A compound and an organic electroluminescent device

Abstract

The present invention belongs to the technical field of organic electroluminescence, and discloses a compound and an organic electroluminescent device. The general structural formula of the compound is shown in Formula (1): #imgabs0# Formula (1); wherein: X is selected from NR a , CR b R c , O, S or Se; ET represents an electron-withdrawing group; L is selected from a single bond, a substituted or unsubstituted C6-C60 arylene group or a substituted or unsubstituted C3-C60 heteroarylene group; Ring A is selected from the structures shown in Formula (2) or Formula (3); #imgabs1# Formula (2) #imgabs2# Formula (3); X1-X 12 are each independently selected from CR0 or N; and two adjacent sites among X1-X4, X5-X6, X7-X8, X9-X 12 are fused to the 5-membered ring containing X in Formula (1). The compound has the advantages of high photo and electrical stability, low sublimation temperature, low driving voltage, high luminous efficiency, long device life, etc., and can be used as a red light host material in OLED light-emitting devices.

Description

Technical Field

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

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

[0003] Generally speaking, the basic structure of an OLED device is a thin film of organic functional materials with various functions sandwiched between metal electrodes, like a sandwich structure. Driven by current, holes and electrons are injected from the positive and negative poles respectively. After moving a certain distance, the holes and electrons are recombined in the light-emitting layer and released in the form of light or heat, thereby generating the light emission of the OLED. However, the properties of phosphorescent OLEDs are not only determined by the triplet light emitter used. Other types of materials, such as host materials, are also very important. The host material plays a significant role in reducing the driving voltage of the device, improving the luminous efficiency of the device, and increasing the service life of the device. Therefore, it is necessary to continue to develop new host materials to further improve the performance of organic electroluminescent devices.

[0004] In order to enhance the luminous efficiency, driving voltage, and life characteristics of OLED devices, various host materials for organic electroluminescent devices have been proposed. However, they are not satisfactory in actual use, and most of them have technical problems such as high driving voltage and sublimation temperature, which affect the luminous efficiency and life of the device. Therefore, there is a continuous demand for the development of host materials for improving OLED performance. Summary of the invention

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

[0006] In order to solve the above technical problems, the first aspect of the present invention provides a compound, whose general structural formula is shown in formula (1):

[0007]

[0008] Where: X is selected from NR a , CR b R c , O, S or Se;

[0009] R a , R b , Rc Each is independently selected from C1-C30 alkyl, C1-C30 heteroalkyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C3-C30 alkylsilyl, C6-C30 arylsilyl;

[0010] ET represents an electron-withdrawing group;

[0011] L is selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, or a substituted or unsubstituted C3-C60 heteroarylene group;

[0012] Ring A is selected from the structure represented by formula (2) or formula (3);

[0013]

[0014] X1-X 12 are independently selected from CR0 or N; and X1-X4, X5-X6, X7-X8, X9-X 12 There are two adjacent sites in the formula (1) that are fused to the 5-membered ring containing X;

[0015] R0 is selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphino, C6-C60 monoarylphosphino, C6-C60 diarylphosphino or C6-C60 arylamine; and two adjacent R0 may be connected to form a ring;

[0016] The substitution is substitution 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 from single substitution to the maximum number of substitutions.

[0017] In some embodiments, the R a , R b , R cEach is independently selected from C1-C20 alkyl, C1-C20 heteroalkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C20 aryl, C3-C20 heteroaryl, C3-C20 alkylsilyl and C6-C20 arylsilyl.

[0018] In some embodiments, the R a , R b , R c They are independently selected from C1-C10 alkyl, C1-C10 heteroalkyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C6-C10 aryl and C3-C10 heteroaryl.

[0019] In some embodiments, R0 is selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C30 alkyl, C1-C30 heteroalkyl, C2-C30 alkenyl, C2-C30 alkynyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C1-C30 alkoxy, C6-C30 aryloxy, C3-C30 alkylsilyl, C6-C30 arylsilyl, C1-C30 alkylboryl, C6-C30 arylboryl, C6-C30 arylphosphino, C6-C30 monoarylphosphino, C6-C30 diarylphosphino or C6-C30 arylamine; and two adjacent R0 can be connected to form a ring.

[0020] In some embodiments, R0 is selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C20 alkyl, C1-C20 heteroalkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C20 aryl, C3-C20 heteroaryl, C1-C20 alkoxy, C6-C20 aryloxy, C3-C20 alkylsilyl, C6-C20 arylsilyl, C1-C20 alkylboryl, C6-C20 arylboryl, C6-C20 arylphosphino, C6-C20 monoarylphosphino, C6-C20 diarylphosphino or C6-C20 arylamine; and two adjacent R0 can be connected to form a ring.

[0021] In some embodiments, the R0 is selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C10 alkyl, C1-C10 heteroalkyl, C2-C10 alkenyl, C2-C10 alkynyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C6-C12 aryl, C3-C12 heteroaryl; and two adjacent R0 can be connected to form a ring.

[0022] In some embodiments, adjacent R0 refers to R0 located on adjacent carbon atoms.

[0023] In some embodiments, the substitution is by at least one of deuterium, halogen, cyano, isocyano, phosphino, C1-C6 alkyl, C3-C12 cycloalkyl, C1-C6 alkyl-substituted amine, C6-C18 aryl, or C3-C18 heteroaryl, wherein the number of substitutions ranges from a single substitution to a maximum number of substitutions.

[0024] In some embodiments, the substitution is by at least one of deuterium, halogen, cyano, isocyano, phosphino, C1-C6 alkyl, C3-C10 cycloalkyl, C1-C6 alkyl-substituted amine, C6-C12 aryl, or C3-C12 heteroaryl, wherein the number of substitutions ranges from a single substitution to a maximum number of substitutions.

[0025] In some embodiments, the heteroatoms in the heteroaryl, heteroalkyl and heterocycloalkyl groups are independently selected from at least one of O, S, N, Se, Si and Ge.

[0026] In some embodiments, the structure represented by formula (2) or formula (3) is selected from the structures represented by formula (A-1) to (A-8):

[0027]

[0028] Wherein: * represents the site of fusion with the 5-membered ring containing X in formula (1);

[0029] m is an integer of 0-10; if m is an integer not less than 2, each R0 may be the same or different, and two adjacent R0 may be connected to form a ring.

[0030] In some embodiments, the structure represented by formula (2) or formula (3) is selected from the structures represented by formula (A-9) to (A-16):

[0031]

[0032] Wherein, * represents the site of fusion with the 5-membered ring containing X in formula (1);

[0033] t is an integer of 0-6; if t is an integer not less than 2, each R0 may be the same or different, and two adjacent R0 may be connected to form a ring.

[0034] In some embodiments, the electron withdrawing group is selected from the structures shown in formula (B-1) to (B-10):

[0035]

[0036]

[0037] Wherein: * represents the site of connection with L in formula (1);

[0038] Z is selected from N or CR d , and at least one Z is N, and two adjacent Zs in formula (B-10) are not N at the same time;

[0039] W is selected from NR e 、O、S、SO、SO2、CR f R g or SiR h R j ;

[0040] Y is selected from NR a , CR b R c , O, S or Se, and Ra, R b , R c R of X in claim 1 a , R b , R c The definition is consistent;

[0041] R1, R d -R h , R j are independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C1-C40 alkoxy substituted or unsubstituted C a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C3-C60 heteroaryl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylboryl group, a substituted or unsubstituted C6-C60 arylphosphyl group, a substituted or unsubstituted C6-C60 monoarylphosphino group, a substituted or unsubstituted C6-C60 diarylphosphino group, or a substituted or unsubstituted C6-C60 arylamine group;

[0042] The substitution is substituted by 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 ranges from single substitution to the maximum number of substitutions;

[0043] n is an integer of 0-10; if n is an integer not less than 2, each R1 may be the same or different, and two adjacent R1 may be connected to form a ring.

[0044] In some embodiments, adjacent R1 refers to R1 located on adjacent carbon atoms.

[0045] In some embodiments, the R d -R h , R j are independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C30 alkyl, C1-C30 heteroalkyl, C2-C30 alkenyl, C2-C30 alkynyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C3-C30 alkylsilyl, C6-C30 arylsilyl, C1-C30 alkylboryl, C1-C30 alkoxy substituted or unsubstituted C The present invention may include a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C6-C30 arylboronyl group, a substituted or unsubstituted C6-C30 arylphosphinyl group, a substituted or unsubstituted C6-C30 monoarylphosphinyl group, a substituted or unsubstituted C6-C30 diarylphosphinyl group or a substituted or unsubstituted C6-C30 arylamine group.

[0046] In some embodiments, the R d -R h , R j are independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C20 alkyl, C1-C20 heteroalkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C3-C20 alkylsilyl, C6-C20 arylsilyl, C1-C20 alkylboryl, C1-C20 alkoxy substituted or unsubstituted C The present invention may include a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C20 heteroaryl group, a substituted or unsubstituted C6-C20 aryloxy group, a substituted or unsubstituted C6-C20 arylboronyl group, a substituted or unsubstituted C6-C20 arylphosphinyl group, a substituted or unsubstituted C6-C20 monoarylphosphinyl group, a substituted or unsubstituted C6-C20 diarylphosphinyl group or a substituted or unsubstituted C6-C20 arylamine group.

[0047] In some embodiments, the R d -R h , R jare independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C10 alkyl, C1-C10 heteroalkyl, C2-C10 alkenyl, C2-C10 alkynyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C3-C10 alkylsilyl, C6-C10 arylsilyl, C1-C10 alkylboryl, C1-C10 alkoxy substituted or unsubstituted C The present invention may include a substituted or unsubstituted C6-C10 aryl group, a substituted or unsubstituted C3-C10 heteroaryl group, a substituted or unsubstituted C6-C10 aryloxy group, a substituted or unsubstituted C6-C10 arylboronyl group, a substituted or unsubstituted C6-C10 arylphosphinyl group, a substituted or unsubstituted C6-C10 monoarylphosphinyl group, a substituted or unsubstituted C6-C10 diarylphosphinyl group or a substituted or unsubstituted C6-C10 arylamine group.

[0048] In some embodiments, the R d -R h , R j They are each independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C10 alkyl, C1-C10 heteroalkyl, C2-C10 alkenyl, C2-C10 alkynyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C6-C10 aryl, C3-C10 heteroaryl, C6-C10 aryloxy, C6-C10 arylboronyl, C6-C10 arylphosphinyl, C6-C10 monoarylphosphinyl, C6-C10 diarylphosphinyl or C6-C10 arylamine.

[0049] In some embodiments, the electron withdrawing group is selected from the structures shown in formula (B-11) to (B-36):

[0050]

[0051] Wherein: R1 and R2 are independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C1-C40 alkoxy substituted or unsubstituted a substituted C6-C60 aryl group, a substituted or unsubstituted C3-C60 heteroaryl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylboronyl group, a substituted or unsubstituted C6-C60 arylphosphinyl group, a substituted or unsubstituted C6-C60 monoarylphosphinyl group, a substituted or unsubstituted C6-C60 diarylphosphinyl group or a substituted or unsubstituted C6-C60 arylamine group.

[0052] In some embodiments, R1 and R2 are independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C30 alkyl, C1-C30 heteroalkyl, C2-C30 alkenyl, C2-C30 alkynyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C3-C30 alkylsilyl, C6-C30 arylsilyl, C1-C30 alkylboryl, C1-C30 alkoxy a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C6-C30 arylboronyl group, a substituted or unsubstituted C6-C30 arylphosphinyl group, a substituted or unsubstituted C6-C30 monoarylphosphinyl group, a substituted or unsubstituted C6-C30 diarylphosphinyl group or a substituted or unsubstituted C6-C30 arylamine group.

[0053] In some embodiments, R1 and R2 are independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C20 alkyl, C1-C20 heteroalkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C3-C20 alkylsilyl, C6-C20 arylsilyl, C1-C20 alkylboryl, C1-C20 alkoxy a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C20 heteroaryl group, a substituted or unsubstituted C6-C20 aryloxy group, a substituted or unsubstituted C6-C20 arylboronyl group, a substituted or unsubstituted C6-C20 arylphosphinyl group, a substituted or unsubstituted C6-C20 monoarylphosphinyl group, a substituted or unsubstituted C6-C20 diarylphosphinyl group or a substituted or unsubstituted C6-C20 arylamine group.

[0054] In some embodiments, R1 and R2 are independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C10 alkyl, C1-C10 heteroalkyl, C2-C10 alkenyl, C2-C10 alkynyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C3-C10 alkylsilyl, C6-C10 arylsilyl, C1-C10 alkylboryl, C1-C10 alkoxy a substituted or unsubstituted C6-C10 aryl group, a substituted or unsubstituted C3-C10 heteroaryl group, a substituted or unsubstituted C6-C10 aryloxy group, a substituted or unsubstituted C6-C10 arylboryl group, a substituted or unsubstituted C6-C10 arylphosphyl group, a substituted or unsubstituted C6-C10 monoarylphosphino group, a substituted or unsubstituted C6-C10 diarylphosphino group or a substituted or unsubstituted C6-C10 arylamine group.

[0055] In some embodiments, R1 and R2 are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C6-C20 arylene or substituted or unsubstituted C3-C20 heteroarylene; and each R1 may be the same or different, and two adjacent R1s may be connected to form a ring.

[0056] In some embodiments, R1 and R2 are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted phenyl, 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 spirobifluorenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted The invention may be a substituted or unsubstituted carbazolyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted fluoranthene, a substituted or unsubstituted benzoxazolyl, a substituted or unsubstituted benzimidazolyl, a substituted or unsubstituted benzotriazolyl, a substituted or unsubstituted triphenylene radical, a substituted or unsubstituted naphthoxazolyl, a substituted or unsubstituted phenanthroxazolyl, a substituted or unsubstituted quinolyl, a substituted or unsubstituted benzocycloalkyl, a substituted or unsubstituted benzocarbazolyl, a substituted or unsubstituted naphthobenzofuranyl, a substituted or unsubstituted azaphenanthrenyl, or a combination of at least two of the foregoing.

[0057] In some embodiments, X is selected from CR b R c , O or S; and R in X b , R c They are each independently selected from C1-C10 alkyl, C1-C10 heteroalkyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C6-C10 aryl or C3-C10 heteroaryl.

[0058] In some embodiments, L is selected from a single bond, a substituted or unsubstituted C6-C20 arylene group, or a substituted or unsubstituted C3-C20 heteroarylene group.

[0059] In some embodiments, the L is selected from a single bond or structures represented by formula (L-1) to formula (L-14):

[0060]

[0061]

[0062] Wherein: R is a substituent, each R is independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C20 alkyl, C1-C20 heteroalkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C1-C20 alkoxy, C6-C30 aryloxy, C3-C20 alkylsilyl, C6-C30 arylsilyl, C1-C20 alkylboryl, C6-C30 arylboryl, C6-C30 arylphosphino, C6-C30 monoarylphosphino, C6-C30 diarylphosphino or C6-C30 arylamine; wherein the number of substitutions is from a single substitution to the maximum number of substitutions.

[0063] In some embodiments, R is a substituent, each R is independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C10 alkyl, C1-C10 heteroalkyl, C2-C10 alkenyl, C2-C10 alkynyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C6-C20 aryl, C3-C20 heteroaryl, C1-C10 alkoxy, C6-C20 aryloxy, C3-C10 alkylsilyl, C6-C20 arylsilyl, C1-C10 alkylboryl, C6-C20 arylboryl, C6-C20 arylphosphino, C6-C20 monoarylphosphino, C6-C20 diarylphosphino or C6-C20 arylamine; wherein the number of substitutions is from monosubstitution to the maximum number of substitutions.

[0064] In some embodiments, the structural formula of the compound is one of the structural formulas shown in formulas CPD1 to CPD645, or a structure in which hydrogen in formulas CPD1 to CPD645 is partially or completely replaced by deuterium, or a structure in which hydrogen in formulas CPD1 to CPD645 is partially or completely replaced by fluorine:

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084] A second aspect of the present invention provides an organic electroluminescent device, comprising a light-emitting layer, wherein the light-emitting layer comprises the above compound.

[0085] In some embodiments, the organic electroluminescent device comprises a cathode, an anode and a light-emitting layer, wherein the cathode and the anode are arranged opposite to each other, the light-emitting layer is arranged between the cathode and the anode, and the light-emitting layer comprises the above-mentioned organic electroluminescent compound. The organic electroluminescent compound of the present invention can be used alone or after doping to prepare the light-emitting layer.

[0086] In some embodiments, the light-emitting layer is a red light-emitting layer, and the red light-emitting layer includes a red light-emitting material and at least one of the above-mentioned organic electroluminescent compounds. The organic electroluminescent compound of the present invention is used as a main material of the red light-emitting layer.

[0087] Compared with the prior art, the above technical solution of the present invention has at least the following technical effects or advantages:

[0088] The compound synthesized by the present invention has the advantages of high optical and electrical stability, low sublimation temperature, low driving voltage, high luminous efficiency, long device life, etc., and can be used as a red light main material in an OLED light-emitting device. At the same time, the compound synthesized by the present invention has a low melting point, and as a molten material, it is beneficial to the stability of material evaporation. It is used as a main material and has the possibility of being applied to the active matrix organic light-emitting diode (AMOLED) industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0089] Figure 1The compound CPD59 of the present invention 1 H NMR spectrum;

[0090] Figure 2 FIG. 4 is a schematic structural diagram of an organic electroluminescent device according to an embodiment of the present invention. DETAILED DESCRIPTION

[0091] The present invention is described in detail below in conjunction with the examples, so that the technical personnel of the relevant technical field can understand the present invention. It is necessary to point out here that the examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. The non-essential improvements and adjustments made to the present invention by the skilled person in the relevant field according to the above invention content should still belong to the scope of protection of the present invention. At the same time, the raw materials mentioned below that are not described in detail are all commercially available products; the process steps or preparation methods that are not mentioned in detail are all process steps or preparation methods known to those skilled in the art.

[0092] A compound, the general structural formula of which is shown in formula (1):

[0093]

[0094] Where: X is selected from NR a , CR b R c , O, S or Se;

[0095] R a , R b , R c Each is independently selected from C1-C30 alkyl, C1-C30 heteroalkyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C3-C30 alkylsilyl, C6-C30 arylsilyl;

[0096] ET represents an electron-withdrawing group;

[0097] L is selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, or a substituted or unsubstituted C3-C60 heteroarylene group;

[0098] Ring A is selected from the structure represented by formula (2) or formula (3);

[0099]

[0100] X1-X 12 are independently selected from CR0 or N; and X1-X4, X5-X6, X7-X8, X9-X 12 There are two adjacent sites in the formula (1) that are fused to the 5-membered ring containing X;

[0101] R0 is selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphino, C6-C60 monoarylphosphino, C6-C60 diarylphosphino or C6-C60 arylamine; and two adjacent R0 may be connected to form a ring;

[0102] The substitution is substitution 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 from single substitution to the maximum number of substitutions.

[0103] Hereinafter, each group of the compound represented by formula (1), (2) and (3) will be described.

[0104] It should be noted that in the present invention, the "carbon number ab" in the expression "substituted or unsubstituted X group having ab carbon numbers" means the carbon number when the X group is unsubstituted, and does not include the carbon number of the substituent when the X group is substituted.

[0105] Specific examples of C1-C10 alkyl groups are linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl and its isomers, n-hexyl and its isomers, n-heptyl and its isomers, n-octyl and its isomers, n-nonyl and its isomers, n-decyl and its isomers, etc.; preferably, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl; more preferably, propyl, isopropyl, isobutyl, sec-butyl and tert-butyl.

[0106] Specific examples of the C3-C20 cycloalkyl group include propyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like, and cyclopentyl and cyclohexyl are preferred.

[0107] Specific examples of the C2-C10 alkenyl group include vinyl, propenyl, allyl, 1-butadienyl, 2-butadienyl, 1-hexatrienyl, 2-hexatrienyl, 3-hexatrienyl and the like, and propenyl and allyl are preferred.

[0108] Specific examples of C1-C10 heteroalkyl groups include straight-chain or branched alkyl groups, cycloalkyl groups, etc. consisting of atoms other than carbon and hydrogen, and include mercaptomethylmethane, methoxymethane, ethoxymethane, tert-butoxymethane, N,N-dimethylmethane, butylene oxide, cyclopentyl, hexyl oxide, etc.; preferably, methoxymethane and cyclopentyl oxide.

[0109] Specific examples of the aryl group include phenyl, naphthyl, anthracenyl, phenanthrenyl, tetraphenyl, pyrene, chrysene, benzo[c]phenanthrenyl, benzo[g]chrysene, fluorenyl, benzofluorenyl, dibenzofluorenyl, biphenyl, terphenyl, quaterphenyl, and fluoranthenyl, preferably phenyl and naphthyl.

[0110] Specific examples of the heteroaryl group include pyrrolyl, pyrazinyl, pyridyl, pyrimidinyl, triazine, indolyl, isoindolyl, imidazolyl, furyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, azadibenzofuranyl, azadibenzothiophenyl, diazadibenzofuranyl, diazadibenzothiophenyl, quinolyl, isoquinolyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxazinyl, oxazinyl, The following examples are only for the convenience of understanding the technical invention and should not be regarded as specific limitations of the present invention.

[0111] The raw materials and solvents involved in the synthesis of the compounds of the present invention were purchased from suppliers such as Alfa and Acros, which are well known to those skilled in the art.

[0112] Synthesis of compound CPD29

[0113] The synthetic route is:

[0114]

[0115] Synthesis of compound CPD29-3

[0116] CPD29-1 (30.00 g, 106.56 mmol), CPD29-2 (32.47 g, 127.87 mmol), 1,1-bis(diphenylphosphine)dichloropalladium iron (1.56 g, 2.13 mmol), potassium acetate (15.69 g, 159.84 mmol), and 1,4-dioxane (450 ml) were added to a 1000 ml three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. Then, the system was heated to 100 ° C and reacted for 2 hours. The reaction was monitored by TLC (ethyl acetate: n-hexane = 1:10 as the developing solvent). The raw material CPD29-1 was consumed.

[0117] The temperature was lowered to 60°C, and the solvent was removed by concentration under reduced pressure. Ethyl acetate (700 ml) was added, and the mixture was washed three times with deionized water (300 ml*3). The mixture was separated, and the sample was mixed with silica gel and dry-loaded onto a column. Purification was performed by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate:n-hexane=1:15 as eluent). After elution, the mixture was concentrated under reduced pressure at 70°C for 1 hour to obtain a white solid CPD29-3 (27.62 g, purity: 98.05%, yield: 77.07%), mass spectrum: 329.12 (M+H).

[0118] Synthesis of compound CPD29-5

[0119] CPD29-3 (25.00 g, 76.08 mmol), CPD29-4 (17.89 g, 76.08 mmol), tetrakis(triphenylphosphine)palladium (1.75 g, 1.52 mmol), potassium carbonate (15.77 g, 114.12 mmol), tetrahydrofuran (375 ml), and deionized water (125 ml) were added to a 1000 ml three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. Then, the system was heated to 75 ° C for 3 hours. The reaction was monitored by TLC (ethyl acetate: n-hexane = 1:10 as the developing solvent). The raw material CPD29-3 was consumed.

[0120] The temperature was lowered to 60°C, and the solvent was removed by concentration under reduced pressure. Ethyl acetate (700 ml) was added, and the mixture was washed three times with deionized water (300 ml*3). The mixture was separated, and the sample was mixed with silica gel and dry-loaded onto a column. Purification was performed by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate:n-hexane=1:20 as eluent). After elution, the mixture was concentrated under reduced pressure at 70°C for 2 hours to obtain a white solid CPD29-5 (20.45 g, purity: 99.23%, yield: 74.33%), mass spectrum: 357.22 (M+H).

[0121] Synthesis of compound CPD29-7

[0122] CPD29-5 (18.00 g, 50.45 mmol), CPD29-6 (25.94 g, 75.67 mmol), and tetrahydrofuran (270 ml) were added to a 1000 ml three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. Then the system was cooled to 5 ° C, and sodium methoxide (5.45 g, 100.90 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 the developing solvent). The raw material CPD29-5 was consumed.

[0123] Deionized water (500 ml) was added, the solvent was removed by concentration under reduced pressure, ethyl acetate (700 ml) was added for extraction, the layers were separated, and the mixture was concentrated under reduced pressure at 70° C. for 1 hour to obtain a white solid CPD29-7 (18.44 g, yield: 95.00%), mass spectrum: 385.04 (M+H). The obtained compound was used directly in the next step without purification.

[0124] Synthesis of compound CPD29-8

[0125] CPD29-7 (17.00 g, 44.17 mmol) and toluene (170 ml) were added to a 500 ml three-necked round-bottom flask, and the vacuum was replaced with nitrogen three times. Then the system was cooled to 5°C, and methanesulfonic acid (8.49 g, 88.34 mmol) was slowly added dropwise. The addition was completed within 3 minutes, and the reaction was maintained at 5°C for 1 hour. The reaction was monitored by TLC (ethyl acetate: n-hexane = 1:15 as the developing solvent). The raw material CPD29-7 was consumed.

[0126] Methanol (200 ml) was added thereto, and a large amount of white solid precipitated. 17 g of solid was obtained by filtration. The solid was crystallized once with toluene (204 ml) and methanol (170 ml). The filter cake was vacuum dried at 80°C for 1 hour to obtain a white solid CPD29-8 (11.63 g, purity: 99.83%, yield: 74.62%), mass spectrum: 353.06 (M+H).

[0127] Synthesis of compound CPD29-9

[0128] Referring to the synthesis and purification method of compound CPD29-3, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD29-9 (14.22 g, purity: 99.02%, yield: 77.63%), mass spectrum: 445.20 (M+H).

[0129] Synthesis of compound CPD29

[0130] Referring to the synthesis and purification method of compound CPD29-5, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD29 (12.02 g, purity: 99.96%, yield: 75.33%). 12.02 g of crude CPD29 was purified by sublimation to obtain sublimation pure CPD29 (9.23, purity: 99.95%, yield: 78.78%), mass spectrum: 665.25 (M+H).

[0131] 1 HNMR(400MHz, CDCl3)δ8.25(d,J=2.5Hz,1H),8.19-8.14(m,2H),8.07-8.02(m,1H),8.00(d,J=8.6Hz,1H),7.98-7.94( m,2H),7.94-7.88(m,5H),7.87-7.82(m,4H),7.55-7.43(m,8H),7.38-7.35(m,1H),7.32(d,J=7.3Hz,1H),1.74(s,6H).

[0132] Synthesis of compound CPD59

[0133] The synthetic route is:

[0134]

[0135] Compound CPD25-9 (20.00 g, 45.01 mmol), CPD59-1 (16.10 g, 45.01 mmol), tetrakis(triphenylphosphine)palladium (1.04 g, 0.90 mmol), sodium hydroxide (3.6 g, 90.02 mmol), tetrahydrofuran (300 ml), and deionized water (100 ml) were added to a 1000 ml three-necked round-bottom flask, and the atmosphere was replaced with vacuum nitrogen three times, and the temperature was raised to 75°C for 6 hours. TLC (ethyl acetate: n-hexane = 1:10 as the developing solvent) was used to monitor the complete consumption of the raw material CPD25-9.

[0136] After cooling to room temperature, methanol (200 ml) was added and stirred at room temperature for 30 minutes, and a yellow solid was obtained by suction filtration. Xylene (600 ml) was added, and the mixture was heated to 120°C to dissolve the material, and the mixture was cooled to room temperature and filtered once with column chromatography silica gel (50 g, 200-300 mesh). The filter cake was rinsed with 300 ml of toluene until no product remained. The organic phases were combined and concentrated under reduced pressure at 70°C to obtain a yellow solid, which was crystallized twice with xylene and methanol, and dried under vacuum at 100°C for 8 hours to obtain a yellow solid compound CPD59 (21.69 g, purity: 99.97%, yield: 75.33%). 21.69 g of crude CPD59 was purified by sublimation to obtain sublimation pure CPD59 (15.93 g, purity: 99.97%, yield: 73.44), mass spectrum: 640.12 (M+H).

[0137] 1 H NMR (400MHz, CDCl3) δ8.26(d,J=2.5Hz,1H),8.17(d,J=9.1Hz,1H),8.11-8.00(m,4H),7.94(dd,J=8.6,2.0Hz,2H),7.91-7.82(m,5 H),7.65-7.60(m,1H),7.60-7.53(m,2H),7.53-7.47(m,5H),7.47-7.39(m,2H),7.32(d,J=7.3Hz,1H),7.26(dd,J=9.3,6.8Hz,1H).

[0138] Synthesis of compound CPD63

[0139] The synthetic route is:

[0140]

[0141] Synthesis of compound CPD63-2

[0142] Referring to the synthesis and purification method of compound CPD25-3, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD63-2 (28.79 g, purity: 99.02%, yield: 76.82%), mass spectrum: 329.12 (M+H).

[0143] Synthesis of compound CPD63-3

[0144] Referring to the synthesis and purification method of compound CPD25-5, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD63-3 (25.03 g, purity: 99.43%, yield: 73.96%), mass spectrum: 357.22 (M+H).

[0145] Synthesis of compound CPD63-4

[0146] Referring to the synthesis and purification method of compound CPD25-7, only the corresponding raw materials need to be changed to obtain the target compound CPD63-4 (23.02 g, yield: 95.98%) as a white solid, mass spectrum: 385.04 (M+H). The obtained compound was used directly in the next step without purification.

[0147] Synthesis of compound CPD63-5

[0148] Referring to the synthesis and purification method of compound CPD25-8, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD63-5 (16.66 g, purity: 99.85%, yield: 74.63%), mass spectrum: 353.06 (M+H).

[0149] Synthesis of compound CPD63-6

[0150] Referring to the synthesis and purification method of compound CPD25-9, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD63-6 (15.00 g, purity: 99.03%, yield: 75.05%), mass spectrum: 445.12 (M+H).

[0151] Synthesis of compound CPD63

[0152] Referring to the synthesis and purification method of compound CPD59, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD63 (15.63 g, purity: 99.97%, yield: 74.65%). 15.63 grams of crude CPD63 was sublimated and purified to obtain sublimation pure CPD63 (13.00 g, purity: 99.96%, yield: 83.17%), mass spectrum: 626.22 (M+H).

[0153] 1 H NMR (400MHz, CDCl3) δ8.21(d,J=9.7Hz,1H),8.17(d,J=9.1Hz,1H),8.13-8.00(m,3H),7.98-7.91(m,5H),7.91- 7.83(m,3H),7.73-7.66(m,3H),7.64-7.54(m,2H),7.54-7.47(m,5H),7.47-7.38(m,3H),7.32(d,J=7.3Hz,1H).

[0154] Synthesis of compound CPD77

[0155] The synthetic route is:

[0156]

[0157] Synthesis of compound CPD77-3

[0158] Compound CPD77-1 (20.00 g, 88.47 mmol), CPD77-2 (28.42 g, 88.47 mmol), tetrakis(triphenylphosphine)palladium (1.07 g, 0.88 mmol), potassium carbonate (24.45 g, 176.94 mmol), tetrahydrofuran (400 ml), and deionized water (120 ml) were added to a 1000 ml three-necked round-bottom flask, and the atmosphere was replaced with vacuum nitrogen three times, and the temperature was raised to 50°C for reaction for 8 hours. TLC (ethyl acetate: n-hexane = 1:20 as the developing solvent) was used to monitor the complete consumption of the raw material CPD77-1.

[0159] After the reaction solution cooled to room temperature, deionized water (700 ml) was added and stirred at room temperature for 30 minutes, and then filtered with suction, and the filter cake was rinsed with deionized water (200 ml). The filter cake was heated to 80°C with tetrahydrofuran (2000 ml) and stirred to dissolve, filtered once with a chromatography column silica gel (20 g, 200-300 mesh), rinsed with THF (200 ml), and the filtrate was concentrated at 65°C for 2 hours to obtain a light yellow solid, which was crystallized once with tetrahydrofuran and methanol, and dried under vacuum at 80°C for 10 hours to obtain a light yellow solid CPD77-3 (25.57 g, purity: 99.62%, yield: 75.11%), mass spectrum: 385.02 (M+H).

[0160] Synthesis of compound CPD77

[0161] Referring to the synthesis and purification method of compound CPD59, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD77 (18.09 g, purity: 99.95%, yield: 75.74%). 18.09 grams of crude CPD77 was sublimated and purified to obtain sublimation pure CPD77 (14.85 g, purity: 99.95%, yield: 82.09%), mass spectrum: 667.32 (M+H).

[0162] 1 HNMR(400MHz, CDCl3)δ8.21(d,J=9.7Hz,1H),8.17(d,J=9.1Hz,1H),8.12-8.05(m,2H),8.05-8.01(m,1H),7.99-7 .87(m,8H),7.87-7.82(m,3H),7.69(d,J=2.2Hz,1H),7.55-7.47(m,6H),7.47-7.39(m,2H),7.32(d,J=7.3Hz,1H).

[0163] Synthesis of compound CPD119

[0164] The synthetic route is:

[0165]

[0166] Synthesis of compound CPD119-2

[0167] Referring to the synthesis and purification method of compound CPD25-5, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD119-2 (24.25 g, purity: 99.68%, yield: 78.08%), mass spectrum: 519.11 (M+H).

[0168] Synthesis of compound CPD119

[0169] CPD119-2 (20.00 g, 38.54 mmol), CPD77-2 (12.38 g, 38.54 mmol), bis(4-dimethylaminophenyldi-tert-butylphosphine)palladium dichloride (0.23 g, 0.38 mmol), potassium carbonate (10.65 g, 77.08 mmol), toluene (300 ml), ethanol (100 ml), and deionized water (100 ml) were added to a 1000 ml three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. Then, the system was heated to 65 ° C for 2 hours. The reaction was monitored by TLC (ethyl acetate: n-hexane = 1:10 as the developing solvent). The raw material CPD119-2 was consumed.

[0170] Cool to room temperature, add methanol (300ml), stir at room temperature for 1 hour, and a large amount of solid precipitates. Add toluene (450ml), heat the system to 100℃ and dissolve, cool to room temperature, filter once with 200-300 mesh silica gel (20g), add methanol (450ml) to the filtrate at room temperature, stir at room temperature for 1 hour, filter to obtain a white solid wet product, dry at 100℃ for 1 hour to obtain a light yellow solid; crystallize twice with toluene and methanol, filter, and vacuum dry the filter cake at 100℃ for 10 hours to obtain a yellow solid CPD119 (18.83g, purity: 99.98%, yield: 72.11%). 18.83 grams of crude CPD119 was sublimated and purified to obtain sublimation pure CPD119 (14.88g, purity: 99.98%, yield: 79.03%), mass spectrum: 678.24 (M+H).

[0171] 1H NMR (400MHz, CDCl3) δ8.23 (d, J=2.4Hz, 1H), 8.17 (dd, J=8.5, 4.2Hz, 2H), 8.07-8.01 (m, 2H), 7.98-7.87 (m, 6H), 7.85 (dd, J=7.6, 3.0Hz, 2H), 7.76 (dd, J= 7.2,2.4Hz,2H),7.70(d,J=2.0Hz,1H),7.62(dd,J=7.8,2.1Hz,1H),7.60-7 .47(m,5H),7.47-7.40(m,3H),7.37(d,J=7.4Hz,1H),7.32(d,J=7.3Hz,1H).

[0172] Synthesis of compound CPD125

[0173] The synthetic route is:

[0174]

[0175] Referring to the synthesis and purification method of compound CPD119, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD125 (12.63 g, purity: 99.94%, yield: 73.63%). 12.63 g of crude CPD125 was purified by sublimation to obtain sublimation pure CPD125 (10.01 g, purity: 99.94%, yield: 79.25%), mass spectrum: 587.20 (M+H).

[0176] 1 H NMR (400MHz, CDCl3) δ8.64 (d, J = 7.2Hz, 1H), 8.21-8.13 (m, 2H), 8.11 (d, J = 8. 3Hz,1H),8.07-8.02(m,1H),7.94(dd,J=8.6,2.0Hz,2H),7.92-7.87(m,1H),7 .85(dd,J=7.6,3.0Hz,2H),7.72-7.64(m,4H),7.62(dd,J=8.3,2.1Hz,1H),7. 54(d,J=2.2Hz,1H),7.53-7.48(m,2H),7.48-7.40(m,6H),7.37-7.29(m,2H).

[0177] Synthesis of compound CPD137

[0178]

[0179] Synthesis of compound CPD137

[0180] Referring to the synthesis and purification method of compound CPD119, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD137 (14.96 g, purity: 99.95%, yield: 71.09%). 14.96 grams of crude CPD137 was purified by sublimation to obtain sublimation pure CPD137 (10.06 g, purity: 99.95%, yield: 67.25%), mass spectrum: 497.26 (M+H).

[0181] 1 H NMR (400MHz, CDCl3) δ8.93(dd,J=4.1,2.1Hz,1H),8.84(dd,J=3.9,1.7Hz,1H),8.33(dd,J=7.6,2.1Hz,1H),8.28(d,J=2 .1Hz,1H),8.18(dd,J=9.6,8.5Hz,2H),8.12-8.01(m,2H),7.97-7.82(m,5H),7.59-7.45(m,6H),7.32(d,J=7.3Hz,1H).

[0182] Synthesis of compound CPD139

[0183] The synthetic route is:

[0184]

[0185] Referring to the synthesis and purification method of compound CPD119, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD139 (15.00 g, purity: 99.96%, yield: 76.63%). 15.00 g of crude CPD139 was purified by sublimation to obtain sublimation pure CPD139 (12.05 g, purity: 99.96%, yield: 80.33%), mass spectrum: 546.18 (M+H).

[0186] 1 H NMR (400MHz, CDCl3) δ8.82(dd,J=4.1,2.1Hz,1H),8.61(dd,J=7.6,2.1Hz,1H),8.54(dd,J=5.7,3.1Hz,1H),8.28(d,J=2.3Hz,1H),8.20 -8.12(m,2H),8.07-8.01(m,3H),7.97-7.82(m,5H),7.74-7.71(m,2H),7.57-7.46(m,5H),7.43(d,J=7.2Hz,1H),7.32(d,J=7.3Hz,1H).

[0187] Synthesis of compound CPD146

[0188] The synthetic route is:

[0189]

[0190] Synthesis of compound CPD146-2

[0191] Referring to the synthesis and purification method of compound CPD25-3, only the corresponding raw materials need to be changed to obtain the target compound CPD146-2 (25.98 g, purity: 99.02%, yield: 75.63%) as a white solid, with a mass spectrum of 322.15 (M+H).

[0192] Referring to the synthesis and purification method of compound CPD25-5, only the corresponding raw materials need to be changed to obtain the target compound CPD146-4 (22.02 g, purity: 99.52%, yield: 72.63%) as a white solid, with a mass spectrum of 334.06 (M+H).

[0193] Referring to the synthesis and purification method of compound CPD25-7, only the corresponding raw materials need to be changed to obtain the target compound CPD146-5 (21.06 g, yield: 97.65%) as a white solid, mass spectrum: 362.08 (M+H). The obtained compound was used directly in the next step without purification.

[0194] Synthesis of compound CPD146-6

[0195] Referring to the synthesis and purification method of compound CPD25-8, it is only necessary to change the corresponding raw materials to obtain the white solid as the target compound CPD146-6 (17.06 g, purity: 99.81%, yield: 72.96%), mass spectrum: 330.02 (M+H).

[0196] Synthesis of compound CPD146-7

[0197] Referring to the synthesis and purification method of compound CPD25-9, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD146-7 (15.06 g, purity: 99.23%, yield: 78.03%), mass spectrum: 422.18 (M+H).

[0198] Synthesis of compound CPD146-8

[0199] Referring to the synthesis and purification method of compound CPD77-3, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD146-8 (16.86 g, purity: 99.59%, yield: 74.96%), mass spectrum: 485.12 (M+H).

[0200] Synthesis of compound CPD146

[0201] Referring to the synthesis and purification method of compound CPD59, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD146 (18.88 g, purity: 99.95%, yield: 72.63%). 18.88 g of crude CPD146 was purified by sublimation to obtain sublimation pure CPD146 (14.73 g, purity: 99.96%, yield: 78.02%), mass spectrum: 767.24 (M+H).

[0202] 1 H NMR (400MHz, CDCl3) δ8.28(d,J=2.2Hz,1H),8.21(d,J=9.7Hz,1H),8.17(d,J=9.1Hz,1H),8.11-8.00(m,7H),8.00-7.96(m,1H),7 .96-7.87(m,7H),7.85(dd,J=7.6,3.0Hz,2H),7.69(d,J=2.4Hz,1H),7.54-7.46(m,6H),7.46-7.40(m,2H),7.32(d,J=7.3Hz,1H).

[0203] Synthesis of compound CPD169

[0204] The synthetic route is:

[0205]

[0206] Synthesis of compound CPD169-2

[0207] Referring to the synthesis and purification method of compound CPD25-3, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD169-2 (23.33 g, purity: 99.08%, yield: 77.06%), mass spectrum: 329.10 (M+H).

[0208] Synthesis of compound CPD169-3

[0209] Referring to the synthesis and purification method of compound CPD25-5, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD169-3 (20.66 g, purity: 99.73%, yield: 75.63%), mass spectrum: 357.22 (M+H).

[0210] Synthesis of compound CPD169-4

[0211] Referring to the synthesis and purification method of compound CPD25-7, only the corresponding raw materials need to be changed to obtain the target compound CPD169-4 (19.08 g, yield: 97.05%) as a white solid, mass spectrum: 385.04 (M+H). The obtained compound was used directly in the next step without purification.

[0212] Synthesis of compound CPD169-5

[0213] Referring to the synthesis and purification method of compound CPD25-8, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD169-5 (16.88 g, purity: 99.85%, yield: 40.33%), mass spectrum: 353.06 (M+H).

[0214] Synthesis of compound CPD169-6

[0215] Referring to the synthesis and purification method of compound CPD25-9, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD169-6 (14.63 g, purity: 99.12%, yield: 74.63%), mass spectrum: 445.20 (M+H).

[0216] Synthesis of compound CPD169

[0217] Referring to the synthesis and purification method of compound CPD25, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD169 (12.41 g, purity: 99.94%, yield: 73.63%). 12.41 g of crude CPD169 was purified by sublimation to obtain sublimation pure CPD169 (9.35 g, purity: 99.96%, yield: 75.35%), mass spectrum: 573.19 (M+H).

[0218] 1H NMR (400MHz, CDCl3) δ8.62 (s, 1H), 8.32-8.26 (m, 2H), 8.01 (d, J = 8.9Hz, 1H), 7.99-7.92 (m, 3H), 7.92-7.85 (m,5H),7.78(d,J=2.1Hz,1H),7.74-7.67(m,3H),7.62-7.55(m,2H),7.55-7.48(m,2H),7.45-7.35(m,4H).

[0219] Synthesis of compound CPD202

[0220] The synthetic route is:

[0221]

[0222] Synthesis of compound CPD202-2

[0223] Referring to the synthesis and purification method of compound CPD25-3, only the corresponding raw materials need to be changed to obtain the target compound CPD202-2 (24.22 g, purity: 99.18%, yield: 74.96%) as a white solid, with a mass spectrum of 329.10 (M+H).

[0224] Referring to the synthesis and purification method of compound CPD25-5, only the corresponding raw materials need to be changed to obtain the target compound CPD202-3 (19.85 g, purity: 99.76%, yield: 74.62%) as a white solid, with a mass spectrum of 357.22 (M+H).

[0225] Referring to the synthesis and purification method of compound CPD25-7, only the corresponding raw materials need to be changed to obtain the target compound CPD202-4 (17.96 g, yield: 94.56%) as a white solid, mass spectrum: 385.04 (M+H). The obtained compound was used directly in the next step without purification.

[0226] Synthesis of compound CPD202-5

[0227] Referring to the synthesis and purification method of compound CPD25-8, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD202-5 (15.69 g, purity: 99.87%, yield: 42.65%), mass spectrum: 353.06 (M+H).

[0228] Synthesis of compound CPD202

[0229] Referring to the synthesis and purification method of compound CPD119, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD202 (14.85 g, purity: 99.96%, yield: 74.66%). 14.85 g of crude CPD202 was purified by sublimation to obtain sublimation pure CPD202 (11.52 g, purity: 99.96%, yield: 77.58%), mass spectrum: 512.16 (M+H).

[0230] 1 H NMR (400MHz, CDCl3) δ8.59(s,1H),8.33-8.27(m,1H),8.16(d,J=7.8Hz,1H),8.01(d,J=9.0Hz,1H),7.98-7.85(m,7H),7.78(d,J= 2.1Hz,1H),7.70(d,J=2.2Hz,1H),7.62(dd,J=7.8,2.1Hz,1H),7.56(dd,J=7.9,2.2Hz,1H),7.54-7.46(m,4H),7.46-7.37(m,2H).

[0231] Synthesis of compound CPD228

[0232] The synthetic route is:

[0233]

[0234] Synthesis of compound CPD228-2

[0235] Referring to the synthesis and purification method of compound CPD25-3, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD228-2 (20.65 g, purity: 99.00%, yield: 74.98%), mass spectrum: 329.10 (M+H).

[0236] Synthesis of compound CPD228-3

[0237] Referring to the synthesis and purification method of compound CPD25-5, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD228-3 (17.11 g, purity: 99.41%, yield: 72.11%), mass spectrum: 357.22 (M+H).

[0238] Synthesis of compound CPD228-4

[0239] Referring to the synthesis and purification method of compound CPD25-7, only the corresponding raw materials need to be changed to obtain the target compound CPD228-4 (16.33 g, yield: 92.17%) as a white solid, mass spectrum: 385.04 (M+H). The obtained compound was used directly in the next step without purification.

[0240] Synthesis of compound CPD228-5

[0241] Referring to the synthesis and purification method of compound CPD25-8, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD228-5 (14.62 g, purity: 99.63%, yield: 40.00%), mass spectrum: 353.06 (M+H).

[0242] Synthesis of compound CPD228-6

[0243] Referring to the synthesis and purification method of compound CPD25-9, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD228-6 (17.69 g, purity: 98.89%, yield: 72.62%), mass spectrum: 445.20 (M+H).

[0244] Synthesis of compound CPD228

[0245] Referring to the synthesis and purification method of compound CPD59, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD228 (13.05 g, purity: 99.95%, yield: 72.06%). 13.05 g of crude CPD228 was purified by sublimation to obtain sublimation pure CPD228 (10.02 g, purity: 99.96%, yield: 76.82%), mass spectrum: 715.22 (M+H).

[0246] 1 H NMR (400MHz, CDCl3) δ8.33-8.28(m,1H),8.26-8.17(m,4H),8.14-8.04(m,5H),7.97(d,J=7.9Hz,1H),7.92(dd,J=9.7,2.2Hz,1H),7.90 -7.87(m,1H),7.85(d,J=8.0Hz,1H),7.66(d,J=2.2Hz,1H),7.57-7.46(m,8H),7.44-7.41(m,1H),7.37-7.27(m,3H),7.22-7.14(m,3H).

[0247] Synthesis of compound CPD232

[0248] The synthetic route is:

[0249]

[0250] Synthesis of compound CPD232-1

[0251] Referring to the synthesis and purification method of compound CPD25-8, only the corresponding raw materials need to be changed to obtain the target compound CPD232-1 (14.65 g, purity: 99.52%, yield: 39.77%) as a white solid, with a mass spectrum of 353.06 (M+H).

[0252] Referring to the synthesis and purification method of compound CPD25-9, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD232-2 (15.11 g, purity: 98.08%, yield: 75.96%), mass spectrum: 445.20 (M+H).

[0253] Synthesis of compound CPD232

[0254] Referring to the synthesis and purification method of compound CPD59, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD232 (12.85 g, purity: 99.96%, yield: 74.33%). 12.85 g of crude CPD232 was purified by sublimation to obtain sublimation pure CPD232 (9.52 g, purity: 99.96%, yield: 74.08%), mass spectrum: 802.20 (M+H).

[0255] 1 H NMR (400MHz, CDCl3) δ8.37(d,J=8.2Hz,1H),8.33-8.28(m,1H),8.28-8.24(m,1H),8.22(d,J=2.4Hz,1H ),8.11-8.05(m,2H),7.99-7.80(m,15H),7.65-7.60(m,4H),7.57-7.47(m,9H),7.37(d,J=7.1Hz,1H).

[0256] Synthesis of compound CPD263

[0257] The synthetic route is:

[0258]

[0259] Synthesis of compound CPD263-1

[0260] Referring to the synthesis and purification method of compound CPD25-8, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD263-1 (12.41 g, purity: 99.31%, yield: 38.45%), mass spectrum: 353.06 (M+H).

[0261] Synthesis of compound CPD263-2

[0262] Referring to the synthesis and purification method of compound CPD25-9, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD263-2 (14.12 g, purity: 99.20%, yield: 74.10%), mass spectrum: 445.20 (M+H).

[0263] Synthesis of compound CPD263

[0264] Referring to the synthesis and purification method of compound CPD59, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD263 (13.03 g, purity: 99.95%, yield: 73.02%). 13.03 g of crude CPD263 was purified by sublimation to obtain sublimation pure CPD263 (9.32 g, purity: 99.96%, yield: 71.52%), mass spectrum: 790.28 (M+H).

[0265] 1 H NMR (400MHz, CDCl3) δ8.34(dd,J=2.0,0.7Hz,1H),8.33-8.26(m,1H),8.21-8.17(m,2H),8.15(dd,J=9.0,2.4Hz,1H),8.12-8.05(m,3H),8.05-7.98( m,3H),7.96(d,J=8.0Hz,1H),7.94-7.92(m,1H),7.92-7.90(m,1H),7.90- 7.86(m,2H),7.68(d,J=2.3Hz,1H),7.55-7.40(m,12H),7.34-7.27(m,6H).

[0266] Synthesis of compound CPD300

[0267] The synthetic route is:

[0268]

[0269] Synthesis of compound CPD300-3

[0270] Referring to the synthesis and purification method of compound CPD25-5, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD300-3 (19.99 g, purity: 99.53%, yield: 74.63%), mass spectrum: 357.22 (M+H).

[0271] Synthesis of compound CPD300-4

[0272] Referring to the synthesis and purification method of compound CPD25-7, only the corresponding raw materials need to be changed to obtain the target compound CPD300-4 (20.66 g, yield: 93.06%) as a white solid, mass spectrum: 385.04 (M+H). The obtained compound was used directly in the next step without purification.

[0273] Synthesis of compound CPD300-5

[0274] Referring to the synthesis and purification method of compound CPD25-8, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD300-5 (18.52 g, purity: 99.76%, yield: 75.52%), mass spectrum: 353.06 (M+H).

[0275] Synthesis of compound CPD300

[0276] Referring to the synthesis and purification method of compound CPD59, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD300 (16.66 g, purity: 99.97%, yield: 74.85%). 16.66 g of crude CPD300 was purified by sublimation to obtain sublimation pure CPD300 (12.75 g, purity: 99.97%, yield: 76.53%), mass spectrum: 724.23 (M+H).

[0277] 1 H NMR (400MHz, CDCl3) δ8.79(dd,J=7.5,1.4Hz,1H),8.62-8.57(m,1H),8.55(t,J=2.2Hz,1H),8.38(d,J=6.9Hz,1H),8.35-8.29(m,1H),8 .21(d,J=9.7Hz,1H),8.19-8.12(m,2H),8.12-7.99(m,5H),7.97-7.86(m,4H),7.86-7.81(m,1H),7.71-7.59(m,3H),7.58-7.44(m,8H).

[0278] Synthesis of compound CPD344

[0279] The synthetic route is:

[0280]

[0281] Synthesis of compound CPD344-2

[0282] Referring to the synthesis and purification method of compound CPD25-5, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD344-2 (18.78 g, purity: 99.49%, yield: 71.12%), mass spectrum: 357.22 (M+H).

[0283] Synthesis of compound CPD344-3

[0284] Referring to the synthesis and purification method of compound CPD25-7, only the corresponding raw materials need to be changed to obtain the target compound CPD344-3 (19.89 g, yield: 94.66%) as a white solid, mass spectrum: 385.04 (M+H). The obtained compound was used directly in the next step without purification.

[0285] Synthesis of compound CPD344-4

[0286] Referring to the synthesis and purification method of compound CPD25-8, only the corresponding raw materials need to be changed to obtain the target compound CPD344-4 (17.01 g, purity: 99.88%, yield: 76.11%) as a white solid, with a mass spectrum of 353.06 (M+H).

[0287] Referring to the synthesis and purification method of compound CPD25-9, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD344-5 (15.06 g, purity: 99.00%, yield: 77.33%), mass spectrum: 445.06 (M+H).

[0288] Synthesis of compound CPD344

[0289] Referring to the synthesis and purification method of compound CPD25, only the corresponding raw materials need to be changed to obtain the target compound CPD344 (14.66 g, purity: 99.98%, yield: 75.63%) as a yellow solid. 14.66 g of crude CPD344 was purified by sublimation to obtain sublimation-pure CPD344 (11.56 g, purity: 99.98%, yield: 78.85%), mass spectrum: 523.17 (M+H).

[0290] 1H NMR(400MHz, CDCl3)δ8.86(s,1H),8.61(dd,J=8.5,3.7Hz,2H),8.46-8.39(m,1H),8.35-8.27(m,1H),8.16(d,J=9.8Hz,1H) ,8.03-7.92(m,3H),7.90-7.88(m,3H),7.67(d,J=2.3Hz,1H),7.59-7.47(m,4H),7.46-7.38(m,4H),7.32(d,J=7.3Hz,1H).

[0291] Synthesis of compound CPD364

[0292] The synthetic route is:

[0293]

[0294] Referring to the synthesis and purification method of compound CPD59, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD364 (17.56 g, purity: 99.95%, yield: 74.12%). 17.56 g of crude CPD364 was purified by sublimation to obtain sublimation pure CPD364 (13.08 g, purity: 99.98%, yield: 74.48%), mass spectrum: 640.19 (M+H).

[0295] 1 H NMR (400MHz, CDCl3) δ8.61 (dd, J=8.5, 3.7Hz, 2H), 8.49-8.38 (m, 1H), 8.35 -8.27(m,1H),8.21(d,J=9.7Hz,1H),8.13-8.00(m,3H),7.99-7.91(m,2H), 7.91-7.83(m,3H),7.69(d,J=2.3Hz,1H),7.67-7.59(m,1H),7.59-7.47(m, 6H),7.47-7.37(m,2H),7.32(d,J=7.2Hz,1H),7.26(dd,J=9.3,6.8Hz,1H).

[0296] Synthesis of compound CPD395

[0297] The synthetic route is:

[0298]

[0299] Referring to the synthesis and purification method of compound CPD59, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD395 (12.11 g, purity: 99.95%, yield: 75.69%). 12.11 g of crude CPD395 was purified by sublimation to obtain sublimation pure CPD395 (9.88 g, purity: 99.98%, yield: 81.58%), mass spectrum: 656.33 (M+H).

[0300] 1 HNMR(400MHz, CDCl3)δ8.61(dd,J=8.5,3.7Hz,2H),8.46-8.38(m,1H),8.34-8.27(m,1H),8.21(d,J=9.7Hz, 1H),7.97-7.91(m,2H),7.91-7.86(m,2H),7.69(d,J=2.2Hz,1H),7.57-7.46(m,2H),7.32(d,J=7.3Hz,1H).

[0301] Synthesis of compound CPD410

[0302] The synthetic route is:

[0303]

[0304] Synthesis of compound CPD410-2

[0305] Referring to the synthesis and purification method of compound CPD25-5, only the corresponding raw materials need to be changed to obtain the target compound CPD410-2 (17.89 g, purity: 99.63%, yield: 74.63%) as a white solid, with a mass spectrum of 413.12 (M+H).

[0306] Referring to the synthesis and purification method of compound CPD25-7, only the corresponding raw materials need to be changed to obtain the target compound CPD410-3 (16.56 g, yield: 95.55%) as a white solid, mass spectrum: 441.15 (M+H). The obtained compound was used directly in the next step without purification.

[0307] Synthesis of compound CPD410-4

[0308] Referring to the synthesis and purification method of compound CPD25-8, only the corresponding raw materials need to be changed to obtain the target compound CPD410-4 (18.33 g, purity: 99.57%, yield: 74.75%) as a white solid, with a mass spectrum of 409.13 (M+H).

[0309] Referring to the synthesis and purification method of compound CPD25-9, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD410-5 (16.79 g, purity: 99.21%, yield: 76.00%), mass spectrum: 501.02 (M+H).

[0310] Synthesis of compound CPD410

[0311] Referring to the synthesis and purification method of compound CPD59, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD410 (12.00 g, purity: 99.95%, yield: 72.63%). 12.00 g of crude CPD410 was purified by sublimation to obtain sublimation pure CPD410 (9.00 g, purity: 99.95%, yield: 75.00%), mass spectrum: 710.26 (M+H).

[0312] 1 H NMR (400MHz, CDCl3) δ8.60(d,J=9.3Hz,1H),8.53(d,J=8.2Hz,1H),8.33-8.28(m,1H),8.21(d,J=9.8Hz,1H),8.15-8.08(m,2H),8.08-8.00(m,1H),7 .96-7.82(m,5H),7.73-7.67(m,2H),7.66-7.59(m,1H),7.55(dd,J=6.8,1 .1Hz,1H),7.47-7.37(m,3H),7.35-7.23(m,4H),2.36(s,3H),1.34(s,9H).

[0313] Synthesis of compound CPD423

[0314] The synthetic route is:

[0315]

[0316] Synthesis of compound CPD423

[0317] Referring to the synthesis and purification method of compound CPD119, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD423 (13.56 g, purity: 99.96%, yield: 74.85%). 13.56 g of crude CPD423 was purified by sublimation to obtain sublimation pure CPD423 (10.11 g, purity: 99.95%, yield: 74.55%), mass spectrum: 587.20 (M+H).

[0318] 1H NMR(400MHz, CDCl3)δ8.61(dd,J=8.5,3.7Hz,2H),8.47-8.39(m,1H),8.33-8.28(m,1H),8.14-8.09(m,1H),8.01-7.94(m, 3H),7.94-7.85(m,3H),7.82-7.74(m,1H),7.67-7.59(m,3H),7.59-7.46(m,8H),7.46-7.40(m,2H),7.32(d,J=7.3Hz,1H).

[0319] Synthesis of compound CPD434

[0320] The synthetic route is:

[0321]

[0322] Synthesis of compound CPD434

[0323] Referring to the synthesis and purification method of compound CPD119, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD434 (10.52 g, purity: 99.93%, yield: 75.00%). 10.52 g of crude CPD434 was purified by sublimation to obtain sublimation pure CPD434 (8.00 g, purity: 99.93%, yield: 76.04%), mass spectrum: 655.18 (M+H).

[0324] 1 H NMR (400MHz, CDCl3) δ8.61(dd,J=8.5,3.7Hz,2H),8.47-8.39(m,1H),8.33-8.28(m,1H),8.23(dd,J=7.3,1. 2Hz,1H),8.18(d,J=8.8Hz,1H),7.97-7.85(m,6H),7.72-7.64(m,3H),7.60-7.47(m,6H),7.44-7.30(m,5H).

[0325] Synthesis of compound CPD475

[0326]

[0327] Synthesis of compound CPD475-1

[0328] Referring to the synthesis and purification method of compound CPD29-5, only the corresponding raw materials need to be changed to obtain the target compound CPD475-1 (17.07 g, purity: 99.53%, yield: 74.33%) as a white solid, with a mass spectrum of 357.22 (M+H).

[0329] Referring to the synthesis and purification method of compound CPD29-7, only the corresponding raw materials need to be changed to obtain the target compound CPD475-2 (16.56 g, yield: 95.96%) as a white solid, mass spectrum: 385.04 (M+H). The obtained compound was used directly in the next step without purification.

[0330] Synthesis of compound CPD475-3

[0331] Referring to the synthesis and purification method of compound CPD29-8, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD475-3 (17.01 g, purity: 99.50%, yield: 40.33%), mass spectrum: 353.06 (M+H).

[0332] Synthesis of compound CPD475-4

[0333] Referring to the synthesis and purification method of compound CPD29-9, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD475-4 (16.85 g, purity: 99.24%, yield: 75.74%), mass spectrum: 445.06 (M+H).

[0334] Synthesis of compound CPD475

[0335] Referring to the synthesis and purification method of compound CPD59, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD475 (11.01 g, purity: 99.93%, yield: 74.12%). 11.01 g of crude CPD475 was purified by sublimation to obtain sublimation pure CPD475 (7.56 g, purity: 99.94%, yield: 68.66%), mass spectrum: 674.22 (M+H).

[0336] 1H NMR (400MHz, CDCl3) δ8.64(d,J=9.3Hz,1H),8.46-8.41(m,1H),8.41-8.35(m,2H),8.19(dd,J=9.8,8.5Hz,2H),8.17-8.12(m,2H) ,8.11-8.02(m,6H),7.96(d,J=9.3Hz,1H),7.92(dd,J=9.7,2.2Hz,1H),7.91-7.86(m,1H),7.69-7.60(m,3H),7.55-7.46(m,7H).

[0337] Synthesis of compound CPD523

[0338] The synthetic route is:

[0339]

[0340] Synthesis of compound CPD523-1

[0341] Referring to the synthesis and purification method of compound CPD25-8, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD523-1 (14.11 g, purity: 99.31%, yield: 38.02%), mass spectrum: 353.06 (M+H).

[0342] Synthesis of compound CPD523-2

[0343] Referring to the synthesis and purification method of compound CPD25-9, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD523-2 (13.85 g, purity: 99.01%, yield: 76.05%), mass spectrum: 445.06 (M+H).

[0344] Synthesis of compound CPD523-4

[0345] Referring to the synthesis and purification method of compound CPD59, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD523-4 (13.85 g, purity: 99.60%, yield: 70.00%), mass spectrum: 502.10 (M+H).

[0346] Synthesis of compound CPD523

[0347] Referring to the synthesis and purification method of compound CPD59, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD523 (14.62 g, purity: 99.953%, yield: 75.06%). 14.62 g of crude CPD523 was purified by sublimation to obtain sublimation pure CPD523 (11.85 g, purity: 99.94%, yield: 81.05%), mass spectrum: 784.23 (M+H).

[0348] 1 H NMR(400MHz, CDCl3)δ8.61(dd,J=9.0,2.2Hz,2H),8.51-8.42(m,1H),8.21-8.15(m,2H),8.09(d,J=2.5Hz,1H),8. 00-7.87(m,11H),7.84(d,J=9.5Hz,2H),7.78(s,1H),7.68(d,J=2.3Hz,1H),7.58-7.46(m,4H),7.46-7.35(m,4H).

[0349] Synthesis of compound CPD558

[0350] The synthetic route is:

[0351]

[0352] Synthesis of compound CPD558-2

[0353] Referring to the synthesis and purification method of compound CPD25-5, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD558-2 (19.02 g, purity: 99.63%, yield: 75.00%), mass spectrum: 357.22 (M+H).

[0354] Synthesis of compound CPD558-3

[0355] Referring to the synthesis and purification method of compound CPD25-7, only the corresponding raw materials need to be changed to obtain the target compound CPD558-3 (18.06 g, yield: 94.33%) as a white solid, mass spectrum: 385.04 (M+H). The obtained compound was used directly in the next step without purification.

[0356] Synthesis of compound CPD558-4

[0357] Referring to the synthesis and purification method of compound CPD25-8, it is only necessary to change the corresponding raw materials to obtain the white solid as the target compound CPD558-4 (18.96 g, purity: 99.63%, yield: 75.96%), mass spectrum: 353.08 (M+H).

[0358] Synthesis of compound CPD558-5

[0359] Referring to the synthesis and purification method of compound CPD25-9, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD558-5 (20.63 g, purity: 99.01%, yield: 74.12%), mass spectrum: 445.21 (M+H).

[0360] Synthesis of compound CPD558-7

[0361] Referring to the synthesis and purification method of compound CPD25-3, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD558-7 (22.53 g, purity: 99.32%, yield: 76.12%), mass spectrum: 420.21 (M+H).

[0362] Synthesis of compound CPD558-8

[0363] Referring to the synthesis and purification method of compound CPD77-3, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD558-8 (18.88 g, purity: 99.68%, yield: 72.85%), mass spectrum: 420.21 (M+H).

[0364] Synthesis of compound CPD558

[0365] Referring to the synthesis and purification method of compound CPD59, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD558 (15.96 g, purity: 99.95%, yield: 72.96%). 15.96 g of crude CPD558 was purified by sublimation to obtain sublimation pure CPD558 (12.01 g, purity: 99.94%, yield: 75.25%), mass spectrum: 765.26 (M+H).

[0366] 1H NMR (400MHz, CDCl3) δ8.60 (dd, J=8.4, 3.3Hz, 2H), 8.49-8.38 (m, 2H), 8.28 (d d,J=7.5,1.3Hz,1H),8.18-8.11(m,3H),8.10-8.03(m,2H),8.01-7.82(m,6H ),7.73(d,J=7.7Hz,1H),7.66(d,J=2.0Hz,1H),7.58(td,J=7.7,1.3Hz,1H), 7.56-7.46(m,7H),7.42-7.38(m,1H),7.34-7.27(m,2H),7.24-7.11(m,3H).

[0367] Synthesis of compound CPD584

[0368] The synthetic route is:

[0369]

[0370] Synthesis of compound CPD584-2

[0371] Referring to the synthesis and purification method of compound CPD25-3, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD584-2 (25.26 g, purity: 99.02%, yield: 74.63%), mass spectrum: 345.08 (M+H).

[0372] Synthesis of compound CPD584-3

[0373] Referring to the synthesis and purification method of compound CPD25-5, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD584-3 (22.11 g, purity: 99.52%, yield: 72.00%), mass spectrum: 373.04 (M+H).

[0374] Synthesis of compound CPD584-4

[0375] Referring to the synthesis and purification method of compound CPD25-7, only the corresponding raw materials need to be changed to obtain the target compound CPD584-4 (20.63 g, yield: 94.00%) as a white solid, mass spectrum: 401.06 (M+H). The obtained compound was used directly in the next step without purification.

[0376] Synthesis of compound CPD584-5

[0377] Referring to the synthesis and purification method of compound CPD25-8, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD584-5 (19.89 g, purity: 99.72%, yield: 74.63%), mass spectrum: 369.04 (M+H).

[0378] Synthesis of compound CPD584-6

[0379] Referring to the synthesis and purification method of compound CPD25-9, it is only necessary to change the corresponding raw materials to obtain the white solid target compound CPD584-6 (18.08 g, purity: 99.33%, yield: 74.01%), mass spectrum: 461.17 (M+H).

[0380] Synthesis of compound CPD584

[0381] Referring to the synthesis and purification method of compound CPD59, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD584 (17.52 g, purity: 99.95%, yield: 72.11%). 17.52 g of crude CPD584 was purified by sublimation to obtain sublimation pure CPD584 (14.01 g, purity: 99.95, yield: 79.96%), mass spectrum: 783.21 (M+H).

[0382] 1 H NMR (400MHz, CDCl3) δ8.62(d,J=2.2Hz,1H),8.28(d,J=2.2Hz,1H),8.22(d,J=7.0Hz,1H),8. 11-8.01(m,9H),8.00-7.95(m,3H),7.95-7.82(m,7H),7.54-7.46(m,6H),7.46-7.36(m,2H).

[0383] Synthesis of compound CPD609

[0384] The synthetic route is:

[0385]

[0386] Synthesis of compound CPD609-2

[0387] Referring to the synthesis and purification method of compound CPD25-3, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD609-2 (20.33 g, purity: 99.08%, yield: 72.74%), mass spectrum: 477.17 (M+H).

[0388] Synthesis of compound CPD609-3

[0389] Referring to the synthesis and purification method of compound CPD25-5, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD609-3 (19.87 g, purity: 99.63%, yield: 74.85%), mass spectrum: 505.13 (M+H).

[0390] Synthesis of compound CPD609-4

[0391] Referring to the synthesis and purification method of compound CPD25-7, only the corresponding raw materials need to be changed to obtain the target compound CPD609-4 (18.96 g, yield: 96.66%) as a white solid, mass spectrum: 533.16 (M+H). The obtained compound was used directly in the next step without purification.

[0392] Synthesis of compound CPD609-5

[0393] Referring to the synthesis and purification method of compound CPD25-8, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD609-5 (19.45 g, purity: 99.52%, yield: 75.05%), mass spectrum: 501.13 (M+H).

[0394] Synthesis of compound CPD609-6

[0395] Referring to the synthesis and purification method of compound CPD25-9, it is only necessary to change the corresponding raw materials to obtain the white solid as the target compound CPD609-6 (19.86 g, purity: 99.00%, yield: 76.52%), mass spectrum: 593.26 (M+H).

[0396] Synthesis of compound CPD609

[0397] Referring to the synthesis and purification method of compound CPD59, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD609 (18.77 g, purity: 99.94%, yield: 74.87%). 18.77 grams of crude CPD609 was sublimated and purified to obtain sublimation pure CPD609 (14.98 g, purity: 99.94%, yield: 79.80%), mass spectrum: 788.26 (M+H).

[0398] 1H NMR(400MHz, CDCl3)δ8.62(d,J=9.1Hz,1H),8.50(d,J=8.0Hz,1H),8.48-8.4 1(m,1H),8.39(d,J=2.3Hz,1H),8.25(d,J=8.9Hz,1H),8.16(d,J=7.5Hz,1H) ,8.14-7.97(m,8H),7.94(d,J=8.1Hz,1H),7.91-7.82(m,3H),7.73(d,J=9.5 Hz,1H),7.67-7.59(m,1H),7.59-7.38(m,12H),7.26(dd,J=9.3,6.8Hz,1H).

[0399] Synthesis of compound CPD617

[0400] The synthetic route is:

[0401]

[0402] Synthesis of compound CPD617-2

[0403] Referring to the synthesis and purification method of compound CPD25-3, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD617-2 (23.53 g, purity: 99.05%, yield: 74.63%), mass spectrum: 480.18 (M+H).

[0404] Synthesis of compound CPD617-3

[0405] Referring to the synthesis and purification method of compound CPD25-5, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD617-3 (21.85 g, purity: 99.67%, yield: 75.86%), mass spectrum: 508.14 (M+H).

[0406] Synthesis of compound CPD617-4

[0407] Referring to the synthesis and purification method of compound CPD25-7, only the corresponding raw materials need to be changed to obtain the target compound CPD627-4 (20.00 g, yield: 97.06%) as a white solid, mass spectrum: 536.05 (M+H). The obtained compound was used directly in the next step without purification.

[0408] Synthesis of compound CPD617-5

[0409] Referring to the synthesis and purification method of compound CPD25-8, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD617-5 (19.45 g, purity: 99.52%, yield: 75.05%), mass spectrum: 504.14 (M+H).

[0410] Synthesis of compound CPD617-6

[0411] Referring to the synthesis and purification method of compound CPD25-9, it is only necessary to change the corresponding raw materials to obtain a white solid as the target compound CPD617-6 (18.41 g, purity: 99.16%, yield: 74.51%), mass spectrum: 596.27 (M+H).

[0412] Synthesis of compound CPD617

[0413] Referring to the synthesis and purification method of compound CPD59, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD617 (14.96 g, purity: 99.95%, yield: 72.96%). 14.96 grams of crude CPD617 was sublimated and purified to obtain sublimation pure CPD617 (11.76 g, purity: 99.95%, yield: 78.60%), mass spectrum: 777.29 (M+H).

[0414] 1 H NMR (400MHz, CDCl3) δ8.48(d,J=9.4Hz,1H),8.26-8.19(m,2H),8.14(d,J=9.3Hz,1H),8.12-8.01(m,4H),7.99(d,J=6.8Hz,1H),7.97-7.87(m,5H), 7.85(d,J=8.0Hz,1H),7.73-7.66(m,2H),7.62(dd,J=6.9,1.2Hz,1H),7. 61-7.54(m,3H),7.54-7.46(m,7H),7.45-7.37(m,7H),7.25-7.22(m,1H).

[0415] Synthesis of compound CPD632

[0416] The synthetic route is:

[0417]

[0418] Referring to the synthesis and purification method of compound CPD119, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD632 (10.02 g, purity: 99.94%, yield: 76.87%). 10.02 g of crude CPD632 was purified by sublimation to obtain sublimation pure CPD632 (7.88 g, purity: 99.94%, yield: 78.64%), mass spectrum: 572.19 (M+H).

[0419] 1 H NMR (400MHz, CDCl3) δ9.26 (d, J=1.3Hz, 1H), 8.71 (dd, J=4.6, 1.3Hz, 1H), 8.61 (dd,J=8.5,3.7Hz,2H),8.50-8.37(m,1H),8.36-8.24(m,1H),8.11(d,J=7.8Hz ,1H),8.07-7.97(m,2H),7.94(d,J=8.2Hz,1H),7.91-7.83(m,2H),7.61-7.46 (m,7H),7.46-7.36(m,4H),7.32(d,J=7.3Hz,1H),7.16(dd,J=8.0,2.1Hz,1H).

[0420] Synthesis of compound CPD643

[0421] The synthetic route is:

[0422]

[0423] Referring to the synthesis and purification method of compound CPD119, only the corresponding raw materials need to be changed to obtain the yellow solid as the target compound CPD643 (11.84 g, purity: 99.95%, yield: 72.02%). 11.84 g of crude CPD643 was purified by sublimation to obtain sublimation pure CPD643 (8.09 g, purity: 99.95%, yield: 68.32%), mass spectrum: 512.17 (M+H).

[0424] 1HNMR (400MHz, CDCl3) δ8.37(d,J=2.2Hz,1H),8.17(d,J=9.1Hz,1H),8.12(d,J=8.0Hz,1H),8.08-8.03(m,1H),7.99(d,J=8.0Hz,1H),7.96-7. 91(m,5H),7.91-7.86(m,1H),7.85(dd,J=7.6,3.0Hz,2H),7.68-7.56(m,4H),7.55-7.48(m,2H),7.45(t,J=7.1Hz,1H),7.32(d,J=7.2Hz,1H).

[0425] Application example: Preparation of organic electroluminescent devices

[0426] Figure 2 Schematic diagram of the structure of the organic electroluminescent device of the present invention, which includes, from bottom to top, a stacked glass substrate 1, an anode 2 (indium tin oxide), a hole injection layer 3, a first hole transport layer (HTL1) 4, a second hole transport layer (HTL2) 5, a light-emitting layer 6, an electron transport layer (ETL) 7, an electron injection layer 8 (EIL) and a cathode 9.

[0427] A 50 mm×50 mm×1.0 mm glass substrate with an ITO (indium tin oxide, 100 nm) transparent electrode was ultrasonically cleaned in ethanol for 10 minutes, dried at 150° C., and then treated with N2 Plasma (plasma gas) for 30 minutes. The washed glass substrate is mounted on a substrate support of a vacuum evaporation device, and compound NDP-9 and compound HTM1 are evaporated at a weight ratio of 97:3 to form a hole injection layer with a thickness of 10 nm, followed by evaporation of a layer of HTM1 to form a thin film with a thickness of 60 nm as HTL1 (hole transport layer 1), and then a layer of HTM2 is evaporated on the HTM1 thin film to form a thin film with a thickness of 10 nm as HTL2 (hole transport layer 2), and then, a light-emitting layer with a thickness of 40 nm is co-evaporated on the HTM2 film layer in the form of a single main body or a double main body (main material: red light doping material = 97%: 3%, mass fraction), wherein the main materials of the single main body or the double main body are the organic electroluminescent compound synthesized by the present invention, RH-P and comparative compounds 1-4, respectively. On the light-emitting layer, ETL (electron transport layer) material and LiQ are co-evaporated (35nm) in a weight ratio of 50:50 as an electron transport material, and then LiQ (1nm) is evaporated on the electron transport material layer as an electron injection material, and then Mg / Ag (100nm, mass ratio of 1:9) is evaporated as a cathode material using a co-evaporation mode to obtain an organic electroluminescent device.

[0428] The structural formulas of NDP-9, HTM1, HTM2, red light doping material, ETL material, LiQ, RH-P, and comparative compounds 1-4 are as follows:

[0429]

[0430] Performance Testing

[0431] The above organic electroluminescent device was tested for performance, and the organic electroluminescent compound synthesized by the present invention and the comparative compounds 1-4 were used as the main materials for comparison. A constant current power supply (Keithley 2400) was used to flow a fixed current density through the light-emitting element, and the luminescence spectrum was tested by a spectroradiometer (CS2000). At the same time, the luminescent spectrum was tested at 10 mA / cm 2 The IVL (current-voltage-luminance) performance of the device was measured at 50 mA / cm 2 The life of LT95 devices was tested under the following conditions. The results are shown in Tables 1 and 2.

[0432] The performance test results of devices using the organic electroluminescent compounds synthesized by the present invention and comparative compounds 1-3 as single main materials and co-evaporated with red light doping materials to form a light-emitting layer are shown in Table 1 (the examples in Table 1 use the organic electroluminescent compounds of the present invention, and the comparative examples use the above-mentioned comparative compounds).

[0433] Table 1:

[0434]

[0435]

[0436] The performance test results of the device using the organic electroluminescent compounds synthesized by the present invention and comparative compounds 1-4 mixed with RH-P material in a ratio of 5:5 and co-evaporated with red light doping material to form a light-emitting layer are shown in Table 2 (the examples in Table 2 use the organic electroluminescent compounds of the present invention, and the comparative examples use the above-mentioned comparative compounds).

[0437] Table 2:

[0438]

[0439]

[0440] As can be seen from Table 1-2, the light-emitting device prepared by using the organic electroluminescent compound synthesized in the present invention as a single-host red light material has not only a lower driving voltage, higher luminous efficiency, but also a longer device life under the same emission wavelength conditions compared to the light-emitting device prepared by using the comparative compound 1-3. When the organic electroluminescent compound synthesized in the present invention is used in combination with a P-type material as a dual-host material, the luminous efficiency and life are greatly improved compared to the single-host red light material due to the balance of hole and electron transfer rates and the widening of the exciton recombination area in the light-emitting layer; and it is much higher than the light-emitting device prepared by using the comparative compound 1-4.

[0441] The sublimation temperatures of the organic electroluminescent compounds synthesized in the present invention and comparative compounds 1-3 were tested, and the results are shown in Table 3. Wherein: the sublimation temperature is defined as: -7 The vacuum degree is 1000 Torr and the temperature corresponding to the sublimation rate is 1 angstrom per second.

[0442] Table 3:

[0443] Compound Sublimation temperature(℃) CPD59 271 CPD63 265 CPD77 266 CPD364 273 CPD410 270 CPD423 268 Comparative Compound 1 275 Comparative Compound 2 281 Comparative Compound 3 283

[0444] It can be seen from Table 3 that the compounds synthesized by the present invention have lower sublimation temperatures than comparative compounds 1-3, and are more conducive to industrial application.

[0445] Therefore, the compound synthesized by the present invention has the advantages of high optical and electrical stability, low sublimation temperature, low driving voltage, high luminous efficiency, long device life, etc., and can be used as a red light main material in OLED light-emitting devices; at the same time, it has a low melting point, and as a molten material, it is beneficial to the stability of material evaporation. It can be used as a main material and has the possibility of being applied to the AMOLED industry.

[0446] In addition, since it is impossible to enumerate all the organic electroluminescent compounds synthesized by the present invention, the above Tables 1-3 only list some of the compounds or device properties of the present invention. However, within the scope of the present invention, especially the compounds with specific structural formulas given in the present invention, they all have similar advantages as the compounds used in Tables 1-3, such as high optical and electrical stability, low sublimation temperature, low driving voltage, high luminous efficiency, and long device life.

Claims

1. A compound, characterized in that Its general structural formula is shown in formula (1): Where: X is selected from NR a , CR b R c , O, S or Se; R a , R b , R c Each is independently selected from C1-C30 alkyl, C1-C30 heteroalkyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C6-C30 aryl, C3-C30 heteroaryl; ET represents an electron-withdrawing group; L is selected from a single bond, a substituted or unsubstituted C6-C20 arylene group, or a substituted or unsubstituted C3-C20 heteroarylene group; Ring A is selected from the structure represented by formula (2) or formula (3); X1-X 12 are independently selected from CR0; and X1-X4, X5-X6, X7-X8, X9-X 12 There are two adjacent sites in the formula (1) that are fused to the 5-membered ring containing X; R0 is selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl or C3-C60 heteroaryl; the electron withdrawing group is selected from the structures shown in formula (B-14) to (B-36): Wherein: * represents the site of connection with L in formula (1); R1 and R2 are independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C6-C20 arylene or substituted or unsubstituted C3-C20 heteroarylene; The substitution is substituted by at least one of deuterium, halogen, cyano, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl substituted or unsubstituted C6-C30 aryl, C1-C6 alkyl substituted or unsubstituted C3-C30 heteroaryl, wherein the number of substitutions ranges from single substitution to the maximum number of substitutions; The heteroatoms in the heteroaryl, heteroalkyl and heterocycloalkyl groups are independently selected from at least one of O, S, N, Se, Si and Ge; n is an integer of 0-10; if n is an integer not less than 2, each R1 may be the same or different, and two adjacent R1 may be connected to form a ring.

2. The compound according to claim 1, characterized in that The R a , R b , R c Each is independently selected from C1-C20 alkyl, C1-C20 heteroalkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C20 aryl and C3-C20 heteroaryl.

3. The compound according to claim 1, characterized in that The structure represented by formula (2) or formula (3) is selected from the structures represented by formula (A-1) to (A-8): Wherein: * represents the site of fusion with the 5-membered ring containing X in formula (1); m is an integer of 0-10; if m is an integer not less than 2, each R0 may be the same or different.

4. The compound according to any one of claims 1 to 3, characterized in that The structure represented by formula (2) or formula (3) is selected from the structures represented by formula (A-9) to (A-16): Wherein, * represents the site of fusion with the 5-membered ring containing X in formula (1); t is an integer of 0-6; if t is an integer not less than 2, each R0 may be the same or different.

5. The compound according to any one of claims 1 to 3, characterized in that The L is selected from a single bond or a structure represented by formula (L-1) to formula (L-14): Wherein: R is a substituent, each R is independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C20 alkyl, C1-C20 heteroalkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C30 aryl or C3-C30 heteroaryl, wherein the number of substitutions is from a single substitution to the maximum number of substitutions.

6. A compound, characterized in that The structural formula of the compound is one of the structural formulas shown in CPD16 to CPD42, CPD44 to CPD139, CPD141 to CPD165, CPD170 to CPD180, CPD191 to CPD230, CPD236 to CPD255, CPD266 to CPD320, CPD327 to CPD490, CPD501 to CPD645, or CPD16 to CPD42, CPD44 to CPD139, CPD141 to CPD165, CPD170 to CPD180, CPD191 to CPD230, One of the structural formulas in which hydrogen in CPD236 to CPD255, CPD266 to CPD320, CPD327 to CPD490, CPD501 to CPD645 is partially or completely replaced by deuterium, or hydrogen in CPD16 to CPD42, CPD44 to CPD139, CPD141 to CPD165, CPD170 to CPD180, CPD191 to CPD230, CPD236 to CPD255, CPD266 to CPD320, CPD327 to CPD490, CPD501 to CPD645 is partially or completely replaced by fluorine:

7. An organic electroluminescent device, characterized in that: The invention comprises a light-emitting layer, wherein the light-emitting layer comprises the compound according to any one of claims 1 to 6.

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