JPH01100171A - Production of phthalocyanine compound - Google Patents

Abstract

PURPOSE:To readily obtain a phthalocyanine compound having a substituent group of a near absorbing coloring matter useful as information recording materials in high yield, by reacting a phthalic acid derivative having a substituent group in the presence of urea, etc., using trichlorobenzene as a solvent. CONSTITUTION:A phthalic acid derivative, such as 3,6-diphenylthio-4,5- dichlorophthalic anhydride, having a substituent group, such as -R is 1-12C alkyl or aryl, such as phenyl or naphthyl), -X (X is F, Cl, Br or I), -Sr or -OR, is reacted in the presence or absence of urea in the coexistence of ammonium molybdate and vanadium oxychloride in a solvent of trichlorobenzene, such as 1,2,3-, 1,2,4- or 1,3,5-trichlorobenzene, to afford the aimed compound, such as octa-3,6-phenylthio-octa-4,5-dichloroVOphthalocyanine, having a high solubility in organic solvents, liquid crystals, etc., due to the substituent group effects.

Description

Detailed Description of the Invention The phthalocyanines obtained by the present invention have increased solubility in organic solvents, liquid crystals, etc. due to the substituent effect, and have near-infrared absorbing properties that are extremely useful as various information recording materials including optical discs. It is a pigment.

Generally, methods for synthesizing unsubstituted metal phthalocyanine compounds include a dry method in which phthalic anhydride or phthalic acid derivatives in urea are reacted with metal halides, etc., and an inert solvent (e.g. aromatic halogen solvent, A wet method is known in which the reaction is carried out by adding an aromatic nitro compound solvent, sulfolane, DBU, etc.). Among the above-mentioned Niga methods, a method suitable for the purpose has been adopted in consideration of the physical properties, usage, yield, etc. of the phthalocyanine compound. In the synthesis of unsubstituted copper phthalocyanine, it has been reported that a wet method using trichlorobenzene has a slightly higher yield than a dry method.

The present inventors have developed phthalic acid derivatives having substituents (phthalic acid, phthalic anhydride, phthalic acid amide, phthalimide,
When we compared the yields of the dry method and the wet method using phthalonitrile, indolenine, etc., we found that there was a large difference in yield that could not be expected from the known case. The present invention was completed by discovering that phthalocyanine compounds having substituents can be obtained in high yield.

For example, when 3,6-cyphenylthio-4,5-dichlorophthalic anhydride is reacted with vanadium oxychloride in urea, octa-3,6-phenylthio-octa-4,5
It has been found that, while -chlorophthalocyanine is obtained in a yield of 20.2%, the same compound can be obtained in a higher yield of 67.7% when the reaction is carried out in trichlorobenzene.

Substituents: -R, -X, -5R, -OR (R represents an alkyl group having 1 to 12 carbon atoms and an aryl group such as phenyl or naphthyl; X represents fluorine, chlorine, bromine,
The wet method was particularly effective when using a phthalic acid derivative having a phthalic acid derivative having an iodine atom (indicating an iodine atom), and the yield was 2 to 6 times higher than that of the dry method.

In the synthesis of phthalocyanine compounds having substituents as described above, trichlorobenzene (1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1
, 3,5-trichlorobenzene and three types of isomers, each of which can be used alone or in a mixture) has an extremely large effect on improving the yield. This effect is mainly due to the substituents of the phthalocyanine, and in the case of metal phthalocyanine, the influence of the central metal is thought to be small. Metal-free phthalocyanine can also be produced by the method of the present invention, but in the case of metal phthalocyanine, the central metal is
Lithium, beryllium, sodium, magnesium, aluminum, silicon, potassium, calcium, scandium, titanium, vanadium, manganese, iron, cobalt,
Nickel, copper, curved lead, gallium, germanium, arsenic,
Yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rubidium, palladium, silver, cadmium, indium, tin, antimony, barium, lanthanum, hafnium, tantalum, tungsten,
Rhenium, osmium, iridium, platinum, gold, mercury,
Examples include the elements thallium and lead, and their halides and oxides.

The present invention will be explained below by showing typical examples and comparative examples.

[Example 1 Production of co-octa3,6-phenylthio-octa-4,5-dichlorovO phthalocyanine 19.5 g of 3,6-siphenylthio-4,5-dichlorophthalic anhydride, 10.8 g of urea, 0.1 g of ammonium molybdate and 2.4 g of vanadium oxychloride
160-1 in 50g of 1.3.5-trichlorobenzene
After stirring at 65°C for 30 minutes, the mixture was further stirred at 195-200°C for 6 hours. After cooling to below 50℃ methanol 200℃
After refluxing for 30 minutes, the precipitate was clarified and the crude product was recrystallized from 〇-dichlorobenzene to give 13.1 g (yield 67.7%) of octa-3,6-phenylthio-octa. A dark green powder of -4,5=dichloro■0 phthalocyanine was obtained.

Maximum absorption wavelength (0-dichlorobenzene) 773 nm, Durham extinction coefficient (0-dichlorobenzene) 9. OX10
'xrl/g conflict cm Elemental analysis value Cao) I4ocILaNaO58V 0% N% N% Calculated value 55.85 2.35 6.52 Measured value 55.84 2.34 6.65 [Example 2] Hexadeca (Naphthi- Production of 2-ylthio)vO phthalocyanine Tetra-(naphth-2-ylthio)phthalonitrile 20
．． 1g, urea 6.4g, ammonium molybdate 0.
1 g and 2.4 g of vanadium oxychloride in 1.3.5
-Stirred in 50 g of trichlorobenzene at 200-210°C for 5 hours. After cooling, extract with 300ml of toluene,
Washed with 500 ml of 10% hydrochloric acid, and then with 500 ml of 10% aqueous sodium hydroxide solution. After drying the toluene solution over anhydrous magnesium sulfate, the toluene was distilled off to obtain crude product 16.3.
I got g. This was purified by column chromatography, and hexadeca (
naphth-2-ylthio)vO phthalocyanine 10.2g
(yield 49.4%) was obtained as a black powder.

Absorption maximum wavelength (toluene) 839 nm, Durham extinction coefficient (toluene) 3.2 value
74.79 4.04 3.44 [Example 3] Production of tetra(4-te・rt-butyl)vO phthalocyanine 27.5 g of 4-tert-butylphthalic anhydride
, urea 32.4g, ammonium molybdate 0.3g
and 7.1 g of vanadium oxychloride were stirred in 80 g of mixed trichlorobenzene at 160 to 165°C for 30 minutes,
Further, the mixture was stirred at 190 to 200°C for 6 hours. The reaction product was then cooled to below 100°C and extracted with toluene 800°C. The toluene solution was dissolved in 5% hydrochloric acid 700j11, then 10
After washing with 700 ml of % caustic soda aqueous solution, it was washed with saturated saline. After drying over anhydrous magnesium sulfate, column chromatography purification was performed to obtain 15.8 g (yield 58.3%) of tetra(4-tert-butyl)vO phthalocyanine as a blue powder.

Absorption maximum wavelength (toluene) 697 nm, Durham extinction coefficient (Tornizi) 2.4 X lo5ml/g-cm Elemental analysis value C48H48N80v Toshite C% 8%
N% Calculated value 71.70 6.03 '13.94 Measured value 71.82 6.12 13.91 [Comparative example 1] Production of octa-3,6-phenylthio-octa-4,5-dichloro vO phthalocyanine 3 .19.5 g of 6-cyphenylthio-4,5-dichlorophthalic anhydride, 2.4 g of vanadium oxychloride, 0.1 g of ammonium molybdate and 90 g of urea
The mixture was stirred at 5-200°C for 7 hours. After cooling, the reaction product was heated and washed with 500 ml of 5% hydrochloric acid, then heated and washed with 500 ml of 10% caustic soda aqueous solution, washed with hot water, and dried to obtain crude product 12.
．． 2g was obtained. This was recrystallized from 0-dichlorobenzene, and 3.9 g of octa-3,6-phenylthio-octa-4,5-dichloro vO phthalocyanine (yield 20.2%)
) was obtained.

The particle size, IR spectrum, absorption maximum wavelength, and Durham extinction coefficient were the same as those obtained in Example 1.

[Comparative Example 2] Production of hexadeca(naphth-2-ylthio) vO phthalocyanine Tetra(naphth-2-ylthio)phthalodinitrile 20
．． 1 g, 2.4 g of vanadium oxychloride, 0.1 g of ammonium molybdate and 80 g of urea at 200-2
The mixture was stirred at 10°C for 5 hours. After cooling, the reaction mixture was diluted with 5% hydrochloric acid.
Wash with 0 ml of heat, then 10% caustic soda aqueous solution 5
After heating and washing with 00ml, it was washed with hot water and dried. This dried product was purified by column chromatography to obtain 1.9 g (yield 9.2%) of hexadeca(naphth-2-ylthio)vO phthalocyanine.

The particle size, infrared absorption spectrum, and ultraviolet to near-infrared absorption spectrum (maximum wavelength and Durham extinction coefficient) were the same as those obtained in Example 2.

[Comparative Example 3] Production of tetra(4-Lert-butyl)vO phthalocyanine 27.5 g of 4-tert-butylphthalic anhydride,
7.1 g of vanadium oxychloride, 0.3 g of ammonium molybdate, and 140 g of urea were stirred at 200 to 210°C for 6 hours. After cooling, the reaction mixture was added with 700ml of 5% hydrochloric acid.
The sample was then heated and washed with a 10% caustic soda aqueous solution 700 resistant, then washed with hot water and dried. The dried product was purified by column chromatography to obtain 8.1 g (yield 29.9%) of tetra(4-
tert-butyl) vO phthalocyanine was obtained.

The particle size, infrared absorption spectrum, and ultraviolet to near-infrared absorption spectrum (maximum wavelength and Durham extinction coefficient) were the same as those obtained in Example 3 ◎ Procedural report (self-prompted) December 1988 j ten days

Claims (1)

[Claims] A method for producing a phthalocyanine compound having a substituent, the method comprising reacting a phthalic acid derivative having a substituent in trichlorobenzene in the presence or absence of urea.