JPH0753831B2 - Method for producing naphthalocyanines - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing naphthalocyanines, and an object of the present invention is to provide a method for producing naphthalocyanines with high yield and high purity under mild conditions. It is in.

2. Description of the Related Art Conventionally, as a method for producing naphthalocyanines from 2,3-naphthalenedicarboxylic acids or / and their acid anhydrides, for example, there is a method described in Reference Inorganica Chimica Acta 44 209-210.
(1980) and the method described in Russian Patent No. 899,607 are known.

The method described in the former document is to react 2,3-naphthalenedicarboxylic acid, urea and zinc acetate under melting condition at a reaction temperature of 310 ° C. This method requires high temperature, and the yield is as low as 18% and impurities. However, there is a drawback in that sublimation purification is required in many cases.

The method described in the latter Russian patent includes, for example, 2,3-naphthalenedicarboxylic anhydride, aluminum chloride, ammonium molybdate as a catalyst and ammonium sulfate at a reaction temperature of 260 to 270 ° C. for 4 to 5 hours under melting in urea. It is to react. However, this method requires cooling after completion of the reaction, solidification, and then suspending in a dilute hydrochloric acid aqueous solution, resulting in poor workability, low yield of 20 to 50%, and high reaction temperature. is there.

On the other hand, a method for producing naphthalocyanines from 2,3-naphthalenedicarboxylic acids or / and their acid anhydrides using an organic solvent as a solvent is also known. Then, a method using, for example, trichlorobenzene, chloronaphthalene, polyethylene glycol or the like as an organic solvent is known. However, when trichlorobenzene or chloronaphthalene is used as the solvent, the reaction product is likely to be tar-like due to poor compatibility of the reaction intermediate or product with the solvent, and the operability is poor, and the purity of the obtained naphthalocyanines is low. And the purification process is complicated.

When polyethylene glycol is used as a solvent, there is a drawback that the yield is low.

Problems to be Solved by the Invention A method for producing naphthalocyanines having a high yield and a high purity under mild reaction conditions using 2,3-naphthalenedicarboxylic acids or / and acid anhydrides thereof as starting materials is desired. ing.

Means for Solving the Problems The present inventors have achieved the present invention as a result of extensive studies to solve the above-mentioned problems. That is, the present invention has the formula (I) (Wherein, X in the formula (I) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a nitro group or a carboxyl group, and m represents an integer of 1 to 6, respectively). Acid or / and formula (II) (Wherein X and m have the same meaning as described above in formula (II)), 2,3-naphthalenedicarboxylic anhydride, a metal or / and a compound thereof and urea are reacted in the presence of a catalyst to give a compound of the formula (III) (In the formula (III), X and m have the same meanings as described above, and M represents a metal, a metal oxide, or a metal halide).
-Providing a method for producing naphthalocyanines, which comprises carrying out the reaction using dimethyl-2-imidazolidinone.

The present invention will be described in detail below. The general formulas (I) to (II
In I), X represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a nitro group or a carboxyl group, and specific examples thereof include a hydrogen atom; a halogen atom such as a chlorine atom and a bromine atom; methyl. Group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, alkyl group such as octyl group; aryl group such as phenyl group; methoxy group, ethoxy group,
Examples thereof include alkoxy groups such as propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group and octyloxy group; nitro group; and carboxyl group.

Examples of the metal or its compound used as a reaction reagent in the present invention include aluminum, titanium, vanadium,
Chromium, manganese, iron, cobalt, nickel, copper, zinc, potassium, germanium, molybdenum, ruthenium, palladium, silver, cadmium, indium, tin,
Examples thereof include antimony, lead or chlorides, oxides, sulfates, acetates or alkoxides of these metals. The amount of these metals or / and their compounds used is 0.5 to 1.5 mol, preferably 0.8 to 1.2 mol, per 4 mol of 2,3-naphthalenedicarboxylic acid or / and its acid anhydride.

The catalyst used in the present invention may be any of various known catalysts generally used in the production of naphthalocyanines, but specifically, molybdenum compounds such as ammonium molybdate and molybdenum oxide are preferable, and the amount thereof is 0.001 to 0.1 mol per 4 mol of 2,3-naphthalenedicarboxylic acid or / and its acid anhydride, preferably
It is 0.01 to 0.05 mol.

The amount of urea used in the present invention is 2 to 20 mol in terms of ammonia per 4 mol of 2,3-naphthalenedicarboxylic acid or / and its anhydride.

1,3-dimethyl-2-used in the method of the present invention
Imidazolidinone (DMI) functions as a solvent, and in the method of the present invention, DMI may be mixed with another solvent. Examples of other solvents include aromatic hydrocarbons such as alkylbenzene, alkylnaphthalene and tetralin; aliphatic hydrocarbons such as decane and dodecane; alicyclic hydrocarbons such as alkylcyclohexane, decalin and alkyldecalin; nitrobenzene, Nitro compounds such as o-nitrotoluene; halogenated hydrocarbons such as trichlorobenzene, dichlorobenzene, chloronaphthalene, bromonaphthalene; alcohols such as octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, glycerin; diphenyl ether. Ethers such as; sulfur compounds such as sulfolane, dimethyl sulfoxide,
The amount used is 80 or less by weight relative to DMI100, preferably 50.
It is below the weight ratio. And the amount of the mixed solvent consisting of DMI alone or DMI and the solvent as described above is usually 2,3-naphthalenedicarboxylic acid or / and its acid anhydride.
The amount is preferably 0.5 to 10 times, more preferably 2 to 5 times (weight ratio).

In the production method of the present invention, 150 to 250 ° C., preferably 19
The heating may be performed at a temperature of 0 to 220 ° C. for 1 to 25 hours, preferably 5 to 15 hours. When the reaction is completed, the reaction mixture is cooled, passed through a conventional method, and if necessary, washed with dimethylformamide, ethanol, methanol, acetone or the like to obtain the desired compound. The naphthalocyanines obtained by the method of the present invention have sufficient purity, but may be purified by a sublimation method or the like if desired.

According to the production method of the present invention as described above, it is possible to obtain high-purity naphthalocyanines in good yield under mild conditions from 2,3-naphthalenedicarboxylic acid or / and its acid anhydride and other raw materials. The economic advantages of the invention are enormous.

The naphthalocyanines obtained by the method of the present invention are useful as near infrared absorbers, photoconductive agents, colorants, catalysts for chemical reactions and the like.

EXAMPLES The present invention will be described in more detail by way of examples. In addition, the middle part of an Example means a weight part.

Example 1 120 parts of anhydrous 2,3-naphthalenedicarboxylic acid, 144 parts of urea,
20 parts of anhydrous aluminum chloride, 2 parts of ammonium molybdate, and 400 parts of DMI were charged into a reactor and heated and stirred at 210 ° C. for 10 hours. After completion of the reaction, the reaction mixture was cooled, and the precipitated aluminum naphthalocyanine was suctioned off, thoroughly washed with dimethylformamide, acetone and then methanol, and dried. Yield 92 parts, elemental analysis value and structural formula of this product are shown below.

(C ₄₈ H ₂₄ N ₈ ClAl) C (%) H (%) N (%) Cl (%) Al (%) Theoretical value 74.37 3.12 14.45 4.57 3.48 Measured value 74.29 3.10 14.52 4.45 3.40 Visible spectrum maximum absorption wavelength 774 nm log ε5.30 measured as a dimethylformamide solution Example 2 80 parts of zinc naphthalocyanine was prepared in the same manner as in Example 1 except that anhydrous zinc sulfate was used instead of the anhydrous aluminum chloride in Example 1. Obtained. Elemental analysis values and structural formulas are shown below.

(C ₄₈ H ₂₄ N ₈ Zn) C (%) H (%) N (%) Zn (%) Theoretical value 74.08 3.10 14.39 8.40 Measured value 73.89 3.05 14.45 8.31 Visible spectrum maximum absorption wavelength 758 nm log ε5.36 measured as a dimethylformamide solution Example 3 Aluminum naphthalocyanine was prepared in the same manner as in Example 1 except that DMI 400 parts and trichlorobenzene 200 parts were used instead of DMI 400 parts in Example 1. 85 parts (having the same structure as the compound obtained in Example 1) were obtained.

Example 4 130 parts of 2,3-naphthalenedicarboxylic acid, 144 parts of urea, 51 parts of titanium n-butoxide, 2 parts of ammonium molybdate and 400 parts of DMI were charged into a reactor and heated and stirred at 190 ° C. for 10 hours. After completion of the reaction, the reaction mixture was cooled and the precipitated titanylnaphthalocyanine was suctioned off, thoroughly washed with dimethylformamide acetone and then with methanol, and dried. Yield 87
Department. The elemental analysis values and structural formula of this product are shown below.

(C ₄₈ H ₂₄ N ₈ OTi) C (%) H (%) N (%) Ti (%) Theoretical value 74.23 3.11 14.42 6.16 Measured value 74.41 3.10 14.32 6.05 Visible spectrum measured as a dimethylformamide solution maximum absorption wavelength 784 nm log ε3.9 Comparative Example anhydrous 2,3-naphthalenedicarboxylic acid 120 parts, urea 144 parts,
20 parts of anhydrous aluminum chloride, 2 parts of ammonium molybdate, and 400 parts of trichlorobenzene were charged into a reactor and heated and stirred at 210 ° C. for 15 hours. After completion of the reaction, the reaction mixture was cooled and the resulting product was suctioned off, thoroughly washed with dimethylformamide, acetone and then methanol, and dried. yield
17 parts, elemental analysis values of this product are shown below.

(C ₄₈ N ₂₄ N ₈ ClAl) C (%) H (%) N (%) Cl (%) Al (%) Theoretical value 74.37 3.12 14.45 4.57 3.48 Actual value 39.14 3.06 8.66 3.31 14.04 Alumina phthalocyanine is hardly obtained It was

Effects of the Invention By carrying out the reaction using 1,3-dimethyl-2-imidazolidinone (DMI), it becomes possible to produce naphthalocyanines having a high yield and a high purity under mild conditions.

Claims (1)

[Claims] 1. A formula (I) (Wherein, X in the formula (I) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a nitro group or a carboxyl group, and m represents an integer of 1 to 6, respectively). Acid or / and formula (II) (In the formula (II), X and m have the same meanings as described above), 2,3-naphthalenedicarboxylic anhydride, a metal or / and a compound thereof and urea are reacted in the presence of a catalyst to give a compound of the formula (III) (In the formula (III), X and m have the same meanings as described above, and M represents a metal, a metal oxide, or a metal halide).
-A method for producing naphthalocyanines, characterized in that the reaction is carried out using dimethyl-2-imidazolidinone.