JPH0730257B2 - Method for producing alkoxy phthalocyanine - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an alkoxyphthalocyanine useful as a novel recording material for optical disks or an intermediate for a novel phthalocyanine compound.

[0002]

2. Description of the Related Art A β-substituted tetraalkoxyphthalocyanine (in the formula (I) below, --OR group is 2 or 3,
Compounds substituted at the 6 or 7, 10 or 11, 14 or 15 positions)

[0003]

[Chemical 4] The manufacturing method of is described in various documents. For example,
A method for producing 2,6,10,14-tetra-isopropoxyphthalocyanine is described in NOUVEAU JOURNAL.
DE CHIMIE Volume 6, pp. 653-658 (19
1982). The method is a method in which diiminoisoindoline and N, N-dimethylaminoetalol are mixed and reacted at 140 ° C. for 22 hours. However, this method had a low yield of 38%. Further, as an example of the production of an α-position-substituted tetraalkoxyphthalocyanine (a compound in which the —OR group is substituted at the 1-, 4-, 5-, 8-, 9-, 12-, 13- or 16-position in the formula (I)), JP-A-3- 62878 (EP-03736)
43) discloses a method for producing 1,5,9,13-tetraalkoxyphthalocyanine. The method is a method in which phthalonitrile, palladium chloride, 1,8-diazabicyclo [5.4.0] -7-undecene (hereinafter abbreviated as DBU) and n-amyl alcohol are mixed and reacted under reflux. . However, this method also had a low yield of 20%, and was not an industrially applicable method.

[0004]

The object of the present invention is to produce an α-substituted tetra-alkoxy phthalocyanine, especially an alkoxy phthalocyanine having a large steric hindrance in a good yield and without mixing by-products such as metal-free phthalocyanine. To provide a way to do.

[0005]

The inventors of the present invention have completed the present invention as a result of extensive studies to achieve the above object. That is, the present invention provides the following general formula (1)

[0006]

[Chemical 5] (Wherein R ¹ represents a secondary alkyl group having 3 to 20 carbon atoms in the formula (1)), 1 to 4 kinds of 3-alkoxyphthalonitrile and an alcohol solution or suspension of an organic base are used. To 120 ° C., the metal or metal derivative is added at the same temperature, and the reaction is carried out at 90 to 120 ° C.

[0007]

[Chemical 6] (In the formula (2), each R ¹ independently represents a secondary alkyl group having 3 to 20 carbon atoms, Met represents a divalent metal atom or an oxymetal. The substitution position of the —OR ¹ group is 1 Alternatively, the method is a method for producing an alkoxyphthalocyanine represented by 4, 5 or 8, 9 or 12 and 13 or 16 position.

The characteristic feature of the production method of the present invention is that 3-alkoxyphthalonitrile and an organic base are dissolved or suspended in an alcohol solvent and the temperature is raised from 90 to 120 ° C. and then a metal derivative is added. That is, the yield of α-substituted tetraalkoxyphthalocyanine was remarkably improved by reacting at 120 to 120 ° C.

In the above formula (1) or (2), R¹
The secondary alkyl group represented by has 3 to 2 carbon atoms.
0 hydrocarbons or halogenated hydrocarbons, preferred
As a new alkyl group, a secondary to quaternary carbon atom is combined.
It is a group having 2 to 4 in total. As a specific example, is
o-propyl group, sec-butyl group, tert-butyl group
Group, neo-pentyl group, 1,2-dimethylpropyl
Group, cyclohexyl group, 1,3-dimethylbutyl group, 1
-Iso-propylpropyl group, 1,2-dimethylbutyl
Group, 1,4-dimethylpentyl group, 2-methyl-1-
iso-propylpropyl group, 1-ethyl-3-methyl
Butyl group, 3-methyl-1-iso-propylbutyl
Group, 2-methyl-1-iso-propylbutyl group, 1-
hydrocarbon groups such as t-butyl-2-methylpropyl group,
1,1,1,3,3,3-hexafluoro-2-propyi
And a halogenated alkyl group such as a ruthel group. Also R¹
Is C₃~ C ₂₀It may be a linear alkyl group.

As an example of the divalent metal represented by Met,
Cu, Zn, Mn, Fe, Co, Ni, Ru, Rh, P
d, Pt, Pb, and the like, and examples of the oxy metal include VO, TiO, and the like. Among these metals or metal derivatives, the present invention is particularly effective for producing phthalocyanine in which Pd and Pt are central metals.

The conditions for synthesizing the phthalocyanine ring are 3-
Alkoxyphthalonitrile (1) 1 to 4 kinds is heated to 90 to 120 ° C. in an organic base and an alcohol solvent, a metal or a metal derivative is added at the same temperature, and 90 to 120
The reaction is performed by heating at ℃. Especially in the case of a metal such as Pd or Pt, the addition temperature of the metal derivative is 1
When the temperature exceeds 20 ° C, metal-free phthalocyanine is produced as a by-product, and when the temperature is lower than 90 ° C, linear phthalocyanine that does not form a ring is formed, and any of them causes a decrease in yield. Also, when a metal derivative is previously charged simultaneously with 3-alkoxyphthalonitrile and an organic base and the temperature is raised to react, linear-phthalocyanine is produced and the yield decreases.
In addition, it is preferable that the reaction is usually performed under a nitrogen atmosphere.

As the solvent, alcohol having a boiling point of 90 ° C. or higher, preferably 100 ° C. or higher is good. As a specific example, "ORGANIC SOLVENT" J. A.
Riddick and W. B. Bunger, WI
Published by LEY-INTERSCIENCE, 1970 or "THE MERCK INDEX" 11th edition, M
ERCK & CO. N-propyl alcohol, n-butyl alcohol, described in 1989.
Examples include n-amyl alcohol, 1-hexanol, 1-heptanol, 1-octanol and the like. The amount of these alcohol solvents used is 1 to 100 times by weight, preferably 5 to 20 times by weight that of 3-alkoxyphthalonitrile.

The metals or metal derivatives used in the reaction include Ti, V, Mn, Fe, Co, Ni, Cu, Zn,
Pb, Ru, Rh, Pd, Pt and halides thereof,
Examples thereof include acetates, carboxylic acid derivatives, sulfates, nitrates, carbonyl compounds, oxides and complexes. Preferably,
Palladium chloride, palladium bromide, palladium acetate, platinum chloride, platinum bromide, platinum acetate. The amount of metal or metal derivative used is 3-alkoxyphthalonitrile,
It should be 1/4 mol or more, preferably 1/4 to 1 /
2 mol.

DBU or 1,5-diazabicyclo [4.3.0] -5-nonene as an organic base (hereinafter DBN
Abbreviated) is used. The amount of these bases used may be equimolar or more, preferably 1 to 1.5 times the molar amount of 3-alkoxyphthalonitrile as a raw material.

The starting material 3-alkoxyphthalonitrile (1) used in the method of the present invention is synthesized by the method of the following formula (3).

[0016]

[Chemical 7] The starting material, 3-nitrophthalonitrile, is Tokyo Kasei Co., Ltd.
I got more. The synthesis of 3-alkoxyphthalonitrile from 3-nitrophthalonitrile is NOUVEAUJOU
RNAL DE CHIMIE VOL. 6 NO. 1
2, p653-58, 1982. That is, the alcohol was converted to sodium alkoxide with sodium hydride and subsequently reacted with 3-nitrophthalonitrile at 0 to 100 ° C. to obtain the desired 3-alkoxyphthalonitrile.

The α-substituted tetraalkoxyphthalocyanines obtained by the present invention are represented by the following formulas (4) to (7)

[0018]

[Chemical 8] (In the formula (4) (7), R ¹ and Met are. The same meanings as R ¹ and Met in the formula (2)) 4 isomers represented by is considered. Another feature of the production method using phthalonitriliu raw material is that the isomer ratio can be controlled. That is, the synthesized phthalocyanines (4) and (5) were the main products, and the ratio thereof was 60/40 to 40 /.
It was found that the ratio of 60 produced almost the same.
When the sum of the abundance ratios of (4) and (5) is less than 100, formation of isomers of (6) and (7) is recognized. According to the present invention, specific isomers can be created separately. Comparing the organic solvent solubilities of (4) and (5),
Since the isomer of (4) has high solubility and (5) has low solubility, (4) is advantageous for the solvent coating method, and (5) is effective for fields requiring solvent resistance stability.

[0019]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 The following formula (8)

[0021]

[Chemical 9] 22.8 g of phthalonitrile (100 mmo
l), DBU 15.2 g (100 mmol) and n
-Mix 125 g amyl alcohol at room temperature, 110 ° C
The temperature was raised to. Next, at the same temperature, 5.3 g of palladium chloride
(30 mmol) and added at 110 ° C to 120 ° C for 8 hours.
After reacting for a time and cooling to room temperature, the insoluble matter was filtered off, the filtrate was concentrated under reduced pressure, 500 ml of methanol was added, the precipitated crystals were filtered off, and washed with 100 ml of methanol. 60
When dried at ℃, the following formulas (9), (10), (1
22.7 g of a mixture of 1) and (12) was obtained. The yield was 90%. The mixture has a maximum absorption wavelength λ _max = 6
It was 87 nm and ε _max = 3.0 × 10 ⁵ g ^-1 cm ² (toluene). The production ratio is (9) / (10) / (11) / (12) = 5 from the area ratio of the liquid chromatogram.
It was 0/48/1/1.

[0022]

[Chemical 10]

[0023]

[Chemical 11]

[0024]

[Chemical 12]

[0025]

[Chemical 13]

Example 2 The following formula (13)

[0027]

[Chemical 14] 24.2 g of phthalonitrile (100 mmo
l), DBU 15.2 g (100 mmol) and n
100 g of amyl alcohol were mixed at room temperature and the temperature was raised to 90 ° C. Next, at the same temperature, 5.3 g (3
0 mmol), and reacted for 12 hours at 90 ° C. to 100 ° C., cooled to room temperature, filtered through insoluble matter, concentrated the filtrate under reduced pressure, added 400 ml of methanol and filtered through precipitated crystals, It was washed with 100 ml of methanol. When dried at 60 ° C., the following formulas (14), (15), (16)
24.6 g of a mixture of (17) and (17) was obtained. The yield was 92%. The mixture has a maximum absorption wavelength λ _max = 692
nm, ε _max = 2.8 × 10 ⁵ g ^-1 cm ² (toluene)
Met. The production ratio is (14) / (15) / (16) / (17) = 48 / from the area ratio of the liquid chromatogram.
It was 48/2/2.

[0028]

[Chemical 15]

[0029]

[Chemical 16]

[0030]

[Chemical 17]

[0031]

[Chemical 18]

Example 3 The following formula (18)

[0033]

[Chemical 19] 25.6 g of phthalonitrile (100 mm
ol), 12.4 g (100 mmol) of DBN and 120 g of n-amyl alcohol were mixed at room temperature to give 10
The temperature was raised to 0 ° C. Next, at the same temperature, palladium chloride 5.3
g (30 mmol) was added, and 100 ° C to 110 ° C.
React for 12 hours, cool to room temperature, filter insolubles,
The filtrate was concentrated under reduced pressure, 400 ml of methanol was added, and the precipitated crystals were filtered and washed with 100 ml of methanol. When dried at 60 ° C., the following formulas (19) and (2
25.1 g of a mixture of 0), (21) and (22) was obtained. The yield was 89%. The mixture maximum absorption wavelength _{λ max = 692 nm, ε m} ax = 2.5 × 10 5 g -1 c
It was m ² (toluene). The production ratio is (19) / (20) / (21) / from the area ratio of the liquid chromatogram.
(22) = 50/48/1/1.

[0034]

[Chemical 20]

[0035]

[Chemical 21]

[0036]

[Chemical formula 22]

[0037]

[Chemical formula 23]

Example 4 The following formula (23)

[0039]

[Chemical formula 24] 25.6 g of phthalonitrile (100 mm
ol), 15.2 g (100 mmol) of DBU and 120 g of 1-hexanol are mixed at room temperature, and 110 ° C.
The temperature was raised to. Next, at the same temperature, 5.3 g of palladium chloride
(30 mmol) and added at 110 ° C to 120 ° C for 1
After reacting for 2 hours and cooling to room temperature, the insoluble matter was filtered off, the filtrate was concentrated under reduced pressure, 400 ml of methanol was added, the precipitated crystals were filtered off, and washed with 100 ml of methanol.
When dried at 60 ° C., the following formulas (24), (25),
25.9 g of a mixture of (26) and (27) was obtained. The yield was 92%. The mixture has a maximum absorption wavelength λ
_max = 694 nm, ε _max = 2.2 × 10 ⁵ g ⁻¹ cm
It was ² (toluene). The production ratio is (24) / (25) / (26) / from the area ratio of the liquid chromatogram.
(27) = 48/49/2/1.

[0040]

[Chemical 25]

[0041]

[Chemical formula 26]

[0042]

[Chemical 27]

[0043]

[Chemical 28]

Example 5 The following formula (28)

[0045]

[Chemical 29] Phthalonitrile of 18.2 g (79 mmo
l), DBU 12.2 g (80 mmol) and 1-
120 g of hexanol was mixed at room temperature and the temperature was raised to 110 ° C. Next, at the same temperature, 5.3 g of platinum chloride (20 m
mol) was added, the mixture was reacted at 110 ° C. to 120 ° C. for 17 hours, cooled to room temperature, the insoluble matter was filtered off, the filtrate was concentrated under reduced pressure, 300 ml of methanol was added, and the precipitated crystals were filtered off, It was washed with 100 ml of methanol. When dried at 60 ° C., 17.5 g of a mixture of the following formulas (29), (30), (31) and (32) was obtained. Yield 8
It was 0%. The mixture has a maximum absorption wavelength λ _max = 679
nm, ε _max = 2.6 × 10 ⁵ g ^-1 cm ² (toluene)
Met. The production ratio is (29) / (30) / (31) / (32) = 53 / from the area ratio of the liquid chromatogram.
It was 43/2/2.

[0046]

[Chemical 30]

[0047]

[Chemical 31]

[0048]

[Chemical 32]

[0049]

[Chemical 33]

Example 6 The following formula (33)

[0051]

[Chemical 34] 23.1 g of phthalonitrile (90 mmo
l), 116.4 g (108 mmol) of DBU and 100 g of n-amyl alcohol were mixed at room temperature to give 10
The temperature was raised to 0 ° C. Then vanadium trichloride at the same temperature 3.
Add 9 g (25 mmol), 100 ° C-110 ° C
React for 10 hours, cool to room temperature, filter insoluble matter,
The filtrate was concentrated under reduced pressure, 400 ml of methanol was added, and the precipitated crystals were filtered and washed with 100 ml of methanol. When dried at 60 ° C, the following formulas (34) and (3
22.4 g of a mixture of 5), (36) and (37) was obtained. The yield was 91%. The mixture maximum absorption wavelength _{λ max = 742 nm, ε m} ax = 1.6 × 10 5 g -1 c
It was m ² (toluene). The production ratio is (34) / (35) / (36) / from the area ratio of the liquid chromatogram.
(37) = 51/46/2/1.

[0052]

[Chemical 35]

[0053]

[Chemical 36]

[0054]

[Chemical 37]

[0055]

[Chemical 38]

Example 7 24.2 g of phthalonitrile represented by the above formula (13)
(100 mmol), DBU 15.2 g (100
mmol) and 130 g of n-amyl alcohol were mixed at room temperature, and the temperature was raised to 95 ° C. Next, at the same temperature, 2.5 g (25 mmol) of copper (I) chloride was added,
After reacting at 105 ° C. for 10 hours and cooling to room temperature, the insoluble matter was filtered off, the filtrate was concentrated under reduced pressure, 500 ml of methanol was added, the precipitated crystals were filtered off, and washed with 100 ml of methanol. When dried at 60 ° C., the following formula (38),
24.0 g of a mixture of (39), (40) and (41)
was gotten. The yield was 93%. The mixture has a maximum absorption wavelength λ _max = 708 nm, ε _max = 2.8 × 10 ⁵ g ⁻¹
It was cm ² (toluene). The production ratio is (38) / (39) / (40) from the area ratio of the liquid chromatogram.
/ (41) = 46/47/4/3.

[0057]

[Chemical Formula 39]

[0058]

[Chemical 40]

[0059]

[Chemical 41]

[0060]

[Chemical 42]

Comparative Example 1 24.2 g of phthalonitrile represented by the above formula (13)
(100 mmol), DBU 15.2 g (100
mmol), palladium chloride 5.3 g (30 mmo
1) and 100 g of 1-hexanol are mixed at room temperature, heated to 130 ° C., and heated at 130 ° C. to 140 ° C. for 12 hours.
After reacting for a period of time and cooling to room temperature, the insoluble matter was filtered off, the filtrate was concentrated under reduced pressure, 400 ml of methanol was added, the precipitated crystals were filtered off, and washed with 100 ml of methanol. 60
When dried at ℃, the formulas (14), (15), (1
13.2 g of a mixture of 6) and (17) was obtained. The yield was 49%. The mixture has a maximum absorption wavelength λ _max = 6
It was 92 nm and ε _max = 2.8 × 10 ⁵ g ^-1 cm ² (toluene). The production ratio is (14) / (15) / (16) / (17) = from the area ratio of the liquid chromatogram.
It was 41/45/8/6. In addition to these, 22% of a mixture of metal-free phthalocyanines represented by the following formulas (42) and (43) was by-produced.

[0062]

[Chemical 43]

[0063]

[Chemical 44]

Comparative Example 2 24.2 g of phthalonitrile represented by the above formula (13)
(100 mmol), DBU 15.2 g (100
mmol), palladium chloride 5.3 g (30 mmo
1) and 100 g of n-amyl alcohol are mixed at room temperature, heated to 75 ° C., reacted at 75 ° C. to 85 ° C. for 30 hours, cooled to room temperature, filtered with insoluble matter, and the filtrate is decompressed. After concentrating and adding 400 ml of methanol, the precipitated crystals were filtered and washed with 100 ml of methanol. When dried at 60 ° C., the above formulas (14), (15) and (16) were obtained.
8.6 g of a mixture of (17) and (17) was obtained. Yield is 3
It was 2%. The mixture has a maximum absorption wavelength λ _max = 692
nm, ε _max = 2.8 × 10 ⁵ g ^-1 cm ² (toluene)
Met. The production ratio is (14) / (15) / (16) / (17) = 41 / from the area ratio of the liquid chromatogram.
It was 51/4/4.

[0065]

[Effects of the Invention] A mixture of phthalonitrile and an organic base is heated in alcohol from 90 to 120 ° C, and a metal derivative is added and reacted at the same temperature to give α-tetraalkoxyphthalocyanine having a large steric hindrance in good yield. It can be synthesized. Further, it has become possible to control the production ratio of α-tetraalkoxyphthalocyanine isomers.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Nobuo Aihara 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Naoto Ito 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Kagaku Within the corporation

Claims (6)

[Claims] 1. The following general formula (1): (Wherein R ¹ represents a secondary alkyl group having 3 to 20 carbon atoms in the formula (1)), 1 to 4 kinds of 3-alkoxyphthalonitrile and an alcohol solution or suspension of an organic base are used. To 120 ° C., the metal or metal derivative is added at the same temperature, and the reaction is carried out at 90 to 120 ° C. The following general formula (2): (In the formula (2), each R ¹ independently represents a secondary alkyl group having 3 to 20 carbon atoms, Met represents a divalent metal atom or an oxymetal. The substitution position of the —OR ¹ group is 1 Or at the 4, 5 or 8, 9 or 12 and 13 or 16 positions). 2. The method for producing an alkoxyphthalocyanine according to claim 1, wherein the metal derivative is palladium halide, palladium acetate, platinum halide or platinum acetate. 3. The method according to claim 2, wherein R ¹ is 1,3-dimethylbutyl group, 1,2-dimethylbutyl group, 2-methyl-1-iso-propylpropyl group, 1-ethyl-3-
Methylbutyl group, 3-methyl-1-iso-propylbutyl group, 2-methyl-1-iso-propylbutyl group,
And a method for producing an alkoxyphthalocyanine which is one kind selected from the group consisting of 1-t-butyl-2-methylpropyl group. 4. The method for producing an alkoxyphthalocyanine according to claim 3, wherein the amount of the solvent used is 1 to 100 times that of phthalonitrile. 5. The organic base according to claim 4, wherein the organic base is 1,8-
A method for producing an alkoxyphthalocyanine which is diazabicyclo [5.4.0] -7-undecene or 1,5-diazabicyclo [4.3.0] -5-nonene. 6. The phthalocyanine produced according to claim 5, wherein the phthalocyanine has the following formulas (4) and (5): (In the formula (4) and (5), R ¹ and Met are. The same meanings as R ¹ and Met in the formula (2)) is a mixture of isomers represented by the abundance of the formula (4) A Is 40 ≦ A ≦ 60,
The abundance ratio B of the formula (5) is 40 ≦ B ≦ 60, and A + B ≦
A method for producing an alkoxy phthalocyanine which is 100.