Host material and organic electroluminescent device

Abstract

The application belongs to the technical field of organic electroluminescence, and discloses a host material and an organic electroluminescent device. The host material comprises at least one first host compound and at least one second host compound, wherein the first host compound is represented by the following formula (1): wherein ring A is selected from X1-X 12 are independently selected from CR0 or N, X is selected from NR a , CR b R c or an oxygen group element; the second host compound is represented by formula (2): wherein Z1, Z2, Z3 are each independently selected from N or CR d ; at least one of Ar3, Ar4, Ar5 is selected from formula (3): Y is selected from O, S, Se. The compound has the advantages of high optical and electrical stability, low sublimation temperature, low driving voltage, high luminous efficiency, long device life and the like, and can be used as a host material in an OLED light-emitting device.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of organic electroluminescence, and particularly relates to a host material and an organic electroluminescence device. BACKGROUND

[0002] At present, an organic electroluminescence device (OLED) as a new generation of display technology has obtained more and more attention in display and lighting technology, and has a very wide application prospect. However, compared with the market application requirements, the performance of the OLED device such as the luminous efficiency, the driving voltage and the service life still needs to be improved.

[0003] Generally, the basic structure of the OLED device is a sandwich structure in which various different functional organic functional material thin films are interposed in the middle of the metal electrode, and under the driving of the current, electrons and holes are injected from the cathode and the anode respectively, the holes and the electrons are combined in the light-emitting layer after moving a distance, and are released in the form of light or heat, so as to achieve the light-emitting effect. The performance of the organic functional material affects the movement of the holes and the electrons, and further affects the light-emitting performance of the OLED. However, the properties of the phosphorescent OLED are not only determined by the used triplet light emitter. Other types of materials, such as the host material, are also quite important. The host material has a significant effect on reducing the driving voltage of the device, improving the luminous efficiency of the device and improving the service life of the device. Therefore, it is necessary to continue to develop new host materials and their compositions, so as to further improve the performance of the organic electroluminescence device, and to solve the above-mentioned problems existing in the light-emitting device. SUMMARY

[0004] The present application aims at at least solving one of the technical problems existing in the prior art. To this end, the present application proposes a host material and an organic electroluminescence device.

[0005] In a first aspect of the present application, a host material is provided, which comprises at least one first host compound and at least one second host compound, wherein the first host compound is represented by the following formula (1):

[0006]

[0007] wherein ring A is selected from the following formula (1-2) or formula (1-3);

[0008]

[0009] wherein X1-X 12 are independently selected from CR0or N; and X1-X4, X 5- X6, X7-X8, X9-X 12 two adjacent sites are fused with the 5-membered ring containing X in formula (1);

[0010] each R0is independently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C40alkyl, substituted or unsubstituted C1-C40heteroalkyl, substituted or unsubstituted C2-C40alkenyl, substituted or unsubstituted C2-C40alkynyl, substituted or unsubstituted C3-C40cycloalkyl, substituted or unsubstituted C3-C40heterocycloalkyl, substituted or unsubstituted C6-C60aryl, substituted or unsubstituted C3-C60heteroaryl, substituted or unsubstituted C1-C40alkoxy, substituted or unsubstituted C6-C60aryloxy, substituted or unsubstituted C1-C40alkylsilyl, substituted or unsubstituted C6-C60arylsilyl, substituted or unsubstituted C1-C40alkylboronyl, substituted or unsubstituted C6-C60arylboryl, substituted or unsubstituted C6-C60arylphosphino, or substituted or unsubstituted C6-C60arylamino; or, two adjacent R0may be joined into a ring;

[0011] Ring B is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, or a substituted or unsubstituted phenanthrene ring;

[0012] X in formula (1) is selected from NR a , CR b R c , or a chalcogen element;

[0013] R a , R b , R c are each independently selected from substituted or unsubstituted C1-C30alkyl, substituted or unsubstituted C1-C30heteroalkyl, substituted or unsubstituted C3-C30cycloalkyl, substituted or unsubstituted C3-C30heterocycloalkyl, substituted or unsubstituted C6-C30aryl, substituted or unsubstituted C3-C30heteroaryl, substituted or unsubstituted C3-C30alkylsilyl, substituted or unsubstituted C6-C30arylsilyl; or, R b and R c are joined into a ring;

[0014] L is selected from a single bond, substituted or unsubstituted C6-C60arylene, or substituted or unsubstituted C3-C60heteroarylene;

[0015] Ar1and Ar2are each independently selected from substituted or unsubstituted C6-C60aryl, substituted or unsubstituted C3-C60heteroaryl;

[0016] wherein the second host compound is represented by the following formula (2):

[0017]

[0018] wherein Z1, Z2, Z3are each independently selected from N or CR d ;

[0019] R d selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C40alkyl, substituted or unsubstituted C1-C40heteroalkyl, substituted or unsubstituted C2-C40alkenyl, substituted or unsubstituted C2-C40alkynyl, substituted or unsubstituted C3-C40cycloalkyl, substituted or unsubstituted C3-C40heterocycloalkyl, substituted or unsubstituted C6-C60aryl, substituted or unsubstituted C3-C60heteroaryl, substituted or unsubstituted C1-C40alkoxy, substituted or unsubstituted C6-C60aryloxy, substituted or unsubstituted C1-C40alkylsilyl, substituted or unsubstituted C6-C60arylsilyl, substituted or unsubstituted C1-C40alkylboronyl, substituted or unsubstituted C6-C60arylboryl, substituted or unsubstituted C6-C60arylphosphino, or substituted or unsubstituted C6-C60arylamino;

[0020] L1, L2, L3are each independently selected from a single bond, substituted or unsubstituted C6-C60arylene, substituted or unsubstituted C3-C60heteroarylene, or substituted or unsubstituted C3-C30cycloalkylene;

[0021] Ar3to Ar5each independently represent hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C60alkyl, substituted or unsubstituted C6-C60aryl, substituted or unsubstituted C3-C60heteroaryl, substituted or unsubstituted C3-C60cycloalkyl, substituted or unsubstituted C1-C30alkoxy, substituted or unsubstituted tri(C1-C30)alkylsilyl, substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, substituted or unsubstituted tri(C6-C30)arylsilyl, or -N-(R’)(R”); or Ar3to Ar5each independently and the substituents on the carbon atoms or heteroatoms adjacent to the substitution sites thereof are linked to form a ring;

[0022] R’ and R” each independently represent substituted or unsubstituted C1-C30alkyl, substituted or unsubstituted C2-C30alkenyl, substituted or unsubstituted C6-C30aryl, or substituted or unsubstituted C3-C30heteroaryl;

[0023] and, at least one of Ar3, Ar4, Ar5is selected from the following formula (3):

[0024]

[0025] Y is selected from O, S or Se;

[0026] represents the connection site with L1, L2, L3 in formula (2);

[0027] ring C is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring or a substituted or unsubstituted phenanthrene ring;

[0028] Ar6 is selected from a substituted or unsubstituted C6-C36 aryl group, a substituted or unsubstituted C2-C36 heteroaryl group;

[0029] wherein, the R0, R a ~R d , L, L1~L3, Ar1~Ar6, R', R" are each independently substituted with at least one of deuterium, halogen, cyano, isocyano, phosphino, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl-substituted amine, C1-C6 hydrocarbon-substituted or unsubstituted C6-C30 aryl, C1-C6 hydrocarbon-substituted or unsubstituted C3-C30 heteroaryl, wherein the number of substitutions is mono-substitution to the maximum number of substitutions;

[0030] the heteroatom in the heteroaromatic group, heteroaryl group, heteroalkyl group, heterocycloalkyl group or heteroatom is independently selected from at least one of O, S, N, Se, Si or Ge.

[0031] The beneficial effects of the present application relative to the prior art are as follows:

[0032] The various host materials in the present application have the advantages of low sublimation temperature, low driving voltage, high luminous efficiency, long device lifetime, etc., and can be used as host materials in OLED light-emitting devices. At the same time, they have a relatively low melting point, which is beneficial to the stability of material evaporation as a molten material. The various host materials as red light host materials have the possibility of application in the AMOLED industry. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 A226 is a compound of the present application 1 H NMR spectrum;

[0034] Figure 2 The organic electroluminescent device structure schematic diagram of an embodiment of the present application. DETAILED DESCRIPTION

[0035] In order to make those skilled in the art more clearly understand the technical solutions described in the present application, the following examples are given for illustration. It should be pointed out that the following examples do not constitute a limitation on the scope of protection required by the present application.

[0036] The starting materials, reagents, or the like used in the following examples are commercially available unless otherwise specified, or can be obtained by known methods.

[0037] The host material includes at least one first host compound and at least one second host compound, wherein the first host compound is represented by the following formula (1):

[0038]

[0039] wherein ring A is selected from the following formula (1-2) or formula (1-3);

[0040]

[0041] wherein X1-X 12 are each independently selected from CR0or N; and X1-X4, X 5- X6, X7-X8, X9-X 12 two adjacent sites are fused to the 5-membered ring containing X in formula (1);

[0042] R0are each independently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C40alkyl, substituted or unsubstituted C1-C40heteroalkyl, substituted or unsubstituted C2-C40alkenyl, substituted or unsubstituted C2-C40alkynyl, substituted or unsubstituted C3-C40cycloalkyl, substituted or unsubstituted C3-C40heterocycloalkyl, substituted or unsubstituted C6-C60aryl, substituted or unsubstituted C3-C60heteroaryl, substituted or unsubstituted C1-C40alkoxy, substituted or unsubstituted C6-C60aryloxy, substituted or unsubstituted C1-C40alkylsilyl, substituted or unsubstituted C6-C60arylsilyl, substituted or unsubstituted C1-C40alkylboronyl, substituted or unsubstituted C6-C60arylboryl, substituted or unsubstituted C6-C60arylphosphino, or substituted or unsubstituted C6-C60arylamino; or, two adjacent R0may be connected into a fused ring;

[0043] Ring B is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, or a substituted or unsubstituted phenanthrene ring;

[0044] X in formula (1) is selected from NR a , CR b R c or an oxygen group element;

[0045] R a , R b , R cEach is independently selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 heteroalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C1-C30 alkylsilyl, substituted or unsubstituted C6-C30 arylsilyl; or, R b and R c Connect them into a ring;

[0046] L is selected from single-bonded, substituted or unsubstituted C6-C60 arylene or substituted or unsubstituted C3-C60 heteroarylene;

[0047] Ar1 and Ar2 are independently selected from substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl, respectively;

[0048] The second main compound is represented by the following formula (2):

[0049]

[0050] Among them, Z1, Z2, and Z3 are each independently selected from N or CR. d ;

[0051] R d Selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C1-C40 heteroalkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 ynyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C3-C40 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl Substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C1-C40 alkylsilyl, substituted or unsubstituted C6-C60 arylsilyl, substituted or unsubstituted C1-C40 alkylboron, substituted or unsubstituted C6-C60 arylboron, substituted or unsubstituted C6-C60 arylphosphine, or substituted or unsubstituted C6-C60 arylamine;

[0052] L1, L2, and L3 are each independently selected from single-bonded, substituted or unsubstituted C6-C60 arylene, substituted or unsubstituted C3-C60 heteroarylene, or substituted or unsubstituted C3-C30 cycloalkylene.

[0053] Ar3to Ar5each independently represent hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C60alkyl, substituted or unsubstituted C6-C60aryl, substituted or unsubstituted C3-C60heteroaryl, substituted or unsubstituted C3-C60cycloalkyl, substituted or unsubstituted C1-C30alkoxy, substituted or unsubstituted tri(C1-C30)alkylsilyl, substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, substituted or unsubstituted tri(C6-C30)arylsilyl, or -N-(R')(R"); or Ar3to Ar5each independently and the substituents on the carbon atom or heteroatom adjacent to the substitution site thereof are linked to form a ring;

[0054] R' and R" each independently represent substituted or unsubstituted C1-C30alkyl, substituted or unsubstituted C2-C30alkenyl, substituted or unsubstituted C6-C30aryl, or substituted or unsubstituted C3-C30heteroaryl;

[0055] wherein at least one of Ar3, Ar4, Ar5is selected from the following formula (3):

[0056]

[0057] wherein Y is selected from O, S, or Se;

[0058] represents the connection site with L1, L2, L3in formula (2);

[0059] ring C is selected from substituted or unsubstituted benzene ring, substituted or unsubstituted naphthalene ring, or substituted or unsubstituted phenanthrene ring;

[0060] Ar6is selected from substituted or unsubstituted C6-C36aryl, substituted or unsubstituted C2-C36heteroaryl;

[0061] wherein the R0, R a ~R d , L, L1~L3, Ar1~Ar6, R', R" are each independently substituted with at least one of deuterium, halogen, cyano, isocyano, phosphino, C1-C6alkyl, C3-C16cycloalkyl, C1-C6alkyl-substituted amine, C1-C6hydrocarbyl-substituted or unsubstituted C6-C30aryl, C1-C6hydrocarbyl-substituted or unsubstituted C3-C30heteroaryl, wherein the number of substitutions is mono-substitution to the maximum number of substitutions;

[0062] the heteroatom in the heteroarylene, heteroaryl, heteroalkyl, heterocycloalkyl, or heteroatom is independently selected from at least one of O, S, N, Se, Si, or Ge.

[0063] Ar3to Ar5each independently and the substituents on the carbon atoms or heteroatoms adjacent to the substitution sites of Ar3to Ar5may be connected to form a ring; or, when L1to L3are single bonds, then the substituents on the substitution sites of Ar3to Ar5may be connected to Z1, Z2, Z3to form a ring; the ring formed by the connection can be a substituted or unsubstituted five- to seven-membered aromatic or aliphatic ring: for example, a substituted or unsubstituted naphthalene, fluorenyl, quinoline, dibenzothiophene, dibenzofuran, carbazole, benzofuro-pyridine, benzothienopyridine, indenopyridine, benzofuroquinoline, benzothienoquinoline, or indenoquinoline ring.

[0064] In some embodiments, X1to X 12 contain at least one N.

[0065] In some embodiments, X1to X 12 are each independently selected from CR0.

[0066] In some embodiments, the structure represented by formula (1-2) and formula (1-3) is selected from one of the structures represented by formula (1-4) to formula (1-11):

[0067]

[0068] wherein * represents the site of the fusion with the X-containing 5-membered ring in formula (1);

[0069] wherein a is an integer from 0 to 10; if a is an integer from 2 to 10, then each R0may be the same or different, and adjacent R0may be connected to form a fused ring (for example, a substituted or unsubstituted fused ring containing a C3-C30 aliphatic ring and a C6-C60 aromatic ring; wherein the carbon atoms can be replaced by at least one heteroatom selected from N, O, S, Si, Se, and P).

[0070] In some embodiments, the structure represented by formula (1-2) and formula (1-3) is selected from one of the structures represented by formula (1-12) to formula (1-19):

[0071]

[0072] wherein * represents the site of the fusion with the X-containing 5-membered ring in formula (1);

[0073] a is an integer from 0 to 6; if a is an integer from 2 to 6, then each R0may be the same or different, and adjacent two R0may be connected to form a fused ring.

[0074] In some embodiments, each R0is independently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C30alkyl, substituted or unsubstituted C1-C30heteroalkyl, substituted or unsubstituted C2-C30alkenyl, substituted or unsubstituted C2-C30alkynyl, substituted or unsubstituted C3-C30cycloalkyl, substituted or unsubstituted C3-C30heterocycloalkyl, substituted or unsubstituted C6-C30aryl, substituted or unsubstituted C3-C30heteroaryl, substituted or unsubstituted C1-C30alkoxy, substituted or unsubstituted C6-C30aryloxy, substituted or unsubstituted C1-C30alkylsilyl, substituted or unsubstituted C6-C30arylsilyl, substituted or unsubstituted C1-C30alkylboronyl, substituted or unsubstituted C6-C30arylboryl, substituted or unsubstituted C6-C30arylphosphino, or substituted or unsubstituted C6-C30arylamino.

[0075] In some embodiments, R0is selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C20alkyl, substituted or unsubstituted C1-C20heteroalkyl, substituted or unsubstituted C2-C20alkenyl, substituted or unsubstituted C2-C20alkynyl, substituted or unsubstituted C3-C20cycloalkyl, substituted or unsubstituted C3-C20heterocycloalkyl, substituted or unsubstituted C6-C20aryl, substituted or unsubstituted C3-C20heteroaryl, substituted or unsubstituted C1-C20alkoxy, substituted or unsubstituted C6-C20aryloxy, substituted or unsubstituted C1-C20alkylsilyl, substituted or unsubstituted C6-C20arylsilyl, substituted or unsubstituted C1-C20alkylboronyl, substituted or unsubstituted C6-C20arylboryl, substituted or unsubstituted C6-C20arylphosphino, or substituted or unsubstituted C6-C20arylamino.

[0076] In some embodiments, each R0is independently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C10alkyl, substituted or unsubstituted C1-C10heteroalkyl, substituted or unsubstituted C2-C10alkenyl, substituted or unsubstituted C2-C10alkynyl, substituted or unsubstituted C3-C10cycloalkyl, substituted or unsubstituted C3-C10heterocycloalkyl, substituted or unsubstituted C6-C12aryl, substituted or unsubstituted C3-C12heteroaryl, or substituted or unsubstituted C1-C10alkylsilyl.

[0077] In some embodiments, adjacent R0refers to R0on two adjacent carbon atoms.

[0078] In some embodiments, each of the ring B shown in formula (1) or ring C of formula (3) is independently selected from one of the structures shown in formulae (1-20) to (1-26):

[0079]

[0080] wherein * indicates a site of fusion with the 5-membered ring containing X in formula (1) or the 5-membered ring containing Y in formula (3);

[0081] q is an integer from 0 to 10; if q is an integer from 2 to 10, each R1may be the same or different, and adjacent R1may be joined to form a fused ring;

[0082] R1is selected from at least one of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C40alkyl, substituted or unsubstituted C1-C40heteroalkyl, substituted or unsubstituted C2-C40alkenyl, substituted or unsubstituted C2-C40alkynyl, substituted or unsubstituted C3-C40cycloalkyl, substituted or unsubstituted C3-C40heterocycloalkyl, substituted or unsubstituted C6-C60aryl, substituted or unsubstituted C3-C60heteroaryl, substituted or unsubstituted C1-C40alkoxy, substituted or unsubstituted C6-C60aryloxy, substituted or unsubstituted C1-C40alkylsilyl, substituted or unsubstituted C6-C60arylsilyl, substituted or unsubstituted C1-C40alkylboron, substituted or unsubstituted C6-C60arylboron, substituted or unsubstituted C6-C60arylphosphine, or substituted or unsubstituted C6-C60arylamines;

[0083] The substitution in R1is substitution with at least one of deuterium, halogen, cyano, isocyano, phosphine, C1-C6alkyl, C3-C16cycloalkyl, C1-C6alkyl-substituted amine, C1-C6hydrocarbyl-substituted or unsubstituted C6-C30aryl, or C1-C6hydrocarbyl-substituted or unsubstituted C3-C30heteroaryl, wherein the number of substitutions is from mono-substitution to the maximum number of substitutions.

[0084] In some embodiments, each R1is independently selected from at least one of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C30alkyl, substituted or unsubstituted C1-C30heteroalkyl, substituted or unsubstituted C2-C30alkenyl, substituted or unsubstituted C2-C30alkynyl, substituted or unsubstituted C3-C30cycloalkyl, substituted or unsubstituted C3-C30heterocycloalkyl, substituted or unsubstituted C6-C30aryl, substituted or unsubstituted C3-C30heteroaryl, substituted or unsubstituted C1-C30alkoxy, substituted or unsubstituted C6-C30aryloxy, substituted or unsubstituted C1-C30alkylsilyl, substituted or unsubstituted C6-C30arylsilyl, substituted or unsubstituted C1-C30alkylboronyl, substituted or unsubstituted C6-C30arylboryl, substituted or unsubstituted C6-C30arylphosphino, or substituted or unsubstituted C6-C30arylamino.

[0085] In some embodiments, each R1is independently selected from at least one of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C20alkyl, substituted or unsubstituted C1-C20heteroalkyl, substituted or unsubstituted C2-C20alkenyl, substituted or unsubstituted C2-C20alkynyl, substituted or unsubstituted C3-C20cycloalkyl, substituted or unsubstituted C3-C20heterocycloalkyl, substituted or unsubstituted C6-C20aryl, substituted or unsubstituted C3-C20heteroaryl, substituted or unsubstituted C1-C20alkoxy, substituted or unsubstituted C6-C20aryloxy, substituted or unsubstituted C1-C20alkylsilyl, substituted or unsubstituted C6-C20arylsilyl, substituted or unsubstituted C1-C20alkylboronyl, substituted or unsubstituted C6-C20arylboryl, substituted or unsubstituted C6-C20arylphosphino, or substituted or unsubstituted C6-C20arylamino.

[0086] In some embodiments, each R1is independently selected from at least one of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C10alkyl, substituted or unsubstituted C1-C10heteroalkyl, substituted or unsubstituted C2-C10alkenyl, substituted or unsubstituted C2-C10alkynyl, substituted or unsubstituted C3-C10cycloalkyl, substituted or unsubstituted C3-C10heterocycloalkyl, substituted or unsubstituted C6-C12aryl, or substituted or unsubstituted C3-C12heteroaryl.

[0087] In some embodiments, adjacent R1refers to R1on two adjacent carbon atoms.

[0088] In some embodiments, the chalcogen element is selected from O, S, or Se.

[0089] In some embodiments, X is selected from NR a , CR b R c , O, S, or Se; wherein,

[0090] R a , R b , R c are each independently selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C5-C20 heteroaryl, substituted or unsubstituted C3-C20 alkylsilyl, substituted or unsubstituted C6-C20 arylsilyl; or, R b and R c are linked to form a ring (e.g., a substituted or unsubstituted C3-C30 aliphatic ring, a substituted or unsubstituted C6-C60 aromatic ring, or a substituted or unsubstituted fused ring containing a C3-C30 aliphatic ring and a C6-C60 aromatic ring; wherein carbon atoms can be replaced with at least one heteroatom selected from N, O, S, Si, Se, and P).

[0091] R a , R b , R c are each independently selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C5-C20 heteroaryl, substituted or unsubstituted C3-C20 alkylsilyl, substituted or unsubstituted C6-C20 arylsilyl; or, R b and R c are linked to form a fluorene group.

[0092] In some embodiments, X is selected from CR b R c , O, or S; wherein,

[0093] R b , R c are each independently selected from substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C6-C10 aryl, substituted or unsubstituted C5-C10 heteroaryl; or, R b and R c are linked to form a fluorene group (e.g., ).

[0094] In some embodiments, Ar1and Ar2are each independently selected from substituted or unsubstituted C6-C30aryl, substituted or unsubstituted C3-C30heteroaryl.

[0095] In some embodiments, at least two of Z1, Z2, and Z3are N.

[0096] In some embodiments, L, L1, L2, and L3are each independently selected from a single bond, substituted or unsubstituted C6-C40arylene, substituted or unsubstituted C3-C40heteroarylene.

[0097] In some embodiments, L, L1, L2, and L3are each independently selected from a single bond, substituted or unsubstituted C6-C30arylene, substituted or unsubstituted C3-C30heteroarylene.

[0098] In some embodiments, L, L1, L2, and L3are each independently selected from a single bond or one of the structures represented by Formula (4-1) to Formula (4-17):

[0099]

[0100]

[0101] wherein “*” indicates the bonding position of L, L1, L2, and L3.

[0102] In some embodiments, Ar3to Ar5each independently represent hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30alkyl, substituted or unsubstituted C6-C30aryl, substituted or unsubstituted C3-C30heteroaryl, substituted or unsubstituted C3-C30cycloalkyl, substituted or unsubstituted C1-C20alkoxy, substituted or unsubstituted tri(C1-C20)alkylsilyl, substituted or unsubstituted di(C1-C20)alkyl(C6-C30)arylsilyl, substituted or unsubstituted (C1-C20)alkyl-di(C6-C30)arylsilyl, substituted or unsubstituted tri(C6-C20)arylsilyl, or -N-(R’)(R”); or Ar3to Ar5each independently form a ring with the substituents on the carbon atom or heteroatom adjacent thereto;

[0103] R’ and R” each independently represent substituted or unsubstituted C1-C20alkyl, substituted or unsubstituted C2-C20alkenyl, substituted or unsubstituted C6-C30aryl, or substituted or unsubstituted C3-C30heteroaryl.

[0104] In some embodiments, Ar3to Ar5each independently represent hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C20alkyl, substituted or unsubstituted C6-C20aryl, substituted or unsubstituted C3-C20heteroaryl, substituted or unsubstituted C3-C20cycloalkyl, substituted or unsubstituted C1-C10alkoxy, or -N-(R’)(R”); or Ar3to Ar5each independently and the substituents on the carbon atoms or heteroatoms adjacent to the substitution site thereof are linked to form a ring.

[0105] R’ and R” each independently represent substituted or unsubstituted C1-C10alkyl, substituted or unsubstituted C2-C10alkenyl, substituted or unsubstituted C6-C30aryl, substituted or unsubstituted C3-C30heteroaryl.

[0106] In some embodiments, the structure of formula (3) in the second host compound is selected from one of the following structures of formula (2-1) to formula (2-11):

[0107]

[0108] wherein R1, Ar6are defined as above.

[0109] In some embodiments, the Ar6is selected from substituted or unsubstituted C6-C30aryl, substituted or unsubstituted C3-C30heteroaryl.

[0110] In some embodiments, the Ar1to Ar6are each independently selected from at least one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted 9,9-spirobifluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted In some embodiments, the Ar1to Ar6are each independently selected from at least one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted 9,9-spirobifluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted

[0111] In some embodiments, the substituents are at least one of deuterium, halogen, cyano, isocyano, phosphino, C1-C6 alkyl, C3-C12 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 hydrocarbyl substituted or unsubstituted C6-C18 aryl, C1-C6 hydrocarbyl substituted or unsubstituted C3-C18 heteroaryl, wherein the number of substitutions ranges from mono-substitution to the maximum number of substitutions.

[0112] In some embodiments, the substituents are at least one of deuterium, halogen, cyano, isocyano, phosphino, C1-C6 alkyl, C3-C10 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 hydrocarbyl substituted or unsubstituted C6-C12 aryl, C1-C6 hydrocarbyl substituted or unsubstituted C3-C12 heteroaryl, wherein the number of substitutions ranges from mono-substitution to the maximum number of substitutions.

[0113] In some embodiments, the aryl group is selected from phenyl, naphthyl, anthryl, phenanthryl, tetracenyl, pyrenyl, perylenyl, In some embodiments, the aryl group is selected from phenyl, naphthyl, anthryl, phenanthryl, tetracenyl, pyrenyl, perylenyl,

[0114] In some embodiments, the heteroaryl group is selected from pyrrolyl, pyrrolopyrrolyl, furopyrrolyl, thienopyrrolyl, pyridyl, pyrazolyl, pyrimidinyl, pyrazinyl, pyridazinyl, phenoxazinyl, phenothiazinyl, phenoxazinyl, indolyl, isoindolyl, imidazolyl, benzimidazolyl, triazolyl, tetrazolyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, furopyranyl, azadibenzofuranyl, thienofuranyl, diazadibenzofuranyl, benzo[B]naphtho[1,2-D]furanyl, quinolyl, isoquinolyl, quinoxalyl, quinazolinyl, quinazolinonyl, carbazolyl, azacarbazolyl, diazacarbazolyl, phenanthridinyl, perimidinyl, acridinyl, dihydroacridinyl, phenanthrolinyl, oxazolinyl, oxazolyl, oxadiazolyl, benzisoxazolyl, thiazolyl, benzothiazolyl, benzisothiazolyl, pyrroloimidazolyl, furazanyl, thienyl, benzothienyl, dibenzothienyl, azadibenzothienyl, diazadibenzothienyl, thienothienyl, or phthalazinyl.

[0115] In some embodiments, X in the first host compound of formula (1) is selected from O, and Z1, Z2, Z3 in the second host compound of formula (2) are all N.

[0116] In some embodiments, wherein the compound represented by formula (1) is selected from one of the following structural formulae, or one of the following structural formulae in which the hydrogens are partially or completely replaced by deuterium, fluorine:

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136] In some embodiments, wherein the compound represented by formula (2) is selected from one of the following structural formulae, or one of the following structural formulae in which the hydrogen is partially or completely replaced by deuterium, a fluorine:

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144] In some embodiments, the host material comprises a first host compound and a second host compound, and the weight ratio of the first host compound to the second host compound can be in the range of 1 :99 to 99: 1, preferably 10:90 to 90: 10, more preferably selected from 20:80 to 80:20, 30:70 to 70:30, or 40:60 to 60:40, even more preferably 50:50.

[0145] In some embodiments, wherein the host material further comprises at least one third host compound, the third host compound is represented by the formula (1) or formula (2), but is different from the first host compound or the second host compound.

[0146] In some embodiments, the first host compound is represented by formula (1), the second host compound and the third host compound are both represented by formula (2), the second host compound is selected from one of the structures represented by B1-B106, and the third host compound is selected from one of the structures represented by C1-C40.

[0147] In some embodiments, the host material composition comprises a first host compound, a second host compound, and a third host compound, the third host compound being different from the first host compound and the second host compound. The weight ratio of the first host compound in the host material composition is about 5 wt% to about 90 wt%, preferably selected from 10 wt% to 90 wt%, 10 wt% to 80 wt%, 20 wt% to 80 wt%, 15 wt% to 70 wt%, 30 wt% to 70 wt%, 20 wt% to 60 wt%, or 30 wt% to 60 wt%; the weight ratio of the second host compound is about 5 wt% to about 90 wt%, preferably selected from 10 wt% to 90 wt%, 10 wt% to 80 wt%, 10 wt% to 40 wt%, 15 wt% to 70 wt%, 30 wt% to 70 wt%, 20 wt% to 60 wt%, or 30 wt% to 60 wt%; and the weight ratio of the third host compound is about 5 wt% to about 90 wt%, preferably selected from 10 wt% to 90 wt%, 10 wt% to 80 wt%, 10 wt% to 40 wt%, 15 wt% to 70 wt%, 30 wt% to 70 wt%, 20 wt% to 60 wt%, or 30 wt% to 60 wt%. For example, the host material composition can comprise a first host compound in a weight ratio of 5 wt% to 70 wt%, a second host compound in a weight ratio of 5 wt% to 70 wt%, and a third host compound in a weight ratio of 10 wt% to 90 wt%. The host material composition can also comprise a first host compound in a weight ratio of 20 wt% to 80 wt%, a second host compound in a weight ratio of 10 wt% to 40 wt%, and a third host compound in a weight ratio of 10 wt% to 40 wt%.

[0148] The second aspect of the present application provides an organic electroluminescent device.

[0149] Specifically, the organic electroluminescent device comprises the above-mentioned plurality of host materials.

[0150] In some embodiments, the organic electroluminescent device comprises: an anode, a cathode, and at least one light-emitting layer between the anode and the cathode, wherein the light-emitting layer comprises the above-mentioned plurality of host materials.

[0151] In an embodiment, the light-emitting layer is a red light-emitting layer comprising a red light-emitting material and the above-mentioned plurality of host materials. In this embodiment, the plurality of host materials of the present application serve as host materials for the red light-emitting layer.

[0152] The third aspect of the present application provides the use of the above-mentioned compound in the field of semiconductors.

[0153] Specifically, the above-mentioned plurality of host materials are used in the preparation of a semiconductor device.

[0154] In some embodiments, the semiconductor device comprises an optoelectronic device.

[0155] The beneficial effects of the present application relative to the prior art are as follows:

[0156] The various host materials of the present application have the advantages of low sublimation temperature, low driving voltage, high luminous efficiency, long device lifetime, etc., and can be used as host materials in OLED light-emitting devices. At the same time, they have a relatively low melting point, which is beneficial to the stability of material evaporation as a melt type material. The various host materials as red light host materials have the possibility of application in the AMOLED industry.

[0157] Hereinafter, examples of each group of the compounds represented by formula (1) to formula (4) will be described. In addition, many terms will be mentioned in the present specification and claims, and these terms shall have the following definitions:

[0158] The "carbon number a~b" in the expression "substituted or unsubstituted X group having a carbon number of a~b" refers to the carbon number of the X group in the unsubstituted case, excluding the carbon number of the substituent when the X group is substituted.

[0159] The term "plurality" means a number greater than or equal to 2, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.

[0160] The term "alkyl" refers to a straight chain or branched chain saturated hydrocarbon group. Non-limiting examples of alkyl groups include methyl, ethyl, propyl, butyl, heptyl, decyl, etc. Each group includes various isomers, such as butyl which includes n-butyl, isobutyl, sec-butyl, t-butyl, and the like. In some embodiments, the alkyl group can be a C1-C60(e.g., C1-C30, C1-C20, C1-C12, C1-C10, C1-C6, C1-C3) alkyl group.

[0161] The term "heteroalkyl" refers to at least one carbon atom in an alkyl group being replaced by a non-carbon atom or a group containing a non-carbon atom, which can be selected from at least one of O, S, N, P, B, Si, or Se, but excluding the case where the carbon atom connected to the main structure in the alkyl group is replaced by a non-carbon atom. In some embodiments, the heteroalkyl group is a C1-C60(e.g., C1-C40, C1-C30, C1-C20, C1-C12, C1-C10, C1-C3) heteroalkyl group. Non-limiting examples of heteroalkyl groups include mercaptomethane group, methoxymethane group, ethoxymethane group, t-butoxymethane group, N,N-dimethylmethane group.

[0162] The term "alkenyl" refers to a hydrocarbyl group comprising at least one unsaturated double bond. Non-limiting examples of alkenyl groups include: ethenyl, propenyl, allyl, isopropenyl. In some embodiments, an alkenyl group can be a C2-C40(e.g., C2-C30, C2-C20, C2-C12, C2-C10, C2-C6, C2-C4) alkenyl group.

[0163] The term "alkynyl" refers to a hydrocarbyl group comprising at least one unsaturated triple bond. Non-limiting examples of alkynyl groups include: ethynyl and propargyl. In some embodiments, an alkynyl group can be a C2-C40(e.g., C2-C30, C2-C20, C2-C12, C2-C10, C2-C6, C2-C4) alkynyl group.

[0164] The term "cycloalkyl" refers to a non-aromatic carbon-based ring consisting of at least 3 carbon atoms, which can include monocyclic, polycyclic, and spiroalkyl groups. Non-limiting examples of cycloalkyl groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, norbornyl. In some embodiments, a cycloalkyl group can be, for example, a C3-C60cycloalkyl group (a cycloalkyl group comprising 3 to 60 carbon atoms), such as a C3-C40, C3-C3, C3-C20, C3-C18, C3-C16, C3-C14, C3-C12, C3-C10, C3-C8, or C3-C6cycloalkyl group.

[0165] The term "heterocycloalkyl" refers to at least one carbon atom of a cycloalkyl group being replaced by a non-carbon atom, which can be selected from O, S, N, P, B, Si, Se, Ge. In some embodiments, a heterocycloalkyl group refers to a C3-C60heterocycloalkyl group, such as, for example, a C3-C40, C3-C30, C3-C20, C3-C18, C3-C16, C3-C14, C3-C12, C3-C10, C3-C8, C4-C7heterocycloalkyl group.

[0166] The term "aryl" refers to an aromatic hydrocarbon group derived from a parent aromatic ring compound by removal of one hydrogen atom, and can be a monocyclic aryl group, or a polycyclic aryl group. At least one ring in a polycyclic aryl group is an aromatic ring system. Multiple rings in a polycyclic aryl group can be joined via single bonds or can be fused together. In some embodiments, aryl groups can be, for example, C6-C60 aryl groups (aryl groups comprising 6 to 60 carbon atoms), C6-C50 aryl groups, C6-C40 aryl groups, C6-C30 aryl groups, C6-C20 aryl groups, C6-C12 aryl groups, or C6-C10 aryl groups. When a polycyclic aryl group contains a fused ring structure, it can be formed from a combination of aliphatic (saturated or unsaturated aliphatic) and aromatic rings. For example, from a fused ring group of at least one aliphatic ring having 3 to 30 ring skeleton carbon atoms (e.g., 3 to 25, 3 to 18, 3 to 15, 3 to 12, 3 to 9, or 3 to 7 ring skeleton carbon atoms) and at least one aromatic ring having 6 to 30 ring skeleton carbon atoms (e.g., 6 to 25, 6 to 18, 6 to 12, or 6 to 10 ring skeleton carbon atoms). Understandably, the term "arylene" refers to a divalent group derived from an aromatic ring compound by removal of two hydrogen atoms.

[0167] The term "heteroaryl" refers to a monovalent radical of a heterocyclic aromatic system in which at least one carbon atom is replaced by a non-carbon atom, which can be selected from O, S, N, Se, Si, or Ge, based on aryl. In some embodiments, a heteroaryl group can be a C3-C60 (e.g., C3-C50, C3-C40, C3-C30, C3-C20, C3-C12, C3-C10) heteroaryl group containing one or more (e.g., two or three) heteroatoms independently selected from O, S, N, Se. Understandably, the term "heteroarylene" refers to a divalent group having the same structure as a heteroaryl group.

[0168] The term "substituted or unsubstituted" in the term "substituted" means that one or more hydrogen atoms are replaced by another atom or functional group (i.e., a substituent), which also includes one or more hydrogen atoms being replaced by a group formed by the linking of two or more of the above-mentioned substituents, unless otherwise limited by definition.

[0169] The following examples are merely for the purpose of facilitating the understanding of the technical invention, and should not be regarded as specific limitations of the present application.

[0170] The raw materials and solvents involved in the synthesis of the compounds in the present application are purchased from suppliers well known to those skilled in the art, such as Alfa, Acros, etc.

[0171] Synthesis of Compound A1

[0172]

[0173] Synthesis of Compound A1-3

[0174] A1-1 (30.00 g, 106.56 mmol), A1-2 (32.47 g, 127.87 mmol), Pd(dppf)Cl2(1.56 g, 2.13 mmol), KOAc (15.69 g, 159.84 mmol), 1,4-Dioxane (450 ml) were added into a 1000 ml three-necked round-bottom flask, replaced with nitrogen three times, then the system was heated to 100°C for 2 hours, and the reaction was monitored by TLC (ethyl acetate: n-hexane = 1:10 as developing agent), and A1-1 was consumed.

[0175] The temperature was lowered to 60°C, the solvent was removed by concentration under reduced pressure, ethyl acetate (700 ml) was added, washed with deionized water three times (300 ml*3), separated, and the silica gel was mixed and dried for column chromatography. Silica gel column chromatography purification (200-300 mesh silica gel, ethyl acetate: n-hexane = 1:15 as eluent) was performed, and after elution, white solid A1-3 (27.62 g, purity: 98.01%, yield: 78.88%) was obtained by concentration under reduced pressure at 70°C for 1 hour.

[0176] Synthesis of compound A1-5

[0177] A1-3 (25.00 g, 76.08 mmol), A1-4 (17.89 g, 76.08 mmol), Pd(PPh3)4(1.75 g, 1.52 mmol), K2CO3(15.77 g, 114.12 mmol), THF (375 ml), deionized water (125 ml) were added into a 1000 ml three-necked round-bottom flask, replaced with nitrogen three times, then the system was heated to 75°C for 3 hours, and the reaction was monitored by TLC (ethyl acetate: n-hexane = 1:10 as developing agent), and A1-3 was consumed.

[0178] The temperature was lowered to 60°C, the solvent was removed by concentration under reduced pressure, ethyl acetate (700 ml) was added, washed with deionized water three times (300 ml*3), separated, and the silica gel was mixed and dried for column chromatography. Silica gel column chromatography purification (200-300 mesh silica gel, ethyl acetate: n-hexane = 1:20 as eluent) was performed, and after elution, white solid A1-5 (20.45 g, purity: 99.21%, yield: 75.32%) was obtained by concentration under reduced pressure at 70°C for 2 hours.

[0179] Synthesis of compound A1-7

[0180] A1-5 (18.00 g, 50.45 mmol), A1-6 (25.94 g, 75.67 mmol), tetrahydrofuran (270 ml) were added into a 1000 ml three-necked round-bottom flask, and the system was replaced with nitrogen three times under vacuum, then the system was cooled to 5°C, sodium methoxide (NaOMe, 5.45 g, 100.90 mmol) was added at one time, and the reaction was maintained at 5°C for 1 hour. TLC (ethyl acetate: n-hexane = 1:10 as developing agent) was used to monitor the reaction, and the consumption of the starting material A1-5 was complete.

[0181] Deionized water (500 ml) was added, and the solvent was removed by concentration under reduced pressure. Ethyl acetate (700 ml) was added for extraction, and the mixture was separated. The white solid A1-7 (18.44 g, yield: 95.00%) was obtained by concentration under reduced pressure at 70°C for 1 hour. Mass spectrum: 385.04 (M+H). The obtained compound was used directly in the next step without purification.

[0182] Synthesis of compound A1-8

[0183] A1-7 (17.00 g, 44.17 mmol), toluene (170 ml) were added into a 500 ml three-necked round-bottom flask, and the system was replaced with nitrogen three times under vacuum, then the system was cooled to 5°C, and methyl sulfonic acid (MsOH, 8.49 g, 88.34 mmol) was slowly added dropwise. The dropwise addition was completed in 3 minutes, and the reaction was maintained at 5°C for 1 hour. TLC (ethyl acetate: n-hexane = 1:15 as developing agent) was used to monitor the reaction, and the consumption of the starting material A1-7 was complete.

[0184] Methanol (200 ml) was added, and a large amount of white solid was precipitated. Filtration under suction gave 17 g of solid. The solid was crystallized once with toluene (204 ml) and methanol (170 ml), and then filtered under suction. The filter cake was dried under vacuum at 80°C for 1 hour to give white solid A1-8 (11.63 g, purity: 99.83%, yield: 74.62%). Mass spectrum: 353.06 (M+H).

[0185] Synthesis of compound A1

[0186] A1-8 (10.00 g, 28.34 mmol), A1-9 (7.30 g, 29.76 mmol), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3, 0.52 g, 0.57 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (X-Phos, 0.54 g, 1.14 mmol), sodium tert-butoxide (NaOtBu, 4.09 g, 42.51 mmol), toluene (150 ml) were charged into a 500 ml three-necked round-bottomed flask, purged with vacuum-nitrogen three times, then the system was heated to 105 °C for 2 hours, TLC (ethyl acetate: n-hexane = 1:15 as developing agent) was used to monitor the reaction, and the starting material A1-8 was consumed.

[0187] The temperature was lowered to 60 °C, methanol (150 ml) was added, and the system was stirred at room temperature for 30 minutes to precipitate a large amount of solid. Filtration under suction gave 20 g of solid. Toluene (300 ml) was added, and then the system was heated to 100 °C to dissolve and clarify. After filtration, the surface of the silica gel was rinsed with toluene (50 ml), and the filtrate was combined and concentrated to give 18 g. Crystallization was performed twice using toluene (180 ml) and methanol (90 ml). Filtration under suction was performed, and the filter cake was dried at 90 °C under vacuum for 3 hours to give A1 (14.07 g, purity: 99.94%, yield: 88.41%) as a light yellow solid. Sublimation purification of 14.07 g of the crude A1 gave sublimed A1 (11.26 g, purity: 99.95%, yield: 80.02%) as a light yellow solid. Mass: 562.22 (M+H).

[0188] 1 H NMR (400 MHz, CDCl3) δ 8.17 (d, J = 9.1 Hz, 1H), 8.07-8.00 (m, 1H), 7.97-7.87 (m, 4H), 7.85 (dd, J = 7.5, 3.0 Hz, 2H), 7.60-7.55 (m, 2H), 7.55-7.48 (m, 4H), 7.42-7.39 (m, 3H), 7.32 (d, J = 7.3 Hz, 1H), 7.31-7.24 (m, 2H), 7.16-7.07 (m, 5H), 7.02-6.97 (m, 2H).

[0189] Synthesis of compound A54

[0190]

[0191] Synthesis of compound A54-2

[0192] The synthesis and purification method of compound A1-3 was referred to, only the corresponding raw material was changed, to obtain the target compound A54-2 (28.02 g, purity: 98.52%, yield: 77.65%) as a white solid, mass spectrum: 329.12 (M+H).

[0193] Synthesis of compound A54-3

[0194] The synthesis and purification method of compound A1-5 was referred to, only the corresponding raw material was changed, to obtain the target compound A54-3 (26.33 g, purity: 99.45%, yield: 75.09%) as a white solid, mass spectrum: 357.22 (M+H).

[0195] Synthesis of compound A54-4

[0196] The synthesis and purification method of compound A1-7 was referred to, only the corresponding raw material was changed, to obtain the target compound A54-4 (24.44 g, yield: 97.89%) as a white solid, mass spectrum: 385.04 (M+H). The obtained compound was directly used in the next step without purification.

[0197] Synthesis of compound A54-5

[0198] The synthesis and purification method of compound A1-8 was referred to, only the corresponding raw material was changed, to obtain the target compound A54-5 (16.85 g, purity: 99.79%, yield: 76.85%) as a white solid, mass spectrum: 353.06 (M+H).

[0199] Synthesis of compound A54

[0200] The synthesis and purification method of compound A1 was referred to, only the corresponding raw material was changed, to obtain the target compound A54 (16.74 g, purity: 99.95%, yield: 78.65%) as a light yellow solid. After sublimation purification of 16.74 g of A54 crude product, sublimation pure A54 (13.10 g, purity: 99.95%, yield: 78.26%) was obtained, mass spectrum: 612.22 (M+H).

[0201] 1H NMR (400 MHz, CDC13) δ 8.64 (s, 1H), 8.33 - 8.26 (m, 1H), 8.01 (d, J = 8.9 Hz, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.93 - 7.75 (m, 8H), 7.61 - 7.53 (m, 3H), 7.53 - 7.47 (m, 5H), 7.44 - 7.37 (m, 3H), 7.22 (t, J = 2.2 Hz, 1H), 7.09 - 7.01 (m, 2H), 7.01 - 6.97 (m, 2H), 6.86 (dd, J = 7.6, 2.2 Hz, 1H).

[0202] Synthesis of compound A73

[0203]

[0204] Synthesis of compound A73-2

[0205] Referring to the synthesis and purification method of compound A1-3, only the corresponding starting materials need to be changed to obtain the target compound A73-2 (30.54 g, purity: 98.44%, yield: 77.12%) as a white solid, mass spectrum: 329.12 (M+H).

[0206] Synthesis of compound A73-3

[0207] Referring to the synthesis and purification method of compound A1-5, only the corresponding starting materials need to be changed to obtain the target compound A73-3 (27.09 g, purity: 99.66%, yield: 76.36%) as a white solid, mass spectrum: 357.22 (M+H).

[0208] Synthesis of compound A73-4

[0209] Referring to the synthesis and purification method of compound A1-7, only the corresponding starting materials need to be changed to obtain the target compound A73-4 (23.12 g, yield: 93.93%) as a white solid, mass spectrum: 385.04 (M+H). The obtained compound is directly used in the next step without purification.

[0210] Synthesis of compound A73-5

[0211] Referring to the synthesis and purification method of compound A1-8, only the corresponding starting materials need to be changed to obtain the target compound A73-5 (18.08 g, purity: 99.65%, yield: 40.20%) as a white solid, mass spectrum: 353.06 (M+H).

[0212] Synthesis of compound A73-8

[0213] The synthesis and purification method of Compound A1 were referred to, only the corresponding raw materials were changed, to obtain the target compound A73-8 (23.11 g, purity: 99.60%, yield: 76.44%) as a white solid, mass spectrum: 337.13 (M+H).

[0214] Synthesis of compound A73

[0215] The synthesis and purification method of Compound A1 were referred to, only the corresponding raw materials were changed, to obtain the target compound A73 (16.76 g, purity: 99.92%, yield: 76.22%) as a light yellow solid. After sublimation purification of 16.76 g of A73 crude product, sublimation pure A73 (14.21 g, purity: 99.92%, yield: 84.78%) was obtained, mass spectrum: 653.21 (M+H).

[0216] 1 H NMR (400 MHz, CDCI3) δ 8.33-8.26 (m, 1H), 8.21 (dd, J = 17.5, 8.8 Hz, 2H), 8.13-8.03 (m, 2H), 8.02-7.79 (m, 10H), 7.55-7.46 (m, 3H), 7.46-7.39 (m, 3H), 7.34-7.24 (m, 3H), 7.15-7.06 (m, 3H), 6.98-6.96 (m, 1H).

[0217] Synthesis of compound A89

[0218]

[0219] Synthesis of compound A89-3

[0220] The synthesis and purification method of Compound A1-5 were referred to, only the corresponding raw materials were changed, to obtain the target compound A89-3 (19.88 g, purity: 99.57%, yield: 78.08%) as a white solid, mass spectrum: 357.04 (M+H).

[0221] Synthesis of compound A89-4

[0222] The synthesis and purification method of Compound A1-7 were referred to, only the corresponding raw materials were changed, to obtain the target compound A89-4 (25.58 g, yield: 94.35%) as a white solid, mass spectrum: 385.04 (M+H). The obtained compound was directly used in the next step without purification.

[0223] Synthesis of compound A89-5

[0224] The synthesis and purification method of Compound A1-8 were referred to, only the corresponding raw materials were changed, and the target compound A89-5 was obtained as a white solid (20.01 g, purity: 99.74%, yield: 78.63%). Mass spectrum: 353.06 (M+H).

[0225] Synthesis of compound A89

[0226] The synthesis and purification method of Compound A1 were referred to, only the corresponding raw materials were changed, and the target compound A89 was obtained as a yellow solid (17.77 g, purity: 99.94%, yield: 71.06%). After sublimation purification of 17.77 g of A89 crude product, sublimed A89 (15.02 g, purity: 99.94%, yield: 84.52%) was obtained. Mass spectrum: 678.22 (M+H).

[0227] 1 H NMR (400 MHz, CDCl3) δ 8.47 (dd, J = 7.6, 1.4 Hz, 1H), 8.16-8.10 (m, 1H), 8.10-8.02 (m, 4H), 7.93-7.86 (m, 3H), 7.82 (d, J = 7.1 Hz, 1H), 7.61-7.34 (m, 15H), 7.32-7.30 (m, 1H), 7.17 (dd, J = 7.2, 2.1 Hz, 1H), 7.03-6.97 (m, 2H), 1.74 (s, 6H).

[0228] Synthesis of compound A97

[0229]

[0230] Synthesis of compound A97-2

[0231] The synthesis and purification method of Compound A1-3 were referred to, only the corresponding raw materials were changed, and the target compound A97-2 was obtained as a white solid (32.65 g, purity: 98.78%, yield: 79.05%). Mass spectrum: 345.02 (M+H).

[0232] Synthesis of compound A97-3

[0233] The synthesis and purification method of Compound A1-5 were referred to, only the corresponding raw materials were changed, and the target compound A97-3 was obtained as a white solid (29.63 g, purity: 99.75%, yield: 76.03%). Mass spectrum: 373.04 (M+H).

[0234] Synthesis of compound A97-4

[0235] The synthesis and purification method of compound A1-7 were referred to, only the corresponding raw materials were changed, and the target compound A97-4 was obtained as a white solid (25.63 g, yield: 95.39%), mass spectrum: 401.14 (M+H). The obtained compound was directly used in the next step without purification.

[0236] Synthesis of compound A97-5

[0237] The synthesis and purification method of compound A1-8 were referred to, only the corresponding raw materials were changed, and the target compound A97-5 was obtained as a white solid (20.00 g, purity: 99.76%, yield: 78.80%), mass spectrum: 369.02 (M+H).

[0238] Synthesis of compound A97

[0239] The synthesis and purification method of compound A1 were referred to, only the corresponding raw materials were changed, and the target compound A97 was obtained as a light yellow solid (14.33 g, purity: 99.95%, yield: 74.63%). After sublimation purification of 14.33 g of A97 crude product, sublimed A97 was obtained (12.01 g, purity: 99.95%, yield: 83.81), mass spectrum: 731.93 (M+H).

[0240] 1 H NMR (400 MHz, CDCl3) δ 8.21 (d, J = 7.1 Hz, 1H), 8.11-8.02 (m, 2H), 8.02-7.97 (m, 1H), 7.96-7.87 (m, 4H), 7.85 (d, J = 8.1 Hz, 1H), 7.75-7.68 (m, 2H), 7.61-7.54 (m, 4H), 7.54-7.47 (m, 8H), 7.42-7.39 (m, 6H), 7.16 (dd, J = 7.0, 2.2 Hz, 1H), 7.04-6.97 (m, 2H), 6.97-6.87 (m, 2H).

[0241] Synthesis of compound A118

[0242]

[0243] Synthesis of compound A118-1

[0244] The synthesis and purification method of compound A1 were referred to, only the corresponding raw materials were changed, and the target compound A118-1 was obtained as a light yellow solid (12.11 g, purity: 99.95%, yield: 76.87%), mass spectrum: 562.32 (M+H).

[0245] 1H NMR (400 MHz, CDC13) δ 8.33 - 8.26 (m, 1H), 8.21 (dd, J = 17.5, 8.8 Hz, 2H), 8.13 - 8.08 (m, 1H), 8.06 (d, J = 9.5 Hz, 1H), 8.00 - 7.94 (m, 2H), 7.93 - 7.82 (m, 2H), 7.61 - 7.47 (m, 6H), 7.46 - 7.37 (m, 4H), 7.34 - 7.25 (m, 3H), 7.17 - 7.06 (m, 3H), 7.03 - 6.97 (m, 2H).

[0246] Synthesis of compound A118

[0247] A118-1 (30.00 g, 54.31 mmol), deuterated benzene-D6 (114.44 g, 1.36 mol), trifluoroacetic acid (6.19 g, 54.31 mmol) were added into a 500 ml single necked round bottom flask, replaced with vacuum nitrogen for three times, then the system was heated to 50 °C and stirred for 24 hours.

[0248] The system was cooled to room temperature, and heavy water (40 ml) was added dropwise to quench the reaction, stirred at room temperature for 0.5 hours, then ethyl acetate (300 ml) and deionized water (200 ml) were added and washed three times, and then the system was stirred at room temperature for 30 minutes, and filtered to obtain 35 g of solid, which was dried at 90 °C under vacuum for 1 hour to obtain 29 g of light yellow solid, which was crystallized twice with toluene (290 ml) and methanol (120 ml), filtered, and the filter cake was dried at 90 °C under vacuum for 3 hours to obtain light yellow solid as A118 (25.20 g, purity: 99.94%, yield: 80.12%). After sublimation purification of 25.20 g of crude A118, sublimed A118 (21.53 g, purity: 99.95%, deuterium substitution rate of 27 D: 95.33%, yield: 85.46%) was obtained, mass spectrum: 589.22 (M+H).

[0249] Synthesis of compound A136

[0250]

[0251] Synthesis of compound A136-2

[0252] Referring to the synthesis and purification method of compound A1-5, only the corresponding starting materials need to be changed, and the target compound A136-2 (22.65 g, purity: 99.52%, yield: 75.98%) is obtained as a white solid, mass spectrum: 382.12 (M+H).

[0253] Synthesis of compound A136-3

[0254] The synthesis and purification method of compound A1-7 were referred to, only the corresponding raw materials were changed, and the target compound A136-3 was obtained as a white solid (20.00 g, yield: 96.08%), mass spectrum: 410.10 (M+H). The obtained compound was directly used in the next step without purification.

[0255] Synthesis of compound A136-4

[0256] The synthesis and purification method of compound A1-8 were referred to, only the corresponding raw materials were changed, and the target compound A136-4 was obtained as a white solid (16.78 g, purity: 99.78%, yield: 42.56%), mass spectrum: 378.26 (M+H).

[0257] Synthesis of compound A136

[0258] The synthesis and purification method of compound A1 were referred to, only the corresponding raw materials were changed, and the target compound A136 was obtained as a light yellow solid (15.33 g, purity: 99.92%, yield: 77.52%). After sublimation purification of 15.33 g of A136 crude, sublimed A136 was obtained (12.01 g, purity: 99.93%, yield: 78.35%), mass spectrum: 601.18 (M+H).

[0259] 1 H NMR (400 MHz, CDCl3) δ 8.44 (d, J = 2.0 Hz, 1H), 8.37 (d, J = 8.1 Hz, 1H), 8.28-8.22 (m, 1H), 8.13 (d, J = 7.5 Hz, 1H), 8.10-8.05 (m, 1H), 8.04-7.92 (m, 3H), 7.90 (d, J = 7.5 Hz, 1H), 7.82 (d, J = 7.2 Hz, 1H), 7.70-7.59 (m, 2H), 7.47-7.34 (m, 3H), 7.32-7.24 (m, 2H), 7.17 (dd, J = 7.3, 2.0 Hz, 1H), 7.15-7.08 (m, 4H), 7.07 (d, J = 2.1 Hz, 1H), 7.04-7.02 (m, 1H).

[0260] Synthesis of compound A145

[0261]

[0262] Synthesis of compound A145-1

[0263] The synthesis and purification of the reference compound A1-8 were repeated, except that the corresponding starting materials were changed, to obtain the target compound A145-1 (20.52 g, purity: 99.63%, yield: 75.82%) as a white solid.

[0264] Synthesis of compound A145-3

[0265] The synthesis and purification of the reference compound A1 were repeated, except that the corresponding starting materials were changed, to obtain the target compound A145-3 (25.63 g, purity: 99.87%, yield: 74.25%) as a white solid. Mass: 320.12 (M+H).

[0266] Synthesis of compound A145

[0267] The synthesis and purification of the reference compound A1 were repeated, except that the corresponding starting materials were changed, to obtain the target compound A145 (17.63 g, purity: 99.94%, yield: 77.06%) as a yellow solid. After sublimation purification of 17.63 g of the crude A145, sublimed A145 (14.76 g, purity: 99.94%, yield: 83.72%) was obtained. Mass: 636.22 (M+H).

[0268] 1 H NMR (400 MHz, CDCl3) δ 8.62 (d, J = 9.2 Hz, 1H), 8.57 (d, J = 9.3 Hz, 1H), 8.50-8.43 (m, 1H), 8.37 (d, J = 8.3 Hz, 1H), 8.33-8.27 (m, 1H), 8.25 (d, J = 8.1 Hz, 1H), 8.01-7.95 (m, 3H), 7.92-7.87 (m, 5H), 7.82 (d, J = 7.2 Hz, 1H), 7.73 (d, J = 2.0 Hz, 1H), 7.56-7.47 (m, 4H), 7.37 (d, J = 7.1 Hz, 1H), 7.32-7.24 (m, 2H), 7.17-7.06 (m, 5H), 6.89 (dd, J = 7.5, 2.2 Hz, 1H).

[0269] Synthesis of compound A167

[0270]

[0271] Synthesis of compound A167-1

[0272] The synthesis and purification of the reference compound A1-8 were repeated, except that the corresponding starting materials were changed, to obtain the target compound A167-1 (15.63 g, purity: 99.71%, yield: 42.52%) as a white solid.

[0273] Synthesis of compound A167-4

[0274] The synthesis and purification of the reference compound A1 were repeated, except that the corresponding starting materials were changed, to obtain the target compound A167 (20.62 g, purity: 99.75%, yield: 78.43%) as a white solid. Mass: 410.20 (M+H).

[0275] Synthesis of compound A167

[0276] The synthesis and purification of the reference compound A1 were repeated, except that the corresponding starting materials were changed, to obtain the target compound A167 (14.52 g, purity: 99.93%, yield: 74.62%) as a light yellow solid. After sublimation purification of 14.52 g of the crude A167, sublimed A167 (11.11 g, purity: 99.93%, yield: 76.52%) was obtained. Mass: 726.28 (M+H).

[0277] 1 H NMR (400 MHz, CDCl3) δ 8.33 - 8.27 (m, 1H), 8.25 - 8.18 (m, 2H), 8.15 (dd, J = 8.9, 2.4 Hz, 1H), 8.02 (s, 1H), 8.00 (d, J = 2.2 Hz, 1H), 7.98 - 7.86 (m, 6H), 7.85 (d, J = 2.0 Hz, 1H), 7.55 - 7.48 (m, 5H), 7.42 (d, J = 7.6 Hz, 1H), 7.31 (dd, J = 7.5, 2.2 Hz, 1H), 7.07 - 7.01 (m, 2H), 6.89 - 6.84 (m, 2H), 2.16 - 2.09 (m, 3H), 1.96 (d, J = 4.9 Hz, 6H), 1.79 (t, J = 5.5 Hz, 6H).

[0278] Synthesis of compound A183

[0279]

[0280] Synthesis of compound A183-2

[0281] The synthesis and purification method of the reference compound A1-3 was referred to, only the corresponding raw material was changed, to obtain the target compound A183-2 (28.74 g, purity: 99.21%, yield: 74.56%) as a white solid, mass spectrum: 329.12 (M+H).

[0282] Synthesis of compound A183-3

[0283] The synthesis and purification method of the reference compound A1-5 was referred to, only the corresponding raw material was changed, to obtain the target compound A183-3 (26.32 g, purity: 99.66%, yield: 76.36%) as a white solid, mass spectrum: 357.22 (M+H).

[0284] Synthesis of compound A183-4

[0285] The synthesis and purification method of the reference compound A1-7 was referred to, only the corresponding raw material was changed, to obtain the target compound A183-4 (21.65 g, yield: 92.84%) as a white solid, mass spectrum: 385.04 (M+H). The obtained compound was directly used in the next step without purification.

[0286] Synthesis of compound A183-5

[0287] The synthesis and purification method of the reference compound A1-8 was referred to, only the corresponding raw material was changed, to obtain the target compound A183-5 (18.65 g, purity: 99.73%, yield: 76.85%) as a white solid, mass spectrum: 353.06 (M+H).

[0288] Synthesis of compound A183-7

[0289] The synthesis and purification method of the reference compound A1 was referred to, only the corresponding raw material was changed, to obtain the target compound A183-7 (19.99 g, purity: 99.87%, yield: 78.63%) as a white solid, mass spectrum: 310.22 (M+H).

[0290] Synthesis of compound A183

[0291] The synthesis and purification method of the reference compound A1 was referred to, only the corresponding raw material was changed, to obtain the target compound A183 (14.65 g, purity: 99.96%, yield: 77.14%) as a light yellow solid. After sublimation purification of 14.65 g of the crude A183, sublimed A183 (11.24 g, purity: 99.96%, yield: 76.73%) was obtained, mass spectrum: 626.24 (M+H).

[0292] 1H NMR (400 MHz, CDC13) δ 8.36 - 8.28 (m, 2H), 8.05 - 7.98 (m, 3H), 7.97 - 7.87 (m, 5H), 7.85 (d, J = 8.0 Hz, 1H), 7.74 - 7.68 (m, 1H), 7.57 - 7.47 (m, 5H), 7.42 - 7.41 (m, 1H), 7.37 - 7.23 (m, 5H), 7.20 - 7.06 (m, 4H).

[0293] Synthesis of compound A207

[0294]

[0295] Synthesis of compound A207-2

[0296] Referring to the synthesis and purification method of compound A1-5, only the corresponding starting materials need to be changed to obtain the target compound A207-2 (28.78 g, purity: 99.74%, yield: 76.11%) as a white solid, mass spectrum: 357.24 (M+H).

[0297] Synthesis of compound A207-3

[0298] Referring to the synthesis and purification method of compound A1-7, only the corresponding starting materials need to be changed to obtain the target compound A207-3 (22.65 g, yield: 95.63%) as a white solid, mass spectrum: 385.04 (M+H). The obtained compound is directly used in the next step without purification.

[0299] Synthesis of compound A207-4

[0300] Referring to the synthesis and purification method of compound A1-8, only the corresponding starting materials need to be changed to obtain the target compound A207-4 (18.08 g, purity: 99.65%, yield: 41.20%) as a white solid, mass spectrum: 353.06 (M+H).

[0301] Synthesis of compound A207-5

[0302] Referring to the synthesis and purification method of compound A1-3, only the corresponding starting materials need to be changed to obtain the target compound A207-5 (20.63 g, purity: 99.00%, yield: 75.41%) as a white solid, mass spectrum: 445.20 (M+H).

[0303] Synthesis of compound A207

[0304] The synthesis and purification method of reference compound A1-5 was referred to, only the corresponding raw materials were changed, and the target compound A207 was obtained as a light yellow solid (15.12 g, purity: 99.94%, yield: 75.85%). After sublimation purification of 15.12 g of A207 crude product, sublimed A207 (12.02 g, purity: 99.94%, yield: 79.50%) was obtained, mass spectrum: 638.24 (M+H).

[0305] 1 H NMR (400 MHz, CDCl3) δ 8.64 (d, J = 9.3 Hz, 1H), 8.46-8.40 (m, 1H), 8.38 (d, J = 9.6 Hz, 1H), 8.21 (d, J = 1.1 Hz, 2H), 8.04 (d, J = 9.5 Hz, 1H), 8.01-7.93 (m, 2H), 7.92-7.86 (m, 1H), 7.78 (dd, J = 7.1, 2.4 Hz, 1H), 7.63-7.55 (m, 2H), 7.55-7.47 (m, 5H), 7.44-7.38 (m, 4H), 7.36-7.31 (m, 2H), 7.31-7.22 (m, 2H), 7.17-7.07 (m, 4H), 7.03-6.96 (m, 2H).

[0306] Synthesis of compound A219

[0307]

[0308] Synthesis of compound A219-2

[0309] The synthesis and purification method of reference compound A1-3 was referred to, only the corresponding raw materials were changed, and the target compound A219-2 was obtained as a white solid (22.54 g, purity: 98.98%, yield: 78.15%), mass spectrum: 329.12 (M+H).

[0310] Synthesis of compound A219-3

[0311] The synthesis and purification method of reference compound A1-5 was referred to, only the corresponding raw materials were changed, and the target compound A219-3 was obtained as a white solid (22.62 g, purity: 99.81%, yield: 77.63%), mass spectrum: 357.22 (M+H).

[0312] Synthesis of compound A219-4

[0313] The synthesis and purification method of compound A1-7 were referred to, only the corresponding raw materials were changed, and the target compound A219-4 was obtained as a white solid (19.02 g, yield: 92.06%), mass spectrum: 385.04 (M+H). The obtained compound was directly used in the next step without purification.

[0314] Synthesis of compound A219-5

[0315] The synthesis and purification method of compound A1-8 were referred to, only the corresponding raw materials were changed, and the target compound A219-5 was obtained as a white solid (187.85 g, purity: 99.23%, yield: 43.05%), mass spectrum: 353.06 (M+H).

[0316] Synthesis of compound A219-7

[0317] The synthesis and purification method of compound A1 were referred to, only the corresponding raw materials were changed, and the target compound A219-7 was obtained as a white solid (18.63 g, purity: 99.55%, yield: 78.06%), mass spectrum: 520.20 (M+H).

[0318] Synthesis of compound A219

[0319] The synthesis and purification method of compound A1 were referred to, only the corresponding raw materials were changed, and the target compound A219 was obtained as a light yellow solid (17.96 g, purity: 99.93%, yield: 77.61%). After sublimation purification of 17.96 g of A219 crude product, sublimation pure A219 was obtained (15.00 g, purity: 99.93%, yield: 83.51%), mass spectrum: 836.28 (M+H).

[0320] 1 H NMR (400 MHz, CDCl3) δ 8.65-8.58 (m, 3H), 8.50-8.44 (m, 1H), 8.33 (d, J = 2.2 Hz, 2H), 8.26 (d, J = 7.8 Hz, 2H), 8.10 (d, J = 2.1 Hz, 1H), 8.07-8.02 (m, 1H), 8.02-7.94 (m, 5H), 7.94-7.87 (m, 2H), 7.58-7.45 (m, 4H), 7.42 (d, J = 7.6 Hz, 1H), 7.34 (dd, J = 7.7, 2.2 Hz, 2H), 7.32-7.25 (m, 3H), 7.17 (dd, J = 7.2, 2.1 Hz, 1H), 7.16-7.12 (m, 2H), 7.11-7.08 (m, 1H), 1.33 (s, 18H).

[0321] Synthesis of compound A226

[0322]

[0323] Synthesis of compound A226-2

[0324] Referring to the synthesis and purification method of compound A1-3, only the corresponding starting materials need to be changed to obtain the target compound A226-2 (35.23 g, purity: 99.21%, yield: 79.08%) as a white solid, mass spectrum: 329.12 (M+H).

[0325] Synthesis of compound A226-3

[0326] Referring to the synthesis and purification method of compound A1-5, only the corresponding starting materials need to be changed to obtain the target compound A226-3 (30.68 g, purity: 99.78%, yield: 74.62%) as a white solid, mass spectrum: 357.24 (M+H).

[0327] Synthesis of compound A226-4

[0328] Referring to the synthesis and purification method of compound A1-7, only the corresponding starting materials need to be changed to obtain the target compound A226-4 (24.55 g, yield: 96.33%) as a white solid, mass spectrum: 385.04 (M+H). The obtained compound is directly used in the next step without purification.

[0329] Synthesis of compound A226-5

[0330] Referring to the synthesis and purification method of compound A1-8, only the corresponding starting materials need to be changed to obtain the target compound A226-5 (17.99 g, purity: 99.86%, yield: 78.63%) as a white solid, mass spectrum: 353.06 (M+H).

[0331] Synthesis of compound A226

[0332] Referring to the synthesis and purification method of compound A1, only the corresponding starting materials need to be changed to obtain the target compound A226 (17.11 g, purity: 99.95%, yield: 78.74%) as a light yellow solid. After sublimation purification of 17.11 g of crude A226, sublimed A226 (13.75 g, purity: 99.95%, yield: 80.37%) is obtained, mass spectrum: 562.24 (M+H).

[0333] 1H NMR (400 MHz, CDC13) δ 8.75-8.71 (m, 2H), 8.66 (d, J = 8.9 Hz, 1H), 8.42 (d, J = 2.2 Hz, 1H), 8.03 (dd, J = 18.4, 8.8 Hz, 2H), 7.87 (d, J = 8.7 Hz, 1H), 7.75-7.52 (m, 8H), 7.47 (t, J = 7.7 Hz, 2H), 7.43-7.30 (m, 5H), 7.26-7.19 (m, 4H), 7.12-7.11 (m, 1H). Hydrogen spectrum data as shown in Figure 1

[0334] Synthesis of compound A252

[0335]

[0336] Synthesis of compound A252-2

[0337] Referring to the synthesis and purification method of compound A1-5, only the corresponding raw materials need to be changed to obtain the target compound A252-2 (18.42 g, purity: 99.52%, yield: 74.62%) as a white solid, mass spectrum: 433.20 (M+H).

[0338] Synthesis of compound A252-3

[0339] Referring to the synthesis and purification method of compound A1-7, only the corresponding raw materials need to be changed to obtain the target compound A252-3 (20.06 g, yield: 94.26%) as a white solid, mass spectrum: 461.12 (M+H). The obtained compound is directly used in the next step without purification.

[0340] Synthesis of compound A252-4

[0341] Referring to the synthesis and purification method of compound A1-8, only the corresponding raw materials need to be changed to obtain the target compound A252-4 (16.75 g, purity: 99.71%, yield: 74.29%) as a white solid, mass spectrum: 429.12 (M+H).

[0342] Synthesis of compound A252

[0343] Referring to the synthesis and purification method of compound A1, only the corresponding raw materials need to be changed to obtain the target compound A252 (14.02 g, purity: 99.93%, yield: 74.00%) as a light yellow solid. After sublimation purification of 14.02 g of crude A252, sublimed A252 (10.58 g, purity: 99.93%, yield: 75.47%) is obtained, mass spectrum: 638.22 (M+H).​

[0344] 1 H NMR (400 MHz, CDC13) δ 8.63 - 8.60 (m, 2H), 8.26 (d, J = 9.0 Hz, 1H), 8.00 - 7.95 (m, 3H), 7.93 - 7.89 (m, 2H), 7.80 (dd, J = 8.1, 2.4 Hz, 1H), 7.61 - 7.49 (m, 6H), 7.43 - 7.39 (m, 6H), 7.32 (d, J = 7.2 Hz, 1H), 7.31 - 7.24 (m, 2H), 7.17 - 7.07 (m, 5H), 7.02 - 6.96 (m, 2H).

[0345] Synthesis of compound A265

[0346]

[0347] Synthesis of compound A265

[0348] Referring to the synthesis and purification method of compound A1, only the corresponding starting materials need to be changed to obtain the target compound A265 (10.33 g, purity: 99.94%, yield: 78.63%) as a light yellow solid. After sublimation purification of 10.33 g of A265 crude product, sublimed A265 (8.13 g, purity: 99.94%, yield: 78.71%) was obtained, mass spectrum: 668.34 (M+H).

[0349] 1 H NMR (400 MHz, CDC13) δ 8.63 - 8.60 (m, 2H), 8.26 (d, J = 9.0 Hz, 1H), 8.00 - 7.95 (m, 3H), 7.93 - 7.89 (m, 2H), 7.80 (dd, J = 8.1, 2.4 Hz, 1H), 7.61 - 7.49 (m, 6H), 7.43 - 7.39 (m, 6H), 7.32 (d, J = 7.2 Hz, 1H), 7.31 - 7.24 (m, 2H), 7.17 - 7.07 (m, 5H), 7.02 - 6.96 (m, 2H).

[0350] Synthesis of compound A280

[0351]

[0352] Synthesis of compound A280-2

[0353] Referring to the synthesis and purification method of compound A1-3, only the corresponding starting materials need to be changed to obtain the target compound A280-2 (33.59 g, purity: 99.41%, yield: 74.02%) as a white solid, mass spectrum: 329.12 (M+H).

[0354] Synthesis of compound A280-3

[0355] The synthesis and purification process of reference compound A1-5 was followed, only by changing the corresponding starting materials, to obtain the target compound A280-3 as a white solid (32.63 g, purity: 99.69%, yield: 74.69%), mass: 357.24 (M+H).

[0356] Synthesis of compound A280-4

[0357] The synthesis and purification process of reference compound A1-7 was followed, only by changing the corresponding starting materials, to obtain the target compound A280-4 as a white solid (27.96 g, yield: 94.12%), mass: 385.04 (M+H). The obtained compound was used directly in the next step without purification.

[0358] Synthesis of compound A280-5

[0359] The synthesis and purification process of reference compound A1-8 was followed, only by changing the corresponding starting materials, to obtain the target compound A280-5 as a white solid (21.21 g, purity: 99.59%, yield: 74.63%), mass: 353.06 (M+H).

[0360] Synthesis of compound A280

[0361] The synthesis and purification process of reference compound A1 was followed, only by changing the corresponding starting materials, to obtain the target compound A280 as a light yellow solid (16.06 g, purity: 99.95%, yield: 74.44%). After sublimation purification of 16.06 g of A280 crude, sublimed A280 (12.90 g, purity: 99.95%, yield: 80.33%) was obtained, mass: 712.22 (M+H).

[0362] 1 H NMR (400 MHz, CDC13) 8.64 (d, J = 8.9 Hz, 1H), 8.47-8.39 (m, 1H), 8.34-8.24 (m, 2H), 8.19-8.15 (m, 3H), 8.08 (dd, J = 17.6, 7.8 Hz, 2H), 8.01-7.96 (m, 3H), 7.94 (d, J = 2.0 Hz, 1H), 7.92-7.85 (m, 1H), 7.66 (d, J = 8.0 Hz, 1H), 7.61-7.57 (m, 1H), 7.57-7.47 (m, 9H), 7.46-7.37 (m, 4H), 7.32-7.26 (m, 2H), 7.03-6.97 (m, 2H).

[0363] Synthesis of compound A289

[0364]

[0365] Synthesis of compound A289-3

[0366] Referring to the synthesis and purification method of compound A1, only the corresponding starting materials need to be changed to obtain the target compound A289-3 (20.06 g, purity: 99.87%, yield: 74.63%) as a white solid, mass spectrum: 356.23 (M+H).

[0367] Synthesis of compound A289-4

[0368] Referring to the synthesis and purification method of compound A1-8, only the corresponding starting materials need to be changed to obtain the target compound A289-4 (10.05, purity: 99.43%, yield: 39.85%) as a white solid, mass spectrum: 353.06 (M+H).

[0369] Synthesis of compound A289

[0370] Referring to the synthesis and purification method of compound A1, only the corresponding starting materials need to be changed to obtain the target compound A289 (10.96 g, purity: 99.93%, yield: 78.65%) as a light yellow solid. After sublimation purification of 10.96 grams of A289 crude product, sublimation pure A289 (8.88 g, purity: 99.93%, yield: 81.03%) was obtained, mass spectrum: 672.32 (M+H).

[0371] 1 H NMR (400 MHz, CDCl3) δ 8.61 (dd, J = 9.1, 2.3 Hz, 2H), 8.48-8.44 (m, 1H), 8.21 (d, J = 2.3 Hz, 1H), 8.17 (dd, J = 9.0, 2.3 Hz, 1H), 8.00 (d, J = 2.2 Hz, 1H), 7.96 (d, J = 9.3 Hz, 1H), 7.91-7.87 (m, 1H), 7.78 (s, 1H), 7.58-7.56 (m, 2H), 7.55-7.48 (m, 4H), 7.44-7.38 (m, 4H), 7.31 (dd, J = 7.5, 2.2 Hz, 1H), 7.13 (d, J = 6.6 Hz, 1H), 7.05-6.96 (m, 4H), 2.13-1.90 (m, 4H), 1.33 (s, 12H).

[0372] Synthesis of compound A305

[0373]

[0374] Synthesis of compound A305-3

[0375] The synthesis and purification of compound A1 were referred to, and only the corresponding starting materials were changed to obtain the target compound A305-3 (29.45 g, purity: 99.85%, yield: 75.44%) as a white solid, mass spectrum: 500.20 (M+H).

[0376] Synthesis of compound A305-4

[0377] The synthesis and purification of compound A1-8 were referred to, and only the corresponding starting materials were changed to obtain the target compound A305-4 (22.44 g, purity: 99.53%, yield: 38.43%) as a white solid, mass spectrum: 353.06 (M+H).

[0378] Synthesis of compound A305

[0379] The synthesis and purification of compound A1 were referred to, and only the corresponding starting materials were changed to obtain the target compound A305 (17.89 g, purity: 99.94%, yield: 74.85%) as a light yellow solid. After sublimation purification of 17.89 g of A305 crude, sublimed A305 (14.88 g, purity: 99.94%, yield: 83.18%) was obtained, mass spectrum: 816.28 (M+H).

[0380] 1 H NMR (400 MHz, CDCl3) δ 8.69 (d, J = 8.2 Hz, 1H), 8.62 (d, J = 9.3 Hz, 1H), 8.50-8.43 (m, 1H), 8.24 (d, J = 2.1 Hz, 1H), 8.11-8.03 (m, 3H), 7.99-7.92 (m, 2H), 7.92-7.85 (m, 1H), 7.76 (d, J = 7.1 Hz, 1H), 7.70-7.63 (m, 3H), 7.60 (dd, J = 8.0, 1.3 Hz, 1H), 7.56-7.22 (m, 19H), 7.14-7.06 (m, 2H), 7.03 (dd, J = 7.0, 1.4 Hz, 1H).

[0381] Synthesis of compound A340

[0382]

[0383] Synthesis of compound A340-2

[0384] The synthesis and purification method of the reference compound A1-5 was referred to, only the corresponding raw material was changed, to obtain the target compound A340-2 (20.20 g, purity: 99.52%, yield: 77.74%) as a white solid, mass spectrum: 357.22 (M+H).

[0385] Synthesis of compound A340-3

[0386] The synthesis and purification method of the reference compound A1-7 was referred to, only the corresponding raw material was changed, to obtain the target compound A340-3 (15.86 g, yield: 94.63%) as a white solid, mass spectrum: 385.04 (M+H). The obtained compound was directly used in the next step without purification.

[0387] Synthesis of compound A340-4

[0388] The synthesis and purification method of the reference compound A1-8 was referred to, only the corresponding raw material was changed, to obtain the target compound A340-4 (14.36 g, purity: 99.76%, yield: 76.33%) as a white solid, mass spectrum: 353.06 (M+H).

[0389] Synthesis of compound A340-5

[0390] The synthesis and purification method of the reference compound A1-3 was referred to, only the corresponding raw material was changed, to obtain the target compound A340-4 (12.37 g, purity: 98.08%, yield: 75.55%) as a white solid, mass spectrum: 445.20 (M+H).

[0391] Synthesis of compound A340-7

[0392] The synthesis and purification method of the reference compound A1-5 was referred to, only the corresponding raw material was changed, to obtain the target compound A340-7 (10.23 g, purity: 98.88%, yield: 78.96%) as a white solid, mass spectrum: 523.04 (M+H).

[0393] Synthesis of compound A340

[0394] The synthesis and purification method of the reference compound A1 was referred to, only the corresponding raw material was changed, to obtain the target compound A340 (10.28 g, purity: 99.95%, yield: 78.26%) as a light yellow solid. After sublimation purification of 10.28 g of A340 crude product, sublimation pure A340 (8.02 g, purity: 99.95%, yield: 78.02%) was obtained, mass spectrum: 764.22 (M+H).

[0395] 1H NMR (400 MHz, CDC13) δ 8.61-8.59 (m, 2H), 8.29-8.27 (m, 1H), 8.16-8.14 (m, 1H), 8.06-8.01 (m, 2H), 7.96-7.86 (m, 3H), 7.80 (d, J = 7.7 Hz, 1H), 7.69 (dd, J = 7.2, 2.5 Hz, 1H), 7.64-7.45 (m, 14H), 7.45-7.36 (m, 7H), 7.32 (d, J = 7.6 Hz, 1H), 6.96-6.91 (m, 4H).

[0396] Synthesis of compound A424

[0397]

[0398] Synthesis of compound A424-1

[0399] Referring to the synthesis and purification method of compound A1-5, only the corresponding raw materials need to be changed to obtain the target compound A424-1 (26.52 g, purity: 99.46%, yield: 74.52%) as a white solid, mass spectrum: 357.24 (M+H).

[0400] Synthesis of compound A424-2

[0401] Referring to the synthesis and purification method of compound A1-7, only the corresponding raw materials need to be changed to obtain the target compound A424-2 (18.06 g, yield: 93.06%) as a white solid, mass spectrum: 385.04 (M+H). The obtained compound is directly used in the next step without purification.

[0402] Synthesis of compound A424-3

[0403] Referring to the synthesis and purification method of compound A1-8, only the corresponding raw materials need to be changed to obtain the target compound A424-3 (18.85 g, purity: 99.23%, yield: 40.05%) as a white solid, mass spectrum: 353.06 (M+H).

[0404] Synthesis of compound A424-5

[0405] Referring to the synthesis and purification method of compound A1, only the corresponding raw materials need to be changed to obtain the target compound A424-5 (15.96 g, purity: 99.77%, yield: 79.06%) as a white solid, mass spectrum: 385.16 (M+H).

[0406] Synthesis of compound A424

[0407] The synthesis and purification method of compound A1 were referred to, only the corresponding raw materials were changed, and the target compound A424 was obtained as a light yellow solid (13.06 g, purity: 99.94%, yield: 78.61%). After sublimation purification of 13.06 g of A424 crude product, sublimed A424 (10.00 g, purity: 99.94%, yield: 76.57%) was obtained, mass spectrum: 701.25 (M+H).

[0408] 1 H NMR (400 MHz, CDC13) δ 8.62 (s, 1H), 8.48 - 8.41 (m, 1H), 8.35 - 8.25 (m, 1H), 8.16 (d, J = 2.2 Hz, 1H), 8.04 - 7.98 (m, 2H), 7.96 (dd, J = 7.4, 2.7 Hz, 2H), 7.93 - 7.84 (m, 6H), 7.78 (d, J = 2.1 Hz, 1H), 7.55 - 7.46 (m, 4H), 7.42 (d, J = 7.6 Hz, 1H), 7.38 (dd, J = 7.2, 2.1 Hz, 1H), 7.35 - 7.25 (m, 5H), 7.25 - 7.16 (m, 3H), 7.16 - 7.05 (m, 3H).

[0409] Synthesis of compound A481

[0410]

[0411] Synthesis of compound A481-2

[0412] The synthesis and purification method of compound A1-3 were referred to, only the corresponding raw materials were changed, and the target compound A481-2 was obtained as a white solid (25.77 g, purity: 98.88%, yield: 74.12%), mass spectrum: 355.12 (M+H).

[0413] Synthesis of compound A481-4

[0414] The synthesis and purification method of compound A1-5 were referred to, only the corresponding raw materials were changed, and the target compound A481-4 was obtained as a white solid (20.11 g, purity: 99.54%, yield: 71.52%), mass spectrum: 439.18 (M+H).

[0415] Synthesis of compound A481-5

[0416] The synthesis and purification method of compound A1-7 was referred to, only the corresponding raw materials were changed, to obtain the target compound A481-5 (22.53 g, yield: 95.86%) as a white solid, mass spectrum: 467.22 (M+H). The obtained compound was directly used in the next step without purification.

[0417] Synthesis of compound A481-6

[0418] The synthesis and purification method of compound A1-8 was referred to, only the corresponding raw materials were changed, to obtain the target compound A481-6 (18.88 g, purity: 99.75%, yield: 75.62%) as a white solid, mass spectrum: 435.16 (M+H).

[0419] Synthesis of compound A481

[0420] The synthesis and purification method of compound A1 was referred to, only the corresponding raw materials were changed, to obtain the target compound A481 (15.55 g, purity: 99.94%, yield: 76.22%) as a light yellow solid. After sublimation purification of 15.55 g of A481 crude, sublimed A481 (11.85 g, purity: 99.94%, yield: 76.21%) was obtained, mass spectrum: 658.30 (M+H).

[0421] 1 H NMR (400 MHz, CDCl3) δ 8.63-8.57 (m, 1H), 8.50 (d, J = 8.1 Hz, 1H), 8.28-8.22 (m, 1H), 8.16-8.07 (m, 2H), 8.06 (d, J = 2.2 Hz, 1H), 7.99-7.92 (m, 3H), 7.89-7.84 (m, 1H), 7.77 (d, J = 7.1 Hz, 1H), 7.67-7.60 (m, 1H), 7.56 (d, J = 7.9 Hz, 1H), 7.47-7.43 (m, 1H), 7.43-7.35 (m, 2H), 7.31-7.24 (m, 2H), 7.19 (dd, J = 7.2, 2.1 Hz, 1H), 7.17-7.12 (m, 2H), 7.12-7.05 (m, 2H), 7.03 (dd, J = 7.3, 2.2 Hz, 1H), 1.80 (s, 6H), 1.34 (s, 9H).

[0422] Synthesis of compound A488

[0423]

[0424]

[0425] Synthesis of compound A488-2

[0426] The synthesis and purification of reference compound A1-3 were repeated by changing the corresponding starting materials to obtain the target compound A488-2 (28.77 g, purity: 99.02%, yield: 76.74%) as a white solid. Mass: 404.14 (M+H).

[0427] Synthesis of compound A488-3

[0428] The synthesis and purification of reference compound A1-5 were repeated by changing the corresponding starting materials to obtain the target compound A488-3 (24.85 g, purity: 99.67%, yield: 73.62%) as a white solid. Mass: 432.21 (M+H).

[0429] Synthesis of compound A488-4

[0430] The synthesis and purification of reference compound A1-7 were repeated by changing the corresponding starting materials to obtain the target compound A488-4 (23.41 g, yield: 96.66%) as a white solid. Mass: 460.04 (M+H). The obtained compound was used directly in the next step without purification.

[0431] Synthesis of compound A488-5

[0432] The synthesis and purification of reference compound A1-8 were repeated by changing the corresponding starting materials to obtain the target compound A488-5 (20.00 g, purity: 99.87%, yield: 77.01%) as a white solid. Mass: 428.02 (M+H).

[0433] Synthesis of compound A488

[0434] The synthesis and purification of reference compound A1 were repeated by changing the corresponding starting materials to obtain the target compound A488 (18.11 g, purity: 99.92%, yield: 75.98%) as a light yellow solid. After sublimation purification of 18.11 g of crude A488, sublimed A488 (15.00 g, purity: 99.93%, yield: 82.83%) was obtained. Mass: 713.24 (M+H).

[0435] 1H NMR (400 MHz, CDC13) δ 8.60 (d, J = 9.0 Hz, 1H), 8.52 (d, J = 8.0 Hz, 1H), 8.47-8.41 (m, 1H), 8.27-8.22 (m, 1H), 8.14-8.07 (m, 2H), 8.06-8.04 (m, 1H), 7.94 (d, J = 8.1 Hz, 1H), 7.92-7.87 (m, 2H), 7.63-7.55 (m, 4H), 7.55-7.48 (m, 6H), 7.44-7.35 (m, 7H), 7.34-7.27 (m, 2H), 7.23-7.13 (m, 3H), 7.04-6.97 (m, 4H).

[0436] Synthesis of compound A496

[0437]

[0438] Synthesis of compound A496-2

[0439] Referring to the synthesis and purification method of compound A1-5, only the corresponding starting materials need to be changed to obtain the target compound A496-2 (18.81 g, purity: 99.72%, yield: 73.62%) as a white solid, mass spectrum: 429.10 (M+H).

[0440] Synthesis of compound A496-3

[0441] Referring to the synthesis and purification method of compound A1-7, only the corresponding starting materials need to be changed to obtain the target compound A496-3 (18.77 g, yield: 92.626%) as a white solid, mass spectrum: 457.13 (M+H). The obtained compound is directly used in the next step without purification.

[0442] Synthesis of compound A496-4

[0443] Referring to the synthesis and purification method of compound A1-8, only the corresponding starting materials need to be changed to obtain the target compound A496-4 (16.85 g, purity: 99.45%, yield: 75.11%) as a white solid, mass spectrum: 425.24 (M+H)

[0444] Synthesis of compound A496-5

[0445] Referring to the synthesis and purification method of compound A1-5, only the corresponding starting materials need to be changed to obtain the target compound A496-5 (19.78 g, purity: 99.62%, yield: 74.44%) as a white solid, mass spectrum: 591.15 (M+H).

[0446] Synthesis of compound A496

[0447] Referring to the synthesis and purification method of compound A1, only the corresponding starting material needs to be changed to obtain the target compound A496 (12.71, purity: 99.95%, yield: 62.71%) as a light yellow solid. After sublimation purification of 12.71 g of A496 crude product, sublimed A496 (9.84 g, purity: 99.97%, yield: 11.41%) was obtained, mass spectrum: 800.07 (M+H).

[0448] 1 H NMR (400 MHz, CDCl3) δ 8.62 (dd, J = 13.1, 8.5 Hz, 2H), 8.30 (dd, J = 9.0, 0.7 Hz, 1H), 8.16 (d, J = 7.9 Hz, 1H), 8.06 - 7.98 (m, 3H), 7.89 (dt, J = 7.0, 0.7 Hz, 1H), 7.83 (d, J = 2.2 Hz, 1H), 7.79 - 7.70 (m, 2H), 7.67 (dd, J = 9.2, 2.1 Hz, 1H), 7.61 - 7.50 (m, 6H), 7.46 - 7.37 (m, 5H), 7.35 - 7.24 (m, 4H), 7.17 - 7.06 (m, 3H), 7.03 - 6.97 (m, 2H), 0.39 (s, 9H).

[0449] Synthesis of compound A515

[0450]

[0451] Synthesis of compound A515-2

[0452] Referring to the synthesis and purification method of compound A1-3, only the corresponding starting material needs to be changed to obtain the target compound A515-2 (25.33 g, purity: 99.23%, yield: 78.46%) as a white solid, mass spectrum: 379.12 (M+H).

[0453] Synthesis of compound A515-3

[0454] Referring to the synthesis and purification method of compound A1-5, only the corresponding starting material needs to be changed to obtain the target compound A515-3 (22.11 g, purity: 99.43%, yield: 75.12%) as a white solid, mass spectrum: 407.06 (M+H).

[0455] Synthesis of compound A515-4

[0456] The synthesis and purification method of compound A1-7 were referred to, only the corresponding raw materials were changed, and the target compound A515-4 was obtained as a white solid (20.63 g, yield: 95.12%), mass spectrum: 435.12 (M+H). The obtained compound was directly used in the next step without purification.

[0457] Synthesis of compound A515-5

[0458] The synthesis and purification method of compound A1-8 were referred to, only the corresponding raw materials were changed, and the target compound A515-5 was obtained as a white solid (18.96 g, purity: 99.90%, yield: 79.63%), mass spectrum: 403.08 (M+H).

[0459] Synthesis of compound A515

[0460] The synthesis and purification method of compound A1 were referred to, only the corresponding raw materials were changed, and the target compound A515 was obtained as a light yellow solid (16.96 g, purity: 99.93%, yield: 76.68%). After sublimation purification of 16.96 g of A515 crude product, sublimed A515 was obtained (14.33 g, purity: 99.93%, yield: 84.49%), mass spectrum: 612.75 (M+H).

[0461] 1 H NMR (400 MHz, CDCl3) δ 8.61 (dd, J = 8.5, 3.7 Hz, 2H), 8.47-8.39 (m, 1H), 8.33-8.26 (m, 2H), 8.02 (d, J = 2.0 Hz, 1H), 7.94 (d, J = 8.2 Hz, 1H), 7.91-7.85 (m, 2H), 7.83 (dd, J = 7.4, 2.1 Hz, 1H), 7.61-7.49 (m, 6H), 7.45-7.37 (m, 4H), 7.35-7.24 (m, 3H), 7.17-7.07 (m, 3H), 7.03-6.97 (m, 2H), 6.88 (dd, J = 7.6, 2.3 Hz, 1H).

[0462] Synthesis of compound A527

[0463]

[0464] Synthesis of compound A527-2

[0465] The synthesis and purification method of compound A1-3 was referred to, only the corresponding raw material was changed, to obtain the target compound A527-2 (22.10 g, purity: 99.10%, yield: 70.01%) as a white solid, mass spectrum: 405.14 (M+H).

[0466] Synthesis of compound A527-3

[0467] The synthesis and purification method of compound A1-5 was referred to, only the corresponding raw material was changed, to obtain the target compound A527-3 (20.06 g, purity: 99.21%, yield: 72.32%) as a white solid, mass spectrum: 433.08 (M+H).

[0468] Synthesis of compound A527-4

[0469] The synthesis and purification method of compound A1-7 was referred to, only the corresponding raw material was changed, to obtain the target compound A527-4 (18.06 g, yield: 94.33%) as a white solid, mass spectrum: 461.22 (M+H). The obtained compound was directly used in the next step without purification.

[0470] Synthesis of compound A527-5

[0471] The synthesis and purification method of compound A1-8 was referred to, only the corresponding raw material was changed, to obtain the target compound A527-5 (17.63 g, purity: 99.88%, yield: 42.03%) as a white solid, mass spectrum: 429.12 (M+H).

[0472] Synthesis of compound A527

[0473] The synthesis and purification method of compound A1 was referred to, only the corresponding raw material was changed, to obtain the target compound A527 (14.63 g, purity: 99.93%, yield: 74.95%) as a light yellow solid. After sublimation purification of 14.63 g of A527 crude product, sublimation pure A527 (12.00 g, purity: 99.93%, yield: 82.02%) was obtained, mass spectrum: 668.20 (M+H).

[0474] 1H NMR (400 MHz, CDC13) δ 8.44 (s, 1H), 8.33-8.26 (m, 1H), 8.23-8.16 (m, 1H), 8.01 (d, J = 9.0 Hz, 1H), 7.98-7.83 (m, 7H), 7.78-7.75 (m, 2H), 7.55-7.47 (m, 7H), 7.44-7.38 (m, 3H), 7.32-7.24 (m, 2H), 7.17-7.06 (m, 4H).

[0475] Synthesis of compound A539

[0476]

[0477] Synthesis of compound A539-2

[0478] Referring to the synthesis and purification method of compound A1-3, only the corresponding starting materials need to be changed to obtain the target compound A539-2 (18.63 g, purity: 99.22%, yield: 76.52%) as a white solid, mass spectrum: 504.16 (M+H).

[0479] Synthesis of compound A539-3

[0480] Referring to the synthesis and purification method of compound A1-5, only the corresponding starting materials need to be changed to obtain the target compound A539-3 (17.26 g, purity: 99.12%, yield: 75.63%) as a white solid, mass spectrum: 532.14 (M+H).

[0481] Synthesis of compound A539-4

[0482] Referring to the synthesis and purification method of compound A1-7, only the corresponding starting materials need to be changed to obtain the target compound A539-4 (15.12 g, yield: 96.33%) as a white solid, mass spectrum: 560.12 (M+H). The obtained compound is directly used in the next step without purification.

[0483] Synthesis of compound A539-5

[0484] Referring to the synthesis and purification method of compound A1-8, only the corresponding starting materials need to be changed to obtain the target compound A539-5 (14.00 g, purity: 99.87%, yield: 41.26%) as a white solid, mass spectrum: 528.24 (M+H).

[0485] Synthesis of compound A539

[0486] Referring to the synthesis and purification method of compound A1, only the corresponding starting material needs to be changed to obtain the target compound A539 as a light yellow solid (14.00 g, purity: 99.92%, yield: 76.78%). After sublimation purification of 14.00 g of A539 crude product, sublimed A539 (11.52 g, purity: 99.92%, yield: 82.28%) was obtained, mass spectrum: 813.32 (M+H).

[0487] 1 H NMR (400 MHz, CDC13) δ 8.87 (s, 1H), 8.51-8.49 (m, 1H), 8.33-8.26 (m, 2H), 8.21-8.19 (m, 1H), 8.12 (d, J = 2.2 Hz, 1H), 8.04-7.99 (m, 2H), 7.96 (d, J = 8.0 Hz, 1H), 7.92-7.83 (m, 3H), 7.63-7.48 (m, 11H), 7.48-7.37 (m, 8H), 7.34-7.26 (m, 2H), 7.20-7.10 (m, 3H), 7.03-6.97 (m, 4H).

[0488] Synthesis of compound B5

[0489]

[0490] Synthesis of compound B5-3

[0491] Compound B5-1 (20.00 g, 72.96 mmol), compound B5-2 (22.23 g, 87.56 mmol), 1,1-bis(diphenylphosphino)ferrocene palladium dichloride (0.53 g, 0.73 mmol), potassium acetate (17.90 g, 182.41 mol), 1,4-dioxane (375 ml) were added to a 1000 ml three-necked round-bottom flask, replaced with vacuum nitrogen three times, and then the system was heated to 100°C for 2 hours. TLC (ethyl acetate: n-hexane = 1:15 as developing agent) was used to monitor the reaction, and compound B5-1 was consumed.

[0492] The temperature was lowered to 60°C, and the solvent was removed by concentration under reduced pressure. Ethyl acetate (700 ml) was added, and deionized water was washed three times (300 ml*3). After separation, the silica gel sample was mixed and dried, and silica gel column chromatography purification was performed (200-300 mesh silica gel, ethyl acetate: n-hexane = 1:15 as eluent). After elution, 70°C reduced pressure concentration for 1 hour obtained white solid as compound B5-3 (18.95 g, purity: 98.51%, yield: 80.87%), mass spectrum: 322.08 (M+H).

[0493] Synthesis of compound B5-5

[0494] Compound B5-3 (18.50 g, 57.60 mmol), compound B5-4 (12.64 g, 57.60 mmol), tetrakis(triphenylphosphine)palladium (0.66 g, 0.58 mmol), potassium carbonate (19.90 g, 114.00 mmol), tetrahydrofuran (375 ml), deionized water (125 ml) were added into a 1000 ml three-necked round-bottom flask, replaced with vacuum nitrogen three times, then the system was heated to 75 °C for 3 hours, and the reaction was monitored by TLC (ethyl acetate: n-hexane = 1:10 as developing agent). Compound B5-3 was consumed completely.

[0495] The temperature was lowered to 60 °C, and the solvent was removed by concentration under reduced pressure. Ethyl acetate (700 ml) was added, and deionized water was washed three times (300 ml*3). The liquid was separated, and the silica gel was mixed and dried. The sample was column-purified by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate: n-hexane = 1:20 as eluent). After elution, the white solid was obtained by concentration under reduced pressure at 70 °C for 2 hours. Compound B5-5 (14.26 g, purity: 99.21%, yield: 74.17%) was obtained. Mass: 334.02 (M+H).

[0496] Synthesis of compound B5-7

[0497] Compound B5-5 (14.00 g, 41.95 mmol), compound B5-6 (21.57 g, 62.92 mmol), tetrahydrofuran (270 ml) were added into a 1000 ml three-necked round-bottom flask, replaced with vacuum nitrogen three times, then the system was cooled to 5 °C, and sodium methoxide (4.53 g, 83.89 mmol) was added at one time. The reaction was maintained at 5 °C for 1 hour, and the reaction was monitored by TLC (ethyl acetate: n-hexane = 1:10 as developing agent). Compound B5-5 was consumed completely.

[0498] Deionized water (500 ml) was added, and the solvent was removed by concentration under reduced pressure. Ethyl acetate (700 ml) was added for extraction, and the liquid was separated. The white solid was obtained by concentration under reduced pressure at 70 °C for 1 hour. Compound B5-7 (14.17 g, yield: 93.37%) was obtained. Mass: 362.04 (M+H). The obtained compound was used directly in the next step without purification.

[0499] Synthesis of compound B5-8

[0500] Compound B5-7 (14.00 g, 38.69 mmol), toluene (150 ml) were added into a 500 ml three-necked round-bottom flask, which was replaced with vacuum nitrogen for three times, then the system was cooled to 5 °C, methyl sulfonic acid (7.44 g, 77.39 mmol) was slowly added dropwise, which was completed in 3 minutes, and the reaction was maintained at 5 °C for 1 hour. TLC (ethyl acetate: n-hexane = 1:15 as developing agent) was used to monitor the reaction, and compound B5-7 was consumed completely.

[0501] Methanol (200 ml) was added thereto, and a large amount of white solid was precipitated. Filtration under suction gave 14 g of solid. The solid was crystallized once with toluene (190 ml) and methanol (150 ml), and then filtered under suction. The filter cake was dried at 80 °C under vacuum for 1 hour to give white solid as compound B5-8 (9.25 g, purity: 99.76%, yield: 72.49%).

[0502] Synthesis of compound B5-9

[0503] Referring to the synthesis and purification method of compound B5-3, only the corresponding starting material was changed to obtain white solid as target compound B5-9 (9.16 g, purity: 99.17%, yield: 79.67%).

[0504] Synthesis of compound B5

[0505] Compound B5-9 (9.00 g, 21.36 mmol), B5-10 (7.64 g, 21.36 mmol), tetrakis(triphenylphosphine)palladium (0.49 g, 0.43 mmol), sodium hydroxide (2.14 g, 53.41 mmol), tetrahydrofuran (300 ml), and deionized water (100 ml) were added into a 1000 ml three-necked round-bottom flask, which was replaced with vacuum nitrogen for three times, and then the system was warmed to 75 °C for 6 hours. TLC (ethyl acetate: n-hexane = 1:10 as developing agent) was used to monitor the consumption of compound B5-9.

[0506] After cooling to room temperature, methanol (300 ml) was added and stirred at room temperature for 30 minutes, suction filtered to obtain a yellow solid. Xylene (450 ml) was added, and the material was dissolved by heating to 120°C, and filtered once by column chromatography on silica gel (60 g, 200-300 mesh) after cooling to room temperature. The filter cake was washed with 200 ml of xylene until no product residue was left, and the organic phase was concentrated under reduced pressure at 70°C to obtain a yellow solid, which was crystallized twice with xylene and methanol, and dried at 100°C under vacuum for 8 hours to obtain light yellow solid as compound B5 (10.21 g, purity: 99.93%, yield: 77.50%). After sublimation purification of 10.21 g of the crude compound B5, sublimation purified compound B5 (6.25 g, purity: 99.93%, yield: 61.21%) was obtained. Mass: 617.20 (M+H).

[0507] 1 H NMR (400 MHz, CDCl3) δ 9.69 (d, J = 2.9 Hz, 1H), 8.52 (dd, J = 15.0, 3.0 Hz, 1H), 8.42 - 8.31 (m, 2H), 8.22 - 8.13 (m, 3H), 8.11 (d, J = 1.4 Hz, 2H), 7.98 (dd, J = 14.6, 3.4 Hz, 1H), 7.92 (m, 1H), 7.75 (dd, J = 15.0, 3.0 Hz, 1H), 7.70 - 7.45 (m, 10H), 7.45 - 7.35 (m, 1H), 7.31 (m, 1H).

[0508] Synthesis of compound B20

[0509]

[0510] Synthesis of compound B20-2

[0511] Referring to the synthesis and purification method of compound B5-3, only the corresponding starting materials need to be changed to obtain the target compound B20-2 (18.15 g, purity: 98.91%, yield: 79.63%). Mass: 386.01 (M+H).

[0512] Synthesis of compound B20-3

[0513] Referring to the synthesis and purification method of compound B5-5, only the corresponding starting materials need to be changed to obtain the target compound B20-3 (13.84 g, purity: 99.42%, yield: 74.45%). Mass: 397.98 (M+H).

[0514] Synthesis of compound B20-4

[0515] The synthesis and purification method of compound B5-7 were referred to, only the corresponding raw materials were changed, the target compound B20-4 (13.29 g, yield: 91.94%) was obtained, mass spectrum: 426.01 (M+H).

[0516] Synthesis of compound B20-5

[0517] The synthesis and purification method of compound B5-8 were referred to, only the corresponding raw materials were changed, the target compound B20-5 (8.61 g, purity: 99.74%, yield: 71.63%) was obtained, mass spectrum: 393.95 (M+H).

[0518] Synthesis of compound B20-6

[0519] The synthesis and purification method of compound B5-3 were referred to, only the corresponding raw materials were changed, the target compound B20-6 (8.27 g, purity: 99.16%, yield: 78.91%) was obtained, mass spectrum: 486.11 (M+H).

[0520] Synthesis of compound B20

[0521] The synthesis and purification method of compound B5 were referred to, only the corresponding raw materials were changed, the target compound B20 (8.36 g, purity: 99.95%, yield: 74.46%) was obtained. After sublimation purification of 8.36 g of compound B20 crude product, sublimation purified compound B20 (5.23 g, purity: 99.94%, yield: 62.56%) was obtained, mass spectrum: 681.11 (M+H).

[0522] 1 H NMR (400 MHz, CDCl3) δ 9.67 (d, J = 2.9 Hz, 1H), 8.52 (dd, J = 15.0, 3.0 Hz, 1H), 8.42 - 8.31 (m, 2H), 8.22 (t, J = 4.0 Hz, 1H), 8.21 - 8.10 (m, 5H), 7.98 (dd, J = 14.6, 3.4 Hz, 1H), 7.92 (dd, J = 15.0, 1.7 Hz, 1H), 7.78 (d, J = 15.0 Hz, 1H), 7.76 - 7.72 (m, 1H), 7.70 - 7.60 (m, 3H), 7.57 (dd, J = 12.8, 2.1 Hz, 1H), 7.56 - 7.46 (m, 4H), 7.39 (m, 1H), 7.31 (m, 1H).

[0523] Synthesis of compound B38

[0524]

[0525] Synthesis of compound B38-2

[0526] The synthesis and purification method of reference compound B5-3 was referred to, and only the corresponding raw materials were changed to obtain the target compound B38-2 (28.38 g, purity: 99.03%, yield: 80.74%). Mass spectrum: 322.15 (M+H).

[0527] Synthesis of compound B38-4

[0528] The synthesis and purification method of reference compound B5-5 was referred to, and only the corresponding raw materials were changed to obtain the target compound B38-4 (21.51 g, purity: 99.42%, yield: 73.92%). Mass spectrum: 334.06 (M+H).

[0529] Synthesis of compound B38-5

[0530] The synthesis and purification method of reference compound B5-7 was referred to, and only the corresponding raw materials were changed to obtain the target compound B38-5 (21.82 g, yield: 87.51%). Mass spectrum: 362.09 (M+H).

[0531] Synthesis of compound B38-6

[0532] The synthesis and purification method of reference compound B5-8 was referred to, and only the corresponding raw materials were changed to obtain the target compound B38-6 (13.50 g, purity: 99.39%, yield: 70.53%). Mass spectrum: 330.06 (M+H).

[0533] Synthesis of compound B38-7

[0534] The synthesis and purification method of reference compound B5-3 was referred to, and only the corresponding raw materials were changed to obtain the target compound B38-7 (13.05 g, purity: 99.24%, yield: 78.58%). Mass spectrum: 422.18 (M+H).

[0535] Synthesis of compound B38

[0536] The synthesis and purification method of reference compound B5 was referred to, and only the corresponding raw materials were changed to obtain the target compound B38 (6.45 g, purity: 99.92%, yield: 73.16%). After sublimation purification of 7.51 g of crude compound B38, sublimation purified compound B38 (4.13 g, purity: 99.94%, yield: 64.12%) was obtained. Mass spectrum: 577.20 (M+H).

[0537] 1H NMR (400 MHz, CDC13) δ 9.11 (d, J = 14.9 Hz, 1H), 9.09 (d, J = 2.9 Hz, 1H), 8.84 (s, 1H), 8.49 (dd, J = 15.0, 3.0 Hz, 1H), 8.41 - 8.31 (m, 2H), 8.24 - 8.03 (m, 7H), 8.03 - 7.97 (m, 1H), 7.92 (t, J = 1.4 Hz, 2H), 7.70 - 7.55 (m, 5H), 7.55 - 7.46 (m, 3H).

[0538] Synthesis of compound B42

[0539]

[0540] Synthesis of compound B42

[0541] Referring to the synthesis and purification method of compound B5, only the corresponding raw materials need to be changed to obtain the target compound B42 (6.31 g, purity: 99.93%, yield: 71.85%). After sublimation purification of 6.31 g of compound B42 crude product, sublimation purified compound B42 (4.29 g, purity: 99.94%, yield: 67.98%) was obtained, mass spectrum: 617.19 (M+H).

[0542] 1 H NMR (400 MHz, CDC13) δ 9.11 (d, J = 14.9 Hz, 1H), 9.09 (d, J = 2.9 Hz, 1H), 8.84 (s, 1H), 8.49 (dd, J = 15.0, 3.0 Hz, 1H), 8.41 - 8.31 (m, 2H), 8.24 - 8.03 (m, 7H), 8.03 - 7.97 (m, 1H), 7.92 (t, J = 1.4 Hz, 2H), 7.70 - 7.55 (m, 5H), 7.55 - 7.46 (m, 3H).

[0543] Synthesis of compound B56

[0544]

[0545] Synthesis of compound B56-2

[0546] Referring to the synthesis and purification method of compound B5-3, only the corresponding raw materials need to be changed to obtain the target compound B56-2 (16.37 g, purity: 99.16%, yield: 71.82%), mass spectrum: 386.07 (M+H).

[0547] Synthesis of compound B56-3

[0548] The synthesis and purification method of compound B5-5 were referred to, only the corresponding raw materials were changed, the target compound B56-3 (12.54 g, purity: 99.47%, yield: 75.89%) was obtained, mass spectrum: 397.98 (M+H).

[0549] Synthesis of compound B56-4

[0550] The synthesis and purification method of compound B5-7 were referred to, only the corresponding raw materials were changed, the target compound B56-4 (11.51 g, yield: 89.58%) was obtained, mass spectrum: 426.00 (M+H).

[0551] Synthesis of compound B56-5

[0552] The synthesis and purification method of compound B5-8 were referred to, only the corresponding raw materials were changed, the target compound B56-5 (8.14 g, purity: 99.54%, yield: 80.04%) was obtained, mass spectrum: 393.98 (M+H).

[0553] Synthesis of compound B56-6

[0554] The synthesis and purification method of compound B5-3 were referred to, only the corresponding raw materials were changed, the target compound B56-6 (7.49 g, purity: 99.08%, yield: 80.99%) was obtained, mass spectrum: 486.11 (M+H).

[0555] Synthesis of compound B56

[0556] The synthesis and purification method of compound B5 were referred to, only the corresponding raw materials were changed, the target compound B56 (7.17 g, purity: 99.94%, yield: 73.09%) was obtained. After sublimation purification of 7.17 g of crude compound B56, sublimation purified compound B56 (4.25 g, purity: 99.94%, yield: 59.27%) was obtained, mass spectrum: 680.12 (M+H).

[0557] 1H NMR (400 MHz, CDC13) δ 9.65 (d, J = 3.1 Hz, 1H), 8.52 (dd, J = 15.0, 3.0 Hz, 1H), 8.23 (s, 1H), 8.21 - 8.17 (m, 2H), 8.17 - 8.13 (m, 1H), 8.11 (dd, J = 15.3, 3.2 Hz, 1H), 8.02 - 7.98 (m, 1H), 7.98 - 7.89 (m, 4H), 7.75 (dd, J = 15.0, 3.0 Hz, 1H), 7.66 - 7.61 (m, 3H), 7.61 - 7.43 (m, 7H), 7.39 (m, 1H), 7.31 (m, 1H).

[0558] Synthesis of compound B64

[0559]

[0560] Synthesis of compound B64-3

[0561] Referring to the synthesis and purification method of compound B5-5, only the corresponding raw materials need to be changed to obtain the target compound B64-3 (23.51 g, purity: 99.31%, yield: 74.27%), mass spectrum: 284.04 (M+H).

[0562] Synthesis of compound B64-4

[0563] Referring to the synthesis and purification method of compound B5-7, only the corresponding raw materials need to be changed to obtain the target compound B64-4 (21.68 g, yield: 85.78%), mass spectrum: 312.07 (M+H).

[0564] Synthesis of compound B64-5

[0565] Referring to the synthesis and purification method of compound B5-8, only the corresponding raw materials need to be changed to obtain the target compound B64-5 (14.72 g, purity: 99.38%, yield: 76.31%), mass spectrum: 280.04 (M+H).

[0566] Synthesis of compound B64-6

[0567] Referring to the synthesis and purification method of compound B5-3, only the corresponding raw materials need to be changed to obtain the target compound B64-6 (15.23 g, purity: 99.07%, yield: 79.14%), mass spectrum: 372.16 (M+H).

[0568] Synthesis of compound B64

[0569] The synthesis and purification method of compound B5 were referred to, only the corresponding raw materials were changed, the target compound B64 (10.17 g, purity: 99.90%, yield: 70.30%) was obtained. After sublimation purification of 10.17 g of compound B64 crude product, sublimation compound B64 (6.64, purity: 99.92%, yield: 65.28%) was obtained, mass spectrum: 553.19 (M+H).

[0570] 1 H NMR (400 MHz, CDCl3) δ 8.49 (dd, J = 14.6, 3.0 Hz, 1H), 8.46 (d, J = 2.9 Hz, 1H), 8.41 - 8.31 (m, 2H), 8.21 - 8.14 (m, 2H), 8.00 - 7.95 (m, 2H), 7.94 - 7.91 (m, 1H), 7.91 - 7.86 (m, 1H), 7.78 - 7.72 (m, 2H), 7.70 - 7.59 (m, 3H), 7.54 - 7.45 (m, 5H), 7.43 (dd, J = 10.6, 7.3 Hz, 1H), 7.28 - 7.21 (m, 3H).

[0571] Synthesis of compound B81

[0572]

[0573] Synthesis of compound B81-2

[0574] The synthesis and purification method of compound B5-5 were referred to, only the corresponding raw materials were changed, the target compound B81-2 (7.68 g, purity: 99.42%, yield: 76.17%) was obtained, mass spectrum: 406.09 (M+H).

[0575] Synthesis of compound B81-3

[0576] The synthesis and purification method of compound B5-3 were referred to, only the corresponding raw materials were changed, the target compound B81-3 (7.26 g, purity: 99.18%, yield: 78.99%) was obtained, mass spectrum: 498.21 (M+H).

[0577] Synthesis of compound B81

[0578] The synthesis and purification method of compound B5 were referred to, only the corresponding raw materials were changed, the target compound B81 (6.49 g, purity: 99.93%, yield: 76.52%) was obtained. After sublimation purification of 6.49 g of compound B81 crude product, sublimation compound B81 (4.01 g, purity: 99.95%, yield: 61.78%) was obtained, mass spectrum: 603.21 M+H).

[0579] 1 H NMR (400 MHz, CDCl3) δ 8.41-8.29 (m, 6H), 8.21-8.14 (m, 2H), 8.09 (d, J = 15.0 Hz, 1H), 8.06-7.88 (m, 4H), 7.83 (dd, J = 14.6, 3.3 Hz, 1H), 7.70-7.60 (m, 3H), 7.54-7.44 (m, 7H), 7.38 (dd, J = 14.8, 3.0 Hz, 1H), 7.25 (d, J = 14.9 Hz, 1H).

[0580] Synthesis of compound B101

[0581]

[0582] Synthesis of compound B101-2

[0583] Referring to the synthesis and purification method of compound B5-3, only the corresponding raw materials need to be changed to obtain the target compound B101-2 (4.47 g, purity: 99.12%, yield: 76.30%). Mass spectrum: 322.15 (M+H).

[0584] Synthesis of compound B101

[0585] Referring to the synthesis and purification method of compound B5, only the corresponding raw materials need to be changed to obtain the target compound B101 (5.28 g, purity: 99.91%, yield: 73.26%). After sublimation purification of 5.28 grams of compound B101 crude product, sublimation purified compound B101 (3.41 g, purity: 99.92%, yield: 64.58%) was obtained. Mass spectrum: 579.21 (M+H).

[0586] 1 H NMR (400 MHz, CDCl3) δ 8.21-8.15 (m, 2H), 8.09 (d, J = 2.9 Hz, 1H), 8.00-7.92 (m, 4H), 7.84 (d, J = 14.9 Hz, 1H), 7.80-7.71 (m, 5H), 7.69-7.60 (m, 3H), 7.54-7.36 (m, 6H), 7.29-7.22 (m, 4H).

[0587] Synthesis of compound C4

[0588]

[0589] Synthesis of compound C4

[0590] Referring to the synthesis and purification method of compound A1, only the corresponding raw materials need to be changed, to obtain the target compound C4 (6.52 g, purity: 99.97%, yield: 63.42%) as a light yellow solid, mass spectrum: 629.21 (M+H).

[0591] 1 H NMR (400 MHz, CDCl3) δ 8.88 (d, J = 3.1 Hz, 1H), 8.21-8.15 (m, 2H), 8.12-8.04 (m, 3H), 8.03 (d, J = 3.1 Hz, 1H), 8.01-7.89 (m, 4H), 7.76 (m, 4H), 7.67-7.57 (m, 5H), 7.57-7.51 (m, 4H), 7.48-7.43 (m, 2H), 7.43-7.35 (m, 4H), 7.35-7.27 (m, 2H).

[0592] Synthesis of compound C12

[0593]

[0594] Synthesis of compound C12

[0595] Referring to the synthesis and purification method of compound C4, only the corresponding raw materials need to be changed, to obtain the target compound C12 (8.41 g, purity: 99.93%, yield: 78.70%). After sublimation purification of 8.41 g of compound C12 crude product, sublimation purified compound C12 (5.19 g, purity: 99.94%, yield: 61.71%) was obtained, mass spectrum: 705.84 (M+H).

[0596] 1 H NMR (400 MHz, CDCl3) δ 8.88 (d, J = 3.1 Hz, 1H), 8.21-8.15 (m, 2H), 8.12-8.04 (m, 3H), 8.03 (d, J = 3.1 Hz, 1H), 8.01-7.89 (m, 4H), 7.76 (m, 4H), 7.67-7.57 (m, 5H), 7.57-7.51 (m, 4H), 7.48-7.43 (m, 2H), 7.43-7.35 (m, 4H), 7.35-7.27 (m, 2H).

[0597] Application Example: Preparation of an organic electroluminescent device

[0598] In an embodiment, as shown in Figure 2 Figure 2 ​The organic electroluminescent device structure schematic diagram, the organic electroluminescent device includes the glass substrate 1, the anode 2 (indium tin oxide), the hole injection layer 3, the first hole transport layer (HTL1) 4, the second hole transport layer (HTL2) 5, the light-emitting layer 6, the electron transport layer (ETL) 7, the electron injection layer 8 (EIL) and the cathode 9 arranged in layers.

[0599] The glass substrate with ITO (anode 2, indium tin oxide, 100 nm) transparent electrode of 50 mm*50 mm*1.0 mm is ultrasonically cleaned in ethanol for 10 minutes, and then dried at 150 DEG C and treated by N2 Plasma (plasma gas) for 30 minutes. The washed glass substrate is installed on the substrate support of a vacuum evaporation device, and compound NDP-9 and compound HTM 1 are evaporated to form a hole injection layer with a film thickness of 10 nm in a weight ratio of 97:3, followed by evaporating a layer of HTM1 to form a film with a film thickness of 60 nm as HTL1 (hole transport layer 1), and then evaporating a layer of HTM2 on the HTM1 film to form a film with a film thickness of 10 nm as HTL2 (hole transport layer 2), and then co-evaporating a light-emitting layer (host material: red dopant material = 97%:3%, mass fraction) with a film thickness of 40 nm on the HTM2 film in the form of a single host or multiple hosts, wherein the host materials of the single host or multiple hosts are the compound of the application and comparative compounds 1-4, respectively. The ETL (electron transport layer) material and LiQ are co-evaporated (35 nm) on the light-emitting layer as an electron transport material in a weight ratio of 50:50, followed by evaporating LiQ (1 nm) on the electron transport material layer as an electron injection material to form an electron injection layer, and then Mg / Ag (100 nm, mass ratio 1:9) is evaporated as a cathode material by co-evaporation, to obtain an organic electroluminescent device.

[0600] The structural formulas of NDP-9, HTM1, HTM2, ETL material, red dopant material, LiQ and comparative compounds 1-4 are as follows:

[0601]

[0602] Evaluation:

[0603] The above organic electroluminescent device is tested for device performance, and the compound prepared in the application and comparative compounds 1-4 are used as host materials for comparison. A constant current power supply (Keithley 2400) is used, a fixed current density is used to flow through the light-emitting element, and a spectroradiometer (CS2000) is used to test the luminescence spectrum. At the same time, the IVL (current-voltage-luminance) performance of the device is determined at 10 mA / cm 2 , and the LT95 device lifetime is tested at 50 mA / cm 2 . The results are shown in Tables 1 and 2.

[0604] The device performance data of the devices in which the compound of the present application is used as a double host, the comparative compound 1-4 is used as a single host or a double host (except that the mass ratio of A54 to B5 is 8:2 in Example 29 and the mass ratio of A54 to B5 is 2:8 in Example 30, and the mass ratio of the first host to the second host is 1:1 in the remaining examples and comparative examples) and co-evaporated with a red light dopant to form a light-emitting layer are shown in Table 1 (the examples in Table 1 use the compound of the present application, and the comparative examples use the comparative compound).

[0605] Table 1

[0606]

[0607]

[0608] The device data of the devices in which the first host compound, the second host compound and the third host compound in the present example are mixed by evaporation at a weight ratio of 2:1:1 (first host: second host: third host) and co-evaporated with a red light dopant to form a light-emitting layer are shown in Table 2.

[0609] Table 2

[0610]

[0611] As can be seen from Tables 1-2, the device prepared using the compound of the present application has significantly better efficiency and longer lifetime than the device prepared using the comparative compound 1-4.

[0612] Sublimation temperature comparison: The definition of sublimation temperature is: the temperature corresponding to a sublimation rate of 1 angstrom per second at a vacuum degree of 10 -7 Torr. The test results are shown in Table 3.

[0613] Table 3

[0614] Material Sublimation temperature / °C A1 252 A54 260 A226 257 A418 256 A515 262 B5 290 Comparative compound 1 273 Comparative compound 2 278 Comparative compound 3 284 Comparative compound 4 282

[0615] As can be seen from Table 3, the compound of the present application has a lower sublimation temperature than the comparative compound 1-4, which is beneficial to industrial application.

[0616] The compound of the present application as a double host red light material has lower voltage, higher current efficiency and longer lifetime than the comparative compound. Since the hole and electron transport rates are balanced, the exciton recombination region in the light-emitting layer is widened, which greatly improves the efficiency and lifetime of the device compared with Comparative Examples 1-6. Meanwhile, when the compound of the present application is used as a triple host material, the efficiency and lifetime of the device are greatly improved compared with Comparative Example 7.

[0617] Therefore, the compound material of the present application has the advantages of high photoelectric stability, low sublimation temperature, low driving voltage, high luminous efficiency, long device life, etc., and can be used as a host material in an OLED light-emitting device. At the same time, it has a relatively low melting point, which is beneficial to the stability of material evaporation as a melt-type material. The compound of the present application as a host material has the possibility of being applied to the AMOLED industry.

[0618] In addition, since it is impossible to enumerate all the compounds of the present application, the above Tables 1-3 only list the performance of some compounds or devices of the present application, but within the scope of the present application, in particular, the compounds of formula (1) specifically given by the structural formula of the present application are similar to A1, and the compounds of formula (2) specifically given by the structural formula of the present application are similar to B5, which have the advantages of high photoelectric stability, low sublimation temperature, low driving voltage, high luminous efficiency, long device life, etc.

Claims

1. A host material characterized in that, The host material is composed of at least one first host compound and at least one second host compound, wherein the first host compound is represented by the following formula (1): wherein ring A is selected from one of the following structures represented by formula (1-2) or formula (1-3); wherein X1-X 12 are each independently selected from CR0or N; and X1-X 12 contains at least one N, X1-X4, X 5- X6, X7-X8, X9-X 12 two adjacent positions are fused to the X-containing 5-membered ring of formula (1); Alternatively, ring A is selected from one of the following structures represented by formula (1-4) to formula (1-11): wherein * represents the site of fusion with the 5-membered ring containing X in formula (1); a is an integer from 0 to 10; if a is an integer from 2 to 10, each R0may be the same or different; each R0is independently selected from hydrogen, deuterium, cyano, C1-C20alkyl, C6-C30aryl, or C1-C20alkylsilyl; ring B is selected from one of the following structures represented by formula (1-20) to formula (1-26): wherein * represents the site of fusion with the 5-membered ring containing X in formula (1); R1is independently selected from hydrogen, deuterium, C1-C10alkyl, or C6-C30aryl; q is an integer from 0 to 10; if q is an integer from 2 to 10, each R1may be the same or different; X in formula (1) is selected from NR a , CR b R c or an oxygen group element; Ra is selected from C6-C18aryl, Rb, Rc are each independently selected from C1-C10alkyl; L is selected from a single bond, C6-C60arylene, or C3-C60heteroarylene; Ar1and Ar2are each independently selected from substituted or unsubstituted C6-C60aryl, substituted or unsubstituted C3-C60heteroaryl, or substituted or unsubstituted benzo C3-C6cycloalkyl, the substitution being deuterium, C1-C6alkyl, C3-C16cycloalkyl, or C6-C30aryl substitution, wherein the number of substitution is mono-substitution to the maximum number of substitution; The second host compound is represented by the following formula (2): wherein Z1, Z2, Z3are each independently selected from N or CH; L1, L2, L3are each independently selected from a single bond or C6-C30arylene; Ar3to Ar5each independently represent hydrogen, C1-C10alkyl, substituted or unsubstituted C6-C30aryl, substituted or unsubstituted C3-C30heteroaryl, or -N-(R’)(R”), wherein R’ and R” each independently represent C6-C30aryl or C3-C30heteroaryl; the substitution being C6-C20aryl substitution; and at least one of Ar3, Ar4, Ar5is selected from the following formula (3): wherein Y is selected from O, S, or Se; represents the point of attachment to L1, L2, L3 in formula (2); ring C is selected from a benzene ring, a naphthalene ring, or a phenanthrene ring; Ar6is selected from C6-C36aryl; the heteroatoms in the heteroarylene or heteroaryl are independently selected from at least one of O, S, N, Se, Si, or Ge.

2. The host material of claim 1, wherein, the structure represented by ring A is selected from one of the following structures represented by formula (1-12) to formula (1-19): wherein * represents the site of fusion with the 5-membered ring containing X in formula (1); a is an integer from 0 to 6; if a is an integer from 2 to 6, each R0may be the same or different.

3. The host material of claim 1, wherein, the L is selected from a single bond or one of the following structures represented by formula (4-1) to formula (4-17): the L1, L2, L3are each independently selected from a single bond or one of the following structures represented by formula (4-1), formula (4-3) to formula (4-14): wherein "*" indicates the position of the bond connection of L, L1, L2, L3.

4. The host material of claim 1, wherein, The ring C shown in the formula (3) is selected from one of the following structures shown in formula (1-20) to formula (1-26): wherein "*" indicates the position of the bond connection of L, L1, L2, L3.

5. The host material of claim 4, wherein, The ring C shown in the formula (3) is selected from one of the following structures shown in formula (1-20) to formula (1-26): wherein Ar6 is as defined in claim 1.

6. The host material of claim 1, wherein, each of Ar1to Ar2is independently selected from at least one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted 9,9-spirobifluorenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted substituted or unsubstituted carbazolyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted benzotriazolyl, substituted or unsubstituted benzophenanthrenyl, substituted or unsubstituted naphthoxazolyl, substituted or unsubstituted benzocyclohexyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted phenothiazinyl, oxaspirofluorenyl, or substituted or unsubstituted benzocarbazolyl; each of Ar3to Ar5is independently selected from at least one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted 9,9-spirobifluorenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted substituted or unsubstituted carbazoyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted benzotriazolyl, substituted or unsubstituted benzophenanthrenyl, substituted or unsubstituted naphthoxazolyl, substituted or unsubstituted phenanthroxazolyl, oxaspirofluorenyl, or substituted or unsubstituted benzocarbazolyl; said Ar6is selected from at least one of phenyl, biphenyl, naphthyl, anthryl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9,9-spirobi-fluorenyl, phenanthryl, pyrenyl, fluoranthene, triphenylenyl, chrysenyl, phenanthrenyl, 7. The host material of claim 1, wherein, wherein the compound represented by formula (1) is selected from one of the following structural formulae: The second host compound represented by formula (2) is selected from one of the following structural formulae:

8. An organic electroluminescent device, characterized by The host material is the host material according to any one of claims 1 to 7.

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