KR101553590B1 - Process for the preparation of ligand of blue phosphorescence - Google Patents

Process for the preparation of ligand of blue phosphorescence Download PDF

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KR101553590B1
KR101553590B1 KR1020130030882A KR20130030882A KR101553590B1 KR 101553590 B1 KR101553590 B1 KR 101553590B1 KR 1020130030882 A KR1020130030882 A KR 1020130030882A KR 20130030882 A KR20130030882 A KR 20130030882A KR 101553590 B1 KR101553590 B1 KR 101553590B1
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허현수
정준영
김명석
강성철
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주식회사 네패스
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/0032Selection of organic semiconducting materials, e.g. organic light sensitive or organic light emitting materials
    • H01L51/0077Coordination compounds, e.g. porphyrin
    • H01L51/0084Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H01L51/0085Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising Iridium
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/50Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for light emission, e.g. organic light emitting diodes [OLED] or polymer light emitting devices [PLED];
    • H01L51/5012Electroluminescent [EL] layer
    • H01L51/5016Triplet emission
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/50Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for light emission, e.g. organic light emitting diodes [OLED] or polymer light emitting devices [PLED];
    • H01L51/56Processes or apparatus specially adapted for the manufacture or treatment of such devices or of parts thereof

Abstract

The present invention relates to a method for preparing a ligand of a blue phosphorescent dopant, wherein one aspect of the present invention is a process for producing a compound of formula (III)
(2)
Figure 112013025004492-pat00024

(3)
Figure 112013025004492-pat00025

(B) adding a compound of the formula (4) and a catalyst to the compound of the formula (3) to produce a compound of the formula (5)
Formula 4
Figure 112013025004492-pat00026

Formula 5
Figure 112013025004492-pat00027

In the compounds of formula 2, X can be hydrogen (-H), bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl -), and toluenesulphonyl (-TsO). The reactant of step A is trimethylborate (B (OMe) 3 ), n-butyllithium (n-BuLi) , n- tree view tiltin chloride (n-tributyltin chloride, n- Bu 3 SnCl), zinc (zinc, Zn), copper chloride (I) (copper (I) chloride, CuCl), hexamethyl trisiloxane cycloalkyl (hexamethylcyclotrisiloxane, (Me 2 SiO) 3 ), wherein R is a boronic acid, B (OH) 2 , trialkyltin, SnR ' 3 derivative, , A zinc halide derivative, an alkylsilicon (SiR ') derivative, a magnesium halide derivative, an organic lead derivative, and copper (Cu) In Formula 4, X 'is bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-), toluenesulfonyl (Pd), nickel (Ni), ruthenium (Ru), iron (Fe), iron (Fe), osmium (Os) Os, platinum, Pt, gold, copper, copper, zinc, rhodium, rhodium, iridium, ir, cadmium, cadmium, ), Mercury (Hg), silver (Ag), tin (Sn), and R 'is a linear or branched C 1-20 alkyl , C < / RTI > 3-20 cyclic alkyl, and the like.
Another aspect of the present invention is a process for producing a compound of formula 7 from a compound of formula 6,
6
Figure 112013025004492-pat00028

Formula 7
Figure 112013025004492-pat00029

(D) adding a compound of formula (VIII) and a catalyst to a compound of formula (VII) to produce a compound of formula (5)
8
Figure 112013025004492-pat00030

Formula 5
Figure 112013025004492-pat00031

In the compound of formula (VI), X can be hydrogen (-H), bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl -), and toluenesulphonyl (-TsO). The reactant of step A is trimethylborate (B (OMe) 3 ), n-butyllithium (n-BuLi) , n- tree view tiltin chloride (n-tributyltin chloride, n- Bu 3 SnCl), zinc (zinc, Zn), copper chloride (I) (copper (I) chloride, CuCl), hexamethyl trisiloxane cycloalkyl (hexamethylcyclotrisiloxane, (Me 2 SiO) 3 ), wherein R is a boronic acid, B (OH) 2 , trialkyltin, SnR ' 3 derivative, , A zinc halide derivative, an alkylsilicon (SiR ') derivative, a magnesium halide derivative, an organic lead derivative, and copper (Cu) In the compound of formula 8, X 'is bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-) (Pd), nickel (Ni), ruthenium (Ru), ruthenium (Ru), iron (Fe), and osmium (Fe) Osmium, Os, platinum, Pt, gold, copper, copper, zinc, rhodium, rhodium, iridium, iridium, cadmium, , Cd), mercury (Hg), silver (Ag), tin (Sn), and R 'is a linear or branched C 1- Lt; RTI ID = 0.0 > Cl- 20 < / RTI > alkyl, C3-20 cyclic alkyl.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for preparing a ligand of a blue phosphorescent dopant,

The present invention relates to a method for preparing a ligand of a dopant used in an organic light emitting device, and more particularly to a method for preparing a ligand of a blue phosphorescent dopant applicable to a device such as a flat panel display or various electronic devices.

Blue phosphorescent dopant and organic light emitting diode (OLED):

A long pursued goal in the art of phosphorescent light emitting materials as organic light emitting devices is to develop materials that emit more efficiently at various wavelengths. With respect to the phosphorescent light emitting material, research is continuously carried out to increase the amount of energy absorbed and emitted by the amount of a given luminescent material, which emits light in the visible light region.

Phosphorescent light emitting materials including transition metal complexes are attracting interest by efficiently emitting phosphorescence from triplet metal-to-charge and charge-transfer states. The rate of transition from a triplet excited state to a singlet ground state is very slow due to the time required for the charge to separate, but when there are large atomic number elements, the spin- Due to the promotion of spin orbit coupling interactions, efficient cross-over from triplet excited states to triplet excited states occurs.

Such a light emitting material is used as a light emitting guest material in an emissive layer of an organic light emitting device. The heavy metal ions here are transition metal ions such as Ir (III), Pt (II), Os (III) and Au (III) The osmium complex has the disadvantage that the luminous efficiency is lowered because one or more possible luminescent path is interrupted due to the reduction of the triplet state (JN Demas and GA Crosby, J. Am. Chem. Soc. 93, pp. 2841-2847 , 1971). Application of an osmium complex in an organic light emitting device was first introduced by Y. Ma et al. In which poly (N-vinyl carbazole) doped with several osmium complexes (Y. Ma et al., Synth. Met 94, p 245, 1998). However, the quantum efficiency of an electroluminescent device using such an osmium complex as a light emitting material was as low as 0.1% or less. Although several other Os (III) complexes exhibited relatively high quantum efficiency (X. Jiang et al., Appl. Phys. Lett., 80, pp. 713-715, 2002, The quantum efficiency obtained by using this as a light emitting layer was not as high as that of an OLED using a fluorescent material as a light emitting material.

Electrophotorescent devices containing organometallic Au (I) and Cu (I) complexes have been reported by the same authors (Y. Ma, et al., Adv. Mat., 11, p. In the case of the two phosphors, the quantum efficiency of the device was very low, less than 0.1%, despite effective intersystem crossing (ISC) and high PL emission efficiency of 23% and 42%. This low luminous efficiency is due to the low energy recovery of the luminescent material (M. Baldo, et al., Pure. Appl. Chem. 71, pp. 2095-2106, 1999).

Highly efficient electrophosphorescent devices include Pt (II) organometallic complexes such as PtOEP (2,3,7,8,12,13,17,18, -octaethyl-21H, 23H-porphine platinum (II) It was first developed in use. In the case of PtOEP, no luminescence was observed in the singlet state (580 nm), whereas in the triplet state (650 nm), effective red phosphorescence was shown (RC Kwong et al., Chem. DF O'Brien et al., Appl. Phys. Lett., 74, pp. 442-444, 1999). However, PtOEP increases triplet-triplet annihilation due to a long lifetime of 65 μs at room temperature, and consequently has a disadvantage in that quantum efficiency decreases rapidly with increasing current.

These points are of interest in connection with passively driven display devices, since they require the OLED to be strongly excited by short electrical pulses. Since the triplet-triplet extinction increases with the square of the concentration of the triplet exciton (M. Klessinger, J. Michl. Excited States and Photochemistry of Organic Molecules, VCH Publishers, New York, 1995) Pulses that are faster than the speed can be used to avoid a significant reduction in efficiency (MA Baldo, et al., Pure. Appl. Chem., 71, pp. 2095-2106, 1999). The triplet-triplet extinction and the saturation of the light emitting layer can be minimized by using a phosphorescent material having a short lifetime as a light emitting material. In the case of iridium (III) complexes, lifetime in the excited state is not as long as about 1 to 2 ㎲, so that it is known as the most efficient phosphorescent emitter due to intermetallic transition or energy transfer (MA Baldo, et al., Appl. 75, pp. 4-6, 1999).

(MA Baldo, et. Al., Nature, 395, 1985), the result of doping Alq3 (tris- (8-hydroxyl quinoline) aluminum (III)) as a light emitting layer with platinum octaethylporphylene as a triplet light- pp. 151-154, 1998. Since the publication of DF O'Brien et al., Appl. Phys. Lett., 74, pp. 442-444, 1999, US Patent No. 6,303,238 to Thompson et al. Efforts have been made to find luminescent materials that emit light at various wavelengths in the visible light region.

Successful use of facial- [Ir (ppy) 3] and derivatives thereof as a green illuminant (MA Baldo et al., Appl. Phys. Lett., 75, pp. 4-6, 1999; T. Tsutsui et al. , Appl. Phys. Lett., 77, pp. 904-906, 2000, CL Lee et al., Appl. Phys.Lett. 77, pp. 2280-2282, 2000. X. Gong et al., Adv.Mater. 14, pp. 581-585, 2002. W. Zhu et al. 80, pp. 2045-2047, 2002; HA Xie et al., Adv. Mater. 13, pp. 1245-1258, 2001. Y. Wang et al., Appl. Phys. Lett. -451, 2001) relies on the use of transition metal complexes to obtain green luminescence with high quantum yield.

Color tuning of iridium (III) complexes can be done from blue to red by changing the organic ligand (S. Ramansky et al., J. Am. Chem. Soc. 123, pp. 4304-4312, 2001 ). Red electroluminescent phosphors were prepared by reacting an iridium (III) complex (S. Lamansky et al., J. Am. Chem. Soc. 123, pp. 4304-4312, 2001; S. Lamamnsky, et al. 2002, pp. 1570-1575, 1992) and Os (III) complex (X. Jiang et al., Appl. Phys. Lett., 80, pp. 713-715, 2002; , Appl. Phys. Lett., 81, pp. 3125-3127, 2002). It has also been reported that yellow and orange luminescence is also obtained from iridium (III) complexes (S. Lamansky et al., J. Am. Chem. Soc. 123, pp. 4304-4312, 2001. S. Lamamnsky, et al., J. Appl. Phys., 92, pp. 1570-1575, 1992).

However, the realization of blue light emission by the change of the ligand is a very difficult problem in the field of the electric phosphorescent device. A blue electroluminescent device using a mixed iridium (III) ligand complex used with a chlorine ion substituted with 2-phenyl pyridine and picolinate as a phosphorescent light-emitting layer has been reported (Adachi, et al., Appl. Phys. Lett., 79, pp. 2082-2084, 2001). It has also been reported that a similar compound with the same orthometalating ligand and another bidentate ligand and two platinum compounds emit white light using a triplet excimer in an electrophosphorescent device (BW D ' et al., 14, pp. 147-15, 2002). < / RTI >

Due to the accumulation of various excited states at high energy, it is very difficult to rationally design the blue luminescence. This blue emission can be achieved by carefully reducing the number of potential emission states (H. Kunkely, et al., Chem. Phys. Lett. 319, pp. 486-488, 2000). The energy difference between HOMO and ligand π * can be increased by selection of the appropriate ligand. For efficient blue emission, the ligand field (LF) state must be located above the emission state to prevent non-radiative deactivation by the amount of activated LF state. Such an attempt can be made by using strong ligands in the ligand field.

Korean Patent Laid-Open No. 10-2010-0092572 discloses a process for the preparation of 2- (2,4-difluoro-3- (trifluoromethyl) phenyl) -4-methylpyridine A patent for a heterolitic iridium complex containing 2- (2,4-difluoro-3- (trifluoromethyl) phenyl) -4-methylpyridine) has been filed and this material is superior as a dark blue phosphorescent dopant Lt; / RTI > This substance contains a large amount of fluorine elements having a high electronegativity and acts as a strong electron attractant. The deep blue light emission lowers the electron density of the phenyl derivative of the phenylpyridine ligand to lower the HOMO energy level and the methyl group in the pyridine derivative, And increased the electron density to increase the LUMO energy level, resulting in an increase in the HOMO-LUMO energy bandgap. The phenylpyridine ligand is prepared by the following reaction scheme 1.

[Reaction Scheme 1]

Figure 112013025004492-pat00001

As can be seen from the above procedure, a pairing reaction is generally performed to produce the desired ligand. The coupling reaction is generally referred to as a reaction in which two kinds of organic compounds cause a condensation reaction between different functional groups to generate a new covalent bond. Typical examples are diazo coupling and reactions in which the same species of compound reacts between the functional groups of different species to form new covalent bonds. Aldol condensation, for example, can also be considered as a coupling reaction.

Have made many advances in forming a new carbon-carbon bond through a coupling reaction. The formation of a carbon-carbon bond through a general coupling reaction takes place through a mechanism of the following formula (1).

Figure 112013025004492-pat00002

2,4-difluorophenylboronic acid and 2-bromo-4-methylpyridine are reacted with palladium (Pd) Synthesis of 2- (2,4-difluorophenyl) -4-methylpyridine using a Suzuki coupling catalysis yield: 70%, the following lithium di (2,4-difluoro-3-iodo-phenyl) -4-methylpyridine (LDA) (in a CF 3 substituted reaction product of 2- (2,4-difluoro with Me 3 SiCF 3) -3- (trifluoromethyl) 4-methylpyridine) synthesis yield of 25%, and finally the methyl trimethylsilane-trifluorophenyl) (2,4-difluoro-3- (trifluoromethyl) phenyl) -4-methylpyridine was obtained in a yield of 20% and a total yield of only 9% 2,4-difluoro-3- (trifluoromethyl) phenyl) -4-methylpyridine (2- (2,4-d 3-trifluoromethyl) phenyl) -4-methylpyridine, it takes two weeks.

Therefore, the above materials are used in the industry as a blue phosphorescent dopant based on the above advantages, but their synthesis is very difficult.

Korean Patent Publication No. 10-2010-0092572

The preparation method according to the present invention is characterized in that a blue phosphorescent dopant material such as 2- (2,4-difluoro-3- (trifluoromethyl) phenyl) -4-methylpyridine (2- (trifluoromethyl) phenyl) -4-methylpyridine ligand in the reaction step to reduce the synthesis time.

The present invention relates to a method for preparing a ligand of a blue phosphorescent dopant, wherein one aspect of the present invention is a process for producing a compound of formula (III)

Figure 112013025004492-pat00003

Figure 112013025004492-pat00004

(B) adding a compound of the formula (4) and a catalyst to the compound of the formula (3) to produce a compound of the formula (5)

Figure 112013025004492-pat00005

Figure 112013025004492-pat00006

In the compounds of formula 2, X can be hydrogen (-H), bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl -), and toluenesulphonyl (-TsO). The reactant of step A is trimethylborate (B (OMe) 3 ), n-butyllithium (n-BuLi) , n- tree view tiltin chloride (n-tributyltin chloride, n- Bu 3 SnCl), zinc (zinc, Zn), copper chloride (I) (copper (I) chloride, CuCl), hexamethyl trisiloxane cycloalkyl (hexamethylcyclotrisiloxane, (Me 2 SiO) 3 ), wherein R is a boronic acid, B (OH) 2 , trialkyltin, SnR ' 3 derivative, , A zinc halide derivative, an alkylsilicon (SiR ') derivative, a magnesium halide derivative, an organic lead derivative, and copper (Cu) In Formula 4, X 'is bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-), toluenesulfonyl (Pd), nickel (Ni), ruthenium (Ru), iron (Fe), iron (Fe), osmium (Os) Os, platinum, Pt, gold, copper, copper, zinc, rhodium, rhodium, iridium, ir, cadmium, cadmium, ), Mercury (Hg), silver (Ag), tin (Sn), and R 'is a linear or branched C 1-20 alkyl , C < / RTI > 3-20 cyclic alkyl, and the like.

Another aspect of the present invention is a process for producing a compound of formula 7 from a compound of formula 6,

Figure 112013025004492-pat00007

Figure 112013025004492-pat00008

(D) adding a compound of formula (VIII) and a catalyst to a compound of formula (VII) to produce a compound of formula (5)

Figure 112013025004492-pat00009

In the compound of formula (VI), X can be hydrogen (-H), bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl -), and toluenesulphonyl (-TsO). The reactant of step A is trimethylborate (B (OMe) 3 ), n-butyllithium (n-BuLi) , n- tree view tiltin chloride (n-tributyltin chloride, n- Bu 3 SnCl), zinc (zinc, Zn), copper chloride (I) (copper (I) chloride, CuCl), hexamethyl trisiloxane cycloalkyl (hexamethylcyclotrisiloxane, (Me 2 SiO) 3 ), wherein R is a boronic acid, B (OH) 2 , trialkyltin, SnR ' 3 derivative, , A zinc halide derivative, an alkylsilicon (SiR ') derivative, a magnesium halide derivative, an organic lead derivative, and copper (Cu) In the compound of formula 8, X 'is bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-) (Pd), nickel (Ni), ruthenium (Ru), ruthenium (Ru), iron (Fe), and osmium (Fe) Osmium, Os, platinum, Pt, gold, copper, copper, zinc, rhodium, rhodium, iridium, iridium, cadmium, , Cd), mercury (Hg), silver (Ag), tin (Sn), and R 'is a linear or branched C 1- Lt; RTI ID = 0.0 > Cl- 20 < / RTI > alkyl, C3-20 cyclic alkyl.

In another aspect of the present invention, X is at least one of hydrogen (-H), bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulphonyl Wherein the reaction material of step A or step C is trimethylborate (B (OMe) 3 ), R is one selected from the group consisting of boron oxide (TfO-) and toluene sulfonyl (-TsO) A method for producing a ligand of a blue phosphorescent dopant which is a derivative can be provided.

In another aspect of the present invention, X is bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-), toluene (N-butyllithium, n-BuLi) and n-tributyltin chloride (-TsO), and the reaction material of step A or step C is selected from the group consisting of n-butyllithium, n-Bu 3 SnCl) and R is a trialkyltin (SnR ' 3 ) derivative.

X includes bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-), and toluenesulfonyl And the reactive material of step A or step C is zinc (Zn), and R is a zinc halide derivative. The method for producing the ligand of the blue phosphorescent dopant is as follows.

X includes bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-), and toluenesulfonyl And the reaction material of step A or step C is selected in order of n-butyllithium, n-BuLi and hexamethylcyclotrisiloxane (Me 2 SiO) 3 , R can provide a method for preparing a ligand of a blue phosphorescent dopant that is an alkylsilicon derivative.

In another aspect of the present invention, X is bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-), toluene (-TsO), the reaction material of step A or step C is magnesium (Mg), and R is an organomagnesium derivative, can provide a method for producing a ligand of a blue phosphorescent dopant .

In another aspect of the present invention, X is bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-), toluene (I) chloride (CuCl), and R is at least one selected from the group consisting of copper (Cu), copper (I) chloride In the method for producing a ligand of a blue phosphorescent dopant, it is possible to provide a method for producing a ligand of a blue phosphorescent dopant through which X is further reacted with magnesium (Mg, Mg).

In addition, another aspect of the present invention, a metal catalyst comprising a palladium tetrakis (triphenylphosphine) palladium (Tetrakis (triphenylphosphine) palladium, Pd (PPh 3) 4), bis (dibenzylideneacetone) palladium, (Bis ( dibenzylideneacetone) palladium, Pd (dba) 2), palladium (II) acetate (palladium (II) acetate, Pd (OAc) 2), bis (acetonitrile) dichloropalladium (II) (bis (acetonitrile) dichloropalladium (II) , PdCl 2 (MeCN) 2) , bis (triphenylphosphine) palladium (II) dichloride (Dichlorobis (triphenylphosphane) palladium (II ), PdCl 2 (PPh 3) 2), or benzyl bis (triphenylphosphine) A method for producing a ligand of a blue phosphorescent dopant can be provided which is a palladium (II) chloride (benzyl (chloro) bis (triphenylphosphine) palladium (II)) or BnPdCl (PPh 3 ) 2 .

In another aspect of the present invention, the metal catalyst comprising nickel is at least one selected from the group consisting of [1,3-bis (diphenylphosphino) propane] nickel (II) , Ni (dppp) Cl 2) , 1,2- bis (diphenylphosphino) ethane nickel chloride (II) (1,2-bis ( diphenylphosphino) ethane nickel (II) chloride, Ni (dppe) Cl 2), Bis (trialkylphosphino) butane nickel (II) (Dichlorobis (trialkylphosphine) nickel (II), Ni (PR3) 2Cl2), Bis (diphenylphosphino) butane nickel (II) chloride, Ni (dppb) Cl 2 , and 1,2-bis (dimethylphosphanyl) ethane chloride (II) 2 ), (dimethylphosphinoferrocene) dichlorophosphate nickel (II), Ni (dmpf) Cl2).

In another aspect of the present invention, step A or step C comprises the steps of adding a compound of formula 2 or a compound of formula 6 to tetrahydrofuran (THF), dropping lithium diisopropylamide (LDA) Stirring at -78 ° C and stirring at room temperature, and extraction with diethyl ether followed by evaporation of the organic solvent.

In another aspect of the present invention, step B or step D comprises the steps of adding a compound of formula 6 to a compound of formula 3 or a compound of formula 8 to a compound of formula 8, Followed by extraction with diethyl ether followed by evaporation of the organic solvent, to prepare a blue phosphorescent dopant ligand.

According to the preparation method according to the present invention, the blue phosphorescent dopant material 2- (2,4-difluoro-3- (trifluoromethyl) phenyl) -4-methylpyridine - (trifluoromethyl) phenyl) -4-methylpyridine) ligand in a short period of time.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic diagram of a process for preparing 2- (2,4-difluoro-3- (trifluoromethyl) phenyl) -4-methylpyridine ) Can be easily produced.
Figure 2 is a schematic diagram of the synthesis of 2- (2,4-difluoro-3- (trifluoromethyl) phenyl) -4-methylpyridine Bromo-4-methylpyridine, and a synthetic process for the intermediate structure, which is capable of a metal catalyst coupling reaction with 2-bromo-4-methylpyridine.
3 is a schematic diagram of each of the pairing reactions during the process according to the invention.
FIG. 4 is a graph showing the relationship between the target substance 2- (2,4-difluoro-3- (trifluoromethyl) phenyl) -4-methylpyridine (2- -4-methylpyridine).

2- (2,4-difluoro-3- (trifluoromethyl) phenyl) -4-methylpyridine, which exhibits excellent properties as the above-mentioned deep blue phosphorescent dopant, (trifluoromethyl) phenyl) -4-methylpyridine ligand, the yield is very high in the reaction of replacing the iodine (I) functional group of the phenyl group with the trifluoromethyl (CF 3 ) The problem should be solved. The reaction is not only very low in yield of about 20% but also takes a long time to separate the column.

Thus, if it is seen from FIG. 1 that 2- (2,4-difluoro-3- (trifluoromethyl) phenyl) -4-methylpyridine (2- 4-methylpyridine) ligand. As a result of experiments on the theoretical background, it has been found that 1,3-difluoro-2- (trifluoromethyl) benzene is reacted with lithium diisopropylamide (LDA) and trimethyl-laid beam (B (OMe) 3) and in response to order meals boronic derivative 2,4 to the mating reaction -3- (oro methyl triple) phenyl Boro Nick acid (2,4 -difluoro-3- (trifluoromethyl) phenyl boronic acid in 80% yield without column separation. This boronic acid derivative is reacted with 2-bromo-4-methylpyridine in an appropriate palladium catalyzed reaction to obtain the desired compound 2- (2,4-difluoro-3- (2,4-difluoro-3- (trifluoromethyl) phenyl) -4-methylpyridine was easily synthesized in 90% yield without column separation. The overall yield according to the present invention was 72%, which was a yield increase of 8-fold compared to the previously known yield of 9%. The synthesis time according to the present invention is also based on 1 g of 2- (2,4-difluoro-3- (trifluoromethyl) phenyl) pyridine (2- (2,4- , While the known reaction had a 4-fold reduction to 96 hours.

The core of the present invention is 1,3-difluoro-2- (trifluoromethyl) benzene in which trifluoromethyl (CF 3 ) is substituted as a starting material. Or 4-methylpyridine (4-methylpyridine). However, the starting material in the present invention is not limited to 1,3-difluoro-2- (trifluoromethyl) benzene. 1,3-difluoro-2- (trifluoromethyl) benzene is a compound that is substituted with hydrogen at position 4 and leaving a good leaving group at position 4 group can be used to facilitate the reaction more readily if the substituted starting material is used. Also, it is not necessary to define 4-methylpyridine as another starting material. 4-Methylpyridine (4-methylpyridine) is a compound in which hydrogen is substituted at the 2-position. If the starting material is substituted with a leaving group at the 2-position, the reaction can proceed more easily. 2 shows an example of the first reaction that takes place when a starting material substituted with a good leaving group is used. Examples of good leaving groups include bromo (Br-), iodo (I-), chloro (Cl-) (Ms-), trifluoromethanesulfonyl (TfO-), and toluenesulfonyl (TsO-).

A good leaving group means a leaving group with high stability after leaving. The stability criterion may be various, but it is mainly a leaving group that the basicity is weaker. In the case of bromo (Br-), iodo (I-) and chloro (Cl-) The stability is increased. In the case of methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-), and toluenesulfonyl (TsO-), since the resonance stability after removal is increased, . However, the good leaving group of the present invention is not limited thereto and includes good leaving groups that can be derived by a person skilled in the art.

1, the step of preparing 2,4-difluoro-3- (trifluoromethyl) phenyl boronic acid as an intermediate, a boronic acid derivative, The intermediate for the preparation of the starting material for the coupling reaction and the coupling reaction with 2-bromo-4-methylpyridine is not limited to the boronic acid derivative alone, The intermediate actually synthesized will have some variation.

Trialkyltin, SnR ' 3 derivative, a zinc halide derivative, an alkylsilicon (SiR') derivative, a magnesium halide derivative, an organic lead derivative , And copper (Cu) derivatives may have the form of an intermediate. This depends on what is substituted in the B (OH) 2 position of the intermediate in FIG. 1, which is why the 2-bromo-4-methylpyridine and the mating catalysis .

Also, R 'is one selected from the group consisting of straight or branched C 1-20 alkyl, C 3-20 cyclic alkyl.

Figure 3 is a diagram schematically illustrating pairing reactions. As can be seen from FIG. 3, in FIG. 1, a stille coupling reaction using a trialkyltin derivative such as a trialkyltin (SnR'3) derivative as well as a boronic acid derivative capable of an acceptor coupling reaction, Hiyama coupling reaction using an alkylsilicon (SiR ') derivative, Sonogashira reaction using a copper (Cu) derivative, organic lead (organic) lead) derivative, the objective compound 2- (2,4-difluoro-3- (trifluoromethyl) phenyl) -4-methylpyridine (2- - (trifluoromethyl) phenyl) -4-methylpyridine.

Examples of the metal catalyst include palladium (Pd), nickel (Ni), ruthenium (Ru), iron (Fe), osmium (Os), platinum Ionium, Ir, Cadmium, Cd, Mercury, Hg, Silver, Rhodium, Rhodium, Copper, Cu, (Silver, Ag), and tin (Tin, Sn), all of which are easily selectable by a person skilled in the art in producing a coupling reaction.

The Stille coupling reaction is a reaction that forms a carbon-carbon bond between an organic tin compound and an organic halogen compound using a palladium metal as a catalyst and is a functional group that is bonded to an organic tin There are few restrictions on the use of the various reactions. Organic tin compounds, unlike other organometallic compounds, are stable to oxygen or moisture but have low solubility in water due to their low polarity and toxicity is a major disadvantage of the Stille coupling reaction. Suzuki: Similar reactions to boronic acids and derivatives used in the Suzuki coupling reaction. In addition to palladium, manganese, nickel, and copper may be used as the metal catalyst used in the Stille coupling reaction. Examples of the palladium metal catalyst include tetrakis (triphenylphosphine) palladium, Pd (PPh 3 ) 4 , bis (dibenzylideneacetone) palladium, Pd ) 2), palladium (II) acetate (palladium (II) acetate, Pd (OAc) 2), bis (acetonitrile) dichloropalladium (II) (bis (acetonitrile) dichloropalladium (II), PdCl 2 (MeCN) 2 ), Bis (triphenylphosphine) palladium (II) dichloride (Dichlorobis (triphenylphosphane) palladium (II), PdCl 2 (PPh 3 ) 2 ), or benzylbis (triphenylphosphine) palladium (triphenylphosphine) palladium (II)) and BnPdCl (PPh 3 ) 2 ) are mainly used, but not limited thereto, metal catalysts containing the above-mentioned metals and all those that can be derived by those skilled in the art . The following Scheme 2 shows the reaction for making the starting material for performing the Stille coupling reaction.

[Reaction Scheme 2]

Figure 112013025004492-pat00010

The Negishi coupling reaction was the first reaction to synthesize asymmetric biaryl compounds in high yield. The Negishi coupling reaction is a reaction that forms a carbon-carbon bond between an organozinc compound and a variety of organohalogen compounds using nickel (Ni) or palladium (Pd) metal catalysts. And various organic zinc compounds can be prepared by reacting them. The organic zinc compounds generally have no side reaction and little toxicity. The following Scheme 3 shows the reaction for making the starting material for Negishi coupling reaction.

[Reaction Scheme 3]

Figure 112013025004492-pat00011

The Hiyama coupling reaction is a reaction that uses a palladium metal catalyst to form a carbon-carbon bond that occurs between an organosilicon compound and an organohalogen compound. Because the organosilicon compound is not active due to the comparable reaction to the Suzuki coupling reaction, an activator such as a fluorine anion or a basic substance is needed. The following Reaction Scheme 4 shows the reaction for making the starting material for the Hiyama coupling reaction.

[Reaction Scheme 4]

Figure 112013025004492-pat00012

Kumada coupling reaction is the first reaction using palladium (Pd) or nickel (Ni) metal as catalyst. A palladium or nickel metal catalyst is mainly used as a reaction for forming a carbon-carbon bond between the organomagnesium reactant or the organolithium reactant and the organohalogen compound. Nickel metal catalysts are used for economical conversion reactions, but in this case limited to organomagnesium compounds. Organic lithium reactants are used in a wide variety of ways because they are made in a variety of ways. Nickel metal catalyst is [1,3-bis (diphenylphosphino) propane] nickel (II) ([1,3-Bis (diphenylphosphino) propane] nickel (II) Chloride, Ni (dppp) Cl 2), 1 (Diphenylphosphino) ethane nickel (II) chloride, Ni (dppe) Cl 2 ), bis (trialkylphosphine) nickel dichloride (II) (Dichlorobis (trialkylphosphine) nickel (II), Ni (PR 3) 2 Cl 2 ) ,, bis (diphenylphosphino) butane nickel chloride (II) (Bis (diphenylphosphino) butane nickel (II) chloride, Ni (dppb) Cl 2), 1,2- bis ( (Dimethylphosphonyl) ethane chloride (II) (1,2-bis (dimethylphosphanyl) ethane nickel (II) chloride, Ni (dmpe) Cl 2 ), (dimethylphosphinoferrocene) ) nickel (II), and Ni (dmpf) Cl 2 ) are mainly used.

In order to produce a Kumada coupling reaction, an organomagnesium reaction product is prepared. The organomagnesium reaction product is prepared mainly through Grignard reaction in the first reaction product having a good leaving group. The following Scheme 5 illustrates the Grignard reaction to produce the starting material to initiate the Kumada coupling reaction.

[Reaction Scheme 5]

Figure 112013025004492-pat00013

The Sonogashira coupling reaction is a carbon-carbon bond formation reaction between an organic copper compound and an organic halogen compound using a palladium metal catalyst. A method of synthesizing an organic copper compound uses Grignard reaction or organolithium. The following Scheme 6 shows a reaction involving a Grignard reaction to produce organomagnesium in the starting material to initiate the Sonogashira coupling reaction.

[Reaction Scheme 6]

Figure 112013025004492-pat00014

Applying the above coupling reactions, it can be seen that the same result is obtained even if a chemical with a leaving group is exchanged with a chemical that undergoes a substitution reaction. As a result, the starting material in which 2-bromo-4-methylpyridine substituted 2-bromo-4-methylpyridine instead of 2-bromo-4-methylpyridine and the leaving group was replaced with the starting material A (2,4-difluoro-3- (trifluoromethyl) phenyl) -4-methylpyridine (hereinafter, referred to as " target compound " (2- (2,4-difluoro-3- (trifluoromethyl) phenyl) -4-methylpyridine can also be easily synthesized.

In Scheme 7, X is bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO -), and toluene sulfonyl (-TsO), and X 'is selected from the group consisting of bromo (-Br), iodo (-I), chloro (-Cl), methanesulfanyl (Ms-), trifluoromethanesulfonyl (TfO-), and toluenesulfonyl (-TsO).

[Reaction Scheme 7]

Figure 112013025004492-pat00015

The same result can be derived through the usual modification of such chemicals.

The following examples are synthetic examples actually selected by selecting one of the above reactions.

≪ Synthesis Example 1 &

 Synthesis of 2,4-difluoro-3- (trifluoromethyl) phenylboronic acid (2,4-difluoro-3- (trifluoromethyl) phenyl boronic acid)

A reaction vessel containing 80 mL of tetrahydrofuran (THF) was charged with 1,3-difluoro-2- (trifluoromethyl) benzene (5.00 g, 27.5 mmol (33.0 mmol) of lithium diisopropyl amide (LDA) was added dropwise at -78 ° C over 30 minutes and stirred for 1 hour. Trimethyl borate (B (OMe) 3 ) After stirring at 78 ° C for 30 minutes, the mixture is stirred at room temperature for 1 hour. Thereafter, the reaction is terminated by adding 5% aqueous solution of sodium hydroxide (NaOH) (60 mL), and after 10 minutes, 3 normal aqueous hydrochloric acid (HCl) solution is added dropwise to acidify. After extraction with diethyl ether, the organic solvent is evaporated by rotary vacuum distillation. The resultant was precipitated with dichloromethane and filtered to obtain a white solid in a yield of 80.6% (5.02 g). The results are as follows. 1 H NMR (DMSO-d 6 , 300 MHz)? (Ppm) = 7.33 (t, 1H), 7.99 (ddd, 1H), 3.57 (br, OH). MS (EI): m / z (%) 225

≪ Synthesis Example 2 &

Synthesis of 2- (2,4-difluoro-3- (trifluoromethyl) phenyl) -4-methylpyridine (2- (2,4-difluoro-3-

The reaction vessel was charged with 2,4-difluoro-3- (trifluoromethyl) phenyl boronic acid (8.00 g, 35.4 mmol), 2- Mo-4-methylpyridine (2-bromo-4-methylpyridine ) (5.54g, 32.2mmol), tetrakis (triphenylphosphine) palladium (tetrakis (triphenylphosphine) palladium, Pd (PPh 3) 4) (5mol%, 1.61 mmol) and dissolve in 100 mL of tetrahydrofuran (THF). After adding an aqueous 5% potassium carbonate (K 2 CO 3 ) solution (80 mL), reflux for 30 hours in a nitrogen atmosphere. Water is added at room temperature, and the mixture is extracted with diethyl ether. The organic layer is dried using anhydrous sodium sulfate (Na 2 SO 4 ) and the organic solvent is removed by rotary vacuum distillation. The resultant was purified by silica gel column chromatography to obtain a white solid in a yield of 90.0% (7.91 g). The results are shown in FIG. 1 H NMR (CDCl 3 , 300 MHz)? (Ppm) = 2.44 (s, 3H), 7.13 (m, 2H), 7.59 (s, 1H), 8.17 (dd, 1H), 8.58 (d, MS (EI): m / z (%) 273

Claims (18)

  1. A step of producing a compound of formula (3) from a compound of formula (2);
    (2)
    Figure 112013025004492-pat00016

    (3)
    Figure 112013025004492-pat00017

    (B) adding a compound of the formula (4) and a catalyst to the compound of the formula (3) to produce a compound of the formula (5)
    Formula 4
    Figure 112013025004492-pat00018

    Formula 5
    Figure 112013025004492-pat00019

    In the compound of Formula 2,
    X is selected from the group consisting of hydrogen (-H), bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-) (-TsO), < / RTI >
    A reactant of the step A is trimethyl borate (trimethylborate, B (OMe) 3 ), n- butyllithium (n-butyllithuim, n-BuLi ), n- tree view tiltin chloride (n-tributyltin chloride, n- Bu 3 SnCl ), Zinc (Zn), copper (I) chloride (CuCl), hexamethylcyclotrisiloxane (Me 2 SiO) 3 ,
    In the compound of Formula 3,
    R is boric acid (Boronic Acid, B (OH) 2) derivatives, trialkyltin (Trialkyltin, SnR '3) derivative, a halo-zinc (zinc halide) derivative, an alkyl silicon (alkylsilicon, SiR') derivative, a halo-magnesium (magnesium halide derivatives, organic lead derivatives, copper (Cu), and the like.
    In the compound of Formula 4,
    X 'is bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-), toluenesulfonyl , ≪ / RTI >
    In step B, the catalyst may be at least one selected from the group consisting of Palladium, Pd, Nickel, Ni, Ruthenium, Ru, Iron, Fe, Osmium, Os, (Gold, Au), Copper, Cu, Zinc, Zn, Rhodium, Rh, Iridium, Ir, Cadmium, Cd, Mercury, Silver, Ag), tin (Sn, Sn)
    Wherein R 'is independently selected from the group comprising straight or branched C 1-20 alkyl, C 3-20 cyclic alkyl.
  2. The method according to claim 1,
    Wherein X is at least one of hydrogen (-H), bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-) (-TsO), < / RTI >
    The reaction material in the step A is trimethylborate (B (OMe) 3 )
    Wherein R is the boronic acid derivative.
  3. The method according to claim 1,
    The above X may be prepared by reacting bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-), and toluenesulfonyl , ≪ / RTI >
    The reaction material of step A is n-butyllithium, n-BuLi and n-tributyltin chloride, n-Bu 3 SnCl,
    Wherein the R is a trialkyltin (SnR ' 3 ) derivative.
  4. The method according to claim 1,
    The above X may be prepared by reacting bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-), and toluenesulfonyl , ≪ / RTI >
    The reactant in step A is zinc (Zn)
    Wherein said R is a zinc halide derivative.
  5. The method according to claim 1,
    The above X may be prepared by reacting bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-), and toluenesulfonyl , ≪ / RTI >
    The reaction material of the step A is selected in order of n-butyllithium (n-BuLi) and hexamethylcyclotrisiloxane (Me 2 SiO) 3 ,
    Wherein R is an alkylsilicon derivative.
  6. The method according to claim 1,
    The above X may be prepared by reacting bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-), and toluenesulfonyl , ≪ / RTI >
    The reaction material in the step A is magnesium (Mg)
    Wherein R is an organic magnesium derivative.
  7. The method according to claim 1,
    The above X may be prepared by reacting bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-), and toluenesulfonyl , ≪ / RTI >
    The reactant in step A is copper (I) chloride (CuCl)
    In the method for producing a ligand of a blue phosphorescent dopant in which R is copper (Cu)
    Wherein the X is further reacted with magnesium (Mg) to form a ligand of the blue phosphorescent dopant.
  8. A step C for producing a compound of the formula 7 from a compound of the formula 6 below;
    6
    Figure 112013025004492-pat00020

    Formula 7
    Figure 112013025004492-pat00021

    (D) adding a compound of the formula (8) and a catalyst to the compound of the formula (7) to produce a compound of the formula (5)
    8
    Figure 112013025004492-pat00022

    Formula 5
    Figure 112013025004492-pat00023

    In the compound of Formula 6,
    X is selected from the group consisting of hydrogen (-H), bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-) (-TsO), < / RTI >
    A reactant of the step A is trimethyl borate (trimethylborate, B (OMe) 3 ), n- butyllithium (n-butyllithuim, n-BuLi ), n- tree view tiltin chloride (n-tributyltin chloride, n- Bu 3 SnCl ), Zinc (Zn), copper (I) chloride (CuCl), hexamethylcyclotrisiloxane (Me 2 SiO) 3 ,
    In the compound of Formula 7,
    R is boric acid (Boronic Acid, B (OH) 2) derivatives, trialkyltin (Trialkyltin, SnR '3) derivative, a halo-zinc (zinc halide) derivative, an alkyl silicon (alkylsilicon, SiR') derivative, a halo-magnesium (magnesium halide derivatives, organic lead derivatives, copper (Cu), and the like.
    In the compound of Formula 8,
    X 'is bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-), toluenesulfonyl , ≪ / RTI >
    In step D, the catalyst may be palladium (Pd), nickel (Ni), ruthenium (Ru), iron (Fe), osmium (Gold, Au), Copper, Cu, Zinc, Zn, Rhodium, Rh, Iridium, Ir, Cadmium, Cd, Mercury, Silver, Ag), tin (Sn, Sn)
    Wherein R 'is independently selected from the group comprising straight or branched C 1-20 alkyl, C 3-20 cyclic alkyl.
  9. 9. The method of claim 8,
    Wherein X is at least one of hydrogen (-H), bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-) (-TsO), < / RTI >
    The reaction material in the step C is trimethylborate (B (OMe) 3 )
    Wherein R is the boronic acid derivative.
  10. 9. The method of claim 8,
    The above X may be prepared by reacting bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-), and toluenesulfonyl , ≪ / RTI >
    The reaction material in the step C is n-butyllithium (n-BuLi) and n-tributyltin chloride (n-Bu 3 SnCl)
    Wherein the R is a trialkyltin (SnR ' 3 ) derivative.
  11. 9. The method of claim 8,
    The above X may be prepared by reacting bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-), and toluenesulfonyl , ≪ / RTI >
    The reaction material in step C is zinc (Zn)
    Wherein said R is a zinc halide derivative.
  12. delete
  13. 9. The method of claim 8,
    The above X may be prepared by reacting bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-), and toluenesulfonyl , ≪ / RTI >
    The reaction material in Step C is magnesium (Mg)
    Wherein R is an organic magnesium derivative.
  14. 9. The method of claim 8,
    The above X may be prepared by reacting bromo (-Br), iodo (-I), chloro (-Cl), methanesulfonyl (Ms-), trifluoromethanesulfonyl (TfO-), and toluenesulfonyl , ≪ / RTI >
    The reactant in step C is copper (I) chloride (CuCl)
    In the method for producing a ligand of a blue phosphorescent dopant in which R is copper (Cu)
    Wherein the X is further reacted with magnesium (Mg) to form a ligand of the blue phosphorescent dopant.
  15. 15. The method according to any one of claims 1 to 11, 13 and 14,
    The palladium-containing metal catalyst may be at least one selected from the group consisting of tetrakis (triphenylphosphine) palladium, Pd (PPh 3 ) 4 , bis (dibenzylideneacetone) palladium, ) 2), palladium (II) acetate (palladium (II) acetate, Pd (OAc) 2), bis (acetonitrile) dichloropalladium (II) (bis (acetonitrile) dichloropalladium (II), PdCl 2 (MeCN) 2 ), Bis (triphenylphosphine) palladium (II) dichloride (Dichlorobis (triphenylphosphane) palladium (II), PdCl 2 (PPh 3 ) 2 ), or benzylbis (triphenylphosphine) palladium (chloro) bis (triphenylphosphine) palladium (II)), BnPdCl (PPh 3 ) 2 ).
  16. 15. The method according to any one of claims 1 to 11, 13 and 14,
    Metal catalyst comprising the nickel is [1,3-bis (diphenylphosphino) propane] nickel (II) ([1,3-Bis (diphenylphosphino) propane] nickel (II) Chloride, Ni (dppp) Cl 2 ), 1,2-bis (diphenylphosphino) ethane nickel chloride (II) (1,2-bis (diphenylphosphino) ethane nickel (II) chloride, Ni (dppe) Cl 2), bis (trialkylphosphine) (II) (Dichlorobis (trialkylphosphine) nickel (II), Ni (PR3) 2Cl2), bis (diphenylphosphino) butane nickel (II) dppb) Cl 2), 1,2- bis (dimethyl phosphine isoquinoline) ethane nickel chloride (II) (1,2-bis ( dimethylphosphanyl) ethane nickel (II) chloride, Ni (dmpe) Cl 2), ( dimethyl phosphino A process for preparing a ligand of a blue phosphorescent dopant, wherein the phosphorus is nickel (II) (Dichloro (dimethylphosphinoferrocene) nickel (II), Ni (dmpf) Cl2).
  17. 15. The method according to any one of claims 1 to 11, 13 and 14,
    The step (A) or the step (C)
    Adding the compound of Formula 2 or the compound of Formula 6 to tetrahydrofuran (THF);
    Dropwise adding lithium diisopropylamide (LDA) at -78 deg. C, stirring at -78 deg. C, and stirring at room temperature; And
    Extracting with diethyl ether, and evaporating the organic solvent. The method for producing a blue phosphorescent dopant ligand according to claim 1,
  18. 15. The method according to any one of claims 1 to 11, 13 and 14,
    The step (B) or (D)
    Adding the compound of Formula 6 to the compound of Formula 3 or the compound of Formula 8 to the compound of Formula 8;
    Further adding the metal catalyst; And
    Extracting with diethyl ether, and evaporating the organic solvent. The method for producing a blue phosphorescent dopant ligand according to claim 1,
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020064681A1 (en) 2000-09-26 2002-05-30 Takao Takiguchi Luminescence device, display apparatus and metal coordination compound
US20020121638A1 (en) 2000-06-30 2002-09-05 Vladimir Grushin Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds
US7011897B2 (en) 2002-08-16 2006-03-14 The University Of Southern California Organic light emitting materials and devices

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020121638A1 (en) 2000-06-30 2002-09-05 Vladimir Grushin Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds
US20020064681A1 (en) 2000-09-26 2002-05-30 Takao Takiguchi Luminescence device, display apparatus and metal coordination compound
US7011897B2 (en) 2002-08-16 2006-03-14 The University Of Southern California Organic light emitting materials and devices

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