26201-32-1

Basic information

• Product Name: Titanyl phthalocyanine
• Synonyms: Phthalocyanine titanium oxide §Oxytitanium phthalocyanine;TITANYL PHTHALOCYANINE, BETA MODIFICATI&;PhthalocyanineTitanyl;PHTHALOCYANINE TITANIUM OXIDE COMPLEX, Y-MODIFICATION;Oxytitamiumphthalocyanine;oxo[29H,31H-phthalocyaninato-N29, N30, N31, N32]-, (SP-5-12)-Titanium;29H,31H-Phthalocyanine titanium oxide
• CAS NO: 26201-32-1
• Molecular Formula: C₃₂H₁₆N₈OTi
• Molecular Weight: 576.39
• EINECS: 419-970-5
• Product Categories: Organometallics;electronic;pharmacetical;Infrared (IR) DyesPhotonic and Optical Materials;Organic Electronics and Photonics;Photonic and Optical Materials;Phthalocyanine and Porphyrin Dyes;Phthalocyanines;Hole Transporting MaterialsOrganic Electronics and Photonics;OLED and PLED Materials;oled materials
• Mol File: 26201-32-1.mol

Chemical Properties

• Melting Point: 395.1 °C (dec.)(lit.)
• Appearance: /
• Storage Temp.: Keep in dark place,Sealed in dry,Room Temperature
• Solubility: Chlorobenzene [7]
• CAS DataBase Reference: Titanyl phthalocyanine(CAS DataBase Reference)
• NIST Chemistry Reference: Titanyl phthalocyanine(26201-32-1)
• EPA Substance Registry System: Titanyl phthalocyanine(26201-32-1)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36
• WGK Germany: 3
• TSCA: No
• Hazardous Substances Data: 26201-32-1(Hazardous Substances Data)

Usage

Uses

1. Used in Electrophotography:
Titanyl phthalocyanine is used as a sensitizer in the electrophotography industry, taking advantage of its high photosensitivity to NIR light.
2. Used in Water Photo-oxidation:
Titanyl phthalocyanine serves as a water photo-oxidation agent, playing a crucial role in the process of breaking down water molecules using light energy.
3. Used in NO2 Detection Sensors:
Titanyl phthalocyanine is integrated into sensors designed for the detection of nitrogen dioxide (NO2), leveraging its photochemical properties.
4. Used in Organic Light-Emitting Diodes (OLEDs):
Titanyl phthalocyanine is employed in the construction of OLEDs, where it functions as a light-harvesting dye. Devices utilizing TiOPc have demonstrated photon to current efficiency (PCE) exceeding 4% when paired with C60 as the electron acceptor.
5. Used in Organic Photovoltaics (OPVs):
Similar to its application in OLEDs, Titanyl phthalocyanine is also used in OPVs as a light-harvesting dye, contributing to the efficiency of these solar energy conversion devices.

InChI:InChI=1/C32H16N8.O.Ti/c1-2-10-18-17(9-1)25-33-26(18)38-28-21-13-5-6-14-22(21)30(35-28)40-32-24-16-8-7-15-23(24)31(36-32)39-29-20-12-4-3-11-19(20)27(34-29)37-25;;/h1-16H;;/q-2;;+2/rC32H16N8.OTi/c1-2-10-18-17(9-1)25-33-26(18)38-28-21-13-5-6-14-22(21)30(35-28)40-32-24-16-8-7-15-23(24)31(36-32)39-29-20-12-4-3-11-19(20)27(34-29)37-25;1-2/h1-16H;/q-2;+2

Synthetic route

dichloro(phthalocyaninato)titanium(IV) (1208497-30-6, 16903-42-7) + water (7732-18-5) → oxotitanium(IV) phthalocyanine (26201-32-1)

Conditions	Yield
In pyridine Ti-complex was boiled in aq. pyridine for 2 h, cooled; filtered, washed with water, dried in vacuo at 100°C; elem. anal.;	97%
With hydrogenchloride In DMF (N,N-dimethyl-formamide); water at 100 - 120℃; for 1h;

titanium tetrachloride (7550-45-0) + phthalonitrile (91-15-6) → oxotitanium(IV) phthalocyanine (26201-32-1)

Conditions	Yield
In quinoline at 180℃; for 6h; Product distribution / selectivity;	76.8%
With thiourea In further solvent(s) TiCl4 was mixed with heptanol, heated to boiling, ligand was added, withor without thiourea, heated to 170°C, kept for 6 h; cooled, filtered, washed with toluene and MeOH, extd. with MeOH in Soxhlet for 4 h, dried in air; elem. anal.;	60%
In ethanol at -20.01℃; under 46504.7 Torr; for 1h;	60%

isoindole-1,3-diylidenediamine (160956-25-2, 160956-26-3, 160956-27-4, 160956-28-5, 160956-29-6) + titanium tetra-n-propoxide (3087-37-4) + phthalonitrile (91-15-6) → oxotitanium(IV) phthalocyanine (26201-32-1)

Conditions	Yield
In 1-methyl-pyrrolidin-2-one at 198℃; for 2h; Product distribution / selectivity; Heating / reflux;	76%

tetrabutoxytitanium + isoindole-1,3-diylidenediamine (160956-25-2, 160956-26-3, 160956-27-4, 160956-28-5, 160956-29-6) → oxotitanium(IV) phthalocyanine (26201-32-1) + butan-1-ol (71-36-3)

Conditions	Yield
In 1-chloronaphthalene (CINp) at 140 - 200℃; for 2h; Product distribution / selectivity;	A 72% B n/a

→ oxotitanium(IV) phthalocyanine

Conditions	Yield
In 1-Chloronaphthalene at 195℃; for 3h; Product distribution / selectivity; Heating / reflux;	70%
In 1-methyl-pyrrolidin-2-one at 50 - 95℃; for 6h; Product distribution / selectivity;	1.5%
In 1-methyl-pyrrolidin-2-one at 24 - 100℃; Product distribution / selectivity; Electrochemical reaction;
In ethylene glycol at 24 - 100℃; Product distribution / selectivity; Electrochemical reaction;
In sulfolane Inert atmosphere;

dichlorotitanium phthalocyanine (1208497-30-6, 16903-42-7) → oxotitanium(IV) phthalocyanine (26201-32-1)

Conditions	Yield
With hydrogenchloride; N,N-dimethyl-formamide In water at 100 - 120℃; for 1h; pH=>= 6;

tetrabutoxytitanium + phthalonitrile (91-15-6) → oxotitanium(IV) phthalocyanine (26201-32-1)

Conditions	Yield
With pentan-1-ol; benzamide In xylene at 144℃; for 6h; Heating / reflux;

oxygen (80937-33-3) + titanium tetrachloride (7550-45-0) + phthalonitrile (91-15-6) → oxotitanium(IV) phthalocyanine (26201-32-1)

Conditions	Yield
In 1-Chloronaphthalene at 25 - 210℃; for 5h;
In Diphenylmethane; 1,1,2,2-tetrachloroethane at 40 - 210℃; for 6 - 8h; Product distribution / selectivity;

urea (57-13-6) + phthalonitrile (91-15-6) → oxotitanium(IV) phthalocyanine (26201-32-1)

Conditions	Yield
With tetrabutoxytitanium In nonyl alcohol at 160 - 170℃; for 0.1 - 6h; Product distribution / selectivity; Microwave and ultrasonic energy;

isoindole-1,3-diylidenediamine (160956-25-2, 160956-26-3, 160956-27-4, 160956-28-5, 160956-29-6) → oxotitanium(IV) phthalocyanine (26201-32-1)

Conditions	Yield
With quinoline; tetrabutoxytitanium at 170 - 180℃; for 0.1 - 6h; Product distribution / selectivity;

tetrabutoxytitanium + 4,5-dichlorophthalonitrile (139152-08-2) + phthalonitrile (91-15-6) → oxotitanium(IV) phthalocyanine (26201-32-1) + C32H14Cl2N8OTi

Conditions	Yield
With benzamide In pentan-1-ol; xylene Reflux;

tetrabutoxytitanium + urea (57-13-6) + phthalonitrile (91-15-6) → oxotitanium(IV) phthalocyanine (26201-32-1)

Conditions	Yield
With tin(IV) chloride In octanol at 155 - 159℃; for 6h; Inert atmosphere;	22.77 g

oxotitanium(IV) phthalocyanine (26201-32-1) + 2,6-diisopropylphenyl isocyanate (28178-42-9) → (2,6-diisopropylphenylimido)phthalocyaninatotitanium(IV) (1276014-86-8)

Conditions	Yield
In further solvent(s) byproducts: CO2; under N2; mixt. of Ti complex and ((CH3)2CH)2C6H3NCO (20-fold excess) inchloronaphthalene heated at 180°C for 6 h, released CO2 replaced by N2 from time to time; mixt. cooled, pptn. by addn. of hexane, solid filtered off, extd. repeatedly with MeCN and toluene (10x50 mL each) under reflux, washed with pentane, dried at 120°C under vac. for 3 h; elem. anal.;	83%

oxotitanium(IV) phthalocyanine (26201-32-1) + p-Tolylisocyanate (622-58-2) → (N,N'-di(p-tolyl)ureato-κ2N,N')phthalocyaninatotitanium(IV) (1217488-65-7)

Conditions	Yield
In further solvent(s) byproducts: CO2; under N2; mixt. of Ti complex and p-tolyl isocyanate in chloronaphthalene heated at 180°C for 6 h, released CO2 replaced by N2 from time to time; soln. cooled, pptn. by addn. of hexane, solid filtered off, extd. with rMeCN and toluene (10x50 mL each) under reflux, washed with pentane, dried at 120°C under vac. for 3 h; elem. anal.;	76%
In further solvent(s) according to Darwish, W. et al., Acta Cryst. E61 2005, m1280-1282; Darwish, W., Dissertation, Philipps University, Marburg, Germany, 2006; solvent: chloronaphthalene;

oxotitanium(IV) phthalocyanine (26201-32-1) + tetrapentylammonium bromide (866-97-7)

Conditions	Yield
With fluorenone radical anion sodium contact ion pair In 1,2-dichloro-benzene at 80℃; for 24h;	74%

Conditions	Yield
In further solvent(s) byproducts: CO2; under N2; mixt. of Ti complex and mesityl isocyanate in chloronaphthalene heated at 180°C for 6 h, released CO2 replaced by N2 from time to time; soln. cooled, pptn. by addn. of hexane, solid filtered off, extd. with rMeCN and toluene (10x50 mL each) under reflux, washed with pentane, dried at 120°C under vac. for 3 h; elem. anal.;	73%

oxotitanium(IV) phthalocyanine (26201-32-1) + tetrahexylammonium bromide (4328-13-6) + 1,2-dichloro-benzene (95-50-1) → C32H16N8OTi(1-)*C24H52N(1+)*C6H4Cl2

Conditions	Yield
With fluorenone radical anion sodium contact ion pair at 80℃; for 24h;	66%

oxotitanium(IV) phthalocyanine (26201-32-1) + triptycene (477-75-8) + tetramethylphosphonium bromide (4519-28-2) + 1,2-dichloro-benzene (95-50-1)

Conditions	Yield
Stage #1: oxotitanium(IV) phthalocyanine; tetramethylphosphonium bromide; 1,2-dichloro-benzene With fluorenone radical anion sodium contact ion pair at 100℃; for 2h; Glovebox; Inert atmosphere; Stage #2: triptycene In benzonitrile at 20 - 100℃; for 3h;	65%

→ sulfido(phthalocyaninato)titanium(IV)

Conditions

Yield

With triphenylphosphine In further solvent(s) (N2); Schlenk techniques; phthalocyanine deriv. and P4S10 heated in chloronaphthalene at 160°C for 10 h; pptd. by addn. of hexane; washedby extn. with refluxing MeCN, toluene; washed with pentane; dried at 12 0.degre.C for 1 h under 1E-3 mbar; heated with triphenylphosphine to a melt at 160°C for 4 h; washedwith refluxing MeCN, toluene; washed with ether; dried at 120.degre.C f or 1 h under 1E-3 mbar;

57%

oxotitanium(IV) phthalocyanine (26201-32-1) + 4-aza-1-methylazoniabicyclo<2.2.2>octane iodide (14968-74-2) → C32H16N8OTi(1-)*C7H15N2(1+)*C20H14

Conditions	Yield
With fluorenone radical anion sodium contact ion pair In 1,2-dichloro-benzene at 100℃; for 24h;	43%

oxotitanium(IV) phthalocyanine (26201-32-1) + 4-aza-1-methylazoniabicyclo<2.2.2>octane iodide (14968-74-2)

Conditions	Yield
With fluorenone radical anion sodium contact ion pair In 1,2-dichloro-benzene at 100℃; for 24h;	38%

+ 4-aza-1-methylazoniabicyclo<2.2.2>octane iodide (14968-74-2) → C32H16N8OTi(1-)*C7H15N2(1+)*C20H14

Conditions	Yield
Stage #1: oxotitanium(IV) phthalocyanine; N-methyl-1,4-diazabicyclo<2.2.2>octanium iodide With fluorenone radical anion sodium contact ion pair In 1,2-dichloro-benzene at 100℃; for 24h; Stage #2: triptycene In benzonitrile; 1,2-dichloro-benzene at 20℃; for 4h;	27%

oxotitanium(IV) phthalocyanine (26201-32-1) + haematoxylin (1621-46-1, 17647-60-8, 98092-70-7, 517-28-2) → ((C32H16N8)Ti)2C16H9O(OH)(O)4

Conditions	Yield
In further solvent(s) Ti-complex was dissolved in 1-chloronaphthalene at 180°C under N2, hematoxylin was added, the soln. was stirred for 15 min; filtd., hexane was added to induce pptn., ppt. was collected and recrystd. from 1-chloronaphthalene/MeOH;	19.1%

oxotitanium(IV) phthalocyanine (26201-32-1) + gallium phthalocyanine hydroxide (63371-84-6) + μ-oxogallium phthalocyanine → PcGa-O-TiPc

Conditions	Yield
With hydrogenchloride; N,N-dimethyl-formamide In water at 100 - 120℃; for 1h; pH=>= 6;

Upstream product

• 91-15-6 phthalonitrile 
• 160956-25-2 isoindole-1,3-diylidenediamine 
• 1208497-30-6 dichlorotitanium phthalocyanine 
• 7732-18-5 water 
• 5593-70-4 titanium (IV) butoxide 
• 57-13-6 urea 
• 60-35-5 acetamide 
• 7664-41-7 ammonia 
• 55-21-0 benzamide 
• 574-93-6 29H,31H-phthalocyanine 
• 7550-45-0 titanium tetrachloride 
• 1208497-30-6 titanium(IV) chloride phthalocyaninate 
• 139152-08-2 4,5-dichlorophthalonitrile 
• 80937-33-3 oxygen 

Downstream Products

• 1276014-89-1 (N,N'-dimesitylureato-κ2N,N')phthalocyaninatotitanium(IV) 
• 1217488-65-7 (N,N'-di(p-tolyl)ureato-κ2N,N')phthalocyaninatotitanium(IV) 
• 1276014-86-8 (2,6-diisopropylphenylimido)phthalocyaninatotitanium(IV) 

Relevant articles and documents

The metal phthalocyanine compound crystal and its manufacturing method, using the electrophotographic photosensitive member, method, Image forming device, and Image forming apparatus and process cartridge for

PROBLEM TO BE SOLVED: To provide a novel metal phthalocyanine mixture crystal useful as an organic photoconductor used in an electrophotographic photoreceptor which is excellent in sensitivity from the visible to the near-infrared region, charging stability in repeated fatigue and stability to variation of temperature and humidity.SOLUTION: A metal phthalocyanine mixture crystal is formed by a crystal conversion treatment of a metal phthalocyanine mixture consisting of a titanyl phthalocyanine obtained by reacting phthalonitrile, a titanium compound and a halide of a metal other than titanium and a metal phthalocyanine of formula (1), where M is a metal atom other than titanium; Q is a bond group selected from a hydroxy group, an oxygen atom and a halogen atom; and n is an integer of 0-2.

MANUFACTURING METHOD OF PHTHALOCYANINE CRYSTAL AND ELECTROPHOTOGRAPHIC PHOTORECEPTOR

PROBLEM TO BE SOLVED: To provide a manufacturing method of a phthalocyanine crystal having improved level of ghost at use initiation and after repeated use and suppressed variation. SOLUTION: There is provided a manufacturing method for obtaining a phthalocyanine crystal by mixing a phthalocyanine compound obtained by acid pasting and an organic compound and conducting crystal transformation, having a process for conducting the crystal transformation by using a dispersion machine having a rotatable rotor and a jacket covering the rotor, and a structure in which at least the rotor has a flow passage of a coolant or a catalyst inside, gap sandwiched by the rotor and an inside wall of the jacket has a part forming an annular space, the rotor and the inner wall of the jacket forming the gap have smooth surfaces respectively and a mixture of the phthalocyanine compound and the organic compound flow between gaps to which media particles are filled. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT

Electrophotographic photoreceptor, electrophotographic image forming method, electrophotographic image forming apparatus, and process cartridge for electrophotographic image forming apparatus

An N-phenyl-diphenylisoindole derivative having the following formula (1): wherein each of R1 and R2 represents a hydrogen atom, a substituted or an unsubstituted alkyl group, a substituted or an unsubstituted alkoxy group, a substituted or an unsubstituted phenyl group, or a substituted or an unsubstituted phenoxy group; R3 represents a hydrogen atom, a substituted or an unsubstituted alkyl group, a substituted or an unsubstituted alkoxy group, a substituted or an unsubstituted phenyl group, a substituted or an unsubstituted phenoxy group, or has the following formula (2): wherein each of R4 and R5 represents a substituted or an unsubstituted alkyl group, or a substituted or an unsubstituted phenyl group; 1 represents an integer of from 1 to 4; and each of m and n represents an integer of from 1 to 5.

Titanyl phthalocyanine with improved milling properties

The invention is directed to mixtures of PcTiO and a minor amount of another, substituted titanyl phthalocyanine and the synthesis of mixtures of PcTiO and a minor amount of another, substituted titanyl phthalocyanine. The invention is further directed towards milled pigment compositions of such mixtures, and to use of such milled pigment compositions in an electrophotographic element.

TITANYL PHTHALOCYANINE PROCESSES AND PHOTOCONDUCTORS THEREOF

A process which includes treating, mixing, or contacting a Type I titanyl phthalocyanine with a weak acid with a pKa of at least equal to or greater than about 0; dissolving the acid treated Type I titanyl phthalocyanine in a solution of a trihaloacetic acid and an alkylene halide; adding the formed mixture to a solution of an alcohol and an alkylene halide thereby precipitating a Type Y titanyl phthalocyanine; and treating the Type Y titanyl phthalocyanine with monohalobenzene thereby resulting in a high sensitivity titanyl phthalocyanine.

Method for producing alpha-form titanylphthalocyanine and electrophotographic photoreceptor comprising alpha-form titanylphthalocyanine

The present invention relates to a method for producing an α-form titanylphthalocyanine represented by the formula (1): which has a peak at a Bragg angle (2θ ± 0.2°) in X-ray diffraction spectrum with CuK α-ray: 7.5°, 10.2°, 12.6°, 13.2°, 15.1°, 16.3°, 17.3°, 18.3°, 22.5°, 24.2°, 25.3° and 28.6°, wherein the method includes steps of: (I) subjecting a crude titanylphthalocyanine having an α-form polymorph to an acid pasting treatment, and then filtering and washing with water to give a water-containing wet cake, and then subjecting the wet cake to drying and crushing to give a low crystalline titanylphthalocyanine; (II) adding a dispersing aid to the low crystalline titanylphthalocyanine and dispersing at room temperature, in DMF, to prepare a polymorph; and (III) filtering, washing, and drying under a reduced pressure. The present invention consists in a provision of a method for conveniently producing the α-form titanylphthalocyanine having a peak at a Bragg angle (2θ ± 0.2°) in X-ray diffraction spectrum with CuK α-ray: 7. 5°, 10. 2°, 12. 6°, 13.2°, 15.1°, 16.3°, 17.3°, 18.3°, 22.5°, 24.2°, 25.3° and 28.6°, wherein a crude titanylphthalocyanine having an α-form polymorph is used as a starting material, as well as a provision of an electrophotographic photoreceptor comprising a charge generating material of the α-form titanylphthalocyanine which has excellent photosensitive characteristics.

Oxo-titanylphthalocyanine crystal, method for producing the same, and electrographic photoreceptor

The invention provides an oxo-titanylphthalocyanine crystal which is stable, is superior in dispersibility in a photoreceptive layer and efficiently contributes to improvements in sensitivity and charge retention rate of an electrophotographic photoreceptor when it is used as a charge generating agent, a method for producing the oxo-titanylphthalocyanine crystal, and an electrophotographic photoreceptor. The oxo-titanylphthalocyanine crystal has predetermined optical characteristics and thermal properties and is produced by a production method including the following steps (a) to (d): (a) a step of dissolving a crude oxo-titanylphthalocyanine crystal in an acid to obtain an oxo-titanylphthalocyanine solution; (b) a step of adding the oxo-titanylphthalocyanine solution dropwise in a poor solvent to obtain a wet cake; (c) a step of washing the wet cake with an alcohol having 1 to 4 carbon atoms; and (d) a step of stirring the washed wet cake under heating in a nonaqueous solvent to obtain an oxo-titanylphthalocyanine crystal.

Titanylphthalocyanine comprising specific polymorph and method for producing thereof, and electrophotographic photoreceptor comprising charge generating material thereof

The present invention relates to a titanylphthalocyanine represented by the formula (1): comprising a polymorph having a peak at a Bragg angle (2θ ± 0.2°) in X-ray diffraction spectrum with CuK α-ray: 9.0°, 9.6°, 14.1°, 14.9°, 17.9°, 18.3°, 23.4°, 24.5° and 27.2°; and and wherein Ir1 is the ratio (9.6°/9.0°) of the intensity of the peak at Bragg angle of 9.6° to the intensity of the peak at Bragg angle of 9.0°; Ir2 is the ratio (14.1°/14.9°) of the intensity of the peak at Bragg angle of 14.1 ° to the intensity of the peak at Bragg angle of 14.9°; Ir3 is the ratio (17.9°/18.3°) of the intensity of the peak at Bragg angle of 17.9° to the intensity of the peak at Bragg angle of 18.3°; and Ir4 is the ratio (24.5°/23.4°) of the intensity of the peak at Bragg angle of 24.5° to the intensity of the peak at Bragg angle of 23.4°. The present invention can provide the above novel titanylphthalocyanine having superior photoreceptor characteristics, particularly superior chargeability and photosensitivity to those of the conventional titanylphthalocyanines, and a method for producing the present titanylphthalocyanine, as well as an electrophotographic photoreceptor comprising a charge generating material of the present titanylphthalocyanine, which has excellent photosensitive characteristics.

METHOD FOR PRODUCING A PIGMENT

Provided is a method for producing a pigment, in particular, a metal phthalocyanine, in high yield and in a green process. The method has (1) a step of obtaining a solution mixture by mixing at least one type of compound serving as a raw material for a pigment with a solvent, and (2) a step of obtaining the pigment by reacting the compound while holding the solution mixture at not less than a temperature where a subcritical state or a supercritical state of the solvent occurs.

Organic photosensitive pigment

Processes for making organic photosensitive pigments for charge generating layers of imaging members. The pigments may include titanyl phthalocyanine. The pigments may be synthesized through a partially electrochemical or purely electrochemical process. The pigments may be used in a charge generating layer of an imaging member having a substrate, the charge generating layer, and a charge transfer layer.