not particularly limited, but includes phenols, nitrobenzenes, styrenes, etc., and one or more of these may be used simultaneously. You may.

The dehydrogenation catalyst used for synthesizing the acridine derivative of the present invention is not particularly limited.
d / carbon, Pd / alumina, Pt / carbon, Pt
/ Alumina, Ru / carbon, Ru / alumina, Ni, etc., and preferably Pd / carbon.

When used as a UV-B absorber, it may be used after purification or 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.

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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 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.

[0046]

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,
112.17 g of 4-methylcyclohexanone (1.0 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. P-Cresol, a hydrogen acceptor, was added to the concentrate at 21.
6.28 g (2.0 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 recrystallization slurry was filtered and dried to obtain 81.5 g of crystals. Analysis by HPLC revealed a purity of 90.0%. The crystals were further purified using a silica gel column to give a purity of 9
8.5% of pure crystals were obtained. To determine the structure of the crystal, MS (FIG. 1), IR (FIG. 2), ¹ H-NMR (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).

[0048]

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 is a ¹³ C-NMR spectrum of the compound shown in Example 1.

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

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Masaru Wada F-term (reference) 4C034 CK07 4C083 AC851 AC852 BB51 EE12 EE17 4C086 AA01 AA02 AA03 BC27 MA01 MA04 NA14 ZA89 ZB26

Claims (3)

[Claims] 1. An acridine derivative represented by the following general formula (1). Embedded image (Wherein R ₁ and R ₂ independently represent a hydrogen atom and a carbon atom of 1
To 6 linear or branched alkyl groups, 1 to 6 carbon atoms
Linear or branched alkoxy group, linear or branched acyl group having from 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, a nitro group and a substituted or unsubstituted amino group, R ₃ is a hydrogen atom and a carbon number 1 A straight-chain or branched alkyl group having 1 to 6 carbon atoms; and a straight-chain or branched acyl group having 1 to 6 carbon atoms. ) 2. An acridine derivative represented by the following formula (2). Embedded image 3. An ultraviolet absorber comprising the acridine derivative according to claim 1.