Phthalocyanine compounds

A phthalocyanine compound of formula (I): ##STR1## wherein FIGS. 1 to 16 around the phthalocyanine skeleton indicate the positions of carbon atoms in each benzene ring thereof; an oxygen atom is bonded to the carbon atom with position 1 or 4, to the carbon atom with position 5 or 8, to the carbon atom with position 9 or 12, and to the carbon atom with position 13 or 16; R.sup.1 is a fluorine-atom substituted alkyl group; R.sup.2 is an unsubstituted phenyl group or an alkyl-group-substituted phenyl group; R.sup.3 is an unsubstituted alkyl group, a fluorine-atom substituted alkyl group or a hydrogen atom; and M represents Zn, Cu or Ni.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to phthalocyanine compounds which can be 
employed as a dye for optical recording, a dye for color filter, and a 
material for use in photoelectric conversion device, electrophotographic 
photoconductor, organic semiconductor device, catalysts, gas sensor, and 
color filter. 
2. Discussion of Background 
Phathalocyanine compounds attract attention not only as conventionally 
employed pigments, but also as dyes for optical recording media, dyes for 
color filter, and materials for use in photoelectric conversion device, 
electrophotographic photoconductor, organic semiconductor device, 
catalysts, gas sensor, and color filter. 
However, unsubstituted phthalocyanine compounds are slightly soluble or 
insoluble in most solvents and therefore considerably lack workability. 
For instance, when a thin film of the unsubstituted phthalocyanine compound 
is formed for the above-mentioned applications, vacuum deposition or ultra 
fine particle dispersion method is generally employed. In either method, 
the productivity is extremely low. Thus, the slight solubility or 
insolubility in solvents of conventional phthalocyanine compounds is a 
great obstacle to the mass production of the above-mentioned media and 
devices. 
In particular, when a phthalocyanine compound film prepared by vacuum 
deposition is used as a recording layer for an optical disk, it is 
necessary to perform crystal transformation of the recording layer into 
such a crystal form that is suitable for obtaining the recording 
characteristics required for the optical disk. This crystal transformation 
has to be conducted by heating the vacuum deposited phthalocyanine 
recording layer or exposing the vacuum deposited phthalocyanine recording 
layer to the vapor of an organic solvent for an extended period of time 
and the productivity of this method is significantly poor and therefore 
not used in practice for the production of optical disks. 
With respect to optical disks, in particular, with compact disks, write 
once read many type compact disks have been actively developed in recent 
years. As organic dyes used as the materials for such write once read many 
type compact disks, cyanine dyes have been mainly used. Cyanine dyes are 
excellent in that they have large absorptivity coefficients, but have the 
shortcoming of not being light resistant. In order to eliminate this 
shortcoming, it has been proposed to add a photostabilizer such as a 
singlet oxygen quencher to the cyanine dyes. However, the addition of such 
a stabilizer is not sufficiently effective. 
In sharp contrast to this, phthalocyanine dyes are comparable to the 
cyanine dyes and therefore the cyanine dyes can be replaced by 
phthalocyanine dyes with respect to the light absorption wavelength, and 
phthalocyanine dyes have high light resistance and therefore expected to 
find many applications in the field of recording materials. However, for 
such applications, the problem of phthalocyanine dyes that the 
solubilities thereof in organic solvents are extremely low has to be 
solved. 
In order to solve this problem, it has been proposed to introduce some 
substituents into a phthalocyanine compound to improve the solubility 
thereof in organic solvents and use the phthalocyanine compound in the 
form of a coating liquid by dissolving the phthalocyanine compound in a 
solvent. For instance, in Japanese Laid-Open Patent Applications 1-180865, 
2-265788 and 63-312888, there are disclosed phthalocyanine compounds with 
improved solubilities in organic solvents such as hydrocarbons with the 
introduction of an alkyl group, an alkoxyl group, or an alkylthio group in 
each benzene ring of phthalocyanine compounds. 
Furthermore, it has been tried to introduce various functional groups such 
as ester group and polyether group into each benzene group of 
phthalocyanine dye compounds to increase the solubilities of 
phthalocyanine dye compounds in organic solvents. 
However, when phthalocyanine compounds are used in a light absorption layer 
for an optical information recording medium, the phthalocyanine dye 
compounds have not only the problems of extremely low solubilities in 
organic solvents and poor workability, but also the problems that the 
absorptivity coefficients thereof on a longer wavelength side are lowered 
by the association of the molecules of the phthalocyanine dye compound in 
a superimposed manner when a film thereof is prepared because of the 
exceedingly high flatness of each phthalocyanine dye compound molecule, 
and that when used in write once read many type compact disks, with 
application of laser beams thereto, the recording sensitivity is not high 
due to the exceedingly high thermal stability of the phthalocyanine dye 
compounds. 
The phthalocyanine dye compounds disclosed in the above-mentioned Japanese 
Patent Applications are improved with respect to the film formation 
properties, but the optical characteristics and thermal characteristics 
thereof are unsatisfactory and the above-mentioned problems have not yet 
been solved. 
SUMMARY OF THE INVENTION 
It is therefore an object of the present invention to provide a 
phthalocyanine compound free from the above-mentioned conventional 
shortcomings. 
This object of the present invention can be achieved by a phthalocyanine 
compound of formula (I): 
##STR2## 
wherein FIGS. 1 to 16 around the phthalocyanine skeleton indicate the 
positions of carbon atoms in each benzene ring thereof; an oxygen atom is 
bonded to the carbon atom with position 1 or 4, to the carbon atom with 
position 5 or 8, to the carbon atom with position 9 or 12, and to the 
carbon atom with position 13 or 16; R.sup.1 is a fluorine-atom substituted 
alkyl group; R.sup.2 is an unsubstituted phenyl group or an 
alkyl-group-substituted phenyl group; R.sup.3 is an unsubstituted alkyl 
group, a fluorine-atom substituted alkyl group or a hydrogen atom; and M 
represents Zn, Cu or Ni. 
DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The phthalocyanine compound of the present invention is represented by 
formula (I): 
##STR3## 
wherein FIGS. 1 to 16 around the phthalocyanine skeleton indicate the 
positions of carbon atoms in each benzene ring thereof; an oxygen atom is 
bonded to the carbon atom with position 1 or 4, to the carbon atom with 
position 5 or 8, to the carbon atom with position 9 or 12, and to the 
carbon atom with position 13 or 16; R.sup.1 is a fluorine-atom substituted 
alkyl group; R.sup.2 is an unsubstituted phenyl group or an 
alkyl-group-substituted phenyl group; R.sup.3 is an unsubstituted alkyl 
group, a fluorine-atom substituted alkyl group or a hydrogen atom; and M 
represents zn, Cu or Ni. 
In the phthalocyanine compound of the above formula (I), specific examples 
of the fluorine-atom substituted alkyl group represented by R.sup.1 are 
trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, 
heptafluoro-iso-propyl group, and nonafluoro-n-butyl group. 
Specific examples of the unsubstituted phenyl group or 
alkyl-group-substituted phenyl group represented by R.sup.2 are phenyl 
group, 2-methylphenyl group, 4-methylphenyl group, 2,5-dimethylphenyl 
group, 2,4-dimethylphenyl group, 2,4,6-trimethylphenyl group, and 
2,5-di-tert-butylphenyl group. 
Specific examples of the unsubstituted alkyl group represented by R.sup.3 
are methyl group, ethyl group, n-propyl group, iso-propyl group, and 
straight-chain or branched butyl group, pentyl group, hexyl group, heptyl 
group and octyl group. 
Specific examples of the fluorine-atom substituted alkyl group represented 
by R.sup.3 are the same as those in the description of R.sup.1. 
The phthalocyanine compound of formula (I) of the present invention can be 
synthesized by allowing a phthalonitrile derivative, which is synthesized 
in accordance with a procedure as will be explained later, to react with a 
necessary metal salt in the presence of a strong organic base such as 
1,8-diazabicyclo[5.4.0]-7-undecene (DBU) or 
1,5-diazabicyclo[4.3.0]-5-nonene (DBN), in an alcohol solvent such as 
methanol, ethanol or n-pentanol. 
The thus obtained phthalocyanine compound is highly soluble in various 
organic solvents such as hydrocarbon solvents, ether solvents, ketone 
solvents, ester solvents, alcohol solvents, and aromatic solvents, 
assuming a blue green or green color when dissolved in these solvents. 
By spin-coating a solution of the phthalocyanine compound using any of the 
above solvents, for instance, on a polycarbonate substrate, a uniform thin 
layer of the phthalocyanine compound can be formed. 
The thus prepared thin layer of the phthalocyanine compound does not 
exhibit a decreased absorptivity coefficient in a visible wavelength area, 
unlike thin layers of conventional phthalocyanine compounds, so that the 
thin layer of the phthalocyanine compound according to the present 
invention is suitable for the application of an optical information 
recording medium. 
In the phthalocyanine compound of the present invention, the phenyl group 
or fluorine-atom substituted alkyl group is bulky, so that the association 
of the molecules of the phthalocyanine compound, which causes a 
significant reduction in absorptivity coefficient, is effectively 
hindered. 
It is considered that the above-mentioned preferable absorption spectrum 
characteristics of the phthalocyanine compound of the present invention 
are available due to the above-mentioned hindering of the association of 
the molecules of the phthalocyanine compound. 
Further, with respect to the thermal characteristics of the phthalocyanine 
compound, a moiety of the phenyl-methyloxy group, which is contained in 
the phthalocyanine compound of the present invention, is generally 
considered to have an easily thermally decomposable structure. As a matter 
of fact, the phthalocyanine compound represented by formula (I) of the 
present invention is exothermically decomposed at temperatures in the 
range of 200.degree. C. to 400.degree. C., so that the phthalocyanine 
compound of the present invention is suitable as the material for write 
once read many type compact disks. 
Furthermore, the fluorine-atom substituted alkyl group contained in the 
phthalocyanine compound of the present invention imparts sufficient light 
stability and thermal stability, which are desirable for the application 
of the recording material, to the obtained phthalocyanine compound. 
The overall characteristics of the molecule of the phthalocyanine compound 
of the present invention can be flexibly controlled with the balance 
between the abovementioned characteristic atoms and substituents being 
taken into consideration. Thus, the phthalocyanine compound of the present 
invention has high adaptability to the optical recording material which 
requires delicate adjustments to the characteristics of the molecule of 
the phthalocyanine compound. 
The phthalonitrile derivative with a fluorine-containing substituent, which 
is necessary for the synthesis of the phthalocyanine compound of the 
present invention, can be prepared by allowing a fluorine-containing 
benzyl alcohol derivative, which can be synthesized by any of the 
following methods (a), (b), (c), (d), and (e), to react with 
3-nitrophthalonitrile: 
(a) a benzene derivative is allowed to react with a fluorine-containing 
carboxylic anhydride or a fluorine-containing halogenated carboxylic acid 
by Friedel-Crafts reaction to prepare a fluorine-containing acetophenone 
derivative, and the thus prepared fluorine-containing acetophenone 
derivative is reduced. 
(b) a benzene derivative and a fluorine-containing acetone derivative are 
subjected to Friedel-Crafts reaction. 
(c) a halogenated benzoyl derivative is allowed to react with a 
fluorine-containing unsaturated hydrocarbon in the presence of a fluoride 
ion to prepare a fluorine-containing acetophenone derivative, and the thus 
prepared fluorine-containing acetophenone derivative is reduced. 
(d) an organic metallic compound such as phenyl lithium or phenyl magnesium 
bromide is allowed to react with a fluorine-containing carbonate to 
prepare a fluorine-containing acetophenone derivative, and the thus 
prepared fluorine-containing acetophenone derivative is reduced. 
(e) a benzaldehyde derivative is allowed to react with a 
fluorine-containing alkyl halide in the presence of metallic zinc.

Other features of this invention will become apparent in the course of the 
following description of exemplary embodiments, which are given for 
illustration of the invention and are not intended to be limiting thereof. 
EXAMPLE 1 
Synthesis of Phthalocyanine Compound No. 1 in TABLE 1 
Step (1-1) (Synthesis of benzyl alcohol derivative of 
1-phenyl-2,2,2-trifluoroethanol) 
5.0 q of 2,2,2-trifluoroacetophenone (available from Tokyo Kasei Kogyo Co., 
Ltd.), 11.8 g of aluminum triisopropoxide, and 100 ml of isopropyl alcohol 
were placed in a flask equipped with a reflux condenser. This reaction 
mixture was heated with stirring to a refluxing temperature thereof and 
refluxed with stirring for 1.5 hours. 
This reaction mixture was then allowed to stand at room temperature and 
cooled to room temperature. The reaction mixture was then poured into 1000 
ml of iced water, and the pH of the mixture was adjusted to 3 with the 
addition of a 20% aqueous solution of hydrochloric acid thereto. 
The above reaction mixture was extracted with 200 ml of toluene. The 
toluene extract layer was separated from the mixture and dried over 
magnesium sulfate. Toluene was distilled away from the toluene extract 
layer, whereby a benzyl alcohol was obtained as the residue in a yield of 
5.1 g. 
The analysis data of the thus obtained benzyl alcohol was as follows: 
______________________________________ 
Mass spectrum: 176 (M.sup.+) 
IR spectrum: 3500 cm.sup.-1 (.nu.OH) 
1120 to 1170 cm.sup.-1 (.nu.CF) 
______________________________________ 
Step (1-2) (Synthesis of phthalonitrile derivative) 
5.0 g of the benzyl alcohol derivative obtained in the above Step (1-1), 
7.9 g of anhydrous potassium carbonate, 30 ml of dimethyl sulfoxide, and 
4.5 g of 3-nitrophthalonitrile were placed in a flask. 
This reaction mixture was stirred in a stream of nitrogen at 70.degree. C. 
for 4 hours and then poured into 1000 ml of water. Crystals which 
separated out in the mixture were filtered off and dried, whereby a 
phthalonitrile derivative was obtained in a yield of 6 g. 
The analysis data of the thus obtained phthalonitrile derivative was as 
follows: 
______________________________________ 
Mass spectrum: 302 (M.sup.+) 
IR spectrum (KBr): 2230 cm.sup.-1 (.nu.CN), 
1140 to 1180 cm.sup.-1 (.nu.CF) 
Melting point: 165 to 167.degree. C. 
______________________________________ 
Step (1-3) (Synthesis of phthalocyanine compound No. 1 in TABLE 1) 
5.0 g of the phthalonitrile derivative prepared in the above Step (1-2), 
4.5 g of 1,8-diazabicyclo[5.4.0]-7-undecene (hereinafter referred to as 
DBU), 33 ml of 1-pentanol, and 0.64 g of zinc chloride were placed in a 
flask. 
This reaction mixture was stirred in a stream of nitrogen at 100.degree. C. 
for 5 hours. 
This reaction mixture was then poured into 100 ml of methanol. To this 
mixture, 20 ml of water was further added. Crystals which separated out in 
the mixture were filtered off and dried, whereby a crude product of a 
phthalocyanine compound No. 1 was obtained in a yield of 4.4 g. 
3 g of this crude product was chromatographed on silica gel and eluted with 
a mixed solvent of toluene and ethyl acetate (20:1), whereby 1.6 g of a 
purified phthalocyanine compound No. 1 was obtained. 
The analysis data of the thus obtained phthalocyanine compound No. 1 was as 
follows: 
______________________________________ 
IR spectrum (KBr): 
1110 to 1180 cm.sup.-1 (.nu.CF) 
Solubility in 1,2- 2% or more at room temperature 
dichloroethane: 
Solubility in 2% or more at room temperature 
toluene: 
Solubility in 2% or more at room temperature 
ethyl cellosolve: 
DSC analysis: Exothermic peaks near 247.degree. C. 
TG analysis: Reduction in weight began to be 
observed near 240.degree. C. 
______________________________________ 
The result of the elemental analysis of the phthalocyanine compound No. 1 
was as follows: 
______________________________________ 
% C % H % N 
______________________________________ 
Found 60.48 2.90 8.66 
Calculated 60.32 2.85 8.79 
______________________________________ 
The calculation is based on the formula for C.sub.54 H.sub.26 N.sub.8 
O.sub.4 F.sub.12 Zn. 
EXAMPLE 2 
Synthesis of Phthaloacyanine Compound No. 2 in TABLE 1 
Step (2-1) (Synthesis of acetophenone derivative of 
2,2,3,3-pentafluoro-1-phenylpropanone) 
25 g of methyl pentafluoropropionate and 630 ml of anhydrous ethyl ether 
were placed in a flask equipped with a reflux condenser. This reaction 
mixture was cooled using dry ice and acetone. When the reaction mixture 
was cooled to temperature in the range of -45 to -60.degree. C., 78 ml of 
phenyl lithium was added dropwise to the reaction mixture over a period of 
30 minutes, and then the reaction mixture was stirred for one hour with 
the temperature being maintained at -45.degree. C. or less. Thereafter, 
the reaction mixture was further stirred for 2.5 hours as being allowed to 
stand at room temperature. 
When the reaction mixture was returned to room temperature, the reaction 
mixture was poured into 1000 ml of a 7% aqueous solution of hydrochloric 
acid, and the resultant ether layer was separated from the reaction 
mixture. The ether layer was successively washed with 1000 ml of a 5% 
aqueous solution of sodium carbonate, and 1000 ml of an aqueous solution 
of sodium chloride, and dried over magnesium sulfate. Magnesium sulfate 
was removed from the mixture by filtration, and then the ether was 
distilled away from the resulting filtrate, whereby 22 g of an 
acetophenone derivative was obtained as a light brown-yellow oily 
material. 
The analysis data of the thus obtained acetophenone derivative was as 
follows: 
______________________________________ 
Mass spectrum: 224 (M.sup.+) 
IR spectrum: 1709 cm.sup.-1 (.nu.CO) 
1100 to 1217 cm.sup.-1 (.nu.CF) 
______________________________________ 
Step (1-2) (Synthesis of benzyl alcohol derivative of 
2,2,3,3,3-pentafluoro-1-phenylpropanol) 
22 g of the acetophenone derivative obtained in the above step (1-1) and 
300 ml of isopropyl alcohol were placed in a flask . This reaction mixture 
was heated to 40.degree. C. with stirring. 15 g of sodium boron hydroxide 
was added to the reaction mixture, and the mixture was further stirred at 
40.degree. C. for 3.5 hours. 
This reaction mixture was then allowed to stand at room temperature and 
cooled to room temperature. The reaction mixture was then poured into 1500 
ml of water, and extracted with diethyl ether. The extract layer was 
washed with water and dried over magnesium sulfate, and then concentrated 
, whereby a benzyl alcohol derivative was obtained as a light brown oily 
material in a yield of 19 g. 
The analysis data of the thus obtained benzyl alcohol was a follows: 
______________________________________ 
Mass spectrum: 226 (M.sup.+) 
IR spectrum: no absorption peak (.nu.CO) 
3360 cm.sup.-1 (.nu.OH) 
1130 to 1210 cm.sup.-1 (.nu.CF) 
______________________________________ 
Step (1-3) (Synthesis of phthalonitrile derivative) 
19 g of the benzyl alcohol derivative obtained in the above Step (1-2), 9.4 
g of anhydrous potassium carbonate, and 50 ml of dimethyl sulfoxide were 
placed in a flask. A solution prepared by dissolving 5.9 g of 
3-nitrophthalonitrile in 20 ml of dimethyl sulfoxide was added dropwise to 
the reaction mixture at 45.degree. C. with stirring over a period of one 
hour. 
After this reaction mixture was stirred at 60.degree. C. for 4 hours, the 
reaction mixture was poured into 600 ml of water and extracted with ethyl 
acetate. The resultant extract layer was washed with water, and ethyl 
acetate was distilled away from the extract layer. Thus, a phthalonitrile 
derivative was obtained as a light brown oily material in a yield of 8 g. 
The analysis data of the thus obtained phthalonitrile derivative was as 
follows: 
______________________________________ 
Mass spectrum: 352 (M.sup.+) 
______________________________________ 
Step (1-4) (Synthesis of phthalocyanine compound No. 2 in TABLE 1) 
8 g of the phthalonitrile derivative obtained in the above Step (1-3), 6.0 
g of DBU, and 25 ml of 1-pentanol were placed in a flask. The reaction 
mixture was heated to 90.degree. C. with stirring in a stream of nitrogen. 
With the addition of 0.45 g of zinc chloride, the reaction mixture was 
stirred at 100.degree. C. for 6 hours. 
This reaction mixture was then allowed to stand at room temperature and 
poured into 200 ml of methanol. To this mixture, 100 ml of water was 
further added. Crystals which separated out in the mixture were filtered 
off and dried, whereby a crude product of a phthalocyanine compound No. 2 
was obtained in a yield of 6.9 g. 
This crude product was chromatographed on silica gel and eluted with a 
mixed solvent of toluene and ethyl acetate (40;1), whereby 2.5 g of a 
purified phthalocyanine compound No. 2 was obtained. 
The analysis data of the thus obtained phthalocyanine compound No. 2 was as 
follows; 
______________________________________ 
Solubility in 2% more at room temperature 
ethyl cellosolve: 
DSC analysis: Exothermic peaks near 215.degree. C. and 
373.degree. C. 
TG analysis: Reduction in weight began to be 
observed near 200.degree. C. 
______________________________________ 
EXAMPLE 3 
Synthesis of Phthalocyanine Compound No. 3 in TABLE 1 
Step (1-1) (Synthesis of phthalonitrile derivative) 
10 g of 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol (available from Central 
Glass Co., Ltd.), 16 g of anhydrous potassium carbonate, and 25 ml of 
N,N-dimethylformamide were placed in a flask. 4.8 g of 
3-nitrophthalonitrile was added dropwise to the above reaction mixture 
over a period of 40 minutes with stirring with the temperature of the 
reaction mixture being maintained in the range of 40 to 50.degree. C. 
This reaction mixture was stirred at 70.degree. C. for 6 hours and then 
poured into 600 ml of water. Crystals which separated out in the mixture 
were filtered off and dried, whereby a phthalonitrile derivative was 
obtained in a yield of 5.2 g. 
The analysis data of the thus obtained phthalonitrile derivative was as 
follows: 
______________________________________ 
Mass spectrum: 370 (M.sup.+) 
Melting point: 150 to 152.degree. C. 
______________________________________ 
Step (1-2) (Synthesis of phthalocyanine compound No. 3 in TABLE 1) 
5.2 g of the phthalonitrile derivative obtained in the above Step (1-1), 
5.1 g of DBU, 30 ml of 1-pentanol, and 0.64 g of zinc chloride were placed 
in a flask. 
This reaction mixture was stirred in a stream of nitrogen at temperature in 
the range of 90 to 95.degree. C. for 5 hours. 
This reaction mixture was then poured into 300 ml of methanol. To this 
mixture, 100 ml of water was further added. Crystals which separated out 
in the mixture were filtered off and dried, whereby a crude product of a 
phthalocyanine compound No. 3 was obtained in a yield of 5.3 g. 
This crude product was chromatographed on silica gel and eluted with 
toluene, whereby 2.0 g of a purified phthalocyanine compound No. 3 was 
obtained. 
The analysis data of the thus obtained phthalocyanine compound No. 3 was as 
follows: 
______________________________________ 
Solubilities in 1% or more at room temperature 
tetrahydrofuran, 
acetone, ethanol, 
ethyl acetate and 
toluene: 
DSC analysis: Exothermic peaks near 245.degree. C. 
TG analysis: Reduction in weight began to be 
observed near 230.degree. C. 
IR spectrum (KBr): 1110 to 1150 cm.sup.-1 (.nu.CF) 
.iota.H-NHR (tetrahydrofuran): .delta. (ppm from TMS) 
7.1-7.5 (8H,m), 
7.6-8.1 (20H,m), 
c9.2-9.4 (4H,m) 
______________________________________ 
EXAMPLE 4 
Synthesis of Phthalocyanine Compound No. 4 in TABLE 1 
Step (1-1) (Synthesis of benzyl alcohol derivative of 
2,2,3,3,4,4,5,5,5-nonafluoro-1-phenylpentanol) 
7.5 g of benzaldehyde, 175 ml of dimethylformamide, and 11 g of zinc powder 
were placed in a flask. This reaction mixture was maintained at room 
temperature on a water bath, and irradiated by ultrasonic wave of 45 kHz. 
29.5 g of nonafluorobutyl iodide was added dropwise to the reaction 
mixture over a period of 30 minutes. 
After the reaction mixture was further irradiated by ultrasonic wave for 4 
hours with the temperature thereof being maintained at 20 to 30.degree. 
C., the reaction mixture was poured into 1000 ml of a 5% aqueous solution 
of hydrochloric acid. 
200 ml of toluene was added to the reaction mixture, and zinc powder was 
removed from the reaction mixture by filtration. The resultant toluene 
layer was separated from the filtrate, and successively washed with a 2% 
aqueous solution of sodium carbonate and water, and then toluene was 
distilled away, whereby a benzyl alcohol was obtained as a light brown 
oily material in a yield of 4 g. 
The analysis data of the thus obtained benzyl alcohol was as follows: 
______________________________________ 
Mass spectrum: 326 (M.sup.+) 
IR spectrum: 3450 cm.sup.-1 (.nu.OH) 
1140 to 1350 cm.sup.-1 (.nu.CF) 
______________________________________ 
Step (1-2) (Synthesis of phthalonitrile derivative) 
4 g of the benzyl alcohol derivative obtained in the above Step (1-1), 5.5 
g of anhydrous potassium carbonate, 1.7 g of 3-nitrophthalonitrile, and 20 
ml of dimethyl sulfoxide were placed in a flask. 
This reaction mixture was stirred at temperature in the range of 50 to 
60.degree. C. for 3 hours, and then allowed to stand at room temperature. 
Thereafter, the reaction mixture was poured into 500 ml of water. Crystals 
which separated out in the mixture were filtered off and dried, whereby a 
phthalonitrile derivative was obtained as a light brown solid in a yield 
of 3.5 g. 
The analysis data of the thus obtained phthalonitrile derivative was as 
follows: 
______________________________________ 
Mass spectrum: 452 (M.sup.+) 
IR spectrum (KBr): 2230 cm.sup.-1 (.nu.CN), 
1130 to 1350 cm.sup.-1 (.nu.CF) 
Melting point: 100 to 110.degree. C. 
______________________________________ 
Step (1-3) (Synthesis of phthalocyanine compound No. 4 in TABLE 1) 
3.5 g of the phthalonitrile derivative obtained in the above Step (1-2), 20 
ml of 1-pentanol, and 0.35 g of zinc chloride were placed in a flask. 
This reaction mixture was heated to 90.degree. C. with stirring in a stream 
of nitrogen, and 3.6 g of DBU was added dropwise to the reaction mixture 
over a period of 30 minutes. 
After the completion of addition of DBU, this reaction mixture was stirred 
at 95.degree. C. for 6 hours. 
Thereafter, the reaction mixture was allowed to stand at room temperature 
and poured into 200 ml of methanol. To this mixture, 100 ml of water was 
further added. Crystals which separated out in the mixture were filtered 
off and dried, whereby a crude product of a phthalocyanine compound No. 4 
was obtained in a yield of 3.1 g. 
This crude product was chromatographed on silica gel and eluted with 
toluene, whereby 0.4 g of a purified phthalocyanine compound No. 4 was 
obtained. 
The analysis data of the thus obtained phthalocyanine compound No. 4 was as 
follows: 
______________________________________ 
Solubility in 1% or more at room temperature 
ethyl cellosolve: 
Solubility in 1,2- 1% or more at room temperature 
dichloroethane: 
______________________________________ 
EXAMPLE 5 
Synthesis of Phthalocyanine Compound No. 5 in TABLE 1 
The procedure for synthesis of the phthalocyanine compound No. 3 in Example 
3 was repeated except that zinc chloride in an amount of 0.64 g used in 
the step (1-2) in Example 3 was replaced by cuprous chloride. Thus, a 
purified phthalocyanine compound No. 5 was obtained in a yield of 2.5 g. 
The analysis data of the thus obtained phthalocyanine compound No. 5 was as 
follows: 
______________________________________ 
Solubility in 1% or more at room temperature 
tetrahydrofuran; 
DSC analysis: Exothermic peaks near 233 to 
265.degree. C. 
TG analysis: Reduction in weight began to be 
observed near 220.degree. C. 
______________________________________ 
EXAMPLE 6 
Synthesis of Phthalocyanine Compound No. 6 in TABLE 1 
The procedure for synthesis of the phthalocyanine compound No. 1 in Example 
1 was repeated except that zinc chloride in an amount of 0.64 g used in 
the step (1-3) in Example 1 was replaced by nickel chloride. Thus, a 
purified phthalocyanine compound No. 6 was obtained in a yield of 0.8 g. 
The analysis data of the thus obtained phthalocyanine compound No. 6 was as 
follows: 
______________________________________ 
Solubility in 1% or more at room temperature 
1,2-dichloroethane: 
______________________________________ 
Reference Example 1 
Synthesis of Reference Phthalocyanine Compound No. 7 in TABLE 1 
The procedure for synthesis of the phthalocyanine compound No. 5 in Example 
5 was repeated except that cuprous chloride in an amount of 0.64 g used in 
Example 5 was replaced by vanadium trichloride. Thus, a reference 
phthalocyanine compound No. 7 was obtained. 
TABLE 1 shows the substituent (-O-CR.sup.1 R.sup.2 R.sup.3), the central 
metal and the absorption maximum wavelength (.lambda..sub.max) of the 
absorption spectrum in tetrahydrofuran of each phthalocyanine compound 
synthesized in Examples 1 to 6 and Reference Example 1. 
TABLE 1 
______________________________________ 
Com- 
pound Substituent Central max 
No. (--O--CR.sup.1 R.sup.2 R.sup.3) Metal M (nm) 
______________________________________ 
Ex. 1 1 
Zn 690 
- Ex. 2 2 
Zn 689 
- Ex. 3 3 
Zn 685 
- Ex. 4 4 
Zn 686 
- Ex. 5 5 
Cu 687 
- Ex. 6 6 
Ni 688 
Reference Ex. 1 7 
vo 718## 
______________________________________ 
Application Example 
Fabrication of Optical Recording Medium 
A pattern of guide groove with a depth of about 1500 .ANG. was formed on 
the surface of a polycarbonate substrate with a diameter of 120 mm and a 
thickness of 1.2 mm. 
A coating liquid for a light absorption layer was prepared by mixing the 
phthalocyanine compound No. 3 in TABLE 1 and the phthalocyanine compound 
No. 7 serving as a sensitizer in the ratio by weight of 3:2, and the thus 
prepared mixture was dissolved in a mixed solvent of tetrahydrofuran, 
1-methoxy-2-butanol and ethyl cyclohexane. The coating liquid thus 
prepared was applied to the polycarbonate substrate by spin-coating, so 
that the light absorption layer was provided on the polycarbonate 
substrate. 
The absorption maximum wavelength (.lambda..sub.max) of the light 
absorption layer thus obtained was 710 nm, and the thickness of the light 
absorption layer was about 1500 .ANG.. 
A light reflection layer with a thickness of about 1000 .ANG. was provided 
on the light absorption layer by sputtering of Au. 
Further, there was provided on the light reflection layer a 5-.mu.m-thick 
protective layer comprising an ultraviolet-curing resin (Trademark 
SD-1700", made by Dainippon Ink & Chemicals, Incorporated). 
Thus, a write once read many type compact disk was fabricated. 
Information was recorded in the thus fabricated compact disk using a 
commercially available CD-writer (Trademark CDW-900E, made by Sony 
Corporation) at a 2.times.nominal CD speed, and the recorded information 
was reproduced using a commercially available CD player (Trademark 
CDP-M51/2, made by Sony Corporation). In this reproduction test, the 
reproducing operation was normally carried out. In addition, the number of 
C1 errors decoded from the CD player was 50 or less, which satisfied the 
CD standard (220 or less). 
As previously explained, the phthalocyanine compound of the present 
invention is readily soluble in a variety of organic solvents at room 
temperature, so that this phthalocyanine compound shows excellent 
workability when formed into a thin film. In addition, since the film of 
the phthalocyanine compound exhibits high absorptivity coefficient and 
excellent thermal response performance, the phthalocyanine compound of the 
present invention can be used in various applications, for example, as the 
optical recording material. 
Japanese Patent Application No. 09-221924 filed Aug. 4, 1997 is hereby 
incorporated by reference.