Heterocyclic compounds and organic electroluminescence devices containing heterocyclic compounds

Abstract

The present invention relates to a specific heterocyclic compound, a material for an organic electroluminescence device comprising said specific heterocyclic compound, preferably an emitter material, an organic electroluminescence device comprising said specific heterocyclic compound, an electronic device comprising said organic electroluminescence device, a light-emitting layer comprising at least one host and at least one dopant, wherein the dopant comprises at least one of said specific heterocyclic compound, and a use of said heterocyclic compound in an organic electroluminescence device.

Description

Technology Field

[0001] The present invention relates to a specific heterocyclic compound, a material for an organic electroluminescence device comprising said specific heterocyclic compound, preferably an emitter material, an organic electroluminescence device comprising said specific heterocyclic compound, an electronic device comprising said organic electroluminescence device, a light-emitting layer comprising at least one host and at least one dopant, wherein the dopant comprises at least one of said specific heterocyclic compound, and a use of said heterocyclic compound in an organic electroluminescence device. Background Technology

[0002] When a voltage is applied to an organic electroluminescence device (hereinafter 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 recombine to form excitons.

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

[0004] US 2019 / 0067577 A1 relates to a boron-containing heterocyclic compound for organic electronic devices, such as organic light-emitting devices, having a structure according to the following chemical formula I.

[0005]

[0006] During the meal,

[0007] Rings A, B, C, and D are each independently 5 or 6-membered aryl or heteroaryl rings;

[0008] R1, R2, R3, and R4 each independently represent non-substitutions or up to the maximum available substitution;

[0009] Y is NR, O, PR, S, or Se;

[0010] Z is N or P.

[0011] Examples of compounds of chemical formula I are the following compounds:

[0012]

[0013] However, the specific structure and substitution patterns of polycyclic compounds have a significant impact on the performance of polycyclic compounds in organic electronic devices.

[0014] Despite the aforementioned advancements, organic electroluminescence devices containing new materials, particularly dopant (=emitter) materials, are still needed to provide improved performance of electroluminescence devices.

[0015] Accordingly, the object of the present invention is to provide a material suitable for providing an organic electroluminescence device that ensures good performance, particularly good EQE and / or long lifespan, in relation to the aforementioned related technology. More specifically, a dopant (= emitter) material, particularly a blue-emitting dopant material having a narrow spectrum (smaller FWHM), that is, a material that can provide good color purity when used as a dopant in an organic electroluminescence device.

[0016] The above objective is solved by a heterocyclic compound represented by the following chemical formula (I) according to one aspect of the present invention:

[0017]

[0018] During the meal,

[0019] Rings A1, B1, C1, and D1 each independently represent a substituted or unsubstituted aromatic group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 cyclic carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 cyclic atoms;

[0020] or

[0021] Rings C1 and D1 are directly bonded, O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 It can be connected through, preferably through direct coupling;

[0022] R E is hydrogen; an unsubstituted or substituted aryl group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 cyclic atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms; an unsubstituted or substituted alkenyl group having 2 to 20 carbon atoms; an iminyl group R 23 -C=N; representing an unsubstituted or substituted alkynyl group having 2 to 20 carbon atoms;

[0023] or

[0024] R E or R E Substituents on the upper surface can be bonded to ring A1 and / or ring B1 or to substituents on ring A1 and / or ring B1 to form unsubstituted or substituted ring structures, and

[0025] Y is directly coupled, O, S, NR 23 , SiR24 R 25 or CR 27 R 28 , preferably exhibiting direct bonding;

[0026] If Y is a direct bond, rings B1 and C1 are O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 It can be additionally connected through;

[0027] R 23 , R 24 , R 25 , R 27 and R 28 Each independently represents an unsubstituted or substituted aryl group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 cyclic atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; or an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms;

[0028] and / or

[0029] 2 remaining R 24 and R 25 and / or 2 residues R 27 and R 28 silver They form a ring structure that is either unsubstituted or substituted together.

[0030] In principle, the compound of formula (I) can be used in any layer of an EL device. Preferably, the compound of formula (I) is a dopant (=emitter) in an organic EL device, particularly in a light-emitting layer, and more preferably, a fluorescent dopant. In particular, the compound of formula (I) is used as a fluorescent dopant in an organic EL device, particularly in a light-emitting layer.

[0031] The term organic EL device (organic electroluminescence device) is used interchangeably with the term organic light-emitting diode (OLED) in this application.

[0032] A specific compound of formula (I) has been found to exhibit a narrow luminescence characteristic, preferably a narrow fluorescence, more preferably a narrow blue fluorescence. This narrow luminescence characteristic is suitable for preventing energy loss due to outcoupling. The compound of formula (I) according to the present invention preferably has a full width at half maximum (FWHM) of less than 30 nm, more preferably less than 25 nm.

[0033] Additionally, it has been found that an organic EL device comprising a compound of the present invention is generally characterized by high external quantum efficiency (EQE) and a long lifetime, particularly when a specific compound of formula (I) is used as a dopant (luminescent material), particularly a fluorescent dopant, in an organic electroluminescence device. Brief explanation of the drawing

[0563] Brief explanation of the drawing Specific details for implementing the invention

[0034] Examples of any substituent(s) indicated as “substituted or unsubstituted” and “substituteable” as referred to above or below include: an aryl group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 cyclic carbon atoms and sequentially unsubstituted or substituted; a heteroaryl group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 cyclic atoms and sequentially unsubstituted or substituted; an alkyl group having 1 to 20, preferably 1 to 8 carbon atoms; a cycloalkyl group having 3 to 20, preferably 3 to 6 carbon atoms; a group OR 20 , an alkyl halide group having 1 to 20, preferably 1 to 8, carbon atoms, group N(R 22)2, halogen atom (fluorine, chlorine, bromine, iodine), cyano group, 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms carboxyalkyl group, 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms carboxyamidealkyl group, silyl group SiR 24 R 25 R 26 , B(R 21 )2, Gi SR 20 , comprising a carboxyryl group having 6 to 18 cyclic carbon atoms in an aryl residue and a carboxymidaryl group having 6 to 18 cyclic carbon atoms in an aryl residue;

[0035] or

[0036] Two adjacent substituents together form an unsubstituted or substituted ring structure in turn;

[0037] R 20 , R 21 , and R 22 Each independently represents an unsubstituted or substituted aryl group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 cyclic carbon atoms; a heteroaryl group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 cyclic atoms, which is unsubstituted or substituted and connected to N, O, S, or B through carbon atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; or an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms;

[0038] and / or

[0039] 2 remaining R 22 and / or 2 residues R 21 silver Together forming unsubstituted or substituted ring structures;

[0040] or

[0041] R 20 , R 21 , and / or R22 It forms an unsubstituted or substituted ring structure together with adjacent substituents;

[0042] R 26 It represents an unsubstituted or substituted aryl group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 cyclic carbon atoms; a heteroaryl group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 cyclic atoms, which is unsubstituted or substituted and connected to N or Si through carbon atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; or an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms;

[0043] R 24 , R 25 is defined above.

[0044] The term hydrogen, halogen, an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted alkyl halide group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms, a substituted or unsubstituted aromatic group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 cyclic carbon atoms; A substituted or unsubstituted heteroaromatic group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms; a carboxyalkyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms; a carboxymidalkyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms; a carboxyaryl group having 6 to 18 ring carbon atoms in an aryl residue; a carboxymidaryl group having 6 to 18 ring carbon atoms in an aryl residue; N(R 22 )2, OR 20 , SR 20 , SR 20 , SiR 24R 25 R 26 and B(R 21 )2 is known in the art and generally has the following meaning unless further specified in the specific embodiments mentioned below:

[0045] In the present invention, hydrogen includes isomers with different numbers of neutrons, namely protium, deuterium, and tritium.

[0046] A substituted or unsubstituted aromatic group (also referred to as an aryl group) having 6 to 60, preferably 6 to 30, more preferably 6 to 18 cyclic carbon atoms, most preferably 6 to 13 cyclic carbon atoms, may be a non-condensing aromatic group or a condensing aromatic group. Specific examples thereof include phenyl groups, naphthyl groups, phenanthryl groups, biphenyl groups, terphenyl groups, fluoranthenyl groups, triphenylenyl groups, phenanthrenyl groups, fluorenyl groups, indenyl groups, anthracenyl, crisenyl, spirofluorenyl groups, and benzo[c]phenanthrenyl groups, wherein phenyl groups, naphthyl groups, biphenyl groups, terphenyl groups, phenanthryl groups, triphenylenyl groups, fluorenyl groups, indenyl groups, and fluoranthenyl groups are preferred, and phenyl groups, 1-naphthyl groups, 2-naphthyl groups, biphenyl-2-yl groups, biphenyl-3-yl groups, biphenyl-4-yl groups, phenanthren-9-yl groups, phenanthren-3-yl groups, phenanthren-2-yl groups, triphenylen-2-yl groups, fluoren-2-yl groups, particularly 9,9-di-C 1-20 Alkylfluorene-2-yl group, e.g., 9,9-dimethylfluorene-2-yl group, 9,9-di-C 6-18 arylfluorene-2-yl group, e.g. 9,9-diphenylfluorene-2-yl group, or 9,9-di-C 5-18 Heteroarylfluorene-2-yl group, 1,1-dimethyldenyl group, fluoranthen-3-yl group, fluoranthen-2-yl group and fluoranthen-8-yl group are more preferred, and a phenyl group is most preferred.

[0047] For rings A1, B1, C1 and D1, a substituted or unsubstituted preferred aromatic group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms is mentioned below.

[0048] A substituted or unsubstituted heteroaromatic group (also referred to as a heteroaryl group) having 5 to 60, preferably 5 to 30, more preferably 5 to 18, and most preferably 5 to 13, ring atoms may be a non-condensing heteroaromatic group or a condensing heteroaromatic group. Specific examples thereof include a pyrrole ring, an isoindole ring, a benzofuran ring, an isobenzofuran ring, benzothiophene, a dibenzothiophene ring, an isoquinoline ring, a quinoxaline ring, a quinazoline, a phenanthridine ring, a phenanthroline ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indole ring, a quinoline ring, an acridine ring, a carbazole ring, a furan ring, a thiophene ring, and a benzoxazole ring. It comprises residues of a ring, a benzothiazole ring, a benzimidazole ring, a dibenzofuran ring, a triazine ring, an oxazole ring, an oxadiazole ring, a thiazole ring, a thiadiazole ring, a triazole ring, an imidazole ring, an indolidine ring, an imidazopyridine ring, 4-imidazoo[1,2-a]benzimidazooyl, 5-benzimidazoo[1,2-a]benzimidazooyl, and benzimidazole[2,1-b][1,3]benzothiazoyl, and residues of a benzofuran ring, an indole ring, a benzothiophene ring, a dibenzofuran ring, a carbazole ring, and a dibenzothiophene ring are preferred, and a benzofuran ring, a 1-phenylindole ring, a benzothiophene ring, a dibenzofuran-1-yl group, a dibenzofuran-3-yl group, Residues of dibenzofuran-2-yl, dibenzofuran-4-yl, 9-phenylcarbazole-3-yl, 9-phenylcarbazole-2-yl, 9-phenylcarbazole-4-yl, dibenzothiophen-2-yl, and dibenzothiophen-4-yl, dibenzothiophen-1-yl, and dibenzothiophen-3-yl are more preferable.

[0049] For rings A1, B1, C1 and D1, a preferred substituted or unsubstituted heteroaromatic group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms is mentioned below.

[0050] Examples of unsubstituted or substituted alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, and 1-methylpentyl groups, and methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, isobutyl, and t-butyl groups are preferred. An alkyl group having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, is preferred. Suitable examples for alkyl groups having 1 to 8 carbon atoms and each having 1 to 4 carbon atoms have been described above.

[0051] Examples of unsubstituted or substituted alkyl halides having 1 to 20 carbon atoms include those disclosed as alkyl groups in which a hydrogen atom of the alkyl group is partially or wholly substituted by a halogen atom. A preferred alkyl halide is a fluoroalkyl group having 1 to 20 carbon atoms including the aforementioned alkyl group in which a hydrogen atom of the alkyl group is partially or wholly substituted by a fluorine atom, e.g., CF3.

[0052] Examples of unsubstituted or substituted cycloalkyl groups having 3 to 20 cyclic carbon atoms include cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, cyclooctyl groups, and adamantyl groups, with cyclopentyl groups and cyclohexyl groups preferred. Cycloalkyl groups having 3 to 6 carbon atoms are preferred. Suitable examples for cycloalkyl groups having 3 to 6 carbon atoms have been described above.

[0053] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, with fluorine being preferred.

[0054] OR 20 The group is preferably C 1- 20 Alkoxy group or C 6- 18 It is an aryloxy group. Examples of alkoxy groups having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, include those having an alkyl portion selected from the alkyl groups mentioned above. Examples of aryloxy groups having 6 to 18 cyclic carbon atoms include those having an aryl portion selected from the aryl groups mentioned above, for example, -OPh.

[0055] SR 20 The group is preferably C 1- 20 alkylthio group or C 6- 18 It is an arylthio group. Examples of alkylthio groups having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, include those having an alkyl portion selected from the alkyl groups described above. Examples of arylthio groups having 6 to 18 cyclic carbon atoms include those having an aryl portion selected from the aryl groups described above, for example, -Sph.

[0056] N(R 22 )2nd stage is preferably C 1- 20 Alkyl and / or C 6- 18It is an aryl and / or heteroaryl (having 5 to 18 ring atoms) substituted amino group. Examples of alkyl amino groups (alkyl-substituted amino groups) having 1 to 20 ring carbon atoms include those having an alkyl portion selected from the alkyl groups described above. Examples of aryl amino groups (aryl-substituted amino groups) having 6 to 18 ring carbon atoms include those having an aryl portion selected from the aryl groups described above, for example, -NPh2. Examples of heteroaryl amino groups (heteroaryl-substituted amino groups), preferably heteroaryl amino groups having 5 to 18 ring atoms, include those having an aryl portion selected from the heteroaryl groups mentioned above.

[0057] B(R 21 )2nd stage is preferably C 1- 20 Alkyl and / or C 6- 18 It is an aryl and / or heteroaryl (having 5 to 18 ring atoms) substituted boron group. Examples of alkyl boron groups (alkyl-substituted boron groups) having 1 to 20 ring carbon atoms include those having an alkyl portion selected from the alkyl groups described above. Examples of aryl boron groups (aryl-substituted boron groups) having 6 to 18 ring carbon atoms include those having an aryl portion selected from the aryl groups described above. Examples of heteroaryl boron groups (heteroaryl-substituted boron groups), preferably heteroaryl boron groups having 5 to 18 ring atoms, include those having an aryl portion selected from the heteroaryl groups described above.

[0058] SiR 24 R 25 R 26 The group is preferably C 1- 20 Alkyl and / or C 6- 18 It is an aryl-substituted silyl group. C 1-20 Alkyl and / or C 6- 18Preferred examples of aryl-substituted silyl groups include an alkylsilyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, in each alkyl residue comprising a trimethylsilyl group, a triethylsilyl group, a tributylsilyl group, a dimethylethylsilyl group, a t-butyldimethylsilyl group, a propyldimethylsilyl group, a dimethylisopropylsilyl group, a dimethylbutylsilyl group, a dimethylt-butylsilyl group, and a diethylisopropylsilyl group; Each aryl residue comprises an arylsilyl group having 6 to 18 ring carbon atoms, preferably a triphenylsilyl group, and an alkyl / arylsilyl group, preferably a phenyldimethylsilyl group, a diphenylmethylsilyl group, and a diphenyl t-butylsilyl group, wherein the diphenyl t-butylsilyl group and the t-butyldimethylsilyl group are preferred.

[0059] Examples of carboxyalkyl groups having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, include those having an alkyl portion selected from the alkyl groups described above.

[0060] Examples of fluoroalkyl groups having 1 to 20 carbon atoms include the aforementioned alkyl groups in which the hydrogen atoms of the alkyl group are partially or wholly substituted by fluorine atoms.

[0061] Examples of carboxymidalkyl groups (alkyl-substituted amide groups) having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, include those having an alkyl portion selected from the alkyl groups mentioned above.

[0062] Examples of carboxymidaryl groups (aryl-substituted amide groups) having 6 to 18 carbon atoms, preferably 6 to 13 carbon atoms, include those having an aryl portion selected from the aryl groups described above.

[0063] Any substituent preferably comprises an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms, each independently; an unsubstituted or substituted heteroaryl group having 5 to 18 cyclic atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms; CN; N(R 22 )2; SiR 24 R 25 R 26 , SR 20 or OR 20 Representing;

[0064] or

[0065] Two adjacent substituents together form a ring structure that is alternately unsubstituted or substituted;

[0066] R 20 and R 22 Each independently represents an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms; a heteroaryl group having 5 to 18 cyclic atoms, which is unsubstituted or substituted and connected to N, O, or S through carbon atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; or an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms;

[0067] or

[0068] R 20 and / or R 22 It forms a ring structure that is sequentially unsubstituted or substituted with adjacent substituents;

[0069] R 24 , R 25 and R 26It represents an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 18 cyclic carbon atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; and an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms.

[0070] More preferably, any substituent is an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 18 cyclic carbon atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms; CN; or N(R 22 Representing )2;

[0071] or

[0072] Two adjacent substituents together form a ring structure that is alternately unsubstituted or substituted;

[0073] R 22 ...represents an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms; or an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms;

[0074] or

[0075] R 22 It forms a ring structure that is successively unsubstituted or substituted with adjacent substituents.

[0076] Most preferably, any substituent is an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 6 cyclic carbon atoms; an unsubstituted or substituted aryl group having 6 to 13 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 13 cyclic atoms; CN; or N(R 22 Representing )2;

[0077] or

[0078] Two adjacent substituents together form a ring structure that is alternately unsubstituted or substituted;

[0079] R 22 represents an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms; or an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms.

[0080] Any substituent mentioned above may be further substituted by one or more of any substituents mentioned above.

[0081] The number of any substituents depends on the group substituted by the substituent(s). The maximum number of possible substituents is limited by the number of hydrogen atoms present. One, two, three, five, six, seven, eight, or nine any substituents per substituted group is preferred, one, two, three, five, six, or seven any substituents are more preferred, one, two, three, four, or five any substituents are most preferred, one, two, three, four, or five any substituents are even more preferred, one, two, three, or four any substituents are even more preferred, and one or two any substituents per substituted group are much more preferred. In a further preferred embodiment, some or all of the groups mentioned above are unsubstituted.

[0082] In a further 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, i.e., the remaining residues are hydrogen.

[0083] In the expression "substituted or unsubstituted X group having a to b carbon atoms," "a to b carbon atoms" refers to the number of carbon atoms of the unsubstituted X group and does not include carbon atoms of any substituent.

[0084] The term "unsubstituted," referred to by "unsubstituted or substituted," means that the hydrogen atom is not substituted by any of the aforementioned groups.

[0085] In the definition of any chemical formula mentioned above and below, the exponent 0 means that a hydrogen atom is present at the position defined by the exponent.

[0086] Compound of chemical formula (I)

[0087] In heterocyclic compounds represented by the following chemical formula (I)

[0088]

[0089] The remaining parts have the following meanings:

[0090] Rings A1, B1, C1, and D1 each independently represent a substituted or unsubstituted aromatic group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 cyclic carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 cyclic atoms;

[0091] or

[0092] Rings C1 and D1 are directly bonded, O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 It can be connected through, preferably through direct coupling;

[0093] R Eis hydrogen; an unsubstituted or substituted aryl group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 cyclic atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms; an unsubstituted or substituted alkenyl group having 2 to 20 carbon atoms; an iminyl group R 23 -C=N; representing an unsubstituted or substituted alkynyl group having 2 to 20 carbon atoms;

[0094] or

[0095] R E or R E Substituents on the upper surface may bind to ring A1 and / or ring B1 or to substituents on ring A1 and / or ring B1 to form unsubstituted or substituted ring structures, and

[0096] Y is directly coupled, O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 , preferably exhibiting direct bonding;

[0097] If Y is a direct bond, rings B1 and C1 are O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 It can be additionally connected through;

[0098] R 23 , R 24 , R 25 , R 27 and R 28Each independently represents an unsubstituted or substituted aryl group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 cyclic carbon atoms; a heteroaryl group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 cyclic atoms, which is unsubstituted or substituted and connected to N or Si through carbon atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; or an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms;

[0099] and / or

[0100] 2 remaining R 24 and R 25 and / or 2 residues R 27 and R 28 silver They form a ring structure that is either unsubstituted or substituted together.

[0101] Preferably, rings A1, B1, C1 and D1 each independently represents a substituted or unsubstituted aromatic group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 cyclic carbon atoms of the following formula, or a substituted or unsubstituted heteroaromatic group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 cyclic atoms;

[0102]

[0103] During the meal,

[0104] ring C1 and Ring D1 is directly bonded, O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 It can be connected through, preferably through direct coupling;

[0105] The asterisk is ring C1 and It is the location of a desirable arbitrary connection site between rings D1;

[0106] The dotted line is the joint area.

[0107] More desirable rings A1, B1, C1 and D1 is the following:

[0108] Non-condensing aromatic groups or condensing aromatic groups. Specific examples thereof are based on phenyl, naphthyl, phenanthrene, biphenyl, terphenyl, fluorantene, triphenylene, fluorene, indene, anthracene, chrysene, spirofluorene, and benzo[c]phenanthrene, wherein phenyl, naphthyl, biphenyl, terphenyl, phenanthrene, triphenylene, fluorene, indene, and fluorantene are preferred, and phenyl and naphthyl are most preferred;

[0109] or

[0110] Non-condensing heteroaromatic group or condensing heteroaromatic group. Specific examples of this are pyrrole, isoindole, benzofuran, isobenzofuran, benzothiophen, dibenzothiophen, isoquinoline, quinoxaline, quinazolin, phenanthroid, phenanthroline, pyridine, pyrazine, pyrimidine, pyridazine, indole, quinoline, acridine, carbazole, furan, thiophene, benzoxazole, benzothiazole, benzimidazole, dibenzofuran, triazine, oxazole, oxadiazole, thiazole, thiadiazole, triazole, imidazole, indolidine, imidazopyridine, 4-imidazoo[1,2-a]benzimidazole, 5-benzimidazoo[1,2-a]benzimidazole, and based on benzimidazole[2,1-b][1,3]benzothiazole And, indole, especially 1-phenylindole, benzothiophene, dibenzofuran, carbazole, dibenzothiophene, benzofuran, and benzothiophene are preferred.

[0111] More preferably, rings A1, B1, C1 and D1 is represented by the following chemical formula:

[0112]

[0113] In the formula, the dotted line represents the binding site, and residue R 12, R 13 , R 14 and R 15 is defined as follows;

[0114]

[0115] In the formula, the dotted line represents the binding site, and residue R 4 , R 5 and R 6 is defined as follows;

[0116]

[0117] In the formula, the dotted line represents the binding site, and residue R 1 , R 2 and R 3 is defined as follows;

[0118] Here, ring C1 and Ring D1 is directly bonded, O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 It can be connected through, preferably through direct coupling, and the asterisk is the location of a preferred optional coupling site to ring D1;

[0119]

[0120] In the equation, the dotted line represents a combination, and residue R 16 , R 17 , R 18 and R 19 is defined as follows;

[0121] Here, ring C1 and Ring D1 is directly bonded, O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 It can be connected through, preferably through direct connection, and the asterisk is the location of a preferred optional connection site to ring C1.

[0122] Examples of ring structures formed by two adjacent substituents are shown below (the ring structures below may be substituted by one or more of the substituents mentioned above):

[0123]

[0124]

[0125]

[0126] In the formula, X is O, CR a R b , S or NR c And,

[0127] X'' and Y'' are independently O, CR a R b , S, BR c or NR c Represents,

[0128] R a and R b Each is independently a C1 to C8 alkyl or a substituted or unsubstituted C6 to C 18 Aryl, preferably C1 to C4 alkyl or substituted or unsubstituted C6 to C 10 Representing an aryl, more preferably a methyl or unsubstituted or substituted phenyl,

[0129] R c is a C1 to C8 alkyl, preferably a C1 to C4 alkyl, or a substituted or unsubstituted C6 to C 10 Representing an aryl, preferably an unsubstituted or substituted phenyl,

[0130] E1, F1, F2, G1, H1, I1, I2, K1, L1, M1 and N1 each independently represents a substituted or unsubstituted aromatic group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 cyclic carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 cyclic atoms, and

[0131] The dotted line is the joint area.

[0132] R E or R E Examples of cases where substituents on ring A1 and / or ring B1 can bind to substituents on ring A1 and / or ring B1 to form unsubstituted or substituted ring structures are as follows:

[0133]

[0134] During the meal,

[0135] R E1 , R E2 , R E3 , R E5 and R E6 Each is independently a C1 to C8 alkyl or a substituted or unsubstituted C6 to C 18 Aryl, preferably C1 to C4 alkyl or substituted or unsubstituted C6 to C 10 Representing an aryl, more preferably a methyl or unsubstituted or substituted phenyl,

[0136] or

[0137] 2 adjacent residues R E2 and R E3 or R E5 and R E6 It forms a ring structure that is either substituted or unsubstituted together, and

[0138] X' is directly coupled, O, S, NR 23 , SiR 24 R 25 , CR 27 R 28, or BR 21 Represents,

[0139] Rings A1, B1, C1, D1, R 21 , R 23 , R 24 , R 25 , R 27 , R 28 and Y is defined above and below, and

[0140] R 7 , R 8 , R 9 , R 10 and R 11 is defined as follows.

[0141] Y is directly coupled, O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 , preferably exhibiting direct bonding;

[0142] If Y is a direct bond, ring B1 and C1 is O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 It can be additionally connected through.

[0143] Y is a direct bond and ring B1 and C1 is O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 Cases where additional connections are made through are shown below:

[0144]

[0145] In the formula, Z is O, S, NR 23 , SiR 24 R 25 or CR 27 R 28And, the residuals and indices are mentioned above.

[0146] Preferably, Y is a direct bond.

[0147] A preferred heterocyclic compound according to the present invention is represented by the following chemical formula (II):

[0148] ,

[0149] Among the formulas, the residue and index are mentioned above.

[0150] In a more preferred embodiment, the heterocyclic compound according to the present invention is represented by the following formula (III):

[0151] ,

[0152] Among the formulas, the residue and index are mentioned above.

[0153] In one embodiment, in the heterocyclic compound according to the present invention, ring A1 is a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms. Suitable heteroaromatic groups are mentioned above.

[0154] R E is preferably a group of the following formula (IV):

[0155]

[0156] During the meal,

[0157] R 7 , R 8 , R 9 , R 10 and R 11Each independently hydrogen; an unsubstituted or substituted aryl group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 cyclic atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted alkyl halide group having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms; CN; N(R 22 )2; OR 20 ; SR 20 ; B(R 21 )2; SiR 24 R 25 R 26 or represents a halogen;

[0158] and / or

[0159] 2 adjacent residues R 7 , R 8 , R 9 , R 10 and / or R 11 They together form unsubstituted or substituted ring structures;

[0160] and / or

[0161] R 7 and / or R 11 It is connected to a substituent on ring B1 and / or ring A1 or on ring A1 and / or ring B1 to form an unsubstituted or substituted ring structure;

[0162] The dotted line is the joint area.

[0163] Most preferably, the heterocyclic compound according to the present invention is represented by the following chemical formula (V):

[0164]

[0165] During the meal,

[0166] R 1 , R2 , 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 hydrogen; an unsubstituted or substituted aryl group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 cyclic atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted alkyl halide group having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms; CN; N(R 22 )2; OR 20 ; SR 20 ; B(R 21 )2; SiR 24 R 25 R 26 or represents a halogen;

[0167] or

[0168] 2 adjacent residues R 1 , R 2 and / or R 3 and / or 2 adjacent residues R 4 , R 5 and / or R 6 and / or 2 adjacent residues R 12 , R 13 , R 14 and / or R 15 , and / or 2 adjacent residues R 16 , R 17 , R 18 and / or R 19 It forms an unsubstituted or substituted ring structure together, and

[0169] and / or

[0170] 2 adjacent residues R 7 , R 8 , R 9 , R 10 and / or R 11 They form unsubstituted or substituted ring structures together;

[0171] and / or

[0172] R 7 and / or R 11 is R 6 and / or R 12 Connected to form an unsubstituted or substituted ring structure;

[0173] R 20 , R 21 , and R 22 Each independently represents an unsubstituted or substituted aryl group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 cyclic atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; or an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms;

[0174] and / or

[0175] 2 remaining R 22 and / or 2 residues R 21 silver Together forming unsubstituted or substituted ring structures;

[0176] or

[0177] R 20 , R 21 , and / or R 22 is 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 , R 17 , R 18 or R 19 Together with, it forms an unsubstituted or substituted ring structure;

[0178] R 24 , R 25 and R 26 Each represents an unsubstituted or substituted aryl group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 cyclic atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; or an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms.

[0179] 2 adjacent residues R 1 , R 2 and / or R 3 and / or 2 adjacent residues R 4 , R 5 and / or R 6 and / or 2 adjacent residues R 7 , R 8 , R 9 , R 10 and / or R 11 and / or 2 adjacent residues R 12 , R 13 , R 14 and / or R 15 , and / or 2 adjacent residues R 16 , R 17 , R 18 and / or R 19Examples of ring structures formed by are shown below (the ring structures below may be substituted by one or more of the substituents mentioned above):

[0180]

[0181] In the formula, X is O, CR a R b , S or NR c And,

[0182] R a and R b Each is independently a C1 to C8 alkyl or a substituted or unsubstituted C6 to C 18 Aryl, preferably C1 to C4 alkyl or substituted or unsubstituted C6 to C 10 Representing an aryl, more preferably a methyl or unsubstituted or substituted phenyl,

[0183] R c is a C1 to C8 alkyl, preferably a C1 to C4 alkyl, or a substituted or unsubstituted C6 to C 10 It represents an aryl, preferably an unsubstituted or substituted phenyl.

[0184] R 7 and / or R 11 This R 6 and / or R 12 Examples of cases where they are connected to form unsubstituted or substituted ring structures are as follows:

[0185]

[0186] During the meal,

[0187] X' is directly coupled, O, S, NR 23 , SiR 24 R 25 , CR 27 R 28 , or BR 21 Represents,

[0188] All other residues are defined above and below.

[0189] 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 comprises hydrogen, an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 18 cyclic atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms; CN; N(R 22 )2; SiR 24 R 25 R 26 , SR 20 or OR 20 Representing;

[0190] or

[0191] 2 adjacent residues R 1 , R 2 and / or R 3 and / or 2 adjacent residues R 4 , R 5 and / or R 6 and / or 2 adjacent residues R 7 , R 8 , R 9 , R 10 and / or R 11 and / or 2 adjacent residues R 12 , R 13 , R 14 and / or R 15 , and / or 2 adjacent residues R 16 , R 17, R 18 and / or R 19 It forms an unsubstituted or substituted ring structure together, and

[0192] and / or

[0193] R 7 and / or R 11 is R 6 and / or R 12 Connected to form an unsubstituted or substituted ring structure;

[0194] R 20 and R 22 Each independently represents an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 18 cyclic atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; or an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms;

[0195] or

[0196] R 20 and / or R 22 is 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 , R 17 , R 18 or R 19 Together with, it forms an unsubstituted or substituted ring structure;

[0197] R 24 , R 25 and R 26It represents an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms; an unsubstituted heteroaryl group having 5 to 18 cyclic carbon atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; or an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms.

[0198] 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 R 19 Each independently comprises hydrogen, an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 18 cyclic atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms; CN; or N(R 22 Representing )2;

[0199] or

[0200] 2 adjacent residues R 1 , R 2 and / or R 3 and / or 2 adjacent residues R 4 , R 5 and / or R 6 and / or 2 adjacent residues R 7 , R 8 , R 9 , R 10 and / or R 11 and / or 2 adjacent residues R12 , R 13 , R 14 and / or R 15 , and / or 2 adjacent residues R 16 , R 17 , R 18 and / or R 19 It forms an unsubstituted or substituted ring structure together, and

[0201] and / or

[0202] R 7 and / or R 11 is R 6 and / or R 12 Connected to form an unsubstituted or substituted ring structure;

[0203] R 22 represents an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms; or an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms;

[0204] or

[0205] R 22 is 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 , R 17 , R 18 or R 19 It forms an unsubstituted or substituted ring structure together with.

[0206] Most preferably, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R7 , 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 alkyl group having 1 to 4 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 6 cyclic carbon atoms; an unsubstituted or substituted aryl group having 6 to 13 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 13 cyclic atoms; CN; or N(R 22 Representing )2;

[0207] or

[0208] 2 adjacent residues R 1 , R 2 and / or R 3 and / or 2 adjacent residues R 4 , R 5 and / or R 6 and / or 2 adjacent residues R 7 , R 8 , R 9 , R 10 and / or R 11 and / or 2 adjacent residues R 12 , R 13 , R 14 and / or R 15 , and / or 2 adjacent residues R 16 , R 17 , R 18 and / or R 19 It forms an unsubstituted or substituted ring structure together, and

[0209] and / or

[0210] R 7 and / or R 11 is R 6 and / or R 12Connected to form an unsubstituted or substituted ring structure;

[0211] R 22 represents an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms; or an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms.

[0212] In an additional preferred embodiment, 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 these, 0, 1, 2, 3, 4, 5, 6, 7, or 8, preferably 0, 1, 2, 3, 4, 5, or 6 are not hydrogen; that is, the remaining residues are hydrogen. More preferably, residue R 2 , R 5 , R 9 , R 12 , R 13 , R 14 , R 15 , and R 18 Of these, 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; that is, the remaining residues are hydrogen.

[0213] In a preferred embodiment, the heterocyclic compound according to the present invention is represented by one of the following chemical formulas:

[0214]

[0215] Among the formulas, the residue is defined as mentioned above, and

[0216] -In chemical formula (VA) and chemical formula (VB)-

[0217] 2 adjacent residues R 1 , R 2 and / or R 3 and / or 2 adjacent residues R 4 and R 5 and / or 2 adjacent residues R 8 , R 9 , R 10 and / or R 11 and / or 2 adjacent residues R 12 , R 13 , R 14 and / or R 15 , and / or 2 adjacent residues R 16 , R 17 , R 18 and / or R 19 It can form unsubstituted or substituted ring structures together;

[0218] -From the chemical formula (VC)-

[0219] 2 adjacent residues R 1 , R 2 and / or R 3 and / or 2 adjacent residues R 4 , R 5 and / or R 6 and / or 2 adjacent residues R 7 , R 8 , R 9 and / or R 10 and / or 2 adjacent residues R 13 , R 14 and / or R 15 , and / or 2 adjacent residues R 16 , R 17 , R 18 and / or R 19 It can form unsubstituted or substituted ring structures together.

[0220] More preferably, the heterocyclic compound according to the present invention is represented by one of the following chemical formulas:

[0221]

[0222] Among the formulas, the residue is defined as mentioned above, and

[0223] -In chemical formulas (VAa) and (VBa)-

[0224] 2 adjacent residues R 12 , R 13 , R 14 and / or R 15 It can form unsubstituted or substituted ring structures together;

[0225] -From chemical formula (VCa-

[0226] 2 adjacent residues R 13 , R 14 and / or R 15 It can form unsubstituted or substituted ring structures together.

[0227] In a preferred embodiment, the heterocyclic compound according to the present invention is represented by the formula (VA), wherein two adjacent residues R 1 , R 2 and / or R 3 and / or 2 adjacent residues R 16 , R 17 , R 18 and / or R 19 It forms a ring structure that is either unsubstituted or substituted together.

[0228] In a preferred embodiment, the heterocyclic compound according to the present invention is represented by the formula (VA), wherein at least one R 1 to R 3 and / or R 16 to R 19is an unsubstituted or substituted aryl group having 6 to 60 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 60 cyclic carbon atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted alkyl halide group having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms; CN; N(R 22 )2; OR 20 ; SR 20 ; B(R 21 )2; SiR 24 R 25 R 26 or represents a halogen;

[0229] At least one R 4 to R 5 and / or R 12 to R 15 is an unsubstituted or substituted aryl group having 6 to 60 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 60 cyclic carbon atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted alkyl halide group having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms; CN; N(R 22 )2; OR 20 ; SR 20 ; B(R 21 )2; SiR 24 R 25 R 26 or represents a halogen.

[0230] In a further preferred embodiment, the heterocyclic compound according to the present invention is represented by the formula (VA), wherein at least one R 1 to R 3 and At least one R 16 to R 19 and At least one R 4 to R 5 and At least one R 12 to R 15 is an unsubstituted or substituted aryl group having 6 to 60 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 60 cyclic carbon atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted alkyl halide group having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms; CN; N(R 22 )2; OR 20 ; SR 20 ; B(R 21 )2; SiR 24 R 25 R 26 or represents a halogen.

[0231] In a preferred embodiment, the heterocyclic compound according to the present invention is represented by the chemical formula (VA), where R 9 is an unsubstituted or substituted heteroaryl group having 5 to 60 ring atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted alkyl halide group having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 20 ring carbon atoms; CN; N(R 22 )2; OR 20 ; SR 20 ; B(R 21 )2; SiR 24 R 25 R 26 or is a halogen;

[0232] At least one R 12 to R 15is an unsubstituted or substituted aryl group having 6 to 60 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 60 cyclic carbon atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted alkyl halide group having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms; CN; N(R 22 )2; OR 20 ; SR 20 ; B(R 21 )2; SiR 24 R 25 R 26 or represents a halogen.

[0233] In a preferred embodiment, the heterocyclic compound according to the present invention is represented by the chemical formula (VC), wherein at least one R 4 to R 6 , R 13 to R 15 is an unsubstituted or substituted aryl group having 6 to 60 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 60 cyclic carbon atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted alkyl halide group having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms; CN; N(R 22 )2; OR 20 ; SR 20 ; B(R 21 )2; SiR 24 R 25 R 26 or represents a halogen.

[0234] In a preferred embodiment, the heterocyclic compound according to the present invention is represented by the formula (VC) or (VB), wherein at least one residue R 4 , R 5 , R 6 , R 12 , R 13, R 14 or R 15 is C1-C 10 Alkyl, C3-C 12 Cycloalkyl, or C6-C 10 Aryl, preferably C1-C4 alkyl, C5-C 10 Cycloalkyl, or phenyl, more preferably tert - It is butyl.

[0235] Below, examples of compounds of chemical formula (I) are as follows:

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254] Preparation of the compound of chemical formula (I)

[0255] The compound represented by chemical formula (I) can be synthesized according to the reaction performed in the examples of the present application, and can be synthesized using alternative reactions or raw materials suitable for the intended product that are similar to reactions and raw materials known in the art.

[0256] The compound of formula (I) is prepared, for example, by the following steps:

[0257] (i) Add BHal3 to intermediate (II) to obtain the compound of formula (I):

[0258]

[0259] During the meal,

[0260] Hal represents a halogen, preferably F, Cl, Br, or I, more preferably Cl or Br, most preferably Br;

[0261] R is a C1-C8 alkyl or C6-C 10 Representing an aryl, preferably a C1-C4 alkyl or phenyl, more preferably a methyl;

[0262] All other residues and indices are as defined above.

[0263] Suitable reaction conditions are mentioned in the examples of the present application.

[0264] The intermediate (II) starts from, for example, a compound of the following chemical formula (III), and

[0265] ,

[0266] (i) an amino compound (IVa) that can be further modified after reaction with compound (III), or the reaction of Hal2 of compound (III) with amino compound (IVb), and

[0267] (ii) Reaction of Hal1 of carbazole derivative (V) and compound (III)

[0268] It is manufactured as,

[0269] Among the above formulas,

[0270] Hal1 represents a halogen, preferably Cl, and

[0271] Hal2 represents a halogen, preferably Br, and

[0272] R is a C1-C8 alkyl or C6-C 10 Representing an aryl, preferably a C1-C4 alkyl or phenyl, more preferably a methyl;

[0273] All other residues and indices are as defined above.

[0274] Generally, step (i) is performed first, followed by step (ii).

[0275] ,

[0276] This can be modified as follows: Here, the dotted line is the binding site to the compound of formula (III) at the position of Hal2.

[0277]

[0278] Here, X' is a direct combination (i.e., R E and Ring A1 is connected via direct bonding), O, S, NR 23 , SiR 24 R 25 , CR 27 R 28 or BR 21 , preferably a direct bond;

[0279] ,

[0280] Here, all residues and indices are as defined above.

[0281] A preferred compound of formula (V) is prepared, for example, by the following steps:

[0282] (i) Add BHal3 to intermediate (VI) to obtain a compound of formula (V);

[0283]

[0284] During the meal,

[0285] Hal represents a halogen, preferably F, Cl, Br, or I, more preferably Cl or Br, most preferably Br;

[0286] R is a C1-C8 alkyl or C6-C 10 Representing an aryl, preferably a C1-C4 alkyl or phenyl, more preferably a methyl;

[0287] All other residues and indices are as defined above.

[0288] The intermediate (VI) starts from, for example, a compound of the following formula (VII), and

[0289]

[0290] (i) an amino compound (VIIa) that can be further modified after reaction with compound (VII), or the reaction of Hal2 of compound (VII) with amino compound (VIIIb), and

[0291] (ii) Reaction of Hal1 of carbazole derivative (IX) and compound (VII)

[0292] It is manufactured as,

[0293] Among the above formulas,

[0294] Hal1 represents a halogen, preferably Cl, and

[0295] Hal2 represents a halogen, preferably Br, and

[0296] R is a C1-C8 alkyl or C6-C 10 Representing an aryl, preferably a C1-C4 alkyl or phenyl, more preferably a methyl;

[0297] All other residues and indices are as defined above.

[0298] Generally, step (i) is performed first, followed by step (ii).

[0299] ,

[0300] This can be modified as follows: , the dotted line in the formula is the binding site to the compound of formula (VII) at the position of Hal2.

[0301]

[0302] In the formula, all residues and indices are as defined above.

[0303] In a further embodiment, the compound of formula (I) is prepared, for example, as follows:

[0304] ia) Add BHal3 to intermediate (IIa) to obtain formula (I):

[0305]

[0306] During the meal,

[0307] Hal represents a halogen, preferably F, Cl, Br, or I, more preferably Cl or Br, most preferably Br;

[0308] All other residues and indices are as defined above.

[0309] Suitable reaction conditions are mentioned in the examples of the present application.

[0310] The intermediate (IIa) starts from, for example, a compound of the following chemical formula (IIIa), and

[0311]

[0312] (i) an amino compound (IVa) that can be further modified after reaction with compound (IIIa), or the reaction of Hal2 of compound (IIIa) with amino compound (IVb), and

[0313] (ii) Reaction of Hal1 of carbazole derivative (V) and compound (IIIa)

[0314] It is manufactured as,

[0315] Among the above formulas,

[0316] Hal1 represents a halogen, preferably Cl, and

[0317] Hal2 represents a halogen, preferably Br, and

[0318] All other residues and indices are as defined above.

[0319] Generally, step (i) is performed first, followed by step (ii).

[0320] ,

[0321] This can be modified as follows: In the formula, the dotted line is the binding site to the compound of formula (III) at the position of Hal2.

[0322] ,

[0323] In the expression, X' is a direct combination (i.e., R E and Ring A1 is connected via direct bonding), O, S, NR 23 , SiR 24 R 25 , CR 27 R 28 or BR 21 , preferably a direct bond;

[0324] ,

[0325] In the formula, all residues and indices are as defined above.

[0326] A preferred compound of the chemical formula (Va) is prepared, for example, by the following steps:

[0327] Ia) Add BHal3 to intermediate (VIa) to obtain a compound of formula (Va):

[0328]

[0329] During the meal,

[0330] Hal represents a halogen, preferably F, Cl, Br, or I, more preferably Cl or Br, most preferably Br;

[0331] R 5 is C1-C 10 Alkyl, C3-C 12 Cycloalkyl, or C6-C 10 Aryl, preferably C1-C4 alkyl, C5-C 10 Cycloalkyl, or phenyl, more preferably tert - Representing butyl;

[0332] All other residues and indices are as defined above.

[0333] The intermediate (VIa) starts from, for example, a compound of the following chemical formula (VIIa), and

[0334] ,

[0335] (i) an amino compound (VIIIa) that can be further modified after reaction with compound (VIIa), or the reaction of Hal2 of compound (VIIa) with amino compound (VIIIb), and

[0336] (ii) Reaction of Hal1 of carbazole derivative (IX) and compound (VIIa)

[0337] It is manufactured as,

[0338] Among the above formulas,

[0339] Hal1 represents a halogen, preferably Cl, and

[0340] Hal2 represents a halogen, preferably Br, and

[0341] R 5 is C1-C 10 Alkyl, C3-C 12 Cycloalkyl, or C6-C 10 Aryl, preferably C1-C4 alkyl, C5-C 10 Cycloalkyl, or phenyl, more preferably tert - Represents butyl;

[0342] All other residues and indices are as defined above.

[0343] Generally, step (i) is performed first, followed by step (ii).

[0344] ,

[0345] This can be modified as follows: In the formula, the dotted line is the binding site to the compound of formula (VIIa) at the position of Hal2.

[0346]

[0347] In the formula, all residues and indices are as defined above.

[0348] Examples of suitable manufacturing methods are mentioned below.

[0349] Organic Electroluminescence device

[0350] According to one aspect of the present invention, a material for an organic electroluminescence device is provided, comprising at least one compound of formula (I).

[0351] According to another aspect of the present invention, an organic electroluminescence device comprising at least one compound of formula (I) is provided.

[0352] According to another aspect of the present invention, the following organic electroluminescence device is provided: an organic electroluminescence device comprising one or more organic thin film layers, the cathode, an anode, and a light-emitting layer disposed between the cathode and the anode, wherein at least one of the organic thin film layers comprises a compound of at least one formula (I).

[0353] According to another aspect of the present invention, an organic electroluminescence device is provided in which the light-emitting layer comprises at least one compound of formula (I).

[0354] According to another aspect of the present invention, an organic electroluminescence device is provided in which the light-emitting layer comprises at least one compound of formula (I) as a dopant material and an anthracene compound as a host material.

[0355] According to another aspect of the present invention, an electronic device is provided that includes an organic electroluminescence device according to the present invention.

[0356] According to another aspect of the present invention, an emitter material comprising at least one compound of formula (I) is provided.

[0357] According to another aspect of the present invention, a light-emitting layer is provided comprising at least one host and at least one dopant, wherein the dopant comprises at least one compound of formula (I).

[0358] According to another aspect of the present invention, a use of a compound of formula (I) according to the present invention is provided in an organic electroluminescence device.

[0359] In one embodiment, the organic EL device includes a hole transport layer between the anode and the light-emitting layer.

[0360] In one embodiment, the organic EL device includes an electron transport layer between the cathode and the light-emitting layer.

[0361] In this specification, with respect to "one or more organic thin film layers between the light-emitting layer and the anode," if only one organic layer exists between the light-emitting layer and the anode, this refers to that organic layer, and if multiple organic layers exist, this refers to at least one of the multiple organic layers. For example, if two or more organic layers exist between the light-emitting layer and the anode, the organic layer closer to the light-emitting layer is called a "hole transport layer," and the organic layer closer to the anode is called a "hole injection layer." Each of the "hole transport layer" and the "hole injection layer" may be a single layer or may form two or more layers. One of these layers may be a single layer, and the other may form two or more layers.

[0362] Similarly, with respect to "one or more organic thin film layers between the light-emitting layer and the cathode," if only one organic layer exists between the light-emitting layer and the cathode, this refers to that organic layer, and if multiple organic layers exist, this refers to at least one of the multiple organic layers. For example, if two or more organic layers exist between the light-emitting layer and the cathode, the organic layer closer to the light-emitting layer is called the "electron transport layer," and the organic layer closer to the cathode is called the "electron injection layer." Each of the "electron transport layer" and the "electron injection layer" may be a single layer or may form two or more layers. One of these layers may be a single layer, and the other may form two or more layers.

[0363] The above-mentioned "one or more organic thin film layers comprising a light-emitting layer," preferably, the light-emitting layer comprises a compound represented by the formula (I). The compound represented by the formula (I) preferably functions as an emitter material, more preferably as a fluorescent emitter material, and most preferably as a blue fluorescent emitter material. By the presence of the compound of the formula (I) in the organic EL device, preferably in the light-emitting layer, an organic EL device is provided that is characterized by high external quantum efficiency (EQE) and a long lifetime.

[0364] According to another aspect of the present invention, a light-emitting layer of an organic electroluminescence device comprising at least one compound of formula (I) is provided.

[0365] Preferably, the light-emitting layer comprises at least one light-emitting material (dopant material) and at least one host material, said light-emitting material is at least one compound of formula (I).

[0366] In one embodiment, the host is CBP(4,4'-bis-(N-carbazolyl)-biphenyl), mCP, mCBP Sif87(dibenzo[b,d]thiophene-2-yltriphenylsilane), CzSi, Sif88(dibenzo[b,d]thiophene-2-yl)diphenylsilane), DPEPO(bis[2-(diphenylphosphino)phenyl]etheroxide), 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) is not selected from.

[0367] A preferred host material is a substituted or unsubstituted polyaromatic hydrocarbon (PAH) compound, a substituted or unsubstituted polyheteroaromatic compound, a substituted or unsubstituted anthracene compound, or a substituted or unsubstituted pyrene compound.

[0368] More preferably, the organic electroluminescence device according to the present invention comprises, as a dopant material in the light-emitting layer, at least one compound of formula (I), and at least one host material selected from the group consisting of substituted or unsubstituted polyaromatic hydrocarbon (PAH) compounds, substituted or unsubstituted polyheteroaromatic 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.

[0369] In a further preferred embodiment, an organic electroluminescence device according to the present invention comprises, as a dopant material in the light-emitting layer, at least one compound of formula (I), and at least one host material selected from the group consisting of substituted or unsubstituted polyaromatic hydrocarbon (PAH) 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.

[0370] According to another aspect of the present invention, an emitting layer of an organic electroluminescence device is provided, comprising at least one compound of formula (I) as a dopant material and an anthracene compound as a host material.

[0371] Suitable anthracene compounds are represented by the following chemical formula (10):

[0372]

[0373] During the meal,

[0374] 2 or more adjacent Rs101 to R 110 One or more of the pairs may form substituted or unsubstituted saturated or unsaturated rings;

[0375] R that does not form substituted or unsubstituted saturated or unsaturated rings 101 to R 110 ...independently a hydrogen atom, a substituted or unsubstituted alkyl group comprising 1 to 50 carbon atoms, a substituted or unsubstituted haloalkyl group comprising 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group comprising 2 to 50 carbon atoms, a substituted or unsubstituted alkynyl group comprising 2 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group comprising 3 to 50 cyclic carbon atoms, a substituted or unsubstituted alkoxy group comprising 1 to 50 carbon atoms, a substituted or unsubstituted alkylene group comprising 1 to 50 carbon atoms, a substituted or unsubstituted aryloxy group comprising 6 to 50 cyclic carbon atoms, a substituted or unsubstituted arylthio group comprising 6 to 50 cyclic carbon atoms, a substituted or unsubstituted aralkyl group comprising 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 comprising 6 to 50 cyclic carbon atoms, a substituted or unsubstituted monovalent heterocyclic group comprising 5 to 50 cyclic atoms, or a group represented by the following chemical formula (31);

[0376] R 121 to R 127is independently a hydrogen atom, a substituted or unsubstituted alkyl group comprising 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group comprising 3 to 50 cyclic carbon atoms, a substituted or unsubstituted aryl group comprising 6 to 50 cyclic carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group comprising 5 to 50 cyclic atoms; and each R 121 to R 127 In cases where this exists in the plural, each plural R 121 to R 127 It may be the same or different;

[0377] However, R that does not form substituted or unsubstituted saturated or unsaturated rings 101 to R 110 At least one of them is a group represented by the following chemical formula (31). If there are two or more groups represented by the chemical formula (31), each of these groups may be the same or different;

[0378] -L 101 -Ar 101 (31)

[0379] In chemical formula (31),

[0380] L 101 is a single bond, a substituted or unsubstituted arylene group comprising 6 to 30 cyclic carbon atoms, or a substituted or unsubstituted divalent heterocyclic group comprising 5 to 30 cyclic atoms;

[0381] Ar 101 It is a substituted or unsubstituted aryl group containing 6 to 50 cyclic carbon atoms or a substituted or unsubstituted monovalent heterocyclic group containing 5 to 50 cyclic atoms.

[0382] Specific examples of each substituent, "substituted or unsubstituted" substituent and halogen atom in compound (10) are the same as those mentioned above.

[0383] 2 or more adjacent R 101to R 110 One or more pairs of them may form substituted or unsubstituted saturated or unsaturated rings.

[0384] 2 or more adjacent R 101 to R 110 "One pair of" is, 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 , R 102 and R 103 It is a combination of the back.

[0385] The substituents of the “substituted” in the “substituted or unsubstituted” of the saturated or unsaturated ring are the same as those for the “substituted or unsubstituted” mentioned in the chemical formula (10).

[0386] "Saturated or unsaturated ring" is R 101 class R 102 In the case where it forms a ring, for example, R 101 Carbon atom bonded to, R 102 It refers to a ring formed by a carbon atom bonded to and one or more arbitrary elements. Specifically, R 101 class R 102 In the case where a ring is formed by, R 101 Carbon atom bonded to, R 102 In the case where an unsaturated ring is formed by a carbon atom bonded to and four carbon atoms, R 101 class R 102 The ring formed by is a benzene ring.

[0387] "Any element" is preferably a C element, an N element, an O element, or an S element. In any element (e.g., a C element or an N element), atomic bonds that do not form a ring may be terminated by hydrogen atoms, etc.

[0388] "One or more arbitrary elements" are preferably 2 to 15, more preferably 3 to 12, and even more preferably 3 to 5 arbitrary elements.

[0389] For example, R 101 class R 102 can form a ring, and at the same time R 105 and R 106 It can form a ring. In this case, the compound represented by chemical formula (10) is, for example, the compound represented by the following chemical formula (10A):

[0390]

[0391] In one embodiment, R 101 to R 110 The group is independently a hydrogen atom, a substituted or unsubstituted alkyl group comprising 1 to 50 carbon atoms, a substituted or unsubstituted aryl group comprising 6 to 50 cyclic carbon atoms, a substituted or unsubstituted heterocyclic group comprising 5 to 50 cyclic atoms, or a group represented by the formula (31).

[0392] Preferably, R 101 to R 110 It is independently a hydrogen atom, a substituted or unsubstituted aryl group comprising 6 to 50 cyclic carbon atoms, a substituted or unsubstituted heterocyclic group comprising 5 to 50 cyclic atoms, or a group represented by the formula (31).

[0393] More preferably, R 101 to R 110It is independently a hydrogen atom, a substituted or unsubstituted aryl group comprising 6 to 18 cyclic carbon atoms, a substituted or unsubstituted heterocyclic group comprising 5 to 18 cyclic atoms, or a group represented by the formula (31).

[0394] Most preferably, at least one R 109 and R 110 is a group represented by the chemical formula (31).

[0395] Even more preferably, R 109 and R 110 is a group independently represented by the chemical formula (31).

[0396] In one embodiment, compound (10) is a compound represented by the following chemical formula (10-1):

[0397]

[0398] In the chemical formula (10-1), R 101 to R 108 , L 101 and Ar 101 It is as defined in the chemical formula (10).

[0399] In one embodiment, compound (10) is a compound represented by the following chemical formula (10-2):

[0400]

[0401] In the chemical formula (10-2), R 101 , R 103 to R 108 , L 101 and Ar 101 It is as defined in the chemical formula (10).

[0402] In one embodiment, compound (10) is a compound represented by the following chemical formula (10-3):

[0403]

[0404] In the chemical formula (10⁻³),

[0405] R 101A to R 108A is independently a substituted or unsubstituted aryl group comprising a hydrogen atom or 6 to 50 cyclic carbon atoms;

[0406] L 101A is a substituted or unsubstituted arylene group comprising a single bond or 6 to 30 cyclic carbon atoms, and 2 L 101A It may be the same or different;

[0407] Ar 101A is a substituted or unsubstituted aryl group containing 6 to 50 cyclic carbon atoms, and 2 Ar 101A It may be the same or different.

[0408] In one embodiment, compound (10) is a compound represented by the following chemical formula (10-4):

[0409]

[0410] In the chemical formula (10⁻⁴),

[0411] L 101 and Ar 101 is as defined in chemical formula (10);

[0412] R 101A to R 108A is independently a substituted or unsubstituted aryl group comprising a hydrogen atom or 6 to 50 cyclic carbon atoms;

[0413] X 11 is O, S, or N(R 61 ) and;

[0414] R 61 It is a hydrogen atom, a substituted or unsubstituted alkyl group comprising 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group comprising 6 to 50 cyclic carbon atoms;

[0415] R 62 to R 69One of them is L 101 It is an aromatic bond combined with;

[0416] L 101 Adjacent R that is not combined with 62 to R 69 One or more pairs of these may be combined to form substituted or unsubstituted saturated or unsaturated rings;

[0417] L 101 R that is not bonded to and does not form substituted or unsubstituted saturated or unsaturated rings 62 to R 69 is independently a hydrogen atom, a substituted or unsubstituted alkyl group comprising 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group comprising 6 to 50 cyclic carbon atoms.

[0418] In one embodiment, compound (10) is a compound represented by the following formula (10-4A):

[0419]

[0420] In the chemical formula (10⁻⁴A),

[0421] L 101 and Ar 101 is as defined in chemical formula (10);

[0422] R 101A to R 108A is independently a substituted or unsubstituted aryl group comprising a hydrogen atom or 6 to 50 cyclic carbon atoms;

[0423] X 11 is O, S, or N(R 61 ) and;

[0424] R 61 is a hydrogen atom, a substituted or unsubstituted alkyl group comprising 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group comprising 6 to 50 cyclic carbon atoms;

[0425] Two or more adjacent Rs 62Ato R 69A One or more pairs of these may form substituted or unsubstituted saturated or unsaturated rings, and R 62A to R 69A Two adjacent groups form a ring represented by the following chemical formula (10-4A-1);

[0426] R that does not form substituted or unsubstituted saturated or unsaturated rings 62A to R 69A is independently a hydrogen atom, a substituted or unsubstituted alkyl group comprising 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group comprising 6 to 50 cyclic carbon atoms.

[0427]

[0428] In the chemical formula (10⁻⁴A⁻¹),

[0429] Each of the two atomic bonds * is R 62A to R 69A Combined with 2 adjacent ones;

[0430] R 70 to R 73 One of them is L 101 It is an atomic bond combined with;

[0431] L 101 R that is not combined with 70 to R 73 It is independently a hydrogen atom, a substituted or unsubstituted alkyl group comprising 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group comprising 6 to 50 cyclic carbon atoms.

[0432] In one embodiment, compound (10) is a compound represented by the following chemical formula (10-6):

[0433]

[0434] In the chemical formula (10⁻⁶),

[0435] L 101 and Ar 101is as defined in chemical formula (10);

[0436] R 101A to R 108A is as defined in the chemical formula (10⁻⁴);

[0437] R 66 to R 69 is as defined in the chemical formula (10⁻⁴);

[0438] X 12 is O or S.

[0439] In one embodiment, the compound represented by the formula (10-6) is a compound represented by the following formula (10-6H):

[0440]

[0441] In the chemical formula (10⁻⁶H),

[0442] L 101 and Ar 101 is as defined in chemical formula (10);

[0443] R 66 to R 69 is as defined in the chemical formula (10⁻⁴);

[0444] X 12 is O or S.

[0445] In one embodiment, the compound represented by the formulas (10-6) and (10-6H) is the compound represented by the following formula (10-6Ha):

[0446]

[0447] In the chemical formula (10⁻⁶Ha),

[0448] L 101 and Ar 101 is as defined in chemical formula (10);

[0449] X 12 is O or S.

[0450] In one embodiment, the compound represented by the formulas (10-6), (10-6H) and (10-6Ha) is a compound represented by the following formulas (10-6Ha-1) or (10-6Ha-2):

[0451]

[0452] In chemical formulas (10⁻⁶Ha⁻¹) and (10⁻⁶Ha⁻²),

[0453] L 101 and Ar 101 is as defined in chemical formula (10);

[0454] X 12 is O or S.

[0455] In one embodiment, compound (10) is a compound represented by the following chemical formula (10-7):

[0456]

[0457] In the chemical formula (10⁻⁷),

[0458] L 101 and Ar 101 is as defined in chemical formula (10);

[0459] R 101A to R 108A is as defined in the chemical formula (10⁻⁴);

[0460] X 11 is as defined in the chemical formula (10⁻⁴);

[0461] R 62 to R 69 is as defined in the chemical formula (10-4), provided that R 66 class R 67 , R 67 class R 68 , and R 68 class R 69Any pair of them combines to form a substituted or unsubstituted saturated or unsaturated ring.

[0462] In one embodiment, compound (10) is a compound represented by the following chemical formula (10-7H):

[0463]

[0464] In the chemical formula (10⁻⁷H),

[0465] L 101 and Ar 101 is as defined in chemical formula (10);

[0466] X 11 is as defined in the chemical formula (10⁻⁴);

[0467] R 62 to R 69 is as defined in the chemical formula (10⁻⁴), where R 66 class R 67 , R 67 class R 68 , and R 68 class R 69 Any pair of them combines to form a substituted or unsubstituted saturated or unsaturated ring.

[0468] In one embodiment, compound (10) is a compound represented by the following chemical formula (10-8):

[0469]

[0470] In the chemical formula (10⁻⁸),

[0471] L 101 and Ar 101 is as defined in chemical formula (10);

[0472] R 101A to R 108A is as defined in the chemical formula (10⁻⁴);

[0473] X 12is O or S;

[0474] R 66 to R 69 is as defined in the chemical formula (10⁻⁴), where R 66 class R 67 , R 67 class R 68 , and R 68 class R 69 Any pair of them combines to form a substituted or unsubstituted saturated or unsaturated ring.

[0475] In one embodiment, the compound represented by the formula (10-8) is a compound represented by the following formula (10-8H):

[0476]

[0477] In the chemical formula (10⁻⁸H), L 101 and Ar 101 It is as defined in the chemical formula (10).

[0478] R 66 to R 69 is as defined in the chemical formula (10⁻⁴), where R 66 class R 67 , R 67 class R 68 , and R 68 class R 69 Any pair of these combines to form a substituted or unsubstituted saturated or unsaturated ring. R 66 class R 67 , R 67 class R 68 , and R 68 class R 69 Any one of the pairs can preferably be combined with each other to form an unsubstituted benzene ring;

[0479] X 12is O or S.

[0480] In one embodiment, in a compound represented by the formula (10-7), (10-8) or (10-8H), R 66 class R 67 , R 67 class R 68 , and R 68 class R 69 Any pair of them are combined to form a ring represented by the following chemical formula (10-8-1) or (10-8-2), and R does not form a ring represented by the chemical formula (10-8-1) or (10-8-2). 66 to R 69 It does not form substituted or unsubstituted saturated or unsaturated rings.

[0481]

[0482] In chemical formulas (10-8-1) and (10-8-2),

[0483] The two atomic bonds * are independently R 66 class R 67 , R 67 class R 68 , or R 68 class R 69 Combined with one pair of them;

[0484] R 80 to R 83 is independently a hydrogen atom, a substituted or unsubstituted alkyl group comprising 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group comprising 6 to 50 cyclic carbon atoms;

[0485] X 13 is O or S.

[0486] In one embodiment, compound (10) is a compound represented by the following chemical formula (10-9):

[0487]

[0488] In the chemical formula (10⁻⁹),

[0489] L 101 and Ar 101 is as defined in chemical formula (10);

[0490] R 101A to R 108A is as defined in the chemical formula (10⁻⁴);

[0491] R 66 inside R 69 is as defined in the chemical formula (10⁻⁴), where R 66 class R 67 , R 67 class R 68 , and R 68 class R 69 They are not bonded to each other and do not form substituted or unsubstituted saturated or unsaturated rings;

[0492] X 12 is O or S.

[0493] 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).

[0494]

[0495] In chemical formulas (10-10-1H) to (10-10-4H), L 101A and Ar 101A is as defined in the chemical formula (10-3).

[0496] For compounds represented by the chemical formula (10), the following compounds can be given as specific examples.

[0497]

[0498]

[0499]

[0500]

[0501]

[0502]

[0503]

[0504]

[0505]

[0506]

[0507]

[0508]

[0509]

[0510]

[0511]

[0512]

[0513]

[0514]

[0515]

[0516]

[0517]

[0518]

[0519]

[0520]

[0521]

[0522]

[0523]

[0524] The light-emitting layer comprises a compound represented by formula (I) as a dopant and at least one host, wherein the preferred host is mentioned above and 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 mass% to 70 mass%, more preferably 0.5 to 30 mass%, even more preferably 1 to 30 mass%, even more preferably 1 to 20 mass% with respect to the total mass of the light-emitting layer, particularly preferably 1 to 10 mass%, and even more particularly preferably 1 to 5 mass%.

[0525] The content of at least one host, preferably represented by the formula (10), which is a preferred host mentioned above, is preferably 30 to 99.9 mass%, more preferably 70 to 99.5 mass%, even more preferably 70 to 99 mass%, even more preferably 80 to 99 mass%, particularly preferably 90 to 99 mass%, and even more particularly preferably 95 to 99 mass% with respect to the total mass of the light-emitting layer.

[0526] The description of the present invention On one side Organic EL according to device's It is about the layer composition.

[0527] An organic EL device according to one aspect of the present invention comprises one or more organic thin film layers, including a cathode, an anode, and a light-emitting layer disposed between the cathode and the anode. The organic layer comprises at least one layer composed of an organic compound. Alternatively, the organic layer is formed by stacking a plurality of layers composed of organic compounds. The organic layer may further comprise an inorganic compound in addition to the organic compound.

[0528] At least one organic layer is a light-emitting layer. The organic layer may be composed, 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 device. The layers that can be adopted in the layer structure of the organic EL device are not particularly limited, but examples thereof include a hole transport zone (at least one hole transport layer, and preferably further including at least one hole injection layer, electron blocking layer, exciton blocking layer, etc.), a light-emitting layer, a spacing layer, and an electron transport zone provided between the cathode and the light-emitting layer (at least one electron transport layer and preferably further including at least one electron injection layer, hole blocking layer, etc.).

[0529] An organic EL device according to one aspect of the present invention may be, for example, a fluorescent or phosphorescent monochromatic light-emitting device or a fluorescent / phosphorescent hybrid white light-emitting device. Preferably, the organic EL device is a fluorescent monochromatic light-emitting device, more preferably a blue fluorescent monochromatic light-emitting device or a fluorescent / phosphorescent hybrid white light-emitting device. Blue fluorescence refers to fluorescence at 400 to 500 nm (peak maximum), preferably at 430 nm to 490 nm (peak maximum).

[0530] Additionally, it may be a simple device having a single light-emitting unit or a tandem device having multiple light-emitting units.

[0531] In this specification, the "emitting unit" is a minimum unit comprising an organic layer, wherein at least one organic layer is an emitting layer and light is emitted by the recombination of injected holes and electrons.

[0532] In addition, the "emissive layer" described in this specification is an organic layer having a light-emitting function. The emissive layer is, for example, a phosphorescent emissive layer, a fluorescent emissive layer, etc., preferably a fluorescent emissive layer, more preferably a blue fluorescent emissive layer, and may be a single layer or a stack of multiple layers.

[0533] 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 spacing layer may be provided between each light-emitting layer to prevent excitons generated in the phosphorescent light-emitting layer from diffusing into the fluorescent light-emitting layer.

[0534] As a simple organic EL device, a device configuration such as an anode / emissive unit / cathode can be presented.

[0535] Examples of representative layer structures of luminescent units are shown below. The layers in parentheses are provided arbitrarily.

[0536] (a) (hole injection layer / ) hole transport layer / fluorescent emitting layer( / electron transport layer / electron injection layer)

[0537] (b) (hole injection layer / ) hole transport layer / phosphorescent emission layer( / electron transport layer / electron injection layer)

[0538] (c) (hole injection layer / ) hole transport layer / first fluorescent emitting layer / second fluorescent emitting layer( / electron transport layer / electron injection layer)

[0539] (d) (hole injection layer / ) hole transport layer / first phosphorescent layer / second phosphorescent layer( / electron transport layer / electron injection layer)

[0540] (e) (hole injection layer / ) hole transport layer / phosphorescent emitting layer / separation layer / fluorescent emitting layer( / electron transport layer / electron injection layer)

[0541] (f) (hole injection layer / ) hole transport layer / first phosphorescent emitting layer / second phosphorescent emitting layer / separation layer / fluorescent emitting layer( / electron transport layer / electron injection layer)

[0542] (g) (hole injection layer / ) hole transport layer / first phosphorescent layer / separator layer / second phosphorescent emitting layer / separator layer / fluorescent emitting layer( / electron transport layer / electron injection layer)

[0543] (h) (hole injection layer / ) hole transport layer / phosphorescent emitting layer / separation layer / first fluorescent emitting layer / second fluorescent emitting layer( / electron transport layer / electron injection layer)

[0544] (i) (hole injection layer / ) hole transport layer / electron blocking layer / fluorescent emitting layer( / electron transport layer / electron injection layer)

[0545] (j) (hole injection layer / ) hole transport layer / electron blocking layer / phosphor emissive layer( / electron transport layer / electron injection layer)

[0546] (k) (hole injection layer / ) hole transport layer / exciton blocking layer / fluorescent emitting layer( / electron transport layer / electron injection layer)

[0547] (l) (hole injection layer / ) hole transport layer / exciton blocking layer / phosphor emissive layer( / electron transport layer / electron injection layer)

[0548] (m) (hole injection layer / ) first hole transport layer / second hole transport layer / fluorescent emitting layer( / electron transport layer / electron injection layer)

[0549] (n) (hole injection layer / ) first hole transport layer / second hole transport layer / fluorescent emitting layer( / first electron transport layer / second electron transport layer / electron-injection layer)

[0550] (o) (hole injection layer / ) first hole transport layer / second hole transport layer / phosphorescent emitting layer( / electron transport layer / electron injection layer)

[0551] (p) (hole injection layer / ) first hole transport layer / second hole transport layer / phosphor emissive layer( / first electron transport layer / second electron transport layer / electron injection layer)

[0552] (q) (hole injection layer / ) hole transport layer / fluorescent emitting layer / hole blocking layer( / electron transport layer / electron injection layer)

[0553] (r) (hole injection layer / ) hole transport layer / phosphorescent emitting layer / hole blocking layer( / electron transport layer / electron injection layer)

[0554] (s) (hole injection layer / ) hole transport layer / fluorescent emitting layer / exciton blocking layer( / electron transport layer / electron injection layer)

[0555] (t) (hole injection layer / ) hole transport layer / phosphorescent emission layer / exciton blocking layer( / electron transport layer / electron injection layer)

[0556] The layer structure of an organic EL device according to one aspect of the present invention is not limited to the examples mentioned above.

[0557] For example, if an organic EL device has a hole injection layer and a hole transport layer, it is preferable that the hole injection layer be provided between the hole transport layer and the anode. Additionally, if an organic EL device has an electron injection layer and an electron transport layer, it is preferable that the electron injection layer be provided between the electron transport layer and the cathode. Furthermore, each of the hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer may be formed as a single layer or as a plurality of layers.

[0558] A plurality of phosphorescent emitting layers, and a plurality of phosphorescent emitting layers and fluorescent emitting layers may be emitting layers that emit different colors. For example, the emitting unit (f) may include a hole transport layer / a first phosphorescent layer (red emission) / a second phosphorescent emitting layer (green emission) / a spacing layer / a fluorescent emitting layer (blue emission) / an electron transport layer.

[0559] An electron blocking layer may be provided between each emitting layer and a hole transport layer or a spacing layer. Additionally, a hole blocking layer may be provided between each emitting layer and an electron transport layer. By providing an electron blocking layer or a hole blocking layer, electrons or holes can be confined in the emitting layer, thereby improving the carrier recombination probability in the emitting layer and improving luminous efficiency.

[0560] Typical device configurations of a tandem organic EL device include, for example, an anode / first light-emitting unit / intermediate layer / second light-emitting unit / cathode.

[0561] The first light-emitting unit and the second light-emitting unit are selected independently from, for example, the light-emitting units mentioned above.

[0562] The intermediate layer is also generally referred to as an intermediate electrode, intermediate conductive layer, charge generating layer, electron-attracting layer, connection layer, connector layer, or intermediate insulating layer. The intermediate layer is a layer that supplies electrons to a first light-emitting unit and supplies holes to a second light-emitting unit, and can be formed from a known material.

[0564] Fig. 1 The figure shows a schematic configuration of an example of an organic EL device of the present invention. The organic EL device (1) comprises 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 comprises a light-emitting layer (5) comprising a host material and a dopant. A hole injection and transport layer (6), etc., 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), etc. (electron injection and transport unit (11)) may be provided between the light-emitting layer (5) and the cathode (4). An electron barrier layer may be provided on the anode (3) side of the light-emitting layer (5), and a hole barrier layer may be provided on the cathode (4) side of the light-emitting layer (5). Due to this configuration, electrons or holes are confined in the light-emitting layer (5), thereby improving the possibility of generating excitons in the light-emitting layer (5).

[0565] Hereinafter, the organic EL described in this specification The device Explain the function, materials, etc. of each constituent layer.

[0566] (Circuit board)

[0567] The substrate is used as a support for the organic EL device. The substrate is preferably a smooth substrate with a light transmittance of 50% or more in the visible light region of wavelengths from 400 to 700 nm. Examples of substrate materials include soda-lime glass, aluminosilicate glass, quartz glass, plastic, etc. A flexible substrate may be used as the substrate. A flexible substrate refers to a substrate that can be bent (flexible), and examples thereof include plastic substrates. Specific examples of materials forming the plastic substrate include polycarbonate, polyallylate, polyether sulfone, polypropylene, polyester, polyvinyl fluoride, polyvinyl chloride, polyimide, polyethylene naphthalate, etc. Additionally, an inorganic vapor deposition film may be used.

[0568] ( Anode )

[0569] As an anode, it is preferable to use, for example, a metal, alloy, conductive compound, or mixture thereof having a high work function (specifically 4.0 eV or higher). Specific examples of anode materials include indium tin oxide (ITO), indium tin oxide containing silicon or silicon oxide, indium zinc oxide, indium oxide containing tungsten oxide or zinc oxide, graphene, etc. In addition, it is also possible to use gold, silver, platinum, nickel, tungsten, chromium, molybdenum, iron, cobalt, copper, palladium, titanium, and nitrides of these metals (e.g., titanium oxide).

[0570] The anode is generally formed by depositing these materials on a substrate by a sputtering method. For example, indium oxide-zinc oxide can be formed by a sputtering method using a target to which 1 to 10 mass% of zinc oxide is added to indium oxide. In addition, indium oxide containing tungsten oxide or zinc oxide can be formed by a sputtering method using a target to which 0.5 to 5 mass% of tungsten oxide or 0.1 to 1 mass% of zinc oxide is added to indium oxide.

[0571] Other methods for forming an anode include vacuum deposition, coating, inkjet, and spin coating. When using silver paste, it is possible to use coating or inkjet methods.

[0572] The hole injection layer formed in contact with the anode is formed using a material that facilitates hole injection regardless of the work function of the anode. For this reason, it is possible to use common electrode materials for the anode, such as metals, alloys, conductive compounds, and mixtures thereof. Specifically, there are materials with small work functions, such as alkali metals like lithium and cesium; alkaline earth metals like calcium and strontium; alloys containing these metals (e.g., magnesium-silver and aluminum-lithium); rare earth metals like europium and ytterbium; and alloys containing rare earth metals.

[0573] (Jeongong Transport layer ) / (정공 Injection layer )

[0574] The hole transport layer is an organic layer formed between the emissive layer and the anode, and has the function of transporting holes from the anode to the emissive layer. When the hole transport layer consists of multiple layers, the organic layer closer to the anode can often be defined as the hole injection layer. The hole injection layer has the function of efficiently injecting holes from the anode into the organic layer. The hole injection layer is generally used to stabilize the injection of holes from the anode into the hole transport layer, which is typically composed of an organic material. It is preferable to use an organic material with good contact with the anode or a p-type doped organic material as the hole injection layer.

[0575] p-doping generally consists of one or more p-dopant materials and one or more matrix materials. To enhance the carrier density of the layer, the matrix material preferably has a shallower HOMO level, and the p-dopant preferably has a deeper LUMO level. Specific examples of p-dopants are the acceptor materials mentioned below. Suitable matrix materials are the hole transport materials mentioned below, preferably aromatic or heterocyclic amine compounds.

[0576] As a p-dopant material for the hole injection layer, an acceptor material, or a fused aromatic hydrocarbon material having high planarity, or a fused heterocycle is preferably used. Specific examples of acceptor materials are quinone compounds having one or more electron-withdrawing groups, such as F4TCNQ (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; hexa-azatriphenylene compounds having one or more electron-withdrawing groups, such as hexa-azatriphenylene-hexanitrile; aromatic hydrocarbon compounds having one or more electron-withdrawing groups; and aryl boron compounds having one or more electron-withdrawing groups. A preferred p-dopant is a quinone compound having one or more electron-withdrawing groups, such as F4TCNQ, 1,2,3-tris[(cyano)(4-cyano-2,3,5,6-tetrafluorophenyl)methylene]cyclopropane.

[0577] The proportion of p-type dopant is preferably less than 20% molar ratio with respect to the matrix material, more preferably less than 10%, e.g. 1%, 3%, or 5%.

[0578] Hole transport layers are generally used to efficiently inject and transport holes, and aromatic or heterocyclic amine compounds are preferably used.

[0579] Specific examples of compounds for the hole transport layer are represented by the following general chemical formula (H):

[0580]

[0581] During the meal,

[0582] Ar1 to Ar3 each independently represent a substituted or unsubstituted aryl group having 5 to 50 carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 50 cyclic 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; Ar 1 or Ar 3 Two or more selected substituents can be combined to form a ring structure such as a carbazole ring structure or an acridane ring structure.

[0583] Preferably, at least one of Ar1 to Ar3 has an additional aryl or heterocyclic amine substituent, and more preferably, Ar1 has an additional aryl amino substituent, wherein Ar1 preferably represents a substituted or unsubstituted biphenylene group or a substituted or unsubstituted fluorenylene group. Specific examples of hole transport materials are

[0584] and

[0585] It is the back.

[0586] It is desirable to insert a second hole transport layer between the first hole transport layer and the light-emitting layer to improve device performance 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. It is desirable for the second hole transport layer to have a higher triplet energy to block triplet excitons, and particularly for phosphorescent devices, examples such as bicarbazole compounds, biphenylamine compounds, triphenylenylamine compounds, fluorenylamine compounds, carbazole-substituted arylamine compounds, dibenzofuran-substituted arylamine compounds, and dibenzothiophene-substituted arylamine compounds are preferred.

[0587] ( light-emitting layer )

[0588] The emissive layer is a layer containing a material with high luminescence properties (emitter material or dopant material). Various materials can be used as dopant materials. For example, fluorescent emitting compounds (fluorescent dopants) and phosphorescent emitting compounds (phosphorescent dopants) may be used. A fluorescent emitting compound is a compound capable of emitting light from a singlet excited state, and an emissive layer containing a fluorescent emitting compound is referred to as a fluorescent emitting layer. Additionally, a phosphorescent emitting compound is a compound capable of emitting light from a triplet excited state, and an emissive layer containing a phosphorescent emitting compound is referred to as a phosphorescent emitting layer.

[0589] Preferably, in the organic EL device of the present application, the light-emitting layer comprises a compound of formula (I) as a dopant material.

[0590] The emissive layer preferably comprises at least one dopant material and at least one host material capable of efficiently emitting light. In some literature, the dopant material is referred to as a guest material, emitter, or emissive material. In some literature, the host material is referred to as a matrix material.

[0591] A single light-emitting layer may include a plurality of dopant materials and a plurality of host materials. Additionally, a plurality of light-emitting layers may exist.

[0592] 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 solely by their molecular structure. A phosphorescent host is a material for forming a phosphorescent emitting layer containing a phosphorescent dopant, but this does not mean that it cannot be used as a material for forming a fluorescent emitting layer. The same applies to fluorescent hosts.

[0593] In one embodiment, the light-emitting layer preferably comprises a compound represented by the formula (I) according to the present invention (hereinafter, such a compound may be referred to as "compound (I)"). More preferably, it is contained as a dopant material. Additionally, compound (I) is preferably contained in the light-emitting layer as a fluorescent dopant. Furthermore, compound (I) is preferably contained in the light-emitting layer as a blue fluorescent dopant.

[0594] In one embodiment, no specific limitation is imposed on the content of compound (I) as a dopant material in the light-emitting layer. For sufficient light emission and concentration quenching, the content is preferably 0.5 to 70 mass%, more preferably 0.8 to 30 mass%, even more preferably 1 to 30 mass%, even more preferably 1 to 20 mass%, particularly preferably 1 to 10 mass%, even more particularly preferably 1 to 5 mass%, and even more particularly preferably 2 to 4 mass% with respect to the mass of the light-emitting layer.

[0595] (fluorescence dopant )

[0596] Examples of fluorescent dopants other than compound (I) include fused polycyclic aromatic compounds, styrylamine compounds, fused cyclic amine compounds, boron-containing compounds, pyrrole compounds, indole compounds, and carbazole compounds. Among these, fused cyclic amine compounds, boron-containing compounds, and carbazole compounds are preferred.

[0597] Examples of fused ring amine compounds include diaminofluorene compounds, diaminopyrene compounds, diaminochrysene compounds, diaminoanthracene compounds, and diaminofluorene compounds in which one or more benzofuro skeletons are fused.

[0598] Examples of boron-containing compounds include pyromethane compounds and triphenylborane compounds.

[0599] Examples of blue fluorescent dopants include pyrene compounds, styrylamine compounds, chrysene compounds, fluoranthene compounds, fluorene compounds, diamine compounds, triarylamine compounds, etc. Specifically, N,N'-bis[4-(9H-carbazole-9-yl)phenyl]-N,N'-diphenylstilbene-4,4'-diamine (abbreviation: YGA2S), 4-(9H-carbazole-9-yl)-4'-(10-phenyl-9-anthryl)triphenylamine (abbreviation: YGAPA), 4-(10-phenyl-9-anthryl)-4'-(9-phenyl-9H-carbazole-3-yl)triphenylamine (abbreviation: PCBAPA), etc.

[0600] Examples of green fluorescent dopants include aromatic amine compounds. Specifically, examples include 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), and N-[9,10-bis(1,1'-biphenyl-2-yl)-2-anthryl]-N,N',N'-triphenyl-1,4-phenylenediamine (abbreviation: 2DPABPhA). Examples include N-[9,10-bis(1,1'-biphenyl-2-yl)]-N-[4-(9H-carbazole-9-yl)phenyl]-N-phenylanthracen-2-amine (abbreviation: 2YGABPhA), N,N,9-triphenylanthracen-9-amine (abbreviation: DPhAPhA), etc.

[0601] Examples of red fluorescent dopants include tetracene compounds and diamine compounds. Specifically, examples include N,N,N',N'-tetrakis(4-methylphenyl)tetracene-5,11-diamine (abbreviation: p-mPhTD), 7,14-diphenyl-N,N,N',N'-tetrakis(4-methylphenyl)acenaphthor[1,2-a]fluoranthene-3,10-diamine (abbreviation: p-mPhAFD).

[0602] (Phosphorescent) dopant)

[0603] Examples of phosphorescent dopants include phosphorescent heavy metal complexes and phosphorescent rare earth metal complexes.

[0604] Examples of heavy metal complexes include iridium complexes, osmium complexes, and platinum complexes. Heavy metal complexes are, for example, ortho-metallic complexes of metals selected from iridium, osmium, and platinum.

[0605] Examples of rare earth metal complexes include terbium complexes and europium complexes. Specifically, tris(acetylacetonate)(monophenanthrolin)terbium(III) (abbreviation: Tb(acac)3(Phen)), tris(1,3-diphenyl-1,3-propandionate)(monophenanthrolin)europium(III) (abbreviation: Eu(DBM)3(Phen)), and tris[1-(2-tenoyl)-3,3,3-trifluoroacetonate](monophenanthrolin)europium(III) (abbreviation: Eu(TTA)3(Phen)) can be cited. These rare earth metal complexes are desirable as phosphorescent dopants because the rare earth metal ions emit light due to electron transitions between different multiplicityes.

[0606] Examples of blue phosphorescent dopants include iridium complexes, osmium complexes, platinum complexes, etc. Specifically, examples include bis[2-(4',6'-difluorophenyl)pyridinate-N,C2']iridium(III)tetrakis(1-pyrazolyl)borate (abbreviation: FIr6), bis[2-(4',6'-difluorophenyl)pyridinate-N,C2']iridium(III)picolinate (abbreviation: Ir(CF3ppy)2(pic)), bis[2-(4',6'-difluorophenyl)pyridinate-N,C2']iridium(III)acetylacetonate (abbreviation: FIracac), etc.

[0607] Examples of green phosphorescent dopants include iridium complexes. Specifically, examples include tris(2-phenylpyridinato-N,C2')iridium(III) (abbreviation: Ir(ppy)3), bis(1,2-diphenyl-1H-benzimidazoleto)iridium(III)acetylacetonate (abbreviation: Ir(pbi)2(acac)), and bis(benzo[h]quinolinato)iridium(III)acetylacetonate (abbreviation: Ir(bzq)2(acac)).

[0608] Examples of red phosphorescent dopants include iridium complexes, platinum complexes, terbium complexes, europium complexes, etc. Specifically, examples include 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).

[0609] As mentioned above, the light-emitting layer preferably comprises at least one compound (I) as a dopant.

[0610] (Host substance)

[0611] Examples of host materials include, for instance, 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, quinazolin compounds, dibenzofuran compounds, dibenzothiophene compounds, oxadiazole compounds, benzimidazole compounds, and phenanthroline compounds; fused polyaromatic 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 fused polycyclic aromatic amine compounds. Multiple types of host materials may be used in combination.

[0612] As a fluorescent host, a compound having a singlet energy level higher than that of the fluorescent dopant is preferred. Examples include heterocyclic compounds and fused aromatic compounds. As fused aromatic compounds, anthracene compounds, pyrene compounds, chrysene compounds, and naphthacene compounds are preferred. Anthracene compounds are preferentially used as blue fluorescent hosts.

[0613] When compound (I) is used as at least one dopant material, the preferred host material is a substituted or unsubstituted polyaromatic hydrocarbon (PAH) compound, a substituted or unsubstituted polyheteroaromatic compound, a substituted or unsubstituted anthracene compound, or a substituted or unsubstituted pyrene compound, preferably a substituted or unsubstituted anthracene compound or a substituted or unsubstituted pyrene compound, more preferably a substituted or unsubstituted anthracene compound, most preferably an anthracene compound represented by the formula (10) mentioned above.

[0614] As a phosphorescent host, a compound having a triplet energy level higher than that of a phosphorescent dopant is preferred. Examples include metal complexes, heterocyclic compounds, and fused aromatic compounds. Among these, examples include indole compounds, carbazole compounds, pyridine compounds, pyrimidine compounds, triazine compounds, quinolone compounds, isoquinoline compounds, quinazolin compounds, dibenzofuran compounds, dibenzothiophene compounds, naphthalene compounds, triphenylene compounds, phenanthrene compounds, and fluoranthene compounds.

[0615] (former Transport layer ) / (former Injection layer )

[0616] The electron transport layer is an organic layer formed between the light-emitting layer and the cathode, and has the function of transporting electrons from the cathode to the light-emitting layer. When the electron transport layer is formed in multiple layers, the organic or inorganic layer closer to the cathode is often defined as the electron injection layer (e.g., see layer (8) in FIG. 1, where the electron injection layer (8) and the electron transport layer (7) form an electron injection and transport unit (11)). The electron injection layer has the function of efficiently injecting electrons from the cathode to 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.

[0617] According to one embodiment, the electron transport layer preferably further comprises one or more layers such as a second electron transport layer, an electron injection layer for improving the efficiency and lifespan of the device, a hole blocking layer, an exciton blocking layer, or a triplet blocking layer.

[0618] According to one embodiment, it is preferable to include an electron-donating dopant in the interface region between the cathode and the light-emitting unit. Due to this configuration, the organic EL device may have increased brightness or a long lifetime. Here, the electron-donating dopant means having a metal having a work function of 3.8 eV or less. Specific examples thereof may 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.

[0619] 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. It is particularly desirable that the work function is 2.9 eV or less. Among these, K, Rb, and Cs are preferred. Rb or Cs are 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. It is particularly desirable that the work function is 2.9 eV or less. Examples of rare earth metals include Sc, Y, Ce, Tb, Yb, etc. It is particularly desirable that the work function is 2.9 eV or less.

[0620] Examples of alkali metal compounds include alkali oxides such as Li2O, Cs2O, or K2O, and alkali halides such as LiF, NaF, CsF, and KF. Among these, LiF, Li2O, and NaF are preferred. Examples of alkaline earth metal compounds include BaO, SrO, CaO, and mixtures thereof, such as Ba x Sr1 - x O(0 <x<1) 및 Ba x Ca1 - xO(0 <x<1)를 포함한다. 이들 중에서, BaO, SrO 및 CaO가 바람직하다. 희토류 금속 화합물의 예는 YbF3, ScF3, ScO3, Y2O3, Ce2O3, GdF3및 It includes TbF3. Among these, YbF3, ScF3 and TbF3 is desirable.

[0621] Alkali metal complexes, alkaline earth metal complexes, and rare earth metal complexes are not particularly limited as long as they contain at least one alkali metal ion, alkaline earth metal ion, and rare earth metal ion as a metal ion. Meanwhile, preferred examples of ligands include, but are not limited to, quinolinol, benzoquinolinol, acridinol, phenantridinol, hydroxyphenyloxazole, hydroxyphenylthiazole, hydroxydiaryloxadiazole, hydroxydiarylthiadiazole, hydroxyphenylpyridine, hydroxyphenylbenzimidazole, hydroxybenzotriazole, hydroxyfluborane, bipyridyl, phenanthroline, phthalocyanine, porphyrin, cyclopentadiene, β-diketone, and azomethine.

[0622] Regarding the form of addition of the electron-donating dopant, it is preferable that the electron-donating dopant be formed in the shape of a layer or an island in the interfacial region. A preferred formation method is to disperse the electron-donating dopant in an organic compound by depositing an organic compound (a luminescent material or an electron injection material) to form the interfacial region simultaneously with the deposition of the electron-donating dopant by resistance heating deposition.

[0623] When the electron-donating dopant is formed in a layer shape, a luminescent material or electron injection material acting as an organic layer at the interface is formed in a layer shape. Subsequently, a reducing dopant is deposited alone by resistance heating deposition to form a layer preferably having a thickness of 0.1 nm to 15 nm. When the electron-donating dopant is formed in an island shape, a luminescent material or electron injection material acting as an organic layer at the interface is formed in an island shape. Subsequently, the electron-donating dopant is deposited alone by resistance heating deposition to form an island preferably having a thickness of 0.05 nm to 1 nm. As an electron transport material used in the electron transport layer other than the compound of Formula (I), an aromatic heterocyclic compound having one or more heteroatoms within the molecule may be preferably used. In particular, a nitrogen-containing heterocyclic compound is preferred.

[0624] According to one embodiment, the electron transport layer preferably comprises a nitrogen-containing heterocyclic metal chelate.

[0625] According to another embodiment, the electron transport layer preferably comprises a substituted or unsubstituted nitrogen-containing heterocyclic compound. Specific examples of preferred heterocyclic compounds for the electron transport layer include hexavalent azine compounds; e.g., pyridine compounds, pyrimidine compounds, triazine compounds, pyrazine compounds, preferably pyrimidine compounds or triazine compounds; hexavalent fused azine compounds, e.g., quinolone compounds, isoquinoline compounds, quinoxaline compounds, quinazoline compounds, phenanthroline compounds, benzoquinoline compounds, benzisoquinoline compounds, dibenzoquinoxaline compounds, preferably quinolone compounds, isoquinoline compounds, phenanthroline compounds; pentary heterocyclic compounds, e.g., imidazole compounds, oxazole compounds, oxadiazole compounds, triazole compounds, thiazole compounds, thiadiazole compounds; It is a fused imidazole compound, such as a benzimidazole compound, an imidazopyridine compound, a naphthomidazole compound, a benzimidazophenantridine compound, a benzimidozobenzimidazole compound, preferably a benzimidazole compound, an imidazopyridine compound, or a benzimidazophenantridine compound.

[0626] According to another embodiment, the electron transport layer is Ar p1 Ar p2 Ar P3 It is preferable to include a phosphine oxide compound represented as P=O.

[0627] Ar p1 or Ar p3 The phosphor is a substituent of the phosphor atoms and represents the aforementioned aryl group, which is either substituted or unsubstituted, or the aforementioned heterocyclic group, which is either substituted or unsubstituted, respectively.

[0628] According to another embodiment, the electron transport layer preferably comprises an aromatic hydrocarbon compound. Specific examples of aromatic hydrocarbon compounds preferred for the electron transport layer are oligophenylene compounds, naphthalene compounds, fluorene compounds, fluoranthenyl groups, anthracene compounds, phenanthrene compounds, pyrene compounds, triphenylene compounds, benzanthracene compounds, chrysene compounds, benzphenanthrene compounds, naphthacene compounds, and benzochrysene compounds, preferably anthracene compounds, pyrene compounds, and fluoranthene compounds.

[0629] ( cathode )

[0630] As the cathode, metals, alloys, electrically conductive compounds, and mixtures thereof, each having a small work function (specifically, a work function of 3.8 eV or less) are preferably used. Specific examples of cathode materials include alkali metals such as lithium and cesium; alkaline earth metals such as magnesium, calcium, and strontium; aluminum, alloys containing these metals (e.g., magnesium-silver, aluminum-lithium); rare earth metals such as europium and ytterbium; and alloys containing rare earth metals.

[0631] The cathode is generally formed by vacuum vapor deposition or sputtering. In addition, when using silver paste, coating methods, inkjet methods, etc., can be used.

[0632] Furthermore, various electrically conductive materials selected regardless of the work function, such as silver, ITO, graphene, silicon, or indium tin oxide containing silicon oxide, can be used to form the cathode. These electrically conductive materials are prepared into films using sputtering, inkjet, spin coating, etc.

[0633] ( insulating layer )

[0634] In organic EL devices, pixel defects based on leakage or short circuits are easily generated because an electric field is applied to the thin film. To prevent this, it is desirable to insert an insulating thin film between a pair of electrodes. Examples of materials used in 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 may be used in the insulating layer, and a multilayer laminate containing these materials may also be used in the insulating layer.

[0635] ( Separation layer )

[0636] A spacing layer is a layer provided between a fluorescent emitting layer and a phosphorescent emitting layer to prevent excitons generated in the phosphorescent emitting layer from diffusing into the fluorescent emitting layer or to adjust the carrier balance when the fluorescent emitting layer and the phosphorescent emitting layer are stacked. Additionally, a spacing layer may be provided between multiple phosphorescent emitting layers.

[0637] Since a spacing layer is provided between the emitting layers, the material used for the spacing layer is preferably a material having both electron transport capability and hole transport capability. To prevent the diffusion of triplet energy from adjacent phosphorescent emitting layers, it is preferable that the spacing layer has a triplet energy of 2.6 eV or higher. As a material used for the spacing layer, the same material used for the hole transport layer mentioned above may be used.

[0638] (former Blocking layer , Jeonggong Blocking layer , exciton Blocking layer )

[0639] An electron blocking layer, a hole blocking layer, an exciton (triplet) blocking layer, etc., may be provided adjacent to the light-emitting layer.

[0640] The electron blocking layer has the function of preventing electrons from leaking from the emissive layer to the hole transport layer. The hole blocking layer has the function of preventing holes from leaking from the emissive layer to the electron transport layer. To improve hole blocking capability, a material with a deep HOMO level is preferably used. The exciton blocking layer has the function of preventing excitons generated in the emissive layer from diffusing into adjacent layers and confining excitons within the emissive layer. To improve triplet blocking capability, a material with a high triplet level is preferably used.

[0641] (Layer formation method)

[0642] The method of forming each layer of the organic EL device of the present invention is not particularly limited unless otherwise specified. Known deposition methods, such as dry deposition and wet deposition, may be used. Specific examples of dry deposition methods include vacuum deposition, sputtering, plasma deposition, and ion plating. Specific examples of wet deposition methods include various coating methods such as spin coating, immersion, flow coating, and inkjet coating.

[0643] (Membrane thickness)

[0644] The film thickness of each layer of the organic EL device 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 difficult to obtain sufficient brightness. If the film thickness is too thick, it is necessary to apply a high driving voltage, which leads to a decrease in efficiency. In this regard, the film thickness is preferably 0.1 nm to 10 μm, and more preferably 5 nm to 0.2 μm.

[0645] (Electronic device (electronic equipment))

[0646] In addition, the present invention relates to an electronic device (electronic apparatus) comprising an organic electroluminescence device according to the present application. Examples of electronic apparatus include display components such as organic EL panel modules; display devices such as television sets, mobile phones, smartphones, and personal computers; and light-emitting devices of lighting devices and vehicle lighting devices.

[0647] Examples

[0648] 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 invention.

[0649] The percentages and ratios mentioned in the following examples are weight% and weight ratios, unless otherwise specified.

[0650] I Synthetic example

[0651] All experiments are conducted in a protective gas atmosphere.

[0652] Compound 1

[0653] Intermediate 1-1

[0654]

[0655] 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 fresh LDA (lithium diisopropylamide) solution.

[0656] 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 clear, colorless solution was cooled to -78°C, and a freshly prepared LDA solution was slowly added to it. The temperature was maintained at -78°C for 10 minutes, then raised to -30°C and maintained for 1.5 hours. Subsequently, the bright orange solution was slowly warmed to room temperature and stirred for 17 hours to obtain a yellow milk solution. The reaction mixture was poured into water and extracted with ethyl acetate. The organic extract was then dried over MgSO4, filtered, and the solvent removed over a rotary evaporator. The residue was purified by silica gel column chromatography using cyclohexane as the eluent to obtain 12.61 g (92% yield) of intermediate 1-1 as a clear, colorless oil.

[0657] 1 ¹H 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).

[0658] Intermediate 1-2

[0659]

[0660] 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-pump-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-pump-thaw cycles, the reaction mixture was heated to 60°C for 25 hours. The reaction mixture was cooled to room temperature and diluted with toluene. The organic extract was washed with water, dried over MgSO4, filtered, and the solvent removed over a rotary evaporator. The residue was purified by silica gel column chromatography using cyclohexane as the eluent to obtain 4.21 g (67% yield) of intermediate 1-2 as a light orange oil.

[0661] 1 ¹H 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).

[0662] Intermediate 1-3

[0663]

[0664] 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-pump-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-pump-thaw cycles, the reaction mixture was heated to 60°C for 19 hours. The reaction mixture was cooled to room temperature and diluted with toluene. The organic extract was washed with water, dried over MgSO4, filtered over a silica pad, and the pad was further washed with toluene. The solvent was removed over a 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 under high vacuum at 300°C to obtain 3.74 g (98% yield) of intermediate 1-3 as a transparent colorless resin.

[0665] 1 ¹H 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).

[0666] Intermediate 1-4

[0667]

[0668] 10.0 g (40.6 mmol) of 1-bromo-9H-carbazole, 13.4 g (52.8 mmol) of bis(pinacolato)diborone, and 16.0 g (168.2 mmol) of potassium acetate were suspended in 100 ml of anhydrous N,N-dimethylformamide. The suspension was degassed by evacuating the reaction vessel to a high vacuum and backfilling with argon. This procedure was repeated 7 times, and 2.32 g (7 mol%) of [1,1'-bis(diphenylphosphino)ferrocene-palladium(II)] complex with dichloromethane was added to the reaction mixture, followed by evacuating and backfilling 2 times. The reaction mixture was then heated to 80°C for 19 hours. After cooling to room temperature, the reaction mixture 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 300 ml of a 5:1 mixture of cyclohexane and diethyl ether. The solvent was removed over a 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 over a rotary evaporator until a white solid precipitated. The suspension was filtered to obtain 10.25 g (86% yield) of intermediate 1-4 as a white solid.

[0669] 1 ¹H 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, 0.9 Hz, 1H), 7.71(dd, J = 7.2, 1.3 Hz, 1H), 7.44 - 7.36(m, 1H), 7.23 - 7.13(m, 2H), 1.41(s, 12H).

[0670] Intermediate 1-5

[0671]

[0672] 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 K3PO4 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-pump-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 additional freeze-pump-thaw cycles, the reaction mixture was heated at 90°C for 20 hours, then an additional 8.8 mg (0.5 mol%) of palladium(II) acetate and 96.9 mg (3 mol%) of SPhos were added, and the reaction mixture was heated at 90°C for 1 hour. The reaction mixture was then cooled to room temperature and extracted with dichloromethane; the organic extract was dried over anhydrous MgSO4 and filtered over a small silica pad. The pad was washed with dichloromethane, and the solvent of the filtrate was removed over 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 colorless foam. The product was further purified by grinding with 40 ml of cyclohexane followed by 40 ml of reflux petroleum ether 60-80 at room temperature. 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.

[0673] 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).

[0674] Compound 1

[0675]

[0676] 0.50 g (0.84 mmol) of intermediate 1-5 was dissolved in 10 ml of 1,2-dichlorobenzene and degassed using three freeze-pump-thaw cycles. After adding 0.34 g (3.36 mmol) of triethylamine to the reaction mixture, 1.68 ml (1.68 mmol) of trichloroborane (1 M solution in heptane) was slowly added. The reaction mixture was heated at 180°C for 42 hours to prepare a clear oil 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 over a rotary evaporator, and the unrefined product was purified by silica gel column chromatography using a mixture of heptane and toluene (0-20% gradient) to obtain the product as an oil, which was then crystallized using a few drops of diethyl ether. The solid was collected by filtration to obtain 0.13 g (29% yield) of Compound 1 as a bright yellow powder.

[0677] 1H NMR(300 MHz, 디클로로메탄- 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).

[0678] Compound 2

[0679] Intermediate 2-1

[0680]

[0681] 5.00 g (18.97 mmol) of intermediate 1-1, 5.8, 3 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-pump-thaw cycles, and 347 mg (2 mol%) of tris(dibenzylideneacetone)dipalladium (0) and 329 mg (3 mol%) of xanthophosph (4,5-bis(diphenylphosphino)-9,9-dimethylxanthen) were added to the reaction mixture. After two additional freeze-pump-thaw cycles, the reaction mixture was heated to 120°C for 15 hours. An additional 347 mg (2 mol%) of tris(dibenzylideneacetone)dipalladium (0) and 329 mg (3 mol%) of xanthophos were added to the reaction mixture, and the reaction mixture was heated for a total of 50 hours. Afterward, the reaction mixture was cooled to room temperature, extracted with toluene, and the organic extract was dried over anhydrous MgSO4 and filtered over a small silica pad. The pad was washed with toluene, and the solvent of the filtrate was removed over a rotary evaporator. The unrefined product was purified by silica gel column chromatography using heptane to obtain 3.25 g (37% yield) of intermediate 2-1 as a colorless foam.

[0682] 1 ¹H 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).

[0683] Intermediate 2-2

[0684]

[0685] 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 in small amounts to the white suspension. After 4 hours, 200 ml of water was added, and the reaction mixture was stirred for another 30 minutes. The resulting precipitate was filtered, and the solid was washed with water and a saturated NaHCO3 solution, and then washed again with water. The unrefined product was purified by silica gel column chromatography using a mixture of heptane and toluene (0-40% gradient), and then further purified by silica gel column chromatography using a mixture of cyclohexane and dichloromethane (0-3% gradient). The pure fraction was combined and the solvent was removed over a rotary evaporator to obtain 3.42 g (45% yield) of intermediate 2-2 as a clear, colorless oil.

[0686] 1 ¹H 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).

[0687] Intermediate 2-3

[0688]

[0689] 3.40 g (9.49 mmol) of intermediate 2-2, 3.13 g (12.34 mmol) of bis(pinacolato)diborone, and 3.73 g (39.20 mmol) of potassium acetate were suspended in 40 ml of anhydrous N,N-dimethylformamide. The suspension was degassed by evacuating the reaction vessel to a high vacuum and backfilling with argon. This procedure was repeated 7 times, and after adding 542 mg (7 mol%) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) complex with dichloromethane to the reaction mixture, the evacuation-backfilling process was repeated 2 times. Subsequently, the reaction mixture was heated to 80°C for 21 hours. After cooling to room temperature, the reaction mixture was diluted with diethyl ether, washed with water, dried over MgSO4, and filtered on a small silica gel pad. The pad was washed with 300 ml of a 5:1 mixture of cyclohexane and diethyl ether. The solvent was removed over a rotary evaporator, and 30 ml of petroleum ether 60-80 was added to the brown residue. Then, the solution was concentrated until a white powder precipitated. The solid was filtered and washed with cold petroleum ether to obtain 3.05 g (79% yield) of intermediate 2-3 as a white powder.

[0690] 1 ¹H 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).

[0691] Intermediate 2-4

[0692]

[0693] 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 K3PO4 were 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-pump-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-pump-thaw cycles, the reaction mixture was heated at 80°C for 10 hours, then an additional 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 mixture was heated at 80°C for an additional 12 hours. Subsequently, the reaction mixture was cooled to room temperature and extracted with toluene, and the organic extract was extracted with anhydrous MgSO4 The product was dried on a sieve 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 unrefined product was purified by silica gel column chromatography using a mixture of heptane and tetrahydrofuran (0-1% gradient) to obtain 2.80 g (92% yield) of intermediate 2-4 as a white foam.

[0694] 1 ¹H NMR(300 MHz, DMSO- d6)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).

[0695] Compound 2

[0696]

[0697] 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 before cooling to room temperature. 15 ml of methanol was slowly added to quench the reaction mixture, and the resulting solution was poured into 200 ml of methanol. The yellow precipitate was stirred for 5 minutes, filtered, washed with methanol, and dried to obtain 1.11 g (50% yield) of compound 2 as a yellow solid.

[0698] 1H NMR (300 MHz, THF-d8)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).

[0699] Compound 3

[0700] Intermediate 3-1

[0701]

[0702] Intermediate 1-1 of 6.00 g (22.76 mmol), literature [ New Journal of Chemistry , 201910.81 g (25.03 mmol) of 3,6-bis(4-(tert-butyl)phenyl)-9H-carbazole and 4.37 g (45.5 mmol) of sodium tert-butoxide synthesized according to the procedure described in

[16629] were added to 175 mL of xylene. The suspension was degassed using three freeze-pump-thaw cycles, and 417 mg (2 mol%) of tris(dibenzylideneacetone)dipalladium (0) and 527 mg (4 mol%) of xanthophos (4,5-bis(diphenylphosphino)-9,9-dimethylxanthen) were added to the reaction mixture. After two additional freeze-pump-thaw cycles, the reaction mixture was heated to 120°C for 15 hours. An additional 347 mg (2 mol%) of tris(dibenzylideneacetone)dipalladium (0) and 329 mg (3 mol%) of xanthophos were added to the reaction mixture, and the reaction mixture was heated for a total of 41 hours. Afterward, the reaction mixture was cooled to room temperature, extracted with toluene, the organic extract was dried over anhydrous magnesium sulfate, and filtered over a small silica pad. The pad was washed with toluene, and the solvent of the filtrate was removed over a rotary evaporator. The unrefined product was purified by silica gel column chromatography using heptane / THF 95 / 5 to obtain 1.6 g (11% yield) of intermediate 3-1 as a pale yellow foam.

[0703] ESI-MS: 614.3[M+H] +

[0704] Intermediate 3-2

[0705]

[0706] 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 using three freeze-pump-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-pump-thaw cycles, the reaction mixture was heated at 90°C for 15 hours. Subsequently, the reaction mixture was cooled to room temperature and extracted with toluene; the organic extract was dried over anhydrous magnesium sulfate and dry-deposited on silica. The unrefined product was purified by silica gel column chromatography using a mixture of heptane and toluene (0-35% gradient) to obtain 1.4 g (41% yield) of intermediate 3-2 as a pale yellow foam.

[0707] ESI-MS: 857.5 [M+H]+

[0708] Compound 3

[0709]

[0710] 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 hours before cooling to room temperature. The reaction mixture was quenched by slowly adding 5 mL of 10% aqueous sodium acetate solution. The aqueous phase was extracted with toluene (2 x 20 mL). The combined organic phase was filtered over a silica plug and rinsed with toluene (40 mL). The filtrate was poured into 500 mL of methanol. After stirring the yellow precipitate for 5 minutes, it was filtered, washed with methanol, and dried to obtain 2.24 g (66% yield) of compound 3 as a yellow solid.

[0711] ESI-MS: 793.5 [M+H] +

[0712] Compound 4

[0713] Intermediate 4-1

[0714]

[0715] 41.0 g (0.13 mol) of 1-bromo-3-chloro-5-iodobenzene, 23.0 g (0.13 mol) of 4-tert-butylphenyl-boronic acid, 4.48 g (3.88 mmol) of tetrakis(triphenylphosphine)palladium (0), and 300 g of a 10% aqueous sodium carbonate solution were suspended in 120 mL of toluene and 120 mL of ethanol. The suspension was evacuated three times, backfilled with argon, and heated at 73°C for 22 hours. The light yellow suspension was cooled to room temperature and quenched with 200 mL of water. The organic phase was washed with water (2 x 200 mL) and dried over sodium sulfate. The product Combi-flash CombiFlash CompanionIntermediate 4-1 was further purified by MPLC using (silica gel, heptane) to obtain 39.6 g (93% yield) of the intermediate as a white solid.

[0716] 1 H NMR (300 MHz, CDCl3)δ 7.64(t, 1H), 7.52(t, 1H), 7.51 - 7.46(m, 5H), 1.40(s, 9H).

[0717] Intermediate 4-2

[0718]

[0719] 16 mL (0.11 mol) of diisopropylamine was dissolved in 100 mL of tetrahydrofuran and added dropwise with 45 mL of n-butyllithium (2.5 M in hexane) at -30°C. This solution was slowly added at a maximum temperature of -70°C to a pre-cooled solution of 30.0 g (93 mmol) of intermediate 4-1 and 14.1 mL (0.11 mol) of chlorotrimethylsilane in 200 mL of tetrahydrofuran. After the addition was complete, the pale yellow solution was stirred for 45 minutes at -75°C. 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 Combi-flash Companion 36.7 g (98% yield) of intermediate 4-2 was obtained as a colorless oil by further purification by MPLC using (silica gel, heptane).

[0720] 1 H NMR (300 MHz, CDCl3) δ 7.73 (d, 1H), 7.54 (d, 1H), 7.52 (d, 4H), 1.39 (s, 9H), 0.60 (s, 9H).

[0721] Intermediate 4-3

[0722]

[0723] 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, backfilled 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, and extracted with 100 ml of water. The organic phase was washed with 100 ml of water and 100 ml of saturated aqueous sodium chloride, dried over sodium sulfate, and concentrated under vacuum. The product CombiFlash Companion It was further purified by MPLC using (silica gel, heptane). The resulting oil was treated with 100 mL of methanol and stirred at 40°C until a suspension was formed to obtain 1.37 g (30% yield) of intermediate 4-3 as a white solid.

[0724] ESI-MS(yang, m / z): C 39 H 48 Accurate mass of ClNSi = 593.32; measured value 594.4 [M+1] + .

[0725] Intermediate 4-4

[0726]

[0727] 2.00 g (3.4 mmol) of intermediate 4-3, 1.64 (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, backfilled with argon, and heated at 77°C for 20 hours. The reaction mixture was cooled to room temperature, poured into 100 mL of water, and stirred for 10 minutes. 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 eluent was concentrated under vacuum. The product was dissolved in ethanol and water was added to form a suspension. The suspension was stirred for 30 minutes, then filtered, and the solid was washed with water. The solid was dissolved in dichloromethane, dried over sodium sulfate, and concentrated under vacuum to obtain 1.8 g (64%) of intermediate 4-4 as a white solid.

[0728] ESI-MS(sound, m / z): C 59 H 72 Accurate mass of N2Si = 836.55; measured value 835.6 [M-1] + .

[0729] Compound 4

[0730]

[0731] 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 hours, cooled to room temperature, and slowly poured into 300 mL of methanol. The suspension was stirred for 10 minutes, filtered, and the solid was washed with methanol and ethanol. The solid was dried under vacuum to obtain 1.15 g (69% yield) of compound 4 as a yellow solid.

[0732] ESI-MS(yang, m / z): C 56 H 61 Accurate mass of BN2 = 772.49; measured value 773.8 [M+1] + .

[0733] Compound 5

[0734] Intermediate 5-1

[0735]

[0736] 12.0 g (47.7 mmol) of 8-chloro-7H-benzo[c]carbazole, 18.2 g (71.5 mmol) of bis(pinacolato)diborone, 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 eluent was concentrated under vacuum, and the solid was recrystallized from 50 mL of heptane. The solid was washed with 30 mL of cold heptane and further dried under vacuum to obtain 12.3 g (75% yield) of intermediate 5-1 as a white solid.

[0737] Intermediate 5-2

[0738]

[0739] 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, backfilled 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 x 40 mL), dried over sodium sulfate, and concentrated under vacuum. The product was Combi-flash CompanionIt was further purified by MPLC using silica gel and toluene. The resulting white foam was heated to 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 obtain 3.40 g (82% yield) of intermediate 5-2 as a white solid.

[0740] ESI-MS(sound, m / z): C 45 H 46 Accurate mass of N2Si = 642.34; measured value 641.6 [M-1] + .

[0741] Compound 5

[0742]

[0743] 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 hours. The orange solution was cooled, and 4 mL of 10% aqueous sodium acetate solution was slowly added. The mixture was added dropwise to 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 obtain 2.12 g (69% yield) of compound 5 as a yellow solid.

[0744] ESI-MS(sound, m / z): C 42 H 35 Accurate mass of BN2 = 578.29; measured value 579.7 [M-1] + .

[0745] Compound 6

[0746] Intermediate 6-1

[0747]

[0748] 17.3 g (70.0 mmol) of 4-bromodibenzo[b,d]furan, 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 mixture was cooled to room temperature, diluted with toluene and water, and filtered over Celite. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extract was washed with water and 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.

[0749] ESI-MS: 328.3 [M+H] +

[0750] Intermediate 6-2

[0751]

[0752] 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 mixture was cooled to room temperature, diluted with toluene and water, and filtered over Celite. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extract was washed with water and 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.

[0753] ESI-MS: 290.0[MH] -

[0754] Intermediate 6-3

[0755]

[0756] 9.63 g (33.0 mmol) of intermediate 6-2, 10.06 g (39.6 mmol) of bis(pinacolato)diborone, 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 at 105°C for 4 hours. The reaction mixture was cooled to room temperature, diluted with toluene and water, and filtered over Celite. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extract was washed with water and 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 under vacuum. 11.40 g (90% yield) of intermediate 6-3 was obtained as a beige solid.

[0757] ESI-MS: 382.3 [MH] -

[0758] Intermediate 6-4

[0759]

[0760] 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 / 20 / 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 to 60°C for 2.5 hours. The reaction mixture 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 extract was washed with water and 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 4.46 g (84% yield) of intermediate 6-4 as a white foam.

[0761] ESI-MS: 813.6 [MH] -

[0762] Compound 6

[0763]

[0764] 3.26 g (4.00 mmol) of intermediate 6-4 was dissolved in 50 mL of 1,2-dichlorobenzene and degassed with Ar. 2.79 mL (16.0 mmol) of N-ethyl-N-isopropylpropane-2-amine was added to the reaction mixture, followed by the slow addition of 6.00 mL (6.00 mmol) of tribromoborane (1 M solution in heptane). The reaction mixture was heated at 160°C for 28.5 hours. Subsequently, an additional 2.00 mL (2.00 mmol) of tribromoborane (1 M solution in heptane) was added, followed by heating at 160°C for 16.5 hours. After cooling to room temperature, the reaction mixture was quenched with water and extracted with 1,2-dichlorobenzene. The combined organic layer was washed with 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 1.36 g (45% yield) of compound 6 as a yellow solid.

[0765] ESI-MS: 751.9 [M+H] +

[0766] Compound 7

[0767] Intermediate 7-1

[0768]

[0769] 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 over 45 minutes at a maximum temperature of -71°C. 45.9 g (0.18 mol) of iodine was added in several portions over 15 minutes at a maximum temperature of -55°C, and the resulting suspension was stirred further at -78°C for 45 minutes. 400 ml of 10% aqueous sodium sulfite 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 cyclohexane (2 x 150 ml). The combined organic phase was washed with water (2 x 200 ml) and saturated aqueous sodium chloride. The organic phase was dried over sodium sulfate and concentrated under vacuum to obtain 54.7 g (83% yield) of intermediate 7-1 as an orange oil.

[0770] 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).

[0771] Intermediate 7-2

[0772]

[0773] 3.22 g (10.00 mmol) of 9,9-dimethyl-2,7-di(tert-butyl)-9,10-dihydroacryline, 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-pump-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. Subsequently, after two additional freeze-pump-thaw cycles, the reaction mixture was stirred at 100°C for 1 hour. The reaction mixture 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.

[0774] ESI-MS: 534.6 [M+H] +

[0775] Intermediate 7-3

[0776]

[0777] 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-pump-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. Subsequently, after two additional freeze-pump-thaw cycles, the mixture was stirred at 85°C for 14.5 hours. The reaction mixture was cooled to room temperature and diluted with toluene. The organic extract was washed with water, dried over sodium sulfate, filtered, and the solution concentrated. The residue was purified by silica gel column chromatography using a mixed solvent of heptane and dichloromethane as the eluent to obtain 4.17 g (89% yield) of intermediate 7-3 as a white solid.

[0778] ESI-MS: 731.9 [M+H] +

[0779] Compound 7

[0780]

[0781] 4.14 g (5.66 mmol) of intermediate 7-3 was dissolved in 190 mL of dichlorobenzene. Then, 11.9 mL (11.9 mmol) of 1.0 M boron tribromide in heptane was added to the solution, followed by 4.2 mL (23.78 mmol) of N,N-diisopropylethylamine, and the mixture was stirred at 185°C for 40 hours. The reaction mixture was cooled to room temperature and diluted with toluene. The reaction mixture was quenched with 1.0 M sodium acetate aq., and the aqueous layer was extracted with toluene. The organic extract was washed with water, dried over magnesium sulfate, filtered, and the solution concentrated. The residue was purified by silica gel column chromatography using heptane as the eluent to obtain 2.49 g (54% yield) of compound 7 as a yellow solid.

[0782] ESI-MS: 739.9 [M+H] +

[0783] Compound 8

[0784] Intermediate 8-1

[0785]

[0786] 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 then the silica gel was rinsed with 100 ml of dioxane. The eluent was concentrated under vacuum, and the product Combi-flash Companion 6.9 g (91%) of intermediate 8-1 was obtained by further purification by MPLC using (silica gel, heptane / 0-5% gradient dichloromethane).

[0787] ESI-MS(yang, m / z): C 42 H 44 Exact mass of BrN = 641.27; measured value 642.7 [M+1] + .

[0788] Intermediate 8-1

[0789]

[0790] 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, backfilled 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 x 50 mL), dried over sodium sulfate, and concentrated under vacuum. The generated oil was diluted with 30 ml of dichloromethane and 50 ml of ethanol. The solution was concentrated to a volume of 50 ml under vacuum, the resulting suspension was filtered, and the solid was washed with 50 ml of ethanol to obtain 2.19 g (76% yield) of intermediate 8-3 as a white solid.

[0791] ESI-MS(sound, m / z): C 62 H 68 Accurate mass of N2 = 840.54; measured value 840.0 [M-1] + .

[0792] Compound 8

[0793]

[0794] 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 hours. The reaction mixture was cooled, and 100 mL of methanol was added. The suspension was stirred for 15 minutes and then filtered. The solid was washed with 50 mL of methanol, followed by 30 mL of water, and then washed with 50 mL of methanol and 30 mL of heptane. The solid Combi-flash Companion Compound 8 was further purified by MPLC using (silica gel, dichloromethane) to obtain 1.84 g (91% yield) of compound 8 as a yellow solid.

[0795] ESI-MS(yang, m / z): C 62 H 65 Accurate mass of BN2 = 848.52; measured value 849.8 [M+1] + .

[0796] Compound 9

[0797] Intermediate 9-1

[0798]

[0799] 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 cyclohexyl magnesium chloride solution (1 M in 2-methyltetrahydrofuran) was added for 10 minutes at a maximum temperature of 25°C. The reaction mixture was stirred for another 10 minutes at 0°C, and then slowly added at a maximum temperature of 15°C to a pre-cooled solution of 54.0 g (0.24 mol) of 6-bromo-2-tetraron, 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 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 on a Celite filtration aid pad, after which the filtration aid was rinsed with 500 mL of cyclohexane. The combined eluent 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 sodium chloride aqueous solution. The organic phase was dried on a sodium sulfate plate and filtered on a silica gel pad, after which the silica gel was rinsed with 300 ml of a solvent mixture of cyclohexane and ethyl acetate (2:1) followed by 300 ml of ethyl acetate. The combined eluent was concentrated under vacuum to obtain 59.6 g (87% yield) of intermediate 9-1.

[0800] 1H NMR (300 MHz, CD2Cl2) 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).

[0801] Intermediate 9-2

[0802]

[0803] 30.0 g (0.13 mol) of 1-bromo-4-(tert-butyl)aniline was suspended in 300 ml of 37% aqueous hydrochloride solution and cooled to 0°C. 60.5 g (0.13 mol) of 15% aqueous sodium nitrite solution was added dropwise over 15 minutes at a maximum temperature of 2°C. 74.8 g (0.40 mol) of tin chloride solution in 74.8 g of 37% aqueous hydrochloride was added dropwise over 40 minutes at a maximum temperature of 5°C. The concentrated 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 next reaction step.

[0804] 1 ¹H 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).

[0805] Intermediate 9-3

[0806]

[0807] 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 hydrochloride solution in 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 a sodium bicarbonate solution until a basic pH was reached, then washed with a saturated aqueous sodium chloride solution, and dried over a sodium sulfate layer. The mixture was filtered over a silica gel plug, and the silica gel layer was rinsed with cyclohexane. The collected eluent was concentrated under vacuum. The product is Combi-flash Companion 14.7 g (69% yield) of intermediate 9-3 was obtained as an orange solid by purification by MPLC using (silica gel, heptane / ethyl acetate with an 0-2% gradient).

[0808] ESI-MS(sound, m / z): C 26 H 30 Exact mass of BrN = 435.16; measured value 434.4 [M+1] + .

[0809] Intermediate 9-4

[0810]

[0811] 10.3 g (23.6 mmol) of intermediate 9-3 and 6.10 g (24.8 mmol) of p-collanyl 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 a solution was formed. This solution was mixed with 20 g of silica gel and concentrated under vacuum. The solid was Combi-flash Companion9.2 g (89% yield) of intermediate 9-4 was obtained as an orange solid by further purification by MPLC using (silica gel, heptane / ethyl acetate with an 0-2% gradient).

[0812] ESI-MS(yang, m / z): C 26 H 28 Exact mass of BrN = 433.14; measured value 434.3 [M+1] + .

[0813] Intermediate 9-5

[0814]

[0815] 11.7 g (26.9 mmol) of intermediate 9-4, 10.3 g (40.4 mmol) of bis(pinacolato)diborone, 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 hours. 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 filtration aid was added. The mixture was concentrated under vacuum and Combi-flash Companion 9.3 g (72% yield) of intermediate 9-5 was obtained as a pale yellow solid by purification by MPLC using (silica gel, heptane / ethyl acetate 9:1).

[0816] ESI-MS(yang, m / z): C 32 H 40 Accurate mass of BNO2 = 481.32; measured value 482.7 [M+1] + .

[0817] Intermediate 9-6

[0818]

[0819] 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% sodium carbonate aqueous solution were suspended in 260 ml of toluene and 260 ml of ethanol. The suspension was evacuated three times, backfilled 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, then dissolved in hot toluene. The hot solution was filtered over a silica gel pad, and the silica was rinsed with hot toluene. The combined eluent was concentrated under vacuum until a suspension was formed, and then cooled to room temperature. The suspension was filtered and the solid was washed with toluene to obtain 33.0 g (55% yield) of intermediate 9-6 as a white solid.

[0820] ESI-MS(yang, m / z): C 32 H 33 Accurate mass of N = 431.26; measured value 432.6 [M+1] + .

[0821] Intermediate 9-7

[0822]

[0823] 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 eluent was concentrated under vacuum, and the product is Combiple lassie Companion5.46 g (90%) of intermediate 9-7 was obtained by further purification by MPLC using (silica gel, heptane / dichloromethane with a 0-20% gradient).

[0824] ESI-MS(yang, m / z): C 42 H 44 Exact mass of BrN = 641.27; measured value 642.6 [M+1] + .

[0825] Intermediate 9-8

[0826]

[0827] 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, backfilled 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 x 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 a volume of 100 ml, the resulting suspension was filtered, and the solid was washed with 50 ml of ethanol to obtain 4.7 g (66% yield) of intermediate 9-8 as a white solid.

[0828] ESI-MS(yang, m / z): C 68 H 72 Accurate mass of N2 = 916.57; measured value 918.0 [M+1] + .

[0829] Compound 9

[0830]

[0831] 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 Combi-flash Companion It was purified by MPLC using (silica gel, dichloromethane). 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 obtain 3.86 g (85% yield) of compound 9 as a yellow solid.

[0832] ESI-MS(yang, m / z): C 68 H 69 Accurate mass of BN2 = 924.56; measured value 926.0 [M+1] + .

[0833] Compound 10

[0834] Intermediate 10-1

[0835]

[0836] 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, 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 were added. The mixture was stirred at 95°C for 6.5 hours. After cooling the reaction mixture to room temperature, the solid was filtered and washed with toluene. The solution was washed with 3-amino-2-propanol in water. 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 a beige solid.

[0837] ESI-MS: 491 [M+H] +

[0838] Intermediate 10-2

[0839]

[0840] 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-pump-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-pump-thaw cycles, the reaction mixture was heated to 110°C for 6 hours. The reaction mixture was cooled to room temperature and diluted with toluene and water. The aqueous layer was extracted with toluene, the organic layer was washed with brine, dried over magnesium sulfate, filtered, and the solution concentrated. The unrefined product was recrystallized with dichloromethane and acetonitrile to obtain 2.69 g (80% yield) of intermediate 10⁻² as a white solid.

[0841] ESI-MS: 538.8 [M+H] +

[0842] Intermediate 10-3

[0843]

[0844] 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 in small amounts. The mixture was stirred at room temperature for 50 minutes, after which the reaction mixture was filtered. The filtrate was concentrated. The unrefined product was purified by silica gel column chromatography using a mixed solvent of heptane and dichloromethane as the eluent. The product was precipitated in the mixed solvent of dichloromethane and heptane to obtain 10.21 g (85% yield) of intermediate 10-3 as a white solid.

[0845] ESI-MS: 508 [MH] -

[0846] Intermediate 10⁻⁴

[0847]

[0848] 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-pump-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. Subsequently, after two additional freeze-pump-thaw cycles, the mixture was stirred at 85°C for 16.5 hours. The reaction mixture was cooled to room temperature and diluted with toluene. The organic extract was washed with water, dried over sodium sulfate, filtered, and the solution concentrated. The residue was purified by silica gel column chromatography using a mixed solvent of heptane and toluene as the eluent, and 2.11 g (93% yield) of intermediate 7-2 was obtained as a white solid.

[0849] ESI-MS: 839.8 [M+H] +

[0850] Compound 10

[0851]

[0852] 2.11 g (2.51 mmol) of intermediate 10-4 was dissolved in 36 mL of dichlorobenzene. Then, 5.14 mL (5.12 mmol) of 1.0 M boron tribromide in heptane was added to the solution, followed by 1.8 mL (10.28 mmol) of N,N-diisopropylethylamine, and the mixture was stirred at 180°C for 15 hours. The reaction mixture was cooled to room temperature and diluted with methanol. The precipitate was collected by filtration and washed with ethanol and water. The unpurified product was dissolved in dichloromethane, precipitated with isopropanol, and filtered to obtain 1.77 g (83% yield) of compound 10 as a yellow solid.

[0853] ESI-MS: 849.7 [M+H] +

[0854] Compound 11

[0855] Intermediate 11-1

[0856]

[0857] 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. The mixture was degassed by bubbling N2 gas for 30 minutes, and 3.9 g (3 mol%) of tetrakis(triphenylphosphine)palladium (0) was added to the reaction mixture under a light N2 stream. The reaction mixture was heated under 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 brine, dried over magnesium sulfate, and filtered over a small silica gel pad. The product was eluted with heptane, and the solvent was removed over a rotary evaporator. The unpurified product was used as intermediate 11-1 without further purification.

[0858] 1 ¹H NMR(300 MHz, methylene chloride-d 2) δ 7.68(dd, J = 7.1, 2.3 Hz, 1H), 7.53(m, 5H), 7.26(t, J = 8.8 Hz, 1H), 1.40(s, 9H).

[0859] 19 F NMR(282 MHz, methylene chloride- d 2) δ -119.44.

[0860] Intermediate 11-2

[0861]

[0862] 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. The mixture was stirred at 170°C for 90 hours. The reaction mixture was cooled to room temperature and water was added. The organic layer was collected. After concentration, the residue was purified by silica gel column chromatography using heptane as the eluent to obtain 409 g (90% yield) of intermediate 11-2 as a beige solid.

[0863] The product was used without further purification.

[0864] Intermediate 11-3

[0865]

[0866] 399 g (1.10 mol) of intermediate 11-2 was dissolved in 1.40 L of N-methylpyrrolidone, and then 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 brine. After concentration, the residue was purified by silica gel column chromatography using toluene as the eluent. The main fraction was partially concentrated, the solvent was replaced with hepan to precipitate, and then filtered to obtain 227 g (73% yield) of intermediate 11-3 as a white solid.

[0867] ESI-MS: 280 [M+H] +

[0868] Intermediate 11-4

[0869]

[0870] 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 cooling the reaction mixture 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 brine. After concentration, the residue was purified by silica gel column chromatography using toluene as the eluent. The major fraction was concentrated. The product was dissolved in high-temperature heptane and recrystallized using an ice-water bath to obtain 77 g (51% yield) of intermediate 11-4 as a white solid.

[0871] ESI-MS: 360 [M+H] +

[0872] Intermediate 11-5

[0873]

[0874] Under an inert atmosphere, 9.57 ml of n-butyllithium (1.6 M in hexane) was added dropwise to a solution of intermediate 11-4 containing 5.00 g (13.9 mmol) 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 mixture was stirred at -78°C for 15 minutes. Then, 2.20 mL (19.7 mmol) of trimethylborate 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 minutes, then slowly heated to room temperature and stirred for 17 hours to obtain a milk solution. 50 mL of 10% HCl solution was added to the reaction mixture, and the yellow two-phase mixture was stirred for 1 hour. The resulting mixture was extracted with ethyl acetate, the organic extract was washed with water and brine, dried over magnesium sulfate, and filtered over a short silica gel pad. The solvent was removed over a rotary evaporator to obtain 4.25 g (60% yield) of intermediate 11-5 as a white solid.

[0875] 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).

[0876] Intermediate 11-6

[0877]

[0878] 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. The mixture was degassed by bubbling N2 gas for 30 minutes, and 0.80 g (2.2 mol%) of tetrakis(triphenylphosphine)palladium (0) was added to the reaction mixture under a light N2 stream. The reaction mixture was heated under reflux for 2 hours and then cooled to room temperature. The reaction mixture was extracted with heptane, the organic phase was washed with water and brine, dried over magnesium sulfate, and the solvent was removed over a rotary evaporator. The crude product was dissolved in a 1:1 mixture of dichloromethane / ethanol and concentrated over 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 (80% yield) of intermediate 11-6 as a bright yellow solid.

[0879] 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).

[0880] Intermediate 11-7

[0881]

[0882] 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 under reflux for 3 hours. Subsequently, 1,2-dichlorobenzene and triphenylphosphine were distilled under reduced pressure, the red oil was cooled, and heptane was added while stirring. The resulting orange suspension was stirred at room temperature and then at 0°C for 30 minutes, after which it was filtered. The solvent from the filtrate was removed over a rotary evaporator, and the unrefined 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 refluxed ethanol, and precipitated by adding water at room temperature. The resulting suspension was filtered, and the subsequent harvests were combined to obtain 8.0 g (83% yield) of intermediate 11-7 as a white solid.

[0883] ESI-MS: 402.4 [MH] -

[0884] Intermediate 11-8

[0885]

[0886] 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 at 110°C for 5 hours. Afterward, the suspension was cooled to 100°C, and water was slowly added. The resulting grayish-white suspension was cooled to room temperature and filtered. The unpurified solid was ground three times in a 9:1 mixture of hot ethanol and water to obtain 12.5 g (96% yield) of intermediate 11-8 as a white solid.

[0887] ESI-MS: 646.6 [M+H] +

[0888] Intermediate 11-9

[0889]

[0890] 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 N2. 312 mg (12 mol%) of SPhos and 30 mg (2 mol%) of palladium(II) acetate were added, and the reaction mixture was heated to 85°C. A pre-degassed solution of 3.52 g (8.68 mmol) of intermediate 2-3 in 56 mL of dioxane (0.155 M) was added dropwise over 45 minutes, and the reaction mixture was heated to 95°C for 3 hours. The reaction mixture 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 brine. The organic material was dried over magnesium sulfate, 0.5 g of activated carbon was added, and the mixture was refluxed for 30 minutes. The suspension was filtered over a silica gel pad, and the product was further eluted with dichloromethane. Methanol was added to the filtrate, and the mixture was concentrated over a rotary evaporator until a precipitate was 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 obtain 3.1 g (28% yield) of intermediate 11-9 as a white foam.

[0891] ESI-MS: 889.9 [M+H] +

[0892] Compound 11

[0893]

[0894] Under an inert atmosphere, 3.50 mL of tert-butyllithium (1.9 M in hexane) was added dropwise to a solution of intermediate 11-9 containing 1.95 g (2.19 mmol) in 200 mL of tert-butylbenzene using an acetone-dry ice bath while maintaining the temperature below -50°C. After the addition was completed, the reaction mixture was heated to 45°C for 1 hour, cooled to -78°C, and 0.35 mL (3.70 mmol) of borontribromide was slowly added while maintaining the temperature below -60°C. The reaction mixture was heated 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. Afterward, the reaction mixture was cooled to room temperature, quenched with water, and filtered. The 2-phase filtrate was extracted with toluene, and the organic phase was washed twice with 10% aqueous sodium carbonate, followed by washing with brine. The organic extract was dried over magnesium sulfate and filtered over a silica gel pad. The bright orange solution was concentrated to approximately 100 mL over a rotary evaporator, to which 300 mL of ethanol was added. The precipitate was cooled to room temperature and stirred for 17 hours before filtration. 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 over a rotary evaporator at 60°C until a suspension was formed. Subsequently, this was hot-filtered, and the solid was washed with a small amount of cold ethanol to obtain 215 mg (11.4% yield) of Compound 11 as a bright yellow solid.

[0895] ESI-MS: 864.0 [M+H] +

[0896] Compound 12

[0897] Intermediate 12-1

[0898]

[0899] 20.7 g (134 mmol) of 4-(tert-butyl)cyclohexan-1-one was added dropwise to 30.0 g (134 mmol) of 4-bromophenylhydrazine hydrochloride in 270 mL of acetic acid at 80°C under nitrogen. The reaction mixture was then stirred at 100°C for 5 hours.

[0900] The solvent was removed under vacuum, and the reaction mixture was dissolved in toluene. The organic phase was washed with water and then with a sodium bicarbonate solution. The organic phase was dried with magnesium sulfate, and the solvent was removed under vacuum. The product was used in the next reaction step without purification. Yield 41.0 g.

[0901] Intermediate 12-2

[0902]

[0903] 41.0 g (134 mmol) of 6-bromo-3-(tert-butyl)-2,3,4,9-tetrahydro-1H-carbazole and 60.8 g (268 mmol) of 2,3-dichloro-5,6-dicyanoquinone were added to 250 mL of toluene under nitrogen for 10 minutes. The reaction was exothermic. The reaction mixture was then stirred at 25°C for 1 hour. The solid was filtered and washed with toluene. The organic phase was washed with a 10% sodium hydroxide solution in water. The organic phase was washed with water and brine and dried with magnesium sulfate. The solvent was removed under vacuum. The product was obtained by silica gel column chromatography using heptane / ethyl acetate 95 / 5. Yield 21.6 g (52%).

[0904] 1 H-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, 9 H).

[0905] Intermediate 12-3

[0906]

[0907] To 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, 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 were added. The reaction mixture was degassed with 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 with argon. The reaction mixture was stirred under argon at 110°C for 8 hours. The solid was filtered and the aqueous phase was removed. The solvent was removed under vacuum. The product was obtained by silica gel column chromatography using heptane / ethyl acetate 90 / 10. Yield 11.7 g (55%).

[0908] 1 H-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).

[0909] Intermediate 12-4

[0910]

[0911] 9.81 g (36.8 mmol) of 2-chloro-4,6-diphenylpyrimidine and 11.6 g (84.0 mmol) of potassium carbonate were added to 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. The reaction mixture was degassed with argon. 1.16 g (1.00 mmol) of tetrakis(triphenylphosphine)palladium (0) was added. The reaction mixture was degassed with argon. The reaction mixture was stirred at 110°C for 8 hours under argon. The aqueous phase was removed. The solvent was removed under vacuum. The product was obtained by silica gel column chromatography using heptane / ethyl acetate 95 / 5 and heptane / ethyl acetate 90 / 10. Yield 6.75 g (44%)

[0912] ESI-MS: 454 [M+1] +

[0913] 1 H-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).

[0914] Intermediate 12-5

[0915]

[0916] 2.65 g (14.9 mmol) of N-bromosuccinimide was added to 6.75 g (14.9 mmol) of 3-(tert-butyl)-6-(4,6-diphenylpyrimidine-2-yl)-9H-carbazole in 60 mL of acetic acid, and the reaction mixture was stirred under nitrogen at 20°C. After 2.5 hours, the product was filtered and washed with acetic acid and then with methanol. The product was obtained by silica gel column chromatography using heptane / ethyl acetate 97 / 3. Yield 4.00 g (39%). The product was crystallized from toluene.

[0917] 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)

[0918] Intermediate 12-6

[0919]

[0920] 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 were added to 1.52 g (2.85 mmol) of 1-bromo-3-(tert-butyl)-6-(4,6-diphenylpyrimidine-2-yl)-9H-carbazole in 30 ml of toluene, 15 ml of dioxane, and 10 ml of water. The reaction mixture was degassed with 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 with argon. The reaction mixture was stirred at 70°C for 1 h under argon. The solid was filtered and washed with heptane. The organic phase was dried with magnesium sulfate, and the solvent was removed under vacuum. The product was obtained by silica gel column chromatography using heptane / ethyl acetate 95 / 5. Yield 2.19 g (88%).

[0921] 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, 15 H), 1.51(s, 18 H), 1.43(s, 18 H).

[0922] Compound 12

[0923]

[0924] 1.19 g (9.18 mmol) of N-ethyl-N-isopropylpropane-2-amine was added under argon to 1.98 g (2.29 mmol) of 3-(tert-butyl)-1-(3-(tert-butyl)-5-(3,6-di-tert-butyl-9H-carbazole-9-yl)phenyl)-6-(4,6-diphenylpyrimidine-2-yl)-9H-carbazole in 26 mL of o-dichlorobenzene. 4.59 mL (4.50 mmol) of a 1 M solution of tribromoborane in heptane was added to the reaction mixture under argon for 5 minutes. The reaction mixture was stirred under argon at 185°C for 2.5 hours. The reaction mixture was cooled to 25°C and methanol was added. The product was filtered and washed with methanol. The product was obtained by silica gel column chromatography using 100% dichloromethane. Yield 1.71 g (77%).

[0925] ESI-MS: 871.8 [M+1] +

[0926] 1 H-NMR (300 MHz, CDCl3)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, 18 H), 1.68(s, 9H), 1.58(s, 9H).

[0927] Compound 13

[0928] Intermediate 13-1

[0929]

[0930] 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 cooling the reaction mixture to room temperature, the solid was filtered and collected and washed with ethyl acetate. The filtrate was concentrated, and 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 (54% yield) of intermediate 13-1 as a white solid.

[0931] ESI-MS: 433 [M+H] +

[0932] Intermediate 13-2

[0933]

[0934] 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 cooling the reaction mixture to room temperature, the solid was removed by filtration and washed with toluene. The filtrate was concentrated, and 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 (68% yield) of intermediate 13-2 as a beige powder.

[0935] ESI-MS: 427 [M+H] +

[0936] Intermediate 13-3

[0937]

[0938] 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-pump-thaw cycles, 578 mg (0.50 mmol) of tetrakis(triphenylphosphine)palladium was added to the mixture. Subsequently, after two additional freeze-pump-thaw cycles, the mixture was stirred at 70°C for 20 hours. The reaction mixture was cooled to room temperature and diluted with toluene. The organic extract was washed with water, dried over sodium sulfate, filtered, and the solution concentrated. The residue was purified by silica gel column chromatography using a mixed solvent of heptane and toluene as the eluent to obtain 3.56 g (82% yield) of intermediate 13-3 as a white solid.

[0939] ESI-MS: 433 [MH] -

[0940] Intermediate 13-4

[0941]

[0942] 3.40 g (5.30 mmol) of intermediate 8-1, 1.38 g (5.4 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-pump-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-pump-thaw cycles, the reaction mixture was heated at 110°C for 6 hours. The reaction mixture was cooled to room temperature and diluted with toluene and water. The aqueous layer was extracted with toluene, the organic layer was washed with brine and dried over magnesium sulfate, filtered, and the solution concentrated. The unrefined product was recrystallized with dichloromethane and acetonitrile to obtain 2.74 g (75% yield) of intermediate 13-4 as a white solid.

[0943] ESI-MS: 690 [M+H]

[0944] Intermediate 13-5

[0945]

[0946] 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-pump-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. Subsequently, after two additional freeze-pump-thaw cycles, the mixture was stirred at 85°C for 16.5 hours. The reaction mixture was cooled to room temperature and diluted with toluene. The organic extract was washed with water, dried over sodium sulfate, filtered, and the solution concentrated. The residue was purified by silica gel column chromatography using a mixed solvent of heptane and toluene as the eluent, and 2.15 g (79% yield) of intermediate 13-5 was obtained as a white solid.

[0947] ESI-MS: 918 [M+H] +

[0948] Compound 13

[0949]

[0950] 1.83 g (2.00 mmol) of intermediate 13-5 was dissolved in 28 mL of dichlorobenzene. Then, 4.10 mL (4.10 mmol) of 1.0 M boron tribromide in heptane was followed by 1.4 mL (8.19 mmol) of N,N-diisopropylethylamine being added to the solution, and the mixture was stirred at 180°C for 15 hours. The reaction mixture was cooled to room temperature and diluted with methanol. The precipitate was collected by filtration and washed with ethanol and water. The unpurified product was dissolved in dichloromethane, precipitated with isopropanol, and filtered to obtain 1.39 g (75% yield) of compound 13 as a yellow solid.

[0951] ESI-MS: 925 [M+H] +

[0952] Compound 14

[0953] Intermediate 14-1

[0954]

[0955] 40.0 g (178 mmol) of 6-bromo-3,4-dihydronaphthalene-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-pump-thaw cycles, 3.08 g (2.67 mmol) of tetrakis(triphenylphosphine)palladium was added to the mixture. Subsequently, after two additional freeze-pump-thaw cycles, the mixture was stirred at 80°C for 1.5 hours. The reaction mixture 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 minutes. The organic extract was washed with water, dried over sodium sulfate, filtered, and the solution concentrated to obtain 21.0 g (42% yield) of intermediate 14-1 as a white solid. This was used in the following reaction without further purification.

[0956] Intermediate 14-2

[0957]

[0958] 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 in a dioxane solution and stirred at 110°C for 3 hours. 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 obtain 18.8 g (47% yield) of intermediate 14-2 as a white solid.

[0959] ESI-MS: 556.2 [MH] -

[0960] Intermediate 14-3

[0961]

[0962] 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 h. After cooling the reaction mixture to room temperature, the reaction mixture was suspended in 200 mL of heptane. The suspension was filtered and washed with heptane, and the filtrate was concentrated. The crude product was dissolved in toluene under reflux. After cooling the solution to room temperature, the formed solid was collected by filtration and washed with heptane to obtain 11.25 g (63% yield) of intermediate 14-3 as a pale gray solid.

[0963] ESI-MS: 552.2 [MH] -

[0964] Intermediate 14-4

[0965]

[0966] 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-pump-thaw cycles, 688 mg (0.60 mmol) of tetrakis(triphenylphosphine)palladium was added to the mixture. Subsequently, after two additional freeze-pump-thaw cycles, the mixture was stirred at 80°C for 4 hours. The reaction mixture was cooled to room temperature, and 1 g of sodium cyanide dissolved in 50 mL of water was added, after which the reaction mixture was stirred for 30 minutes. The organic extract was washed with water, dried over sodium sulfate, filtered, and the solution concentrated. The unrefined product was purified by silica gel column chromatography using a mixed solvent of heptane and dichloromethane as the eluent to obtain 7.33 g (65% yield) of intermediate 14-4 as a beige solid.

[0967] ESI-MS: 560.5 [MH] -

[0968] Intermediate 14-5

[0969]

[0970] 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-pump-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. Subsequently, after two additional freeze-pump-thaw cycles, the mixture was stirred at 85°C for 21 hours. The reaction mixture was cooled to room temperature and diluted with toluene. The organic extract was washed with water, dried over sodium sulfate, filtered, and the solution 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 (72% yield) of intermediate 14-5 as a white solid.

[0971] ESI-MS: 891 [MH] -

[0972] Compound 14

[0973]

[0974] 1.78 g (2.00 mmol) of intermediate 14-5 was dissolved in 28 mL of dichlorobenzene. Then, 4.10 mL (4.10 mmol) of 1.0 M boron tribromide in heptane was added to the solution, followed by 1.4 mL (8.19 mmol) of N,N-diisopropylethylamine, and the mixture was stirred at 180°C for 15 hours. The reaction mixture was cooled to room temperature and diluted with methanol. The precipitate was collected by filtration and washed with ethanol and water. The unpurified product was dissolved in dichloromethane, precipitated with isopropanol, and filtered to obtain 1.41 g (83% yield) of compound 14 as a yellow solid.

[0975] ESI-MS: 900 [M+H] +

[0976] Compound 15

[0977] Intermediate 15-1

[0978]

[0979] 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 iodide, and 2.73 mL (22.75 mmol) of cyclohexane-1,2-diamine were added to a solution of intermediate 7-1 containing 26.4 g (78.0 mmol) of 1,4-dioxane in 250 mL of 1,4-dioxane. The suspension was degassed with Ar and heated at 85°C for 1.5 hours. After cooling to room temperature, the suspension was filtered over Celite and rinsed with warm toluene (4 x 100 mL). The filtrate was evaporated, and the resulting residue was purified by silica gel column chromatography using heptane as the eluent. The resulting white solid was further recrystallized from cyclohexane (2 x 150 mL) to obtain 14.66 g (80% yield) of intermediate 15-1 as a white solid.

[0980] 1 ¹H 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).

[0981] Intermediate 15-2

[0982]

[0983] 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 and water (120 / 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 mixture was cooled to room temperature and diluted with toluene and water. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extract was washed with water and 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.

[0984] ESI-MS: 643.4[MH] -

[0985] Intermediate 15-3

[0986]

[0987] 17.43 g (27.0 mmol) of intermediate 15-2 was dissolved in 225 ml of 1,2-dichlorobenzene and degassed with Ar. 18.49 mL (108 mmol) of N-ethyl-N-isopropylpropane-2-amine was added to the reaction mixture, after which 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 and rinsed with 1,2-dichlorobenzene, methanol, and heptane to obtain 13.76 g (78% yield) of intermediate 15-3 as a yellow solid. The molecular weight of the product was confirmed by LC-MS [M+H] 653.3.

[0988] ESI-MS: 653.3[M+H] +

[0989] Compound 15

[0990]

[0991] 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 / 12 / 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 hours. The reaction mixture 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 extract was washed with water and 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 2.98 g (94% yield) of compound 15 as a yellow solid.

[0992] ESI-MS: 881.5[M+H] +

[0993] Compound 16

[0994]

[0995] 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 / 12 / 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 hours. The reaction mixture 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 extract was washed with water and 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 3.15 g (96% yield) of compound 16 as a yellow solid.

[0996] ESI-MS: 821.5 [M+H] +

[0997] Compound 17

[0998] Intermediate 17-1

[0999]

[1000] 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 over 3 hours at room temperature. The yellow suspension was stirred for 30 minutes, then treated with 1.5 l of water and stirred for another 1 hour. The suspension was filtered, and the solid was washed with 500 ml of water. The solid was suspended in 400 ml of a 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, filtered, and the solid was washed with 50 ml of ethanol to obtain 43.2 g (93% yield) of intermediate 17-1 as a white solid.

[1001] 1 ¹H NMR(300 MHz, DMSO- d 6)δ 7.98(s, 1H), 7.80(s, 1H), 1.66(s, 4H), 1.27(d, 12H).

[1002] Intermediate 17-2

[1003]

[1004] 20.0 g (61.7 mmol) of 2-bromo-N,N-diphenylaniline in 200 ml of tetrahydrofuran was added dropwise with 25.9 mL of n-butyllithium (2.5 M in hexane) at -78°C for 15 minutes. 32.5 mL of zinc chloride solution (1.9 M in 2-methyltetrahydrofuran) was added at -78°C. The yellow solution was heated to room temperature for 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 and filtered through a 3 cm silica gel layer, after which 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 hot 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 Combi-flash Companion Intermediate 17-2 was purified by MPLC using (silica gel, heptane / toluene with a 0-40% gradient) to obtain 20.3 g (73% yield) of the intermediate 17-2 as a white solid.

[1005] ESI-MS(yang, m / z): C 32 H 32 Accurate mass of N2O2 = 476.25; measured value 477.4 [M+1] + .

[1006] Intermediate 17-3

[1007]

[1008] 20.0 g (42.0 mmol) of intermediate 17-2 and 33.0 g (126 mmol) of triphenylphosphane 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; after filtration through a 4 cm silica gel layer, the silica gel layer was rinsed with 150 mL of dichloromethane. The combined eluent was concentrated under vacuum, and the product Combi-flash Companion Purification was performed by MPLC using (silica gel, heptane / dichloromethane). 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 was formed. The suspension was filtered, and the solid was washed with heptane. The solid was suspended in 70 mL of tert-butylmethyl ether. The suspension was filtered, and the solid was washed with tert-butylmethyl ether. The combined filtrate from the tert-butylmethyl ether wash was concentrated under vacuum to obtain 6.9 g (37% yield) of intermediate 17-3 as a solid.

[1009] ESI-MS (Yang, m / z): C 32 H 32 Accurate mass of N2 = 444.26; measured value 445.4 [M+1] + .

[1010] Intermediate 17-4

[1011]

[1012] 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 hours. The suspension 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 dioxane. The eluent 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 obtain 2.56 g (87% yield) of intermediate 17-4 as a white solid.

[1013] ESI-MS (Yang, m / z): C 42 H 43 Exact mass of BrN2 = 654.26; found 657.4 [M+3] + .

[1014] Intermediate 17-5

[1015]

[1016] 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 evacuated three times, backfilled with argon, 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 x 50 mL), dried over a sodium sulfate layer, and filtered over a 3 cm silica gel layer. The silica gel layer was rinsed with toluene, and the combined eluent was concentrated under vacuum. The product Combi-flash Companion It was purified by MPLC using (silica gel, heptane). The resulting product was diluted with 30 ml of dichloromethane and 50 ml of ethanol. The solution was concentrated under vacuum to a volume of 50 ml until a suspension was formed. The suspension was filtered and the solid was washed with ethanol to obtain 2.4 g (74% yield) of intermediate 17-5 as a white solid.

[1017] ESI-MS (Yang, m / z): C 62 H 67 Accurate mass of N3 = 853.53; measured value 854.7 [M+1] + .

[1018] Compound 17

[1019]

[1020] 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 cooled to 36°C. 5.4 mL of tribromoborane (1.0 M in heptane) was added dropwise, and heating 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 x 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 a volume of 50 mL until a suspension was formed. The suspension was filtered, and the solid was washed with ethanol. The product Combi-flash Companion It was purified by MPLC using (silica gel, heptane / 0-10% gradient dichloromethane). The isolated product was dissolved in 20 ml of dichloromethane and 60 ml of ethanol. The solution was concentrated to a volume of 50 ml until a suspension was formed. The suspension was filtered, and the solid was washed with 30 ml of ethanol to obtain 0.85 g (37% yield) of compound 17 as a yellow solid.

[1021] ESI-MS(yang, m / z): C 62 H 64 Accurate mass of BN3 = 861.52; measured value 862.6 [M+1] + .

[1022] Compound 18

[1023]

[1024] 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 / 2 / 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 mixture 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 extract was washed with water and brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane / dichloromethane as the eluent to obtain 123 mg (62% yield) of compound 18 as a yellow solid.

[1025] ESI-MS: 797.5 [M+H] +

[1026] Compound 19

[1027]

[1028] 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 / 2 / 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 hours. The reaction mixture 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 extract was washed with water and 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 166 mg (70% yield) of compound 19 as a yellow solid.

[1029] ESI-MS: 773.4 [M+H] +

[1030] Compound 20

[1031] Intermediate 20-1

[1032]

[1033] 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 three times, backfilled with argon, and heated at 72°C for 90 minutes. The concentrated suspension was cooled to room temperature and washed with water (2 x 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 obtain 18.8 g (76% yield) of intermediate 20-1 as a white solid.

[1034] ESI-MS(yang, m / z): C 46 H 55 Accurate mass of ClN2 = 670.41; measured value 671.4 [M+H] + .

[1035] Intermediate 20-2

[1036]

[1037] 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 three times, backfilled with argon, and heated at 82°C for 5 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 x 100 mL) and dried over sodium sulfate, after which 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 was formed. The suspension was filtered, and the solid was washed with 100 mL of ethanol and 100 mL of heptane to obtain 6.9 g (68% yield) of intermediate 20-2 as a white solid.

[1038] ESI-MS(sound, m / z): C 62 H 65 Accurate mass of N3 = 851.52; measured value 850.4 [M-1] + .

[1039] Compound 20

[1040]

[1041] 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 with 30 mL of water, and then with 50 mL of methanol and 30 mL of heptane. The solid Combi-flash Companion Compound 20 was further purified by MPLC using (silica gel, dichloromethane) to obtain 2.1 g (69% yield) of compound 20 as a yellow solid.

[1042] ESI-MS(yang, m / z): C 62 H 62 Accurate mass of BN3 = 859.50; measured value 860.7 [M+1] + .

[1043] Compound 21

[1044] Intermediate 21-1

[1045]

[1046] 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 three times, backfilled with argon, and heated at 86°C for 26 hours. 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 x 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 Combi-flash Companion It was further purified by MPLC using (silica gel, cyclohexane / ethyl acetate with an 0-10% gradient). 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 obtain 3.65 g (53% yield) of intermediate 21-1 as a white solid.

[1047] ESI-MS(sound, m / z): C 45 H 48 Accurate mass of N2Si = 644.36; measured value 643.3 [M-1] + .

[1048] Compound 21

[1049]

[1050] 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 hours. 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 metnol, 50 mL of water, and 50 mL of methanol. The product Combi-flash Companion Compound 21 was further purified by MPLC using (silica gel, dichloromethane) to obtain 1.02 g (32% yield) of compound 21 as a yellow solid.

[1051] ESI-MS(yang, m / z): C 42 H 37 Accurate mass of BN2 = 580.30; measured value 581.7 [M+1] + .

[1052] Compound 22

[1053] Intermediate 22-1

[1054]

[1055] 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-pump-thaw cycles, 295 mg (0.51 mmol) of xanthophos and 117 mg (0.13 mmol) of tris(dibenzylideneacetone)dipalladium (0) were added to the mixture. After two additional freeze-pump-thaw cycles, the reaction mixture was stirred at 100°C for 14.5 hours. The reaction mixture was cooled to room temperature and diluted with toluene and water. The aqueous layer was extracted with toluene. The organic extract was washed with 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 obtain 10.8 g (79% yield) of intermediate 22-1 as a beige foam.

[1056] ESI-MS: 494.6 [MH] -

[1057] Intermediate 22-2

[1058]

[1059] 2.96 g (6.01 mmol) of intermediate 22-1, 1.98 g (7.81 mmol) of bis(pinacolato)diborane, and 1.18 g (12.02 mmol) of sodium acetate were suspended in 30 mL of toluene. The suspension was degassed using three freeze-pump-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-pump-thaw cycles, the reaction mixture was heated to 110°C for 16 hours. The reaction mixture was cooled to room temperature and diluted with toluene and water. The aqueous layer was extracted with toluene, the organic layer was washed with brine and dried over magnesium sulfate, filtered, and the solution concentrated. The unrefined product was recrystallized with dichloromethane and acetonitrile to obtain 2.56 g (79% yield) of intermediate 22-2 as a white solid.

[1060] ESI-MS: 540.7 [M+H] +

[1061] Intermediate 22-3

[1062]

[1063] 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-pump-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. Subsequently, after two additional freeze-pump-thaw cycles, the mixture was stirred at 85°C for 21 hours. The reaction mixture was cooled to room temperature and diluted with toluene. The organic extract was washed with water, dried over sodium sulfate, filtered, and the solution 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.

[1064] ESI-MS: 893.8 [MH] -

[1065] Compound 22

[1066]

[1067] 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 was followed by 2.3 mL (10.28 mmol) of N,N-diisopropylethylamine being added to the solution, and the mixture was stirred at 180°C for 20 hours. The reaction mixture was cooled to room temperature and diluted with methanol. The precipitate was collected by filtration and washed with ethanol and water. The unpurified 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 and precipitated by adding acetonitrile, and then filtered to obtain 2.19 g (76% yield) of compound 22.

[1068] ESI-MS: 901.2 [M+H] +

[1069] Compound 23

[1070] Intermediate 23-1

[1071]

[1072] 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. The mixture was degassed by bubbling N2 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, then cooled to room temperature. The reaction mixture was filtered over a silica gel pad, and the product was eluted with heptane. The filtrate and washing solution were combined, the solvent was removed over a rotary evaporator, and then dried at 200°C under high vacuum. The oil was crystallized from a minimal amount of hot heptane. The brown solid was then dissolved in dichloromethane and washed twice with a 0.05% aqueous sodium cyanide solution followed by brine. The organic matter was dried over magnesium sulfate, and the solvent was removed over a rotary evaporator. The oil was crystallized from a minimal amount of hot heptane, filtered, and washed with pentane to obtain 10.9 g (28.4% yield) of intermediate 23-1 as a white solid.

[1073] 1 ¹H 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).

[1074] Intermediate 23-2

[1075]

[1076] 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 using an acetone-dry ice bath while maintaining the temperature below -60°C. After the addition was complete, the reaction mixture was stirred at -78°C for 1.5 hours. Subsequently, 30 mL (268 mmol) of trimethylborate 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 minutes, then slowly heated to room temperature and stirred for 20 minutes to obtain a milk solution. 400 mL of 10% HCl solution was added to the reaction mixture, and the two-phase mixture was stirred for 1 hour. The organic solvent was removed over a rotary evaporator, and the resulting suspension was filtered. The solid was ground in 500 mL of heptane under reflux for 1 hour. Afterward, the white suspension was concentrated to half its volume on a rotary evaporator, stirred at 0°C for 1 hour, and then filtered to obtain 22.3 g (71.3% yield) of intermediate 23-2 as a white solid.

[1077] ESI-MS: 400.2 [M+H] +

[1078] Intermediate 23-3

[1079]

[1080] 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, and the mixture was degassed by bubbling N2. 547 mg (3 mol%) of tetrakis(triphenylphosphine)palladium (0) was added, and the reaction mixture was heated to 85°C for 3 hours. The reaction mixture was cooled to room temperature, poured into water, extracted with dichloromethane, and the organic phase was washed with water and brine. The organic matter was dried over magnesium sulfate, and after adding heptane, the dichloromethane was removed over a rotary evaporator until a precipitate began to form. After stirring the precipitate at approximately 15°C, 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 to about 50 mL on a rotary evaporator and stirred at room temperature for 1 hour. The yellow suspension was filtered to obtain 4.72 g (55% yield) of intermediate 23-3 as a yellow solid.

[1081] ESI-MS: 533.3 [M+H] +

[1082] Intermediate 23-4

[1083]

[1084] 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 under reflux for 11 hours. The 1,2-dichlorobenzene and most of the triphenylphosphine were then distilled under reduced pressure, and the remaining black tar was cooled to room temperature. The residue was then dissolved in refluxed heptane, 15 g of Hyflo® Super-Cel® was added, followed by the addition of 5 g of activated carbon. The suspension was then hot-filtered over a Hyflo® Super-Cel® pad, the pad was washed with heptane, and the combined filtrate was filtered over a silica pad. The pad was washed with heptane, and the colorless filtrate was discarded. The product was then eluted with toluene to obtain an orange filtrate. The solvent from the filtrate was removed over a rotary evaporator, and the unpurified 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 the dichloromethane was removed over a rotary evaporator. The resulting solution was cooled to 0°C, during which time a precipitate formed. After stirring for 2 hours, the suspension was filtered to obtain 4.53 g (30% yield) of intermediate 23-4 as a white solid.

[1085] ESI-MS: 499.4 [MH] -

[1086] Intermediate 23-5

[1087]

[1088] 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 the reaction mixture was degassed by bubbling N2. Then, 66 mg (2 mol%) of tris(dibenzylideneacetone)dipalladium (0) and 137 mg (8 mol%) of Xphos were added, and the reaction mixture was heated at 90°C for 24 hours. Then, an additional 33 mg (1 mol%) of tris(dibenzylideneacetone)dipalladium (0) and 69 mg (4 mol%) of Xphos were added, and the reaction mixture was heated at 90°C for 3 more hours, and then cooled to room temperature. The reaction mixture was poured into 200 mL of saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The organic phase was washed with water and brine, dried over magnesium sulfate, and filtered over a silica gel pad. The pad was washed with ethyl acetate, and the solvent of the filtrate was evaporated over a rotary evaporator. The unrefined product was purified by silica gel column chromatography using a mixture of heptane and ethyl acetate as the eluent, followed by 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 over a rotary evaporator at room temperature until a precipitate formed. The suspension was stirred at -40°C for 20 minutes and filtered. The second harvest was filtered from the mother liquor, and the white solid was combined to obtain 1.49 g (47% yield) of intermediate 23-5 as a white solid.

[1089] ESI-MS: 878.7 [M+H] + , 876.6 [MH] -

[1090] Compound 23

[1091]

[1092] Under an inert atmosphere, 0.75 mL of n-butyllithium (2.5 M in hexane) was added dropwise to a solution of intermediate 23-5 containing 1.50 g (1.71 mmol) 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 to room temperature for 20 minutes, then cooled to -15°C, and 3.5 mL of borontribromide (1 M in heptane) was slowly added while maintaining the temperature below -10°C. The reaction mixture was heated to 120°C for 5 hours. Subsequently, the reaction mixture was cooled to room temperature and quenched with 100 mL of a 10% aqueous sodium bicarbonate solution. The organic phase was washed twice with water, dried over a sodium sulfate bath, and filtered over a silica gel pad. The pad was washed with toluene, and the filtrate was concentrated over a rotary evaporator to remove the toluene. The yellow solution was cooled to 0°C, and 300 mL of acetonitrile was added. A precipitate was allowed to form slowly over 2 hours, and the resulting solid was filtered. The mother liquor was concentrated into oil over a rotary evaporator and dissolved in dichloromethane. 70 mL of acetonitrile was added, and the solution was concentrated to approximately 40 mL over a rotary evaporator. The solution was cooled to room temperature, crystals from the previous precipitate were seeded, and the mixture was left to be stirred for 1 hour. Subsequently, the resulting precipitate was filtered, and the combined 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 was formed. The suspension was stirred at room temperature for 30 minutes and filtered to obtain 870 mg (58% yield) of compound 23 as a bright yellow solid.

[1093] ESI-MS: 886.7 [M+H] +

[1094] Compound 24

[1095] Intermediate 24-1

[1096]

[1097] 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 and water (54 / 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 hours. The reaction mixture was cooled to room temperature and diluted with toluene and water. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extract was washed with water and 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 4.30 g (73% yield) of intermediate 24-1 as a white foam.

[1098] ESI-MS:490.2 [MH] -

[1099] Intermediate 24-2

[1100]

[1101] 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-dimethylxanthine and 134 mg (3 mol%) of tris(dibenzylideneacetone)dipalladium (0) were added to the reaction mixture. The reaction mixture was heated at 90°C for 45 minutes. The reaction mixture was cooled to room temperature, diluted with toluene and water, and filtered over Celite. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extract was washed with water and 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 1.4 g (61% yield) of intermediate 24-2 as a white solid.

[1102] ESI-MS [M+H] 474.4.

[1103] Intermediate 24-3

[1104]

[1105] 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-dimethylxanthine and 101 mg (4 mol%) of tris(dibenzylideneacetone)dipalladium (0) were added to the reaction mixture. The reaction mixture was heated at 90°C for 2.5 hours. The reaction mixture was cooled to room temperature, diluted with toluene and water, and filtered over Celite. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extract was washed with water and 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 (94% yield) of intermediate 24-3 as a beige foam.

[1106] ESI-MS: 883.7 [M+H] +

[1107] Compound 24

[1108]

[1109] 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. 4.07 mL (6.51 mmol) of tert-butyllithium (1.6 M solution in pentane) was added dropwise, and the mixture was stirred at the same temperature for 5 minutes. Subsequently, the reaction mixture was stirred at room temperature for 2 hours. Then, 4.20 mL (4.20 mmol) of tribromoborane (1 M solution in heptane) was added dropwise, and the reaction mixture was stirred for 5 minutes, after which 1.44 mL (8.40 mmol) of N-ethyl-N-isopropylpropane-2-amine was added. The reaction mixture was stirred at room temperature for 3 hours, and then quenched with water / toluene. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extract was washed with water and 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 (66% yield) of compound 24 as a yellow solid.

[1110] ESI-MS [M+H] 891.6.

[1111] Compound 25

[1112] Intermediate 25-1

[1113]

[1114] 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 vigorously stirred 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 x 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. The suspension was cooled and filtered, and the solid was washed with cold ethanol to obtain 31.6 g (63% yield) of intermediate 25-1 as a white solid.

[1115] ESI-MS(yang, m / z): C 26 H 30 Accurate mass of Cl2N2 = 440.18; measured value 441.3 [M+1] + .

[1116] Intermediate 25-2

[1117]

[1118] 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 and filtered through a 3 cm silica gel layer, after which the silica gel layer was rinsed with 600 mL of dichloromethane and 1000 mL of ethyl acetate. The collected eluent was concentrated to a volume of 100 mL under vacuum, 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 obtain 25.0 g (quantitative yield) of intermediate 25-2.

[1119] ESI-MS(yang, m / z): C 26 H 28 Accurate mass of N2 = 368.23; measured value 369.5 [M+1] + .

[1120] Intermediate 25-3

[1121]

[1122] 25.0 g (67.8 mmol) of intermediate 25-2 and 32.6 g (0.15 mol) of di-tert-butyldicarbonate 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 obtain 29.4 g (76% yield) of intermediate 25-3 as a white solid.

[1123] Intermediate 25-4

[1124]

[1125] 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 obtain 10.2 g (43% yield) of intermediate 25-4 as a white solid.

[1126] ESI-MS(sound, m / z): C 31 H 36 Accurate mass of N2O2 = 468.28; measured value 467.4 [M-1] + .

[1127] Intermediate 25-5

[1128]

[1129] 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 eluent 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 was formed. The suspension was filtered, and the solid was washed with ethanol to obtain 13.8 g (67% yield) of intermediate 25-5.

[1130] ESI-MS(yang, m / z): C 41 H 48 Accurate mass of N2O2 = 600.37; measured value 601.8 [M+1] + .

[1131] Intermediate 25-6

[1132]

[1133] 13.5 g (22.5 mmol) of intermediate 25-5 was heated at 230°C for 90 minutes. The molten solid was cooled and Combi-flash Companion 8.7 g (77%) of intermediate 25-6 was obtained as a white solid by purification by MPLC using (silica gel, heptane / ethyl acetate with an 0-8% gradient).

[1134] ESI-MS(yang, m / z): C 36 H 40 Accurate mass of N2 = 500.32; measured value 501.7 [M+1] + .

[1135] Intermediate 25-7

[1136]

[1137] 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, filtered through a 3 cm silica gel layer, and the silica gel layer was rinsed with 30 mL of dioxane. The collected eluent was concentrated under vacuum, and the product Combi-flash CompanionThe intermediate 25-7 was further purified by MPLC using (silica gel, heptane / dichloromethane with a 0-25% gradient) to obtain 2.45 g (64% yield) of the intermediate as a white solid.

[1138] ESI-MS(yang, m / z): C 46 H 51 Exact mass of BrN2 = 710.32; measured value 711.6 [M+1] + .

[1139] Intermediate 25-8

[1140]

[1141] 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 hours. 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 hours. The reaction mixture was cooled to room temperature, and 1 g of sodium cyanide and 100 mL of water were added. The mixture was stirred for 1 hour and then washed with water (3 x 100 mL). The organic phase was dried over sodium sulfate and concentrated under vacuum. The product was dissolved in 300 mL of hot methanol, and the solution was stirred at room temperature for 18 hours. The resulting suspension was filtered, and the solid was washed with cold methanol to obtain 24.3 g (51% yield) of intermediate 25-8 as a gray solid.

[1142] ESI-MS(yang, m / z): C 20 H 26 Exact mass of BrN = 359.12; measured value 362.4 [M+3]+ .

[1143] Intermediate 25-9

[1144]

[1145] 5.80 g (16.1 mmol) of intermediate 25-8, 6.13 g (24.1 mmol) of bis(pinacolato)diborone, 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 x 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 under vacuum to a volume of 100 mL. The resulting suspension was filtered, and the solid was washed with 50 mL of ethanol to obtain 3.8 g (58% yield) of intermediate 25-9.

[1146] ESI-MS(yang, m / z): C 26 H 38 Accurate mass of BNO2 = 407.30; measured value 408.7 [M+1] + .

[1147] Intermediate 25-10

[1148]

[1149] 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 hour 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 x 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 was formed. The suspension was filtered, and the solid was washed with 50 mL of ethanol. The product Combi-play city Companion 1.59 g (52% yield) of intermediate 25-10 was obtained as a white solid by further purification by MPLC using (silica gel, heptane / dichloromethane with an 0-16% gradient).

[1150] ESI-MS(yang, m / z): C 66 H 77 Accurate mass of N3 = 911.61; measured value 912.7 [M+1] + .

[1151] Compound 25

[1152]

[1153] 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 hours. 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 hours. The reaction mixture was cooled to room temperature, diluted with 200 mL of ethanol, and stirred for 1 hour. The suspension was filtered, and the solid Combi-flash Companion Compound 25 was further purified by MPLC using (silica gel, heptane / dichloromethane with a 0-50% gradient) to obtain 212 mg (14% yield) of compound 25 as a yellow solid.

[1154] ESI-MS(yang, m / z): C 66 H 74 Accurate mass of BN3 = 919.60; measured value 920.9 [M+1] + .

[1155] Compound 26

[1156] Intermediate 26-1

[1157]

[1158] 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 three times, backfilled with argon, and heated at 105°C for 18 hours. The concentrated 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 x 50 mL), dried over sodium sulfate, and concentrated under vacuum. The product Combi-flash Companion Intermediate 26-1 of 10.5 g (79% yield) was obtained by further purification by MPLC using (silica gel, cyclohexane / ethyl acetate with an 0-2% gradient).

[1159] ESI-MS(yang, m / z): C 18 H 19 Accurate mass of NS = 281.12; measured value 282.4 [M+1] + .

[1160] Intermediate 26-2

[1161]

[1162] 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 x 100 mL), and dried over a sodium sulfate layer. 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 eluent is concentrated under vacuum and the product Combi-flash Companion Intermediate 26-2 of 2.7 g (51% yield) was obtained by further purification by MPLC using (silica gel, heptane).

[1163] ESI-MS(yang, m / z): C 28 H 30 Exact mass of BrNS = 491.13; measured value 492.6 [M+1] + .

[1164] Intermediate 26-3

[1165]

[1166] 3.00 g (6.09 mmol) of intermediate 26-2, 2.30 g (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 three times, backfilled with argon, 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 x 100 mL), dried over sodium sulfate, and concentrated under vacuum. The product Combi-flash Companion The product was further purified by MPLC using (silica gel, heptane / ethyl acetate with an 0-10% gradient). The isolated product was dissolved in 30 mL of dichloromethane and 50 mL of ethanol and concentrated under vacuum until a suspension was formed. The suspension was filtered, and the solid was washed with 50 mL of ethanol to obtain 2.9 g (76% yield) of intermediate 26-3.

[1167] ESI-MS(yang, m / z): C 44 H 40 Accurate mass of N2S = 628.29; measured value 629.8 [M+1]+.

[1168] Compound 26

[1169]

[1170] 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 obtain 142 mg (9% yield) of compound 26 as a yellow solid.

[1171] ESI-MS(yang, m / z): C 44 H 40 Accurate mass of N2S = 628.29; measured value 629.8 [M+1] + .

[1172] Compound 27

[1173] Intermediate 27-1

[1174]

[1175] 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-dimethylxanthine 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 mixture was cooled to room temperature, diluted with toluene and water, and filtered over Celite. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extract was washed with water and brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane as the eluent to obtain 15.1 g (89% yield) of intermediate 27-1 as a clear oil.

[1176] 1 ¹H 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 (br s, 1H), 1.38(s, 9H).

[1177] Intermediate 27-2

[1178]

[1179] 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 at 120°C for 30 hours. The reaction mixture was cooled to room temperature, diluted with toluene and water, and filtered over Celite. The layers were separated, and the aqueous layer was further extracted with toluene. The organic extract was washed with water and 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 weight of the product was LC-MS [MH] - It was confirmed to be 256.5.

[1180] Intermediate 27-3

[1181]

[1182] 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. The suspension was degassed with Ar and then heated at 195°C for 3 days. The reaction mixture was cooled to room temperature, diluted with toluene, and filtered over 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 combined organic extract was washed with 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 weight of the product was LC-MS [M+H] + It was confirmed to be 374.5.

[1183] Intermediate 27-4

[1184]

[1185] 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 / 9 / 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 mixture was cooled to room temperature, diluted with toluene, and filtered over a Celite pad. Water was added to the filtrate, the layers were separated, and the aqueous layer was further extracted with toluene. The organic extract was washed with water and brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane / toluene, followed by secondary chromatography using heptane / dichloromethane as the eluent to obtain 2.1 g (55% yield) of intermediate 27-4 as a white solid. The molecular mass of the product was LC-MS [MH] - It was confirmed as 615.4.

[1186] Compound 27

[1187]

[1188] 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. 0.51 mL (0.973 mmol) of tert-butyllithium (1.9 M solution in pentane) was added dropwise and stirred for 5 minutes at the same temperature. Subsequently, the reaction mixture was stirred at 85°C for 2 hours. Then, 0.81 mL (0.81 mmol) of tribromoborane (1 M solution in heptane) was added dropwise at 0°C, and the reaction mixture was heated to room temperature over 45 minutes, after which 1.44 mL (8.40 mmol) of N-ethyl-N-isopropylpropane-2-amine was added. The reaction mixture was stirred at 155°C for 16 hours. The reaction mixture 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 extract was washed with water and 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 5 mg (2% yield) of Compound 27 as a yellow solid. The molecular mass of the product was determined by LC-MS [M+H] + It was confirmed to be 624.7.

[1189] II of the compound evaluation

[1190] Next, the properties of the compounds used in the examples were measured. The measurement and calculation methods are shown below.

[1191] 1.1 Photoluminescence Application data

[1192] The toluene solution of the compounds mentioned in the table is 10 of the corresponding compounds - 6 It was prepared by dissolving in toluene at a concentration of mol / L. The total fluorescence spectrum was measured in the toluene solution using an FP-8300 JASCO spectrofluorometer.

[1193] Photoluminescence (PL) data of compounds 1 to 27 of the present invention in toluene solution were measured and summarized in the table below. As a comparative example, PL data of comparative compound 1 in toluene solution according to US 2019 / 0067577 A1

[0122] is disclosed in the table below:

[1194]

[1195] These results demonstrate that compounds 1 to 6 and 8 to 27 of the present invention provide a narrower spectrum (smaller FWHM), i.e., better color purity, than comparative compound 1. The PL of compound 7 of the present invention is longer than that of comparative compound 1.

[1196]

[1197] 1.2. device Application data ( two meters As a dopant Compound of the present invention)

[1198] Manufacturing and Evaluation of Organic EL Devices

[1199] An organic EL device was fabricated and evaluated as follows:

[1200] Application example 1

[1201] A glass substrate using a 130 nm thick indium tin oxide (ITO) transparent electrode (manufactured by Geomatec Co., Ltd.) as the anode was first treated with N2 plasma for 100 seconds. This treatment also improved the hole injection characteristics of the ITO. The cleaned substrate was mounted in a substrate holder and placed in a vacuum chamber. Subsequently, the organic material specified below was applied approximately 10 -6 -10 -8The device was applied to an ITO substrate by vapor deposition at a rate of approximately 0.2–1 Å / sec at mbar. As a hole injection layer, a 10 nm thick mixture of compound HT-1 and 3 wt% of compound HI was applied. Subsequently, 80 nm thick compound HT-1 and 10 nm thick compound HT-2 were applied as hole transport layer 1 and hole transport layer 2, respectively. Next, a 25 nm thick fluorescent emitting layer was formed by applying a mixture of 2 wt% of emitter compound 2 and 98 wt% of host compound BH-1. On the emitting layer, 10 nm thick compound ET-1 was applied as electron transport layer 1 and 15 nm thick compound ET-2 as electron transport layer 2. Finally, 1 nm thick LiF was deposited as an electron injection layer, and then 80 nm thick Al was deposited as a cathode to complete the device. The device was sealed with a glass lid and getter in an inert nitrogen atmosphere with less than 1 ppm of water and oxygen. To characterize the OLED, electroluminescence (EL) spectra were recorded at various currents and voltages. The EL peak maximum and full width at half maximum (FWHM) were set at 10 mA / cm². 2 It was recorded in [location]. In addition, luminous efficiency and external quantum efficiency (EQE) were measured by measuring the current-voltage characteristics in combination with luminance. The driving voltage was 10 mA / cm². 2 It was given at the current density. The device results are shown in Table 1 below.

[1202]

[1203]

[1204]

[1205]

[1206]

[1207]

[1208]

[1209]

[1210] These results demonstrate that when the compounds of the present invention are used as fluorescent light-emitting materials in OLEDs, they provide good EQE and a narrow spectrum (smaller FWHM), i.e., good color purity.

[1211] 1.3 added Application example

[1212] Application Example 1 was repeated except that compounds 3-6, 8, 11, 12, 15-17, 20, 21, and 23 were used instead of compound 2 as the emitter in the fluorescent emitting layer.

[1213]

Claims

Claim 1 Heterocyclic compounds represented by the following chemical formula (VC): During the meal, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 Each independently hydrogen; an unsubstituted or substituted aryl group having 6 to 60 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 60 cyclic carbon atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted alkyl halide group having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms; CN; N(R 22 )2; OR 20 ; SR 20 ; B(R 21 )2; SiR 24 R 25 R 26 or indicates a halogen; R 1 , R 2 and R 3 Two adjacent residues among, R 4 , R 5 and R 6 Two adjacent residues among, R 7 , R 8 , R 9 and R 10 Two adjacent residues among, R 13 , R 14 and R 15 Two adjacent residues among, R 16 , R 17 , R 18 and R 19 Two adjacent residues among them can form an unsubstituted or substituted ring structure together, R 7 is R 6 It can be connected to form an unsubstituted or substituted ring structure; R 20 , R 21 , and R 22 Each independently represents an unsubstituted or substituted aryl group having 6 to 60 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 60 cyclic carbon atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; or an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms; and two residues R 22 and 2 residues R 21 One or more of They can form unsubstituted or substituted ring structures together;R 20 , R 21 , and R 22 One or more of are adjacent residues R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 or R 19 It can form unsubstituted or substituted ring structures together with;R 24 , R 25 and R 26 Each independently represents an unsubstituted or substituted aryl group having 6 to 60 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 60 cyclic atoms and connected to N or Si through carbon atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; or an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms; and two residues R 24 and R 25 They can form unsubstituted or substituted ring structures together, provided that the heterocyclic compound is not any of the following chemical formulas: . Claim 2 In paragraph 1, R in the formula 4 to R 6 , and R 13 to R 15 At least one of which is an unsubstituted or substituted aryl group having 6 to 60 cyclic carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 60 cyclic carbon atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted alkyl halide group having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 20 cyclic carbon atoms; CN; N(R 22 )2; OR 20 ; SR 20 ; B(R 21 )2; SiR 24 R 25 R 26 or a heterocyclic compound that represents a halogen. Claim 3 A material for an organic electroluminescence device comprising at least one compound according to claim 1 or 2. Claim 4 An organic electroluminescence device comprising at least one compound according to claim 1 or 2. Claim 5 An organic electroluminescence device according to claim 4, comprising one or more organic thin film layers including a cathode, an anode, and a light-emitting layer disposed between the cathode and the anode, wherein at least one of the organic thin film layers comprises the at least one compound. Claim 6 An organic electroluminescence device according to claim 5, wherein the light-emitting layer comprises at least one of the above compounds. Claim 7 An organic electroluminescence device according to claim 6, wherein the light-emitting layer comprises at least one host and at least one dopant, and the dopant comprises the at least one compound. Claim 8 An organic electroluminescence device according to claim 7, wherein the host comprises at least one substituted or unsubstituted fused aromatic hydrocarbon compound and / or at least one substituted or unsubstituted anthracene compound. Claim 9 An electronic device comprising an organic electroluminescence device according to paragraph 4. Claim 10 A light-emitting layer comprising at least one host and at least one dopant, wherein the dopant comprises at least one compound according to claim 1 or 2. Claim 11 delete Claim 12 delete Claim 13 delete Claim 14 delete Claim 15 delete Claim 16 delete Claim 17 delete Claim 18 delete Claim 19 delete Claim 20 delete Claim 21 delete Claim 22 delete

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