Patent Application
20230090371
The present specification relates to an organic light emitting device.
In general, an organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy by using an organic material. An organic light emitting device using the organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer interposed therebetween. Here, the organic material layer has in many cases a multi-layered structure composed of different materials in order to improve the efficiency and stability of the organic light emitting device, and for example, may be composed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In such a structure of the organic light emitting device, if a voltage is applied between the two electrodes, holes are injected from the anode into the organic material layer and electrons are injected from the cathode into the organic material layer, and when the injected holes and electrons meet each other, an exciton is formed, and light is emitted when the exciton falls down again to a ground state.
There is a continuous need for developing a new material for the aforementioned organic light emitting device.
The present specification provides an organic light emitting device.
The present specification provides an organic light emitting device including: an anode; a cathode; and an organic material layer including a light emitting layer provided between the anode and the cathode,
in which the light emitting layer includes one or more of compounds represented by the following Formulae 1-1 to 1-3, and a compound represented by the following Formula 2.
In Formulae 1-1 to 1-3 and 2, L1 to L3 are the same as or different from each other, and are each independently a direct bond; or a substituted or unsubstituted arylene group,
D is deuterium, n11, n21, and n31 are each an integer from 0 to 6, n12, n13, n22, n32, and n33 are each an integer from 0 to 7, and n23 is an integer from 0 to 5, Ar11, Ar21, and Ar22 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group,
Ar12, Ar13, Ar23, Ar24, Ar31, and Ar32 are the same as or different from each other, and are each independently hydrogen; deuterium; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group,
m11 and m21 are an integer from 0 to 4, m22 is an integer from 0 to 5, and when m11, m21, and m22 are each 2 or higher, substituents in the parenthesis are the same as or different from each other,
the compounds of Formulae 1-1 to 1-3 each have at least one or more deuteriums,
Y5 is C or Si,
R1 to R5, Z7, and Z8 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted alkylthio group; a substituted or unsubstituted arylthio group; or a substituted or unsubstituted amine group, or are bonded to an adjacent substituent to form a substituted or unsubstituted ring, and
r1 to r3 are an integer from 0 to 3, and substituents in the parenthesis are the same as or different from each other when r1 to r3 are each 2 or higher.
The organic light emitting device described in the present specification has a low driving voltage and has excellent efficiency characteristics and an excellent service life by including one or more of compounds represented by Formulae 1-1 to 1-3, and a compound represented by Formula 2 in a light emitting layer.
Hereinafter, the present specification will be described in more detail.
The present specification provides an organic light emitting device including a light emitting layer including compounds represented by Formulae 1-1 to 1-3, and a compound represented by Formula 2. Specifically, the compounds represented by Formulae 1-1 to 1-3 and the compound represented by Formula 2 are included as a host and a dopant, respectively.
The compound represented by Formula 2 has excellent light emission characteristics due to a narrow full-width at half-maximum, but the service life performance thereof is slightly insufficient.
Since the structures of Formulae 1-1 to 1-3 have good movement and injection of holes and electrons, the driving voltage is stabilized, so that the compounds represented by Formulae 1-1 to 1-3 have low voltage and high efficiency characteristics when used as a host of a light emitting layer of an organic light emitting device.
Further, Formulae 1-1 to 1-3 include deuterium. When the compounds of Formulae 1-1 to 1-3 include deuterium, the service life of a device is improved. Specifically, when hydrogen is replaced with deuterium, chemical properties of the compound are rarely changed. However, since the atomic weight of deuterium is twice that of hydrogen, physical properties of a deuterated compound may be changed. As an example, a compound substituted with deuterium has a lower level of vibrational energy. Quantum calculations revealed changes in the vibrational energy according to the deuterium substitution rate of the compound, but a vibrational energy of about 2 kcal/mol was decreased constantly for each number of deuterium substitutions. Accordingly, the compound substituted with deuterium may prevent a decrease in quantum efficiency caused by a decrease in intermolecular Van der Waals force or a collision due to intermolecular vibration. In addition, the stability of the compound may be improved by a C-D bond, which is stronger than a C—H bond.
The organic light emitting device of the present invention may include compounds represented by Formulae 1-1 to 1-3 and a compound represented by Formula 2 together, thereby improving a service life problem while maintaining excellent light emission characteristics of the compound of Formula 2.
The compounds of Formulae 1-1 to 1-3 including deuterium may be prepared by a publicly-known deuteration reaction. According to an exemplary embodiment of the present specification, the compounds represented by Formulae 1-1 to 1-3 may be formed using a deuterated compound as a precursor, or deuterium may also be introduced into a compound via a hydrogen-deuterium exchange reaction in the presence of an acid catalyst using a deuterated solvent.
In the present specification, N % substitution with deuterium means that N % of hydrogen available in the corresponding structure is substituted with deuterium. For example, 25% substitution of dibenzofuran with deuterium means that two of eight hydrogens of dibenzofuran are substituted with deuteriums.
In the present specification, the degree of deuteration may be confirmed by a publicly-known method such as nuclear magnetic resonance spectroscopy PH NMR) or GC/MS.
In Formulae 1-1 to 1-3 and 2 of the present specification, the substitution includes being substituted with deuterium even when the substituted substituent is not specified.
In the present specification, * or
means a bonding site that is fused or linked.
In the present specification, Cn means n carbon atoms.
In the present specification, “Cn-Cm” means “n to m carbon atoms”.
Examples of the substituents in the present specification will be described below, but are not limited thereto.
The term “substitution” means that a hydrogen atom bonded to a carbon atom of a compound is changed into another substituent, and a position to be substituted is not limited as long as the position is a position at which the hydrogen atom is substituted, that is, a position at which the substituent may be substituted, and when two or more are substituted, the two or more substituents may be the same as or different from each other.
In the present specification, the term “substituted or unsubstituted” means being substituted with one or two or more substituents selected from the group consisting of deuterium; a halogen group; a cyano group (—CN); a silyl group; a boron group; an alkyl group; a cycloalkyl group; an aryl group; and a heterocyclic group, being substituted with a substituent to which two or more substituents among the exemplified substituents are linked, or having no substituent. For example, “the substituent to which two or more substituents are linked” may be a biphenyl group. That is, the biphenyl group may also be an aryl group, and may be interpreted as a substituent to which two phenyl groups are linked.
In an exemplary embodiment of the present invention, the “substituted or unsubstituted” means being substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a cyano group (—CN); a silyl group; a C1-C20 alkyl group; a C3-C60 cycloalkyl group; a C6-C60 aryl group; and a C2-C60 heterocyclic group, being substituted with a substituent to which two or more groups selected from the above group are linked, or having no substituent.
In an exemplary embodiment of the present invention, the “substituted or unsubstituted” means being substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a cyano group (—CN); a silyl group; a C1-C10 alkyl group; a C3-C30 cycloalkyl group; a C6-C30 aryl group; and a C2-C30 heterocyclic group, being substituted with a substituent to which two or more groups selected from the above group are linked, or having no substituent.
In an exemplary embodiment of the present invention, the “substituted or unsubstituted” means being substituted with one or more substituents selected from the group consisting of deuterium; a halogen group; a cyano group (—CN); a silyl group; a C1-C6 alkyl group; a C3-C20 cycloalkyl group; a C6-C20 aryl group; and a C2-C20 heterocyclic group, being substituted with a substituent to which two or more groups selected from the above group are linked, or having no substituent.
In the present specification, the fact that two or more substituents are linked indicates that hydrogen of any one substituent is changed into another substituent. For example, an isopropyl group and a phenyl group may be linked to each other to become a substituent of
or
In the present specification, the case where three substituents are linked to one another includes not only a case where (Substituent 1)-(Substituent 2)-(Substituent 3) are consecutively linked to one another, but also a case where (Substituent 2) and (Substituent 3) are linked to (Substituent 1). For example, two phenyl groups and an isopropyl group may be linked to each other to become a substituent of
or
The same also applies to the case where four or more substituents are linked to one another.
In the present specification, “substituted with A or B” includes not only the case of being substituted with A alone or with B alone, but also the case of being substituted with A and B.
In the present specification, an alkyl group may be straight-chained or branched, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 20. Specifically, the number of carbon atoms is more preferably 1 to 10; or 1 to 6. Specific examples thereof include: 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-methylbutyl group; a 2-methylbutyl group; a 1-ethylbutyl 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-methylpentyl 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-ethylpropyl group; a tert-amyl group (a 1,1-dimethylpropyl 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 alkoxy group is one in which an alkyl group is linked to an oxygen atom, the alkylthio group is one in which an alkyl group is linked to a sulfur atom, and the above-described description on the alkyl group may be applied to the alkyl group of the alkoxy group and the alkylthio group.
In the present specification, an alkenyl group may be straight-chained or branched, and the number of carbon atoms thereof is not particularly limited, but is preferably 2 to 30; 2 to 20; 2 to 10; or 2 to 5. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, a stilbenyl group, a styrenyl group, and the like, but are not limited thereto.
In the present specification, a cycloalkyl group is not particularly limited, but has preferably 3 to 60 carbon atoms, and according to an exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 30. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to yet another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. The cycloalkyl group includes not only a single ring group, but also a double ring group such as a bridgehead, a fused ring, and a spiro ring. Specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, and the like, but are not limited thereto.
In the present specification, cycloalkene is a ring group which has a double bond present in a hydrocarbon ring, but is not aromatic, and the number of carbon atoms thereof is not particularly limited, but may be 3 to 60, and may be 3 to 30 according to an exemplary embodiment. The cycloalkene includes not only a single ring group, but also a double ring group such as a bridgehead, a fused ring, and a spiro ring. Examples of the cycloalkene include cyclopropene, cyclobutene, cyclopentene, cyclohexene, and the like, but are not limited thereto.
In the present specification, a silyl group may be represented by a formula of —SiY11Y12Y13, and the Y11, Y12, and Y13 may be each hydrogen; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group. Specific examples of the silyl group include 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, an amine group may be selected from the group consisting of —NH2; an alkylamine group; an alkylarylamine group; an arylamine group; an arylheteroarylamine group; an alkylheteroarylamine group; and a heteroarylamine group, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 60. In the case of an arylamine group, the number of carbon atoms thereof is 6 to 60. According to another exemplary embodiment, the number of carbon atoms of the arylamine group is 6 to 40. Specific examples of the amine group include a methylamine group; a dimethylamine group; an ethylamine group; a diethylamine group; a phenylamine group; a naphthylamine group; a biphenylamine group; an anthracenylamine group; a 9-methylanthracenylamine group; a diphenylamine group; an N-phenylnaphthylamine group; a ditolylamine group; an N-phenyltolylamine group; a triphenylamine group; an N-phenylbiphenylamine group; an N-phenylnaphthylamine group; an N-biphenylnaphthylamine group; an N-naphthylfluorenylamine group; an N-phenylphenanthrenylamine group; an N-biphenylphenanthrenylamine group; an N-phenylfluorenylamine group; an N-phenyl terphenylamine group; an N-phenanthrenylfluorenylamine group; an N-biphenylfluorenylamine group; an N-(4-(tert-butyl)phenyl)-N-phenylamine group; an N,N-bis(4-(tert-butyl)phenyl)amine group; an N,N-bis(3-(tert-butyl)phenyl)amine group, and the like, but are not limited thereto.
In the present specification, the alkylamine group means an amine group in which an alkyl group is substituted with N of the amine group, and includes a dialkylamine group, an alkylarylamine group, and an alkylheteroarylamine group.
In the present specification, the arylamine group means an amine group in which an aryl group is substituted with N of the amine group, and includes a diarylamine group, an arylheteroarylamine group, and an alkylarylamine group.
In the present specification, the heteroarylamine group means an amine group in which a heteroaryl group is substituted with N of the amine group, and includes a diheteroarylamine group, an arylheteroarylamine group, and an alkylheteroarylamine group.
In the present specification, an alkylarylamine group means an amine group in which an alkyl group and an aryl group are substituted with N of the amine group.
In the present specification, an arylheteroarylamine group means an amine group in which an aryl group and a heteroaryl group are substituted with N of the amine group.
In the present specification, an alkylheteroarylamine group means an amine group in which an alkyl group and a heteroaryl group are substituted with N of the amine group.
In the present specification, an aryl group is not particularly limited, but has preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the number of carbon atoms of the aryl group is 6 to 30. According to an exemplary embodiment, the number of carbon atoms of the aryl group is 6 to 20. Examples of a monocyclic aryl group as the aryl group include a phenyl group, a biphenyl group, a terphenyl group, and the like, but are not limited thereto. Examples of the polycyclic aryl group include a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, a triphenyl group, a chrysenyl group, a fluorenyl group, and the like, but are not limited thereto.
In the present specification, No. 9 carbon atom (C) of a fluorenyl group may be substituted with an alkyl group, an aryl group, or the like, and two substituents may be bonded to each other to form a spiro structure such as cyclopentane or fluorene.
In the present specification, the substituted aryl group may also include a form in which an aliphatic ring is fused to the aryl group. For example, a tetrahydronaphthalene group, a dihydroindene group and a dihydroanthracene group having the following structures are included in the substituted aryl group. In the following structure, one of the carbons of a benzene ring may be linked to another position.
In the present specification, a fused hydrocarbon ring group means a fused ring group of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring, and is a form in which the aromatic hydrocarbon ring and the aliphatic hydrocarbon ring are fused. Examples of the fused ring group of the aromatic hydrocarbon ring and the aliphatic hydrocarbon ring include a tetrahydronaphthalene group, a dihydroindene group, and a dihydroanthracene group, but are not limited thereto.
In the present specification, the alkylaryl group means an aryl group substituted with an alkyl group, and a substituent other than the alkyl group may be further linked.
In the present specification, an arylalkyl group means an alkyl group substituted with an aryl group, and a substituent other than the aryl group may be further linked.
In the present specification, the aryloxy group is one in which an aryl group is linked to an oxygen atom, the arylthio group is one in which an aryl group is linked to a sulfur atom, and the above-described description on the aryl group may be applied to the aryl group of the aryloxy group and the arylthio group. An aryl group of an aryloxy group is the same as the above-described examples of the aryl group. Specifically, examples of the aryloxy group include a phenoxy group, a p-tolyloxy group, an m-tolyloxy group, a 3,5-dimethyl-phenoxy group, a 2,4,6-trimethylphenoxy group, a p-tert-butylphenoxy group, a 3-biphenyloxy group, a 4-biphenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methyl-1-naphthyloxy group, a 5-methyl-2-naphthyloxy group, a 1-anthryloxy group, a 2-anthryloxy group, a 9-anthryloxy group, a 1-phenanthryloxy group, a 3-phenanthryloxy group, a 9-phenanthryloxy group, and the like, and examples of the arylthioxy group include a phenylthioxy group, a 2-methylphenylthioxy group, a 4-tert-butylphenylthioxy group, and the like, but the examples are not limited thereto.
In the present specification, a heterocyclic group is a cyclic group including one or more of N, O, P, S, Si, and Se as a heteroatom, and the number of carbon atoms thereof is not particularly limited, but is preferably 2 to 60. According to an exemplary embodiment, the number of carbon atoms of the heterocyclic group is 2 to 30. According to an exemplary embodiment, the number of carbon atoms of the heterocyclic group is 2 to 20. Examples of the heterocyclic group include a pyridyl group; a quinoline group; a thiophene group; a dibenzothiophene group; a furan group; a dibenzofuran group; a naphthobenzofuran group; a carbazole group; a benzocarbazole group; a naphthobenzothiophene group; a dibenzosilole group; a naphthobenzosilole group; a hexahydrocarbazole group; dihydroacridine group; a dihydrodibenzoazasiline group; a phenoxazine group; a phenothiazine group; a dihydrodibenzoazasiline group; a spiro(dibenzosilole-dibenzoazasiline) group; a spiro(acridine-fluorene) group, and the like, but are not limited thereto.
In the present specification, the above-described description on the heterocyclic group may be applied to a heteroaryl group except for being aromatic.
In the present specification, an aromatic hydrocarbon ring means a hydrocarbon ring in which pi electrons are completely conjugated and are planar, and the description on the aryl group may be applied to an aromatic hydrocarbon ring except for being divalent. The number of carbon atoms of the aromatic hydrocarbon ring may be 6 to 60; 6 to 30; 6 to 20; or 6 to 10.
In the present specification, an aliphatic hydrocarbon ring has a cyclically bonded structure, and means a non-aromatic ring. Examples of the aliphatic hydrocarbon ring include cycloalkyl or cycloalkene, and the above-described description on the cycloalkyl group or cycloalkenyl group may be applied to the aliphatic hydrocarbon ring except for being divalent. The number of carbon atoms of the aliphatic hydrocarbon ring may be 3 to 60; 3 to 30; 3 to 20; 3 to 10; 5 to 50; 5 to 30; 5 to 20; 5 to 10; or 5 and 6. Further, a substituted aliphatic hydrocarbon ring also includes an aliphatic hydrocarbon ring in which aromatic rings are fused.
In the present specification, a fused ring of an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring means that an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring form a fused ring. Examples of the fused ring of the aromatic ring and the aliphatic ring include a 1,2,3,4-tetrahydronaphthalene group, a 2,3-dihydro-1H-indene group, and the like, but are not limited thereto.
In the present specification, the “adjacent” group may mean a substituent substituted with an atom directly linked to an atom in which the corresponding substituent is substituted, a substituent disposed to be sterically closest to the corresponding substituent, or another substituent substituted with an atom in which the corresponding substituent is substituted. For example, two substituents substituted at the ortho position in a benzene ring and two substituents substituted with the same carbon in an aliphatic ring may be interpreted as groups which are “adjacent” to each other. In addition, substituents (four in total) linked to two consecutive carbons in an aliphatic ring may be interpreted as “adjacent” groups.
In the present specification, the “adjacent groups are bonded to each other to form a ring” among the substituents means that a substituent is bonded to an adjacent group to form a substituted or unsubstituted hydrocarbon ring; or a substituted or unsubstituted hetero ring.
In the present specification, “a five-membered or six-membered ring formed by bonding adjacent groups” means that a ring including a substituent participating in the ring formation is five-membered or six-membered. It is possible to include an additional ring fused to the ring including the substituent participating in the ring formation.
In the present specification, when a substituent of an aromatic hydrocarbon ring or an aryl group is bonded to an adjacent substituent to form an aliphatic hydrocarbon ring, the aliphatic hydrocarbon ring includes two pi electrons (carbon-carbon double bond) of an aromatic hydrocarbon ring or an aryl group, even though a double bond is not specified.
In the present specification, the above-described description on the aryl group may be applied to an arylene group except for being divalent.
In the present specification, the above-described description on the cycloalkyl group may be applied to a cycloalkylene group except for being divalent.
Hereinafter, the following Formulae 1-1 to 1-3 will be described.
In an exemplary embodiment of the present specification, the compounds of Formulae 1-1 to 1-3 each include at least one or more deuteriums.
In an exemplary embodiment of the present specification, Ar11, Ar21, and Ar22 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group.
In an exemplary embodiment of the present application, Ar11, Ar21, and Ar22 are the same as or different from each other, and are each independently a substituted or unsubstituted C6-C30 aryl group.
In an exemplary embodiment of the present specification, Ar11, Ar21, and Ar22 are the same as or different from each other, and are each independently a C6-C20 aryl group which is unsubstituted or substituted with deuterium or a C1-C10 alkyl group.
In an exemplary embodiment of the present specification, Ar11, Ar21, and Ar22 are the same as or different from each other, and are each independently a C6-C13 aryl group which is unsubstituted or substituted with deuterium or a C1-C6 alkyl group.
In an exemplary embodiment of the present specification, Ar11, Ar21, and Ar22 are the same as or different from each other, and are each independently a C6-C10 aryl group which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, Ar11, Ar21, and Ar22 are the same as or different from each other, and are each independently a phenyl group which is unsubstituted or substituted with deuterium; a biphenyl group which is unsubstituted or substituted with deuterium; a naphthyl group which is unsubstituted or substituted with deuterium; or a fluorenyl group which is unsubstituted or substituted with deuterium or a methyl group.
In an exemplary embodiment of the present specification, Ar11, Ar21, and Ar22 are the same as or different from each other, and are each independently a phenyl group which is unsubstituted or substituted with deuterium; a 1-naphthyl group which is unsubstituted or substituted with deuterium; or a 2-naphthyl group which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, Ar11 is a phenyl group which is unsubstituted or substituted with deuterium; a biphenyl group which is unsubstituted or substituted with deuterium; or a naphthyl group which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, Ar11 is a phenyl group which is unsubstituted or substituted with deuterium; a 1-naphthyl group which is unsubstituted or substituted with deuterium; or a 2-naphthyl group which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, Ar21 and Ar22 are the same as or different from each other, and are each independently a phenyl group which is unsubstituted or substituted with deuterium; a biphenyl group which is unsubstituted or substituted with deuterium; a naphthyl group which is unsubstituted or substituted with deuterium; or a fluorenyl group which is unsubstituted or substituted with deuterium or a methyl group.
In an exemplary embodiment of the present specification, Ar21 and Ar22 are the same as or different from each other, and are each independently a phenyl group which is unsubstituted or substituted with deuterium; a 1-naphthyl group which is unsubstituted or substituted with deuterium; or a 2-naphthyl group which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, one of Ar12 and Ar13 is hydrogen; or deuterium, and the other is a substituted or unsubstituted aryl group.
In an exemplary embodiment of the present specification, one of Ar12 and Ar13 is hydrogen; or deuterium, and the other is a substituted or unsubstituted C6-C30 aryl group.
In an exemplary embodiment of the present specification, one of Ar12 and Ar13 is hydrogen; or deuterium, and the other is a C6-C20 aryl group which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, one of Ar12 and Ar13 is hydrogen; or deuterium, and the other is a C6-C10 aryl group which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, one of Ar12 and Ar13 is hydrogen; or deuterium, and the other is a phenyl group which is unsubstituted or substituted with deuterium; a biphenyl group which is unsubstituted or substituted with deuterium; or a naphthyl group which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, Ar12 and Ar13 are each hydrogen; or deuterium.
In an exemplary embodiment of the present specification, one of Ar23 and Ar24 is hydrogen; or deuterium, and the other is a substituted or unsubstituted aryl group.
In an exemplary embodiment of the present specification, one of Ar23 and Ar24 is hydrogen; or deuterium, and the other is a substituted or unsubstituted C6-C30 aryl group.
In an exemplary embodiment of the present specification, one of Ar23 and Ar24 is hydrogen; or deuterium, and the other is a C6-C20 aryl group which is unsubstituted or substituted with deuterium or a C1-C10 alkyl group.
In an exemplary embodiment of the present specification, one of Ar23 and Ar24 is hydrogen; or deuterium, and the other is a C6-C13 aryl group which is unsubstituted or substituted with deuterium or a C1-C6 alkyl group.
In an exemplary embodiment of the present specification, one of Ar23 and Ar24 is hydrogen; or deuterium, and the other is a C6-C10 aryl group which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, one of Ar23 and Ar24 is hydrogen; or deuterium, and the other is a phenyl group which is unsubstituted or substituted with deuterium; a biphenyl group which is unsubstituted or substituted with deuterium; a naphthyl group unsubstituted or substituted with deuterium; or a fluorenyl group which is unsubstituted or substituted with deuterium or a methyl group.
In an exemplary embodiment of the present specification, Ar23 and Ar24 are each hydrogen; or deuterium.
In an exemplary embodiment of the present specification, one of Ar31 and Ar32 is hydrogen; or deuterium, and the other is a substituted or unsubstituted aryl group.
In an exemplary embodiment of the present specification, one of Ar31 and Ar32 is hydrogen; or deuterium, and the other is a substituted or unsubstituted C6-C30 aryl group.
In an exemplary embodiment of the present specification, one of Ar31 and Ar32 is hydrogen; or deuterium, and the other is a C6-C20 aryl group which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, one of Ar31 and Ar32 is hydrogen; or deuterium, and the other is a C6-C10 aryl group which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, one of Ar31 and Ar32 is hydrogen; or deuterium, and the other is a phenyl group which is unsubstituted or substituted with deuterium; a biphenyl group which is unsubstituted or substituted with deuterium; or a naphthyl group which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, Ar31 and Ar32 are each hydrogen; or deuterium.
In an exemplary embodiment of the present specification, L1 to L3 are the same as or different from each other, and are each independently a direct bond; or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.
In an exemplary embodiment of the present specification, L1 to L3 are the same as or different from each other, and are each independently a direct bond; or an arylene group having 6 to 20 carbon atoms, which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, L1 to L3 are the same as or different from each other, and are each independently a direct bond; or an arylene group having 6 to 10 carbon atoms, which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, L1 to L3 are the same as or different from each other, and are each independently a direct bond; a substituted or unsubstituted phenylene group; a substituted or unsubstituted biphenylene group; a substituted or unsubstituted terphenylene group; or a substituted or unsubstituted naphthylene group.
In an exemplary embodiment of the present specification, L1 to L3 are the same as or different from each other, and are each independently a direct bond; a phenylene group which is unsubstituted or substituted with deuterium; or a naphthylene group which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, L1 to L3 are the same as or different from each other, and are each independently a direct bond or any one selected from the following structures.
In the structures, D means deuterium, k1 is an integer from 0 to 4, and k2 is an integer from 0 to 6.
In an exemplary embodiment of the present specification, k1 is an integer from 1 to 4.
In an exemplary embodiment of the present specification, k2 is an integer from 1 to 6.
In an exemplary embodiment of the present specification, k1 is 1 or higher. In another exemplary embodiment, k1 is 2 or higher. In still another exemplary embodiment, k1 is 3 or higher. In yet another exemplary embodiment, k1 is 4.
In an exemplary embodiment of the present specification, k2 is 1 or higher. In another exemplary embodiment, k2 is 2 or higher. In still another exemplary embodiment, k2 is 3 or higher. In yet another exemplary embodiment, k2 is 4 or higher. In yet another exemplary embodiment, k2 is 5 or higher. In yet another exemplary embodiment, k2 is 6.
In an exemplary embodiment of the present specification, m11 is 0.
In an exemplary embodiment of the present specification, m11 is 1.
In an exemplary embodiment of the present specification, m21 is 1 or higher.
In an exemplary embodiment of the present specification, m21 is 1.
In an exemplary embodiment of the present specification, m22 is 0.
In an exemplary embodiment of the present specification, m22 is 1 or higher.
In an exemplary embodiment of the present specification, m22 is 1.
In an exemplary embodiment of the present specification, m11+n12 is an integer from 0 to 7.
In an exemplary embodiment of the present specification, m21+n22 is an integer from 0 to 7.
In an exemplary embodiment of the present specification, m22+n23 is an integer from 0 to 7.
In an exemplary embodiment of the present specification, n11 is 1 or higher. In another exemplary embodiment, n11 is 2 or higher. In still another exemplary embodiment, n11 is 3 or higher. In yet another exemplary embodiment, n11 is 4 or higher. In yet another exemplary embodiment, n11 is 5 or higher. In yet another exemplary embodiment, n11 is 6.
In an exemplary embodiment of the present specification, n12 is 1 or higher. In another exemplary embodiment, n12 is 2 or higher. In still another exemplary embodiment, n12 is 3 or higher. In yet another exemplary embodiment, n12 is 4 or higher. In yet another exemplary embodiment, n12 is 5 or higher. In yet another exemplary embodiment, n12 is 6 or higher. In yet another exemplary embodiment, n12 is 7.
In an exemplary embodiment of the present specification, n13 is 1 or higher. In another exemplary embodiment, n13 is 2 or higher. In still another exemplary embodiment, n13 is 3 or higher. In yet another exemplary embodiment, n13 is 4 or higher. In yet another exemplary embodiment, n13 is 5 or higher. In yet another exemplary embodiment, n13 is 6 or higher. In yet another exemplary embodiment, n13 is 7.
In an exemplary embodiment of the present specification, n11+n12+n13 is 2 or higher. In another exemplary embodiment, n11+n12+n13 is 4 or higher. In still another exemplary embodiment, n11+n12+n13 is 6 or higher. In yet another exemplary embodiment, n11+n12+n13 is 8 or higher. In yet another exemplary embodiment, n11+n12+n13 is 10 or higher. In yet another exemplary embodiment, n11+n12+n13 is 12 or higher. In yet another exemplary embodiment, n11+n12+n13 is 14 or higher. In yet another exemplary embodiment, n11+n12+n13 is 16 or higher. In yet another exemplary embodiment, n11+n12+n13 is 18 or higher. In yet another exemplary embodiment, n11+n12+n13 is 20.
In an exemplary embodiment of the present specification, n11+n12+n13 is 19 or lower. In another exemplary embodiment, n11+n12+n13 is 17 or lower. In still another exemplary embodiment, n11+n12+n13 is 15 or lower. In yet another exemplary embodiment, n11+n12+n13 is 13 or lower. In yet another exemplary embodiment, n11+n12+n13 is 11 or lower. In yet another exemplary embodiment, n11+n12+n13 is 9 or lower. In yet another exemplary embodiment, n11+n12+n13 is 7 or lower. In yet another exemplary embodiment, n11+n12+n13 is 5 or lower.
In an exemplary embodiment of the present specification, n11+n12+n13+k1 is 2 or higher. In another exemplary embodiment, n11+n12+n13+k1 is 4 or higher. In still another exemplary embodiment, n11+n12+n13+k1 is 6 or higher. In yet another exemplary embodiment, n11+n12+n13+k1 is 8 or higher. In yet another exemplary embodiment, n11+n12+n13+k1 is 10 or higher. In yet another exemplary embodiment, n11+n12+n13+k1 is 12 or higher. In yet another exemplary embodiment, n11+n12+n13+k1 is 14 or higher. In yet another exemplary embodiment, n11+n12+n13+k1 is 16 or higher. In yet another exemplary embodiment, n11+n12+n13+k1 is 18 or higher. In yet another exemplary embodiment, n11+n12+n13+k1 is 20 or higher. In yet another exemplary embodiment, n11+n12+n13+k1 is 22 or higher. In yet another exemplary embodiment, n11+n12+n13+k1 is 24.
In an exemplary embodiment of the present specification, n11+n12+n13+k1 is 23 or lower. In another exemplary embodiment, n11+n12+n13+k1 is 21 or lower. In still another exemplary embodiment, n11+n12+n13+k1 is 19 or lower. In yet another exemplary embodiment, n11+n12+n13+k1 is 17 or lower. In yet another exemplary embodiment, n11+n12+n13+k1 is 15 or lower. In yet another exemplary embodiment, n11+n12+n13+k1 is 13 or lower. In yet another exemplary embodiment, n11+n12+n13+k1 is 11 or lower. In yet another exemplary embodiment, n11+n12+n13+k1 is 9 or lower. In yet another exemplary embodiment, n11+n12+n13+k1 is 7 or lower. In yet another exemplary embodiment, n11+n12+n13+k1 is 5 or lower.
In an exemplary embodiment of the present specification, n11+n12+n13+k2 is 2 or higher. In another exemplary embodiment, n11+n12+n13+k2 is 4 or higher. In still another exemplary embodiment, n11+n12+n13+k2 is 6 or higher. In yet another exemplary embodiment, n11+n12+n13+k2 is 8 or higher. In yet another exemplary embodiment, n11+n12+n13+k2 is 10 or higher. In yet another exemplary embodiment, n11+n12+n13+k2 is 12 or higher. In yet another exemplary embodiment, n11+n12+n13+k2 is 14 or higher. In yet another exemplary embodiment, n11+n12+n13+k2 is 16 or higher. In yet another exemplary embodiment, n11+n12+n13+k2 is 18 or higher. In yet another exemplary embodiment, n11+n12+n13+k2 is 20 or higher. In yet another exemplary embodiment, n11+n12+n13+k2 is 22 or higher. In yet another exemplary embodiment, n11+n12+n13+k2 is 24 or higher. In yet another exemplary embodiment, n11+n12+n13+k2 is 26.
In an exemplary embodiment of the present specification, n11+n12+n13+k2 is 25 or lower. In another exemplary embodiment, n11+n12+n13+k2 is 23 or lower. In still another exemplary embodiment, n11+n12+n13+k2 is 21 or lower. In yet another exemplary embodiment, n11+n12+n13+k2 is 19 or lower. In yet another exemplary embodiment, n11+n12+n13+k2 is 17 or lower. In yet another exemplary embodiment, n11+n12+n13+k2 is 15 or lower. In yet another exemplary embodiment, n11+n12+n13+k2 is 13 or lower. In yet another exemplary embodiment, n11+n12+n13+k2 is 11 or lower. In yet another exemplary embodiment, n11+n12+n13+k2 is 9 or lower. In yet another exemplary embodiment, n11+n12+n13+k2 is 7 or lower.
In an exemplary embodiment of the present specification, n21 is 1 or higher. In another exemplary embodiment, n21 is 2 or higher. In still another exemplary embodiment, n21 is 3 or higher. In yet another exemplary embodiment, n21 is 4 or higher. In yet another exemplary embodiment, n21 is 5 or higher. In yet another exemplary embodiment, n21 is 6.
In an exemplary embodiment of the present specification, n22 is 1 or higher. In another exemplary embodiment, n22 is 2 or higher. In still another exemplary embodiment, n22 is 3 or higher. In yet another exemplary embodiment, n22 is 4 or higher. In yet another exemplary embodiment, n22 is 5 or higher. In yet another exemplary embodiment, n22 is 6 or higher. In yet another exemplary embodiment, n22 is 7.
In an exemplary embodiment of the present specification, n23 is 1 or higher. In another exemplary embodiment, n23 is 2 or higher. In still another exemplary embodiment, n23 is 3 or higher. In yet another exemplary embodiment, n23 is 4 or higher. In yet another exemplary embodiment, n23 is 5.
In an exemplary embodiment of the present specification, n21+n22+n23 is 2 or higher. In another exemplary embodiment, n21+n22+n23 is 4 or higher. In still another exemplary embodiment, n21+n22+n23 is 6 or higher. In yet another exemplary embodiment, n21+n22+n23 is 8 or higher. In yet another exemplary embodiment, n21+n22+n23 is 10 or higher. In yet another exemplary embodiment, n21+n22+n23 is 12 or higher. In yet another exemplary embodiment, n21+n22+n23 is 14 or higher. In yet another exemplary embodiment, n21+n22+n23 is 16 or higher. In yet another exemplary embodiment, n21+n22+n23 is 18.
In an exemplary embodiment of the present specification, n21+n22+n23 is 17 or lower. In another exemplary embodiment, n21+n22+n23 is 15 or lower. In still another exemplary embodiment, n21+n22+n23 is 13 or lower. In yet another exemplary embodiment, n21+n22+n23 is 11 or lower. In yet another exemplary embodiment, n21+n22+n23 is 9 or lower. In yet another exemplary embodiment, n21+n22+n23 is 7 or lower. In yet another exemplary embodiment, n21+n22+n23 is 5 or lower.
In an exemplary embodiment of the present specification, n21+n22+n23+k1 is 2 or higher. In yet another exemplary embodiment, n21+n22+n23+k1 is 4 or higher. In yet another exemplary embodiment, n21+n22+n23+k1 is 6 or higher. In yet another exemplary embodiment, n21+n22+n23+k1 is 8 or higher. In yet another exemplary embodiment, n21+n22+n23+k1 is 10 or higher. In yet another exemplary embodiment, n21+n22+n23+k1 is 12 or higher. In yet another exemplary embodiment, n21+n22+n23+k1 is 14 or higher. In yet another exemplary embodiment, n21+n22+n23+k1 is 16 or higher. In yet another exemplary embodiment, n21+n22+n23+k1 is 18 or higher. In yet another exemplary embodiment, n21+n22+n23+k1 is 20 or higher. In yet another exemplary embodiment, n21+n22+n23+k1 is 22.
In an exemplary embodiment of the present specification, n21+n22+n23+k1 is 21 or lower. In yet another exemplary embodiment, n21+n22+n23+k1 is 19 or lower. In yet another exemplary embodiment, n21+n22+n23+k1 is 17 or lower. In yet another exemplary embodiment, n21+n22+n23+k1 is 15 or lower. In yet another exemplary embodiment, n21+n22+n23+k1 is 13 or lower. In yet another exemplary embodiment, n21+n22+n23+k1 is 11 or lower. In yet another exemplary embodiment, n21+n22+n23+k1 is 9 or lower. In yet another exemplary embodiment, n21+n22+n23+k1 is 7 or lower. In yet another exemplary embodiment, n21+n22+n23+k1 is 5 or lower.
In an exemplary embodiment of the present specification, n21+n22+n23+k2 is 2 or higher. In another exemplary embodiment, n21+n22+n23+k2 is 4 or higher. In still another exemplary embodiment, n21+n22+n23+k2 is 6 or higher. In yet another exemplary embodiment, n21+n22+n23+k2 is 8 or higher. In yet another exemplary embodiment, n21+n22+n23+k2 is 10 or higher. In yet another exemplary embodiment, n21+n22+n23+k2 is 12 or higher. In yet another exemplary embodiment, n21+n22+n23+k2 is 14 or higher. In yet another exemplary embodiment, n21+n22+n23+k2 is 16 or higher. In yet another exemplary embodiment, n21+n22+n23+k2 is 18 or higher. In yet another exemplary embodiment, n21+n22+n23+k2 is 20 or higher. In yet another exemplary embodiment, n21+n22+n23+k2 is 22 or higher. In yet another exemplary embodiment, n21+n22+n23+k2 is 24.
In an exemplary embodiment of the present specification, n21+n22+n23+k2 is 23 or lower. In another exemplary embodiment, n21+n22+n23+k2 is 21 or lower. In yet another exemplary embodiment, n21+n22+n23+k2 is 19 or lower. In yet another exemplary embodiment, n21+n22+n23+k2 is 17 or lower. In yet another exemplary embodiment, n21+n22+n23+k2 is 15 or lower. In yet another exemplary embodiment, n21+n22+n23+k2 is 13 or lower. In yet another exemplary embodiment, n21+n22+n23+k2 is 11 or lower. In yet another exemplary embodiment, n21+n22+n23+k2 is 9 or lower. In yet another exemplary embodiment, n21+n22+n23+k2 is 7 or lower. In yet another exemplary embodiment, n21+n22+n23+k2 is 5 or lower.
In an exemplary embodiment of the present specification, n31 is 1 or higher. In another exemplary embodiment, n31 is 2 or higher. In still another exemplary embodiment, n31 is 3 or higher. In yet another exemplary embodiment, n31 is 4 or higher. In yet another exemplary embodiment, n31 is 5 or higher. In yet another exemplary embodiment, n31 is 6.
In an exemplary embodiment of the present specification, n32 is 1 or higher. In another exemplary embodiment, n32 is 2 or higher. In still another exemplary embodiment, n32 is 3 or higher. In yet another exemplary embodiment, n32 is 4 or higher. In yet another exemplary embodiment, n32 is 5 or higher. In yet another exemplary embodiment, n32 is 6 or higher. In yet another exemplary embodiment, n32 is 7.
In an exemplary embodiment of the present specification, n33 is 1 or higher. In another exemplary embodiment, n33 is 2 or higher. In still another exemplary embodiment, n33 is 3 or higher. In yet another exemplary embodiment, n33 is 4 or higher. In yet another exemplary embodiment, n33 is 5 or higher. In yet another exemplary embodiment, n33 is 6 or higher. In yet another exemplary embodiment, n33 is 7.
In an exemplary embodiment of the present specification, n31+n32+n33 is 2 or higher. In another exemplary embodiment, n31+n32+n33 is 4 or higher. In still another exemplary embodiment, n31+n32+n33 is 6 or higher. In yet another exemplary embodiment, n31+n32+n33 is 8 or higher. In yet another exemplary embodiment, n31+n32+n33 is 10 or higher. In yet another exemplary embodiment, n31+n32+n33 is 12 or higher. In yet another exemplary embodiment, n31+n32+n33 is 14 or higher. In yet another exemplary embodiment, n31+n32+n33 is 16 or higher. In yet another exemplary embodiment, n31+n32+n33 is 18 or higher. In yet another exemplary embodiment, n31+n32+n33 is 20.
In an exemplary embodiment of the present specification, n31+n32+n33 is 19 or lower. In another exemplary embodiment, n31+n32+n33 is 17 or lower. In still another exemplary embodiment, n31+n32+n33 is 15 or lower. In yet another exemplary embodiment, n31+n32+n33 is 13 or lower. In yet another exemplary embodiment, n31+n32+n33 is 11 or lower. In yet another exemplary embodiment, n31+n32+n33 is 9 or lower. In yet another exemplary embodiment, n31+n32+n33 is 7 or lower. In yet another exemplary embodiment, n31+n32+n33 is 5 or lower.
In an exemplary embodiment of the present specification, n31+n32+n33+k1 is 2 or higher. In another exemplary embodiment, n31+n32+n33+k1 is 4 or higher. In still another exemplary embodiment, n31+n32+n33+k1 is 6 or higher. In yet another exemplary embodiment, n31+n32+n33+k1 is 8 or higher. In yet another exemplary embodiment, n31+n32+n33+k1 is 10 or higher. In yet another exemplary embodiment, n31+n32+n33+k1 is 12 or higher. In yet another exemplary embodiment, n31+n32+n33+k1 is 14 or higher. In yet another exemplary embodiment, n31+n32+n33+k1 is 16 or higher. In yet another exemplary embodiment, n31+n32+n33+k1 is 18 or higher. In yet another exemplary embodiment, n31+n32+n33+k1 is 20 or higher. In yet another exemplary embodiment, n31+n32+n33+k1 is 22 or higher. In yet another exemplary embodiment, n31+n32+n33+k1 is 24.
In an exemplary embodiment of the present specification, n31+n32+n33+k1 is 23 or lower. In another exemplary embodiment, n31+n32+n33+k1 is 21 or lower. In still another exemplary embodiment, n31+n32+n33+k1 is 19 or lower. In yet another exemplary embodiment, n31+n32+n33+k1 is 17 or lower. In yet another exemplary embodiment, n31+n32+n33+k1 is 15 or lower. In yet another exemplary embodiment, n31+n32+n33+k1 is 13 or lower. In yet another exemplary embodiment, n31+n32+n33+k1 is 11 or lower. In yet another exemplary embodiment, n31+n32+n33+k1 is 9 or lower. In yet another exemplary embodiment, n31+n32+n33+k1 is 7 or lower. In yet another exemplary embodiment, n31+n32+n33+k1 is 5 or lower.
In an exemplary embodiment of the present specification, 30% or more of Formulae 1-1 to 1-3 are substituted with deuterium. In another exemplary embodiment, 40% or more of Formulae 1-1 to 1-3 are substituted with deuterium. In still another exemplary embodiment, 60% or more of Formulae 1-1 to 1-3 are substituted with deuterium. In yet another exemplary embodiment, 80% or more of Formulae 1-1 to 1-3 are substituted with deuterium. In yet another exemplary embodiment, 100% of Formulae 1-1 to 1-3 are substituted with deuterium.
In Formulae 1-1 to 1-3, the higher the deuterium substitution rate is, the more conspicuous the long service life characteristics of a device are.
In an exemplary embodiment of the present specification, n11 is 6, and Ar12 and Ar13 are deuterium.
In an exemplary embodiment of the present specification, n21 is 6, and Ar23 and Ar24 are deuterium.
In an exemplary embodiment of the present specification, n31 is 6, and Ar31 and Ar32 are deuterium.
When deuterium is linked to anthracene, the long service life effect of a device is enhanced as compared to the case where deuterium is linked to other substituents.
In an exemplary embodiment of the present specification, Formulae 1-1 to 1-3 include at least one hydrogen. That is, Formulae 1-1 to 1-3 are deuterated to less than 100%.
In an exemplary embodiment of the present specification, the compound of Formula 1-1 is represented by any one selected from the following Formulae 101 to 104.
In Formulae 101 to 104, Ar11 to Ar13, D, n11 to n13, m11, and L1 are the same as defined in Formula 1-1.
In an exemplary embodiment of the present specification, the compound of Formula 1-2 is represented by any one selected from the following Formulae 111 to 114.
In Formulae 111 to 114, D, n21 to n23, Ar21 to Ar24, m21, m22, and L2 are the same as defined in Formula 1-2.
In an exemplary embodiment of the present specification, the compound of Formula 1-3 is represented by any one selected from the following Formulae 121 to 124.
In Formulae 121 to 124, Ar31, Ar32, D, n31 to n33, and L3 are the same as defined in Formula 1-3.
In an exemplary embodiment of the present specification, Formulae 1-1 and 1-2 are represented by Formula 101, 102, 111, or 112. When dibenzofuran is linked to anthracene via No. 1 or No. 2 carbon of dibenzofuran as in Formula 101, 102, 111, or 112, the driving voltage of the device is low, which is advantageous in constructing a highly efficient device.
In an exemplary embodiment of the present specification, the compound represented by Formula 1-1 is any one selected from the following compounds.
In an exemplary embodiment of the present specification, the compound represented by Formula 1-2 is any one selected from the following compounds.
In an exemplary embodiment of the present specification, the compound represented by Formula 1-3 is any one selected from the following compounds.
Hereinafter, Formula 2 will be described.
The present specification provides a compound represented by the following Formula 2.
In Formula 2,
Y5 is C or Si,
R1 to R5, Z7, and Z8 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted alkylthio group; a substituted or unsubstituted arylthio group; or a substituted or unsubstituted amine group, or are bonded to an adjacent substituent to form a substituted or unsubstituted ring, and
r1 to r3 are an integer from 0 to 3, and substituents in the parenthesis are the same as or different from each other when r1 to r3 are each 2 or higher.
In an exemplary embodiment of the present specification, the compound of Formula 2 includes at least one deuterium.
In an exemplary embodiment of the present specification, when r1 is 2 or higher, a plurality of R1's are the same as or different from each other. In another exemplary embodiment, when r2 is 2 or higher, a plurality of R2's are the same as or different from each other. In still another exemplary embodiment, when r3 is 2 or higher, a plurality of R3's are the same as or different from each other.
In an exemplary embodiment of the present specification, Z7 and Z8 are the same as or different from each other, and are each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group, or are bonded to each other to form a substituted or unsubstituted ring.
In an exemplary embodiment of the present specification, Z7 and Z8 are the same as or different from each other, and are each independently hydrogen; deuterium; a substituted or unsubstituted C1-C10 alkyl group; or a substituted or unsubstituted C6-C30 aryl group, or are bonded to each other to form a substituted or unsubstituted C5-C30 ring.
In an exemplary embodiment of the present specification, Z7 and Z8 are the same as or different from each other, and are each independently a substituted or unsubstituted C1-C6 alkyl group; or a substituted or unsubstituted C6-C20 aryl group, or are bonded to each other to form a substituted or unsubstituted C5-C20 ring.
In an exemplary embodiment of the present specification, Z7 and Z8 are the same as or different from each other, and are each independently a methyl group; or a phenyl group which is unsubstituted or substituted with deuterium or a tert-butyl group, or are bonded to each other to form a fluorene ring which is unsubstituted or substituted with deuterium or a tert-butyl group; or a dibenzosilole ring which is unsubstituted or substituted with deuterium or a tert-butyl group while being a phenyl group which is unsubstituted or substituted with deuterium or a tert-butyl group.
In an exemplary embodiment of the present specification, R4 and R5 are the same as or different from each other, and are each independently a substituted or unsubstituted cycloalkyl group; or a group represented by the following Formula 3-A, or are bonded to an adjacent substituent to form a substituted or unsubstituted ring.
In an exemplary embodiment of the present specification, R4 and R5 are bonded to adjacent R1 or R2 to form a substituted or unsubstituted ring while being a substituted or unsubstituted cycloalkyl group.
In an exemplary embodiment of the present specification, R4 and R5 are the same as or different from each other, and are each independently a substituted or unsubstituted C3-C30 cycloalkyl group; or a group represented by the following Formula 3-A, or are bonded to an adjacent substituent to form a substituted or unsubstituted C5-C30 hydrocarbon ring.
In an exemplary embodiment of the present specification, R4 and R5 are the same as or different from each other, and are each independently a substituted or unsubstituted cyclohexyl group; or a substituted or unsubstituted adamantyl group; or a group represented by the following Formula 3-A; or are bonded to adjacent R1 or R2 to form a substituted or unsubstituted ring while being a substituted or unsubstituted cyclohexyl group.
In an exemplary embodiment of the present specification, R4 and R5 are the same as or different from each other, and are bonded to adjacent R1 or R2 to form a ring which is unsubstituted or substituted with a methyl group, while being each independently a cyclohexyl group which is unsubstituted or substituted with a methyl group.
In an exemplary embodiment of the present specification, R4 and R5 are a group represented by the following Formula 3-A.
In Formula 3-A,
R31 is hydrogen; deuterium; a cyano group; a halogen group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted silyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; or a substituted or unsubstituted amine group, or are bonded to an adjacent substituent to form a substituted or unsubstituted ring,
r31 is an integer from 0 to 5, and R31's are the same as or different from each other when r31 is 2 or higher, and
is a bonding site.
In an exemplary embodiment of the present specification, when r31 is 2 or higher, a plurality of R31's are the same as or different from each other.
In an exemplary embodiment of the present specification, R31 may be bonded to adjacent R1 or R2 to form a ring.
In an exemplary embodiment of the present specification, R1 to R3 and R31 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted alkylthio group; a substituted or unsubstituted arylthio group; or a substituted or unsubstituted amine group, or are bonded to an adjacent substituent to form a substituted or unsubstituted ring.
In an exemplary embodiment of the present specification, R1 to R3 and R31 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted C1-C10 alkyl group; a substituted or unsubstituted C3-C30 cycloalkyl group; a substituted or unsubstituted C1-C30 alkylsilyl group; a substituted or unsubstituted C6-C60 arylsilyl group; a substituted or unsubstituted C6-C30 aryl group; a substituted or unsubstituted C2-C30 heterocyclic group; a substituted or unsubstituted C1-C10 alkoxy group; a substituted or unsubstituted C6-C60 arylamine group; or a substituted or unsubstituted heteroarylamine group, or are bonded to an adjacent substituent to form a substituted or unsubstituted C2-C30 ring.
In an exemplary embodiment of the present specification, R1 to R3, and R31 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a C1-C10 alkyl group which is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a C1-C10 alkyl group, and a C6-C30 aryl group or a substituent to which two or more groups selected from the above group are linked; a C3-C30 cycloalkyl group; a C1-C30 alkylsilyl group; a C6-C60 arylsilyl group; a C6-C30 aryl group which is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a cyano group, a C1-C10 alkyl group, a silyl group, a C6-C30 aryl group, and a C9-C30 fused ring group or a substituent to which two or more groups selected from the above group are linked; a C9-C30 fused hydrocarbon ring group which is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium and a C1-C10 alkyl group or a substituent to which two or more groups selected from the above group are linked; a C2-C30 heterocyclic group which is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a cyano group, a C1-C10 alkyl group, a silyl group, and a C6-C30 aryl group or a substituent to which two or more groups selected from the above group are linked; a C1-C10 alkoxy group which is unsubstituted or substituted with a halogen group; or an amine group which is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a cyano group, a C1-C10 alkyl group, a silyl group, a C6-C30 aryl group, and a C9-C30 fused hydrocarbon ring group or a substituent to which two or more groups selected from the above group are linked, or are bonded to an adjacent substituent to form a C2-C30 ring which is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a C1-C10 alkyl group, a silyl group, and a C6-C30 aryl group or a substituent to which two or more groups selected from the above group are linked.
In an exemplary embodiment of the present specification, R1 to R3 and R31 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; an alkyl group which is unsubstituted or substituted with deuterium or a C6-C30 aryl group; a C3-C30 cycloalkyl group; a C1-C30 alkylsilyl group; a C6-C60 arylsilyl group; a C6-C30 aryl group which is unsubstituted or substituted with deuterium, a halogen group, a cyano group, a C1-C10 alkyl group, a C1-C10 alkyl group substituted with deuterium, a C1-C10 haloalkyl group, a C9-C30 fused hydrocarbon ring group, a C9-C30 fused hydrocarbon ring group substituted with a C1-C10 alkyl group, or a C1-C30 alkylsilyl group; a C2-C30 heterocyclic group which is unsubstituted or substituted with deuterium, a C1-C10 alkyl group, a C1-C10 alkyl group substituted with deuterium, a C6-C30 aryl group, a C6-C30 aryl group substituted with deuterium, or a C1-C30 alkylsilyl group; a C1-C10 alkoxy group which is unsubstituted or substituted with a halogen group; or a C6-C60 arylamine group which is unsubstituted or substituted with deuterium, a C1-C10 alkyl group, a C1-C10 alkyl group substituted with deuterium, a C1-C30 alkylsilyl group, or a C6-C60 arylsilyl group, and which is unfused or fused with a C5-C30 aliphatic hydrocarbon ring, or are bonded to an adjacent substituent to form a C2-C30 ring which is unsubstituted or substituted with deuterium, a C1-C10 alkyl group, a C1-C10 alkyl group substituted with deuterium, a C6-C30 aryl group, or a C6-C30 aryl group substituted with deuterium, or a C1-C30 alkylsilyl group.
In an exemplary embodiment of the present specification, R1 to R3 and R31 are the same as or different from each other, and are each independently hydrogen; deuterium; a fluoro group; a cyano group; a methyl group which is unsubstituted or substituted with deuterium; an ethyl group; an isopropyl group which is unsubstituted or substituted with deuterium; a tert-butyl group which is unsubstituted or substituted with deuterium; an isopropyl group substituted with a phenyl group and deuterium; a cyclohexyl group; an adamantyl group; a trimethylsilyl group; a triphenylsilyl group; a phenyl group which is unsubstituted or substituted with deuterium, a fluoro group, a cyano group, a methyl group, an isopropyl group, a tert-butyl group, CD3, C(CD3), CF3, a trimethylsilyl group, a tert-butyldimethylsilyl group, a tetramethyltetrahydronaphthalene group, a dimethyldihydroindene group, or a tetramethyldihydroindene group; a biphenyl group which is unsubstituted or substituted with deuterium, a fluoro group, a cyano group, a methyl group, an isopropyl group, a tert-butyl group, CD3, CF3, C(CD3), a trimethylsilyl group, a tert-butyldimethylsilyl group, a tetramethyltetrahydronaphthalene group, a dimethyldihydroindene group, or a tetramethyldihydroindene group; a naphthyl group; a fluorene group which is unsubstituted or substituted with a methyl group or a phenyl group; a benzofluorene group which is unsubstituted or substituted with a methyl group or a phenyl group; a hydronaphthalene group which is unsubstituted or substituted with a methyl group; a dihydroindene group which is unsubstituted or substituted with a methyl group; a diphenyl amine group which is unsubstituted or substituted with deuterium, a methyl group, an isopropyl group, a tert-butyl group, CD3, C(CD3), a trimethylsilyl group, a triphenylsilyl group, or a phenyl group, and which is unfused or fused with a cyclopentene ring or a cyclohexene ring; a methoxy group which is unsubstituted or substituted with a fluoro group; a dibenzofuran group which is unsubstituted or substituted with a methyl group, a tert-butyl group, or a phenyl group; a naphthobenzofuran group; a dibenzothiophene group which is unsubstituted or substituted with a methyl group, a tert-butyl group, or a phenyl group; a naphthobenzothiophene group; a dibenzosilole group which is unsubstituted or substituted with a methyl group or a phenyl group; a naphthobenzosilole group which is unsubstituted or substituted with a methyl group or a phenyl group; a pyridyl group which is unsubstituted or substituted with deuterium, a methyl group, an isopropyl group, or a tert-butyl group; and a group represented by one of the following Formulae 2-A-1 to 2-A-6.
In an exemplary embodiment of the present specification, R1 to R3 and R31 are bonded to an adjacent substituent to form a substituted or unsubstituted aromatic hydrocarbon ring; a substituted or unsubstituted aliphatic hydrocarbon ring; a substituted or unsubstituted aromatic hetero ring; or a substituted or unsubstituted aliphatic hetero ring.
In an exemplary embodiment of the present specification, R1 is bonded to adjacent R1 to form a substituted or unsubstituted ring. In another exemplary embodiment, R2 is bonded to adjacent R2 to form a substituted or unsubstituted ring. In still another exemplary embodiment, R3 is bonded to adjacent R3 to form a substituted or unsubstituted ring. In yet another exemplary embodiment, R31 is bonded to adjacent R31 to form a substituted or unsubstituted ring.
“An aliphatic hydrocarbon ring formed by bonding two of adjacent R1's, two of adjacent R2's, two of adjacent R3's, or two of adjacent R31's to each other” may become a C5-C20 aliphatic hydrocarbon ring. Specifically, the aliphatic hydrocarbon ring may be a cyclohexene ring; a cyclopentene ring; a bicyclo[2.2.1]heptene ring; or a bicyclo[2.2.2]octene ring, and the ring is unsubstituted or substituted with a methyl group.
Further, “an aromatic hydrocarbon ring formed by bonding two of adjacent R1's, two of adjacent R2's, two of adjacent R3's, or two of adjacent R31's to each other” may become a C6-C20 aromatic hydrocarbon ring. Specifically, the aromatic hydrocarbon ring may be an indene ring; or a spiro[indene-fluorene]ring, and the ring is unsubstituted or substituted with a methyl group, an isopropyl group, a tert-butyl group, or a phenyl group.
In addition, “an aromatic hetero ring formed by bonding two of adjacent R1's, two of adjacent R2's, two of adjacent R3's, or two of adjacent R31's to each other” may be a C5-C20 aromatic hetero ring including one or more of O, S, Si, and N. Specifically, the aromatic hetero ring may be a furan ring; a dihydrofuran ring; a benzofuran ring; a naphthofuran ring; a thiophene ring; a dihydrothiophene ring; a benzothiophene ring; a naphthofuran ring; an indole ring; a benzoindole ring; a silole ring; a benzosilole ring; or a naphthosilole ring, and the ring is unsubstituted or substituted with a methyl group, an isopropyl group, a tert-butyl group, or a phenyl group.
In an exemplary embodiment of the present specification, two of adjacent R1's, two of adjacent R2's, two of adjacent R3's, or two of adjacent R31's are bonded to each other to form one ring of Cy1 to Cy3 to be described below.
In an exemplary embodiment of the present specification, R31 is linked to the ortho position with respect to nitrogen (N) while being a substituent other than hydrogen. Specifically, in the following formula, a substituent other than hydrogen (R31 of a halogen group, a cyano group, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a heterocyclic group, a cycloalkyl group, an alkylsilyl group, an arylsilyl group, an arylalkyl group, an alkylamine group, an arylamine group, a heteroarylamine group, and the like) is linked to one or two of the positions represented by a dotted line. In this case, a substituent may be further linked to or a ring may be formed at the meta or para position with respect to nitrogen (N).
In an exemplary embodiment of the present specification, a ring formed by bonding two of adjacent R1's, two of adjacent R2's, two of adjacent R3's, or two of adjacent R6's to each other is one of the following rings Cy1 to Cy3.
In Cy1 to Cy3,
* is a carbon that participates in the formation of a ring among R1 to R3, R6, and R7,
Y10 is 0; S; Si(Ra3) (Ra4); or N(Ra5),
Y11 is 0; S; Si(Ra3) (Ra4); C(Ra3) (Ra4); or N(Ra5),
R41 to R43 and Ra3 to Ra5 are the same as or different from each other, and are each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group, and are bonded to an adjacent substituent to form a substituted or unsubstituted ring,
p6 is an integer from 1 to 3, and
r41 is an integer from 0 to 10, r42 is an integer from 0 to 4, r43 is an integer from 0 to 2, and when r41 to r43 are each 2 or higher, substituents in the parenthesis are the same as or different from each other.
In an exemplary embodiment of the present specification, when r41 is 2 or higher, a plurality of R41's are the same as or different from each other. In another exemplary embodiment, when r42 is 2 or higher, a plurality of R42's are the same as or different from each other. In still another exemplary embodiment, when r43 is 2 or higher, a plurality of R43's are the same as or different from each other.
In the structures, * is a position in which a substituent is fused with Formula 2.
In an exemplary embodiment of the present specification, p6 is 1 or 2.
In an exemplary embodiment of the present specification, R41 to R43 and Ra3 to Ra5 are the same as or different from each other, and are each independently hydrogen; deuterium; a substituted or unsubstituted C1-C10 alkyl group; a substituted or unsubstituted C6-C30 aryl group, or are bonded to an adjacent substituent to form a substituted or unsubstituted ring.
In an exemplary embodiment of the present specification, R41 to R43 and Ra3 to Ra5 are the same as or different from each other, and are each independently hydrogen; deuterium; a C1-C6 alkyl group which is unsubstituted or substituted with deuterium; or a C6-C20 aryl group which is unsubstituted or substituted with deuterium or a C1-C6 alkyl group, and are bonded to an adjacent substituent to form a C5-C20 hydrocarbon ring which is unsubstituted or substituted with deuterium, a C1-C6 alkyl group, or a C6-C20 aryl group; or a C2-C20 hetero ring which is unsubstituted or substituted with deuterium, a C1-C6 alkyl group, or a C6-C20 aryl group.
In an exemplary embodiment of the present specification, R41 to R43 are the same as or different from each other, and are each independently hydrogen; deuterium; a methyl group which is unsubstituted or substituted with deuterium; an isopropyl group; a tert-butyl group; or a phenyl group.
In an exemplary embodiment of the present specification, R41 is bonded to R41 to make a form in which a Cy1 ring is a double ring (a bicycloalkyl ring or a bicycloalkene ring), such as a bridgehead, or a fused ring. Specifically, the Cy1 is a bicyclo[2.2.2]octene ring; or a bicyclo[2.2.1]heptene ring, and the ring is unsubstituted or substituted with R41.
In an exemplary embodiment of the present specification, R42 is bonded to adjacent R42 to form a substituted or unsubstituted aliphatic hydrocarbon ring.
In an exemplary embodiment of the present specification, R42 is bonded to adjacent R42 to form a C5-C30 aliphatic hydrocarbon ring which is unsubstituted or substituted with deuterium, a C1-C10 alkyl group, or a C1-C10 alkyl group substituted with deuterium.
In an exemplary embodiment of the present specification, R42 is bonded to adjacent R42 to form a C5-C20 aliphatic hydrocarbon ring which is unsubstituted or substituted with deuterium, a C1-C6 alkyl group, or a C1-C6 alkyl group substituted with deuterium.
In an exemplary embodiment of the present specification, R43 is bonded to adjacent R43 to form a substituted or unsubstituted C6-C30 aromatic hydrocarbon ring; or a substituted or unsubstituted C5-C30 aliphatic hydrocarbon ring.
In an exemplary embodiment of the present specification, R43 is bonded to adjacent R43 to form a benzene ring; a naphthalene ring; a cyclopentene ring; a cyclohexene ring; a tetrahydronaphthalene ring; a bicyclo[2.2.2]octene ring; or a bicyclo[2.2.1]heptene ring, and the ring is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a C1-C6 alkyl group, and a C6-C20 aryl group or a substituent to which two or more groups selected from the above group are linked.
In an exemplary embodiment of the present specification, Ra3 to Ra5 are the same as or different from each other, and are each independently a substituted or unsubstituted C1-C10 alkyl group; a substituted or unsubstituted C6-C30 aryl group, or are bonded to an adjacent substituent to form a substituted or unsubstituted C5-C30 hydrocarbon ring.
In an exemplary embodiment of the present specification, Ra3 and Ra4 are the same as or different from each other, and are each independently a C1-C6 alkyl group which is unsubstituted or substituted with deuterium; a C6-C20 aryl group which is unsubstituted or substituted with deuterium or a C1-C6 alkyl group, or are bonded to an adjacent substituent to form a C5-C20 hydrocarbon ring which is unsubstituted or substituted with deuterium or a C1-C6 alkyl group.
In an exemplary embodiment of the present specification, Ra3 and Ra4 are the same as or different from each other, and are each independently a methyl group; or a phenyl group, or are bonded to each other to form a fluorene ring which is unsubstituted or substituted with a methyl group, an isopropyl group, or a tert-butyl group.
In an exemplary embodiment of the present specification, Ra5 is a C6-C30 aryl group which is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a C1-C10 alkyl group, and a C1-C10 alkoxy group, or a substituent to which two or more groups selected from the above group are linked.
In an exemplary embodiment of the present specification, Ra5 is a C6-C20 aryl group which is unsubstituted or substituted with deuterium, a halogen group, a C1-C6 alkyl group, a C1-C6 alkyl group substituted with deuterium, a C1-C6 haloalkyl group, or a C1-C6 haloalkoxy group.
In an exemplary embodiment of the present specification, Ra5 is a phenyl group which is unsubstituted or substituted with deuterium, a methyl group, a methyl group substituted with deuterium, a trifluoromethyl group, a trifluoromethoxy group, an isopropyl group, or a tert-butyl group; a biphenyl group; or a terphenyl group.
In an exemplary embodiment of the present specification, Y10 is 0; S; Si(Ra3) (Ra4); or N(Ra5).
In an exemplary embodiment of the present specification, Cy1 is one selected from the following structures.
In an exemplary embodiment of the present specification, Cy2 is one selected from the following structures, and Y10 is the same as that described above.
In an exemplary embodiment of the present specification, Cy3 is one selected from the following structures.
In the structures, Y11 is the same as that described above,
R431 is hydrogen; deuterium; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group, r431 is an integer from 0 to 2, r432 is an integer from 0 to 4, and r433 is an integer from 0 to 6, and
when r431 is 2 or r432 and r433 are 2 or higher, R431's are the same as or different from each other.
In an exemplary embodiment of the present specification, R431 is the same except that R431 forms a ring in the above-described definition of R43.
In an exemplary embodiment of the present specification, R43 is hydrogen; deuterium; a methyl group; an isopropyl group; a tert-butyl group; or a phenyl group.
In an exemplary embodiment of the present specification, the heterocyclic group of R1 to R3 and R6 includes one or more of N, O, S, and Si as a heteroatom.
In an exemplary embodiment of the present specification, the O-containing heterocyclic group of R1 to R3 and R6 may be a benzofuran group; a dibenzofuran group; or a naphthobenzofuran group, and is unsubstituted or substituted with deuterium, a C1-C6 alkyl group, or a C6-C20 aryl group.
In an exemplary embodiment of the present specification, the S-containing heterocyclic group of R1 to R3 and R6 may be a benzothiophene group; a dibenzothiophene group; or a naphthobenzothiophene group, and is unsubstituted or substituted with deuterium, a C1-C6 alkyl group, or a C6-C20 aryl group.
In an exemplary embodiment of the present specification, the Si-containing heterocyclic group of R1 to R3 and R6 may be a benzosilole group; a dibenzosilole group; or a naphthobenzosilole group, and is unsubstituted or substituted with deuterium, a C1-C6 alkyl group, or a C6-C20 aryl group.
In an exemplary embodiment of the present specification, the N-containing heterocyclic group of R1 to R3 and R6 is represented by a substituted or unsubstituted pyridyl group; or one of the following Formulae 2-A-1 to 2-A-6.
In Formulae 2-A-1 to 2-A-6,
* is a bonding site,
Y1 is C or Si,
p1 is 0 or 1,
Y6 and Y7 are the same as or different from each other, and are each independently O; S; C(T26) (T27); or Si (T26) (T27),
T11 to T16 and T20 to T29 are the same as or different from each other, and are each independently hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heterocyclic group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; a substituted or unsubstituted alkylthio group; a substituted or unsubstituted arylthio group; or a substituted or unsubstituted amine group, or are bonded to an adjacent substituent to form a substituted or unsubstituted ring,
Cy5 is an aliphatic hydrocarbon ring,
Cy6 is an aromatic hydrocarbon ring, and
t28 is an integer from 0 to 10, t29 is an integer from 0 to 10, and when t28 and t29 are each 2 or higher, substituents in the parenthesis are the same as or different from each other.
In an exemplary embodiment of the present specification, Y6 is 0; or S.
In an exemplary embodiment of the present specification, Y6 is C(T26) (T27); or Si(T26) (T27).
In an exemplary embodiment of the present specification, Y6 is C(T26) (T27).
In an exemplary embodiment of the present specification, Y7's are the same as or different from each other, and are each independently O; S; or C(T26) (T27).
In an exemplary embodiment of the present specification, t28 is an integer from 0 to 6, and when t28 is 2 or higher, a plurality of T28's are the same as or different from each other.
In an exemplary embodiment of the present specification, t29 is an integer from 0 to 10, and when t29 is 2 or higher, a plurality of T29's are the same as or different from each other.
In an exemplary embodiment of the present specification, T11 to T14 are the same as or different from each other, and are each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted alkylsilyl group; or a substituted or unsubstituted arylsilyl group, or are bonded to an adjacent substituent to form a ring.
In an exemplary embodiment of the present specification, T11 to T14 are the same as or different from each other, and are each independently hydrogen; deuterium; a substituted or unsubstituted C1-C10 alkyl group; a substituted or unsubstituted C6-C30 aryl group; a substituted or unsubstituted C1-C30 alkylsilyl group; or a substituted or unsubstituted C6-C60 arylsilyl group, or are bonded to an adjacent substituent to form a substituted or unsubstituted C6-C30 aromatic hydrocarbon ring.
In an exemplary embodiment of the present specification, T11 to T14 are the same as or different from each other, and are each independently hydrogen; deuterium; a C1-C6 alkyl group which is unsubstituted or substituted with deuterium; a C6-C20 aryl group which is unsubstituted or substituted with deuterium or a C1-C6 alkyl group; or a C1-C30 alkylsilyl group, or are bonded to an adjacent substituent to form a C6-C30 aromatic hydrocarbon ring which is unsubstituted or substituted with deuterium or a C1-C6 alkyl group.
In an exemplary embodiment of the present specification, T11 to T14 are the same as or different from each other, and are each independently hydrogen; deuterium; a methyl group which is unsubstituted or substituted with deuterium; an isopropyl group; a tert-butyl group; a phenyl group which is unsubstituted or substituted with deuterium, a methyl group, an isopropyl group, or a tert-butyl group; or a trimethylsilyl group, or are bonded to an adjacent substituent to form a benzene ring which is unsubstituted or substituted with deuterium, a methyl group, an isopropyl group, or a tert-butyl group.
In an exemplary embodiment of the present specification, T15 and T16 are the same as or different from each other, and are each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group, or are bonded to each other to form a substituted or unsubstituted hydrocarbon ring.
In an exemplary embodiment of the present specification, T15 and T16 are the same as or different from each other, and are each independently hydrogen; deuterium; a substituted or unsubstituted C1-C6 alkyl group; or a substituted or unsubstituted C6-C20 aryl group, or are bonded to each other to form a substituted or unsubstituted C5-C20 hydrocarbon ring.
In an exemplary embodiment of the present specification, T15 and T16 are the same as or different from each other, and are each independently hydrogen; deuterium; or a methyl group, or are bonded to each other to form a fluorene ring; or a dibenzosilole ring which is unsubstituted or substituted with a tert-butyl group, while being a phenyl group which is unsubstituted or substituted with a tert-butyl group.
In an exemplary embodiment of the present specification, Y1 is C.
In an exemplary embodiment of the present specification, Y1 is Si.
In an exemplary embodiment of the present specification, when p1 is 0, a site including Y1 is a direct bond.
In an exemplary embodiment of the present specification, T20 to T27 are the same as or different from each other, and are each independently hydrogen; deuterium; a substituted or unsubstituted C1-C10 alkyl group; a substituted or unsubstituted C6-C30 aryl group; or a substituted or unsubstituted C1-C30 alkylsilyl group.
In an exemplary embodiment of the present specification, T20 to T27 are the same as or different from each other, and are each independently hydrogen; deuterium; a C1-C6 alkyl group which is unsubstituted or substituted with deuterium; a C6-C20 aryl group which is unsubstituted or substituted with deuterium; or a substituted or unsubstituted C1-C18 alkylsilyl group.
In an exemplary embodiment of the present specification, T20 to T27 are the same as or different from each other, and are each independently hydrogen; deuterium; a methyl group; a phenyl group; or a trimethylsilyl group.
In an exemplary embodiment of the present specification, T26 and T27 are each a methyl group.
In an exemplary embodiment of the present specification, T20 to T27 are each a methyl group.
In an exemplary embodiment of the present specification, T28 and T29 are the same as or different from each other, and are each independently hydrogen; deuterium; a substituted or unsubstituted C1-C6 alkyl group; or a substituted or unsubstituted C6-C20 aryl group.
In an exemplary embodiment of the present specification, T28 and T29 are the same as or different from each other, and are each independently hydrogen; deuterium; a C1-C6 alkyl group which is unsubstituted or substituted with deuterium; or a C6-C20 aryl group which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, T28 and T29 are the same as or different from each other, and are each independently hydrogen; deuterium; a tert-butyl group; or a phenyl group.
In an exemplary embodiment of the present specification, T28 and T29 are the same as or different from each other, and are each independently hydrogen; deuterium; or a tert-butyl group.
In an exemplary embodiment of the present specification, T29 is optionally bonded to adjacent T29 to form a substituted or unsubstituted aromatic hydrocarbon ring.
In an exemplary embodiment of the present specification, T29 is bonded to adjacent T29 to form a benzene ring.
In an exemplary embodiment of the present specification, T28 is hydrogen; deuterium; a tert-butyl group; or a phenyl group.
In an exemplary embodiment of the present specification, T28 is hydrogen; deuterium; or a tert-butyl group.
In an exemplary embodiment of the present specification, T28 is hydrogen; or deuterium.
In an exemplary embodiment of the present specification, T29 is hydrogen; or deuterium.
In an exemplary embodiment of the present specification, Cy5 is a C5-C20 aliphatic hydrocarbon ring.
In an exemplary embodiment of the present specification, Cy5 is a cyclopentane ring; a cyclohexane ring; or a cycloheptane ring.
In an exemplary embodiment of the present specification, Cy5 is a cyclohexane ring.
In an exemplary embodiment of the present specification, Cy6 is a C6-C20 aromatic hydrocarbon ring.
In an exemplary embodiment of the present specification, Cy6 is a benzene ring; or a naphthalene ring.
In an exemplary embodiment of the present specification, Cy6 is a benzene ring.
In an exemplary embodiment of the present specification, T17 to T19 are the same as or different from each other, and are each independently a substituted or unsubstituted alkyl group; or a substituted or unsubstituted aryl group, and at least one of T17 to T19 is a substituted or unsubstituted aryl group.
In an exemplary embodiment of the present specification, T17 to T19 are the same as or different from each other, and are each independently a substituted or unsubstituted C1-C10 alkyl group; or a substituted or unsubstituted C6-C30 aryl group, and at least one of T17 to T19 is a substituted or unsubstituted C6-C30 aryl group.
In an exemplary embodiment of the present specification, T17 to T19 are the same as or different from each other, and are each independently a C1-C6 alkyl group which is unsubstituted or substituted with deuterium; or a C6-C20 aryl group which is unsubstituted or substituted with deuterium, and at least one of T17 to T19 is a C6-C20 aryl group which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, one of T17 to T19 is a C6-C20 aryl group which is unsubstituted or substituted with deuterium, and two of T17 to T19 are a C1-C6 alkyl group which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, T17 to T19 are the same as or different from each other, and are each independently a C1-C6 alkyl group; or a C6-C20 aryl group, and at least one of T17 to T19 is a C6-C20 aryl group.
In an exemplary embodiment of the present specification, T17 is a substituted or unsubstituted aryl group, T18 is a substituted or unsubstituted alkyl group, and T19 is a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
In an exemplary embodiment of the present specification, T17 to T19 are the same as or different from each other, and are each independently a methyl group which is unsubstituted or substituted with deuterium; or a phenyl group which is unsubstituted or substituted with deuterium, and at least one of T17 to T19 is a phenyl group which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, one of T17 to T19 is a phenyl group which is unsubstituted or substituted with deuterium, and two of T17 to T19 are a methyl group which is unsubstituted or substituted with deuterium.
In an exemplary embodiment of the present specification, T17 to T19 are the same as or different from each other, and are each independently a methyl group; or a phenyl group, and at least one of T17 to T19 is a phenyl group.
In an exemplary embodiment of the present specification, one of T17 to T19 is a phenyl group, and the other two are a methyl group.
In an exemplary embodiment of the present specification, Formula 2 is asymmetric with respect to a center line. In this case, the center line is a line penetrating B of a mother nucleus structure and a benzene ring at the bottom. That is, in the following structure, the left and right substituents or structures are different with respect to the dotted line.
In an exemplary embodiment of the present specification, the compound represented by Formula 2 is any one selected from the following compounds.
According to an exemplary embodiment of the present invention, the compounds of Formulae 1-1 to 1-3 may be prepared as in the following Reaction Schemes 1 to 6, and the compound of Formula 2 may be prepared as in the following Reaction Scheme 7. The following Reaction Schemes 1 to 7 describe synthesis procedures of partial compounds corresponding to Formulae 1-1 to 1-3 and 2 of the present application, but various compounds corresponding to Formulae 1-1 to 1-3 and 2 of the present application may be synthesized using the synthesis procedures as in the following Reaction Schemes 1 to 7, a substituent may be bonded by methods known in the art, and the type and position of substituent and the number of substituents may be changed according to the technology known in the art.
The organic light emitting device of the present specification may be manufactured by typical methods and materials for manufacturing an organic light emitting device, except that a light emitting layer is formed using one or more of the compounds represented by Formulae 1-1 to 1-3, and the compound represented by Formula 2.
A light emitting layer including one or more of the compounds represented by Formulae 1-1 to 1-3, and the compound represented by Formula 2 may be formed as an organic material layer by not only a vacuum deposition method, but also a solution application method. Here, the solution application 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 specification may also be composed of a structure including the light emitting layer, but may be composed of a structure further including an additional organic material layer. The additional organic material layer may be one or more layers of a hole injection layer, a hole transport layer, a layer which simultaneously transports and injects holes, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, a layer which simultaneously transports and injects electrons, and a hole blocking layer. However, the structure of the organic light emitting device is not limited thereto, and may include a fewer or greater number of organic material layers.
In the organic light emitting device according to an exemplary embodiment of the present specification, the light emitting layer includes one or more of the compounds represented by Formulae 1-1 to 1-3 as a host, and includes the compound represented by Formula 2 as a dopant.
In an exemplary embodiment of the present specification, the light emitting layer includes one of the compounds represented by Formulae 1-1 to 1-3 as a host.
In an exemplary embodiment of the present specification, the light emitting layer includes two of the compounds represented by Formulae 1-1 to 1-3 as a host. In this case, one of the compounds represented by Formulae 1-1 to 1-3 is referred to as a first host, and the other compound is referred to as a second host.
In an exemplary embodiment of the present specification, a weight ratio of the first host and the second host is 1:9 to 9:1, preferably 3:7 to 7:3.
In the organic light emitting device according to an exemplary embodiment of the present specification, the dopant in the light emitting layer may be included in an amount of 0.1 part by weight to 50 parts by weight, preferably 1 part by weight to 30 parts by weight, and more preferably 1 part by weight to 10 parts by weight, based on 100 parts by weight of the host. Within the above range, energy transfer from the host to the dopant occurs efficiently.
According to an exemplary embodiment of the present invention, the maximum light emission peak of the light emitting layer including one or more of the compounds represented by any one of Formulae 1-1 to 1-3 and the compound represented by Formula 2 is present within a range from 400 nm to 500 nm. That is, the light emitting layer is a blue light emitting layer.
The structure of the organic light emitting device of the present specification may have a structure as illustrated in
The organic light emitting device according to the present specification may be manufactured by depositing a metal or a metal oxide having conductivity, or an alloy thereof on a substrate to form an anode, forming an organic material layer including the first organic material layer and the second organic material layer described above thereon, and then depositing a material, which may be used as a cathode, thereon, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. In addition to the method described above, an organic electronic device may also be made by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.
The organic material layer may also have a multi-layered structure further including a hole injection layer, a hole transport layer, a layer which simultaneously injects and transports electrons, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, a layer which simultaneously injects and transports electrons, a hole blocking layer, and the like. Further, the organic material layer may be manufactured to include a fewer number of layers by a method such as a solvent process, for example, spin coating, dip coating, doctor blading, screen printing, inkjet printing, or a thermal transfer method instead of a deposition method, using various polymer materials.
The anode is an electrode which injects holes, and as an anode material, materials having a high work function are usually preferred so as to facilitate the injection of holes into an organic material layer. Specific examples of the anode material which may be used in the present invention include: a metal, such as vanadium, chromium, copper, zinc, and gold, or an alloy thereof; a metal oxide, such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); a combination of a metal and an oxide, such as ZnO:Al or SnO2:Sb; a conductive polymer, 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.
The cathode is an electrode which injects electrons, and as a cathode material, materials having a low work function are usually preferred so as to facilitate the injection of electrons into an organic material layer. Specific examples of the cathode material include: a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or an alloy thereof; a multi-layer structured material, such as LiF/Al or LiO2/Al; and the like, but are not limited thereto.
The hole injection layer is a layer serving to facilitate the injection of holes from the anode to the light emitting layer, and may have a single-layered or multi-layered structure. A hole injection material is a material which may proficiently receive holes from an anode at low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably a value between the work function of the anode material and the HOMO of the neighboring organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene-based organic materials, anthraquinone, polyaniline-based and polythiophene-based conductive polymers, and the like, but are not limited thereto.
In an exemplary embodiment of the present specification, a hole injection layer has a multi-layered structure of two or more layers, and each layer includes a material different from each other.
The hole transport layer may serve to facilitate the transport of holes. A hole transport material is suitably a material having high hole mobility which may receive holes from an anode or a hole injection layer and transfer the holes to a light emitting layer. Specific examples thereof include arylamine-based organic materials, conductive polymers, block copolymers having both conjugated portions and non-conjugated portions, and the like, but are not limited thereto.
As the layer which simultaneously transports and injects holes, a hole transport layer material and/or a hole injection layer material known in the art may be used.
As the layer which simultaneously transports and injects electrons, an electron transport layer material and/or an electron injection layer material known in the art may be used.
An electron blocking layer may be provided between the hole transport layer and the light emitting layer. For the electron blocking layer, materials known in the art may be used.
The light emitting layer may emit red, green, or blue light, and may be composed of a phosphorescent material or a fluorescent material. The light emitting material is a material which may accept holes and electrons from a hole transport layer and an electron transport layer, respectively, and combine the holes and the electrons to emit light in a visible ray region, and is preferably a material having high quantum efficiency for fluorescence or phosphorescence. Specific examples thereof include: 8-hydroxy-quinoline aluminum complexes (Alq3); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzoxazole-based, benzthiazole-based and benzimidazole-based compounds; poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, lubrene, and the like, but are not limited thereto.
Examples of the host material for the light emitting layer include fused aromatic ring derivatives, or hetero ring-containing compounds, and the like. Specifically, examples of the fused aromatic ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and examples of the hetero ring-containing compound include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but the examples thereof are not limited thereto.
When the light emitting layer emits red light, it is possible to use a phosphorescent material such as bis(1-phenylisoquinoline) acetylacetonate iridium (PIQIr(acac)), bis(1-phenylquinoline)acetylacetonate iridium (PQIr(acac)), tris(1-phenylquinoline)iridium (PQIr), or octaethylporphyrin platinum (PtOEP), or a fluorescent material such as tris(8-hydroxyquinolino)aluminum (Alq3) as a light emitting dopant, but the light emitting dopant is not limited thereto. When the light emitting layer emits green light, it is possible to use a phosphorescent material such as fac tris(2-phenylpyridine)iridium (Ir(ppy)3), or a fluorescent material such as tris(8-hydroxyquinolino)aluminum (Alq3), as the light emitting dopant, but the light emitting dopant is not limited thereto. When the light emitting layer emits blue light, it is possible to use a phosphorescent material such as (4,6-F2ppY)2Irpic, or a fluorescent material such as spiro-DPVBi, spiro-6P, distyryl benzene (DSB), distyryl arylene (DSA), a PFO-based polymer or a PPV-based polymer as the light emitting dopant, but the light emitting dopant is not limited thereto.
A hole blocking layer may be provided between the electron transport layer and the light emitting layer, and materials known in the art may be used.
The electron transport layer serves to facilitate the transport of electrons, and has a single-layered or multi-layered structure. An electron transport material is suitably a material having high electron mobility which may proficiently accept electrons from a cathode and transfer the electrons to a light emitting layer. Specific examples thereof include: Al complexes of 8-hydroxyquinoline; complexes including Alq3; organic radical compounds; hydroxyflavone-metal complexes; and the like, but are not limited thereto.
In an exemplary embodiment of the present specification, an electron transport layer has a multi-layered structure of two or more layers, and each layer includes a material different from each other.
The electron injection layer serves to facilitate the injection of electrons. An electron injection material is preferably a compound which has a capability of transporting electrons, an effect of injecting electrons from a cathode, and an excellent effect of injecting electrons into a light emitting layer or a light emitting material, and is also excellent in the ability to form a thin film. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidene methane, anthrone, and the like, and derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.
Examples of the metal complex compounds include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato) zinc, bis(8-hydroxyquinolinato) copper, bis(8-hydroxyquinolinato) manganese, tris(8-hydroxyquinolinato) aluminum, tris(2-methyl-8-hydroxyquinolinato) aluminum, tris(8-hydroxyquinolinato) gallium, bis(10-hydroxybenzo[h]quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato) zinc, bis(2-methyl-8-quinolinato) chlorogallium, bis(2-methyl-8-quinolinato) (o-cresolato) gallium, bis(2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis(2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, but are not limited thereto.
The organic light emitting device according to the present specification may be a top emission type, a bottom emission type, or a dual emission type according to the material to be used.
Hereinafter, the present specification will be described in detail with reference to Examples, Comparative Examples, and the like for specifically describing the present specification. However, the Examples and the Comparative Examples according to the present specification may be modified in various forms, and it is not interpreted that the scope of the present specification is limited to the Examples and the Comparative Examples described below in detail. The Examples and the Comparative Examples of the present specification are provided to more completely explain the present specification to a person with ordinary skill in the art.
<1-a> Preparation of Compound BH-1-a
After 9-bromo-10-phenylanthracene (50 g, 150 mmol) and dibenzo[b,d]furan-2-ylboronic acid (31.8 g, 150 mmol) were dissolved in Dioxane (500 ml), Pd(PPh3)4 (8.7 g, 7.5 mmol) and 100 ml of an aqueous 2 M K2CO3 solution were added thereto, and the resulting solution was refluxed for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate, and then dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain Compound BH-1-a (39.1 g, yield 62%). MS: [M+H]+=421
<1-b> Preparation of Compound BH-1
Compound BH-1-a (45 g) and AlCl3 (9 g) were put into C6D6 (900 ml), and the resulting solution was stirred for 2 hours. After the reaction was completed, D2O (60 ml) was added thereto, the resulting solution was stirred for 30 minutes, and then trimethylamine (6 ml) was added dropwise thereto. The reaction solution was transferred to a separatory funnel, and an extraction with water and toluene was performed. The extract was dried over MgSO4, and then the residue was recrystallized with ethyl acetate to obtain BH-1 at a yield of 67%. MS: [M+H]+=441
<2-a> Preparation of Compound BH-2-a
Compound BH-2-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-a, except that dibenzo[b,d]furan-2-ylboronic acid was changed into dibenzo[b,d]furan-1-ylboronic acid. MS: [M+H]+=421
<2-b> Preparation of Compound BH-2
Compound BH-2 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-b, except that Compound BH-1-a was changed into Compound BH-2-a. MS: [M+H]+=441
<3-a> Preparation of Compound BH-3-a
Compound BH-3-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-a, except that dibenzo[b,d]furan-2-ylboronic acid was changed into (4-dibenzo[b,d]furan-2-yl)phenyl)boronic acid. MS: [M+H]+=497
<3-b> Preparation of Compound BH-3
Compound BH-3 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-b, except that Compound BH-1-a was changed into Compound BH-3-a. MS: [M+H]+=521
<4-a> Preparation of Compound BH-4-a
Compound BH-4-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-a, except that dibenzo[b,d]furan-2-ylboronic acid was changed into (6-dibenzo[b,d]furan-2-yl)naphthalen-2-yl)boronic acid. MS: [M+H]+=547
<4-b> Preparation of Compound BH-4
Compound BH-4 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-b, except that Compound BH-1-a was changed into Compound BH-4-a. MS: [M+H]+=573
<5-a> Preparation of Compound BH-5-a
Compound BH-5-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-a, except that dibenzo[b,d]furan-2-ylboronic acid was changed into (7-phenyldibenzo[b,d]furan-2-yl)boronic acid. MS: [M+H]+=497
<5-b> Preparation of Compound BH-5
Compound BH-5 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-b, except that Compound BH-1-a was changed into Compound BH-5-a. MS: [M+H]+=521
<6-a> Preparation of Compound BH-6-a Compound BH-6-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-a, except that dibenzo[b,d]furan-2-ylboronic acid was changed into (8-phenyldibenzo[b,d]furan-2-yl)boronic acid. MS: [M+H]+=497
<6-b> Preparation of Compound BH-6
Compound BH-6 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-b, except that Compound BH-1-a was changed into Compound BH-6-a. MS: [M+H]+=521
<8-a> Preparation of Compound BH-8-a
Compound BH-8-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-a, except that dibenzo[b,d]furan-2-ylboronic acid was changed into 2-(4-(dibenzo[b,d]furan-1-yl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. MS: [M+H]+=497
<8-b> Preparation of Compound BH-8
Compound BH-8 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-b, except that Compound BH-1-a was changed into Compound BH-8-a. MS: [M+H]+=521
<9-a> Preparation of Compound BH-9-a
Compound BH-9-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-a, except that dibenzo[b,d]furan-2-ylboronic acid was changed into 4,4,5,5-tetramethyl-2-(4-(6-phenyldibenzo[b,d]furan-4-yl)phenyl)-1,3,2-dioxaborolane. MS: [M+H]+=573
<9-b> Preparation of Compound BH-9
Compound BH-9 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-b, except that Compound BH-1-a was changed into Compound BH-9-a. MS: [M+H]+=601
<10-a> Preparation of Compound BH-10-a
Compound BH-10-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-a, except that 9-bromo-10-phenylanthracene was changed into 9-([1,1′-biphenyl]-4-yl)-10-bromoanthracene. MS: [M+H]+=497
<10-b> Preparation of Compound BH-10
Compound BH-10 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-b, except that Compound BH-1-a was changed into Compound BH-10-a. MS: [M+H]+=521
<11-a> Preparation of Compound BH-11-a
Compound BH-11-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-a, except that 9-bromo-10-phenylanthracene was changed into 9-bromo-10-(4-(naphthalen-1-yl)phenyl)anthracene and dibenzo[b,d]furan-2-ylboronic acid was changed into dibenzo[b,d]furan-1-ylboronic acid. MS: [M+H]+=547
<11-b> Preparation of Compound BH-11
Compound BH-11 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-b, except that Compound BH-1-a was changed into Compound BH-11-a. MS: [M+H]+=573
<12-a> Preparation of Compound BH-12-a
Compound BH-12-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-a, except that 9-bromo-10-phenylanthracene was changed into 9-bromo-10-(3-(naphthalen-1-yl)phenyl)anthracene, and dibenzo[b,d]furan-2-ylboronic acid was changed into dibenzo[b,d]furan-1-ylboronic acid. MS: [M+H]+=547
<12-b> Preparation of Compound BH-12
Compound BH-12 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-b, except that Compound BH-1-a was changed into Compound BH-12-a. MS: [M+H]+=573
<13-a> Preparation of Compound BH-13-a
Compound BH-13-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-a, except that 9-bromo-10-phenylanthracene was changed into 1-(10-bromoanthracen-9-yl)dibenzo[b,d]furan, and dibenzo[b,d]furan-2-ylboronic acid was changed into (4-(naphthalen-2-yl)phenyl)boronic acid. MS: [M+H]+=547
<13-b> Preparation of BH-13
Compound BH-13 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-b, except that Compound BH-1-a was changed into Compound BH-13-a. MS: [M+H]+=573
<14-a> Preparation of Compound BH-14-a
Compound BH-14-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-a, except that 9-bromo-10-phenylanthracene was changed into 1-(10-bromoanthracen-9-yl)dibenzo[b,d]furan, and dibenzo[b,d]furan-2-ylboronic acid was changed into (3-(naphthalen-2-yl)phenyl)boronic acid. MS: [M+H]+=547
<14-b> Preparation of BH-14
Compound BH-14 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-b, except that Compound BH-1-a was changed into Compound BH-14-a. MS: [M+H]+=573
<15-a> Preparation of Compound BH-15-a
After 2-(1-naphthyl)anthracene (50 g, 164 mmol) was dispersed in 500 ml of dimethylformamide, a solution of n-bromosuccinimide (29.2 g, 164 mmol) dissolved in 50 ml of dimethylformamide was slowly added dropwise thereto. After reaction at room temperature for 2 hours, 1 L of water was added dropwise thereto. When a solid was produced, the solid was filtered, and then dissolved in ethyl acetate, and the resulting solution was put into a separatory funnel, and then washed several times with distilled water. The resulting product was recrystallized in ethyl acetate to obtain Compound BH-15-a (56 g, yield 89%). MS: [M+H]+=383
<15-b> Preparation of Compound BH-15-b
Compound BH-15-b was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-a, except that 9-bromo-10-phenylanthracene was changed into BH-15-a, and dibenzo[b,d]furan-2-ylboronic acid was changed into phenylboronic acid. MS: [M+H]+=381
<15-c> Preparation of Compound BH-15-c
Compound BH-15-c was obtained by performing synthesis and purification in the same manner as in Synthesis Example 15-a, except that 2-(1-naphthyl)anthracene was changed into Compound BH-15-b. MS: [M+H]+=459<15-d> Preparation of Compound BH-15-d Compound BH-15-d was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-a, except that 9-bromo-10-phenylanthracene was changed into Compound BH-15-c. MS: [M+H]+=547 <15-e> Preparation of Compound BH-15 Compound BH-15 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-b, except that Compound BH-1-a was changed into Compound BH-15-d. MS: [M+H]+=573
<16-a> Preparation of Compound BH-16-a
Compound BH-16-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 15-a, except that 2-(1-naphthyl)anthracene was changed into Compound 9-(phenyl-d5)anthracene. MS: [M+H]+=338
<16-b> Preparation of Compound BH-16
Compound BH-16 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-b, except that Compound BH-1-a was changed into Compound BH-16-a. MS: [M+H]+=433
<17-a> Preparation of Compound BH-17-a
Compound BH-17-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-b, except that Compound BH-1-a was changed into 9-phenylanthracene. MS: [M+H]+=269
<17-b> Preparation of Compound BH-17-b
Compound BH-17-b was obtained by performing synthesis and purification in the same manner as in Synthesis Example 15-a, except that 2-(1-naphthyl)anthracene was changed into Compound BH-17-a. MS: [M+H]+=346
<17-c> Preparation of Compound BH-17
Compound BH-17 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-a, except that 9-bromo-10-phenylanthracene was changed into Compound BH-17-b. MS: [M+H]+=454
<18-a> Preparation of Compound BH-18-H
After 1-(10-bromoanthracen-9-yl)dibenzo[b,d]furan (50 g, 118 mmol) and 2-naphthylboronic acid (20.3 g, 118 mmol) were dissolved in THF (600 ml), Pd(PPh3)4 (6.82 g, 5.9 mmol) and 120 ml of an aqueous 2 M K2CO3 solution were added thereto, and the resulting solution was refluxed for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate, and then dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain Compound BH-18-H (45 g, yield 81%). (MS[M+H]+=471)
<18-b> Preparation of Compound BH-18
The synthesized Compound BH-18-H (45 g) and AlCl3 (9 g) were put into C6D6 (900 ml), and the resulting solution was stirred for 2 hours. After the reaction was completed, D2O (60 ml) was added thereto, the resulting solution was stirred for 30 minutes, and then trimethylamine (6 ml) was added dropwise thereto. The reaction solution was transferred to a separatory funnel, and an extraction with water and toluene was performed. The extract was dried over MgSO4, and then the residue was recrystallized with ethyl acetate to obtain BH-18 at a yield of 60%. (MS[M+H]+=493)
<19-a> Preparation of Compound BH-19-H
BH-19-H was obtained by reacting 2-(10-bromoanthracen-9-yl)dibenzo[b,d]furan with 2-naphthylboronic acid in the same manner as in Synthesis Example <18-a>. (Yield 78%, MS[M+H]+=471)
<19-b> Preparation of Compound BH-19
BH-19 was obtained from BH-19-H in the same manner as in Synthesis Example <18-b>. (Yield 62%, MS[M+H]+=493)
<20-a> Preparation of Compound BH-20-H
BH-20-H was obtained by reacting 3-(10-bromoanthracen-9-yl)dibenzo[b,d]furan with 2-naphthylboronic acid in the same manner as in Synthesis Example <18-a>. (Yield 69%, MS[M+H]+=471)
<20-b> Preparation of Compound BH-20
BH-20 was obtained from BH-20-H in the same manner as in Synthesis Example <18-b>. (Yield 65%, MS[M+H]+=493)
<21-a> Preparation of Compound BH-21-H BH-21-H was obtained by reacting 4-(10-bromoanthracen-9-yl)dibenzo[b,d]furan with 2-naphthylboronic acid in the same manner as in Synthesis Example <18-a>. (Yield 71%, MS[M+H]+=471, Dipole moment=0.58 D)
<21-b> Preparation of Compound BH-21
BH-21 was obtained from BH-21-H in the same manner as in Synthesis Example <18-b>. (Yield 55%, MS[M+H]+=493)
<22-a> Preparation of Compound BH-22-H BH-22-H was obtained by reacting 2-(10-bromoanthracen-9-yl)dibenzo[b,d]furan with 1-naphthylboronic acid in the same manner as in Synthesis Example <18-a>. (Yield 82%, MS[M+H]+=471)
<22-b> Preparation of Compound BH-22
BH-22 was obtained from BH-22-H in the same manner as in Synthesis Example <18-b>. (Yield 68%, MS[M+H]+=493)
<23-a> Preparation of Compound BH-23-H
BH-23-H was obtained by reacting 9-bromo-10-(naphthalen-1-yl)anthracene with (4-(dibenzo[b,d]furan-2-yl)phenyl)boronic acid in the same manner as in Synthesis Example <18-a>. (Yield 73%, MS[M+H]+=547)
<23-b> Preparation of Compound BH-23
BH-23 was obtained from BH-23-H in the same manner as in Synthesis Example <18-b>. (Yield 60%, MS[M+H]+=573)
<24-a> Preparation of Compound BH-24-H BH-24-H was obtained by reacting 9-bromo-10-(naphthalen-1-yl)anthracene with (3-(dibenzo[b,d]furan-2-yl)phenyl)boronic acid in the same manner as in Synthesis Example <18-a>. (Yield 70%, MS[M+H]+=547)
<24-b> Preparation of Compound BH-24 BH-24 was obtained from BH-24-H in the same manner as in Synthesis Example <18-b>. (Yield 66%, MS[M+H]+=573)
<25-a> Preparation of Compound BH-25-H
BH-25-H was obtained by reacting 9-bromo-10-(naphthalen-1-yl)anthracene with (4-(dibenzo[b,d]furan-2-yl)naphthalen-1-yl)boronic acid in the same manner as in Synthesis Example <18-a>. (Yield 73%, MS[M+H]+=597)
<25-b> Preparation of Compound BH-25
BH-25 was obtained from BH-25-H in the same manner as in Synthesis Example <18-b>. (Yield 64%, MS[M+H]+=625)
<26-a> Preparation of Compound BH-26-H
BH-26-H was obtained by reacting 9-bromo-10-(naphthalen-1-yl)anthracene with (9-(naphthalen-1-yl)dibenzo[b,d]furan-2-yl)boronic acid in the same manner as in Synthesis Example <18-a>. (Yield 64%, MS[M+H]+=597)
<26-b> Preparation of Compound BH-26
BH-26 was obtained from BH-26-H in the same manner as in Synthesis Example <18-b>. (Yield 62%, MS[M+H]+=625)
<27-a> Preparation of Compound BH-27-H
BH-27-H was obtained by reacting 9-bromo-10-(naphthalen-2-yl)anthracene with (6-phenyldibenzo[b,d]furan-2-yl)boronic acid in the same manner as in Synthesis Example <18-a>. (Yield 67%, MS[M+H]+=547)
<27-b> Preparation of Compound BH-27
BH-27 was obtained from BH-27-H in the same manner as in Synthesis Example <18-b>. (Yield 65%, MS[M+H]+=573)
<28-a> Preparation of Compound BH-28-a
9-(naphthalen-1-yl)anthracene (54 g) and AlCl3 (9 g) were put into C6D6 (900 ml), and the resulting mixture was stirred for 2 hours. After the reaction was completed, D2O (60 ml) was added thereto, the resulting solution was stirred for 30 minutes, and then trimethylamine (6 ml) was added dropwise thereto. The reaction solution was transferred to a separatory funnel, and an extraction with water and toluene was performed. The extract was dried over MgSO4, and then the residue was recrystallized with ethyl acetate to obtain BH-28-a at a yield of 67%. (MS[M+H]+=321)
<28-b> Preparation of Compound BH-28-b
After Compound BH-28-a (36 g, 112 mmol) was dispersed in 500 ml of dimethylformamide, a solution of n-bromosuccinimide (19.9 g, 111 mmol) dissolved in 50 ml of dimethylformamide was slowly added dropwise thereto. After reaction at room temperature for 2 hours, 1 L of water was added dropwise thereto. When a solid was produced, the solid was filtered, and then dissolved in ethyl acetate, and the resulting solution was put into a separatory funnel, and then washed several times with distilled water. The solution was recrystallized in ethyl acetate to obtain Compound BH-28-b (37 g, yield 83%). (MS[M+H]+=398)
<28-c> Preparation of Compound BH-28
After Compound BH-28-b (37 g, 93 mmol) and dibenzo[b,d]furan-2-ylboronic acid (19.6 g, 92 mmol) were dissolved in THF (450 ml), Pd(PPh3)4 (5.3 g, 4.6 mmol) and 100 ml of an aqueous 2 M K2CO3 solution were added thereto, and the resulting solution was refluxed for 24 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate, and then dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain Compound BH-28 (25 g, yield 62%). (MS[M+H]+=486)
<29-a> Preparation of Compound BH-29-a
BH-29-a was obtained from 9-(naphthalen-2-yl)anthracene in the same manner as in Synthesis Example <28-a>. (Yield 69%, MS[M+H]+=321)
<29-b> Preparation of Compound BH-29-b
BH-29-b was obtained from BH-29-a in the same manner as in Synthesis Example <28-b>. (Yield 79%, MS[M+H]+=398)
<29-b> Preparation of Compound BH-29
BH-29 was obtained from BH-29-b and (4-(dibenzo[b,d]furan-1-yl)phenyl)boronic acid in the same manner as in Synthesis Example <28-c>. (Yield 61%, MS[M+H]+=562)
<31-a> Preparation of Compound BH-31-a
After 9-bromoanthracene (70 g, 272.2 mmol) and (4-(naphthalen-1-yl)phenyl)boronic acid were dissolved in THF (1400 ml), Pd(PPh3)4 (15.7 g, 13.6 mmol) and 300 ml of an aqueous 2M K2CO3 solution were added thereto, and the resulting solution was refluxed for 8 hours. The reaction solution was cooled, and the organic layer was extracted with ethyl acetate, and then dried over anhydrous magnesium sulfate. The organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain Compound BH-31-a (72.5 g, yield 70%). MS: [M+H]+=381
<31-b> Preparation of Compound BH-31-b
Compound BH-31-a (50 g, 131.4 mmol) and AlCl3 (8.6 g, 65.7 mmol) were put into C6D6 (1000 ml), and the resulting solution was stirred for 2 hours. After the reaction was completed, D2O (100 ml) was added thereto, the resulting solution was stirred for 30 minutes, and then trimethylamine (10 ml) was added dropwise thereto. The reaction solution was transferred to a separatory funnel, and an extraction with water and toluene was performed. After the extracted reaction solution was dried over anhydrous magnesium sulfate, the organic solvent was removed under reduced pressure, and the residue was purified using column chromatography to obtain Compound BH-31-b (33.1 g, yield 63%). MS: [M+H]+=401
<31-c> Preparation of Compound BH-31-c
After Compound BH-31-b (30 g, 74.9 mmol) was dispersed in 500 ml of dimethylformamide, a solution of n-bromosuccinimide (13.4 g, 74.9 mmol) dissolved in 50 ml of dimethylformamide was slowly added dropwise thereto. After reaction at room temperature for 2 hours, 1 L of water was added dropwise thereto. When a solid was produced, the solid was filtered, and then dissolved in ethyl acetate, and the resulting solution was put into a separatory funnel, and then washed several times with distilled water. The solution was recrystallized in ethyl acetate to obtain Compound BH-31-c (23.3 g, yield 65%). MS: [M+H]+=479
<31-d> Preparation of Compound BH-31
Compound BH-31 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-31-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into naphthalene-1-ylboronic acid. MS: [M+H]+=526
<32-a> Preparation of Compound BH-32
Compound BH-32 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-31-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into naphthalene-2-ylboronic acid. MS: [M+H]+=526
<33-a> Preparation of Compound BH-33
Compound BH-33 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-31-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into B-(1-naphthalenyl-2,3,4,5,6,7,8-d7)-boronic acid. MS: [M+H]+=533
<34-a> Preparation of Compound BH-34
Compound BH-34 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-31-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into B-(2-naphthalenyl-1,3,4,5,6,7,8-d7)-boronic acid. MS: [M+H]+=533
<35-a> Preparation of Compound BH-35-a
Compound BH-35-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that (4-(naphthalen-1-yl)phenyl)boronic acid was changed into (3-(naphthalen-1-yl)phenyl)boronic acid. MS: [M+H]+=381
<35-b> Preparation of Compound BH-35-b
Compound BH-35-b was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-b, except that Compound BH-31-a was changed into Compound BH-35-a. MS: [M+H]+=401
<35-c> Preparation of Compound BH-35-c
Compound BH-35-c was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-c, except that Compound BH-31-b was changed into Compound BH-35-b. MS: [M+H]+=479
<35-d> Preparation of Compound BH-35
Compound BH-35 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-35-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into naphthalene-2-ylboronic acid. MS: [M+H]+=526
<36-a> Preparation of Compound BH-36
Compound BH-36 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-35-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into B-(1-naphthalenyl-2,3,4,5,6,7,8-d7)-boronic acid. MS: [M+H]+=533
<37-a> Preparation of Compound BH-37-a
Compound BH-37-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that (4-(naphthalen-1-yl)phenyl)boronic acid was changed into naphthalene-1-ylboronic acid. MS: [M+H]+=305
<37-b> Preparation of Compound BH-37-b
Compound BH-37-b was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-b, except that Compound BH-31-a was changed into Compound BH-37-a. MS: [M+H]+=321
<37-c> Preparation of Compound BH-37-c
Compound BH-37-c was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-c, except that Compound BH-31-b was changed into Compound BH-37-b. MS: [M+H]+=399
<37-d> Preparation of Compound BH-37
Compound BH-37 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-37-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into (4-(naphthalen-2-yl)phenyl-2,3,5,6-d4)-boronic acid. MS: [M+H]+=526
<38-a> Preparation of Compound BH-38-a
Compound BH-38-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that (4-(naphthalen-1-yl)phenyl)boronic acid was changed into naphthalene-2-ylboronic acid. MS: [M+H]+=305
<38-b> Preparation of Compound BH-38-b
Compound BH-38-b was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-b, except that Compound BH-31-a was changed into Compound BH-38-a. MS: [M+H]+=321
<38-c> Preparation of Compound BH-38-c
Compound BH-38-c was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-c, except that Compound BH-31-b was changed into Compound BH-38-b. MS: [M+H]+=399
<38-d> Preparation of Compound BH-38
Compound BH-38 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-38-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into (4-(naphthalen-2-yl)phenyl-2,3,5,6-d4)-boronic acid. MS: [M+H]+=526
<39-a> Preparation of Compound BH-39-a
Compound BH-39-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that (4-(naphthalen-1-yl)phenyl)boronic acid was changed into (4-(naphthalen-2-yl)phenyl)boronic acid. MS: [M+H]+=381
<39-b> Preparation of Compound BH-39-b
Compound BH-39-b was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-b, except that Compound BH-31-a was changed into Compound BH-39-a. MS: [M+H]+=401
<39-c> Preparation of Compound BH-39-c
Compound BH-39-c was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-c, except that Compound BH-31-b was changed into Compound BH-39-b. MS: [M+H]+=479
<39-d> Preparation of Compound BH-39
Compound BH-39 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-39-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into naphthalene-1-ylboronic acid. MS: [M+H]+=526
<40-a> Preparation of Compound BH-40
Compound BH-40 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-39-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into naphthalene-2-ylboronic acid. MS: [M+H]+=526
<41-a> Preparation of Compound BH-41
Compound BH-41 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-39-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into B-(1-naphthalenyl-2,3,4,5,6,7,8-d7)-boronic acid. MS: [M+H]+=533
<42-a> Preparation of Compound BH-42
Compound BH-42 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-39-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into B-(2-naphthalenyl-1,3,4,5,6,7,8-d7)-boronic acid. MS: [M+H]+=533
<43-a> Preparation of Compound BH-43-a
Compound BH-43-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that (4-(naphthalen-1-yl)phenyl)boronic acid was changed into (3-(naphthalen-2-yl)phenyl)boronic acid. MS: [M+H]+=381
<43-b> Preparation of Compound BH-43-b
Compound BH-43-b was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-b, except that Compound BH-31-a was changed into Compound BH-43-a. MS: [M+H]+=401
<43-c> Preparation of Compound BH-43-c
Compound BH-43-c was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-c, except that Compound BH-31-b was changed into Compound BH-43-b. MS: [M+H]+=479
<43-d> Preparation of Compound BH-43
Compound BH-43 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-43-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into B-(2-naphthalenyl-1,3,4,5,6,7,8-d7)-boronic acid. MS: [M+H]+=533
<44-a> Preparation of Compound BH-44
Compound BH-44 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-43-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into B-(1-naphthalenyl-2,3,4,5,6,7,8-d7)-boronic acid. MS: [M+H]+=533
<45-a> Preparation of Compound BH-45
Compound BH-45 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-43-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into naphthalene-2-ylboronic acid. MS: [M+H]+=526
<46-a> Preparation of Compound BH-46
Compound BH-46 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-43-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into naphthalene-1-ylboronic acid. MS: [M+H]+=526
<47-a> Preparation of Compound BH-47-a
Compound BH-47-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that (4-(naphthalen-1-yl)phenyl)boronic acid was changed into naphthalene-1-ylboronic acid. MS: [M+H]+=305
<47-b> Preparation of Compound BH-47-b
Compound BH-47-b was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-b, except that Compound BH-31-a was changed into Compound BH-47-a. MS: [M+H]+=321
<47-c> Preparation of Compound BH-47-c
Compound BH-47-c was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-c, except that Compound BH-31-b was changed into Compound BH-47-b. MS: [M+H]+=399
<47-d> Preparation of Compound BH-47
Compound BH-47 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-47-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into B-(2-naphthalenyl-1,3,4,5,6,7,8-d7)-boronic acid. MS: [M+H]+=453
<48-a> Preparation of Compound BH-48
Compound BH-48 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-38-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into B-[4-(1-naphthalenyl)phenyl-2,3,5,6-d4]-boronic acid. MS: [M+H]+=526
<49-a> Preparation of Compound BH-49
Compound BH-49 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-37-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into (4-(naphthalen-1-yl)phenyl-2,3,5,6-d4)-boronic acid. MS: [M+H]+=526
<50-a> Preparation of Compound BH-50
Compound BH-50 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-37-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into (3-(naphthalen-2-yl)phenyl)-boronic acid. MS: [M+H]+=522
<51-a> Preparation of Compound BH-51
Compound BH-51 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-38-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into (3-(naphthalen-2-yl)phenyl)-boronic acid. MS: [M+H]+=522
<52-a> Preparation of Compound BH-52
Compound BH-52 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-37-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into naphthalene-1-ylboronic acid. MS: [M+H]+=446
<53-a> Preparation of Compound BH-53
Compound BH-53 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-37-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into naphthalene-2-ylboronic acid. MS: [M+H]+=446
<54-a> Preparation of Compound BH-54
Compound BH-54 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-37-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into (naphthalen-1-yl-d7)boronic acid. MS: [M+H]+=453
<55-a> Preparation of Compound BH-55
Compound BH-55 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-38-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into naphthalene-1-ylboronic acid. MS: [M+H]+=456
<56-a> Preparation of Compound BH-56
Compound BH-56 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-38-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into naphthalene-2-ylboronic acid. MS: [M+H]+=456
<57-a> Preparation of Compound BH-57-a
Compound BH-57-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into 9-bromoanthracene-1,2,3,4,5,6,7,8,10-d9, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into naphthalene-1-ylboronic acid. MS: [M+H]+=314
<57-b> Preparation of Compound BH-57-b
Compound BH-57-b was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-c, except that Compound BH-31-b was changed into Compound BH-57-a. MS: [M+H]+=392
<57-c> Preparation of Compound BH-57
Compound BH-57 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-57-b, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into (4-(naphthalen-2-yl)phenyl)-boronic acid. MS: [M+H]+=515
<58-a> Preparation of Compound BH-58
Compound BH-58 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-37-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into (3-(naphthalen-1-yl)phenyl)-boronic acid. MS: [M+H]+=522
<59-a> Preparation of Compound BH-59
Compound BH-59 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 31-a, except that 9-bromoanthracene was changed into Compound BH-38-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into (3-(naphthalen-1-yl)phenyl)-boronic acid. MS: [M+H]+=522
A flask containing starting materials S-1 (10 g), S-2 (20.6 g, 1.1 equivalents), Pd(PtBu3)2 (0.31 g, 0.02 equivalent), NaOtBu (8.8 g, 3 equivalents), and toluene (300 ml) was heated at 110° C. and stirred for 16 hours. The reaction solution was cooled to room temperature, the solution was aliquoted by adding water and toluene thereto, and then the solvent was distilled off under reduced pressure. The residue was purified with silica gel column chromatography (eluent: toluene/hexane) to obtain Compound S-3 (9.7 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H]+=781.
Here, tBu means a tert-butyl group.
An n-butyllithium pentane solution (8.2 ml, 2.5 M in hexane, 2 equivalents) was added to a flask containing Intermediate S-3 (8 g) and toluene (70 ml) at 0° C. under nitrogen atmosphere. After the completion of dropwise addition, the resulting solution was warmed to 50° C. and stirred for 2 hours. The resulting solution was cooled to −40° C., boron tribromide (1.5 ml, 1.5 equivalents) was added thereto, and the resulting solution was stirred for 4 hours while being warmed to room temperature. Thereafter, the solution was again cooled to 0° C., Sat.aq.NaHCO3 and ethyl acetate were added thereto, and the resulting solution was aliquoted, and then the solvent was distilled off under reduced pressure. The resulting product was purified with a silica gel column chromatography (eluent: hexane/toluene) to obtain Compound A-2 (1.2 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H+]=711.
11.8 g of Intermediate S-5 was obtained using S-4 (20.6 g) in the same manner as in the method for producing Compound S-3 in Synthesis Example 60. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H]+=997.
1.2 g of Compound A-5 was obtained using S-5 (10 g) in the same manner as in the method for producing Compound A-2 in Synthesis Example 61. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H]+=927.
11.4 g of Intermediate S-7 was obtained using S-6 (10 g) and S-1 (22.2 g) in the same manner as in the method for producing Compound S-3 in Synthesis Example 60. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H]+=757.
A flask containing Intermediate S-7 (9.5 g), S-8 (3.7 g, 1.05 equivalents), Pd(PtBu3)2 (0.13 g, 0.02 equivalent), NaOtBu (1.8 g, 1.5 equivalents), and toluene (40 ml) was heated at 110° C. and stirred for 4 hours. The reaction solution was cooled to room temperature, the solution was aliquoted by adding water and toluene thereto, and then the solvent was distilled off under reduced pressure. The resulting product was purified with recrystallization (ethyl acetate/hexane) to obtain Compound S-9 (10.5 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H]+=1001.
12.9 g of Intermediate S-11 was obtained using S-6 (10 g) and S-10 (25.7 g) in the same manner as in the method for producing Compound S-3 in Synthesis Example 60. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H]+=853.
10.6 g of Intermediate S-13 was obtained using S-11 (11 g) and S-12 (3.3 g) in the same manner as in the method for producing Compound S-9 in Synthesis Example 65. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H]+=1058.
A 1.7 M tert-butyllithium pentane solution (21.1 ml, 4 equivalents) was added to a flask containing Intermediate S-9 (9.0 g) and toluene (60 ml) at 0° C. under nitrogen atmosphere. After the completion of dropwise addition, the resulting solution was warmed to 70° C. and stirred for 2 hours. The resulting solution was cooled to −40° C., boron tribromide (1.7 ml, 2 equivalents) was added thereto, and the resulting solution was stirred for 4 hours while being warmed to room temperature. When the reaction was terminated, the resulting product was aliquoted by adding sat.aq. Na2S2O3 and sat.aq. NaHCO3 thereto, and then the solvent was distilled off under reduced pressure. The resulting product was purified with recrystallization (hexane/toluene) to obtain Compound A-4 (1.4 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H]+=975.
0.9 g of Compound A-6 was obtained using S-13 (9.6 g) in the same manner as in the method for producing Compound A-4 in Synthesis Example 68. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H]+=1032.
12.5 g of Intermediate S-15 was obtained using S-2 (10 g) and S-14 (20.6 g) in the same manner as in the method for producing Compound S-3 in Synthesis Example 60. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H]+=933.
2.1 g of Compound A-3 was obtained using S-15 (11 g) in the same manner as in the method for producing Compound A-2 in Synthesis Example 61. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H]+=863.
14.2 g of Intermediate S-17 was obtained using S-2 (15 g) and S-16 (28 g) in the same manner as in the method for producing Compound S-3 in Synthesis Example 60. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H]+=724.
1.3 g of Compound B-2 was obtained using S-17 (13 g) in the same manner as in the method for producing Compound A-2 in Synthesis Example 61. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H]+=654.
10.6 g of Intermediate S-19 was obtained using S-2 (10 g) and S-18 (20.9 g) in the same manner as in the method for producing Compound S-3 in Synthesis Example 60. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H]+=792.
1.2 g of Compound B-3 was obtained using S-19 (9.6 g) in the same manner as in the method for producing Compound A-2 in Synthesis Example 61. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H]+=722.
9.3 g of Intermediate S-34 was obtained using S-2 (10 g) and S-33 (21.5 g) in the same manner as in the method for producing Compound S-3 in Synthesis Example 60. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H]+=809.
1.3 g of Compound E-1 was obtained using S-34 (8.3 g) in the same manner as in the method for producing Compound A-2 in Synthesis Example 61. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H]+=740.
10.7 g of Intermediate S-36 was obtained using S-2 (10 g) and S-35 (21.8 g) in the same manner as in the method for producing Compound S-3 in Synthesis Example 60. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H]+=819.
1.2 g of Compound E-2 was obtained using S-36 (9.7 g) in the same manner as in the method for producing Compound A-2 in Synthesis Example 61. As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at [M+H]+=749.
1,3-dibromobenzene (10 g, 40 mmol) was dissolved in 100 mL of diethyl ether, and the resulting solution was cooled to −78° C. under nitrogen conditions. Next, a 1.6 M n-BuLi hexane solution (26 mL, 40 mmol) was slowly added dropwise hereto, and the resulting solution was stirred at −78° C. for 2 hours. Dichlorodiphenylsilane (5.10 g, 20 mmol) was put thereinto, and the resulting solution was stirred while being slowly warmed to room temperature for 10 hours. The reaction was terminated by putting distilled water thereinto, 100 mL of diethyl ether was further put thereinto for extraction, and then the extract was dried over anhydrous sodium sulfate. The resulting product was purified with a silica gel column chromatography (eluent: hexane/ethyl acetate=50%/50% (volume ratio)) to obtain Intermediate SA-1 (5.0 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at M/Z=494.
A flask containing 2-chloro-5-methyl-N1,N3-diphenylbenzene-1,3-diamine (12.4 g, 40 mmol), Intermediate SA-1 (19.8 g, 40 mmol), Pd(PtBu3)2 (0.5 g, 1.0 mmol), NaOtBu (6.2 g, 64 mmol), and xylene (70 ml) was heated at 130° C. and stirred for 4 hours. The reaction solution was cooled to room temperature, the liquid was aliquoted by adding water and ethyl acetate thereto, and then the solvent was distilled off under reduced pressure. The resulting product was purified with a silica gel column chromatography (eluent: hexane/ethyl acetate=50%/50% (volume ratio)) to obtain Intermediate SB-2 (1.4 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at M/Z=641.
Intermediate SB-2 (1.0 g, 1.6 mmol) was dissolved in tert-butylbenzene (t-BuPh, 160 mL) in a round bottom flask under nitrogen atmosphere. 1.7 M t-butyllithium (1.9 mL, 3.2 mmol) was slowly added dropwise to this solution at room temperature, and then the resulting solution was stirred at 60° C. for 1 hour. The solution was cooled to room temperature, and then boron tribromide (0.3 mL, 3.2 mmol) was slowly added dropwise thereto, and then the resulting solution was stirred at 60° C. for 4 hours. When the reaction was terminated, the product was cooled to room temperature, and then water was added thereto, extraction with toluene was performed, and then the aqueous layer was removed. The residue was treated with anhydrous magnesium sulfate, and then filtered and concentrated under reduced pressure. The product was separated and purified with column chromatography, and then recrystallized with ethyl acetate and hexane to obtain Final Compound F-1 (0.21 g, 22%). MS: [M+H]+=615
Compound F-2 was prepared by the same method as that for Compound F-1, except that Intermediate SB-3 was used instead of Intermediate SB-2 in the synthesis of Compound F-1. (0.34 g, yield 29%, MS: [M+H]+=727
Compound F-3 was prepared by the same method as that for Compound F-1, except that Intermediate SB-4 was used instead of Intermediate SB-2 in the synthesis of Compound F-1. (0.36 g, yield 28%, MS: [M+H]+=795
Compound F-4 was prepared by the same method as that for Compound F-1, except that Intermediate SB-5 was used instead of Intermediate SB-2 in the synthesis of Compound F-1. (0.36 g, yield 26%, MS: [M+H]+=879
Compound F-5 was prepared by the same method as that for Compound F-1, except that Intermediate SB-6 was used instead of Intermediate SB-2 in the synthesis of Compound F-1. (0.38 g, yield 27%, MS: [M+H]+=879
Compound F-6 was prepared by the same method as that for Compound F-1, except that Intermediate SB-7 was used instead of Intermediate SB-2 in the synthesis of Compound F-1. (0.38 g, yield 28%, MS: [M+H]+=839
A flask containing 2-bromo-5-chloro-N1,N3-diphenylbenzene-1,3-diamine (14.9 g, 40 mmol), Intermediate SA-1 (19.8 g, 40 mmol), Pd(PtBu3)2 (0.5 g, 1.0 mmol), NaOtBu (6.2 g, 64 mmol), and xylene (70 ml) was heated at 130° C. and stirred for 4 hours. The reaction solution was cooled to room temperature, the liquid was aliquoted by adding water and ethyl acetate thereto, and then the solvent was distilled off under reduced pressure. The resulting product was purified with a silica gel column chromatography (eluent: hexane/ethyl acetate=50%/50% (volume ratio)) to obtain Intermediate SB-8 (1.4 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at M/Z=705.
Intermediate SB-8 (4.5 g, 6.4 mmol) was dissolved in tert-butylbenzene (t-BuPh, 320 mmL) in a round bottom flask under nitrogen atmosphere. 1.7 M t-butyllithium (7.6 mL, 12.8 mmol) was slowly added dropwise to this solution at room temperature, and then the resulting solution was stirred at 60° C. for 1 hour. The solution was cooled to room temperature, and then boron tribromide (1.2 mL, 12.8 mmol) was slowly added dropwise thereto, and then the resulting solution was stirred at 60° C. for 4 hours. When the reaction was terminated, the product was cooled to room temperature, and then water was added thereto, extraction with toluene was performed, and then the aqueous layer was removed. The residue was treated with anhydrous magnesium sulfate, and then filtered and concentrated under reduced pressure. The product was separated and purified with column chromatography, and then recrystallized with ethyl acetate and hexane to obtain 0.90 g of SC-1.
Next, a flask containing SC-1 (0.90 g) obtained above, diphenylamine (0.3 g, 1.5 mmol), Pd(PtBu3)2 (0.05 g, 0.1 mmol), NaOtBu (0.62 g, 6.4 mmol), and xylene (7 ml) was heated at 130° C. and stirred for 4 hours. The reaction solution was cooled to room temperature, the liquid was aliquoted by adding water and ethyl acetate thereto, and then the solvent was distilled off under reduced pressure. The resulting product was purified with a silica gel column chromatography (eluent: hexane/ethyl acetate=50%/50% (volume ratio)) to obtain Intermediate F-7 (0.4 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at M/Z=768.
Compound F-8 was prepared by the same method as that for Compound F-7, except that Intermediate SB-9 was used instead of Intermediate SB-8 in the synthesis of Compound F-7. (0.42 g, yield 7.5%, MS: [M+H]+=880.
Intermediate SA-2 was prepared by the same method as that for Intermediate SA-1, except that 1,3-dibromo-5-methylbenzene was used instead of 1,3-dibromobenzene (10 g, 40 mmol) in the synthesis of Compound SA-1.
Intermediate SB-10 was prepared by the same method as that for Intermediate SB-8, except that Intermediate SA-2 was used instead of Intermediate SA-1 (19.8 g, 40 mmol) in the synthesis of Intermediate SB-8.
Compound F-9 was prepared by the same method as that for Compound F-1, except that Intermediate SB-10 was used instead of Intermediate SB-2 (1.0 g, 1.6 mmol) in the synthesis of Compound F-1. MS: [M+H]+=643
Intermediate SA-3 was prepared by the same method as that for Intermediate SA-1, except that 1,3-dibromo-5-butylbenzene was used instead of 1,3-dibromobenzene (10 g, 40 mmol) in the synthesis of Compound SA-4.
A flask containing N1-([1,1′-biphenyl]-4-yl)-N3-(4-(tert-butyl)phenyl)-2-chlorobenzene-1,3-diamine (17.1 g, 40 mmol), Intermediate SA-3 (21.8 g, 40 mmol), Pd(PtBu3)2 (0.5 g, 1.0 mmol), NaOtBu (6.2 g, 64 mmol), and xylene (70 ml) was heated at 130° C. and stirred for 4 hours. The reaction solution was cooled to room temperature, the liquid was aliquoted by adding water and ethyl acetate thereto, and then the solvent was distilled off under reduced pressure. The resulting product was purified with a silica gel column chromatography (eluent: hexane/ethyl acetate=50%/50% (volume ratio)) to obtain Intermediate SB-11 (2.0 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at M/Z=809.
Intermediate SB-11 (1.3 g, 1.6 mmol) was dissolved in tert-butylbenzene (t-BuPh, 160 mmL) in a round bottom flask under nitrogen atmosphere. 1.7 M t-butyllithium (1.9 mL, 3.2 mmol) was slowly added dropwise to this solution at room temperature, and then the resulting solution was stirred at 60° C. for 1 hour. The solution was cooled to room temperature, and then boron tribromide (0.3 mL, 3.2 mmol) was slowly added dropwise thereto, and then the resulting solution was stirred at 60° C. for 4 hours. When the reaction was terminated, the product was cooled to room temperature, and then water was added thereto, extraction with toluene was performed, and then the aqueous layer was removed. The residue was treated with anhydrous magnesium sulfate, and then filtered and concentrated under reduced pressure. The product was separated and purified with column chromatography, and then recrystallized with ethyl acetate and hexane to obtain Final Compound F-10 (0.30 g, 24%). MS: [M+H]+=783
Intermediate SA-4 was prepared by the same method as that for Intermediate SA-1, except that dichloro(methyl) (phenyl)silane was used instead of dichlorodiphenylsilane (5.10 g, 20 mmol) in the synthesis of Compound SA-1.
A flask containing 2-bromo-N1,N3-bis(4-(tert-butyl)phenyl)-5-chlorobenzene-1,3-diamine (19.4 g, 40 mmol), Intermediate SA-4 (17.3 g, 40 mmol), Pd(PtBu3)2 (0.5 g, 1.0 mmol), NaOtBu (6.2 g, 64 mmol), and xylene (70 ml) was heated at 130° C. and stirred for 4 hours. The reaction solution was cooled to room temperature, the liquid was aliquoted by adding water and ethyl acetate thereto, and then the solvent was distilled off under reduced pressure. The resulting product was purified with a silica gel column chromatography (eluent: hexane/ethyl acetate=50%/50% (volume ratio)) to obtain Intermediate SB-12 (2.0 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at M/Z=755.
Intermediate SB-12 (4.8 g, 6.4 mmol) was dissolved in tert-butylbenzene (t-BuPh, 320 mmL) in a round bottom flask under nitrogen atmosphere. 1.7 M t-butyllithium (7.6 mL, 12.8 mmol) was slowly added dropwise to this solution at room temperature, and then the resulting solution was stirred at 60° C. for 1 hour. The solution was cooled to room temperature, and then boron tribromide (1.2 mL, 12.8 mmol) was slowly added dropwise thereto, and then the resulting solution was stirred at 60° C. for 4 hours. When the reaction was terminated, the product was cooled to room temperature, and then water was added thereto, extraction with toluene was performed, and then the aqueous layer was removed. The residue was treated with anhydrous magnesium sulfate, and then filtered and concentrated under reduced pressure. The product was separated and purified with column chromatography, and then recrystallized with ethyl acetate and hexane to obtain 1.0 g of an intermediate.
Next, a flask containing 0.98 g of the intermediated obtained above, diphenylamine (0.3 g, 1.5 mmol), Pd(PtBu3)2 (0.05 g, 0.1 mmol), NaOtBu (0.62 g, 6.4 mmol), and xylene (7 ml) was heated at 130° C. and stirred for 4 hours. The reaction solution was cooled to room temperature, the liquid was aliquoted by adding water and ethyl acetate thereto, and then the solvent was distilled off under reduced pressure. The resulting product was purified with a silica gel column chromatography (eluent: hexane/ethyl acetate=50%/50% (volume ratio)) to obtain Intermediate F-11 (0.54 g). As a result of measuring the mass spectrum of the obtained solid, a peak was confirmed at M/Z=818.
A glass substrate thinly coated with indium tin oxide (ITO) to have a thickness of 1,400 Å was put into distilled water in which a detergent was dissolved, and ultrasonically washed. In this case, a product manufactured by Fischer Co., was used as the detergent, and distilled water, which had been filtered twice with a filter manufactured by Millipore Co., was used as the distilled water. After the ITO was washed for 30 minutes, ultrasonic washing was conducted twice repeatedly using distilled water for 10 minutes. After the washing using distilled water was completed, ultrasonic washing was conducted by using isopropyl alcohol, acetone, and methanol solvents, and the resulting product was dried and then transported to a plasma washing machine. Furthermore, the substrate was cleaned by using oxygen plasma for 5 minutes, and then was transported to a vacuum deposition machine.
The following HI-A and LG-101 were thermally vacuum deposited to have a thickness of 650 Å and 50 Å, respectively, on the ITO transparent electrode prepared as described, thereby forming a hole injection layer. The following HT-A was vacuum deposited to have a thickness of 620 Å on the hole injection layer, thereby forming a hole transport layer. The following HT-B was vacuum deposited to have a thickness of 50 Å on the hole transport layer, thereby forming an electron blocking layer.
Subsequently, the following compound A-2 as a blue light emitting dopant was vacuum deposited at 3 wt % based on a total weight of the light emitting layer and the following BH-1 as a host was vacuum deposited to a thickness of 200 Å on the electron blocking layer, thereby forming a light emitting layer.
Next, the following compound ET-A as a first electron transport layer was vacuum deposited to have a thickness of 50 Å on the light emitting layer, and subsequently, the following ET-B and LiQ were vacuum deposited at a weight ratio of 1:1, thereby forming a second electron transport layer having a thickness of 340 Λ. LiQ was vacuum deposited to have a thickness of 5 Å on the second electron transport layer, thereby forming an electron injection layer. Aluminum and silver were deposited at a weight ratio of 10:1 to have a thickness of 220 Å on the electron injection layer, and aluminum was deposited to have a thickness of 1,000 Å thereon, thereby forming a cathode.
In the aforementioned procedure, the deposition rate of the organic materials was maintained at 0.4 to 0.9 Å/sec, the deposition rate of aluminum of the cathode was maintained at 2 Å/sec, and the degree of vacuum during the deposition was maintained at 1×10−7 to 5×10−8 torr, thereby manufacturing an organic light emitting device.
Organic light emitting devices of Examples 2 to 78 were each manufactured in the same manner as in Example 1, except that in Example 1, compounds described in the following Table 1 were used as dopants of the light emitting layer instead of Compound A-2, and compounds described in the following Table 1 were used as host materials instead of BH-1.
Organic light emitting devices of Comparative Examples 1 to 4 were each manufactured in the same manner as in Example 1, except that in Example 1, compounds described in the following Table 1 were used as dopants of the light emitting layer instead of Compound A-2, and compounds described in the following Table 1 were used as host materials instead of BH-1.
Voltages and efficiencies (cd/A/y) when a current density of 10 mA/cm2 was applied to the organic light emitting devices in Examples 1 to 75 and Comparative Examples 1 to 4 and service lives (LT95) when a current density of 20 mA/cm2 was applied to the devices were measured, and the results are shown in the following Table 1. In this case, for LT95, a time taken for the luminance to decrease to 95% when the initial luminance at the current density of 20 mA/cm2 is set to 100% was shown as the ratio based on Comparative Example 1.
Examples 76 to 78 and Comparative Example 5 Organic light emitting devices of Examples 76 to 78 and Comparative Example 5 were each manufactured in the same manner as in Example 1, except that in Example 1, compounds described in the following Table 2 were used as dopants of the light emitting layer instead of Compound A-2, and compounds described in the following Table 2 were used as host materials instead of BH-1.
A weight ratio of the first host and the second host of the light emitting layer is 50:50.
Voltages and efficiencies (cd/A/y) when a current density of 10 mA/cm2 was applied to the organic light emitting devices in Examples 76 to Example 78 and Comparative Example 5 and service lives (LT95) when a current density of 20 mA/cm2 was applied to the devices were measured, and the results are shown in the following Table 2. In this case, for LT95, a time taken for the luminance to decrease to 95% when the initial luminance at the current density of 20 mA/cm2 is set to 100% was shown as the ratio based on Comparative Example 1.
The conversion efficiency (cd/A/y) takes a current efficiency (cd/A) to color purity (CIEy) of the material into consideration, and is an important reference value for efficiency in small and large organic light emitting devices targeting high luminance and high color gamut.
As can be seen in the device results in Tables 1 and 2, when an organic light emitting device was constructed by combining a host material represented by any one of [Formula 1-1] to [Formula 1-3] according to an exemplary embodiment of the present specification and a dopant material represented by [Formula 2], the organic light emitting device was better in both the conversion efficiency and service life performance of a device than other devices which were not constructed by the combination.
From Examples 37, 39, 41, and 57, it could be confirmed that the higher the deuterium substitution rate was, the longer the service life of the device was, and from Examples 16 and 17, it could be seen that when the skeletons were the same and the deuterium substitution rates were similar, the service life in the case where deuterium was linked to anthracene was increased.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2019-0157386 | Nov 2019 | KR | national |
| 10-2019-0157398 | Nov 2019 | KR | national |
| 10-2019-0157427 | Nov 2019 | KR | national |
This application is a National Phase entry pursuant to 35 U.S.C § 371 of International Application No. PCT/KR2020/017339 filed on Nov. 30, 2020, and claims priority to and the benefit of Korean Patent Application Nos. 10-2019-0157398, 10-2019-0157386, and 10-2019-0157427 filed on Nov. 29, 2019, the disclosures of which are incorporated herein by reference in their entireties.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2020/017339 | 11/30/2020 | WO |
