JPH11116836A - Production of metallophthalocyanine derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a metallophthalocyanine derivative having good solubility to an organic solvent by controlling a ratio of a structural isomer in a product. SOLUTION: This method for producing metallophthalocyanine derivative comprises adding a metal or a metal salt in a state in which an oligomer of a substituted phthalonitrile is produced, in a method for producing a phthalocyanine derivative by subjecting a substituted phthalonitrile to cyclization reaction in the presence of a base and an alcoholic solvent. The addition of the metal or metal salt is preferably carried out when residual amount of unreacted substituted phthalonitrile is <=80 wt.%. Thereby, the content ratio of a structural isomer having low solubility can be lowered.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a metal phthalocyanine derivative having good solubility and stability in an organic solvent and easy to use for various uses.

[0002]

2. Description of the Related Art Phthalocyanine compounds are used as pigments which have been widely used in the past, as well as dyes for optical recording,
It is also attracting attention as a raw material for color filter dyes, photoelectric conversion elements, electrophotographic photoreceptors, organic semiconductor elements, catalysts, gas sensors, color filters, deodorants, medicines, agricultural chemicals, and the like. Optical discs, especially compact discs (CDs), have particular use as recording film materials for write-once CDs.

Conventionally, cyanine dyes have been mainly used as organic dyes for write-once CDs. Although this cyanine dye is excellent in that it has a large extinction coefficient, it has the problem of poor light fastness. In order to improve this, a method of incorporating a light stabilizer has been adopted, but a sufficient effect has not been obtained. On the other hand, phthalocyanine dyes are expected to be applied to write-once CDs as dye materials instead of cyanine dyes, as described above, because of their excellent light resistance and high stability.

[0004]

When a phthalocyanine does not have a substituent, phthalocyanine is hardly soluble or insoluble in most organic solvents, and is extremely poor in processability. Therefore, phthalocyanine is used as a recording film material for CD after a substituent is introduced into the phthalocyanine to improve solubility in a solvent. Examples of the substituent introduced into phthalocyanine include a long-chain alkyl group or alkoxyl group, an ester group, a polyether group, and a thioether group.

[0005] Phthalocyanines having such substituents introduced at, for example, the α-position include the following four structural isomers P
There are 1, P2, P3 and P4. Note that R in the formula represents a substituent.

[0006]

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Hitherto, phthalocyanine has been produced by a template method. According to this production method, a metal or a metal salt is added during the preparation of a starting material, so that the substituent R is coordinated in a swastika type with little steric hindrance. P1 was mainly generated. However, since this swastika type P1 has good crystallinity,
When applied as a recording film for a CD, there are problems that it is crystallized in a coating solution or becomes granular on the applied recording film to cause an error.

Accordingly, the present invention provides four structural isomers P1,
P2, P3 and P other than P1 among P2, P3 and P4
An object of the present invention is to provide a method for producing a metal phthalocyanine derivative which can further improve the solubility and stability of the phthalocyanine derivative in an organic solvent by selectively increasing the content ratio of 4.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that, instead of using substituted phthalonitrile and a metal or a metal salt as starting materials at the same time, an oligomer of substituted phthalonitrile is produced from the substituted phthalonitrile and a base. After that, by adding a metal or a metal salt and reacting,
The present inventors have found that they are not affected by the steric hindrance of the substituent in the process of producing the target substance, and completed the present invention.

That is, the present invention provides a method for producing a phthalocyanine derivative by subjecting a substituted phthalonitrile to a cyclization reaction in the presence of a base and an alcoholic solvent, wherein a metal or a metal salt is added in a state where an oligomer of the substituted phthalonitrile is formed. And a method for producing a metal phthalocyanine derivative.

In the present invention, the term "substituted phthalonitrile oligomer" means a substituted phthalonitrile dimer, trimer or tetramer.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The substituted phthalonitrile used in the present invention is not particularly limited as long as it has at least one substituent on the aromatic ring which does not inhibit the reaction. Can be used.

Examples of the substituent in the substituted phthalonitrile include an alkyl group, an alkoxyl group, an acyl group, an amino group, a mercapto group, an amide group, a halogen atom, a nitro group and a hydroxyl group. Further, these substituents may be further partially substituted, and in this case, as the substituent, an alkyl group, an alkoxyl group, an acyl group, an amino group, a mercapto group, an amide group, a halogen atom, a nitro group, Examples include a hydroxyl group and the like, specific examples of which include a 2-ethylhexyloxy group,
2,2,2,2 ', 2', 2'-hexafluorocumyloxy group, 1-phenyl-2,2,2-trifluoroethoxy group and the like can be mentioned.

As such substituted phthalonitriles,
The following general formula (1):

[0015]

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[Wherein, X represents a hydrogen atom or an aliphatic, alicyclic or aromatic group having 1 to 36 carbon atoms which may have a substituent. Or the following general formula (2):

[0017]

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[In the formula, Y represents a hydrogen atom or an aliphatic, alicyclic or aromatic group having 1 to 36 carbon atoms which may have a substituent. ] Is preferable.

The base used in the present invention is not particularly limited, and known bases can be used. As this base, DBU (1,8-diazabicyclo [5.4.
0] -7-undecene), DBN (1,5-diazabicyclo [4.
3.0] -5-Nonene), among which DBU is preferable.

The amount of the base used in the present invention is preferably from 1 to 1000 mol%, particularly preferably from 10 to 1000 mol%, based on the substituted phthalonitrile, in order to secure an appropriate reaction time.
0 to 500 mol%.

The alcoholic solvents used in the present invention include methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol, pentanol, hexanol, heptanol, octanol, ethylhexanol, decanol, Dodecanol, tetradecanol, hexadecanol, octadecanol, pentaerythritol, sorbitol, glycerin, polyglycerins,
Phenol, dihydroxybenzene, trihydroxybenzene and the like can be mentioned. Among them, pentanol and phenol are preferable, and pentanol is particularly preferable. These alcohol solvents can be used alone or in combination of two or more.

The amount of the solvent used in the present invention is preferably 0.1 to 200 times the weight of the substituted phthalonitrile, particularly preferably 1 to 5 times, in order to carry out a smooth reaction.
It is 0 times the amount.

In the method for producing a metal phthalocyanine derivative of the present invention, when the above-mentioned substituted phthalonitrile is subjected to a cyclization reaction in the presence of a base and an alcohol-based solvent, an oligomer of the substituted phthalonitrile is produced. Add a metal or metal salt.

In this case, in order to selectively produce P2, P3 and P4, the residual amount of unreacted substituted phthalonitrile is preferably 80% by weight or less (the amount of the substituted phthalonitrile oligomer produced is 20% by weight or more). ), Particularly preferably 60% by weight or less (the amount of the substituted phthalonitrile oligomer formed is 40% by weight or more), and further preferably 40% by weight or less (the substituted phthalonitrile oligomer formed amount is 6% or less).
(0% by weight or more), a metal or a metal salt is added.

As the metal or metal salt to be added to the reaction system, metal chlorides, metal acetates and the like can be used in addition to metals and metal oxides corresponding to the metal or metal oxide to be introduced. As the metal or metal oxide that can be introduced, VO, TiO, Mn, Fe, Co, Ni, Cu,
Zn, Pd, Cd, Mg and the like can be mentioned. Among them, VO, Fe, Cu and Zn are preferable.

The amount of the metal or metal salt used is preferably 25 to 500 mol% based on the substituted phthalonitrile in order to reliably obtain the metal phthalocyanine derivative containing the desired metal or metal oxide. And particularly preferably 25 to 100 mol%.

In the production method of the present invention, a dehydrating agent can coexist in the reaction system in order to improve the yield of the metal phthalocyanine derivative. As a dehydrating agent,
There is no particular limitation as long as the cyclization reaction can proceed smoothly and the object of the present invention can be achieved.

As the dehydrating agent, the following general formula (3):
AC (OB) ₃ (3) wherein A represents a hydrogen atom or an aliphatic, alicyclic or aromatic group having 1 to 36 carbon atoms which may have a substituent;
B is an aliphatic having 1 to 36 carbon atoms which may have a substituent,
Shows an alicyclic or aromatic group. Orthocarboxylic acid ester represented by the formula:

Examples of the orthocarboxylic acid ester represented by the general formula (3) include orthoformates such as methyl orthoformate, ethyl orthoformate, propyl orthoformate and butyl orthoformate, methyl orthoacetate, ethyl orthoacetate, and the like. Ortho acetates such as propyl orthoacetate and butyl orthoacetate; orthobenzoates such as methyl orthobenzoate, ethyl orthobenzoate, propyl orthobenzoate and butyl orthobenzoate; tetramethyl orthocarbonate; tetraethyl orthocarbonate Nate,
Examples thereof include tetraisopropyl orthocarbonate. Of these, methyl orthoformate and ethyl orthoformate are preferable. These orthocarboxylic acid esters can be used alone or in combination of two or more.

Further, other dehydrating agents include the following general formula (4):

[0031]

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Wherein Z and W each represent a hydrogen atom or an aliphatic, aliphatic ether, alicyclic or aromatic group having 1 to 36 carbon atoms which may have a substituent. Where Z and W
May form a ring with each other. ] Or glycidyl ethers represented by the formula:

The oxiranes represented by the general formula (4) include ethylene oxide, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, epoxyhexane, epoxyoctane, epoxydecane, epoxydodecane, epoxytetradecane , Epoxy hexadecane,
Epoxy octadecane, butadiene monoxide, epichlorohydrin, glycidol, methylglycidol,
Cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, cyclododecane epoxide, α
-Pinene oxide, limonene oxide, epoxy norbornane, butadiene dioxide, diepoxy octane,
Examples include diepoxycyclooctane, styrene oxide, 2,3-epoxypropylbenzene, 1-phenylpropylene oxide, and stilbene oxide.

The glycidyl ether represented by the general formula (4) includes methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, tert-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidyl ether, 1-methoxy-2-methylpropylene oxide, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,2-epoxy-3-phenoxypropane, 2
-Benzyloxymethyloxirane, glycidyl-2-methylphenyl ether, 4-tert-butylphenyl, 2,3-epoxypropyl ether, 4-chlorophenyl-2,3-epoxypropyl ether, 2,3-epoxypropyl-4- Methoxyphenyl ether, 2-biphenyl glycidyl ether, glycidyl-1-naphthyl ether and the like can be mentioned.

As the oxiranes or glycidyl ethers, propylene oxide, 1,2-epoxybutane, 2,3-epoxybutane, epoxyhexane,
Epoxy octane, epichlorohydrin, glycidol, cyclohexene oxide, styrene oxide, isopropyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 1,2-epoxy-3-phenoxypropane are preferred, and epoxyhexane, cyclohexene oxide, 2 -Ethylhexyl glycidyl ether is particularly preferred. These oxiranes and glycidyl ethers can be used alone or in combination of two or more.

[0036] The amount of the dehydrating agent used in the present invention is preferably 0.1 to 0.1 with respect to the substituted phthalonitrile in order to secure an appropriate reaction time and to give a sufficient dehydrating effect.
500 mol%, particularly preferably 5 to 100 mol%
It is.

The atmosphere of the reaction system in the production method of the present invention is not particularly limited, but it is preferable that the reaction system be a nitrogen gas atmosphere or an inert gas atmosphere such as argon.

The reaction temperature in the production method of the present invention is to prevent the product from being colored by heat and to make the reaction smooth.
Preferably it is -100-250 degreeC, Especially preferably, it is -20-200 degreeC, More preferably, it is 0-150 degreeC.
° C, most preferably from 0 to 80 ° C.

The reaction time in the production method of the present invention varies depending on conditions such as the reaction temperature.
0 minutes to 100 hours.

After completion of the reaction, the desired metal phthalocyanine derivative can be obtained by applying a known refining means such as reprecipitation, neutralization, filtration and extraction to the reaction solution, if necessary. Further, in order to further increase the degree of purification, in addition to the above-mentioned purification means such as reprecipitation and recrystallization, purification means such as silica gel chromatography can also be applied.

[0041]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 5.80 g (15 mmol) of 3- (2,2,2,2 ', 2', 2'-hexafluorocumyloxy) -phthalonitrile, 30 m of 1-pentanol
l, 0.31 g (3.2 mmol) of cyclohexene oxide and 3.43 g (23 mmol) of DBU were placed in a 100 ml four-necked flask, and stirred at 70 ° C for 22 hours while flowing nitrogen gas. At this point, the residual amount of 3- (2,2,2,2 ', 2', 2'-hexafluorocumyloxy) -phthalonitrile was 21% by weight (determined by GC analysis using an internal standard method). .
The same applies to the following.) Then, VCl ₃ 0.5
9 g (3.8 mmol) was added, and the mixture was stirred at 70 ° C. for 32 hours.
After allowing to cool, 39 ml of water was dissolved in 225 ml of methanol and 30 ml of water was added.
After dropwise addition over a period of minutes, the mixture was stirred at room temperature for 2 hours to cause reprecipitation. Suction filtration with a Kiriyama funnel, methanol / water (6 /
1) The solid was washed with 150 ml. This solid content is 100
℃ 3hPa dried for 1 hour, tetra-α- (2,2,2,2 ', 2', 2 '
3.28 g of a crude product (green solid) of -hexafluorocumyloxy) vanadyl phthalocyanine was obtained. Reaction yield is 5
1%. The composition ratio of the structural isomers is P2: P3:
(P1 + P4) = 42: 29: 29. The reaction yield and composition ratio were determined from the HPLC area% of the crude product shown in FIG. 1 (P2, P2 in the chart feed direction in order).
3, peak of P1 + P4). The same applies to the following embodiments.

After dissolving 1 g of the above crude product in 20 ml of each of tetrahydrofuran, chloroform and toluene, the solution was allowed to stand at room temperature for 24 hours, but no change was observed in any of the solutions. This confirmed that the phthalocyanine derivative obtained by the production method of the present invention had good solubility and stability of the solution.

Comparative Example 1 5.80 g (15 mmol) of 3- (2,2,2,2 ', 2', 2'-hexafluorocumyloxy) -phthalonitrile, 0.59 g of VCl ₃ (3.
8 mmol), 30 ml of 1-pentanol and 0.33 g (3.4 mmol) of cyclohexene oxide were charged into a 100 ml four-necked flask, and the mixture was heated to 70 ° C. and stirred while flowing nitrogen gas. While maintaining the temperature of the reaction system at 70 ° C, DBU
3.43 g (23 mmol) were added dropwise over 30 minutes. Thereafter, the mixture was stirred at 70 ° C. for 32 hours. After cooling, methanol 2
The solution was dissolved in 25 ml, and 39 ml of water was added dropwise over 30 minutes, and the mixture was reprecipitated by stirring at room temperature for 2 hours. Suction filtration was performed using a Kiriyama funnel, and the solid content was washed with 150 ml of methanol / water (6/1). The solid content was dried at 100 ° C./3 hPa for 1 hour, and 2.06 g of a crude product of tetra α- (2,2,2,2 ′, 2 ′, 2′-hexafluorocumyloxy) vanadyl phthalocyanine (green solid) was obtained. I got The reaction yield was 42%. The composition ratio of the structural isomers is P2: P3: (P1 + P4) = 2
3:13:64. The reaction yield and composition ratio were determined from the HPLC area% of the crude product shown in FIG. 2 (indicating the peaks of P2, P3, and P1 + P4 in the chart feed direction). The same applies to the following comparative examples.

After dissolving the above crude product in an organic solvent in the same manner as in Example 1, the crystals were deposited when allowed to stand at room temperature for 24 hours.

Example 2 5.80 g (15 mmol) of 3- (2,2,2,2 ', 2', 2'-hexafluorocumyloxy) -phthalonitrile, 30 ml of 1-pentanol
And 3.43 g (23 mmol) of DBU were placed in a 100 ml four-necked flask, and heated at 95 ° C. while flowing nitrogen gas.
Stirred for hours. At this point, the remaining amount of 3- (2,2,2,2 ', 2', 2'-hexafluorocumyloxy) -phthalonitrile is 30.
% By weight. Thereafter, 0.59 g of VCl ₃ (3.8 mmo
l) was added and stirred at 95 ° C for 6 hours. After standing to cool, the mixture was dissolved in methanol (225 ml), water (39 ml) was added dropwise over 30 minutes, and the mixture was reprecipitated by stirring at room temperature for 2 hours. Suction filtration with a Kiriyama funnel, 150 ml of methanol / water (6/1)
To wash the solids. The solid content was dried at 100 ° C./3 hPa for 1 hour, and 2.34 g of a crude product (green solid) of tetra α- (2,2,2,2 ′, 2 ′, 2′-hexafluorocumyloxy) vanadyl phthalocyanine was obtained. I got The reaction yield was 29%. The composition ratio of the structural isomers is P2: P3: (P1 + P
4) = 26: 32: 42.

Comparative Example 2 3.80 g (15 mmol) of 3- (2,2,2,2 ', 2', 2'-hexafluorocumyloxy) -phthalonitrile, 0.59 g of VCl ₃ (3.
8 mmol) and 30 ml of 1-pentanol were charged into a 100 ml four-necked flask, and the mixture was heated to 90 ° C. and stirred while flowing nitrogen gas. While maintaining the temperature of the reaction system at 90 to 95 ° C., 3.43 g (23 mmol) of DBU was added dropwise over 30 minutes. Thereafter, the mixture was stirred at 95 ° C. for 6 hours. After standing to cool, the mixture was dissolved in methanol (225 ml), water (39 ml) was added dropwise over 30 minutes, and the mixture was reprecipitated by stirring at room temperature for 2 hours. Suction filtration was performed using a Kiriyama funnel, and the solid content was washed with 150 ml of methanol / water (6/1). The solid content is 1 at 100 ° C / 3 hPa.
After drying for an hour, 2.76 g of a crude product (green solid) of tetra α- (2,2,2,2 ′, 2 ′, 2′-hexafluorocumyloxy) vanadyl phthalocyanine was obtained. The reaction yield was 25%.
The composition ratio of the structural isomers is P2: P3: (P1 + P4) =
9: 6: 85.

Example 3 5.80 g (15 mmol) of 3- (2,2,2,2 ', 2', 2'-hexafluorocumyloxy) -phthalonitrile, 30 m of 1-pentanol
l, 0.31 g (3.2 mmol) of cyclohexene oxide and 3.43 g (23 mmol) of DBU were charged into a 100 ml four-necked flask, and stirred at 75 ° C for 4 hours while flowing nitrogen gas. Thereafter, 0.59 g (3.8 mmol) of VCl ₃ was added, and the mixture was stirred at 70 ° C. for 32 hours. Thereafter, the first embodiment
In the same manner as described above, a crude product (green solid) of tetra α- (2,2,2,2 ′, 2 ′, 2′-hexafluorocumyloxy) vanadyl phthalocyanine was obtained. Table 1 shows the residual amount of phthalonitrile, the reaction yield, and the composition ratio.

Example 4 5.80 g (15 mmol) of 3- (2,2,2,2 ', 2', 2'-hexafluorocumyloxy) -phthalonitrile, 30 m of 1-pentanol
l, 0.31 g (3.2 mmol) of cyclohexene oxide and 3.43 g (23 mmol) of DBU were charged into a 100 ml four-necked flask, and stirred at 75 ° C for 8 hours while flowing nitrogen gas. Thereafter, 0.59 g (3.8 mmol) of VCl ₃ was added, and the mixture was stirred at 70 ° C. for 32 hours. Thereafter, the first embodiment
In the same manner as described above, a crude product (green solid) of tetra α- (2,2,2,2 ′, 2 ′, 2′-hexafluorocumyloxy) vanadyl phthalocyanine was obtained. Table 1 shows the residual amount of phthalonitrile, the reaction yield, and the composition ratio.

Example 5 5.80 g (15 mmol) of 3- (2,2,2,2 ', 2', 2'-hexafluorocumyloxy) -phthalonitrile, 30 m of 1-pentanol
l, 0.31 g (3.2 mmol) of cyclohexene oxide and 3.43 g (23 mmol) of DBU were charged into a 100 ml four-necked flask, and stirred at 75 ° C for 10 hours while flowing nitrogen gas. Thereafter, 0.59 g (3.8 mmol) of VCl ₃ was added, and the mixture was stirred at 70 ° C. for 32 hours. Thereafter, in the same manner as in Example 1, a crude product (green solid) of tetra α- (2,2,2,2 ′, 2 ′, 2′-hexafluorocumyloxy) vanadyl phthalocyanine was obtained. The residual amount of phthalonitrile,
Table 1 shows the reaction yield and composition ratio.

Example 6 5.80 g (15 mmol) of 3- (2,2,2,2 ', 2', 2'-hexafluorocumyloxy) -phthalonitrile, 30 m of 1-pentanol
l, 0.31 g (3.2 mmol) of cyclohexene oxide and 3.43 g (23 mmol) of DBU were placed in a 100 ml four-necked flask, and stirred at 75 ° C for 12 hours while flowing nitrogen gas. Thereafter, 0.59 g (3.8 mmol) of VCl ₃ was added, and the mixture was stirred at 70 ° C. for 32 hours. Thereafter, in the same manner as in Example 1, a crude product (green solid) of tetra α- (2,2,2,2 ′, 2 ′, 2′-hexafluorocumyloxy) vanadyl phthalocyanine was obtained. The residual amount of phthalonitrile,
Table 1 shows the reaction yield and composition ratio.

Example 7 5.80 g (15 mmol) of 3- (2,2,2,2 ', 2', 2'-hexafluorocumyloxy) -phthalonitrile, 30 m of 1-pentanol
l, 0.31 g (3.2 mmol) of cyclohexene oxide and 3.43 g (23 mmol) of DBU were placed in a 100 ml four-necked flask, stirred at 75 ° C. for 14 hours while flowing nitrogen gas, and then 0.59 g of VCl ₃ (3.8 mmol) and stirred at 70 ° C. for 32 hours. Thereafter, the first embodiment
In the same manner as described above, a crude product (green solid) of tetra α- (2,2,2,2 ′, 2 ′, 2′-hexafluorocumyloxy) vanadyl phthalocyanine was obtained. Table 1 shows the residual amount of phthalonitrile, the reaction yield, and the composition ratio.

Example 8 5.80 g (15 mmol) of 3- (2,2,2,2 ', 2', 2'-hexafluorocumyloxy) -phthalonitrile, 30 m of 1-pentanol
1, 0.31 g (3.2 mmol) of cyclohexene oxide and 3.43 g (23 mmol) of DBU were placed in a 100 ml four-necked flask, and stirred at 75 ° C. for 26 hours while flowing nitrogen gas. Thereafter, 0.59 g (3.8 mmol) of VCl ₃ was added, and the mixture was stirred at 70 ° C. for 32 hours. Thereafter, in the same manner as in Example 1, a crude product (green solid) of tetra α- (2,2,2,2 ′, 2 ′, 2′-hexafluorocumyloxy) vanadyl phthalocyanine was obtained. The residual amount of phthalonitrile,
Table 1 shows the reaction yield and composition ratio.

[0054]

[Table 1]

Example 9 5.80 g (15 mmol) of 3- (2,2,2,2 ', 2', 2'-hexafluorocumyloxy) -phthalonitrile, 30 ml of 1-pentanol
And DBU (3.43 g, 23 mmol) were placed in a 100 ml four-necked flask, and heated at 95 ° C. while flowing nitrogen gas.
Stirred for hours. Then, 0.59 g (3.8 mmol) of VCl ₃
Was added and stirred at 95 ° C. for 6 hours. Thereafter, in the same manner as in Example 2, a crude product (green solid) of tetra α- (2,2,2,2 ′, 2 ′, 2′-hexafluorocumyloxy) vanadyl phthalocyanine was obtained. The residual amount of phthalonitrile,
Table 2 shows the reaction yield and composition ratio.

Example 10 5.80 g (15 mmol) of 3- (2,2,2,2 ', 2', 2'-hexafluorocumyloxy) -phthalonitrile, 30 ml of 1-pentanol
And DBU (3.43 g, 23 mmol) were placed in a 100 ml four-necked flask, and heated at 95 ° C. while flowing nitrogen gas.
Stirred for hours. Then, 0.59 g (3.8 mmol) of VCl ₃
Was added and stirred at 95 ° C. for 6 hours. Thereafter, in the same manner as in Example 2, a crude product (green solid) of tetra α- (2,2,2,2 ′, 2 ′, 2′-hexafluorocumyloxy) vanadyl phthalocyanine was obtained. The residual amount of phthalonitrile,
Table 2 shows the reaction yield and composition ratio.

[0057]

[Table 2]

Example 11 4.55 g (15 mmol) of 3- (1-phenyl-2,2,2-trifluoroethoxy) -phthalonitrile, 30 ml of 1-pentanol,
0.31 g (3.2 mmol) of cyclohexene oxide and DB
2.85 g (23 mmol) of N was charged into a 100 ml four-necked flask and stirred at 75 ° C. for 8 hours while flowing nitrogen gas. Thereafter, 0.52 g (3.8 mmol) of ZnCl ₂ was added, and the mixture was stirred at 70 ° C. for 32 hours. Thereafter, in the same manner as in Example 1, a crude product of tetra α- (1-phenyl-2,2,2-trifluoroethoxy) zinc phthalocyanine (green solid)
I got Table 3 shows the residual amount of phthalonitrile, the reaction yield, and the composition ratio.

Example 12 Instead of stirring at 75 ° C. for 8 hours in Example 11,
In the same manner, tetra α- (1
A crude product (green solid) of -phenyl-2,2,2-trifluoroethoxy) zinc phthalocyanine was obtained. Table 3 shows the residual amount of phthalonitrile, the reaction yield, and the composition ratio.

Comparative Example 3 4.55 g (15 mmol) of 3- (1-phenyl-2,2,2-trifluoroethoxy) -phthalonitrile, 0.52 g of ZnCl ₂ (3.
8 mmol), 30 ml of 1-pentanol and 0.31 g (3.2 mmol) of cyclohexene oxide were charged into a 100 ml four-necked flask, and the mixture was heated to 70 ° C. and stirred while flowing nitrogen gas. While maintaining the temperature of the reaction system at 70 ° C, DBU2.
85 g (23 mmol) were added dropwise over 30 minutes. Then 7
Stirred at 0 ° C. for 32 hours. Thereafter, in the same manner as in Comparative Example 1, a crude product (green solid) of tetra-α- (1-phenyl-2,2,2-trifluoroethoxy) zinc phthalocyanine was obtained. Table 3 shows the residual amount of phthalonitrile, the reaction yield, and the composition ratio.

[0061]

[Table 3]

Example 13 4- (2-ethylhexyloxy) -phthalonitrile 3.3
5 g (15 mmol), 1-pentanol 30 ml, cyclohexene oxide 0.31 g (3.2 mmol) and DBU 3.43 g (2
3 mmol) was placed in a 100 ml four-necked flask, and stirred at 75 ° C. for 8 hours while flowing nitrogen gas. afterwards,
0.38 g (3.8 mmol) of CuCl are added and
Stirred for hours. Thereafter, in the same manner as in Example 1, a crude product (green solid) of tetra β- (2-ethylhexyloxy) copper phthalocyanine was obtained. Table 4 shows the residual amount of phthalonitrile, the reaction yield, and the composition ratio.

Example 14 Instead of stirring at 75 ° C. for 8 hours in Example 13,
Tetra β- (2
A crude product (green solid) of -ethylhexyloxy) copper phthalocyanine was obtained. The residual amount of phthalonitrile,
Table 4 shows the reaction yield and the composition ratio.

Comparative Example 4 4- (2-ethylhexyloxy) -phthalonitrile 3.3
5 g (15 mmol), CuCl 0.38 g (3.8 mmol), 1-pentanol 30 ml and cyclohexene oxide 0.31 g
(3.2 mmol) was charged into a 100 ml four-necked flask, and heated to 75 ° C. and stirred while flowing nitrogen gas. 2.85 g (23 mmol) of DBN while maintaining the temperature of the reaction system at 75 ° C.
Was added dropwise over 30 minutes. Thereafter, the mixture was stirred at 70 ° C. for 32 hours. Thereafter, in the same manner as in Comparative Example 1, tetra-β-
A crude product (green solid) of (2-ethylhexyloxy) copper phthalocyanine was obtained. The residual amount of phthalonitrile,
Table 4 shows the reaction yield and the composition ratio.

[0065]

[Table 4]

[0066]

According to the production method of the present invention, the four structural isomers P1, P2 and P of phthalocyanine in the product are obtained.
3 and P4, the selectivity of structural isomers P2, P3 and P4 other than the swastika-type P1 component having high crystallinity can be improved. Therefore, the obtained metal phthalocyanine derivative has good solubility in an organic solvent and high stability of the solution. Therefore, the metal phthalocyanine derivative obtained by the production method of the present invention is suitable as a recording film material for CDs, especially write-once CDs, and in addition, pigments that have been widely used in the past, and other optical recording materials Dyes, dyes for color filters, photoelectric conversion elements, electrophotographic photoreceptors, organic semiconductor elements, catalysts, gas sensors, color filters,
It can be widely used as a raw material for deodorants, medicines, agricultural chemicals and the like.

[Brief description of the drawings]

FIG. 1 is an HPLC chart of a crude product obtained in Example 1.

FIG. 2 is an HPLC chart of the crude product obtained in Comparative Example 1.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Hiroshi Ueda 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd.

Claims (5)

[Claims] 1. A method for producing a phthalocyanine derivative by subjecting a substituted phthalonitrile to a cyclization reaction in the presence of a base and an alcoholic solvent, wherein a metal or a metal salt is added in a state where an oligomer of the substituted phthalonitrile is formed. A method for producing a metal phthalocyanine derivative, which is characterized in that: 2. The method for producing a metal phthalocyanine derivative according to claim 1, wherein the metal or the metal salt is added after the residual amount of the unreacted substituted phthalonitrile becomes 80% by weight or less. 3. The substituted phthalonitrile has the following general formula (1): [In the formula, X represents a hydrogen atom or an aliphatic, alicyclic or aromatic group having 1 to 36 carbon atoms which may have a substituent. 3. The method for producing a metal phthalocyanine derivative according to claim 1, wherein: 4. The substituted phthalonitrile has the following general formula (2): [In the formula, Y represents a hydrogen atom or an aliphatic, alicyclic or aromatic group having 1 to 36 carbon atoms which may have a substituent. 3. The method for producing a metal phthalocyanine derivative according to claim 1. 5. The method for producing a metal phthalocyanine derivative according to claim 1, further comprising a coexisting dehydrating agent in the reaction system.