JPH10292124A - Method for purifying alkoxyphthalocyanine derivatives - Google Patents

Abstract

PROBLEM TO BE SOLVED: To more easily inexpensively, and industrially advantageously purify the subject derivative to the purity the same as that attained by a column chromatography than the column purification at a low cost, by heating and dissolving a crude alkoxyphthalocyanine in an organic solvent and treating with dispersed silica gel. SOLUTION: This method for purifying alkoxyphthalocyanine derivatives is to dissolve (A) a crude alkoxyphthalocyanine of the formula [R<1> to R<4> are each a straight, branched or cyclic alkyl; X is a halogen; (n) is 0-4; Met is a divalent metal, a trivalent or tetravalent metal derivative or an oxymetal] by heating in (B)an organic solvent, preferably an aromatic hydrocarbon (e.g. toluene) having 100-200 deg.C boiling point to have 5-500 g/l concentration of the ingredient A, treat the solution by dispersing silica gel at 30-200 deg.C for 30 minutes - 2 hours by using (C) 20-400 wt.% of silica gel having 40-500 μm particle size based on the ingredient A and remove the component C by filtration, and distill off the component B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dye, a pigment, a photoelectric functional material, and a recording / memory material, particularly an alkoxyphthalocyanine derivative useful as a recording material for a write-once optical recording medium (write-once compact disc, CD-R). And a method for purifying the same.

[0002]

2. Description of the Related Art A technique using a phthalocyanine derivative, particularly an alkoxyphthalocyanine derivative, in a recording layer of a recording / storage material, particularly an optical recording medium such as an optical disk is disclosed in JP-A-61-197280 and JP-A-61-246091. No. 62-39286 (USP 4,769,
307), JP-A-63-37991 and JP-A-63-393.
No. 88, JP-A-3-62878 and the like. In optical recording media, it is necessary to purify the alkoxyphthalocyanine derivative with high purity in order to obtain sufficient performance in sensitivity, recording characteristics, and the like.

[0003] Since the alkoxyphthalocyanine derivative is a mixture in which a tar-like by-product and several types of isomers are present, the purification method is described in, for example,
As described in JP-A-17477 and JP-A-5-25179, column purification using silica gel or alumina is a general method.

[0004]

The purification method by column purification requires the use of a large amount of expensive silica gel or alumina (40 to 100 times by weight of the crude product), and the time required for column purification is long. Over time,
This is a very disadvantageous purification method. That is, an object of the present invention is to provide a simpler and more inexpensive purification method especially when industrial production is considered.

[0005]

The present inventors have conducted intensive studies on a simple and inexpensive purification method of this alkoxyphthalocyanine derivative. As a result, after dissolving the crude alkoxyphthalocyanine in an organic solvent by heating and dispersing it on silica gel,
By filtering off the silica gel to which the impurities were adsorbed and distilling off the solvent, the amount of silica gel used was reduced and in a short time, an industrially advantageous method for obtaining an alkoxyphthalocyanine derivative having a purity equivalent to that of the column purified product was found. The present invention has been reached.

That is, the present invention is a method for purifying an alkoxyphthalocyanine derivative, comprising dissolving a crude alkoxyphthalocyanine by heating in an organic solvent and subjecting the crude alkoxyphthalocyanine to silica gel dispersion.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The organic solvent used in the present invention must have the following properties: 1) dissolving an alkoxyphthalocyanine derivative; 2) having a boiling point of 50 ° C. or more, preferably 100 ° C. or more. , Benzene, chloroform, dichloromethane, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, trichloroethylene, tetrahydrofuran, diisopropyl ether, dimethoxyethane, toluene, ethylbenzene, isopropylbenzene, xylene, Anisole, 1,1,2,2-tetrachloroethane, tetrachloroethylene, chlorobenzene, dichlorobenzene, 1,3,5-trichlorobenzene, 1-chloronaphthalene, 2-chloronaphthalene, bromobenzene, dibromobenzene, 1-methylnaphthalene, 2-methylnaphthalene, 1 , 4-dioxane, di-n-
Butyl ether, diglyme and the like. Particularly, an aromatic hydrocarbon having a boiling point of 100 ° C. to 200 ° C. is preferable, and examples thereof include toluene, ethylbenzene, and xylene.

As the silica gel used in the present invention, silica gel for column chromatography can be used as it is, and silica gel having a particle diameter of 40 to 500 μm, preferably 40 to 210 μm is used.

The amount of silica gel used is 20 to 400% by weight, preferably 40% by weight, based on the crude alkoxyphthalocyanine.
~ 200% by weight.

[0011] The temperature of the silica gel dispersion treatment is from 30 ° C to 2
The temperature is 00 ° C, preferably 50 to 100 ° C, and the dispersion treatment time is 30 minutes to 2 hours.

In the silica gel dispersion treatment, the concentration of the crude alkoxyphthalocyanine in the above solvent is 5 g / l to 500 g / l, preferably 10 g / l to 300 g / l.
Adjust so that

The phthalocyanine purified according to the present invention has the following general formula (1)

[0014]

Embedded image [In the formula (1), R ¹ , R ² , R ³ and R ⁴ represent a linear, branched or cyclic alkyl group, X represents a halogen atom,
n represents 0 to 4, and Met represents a divalent metal atom, a trivalent or tetravalent metal derivative, or an oxymetal. Or a mixture of isomers thereof.

In the above general formula (1), the linear, branched or cyclic alkyl group represents a hydrocarbon having 3 to 15 carbon atoms or a halogenated hydrocarbon. As a specific example,
Propyl, butyl, pentyl, iso-propyl,
sec-butyl group, t-butyl group, neo-pentyl group, 1,2-dimethylpropyl group, cyclo-hexyl 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-methylbutyl group, 3-methyl-
Hydrocarbon groups such as 1-iso-propylbutyl group, 2-methyl-1-iso-propylbutyl group, 1-t-butyl-2-methylpropyl group, 1,1,1,3,3,3- And a halogenated alkyl group such as a hexafluoro-2-propyl group.

Examples of divalent metal atoms represented by Met include Cu, Zn, Mn, Fe, Co, Ni, Ru, and R.
h, Pd, Pt, Pb and the like. Examples of the trivalent or tetravalent metal derivative include AlCl, AlBr, AlI, and AlO.
H, InCl, InBr, InI, InOH, SiCl
₂ , SiBr ₂ , SiI ₂ , Si (OH) ₂ , GeCl ₂ ,
GeBr ₂ , GeI ₂ , SnCl ₂ , SnBr ₂ , Sn
Examples include I ₂ and Sn (OH) ₂ , and examples of the oxymetal include TiO and VO.

As the halogen atom, F, Cl, Br,
I.

The production of the alkoxyphthalocyanine derivative is carried out by adding 1 to 4 kinds of phthalonitrile (2) or diiminoisoindoline (3) represented by the following general formula in a solvent, preferably in an alcohol at 10 ° C. ~ 300
Heat reaction at ℃. When the raw material is phthalonitrile represented by the formula (2), the reaction temperature is preferably from 80 ° C to 160 ° C. When the starting material is diiminoisoindoline represented by the formula (3),
C. is preferred. As a catalyst for the ring-forming reaction, 1,8-diazabicyclo [5,4,0] -7-undecene (DB
U), 1,5-diazabicyclo [4,3,0] -5-nonene (DB
An auxiliary agent such as N) may be added.

[0019]

Embedded image [In the formula (2), R ⁵ represents a linear, branched or cyclic alkyl group, X represents a halogen atom, and p represents 0 to 3. ]

[0020]

Embedded image [In the formula (3), R ⁶ represents a linear, branched or cyclic alkyl group, X represents a halogen atom, and q represents 0 to 3
Represents ]

The alkoxyphthalonitrile (2) or diiminoisoindoline (3) used in the present invention can be synthesized according to the reaction route of the following formula (4).

[0022]

Embedded image [In the formula (4), R represents the same meaning as R ⁵ and R ⁶ . ]

The starting material 3-nitrophthalonitrile or
4-Nitrophthalonitrile can be obtained from Tokyo Chemical Industry Co., Ltd. The synthesis of alkoxyphthalonitrile (a) from these nitrophthalonitriles is described in NOUVEAU JO
URNAL DE CHIMIE VOL.6 NO.12 PAGE653-58 It can be produced by the method described in 1982. That is, the alcohol is converted into sodium alkoxide with sodium hydride, followed by nitrophthalonitrile and 0 ° C to 100 ° C.
To give alkoxyphthalonitrile (a). Furthermore, diiminoisoindoline (b) can be obtained by reacting this alkoxyphthalonitrile (a) with ammonia in an alcohol solvent using sodium methylate or the like as a catalyst.

The synthesis of halogenated phthalonitrile is carried out according to IT
HARRISON and S. HARRISON co-authored "COMPENDIUM OF ORGANIC"
SYNTHETIC METHODS ", vol. 1-6, published by WILEY-INTERSCIENCE by halogenating alkoxyphthalonitrile.

Further, by halogenating the synthesized alkoxyphthalocyanine in the same manner, a halogenated alkoxyphthalocyanine derivative can be produced.

[0026]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube,
24.2 g of phthalonitrile represented by the following formula (5)
(0.1 mol), 15.2 g (0.1 mol) of DBU and 100 g of n-amyl alcohol were charged and heated to 90 ° C. under a nitrogen atmosphere. 4. Palladium chloride at the same temperature
3 g (0.03 mol) was added and reacted at 100 ° C. for 20 hours. After completion, the solvent was recovered by concentration under reduced pressure, 200 ml of toluene was added to the residue, and the temperature was raised to 50 ° C. to dissolve. Next, silica gel (particle diameter 100 to 210 μm) 40
g was added and the temperature was raised to 80 ° C., followed by stirring at the same temperature for 1 hour.
After cooling to room temperature, the silica gel was filtered and then concentrated under reduced pressure to distill off the solvent to obtain crystals. Palladium tetra α- [3
The yield of the mixture of-(2,4-dimethyl) pentyloxy] phthalocyanine was 20.2 g (75% yield).
The result of purity measurement by high performance liquid chromatography is 9
9%.

[0028]

Embedded image

Example 2 The palladium tetraα- [3- (2,4) obtained in Example 1
-Dimethyl) pentyloxy] phthalocyanine mixture 2
0 g was brominated with bromine in a mixed solvent of 60 ml of chloroform / 60 ml of water. After completion of the bromination, the mixture was washed with water, separated, and discharged into 120 ml of methanol to obtain crystals. The obtained crystals were dissolved by adding 100 ml of xylene and raising the temperature to 50 ° C. Next, silica gel (particle size 100 to 210)
μm) and stirred at the same temperature for 1 hour. The mixture was cooled to room temperature, filtered through silica gel, concentrated under reduced pressure, and the solvent was distilled off to obtain a brominated mixture of palladium tetra-α- [3- (2,4-dimethyl) pentyloxy] phthalocyanine 2
0.1 g (97% yield) was obtained. The result of the purity measurement by high performance liquid chromatography was 99.2%.

Example 3 In a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube,
24. Diiminoisoindoline represented by the following formula (6)
5 g (0.1 mol), 7.6 g (0.05 mol) of DBU, 5.3 g (0.03 mol) of palladium chloride and 100 g of n-octyl alcohol were charged and heated to 170 ° C. under a nitrogen atmosphere. . The reaction was carried out at the same temperature for 4 hours. After completion, the solvent was recovered by concentration under reduced pressure, 200 ml of toluene was added to the residue, and the temperature was raised to 50 ° C. to dissolve. Next, 20 g of silica gel (particle size: 100 to 210 μm) was added, the temperature was raised to 80 ° C., and the mixture was stirred at the same temperature for 1 hour. After cooling to room temperature, the silica gel was filtered and then concentrated under reduced pressure to distill off the solvent to obtain crystals. Palladium tetra α- [2- (4-
The yield of the (methyl) pentyloxy] phthalocyanine mixture was 22.0 g (87% yield). The result of purity measurement by high performance liquid chromatography was 99.6%.

[0031]

Embedded image

Example 4 In a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube,
Diiminoisoindoline represented by the following formula (7) 27.
3 g (0.1 mol), 7.6 g (0.05 mol) of DBU, 5.3 g (0.03 mol) of palladium chloride and 120 g of n-octyl alcohol were charged, and the temperature was raised to 180 ° C. under a nitrogen atmosphere. . The reaction was performed at the same temperature for 3 hours. After completion, the mixture was concentrated under reduced pressure to recover the solvent, 250 ml of ethylbenzene was added to the residue, and the temperature was raised to 50 ° C. to dissolve. Next, silica gel (particle diameter 100 to 210 μm) 30
g was added and the temperature was raised to 80 ° C., followed by stirring at the same temperature for 1 hour.
After cooling to room temperature, the silica gel was filtered, concentrated under reduced pressure, and the solvent was distilled off to remove palladium tetra α- [3- (2,5-
Dimethyl) hexyloxy] phthalocyanine mixture 2
0.3 g (yield 72%) of crystals were obtained. The result of purity measurement by high performance liquid chromatography was 99.5%.

[0033]

Embedded image

Example 5 A brominated mixture of palladium tetra-α- [3- (2,4-dimethyl) pentyloxy] phthalocyanine of Example 2 was dissolved in octane at a concentration of 30 g / l, and the CD-R was spin-coated. Coated on substrate. Gold was sputter-deposited thereon, and subsequently a protective layer was formed using a UV-curable resin to produce a CD-R medium. The manufactured optical disk is
The reflectance is 70% (775 nm to 790 nm), and 78
E at a linear velocity of 1.3 m / s using a semiconductor laser of 0 nm
The FM signal could be written with a sensitivity of 6.0 mW, and the error rate at that time was less than 10, satisfying the CD-R standard.

[0035]

The method for purifying an alkoxyphthalocyanine derivative of the present invention can be carried out more conveniently and inexpensively than conventional column purification without lowering the quality, and can be carried out industrially advantageously.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Taizo Nishimoto 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemical Co., Ltd. Inside (72) Inventor Takeshi Takeda 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Keisuke Takuma 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (8)

[Claims] 1. A method for purifying an alkoxyphthalocyanine derivative, comprising heating and dissolving a crude alkoxyphthalocyanine in an organic solvent and subjecting it to silica gel dispersion treatment. 2. The purification method according to claim 1, wherein after silica gel dispersion treatment in an organic solvent, the silica gel is filtered off and the solvent is distilled off. 3. The heating temperature in an organic solvent is from 30.degree.
The purification method according to claim 1, wherein the temperature is 00 ° C. 4. 4. The purification method according to claim 2, wherein the solvent is distilled off under reduced pressure. 5. The purification method according to claim 1, wherein the organic solvent is an aromatic organic solvent. 6. The method according to claim 5, wherein the aromatic organic solvent is toluene, ethylbenzene or xylene. 7. The purified alkoxyphthalocyanine derivative has the following general formula (1): [In the formula (1), R ¹ , R ² , R ³ and R ⁴ represent a linear, branched or cyclic alkyl group, X represents a halogen atom,
n represents 0 to 4, and Met represents a divalent metal atom, a trivalent or tetravalent metal derivative, or an oxymetal. The purification method according to any one of claims 1 to 6, wherein the compound is a compound represented by the formula: 8. The method according to claim 1, wherein the alkoxyphthalocyanine derivative is α-
The purification method according to claim 7, which is an alkoxyphthalocyanine derivative.