JPH1059974A - Production of phthalocyanine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject compound having high purity from a nitrate of 1-amino-3-iminoisoindolenine compound by a simple process. SOLUTION: The objective phothalocyanine compound of formula I [the ring A is a (substituted) benzene or naphthalene ring; B is two H atoms, a metal or a metal compound] is produced by reacting 1-4 kinds of 1-amino-3- iminoisoindolenine compound nitrates of formula II with a base or a base and a metallic compound at 100-200 deg.C for 1-24hr. The base is e.g. 1,8- diazabicyclo[5.4.0]-7-undecene and the metallic compound is e.g. CuCl or CoCl2 . The compound of the formula I is useful as dyes, pigments, photoelectric functional materials, information recording materials, etc.

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 and a naphthalocyanine compound (hereinafter collectively referred to as a phthalocyanine compound) useful as a dye, a pigment, a photoelectric functional material and an information recording material.

[0002]

2. Description of the Related Art It is well known that phthalocyanine compounds exhibit high fastness to heat, light, acids and alkalis and have high absorption coefficients. In addition, since the semiconductor laser has absorption in the near-infrared region, its use in the information recording field has been expanding in conjunction with the rapid development of semiconductor lasers having a dominant wavelength in that region.

[0003] With respect to the method for producing phthalocyanine compounds,
Various methods have been used since the 1930s. A method in which a phthalonitrile compound and a metal halide are heated in an inert solvent such as quinoline or trichlorobenzene (Barrett et al., J. Chem. Soc., 1936, 1719-1736);
A method in which a phthalic anhydride derivative and a metal salt are heated in urea in the presence of a catalyst such as ammonium molybdate (PB
85172, FIAT FinalReport 1313, Feb. 1, 1948), o
-A method of heating a cyanobenzamide derivative and a metal compound (U.S. Pat. No. 2,025,791; 1935
A method of reacting a metal salt with a 1,3-diiminoisoindoline compound in a hydrophilic solvent (December 31, December)
JP-A-8-22117 and JP-A-49-53624) are known. In particular, it is well known as the Wyler method and is a production method advantageous in terms of availability of raw materials and cost.

However, the processes (1) to (4) have a problem in that it is difficult to obtain a high-purity phthalocyanine compound. Therefore, when a target compound having extremely low solubility is obtained, it is fatal in that simple solvent purification cannot be used as a purification means. In the above method, a phthalocyanine compound having high purity can be obtained without performing a purification operation, but there is a problem in availability of the 1,3-diiminoisoindoline compound as a raw material. The 1,3-diiminoisoindoline compound is generally converted from a readily available substituted phthalic anhydride into a number of reaction steps (from anhydride to imide, amide, dinitrile, 1,1).
It is expensive and has low availability, which is disadvantageous in practical use because it is produced through four steps of a 3-diiminoisoindoline compound).

[0005]

An object of the present invention is to provide a method for producing a phthalocyanine compound with high purity by a simple operation.

[0006]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, the above-mentioned problems are solved by producing a phthalocyanine compound via a specific intermediate. This led to the completion of the present invention.

That is, the present invention provides a compound represented by the general formula (1):

[0008]

Embedded image (In the formula (1), ring A is independently a benzene ring which may have a substituent or a naphthalene ring which may have a substituent, and these substituents are an alkyl group, an alkoxy group, an aryloxy group , An alkylthio group, an arylthio group or a hydroxyl group, and B represents two hydrogen atoms, a metal atom or a metal compound.) In the method for producing a phthalocyanine compound represented by the general formula (2)

[0009]

Embedded image (In formula (2), ring A has the same meaning as ring A in formula (1).) 1 to 4 types of nitrates of a 1-amino-3-iminoisoindolenin compound represented by the following formula: Alternatively, the present invention relates to a method for producing a phthalocyanine compound of the general formula (1), which is produced from a base and a metal compound.

Further, the present invention provides the compounds represented by the following general formulas (3) to (8):

[0011]

Embedded image (In the formulas (3) to (8), the ring A has the same meaning as the ring A in the general formula (1).) In the presence of a catalyst, at least one phthalic acid derivative selected from the group consisting of ammonium nitrate and urea is used. The reaction is carried out to produce a nitrate of the 1-amino-3-iminoisoindolenin compound of the general formula (2), and then 1 to 4 nitrates of the 1-amino-3-iminoisoindolenin compound are added to a base. Alternatively, the present invention relates to a method for producing a phthalocyanine compound represented by the general formula (1), wherein a base and a metal compound are reacted.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The production method of the present invention will be specifically described below.

The present invention relates to the production of a phthalocyanine compound represented by the general formula (1), wherein 1 to 4 nitrates of a 1-amino-3-iminoisoindolenin compound represented by the general formula (2) are used. , A base, or a base and a metal compound.

Ring A in formulas (1) and (2)
Is a benzene ring which may have a substituent or a naphthalene ring which may have a substituent. These substituents include an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and a hydroxyl group.

The alkyl portion of the alkyl group, alkoxy group and alkylthio group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms.

The aryl moiety of the aryloxy group and the arylthio group is particularly preferably a phenyl group or a naphthyl group. The phenyl group or the naphthyl group further has an alkyl group having 1 to 8 carbon atoms or a halogen atom as a substituent. Is also good.

Specific examples of the substituent of the ring A in the general formula (1) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Alkyl groups such as dodecyl group, hexadecyl group, octadecyl group, methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, decyloxy group, hexa Aryloxy groups such as decyloxy group, octadecyloxy group, etc., phenoxy group, 4-t-butylphenoxy group, 4-ethylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, methylthio group, ethylthio Group, propylthio group, butylthio group, pentylthio group, hexyl Alkylthio groups such as thio group, heptylthio group, octylthio group, nonylthio group, decylthio group, dodecylthio group, hexadecylthio group, octadecylthio group, arylthio groups such as phenylthio group, 4-t-butylphenylthio group, naphthylthio group, and hydroxyl group Is mentioned.

B in the general formula (1) is two hydrogen atoms, a metal atom or a metal compound, and examples of the metal compound include a metal halide, a metal oxide and a metal hydroxide.

Specific examples of B include copper, silver, zinc, cadmium, barium, mercury, gallium, tin, lead, vanadium, antimony, chromium, molybdenum, manganese, cobalt, nickel, rhodium, palladium, osmium,
Metal atoms such as platinum, aluminum monochloride, indium monochloride, vanadium dichloride, metal halides such as titanium dichloride, metal oxides such as vanadyl and titanyl, silicon dihydroxide, tin dihydroxide, manganese hydroxide, Metal hydroxides such as aluminum hydroxide can be mentioned.

Preferred specific examples of the phthalocyanine compound represented by the general formula (1) which can be produced by the present invention include metal-free phthalocyanine, copper phthalocyanine, aluminum bromide phthalocyanine, indium bromide phthalocyanine,
Unsubstituted phthalocyanines such as titanyl phthalocyanine, vanadyl phthalocyanine, manganese phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine, palladium phthalocyanine, platinum phthalocyanine, tetramethyl metal-free phthalocyanine, tetramethyl copper phthalocyanine, tetra-t-butyl cobalt phthalocyanine, tetra-t-pentyl nickel Phthalocyanine, alkyl-substituted phthalocyanines such as tetra-t-octylvanadyl phthalocyanine, tetramethoxy metal-free phthalocyanine, tetraethoxypalladium phthalocyanine, tetrabutoxytitanyl phthalocyanine, tetrapentyloxy copper phthalocyanine, tetrahexyloxy platinum phthalocyanine, tetraoctyloxy cobalt phthalocyanine, octa Methoxy banana Alkoxy-substituted phthalocyanines such as luphthalocyanine and hexadecaethoxy copper phthalocyanine; aryloxy-substituted phthalocyanines such as octaphenoxyzinc phthalocyanine and hexadecanaphthyloxyvanadyl phthalocyanine; tetraethylthionickel phthalocyanine, octabutylthiopalladium phthalocyanine and hexadecaoctylthiocopper Alkylthio-substituted phthalocyanines such as phthalocyanine, tetraphenylthiomanganese phthalocyanine, indium octaphenylthiobromide phthalocyanine, hexadeca (4-t-butylphenylthio) copper phthalocyanine, arylthio-substituted phthalocyanines such as hexadecanaphthylthiovanadyl phthalocyanine, tetrahydroxy Metal-free phthalocyanine, octahydroxy copper phthalocyanine Hydroxy-substituted phthalocyanines such as emissions,

Metal-free naphthalocyanine, copper naphthalocyanine, aluminum naphthalocyanine bromide, indium naphthalocyanine bromide, titanyl naphthalocyanine, vanadyl naphthalocyanine, manganese naphthalocyanine,
Unsubstituted naphthalocyanines such as cobalt naphthalocyanine, nickel naphthalocyanine, palladium naphthalocyanine, and platinum naphthalocyanine; alkyl substitution such as tetra-t-butyl copper naphthalocyanine, tetra-t-pentylvanadyl naphthalocyanine, and tetra-t-octyl cobalt naphthalocyanine And naphthalocyanines.

In the process of the present invention, 2 to 4 nitrates of a 1-amino-3-iminoisoindoline compound represented by the general formula (2) are used and reacted with a base or a base and a metal compound. A phthalocyanine compound of the general formula (1) in which a benzene ring and a naphthalene ring are mixed in one molecule and / or a phthalocyanine compound of the general formula (1) having a different substituent on each ring A can also be produced. Examples of these phthalocyanine compounds include, for example, JP-A-63-57289 and JP-A-63-25092.
JP, JP-A-63-139789, JP-A-2-
The compounds disclosed in JP-A-240167 and the like can be mentioned.

In the production method of the present invention, first, a nitrate of a 1-amino-3-iminoisoindoline compound represented by the general formula (2) is formed.

The nitrate of the general formula (2) is preferably at least one compound selected from the following formulas (3) to (8), an inert solvent if necessary in the presence of ammonium nitrate, urea and a catalyst. It is manufactured by heating and stirring using

[0025]

Embedded image (In the formulas (3) to (8), the ring A has the same meaning as the ring A in the formula (1).)

In the nitrate formation reaction, the reaction temperature is 1
The temperature is preferably from 40 to 200 ° C, and the reaction time is preferably from 2 to 48 hours.

The molar ratio of ammonium nitrate to the compounds of the formulas (3) to (8) is preferably 1 to 4 times.

As the catalyst, ammonium molybdate is preferably used, and the molar ratio thereof is 0.0001 to 0.1 times the molar amount of the compound of the formulas (3) to (8).
Preferably it is 0.0001 to 0.001 times mol.

The molar ratio of urea used is determined by the formulas (3) to (8).
2 to 20 moles, preferably 4 to 10 moles with respect to the compound of
It is twice the mole.

An inert solvent can be used to smooth the stirring and to prevent the contents from rising due to foaming. Examples of the inert solvent that can be used include chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene, and chloronaphthalene.

The phthalocyanine compound of the general formula (1) is
It is produced from 1 to 4 nitrates of the 1-amino-3-iminoisoindolenin compound of the general formula (2) and a base or a base and a metal compound.

In the reaction for producing a phthalocyanine compound from this nitrate, a base and a metal compound (unnecessary when a metal-free phthalocyanine compound is obtained) are added to the reaction mixture at the time of producing the nitrate of the general formula (2) described above. Alternatively, once the nitrate of the general formula (2) is isolated, it may be reacted with a base, or a base and a metal compound, if necessary, using a solvent.

In the reaction for forming a phthalocyanine compound from the nitrate of the formula (2), the reaction temperature is 100 to 20.
0 ° C is preferable, and 120 to 185 ° C is more preferable.

The reaction time is preferably 1 to 24 hours.

As the base, DBU (1,8-diazabicyclo [5.4.0] -7-undecene), DABCO
(1,4-diazabicyclo [2.2.2] octane),
Organic bases such as 1,5-diazabicyclo [4.3.0] -5-nonene and metal alcoholates such as sodium methylate, sodium ethylate, sodium t-butylate, potassium methylate, potassium ethylate, potassium t-butylate Kinds are available.

The amount of the base used is 1 to 10 times the molar amount of the nitrate of the general formula (2).

As the metal compound, copper, silver, zinc, cadmium, barium, mercury, aluminum, gallium, indium, titanium, tin, lead, vanadium, antimony, chromium, molybdenum, manganese, cobalt, nickel, rhodium, palladium, Halides such as osmium and platinum, oxides, oxychlorides, carboxylates, carbonyl complexes and acetylacetone complexes can be used.

The amount of the metal compound used is 0.20 to 0.30 times the molar amount of the nitrate of the general formula (2).

Solvents that can be used in the reaction for forming a phthalocyanine compound from nitrate include 1-butanol, 1-butanol and 1-butanol, in addition to inert solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene and chloronaphthalene used in the production of nitrate. Pentanol,
Normal alcohols such as 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, sulfolane, dimethylsulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl- Polar solvents such as 2-imidazolidinone are exemplified. In particular, when 1-butanol, 1-pentanol, and 1-octanol are used, a phthalocyanine compound with extremely high purity can be obtained.

After the reaction, impurities can be removed by subjecting the obtained phthalocyanine compound to solvent washing, alkali washing, acid washing, water washing, and the like as necessary. When nitrate is isolated and used for producing a phthalocyanine compound, a high-purity phthalocyanine compound is often obtained only by washing with a solvent.

The phthalocyanine compound obtained by the present production method has a high purity, and has an extremely higher gram extinction coefficient than those obtained by other methods.

[0042]

The present invention will be described more specifically with reference to the following examples.

Example 1 14.8 g of phthalic anhydride
(0.1 mol), urea 30 g, ammonium nitrate 16
g (0.2 mol), ammonium molybdate 0.1 g
Was added and stirred at 145 to 165 ° C for 6 hours. After cooling,
70 ml of 2-ethylhexanol, 30.4 g of DBU
(0.2 mol) and 2.49 g (0.025 mol) of cuprous chloride were added and reacted at 180 to 190 ° C. for 5 hours.
After cooling, the precipitate was collected by filtration, 5% aqueous sodium hydroxide solution,
Washing was performed three times sequentially with 30% each of a 5% aqueous hydrochloric acid solution and water. After drying, 10.4 g (yield 72%) of a blue powder was obtained.

The product was confirmed to be the desired copper phthalocyanine by elemental analysis and infrared absorption spectrum.

[0045]

[Table 1]

Examples 2 to 7 Example 1 was repeated except that phthalic acid derivatives and metal compounds as raw materials shown in Table 2 were used.
By performing the same operation as described above, corresponding phthalocyanine compounds were obtained. Table 2 summarizes the relative intensity ratios of yield, powder, and gram extinction coefficient.

The relative intensity ratio of the gram extinction coefficient is obtained by assuming that the gram extinction coefficient at the absorption maximum at the longest wavelength side of the phthalocyanine compound obtained by the Wyler method from the same phthalic acid derivative used in this example is 1. Shows the intensity ratio of the gram extinction coefficient of the phthalocyanine compound obtained by the production method according to the present example. The higher the value, the higher the purity.

[0048]

[Table 2] In Examples 1 to 7, Ring A of the phthalic acid derivative is a benzene ring.

Example 8 Naphthalene-2,3-dicarboxylic anhydride (54.9 g, 0.3 mol) was mixed with urea (90 g).
(1.5 mol), 48 g of ammonium nitrate, 0.3 g (0.24 mmol) of ammonium molybdate and 300 ml of orthodichlorobenzene were added, and 150 to 155 ° C.
, And the precipitate was collected by filtration at 60 ° C. After washing with 200 ml of methanol and then with 200 ml of water,
Dried, nitrate of benzodiiminoisoindoline 67.
1 g (86.6% yield) was obtained as white crystals. It was identified as the target 1,3-diimino-5,6-benzoisoindoline nitrate from the elemental analysis value, the mass analysis value and the infrared absorption spectrum. FIG. 1 shows the infrared absorption spectrum of this compound.

The melting point of this compound is 170-170.4
° C.

[0051]

[Table 3] Mass analysis M / e = 195 (not out in the form of nitrate) Infrared absorption spectrum ^{_{ν NH = 3320cm -1, ν C}} = N = 1660cm -1, ν
_NO3 = 1350cm ^-1

The thus obtained 1,3-diimino-
2,5.8 g of 5,6-benzoisoindoline nitrate (0.
1 mol) in 80 ml of n-octanol and DB
U39.1 g (0.26 mol), vanadyl chloride 4.33
g (0.025 mol) were sequentially added and reacted at 120 to 125 ° C. for 10 hours. After cooling to room temperature, the precipitate was collected by filtration and washed with 20 ml of methanol. After drying, 15.38 g (yield 79.4%) of green-blue powder was obtained. It was identified as vanadyl naphthalocyanine from the elemental analysis values and the infrared absorption spectrum.

The gram extinction coefficient of this compound in sulfuric acid was 9.85 × 10 ⁴ ml / g · cm.

[0054]

[Table 4]

(Comparative Example 1) 6.0 g (0.03 mol) of naphthalene-2,3-dicarboxylic anhydride was mixed with 13.7 of urea.
g (0.23 mol), ammonium molybdate tetrahydrate 0.60 g, sulfolane 30 g, vanadyl trichloride 1.
73 g (0.01 mol) were added successively, and 185 to 190
The reaction was performed at 5 ° C. for 5 hours. After cooling to 60 ° C, methanol 1
00 ml was added and refluxed for 30 minutes. The precipitate was collected by filtration while hot, washed twice with 10 ml of methanol, and dried.
8.55 g of a dark green powder were obtained. Its gram extinction coefficient in sulfuric acid is 5.03 × 10 ⁴ ml / g · c
m.

The relative intensity ratio of the vanadyl naphthalocyanine obtained in Example 8 to the gram extinction coefficient obtained with Comparative Example 1 was 1.96.

[0057]

As is clear from Table 2 and the relative intensity ratio of the gram extinction coefficient in Example 8, the phthalocyanine compound could be obtained with high purity by the method of the present invention.

[Brief description of the drawings]

FIG. 1 shows 1,3-diimino-5,6 synthesized in Example 8.
-It is an infrared absorption spectrum of benzoisoindoline nitrate.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Ryu Ooi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemicals Co., Ltd.

Claims (2)

[Claims] 1. A compound of the general formula (1) (In the formula (1), ring A is independently a benzene ring which may have a substituent or a naphthalene ring which may have a substituent, and the substituent is an alkyl group, an alkoxy group, or an aryloxy group. , An alkylthio group, an arylthio group or a hydroxyl group, and B represents two hydrogen atoms, a metal atom or a metal compound.) In the method for producing a phthalocyanine compound represented by the general formula (2): ] (In formula (2), ring A has the same meaning as ring A in formula (1).) 1 to 4 types of nitrates of a 1-amino-3-iminoisoindolenin compound represented by the following formula: Or a method for producing a phthalocyanine compound of the general formula (1), characterized in that it is produced from a base and a metal compound. 2. General formulas (3) to (8) (In the formulas (3) to (8), the ring A is a benzene ring which may have a substituent or a naphthalene ring which may have a substituent, and these substituents are an alkyl group, an alkoxy group, and an aryl group. An oxy group, an alkylthio group, an arylthio group, or a hydroxyl group) is reacted with ammonium nitrate and urea in the presence of a catalyst to give a compound of the general formula (2) ] (In formula (2), ring A has the same meaning as ring A in formula (1).) A nitrate of a 1-amino-3-iminoisoindolenin compound represented by the formula: -3-iminoisoindolenine compound nitrate 1 to
The method for producing a phthalocyanine compound according to claim 1, wherein the four kinds are reacted with a base or a base and a metal compound.