JPH0331247A - Phthalocyanine compound and intermediate thereof - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R<1> and R<2> are 1-4C alkyl; X is O or S;m is 1-8; n is 1-3; M is two H, VO, MnOH, Zn, InCl, bivalent metal atom of the period 4 or 5, group VIII of the periodic table or substituted trivalent or tetravalent metal atom). EXAMPLE:Tetra(2-dimethylaminoethoxy) VO phthalocyanine. USE:Useful as a near infrared absorption dye soluble in polar solvent or as a dye or pigment. PREPARATION:Nitrophthalonitrile is made to react with a dialkylamino(thio) alcohol in an aprotic polar solvent in the presence of a catalyst at 50-120 deg.C to obtain a new intermediate of formula II. The intermediate is reacted with a metal derivative corresponding to the M in the formula I in urea, an alcohol or a high-boiling solvent (e. g. trichlorobenzene) in the presence of a catalyst such as ammonium molybdate at 100-250 deg.C.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel phthalocyanine compound and intermediates thereof, and more particularly, to a novel phthalocyanine compound and its intermediates useful as near-infrared absorbing dyes, dyes, and pigments soluble in polar solvents. Regarding the body. (Prior Art) A method of manufacturing an optical recording medium, that is, a method of forming a layer containing a near-infrared absorber such as a phthalocyanine compound on a substrate, uses an optically transparent substrate such as glass, acrylic resin, polyethylene, etc. There is a method of coating a near-infrared absorber on a substrate such as resin or vinyl chloride resin, or a method of vapor deposition. As a coating method, there is a method in which the binder resin is dissolved in a solvent such that the binder resin is 20% by weight or less and the near-infrared absorber is 0.05 to 20% by weight, and the mixture is coated using a spin coater or the like. Solvents used for coating include halogenated hydrocarbons (e.g. dichloromethane, chloroform, carbon tetrachloride, tetrachloroethylene, dichloroethane, etc.), ketones (e.g. acetone, methyl ethyl ketone, etc.), alcohols (e.g. methanol, ethanol, propatool, etc.), Cellosolves (e.g. methyl cellosolve, ethyl cellosolve, etc.) and hydrocarbons (e.g. hexane, cyclohexane, octane, benzene, toluene, xylene, etc.) are generally widely used. 'torr, 100~3
There is a method of depositing a near-infrared absorber on a substrate at 00°C, but when manufacturing optical recording media on an industrial scale, the coating method is easier to mass-produce, is cheaper, and has a shorter time between products. This is advantageous in that there is little difference in quality. When manufacturing optical recording media using the coating method, near-infrared absorbing dyes,
In other words, phthalocyanine compounds and the like are required to have high solubility in various organic solvents. Recently, there has been a trend toward using alcohols as solvents that cause less damage to the substrate. Alcohols are also excellent solvents because they are less toxic. However, there are few phthalocyanine compounds that have high solubility in alcohols, and examples of optical recording media using phthalocyanine compounds that absorb in the near-infrared region include JP-A-61-154888 and JP-A-61-61-1. 19
No. 27281 and other publications propose phthalocyanine compounds in which a substituent is introduced into the benzene ring of phthalocyanine via an element such as oxygen or sulfur, but even these compounds cannot be said to have sufficient solubility in polar solvents. [Problems to be Solved by the Invention] An object of the present invention is to provide a novel phthalocyanine compound that solves the above-described drawbacks and has sufficient solubility even in polar solvents. [Means for Solving the Problem] As a result of intensive studies to achieve the above object, the present inventors have found that by introducing only a dialkylaminoalkoxy group or a dialkylaminoalkylthio group into the phthalocyanine skeleton, it is possible to solve the problem in an organic solvent. In contrast, we have now provided a highly soluble phthalocyanine compound, particularly a phthalocyanine compound that exhibits high solubility even in polar solvents. That is, the present invention provides a phthalocyanine compound (II
) [Formula (In IIl, R1 and R2 each independently represent an alkyl group having 1 to 4 carbon atoms, X represents an oxygen atom or a sulfur atom, m is an integer of 1 to 8, and n is an integer of 1 to 3 , M is two hydrogen atoms, vOlMnOH, Zn,
InC1 or 2 of the 4th and 5th periods of Group Ⅰ of the Periodic Table of Elements
Represents a valent metal atom, a trivalent or tetravalent substituted metal atom. ] and an intermediate compound represented by the following general formula (I) for producing the compound of general formula (II)

[In formula (I), R1 and R2 each independently represent an alkyl group having 1 to 4 carbon atoms, X represents an oxygen atom or a sulfur atom, m is an integer of 1 to 8, and n is an integer of 1 to 3. It is ]. Preferred compounds as the phthalonitrile compound of the present invention represented by general formula (I) include 4-(2-dimethylaminoethoxy)phthalonitrile, 4-(4-dimethylaminobutoxy)phthalonitrile, 4-(6 -dimethylaminohexyloxy)phthalonitrile, 4-(2-diethylaminoethoxy)phthalonitrile, 4-(2-dibutylaminoethoxy)phthalonitrile, 4-(2-(2-diethylaminoethoxy)ethoxy1phthalonitrile, 3-(2-diethylaminoethoxy)phthalonitrile, 3-[2-(2-diethylaminoethoxy)ethoxy 1
Examples include phthalonitrile, 4-(2-diethylaminoethylthio)phthalonitrile, 3-(2-diethylamineethylthio)phthalonitrile, and the like. Such a phthalonitrile compound can be produced by the following method. Nitrophthalonitrile and dialkylamino alcohol or dialkylaminothioalcohol are used as raw materials, and an aprotic polar solvent such as dimethylformamide (DMF) or dimethylacetamide (DM) is used as a reaction solvent.
AC), dimethyl sulfoxide (DMSO), etc. as a catalyst, for example, sodium hydride, 1.4-diazabicyclo[2,2,2]octane, 1.5-diazabicyclo[4,3,O]-5-nonene, In the presence of 1,8-diazabicyclo[5,4,O]-7-undecene (DBU), etc., heat and stir at 50 to 120°C, drain into water, extract with an organic solvent such as toluene, recrystallize, or Obtained as an oil or powder by column purification. On the other hand, the phthalocyanine compound represented by the general formula (, 11) of the present invention uses the phthalonitrile compound of the general formula (I) as an intermediate thereof, and R = a preferable metal corresponding to M in the formula (II). It can be obtained by reacting with a derivative in an appropriate solvent. For example, the phthalonitrile compound of general formula (I) and the metal derivative are mixed with ammonium molybdate or DB as a catalyst in urea, alcohol, or a high boiling point solvent (e.g. trichlorobenzene, chloronaphthalene, sulfolane, etc.).
It is obtained as blue or green crystals or powder by reacting with U at 100 to 250°C, removing the solvent, and performing column purification or the like. Preferred specific examples of M in general formula (II) include VO,
MnOH, FeCl, Co, Ni, Ru, Rh
, Pd, Cu, Zn. Examples include InCl and the like. Preferred specific examples of the phthalocyanine compound of the present invention include, for example, tetra(2-dimethylaminoethoxy)vO phthalocyanine, tetra(2-diethylaminoethoxy)vO phthalocyanine, tetra(2-diethylaminoethoxy)Cu phthalocyanine, tetra(2-diethylaminoethoxy) ethoxy) Ni phthalocyanine, Tetra (2-diethylaminoethoxy) Mnn Rhapthalocyanine Tetra (4-dimethylaminobutoxy) Go Phthalocyanine, Tetra (4-dimethylaminobutoxy) Cu Phthalocyanine, Tetra (6-dimethylaminohexyloxy) vO Phthalocyanine, Tetra ( 6-dimethylaminohexyloxy) Cu phthalocyanine, Tetra (6-dinithylaminohexyloxy) ■0 Phthalocyanine, Tetra (2-dibutylaminobutoxy) Go Phthalocyanine, Tetra (2-dibutylaminobutoxy) FeCl Phthalocyanine, Tetra (2-dibutylaminobutoxy) ) Rh phthalocyanine, Tetra(2-dibutylaminobutoxy) Ru Phthalocyanine, Tetra[2-(2-diethylaminoethoxy)ethoxy] Ni phthalocyanine, Tetra(2-(2-diethylaminoethoxy)ethoxyIPd Phthalocyanine, Tetra(2-diethylaminoethyl) thio) Ni phthalocyanine, Tetra(2-diethylamineethylthio) InC:l
Examples include phthalocyanine, tetra(2-diethylaminoethylthio)Cu phthalocyanine, and the like. The phthalocyanine compound represented by the general formula (II) of the present invention has an excellent ability to absorb near-infrared light of 650 to 850 nm, and also has excellent light resistance, heat resistance, acid resistance, and alkali resistance. It dissolves well in organic media such as liquid crystals and resins, and is useful as a near-infrared absorbing dye. [Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 Synthesis of 4-(2-diethylaminoethoxy)phthalonitrile 5 g of 4-nitrophthalonitrile and 17.5 g of 2-diethylaminoethanol were dissolved in 50 ml of DMF, and after adding 4.4 g of DBtl under nitrogen atmosphere, 70-8
The mixture was stirred at 0°C for 3 hours. The reaction mixture was discharged into water II2, extracted with 200 ml of toluene, and the toluene layer was separated, washed with hot water, filtered, and the solvent was distilled off. The residue was purified by column (silica gel/toluene:ethanol = 20:1),
7 g of purified product was obtained as a light brown oil. The following analysis results confirmed that this was the desired product. Elemental analysis Cl4H1? N30 CHN Calculated value (%) 69.10 7.06 +7.
27 Actual value (%) 68.98 7.87 17
．． 31M5 m/e: 243 (M") I R (neat): 2230 cm-' (-C
=N) Example 2 Synthesis of 4-(2-dibutylaminoethoxy)phthalonitrile 17.3 g of 4-nitrophthalonitrile and 43.3 g of 2-dibutylaminoethanol were dissolved in 150 ml of DMF, and DBtl 15. After adding 2 g, the mixture was stirred at 70 to 80°C for 5 hours. Add 1 part of the reaction mixture to 1 part of water.
．． After extraction with 300 ml of toluene, the toluene layer was separated, washed with hot water, filtered, and the solvent was distilled off. Column purification of the residue (silica gel/toluene:ethanol = 2
0:1) t, 10 g of purified product was obtained as a light brown oil. The following analysis results confirmed that this was the desired product. Elemental analysis C2aHzsN30 C,1(N Calculated value (%) 72.19 8.43 14.0
4 Actual value (%) 71.96 8.46 14.
10M S m/e: 299 (M") I R (neat): 2230 cm-'
(-CmiN) Example 3 Synthesis of 4-(4-diethylaminoethoxy)phthalonitrile 17.3 g of 4-nitrophthalonitrile and 35.1 g of 4-dimethylaminobutanol were dissolved in 150 ml of DMF, and DBU was added under a nitrogen atmosphere. After adding +5.2g,
The mixture was stirred at 70-80°C for 4 hours. The reaction mixture was diluted with 1.
After extraction with 300 ml of toluene, the toluene layer was separated, washed with hot water, filtered, and the solvent was distilled off. Column purification of the residue (silica gel/toluene:ethanol = 20
:1) L, 11.5 g of purified product was obtained as a light brown oil. The following analysis results confirmed that this was the desired product. Elemental analysis C14817N30 CHN Calculated value (%) 69.10 7.06 17.2
7 Actual value (%) 69.25 7.18 17.
12M5 m/e: 243 (M") I R (neat): 2230 cm-'
(-C'N) Example 4 Synthesis of 4-(6-dimethylaminohexyloxy)phthalonitrile 17.3 g of 4-nitrophthalonitrile and 29 g of 6-dimethylaminohexanol were dissolved in 200 ml of DMF, and under a nitrogen atmosphere. After adding 15.2g of Dell to
The mixture was stirred at 70-80°C for 3 hours. The reaction mixture was diluted with 1.
After extraction with 300 ml of toluene, the toluene layer was separated, washed with hot water, filtered, and the solvent was distilled off. Column purification of the residue (silica gel/toluene:ethanol=
2D: 1) L/, 8 g of purified product was obtained as a light brown oil. The following analysis results confirmed that this was the desired product. Elemental analysis C+Jl□, N30 HN Calculated value (%) 70.80 7.82 15.4
9 Actual value (%) 70.56 7.87 15.
39M5 m/e: 271 (M") I R (neat): 2230 cm-'
(-C3N) Example 5 Synthesis of 4-[2-(2-diethylaminoethoxy)ethoxy]phthalonitrile 20.2 g of 4-nitrophthalonitrile and 23.2 g of 2-(2-diethylaminoethoxy)ethanol were mixed with DMFL.
Dissolve in ooml DBtl 20.4 under nitrogen atmosphere
After adding g, the mixture was stirred at 70 to 80°C for 3 hours. The reaction mixture was drained into 1.51ml of water and 300ml of toluene.
After extraction, the toluene layer was separated, washed with hot water, filtered, and the solvent was distilled off. The residue was purified by column (silica gel/toluene:ethanol=20:l) to obtain 8.3 g of purified product as a pale brown oil. The following analysis results confirmed that this was the desired product. Elemental analysis C'+ aL +N5OzHN Calculated value (%) 66.86 7.38 14.6
2 Actual value (%) 66.71 7.33 14.
60M5 m/e: 287 (M") I R (neat): 2230 cm-'
(-C=N) Example 6 Synthesis of 3-(2-(2-diethylaminoethoxy)ethoxy)phthalonitrile 7g of 3-nitrophthalonitrile, 9.8g of 2-(2-diethylaminoethoxy)ethanol in 50ml of DMF
After adding 6.2 g of DBU under a nitrogen atmosphere, the mixture was stirred at 70 to 80°C for 5 hours. The reaction mixture was discharged into 800 ml of water, extracted with 200 ml of toluene, the toluene layer was separated, washed with hot water, filtered, and the solvent was distilled off. The residue was purified by column (silica gel/toluene; ethanol = 20:l) to obtain 3 g of purified product as a pale brown oil. The following analysis results confirmed that this was the desired product. Elemental analysis Cl8) 1218302CHN Calculated value (%) 66.86 7.38 14.6
2 Actual value (%) 66.71 7.33 14.
60M S m/e: 287 (M") I R (neat) + 2230 am-'
(-C=N) Example 7 Synthesis of 4-(2-diethylaminoethylthio)phthalonitrile 20.7 g of 4-nitrophthalonitrile and 24.4 g of 2-diethylaminoethanethiol hydrochloride were added in DMF 10
After adding 20.4 g of DBU under a nitrogen atmosphere, the mixture was stirred at 70 to 80°C for 6 hours. The reaction mixture was mixed with 1.5 i of water! After extraction with 300 ml of toluene, the toluene layer was separated, washed with hot water, filtered, and the solvent was distilled off. 100 ml of n-hexane was added to the residue and powdered with stirring. After filtering and washing with n-hexane, purified product 2
2 g was obtained as a light brown powder. The melting point of the obtained compound was 60.5-62.5°C. The following analysis results confirmed that this was the desired product. In addition, NM of the obtained compound
The R spectrum and IR spectrum are shown in Figures 1 and 2, respectively. Elemental analysis C14) 117N3s HN Calculated value (%) 64.82 6.62 16.2
0 Actual value (%) 64.79 6.45 16.
23M S' m/e:259 (M”)I R(
KBr): 2230 cm-' (-C=
N) IH-NMRδ: 1.05 (6)1. t,
-N (CHzCfl-) 2) 2, 56 (41(
, q, -N (C12CH3) 2) 2.78 (2
)1. t, -5-CH2CH2-N=13.15 (2
H, t, -5-C)12CH2-N=)7.26-7.
74 (3)1. m) Example 8 Synthesis of 3-(2-diethylaminoethylthio)phthalonitrile 7 g of 3-nitrophthalonitrile 10.3 g of 12-diethylaminoethanethiol hydrochloride was dissolved in 50 ml of DMF and 6.2 g of DBtl was added under nitrogen atmosphere. After that, the mixture was stirred at 70 to 80°C for 6 hours. Pour the reaction mixture into 6 liters of water.
After extraction with 150 ml of toluene, the toluene layer was separated, washed with hot water, filtered, and the solvent was distilled off. 50 ml of n-hexane was added to the residue and powdered with stirring. After filtering, it was washed with n-hexane to obtain 4.8 g of a purified product as a light brown powder. The melting point of the obtained compound is 51-52°C
Met. The following analysis results confirmed that this was the desired product. In addition, the NMR spectrum and I
The R spectra are shown in FIGS. 3 and 4, respectively. Elemental analysis C14H17N3S C)IN Calculated value (%) 64.82 6.62 16.2
0 Actual value (%) 64.90 6.50 16.
45M5 m/e: 259 (M”) I R (KBr): 2230 cm-' (
-CEN)'H-NMRδ: 1.01 (6H,
t, -N(CHzCHs)i)2,57 (4H,q,
-N (CH2CH3) 2)2,78 (2H,t
, -5-(JIaCHa-N=)3,19 (2)
1. t, -5-CHzCt (a-N value) 7.52~
7.71 (3H, m) Example 9 Synthesis of tetra(2-diethylaminoethoxy)Ni phthalocyanine 4-(2-diethylaminoethoxy)phthalonitrile 3
g, nickel(II) chloride 0.8g, urea 3.7g,
After mixing 0.1 g of ammonium molybdate and 20 ml of trichlorobenzene, the mixture was stirred at 170 to 180°C for 2 hours. After cooling, add 150 ml of toluene for extraction, wash with hot water, filter, dry the toluene solution with magnesium sulfate, and then column purify (silica gel/toluene:ethanol = 50:1) L. 1 g of the purified product is made into a blue-green powder. Obtained. The following analysis results confirmed that this was the desired product. In addition, atomic absorption spectrometry was used for metal analysis. Elemental analysis CaaHaaN+zNiOnCHN
Ni Calculated value (%) 65.17 6.65 16.29
5.69 Actual value (%) 65. +3 6.70 16
．． 10 5.65 The toluene solution of the compound thus obtained showed maximum absorption at 673 nm, and the molecular extinction coefficient was 9.87×10′ 42/mol-cm. Moreover, the solubility of the obtained compound in methanol at 25°C was 10% or more. Example 1O Synthesis of tetra(2-diethylaminoethoxy)Zn phthalocyanine 4-(2-diethylaminoethoxy)phthalonitrile 2
．． 43g, zinc chloride (II) 0.34g, DB
After mixing 1.52 g of U and 60 ml of n-amyl alcohol, the mixture was stirred under reflux for 6 hours. After distilling off the solvent, the residue was purified by column 1 (alumina/toluene:ethanol=20:
1) to obtain 1.9 g of purified product as a blue-green powder. The following analysis results confirmed that this was the desired product. Elemental analysis Cs5HsaN+zZn04CHN
Zn Calculated value (%) 64.75 6.61 16.18
6.29 Actual value (%) 64.58 6.67 16
．． 08 6.20 The toluene solution of the compound thus obtained showed maximum absorption at 682 nm, and the molecular extinction coefficient was 1.31 x 10' A/mol-cm. Moreover, the solubility of the obtained compound in methanol at 25°C was 10% or more. Example 11 Synthesis of tetra(2-diethylaminoethoxy) MnOH phthalocyanine 4-(2-diethylaminoethoxy)phthalonitrile 2
．． 4g, manganese(II) chloride 0.5g, DBU
After mixing 1.52 g of n-amyl alcohol and 50 ml of n-amyl alcohol, the mixture was stirred under reflux for 6 hours. After evaporating the solvent, the residue was purified by column (alumina/toluene:ethanol=20:1)
0.9 g of purified product was obtained as a blue-green powder. The following analysis results confirmed that this was the desired product. Elemental analysis Cl5Ja9N+Jn06CHN
Mn Calculated value (%) 64.34 6.67 16.08
5.26 Actual value (%) 64.56 6.53 16
．． 01 5.13 The toluene solution of the compound thus obtained showed maximum absorption at 725 nm, and the molecular extinction coefficient was 1, OIX 10' 42 /mol-cm. Moreover, the solubility of the obtained compound in methanol at 25°C was 10% or more. Example 12 Synthesis of tetra(4-diethylaminobutoxy)Co phthalocyanine 4-(4-diethylaminobutoxy)phthalonitrile 2
g, cobalt(II) chloride 0.4g, DBU 1
．． After mixing 3g of n-amyl alcohol and 50ml of n-amyl alcohol, the mixture was stirred under reflux for 6 hours. After evaporating the solvent, the residue was purified by column (alumina/toluene:ethanol = 50:1)
Then, 0.6 g of purified product was obtained as a blue-green powder. The following analysis results confirmed that this was the desired product. Elemental analysis Cs6HaaN+zCO04CHN
C. Calculated value (%) 65.15 6.65 16.29
5.71 Actual value (%) 65.01 6.73 16
．． 50 5.50 The toluene solution of the compound thus obtained showed maximum absorption at 674 nm, and the molecular extinction coefficient was 1.21X 10' 12 /mol-cm. Moreover, the solubility of the obtained compound in methanol at 25°C was 10% or more. Example 13 Synthesis of tetra(6-dimethylaminohexyloxy) Cu phthalocyanine 2.7 g of 4-(6-dimethylaminohexyloxy) phthalonitrile, Ig of copper(II) chloride, 4.6 g of urea, and 20 ml of trichlorobenzene. After mixing, 190～
The mixture was stirred at 200°C for 5 hours. After cooling, toluene 100
m1 was added, extracted, filtered, and directly purified by column (alumina/toluene:ethanol = 50:I) to obtain purified product 0.
．． 8 g was obtained as a blue-green powder. The following analysis results confirmed that this was the desired product. Elemental analysis CaJaJ+zCu04CHN
Cu calculated value (%) 66.89 7.38 14.63
5.53 Actual value (%) 66.78? ,46 1
4.49 5.43 The toluene solution of the compound thus obtained showed maximum absorption at 682 nm, and the molecular extinction coefficient was 1.02X 10'β/mol·cm. Further, the solubility of the obtained compound in methanol at 25°C was 5% or more. Example 14 Tetra(6-dimethylaminohexyloxy)■. Synthesis of phthalocyanine 2.7 g of 4-(6-dimethylaminohexyloxy)phthalonitrile, 1.3 g of vanadyl trichloride, Ig ammonium molybdate, 4.6 g of urea, 20 ml of trichlorobenzene. After mixing 3.5g of DBIJ, 18
The mixture was stirred at 0 to 190°C for 5 hours. After cooling, toluene 2
00ml was added, extracted, filtered, and then column purified (
Alumina/toluene:ethanol=50:1) to obtain 0.7 g of a purified product as a blue-green powder. The following analysis results confirmed that this was the desired product. Elemental analysis Ca4HaJI+zOsVHNV Calculated value (%) 66.69 7.36 14.59
4.42 Actual value (%) 66.71 7.27 14
．． 61 4.30 The toluene solution of the compound thus obtained showed maximum absorption at 703 nm, and the molecular extinction coefficient was 1.15X 10'β/mol-cm. Moreover, the solubility of the obtained compound in methanol at 25°C was 5% or more. Example 15 Synthesis of tetra(2-dibutylaminoethoxy)Co phthalocyanine 4-(2-dibutylaminoethoxy)phthalonitrile 3
．． 0g, cobalt(II) chloride 0.7g, -
t: 0.1 g of ammonium lipdate, 3.0 g of urea and 201 g of dichlorobenzene. After mixing 3.5 g of DBU, the mixture was stirred at 180 to 190°C for 4 hours. After cooling, add 100 ml of toluene for extraction, filtration, and column purification (alumina/toluene: ethanol = 20
+1) to obtain 1.1 g of purified product as a blue-green powder. The following analysis results confirmed that this was the desired product. Elemental analysis C72) 1100N12COO4CHN
C. Calculated value (%') 6B, 80 8.04 13.38
4.69 Actual value (%) 68.59 7.98 1
3.51 4.39 The toluene solution of the compound thus obtained showed maximum absorption at 673 nm, and the molecular extinction coefficient was 9.83 x 10' (1/moicm). The solubility at 25°C was 5% or more. Example 16 Synthesis of tetra[2-(2-diethylaminoethoxy)ethoxy]Ni phthalocyanine 4-[2-(2-diethylaminoethoxy)ethoxycottalonitrile 8.3 g, Nickel (II) chloride 1
, 9g, urea 8.7g, ammonium molybdate 0.
After mixing 1 g and 30 ml of trichlorobenzene, 17
The mixture was stirred at 0 to 180°C for 3 hours. After cooling, toluene 1
The toluene solution was dried with magnesium sulfate, and then column purified (alumina/toluene:ethanol = 50:1) to obtain purified product 3.
5 g was obtained as a blue-green powder. The following analysis results confirmed that this was the desired product. Elemental analysis CaJaJI+aNiOaCHN
Ni Calculated value (%) 63.61 ? ,02 13.91
4.86 Actual value (%) 63.38 7.11 1
3.96 4.75 The toluene solution of the compound thus obtained showed maximum absorption at 673 nm, and the molecular extinction coefficient was 1.15X 10' (1/mol-cm). The solubility in methanol at 25° C. was 12% or more. Example 17 Synthesis of tetra[2-(2-diethylaminoethoxy)ethoxy] Pd phthalocyanine 3-(2-(2-diethylaminoethoxy)ethoxycottonitrile) 1. 6g, palladium(II) chloride
0.5g, urea 2g, ammonium molybdate 0.1
g, after mixing 20ml of trichlorobenzene, 190
Stirred at ~200°C for 5 hours. After cooling, toluene 10
Add 0ml and filter, then column purification (alumina/
Toluene:ethanol=20:1) L, purified product 0.6
g was obtained as a blue-green powder. The following analysis results confirmed that this was the desired product. Elemental analysis Ca4)1s4N+□PdO. CHN Pd Calculated value (%) 61.20 6.75 13.39
8.47 Actual value (%) 60', 95 6.81
+3.50 8.33 The toluene solution of the compound thus obtained showed maximum absorption at 686 nm, and the molecular extinction coefficient was 1.12x 10' I2/moLcm. Further, the solubility of the obtained compound in methanol at 25°C was 12% or more. Example 18 Synthesis of tetra(2-diethylaminoethylthio)Ni phthalocyanine 5.2 g of 4-(2-diethylaminoethylthio)phthalonitrile, 1.3 g of nickel chloride (TI), 6 g of urea,
After mixing 0.1 g of ammonium molybdate and 20 ml of trichlorobenzene, the mixture was stirred at 170 to 180°C for 2 hours. After cooling, extract by adding 100 ml of toluene, wash with hot water, filter, dry the toluene solution with magnesium sulfate, column purify (alumina/toluene:ethanol = 50:1), and remove 2.8 g of the purified product to a bluish-green color. Obtained as a powder. The following analysis results confirmed that this was the desired product. Elemental analysis C5aHsaN+zNiS4CHN
Ni Calculated value (%) 61.35 6.26 15.34
5.35 Actual value (%) 61.44 6.30 15
．． 55 5.11 The toluene solution of the compound thus obtained showed maximum absorption at 686 nm, and the molecular extinction coefficient was 9.64×10'β/mol-cm. Further, the solubility of the obtained compound in methanol at 25°C was 0.5% or more. Example 19 Synthesis of tetra(2-diethylaminoethylthio) 1nCl phthalocyanine 2.6 g of 3-(2-diethylaminoethylthio) phthalocyanine, 1.1 g of indium chloride (m), 3 g of urea
After mixing 0.1 g of ammonium molybdate and 20 ml of trichlorohensen, the mixture was stirred at 170 to 18° C. for 6 hours. After cooling, 100 ml of toluene was added for extraction, and after filtration, column purification (alumina/toluene:ethanol=20:l) was performed as it was to obtain purified product 1, og as a blue-green powder. The following analysis results confirmed that this was the desired product. Elemental analysis C5aHaaN+zCIInS4CHN
In Calculated value (%) 56.62 5.78 14.15
9.67 Actual value (%) 56.38 5,81 14
．． 06 9.55 The toluene solution of the compound thus obtained showed maximum absorption at 740 nm, and the molecular extinction coefficient was 8.69x 10' A /mo1cm. Moreover, the solubility of the obtained compound in methanol at 25°C was 0.5% or more. Example 20 Synthesis of tetra(2-diethylamineethylthio)Cu phthalocyanine 3-(2-diethylaminoethylthio)phthalonitrile 2.0g, copper(I) chloride 0.5g%DBIJ 1.
After mixing 2 g and 50 ml of n-amyl alcohol,
The mixture was stirred under reflux for 8 hours. After distilling off the solvent, the residue was purified by column (alumina/toluene:ethanol=50:1) L
, 1.0 g of purified product was obtained as a blue-green powder. The following analysis results confirmed that this was the desired product. Elemental analysis C5aHaaN+zCuS4CHN
Cu calculated value (%) 61.08 6.24 15.27
5.77 Actual value (%) 60.89 6.30 15
．． 41 5.49 The toluene solution of the compound thus obtained showed maximum absorption at 713 nm, and the molecular extinction coefficient was 1.27XIO'β/mo 1-cm. Further, the solubility of the obtained compound in methanol at 25°C was 0.5% or more. [Effects of the Invention] As explained above, the present invention makes it possible to provide a novel phthalocyanine compound with high solubility in organic solvents, particularly polar solvents.

[Brief explanation of drawings]

1 and 2 show the 4-(
NM of 2-diethylamineethylthio)phthalonitrile
R and IR spectra, FIGS. 3 and 4 are NMR and IR spectra of 3-(2-diethylaminoethylthio)phthalonitrile produced in Example 8.

Claims (1)

[Claims] (1) A phthalonitrile compound represented by general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In formula (I), R^1 and R^2 each independently represent an alkyl group having 1 to 4 carbon atoms, and x represents an oxygen atom or a sulfur atom. m is an integer of 1 to 8, and n is an integer of 1 to 3. ] (2) Phthalocyanine compound represented by general formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [In formula (II), R^1 and R^2 each independently have a carbon number of 1 to 4 represents an alkyl group, x represents an oxygen atom or a sulfur atom, m represents an integer of 1 to 8, n represents an integer of 1 to 3, M represents two hydrogen atoms, VO, MnOH, Zn, I
nCl or 2 of the 4th and 5th periods of Group VIII of the Periodic Table of Elements
Represents a valent metal atom, trivalent or tetravalent substituted metal atom. ]