Heterocyclic compounds and organic electroluminescent devices comprising the same

Abstract

The present application relates to specific heterocyclic compounds, to materials, preferably emitter materials, for organic electroluminescent devices, containing the specific heterocyclic compounds, to organic electroluminescent devices containing the specific heterocyclic compounds, to electronic devices containing the organic electroluminescent devices, to light-emitting layers containing at least one host and at least one dopant, wherein the dopant contains at least one of the specific heterocyclic compounds, and to the use of the specific heterocyclic compounds in organic electroluminescent devices.

Description

TECHNICAL FIELD

[0001] The present application relates to specific heterocyclic compounds, to materials, preferably emitter materials, for organic electroluminescent devices comprising the specific heterocyclic compounds, to organic electroluminescent devices comprising the specific heterocyclic compounds, to electronic devices comprising the organic electroluminescent devices, to light-emitting layers comprising at least one host and at least one dopant, wherein the dopant comprises at least one of the specific heterocyclic compounds, and to the use of the heterocyclic compounds in organic electroluminescent devices.

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

[0003] An organic EL device includes a light-emitting layer between an anode and a cathode. Furthermore, there can be cases in which it has a stacked structure including organic layers such as a hole-injection layer, a hole-transport layer, an electron-injection layer, an electron-transport layer, and the like.

[0004] US 2019 / 0067577 A1 relates to boron-containing heterocyclic compounds for use in organic electronic devices, for example organic light-emitting devices having a structure according to the following Formula I

[0005] Formula I

[0006] wherein

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

[0008] R1, R2, R3and R4each independently represent no substitution or up to the maximum available substitution;

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

[0010] Z is N or P.

[0011] One example of a compound of Formula I is the following compound

[0012] .

[0013] However, the specific structure and substitution pattern of polycyclic compounds has a significant influence on the performance of polycyclic compounds in organic electronic devices.

[0014] Despite the above developments, there is still a need for organic electroluminescent devices comprising new materials, in particular dopant (= emitter) materials, to provide improved electroluminescent device performance.

[0015] Therefore, the object of the present application is to provide a material suitable for providing an organic electroluminescent device which ensures good performance of the organic electroluminescent device, in particular good EQE and / or long lifetime. More particularly, it should be possible to provide a dopant (= emitter) material, in particular a blue-emitting dopant material having a narrow spectrum (small FWHM), i.e. having a good color purity when used as a dopant in an organic electroluminescent device.

[0016] According to one aspect of the present application, the object is solved by a heterocyclic compound represented by formula (I):

[0017]

[0018] wherein

[0019] ring A1, ring B1, ring C1and ring D1each independently represent a substituted or unsubstituted aryl having 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms, or a substituted or unsubstituted heteroaryl having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms;

[0020] or

[0021] ring C1and ring D1may be connected by a direct bond, O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 , preferably by a direct bond;

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

[0023] or

[0024] R E or R E on R 23 may be bound to ring A1and / or to ring B1or to a substituent on ring A1and / or ring B1to form an unsubstituted or substituted ring structure,

[0025] Y represents a direct bond, O, S, NR 23 , SiR 24 R25 or CR 27 R 28 , preferably a direct bond;

[0026] In case Y is a direct bond, rings B1and C1may additionally be connected by O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 ;

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

[0028] and / or

[0029] two residues R 24 and R 25 and / or two residues R 27 and R 28 together form an unsubstituted or substituted ring structure.

[0030] The compounds of the formula (I) can in principle be used in any layer of an EL device. Preferably, the compounds of the formula (I) are dopants (= emitters), more preferably fluorescent dopants, in organic EL devices, in particular in light-emitting layers. In particular, the compounds of the formula (I) are used as fluorescent dopants in organic EL devices, in particular in light-emitting layers.

[0031] In the present application, the term organic EL device (organic electroluminescent device) is used interchangeably with the term organic light-emitting diode (OLED).

[0032] It has been found that specific compounds of the formula (I) show narrow emission characteristics, preferably narrow fluorescence, more preferably narrow blue fluorescence. This narrow emission characteristic is suitable to prevent energy loss due to out-coupling. The compounds of the formula (I) according to the present application preferably have a full width at half maximum (FWHM) of less than 30 nm, more preferably less than 25 nm.

[0033] It has also been found that organic EL devices containing the compounds of the present invention are generally characterized by high external quantum efficiency (EQE) and long lifetime, especially when a particular compound of formula (I) is used as a dopant (luminescent material), particularly a fluorescent dopant in organic electroluminescent devices.

[0034] Examples of any one or more substituents indicated by "substituted or unsubstituted" and "may be substituted" as mentioned above or below include aryl groups having 6-60, preferably 6-30, more preferably 6-18 cyclic carbon atoms, which are further unsubstituted or substituted; heteroaryl groups having 5-60, preferably 5-30, more preferably 5-18 cyclic atoms, which are further unsubstituted or substituted; alkyl groups having 1-20, preferably 1-8 carbon atoms; cycloalkyl groups having 3-20, preferably 3-6 carbon atoms; and groups OR 20 Having 1-20, preferably 1-8, carbon alkyl halogroups, N(R) 22 2, halogen atom (fluorine, chlorine, bromine, iodine), cyano group, carboxyl group having 1-20 carbon atoms, preferably 1-8 carbon atoms, amide alkyl group having 1-20 carbon atoms, preferably 1-8 carbon atoms, silyl group (SiR) 24 R 25 R 26 , B(R 21 )2, group SR 20 Carboxylaryl groups having 6-18 ring carbon atoms in the aryl residue and amide-aryl groups having 6-18 ring carbon atoms in the aryl residue;

[0035] or

[0036] Two adjacent substituents together form a ring structure, which is then either unsubstituted or substituted;

[0037] R 20 R 21 and R 22 Each of the following 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 carbon atoms connected to N, O, S or B via 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] Two residues R 22 and / or two residues R 21 Together they form unsubstituted or substituted ring structures;

[0040] or

[0041] R 20 , R 21 and / or R 22 form, together with the adjacent substituent, an unsubstituted or substituted ring structure;

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

[0043] R 24 , R 25 are as defined above.

[0044] The terms hydrogen, halogen, unsubstituted or substituted alkyl having 1 to 20 carbon atoms, unsubstituted or substituted halogenalkyl having 1 to 20 carbon atoms, unsubstituted or substituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms; substituted or unsubstituted heteroaryl having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms, carboxyalkyl having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, amidoalkyl having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, carboxyaryl having 6 to 18 ring carbon atoms in the aryl residue, amidoaryl having 6 to 18 ring carbon atoms in the aryl residue, N(R 22 )2, OR 20 , SR 20 , SR 20 , SiR 24 R 25 R 26 and B(R 21 )2,

[0045] are known in the art and, if the groups are not further specified in the specific embodiments mentioned below, generally have the following meanings:

[0046] In the present application, hydrogen includes isomers differing in the number of neutrons, i.e. protium, deuterium and tritium.

[0047] Substituted or unsubstituted aromatic groups (also referred to as aryl groups) having 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms, most preferably having 6 to 13 ring carbon atoms, can be non-fused aryl groups or fused aryl groups. Specific examples thereof include phenyl, naphthyl, phenanthryl, biphenyl, terphenyl, fluoranthenyl, triphenylenyl, phenanthryl, fluorenyl, indenyl, anthryl, perylenyl, spirofluorenyl, benzo[c]phenanthryl, wherein phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, fluorenyl, indenyl, and fluoranthenyl are preferred, more preferably phenyl, 1-naphthyl, 2-naphthyl, biphen-2-yl, biphen-3-yl, biphen-4-yl, phenanthren-9-yl, phenanthren-3-yl, phenanthren-2-yl, triphenylen-2-yl, fluoren-2-yl, in particular 9,9-dimethylfluoren-2-yl, 9,9-di-C 1-20 alkylfluoren-2-yl, such as 9,9-dimethylfluoren-2-yl, 9,9-di-C 6-18 arylfluoren-2-yl, such as 9,9-diphenylfluoren-2-yl,

[0048] or 9,9-di-C 5-18 heteroarylfluoren-2-yl, 1,1 -dimethylindenyl, fluoranthen-3-yl, fluoranthen-2-yl, and fluoranthen-8-yl, most preferably phenyl.

[0049] In the case of rings A1, B1, C1, and D1, preferred substituted or unsubstituted aryl groups having 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms are described below.

[0050] The substituted or unsubstituted heteroaromatic group (also referred to as heteroaryl group) having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms, most preferably having 5 to 13 ring atoms can be a non-fused heteroaryl group or a fused heteroaryl group. Specific examples thereof include a residue of a pyrrole ring, an isoindole ring, a benzofuran ring, an isobenzofuran ring, a benzothiophene, a dibenzothiophene ring, an isoquinoline ring, a quinoxaline ring, a quinazoline, a phenanthridine ring, a phenalene 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, a benzoxazole 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 indoline ring, an imidazopyridine ring, a 4-imidazo[l,2-a]benzimidazolyl group, a 5-benzimidazo[l,2-a]benzimidazolyl group, and a benzimidazo[2,l-b][l,3]benzothiazolyl group, of which residues of a benzofuran ring, an indole ring, a benzothiophene ring, a dibenzofuran ring, a carbazole ring, and a dibenzothiophene ring are preferred, and residues of a benzofuran ring, a 1-phenylindole ring, a benzothiophene ring, a dibenzofuran-l-yl group, a dibenzofuran-3-yl group, a dibenzofuran-2-yl group, a dibenzofuran-4-yl group, a 9-phenylcarbazole-3-yl group, a 9-phenylcarbazole-2-yl group, a 9-phenylcarbazole-4-yl group, a dibenzothiophene-2-yl group, a dibenzothiophene-4-yl group, a dibenzothiophene-l-yl group, and a dibenzothiophene-3-yl group are more preferred.

[0051] In the case of rings A1, B1, C1, and D1, preferred substituted or unsubstituted heteroaryl groups having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms are as described below.

[0052] Examples of unsubstituted or substituted alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-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, 1-methylpentyl, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl. Alkyl groups having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms are preferred. Suitable examples of alkyl groups having 1 to 8 carbon atoms and 1 to 4 carbon atoms, respectively, are as described above.

[0053] Examples of unsubstituted or substituted haloalkyl groups having 1 to 20 carbon atoms include those disclosed as alkyl groups, wherein some or all of the hydrogen atoms thereof are replaced by halogen atoms. Preferred haloalkyl groups are fluoroalkyl groups having 1 to 20 carbon atoms, including the alkyl groups described above, wherein some or all of the hydrogen atoms thereof are replaced by fluorine atoms, for example CF3.

[0054] Examples of unsubstituted or substituted cycloalkyl groups having from 3 to 20 ring carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and adamantyl, preferably cyclopentyl and cyclohexyl. Cycloalkyl groups having from 3 to 6 carbon atoms are preferred. Suitable examples of cycloalkyl groups having from 3 to 6 carbon atoms are as described above.

[0055] Examples of halogen atoms include fluorine, chlorine, bromine and iodine, preferably fluorine.

[0056] the group OR 20 preferably C 1-20 alkoxy or C 6-18 aryloxy. Examples of alkoxy groups having from 1 to 20 carbon atoms, preferably from 1 to 8 carbon atoms, include those having an alkyl moiety selected from the above-mentioned alkyl groups. Examples of aryloxy groups having from 6 to 18 ring carbon atoms include those having an aryl moiety selected from the above-mentioned aryl groups, for example -OPh.

[0057] the group SR 20 preferably C 1-20 alkylthio or C 6-18 arylthio. Examples of alkylthio groups having from 1 to 20 carbon atoms, preferably from 1 to 8 carbon atoms, include those having an alkyl moiety selected from the above-mentioned alkyl groups. Examples of arylthio groups having from 6 to 18 ring carbon atoms include those having an aryl moiety selected from the above-mentioned aryl groups, for example -SPh.

[0058] the group N(R 22 )2preferably C 1-20 alkyl and / or C 6-18 aryl and / or heteroaryl (having from 5 to 18 ring atoms) substituted amino. Examples of alkylamino groups (alkyl substituted amino) having from 1 to 20 ring carbon atoms include those having an alkyl moiety selected from the above-mentioned alkyl groups. Examples of arylamino groups (aryl substituted amino) having from 6 to 18 ring carbon atoms include those having an aryl moiety selected from the above-mentioned aryl groups, for example -NPh2. Examples of heteroarylamino groups (heteroaryl substituted amino), preferably having from 5 to 18 ring atoms, include those having a heteroaryl moiety selected from the above-mentioned heteroaryl groups.

[0059] the group B(R 21 )2preferably C 1-20 alkyl and / or C 6-18Aryl and / or heteroaryl (with 5 to 18 ring atoms) substituted boron radicals. Examples of alkyl boron radicals (alkyl substituted boron radicals) having 1 to 20 ring carbon atoms include those having an alkyl moiety selected from the above-mentioned alkyl groups. Examples of aryl boron radicals (aryl substituted boron radicals) having 6 to 18 ring carbon atoms include those having an aryl moiety selected from the above-mentioned aryl groups. Examples of heteroaryl boron radicals (heteroaryl substituted boron radicals), preferably having 5 to 18 ring atoms include those having a heteroaryl moiety selected from the above-mentioned heteroaryl groups.

[0060] Radicals SiR 24 R 25 R 26 Preferably C 1-20 Alkyl and / or C 6-18 Aryl substituted silyl radicals. Preferred examples of C 1-20 Alkyl and / or C 6-18 Aryl substituted silyl radicals include alkylsilyl radicals having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms in each alkyl residue, including trimethylsilyl, triethylsilyl, tributylsilyl, dimethylethylsilyl, t-butyldimethylsilyl, propyldimethylsilyl, dimethylisopropylsilyl, dimethylpropylsilyl, dimethylbutylsilyl, dimethyl-t- butylsilyl, diethylisopropylsilyl, and arylsilyl radicals having 6 to 18 ring carbon atoms in each aryl residue, preferably triphenylsilyl, and alkyl / α-arylsilyl radicals, preferably phenyldimethylsilyl, diphenylmethylsilyl and diphenyl-t- butylsilyl, preferably diphenyl-t-butylsilyl and t-butyldimethylsilyl.

[0061] Examples of carboxyalkyl radicals having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms include those having an alkyl moiety selected from the above-mentioned alkyl groups.

[0062] Examples of fluoroalkyl radicals having 1 to 20 carbon atoms include the above-mentioned alkyl groups wherein some or all of the hydrogen atoms are replaced by fluorine atoms.

[0063] Examples of amidoalkyl radicals (alkyl substituted amido radicals) having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms include those having an alkyl moiety selected from the above-mentioned alkyl groups.

[0064] Examples of amidoaryl radicals (aryl substituted amido radicals) having 6 to 18 carbon atoms, preferably 6 to 13 carbon atoms include those having an aryl moiety selected from the above-mentioned aryl groups.

[0065] R6and R7each independently represent an unsubstituted or substituted aryl group having 6 to 18 ring carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 18 ring atoms which is attached to N or O or S via a carbon atom; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; or an unsubstituted or substituted cycloalkyl group having 3 to 20 ring carbon atoms; 22 24 R 25 R 2 6、SR 20 or OR 20 ;

[0066] or

[0067] two adjacent substituents together form a ring structure which in turn is unsubstituted or substituted;

[0068] R 20 and R 22 each independently represent an unsubstituted or substituted aryl group having 6 to 18 ring carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 18 ring atoms which is attached to N or O or S via a carbon atom; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; or an unsubstituted or substituted cycloalkyl group having 3 to 20 ring carbon atoms;

[0069] or

[0070] R 20 and / or R 22 together with adjacent substituents form a ring structure which in turn is unsubstituted or substituted;

[0071] R 24 , R 25 and R 26 represent an unsubstituted or substituted aryl group having 6 to 18 ring carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 18 ring atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; or an unsubstituted or substituted cycloalkyl group having 3 to 20 ring carbon atoms.

[0072] More preferably, the optional substituents each independently represent an unsubstituted or substituted aryl group having 6 to 18 ring carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 18 ring atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 20 ring carbon atoms; CN; or N(R 22 )2;

[0073] or

[0074] two adjacent substituents together form a ring structure which in turn is unsubstituted or substituted;

[0075] R​22 represents an unsubstituted or substituted aryl group having 6 to 18 ring carbon atoms; or an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms;

[0076] or

[0077] R 22 together with the adjacent substituent form a ring structure which in turn is unsubstituted or substituted.

[0078] Most preferably, each optional substituent independently represents an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 6 ring carbon atoms; an unsubstituted or substituted aryl group having 6 to 13 ring carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 13 ring atoms; CN; or N(R 22 )2;

[0079] or

[0080] two adjacent substituents together form a ring structure which in turn is unsubstituted or substituted;

[0081] R 22 represents an unsubstituted or substituted aryl group having 6 to 18 ring carbon atoms; or an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms.

[0082] The above optional substituents can be further substituted by one or more of the above optional substituents.

[0083] The number of optional substituents depends on the group which is substituted by said one or more substituents. The maximum number of possible substituents is defined by the number of hydrogen atoms present. Preferably, each substituted group has 1, 2, 3, 5, 6, 7, 8 or 9 optional substituents, more preferably 1, 2, 3, 5, 6 or 7 optional substituents, most preferably 1, 2, 3, 4 or 5 optional substituents, further most preferably 1, 2, 3, 4 or 5 optional substituents, more further most preferably 1, 2, 3 or 4 optional substituents, more further most preferably each substituted group has 1 or 2 optional substituents. In a further preferred embodiment, some or all of the above groups are unsubstituted.

[0084] 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.

[0085] The "number of carbons from a to b" in the expression "substituted or unsubstituted X group having a to b carbon atoms" is the number of carbons of the unsubstituted X group and does not include one or more carbon atoms of optional substituents.

[0086] The term "unsubstituted" mentioned by "unsubstituted or substituted" means that the hydrogen atom is not substituted by one of the above-mentioned groups.

[0087] In the definitions of the above and below formulae, the index 0 means that a hydrogen atom is present at the position defined by said index.

[0088] The compound of formula (I)

[0089] In the heterocyclic compound represented by formula (I)

[0090]

[0091] The residues have the following meanings:

[0092] Ring A1, ring B1, ring C1 and ring D1 each independently represent a substituted or unsubstituted aryl group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms;

[0093] or

[0094] Ring C1 and ring D1 can be linked by a direct bond, O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 , preferably by a direct bond;

[0095] R E represents hydrogen, unsubstituted or substituted aryl having 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms, or unsubstituted or substituted heteroaryl having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms; unsubstituted or substituted alkyl having 1 to 20 carbon atoms; unsubstituted or substituted cycloalkyl having 3 to 20 ring carbon atoms; unsubstituted or substituted alkenyl having 2 to 20 carbon atoms; imine group R 23 -C=N, unsubstituted or substituted alkynyl having 2 to 20 carbon atoms;

[0096] or

[0097] R E or R E on R 23 may be bound to ring A1 and / or to ring B1 or to a substituent on ring A1 and / or ring B1 to form an unsubstituted or substituted ring structure,

[0098] Y represents a direct bond, O, S, NR 23 , SiR 24 R 25 or CR27 R 28 , preferably a direct bond;

[0099] In case Y is a direct bond, ring B 1 and C 1 may additionally be connected by O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 ;

[0100] R 23 , R 24 , R 25 , R 27 and R 28 each independently represent an unsubstituted or substituted aryl group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms, or an unsubstituted or substituted heteroaryl group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms, which is connected to N or Si by a carbon atom; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; or an unsubstituted or substituted cycloalkyl group having 3 to 20 ring carbon atoms;

[0101] and / or

[0102] two residues R 24 and R 25 and / or two residues R 27 and R 28 together form an unsubstituted or substituted ring structure.

[0103] Preferably, rings A1, B1, C1and D1each independently represent a substituted or unsubstituted aryl group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms, of the following formula:

[0104]

[0105] wherein ring C1and ring D1may be connected by a direct bond, O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 , preferably by a direct bond;

[0106] the star is the position of the preferred bonding optional site between ring C1and ring D1;

[0107] and the dotted line is a direct bond.

[0108] More preferred are rings A1, B1, C1and D1which are:

[0109] non-fused or fused aryl. Specific examples thereof are based on phenyl, naphthyl, phenanthrene, biphenyl, terphenyl, fluoranthene, triphenylene, fluorene, indene, anthracene, chrysene, spirofluorene, benzo[c]phenanthrene, wherein phenyl, naphthyl, biphenyl, terphenyl, phenanthrene, triphenylene, fluorene, indene and fluoranthene are preferred, and phenyl and naphthyl are most preferred;

[0110] or

[0111] non-fused or fused heteroaryl. Specific examples thereof are based on pyrrole, isoindole, benzofuran, isobenzofuran, benzothiophene, dibenzothiophene, isoquinoline, quinoxaline, quinazoline, phenanthridine, phenanthroline, pyridine, pyrazine, pyrimidine, pyridazine, indole, quinoline, acridine, carbazole, furan, thiophene, benzoxazole, benzothiazole, benzimidazole, dibenzofuran, triazine, oxazole, oxadiazole, thiazole, thiadiazole, triazole, imidazole, indolizine, imidazopyridine, 4-imidazo[l,2-a]benzimidazole, 5-benzimidazo[l,2-a]benzimidazole and benzoimidazo[2,l-b][l,3]benzothiazole, wherein indole, especially l-phenylindole, benzothiophene, dibenzofuran, carbazole, dibenzothiophene, benzofuran and benzothiophene are preferred.

[0112] More preferably, rings A1, B1, C1and D1are represented by the following formulae:

[0113]

[0114] wherein the dotted line is the bonding site and the residues R 12 , R 13 , R 14 and R 15 are defined as follows:

[0115]

[0116] wherein the dotted line is the bonding site and the residues R 4 , R 5 and R 6 are defined as follows:

[0117]

[0118] wherein the dotted line is the bonding site and the residues R 1 , R 2 and R 3 are defined as follows:

[0119] wherein rings C1and D1may be linked by a direct bond, O, S, NR 23 , SiR 24 R 25or CR 27 R 28 are connected, preferably by a direct bond, and the asterisk is the position of the preferred optional bonding site to ring D1 ;

[0120]

[0121] wherein the dotted line is a bonding site and the residues R 16 , R 17 , R 18 and R 19 are defined as follows; wherein ring C1 and ring D1 can be connected by a direct bond, O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 are connected, preferably by a direct bond, and the asterisk is the position of the preferred optional bonding site to ring C1.

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

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129] wherein X is O, CR a R b , S or NR c ,

[0130] X" and Y" each independently represent O, CR a R b , S, BR c or NR c ,

[0131] R a and R b each independently represent C1 to C8 alkyl, or substituted or unsubstituted C6 to C 18 aryl, preferably C1 to C4 alkyl, or substituted or unsubstituted C6 to C 10 aryl, more preferably methyl or unsubstituted or substituted phenyl,

[0132] R c represents C1to C8alkyl, preferably C1to C4alkyl, or substituted or unsubstituted C6to C 10 aryl, preferably unsubstituted or substituted phenyl,

[0133] E1, F1, F2, G1, H1, I1, I2, K1, L1, M1and N1each independently represent a substituted or unsubstituted aryl group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms,

[0134] and

[0135] The dotted line is a bonding site.

[0136] R E or the substituents on R E may be bonded to ring A1and / or to ring B1or to a substituent on ring A1and / or ring B1to form an unsubstituted or substituted ring structure. Examples of cases where this is the case are:

[0137]

[0138] wherein

[0139] R E1 , R E2 , R E3 , R E5 and R E6 each independently represent C1to C8alkyl, or substituted or unsubstituted C6to C 18 aryl, preferably C1to C4alkyl, or substituted or unsubstituted C6to C 10 aryl, more preferably methyl or unsubstituted or substituted phenyl,

[0140] or

[0141] two adjacent residues R E2 and R E3 , or R E5 and R E6 together form a substituted or unsubstituted ring structure,

[0142] X’ represents a direct bond, O, S, NR 23 , SiR 24 R 25 , CR 27 R 28 or BR 21 ,

[0143] ring A1, B1, C1, D1, R 21 , R 23R 24 R 25 R 27 R 28 and Y are defined above and below, and

[0144] R 7 R 8 R 9 R 10 and R 11 are defined below.

[0145] Y represents a direct bond, O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 , preferably a direct bond;

[0146] In case Y is a direct bond, rings B1and C1may additionally be connected by O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 .

[0147] In case Y is a direct bond and rings B1and C1are additionally connected by O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 , the following applies:

[0148]

[0149] wherein Z is O, S, NR 23 , SiR 24 R 25 or CR 27 R 28 , and the residues and indices have been mentioned above.

[0150] Preferably, Y is a direct bond.

[0151] The preferred heterocyclic compounds according to the application are represented by formula (II)

[0152]

[0153] wherein the residues and indices are as described above.

[0154] In a more preferred embodiment, the heterocyclic compounds according to the application are represented by formula (III)

[0155]

[0156] wherein the residues and indices are as described above.

[0157] In one embodiment, ring A1in the heterocyclic compound according to the application is a substituted or unsubstituted heteroaryl having 5 to 60 ring atoms. Suitable heteroaryls are described above.

[0158] R E is preferably a radical of the following formula (IV):

[0159]

[0160] wherein

[0161] R 7 , R 8 , R 9 , R 10 and R 11 each independently denote hydrogen; unsubstituted or substituted aryl having 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms; unsubstituted or substituted heteroaryl having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms; unsubstituted or substituted alkyl having 1 to 20 carbon atoms; unsubstituted or substituted halogenalkyl having 1 to 20 carbon atoms; unsubstituted or substituted cycloalkyl 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 halogen;

[0162] and / or

[0163] two adjacent residues R 7 , R 8 , R 9 , R 10 and / or R 11 together form an unsubstituted or substituted ring structure;

[0164] and / or

[0165] R 7 and / or R 11 are linked to ring B1and / or to a substituent on ring A1or to ring A1and / or ring B1to form an unsubstituted or substituted ring structure;

[0166] and the dotted line is a bonding site.

[0167] Most preferably, the heterocyclic compound according to the application is represented by formula (V)

[0168]

[0169] wherein

[0170] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 each independently represent hydrogen; unsubstituted or substituted aryl having 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms; unsubstituted or substituted heteroaryl having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms; unsubstituted or substituted alkyl having 1 to 20 carbon atoms; unsubstituted or substituted halogenalkyl having 1 to 20 carbon atoms; unsubstituted or substituted cycloalkyl 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 halogen;

[0171] or

[0172] two adjacent residues R 1 , R 2 and / or R 3 and / or two adjacent residues R 4 , R 5 and / or R 6 and / or two adjacent residues R 12 , R 13 , R 14 and / or R 15 , and / or two adjacent residues R 16 , R 17 , R 18 and / or R 19 form together an unsubstituted or substituted ring structure,

[0173] and / or

[0174] two adjacent residues R 7 , R 8 , R 9 , R 10 and / or R 11together form an unsubstituted or substituted ring structure;

[0175] and / or

[0176] R 7 and / or R 11 is connected to R 6 and / or R 12 together form an unsubstituted or substituted ring structure;

[0177] R 20 , R 21 and R 22 each independently represent unsubstituted or substituted aryl having 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms; unsubstituted or substituted heteroaryl having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms; unsubstituted or substituted alkyl having 1 to 20 carbon atoms; unsubstituted or substituted cycloalkyl having 3 to 20 ring carbon atoms;

[0178] and / or

[0179] two residues R 22 and / or two residues R 21 together form an unsubstituted or substituted ring structure;

[0180] or

[0181] R 20 , R 21 and / or R 22 together with the adjacent residues R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 or R 19 form an unsubstituted or substituted ring structure; and

[0182] R 24 , R 25 and R 26each independently represents an unsubstituted or substituted aryl group having 6 to 60, preferably 6 to 30, more preferably 6 to 18 ring carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 60, preferably 5 to 30, more preferably 5 to 18 ring atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; or an unsubstituted or substituted cycloalkyl group having 3 to 20 ring carbon atoms.

[0183] through two adjacent residues R 1 , R 2 and / or R 3 and / or two adjacent residues R 4 , R 5 and / or R 6 and / or two adjacent residues R 7 , R 8 , R 9 , R 10 and / or R 11 and / or two adjacent residues R 12 , R 13 , R 14 and / or R 15 , and / or two adjacent residues R 16 , R 17 , R 18 and / or R 19 form a ring structure, examples of which are shown below (the following ring structures can be substituted by one or more of the above-mentioned substituents):

[0184]

[0185] wherein X is O, CR a R b , S or NR c ,

[0186] R a and R b each independently represent a Ci to C8alkyl group, or a substituted or unsubstituted C6to C 18 aryl group, preferably a Ci to C4alkyl group, or a substituted or unsubstituted C6to C 10 aryl group, more preferably a methyl group or an unsubstituted or substituted phenyl group,

[0187] R c represents a Ci to C8alkyl group, preferably a Ci to C4alkyl group, or a substituted or unsubstituted C6to C 10 aryl group, preferably an unsubstituted or substituted phenyl group.

[0188] R 7 and / or R 11 are linked to R 6 and / or R 12Examples of cases in which a non-substituted or substituted ring structure is formed are:

[0189]

[0190] wherein

[0191] X' represents a direct bond, O, S, NR 23 , SiR 24 R 25 , CR 27 R 28 or BR 21 , and

[0192] all other residues are defined above or below.

[0193] 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 represent hydrogen; unsubstituted or substituted aryl having 6 to 18 ring carbon atoms; unsubstituted or substituted heteroaryl having 5 to 18 ring atoms; unsubstituted or substituted alkyl having 1 to 20 carbon atoms; unsubstituted or substituted cycloalkyl having 3 to 20 ring carbon atoms; CN; N(R 22 )2; SiR 24 R 25 R 26 , SR 20 or OR 20 ;

[0194] or

[0195] two adjacent residues R 1 , R 2 and / or R 3 and / or two adjacent residues R 4 , R 5 and / or R 6 and / or two adjacent residues R 7 , R 8 , R 9 , R 10and / or R 11 and / or two adjacent residues R 12 , R 13 , R 14 and / or R 15 , and / or two adjacent residues R 16 , R 17 , R 18 and / or R 19 together form an unsubstituted or substituted ring structure,

[0196] and / or

[0197] R 7 and / or R 11 are linked to R 6 and / or R 12 to form an unsubstituted or substituted ring structure;

[0198] R 20 and R 22 each independently represent an unsubstituted or substituted aryl group having 6 to 18 ring carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 18 ring atoms; an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl group having 3 to 20 ring carbon atoms;

[0199] or

[0200] R 20 and / or R 22 form an unsubstituted or substituted ring structure with adjacent residues R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 or R 19 ; and

[0201] R 24 , R 25 and R 26denotes unsubstituted or substituted aryl having 6 to 18 ring carbon atoms; unsubstituted or substituted heteroaryl having 5 to 18 ring atoms; unsubstituted or substituted alkyl having 1 to 20 carbon atoms; unsubstituted or substituted cycloalkyl having 3 to 20 ring carbon atoms.

[0202] 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 or R 19 each independently denotes hydrogen, unsubstituted or substituted aryl having 6 to 18 ring carbon atoms; unsubstituted or substituted heteroaryl having 5 to 18 ring atoms; unsubstituted or substituted alkyl having 1 to 20 carbon atoms; unsubstituted or substituted cycloalkyl having 3 to 20 ring carbon atoms; CN or N(R 22 )2;

[0203] or

[0204] two adjacent residues R 1 , R 2 and / or R 3 and / or two adjacent residues R 4 , R 5 and / or R 6 and / or two adjacent residues R 7 , R 8 , R 9 , R 10 and / or R 11 and / or two adjacent residues R 12 , R 13 , R 14 and / or R 15 , and / or two adjacent residues R 16 , R 17 , R 18 and / or R 19 form together an unsubstituted or substituted ring structure,

[0205] and / or

[0206] R 7 and / or R11 Connect to R 6 and / or R 12 To form unsubstituted or substituted ring structures;

[0207] R 22 It refers to 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;

[0208] or

[0209] R 22 With 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 they form unsubstituted or substituted ring structures.

[0210] Most preferably, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 R 15 R 16 R 17 R 18 or R 19 Each of these can independently represent 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 carbon atoms; CN or N(R) 22 )2;

[0211] or

[0212] two adjacent residues R 1 , R 2 and / or R 3 and / or two adjacent residues R 4 , R 5 and / or R 6 and / or two adjacent residues R 7 , R 8 , R 9 , R 10 and / or R 11 and / or two adjacent residues R 12 , R 13 , R 14 and / or R 15 , and / or two adjacent residues R 16 , R 17 , R 18 and / or R 19 together form an unsubstituted or substituted ring structure,

[0213] and / or

[0214] R 7 and / or R 11 are linked to R 6 and / or R 12 to form an unsubstituted or substituted ring structure;

[0215] R 22 denotes unsubstituted or substituted aryl having 6 to 18 ring carbon atoms; or unsubstituted or substituted alkyl having 1 to 20 carbon atoms.

[0216] In further preferred embodiments, 0, 1, 2, 3, 4, 5, 6, 7 or 8, preferably 0, 1, 2, 3, 4, 5 or 6, of the residues R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 are not hydrogen; i.e. the remaining residues are hydrogen. Further preferably, 0, 1, 2, 3, 4, 5, 6, 7 or 8, preferably 0, 1, 2, 3, 4, 5 or 6, of the residues R 2 , R 5 , R 9 , R12 13 14 15 18 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 of R, R, R, R, R, R, R and R are not hydrogen; i.e. the remaining residues are hydrogen.

[0217] In a preferred embodiment, the heterocyclic compound according to the application is represented by one of the following formulae

[0218]

[0219] wherein the residues are defined as described above,

[0220] wherein

[0221] - in formula (VA) and formula (VB) -

[0222] two adjacent residues R, R, R, R, R, R, R and / or R 1 2 3 4 5 8 9 10 11 12 13 14 15 16 17 18 19 may together form an unsubstituted or substituted ring structure;

[0223] - in formula (VC) -

[0224] two adjacent residues R, R, R, R, R, R, R and / or R 1 2 3 4 5 6 7 8 9 10 13 14 15 16 two adjacent residues R, R, R, R, R, R, R and / or R​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​R 17 R 18 R 19 may together form an unsubstituted or substituted ring structure.

[0225] More preferably, the heterocyclic compound according to the application is represented by one of the following formulae

[0226]

[0227] wherein the residues are defined as described above,

[0228] wherein

[0229] - in formula (VAa) and formula (VBa) -

[0230] two adjacent residues R 12 R 13 R 14 and / or R 15 may together form an unsubstituted or substituted ring structure;

[0231] - in formula (VCa) -

[0232] two adjacent residues R 13 R 14 and / or R 15 may together form an unsubstituted or substituted ring structure.

[0233] In a preferred embodiment, the heterocyclic compound according to the application is represented by formula (VA), wherein two adjacent residues R 1 R 2 and / or R 3 and / or two adjacent residues R 16 R 17 R 18 and / or R 19 together form an unsubstituted or substituted ring structure.

[0234] In a preferred embodiment, the heterocyclic compound according to the application is represented by formula (VA), wherein R 1 to R 3 and / or R 16 to R 19 represents an unsubstituted or substituted aryl having 6 to 60 ring carbon atoms; an unsubstituted or substituted heteroaryl having 5 to 60 ring atoms; an unsubstituted or substituted alkyl having 1 to 20 carbon atoms; an unsubstituted or substituted haloalkyl having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl having 3 to 20 ring carbon atoms; CN; N(R 22 )2; OR 20 ; SR 20 ; B(R21 )2; SiR 24 R 25 R 26 or halogen;

[0235] and R 4 to R 5 and / or R 12 to R 15 at least one of R 22 to R 20 ; SR 20 ; B(R 21 )2; SiR 24 R 25 R 26 or halogen.

[0236] In a further preferred embodiment, the heterocyclic compound according to the application is represented by formula (VA), wherein at least one of R 1 to R 3 , and at least one of R 16 to R 19 , and at least one of R 4 to R 5 , and at least one of R 12 to R 15 represents an unsubstituted or substituted aryl having 6 to 60 ring carbon atoms; an unsubstituted or substituted heteroaryl having 5 to 60 ring atoms; an unsubstituted or substituted alkyl having 1 to 20 carbon atoms; an unsubstituted or substituted haloalkyl having 1 to 20 carbon atoms; an unsubstituted or substituted cycloalkyl 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 halogen.

[0237] In a preferred embodiment, the heterocyclic compound according to the application is represented by formula (VA), wherein R 9unsubstituted or substituted heteroaryl having 5 to 60 ring atoms; unsubstituted or substituted alkyl having 1 to 20 carbon atoms; unsubstituted or substituted haloalkyl having 1 to 20 carbon atoms; unsubstituted or substituted cycloalkyl 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 halogen;

[0238] and at least one of R 12 to R 15 represents unsubstituted or substituted aryl having 6 to 60 ring carbon atoms; unsubstituted or substituted heteroaryl having 5 to 60 ring atoms; unsubstituted or substituted alkyl having 1 to 20 carbon atoms; unsubstituted or substituted haloalkyl having 1 to 20 carbon atoms; unsubstituted or substituted cycloalkyl 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 halogen.

[0239] In a preferred embodiment, the heterocyclic compounds according to the application are represented by formula (VC), wherein at least one of R 4 to R 6 , R 13 to R 15 represents unsubstituted or substituted aryl having 6 to 60 ring carbon atoms; unsubstituted or substituted heteroaryl having 5 to 60 ring atoms; unsubstituted or substituted alkyl having 1 to 20 carbon atoms; unsubstituted or substituted haloalkyl having 1 to 20 carbon atoms; unsubstituted or substituted cycloalkyl 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 halogen.

[0240] In a preferred embodiment, the heterocyclic compounds according to the application are represented by formula (VC) or (VB), wherein the residues R 4 , R 5 , R 6 , R 12 , R13 R1is C1-C4alkyl, C3-C6cycloalkyl or C6-C10aryl, preferably C1-C4alkyl, C5-C6cycloalkyl or phenyl, more preferably tert-butyl. 14 R2is C1-C4alkyl, C3-C6cycloalkyl or C6-C10aryl, preferably C1-C4alkyl, C5-C6cycloalkyl or phenyl, more preferably tert-butyl. 15 R3is C1-C4alkyl, C3-C6cycloalkyl or C6-C10aryl, preferably C1-C4alkyl, C5-C6cycloalkyl or phenyl, more preferably tert-butyl. 10 R4is C1-C4alkyl, C3-C6cycloalkyl or C6-C10aryl, preferably C1-C4alkyl, C5-C6cycloalkyl or phenyl, more preferably tert-butyl. 12 R5is C1-C4alkyl, C3-C6cycloalkyl or C6-C10aryl, preferably C1-C4alkyl, C5-C6cycloalkyl or phenyl, more preferably tert-butyl. 10 R6is C1-C4alkyl, C3-C6cycloalkyl or C6-C10aryl, preferably C1-C4alkyl, C5-C6cycloalkyl or phenyl, more preferably tert-butyl. 10 R7is C1-C4alkyl, C3-C6cycloalkyl or C6-C10aryl, preferably C1-C4alkyl, C5-C6cycloalkyl or phenyl, more preferably tert-butyl.

[0241] Examples of compounds of formula (I) are given below:

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260] Preparation of compounds of formula (I)

[0261] The compounds of formula (I) can be synthesized according to the reactions carried out in the examples of the present application, and by using alternative reactions or starting materials analogous to those known in the art and suitable to the intended product.

[0262] The compounds of formula (I) are prepared, for example, by the following steps:

[0263] (i) adding BHal3 to the intermediate (II), thereby obtaining the compound of formula (I):

[0264]

[0265] wherein

[0266] Hal denotes halogen, preferably F, CI, Br or I, more preferably CI or Br, most preferably Br;

[0267] R denotes Ci-C8alkyl or C6-C 10 aryl, preferably Ci-C4alkyl or phenyl, more preferably methyl; and

[0268] all other residues and indices are as defined above.

[0269] Suitable reaction conditions are mentioned in the examples of the present application.

[0270] The intermediate (II) is prepared, for example, starting from a compound of formula (III)

[0271]

[0272] and

[0273] (i) reacting Hal2 of compound (III) with an amino compound (IVa) which can be further modified after the reaction with compound (III), or with an amino compound (IVb), and

[0274] (ii) reacting Hal1 of compound (III) with a carbazole derivative (V),

[0275] wherein

[0276] Hal1 denotes halogen, preferably CI,

[0277] Hal2 denotes halogen, preferably Br,

[0278] R denotes Ci-C8alkyl or C6-C 10 aryl, preferably Ci-C4alkyl or phenyl, more preferably methyl; and

[0279] all other residues and indices are as defined above.

[0280] Generally, step (i) is performed first, followed by step (ii).

[0281]

[0282] which can be modified as follows: wherein the dotted line is the bonding site of the compound of formula (III) at the position of Hal2.

[0283]

[0284] wherein X' is a direct bond (i.e. R E and ring A1 is connected by a direct bond, O, S, NR 23 , SiR 24 R 25 , CR 27 R 28 or BR 21 , preferably a direct bond;

[0285]

[0286] wherein all residues and indices are defined as above.

[0287] Preferred compounds of formula (V) are prepared, for example, by the following steps:

[0288] (i) adding BHal3 to intermediate (VI), thereby obtaining a compound of formula (V):

[0289]

[0290] wherein

[0291] Hal represents halogen, preferably F, CI, Br or I, more preferably CI or Br, most preferably Br;

[0292] R represents C1-C8 alkyl or C6-C 10 aryl, preferably C1-C4 alkyl or phenyl, more preferably methyl; and

[0293] all other residues and indices are defined as above.

[0294] Intermediate (VI) is prepared, for example, starting from a compound of formula (VII)

[0295]

[0296] and

[0297] (i) reacting Hal2of compound (VII) with an amino compound (Villa) which can be further modified after reaction with compound (VII), or with an amino compound (Vlllb) and

[0298] (ii) reacting Hal1of compound (VII) with a carbazole derivative (IX),

[0299] wherein

[0300] Hal1represents halogen, preferably CI,

[0301] Hal2represents halogen, preferably Br,

[0302] R represents CrC8alkyl or C6-C 10 aryl, preferably CrC4alkyl or phenyl, more preferably methyl; and

[0303] all other residues and indices are defined as above.

[0304] Generally, step (i) is performed first, followed by step (ii).

[0305]

[0306] which can be modified as follows: wherein the dotted line is the bonding site of the compound of formula (VII) at the position of Hal2.

[0307]

[0308] wherein all residues and indices are defined as above.

[0309] In a further embodiment, the compound of formula (I) is prepared, for example, as follows:

[0310] ia) adding BHal3to intermediate (Ha), thereby obtaining a compound of formula (I):

[0311]

[0312] wherein

[0313] Hal represents halogen, preferably F, CI, Br or I, more preferably CI or Br, most preferably Br;

[0314] and

[0315] all other residues and indices are defined as above.

[0316] Suitable reaction conditions are mentioned in the examples of the present application.

[0317] The intermediates (IIa) are prepared, for example, starting from compounds of the formula (IIIa)

[0318]

[0319] and

[0320] (i) reacting Hal2of compound (IIIa) with an amino compound (IVa) which can be further modified after the reaction with compound (IIIa), or with an amino compound (IVb), and

[0321] (ii) reacting Hal1of compound (IIIa) with a carbazole derivative (V),

[0322] wherein

[0323] Hal1denotes halogen, preferably CI,

[0324] Hal2denotes halogen, preferably Br,

[0325] all other residues and indices are defined as above.

[0326] Generally, step (i) is carried out first, followed by step (ii).

[0327]

[0328] which can be modified as follows: wherein the dotted line is the bonding site of the compound of the formula (III) at the position of Hal2.

[0329]

[0330] wherein X’ is a direct bond (i.e. R E and ring A1is connected by a direct bond), O, S, NR 23 , SiR 24 R 25 , CR 27 R 28 or BR 21 , preferably a direct bond;

[0331]

[0332] wherein all residues and indices are defined as above.

[0333] Preferred compounds of the formula (Va) are prepared, for example, by the following steps:

[0334] Ia) adding BHal3to the intermediate (Via), thereby obtaining a compound of the formula (Va):

[0335]

[0336] wherein

[0337] Hal denotes halogen, preferably F, CI, Br or I, more preferably CI or Br, most preferably Br;

[0338] R 5 denotes CrC 10 alkyl, C3-C 12 cycloalkyl or C6-C 10 aryl, preferably CrC4alkyl, C5-C 10 cycloalkyl or phenyl, more preferably tert-butyl; and

[0339] all other residues and indices are defined as above.

[0340] The intermediates (Via) are prepared, for example, starting from compounds of the formula (Vila)

[0341]

[0342] and

[0343] (i) reacting Hal2of compound (Vila) with an amino compound (Villa), which can be further modified after the reaction with compound (Vila), or with an amino compound (Vlllb), and

[0344] (ii) reacting Hal1of compound (Vila) with a carbazole derivative (IX),

[0345] wherein

[0346] Hal1denotes halogen, preferably CI,

[0347] Hal2denotes halogen, preferably Br,

[0348] R 5 denotes CrC 10 alkyl, C3-C 12 cycloalkyl or C6-C 10 aryl, preferably CrC4alkyl, C5-C 10 cycloalkyl or phenyl, more preferably tert-butyl; and

[0349] all other residues and indices are defined as above.

[0350] Generally, step (i) is carried out first, followed by step (ii).

[0351]

[0352] which can be modified as follows: wherein the dotted line is the bonding site of the compound of formula (Vila) at the position of Hal2.

[0353]

[0354] wherein all residues and indices are defined as above.

[0355] Examples of suitable preparation methods are described below.

[0356] Organic electroluminescent device

[0357] According to one aspect of the present application, there is provided a material for an organic electroluminescent device comprising at least one compound of formula (I).

[0358] According to another aspect of the present application, there is provided an organic electroluminescent device comprising at least one compound of formula (I).

[0359] According to another aspect of the present application, there is provided an organic electroluminescent device comprising a cathode, an anode and one or more organic thin film layers, said organic thin film layers comprising an emission layer disposed between the cathode and the anode, wherein at least one of the organic thin film layers comprises at least one compound of formula (I).

[0360] According to another aspect of the present application, there is provided an organic electroluminescent device, wherein the emission layer comprises at least one compound of formula (I).

[0361] According to another aspect of the present application, there is provided an organic electroluminescent device, wherein the emission layer comprises at least one compound of formula (I) as a dopant material and an anthracene compound as a host material.

[0362] According to another aspect of the present application, there is provided an electronic device provided with an organic electroluminescent device according to the present application.

[0363] According to another aspect of the present application, there is provided an emitter material comprising at least one compound of formula (I).

[0364] According to another aspect of the present application, there is provided an emission layer comprising at least one host and at least one dopant, wherein the dopant comprises at least one compound of formula (I).

[0365] According to another aspect of the present application, there is provided the use of a compound of formula (I) according to the present application in an organic electroluminescent device.

[0366] In one embodiment, the organic EL device comprises a hole transport layer between the anode and the emission layer.

[0367] ​In one embodiment, the organic EL device includes an electron transport layer between the cathode and the light-emitting layer.

[0368] In the present specification, with respect to "one or more organic thin film layers between the light-emitting layer and the anode", if there is only one organic layer between the light-emitting layer and the anode, it refers to the layer, and if there are a plurality of organic layers, it refers to at least one of the layers. For example, if there are two or more organic layers between the light-emitting layer and the anode, the organic layer closer to the light-emitting layer is referred to as a "hole transport layer", and the organic layer closer to the anode is referred to as a "hole injection layer". Each of the "hole transport layer" and the "hole injection layer" can be a single layer or can be formed of two or more layers. One of these layers can be a single layer, and the other layer(s) can be formed of two or more layers.

[0369] Similarly, with respect to "one or more organic thin film layers between the light-emitting layer and the cathode", if there is only one organic layer between the light-emitting layer and the cathode, it refers to the layer, and if there are a plurality of organic layers, it refers to at least one of the layers. For example, if there are two or more organic layers between the light-emitting layer and the cathode, the organic layer closer to the light-emitting layer is referred to as an "electron transport layer", and the organic layer closer to the cathode is referred to as an "electron injection layer". Each of the "electron transport layer" and the "electron injection layer" can be a single layer or can be formed of two or more layers. One of these layers can be a single layer, and the other layer(s) can be formed of two or more layers.

[0370] The above "one or more organic thin film layers including the light-emitting layer", preferably the light-emitting layer, contains a compound represented by formula (I). The compound represented by formula (I) is preferably used as a light-emitting material, more preferably as a fluorescent light-emitting material, and most preferably as a blue fluorescent light-emitting material. By the presence of the compound of formula (I) in the organic EL device, preferably in the light-emitting layer, an organic EL device characterized by high external quantum efficiency (EQE) and long lifetime is provided.

[0371] According to another aspect of the present application, there is provided a light-emitting layer of an organic electroluminescent device, which contains at least one compound of formula (I).

[0372] Preferably, the light-emitting layer contains at least one light-emitting material (dopant material) and at least one host material, wherein the light-emitting material is at least one compound of formula (I).

[0373] In one embodiment, the host is not selected from CBP (4,4'-bis-(N-carbazolyl)- biphenyl), mCP, mCBPSif87 (dibenzo[b,d]thiophene-2-yltriphenylsilane), CzSi, Sif88 (dibenzo[b,d]thiophen-2-yl)diphenylsilane), DPEPO (bis[2-(diphenylphosphino)phenyl]ether oxide), 9-[3-(dibenzo furan-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzo furan-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzo thiophen-2-yl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzo furan)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzo thiophen)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'-spirobifluorene-2-yl)-1,3,5-triazine).

[0374] Preferred host materials are substituted or unsubstituted polycyclic aromatic hydrocarbon (PAH) compounds, substituted or unsubstituted polyheteroaromatic compounds, substituted or unsubstituted anthracene compounds, or substituted or unsubstituted pyrene compounds.

[0375] More preferably, the organic electroluminescent device according to the present application comprises in the emission layer at least one compound of formula (I) as dopant material and at least one host material selected from substituted or unsubstituted polycyclic aromatic hydrocarbon (PAH) compounds, substituted or unsubstituted polyheteroaromatic compounds, substituted or unsubstituted anthracene compounds, and substituted or unsubstituted pyrene compounds. Preferably, the at least one host is at least one substituted or unsubstituted anthracene compound.

[0376] In another preferred embodiment, the organic electroluminescent device according to the present application comprises in the emission layer at least one compound of formula (I) as dopant material and at least one host material selected from substituted or unsubstituted polycyclic aromatic hydrocarbon (PAH) compounds, substituted or unsubstituted anthracene compounds, and substituted or unsubstituted pyrene compounds. Preferably, the at least one host is at least one substituted or unsubstituted anthracene compound.

[0377] According to another aspect of the present application, there is provided an emission layer of an organic electroluminescent device comprising at least one compound of formula (I) as dopant material and an anthracene compound as host material.

[0378] Suitable anthracene compounds are represented by the following formula (10):

[0379]

[0380] wherein

[0381] one or more pairs of two or more adjacent R 101 to R 110 may form a substituted or unsubstituted, saturated or unsaturated ring;

[0382] R 101 to R 110 independently a hydrogen atom, a substituted or unsubstituted alkyl group including 1 to 50 carbon atoms, a substituted or unsubstituted haloalkyl group including 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group including 2 to 50 carbon atoms, a substituted or unsubstituted alkynyl group including 2 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group including 3 to 50 ring carbon atoms, a substituted or unsubstituted alkoxy group including 1 to 50 carbon atoms, a substituted or unsubstituted alkylene group including 1 to 50 carbon atoms, a substituted or unsubstituted aryloxy group including 6 to 50 ring carbon atoms, a substituted or unsubstituted arylthio group including 6 to 50 ring carbon atoms, a substituted or unsubstituted aralkyl group including 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 including 6 to 50 ring carbon atoms, an unsubstituted or unsubstituted monovalent heterocyclic group including 5 to 50 ring atoms, or a group represented by the following formula (31);

[0383] R 121 -R 127 independently a hydrogen atom, a substituted or unsubstituted alkyl group including 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group including 3 to 50 ring carbon atoms, a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms, or a substituted or unsubstituted monovalent heterocyclic group including 5 to 50 ring atoms; when each of R 121 to R 127 is present in plural, each of the plural R 121 to R 127 may be the same or different;

[0384] provided that R 101 -R 110At least one of them is a group represented by formula (31). If there are two or more groups represented by formula (31), each of these groups may be the same or different;

[0385]

[0386] In equation (31),

[0387] L 101 It is a single-bonded, substituted or unsubstituted aryl group containing 6 to 30 ring carbon atoms or a substituted or unsubstituted divalent heterocyclic group containing 5 to 30 ring atoms;

[0388] Ar 101 It is an aryl group containing 6 to 50 ring carbon atoms, substituted or unsubstituted, or a monovalent heterocyclic group containing 5 to 50 ring atoms.

[0389] The specific examples of each substituent, "substituted or unsubstituted" substituent, and halogen atom in compound (10) are the same as those described above.

[0390] This will explain "one or more pairs of two or more adjacent R" 101 -R 110 It can form substituted or unsubstituted, saturated or unsaturated rings.

[0391] "A pair of two or more adjacent R" 101 -R 110 "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 and R 103 Combinations of, etc.

[0392] The substituents in “substituted or unsubstituted” of “saturated or unsaturated ring” are the same as those in “substituted or unsubstituted” mentioned in formula (10).

[0393] "Saturated or unsaturated cycle" refers to the condition where R... 101 and R 102 When forming a ring, for example, by R 101 Bonded carbon atoms, and R 102a ring formed by the carbon atom bonded to R 101 and R 102 form a ring when the carbon atom bonded to R 101 the carbon atom bonded to R 102 form an unsaturated ring. The ring formed by R 101 and R 102 is a benzene ring.

[0394] The "arbitrary element" is preferably a C element, a N element, an O element, or an S element. In the arbitrary element (e.g., a C element or a N element), the atomic bond not forming a ring can be capped with a hydrogen atom or the like.

[0395] The "one or more arbitrary elements" are preferably 2 or more and 15 or less, more preferably 3 or more and 12 or less, and further preferably 3 or more and 5 or less.

[0396] For example, R 101 and R 102 may form a ring, and R 105 and R 106 may form a ring. In this case, the compound represented by formula (10) is a compound represented by the following formula (10A), for example:

[0397] .

[0398] In one embodiment, R 101 to R 110 are independently a hydrogen atom, a substituted or unsubstituted alkyl group including 1 to 50 carbon atoms, a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group including 5 to 50 ring atoms, or a group represented by formula (31).

[0399] Preferably, R 101 to R 110 are independently a hydrogen atom, a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group including 5 to 50 ring atoms, or a group represented by formula (31).

[0400] More preferably, R 101 to R 110 are independently a hydrogen atom, a substituted or unsubstituted aryl group including 6 to 18 ring carbon atoms, a substituted or unsubstituted heterocyclic group including 5 to 18 ring atoms, or a group represented by formula (31).

[0401] Most preferably, at least one of R 109 and R 110 is a group represented by formula (31).

[0402] Further most preferably, R 109 and R 110 independently are a group represented by formula (31).

[0403] In one embodiment, the compound (10) is a compound represented by the following formula (10-1):

[0404]

[0405] wherein, in formula (10-1), R 101 to R 108 , L 101 and Ar 101 are as defined in formula (10).

[0406] In one embodiment, the compound (10) is a compound represented by the following formula (10-2):

[0407]

[0408] wherein, in formula (10-2), R 101 , R 103 to R 108 , L 101 and Ar 101 are as defined in formula (10).

[0409] In one embodiment, the compound (10) is a compound represented by the following formula (10-3):

[0410]

[0411] wherein, in formula (10-3),

[0412] R 101A to R 108A independently are a hydrogen atom or a substituted or unsubstituted aryl group containing 6 to 50 ring carbon atoms;

[0413] L 101A is a single bond or a substituted or unsubstituted arylene group containing 6 to 30 ring carbon atoms, and two L 101A may be the same or different;

[0414] Ar 101A is a substituted or unsubstituted aryl group containing 6 to 50 ring carbon atoms, and two Ar 101A may be the same or different.

[0415] In one embodiment, the compound (10) is a compound represented by the following formula (10-4):

[0416]

[0417] In equation (10-4),

[0418] L 101 and Ar 101 As defined in equation (10);

[0419] R 101A To R 108A An aryl group consisting of 6 to 50 cyclic carbon atoms, which is independently composed of hydrogen atoms or substituted or unsubstituted.

[0420] X 11 For O, S or N(R) 61 );

[0421] R 61 It is a hydrogen atom, a substituted or unsubstituted alkyl group containing 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group containing 6 to 50 cyclic carbon atoms;

[0422] R 62 To R 69 One of them is with L 101 Bonded atomic bonds;

[0423] Not with L 101 A bonded pair or more adjacent R 62 -R 69 They can bond with each other to form substituted or unsubstituted, saturated or unsaturated rings; and

[0424] Not with L 101 R bonded and not forming substituted or unsubstituted, saturated or unsaturated rings 62 To R 69 Independently a hydrogen atom, or 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] In one embodiment, compound (10) is a compound represented by the following formula (10-4A):

[0426]

[0427] In equation (10-4A),

[0428] L 101 and Ar 101 As defined in equation (10);

[0429] R 101A To R 108A An aryl group consisting of 6 to 50 cyclic carbon atoms, which is independently composed of hydrogen atoms or substituted or unsubstituted.

[0430] X 11 is O, S, or N(R 61 );

[0431] R 61 is a hydrogen atom, a substituted or unsubstituted alkyl group including 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms;

[0432] one or more pairs of adjacent two or more R 62A to R 69A may form a substituted or unsubstituted, saturated or unsaturated ring, and adjacent two R 62A to R 69A form a ring represented by the following formula (10-4A-1); and

[0433] R 62A to R 69A are independently a hydrogen atom, a substituted or unsubstituted alkyl group including 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms.

[0434]

[0435] wherein in the formula (10-4A-1),

[0436] each of the two atomic bonds is bonded to two of R 62A to R 69A ;

[0437] one of R 70 to R 73 is an atomic bond bonded to L 101 ; and

[0438] R 101 to R 70 to R 73 are independently a hydrogen atom, a substituted or unsubstituted alkyl group including 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms.

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

[0440]

[0441] wherein in the formula (10-6),

[0442] L 101 and Ar 101 are as defined in the formula (10);

[0443] R 101Ato R 108A as defined in formula (10-4);

[0444] R 66 to R 69 as defined in formula (10-4); and

[0445] X 12 is O or S.

[0446] In one embodiment, the compound represented by formula (10-6) is a compound represented by the following formula (10-6H):

[0447]

[0448] wherein in formula (10-6H),

[0449] L 101 and Ar 101 as defined in formula (10);

[0450] R 66 to R 69 as defined in formula (10-4); and

[0451] X 12 is O or S.

[0452] In one embodiment, the compound represented by formula (10-6) and (10-6H) is a compound represented by the following formula (10-6Ha):

[0453]

[0454] wherein in formula (10-6Ha),

[0455] L 101 and Ar 101 as defined in formula (10); and

[0456] X 12 is O or S.

[0457] In one embodiment, the compound represented by formula (10-6), (10-6H) and (10-6Ha) is a compound represented by the following formula (10-6Ha-1) or (10-6Ha-2):

[0458]

[0459] wherein in formula (10-6Ha-1) and (10-6Ha-2),

[0460] L 101 and Ar101 as defined in formula (10); and

[0461] X 12 is O or S.

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

[0463]

[0464] wherein, in formula (10-7),

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

[0466] R 101A to R 108A as defined in formula (10-4);

[0467] X 11 as defined in formula (10-4); and

[0468] R 62 to R 69 as defined in formula (10-4), provided that R 66 and R 67 , R 67 and R 68 , and R 68 and R 69 any one pair of which are bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring.

[0469] In one embodiment, the compound (10) is a compound represented by the following formula (10-7H):

[0470]

[0471] wherein, in formula (10-7H),

[0472] L 101 and Ar 101 as defined in formula (10);

[0473] X 11 as defined in formula (10-4); and

[0474] R 62 to R 69 as defined in formula (10-4), provided that R 66 and R 67 , R 67 and R 68 , and R 68 and R69 Any pair of rings can bond to each other to form substituted or unsubstituted saturated or unsaturated rings.

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

[0476]

[0477] In equation (10-8),

[0478] L 101 and Ar 101 As defined in equation (10);

[0479] R 101A To R 108A As defined in equation (10-4);

[0480] X 12 For O or S; and

[0481] R 66 To R 69 As defined in equation (10-4), the condition is R. 66 and R 67 R 67 and R 68 and R 68 and R 69 Any pair can bond to each other to form a substituted or unsubstituted saturated or unsaturated ring.

[0482] In one embodiment, the compound represented by formula (10-8) is a compound represented by formula (10-8H):

[0483]

[0484] In equation (10-8H), L 101 and Ar 101 As defined in equation (10).

[0485] R 66 To R 69 As defined in equation (10-4), the condition is R. 66 and R 67 R 67 and R 68 and R 68 and R 69 Any pair can bond to each other to form a substituted or unsubstituted saturated or unsaturated ring. R 66 and R 67 R 67 and R 68 and R 68 and Rany one pair of R 69 and R 12 may be preferably bonded to each other to form an unsubstituted benzene ring; and

[0486] X 12 is O or S.

[0487] In one embodiment, for the compound represented by formula (10-7), (10-8), or (10-8H), R 66 and R 67 , R 67 and R 68 , and R 68 and R 69 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group including 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms. 66 to R 69 do not form a substituted or unsubstituted saturated or unsaturated ring.

[0488]

[0489] wherein, in formulae (10-8-1) and (10-8-2),

[0490] two atoms are independently bonded to one pair of R 66 and R 67 , R 67 and R 68 , or R 68 and R 69 ;

[0491] R 80 to R 83 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group including 1 to 50 carbon atoms, or a substituted or unsubstituted aryl group including 6 to 50 ring carbon atoms.

[0492] X 13 is O or S.

[0493] In one embodiment, the compound (10) is a compound represented by the following formula (10-9):

[0494]

[0495] wherein, in formula (10-9),

[0496] L 101 and Ar 101 are as defined in formula (10);

[0497] R 101A to R 108A are as defined in formula (10-4);

[0498] R 66 to R 69 as defined in formula (10-4), provided that R 66 and R 67 , R 67 and R 68 , and R 68 and R 69 are not bonded to each other and do not form a substituted or unsubstituted saturated or unsaturated ring; and

[0499] X 12 is O or S.

[0500] In one embodiment, the compound (10) is selected from the group consisting of compounds represented by the following formulae (10-10-1) to (10-10-4).

[0501]

[0502]

[0503] In formulae (10-10-1H) to (10-10-4H), L 101A and Ar 101A are as defined in formula (10-3).

[0504] For the compound represented by formula (10), the following compounds can be given as specific examples.

[0505]

[0506]

[0507]

[0508]

[0509]

[0510]

[0511]

[0512]

[0513]

[0514]

[0515]

[0516]

[0517]

[0518]

[0519]

[0520]

[0521]

[0522]

[0523]

[0524]

[0525]

[0526]

[0527] In the case where the light-emitting layer contains the compound represented by Formula (I) as a dopant and at least one host, the content of the at least one compound represented by Formula (I) is preferably 0.5 to 70% by mass, more preferably 0.5 to 30% by mass, further preferably 1 to 30% by mass, more further preferably 1 to 20% by mass, particularly preferably 1 to 10% by mass, further particularly preferably 1 to 5% by mass, with respect to the total mass of the light-emitting layer, with the preferred host being as described above, and the host being more preferably at least one compound represented by Formula (10).

[0528] The content of the at least one host (with the preferred host being as described above, preferably at least one compound represented by Formula (10)) is preferably 30 to 99.9% by mass, more preferably 70 to 99.5% by mass, further preferably 70 to 99% by mass, more further preferably 80 to 99% by mass, particularly preferably 90 to 99% by mass, further particularly preferably 95 to 99% by mass, with respect to the total mass of the light-emitting layer.

[0529] The layer structure of the organic EL device according to one aspect of the present application will be explained.

[0530] An organic EL device according to one aspect of the present application includes a cathode, an anode, and one or more organic thin film layers including an emission layer disposed between the cathode and the anode. The organic layer includes at least one layer composed of an organic compound. Alternatively, the organic layer is formed by layering a plurality of layers composed of an organic compound. The organic layer can contain an inorganic compound in addition to the organic compound.

[0531] The at least one organic layer is an emission layer. The organic layer can constitute, for example, a single emission layer, or can include other layers that can be employed in the layer structure of the organic EL device. The layers that can be employed in the layer structure of the organic EL device are not particularly limited, but examples thereof include a hole transport zone (including at least one hole transport layer, and preferably further including at least one of a hole injection layer, an electron blocking layer, an exciton blocking layer, and the like), an emission layer, a spacer layer, and an electron transport zone (including at least one electron transport layer, and preferably further including at least one of an electron injection layer, a hole blocking layer, and the like) disposed between the cathode and the emission layer.

[0532] The organic EL device according to one aspect of the present application can be, for example, a fluorescent or phosphorescent single-color light emitting device or a fluorescent / phosphorescent hybrid white light emitting device. Preferably, the organic EL device is a fluorescent single-color light emitting device, more preferably a blue fluorescent single-color light emitting device or a fluorescent / phosphorescent hybrid white light emitting device. Blue fluorescence refers to fluorescence at 400 to 500 nm (maximum peak), preferably at 430 nm to 490 nm (maximum peak).

[0533] Further, it can be a simple type device having a single light emitting unit or a series type device having a plurality of light emitting units.

[0534] The "light emitting unit" in the present specification is the smallest unit including an organic layer, in which at least one organic layer is an emission layer, and emits light by recombination of injected holes and electrons.

[0535] Further, the "emission layer" described in the present specification is an organic layer having an emission function. The emission layer is, for example, a phosphorescent emission layer, a fluorescent emission layer, or the like, preferably a fluorescent emission layer, more preferably a blue fluorescent emission layer, and can be a single layer or a stack of multiple layers.

[0536] The light emitting unit can be a stack type unit having a plurality of phosphorescent emission layers or fluorescent emission layers. In this case, for example, a spacer layer for preventing excitons generated in the phosphorescent emission layer from diffusing into the fluorescent emission layer can be disposed between the respective emission layers.

[0537] As a simple type organic EL device, a device structure such as anode / light emitting unit / cathode can be given.

[0538] Examples of representative layer structures of the light-emitting unit are shown below. Layers in parentheses are optionally provided.

[0539] (a) (hole injection layer) / hole transport layer / fluorescent light-emitting layer / (electron transport layer / electron injection layer)

[0540] (b) (hole injection layer) / hole transport layer / phosphorescent light-emitting layer / (electron transport layer / electron injection layer)

[0541] (c) (hole injection layer) / hole transport layer / first fluorescent light-emitting layer / second fluorescent light-emitting layer / (electron transport layer / electron injection layer)

[0542] (d) (hole injection layer) / hole transport layer / first phosphorescent layer / second phosphorescent layer / (electron transport layer / electron injection layer)

[0543] (e) (hole injection layer) / hole transport layer / phosphorescent light-emitting layer / spacer layer / fluorescent light-emitting layer / (electron transport layer / electron injection layer)

[0544] (f) (hole injection layer) / hole transport layer / first phosphorescent light-emitting layer / second phosphorescent light-emitting layer / spacer layer / fluorescent light-emitting layer / (electron transport layer / electron injection layer)

[0545] (g) (hole injection layer) / hole transport layer / first phosphorescent layer / spacer layer / second phosphorescent light-emitting layer / spacer layer / fluorescent light-emitting layer / (electron transport layer / electron injection layer)

[0546] (h) (hole injection layer) / hole transport layer / phosphorescent light-emitting layer / spacer layer / first fluorescent light-emitting layer / second fluorescent light-emitting layer / (electron transport layer / electron injection layer)

[0547] (i) (hole injection layer) / hole transport layer / electron blocking layer / fluorescent light-emitting layer / (electron transport layer / electron injection layer)

[0548] (j) (hole injection layer) / hole transport layer / electron blocking layer / phosphorescent light-emitting layer / (electron transport layer / electron injection layer)

[0549] (k) (hole injection layer) / hole transport layer / exciton blocking layer / fluorescent light-emitting layer / (electron transport layer / electron injection layer)

[0550] (l) (hole injection layer) / hole transport layer / exciton blocking layer / phosphorescent light-emitting layer / (electron transport layer / electron injection layer)

[0551] (m) (hole injection layer) / first hole transport layer / second hole transport layer / fluorescent light-emitting layer / (electron transport layer / electron injection layer)

[0552] (n) (hole injection layer / ) first hole transport layer / second hole transport layer / fluorescent light emitting layer ( / first electron transport layer / second electron transport layer / electron injection layer)

[0553] (o) (hole injection layer / ) first hole transport layer / second hole transport layer / phosphorescent light emitting layer ( / electron transport layer / electron injection layer)

[0554] (p) (hole injection layer / ) first hole transport layer / second hole transport layer / phosphorescent light emitting layer ( / first electron transport layer / second electron transport layer / electron injection layer)

[0555] (q) (hole injection layer / ) hole transport layer / fluorescent light emitting layer / hole blocking layer ( / electron transport layer / electron injection layer)

[0556] (r) (hole injection layer / ) hole transport layer / phosphorescent light emitting layer / hole blocking layer ( / electron transport layer / electron injection layer)

[0557] (s) (hole injection layer / ) hole transport layer / fluorescent light emitting layer / exciton blocking layer ( / electron transport layer / electron injection layer)

[0558] (t) (hole injection layer / ) hole transport layer / phosphorescent light emitting layer / exciton blocking layer ( / electron transport layer / electron injection layer).

[0559] The layer structure of the organic EL device according to one aspect of the present application is not limited to the above examples.

[0560] For example, when the organic EL device has a hole injection layer and a hole transport layer, it is preferable to provide the hole injection layer between the hole transport layer and the anode. Further, when the organic EL device has an electron injection layer and an electron transport layer, it is preferable to provide the electron injection layer between the electron transport layer and the cathode. Further, each of the hole injection layer, the hole transport layer, the electron transport layer, and the electron injection layer can be formed of a single layer or of multiple layers.

[0561] The plurality of phosphorescent light emitting layers, the plurality of phosphorescent light emitting layers, and the fluorescent light emitting layer can be light emitting layers that emit a plurality of different colors. For example, the light emitting unit (f) can include a hole transport layer / first phosphorescent layer (emitting red light) / second phosphorescent light emitting layer (emitting green light) / spacer layer / fluorescent light emitting layer (emitting blue light) / electron transport layer.

[0562] An electron blocking layer can be provided between each light emitting layer and the hole transport layer or the spacer layer. Further, a hole blocking layer can be provided between each light emitting layer and the electron transport layer. By providing the electron blocking layer or the hole blocking layer, electrons or holes can be confined in the light emitting layer, thereby increasing the probability of recombination of carriers in the light emitting layer and improving the light emitting efficiency.

[0563] As a representative device structure of a tandem type organic EL device, for example, a device structure such as anode / first light-emitting unit / intermediate layer / second light-emitting unit / cathode can be given.

[0564] The first light-emitting unit and the second light-emitting unit are, for example, independently selected from the above-described light-emitting units.

[0565] The intermediate layer is also generally referred to as an intermediate electrode, an intermediate conductive layer, a charge generation layer, an electron-accepting layer, a connecting layer, a connector layer, or an intermediate insulating layer. The intermediate layer is a layer that supplies electrons to the first light-emitting unit and holes to the second light-emitting unit, and can be formed of a known material.

[0566] Figure 1 A schematic structure of an example of an organic EL device of the present application is shown. The organic EL device 1 includes a substrate 2, an anode 3, a cathode 4, and a light-emitting unit 10 provided between the anode 3 and the cathode 4. The light-emitting unit 10 includes a light-emitting layer 5, which preferably contains a host material and a dopant. A hole injection and transport layer 6 or the like can be provided between the light-emitting layer 5 and the anode 3, and an electron injection layer 8 and an electron transport layer 7 or the like (an electron injection and transport unit 11) can be provided between the light-emitting layer 5 and the cathode 4, an electron blocking layer can be provided on the anode 3 side of the light-emitting layer 5, and a hole blocking layer can be provided on the cathode 4 side of the light-emitting layer 5, and due to such a structure, electrons or holes can be confined in the light-emitting layer 5, and thus the probability of generating an exciton in the light-emitting layer 5 can be increased.

[0567] Hereinafter, the function, material, and the like of each layer constituting the organic EL device described in the present specification will be explained.

[0568] (Substrate)

[0569] The substrate serves as a support of the organic EL device. The substrate is preferably optically transparent at a light transmittance of 50% or more in the visible light region of wavelengths of 400 to 700 nm, and a smooth substrate is preferable. Examples of the material of the substrate include soda lime glass, aluminosilicate glass, quartz glass, plastic, and the like. As the substrate, a flexible substrate can be used. The flexible substrate refers to a substrate that can be bent (flexible), and examples thereof include a plastic substrate and the like. Specific examples of the material for forming the plastic substrate include polycarbonate, polyallylate, polyether sulfone, polypropylene, polyester, polyfluoroethylene, polyvinyl chloride, polyimide, polyethylene naphthalate, and the like. In addition, an inorganic vapor deposition film can be used.

[0570] (Anode)

[0571] As the anode, for example, it is preferable to use a metal, an alloy, an electroconductive compound, a mixture thereof, or the like having a high work function (specifically, 4.0 eV or more). Specific examples of the anode material include indium oxide-tin oxide (ITO: indium tin oxide), indium oxide-tin oxide containing silicon or silicon oxide, indium oxide-zinc oxide, indium oxide containing tungsten oxide or zinc oxide, graphene, and the like. In addition, gold, silver, platinum, nickel, tungsten, chromium, molybdenum, iron, cobalt, copper, palladium, titanium, and nitrides of these metals (for example, titanium oxide) can also be used.

[0572] The anode is usually 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 in 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 in which 0.5 to 5 mass% of tungsten oxide or 0.1 to 1 mass% of zinc oxide is added to indium oxide.

[0573] As other methods of forming the anode, a vacuum deposition method, a coating method, an inkjet method, a spin coating method, and the like can be given. When silver paste or the like is used, a coating method, an inkjet method, or the like can be used.

[0574] The hole injection layer formed in contact with the anode is formed by using a material that allows easy hole injection regardless of the work function of the anode. Therefore, in the anode, ordinary electrode materials, for example, metals, alloys, electroconductive compounds, and mixtures thereof can be used. Specifically, materials having a small work function, for example, alkali metals such as lithium and cesium; alkaline earth metals such as calcium and strontium; alloys containing these metals (for example, magnesium-silver and aluminum-lithium); rare earth metals such as europium and ytterbium; and alloys containing rare earth metals.

[0575] (Hole transport layer) / (Hole injection layer)

[0576] The hole transport layer is an organic layer formed between the light-emitting layer and the anode, and has a function of transporting holes from the anode to the light-emitting layer. If the hole transport layer is composed of multiple layers, the organic layer closer to the anode can sometimes be defined as a hole injection layer. The hole injection layer has a function of efficiently injecting holes from the anode to the organic layer unit. The hole injection layer is usually used to stabilize the injection of holes from the anode to the hole transport layer, which is usually composed of an organic material. An organic material having good contact with the anode or an organic material having p-type doping is preferably used for the hole injection layer.

[0577] The p-doping is usually composed of one or more p-dopant materials and one or more host materials. The host material preferably has a shallower HOMO energy level, and the p-dopant preferably has a deeper LUMO energy level, in order to increase the carrier density of the layer. Specific examples of the p-dopant are the acceptor materials mentioned below. Suitable host materials are the hole transport materials mentioned below, preferably aromatic or heterocyclic amine compounds.

[0578] A high-planarity acceptor material or a fused aromatic hydrocarbon material or a fused heterocycle is preferably used as a p-dopant material for the hole injection layer.

[0579] Specific examples of the acceptor material 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; hexaazatriphenylene compounds having one or more electron-withdrawing groups, such as hexaazatriphenylene hexanitrile; aromatic hydrocarbon compounds having one or more electron-withdrawing groups; and arylboron compounds having one or more electron-withdrawing groups. Preferred p-dopants are quinone compounds having one or more electron-withdrawing groups, such as F4TCNQ and 1,2,3-tris[(cyano)(4-cyano-2,3,5,6-tetrafluorophenyl)methylene]cyclopropane.

[0580] The ratio of the p-type dopant to the matrix material is preferably less than 20% by mole, more preferably less than 10%, such as 1%, 3% or 5%.

[0581] The hole transport layer is generally used to efficiently inject and transport holes, and preferably uses an aromatic or heterocyclic amine compound.

[0582] Specific examples of the compound used for the hole transport layer are represented by the general formula (H),

[0583]

[0584] wherein

[0585] Ar1to Ar3each 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 ring atoms, preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group, a triphenylene group, a fluorenyl group, a spirobifluorenyl group, an indenofluorenyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl-substituted aryl group, a dibenzofuranyl-substituted aryl group, or a dibenzothiophenyl-substituted aryl group; two or more substituents selected from Ar1to Ar3may be bonded to each other to form a ring structure, such as a carbazole ring structure or an acridine ring structure.

[0586] Preferably, at least one of Ar1to Ar3has an additional aryl or heterocyclic amine substituent, more preferably Ar1has an additional arylamino substituent, in which case Ar1preferably represents a substituted or unsubstituted biphenylene group, a substituted or unsubstituted fluorenylene group. Specific examples of the hole transport material are

[0587]

[0588] and the like.

[0589] A second hole-transporting layer is preferably interposed between the first hole-transporting layer and the light-emitting layer to improve device performance by blocking excess electrons or excitons.

[0590] Specific examples of the second hole-transporting layer are the same as those of the first hole-transporting layer. It is preferable that the second hole-transporting layer have a higher triplet energy to block triplet excitons, particularly for phosphorescent devices, such as a bis-carbazole compound, a diphenylenyl amine compound, a fluorene amine compound, a carbazole-substituted arylamine compound, a dibenzofuran-substituted arylamine compound, and a dibenzothiophene-substituted arylamine compound.

[0591] (light-emitting layer)

[0592] The light-emitting layer is a layer containing a substance having high light-emitting properties (an emitter material or a dopant material). As the dopant material, various materials can be used. For example, a fluorescent compound (a fluorescent dopant), a phosphorescent compound (a phosphorescent dopant), or the like can be used. The fluorescent compound is a compound capable of emitting light from a singlet excited state, and a light-emitting layer containing a fluorescent compound is referred to as a fluorescent light-emitting layer. In addition, the phosphorescent compound is a compound capable of emitting light from a triplet excited state, and a light-emitting layer containing a phosphorescent compound is referred to as a phosphorescent light-emitting layer.

[0593] Preferably, the light-emitting layer in the organic EL device of the present application contains a compound of formula (I) as a dopant material.

[0594] The light-emitting layer preferably contains at least one dopant material and at least one host material that allows it to efficiently emit light. In some literature, the dopant material is referred to as a guest material, an emitter, or a light-emitting material. In some literature, the host material is referred to as a matrix material.

[0595] A single light-emitting layer can contain a plurality of dopant materials and a plurality of host materials. In addition, a plurality of light-emitting layers can be present.

[0596] In the present 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". Note that the fluorescent host and the phosphorescent host are not classified only by molecular structure. The phosphorescent host is a material for forming a phosphorescent light-emitting layer containing a phosphorescent dopant, but does not mean that it cannot be used as a material for forming a fluorescent light-emitting layer. The same applies to the fluorescent host.

[0597] In one embodiment, it is preferred that the light-emitting layer contains a compound represented by formula (I) according to the present application (hereinafter, these compounds can be referred to as "compound (I)"). More preferably, it is contained as a dopant material. In addition, it is preferred that compound (I) is contained in the light-emitting layer as a fluorescent dopant. In addition, it is preferred that compound (I) is contained in the light-emitting layer as a blue fluorescent dopant.

[0598] In one embodiment, the content of compound (I) as a dopant material in the light-emitting layer is not particularly limited. In terms of sufficient light emission and concentration quenching, the content is preferably 0.5 to 70% by mass, more preferably 0.8 to 30% by mass, further preferably 1 to 30% by mass, more further preferably 1 to 20% by mass, particularly preferably 1 to 10% by mass, further particularly preferably 1 to 5% by mass, and more further particularly preferably 2 to 4% by mass, with respect to the mass of the light-emitting layer.

[0599] (fluorescent dopant)

[0600] As a fluorescent dopant other than compound (I), for example, a fused polycyclic aromatic compound, a styrylamine compound, a fused ring amine compound, a boron-containing compound, a pyrrole compound, an indole compound, a carbazole compound can be given. Among them, a fused ring amine compound, a boron-containing compound, a carbazole compound are preferred.

[0601] As a fused ring amine compound, a diamino pyrene compound, a diamino chrysene compound, a diamino anthracene compound, a diamino fluorene compound, a diamino fluorene compound fused with one or more benzofuran skeletons, and the like can be given.

[0602] As a boron-containing compound, a pyrromethene compound, a triphenylborane compound, and the like can be given.

[0603] As a blue fluorescent dopant, for example, a pyrene compound, a styrylamine compound, a chrysene compound, a fluoranthene compound, a fluorene compound, a diamine compound, a triarylamine compound, and the like can be given. Specifically, N,N'-bis[4-(9H-carbazol-9-yl)phenyl]-N,N'-diphenylstilbazene-4,4'-diamine (abbreviation: YGA2S), 4-(9H-carbazol-9-yl)-4'-(10-phenyl-9-anthryl)triphenylamine (abbreviation: YGAPA), 4-(10-phenyl-9-anthryl)-4'-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBAPA), and the like can be given.

[0604] As the green fluorescent dopant, for example, an aromatic amine compound or the like can be given. Specifically, for example, N-(9,10-diphenyl-2-anthryl)-N,9-diphenyl-9H-carbazole-3-amine (abbreviation: 2PCAPA), N-[9,10-bis(1,1'-biphenyl-2-yl)-2-anthryl]-N,9-diphenyl-9H-carbazole-3-amine (abbreviation: 2PCABPhA), N-(9,10-diphenyl-2-anthryl)-N,N',N'-triphenyl-1,4-phenylenediamine (abbreviation: 2DPAPA), N-[9,10-bis(1,1'-biphenyl-2-yl)-2-anthryl]-N,N',N'-triphenyl-1,4-phenylenediamine (abbreviation: 2DPABPhA), N-[9,10-bis(1,1'-biphenyl-2-yl)-2-anthryl]-N-[4-(9H-carbazol-9-yl)phenyl]-N-phenylanthracen-2-amine (abbreviation: 2YGABPhA), N,N,9-triphenylanthracen-9-amine (abbreviation: DPhAPhA), and the like can be given.

[0605] As the red fluorescent dopant, a tetracene compound, a diamine compound, or the like can be given. Specifically, N,N,N',N'-tetrakis(4-methylphenyl)tetracene-5,11-diamine (abbreviation: p-mPhTD), 7,14-diphenyl-N,N,N',N'-tetrakis(4-methylphenyl)acronaphtho[1,2-a]fluoranthene-3,10-diamine (abbreviation: p-mPhAFD), and the like can be given.

[0606] (Phosphorescent dopant)

[0607] As the phosphorescent dopant, a phosphorescent heavy metal complex and a phosphorescent rare earth metal complex can be given.

[0608] As the heavy metal complex, an iridium complex, an osmium complex, a platinum complex, or the like can be given. The heavy metal complex is, for example, an ortho-metalated complex of a metal selected from iridium, osmium, and platinum.

[0609] Examples of the rare earth metal complex include a terbium complex, an europium complex, and the like. Specifically, tris(acetylacetonato)(monophenanthroline)terbium(III) (abbreviation: Tb(acac)3(Phen)), tris(1,3-diphenyl-1,3-propanedionate)(monophenanthroline)europium(III) (abbreviation: Eu(DBM)3(Phen)), tris[1-(2-thienoyl)-3,3,3-trifluoropropanetoneato](monophenanthroline)europium(III) (abbreviation: Eu(TTA)3(Phen)), and the like can be given. These rare earth metal complexes are preferably used as the phosphorescent dopant because a rare earth metal ion emits light due to an electronic transition between different multiplets.

[0610] As a blue phosphorescent dopant, for example, iridium complexes, osmium complexes, platinum complexes, and the like can be given. Specifically, bis[2-(4',6'-difluorophenyl)pyridinato-N,C2']iridium(III) tetrakis(l-pyrazolyl)borate (abbreviation: FIr6), bis[2-(4',6'-difluorophenyl)pyridinato-N,C2']iridium(III) picolinate (abbreviation: Ir(CF3ppy)2(pic)), bis[2-(4',6'-difluorophenyl)pyridinato-N,C2']iridium(III) acetylacetonate (abbreviation: FIracac), and the like can be given.

[0611] As a green phosphorescent dopant, for example, iridium complexes, and the like can be given. Specifically, tris(2-phenylpyridinato-N,C2')iridium(III) (abbreviation: Ir(ppy)3), bis(l,2-diphenyl-lH-benzimidazole)iridium(III) acetylacetonate (abbreviation: Ir(pbi)2(acac)), bis(benzo[h]quinoline)iridium(III) acetylacetonate (abbreviation: Ir(bzq)2(acac)), and the like can be given.

[0612] As a red phosphorescent dopant, iridium complexes, platinum complexes, terbium complexes, europium complexes, and the like can be given. Specifically, bis[2-(2'-benzo[4,5-α]thienyl)pyridinato-N,C3']iridium(III) acetylacetonate (abbreviation: Ir(btp)2(acac)), bis(l-phenylisoquinoline-N,C2')iridium(III) acetylacetonate (abbreviation: Ir(piq)2(acac)), (acetylacetonato)bis[2,3-bis(4-fluorophenyl)quinoxaline]iridium(III) (abbreviation: Ir(Fdpq)2(acac)), 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin platinum(II) (abbreviation: PtOEP), and the like can be given.

[0613] As described above, the light-emitting layer preferably contains at least one compound (I) as a dopant.

[0614] (host material)

[0615] As the host material, for example, metal complexes such as aluminum complexes, beryllium complexes, and zinc complexes; heterocyclic compounds such as indole compounds, pyridine compounds, pyrimidine compounds, triazine compounds, quinoline compounds, isoquinoline compounds, quinazoline compounds, dibenzofuran compounds, dibenzothiophene compounds, oxadiazole compounds, benzimidazole compounds, phenanthroline compounds; fused polycyclic aromatic hydrocarbon (PAH) compounds such as naphthalene compounds, triphenylene compounds, carbazole compounds, anthracene compounds, phenanthrene compounds, pyrene compounds, chrysene compounds, tetracene compounds, fluoranthene compounds; and aromatic amine compounds such as triarylamine compounds and fused polycyclic aromatic amine compounds can be given. A plurality of types of host materials can be used in combination.

[0616] As the fluorescent host, a compound having a higher singlet energy level than the fluorescent dopant is preferable. For example, heterocyclic compounds, fused aromatic compounds, and the like can be given. As the fused aromatic compound, anthracene compounds, pyrene compounds, chrysene compounds, tetracene compounds, and the like are preferable. Anthracene compounds are preferably used as a blue fluorescent host.

[0617] In the case where Compound (I) is used as at least one dopant material, the preferable host material is a substituted or unsubstituted polycyclic aromatic 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 above formula (10).

[0618] As the phosphorescent host, a compound having a higher triplet energy level than the phosphorescent dopant is preferable. For example, metal complexes, heterocyclic compounds, fused aromatic compounds, and the like can be given. Among them, indole compounds, carbazole compounds, pyridine compounds, pyrimidine compounds, triazine compounds, quinolone compounds, isoquinoline compounds, quinazoline compounds, dibenzofuran compounds, dibenzothiophene compounds, naphthalene compounds, triphenylene compounds, phenanthrene compounds, fluoranthene compounds, and the like can be given.

[0619] (Electron transport layer) / (Electron injection layer)

[0620] The electron transport layer is an organic layer formed between the light-emitting layer and the cathode, and has a function of transporting electrons from the cathode to the light-emitting layer. When the electron transport layer is formed of a plurality of layers, the organic layer or inorganic layer closer to the cathode is usually defined as the electron injection layer (see, for example, WO 2010 / 085326). Figure 1The electron injection layer has a function of efficiently injecting electrons from the cathode into the organic layer unit. Preferred electron injection materials are alkali metals, alkali metal compounds, alkali metal complexes, alkaline earth metal complexes, and rare earth metal complexes.

[0621] 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 lifetime of the device, a hole blocking layer, an exciton blocking layer, or a triplet blocking layer.

[0622] According to one embodiment, an electron-donating dopant is preferably contained in the interface region between the cathode and the light-emitting unit. Due to this structure, the organic EL device can have increased brightness or long lifetime. Here, the electron-donating dopant refers to a dopant having a metal with a work function of 3.8 eV or less. As specific examples thereof, at least one selected from the group consisting of 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, etc. can be mentioned.

[0623] As the alkali metal, 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. can be given. A material having a work function of 2.9 eV or less is particularly preferred. Among them, K, Rb, and Cs are preferred. Rb or Cs is further preferred. Cs is most preferred. As the alkaline earth metal, Ca (work function: 2.9 eV), Sr (work function: 2.0 eV to 2.5 eV), Ba (work function: 2.52 eV), etc. can be given. A material having a work function of 2.9 eV or less is particularly preferred. As the rare earth metal, Sc, Y, Ce, Tb, Yb, etc. can be given. A material having a work function of 2.9 eV or less is particularly preferred.

[0624] Examples of the alkali metal compound include alkali metal oxides such as Li2O, Cs2O, or K2O, and alkali metal halides such as LiF, NaF, CsF, and KF. Among them, LiF, Li2O, and NaF are preferred. Examples of the alkaline earth metal compound include BaO, SrO, CaO, and mixtures thereof, for example, Ba x Sr 1-x O (0 < x < 1), and Ba x Ca 1-xO (0 < x < 1). Of these, BaO, SrO, and CaO are preferred. Examples of the rare earth metal compound include YbF3, ScF3, ScO3, Y2O3, Ce2O3, GdF3, and TbF3. Of these, YbF3, ScF3, and TbF3are preferred.

[0625] The alkali metal complex, the alkaline earth metal complex, and the rare earth metal complex are not particularly limited as long as they contain at least one of an alkali metal ion, an alkaline earth metal ion, and a rare earth metal ion as a metal ion. Meanwhile, preferred examples of the ligand include, but are not limited to, hydroxyquinoline, benzo-hydroxyquinoline, hydroxyacridine, hydroxyphenanthridine, hydroxyphenyl-oxazole, hydroxyphenyl-thiazole, hydroxydiaryl-oxadiazole, hydroxydiaryl-thiadiazole, hydroxyphenyl-pyridine, hydroxyphenyl-benzimidazole, hydroxybenzotriazole, hydroxyfluborane, bipyridine, phenanthroline, phthalocyanine, porphyrin, cyclopentadiene, β-diketone, and azomethine.

[0626] As for 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 interface region. The preferred formation method is a method in which the electron-donating dopant is dispersed in an organic compound (a light-emitting material or an electron- injecting material) for forming the interface region by resistance heating deposition method while depositing the electron-donating dopant.

[0627] In the case where the electron-donating dopant is formed in the shape of a layer, a light-emitting material or an electron-injecting material to be used as an organic layer in the interface is formed in the shape of a layer. Then, the reducing dopant is deposited separately by resistance heating deposition method to form a layer preferably having a thickness of 0.1 nm to 15 nm. In the case where the electron-donating dopant is formed in the shape of an island, a light-emitting material or an electron-injecting material to be used as an organic layer in the interface is formed in the shape of an island. Then, the electron-donating dopant is deposited separately by resistance heating deposition method to form an island preferably having a thickness of 0.05 nm to 1 nm. As the electron-transporting material used in the electron-transporting layer other than the compound of formula (I), an aromatic heterocyclic compound having one or more heteroatoms in the molecule can be preferably used. In particular, a nitrogen-containing heterocyclic compound is preferred.

[0628] According to one embodiment, the electron-transporting layer comprises a nitrogen-containing heterocyclic metal chelate.

[0629] According to another embodiment, the electron-transporting layer preferably contains a substituted or unsubstituted nitrogen-containing heterocyclic compound. Specific examples of the preferred heterocyclic compound used in the electron-transporting layer are 6-membered azine compounds; for example, pyridine compounds, pyrimidine compounds, triazine compounds, pyrazine compounds, preferably pyrimidine compounds or triazine compounds; 6-membered fused azine compounds such as quinoline compounds, isoquinoline compounds, quinoxaline compounds, quinazoline compounds, phenanthroline compounds, benzoquinoline compounds, benzoisoquinoline compounds, dibenzoquinoxaline compounds, preferably quinoline compounds, isoquinoline compounds, phenanthroline compounds; 5-membered heterocyclic compounds such as imidazole compounds, oxazole compounds, oxadiazole compounds, triazole compounds, thiazole compounds, thiadiazole compounds; fused imidazole compounds such as benzimidazole compounds, imidazopyridine compounds, naphthimidazole compounds, benzimidazophenanthroline compounds, benzimidazobenzimidazole compounds, preferably benzimidazole compounds, imidazopyridine compounds, or benzimidazophenanthroline compounds.

[0630] According to another embodiment, the electron-transporting layer preferably contains an aromatic hydrocarbon compound. Specific examples of the preferred aromatic hydrocarbon compound used in the electron-transporting layer are oligophenylene compounds, naphthalene compounds, fluorene compounds, fluoranthene groups, anthracene compounds, phenanthrene compounds, pyrene compounds, triphenylene compounds, benzanthracene compounds, chrysene compounds, benzophenanthrene compounds, tetracene compounds, and benzochrysene compounds, preferably anthracene compounds, pyrene compounds, and fluoranthene compounds. p1 Ar p2 Ar P3 P =O of a phosphine oxide compound.

[0631] Ar p1 to Ar p3 is a substituent of a phosphorus atom, each independently represents a substituted or unsubstituted aryl group described above or a substituted or unsubstituted heterocyclic group described above.

[0632] According to another embodiment, the electron-transporting layer preferably contains an aromatic hydrocarbon compound. Specific examples of the preferred aromatic hydrocarbon compound used in the electron-transporting layer are oligophenylene compounds, naphthalene compounds, fluorene compounds, fluoranthene groups, anthracene compounds, phenanthrene compounds, pyrene compounds, triphenylene compounds, benzanthracene compounds, chrysene compounds, benzophenanthrene compounds, tetracene compounds, and benzochrysene compounds, preferably anthracene compounds, pyrene compounds, and fluoranthene compounds.

[0633] (cathode)

[0634] For the cathode, it is preferable to use metals, alloys, electrically conductive compounds, and mixtures thereof, each of which has a small work function (specifically, a work function of 3.8 eV or less). Specific examples of the materials used in the cathode include alkali metals such as lithium and cesium; alkaline earth metals such as magnesium, calcium, and strontium; aluminum; alloys containing these metals (for example, magnesium-silver, aluminum-lithium); rare earth metals such as europium and ytterbium; and alloys containing rare earth metals.

[0635] The cathode is usually formed by a vacuum vapor deposition or sputtering method. In addition, in the case of using a silver paste or the like, a coating method, an inkjet method, or the like can be employed.

[0636] In addition, various conductive materials, such as silver, ITO, graphene, indium oxide-tin oxide containing silicon or silicon oxide (independently selected escape work) can be used to form the cathode. These conductive materials are made into a film using a sputtering method, an inkjet method, a spin coating method, or the like.

[0637] (insulating layer)

[0638] In an organic EL device, since an electric field is applied to a thin film, pixel defects based on leakage or short-circuit are easily generated. In order to prevent such a case, it is preferable to insert an insulating thin layer 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. A mixture thereof can be used for the insulating layer, and a laminate of a plurality of layers containing these materials can also be used for the insulating layer.

[0639] (spacer layer)

[0640] The spacer layer is a layer provided between a fluorescent light emitting layer and a phosphorescent light emitting layer when the fluorescent light emitting layer and the phosphorescent light emitting layer are stacked, to prevent excitons generated in the phosphorescent light emitting layer from diffusing to the fluorescent light emitting layer or to adjust the carrier balance. In addition, the spacer layer can be provided between a plurality of phosphorescent light emitting layers.

[0641] Since the spacer layer is provided between light emitting layers, the material used for the spacer layer is preferably a material having electron transport ability and hole transport ability. In order to prevent triplet energy from diffusing in adjacent phosphorescent light emitting layers, it is preferable that the spacer layer have a triplet energy of 2.6 eV or more. As a material used for the spacer layer, the same materials as those used for the above-described hole transport layer can be given.

[0642] (electron blocking layer, hole blocking layer, exciton blocking layer)

[0643] The electron blocking layer, the hole blocking layer, the exciton (triplet) blocking layer, and the like can be provided adjacent to the light emitting layer.

[0644] The electron blocking layer has a function of preventing electrons from leaking from the light emitting layer to the hole transport layer. The hole blocking layer has a function of preventing holes from leaking from the light emitting layer to the electron transport layer. In order to improve the hole blocking ability, it is preferable to use a material having a deep HOMO level. The exciton blocking layer has a function of preventing excitons generated in the light emitting layer from diffusing to an adjacent layer and confining the excitons within the light emitting layer. In order to improve the triplet state blocking ability, it is preferable to use a material having a high triplet state level.

[0645] (method of forming a layer)

[0646] Unless otherwise specified, the method for forming each layer of the organic EL device according to the present application is not particularly limited. Known film formation methods, such as dry film formation methods, wet film formation methods, and the like, can be used. Specific examples of the dry film formation method include vacuum deposition, sputtering, plasma, ion plating, and the like. Specific examples of the wet film formation method include various coating methods, such as spin coating, dip coating, flow coating, inkjet, and the like.

[0647] (film thickness)

[0648] Unless otherwise specified, the film thickness of each layer of the organic EL device according to the present application is not particularly limited. If the film thickness is too small, defects such as pinholes can occur, making it difficult to obtain sufficient brightness. If the film thickness is too large, a high driving voltage needs to be applied, resulting in reduced efficiency. In this regard, the film thickness is preferably from 0.1 nm to 10 μm, more preferably from 5 nm to 0.2 μm.

[0649] (electronic device)

[0650] The present application also relates to an electronic device (electronic apparatus) including the organic electroluminescent device according to the present application. Examples of the electronic apparatus include display components such as organic EL panel modules; display devices of televisions, mobile phones, smartphones, and personal computers, and the like; and light emitting devices of lighting devices and vehicle lighting devices. Examples

[0651] Hereinafter, the present application will be explained in more detail based on the following synthesis examples, examples, and comparative examples, which should not be construed as limiting the scope of the present application.

[0652] Unless otherwise specified, the percentages and ratios mentioned in the following examples are in weight % and weight ratio.

[0653] I. Synthesis Examples

[0654] All experiments were performed in a protective gas atmosphere.

[0655] Compound 1

[0656] Intermediate 1-1

[0657]

[0658] Under an inert atmosphere, 23.2 ml of n-butyllithium (2.7 M in hexane) was added to 6.34 g (62.7 mmol) of N,N-diisopropylamine while maintaining the temperature below 25°C. After stirring at room temperature for 20 minutes, the reaction mixture was diluted with 10 ml of anhydrous tetrahydrofuran to obtain a freshly prepared LDA (lithium diisopropylamide) solution.

[0659] 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 to it was slowly added a freshly prepared solution of LDA. The temperature was maintained at -78°C for 10 minutes, then it was raised to -30°C for 1.5 hours. The bright orange solution was then slowly warmed to room temperature and stirred for 17 hours to give a yellow milky solution. The reaction mixture was poured into water and extracted with ethyl acetate. The organic extract was then dried over MgS04, filtered, and the solvent was removed on a rotary evaporator. The residue was purified by silica gel column chromatography using cyclohexane as eluent to give 12.61 g (92% yield) of intermediate 1-1 as a clear colorless oil.

[0660] 1 H NMR (300 MHz, DMSO- d 6) δ 7.59 (dd, J = 7.9, 1.1 Hz, 1H), 7.43 (dd, J = 8.0, 1.1 Hz, 1H), 7.28 (t, J = 7.9 Hz, 1H), 0.51 (s, 9H).

[0661] Intermediate 1-2

[0662]

[0663] To 100 ml of toluene were added 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. The suspension was degassed using 3 freeze-pump-thaw cycles and to the reaction mixture were added 347 mg (2 mol%) of tris(dibenzylideneacetone)dipalladium(0) and 439 mg (8 mol%) of tri-tert-butylphosphonium tetrafluoroborate. After two additional freeze-pump-thaw cycles, the reaction mixture was heated to 60°C for 25 hours. The reaction was cooled to room temperature, diluted with toluene. The organic extract was washed with water and dried over MgS04, filtered, the solvent was removed on a rotary evaporator. The residue was purified by silica gel column chromatography using cyclohexane as eluent to give 4.21 g (67% yield) of intermediate 1-2 as a light orange oil.

[0664] 1 H NMR (300 MHz, DMSO- d6) 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)。

[0665] Intermediate 1-3

[0666]

[0667] Intermediate 1-3 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 3 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 was cooled to room temperature, diluted with toluene. The organic extract was washed with water and dried over MgS04, filtered over a pad of silica, which was washed with more toluene. The solvent was removed on a rotary evaporator and the residue was purified by column chromatography on silica gel using cyclohexane as eluent to give a mixture of the desired product and 1-bromo-4-tert-butylbenzene. The remaining 1-bromo-4-tert-butylbenzene was removed by distillation at 300 °C under high vacuum to give 3.74 g (98% yield) of Intermediate 1-3 as a clear colorless resin.

[0668] 1 H NMR (300 MHz, DMSO- d 6) δ 7.45 (t, J = 7.9 Hz, 1H), 7.34 (dd, J =7.9, 1.2 Hz, 1H), 7.31 - 7.23 (m, 4H), 6.90 (dd, J = 7.8, 1.2 Hz, 1H), 6.81 -6.71 (m, 4H), 1.25 (s, 18H), 0.17 (s, 9H).

[0669] Intermediate 1-4

[0670]

[0671] Dissolve 10.0 g (40.6 mmol) of 1-bromo-9H-carbazole, 13.4 g (52.8 mmol) of bis(pinacolato)diboron, and 16.0 g (168.2 mmol) of potassium acetate in 100 ml of anhydrous N,N-dimethylformamide. Degas the suspension by evacuating the reaction vessel with high vacuum and backfilling with argon. Repeat this process 7 times and, before repeating the evacuation-backfilling 2 more times, add 2.32 g (7 mol%) of [1,1'-bis(diphenylphosphino)ferrocene-palladium(II) complexed with dichloromethane to the reaction mixture. Then heat the reaction mixture to 80 °C for 19 hours. After cooling to room temperature, dilute the reaction with 10 ml of diethyl ether and 50 ml of cyclohexane and filter over a small pad of silica gel. Wash the pad with 300 ml of a 5:1 mixture of cyclohexane and diethyl ether. Remove the solvent on a rotary evaporator and purify the residue by column chromatography on silica gel using cyclohexane as eluent. Combine the fractions containing product and remove the solvent on a rotary evaporator until a white solid precipitates. Filter the suspension to obtain 10.25 g (86% yield) of intermediate 1-4 as a white solid.

[0672] 1 H NMR (300 MHz, DMSO- d 6) δ 10.33 (s, 1H), 8.31 – 8.23 (m, 1H), 8.14 –8.09 (m, 1H), 7.75 (dt, J = 8.1, 0.9 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)。

[0673] Intermediate 1-5

[0674]

[0675] 3.65 g (7.86 mmol) of intermediates 1-3, 2.54 g (8.65 mmol) of intermediates 1-4, and 6.68 g (31.5 mmol) of K3PO4 were suspended in a mixture of 50 mL toluene, 25 mL tetrahydrofuran, and 20 mL water. The suspension was degassed using three freeze-dip-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-dip-thaw cycles, the reaction mixture was heated to 90 °C for 20 hours, followed by the addition of another 8.8 mg (0.5 mol%) of palladium(II) acetate and 96.9 mg (3 mol%) of SPhos, and the reaction mixture was heated to 90 °C for an additional hour. The reactants were then cooled to room temperature and extracted with dichloromethane. The organic extract was dried over anhydrous MgSO4 and filtered through a silica mat. The mat was washed with dichloromethane, and the solvent in the filtrate was removed by rotary evaporation. The crude product was purified by silica gel column chromatography using a mixture of heptane and dichloromethane (0-20% gradient) to give 2.17 g of colorless foam. The product was further purified by grinding in 40 mL of cyclohexane at room temperature, followed by grinding in 40 mL of refluxed petroleum ether at 60-80°C. The resulting solid was filtered at room temperature, washed with petroleum ether, and dried under vacuum to give 1.76 g (38% yield) of intermediate 1-5 as a white powder.

[0676] 1 H 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).

[0677] Compound 1

[0678]

[0679] Dissolve 0.50 g (0.84 mmol) of Intermediate 1-5 in 10 ml of 1,2-dichlorobenzene and degas using 3 freeze-thaw cycles. To the reaction mixture add 0.34 g (3.36 mmol) of triethylamine followed by 1.68 ml (1.68 mmol) of trichloroborane (1 M in heptane) slowly. Heat the reaction mixture to 180 °C for 42 h to give a clear oily solution. After cooling to room temperature, dilute the gummy mixture with 70 ml of cyclohexane and filter through a pad of silica. Wash the pad with 200 ml of cyclohexane to remove solvent, use 100 ml of toluene then 100 ml of dichloromethane to elute the desired product into separate fractions. Remove the solvent on a rotary evaporator and purify the crude product by column chromatography on silica gel using a mixture of heptane and toluene (0-20% gradient) to give the product as an oil which crystallises using a few drops of diethyl ether. Collect the solid by filtration to give 0.13 g (29% yield) of Compound 1 as a bright yellow powder.

[0680] 1 H NMR (300 MHz, Chloroform-d, 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).

[0681] Compound 2

[0682] Intermediate 2-1

[0683]

[0684] Intermediate 1-1, 5.83 g (2.86 mmol) of 3,6-di-tert-butyl-9H-carbazole and 7.29 g (76.00 mmol) of sodium tert-butoxide were added to 150 ml of xylenes. The suspension was degassed using 3 freeze-thaw- degassing cycles and 347 mg (2 mol%) of tris(dibenzylideneacetone)dipalladium(0) and 329 mg (3 mol%) of Xantphos (4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) were added to the reaction mixture. After two additional freeze-thaw-degassing cycles, the reaction mixture was heated to 120 °C for 15 hours. Additional 347 mg (2 mol%) of tris(dibenzylideneacetone)dipalladium(0) and 329 mg (3 mol%) of Xantphos were added to the reaction mixture and the reaction was further heated for a total of 50 hours. The reaction was then cooled to room temperature, extracted with toluene, the organic extracts were dried over anhydrous MgS04, filtered over a small pad of silica. The pad was washed with toluene and the solvent of the filtrate was removed on a rotary evaporator. The crude product was purified by silica gel column chromatography using heptane to yield 3.25 g (37% yield) of Intermediate 2-1 as a colorless foam.

[0685] 1 H NMR (300 MHz, DMSO- d 6) δ 8.27 (d, J = 1.5 Hz, 2H), 7.66 (dd, J =8.0, 1.3 Hz, 1H), 7.59 (t, J = 7.8 Hz, 1H), 7.45 (dd, J = 8.6, 1.9 Hz, 2H),7.13 (dd, J = 7.6, 1.3 Hz, 1H), 6.89 (d, J = 8.5 Hz, 2H), 1.41 (s, 18H), 0.14(s, 9H).

[0686] Intermediate 2-2

[0687]

[0688] Dissolve 5.00 g (17.89 mmol) 3,6-di-tert-butyl-9H-carbazole in 50 ml acetic acid and add 3.18 g (17.89 mmol) N-bromosuccinimide portionwise to the white suspension. After 4 hours, add 200 ml water and stir the reaction for another 30 minutes. Filter the resulting precipitate and wash the solid with water, saturated NaHC03solution and again with water. Purify the crude product by column chromatography on silica gel using a mixture of heptane and toluene (0-40% gradient) followed by column chromatography on silica gel using a mixture of cyclohexane and dichloromethane (0-3% gradient) again. Combine the pure fractions and remove the solvent on a rotary evaporator to yield 3.42 g (45% yield) of intermediate 2-2 as a clear colorless oil.

[0689] 1 H NMR (300 MHz, DMSO- d 6) δ 11.10 (s, 1H), 8.20 (d, J = 1.5 Hz, 1H), 8.18 (dd, J = 1.4, 0.9 Hz, 1H), 7.57 (d, J = 1.7 Hz, 1H), 7.50 (dd, J = 8.6, 1.8 Hz, 1H), 7.45 (dd, J = 8.7, 0.8 Hz, 1H), 1.40 (s, 18H).

[0690] Intermediate 2-3

[0691]

[0692] To a solution of 3.40 g (9.49 mmol) of intermediate 2-2, 3.13 g (12.34 mmol) of bis(pinacolato)diboron and 3.73 g (39.20 mmol) of potassium acetate in 40 ml of dry N,N-dimethylformamide was added 542 mg (7 mol%) of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) complex with dichloromethane. The reaction mixture was heated to 80°C for 21 hours. After cooling to room temperature, the reaction was diluted with diethyl ether, washed with water, dried over MgS04, and filtered through a small pad of silica gel. The pad was washed with 300 ml of a 5:1 mixture of cyclohexane and diethyl ether. The solvent was removed on a rotary evaporator and 30 ml of petroleum ether 60-80 was added to the brown residue. The solution was then concentrated until a white powder precipitated. The solid was filtered and washed with cold petroleum ether to give 3.05 g (79% yield) of intermediate 2-3 as a white powder.

[0693] 1 H NMR (300 MHz, DMSO- d 6) δ 10.04 (s, 1H), 8.34 (d, J = 2.0 Hz, 1H),8.16 (d, J = 1.9 Hz, 1H), 7.71 (d, J = 2.1 Hz, 1H), 7.60 (d, J = 8.6 Hz, 1H),7.45 (dd, J = 8.6, 2.0 Hz, 1H), 1.41 (s, 30H).

[0694] Intermediate 2-4

[0695]

[0696] Intermediate 2-4 was prepared according to the procedure described in Scheme 2. To a solution of 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 in a mixture of 50 mL of toluene, 25 mL of dioxane and 15 mL of water was added 9.7 mg (1 mol%) of palladium(II) acetate and 107 mg (6 mol%) of SPhos. After three freeze- aspirate-thaw cycles, the reaction mixture was heated to 80 °C for 10 h, 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 was heated to 80 °C for an additional 12 h. The reaction was then cooled to room temperature, extracted with toluene, the organic extracts were dried over anhydrous MgSO4, filtered over a small pad of silica. The pad was washed with toluene and the solvent was removed from the filtrate on a rotary evaporator. The crude product was purified by column chromatography on silica gel using a mixture of heptane and tetrahydrofuran (0-1% gradient) to give 2.80 g (92% yield) of Intermediate 2-4 as a white foam.

[0697] 1 H NMR (300 MHz, DMSO- d 6) δ 10.70 (s, 1H), 8.27 (d, J = 1.9 Hz, 2H),8.22 (d, J = 1.8 Hz, 1H), 8.20 – 8.17 (m, 1H), 7.70 (t, J = 7.6 Hz, 1H), 7.56(dd, J = 7.5, 1.3 Hz, 1H), 7.54 – 7.47 (m, 2H), 7.46 – 7.41 (m, 2H), 7.33 (d,J = 1.8 Hz, 1H), 7.24 (d, J = 8.5 Hz, 1H), 7.20 (dd, J = 7.8, 1.2 Hz, 1H),7.12 (d, J = 8.6 Hz, 1H), 1.47 (s, 9H), 1.45 – 1.43 (m, 18H), 1.42 (s, 9H), -0.72 (s, 9H)。

[0698] Compound 2

[0699]

[0700] Dissolve 2.44 g (3.46 mmol) of intermediate 2-4 in 70 ml of 1,2-dichlorobenzene and purge the reaction vessel with nitrogen. At room temperature, add 2.42 ml (13.84 mmol) of N,N-diisopropylethylamine, then add 5.20 ml (5.20 mmol) of tribromoborane (1 M in heptane) dropwise. Heat the resulting clear, light orange solution to 145 °C for 20 hours, then cool to room temperature. Quench the reaction by slowly adding 15 ml of methanol, pour the resulting solution into 200 ml of methanol. Stir the yellow precipitate for 5 minutes, then filter, wash with methanol, and dry to yield 1.11 g (50% yield) of compound 2 as a yellow solid.

[0701] 1 H NMR (300 MHz, THF-d8) δ 9.00 (d, J = 1.9 Hz, 1H), 8.65 (d, J = 8.7Hz, 1H), 8.58 (d, J = 1.9 Hz, 1H), 8.54 (d, J = 1.7 Hz, 1H), 8.52 (d, J = 8.3Hz, 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).

[0702] Compound 3

[0703] Intermediate 3-1

[0704]

[0705] Intermediate 3-2 Intermediate 3-2 was prepared according to the procedure described above for the preparation of Intermediate 3-1, using 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. The crude product was purified by column chromatography on silica gel using a mixture of heptane and toluene (0-35% gradient) to give 1.4 g (41% yield) of Intermediate 3-2 as a light yellow foam.

[0706] ESI-MS: 614.3 [M+H] + .

[0707] Intermediate 3-2 Intermediate 3-2 was prepared according to the procedure described above for the preparation of Intermediate 3-1, using 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. The crude product was purified by column chromatography on silica gel using a mixture of heptane and toluene (0-35% gradient) to give 1.4 g (41% yield) of Intermediate 3-2 as a light yellow foam.

[0708]

[0709] Intermediate 3-2 Intermediate 3-2 was prepared according to the procedure described above for the preparation of Intermediate 3-1, using 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. The crude product was purified by column chromatography on silica gel using a mixture of heptane and toluene (0-35% gradient) to give 1.4 g (41% yield) of Intermediate 3-2 as a light yellow foam.

[0710] ESI-MS: 857.5 [M+H]+.

[0711] Compound 3

[0712]

[0713] Dissolve 3.70 g (4.32 mmol) of intermediate 3-2 in 80 mL of 1,2-dichlorobenzene and purge the reaction vessel with nitrogen. At room temperature, add 3.02 mL (17.26 mmol) of N,N-diisopropylethylamine, then add dropwise 8.50 mL (8.50 mmol) of tribromoborane (1 M in heptane). Heat the resulting clear light orange solution to 160 °C for 16 hours, then cool to room temperature. Quench the reaction by slow addition of 5 mL of a 10% aqueous sodium acetate solution. Extract the aqueous phase with toluene (2 x 20 mL). Filter the combined organic phases through a plug of silica, rinse the plug with toluene (40 mL). Pour the filtrate into 500 ml of methanol. Stir the yellow precipitate for 5 minutes, then filter, wash with methanol and dry to obtain 2.24 g (66% yield) of compound 3 as a yellow solid.

[0714] ESI-MS: 793.5 [M+H] + .

[0715] Compound 4

[0716] Intermediate 4-1

[0717]

[0718] Dissolve 3.70 g (4.32 mmol) of intermediate 3-2 in 80 mL of 1,2-dichlorobenzene and purge the reaction vessel with nitrogen. At room temperature, add 3.02 mL (17.26 mmol) of N,N-diisopropylethylamine, then add dropwise 8.50 mL (8.50 mmol) of tribromoborane (1 M in heptane). Heat the resulting clear light orange solution to 160 °C for 16 hours, then cool to room temperature. Quench the reaction by slow addition of 5 mL of a 10% aqueous sodium acetate solution. Extract the aqueous phase with toluene (2 x 20 mL). Filter the combined organic phases through a plug of silica, rinse the plug with toluene (40 mL). Pour the filtrate into 500 ml of methanol. Stir the yellow precipitate for 5 minutes, then filter, wash with methanol and dry to obtain 2.24 g (66% yield) of compound 3 as a yellow solid.

[0719] 1H NMR (300 MHz, CDC13) δ 7.64 (t, 1H), 7.52 (t, 1H), 7.51 - 7.46 (m, 5H), 1.40 (s, 9H).

[0720] Intermediate 4-2

[0721]

[0722] Dissolve 16 mL (0.11 mol) diisopropylamine in 100 mL tetrahydrofuran and treat with 45 mL n-butyllithium (2.5 M in hexanes) dropwise at -30 °C. Slowly add this solution to a pre-cooled solution of 30.0 g (93 mmol) Intermediate 4-1 and 14.1 mL (0.11 mol) chlorotrimethylsilane in 200 mL tetrahydrofuran at a maximum temperature of -70 °C. After complete addition, further stir the light yellow solution at -75 °C for 45 minutes. Add 100 mL of a 5% aqueous ammonium chloride solution and stir the reaction mixture until room temperature is reached. Dilute the solution with 200 mL heptane and wash the organic phase with 200 mL water and 100 mL saturated aqueous sodium chloride solution. Dry the organic phase over sodium sulfate and concentrate in vacuo. Purify the product further by MPLC using a CombiFlash Companion (silica gel, heptane) to give 36.7 g (98% yield) of Intermediate 4-2 as a colorless oil.

[0723] 1 H NMR (300 MHz, CDC13) δ 7.73 (d, 1H), 7.54 (d, 1H), 7.52 (d, 4H), 1.39 (s, 9H), 0.60 (s, 9H).

[0724] Intermediate 4-3

[0725]

[0726] Intermediate 4-2, 2.31 g (8.27 mmol) 3,6-di-tert-butyl-9H-carbazole, 0.28 g (0.3 mmol) tris(dibenzylideneacetone)dipalladium(0), 0.35 g (0.6 mmol) 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos), and 2.9 g (30 mmol) sodium tert-butoxide were suspended in 30 mL of o-xylene. The orange suspension was evacuated three times and backfilled with argon and stirred at 117 °C for 22 h. 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 solution, then dried over sodium sulfate and concentrated in vacuo. The product was further purified by MPLC using a CombiFlash Companion (silica gel, heptane). The resulting oil was treated with 100 mL of methanol and stirred at 40 °C until a suspension formed, yielding 1.37 g (30% yield) of Intermediate 4-3 as a white solid.

[0727] ESI-MS (positive, m / z): C 39 H 48 Exact mass of ClNSi = 593.32; found 594.4 [M + 1] + .

[0728] Intermediate 4-4

[0729]

[0730] Intermediate 4-3, 1.64 g (4.0 mmol) of Intermediate 2-3, 16 mg (0.07 mmol) palladium(II) acetate, 171 mg (0.42 mmol) 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos), and 2.86 g (13.4 mmol) potassium phosphate tribasic were dissolved in a mixture of 25 mL of toluene, 15 mL of 1,4-dioxane, and 7 mL of water. The solution was evacuated three times and backfilled with argon and heated at 77 °C for 20 h. The reaction mixture was cooled to room temperature, poured into 100 mL of water, and stirred for 10 min. The passed organics were filtered through a 3 cm silica gel bed, followed by a rinse of the silica gel bed with 200 mL of heptane. The collected eluent was concentrated in vacuo. The product was dissolved in ethanol, water was added, and a suspension formed. The suspension was stirred for 30 min, then filtered, and the solid washed with water. The solid was dissolved in dichloromethane, then dried over sodium sulfate, and concentrated in vacuo to yield 1.8 g (64%) of Intermediate 4-4 as a white solid.

[0731] ESI-MS (negative, m / z): C 59 H 72 Exact mass of N2Si = 836.55; found 835.6 [M-1] + .

[0732] Compound 4

[0733]

[0734] Compound 4

[0735] ESI-MS (positive, m / z): C 56 H 61 Exact mass of BN2 = 772.49; found 773.8 [M +1] + .

[0736] Compound 5

[0737] Intermediate 5-1

[0738]

[0739] Compound 5

[0740] ESI-MS (positive, m / z): C 22 H 22 Exact mass of BNO2= 343.17; Found 344.4 [M + 1] + .

[0741] Intermediate 5-2

[0742]

[0743] Intermediate 5-2 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 potassium phosphate tribasic 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 and backfilled with argon three times and heated at 84 °C for 3 hours. The reaction mixture was cooled, 40 mL of toluene and 40 mL of water were added. The organic phase was washed with water (3 x 40 mL), then dried over sodium sulfate, and concentrated in vacuo. The product was further purified by MPLC using a CombiFlash Companion (silica gel, toluene). The resulting white foam was taken up in 50 mL of toluene, and the resulting hazy solution was cooled to room temperature. 10 mL of water was added, and the mixture was heated until a suspension 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 in vacuo to give 3.40 g (82% yield) of Intermediate 5-2 as a white solid.

[0744] ESI-MS (negative, m / z): C 45 H 46 Exact mass of N2Si = 642.34; Found 641.6 [M - 1] + .

[0745] Compound 5

[0746]

[0747] Dissolve 3.40 g (5.29 mmol) of intermediate 5-2 in 70 mL of 1,2-dichlorobenzene. Add dropwise 3.7 mL (21.2 mmol) of N,N-diisopropylethylamine and 10.6 mL of tribromoborane (1.0 M in heptane). Heat the yellow solution at 150 °C for 18 hours. Cool the orange solution and slowly add 4 mL of 10% aqueous sodium acetate. Add the mixture dropwise to 600 mL of methanol. Filter the yellow suspension and wash the solid with ethanol and heptane. Heat the solid in a mixture of 150 mL of dichloromethane and 100 mL of isopropanol and then slowly cool to room temperature. Filter the suspension and wash the solid with isopropanol to give 2.12 g (69% yield) of compound 5 as a yellow solid.

[0748] ESI-MS (negative, m / z): C 42 H 35 Exact mass of BN2 = 578.29; found 579.7 [M-1] + .

[0749] Compound 6

[0750] Intermediate 6-1

[0751]

[0752] Dissolve 17.3 g (70.0 mmol) of 4-bromodibenzo[ b,d ]furan, 12.48 g (77.0 mmol) of 2,6-dichloroaniline, 10.09 g (105 mmol) of sodium tert-butoxide in 150 mL of o-dichlorobenzene. Degass the suspension with Ar and add 2.62 g (6 mol%) of BINAP and 471 mg (3 mol%) of tris(dibenzylideneacetone)dipalladium(0) to the reaction mixture. Heat the reaction mixture to 155 °C for 3 hours. Cool the reaction to room temperature, dilute with toluene / water and filter through celite. Separate the layers and further extract the aqueous layer with toluene. Dry the organic extracts over sodium sulfate, filter and evaporate. Purify the residue by column chromatography on silica gel using heptane / toluene as eluent to give 19.26 g (84% yield) of intermediate 6-1 as a white solid.

[0753] ESI-MS: 328.3 [M+H] + .

[0754] Intermediate 6-2

[0755]

[0756] Intermediate 6-1, 14.93 g (108 mmol) of potassium carbonate were suspended in N,N-dimethylacetamide. The suspension was degassed with Ar and to the reaction mixture were added 485 mg (4 mol%) of palladium acetate and 1.59 g (8 mol%) of tricyclohexylphosphonium tetrafluoroborate. The reaction mixture was heated to 130 °C for 3.5 hours. The reaction was cooled to room temperature, diluted with toluene / water and filtered through celite. The layers were separated and the aqueous layer was further extracted with toluene. The organic extracts were washed with water, brine, dried over sodium sulfate, filtered and evaporated. The residue was purified by column chromatography on silica gel using heptane / toluene as eluent to give 10.39 g (66% yield) of intermediate 6-2 as a white solid.

[0757] ESI-MS: 290.0 [M-H] - .

[0758] Intermediate 6-3

[0759]

[0760] Intermediate 6-2, 10.06 g (39.6 mmol) of bis(pinacolato)diboron and 8.10 g (83.0 mmol) of potassium acetate were suspended in 125 mL of 1,4-dioxane. The suspension was degassed with Ar and to the reaction mixture were added 453 mg (1.5 mol%) of tris(dibenzylideneacetone)dipalladium(0) and 406 mg (3 mol%) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl. The reaction mixture was heated to 105 °C for 4 hours. The reaction was cooled to room temperature, diluted with toluene / water and filtered through celite. The layers were separated and the aqueous layer was further extracted with toluene. The organic extracts were washed with water, brine, dried over sodium sulfate, filtered and evaporated. The residue was refluxed in 70 mL of heptane for 15 minutes, cooled to room temperature and then the orange suspension was filtered and dried under vacuum. This gave 11.40 g (90% yield) of intermediate 6-3 as a beige solid.

[0761] ESI-MS: 382.3 [M-H] - .

[0762] Intermediate 6-4

[0763]

[0764] Intermediate 6-4 was prepared according to the following procedure. A mixture of 3.86 g (6.5 mmol) of intermediate 4-3, 2.74 g (7.15 mmol) of intermediate 6-3, 4.24 g (13.0 mmol) of cesium carbonate was 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 h. The reaction was cooled to room temperature and diluted with toluene / water. The layers were separated and the aqueous layer was further extracted with toluene. The organic extracts were washed with water, brine, dried over sodium sulfate, filtered and evaporated. The residue was purified by column chromatography on silica gel using heptane / toluene as eluent to give 4.46 g (84% yield) of intermediate 6-4 as a white foam.

[0765] ESI-MS: 813.6 [M-H] - .

[0766] Compound 6

[0767]

[0768] Intermediate 6-4 was prepared according to the following procedure. A mixture of 3.86 g (6.5 mmol) of intermediate 4-3, 2.74 g (7.15 mmol) of intermediate 6-3, 4.24 g (13.0 mmol) of cesium carbonate was 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 h. The reaction was cooled to room temperature and diluted with toluene / water. The layers were separated and the aqueous layer was further extracted with toluene. The organic extracts were washed with water, brine, dried over sodium sulfate, filtered and evaporated. The residue was purified by column chromatography on silica gel using heptane / toluene as eluent to give 4.46 g (84% yield) of intermediate 6-4 as a white foam.

[0769] ESI-MS: 751.9 [M+H] + .

[0770] Compound 7

[0771] Intermediate 7-1

[0772]

[0773] Dissolve 48.0 g (0.16 mol) 1,3-dibromo-5-(tert-butyl)benzene in 500 mL tetrahydrofuran. Add 70.0 mL n-butyllithium (2.5 M in hexanes) dropwise over 45 minutes at a maximum temperature of -71 °C. Add 45.9 g (0.18 mol) iodine in portions over 15 minutes at a maximum temperature of -55 °C and further stir the resulting suspension for 45 minutes at -78 °C. Add 400 mL of a 10% aqueous sodium sulfite solution and further stir the reaction mixture until it reaches room temperature. Separate the organic phase and extract the aqueous phase with cyclohexane (2 x 150 mL). Wash the combined organic phases with water (2 x 200 mL) and saturated aqueous sodium chloride solution. Dry the organic phase over sodium sulfate and concentrate in vacuo to give 54.7 g (83% yield) of intermediate 7-1 as an orange oil.

[0774] 1 H NMR (300 MHz, DMSO- d 6) δ 7.77 (t, 1H), 7.72 (t, 1H), 7.57 (t, 1H),1.26 (s, 9H).

[0775] Intermediate 7-2

[0776]

[0777] Dissolve 3.22 g (10.00 mmol) 9,9-dimethyl-2,7-di(tert-butyl)-9,10- dihydroacridine, 3.73 g (11.00 mmol) of intermediate 7-1 and 2.88 g (30.00 mmol) of sodium acetate in 57 mL of xylenes. After degassing the suspension using 3 freeze- aspirate-thaw cycles, add 225 mg (1.00 mmol) palladium acetate and 554 mg (1.00 mmol) of 1,1'-bis(diphenylphosphino)ferrocene to the mixture. Then, after two additional freeze-aspirate-thaw cycles, stir the reaction mixture to 100 °C for 1 hour. Cool the reaction to room temperature and concentrate. Purify the residue by column chromatography on silica gel with cyclohexane as eluent to give 3.42 g (64% yield) of intermediate 7-2 as a white solid.

[0778] ESI-MS: 534.6 [M+H] + .

[0779] Intermediate 7-3

[0780]

[0781] 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 3 freeze-thaw-aspirate cycles, 29 mg (0.13 mmol) of palladium acetate and 316 mg (0.77 mmol) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl were added to the mixture. Then, after two additional freeze-thaw-aspirate cycles, the mixture was stirred to 85 °C for 14.5 hours. The reaction was cooled to room temperature, diluted with toluene. The organic extract was washed with water, dried over sodium sulfate, filtered and the solution was concentrated. The residue was purified by column chromatography on silica gel using a mixture of heptane and dichloromethane as eluent to give 4.17 g (89% yield) of intermediate 7-3 as a white solid.

[0782] ESI-MS: 731.9 [M+H] + .

[0783] Compound 7

[0784]

[0785] Intermediate 7-3, 4.14 g (5.66 mmol) was dissolved in 190 mL of dichlorobenzene. Then, to the solution was added 11.9 mL (11.9 mmol) of 1.0 M boron tribromide in heptane 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 was cooled to room temperature, diluted with toluene. The reaction mixture was quenched with 1.0 M aqueous sodium acetate solution. The aqueous layer was extracted with toluene. The organic extract was washed with water, dried over magnesium sulfate, filtered and the solution was concentrated. The residue was purified by column chromatography on silica gel using heptane as eluent to give 2.49 g (54% yield) of compound 7 as a yellow solid.

[0786] ESI-MS: 739.9 [M+H] + .

[0787] Compound 8

[0788] Intermediate 8-1

[0789]

[0790] Intermediate 8-1 was prepared according to the procedure described in Example 1, substituting 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 potassium phosphate tribasic for 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 potassium phosphate tribasic, respectively. The product was purified by MPLC using CombiFlash Companion (silica gel, heptane / 0-5% dichloromethane gradient) to give 6.9 g (91%) of Intermediate 8-1.

[0791] ESI-MS (positive, m / z): C 42 H 44 Exact mass of BrN = 641.27; Found 642.7 [M + 1] + .

[0792] Intermediate 8-1

[0793]

[0794] Intermediate 8-3 was prepared according to the procedure described in Example 1, substituting 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 potassium phosphate tribasic for 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 potassium phosphate tribasic, respectively. The product was purified by MPLC using CombiFlash Companion (silica gel, heptane / 0-5% dichloromethane gradient) to give 6.9 g (91%) of Intermediate 8-1.

[0795] ESI-MS (positive, m / z): C 62 H 68 Exact mass of N2 = 840.54; Found 840.0 [M - 1] + .

[0796] Compound 8

[0797]

[0798] 2.00 g (2.38 mmol) of intermediate 8-2 was dissolved in 40 mL of 1,2-dichlorobenzene. 1.7 mL (9.5 mmol) of N,N-diisopropylethylamine and 4.75 mL of tribromoborane (1.0 M, in heptane) were added dropwise. The brown solution was heated at 172 °C for 2.5 h. The reaction mixture was cooled, and 100 mL of methanol was added. The suspension was stirred for 15 min and then filtered. The solid was washed with 50 mL of methanol, then with 30 mL of water, followed by washing with 50 mL of methanol and 30 mL of heptane. The solid was further purified by MPLC using CombiFlash Companion (silica gel, dichloromethane) to give 1.84 g (91% yield) of compound 8 as a yellow solid.

[0799] ESI-MS (positive, m / z): C 62 H 65 Precise mass of BN2 = 848.52; Measured mass 849.8 [M+1] + .

[0800] Compound 9

[0801] Intermediate 9-1

[0802]

[0803] Dilute 175 mL of a zinc chloride solution (1.9 M in 2-methyltetrahydrofuran) with 175 mL of tetrahydrofuran and cool to 0 °C. Add 300 mL of a cyclohexylmagnesium chloride solution (1 M in 2-methyltetrahydrofuran) over 10 minutes at a maximum temperature of 25 °C. Further stir the reaction mixture at 0 °C for 10 minutes and then slowly add to a pre-cooled solution of 54.0 g (0.24 mol) of 6-bromo-2-tetralone, 0.34 g (1.5 mmol) of palladium(II) acetate, and 1.30 g (3.0 mmol) of 2-dicyclohexylphosphino-2',6'-bis(N,N-dimethylamino)biphenyl (CPhos) in 540 mL of tetrahydrofuran at a maximum temperature of 15 °C. Stir the resulting orange suspension at 0 °C for one hour and heat at 31 °C for an additional hour. Add 0.34 g (1.5 mmol) of palladium(II) acetate and 1.30 g (3.0 mmol) of CPhos and continue heating for an additional two hours. Cool the black suspension to room temperature and filter over a pad of diatomaceous earth filter aid followed by a 500 mL rinse of the filter aid with cyclohexane. Combine the eluates with 300 mL of water and remove the organic solvents in vacuo. Stir the residue with 600 mL of cyclohexane and 600 mL of ethyl acetate. Separate the organic phase and wash with 300 mL of water and 200 mL of saturated aqueous sodium chloride solution. Dry the organic phase over sodium sulfate, filter over a pad of silica gel, then rinse the silica gel with 300 mL of a solvent mixture of cyclohexane and ethyl acetate (2:1) and then with 300 mL of ethyl acetate. Concentrate the combined eluates in vacuo to give 59.6 g (87% yield) of intermediate 9-1.

[0804] 1 H 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)。

[0805] Intermediate 9-2

[0806]

[0807] Intermediate 9-2 30.0 g (0.13 mol) of 1-bromo-4-(tert-butyl)aniline was suspended in 300 mL of a 37% aqueous hydrochloric acid solution and cooled to 0°C. 60.5 g (0.13 mol) of a 15% aqueous sodium nitrite solution was added dropwise over 15 minutes at a maximum temperature of 2°C. A solution of 74.8 g (0.40 mol) of tin chloride in 74.8 g of a 37% aqueous hydrochloric acid solution was added dropwise over 40 minutes at a maximum temperature of 5°C. The thick suspension was stirred for 90 minutes at 0°C. The suspension was filtered and the off-white residue was washed with 150 mL of a saturated aqueous sodium chloride solution and 200 mL of heptane. The remaining solid was dried in vacuo at 40°C for 18 hours to give 31 g (84% yield) of intermediate 9-2 as a white powder which was used directly in the next reaction step.

[0808] 1 H NMR (300 MHz, DMSO- d 6) δ 10.43 (br. s, 2H), 7.71 (s, 1H), 7.50 (d,1H), 7.36 (dd, 1H), 7.14 (d, 1H), 1.25 (s, 9H).

[0809] Intermediate 9-3

[0810]

[0811] A mixture of 29.8 g (48.7 mmol) of intermediate 9-1 and 15.0 g (48.7 mmol) of intermediate 9-2 was combined with 150 mL of a 4N hydrochloric acid 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 eluate 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 with a saturated aqueous sodium chloride solution and dried over sodium sulfate. The mixture was filtered over a plug of silica gel followed by a silica gel layer flushed with cyclohexane. The collected eluate was concentrated under vacuum. The product was purified by MPLC using a CombiFlash Companion (silica gel, heptane / 0-2% ethyl acetate gradient) to give 14.7 g (69% yield) of intermediate 9-3 as an orange solid.

[0812] ESI-MS (negative, m / z): C 26 H 30 Exact mass of BrN = 435.16; found 434.4 [M + 1] + .

[0813] Intermediate 9-4

[0814]

[0815] Intermediate 9-3 and 6.10 g (24.8 mmol) of p-choranil in o-xylene was heated at 138 °C for six hours. The reaction mixture was cooled to room temperature and diluted with ethyl acetate until a solution was formed. The solution was mixed with 20 g of silica gel and concentrated under vacuum. The solid was further purified by MPLC using CombiFlash Companion (silica gel, heptane / 0-2% gradient ethyl acetate) to give 9.2 g (89% yield) of Intermediate 9-4 as an orange solid. CombiFlash Companion ESI-MS (positive, m / z): C 26 H 28 Exact mass of BrN = 433.14; Found 434.3 [M + 1] + .

[0816] Intermediate 9-5

[0817]

[0818]

[0819] Intermediate 9-4, 10.3 g (40.4 mmol) of bis(pinacolato)diboron and 5.40 g (55.0 mmol) of potassium acetate was 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 filter aid was added. The mixture was concentrated under vacuum and purified by MPLC using CombiFlash Companion (silica gel, heptane / ethyl acetate 9: 1) to give 9.3 g (72% yield) of Intermediate 9-5 as a light yellow solid.

[0820] ESI-MS (positive, m / z): C 32 H 40 Exact mass of BNO2 = 481.32; Found 482.7 [M + 1] + .

[0821] Intermediate 9-6 ​

[0822]

[0823] A suspension of 40.0 g (0.12 mol) 3,6-dibromo-9H-carbazole, 43.8 g (0.25 mol) 3-tert-butylphenylboronic acid, 2.13 g (1.85 mmol) tetrakis(triphenylphosphine)palladium(0), and 574 g of a 10% aqueous sodium carbonate solution was 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 two 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 pad of silica, followed by a rinse of the silica with hot toluene. The combined eluent was concentrated under vacuum until a suspension formed, and cooled to room temperature. The suspension was filtered, and the solid was washed with toluene to give 33.0 g (55% yield) of intermediate 9-6 as a white solid.

[0824] ESI-MS (positive, m / z): C 32 H 33 Exact mass of N = 431.26; Found 432.6 [M + 1] + .

[0825] Intermediate 9-7

[0826]

[0827] A suspension of 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 potassium phosphate tribasic was suspended in 75 mL of 1,4-dioxane and heated at 91 °C for six hours. The suspension was filtered through a 3 cm layer of silica gel, then the silica gel was rinsed with 100 mL of dioxane. The eluent was concentrated under vacuum, and the product was further purified by MPLC using a CombiFlash Companion (silica gel, heptane / 0-20% gradient in dichloromethane) to give 5.46 g (90%) of intermediate 9-7.

[0828] ESI-MS (positive, m / z): C 42 H 44 Exact mass of N = 641.27; Found 642.6 [M + 1] + .

[0829] Intermediate 9-8

[0830]

[0831] Dissolve 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 potassium phosphate tribasic in a mixture of 30 ml of toluene, 15 ml of 1,4-dioxane and 10 ml of water. Vacuum the solution three times and backfill with argon, and heat at 82°C for three hours. Cool the reaction mixture to room temperature, dilute with 100 ml of toluene, treat with 100 ml of water. Wash the organic phase with water (3 x 50 mL), dry over sodium sulfate and concentrate in vacuo. Dilute the resulting oil with 30 ml of dichloromethane and 100 ml of ethanol. Concentrate the solution in vacuo to a volume of 100 ml, filter the resulting suspension, wash the solid with 50 ml of ethanol to give 4.7 g (66% yield) of intermediate 9-8 as a white solid.

[0832] ESI-MS (positive, m / z): C 68 H 72 Exact mass of N2 = 916.57; found 918.0 [M + 1] + .

[0833] Compound 9

[0834]

[0835] Dissolve 4.50 g (4.91 mmol) of intermediate 9-8 in 120 ml of 1,2-dichlorobenzene. Add dropwise 3.4 ml (19.6 mmol) of N,N-diisopropylethylamine and 9.8 ml of tribromoborane (1.0 M in heptane). Heat the brown solution at 172°C for four hours. Cool the reaction mixture and add 300 ml of methanol. Concentrate the solution in vacuo, purify the product by MPLC using CombiFlash Companion (silica gel, dichloromethane). Dissolve the isolated product in 20 ml of dichloromethane, treat with 100 ml of acetonitrile. Stir the resulting suspension for 30 minutes and filter. Wash the solid with 100 ml of acetonitrile to give 3.86 g (85% yield) of compound 9 as a yellow solid.

[0836] ESI-MS (positive, m / z): C 68 H 69 Exact mass of BN2 = 924.56; found 926.0 [M + 1] + .

[0837] Compound 10

[0838] Intermediate 10-1

[0839]

[0840] Intermediate 10-1 13.2 g (47.2 mmol) 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 was added 1.12 g (5.90 mmol) of copper (I) iodide and 2.02 g (17.7 mmol) of cyclohexane-1,2-diamine and 37.6 g (177 mmol) of potassium phosphate. The mixture was stirred at 95 °C for 6.5 hours. After the reaction mixture was cooled to room temperature, the solids were filtered and washed with toluene. The solution was washed with an aqueous solution of 3-amino-2-propanol. The organic layer was dried over sodium sulfate and the solvent was removed. The residue was purified by silica gel column chromatography using heptane as eluent to give 19.8 g (86% yield) of intermediate 10-1 as a beige solid.

[0841] ESI-MS: 491 [M+H] + .

[0842] Intermediate 10-2

[0843]

[0844] Intermediate 10-2 2.60 g (5.30 mmol) of intermediate 10-1, 1.38 g (5.45 mmol) of bis(pinacolato)diboron and 1.04 g (10.60 mmol) of sodium acetate were suspended in 27 mL of toluene. The suspension was degassed using 3 freeze-thaw-lysis 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-thaw-lysis cycles, the reaction mixture was heated to 110 °C for 6 hours. The reaction was cooled to room temperature, diluted with toluene and water. The aqueous layer was extracted with toluene and the organic layer was washed with brine, dried over magnesium sulfate, filtered, and the solution was concentrated. The crude product was recrystallized from dichloromethane and acetonitrile to give 2.69 g (80% yield) of intermediate 10-2 as a white solid.

[0845] ESI-MS: 538.8 [M+H] + .

[0846] Intermediate 10-3

[0847]

[0848] Intermediate 10-3 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 portionwise. After the mixture was stirred at room temperature for 50 minutes, the reaction mixture was filtered. The filtrate was concentrated. The crude product was purified by column chromatography on silica gel using a mixture of heptane and dichloromethane as eluent. The product was precipitated in a mixture of dichloromethane and heptane to give 10.21 g (85% yield) of intermediate 10-3 as a white solid.

[0849] ESI-MS: 508 [M-H] - .

[0850] Intermediate 10-4

[0851]

[0852] Intermediate 7-2 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 3 freeze-thaw-lysis cycles, 12 mg (0.05 mmol) of palladium acetate and 132 mg (0.32 mmol) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl were added to the mixture. Then, after two additional freeze-thaw-lysis cycles, the mixture was stirred at 85°C for 16.5 hours. The reaction was cooled to room temperature, diluted with toluene. The organic extract was washed with water, dried over sodium sulfate, filtered and the solution was concentrated. The residue was purified by column chromatography on silica gel using a mixture of heptane and toluene as eluent to give 2.11 g (yield 93%) of intermediate 7-2 as a white solid.

[0853] ESI-MS: 839.8 [M+H] + .

[0854] Compound 10

[0855]

[0856] Intermediate 10-4 (2.11 g, 2.51 mmol) was dissolved in 36 mL dichlorobenzene. Then, to the solution was added 5.14 mL (5.12 mmol) of 1.0 M boron tribromide in heptane 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 was cooled to room temperature and diluted with methanol. The precipitate was collected by filtration and washed with ethanol and water. The crude product was dissolved in dichloromethane, precipitated with isopropanol and then filtered to give 1.77 g (83% yield) of compound 10 as a yellow solid.

[0857] ESI-MS: 849.7 [M+H] + .

[0858] Compound 11

[0859] Intermediate 11-1

[0860]

[0861] Intermediate 11-1 (23.5 g, 112 mmol) was dissolved in 130 mL of toluene, 130 mL of ethanol and 250 mL of 10% aqueous sodium carbonate solution. 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 small stream of N2. The reaction mixture was heated to reflux for 2 hours and then cooled to room temperature. The reaction mixture was extracted with toluene, the organic phase was washed with water and brine, dried over magnesium sulfate and filtered through a small pad of silica gel. The product was eluted with heptane and the solvent was removed on a rotary evaporator. The crude product was used without further purification as intermediate 11-1.

[0862] 1 H NMR (300 MHz, dichloromethane-d2) 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). d 2) δ -119.44. J J

[0863] 19 F NMR (282 MHz, dichloromethane-d2) δ -119.44. d

[0864] Intermediate 11-2

[0865] ​​​

[0866] To 260 g (1.26 mol) of 2,4-di-tert-butylphenol and 330 g (1.89 mol) of 1-bromo-2-fluorobenzene was added to 5.70 L of N-methylpyrrolidone, and 821 g (2.52 mol) of cesium carbonate was added. The mixture was stirred at 170 °C for 90 hours. The reaction was cooled to room temperature and water was added to it. The organic layer was collected. After concentration, the residue was purified by silica gel column chromatography using heptane as eluent to give 409 g (90% yield) of intermediate 11-2 as a beige solid.

[0867] The product was used without further purification.

[0868] Intermediate 11-3

[0869]

[0870] To 399 g (1.10 mol) of intermediate 11-2 was dissolved in 1.40 L of N-methylpyrrolidone, and 821 g (2.52 mol) of cesium carbonate was added. Under 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 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 eluent. The main fraction was partially concentrated, precipitated by solvent replacement with heptane, then filtered to give 227 g (73% yield) of intermediate 11-3 as a white solid.

[0871] ESI-MS: 280 [M+H] + .

[0872] Intermediate 11-4

[0873]

[0874] Dissolve 118 g (421 mmol) of intermediate 11-3 in 1.20 L of THF and cool the solution at 5°C. Under an argon atmosphere, add dropwise 400 ml (620 mmol) of 1.55 M n-butyllithium in hexane at 5°C. After cooling the reaction mixture to -60°C, add 118 g (631 mmol) of 1,2-dibromoethane and stir the mixture for 17 hours. Add 500 ml of water to the reaction mixture and extract the aqueous phase with toluene. Collect the organic phase and wash with brine. After concentration, purify the residue by column chromatography on silica gel with toluene as eluent. Concentrate the main fractions. Dissolve the product in hot heptane and recrystallize with an ice water bath to obtain 77 g (51% yield) of intermediate 11-4 as a white solid.

[0875] ESI-MS: 360 [M+H] + .

[0876] Intermediate 11-5

[0877]

[0878] Under an inert atmosphere, add dropwise 9.57 mL of n-butyllithium (1.6 M in hexane) to a solution of 5.00 g (13.9 mmol) of intermediate 11-4 in 50 mL of tetrahydrofuran while maintaining the temperature below -60°C using an acetone-dry ice bath. After the addition is complete, stir the reaction at -78°C for 15 minutes and then slowly add 2.20 mL (19.7 mmol) of trimethylborate while maintaining the temperature below -60°C. After the addition is complete, stir the reaction at -78°C for 15 minutes, then slowly warm to room temperature and stir for 17 hours to obtain a milky solution. Add 50 mL of a 10% HCI solution to the reaction and stir the yellow biphasic mixture for 1 hour. Extract the resulting mixture with ethyl acetate and wash the organic extract with water and brine, dry over magnesium sulfate, and filter through a short pad of silica gel. Remove the solvent on a rotary evaporator to obtain 4.25 g (60% yield) of intermediate 11-5 as a white solid.

[0879] 1 H 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).

[0880] Intermediate 11-6

[0881]

[0882] To a mixture of 7.00 g (29.6 mmol) of 1-bromo-4-chloro-2-nitrobenzene, 10.1 g (31.1 mmol) of Intermediate 11-5 in 70 mL of toluene, 70 mL of ethanol, and 70 mL of 10% aqueous sodium carbonate was added 0.80 g (2.2 mol%) of tetrakis(triphenylphosphine)palladium(0) under a stream of N2. The reaction mixture was heated to reflux for 2 h, then cooled to room temperature. The reaction mixture was extracted with heptane, and the organic phase was washed with water and brine, dried over magnesium sulfate, and the solvent was removed on a rotary evaporator. The crude product was dissolved in a 1:1 mixture of dichloromethane / ethanol and concentrated on a rotary evaporator until a yellow suspension formed. The suspension was stirred at room temperature for 1 h, filtered, to give 10.4 g (80% yield) of Intermediate 11-6 as a bright yellow solid.

[0883] 1 H NMR (300 MHz, Chloroform-d 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).

[0884] Intermediate 11-7

[0885]

[0886] 10.4 g (23.9 mmol) of intermediate 11-6 and 15.8 g (59.6 mmol) of triphenylphosphine were dissolved in 100 mL of 1,2-dichlorobenzene and heated to reflux for 3 hours. The 1,2-dichlorobenzene and triphenylphosphine were then distilled under reduced pressure, the red oil was cooled, and heptane was added with stirring. The resulting orange suspension was stirred at room temperature, then at 0 °C for 30 minutes, and then filtered. The solvent was removed from the filtrate using a rotary evaporator, and the crude product was purified by silica gel column chromatography using a mixture of heptane and toluene to give a grayish-white solid. The solid was dissolved in refluxed ethanol and precipitated by adding water at room temperature. The resulting suspension was filtered, and subsequent products were combined to give 8.0 g (83% yield) of intermediate 11-7 as a white solid.

[0887] ESI-MS: 402.4 [MH] - .

[0888] Intermediate 11-8

[0889]

[0890] 10.4 g (39.6 mmol) of intermediate 11-1, 8.00 g (19.8 mmol) of intermediate 11-7, and 8.41 g (39.6 mmol) of potassium phosphate were suspended in 80 mL of N,N-dimethylformamide and heated to 110 °C for 5 hours. The suspension was then cooled to 100 °C, and water was slowly added. The resulting off-white suspension was cooled to room temperature and filtered. The crude solid was ground three times in a 9:1 mixture of hot ethanol and water to give 12.5 g (96% yield) of intermediate 11-8 as a white solid.

[0891] ESI-MS: 646.6 [M+H] + .

[0892] Intermediate 11-9

[0893]

[0894] Intermediate 11-8 (4.00 g, 6.20 mmol) and 5.2 g (24.8 mmol) potassium phosphate were dissolved in a mixture of 120 mL dioxane and 30 mL water, and the mixture was degassed by bubbling N2. 312 mg (12 mol%) SPhos and 30 mg (2 mol%) palladium(II) acetate were added, and the reaction was heated to 85 °C. A previously degassed solution of Intermediate 2-3 (3.52 g, 8.68 mmol) in 56 mL dioxane (0.155 M) was added dropwise over 45 minutes, and the reaction mixture was heated to 95 °C for 3 hours. The reaction was cooled to room temperature and poured into water. The resulting precipitate was stirred for 30 minutes and filtered. The crude solid was dissolved in dichloromethane, and the organic phase was washed with water and brine. The organics were dried over magnesium sulfate, 0.5 g activated carbon was added, and the mixture was then refluxed for 30 minutes. The suspension was filtered over a pad of silica gel, and the product was eluted with more dichloromethane. Methanol was added to the filtrate, and the mixture was concentrated on a rotary evaporator until a precipitate formed. The suspension was cooled to room temperature and filtered. The solid was purified by silica gel column chromatography using a mixture of heptane and dichloromethane to give 3.1 g (28% yield) of Intermediate 11-9 as a white foam.

[0895] ESI-MS: 889.9 [M+H] + 。

[0896] Compound 11

[0897]

[0898] Under an inert atmosphere, 3.50 mL of tert-butyllithium (1.9 M in hexanes) was added dropwise to a solution of 1.95 g (2.19 mmol) of Intermediate 11-9 in 200 mL of tert-butylbenzene while maintaining the temperature below -50 °C using an acetone-dry ice bath. After the addition was complete, the reaction was heated to 45 °C for 1 hour, cooled to -78 °C, and then 0.35 mL (3.70 mmol) of boron tribromide was added slowly while maintaining the temperature below -60 °C. The reaction was allowed to warm to room temperature, 1.10 mL (6.58 mmol) of N,N-diisopropylethylamine was added, and the mixture was heated to 150 °C for 17 hours. The reaction was then cooled to room temperature, quenched with water, and filtered. The biphasic filtrate was extracted with toluene, and the organic phase was washed twice with 10% aqueous sodium carbonate solution followed by brine. The organic extract was dried over magnesium sulfate and filtered through a pad of silica gel. The bright orange solution was concentrated to approximately 100 mL on a rotary evaporator, and 300 mL of ethanol was added to it. The precipitate was cooled to room temperature and stirred for 17 hours, then filtered. The resulting solid was purified by silica gel chromatography using a mixture of heptane and dichloromethane. The resulting resin was dissolved in 200 mL of dichloromethane and 200 mL of ethanol and concentrated on a rotary evaporator at 60 °C until a suspension formed. The hot filtrate was then filtered, and the solid was washed with some cold ethanol to give 215 mg (11.4% yield) of Compound 11 as a bright yellow solid.

[0899] ESI-MS: 864.0 [M+H] + .

[0900] Compound 12

[0901] Intermediate 12-1

[0902]

[0903] To 30.0 g (134 mmol) of 4-(bromophenyl)hydrazine hydrochloride in 270 mL of acetic acid was added dropwise 20.7 g (134 mmol) of 4-(tert-butyl)cyclohexan-1-one at 80 °C under nitrogen. The reaction mixture was then stirred at 100 °C for 5 hours.

[0904] The solvent was removed in vacuo, and the reaction mixture was dissolved in toluene. The organic phase was washed with water, then with sodium bicarbonate solution. The organic phase was dried over magnesium sulfate, and the solvent was removed in vacuo. The product was used without purification in the next reaction step. Yield 41.0 g.

[0905] Intermediate 12-2

[0906]

[0907] To 41.0 g (134 mmol) of 6-bromo-3-(tert-butyl)-2,3,4,9-tetrahydro-1 H- carbazole in 250 mL of toluene under nitrogen was added 60.8 g (268 mmol) of 2,3- dichloro-5,6-dicyano-1,4-benzoquinone over 10 minutes. The reaction was exothermic. The reaction mixture was then stirred at 25 °C for 1 hour. The solids were filtered and washed with toluene. The organic phase was washed with 10% aqueous sodium hydroxide solution. The organic phase was washed with water, brine, dried over magnesium sulfate. The solvent was removed in vacuo. Column chromatography on silica gel using heptane / ethyl acetate 95 / 5 gave the product. Yield 21.6 g (52%)

[0908] 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).

[0909] Intermediate 12-3

[0910]

[0911] To 17.9 g (59 mmol) of 6-bromo-3-(tert-butyl)-2,3,4,9-tetrahydro-1 H-carbazole in 300 mL of dioxane and 50 mL of water was added 27.1 g (107 mmol) of 4,4,4',4',5,5,5',5'-octamethyl-2,2'-bi(1,3,2-dioxaborolane) and 17.4 g (178 mmol) of potassium acetate. The reaction mixture was degassed with argon. 542 mg (0.592 mmol) of tris(dibenzylideneacetone)dipalladium(0) and 564 mg (1.18 mmol) of 2-dicylohexylphosphino-2',4',6'-triisopropylbiphenyl (XPhos) were added. The reaction mixture was degassed with argon. The reaction mixture was stirred at 110 °C under argon for 8 hours. The solids were filtered and the aqueous phase was removed. The solvent was removed in vacuo. Column chromatography on silica gel using heptane / ethyl acetate 90 / 10 gave the product. Yield 11.7 g (55%)

[0912] 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).

[0913] Intermediate 12-4

[0914]

[0915] 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 was added 9.81 g (36.8 mmol) of 2-chloro-4, 6-diphenylpyrimidine and 11.6 g (84.0 mmol) of potassium carbonate. The reaction mixture was degassed 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 under argon for 8 hours. The aqueous phase was removed. The solvent was removed in vacuo. Silica gel column chromatography using heptane / ethyl acetate 95 / 5 and heptane / ethyl acetate 90 / 10 gave the product. Yield 6.75 g (44%)

[0916] ESI-MS: 454 [M+1] + .

[0917] 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).

[0918] Intermediate 12-5

[0919]

[0920] To 6.75 g (14.9 mmol) of 3- (tert-butyl) -6- (4, 6-diphenylpyrimidin-2-yl) -9H-carbazole in 60 mL of acetic acid was added 2.65 g (14.9 mmol) of N-bromosuccinimide and the reaction mixture was stirred at 20°C under nitrogen. After 2.5 hours, the product was filtered, washed with acetic acid and then with methanol. Silica gel column chromatography using heptane / ethyl acetate 97 / 3 gave the product. Yield 4.00 g (39%). The product was crystallized from toluene.

[0921] 1H-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).

[0922] Intermediate 12-6

[0923]

[0924] To 1.52 g (2.85 mmol) of 1-bromo-3-(tert-butyl)-6-(4,6-diphenylpyrimidin-2-yl)-9H- carbazole in 30 ml of toluene, 15 ml of dioxane and 10 ml of water, 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 potassium phosphate tribasic were added. The reaction mixture was degassed with argon. 94 mg (0.23 mmol) of dicyclohexyl(2',6'-dimethoxy[1,1 '-biphenyl]-2-yl)phosphine 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 under argon for 1 hour, the solid was filtered and washed with heptane. The organic phase was dried over magnesium sulfate and the solvent was removed under vacuum. The product was obtained using silica gel column chromatography with heptane / ethyl acetate 95 / 5. Yield 2.19 g (88%).

[0925] 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, 18H), 1.43 (s, 18 H).

[0926] Compound 12

[0927]

[0928] To 1.98 g (2.29 mmol) of 3- (tert-butyl) -1- (3- (tert-butyl) -5- (3, 6-di-tert-butyl-9H-carbazol-9-yl) phenyl) -6- (4, 6-diphenylpyrimidin-2-yl) -9H-carbazole in 26 mL of o-dichlorobenzene under argon was added 1.19 g (9.18 mmol) of N-ethyl-N-isopropylpropan-2-amine. To the reaction mixture was added 4.59 mL (4.50 mmol) of 1M tribromoborane in heptane over 5 minutes under argon. The reaction mixture was stirred at 185 °C for 2.5 hours under argon. The reaction mixture was cooled to 25 °C and methanol was added. The product was filtered and washed with methanol. Silica gel column chromatography using 100% dichloromethane gave the product. Yield 1.71 g (77%).

[0929] ESI-MS: 871.8 [M+1] +

[0930] 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).

[0931] Compound 13

[0932] Intermediate 13-1

[0933]

[0934] To 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 was added to 95 mL of acetic acid, the mixture was stirred at 100 °C for 2 hours, after the reaction mixture was cooled to room temperature, the solid was collected by filtration and washed with ethyl acetate. The filtrate was concentrated, then the residue was purified by silica gel column chromatography using a mixture of heptane and dichloromethane as eluent to give 11.2 g (54% yield) of intermediate 13-1 as a white solid.

[0935] ESI-MS: 433 [M+H] + .

[0936] Intermediate 13-2

[0937]

[0938] To a solution of 7.03 g (16.27 mmol) of intermediate 13-1 and 7.39 g (32.50 mmol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in 60 mL of toluene, the mixture was stirred at 100 °C for 2.5 hours. After the reaction mixture was cooled to room temperature, the solid was removed by filtration and washed with toluene. The filtrate was concentrated and then the residue was purified by silica gel column chromatography using a mixture of heptane and dichloromethane as eluent to give 4.73 g (68% yield) of intermediate 13-2 as a beige powder.

[0939] ESI-MS: 427 [M+H] + .

[0940] Intermediate 13-3

[0941]

[0942] To a solution of 4.28 g (10.00 mmol) of intermediate 13-2, 1.78 g (10.00 mmol) of 4-tert-butylphenylboronic acid and 2.76 g (19.99 mmol) of potassium carbonate in 50 mL of toluene, 10 mL of ethanol and 10 mL of water, 578 mg (0.50 mmol) of tetrakis(triphenylphosphine)palladium was added to the mixture after the solution was degassed using 3 freeze-pump-thaw cycles. Then, the mixture was stirred at 70 °C for 20 hours after two additional freeze-pump-thaw cycles. The reaction was cooled to room temperature and diluted with toluene. The organic extract was washed with water, dried over sodium sulfate, filtered and the solution was concentrated. The residue was purified by silica gel column chromatography using a mixture of heptane and toluene as eluent to give 3.56 g (yield 82%) of intermediate 13-3 as a white solid.

[0943] ESI-MS: 433 [M-H] - .

[0944] Intermediate 13-4

[0945]

[0946] Intermediate 8-1 (3.40 g, 5.30 mmol), bis(pinacolato)diboron (1.38 g, 5.45 mmol), and sodium acetate (1.04 g, 10.60 mmol) were suspended in 27 mL of toluene. The suspension was degassed using 3 freeze-thaw- defrost cycles, and tris(dibenzylideneacetone)dipalladium(0) (120 mg, 0.13 mmol) and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (152 mg, 0.51 mmol) were added to the mixture. After two additional freeze-thaw-defrost cycles, the reaction mixture was heated to 110 °C for 6 h. The reaction was cooled to room temperature, diluted with toluene and water. The aqueous layer was extracted with toluene, and the organic layer was washed with brine, dried over magnesium sulfate, filtered, and the solution was concentrated. The crude product was recrystallized from dichloromethane and acetonitrile to give 2.74 g (75% yield) of Intermediate 13-4 as a white solid.

[0947] ESI-MS: 690 [M+H].

[0948] Intermediate 13-5

[0949]

[0950] Intermediate 13-3 (1.39 g, 3.22 mmol), Intermediate 10-2 (3.06 g, 4.84 mmol), and potassium phosphate (2.73 g, 12.8 mmol) were dissolved in 21 mL of toluene, 11 mL of dioxane, and 7 mL of water. After degassing the solution using 3 freeze-thaw-defrost cycles, palladium acetate (15 mg, 0.06 mmol) and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (158 mg, 0.38 mmol) were added to the mixture. The mixture was then stirred to 85 °C for 16.5 h after two additional freeze-thaw-defrost cycles. The reaction was cooled to room temperature, diluted with toluene. The organic extract was washed with water, dried over sodium sulfate, filtered, and the solution was concentrated. The residue was purified by silica gel column chromatography using a mixture of heptane and toluene as eluent to give 2.15 g (79% yield) of Intermediate 13-5 as a white solid.

[0951] ESI-MS: 918 [M+H] + .

[0952] Compound 13

[0953]

[0954] Intermediate 13-5 (1.83 g, 2.00 mmol) was dissolved in 28 mL of dichlorobenzene. Then, to the solution was added 4.10 mL (4.10 mmol) of 1.0 M boron tribromide in heptane 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 was cooled to room temperature and diluted with methanol. The precipitate was collected by filtration and washed with ethanol and water. The crude product was dissolved in dichloromethane, precipitated with isopropanol and then filtered to give 1.39 g (75% yield) of compound 13 as a yellow solid.

[0955] ESI-MS: 925 [M+H] + .

[0956] Compound 14

[0957] Intermediate 14-1

[0958]

[0959] Intermediate 14-1 (21.0 g, 85.0 mmol) was dissolved in 210 mL of dichlorobenzene. Then, to the solution was added 42.0 mL (42.0 mmol) of 1.0 M boron tribromide in heptane followed by 14.0 mL (85.0 mmol) of N,N-diisopropylethylamine and the mixture was stirred at 180 °C for 15 hours. The reaction was cooled to room temperature and diluted with methanol. The precipitate was collected by filtration and washed with ethanol and water. The crude product was dissolved in dichloromethane, precipitated with isopropanol and then filtered to give 14.0 g (65% yield) of compound 14 as a yellow solid.

[0960] Intermediate 14-2

[0961]

[0962] Intermediate 14-2 was prepared according to the following scheme:

[0963] ESI-MS: 556.2 [M-H] - .

[0964] Intermediate 14-3

[0965]

[0966] Intermediate 14-2 was prepared according to the following scheme:

[0967] ESI-MS: 552.2 [M-H] - .

[0968] Intermediate 14-4

[0969]

[0970] Intermediate 14-3 (11.0 g, 19.85 mmol), 3,3-dimethyl-l-(4- methoxyphenyl)-lH-inden-5-ylboronic acid (5.00 g, 19.85 mmol) and sodium carbonate (4.63 g, 43.7 mmol) were dissolved in 120 mL of toluene, 120 mL of ethanol and 40 mL of water. After the solution was degassed using 3 freeze-pump-thaw cycles, 688 mg (0.60 mmol) of palladium tetrakis(triphenylphosphine) was added to the mixture. Then, after two additional freeze-pump-thaw cycles, the mixture was stirred to 80 °C for 4 hours. The reaction was cooled to room temperature and 1 g of sodium cyanide dissolved in 50 mL of water was added. The reaction mixture was stirred for 30 minutes. The organic extract was washed with water, dried over sodium sulfate, filtered and the solution was concentrated. The crude product was purified by silica gel column chromatography using a mixture of heptane and dichloromethane as eluent to give 7.33 g (65% yield) of intermediate 14-4 as a beige solid.

[0971] ESI-MS: 560.5 [M-H] - .

[0972] Intermediate 14-5

[0973]

[0974] Intermediate 14-4 (1.50 g, 2.68 mmol), intermediate 10-2 (2.15 g, 4.01 mmol) and potassium phosphate (2.28 g, 10.70 mmol) were dissolved in 22 mL of toluene, 11 mL of dioxane and 7 mL of water. After the solution was degassed using 3 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. Then, after two additional freeze-pump-thaw cycles, the mixture was stirred to 85 °C for 21 hours. The reaction was cooled to room temperature and diluted with toluene. The organic extract was washed with water, dried over sodium sulfate, filtered and the solution was concentrated. The residue was purified by silica gel column chromatography using a mixture of heptane and toluene as eluent to give 1.72 g (72% yield) of intermediate 14-5 as a white solid.

[0975] ESI-MS: 891 [M-H] - .

[0976] Compound 14

[0977]

[0978] Intermediate 14-5 was dissolved in 28 mL dichlorobenzene. Then, to the solution was added 4.10 mL (4.10 mmol) of 1.0 M boron tribromide in heptane 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 was cooled to room temperature and diluted with methanol. The precipitate was collected by filtration and washed with ethanol and water. The crude product was dissolved in dichloromethane, precipitated with isopropanol and then filtered to give 1.41 g (83% yield) of compound 14 as a yellow solid.

[0979] ESI-MS: 900 [M+H] + .

[0980] Compound 15

[0981] Intermediate 15-1

[0982]

[0983] To a solution of 26.4 g (78.0 mmol) of Intermediate 7-1 in 250 mL of 1,4-dioxane was added 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, 2.73 mL (22.75 mmol) of cyclohexane-1,2-diamine. The suspension was degassed with Ar and then heated to 85 °C for 1.5 hours. After cooling to room temperature, the suspension was filtered with celite and washed with warm toluene (4 x 100 mL). The filtrate was evaporated and the resulting residue was purified by column chromatography on silica gel using heptane as eluent. The resulting white solid was further recrystallized from cyclohexane (2 x 150 mL) to give 14.66 g (80% yield) of Intermediate 15-1 as a white solid.

[0984] 1 H NMR (300 MHz, Chloroform-d) 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). 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).

[0985] Intermediate 15-3

[0986]

[0987] Intermediate 15-3 was prepared according to the procedure described in WO2016 / 015449. 12.30 g (27.5 mmol) of intermediate 15-1, 11.15 g (27.5 mmol) of intermediate 2-3, 2.20 g (55.0 mmol) of sodium hydroxide were suspended in a mixture of tetrahydrofuran / 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 was cooled to room temperature and diluted with toluene / water. The layers were separated and the aqueous layer was further extracted with toluene. The organic extracts were washed with water, brine, dried over sodium sulfate, filtered and evaporated. The residue was purified by column chromatography on silica gel using heptane / toluene as eluent to give 17.76 g (100% yield) of intermediate 15-2 as a white foam.

[0988] ESI-MS: 643.4 [M-H] - .

[0989] Intermediate 15-3

[0990]

[0991] Intermediate 15-3 was prepared according to the procedure described in WO2016 / 015449. 12.30 g (27.5 mmol) of intermediate 15-1, 11.15 g (27.5 mmol) of intermediate 2-3, 2.20 g (55.0 mmol) of sodium hydroxide were suspended in a mixture of tetrahydrofuran / 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 was cooled to room temperature and diluted with toluene / water. The layers were separated and the aqueous layer was further extracted with toluene. The organic extracts were washed with water, brine, dried over sodium sulfate, filtered and evaporated. The residue was purified by column chromatography on silica gel using heptane / toluene as eluent to give 17.76 g (100% yield) of intermediate 15-2 as a white foam.

[0992] ESI-MS: 653.3 [M+H] + .

[0993] Compound 15

[0994]

[0995] Intermediate 15-3, 2.80 g (14.4 mmol) of (4-(trimethylsilyl)phenyl)boronic acid, 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 to 80°C for 1.5 hours. The reaction was cooled to room temperature and diluted with toluene / water. The layers were separated and the aqueous layer was further extracted with toluene. The organic extracts were washed with water, brine, dried over sodium sulfate, filtered and evaporated. The residue was purified by column chromatography on silica gel using heptane / toluene as eluent to give 2.98 g (94% yield) of compound 15 as a yellow solid.

[0996] ESI-MS: 881.5 [M+H] + .

[0997] Compound 16

[0998]

[0999] Intermediate 15-3, 2.62 g (16.0 mmol) of (2-isopropylphenyl)boronic acid, 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 to 80°C for 5 hours. The reaction was cooled to room temperature and diluted with toluene / water. The layers were separated and the aqueous layer was further extracted with toluene. The organic extracts were washed with water, brine, dried over sodium sulfate, filtered and evaporated. The residue was purified by column chromatography on silica gel using heptane / toluene as eluent to give 3.15 g (96% yield) of compound 16 as a yellow solid.

[1000] ESI-MS: 821.5 [M+H] + .

[1001] Compound 17

[1002] Intermediate 17-1

[1003]

[1004] 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 three hours at room temperature. The yellow suspension was stirred for 30 minutes, then treated with 1.5 L of water and stirred for another hour. The suspension was filtered, and the solid was washed with 500 mL of water. The solid was then suspended in 400 mL of 10% sodium carbonate aqueous solution. The suspension was filtered again, and the solid was washed with 500 mL of water. The solid was further suspended in 150 mL of ethanol, filtered, and washed with 50 mL of ethanol to give 43.2 g (93% yield) of intermediate 17-1 as a white solid.

[1005] 1 H NMR (300 MHz, DMSO- d 6) δ 7.98 (s, 1H), 7.80 (s, 1H), 1.66 (s, 4H), 1.27 (d, 12H).

[1006] Intermediate 17-2

[1007]

[1008] 20.0 g (61.7 mmol) of 2-bromo-N,N-diphenylaniline was added dropwise over 15 minutes with 25.9 mL of n-butyllithium (2.5 M, in hexane) to 200 mL of tetrahydrofuran at -78 °C. 32.5 mL of zinc chloride solution (1.9 M, in 2-methyltetrahydrofuran) was added at -78 °C, and the yellow solution was warmed to room temperature over 45 minutes. 18.3 g (58.6 mmol) of intermediate 17-2, 565 mg (0.62 mmol) of tris(dibenzylacetone)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 filter, followed by rinsing the silica gel filter 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 was purified by MPLC using a CombiFlash Companion (silica gel, heptane / 0-40% toluene gradient) to give 20.3 g (73% yield) of intermediate 17-2 as a white solid.

[1009] ESI-MS (positive, m / z): C 32 H 32Exact mass for N2O2 = 476.25; Found 477.4 [M + 1] + .

[1010] Intermediate 17-3

[1011]

[1012] Intermediate 17-3 20.0 g (42.0 mmol) of Intermediate 17-2 and 33.0 g (126 mmol) of triphenylphosphine were heated in 100 mL of 1,2-dichlorobenzene at 174 °C for three hours. The reaction mixture was concentrated under vacuum. The product was stirred in 100 mL of heptane for one hour. The suspension was filtered and the solid was washed with heptane. The filtrate was concentrated under vacuum and the solid was dissolved in dichloromethane and then filtered through a 4 cm silica gel plug followed by rinsing the silica gel plug with 150 mL of dichloromethane. The combined eluent was concentrated under vacuum and the product was purified by MPLC using a CombiFlash Companion (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 formed. The suspension was filtered and the solid was washed with heptane. The solid was suspended in 70 mL of t-butyl methyl ether. The suspension was filtered and the solid was washed with t-butyl methyl ether. The combined filtrate from the t-butyl methyl ether wash was concentrated under vacuum to give 6.9 g (37% yield) of Intermediate 17-3 as a solid.

[1013] ESI-MS (positive, m / z): C 32 H 32 Exact mass for N2 = 444.26; Found 445.4 [M + 1] + .

[1014] Intermediate 17-4

[1015]

[1016] 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 iodide (I), 154 mg (1.35 mmol) of cyclohexyl-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 and filtered through a 3 cm silica gel filter, followed by washing the silica gel filter 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 give 2.56 g (87% yield) of intermediate 17-4 as a white solid.

[1017] ESI-MS (positive, m / z): C 42 H 43 Precise mass of BrN2 = 654.26; measured mass 657.4 [M +3] + .

[1018] Intermediate 17-5

[1019]

[1020] 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 toluene, 20 mL of 1,4-dioxane, and 10 mL of water. The solution was evacuated three times and backfilled with argon gas, and heated at 82 °C for 90 min. The reaction mixture was diluted with 50 mL toluene and 100 mL of water. The organic phase was separated, washed with water (3 × 50 mL), dried over sodium sulfate, and filtered through a 3 cm silica gel layer. The silica gel layer was washed with toluene, and the combined eluents were concentrated under vacuum. The product was subjected to MPLC using... CombiFlash Companion Purification (silica gel, heptane). The resulting product was diluted with 30 ml of dichloromethane and 50 ml of ethanol. The solution was concentrated to a volume of 50 ml under vacuum until a suspension was formed. The suspension was filtered, and the solid was washed with ethanol to give 2.4 g (74% yield) of intermediate 17-5 as a white solid.

[1021] ESI-MS (positive, m / z): C 62 H67 The precise mass of N3 is 853.53; the measured mass is 854.7 [M+1] + .

[1022] Compound 17

[1023]

[1024] 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 min and then cooled to 36 °C. 5.4 mL of tribromoborane (1.0 M, in heptane) was added dropwise, and heating was continued at 174 °C for another 90 min. The reaction mixture was cooled to room temperature, and 100 mL of methanol was added. The mixture was concentrated under vacuum, and the residue was dissolved in 100 mL of heptane and 100 mL of water. The organic phase was washed with water (3 × 50 mL), dried over sodium sulfate, filtered, and concentrated under vacuum. The resulting solid was dissolved in 20 mL of dichloromethane and 60 mL of ethanol. The solution was concentrated under vacuum to a volume of 50 mL until a suspension was formed. The suspension was filtered, and the solid was washed with ethanol. The product was passed through MPLC and used CombiFlash Companion Purification (silica gel, heptane / 0-10% dichloromethane gradient). 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 give 0.85 g (37% yield) of compound 17 as a yellow solid.

[1025] ESI-MS (positive, m / z): C 62 H 64 The precise mass of BN3 is 861.52; the measured mass is 862.6 [M+1]. + .

[1026] Compound 18

[1027]

[1028] Intermediate 15-3, 0.152 mg (1.0 mmol) (4-methoxyphenyl)boronic acid, 0.325 mg (1.0 mmol) 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%) palladium acetate and 12.3 mg (12 mol%) 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl were added to the reaction mixture. The reaction mixture was heated to 80 °C for 2 h. The reaction was cooled to room temperature and diluted with toluene / water. The layers were separated and the aqueous layer was further extracted with toluene. The organic extracts were washed with water, brine, dried over sodium sulfate, filtered and evaporated. The residue was purified by silica gel column chromatography using heptane / dichloromethane as eluent to give 123 mg (62% yield) of compound 18 as a yellow solid.

[1029] ESI-MS: 797.5 [M+H] + .

[1030] Compound 19

[1031]

[1032] Intermediate 15-3, 0.171 mg (1.22 mmol) (4-fluorophenyl)boronic acid, 0.399 mg (1.22 mmol) 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%) palladium acetate and 15.1 mg (12 mol%) 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl were added to the reaction mixture. The reaction mixture was heated to 80 °C for 24 h. The reaction was cooled to room temperature and diluted with toluene / water. The layers were separated and the aqueous layer was further extracted with toluene. The organic extracts were washed with water, brine, dried over sodium sulfate, filtered and evaporated. The residue was purified by silica gel column chromatography using heptane / toluene as eluent to give 166 mg (70% yield) of compound 19 as a yellow solid.

[1033] ESI-MS: 773.4 [M+H] + .

[1034] Compound 20

[1035] Intermediate 20-1

[1036]

[1037] A mixture of 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 was suspended in 200 mL of toluene. The suspension was evacuated three times and backfilled with argon and heated at 72 °C for 90 minutes. The dark suspension was cooled to room temperature and washed with water (2 x 100 mL). The organic phase was dried over sodium sulfate and concentrated in vacuo. The solid was recrystallized from 300 mL of ethanol and then washed with cold ethanol to give 18.8 g (76% yield) of intermediate 20-1 as a white solid.

[1038] ESI-MS (positive, m / z): C 46 H 55 Exact mass of CI N2 = 670.41 ; found 671.4 [M + H] + .

[1039] Intermediate 20-2

[1040]

[1041] A mixture of 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 potassium phosphate tribasic was 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 and backfilled with argon and heated at 82 °C for five 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 then dichloromethane was added. The mixture was filtered and the filtrate was concentrated in vacuo. The product was stirred in 30 mL of dichloromethane and 150 mL of ethanol until a suspension formed. The suspension was filtered and the solid was washed with 100 mL of ethanol and 100 mL of heptane to give 6.9 g (68% yield) of intermediate 20-2 as a white solid.

[1042] ESI-MS (negative, m / z): C 62 H 65 Exact mass of N3 = 851.52; found 850.4 [M-1]+ .

[1043] Compound 20

[1044]

[1045] Compound 20 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, 100 mL of methanol was added. The suspension was stirred for 15 minutes, then filtered. The solid was further purified by MPLC using CombiFlash Companion (silica gel, dichloromethane) to give 2.1 g (69% yield) of compound 20 as a yellow solid.

[1046] ESI-MS (positive, m / z): C 62 H 62 Exact mass of BN3 = 859.50; found 860.7 [M + 1] + .

[1047] Compound 21

[1048] Intermediate 21-1

[1049]

[1050] Compound 21 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 potassium phosphate tribasic 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 and backfilled with argon and heated at 86 °C for 26 hours. The reaction mixture was cooled, 50 mL of toluene and 50 mL of water were added. The organic phase was washed with water (3 x 50 mL), then dried over sodium sulfate and concentrated in vacuo. The solid product was suspended in 100 mL of heptane, then filtered and the solid was washed with heptane. The product was purified by MPLC using CombiFlash Companion(Silica gel, cyclohexane / 0-10% gradient ethyl acetate) further purification. The resulting solid was suspended in 30 mL dichloromethane and 50 mL ethanol. The suspension was filtered and the solid was washed with ethanol to give 3.65 g (53% yield) of intermediate 21-1 as a white solid.

[1051] ESI-MS (negative, m / z): C 45 H 48 Exact mass of N2Si = 644.36; found 643.3 [M-1] + .

[1052] Compound 21

[1053]

[1054] Compound 21 CombiFlash Companion (Silica gel, dichloromethane) further purification to give 1.02 g (32% yield) of compound 21 as a yellow solid.

[1055] ESI-MS (negative, m / z): C 42 H 37 Exact mass of BN2 = 580.30; found 581.7 [M +1] + .

[1056] Compound 22

[1057] Intermediate 22-1

[1058]

[1059] Intermediate 22-1 was prepared according to the procedure described in Scheme 22. To a solution of 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 in 102 mL of toluene was added 295 mg (0.51 mmol) of xantphos and 117 mg (0.13 mmol) of tris(dibenzylideneacetone)dipalladium(0) after the suspension was degassed using 3 freeze-pump-thaw cycles. The reaction mixture was then stirred at 100 °C for 14.5 h after two additional freeze-pump-thaw cycles. The reaction was cooled to room temperature, diluted with toluene and water. The aqueous layer was extracted with toluene. The organic extracts were 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 eluent to give 10.8 g (79% yield) of Intermediate 22-1 as a beige foam.

[1060] ESI-MS: 494.6 [M-H] - .

[1061] Intermediate 22-2

[1062]

[1063] A solution of 2.96 g (6.01 mmol) of Intermediate 22-1, 1.98 g (7.81 mmol) of bis(pinacolato)diboron and 1.18 g (12.02 mmol) of sodium acetate in 30 mL of toluene was degassed using 3 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 h. The reaction was cooled to room temperature and diluted with toluene and water. The aqueous layer was extracted with toluene and the organic layer was washed with brine, dried over magnesium sulfate, filtered, and the solution was concentrated. The crude product was recrystallized from dichloromethane and acetonitrile to give 2.56 g (79% yield) of Intermediate 22-2 as a white solid.

[1064] ESI-MS: 540.7 [M+H] + .

[1065] Intermediate 22-3

[1066]

[1067] 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-dip-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. The mixture was then stirred at 85 °C for 21 hours after two additional freeze-dip-thaw cycles. 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 was concentrated. The residue was purified by silica gel column chromatography using a mixture of heptane and toluene as the eluent to give 2.87 g (80% yield) of intermediate 22-3 as a white solid.

[1068] ESI-MS: 893.8 [MH] - .

[1069] Compound 22

[1070]

[1071] 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 a 1.0 M boron tribromide solution in heptane was added, followed by 2.3 mL (10.28 mmol) of N,N-diisopropylethylamine, and the mixture was stirred at 180 °C for 20 h. 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 crude product was purified by silica gel column chromatography using a mixture of heptane and dichloromethane as eluent. The product was dissolved in dichloromethane, precipitated with acetonitrile, and then filtered to give 2.19 g (76% yield) of compound 22.

[1072] ESI-MS: 901.2 [M+H] + .

[1073] Compound 23

[1074] Intermediate 23-1

[1075]

[1076] To a 250 mL flask was added 27.2 g (86.0 mmol) of 2-bromo-4-chloro-l- iodobenzene, 20.0 g (82.0 mmol) of N-phenyl-2-biphenylamine, and 11.0 g (114 mmol) of sodium tert-butoxide. The mixture was degassed by bubbling N2for 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 pad of silica gel and the product was eluted with heptane. The filtrate and washings were combined, the solvent was removed on a rotary evaporator, then dried under high vacuum at 200 °C, and the oil was crystallized from a minimal amount of hot heptane. The brown solid was then dissolved in dichloromethane, washed twice with 0.05% aqueous sodium cyanide, then washed with brine. The organics were dried over magnesium sulfate, and the solvent was removed on a rotary evaporator. The oil was crystallized from a minimal amount of hot heptane, filtered, and washed with pentane to give 10.9 g (28.4% yield) of intermediate 23-1 as a white solid.

[1077] 1 H NMR (300 MHz, DMSO- d 6) δ 7.45 (d, J = 2.4 Hz, 1H), 7.42 - 7.30 (m, 1H), 7.30 - 7.08 (m, 10H), 7.07 - 7.00 (m, 1H), 7.00 - 6.84 (m, 1H), 6.75 (m, 3H).

[1078] Intermediate 23-2

[1079]

[1080] Under an inert atmosphere, 35 mL of n-butyllithium (2.5 M in hexanes) was added dropwise to a solution of 34.0 g (78.2 mmol) of intermediate 23-1 in 360 mL of tetrahydrofuran while maintaining the temperature below -60 °C using an acetone-dry ice bath. After the addition was complete, the reaction was stirred at -78 °C for 1.5 hours. Then 30 mL (268 mmol) of trimethyl borate was added slowly while maintaining the temperature below -60 °C. After the addition was complete, the reaction was stirred at -78 °C for 15 minutes, then warmed to room temperature slowly, and stirred for 20 minutes to give a milky solution. 400 ml of 10% HC1 solution was added to the reaction, and the biphasic mixture was stirred for 1 hour. The organic solvent was removed on a rotary evaporator, and the resulting suspension was filtered. The solid was triturated in 500 mL of heptane under reflux for 1 hour. The white suspension was then concentrated to half volume on a rotary evaporator and stirred at 0 °C for 1 hour, then filtered to give 22.3 g (71.3% yield) of intermediate 23-2 as a white solid.

[1081] ESI-MS: 400.2 [M+H] + .

[1082] Intermediate 23-3

[1083]

[1084] Intermediate 23-3 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 palladium(0) tetrakis(triphenylphosphine) was added, and the reaction was heated to 85 °C for 3 hours. The reaction was cooled to room temperature and poured into water, extracted with dichloromethane, and the organic phase was washed with water and brine. The organics were dried over magnesium sulfate, heptane was added, then the dichloromethane was removed on a rotary evaporator until a precipitate began to form. After stirring the precipitate at about 15 °C, the suspension was filtered and washed with heptane. The solid was dissolved in 50 mL of dichloromethane, 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 give 4.72 g (55% yield) of intermediate 23-3 as a yellow solid.

[1085] ESI-MS: 533.3 [M+H] + .

[1086] Intermediate 23-4

[1087] Intermediate 23-4

[1088] 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 5 g of activated carbon. The suspension was then hot-filtered on a Hyflo® Super-Cel® pad, which was washed with heptane. The combined filtrates were filtered on a silica pad. The pad was washed with heptane, and the colorless filtrate was discarded. The product was then eluted with toluene to give an orange filtrate. The solvent was removed from the filtrate using a rotary evaporator, and the crude product was purified twice by silica gel column chromatography using a mixture of heptane and dichloromethane. The resulting resin was dissolved in a mixture of heptane and dichloromethane, and the dichloromethane was removed using 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 give 4.53 g (30% yield) of intermediate 23-4 as a white solid.

[1089] ESI-MS: 499.4 [MH] - .

[1090] Intermediate 23-5

[1091]

[1092] 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. The reaction mixture was degassed by bubbling with N2. 66 mg (2 mol%) of tris(dibenzylacetone)dipalladium(0) and 137 mg (8 mol%) of Xphos were added, and the reaction mixture was heated to 90 °C for 24 hours. Then, another 33 mg (1 mol%) of tris(dibenzylacetone)dipalladium(0) and 69 mg (4 mol%) of Xphos were added, and the reaction mixture was further heated at 90 °C for 3 hours, then cooled to room temperature. The reaction mixture was poured into 200 mL of saturated ammonium chloride aqueous solution and extracted with ethyl acetate. The organic phase was washed with water and brine, dried over magnesium sulfate, and filtered through a silica gel pad. The pad was washed with ethyl acetate, and the solvent in the filtrate was evaporated on a rotary evaporator. The crude product was purified by silica gel column chromatography using a mixture of heptane and ethyl acetate as eluent, followed by purification using a mixture of heptane and toluene as eluent. The resulting colorless foam was dissolved in dichloromethane and methanol was added. The solution was concentrated at room temperature using a rotary evaporator until a precipitate formed. The suspension was stirred at -40°C for 20 minutes and filtered. A second batch of product was filtered from the mother liquor, and the white solids were combined to give 1.49 g (47% yield) of intermediate 23-5 as a white solid.

[1093] ESI-MS: 878.7 [M+H] + 876.6 [MH] - .

[1094] Compound 23

[1095]

[1096] Under an inert atmosphere, 0.75 mL of n-butyllithium (2.5 M, in hexane) was added dropwise to a solution of 1.50 g (1.71 mmol) of intermediate 23-5 in 70 mL of tert-butylbenzene, while maintaining the temperature below -15 °C using an ice / sodium chloride bath. After the addition was complete, the reaction mixture was heated to room temperature for 20 minutes, then cooled to -15 °C, and 3.5 mL of boron tribromide (1 M, in hexane) was slowly added while maintaining the temperature below -10 °C. The reaction mixture was then heated to 120 °C for 5 hours. The reaction mixture was then cooled to room temperature and quenched with 100 mL of 10% sodium bicarbonate aqueous solution. The organic phase was washed twice with water, dried over sodium sulfate, and filtered through a silica gel pad. The pad was washed with toluene, and the filtrate was concentrated on a rotary evaporator to remove toluene. The yellow solution was cooled to 0 °C, and 300 mL of acetonitrile was added. A precipitate formed slowly over 2 hours, and the resulting solid was filtered off. The mother liquor was concentrated to an oily state using a rotary evaporator and dissolved in dichloromethane. 70 mL of acetonitrile was added, and the solution was concentrated to approximately 40 mL using a rotary evaporator. The solution was cooled to room temperature, seeded with crystals from the previous precipitate, and stirred for 1 hour. The resulting precipitate was then filtered, and the combined solids were purified twice by silica gel column chromatography using a mixture of heptane and dichloromethane as eluent. The purified product was dissolved in 50 mL of dichloromethane and 75 mL of acetonitrile, and the solution was concentrated until a precipitate formed. The suspension was stirred at room temperature for 30 minutes, filtered, and 870 mg (58% yield) of compound 23 was given as a bright yellow solid.

[1097] ESI-MS: 886.7 [M+H] + .

[1098] Compound 24

[1099] Intermediate 24-1

[1100]

[1101] 4.07 g (12.0 mmol) of intermediate 7-1, 4.13 g (10.2 mmol) of intermediate 2-3, and 0.96 g (24.0 mmol) of sodium hydroxide were suspended in a mixture of tetrahydrofuran / water (54 / 27 mL). The suspension was degassed with Ar, and 277 mg (2 mol%) of tetra(triphenylphosphine)palladium(0) was added to the reaction mixture. The reaction mixture was refluxed for 1.5 h. 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 eluent to give 4.30 g (73% yield) of intermediate 24-1 as a white foam.

[1102] ESI-MS: 490.2 [MH] - .

[1103] Intermediate 24-2

[1104]

[1105] 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-dimethylxanthone and 134 mg (3 mol%) of tris(dibenzylacetone)dipalladium(O) were added to the reaction mixture. The reaction mixture was heated to 90 °C for 45 minutes. The reaction mixture was cooled to room temperature, diluted with toluene / water, and filtered through diatomaceous earth. 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 eluent to give 1.4 g (61% yield) of intermediate 24-2 as a white solid.

[1106] ESI-MS [M+H] 474.4.

[1107] Intermediate 24-3

[1108]

[1109] 1.35 g (2.75 mmol) of intermediate 24-1, 1.30 g (2.75 mmol) of intermediate 24-2, and 661 mg (6.88 mmol) of sodium tert-butoxide were suspended in 35 mL of toluene. The suspension was degassed with Ar, and 127 mg (8 mol%) of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene and 101 mg (4 mol%) of tris(dibenzylacetone)dipalladium(O) were added to the reaction mixture. The reaction mixture was heated to 90 °C for 2.5 h. The reaction mixture was cooled to room temperature, diluted with toluene / water, and filtered through diatomaceous earth. 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 eluent to give 2.28 g (94% yield) of intermediate 24-3 as a pale yellow foam.

[1110] ESI-MS: 883.7 [M+H]+ .

[1111] Compound 24

[1112]

[1113] 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 pentane solution) was added dropwise, and the mixture was stirred for 5 min at the same temperature. The reaction mixture was then stirred at room temperature for 2 h. Next, 4.20 mL (4.20 mmol) of tribromoborane (1 M heptane solution) was added dropwise, and the mixture was stirred for 5 min, followed by the addition of 1.44 mL (8.40 mmol) of N-ethyl-N-isopropylpropyl-2-amine. The reaction mixture was stirred at room temperature for 3 h, 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 with heptane / toluene as eluent to give 1.25 g (66% yield) of compound 24 as a yellow solid.

[1114] ESI-MS [M+H] 891.6.

[1115] Compound 25

[1116] Intermediate 25-1

[1117]

[1118] 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(dibenzylacetone)dipalladium(O), 1.06 g (0.6 mmol) of 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (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 four hours. The reaction mixture was cooled to room temperature, and 100 mL of 5% sodium cyanide aqueous solution was added. The mixture was stirred vigorously for 30 minutes and then filtered. The remaining solids were washed with 300 mL of ethyl acetate. The collected filtrate was washed with water (3 × 100 mL), dried over magnesium sulfate, and concentrated under vacuum. The resulting solids were suspended in 400 mL of ethanol, and the suspension was stirred for one hour. The suspension was cooled, then filtered, and the solid was washed with cold ethanol to give 31.6 g (63% yield) of intermediate 25-1 as a white solid.

[1119] ESI-MS (positive, m / z): C 26 H 30 The precise mass of Cl₂N₂ is 440.18; the measured mass is 441.3 [M + 1]. + .

[1120] Intermediate 25-2

[1121]

[1122] 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 neopentanoic 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 eight hours. The reaction mixture was cooled to room temperature and poured into 1000 mL of water. The suspension was stirred for one 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 filter, then the silica gel was washed with 600 mL of dichloromethane and 1000 mL of ethyl acetate. The collected eluent was concentrated under vacuum to 100 mL, and 200 mL of heptane was added. The mixture was stirred until a suspension was formed. The suspension was filtered, and the white solid was washed with heptane to give 25.0 g (quantitative yield) of intermediate 25-2.

[1123] ESI-MS (positive, m / z): C 26 H 28 The precise mass of N2 is 368.23; the measured mass is 369.5 [M +1]. + .

[1124] Intermediate 25-3

[1125]

[1126] 25.0 g (67.8 mmol) of intermediate 25-2 and 32.6 g (0.15 mol) of di-tert-butyl dicarbonate were dissolved in 700 mL of tetrahydrofuran. 1.82 g (14.9 mmol) of 4-(dimethylamino)pyridine was added, and the suspension was stirred at room temperature for two hours. The suspension was filtered, and the solid was washed with 100 mL of tetrahydrofuran and 200 mL of ethyl acetate to give 29.4 g (76% yield) of intermediate 25-3 as a white solid.

[1127] Intermediate 25-4

[1128]

[1129] 29.0 g (51.0 mmol) of intermediate 25-3 was suspended in 600 mL of tert-butylbenzene and heated at 164 °C for three hours. The solution was cooled and stirred at room temperature for 18 hours. The resulting suspension was filtered. The filtrate was concentrated under vacuum to give 10.2 g (43% yield) of intermediate 25-4 as a white solid.

[1130] ESI-MS (negative, m / z): C 31 H 36 The exact mass of N₂O₂ is 468.28; the measured mass is 467.4 [M⁻¹]. + .

[1131] Intermediate 25-5

[1132]

[1133] 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 iodide (I), 1.12 g (10.2 mmol) of cyclohexyl-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 four hours. 1.00 g (3.8 mmol) of 1-(tert-butyl)-4-iodobenzene was added, and the mixture was heated at 91 °C for another four hours. The suspension was filtered through a 3 cm silica gel filter, and the silica gel was washed 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 give 13.8 g (67% yield) of intermediate 25-5.

[1134] ESI-MS (positive, m / z): C 41 H 48 The precise mass of N₂O₂ is 600.37; the measured mass is 601.8 [M + 1]. + .

[1135] Intermediate 25-6

[1136]

[1137] 13.5 g (22.5 mmol) of intermediate 25-5 was heated at 230 °C for 90 minutes. The molten solid was cooled and analyzed by MPLC. CombiFlash CompanionPurified (silica gel, heptane / ethyl acetate gradient 0-8%), giving 8.7 g (77%) intermediate 25-6 as a white solid.

[1138] ESI-MS (positive, m / z): C 36 H 40 The precise mass of N2 is 500.32; the measured mass is 501.7 [M +1]. + .

[1139] Intermediate 25-7

[1140]

[1141] 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 iodide (I), 185 mg (1.62 mmol) of cyclohexyl-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 eight hours. The suspension was cooled to room temperature and filtered through a 3 cm silica gel filter, followed by washing the silica gel with 30 mL of dioxane. The collected eluent was concentrated under vacuum, and the product was analyzed by MPLC. CombiFlash Companion (Silica gel, heptane / 0-25% gradient of dichloromethane) Further purification yielded 2.45 g (64% yield) of intermediate 25-7 as a white solid.

[1142] ESI-MS (positive, m / z): C 46 H 51 Precise mass of BrN2 = 710.32; measured mass 711.6 [M+1] + .

[1143] Intermediate 25-8

[1144]

[1145] 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(diphenylphosphine)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 eight 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 one hour and then washed with water (3 × 100 mL). The organic phase was dried over sodium sulfate and concentrated under vacuum. The product was dissolved in 300 mL of 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 give 24.3 g (51% yield) of intermediate 25-8 as a gray solid.

[1146] ESI-MS (positive, m / z): C 20 H 26 Precise mass of BrN = 359.12; Measured mass 362.4 [M +3] + .

[1147] Intermediate 25-9

[1148]

[1149] 5.80 g (16.1 mmol) of intermediate 25-8, 6.13 g (24.1 mmol) of bis(pinacolyl)diboron, 394 mg (0.48 mmol) of 1,1'-bis(diphenylphosphino)ferrocene-palladium(II) 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 eight hours. The resulting suspension was cooled to room temperature and diluted with 100 mL of water and 100 mL of ethyl acetate. The mixture was washed with water (3 × 50 mL), and the organic phase was dried over sodium sulfate and concentrated under vacuum. The resulting solid was dissolved in 50 mL of dichloromethane and 100 mL of ethanol and concentrated to 100 mL under vacuum. The resulting suspension was filtered, and the solid was washed with 50 mL of ethanol to give 3.8 g (58% yield) of intermediate 25-9.

[1150] ESI-MS (positive, m / z): C 26 H 38Precise mass of BNO2 = 407.30; measured mass 408.7 [M +1] + .

[1151] Intermediate 25-10

[1152]

[1153] 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 toluene, 30 mL of 1,4-dioxane, and 20 mL of water. The reaction mixture was heated at 83 °C for one 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 × 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 solids were washed with 50 mL of ethanol. The product was further processed by MPLC, using... CombiFlash Companion Purification (with silica gel, heptane / 0-16% gradient of dichloromethane) yielded 1.59 g (52% yield) of intermediate 25-10 as a white solid.

[1154] ESI-MS (positive, m / z): C 66 H 77 The precise mass of N3 is 911.61; the measured mass is 912.7 [M +1]. + .

[1155] Compound 25

[1156]

[1157] Dissolve 1.50 g (1.64 mmol) of intermediate 25-10 in 45 mL of 1,2-dichlorobenzene. Add 1.15 mL (6.6 mmol) of N,N-diisopropylethylamine and 3.3 mL of tribromoborane (1.0 M, in heptane) dropwise. Heat the yellow solution at 174 °C for 2.5 h. Cool the solution to room temperature. Add 3.3 mL of tribromoborane (1.0 M, in heptane) and continue heating at 174 °C for 25 h. Cool the reaction mixture to room temperature, dilute with 200 mL of ethanol, and stir for one hour. Filter the suspension, and further pass the solids through MPLC. CombiFlash CompanionPurified (with silica gel, heptane / dichloromethane gradient from 0 to 50%), yielding 212 mg (14% yield) of compound 25 as a yellow solid.

[1158] ESI-MS (positive, m / z): C 66 H 74 Precise mass of BN3 = 919.60; measured mass 920.9 [M+1] + .

[1159] Compound 26

[1160] Intermediate 26-1

[1161]

[1162] 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(dibenzylacetone)dipalladium(O), 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 dark suspension was dissolved, cooled to room temperature, and diluted with 100 mL of toluene and 100 mL of water. The aqueous phase was washed with water (3 × 50 mL), dried over sodium sulfate, and concentrated under vacuum. The product was further analyzed by MPLC using... CombiFlash Companion Purified (with silica gel, cyclohexane / ethyl acetate gradient of 0-2%), yielding 10.5 g (79% yield) of intermediate 26-1.

[1163] ESI-MS (positive, m / z): C 18 H 19 The precise mass of NS is 281.12; the measured mass is 282.4 [M+1]. + .

[1164] Intermediate 26-2

[1165]

[1166] 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-dimethylxanthocyanidin (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 four hours. The reaction mixture was cooled to room temperature and diluted with 100 mL of water and 100 mL of toluene. The organic phase was separated, washed with water (3 × 100 mL), and dried over sodium sulfate. The mixture was filtered through a 3 cm silica gel filter and the silica gel was washed with 50 mL of toluene. The collected eluent was concentrated under vacuum, and the product was analyzed by MPLC. CombiFlash Companion Further purification with silica gel and heptane yielded 2.7 g (51% yield) of intermediate 26-2.

[1167] ESI-MS (positive, m / z): C 28 H 30 Precise mass BrNS = 491.13; measured mass 492.6 [M+1] + .

[1168] Intermediate 26-3

[1169]

[1170] 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 toluene, 30 mL of 1,4-dioxane, and 20 mL of water. The solution was evacuated three times and backfilled with argon, and heated at 84 °C for seven hours. The reaction mixture was cooled to room temperature and diluted with 200 mL toluene and 100 mL of water. The organic phase was washed with water (3 × 100 mL), dried over sodium sulfate, and concentrated under vacuum. The product was analyzed by MPLC. CombiFlash Companion Further purification was performed using silica gel, heptane, and ethyl acetate in a 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 give 2.9 g (76% yield) of intermediate 26-3.

[1171] ESI-MS (positive, m / z): C44 H 40 Precise mass of N2S = 628.29; Measured mass 629.8 [M +1] + .

[1172] Compound 26

[1173]

[1174] 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 three hours. The reaction mixture was cooled to room temperature and diluted with 100 mL of ethanol. The suspension was stirred for 15 minutes and then filtered. The filtrate was concentrated under vacuum, and the residue was stirred in 100 mL of heptane. The suspension was filtered, and the solid was washed with 50 mL of heptane to give 142 mg (9% yield) of compound 26 as a yellow solid.

[1175] ESI-MS (positive, m / z): C 44 H 40 Precise mass of N2S = 628.29; Measured mass 629.8 [M +1] + .

[1176] Compound 27

[1177] Intermediate 27-1

[1178]

[1179] 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(diphenylphosphine)-9,9-dimethylxanthene and 429 mg (0.5 mol%) of tris(dibenzylacetone)dipalladium(O) 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 / water, and filtered through diatomaceous earth. 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 give 15.1 g (89% yield) of intermediate 27-1 as a transparent oil.

[1180] 1 H NMR (300 MHz, chloroform-) d 3 ) δ 7.46-7.39 (m, 3H), 7.22-7.12 (m, 2H), 6.69(dd, 1H), 6.05 (width s, 1H), 1.38 (s, 9H).

[1181] Intermediate 27-2

[1182]

[1183] 15.0 g (44.3 mmol) of intermediate 27-1 and 13.35 mL (89.0 mmol) of 1,8-diazabicyclo[5.4.0]undec-7-ene were suspended in 221 mL of dimethylformamide. The suspension was degassed with Ar, and 451 mg (1.5 mol%) of bis(triphenylphosphine)palladium(II) chloride was added to the reaction mixture. The reaction mixture was heated to 120 °C for 30 hours. The reaction mixture was cooled to room temperature, diluted with toluene / water, and filtered through diatomaceous earth. 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 eluent to give 6.43 g (56% yield) of intermediate 27-2 as a white solid. The final product was purified by LC-MS [MH]. - 256.5 Determine the molecular weight of the product.

[1184] Intermediate 27-3

[1185]

[1186] 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 to 195 °C for 3 days. The reaction mixture was cooled to room temperature, diluted with toluene, and filtered through diatomaceous earth. The organic layer was washed with 10% 3-amino-1-propanol solution until the blue color disappeared. The aqueous layer was further extracted with toluene. The combined organic extracts were washed with brine, dried over sodium sulfate, filtered, and evaporated. The residue was purified by silica gel column chromatography using heptane as eluent to give 2.38 g (41% yield) of intermediate 27-3 as a white foam. The final product was determined by LC-MS [M+H]. + 374.5 confirms the molecular weight of the product.

[1187] Intermediate 27-4

[1188]

[1189] 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 then filtered through a diatomaceous earth mat. Water was added to the filtrate, and the layers were separated. 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 a second chromatographic purification using heptane / dichloromethane as eluent, to give 2.1 g (55% yield) of intermediate 27-4 as a white solid. Further purification was performed by LC-MS [MH]. - 615.4 Determine the molecular weight of the product.

[1190] Compound 27

[1191]

[1192] 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 pentane solution) was added dropwise, followed by stirring at the same temperature for 5 minutes. The reaction mixture was then stirred at 85 °C for 2 hours. Next, 0.81 mL (0.81 mmol) of tribromoborane (1 M heptane solution) was added dropwise at 0 °C, allowing the reaction mixture to reach room temperature over 45 minutes, followed by the addition of 1.44 mL (8.40 mmol) of N-ethyl-N-isopropylpropyl-2-amine. 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 eluent to give 5 mg (2% yield) of compound 27 as a yellow solid. Further purification was performed by LC-MS [M+H]. + 624.7 confirmed the molecular weight of the product.

[1193] Evaluation of Compound II

[1194] Next, the properties of the compounds used in the examples were measured. The measurement and calculation methods are shown below.

[1195] 1.1 Photoluminescence Application Data

[1196] The toluene solutions of the compounds listed in the table are prepared by diluting the corresponding compounds at 10... -6 The solution was prepared by dissolving it in toluene at a concentration of mol / L. The total fluorescence spectrum in the toluene solution was measured using an FP-8300 JASCO spectrophotometer.

[1197] Photoluminescence (PL) data of compounds 1-27 of the present invention in toluene solution have been measured and summarized in the table below. As a comparative example, PL data of comparative compound 1 in toluene solution according to US 2019 / 0067577A1

[0122] are disclosed in the table:

[1198] Compound PL 1) ]]> FWHM 2) ]] Comparative Compound 1 430 nm 34 nm Compound 1 434 nm 17 nm Compound 2 443 nm 18 nm Compound 3 452 nm 20 nm Compound 4 448 nm 19 nm Compound 5 447 nm 20 nm Compound 6 448 nm 20 nm Compound 7 457 nm 38 nm Compound 8 451 nm 20 nm Compound 9 455 nm 20 nm Compound 10 448 nm 19 nm Compound 11 443 nm 18 nm Compound 12 448 nm 19 nm Compound 13 454 nm 20 nm Compound 14 453 nm 18 nm Compound 15 450 nm 19 nm Compound 16 445 nm 19 nm Compound 17 449 nm 18 nm Compound 18 454 nm 21 nm Compound 19 450 nm 20 nm Compound 20 442 nm 16 nm Compound 21 442 nm 17 nm Compound 22 449 nm 17 nm Compound 23 453 nm 21 nm Compound 24 446 nm 19 nm Compound 25 446 nm 20 nm Compound 26 440 nm 16 nm Compound 27 442 nm 11 nm

[1199] 1) Photoluminescence

[1200] 2) Half-peak full width.

[1201] These results demonstrate that compounds 1 to 6, 8 to 27 of the present invention produce a narrower spectrum (smaller FWHM), i.e., better color purity, than comparative compound 1. Compound 7 of the present invention has a longer PL wavelength than comparative compound 1.

[1202]

[1203] 1.2 Device Application Data (The compound of this invention is used as a dopant in the luminescent body)

[1204] Fabrication and evaluation of organic EL devices

[1205] The following describes the fabrication and evaluation of organic EL devices:

[1206] Application Example 1

[1207] First, a glass substrate with a 130 nm thick indium tin oxide (ITO) transparent electrode (manufactured by Geomatec Co., Ltd.) used as the anode was treated with N2 plasma for 100 seconds. This treatment also improves the hole injection properties of ITO. The cleaned substrate was mounted on a substrate holder and loaded into a vacuum chamber. Then, vapor deposition was performed to achieve a hole injection effect of approximately 10 nm. -6 -10 -8The specified organic materials were applied to an ITO substrate at a rate of approximately 0.2–1 Å / s under millibars. A mixture of compound HT-1 (10 nm thick) and 3% by weight of compound HI was applied as a hole injection layer. Then, 80 nm thick layers of compound HT-1 and 10 nm thick layers of compound HT-2 were applied as hole transport layer 1 and hole transport layer 2, respectively. Subsequently, a mixture of 2% by weight of luminescent compound 2 and 98% by weight of host compound BH-1 was applied to form a 25 nm thick fluorescent luminescent layer. A 10 nm thick layer of compound ET-1 was applied as electron transport layer 1, and a 15 nm thick layer of compound ET-2 as electron transport layer 2. Finally, a 1 nm thick layer of LiF was deposited as an electron injection layer, followed by an 80 nm thick layer of Al as a cathode to complete the device. The device was sealed with a glass cap and getter in an inert nitrogen atmosphere containing less than 1 ppm of water and oxygen. To characterize the OLED, electroluminescence (EL) spectra were recorded at various currents and voltages. 2 The maximum EL peak value and full width at half maximum (FWHM) were recorded. Furthermore, the luminance was measured in conjunction with the current-voltage characteristics to determine the luminous efficiency and external quantum efficiency (EQE). This was done at a current density of 10 mA / cm². 2 The driving voltage (voltage) is provided at that time. The device results are shown in Table 1.

[1208]

[1209]

[1210] Table 1

[1211] Application Example Voltage, V EQE, % EL max, nm FWHM, nm Application Example 1 3.69 9.05 448 20

[1212] These results indicate that the compounds of the present invention, when used as fluorescent luminescent materials in OLEDs, provide good EQE and narrow spectrum (smaller FWHM), i.e., good color purity.

[1213] 1.3 Other Application Examples

[1214] 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 luminescent material in the fluorescent luminescent layer.

[1215] Table 2

[1216] Application Example Compound Voltage, V EQE, % EL max, nm FWHM, nm Application Example 2 Compound 3 3.58 11 457 22 Application Example 3 Compound 4 3.64 9.10 453 22 Application Example 4 Compound 5 3.66 7.15 454 21 Application Example 5 Compound 6 3.54 7.39 455 21 Application Example 6 Compound 8 3.61 9.60 455 22 Application Example 7 Compound 11 3.67 9.64 450 21 Application Example 8 Compound 12 3.65 9.90 452 20 Application Example 9 Compound 15 3.66 9.77 455 21 Application Example 10 Compound 16 3.66 9.33 450 21 Application Example 11 Compound 17 3.66 8.95 453 19 Application Example 12 Compound 20 3.55 7.22 447 21 Application Example 13 Compound 21 3.53 7.55 449 18 Application Example 14 Compound 23 3.71 10.07 459 21

Claims

1. Heterocyclic compounds represented by the following formula (V), in R 1 Indicates hydrogen; unsubstituted or substituted alkyl groups having 1 to 4 carbon atoms; or N(R) 22 )2; R 2 It represents hydrogen; an unsubstituted or substituted aryl group having 6 to 18 ring carbon atoms; or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 3 and R 4 Each can be used independently to represent hydrogen; or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 5 Represents hydrogen; unsubstituted or substituted aryl groups having 6 to 18 ring carbon atoms; unsubstituted or substituted alkyl groups having 1 to 4 carbon atoms; or N(R) 22 )2; R 6 and R 7 Each can be used independently to represent hydrogen; or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 8 Indicates hydrogen; or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 9 It represents hydrogen; an unsubstituted or substituted aryl group having 6 to 18 ring carbon atoms; or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 10 Indicates hydrogen; or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 11 and R 12 Each can be used independently to represent hydrogen; or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 13 Indicates hydrogen; unsubstituted or substituted alkyl groups having 1 to 4 carbon atoms; or N(R) 22 )2; R 14 It represents hydrogen; an unsubstituted or substituted aryl group having 6 to 18 ring carbon atoms; or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 15 Indicates hydrogen; or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 16 and R 17 Each can be used independently to represent hydrogen; or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 18 It represents hydrogen; an unsubstituted or substituted aryl group having 6 to 18 ring carbon atoms; an unsubstituted or substituted heteroaryl group having 5 to 13 ring atoms; or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 19 Indicates hydrogen; or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; or Two adjacent residues R 14 and R 15 Two adjacent residues R 16 and R 17 R 18 and R 19 Together they form unsubstituted or substituted ring structures. and / or Two adjacent residues R 8 and R 9 Together they form unsubstituted or substituted ring structures; and / or R 7 Connect to R 6 To form unsubstituted or substituted ring structures; R 11 Connect to R 12 To form unsubstituted or substituted ring structures; R 22 Indicates an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms; 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 R 19 In the aforementioned ring structure, the substituents in "unsubstituted or substituted" are unsubstituted alkyl groups with 1 to 8 carbon atoms. And the following compounds, in, Excluding the following compounds, 。 2. The heterocyclic compound according to claim 1, having one of the following formulas. in In equations (VA) and (VB) - Two adjacent residues R 8 and R 9 Two adjacent residues R 14 and R 15 Two adjacent residues R 16 and R 17 R 18 and R 19 They can form unsubstituted or substituted ring structures together; In equation (VC) - Two adjacent residues R 6 and R 7 R 8 and R 9 Two adjacent residues R 14 and R 15 Two adjacent residues R 16 and R 17 R 18 and R 19 They can form unsubstituted or substituted ring structures together.

3. The heterocyclic compound according to claim 2, represented by formula (VA), wherein two adjacent residues R 16 and R 17 R 18 and R 19 Together they form unsubstituted or substituted ring structures.

4. The heterocyclic compound according to claim 2, represented by formula (VA), wherein R 1 Indicates an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; or N(R) 22 )2; R 2 This refers to an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms; or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 3 Indicates an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 16 and R 17 Each can be used independently to represent an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 18 The following terms are used to indicate unsubstituted or substituted aryl groups having 6 to 18 ring carbon atoms; unsubstituted or substituted heteroaryl groups having 5 to 13 ring atoms; or unsubstituted or substituted alkyl groups having 1 to 4 carbon atoms. R 19 Indicates an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; and R 4 Indicates an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 5 This indicates an unsubstituted or substituted aryl group having 6 to 18 ring carbon atoms; an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; or N(R) 22 )2; R 12 Indicates an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 13 Indicates an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; or N(R) 22 )2; R 14 This refers to an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms; or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 15 This refers to an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms.

5. The heterocyclic compound according to claim 2, represented by formula (VA), wherein... R 1 Indicates an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 2 This refers to an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms; or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 3 Indicates an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 16 and R 17 Each can be used independently to represent an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 18 The following terms are used to indicate unsubstituted or substituted aryl groups having 6 to 18 ring carbon atoms; unsubstituted or substituted heteroaryl groups having 5 to 13 ring atoms; or unsubstituted or substituted alkyl groups having 1 to 4 carbon atoms. R 19 Indicates an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 4 Indicates an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 5 This refers to an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms; or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 12 Indicates an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 13 Indicates an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 14 This refers to an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms; or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 15 This refers to an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms.

6. The heterocyclic compound according to claim 2, represented by formula (VA), wherein R 9 It is an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; And R 12 Indicates an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 13 Indicates an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; or N(R) 22 )2; R 14 This refers to an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms; or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 15 This refers to an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms.

7. The heterocyclic compound according to claim 2, represented by formula (VC), wherein R 4 Indicates an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 5 This indicates an unsubstituted or substituted aryl group having 6 to 18 ring carbon atoms; an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; or N(R) 22 )2; R 6 Indicates an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 13 Indicates an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; or N(R) 22 )2; R 14 This refers to an unsubstituted or substituted aryl group having 6 to 18 cyclic carbon atoms; or an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms; R 15 This refers to an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms.

8. A material for use in an organic electroluminescent device, comprising at least one compound according to claim 1 or 2.

9. An organic electroluminescent device comprising at least one compound according to claim 1 or 2.

10. The organic electroluminescent device of claim 9, comprising a cathode, an anode, and one or more organic thin film layers, said one or more organic thin film layers comprising a light-emitting layer disposed between the cathode and the anode, wherein at least one of said organic thin film layers comprises at least one compound according to claim 1 or 2.

11. The organic electroluminescent device of claim 10, wherein the light-emitting layer comprises at least one compound according to claim 1 or 2.

12. The organic electroluminescent device of claim 11, wherein the light-emitting layer comprises at least one host and at least one dopant, wherein the dopant comprises at least one compound of claim 1 or 2.

13. The organic electroluminescent device according to claim 12, wherein the host comprises at least one substituted or unsubstituted fused aromatic compound.

14. The organic electroluminescent device according to claim 12, wherein the host comprises at least one substituted or unsubstituted anthracene compound.

15. An electronic device comprising the organic electroluminescent device according to claim 9.

16. 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.

17. Use of the compound according to claim 1 or 2 in organic electroluminescent devices.

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