Heterocyclic compound and organic electroluminescence device containing heterocyclic compound

Abstract

The present invention relates to a specific heterocyclic compound, a material for an organic electroluminescent device, preferably an emitter material, containing the specific heterocyclic compound, an organic electroluminescent device containing the specific heterocyclic compound, an electronic device including the organic electroluminescent device, an emitting layer containing at least one host and at least one dopant, wherein the dopant contains at least one of the specific heterocyclic compounds, and use of the heterocyclic compound in an organic electroluminescent device. JPEG2023531421000254.jpg5652

Description

Technical Field

[0001] The present invention relates to a specific heterocyclic compound, a material for an organic electroluminescence device containing the specific heterocyclic compound, preferably a light-emitting material, an organic electroluminescence device containing the specific heterocyclic compound, an electronic device including the organic electroluminescence device, a light-emitting layer containing at least one host and at least one dopant, and the use of the heterocyclic compound in an organic electroluminescence device, wherein the dopant contains at least one of the specific heterocyclic compounds.

Background Art

[0002] When a voltage is applied to an organic electroluminescence device (hereinafter sometimes referred to as an organic EL device), holes are injected from the anode into the light-emitting layer, and electrons are injected from the cathode into the light-emitting layer. In the light-emitting layer, the injected holes and electrons are recombined to form excitons.

[0003] The organic EL device includes a light-emitting layer between an anode and a cathode. Further, it may have a laminated structure including organic layers such as a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer.

[0004] Patent Document 1 relates to a boron-containing heterocyclic compound for an organic electronic device such as an organic light-emitting device having a structure of the following formula I.

Chemical Formula

[0005] In the formula, ring A, ring B, ring C, and ring D are each independently a 5- or 6-membered aryl ring or heteroaryl ring, R 1 、R 2 、R 3 、and R 4 each independently represent unsubstituted or up to the maximum possible substitution, Y is NR, O, PR, S, or Se, Z is N or P.

[0006] An example of the compound of formula I is the following compound.

Chemical formula

[0007] However, the specific structure and substitution pattern of the polycyclic compound greatly affect the performance of the polycyclic compound in the organic electronic device.

[0008] Despite the above developments, there is still a need for new materials, particularly organic electroluminescent devices including dopant (= emitter) materials, to provide improved performance of electroluminescent devices.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0010] Accordingly, an object of the present invention is to provide a material suitable for providing an organic electroluminescent device having excellent performance, particularly excellent EQE and / or long life, with respect to the related art described above. More specifically, it is possible to provide a blue light-emitting dopant material having a narrow spectrum (smaller FWHM), that is, good color purity, when used as a dopant in an organic electroluminescent device.

Means for Solving the Problems

[0011] According to one aspect of the present invention, the above problem is solved by a heterocyclic compound represented by formula (I).

Chemical formula

[0012] In the formula, ring A 1 , ring B 1 , ring C 1 , and ring D 1 each independently represents a substituted or unsubstituted aromatic group having 6 to 60 ring-forming carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring-forming atoms, ring C 1 and ring D 1 may be linked via a direct bond, O, S, NR 23 , SiR 24 R 25 , or CR 27 R 28 , R E represents hydrogen, an unsubstituted or substituted aryl group having 6 to 60 ring-forming carbon atoms, an unsubstituted or substituted heteroaryl group having 5 to 60 ring-forming atoms, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, an unsubstituted or substituted alkenyl group having 2 to 20 carbon atoms, an iminyl group R 23 -C=N, or an unsubstituted or substituted alkynyl group having 2 to 20 carbon atoms, R E or R E The substituents on 1 the above ring A 1 and / or the above ring B 1 may be bonded to the above ring A 1 and / or the above ring B 23 and form an unsubstituted or substituted ring structure, Y represents a direct bond, O, S, NR 24 , SiR 25 , or CR 27 R 28 , When Y is a direct bond, ring B 1 and ring C1 is further connected via O, S, NR 23 , SiR 24 R 25 , or CR 27 R 28 and may be connected, R 23 R 24 R 25 R 27 , and R 28 each independently represents an unsubstituted or substituted aryl group having 6 to 60 ring-forming carbon atoms, an unsubstituted or substituted heteroaryl group having 5 to 60 ring-forming atoms, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, and / or, two residues R 24 and R 25 and / or two residues R 27 and R 28 together form an unsubstituted or substituted ring structure.

Brief Description of the Drawings

[0013]

Figure 1

Embodiments for Carrying Out the Invention

[0014] The compound of formula (I) can in principle be used in any layer of the EL element. Preferably, the compound of formula (I) is a dopant (= emitter) in an organic EL element, particularly in the light-emitting layer, more preferably a fluorescent dopant. In particular, the compound of formula (I) is used as a fluorescent dopant in an organic EL element, particularly in the light-emitting layer.

[0015] The term organic EL element (organic electroluminescence element) is used interchangeably with the term organic light-emitting diode (OLED) in this application.

[0016] Certain compounds of formula (I) have been found to exhibit narrow emission characteristics, preferably narrow fluorescence, more preferably narrow blue fluorescence. Such narrow emission characteristics are suitable for preventing energy loss due to outcoupling. The compounds of formula (I) according to the present invention preferably have a full width at half maximum (FWHM) of less than 30 nm, more preferably less than 25 nm.

[0017] Furthermore, organic EL elements containing the compounds of the present invention generally feature high external quantum efficiency (EQE) and long lifespan, especially when certain compounds of formula (I) are used as dopants (luminescent materials), particularly fluorescent dopants, in organic electroluminescence elements.

[0018] Examples of any substituent(s) indicated by "substituted or unsubstituted" and "optionally substituted" mentioned above or below include unsubstituted or substituted aryl groups having 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring-forming carbon atoms, unsubstituted or substituted heteroaryl groups having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring-forming atoms, alkyl groups having 1 to 20, preferably 1 to 8 carbon atoms, cycloalkyl groups having 3 to 20, preferably 3 to 6 carbon atoms, OR 20 groups, halogenated alkyl groups having 1 to 20, preferably 1 to 8 carbon atoms, N(R 22 ) 2 groups, halogen atoms (fluorine, chlorine, bromine, iodine), cyano groups, carboxyalkyl groups having 1 to 20, preferably 1 to 8 carbon atoms, carboxamidealkyl groups having 1 to 20, preferably 1 to 8 carbon atoms, silyl groups SiR 24 R 25 R 26 , B(R 21 ) 2 , SR 20 groups, carboxyaryl groups having 6 to 18 ring-forming carbon atoms of an aryl residue, and carboxamidearyl groups having 6 to 18 ring-forming carbon atoms of an aryl residue, or, two adjacent substituents together form an unsubstituted or substituted ring structure, R 20 , R 21, and R 22 is each independently an unsubstituted or substituted aryl group having 6 to 60 ring-forming carbon atoms, preferably 6 to 30, more preferably 6 to 18, an unsubstituted or substituted heteroaryl group having 5 to 60 ring-forming atoms, preferably 5 to 30, more preferably 5 to 18 and bonded to N, O, S, or B via a carbon atom, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, and / or, two residues R 22 and / or two residues R 21 together form an unsubstituted or substituted ring structure, or, R 20 R 21 and / or R 22 form an unsubstituted or substituted ring structure together with adjacent substituents.

[0019] R 26 is an unsubstituted or substituted aryl group having 6 to 60 ring-forming carbon atoms, preferably 6 to 30, more preferably 6 to 18, an unsubstituted or substituted heteroaryl group having 5 to 60 ring-forming atoms, preferably 5 to 30, more preferably 5 to 18 and bonded to N or Si via a carbon atom, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, R 24 and R 25 are as defined above.

[0020] Hydrogen, halogen, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted halogenated alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, a substituted or unsubstituted aromatic group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring-forming carbon atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring-forming atoms, a carboxyalkyl group having 1 to 20, preferably 1 to 8 carbon atoms, a carboxamidealkyl group having 1 to 20, preferably 1 to 8 carbon atoms, a carboxyaryl group having 6 to 18 ring-forming atoms of an aryl residue, a carboxamidearyl group having 6 to 18 ring-forming atoms of an aryl residue, N(R 22 ) 2 , OR 20 , SR 20 , SR 20 , SiR 24 R 25 R 26 , and B(R 21 ) 2 are known in the art and generally have the following meanings unless the above groups are further specified in the specific embodiments described below.

[0021] In the present invention, hydrogen includes isomers having different numbers of neutrons, namely protium, deuterium, and tritium.

[0022] The substituted or unsubstituted aromatic group having 6 to 60, preferably 6 to 30, more preferably 6 to 18, and most preferably 6 to 13 carbon atoms forming the ring (also referred to as an aryl group) may be a non-condensed aromatic group or a condensed aromatic group. Specific examples thereof include a phenyl group, a naphthyl group, a phenanthryl group, a biphenyl group, a terphenyl group, a fluoranthenyl group, a triphenylenyl group, a phenanthrenyl group, a fluorenyl group, an indenyl group, an anthracenyl, a chrysenyl, a spirofluorenyl group, and a benzo[c]phenanthrenyl group. Among them, a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, a triphenylenyl group, a fluorenyl group, an indenyl group, and a fluoranthenyl group are preferable, and a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a biphenyl-2-yl group, a biphenyl-3-yl group, a biphenyl-4-yl group, a phenanthren-9-yl group, a phenanthren-3-yl group, a phenanthren-2-yl group, a triphenylene-2-yl group, a fluorene-2-yl group, particularly a 9,9-dimethylfluorene-2-yl group such as a 9,9-di-C 1~20 alkylfluorene-2-yl group, a 9,9-diphenylfluorene-2-yl group such as a 9,9-di-C 6~18 arylfluorene-2-yl group, or a 9,9-di-C 5~18 heteroarylfluorene-2-yl group, a 1,1-dimethylindenyl group, a fluoranthene-3-yl group, a fluoranthene-2-yl group, and a fluoranthene-8-yl group are more preferable, and a phenyl group is most preferable.

[0023] Ring A 1 , Ring B 1 , Ring C 1 and Ring D 1 The preferable aromatic groups having 6 to 60, preferably 6 to 30, more preferably 6 to 18 carbon atoms forming the ring in are listed below.

[0024] The substituted or unsubstituted heteroaromatic group having 5 to 60 ring-forming atoms, preferably 5 to 30, more preferably 5 to 18, and most preferably 5 to 13 (also referred to as a heteroaryl group) may be a non-condensed heteroaromatic group or a condensed heteroaromatic group. Specific examples thereof include residues such as pyrrole ring, isoindole ring, benzofuran ring, isobenzofuran ring, benzothiophene ring, dibenzothiophene ring, isoquinoline ring, quinoxaline ring, quinazoline ring, phenanthridine ring, phenanthroline ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indole ring, quinoline ring, acridine ring, carbazole ring, furan ring, thiophene ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, dibenzofuran ring, triazine ring, oxazole ring, oxadiazole ring, thiazole ring, thiadiazole ring, triazole ring, imidazole ring, indolizine ring, imidazopyridine ring, 4-imidazo[1,2-a]benzimidazolyl, 5-benzimidazo[1,2-a]benzimidazolyl, and benzimidazolo[2,1-b][1,3]benzothiazolyl. Residues such as indole ring, benzothiophene ring, dibenzofuran ring, carbazole ring, and dibenzothiophene ring are preferred, and residues such as benzofuran ring, 1-phenylindole ring, benzothiophene ring, dibenzofuran-1-yl group, dibenzofuran-3-yl group, dibenzofuran-2-yl group, dibenzofuran-4-yl group, 9-phenylcarbazole-3-yl group, 9-phenylcarbazole-2-yl group, 9-phenylcarbazole-4-yl group, dibenzothiophene-2-yl group, and dibenzothiophene-4-yl group, dibenzothiophene-1-yl group, and dibenzothiophene-3-yl group are more preferred.

[0025] Ring A 1 、 Ring B 1 、 Ring C 1 、 and Ring D 1 The preferred heteroaromatic groups having 5 to 60 ring-forming atoms, preferably 5 to 30, more preferably 5 to 18, which may be substituted or unsubstituted, in are listed below.

[0026] Examples of unsubstituted or substituted alkyl groups having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, neopentyl group, 1-methylpentyl group, and among them, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group are preferred. An alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms is preferred. An alkyl group having preferably 1 to 8, more preferably 1 to 4 carbon atoms is preferred. Examples of suitable alkyl groups having 1 to 8 and 1 to 4 carbon atoms are as described above.

[0027] Examples of unsubstituted or substituted alkyl halide groups having 1 to 20 carbon atoms include groups in which the hydrogen atoms of the groups disclosed as alkyl groups are partially or completely substituted by halogen atoms. Preferred alkyl halide groups are groups in which the hydrogen atoms of the above-described alkyl groups having 1 to 20 carbon atoms are partially or completely substituted by fluorine atoms, for example, CF 3 is.

[0028] Examples of unsubstituted or substituted cycloalkyl groups having 3 to 20 ring-forming carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, and adamantyl group, and cyclopentyl group and cyclohexyl group are preferred. Preferably, it is a cycloalkyl group having 3 to 6 carbon atoms. Examples of suitable cycloalkyl groups having 3 to 6 carbon atoms are as described above.

[0029] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, and fluorine is preferred.

[0030] OR 20 group is preferably C 1~20An alkoxy group or a C 6~18 is an aryloxy group. Examples of the alkoxy group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, include those having an alkyl moiety selected from the above-described alkyl groups. Examples of the aryloxy group having 6 to 18 ring-forming carbon atoms include those having an aryl moiety selected from the above-described aryl groups, such as -OPh.

[0031] SR 20 group is preferably a C 1~20 alkylthio group or a C 6~18 is an arylthio group. Examples of the alkylthio group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, include those having an alkyl moiety selected from the above-described alkyl groups. Examples of the arylthio group having 6 to 18 ring-forming carbon atoms include those having an aryl moiety selected from the above-described aryl groups, such as -SPh.

[0032] N(R 22 ) 2 group is preferably a C 1~20 alkyl and / or C 6~18 is an amino group substituted with an aryl and / or (a heteroaryl having 5 to 18 ring-forming atoms). Examples of the alkylamino group (alkyl-substituted amino group) having 1 to 20 ring-forming carbon atoms include those having an alkyl moiety selected from the above-described alkyl groups. Examples of the arylamino group (aryl-substituted amino group) having 6 to 18 ring-forming carbon atoms include those having an aryl moiety selected from the above-described aryl groups, such as -NPh 2 is mentioned. Examples of the heteroarylamino group (heteroaryl-substituted amino group), preferably the heteroarylamino group having 5 to 18 ring-forming atoms, include those having an aryl moiety selected from the above-described heteroaryl groups.

[0033] B(R 21 ) 2 group is preferably a C 1~20 alkyl and / or C 6~18It is a boron group substituted with aryl and / or heteroaryl (having 5 to 18 ring-forming atoms). Examples of the alkyl boron group (alkyl-substituted boron group) having 1 to 20 ring-forming carbon atoms include those having an alkyl moiety selected from the above-mentioned alkyl groups. Examples of the aryl boron group (aryl-substituted boron group) having 6 to 18 ring-forming carbon atoms include those having an aryl moiety selected from the above-mentioned aryl groups. Examples of the heteroaryl boron group (heteroaryl-substituted boron group), preferably the heteroaryl boron group having 5 to 18 ring-forming atoms, include those having an aryl moiety selected from the above-mentioned heteroaryl groups.

[0034] SiR 24 R 25 R 26 The group is preferably a C 1~20 alkyl and / or C 6~18 silyl group substituted with aryl. Preferred examples of the silyl group substituted with C 1~20 alkyl and / or C 6~18 aryl include alkylsilyl groups containing 1 to 8, preferably 1 to 4 carbon atoms in each alkyl residue, such as trimethylsilyl group, triethylsilyl group, tributylsilyl group, dimethylethylsilyl group, t-butyldimethylsilyl group, propyldimethylsilyl group, dimethylisopropylsilyl group, dimethylpropylsilyl group, dimethylbutylsilyl group, dimethyltertiarybutylsilyl group, diethylisopropylsilyl group, and arylsilyl groups containing 6 to 18 carbon atoms in each aryl residue, preferably triphenylsilyl group, and alkyl / arylsilyl groups, preferably phenyldimethylsilyl group, diphenylmethylsilyl group, and diphenyltertiarybutylsilyl group. Diphenyltertiarybutylsilyl group and t-butyldimethylsilyl group are preferred.

[0035] Examples of the carboxyalkyl group having 1 to 20, preferably 1 to 8 carbon atoms include those having an alkyl moiety selected from the above-mentioned alkyl groups.

[0036] Examples of fluoroalkyl groups having 1 to 20 carbon atoms include the above alkyl groups in which hydrogen atoms are partially or entirely substituted by fluorine atoms.

[0037] Examples of carboxamidealkyl groups (alkyl-substituted amide groups) having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, include those having an alkyl moiety selected from the above alkyl groups.

[0038] Examples of carboxamidearyl groups (aryl-substituted amide groups) having 6 to 18 carbon atoms, preferably 6 to 13 carbon atoms, include those having an aryl moiety selected from the above aryl groups.

[0039] Any substituent is preferably, each independently, an unsubstituted or substituted aryl group having 6 to 18 ring-forming carbon atoms, an unsubstituted or substituted heteroaryl group having 5 to 18 ring-forming atoms, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, CN, N(R 22 ) 2 , SiR 24 R 25 R 26 , SR 20 , or OR 20 and represents or, two adjacent substituents together form an unsubstituted or substituted ring structure, R 20 and R 22 each independently represent an unsubstituted or substituted aryl group having 6 to 18 ring-forming carbon atoms, an unsubstituted or substituted heteroaryl group having 5 to 18 ring-forming atoms and bonded to N or O or S via a carbon atom, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, or, R 20 and / or R 22 together with an adjacent substituent form an unsubstituted or substituted ring structure, R 24 , R 25 , and R26 represents an unsubstituted or substituted aryl group having 6 to 18 ring-forming carbon atoms, an unsubstituted or substituted heteroaryl group having 5 to 18 ring-forming atoms, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms.

[0040] More preferably, each of the optional substituents is independently an unsubstituted or substituted aryl group having 6 to 18 ring-forming carbon atoms, an unsubstituted or substituted heteroaryl group having 5 to 18 ring-forming atoms, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, CN, or N(R 22 ) 2 represents, or, two adjacent substituents together form an unsubstituted or substituted ring structure, R 22 represents an unsubstituted or substituted aryl group having 6 to 18 ring-forming carbon atoms, or an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or, R 22 forms an unsubstituted or substituted ring structure together with an adjacent substituent.

[0041] Most preferably, each of the optional substituents is independently an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 6 ring-forming carbon atoms, an unsubstituted or substituted aryl group having 6 to 13 ring-forming carbon atoms, an unsubstituted or substituted heteroaryl group having 5 to 13 ring atoms, CN, or N(R 22 ) 2 represents, or, two adjacent substituents together form an unsubstituted or substituted ring structure, R 22 represents an unsubstituted or substituted aryl group having 6 to 18 ring-forming carbon atoms, or an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms.

[0042] Any of the above-mentioned substituents may be further substituted by one or more of the above-mentioned substituents.

[0043] The number of any substituents depends on the group being substituted by the above substituents (including plural ones). The maximum number of possible substituents is defined by the number of hydrogen atoms present. 1, 2, 3, 5, 6, 7, 8, or 9 arbitrary substituents per substituted group are preferred, 1, 2, 3, 5, 5, 6, or 7 arbitrary substituents per substituted group are more preferred, 1, 2, 3, 4, or 5 arbitrary substituents are most preferred, 1, 2, 3, 4, or 5 arbitrary substituents are even most preferred, 1, 2, 3, or 4 arbitrary substituents are even more most preferred, and 1 or 2 arbitrary substituents are even more most preferred. In a further preferred embodiment, some or all of the above groups are unsubstituted.

[0044] In a more preferred embodiment, the total number of substituents in the compound of formula (I) is 0, 1, 2, 3, 4, 5, 6, 7, or 8, preferably 0, 1, 2, 3, 4, 5, or 6, that is, the remaining residues are hydrogen.

[0045] In the expression "substituted or unsubstituted X group having a carbon number of a to b", "carbon number of a to b" is the carbon number of the unsubstituted X group and does not include the carbon atoms (including plural ones) of any substituents.

[0046] The term "unsubstituted" referred to by "unsubstituted or substituted" means that a hydrogen atom is not substituted by the above groups.

[0047] In the definitions in any of the formulas listed above and below, a coefficient of 0 means that a hydrogen atom is present at the position defined by the above coefficient.

[0048] The compound of formula (I) In the heterocyclic compound represented by formula (I),

[0049]

Chemical formula

[0050] Ring A 1 , Ring B 1 , Ring C 1 , and Ring D 1 each independently represents a substituted or unsubstituted aromatic group having 6 to 60 ring-forming carbon atoms, preferably 6 to 30, more preferably 6 to 18, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring-forming atoms, preferably 5 to 30, more preferably 5 to 18, Ring C 1 and Ring D 1 may be linked via a direct bond, O, S, NR 23 , SiR 24 R 25 , or CR 27 R 28 , preferably via a direct bond, R E represents hydrogen, an unsubstituted or substituted aryl group having 6 to 60 ring-forming carbon atoms, preferably 6 to 30, more preferably 6 to 18, an unsubstituted or substituted heteroaryl group having 5 to 60 ring-forming atoms, preferably 5 to 30, more preferably 5 to 18, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, an unsubstituted or substituted alkenyl group having 2 to 20 carbon atoms, an iminyl group R 23 -C=N, or an unsubstituted or substituted alkynyl group having 2 to 20 carbon atoms, R E or R E The substituents on 1 Ring A 1 and / or Ring B 1 may be bonded to Ring A 1 and / or Ring B and form an unsubstituted or substituted ring structure, Y represents a direct bond, O, S, NR 23 , SiR 24 R 25 , or CR 27 R 28 , preferably represents a direct bond, When Y is a direct bond, Ring B 1 and Ring C 1 further may be O, S, NR 23 , SiR24 R 25 、 or CR 27 R 28 may be combined via, R 23 、R 24 、R 25 、R 27 、 and R 28 each independently represents an unsubstituted or substituted aryl group having 6 to 60 ring-forming carbon atoms, preferably 6 to 30, more preferably 6 to 18, an unsubstituted or substituted heteroaryl group having 5 to 60 ring-forming atoms, preferably 5 to 30, more preferably 5 to 18 and bonded to N or Si via a carbon atom, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms. and / or, two residues R 24 and R 25 and / or two residues R 27 and R 28 together form an unsubstituted or substituted ring structure.

[0051] Preferably, ring A 1 、 ring B 1 、 ring C 1 、 and ring D 1 each independently represents a substituted or unsubstituted aromatic group having 6 to 60 ring-forming carbon atoms, preferably 6 to 30, more preferably 6 to 18, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring-forming atoms, preferably 5 to 30, more preferably 5 to 18, represented by the following formula.

[0052] [Chemical formula]

[0053] In the formula, ring C 1 and ring D 1 are a direct bond, O, S, NR 23 、 SiR 24 R 25 、 or CR 27 R 28It may be linked via, preferably directly linked via, The star mark is for ring C 1 and ring D 1 at any preferred position of the bonding site between them, The dotted line is the bonding site.

[0054] More preferably, ring A 1 , ring B 1 , ring C 1 , and ring D 1 are a non-condensed aromatic group or a condensed aromatic group, and specific examples thereof are phenyl, naphthyl, phenanthrene, biphenyl, terphenyl, fluoranthene, triphenylene, fluorene, indene, anthracene, chrysene, spirofluorene, benzo[c]phenanthrene, and phenyl, naphthyl, biphenyl, terphenyl, phenanthrene, triphenylene, fluorene, indene, and fluoranthene are preferred, and phenyl and naphthyl are most preferred, or, a non-condensed heteroaromatic group or a condensed heteroaromatic group, and specific examples thereof are pyrrole, isoindole, benzofuran, isobenzofuran, benzothiophene, dibenzothiophene, isoquinoline, quinoxaline, quinazoline, phenanthridine, phenanthroline, pyridine, pyrazine, pyrimidine, pyridazine, indole, quinoline, acridine, carbazole, furan, thiophene, benzoxazole, benzothiazole, benzimidazole, dibenzofuran, triazine, oxazole, oxadiazole, thiazole, thiadiazole, triazole, imidazole, indolizine, imidazopyridine, 4-imidazo[1,2-a]benzimidazole, 5-benzimidazo[1,2-a]benzimidazole, and benzimidazolo[2,1-b][1,3]benzothiazole, and indole, especially 1-phenylindole, benzothiophene, dibenzofuran, carbazole, dibenzothiophene, benzofuran, and benzothiophene are preferred.

[0055] More preferably, ring A 1 , ring B 1 , ring C1 and ring D 1 is represented by the following formula.

[0056]

Chem.

[0057] In the formula, the dotted line is a binding site, and the residue R 12 , residue R 13 , residue R 14 , and residue R 15 are defined as follows.

[0058]

Chem.

[0059] In the formula, the dotted line is a binding site, and the residue R 4 , residue R 5 , and residue R 6 are defined as follows.

[0060]

Chem.

[0061] In the formula, the dotted line is a binding site, residue R 1 , residue R 2 , and residue R 3 are defined as follows, ring C 1 and ring D 1 are directly bonded, O, S, NR 23 , SiR 24 R 25 , or CR 27 R 28 and may be linked via, preferably directly, and the asterisk indicates the position of any preferred binding site to ring D 1 .

[0062]

Chem.

[0063] In the formula, the dotted line is the binding site and residue R 16 , residue R 17 , residue R 18 , and residue R 19 are defined as follows. Ring C 1 and ring D 1 may be linked directly, via O, S, NR 23 , SiR 24 R 25 , or CR 27 R 28 , preferably via a direct bond, and the asterisk indicates the position of any preferred binding site to ring C 1 . It is represented by .

[0064] Examples of ring structures formed by two adjacent substituents are shown below (the following ring structures may be substituted by one or more of the above substituents).

[0065]

Chemical Structure

[0066] In the formula, X is O, CR a R b , S, or NR c . X’’ and Y’’ are each independently O, CR a R b , S, BR c , or NR c . R a and R b are each independently C 1 ~C 8 alkyl or substituted or unsubstituted C 6 ~C 18 aryl, preferably C 1 ~C 4 alkyl or substituted or unsubstituted C 6 ~C 10 aryl, more preferably methyl or unsubstituted or substituted phenyl. R c is C 1 ~C 8 alkyl, preferably C 1 ~C 4 alkyl, or substituted or unsubstituted C 6 ~C 10 aryl, preferably unsubstituted or substituted phenyl, and E 1 , F 1 , F 2 , G 1 , H 1 , I 1 , I 2 , K 1 , L 1 , M 1 , and N 1 each independently represents a substituted or unsubstituted aromatic group having 6 to 60 ring-forming carbon atoms, preferably 6 to 30, more preferably 6 to 18, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring-forming atoms, preferably 5 to 30, more preferably 5 to 18, and The dotted line represents a bonding site.

[0067] R E or R E When the substituent on forms an unsubstituted or substituted ring structure by bonding to ring A 1 and / or ring B 1 or to the substituent on ring A 1 and / or ring B 1 Examples are as follows.

[0068]

Chemical formula

[0069] In the formula, R E1 , R E2 , R E3 , R E5 , and R E6 each independently represents C 1 ~C 8 alkyl or substituted or unsubstituted C 6 ~C 18 aryl, preferably C1 ~C 4 alkyl or substituted or unsubstituted C 6 ~C 10 represents aryl, more preferably methyl or unsubstituted or substituted phenyl, or, two adjacent residues R E2 and R E3 or R E5 and R E6 together form a substituted or unsubstituted ring structure, X’ is a direct bond, O, S, NR 23 , SiR 24 R 25 , CR 27 R 28 , or BR 21 represents, ring A 1 ring B 1 ring C 1 ring D 1 R 21 R 23 R 24 R 25 R 27 R 28 and Y are defined above and below, R 7 R 8 R 9 R 10 and R 11 are defined below.

[0070] Y is a direct bond, O, S, NR 23 , SiR 24 R 25 , or CR 27 R 28 preferably represents a direct bond, when Y is a direct bond, ring B 1 and ring C 1 may further be bonded via O, S, NR 23 , SiR 24 R 25 , or CR 27 R 28 .

[0071] Y is a direct bond, and ring B1 and ring C 1 further includes O, S, NR 23 , SiR 24 R 25 , or CR 27 R 28 The case of bonding through is shown below.

[0072]

Chemical formula

[0073] Preferably, Y is a direct bond.

[0074] A preferred heterocyclic compound according to the present invention is represented by formula (II).

[0075]

Chemical formula

[0076] In the formula, the residues and coefficients are as described above.

[0077] In a more preferred embodiment, the heterocyclic compound according to the present invention is represented by formula (III).

[0078]

Chemical formula

[0079] In one embodiment, ring A in the heterocyclic compound according to the present invention 1 is a substituted or unsubstituted heteroaromatic group having 5 to 60 ring-forming atoms. Preferred heteroaromatic groups are as described above.

[0080] R E is preferably a group of the following formula (IV).

[0081]

Chemical formula

[0082] In the formula, R 7 , R 8 , R 9 , R 10 , and R 11 are each independently hydrogen, an unsubstituted or substituted aryl group having 6 to 60 ring-forming carbon atoms, preferably 6 to 30, more preferably 6 to 18, an unsubstituted or substituted heteroaryl group having 5 to 60 ring-forming atoms, preferably 5 to 30, more preferably 5 to 18, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted halogenated alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, CN, N(R 22 ) 2 , OR 20 , SR 20 , B(R 21 ) 2 , SiR 24 R 25 R 26 , or halogen, and and / or, two adjacent residues R 7 , R 8 , R 9 , R 10 , and / or R 11 together form an unsubstituted or substituted ring structure, and / or, R 7 and / or R 11 is bonded to ring B 1 and / or ring A 1 , or to a substituent on ring A 1 and / or ring B 1 to form an unsubstituted or substituted ring structure, The dotted line represents the bonding site.

[0083] Most preferably, the heterocyclic compound according to the present invention is represented by formula (V).

[0084]

Chemical formula

[0085] In the formula, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、and R 19 each independently represents hydrogen, an unsubstituted or substituted aryl group having 6 to 60 ring-forming carbon atoms, preferably 6 to 30, more preferably 6 to 18, an unsubstituted or substituted heteroaryl group having 5 to 60 ring-forming atoms, preferably 5 to 30, more preferably 5 to 18, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted halogenated alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, CN, N(R 22 ) 2 、OR 20 、SR 20 、B(R 21 ) 2 、SiR 24 R 25 R 26 、or halogen, or, two adjacent residues R 1 、R 2 、and / or R 3 、and / or two adjacent residues R 4 、R 5 、and / or R 6 、and / or two adjacent residues R 12 、R 13 、R 14 、and / or R 15and / or two adjacent residues R 16 R 17 R 18 and / or R 19 both form an unsubstituted or substituted ring structure, and / or, two adjacent residues R 7 R 8 R 9 R 10 and / or R 11 both form an unsubstituted or substituted ring structure, and / or, R 7 and / or R 11 is R 6 and / or R 12 binds to R R 20 R 21 and R 22 each independently represents an unsubstituted or substituted aryl group having 6 to 60 ring-forming carbon atoms, preferably 6 to 30, more preferably 6 to 18, an unsubstituted or substituted heteroaryl group having 5 to 60 ring-forming atoms, preferably 5 to 30, more preferably 5 to 18, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, and / or, two residues R 22 and / or two residues R 21 both form an unsubstituted or substituted ring structure, or, R 20 R 21 and / or R 22 is the adjacent residue R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 R 15 R 16 R17 , R 18 , or R 19 together form an unsubstituted or substituted ring structure, R 24 , R 25 , and R 26 each independently represents an unsubstituted or substituted aryl group having 6 to 60 ring-forming carbon atoms, preferably 6 to 30, more preferably 6 to 18, an unsubstituted or substituted heteroaryl group having 5 to 60 ring-forming atoms, preferably 5 to 30, more preferably 5 to 18, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms.

[0086] Two adjacent residues R 1 , R 2 , and / or R 3 , and / or two adjacent residues R 4 , R 5 , and / or R 6 , and / or two adjacent residues R 7 , R 8 , R 9 , R 10 , and / or R 11 , and / or two adjacent residues R 12 , R 13 , R 14 , and / or R 15 , and / or two adjacent residues R 16 , R 17 , R 18 , and / or R 19 Examples of the ring structures formed by are shown below (the following ring structures may be substituted by one or more of the above substituents).

[0087]

Chemical formula

[0088] In the formula, X is O, CR a R b , S, or NR c , and R aand R b is, independently of one another, C 1 ~C 8 alkyl or substituted or unsubstituted C 6 ~C 18 aryl, preferably C 1 ~C 4 alkyl or substituted or unsubstituted C 6 ~C 10 aryl, more preferably methyl or unsubstituted or substituted phenyl, and R c is C 1 ~C 8 alkyl, preferably C 1 ~C 4 alkyl, or substituted or unsubstituted C 6 ~C 10 aryl, preferably unsubstituted or substituted phenyl.

[0089] R 7 and / or R 11 is bonded to R 6 and / or R 12 to form an unsubstituted or substituted ring structure, examples of which are as follows.

[0090] [Chemical formula]

[0091] In the formula, X’ represents a direct bond, O, S, NR 23 , SiR 24 R 25 , CR 27 R 28 , or BR 21 and, all other residues are as defined above and below.

[0092] Preferably, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8, R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 are each independently hydrogen, an unsubstituted or substituted aryl group having 6 to 18 ring-forming carbon atoms, an unsubstituted or substituted heteroaryl group having 5 to 18 ring-forming atoms, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, CN, N(R 22 ), 2 , SiR 24 R 25 R 26 , SR 20 , or OR 20 , or, Two adjacent residues R 1 , R 2 , and / or R 3 , and / or two adjacent residues R 4 , R 5 , and / or R 6 , and / or two adjacent residues R 7 , R 8 , R 9 , R 10 , and / or R 11 , and / or two adjacent residues R 12 , R 13 , R 14 , and / or R 15 , and / or two adjacent residues R 16 , R 17 , R 18 , and / or R 19 together form an unsubstituted or substituted ring structure, and / or, R 7 and / or R 11 is, R 6 and / or R 12 are bonded to form an unsubstituted or substituted ring structure, R 22 and R 22each independently represents an unsubstituted or substituted aryl group having 6 to 18 ring-forming carbon atoms, an unsubstituted or substituted heteroaryl group having 5 to 18 ring-forming atoms, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, or, R 20 and / or R 22 together with adjacent residues R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、or R 19 form an unsubstituted or substituted ring structure, R 24 、R 25 、and R 26 each represents an unsubstituted or substituted aryl group having 6 to 18 ring-forming carbon atoms, an unsubstituted or substituted heteroaryl group having 5 to 18 ring-forming atoms, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms.

[0093] More preferably, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、and R19 is, independently of one another, hydrogen, an unsubstituted or substituted aryl group having 6 to 18 ring-forming carbon atoms, an unsubstituted or substituted heteroaryl group having 5 to 18 ring-forming atoms, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, CN, or N(R 22 ) 2 represents, or, two adjacent residues R 1 , R 2 , and / or R 3 , and / or two adjacent residues R 4 , R 5 , and / or R 6 , and / or two adjacent residues R 7 , R 8 , R 9 , R 10 , and / or R 11 , and / or two adjacent residues R 12 , R 13 , R 14 , and / or R 15 , and / or two adjacent residues R 16 , R 17 , R 18 , and / or R 19 together form an unsubstituted or substituted ring structure, and / or, R 7 and / or R 11 is bonded to R 6 and / or R 12 to form an unsubstituted or substituted ring structure, R 22 represents an unsubstituted or substituted aryl group having 6 to 18 ring-forming carbon atoms, or an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, or, R 22 is adjacent to the residue R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , or R 19 together form an unsubstituted or substituted ring structure.

[0094] Most preferably, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 each independently represents hydrogen, an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 6 ring-forming carbon atoms, an unsubstituted or substituted aryl group having 6 to 13 ring-forming carbon atoms, an unsubstituted or substituted heteroaryl group having 5 to 13 ring-forming atoms, CN, or N(R 22 ) 2 . Or, two adjacent residues R 1 , R 2 , and / or R 3 , and / or two adjacent residues R 4 , R 5 , and / or R 6 , and / or two adjacent residues R 7 , R 8 , R 9 , R 10 , and / or R 11 , and / or two adjacent residues R 12 , R 13 , R 14 , and / or R 15and / or two adjacent residues R 16 R 17 R 18 and / or R 19 both form an unsubstituted or substituted ring structure, and / or, R 7 and / or R 11 is R 6 and / or R 12 is bonded to R R 22 to form an unsubstituted or substituted ring structure,

[0095] In a further preferred embodiment, the residue R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 and R 19 of 0, 1, 2, 3, 4, 5, 6, 7, or 8, preferably 0, 1, 2, 3, 4, 5, or 6 are not hydrogen, i.e., the remaining residues are hydrogen. More preferably, the residue R 2 R 5 R 9 R 12 R 13 R 14 R 15 and R 18 of 0, 1, 2, 3, 4, 5, 6, 7, or 8, preferably 0, 1, 2, 3, 4, 5, or 6, more preferably 0, 1, 2, 3, or 4 are not hydrogen, i.e., the remaining residues are hydrogen.

[0096] In a preferred embodiment, the heterocyclic compound according to the present invention is represented by one of the following formulas.

[0097]

Chemical formula

[0098] In the formula, the residues are defined as described above. In formulas (VA) and (VB), two adjacent residues R 1 , R 2 , and / or R 3 , and / or two adjacent residues R 4 and R 5 , and / or two adjacent residues R 8 , R 9 , R 10 , and / or R 11 , and / or two adjacent residues R 12 , R 13 , R 14 , and / or R 15 , and / or two adjacent residues R 16 , R 17 , R 18 , and / or R 19 may together form an unsubstituted or substituted ring structure. In formula (VC), two adjacent residues R 1 , R 2 , and / or R 3 , and / or two adjacent residues R 4 , R 5 , and / or R 6 , and / or two adjacent residues R 7 , R 8 , R 9 , and / or R 10 , and / or two adjacent residues R 13 , R 14 , and / or R 15 , and / or two adjacent residues R 16 , R 17 , R 18 , and / or R 19Both may form an unsubstituted or substituted ring structure.

[0099] More preferably, the heterocyclic compound according to the present invention is represented by one of the following formulas.

[0100]

Chemical formula

[0101] In the formula, the residues are defined as described above, In formulas (VAa) and (VBa), Two adjacent residues R 12 , R 13 , R 14 , and / or R 15 Both may form an unsubstituted or substituted ring structure, In formula (VCa), Two adjacent residues R 13 , R 14 , and / or R 15 Both may form an unsubstituted or substituted ring structure.

[0102] In a preferred embodiment, the heterocyclic compound according to the present invention is represented by formula (VA), wherein two adjacent residues R 1 , R 2 , and / or R 3 , and / or two adjacent residues R 16 , R 17 , R 18 , and / or R 19 Both form an unsubstituted or substituted ring structure.

[0103] In a preferred embodiment, the heterocyclic compound according to the present invention is represented by formula (VA), wherein R 1 ~R 3 and / or R 16 ~R 19At least one of them is an unsubstituted or substituted aryl group having 6 to 60 ring-forming carbon atoms, an unsubstituted or substituted heteroaryl group having 5 to 60 ring-forming atoms, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted halogenated alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, CN, N(R 22 ) 2 , OR 20 , SR 20 , B(R 21 ) 2 , SiR 24 R 25 R 26 , or halogen, and R 4 ~R 5 and / or R 12 ~R 15 At least one of them is an unsubstituted or substituted aryl group having 6 to 60 ring-forming carbon atoms, an unsubstituted or substituted heteroaryl group having 5 to 60 ring-forming atoms, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted halogenated alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, CN, N(R 22 ) 2 , OR 20 , SR 20 , B(R 21 ) 2 , SiR 24 R 25 R 26 , or represents halogen.

[0104] In a further preferred embodiment, the heterocyclic compound according to the invention is represented by formula (VA), wherein R 1 ~R 3 At least one of and / or R 16 ~R 19 At least one of and R 4 ~R 5 At least one of and R 12 ~R 15At least one of them is an unsubstituted or substituted aryl group having 6 to 60 ring-forming carbon atoms, an unsubstituted or substituted heteroaryl group having 5 to 60 ring-forming atoms, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted halogenated alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, CN, N(R 22 ) 2 , OR 20 , SR 20 , B(R 21 ) 2 , SiR 24 R 25 R 26 , or halogen.

[0105] In a preferred embodiment, the heterocyclic compound according to the present invention is represented by formula (VA), wherein R 9 is an unsubstituted or substituted heteroaryl group having 5 to 60 ring-forming atoms, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted halogenated alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, CN, N(R 22 ) 2 , OR 20 , SR 20 , B(R 21 ) 2 , SiR 24 R 25 R 26 , or halogen, and at least one of R 12 to R 15 is an unsubstituted or substituted aryl group having 6 to 60 ring-forming carbon atoms, an unsubstituted or substituted heteroaryl group having 5 to 60 ring-forming atoms, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted halogenated alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, CN, N(R 22 ) 2 , OR 20 , SR 20 , B(R 21 ) 2 , SiR 24 R 25 R 26represents C or halogen.

[0106] In a preferred embodiment, the heterocyclic compound according to the present invention is represented by formula (VC), wherein R 4 ~R 6 , R 13 ~R 15 at least one of is an unsubstituted or substituted aryl group having 6 to 60 ring-forming carbon atoms, an unsubstituted or substituted heteroaryl group having 5 to 60 ring-forming atoms, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted halogenated alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 ring-forming carbon atoms, CN, N(R 22 ) 2 , OR 20 , SR 20 , B(R 21 ) 2 , SiR 24 R 25 R 26 represents C or halogen.

[0107] In a preferred embodiment, the heterocyclic compound according to the present invention is represented by formula (VC) or formula (VB), wherein the residue R 4 , R 5 , R 6 , R 12 , R 13 , R 14 , or R 15 at least one of is C 1 ~C 10 alkyl, C 3 ~C 12 cycloalkyl, or C 6 ~C 10 aryl, preferably C 1 ~C 4 alkyl, C 5 ~C 10 cycloalkyl, or phenyl, more preferably tert-butyl.

[0108] Examples of the compound of formula (I) are shown below.

[0109]

Chemical formula

[0110]

Chem.

[0111]

Chem.

[0112]

Chem.

[0113]

Chem.

[0114]

Chem.

[0115]

Chem.

[0116]

Chem.

[0117]

Chem.

[0118]

Chem.

[0119]

Chem.

[0120] [Chemistry]

[0121] [Chemistry]

[0122] [Chemistry]

[0123] [Chemistry]

[0124] [Chemistry]

[0125] [Chemistry]

[0126] Production of the compound of formula (I): The compound represented by formula (I) can be synthesized by following the reactions performed in the examples of this application and by using alternative reactions or raw materials suitable for the target product, similar to the reactions and raw materials known in the art.

[0127] The compound of formula (I) is produced, for example, by the following steps.

[0128] (i) BHal 3 By adding to intermediate (II), the compound of formula (I) is obtained.

[0129] [Chemistry]

[0130] Wherein, Hal represents a halogen, preferably F, Cl, Br, or I, more preferably Cl or Br, and most preferably Br. R is C 1 ~C 8 alkyl or C 6 ~C 10 aryl, preferably C 1 ~C 4 alkyl or phenyl, more preferably methyl. All other residues and coefficients are as defined above.

[0131] Suitable reaction conditions are described in the examples of this application.

[0132] Intermediate (II) is prepared, for example, starting from a compound of formula (III).

[0133]

Chemical formula

[0134] (i) Reaction of Hal of compound (III) 2 with an amino compound (IVa) (which may be further modified after reaction with compound (III)), or an amino compound (IVb), and (ii) Reaction of Hal of compound (III) 1 with a carbazole derivative (V). It is prepared by Hal 1 represents a halogen, preferably Cl. Hal 2 represents a halogen, preferably Br. R is C 1 ~C 8 alkyl or C 6 ~C 10 aryl, preferably C 1 ~C 4 alkyl or phenyl, more preferably methyl. All other residues and coefficients are as defined above.

[0135] Generally, step (ii) is carried out after step (i) is first performed.

[0136]

Chem.

[0137]

Chem.

[0138] In the formula, the dotted line is the site where it binds at the position of Hal in the compound of formula (III). 2 of the position where it binds.

[0139]

Chem.

[0140] In the formula, X’ is a direct bond (i.e., R E and ring A 1 are linked via a direct bond.), O, S, NR 23 , SiR 24 R 25 , CR 27 R 28 , or BR 21 , preferably a direct bond.

[0141]

Chem.

[0142] Preferred compounds of formula (V) are produced, for example, by the following steps.

[0143] (i) By adding BHal 3 to the intermediate (VI), a compound of formula (V) is obtained.

[0144] [Chemical formula]

[0145] In the formula, Hal represents a halogen, preferably F, Cl, Br, or I, more preferably Cl or Br, and most preferably Br. R is C 1 ~C 8 alkyl or C 6 ~C 10 aryl, preferably C 1 ~C 4 alkyl or phenyl, more preferably methyl. All other residues and coefficients are as defined above.

[0146] The intermediate (VI) is prepared, for example, starting from a compound of formula (VII).

[0147] [Chemical formula] (VII)

[0148] (i) The reaction of Hal 2 in compound (VII) with an amino compound (VIIIa), which may be further modified after reaction with compound (VII), or an amino compound (VIIIb), and (ii) The reaction of Hal 1 in compound (VII) with a carbazole derivative (IX). It is produced by Hal 1 represents a halogen, preferably Cl. Hal 2 represents a halogen, preferably Br. R is C 1 ~C 8 alkyl or C 6 ~C 10 aryl, preferably C 1 ~C 4 alkyl or phenyl, more preferably methyl. All other residues and coefficients are as defined above.

[0149] Generally, after step (i) is performed first, step (ii) is carried out.

[0150]

Chem.

[0151] This may be modified as follows.

[0152]

Chem.

[0153]

Chem.

[0154] In the formula, all residues and coefficients are as defined above.

[0155] In still other embodiments, the compound of formula (I) is produced, for example, as follows.

[0156] ia) By adding BHal 3 to intermediate (IIa), the compound of formula (I) is obtained.

[0157]

Chem.

[0158] In the formula, Hal represents a halogen, preferably F, Cl, Br, or I, more preferably Cl or Br, and most preferably Br, and all other residues and coefficients are as defined above.

[0159] Suitable reaction conditions are described in the examples of this application.

[0160] Intermediate (IIa) is obtained, for example, starting from a compound of formula (IIIa),

[0161]

Chemical formula

[0162] (i) by reacting Hal 2 of compound (IIIa) with an amino compound (IVa) (which may be further modified after reaction with compound (IIIa)), or an amino compound (IVb), and (ii) by reacting Hal 1 of compound (IIIa) with a carbazole derivative (V), and is produced by Hal 1 represents a halogen, preferably Cl, Hal 2 represents a halogen, preferably Br, All other residues and coefficients are as defined above.

[0163] Generally, step (ii) is carried out after step (i) is first carried out.

[0164]

Chemical formula

[0165]

Chemical formula

[0166] In the formula, the dotted line is the site where it binds at the position of Hal 2 in the compound of formula (III).

[0167]

Chemical formula

[0168] Wherein, X’ is a direct bond (i.e., R E and ring A 1 are bonded via a direct bond.), O, S, NR 23 , SiR 24 R 25 , CR 27 R 28 , or BR 21 , preferably a direct bond.

[0169]

Chemical formula

[0170] Wherein, all residues and coefficients are as defined above.

[0171] Preferred compounds of formula (Va) are prepared, for example, by the following steps.

[0172] Ia) Adding BHal 3 to intermediate (VIa) gives a compound of formula (Va).

[0173]

Chemical formula

[0174] Wherein, Hal represents a halogen, preferably F, Cl, Br, or I, more preferably Cl or Br, and most preferably Br, R 5 is C 1 ~C 10 alkyl, C 3 ~C 12 cycloalkyl, or C 6 ~C 10 aryl, preferably C 1 ~C 4 alkyl, C 5 ~C 10 cycloalkyl, or phenyl, more preferably tert-butyl, All other residues and coefficients are as defined above.

[0175] The intermediate (VIa) is, for example, starting from a compound of formula (VIIa),

[0176]

Chemical formula

[0177] (i) the reaction of Hal of the compound (VIIa) 2 with an amino compound (VIIIa) (which may be further modified after reaction with the compound (VIIa)), or an amino compound (VIIIb), and (ii) the reaction of Hal of the compound (VIIa) 1 with a carbazole derivative (IX), is produced by Hal 1 represents a halogen, preferably Cl, Hal 2 represents a halogen, preferably Br, R 5 is C 1 ~C 10 alkyl, C 3 ~C 12 cycloalkyl, or C 6 ~C 10 aryl, preferably C 1 ~C 4 alkyl, C 5 ~C 10 cycloalkyl, or phenyl, more preferably represents tert-butyl All other residues and coefficients are as defined above.

[0178] Generally, after step (i) is carried out first, step (ii) is carried out.

[0179]

Chemical formula

[0180] This may be modified as follows.

[0181] [Chemical Formula]

[0182] In the formula, the dotted line indicates the site where it binds to the compound of formula (VIIa) at the position of Hal 2 ().

[0183] [Chemical Formula]

[0184] In the formula, all residues and coefficients are as defined above.

[0185] Examples of suitable production methods are given below.

[0186] Organic electroluminescence device According to one aspect of the present invention, a material for an organic electroluminescence device containing at least one compound of formula (I) is provided.

[0187] According to another aspect of the present invention, an organic electroluminescence device containing at least one compound of formula (I) is provided.

[0188] According to another aspect of the present invention, the following organic electroluminescence device is provided. It includes a cathode, an anode, and one or more organic thin film layers including a light emitting layer disposed between the cathode and the anode, and at least one layer of the organic thin film layer contains at least one compound of formula (I).

[0189] According to another aspect of the present invention, an organic electroluminescence device in which the light emitting layer contains at least one compound of formula (I) is provided.

[0190] According to another aspect of the present invention, there is provided an organic electroluminescence device in which a light-emitting layer contains at least one compound of formula (I) as a dopant material and an anthracene compound as a host material.

[0191] According to another aspect of the present invention, there is provided an electronic device including the organic electroluminescence device according to the present invention.

[0192] According to another aspect of the present invention, there is provided a phosphor material containing at least one compound of formula (I).

[0193] According to another aspect of the present invention, there is provided a light-emitting layer containing at least one host and at least one dopant, wherein the dopant contains at least one compound of formula (I).

[0194] According to another aspect of the present invention, there is provided the use of the compound of formula (I) according to the present invention in an organic electroluminescence device.

[0195] In one embodiment, the organic EL device includes a hole transport layer between the anode and the light-emitting layer.

[0196] In one embodiment, the organic EL device includes an electron transport layer between the cathode and the light-emitting layer.

[0197] As used herein, "one or more organic thin film layers between the light-emitting layer and the anode" means that layer when only one organic layer exists between the light-emitting layer and the anode, and means at least one of them when a plurality of organic layers exist. For example, when two or more organic layers exist between the light-emitting layer and the anode, the organic layer closer to the light-emitting layer is referred to as a "hole transport layer", and the organic layer closer to the anode is referred to as a "hole injection layer". Each of the "hole transport layer" and the "hole injection layer" may be a single layer or may be composed of two or more layers. One of these layers may be a single layer, and the other layer may be two or more layers.

[0198] Similarly, the "one or more organic thin film layers disposed between the light-emitting layer and the cathode" means that layer when only one organic layer exists between the light-emitting layer and the cathode, and means at least one of those layers when a plurality of organic layers exist. For example, when two or more organic layers exist between the light-emitting layer and the cathode, the organic layer closer to the light-emitting layer is referred to as the "electron transport layer", and the organic layer closer to the cathode is referred to as the "electron injection layer". Each of the "electron transport layer" and the "electron injection layer" may be a single layer or may be composed of two or more layers. One of these layers may be a single layer, and the other layer may be two or more layers.

[0199] The above-mentioned "one or more organic thin film layers including the light-emitting layer", preferably the light-emitting layer, contains a compound represented by formula (I). The compound represented by formula (I) preferably functions as a luminescent material, more preferably as a fluorescent luminescent material, and most preferably as a blue fluorescent luminescent material. By the presence of the compound of formula (I) in the organic EL element, preferably in the light-emitting layer, an organic EL element characterized by high external quantum efficiency (EQE) and long life is provided.

[0200] According to another aspect of the present invention, a light-emitting layer of an organic electroluminescence element containing at least one compound of formula (I) is provided.

[0201] Preferably, the light-emitting layer contains at least one luminescent material (dopant material) and at least one host material, where the luminescent material is at least one compound of formula (I).

[0202] In one embodiment, the host is not selected from CBP (4,4'-bis-(N-carbazolyl)-biphenyl), mCP, mCBP Sif87 (dibenzothiophen-2-yltriphenylsilane), CzSi, Sif88 ((dibenzothiophen-2-yl)diphenylsilane), DPEPO (bis[2-(diphenylphosphino)phenyl]ether oxide), 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzothiophen-2-yl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzofuranyl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzothiophenyl)phenyl]-9H-carbazole, T2T (2,4,6-tris(biphenyl-3-yl)-1,3,5-triazine), T3T (2,4,6-tris(triphenyl-3-yl)-1,3,5-triazine), and / or TST (2,4,6-tris(9,9'-spirobifluoren-2-yl)-1,3,5-triazine).

[0203] Preferred host materials are substituted or unsubstituted polycyclic aromatic hydrocarbon (PAH) compounds, substituted or unsubstituted polycyclic heteroaromatic compounds, substituted or unsubstituted anthracene compounds, or substituted or unsubstituted pyrene compounds.

[0204] More preferably, the organic electroluminescence device according to the present invention includes at least one compound of formula (I) as a dopant material in the light-emitting layer and at least one host material selected from the group consisting of substituted or unsubstituted polycyclic aromatic hydrocarbon (PAH) compounds, substituted or unsubstituted polycyclic heteroaromatic compounds, substituted or unsubstituted anthracene compounds, and substituted or unsubstituted pyrene compounds. Preferably, at least one host is at least one substituted or unsubstituted anthracene compound.

[0205] In a further preferred embodiment, the organic electroluminescence device according to the present invention includes at least one compound of formula (I) as a dopant material and at least one host material selected from the group consisting of a substituted or unsubstituted polycyclic aromatic hydrocarbon (PAH) compound, a substituted or unsubstituted anthracene compound, and a substituted or unsubstituted pyrene compound in the light-emitting layer. Preferably, at least one host is at least one substituted or unsubstituted anthracene compound.

[0206] According to another aspect of the present invention, there is provided a light-emitting layer of an organic electroluminescence device containing at least one compound of formula (I) as a dopant material and an anthracene compound as a host material.

[0207] A suitable anthracene compound is represented by the following formula (10).

[0208]

Chemical formula

[0209] In the formula, Two or more adjacent R 101 ~R 110 One or more pairs of may form a substituted or unsubstituted saturated or unsaturated ring, R that does not form a substituted or unsubstituted saturated or unsaturated ring 101 ~R 110 are independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted haloalkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 50 ring-forming carbon atoms, a substituted or unsubstituted arylthio group having 6 to 50 ring-forming carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, -Si(R 121)(R 122 )(R 123 )、 -C(=O)R 124 、 -COOR 125 、 -N(R 126 )(R 127 )、 a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, a substituted or unsubstituted monovalent heterocyclic group having 5 to 50 ring-forming atoms, or a group represented by the following formula (31), R 121 ~R 127 are, independently, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group having 5 to 50 ring-forming atoms, and when there are a plurality of each of R 121 ~R 127 , the plurality of R 121 ~R 127 may be the same or different, provided that at least one of R 101 ~R 110 that does not form a substituted or unsubstituted saturated or unsaturated ring is a group represented by the following formula (31). When there are two or more groups represented by formula (31), these groups may be the same or different. -L 101 -Ar 101 (31) In formula (31), L 101 is a single bond, a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or a substituted or unsubstituted divalent heterocyclic group having 5 to 50 ring-forming atoms, Ar 101 is a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group having 5 to 50 ring-forming atoms.

[0210] Specific examples of each substituent in compound (10), the substituent in the case of "substituted or unsubstituted", and the halogen atom are the same as those described above.

[0211] "One or more pairs of two or more adjacent R 101 ~R 110 may form a substituted or unsubstituted saturated or unsaturated ring." will be described.

[0212] "One pair of two or more adjacent R 101 ~R 110 ", for example, R 101 and R 102 , R 102 and R 103 , R 103 and R 104 , R 105 and R 106 , R 106 and R 107 , R 107 and R 108 , R 108 and R 109 , R 101 and R 102 and R 103 and so on.

[0213] The substituents in the "substituted" case of "substituted or unsubstituted" for the saturated or unsaturated ring are the same as those in the "substituted or unsubstituted" case listed in formula (10).

[0214] "Saturated or unsaturated ring" means the case where R 101 and R 102 form a ring, for example, a ring formed by the carbon atom to which R 101 is bonded, the carbon atom to which R 102 is bonded, and one or more arbitrary elements. Specifically, when a ring is formed by R 101 and R 102 , if an unsaturated ring is formed by the carbon atom to which R 101 is bonded, the carbon atom to which R 102 is bonded, and four carbon atoms, the ring formed by R 101 and R 102 is a benzene ring.

[0215] "Any element" is preferably a C element, an N element, an O element, or an S element. In any element (for example, a C element or an N element), an atomic bond that does not form a ring may be terminated with a hydrogen atom or the like.

[0216] "One or more arbitrary elements" are preferably two or more and fifteen or less, more preferably three or more and twelve or less, and still more preferably three or more and five or less arbitrary elements.

[0217] For example, R 101 and R 102 may form a ring, and at the same time R 105 and R 106 may form a ring. In this case, the compound represented by formula (10) is, for example, the compound represented by the following formula (10A).

[0218]

Chemical formula

[0219] In one embodiment, R 101 to R 110 are independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring-forming atoms, or a group represented by formula (31).

[0220] Preferably, R 101 to R 110 are independently a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring-forming atoms, or a group represented by formula (31).

[0221] More preferably, R 101 to R 110 are independently a hydrogen atom, a substituted or unsubstituted aryl group containing 6 to 18 ring carbon atoms, a substituted or unsubstituted heterocyclic group containing 5 to 18 ring atoms, or a group represented by formula (31).

[0222] Most preferably, R 109 and R 110 at least one of which is a group represented by formula (31).

[0223] Even more preferably, R 109 and R 110 are each independently a group represented by formula (31).

[0224] In one embodiment, compound (10) is a compound represented by the following formula (10-1).

[0225]

Chemical formula

[0226] In formula (10-1), R 101 ~R 108 , L 101 , and Ar 101 are as defined in formula (10).

[0227] In one embodiment, compound (10) is a compound represented by the following formula (10-2).

[0228]

Chemical formula

[0229] In formula (10-2), R 101 , R 103 ~R 108 , L 101 , and Ar 101 are as defined in formula (10).

[0230] In one embodiment, compound (10) is a compound represented by the following formula (10-3).

[0231]

Chemical formula

[0232] In formula (10-3), R 101A ~R 108A are each independently a hydrogen atom, or a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, L 101A is a single bond or a substituted or unsubstituted arylene group having 6 to 50 ring-forming carbon atoms, and two L's 101A may be the same or different, Ar 101A is a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, and two Ar's 101A may be the same or different.

[0233] In one embodiment, compound (10) is a compound represented by the following formula (10-4).

[0234]

Chemical formula

[0235] In formula (10-4), L 101 and Ar 101 are as defined in formula (10), R 101A ~R 108A are each independently a hydrogen atom, or a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, X 11 is O, S, or N(R 61 ), R 61 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, R 62 ~R 69 One of 101 is a bond connecting to L L 101 and the adjacent R 62 ~R 69One or more pairs of them may be combined with each other to form a substituted or unsubstituted saturated or unsaturated ring. L 101 R which does not combine with 101 and does not form a substituted or unsubstituted saturated or unsaturated ring 62 ~R 69 Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms.

[0236] In one embodiment, the compound (10) is a compound represented by the following formula (10-4A).

[0237]

Chemical formula

[0238] In formula (10-4A), L 101 and Ar 101 are as defined in formula (10), R 101A ~R 108A Each independently represents a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, X 11 is O, S, or N(R 61 ), R 61 is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, One or more pairs of two or more adjacent R 62A ~R 69A may form a substituted or unsubstituted saturated or unsaturated ring, Two adjacent R 62A ~R 69A form a ring represented by the following formula (10-4A-1), R 62A ~R 69Ais independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms.

[0239]

Chemical formula

[0240] In formula (10-4A-1), each of the two atomic bonds * is bonded to two adjacent ones of R 62A ~R 69A and one of R R 70 ~R 73 that is not bonded to L 101 is an atomic bond that bonds to L L 101 and R 70 ~R 73 are independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms.

[0241] In one embodiment, the compound (10) is a compound represented by the following formula (10-6).

[0242]

Chemical formula

[0243] In formula (10-6), L 101 and Ar 101 are as defined in formula (10), R 101A ~R 108A are as defined in formula (10-4), R 66 ~R 69 are as defined in formula (10-4), X 12 is O or S.

[0244] In one embodiment, the compound represented by formula (10-6) is a compound represented by the following formula (10-6H).

[0245]

Chemical formula

[0246] (In formula (10-6H), L 101 and Ar 101 are as defined in formula (10), R 66 ~R 69 are as defined in formula (10-4), X 12 is O or S.)

[0247] In one embodiment, the compounds represented by formula (10-6) and formula (10-6H) are compounds represented by the following formula (10-6Ha).

[0248]

Chemical formula

[0249] In formula (10-6Ha), L 101 and Ar 101 are as defined in formula (10), X 12 is O or S.)

[0250] In one embodiment, the compounds represented by formula (10-6), formula (10-6H), and formula (10-6Ha) are compounds represented by the following formula (10-6Ha-1) or formula (10-6Ha-2).

[0251]

Chemical formula

[0252] In formula (10-6Ha-1) and formula (10-6Ha-2), L 101 and Ar 101 are as defined in formula (10), X 12 is O or S.

[0253] In one embodiment, compound (10) is a compound represented by the following formula (10-7).

[0254]

Chemical formula

[0255] In formula (10-7), L 101 and Ar 101 are as defined in formula (10), R 101A ~R 108A are as defined in formula (10-4), X 11 is as defined in formula (10-4), R 62 ~R 69 are as defined in formula (10-4), provided that any one pair of R 66 and R 67 , R 67 and R 68 , and R 68 and R 69 are bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring.

[0256] In one embodiment, compound (10) is a compound represented by the following formula (10-7H).

[0257]

Chemical formula

[0258] In formula (10-7H), L 101 and Ar 101 are as defined in formula (10), X11 is as defined by formula (10-4), and R 62 ~R 69 is as defined by formula (10-4), provided that any one pair of R 66 and R 67 , R 67 and R 68 , and any one pair of R 68 and R 69 are bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring.

[0259] In one embodiment, compound (10) is a compound represented by the following formula (10-8).

[0260]

Chemical formula

[0261] In formula (10-8), L 101 and Ar 101 are as defined by formula (10), R 101A ~R 108A are as defined by formula (10-4), X 12 is O or S, R 66 ~R 69 are as defined by formula (10-4), provided that any one pair of R 66 and R 67 , R 67 and R 68 , and any one pair of R 68 and R 69 are bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring.

[0262] In one embodiment, the compound represented by formula (10-8) is a compound represented by the following formula (10-8H).

[0263]

Chemical formula

[0264] In formula (10-8H), L 101 and Ar 101 are as defined in formula (10).

[0265] R 66 ~R 69 are as defined in formula (10-4), provided that any one pair of R 66 and R 67 , R 67 and R 68 , and R 68 and R 69 is bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring. R 66 and R 67 , R 67 and R 68 , and R 68 and R 69 is preferably bonded to each other to form an unsubstituted benzene ring, X 12 is O or S.

[0266] In one embodiment, for the compound represented by formula (10-7), formula (10-8), or formula (10-8H), any one pair of R 66 and R 67 , R 67 and R 68 , and R 68 and R 69 is bonded to each other to form a ring represented by the following formula (10-8-1) or formula (10-8-2), and R 66 ~R 69 that does not form a ring represented by formula (10-8-1) or formula (10-8-2) does not form a substituted or unsubstituted saturated or unsaturated ring.

[0267]

Chemical formula

[0268] In formula (10-8-1) and formula (10-8-2), Two atomic bonds * are, independently, R 66 and R 67 , R 67 and R 68 , or R 68 and R 69 and combine with one pair of, R 80 ~R 83 are, independently, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, X 13 is O or S.

[0269] In one embodiment, the compound (10) is a compound represented by the following formula (10-9).

[0270]

Chemical formula

[0271] In formula (10-9), L 101 and Ar 101 are as defined in formula (10), R 101A ~R 108A are as defined in formula (10-4), R 66 ~R 69 are as defined in formula (10-4), provided that R 66 and R 67 , R 67 and R 68 , and R 68 and R 69 do not bond to each other and do not form a substituted or unsubstituted saturated or unsaturated ring., X 12 is O or S.

[0272] In one embodiment, the compound (10) is selected from the group consisting of compounds represented by the following formulas (10-10-1) to (10-10-4).

[0273]

Chem.

[0274] In formulas (10-10-1H) to (10-10-4H), L 101A and Ar 101A are as defined in formula (10-3).

[0275] Regarding the compound represented by formula (10), the following compounds can be cited as specific examples.

[0276]

Chem.

[0277]

Chem.

[0278]

Chem.

[0279]

Chem.

[0280]

Chem.

[0281]

Chem.

[0282]

Chem.

[0283]

Chem.

[0284]

Chem.

[0285]

Chem.

[0286]

Chem.

[0287]

Chem.

[0288]

Chem.

[0289]

Chem.

[0290]

Chem.

[0291]

Chem.

[0292]

Chem.

[0293]

Chem.

[0294] [Chemistry]

[0295] [Chemistry]

[0296] [Chemistry]

[0297] [Chemistry]

[0298] [Chemistry]

[0299] [Chemistry]

[0300] [Chemistry]

[0301] [Chemistry]

[0302] [Chemistry]

[0303] [Chemistry]

[0304] The light-emitting layer contains a compound represented by formula (I) as a dopant and at least one host, where the preferred hosts are as described above. When the host is more preferably at least one compound represented by formula (10), the content of at least one compound represented by formula (I) is preferably 0.5 to 70% by mass, more preferably 0.5 to 30% by mass, still more preferably 1 to 30% by mass, yet more preferably 1 to 20% by mass, particularly preferably 1 to 10% by mass, and even more particularly preferably 1 to 5% by mass based on the total mass of the light-emitting layer.

[0305] The content of at least one host (where the preferred hosts are as described above), preferably at least one compound represented by formula (10), is preferably 30 to 99.9% by mass, more preferably 70 to 99.5% by mass, still more preferably 70 to 99% by mass, yet more preferably 80 to 99% by mass, particularly preferably 90 to 99% by mass, and even more particularly preferably 95 to 99% by mass based on the total mass of the light-emitting layer.

[0306] The layer structure of the organic EL element according to one aspect of the present invention will be described.

[0307] The organic EL element according to one aspect of the present invention includes a cathode, an anode, and one or more organic thin film layers including a light-emitting layer disposed between the cathode and the anode. The organic layer includes at least one layer composed of an organic compound. Alternatively, the organic layer is formed by laminating a plurality of layers composed of an organic compound. The organic layer may further include an inorganic compound in addition to the organic compound.

[0308] At least one of the organic layers is a light-emitting layer. The organic layer may be configured, for example, as a single light-emitting layer, or may include other layers that can be adopted in the layer structure of the organic EL element. The layers that can be adopted in the layer structure of the organic EL element are not particularly limited, but examples thereof include a hole transport region (including at least one hole transport layer, and preferably at least one of a hole injection layer, an electron blocking layer, an exciton blocking layer, etc. additionally), a light-emitting layer, a spacer layer, and an electron transport region (including at least one electron transport layer, and preferably at least one of an electron injection layer, a hole blocking layer, etc.) provided between the cathode and the light-emitting layer.

[0309] The organic EL element according to one aspect of the present invention may be, for example, a fluorescent single-color light-emitting element, a phosphorescent single-color light-emitting element, or a fluorescent / phosphorescent hybrid white light-emitting element. Preferably, the organic EL element is a fluorescent single-color light-emitting element, more preferably a blue fluorescent single-color light-emitting element, or a fluorescent / phosphorescent hybrid white light-emitting element. Blue fluorescence means fluorescence at 400 nm to 500 nm (peak maximum value), preferably 430 nm to 490 nm (peak maximum value).

[0310] Furthermore, the organic EL element may be a simple element having a single light-emitting unit, or a tandem element having a plurality of light-emitting units.

[0311] The "light-emitting unit" in this specification is the minimum unit including an organic layer, where at least one of the organic layers is a light-emitting layer, and light is emitted by the recombination of the injected holes and electrons.

[0312] Furthermore, the "light-emitting layer" described in this specification is an organic layer having a light-emitting function. The light-emitting layer may be, for example, a phosphorescent light-emitting layer, a fluorescent light-emitting layer, etc., preferably a fluorescent light-emitting layer, more preferably a blue fluorescent light-emitting layer, and may be a single layer or a laminate of a plurality of layers.

[0313] The light-emitting unit may be a stacked unit having a plurality of phosphorescent light-emitting layers or fluorescent light-emitting layers. In this case, for example, a spacer layer that prevents excitons generated in the phosphorescent light-emitting layer from diffusing into the fluorescent light-emitting layer may be provided between each light-emitting layer.

[0314] Examples of simple organic EL elements include element configurations such as anode / light-emitting unit / cathode.

[0315] Examples of typical layer structures of the light-emitting unit are shown below. The layers in parentheses are provided optionally. (a) (Hole injection layer / ) Hole transport layer / Fluorescent light-emitting layer ( / Electron transport layer / Electron injection layer) (b) (Hole injection layer / ) Hole transport layer / Phosphorescent light-emitting layer ( / Electron transport layer / Electron injection layer) (c) (Hole injection layer / ) Hole transport layer / First fluorescent light-emitting layer / Second fluorescent light-emitting layer ( / Electron transport layer / Electron injection layer) (d) (Hole injection layer / ) Hole transport layer / First phosphorescent layer / Second phosphorescent layer ( / Electron transport layer / Electron injection layer) (e) (Hole injection layer / ) Hole transport layer / Phosphorescent light-emitting layer / Spacer layer / Fluorescent light-emitting layer ( / Electron transport layer / Electron injection layer) (f) (Hole injection layer / ) Hole transport layer / First phosphorescent light-emitting layer / Second phosphorescent light-emitting layer / Spacer layer / Fluorescent light-emitting layer ( / Electron transport layer / Electron injection layer) (g) (Hole injection layer / ) Hole transport layer / First phosphorescent layer / Spacer layer / Second phosphorescent light-emitting layer / Spacer layer / Fluorescent light-emitting layer ( / Electron transport layer / Electron injection layer) (h) (Hole injection layer / ) Hole transport layer / Phosphorescent light-emitting layer / Spacer layer / First fluorescent light-emitting layer / Second fluorescent light-emitting layer ( / Electron transport layer / Electron injection layer) (i) (Hole injection layer / ) Hole transport layer / Electron blocking layer / Fluorescent light-emitting layer ( / Electron transport layer / Electron injection layer) (j) (Hole injection layer / ) Hole transport layer / Electron blocking layer / Phosphorescent light-emitting layer ( / Electron transport layer / Electron injection layer) (k) (Hole injection layer / ) Hole transport layer / Exciton blocking layer / Fluorescent light-emitting layer ( / Electron transport layer / Electron injection layer) (l) (Hole injection layer / ) Hole transport layer / Exciton blocking layer / Phosphorescent light-emitting layer ( / Electron transport layer / Electron injection layer) (m) (Hole injection layer / ) First hole transport layer / Second hole transport layer / Fluorescent emission layer ( / Electron transport layer / Electron injection layer) (n) (Hole injection layer / ) First hole transport layer / Second hole transport layer / Fluorescent emission layer ( / First electron transport layer / Second electron transport layer / Electron injection layer) (o) (Hole injection layer / ) First hole transport layer / Second hole transport layer / Phosphorescent emission layer ( / Electron transport layer / Electron injection layer) (p) (Hole injection layer / ) First hole transport layer / Second hole transport layer / Phosphorescent emission layer ( / First electron transport layer / Second electron transport layer / Electron injection layer) (q) (Hole injection layer / ) Hole transport layer / Fluorescent emission layer / Hole blocking layer ( / Electron transport layer / Electron injection layer) (r) (Hole injection layer / ) Hole transport layer / Phosphorescent emission layer / Hole blocking layer ( / Electron transport layer / Electron injection layer) (s) (Hole injection layer / ) Hole transport layer / Fluorescent emission layer / Exciton blocking layer ( / Electron transport layer / Electron injection layer) (t) (Hole injection layer / ) Hole transport layer / Phosphorescent emission layer / Exciton blocking layer ( / Electron transport layer / Electron injection layer).

[0316] The layer structure of the organic EL element according to one aspect of the present invention is not limited to the above examples.

[0317] For example, when the organic EL element has a hole injection layer and a hole transport layer, it is preferable to provide a hole injection layer between the hole transport layer and the anode. Further, when the organic EL element has an electron injection layer and an electron transport layer, it is preferable to provide an electron injection layer between the electron transport layer and the cathode. Further, each of the hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer may be a single layer or a plurality of layers.

[0318] The plurality of phosphorescent emission layers, as well as the plurality of phosphorescent emission layers and fluorescent emission layers, can each exhibit different emission colors. For example, the light-emitting unit (f) may include a hole transport layer / First phosphorescent layer (red emission) / Second phosphorescent emission layer (green emission) / Space layer / Fluorescent emission layer (blue emission) / Electron transport layer.

[0319] An electron blocking layer may be provided between each light-emitting layer and the hole transport layer or the spacer layer. Further, a hole blocking layer may be provided between each light-emitting layer and the electron transport layer. By providing the electron blocking layer or the hole blocking layer, electrons or holes can be confined in the light-emitting layer, thereby increasing the charge recombination probability in the light-emitting layer and improving the light-emitting efficiency.

[0320] As a typical element structure of the tandem organic EL element, for example, element structures such as anode / first light-emitting unit / intermediate layer / second light-emitting unit / cathode can be cited.

[0321] The first light-emitting unit and the second light-emitting unit can be independently selected from the above-described light-emitting units, for example.

[0322] The intermediate layer is generally also called an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron extraction layer, a connection layer, a connector layer, or an intermediate insulating layer. The intermediate layer is a layer that supplies electrons to the first light-emitting unit and holes to the second light-emitting unit, and known materials can be used.

[0323] FIG. 1 is a schematic diagram showing an example of the structure of the organic EL element of the present invention. The organic EL element 1 includes a substrate 2, an anode 3, a cathode 4, and a light-emitting unit 10 provided between the anode 3 and the cathode 4. The light-emitting unit 10 preferably includes a light-emitting layer 5 containing a host material and a dopant. A hole injection transport layer 6 or the like may be provided between the light-emitting layer 5 and the anode 3, and an electron injection layer 8 and an electron transport layer 7 or the like (electron injection transport unit 11) may be provided between the light-emitting layer 5 and the cathode 4. An electron blocking layer may be provided on the anode 3 side of the light-emitting layer 5, and a hole blocking layer may be provided on the cathode 4 side of the light-emitting layer 5. With such a configuration, electrons or holes can be confined in the light-emitting layer 5, thereby improving the possibility of exciton generation in the light-emitting layer 5.

[0324] Hereinafter, the functions, materials, etc. of each layer constituting the organic EL element described in this specification will be described.

[0325] (Substrate) The substrate is used as a support for the organic EL element. The substrate preferably has a light transmittance of 50% or more in the visible region having a wavelength of 400 nm to 700 nm, and a smooth substrate is preferred. Examples of the material of the substrate include soda-lime glass, aluminosilicate glass, quartz glass, plastic, and the like. As the substrate, a flexible substrate can be used. A flexible substrate means a substrate that can be bent (flexible), and examples thereof include a plastic substrate. Specific examples of the material for forming the plastic substrate include polycarbonate, polyarylate, polyethersulfone, polypropylene, polyester, polyvinyl fluoride, polyvinyl chloride, polyimide, polyethylene naphthalate, and the like. Further, an inorganic vapor deposition film can be used.

[0326] (Anode) For example, as the anode, it is preferable to use a metal, an alloy, a conductive compound, a mixture thereof, etc. having a high work function (specifically, 4.0 eV or more). Specific examples of the material of the anode include indium tin oxide (ITO: indium tin oxide), indium tin oxide containing silicon or silicon oxide, indium zinc oxide, indium oxide containing tungsten oxide or zinc oxide, graphene, and the like. Further, it is also possible to use gold, silver, platinum, nickel, tungsten, chromium, molybdenum, iron, cobalt, copper, palladium, titanium, and nitrides of these metals (for example, titanium oxide).

[0327] The anode is usually formed by depositing these materials on the substrate by a sputtering method. For example, indium zinc oxide can be formed by a sputtering method using a target in which 1 to 10% by mass of zinc oxide is added to indium oxide. Further, indium oxide containing tungsten oxide or zinc oxide can be formed by a sputtering method using a target in which 0.5% to 5% by mass of tungsten oxide or 0.1% to 1% by mass of zinc oxide is added to indium oxide.

[0328] As other methods for forming the anode, a vacuum evaporation method, a coating method, an inkjet method, a spin coating method, etc. can be mentioned. When a silver paste or the like is used, it is possible to use a coating method, an inkjet method, etc.

[0329] The hole injection layer formed in contact with the anode is formed by using a material that enables easy hole injection regardless of the work function of the anode. For this purpose, it is possible to use a common electrode material in the anode, for example, a metal, an alloy, a conductive compound, and a mixture thereof. Specifically, materials having a small work function, such as alkali metals such as lithium and cesium, alkaline earth metals such as calcium and strontium, alloys containing these metals (for example, magnesium-silver and aluminum-lithium), rare earth metals such as europium and ytterbium, and alloys containing rare earth metals, etc. can be mentioned.

[0330] (Hole transport layer) / (Hole injection layer) The hole transport layer is an organic layer formed between the light-emitting layer and the anode and has a function of transporting holes from the anode to the light-emitting layer. When the hole transport layer is composed of a plurality of layers, the organic layer closer to the anode is often defined as the hole injection layer. The hole injection layer has a function of efficiently injecting holes from the anode into the organic layer unit. The above hole injection layer is generally used to stabilize the hole injection from the anode to the hole transport layer generally made of an organic material. For the hole injection layer, preferably, an organic material having good contact with the anode or an organic material having p-type doping is used.

[0331] p-type doping usually consists of one or more p-type dopant materials and one or more matrix materials. To increase the carrier density of the layer, the matrix material preferably has a shallower HOMO level, and the p-type dopant preferably has a deeper LUMO level. Specific examples of p-type dopants are acceptor materials listed below. Suitable matrix materials are hole transport materials listed below, preferably aromatic amine compounds or heterocyclic amine compounds.

[0332] As the p-type dopant material for the hole injection layer, preferably, an acceptor material, i.e., a condensed aromatic hydrocarbon material or a condensed heterocycle having high planarity, is used.

[0333] Specific examples of acceptor materials are quinone compounds having one or more electron-withdrawing groups, such as F 4 TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane), and 1,2,3-tris[(cyano)(4-cyano-2,3,5,6-tetrafluorophenyl)methylene]cyclopropane, hexaazatriphenylene compounds having one or more electron-withdrawing groups, such as hexaazatriphenylene-hexanitrile, aromatic hydrocarbon compounds having one or more electron-withdrawing groups, and arylboron compounds having one or more electron-withdrawing groups. Preferred p-type dopants are quinone compounds having one or more electron-withdrawing groups, such as F 4 TCNQ, 1,2,3-tris[(cyano)(4-cyano-2,3,5,6-tetrafluorophenyl)methylene]cyclopropane.

[0334] The ratio of the p-type dopant is preferably less than 20%, more preferably less than 10%, for example, a molar ratio of 1%, 3%, or 5% with respect to the matrix material.

[0335] The hole transport layer is generally used to efficiently inject and transport holes, and preferably, aromatic amine compounds or heterocyclic amine compounds are used.

[0336] Specific examples of the compound for the positive hole transport layer are represented by the general formula (H).

[0337] [Chemical formula]

[0338] In the formula, Ar 1 ~Ar 3 each independently represents a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring-forming atoms, preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group, a triphenylenyl group, a fluorenyl group, a spirobifluorenyl group, an indenofluorenyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazole-substituted aryl group, a dibenzofuran-substituted aryl group, or a dibenzothiophene-substituted aryl group. Two or more substituents selected from Ar 1 ~Ar 3 may be bonded to each other to form a ring structure such as a carbazole ring structure or an acridan ring structure.

[0339] Preferably, at least one of Ar 1 ~Ar 3 further has one arylamine substituent or heterocyclic amine substituent. More preferably, Ar 1 further has an arylamino substituent. In that case, Ar 1 preferably represents a substituted or unsubstituted biphenylene group or a substituted or unsubstituted fluorenylene group. Specific examples of the hole transport material are

[0340] [Chemical formula]

[0341] and are as follows.

[0342] [Chemical formula]

[0343] The second hole transport layer is preferably inserted between the first hole transport layer and the light-emitting layer, and the performance of the device is enhanced by blocking excess electrons or excitons. Specific examples of the second hole transport layer are the same as those of the first hole transport layer. Particularly in the case of a phosphorescent device, it is preferable that the second hole transport layer has a higher triplet energy for blocking triplet excitons (for example, a bicarbazole compound, a biphenylamine compound, a triphenylenylamine compound, a fluorenylamine compound, a carbazole-substituted arylamine compound, a dibenzofuran-substituted arylamine compound, and a dibenzothiophene-substituted arylamine compound).

[0344] (Light-emitting layer) The light-emitting layer is a layer containing a substance having high light-emitting characteristics (a light-emitting material or a dopant material). Various materials can be used as the dopant material. For example, a fluorescent light-emitting compound (fluorescent dopant), a phosphorescent light-emitting compound (phosphorescent dopant), etc. can be used. A fluorescent light-emitting compound is a compound that can emit light from a singlet excited state, and a light-emitting layer containing a fluorescent light-emitting compound is called a fluorescent light-emitting layer. Further, a phosphorescent light-emitting compound is a compound that can emit light from a triplet excited state, and a light-emitting layer containing a phosphorescent light-emitting compound is called a phosphorescent light-emitting layer.

[0345] Preferably, the light-emitting layer in the organic EL device of the present application contains a compound of formula (I) as a dopant material.

[0346] The light-emitting layer preferably contains at least one dopant material and at least one host material that enable it to efficiently emit light. In some documents, the dopant material is referred to as a guest material, a light-emitting body, or a light-emitting material. In some documents, the host material is referred to as a matrix material.

[0347] A single light-emitting layer may contain a plurality of dopant materials and a plurality of host materials. Further, there may be a plurality of light-emitting layers.

[0348] In this specification, a host material combined with a fluorescent dopant is referred to as a "fluorescent host", and a host material combined with a phosphorescent dopant is referred to as a "phosphorescent host". It should be noted that fluorescent hosts and phosphorescent hosts are not classified only by their molecular structures. A phosphorescent host is a material for forming a phosphorescent emission layer containing a phosphorescent dopant, but it does not mean that it cannot be used as a material for forming a fluorescent emission layer. The same may apply to fluorescent hosts.

[0349] In one embodiment, the emission layer preferably contains a compound represented by formula (I) according to the present invention (hereinafter, these compounds may be referred to as "compound (I)"). More preferably, compound (I) is contained as a dopant material. Further, compound (I) is preferably contained in the emission layer as a fluorescent dopant. Even further, compound (I) is preferably contained in the emission layer as a blue fluorescent dopant.

[0350] In one embodiment, there is no specific limitation on the content of compound (I) as a dopant material in the emission layer. Regarding sufficient emission and concentration quenching, the content is preferably 0.5 to 70% by mass, more preferably 0.8 to 30% by mass, still more preferably 1 to 30% by mass, even more preferably 1 to 20% by mass, particularly preferably 1 to 10% by mass, even more particularly preferably 1 to 5% by mass, and even further particularly preferably 2 to 4% by mass, based on the mass of the emission layer.

[0351] (Fluorescent dopant) Examples of fluorescent dopants other than compound (I) include condensed polycyclic aromatic compounds, styrylamine compounds, condensed ring amine compounds, boron-containing compounds, pyrrole compounds, indole compounds, and carbazole compounds. Among these, condensed ring amine compounds, boron-containing compounds, and carbazole compounds are preferred.

[0352] Examples of the condensed ring amine compound include a diaminopyrene compound, a diaminochrysene compound, a diaminoanthracene compound, a diaminofluorene compound, and a diaminofluorene compound condensed with one or more benzofuro skeletons.

[0353] Examples of the boron-containing compound include a pyromethene compound and a triphenylborane compound.

[0354] Examples of the blue fluorescent dopant include, for example, a pyrene compound, a styrylamine compound, a chrysene compound, a fluoranthene compound, a fluorene compound, a diamine compound, and a triarylamine compound. Specifically, N,N'-bis[4-(9H-carbazol-9-yl)phenyl]-N,N'-diphenylstilbene-4,4'-diamine (abbreviation: YGA2S), 4-(9H-carbazol-9-yl)-4'-(10-phenyl-9-anthryl)triphenylamine (abbreviation: YGAPA), 4-(10-phenyl-9-anthryl)-4'-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBAPA), and the like can be mentioned.

[0355] Examples of the green fluorescent dopant include aromatic amine compounds. Specifically, N-(9,10-diphenyl-2-anthryl)-N,9-diphenyl-9H-carbazole-3-amine (abbreviation: 2PCAPA), N-[9,10-bis(1,1'-biphenyl)-2-yl)-2-anthryl]-N,9-diphenyl-9H-carbazole-3-amine (abbreviation: 2PCABPhA), N-(9,10-diphenyl-2-anthryl)-N,N',N'-triphenyl-1,4-phenylenediamine (abbreviation: 2DPAPA), N-[9,10-bis(1,1'-biphenyl-2-yl)-2-anthryl]-N,N',N'-triphenyl-1,4-phenylenediamine (abbreviation: 2DPABPhA), N-[9,10-bis(1,1'-biphenyl-2-yl)]-N-[4-(9H-carbazol-9-yl)phenyl]-N-phenylanthracene-2-amine (abbreviation: 2YGABPhA), N,N,9-triphenylanthracene-9-amine (abbreviation: DPhAPhA), etc. can be mentioned.

[0356] Examples of the red fluorescent dopant include tetracene compounds, diamine compounds, etc. Specifically, N,N,N',N'-tetrakis(4-methylphenyl)tetracene-5,11-diamine (abbreviation: p-mPhTD), 7,14-diphenyl-N,N,N',N'-tetrakis(4-methylphenyl)acenaphtho[1,2-a]fluoranthene-3,10-diamine (abbreviation: p-mPhAFD), etc. can be mentioned.

[0357] (Phosphorescent dopant) Examples of the phosphorescent dopant include heavy metal complexes that emit phosphorescence and rare earth metal complexes that emit phosphorescence.

[0358] Examples of the heavy metal complexes include iridium complexes, osmium complexes, platinum complexes, etc. The heavy metal complexes are, for example, orthometalated complexes of metals selected from iridium, osmium, and platinum.

[0359] Examples of rare earth metal complexes include terbium complexes, europium complexes, etc. Specifically, tris(acetylacetonato)(monophenanthroline)terbium(III) (abbreviation: Tb(acac) 3 (Phen)), tris(1,3-diphenyl-1,3-propanedionato)(monophenanthroline)europium(III) (abbreviation: Eu(DBM) 3 (Phen)), tris[1-(2-thenoyl)-3,3,3-trifluoroacetonato](monophenanthroline)europium(III) (abbreviation: Eu(TTA) 3 (Phen)), etc. can be mentioned. These rare earth metal complexes are preferable as phosphorescent dopants because rare earth metal ions emit light due to electron transitions between different multiplicities.

[0360] Examples of blue phosphorescent dopants include iridium complexes, osmium complexes, platinum complexes, etc. Specifically, bis[2-(4’,6’-difluorophenyl)pyridinato-N,C2’]iridium(III) tetrakis(1-pyrazolyl)borate (abbreviation: FIr6), bis[2-(4’,6’-difluorophenyl)pyridinato-N,C2’]iridium(III) picolinate (abbreviation: Ir(CF 3 ppy) 2 (pic)), bis[2-(4’,6’-difluorophenyl)pyridinato-N,C2’]iridium(III) acetylacetonate (abbreviation: FIr acac), etc. can be mentioned.

[0361] Examples of green phosphorescent dopants include iridium complexes, etc. Specifically, tris(2-phenylpyridinato-N,C2’)iridium(III) (abbreviation: Ir(ppy) 3 ), bis(1,2-diphenyl-1H-benzimidazolato)iridium(III) acetylacetonate (abbreviation: Ir(pbi)) 2 (acac)), bis(benzo[h]quinolinato)iridium(III) acetylacetonate (abbreviation: Ir(bzq) 2Examples include (acac), etc.

[0362] Examples of the red phosphorescent dopant include iridium complexes, platinum complexes, terbium complexes, europium complexes, etc. Specifically, bis[2-(2'-benzo[4,5-α]thienyl)pyridinato-N,C3']iridium(III) acetylacetonate (abbreviation: Ir(btp) 2 (acac)), bis(1-phenylisoquinolinato-N,C2')iridium(III) acetylacetonate (abbreviation: Ir(piq) 2 (acac)), (acetylacetonato)bis[2,3-bis(4-fluorophenyl)quinoxalinato]iridium(III) (abbreviation: Ir(Fdpq) 2 (acac)), 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin platinum(II) (abbreviation: PtOEP), etc.

[0363] As described above, the light-emitting layer preferably contains at least one compound (I) as a dopant.

[0364] (host material) Examples of the host material include metal complexes such as aluminum complexes, beryllium complexes, and zinc complexes; heterocyclic compounds such as indole compounds, pyridine compounds, pyrimidine compounds, triazine compounds, quinoline compounds, isoquinoline compounds, quinazoline compounds, dibenzofuran compounds, dibenzothiophene compounds, oxadiazole compounds, benzimidazole compounds, and phenanthroline compounds; condensed polycyclic aromatic hydrocarbon (PAH) compounds such as naphthalene compounds, triphenylene compounds, carbazole compounds, anthracene compounds, phenanthrene compounds, pyrene compounds, chrysene compounds, naphthacene compounds, and fluoranthene compounds; and aromatic amine compounds such as triarylamine compounds and condensed polycyclic aromatic amine compounds. A plurality of types of host materials can be used in combination.

[0365] As the fluorescent host, a compound having a singlet energy level higher than that of the fluorescent dopant is preferable. For example, a heterocyclic compound, a condensed aromatic compound, etc. can be mentioned. As the condensed aromatic compound, an anthracene compound, a pyrene compound, a chrysene compound, a naphthacene compound, etc. are preferable. The anthracene compound is advantageously used as a blue fluorescent host.

[0366] When compound (I) is used as at least one dopant material, preferable host materials are substituted or unsubstituted polycyclic aromatic hydrocarbon (PAH) compounds, substituted or unsubstituted polycyclic heteroaromatic compounds, substituted or unsubstituted anthracene compounds, or substituted or unsubstituted pyrene compounds, preferably substituted or unsubstituted anthracene compounds, or substituted or unsubstituted pyrene compounds, more preferably substituted or unsubstituted anthracene compounds, and most preferably the anthracene compound represented by the above formula (10).

[0367] As the phosphorescent host, a compound having a triplet energy level higher than that of the phosphorescent dopant is preferable. For example, a metal complex, a heterocyclic compound, a condensed aromatic compound, etc. can be mentioned. Among these, an indole compound, a carbazole compound, a pyridine compound, a pyrimidine compound, a triazine compound, a quinoline compound, an isoquinoline compound, a quinazoline compound, a dibenzofuran compound, a dibenzothiophene compound, a naphthalene compound, a triphenylene compound, a phenanthrene compound, a fluoranthene compound, etc. can be mentioned.

[0368] (Electron transport layer) / (Electron injection layer) The electron transport layer is an organic layer formed between the light-emitting layer and the cathode, and has a function of transporting electrons from the cathode to the light-emitting layer. When the electron transport layer is formed of a plurality of layers, the organic layer or inorganic layer closer to the cathode is often defined as an electron injection layer (for example, refer to layer 8 in FIG. 1, where the electron injection layer 8 and the electron transport layer 7 form the electron injection transport unit 11). The electron injection layer has a function of efficiently injecting electrons from the cathode into the organic layer unit. Preferred electron injection materials are alkali metals, alkali metal compounds, alkali metal complexes, alkaline earth metal complexes, and rare earth metal complexes.

[0369] According to one embodiment, the electron transport layer preferably further includes one or more layers such as a second electron transport layer, an electron injection layer that enhances the efficiency and lifetime of the device, a hole blocking layer, an exciton blocking layer, or a triplet blocking layer.

[0370] According to one embodiment, the electron-donating dopant is preferably included in the interface region between the cathode and the light-emitting unit. Due to such a configuration, the organic EL device can have enhanced luminance or long lifetime. Here, the electron-donating dopant means one having a metal with a work function of 3.8 eV or less. Specific examples thereof include at least one selected from alkali metals, alkali metal complexes, alkali metal compounds, alkaline earth metals, alkaline earth metal complexes, alkaline earth metal compounds, rare earth metals, rare earth metal complexes, and rare earth metal compounds.

[0371] Examples of alkali metals include Li (work function: 2.9 eV), Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV), Cs (work function: 1.95 eV), etc. Alkali metals having a work function of 2.9 eV or less are particularly preferred. Among them, K, Rb, and Cs are preferred. Rb or Cs is more preferred. Cs is most preferred. Examples of alkaline earth metals include Ca (work function: 2.9 eV), Sr (work function: 2.0 eV to 2.5 eV), Ba (work function: 2.52 eV), etc. Alkaline earth metals having a work function of 2.9 eV or less are particularly preferred. Examples of rare earth metals include Sc, Y, Ce, Tb, Yb, etc. Rare earth metals having a work function of 2.9 eV or less are particularly preferred.

[0372] Examples of alkali metal compounds include alkali metal oxides such as Li 2 O, Cs 2 O, or K 2 O, and alkali metal halides such as LiF, NaF, CsF, and KF. Among them, LiF, Li 2 O, and NaF are preferred. Examples of alkaline earth metal compounds include BaO, SrO, CaO, and mixtures thereof, such as Ba x Sr 1-x O (0 < x < 1) and Ba x Ca 1-x O (0 < x < 1). Among them, BaO, SrO, and CaO are preferred. Examples of rare earth metal compounds include YbF 3 , ScF 3 , ScO 3 , Y 2 O 3 , Ce 2 O 3 , GdF 3 , and TbF 3 . Among these, YbF 3 , ScF 3 , and TbF 3 are preferred.

[0373] The alkali metal complex, alkaline earth metal complex, and rare earth metal complex are not particularly limited as long as they contain at least one of alkali metal ions, alkaline earth metal ions, and rare earth metal ions as metal ions. On the other hand, preferable examples of the ligand include, but are not limited to, quinolinol, benzoquinolinol, acridinol, phenanthridinol, hydroxyphenyloxazole, hydroxyphenylthiazole, hydroxydiaryloxadiazole, hydroxydiarylthiadiazole, hydroxyphenylpyridine, hydroxyphenylbenzimidazole, hydroxybenzotriazole, hydroxyfulvene, bipyridyl, phenanthroline, phthalocyanine, porphyrin, cyclopentadiene, β-diketone, and azomethine.

[0374] Regarding the addition form of the electron-donating dopant, it is preferable that the electron-donating dopant is formed in the shape of a layer or an island in the interface region. A preferable method for the formation is a method of dispersing the electron-donating dopant in the organic compound by depositing an organic compound (light-emitting material or electron-injecting material) that forms the interface region simultaneously with the deposition of the electron-donating dopant by a resistance heating deposition method.

[0375] When the electron-donating dopant is formed in the shape of a layer, the light-emitting material or electron-injecting substance that functions as an organic layer is formed in the shape of a layer at the interface. Then, the reducing dopant is deposited only by a resistance heating deposition method, and a layer having a thickness of preferably 0.1 nm to 15 nm is formed. When the electron-donating dopant is formed in the shape of an island, the light-emitting material or electron-injecting substance that functions as an organic layer is formed in the shape of an island at the interface. Then, the electron-donating dopant is deposited only by a resistance heating deposition method, and an island having a thickness of preferably 0.05 nm to 1 nm is formed. As the electron transport material used for the electron transport layer other than the compound of formula (I), an aromatic heterocyclic compound having one or more heteroatoms in the molecule can preferably be used. In particular, a nitrogen-containing heterocyclic compound is preferable.

[0376] According to one embodiment, the electron transport layer preferably contains a nitrogen-containing heterocyclic metal chelate.

[0377] According to another embodiment, the electron transport layer preferably contains a substituted or unsubstituted nitrogen-containing heterocyclic compound. Specific examples of preferred heterocyclic compounds for the electron transport layer are 6-membered azine compounds, such as pyridine compounds, pyrimidine compounds, triazine compounds, pyrazine compounds, preferably pyrimidine compounds, or triazine compounds, 6-membered condensed azine compounds, such as quinoline compounds, isoquinoline compounds, quinoxaline compounds, quinazoline compounds, phenanthroline compounds, benzoquinoline compounds, benzoisoquinoline compounds, dibenzoquinoxaline compounds, preferably quinoline compounds, isoquinoline compounds, phenanthroline compounds, 5-membered heterocyclic compounds, such as imidazole compounds, oxazole compounds, oxadiazole compounds, triazole compounds, thiazole compounds, thiadiazole compounds, condensed imidazole compounds, such as benzimidazole compounds, imidazopyridine compounds, naphthimidazole compounds, benzimidophenanthridine compounds, benzimidobenzimidazole compounds, preferably benzimidazole compounds, imidazopyridine compounds, or benzimidophenanthridine compounds.

[0378] According to another embodiment, the electron transport layer is Ar p1 Ar p2 Ar p3 preferably contains a phosphine oxide compound represented as P=O.

[0379] Ar p1 ~Ar p3 are substituents of the phosphorus atom and each independently represents a substituted or unsubstituted aryl group as described above, or a substituted or unsubstituted heterocyclic group as described above.

[0380] According to another embodiment, the electron transport layer preferably contains an aromatic hydrocarbon compound. Specific examples of the aromatic hydrocarbon compound preferable for the electron transport layer include an oligophenylene compound, a naphthalene compound, a fluorene compound, a fluoranthenyl group, an anthracene compound, a phenanthrene compound, a pyrene compound, a triphenylene compound, a benzanthracene compound, a chrysene compound, a benzophenanthrene compound, a naphthacene compound, and a benzochrysene compound, preferably an anthracene compound, a pyrene compound, and a fluoranthene compound.

[0381] (Cathode) For the cathode, a metal, an alloy, an electrically conductive compound, and a mixture thereof having a small work function (specifically, a work function of 3.8 eV or less) are preferably used. Specific examples of the material for the cathode include alkali metals such as lithium and cesium, alkaline earth metals such as magnesium, calcium, and strontium, aluminum, alloys containing these metals (for example, magnesium-silver, aluminum-lithium), rare earth metals such as europium and ytterbium, and alloys containing rare earth metals.

[0382] The cathode is usually formed by vacuum evaporation or sputtering method. Further, when using a silver paste or the like, a coating method, an inkjet method, or the like can be used.

[0383] Furthermore, the cathode can be formed using various electrically conductive materials such as silver, ITO, graphene, silicon or silicon oxide containing indium oxide-tin oxide, which are selected regardless of the work function. These electrically conductive materials are coated using a sputtering method, an inkjet method, a spin coating method, or the like.

[0384] (Insulating layer) In an organic EL element, since an electric field is applied to a thin film, pixel defects due to leakage or short circuit are likely to occur. To prevent this, it is preferable to insert an insulating thin layer between a pair of electrodes. Examples of materials used for the insulating layer include aluminum oxide, lithium fluoride, lithium oxide, cesium fluoride, cesium oxide, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, aluminum nitride, titanium oxide, silicon oxide, germanium oxide, silicon nitride, boron nitride, molybdenum oxide, ruthenium oxide, and vanadium oxide. Mixtures thereof can be used for the insulating layer, and laminates of a plurality of layers containing these materials can also be used for the insulating layer.

[0385] (Spacer layer) The spacer layer is a layer provided between a fluorescent light-emitting layer and a phosphorescent light-emitting layer when the fluorescent light-emitting layer and the phosphorescent light-emitting layer are laminated to prevent excitons generated in the phosphorescent light-emitting layer from diffusing into the fluorescent light-emitting layer, or when adjusting carrier balance. Further, the spacer layer can be provided between a plurality of phosphorescent light-emitting layers.

[0386] Since the spacer layer is provided between the light-emitting layers, the material used for the spacer layer is preferably a material having both electron transport ability and hole transport ability. In order to prevent the diffusion of triplet energy in adjacent phosphorescent light-emitting layers, it is preferable that the spacer layer has a triplet energy of 2.6 eV or more. Examples of the material used for the spacer layer include the same materials as those used for the hole transport layer described above.

[0387] (Electron blocking layer, hole blocking layer, exciton blocking layer) An electron blocking layer, a hole blocking layer, an exciton (triplet) blocking layer, etc. can be provided adjacent to the light-emitting layer.

[0388] The electron blocking layer has the function of preventing the leakage of electrons from the light-emitting layer to the hole transport layer. The hole blocking layer has the function of preventing the leakage of holes from the light-emitting layer to the electron transport layer. In order to improve the hole blocking ability, a material having a deep HOMO level is preferably used. The exciton blocking layer has the function of preventing the excitons generated in the light-emitting layer from diffusing into the adjacent layer and confining the excitons within the light-emitting layer. In order to improve the triplet blocking ability, a material having a high triplet level is preferably used.

[0389] (Method for forming the layer) The method for forming each layer of the organic EL element of the present invention is not particularly limited unless otherwise specified. Known film formation methods such as dry film formation methods and wet film formation methods can be used. Specific examples of the dry film formation method include vacuum deposition method, sputtering method, plasma method, ion plating method, etc. Specific examples of the wet film formation method include various coating methods such as spin coating method, dipping method, flow coating method, inkjet method, etc.

[0390] (Film thickness) The film thickness of each layer of the organic EL element of the present invention is not particularly limited unless otherwise specified. If the film thickness is too small, defects such as pinholes may occur, making it highly likely that sufficient luminance cannot be obtained. If the film thickness is too large, a high driving voltage needs to be applied, resulting in a decrease in efficiency. In this regard, the film thickness is preferably 0.1 nm to 10 μm, more preferably 5 nm to 0.2 μm.

[0391] (Electronic device (electronic equipment)) Furthermore, the present invention relates to an electronic device (electronic apparatus) including the organic electroluminescence element according to this application. Examples of the electronic device include display components such as organic EL panel modules, display devices such as television receivers, mobile phones, smartphones, and personal computers, and light-emitting devices for lighting and vehicle lamps.

Examples

[0392] Next, the present invention will be described in more detail according to the following synthesis examples, examples, and comparative examples, which should not be construed as limiting the scope of the present invention.

[0393] The percentages and ratios cited in the following examples are, unless otherwise specified, % by mass and mass ratio.

[0394] I Synthesis Example All experiments are carried out in a protective gas atmosphere.

[0395] Compound 1 Intermediate 1-1

[0396]

Chemical formula

[0397] Under an inert atmosphere, while maintaining the temperature below 25°C, 23.2 ml of n-butyllithium (2.7 M in hexane) was added to 6.34 g (62.7 mmol) of N,N-diisopropylamine. After stirring at room temperature for 20 minutes, the reaction mixture was diluted with 10 ml of anhydrous tetrahydrofuran to obtain a freshly prepared solution of LDA (lithium diisopropylamide).

[0398] Under an inert atmosphere, 10.00 g (52.2 mmol) of 1-bromo-3-chlorobenzene and 6.81 g (62.7 mmol) of chlorotrimethylsilane were dissolved in 30 ml of anhydrous tetrahydrofuran. The colorless clear solution was cooled to -78°C, and the prepared solution of LDA was slowly added thereto. After maintaining the temperature at -78°C for 10 minutes, the temperature was raised to -30°C and maintained for 1.5 hours. Then, the bright orange solution was slowly warmed to room temperature and stirred for 17 hours to obtain a yellow milky solution. The reaction mixture was poured into water and extracted with ethyl acetate. Then, the organic extract was treated with MgSO 4It was dried using [specific method], filtered, and the solvent was removed by a rotary evaporator. The residue was purified by silica gel column chromatography using cyclohexane as the eluent to obtain 12.61 g (yield 92%) of Intermediate 1-1 as a colorless transparent oil. 1 H NMR (300 MHz, DMSO-d 6 ) δ 7.59 (dd, J = 7.9, 1.1 Hz, 1H), 7.43 (dd, J = 8.0, 1.1 Hz, 1H), 7.28 (t, J = 7.9 Hz, 1H), 0.51 (s, 9H).

[0399] Intermediate 1-2

[0400]

Chemical Structure

[0401] 5.00 g (18.97 mmol) of Intermediate 1-1, 2.97 g (19.91 mmol) of 4-tert-butylaniline, and 7.29 g (76.00 mmol) of sodium tert-butoxide were added to 100 ml of toluene. The suspension was degassed using three freeze-degas-thaw cycles, and 347 mg (2 mol%) of tris(dibenzylideneacetone)dipalladium(0) and 439 mg (8 mol%) of tri-tert-butylphosphonium tetrafluoroborate were added to the reaction mixture. After two additional freeze-degas-thaw cycles, the reaction mixture was heated at 60 °C for 25 h. The reaction was cooled to room temperature and diluted with toluene. The organic extract was washed with water and dried using MgSO 4 It was dried using [specific method], filtered, and the solvent was removed by a rotary evaporator. The residue was purified by silica gel column chromatography using cyclohexane as the eluent to obtain 4.21 g (yield 67%) of Intermediate 1-2 as a pale orange oil. 1 H NMR (300 MHz, DMSO-d 6)δ 7.31 - 7.25 (m, 2H), 7.20 - 7.16 (m, 2H), 7.13 (dd, J = 8.1, 0.9 Hz, 1H), 7.09 (dd, J = 7.5, 0.9 Hz, 1H), 6.71 - 6.68 (m, 2H), 1.24 (s, 9H), 0.36 (s, 9H).

[0402] Intermediate 1-3

[0403]

Chem.

[0404] 3.00 g (9.04 mmol) of Intermediate 1-2, 2.12 g (9.94 mmol) of 1-bromo-4-tert-butylbenzene, and 3.47 g (36.1 mmol) of sodium tert-butoxide were added to 50 ml of toluene. The suspension was degassed using three freeze-degas-thaw cycles, and 166 mg (2 mol%) of tris(dibenzylideneacetone)dipalladium(0) and 209 mg (8 mol%) of tri-tert-butylphosphonium tetrafluoroborate were added to the reaction mixture. After two additional freeze-degas-thaw cycles, the reaction mixture was heated at 60 °C for 19 h. The reaction was cooled to room temperature and diluted with toluene. The organic extract was washed with water, dried over MgSO 4 and filtered through a silica pad, and the pad was further washed with toluene. The solvent was removed by rotary evaporator, and the residue was purified by silica gel column chromatography using cyclohexane as the eluent to obtain a mixture of the desired product and 1-bromo-4-tert-butylbenzene. The remaining 1-bromo-4-tert-butylbenzene was removed by distillation at 300 °C under high vacuum to give 3.74 g (98% yield) of Intermediate 1-3 as a colorless transparent resin. 1 H NMR (300 MHz, DMSO-d 6)δ 7.45 (t, J = 7.9 Hz, 1H), 7.34 (dd, J = 7.9, 1.2 Hz, 1H), 7.31 - 7.23 (m, 4H), 6.90 (dd, J = 7.8, 1.2 Hz, 1H), 6.81 - 6.71 (m, 4H), 1.25 (s, 18H), 0.17 (s, 9H).

[0405] Intermediate 1-4

[0406]

Chem.

[0407] 10.0 g (40.6 mmol) of 1-bromo-9H-carbazole, 13.4 g (52.8 mmol) of bis(pinacolato)diboron, and 16.0 g (168.2 mmol) of potassium acetate were suspended in 100 ml of anhydrous N,N-dimethylformamide. The reaction vessel was evacuated to high vacuum and the suspension was degassed by filling with argon. This operation was repeated 7 times. After adding 2.32 g (7 mol%) of the complex of [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) with dichloromethane to the reaction mixture, evacuation-filling was repeated 2 times. Then, the reaction mixture was heated at 80 °C for 19 hours. After cooling to room temperature, the reaction was diluted with 10 ml of diethyl ether and 50 ml of cyclohexane and filtered through a small silica gel pad. The pad was washed with a 5:1 mixture of 300 ml of cyclohexane and diethyl ether. The solvent was removed by rotary evaporator and the residue was purified by silica gel column chromatography using cyclohexane as the eluent. The fractions containing the product were combined and the solvent was removed by rotary evaporator until a white solid precipitated. The suspension was filtered to obtain 10.25 g (yield 86%) of Intermediate 1-4 as a white solid. 1 H NMR (300 MHz, DMSO-d 6)δ 10.33(s,1H),8.31 - 8.23(m,1H),8.14 - 8.09(m,1H),7.75(dt,J = 8.1,0.9Hz,1H),7.71(dd,J = 7.2,1.3Hz,1H),7.44 - 7.36(m,1H),7.23 - 7.13(m,2H),1.41(s,12H).

[0408] Intermediate 1 - 5

[0409]

Chem.

[0410] 3.65 g (7.86 mmol) of Intermediate 1 - 3, 2.54 g (8.65 mmol) of Intermediate 1 - 4, and 6.68 g (31.5 mmol) of K 3 PO 4 were suspended in a mixture of 50 ml of toluene, 25 ml of tetrahydrofuran, and 20 ml of water. The suspension was degassed using three freeze - degassing - thaw cycles, and 17.7 mg (1 mol%) of palladium(II) acetate and 193.7 mg (6 mol%) of SPhos (2 - dicyclohexylphosphino - 2’,6’ - dimethoxybiphenyl) were added to the reaction mixture. After two more freeze - degassing - thaw cycles, the reaction mixture was heated at 90 °C for 20 h, then 8.8 mg (0.5 mol%) of palladium(II) acetate and 96.9 mg (3 mol%) of SPhos were added, and the reaction was heated at 90 °C for an additional 1 h. The reaction was then cooled to room temperature, extracted with dichloromethane, and the organic extract was dried over anhydrous MgSO 4It was dried using [specific method] and filtered through a small silica pad. The pad was washed with dichloromethane and the solvent of the filtrate was removed using a rotary evaporator. The crude product was purified by silica gel column chromatography using a mixture of heptane and dichloromethane (0 - 20% gradient) to obtain 2.17 g of a colorless foam. The product was further purified by triturating in 40 ml of cyclohexane at room temperature and then in 40 ml of refluxing petroleum ether 60 - 80. The resulting solid was filtered at room temperature, washed with petroleum ether and dried under vacuum to obtain 1.76 g (38% yield) of Intermediate 1 - 5 as a white powder. 1 1H NMR (300 MHz, dichloromethane - d 2 ) δ 8.14 (dt, J = 6.5, 1.0 Hz, 2H), 8.10 (dd, J = 7.5, 1.3 Hz, 1H), 7.54 - 7.47 (m, 1H), 7.46 - 7.41 (m, 2H), 7.40 - 7.35 (m, 2H), 7.35 - 7.31 (m, 2H), 7.31 - 7.24 (m, 3H), 7.21 (dd, J = 7.3, 1.3 Hz, 1H), 7.16 (dd, J = 7.9, 1.3 Hz, 1H), 7.14 - 7.06 (m, 2H), 7.01 - 6.93 (m, 2H), 1.38 (s, 9H), 1.36 (s, 9H), 0.45 (s, 9H).

[0411] Compound 1

[0412]

Chemical Structure

[0413] 0.50 g (0.84 mmol) of Intermediate 1-5 was dissolved in 10 ml of 1,2-dichlorobenzene and degassed using three freeze-degas-thaw cycles. 0.34 g (3.36 mmol) of triethylamine was added to the reaction mixture, followed by the slow addition of 1.68 ml (1.68 mmol) of trichloroborane (1 M solution in heptane). The reaction mixture was heated at 180 °C for 42 h to give a clear oily solution. After cooling to room temperature, the gel-like mixture was diluted with 70 ml of cyclohexane and filtered through a silica pad. The pad was washed with 200 ml of cyclohexane to remove the solvent, and the desired product was eluted into different fractions using 100 ml of toluene followed by 100 ml of dichloromethane. The solvent was removed using a rotary evaporator, and the crude product was purified by silica gel column chromatography using a mixture of heptane and toluene (0 - 20% gradient) to give the product as an oil, which was crystallized using a few drops of diethyl ether. The solid was collected by filtration to give 0.13 g (29% yield) of Compound 1 as a pale yellow powder. 1 H NMR (300 MHz, dichloromethane-d 2 ) δ 8.77 (d, J = 2.5 Hz, 1H), 8.54 - 8.44 (m, 1H), 8.39 (dd, J = 7.9, 1.0 Hz, 1H), 8.29 - 8.15 (m, 2H), 8.08 - 7.99 (m, 1H), 7.83 - 7.73 (m, 2H), 7.68 - 7.49 (m, 4H), 7.47 (td, J = 7.4, 1.1 Hz, 1H), 7.42 - 7.31 (m, 2H), 6.82 (d, J = 9.0 Hz, 1H), 6.72 (dd, J = 8.5, 0.7 Hz, 1H), 1.52 (s, 9H), 1.42 (s, 9H).

[0414] Compound 2

[0415]

Chemical Structure

[0416] 5.00 g (18.97 mmol) of Intermediate 1-1, 5.83 g (2.86 mmol) of 3,6-di-tert-butyl-9H-carbazole, and 7.29 g (76.00 mmol) of sodium tert-butoxide were added to 150 ml of xylene. The suspension was degassed using three freeze-degas-thaw cycles, and 347 mg (2 mol%) of tris(dibenzylideneacetone)dipalladium(0) and 329 mg (3 mol%) of Xantphos (4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) were added to the reaction mixture. After two additional freeze-degas-thaw cycles, the reaction mixture was heated at 120 °C for 15 hours. Further, 347 mg (2 mol%) of tris(dibenzylideneacetone)dipalladium(0) and 329 mg (3 mol%) of Xantphos were added to the reaction mixture, and the reaction was heated for a total of 50 hours. The reaction was then cooled to room temperature, extracted with toluene, and the organic extract was dried over anhydrous MgSO 4 and filtered through a small silica pad. The pad was washed with toluene, and the solvent of the filtrate was removed using a rotary evaporator. The crude product was purified by silica gel column chromatography using heptane to obtain 3.25 g (yield 37%) of Intermediate 2-1 as a colorless foam. 1 H NMR (300 MHz, DMSO-d 6 ) δ 8.27 (d, J = 1.5 Hz, 2H), 7.66 (dd, J = 8.0, 1.3 Hz, 1H), 7.59 (t, J = 7.8 Hz, 1H), 7.45 (dd, J = 8.6, 1.9 Hz, 2H), 7.13 (dd, J = 7.6, 1.3 Hz, 1H), 6.89 (d, J = 8.5 Hz, 2H), 1.41 (s, 18H), 0.14 (s, 9H).

[0417] Intermediate 2-2

[0418]

Chemical formula

[0419] 5.00 g (17.89 mmol) of 3,6-di-tert-butyl-9H-carbazole was dissolved in 50 ml of acetic acid, and 3.18 g (17.89 mmol) of N-bromosuccinimide was added little by little to the white suspension. After 4 hours, 200 ml of water was added and the reaction mixture was stirred for an additional 30 minutes. The resulting precipitate was filtered and the solid was washed with water, saturated NaHCO 3 solution, and then with water again. The crude product was purified by silica gel column chromatography using a mixture of heptane and toluene (0 - 40% gradient), followed by re-purification by silica gel column chromatography using a mixture of cyclohexane and dichloromethane (0 - 3% gradient). The pure fractions were combined and the solvent was removed by rotary evaporator to obtain 3.42 g (45% yield) of Intermediate 2-2 as a colorless transparent oil. 1 H NMR (300 MHz, DMSO-d 6 ) δ 11.10 (s, 1H), 8.20 (d, J = 1.5 Hz, 1H), 8.18 (dd, J = 1.4, 0.9 Hz, 1H), 7.57 (d, J = 1.7 Hz, 1H), 7.50 (dd, J = 8.6, 1.8 Hz, 1H), 7.45 (dd, J = 8.7, 0.8 Hz, 1H), 1.40 (s, 18H).

[0420] Intermediate 2-3

[0421]

Chemical Structure

[0422] 3.40 g (9.49 mmol) of Intermediate 2-2, 3.13 g (12.34 mmol) of bis(pinacolato)diboron, and 3.73 g (39.20 mmol) of potassium acetate were suspended in 40 ml of anhydrous N,N-dimethylformamide. The reaction vessel was evacuated to high vacuum and backfilled with argon to degas the suspension. This operation was repeated 7 times. After adding a complex of 542 mg (7 mol%) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) with dichloromethane to the reaction mixture, evacuation-backfilling was repeated 2 times. The reaction mixture was then heated at 80 °C for 21 h. After cooling to room temperature, the reaction was diluted with diethyl ether, washed with water, dried over MgSO 4 and filtered through a small silica gel pad. The pad was washed with a 5:1 mixture of 300 ml of cyclohexane and diethyl ether. The solvent was removed by rotary evaporator and 30 ml of petroleum ether 60-80 was added to the brown residue. The solution was then concentrated until a white powder precipitated. The solid was filtered and washed with cold petroleum ether to afford 3.05 g (79% yield) of Intermediate 2-3 as a white powder. 1 H NMR (300 MHz, DMSO-d 6 ) δ 10.04 (s, 1H), 8.34 (d, J = 2.0 Hz, 1H), 8.16 (d, J = 1.9 Hz, 1H), 7.71 (d, J = 2.1 Hz, 1H), 7.60 (d, J = 8.6 Hz, 1H), 7.45 (dd, J = 8.6, 2.0 Hz, 1H), 1.41 (s, 30H).

[0423] Intermediate 2-4

[0424]

Chemical formula

[0425] 2.00 g (4.33 mmol) of Intermediate 2-1, 2.46 g (6.06 mmol) of Intermediate 2-3, and 3.67 g (17.3 mmol) of K 3 PO 4was suspended in a mixture of 50 ml of toluene, 25 ml of dioxane, and 15 ml of water. The suspension was degassed using three freeze-degassing-thaw cycles, and 9.7 mg (1 mol%) of palladium(II) acetate and 107 mg (6 mol%) of SPhos were added to the reaction mixture. After two additional freeze-degassing-thaw cycles, the reaction mixture was heated at 80 °C for 10 h, then 0.35 g (0.86 mmol) of intermediate 2-3, 9.7 mg (1 mol%) of palladium(II) acetate, and 107 mg (6 mol%) of SPhos were added, and the reaction was heated to 80 °C for an additional 12 h. The reaction was then cooled to room temperature, extracted with toluene, and the organic extract was dried over anhydrous MgSO 4 and filtered through a small silica pad. The pad was washed with toluene, and the solvent of the filtrate was removed using a rotary evaporator. The crude product was purified by silica gel column chromatography using a mixture of heptane and tetrahydrofuran (0 - 1% gradient) to give 2.80 g (92% yield) of intermediate 2-4 as a white foam. 1 H NMR (300 MHz, DMSO-d 6 ) δ 10.70 (s, 1H), 8.27 (d, J = 1.9 Hz, 2H), 8.22 (d, J = 1.8 Hz, 1H), 8.20 - 8.17 (m, 1H), 7.70 (t, J = 7.6 Hz, 1H), 7.56 (dd, J = 7.5, 1.3 Hz, 1H), 7.54 - 7.47 (m, 2H), 7.46 - 7.41 (m, 2H), 7.33 (d, J = 1.8 Hz, 1H), 7.24 (d, J = 8.5 Hz, 1H), 7.20 (dd, J = 7.8, 1.2 Hz, 1H), 7.12 (d, J = 8.6 Hz, 1H), 1.47 (s, 9H), 1.45 - 1.43 (m, 18H), 1.42 (s, 9H), -0.72 (s, 9H).

[0426] Compound 2

[0427]

Chemical Structure

[0428] 2.44 g (3.46 mmol) of Intermediate 2-4 was dissolved in 70 mL of 1,2-dichlorobenzene, and the reaction vessel was purged with nitrogen. 2.42 mL (13.84 mmol) of N,N-diisopropylethylamine was added at room temperature, followed by the dropwise addition of 5.20 mL (5.20 mmol) of tribromoborane (1 M solution in heptane). The resulting clear, pale orange solution was heated at 145 °C for 20 hours and then cooled to room temperature. 15 mL of methanol was slowly added to quench the reaction, and the resulting solution was poured into 200 mL of methanol. The yellow precipitate was stirred for 5 minutes, then filtered, washed with methanol, and dried to obtain 1.11 g (50% yield) of Compound 2 as a yellow solid. 1 H NMR (300 MHz, THF-d 8 ) δ 9.00 (d, J = 1.9 Hz, 1H), 8.65 (d, J = 8.7 Hz, 1H), 8.58 (d, J = 1.9 Hz, 1H), 8.54 (d, J = 1.7 Hz, 1H), 8.52 (d, J = 8.3 Hz, 1H), 8.46 - 8.35 (m, 3H), 8.35 (d, J = 1.6 Hz, 1H), 8.31 (d, J = 1.9 Hz, 1H), 7.95 (t, J = 8.1 Hz, 1H), 7.70 (dd, J = 8.9, 2.0 Hz, 1H), 7.62 (dd, J = 8.7, 2.1 Hz, 1H), 1.61 (s, 18H), 1.54 - 1.50 (m, 18H).

[0429] Compound 3 Intermediate 3-1

[0430]

Chemical Structure

[0431] 6.00 g (22.76 mmol) of Intermediate 1-1, 10.81 g (25.03 mmol) of 3,6-bis(4-(tert-butyl)phenyl)-9H-carbazole (synthesized according to the procedure described in New Journal of Chemistry, 2019, page 16629), and 4.37 g (45.5 mmol) of sodium tert-butoxide were added to 175 mL of xylene. The suspension was degassed by three freeze-degas-melt cycles, and 417 mg (2 mol%) of tris(dibenzylideneacetone)dipalladium(0) and 527 mg (4 mol%) of Xantphos (4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) were added to the reaction mixture. After two additional freeze-degas-melt cycles, the reaction mixture was heated at 120 °C for 15 h. A further 347 mg (2 mol%) of tris(dibenzylideneacetone)dipalladium(0) and 329 mg (3 mol%) of Xantphos were added to the reaction mixture, and the reaction was heated for a further total of 41 h. The reaction was then cooled to room temperature, extracted with toluene, the organic extract was dried over anhydrous magnesium sulfate, and filtered through a small silica pad. The pad was washed with toluene, and the solvent of the filtrate was removed on a rotary evaporator. The crude product was purified by silica gel column chromatography using heptane / THF (95 / 5) to give 1.6 g (yield 11%) of Intermediate 3-1 as a pale yellow foam. ESI-MS: 614.3 [M+H] +

[0432] Intermediate 3-2

[0433]

Chemical Structure

[0434] 2.46 g (4.00 mmol) of Intermediate 3-1, 2.11 g (5.21 mmol) of Intermediate 2-3, and 3.40 g (16.0 mmol) of potassium phosphate were suspended in a mixture of 40 mL of toluene, 10 mL of dioxane, and 10 mL of water. The suspension was degassed by three freeze-degas-thaw cycles, and 18 mg (2 mol%) of palladium(II) acetate and 197 mg (12 mol%) of SPhos were added to the reaction mixture. After two additional freeze-degas-thaw cycles, the reaction mixture was heated at 90 °C for 15 h. The reaction was then cooled to room temperature, extracted with toluene, and the organic extract was dried over anhydrous magnesium sulfate and dry deposited onto silica. The crude product was purified by silica gel column chromatography using a mixture of heptane and toluene (0 - 35% gradient) to give 1.4 g (41% yield) of Intermediate 3-2 as a pale yellow foam. ESI-MS: 857.5 [M+H] +

[0435] Compound 3

[0436]

Chemical Structure

[0437] 3.70 g (4.32 mmol) of Intermediate 3-2 was dissolved in 80 mL of 1,2-dichlorobenzene, and the reaction vessel was purged with nitrogen. 3.02 mL (17.26 mmol) of N,N-diisopropylethylamine was added at room temperature, followed by the dropwise addition of 8.50 mL (8.50 mmol) of tribromoborane (1 M solution in heptane). The resulting clear pale orange solution was heated to 160 °C for 16 h and then cooled to room temperature. 5 mL of a 10% aqueous solution of sodium acetate was slowly added to quench the reaction. The aqueous phase was extracted with toluene (2 × 20 mL). The organic phase was filtered through a silica plug, which was rinsed with toluene (40 mL). The filtrate was poured into 500 mL of methanol. The yellow precipitate was stirred for 5 min, then filtered, washed with methanol, and dried to give 2.24 g (66% yield) of Compound 3 as a yellow solid. ESI-MS: 793.5 [M+H] +

[0438] Compound 4 Intermediate 4-1

[0439]

Chem.

[0440] 41.0 g (0.13 mol) of 1-bromo-3-chloro-5-iodobenzene, 23.0 g (0.13 mol) of 4-tert-butylphenylboronic acid, 4.48 g (3.88 mmol) of tetrakis(triphenylphosphine)palladium(0), and 300 g of 10% aqueous sodium carbonate solution were suspended in 120 mL of toluene and 120 mL of ethanol. The suspension was evacuated three times and refilled with argon, and heated at 73 °C for 22 h. The pale yellow suspension was cooled to room temperature and quenched with 200 mL of water. The organic phase was washed with water (2 × 200 mL) and dried over sodium sulfate. The product was further purified by MPLC (silica gel, heptane) using CombiFlash Companion to give 39.6 g (93% yield) of Intermediate 4-1 as a white solid. 1 H NMR (300 MHz, CDCl 3 ) δ 7.64 (t, 1H), 7.52 (t, 1H), 7.51 - 7.46 (m, 5H), 1.40 (s, 9H).

[0441] Intermediate 4-2

[0442]

Chem.

[0443] 16 mL (0.11 mol) of diisopropylamine was dissolved in 100 mL of tetrahydrofuran and was added dropwise with 45 mL of n-butyllithium (2.5 M in hexane) at -30 °C. This solution was slowly added to a pre-cooled solution containing 200 ml of tetrahydrofuran, 30.0 g (93 mmol) of Intermediate 4-1 and 14.1 ml (0.11 mol) of chlorotrimethylsilane at a maximum temperature of -70 °C. After the addition was complete, the pale yellow solution was further stirred at -75 °C for 45 minutes. 100 mL of 5% aqueous ammonium chloride solution was added and the reaction mixture was stirred until it reached room temperature. The solution was diluted with 200 mL of heptane and the organic phase was washed with 200 mL of water and 100 mL of saturated aqueous sodium chloride solution. The organic phase was dried over sodium sulfate and concentrated under vacuum. The product was further purified by MPLC (silica gel, heptane) using CombiFlash Companion to obtain 36.7 g (98% yield) of Intermediate 4-2 as a colorless oil. 1 H NMR (300 MHz, CDCl 3 ) δ 7.73 (d, 1H), 7.54 (d, 1H), 7.52 (d, 4H), 1.39 (s, 9H), 0.60 (s, 9H).

[0444] Intermediate 4-3

[0445]

Chemical Structure

[0446] 2.98 g (7.52 mmol) of intermediate 4-2, 2.31 g (8.27 mmol) of 3,6-di-tert-butyl-9H-carbazole, 0.28 g (0.3 mmol) of tris(dibenzylideneacetone)dipalladium(0), 0.35 g (0.6 mmol) of 4,5-bis(di-phenylphosphino)-9,9-dimethylxanthene (xantphos), and 2.9 g (30 mmol) of sodium tert-butoxide were suspended in 30 mL of o-xylene. The orange suspension was evacuated three times and filled with argon, and stirred at 117 °C for 22 hours. The dark brown reaction mixture was cooled to room temperature, diluted with 100 ml of toluene, then extracted with 100 ml of water and 100 ml of saturated aqueous sodium chloride solution, dried over sodium sulfate, and concentrated under vacuum. The product was further purified by MPLC (silica gel, heptane) using a CombiFlash Companion. The resulting oil was treated with 100 mL of methanol and stirred at 40 °C until a suspension was formed, and 1.37 g (yield 30%) of intermediate 4-3 was obtained as a white solid. ESI-MS (positive, m / z): C 39 H 48 The exact mass of ClNSi = 593.32; found 594.4 [M+1] +

[0447] Intermediate 4-4

[0448]

Chemical Structure

[0449] 2.00 g (3.4 mmol) of intermediate 4-3, 1.64 g (4.0 mmol) of intermediate 2-3, 16 mg (0.07 mmol) of palladium(II) acetate, 171 mg (0.42 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos), and 2.86 g (13.4 mmol) of tripotassium phosphate were dissolved in a mixture of 25 mL of toluene, 15 mL of 1,4-dioxane, and 7 mL of water. The solution was evacuated three times and refilled with argon, and heated at 77 °C for 20 h. The reaction mixture was cooled to room temperature, poured into 100 mL of water, and stirred for 10 min. The passed organic matter was filtered through a 3-cm silica gel layer, and the silica gel layer was rinsed with 200 mL of heptane. The collected eluate was concentrated under vacuum. The product was dissolved in ethanol, and when water was added, a suspension formed. The suspension was stirred for 30 min, then filtered, and the solid was washed with water. The solid was dissolved in dichloromethane, dried over sodium sulfate, and concentrated under vacuum to give 1.8 g (64%) of intermediate 4-4 as a white solid. ESI-MS (negative, m / z): C 59 H 72 N 2 Exact mass of Si = 836.55; found 835.6 [M−1] +

[0450] Compound 4

[0451]

Chemical Structure

[0452] 1.80 g (2.15 mmol) of intermediate 4-4 was dissolved in 40 mL of 1,2-dichlorobenzene. 1.5 mL (8.6 mmol) of N,N-diisopropylethylamine and 3.2 mL of tribromoborane (1.0 M in heptane) were added dropwise. The pale yellow solution was heated at 145 °C for 24 h, cooled to room temperature, and slowly poured into 300 mL of methanol. The suspension was stirred for 10 min, then filtered, and the solid was washed with methanol and ethanol. The solid was dried under vacuum to give 1.15 g (69% yield) of Compound 4 as a yellow solid. ESI-MS (positive, m / z): C 56 H 61 BN 2 Exact mass of = 772.49; measured value 773.8 [M+1] +

[0453] Compound 5 Intermediate 5-1

[0454]

Chem.

[0455] 12.0 g (47.7 mmol) of 8-chloro-7H-benzo[c]carbazole, 18.2 g (71.5 mmol) of bis(pinacolato)diboron, 1.81 g (3.8 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (XPhos), and 9.4 g (95 mmol) of potassium acetate were suspended in 200 mL of dioxane. 873 mg (0.95 mmol) of tris(dibenzylideneacetone)dipalladium(0) was added, and the suspension was heated at 101 °C for 40 minutes. The suspension was cooled and diluted with 40 mL of dioxane. The suspension was filtered through a 3-cm silica gel layer, and the silica gel layer was rinsed with 100 mL of dioxane. The collected eluate was concentrated under vacuum, and the solid was recrystallized from 50 mL of heptane. The solid was washed with 30 mL of cooled heptane and further dried under vacuum to obtain 12.3 g (yield 75%) of Intermediate 5-1 as a white solid. ESI-MS (positive, m / z): C 22 H 22 BNO 2 Exact mass of = 343.17; measured value 344.4 [M+1] +

[0456] Intermediate 5-2

[0457]

Chem.

[0458] 3.00 g (6.49 mmol) of Intermediate 2-1, 2.45 g (7.14 mmol) of Intermediate 5-1, 29 mg (0.13 mmol) of palladium(II) acetate, 320 mg (0.78 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos), and 5.51 g (26.0 mmol) of tripotassium phosphate were dissolved in a mixture of 55 mL of o-xylene, 30 mL of 1,4-dioxane, and 15 mL of water. The reaction mixture was evacuated three times and refilled with argon, and heated at 84 °C for 3 hours. The reaction mixture was cooled, and 40 mL of toluene and 40 mL of water were added. The organic phase was washed with water (3 × 40 mL), dried over sodium sulfate, and concentrated under vacuum. The product was further purified by MPLC (silica gel, toluene) using a CombiFlash Companion. The resulting white foam was heated with 50 mL, and the resulting turbid solution was cooled to room temperature. 10 mL of water was added, and the mixture was heated until a suspension was formed. The suspension was stirred for 20 minutes, cooled to room temperature, and filtered. The solid was dissolved in dichlorobenzene, dried over magnesium sulfate, and the solution was concentrated under vacuum to give 3.40 g (yield 82%) of Intermediate 5-2 as a white solid. ESI-MS (negative, m / z): C 45 H 46 N 2 Exact mass of Si = 642.34; found 641.6 [M−1] +

[0459] Compound 5

[0460]

Chemical Structure

[0461] 3.40 g (5.29 mmol) of Intermediate 5-2 was dissolved in 70 mL of 1,2-dichlorobenzene. 3.7 mL (21.2 mmol) of N,N-diisopropylethylamine and 10.6 mL of tribromoborane (1.0 M in heptane) were added dropwise. The yellow solution was heated at 150 °C for 18 h. The orange solution was cooled and 4 mL of 10% aqueous sodium acetate solution was slowly added. The mixture was added dropwise into 600 mL of methanol. The yellow suspension was filtered and the solid was washed with ethanol and heptane. The solid was heated in a mixture of 150 mL of dichloromethane and 100 mL of isopropanol and then slowly cooled to room temperature. The suspension was filtered and the solid was washed with isopropanol to give 2.12 g (69% yield) of Compound 5 as a yellow solid. ESI-MS (negative, m / z): C 42 H 35 BN 2 exact mass of = 578.29; found 579.7 [M-1] +

[0462] Compound 6 Intermediate 6-1

[0463]

Chemical Structure

[0464] 17.3 g (70.0 mmol) of 4-bromodibenzofuran, 12.48 g (77.0 mmol) of 2,6-dichloroaniline, and 10.09 g (105 mmol) of sodium tert-butoxide were suspended in 150 mL of o-xylene. The suspension was degassed with Ar, and 2.62 g (6 mol%) of BINAP and 471 mg (3 mol%) of tris(dibenzylideneacetone)dipalladium(0) were added to the reaction mixture. The reaction mixture was heated to 155 °C for 3 hours. The reaction was cooled to room temperature, diluted with toluene / water, and filtered through celite. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extracts were washed with water, saturated brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane / toluene as the eluent to obtain 19.26 g (84% yield) of Intermediate 6-1 as a white solid. ESI-MS: 328.3 [M+H] +

[0465] Intermediate 6-2

[0466]

Chemical Structure

[0467] 17.72 g (54.0 mmol) of Intermediate 6-1 and 14.93 g (108 mmol) of potassium carbonate were suspended in N,N-dimethylacetamide. The suspension was degassed with Ar, and 485 mg (4 mol%) of palladium acetate and 1.59 g (8 mol%) of tricyclohexylphosphonium tetrafluoroborate were added to the reaction mixture. The reaction mixture was heated at 130 °C for 3.5 hours. The reaction was cooled to room temperature, diluted with toluene / water, and filtered through celite. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extracts were washed with water, brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane / toluene as the eluent to obtain 10.39 g (66% yield) of Intermediate 6-2 as a white solid. ESI-MS: 290.0 [M-H]-

[0468] Intermediate 6-3

[0469]

Chem.

[0470] 9.63 g (33.0 mmol) of Intermediate 6-2, 10.06 g (39.6 mmol) of bis(pinacolato)diboron, and 8.10 g (83.0 mmol) of potassium acetate were suspended in 125 mL of 1,4-dioxane. The suspension was degassed with Ar, and 453 mg (1.5 mol%) of tris(dibenzylideneacetone)dipalladium(0) and 406 mg (3 mol%) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl were added to the reaction mixture. The reaction mixture was heated to 105 °C for 4 hours. The reaction was cooled to room temperature, diluted with toluene / water, and filtered through celite. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extract was washed with water, brine, dried over sodium sulfate, filtered, and evaporated. The residue was refluxed in 70 mL of heptane for 15 minutes, cooled to room temperature, and then the orange suspension was filtered and dried in vacuo. 11.40 g (yield 90%) of Intermediate 6-3 was obtained as a beige solid. ESI-MS: 382.3 [M-H] -

[0471] Intermediate 6-4

[0472]

Chem.

[0473] 3.86 g (6.5 mmol) of Intermediate 4-3, 2.74 g (7.15 mmol) of Intermediate 6-3, and 4.24 g (13.0 mmol) of cesium carbonate were suspended in a mixture of toluene / ethanol / water (60 mL / 20 mL / 10 mL). The suspension was degassed with Ar, and 44 mg (3 mol%) of palladium acetate and 186 mg (6 mol%) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl were added to the reaction mixture. The reaction mixture was heated at 60 °C for 2.5 h. The reaction was cooled to room temperature and diluted with toluene / water. The layers were separated and the aqueous layer was further extracted with toluene. The organic extracts were washed with water and saturated brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane / toluene as the eluent to give 4.46 g (84% yield) of Intermediate 6-4 as a white foam. ESI-MS: 813.6 [M-H] -

[0474] Compound 6

[0475]

Chemical formula

[0476] 3.26 g (4.00 mmol) of intermediate 6-4 was dissolved in 50 mL of 1,2-dichlorobenzene and degassed with Ar. After adding 2.79 mL (16.0 mmol) of N-ethyl-N-isopropylpropan-2-amine to the reaction mixture, 6.00 mL (6.00 mmol) of tribromoborane (1 M solution in heptane) was slowly added. The reaction mixture was heated at 160 °C for 28.5 h. Then, after adding an additional 2.00 mL (2.00 mmol) of tribromoborane (1 M solution in heptane), it was heated at 160 °C for 16.5 h. After cooling to room temperature, the reaction was quenched with water and extracted with 1,2-dichlorobenzene. The organic layer was washed with saturated brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane / toluene as the eluent to give 1.36 g (45% yield) of compound 6 as a yellow solid. ESI-MS: 751.9 [M+H] +

[0477] Compound 7 Intermediate 7-1

[0478]

Chemical formula

[0479] 48.0 g (0.16 mol) of 1,3-dibromo-5-(tert-butyl)benzene was dissolved in 500 mL of tetrahydrofuran. 70.0 mL of n-butyllithium (2.5 M in hexane) was added dropwise at a maximum temperature of -71 °C over 45 min. 45.9 g (0.18 mol) of iodine was added in portions over 15 min at a maximum temperature of -55 °C, and the resulting suspension was stirred at -78 °C for an additional 45 min. 400 mL of 10% aqueous sodium sulfite solution was added, and the reaction mixture was stirred further until it reached room temperature. The organic phase was separated, and the aqueous phase was extracted with chlorohexane (2 × 150 mL). The organic phase was washed with water (2 × 200 mL) and saturated aqueous sodium chloride solution. The organic phase was dried over sodium sulfate and concentrated under vacuum to give 54.7 g (83% yield) of intermediate 7-1 as an orange oil. 1 1H NMR (300 MHz, DMSO-d 6 ) δ 7.77 (t, 1H), 7.72 (t, 1H), 7.57 (t, 1H), 1.26 (s, 9H).

[0480] Intermediate 7-2

[0481]

Chemical Structure

[0482] 3.22 g (10.00 mmol) of 9,9-dimethyl-2,7-di(tert-butyl)-9,10-dihydroacridine, 3.73 g (11.00 mmol) of Intermediate 7-1, and 2.88 g (30.00 mmol) of sodium acetate were suspended in 57 mL of xylene. After degassing the suspension using three freeze-degas-thaw cycles, 225 mg (1.00 mmol) of palladium acetate and 554 mg (1.00 mmol) of 1,1'-bis(diphenylphosphino)ferrocene were added to the mixture. Then, after two additional freeze-degas-thaw cycles, the reaction mixture was stirred at 100 °C for 1 hour. The reaction was cooled to room temperature and concentrated. The residue was purified by silica gel column chromatography using cyclohexane as the eluent to obtain 3.42 g (64% yield) of Intermediate 7-2 as a white solid. ESI-MS: 534.6 [M+H] +

[0483] Intermediate 7-3

[0484]

Chemical Structure

[0485] 3.42 g (6.42 mmol) of intermediate 7-1, 2.86 g (7.06 mmol) of intermediate 2-3, and 5.45 g (25.68 mmol) of potassium phosphate were dissolved in 54 mL of toluene, 27 mL of dioxane, and 16 mL of water. After degassing the solution using three freeze-degas-thaw cycles, 29 mg (0.13 mmol) of palladium acetate and 316 mg (0.77 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl were added to the mixture. Then, after two additional freeze-degas-thaw cycles, the mixture was stirred at 85 °C for 14.5 h. The reaction was cooled to room temperature and diluted with toluene. The organic extract was washed with water, dried over sodium sulfate, filtered, and the solution was concentrated. The residue was purified by silica gel column chromatography using a mixed solvent of heptane and dichloromethane as the eluent to afford 4.17 g (89% yield) of intermediate 7-3 as a white solid. ESI-MS: 731.9 [M+H] +

[0486] Compound 7

[0487]

Chemical Structure

[0488] 4.14 g (5.66 mmol) of intermediate 7-3 was dissolved in 190 mL of dichlorobenzene. Then, following 11.9 mL (11.9 mmol) of 1.0 M boron tribromide in heptane, 4.2 mL (23.78 mmol) of N,N-diisopropylethylamine was added to the solution and the mixture was stirred at 185 °C for 40 h. The reaction was cooled to room temperature and diluted with toluene. The reaction mixture was quenched with 1.0 M aqueous sodium acetate and the aqueous layer was extracted with toluene. The organic extract was washed with water, dried over magnesium sulfate, filtered, and the solution was concentrated. The residue was purified by silica gel column chromatography using heptane as the eluent to afford 2.49 g (54% yield) of Compound 7 as a yellow solid. ESI-MS: 739.9 [M+H] +

[0489] Compound 8 Intermediate 8-1

[0490]

Chem.

[0491] 5.00 g (14.8 mmol) of Intermediate 7-1, 5.09 g (11.8 mmol) of 3,6-bis(4-(tert-butyl)phenyl)-9H-carbazole, 0.28 g (1.5 mmol) of copper(I) iodide, 0.51 g (4.42 mmol) of cyclohexane-1,2-diamine, and 9.39 g (44.2 mmol) of tripotassium phosphate were suspended in 75 ml of 1,4-dioxane and heated at 91 °C for 5 hours. The suspension was filtered through a 3 cm silica gel layer, and the silica gel was rinsed with 100 ml of dioxane. The collected eluate was concentrated under vacuum, and the product was further purified by MPLC (silica gel, 0 - 5% gradient of heptane / dichloromethane) using a CombiFlash Companion to obtain 6.9 g (91%) of Intermediate 8-1. ESI-MS (positive, m / z): C 42 H 44 BrN exact mass = 641.27; found 642.7 [M+1] +

[0492] Intermediate 8-1

[0493]

Chem.

[0494] 2.20 g (3.42 mmol) of intermediate 8-2, 1.53 g (3.77 mmol) of intermediate 2-3, 15 mg (0.07 mmol) of palladium(II) acetate, 154 mg (0.41 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos), and 2.91 g (13.7 mmol) of tripotassium phosphate were dissolved in a mixture of 30 ml of toluene, 15 mL of 1,4-dioxane, and 10 ml of water. The solution was evacuated three times and refilled with argon, and heated at 82 °C for 3 hours. The reaction mixture was diluted with 100 mL of toluene and treated with 100 mL of water. The organic phase was washed with water (3 × 50 mL), dried over sodium sulfate, and concentrated under vacuum. The resulting oil was diluted with 30 ml of dichloromethane and 50 mL of ethanol. The solution was concentrated under vacuum to a volume of 50 mL, and the resulting suspension was filtered. The solid was washed with 50 mL of ethanol to give 2.19 g (76% yield) of intermediate 8-3 as a white solid. ESI-MS (negative, m / z): C 62 H 68 N 2 exact mass of = 840.54; found 840.0 [M−1] +

[0495] Compound 8

[0496]

Chem.

[0497] 2.00 g (2.38 mmol) of Intermediate 8-2 was dissolved in 40 mL of 1,2-dichlorobenzene. 1.7 mL (9.5 mmol) of N,N-diisopropylethylamine and 4.75 ml of tribromoborane (1.0 M in heptane) were added dropwise. The brown solution was heated at 172 °C for 2.5 h. The reaction mixture was cooled and 100 mL of methanol was added. The suspension was stirred for 15 min and then filtered. The solid was washed with 50 mL of methanol, then 30 mL of water, and then with 50 mL of methanol and 30 mL of heptane. The solid was further purified by MPLC (silica gel, dichloromethane) using CombiFlash Companion to give 1.84 g (91% yield) of Compound 8 as a yellow solid. ESI-MS (positive, m / z): C 62 H 65 BN 2 exact mass of = 848.52; found 849.8 [M+1] +

[0498] Compound 9 Intermediate 9-1

[0499]

Chemical Structure

[0500] 175 mL of zinc chloride solution (1.9 M in 2-methyltetrahydrofuran) was diluted with 175 mL of tetrahydrofuran and cooled to 0 °C. 300 ml of cyclohexylmagnesium chloride solution (1 M in 2-methyltetrahydrofuran) was added over 10 minutes at a maximum temperature of 25 °C. After the reaction mixture was stirred at 0 °C for an additional 10 minutes, it was slowly added at a maximum temperature of 15 °C to a pre-cooled solution containing 54.0 g (0.24 mol) of 6-bromo-2-tetralone, 0.34 g (1.5 mmol) of palladium(II) acetate, and 1.30 g (3.0 mmol) of 2-dicyclohexylphosphino-2′,6′-bis(N,N-dimethylamino)biphenyl (CPhos) in 540 mL of tetrahydrofuran. The resulting orange suspension was stirred at 0 °C for 1 hour and then heated at 31 °C for an additional 1 hour. 0.34 g (1.5 mmol) of palladium(II) acetate and 1.30 g (3.0 mmol) of CPhos were added and heating was continued for an additional 2 hours. The black suspension was cooled to room temperature and filtered through a pad of celite filter aid, and the filter aid was rinsed with 500 mL of cyclohexane. The collected eluate was mixed with 300 mL of water and the organic solvent was removed under vacuum. The residue was stirred with 600 mL of cyclohexane and 600 mL of ethyl acetate. The organic phase was separated and washed with 300 mL of water and 200 mL of saturated aqueous sodium chloride solution. The organic phase was dried over sodium sulfate and filtered through a pad of silica gel, and the silica gel was rinsed with 300 ml of a solvent mixture of cyclohexane and ethyl acetate (2:1) and then with 300 mL of ethyl acetate. The collected eluate was concentrated under vacuum to give 59.6 g (87% yield) of Intermediate 9-1. 1 H NMR (300 MHz, CD 2 Cl 2 ) δ 7.20 - 6.91 (m, 3H), 3.56 (s, 2H), 3.07 (t, 2H), 2.54 (m, 3H), 1.88 (m, 5H), 1.45 (m, 5H).

[0501] Intermediate 9-2

[0502]

Chemical Structure

[0503] 30.0 g (0.13 mol) of 1-bromo-4-(tert-butyl)aniline was suspended in 300 ml of 37% aqueous hydrochloric acid and cooled to 0 °C. 60.5 g (0.13 mol) of a 15% aqueous sodium nitrite solution was added dropwise over 15 minutes at a maximum temperature of 2 °C. A solution containing 74.8 g (0.40 mol) of tin(II) chloride in 74.8 g of 37% aqueous hydrochloric acid was added dropwise over 40 minutes at a maximum temperature of 5 °C. The thick suspension was stirred at 0 °C for 90 minutes. The suspension was filtered, and the off-white residue was washed with 150 mL of saturated aqueous sodium chloride and 200 ml of heptane. The remaining solid was dried under vacuum at 40 °C for 18 hours to obtain 31 g (84% yield) of Intermediate 9-2 as a white powder, which was used directly in the subsequent reaction step. 1 H NMR (300 MHz, DMSO-d 6 ) δ 10.43 (br.s, 2H), 7.71 (s, 1H), 7.50 (d, 1H), 7.36 (dd, 1H), 7.14 (d, 1H), 1.25 (s, 9H).

[0504] Intermediate 9-3

[0505]

Chemical Structure

[0506] 29.8 g (48.7 mmol) of Intermediate 9-1 and 15.0 g (48.7 mmol) of Intermediate 9-2 were mixed with 150 mL of 4N hydrochloric acid solution containing dioxane and 100 mL of dioxane. The yellow suspension was heated at 110 °C for 90 minutes. The orange suspension was cooled to room temperature and filtered. The white solid was washed with dioxane, and the collected eluent was diluted with water and 250 mL of toluene. The organic phase was separated, washed with sodium bicarbonate solution until it reached a basic pH, then washed with saturated aqueous sodium chloride solution, and dried over sodium sulfate. The mixture was filtered through a silica gel plug, and the silica gel layer was rinsed with cyclohexane. The collected eluent was concentrated under vacuum. The product was purified by MPLC (silica gel, 0 - 2% gradient of heptane / ethyl acetate) using CombiFlash Companion to obtain 14.7 g (yield 69%) of Intermediate 9-3 as an orange solid. ESI-MS (negative, m / z): C 26 H 30 BrN exact mass = 435.16; found 434.4 [M+1] +

[0507] Intermediate 9-4

[0508]

Chemical Structure

[0509] 10.3 g (23.6 mmol) of Intermediate 9-3 and 6.10 g (24.8 mmol) of p-chloranil in o-xylene were heated at 138 °C for 6 hours. The reaction mixture was cooled to room temperature and diluted with ethyl acetate until it became a solution. The solution was mixed with 20 g of silica gel and concentrated under vacuum. The solid was further purified by MPLC (silica gel, 0 - 2% gradient of heptane / ethyl acetate) using CombiFlash Companion to obtain 9.2 g (yield 89%) of Intermediate 9-4 as an orange solid. ESI-MS (positive, m / z): C 26 H 28 BrN exact mass = 433.14; found 434.3 [M+1]+

[0510] Intermediate 9-5

[0511]

Chem.

[0512] 11.7 g (26.9 mmol) of Intermediate 9-4, 10.3 g (40.4 mmol) of bis(pinacolato)diboron, and 5.40 g (55.0 mmol) of potassium acetate were suspended in 110 mL of dioxane. 520 mg (1.09 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (XPhos) and 250 mg (0.27 mmol) of tris(dibenzylideneacetone)dipalladium(0) were added, and the suspension was heated at 66 °C for 15 h. The orange suspension was cooled and diluted with 140 mL of water. The suspension was stirred at room temperature and filtered. The solid was dissolved in ethyl acetate, and 50 g of celite filter aid was added. The mixture was concentrated under vacuum and purified by MPLC (silica gel, heptane / ethyl acetate (9:1)) using a CombiFlash Companion to give 9.3 g (72% yield) of Intermediate 9-5 as a pale yellow solid. ESI-MS (positive, m / z): C 32 H 40 BNO 2 exact mass of = 481.32; found 482.7 [M+1] +

[0513] Intermediate 9-6

[0514]

Chem.

[0515] 40.0 g (0.12 mol) of 3,6-dibromo-9H-carbazole, 43.8 g (0.25 mol) of 3-tert-butylphenylboronic acid, 2.13 g (1.85 mmol) of tetrakis(triphenylphosphine)palladium(0), and 574 g of 10% aqueous sodium carbonate solution were suspended in 260 ml of toluene and 260 mL of ethanol. The suspension was evacuated three times and refilled with argon, and heated at 74 °C for 2 hours. The orange suspension was cooled to room temperature and filtered. The solid was washed with toluene and water and then dissolved in heated toluene. The heated solution was filtered through a silica gel pad, and the silica was rinsed with heated toluene. The collected eluate was concentrated under vacuum until a suspension formed, and cooled to room temperature. The suspension was filtered, and the solid was washed with toluene to give 33.0 g (55% yield) of Intermediate 9-6 as a white solid. ESI-MS (positive, m / z): C 32 H 33 exact mass of N = 431.26; found 432.6 [M+1] +

[0516] Intermediate 9-7

[0517]

Chemical formula

[0518] 4.00 g (11.8 mmol) of Intermediate 7-1, 4.07 g (9.44 mmol) of Intermediate 9-6, 225 mg (1.18 mmol) of copper(I) iodide, 404 mg (3.54 mmol) of cyclohexane-1,2-diamine, and 7.51 g (35.4 mmol) of tripotassium phosphate were suspended in 75 mL of 1,4-dioxane and heated at 91 °C for 6 hours. The suspension was filtered through a 3 cm silica gel layer, and the silica gel was rinsed with 100 mL of dioxane. The collected eluate was concentrated under vacuum, and the product was further purified by MPLC (silica gel, 0 - 20% gradient of heptane / dichloromethane) using a CombiFlash Companion to give 5.46 g (90%) of Intermediate 9-7. ESI-MS (positive, m / z): C 42 H 44 The exact mass of BrN = 641.27; measured value 642.6 [M+1] +

[0519] Intermediate 9-8

[0520]

Chem.

[0521] 5.00 g (7.78 mmol) of Intermediate 9-7, 4.12 g (8.56 mmol) of Intermediate 9-5, 35 mg (0.16 mmol) of palladium(II) acetate, 383 mg (0.93 mmol) of 2-dicyclohexylphosphino-2’,6’-dimethoxybiphenyl (SPhos), and 6.61 g (31.1 mmol) of tripotassium phosphate were dissolved in a mixture of 30 ml of toluene, 15 ml of 1,4-dioxane, and 10 ml of water. The solution was evacuated three times and refilled with argon, and heated at 82 °C for 3 hours. The reaction mixture was cooled to room temperature, diluted with 100 ml of toluene, and treated with 100 ml of water. The organic phase was washed with water (3 × 50 ml), dried over sodium sulfate, and concentrated under vacuum. The resulting oil was diluted with 30 ml of dichloromethane and 100 ml of ethanol. The solution was concentrated under vacuum to 100 ml in volume, and the resulting suspension was filtered. The solid was washed with 50 ml of ethanol to give 4.7 g (66% yield) of Intermediate 9-8 as a white solid. ESI-MS (positive, m / z): C 68 H 72 N 2 The exact mass of = 916.57; measured value 918.0 [M+1] +

[0522] Compound 9

[0523]

Chem.

[0524] 4.50 g (4.91 mmol) of Intermediate 9-8 was dissolved in 120 ml of 1,2-dichlorobenzene. 3.4 ml (19.6 mmol) of N,N-diisopropylethylamine and 9.8 ml of tribromoborane (1.0 M in heptane) were added dropwise. The brown solution was heated at 172 °C for 4 hours. The reaction mixture was cooled and 300 ml of methanol was added. The solution was concentrated under vacuum and the product was purified by MPLC (silica gel, dichloromethane) using CombiFlash Companion. The isolated product was dissolved in 20 ml of dichloromethane and treated with 100 ml of acetonitrile. The resulting suspension was stirred for 30 minutes and filtered. The solid was washed with 100 ml of acetonitrile to give 3.86 g (85% yield) of Compound 9 as a yellow solid. ESI-MS (positive, m / z): C 68 H 69 BN 2 exact mass of = 924.56; found 926.0 [M+1] +

[0525] Compound 10 Intermediate 10-1

[0526]

Chemical Structure

[0527] 13.2 g (47.2 mmol) of 3,6-di-tert-9H-carbazole and 20.0 g (59.0 mmol) of Intermediate 7-1 were dissolved in 230 mL of dioxane. To this solution were added 1.12 g (5.90 mmol) of copper(I) iodide, 2.02 g (17.7 mmol) of cyclohexane-1,2-diamine, and 37.6 g (177 mmol) of potassium phosphate. The mixture was stirred at 95 °C for 6.5 hours. After the reaction mixture was cooled to room temperature, the solid was filtered and washed with toluene. The solution was washed with water containing 3-amino-2-propanol. The organic layer was dried over sodium sulfate and the solvent was removed. The residue was purified by silica gel column chromatography using heptane as the eluent to obtain 19.8 g (86% yield) of Intermediate 10-1 as an off-white solid. ESI-MS: 491 [M+H] +

[0528] Intermediate 10-2

[0529]

Chemical formula

[0530] 2.60 g (5.30 mmol) of Intermediate 10-1, 1.38 g (5.45 mmol) of bis(pinacolato)diborane, and 1.04 g (10.60 mmol) of sodium acetate were suspended in 27 mL of toluene. The suspension was degassed using three freeze-degas-thaw cycles, and 120 mg (0.13 mmol) of tris(dibenzylideneacetone)dipalladium(0) and 152 mg (0.51 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl were added to the mixture. After two more freeze-degas-thaw cycles, the reaction mixture was heated at 110 °C for 6 hours. The reaction was cooled to room temperature and diluted with toluene and water. The aqueous layer was extracted with toluene, the organic layer was washed with saturated brine, dried over magnesium sulfate, filtered, and the solution was concentrated. The crude product was recrystallized from dichloromethane and acetonitrile to obtain 2.69 g (80% yield) of Intermediate 10-2 as a white solid. ESI-MS: 538.8 [M+H] +

[0531] Intermediate 10-3

[0532]

Chem.

[0533] 10.15 g (23.52 mmol) of 3,6-bis(4-(tert-butyl)phenyl)-9H-carbazole was suspended in THF, and 4.19 g (23.52 mmol) of N-bromosuccinimide was added little by little. After the mixture was stirred at room temperature for 50 minutes, the reaction mixture was filtered off. The filtrate was concentrated. The crude product was purified by silica gel column chromatography using a mixed solvent of heptane and dichloromethane as the eluent. The product was precipitated in a mixed solvent of dichloromethane and heptane to obtain 10.21 g (yield 85%) of Intermediate 10-3 as a white solid. ESI-MS: 508 [M-H] -

[0534] Intermediate 10-4

[0535]

Chem.

[0536] 1.37 g (2.68 mmol) of Intermediate 10-3, 2.55 g (4.03 mmol) of Intermediate 10-2, and 2.28 g (10.73 mmol) of potassium phosphate were dissolved in 18 mL of toluene, 9 mL of dioxane, and 6 mL of water. After degassing the solution using three freeze-degas-thaw cycles, 12 mg (0.05 mmol) of palladium acetate and 132 mg (0.32 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl were added to the mixture. Then, after two additional freeze-degas-thaw cycles, the mixture was stirred at 85 °C for 16.5 h. The reaction was cooled to room temperature and diluted with toluene. The organic extract was washed with water, dried over sodium sulfate, filtered, and the solution was concentrated. The residue was purified by silica gel column chromatography using a mixed solvent of heptane and toluene as the eluent to afford 2.11 g (93% yield) of Intermediate 7-2 as a white solid. ESI-MS: 839.8 [M+H] +

[0537] Compound 10

[0538]

Chemical formula

[0539] 2.11 g (2.51 mmol) of Intermediate 10-4 was dissolved in 36 mL of dichlorobenzene. Then, following 5.14 mL (5.12 mmol) of 1.0 M boron tribromide in heptane, 1.8 mL (10.28 mmol) of N,N-diisopropylethylamine was added to the solution and the mixture was stirred at 180 °C for 15 h. The reaction was cooled to room temperature and diluted with methanol. The precipitate was collected by filtration and washed with ethanol and water. The crude product was dissolved in dichloromethane, precipitated with isopropanol, and then filtered to afford 1.77 g (83% yield) of Compound 10 as a yellow solid. ESI-MS: 849.7 [M+H] +

[0540] Compound 11 Intermediate 11-1

[0541]

Chem.

[0542] 23.5 g (112 mmol) of 4-bromo-2-chloro-1-fluorobenzene and 20.2 g (112 mmol) of 4-(tert-butyl)phenylboronic acid were suspended in a mixture of 130 mL of toluene, 130 mL of ethanol, and 250 mL of 10% aqueous sodium carbonate solution. N 2 The mixture was degassed by bubbling N 2 gas through it for 30 minutes, and 3.9 g (3 mol%) of tetrakis(triphenylphosphine)palladium(0) was added to the reaction mixture under gentle N 1 flow. The reaction mixture was heated to reflux for 2 hours and then cooled to room temperature. The reaction mixture was extracted with toluene, the organic phase was washed with water and saturated brine, dried over magnesium sulfate, and filtered through a small silica gel pad. The product was eluted with heptane, and the solvent was removed using a rotary evaporator. The crude product was used as Intermediate 11-1 without further purification. 2 H NMR (300 MHz, methylene chloride-d 19 F NMR (282 MHz, methylene chloride-d 2 ) δ -119.44.

[0543] Intermediate 11-2

[0544]

Chem.

[0545] 260 g (1.26 mol) of 2,4 - di - tert - butylphenol and 330 g (1.89 mol) of 1 - bromo - 2 - fluorobenzene were added to 5.70 L of N - methylpyrrolidone, and 821 g (2.52 mol) of cesium carbonate was added. The mixture was stirred at 170 °C for 90 hours. The reaction mixture was cooled to room temperature and water was added thereto. The organic layer was collected. After concentration, the residue was purified by silica gel column chromatography using heptane as an eluent to obtain 409 g (yield 90%) of Intermediate 11 - 2 as a beige solid. The product was used without further purification.

[0546] Intermediate 11 - 3

[0547]

Chemical formula

[0548] After dissolving 399 g (1.10 mol) of Intermediate 11 - 2 in 1.40 L of N - methylpyrrolidone, 821 g (2.52 mol) of cesium carbonate was added. Under an argon atmosphere, 17.38 g (66.3 mmol) of triphenylphosphine and 7.44 g (33.1 mmol) of palladium(II) acetate were added. The mixture was stirred at 120 °C for 3 hours. The reaction mixture was cooled to room temperature and water was added. The organic layer was collected and washed with saturated brine. After concentration, the residue was purified by silica gel column chromatography using toluene as an eluent. The main fraction was partially concentrated, precipitated by replacing the solvent with heptane, and then filtered to obtain 227 g (yield 73%) of Intermediate 11 - 3 as a white solid. ESI - MS: 280[M + H] +

[0549] Intermediate 11 - 4

[0550]

Chemical formula

[0551] 118 g (421 mmol) of Intermediate 11-3 was dissolved in 1.20 L of THF, and the solution was cooled to 5 °C. Under an argon atmosphere, 400 mL (620 mmol) of 1.55 M n-butyllithium in hexane was added dropwise at 5 °C. After the reaction mixture was cooled to -60 °C, 118 g (631 mmol) of 1,2-dibromoethane was added, and the mixture was stirred for 17 hours. 500 mL of water was added to the reaction mixture, and the aqueous phase was extracted with toluene. The organic phase was collected and washed with saturated brine. After concentration, the residue was purified by silica gel column chromatography using toluene as the eluent. The main fraction was concentrated. The product was dissolved in heated heptane and recrystallized using an ice-water bath to obtain 77 g (yield 51%) of Intermediate 11-4 as a white solid. ESI-MS: 360 [M+H] +

[0552] Intermediate 11-5

[0553]

Chemical formula

[0554] Under an inert atmosphere, 9.57 mL of n-butyllithium (1.6 M in hexane) was added dropwise to a solution containing 5.00 g (13.9 mmol) of Intermediate 11-4 in 50 mL of tetrahydrofuran while maintaining the temperature below -60 °C using an acetone-dry ice bath. After the addition was complete, the reaction was stirred at -78 °C for 15 minutes. Then, 2.20 mL (19.7 mmol) of trimethyl borate was slowly added while maintaining the temperature below -60 °C. After the addition was complete, the reaction was stirred at -78 °C for 15 minutes, then slowly warmed to room temperature and stirred for 17 hours to obtain an emulsion solution. 50 mL of 10% HCl solution was added to the reaction, and the yellow two-phase mixture was stirred for 1 hour. The resulting mixture was extracted with ethyl acetate, and the organic extract was washed with water and saturated brine, dried over magnesium sulfate, and filtered through a short silica gel pad. The solvent was removed using a rotary evaporator to obtain 4.25 g (yield 60%) of Intermediate 11-5 as a white solid. 1 1H NMR (300 MHz, DMSO-d 6 ) δ 8.24 - 8.14 (m, 2H), 7.97 (d, J = 1.9 Hz, 1H), 7.41 - 7.33 (m, 2H), 1.48 (s, 9H), 1.39 (s, 9H).

[0555] Intermediate 11 - 6

[0556]

Chemical formula

[0557] 7.00 g (29.6 mmol) of 1 - bromo - 4 - chloro - 2 - nitrobenzene and 10.1 g (31.1 mmol) of Intermediate 11 - 5 were suspended in a mixture of 70 mL of toluene, 70 mL of ethanol, and 70 mL of 10% aqueous sodium carbonate solution. N 2 The mixture was degassed by bubbling N gas for 30 minutes, and 0.80 g (2.2 mol%) of tetrakis(triphenylphosphine)palladium(0) was added to the reaction mixture under gentle N 2 flow. After the reaction mixture was heated to reflux for 2 hours, it was cooled to room temperature. The reaction mixture was extracted with heptane, the organic phase was washed with water and saturated brine, dried over magnesium sulfate, and the solvent was removed using a rotary evaporator. The crude product was dissolved in a 1:1 mixture of dichloromethane / ethanol and concentrated using a rotary evaporator until a yellow suspension was formed. The suspension was stirred at room temperature for 1 hour and filtered to obtain 10.4 g (yield 80%) of Intermediate 11 - 6 as a bright yellow solid. 1 1H NMR (300 MHz, methylene chloride - d 2 ) δ 8.20 (d, J = 2.2 Hz, 1H), 8.08 (dd, J = 7.4, 1.6 Hz, 1H), 7.92 (d, J = 2.0 Hz, 1H), 7.79 (dd, J = 8.3, 2.2 Hz, 1H), 7.65 (d, J = 8.3 Hz, 1H), 7.55 - 7.36 (m, 3H), 1.47 (d, J = 3.2 Hz, 18H).

[0558] Intermediate 11 - 7

[0559]

Chem.

[0560] 10.4 g (23.9 mmol) of intermediate 11-6 and 15.8 g (59.6 mmol) of triphenylphosphine were dissolved in 100 mL of 1,2-dichlorobenzene and heated to reflux for 3 hours. Subsequently, 1,2-dichlorobenzene and triphenylphosphine were distilled off under reduced pressure, the red oil was cooled, and heptane was added with stirring. The resulting orange suspension was stirred at room temperature and then at 0 °C for 30 minutes, and then filtered. The solvent was removed from the filtrate using a rotary evaporator, and the crude product was purified by silica gel column chromatography using a mixture of heptane and toluene to obtain an off-white solid. The solid was dissolved in refluxing ethanol and precipitated by adding water at room temperature. The resulting suspension was filtered, and the subsequent crops were combined to obtain 8.0 g (yield 83%) of intermediate 11-7 as a white solid. ESI-MS: 402.4 [M-H] -

[0561] Intermediate 11-8

[0562]

Chem.

[0563] 10.4 g (39.6 mmol) of intermediate 11-1, 8.00 g (19.8 mmol) of intermediate 11-7, and 8.41 g (39.6 mmol) of potassium phosphate were suspended in 80 ml of N,N-dimethylformamide and heated to 110 °C for 5 hours. Subsequently, the suspension was cooled to 100 °C and water was slowly added. The resulting off-white suspension was cooled to room temperature and filtered. The crude solid was triturated three times in a heated 9:1 mixture of ethanol / water to obtain 12.5 g (yield 96%) of intermediate 11-8 as a white solid. ESI-MS: 646.6 [M+H] +

[0564] Intermediate 11-9

[0565]

Chem.

[0566] 4.00 g (6.20 mmol) of Intermediate 11-8 and 5.2 g (24.8 mmol) of potassium phosphate were dissolved in a mixture of 120 mL of dioxane and 30 mL of water, and the mixture was degassed by bubbling N 2 through it. 312 mg (12 mol%) of SPhos and 30 mg (2 mol%) of palladium(II) acetate were added, and the reaction was heated to 85 °C. A solution (0.155 M) containing 3.52 g (8.68 mmol) of Intermediate 2-3 in 56 mL of dioxane, which had been degassed beforehand, was added dropwise over 45 minutes, and then the reaction mixture was heated at 95 °C for 3 hours. The reaction was cooled to room temperature and poured into water. The resulting precipitate was stirred for 30 minutes and filtered. The crude solid was dissolved in dichloromethane, and the organic phase was washed with water and saturated brine. The organic matter was dried over magnesium sulfate, 0.5 g of activated carbon was added, and then it was refluxed for 30 minutes. The suspension was filtered through a silica gel pad, and the product was eluted with additional dichloromethane. Methanol was added to the filtrate, and the mixture was concentrated on a rotary evaporator until a precipitate formed. The suspension was cooled to room temperature and filtered. The solid was purified by silica gel column chromatography using a mixture of heptane and dichloromethane to give 3.1 g (yield 28%) of Intermediate 11-9 as a white foam. ESI-MS: 889.9 [M+H] +

[0567] Compound 11

[0568]

Chem.

[0569] Under an inert atmosphere, 3.50 mL of tert-butyllithium (1.9 M in hexane) was added dropwise to a solution containing 1.95 g (2.19 mmol) of Intermediate 11-9 in 200 mL of tert-butylbenzene while maintaining the temperature below -50 °C using an acetone-dry ice bath. After the addition was complete, the reaction mixture was heated to 45 °C for 1 hour, cooled to -78 °C, and then 0.35 mL (3.70 mmol) of boron tribromide was slowly added while maintaining the temperature below -60 °C. The reaction mixture was warmed to room temperature, 1.10 mL (6.58 mmol) of N,N-diisopropylethylamine was added, and the mixture was heated to 150 °C for 17 hours. The reaction mixture was then cooled to room temperature, quenched with water, and filtered. The biphasic filtrate was extracted with toluene, and the organic phase was washed twice with a 10% aqueous sodium carbonate solution and then with saturated brine. The organic extract was dried over magnesium sulfate and filtered through a silica gel pad. The bright orange solution was concentrated to approximately 100 mL on a rotary evaporator, and 300 mL of ethanol was added thereto. The precipitate was cooled to room temperature, stirred for 17 hours, and then filtered. The resulting solid was purified by silica gel chromatography using a mixture of heptane and dichloromethane. The resulting resin was dissolved in 200 mL of dichloromethane and 200 mL of ethanol and concentrated at 60 °C on a rotary evaporator until a suspension formed. It was then filtered while hot, and the solid was washed with a little cold ethanol to obtain 215 mg (yield 11.4%) of Compound 11 as a bright yellow solid. ESI-MS: 864.0 [M+H] +

[0570] Compound 12 Intermediate 12-1

[0571]

Chemical Structure

[0572] A solution containing 30.0 g (134 mmol) of 4-(bromophenyl)hydrazine hydrochloride in 270 mL of acetic acid was added dropwise with 20.7 g (134 mmol) of 4-(tert-butyl)cyclohexan-1-one at 80 °C under nitrogen. Subsequently, the reaction mixture was stirred at 100 °C for 5 hours. The solvent was removed in vacuo, and the reaction mixture was dissolved in toluene. The organic phase was washed with water and then with a sodium hydrogen carbonate solution. The organic phase was dried over magnesium sulfate, and the solvent was removed in vacuo. The product was used in the subsequent reaction step without purification. Yield: 41.0 g.

[0573] Intermediate 12-2

[0574]

Chemical formula

[0575] To a solution containing 41.0 g (134 mmol) of 6-bromo-3-(tert-butyl)-2,3,4,9-tetrahydro-1H-carbazole in 250 mL of toluene, 60.8 g (268 mmol) of 2,3-dichloro-5,6-dicyanoquinone was added under nitrogen over 10 minutes. The reaction was exothermic. Subsequently, the reaction mixture was stirred at 25 °C for 1 hour. The solid was filtered off and washed with toluene. The organic phase was washed with a 10% aqueous sodium hydroxide solution. The organic phase was washed with water and saturated brine, and dried over magnesium sulfate. The solvent was removed in vacuo. The product was obtained by column chromatography on silica gel using heptane / ethyl acetate (95 / 5). Yield: 21.6 g (52%). 1 1H-NMR (300 MHz, DMSO-d6) δ = 11.3 (s, 1H), 8.39 (s, 1H), 8.19 (s, 1H), 7.45 (m, 4H), 1.40 (s, 9H).

[0576] Intermediate 12-3

[0577]

Chemical formula

[0578] To a solution containing 17.9 g (59 mmol) of 6-bromo-3-(tert-butyl)-2,3,4,9-tetrahydro-1H-carbazole in 300 mL of dioxane and 50 mL of water were added 27.1 g (107 mmol) of 4,4,4’,4’,5,5,5’,5’-octamethyl-2,2’-bi(1,3,2-dioxaborolane) and 17.4 g (178 mmol) of potassium acetate. The reaction mixture was degassed using argon. 542 mg (0.592 mmol) of tris(dibenzylideneacetone)dipalladium(0) and 564 mg (1.18 mmol) of 2-dicyclohexylphosphino-2’,4’,6’-triisopropylbiphenyl (XPhos) were added. The reaction mixture was degassed using argon. The reaction mixture was stirred under argon at 110 °C for 8 hours. The solid was filtered off and the aqueous phase was removed. The solvent was removed in vacuo. The product was obtained by column chromatography on silica gel using heptane / ethyl acetate (90 / 10). Yield 11.7 g (55%). 1 1H-NMR (300 MHz, DMSO-d6) δ = 11.27 (s, 1H), 8.52 (d, 1H), 8.51 (s, 1H), 7.71 (d, 1H), 7.45 (m, 3H), 1.41 (s, 9H), 1.33 (s, 12H).

[0579] Intermediate 12-4

[0580]

Chemical Structure

[0581] A solution containing 11.7 g (33.4 mmol) of 3-(tert-butyl)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole in 120 ml of xylene, 70 mL of dioxane, and 50 ml of water was added with 9.81 g (36.8 mmol) of 2-chloro-4,6-diphenylpyrimidine and 11.6 g (84.0 mmol) of potassium carbonate. The reaction mixture was degassed using argon. 1.16 g (1.00 mmol) of tetrakis(triphenylphosphine)palladium(0) was added. The reaction mixture was degassed using argon. The reaction mixture was stirred under argon at 110 °C for 8 hours. The aqueous phase was removed. The solvent was removed in vacuo. The product was obtained by column chromatography on silica gel using heptane / ethyl acetate (95 / 5) and heptane / ethyl acetate (90 / 10). Yield 6.75 g (44%). ESI-MS: 454 [M+1] + 1 1H-NMR (300 MHz, DMSO-d6) δ = 11.42 (s, 1H), 9.42 (d, 1H), 8.76 (m, 1H), 8.58 (m, 4H), 8.47 (s, 1H), 8.35 (s, 1H), 7.66 (m, 9H), 1.46 (s, 9H).

[0582] Intermediate 12-5

[0583]

Chemical Structure

[0584] To a solution containing 6.75 g (14.9 mmol) of 3-(tert-butyl)-6-(4,6-diphenylpyrimidin-2-yl)-9H-carbazole in 60 mL of acetic acid was added 2.65 g (14.9 mmol) of N-bromosuccinimide, and the reaction mixture was stirred at 20 °C under nitrogen. After 2.5 hours, the product was filtered off and washed successively with acetic acid and then methanol. The product was obtained by column chromatography on silica gel using heptane / ethyl acetate (97 / 3). Yield 4.00 g (39%). The product was crystallized using toluene. 1 H-NMR (300 MHz, DMSO-d6) δ = 11.61 (s, 1H), 9.45 (m, 1H), 8.84 (m, 1H), 8.58 (m, 4H), 8.49 (s, 1H), 8.41 (s, 1H), 7.67 (m, 8H), 1.46 (s, 9H).

[0585] Intermediate 12-6

[0586]

Chem.

[0587] To a solution containing 1.52 g (2.85 mmol) of 1-bromo-3-(tert-butyl)-6-(4,6-diphenylpyrimidin-2-yl)-9H-carbazole in 30 ml of toluene, 15 ml of dioxane, and 10 ml of water were added 1.61 g (3.00 mmol) of 3,6-di-tert-butyl-9-(3-(tert-butyl)-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-9H-carbazole and 1.82 g (8.56 mmol) of tripotassium phosphate. The reaction mixture was degassed using argon. 94 mg (0.23 mmol) of dicyclohexyl(2’,6’-dimethoxy[1,1’-biphenyl]-2-yl)phosphane SPhos and 26 mg (0.114 mmol) of palladium(II) acetate were added. The reaction mixture was degassed using argon. The reaction mixture was stirred under argon at 70 °C for 1 hour. The solid was filtered off and washed with heptane. The organic phase was dried over magnesium sulfate and the solvent was removed in vacuo. The product was obtained by column chromatography on silica gel using heptane / ethyl acetate (95 / 5). Yield 2.19 g (88%). 1 H-NMR (300 MHz, DMSO-d6) δ = 11.38 (s, 1H), 9.49 (d, 1H), 8.78 (d, 1H), 8.58 (m, 4H), 8.45 (m, 2H), 8.33 (m, 2H), 7.64 (m, 15H), 1.51 (s, 18H), 1.43 (s, 18H).

[0588] Compound 12

[0589]

Chem.

[0590] To a solution containing 1.98 g (2.29 mmol) of 3-(tert-butyl)-1-(3-(tert-butyl)-5-(3,6-di-tert-butyl-9H-carbazol-9-yl)phenyl)-6-(4,6-diphenylpyrimidin-2-yl)-9H-carbazole in 26 mL of o-dichlorobenzene was added 1.19 g (9.18 mmol) of N-ethyl-N-isopropylpropan-2-amine under argon. To the reaction mixture was added dropwise a solution containing 4.59 mL (4.50 mmol) of 1 M tribromoborane in heptane under argon over 5 minutes. The reaction mixture was stirred at 185 °C for 2.5 hours under argon. The reaction mixture was cooled to 25 °C and methanol was added. The product was filtered off and washed with methanol. The product was obtained by column chromatography on silica gel using dichloromethane (100%). Yield 1.71 g (77%). ESI-MS: 871.8 [M+1] + 1 1H-NMR (300 MHz, CDCl 3 ) δ = 9.65 (s, 1H), 9.06 (m, 2H), 8.91 (d, 1H), 8.65 (m, 3H), 8.49 (m, 9H), 7.81 (m, 1H), 7.63 (m, 6H), 1.71 (s, 18H), 1.68 (s, 9H), 1.58 (s, 9H).

[0591] Compound 13 Intermediate 13-1

[0592]

Chem.

[0593] 16.62 g (47.70 mmol) of (2-bromo-4-iodophenyl)hydrazine hydrochloride and 7.36 g (47.70 mmol) of 4-(tert-butyl)cyclohexanone were added to 95 mL of acetic acid, and the mixture was stirred at 100 °C for 2 hours. After the reaction mixture was cooled to room temperature, the solid was collected by filtration and washed with ethyl acetate. After concentrating the filtrate, the residue was purified by silica gel column chromatography using a mixed solvent of heptane and dichloromethane as the eluent to obtain 11.2 g (yield 54%) of Intermediate 13-1 as a white solid. ESI-MS: 433 [M+H] +

[0594] Intermediate 13-2

[0595]

Chemical formula

[0596] 7.03 g (16.27 mmol) of Intermediate 13-1 and 7.39 g (32.50 mmol) of 2,3-dichloro-5,6-dicyanoquinone were added to 60 mL of toluene, and the mixture was stirred at 100 °C for 2.5 hours. After the reaction mixture was cooled to room temperature, the solid was removed by filtration and washed with toluene. After concentrating the filtrate, the residue was purified by silica gel column chromatography using a mixed solvent of heptane and dichloromethane as the eluent to obtain 4.73 g (yield 68%) of Intermediate 13-2 as a beige powder. ESI-MS: 427 [M+H] +

[0597] Intermediate 13-3

[0598]

Chemical formula

[0599] 4.28 g (10.00 mmol) of Intermediate 13-2, 1.78 g (10.00 mmol) of 4-tert-butylbenzeneboronic acid, and 2.76 g (19.99 mmol) of potassium carbonate were dissolved in 50 mL of toluene, 10 mL of ethanol, and 10 mL of water. After degassing the solution using three freeze-degas-thaw cycles, 578 mg (0.50 mmol) of tetrakis(triphenylphosphine)palladium was added to the mixture. Then, after two additional freeze-degas-thaw cycles, the mixture was stirred at 70 °C for 20 hours. The reaction was cooled to room temperature and diluted with toluene. The organic extract was washed with water, dried over sodium sulfate, filtered, and the solution was concentrated. The residue was purified by silica gel column chromatography using a mixed solvent of heptane and toluene as the eluent to give 3.56 g (82% yield) of Intermediate 13-3 as a white solid. ESI-MS: 433 [M-H] -

[0600] Intermediate 13-4

[0601] [Chemical formula]

[0602] 3.40 g (5.30 mmol) of Intermediate 8-1, 1.38 g (5.45 mmol) of bis(pinacolato)diborane, and 1.04 g (10.60 mmol) of sodium acetate were suspended in 27 mL of toluene. The suspension was degassed using three freeze-degas-thaw cycles, and 120 mg (0.13 mmol) of tris(dibenzylideneacetone)dipalladium(0) and 152 mg (0.51 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl were added to the mixture. After two additional freeze-degas-thaw cycles, the reaction mixture was heated at 110 °C for 6 h. The reaction was cooled to room temperature and diluted with toluene and water. The aqueous layer was extracted with toluene, the organic layer was washed with saturated brine, dried over magnesium sulfate, filtered, and the solution was concentrated. The crude product was recrystallized from dichloromethane and acetonitrile to afford 2.74 g (75% yield) of Intermediate 13-4 as a white solid. ESI-MS: 690 [M+H]

[0603] Intermediate 13-5

[0604]

Chemical Structure

[0605] 1.39 g (3.22 mmol) of Intermediate 13-3, 3.06 g (4.84 mmol) of Intermediate 10-2, and 2.73 g (12.8 mmol) of potassium phosphate were dissolved in 21 mL of toluene, 11 mL of dioxane, and 7 mL of water. After degassing the solution using three freeze-degas-thaw cycles, 15 mg (0.06 mmol) of palladium acetate and 158 mg (0.38 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl were added to the mixture. Then, after two additional freeze-degas-thaw cycles, the mixture was stirred at 85 °C for 16.5 h. The reaction was cooled to room temperature and diluted with toluene. The organic extract was washed with water, dried over sodium sulfate, filtered, and the solution was concentrated. The residue was purified by silica gel column chromatography using a mixed solvent of heptane and toluene as the eluent to give 2.15 g (79% yield) of Intermediate 13-5 as a white solid. ESI-MS: 918 [M+H] +

[0606] Compound 13

[0607]

Chemical Structure

[0608] 1.83 g (2.00 mmol) of Intermediate 13-5 was dissolved in 28 mL of dichlorobenzene. Then, following 4.10 mL (4.10 mmol) of 1.0 M boron tribromide in heptane, 1.4 mL (8.19 mmol) of N,N-diisopropylethylamine was added to the solution and the mixture was stirred at 180 °C for 15 h. The reaction was cooled to room temperature and diluted with methanol. The precipitate was collected by filtration and washed with ethanol and water. The crude product was dissolved in dichloromethane and precipitated using isopropanol and then filtered to give 1.39 g (75% yield) of Compound 13 as a yellow solid. ESI-MS: 925 [M+H] +

[0609] Compound 14 Intermediate 14-1

[0610]

Chem.

[0611] 40.0 g (178 mmol) of 6-bromo-3,4-dihydronaphthalen-2(1H)-one, 38.0 g (213 mmol) of (3-(tert-butyl)phenyl)boronic acid, and 38.6 g (364 mmol) of sodium carbonate were dissolved in 523 mL of toluene, 261 mL of ethanol, and 105 mL of water. After degassing the solution using three freeze-degas-thaw cycles, 3.08 g (2.67 mmol) of tetrakis(triphenylphosphine)palladium was added to the mixture. Then, after two additional freeze-degas-thaw cycles, the mixture was stirred at 80 °C for 1.5 h. The reaction was cooled to room temperature, 5 g of sodium cyanide dissolved in 50 mL of water was added, and the reaction mixture was stirred for 30 min. The organic extract was washed with water, dried over sodium sulfate, filtered, and the solution was concentrated to give 21.0 g (42% yield) of Intermediate 14-1 as a white solid. This was used in the subsequent reaction without further purification.

[0612] Intermediate 14-2

[0613]

Chem.

[0614] 27.9 g (71.8 mmol) of (2-bromo-4-iodophenyl)hydrazine hydrochloride and 20.0 g (71.8 mmol) of Intermediate 14-1 were added to 198 mL of 4N HCl dioxane solution, and the mixture was stirred at 110 °C for 3 h. After cooling the reaction mixture to room temperature, the reaction mixture was poured into 500 mL of water. After adding 600 mL of dichloromethane, the aqueous layer was extracted with dichloromethane, and the collected organic layer was dried over sodium sulfate. After filtration, the solution was concentrated to give 18.8 g (47% yield) of Intermediate 14-2 as a white solid. ESI-MS: 556.2 [M-H] -

[0615] Intermediate 14-3

[0616]

Chem.

[0617] 18.0 g (32.4 mmol) of Intermediate 14-2 and 8.75 g (35.6 mmol) of 2,3-dichloro-5,6-dicyanoquinone were added to 180 mL of o-xylene, and the mixture was stirred at 130 °C for 2.5 hours. After the reaction mixture was cooled to room temperature, the reaction mixture was suspended in 200 mL of heptane. The suspension was filtered, washed with heptane, and the filtrate was concentrated. The crude product was dissolved in toluene under reflux. After the solution was cooled to room temperature, the formed solid was collected by filtration and washed with heptane to obtain 11.25 g (yield 63%) of Intermediate 14-3 as a light gray solid. ESI-MS: 552.2 [M-H] -

[0618] Intermediate 14-4

[0619]

Chem.

[0620] 11.0 g (19.85 mmol) of Intermediate 14-3, 3.53 g (19.85 mmol) of (4-(tert-butyl)phenyl)boronic acid, and 4.63 g (43.7 mmol) of sodium carbonate were dissolved in 120 mL of toluene, 120 mL of ethanol, and 40 mL of water. After degassing the solution using three freeze-degas-thaw cycles, 688 mg (0.60 mmol) of tetrakis(triphenylphosphine)palladium was added to the mixture. Then, after two additional freeze-degas-thaw cycles, the mixture was stirred at 80 °C for 4 h. The reaction was cooled to room temperature, 1 g of sodium cyanide dissolved in 50 mL of water was added, and the reaction mixture was stirred for 30 min. The organic extract was washed with water, dried over sodium sulfate, filtered, and the solution was concentrated. The crude product was purified by silica gel column chromatography using a mixed solvent of heptane and dichloromethane as the eluent to afford 7.33 g (65% yield) of Intermediate 14-4 as an off-white solid. ESI-MS: 560.5 [M-H] -

[0621] Intermediate 14-5

[0622]

Chemical Structure

[0623] 1.50 g (2.68 mmol) of Intermediate 14-4, 2.15 g (4.01 mmol) of Intermediate 10-2, and 2.28 g (10.70 mmol) of potassium phosphate were dissolved in 22 mL of toluene, 11 mL of dioxane, and 7 mL of water. After degassing the solution using three freeze-degas-thaw cycles, 21 mg (0.09 mmol) of palladium acetate and 231 mg (0.56 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl were added to the mixture. Then, after two additional freeze-degas-thaw cycles, the mixture was stirred at 85 °C for 21 hours. The reaction was cooled to room temperature and diluted with toluene. The organic extract was washed with water, dried over sodium sulfate, filtered, and the solution was concentrated. The residue was purified by silica gel column chromatography using a mixed solvent of heptane and toluene as the eluent to obtain 1.72 g (yield 72%) of Intermediate 14-5 as a white solid. ESI-MS: 891 [M-H] -

[0624] Compound 14

[0625]

Chemical Structure

[0626] 1.78 g (2.00 mmol) of Intermediate 14-5 was dissolved in 28 mL of dichlorobenzene. Then, following 4.10 mL (4.10 mmol) of 1.0 M boron tribromide in heptane, 1.4 mL (8.19 mmol) of N,N-diisopropylethylamine was added to the solution and the mixture was stirred at 180 °C for 15 hours. The reaction was cooled to room temperature and diluted with methanol. The precipitate was collected by filtration and washed with ethanol and water. The crude product was dissolved in dichloromethane and precipitated using isopropanol and then filtered to obtain 1.41 g (yield 83%) of Compound 14 as a yellow solid. ESI-MS: 900 [M+H] +

[0627] Compound 15 Intermediate 15-1

[0628]

Chem.

[0629] To a solution containing 26.4 g (78.0 mmol) of Intermediate 7-1 in 250 mL of 1,4-dioxane, 15.35 g (65.0 mmol) of 3,6-dichloro-9H-carbazole, 41.4 g (195.0 mmol) of potassium phosphate, 1.55 g (8.13 mmol) of copper(I) iodide, and 2.73 mL (22.75 mmol) of cyclohexane-1,2-diamine were added. After the suspension was degassed with Ar, it was heated at 85 °C for 1.5 hours. After cooling to room temperature, the suspension was filtered through Celite and washed with warm toluene (4 × 100 mL). The filtrate was evaporated, and the resulting residue was purified by silica gel column chromatography using heptane as the eluent. The obtained white solid was further recrystallized using cyclohexane (2 × 150 mL) to give 14.66 g (80% yield) of Intermediate 15-1 as a white solid. 1 H NMR (300 MHz, chloroform-d 3 ) δ 8.05 (dd, 2H), 7.67 (t, 1H), 7.50 (dt, 2H), 7.42 (dd, 2H), 7.32 (dd, 2H), 1.41 (s, 9H).

[0630] Intermediate 15-3

[0631]

Chem.

[0632] 12.30 g (27.5 mmol) of Intermediate 15-1, 11.15 g (27.5 mmol) of Intermediate 2-3, and 2.20 g (55.0 mmol) of sodium hydroxide were suspended in a mixture of tetrahydrofuran / water (120 mL / 60 mL). The suspension was degassed with Ar, and 477 mg (1.5 mol%) of tetrakis(triphenylphosphine)palladium(0) was added to the reaction mixture. The reaction mixture was refluxed for 1 hour. The reaction was cooled to room temperature and diluted with toluene / water. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extracts were washed with water, saturated brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane / toluene as the eluent to obtain 17.76 g (100% yield) of Intermediate 15-2 as a white foam. ESI-MS: 643.4 [M-H] -

[0633] Intermediate 15-3

[0634]

Chemical formula

[0635] 17.43 g (27.0 mmol) of Intermediate 15-2 was dissolved in 225 ml of 1,2-dichlorobenzene and degassed with Ar. After adding 18.49 mL (108 mmol) of N-ethyl-N-isopropylpropan-2-amine to the reaction mixture, 54.0 ml (54.0 mmol) of tribromoborane (1 M solution in heptane) was slowly added. The reaction mixture was heated at 180 °C for 5 hours. After cooling to room temperature, the precipitate formed in the reaction was filtered, washed with 1,2-dichlorobenzene, methanol, and heptane to obtain 13.76 g (78% yield) of Intermediate 15-3 as a yellow solid. The molecular mass of the product was confirmed by LC-MS [M+H] 653.3. ESI-MS: 653.3 [M+H] +

[0636] Compound 15

[0637] [Chem.]

[0638] 2.35 g (3.6 mmol) of Intermediate 15-3, 2.80 g (14.4 mmol) of (4-(trimethylsilyl)phenyl)boronic acid, and 4.69 g (14.4 mmol) of cesium carbonate were suspended in a mixture of toluene / ethanol / water (36 mL / 12 mL / 6 mL). The suspension was degassed with Ar, and 40 mg (5 mol%) of palladium acetate and 148 mg (10 mol%) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl were added to the reaction mixture. The reaction mixture was heated at 80 °C for 1.5 h. The reaction was cooled to room temperature and diluted with toluene / water. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extracts were washed with water and saturated brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane / toluene as the eluent to give 2.98 g (94% yield) of Compound 15 as a yellow solid. ESI-MS: 881.5 [M+H] +

[0639] Compound 16

[0640] [Chem.]

[0641] 2.61 g (4.0 mmol) of Intermediate 15-3, 2.62 g (16.0 mmol) of (2-isopropylphenyl)boronic acid, and 5.21 g (16.0 mmol) of cesium carbonate were suspended in a mixture of toluene / ethanol / water (36 mL / 12 mL / 6 mL). The suspension was degassed with Ar, and 45 mg (5 mol%) of palladium acetate and 164 mg (10 mol%) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl were added to the reaction mixture. The reaction mixture was heated at 80 °C for 5 h. The reaction was cooled to room temperature and diluted with toluene / water. The layers were separated and the aqueous layer was further extracted with toluene. The organic extracts were washed with water, saturated brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane / toluene as the eluent to give 3.15 g (96% yield) of Compound 16 as a yellow solid. ESI-MS: 821.5 [M+H] +

[0642] Compound 17 Intermediate 17-1

[0643]

Chemical Structure

[0644] 40.0 g (0.15 mol) of 6-bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene was suspended in 150 ml of acetic anhydride. 78 mL (1.12 mol) of nitric acid was added dropwise at room temperature over 3 h. The yellow suspension was stirred for 30 min and then treated with 1.5 l of water and stirred for an additional 1 h. The suspension was filtered and the solid was washed with 500 mL of water. The solid was suspended in 400 mL of 10% aqueous sodium carbonate solution. The suspension was filtered and the solid was washed with 500 mL of water. The solid was further suspended in 150 mL of ethanol and then filtered, and the solid was washed with 50 ml of ethanol to give 43.2 g (93% yield) of Intermediate 17-1 as a white solid. 1 H NMR (300 MHz, DMSO-d 6)δ 7.98(s,1H),7.80(s,1H),1.66(s,4H),1.27(d,12H).

[0645] Intermediate 17-2

[0646]

Chem.

[0647] A solution containing 20.0 g (61.7 mmol) of 2-bromo-N,N-diphenylaniline in 200 ml of tetrahydrofuran was added dropwise at -78 °C for 15 minutes with 25.9 mL of n-butyllithium (2.5 M in hexane). 32.5 mL of zinc chloride solution (1.9 M in 2-methyltetrahydrofuran) was added at -78 °C. The yellow solution was warmed to room temperature over 45 minutes. 18.3 g (58.6 mmol) of Intermediate 17-2, 565 mg (0.62 mmol) of tris(dibenzylideneacetone)dipalladium(0), and 358 mg (1.23 mmol) of tri-tert-butylphosphonium tetrafluoroborate were added, and the resulting solution was heated at 55 °C for 15 minutes. The reaction mixture was cooled to room temperature, filtered through a 3-cm silica gel layer, and then the silica gel layer was rinsed with 50 ml of tetrahydrofuran. The filtrate was concentrated under vacuum, and the resulting solid was dissolved in 100 ml of heated ethanol. The solution was cooled to room temperature until a suspension was formed. The suspension was filtered, and the solid was washed with 80 ml of ethanol. The product was purified by MPLC (silica gel, 0-40% gradient of heptane / toluene) using CombiFlash Companion to give 20.3 g (yield 73%) of Intermediate 17-2 as a white solid. ESI-MS (positive, m / z): C 32 H 32 N 2 O 2 exact mass of = 476.25; found 477.4 [M+1] +

[0648] Intermediate 17-3

[0649] [Chemistry]

[0650] 20.0 g (42.0 mmol) of Intermediate 17-2 and 33.0 g (126 mmol) of triphenylphosphine were heated in 100 mL of 1,2-dichlorobenzene at 174 °C for 3 hours. The reaction mixture was concentrated under vacuum. The product was stirred in 100 mL of heptane for 1 hour. The suspension was filtered and the solid was washed with heptane. The filtrate was concentrated under vacuum, and the solid was dissolved in dichloromethane and then filtered through a 4 cm silica gel layer, followed by rinsing the silica gel layer with 150 mL of dichloromethane. The collected eluent was concentrated under vacuum, and the product was purified by MPLC (silica gel, heptane / dichloromethane) using a CombiFlash Companion. The product was dissolved in 30 mL of dichloromethane and diluted with 50 mL of heptane. The solution was concentrated under vacuum to a volume of 50 mL until a suspension formed. The suspension was filtered and the solid was washed with heptane. The solid was suspended in 70 mL of tert-butyl methyl ether. The suspension was filtered and the solid was washed with tert-butyl methyl ether. The combined filtrates from the tert-butyl methyl ether washes were concentrated under vacuum to give 6.9 g (37% yield) of Intermediate 17-3 as a solid. ESI-MS (positive, m / z): C 32 H 32 N 2 Exact mass of = 444.26; found 445.4 [M+1] +

[0651] Intermediate 17-4

[0652] [Chemistry]

[0653] 1.53 g (4.50 mmol) of Intermediate 7-1, 2.00 g (4.50 mmol) of Intermediate 17-3, 86 mg (0.45 mmol) of copper(I) iodide, 154 mg (1.35 mmol) of cyclohexane-1,2-diamine, and 2.86 g (13.5 mmol) of tripotassium phosphate were suspended in 50 mL of 1,4-dioxane and heated at 91 °C for 12 h. The suspension was cooled to room temperature and filtered through a 3-cm silica gel layer, which was then rinsed with 50 mL of dioxane. The collected eluate was concentrated under vacuum, and the resulting solid was dissolved in 30 mL of dichloromethane and 50 mL of ethanol. The solution was concentrated under vacuum to a volume of 40 mL. The suspension was filtered, and the solid was washed with ethanol to give 2.56 g (87% yield) of Intermediate 17-4 as a white solid. ESI-MS (positive, m / z): C 42 H 43 BrN 2 exact mass of = 654.26; found 657.4 [M+3] +

[0654] Intermediate 17-5

[0655]

Chem.

[0656] 2.50 g (3.81 mmol) of Intermediate 17-4, 1.70 g (4.19 mmol) of Intermediate 2-3, 17 mg (0.08 mmol) of palladium(II) acetate, 188 mg (0.46 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos), and 3.24 g (15.3 mmol) of tripotassium phosphate were dissolved in a mixture of 40 ml of toluene, 20 mL of 1,4-dioxane, and 10 mL of water. The solution was degassed and refilled with argon three times and heated at 82 °C for 90 minutes. The reaction mixture was diluted with 50 mL of toluene and 100 ml of water. The organic phase was separated, washed with water (3 × 50 mL), dried over sodium sulfate, and filtered through a 3-cm silica gel layer. The silica gel layer was rinsed with toluene, and the collected eluate was concentrated under vacuum. The product was purified by MPLC (silica gel, heptane) using a CombiFlash Companion. The resulting product was diluted with 30 ml of dichloromethane and 50 ml of ethanol. The solution was concentrated under vacuum to 50 ml in volume until a suspension was formed. The suspension was filtered, and the solid was washed with ethanol to obtain 2.4 g (yield 74%) of Intermediate 17-5 as a white solid. ESI-MS (positive, m / z): C 62 H 67 N 3 Exact mass of = 853.53; found 854.7 [M+1] +

[0657] Compound 17

[0658]

Chemical Structure

[0659] 2.30 g (2.69 mmol) of Intermediate 17-5 was dissolved in 46 mL of 1,2-dichlorobenzene. 1.9 mL (10.8 mmol) of N,N-diisopropylethylamine and 5.4 mL of tribromoborane (1.0 M in heptane) were added dropwise. The brown solution was heated at 174 °C for 90 minutes and then cooled to 36 °C. 5.4 mL of tribromoborane (1.0 M in heptane) was added dropwise and heating was continued at 174 °C for 90 minutes. The reaction mixture was cooled to room temperature and 100 mL of methanol was added. The mixture was concentrated under vacuum and the residue was dissolved in 100 mL of heptane and 100 mL of water. The organic phase was washed with water (3 × 50 mL), dried over sodium sulfate, filtered, and concentrated under vacuum. The resulting solid was dissolved in 20 mL of dichloromethane and 60 mL of ethanol. The solution was concentrated under vacuum to 50 mL in volume until a suspension was formed. The suspension was filtered and the solid was washed with ethanol. The product was purified by MPLC (silica gel, 0 - 10% gradient of heptane / dichloromethane) using CombiFlash Companion. The isolated product was dissolved in 20 mL of dichloromethane and 60 mL of ethanol. The solution was concentrated to 50 mL in volume until a suspension was formed. The suspension was filtered and the solid was washed with 30 mL of ethanol to give 0.85 g (yield 37%) of Compound 17 as a yellow solid. ESI-MS (positive, m / z): C 62 H 64 BN 3 exact mass of = 861.52; found 862.6 [M+1] +

[0660] Compound 18

[0661]

Chemical Structure

[0662] 163 mg (0.249 mmol) of Intermediate 15-3, 0.152 mg (1.0 mmol) of (4-methoxyphenyl)boronic acid, and 0.325 mg (1.0 mmol) of cesium carbonate were suspended in a mixture of toluene / ethanol / water (6 mL / 2 mL / 1 mL). The suspension was degassed with Ar, and 3.4 mg (6 mol%) of palladium acetate and 12.3 mg (12 mol%) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl were added to the reaction mixture. The reaction mixture was heated at 80 °C for 2 hours. The reaction was cooled to room temperature and diluted with toluene / water. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extracts were washed with water and saturated brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane / dichloromethane as the eluent to give 123 mg (62% yield) of Compound 18 as a yellow solid. ESI-MS: 797.5 [M+H] +

[0663] Compound 19

[0664]

Chemical Structure

[0665] 200 mg (0.306 mmol) of Intermediate 15-3, 0.171 mg (1.22 mmol) of (4-fluorophenyl)boronic acid, and 0.399 mg (1.22 mmol) of cesium carbonate were suspended in a mixture of toluene / ethanol / water (6 mL / 2 mL / 1 mL). The suspension was degassed with Ar, and 4.1 mg (6 mol%) of palladium acetate and 15.1 mg (12 mol%) of 2-dicyclohexylphosphino-2’,6’-dimethoxybiphenyl were added to the reaction mixture. The reaction mixture was heated at 80 °C for 24 h. The reaction was cooled to room temperature and diluted with toluene / water. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extracts were washed with water, saturated brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane / toluene as the eluent to afford 166 mg (70% yield) of Compound 19 as a yellow solid. ESI-MS: 773.4 [M+H] +

[0666] Compound 20 Intermediate 20-1

[0667]

Chemical Structure

[0668] 10.0 g (37.0 mmol) of 1,3-dibromo-5-chlorobenzene, 21.3 g (76.0 mmol) of bis(4-(tert-butyl)phenyl)amine, 703 mg (0.77 mmol) of tris(dibenzylideneacetone)dipalladium(0), 892 mg (3.07 mmol) of tri-tert-butylphosphonium tetrafluoroborate, and 8.89 g (92.0 mmol) of sodium tert-butoxide were suspended in 200 mL of toluene. The suspension was evacuated and refilled with argon three times and heated at 72 °C for 90 minutes. The dark suspension was cooled to room temperature and washed with water (2 × 100 mL). The organic phase was dried over sodium sulfate and concentrated under vacuum. The solid was recrystallized from 300 mL of ethanol and then washed with cold ethanol to give 18.8 g (76% yield) of Intermediate 20-1 as a white solid. ESI-MS (positive, m / z): C 46 H 55 ClN 2 exact mass of = 670.41; found 671.4 [M + H] +

[0669] Intermediate 20-2

[0670]

Chemical Structure

[0671] 8.00 g (11.9 mmol) of Intermediate 20-1, 4.50 g (13.1 mmol) of Intermediate 5-1, 54 mg (0.24 mmol) of palladium(II) acetate, 587 mg (1.43 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos), and 10.1 g (47.7 mmol) of tripotassium phosphate were dissolved in a mixture of 100 mL of o-xylene, 50 mL of 1,4-dioxane, and 30 mL of water. The reaction mixture was evacuated and refilled with argon three times and heated at 82 °C for 5 h. The reaction mixture was cooled to room temperature and diluted with 200 mL of toluene and 100 mL of water. The organic phase was washed with water (3 × 100 mL), dried over sodium sulfate, and dichloromethane was added. The mixture was filtered and the filtrate was concentrated under vacuum. The product was stirred in 30 mL of dichloromethane and 150 mL of ethanol until a suspension formed. The suspension was filtered and the solid was washed with 100 mL of ethanol and 100 mL of heptane to give 6.9 g (68% yield) of Intermediate 20-2 as a white solid. ESI-MS (negative, m / z): C 62 H 65 N 3 exact mass of = 851.52; found 850.4 [M−1] +

[0672] Compound 20

[0673]

Chemical Structure

[0674] 3.00 g (3.52 mmol) of Intermediate 20-2 was suspended in 50 mL of 1,2-dichlorobenzene. 2.5 mL (14 mmol) of N,N-diisopropylethylamine and 7 mL of tribromoborane (1.0 M in heptane) were added dropwise. The yellow suspension was heated at 181 °C for 4 hours. The reaction mixture was cooled and 100 mL of methanol was added. The suspension was stirred for 15 minutes and then filtered. The suspension was stirred for 15 minutes and then filtered. The solid was washed with 50 mL of methanol, then 30 mL of water, and then with 50 mL of methanol and 30 mL of heptane. The solid was further purified by MPLC (silica gel, dichloromethane) using CombiFlash Companion to give 2.1 g (69% yield) of Compound 20 as a yellow solid. ESI-MS (positive, m / z): C 62 H 62 BN 3 exact mass of = 859.50; found 860.7 [M+1] +

[0675] Compound 21 Intermediate 21-1

[0676]

Chemical Structure

[0677] 5.00 g (10.8 mmol) of Intermediate 1-3, 4.07 g (11.9 mmol) of Intermediate 5-1, 48 mg (0.22 mmol) of palladium(II) acetate, 531 mg (1.29 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos), and 9.15 g (43.1 mmol) of tripotassium phosphate were dissolved in a mixture of 100 mL of o-xylene, 50 mL of 1,4-dioxane, and 30 mL of water. The emulsion was evacuated and refilled with argon three times and heated at 86 °C for 26 h. The reaction mixture was cooled and 50 mL of toluene and 50 mL of water were added. The organic phase was washed with water (3 × 50 mL), dried over sodium sulfate, and concentrated under vacuum. The solid product was suspended in 100 mL of heptane, filtered, and the solid was washed with heptane. The product was further purified by MPLC (silica gel, 0–10% gradient of cyclohexane / ethyl acetate) using a CombiFlash Companion. The resulting solid was suspended in 30 mL of dichloromethane and 50 mL of ethanol. The suspension was filtered and the solid was washed with ethanol to give 3.65 g (53% yield) of Intermediate 21-1 as a white solid. ESI-MS (negative, m / z): C 45 H 48 N 2 Exact mass of Si = 644.36; found 643.3 [M−1] +

[0678] Compound 21

[0679]

Chemical Structure

[0680] 3.50 g (5.43 mmol) of Intermediate 21-1 was dissolved in 200 mL of 1,2-dichlorobenzene. 3.8 mL (21.7 mmol) of N,N-diisopropylethylamine and 8.1 mL of tribromoborane (1.0 M in heptane) were added dropwise. The suspension was heated at 142 °C for 18 h. The reaction mixture was cooled and 300 mL of methanol was added. The suspension was filtered and the solid was washed with 100 mL of methanol, 50 mL of water, and 50 mL of methanol. The product was further purified by MPLC (silica gel, dichloromethane) using CombiFlash Companion to give 1.02 g (32% yield) of Compound 21 as a yellow solid. ESI-MS (positive, m / z): C 42 H 37 BN 2 exact mass of = 580.30; found 581.7 [M+1] +

[0681] Compound 22 Intermediate 22-1

[0682]

Chem.

[0683] 7.18 g (25.50 mmol) of bis(4-(tert-butyl)phenyl)amine, 10.67 g (25.50 mmol) of Intermediate 7-1, and 3.43 g (35.70 mmol) of sodium tert-butoxide were suspended in 102 mL of toluene. After degassing the suspension using three freeze-degas-thaw cycles, 295 mg (0.51 mmol) of xanthphos and 117 mg (0.13 mmol) of tris(dibenzylideneacetone)dipalladium(0) were added to the mixture. Then, after two additional freeze-degas-thaw cycles, the reaction mixture was stirred at 100 °C for 14.5 hours. The reaction was cooled to room temperature and diluted with toluene and water. The aqueous layer was extracted with toluene. The organic extract was washed with saturated brine, dried over sodium sulfate, filtered, and the solution was concentrated. The residue was purified by silica gel column chromatography using cyclohexane as the eluent to afford 10.8 g (79% yield) of Intermediate 22-1 as a beige foam. ESI-MS: 494.6 [M-H] -

[0684] Intermediate 22-2

[0685]

Chemical formula

[0686] 2.96 g (6.01 mmol) of Intermediate 22-1, 1.98 g (7.81 mmol) of bis(pinacolato)diboron, and 1.18 g (12.02 mmol) of sodium acetate were suspended in 30 mL of toluene. The suspension was degassed using three freeze-degas-thaw cycles, and 110 mg (0.12 mmol) of tris(dibenzylideneacetone)dipalladium(0) and 229 mg (0.48 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl were added to the mixture. After two additional freeze-degas-thaw cycles, the reaction mixture was heated at 110 °C for 16 h. The reaction was cooled to room temperature and diluted with toluene and water. The aqueous layer was extracted with toluene, the organic layer was washed with saturated brine, dried over magnesium sulfate, filtered, and the solution was concentrated. The crude product was recrystallized using dichloromethane and acetonitrile to give 2.56 g (79% yield) of Intermediate 22-2 as a white solid. ESI-MS: 540.7 [M+H] +

[0687] Intermediate 22-3

[0688]

Chemical Structure

[0689] 1.50 g (2.68 mmol) of Intermediate 14-4, 2.16 g (4.01 mmol) of Intermediate 22-2, and 2.28 g (10.70 mmol) of potassium phosphate were dissolved in 22 mL of toluene, 11 mL of dioxane, and 7 mL of water. After degassing the solution using three freeze-degas-thaw cycles, 21 mg (0.09 mmol) of palladium acetate and 231 mg (0.56 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl were added to the mixture. Then, after two additional freeze-degas-thaw cycles, the mixture was stirred at 85 °C for 21 hours. The reaction was cooled to room temperature and diluted with toluene. The organic extract was washed with water, dried over sodium sulfate, filtered, and the solution was concentrated. The residue was purified by silica gel column chromatography using a mixed solvent of heptane and toluene as the eluent to obtain 2.87 g (80% yield) of Intermediate 22-3 as a white solid. ESI-MS: 893.8 [M-H] -

[0690] Compound 22

[0691]

Chemical formula

[0692] 2.87 g (3.21 mmol) of Intermediate 22-3 was dissolved in 46 mL of dichlorobenzene. Then, 6.59 mL (6.59 mmol) of 1.0 M boron tribromide in heptane, followed by 2.3 mL (10.28 mmol) of N,N-diisopropylethylamine were added to the solution, and the mixture was stirred at 180 °C for 20 hours. The reaction was cooled to room temperature and diluted with methanol. The precipitate was collected by filtration and washed with ethanol and water. The crude product was purified by silica gel column chromatography using a mixed solvent of heptane and dichloromethane as the eluent. The product was dissolved in dichloromethane, precipitated by the addition of acetonitrile, and then filtered to obtain 2.19 g (76% yield) of Compound 22. ESI-MS: 901.2 [M+H] +

[0693] Compound 23 Intermediate 23-1

[0694]

Chem.

[0695] 27.2 g (86.0 mmol) of 2-bromo-4-chloro-1-iodobenzene, 20.0 g (82.0 mmol) of N-phenyl-2-biphenylamine, and 11.0 g (114 mmol) of sodium tert-butoxide were added to 250 mL of toluene. N 2 The mixture was degassed by bubbling N gas for 30 minutes, and 933 mg (1.25 mol%) of tris(dibenzylideneacetone)dipalladium(0) and 1.18 g (5 mol%) of tri-tert-butylphosphonium tetrafluoroborate were added. The reaction mixture was heated to 70 °C for 2 hours and then cooled to room temperature. The reaction mixture was filtered through a silica gel pad, and the product was eluted with heptane. The filtrate and washings were collected, the solvent was removed by rotary evaporator, and then dried at 200 °C under high vacuum. The oil was crystallized using a minimal amount of heated heptane. The brown solid was then dissolved in dichloromethane, washed twice with a 0.05% aqueous solution of sodium cyanide, and then washed with saturated brine. The organic matter was dried over magnesium sulfate, and the solvent was removed by rotary evaporator. The oil was crystallized using a minimal amount of heated heptane, filtered, and washed with pentane to obtain 10.9 g (yield 28.4%) of Intermediate 23-1 as a white solid. 1 H NMR (300 MHz, DMSO-d 6 ) δ 7.45 (d, J = 2.4 Hz, 1H), 7.42 - 7.30 (m, 1H), 7.30 - 7.08 (m, 10H), 7.07 - 7.00 (m, 1H), 7.00 - 6.84 (m, 1H), 6.75 (m, 3H).

[0696] Intermediate 23-2

[0697]

Chem.

[0698] Under an inert atmosphere, 35 mL of n-butyllithium (2.5 M in hexane) was added dropwise to a solution of 34.0 g (78.2 mmol) of Intermediate 23-1 in 360 mL of tetrahydrofuran while maintaining the temperature below -60 °C using an acetone-dry ice bath. After the addition was complete, the reaction mixture was stirred at -78 °C for 1.5 h. Then, 30 mL (268 mmol) of trimethyl borate was slowly added while maintaining the temperature below -60 °C. After the addition was complete, the reaction mixture was stirred at -78 °C for 15 min, then slowly warmed to room temperature and stirred for 20 min to obtain an emulsion solution. 400 mL of 10% HCl solution was added to the reaction mixture, and the two-phase mixture was stirred for 1 h. The organic solvent was removed using a rotary evaporator, and the resulting suspension was filtered. The solid was refluxed and pulverized in 500 mL of heptane for 1 h. Then, the white suspension was concentrated to half its volume using a rotary evaporator, stirred at 0 °C for 1 h, and then filtered to obtain 22.3 g (yield 71.3%) of Intermediate 23-2 as a white solid. ESI-MS: 400.2 [M+H] +

[0699] Intermediate 23-3

[0700]

Chem.

[0701] 4.88 g (18.9 mmol) of 2-bromo-4-(tert-butyl)-1-nitrobenzene, 6.3 g (15.8 mmol) of Intermediate 23-2, and 1.87 g (81.3 mmol) of sodium hydroxide were dissolved in a mixture of 75 mL of dioxane and 30 mL of water, N 2The mixture was degassed by bubbling. 547 mg (3 mol%) of tetrakis(triphenylphosphine)palladium(0) was added and the reaction mixture was heated at 85 °C for 3 h. The reaction mixture was cooled to room temperature, poured into water, extracted with dichloromethane, and the organic phase was washed with water and saturated brine. The organic matter was dried over magnesium sulfate, heptane was added, and dichloromethane was removed on a rotary evaporator until a precipitate began to form. The precipitate was stirred at approximately 15 °C, then the suspension was filtered and washed with heptane. The solid was dissolved in 50 mL of dichloromethane and 100 mL of heptane was added. The solution was concentrated on a rotary evaporator to approximately 50 mL and stirred at room temperature for 1 h. The yellow suspension was filtered to give 4.72 g (55% yield) of Intermediate 23-3 as a yellow solid. ESI-MS: 533.3 [M+H] +

[0702] Intermediate 23-4

[0703]

Chemical Structure

[0704] 16.2 g (30.5 mmol) of Intermediate 23-3 and 40.0 g (152 mmol) of triphenylphosphine were dissolved in 160 mL of 1,2-dichlorobenzene and heated to reflux for 11 hours. Then, 1,2-dichlorobenzene and most of the triphenylphosphine were distilled off under reduced pressure, and the remaining black tarry substance was cooled to room temperature. Then, the residue was dissolved in refluxing heptane, 15 g of Hyflo® Super-Cel® was added, and then 5 g of activated carbon was added. Then, the suspension was hot-filtered through a pad of Hyflo® Super-Cel®, the pad was washed with heptane, and the collected filtrate was filtered through a silica pad. The pad was washed with heptane, and the colorless filtrate was discarded. Then, the product was eluted with toluene to obtain an orange filtrate. The solvent was removed from the filtrate using a rotary evaporator, and the crude product was purified twice by silica gel column chromatography using a mixture of heptane and dichloromethane. The resulting resin was dissolved in a mixture of heptane and dichloromethane, and dichloromethane was removed using a rotary evaporator. When the resulting solution was cooled to 0 °C, a precipitate formed during that time. After stirring for 2 hours, the suspension was filtered to obtain 4.53 g (yield 30%) of Intermediate 23-4 as a white solid. ESI-MS: 499.4 [M-H] -

[0705] Intermediate 23-5

[0706]

Chemical Structure

[0707] 2.04 g (3.77 mmol) of Intermediate 22-2, 1.8 g (3.59 mmol) of Intermediate 23-4, and 1.91 g (8.98 mmol) of potassium phosphate were suspended in 35 mL of toluene, 23 mL of dioxane, and 12 mL of water, and N 2The reaction mixture was degassed by bubbling. Then, 66 mg (2 mol%) of tris(dibenzylideneacetone)dipalladium(0) and 137 mg (8 mol%) of Xphos were added, and the reaction was heated at 90 °C for 24 h. Then, an additional 33 mg (1 mol%) of tris(dibenzylideneacetone)dipalladium(0) and 69 mg (4 mol%) of Xphos were added, and the reaction was heated at 90 °C for an additional 3 h and then cooled to room temperature. The reaction was poured into 200 mL of saturated aqueous ammonium chloride and extracted with ethyl acetate. The organic phase was washed with water and saturated brine, dried over magnesium sulfate, and filtered through a silica gel pad. The pad was washed with ethyl acetate, and the solvent of the filtrate was evaporated on a rotary evaporator. The crude product was purified by silica gel column chromatography using a mixture of heptane and ethyl acetate as the eluent and then purified again by silica gel column chromatography using a mixture of heptane and toluene as the eluent. The resulting colorless foam was dissolved in dichloromethane and methanol was added. The solution was concentrated at room temperature on a rotary evaporator until a precipitate formed. The suspension was stirred at -40 °C for 20 min and filtered. The second collection was filtered from the mother liquor, and the white solids were combined to give 1.49 g (47% yield) of Intermediate 23-5 as a white solid. ESI-MS: 878.7 [M+H] + , 876.6 [M-H] -

[0708] Compound 23

[0709]

Chemical Structure

[0710] Under an inert atmosphere, 0.75 mL of n-butyllithium (2.5 M in hexane) was added dropwise to a solution containing 1.50 g (1.71 mmol) of Intermediate 23-5 in 70 mL of tert-butylbenzene while maintaining the temperature below -15 °C using an ice / sodium chloride bath. After the addition was complete, the reaction mixture was heated at room temperature for 20 minutes, then cooled to -15 °C, and 3.5 mL of boron tribromide (1 M in heptane) was slowly added while maintaining the temperature below -10 °C. The reaction mixture was warmed at 120 °C for 5 hours. Then, the reaction mixture was cooled to room temperature and quenched with 100 mL of 10% aqueous sodium bicarbonate solution. The organic phase was washed twice with water, dried over sodium sulfate, and filtered through a silica gel pad. The pad was washed with toluene, and the filtrate was concentrated on a rotary evaporator to remove toluene. The yellow solution was cooled to 0 °C, and 300 mL of acetonitrile was added. The precipitate was slowly formed over 2 hours, and the resulting solid was filtered off. The mother liquor was concentrated on a rotary evaporator until it became an oil, dissolved in dichloromethane. 70 mL of acetonitrile was added, and the solution was concentrated on a rotary evaporator to approximately 40 mL. The solution was cooled to room temperature, seeded with crystals from the previous precipitate, and stirred for an additional 1 hour. The resulting precipitate was then filtered, and the collected solid was purified twice by silica gel column chromatography using a mixture of heptane and dichloromethane as the eluent. The purified product was dissolved in 50 mL of dichloromethane and 75 mL of acetonitrile, and the solution was concentrated until a precipitate formed. The suspension was stirred at room temperature for 30 minutes, filtered, and 870 mg (58% yield) of Compound 23 was obtained as a bright yellow solid. ESI-MS: 886.7 [M+H] +

[0711] Compound 24 Intermediate 24-1

[0712]

Chemical Structure

[0713] 4.07 g (12.0 mmol) of intermediate 7-1, 4.13 g (10.2 mmol) of intermediate 2-3, and 0.96 g (24.0 mmol) of sodium hydroxide were suspended in a mixture of tetrahydrofuran / water (54 mL / 27 mL). The suspension was degassed with Ar, and 277 mg (2 mol%) of tetrakis(triphenylphosphine)palladium(0) was added to the reaction mixture. The reaction mixture was refluxed for 1.5 h. The reaction was cooled to room temperature and diluted with toluene / water. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extracts were washed with water and saturated brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane / toluene as the eluent to give 4.30 g (73% yield) of intermediate 24-1 as a white foam. ESI-MS: 490.2 [M-H] -

[0714] Intermediate 24-2

[0715]

Chemical formula

[0716] 1.74 g (4.97 mmol) of 6-bromo-2,3-diphenylbenzofuran, 1.00 g (4.87 mmol) of 3,5-di-tert-butylaniline, and 1.17 g (12.17 mmol) of sodium tert-butoxide were suspended in 24 mL of toluene. The suspension was degassed with Ar, and 166 mg (6 mol%) of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene and 134 mg (3 mol%) of tris(dibenzylideneacetone)dipalladium(0) were added to the reaction mixture. The reaction mixture was heated to 90 °C for 45 min. The reaction was cooled to room temperature, diluted with toluene / water, and filtered through Celite. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extracts were washed with water and saturated brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane / toluene as the eluent to give 1.4 g (61% yield) of intermediate 24-2 as a white solid. ESI-MS [M+H] 474.4

[0717] Intermediate 24-3

[0718]

Chem.

[0719] 1.35 g (2.75 mmol) of Intermediate 24-1, 1.30 g (2.75 mmol) of Intermediate 24-2, and 661 mg (6.88 mmol) of sodium tert-butoxide were suspended in 35 mL of toluene. The suspension was degassed with Ar, and 127 mg (8 mol%) of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene and 101 mg (4 mol%) of tris(dibenzylideneacetone)dipalladium(0) were added to the reaction mixture. The reaction mixture was heated to 90 °C for 2.5 h. The reaction was cooled to room temperature, diluted with toluene / water, and filtered through celite. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extracts were washed with water, saturated brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane / toluene as the eluent to obtain 2.28 g (yield 94%) of Intermediate 24-3 as a beige foam. ESI-MS: 883.7 [M+H] +

[0720] Compound 24

[0721]

Chem.

[0722] 1.86 g (2.1 mmol) of Intermediate 24-3 was dissolved in 40 mL of tert-butylbenzene, degassed with Ar, and cooled to 0 °C. After dropwise addition of 4.07 mL (6.51 mmol) of tert-butyllithium (1.6 M solution in pentane), the mixture was stirred at the same temperature for 5 minutes. Then, the reaction mixture was stirred at room temperature for 2 hours. Next, 4.20 mL (4.20 mmol) of tribromoborane (1 M solution in heptane) was added dropwise, and after stirring the reaction mixture for 5 minutes, 1.44 mL (8.40 mmol) of N-ethyl-N-isopropylpropan-2-amine was added. After stirring the reaction mixture at room temperature for 3 hours, it was quenched with water / toluene. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extracts were washed with water and saturated brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane / toluene as the eluent to obtain 1.25 g (yield 66%) of Compound 24 as a yellow solid. ESI-MS [M+H] 891.6

[0723] Compound 25 Intermediate 25-1

[0724]

Chemical Structure

[0725] 20.0 g (0.11 mol) of 2,5-dichlorobenzene-1,4-diamine, 48.2 g (0.23 mol) of 1-bromo-4-(tert-butyl)benzene, 517 mg (0.57 mmol) of tris(dibenzylideneacetone)dipalladium(0), 1.06 g (0.6 mmol) of 2,2'-bis(diphenylphosphino)-1,1'-binaphthalene (BINAP), and 32.6 g (0.34 mol) of sodium tert-butoxide were suspended in 400 mL of o-xylene. The suspension was heated at 126 °C for 4 hours. The reaction mixture was cooled to room temperature, and 100 ml of 5% aqueous sodium cyanide solution was added. The mixture was stirred vigorously for 30 minutes and then filtered. The remaining solid was washed with 300 mL of ethyl acetate. The collected filtrate was washed with water (3 × 100 mL), dried over magnesium sulfate, and concentrated under vacuum. The resulting solid was suspended in 400 mL of ethanol, and the suspension was stirred for 1 hour. After the suspension was cooled, it was filtered, and the solid was washed with cold ethanol to obtain 31.6 g (yield 63%) of Intermediate 25-1 as a white solid. ESI-MS (positive, m / z): C 26 H 30 Cl 2 N 2 exact mass of = 440.18; found 441.3 [M+1] +

[0726] Intermediate 25-2

[0727]

Chemical Structure

[0728] 30.0 g (68.0 mmol) of Intermediate 25-1, 517 mg (0.57 mmol) of palladium(II) acetate, 789 mg (0.6 mmol) of tri-tert-butylphosphonium tetrafluoroborate, 5.2 g (51 mmol) of pivalic acid, and 47 g (0.34 mol) of potassium carbonate were suspended in 300 mL of N,N-dimethylacetamide. The suspension was heated at 152 °C for 8 hours. The reaction mixture was cooled to room temperature and poured into 1000 mL of water. The suspension was stirred for 1 hour, then filtered, and the solid was washed with 400 mL of water. The solid was dissolved in 300 mL of dichloromethane, filtered through a 3 cm silica gel layer, and the silica gel layer was rinsed with 600 mL of dichloromethane and 1000 mL of ethyl acetate. The collected eluent was concentrated under vacuum to 100 mL volume, and 200 mL of heptane was added. The mixture was stirred until a suspension was formed. The suspension was filtered, and the white solid was washed with heptane to give 25.0 g (quantitative yield) of Intermediate 25-2. ESI-MS (positive, m / z): C 26 H 28 N 2 exact mass of = 368.23; found 369.5 [M+1] +

[0729] Intermediate 25-3

[0730]

Chemical formula

[0731] 25.0 g (67.8 mmol) of Intermediate 25-2 and 32.6 g (0.15 mol) of di-tert-butyl dicarbonate were dissolved in 700 mL of tetrahydrofuran. 1.82 g (14.9 mmol) of 4-(dimethylamino)pyridine was added, and the suspension was stirred at room temperature for 2 hours. The suspension was filtered, and the solid was washed with 100 mL of tetrahydrofuran and 200 mL of ethyl acetate to give 29.4 g (76% yield) of Intermediate 25-3 as a white solid.

[0732] Intermediate 25-4

[0733]

Chem.

[0734] 29.0 g (51.0 mmol) of Intermediate 25-3 was suspended in 600 mL of tert-butylbenzene and heated at 164 °C for 3 hours. The solution was cooled and stirred at room temperature for 18 hours. The resulting suspension was filtered. The filtrate was concentrated under vacuum to give 10.2 g (43% yield) of Intermediate 25-4 as a white solid. ESI-MS (negative, m / z): C 31 H 36 N 2 O 2 exact mass = 468.28; found 467.4 [M−1] +

[0735] Intermediate 25-5

[0736]

Chem.

[0737] 16.0 g (34.1 mmol) of Intermediate 25-4, 10.7 g (41 mmol) of 1-(tert-butyl)-4-iodobenzene, 650 mg (3.41 mmol) of copper(I) iodide, 1.12 g (10.2 mmol) of cyclohexane-1,2-diamine, and 21.7 g (102 mmol) of tripotassium phosphate were suspended in 350 mL of 1,4-dioxane and heated at 91 °C for 4 hours. 1.00 g (3.8 mmol) of 1-(tert-butyl)-4-iodobenzene was added and heating was continued at 91 °C for 4 hours. The suspension was filtered through a 3 cm silica gel layer and the silica gel layer was rinsed with 200 mL of dioxane. The collected eluate was concentrated under vacuum and the product was dissolved in 50 mL of dichloromethane. 200 mL of ethanol was added and the solution was concentrated to 200 mL until a suspension formed. The suspension was filtered and the solid was washed with ethanol to give 13.8 g (67% yield) of Intermediate 25-5. ESI-MS (positive, m / z): C41 H 48 N 2 O 2 Exact mass of = 600.37; measured value 601.8 [M+1] +

[0738] Intermediate 25-6

[0739]

Chem.

[0740] 13.5 g (22.5 mmol) of Intermediate 25-5 was heated at 230 °C for 90 minutes. The melted solid was cooled and purified by MPLC using CombiFlash Companion (silica gel, 0 - 8% gradient of heptane / ethyl acetate) to give 8.7 g (77%) of Intermediate 25-6 as a white solid. ESI-MS (positive, m / z): C 36 H 40 N 2 Exact mass of = 500.32; measured value 501.7 [M+1] +

[0741] Intermediate 25-7

[0742]

Chem.

[0743] 2.4 g (7.0 mmol) of intermediate 7-1, 2.70 g (5.39 mmol) of intermediate 25-6, 103 mg (0.54 mmol) of copper(I) iodide, 185 mg (1.62 mmol) of cyclohexane-1,2-diamine, and 3.43 g (16.2 mmol) of tripotassium phosphate were suspended in 100 mL of 1,4-dioxane and heated at 91 °C for 8 hours. The suspension was cooled to room temperature and filtered through a 3 cm silica gel layer, which was then rinsed with 30 mL of dioxane. The collected eluate was concentrated under vacuum, and the product was further purified by MPLC (silica gel, 0 - 25% gradient of heptane / dichloromethane) using a CombiFlash Companion to give 2.45 g (64% yield) of intermediate 25-7 as a white solid. ESI-MS (positive, m / z): C 46 H 51 BrN 2 exact mass of = 710.32; found 711.6 [M+1] +

[0744] Intermediate 25-8

[0745]

Chemical Structure

[0746] 30.0 g (0.13 mol) of 2-bromo-(tert-butyl)aniline, 34.2 g (0.13 mol) of 1-(tert-butyl)-4-iodobenzene, 295 mg (1.32 mmol) of palladium(II) acetate, 729 mg (1.32 mmol) of 1,1'-bis(diphenylphosphino)ferrocene (dppf), and 19.0 g (0.20 mol) of sodium tert-butoxide were suspended in 300 mL of toluene. The suspension was heated at 108 °C for 18 h. 148 mg (0.66 mmol) of palladium(II) acetate and 365 mg (0.66 mmol) of dppf were added, and heating was continued at 108 °C for 8 h. The reaction mixture was cooled to room temperature, 1 g of sodium cyanide and 100 mL of water were added. The mixture was stirred for 1 h and then washed with water (3 × 100 mL). The organic phase was dried over sodium sulfate and concentrated under vacuum. The product was dissolved in 300 mL of heated methanol, and the solution was stirred at room temperature for 18 h. The resulting suspension was filtered, and the solid was washed with cold methanol to give 24.3 g (51% yield) of Intermediate 25-8 as a gray solid. ESI-MS (positive, m / z): C 20 H 26 BrN exact mass = 359.12; found 362.4 [M+3] +

[0747] Intermediate 25-9

[0748]

Chem.

[0749] 5.80 g (16.1 mmol) of Intermediate 25-8, 6.13 g (24.1 mmol) of bis(pinacolato)diboron, 394 mg (0.48 mmol) of 1,1'-bis(diphenylphosphino)ferrocene-palladium(II) dichloride dichloromethane complex, and 6.32 g (64.4 mmol) of potassium acetate were suspended in 150 mL of 1,4-dioxane. The reaction mixture was heated at 89 °C for 8 hours. The resulting suspension was cooled to room temperature and diluted with 100 mL of water and 100 mL of ethyl acetate. The mixture was washed with water (3 × 50 mL), the organic phase was dried over sodium sulfate, and concentrated under vacuum. The resulting solid was dissolved in 50 mL of dichloromethane and 100 mL of ethanol and concentrated to 100 mL volume under vacuum. The resulting suspension was filtered and the solid was washed with 50 mL of ethanol to give 3.8 g (yield 58%) of Intermediate 25-9. ESI-MS (positive, m / z): C 26 H 38 BNO 2 exact mass of = 407.30; found 408.7 [M+1] +

[0750] Intermediate 25-10

[0751]

Chemical Structure

[0752] 1.51 g (3.71 mmol) of Intermediate 25-9, 2.40 g (3.37 mmol) of Intermediate 25-7, 151 mg (0.67 mmol) of palladium(II) acetate, 166 mg (0.41 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos), and 2.86 g (13.5 mmol) of tripotassium phosphate were dissolved in a mixture of 60 mL of toluene, 30 mL of 1,4-dioxane, and 20 mL of water. The reaction mixture was heated at 83 °C for 1 h and then cooled to room temperature. 200 mL of toluene and 100 mL of water were added. The organic phase was washed with water (3 × 100 mL), dried over sodium sulfate, and concentrated under vacuum. The product was dissolved in 20 mL of dichloromethane and 70 mL of ethanol. The solution was concentrated under vacuum to a volume of 60 mL until a suspension formed. The suspension was filtered and the solid was washed with 50 mL of ethanol. The product was further purified by MPLC (silica gel, 0–16% gradient of heptane / dichloromethane) using a CombiFlash Companion to give 1.59 g (52% yield) of Intermediate 25-10 as a white solid. ESI-MS (positive, m / z): C 66 H 77 N 3 exact mass of = 911.61; found 912.7 [M+1] +

[0753] Compound 25

[0754]

Chemical Structure

[0755] 1.50 g (1.64 mmol) of Intermediate 25-10 was dissolved in 45 mL of 1,2-dichlorobenzene. 1.15 mL (6.6 mmol) of N,N-diisopropylethylamine and 3.3 mL of tribromoborane (1.0 M in heptane) were added dropwise. The yellow solution was heated at 174 °C for 2.5 h. The solution was cooled to room temperature. 3.3 mL of tribromoborane (1.0 M in heptane) was added and heating was continued at 174 °C for 25 h. The reaction mixture was cooled to room temperature, diluted with 200 mL of ethanol and stirred for 1 h. The suspension was filtered and the solid was further purified by MPLC (silica gel, 0 - 50% gradient of heptane / dichloromethane) using CombiFlash Companion to give 212 mg (14% yield) of Compound 25 as a yellow solid. ESI-MS (positive, m / z): C 66 H 74 BN 3 exact mass of = 919.60; found 920.9 [M+1] +

[0756] Compound 26 Intermediate 26-1

[0757]

Chemical Structure

[0758] 10.0 g (46.9 mmol) of 3-bromobenzo[b]thiophene, 7.00 g (46.9 mmol) of 4-(tert-butyl)aniline, 540 mg (0.94 mmol) of tris(dibenzylideneacetone)dipalladium(0), 876 mg (3.07 mmol) of 2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl (RuPhos), and 9.02 g (94.0 mmol) of sodium tert-butoxide were suspended in 120 mL of toluene. The suspension was evacuated and refilled with argon three times and heated at 105 °C for 18 h. The dark suspension was dissolved, cooled to room temperature, and diluted with 100 ml of toluene and 100 mL of water. The aqueous phase was washed with water (3 × 50 mL), dried over sodium sulfate, and concentrated under vacuum. The product was further purified by MPLC (silica gel, 0–2% gradient of cyclohexane / ethyl acetate) using a CombiFlash Companion to give 10.5 g (79% yield) of Intermediate 26-1. ESI-MS (positive, m / z): C 18 H 19 NS exact mass = 281.12; found 282.4 [M+1] +

[0759] Intermediate 26-2

[0760]

Chemical Structure

[0761] 3.61 g (10.7 mmol) of Intermediate 7-1, 3.00 g (10.7 mmol) of Intermediate 26-1, 24 mg (0.11 mmol) of palladium(II) acetate, 63 mg (0.11 mmol) of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos), and 1.54 g (16.0 mmol) of sodium tert-butoxide were suspended in 60 mL of toluene. The suspension was heated at 77 °C for 4 hours. The reaction mixture was cooled to room temperature and diluted with 100 mL of water and 100 mL of toluene. The organic phase was separated, washed with water (3 × 100 mL), and dried over sodium sulfate. The mixture was filtered through a 3-cm silica gel layer, and the silica gel layer was rinsed with 50 mL of toluene. The collected eluate was concentrated under vacuum, and the product was further purified by MPLC (silica gel, heptane) using a CombiFlash Companion to give 2.7 g (51% yield) of Intermediate 26-2. ESI-MS (positive, m / z): C 28 H 30 The exact mass of BrNS = 491.13; found 492.6 [M+1] +

[0762] Intermediate 26-3

[0763]

Chemical Structure

[0764] 3.00 g (6.09 mmol) of Intermediate 26-2, 2.30 (6.70 mmol) of Intermediate 5-1, 27 mg (0.12 mmol) of palladium(II) acetate, 300 mg (0.73 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (SPhos), and 5.17 g (24.4 mmol) of tripotassium phosphate were dissolved in a mixture of 60 mL of toluene, 30 mL of 1,4-dioxane, and 20 mL of water. The solution was evacuated and refilled with argon three times and heated at 84 °C for 7 hours. The reaction mixture was cooled to room temperature and diluted with 200 mL of toluene and 100 mL of water. The organic phase was washed with water (3 × 100 mL), dried over sodium sulfate, and concentrated under vacuum. The product was further purified by MPLC (silica gel, 0 - 10% gradient of heptane / ethyl acetate) using a CombiFlash Companion. The isolated product was dissolved in 30 mL of dichloromethane and 50 mL of ethanol and concentrated under vacuum until a suspension formed. The suspension was filtered and the solid was washed with 50 mL of ethanol to give 2.9 g (76% yield) of Intermediate 26-3. ESI-MS (positive, m / z): C 44 H 40 N 2 Exact mass of S = 628.29; found 629.8 [M + 1] +

[0765] Compound 26

[0766]

Chemical Structure

[0767] 1.50 g (2.39 mmol) of Intermediate 26-3 was suspended in 25 mL of 1,2-dichlorobenzene. 1.7 mL (9.5 mmol) of N,N-diisopropylethylamine and 4.8 mL of tribromoborane (1.0 M in heptane) were added dropwise. The yellow suspension was heated at 176 °C for 3 hours. The reaction mixture was cooled to room temperature and diluted with 100 mL of ethanol. The suspension was stirred for 15 minutes and then filtered. The filtrate was concentrated under vacuum and the residue was stirred in 100 mL of heptane. The suspension was filtered and the solid was washed with 50 mL of heptane to give 142 mg (yield 9%) of Compound 26 as a yellow solid. ESI-MS (positive, m / z): C 44 H 40 N 2 Exact mass of S = 628.29; found 629.8 [M+1] +

[0768] Compound 27 Intermediate 27-1

[0769]

Chemical Structure

[0770] 10.32 g (50.0 mmol) of 2-bromo-5-chloroaniline, 9.13 mL (51.5 mmol) of 1-(tert-butyl)-4-iodobenzene, and 6.73 g (70.0 mmol) of sodium tert-butoxide were suspended in 250 mL of toluene. The suspension was degassed with Ar, and 289 mg (1 mol%) of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene and 429 mg (0.5 mol%) of tris(dibenzylideneacetone)dipalladium(0) were added to the reaction mixture. The reaction mixture was heated to 105 °C for 50 minutes. The reaction was cooled to room temperature, diluted with toluene / water, and filtered through celite. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extract was washed with water, saturated brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane as the eluent to give 15.1 g (89% yield) of Intermediate 27-1 as a clear oil. 1 H NMR (300 MHz, chloroform-d 3 ) δ 7.46 - 7.39 (m, 3H), 7.22 - 7.12 (m, 2H), 6.69 (dd, 1H), 6.05 (broad s, 1H), 1.38 (s, 9H).

[0771] Intermediate 27-2

[0772]

Chemical Structure

[0773] 15.0 g (44.3 mmol) of Intermediate 27-1 and 13.35 mL (89.0 mmol) of 1,8-diazabicyclo[5.4.0]undec-7-ene were suspended in 221 mL of dimethylformamide. The suspension was degassed with Ar, and 451 mg (1.5 mol%) of bis(triphenylphosphine)palladium(II) chloride was added to the reaction mixture. The reaction mixture was heated to 120 °C for 30 hours. The reaction was cooled to room temperature, diluted with toluene / water, and filtered through celite. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extracts were washed with water and saturated brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane / toluene as the eluent to obtain 6.43 g (56% yield) of Intermediate 27-2 as a white solid. The molecular mass of the product was confirmed by LC-MS [M-H] - at 256.5.

[0774] Intermediate 27-3

[0775]

Chemical formula

[0776] 4.00 g (15.52 mmol) of Intermediate 27-2, 4.59 g (23.28 mmol) of 3-bromobenzofuran, 6.43 g (46.6 mmol) of potassium carbonate, and 986 mg (15.52 mmol) of copper were suspended in 52 mL of nitrobenzene. After degassing the suspension with Ar, it was heated to 195 °C for 3 days. The reaction was cooled to room temperature, diluted with toluene, and filtered through celite. The organic layer was washed with a 10% solution of 3-amino-1-propanol until the blue color disappeared. The aqueous layer was further extracted with toluene. The collected organic extracts were washed with saturated brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane as the eluent to obtain 2.38 g (41% yield) of Intermediate 27-3 as a white foam. The molecular mass of the product was confirmed by LC-MS [M+H] + at 374.5.

[0777] Intermediate 27-4

[0778]

Chem.

[0779] 2.30 g (6.15 mmol) of Intermediate 27-3, 2.74 g (6.77 mmol) of Intermediate 2-3, and 4.01 g (12.3 mmol) of cesium carbonate were suspended in a mixture of toluene / ethanol / water (28 mL / 9 mL / 5 mL). The suspension was degassed with Ar, and 55 mg (4 mol%) of palladium acetate and 235 mg (8 mol%) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl were added to the reaction mixture. The reaction mixture was heated to 85 °C for 3 hours. The reaction was cooled to room temperature, diluted with toluene, and then filtered through a Celite pad. Water was added to the filtrate, the layers were separated, and the aqueous layer was further extracted with toluene. The organic extracts were washed with water and saturated brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane / toluene and then by a second chromatographic purification using heptane / dichloromethane as the eluent to give 2.1 g (55% yield) of Intermediate 27-4 as a white solid. The molecular mass of the product was confirmed by LC-MS [M-H] - 615.4. - confirmed to be 615.4.

[0780] Compound 27

[0781]

Chem.

[0782] 200 mg (0.324 mmol) of Intermediate 27-4 was dissolved in 32 mL of tert-butylbenzene, degassed with Ar, and cooled to 0 °C. After dropwise addition of 0.51 mL (0.973 mmol) of tert-butyllithium (1.9 M solution in pentane), the mixture was stirred at the same temperature for 5 minutes. Then, the reaction mixture was stirred at 85 °C for 2 hours. Next, 0.81 mL (0.81 mmol) of tribromoborane (1 M solution in heptane) was added dropwise at 0 °C, and the reaction mixture was warmed to room temperature over 45 minutes, after which 1.44 mL (8.40 mmol) of N-ethyl-N-isopropylpropan-2-amine was added. The reaction mixture was stirred at 155 °C for 16 hours. The reaction was cooled to room temperature and diluted with toluene / water. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extracts were washed with water and saturated brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane / toluene as the eluent to give 5 mg (yield 2%) of Compound 27 as a yellow solid. The molecular mass of the product was confirmed by LC-MS [M+H] + at 624.7.

[0783] II Evaluation of Compounds Next, the properties of the compounds used in the examples were measured. The measurement methods and calculation methods are shown below.

[0784] 1.1 Photoluminescence Application Data Toluene solutions of the compounds listed in the table were prepared by dissolving the corresponding compounds in toluene at a concentration of 10 -6 mol / L. The total fluorescence spectra were measured for the toluene solutions using an FP-8300 JASCO spectrofluorometer.

[0785] The photoluminescence (PL) data of Compounds 1 - 27 of the present invention in toluene solution were determined. These are summarized in the following table. As a comparative example, the PL data of Comparative Compound 1 in toluene solution according to paragraph

[0122] of US Patent Application Publication No. 2019 / 0067577 are disclosed in the table.

[0786]

Table 1

[0787] These results support that for Compounds 1 - 6 and 8 - 27 of the present invention, a narrower spectrum (smaller FWHM), that is, better color purity, is obtained compared to Comparative Compound 1. The PL of Compound 7 of the present invention is at a longer wavelength than the PL of Comparative Compound 1.

[0788]

Chemical formula

[0789] 1.2 Device application data (compounds of the present invention as light - emitting dopants) Manufacture and evaluation of organic EL devices Organic EL devices were manufactured and evaluated as follows. Application Example 1 First, a glass substrate with a 130 - nm - thick indium tin oxide (ITO) transparent electrode (manufactured by Geomatec Co., Ltd) as the anode was treated with N 2 plasma for 100 seconds. By this treatment, the hole - injection characteristics of ITO were also improved. The cleaned substrate was attached to a substrate holder and loaded into a vacuum chamber. Then, the organic materials specified below were deposited at about 10 -6 ~10 -8It was deposited on the ITO substrate at a rate of approximately 0.2 to 1 Å / second in mbar. As a hole injection layer, a mixture of compound HT-1 and compound HI at 3 mass% was formed into a film with a thickness of 10 nm. Subsequently, compound HT-1 with a thickness of 80 nm and compound HT-2 with a thickness of 10 nm were formed into films as hole transport layer 1 and hole transport layer 2, respectively. Subsequently, a fluorescent emission layer with a thickness of 25 nm was formed from a mixture of 2 mass% of phosphor compound 2 and 98 mass% of host compound BH-1. On the emission layer, compound ET-1 with a thickness of 10 nm was formed as electron transport layer 1, and compound ET-2 with a thickness of 15 nm was formed as electron transport layer 2. Finally, after depositing 1 nm of LiF as an electron injection layer, 80 nm of Al was deposited as the cathode to complete the device. The device was sealed using a glass lid and a getter in an inert nitrogen atmosphere containing less than 1 ppm of water and oxygen. To evaluate the characteristics of the OLED, the electroluminescence (EL) spectrum was measured at various currents and voltages. The maximum EL peak and full width at half maximum (FWHM) were measured at 10 mA / cm 2 2. Further, the current-voltage characteristics were measured in combination with the luminance to obtain the luminous efficiency and the external quantum efficiency (EQE). The driving voltage (voltage) was obtained at a current density of 10 mA / cm 2 2. The results of the device are shown in Table 1.

[0790] [Chemical formula]

[0791] [Chemical formula]

[0792] [Table 2]

[0793] These results confirm that when the compounds of the present invention are used as fluorescent emission materials in OLEDs, good EQE and a narrow spectrum (smaller FWHM), that is, good color purity, can be obtained.

[0794] 1.3 Additional application examples Application Example 1 was repeated except that Compounds 3 to 6, 8, 11, 12, 15 to 17, 20, 21, and 23 were used instead of Compound 2 as the luminescent substance in the fluorescent emission layer.

[0795] [Table 3]

Claims

**Claim 1**: A heterocyclic compound represented by formula (VC). 【Chemical 1】 In formula (VC), R9 and R14 are each independently an unsubstituted or substituted aryl group having 6 to 18 ring-forming carbon atoms, or R2 and R18 are each independently an unsubstituted or substituted aryl group having 6 to 18 ring-forming carbon atoms, when R9 and R14 are each independently an unsubstituted or substituted aryl group having 6 to 18 ring-forming carbon atoms, R1, R3, R4, R5, R6, R7, R8, R10, R13, R15, R16, R17, and R19 are each independently hydrogen, an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 6 ring-forming carbon atoms, an unsubstituted or substituted aryl group having 6 to 13 ring-forming carbon atoms, or an unsubstituted or substituted heteroaryl group having 5 to 13 ring-forming atoms; R2 and R18 are each independently hydrogen, an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 6 ring-forming carbon atoms, or an unsubstituted or substituted heteroaryl group having 5 to 13 ring-forming atoms; and two adjacent residues R1, R2, and / or R3, and / or two adjacent residues R16, R17, R18, and / or R19 may together form a ring structure represented by the following unsubstituted or substituted structure. [Chemical 2] When R2 and R18 are each independently an unsubstituted or substituted aryl group having 6 to 18 ring-forming carbon atoms, R1, R3, R4, R5, R6, R7, R8, R10, R13, R15, R16, R17, and R19 are each independently hydrogen, an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 6 ring-forming carbon atoms, an unsubstituted or substituted aryl group having 6 to 13 ring-forming carbon atoms, or an unsubstituted or substituted heteroaryl group having 5 to 13 ring-forming atoms; R9 and R14 are each independently hydrogen, an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 6 ring-forming carbon atoms, or an unsubstituted or substituted heteroaryl group having 5 to 13 ring-forming atoms; and two adjacent residues R7, R8, R9, and / or R10, and / or two adjacent residues R13, R14, and / or R15 may together form a ring structure represented by the following unsubstituted or substituted structure: 【Chemical 3】 R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R13, R14, R15, R16, R17, R18, R19, the substituents in the case of "substituted or unsubstituted" in the ring structure, and the substituents in the case of "unsubstituted or substituted ring structure" are unsubstituted alkyl groups having 1 to 8 carbon atoms, provided that the following compounds are excluded.) [Chemical 3]

2. The heterocyclic compound according to Claim 1, wherein R9 and R14 are unsubstituted or substituted phenyl groups.

3. A material for an organic electroluminescence device, comprising at least one compound according to Claim 1 or 2.

4. An organic electroluminescence device, comprising at least one compound according to Claim 1 or 2.

5. The organic electroluminescence device according to Claim 4, comprising a cathode, an anode, and one or more organic thin film layers including a light-emitting layer disposed between the cathode and the anode, wherein at least one layer of the organic thin film layers contains at least one compound according to Claim 1 or 2.

6. The light-emitting layer is the organic electroluminescence device according to claim 5, containing at least one compound according to claim 1 or 2.

7. The light-emitting layer contains at least one host and at least one dopant, and the dopant contains at least one compound according to claim 1 or 2. The organic electroluminescence device according to claim 6.

8. The host contains at least one substituted or unsubstituted condensed aromatic hydrocarbon compound and / or at least one substituted or unsubstituted anthracene compound. The organic electroluminescence device according to claim 7.

9. An electronic device including the organic electroluminescence device according to any one of claims 4 to 8.

10. A light-emitting layer containing at least one host and at least one dopant, wherein the dopant contains at least one compound according to claim 1 or 2.

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