JPH0749533B2 - Method for producing phthalocyanine compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a halogenated alkylthiophthalocyanine useful as a near infrared absorber.

[Conventional technology]

As a method for producing a halogenated alkylthiophthalocyanine or a halogenated arylthiophthalocyanine,
It has already been disclosed in JP-A-60-209583, which is a method for producing a desired halogenated alkylthiophthalocyanine or halogenated arylthiophthalocyanine by substituting a halogenated phthalocyanine with an alkylthiol or an arylthiol. Separately from this, the present applicant has applied for a method for producing a desired halogenated alkylthiophthalocyanine by ring closure of dialkylthiodihalogenophthalonitrile in Japanese Patent Application No. 1-322761.

[Problems to be Solved by the Invention]

As the near-infrared absorbing agent, particularly, a halogenated alkylthiophthalocyanine useful as a recording material of 830 nm of a write-once type CD (CD-WO), one having a halogenation rate of 1 to 4 is preferable. If the halogenation rate is 5 or more, the standard of the refractive index and the reflectance cannot be satisfied. In the above-mentioned method, the amount of halogen atoms introduced cannot be controlled, and it cannot be said that the method is still sufficient as a near-infrared absorber for CD-WO.

[Means for Solving the Problems]

As a result of intensive studies to solve the above-mentioned problem, the present inventors have obtained a halogenated alkylthiophthalocyanine with a controlled halogenation ratio from alkylthiophthalocyanine by controlling the reaction temperature and the amount of solvent in acetic acid. Then, the present invention was reached.

That is, the present invention provides the following general formula (I) [In the formula (I), R represents a substituted or unsubstituted alkyl group, and Met represents two hydrogen atoms, a divalent metal atom, a substituted trivalent metal atom or a disubstituted tetravalent metal atom. ] The phthalocyanine compound represented by the following formula (II) characterized by reacting with a halogenating agent in acetic acid at 20 ~ 90 ℃. [In the formula (II), R and Met have the same meanings as in the formula (I), X represents chlorine, bromine or iodine, and n is 1 ≦
n ≦ 4. ] It is a manufacturing method of the phthalocyanine compound shown by these.

In the general formulas (I) and (II), examples of the substituted or unsubstituted alkyl group represented by R include a methyl group, an ethyl group,
n-propyl group, iso-propyl group, n-butyl group, iso
-Butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, 1,2-
Dimethylpropyl group, n-hexyl group, 1,3-dimethylbutyl group, cyclohexyl group, n-heptyl group, 1,4-
Dimethylpentyl group, 2-methyl-1-iso-propylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-is
Hydrocarbon groups such as o-propylbutyl group, n-nonyl group, 3,5,5-trimethylhexyl group, 3-methyl-1-iso-butylbutyl group, n-decyl group, methoxymethyl group, ethoxymethyl group, Methoxyethyl group, ethoxyethyl group, butoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, 2-methoxypropyl group, 2-ethoxypropyl group, 2,3-dimethoxypropyl group, 2,2-dimethoxyethyl group, 2-methoxybutyl group, 1-methyl-2-methoxyethyl group, 1-ethyl-
2-ethoxyethyl group, alkoxyalkyl group such as ethoxybutyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, hydroxyalkyl group such as 6-hydroxyhexyl group, trifluoromethyl group, Examples thereof include halogenated alkyl groups such as 2,2,2-trichloroethyl group, hexafluoro-iso-propyl group and pentafluoroethyl group.

Further, as an example of the divalent metal represented by Met, Cu ^(II) , Zn
^(II) , Fe ^(II) , Co ^(II) , Ni ^(II) , Ru ^(II) , Rh ^(II) , Pd ^(II) , Pt
^(II) , Mn ^(II) , Mg ^(II) , Be ^(II) , Ca ^(II) , Ba ^(II) , Cd ^(II) , Hg
Examples of monosubstituted trivalent metals such as ^(II) and Sn ^(II) include Al-C
l, Al-Br, Al-F, Al-I, Ga-Cl, Ga-F, Ga-I, Ga-Br, In
-Cl, In-Br, In-I, In-F, Tl-Cl, Tl-Br, Tl-I, Tl-F,
_{Al-C 6 H 5, Al} -C 6 H 4 CH 3, In-C 6 H 5, In-C 6 H 4 CH 3, In-C 10 H
₇ , Mn (OH), etc.

Examples of disubstituted tetravalent metals include CrCl ₂ , SiCl ₂ , SiBr ₂ and Si.
F ₂ , SiI ₂ , ZrCl ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , GeF ₂ , SnCl ₂ , SnBr ₂ , Sn
I ₂ , SnF ₂ , TiCl ₂ , TiBr ₂ , TiF ₂ , Si (OH) ₂ , Ge (OH) ₂ , Zr (O
H) ₂ , Mn (OH) ₂ , Sn (OH) ₂ , TiR ₂ , CrR ₂ , SiR ₂ , SnR ₂ , GeR ₂ ,
[R represents an alkyl group, a phenyl group, a naphthyl group and its derivatives], Si (OR ') ₂ , Sn (OR') ₂ , Ge (OR ')
₂ , Ti (OR ′) ₂ , Cr (OR ′) ₂ [R ′ represents a derivative of an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group or a dialkylalkoxysilyl group], Sn (SR ″)
₂ , Ge (SR ″) ₂ [R ″ represents an alkyl group, a phenyl group, a naphthyl group or a derivative thereof] and the like.

Examples of oxymetals include VO, MnO, TiO and the like.

The method for synthesizing the alkylthiophthalocyanine compound represented by the formula (I) includes the following formulas (III) or (IV) 1 to 4 of the compounds represented by
It can be obtained by reacting with heating in butanol in the presence of diazabicyclo [5.4.0] -7-undecene (DBU) under heating.

Examples of the halogenating agent usable in the present invention include chlorine, bromine, iodine, thrifryl chloride, thionyl chloride, iodine monochloride, quaternary ammonium chloride, quaternary ammonium bromide, quaternary ammonium iodide, and t-hypochlorous acid.
Butyl, potassium iodide and the like are preferred. Further, a catalyst such as an oxidizing agent or iron powder may be used if necessary. The amount of the halogenating agent is preferably 1 to 6 molar ratio with respect to the raw material phthalocyanine of the formula (I).

The amount of the acetic acid solvent is 5 to 500 times by weight, preferably 10 to 200 times by weight with respect to the phthalocyanine as a raw material, and the amount thereof is the required halogenation rate (n in the formula (II) is 1 to 1 times).
It is appropriately adjusted by 4).

The reaction temperature is 20 to 90 ° C, preferably 40 to 70 ° C. If the reaction temperature is lower than 20 ° C, the reaction does not proceed well, and if it exceeds 90 ° C, it becomes difficult to control the halogenation rate.

In the present invention, the reaction temperature and the amount of solvent are adjusted so that the resulting halogenated alkylthiophthalocyanine is reacted and precipitated from the reaction system.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 Palladium tetra α- (1,3-dimethylbutylthio)
15 g of phthalocyanine was charged in 375 ml of acetic acid and the temperature was raised to 45 ° C. to dissolve it. Next, 18 g of bromine was added dropwise, and the mixture was stirred at 50 ° C for 1 hour. The reaction liquid was cooled to 40 ° C, and the precipitated crystals were separated by filtration. The obtained crystals were sludged with 200 ml of methanol three times and dried under reduced pressure. The yield was 17.5g.

Elemental analysis revealed that the number of bromine substitutions was three.

Elemental analysis: C ₅₆ H ₆₁ N ₈ S ₄ Br ₃ Pd C H N S Br theoretical value (%) 50.93 4.66 8.49 9.71 18.15 analytical value (%) 50.51 4.45 8.35 9.59 18.55 Example 2 Palladium tetra α- (1,3 -Dimethylbutylthio)
Phthalocyanine (10 g) was charged into acetic acid (150 ml) and the temperature was raised to 40 ° C. to dissolve the phthalocyanine. Next, 6 g of bromine was added dropwise, and the mixture was stirred at 40 ° C for 30 minutes. Crystals precipitated at the same temperature were filtered off. The obtained crystals were sludged three times with 100 ml of methanol and dried under reduced pressure. The yield was 11g.

Elemental analysis revealed that the number of bromine substitutions was two.

Elemental analysis: C ₅₆ H ₆₂ N ₈ S ₄ Br ₂ Pd C H N S Br theoretical value (%) 54.96 5.11 9.16 10.48 13.06 Analytical value (%) 55.63 5.01 8.97 10.22 13.73 Example 3 Palladium tetra α- (1-iso 10 g of -propyl-2-methylbutylthio) phthalocyanine was charged into 400 ml of acetic acid and the temperature was raised to 40 ° C to dissolve it. Next, 12 g of bromine was added dropwise, and the mixture was stirred at 70 ° C for 5 hours. The reaction solution was cooled to 40 ° C. and the precipitated crystals were filtered off. 100 ml of the obtained crystals
Was sludged 3 times and dried under reduced pressure. The yield was 12.2g.

Elemental analysis revealed that the number of bromine substitutions was four.

Elemental analysis: C ₆₀ H ₆₈ N ₈ S ₄ Br ₄ Pd C H N S Br theoretical value (%) 49.51 4.71 7.70 8.81 21.96 analytical value (%) 50.42 4.98 7.95 8.97 21.53 Example 4 Palladium tetra α- (2-ethylhexyl) 2 g of thio) phthalocyanine was charged into 400 ml of acetic acid, and the temperature was raised to 40 ° C. to dissolve it. Next, 2 g of bromine was added dropwise, and the mixture was stirred at 50 ° C for 1 hour. The reaction solution was cooled to 40 ° C. and the precipitated crystals were filtered off. The obtained crystals were sludged with 30 ml of methanol three times and dried under reduced pressure. The yield was 2.2 g.

As a result of elemental analysis, it was found that the obtained product had an intermediate value between 2 and 3 in bromine substitution, and was a mixture of 2- and 3-substituted bromine phthalocyanines.

Elemental analysis: C H N S Br theoretical value (%) n = 2 56.78 5.81 8.28 9.47 11.80 theoretical value (%) n = 3 53.65 5.42 7.82 8.95 16.73 analytical value (%) 55.22 5.62 8.05 9.21 14.27 Example 5 dichlorosilicon tetra 5 g of α- (2-ethylhexylthio) phthalocyanine was charged into 100 ml of acetic acid and the temperature was raised to 40 ° C. to dissolve it. Next, 5.5 g of bromine was added dropwise, and the mixture was stirred at 50 ° C for 1 hour. The reaction solution was cooled to 40 ° C. and the precipitated crystals were filtered off. The obtained crystals were sludged three times with 100 ml of methanol and dried under reduced pressure.

The yield was 5.6g.

Elemental analysis revealed that the number of bromine substitutions was three.

Elemental analysis: C ₆₄ H ₇₇ N ₈ S ₄ Br ₃ Cl ₂ Si C H N S Br Cl Theoretical value (%) 53.93 5.45 7.86 9.00 16.82 4.97 Analytical value (%) 53.63 5.39 7.72 8.81 17.32 4.85 Example 6 Palladium tetra α -(1,3-Dimethylbutylthio)
Phthalocyanine (2 g) was charged into acetic acid (40 ml) and the temperature was raised to 35 ° C. to dissolve it. Next, add 2 g of sulfuryl chloride dropwise, and at 1.50 ° C 1.
Stir for 5 hours. The reaction liquid was cooled to 35 ° C., and the precipitated crystals were filtered off. The obtained crystals were washed twice with 50 ml of water, sludged with 50 ml of methanol three times, and dried under reduced pressure. Yield is 2.
It was 2 g.

Elemental analysis revealed that the number of chlorine substitutions was four.

Elemental analysis: C ₅₆ H ₆₀ N ₈ S ₄ Cl ₄ Pd C H N S S Cl Theoretical value (%) 55.06 4.95 9.18 10.50 11.61 Analytical value (%) 54.78 4.79 9.00 10.35 11.99 [Effect of the invention] Alkylthiophthalocyanine It has become possible to control the amount of introduction of halogen atoms and replace them.

Claims (3)

[Claims] 1. The following general formula (I): [In the formula (I), R represents a substituted or unsubstituted alkyl group, and Met represents two hydrogen atoms, a divalent metal atom, a substituted trivalent metal atom or a disubstituted tetravalent metal atom. ] The phthalocyanine compound represented by the following formula (II) characterized by reacting with a halogenating agent in acetic acid at 20 ~ 90 ℃. [In the formula (II), R and Met have the same meanings as in the formula (I), X represents chlorine, bromine, or iodine, and n is 1 ≦
n ≦ 4. ] The manufacturing method of the phthalocyanine compound shown by these. 2. The method according to claim 1, wherein the amount of acetic acid used is 10 to 200 times by weight that of the phthalocyanine compound of formula (I). 3. The method according to claim 2, wherein the amount of the halogenating agent used is 1 to 6 molar ratio with respect to the phthalocyanine compound of formula (I).