JPH075529B2 - Naphthoquinone-2,3-dicarboxylic acid esters and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a novel naphthoquinone-2,3-which is useful for coloring a filter or a polymer material for controlling light in the region from visible light to near infrared light. The present invention relates to dicarboxylic acid esters and a method for producing the same.

<Prior Art> A naphthoquinone compound has been studied for a long time because a colored compound having a wide range of color tone can be obtained by introducing various substituents. However, although the naphthoquinone compounds known so far are colored, many studies have been made as pigments, but their use as dyes is still greatly limited due to their low light resistance. There is.

However, due to the recent development of the electronic industry,
Light in the so-called near-infrared region up to 0 nm has begun to be used for sensors used for monitoring, identification, etc. or for communication and control, so filters, markings, recording materials, etc. of compounds that absorb this near-infrared region There has been an increasing interest in using it for.

<Problems to be Solved by the Invention> Since naphthoquinone compounds have long been known for bathochromic properties, research has recently been conducted again for this type of application. For example, general formula (A) [In the formula, X represents an arbitrary substituent. ] 2,3
-Dicyano-1,4-naphthoquinones are known to have absorption in the near infrared region.

However, 2,3-dicyano-1,4-naphthoquinones generally tend to be poorly soluble, and are not suitable for use in processing by a solution coating method, and improvements have been desired.

<Means for Solving Problems> Accordingly, the inventors of the present invention have conducted intensive studies for a naphthoquinone compound that exhibits good solubility from visible light to the near infrared region, and as a result, specific 1,4-naphthoquinone-2 was obtained. It has been found that 3,3-dicarboxylic acid esters are suitable for the purpose. That is, the present invention has the general formula (I) [In the formula, R ¹ is an alkyl group or cycloalkyl group having 1 to 5 carbon atoms which may be substituted with a methoxy group, R ² is a phenyloxy group, an alkyl group, an alkoxy group, a hydroxy group, a halogen or a dialkylamine group. , Phenylamine group, hydroxyalkyl group, methylthio group, CF ₃ group, SO ₂
CH ₃ group, an alkoxycarbonyl phenyl group which may be substituted with a group, R ³ represents a group represented by hydrogen or a substituent R ^2, R ² and R ³ may be different even in the same . ]
And naphthoquinone-2,3-dicarboxylic acid esters represented by

More specifically, in the compound represented by the general formula (I), the group represented by R ¹ is a linear, branched or cyclic alkyl group, for example, a methyl group, an ethyl group,
n-propyl group, i-propyl group, n-butyl group, i-
A butyl group, a tert-butyl group, an n-pentyl group, a cyclohexyl group and the like, and these groups may be further substituted with a methoxy group in some cases. The phenyl group of R ² or R ³ may have the above-mentioned substituent, and the number and position of this substituent are arbitrary. Also, different substituents may exist on the same phenyl group.

The compound represented by the general formula (I) can be produced by the following two methods.

That is, (a) general formula (II) [In the formula, R ¹ represents the above meaning. ] 5-aminonaphthoquinone 2,3-dicarboxylic acid ester represented by the following general formula (III) NH ₂ -R ² (III) [In the formula, R ² represents the above meaning. ] It is made to react with the aromatic amine shown by these in an inert solvent.

(B) General formula (V) [In the formula, R ¹ and R ² each have the above-mentioned meaning. A naphthoquinone-2,3-dicarboxylic acid ester represented by the following general formula (VI) NH ₂ -R ⁴ (VI) [in the formula, R ⁴ represents a phenyloxy group, an alkyl group, an alkoxy group, a hydroxy group, a halogen group] , A dialkylamine group,
It represents a phenyl group which may be substituted with a phenylamine group, a hydroxyalkyl group, a methylthio group, a CF ₃ group, a SO ₂ CH ₃ group or an alkoxycarbonyl group. R ⁴ may be the same as or different from R ² in the general formula (V). ] It is made to react with the aromatic amine shown by these in an inert solvent.

In the method (a), R ³ in the general formula (I) is a hydrogen atom, that is, naphthoquinone-2,3-dicarboxylic acid esters represented by the general formula (V), or R ² and R ³ are the same. It is an advantageous method for producing what is an aromatic group. On the other hand, the method (b) is the same as R ² in the general formula (I).
This is an advantageous method for producing in good yield those in which R ³ is different aromatic groups.

More specifically, for example, in the case of the methods (a) and (b), it can be performed as follows.

(A-1) The 5-aminonaphthoquinone-2,3-dicarboxylic acid ester represented by the above general formula (II) is prepared by adding at least an inert solvent sufficient to form a slurry thereof and the above general formula (III). ) Is added at room temperature to 2
The reaction is performed by heating to 00 ° C, preferably 60 to 150 ° C.

At this time, the aromatic amine represented by the general formula (III) is replaced with 5-aminonaphthoquinone-2,3-
When used in an amount of not more than 0.6 mol ratio, preferably 0.40 to 0.55 mol ratio, based on the dicarboxylic acid ester, the formula (V) is mainly used. [In the formula, R ¹ and R ² each have the above-mentioned meaning. ] The naphthoquinone-2,3-dicarboxylic acid ester shown by these is obtained. When the aromatic amine represented by the general formula (III) is used in an amount of 0.8 molar ratio or more, preferably 1.0 molar ratio or more, general formula (VIII) [In the formula, R ¹ and R ² each have the above-mentioned meaning. ] The naphthoquinone-2,3-dicarboxylic acid ester shown by these is obtained.

(A-2) In the above method (a-1), the aromatic amine represented by the general formula (II) may be optionally dissolved or diluted in an inert solvent, and the reaction may be carried out by dropwise addition. Good.

(B-1) A naphthoquinone-2,3-dicarboxylic acid ester represented by the general formula (V), an inert solvent sufficient to form a slurry thereof, and a compound represented by the general formula (V
The aromatic amine represented by I) is added, and the mixture is heated at room temperature to 200 ° C, preferably 60 to 150 ° C to react.

At this time, the aromatic amine represented by the general formula (VI) is
The naphthoquinone-2,3-dicarboxylic acid ester represented by the general formula (V) is preferably used in a molar ratio of 1.0 or more.

Further, in the aromatic amine represented by the general formula (VI), R ⁴ is naphthoquinone represented by the general formula (V).
When it is the same as R ² in the 2,3-dicarboxylic acid ester, the naphthoquinone-2,3-dicarboxylic acid ester represented by the general formula (VIII) is obtained, and R ⁴ is different from R ^2. Has the general formula (IX) [In the formula (IX), R ¹ and R ² each have the above-mentioned meaning,
R ⁵ has the same meaning as R ⁴ . However, R ² and R ⁵ are not the same. ] The naphthoquinone-2,3-dicarboxylic acid ester shown by these is obtained.

As the inert solvent that can be used in the reaction, for example,
Lower alcohols such as methanol, ethanol, propanol and butanol, polyhydric alcohols such as ethylene glycol and glycerin or derivatives thereof, ethyl acetate,
In addition to esters such as butyl acetate, ethers such as dioxane and tetrahydrofuran, aromatic solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane and the like can be used.

When an acid is added to an inert solvent to carry out the reaction, the reactivity is good, and it is effective in improving the yield and shortening the reaction time. Examples of such acids include acetic acid, formic acid, propionic acid, lactic acid,
Aliphatic carboxylic acids such as oxalic acid, citric acid, tartaric acid, monochloroacetic acid, trichloroacetic acid and trichloroacetic acid, aromatic carboxylic acids such as benzoic acid, salicylic acid and phthalic acid, sulfonic acids such as benzenesulfonic acid and toluenesulfonic acid, and further Inorganic acids such as phosphoric acid, sulfuric acid and hydrochloric acid can also be used. Among them, liquid lower carboxylic acids can be used as a reaction solvent by themselves, and good results can be obtained.

The amount of the inert solvent used may be an amount sufficient to make the naphthoquinone compound represented by the general formula (II) or the general formula (V) into a slurry, but it is usually a weight ratio to the naphthoquinone compound. It is easy to operate if the amount is about 10 to 50 times. If necessary, two or more inert solvents may be mixed and used.

The reaction temperature is as described above, but if the boiling point of the inert solvent used in the reaction is within the above reaction temperature range, usually reflux heating may be performed.

The reaction time varies greatly depending on the type of solvent used in the reaction, the type and amount of added acid, the reaction temperature and the like. It also depends on the type of aromatic amine used, but usually 0.5
You can choose the conditions that range from hours to over ten hours.

After the reaction is completed, the target product is separated by a commonly used separation and take-out operation. The simplest way is to cool down to room temperature and pass.

The naphthoquinone-2,3-dicarboxylic acid ester represented by the general formula (I) thus obtained is a dark green to black crystal or solid and is usually well dissolved in toluene, ethyl acetate, chloroform, dimethylformamide, etc. It has a green color.

<Effect of the Invention> As described above, according to the present invention, useful and novel naphthoquinone-2,3-dicarboxylic acid esters represented by the general formula (I) can be produced.

<Examples> Specific examples will be described below. In the examples, "parts" means "parts by weight" unless otherwise specified.

Example 1 5-amino-1,4-naphthoquinone-2,3-in 930 parts of acetic acid
Dicarboxylic acid diethyl ester 46.5 parts and p-phenetidine 10.1 parts were added, and the mixture was heated under reflux (about 118 ° C.) for 2 hours. After cooling, it was washed with a small amount of methanol and then with water. Dry cake at 60 ℃
I got 30.2 parts. This crude cake was recrystallized twice using 10 times ethanol to obtain 24.5 parts of the naphthoquinone compound represented by the formula (1).

Molecular ion mass by mass spectrometer; 452 Elemental analysis results mp167-169 ° C λmax 680 nm ε = 1.35 × 10 ⁴ (acetone) Example 2 5-amino-1,4-naphthoquinone-2,3-in 635 parts of acetic acid
31.7 parts of dicarboxylic acid diethyl ester and 20.6 parts of p-phenetidine were added, and the mixture was heated under reflux for 4 hours. After cooling, it was filtered and washed with a small amount of methanol and then with water. Drying was performed at 60 ° C., and 22.0 parts of a black solid crude cake was performed. This crude cake was recrystallized twice with 10 times ethanol to obtain 17.4 parts of the naphthoquinone compound represented by the formula (2).

Molecular ion mass by mass spectrometer; 572 Elemental analysis results mp 141-143 ° C. λmax 705 nm, ε = 1.41 × 10 ⁴ (acetone) Example 3 5-amino-1,4-naphthoquinone-2,3-in 104 parts of acetic acid
Dicarboxylic acid diethyl ester (5.2 parts) and p-aminodiphenylamine (6.0 parts) were added, and the mixture was heated under reflux for 4 hours.
After cooling, it was filtered and washed with a small amount of methanol and then with water. When dried at 60 ° C., 3.8 parts of a black solid crude cake was obtained. The crude cake was dissolved in chloroform, the tar component was removed through a short silica gel column, and then chloroform was distilled off. Then, heat treatment was carried out in 100 parts of n-hexane and further 60 parts of methanol to obtain 1.7 parts of a purified product of the naphthoquinone compound of the formula (3).

Molecular ion mass by mass spectrometer; 666 Elemental analysis results mp214 to 216 ° C. λmax 710 nm, ε = 1.69 × 10 ⁴ (acetone) Example 4 5-amino-1,4-naphthoquinone-2,3-in 96.0 parts of acetic acid
Dicarboxylic acid diethyl ester (4.8 parts) and p-aminodiphenylamine (1.4 parts) were added, and the mixture was heated under reflux for 0.5 hours.
After cooling, it was filtered and washed with a small amount of methanol and then with water. When dried at 60 ° C, 3.2 parts of a black solid crude cake was obtained.

The crude cake was recrystallized twice with 10 times ethanol to obtain a purified product of the naphthoquinone compound represented by the formula (4).

Molecular ion mass by mass spectrometer; 422 Elemental analysis results mp177-179 ° C. λmax 683 nm, ε = 1.58 × 10 ⁴ (acetone) Example 5 In the same manner as in Example 1, the naphthoquinone compounds shown in Table 1 are obtained.

Example 6 The naphthoquinone compound shown in Table 2 is obtained in the same manner as in Example 2.

Example 7 To 100 parts of acetic acid, 4.5 parts of the naphthoquinone compound of the formula (1) obtained in Example 1 and 2.8 parts of p-phenetidine were added and heated under reflux for 4 hours. After cooling, it was filtered and washed with a small amount of methanol and then with water. After drying at 60 ° C., 4.7 parts of a naphthoquinone compound represented by the formula (2) was obtained.

Example 8 In Example 7, instead of p-phenetidine, p-
4.2 parts of a naphthoquinone compound represented by the formula (39) was obtained in the same manner as in Example 7 except that 2.2 parts of toluidine was used.

Example 9 5-amino-1,4-in 1200 parts methanol and 400 parts acetic acid
Naphthoquinone-2,3-dicarboxylic acid diethyl ester 32
Parts were added and heated until reflux began. Then p-phenetidine dissolved in 50 parts of methanol while maintaining the reflux.
6.9 parts was added dropwise over 4 hours. After completion of the dropping, the mixture is heated under reflux for another 16 hours and then cooled to room temperature. After cooling, it was filtered and washed with a small amount of methanol and then with water. After drying at 60 ° C., 19.9 parts of a black solid crude cake of the naphthoquinone compound represented by the formula (1) was obtained. Then, the same operation as in Example 1 was carried out to obtain a purified product 1 of the naphthoquinone compound of the formula (1).
I got 6.3 copies.

Claims (3)

[Claims] 1. The following general formula (I): [In the formula, R ¹ is an alkyl group or cycloalkyl group having 1 to 5 carbon atoms which may be substituted with a methoxy group, R ² is a phenyloxy group, an alkyl group, an alkoxy group, a hydroxy group, a halogen or a dialkylamine group. , Phenylamine group, hydroxyalkyl group, methylthio group, CF ₃ group, SO ₂
CH ₃ group, alkoxycarbonyl optionally substituted phenyl group with a group, R ³ represents a substituent represented by hydrogen or a substituent R ^2, even if R ² and R ³ are optionally substituted by one or more identical Good. ] Naphthoquinone-2,3-dicarboxylic acid ester shown by these. 2. The following general formula (II) [In the formula, R ¹ represents an alkyl group having 1 to 5 carbon atoms or a cycloalkyl group which may be substituted with a methoxy group. And 5-amino-naphthoquinone-2,3-dicarboxylic acid esters represented by] the general formula ^{_{(III) NH 2 -R 2 (}} III) wherein, R ² is a phenyl group, an alkyl group, an alkoxy group, hydroxy Group, halogen, dialkylamine group,
It represents a phenyl group which may be substituted with a phenylamine group, a hydroxyalkyl group, a methylthio group, a CF ₃ group, a SO ₂ CH ₃ group or an alkoxycarbonyl group. ] The aromatic amine represented by the following general formula (IV) characterized by reacting in an inert solvent [In the formula, R ¹ is an alkyl group or cycloalkyl group having 1 to 5 carbon atoms which may be substituted with a methoxy group, R ² is a phenyloxy group, an alkyl group, an alkoxy group, a hydroxy group, a halogen or a dialkylamine group. , Phenylamine group, hydroxyalkyl group, methylthio group, CF ₃ group, SO ₂
A CH ₃ group, a phenyl group which may be substituted with an alkoxycarbonyl group, and R ³ ′ represent hydrogen or the substituent represented by the substituent R ² . ] The manufacturing method of naphthoquinone-2,3-dicarboxylic acid ester shown by these. 3. The following general formula (V) [In the formula, R ¹ is an alkyl group or cycloalkyl group having 1 to 5 carbon atoms which may be substituted with a methoxy group, R ² is a phenyloxy group, an alkyl group, an alkoxy group, a hydroxy group, a halogen or a dialkylamine group. , Phenylamine group, hydroxyalkyl group, methylthio group, CF ₃ group, SO ₂
It represents a CH ₃ group or a phenyl group which may be substituted with an alkoxycarbonyl group. ] Naphthoquinone-2 represented by
3-dicarboxylic acid esters and general formula (VI) NH ₂ —R ⁴ (VI) [wherein, R ⁴ is a phenyloxy group, an alkyl group, an alkoxy group, a hydroxy group, a halogen, a dialkylamine group,
It represents a phenyl group which may be substituted with a phenylamine group, a hydroxyalkyl group, a methylthio group, a CF ₃ group, a SO ₂ CH ₃ group or an alkoxycarbonyl group. R ⁴ may be the same as or different from R ² in the general formula (V). ] The aromatic amine represented by the following general formula (VII) characterized by reacting in an inert solvent [In the formula, R ¹ is an alkyl group or cycloalkyl group having 1 to 5 carbon atoms which may be substituted with a methoxy group, R ² and R ⁴ are each independently a phenyloxy group, an alkyl group, an alkoxy group, a hydroxy group. Represents a phenyl group which may be substituted with a halogen, a dialkylamine group, a phenylamine group, a hydroxyalkyl group, a methylthio group, a CF ₃ group, a SO ₂ CH ₃ group or an alkoxycarbonyl group. ] The manufacturing method of naphthoquinone-2,3-dicarboxylic acid ester shown by these.