Patent Application
20210226133
The present specification relates to a heterocyclic compound and an organic light emitting device comprising the same.
An electroluminescent device is one type of self-emissive display devices, and has an advantage of having a wide viewing angle, and a high response speed as well as having an excellent contrast.
An organic light emitting device has a structure disposing an organic thin film between two electrodes. When a voltage is applied to an organic light emitting device having such a structure, electrons and holes injected from the two electrodes bind and pair in the organic thin film, and light emits as these annihilate. The organic thin film may be formed in a single layer or a multilayer as necessary.
A material of the organic thin film may have a light emitting function as necessary. For example, as a material of the organic thin film, compounds capable of forming a light emitting layer themselves alone may be used, or compounds capable of performing a role of a host or a dopant of a host-dopant-based light emitting layer may also be used. In addition thereto, compounds capable of performing roles of hole injection, hole transfer, electron blocking, hole blocking, electron transfer, electron injection and the like may also be used as a material of the organic thin film.
Development of an organic thin film material has been continuously required for enhancing performance, lifetime or efficiency of an organic light emitting device.
The present disclosure is directed to providing a heterocyclic compound and an organic light emitting device comprising the same.
One embodiment of the present application provides a heterocyclic compound represented by the following Chemical Formula 1.
In Chemical Formula 1,
X is O or S,
L1 and L2 are the same as or different from each other, and each independently a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group,
Z1 and Z2 are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; —SiRR′R″; or —P(═O)RR′,
Ra and Rb are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; a halogen group; —CN; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; —SiRR′R″; —P(═O)RR′; and an amine group unsubstituted or substituted with a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or two or more groups adjacent to each other bond to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,
R, R′ and R″ are the same as or different from each other, and each independently hydrogen; deuterium; —CN; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group,
p and n are an integer of 1 to 3,
m, q and s are an integer of 1 to 4,
r is an integer of 0 to 4, and
when r is an integer of 0 and Z2 is hydrogen, n is an integer of 2 or 3, and Rb is a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or two or more groups adjacent to each other bond to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring.
Another embodiment of the present application provides an organic light emitting device comprising a first electrode; a second electrode provided opposite to the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers comprise the heterocyclic compound represented by Chemical Formula 1.
The compound described in the present specification can be used as an organic material layer material of an organic light emitting device. The compound is capable of performing a role of a hole injection material, a hole transfer material, a light emitting material, an electron transfer material, an electron injection material and the like in the organic light emitting device. Particularly, the heterocyclic compound represented by Chemical Formula 1 can be used as an electron transfer layer material, a hole blocking layer material or a charge generation layer material of the organic light emitting device. In addition, when using the compound represented by Chemical Formula 1 in the organic material layer, a driving voltage is lowered and light efficiency is enhanced in the device, and device lifetime properties can be enhanced by thermal stability of the compound.
Particularly, the heterocyclic compound represented by Chemical Formula 1 has both N-type and P-type substituents in one core structure, and by having a P-type substituent, hole properties can be strengthened in the molecule. The compound of Chemical Formula 1 is a bipolar type having both a P-type and an N-type, and is thereby capable of blocking hole leakage and effectively trapping excitons in a light emitting layer. In addition, hole properties are strengthened in a specific device structure changing electron mobility relatively slowly, which balances electrons and holes in the light emitting layer properly forming a recombination region of the excitons, and as a result, efficiency and lifetime increase.
Hereinafter, the present application will be described in detail.
The term “substituted” means a hydrogen atom bonding to a carbon atom of a compound is changed to another substituent, and the position of substitution is not limited as long as it is a position at which the hydrogen atom is substituted, that is, a position at which a substituent can substitute, and when two or more substituents substitute, the two or more substituents may be the same as or different from each other.
In the present specification, the halogen may be fluorine, chlorine, bromine or iodine.
In the present specification, the alkyl group comprises linear or branched having 1 to 60 carbon atoms, and may be further substituted with other substituents. The number of carbon atoms of the alkyl group may be from 1 to 60, specifically from 1 to 40 and more specifically from 1 to 20. Specific examples thereof may comprise a methyl group, an ethyl group, a propyl group, an n-propyl group, an isopropyl group, a butyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a 1-methyl-butyl group, a 1-ethyl-butyl group, a pentyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, an n-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 4-methyl-2-pentyl group, a 3,3-dimethylbutyl group, a 2-ethylbutyl group, a heptyl group, an n-heptyl group, a 1-methylhexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, an octyl group, an n-octyl group, a tert-octyl group, a 1-methylheptyl group, a 2-ethylhexyl group, a 2-propylpentyl group, an n-nonyl group, a 2,2-dimethylheptyl group, a 1-ethyl-propyl group, a 1,1-dimethyl-propyl group, an isohexyl group, a 2-methylpentyl group, a 4-methylhexyl group, a 5-methylhexyl group and the like, but are not limited thereto.
In the present specification, the alkenyl group comprises linear or branched having 2 to 60 carbon atoms, and may be further substituted with other substituents. The number of carbon atoms of the alkenyl group may be from 2 to 60, specifically from 2 to 40 and more specifically from 2 to 20. Specific examples thereof may comprise a vinyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 3-methyl-1-butenyl group, a 1,3-butadienyl group, an allyl group, a 1-phenylvinyl-1-yl group, a 2-phenylvinyl-1-yl group, a 2,2-diphenylvinyl-1-yl group, a 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl group, a 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, a stilbenyl group, a styrenyl group and the like, but are not limited thereto.
In the present specification, the alkynyl group comprises linear or branched having 2 to 60 carbon atoms, and may be further substituted with other substituents. The number of carbon atoms of the alkynyl group may be from 2 to 60, specifically from 2 to 40 and more specifically from 2 to 20.
In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably from 1 to 20. Specific examples thereof may comprise methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benxyloxy, p-methylbenzyloxy and the like, but are not limited thereto.
In the present specification, the cycloalkyl group comprises monocyclic or multicyclic having 3 to 60 carbon atoms, and may be further substituted with other substituents. Herein, the multicyclic means a group in which the cycloalkyl group is directly linked to or fused with other cyclic groups. Herein, the other cyclic groups may be a cycloalkyl group, but may also be different types of cyclic groups such as a heterocycloalkyl group, an aryl group and a heteroaryl group. The number of carbon groups of the cycloalkyl group may be from 3 to 60, specifically from 3 to 40 and more specifically from 5 to 20. Specific examples thereof may comprise a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 3-methylcyclopentyl group, a 2,3-dimethylcyclopentyl group, a cyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a 2,3-dimethylcyclohexyl group, a 3,4,5-trimethylcyclohexyl group, a 4-tert-butylcyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like, but are not limited thereto.
In the present specification, the heterocycloalkyl group comprises O, S, Se, N or Si as a heteroatom, comprises monocyclic or multicyclic having 2 to 60 carbon atoms, and may be further substituted with other substituents. Herein, the multicyclic means a group in which the heterocycloalkyl group is directly linked to or fused with other cyclic groups. Herein, the other cyclic groups may be a heterocycloalkyl group, but may also be different types of cyclic groups such as a cycloalkyl group, an aryl group and a heteroaryl group. The number of carbon atoms of the heterocycloalkyl group may be from 2 to 60, specifically from 2 to 40 and more specifically from 3 to 20.
In the present specification, the aryl group comprises monocyclic or multicyclic having 6 to 60 carbon atoms, and may be further substituted with other substituents. Herein, the multicyclic means a group in which the aryl group is directly linked to or fused with other cyclic groups. Herein, the other cyclic groups may be an aryl group, but may also be different types of cyclic groups such as a cycloalkyl group, a heterocycloalkyl group and a heteroaryl group. The aryl group comprises a spiro group. The number of carbon atoms of the aryl group may be from 6 to 60, specifically from 6 to 40 and more specifically from 6 to 25. Specific examples of the aryl group may comprise a phenyl group, a biphenyl group, a triphenyl group, a naphthyl group, an anthryl group, a chrysenyl group, a phenanthrenyl group, a perylenyl group, a fluoranthenyl group, a triphenylenyl group, a phenalenyl group, a pyrenyl group, a tetracenyl group, a pentacenyl group, a fluorenyl group, an indenyl group, an acenaphthylenyl group, a benzofluorenyl group, a spirobifluorenyl group, a 2,3-dihydro-1H-indenyl group, a fused ring thereof, and the like, but are not limited thereto.
In the present specification, the silyl group is a substituent comprising Si, having the Si atom directly linked as a radical, and is represented by —SiR104R105R106. R104 to R106 are the same as or different from each other, and may be each independently a substituent formed with at least one of hydrogen; deuterium; a halogen group; an alkyl group; an alkenyl group; an alkoxy group; a cycloalkyl group; an aryl group; and a heterocyclic group. Specific examples of the silyl group may comprise a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group and the like, but are not limited thereto.
In the present specification, the fluorenyl group may be substituted, and adjacent substituents may bond to each other to form a ring.
When the fluorenyl group is substituted,
and the like may be included. However, the structure is not limited thereto.
In the present specification, the heteroaryl group comprises O, S, Se, N or Si as a heteroatom, comprises monocyclic or multicyclic having 2 to 60 carbon atoms, and may be further substituted with other substituents. Herein, the multicyclic means a group in which the heteroaryl group is directly linked to or fused with other cyclic groups. Herein, the other cyclic groups may be a heteroaryl group, but may also be different types of cyclic groups such as a cycloalkyl group, a heterocycloalkyl group and an aryl group. The number of carbon atoms of the heteroaryl group may be from 2 to 60, specifically from 2 to 40 and more specifically from to 25. Specific examples of the heteroaryl group may comprise a pyridyl group, a pyrrolyl group, a pyrimidyl group, a pyridazinyl group, a furanyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a triazolyl group, an isothiazolyl group, a triazolyl group, a furazanyl group, an oxadiazolyl group, a thiadiazolyl group, a dithiazolyl group, a tetrazolyl group, a pyranyl group, a thiopyranyl group, a diazinyl group, an oxazinyl group, a triazinyl group, a dioxynyl group, a triazinyl group, a tetrazinyl group, a quinolyl group, an isoquinolyl group, a quinazolinyl group, an isoquinazolinyl group, a qninozolinyl group, a naphthyridyl group, an acridinyl group, a phenanthridinyl group, an imidazopyridinyl group, a diazanaphthalenyl group, a triazaindene group, an indolyl group, an indolizinyl group, a benzothiazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiophene group, a benzofuran group, a dibenzothiophene group, a dibenzofuran group, a carbazolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a phenazinyl group, a dibenzosilole group, spirobi(dibenzosilole), a dihydrophenazinyl group, a phenoxazinyl group, a phenanthridyl group, an imidazopyridinyl group, a thienyl group, an indolo[2,3-a]carbazolyl group, an indolo[2,3-b]carbazolyl group, an indolinyl group, a 10,11-dihydro-dibenzo[b,f]azepine group, a 9,10-dihydroacridinyl group, a phenanthrazinyl group, a phenothiathiazinyl group, a phthalazinyl group, a naphthylidinyl group, a phenanthrolinyl group, a benzo[c][1,2,5]thiadiazolyl group, a 5,10-dihydrobenzo[b,e][1,4]azasilinyl, a pyrazolo[1,5-c]quinazolinyl group, a pyrido[1,2-b]indazolyl group, a pyrido[1,2-a]imidazo[1,2-e]indolinyl group, a 5,11-dihydroindeno[1,2-b]carbazolyl group and the like, but are not limited thereto.
In the present specification, the amine group may be selected from the group consisting of a monoalkylamine group; a monoarylamine group; a monoheteroarylamine group; —NH2; a dialkylamine group; a diarylamine group; a diheteroarylamine group; an alkylarylamine group; an alkylheteroarylamine group; and an arylheteroarylamine group, and although not particularly limited thereto, the number of carbon atoms is preferably from 1 to 30. Specific examples of the amine group may comprise a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, a dibiphenylamine group, an anthracenylamine group, a 9-methyl-anthracenylamine group, a diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a triphenylamine group, a biphenylnaphthylamine group, a phenylbiphenylamine group, a biphenylfluorenylamine group, a phenyltriphenylenylamine group, a biphenyltriphenylenylamine group and the like, but are not limited thereto.
In the present specification, the arylene group means the aryl group having two bonding sites, that is, a divalent group. Descriptions on the aryl group provided above may be applied thereto except for each being a divalent. In addition, the heteroarylene group means the heteroaryl group having two bonding sites, that is, a divalent group. Descriptions on the heteroaryl group provided above may be applied thereto except for each being a divalent.
In the present specification, specific examples of the phosphine oxide group may comprise a diphenylphosphine oxide group, a dinaphthylphosphine oxide group and the like, but are not limited thereto.
In the present specification, an “adjacent” group may mean a substituent substituting an atom directly linked to an atom substituted by the corresponding substituent, a substituent sterically most closely positioned to the corresponding substituent, or another substituent substituting an atom substituted by the corresponding substituent. For example, two substituents substituting ortho positions in a benzene ring, and two substituents substituting the same carbon in an aliphatic ring may be interpreted as groups “adjacent” to each other.
In the present specification, the term “substituted” means a hydrogen atom bonding to a carbon atom of a compound is changed to another substituent, and the position of substitution is not limited as long as it is a position at which the hydrogen atom is substituted, that is, a position at which a substituent can substitute, and when two or more substituents substitute, the two or more substituents may be the same as or different from each other.
In the present specification, “substituted or unsubstituted” means being substituted with one or more substituents selected from the group consisting of C1 to C60 linear or branched alkyl; C2 to C60 linear or branched alkenyl; C2 to C60 linear or branched alkynyl; C3 to C60 monocyclic or polycyclic cycloalkyl; C2 to C60 monocyclic or polycyclic heterocycloalkyl; C6 to C60 monocyclic or polycyclic aryl; C2 to C60 monocyclic or polycyclic heteroaryl; —SiRR′R″; P(═O)RR′; C1 to C20 alkylamine; C6 to C60 monocyclic or polycyclic arylamine; and C2 to C60 monocyclic or polycyclic heteroarylamine, or being unsubstituted, or being substituted with a substituent linking two or more substituents selected from among the substituents illustrated above, or being unsubstituted.
One embodiment of the present application provides a compound represented by Chemical Formula 1.
In one embodiment of the present application, X of Chemical Formula 1 may be 0 or S.
In one embodiment of the present application, X of Chemical Formula 1 may be O.
In one embodiment of the present application, X of Chemical Formula 1 may be S.
In one embodiment of the present application, Ra of Chemical Formula 1 may be selected from the group consisting of hydrogen; deuterium; a halogen group; —CN; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; —SiRR′R″; —P(═O)RR′; and an amine group unsubstituted or substituted with a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or two or more groups adjacent to each other may bond to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring.
In another embodiment, Ra of Chemical Formula 1 may be hydrogen; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group.
In another embodiment, Ra of Chemical Formula 1 may be hydrogen; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.
In another embodiment, Ra of Chemical Formula 1 may be hydrogen; a C6 to C30 aryl group; or a C2 to C30 heteroaryl group.
In another embodiment, Ra of Chemical Formula 1 may be hydrogen.
In one embodiment of the present application, L1 may be a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group.
In another embodiment, L1 may be a substituted or unsubstituted C6 to C60 arylene group; or a substituted or unsubstituted C2 to C60 heteroarylene group.
In another embodiment, L1 may be a substituted or unsubstituted C6 to C40 arylene group; or a substituted or unsubstituted C2 to C40 heteroarylene group.
In another embodiment, L1 may be a substituted or unsubstituted monocyclic or polycyclic C6 to C40 arylene group; or a substituted or unsubstituted C2 to C40 N-containing heteroarylene group.
In another embodiment, L1 may be a monocyclic or polycyclic C6 to C40 arylene group; or a C2 to C40 N-containing heteroarylene group.
In another embodiment, L1 may be a phenylene group; a biphenylene group; a triphenylenylene group; a naphthylene group; a phenanthrenylene group; a divalent pyridine group; a divalent pyrimidine group; a divalent phenanthroline group or a divalent triazine group.
In one embodiment of the present application, Z1 may be hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; —SiRR′R″; or —P(═O)RR′.
In another embodiment, Z1 may be hydrogen; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; —SiRR′R″; or —P(═O)RR′.
In another embodiment, Z1 may be hydrogen; a substituted or unsubstituted C1 to C40 alkyl group; a substituted or unsubstituted C6 to C40 aryl group; a substituted or unsubstituted C2 to C40 heteroaryl group; —SiRR′R″; or —P(═O)RR′.
In another embodiment, Z1 may be hydrogen; a substituted or unsubstituted C6 to C40 aryl group; a substituted or unsubstituted C2 to C40 heteroaryl group; or —P(═O)RR′.
In another embodiment, Z1 may be hydrogen; a C6 to C40 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of a C6 to C40 aryl group and a C2 to C40 heteroaryl group; a C2 to C40 heteroaryl group; or —P(═O)RR′.
In another embodiment, Z1 may be hydrogen; a phenyl group unsubstituted or substituted with a carbazole group, a dibenzofuran group or a dibenzothiophene group; a biphenyl group; a dibenzofuran group; a dibenzothiophene group; a pyridine group; a pyrimidine group; a triazine group; or —P(═O)RR′.
In one embodiment of the present application, Rb of Chemical Formula 1 may be selected from the group consisting of hydrogen; deuterium; a halogen group; —CN; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; —SiRR′R″; —P(═O)RR′; and an amine group unsubstituted or substituted with a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or two or more groups adjacent to each other may bond to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring.
In another embodiment, Rb of Chemical Formula 1 may be selected from the group consisting of hydrogen; a substituted or unsubstituted C1 to C60 alkyl group; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; —SiRR′R″; —P(═O)RR′; and an amine group unsubstituted or substituted with a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or two or more groups adjacent to each other may bond to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring.
In another embodiment, Rb of Chemical Formula 1 may be selected from the group consisting of hydrogen; a substituted or unsubstituted C6 to C60 aryl group; and a substituted or unsubstituted C2 to C60 heteroaryl group, or two or more groups adjacent to each other may bond to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring.
In another embodiment, Rb of Chemical Formula 1 may be selected from the group consisting of hydrogen; a substituted or unsubstituted C6 to C40 aryl group; and a substituted or unsubstituted C2 to C40 heteroaryl group, or two or more groups adjacent to each other may bond to each other to form a substituted or unsubstituted aromatic hydrocarbon ring.
In another embodiment, Rb of Chemical Formula 1 may be selected from the group consisting of hydrogen; a C6 to C40 aryl group unsubstituted or substituted with one or more substituents selected from the group consisting of a C6 to C40 aryl group and a C2 to C40 heteroaryl group; and a C2 to C40 heteroaryl group, or two or more groups adjacent to each other may bond to each other to form C6 to C40 aromatic hydrocarbon ring.
In another embodiment, Rb of Chemical Formula 1 may be selected from the group consisting of hydrogen; a phenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of a triphenylene group, a phenanthrene group, a dibenzothiophene group and a dibenzofuran group; a biphenyl group; a naphthyl group; a phenanthrene group; a triphenylene group; a dibenzofuran group; and a dibenzothiophene group, or two or more groups adjacent to each other may bond to each other to form a benzene ring.
In one embodiment of the present application, L2 may be a substituted or unsubstituted arylene group; or a substituted or unsubstituted heteroarylene group.
In another embodiment, L2 may be a substituted or unsubstituted C6 to C60 arylene group; or a substituted or unsubstituted C2 to C60 heteroarylene group.
In another embodiment, L2 may be a substituted or unsubstituted C6 to C40 arylene group; or a substituted or unsubstituted C2 to C40 heteroarylene group.
In another embodiment, L2 may be a C6 to C40 arylene group; or a C2 to C40 heteroarylene group.
In another embodiment, L2 may be a phenylene group; a biphenylene group; a triphenylenylene group; a phenanthrenylene group; a divalent pyridine group; a divalent pyrimidine group; a divalent quinoline group; a divalent phenanthroline group or a divalent triazine group.
In one embodiment of the present application, Z2 may be hydrogen; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; or P(═O)RR′.
In another embodiment, Z2 may be hydrogen; a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; or P(═O)RR′.
In another embodiment, Z2 may be hydrogen; a substituted or unsubstituted C6 to C40 aryl group; a substituted or unsubstituted C2 to C40 heteroaryl group; or P(═O)RR′.
In another embodiment, Z2 may be hydrogen; a C6 to C40 aryl group unsubstituted or substituted with a C6 to C40 heteroaryl group; a C2 to C40 heteroaryl group; or P(═O)RR′.
In another embodiment, Z2 may be hydrogen; a phenyl group unsubstituted or substituted with a carbazole group, a dibenzofuran group or a dibenzothiophene group; a biphenyl group; a pyridine group; a pyrimidine group; a triazine group; or P(═O)RR′.
In one embodiment of the present application, R, R′ and R″ are the same as or different from each other, and may be each independently hydrogen; deuterium; —CN; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group.
In another embodiment, R, R′ and R″ are the same as or different from each other, and may be each independently hydrogen; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group.
In another embodiment, R, R′ and R″ are the same as or different from each other, and may be each independently hydrogen; a substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heteroaryl group.
In another embodiment, R, R′ and R″ are the same as or different from each other, and may be each independently a substituted or unsubstituted C6 to C60 aryl group.
In another embodiment, R, R′ and R″ are the same as or different from each other, and may be each independently a C6 to C60 aryl group.
In another embodiment, R, R′ and R″ are the same as or different from each other, and may be each independently a C6 to C40 aryl group.
In another embodiment, R, R′ and R″ are the same as or different from each other, and may be each independently a phenyl group.
In one embodiment of the present application, p of Chemical Formula 1 may be 1.
In one embodiment of the present application, p of Chemical Formula 1 may be 2.
In one embodiment of the present application, p of Chemical Formula 1 may be 3.
In one embodiment of the present application, q of Chemical Formula 1 may be 1.
In one embodiment of the present application, q of Chemical Formula 1 may be 2.
In one embodiment of the present application, q of Chemical Formula 1 may be 3.
In one embodiment of the present application, r of Chemical Formula 1 may be 0.
In one embodiment of the present application, r of Chemical Formula 1 may be 1.
In one embodiment of the present application, r of Chemical Formula 1 may be 2.
In one embodiment of the present application, r of Chemical Formula 1 may be 3.
In one embodiment of the present application, s of Chemical Formula 1 may be 1.
In one embodiment of the present application, s of Chemical Formula 1 may be 2.
In one embodiment of the present application, s of Chemical Formula 1 may be 3.
In one embodiment of the present application, s of Chemical Formula 1 may be 4.
In one embodiment of the present application, when r is an integer of 0 and Z2 is hydrogen in Chemical Formula 1, n is an integer of 2 or 3, and Rb is a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or two or more groups adjacent to each other bond to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring.
In another embodiment, when r is an integer of 0 and Z2 is hydrogen in Chemical Formula 1, n is an integer of 2, and adjacent two Rbs may bond to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring.
In another embodiment, when r is an integer of 0 and Z2 is hydrogen in Chemical Formula 1, n is an integer of 2, and adjacent two Rbs may bond to each other to form a substituted or unsubstituted aromatic hydrocarbon ring.
In another embodiment, when r is an integer of 0 and Z2 is hydrogen in Chemical Formula 1, n is an integer of 2, and adjacent two Rbs may bond to each other to form a substituted or unsubstituted C3 to C60 aromatic hydrocarbon ring.
In another embodiment, when r is an integer of 0 and Z2 is hydrogen in Chemical Formula 1, n is an integer of 2, and adjacent two Rbs may bond to each other to form a substituted or unsubstituted C3 to C30 aromatic hydrocarbon ring.
In another embodiment, when r is an integer of 0 and Z2 is hydrogen in Chemical Formula 1, n is an integer of 2, and adjacent two Rbs may bond to each other to form a C3 to C30 aromatic hydrocarbon ring.
In another embodiment, when r is an integer of 0 and Z2 is hydrogen in Chemical Formula 1, n is an integer of 2, and adjacent two Rbs may bond to each other to form a benzene ring.
In the heterocyclic compound provided in one embodiment of the present application, Chemical Formula 1 is represented by any one of the following Chemical Formulae 2 to 5.
In Chemical Formulae 2 to 5,
L1, L2, Z1, Z2, X, p, q, r and s each have the same definition as in Chemical Formula 1.
In the heterocyclic compound provided in one embodiment of the present application, Chemical Formula 1 is represented by any one of the following Chemical Formulae 6 to 11.
In Chemical Formulae 6 to 11,
Ra, L1, Z1, p, q and m each have the same definition as in Chemical Formula 1.
The heterocyclic compound represented by Chemical Formula 1 has both N-type and P-type substituents in one core structure, and by having a P-type substituent, hole properties may be strengthened in the molecule. The compound of Chemical Formula 1 is a bipolar type having both a P-type and an N-type, and is thereby capable of blocking hole leakage and effectively trapping excitons in a light emitting layer. In addition, hole properties are strengthened in a specific device structure changing electron mobility relatively slowly, which balances electrons and holes in the light emitting layer properly forming a recombination region of the excitons, and as a result, efficiency and lifetime increase.
In the heterocyclic compound provided in one embodiment of the present application, Chemical Formula 1 is represented by any one of the following compounds.
The compound according to one embodiment of the present application may be prepared according to the following General Formula 1.
In General Formula 1, X has the same definition as X in Chemical Formula 1, and R10 or R11 has the same definition as
In addition, by introducing various substituents to the structures of Chemical Formulae 1 to 11, compounds having unique properties of the introduced substituents may be synthesized. For example, by introducing substituents normally used as hole injection layer materials, hole transfer layer materials, light emitting layer materials, electron transfer layer materials and charge generation layer materials used for manufacturing an organic light emitting device to the core structure, materials satisfying conditions required for each organic material layer may be synthesized.
In addition, by introducing various substituents to the structures of Chemical Formulae 1 to 11, the energy band gap may be finely controlled, and meanwhile, properties at interfaces between organic materials are enhanced, and material applications may become diverse.
Meanwhile, the compound has a high glass transition temperature (Tg), and has excellent thermal stability. Such an increase in the thermal stability becomes an important factor providing driving stability to a device.
Another embodiment of the present application provides an organic light emitting device comprising a first electrode; a second electrode provided opposite to the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers comprise the heterocyclic compound.
In one embodiment of the present application, the first electrode may be an anode, and the second electrode may be a cathode.
In another embodiment, the first electrode may be a cathode, and the second electrode may be an anode.
In one embodiment of the present application, the organic light emitting device may be a blue organic light emitting device, and the heterocyclic compound according to Chemical Formula 1 may be used as a material of the blue organic light emitting device.
In one embodiment of the present application, the organic light emitting device may be a green organic light emitting device, and the heterocyclic compound according to Chemical Formula 1 may be used as a material of the green organic light emitting device.
In one embodiment of the present application, the organic light emitting device may be a red organic light emitting device, and the heterocyclic compound according to Chemical Formula 1 may be used as a material of the red organic light emitting device.
Specific descriptions on the heterocyclic compound represented by Chemical Formula 1 are the same as the descriptions provided above.
The organic light emitting device of the present disclosure may be manufactured using common organic light emitting device manufacturing methods and materials except that one or more organic material layers are formed using the heterocyclic compound described above.
The heterocyclic compound may be formed into an organic material layer through a solution coating method as well as a vacuum deposition method when manufacturing the organic light emitting device. Herein, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, a spray method, roll coating and the like, but is not limited thereto.
The organic material layer of the organic light emitting device of the present disclosure may be formed in a single layer structure, or may also be formed in a multilayer structure in which two or more organic material layers are laminated. For example, the organic light emitting device according to one embodiment of the present disclosure may have a structure comprising a hole injection layer, a hole transfer layer, a light emitting layer, an electron transfer layer, an electron injection layer and the like as the organic material layer. However, the structure of the organic light emitting device is not limited thereto, and may comprise less numbers of organic material layers.
In the organic light emitting device of the present disclosure, the organic material layer may comprise a light emitting layer, and the light emitting layer may comprise the heterocyclic compound represented by Chemical Formula 1.
In another organic light emitting device, the organic material layer comprises a light emitting layer, the light emitting layer comprises a host material, and the host material may comprise the heterocyclic compound represented by Chemical Formula 1.
In another embodiment, the organic material layer comprising the heterocyclic compound comprises the heterocyclic compound represented by Chemical Formula 1 as a host, and may be used together with a phosphorescent dopant.
In another embodiment, the organic material layer comprising the heterocyclic compound comprises the heterocyclic compound represented by Chemical Formula 1 as a host, and may be used together with an iridium-based dopant.
As a material of the phosphorescent dopant, those known in the art may be used.
For example, phosphorescent dopant materials represented by LL′MX, LL′L″M, LMXX′, L2MX and L3M may be used, however, the scope of the present disclosure is not limited to these examples.
Herein, L, L′, L″, X and X′ are bidentate ligands different from each other, and M is a metal forming an octahedral complex.
M may comprise iridium, platinum, osmium or the like.
L is an anionic bidentate ligand coordinated to M as the iridium-based dopant by sp2 carbon and heteroatom, and X may perform a function of trapping electrons or holes. Nonlimiting examples of L may comprise 2-(1-naphthyl)benzoxazole, (2-phenylbenzoxazole), (2-phenylbenzothiazole), (2-phenylbenzothiazole), (7,8-benzoquinoline), (thiophene group pyrizine), phenylpyridine, benzothiophene group pyrizine, 3-methoxy-2-phenylpyridine, thiophene group pyrizine, tolylpyridine and the like. Nonlimiting examples of X may comprise acetylacetonate (acac), hexafluoroacetylacetonate, salicylidene, picolinate, 8-hydroxyquinolate and the like.
More specific examples thereof are presented below, however, the phosphorescent dopant is not limited to these examples.
In one embodiment of the present application, as the iridium-based dopant, Ir(ppy)3 may be used as a green phosphorescent dopant.
In one embodiment of the present application, the dopant content may be from 1% to 15%, preferably from 3% to 10% and more preferably from 5% to 10% based on the whole light emitting layer.
In the organic light emitting device of the present disclosure, the organic material layer comprises an electron injection layer or an electron transfer layer, and the electron injection layer or the electron transfer layer may comprise the heterocyclic compound.
In another organic light emitting device, the organic material layer comprises an electron blocking layer or a hole blocking layer, and the electron blocking layer or the hole blocking layer may comprise the heterocyclic compound.
In another organic light emitting device, the organic material layer comprises an electron transfer layer, a light emitting layer or a hole blocking layer, and the electron transfer layer, the light emitting layer or the hole blocking layer may comprise the heterocyclic compound.
The organic light emitting device of the present disclosure may further comprise one, two or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transfer layer, an electron injection layer, an electron transfer layer, an electron blocking layer and a hole blocking layer.
The organic material layer comprising Chemical Formula 1 may further comprise other materials as necessary.
In addition, the organic light emitting device according to one embodiment of the present application comprises a first electrode, a second electrode, and two or more stacks provided between the first electrode and the second electrode, wherein the two or more stacks each independently comprise a light emitting layer, a charge generation layer is included between the two or more stacks, and the charge generation layer comprises the heterocyclic compound represented by Chemical Formula 1.
In addition, the organic light emitting device according to one embodiment of the present application may comprise a first electrode, a first stack provided on the first electrode and comprising a first light emitting layer, a charge generation layer provided on the first stack, a second stack provided on the charge generation layer and comprising a second light emitting layer, and a second electrode provided on the second stack. Herein, the charge generation layer may comprise the heterocyclic compound represented by Chemical Formula 1. In addition, the first stack and the second stack may each independently further comprise one or more types of the hole injection layer, the hole transfer layer, the hole blocking layer, the electron transfer layer, the electron injection layer described above and the like.
The charge generation layer may be an N-type charge generation layer, and the charge generation layer may further comprise a dopant known in the art in addition to the heterocyclic compound represented by Chemical Formula 1.
As the organic light emitting device according to one embodiment of the present application, an organic light emitting device having a 2-stack tandem structure is schematically illustrated in
The organic material layer comprising Chemical Formula 1 may further comprise other materials as necessary.
In the organic light emitting device according to one embodiment of the present application, materials other than the compound of Chemical Formula 1 are illustrated below, however, these are for illustrative purposes only and not for limiting the scope of the present application, and may be replaced by materials known in the art.
As the anode material, materials having relatively large work function may be used, and transparent conductive oxides, metals, conductive polymers or the like may be used. Specific examples of the anode material comprise metals such as vanadium, chromium, copper, zinc and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.
As the cathode material, materials having relatively small work function may be used, and metals, metal oxides, conductive polymers or the like may be used. Specific examples of the cathode material comprise metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; multilayer structure materials such as LiF/Al or LiO2/Al, and the like, but are not limited thereto.
As the hole injection material, known hole injection materials may be used, and for example, phthalocyanine compounds such as copper phthalocyanine disclosed in U.S. Pat. No. 4,356,429, or starburst-type amine derivatives such as tris(4-carbazoyl-9-ylphenyl)amine (TCTA), 4,4′,4″-tri[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA) or 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB) described in the literature [Advanced Material, 6, p. 677 (1994)], polyaniline/dodecylbenzene sulfonic acid, poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate), polyaniline/camphor sulfonic acid or polyaniline/poly(4-styrene-sulfonate) that are conductive polymers having solubility, and the like, may be used.
As the hole transfer material, pyrazoline derivatives, arylamine-based derivatives, stilbene derivatives, triphenyldiamine derivatives and the like may be used, and low molecular or high molecular materials may also be used.
As the electron transfer material, metal complexes of oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, 8-hydroxyquinoline and derivatives thereof, and the like, may be used, and high molecular materials may also be used as well as low molecular materials.
As examples of the electron injection material, LiF is typically used in the art, however, the present application is not limited thereto.
As the light emitting material, red, green or blue light emitting materials may be used, and as necessary, two or more light emitting materials may be mixed and used. Herein, two or more light emitting materials may be used by being deposited as individual sources of supply or by being premixed and deposited as one source of supply. In addition, fluorescent materials may also be used as the light emitting material, however, phosphorescent materials may also be used. As the light emitting material, materials emitting light by bonding electrons and holes injected from an anode and a cathode, respectively, may be used alone, however, materials having a host material and a dopant material involved in light emission together may also be used.
When mixing light emitting material hosts, same series hosts may be mixed, or different series hosts may be mixed. For example, any two or more types of materials among n-type host materials or P-type host materials may be selected, and used as a host material of a light emitting layer.
The organic light emitting device according to one embodiment of the present application may be a top-emission type, a bottom-emission type or a dual-emission type depending on the materials used.
The heterocyclic compound according to one embodiment of the present application may also be used in an organic electronic device comprising an organic solar cell, an organic photo conductor, an organic transistor and the like under a similar principle used in the organic light emitting device.
Hereinafter, the present specification will be described in more detail with reference to examples, however, these are for illustrative purposes only, and the scope of the present application is not limited thereto.
After dissolving benzo[b]thiophen-3-ylboronic acid (162 g, 1000 mmol) and 2-bromo-6-chloroaniline (189 g, 1100 mmol) in toluene, EtOH and H2O (2000 mL:400 mL:400 mL), Pd(PPh3)4 (58 g, 50 mmol) and NaHCO3 (252 g, 3000 mmol) were introduced thereto, and the result was refluxed for 4 hours. After the reaction was completed, the result was cooled to room temperature and extracted with MC. The result was dried with anhydrous MgSO4, and then the solvent was removed using a rotary evaporator. Target Compound 1-5 was obtained using column chromatography (MC:Hx=1:3). (190 g, 91%, brown oil)
Compound 1-5 (95 g, 428 mmol) and triethylamine (190 mL, 1362 mmol) were introduced to MC (1500 mL) and dissolved therein. 4-Bromobenzoyl chloride (149 g, 681 mmol) dissolved in MC (300 mL) was slowly added dropwise to the mixture at 0° C. After the reaction was completed, MC and distilled water were introduced to the reaction solution for extraction. After that, the result was dried with anhydrous MgSO4, and, after removing the solvent using a rotary evaporator, recrystallized with EA/Hx to obtain Compound 1-4. (82 g, 91%, white solid)
After dissolving Compound 1-4 (82 g, 210 mmol) in nitrobenzene (1000 mL), POCl3 (24 mL, 210 mmol) was slowly added dropwise thereto. After that, the result was stirred for 12 hours at 150° C. After the reaction was completed, the reaction solution was neutralized with an aqueous NaHCO3 solution. Solids produced from the neutralization were filtered. The solids were recrystallized with MC/MeOH to obtain target Compound 1-3. (69 g, 88%, white solid)
After dissolving Compound 1-3 (61 g, 163 mmol), bis(pinacolato)diboron (62 g, 244 mmol), Pd(dppf)Cl2 (6 g, 8.2 mmol) and KOAc (48 g, 489 mmol) in 1,4-dioxane (600 mL), the result was refluxed for 12 hours. After the reaction was completed, MC and distilled water were introduced to the reaction solution for extraction. After that, the result was dried with anhydrous MgSO4, and the solvent was removed using a rotary evaporator. After passing silica, the result went through MeOH slurry to obtain Compound 1-2. (69 g, 95%, pale pink solid)
After dissolving Compound 1-2 (9cw g, 21.4 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (8.2 g, 21.4 mmol) in toluene, EtOH and H2O (100 mL:20 mL:20 mL), Pd(PPh3)4 (1.3 g, 1.07 mmol) and K2CO3 (8.9 g, 64.2 mol) were introduced thereto, and the result was refluxed for 5 hours. After the reaction was completed, produced solids were filtered to obtain Compound 1-1. (11.4 g, 88%, white solid)
After dissolving Compound 1-1 (10 g, 17.3 mmol), triphenylen-2-ylboronic acid (5.7 g, 20.8 mmol), Pd2(dba)3 (1.6 g, 1.7 mmol), XPhos (1.7 g, 3.4 mmol) and K3PO4 (11 g, 52 mmol) in 1,4-dioxane (100 mL), the result was refluxed for 12 hours. After the reaction was finished, produced solids were filtered. The solids were washed with distilled water and acetone to obtain target Compound 1. (9 g, 65%, white solid)
A target compound was synthesized in the same manner as in Preparation Example 1 except that Intermediate A of the following Table 1 was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, and Intermediate B of the following Table 1 was used instead of triphenylen-2-ylboronic acid.
A target compound was synthesized in the same manner as in Preparation Example 1 except that 3-bromobenzoyl chloride was used instead of 4-bromobenzoyl chloride, Intermediate C of the following Table 2 was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, and Intermediate D of the following Table 2 was used instead of triphenylen-2-ylboronic acid.
A target compound was synthesized in the same manner as in Preparation Example 1 except that 2-bromo-5-chloroaniline was used instead of 2-bromo-6-chloroaniline, Intermediate E of the following Table 3 was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, and Intermediate F of the following Table 3 was used instead of triphenylen-2-ylboronic acid.
A target compound was synthesized in the same manner as in Preparation Example 1 except that 2-bromo-5-chloroaniline was used instead of 2-bromo-6-chloroaniline, 3-bromobenzoyl chloride was used instead of 4-bromobenzoyl chloride, Intermediate G of the following Table 4 was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, and Intermediate H of the following Table 4 was used instead of triphenylen-2-ylboronic acid.
A target compound was synthesized in the same manner as in Preparation Example 1 except that 2-bromo-4-chloroaniline was used instead of 2-bromo-6-chloroaniline, Intermediate I of the following Table 5 was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, and Intermediate J of the following Table 5 was used instead of triphenylen-2-ylboronic acid.
A target compound was synthesized in the same manner as in Preparation Example 1 except that 2-bromo-3-chloroaniline was used instead of 2-bromo-6-chloroaniline, Intermediate K of the following Table 6 was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, and Intermediate L of the following Table 6 was used instead of triphenylen-2-ylboronic acid.
A target compound was synthesized in the same manner as in Preparation Example 1 except that 2-bromo-3-chloroaniline was used instead of 2-bromo-6-chloroaniline, 3-bromobenzoyl chloride was used instead of 4-bromobenzoyl chloride, Intermediate M of the following Table 7 was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, and Intermediate N of the following Table 7 was used instead of triphenylen-2-ylboronic acid.
1) Preparation of Compound 212-4
After dissolving benzo[b]thiophen-3-ylboronic acid (80 g, 500 mmol) and 2-bromo-6-chloroaniline (95 g, 550 mmol) in toluene, EtOH and H2O (1500 mL:300 mL:300 mL), Pd(PPh3)4 (29 g, 25 mmol) and NaHCO3 (126 g, 1500 mmol) were introduced thereto, and the result was refluxed for 4 hours. After the reaction was completed, the result was cooled to room temperature and extracted with MC. The result was dried with anhydrous MgSO4, and then the solvent was removed using a rotary evaporator. Target Compound 212-4 was obtained using column chromatography (MC:Hx=1:3). (90 g, 91%, brown oil)
2) Preparation of Compound 212-3
Compound 212-4 (90 g, 219 mmol) and triethylamine (95 mL, 660 mmol) were introduced to MC (1500 mL) and dissolved therein. Benzoyl chloride (80 g, 250 mmol) dissolved in MC (300 mL) was slowly added dropwise to the mixture at 0° C. After the reaction was completed, MC and distilled water were introduced to the reaction solution for extraction. After that, the result was dried with anhydrous MgSO4, and, after removing the solvent using a rotary evaporator, recrystallized with EA/Hx to obtain Compound 212-3. (100 g, 91%, white solid)
3) Preparation of Compound 212-2
After dissolving Compound 212-3 (40 g, 110 mmol) in nitrobenzene (400 mL), POCl3 (13 mL, 110 mmol) was slowly added dropwise thereto. After that, the result was stirred for 12 hours at 150° C. After the reaction was completed, the reaction solution was neutralized with an aqueous NaHCO3 solution. Solids produced from the neutralization were filtered. The solids were recrystallized with MC/MeOH to obtain target Compound 212-2. (30 g, 88%, white solid)
4) Preparation of Compound 212-1
After dissolving Compound 212-2 (30 g, 70 mmol), bis(pinacolato)diboron (27 g, 105 mmol), Pd(dba)2 (4 g, 7 mmol), XPhos (6.8 g, 14 mmol) and KOAc (48 g, 210 mmol) in 1,4-dioxane (300 mL), the result was refluxed for 12 hours. After the reaction was completed, MC and distilled water were introduced to the reaction solution for extraction. After that, the result was dried with anhydrous MgSO4, and the solvent was removed using a rotary evaporator. After passing silica, the result went through MeOH slurry to obtain Compound 212-1. (34 g, 85%, white solid)
5) Preparation of Compound 212
After dissolving Compound 212-1 (10 g, 22.9 mmol), 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole (13 g, 22.9 mmol), Pd(PPh3)4 (1.3 g, 1.2 mmol) and K2CO3 (10 g, 69 mmol) in toluene, EtOH and H2O (100 mL:20 mL:20 mL), the result was refluxed for 12 hours. After the reaction was finished, produced solids were filtered. The solids were washed with distilled water and acetone to obtain target Compound 212. (9 g, 65%, white solid)
A target compound was synthesized in the same manner as in Preparation Example 2 except that Intermediate 0 of the following Table 8 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 2 except that 1-naphthoyl chloride was used instead of benzoyl chloride, and Intermediate P of the following Table 9 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 2 except that phenanthrene-9-carbonyl chloride was used instead of benzoyl chloride, and Intermediate Q of the following Table 10 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 2 except that 2-bromo-5-chloroaniline was used instead of 2-bromo-6-chloroaniline, and Intermediate R of the following Table 11 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 2 except that 2-bromo-5-chloroaniline was used instead of 2-bromo-6-chloroaniline, 1-naphthoyl chloride was used instead of benzoyl chloride, and Intermediate S of the following Table 12 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 2 except that 2-bromo-5-chloroaniline was used instead of 2-bromo-6-chloroaniline, phenanthrene-9-carbonyl chloride was used instead of benzoyl chloride, and Intermediate T of the following Table 13 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 2 except that 2-bromo-5-chloroaniline was used instead of 2-bromo-6-chloroaniline, triphenylene-2-carbonyl chloride was used instead of benzoyl chloride, and Intermediate U of the following Table 14 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 2 except that 2-bromo-4-chloroaniline was used instead of 2-bromo-6-chloroaniline, and Intermediate V of the following Table 15 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 2 except that 2-bromo-4-chloroaniline was used instead of 2-bromo-6-chloroaniline, 1-naphthoyl chloride was used instead of benzoyl chloride, and Intermediate W of the following Table 16 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 2 except that 2-bromo-4-chloroaniline was used instead of 2-bromo-6-chloroaniline, phenanthrene-9-carbonyl chloride was used instead of benzoyl chloride, and Intermediate X of the following Table 17 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 2 except that 2-bromo-4-chloroaniline was used instead of 2-bromo-6-chloroaniline, triphenylene-2-carbonyl chloride was used instead of benzoyl chloride, and Intermediate Y of the following Table 18 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 2 except that 2-bromo-3-chloroaniline was used instead of 2-bromo-6-chloroaniline, and Intermediate Z of the following Table 19 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 2 except that 2-bromo-3-chloroaniline was used instead of 2-bromo-6-chloroaniline, 1-naphthoyl chloride was used instead of benzoyl chloride, and Intermediate AA of the following Table 20 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 2 except that 2-bromo-3-chloroaniline was used instead of 2-bromo-6-chloroaniline, phenanthrene-9-carbonyl chloride was used instead of benzoyl chloride, and Intermediate AB of the following Table 21 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 2 except that 2-bromo-3-chloroaniline was used instead of 2-bromo-6-chloroaniline, phenanthrene-9-carbonyl chloride was used instead of benzoyl chloride, and Intermediate AC of the following Table 22 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
<Preparation Example 3>—Preparation of Compound 425
1) Preparation of Compound 425-4
After dissolving benzo[b]thiophen-3-ylboronic acid (40 g, 250 mmol) and 2-bromonaphthalen-1-amine (67 g, 300 mmol) in toluene, EtOH and H2O (1000 mL:200 mL:200 mL), Pd(PPh3)4 (15 g, 13 mmol) and NaHCO3 (63 g, 750 mmol) were introduced thereto, and the result was refluxed for 4 hours. After the reaction was completed, the result was cooled to room temperature and extracted with MC. The result was dried with anhydrous MgSO4, and then the solvent was removed using a rotary evaporator. Target Compound 425-4 was obtained using column chromatography (MC:Hx=1:3). (60 g, 88%, brown solid)
2) Preparation of Compound 425-3
Compound 425-4 (60 g, 218 mmol) and triethylamine (93 mL, 650 mmol) were introduced to MC (1500 mL) and dissolved therein. 4-Bromobenzoyl chloride (53 g, 240 mmol) dissolved in MC (300 mL) was slowly added dropwise to the mixture at 0° C. After the reaction was completed, MC and distilled water were introduced to the reaction solution for extraction. After that, the result was dried with anhydrous MgSO4, and, after removing the solvent using a rotary evaporator, recrystallized with EA/Hx to obtain Compound 425-3. (90 g, 90%, white solid)
3) Preparation of Compound 425-2
After dissolving Compound 425-3 (90 g, 200 mmol) in nitrobenzene (400 mL), POCl3 (24 mL, 200 mmol) was slowly added dropwise thereto. After that, the result was stirred for 12 hours at 150° C. After the reaction was completed, the reaction solution was neutralized with an aqueous NaHCO3 solution. Solids produced from the neutralization were filtered. The solids were recrystallized with MC/MeOH to obtain target Compound 425-2. (70 g, 80%, white solid)
4) Preparation of Compound 425-1
After dissolving Compound 425-2 (70 g, 159 mmol), bis(pinacolato)diboron (50 g, 191 mmol), Pd(dppf)Cl2 (5.8 g, 8 mmol) and KOAc (48 g, 477 mmol) in 1,4-dioxane (300 mL), the result was refluxed for 12 hours. After the reaction was completed, MC and distilled water were introduced to the reaction solution for extraction. After that, the result was dried with anhydrous MgSO4, and the solvent was removed using a rotary evaporator. After passing silica, the result went through MeOH slurry to obtain Compound 425-1. (66 g, 85%, white solid)
5) Preparation of Compound 425
After dissolving Compound 425-1 (10 g, 20.5 mmol), 4-([1,1′-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine (7 g, 20.5 mmol), Pd(PPh3)4 (1.2 g, 1.1 mmol) and K2CO3 (8.5 g, 62 mmol) in toluene, EtOH and H2O (100 mL:20 mL:20 mL), the result was refluxed for 12 hours. After the reaction was finished, produced solids were filtered. The solids were washed with distilled water and acetone to obtain target Compound 425. (11 g, 82%, white solid)
A target compound was synthesized in the same manner as in Preparation Example 3 except that Intermediate AD of the following Table 23 was used instead of 4-([1,1′-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine
A target compound was synthesized in the same manner as in Preparation Example 3 except that 3-bromonaphthalen-2-amine was used instead of 2-bromonaphthalen-1-amine, and Intermediate AE of the following Table 24 was used instead of 4-([1,1′-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine
A target compound was synthesized in the same manner as in Preparation Example 3 except that 1-bromonaphthalen-2-amine was used instead of 2-bromonaphthalen-1-amine, and Intermediate AF of the following Table 25 was used instead of 4-([1,1′-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine.
1) Preparation of Compound 461-5
After dissolving benzofuran-3-ylboronic acid (162 g, 1000 mmol) and 2-bromo-6-chloroaniline (189 g, 1100 mmol) in toluene, EtOH and H2O (2000 mL:400 mL:400 mL), Pd(PPh3)4 (58 g, 50 mmol) and NaHCO3 (252 g, 3000 mmol) were introduced thereto, and the result was refluxed for 4 hours. After the reaction was completed, the result was cooled to room temperature and extracted with MC. The result was dried with anhydrous MgSO4, and then the solvent was removed using a rotary evaporator. Target Compound 461-5 was obtained using column chromatography (MC:Hx=1:3). (190 g, 91%, brown oil)
2) Preparation of Compound 461-4
Compound 461-5 (95 g, 428 mmol) and triethylamine (190 mL, 1362 mmol) were introduced to MC (1500 mL) and dissolved therein. 4-Bromobenzoyl chloride (149 g, 681 mmol) dissolved in MC (300 mL) was slowly added dropwise to the mixture at 0° C. After the reaction was completed, MC and distilled water were introduced to the reaction solution for extraction. After that, the result was dried with anhydrous MgSO4, and, after removing the solvent using a rotary evaporator, recrystallized with MC/Hx to obtain Compound 461-4. (82 g, 91%, white solid)
3) Preparation of Compound 461-3
After dissolving Compound 461-4 (82 g, 210 mmol) in nitrobenzene (1000 mL), POCl3 (24 mL, 210 mmol) was slowly added dropwise thereto. After that, the result was stirred for 12 hours at 150° C. After the reaction was completed, the reaction solution was neutralized with an aqueous NaHCO3 solution. Solids produced from the neutralization were filtered. The solids were recrystallized with MC/MeOH to obtain target Compound 461-3. (69 g, 88%, white solid)
4) Preparation of Compound 461-2
After dissolving Compound 461-2 (61 g, 163 mmol), bis(pinacolato)diboron (62 g, 244 mmol), Pd(dppf)Cl2 (6 g, 8.2 mmol) and KOAc (48 g, 489 mmol) in 1,4-dioxane (600 mL), the result was refluxed for 12 hours. After the reaction was completed, MC and distilled water were introduced to the reaction solution for extraction. After that, the result was dried with anhydrous MgSO4, and the solvent was removed using a rotary evaporator. After passing silica, the result went through MeOH slurry to obtain Compound 461-2. (69 g, 95%, pale pink solid)
5) Preparation of Compound 461-1
After dissolving Compound 461-2 (9cw g, 21.4 mmol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (8.2 g, 21.4 mmol) in toluene, EtOH and H2O (100 mL:20 mL:20 mL), Pd(PPh3)4 (1.3 g, 1.07 mmol) and K2CO3 (8.9 g, 64.2 mol) were introduced thereto, and the result was refluxed for 5 hours. After the reaction was completed, produced solids were filtered to obtain Compound 461-1. (10 g, 78%, white solid)
5) Preparation of Compound 461
After dissolving Compound 461-1 (10 g, 17.3 mmol), triphenylen-2-ylboronic acid (5.7 g, 20.8 mmol), Pd2(dba)3 (1.6 g, 1.7 mmol), XPhos (1.7 g, 3.4 mmol) and K3PO4 (11 g, 52 mmol) in 1,4-dioxane (100 mL), the result was refluxed for 12 hours. After the reaction was finished, produced solids were filtered. The solids were washed with distilled water and acetone to obtain target Compound 461. (9 g, 65%, white solid)
A target compound was synthesized in the same manner as in Preparation Example 4 except that Intermediate AG of the following Table 26 was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, and Intermediate AH of the following Table 26 was used instead of triphenylen-2-ylboronic acid.
A target compound was synthesized in the same manner as in Preparation Example 4 except that 3-bromobenzoyl chloride was used instead of 4-bromobenzoyl chloride, Intermediate AI of the following Table 27 was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, and Intermediate AJ of the following Table 27 was used instead of triphenylen-2-ylboronic acid.
A target compound was synthesized in the same manner as in Preparation Example 4 except that 2-bromo-5-chloroaniline was used instead of 2-bromo-6-chloroaniline, Intermediate AK of the following Table 28 was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, and Intermediate AL of the following Table 28 was used instead of triphenylen-2-ylboronic acid.
A target compound was synthesized in the same manner as in Preparation Example 4 except that 2-bromo-5-chloroaniline was used instead of 2-bromo-6-chloroaniline, 3-bromobenzoyl chloride was used instead of 4-bromobenzoyl chloride, Intermediate AM of the following Table 29 was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, and Intermediate AN of the following Table 29 was used instead of triphenylen-2-ylboronic acid.
A target compound was synthesized in the same manner as in Preparation Example 4 except that 2-bromo-4-chloroaniline was used instead of 2-bromo-6-chloroaniline, Intermediate AO of the following Table 30 was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, and Intermediate AP of the following Table 30 was used instead of triphenylen-2-ylboronic acid.
A target compound was synthesized in the same manner as in Preparation Example 4 except that 2-bromo-3-chloroaniline was used instead of 2-bromo-6-chloroaniline, Intermediate AQ of the following Table 31 was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, and Intermediate AR of the following Table 31 was used instead of triphenylen-2-ylboronic acid.
A target compound was synthesized in the same manner as in Preparation Example 4 except that 2-bromo-3-chloroaniline was used instead of 2-bromo-6-chloroaniline, 3-bromobenzoyl chloride was used instead of 4-bromobenzoyl chloride, Intermediate AS of the following Table 32 was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, and Intermediate AT of the following Table 32 was used instead of triphenylen-2-ylboronic acid.
1) Preparation of Compound 672-4
After dissolving benzofuran-3-ylboronic acid (80 g, 500 mmol) and 2-bromo-6-chloroaniline (95 g, 550 mmol) in toluene, EtOH and H2O (1500 mL:300 mL:300 mL), Pd(PPh3)4 (29 g, 25 mmol) and NaHCO3 (126 g, 1500 mmol) were introduced thereto, and the result was refluxed for 4 hours. After the reaction was completed, the result was cooled to room temperature and extracted with MC. The result was dried with anhydrous MgSO4, and then the solvent was removed using a rotary evaporator. Target Compound 672-4 was obtained using column chromatography (MC:Hx=1:3). (80 g, 80%, brown oil)
2) Preparation of Compound 672-3
Compound 672-4 (90 g, 219 mmol) and triethylamine (95 mL, 660 mmol) were introduced to MC (1500 mL) and dissolved therein. Benzoyl chloride (80 g, 250 mmol) dissolved in MC (300 mL) was slowly added dropwise to the mixture at 0° C. After the reaction was completed, MC and distilled water were introduced to the reaction solution for extraction. After that, the result was dried with anhydrous MgSO4, and, after removing the solvent using a rotary evaporator, recrystallized with MC/Hx to obtain Compound 672-3. (100 g, 91%, white solid)
3) Preparation of Compound 672-2
After dissolving Compound 672-3 (40 g, 110 mmol) in nitrobenzene (400 mL), POCl3 (13 mL, 110 mmol) was slowly added dropwise thereto. After that, the result was stirred for 12 hours at 150° C. After the reaction was completed, the reaction solution was neutralized with an aqueous NaHCO3 solution. Solids produced from the neutralization were filtered. The solids were recrystallized with MC/MeOH to obtain target Compound 672-2. (30 g, 88%, white solid)
4) Preparation of Compound 672-1
After dissolving Compound 672-2 (30 g, 70 mmol), bis(pinacolato)diboron (27 g, 105 mmol), Pd(dba)2 (4 g, 7 mmol), XPhos (6.8 g, 14 mmol) and KOAc (48 g, 210 mmol) in 1,4-dioxane (300 mL), the result was refluxed for 12 hours. After the reaction was completed, MC and distilled water were introduced to the reaction solution for extraction. After that, the result was dried with anhydrous MgSO4, and the solvent was removed using a rotary evaporator. After passing silica, the result went through MeOH slurry to obtain Compound 672-2. (34 g, 85%, white solid)
5) Preparation of Compound 672
After dissolving Compound 672-1 (10 g, 22.9 mmol), 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole (13 g, 22.9 mmol), Pd(PPh3)4 (1.3 g, 1.2 mmol) and K2CO3 (10 g, 69 mmol) in toluene, EtOH and H2O (100 mL:20 mL:20 mL), the result was refluxed for 12 hours. After the reaction was finished, produced solids were filtered. The solids were washed with distilled water and acetone to obtain target Compound 672. (10 g, 70%, white solid)
A target compound was synthesized in the same manner as in Preparation Example 5 except that Intermediate AU of the following Table 33 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 5 except that 1-naphthoyl chloride was used instead of benzoyl chloride, and Intermediate AV of the following Table 34 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 5 except that phenanthrene-9-carbonyl chloride was used instead of benzoyl chloride, and Intermediate AW of the following Table 35 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 5 except that 2-bromo-5-chloroaniline was used instead of 2-bromo-6-chloroaniline, and Intermediate AX of the following Table 36 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 5 except that 2-bromo-5-chloroaniline was used instead of 2-bromo-6-chloroaniline, 1-naphthoyl chloride was used instead of benzoyl chloride, and Intermediate AY of the following Table 37 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 5 except that 2-bromo-5-chloroaniline was used instead of 2-bromo-6-chloroaniline, phenanthrene-9-carbonyl chloride was used instead of benzoyl chloride, and Intermediate AZ of the following Table 38 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 5 except that 2-bromo-5-chloroaniline was used instead of 2-bromo-6-chloroaniline, triphenylene-2-carbonyl chloride was used instead of benzoyl chloride, and Intermediate BA of the following Table 39 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 5 except that 2-bromo-4-chloroaniline was used instead of 2-bromo-6-chloroaniline, and Intermediate BB of the following Table 40 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 5 except that 2-bromo-4-chloroaniline was used instead of 2-bromo-6-chloroaniline, 1-naphthoyl chloride was used instead of benzoyl chloride, and Intermediate BC of the following Table 41 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 5 except that 2-bromo-4-chloroaniline was used instead of 2-bromo-6-chloroaniline, phenanthrene-9-carbonyl chloride was used instead of benzoyl chloride, and Intermediate BD of the following Table 42 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 5 except that 2-bromo-4-chloroaniline was used instead of 2-bromo-6-chloroaniline, triphenylene-2-carbonyl chloride was used instead of benzoyl chloride, and Intermediate BE of the following Table 43 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 5 except that 2-bromo-3-chloroaniline was used instead of 2-bromo-6-chloroaniline, and Intermediate BF of the following Table 44 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 5 except that 2-bromo-3-chloroaniline was used instead of 2-bromo-6-chloroaniline, 1-naphthoyl chloride was used instead of benzoyl chloride, and Intermediate BG of the following Table 45 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 5 except that 2-bromo-3-chloroaniline was used instead of 2-bromo-6-chloroaniline, phenanthrene-9-carbonyl chloride was used instead of benzoyl chloride, and Intermediate BH of the following Table 46 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
A target compound was synthesized in the same manner as in Preparation Example 5 except that 2-bromo-3-chloroaniline was used instead of 2-bromo-6-chloroaniline, phenanthrene-9-carbonyl chloride was used instead of benzoyl chloride, and Intermediate BI of the following Table 47 was used instead of 9-(4-(4-(4-bromophenyl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)-9H-carbazole.
1) Preparation of Compound 885-4
After dissolving benzofuran-3-ylboronic acid (40 g, 250 mmol) and 2-bromonaphthalen-1-amine (67 g, 300 mmol) in toluene, EtOH and H2O (1000 mL:200 mL:200 mL), Pd(PPh2)4 (15 g, 13 mmol) and NaHCO3 (63 g, 750 mmol) were introduced thereto, and the result was refluxed for 4 hours. After the reaction was completed, the result was cooled to room temperature and extracted with MC. The result was dried with anhydrous MgSO4, and then the solvent was removed using a rotary evaporator. Target Compound 885-4 was obtained using column chromatography (MC:Hx=1:3). (50 g, 78%, brown solid)
2) Preparation of Compound 885-3
Compound 885-4 (60 g, 218 mmol) and triethylamine (93 mL, 650 mmol) were introduced to MC (1500 mL) and dissolved therein. 4-Bromobenzoyl chloride (53 g, 240 mmol) dissolved in MC (300 mL) was slowly added dropwise to the mixture at 0° C. After the reaction was completed, MC and distilled water were introduced to the reaction solution for extraction. After that, the result was dried with anhydrous MgSO4, and, after removing the solvent using a rotary evaporator, recrystallized with EA/Hx to obtain Compound 885-3. (90 g, 90%, white solid)
3) Preparation of Compound 885-2
After dissolving Compound 885-3 (90 g, 200 mmol) in nitrobenzene (400 mL), POCl3 (24 mL, 200 mmol) was slowly added dropwise thereto. After that, the result was stirred for 12 hours at 150° C. After the reaction was completed, the reaction solution was neutralized with an aqueous NaHCO3 solution. Solids produced from the neutralization were filtered. The solids were recrystallized with MC/MeOH to obtain target Compound 885-2. (60 g, 70%, white solid)
4) Preparation of Compound 885-1
After dissolving Compound 885-2 (70 g, 159 mmol), bis(pinacolato)diboron (50 g, 191 mmol), Pd(dppf)Cl2 (5.8 g, 8 mmol) and KOAc (48 g, 477 mmol) in 1,4-dioxane (300 mL), the result was refluxed for 12 hours. After the reaction was completed, MC and distilled water were introduced to the reaction solution for extraction. After that, the result was dried with anhydrous MgSO4, and the solvent was removed using a rotary evaporator. After passing silica, the result went through MeOH slurry to obtain Compound 885-1. (66 g, 85%, white solid)
5) Preparation of Compound 885
After dissolving Compound 885-1 (10 g, 20.5 mmol), 4-([1,1′-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine (7 g, 20.5 mmol), Pd(PPh3)4 (1.2 g, 1.1 mmol) and K2CO3 (8.5 g, 62 mmol) in toluene, EtOH and H2O (100 mL:20 mL:20 mL), the result was refluxed for 12 hours. After the reaction was finished, produced solids were filtered. The solids were washed with distilled water and acetone to obtain target Compound 885. (9 g, 72%, white solid)
A target compound was synthesized in the same manner as in Preparation Example 6 except that Intermediate BJ of the following Table 48 was used instead of 4-([1,1′-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine.
A target compound was synthesized in the same manner as in Preparation Example 6 except that 3-bromonaphthalen-2-amine was used instead of 2-bromonaphthalen-1-amine, and Intermediate BK of the following Table 49 was used instead of 4-([1,1′-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine.
A target compound was synthesized in the same manner as in Preparation Example 6 except that 1-bromonaphthalen-2-amine was used instead of 2-bromonaphthalen-1-amine, and Intermediate BL of the following Table 50 was used instead of 4-([1,1′-biphenyl]-4-yl)-6-chloro-2-phenylpyrimidine.
The following Table 51 and Table 52 present 1H NMR data and FD-MS data of the synthesized compounds, and through the following data, syntheses of target compounds are identified.
1H NMR (CDCl3, 400 Mhz)
1) Manufacture of Organic Light Emitting Device
A transparent ITO electrode thin film obtained from glass for an OLED (manufactured by Samsung-Corning Co., Ltd.) was ultrasonic cleaned using trichloroethylene, acetone, ethanol and distilled water consecutively for 5 minutes each, stored in isopropanol, and used.
Next, an ITO substrate was installed in a substrate folder of a vacuum depositor, and the following 4,4′,4″-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) was introduced to a cell in the vacuum depositor.
Subsequently, the chamber was evacuated until the degree of vacuum therein reached 10−6 torr, and then 2-TNATA was evaporated by applying a current to the cell to deposit a hole injection layer having a thickness of 600 Å on the ITO substrate.
To another cell of the vacuum depositor, the following N,N′-bis(α-naphthyl)-N,N′-diphenyl-4,4′-diamine (NPB) was introduced, and evaporated by applying a current to the cell to deposit a hole transfer layer having a thickness of 300 Å on the hole injection layer.
After forming the hole injection layer and the hole transfer layer as above, a blue light emitting material having a structure as below was deposited thereon as a light emitting layer. Specifically, in one side cell in the vacuum depositor, H1, a blue light emitting host material, was vacuum deposited to a thickness of 200 Å, and D1, a blue light emitting dopant material, was vacuum deposited thereon by 5% with respect to the host material.
Subsequently, one of compounds described in the following Table 53 was deposited to a thickness of 300 Å as an electron transfer layer.
As an electron injection layer, lithium fluoride (LiF) was deposited to a thickness of 10 Å, and an Al cathode was employed to have a thickness of 1,000 Å to manufacture an OLED. Meanwhile, all the organic compounds required to manufacture the OLED were vacuum sublimation purified under 10−6 torr to 10−8 torr by each material to be used in the OLED manufacture.
For the organic electroluminescent device manufactured as above, electroluminescent light emission (EL) properties were measured using M7000 manufactured by McScience Inc., and with the measurement results, T95 when standard luminance was 700 cd/m2 was measured using a lifetime measurement system (M6000) manufactured by McScience Inc. Results of measuring a driving voltage, light emission efficiency, external quantum efficiency and a color coordinate (CIE) of the blue organic electroluminescent device manufactured according to the present disclosure are as shown in the following Table 53.
As seen from the results of Table 53, the organic electroluminescent device using the electron transfer layer material of the blue organic electroluminescent device of the present disclosure had a lower driving voltage, and significantly improved light emission efficiency and lifetime compared to Comparative Examples 1-1, 1-2, 1-3, 1-4 and 1-5.
Such a result is considered to be due to the fact that, when using the disclosed compound having proper length, strength and flat properties as an electron transfer layer, a compound in an excited state is made by receiving electrons under a specific condition, and particularly when a hetero-skeleton site of the compound is formed in an excited state, excited energy moves to a stable state before the excited hetero-skeleton site goes through other reactions, and a relatively stabilized compound is capable of efficiently transfer electrons without the compound being decomposed or destroyed. For reference, those that are stable when excited are considered to be aryl or acene compounds, or polycyclic hetero-compounds. Accordingly, it is considered that excellent results in all aspects of driving, efficiency and lifetime are obtained by the compound of the present disclosure enhancing enhanced electron-transfer properties or improved stability.
1) Manufacture of Organic Light Emitting Device
A transparent ITO electrode thin film obtained from glass for an OLED (manufactured by Samsung-Corning Co., Ltd.) was ultrasonic cleaned using trichloroethylene, acetone, ethanol and distilled water consecutively for 5 minutes each, stored in isopropanol, and used.
Next, an ITO substrate was installed in a substrate folder of a vacuum depositor, and the following 4,4′,4″-tris(N,N-(2-naphthyl)-phenylamino)triphenylamine (2-TNATA) was introduced to a cell in the vacuum depositor.
After forming the hole injection layer and the hole transfer layer as above, a blue light emitting material having a structure as below was deposited thereon as a light emitting layer. Specifically, in one side cell in the vacuum depositor, H1, a blue light emitting host material, was vacuum deposited to a thickness of 200 Å, and D1, a blue light emitting dopant material, was vacuum deposited thereon by 5% with respect to the host material.
Subsequently, a compound of the following structural formula E1 was deposited to a thickness of 300 Å as an electron transfer layer.
As an electron injection layer, lithium fluoride (LiF) was deposited to a thickness of 10 Å, and an Al cathode was employed to have a thickness of 1,000 Å to manufacture an OLED. Meanwhile, all the organic compounds required to manufacture the OLED were vacuum sublimation purified under 10−6 torr to 10−8 torr by each material to be used in the OLED manufacture.
An organic electroluminescent device was manufactured in the same manner as in Experimental Example 2 except that, after forming the electron transfer layer E1 to a thickness of 250 Å, a hole blocking layer was formed on the electron transfer layer to a thickness of 50 Å using a compound presented in the following Table 54.
For the organic electroluminescent device manufactured as above, electroluminescent light emission (EL) properties were measured using M7000 manufactured by McScience Inc., and with the measurement results, T95 when standard luminance was 700 cd/m2 was measured using a lifetime measurement system (M6000) manufactured by McScience Inc. Results of measuring a driving voltage, light emission efficiency, external quantum efficiency and a color coordinate (CIE) of the blue organic electroluminescent device manufactured according to the present disclosure are as shown in Table 54.
As seen from the results of Table 54, the organic light emitting device using the hole blocking layer material of the blue organic light emitting device of the present disclosure had a lower driving voltage, and significantly improved light emission efficiency and lifetime compared to Comparative Examples 2-1, 2-2, 2-3, 2-4 and 2-5.
Such a reason is due to the fact that the heterocyclic compound of Chemical Formula 1 of the present application is a bipolar type having both a P-type and an N-type, and is capable of blocking hole leakage and effectively trapping excitons in the light emitting layer.
1) Manufacture of Organic Light Emitting Device
A glass substrate on which ITO was coated as a thin film to a thickness of 1500 Å was cleaned with distilled water ultrasonic waves. After the cleaning with distilled water was finished, the substrate was ultrasonic cleaned with solvents such as acetone, methanol and isopropyl alcohol, then dried, and UVO treatment was carried out for 5 minutes in a UV cleaner using UV. After that, the substrate was transferred to a plasma cleaner (PT), and plasma treatment was carried out under vacuum for ITO work function and remaining film removal, and the substrate was transferred to a thermal deposition apparatus for organic deposition.
On the transparent ITO electrode (anode), an organic material was formed in a 2 stack white organic light emitting device (WOLED) structure. As for the first stack, TAPC was thermal vacuum deposited to a thickness of 300 Å first to form a hole transfer layer. After forming the hole transfer layer, a light emitting layer was thermal vacuum deposited thereon as follows. The light emitting layer was deposited to 300 Å by doping Flrpic to TCzl, a host, by 8% as a blue phosphorescent dopant. After forming an electron transfer layer to 400 Å using TmPyPB, a charge generation layer was formed to 100 Å by doping Cs2CO3 to the compound described in the following Table 55 by 20%.
As for the second stack, MoO3 was thermal vacuum deposited to a thickness of 50 Å first to form a hole injection layer. A hole transfer layer, a common layer, was formed by doping MoO3 to TAPC by 20% to 100 Å and depositing TAPC to 300 Å. A light emitting layer was deposited thereon to 300 Å by doping Ir(ppy)3, a green phosphorescent dopant, to TCzl, a host, by 8%, and an electron transfer layer was formed to 600 Å using TmPyPB. Lastly, an electron injection layer was formed on the electron transfer layer by depositing lithium fluoride (LiF) to a thickness of 10 Å, and then a cathode was formed on the electron injection layer by depositing an aluminum (Al) cathode to a thickness of 1,200 Å to manufacture an organic electroluminescent device.
Meanwhile, all the organic compounds required to manufacture the OLED were vacuum sublimation purified under 10−6 torr to 10−8 torr by each material to be used in the OLED manufacture.
For the organic electroluminescent devices manufactured as above, electroluminescent light emission (EL) properties were measured using M7000 manufactured by McScience Inc., and with the measurement results, 195 when standard luminance was 3,500 cd/m2 was measured using a lifetime measurement system (M6000) manufactured by McScience Inc. Results of measuring a driving voltage, light emission efficiency, external quantum efficiency and a color coordinate (CIE) of the white organic electroluminescent device manufactured according to the present disclosure are as shown in Table 55.
As seen from the results of Table 55, the organic electroluminescent device using the charge generation layer material of the 2-stack white organic electroluminescent device of the present disclosure had a lower driving voltage and improved light emission efficiency compared to Comparative Examples 3-1, 3-2, 3-3 and 3-4.
Such a result is considered to be due to the fact that the compound of the present disclosure used as the N-type charge generation layer formed with the disclosed skeleton having proper length, strength and flat properties and a proper hetero-compound capable of binding with a metal forms a gap state in the N-type charge generation layer by doping an alkali metal or an alkaline earth metal, and electrons produced from the P-type charge generation layer are readily injected to the electron transfer layer through the gap state produced in the N-type charge generation layer. Accordingly, it is considered that the P-type charge generation layer favorably injects and transfers electrons to the N-type charge generation layer, and as a result, a driving voltage was lowered, and efficiency and lifetime were improved in the organic light emitting device.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2018/011605 | 9/28/2018 | WO | 00 |
