JPH11349588A - Production of phthalocyanine derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject phthalocyanine derivative that is useful for an optically recording medium or the like and has excellent resistance to light in high yield under mild reaction conditions by selecting a specific solvent in the synthesis of phthalocyanine derivatives from a phthalic derivative or (its anhydride). SOLUTION: (A) A phthalic anhydride derivative and/or (B) a phthalic acid derivative, (C) a metal or its salt and (D) urea are allowed to react with each other in the presence of (E) a catalyst by using (F) an aromatic compound bearing 3 or more carboxylic ester groups as a solvent to give (G) the objective phthalocyanine derivative. As the component A, is cited a derivative of formula I (R is H, a halogen, nitro; m is an integer of 1-4; the dotted line shows that the benzene ring may be condensed). The component B is a derivative of formula II, while the component G is a derivative of formula III (M is a metal or an oxy metal or the like). According to the present invention, the objective compound can be obtained safely and inexpensively in a shortened time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a phthalocyanine compound. More specifically, the present invention is suitable for optical recording media, optical cards, toners for laser printers, near-infrared absorbing filters, agricultural films for cutting sunlight, automobiles or buildings, etc. A light-shielding film used, a phthalocyanine compound having good light resistance used for safety glasses and the like, with a high yield,
The present invention relates to a method for producing inexpensively with a short reaction time.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a phthalocyanine-based compound from phthalic anhydride, 2,3-naphthalenedicarboxylic anhydride, or a dicarboxylic acid thereof, Inorganica Chimica Acta is used.
44 209-210 (1980), JP-A-61-1
5113, JP-A-63-159386, JP-A-63-1
No. 54767 and JP-A-8-151535 are known. The method described in the first document is a method in which 2,3-naphthalenedicarboxylic anhydride, urea, and zinc acetate are melt-reacted at 310 ° C. under a solvent-free condition, and this method is performed at a high temperature. , The yield is as low as 18%, and the purity is low, so that it is necessary to carry out sublimation purification.
In the second reference, 2,3-naphthalenedicarboxylic anhydride, urea and indium trichloride are heated and refluxed with α-chloronaphthalene as a reaction solvent in the presence of a reaction catalyst such as boric acid and ammonium molybdate. It has low purity, needs to be purified, has high cost of α-chloronaphthalene used as a solvent, and has a problem of environmental hygiene and safety due to its strong odor and toxicity. There are drawbacks. The third document is
A 2,3-naphthalenedicarboxylic anhydride derivative, urea and vanadium trichloride are heated and refluxed with quinoline as a reaction solvent, and the quinoline solvent is also expensive, has strong odor, and has toxicity. Therefore, there is a drawback that there are environmental health and safety problems. The method described in the fourth reference comprises metal sources such as 2,3-naphthalenedicarboxylic acid, urea and anhydrous aluminum chloride,
And ammonium molybdate with 1,3-dimethyl-
210 ° C. using 2-imidazolidinone as a reaction solvent
The reaction is performed at a reaction temperature of about 10 hours, and the reaction time is as long as about 10 hours, and also in this case, the cost of 1,3-dimethyl-2-imidazolidinone used as a solvent is high. . The method described in the fifth document is a method in which phthalic anhydride and a metal source such as urea and copper (I) chloride, and ammonium molybdate are used at a reaction temperature of about 185 ° C. using a phthalic acid ester as a reaction solvent. However, the phthalate used as a solvent has a problem of safety such as environmental hormones.

On the other hand, a method of synthesizing a phthalocyanine compound using trichlorobenzene as a reaction solvent is widely known. JP-A-1-100171 describes a method for synthesizing phthalocyanines, and is disclosed in JP-A-63-154767.
As described in the description, synthesis of naphthalocyanines is also known. However, the phthalocyanine-based compounds obtained by the synthesis method in trichlorobenzene have low purity and need to be purified, and trichlorobenzene has a problem of environmental health and safety because it has a strong odor. There are disadvantages, and there is a disadvantage that the cost of the solvent is high and there is a problem.

[0004]

An object of the present invention is to provide a novel method for producing a phthalocyanine derivative which overcomes the above-mentioned problems.

[0005]

As a result of various studies to achieve the above object, the present inventors have found that the desired compound can be obtained industrially and advantageously by selecting a specific solvent. That is, the present invention provides a reaction of a phthalic anhydride derivative and / or a phthalic acid derivative, a metal and / or a compound thereof, and urea in the presence of a catalyst,
In producing the phthalocyanine derivative, a gist of the production method is characterized in that the reaction is performed using an aromatic compound having three or more carboxylic acid ester groups as a solvent. Preferably, the phthalic anhydride derivative is
The following general formula (I)

[0006]

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(Wherein R is independently a hydrogen atom, a halogen atom, a nitro group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, Represents an aryloxy group which may have, an alkylthio group which may have a substituent, an arylthio group which may have a substituent or an aminocarbonyl group which may have a substituent, m represents an integer of 1 to 4, and the dotted line represents that the benzene ring may be condensed.) is a phthalic anhydride derivative represented by the formula (II)

[0008]

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(In the formula (II), R, m and the dotted line have the same meanings as described above).
The phthalocyanine derivative has the following formula (III)

[0010]

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(In the formula (III), R, m and the dotted line have the same meanings as described above, and M represents a metal, an oxymetal or a metal halide.) The aromatic compound is trimellitic acid ester.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
Examples of the phthalic anhydride derivative as the reaction raw material include a phthalic anhydride derivative and a 2,3-naphthalenedicarboxylic anhydride derivative. Examples of the phthalic acid derivative include phthalic acid and salts thereof (preferably, Na, K And 3,3-naphthalenedicarboxylic acid and salts thereof (preferably, alkali metal salts such as Na and K).

The substituent R in the general formulas (I) to (III) is
Each independently represents a hydrogen atom, a halogen atom, a nitro group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aryloxy group which may have a substituent Represents an alkylthio group which may have a substituent, an arylthio group which may have a substituent or an aminocarbonyl group which may have a substituent, and specific examples thereof include a hydrogen atom, Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; nitro group; alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group; fluoromethyl group An alkyl group substituted with a halogen atom such as, a difluoromethyl group, a trifluoromethyl group; a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group; Alkoxy groups such as methoxy, ethoxy, ethoxy, propoxy, butoxy, methoxy, ethoxy, ethoxy, and ethoxy ethoxy groups; and alkoxy groups, such as methoxy, ethoxy, ethoxy, and ethoxy groups. A benzyloxy group, a phenethyloxy group,
An alkoxy group substituted by a 5- or 6-membered ring such as a tetrahydrofurfuryloxy group or a furfuryloxy group;
An alkoxy group substituted with a halogen atom such as a fluoromethoxy group, a difluoromethoxy group and a trifluoromethoxy group; a phenyloxy group; an alkyl group such as a 4-methylphenyloxy group, a 4-ethylphenyloxy group and a 4-butylphenyloxy group Phenyloxy group substituted by a halogen atom such as 4-chlorophenyloxy group, 4-bromophenyloxy group, and 4-fluorophenyloxy group; 4-methoxyphenyloxy group and 4-ethoxy A phenyloxy group substituted with an alkoxy group such as a phenyloxy group, a 4-butoxyphenyloxy group, a 4-hexyloxyphenyloxy group, a 4-octyloxyphenyloxy group; a 2-naphthyloxy group; a butylthio group, a heptylthio group; Alkylthio such as octylthio group Arylthio groups such as phenylthio group, 4-methylphenylthio group, 2-aminophenylthio group, 4-aminophenylthio group, and 2-naphthylthio group; diethylaminocarbonyl group, di-isopropylaminocarbonyl group, and dibutylaminocarbonyl group ,
An aminocarbonyl group substituted with an alkyl group such as a dipentylaminocarbonyl group, a dihexylaminocarbonyl group, a dioctylaminocarbonyl group, an ethylaminocarbonyl group, a butylaminocarbonyl group, a heptylaminocarbonyl group, an octylaminocarbonyl group; a phenylaminocarbonyl group And an aminocarbonyl group substituted with an aryl group such as a 4-methylphenylcarbonyl group and a 4-butylphenylaminocarbonyl group.

The metals and / or compounds thereof used in the present invention include tin, titanium, cobalt, vanadium,
Silicon, aluminum, chromium, manganese, iron, nickel, copper, zinc, germanium, gallium, molybdenum, indium, antimony, metals such as lead,
Examples of the metal compound include chlorides and fluorides of the above metals,
Examples thereof include halides such as bromide and iodide, oxides, alkoxides, and the like. This metal or metal compound is a metal that forms a complex with the resulting phthalocyanine derivative, and usually a metal compound is used. The amount of the metal and / or the compound thereof is 1 mol of the dicarboxylic acid anhydride of the general formula (I) and / or 1 mol of the dicarboxylic acid compound of the general formula (II). 0.1 mol to 2 mol, and preferably 0.2 mol to 0.4 mol.

[0015] The amount of urea used in the present invention depends on the dicarboxylic acid anhydride of the general formula (I) and / or the general formula (II).
0.1 mol to 10 mol per 1 mol of the dicarboxylic acid compound
Mol, preferably 0.5 mol to 5 mol. As the catalyst used in the present invention, a catalyst generally used for producing a phthalocyanine derivative is used. Specific examples include molybdenum compounds such as ammonium molybdate and molybdenum oxide, titanium compounds such as titanium tetrachloride, titanium sulfate and organic titanate, zirconium compounds such as zirconium tetrachloride, and boric acid. , Ammonium molybdate, molybdenum oxide and the like are preferable.
The amount used is 0.0001 mol to 0.02 mol per 1 mol of the dicarboxylic acid compound and / or dicarboxylic anhydride.
Mole, preferably 0.002 to 0.02 mole. When a compound having catalytic activity is used as the metal compound, the catalyst can serve as both.

As the aromatic compound having three or more carboxylic acid ester groups used as a solvent in the present invention, a triester and a tetraester are usually mentioned, but a triester is preferable. Trialkyl trimellitate (C1 to C8) or triallyl ester, trialkyl hemimellitate (C1
To C8) or a triallyl ester, a trialkyl trimesate (C1 to C8) or a triallyl ester, a trialkyl pyromellitic acid (C1 to C8) or a triallyl ester, and a trialkyl trimellitate is more preferable. .

Examples of the trialkyl trimellitate include trimethyl trimellitate, triethyl trimellitate, tri-n-propyl trimellitate, tri-isopropyl trimellitate and tri-n-butyl trimellitate. Esters, trimellitic acid tri-n-pentyl ester, trimellitic acid tri-n-hexyl ester, trimellitic acid tri-n-heptyl ester, trimellitic acid tri-n-octyl ester, trimellitic acid tris (2-ethylhexyl) ) Esters and the like, and trimellitic esters. Examples of the tetraester include tetraalkyl biphenyltetracarboxylates (C3 to C1).
0) and the like.

In the present invention, the above-mentioned solvents are used, but they may be used as a mixture with other solvents. Examples thereof include halogenated hydrocarbons such as trichlorobenzene, dichlorobenzene, chloronaphthalene, and bromonaphthalene; aromatic hydrocarbons such as alkylbenzene, alkylnaphthalene, and tetralin; ethers such as diphenylether; dimethylsulfoxide, sulfolane, and the like. And the like. The amount of the aromatic compound having three or more carboxylic acid ester groups is 0.5 to 20 parts by weight, preferably 2 to 8 parts by weight, based on 1 part by weight of the phthalic anhydride derivative and / or the phthalic acid derivative. It is.

The reaction temperature and the reaction time of the production method of the present invention can be set arbitrarily. However, if the reaction temperature is made higher than necessary or the reaction time is made longer than necessary, the reaction product is decomposed. Therefore, usually, the reaction temperature is 150
The reaction is carried out at a temperature in the range of -300 ° C, preferably 190-230 ° C, and the reaction time is 1-12 hours, preferably 2-6 hours. After completion of the reaction, the mixture is cooled to about 120 ° C. or lower, and if necessary, a polar solvent such as N-methylpyrrolidone or dimethylformamide is added. The mixture is stirred and filtered, and further, if necessary, N-methylpyrrolidone or dimethylformamide is added. Amide,
The target compound is obtained by washing with ethanol, methanol, acetone or the like. According to the production method of the present invention described above, a phthalocyanine derivative can be produced in good yield, in a short reaction time and at low cost, and the economic advantage is extremely large.

[0020]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

Example 1 13.5 g of 2,3-naphthalenedicarboxylic anhydride, 13.5 g of urea, 6.4 g of tin (II) chloride, 0.5 g of ammonium molybdate and 120 ml of trimellitic acid tri-n-butyl ester Was added to a reaction apparatus, and heated and stirred at 200 ° C. for 4 hours to cause a reaction. 100 ° C after the end of the reaction
After cooling to 120 ml, N-methylpyrrolidone (120 ml) was added, the mixture was stirred at 100 ° C. for 1 hour, and then filtered. The obtained reaction product was washed with N-methylpyrrolidone, water and methanol in that order, dried and dried to obtain 11.4 of dichlorotin naphthalocyanine.
g was obtained.

0.5 g of dichlorotin naphthalocyanine synthesized above, 49.5 g of toluene and 50 ml of glass beads having a particle diameter of 0.8 mm were added to a 300 ml glass container, and treated with a paint conditioner for 8 hours. The mixture was filtered and 1 part of dichlorotin naphthalocyanine was mixed with a polyester resin (manufactured by Toyobo Co., Ltd., Byron 2).
00) 100 parts were added and dissolved to prepare a fine particle dispersion. The solution was dried on a polyester film having a thickness of 100 μm and dried and coated with a bar coater to a thickness of 5 μm to obtain a film containing dichlorotin naphthalocyanine. When the spectral characteristics were measured with a Hitachi spectrophotometer (U-3500), the maximum absorption was 892 nm.

Example 2 In place of 6.4 g of tin (II) chloride of Example 1, an equimolar tin (II) fluoride was used, and the other components were treated in the same manner as in Example 1 to obtain difluorotin sodium. 9.4g phthalocyanine
I got When the maximum absorption was measured in the same manner as in Example 1, it was 944 nm.

Example 3 In place of 6.4 g of tin (II) chloride of Example 1, an equimolar cobalt (II) chloride was used, and the other parts were treated in the same manner as in Example 1 to obtain cobalt naphthalocyanine. 7.2 g were obtained. The maximum absorption was measured in the same manner as in Example 1 and found to be 692 nm.

Example 4 In place of 6.4 g of tin (II) chloride of Example 1, chlorogallium naphthalocyanine was treated in the same manner as in Example 1 except that equimolar gallium (II) chloride was used. To 8.
0 g was obtained. When the maximum absorption was measured in the same manner as in Example 1, it was 778 nm.

Examples 5 to 25 Instead of 2,3-naphthalenedicarboxylic acid anhydride in Example 1, dicarboxylic acid anhydrides shown in the following table, tin (II) chloride instead of metal compounds shown in the following table, trimellit The phthalocyanine compounds shown in the following table were obtained by treating the same compounds as in Example 1 except that the ester compounds shown in the following table were used instead of the acid tri-n-butyl ester. The maximum absorption was measured in the same manner as in Example 1. The results are shown in the table below.

[0027]

[Table 1]

* 1 2,3-Naphthalenedicarboxylic anhydride * 2 Represents vanadyl naphthalocyanine. The same applies hereinafter. * 3 5,8-Dibromo-2,3-naphthalenedicarboxylic anhydride

Comparative Example 1 Trimellitic acid tri-n-butyl ester 1 of Example 1
Instead of 20 ml, 120 ml of trichlorobenzene was used, and the other conditions were treated in the same manner as in Example 1 to obtain 7.5 g of dichlorotin naphthalocyanine. When the maximum absorption was measured in the same manner as in Example 1, the absorption intensity was measured as in Example 1.
Of 60.4%, and the purity was poor.

Comparative Example 2 Trimellitic acid tri-n-butyl ester 1 of Example 2
In place of 20 ml, 120 ml of trichlorobenzene was used, and the others were treated in the same manner as in Example 3 to obtain 5.4 g of difluorotin naphthalocyanine. When the maximum absorption was measured by the same method as in Example 1, the absorption intensity was 60.0% of Example 2, and the purity was inferior.

Comparative Example 3 Trimellitic acid tri-n-butyl ester 1 of Example 8
In place of 20 ml, 120 ml of trichlorobenzene was used, and otherwise the same treatment as in Example 13 was carried out to obtain 6.8 g of dichlorotin phthalocyanine. When the maximum absorption was measured by the same method as in Example 1, it was 696 nm. However, the absorption intensity was 67.6% of Example 8, and the purity was inferior.

[0032]

According to the method for producing a phthalocyanine derivative of the present invention, it is used for an optical recording medium, an optical card, a toner for a laser printer, a near-infrared absorbing filter, an agricultural film for cutting sunlight, an automobile or a building. A phthalocyanine compound having good light resistance, which is used for a light-shielding film, protective glasses, and the like, can be produced in good yield, with a short reaction time, and at low cost.

Claims (3)

[Claims] 1. A phthalocyanine derivative is produced by reacting a phthalic anhydride derivative and / or a phthalic acid derivative, a metal and / or a compound thereof, and urea in the presence of a catalyst. A production method, characterized in that the reaction is carried out by using the aromatic compound as described above as a solvent. 2. The phthalic anhydride derivative is represented by the following general formula (I): (Wherein, R independently represents a hydrogen atom, a halogen atom, a nitro group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, Represents an aryloxy group which may be substituted, an alkylthio group which may have a substituent, an arylthio group which may have a substituent or an aminocarbonyl group which may have a substituent, and m is 1 And the dotted line represents that the benzene ring may be condensed.), And the phthalic acid derivative is represented by the formula (II): (In the formula (II), R, m and the dotted line have the same meanings as described above.) The phthalocyanine derivative is represented by the following formula (III): 2. The method according to claim 1, wherein in formula (III), R, m and the dotted line have the same meaning as described above, and M represents a metal, an oxymetal or a metal halide. 3. The method according to claim 1, wherein the aromatic compound having three or more carboxylic acid ester groups is trimellitic acid ester.