JPH0730080B2 - Phthalocyanine derivative - Google Patents

Description

TECHNICAL FIELD The present invention relates to a phthalocyanine derivative, and more particularly to a phthalocyanine dimer, trimer, tetramer and pentamer.

[Conventional technology]

Conventionally, (metal) phthalocyanine (hereinafter referred to as MPc) has been widely used as a colorant having high weather resistance, and in recent years, it has been used as a member of a charge generation layer for electrophotography as an organic optical semiconductor (hereinafter referred to as OPC).

However, the wavelength range in which the semiconductor laser can oscillate is 780 to 8
In contrast to 30 nm, the conventional MPc has an absorption wavelength band in a wavelength range slightly shorter than the wavelength range. Therefore, conventional MPc
When used as a PC, matching between the absorption wavelength band of MPc and the wavelength region in which the semiconductor laser can oscillate has become a problem.

Therefore, it has been attempted to extend the absorption wavelength region of MPc by controlling the crystal type, grain size, stacking, etc. (eg RO Loutfy).
J. Image Science, 29 , 116.
(1985)]. However, their absorption properties were unsatisfactory.

[Problems to be Solved by the Invention] Therefore, an object of the present invention is to provide a phthalocyanine derivative useful as an OPC having an absorption wavelength band (sensitivity) in a long-wave region in which a semiconductor laser can oscillate, and a method for producing the same. It is in.

[Means for solving problems]

The present invention relates to general formulas (I), (II), (III) and (IV)
And a phthalocyanine derivative represented by

(In the formula, R _{1 to} R ₁₂ are a hydrogen atom, a t-butyl group, and a carbon number of 20.
The following linear or branched alkoxy group, a linear or branched alkylthio group having 20 or less carbon atoms, an aryloxy group having 20 or less carbon atoms, an aralkyloxy group having 20 or less carbon atoms, an arylthio group having 20 or less carbon atoms or 20 or less carbon atoms It is an aralkylthio group, and M ₁ or M ₂ has two hydrogen atoms, which can form a complex.
A combination of a valent metal ion or a trivalent to hexavalent metal ion and a counter anion, and a combination of a metal ion and anion having a valence of +2, or R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and
1-3 selected from R ₆ , R ₇ and R ₈ , R ₉ and R ₁₀ and R ₁₁ and R ₁₂
Two sets are general formula (V) (Wherein R _{13 to} R ₁₈ are a hydrogen atom, a t-butyl group, a linear or branched alkoxy group having 20 or less carbon atoms, a linear or branched alkylthio group having 20 or less carbon atoms, an aryloxy group having 20 or less carbon atoms, carbon An aralkyloxy group having a number of 20 or less, an arylthio group having a carbon number of 20 or less, or an aralkylthio group having a carbon number of 20 or less, M ₃ is two hydrogen atoms, a divalent metal ion capable of forming a complex, or a trivalent to hexavalent A combination of a metal ion and a counter anion, which is a combination of a metal ion and an anion having a valence of +2.). ) (Wherein R ₂₁ and R ₂₂ , R ₂₃ and R ₂₄ , R ₂₅ and R ₂₆ , R ₃₁ and R ₃₂ and R
Two groups selected from ₃₃ and R ₃₄ are phthalocyanine derivative groups represented by the general formula (V), and R _{19 to} R ₃₄ other than the phthalocyanine derivative group of the general formula (V) are hydrogen atoms, t- Butyl group, linear or branched alkoxy group having 20 or less carbon atoms, linear or branched alkylthio group having 20 or less carbon atoms, aryloxy group having 20 or less carbon atoms, aralkyloxy group having 20 or less carbon atoms, arylthio group having 20 or less carbon atoms Or an aralkylthio group having 20 or less carbon atoms, M _{4 to} M ₆ are two hydrogen atoms, a divalent metal ion capable of forming a complex, or 3 to
It is a combination of a hexavalent metal ion and a counter anion, and has a valence of +2. ) (Where R ₃₉ and R ₄₀ , R ₄₁ and R ₄₂ , R ₄₃ and R ₄₄ , R ₄₅ and R ₄₆ , R
Two groups selected from ₄₇ and R ₄₈ and R ₄₉ and R ₅₀ are phthalocyanine derivatives represented by the general formula (V), and R _{35 to} R ₅₀ other than the phthalocyanine derivative group of the general formula (V).
Is a hydrogen atom, a t-butyl group, a linear or branched alkoxy group having 20 or less carbon atoms, a linear or branched alkylthio group having 20 or less carbon atoms, an aryloxy group having 20 or less carbon atoms, an aralkyloxy group having 20 or less carbon atoms, It is an arylthio group having 20 or less carbon atoms or an aralkylthio group having 20 or less carbon atoms, M _{7 to} M ₉ are two hydrogen atoms, a divalent metal ion capable of forming a complex, or a trivalent to hexavalent metal ion. It is a combination of an anion and a metal ion having a valence of +2 and an anion. ) (In the formula, R _{51 to} R ₆₆ are a hydrogen atom, a t-butyl group, and a carbon number of 20.
The following linear or branched alkoxy group, a linear or branched alkylthio group having 20 or less carbon atoms, an aryloxy group having 20 or less carbon atoms, an aralkyloxy group having 20 or less carbon atoms, an arylthio group having 20 or less carbon atoms or 20 or less carbon atoms An aralkylthio group, or a combination of R ₅₁ and R ₅₂ is a phthalocyanine derivative group of the general formula (V), M ₁₁ or M ₁₄ is two hydrogen atoms, a divalent metal ion capable of forming a complex. Or a combination of a trivalent to hexavalent metal ion and a counter anion with a valence of +2
Is a combination of a metal ion and an anion. ) Specific examples of the functional groups in the compounds of the general formulas (I) to (IV) and the phthalocyanine derivative group of the general formula (V) of the present invention are shown.

"Having 20 or less linear or branched alkoxy group having a carbon" as, for example methoxy (C _1), ethoxy (C _2), n- propoxy (C _3), i- propoxy (C _3), n- butoxy (C ₄ ), I-butoxy (C ₄ ), t-butoxy (C ₄ ), n
- pentyloxy (C _5), 2- methylbutoxy (C _5), 3
- methylbutoxy (C _5), neo- pentyloxy (C _5),
Examples thereof include n-decanoxy (C ₁₀ ), n-hexadecanoxy (C ₁₆ ), and n-docoxy (C ₂₀ ).

Examples of the “linear or branched alkylthio group having 20 or less carbon atoms” include methylthio (C ₁ ), ethylthio (C ₂ ), n-propylthio (C ₃ ), i-propylthio (C ₃ ), n-butylthio (C ₄ ). ), I-butylthio (C ₄ ), t-butylthio (C ₄ ), n-pentylthio (C ₅ ), 2-methylbutylthio (C ₅ ), 3-methylbutylthio (C ₅ ), neo-pentylthio ( C _5), n-Dekaniruchio (C _10), n- hexadecene crab thio (C _16), n- eicosylthio (C _20), and the like.

The "number of 20 or less aryloxy group having a carbon", such as phenoxy (C _6), o-methylphenoxy (C _7), m-methylphenoxy (C _7), p-methylphenoxy (C _7),
2,6-dimethyl-phenoxy (C _8), alpha-Nefuchirokishi (C
₁₀ ), β-naphthyloxy (C ₁₀ ), o-phenylphenoxy (C ₁₂ ), m-phenylphenoxy (C ₁₂ ), p-phenylphenoxy (C ₁₂ ), 2,6-diphenylphenoxy (C ₁₈ ), etc. Can be mentioned.

For example, the "number of 20 or less Ararukirokishi group atoms" benzyloxy (C _7), phenylethoxy (C _8), 1- Nafuchiruetokishi (C _12), and the like.

Examples of the “arylthio group having 20 or less carbon atoms” include phenylthio (C ₆ ), α-naphthylthio (C ₁₀ ), β-naphthylthio (C ₁₀ ), and the like.

Examples of the “aralkylthio group having 20 or less carbon atoms” include benzylthio (C ₇ ).

Specific examples of M _{1 to} M ₁₄ in the compounds of the general formulas (I) to (IV) and the phthalocyanine derivative group of the general formula (V) of the present invention are shown below.

Examples of the “divalent metal ion capable of forming a complex” include divalent transition metal ions “Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zu”.
²⁺ , Hg ²⁺ , Pb ²⁺ , Cd ^{2+ and the} like (but not limited thereto) can be mentioned.

"A combination of a metal ion having a valence of 3 to 6 and a counter anion and having a valence of +2 (a combination capable of forming a complex)" means the following (a).
The combination of (d) is mentioned.

(A) a trivalent metal ion + anion (M ³⁺ -X ^-) for example, trivalent metal ions M ^{3+ is, Al 3+, Mn 3+, Cr} 3+, C
o ³⁺ , rare earth metal ions (Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, H
o, Er, Tm, Yb, Lu) ³⁺ etc. (but not limited to this)
And the anion X ⁻ is a halogen (F ⁻ , Cl ⁻ , Br ₋ ,
X ^-), pseudohalogen ^{(CN -, SCN -),} 0H -, NO 3 -, ClO 4 -, H
_{^{SO 4 -, CF 3 SO 3}} - may be mentioned those which are such as (but not limited to).

(B) Tetravalent metal ion + anion (M ⁴⁺ − (X ⁻ ) ₂ ) For example, the tetravalent metal ion M ⁴⁺ is Si ⁴⁺ , Ge ⁴⁺ , Ti ⁴⁺ , V
^{4+ and the} like (but not limited ^thereto ), wherein the anion is X ⁻ or X ^{2 −} is halogen (F ⁻ , Cl ⁻ , Br ₋ ,
X ^-), pseudohalogen ^{(CN -, SCN -),} 0H -, NO 3 -, ClO 4 -, H
_{^{SO 4 -, CF 3 SO 3}} - ( not limited however to) such,
Alternatively, examples thereof include, but are not limited to, O ²⁻ , S ²⁻ , Se ²⁻ , SO ₄ ^{2− and the} like.

(C) 5-valent metal ion + anion _{^{[M 5+ - (X -) 3}} , M 5+
− (X ² −) X or M ⁵⁺ −X ³ ]] For example, a pentavalent metal ion is V ⁵⁺ , Nb ⁵⁺ , Ta ⁵⁺ , M
o ⁵⁺ , W ⁵⁺ , Re ^5+, etc., but not limited to, where the anion X ⁻ or X ^{2 −} or X ^{3 −} is halogen (F ⁻ , Cl ⁻ , Br ₋ , X ^-), pseudo halogen ^{(CN -, SCN -),} 0
^{_{H -, NO 3 -, ClO}} 4 -, HSO 4 -, CF 3 SO 3 - or O ^2-, S ^2-, Se
^Examples thereof include, but are not limited to, ^2- , SO ₄ ^{2-, and} PO ₄ ^3- .

(D) 6-valent metal ion + anion _{^{[M 6+ - (X -) 4}} , M 6+
^{- (X 2-) · (X} -) 2, M 5+ - (X 2-) 2 or M ⁶⁺ - (X ^3-) ·
(X ⁻ ) For example, the pentavalent metal ion is U ⁶⁺ , Mo ⁶⁺ , W ^{6+ and the} like (but is not limited ^thereto ), and the anion X ⁻ or X ²⁻ or X ³⁻ but halogen ^{(F -, Cl -, Br} -, X -),
Pseudohalogen ^{(CN -, SCN -),} 0H -, NO 3 -, ClO 4 -, HSO 4 -,
Examples thereof include, but are not limited to, CF ₃ SO _{3 −} or O ²⁻ , S ²⁻ , Se ²⁻ , SO ₄ ^2−, PO ₄ ^{3−, and the} like.

The method for producing the phthalocyanine derivative of the present invention will be described below.

(Dimer) The phthalocyanine dimer of the present invention is a compound represented by the general formula (I), wherein none of R _{1 to} R ₁₂ is a phthalocyanine derivative group represented by the general formula (V). is there.

An example of the method for producing the phthalocyanine dimer of the present invention will be described according to scheme 1.

Describes the synthesis of octacyanophthalocyanine
Report by D. Wohrle et al. [D. Wohrle.G. Meyer: Makromol. Chem.,
181 , 2127 (1980)] with a 3: 1 mixture of 4,5-disubstituted phthalonitrile and tetracyanobenzene in a solvent such as dehydrated isopropyl alcohol in a dilute condition in the presence of lithium isopropylate. The reaction is performed to synthesize the corresponding dicyanophthalocyanine derivative [Scheme 1, step (1)].

As a result of this reaction, a mixture of an unreacted product, a linear condensate that did not become a cyclic, an MPc derivative containing no cyano group, a dicyanophthalocyanine derivative, a tetracyanophthalocyanine derivative, a hexacyanophthalocyanine derivative, and octacyanophthalocyanine is obtained. . The former two are removed from the crude solid by extraction with methanol, and the remaining MPc mixture is separated by alumina or silica gel column chromatography to isolate the dicyanophthalocyanine derivative. However, the column member and the developing solvent at this time are
It depends on the type of R _a and R _b .

Next, when M ₁ is the above-mentioned metal ion, the dicyanophthalocyanine derivative obtained by the formula (1) is dissolved or dispersed in, for example, dimethylformamide, and excess metal hydrochloride or metal acetate or acetylacetone complex or metal carbonyl is used. The central metal is introduced when the reaction is carried out at 80 to 150 ° C. However, when a metal hydrochloride or metal acetate is used, it is preferable to allow an equivalent amount of pyridine to be present from the viewpoint of completely introducing the metal. Excess metal salt or by-products can be removed by washing with methanol.

The thus obtained central metal-incorporated or metal-free dicyanophthalocyanine derivative was dehydrated with methanol / N-
Ammonia gas is added in the presence of sodium methylate in a mixed solvent of methylpyrrolidone equivalents to give a bis (diiminoisoindolenin) derivative (Scheme 1, step (2)).

On the other hand, in exactly the same manner, but using dehydrated methanol in the solution, a diiminoisoindolenin derivative is prepared as in formula (3). When the substituent in formula (3) is not a hydrogen atom, it is a starting material in the reaction of formula (4) according to the method disclosed in detail in JP-A-61-207431.
(5)-(di) Substituted phthalonitrile is synthesized.

A diiminoisoindolenine derivative is synthesized in the same manner as in step (2) except that dehydrated methanol is used in the solution [Scheme 1, step (3)]. The mono- or di-substituted phthalonitrile, which is a variable in step (3), is disclosed in JP-A-61-2704.
It can be synthesized by the method disclosed in No. 31 as shown below.

Next, with respect to 1 equivalent of the diiminoisoindoleninophthalocyanine derivative obtained in the step (3), 9 to 15 equivalents of the diiminoindolenine derivative obtained in the step (3) (provided that M ₂ is a metal ion 12.5 equivalents or more of metal salt of M ₂ ) if dehydrated N,
When dissolved in N-dimethylamino-2-ethanol and subjected to boiling point reflux under an inert gas atmosphere, the desired phthalocyanine dimer is liberated as a black-green precipitate [Scheme 1, step (4)].

In the step (4), it is better to use the diiminoisoindolenine derivative in excess so that the yield of the desired product is better. It is considered that this is because the cyclization reaction of the diiminoisoindolenine derivative itself is fast and the reaction is completed without reacting with the bis (diiminoisoindolenine) derivative. An excess amount is preferable, and an amount of 12 to 14 equivalents is most preferable. Metal salt
20 equivalents or more is not necessary, and most preferably 15 to 18 equivalents. The crude product obtained as a black-green precipitate is unreacted,
Non-cyclic linear condensate and tetra substitution
It contains an MPc derivative as an impurity. Unrefined material should be extracted with dimethylformamide, and then, when R _a , R _b , R _e , and R _f are H, vacuum treatment should be performed at 300 ℃ to 400 ℃ under high vacuum of 10 ^-5 torr or more. When R _a , R _b , R _e , and R _f are not H, the target phthalocyanine dimer can be isolated in good yield by separation by alumina or silica gel column chromatography. However, the column member and the developing solvent at this time differ depending on the types of R _a , R _b , R _e , and R _f .

(Trimer) The phthalocyanine trimer of the present invention is a compound of the general formula (I), wherein any one of R ₃ and R ₄ or R ₅ and R ₆ is a phthalocyanine derivative group of the general formula (V). Is a compound.

The method for producing the phthalocyanine trimer of the present invention is described in Scheme 2
Follow the instructions below.

Describes the synthesis of octacyanophthalocyanine
Report by D. Wohrle et al. [D. Wohrle.G. Meyer: Makromol. Chem.,
181 , 2127 (1980)], and reacted with an equivalent mixture of 4,5-disubstituted phthalonitrile and tetracyanobenzene in a solvent such as dehydrated isopropyl alcohol in a dilute condition in the presence of lithium isoprobilate. The corresponding tetracyanophthalocyanine derivative is synthesized [Scheme 2, step (5)].

As a result of this reaction, a mixture of an unreacted product, a linear condensate that did not become a cyclic, an MPc derivative containing no cyano group, a dicyanophthalocyanine derivative, a tetracyanophthalocyanine derivative, a hexacyanophthalocyanine derivative, and octacyanophthalocyanine is obtained. . The former two are removed from the unpurified solid by extraction with methanol, and the remaining MPc mixture is separated by alumina or silica gel chromatography to isolate the tetracyanophthalocyanine derivative. However, the column member and the developing solvent at this time are
It depends on the type of R _a and R _b .

Next, when M ₁ is the metal ion described above, the tetrasiaphthalocyanine derivative obtained in step (5) is dissolved or dispersed in, for example, dimethylformamide, and excess metal hydrochloride or metal acetate or acetylacetone complex or metal is added. The central metal is introduced by reaction with carbonyl at 80 to 150 ° C. However, when a metal hydrochloride or metal acetate is used, it is preferable to allow an equivalent amount of pyridine to be present from the viewpoint of completely introducing the metal. Excess metal salt or by-products can be removed by washing with methanol.

The central metal-introduced or metal-free tetracyanophthalocyanine derivative thus obtained is dehydrated with methanol.
Ammonia gas is added in the presence of sodium methylate in a mixed solvent of the same amount of / N-methylpyrrolidone to give a bis (diiminoisoindolenin) derivative (Scheme 2, step (6)).

Next, with respect to 1 equivalent of the bis (diiminoisoindolenine) derivative obtained in the step (6), 6 to 12 equivalents of the diiminoisoindolenine derivative obtained in the above step (3) (provided that M ₂ , M ₃
When is a metal ion [M ₂ metal salt + M ₃ metal salt]
(12.5 equivalents or more) is dissolved in dehydrated N, N-dimethylamino-2-ethanol, and the phthalocyanine trimer of interest is liberated as a black-green precipitate when the boiling point is refluxed in an inert gas atmosphere [Scheme 2, Step (7)].

At this time, it is better to use the diiminoisoindolenine derivative in excess, because the yield of the target substance is better. This is because the cyclization reaction of the diiminoisoindolenine derivative itself is faster, so that the bis (diiminoisoindolenine) derivative is reacted. It is thought that this is because it ends without doing. Therefore, it is preferable that the above-mentioned diiminoisoindolenine derivative equivalent is in excess, and particularly
Most preferred is about 10 to 12 equivalents. No more than 20 equivalents of metal salt are required, most preferably 15-18 equivalents. The crude product obtained as a black-green precipitate contains unreacted substances, non-cyclic linear condensates, and tetra-substituted MPc derivatives as impurities. These extraction with dimethylformamide, then R _a to R _f are vacuum treated at 300 ° C. or higher 400 ° C. or less under a high vacuum of more than 10 ^-5 torr at H but, R _a to R _f
When is not H, the target phthalocyanine trimer can be isolated in good yield by separating it by alumina or disilica gel column chromatography. However, the column member and the developing solvent at this time differ depending on the types of R _{a to} R _f .
When the charged metal ion species are M ₂ ′ and M ₃ ′,
When M ₂ ′ ≠ M ₃ ′, the phthalocyanine trimer formed is [M ₂ = M ₂ ′, M ₃ = M ₂ ′], [M ₂ = M ₃ ′, M ₃ =
M ₃ ']. With three mixtures [M ₂ = M ₂ ′, M ₃ = M ₃ ′], these are further resolved by HPLC when R _a ˜R _f are suitable substituents. For example, in the case of an insoluble phthalocyanine trimer in which all of _{Ra to Rf} are -H, the mixture of these three types cannot be separated.

(Tetramer) The phthalocyanine tetramer of the present invention is a compound of the general formula (I), wherein R ₃ and R ₄ and R ₉ and R ₁₀ , R ₃ and R ₄ and R ₅ and R ₆ , R _{3 are used.}
And R ₄ and R ₇ and R ₈ , R ₁ and R ₂ and R ₁₁ and R ₁₂ , and combinations of R ₁ and R ₂ and R ₇ and R ₈ (any two combinations) Is a phthalocyanine derivative group of the general formula (V) and a compound of the general formula (IV), wherein R ₅₁
~ R ₆₆ is a compound which is not a phthalocyanine derivative group of the general formula (V).

In the following, the production method will be described in accordance with Scheme 3 in the case where both R ₃ and R ₄ and R ₅ and R ₆ are the phthalocyanine derivative group of the general formula (V).

Describes the synthesis of octacyanophthalocyanine
Report by D. Wohrle et al. [D. Wohrle.G. Meyer: Makromol. Chem.,
181 , 2127 (1980)], tetracyanobenzene (TCB) is replaced with phthalonitrile (P) as shown in formula (9).
N) to 4-substituted phthalonitrile (RPN) are reacted in dehydrated isopropyl alcohol under dilute conditions in the presence of lithium isopropylate to synthesize the corresponding hexacyanophthalocyanine [Scheme 3, step (8)]. TCB
The molar ratio of PN to RPN is suitably 3 to 4: 1 and preferably 3.3: 1 to 3.5: 1.

As a result of this reaction, a mixture of unreacted product, linear condensate that did not form a ring, phthalocyanine in which only RPN was cyclocondensed, dicyanophthalocyanine, tetracyanophthalocyanine, hexacyanophthalocyanine (target compound), octacyanophthalocyanine was obtained. To be The former two can be removed from the crude solid by extraction with methanol. Next, from the phthalocyanine mixture, dimethylformamide (DM
Soxhlet extraction by F) leaves only phthalocyanine as a solid, and further separation by neutral alumina column chromatography (Grade-111, chloroform / methanol / DMF = 1: 1: 1 effluent) yields The target hexacyanophthalocyanine is obtained as the three components.

Next, when M ₁ is the above-mentioned metal ion, the obtained hexacyanophthalocyanine is dissolved in DMF and reacted with excess metal hydrochloride or metal acetate or acetylacetone complex or metal carbonyl at 80 to 150 ° C. Metal is introduced. However, when a metal hydrochloride or a metal acetate is used, it is easier to completely introduce the compound in the presence of an equivalent amount of pyridine. Excess metal salt or by-products can be removed by washing with methanol.

The thus-obtained central metal-introduced or metal-free hexacyanophthalocyanine derivative is added to tris (diiminoamine) by adding ammonia gas in the presence of sodium methylate in a mixed solvent of dehydrated methanol / N-methylpyrrolidone equivalent. Isoindolenin) derivative (Scheme 3, step (9)].

Next, for 1 equivalent of the tris (diiminoisoindolenine) phthalocyanine derivative obtained in the step (9), the diiminoisoindolenine derivative obtained in the step (3) is added in an amount of 15 to 20.
An equivalent amount (however, when M _{2 to} M ₄ are metal ions, 12 equivalents or more as the total amount of the metal salt) is dehydrated N, N-dimethylamino-
When dissolved in 2-ethanol and subjected to boiling point reflux under an inert gas atmosphere, the target phthalocyanine tetramer is liberated as a black-green precipitate [Scheme 3, step (10)].

At this time, it is better to use the diiminoisoindolenine derivative in an excess amount because the yield of the desired product is higher. It is thought that this is due to termination without reaction. Therefore, it is preferable that the equivalent of the above-mentioned diiminoisoindolenine derivative is excessive, and most preferably about 17 to 18 equivalents. No more than 16 equivalents of metal salt are required, most preferably 13-14 equivalents. The crude product obtained as a black-green precipitate contains unreacted products, non-cyclic linear condensates, and (metal) phthalocyanine or (metal) tetra R-substituted phthalocyanine as impurities. Purification of the crude product is performed as follows. The crude product was extracted with DMF, then R _a , R
_{When b} , R _e and R _f are H, they are formed by a single cyclocondensation of diiminoisoindolenin by vacuum treatment at a temperature of 300 ° C to 400 ° C under a high vacuum of 10 ^-5 torr or more (metal). The phthalocyanine is sublimated away. When R _a , R _b , R _e , and R _f are not H, they can be separated by alumina or silica gel column chromatography to isolate the desired phthalocyanine tetramer in good yield. However, the column member and the developing solvent at this time are
It depends on the types of R _a , R _b , R _e , and R _f .

In the step (10), when two or more kinds of metal salts are used for the purpose of introducing different metals into M _{2 to} M ₄ , the metal phthalocyanine tetramer formed is not only the object but also the kind of central metal. And different arrangements can be by-produced, where R _a ,
If R _b , R _e , and R _f are not H, each can be separated by means such as HPLC, but when R _a , R _b , R _e , and R _f are H, they cannot be separated. However, even if the mixture is used as it is, it does not hinder the ripple effect of the present invention. This value is unchanged.

(Pentamer) The phthalocyanine pentamer of the present invention is a compound of the general formula (I), which comprises three groups of R ₁ and R ₂ , R ₃ and R _4, R ₅ and R ₆ , and R ₁ and
3 sets of R ₂ , R ₅ and R ₆ and R ₉ and R ₁₀ , R ₁ and R ₂ , R ₃ and R ₄ and R ₁₁
A compound having three phthalocyanine derivative groups of the general formula (V), three groups of R and R ₁₂ , three groups of R ₁ and R ₂ , R ₃ and R _4, and R ₇ and R ₈ , respectively, and general formulas (II) and (III) And a compound of the general formula (IV) in which the pair of R ₅₁ and R ₅₂ is a phthalocyanine derivative group of the general formula (V).

Taking the compound of the general formula (I), in which three groups of R ₁ and R ₂ , R ₃ and R ₄ and R ₅ and R ₆ are phthalocyanine derivative groups of the general formula (V), as an example, The production method will be described according to scheme 4.

Describes the synthesis of octacyanophthalocyanine
Report by D. Wohrle et al. [D. Wohrle.G. Meyer: Makromol. Chem.,
181 , 2127 (1980)], tetracyanobenzene is reacted in dehydrated isopropyl alcohol in the presence of lithium isopropylate under dilute conditions as shown in formula (3) to synthesize the corresponding octacyanophthalocyanine. [Scheme 4, step (11)]. As a result of this reaction, a mixture of an unreacted substance, a linear condensate which has not been formed into a ring, and octacyanophthalocyanine is obtained. The former two can be removed from the crude solid by extraction with methanol.

Next, when M ₁ is the metal ion described above, the octacyanophthalocyanine obtained in step (11) is dissolved in dimethylformamide, and the excess metal hydrochloride or metal acetate or acetylacetone complex or metal carbonyl is mixed with 80
The central metal is introduced when the reaction is carried out at ~ 150 ° C. However,
When a metal hydrochloride or metal acetate is used, the introduction can be completed completely in the presence of an equivalent amount of pyridine. Excess metal salt or by-products can be removed by washing with methanol.

The central metal-introduced or metal-free octacyanophthalocyanine derivative thus obtained is dehydrated with methanol.
Ammonia gas is added to the tetrakis (diiminoisoindolenin) derivative in the presence of sodium methylate in a mixed solvent of N-methylpyrrolidone equivalent amount (Scheme 4, step (12)).

Next, 20 to 25 parts of the diiminoisoindolenine derivative obtained in the step (3) is added to 1 equivalent of the tetrakis (diiminoisoindolenine) phthalocyanine derivative obtained in the step (12).
When M _{2 to} M ₅ are metal ions, 15 equivalents or more of the total amount of metal ion salts are dehydrated N, N-dimethylamino-
When dissolved in 2-ethanol and subjected to boiling point reflux under an inert gas atmosphere, the target phthalocyanine dimer is liberated as a black-green precipitate [Scheme 4, step (13)].

In this case, it is better to use the diiminoisoindolenine derivative in an excess amount because the yield of the desired product is better. It is thought that this is due to termination without reaction. Therefore, it is preferable that the equivalent of the above-mentioned diiminoisoindolenine derivative is in excess, and most preferably about 22 to 24 equivalents.
No more than 20 equivalents of metal salt are required, most preferably 15-
It is 15 equivalents. The crude product obtained as a black-green precipitate is
Unreacted substances, linear condensates that did not become cyclic, and MPc other than the target substance are contained as impurities, but these are extracted with dimethylformamide, and then when R _e and R _f are H, 10
Vacuum treatment at a temperature of 300 ° C to 400 ° C under a high vacuum of ^-5 torr or more, or if R _{1 to} R ₂₄ are not H, separate them by alumina or silica gel column chromatography to obtain the target phthalocyanine dimer. It can be isolated in good yield.

However, the column member and the developing solvent at this time differ depending on the types of R _e and R _f .

In the step (13), when two kinds of metal salts are used for the purpose of introducing different metals into M _{2 to} M ₅ , the metal phthalocyanine pentamer formed is a kind of central metal and Those with different arrangements are by-products. At this time, if R _e and R _f are not H, each can be separated by means such as HPLC, but when R _e and R _f are H, they cannot be separated. However, even if the mixture is used as it is, it does not hinder the ripple effect of the present invention and its value is not changed.

〔The invention's effect〕

The phthalocyanine dimer, trimer, tetramer and pentamer of the present invention have p-type semiconductor properties and have an absorption wavelength range in the near infrared region of 750 to 1000 nm. It is suitable for laser recording materials and laser printer materials.
Further, since it is in the form of a binuclear metal complex, it can be subjected to a multi-electron redox reaction and can be used, for example, as an electrochemical catalyst.

Next, the present invention will be described with reference to examples, but prior to that, examples of synthesis of respective starting materials will be shown.

(Phthalocyanine Dimer) Synthesis Example 1 Report by D. Wohrle et al. [D. Wohrle. G. Meyer: Makromol. Chem.,
181 , 2127 (1980)], o-phthalonitrile (hereinafter, abbreviated as PN, 19.73 g, 0.15 mol) and tetracyanobenzene (hereinafter, TCB, abbreviated as 8.91 g, 0.05 mol) in 2.5 l of isopropyl alcohol, lithium isopropyl Latte (3.3g, 0.05
mol) in the presence of reflux for 4 hours, and the precipitate for purification was collected by filtration (yield 14.5 g). Soxhlet used methanol as a solvent, after removing impurities for 48 hours,
The rest is dissolved in n-methylpyrrolidone (hereinafter abbreviated as NMP) and neutral alumina column (Grade-111, 90 mesh, φ
The mixture was developed with the same solvent at 7.5 × 25 cm), a small amount of the first and second colored bands were flowed out, and then the third main colored fraction was collected. After concentration under reduced pressure, the mixture was poured into a large amount of methanol to cause precipitation, which was collected by filtration and dried under reduced pressure. As a result of the analysis, it was found that the third colored portion was a dicyanophthalocyanine of the formula (I).

(1) Yield 10.5g FD-mass: m ^{+ /} e ⁼ 565 (Mw ⁼ 564.57) IR: ν _CN 2240, ν _ring 1605, 1495cm ^-1 Elemental analysis (calculated in parentheses, the same below) C72.41 (72.33) ) H2.78 (2.86) N24.81 (24.81)% Synthesis Example 2 0.57 g (1 mmol) of the compound (1) obtained in Example 1 was dissolved in 200 ml of dimethylformamide (hereinafter abbreviated as DMF), After substituting argon for 12mmol of pyridine (hereinafter Py
Was added) and cuprous chloride were added and reacted at 70 ° C. for 17 hours. After concentration under reduced pressure, the solution was poured into a large amount of methanol, and the generated precipitate was collected by filtration. The obtained solid was subjected to Soxhlet with methanol as a solvent to extract impurities for 48 hours and then dried under reduced pressure. As a result of the analysis, it was found to be copper tetracyanophthalocyanine of the formula (2).

(2) Yield 0.52g FD-mass: m ^{+ /} e = 626 (Mw ⁼ 626.10) Elemental analysis C65.17 (65.23) H2.32 (2.25) N22.39 (23.37)% Synthetic example 3 Synthetic example 2 and completely Similarly, however, anhydrous nickel acetate was used instead of cuprous chloride. As a result of analyzing the product, it was found to be a compound represented by the formula (3).

(3) Yield 0.55g FD-mass: m ^{+ /} e = 622 (Mw ⁼ 621.242) Elemental analysis C65.77 (65.74) H2.31 (2.27) N22.66 (22.55)% Synthetic example 4 Based on o-dibromobenzene t-Butyl chloride / Al
Ordinary Friedel-Crafts reaction of Cl ₃ (Reference: sANikh
alenko et al., Z. Obs. Khim., 41 , 2735-2739 (1971)) to give 4- (t-butyl) -o-dibromobenzene,
Furthermore, by Br / CN substitution reaction with cuprous cyanide, 4-
(T-Butyl) -o-phthalonitrile was obtained. 4- (t-butyl) -o-phthalonitrile 0.1m instead of PN
except that ol was used, the synthetic reaction was performed in exactly the same manner as in Synthesis Example 1, and column separation was performed in the same manner except that a mixed solvent of chloroform / NMP (1/1) was used as the solvent. Each minute was collected. After each of them was concentrated under reduced pressure, the mixture was poured into a large amount of methanol for precipitation, collected by filtration, and dried under reduced pressure. As a result of the analysis, it was found that the third colored portion was dicyanophthalocyanine of the formula (4).

(4) Yield 17.25g FD-mass: m ^{+ /} e = 733 (Mw ⁼ 732.89) IR: ν _CH 3015, ν _CN 2240, ν _ring 1605, 1495cm ⁻¹ Elemental analysis C75.41 (75.39) H5.40 ( 5.50) N19.19 (19.11)% Synthesis Example 5 Using 0.67 g (1 mmol) of the compound (4) obtained in Synthesis Example 4, bisacetylacetovanadium (IV) was used instead of cuprous chloride.
In the other synthesis example 2 using 1.2 mmol of oxide, a central metal was introduced in exactly the same manner and the same treatment was carried out to obtain a compound (5).

(5) Yield 0.51 g FD-mass: m ^{+ /} e = 798 (Mw ⁼ 797.82) Elemental analysis C69.33 (69.25) H4.84 (4.80) N17.53 (17.56)% Synthesis Example 6 JP-A-61-1 According to the method disclosed in 207431, 4-
Nitrophthalonitrile (50 g, 0.29 mol), 1.2 times equivalent of n-propyl alcohol and 1.2 times equivalent of diazabicycloundecene (abbreviated as DBU) in 200 ml of dehydrated DMF at 75 ° C. under an inert atmosphere at 12 ° C. After reacting for a period of time, concentrated under reduced pressure, poured into 1.2 l of cold 6N-HCl, extracted with chloroform, the organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and then concentrated under reduced pressure on a silica gel column (100 mesh, φ10 × 35c).
m), collect the first transparent outflow portion, concentrate under reduced pressure and dry to obtain the desired 4- (n-propoxy) phthalonitrile 3
Obtained 5.5 g.

Synthesis Example 7 Exactly the same as in Example 6, except that phenol, thiophenol, benzyl alcohol, n-hexadecyl alcohol, neo-pentyl alcohol were used in place of n-propyl alcohol, and 4- (phenoxy) phthalonitrile, respectively. 4- (thiophenyl) phthalonitrile, 4-
48.5 g, 52.7 g, 42.6 g, 44.1 g, and 48.5 g of (benzyloxy) phthalonitrile, 4- (hexadecanoxy) phthalonitrile, and 4- (neo-bentoxy) phthalonitrile, respectively.
Obtained 0.9 g.

Synthesis Example 8 20 g of o-phthalonitrile was dissolved in 200 ml of dehydrated methanol, and vigorously dried ammonia gas was passed through, and then an alcoholate solution of 0.2 g of metallic sodium dissolved in 50 ml of dehydrated methanol was added, and the boiling point was at room temperature for 1 hour. The mixture was reacted under reflux for 2 hours, and distilled off under reduced pressure at 30 ° C. or lower to obtain 21 g of diiminoisoindolenin (hereinafter, abbreviated as 6). This thing is a strong hygroscopic, the disappearance of the ν _CN in the vicinity of IR2200cm ^-1 because there is no performed instrumental analysis, it was confirmed from the appearance of the imino absorption band of 3400,1600~1750cm ^-1 to replace it.

Synthesis Example 9 Among the 4-substituted phthalonitriles described in Synthesis Examples 6 and 7,
In the same manner as in Synthesis Example 8 in which the substituents contained an ether bond, and in the same manner as in Synthesis Example 8 in the case where the substituents contained a thioether bond, a mixed solvent of methanol / tetrahydrofuran (1/1) was used as a solvent. 5- (n-propoxy) diiminoisoindolenin (hereinafter abbreviated as 7), 5-
(Phenoxy) diiminoisoindolenin (hereinafter abbreviated as 8), 5- (thiophenyl) diiminoisoindolenine (hereinafter abbreviated as 9), 5- (benzyloxy) diiminoisoindolenin (hereinafter abbreviated as 10), 5 -(N-hexadecanoxy) diiminoisoindolenin (hereinafter abbreviated as 11), 5-
(Neo-pentoxy) diiminoisoindolenin (hereinafter 1
I got 2). The yield was quantitative, and all were 95% or more. Similarly, a These are strongly hygroscopic, the disappearance of the ν _CN in the vicinity of IR2200cm ^-1 because the instrumental analysis can not be performed, it was confirmed from the appearance of the imino absorption band of 3400,1600~1750cm ^-1 to replace it.

Synthesis Example 11 The whole amount of Compound 1 was dissolved in a minimum amount of methanol / NMP mixed solvent, dry ammonia gas was vigorously passed through, 0.2 equivalent of lithium methylad to the nitrile group was added, and the flow rate of ammonia was set to about 200 ml for 1 minute. Then, the mixture was reacted at 80 ° C. After a suitable period of time, a part of the reaction mixture was sampled, dried under reduced pressure, and the IR spectrum was observed.
Disappearance of ν _CN near cm ^-1 and 3400, 1600 as an alternative
The reaction was continued (approx. 48 hours) until the appearance of the ~ 1750 cm ^-1 imino absorption band was completed. The solvent was distilled off under reduced pressure at 50 ° C or lower to quantitatively obtain the diiminoisoindoleninophthalocyanine derivative represented by (13). It has a strong hygroscopic property and cannot be analyzed by other instruments.

Synthesis Example 12 With respect to the compounds (2) to (5), corresponding diiminoisoindoleninophthalocyanine derivatives (14) to (17) were quantitatively obtained in the same manner as in Synthesis Example 11. These are still highly hygroscopic and cannot be analyzed by instruments other than IR.

R: H, M: Cu; (14) (derived from (2)) R: H, M: Ni; (15) (derived from (3)) R: t-butyl, M: H2; (16) ( R: t-butyl, M: V = 0; (17) (derived from (4)) Example 1 Compound (13) 5.7 g (10 mmol), (6) 21.8 g (0.15 mol)
Was dissolved in a minimum amount (about 80 ml) of N, N-dimethylamino-2-ethanol (hereinafter abbreviated as DMAE), and the mixture was refluxed at the boiling point for 18 hours under a dry argon atmosphere. The solution with the black-green precipitate
The mixture was cooled to about 50 ° C., poured into a large amount of cold methanol (about 1), and the blackish green precipitate was collected by filtration. This was transferred to a Soxhlet extractor and extracted with methanol until the reflux liquid became colorless. From the FD-mass spectrum after drying, it was found that this was a mixture of the target substance and metal-free phthalocyanine. Next, the metal-free phthalocyanine was sublimated and removed by heating under reduced pressure at 2.5 · 10 ⁻⁵ torr and 325 ° C. Yield 2.31g. As a result of the analysis, it was found to be a phthalocyanine dimer represented by the formula (2-a). An IR spectrum could not be observed because it has a deep absorption band in the near infrared to infrared region.

(2-a) FD-mass: m ^{+ /} e = 952 (Mw = 950.98) Visible absorption spectrum λ _max = 782,840,920nm (KBr pellet) Elemental analysis C73.28 (73.25) H3.21 (4.80) N23.51 ( 23.57) Example 2 6.3 g (10 mmol) of compound (14), 21.8 g (0.1) of compound (6)
5mol), bis (acetylacetonato) manganese 17.55g
The same reaction and treatment as in Example 1 were carried out except using (0.15 mol) to obtain a phthalocyanine dimer of the formula (2-b). Yield 2.76g.

(2-b) FD-mass: m ^{+ /} e = 1066 (Mw = 1065.44) Visible absorption spectrum λ _max = 794,856,932nm (KBr pellet) Elemental analysis C65.45 (65.39) H2.52 (2.46) N21.02 ( 21.03) Cu5.82
(5.96) Mn5.19 (5.16) Examples 3 to 9 The same phthalocyanine dimers (2-c) to (2-) as in Example 1 but under the charging and reaction conditions shown in Table 1.
i) was obtained. The results of those analyzes are summarized in Table 2.

(2-c) M ₁ = Ni, M ₂ = Co, R _{1 to} R ₄ = H, either an odd number or an even number of R _{5 to} R ₁₂ is an —OC ₃ H ₇ group, (2-d) M _{1 = H 2, M 2 =} AlCl, R 1 either t- butyl group to R ₄ in odd or even numbers, either -o- phenyl odd or even number of R ₅ to R _12, ( _{2-e) M 1 = V0} , M 2 = Zn, either t- butyl odd or even number of R ₁ to R _4, either odd or even number of R ₅ to R ₁₂ is -S- A phenyl group, (2-f) M ₁ = H ₂ , M ₂ = SnCl ₂ , R _{1 to} R ₄ = H, and an odd or even number of R _{5 to} R ₁₂ is an -o-benzyl group; -G) M ₁ = H ₂ , M ₂ = ErCl, R _{1 to} R ₄ = H, and an odd or even number of R _{5 to} R ₁₂ is —OC ₁₆ H ₃₃ group, (2-h) M _{1 = H 2, M 2 = Fe} , R 1 ~R 4 = H, either -neo-C ₁₅ H ₁₁ groups odd or even number of R ₅ ~R _12, (2- _{) M 1 = H 2, M} 2 = VOCl, R 1 ~R 4 = H, either -neo-OC ₃ H ₇ group odd or even number of R ₅ ~R _12, (phthalocyanine trimer) Synthesis Example 13 Report by D. Wohrle et al. [D. Wohrle. G. Meyer: Makromol. Chem.,
181 , 2127 (1980)], o-phthalonitrile (hereinafter abbreviated as PN, 13.15 g, 0.1 mol) and tetracyanobenzene (hereinafter TCB, abbreviated as 17.82 g, 0.1 mol) in 2.5 l of isopropyl alcohol, lithium isopropyl Latte (3.3g, 0.05
mol) in the presence of reflux for 4 hours to react, and the precipitate for purification was collected by filtration (yield 15.5 g). Soxhlet used methanol as a solvent, after removing impurities for 48 hours,
The rest is dissolved in n-methylpyrrolidone (hereinafter abbreviated as NMP) and neutral alumina column (Grade-111, 90 mesh, φ
The mixture was developed with the same solvent at 7.5 × 25 cm), a small amount of the first colored band was flown off, and then the second and third colored mainstream fractions were separately collected. After each of them was concentrated under reduced pressure, the mixture was poured into a large amount of methanol for precipitation, collected by filtration, and dried under reduced pressure. As a result of the analysis, the second coloring part and the third coloring part are respectively expressed by equations (18) and (1
It was found to be tetracyanophthalocyanine from 9).

(18) Yield 9.4g FD-mass: m ⁺ / e = 615 (Mw = 614.6) 1/2 (m ⁺ / e) = 308 IR: ν _CN 2240, ν _ring 1605,1495cm ^-1 Elemental analysis (in parentheses) Calculated value, the same as below) C70.41 (70.35) H2.28 (2.30) N27.31 (27.35)% (19) Yield 3.7 g FD-mass: m ⁺ / e = 615 (Mw = 614.6) 1/2 (m ⁺ / e) = 308 (cut along dotted line A) = 360 (cut along dotted line B) = 255 (same as above) ) IR: ν _CN 2240,220, ν _ring 1605,1495cm ^-1 Elemental analysis C70.38 (70.35) H2.41 (2.30) N27.21 (27.35)% Synthesis Example 13 Compound obtained in Synthesis Example 12 (18) And (19) to 0.61 respectively
Dissolve each of g (1 mmol) and 200 ml of dimethylformamide (hereinafter abbreviated as DMF).
Pichidine (hereinafter, abbreviated as Py) and cuprous chloride (each in mmol) were added to each, and reacted at 70 ° C for 17 hours. After concentration under reduced pressure, each solution was poured into a large amount of methanol, and the formed precipitate was collected. The solids thus obtained were each extracted with Soxhlet using methanol as a solvent, impurities were extracted for 48 hours, and then dried under reduced pressure. As a result of the analysis, the formula (2
It was found to be copper tetracyanophthalocyanine of (0) and (21).

(20) Yield ^{0.52g FD-mass: m + /e=676(Mw=676.13} ) 1/2 (m + / e) = 338 Elemental analysis C63.95 (63.86) H1.82 (1.79) N24.79 ( 24.86)% (21) Yield 0.54g FD-mass: m ⁺ / e = 676 (Mw = 676.13) 1/2 (m ⁺ / e) = 338 = 390 = 286 Elemental analysis C63.82 (63.86) H1.84 (1.79) N24.82 (24.86)% Synthesis Example 14 Exactly the same as Synthesis Example 13, except that anhydrous nickel acetate was used instead of cuprous chloride. As a result of analyzing the product, the formula (2
It was found that there are compounds shown in 2) and (23).

(22) Yield ^{0.55g FD-mass: m + /e=670(Mw=669.25} ) 1/2 (m + / e) = 335 Elemental analysis C64.57 (64.61) H1.81 (1.80) N25.06 ( 25.12)% (23) Yield 0.57g FD-mass: m ⁺ / e = 670 (Mw = 669.25) 1/2 (m ⁺ / e) = 335 = 387 = 283 Elemental analysis C64.63 (64.61) H1.81 (1.80) N25.17 (25.12)% Synthesis Example 15 t-Butyl chloride / Al for o-dibromobenzene
Ordinary Zriedel-Crafts reaction of Cl ₃ (Reference: SANikh
alenko et al., Z. Obs. Khim., 41 , 2735-2739 (1971)) to give 4- (t-butyl) -o-dibromobenzene,
Furthermore, by Br / CN substitution reaction with cuprous cyanide, 4-
(T-Butyl) -o-phthalonitrile was obtained. 4- (t-butyl) -o-phthalonitrile 0.1m instead of PN
Except that ol was used, the synthesis reaction was performed in exactly the same manner as in Synthesis Example 1, and column separation was performed in the same manner except that a mixed solvent of chloroform / NMP (1/1) was used as the solvent. The third colored mainstream fraction was separately collected. After concentration under reduced pressure, the mixture was poured into a large amount of methanol for precipitation, collected by filtration, and concentrated under reduced pressure. As a result of the analysis, it was found that the second colored part and the third colored part were tetracyanophthalocyanines of the formulas (24) and (25), respectively.

(24) Yield 17.25g FD-mass: m ⁺ / e = 729 (Mw = 728.82) 1/2 (m ⁺ / e) = 365 IR: ν _CH 3015, ν _CN 2240, ν _ring 1605, 1495cm ^-1 element Analysis C72.56 (72.51) H4.40 (4.43) N23.01 (23.06)% (25) Yield 2.68 g FD-mass: m ⁺ / e = 729 (Mw = 728.82) 1/2 (m ⁺ / e) = 365 (cut at dotted line A) = 417 (cut at dotted line B) = 313 (Same as above) IR: ν _CH 3015, ν _CN 2240,2225, ν _ring 1605,1495cm ^-1 Elemental analysis C72.52 (72.51) H4.37 (4.43) N23.11 (23.06)% Synthetic example 16 Synthetic example 15 The obtained compounds (24) and (25) respectively 0.67 g (1
was used in the same manner as in Synthesis Example 13 except that 1.2 mmol of bisacetylacetonatovanadium (IV) oxide was used instead of cuprous chloride. ), (27) was obtained.

(26) Yield ^{0.51g FD-mass: m + /e=796(Mw=795.76} ) 1/2 (m + / e) = 398 Elemental analysis C66.43 (66.41) H3.84 (3.80) N29.73 ( 29.79)% (27) Yield 0.49g FD-mass: m ⁺ / e = 796 (Mw = 795.76) 1/2 (m ⁺ / e) = 398 = 450 = 346 Elemental analysis C66.47 (66.41) H3.72 (3.80) N29.81 (29.79)% Synthetic Example 17 According to the method disclosed in JP-A-61-207431, 4-
Nitrophthalonitrile (50 g, 0.29 mol) and 1.2 times equivalent of n-propyl alcohol and 1.2 times equivalent of diazabicycloundecene (abbreviated as DBU) in 200 ml of dehydrated DMF at 75 ° C. for 12 hours in an inert atmosphere. After reacting and concentrating under reduced pressure, 1.2 l of cold
It is poured into 6N-HCl, extracted with chloroform, the organic layer is dried over anhydrous sodium sulfate, and then concentrated under reduced pressure, and the silica gel column (100 mesh, φ10 × 35c) is used with chloroform.
m), collect the first transparent outflow portion, concentrate under reduced pressure and dry to obtain the desired 4- (n-propoxy) phthalonitrile 3
Obtained 5.5 g.

Synthesis Example 18 In exactly the same manner as in Synthesis Example 17, except that phenol, thiophenol, benzyl alcohol, n-hexadecyl alcohol and neo-pentyl alcohol were used in place of n-propyl alcohol, 4- (phenoxy) phthalonitrile, 4- (thiophenyl) phthalonitrile, 4-
48.5 g, 52.7 g, 42.6 g, 44.1 g, and 48.5 g of (benzyloxy) phthalonitrile, 4- (hexadecanoxy) phthalonitrile, and 4- (neo-bentoxy) phthalonitrile, respectively.
Obtained 0.9 g.

Synthesis Example 19 20 g of o-phthalonitrile was dissolved in 200 ml of dehydrated methanol, and vigorously dried ammonia gas was passed, and then an alcoholate solution of 0.2 g of metallic sodium dissolved in 50 ml of dehydrated methanol was added, and the boiling point was at room temperature for 1 hour. The mixture was reacted under reflux for 2 hours, and distilled off under reduced pressure at 30 ° C. or lower to obtain 21 g of diiminoisoindolenin (hereinafter, abbreviated as 28). This thing is a strong hygroscopic, the disappearance of the ν _CN in the vicinity of IR2200cm ^-1 because there is no performed instrumental analysis, it was confirmed from the appearance of the imino absorption band of 3400,1600~1750cm ^-1 to replace it.

Synthesis Example 20 Among the 4-substituted phthalonitriles described in Synthesis Examples 17 and 18,
Those having a substituent containing an ether bond are exactly the same as in Synthesis Example 19, and those having a substituent containing a thioether bond are the same as in Synthesis Example 19 using a mixed solvent of methanol / tetrahydrofuran (1/1) as a solvent. 5- (n-propoxy) diiminoisoindolenin (hereinafter abbreviated as 29), 5-
(Phenoxy) diiminoisoindolenin (hereinafter abbreviated as 30), 5- (thiophenyl) diiminoisoindolenine (hereinafter abbreviated as 31), 5- (benzyloxy) diiminoisoindolenine (hereinafter abbreviated as 32), 5 -(N-hexadecanoxy) diiminoisoindolenin (hereinafter abbreviated as 33), 5-
(Neo-Bentoxy) diiminoisoindolenine (hereinafter 3
I got 4). The yield was quantitative, and all were 95% or more. Similarly, a These are strong absorption, the disappearance of the ν _CN in the vicinity of 1R2200cm ^-1 because the instrumental analysis can not be performed, it was confirmed from the appearance of the imino absorption band of 3400,1600~1750cm ^-1 to replace it.

Synthesis Example 21 The entire amount of compound (18) was dissolved in a minimum amount of methanol / NMP mixed solvent, dry ammonia gas was vigorously passed through, 0.2 equivalent of lithium methylate was added to the nitrile group, and the flow rate of ammonia was about 200 ml for 1 minute. After that, the reaction was carried out at 80 ° C. A part of the reaction mixture was sampled at an appropriate time, dried under reduced pressure, and then the IR spectrum was observed.
Disappearance of ν _CN near 2200 cm ^-1, 3400, 1600 ~
The reaction was continued until the appearance of the 1750 cm ^-1 imino absorption band was completed (it took about 48 hours). The solvent was distilled off under reduced pressure at 50 ° C or lower to quantitatively obtain the bis (diiminoisoindolenin) derivative represented by (35). This product is still strongly hygroscopic and cannot be analyzed by other instruments.

Synthesis Example 22 Compounds (19) to (27) were quantitatively obtained as the corresponding bis (diiminoisoindolenine) derivatives (36) to (44) in the same manner as in Synthesis Example 21. These are still highly hygroscopic and cannot be analyzed by instruments other than IR.

R: H, M: H ₂ ; (36) (induced by (19)) R: H, M: Cu; (38) (induced by (21)) R: H, M: Ni; (40) (( 23)) R: t-butyl, M: H ₂ ; (42) (derived from (25)) R: t-butyl, M: V = 0; (41) (derived from (27)) R: H, M: Cu; (37) (induced by (20)) R: H, M: Ni; (39) (induced by (22)) R: t-butyl, M: H ₂ ; (41) (Derived from (24)) R: t-butyl, M: V = 0; (43) (Derived from (36)) Example 10 Compound (35) 6.49 g (10 mmol), (28) 14.5 g (0.1 mol )
Was dissolved in a minimum amount (about 80 ml) of N, N-dimethylamino 2-ethanol (hereinafter abbreviated as DMAE), and the mixture was boiled under reflux for 18 hours under a dry argon gas atmosphere. The solution in which the black-green precipitate was deposited was cooled to 50 ° C., poured into a large amount of cold methanol (about 1), and the black-green precipitate was collected by filtration. This was transferred to a Soxhlet extractor and extracted with methanol until the reflux liquid became colorless. From the FD-mass spectrum after drying, it was found that this was a mixture of the target substance and metal-free phthalocyanine. Next, the metal-free phthalocyanine was sublimated and removed by heating under reduced pressure at 2.5 · 10 ⁻⁵ torr and 325 ° C. Yield 2.15g. As a result of the analysis, it was found to be a phthalocyanine trimer of the formula (3-a). An IR spectrum could not be observed because it has a deep absorption band in the near infrared to infrared region.

(3-a) FD-mass spectrum m ^{+ /} e = 1388 (Mw = 1387.42) Visible absorption spectrum λ _max = 782,840,920nm (KBr pellet) Elemental analysis C72.78 (72.72) H3.01 (3.05) N24.21 ( 24.23) Example 11 6.49 g (10 mmol) of compound (31), 14.5 g (0.
1mol), bis (acetylacetonato) manganese 17.55g
The reaction and treatment were carried out in the same manner as in Example 1 except that (0.15 mol) was used to obtain a phthalocyanine trimer of the formula (3-b). Yield 2.89g.

(3-b) FD-mass spectrum m ^{+ /} e = 1496 (Mw = 1495.28) Visible absorption spectrum λ _max = 802,866,934nm (KBr pellet) Elemental analysis C67.40 (67.47) H2.52 (2.56) N22.52 ( 22.48) Mn7.56
(7.49) Examples 12 to 18 In the same manner as in Example 10, but under the charging and reaction conditions shown in Table 3, corresponding phthalocyanine trimers (3-c) to (3-).
i) was obtained. The results of those analyzes are summarized in Table 4.

(3-c) M ₁ = Cu, M ₂ = M ₃ = Co, R _{1 to} R ₄ = H, R _{5 to} R ₁₆
Is an -OC ₃ H ₇ group, (3-d) M ₁ = Cu, M ₂ = M ₃ = AlCl, R _{1 to} R _{1 to} R ₄ = H, R ₅
Any of the odd or even numbers of -R ₁₆ is a -O-phenyl group, (3-e) M ₁ = Ni, M ₂ = M ₃ = Zn, R _{1 to} R ₄ = H, R _{5 to} R ₁₆
Odd or any even numbered -S- phenyl _{group, (3-f) M 1} = Ni, M 2 = M 3 = SnCl 2, R 1 ~R 4 = H, R 5 ~R
Either -O- benzyl group ₁₆ odd or even _{number, (3-g) M 1} = H 2, M 2 = M 3 = ErCl, either odd or even number of R ₁ to R ₄ is t - butyl, or it is -OC ₁₆ H ₃₃ groups odd or even number of _{R 5 ~R 16, (3-} h) M 1 = VO, M 2 = M 3 = Fe, odd R ₁ to R ₄ or either even-numbered t- butyl, odd or even numbers either -neo-C ₅ H ₁₁ group of _{R 5 ~R 16, (3-} i) M 1 = VO, M 2 = M 3 = VOCl ₂ , either odd or even number of R _{1 to} R ₄ is t-butyl, either odd or even number of R _{5 to} R ₁₆ is -neo-OC ₃ H ₇ group, Example 19 Compound (44) 8.3 g (10 mmol), compound (29) 20.3 g (0.1
mol), bis (acetylacetonato) manganese 8.8g (0.0
75mol), and further dioxobis (acetylacetonato)
The reaction and treatment were carried out in the same manner as in Example 10 except that 22.81 g (0.075 mol) of molybdenum was used. After that, the FD-mass spectrum showed that the obtained black-green solid had [M ₁ = VO, M ₂ = M
n, M ₃ = MoO ₂ ] [M ₁ = VO, M ₂ = M ₃ = Mn] [M ₁ = VO, M ₂ = M
₃ = MnO ₂ ], it was found to be a mixture of three phthalocyanine trimers, so silica gel column chromatography (80-100 mesh, φ7.5 × 35 cm), chloroform / methanol / water (65/24/1 ), And a small amount of the colored impurity band was flowed out, the first to third colored bands were roughly separated (not completely separated). Next, each main stream is separately separated and scanned by HPLC (Lichosorb RP-2 column, chloroform / DMF / methanol 60/5/35, 3 ml / min, 37 kg / cm ² ) to separate each main stream. It was isolated, concentrated under reduced pressure and dried. The result of the analysis,
The first to third mainstream components are (3-j) and (3-j), respectively.
k), and it was found to be a phthalocyanine trimer having a structure of (3-1).

(3-j) Yield 0.89 g FD-mass (m ^{+ /} e) = 2128 (Mw ⁼ 2176.89) Elemental analysis C59.64 (59.59) H4.33 (4.26) N15.37 (15.44) V2.33
(2.34) Mo8.88 (8.81) (3-k) Yield 1.05 g FD-mass (m ⁺ / e) = 2105 (Mw ⁼ 2103.89) Elemental analysis C61.62 (61.66) H4.53 (4.41) N15.87 (15.98) V2.43
(2.42) Mn2.66 (2.61) Mo4.51 (4.56) (3-1) Yield 0.72g FD-mass (m ⁺ / e) = 2032 (Mw ⁼ 2030.89) Elemental analysis C63.72 (63.87) H4.53 (4.57) N16.77 (16.55) V2.43
(2.50) Mn5.46 (5.41) (Phthalocyanine tetramer) Synthesis Example 23 Report by D. Wohrle et al. [D. Wohrle, G. Meyer: Mahromol. Chem.,
181 , 2127 (1980)], tetracyanobenzene (hereinafter TCB, abbreviated as 8.91 g, 0.05 ml) and phthalonitrile (hereinafter PN as abbreviated as 25.63 g, 0.20 mol) in isopropyl alcohol 2.5 l lithium isopropylate ( 3.3g, 0.05
mol) in the presence of reflux for 4 hours, and the precipitate formed was collected by filtration (yield 19.5 g). Soxhlet used methanol as a solvent, after removing impurities for 48 hours,
The residue is dissolved in n-methylpyrrolidone (hereinafter abbreviated as NMP),
Neutral alumina column (Grade-111, 90 mesh, φ7.5 x
25 cm) and developed with the same solvent, and the main colored fraction was collected. Since the second mainstream fraction was the target hexacyanophthalocyanine from the subsequent analysis results, the portion was concentrated under reduced pressure, then poured into a large amount of methanol to cause precipitation, collected by filtration, and dried under reduced pressure.

(45) Yield 17.5g FD-mass (m ^{+ /} e) ⁼ 665 (Mw ⁼ 664.61) IR: ν _CN 2235,2240 ν _ring 1605,1495cm ^-1 Elemental analysis (calculated in parentheses, the same below) C68.71 (68.67) H1.78 (1.82) N29.45 (29.51)% Synthetic Example 24 1.28 g (2 mmol) of the compound (45) obtained in Synthetic Example 23 was dissolved in 200 ml of dimethylformamide (hereinafter abbreviated as DMF), After sufficiently substituting with argon, 2.4 mmol of pyridine (hereinafter abbreviated as Py) and cuprous chloride were added, and the mixture was reacted at 70 ° C. for 17 hours. After concentration under reduced pressure, the solution was poured into a large amount of methanol, and the generated precipitate was collected by filtration. Each of the obtained solids was subjected to Soxhlet with methanol as a solvent, impurities were extracted and removed for 48 hours, and then dried under reduced pressure. As a result of the analysis, the formula (4
It was found to be copper hexacyanophthalocyanine of 6).

(46) Yield 1.16g FD-mass: m ^{+ /} e = 727 (Mw ⁼ 726.14) Elemental analysis C62.90 (62.86) H1.42 (1.39) N26.92 (27.01) Cu8.77
(8.75)% Synthesis Example 25 Exactly the same as Synthesis Example 24, except that anhydrous nickel acetate was used instead of cuprous chloride. As a result of analyzing the product, the formula (4
It was found that there is a compound shown in 7).

(47) Yield 1.07g FD-mass: m ⁺ /e=722(Mw=721.28) Elemental analysis C63.37 (63.28) H1.42 (1.40) N27.49 (27.40) Ni8.22
(8.14) Synthesis Example 26 Synthesis Example 24 except that 1.28 g (2 mmol) of the compound (45) obtained in Synthesis Example 23 was used and 2.3 mmol of bisacetylacetonatovanadium (IV) oxide was used instead of cuprous chloride. A central metal was introduced and treated in the same manner as above to obtain the compound (48).

(48) Yield 1.25g FD-mass: m ⁺ /e=730(Mw=729.54) Elemental analysis C62.61 (62.56) H1.44 (1.44) N26.93 (26.88) V7.05
(6.98)% SYNTHESIS EXAMPLE 27 According to the method disclosed in JP-A-61-207431, 4-
Nitrophthalonitrile (50 g, 0.29 mol), 1.2 times equivalent of n-propyl alcohol and 1.2 times equivalent of diazabicycloundecene (abbreviated as DBU) in 200 ml of dehydrated DMF at 75 ° C. under an inert atmosphere at 12 ° C. After reacting for a period of time, concentrated under reduced pressure, poured into 1.2 l of cold 6N-HCl, extracted with chloroform, the organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and then concentrated on a silica gel column with chloroform (100 mesh, φ10 × 35c).
m), collect the first transparent outflow portion, concentrate under reduced pressure and dry to obtain the desired 4- (n-propoxy) phthalonitrile 3
Obtained 5.5 g.

Synthesis Example 28 Exactly the same as Synthesis Example 5, except that phenol, thiophenol, benzyl alcohol, n-hexadecyl alcohol, neo-pentyl alcohol were used in place of n-propyl alcohol, 4- (phenoxy) phthalonitrile, 4- (thiophenyl) phthalonitrile, 4-
48.5 g, 52.7 g, 42.6 g, 44.1 g, and 48.5 g of (benzyloxy) phthalonitrile, 4- (hexadecanoxy) phthalonitrile, and 4- (neo-bentoxy) phthalonitrile, respectively.
Obtained 0.9 g.

Synthesis Example 29 t-Butyrochloride / Al for o-dibromobenzene
Ordinary Friedel-Crafts reaction of Cl ₃ (Reference: SANikh
alenko et al., Z. Obs. Khim., 41 , 2735-2739 (1971)) to give 4- (t-butyl) -o-dibromobenzene,
Furthermore, by Br / CN substitution reaction with cuprous cyanide, 4-
(T-Butyl) -o-phthalonitrile was obtained.

Synthesis Example 30 20 g of o-phthalonitrile was dissolved in 200 ml of dehydrated methanol, and vigorously dried ammonia gas was passed through, and then an alcoholate solution of 0.2 g of metallic sodium dissolved in 50 ml of dehydrated methanol was added, and the boiling point was at room temperature for 1 hour. The mixture was reacted under reflux for 2 hours and distilled under reduced pressure at 30 ° C. or lower to obtain 21 g of diiminoisoindolenine (hereinafter, abbreviated as 49). This thing is a strong hygroscopic, the disappearance of the ν _CN in the vicinity of IR2200cm ^-1 because there is no performed instrumental analysis, it was confirmed from the appearance of the imino absorption band of 3400,1600~1750cm ^-1 to replace it.

Synthetic Example 31 Among the 4-substituted phthalonitriles described in Synthetic Examples 28, 29 and 30, those having a substituent of t-butyl or containing an ether bond have the same substituents as in Synthetic Example 8. Those containing a thioether bond were mixed with 5-/ (n-propoxy) diiminoisoindolenin (hereinafter abbreviated as 50) in the same manner as in Synthesis Example 30 using a mixed solvent of methanol / tetrahydrofuran (1/1) as a solvent. 5- (phenoxy) diiminoisoindolenin (hereinafter abbreviated as 51), 5- (thiophenyl) diiminoisoindolenine (hereinafter abbreviated as 52), 5-
(Benzyloxy) diiminoisoindolenine (hereinafter abbreviated as 53), 5- (n-hexadecanooxy) diiminoisoindolenine (hereinafter abbreviated as 54), 5- (neo-pentoxy) diiminoisoindolenine (hereinafter 55) , And 5- (t-butyl) diiminoisoindolenin (hereinafter abbreviated as 56) were obtained. The yield was quantitative, and all were 95% or more.
Similarly, since these are strongly hygroscopic, and instrumental analysis cannot be performed, disappearance of ν _CN near IR2200cm ^-1 , 3400 instead,
It was confirmed from the appearance of the imino absorption band at 1600 to 1750 cm ^-1 .

Synthesis Example 32 10 g of compound (45) was dissolved in a minimum amount of methanol / NMP mixed solvent, dry ammonia gas was vigorously passed through, 0.2 equivalent of lithium methylate was added to the nitrile group, and the flow rate of ammonia was adjusted to about 200 ml for 1 minute. After that, the mixture was reacted at 80 ° C. A part of the reaction mixture was sampled at an appropriate time, dried under reduced pressure, and the IR spectrum was observed.
Disappearance of ν _CN near 00cm ^-1, 3400, 1600-17
The reaction was continued until the appearance of the 50 cm ^-1 imino absorption band was completed (it took about 48 hours). The solvent was distilled off under reduced pressure at 50 ° C or less, and tris (diiminoisoindolenin) shown in (57) was used.
The phthalocyanine was obtained quantitatively. This product is still strongly hygroscopic and cannot be analyzed by other instruments.

Synthetic Example 33 With respect to the compounds (46) to (50), the corresponding tris (diiminoisoindolenine) phthalocyanine derivatives (58) to (60) were quantitatively obtained in the same manner as in Synthetic Example 32. These are still highly hygroscopic and cannot be analyzed by instruments other than IR.

M: Cu; (58) (derived from (46)) M: Ni; (59) (derived from (47)) M: V = O; (60) (derived from (48)) Example 20 Compound (57 ) 7.2g (10mmol), (49) 26.19g (0.18mo
l) was dissolved in a minimum amount (about 80 ml) of N, N-dimethylamino-2-ethanol (hereinafter abbreviated as DMAE), and the mixture was boiled under reflux for 18 hours under a dry argon atmosphere. Cool the black-green precipitate solution to about 50 ° C, and cool a large amount of cold methanol (1).
It was thrown in and the black-green precipitate was collected by filtration. This was transferred to a Soxhlet extractor and extracted with methanol until the reflux liquid became colorless. From the FD-mass spectrum after drying, it was found that this was a mixture of the target substance and metal-free phthalocyanine. Next, the metal-free phthalocyanine was sublimated and removed by heating under reduced pressure at 2.5 · 10 ⁻⁵ torr and 325 ° C. Yield 2.43g. As a result of the analysis, it was found to be a phthalocyanine tetramer of the formula (4-a). An IR spectrum could not be observed because it has a deep absorption band in the near infrared to infrared region.

(M _{1 to} M ₄ = 2H) (4-a) FD-mass spectrum m ^{+ /} e = 1825 (Mw = 1823.86) Visible absorption spectrum λ _max = 828,9550,977nm (KBr pellet) Elemental analysis C72.49 ( 72.44) H3.01 (2.98) N24.61 (24.58) Example 21 Compound (58) 7.8 g (10 mmol), Compound (49) 26.19 g (0.
18mol), bis (acetylacetonato) manganese 16.38g
Except that (0.14 mol) was used, the reaction and treatment were carried out in the same manner as in Example 20, and the phthalocyanine tetramer of formula (4-b) [having the same general formula as formula (4-a), M ₁ = Cu, M _{2 to} M ₄ = M
n] was obtained. Yield 2.55g.

(4-b) FD-mass spectrum m ^{+ /} e = 2101 (Mw = 2099.095) Visible absorption spectrum λ _max = 890,961,982nm (KBr pellet) Elemental analysis C63.02 (62.94) H2.22 (2.21) N21.28 ( 21.35) Cu3.12
(3.03) Mn7.73 (7.85) Examples 22 to 27 In the same manner as in Example 20, except that the phthalocyanine pentamers (4-c) to (4-) corresponding to the charging and reaction conditions in Table 5 were used.
h) was obtained. The results of those analyzes are summarized in Table 6.

(4-c) M ₁ = Ni, M _{2 to} M ₄ = Co, R ₁ = R ₂ = H, R _{2 to} R ₂₀
Is a phenoxy group, (4-d) M ₁ = VO, M _{2 to} M ₄ = AlCl, R ₁ = R ₂ = H, R _{3 to} R
Either an odd number or an even number of ₂₀ is a -S-phenyl group, (4-e) M ₁ = VO, M _{2 to} M ₄ = Zn, R ₁ = R ₂ = H, R _{3 to} R ₂₀
Either -O- benzyl group of odd or even _{number, (4-f) M 1} = Cu, M 2 ~M 4 = Sn, R 1 = R 2 = H, R 3 ~R 20
Is an -OC ₁₆ H ₃₃ group, (4-g) M ₁ = Cu, M _{2 to} M ₄ = Er, R ₁ = R ₃ = H, R _{3 to} R _20.
Either an odd number or an even number of -neo-C ₅ H ₁₁ group, (3-h) M ₁ = Cu, M _{2 to} M ₄ = Fe, R ₁ = R ₂ = H, R _{3 to} R ₂₀
Either odd or even number of tert-butyl group, Example 28 diiminoisoindolenin (50) 366.3 g (1.8 mol),
Compound (58) 77.7g (0.1mol), nickel acetate 127.3g
(0.72 mol), zinc acetate 132.1 g (0.72 mol), and cobalt acetate 127.5 g (0.72 mol) were dissolved in 750 ml of N, N-dimethylaminoethanol, and the boiling point was refluxed while stirring under a dry argon atmosphere. Black-green solution containing the obtained precipitate
The mixture was concentrated to 100 ml, poured into 1.5 l of methanol, and a blackish green precipitate was collected by filtration. This was dissolved in a minimum amount of chloroform, and the solution was added dropwise to about 2 l of methanol with stirring, and the resulting black-green precipitate was collected by filtration and dried. Then, the colored components were separated into approximately three components by silica gel column chromatography (200 mesh, φ10 × 40 cm, chloroform). As a result of the analysis, the first component was tetrapropoxy metal phthalocyanine (a single cyclized condensate of (50) having any one of Ni, Zn, and Co as the central metal), and the third component was adsorption at the origin and poly (linia). -Phthalocyanine), the second component (Rf = 0.35, silica gel 200mesh thin layer chlorto, chloroform) was subjected to HPLC resolution. The results are summarized in Table 7. However, in addition to those shown in Table 7, some trace components that could not be separated and analyzed were observed.

(Phthalocyanine pentamer) Synthesis Example 34 Report by D. Wohrle et al. [D. Wohrle, G. Meyer: Mahromol. Chem.,
181 , 2127 (1980)], tetracyanobenzene (hereinafter referred to as TCB, 8.91 g,
0.05 mol) was refluxed for 4 hours in the presence of lithium isopropylate (3.3 g, 0.05 mol) in 2.5 l of isopropyl alcohol, and the resulting precipitate was collected by filtration (yield 1
4.5g). Use soxhlet with methanol as the solvent, 48
After removing impurities for a period of time, the residue was dissolved in n-methylpyrrolidone (hereinafter abbreviated as NMP), and a neutral alumina column (Gra
de-111, 90 mesh, φ7.5 × 25 cm) was developed with the same solvent, and the first main coloring fraction was collected. After concentration under reduced pressure, the mixture was poured into a large amount of methanol to cause precipitation, which was collected by filtration and dried under reduced pressure. As a result of the analysis, it was found that the first colored portion was octacyanophthalocyanine of the formula (61).

(61) Yield 11.5g FD-mass: m ^{2 /} e = 713 (Mw = 712.62) IR: ν _CN 2240, ν _ring 1605,1495cm ^-1 Elemental analysis (calculated in parentheses, the same below) C67.41 (67.42) ) H1.08 (1.13) N31.51 (31.45)% Synthesis Example 35 0.71 g (1 mmol) of the compound (61) obtained in Synthesis Example 34 was dissolved in 200 ml of dimethylformamide (hereinafter abbreviated as DMF), and thoroughly After substituting with argon, 1.2 mmol of pyridine (hereinafter abbreviated as Py) and cuprous chloride were added, and the mixture was reacted at 70 ° C. for 17 hours. After concentration under reduced pressure, the solution was poured into a large amount of methanol, and the generated precipitate was collected by filtration. Each of the obtained solids was subjected to Soxhlet with methanol as a solvent, impurities were extracted and removed for 48 hours, and then dried under reduced pressure. As a result of analysis, it was found that copper octacyanophthalocyanine (62) [M ₁ = Cu] in the same general formula as (61).

(62) Yield 0.54g FD-mass: m ⁺ /e=775(Mw=774.145) Elemental analysis C62.10 (62.06) H0.82 (0.78) N28.92 (28.59)% Synthetic example 36 Synthetic example 24 However, anhydrous nickel acetate was used instead of cuprous chloride. As a result of analyzing the product, the compound (6
3) It was found that M ₁ = Ni] in the same general formula as (61).

(63) Yield 0.57g FD-mass: m ^{+ /} e = 770 (Mw ⁼ 769.29) Elemental analysis C62.57 (62.45) H0.81 (0.79) N29.16 (29.13)% Synthetic Example 37 Obtained in Synthetic Example 34 In the same manner as in Synthesis Example 2 except that 0.67 g (1 mmol) of the compound (61) was used and 1.2 mmol of bisacetylacetonatovanadium (IV) oxide was used instead of cuprous chloride, a central metal was introduced, By the same treatment, compound (64) [M ₁ = V = O] having the same general formula as (61) was obtained.

(64) Yield 0.50 g FD-mass: m ^{+ /} e = 778 (Mw ⁼ 774.54) Elemental analysis C61.83 (61.79) H0.84 (0.78) N28.93 (28.82)% Synthesis Example 38 JP-A-61- According to the method disclosed in 207431, 4-
Nitrophthalonitrile (50 g, 0.29 mol), 1.2 times equivalent of n-propyl alcohol and 1.2 times equivalent of diazabicycloundecene (abbreviated as DBU) in 200 ml of dehydrated DMF at 75 ° C. under an inert atmosphere at 12 ° C. After reacting for a period of time, concentrated under reduced pressure, poured into 1.2 l of cold 6N-HCl, extracted with chloroform, the organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and then concentrated on a silica gel column with chloroform (100 mesh, φ10 × 35c).
m), collect the first transparent outflow portion, concentrate under reduced pressure and dry to obtain the desired 4- (n-propoxy) phthalonitrile 3
Obtained 5.5 g.

Synthesis Example 39 In exactly the same manner as in Synthesis Example 38, except that phenol, thiophenol, benzyl alcohol, n-hexadecyl alcohol, neo-pentyl alcohol were used in place of n-propyl alcohol, 4- (phenoxy) phthalonitrile, 4- (thiophenyl) phthalonitrile, 4-
48.5 g, 52.7 g, 42.6 g, 44.1 g, and 48.5 g of (benzyloxy) phthalonitrile, 4- (hexadecanoxy) phthalonitrile, and 4- (neo-bentoxy) phthalonitrile, respectively.
Obtained 0.9 g.

Synthesis Example 40 t-Butyrochloride / Al for o-dibromobenzene
Ordinary Friedel-Crafts reaction of Cl ₃ (Reference: SANikh
alenko et al., Z. Obs. Khim., 41 , 2735-2739 (1971)) to give 4- (t-butyl) -o-dibromobenzene,
Furthermore, by Br / CN substitution reaction with cuprous cyanide, 4-
(T-Butyl) -o-phthalonitrile was obtained.

Synthetic Example 41 20 g of o-phthalonitrile was dissolved in 200 ml of dehydrated methanol, and vigorously dried ammonia gas was passed through, then an alcoholate solution of 0.2 g of metallic sodium dissolved in 50 ml of dehydrated methanol was added, and the boiling point was at room temperature for 1 hour. The mixture was reacted under reflux for 2 hours, and distilled off under reduced pressure at 30 ° C. or lower to obtain 21 g of diiminoisoindolenin (hereinafter, abbreviated as V). This thing is a strong hygroscopic, the disappearance of the ν _CN in the vicinity of IR2200cm ^-1 because there is no performed instrumental analysis, it was confirmed from the appearance of the imino absorption band of 3400,1600~1750cm ^-1 to replace it.

Synthetic Example 42 Among the 4-substituted phthalonitriles described in Synthetic Examples 39, 40 and 41, those having a substituent of t-butyl or containing an ether bond have the same substituents as in Synthetic Example 41. Those containing a thioether bond were mixed with 5- (n-propoxy) diiminoisoindolenin (hereinafter abbreviated as 66) in the same manner as in Synthesis Example 41 using a mixed solvent of methanol / tetrahydrofuran (1/1) as a solvent. 5- (phenoxy) diiminoisoindolenine (hereinafter abbreviated as 67), 5- (thiophenyl) diiminoisoindolenine (hereinafter abbreviated as 68), 5-
(Benzyloxy) diiminoisoindolenin (hereinafter abbreviated as 69), 5- (n-hexadecanooxy) diiminoisoindolenine (hereinafter abbreviated as 70), 5- (neo-pentoxy) diiminoisoindolenine (hereinafter 71 and , And 5- (t-butyl) diiminoisoindolenine (hereinafter abbreviated as 72) were obtained. The yield was quantitative, and all were 95% or more.
Similarly, since these are strongly hygroscopic, and instrumental analysis cannot be performed, disappearance of ν _CN near IR2200cm ^-1 , 3400 instead,
It was confirmed from the appearance of the imino absorption band at 1600 to 1750 cm ^-1 .

Synthesis Example 43 The whole amount of compound (61) was dissolved in a minimum amount of methanol / NMP mixed solvent, dry ammonia gas was vigorously passed through, 0.2 equivalent of lithium methylate was added to the nitrile group, and the flow rate of ammonia was about 200 ml for 1 minute. After that, the reaction was carried out at 80 ° C. A part of the reaction mixture was sampled at an appropriate time, dried under reduced pressure, and then the IR spectrum was observed.
Disappearance of ν _CN near 2200 cm ^-1, 3400, 1600 ~
The reaction was continued until the appearance of the 1750 cm ^-1 imino absorption band was completed (it took about 48 hours). The solvent was distilled off under reduced pressure at 50 ° C or lower to quantitatively obtain tetrakis (diiminoisoindolenin) phthalocyanine represented by (68). This product is still strongly hygroscopic and cannot be analyzed by other instruments.

Synthesis Example 44 With respect to the compounds (62) to (64), the corresponding tetrakis (diiminoisoindolenine) phthalocyanine derivatives (74) to (76) were quantitatively obtained in the same manner as in Synthesis Example 43 [(68) And the same general formula]. These are still highly hygroscopic and cannot be analyzed by instruments other than IR.

M ₁ : Cu; (74) (derived from (62)) M ₁ : Ni; (75) (derived from (63)) M ₂ : V = O; (76) (derived from (64)) Example 29 7.2 g (10 mmol) of compound (73) and V29.1 g (0.20 mol) were dissolved in a minimum amount (about 80 ml) of N, N-dimethylamino-2-ethanol (hereinafter abbreviated as DMAE), and the mixture was placed under a dry argon atmosphere. Refluxed at boiling point for 18 hours. 50 times the solution of the black-green precipitate
The mixture was cooled to about 0 ° C., poured into a large amount of cold methanol (1), and a blackish green precipitate was collected by filtration. This was transferred to a Soxhlet extractor and extracted with methanol until the reflux liquid became colorless. From the FD-mass spectrum after drying, it was found that this was a mixture of the target substance and metal-free phthalocyanine. Next, the metal-free phthalocyanine was sublimated and removed by heating under reduced pressure at 2.5 · 10 ⁻⁵ torr and 325 ° C. Yield 2.51g. As a result of the analysis, it was found to be a phthalocyanine pentamer represented by the formula (5-a). Near-infrared ~
The IR spectrum could not be observed due to the deep absorption band extending to the infrared region.

(5-a) FD-mass spectrum m ^{+ /} e = 2268 (Mw = 2266.34) visible absorption spectrum λ _max = 832,960,980nm (KBr pellet) Elemental analysis C72.18 (72.08) H3.11 (3.20) N24.71 ( 24.72) Example 30 Compound (74) 7.8 g (10 mmol), Compound (65) 29.1 g (0.2
0mol), bis (acetylacetonato) manganese 29.25g
Except that (0.25 mol) was used, the reaction and treatment were carried out in the same manner as in Example 29, and the phthalocyanine pentamer (5-b) [(5-
The same general formula as a), M ₁ = Cu, M _{2 to} M ₅ = Mn] was obtained. Yield 2.76g.

(5-b) FD-mass spectrum m ^{+ /} e = 2541 (Mw = 2539.56) Visible absorption spectrum λ _max = 894,956,982nm (KBr pellet) Elemental analysis C64.45 (64.32) H2.42 (2.46) N21.98 ( 22.06) Cu2.42
(2.50) Mn8.73 (8.65) Examples 31 to 36 The same phthalocyanine pentamers (5-c) to (5-) as in Example 29, except that the charging and reaction conditions shown in Table 8 were used.
h) was obtained. The results of those analyzes are summarized in Table 9.

(5-c) M ₁ = Ni, M _{2 to} M ₅ = Co, any of the odd or even numbers of R _{1 to} R ₂₄ is a —O-phenyl group, (5-d) M ₁ = VO, M ₂ ~M ₅ = AlCl, either -S- phenyl odd or even number of _{R 1 ~R 24, (5-} e) M 1 = Cu, M 2 ~M 5 = Zn, of R ₁ to R ₂₄ either -O- benzyl odd or even _{number, (5-f) M 1} = Cu, one of _{M 2 ~M 5 = SnCl 2,} R 1 ~R 24 odd or even number is -OC ₁₆ H ₃₃ group, (5-g) M ₁ = Cu, M _{2 to} M ₅ = ErCl, either odd or even number of R _{1 to} R ₂₄ is -neo-C ₅ H ₁₁ group, (5-h) M ₁ = Cu, M _{2 to} M ₅ = Fe, either odd or even number of R _{1 to} R ₂₄ is tert-butyl group, Example 37 Diiminoisoindolenine VI 162.8 g (0.8 mol), compound XIV 84.4g (0.1mol), nickel acetate 127.3g (0.72mo
l), zinc acetate 132.1g (0.72mol), cobalt acetate 127.5g
(0.72 mol) and bisacetylacetonatooxovanadium 190.9 g (0.72 mol) were dissolved in 750 ml of N, N-dimethylaminoethanol, and the boiling point was refluxed while stirring under a dry argon atmosphere. Black-green solution containing the obtained precipitate
The mixture was concentrated to 100 ml, poured into 1.5 l of methanol, and a blackish green precipitate was collected by filtration. This was dissolved in a minimum amount of chloroform and added dropwise to about 2 l of methanol with stirring. The black-green precipitate formed was collected by filtration and dried. Then, the colored components were separated into approximately three components by silica gel column chromatography (200 mesh, φ10 × 40 cm, chloroform). As a result of the analysis, the first component was tetrapropoxy metal phthalocyanine (a single cyclized condensate of VI having any one of Ni, Zn, Co, and V = O in the central metal), and the third component was adsorption at the origin and Since it was (linia-phthalocyanine), HPLC resolution was performed on the second component (Rf = 0.35, silica gel 200mesh thin layer chlorto, chloroform). The results are summarized in Table 10. However, in addition to those shown in Table 10, there were some trace components 17 that could not be separated and analyzed.

Claims (1)

[Claims] 1. General formulas (I), (II), (III) and (I
Phthalocyanine derivative represented by V). (In the formula, R _{1 to} R ₁₂ are a hydrogen atom, a t-butyl group, and a carbon number of 20.
The following linear or branched alkoxy group, a linear or branched alkylthio group having 20 or less carbon atoms, an aryloxy group having 20 or less carbon atoms, an aralkyloxy group having 20 or less carbon atoms, an arylthio group having 20 or less carbon atoms or 20 or less carbon atoms It is an aralkylthio group, and M ₁ or M ₂ has two hydrogen atoms, which can form a complex.
A combination of a valent metal ion or a trivalent to hexavalent metal ion and a counter anion, and a combination of a metal ion and anion having a valence of +2, or R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ ,
1 to 3 pairs selected from R ₇ and R ₈ , R ₉ and R ₁₀ and R ₁₁ and R ₁₂ are represented by the general formula (V) (In the formula, R _{13 to} R ₁₈ are a hydrogen atom, a t-butyl group, and a carbon number of 20.
The following linear or branched alkoxy group, a linear or branched alkylthio group having 20 or less carbon atoms, an aryloxy group having 20 or less carbon atoms, an aralkyloxy group having 20 or less carbon atoms, an arylthio group having 20 or less carbon atoms or 20 or less carbon atoms An aralkylthio group, M ₃ is two hydrogen atoms, a divalent metal ion capable of forming a complex, or a metal ion having a valence of +2, which is a combination of a trivalent to hexavalent metal ion and a counter anion. It is a combination of anions. ) Is a phthalocyanine derivative group. ) (Wherein R ₂₁ and R ₂₂ , R ₂₃ and R ₂₄ , R ₂₅ and R ₂₆ , R ₃₁ and R ₃₂ and R
Two groups selected from ₃₃ and R ₃₄ are phthalocyanine derivative groups represented by the general formula (V), and R _{19 to} R ₃₄ other than the phthalocyanine derivative group of the general formula (V) are hydrogen atoms, t- Butyl group, linear or branched alkoxy group having 20 or less carbon atoms, linear or branched alkylthio group having 20 or less carbon atoms, aryloxy group having 20 or less carbon atoms, aralkyloxy group having 20 or less carbon atoms, arylthio group having 20 or less carbon atoms Or an aralkylthio group having 20 or less carbon atoms, M _{4 to} M ₆ are two hydrogen atoms, a divalent metal ion capable of forming a complex, or 3 to
It is a combination of a hexavalent metal ion and a counter anion, and has a valence of +2. ) (Where R ₃₉ and R ₄₀ , R ₄₁ and R ₄₂ , R ₄₃ and R ₄₄ , R ₄₅ and R ₄₆ , R
Two groups selected from ₄₇ and R ₄₈ and R ₄₉ and R ₅₀ are phthalocyanine derivative groups represented by the general formula (V),
R ₃₅ other than the phthalocyanine derivative group of the general formula (V)
To R ₅₀ are hydrogen atom, t-butyl group, linear or branched alkoxy group having 20 or less carbon atoms, linear or branched alkylthio group having 20 or less carbon atoms, aryloxy group having 20 or less carbon atoms, and 20 or less carbon atoms An aralkyloxy group, an arylthio group having 20 or less carbon atoms or an aralkylthio group having 20 or less carbon atoms, M ₇
To M ₉ are two hydrogen atoms, a divalent metal ion capable of forming a complex, or a combination of a trivalent to hexavalent metal ion and a counter anion, and a combination of a metal ion and anion having a valence of +2. . ) (In the formula, R _{51 to} R ₆₆ are a hydrogen atom, a t-butyl group, and a carbon number of 20.
The following linear or branched alkoxy group, a linear or branched alkylthio group having 20 or less carbon atoms, an aryloxy group having 20 or less carbon atoms, an aralkyloxy group having 20 or less carbon atoms, an arylthio group having 20 or less carbon atoms or 20 or less carbon atoms An aralkylthio group, or a combination of R ₅₁ and R ₅₂ is a phthalocyanine derivative group of the general formula (V), M ₁₁ or M ₁₄ is two hydrogen atoms, a divalent metal ion capable of forming a complex. Or a combination of a trivalent to hexavalent metal ion and a counter anion with a valence of +2
Is a combination of a metal ion and an anion. )