Patent Application
20230114182
The present specification relates to an organic light emitting device.
This application claims priority to and the benefit of Korean Patent Application Nos. 10-2019-0157398, 10-2019-0157386, and 10-2019-0157427 filed in the Korean Intellectual Property Office on Nov. 29, 2019, the entire contents of which are incorporated herein by reference.
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 a positive electrode, a negative electrode, 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 positive electrode into the organic material layer and electrons are injected from the negative electrode 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: a positive electrode; a negative electrode; and an organic material layer including a light emitting layer provided between the positive electrode and the negative electrode,
wherein the light emitting layer includes one or more of compounds represented by any one of the following Formulae 1-1 to 1-3 and a compound represented by the following Formula 2.
In Formulae 1-1 to 1-3, 2, and 2-C,
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 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 or 4, and m22 is an integer from 1 to 5,
when m11, m21, and m22 are 2 or higher, substituents in the parenthesis are the same as or different from each other,
Formulae 1-1 to 1-3 each have at least one or more deuteriums,
A1 to A3 are the same as or different from each other, and are each independently one ring selected from the group consisting of an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring, an aromatic hetero ring, and an aliphatic hetero ring; or a ring in which two or more rings selected from the above group are fused,
at least one of A1 and A2 is represented by Formula 2-C,
X is NRa1; O; or S,
E1 is one ring selected from the group consisting of an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring, an aromatic hetero ring, and an aliphatic hetero ring; or a ring in which two or more rings selected from the above group are fused,
R1 to R5 and Ra1 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,
r1 to r3 are an integer from 1 to 4, and when r1 to r3 are 2 or higher, substituents in the parenthesis are the same as or different from each other, and
* is a position in which a substituent is fused with Formula 2.
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 any one of 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 any one of Formulae 1-1 to 1-3 and a compound represented by Formula 2. Specifically, the compounds represented by any one of 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 (1H 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, * means a moiety 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
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
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 alkyl 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, 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 or 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 or 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, kl 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, 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 another exemplary embodiment, n11 is 3 or higher. In another exemplary embodiment, n11 is 4 or higher. In 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 another exemplary embodiment, n21+n22+n23+k1 is 19 or lower. In still 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 yet another exemplary embodiment, n21+n22+n23+k2 is 4 or higher. In yet 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 still 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, Formula 1-1 is any one selected from the following Formulae 101 to 104.
In Formulae 101 to 104, definitions of Ar11 to Ar13, D, n11 to n13, m11, and L1 are the same as those defined in Formula 1-1.
In an exemplary embodiment of the present specification, Formula 1-2 is any one selected from the following Formulae 111 to 114.
In Formulae 111 to 114, definitions of D, n21 to n23, Ar21 to Ar24, m21, m22, and L2 are the same as those defined in Formula 1-2.
In an exemplary embodiment of the present specification, Formula 1-3 is any one selected from the following Formulae 121 to 124.
In Formulae 121 to 124, definitions of Ar31, Ar32, D, n31 to n33, and L3 are the same as those 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 deuterium 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 an exemplary embodiment of the present specification, A1 to A3 are the same as or different from each other, and are each independently one ring selected from the group consisting of an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring, an aromatic hetero ring, and an aliphatic hetero ring; or a ring in which two or more rings selected from the above group are fused.
In an exemplary embodiment of the present specification, at least one of A1 and A2 is represented by the following Formula 2-C.
In Formula 2-C, * is a position in which a substituent is fused with Formula 2.
In an exemplary embodiment of the present specification, X is NRa1; 0; or S.
In an exemplary embodiment of the present specification, Ra1 is 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, Ra1 is a substituted or unsubstituted aryl group.
In an exemplary embodiment of the present specification, Ra1 is a substituted or unsubstituted C6-C30 aryl group.
In an exemplary embodiment of the present specification, Ra1 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, and a C1-C10 alkyl 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, Ra1 is a C6-C20 aryl group which is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, and a C1-C6 alkyl group, a substituent to which two or more groups selected from the above group are linked.
In an exemplary embodiment of the present specification, Ra1 is a C6-C20 aryl group which is unsubstituted or substituted with deuterium, a halogen group, a C1-C6 alkyl group substituted with deuterium, a C1-C6 haloalkyl group, or a C1-C6 alkyl group.
In an exemplary embodiment of the present specification, Ra1 is a phenyl group which is unsubstituted or substituted with deuterium, a fluoro group, a methyl group, an ethyl group, a propyl group, a butyl group, a trifluoromethyl group, or CD3.
In an exemplary embodiment of the present specification, E1 is one ring selected from the group consisting of an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring, an aromatic hetero ring, and an aliphatic hetero ring; or a ring in which two or more rings selected from the above group are fused,
In an exemplary embodiment of the present specification, E1 is one ring selected from the group consisting of a C6-C20 aromatic hydrocarbon ring, a C5-C20 aliphatic hydrocarbon ring, a C2-C20 aromatic hetero ring containing 0, a C2-C20 aliphatic hetero ring containing 0, a C2-C20 aromatic hetero ring containing S, a C2-C20 aliphatic hetero ring containing S, a C2-C20 aromatic hetero ring containing N, and a C2-C20 aliphatic hetero ring containing N; or a ring in which two or more rings selected from the above group are fused.
In an exemplary embodiment of the present specification, E1 is one ring selected from the group consisting of a C6-C10 aromatic hydrocarbon ring, a C5-C10 aliphatic hydrocarbon ring, a C2-C10 aromatic hetero ring containing 0, a C2-C10 aliphatic hetero ring containing 0, a C2-C10 aromatic hetero ring containing S, a C2-C10 aliphatic hetero ring containing S, a C2-C10 aromatic hetero ring containing N, and a C2-C10 aliphatic hetero ring containing N; or a ring in which two or more rings selected from the above group are fused.
In an exemplary embodiment of the present specification, E1 is one ring selected from the group consisting of a monocyclic or bicyclic aromatic hydrocarbon ring, a monocyclic or bicyclic aliphatic hydrocarbon ring, a monocyclic or bicyclic aromatic hetero ring containing O, a monocyclic or bicyclic aliphatic hetero ring containing O, a monocyclic or bicyclic aromatic hetero ring containing S, a monocyclic or bicyclic aliphatic hetero ring containing S, a monocyclic or bicyclic aromatic hetero ring containing N, and a monocyclic or bicyclic aliphatic hetero ring containing N; or a ring in which two or more rings selected from the above group are fused.
In an exemplary embodiment of the present specification, E1 forms one ring selected from the group consisting of a benzene ring; an indene ring; a furan ring; a benzofuran ring; a thiophene ring; a benzothiophene ring; a silole ring; a benzosilole ring; a pyrrole ring; an indole ring; a cyclopentene ring; a cyclohexene ring; a bicyclo[2.2.1]heptene ring; a bicyclo[2.2.2]octene ring; a dihydrofuran ring; a dihydrothiophene ring; and a dihydrosilole ring, or a ring in which two selected from the above group are fused.
In an exemplary embodiment of the present specification, E1 is a benzene ring; a cyclopentene ring; a cyclohexne ring; a bicyclo[2.2.1]heptene ring; a bicyclo[2.2.2]octene ring; a tetrahydronaphthalene ring; a dihydroindene ring; a tetrahydromethanonaphthalene ring; or a tetrahydroethanonaphthalene ring.
In an exemplary embodiment of the present specification, E1 is selected from the following structures. The rings having the following structure are unsubstituted or substituted with R1 or R2.
In the structures,
* is a position in which a substituent is fused,
Y3 is O; S; Si(Ra6) (Ra7); or N(Ra8),
Y4 is O; S; Si(Ra6) (Ra7); C(Ra6) (Ra7); or N(Ra8), and
Ra6 to Ra8 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.
In an exemplary embodiment of the present specification, Ra6 to Ra8 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, Ra6 to Ra8 are the same as or different from each other, and are each independently C1-C6 alkyl group which is unsubstituted or substituted with deuterium; a C6-C20 aryl group which is unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a C1-C6 alkyl group, and a C1-C6 alkoxy 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 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, Ra6 to Ra8 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, Ra8 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, Ra8 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, Ra8 is a phenyl group which is unsubstituted or substituted with deuterium, a fluoro group, 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, at least one of A1 and A2 of Formula 2 is represented by Formula 2-C, and the other is a C6-C30 aromatic hydrocarbon ring in which a C5-C30 hydrocarbon ring or a C2-C30 hetero ring is fused or unfused.
In an exemplary embodiment of the present specification, at least one of A1 and A2 of Formula 2 is represented by Formula 2-C, and the other is a C6-C10 aromatic hydrocarbon ring in which a C5-C10 hydrocarbon ring or a C2-C10 hetero ring is fused or unfused.
In an exemplary embodiment of the present specification, at least one of A1 and A2 of Formula 2 is represented by Formula 2-C, and the other is a benzene ring; or a naphthalene ring.
In an exemplary embodiment of the present specification, A1 is represented by Formula 2-C, and A2 is a benzene ring.
In an exemplary embodiment of the present specification, A1 is a benzene ring, and A2 is represented by Formula 2-C.
In an exemplary embodiment of the present specification, A1 and A2 are the same as or different from each other, and are each independently represented by Formula 2-C.
In an exemplary embodiment of the present specification, A3 is a benzene ring.
In an exemplary embodiment of the present specification, Formula 2 is represented by any one selected from the following Formulae 204 to 207.
In Formulae 204 to 207,
definitions of R1 to R5, r1, and r3 are the same as those defined in Formula 2,
E1 and E2 are the same as or different from each other, and are each independently one ring selected from the group consisting of an aromatic hydrocarbon ring, an aliphatic hydrocarbon ring, an aromatic hetero ring, and an aliphatic hetero ring; or a ring in which two or more rings selected from the above group are fused,
X1 and X2 are the same as or different from each other, and are each independently NRa1; O; or S,
Ra1's 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″ and r2″ are an integer of 1 or higher, and when r1″ and r2″ 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 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 an exemplary embodiment of the present specification, r1, r2, r1″, and r2″ are an integer of 10 or lower. In another exemplary embodiment, r1, r2, r1″, and r2″ are an integer of 8 or lower. In still another exemplary embodiment, r1, r2, r1″, and r2″ are an integer of 4 or lower.
In an exemplary embodiment of the present specification, E1 and E2 are the same as or different from each other, and are each independently a C6-C20 aromatic hydrocarbon ring; a C5-C20 aliphatic hydrocarbon ring; or a fused ring of a C6-C20 aromatic hydrocarbon ring and a C5-C20 aliphatic hydrocarbon ring.
In an exemplary embodiment of the present specification, E1 and E2 are the same as or different from each other, and are each independently a monocyclic to bicyclic aromatic hydrocarbon ring; a monocyclic to bicyclic aliphatic hydrocarbon ring; or a fused ring of a monocyclic aromatic hydrocarbon ring and a monocyclic aliphatic hydrocarbon ring.
In an exemplary embodiment of the present specification, E1 and E2 are the same as or different from each other, and each independently form one ring selected from the group consisting of a benzene ring; an indene ring; a furan ring; a benzofuran ring; a thiophene ring; a benzothiophene ring; a silole ring; a benzosilole ring; a pyrrole ring; an indole ring; a cyclopentene ring; a cyclohexene ring; a bicyclo[2.2.1]heptene ring; a bicyclo[2.2.2]octene ring; a dihydrofuran ring; a dihydrothiophene ring; and a dihydrosilole ring, or a ring in which two selected from the above group are fused.
In an exemplary embodiment of the present specification, E1 and E2 are the same as or different from each other, and are each independently a benzene ring; a cyclopentene ring; a cyclohexne ring; a bicyclo[2.2.1]heptene ring; a bicyclo[2.2.2]octene ring; a tetrahydronaphthalene ring; a dihydroindene ring; a tetrahydromethanonaphthalene ring; or a tetrahydroethanonaphthalene ring.
In an exemplary embodiment of the present specification, E1 and E2 are the same as or different from each other, and are each independently selected from the following structures. The rings having the following structure are unsubstituted or substituted with R1 or R2.
In the structures,
* is a position in which a substituent is fused,
Y3 is O; S; Si(Ra6) (Ra7); or N(Ra8),
Y4 is O; S; Si(Ra6) (Ra7); C(Ra6) (Ra7); or N(Ra8), and
Ra6 to Ra8 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.
In an exemplary embodiment of the present specification, E1 and E2 are the same as or different from each other, and are each independently a benzene ring; a cyclopentene ring; or a cyclohexene ring.
In an exemplary embodiment of the present specification, Ra1 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, Ra1 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, Ra1 is a phenyl group which is unsubstituted or substituted with deuterium, a fluoro group, 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, 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 R4 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 ach 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.
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 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 R31, while being each independently a group represented by the following Formula 3-A.
In an exemplary embodiment of the present specification, R4 and R5 are a group represented by the following Formula 3-A.
In Formula R31,
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 when r31 is 2 or higher, R31's are the same as or different from each other, and
is a moiety linked to Formula 2.
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, R31 is linked to the ortho position with respect to nitrogen (N) while being a substituent other than hydrogen. Specifically, in 2-A of the following structure,
is a position which is linked to nitrogen (N) of Formula 1, and in this regard, 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, which is the ortho position. 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, 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 halogen group, 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 C1-C10 alkoxy 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 C6-C30 aryloxy group; 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 C1-C10 alkoxy group, a C6-C30 aryl group, a C9-C30 fused ring group, and a C2-C30 heterocyclic 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 cyano group, a halogen group, a C1-C10 alkyl group, a C1-C10 alkoxy 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, a halogen group, 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 C1-C10 alkoxy group, a C1-C10 haloalkoxy 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 C6-C30 aryloxy 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, a C6-C60 arylsilyl group, a C2-C30 heterocyclic group, a heterocyclic group substituted with a C1-C10 alkyl group, or a C7-C30 arylalkyl 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)3, 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)3, a trimethylsilyl group, a tert-butyldimethylsilyl group, a tetramethyltetrahydronaphthalene group, a dimethyldihydroindene group, or a tetramethyldihydroindene group; a naphthyl group; a phenanthrenyl 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 phenylamine group which is unsubstituted or substituted with deuterium, a methyl group, an isopropyl group, a tert-butyl group, CD3, C(CD3)3, an isopropyl group substituted with a phenyl group, a trimethylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, a phenyl group, a biphenyl group, a dimethylfluorene group, a dibenzofuran group, or a dibenzothiophene 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 0, 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 Cy4 to be described below.
In Cy1 to Cy4,
* is a carbon that participates in the formation of a ring among R1 to R3, R6, and R7,
Y10 is O; S; Si(Ra3) (Ra4); or N(Ra5),
Y11 is O; S; Si(Ra3) (Ra4); C(Ra3) (Ra4); or N(Ra5),
R41 to R44 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, r44 is an integer from 0 to 4, and when r41 to r44 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 yet another exemplary embodiment, when r44 is 2 or higher, a plurality of R44'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 C5-C30 aromatic hydrocarbon ring; a substituted or unsubstituted C5-C30 aliphatic hydrocarbon ring; a substituted or unsubstituted C2-C30 aromatic hetero ring; or a substituted or unsubstituted C2-C30 aliphatic hydrocarbon ring.
In an exemplary embodiment of the present specification, R43 is bonded to adjacent R43 to form an indene ring; a benzene ring; a naphthalene ring; a cyclopentene ring; a cyclohexene ring; a tetrahydronaphthalene ring; a bicyclo[2.2.2]octene ring; a bicyclo[2.2.1]heptene ring; a benzofuran ring; a benzothiophene ring; a benzosilole ring; or an indole 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, the above-described definition on R1 to R3 and R31 may be applied to R44.
In an exemplary embodiment of the present specification, R44 is bonded to adjacent R44 to form a substituted or unsubstituted hydrocarbon ring.
In an exemplary embodiment of the present specification, R44 is bonded to adjacent R44 to form a benzene ring which is unsubstituted or substituted with R1 to R3.
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 O; 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, R42, and r42 are the same as those described above.
In the structures, p7 is 1 to 3, r421 is an integer from 0 to 10, and when r421 is 2 or higher, R42's are the same as or different from each other.
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-3 to 2-A-6
* is a moiety linked to Formula 2,
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 O; 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 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 halogen group; a cyano group; 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 halogen group; a cyano group; 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 halogen group; a cyano group; 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 halogen group; a cyano group; 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 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 includes one or more aliphatic hydrocarbon rings. Specifically, an aliphatic hydrocarbon ring may be included in one or more of A1 to A3, E1, and E2, R1 to R5 may be bonded to an adjacent substituent to form an aliphatic hydrocarbon ring, or R4 or R5 may be an aryl group in which an aliphatic hydrocarbon ring is fused. In this case, the aliphatic hydrocarbon ring may be specifically a cyclopentene ring substituted with a methyl group, or a cyclohexene ring substituted with 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, when the compound represented by Formula 2 is one selected among the following Group Z1, Formulae 1-1 to 1-3 include one or more hydrogens.
In an exemplary embodiment of the present specification, when Formula 2 includes four or more tert-butyl groups and A3 and E1 are a benzene ring, Formulae 1-1 to 1-3 include one or more hydrogens. In this case, the case where Formula 2 includes a tert-butyl group includes not only the case where a substituent (for example, R1 to R3) defined in Formula 2 is a tert-butyl group, but also the case where a substituent linked to a substituent (for example, R4 and R5) defined in Formula 2 is a tert-butyl group.
In an exemplary embodiment of the present specification, when Formula 2 includes four or more tert-amyl groups and A3 and E1 are a benzene ring, Formulae 1-1 to 1-3 include one or more hydrogens. In this case, the case where Formula 2 includes a tert-amyl group includes not only the case where a substituent (for example, R1 to R3) defined in Formula 2 is a tert-amyl group, but also the case where a substituent linked to a substituent (for example, R4 and R5) defined in Formula 2 is a tert-amyl group.
In an exemplary embodiment of the present specification, when A3 and E1 are a benzene ring, R1 to R3 are a tert-butyl group, and R4 and R5 are a phenyl group substituted with a tert-butyl group, Formulae 1-1 to 1-3 include one or more hydrogens.
In an exemplary embodiment of the present specification, when A3 and E1 are a benzene ring, R1 and R2 are a tert-butyl group, R4 and R5 are a phenyl group substituted with a tert-butyl group, and R3 is a diphenylamine group or a carbazole group, Formulae 1-1 to 1-3 include one or more hydrogens.
In an exemplary embodiment of the present specification, when Formula 2 includes four or more tert-butyl groups and A3 and E1 are a benzene ring, Formulae 1-1 to 1-3 include one or more hydrogens. In this case, the case where Formula 2 includes a tert-butyl group includes not only the case where a substituent (for example, R1 to R3) defined in Formula 2 is a tert-butyl group, but also the case where a substituent linked to a substituent (for example, R4 and R5) defined in Formula 2 is a tert-butyl group.
In an exemplary embodiment of the present specification, when Formula 2 includes four or more tert-amyl groups and A3 and E1 are a benzene ring, Formulae 1-1 to 1-3 include one or more hydrogens. In this case, the case where Formula 2 includes a tert-amyl group includes not only the case where a substituent (for example, R1 to R3) defined in Formula 2 is a tert-amyl group, but also the case where a substituent linked to a substituent (for example, R4 and R5) defined in Formula 2 is a tert-amyl group.
In an exemplary embodiment of the present specification, when A3 and E1 are a benzene ring, R1 to R3 are a tert-butyl group, and R4 and R5 are a phenyl group substituted with a tert-butyl group, Formulae 1-1 to 1-3 include one or more hydrogens.
In an exemplary embodiment of the present specification, when A3 and E1 are a benzene ring, R1 and R2 are a tert-butyl group, R4 and R5 are a phenyl group substituted with a tert-butyl group, and R3 is a diphenylamine group or a carbazole group, Formulae 1-1 to 1-3 include one or more hydrogens.
In an exemplary embodiment of the present specification, when the compound represented by Formula 2 is one selected among Group Z1, one or more of Ar11 to Ar13 of Formula 1-1, one or more of Ar21 to Ar24 of Formula 1-2, and one or more of Ar31 and Ar32 of Formula 1-3 are a substituent other than hydrogen.
In an exemplary embodiment of the present specification, when Formula 2 includes four or more tert-butyl groups, one or more of Ar11 to Ar13 of Formula 1-1, one or more of Ar21 to Ar24 of Formula 1-2, and one or more of Ar31 and Ar32 of Formula 1-3 are a substituent other than hydrogen.
In an exemplary embodiment of the present specification, when Formula 2 includes four or more tert-amyl groups, one or more of Ar11 to Ar13 of Formula 1-1, one or more of Ar21 to Ar24 of Formula 1-2, and one or more of Ar31 and Ar32 of Formula 1-3 are a substituent other than hydrogen.
In an exemplary embodiment of the present specification, when R1 to R3 are a tert-butyl group and R4 and R5 are a phenyl group substituted with a tert-butyl group, one or more of Ar11 to Ar13 of Formula 1-1, one or more of Ar21 to Ar24 of Formula 1-2, and one or more of Ar31 and Ar32 of Formula 1-3 are a substituent other than hydrogen.
In an exemplary embodiment of the present specification, when R1 and R2 are a tert-butyl group, R4 and R5 are a phenyl group substituted with a tert-butyl group, and R3 is a diphenylamine group or a carbazole group, one or more of Ar11 to Ar13 of Formula 1-1, one or more of Ar21 to Ar24 of Formula 1-2, and one or more of Ar31 and Ar32 of Formula 1-3 are a substituent other than hydrogen.
In an exemplary embodiment of the present specification, Formula 2 excludes compounds of Group Z1. 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 any one of 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 any one of 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 any one of 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 any one of 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 any one of Formulae 1-1 to 1-3 as a host. In this case, one of the compounds represented by any one of 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, the 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, a 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 a positive electrode, 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 negative electrode, 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 negative electrode material, an organic material layer, and a positive electrode 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 positive electrode is an electrode which injects holes, and as a positive electrode 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 positive electrode 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 negative electrode is an electrode which injects electrons, and as a negative electrode 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 negative electrode 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 positive electrode 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 a positive electrode 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 positive electrode 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 a positive electrode 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 negative electrode and transfer the electrons to a light emitting layer. Specific examples thereof include: A1 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 negative electrode, 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.
After 9-([1,1′-biphenyl]-3-yl)-10-bromoanthracene (50 g, 122 mmol) and dibenzo[b,d]furan-2-ylbronic acid (31.8 g, 150 mmol) were dissolved in THF (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 mixture 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]+=497
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]+=521
Compound BH-2-a was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-a, except that 9-([1,1′-biphenyl]-3-yl)-10-bromoanthracene was changed into 9-bromo-10-(4-(naphthalen-2-yl)phenyl)anthracene, and dibenzo[b,d]furan-2-ylboronic acid was changed into dibenzo[b,d]furan-3-ylboronic acid. MS: [M+H]+=547
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]+=573
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]+=421
Compound BH-3-b was obtained by performing synthesis and purification in the same manner as in Synthesis Example 15-a, except that 2-phenylanthracene was changed into Compound BH-3-a. MS: [M+H]+=499
Compound BH-3 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 (3-naphthalen-2-yl-d7)phenyl-2,4,5,6-d4)boronic acid. MS: [M+H]+=634
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]+=623
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]+=653
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]+=573
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]+=601
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. [M+H]+=573
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. [M+H]+=601
Compound BH-7-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-(dibenzo[b,d]furan-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane. [M+H]+=497
Compound BH-7 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-7-a. [M+H]+=521
Compound BH-8-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-([1,1′-biphenyl]-3-yl)-anthracene. [M+H]+=349
Compound BH-8-b was obtained by performing synthesis and purification in the same manner as in Synthesis Example 15-a, except that 2-phenylanthracene was changed into Compound BH-8-a. MS: [M+H]+=426
Compound BH-8 was obtained by performing synthesis and purification in the same manner as in Synthesis Example 1-a. [M+H]+=514
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. [M+H]+=699
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. [M+H]+=733
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
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
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
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
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
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
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
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
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
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
After 2-(1-naphthyl)anthracene (50 g, 164 mmol) was dispersed in 500 ml of dimethylformamide, a solution of n-bromosuccinimide (35 g, 197 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 EA to obtain Compound BH-15-a (56 g, yield 85%). [M+H]+=383
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 9-bromo-2-(1-naphthyl)anthracene, and dibenzo[b,d]furan-2-ylboronic acid was changed into [1,1′-biphenyl]-3-ylboronic acid. [M+H]+=457
Compound BH-15-c was obtained by performing synthesis and purification in the same manner as in Synthesis Example 15-a, except that 2-phenylanthracene was changed into Compound BH-15-b. [M+H]+=535
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. [M+H]+=623
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. [M+H]+=653
Compound BH-16 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-2-yl)phenyl)anthracene-1,2,3,4,5,6,7,8-d, and dibenzo[b,d]furan-2-ylboronic acid was changed into dibenzo[b,d]furan-1-ylboronic acid. [M+H]+=555
Compound BH-17-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-bromoanthracene, and dibenzo[b,d]furan-2-ylboronic acid was changed into [1,1′-biphenyl-d9]-3-ylboronic acid. [M+H]+=339
Compound BH-17-b was obtained by performing synthesis and purification in the same manner as in Synthesis Example 15-a, except that 2-phenylanthracene was changed into Compound BH-17-a. [M+H]+=417
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, and dibenzo[b,d]furan-2-ylboronic acid was changed into (dibenzo[b,d]furan-2-yl-d7)boronic acid. [M+H]+=512
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)
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)
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)
BH-19 was obtained from BH-19-H in the same manner as in Synthesis Example <18-b>. (Yield 62%, MS[M+H]+=493)
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)
BH-20 was obtained from BH-20-H in the same manner as in Synthesis Example <18-b>. (Yield 65%, MS[M+H]+=493)
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)
BH-21 was obtained from BH-21-H in the same manner as in Synthesis Example <18-b>. (Yield 55%, MS[M+H]+=493)
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)
BH-22 was obtained from BH-22-H in the same manner as in Synthesis Example <18-b>. (Yield 68%, MS[M+H]+=493)
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)
BH-23 was obtained from BH-23-H in the same manner as in Synthesis Example <18-b>. (Yield 60%, MS[M+H]+=573)
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)
BH-24 was obtained from BH-24-H in the same manner as in Synthesis Example <18-b>. (Yield 66%, MS[M+H]+=573)
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)
BH-25 was obtained from BH-25-H in the same manner as in Synthesis Example <18-b>. (Yield 64%, MS[M+H]+=625)
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)
BH-26 was obtained from BH-26-H in the same manner as in Synthesis Example <18-b>. (Yield 62%, MS[M+H]+=625)
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)
BH-27 was obtained from BH-27-H in the same manner as in Synthesis Example <18-b>. (Yield 65%, MS[M+H]+=573)
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)
After Compound BH-11-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)
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 was 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)
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)
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)
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)
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 2 M 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
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
After Compound 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
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
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
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
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
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
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
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
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
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
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
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
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
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 Synthesis Example 38. Synthesis of BH-38
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
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
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
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-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
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
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-8-a. MS: [M+H]+=401
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-38-b. MS: [M+H]+=479
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-38-c, and (4-(naphthalen-1-yl)phenyl)boronic acid was changed into naphthalene-1-ylboronic acid. MS: [M+H]+=526
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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
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 Synthesis Example 55. Synthesis of 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
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
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
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
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
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
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
After 1,3-dibromo-5-chlorobenzene (1 eq.) and 3,6-di-tert-butyl-9H-carbazole (1 eq.) were dissolved in toluene (0.3 M) in a three-neck flask and sodium tert-butoxide (1.2 eq.) and bis(tri-tert-butylphosphine)palladium(0) (0.01 eq.) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 3 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain Compound BD-1-a. (Yield 77%, MS[M+H]+=469)
BD-1-b was obtained from BD-1-a and 3-((4-tert-butyl-2,6-dimethylphenyl)amino)benzofuran-5-carbonitrile in the same manner as in Synthesis Example <60-a>. (Yield 68%, MS[M+H]+=706)
After Compound BD-1-b was dissolved in 1,2-dichlorobenzene (0.1 M) in a three-neck flask and boron triiodide (2 eq.) was added thereto, the resulting mixture was stirred in an argon atmosphere at 140° C. for 3 hours. The reaction product was cooled to 0° C., N,N-diisopropylethylamine (20 eq.) was added thereto, and then the resulting mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain Compound BD-1-c. (Yield 24%, MS[M+H]+=714)
After Compound BD-1-c and bis(4-tert-butylphenyl)amine (1.2 eq.) were dissolved in toluene (0.3 M) in a three-neck flask and sodium tert-butoxide (2 eq.) and bis(tri-tert-butylphosphine)palladium(0) (0.01 eq.) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 24 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography, and then subjected to sublimation purification to obtain Compound BD-1. (Yield 67%, MS[M+H]+=959)
BD-2-a was obtained from 1-bromo-3-chloro-5-(methyl-d3)benzene and N1-(4-tert-butylphenyl)-N3,N3-diphenylbenzene-1,3-diamine in the same manner as in Synthesis Example <60-a>. (Yield 79%, MS[M+H]+=520)
BD-2-b was obtained from BD-2-a and 1-([1,1′-biphenyl]-2-yl)-5-tert-butyl-N-(5-tert-butyl-[1,1′-biphenyl]-2-yl)-1H-indole-2-amine in the same manner as in
<61-c> Preparation of Compound BD-2 BD-2 was obtained from BD-2-b in the same manner as in Synthesis Example <60-c>. (Yield 19%, MS[M+H]+=1040)
BD-3-a was obtained from 5-tert-butyl-N-(3-(2-phenylpropan-2-yl)phenyl)-[1,1′-biphenyl]-2-amine in the same manner as in Synthesis Example <60-a>. (Yield 79%, MS[M+H]+=609)
BD-3-b was obtained from BD-3-a and 5-tert-butyl-N-(5-tert-butyl-[1,1′-biphenyl]-2-yl)benzo[b]thiophene-3-amine in the same manner as in Synthesis Example <60-a>. (Yield 75%, MS[M+H]+=942)
BD-3-c was obtained from BD-3-b in the same manner as in Synthesis Example <60-c>. (Yield 26%, MS[M+H]+=950)
BD-3-d was obtained from BD-3-c and diphenylamine in the same manner as in Synthesis Example <60-d>. (Yield 88%, MS[M+H]+=1082)
BD-3 was obtained from BD-3-d in the same manner as in Synthesis Example <1-b>. (Yield 58%, MS[M+H]+=1122)
After 1-bromo-3-chloro-5-methylbenzene and bis(4-tert-butylphenyl)amine were dissolved in toluene in a three-neck flask and sodium tert-butoxide and bis(tri-tert-butylphosphine)palladium(0) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 3 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 234 g of Compound BD-4-a. (Yield 92%, MS[M+H]+=523)
BD-4-b was obtained from BD-4-a and N-(4-tert-butylphenyl)-4,5,6,7-tetramethyl-tetrahydrobenzo[b]thiophene-3-amine in the same manner as in Synthesis Example <60-a>. (Yield 72%, MS[M+H]+=711)
BD-4 was obtained from BD-4-b in the same manner as in Synthesis Example <60-d>. (Yield 21%, MS[M+H]+=719)
BD-5-a was obtained from 1,3-dibromo-5-chlorophenyl and 5-tert-butyl-N-(3-(2-phenylpropan-2-yl)phenyl)-[1,1′-biphenyl]-2-amine in the same manner as in Synthesis Example <60-a>. (Yield 83%, MS[M+H]+=609)
BD-25-b was obtained from BD-5-a and N-(4-tert-butylphenyl)-6,6-dimethyl-6,7-dihydro-5H-indeno[5,6-b]thiophene-3-amine in the same manner as in Synthesis Example <60-a>. (Yield 76%, MS[M+H]+=878)
BD-5-c was obtained from BD-5-b in the same manner as in Synthesis Example <60-c>. (Yield 21%, MS[M+H]+=885)
BD-5 was obtained from BD-5-c and 4a,9a-dimethyl-2,3,4,4a,9,9a-hexahydro-1H-carbazole in the same manner as in Synthesis Example <60-d>. (Yield 81%, MS[M+H]+=1050)
After 1,3-dibromo-5-methylbenzene (1 eq.) and 5-tert-butyl-N-(4-tert-butylphenyl)benzo[b]thiophene-3-amine (2 eq.) were dissolved in toluene (0.3 M) in a three-neck flask and sodium tert-butoxide (2.5 eq.) and bis(tri-tert-butylphosphine)palladium(0) (0.01 eq.) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 8 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain Compound BD-6-a. (Yield 68%, MS[M+H]+=763)
BD-6 was obtained from BD-6-a in the same manner as in Synthesis Example <60-c>. (Yield 27%, MS[M+H]+=771)
BD-7-a was obtained from 1-bromo-3-chloro-5-methylbenzene and N-(5-tert-butyl-[1,1′-biphenyl]-2-yl)-1-(4-fluorophenyl)-5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1H-benzo[f]indole-3-amine in the same manner as in Synthesis Example <60-a>. (Yield 84%, MS[M+H]+=669)
BD-7-b was obtained from BD-7-a and N-(5-tert-butyl-[1,1′-biphenyl]-2-yl)-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphtho[2,3-b]thiophene-3-amine in the same manner as in Synthesis Example <60-a>. (Yield 79%, MS[M+H]+=1101)
BD-7 was obtained from BD-7-b in the same manner as in Synthesis Example <60-c>. (Yield 21%, MS[M+H]+=1108)
BD-8-a was obtained from 1-bromo-3-chloro-5-methylbenzene and 5-tert-butyl-N-(5-tert-butyl-[1,1′-biphenyl]-2-yl)benzofuran-3-amine in the same manner as in Synthesis Example <60-a>. (Yield 77%, MS[M+H]+=522)
BD-8-b was obtained from BD-8-a and N-(5-tert-butyl-[1,1′-biphenyl]-2-yl)-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphtho[2,3-b]thiophene-3-amine in the same manner as in Synthesis Example <60-a>. (Yield 80%, MS[M+H]+=953)
BD-8 was obtained from BD-8-b in the same manner as in Synthesis Example <60-c>. (Yield 24%, MS[M+H]+=961)
BD-9-a was obtained from 1,3-dibromo-5-chlorophenyl and 5-tert-butyl-N-(4-tert-butylphenyl)benzofuran-2-amine in the same manner as in Synthesis Example <60-a>. (Yield 63%, MS[M+H]+=511)
BD-9-b was obtained from BD-9-a and N-(4-tert-butylphenyl)-5,8-dimethyl-5,6,7,8-tetrahydro-5,8-ethanonaphtho[2,3-b]thiophene-3-amine in the same manner as in Synthesis Example <60-a>. (Yield 85%, MS[M+H]+=820)
BD-9-c was obtained from BD-9-b in the same manner as in Synthesis Example <60-c>. (Yield 24%, MS[M+H]+=827)
BD-9 was obtained from BD-9-c and diphenylamine in the same manner as in Synthesis Example <60-d>. (Yield 76%, MS[M+H]+=960)
BD-10-a was obtained from 1,3-dibromo-5-chlorophenyl and 5-tert-butyl-1-(5-tert-butyl-[1,1′-biphenyl]-2-yl)-N-(4-tert-butylphenyl)-1H-indole-2-amine in the same manner as in Synthesis Example <60-a>. (Yield 72%, MS[M+H]+=718)
BD-10-b was obtained from BD-10-a and N-(4-tert-butylphenyl)-5-phenylbenzo[b]thiophene-3-amine in the same manner as in Synthesis Example <60-a>. (Yield 79%, MS[M+H]+=995)
BD-10-c was obtained from BD-10-b in the same manner as in Synthesis Example <60-c>. (Yield 19%, MS[M+H]+=1003)
BD-10 was obtained from BD-10-c and bis(4-tert-butylphenyl)amine in the same manner as in Synthesis Example <60-d>. (Yield 81%, MS[M+H]+=1248)
BD-11-a was obtained from 1-bromo-3-chloro-5-methylbenzene and 5-tert-butyl-N-(3-(2-phenylpropan-2-yl)phenyl)-[1,1′-biphenyl]-2-amine in the same manner as in Synthesis Example <60-a>. (Yield 89%, MS[M+H]+=544)
BD-11-b was obtained from BD-11-a and N-(4-tert-butylphenyl)-4,4-dimethyl-4H-indeno[1,2-b]furan-1-amine in the same manner as in Synthesis Example <60-a>. (Yield 63%, MS[M+H]+=839)
BD-11 was obtained from BD-11-b in the same manner as in Synthesis Example <60-c>. (Yield 15%, MS[M+H]+=847)
BD-13-a was obtained from BD-4-a and N-(5-tert-butyl-[1,1′-biphenyl]-2-yl)-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphtho[2,3-b]thiophene-3-amine in the same manner as in Synthesis Example <60-a>. (Yield 87%, MS[M+H]+=837)
BD-13 was obtained from BD-13-a in the same manner as in Synthesis Example <60-c>. (Yield 19%, MS[M+H]+=845)
BD-14-a was obtained from 1-bromo-3-chloro-5-methylbenzene and bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)amine in the same manner as in Synthesis Example <60-a>. (Yield 92%, MS[M+H]+=514)
BD-14-b was obtained from BD-14-a and 7-tert-butyl-N-(4-tert-butyl-2-methylphenyl)-4,4-dimethyl-4H-indeno[1,2-b]thiophene-2-amine in the same manner as in Synthesis Example <60-a>. (Yield 74%, MS[M+H]+=895)
BD-14 was obtained from BD-14-b in the same manner as in Synthesis Example <60-c>. (Yield 23%, MS[M+H]+=903)
BD-15-a was obtained from BD-4-a and N-(5-tert-butyl-[1,1′-biphenyl]-2-yl)naphtho[2,3-b]thiophene-3-amine in the same manner as in Synthesis Example <60-a>. (Yield 85%, MS[M+H]+=777)
BD-15 was obtained from BD-15-a in the same manner as in Synthesis Example <60-c>. (Yield 29%, MS[M+H]+=785)
BD-16-a was obtained from BD-4-a and 1-([1,1′-biphenyl]-4-yl)-4,4,7,7-tetramethyl-N-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-4,5,6,7-tetrahydro-1H-indole-3-amine in the same manner as in Synthesis Example <60-a>. (Yield 77%, MS[M+H]+=900)
BD-16 was obtained from BD-16-a in the same manner as in Synthesis Example <60-c>. (Yield 16%, MS[M+H]+=908)
BD-17-a was obtained from 1-bromo-3-chloro-5-methylbenzene and N-mesityl-5a,10a-dimethyl-5-phenyl-5,5a,6,7,8,9,10,10-octahydrocyclohepta[b]indole-2-amine in the same manner as in Synthesis Example <60-a>. (Yield 83%, MS[M+H]+=549)
BD-17-b was obtained from BD-17-a and N-(4-tert-butylphenyl)-4,4,6,6-tetramethyl-5,6-dihydro-4H-cyclopenta[b]thiophene-3-amine in the same manner as in
BD-17 was obtained from BD-17-b in the same manner as in Synthesis Example <60-c>. (Yield 16%, MS[M+H]+=848)
6-bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene (25.0 g, 93.6 mmol), 5-(tert-butyl)-[1,1′-biphenyl]-2-amine (21.08 g, 93.6 mmol), Pd(Pt-Bu3)2 (0.96 g, 1.9 mmol), and NaOt-Bu(17.98 g, 187.1 mmol) were dissolved in toluene (467 ml) and stirred while being refluxed. When the reaction was completed, the reaction product was transferred to a separatory funnel after being cooled to room temperature, and then extracted. The extract was dried over MgSO4, filtered, concentrated, and purified with column chromatography to obtain BD-18-a (31.19 g, yield 81%). MS: [M+H]+=412
BD-18-a (31.19 g, 75.8 mmol), 1-bromo-3-chloro-5-methylbenzene (15.57 g, 75.8 mmol), Pd(Pt-Bu3)2 (0.77 g, 1.9 mmol), and NaOt-Bu (14.56 g, 151.5 mmol) were dissolved in toluene (378 ml) and stirred while being refluxed. When the reaction was completed, the reaction product was transferred to a separatory funnel after being cooled to room temperature, and then extracted. The extract was dried over MgSO4, filtered, concentrated, and purified with column chromatography to obtain BD-18-b (30.47 g, yield 75%). MS: [M+H]+=537
BD-18-b (30.47 g, 56.8 mmol), 4-(tert-butyl)aniline (8.48 g, 56.8 mmol), Pd(Pt-Bu3)2 (0.58 g, 1.1 mmol), and NaOt-Bu (10.92 g, 113.7 mmol) were dissolved in toluene (284 ml) and stirred while being refluxed. When the reaction was completed, the reaction product was transferred to a separatory funnel after being cooled to room temperature, and then extracted. The extract was dried over MgSO4, filtered, concentrated, and purified with column chromatography to obtain BD-18-c (26.55 g, yield 72%).
MS: [M+H]+=649
BD-18-c (26.55 g, 40.9 mmol), 3-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphtho[2,3-b]thiophene (13.23 g, 40.9 mmol), Pd(Pt-Bu3)2 (0.42 g, 0.8 mmol), and NaOt-Bu (7.86 g, 81.8 mmol) were dissolved in toluene (204 ml) and stirred while being refluxed. When the reaction was completed, the reaction product was transferred to a separatory funnel after being cooled to room temperature, and then extracted. The extract was dried over MgSO4, filtered, concentrated, and purified with column chromatography to obtain BD-18-d (30.27 g, yield 83%). MS: [M+H]+=892
BD-18-d (30.27 g, 34.0 mmol) was dissolved in DCB (340 ml), BI3 (19.94 g, 50.9 mmol) was added thereto, and the resulting mixture was stirred at 130° C. When the reaction was completed, DIPEA (17.56 g, 135.8 mmol) was added thereto at 0° C. Then, the reaction product was transferred to a separatory funnel, and then extracted. The extract was dried over MgSO4, filtered, concentrated, and purified with column chromatography to obtain BD-18 (9.16 g, yield 30%). MS: [M+H]+=900
BD-19-a was obtained in the same manner as in Synthesis Example <77-a>. MS: [M+H]+=390
BD-19-b was obtained from BD-19-a and 1-bromo-3,5-dichlorobenzene in the same manner as in Synthesis Example
BD-19-c was obtained from BD-19-b and 5-(tert-butyl)-[1,1′-biphenyl]-2-amine in the same manner as in Synthesis Example <77-a>. MS: [M+H]+=724
BD-19-d was obtained from BD-19-c and 3-bromo-5-(tert-butyl)benzo[b]thiophene in the same manner as in Synthesis Example <77-d>. MS: [M+H]+=912
BD-19-e was obtained from BD-19-d in the same manner as in Synthesis Example <77-e>. MS: [M+H]+=920
BD-19 was obtained from BD-19-e and diphenylamine in the same manner as in Synthesis Example <77-b>. MS: [M+H]+=1053
BD-20-a was obtained from BD-14-a and 4-(tert-butyl)-2-methylaniline in the same manner as in Synthesis Example
BD-20-b was obtained from BD-20-a and 3-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphtho[2,3-b]furan in the same manner as in Synthesis Example <77-d>. MS: [M+H]+=868
BD-20 was obtained from BD-20-b in the same manner as in Synthesis Example <77-e>. MS: [M+H]+=876
BD-21-a was obtained from N-(4-(tert-butyl)phenyl)-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-amine and 1-bromo-3-dichloro-5-methylbenzene in the same manner as in Synthesis Example <77-b>. MS: [M+H]+=535
BD-21-b was obtained from BD-21-a and 4′,5-di-tert-butyl-[1,1′-biphenyl]-2-amine in the same manner as in
BD-21-c was obtained from BD-21-b and 3-bromo-5-(tert-butyl)benzo[b]thiophene in the same manner as in Synthesis Example <77-d>. MS: [M+H]+=894
BD-21 was obtained from BD-21-c in the same manner as in Synthesis Example <77-e>. MS: [M+H]+=902
BD-22-a was obtained from BD-4-a and 4′-(tert-butyl)-5-(trimethylsilyl)-[1,1′-biphenyl]-2-amine in the same manner as in Synthesis Example <77-c>. MS: [M+H]+=668
BD-22-b was obtained from BD-22-a and 3-bromo-5,8-dimethyl-5,6,7,8-tetrahydro-5,8-ethanonaphtho[2,3-b]thiophene in the same manner as in Synthesis Example <77-d>. MS: [M+H]+=908
BD-22 was obtained from BD-22-b in the same manner as in Synthesis Example <77-e>. MS: [M+H]+=916
After 1-adamantylamine (132.2 mmol, 20 g) and 6-tert-butyl-3-bromobenzofuran (132.2 mmol, 33.5 g) were dissolved in toluene (0.2 M, 661 ml) in a three-neck flask and sodium tert-butoxide (198 mmol, 19 g) and bis(tri-tert-butylphosphine)palladium(0) (1.32 mmol, 0.68 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 6 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 31.2 g of Compound BD-23-a. (Yield 73%, MS[M+H]+=323)
After Compound BD-4-a (61.6 mmol, 25 g) and Compound BD-23-a (61.6 mmol, 19.9 g) were dissolved in toluene (0.2 M, 307 ml) in a three-neck flask and sodium tert-butoxide (92.4 mmol, 8.9 g) and bis(tri-tert-butylphosphine)palladium(0) (0.62 mmol, 0.31 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 12 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 24.4 g of Compound BD-23-b. (Yield 57%, MS[M+H]+=693)
After Compound BD-23-b (30.8 mmol, 22.4 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 308 ml) in a three-neck flask and boron triiodide (49.3 mmol, 19.3 g) was added thereto, the resulting mixture was stirred in an argon atmosphere at 140° C. for 3 hours. The reaction product was cooled to 0° C., N,N-diisopropylethylamine (277 mmol, 36 g) was added thereto, and then the resulting mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography, and then subjected to sublimation purification to obtain 3.4 g of Compound BD-23. (Yield 16%, MS[M+H]+=701)
After 1,3-dibromo-5-chlorobenzene (111 mmol, 30 g) and bis(4-tert-butylphenyl)amine (111 mmol, 31.2 g) were dissolved in toluene (0.2 M, 555 ml) in a three-neck flask and sodium tert-butoxide (166.5 mmol, 16 g) and bis(tri-tert-butylphosphine)palladium(0) (1.1 mmol, 0.58 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 1 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 30.6 g of Compound BD-24-a. (Yield 59%, MS[M+H]+=471)
After 3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene-2-amine (79.1 mmol, 21.7 g) and 5-tert-butyl-3-bromobenzofuran (79.1 mmol, 20 g) were dissolved in toluene (0.2 M, 395 ml) in a three-neck flask and sodium tert-butoxide (118.6 mmol, 11.4 g) and bis(tri-tert-butylphosphine)palladium(0) (0.79 mmol, 0.40 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 6 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 25.3 g of Compound BD-24-b. (Yield 82%, MS[M+H]+=390)
After Compound BD-24-a (63.7 mmol, 39 g) and Compound BD-24-a (63.7 mmol, 24.8 g) were dissolved in toluene (0.2 M, 319 ml) in a three-neck flask and sodium tert-butoxide (95.6 mmol, 9.2 g) and bis(tri-tert-butylphosphine)palladium(0) (0.64 mmol, 0.33 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 3 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 27.7 g of Compound BD-24-c. (Yield 56%, MS[M+H]+=780)
After Compound BD-24-c (35.5 mmol, 27.7 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 355 ml) in a three-neck flask and boron triiodide (56.9 mmol, 22.3 g) was added thereto, the resulting mixture was stirred in an argon atmosphere at 140° C. for 3 hours. The reaction product was cooled to 0° C., N,N-diisopropylethylamine (320 mmol, 41 g) was added thereto, and then the resulting mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 6.2 g of Compound BD-24-d. (Yield 22%, MS[M+H]+=787) Step 5) Synthesis of Compound BD-24
After Compound BD-24-d (7.9 mmol, 6.2 g) and 9,9-dimethyl-9,10-dihydroacridine (9.4 mmol, 2 g) were dissolved in toluene (0.2 M, 47 ml) in a three-neck flask and sodium tert-butoxide (11.8 mmol, 1.1 g) and bis(tri-tert-butylphosphine)palladium(0) (0.08 mmol, 0.04 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 18 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography, and then subjected to sublimation purification to obtain 24.7 g of Compound BD-24. (Yield 77%, MS[M+H]+=960)
After 1-bromo-3-chloro-5-tert-butylbenzene (121 mmol, 30 g) and 4-tert-butyl-N-(4-tert-butylphenyl)-2,6-dimethylaniline (121 mmol, 37.5 g) were dissolved in toluene (0.2 M, 605 ml) in a three-neck flask and sodium tert-butoxide (182 mmol, 17.5 g) and bis(tri-tert-butylphosphine)palladium(0) (1.2 mmol, 0.62 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 4 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 51.2 g of Compound BD-25-a. (Yield 89%, MS[M+H]+=476)
After 3-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphtho[2,3-b]furan (97.6 mmol, 30 g) and 4-tert-butylaniline (97.6 mmol, 14.6 g) were dissolved in toluene (0.2 M, 488 ml) in a three-neck flask and sodium tert-butoxide (146.5 mmol, 14.1 g) and bis(tri-tert-butylphosphine)palladium(0) (0.98 mmol, 0.5 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 6 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 35.4 g of Compound BD-25-b. (Yield 97%, MS[M+H]+=376)
After Compound BD-25-a (44.1 mmol, 21 g) and Compound 25-b (44.1 mmol, 16.6 g) were dissolved in toluene (0.2 M, 220 ml) in a three-neck flask and sodium tert-butoxide (66.2 mmol, 6.4 g) and bis(tri-tert-butylphosphine)palladium(0) (0.44 mmol, 0.23 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 6 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 21.8 g of Compound BD-25-c. (Yield 61%, MS[M+H]+=815)
After Compound BD-25-c (26.7 mmol, 21.8 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 267 ml) in a three-neck flask and boron triiodide (42.8 mmol, 16.8 g) was added thereto, the resulting mixture was stirred in an argon atmosphere at 140° C. for 3 hours. The reaction product was cooled to 0° C., N,N-diisopropylethylamine (241 mmol, 31 g) was added thereto, and then the resulting mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography, and then subjected to sublimation purification to obtain 3.4 g of Compound BD-25. (Yield 15%, MS[M+H]+=823)
After 4-tert-butylaniline (33.5 mmol, 5 g) and 9-(3-bromobenzofuran-6-yl)-4a,9a-dimethyl-2,3,4,4a,9,9a-hexahydro-1H-carbazole (33.5 mmol, 13.3 g) were dissolved in toluene (0.2 M, 168 ml) in a three-neck flask and sodium tert-butoxide (50.3 mmol, 4.83 g) and bis(tri-tert-butylphosphine)palladium(0) (0.335 mmol, 0.171 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 3 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 13.2 g of Compound BD-26-a. (Yield 85%, MS[M+H]+=465)
After Compound BD-4-a (25.9 mmol, 10.5 g) and Compound BD-26-a (25.9 mmol, 12.0 g) were dissolved in toluene (0.2 M, 129 ml) in a three-neck flask and sodium tert-butoxide (38.8 mmol, 3.73 g) and bis(tri-tert-butylphosphine)palladium(0) (0.259 mmol, 0.132 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 6 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 19.4 g of Compound BD-26-b. (Yield 90%, MS[M+H]+=834)
After Compound BD-26-b (23.3 mmol, 19.4 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 233 ml) in a three-neck flask and boron triiodide (37.2 mmol, 14.6 g) was added thereto, the resulting mixture was stirred in an argon atmosphere at 140° C. for 3 hours. The reaction product was cooled to 0° C., N,N-diisopropylethylamine (209 mmol, 27.1 g) was added thereto, and then the resulting mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography, and then subjected to sublimation purification to obtain 3.7 g of Compound BD-26. (Yield 19%, MS[M+H]+=842)
After 5-trimethylsilyl-N-(4-trimethylsilylphenyl)-[1,1′-biphenyl]-2-amine (51.3 mmol, 20 g) and 1-bromo-3-chloro-5-tert-butylbenzene (51.3 mmol, 12.7 g) were dissolved in toluene (0.2 M, 257 ml) in a three-neck flask and sodium tert-butoxide (77.0 mmol, 7.40 g) and bis(tri-tert-butylphosphine)palladium(0) (0.513 mmol, 0.262 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 4 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 26.7 g of Compound BD-27-a. (Yield 94%, MS[M+H]+=556)
After 3-bromo-8,8-dimethyl 8H-indeno[2,1-b]furan (76.0 mmol, 20 g) and 4-tert-butylaniline (76.0 mmol, 11.3 g) were dissolved in toluene (0.2 M, 380 ml) in a three-neck flask and sodium tert-butoxide (114 mmol, 11.0 g) and bis(tri-tert-butylphosphine)palladium(0) (0.760 mmol, 0.388 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 12 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 17.3 g of Compound BD-27-b. (Yield 69%, MS[M+H]+=331)
After Compound BD-27-a (41.3 mmol, 23 g) and Compound BD-27-b (41.3 mmol, 13.7 g) were dissolved in toluene (0.2 M, 207 ml) in a three-neck flask and sodium tert-butoxide (62.0 mmol, 6.00 g) and bis(tri-tert-butylphosphine)palladium(0) (0.413 mmol, 0.211 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 18 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 23.7 g of Compound BD-27-c. (Yield 67%, MS[M+H]+=839)
After Compound BD-27-c (27.8 mmol, 23.7 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 280 ml) in a three-neck flask and boron triiodide (44.5 mmol, 17.4 g) was added thereto, the resulting mixture was stirred in an argon atmosphere at 140° C. for 3 hours. The reaction product was cooled to 0° C., N,N-diisopropylethylamine (251 mmol, 32.4 g) was added thereto, and then the resulting mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography, and then subjected to sublimation purification to obtain 3.5 g of Compound BD-27. (Yield 15%, MS[M+H]+=859)
After N,N-bis(2-fluorophenyl)-4a,9a-dimethyl-2,3,4,4a,9,9a-hexahydro-1H-carbazol-5-amine (34.1 mmol, 13.8 g) and 1-bromo-3-chloro-5-methylbenzene (34.1 mmol, 7 g) were dissolved in toluene (0.2 M, 170 ml) in a three-neck flask and sodium tert-butoxide (51.1 mmol, 4.91 g) and bis(tri-tert-butylphosphine)palladium(0) (0.341 mmol, 0.174 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 4 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 15.3 g of Compound BD-28-a. (Yield 85%, MS[M+H]+=15.3)
After 3-bromo-5-tert-butylbenzo[b]thiophene (149 mmol, 40 g) and 4-tert-butylaniline (149 mmol, 22.2 g) were dissolved in toluene (0.2 M, 745 ml) in a three-neck flask and sodium tert-butoxide (223 mmol, 21.4 g) and bis(tri-tert-butylphosphine)palladium(0) (1.49 mmol, 0.759 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 18 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 45.6 g of Compound BD-28-b. (Yield 91%, MS[M+H]+=338)
After Compound BD-28-a (28.4 mmol, 15 g) and Compound BD-28-b (28.4 mmol, 9.57 g) were dissolved in toluene (0.2 M, 140 ml) in a three-neck flask and sodium tert-butoxide (42.5 mmol, 4.09 g) and bis(tri-tert-butylphosphine)palladium(0) (0.284 mmol, 0.145 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 24 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 18.4 g of Compound BD-28-c. (Yield 78%, MS[M+H]+=830)
After Compound BD-28-c (22.2 mmol, 18.4 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 220 ml) in a three-neck flask and boron triiodide (35.5 mmol, 13.9 g) was added thereto, the resulting mixture was stirred in an argon atmosphere at 140° C. for 3 hours. The reaction product was cooled to 0° C., N,N-diisopropylethylamine (199 mmol, 25.8 g) was added thereto, and then the resulting mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography, and then subjected to sublimation purification to obtain 3.8 g of Compound BD-28. (Yield 20%, MS[M+H]+=838)
After bis-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)amine (77.0 mmol, 30 g) and 1-bromo-3-chloro-5-methylbenzene (77.0 mmol, 15.8 g) were dissolved in toluene (0.2 M, 385 ml) in a three-neck flask and sodium tert-butoxide (115 mmol, 11.1 g) and bis(tri-tert-butylphosphine)palladium(0) (0.77 mmol, 0.393 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 6 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 36.6 g of Compound BD-29-a. (Yield 92%, MS[M+H]+=514)
After 2-bromo-7-tert-butyl-4,4-dimethyl-4H-indeno[1,2-b]thiophene (35.8 mmol, 12 g) and 4-tert-butyl-2-methylaniline (35.8 mmol, 5.84 g) were dissolved in toluene (0.2 M, 180 ml) in a three-neck flask and sodium tert-butoxide (53.7 mmol, 5.16 g) and bis(tri-tert-butylphosphine)palladium(0) (0.358 mmol, 0.183 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 12 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 13.4 g of Compound BD-29-b. (Yield 90%, MS[M+H]+=418)
After Compound BD-29-a (29.2 mmol, 15 g) and Compound BD-29-b (29.2 mmol, 12.2 g) were dissolved in toluene (0.2 M, 145 ml) in a three-neck flask and sodium tert-butoxide (43.8 mmol, 4.21 g) and bis(tri-tert-butylphosphine)palladium(0) (0.292 mmol, 0.149 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 15 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 19.2 g of Compound BD-29-c. (Yield 74%, MS[M+H]+=895)
After Compound BD-29-c (21.4 mmol, 19.2 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 215 ml) in a three-neck flask and boron triiodide (34.3 mmol, 13.4 g) was added thereto, the resulting mixture was stirred in an argon atmosphere at 140° C. for 3 hours. The reaction product was cooled to 0° C., N,N-diisopropylethylamine (193 mmol, 24.9 g) was added thereto, and then the resulting mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography, and then subjected to sublimation purification to obtain 4.5 g of Compound BD-29. (Yield 23%, MS[M+H]+=903)
After 3-bromo-4,4-dimethyl-4H-indeno[1,2-b]thiophene (36.1 mmol, 10 g) and 4-(2-phenylpropan-2-yl)aniline (36.1 mmol, 8 g) were dissolved in toluene (0.2 M, 180 ml) in a three-neck flask and sodium tert-butoxide (54.2 mmol, 5.21 g) and bis (tri-tert-butylphosphine)palladium(0) (0.361 mmol, 0.185 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 4 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 12.5 g of Compound BD-30-a. (Yield 84%, MS[M+H]+=410)
After Compound BD-4-a (29.6 mmol, 12 g) and Compound BD-30-a (29.6 mmol, 12.1 g) were dissolved in toluene (0.2 M, 150 ml) in a three-neck flask and sodium tert-butoxide (44.3 mmol, 4.26 g) and bis(tri-tert-butylphosphine)palladium(0) (0.296 mmol, 0.151 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 24 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 17.3 g of Compound BD-30-b. (Yield 75%, MS[M+H]+=779)
After Compound BD-30-b (22.2 mmol, 17.3 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 220 ml) in a three-neck flask and boron triiodide (35.5 mmol, 13.9 g) was added thereto, the resulting mixture was stirred in an argon atmosphere at 140° C. for 3 hours. The reaction product was cooled to 0° C., N,N-diisopropylethylamine (200 mmol, 25.8 g) was added thereto, and then the resulting mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography, and then subjected to sublimation purification to obtain 3.8 g of Compound BD-30. (Yield 22%, MS[M+H]+=787)
After 3-bromo-5-methylphenol (53.5 mmol, 10 g) and N-(4-tert-butylphenyl)-3-chloroaniline (53.5 mmol, 13.9 g) were dissolved in toluene (0.2 M, 270 ml) in a three-neck flask and sodium tert-butoxide (80.2 mmol, 7.71 g) and bis(tri-tert-butylphosphine)palladium(0) (0.535 mmol, 0.273 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 4 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 17.6 g of Compound BD-31-a. (Yield 90%, MS[M+H]+=366)
After Compound BD-31-a (48.1 mmol, 17.6 g) and potassium carbonate (144 mmol, 20 g) were dissolved in tetrahydrofuran and water (0.1 M, 480 ml) in a three-neck flask and perfluoro-1-butanesulfonyl fluoride (144 mmol, 43.6 g) was added thereto, the resulting mixture was stirred at room temperature for 5 hours. When the reaction was completed, toluene and water were added thereto and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 30.2 g of Compound BD-31-b. (Yield 97%, MS[M+H]+=648)
After Compound BD-31-b (46.6 mmol, 30.2 g) and N-(5-tert-butyl-[1,1′-biphenyl]-2-yl)-5,5,8,8-tetramethyl-5,6,7,8-tetranaphtho[2,3-b]thiophene-3-amine (46.6 mmol, 21.8 g) were dissolved in toluene (0.2 M, 233 ml) in a three-neck flask and sodium tert-butoxide (69.9 mmol, 6.72 g) and bis (tri-tert-butylphosphine)palladium(0) (0.466 mmol, 0.238 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 24 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 27.4 g of Compound BD-31-c. (Yield 72%, MS[M+H]+=816)
After Compound BD-31-c (33.6 mmol, 27.4 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 335 ml) in a three-neck flask and boron triiodide (53.8 mmol, 21.0 g) was added thereto, the resulting mixture was stirred in an argon atmosphere at 140° C. for 8 hours. The reaction product was cooled to 0° C., N,N-diisopropylethylamine (302 mmol, 39.1 g) was added thereto, and then the resulting mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography, and then subjected to sublimation purification to obtain 5.3 g of Compound BD-31-d. (Yield 19%, MS[M+H]+=824)
After Compound BD-31-d (6.44 mmol, 5.3 g) and bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)amine (7.72 mmol, 3 g) were dissolved in toluene (0.2 M, 39 ml) in a three-neck flask and sodium tert-butoxide (9.66 mmol, 0.928 g) and bis (tri-tert-butylphosphine)palladium(0) (0.064 mmol, 0.033 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 6 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography, and then subjected to sublimation purification to obtain 4.1 g of Compound BD-31. (Yield 54%, MS[M+H]+=1177)
After 3-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphtho[2,3-b]thiophene (155 mmol, 50 g) and 5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-amine (155 mmol, 31.4 g) were dissolved in toluene (0.2 M, 775 ml) in a three-neck flask and sodium tert-butoxide (232 mmol, 22.3 g) and bis(tri-tert-butylphosphine)palladium(0) (1.55 mmol, 0.79 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 4 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 47.6 g of Compound BD-32-a. (Yield 69%, MS[M+H]+=446)
After Compound BD-25-a (35.7 mmol, 17 g) and Compound BD-32-a (35.7 mmol, 15.9 g) were dissolved in toluene (0.2 M, 180 ml) in a three-neck flask and sodium tert-butoxide (53.6 mmol, 5.15 g) and bis(tri-tert-butylphosphine)palladium(0) (0.357 mmol, 0.182 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 13 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 22.1 g of Compound BD-32-b. (Yield 70%, MS[M+H]+=886)
After Compound BD-32-b (25.0 mmol, 22.1 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 250 ml) in a three-neck flask and boron triiodide (39.9 mmol, 15.6 g) was added thereto, the resulting mixture was stirred in an argon atmosphere at 140° C. for 8 hours. The reaction product was cooled to 0° C., N,N-diisopropylethylamine (225 mmol, 29 g) was added thereto, and then the resulting mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography, and then subjected to sublimation purification to obtain 2.9 g of Compound BD-32. (Yield 13%, MS[M+H]+=893)
After 3-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphtho[2,3-b]thiophene (46.4 mmol, 15 g) and dibenzo[b,d]furan-1-amine (46.4 mmol, 8.5 g) were dissolved in toluene (0.2 M, 230 ml) in a three-neck flask and sodium tert-butoxide (69.6 mmol, 6.69 g) and bis(tri-tert-butylphosphine)palladium(0) (0.464 mmol, 0.237 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 10 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 17.4 g of Compound BD-33-a. (Yield 88%, MS[M+H]+=426)
After Compound BD-24-a (36.1 mmol, 17 g) and Compound BD-33-a (36.1 mmol, 15.4 g) were dissolved in toluene (0.2 M, 180 ml) in a three-neck flask and sodium tert-butoxide (54.2 mmol, 5.2 g) and bis(tri-tert-butylphosphine)palladium(0) (0.361 mmol, 0.185 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 9 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 24.6 g of Compound BD-33-b. (Yield 84%, MS[M+H]+=816)
After Compound BD-33-b (30.2 mmol, 24.6 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 300 ml) in a three-neck flask and boron triiodide (48.3 mmol, 18.9 g) was added thereto, the resulting mixture was stirred in an argon atmosphere at 140° C. for 6 hours. The reaction product was cooled to 0° C., N,N-diisopropylethylamine (271 mmol, 35 g) was added thereto, and then the resulting mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 5.2 g of Compound BD-33-c. (Yield 21%, MS[M+H]+=823)
After Compound BD-33-c (6.32 mmol, 5.2 g) and diphenylamine (7.58 mmol, 1.3 g) were dissolved in toluene (0.2 M, 38 ml) in a three-neck flask and sodium tert-butoxide (9.47 mmol, 0.91 g) and bis(tri-tert-butylphosphine)palladium(0) (0.06 mmol, 0.032 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 12 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography, and then subjected to sublimation purification to obtain 3.3 g of Compound BD-33. (Yield 55%, MS[M+H]+=956)
After 9,9-dimethyl-9H-fluoren-4-amine (92.8 mmol, 30 g) and 3-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphtho[2,3-b]thiophene (92.8 mmol, 19.4 g) were dissolved in toluene (0.2 M, 465 ml) in a three-neck flask and sodium tert-butoxide (139 mmol, 13.4 g) and bis(tri-tert-butylphosphine)palladium(0) (0.928 mmol, 0.474 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 4 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 37.4 g of Compound BD-34-a. (Yield 89%, MS[M+H]+=452)
After 1-bromo-3-chloro-5-methylbenzene (29.2 mmol, 6 g) and 5,5,8,8-tetramethyl-3-phenyl-N-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-5,6,7,8-tetrahydronaphthalen-2-amine (29.2 mmol, 13.6 g) were dissolved in toluene (0.2 M, 150 ml) in a three-neck flask and sodium tert-butoxide (30.5 mmol, 2.93 g) and bis(tri-tert-butylphosphine)palladium(0) (0.292 mmol, 0.15 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 24 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 12.3 g of Compound BD-34-b. (Yield 71%, MS[M+H]+=590)
After Compound BD-34-a (20.3 mmol, 9.18 g) and Compound BD-34-b (20.3 mmol, 12 g) were dissolved in toluene (0.2 M, 100 ml) in a three-neck flask and sodium tert-butoxide (30.5 mmol, 2.93 g) and bis(tri-tert-butylphosphine)palladium(0) (0.2 mmol, 0.1 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 24 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 14.2 g of Compound BD-34-c. (Yield 69%, MS[M+H]+=1006)
After Compound BD-34-c (14.1 mmol, 14.2 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 140 ml) in a three-neck flask and boron triiodide (22.6 mmol, 8.85 g) was added thereto, the resulting mixture was stirred in an argon atmosphere at 140° C. for 10 hours. The reaction product was cooled to 0° C., N,N-diisopropylethylamine (127 mmol, 16.5 g) was added thereto, and then the resulting mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography, and then subjected to sublimation purification to obtain 2.6 g of Compound BD-34. (Yield 18%, MS[M+H]+=1013)
After N-(4-tert-butylphenyl)-7,7,10,10-tetramethyl-7,8,9,10-tetrahydronaphtho[2,3-b]benzofuran (35.2 mmol, 15 g) and 1-bromo-3-chloro-5-tert-butylbenzene (35.2 mmol, 8.7 g) were dissolved in toluene (0.2 M, 175 ml) in a three-neck flask and sodium tert-butoxide (52.9 mmol, 5.08 g) and bis(tri-tert-butylphosphine)palladium(0) (0.352 mmol, 0.18 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 6 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 18.2 g of Compound BD-35-a. (Yield 87%, MS[M+H]+=592)
After Compound BD-35-a (30.7 mmol, 18.2 g) and N-(4-tert-butylphenyl)-5-(2-phenylpropan-2-yl)benzo[b]thiophen-3-amine (41.6 mmol, 19.6 g) were dissolved in toluene (0.2 M, 155 ml) in a three-neck flask and sodium tert-butoxide (46.1 mmol, 4.43 g) and bis(tri-tert-butylphosphine)palladium(0) (0.307 mmol, 0.157 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 24 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 21.5 g of Compound BD-35-b. (Yield 73%, MS[M+H]+=955)
After Compound BD-35-b (22.5 mmol, 21.5 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 225 ml) in a three-neck flask and boron triiodide (36 mmol, 14.1 g) was added thereto, the resulting mixture was stirred in an argon atmosphere at 140° C. for 3 hours. The reaction product was cooled to 0° C., N,N-diisopropylethylamine (203 mmol, 26.2 g) was added thereto, and then the resulting mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography, and then subjected to sublimation purification to obtain 3.8 g of Compound BD-35. (Yield 18%, MS[M+H]+=963)
After 6-tert-butyl-9-phenyl-N-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-9H-carbazol-3-amine (39.9 mmol, 20 g) and 1-bromo-3-chloro-5-methylbenzene (39.9 mmol, 8.21 g) were dissolved in toluene (0.2 M, 200 ml) in a three-neck flask and sodium tert-butoxide (60 mmol, 5.76 g) and bis(tri-tert-butylphosphine)palladium(0) (0.4 mmol, 0.204 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 5 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 20.9 g of Compound BD-36-a. (Yield 84%, MS[M+H]+=625)
After Compound BD-36-a (33.4 mmol, 20.9 g) and 6-tert-butyl-N-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)benzo[b]thiophen-2-amine (33.4 mmol, 13.1 g) were dissolved in toluene (0.2 M, 170 ml) in a three-neck flask and sodium tert-butoxide (50.1 mmol, 4.82 g) and bis(tri-tert-butylphosphine)palladium(0) (0.334 mmol, 0.171 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 24 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 25.2 g of Compound BD-36-b. (Yield 77%, MS[M+H]+=980)
After Compound BD-36-b (25.7 mmol, 25.2 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 260 ml) in a three-neck flask and boron triiodide (41.1 mmol, 16.1 g) was added thereto, the resulting mixture was stirred in an argon atmosphere at 140° C. for 3 hours. The reaction product was cooled to 0° C., N,N-diisopropylethylamine (231 mmol, 30 g) was added thereto, and then the resulting mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography, and then subjected to sublimation purification to obtain 4.1 g of Compound BD-36. (Yield 16%, MS[M+H]+=988)
After bis-(4-tert-butylphenyl)-amine (107 mmol, 30 g) and 1-bromo-3-chloro-5-(methyl-d-3)benzene (107 mmol, 22.2 g) were dissolved in toluene (0.2 M, 535 ml) in a three-neck flask and sodium tert-butoxide (160 mmol, 15.4 g) and bis(tri-tert-butylphosphine)palladium(0) (1.07 mmol, 0.545 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 4 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 36.2 g of Compound BD-37-a. (Yield 83%, MS[M+H]+=409)
After 7-bromo-3,3-dimethyl-2,3-dihydrothieno[2,3-f]benzofuran (53.0 mmol, 15 g) and 4-tert-butylaniline (53.0 mmol, 7.9 g) were dissolved in toluene (0.2 M, 265 ml) in a three-neck flask and sodium tert-butoxide (79.5 mmol, 7.64 g) and bis(tri-tert-butylphosphine)palladium(0) (0.530 mmol, 0.271 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 18 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 12.7 g of Compound BD-37-b. (Yield 68%, MS[M+H]+=352)
After Compound BD-37-a (34.2 mmol, 14 g) and Compound BD-37-b (34.2 mmol, 12 g) were dissolved in toluene (0.2 M, 170 ml) in a three-neck flask and sodium tert-butoxide (51.3 mmol, 4.93 g) and bis(tri-tert-butylphosphine)palladium(0) (0.342 mmol, 0.175 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 24 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 20.3 g of Compound BD-37-c. (Yield 82%, MS[M+H]+=724)
After Compound BD-37-c (28.0 mmol, 20.3 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 280 ml) in a three-neck flask and boron triiodide (44.9 mmol, 17.6 g) was added thereto, the resulting mixture was stirred in an argon atmosphere at 140° C. for 3 hours. The reaction product was cooled to 0° C., N,N-diisopropylethylamine (252 mmol, 32.6 g) was added thereto, and then the resulting mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography, and then subjected to sublimation purification to obtain 4.1 g of Compound BD-37. (Yield 20%, MS[M+H]+=732)
After N1,N1-bis (phenyl-d5)—N3-(4-trimethylsilylphenyl)benzene-1,3-diamine (47.8 mmol, 20 g) and 1-bromo-3-chloro-5-methylbenzene (47.8 mmol, 9.82 g) were dissolved in toluene (0.2 M, 240 ml) in a three-neck flask and sodium tert-butoxide (71.7 mmol, 6.89 g) and bis(tri-tert-butylphosphine)palladium(0) (0.478 mmol, 0.244 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 2 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 24.5 g of Compound BD-38-a. (Yield 94%, MS[M+H]+=543)
After 3-bromo-4,4,7,7-tetramethyl-4,5,6,7-tetrahydrofuran (38.9 mmol, 10 g) and 4-tert-butylaniline (38.9 mmol, 5.80 g) were dissolved in toluene (0.2 M, 195 ml) in a three-neck flask and sodium tert-butoxide (58.3 mmol, 5.60 g) and bis(tri-tert-butylphosphine)palladium(0) (0.389 mmol, 0.200 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 4 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 11.2 g of Compound BD-38-b. (Yield 88%, MS[M+H]+=331)
After Compound BD-38-a (33.1 mmol, 18 g) and Compound BD-38-b (33.1 mmol, 10.8 g) were dissolved in toluene (0.2 M, 165 ml) in a three-neck flask and sodium tert-butoxide (49.7 mmol, 4.78 g) and bis(tri-tert-butylphosphine)palladium(0) (0.331 mmol, 0.169 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 24 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 21.2 g of Compound BD-38-c. (Yield 77%, MS[M+H]+=832)
After Compound BD-38-c (25.5 mmol, 21.2 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 255 ml) in a three-neck flask and boron triiodide (40.8 mmol, 16.0 g) was added thereto, the resulting mixture was stirred in an argon atmosphere at 140° C. for 3 hours. The reaction product was cooled to 0° C., N,N-diisopropylethylamine (229 mmol, 29.6 g) was added thereto, and then the resulting mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography, and then subjected to sublimation purification to obtain 2.9 g of Compound BD-38. (Yield 14%, MS[M+H]+=840)
After bis-(4-tert-butylphenyl)-amine (142 mmol, 40 g) and (3r,5r,7r)-1-(3-bromo-5-chlorophenyl)adamantane (142 mmol, 46.3 g) were dissolved in toluene (0.2 M, 710 ml) in a three-neck flask and sodium tert-butoxide (213 mmol, 20.5 g) and bis (tri-tert-butylphosphine)palladium(0) (1.42 mmol, 0.726 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 3 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 63.8 g of Compound BD-39-a. (Yield 85%, MS[M+H]+=526)
After 3-bromo-4,4,7,7-tetramethyl-4,5,6,7-tetrahydrobenzo[b]thiophene (54.9 mmol, 15 g) and 3,5-bis(trifluoromethyl)aniline (54.9 mmol, 12.6 g) were dissolved in toluene (0.2 M, 275 ml) in a three-neck flask and sodium tert-butoxide (82.3 mmol, 7.91 g) and bis(tri-tert-butylphosphine)palladium(0) (0.549 mmol, 0.281 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 18 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 16.7 g of Compound BD-39-b. (Yield 72%, MS[M+H]+=421)
After Compound BD-39-a (38.0 mmol, 20 g) and Compound BD-39-b (38.0 mmol, 16 g) were dissolved in toluene (0.2 M, 190 ml) in a three-neck flask and sodium tert-butoxide (57.0 mmol, 5.48 g) and bis(tri-tert-butylphosphine)palladium(0) (0.380 mmol, 0.194 g) were added thereto, the resulting mixture was stirred under reflux conditions in an argon atmosphere for 12 hours. When the reaction was completed, the flask was cooled to room temperature, H2O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography to obtain 22.7 g of Compound BD-39-c. (Yield 66%, MS[M+H]+=911)
After Compound BD-39-c (24.9 mmol, 22.7 g) was dissolved in 1,2-dichlorobenzene (0.1 M, 250 ml) in a three-neck flask and boron triiodide (39.9 mmol, 15.6 g) was added thereto, the resulting mixture was stirred in an argon atmosphere at 140° C. for 3 hours. The reaction product was cooled to 0° C., N,N-diisopropylethylamine (224 mmol, 29.0 g) was added thereto, and then the resulting mixture was stirred for 1 hour. Extraction was performed in a separatory funnel using toluene and H2O. The extract was dried over MgSO4 and concentrated, and the sample was purified with silica gel column chromatography, and then subjected to sublimation purification to obtain 3.9 g of Compound BD-39. (Yield 17%, MS[M+H]+=919)
18.2 g of Compound BD-40-a was obtained from compounds 3-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphtho[2,3-b]thiophene and 5-(tert-butyl)-[1,1′-biphenyl]-2′,3,3′,4,4′,5′,6,6′-d8-2-amine in the same manner as in
18.4 g of BD-40-b was obtained from BD-4-a and BD-40-a in the same manner as in Synthesis Example <60-a>. (Yield 59%, MS[M+H]+=845)
3.2 g of BD-40 was obtained from BD-40-b in the same manner as in Synthesis Example <60-c>. (Yield 59%, MS[M+H]+=853)
18.5 g of BD-41-a was obtained from 2-bromo-3-chloro-5-methylbenzene and N-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)dibenzo[b,d]furan-1-amine in the same manner as in Synthesis Example <60-a>. (Yield 77%, MS[M+H]+=494)
9.9 g of Compound BD-41-b was obtained from compounds BD-41-a (9 g. 1 eq.) and N-(4-(tert-butyl)phenyl)-5,5,8,8-tetramethyl-5,6,7,8-tetrahydrohaphtho [2,3-b] thiophen-3-amine (7.1 g. 1 eq.) in the same manner as in Synthesis Example <60-a>. (Yield 64%, MS[M+H]+=849)
3.5 g of BD-41 was obtained from BD-41-b in the same manner as in Synthesis Example <60-c>. (Yield 35%, MS[M+H]+=857)
18.0 g of Compound BD-42-a was obtained from 2-bromo-3-chloro-5-methylbenzene and N1-(4-(tert-butyl)phenyl)-N3,N3-bis (4-isopropylphenyl)benzene-1,3-diamine in the same manner as in Synthesis Example <60-a>. (Yield 77%, MS[M+H]+=601)
BD-42-b was obtained from BD-42-a and BD-32-a in the same manner as in Synthesis Example <60-a>. (Yield 71%, MS[M+H]+=1010)
3.2 g of Compound BD-42 was obtained from BD-42-b in the same manner as in Synthesis Example <60-c>. (Yield 22%, MS[M+H]+=1017)
16.3 g of Compound BD-43-a was obtained from 2-bromo-3-chloro-5-methylbenzene and N-(3,5-di-tert-butylphenyl)-2′,4′,6′-trimethyl-[1,1′-biphenyl]-3-amine in the same manner as in Synthesis Example <60-a>. (Yield 73%, MS[M+H]+=524)
Compounds BD-43-a (14 g, 26.7 mmol, 1 eq.), 5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthale-2-amine (5.7 g, 28.0 mmol, 1.05 eq), Pd(Pt-Bu3)2 (0.14 g, 0.01 eq.), and NaOt-Bu (3.85 g, 1.5 eq.) were dissolved in toluene (90 ml) and stirred while being refluxed. When the reaction was completed, the reaction product was transferred to a separatory funnel after being cooled to room temperature, and then extracted. The extract was dried over MgSO4, filtered, and concentrated, and the following reaction was performed without an additional purification process. 3-bromo-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphtho[2,3-b]furan (12.3 g, 40.1 mmol, 1.5 eq.), Pd(Pt-Bu3)2 (0.14 g, 0.01 eq.), and NaOt-Bu(3.85 g, 1.5 eq) were together put into a flask, dissolved in toluene (90 ml), and stirred while being refluxed. When the reaction was completed, the reaction product was transferred to a separatory funnel after being cooled to room temperature, and then extracted. The extract was dried over MgSO4, filtered, concentrated, and purified with column chromatography to obtain Compound BD-43-b (12.8 g, 52%). (MS[M+H]+=918)
2.8 g of Compound BD-43 was obtained from BD-43-b (11 g, 1 eq.) in the same manner as in Synthesis Example <60-c>. (Yield 25%, MS[M+H]+=926)
17.8 g of Compound BD-44-a was obtained from 2-bromo-3-chloro-5-methylbenzene and N-(5′-(tert-butyl)-[1,1′:3′,1″-terphenyl]-2′-yl)-5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-amine in the same manner as in
2.8 g of Compound BD-44 was obtained from BD-44-a in the same manner as in Synthesis Example 102-(Step 2). (Yield 9%, MS[M+H]+=980)
13.2 g of Compound BD-45-a was obtained from 2-bromo-3-chloro-5-methylbenzene and N1-(4-(tert-butyl) phenyl)-N3, N3-di-p-tolylbenzene-1,3-diamine in the same manner as in Synthesis Example <60-a>. (Yield 82%, MS[M+H]+=545)
2.7 g of Compound BD-45 was obtained from BD-45-a in the same manner as in Synthesis Example 102-(Step 2). (Yield 15%, MS[M+H]+=893)
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 first and second hole injection layers. The following HT-A was vacuum deposited to have a thickness of 600 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 BD-6 as a blue light emitting dopant was vacuum deposited at 4 wt % based on a total weight of the light emitting layer and the following BH-1 as a host was vacuum deposited at 96 wt % based on a total weight of the light emitting layer 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 360 Å. 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 negative electrode.
In the aforementioned procedure, the deposition rates of the organic material were maintained at 0.4 to 0.9 Å/sec, the deposition rate of aluminum of the negative electrode was maintained at 2 Å/sec, and the degree of vacuum during the deposition was maintained at 1×10−7 to 1×10−8 torr, thereby manufacturing an organic light emitting device.
Organic light emitting devices of Examples 2 to 96 and Comparative Examples 1 to 3 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 respectively as dopants of the light emitting layer instead of Compound BD-6, and compounds described in the following Table 1 were used respectively as host materials instead of BH-1.
Organic light emitting devices of Comparative Examples 1 to 3 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 respectively as dopants of the light emitting layer instead of Compound BD-6, and compounds described in the following Table 1 were used respectively 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 96 and Comparative Examples 1 to 3 and service lives (T95) 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, LT95 means 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%, and the ratio is shown based on Comparative Example 1.
Organic light emitting devices of Examples 97 to 101 and Comparative Example 4 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 respectively as dopants of the light emitting layer instead of Compound BD-6, and two compounds (the weight ratio of the first host to the second host was 50:50) described in the following Table 2 were used respectively 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 97 to Example 101 and Comparative Example 4 and service lives (T95) 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, LT95 means 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%, and the ratio is shown 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.
Furthermore, it was confirmed that even when a host in which deuterium was partially substituted was used, a device having a long service life was constructed.
Although the preferred exemplary embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications can be made and carried out within the scopes of the claims and the detailed description of the invention, and also fall within the scope of the invention.
| 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 |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2020/017337 | 11/30/2020 | WO |
