US20070249866A1 - Method for producing aromatic amino compound - Google Patents
Method for producing aromatic amino compound Download PDFInfo
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- US20070249866A1 US20070249866A1 US11/764,912 US76491207A US2007249866A1 US 20070249866 A1 US20070249866 A1 US 20070249866A1 US 76491207 A US76491207 A US 76491207A US 2007249866 A1 US2007249866 A1 US 2007249866A1
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- 0 [1*]N(C)[Ar].[Ar] Chemical compound [1*]N(C)[Ar].[Ar] 0.000 description 4
- QDQORUIDUMJBEM-UHFFFAOYSA-N [Ar].[H]N(C)[Ar] Chemical compound [Ar].[H]N(C)[Ar] QDQORUIDUMJBEM-UHFFFAOYSA-N 0.000 description 4
- RPVFMORXFFZQTN-UHFFFAOYSA-N CN([Ar])[Ar].[Ar].[Ar].[Ar] Chemical compound CN([Ar])[Ar].[Ar].[Ar].[Ar] RPVFMORXFFZQTN-UHFFFAOYSA-N 0.000 description 3
- NWXBCEGZDCZORM-UHFFFAOYSA-N [Ar].[Ar].[H]N([Ar])[Ar] Chemical compound [Ar].[Ar].[H]N([Ar])[Ar] NWXBCEGZDCZORM-UHFFFAOYSA-N 0.000 description 2
- NUJLWADQTBPUFT-UHFFFAOYSA-N BrC1=CC2=C(C=CC=C2)C=C1.C1=CC=C(C2=CC=C(N(C3=CC=C(C4=CC=C(N(C5=CC=C(C6=CC=CC=C6)C=C5)C5=CC=C6C=CC=CC6=C5)C=C4)C=C3)C3=CC=C4C=CC=CC4=C3)C=C2)C=C1.C1=CC=C(C2=CC=C(NC3=CC=C(C4=CC=C(NC5=CC=C(C6=CC=CC=C6)C=C5)C=C4)C=C3)C=C2)C=C1 Chemical compound BrC1=CC2=C(C=CC=C2)C=C1.C1=CC=C(C2=CC=C(N(C3=CC=C(C4=CC=C(N(C5=CC=C(C6=CC=CC=C6)C=C5)C5=CC=C6C=CC=CC6=C5)C=C4)C=C3)C3=CC=C4C=CC=CC4=C3)C=C2)C=C1.C1=CC=C(C2=CC=C(NC3=CC=C(C4=CC=C(NC5=CC=C(C6=CC=CC=C6)C=C5)C=C4)C=C3)C=C2)C=C1 NUJLWADQTBPUFT-UHFFFAOYSA-N 0.000 description 1
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- IBYLKPBDWVJEQI-UHFFFAOYSA-N BrC1=CC=C(C2=CC=CC=C2)C=C1.C1=CC=C(CN(C2=CC=C(C3=CC=CC=C3)C=C2)C2=CC=C(C3=CC=CC=C3)C=C2)C=C1.NCC1=CC=CC=C1 Chemical compound BrC1=CC=C(C2=CC=CC=C2)C=C1.C1=CC=C(CN(C2=CC=C(C3=CC=CC=C3)C=C2)C2=CC=C(C3=CC=CC=C3)C=C2)C=C1.NCC1=CC=CC=C1 IBYLKPBDWVJEQI-UHFFFAOYSA-N 0.000 description 1
- YDKANDTZUQIGGM-UHFFFAOYSA-N BrC1=CC=C(C2=CC=CC=C2)C=C1.C1=CC=C(CNC2=CC=C(C3=CC=CC=C3)C=C2)C=C1.NCC1=CC=CC=C1 Chemical compound BrC1=CC=C(C2=CC=CC=C2)C=C1.C1=CC=C(CNC2=CC=C(C3=CC=CC=C3)C=C2)C=C1.NCC1=CC=CC=C1 YDKANDTZUQIGGM-UHFFFAOYSA-N 0.000 description 1
- FZLWEPBKXJKQIX-UHFFFAOYSA-N BrC1=CC=C2C=CC=CC2=C1.C1=CC=C(CN(C2=CC3=C(C=CC=C3)C=C2)C2=CC3=C(C=CC=C3)C=C2)C=C1.NCC1=CC=CC=C1 Chemical compound BrC1=CC=C2C=CC=CC2=C1.C1=CC=C(CN(C2=CC3=C(C=CC=C3)C=C2)C2=CC3=C(C=CC=C3)C=C2)C=C1.NCC1=CC=CC=C1 FZLWEPBKXJKQIX-UHFFFAOYSA-N 0.000 description 1
- KRBFBHKHFKBIRR-UHFFFAOYSA-N C1=CC=C(C2=CC=C(NC3=CC=C(C4=CC=C(NC5=CC=C(C6=CC=CC=C6)C=C5)C=C4)C=C3)C=C2)C=C1.C1=CC=C(CN(C2=CC=C(C3=CC=CC=C3)C=C2)C2=CC=C(C3=CC=C(N(CC4=CC=CC=C4)C4=CC=C(C5=CC=CC=C5)C=C4)C=C3)C=C2)C=C1.ClC(Cl)Cl Chemical compound C1=CC=C(C2=CC=C(NC3=CC=C(C4=CC=C(NC5=CC=C(C6=CC=CC=C6)C=C5)C=C4)C=C3)C=C2)C=C1.C1=CC=C(CN(C2=CC=C(C3=CC=CC=C3)C=C2)C2=CC=C(C3=CC=C(N(CC4=CC=CC=C4)C4=CC=C(C5=CC=CC=C5)C=C4)C=C3)C=C2)C=C1.ClC(Cl)Cl KRBFBHKHFKBIRR-UHFFFAOYSA-N 0.000 description 1
- NABNYGOPTWPMRG-UHFFFAOYSA-N C1=CC=C(C2=CC=C(NC3=CC=C(C4=CC=CC=C4)C=C3)C=C2)C=C1.C1=CC=C(CN(C2=CC=C(C3=CC=CC=C3)C=C2)C2=CC=C(C3=CC=CC=C3)C=C2)C=C1 Chemical compound C1=CC=C(C2=CC=C(NC3=CC=C(C4=CC=CC=C4)C=C3)C=C2)C=C1.C1=CC=C(CN(C2=CC=C(C3=CC=CC=C3)C=C2)C2=CC=C(C3=CC=CC=C3)C=C2)C=C1 NABNYGOPTWPMRG-UHFFFAOYSA-N 0.000 description 1
- ROTAWRBTSNDFNM-UHFFFAOYSA-N C1=CC=C(CN(C2=CC3=C(C=CC=C3)C=C2)C2=CC3=C(C=CC=C3)C=C2)C=C1.C1=CC=C2C=C(NC3=CC4=C(C=CC=C4)C=C3)C=CC2=C1 Chemical compound C1=CC=C(CN(C2=CC3=C(C=CC=C3)C=C2)C2=CC3=C(C=CC=C3)C=C2)C=C1.C1=CC=C2C=C(NC3=CC4=C(C=CC=C4)C=C3)C=CC2=C1 ROTAWRBTSNDFNM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
Definitions
- the present invention relates to a novel method for producing an aromatic amino compound. More particularly, the present invention relates to a method for producing an aromatic amino compound useful as the charge transporting material in the fields of the electronic photosensitive materials and the organic electroluminescence devices without using highly toxic raw materials.
- the Ullmann reaction As the method for synthesizing the aromatic amino compounds, the Ullmann reaction is widely known. In accordance with the Ullmann reaction, an amino compound and an aromatic halogen compound are mixed together under stirring in the presence of a metal catalyst at a high temperature. This reaction has a drawback in that the yield is small.
- the Ullmann reaction using aromatic amines is disclosed in Japanese Patent Application Laid-Open No. Heisei 8-48656 but the yield of the reaction is as small as 10 to 20%.
- the present invention has been made to overcome the above drawbacks and has an object of providing a method for producing an aromatic amino compound useful as the charge transporting material in the fields of the electronic photosensitive materials and the organic electroluminescence devices efficiently at a great yield without using highly toxic raw materials.
- the present invention provides a process for producing an aromatic amino compound in accordance with any one of the following four reaction routes 1 to 4:
- R 1 in the above formulae represents a substituent having 2 to 50 carbon atoms.
- substituent for example, alkyl groups and arylalkyl groups are preferable and these groups having benzyl group or carbonyl group are more preferable. These groups may be substituted.
- group having benzyl group include benzyl group, methoxybenzyl group and dimethoxybenzyl group.
- group having carbonyl group include t-butoxycarbonyl group, benzyloxycarbonyl group, acetyl group, trifluoroacetyl group and benzoyl group. These groups are easily eliminated from the nitrogen atom by addition of an acid, an alkali, a reducing agent or an oxidizing agent.
- the above substituent is not particularly limited as long as the group has the above property.
- Ar 1 and Ar 2 in the above formulae each independently represent a substituted or unsubstituted hydrocarbon group or heterocyclic group having 6 to 50 carbon atoms.
- the group represented by Ar 1 or Ar 2 include phenyl group, naphthyl group, anthranyl group, phenanthryl group, pyrenyl group, coronyl group, biphenyl group, terphenyl group, pyrrolyl group, furanyl group, thiophenyl group, benzothiophenyl group, oxadiazolyl group, indolyl group, carbazolyl group, pyridyl group, benzoquinolyl group, styrylphenyl group.
- biphenyl group, terphenyl group, 1-naphthyl group and 2-naphthyl group are preferable. These groups may be substituted.
- Ar 3 in the above formulae represents a substituted or unsubstituted aromatic residue group having 6 to 60 carbon atoms.
- Examples of the group represented by A 3 include divalent groups such as phenylene group, naphthylene group, anthranylene group, phenanthrylene group, pyrenylene group, coronylene group, chrysenylene group, penylenylene group, bisanthracenylene group, biphenylene group, terphenylene group, pyrrolylene group, furanylene group, thiophenylene group, benzothiophenylene group, oxadiazolylene group, diphenyl-anthranylene group, indolylene group, carboxylylene group, pyridylene group, benzoquinolylene group, stilbene group, N,N,N-triarylamiono groups and N,N,N′,N′-tetraaryldiamionoaryl groups.
- biphenylene group, terphenylene group, anthranylene group, tri-4-biphenylylamino group, N,N,N′,N′-tetra(4-biphenylyl)benzidine group and stilbene group are preferable.
- the above groups may be substituted or unsubstituted.
- the preferable substituent include alkyl groups having 1 to 6 carbon atoms such as ethyl group, methyl group, i-propyl group, n-propyl group, s-butyl group, t-butyl group, n-butyl group, pentyl group, hexyl group, cyclopentyl group and cyclohexyl group; alkoxyl groups having 1 to 6 carbon atoms such as ethoxyl group, methoxyl group, i-propoxyl group, n-propoxyl group, s-butoxyl group, t-butoxyl group, pentoxyl group, hexyloxy group, cyclopentoxyl group and cyclohexyloxyl group; and alkylamino groups having 1 to 8 carbon atoms such as dimethylamino group, diethylamino group, di-n-propylamino group,
- X in the above formulae represents a halogen atom.
- the halogen atom include chlorine atom, bromine atom and iodine atom.
- X may represent triflate group which works in a manner similar to that of halogen atoms.
- a noble metal catalyst is used for forming the N—C bond.
- the noble metal catalyst include Pd(OAc) 2 (palladium acetate(II)), Pd 2 (dba) 3 (tris(dibenzylideneacetone)-dipalladium(0), Pd(dba) 2 (bis(dibenzylideneacetone)palladium(0) and Pd(dppf)Cl 2 (1,1′-bis(diphenylphosphino)ferrocene)dichloropalladium (II).
- Examples of the ligand include P(t-Bu) 3 (tri-t-butylphosphine), BINAP ((2,2′-bis(diphenylphoshino)-1,1′-binaphthyl), P(o-Tol) 3 (tri-o-toluyl-phosphine), DPPF (1,1′-bis(diphenylphosphino)ferrocene) and DPPP (1,3-bis(diphenylphosphino)propane.
- Examples of the base include NaOtBu, CsCO 3 , K 2 CO 3 and NaOPh (sodium phenoxide).
- Examples of the solvent include toluene, xylene, mesitylene, THF and 1,4-dioxane. A suitable combination of these components is selected in accordance with the type of the substrate.
- the N—C bond is broken and the substituent is eliminated from the nitrogen atom in an acidic or alkaline condition or by addition of a reducing agent.
- a reducing agent examples include trifluoroacetic acid and hydrochloric acid.
- the base examples include KOH and NaOH.
- a solvent such as CH 3 OH, C 2 H 5 OH and water is suitably added.
- the reducing agent examples include Pd, PdO and Pd/C and these compounds are used in combination with a compound supplying a hydride such as hydrogen gas, HCO 2 NH 4 and silyl compounds.
- a compound supplying a hydride such as hydrogen gas, HCO 2 NH 4 and silyl compounds.
- At least one solvent selected from methanol, ethanol, chloroform, acetic acid, ethyl acetate and dichloromethane is suitably used in accordance with the substrate although the solvent is not particularly limited.
- a reagent specifically interacting with the substrate may be used.
- trinethylsilyl iodide may be used when benzyloxycarbonyl group which is a substituent represented by R 1 is eliminated.
- Examples of the aromatic amino compound represented by general formula (V) which is produced in accordance with the method of the present invention include di-4-biphenylylamine, di-1,1′:4′,1′′-terphenylyl-amine, di-1-naphthylamine, di-2-naphthylamine, (4-biphenylyl)-(2-naphthy-amine and (4-biphenylyl)(1,1′:4′,1′′-terphenylyl)amine.
- Examples of the aromatic amino compound represented by general formula (VII) which is produced in accordance with the method of the present invention include N,N,N′,N′-tetra(4-biphenylyl)benzidine, N,N′-(2-naphthyl)(4-biphenylyl)benzidine, N,N′-(4-biphenylyl)(1,1′:4′,1′′-terphenylyl)benzidine, N,N,N′,N′-tetra(4-biphenylyl)-9,10-diamino-anthracene, N,N,N′,N′-tetra(2-naphthyl)-6,12 -diaminochrysene, N,N,N′,N′-tetra(4-biphenylyl)-3,9-diaminoperylene, N,N,N′,N′,N′′,N′′-hexa(4-biphen
- Examples of the aromatic amino compound represented by general formula (X) which is produced in accordance with the method of the present invention include N,N′-di(4-biphenylyl)benzidine, N,N′-di-(2-naphthyl)benzidine, N,N′,N′′-tri(4-biphenylyl)triaminobenzene, N,N′-di-(1,1′:4′,1′′-terphenylyl)benzidine, N,N′-di(4-biphenylyl)-6,12-diamino-chrysene, N,N′-di(4-biphenylyl)-4,4′′-diamino-p-terphenyl, N,N′-di-(2-naphthyl) -4,4′-diaminostilbene and N,N′-di(1-naphthyl) -4,4′-diamino-stilbene
- a coiled tube condenser for reiuxing was attached to the central opening of the flask and a three-way stopcock attached with a balloon containing the argon gas was attached to the top of the coiled tube condenser.
- the atmosphere in the system was purged with the argon gas in the balloon 3 times using a vacuum pump.
- the reaction mixture was transferred to a separation funnel. Dichloromethane in an amount of 300 ml was added and precipitates were dissolved. After washing with 60 ml of a saturated aqueous solution of sodium chloride, the organic layer was dried with anhydrous potassium carbonate. After potassium carbonate was removed by filtration, the organic solvent was removed by distillation from the organic layer. To the obtained residue., 200 ml of toluene and 40 ml of ethanol were added and the residue was completely dissolved by heating at 80° C. with attachment of a drying tube. The resultant solution was slowly cooled to the room temperature by being left standing for one night and the recrystallization was conducted. The formed crystals were separated by filtration using a Kirnyama funniel. After drying the crystals at 60° C. in vacuo, 6.73 g (16.4 mmol) of N,N-di(4-biphenylyl)benzylamine was obtained at a yield of 87%.
- the hydrogen gas in the decreased amount was replenished and the volume of the hydrogen gas was adjusted at 2 liters.
- the resultant fluid was vigorously stirred at the room temperature. After the fluid was stirred for the total time of 30 hours at the room temperature, 100 ml of dichloromethane was added and the catalyst was removed by filtration. The obtained solution was transferred to a separation funnel and washed with 50 ml of a saturated solution of sodium hydrogencarbonate. The organic layer was separated, dried with anhydrous potassium carbonate and filtered and the solvent was removed by distillation. To the obtained residue, 50 ml of toluene was added and the recrystallization was conducted. The formed crystals were separated using a Kiryama funnel and dried in vacuo at 50° C. and 990 mg (3.08 mmol) of di-4-biphenylyl- amine was obtained at a yield of 94%.
- a coiled tube condenser for refluxing was attached to the central opening of the flask and a three-way stopcock attached with a balloon containing the argon gas was attached to the top of the coiled tube condenser.
- the atmosphere in the system was purged with the argon gas in the balloon 3 times using a vacuum pump.
- the formed precipitates were completely dissolved in 500 ml of dichloromethane. After the resultant solution was transferred to a separation funnel and washed with 100 ml of a saturated aqueous solution of sodium chloride, the organic layer (yellow) was dried with anhydrous potassium carbonate. After filtration, the organic solvent was removed by distillation and 150 ml of toluene and 50 ml of ethanol were added to the obtained residue. After a drying tube was attached, the precipitates were dissolved to some degree by heating at 80° C. and the resultant mixture was slowly cooled to the room temperature. The crystals in the system were separated by filtration using a Kinyama funnel.
- HPLC The chemical purity: 99.5% or greater
- N,N′-Di(4-biphenylyl)benzidine and N,N′-(2-naphthyl)-(4-biphenylyl)benzidine were prepared in accordance with the following reaction schemes.
- a coiled tube condenser for refluxing was attached to the central opening of the flask and a three-way stopcock attached with a balloon containing the argon gas was attached to the top of the coiled tube condenser.
- the atmosphere in the system was purged with the argon gas in the balloon 3 times using a vacuum pump.
- the reaction mixture was transferred to a separation funnel. Dichloromethane in an amount of 200 ml was added and precipitates were dissolved. After washing with 50 ml of a saturated aqueous solution of sodium chloride, the organic layer was dried with anhydrous potassium carbonate. After potassium carbonate was removed by filtration, the organic solvent was removed by distillation from an organic layer. The obtained product was separated and purified in accordance with the silica gel column chromatography and 3.82 g (16.4 mmol) of 4-biphenylyl-benzylamine was obtained at a yield of 79%.
- a coiled tube condenser for refluxing was attached to the central opening of the flask and a three-way stopcock attached with a balloon containing the argon gas was attached to the top of the coiled tube condenser.
- the atmosphere in the system was purged with the argon gas in the balloon 3 times using a vacuum pump.
- the formed precipitates were completely dissolved in 300 ml of dichloromethane. After the resultant solution was transferred to a separation funnel and washed with 100 ml of a saturated aqueous solution of sodium chloride, the organic layer was dried with anhydrous potassium carbonate. After filtration, the organic solvent was removed by distillation The product was recrystallized from a mixed solvent containing toluene and ethanol, separated by filtration and dried at 60° C. for 3 hours in a vacuum drying chamber and 3.80 g (5.69 mmol) of N,N-dibenzyl-N′,N′-di-4-biphenylylbenzidine was obtained at a yield of 88%.
- a three-way stopcock attached with a balloon (a gas bag) containing 2 liters of the hydrogen gas was attached to the flask and the inside of the flask system was purged with the hydrogen gas 10 times using a vacuum pump.
- the hydrogen gas in the decreased amount was replenished and the volume of the hydrogen gas was adjusted at 2 liters.
- the resultant fluid was vigorously stirred at 35° C. After the fluid was stirred for the total time of 24 hours, the catalyst was removed by filtration.
- the obtained solution was transferred to a separation funnel and washed with 50 ml of a saturated solution of sodium hydrogencarbonate.
- the organic layer was separated, dried with anhydrous potassium carbonate and filtered and the solvent was removed by distillation.
- a rubber cap was placed at each of two openings at the sides of the flask.
- a coiled tube condenser for refluxing was attached to the central opening of the flask and a three-way stopcock attached with a balloon containing the argon gas was attached to the top of the coiled tube condenser.
- the atmosphere in the system was purged with the argon gas in the balloon 3 times using a vacuum pump.
- HPLC The chemical purity: 99.8% or greater
- N,N, N′,N′-Tetra(2-naphthyl)-4,4′-diaminostilbene was prepared in accordance with the following reaction routes.
- the reaction system slowly changed to yellow and then to brown with the formation of white precipitates after 3 hours. Seven and a half hours after the temperature reached 120° C., the flask was removed from the oil bath to stop the reaction and left standing for one night under the atmosphere of argon.
- the reaction mixture was transferred to a separation funnel. Dichloromethane in an amount of 300 ml was added and precipitates were dissolved. After washing with 60 ml of a saturated aqueous solution of sodium chloride, the organic layer was dried with anhydrous potassium carbonate. After potassium carbonate was removed by filtration with a filter paper and the filtrate was placed into a 500 ml egg-plant shaped flask, the organic solvent was removed by distillation from an organic layer. To the obtained residue, 200 ml of toluene and 40 ml of ethanol were added and the residue was completely dissolved by heating at 80° C. with attachment of a drying tube. The resultant solution was slowly cooled to the room temperature by being left standing for one night and the recrystallization was conducted.
- the formed crystals were separated by filtration using a Kiriyama funnel. After drying the crystals at 60° C. in vacuo, 3.94 g of white needle crystals having the shape of cotton were obtained. Using the filtrate, the crystallization was repeated and 1.48 g of the second product and 0.15 g of the third product were obtained. N,N-Di(2-naphthyl)benzylamine was obtained in a total amount of 5.57 g (15.5 mmol) at a yield of 83%.
- a three-way stopcock attached with a balloon (a gas bag) containing 2 liters of the hydrogen gas was attached to the flask and the inside of the flask system was purged with the hydrogen gas 10 times using a vacuum pump.
- the hydrogen gas in the decreased amount was replenished and the volume of the hydrogen gas was adjusted at 2 liters.
- the resultant fluid was vigorously stirred at the room temperature. After the fluid was stirred for the total time of 30 hours at the room temperature, 100 ml of dichloromethane was added and the catalyst was removed by filtration. The obtained solution was transferred to a separation funnel and washed with 50 ml of a saturated solution of sodium hydrogencarbonate.
- the organic layer was separated, dried with anhydrous potassium carbonate and filtered and the solvent was removed by distillation.
- 50 ml of toluene was added.
- a drying tube was attached to the flask and the temperature was raised to 85° C. to dissolve the residue.
- the recrystallization was conducted by slowly cooling the resultant solution to the room temperature while the flask was left standing for one night.
- the formed crystals were separated using a Kiriyama funnel and dried in vacuo at 50° C. and 710 mg (2.62 mmol) of di-2-naphthylamine was obtained at a yield of 80%.
- a coiled tube condenser for refluxing was attached to the central opening of the flask and a three-way stopcock attached with a balloon containing the argon gas was attached to the top of the coiled tube condenser.
- the atmosphere in the system was purged with the argon gas in the balloon 3 times using a vacuum pump.
- the formed precipitates were completely dissolved in 500 ml of dichloromethane. After the resultant fluid was transferred to a separation funnel and washed with 100 ml of a saturated aqueous solution of sodium chloride, the organic layer (yellow) was dried with anhydrous potassium carbonate. After filtration, the organic solvent was removed by distillation and 150 ml of toluene and 50 ml of ethanol were added to the obtained residue. After a drying tube was attached to the flask, the precipitates were dissolved to some degree by heating at 80° C. and the resultant mixture was slowly cooled to the room temperature. The crystals of the ivory color in the system were separated by filtration using a Kiriyama funnel.
- N,N,N′,N′-Tetra(4-biphenylyl)benzidine was prepared in accordance with a conventional method.
- the obtained mixture was cooled and the formed crystals were separated by filtration.
- the obtained crystals in an amount of 49 g were dissolved into 250 ml of dimethylformamide (DMF) by heating.
- the resultant solution was cooled with water and tribiphenylamine of a byproduct precipitated by the cooling was removed by filtration.
- the filtrate was added into 1,000 ml of water and the formed crystals were separated by filtration, washed with water and methanol.
- the obtained crystals in an amount of 35 g which contained water were recrystallized from 750 ml of toluene and yellowish green scale-like crystals of di(4-biphenyl)amine were obtained.
- the mother liquor was concentrated and secondary crystals were obtained.
- the amount of the obtained product was 19 g (the yield: 13.8%).
- 15 g (0.0467 moles) of di(4-biphenyl)amine, 9.5 g (0.0234 moles) of 4,4′-diiodobiphenyl, 9.7 g (0.0702 moles) of potassium carbonate, 0.74 g (0.0117 moles) of copper and 76 ml of nitrobenzene were placed and the reaction was allowed to proceed at 220° C. for 2 days.
- 750 ml of DMF was added and copper salts were removed by filtration while the temperature of the reaction mixture remained high.
- the filtrate was cooled and the formed crystals were separated by filtration.
- the obtained crystals in an amount of 25 g which contained water were recrystallized 3 times from toluene in an amount 100 time as much as that of the crystals and light yellow crystals of N,N,N′,N′-tetra(4-biphenyl)benzidine as the object compound were obtained (the amount of the obtained product: 9 g; the yield: 48.6%).
- the aromatic amino compounds useful as the charge transporting material in the fields of the electronic photosensitive materials and the organic electroluminescence devices can be produced efficiently at a great yield without using highly toxic raw materials.
Abstract
A method for producing aromatic amino compound (V):
by synthesizing intermediate compound (IV):
by the reaction of compound (I): H2N—R1 with a mixture of halogenated aryl compounds (II): Ar1-X and (III): Ar2-X in the presence of a noble metal catalyst, followed by eliminating the substituent R1 from the nitrogen atom in compound (IV) under an acidic condition or an alkaline condition or by addition of a reducing agent or an oxidizing agent. (R1: a substituent having 2 to 50 carbon atoms; Ar1 and Ar2: a substituted or unsubstituted hydrocarbon group or heterocyclic group having 6 to 50 carbon atoms and the same with or different from each other; and X: a halogen group). The aromatic amino compound useful as the charge transporting material can be produced efficiently at a great yield without using highly toxic raw materials.
by synthesizing intermediate compound (IV):
by the reaction of compound (I): H2N—R1 with a mixture of halogenated aryl compounds (II): Ar1-X and (III): Ar2-X in the presence of a noble metal catalyst, followed by eliminating the substituent R1 from the nitrogen atom in compound (IV) under an acidic condition or an alkaline condition or by addition of a reducing agent or an oxidizing agent. (R1: a substituent having 2 to 50 carbon atoms; Ar1 and Ar2: a substituted or unsubstituted hydrocarbon group or heterocyclic group having 6 to 50 carbon atoms and the same with or different from each other; and X: a halogen group). The aromatic amino compound useful as the charge transporting material can be produced efficiently at a great yield without using highly toxic raw materials.
Description
- The present invention relates to a novel method for producing an aromatic amino compound. More particularly, the present invention relates to a method for producing an aromatic amino compound useful as the charge transporting material in the fields of the electronic photosensitive materials and the organic electroluminescence devices without using highly toxic raw materials.
- Application of aromatic amino compounds to the electronics field as functional material has been studied and the aromatic amino compounds are widely used as the charge transporting material in the fields of the electronic photosensitive materials and the organic electroluminescence devices. As the method for synthesizing the aromatic amino compounds, the Ullmann reaction is widely known. In accordance with the Ullmann reaction, an amino compound and an aromatic halogen compound are mixed together under stirring in the presence of a metal catalyst at a high temperature. This reaction has a drawback in that the yield is small. For example, the Ullmann reaction using aromatic amines is disclosed in Japanese Patent Application Laid-Open No. Heisei 8-48656 but the yield of the reaction is as small as 10 to 20%.
- For synthesis of an aromatic amino compound, heretofore, the reaction routes using α-naphthylamine, β-naphthylamine, 4-aminodiphenyl or benzidine are known but these compounds exhibits strong toxicity. In particular, β-naphthylamine, 4-aminodiphenyl and benzidine are compounds listed as “Specified Chemical Substances” and the production of these compounds are prohibited.
- The present invention has been made to overcome the above drawbacks and has an object of providing a method for producing an aromatic amino compound useful as the charge transporting material in the fields of the electronic photosensitive materials and the organic electroluminescence devices efficiently at a great yield without using highly toxic raw materials.
- The present invention provides a process for producing an aromatic amino compound in accordance with any one of the following four reaction routes 1 to 4:
- 1. A method for producing an aromatic amino compound represented by following general formula (V):
wherein Ar1 and Ar2 each independently represent a substituted or unsubstituted hydrocarbon group or heterocyclic group having 6 to 50 carbon atoms and may represent a same group or different groups, which comprises - synthesizing an intermediate compound for an aromatic amino compound which is represented by following general formula (IV):
wherein R1 represents a substituent having 2 to 50 carbon atoms, by reacting an amino compound represented by following general formula (I):
H2N—R1 (I)
wherein R1 is as defined above, with a mixture of halogenated aryl compounds represented by following general formulae (II) and (III):
Ar1-X (II)
Ar2-X (III)
wherein Ar1 and Ar2 are as defines above, and X represents a halogen group, in a presence of a noble metal catalyst; and - eliminating the substituent represented by R1 from the nitrogen atom in the compound represented by general formula (IV) either under an acidic condition or an alkaline condition or by addition of a reducing agent or an oxidizing agent.
- 2. A method for producing an aromatic amino compound represented by following general formula (VII):
wherein Ar1 and Ar2 each independently represent a substituted or unsubstituted hydrocarbon group or heterocyclic group having 6 to 50 carbon atoms and may represent a same group or different groups, Ar3 represents a substituted or unsubstituted aromatic residue group having 6 to 60 carbon atoms, and n represents an integer of 1 to 4, which comprises - reacting an intermediate compound for an aromatic amino compound which is represented by following general formula (V):
wherein Ar1 and A12 are as defined above, and X represents a halogen group, with a mixture of halogenated aryl compounds represented by following general formula (VI):
Ar3-(X)n (VI)
wherein Ar3, X and n are as defined above, in a presence of a noble metal catalyst. - 3. A method for producing an aromatic amino compound represented by following general formula (X):
wherein Ar1 represents a substituted or unsubstituted hydrocarbon group or heterocyclic group having 6 to 50 carbon atoms, Ar3 represents a substituted or unsubstituted aromatic residue group having 6 to 60 carbon atoms, and n represents an integer of 1 to 4, which comprises synthesizing an intermediate compound of an aromatic amino compound represented by following general formula (VIII):
wherein R1 represents a substituent having 2 to 50 carbon atoms, and Ar1 is as defined above, by reacting an amino compound represented by following general formula (I):
H2N—R1 (I)
wherein R1 is as defined above, with a halogenated aryl compound represented by following general formula (II):
Ar1-X (II)
wherein Ar1 is as defined above and X represents a halogen group, in a presence of a noble metal catalyst; - synthesizing another intermediate compound for an aromatic amino compound which is represented by following general formula (IX):
wherein R1, Ar1, Ar3 and n are as defined above, by reacting the compound represented by general formula (VIII) with a halogenated aryl compound represented by following general formula (VI):
Ar3-(X)n (VI)
wherein Ar3, X and n are as defined above, in a presence of a noble metal catalyst; and - eliminating the substituent represented by R1 from the nitrogen atom in the compound represented by general formula (IX) either under an acidic condition or an alkaline condition or by addition of a reducing agent.
- 4. A method for producing an aromatic amino compound represented by general formula (VII):
wherein Ar1 and Ar2 each independently represent a substituted or unsubstituted hydrocarbon group or heterocyclic group having 6 to 50 carbon atoms and may represent a same group or different groups, Ar3 represents a substituted or unsubstituted aromatic residue group having 6 to 60 carbon atoms, and n represents an integer of 1 to 4, which comprises - reacting a compound represented by following general formula (X):
wherein Ar1, Ar3 and n are as defined above, with a halogenated aryl compound represented by following general formula (III):
Ar2-X (III)
wherein Ar2 is as defined above, and X represents a halogen group, in a presence of a noble metal catalyst. - The present invention will be described in detail in the following.
- In the present invention, R1, in the above formulae represents a substituent having 2 to 50 carbon atoms. As the substituent, for example, alkyl groups and arylalkyl groups are preferable and these groups having benzyl group or carbonyl group are more preferable. These groups may be substituted. Examples of the group having benzyl group include benzyl group, methoxybenzyl group and dimethoxybenzyl group. Examples of the group having carbonyl group include t-butoxycarbonyl group, benzyloxycarbonyl group, acetyl group, trifluoroacetyl group and benzoyl group. These groups are easily eliminated from the nitrogen atom by addition of an acid, an alkali, a reducing agent or an oxidizing agent. The above substituent is not particularly limited as long as the group has the above property.
- In the present invention, Ar1 and Ar2 in the above formulae each independently represent a substituted or unsubstituted hydrocarbon group or heterocyclic group having 6 to 50 carbon atoms. Examples of the group represented by Ar1 or Ar2 include phenyl group, naphthyl group, anthranyl group, phenanthryl group, pyrenyl group, coronyl group, biphenyl group, terphenyl group, pyrrolyl group, furanyl group, thiophenyl group, benzothiophenyl group, oxadiazolyl group, indolyl group, carbazolyl group, pyridyl group, benzoquinolyl group, styrylphenyl group. Among these groups, biphenyl group, terphenyl group, 1-naphthyl group and 2-naphthyl group are preferable. These groups may be substituted.
- In the present invention, Ar3 in the above formulae represents a substituted or unsubstituted aromatic residue group having 6 to 60 carbon atoms. Examples of the group represented by A3 include divalent groups such as phenylene group, naphthylene group, anthranylene group, phenanthrylene group, pyrenylene group, coronylene group, chrysenylene group, penylenylene group, bisanthracenylene group, biphenylene group, terphenylene group, pyrrolylene group, furanylene group, thiophenylene group, benzothiophenylene group, oxadiazolylene group, diphenyl-anthranylene group, indolylene group, carboxylylene group, pyridylene group, benzoquinolylene group, stilbene group, N,N,N-triarylamiono groups and N,N,N′,N′-tetraaryldiamionoaryl groups. Among these groups, biphenylene group, terphenylene group, anthranylene group, tri-4-biphenylylamino group, N,N,N′,N′-tetra(4-biphenylyl)benzidine group and stilbene group are preferable.
- The above groups may be substituted or unsubstituted. Examples of the preferable substituent include alkyl groups having 1 to 6 carbon atoms such as ethyl group, methyl group, i-propyl group, n-propyl group, s-butyl group, t-butyl group, n-butyl group, pentyl group, hexyl group, cyclopentyl group and cyclohexyl group; alkoxyl groups having 1 to 6 carbon atoms such as ethoxyl group, methoxyl group, i-propoxyl group, n-propoxyl group, s-butoxyl group, t-butoxyl group, pentoxyl group, hexyloxy group, cyclopentoxyl group and cyclohexyloxyl group; and alkylamino groups having 1 to 8 carbon atoms such as dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group and piperidine group.
- In the present invention, X in the above formulae represents a halogen atom. Examples of the halogen atom include chlorine atom, bromine atom and iodine atom. X may represent triflate group which works in a manner similar to that of halogen atoms.
- In the present invention, a noble metal catalyst is used for forming the N—C bond. Examples of the noble metal catalyst include Pd(OAc)2 (palladium acetate(II)), Pd2(dba)3 (tris(dibenzylideneacetone)-dipalladium(0), Pd(dba)2 (bis(dibenzylideneacetone)palladium(0) and Pd(dppf)Cl2 (1,1′-bis(diphenylphosphino)ferrocene)dichloropalladium (II). Examples of the ligand include P(t-Bu)3 (tri-t-butylphosphine), BINAP ((2,2′-bis(diphenylphoshino)-1,1′-binaphthyl), P(o-Tol)3 (tri-o-toluyl-phosphine), DPPF (1,1′-bis(diphenylphosphino)ferrocene) and DPPP (1,3-bis(diphenylphosphino)propane. Examples of the base include NaOtBu, CsCO3, K2CO3 and NaOPh (sodium phenoxide). Examples of the solvent include toluene, xylene, mesitylene, THF and 1,4-dioxane. A suitable combination of these components is selected in accordance with the type of the substrate.
- In the present invention, the N—C bond is broken and the substituent is eliminated from the nitrogen atom in an acidic or alkaline condition or by addition of a reducing agent. Examples of the acid used above include trifluoroacetic acid and hydrochloric acid. Examples of the base include KOH and NaOH. A solvent such as CH3OH, C2H5 OH and water is suitably added.
- Examples of the reducing agent include Pd, PdO and Pd/C and these compounds are used in combination with a compound supplying a hydride such as hydrogen gas, HCO2NH4 and silyl compounds. At least one solvent selected from methanol, ethanol, chloroform, acetic acid, ethyl acetate and dichloromethane is suitably used in accordance with the substrate although the solvent is not particularly limited. A reagent specifically interacting with the substrate may be used. For example, trinethylsilyl iodide may be used when benzyloxycarbonyl group which is a substituent represented by R1 is eliminated.
- Examples of the aromatic amino compound represented by general formula (V) which is produced in accordance with the method of the present invention include di-4-biphenylylamine, di-1,1′:4′,1″-terphenylyl-amine, di-1-naphthylamine, di-2-naphthylamine, (4-biphenylyl)-(2-naphthy-amine and (4-biphenylyl)(1,1′:4′,1″-terphenylyl)amine.
- Examples of the aromatic amino compound represented by general formula (VII) which is produced in accordance with the method of the present invention include N,N,N′,N′-tetra(4-biphenylyl)benzidine, N,N′-(2-naphthyl)(4-biphenylyl)benzidine, N,N′-(4-biphenylyl)(1,1′:4′,1″-terphenylyl)benzidine, N,N,N′,N′-tetra(4-biphenylyl)-9,10-diamino-anthracene, N,N,N′,N′-tetra(2-naphthyl)-6,12 -diaminochrysene, N,N,N′,N′-tetra(4-biphenylyl)-3,9-diaminoperylene, N,N,N′,N′,N″,N″-hexa(4-biphenylyl)-1,3,5-triaminobenzene and N,N,N′,N′-tetra-(2-naphthyl)-4,4′-diaminostilbene.
- Examples of the aromatic amino compound represented by general formula (X) which is produced in accordance with the method of the present invention include N,N′-di(4-biphenylyl)benzidine, N,N′-di-(2-naphthyl)benzidine, N,N′,N″-tri(4-biphenylyl)triaminobenzene, N,N′-di-(1,1′:4′,1″-terphenylyl)benzidine, N,N′-di(4-biphenylyl)-6,12-diamino-chrysene, N,N′-di(4-biphenylyl)-4,4″-diamino-p-terphenyl, N,N′-di-(2-naphthyl) -4,4′-diaminostilbene and N,N′-di(1-naphthyl) -4,4′-diamino-stilbene.
- The present invention will be described more specifically with reference to examples in the following. However, the present invention is not limited to the examples.
- Di-4-biphenylylamine and N,N,N′,N′-tetra(4-biphenylyl)benzidine were prepared in accordance with the following reaction routes.
- (1) N,N-Di(4-biphenylyl)benzylamine was prepared. The reaction scheme is shown in the following:
- Into a 100 ml three-necked flask, 10.0 g (42.9 mmol, 2.3 eq) of 4-bromobiphenyl, 4.32 g (44.9 mmol, 2.4 eq) of sodium t-butoxide and 42.0 mg (0.187 mmol, 1.0% by mole) of palladium acetate were placed. A stirrer rod having the shape of a rugby ball was placed into the flask. A rubber cap was placed at each of two openings at the sides of the flask. A coiled tube condenser for reiuxing was attached to the central opening of the flask and a three-way stopcock attached with a balloon containing the argon gas was attached to the top of the coiled tube condenser. The atmosphere in the system was purged with the argon gas in the balloon 3 times using a vacuum pump.
- To the above system, 60 ml of dehydrated toluene, 2.04 ml (18.7 mmol) of benzylamine and 169 μl (0.374 mmol, 2.0% by mole) of a 2.22 moles/liter toluene solution of tris-t-butylphosphine were added using a syringe through a rubber septum and the resultant mixture was stirred at the room temperature for 5 minutes. Then, the flask was set into an oil bath and the temperature was raised slowly to 120° C. while the solution was stirred. After 7 and a half hours, the flask was removed from the oil bath to stop the reaction and left standing for one night under the atmosphere of argon.
- The reaction mixture was transferred to a separation funnel. Dichloromethane in an amount of 300 ml was added and precipitates were dissolved. After washing with 60 ml of a saturated aqueous solution of sodium chloride, the organic layer was dried with anhydrous potassium carbonate. After potassium carbonate was removed by filtration, the organic solvent was removed by distillation from the organic layer. To the obtained residue., 200 ml of toluene and 40 ml of ethanol were added and the residue was completely dissolved by heating at 80° C. with attachment of a drying tube. The resultant solution was slowly cooled to the room temperature by being left standing for one night and the recrystallization was conducted. The formed crystals were separated by filtration using a Kirnyama funniel. After drying the crystals at 60° C. in vacuo, 6.73 g (16.4 mmol) of N,N-di(4-biphenylyl)benzylamine was obtained at a yield of 87%.
- The results of the measurements of NMR and FD-MASS on the obtained N,N-di(4-biphenylyl)benzylamine were as follows:
- NMR: δ90 MHz 5.07 (2H, s), 7.1 to 7.7 (23H, m)
- FD-MASS: 411
- (2) Di-4-biphenylylamine was prepared. The reaction scheme is shown in the following:
- Into a 300 ml single-necked flask, 1.35 g (3.28 mmol) of N,N-di(4-biphenyl)benzylamine obtained in (1) and 135 mg (10% by weight) of palladium-active carbon (the content of palladium: 10% by weight) were placed. To the resultant mixture, 100 ml of chloroform and 20 ml of ethanol were added and the substrate was dissolved. A stirrer rod having the shape of a rugby ball was placed into the flask. A three-way stopcock attached with a balloon (a gas bag) containing 2 liters of the hydrogen gas was attached to the flask and the inside of the flask system was purged with the hydrogen gas 3 times using a vacuum pump. The hydrogen gas in the decreased amount was replenished and the volume of the hydrogen gas was adjusted at 2 liters. The resultant fluid was vigorously stirred at the room temperature. After the fluid was stirred for the total time of 30 hours at the room temperature, 100 ml of dichloromethane was added and the catalyst was removed by filtration. The obtained solution was transferred to a separation funnel and washed with 50 ml of a saturated solution of sodium hydrogencarbonate. The organic layer was separated, dried with anhydrous potassium carbonate and filtered and the solvent was removed by distillation. To the obtained residue, 50 ml of toluene was added and the recrystallization was conducted. The formed crystals were separated using a Kiryama funnel and dried in vacuo at 50° C. and 990 mg (3.08 mmol) of di-4-biphenylyl- amine was obtained at a yield of 94%.
- The results of the measurements of NMR and FD-MASS on the obtained di-4-biphenylylamine were as follows:
- NMR: δ90 MHz 5.83 (1H, bs), 7.0 to 7.8 (18H, m)
- FD-MASS: 321
- (3) N,N,N′,N′-tetra(4-biphenylyl)benzidine was prepared. The reaction scheme is shown in the following:
- Into a 50 ml two-necked flask, 500 mg (1.56 mmol, 2.1 eq) of di-4-biphenylylamine obtained in (2), 231 mg (0.741 mmol) of 4,4′-dibromobiphenyl, 3.4 mg (0.0148 mmol, 2.0% by mole) of palladium acetate and 157 mg (1.63 mmol, 2.2 eq) of sodium t-butoxide were placed. A rubber cap was placed at the side opening of the flask. A coiled tube condenser for refluxing was attached to the central opening of the flask and a three-way stopcock attached with a balloon containing the argon gas was attached to the top of the coiled tube condenser. The atmosphere in the system was purged with the argon gas in the balloon 3 times using a vacuum pump.
- To the above system, 10 ml of dehydrated toluene and 13.4 μl (0.0296 mmol, 4.0% by mole) of a 2.22 moles/liter toluene solution of tris-t-butylphosphine were added using a syringe through a rubber septum. Then, the flask was set into an oil bath and the temperature was raised slowly to 115° C. while the solution was stirred. After heating at 115° C. for 6 hours under stirring, the flask was removed from the oil bath and left standing at the room temperature for one night.
- The formed precipitates were completely dissolved in 500 ml of dichloromethane. After the resultant solution was transferred to a separation funnel and washed with 100 ml of a saturated aqueous solution of sodium chloride, the organic layer (yellow) was dried with anhydrous potassium carbonate. After filtration, the organic solvent was removed by distillation and 150 ml of toluene and 50 ml of ethanol were added to the obtained residue. After a drying tube was attached, the precipitates were dissolved to some degree by heating at 80° C. and the resultant mixture was slowly cooled to the room temperature. The crystals in the system were separated by filtration using a Kinyama funnel. After the crystals were washed with small amounts of toluene and ethanol and dried at 60° C. for 3 hours in a vacuum drying chamber, 453 mg (0.571 mmol) of N,N,N′.N′-tetra(4-biphenylyl)benzidine was obtained at a yield of 77%.
- The results of the measurements of NMR, FD-MASS and HPLC (high performance liquid chromatograph) on the obtained N,N,N′.N′-tetra-(4-biphenylyl) benzidine were as follows:
- NMR: δ90 MHz 7.1 to 7.8 (44H, m)
- FD-MASS: 792, 396
- HPLC: The chemical purity: 99.5% or greater
- N,N′-Di(4-biphenylyl)benzidine and N,N′-(2-naphthyl)-(4-biphenylyl)benzidine were prepared in accordance with the following reaction schemes.
- (1) 4-Biphenylylbenzylamine was prepared. The reaction scheme is shown in the following:
- Into a 100 ml three-necked flask, 5.0 g (21.5 mmol, 1.15 eq) of 4-bromobiphenyl, 2.16 g (22.5 mmol, 1.2 eq) of sodium t-butoxide, 342 mg (0.374 mmol, 2.0% by mole) of Pd2(dba)3 and 467 mg (0.748 mmol, 4.0% by mole) of (s)-BINAP were placed. A stirrer rod having the shape of a rugby ball was placed into the flask. A rubber cap was placed at each of two openings at the sides of the flask. A coiled tube condenser for refluxing was attached to the central opening of the flask and a three-way stopcock attached with a balloon containing the argon gas was attached to the top of the coiled tube condenser. The atmosphere in the system was purged with the argon gas in the balloon 3 times using a vacuum pump.
- To the above system, 60 ml of dehydrated toluene and 2.04 ml (18.7 mmol) of benzylamine were added using a syringe through a rubber septum and the resultant mixture was stirred at the room temperature for 5 minutes. Then, the flask was set into an oil bath and the temperature was raised slowly to 120° C. while the solution was stirred. After 6 hours, the flask was removed from the oil bath to stop the reaction and left standing for one night under the atmosphere of argon.
- The reaction mixture was transferred to a separation funnel. Dichloromethane in an amount of 200 ml was added and precipitates were dissolved. After washing with 50 ml of a saturated aqueous solution of sodium chloride, the organic layer was dried with anhydrous potassium carbonate. After potassium carbonate was removed by filtration, the organic solvent was removed by distillation from an organic layer. The obtained product was separated and purified in accordance with the silica gel column chromatography and 3.82 g (16.4 mmol) of 4-biphenylyl-benzylamine was obtained at a yield of 79%.
- The results of the measurements of NMR and FD-MASS on the obtained 4-biphenylylbenzylamine were as follows:
- NMR: δ90 MHz 5.07 (2H, s), 5.78 (1H, bs), 7.1 to 7.7 (14H, m)
- FD-MASS: 259
- (2) N,N-Dibenzyl-N′,N′-di-4-biphenylylbenzidine was prepared. The reaction scheme is shown in the following:
- Into a 100 ml two-necked flask, 3.5 g (13.5 mmol, 2.1 eq) of 4-biphenylybenzylamine obtained in (1), 2.0 g mg (6.43 mmol) of 4,4′-dibromobiphenyl, 30 mg (0.128 mmol, 2.0% by mole) of palladium acetate and 1.36 g (14.8 mmol, 2.2 eq) of sodium t-butoxide were placed. A rubber cap was placed at the side opening of the flask. A coiled tube condenser for refluxing was attached to the central opening of the flask and a three-way stopcock attached with a balloon containing the argon gas was attached to the top of the coiled tube condenser. The atmosphere in the system was purged with the argon gas in the balloon 3 times using a vacuum pump.
- To the above system, 60 ml of dehydrated toluene and 116 μl (0.256 mmol, 4.0% by mole) of a 2.22 moles/liter toluene solution of tris-t-butylphosphine were added using a syringe through a rubber septum. Then, the flask was set into an oil bath and the temperature was raised slowly to 115° C. while the solution was stirred. After heating for 6 hours under stirring, the flask was removed from the oil bath and left standing for one night.
- The formed precipitates were completely dissolved in 300 ml of dichloromethane. After the resultant solution was transferred to a separation funnel and washed with 100 ml of a saturated aqueous solution of sodium chloride, the organic layer was dried with anhydrous potassium carbonate. After filtration, the organic solvent was removed by distillation The product was recrystallized from a mixed solvent containing toluene and ethanol, separated by filtration and dried at 60° C. for 3 hours in a vacuum drying chamber and 3.80 g (5.69 mmol) of N,N-dibenzyl-N′,N′-di-4-biphenylylbenzidine was obtained at a yield of 88%.
- The results of the measurements of NMR and FD-MASS on the obtained N,N-dibenzyl-N′,N′-di-4-biphenylylbenzidine were as follows:
- NMR: δ90 MHz 5.08 (4H, s), 7.0 to 7.9 (36H, m)
- FD-MASS: 668
- (3) N,N′-Di-(4-biphenylyl)benzidine was prepared. The reaction scheme is shown in the following:
- Into a 500 ml single-necked egg plant-shaped flask, 3.5 g (5.24 mmol) of N,N-dibenzyl-N′,N′-di-4-biphenylylbenzidine obtained in (2) and 350 mg (10% by mole) of palladium-active carbon (the content of palladium: 5% by weight) were placed. To the resultant mixture, 350 ml of chloroform was added and the substrate was dissolved. A stirrer rod having the shape of a rugby ball was placed into the flask. A three-way stopcock attached with a balloon (a gas bag) containing 2 liters of the hydrogen gas was attached to the flask and the inside of the flask system was purged with the hydrogen gas 10 times using a vacuum pump. The hydrogen gas in the decreased amount was replenished and the volume of the hydrogen gas was adjusted at 2 liters. The resultant fluid was vigorously stirred at 35° C. After the fluid was stirred for the total time of 24 hours, the catalyst was removed by filtration. The obtained solution was transferred to a separation funnel and washed with 50 ml of a saturated solution of sodium hydrogencarbonate. The organic layer was separated, dried with anhydrous potassium carbonate and filtered and the solvent was removed by distillation. To the obtained residue, toluene was added and the recrystallization was conducted. The formed crystals were separated using a Kiriyama funnel and dried in vacuo at 50° C. and 2.33 g (4.77 mmol) of N,N′-di-(4-biphenylyl)benzidine was obtained at a yield of 91%.
- The results of the measurements of NMR and FD-MASS on the obtained N,N′-di-(4-biphenylyl)benzidine were as follows:
- NMR: δ90 MHz 5.80 (2H, bs), 7.0 to 7.8 (26H, m)
- FD-MASS: 488
- (4) N,N′-(2-Naphthyl)(4-biphenylyl)benzidine was prepared. The reaction scheme is shown in the following:
- Into a 100 ml three-necked flask, 2.0 g (4.10 mmol) of N,N′-di(4-biphenylyl)benzidine obtained in (3), 1.87 g (9.02 mmol, 2.2 eq) of 2-bromonaphthalene, 945 mg (9.84 mmol, 2.4 eq) of sodium t-butoxide, 75 mg (0.082 mmol, 2.0% by mole) of Pd2(dba)3 and 103 mg (0.164 mmol, 4.0% by mole) of (s)-BINAP were placed. A stirrer rod having the shape of a rugby ball was placed into the flask. A rubber cap was placed at each of two openings at the sides of the flask. A coiled tube condenser for refluxing was attached to the central opening of the flask and a three-way stopcock attached with a balloon containing the argon gas was attached to the top of the coiled tube condenser. The atmosphere in the system was purged with the argon gas in the balloon 3 times using a vacuum pump.
- To the above system, 50 ml of dehydrated toluene was added using a syringe through a rubber septum and the resultant mixture was stirred at the room temperature for 3 minutes. Then, the flask was set into an oil bath and the temperature was raised slowly to 120° C. while the solution was stirred. After 7 hours, the flask was removed from the oil bath to stop the reaction and left standing for one night under the atmosphere of argon.
- The reaction mixture was filtered. The residue was washed with toluene, water and ethanol and recrystallized from xylene and 2.55 g (3.45 mmol) of N,N′-(2-naphthyl)(4-biphenylyl)benzidine was obtained at a yield of 84%.
- The results of the measurements of NMR, FD-MASS and HPLC on the obtained N,N′-(2-naphthyl)(4-biphenylyl)benzidine were as follows:
- NMR: δ90 MHz 7.0 to 7.9 (40H, m)
- FD-MASS: 740, 370
- HPLC: The chemical purity: 99.8% or greater
- N,N, N′,N′-Tetra(2-naphthyl)-4,4′-diaminostilbene was prepared in accordance with the following reaction routes.
- (1) N,N-Di(2-naphthyl)benzylamine was prepared. The reaction scheme is shown in the following:
- Into a 100 ml three-necked flask, 8.9 g (42.9 mmol, 2.3 eq) of 2-bromonaphthalene, 4.32 g (44.9 mmol, 2.4 eq) sodium t-butoxide and 42.0 mg (0.187 mmol, 1.0% by mole) of palladium acetate were placed. A stirrer rod having the shape of a rugby ball was placed into the flask. A rubber cap was placed at each of two openings at the sides of the flask. A coiled tube condenser for refluxing was attached to the central opening of the flask and a three-way stopcock attached with a balloon containing the argon gas was attached to the top of the coiled tube condenser. The atmosphere in the system was purged with the argon gas in the balloon 3 times using a vacuum pump.
- To the above system, 60 ml of dehydrated toluene, 2.04 ml (18.7 mmol) of benzylamine and 169 μl (0.374 mmol, 2.0% by mole) of a 2.22 moles/liter toluene solution of tris-t-butylphosphine were added using a syringe through a rubber septum and the resultant mixture was stirred at the room temperature for 5 minutes. Then, the flask was set into an oil bath and the temperature was raised slowly while the solution was stirred. Formation of bubbles was observed when the temperature was about 80° C. and it was confirmed that the reaction was proceeding. The temperature was raised to 120° C. while the stirring was continued. The reaction system slowly changed to yellow and then to brown with the formation of white precipitates after 3 hours. Seven and a half hours after the temperature reached 120° C., the flask was removed from the oil bath to stop the reaction and left standing for one night under the atmosphere of argon.
- The reaction mixture was transferred to a separation funnel. Dichloromethane in an amount of 300 ml was added and precipitates were dissolved. After washing with 60 ml of a saturated aqueous solution of sodium chloride, the organic layer was dried with anhydrous potassium carbonate. After potassium carbonate was removed by filtration with a filter paper and the filtrate was placed into a 500 ml egg-plant shaped flask, the organic solvent was removed by distillation from an organic layer. To the obtained residue, 200 ml of toluene and 40 ml of ethanol were added and the residue was completely dissolved by heating at 80° C. with attachment of a drying tube. The resultant solution was slowly cooled to the room temperature by being left standing for one night and the recrystallization was conducted. The formed crystals were separated by filtration using a Kiriyama funnel. After drying the crystals at 60° C. in vacuo, 3.94 g of white needle crystals having the shape of cotton were obtained. Using the filtrate, the crystallization was repeated and 1.48 g of the second product and 0.15 g of the third product were obtained. N,N-Di(2-naphthyl)benzylamine was obtained in a total amount of 5.57 g (15.5 mmol) at a yield of 83%.
- The result of the measurements of FD-MASS on the obtained N -di(2-naphthyl)benzylamine was as follows:
- FD-MASS: 359
- (2) Di-2-naphthylamine was prepared. The reaction scheme is shown in the following:
- Into a 300 ml single-necked flask, 1.18 g (3.28 mmol) of N,N-di(2-naphthyl)benzylamine obtained in (1) and 135 mg (10% by weight) of palladium-active carbon (the content of palladium: 10% by weight) were placed. To the resultant mixture, 100 ml of chloroform and 20 ml of ethanol were added and the substrate was dissolved. A stirrer rod having the shape of a rugby ball was placed into the flask. A three-way stopcock attached with a balloon (a gas bag) containing 2 liters of the hydrogen gas was attached to the flask and the inside of the flask system was purged with the hydrogen gas 10 times using a vacuum pump. The hydrogen gas in the decreased amount was replenished and the volume of the hydrogen gas was adjusted at 2 liters. The resultant fluid was vigorously stirred at the room temperature. After the fluid was stirred for the total time of 30 hours at the room temperature, 100 ml of dichloromethane was added and the catalyst was removed by filtration. The obtained solution was transferred to a separation funnel and washed with 50 ml of a saturated solution of sodium hydrogencarbonate. The organic layer was separated, dried with anhydrous potassium carbonate and filtered and the solvent was removed by distillation. To the obtained residue, 50 ml of toluene was added. A drying tube was attached to the flask and the temperature was raised to 85° C. to dissolve the residue. The recrystallization was conducted by slowly cooling the resultant solution to the room temperature while the flask was left standing for one night. The formed crystals were separated using a Kiriyama funnel and dried in vacuo at 50° C. and 710 mg (2.62 mmol) of di-2-naphthylamine was obtained at a yield of 80%.
- The result of the measurements of FD-MASS on the obtained di-2-naphthylamine was as follows:
- FD-MASS: 269
- (3) N,N,N′,N′-tetra(2-naphthyl)-4,4′-diaminostilbene was prepared. The reaction scheme is shown in the following:
- Into a 50 ml two-necked flask, 420 mg (1.56 mmol, 2.1 eq) of di-2-naphthylamine obtained in (2), 250 mg (0.741 mmol) of 4,4′-dibromostilbene, 3.4 mg (0.0148 mmol, 2.0% by mole) of palladium acetate and 157 mg (1.63 mmol, 2.2 eq) of sodium t-butoxide were placed. A rubber cap was placed at the side opening of the flask. A coiled tube condenser for refluxing was attached to the central opening of the flask and a three-way stopcock attached with a balloon containing the argon gas was attached to the top of the coiled tube condenser. The atmosphere in the system was purged with the argon gas in the balloon 3 times using a vacuum pump.
- To the above system, 10 ml of dehydrated toluene and 13.4 μl (0.0296 mmol, 4.0% by mole) of a 2.22 moles/liter toluene solution of tris-t-butylphosphine were added using a syringe through a rubber septum. Then, the flask was set into an oil bath and the temperature was raised slowly to 115° C. while the solution was stirred. Brownish white precipitates were formed in the reaction solution after 30 minutes. After heating at 115° C. for 6 hours under stirring, the flask was removed from the oil bath and left standing for one night.
- The formed precipitates were completely dissolved in 500 ml of dichloromethane. After the resultant fluid was transferred to a separation funnel and washed with 100 ml of a saturated aqueous solution of sodium chloride, the organic layer (yellow) was dried with anhydrous potassium carbonate. After filtration, the organic solvent was removed by distillation and 150 ml of toluene and 50 ml of ethanol were added to the obtained residue. After a drying tube was attached to the flask, the precipitates were dissolved to some degree by heating at 80° C. and the resultant mixture was slowly cooled to the room temperature. The crystals of the ivory color in the system were separated by filtration using a Kiriyama funnel. After the crystals were washed with small amounts of toluene and ethanol and dried at 60° C. for 3 hours in a vacuum drying chamber, 428 mg (0.600 mmol) of N,N,N′,N′-tetra(2-naphthyl)-4,4′-diaminostilbene was obtained at a yield of 81%.
- The results of the measurements of NMR and FD-MASS on the obtained N,N,N′,N′-tetra(2-naphthyl)-4,4′-diaminostilbene were as follows:
- NMR: δ90 MHz 6.9 to 7.9 (38H, m)
- FD-MASS: 714
- N,N,N′,N′-Tetra(4-biphenylyl)benzidine was prepared in accordance with a conventional method.
- 4-Aminobiphenyl in an amount of 72.5 g (0.429 moles), 120 g (0.429 moles) of 4-iodobiphenyl, 32.6 g (0.236 moles) of potassium carbonate, 6.8 g (0.107 moles) of copper and 430 ml of nitrobenzene were placed into a reactor and the reaction was allowed to proceed at 210° C. for one night. When the reaction was completed, the reaction mixture was cooled by being left standing. Copper salts were removed by filtration under a reduced pressure. The filtrate was washed with chloroform and the solvent in the filtrate was removed by distillation under a reduced pressure. To the resultant residue, 500 ml of methanol was added. The obtained mixture was cooled and the formed crystals were separated by filtration. The obtained crystals in an amount of 49 g were dissolved into 250 ml of dimethylformamide (DMF) by heating. The resultant solution was cooled with water and tribiphenylamine of a byproduct precipitated by the cooling was removed by filtration. The filtrate was added into 1,000 ml of water and the formed crystals were separated by filtration, washed with water and methanol. The obtained crystals in an amount of 35 g which contained water were recrystallized from 750 ml of toluene and yellowish green scale-like crystals of di(4-biphenyl)amine were obtained. The mother liquor was concentrated and secondary crystals were obtained. The amount of the obtained product was 19 g (the yield: 13.8%). Into a reactor, 15 g (0.0467 moles) of di(4-biphenyl)amine, 9.5 g (0.0234 moles) of 4,4′-diiodobiphenyl, 9.7 g (0.0702 moles) of potassium carbonate, 0.74 g (0.0117 moles) of copper and 76 ml of nitrobenzene were placed and the reaction was allowed to proceed at 220° C. for 2 days. When the reaction was completed, 750 ml of DMF was added and copper salts were removed by filtration while the temperature of the reaction mixture remained high. The filtrate was cooled and the formed crystals were separated by filtration. The obtained crystals in an amount of 25 g which contained water were recrystallized 3 times from toluene in an amount 100 time as much as that of the crystals and light yellow crystals of N,N,N′,N′-tetra(4-biphenyl)benzidine as the object compound were obtained (the amount of the obtained product: 9 g; the yield: 48.6%).
- As described in detail in the above, in accordance with the method of the present invention, the aromatic amino compounds useful as the charge transporting material in the fields of the electronic photosensitive materials and the organic electroluminescence devices can be produced efficiently at a great yield without using highly toxic raw materials.
Claims (7)
1-9. (canceled)
10. A method for producing an aromatic amino compound represented by formula (VII):
wherein
Ar3-(X)n (VI)
Ar1 and Ar2 each independently represent a substituted or unsubstituted hydrocarbon group or heterocyclic group having 6 to 50 carbon atoms and may represent the same group or different groups,
Ar3 represents a substituted or unsubstituted aromatic residue group having 6 to 60 carbon atoms, and
n represents an integer of 1 to 4, comprising:
reacting an intermediate compound represented by formula (V):
wherein
Ar1 and Ar2 are as defined above, and
X represents a halogen group, with a mixture of halogenated aryl compounds represented by formula (VI):
Ar3-(X)n (VI)
wherein Ar3, X and n are as defined above,
in the presence of a noble metal catalyst.
11. The method according to claim 10 , wherein the substituent represented by R1 is a substituted or unsubstituted arylalkyl group.
12. The method according to claim 10 , wherein the substituent represented by R1 has carbonyl group.
13. The method according to claim 10 , wherein Ar1 and Ar2 each independently represent a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted 1 -naphthyl group or a substituted or unsubstituted 2-naphthyl group.
14. The method according to claim 10 , wherein the aromatic amino compound is a charge transporting material.
15. The method according to claim 10 , wherein the aromatic amino compound is a charge transporting material for organic electroluminescence devices.
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PCT/JP2002/002132 WO2002076922A1 (en) | 2001-03-16 | 2002-03-07 | Method for producing aromatic amino compound |
US11/239,116 US7250532B2 (en) | 2001-03-16 | 2005-09-30 | Method for producing aromatic amino compound |
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US20100219405A1 (en) * | 2007-09-13 | 2010-09-02 | Toshiya Sagisaka | Novel arylamine polymer, method for producing the same, ink composition, film, electronic device, organic thin-film transistor, and display device |
Families Citing this family (105)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4287198B2 (en) * | 2002-11-18 | 2009-07-01 | 出光興産株式会社 | Organic electroluminescence device |
US7402699B2 (en) * | 2004-11-22 | 2008-07-22 | Xerox Corporation | Process for arylamine production |
JP2006290818A (en) * | 2005-04-13 | 2006-10-26 | Tosoh Corp | Method for producing high-purity aromatic secondary amine |
JP2006290819A (en) * | 2005-04-13 | 2006-10-26 | Tosoh Corp | Method for producing aromatic secondary amine |
US8546451B2 (en) * | 2005-11-28 | 2013-10-01 | Gtx, Inc. | Estrogen receptor ligands and methods of use thereof |
US8158828B2 (en) * | 2005-11-28 | 2012-04-17 | Gtx, Inc. | Nuclear receptor binding agents |
US8637706B2 (en) | 2005-11-28 | 2014-01-28 | Gtx, Inc. | Nuclear receptor binding agents |
US9409856B2 (en) | 2005-11-28 | 2016-08-09 | Gtx, Inc. | Estrogen receptor ligands and methods of use thereof |
MX2008006885A (en) * | 2005-11-28 | 2008-10-20 | Gtx Inc | Nuclear receptor binding agents. |
DK1963251T3 (en) * | 2005-12-12 | 2012-11-26 | Syngenta Participations Ag | Process for the preparation of amines |
JP4784402B2 (en) * | 2006-06-06 | 2011-10-05 | 東ソー株式会社 | Catalyst for producing arylamines and method for producing arylamines using the same |
JP4227158B2 (en) * | 2006-08-04 | 2009-02-18 | バンドー化学株式会社 | Organic electroluminescence device |
US7408085B2 (en) * | 2006-11-28 | 2008-08-05 | Xerox Corporation | Rapid cost effective method for the synthesis of TPD-type arylamines |
US7838703B2 (en) * | 2007-11-16 | 2010-11-23 | Chemtura Corporation | Diaromatic amine derivatives as antioxidants |
JP5284037B2 (en) * | 2008-10-30 | 2013-09-11 | 保土谷化学工業株式会社 | Method for producing bisarylamine derivative |
US9427418B2 (en) | 2009-02-23 | 2016-08-30 | Gtx, Inc. | Estrogen receptor ligands and methods of use thereof |
US9624161B2 (en) | 2009-02-23 | 2017-04-18 | Gtx, Inc. | Estrogen receptor ligands and methods of use thereof |
WO2011015265A2 (en) | 2009-08-04 | 2011-02-10 | Merck Patent Gmbh | Electronic devices comprising multi cyclic hydrocarbons |
WO2011076326A1 (en) | 2009-12-22 | 2011-06-30 | Merck Patent Gmbh | Electroluminescent functional surfactants |
WO2011076323A1 (en) | 2009-12-22 | 2011-06-30 | Merck Patent Gmbh | Formulations comprising phase-separated functional materials |
WO2011076314A1 (en) | 2009-12-22 | 2011-06-30 | Merck Patent Gmbh | Electroluminescent formulations |
DE102010006280A1 (en) | 2010-01-30 | 2011-08-04 | Merck Patent GmbH, 64293 | color conversion |
JP2013522816A (en) | 2010-03-11 | 2013-06-13 | メルク パテント ゲーエムベーハー | Light emitting fiber |
US9539438B2 (en) | 2010-03-11 | 2017-01-10 | Merck Patent Gmbh | Fibers in therapy and cosmetics |
WO2011147522A1 (en) | 2010-05-27 | 2011-12-01 | Merck Patent Gmbh | Compositions comprising quantum dots |
EP2577734B1 (en) | 2010-05-27 | 2019-11-13 | Merck Patent GmbH | Down conversion |
US20130226268A1 (en) | 2010-07-26 | 2013-08-29 | Merck Patent Gmbh | Nanocrystals in devices |
JP2013539584A (en) | 2010-07-26 | 2013-10-24 | メルク パテント ゲーエムベーハー | Quantum dots and hosts |
DE102010054525A1 (en) | 2010-12-15 | 2012-04-26 | Merck Patent Gmbh | Organic electroluminescent device |
DE102010055901A1 (en) | 2010-12-23 | 2012-06-28 | Merck Patent Gmbh | Organic electroluminescent device |
JP6351974B2 (en) | 2011-02-14 | 2018-07-04 | メルク パテント ゲーエムベーハー | Devices and methods for treatment of cells and cellular tissues |
US9923152B2 (en) | 2011-03-24 | 2018-03-20 | Merck Patent Gmbh | Organic ionic functional materials |
EP2707911B1 (en) | 2011-05-12 | 2017-07-05 | Merck Patent GmbH | Compositions and electronic devices |
EP2737553A1 (en) | 2011-07-25 | 2014-06-04 | Merck Patent GmbH | Copolymers with functionalized side chains |
DE102011117422A1 (en) | 2011-10-28 | 2013-05-02 | Merck Patent Gmbh | Hyperbranched polymers, process for their preparation and their use in electronic devices |
CN102516089A (en) * | 2011-10-28 | 2012-06-27 | 黑龙江省科学院石油化学研究院 | Synthesis method for 9,9-dimethyl-2-(N-biphenyl)-aminofluorene |
KR20140123555A (en) | 2012-01-30 | 2014-10-22 | 메르크 파텐트 게엠베하 | Nanocrystals on fibers |
US8883383B2 (en) * | 2012-11-21 | 2014-11-11 | Xerox Corporation | Charge transport layer comprising fluoroacyl arylamine |
KR102238849B1 (en) | 2013-07-29 | 2021-04-09 | 메르크 파텐트 게엠베하 | Electro-optical device and the use thereof |
US20160181537A1 (en) | 2013-07-29 | 2016-06-23 | Merck Patent Gmbh | Electroluminescence Device |
EP3084855B1 (en) | 2013-12-20 | 2021-08-18 | UDC Ireland Limited | Highly efficient oled devices with very short decay times |
TWI718099B (en) * | 2014-07-11 | 2021-02-11 | 日商日產化學工業股份有限公司 | Charge-transporting varnish and manufacturing method of charge-transporting film |
KR102388865B1 (en) | 2014-09-05 | 2022-04-20 | 메르크 파텐트 게엠베하 | Formulations and electronic devices |
WO2016086885A1 (en) | 2014-12-04 | 2016-06-09 | 广州华睿光电材料有限公司 | Deuterated organic compound, mixture and composition containing said compound, and organic electronic device |
EP3229288B1 (en) | 2014-12-04 | 2019-05-01 | Guangzhou Chinaray Optoelectronic Materials Ltd. | Polymer, and mixture, formulation and organic electronic device containing the same, and monomer thereof |
WO2016091219A1 (en) | 2014-12-11 | 2016-06-16 | 广州华睿光电材料有限公司 | Organic compound, mixture comprising same, composite, and organic electronic component |
US10573827B2 (en) | 2014-12-11 | 2020-02-25 | Guangzhou Chinaray Optoelectronics Materials Ltd. | Organic metal complex, and polymer, mixture, composition and organic electronic device containing same and use thereof |
EP3241248A1 (en) | 2014-12-30 | 2017-11-08 | Merck Patent GmbH | Formulations and electronic devices |
CN107108862B (en) | 2015-01-13 | 2019-08-02 | 广州华睿光电材料有限公司 | Conjugated polymer, the mixture comprising it, composition, organic electronic device and its application of the crosslinked group containing acetenyl |
WO2016155866A1 (en) | 2015-03-30 | 2016-10-06 | Merck Patent Gmbh | Formulation of an organic functional material comprising a siloxane solvent |
WO2016182269A1 (en) * | 2015-05-08 | 2016-11-17 | 머티어리얼사이언스 주식회사 | Method for preparing compound for organic electroluminescent device |
KR101671277B1 (en) * | 2015-05-08 | 2016-11-01 | 머티어리얼사이언스 주식회사 | The method for manufacturing compound for organic electroluminescent device |
EP4060757A1 (en) | 2015-06-03 | 2022-09-21 | UDC Ireland Limited | Highly efficient oled devices with very short decay times |
CN107690720B (en) | 2015-06-12 | 2020-04-03 | 默克专利有限公司 | Esters containing non-aromatic rings as solvents for OLED formulations |
JP2018527733A (en) | 2015-08-28 | 2018-09-20 | メルク パテント ゲーエムベーハー | Formulation of organic functional material containing epoxy group-containing solvent |
WO2017080326A1 (en) | 2015-11-12 | 2017-05-18 | 广州华睿光电材料有限公司 | Printing composition, electronic device comprising same and preparation method for functional material thin film |
US11005042B2 (en) | 2015-12-10 | 2021-05-11 | Merck Patent Gmbh | Formulations containing ketones comprising non-aromatic cycles |
CN111477768B (en) | 2015-12-15 | 2023-04-07 | 默克专利有限公司 | Aromatic group-containing esters as solvents for organic electronic formulations |
EP3390550B1 (en) | 2015-12-16 | 2022-09-28 | Merck Patent GmbH | Formulations containing a mixture of at least two different solvents |
KR20180096676A (en) | 2015-12-16 | 2018-08-29 | 메르크 파텐트 게엠베하 | Formulation containing a solid solvent |
EP3417033B1 (en) | 2016-02-17 | 2021-02-24 | Merck Patent GmbH | Formulation of an organic functional material |
DE102016003104A1 (en) | 2016-03-15 | 2017-09-21 | Merck Patent Gmbh | Container comprising a formulation containing at least one organic semiconductor |
JP2019523997A (en) | 2016-06-16 | 2019-08-29 | メルク パテント ゲーエムベーハー | Formulation of organic functional materials |
CN109312183A (en) | 2016-06-17 | 2019-02-05 | 默克专利有限公司 | The preparation of organic functional material |
TW201815998A (en) | 2016-06-28 | 2018-05-01 | 德商麥克專利有限公司 | Formulation of an organic functional material |
CN109563402B (en) | 2016-08-04 | 2022-07-15 | 默克专利有限公司 | Preparation of organic functional materials |
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5648539A (en) * | 1996-02-29 | 1997-07-15 | Xerox Corporation | Low temperature arylamine processes |
US5654482A (en) * | 1996-02-29 | 1997-08-05 | Xerox Corporation | Triarylamine processes |
US5723669A (en) * | 1997-01-30 | 1998-03-03 | Xerox Corporation | Arylamine processes |
US5837166A (en) * | 1993-09-29 | 1998-11-17 | Idemitsu Kosan Co., Ltd. | Organic electroluminescence device and arylenediamine derivative |
US5902901A (en) * | 1998-05-07 | 1999-05-11 | Xerox Corporation | Arylamine processes |
US5929281A (en) * | 1996-04-19 | 1999-07-27 | Tosoh Corporation | Process for producing heterocyclic aromatic amine or arylamine |
US5977361A (en) * | 1997-10-16 | 1999-11-02 | Yale University | Transition metal-catalyzed process for preparing N-aryl compounds |
US6100398A (en) * | 1998-10-14 | 2000-08-08 | Yale University | Transition metal-catalyzed process for preparing N-aryl amine compounds |
US6476265B1 (en) * | 1997-09-05 | 2002-11-05 | Covion Organic Semiconductors Gmbh | Method for producing aryl oligoamines |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56123964A (en) | 1980-05-10 | 1981-09-29 | Nissan Chem Ind Ltd | 1- n-benzyl-o- 2,6-dichloroanilino phenyl -2-methylsulfinyl- 2-methylthioethylene |
JPS6335548A (en) * | 1986-07-30 | 1988-02-16 | Asahi Chem Ind Co Ltd | Production of triarylamine |
JPH06100503A (en) * | 1992-09-22 | 1994-04-12 | Minolta Camera Co Ltd | Aminobiphenyl derivative and its production |
JP3972405B2 (en) * | 1997-05-09 | 2007-09-05 | 東ソー株式会社 | Method for producing tertiary arylamines |
-
2002
- 2002-03-07 US US10/469,702 patent/US20040082813A1/en not_active Abandoned
- 2002-03-07 WO PCT/JP2002/002132 patent/WO2002076922A1/en active Application Filing
- 2002-03-07 JP JP2002576185A patent/JPWO2002076922A1/en active Pending
- 2002-03-07 CN CNB028066146A patent/CN1271041C/en not_active Expired - Lifetime
- 2002-03-07 CN CNA2006100943896A patent/CN1896048A/en active Pending
- 2002-03-07 KR KR10-2003-7012009A patent/KR20030093240A/en not_active Application Discontinuation
- 2002-03-13 TW TW091104727A patent/TWI301125B/en not_active IP Right Cessation
-
2005
- 2005-09-30 US US11/239,116 patent/US7250532B2/en not_active Expired - Lifetime
-
2007
- 2007-06-19 US US11/764,912 patent/US20070249866A1/en not_active Abandoned
- 2007-06-19 US US11/764,896 patent/US20070249861A1/en not_active Abandoned
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5837166A (en) * | 1993-09-29 | 1998-11-17 | Idemitsu Kosan Co., Ltd. | Organic electroluminescence device and arylenediamine derivative |
US5648539A (en) * | 1996-02-29 | 1997-07-15 | Xerox Corporation | Low temperature arylamine processes |
US5654482A (en) * | 1996-02-29 | 1997-08-05 | Xerox Corporation | Triarylamine processes |
US5929281A (en) * | 1996-04-19 | 1999-07-27 | Tosoh Corporation | Process for producing heterocyclic aromatic amine or arylamine |
US5723669A (en) * | 1997-01-30 | 1998-03-03 | Xerox Corporation | Arylamine processes |
US6476265B1 (en) * | 1997-09-05 | 2002-11-05 | Covion Organic Semiconductors Gmbh | Method for producing aryl oligoamines |
US5977361A (en) * | 1997-10-16 | 1999-11-02 | Yale University | Transition metal-catalyzed process for preparing N-aryl compounds |
US5902901A (en) * | 1998-05-07 | 1999-05-11 | Xerox Corporation | Arylamine processes |
US6100398A (en) * | 1998-10-14 | 2000-08-08 | Yale University | Transition metal-catalyzed process for preparing N-aryl amine compounds |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100219405A1 (en) * | 2007-09-13 | 2010-09-02 | Toshiya Sagisaka | Novel arylamine polymer, method for producing the same, ink composition, film, electronic device, organic thin-film transistor, and display device |
US10011684B2 (en) | 2007-09-13 | 2018-07-03 | Ricoh Company, Ltd. | Arylamine polymer, method for producing the same, ink composition, film, electronic device, organic thin-film transistor, and display device |
Also Published As
Publication number | Publication date |
---|---|
CN1501908A (en) | 2004-06-02 |
CN1896048A (en) | 2007-01-17 |
KR20030093240A (en) | 2003-12-06 |
JPWO2002076922A1 (en) | 2004-07-15 |
US7250532B2 (en) | 2007-07-31 |
US20040082813A1 (en) | 2004-04-29 |
US20070249861A1 (en) | 2007-10-25 |
WO2002076922A1 (en) | 2002-10-03 |
CN1271041C (en) | 2006-08-23 |
TWI301125B (en) | 2008-09-21 |
US20060030736A1 (en) | 2006-02-09 |
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