benzene-1,2-dicarbonitrile

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A suspension of phthalonitrile (70 g, 0.55 mol) in ethanol (100 ml) and chloroform (200 ml) was warmed and then cooled to 0° C. The reaction mixture was saturated with HCl (g) and then aged at 0° C. for 2 weeks. The resultant precipitate was filtered and washed with chloroform. Dilution of the filtrate with ether produced additional 2-cyano-benzimidic acid ethyl ester hydrochloride. was warmed aged at 0° C. for 2 weeks The resultant precipitate was filtered washed with chloroform

Conditions: temp:210.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A zeolite X powder including Co2+-phthalocyanine complex (CoPc) was prepared according to the following procedure. Specifically, a powder (product supplied by Tosoh Corporation) of zeolite X containing sodium ions (NaX) was prepared, and part of sodium ions (Na+) contained in the zeolite were exchanged with cobalt ions (Co2+) through ion exchange to yield NaX containing 0.95 percent by weight of Co2+ ions (Co—NaX). In acetone were stirred 108.96 g of the Co—NaX (containing 18 mmol of Co2+) and 0.127 mol of o-phthalonitrile for one hour, a volatile component was removed from the react ion mixture, and the residue was suspended in 250 mL of ethylene glycol. The suspension was combined with 15 mL of tri-n-butylamine ((n-Bu)3N), and the mixture was stirred at 210° C. for 5 hours to give a solid. The solid was purified through extraction sequentially with methanol, acetone, and pyridine in a Soxhlet extractor to remove unnecessary substances such as unreacted ligand contained in the solid and phthalocyanine that had formed outside the zeolite pores. The purified product was suspended in 400 mL of a saturated aqueous solution of sodium nitrate, followed by stirring for 24 hours, to remove unreacted cobalt ions that had remained without forming the complex through exchange with sodium ions. The resulting substance was washed with water, dried at 60° C., and thereby yielded a pale blue powder. The energy dispersive X-ray spectroscopy (EDX), ultraviolet-visible (UV/vis) absorption spectra, and diffuse reflection spectra of the powder verified that a target substance (CoPc@NaX) composed of NaX and cobalt phthalocyanine encapsulated in the NaX unit cell was obtained. was prepared was prepared to yield NaX a volatile component was removed from the react ion mixture to give a solid The solid was purified through extraction sequentially with methanol, acetone, and pyridine in a Soxhlet extractor to remove unnecessary substances such as unreacted ligand

Conditions: temp:217.51; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Phthalonitrile (1100 grams) and titanium tetrachloride (813 grams) were suspended in 6800 milliliters (ml) of 1-chloronaphthalene and heated to 215-220° C. and maintained for 2.5 hours at this temperature. The reaction mixture was cooled to 140° C., and the dark solid was collected and washed with acetone and methanol. After drying, the dark blue solid (1090 grams) was slurried twice in refluxing 10 liters of distilled water for two hours, filtered hot each time, and washed with acetone to yield crude phthalocyanine. The X-ray diffraction spectrum exhibits major peaks of the Bragg angle at 7.5, 8.3, 10.5, 12.7, 14.2, 14.6, 18.9, 22.1, 24.3, 26.1, and 29.9 (all +/-0.2 degrees). maintained for 2.5 hours at this temperature The reaction mixture was cooled to 140° C. the dark solid was collected washed with acetone and methanol After drying in refluxing 10 liters of distilled water for two hours filtered hot each time washed with acetone

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In this comparative example, α-titanyloxyphthalocyanine was prepared by the method disclosed in Japanese Patent Application Laying-open No.62-134651. That is, a mixture of 40 g of phthalodinitrile, 18 g of titanium tetrachloride, and 500 cc of chloronaphthalene was stirred at the temperature of 240° C. to 250° C. for 3 hours in nitrogenous atmosphere to completely react with each other. The mixture was filtrated after the reaction, and as a result dichlorothitanium phthalocyanine was obtained. The obtained dichlorothitanium was mixed with 300 cc of concentrated ammonium solution to obtain a mixture. Then the mixture was heat-refluxed for 1 hour and subjected to the purification by using a Soxhlet extractor. Consequently, titanyloxyphthalocyanine was obtained by drying the purified product. The resultant titanyloxyphthalocyanine was confirmed as α-type crystal having an X-ray diffraction spectrum which is the same as the one shown in FIG. 3. to completely react with each other The mixture was filtrated after the reaction

Conditions: temp:200.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 29.1 parts of phthalonitrile, 9.2 parts of gallium trimethoxide, and 150 parts of ethylene glycol was stirred for 24 hours at 200° C. in a nitrogen atmosphere, and the product was filtered. The product was successively washed with N,N-dimethylformamide and then methanol, and dried to provide 23.0 parts of gallium phthalocyanine. the product was filtered The product was successively washed with N,N-dimethylformamide methanol, and dried

Conditions: temp:225.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 40 g of o-phthalodinitrile, 18 g of titanium tetrachloride and 500 ml of α-chloronaphthalene were heated and stirred under a nitrogen atmosphere at 200 to 250° C. for 3 hours to react them, and after allowed to be cooled to 100 to 130° C., the reaction product was filtrated while hot and washed with 200 ml of α-chloronaphthalene heated to 100° C., so as to obtain a crude product of dichlorotitanium phthalocyanine. The crude product was washed successively with 200 ml of α-chloronaphthalene and 200 ml of methanol at room temperature, and was washed by dispersing in 500 ml of hot methanol for 1 hour. A crude product obtained by filtration was repeatedly washed by dispersing in 500 ml of hot water until the pH becomes 6 to 7, and oxotitanylphthalocyanine crystal was obtained by drying. to react them to be cooled to 100 to 130° C. the reaction product was filtrated while hot and washed with 200 ml of α-chloronaphthalene heated to 100° C.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 31.8 parts of phthalonitrile, 10.1 parts of gallium trimethoxide, and 150 ml of ethylene glycol were stirred at a temperature of 200° C. in an atmosphere of nitrogen for 24 hours. The resulting product was then filtered. The product was washed with N,N-dimethylformamide and then with methanol, and then dried to obtain 25.1 parts of gallium phthalocyanine. The resulting product was then filtered The product was washed with N,N-dimethylformamide with methanol, and then dried

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 31.8 parts of phthalonitrile, 10.1 parts of gallium trimethoxide, and 150 ml of ethylene glycol were stirred at a temperature of 200° C. in an atmosphere of nitrogen for 24 hours. The resulting product was then filtered. The product was washed with N,N-dimethylformamide and then with methanol, and then dried to obtain 25.1 parts of gallium phthalocyanine. The resulting product was then filtered The product was washed with N,N-dimethylformamide with methanol, and then dried

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of aniline 2,5 disulphonic acid (27.5 g) in water (250 ml) was added to intermediate E (63.2 g) in acetonitrile (800 ml) and heated at 40° C. and at pH 5 to 7 overnight. The reaction solvent was removed under reduced pressure, water (50 ml) was added and then brine (60 ml) the solid which precipitated of filtered off, washed with 10% brine and dried to give product (91.1% strength, 22 g). The reaction solvent was removed under reduced pressure, water (50 ml) was added brine (60 ml) the solid which precipitated of filtered off washed with 10% brine dried to give product (91.1% strength, 22 g)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of intermediate D (32.7 g) in acetone (500 ml) was added to cyanuric chloride (18.5 g) in acetone (150 ml) at 0° C. and stirred at this temperature for 2 hours, maintaining the pH at 6 with 0.5M sodium hydroxide solution. The precipitated solid was filtered off, washed with ice cold water (2×250 ml) and dried to give the damp product (65.2 g). The precipitated solid was filtered off washed with ice cold water (2×250 ml) dried

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 31.8 parts of phthalonitrile, 10.1 parts of gallium trimethoxide and 150 ml of ethylene glycol were stirred under nitrogen atmosphere at 200° C. for 24 hours, and the product obtained was filtered. Then the product was washed with N,N-dimethylformamide and methanol successively, and dried to give 25.1 parts of gallium phthalocyanine. the product obtained was filtered Then the product was washed with N,N-dimethylformamide and methanol successively dried

Conditions: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 2000 mL, three-necked flask fitted with a thermometer and a nitrogen inlet were added 1,3-dihydroxybenzene (48.2 g, 0.438 mol), bis(chloromethyl)tetramethyl disiloxane (50.1 g, 0.217 mol), powdered anhydrous K2CO3 (150 g, 1.09 mol), and dimethylsulfoxide (DMSO) (1000 mL). The resulting mixture was degassed with nitrogen at ambient temperature and heated at 90° C. under a nitrogen atmosphere for 8-16 hr. The mixture was cooled to 50° C. At this time, 4-nitrophthalonitrile (76.1 g, 0.440 mol) was added in one portion and the reaction mixture was heated at 80° C. for 6-8 hr. The mixture was allowed to cool to ambient temperature and poured into 1000 mL of distilled water. The mixture was made acidic by the addition of 6 M aqueous HCl and the resin was extracted out of the water layer by toluene (200 mL). The toluene extracts were washed 3 times with 500 mL of distilled water and the toluene extracts were dried using magnesium sulfate. Removal of the toluene resulted in an amber oil, which was dried at 80° C. under vacuum. The 2:1 oligomeric phthalonitrile was isolated as an amber glassy solid (131 g, 95%). 1H-NMR [CDCl3]: λ 7.70 (m, aromatic-HR), 7.69 (m, aromatic-HR), 7.35 (m, aromatic-HR), 7.10 (m, aromatic-HR), 6.98 (m, aromatic-HR), 6.88 (m, aromatic-HR), 3.73 (m, aliphatic-HR), 3.46 (m, aliphatic-HR), 0.22 (s, Si—CH3), 0.06 (s, Si—CH3). To a 2000 mL, three-necked flask fitted with a thermometer and a nitrogen inlet The resulting mixture was degassed with nitrogen at ambient temperature The mixture was cooled to 50° C the reaction mixture was heated at 80° C. for 6-8 hr to cool to ambient temperature the resin was extracted out of the water layer by toluene (200 mL) The toluene extracts were washed 3 times with 500 mL of distilled water the toluene extracts were dried Removal of the toluene resulted in an amber oil, which was dried at 80° C. under vacuum