Compound and organic electroluminescent device

Abstract

The invention belongs to the technical field of organic electroluminescence, and discloses a compound and an organic electroluminescence device. The compound has a structure as shown in a formula (1): # imgabs0 #, has the advantages of high luminous efficiency, low voltage, long service life and the like, and can be applied to organic electroluminescent devices.

Description

Technical Field

[0001] The invention belongs to the technical field of organic electroluminescence, and particularly relates to a compound and an organic electroluminescence device. Background Art

[0002] At present, organic electroluminescent devices (OLEDs), as a new generation of display technology, have received more and more attention in both display and lighting technology, and have a wide range of application prospects. However, compared with market application requirements, the performance of OLED devices such as luminous efficiency, driving voltage, and service life still needs to be further strengthened and improved.

[0003] Generally speaking, the basic structure of an OLED device is a thin film of organic functional material sandwiched between metal electrodes, like a sandwich structure. Driven by electric current, electrons and holes are injected from the positive and negative poles respectively. After moving a certain distance, the holes and electrons are recombined in the light-emitting layer and released in the form of light or heat, thereby producing a luminous effect. Organic functional materials are the core components of OLED devices. Their thermal stability, photochemical stability, electrochemical stability, quantum yield, film formation stability, crystallinity, color saturation, etc. are all important factors affecting device performance. However, the organic functional materials reported in related technologies, such as hole blocking materials or electron transport materials, still need to be further improved in terms of device voltage, efficiency or service life.

[0004] Based on the above problems of existing organic functional materials, it is necessary to develop a new organic compound to further improve the performance of OLED devices. Summary of the invention

[0005] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention provides a compound and an organic electroluminescent device.

[0006] The first embodiment of the present invention relates to a compound having a structure shown in formula (1):

[0007]

[0008] Wherein, X1 and X2 are independently selected from N or CH, and X1 and X2 are different;

[0009] Z1, Z2, Z3, and Z4 are independently selected from N or CR1, and only one of them is selected from N;

[0010] L is selected from a single bond, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 6 to 30 ring atoms;

[0011] Ar1, Ar2, Ar3 are independently selected from a substituted or unsubstituted aromatic group having 5-60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5-60 ring atoms, a substituted or unsubstituted aryloxy group having 5-60 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5-60 ring atoms, or a combination of these groups, which can form a monocyclic or polycyclic aliphatic or aromatic ring system with the ring bonded to the group;

[0012] R1 is independently selected from hydrogen, deuterium, halogen, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, silyl, linear alkyl having 1 to 20 C atoms, linear alkoxy having 1 to 20 C atoms, linear thioalkoxy having 1 to 20 C atoms, branched or cyclic alkyl having 3 to 20 C atoms, branched or cyclic alkoxy having 3 to 20 C atoms, a branched or cyclic thioalkoxy group having 1 to 20 C atoms, a keto group having 1 to 20 C atoms, an alkoxycarbonyl group having 2 to 20 C atoms, an aryloxycarbonyl group having 7 to 20 C atoms, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, or a heteroaryloxy group having 5 to 60 ring atoms; or a combination of these groups, and two adjacent groups may be fused to form a ring;

[0013] In the L and R1, the substitution is independently substituted by at least one of deuterium, halogen, cyano, isocyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C16 cycloalkyl, C6-C30 aryl, and triphenylsilyl, wherein the number of substitutions is from a single substitution to a maximum number of substitutions;

[0014] The heteroatoms in the heteroaromatic group, heteroaromatic group or heteroaryloxy group are independently selected from at least one of O, S, N, P, Si, Se or Ge.

[0015] The beneficial effects of the present invention are as follows:

[0016] By introducing an aliphatic condensed ring into the molecule as a steric hindering group to obtain a compound represented by formula (1), the performance of an OLED device using the compound can be improved.

[0017] The compound has good film-forming properties, high luminous efficiency, low voltage, and long service life, and can be used in OLEDs. For example, it is particularly suitable for use as a hole blocking layer material and an electron transport layer material, and has the potential to be applied to the AMOLED (active matrix organic light-emitting diode) industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1FIG. 1 is a schematic structural diagram of an organic electroluminescent device according to an embodiment of the present invention. DETAILED DESCRIPTION

[0019] In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the following embodiments are listed for illustration. It should be pointed out that the following embodiments do not limit the protection scope of the present invention.

[0020] Unless otherwise specified, the scientific and technical terms used herein have the meanings commonly understood by those skilled in the art, but for a better understanding of the present invention, the definitions of some terms are provided below. When the definitions of terms provided by the present invention are inconsistent with the meanings commonly understood by those skilled in the art, the definitions and interpretations of the terms provided by the present invention shall prevail.

[0021] In the present invention, the "number of ring atoms" refers to the number of atoms in the atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring atoms. The same is true for the "number of ring atoms" described below unless otherwise specified. For example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, and the number of ring atoms of a thienyl group is 5.

[0022] In the present invention, an aromatic ring system or aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including monocyclic groups and polycyclic ring systems. A heteroaromatic group refers to a hydrocarbon group (containing heteroatoms) containing at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. The heteroatoms can be selected from Si, N, P, O, S and / or Ge, and are particularly preferably selected from Si, N, P, O and / or S. These polycyclic rings can have two or more rings, in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. At least one of these polycyclic ring species is aromatic or heteroaromatic. For the purposes of the present invention, an aromatic group or heteroaromatic group includes not only a system of aromatic or heteroaromatic groups, but also, wherein multiple aromatic or heteroaromatic groups can also be interrupted by short non-aromatic units (<10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N, O, Si atoms). Therefore, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc. should also be included in the definition of aromatic group or heteroaromatic group.

[0023] It is understood that the terms "lene aromatic group" and "lene heteroaromatic group" correspond to divalent groups having the same structure as the aromatic group and the heteroaromatic group, respectively.

[0024] In the present invention, "aryloxy" refers to a group having an -O-aryl group, wherein the oxygen atom is used as the attachment site, and the aryl group is an aromatic group as defined above. Non-limiting examples of aryloxy include benzyloxy, p-methylbenzyloxy, and the like.

[0025] In the present invention, "aryloxycarbonyl" refers to a group having a -C(O)-O-aryl group, wherein the carbonyl group (-C(O)-) is the attachment point and the aryl group is an aromatic group as defined above.

[0026] In the present invention, "alkyl" may represent a straight chain, branched chain and / or cyclic alkyl (i.e., cycloalkyl). Non-limiting examples of straight chain or branched chain alkyl include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl to triacontanyl, etc.; each group includes various isomers, such as butyl including isomers such as n-butyl, isobutyl, sec-butyl, tert-butyl, etc. Non-limiting examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, bicyclo [3.1.1] heptyl, spiro [4.5] decyl, spiro [5.5] undecyl, adamantyl, and norbornyl.

[0027] In the present invention, "alkoxy" refers to a group having -O-alkyl, wherein an oxygen atom is used as a connection site, and the alkyl group is as defined above. The alkoxy group may be a linear, branched or cyclic structure. The number of carbon atoms in the alkoxy group is not particularly limited, for example, 1 to 20. Non-limiting examples of alkoxy groups include: methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, nonyloxy, decyloxy. Each group includes various isomers, such as butoxy includes isomers such as n-butoxy, isobutoxy, tert-butoxy, and sec-butoxy.

[0028] In the present invention, "thioalkoxy" means that at least one carbon atom in the alkoxy group as defined above is substituted by a sulfur atom.

[0029] In the present invention, "alkylcarbonyl" means that one of the carbon atoms in the alkyl group as defined above is substituted by a carbonyl group, with the carbonyl group serving as the attachment point.

[0030] In the present invention, "alkoxycarbonyl" refers to a group having -C(O)-O-alkyl, wherein the carbonyl group serves as the attachment point and the alkyl group is as defined above.

[0031] In the present invention, keto means that at least one carbon atom in the alkyl group as defined above is substituted by a carbonyl group, and all carbonyl groups are non-attachment sites.

[0032] The term "adjacent" refers to two groups or atoms that are directly bonded to each other, or two groups or atoms that are directly adjacent substituents to each other (ie, the two substituents are directly connected, rather than indirectly connected through other atoms or groups).

[0033] The "substituted" in "substituted or unsubstituted" means that one or more hydrogen atoms are replaced by other atoms or functional groups (i.e., substituents), and unless otherwise limited by the definition, it also includes that one or more hydrogen atoms are replaced by a group formed by connecting two or more of the above-mentioned substituents.

[0034] Specifically, the first embodiment of the present invention provides a compound as shown in formula (1):

[0035]

[0036] Wherein, X1 and X2 are independently selected from N or CH, and X1 and X2 are different;

[0037] Z1, Z2, Z3, and Z4 are independently selected from N or CR1, and only one of them is selected from N;

[0038] L is selected from a single bond, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 6 to 30 ring atoms;

[0039] Ar1, Ar2, Ar3 are independently selected from a substituted or unsubstituted aromatic group having 5-60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5-60 ring atoms, a substituted or unsubstituted aryloxy group having 5-60 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5-60 ring atoms, or a combination of these groups, which can form a monocyclic or polycyclic aliphatic or aromatic ring system with the ring bonded to the group;

[0040] R1 is independently selected from hydrogen, deuterium, halogen, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, silyl, linear alkyl having 1 to 20 C atoms, linear alkoxy having 1 to 20 C atoms, linear thioalkoxy having 1 to 20 C atoms, branched or cyclic alkyl having 3 to 20 C atoms, branched or cyclic alkoxy having 3 to 20 C atoms, a branched or cyclic thioalkoxy group having 1 to 20 C atoms, a keto group having 1 to 20 C atoms, an alkoxycarbonyl group having 2 to 20 C atoms, an aryloxycarbonyl group having 7 to 20 C atoms, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, or a heteroaryloxy group having 5 to 60 ring atoms; or a combination of these groups, and two adjacent groups may be fused to form a ring;

[0041] In the L and R1, the substitution is independently substituted by at least one of deuterium, halogen, cyano, isocyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C16 cycloalkyl, C6-C30 aryl, and triphenylsilyl, wherein the number of substitutions is from a single substitution to a maximum number of substitutions;

[0042] The heteroatoms in the heteroaromatic group, heteroaromatic group or heteroaryloxy group are independently selected from at least one of O, S, N, P, Si, Se or Ge.

[0043] Among them, "the combination of these groups" means that a plurality of groups as defined above are combined to form Ar1, Ar2, Ar3, and R1, for example, an aromatic group with 5-60 ring atoms and a heteroaromatic group with 5-60 ring atoms can form Ar1. "It can form a monocyclic or polycyclic aliphatic ring or aromatic ring with the ring bonded to the group" means that Ar1, Ar2, and Ar3 can form a monocyclic or polycyclic ring. In addition, the group in Ar3 can also form a ring with the benzene ring to which Ar3 is connected, or the group in R1 can also form a ring with the pyridine ring to which R1 is connected.

[0044] In some embodiments, R1 is independently selected from hydrogen, deuterium, halogen, cyano, a linear alkyl group having 1 to 10 C atoms, a branched or cyclic alkyl group having 3 to 10 C atoms, or a substituted or unsubstituted aromatic group having 5 to 30 ring atoms.

[0045] In some embodiments, R1 is independently selected from hydrogen, deuterium, halogen, cyano, a linear alkyl group having 1 to 10 C atoms, a branched or cyclic alkyl group having 3 to 10 C atoms, or a substituted or unsubstituted aromatic group having 5 to 30 ring atoms.

[0046] In some embodiments, R1 is independently selected from hydrogen, deuterium, halogen, cyano, and a linear alkyl group having 1 to 10 C atoms.

[0047] In some embodiments, R1 is selected from hydrogen, that is, any one of Z1, Z2, Z3, and Z4 is selected from N, and the others are selected from CH. Specifically, for example, Z1 is selected from N, and Z2, Z3, and Z4 are selected from CH; or, Z2 is selected from N, and Z1, Z3, and Z4 are selected from CH; or, Z3 is selected from N, and Z1, Z3, and Z4 are selected from CH. 32 , Z4 is selected from CH; or, Z4 is selected from N, and Z1, Z2, and Z3 are selected from CH.

[0048] In some embodiments, the compound represented by formula (1) is selected from one of the structures represented by the following formulas (2-1) to (2-4):

[0049]

[0050] In some embodiments, the substituents in L and R1 are independently selected from at least one of deuterium, halogen, cyano, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 haloalkyl, C6-C30 aryl, and triphenylsilyl, wherein the number of substitutions is from a single substitution to a maximum number of substitutions.

[0051] In some embodiments, the substituents in L and R1 are independently selected from at least one of deuterium, halogen, cyano, C1-C4 alkyl, C3-C10 cycloalkyl, C1-C3 haloalkyl, C6-C25 aryl, and triphenylsilyl, wherein the number of substitutions is from single substitution to the maximum number of substitutions. Specifically, non-limiting examples of the substituents include: D, F, Cl, Br, cyano, methyl, ethyl, propyl or its isomers, butyl or its isomers, trifluoromethyl, phenyl, naphthyl, biphenyl, fluorenyl, spirofluorenyl, triphenylsilyl or C3-C10 cycloalkyl, etc.

[0052] In a more preferred embodiment, when the substituents in L and R1 include at least deuterium, it is preferred that more than 10% of the H is deuterated, more preferably more than 20% of the H is deuterated, most preferably more than 30% of the H is deuterated, and most preferably more than 40% of the H is deuterated.

[0053] In some embodiments, the substituent in L is selected from at least one of halogen, cyano, C1-C4 alkyl, C6-C12 aryl, wherein the number of substitutions is from single substitution to the maximum number of substitutions. Specifically, non-limiting examples of the substituents of L include: fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl or phenyl, etc.

[0054] In some embodiments, L is selected from a single bond, a substituted or unsubstituted aromatic group having 6-25 ring atoms, or a substituted or unsubstituted heteroaromatic group having 6-25 ring atoms.

[0055] In some embodiments, L is selected from a single bond or one of the structures shown in the following formulas A-1 to A-18;

[0056]

[0057] Wherein, "*" represents the bond attachment site of L;

[0058] Formula A-1 to Formula A-18 are optionally substituted by 0 to 3 groups selected from D, F, Cl, Br, cyano, C1-C4 alkyl, C1-C3 haloalkyl, phenyl, naphthyl, fluorenyl, spirofluorenyl and C3-C10 cycloalkyl. Non-limiting examples of alkyl include: methyl, ethyl, propyl or its isomers, butyl or its isomers; non-limiting examples of cycloalkyl include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl; non-limiting examples of haloalkyl include trifluoromethyl; it is understood that when there are 2 or 3 substituents, each substituent may be the same, partially the same, or completely different.

[0059] In some embodiments, Ar1 to Ar3 are independently selected from one of the following structures:

[0060]

[0061] Wherein, each occurrence of W is independently selected from N or CR2;

[0062] Each occurrence of V is independently selected from O, S, S=O, SO2, NR3, CR4R5 or SiR6R7;

[0063] Each occurrence of R2 to R7 is independently selected from hydrogen, deuterium, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, straight-chain alkyl with 1 to 10 C atoms, straight-chain alkoxy with 1 to 10 C atoms, straight-chain thioalkoxy with 1 to 10 C atoms, branched or cyclic alkyl with 3 to 10 C atoms, branched or cyclic alkoxy with 3 to 10 C atoms, A branched or cyclic thioalkoxy group having 3 to 10 C atoms, a silyl group, a keto group having 1 to 10 C atoms, an alkoxycarbonyl group having 2 to 10 C atoms, an aryloxycarbonyl group having 7 to 10 C atoms, a substituted or unsubstituted aromatic group having 5 to 10 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms, an aryloxy group having 5 to 10 ring atoms, a heteroaryloxy group having 5 to 10 ring atoms; or a combination of these groups; R2-R7 may form a ring;

[0064] In the R2 to R7, the substitution is independently substituted by at least one of deuterium, halogen, cyano, isocyano, C1-C3 alkyl, C1-C3 haloalkyl, C3-C5 cycloalkyl, C6-C10 aryl, and triphenylsilyl, wherein the number of substitutions is from a single substitution to a maximum number of substitutions;

[0065] The heteroatoms in the heteroaromatic group or heteroaryloxy group are independently selected from at least one of O, S, N, P, Si, Se or Ge;

[0066] The bonding sites of Ar1 to Ar3 are selected from any substitutable sites of W and V.

[0067] In some embodiments, R2 to R7 are independently selected from hydrogen, deuterium, halogen, cyano, a straight-chain alkyl group having 1 to 10 C atoms, a branched or cyclic alkyl group having 3 to 10 C atoms, a substituted or unsubstituted aromatic group having 5 to 10 ring atoms; or, R4 and R5 are connected to form a ring, for example, R4 and R5 are connected to form a fluorenyl group.

[0068] In a more preferred embodiment, when the substituents in R2 to R7 include at least deuterium, it is preferred that more than 10% of the H are deuterated, more preferably more than 20% of the H are deuterated, most preferably more than 30% of the H are deuterated, and most preferably more than 40% of the H are deuterated.

[0069] In some embodiments, Ar1 to Ar3 are independently selected from one of the following structures:

[0070]

[0071] The definitions of Ra and V are the same as those of R defined above. 1、 V;

[0072] s is an integer from 0 to 5;

[0073] "*" indicates the bonding site of Ar1 to Ar3.

[0074] In some embodiments, Ar1 to Ar3 are independently selected from a substituted or unsubstituted aromatic group having 5-40 ring atoms, a substituted or unsubstituted heteroaromatic group having 5-40 ring atoms, a substituted or unsubstituted aryloxy group having 5-40 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5-40 ring atoms; or a combination of these groups, which can form a monocyclic or polycyclic aliphatic ring or aromatic ring with the ring bonded to the group.

[0075] In some embodiments, Ar1 to Ar3 are independently selected from a substituted or unsubstituted aromatic group having 5-30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5-30 ring atoms, a substituted or unsubstituted aryloxy group having 5-30 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5-30 ring atoms; or a combination of these groups, which can form a monocyclic or polycyclic aliphatic ring or aromatic ring with the ring bonded to the group.

[0076] In some embodiments, Ar1 to Ar3 are the same as or different from each other and are each independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted 9,9-spirobifluorenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted thiophene, substituted or unsubstituted thiophene, substituted or unsubstituted pyridyl, substituted or unsubstituted furanyl, substituted or unsubstituted thiophene ... substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophene, substituted or unsubstituted benzocarbazolyl, substituted or unsubstituted benzofluorenyl, substituted or unsubstituted benzonaphthofuranyl, substituted or unsubstituted benzonaphthothiophene, or substituted or unsubstituted fluoranthenyl.

[0077] In some embodiments, Ar1 to Ar3 are independently selected from one of the following groups:

[0078]

[0079] Wherein, R3 is the same as R3 defined above; “*” represents the bond connection site of Ar1 to Ar3.

[0080] In some embodiments, the substituents in Ar1 to Ar3 are independently selected from fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl, trifluoromethyl, triphenylsilyl, cyclohexyl, adamantyl, phenyl or biphenyl.

[0081] In some embodiments, the compound represented by formula (1) is selected from one of the following structural formulas:

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090] An embodiment of the second aspect of the present invention provides an organic electroluminescent device, comprising a functional layer, wherein the functional layer comprises the compound represented by the above formula (1).

[0091] In some embodiments, the organic electroluminescent device further includes an anode and a cathode, and the functional layer is disposed between the anode and the cathode.

[0092] In some embodiments, the functional layer has one or more layers. When the functional layer has multiple layers, at least one functional layer comprises the compound represented by the above formula (1).

[0093] In some embodiments, the functional layers include, from near to far from the anode, a hole injection layer (HIL), a hole transport layer (HTL), a light-emitting layer (EML), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL), at least one of which includes the compound represented by the above formula (1). Preferably, at least one of the light-emitting layer, the hole blocking layer, and the electron transport layer includes the compound represented by the above formula (1). More preferably, the electron transport layer includes the compound represented by the above formula (1).

[0094] By introducing an aliphatic condensed ring as a steric hindering group into the compound represented by formula (1), the performance of an OLED device using the compound can be improved. The compound has good film-forming properties, high luminous efficiency, low voltage, and long service life, and can be used in OLED, for example, it is particularly suitable for use as a hole blocking layer material and an electron transport layer material, and has the potential to be applied to the AMOLED (active matrix organic light-emitting diode) industry.

[0095] The following embodiments are only for facilitating the understanding of the technical invention and should not be regarded as specific limitations of the present invention.

[0096] The raw materials and solvents involved in the synthesis of the compounds of the present invention were purchased from suppliers familiar to those skilled in the art such as Alfa and Acros. The raw materials, reagents or devices used, unless otherwise specified, can be obtained from conventional commercial channels or can be obtained by existing known methods.

[0097] Synthesis of compound 1

[0098]

[0099] Synthesis of Compounds 1-3

[0100] Compound 1-1 (25.00 g, 59.68 mmol), compound 1-2 (14.04 g, 59.68 mmol), tetrakis(triphenylphosphine)palladium (0.69 g, 0.59 mmol), sodium hydroxide (5.97 g, 149.19 mmol), tetrahydrofuran (450 ml), and deionized water (150 ml) were added to a 1000 ml three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. The oil temperature was raised to 75 ° C. and the reaction was carried out for 6 hours. TLC monitoring (by volume ratio, ethyl acetate: n-hexane = 1:15 as the developing solvent) was performed. When compound 1-1 was completely consumed, heating was stopped.

[0101] After the reaction was completed, a large amount of solid was precipitated, which was directly filtered to obtain 35 g of solid. Dichloromethane (600 ml) was added to dissolve and clarify. Silica gel (60 g, 200-300 mesh chromatography column silica gel) was filtered once, and the filtrates were combined and concentrated at 65°C for 1 hour to obtain 32 g of white solid. Toluene (340 ml) was added, and the oil temperature was raised to 105°C to dissolve and clarify. The temperature was naturally cooled to room temperature and stirred for 1 hour, filtered, and dried in vacuo at 70°C for 3 hours to obtain a white solid as compound 1-3 (23.50 g, purity: 99.51%, yield: 68.61%), mass spectrum: 573.06 (M+H).

[0102] Synthesis of Compounds 1-5

[0103] Compound 1-3 (23.00 g, 40.08 mmol), compound 1-4 (4.89 g, 40.08 mmol), tetrakis(triphenylphosphine)palladium (0.46 g, 0.40 mmol), potassium carbonate (13.85 g, 100.19 mmol), toluene (360 ml), ethanol (120 ml), and deionized water (120 ml) were added to a 2000 ml three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. The oil temperature was raised to 65 ° C. and the reaction was carried out for 3 hours. TLC monitoring (by volume ratio, ethyl acetate: n-hexane = 1:20 as the developing solvent) was performed. When compound 1-3 was completely consumed, heating was stopped.

[0104] After the reaction was completed, a large amount of solid was precipitated, which was directly filtered to obtain 23 g of solid. Dichloromethane (700 ml) was added to dissolve and clarify. Silica gel (50 g, 200-300 mesh chromatography column silica gel) was filtered once, and the filtrates were combined and concentrated at 65°C to obtain 21 g of white solid. Tetrahydrofuran (600 ml) was added, and the oil temperature was raised to 65°C to dissolve and clarify. Methanol (300 ml) was then added, and the temperature was naturally cooled to room temperature and stirred for 2 hours. A large amount of solid was precipitated, which was filtered and dried in vacuo at 70°C for 2 hours to obtain a white solid as compound 1-5 (18.53 g, purity: 99.78%, yield: 80.96%), mass spectrum: 571.18 (M+H).

[0105] Synthesis of Compounds 1-7

[0106] Compound 1-6 (40.00 g, 149.70 mmol) and dry tetrahydrofuran (400 ml) were added to a 1000 ml three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. Then the system was cooled to -78 ° C, and then n-butyl lithium n-hexane solution (65.87 ml, 164.67 mmol, concentration 2.5 mol / L) was added dropwise, and the temperature in the system was controlled not to be higher than -70 ° C. The addition was completed in 20 minutes, and the temperature was maintained at -78 ° C and stirred for 1 hour. Finally, triethyl borate (32.78 g, 224.55 mmol) was slowly added dropwise, and the addition was completed in 10 minutes; the temperature was naturally raised to room temperature and stirred for 2 hours, and TLC monitoring (by volume ratio, ethyl acetate: n-hexane = 1:20 as the developing solvent) showed that compound 1-6 was completely consumed.

[0107] Deionized water (100 ml) was added dropwise to the system to quench the reaction. After warming to room temperature, the liquid was separated directly. The aqueous phase was extracted twice with ethyl acetate (200 ml * 2). The organic phases were combined and concentrated under reduced pressure at 65 ° C for 1 hour to obtain a light yellow solid. Ethyl acetate (20 ml) and n-hexane (200 ml) were added at room temperature and heated to 60 ° C for 2 hours. The mixture was cooled to room temperature and filtered, and vacuum dried at 70 ° C for 2 hours to obtain a white solid as compound 1-7 (21.56 g, purity: 98.87%, yield: 62.05%), mass spectrum: 233.16 (M+H)

[0108] Synthesis of Compounds 1-9

[0109] Compound 1-7 (21.50 g, 92.62 mmol), compound 1-8 (17.82 g, 92.62 mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (0.68 g, 0.93 mmol), sodium carbonate (24.54 g, 231.55 mmol), tetrahydrofuran (375 ml), and deionized water (125 ml) were added to a 1000 ml three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. Then, the system was heated to 75 ° C for 4 hours. The reaction was monitored by TLC (ethyl acetate: n-hexane = 1:20 by volume as the developing solvent). Compound 1-8 was completely consumed.

[0110] After the reaction was completed, a large amount of solid was precipitated, which was directly filtered to obtain 28 g of solid. Tetrahydrofuran (500 ml) was added to dissolve and clarify. Silica gel (60 g, 200-300 mesh chromatography column silica gel) was filtered once, and the filtrates were combined and concentrated at 50°C for 1 hour to obtain 25 g of white solid. Toluene (90 ml) was added, and the oil temperature was raised to 105°C to dissolve and clarify. The temperature was naturally cooled to room temperature and stirred for 1 hour, filtered, and dried in vacuo at 70°C for 3 hours to obtain a white solid as compound 1-9 (20.39 g, purity: 99.20%, yield: 73.43%), mass spectrum: 300.14 (M+H).

[0111] Synthesis of Compound 1-11

[0112] Compound 1-9 (20.00 g, 66.70 mmol), compound 1-10 (21.17 g, 83.38 mmol), tris(dibenzylideneacetone)dipalladium (0.61 g, 0.67 mmol), 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (0.64 g, 1.33 mmol), potassium acetate (16.37 g, 166.76 mmol), 1,4-dioxane (300 ml) were added to a 1000 ml three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. Then, the system was heated to 100 ° C. and reacted for 2 hours. The reaction was monitored by TLC (ethyl acetate: n-hexane = 1:20 by volume as the developing solvent). Compound 1-9 was completely consumed.

[0113] The temperature was lowered to 60°C, and the solvent was removed by concentration under reduced pressure. Ethyl acetate (700 ml) was added, and the mixture was washed three times with deionized water (300 ml*3). The mixture was separated, and the sample was mixed with silica gel and dry-loaded onto a column. Purification was performed by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate: n-hexane = 1:30 by volume as eluent). After elution, the mixture was concentrated under reduced pressure at 70°C for 2 hours to obtain a white solid as compound 1-11 (19.63 g, purity: 99.15%, yield: 75.20%), mass spectrum: 392.26 (M+H).

[0114] Synthesis of compound 1

[0115] Compound 1-5 (18.00 g, 31.52 mmol), compound 1-11 (12.33 g, 31.52 mmol), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) (0.22 g, 0.32 mmol), potassium carbonate (10.89 g, 78.79 mmol), 1,4-dioxane (225 ml), and deionized water (75 ml) were added to a 500 ml three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. The oil temperature was raised to 80 ° C. and the reaction was carried out for 3 hours. TLC monitoring (by volume ratio, ethyl acetate: n-hexane = 1:20 as the developing solvent) was performed. When compound 1-5 was completely consumed, heating was stopped.

[0116] After the reaction, a large amount of solid was precipitated, which was directly filtered to obtain 23g of solid. Xylene (360ml) was added and heated to 130°C to dissolve and clarify. Silica gel (20g, 200-300 mesh chromatography column silica gel) was filtered once. The filtrate was cooled to room temperature and stirred for 2 hours. 21.5g of white solid was obtained by suction filtration. Xylene (240ml) was added, and the oil temperature was raised to 130°C to dissolve and clarify. The temperature was naturally cooled to room temperature and stirred for 2 hours. The filter cake was vacuum dried at 90°C for 3 hours to obtain a white solid compound 1 (19.23g, purity: 99.91%, yield: 76.26%). 19.23g of crude compound 1 was purified by sublimation to obtain sublimation pure compound 1 (12.93g, purity: 99.95%, yield: 67.23%), mass spectrum: 800.39 (M+H).

[0117] 1 H NMR (400MHz, CDCl3) δ8.47 (dd, J=15.0, 3.1Hz, 1H), 8.35 (t, J=3.0Hz, 1H), 8.33–8.25 (m, 5H) ,8.23(s,1H),8.02(t,J=3.0Hz,1H),7.96(dd,J=14.9,3.0Hz,1H),7.90–7.80(m,4H),7.80–7 .69(m,6H),7.57(d,J=2.9Hz,1H),7.52(m,1H),7.49(dd,J=3.9,3.0Hz,3H),7.48–7.45(m,2 H),7.45–7.35(m,4H),7.16(d,J=15.0Hz,1H),7.12–7.08(m,1H),1.69(m,4H),0.91(s,12H).

[0118] Synthesis of compound 2

[0119]

[0120] Synthesis of compound 2-2

[0121] Referring to the synthesis and purification methods of compound 1-3, it is only necessary to change the corresponding raw materials to obtain the target compound 2-2 (18.73 g, purity: 99.56%, yield: 73.41%), mass spectrum: 421.21 (M+H).

[0122] Synthesis of Compound 2-4

[0123] Referring to the synthesis and purification methods of compound 1-5, it is only necessary to change the corresponding raw materials to obtain the target compound 2-4 (16.27 g, purity: 99.73%, yield: 74.77%), mass spectrum: 496.15 (M+H).

[0124] Synthesis of compound 2

[0125] Referring to the synthesis and purification method of compound 1, only the corresponding raw materials need to be changed to obtain the target compound 2 (17.34 g, purity: 99.92%, yield: 74.15%). 17.34 g of crude compound 2 was purified by sublimation to obtain sublimation pure compound 2 (11.67 g, purity: 99.92%, yield: 67.30%), mass spectrum: 725.35 (M+H).

[0126] 1 H NMR (400MHz, CDCl3) δ8.49(d,J=3.1Hz,1H),8.46(d,J=3.1Hz,1H),8.30(t,J=2.9Hz,1H),8.23(s,1 H),8.20(t,J=2.9Hz,1H),8.18(t,J=2.4Hz,1H),8.14(t,J=3.0Hz,1H),8.09(t,J=3.0Hz,1H),7.94( m,5H),7.89(dd,J=15.0,2.9Hz,1H),7.70–7.61(m,2H),7.60–7.52(m,5H),7.52–7.45(m,3H),7.41 (dd,J=15.0,2.9Hz,1H),7.15(t,J=13.8Hz,2H),7.11(d,J=12.7Hz,1H),1.70(m,4H),0.97(s,12H).

[0127] Synthesis of compound 3

[0128]

[0129] Synthesis of compound 3-3

[0130] Compound 3-1 (20.00 g, 90.07 mmol), compound 3-2 (17.24 g, 90.07 mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (0.63 g, 0.63 mmol), sodium carbonate (23.87 g, 225.18 mmol), tetrahydrofuran (375 ml), and deionized water (125 ml) were added to a 1000 ml three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. Then, the system was heated to 60 ° C for 4 hours. The reaction was monitored by TLC (ethyl acetate: n-hexane = 1:15 by volume as the developing solvent). Compound 3-1 was completely consumed.

[0131] After the reaction was completed, a large amount of solid was precipitated, which was directly filtered to obtain 26 g of solid. Tetrahydrofuran (500 ml) was added to dissolve and clarify. Silica gel (60 g, 200-300 mesh chromatography column silica gel) was filtered once, and the filtrates were combined and concentrated at 50°C for 1 hour to obtain 24 g of white solid. Toluene (50 ml) was added, and the oil temperature was raised to 105°C to dissolve and clarify. The temperature was naturally cooled to room temperature and stirred for 1 hour, filtered, and dried in vacuo at 70°C for 3 hours to obtain a white solid as compound 3-3 (23.19 g, purity: 99.34%, yield: 77.27%), mass spectrum: 289.07 (M+H).

[0132] Synthesis of Compound 3-4

[0133] Referring to the synthesis and purification method of compound 1-11, it is only necessary to change the corresponding raw materials to obtain the target compound 3-4 (20.36 g, purity: 99.14%, yield: 77.57%), mass spectrum: 381.16 (M+H).

[0134] Synthesis of Compound 3-5

[0135] Referring to the synthesis and purification methods of compound 1-5, it is only necessary to change the corresponding raw materials to obtain the target compound 3-5 (26.34 g, purity: 99.76%, yield: 84.16%), mass spectrum: 595.13 (M+H).

[0136] Synthesis of compound 3

[0137] Referring to the synthesis and purification method of compound 1, only the corresponding raw materials need to be changed to obtain the target compound 3 (26.13 g, purity: 99.95%, yield: 75.48%). 26.13 grams of crude compound 3 was purified by sublimation to obtain sublimation pure compound 3 (16.93 g, purity: 99.95%, yield: 64.79%), mass spectrum: 824.37 (M+H).

[0138] 1 H NMR(400MHz, CDCl3)δ8.67(dd,J=4.1,2.1Hz,1H),8.46–8.39(m,2H),8.25–8.21(m,2H),8.12–8.07(m,1H),8.02–7.90(m,4 H),7.89–7.80(m,6H),7.69(dd,J=7.7,2.2Hz,1H),7.70–7.49(m,7H),7.47–7.34(m,9H),2.05–1.95(m,4H),1.21(s,12H).

[0139] Synthesis of compound 4

[0140]

[0141] Synthesis of compound 4-2

[0142] Referring to the synthesis and purification method of compound 3-3, it is only necessary to change the corresponding raw materials to obtain the target compound 4-2 (20.56 g, purity: 99.62%, yield: 73.06%), mass spectrum: 300.14 (M+H).

[0143] Synthesis of compound 4-3

[0144] Referring to the synthesis and purification method of compound 1-11, it is only necessary to change the corresponding raw materials to obtain the target compound 4-3 (12.53 g, purity: 99.13%, yield: 71.29%), mass spectrum: 392.23 (M+H).

[0145] Synthesis of Compound 4-5

[0146] Referring to the synthesis and purification methods of compound 1-5, it is only necessary to change the corresponding raw materials to obtain the target compound 4-5 (27.86 g, purity: 99.59%, yield: 79.12%), mass spectrum: 495.17 (M+H).

[0147] Synthesis of compound 4

[0148] Referring to the synthesis and purification method of compound 1, only the corresponding raw materials need to be changed to obtain the target compound 4 (17.56 g, purity: 99.90%, yield: 73.57%). 17.56 grams of crude compound 4 was purified by sublimation to obtain sublimation pure compound 4 (11.37 g, purity: 99.97%, yield: 64.74%), mass spectrum: 724.36 (M+H).

[0149] 1 H NMR (400MHz, CDCl3) δ9.43(d,J=0.6Hz,1H),9.07(d,J=15.0Hz,1H),8.34(t,J=2.9Hz ,1H),8.29(t,J=3.0Hz,1H),8.23(s,1H),8.03(t,J=3.0Hz,1H),7.95(dd,J=6.1,2.4 Hz,2H),7.93(dd,J=3.4,1.5Hz,2H),7.84(d,J=15.0Hz,1H),7.79–7.71(m,2H),7.60 –7.36(m,10H),7.27–7.19(m,5H),7.11(d,J=15.0Hz,1H),1.69(m,4H),1.05(s,12H).

[0150] Synthesis of compound 5

[0151]

[0152] Synthesis of compound 5-2

[0153] Referring to the synthesis and purification method of compound 3-3, it is only necessary to change the corresponding raw materials to obtain the target compound 5-2 (11.56 g, purity: 99.46%, yield: 73.06%), mass spectrum: 300.14 (M+H).

[0154] Synthesis of compound 5-3

[0155] Referring to the synthesis and purification method of compound 1-11, it is only necessary to change the corresponding raw materials to obtain the target compound 5-3 (10.37 g, purity: 99.33%, yield: 79.56%), mass spectrum: 587.33 (M+H).

[0156] Synthesis of compound 5

[0157] Referring to the synthesis and purification method of compound 1, only the corresponding raw materials need to be changed to obtain the target compound 5 (9.76 g, purity: 99.95%, yield: 79.07%). 9.76 grams of crude compound 5 was sublimated and purified to obtain sublimation pure compound 5 (6.88 g, purity: 99.95%, yield: 70.49%), mass spectrum: 724.31 (M+H).

[0158] 1 H NMR (400MHz, CDCl3) δ8.57(t,J=3.0Hz,1H),8.47(dd,J=15.0,3.1Hz,1H),8.29(t,J=3.0Hz,1H),8.24(dd,J=5.9,3.0Hz,2H),7.94(m,4H),7.89 (dd,J=14.9,3.0Hz,1H),7.75(m,2H),7.60–7.36(m,10H),7.27–7.21(m ,5H),7.19–7.12(m,1H),7.12–7.08(m,1H),1.75(m,4H),1.06(s,12H).

[0159] Synthesis of compound 6

[0160]

[0161] Synthesis of compound 6-2

[0162] Referring to the synthesis and purification method of compound 3-3, it is only necessary to change the corresponding raw materials to obtain the target compound 6-2 (15.72 g, purity: 99.49%, yield: 81.82%), mass spectrum: 376.14 (M+H).

[0163] Synthesis of compound 6-3

[0164] Referring to the synthesis and purification method of compound 1-11, it is only necessary to change the corresponding raw materials to obtain the target compound 6-3 (14.72 g, purity: 99.14%, yield: 76.38%), mass spectrum: 468.32 (M+H).

[0165] Synthesis of compound 6-4

[0166] Referring to the synthesis and purification method of compound 1-5, it is only necessary to change the corresponding raw materials to obtain the target compound 6-4 (12.47 g, purity: 99.72%, yield: 75.26%), mass spectrum: 419.16 (M+H).

[0167] Synthesis of compound 6

[0168] Referring to the synthesis and purification method of compound 1, only the corresponding raw materials need to be changed to obtain the target compound 6 (15.91 g, purity: 99.93%, yield: 76.72%). 15.91 grams of crude compound 6 was purified by sublimation to obtain sublimation pure compound 6 (10.18 g, purity: 99.94%, yield: 63.98%), mass spectrum: 724.32 (M+H).

[0169] 1 H NMR (400MHz, CDCl3) δ8.47(dd,J=15.0,3.1Hz,1H),8.35–8.29(m,2H),8.23(s,1H),8.17(t,J=3.0Hz,1H),7.98–7.88(m,5H),7.79–7.71(m ,2H),7.61–7.36(m,10H),7.31(dd,J=14.9,3.0Hz,1H),7.25(s,4H),7.19–7.12(m,1H),7.11(d,J=12.9Hz,1H),1.72(m,4H),1.10(s,12H).

[0170] Synthesis of compound 7

[0171]

[0172] Synthesis of compound 7-2

[0173] Referring to the synthesis and purification methods of compound 1-3, only the corresponding raw materials need to be changed to obtain the target compound 7-2 (24.12 g, purity: 99.61%, yield: 73.12%), mass spectrum: 573.09 (M+H).

[0174] Synthesis of compound 7-3

[0175] Referring to the synthesis and purification method of compound 1-5, it is only necessary to change the corresponding raw materials to obtain the target compound 7-3 (18.21 g, purity: 99.73%, yield: 76.25%), mass spectrum: 571.15 (M+H).

[0176] Synthesis of compound 7

[0177] Referring to the synthesis and purification method of compound 1, only the corresponding raw materials need to be changed to obtain the target compound 7 (15.71 g, purity: 99.90%, yield: 74.76%). 15.71 grams of crude compound 7 was sublimated and purified to obtain sublimation pure compound 7 (9.67 g, purity: 99.95%, yield: 61.55%), mass spectrum: 800.36 (M+H).

[0178] 1 H NMR (400MHz, CDCl3) δ8.47(dd,J=15.0,3.1Hz,1H),8.31(d,J=2.3Hz,1H),8.29(d,J=2.5Hz,1H),8.26( dd,J=2.8,1.9Hz,2H),8.23(s,1H),8.01(t,J=3.0Hz,1H),7.97(d,J=2.3Hz,1H),7.93(dd,J=14.9,3.0H z,2H),7.86(d,J=2.5Hz,1H),7.84(d,J=2.3Hz,1H),7.78–7.71(m,6H),7.55–7.36(m,11H),7.26(d,J=2 .3Hz,1H),7.24(d,J=2.3Hz,1H),7.19–7.12(m,1H),7.11(d,J=12.6Hz,1H),1.73(m,4H),0.91(s,12H).

[0179] Synthesis of compound 8

[0180]

[0181] Synthesis of compound 8-2

[0182] Referring to the synthesis and purification methods of compound 1-3, only the corresponding raw materials need to be changed to obtain the target compound 8-2 (25.61, purity: 99.65%, yield: 77.27%), mass spectrum: 421.06 (M+H).

[0183] Synthesis of compound 8-3

[0184] Referring to the synthesis and purification methods of compound 1-5, it is only necessary to change the corresponding raw materials to obtain the target compound 8-3 (22.71 g, purity: 99.51%, yield: 75.87%), mass spectrum: 495.14 (M+H).

[0185] Synthesis of compound 8

[0186] Referring to the synthesis and purification method of compound 1, only the corresponding raw materials need to be changed to obtain the target compound 8 (10.78 g, purity: 99.94%, yield: 73.71%). 10.78 grams of crude compound 8 was purified by sublimation to obtain sublimation pure compound 8 (6.81 g, purity: 99.94%, yield: 63.17%), mass spectrum: 724.33 (M+H).

[0187] 1 H NMR(400MHz, CDCl3)δ9.43(d,J=0.6Hz,1H),9.07(d,J=15.0Hz,1H),8.41–8.30(m,2H), 8.25(m,2H),8.23(s,1H),8.03(t,J=3.0Hz,1H),7.95(dd,J=6.1,2.4Hz,1H),7.93(dd, J=3.4,1.5Hz,1H),7.84(d,J=15.0Hz,1H),7.76(m,1H),7.74(dd,J=3.2,1.6Hz,1H),7. 61–7.36(m,10H),7.29–7.17(m,5H),7.11(d,J=14.9Hz,1H),1.72(m,4H),1.02(s,12H).

[0188] Synthesis of compound 9

[0189]

[0190] Synthesis of compound 9-1

[0191] Referring to the synthesis and purification methods of compound 1-11, it is only necessary to change the corresponding raw materials to obtain the target compound 9-1 (10.32 g, purity: 99.03%, yield: 72.58%), mass spectrum: 587.25 (M+H).

[0192] Synthesis of compound 9

[0193] Referring to the synthesis and purification method of compound 1, only the corresponding raw materials need to be changed to obtain the target compound 9 (9.51 g, purity: 99.92%, yield: 77.05%). 9.51 grams of crude compound 9 was sublimated and purified to obtain sublimation pure compound 9 (6.11 g, purity: 99.95%, yield: 64.24%), mass spectrum: 724.34 (M+H).

[0194] 1 H NMR (400MHz, CDCl3) δ8.50 (t, J=1.4Hz, 1H), 8.47 (dd, J=7.5, 1.4Hz, 1H), 8.38– 8.32(m,2H),8.25–8.20(m,3H),7.94(dd,J=7.3,1.4Hz,2H),7.88(dd,J=7.5,1. 4Hz,1H),7.75(dd,J=7.5,1.2Hz,2H),7.55(t,J=7.4Hz,2H),7.53–7.46(m,6H) ,7.44–7.38(m,2H),7.25(s,4H),7.19–7.09(m,3H),1.70(m,4H),0.98(s,12H).

[0195] Synthesis of compound 10

[0196]

[0197] Synthesis of compound 10-1

[0198] Referring to the synthesis and purification methods of compound 1-5, it is only necessary to change the corresponding raw materials to obtain the target compound 10-1 (12.51 g, purity: 99.76%, yield: 74.01%), mass spectrum: 419.14 (M+H).

[0199] Synthesis of compound 10

[0200] Referring to the synthesis and purification method of compound 1, only the corresponding raw materials need to be changed to obtain the target compound 10 (15.91 g, purity: 99.94%, yield: 76.72%). 15.91 grams of crude compound 10 was purified by sublimation to obtain sublimation pure compound 10 (9.78 g, purity: 99.95%, yield: 61.47%), mass spectrum: 724.33 (M+H).

[0201] 1H NMR(400MHz, CDCl3)δ8.47(dd,J=7.5,1.4Hz,1H),8.38–8.32(m,2H),8.29(t,J=1.4Hz,1H),8.25( t,J=1.4Hz,1H),8.23(s,1H),8.17(t,J=1.5Hz,1H),7.94(dd,J=7.3,1.4Hz,2H),7.90(dd,J=7.5, 1.4Hz,1H),7.75(dd,J=7.5,1.2Hz,2H),7.59–7.52(m,3H),7.52–7.46(m,6H),7.42(dd,J=5.1,3. 8Hz,1H),7.33(dd,J=7.5,1.4Hz,1H),7.25(s,4H),7.18–7.08(m,2H),1.69(m,4H),0.99(s,12H).

[0202] Application example: Fabrication of organic electroluminescent devices

[0203] like Figure 1 As shown, it is a schematic diagram of the structure of an organic electroluminescent device, including a stacked glass substrate 1, an anode 2, a hole injection layer 3, a first hole transport layer 4, a second hole transport layer 5, a light-emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9, and a cathode 10.

[0204] A 50mm*50mm*1.0mm glass substrate with an ITO (100nm) transparent electrode (anode 2) was ultrasonically cleaned in ethanol for 10 minutes, dried at 150 degrees, and then treated with N2 Plasma (plasma treatment) for 30 minutes. The treated glass substrate was mounted on a substrate support of a vacuum evaporation device, and the compound HATCN was first evaporated on the surface of the transparent electrode line in a manner of covering the transparent electrode to form a film with a thickness of 5nm (hole injection layer 3); then a layer of HTM1 was evaporated to form a film with a thickness of 60nm (first hole transport layer 4); then a layer of HTM2 was evaporated on the HTM1 film to form a film with a thickness of 10nm (second hole transport layer 5); then, the main material and the doping material were evaporated on the HTM2 film layer in a co-evaporation mode to obtain a light-emitting layer 6, wherein the light-emitting layer had a film thickness of 20nm, and the ratio of the main material to the doping material was 97%:3%. HBL (5 nm) is evaporated on the light-emitting layer 6 as a hole blocking layer material to obtain a hole blocking layer 7; then an electron transport layer material (the compound of the present invention or the comparative compound and Liq are matched in a mass ratio of 1:1) is evaporated on the hole blocking layer 7 to obtain an electron transport layer 8, wherein the thickness of the electron transport layer is 30 nm; then LiF (1 nm) is evaporated on the electron transport layer 8 as an electron injection material to obtain an electron injection layer 9; then Al (100 nm) is evaporated as a cathode material to form a cathode 10.

[0205] The relevant materials are described as follows:

[0206]

[0207] The above device was tested for device performance. In each embodiment and comparative example, a constant current power supply (Keithley2400) was used to flow a fixed current density through the light-emitting device, and a spectroradiometer (CS2000) was used to test the luminous spectrum. At the same time, 10 mA / cm 2 The driving voltage and current efficiency under the test 20mA / cm 2 The brightness decay time (LT 90 ). All data are based on Comparative Example 1 as 100% reference standard (for example, driving voltage 96% means: under the same test conditions, the driving voltage is 96% of Comparative Example 1), and the results are shown in Table 1 below:

[0208] Table 1

[0209] Group Electron transport layer Driving voltage % Current efficiency % <![CDATA[LT 90 Life %]]> Device Example 1 Compound 1 96 103 103 Device Example 2 Compound 2 98 104 105 Device Example 3 Compound 3 95 106 107 Device Example 4 Compound 4 97 105 106 Device Example 5 Compound 5 97 101 110 Device Example 6 Compound 6 96 103 108 Device Example 7 Compound 7 98 102 104 Device Example 8 Compound 8 99 103 102 Device Example 9 Compound 9 97 104 101 Device Example 10 Compound 10 98 102 100 Comparative Example 1 Comparative Compound 1 100 100 100 Comparative Example 2 Comparative Compound 2 101 99 91 Comparative Example 3 Comparative Compound 3 103 98 94 Comparative Example 4 Comparative Compound 4 102 98 95 Comparative Example 5 Comparative Compound 5 99 97 95 Comparative Example 6 Comparative Compound 6 103 97 98 Comparative Example 7 Comparative Compound 7 105 94 90 Comparative Example 8 Comparative Compound 8 103 98 96

[0210] As can be seen from Table 1, the compounds of the present invention are applied to organic electroluminescent devices as electron transport layers, and show more superior performance in terms of driving voltage, luminous efficiency, and device life compared to the comparative compounds.

[0211] In addition, the compound of the present invention also has the advantages of good optical, electrical and thermal stability, and the OLED device prepared by using the compound has the advantages of low voltage, long life, high luminous efficiency, etc., and can be used in organic light-emitting devices. In particular, as an electron transport material, it has the possibility of being applied to the AMOLED industry.

Claims

1. A compound, characterized in that It has the structure shown in formula (1): Wherein, X1 and X2 are independently selected from N or CH, and X1 and X2 are different; Z1, Z2, Z3, and Z4 are independently selected from N or CR1, and only one of them is selected from N; L is selected from a single bond, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 6 to 30 ring atoms; Ar1, Ar2, Ar3 are independently selected from a substituted or unsubstituted aromatic group having 5-60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5-60 ring atoms, a substituted or unsubstituted aryloxy group having 5-60 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5-60 ring atoms, or a combination of these groups, which can form a monocyclic or polycyclic aliphatic or aromatic ring system with the ring bonded to the group; R1 is independently selected from hydrogen, deuterium, halogen, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, silyl, linear alkyl having 1 to 20 C atoms, linear alkoxy having 1 to 20 C atoms, linear thioalkoxy having 1 to 20 C atoms, branched or cyclic alkyl having 3 to 20 C atoms, branched or cyclic alkoxy having 3 to 20 C atoms, a branched or cyclic thioalkoxy group having 1 to 20 C atoms, a keto group having 1 to 20 C atoms, an alkoxycarbonyl group having 2 to 20 C atoms, an aryloxycarbonyl group having 7 to 20 C atoms, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, or a heteroaryloxy group having 5 to 60 ring atoms; or a combination of these groups, and two adjacent groups may be fused to form a ring; In the L and R1, the substitution is independently substituted by at least one of deuterium, halogen, cyano, isocyano, C1-C6 alkyl, C1-C6 haloalkyl, C3-C16 cycloalkyl, C6-C30 aryl, and triphenylsilyl, wherein the number of substitutions is from a single substitution to a maximum number of substitutions; The heteroatoms in the heteroaromatic group, heteroaromatic group or heteroaryloxy group are independently selected from at least one of O, S, N, P, Si, Se or Ge.

2. The compound according to claim 1, characterized in that The compound represented by formula (1) is selected from one of the structures represented by the following formulas (2-1) to (2-4):

3. The compound according to claim 1 or 2, characterized in that The L is selected from a single bond, a substituted or unsubstituted aromatic group having 6 to 25 ring atoms, or a substituted or unsubstituted heteroaromatic group having 6 to 25 ring atoms; and / or, Ar1 to Ar3 are independently selected from a substituted or unsubstituted aromatic group having 5-40 ring atoms, a substituted or unsubstituted heteroaromatic group having 5-40 ring atoms, a substituted or unsubstituted aryloxy group having 5-40 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5-40 ring atoms; or a combination of these groups, which can form a monocyclic or polycyclic aliphatic ring or aromatic ring with the ring bonded to the group; And / or, the substituents in L and R1 are independently selected from at least one of deuterium, halogen, cyano, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 haloalkyl, C6-C30 aryl, and triphenylsilyl, wherein the number of substitutions is from a single substitution to a maximum number of substitutions.

4. The compound according to claim 1 or 2, characterized in that The L is selected from a single bond or one of the structures shown in the following formula A-1 to formula A-18; wherein Formula A-1 to Formula A-18 are optionally substituted by 0 to 3 groups selected from D, F, Cl, Br, cyano, C1-C4 alkyl, C1-C3 haloalkyl, phenyl, naphthyl, fluorenyl, spirofluorenyl and C3-C10 cycloalkyl; "*" indicates the bonding site of L.

5. The compound according to claim 1 or 2, characterized in that Ar1 to Ar3 are independently selected from one of the following structures: Wherein, each occurrence of W is independently selected from N or CR2; Each occurrence of V is independently selected from O, S, S=O, SO2, NR3, CR4R5 or SiR6R7; Each occurrence of R2 to R7 is independently selected from hydrogen, deuterium, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, straight-chain alkyl with 1 to 10 C atoms, straight-chain alkoxy with 1 to 10 C atoms, straight-chain thioalkoxy with 1 to 10 C atoms, branched or cyclic alkyl with 3 to 10 C atoms, branched or cyclic alkoxy with 3 to 10 C atoms, A branched or cyclic thioalkoxy group having 3 to 10 C atoms, a silyl group, a keto group having 1 to 10 C atoms, an alkoxycarbonyl group having 2 to 10 C atoms, an aryloxycarbonyl group having 7 to 10 C atoms, a substituted or unsubstituted aromatic group having 5 to 10 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms, an aryloxy group having 5 to 10 ring atoms, a heteroaryloxy group having 5 to 10 ring atoms; or a combination of these groups; R2-R7 may form a ring; In the R2 to R7, the substitution is independently substituted by at least one of deuterium, halogen, cyano, isocyano, C1-C3 alkyl, C1-C3 haloalkyl, C3-C5 cycloalkyl, C6-C10 aryl, and triphenylsilyl, wherein the number of substitutions is from a single substitution to a maximum number of substitutions; The heteroatoms in the heteroaromatic group or heteroaryloxy group are independently selected from at least one of O, S, N, P, Si, Se or Ge.

6. The compound according to claim 5, characterized in that Ar1 to Ar3 are independently selected from one of the following structures: Wherein, Ra and V are defined as R defined in claim 5. 1、 V; s is an integer from 0 to 5; "*" indicates the bonding site of Ar1 to Ar3.

7. The compound according to claim 5, characterized in that Ar1 to Ar3 are the same as or different from each other and are each independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted 9,9-spirobifluorenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted thiophene ... substituted or unsubstituted dibenzothioxanyl, substituted or unsubstituted dibenzodioxinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted indolocarbazolyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted benzocarbazolyl, substituted or unsubstituted benzofluorenyl, substituted or unsubstituted benzonaphthofuranyl, substituted or unsubstituted benzonaphthothiophenyl, or substituted or unsubstituted fluoranthenyl.

8. The compound according to claim 7, characterized in that Ar1 to Ar3 are independently selected from one of the following groups: Wherein, R3 is the same as R3 defined in claim 5; "*" represents the bond connection site of Ar1 to Ar3.

9. The compound according to claim 1, characterized in that The compound represented by formula (1) is selected from one of the following structural formulas:

10. An organic electroluminescent device, characterized in that: The method comprises a functional layer, wherein the functional layer comprises the compound according to any one of claims 1 to 9.

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