A heterocyclic compound and an organic electroluminescent device thereof

Abstract

The present invention provides a heterocyclic compound and an organic electroluminescent device, relating to the technical field of organic electroluminescence. The heterocyclic compound provided by the present invention has a high electron mobility, a high triplet energy level, and appropriate HOMO and LUMO energy levels. When it is applied to an organic electroluminescent device as an electron transport layer material or a hole blocking layer material, it can effectively block the migration of holes to the electron transport layer side, increase the recombination probability of holes and electrons in the light-emitting layer, reduce the driving voltage of the device, and improve the light-emitting efficiency of the device. The heterocyclic compound provided by the present invention also has a relatively high glass transition temperature, good film-forming property and thermal stability, which can effectively improve the service life of the device. In addition, the compound of the present invention has a relatively high refractive index. When it is applied to the cover layer of an organic electroluminescent device, it can effectively improve the light extraction efficiency of the device, thereby improving the light-emitting efficiency and service life of the device.

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescent materials, and particularly relates to a heterocyclic compound and an organic electroluminescent device thereof. Background Art

[0002] In recent years, with the rapid development of electronic technology, human society has been continuously moving forward towards the information age. As one of the most important parts of all technologies in the information industry, display technology has also been continuously progressing with the increasing social demand. Organic Light Emitting Diodes (OLEDs) are regarded as the most ideal new generation of flat panel display technology so far because of their excellent properties such as self-luminescence, light weight, low power consumption, fast response speed, high luminous efficiency, high contrast, high resolution, high brightness, good flexibility, wide color gamut, and wide viewing angle. They are widely used in fields such as display and lighting, and are one of the most promising products in the 21st century.

[0003] Most organic electroluminescent devices now adopt a classic sandwich structure composed of a cathode, an anode, and an organic functional layer. The organic functional layer includes a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cover layer, etc. The multi-layer structure can give full play to the role of each organic layer compared with the single-layer and double-layer structures, which is a better choice for the development of OLEDs so far. The light emitting principle of OLEDs is that under the action of an external electric field, holes generated by the anode and electrons generated by the cathode recombine in the light emitting layer to form excitons. The molecules in the excited state are very unstable and will transition back to the ground state, and the energy is released in the form of light energy, resulting in a light emitting phenomenon.

[0004] Currently, in OLED devices, the hole mobility of hole transport materials is higher than the electron mobility of electron transport materials. After holes enter the light-emitting layer, some holes will continue to migrate to the electron transport region under the action of the driving voltage and recombine with electrons in the electron transport region, resulting in an inability to achieve an effective balance in the carrier transport. The exciton concentration in the light-emitting layer decreases, thereby reducing the efficiency of the device and causing problems such as high driving voltage, low luminous efficiency, and short service life of the device. To achieve the maximum recombination of carriers, it is necessary to reduce the energy barrier during electron injection, improve the electron injection efficiency, and effectively block holes within the light-emitting layer. The hole blocking layer has a special energy level structure that can form a migration barrier for holes and prevent them from migrating to the electron transport region. In addition, most current organic electroluminescent devices have the problem of relatively low light extraction efficiency. A covering layer can be formed on the transparent electrode to improve the light extraction efficiency of the device and thereby improve the luminous efficiency of the device. Therefore, designing electron transport materials and / or hole blocking materials with high electron mobility and excellent hole blocking ability and covering layer materials with a relatively high refractive index is of great significance for improving the luminous efficiency and service life of OLED devices. Summary of the Invention

[0005] To solve the above problems, reduce the driving voltage of OLED devices, and improve the luminous efficiency and service life of OLED devices, the present invention provides a heterocyclic compound and an organic electroluminescent device thereof. The heterocyclic compound provided by the present invention has a relatively high electron mobility and good hole blocking ability, can effectively improve the carrier transport balance of the device, and at the same time, the heterocyclic compound has a relatively high refractive index, which can effectively improve the light extraction efficiency of the device. The technical solution of the present invention is specifically as follows:

[0006] The present invention provides a heterocyclic compound having a structure as shown in Formula 1:

[0007] A-L-B Formula 1

[0008] In Formula 1, A is selected from any one of the structures shown in Formulas 2 to 4:

[0009]

[0010] Each Ry is independently selected from any one of a substituted or unsubstituted C6-C30 aryl group and a substituted or unsubstituted C2-C30 heteroaryl group; or Ry can be directly bonded to L.

[0011] Each Z is independently selected from CH or N, and in the structures shown in Formulas 2 to 4, at least one Z in each structure is N; the Z at the connection with Lx and L is selected from CH.

[0012] The R 1Independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl;

[0013] Said a is independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said b is selected from 0, 1, 2, 3, 4 or 5, said c is selected from 0, 1, 2, 3, 4, 5, 6 or 7. When said a, b or c is greater than 1, two or more Rs 1 Are the same as or different from each other, or two adjacent Rs 1 Can be bonded to form a substituted or unsubstituted ring;

[0014] Said X 1 Is selected from any one of a single bond, O, S, C(R 2 )(R 3 ), and N(R 4 );

[0015] Said R 2 、R 3 Are independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl;

[0016] Said R 4 Is independently selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl;

[0017] Said B is a structure shown in Formula 5:

[0018]

[0019] Said X 2 Is selected from O or S;

[0020] Said ring E is selected from any one of the following groups:

[0021]

[0022] Said Y is independently selected from CH or N, and "*" represents the fusion site;

[0023] Said R 5 、R 7Independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl;

[0024] Said d 1 Independently selected from 0, 1, 2, 3, 4, 5 or 6, said d 2 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, said d 3 Independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; when said d 1 , d 2 Or d 3 Is 1, two or more Rs 7 Are the same or different from each other, or two adjacent Rs 7 Bond to form a substituted or unsubstituted ring;

[0025] Said L and Lx are independently selected from any one of a single bond, substituted or unsubstituted C6-C30 arylene, and substituted or unsubstituted C2-C30 heteroarylene;

[0026] When there are multiple substituents in said "substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene", the multiple substituents are the same or different from each other, or two adjacent substituents can bond to form a substituted or unsubstituted ring.

[0027] The present invention also provides an organic electroluminescent device, comprising an anode, a cathode and one or more organic layers, said organic layers being located between said anode and said cathode or on the outer side of at least one of said anode and said cathode, and said organic layers comprising at least one heterocyclic compound of the present invention.

[0028] Beneficial effects

[0029] The heterocyclic compounds provided by the present invention have high electron mobility, are easy to transport electrons, and enable the transport of holes and electrons to reach equilibrium, thereby improving the light-emitting efficiency of the device. At the same time, the heterocyclic compounds provided by the present invention have high triplet energy levels and appropriate HOMO and LUMO energy levels. When applied to an organic electroluminescent device as an electron transport layer / hole blocking layer, not only can the electron injection and transport barriers be reduced, but also the migration of holes to the electron transport layer side can be effectively blocked, the recombination probability of holes and electrons in the light-emitting layer can be increased, the driving voltage of the device can be reduced, and the light-emitting efficiency of the device can be improved. The compounds of the present invention also have a relatively high glass transition temperature, good film-forming properties and thermal stability, which can effectively improve the service life of the device and further enhance the performance of the device. In addition, the compounds of the present invention have a relatively high refractive index. When applied to the cover layer of an organic electroluminescent device, the light extraction efficiency of the device can be effectively improved, thereby improving the light-emitting efficiency and service life of the device. Detailed Embodiments

[0030] The technical solutions of the specific embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative efforts belong to the protection scope of the present invention.

[0031] In this specification, "*" means the part connected to another substituent. "*" can be connected to any optional position of the connected group / fragment. As used in the present invention, can represent and so on.

[0032] Examples of the halogen atoms described in the present invention may include fluorine, chlorine, bromine and iodine.

[0033] The alkyl group described in the present invention refers to the general term of monovalent groups obtained by removing one hydrogen atom from an alkane molecule, which can be a straight-chain alkyl group or a branched-chain alkyl group, preferably having 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms. The alkyl group can be substituted or unsubstituted. The straight-chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, etc., but are not limited thereto; the branched-chain alkyl groups include isopropyl, isobutyl, sec-butyl, tert-butyl, isomeric groups of n-pentyl, isomeric groups of n-hexyl, isomeric groups of n-heptyl, isomeric groups of n-octyl, isomeric groups of n-nonyl, isomeric groups of n-decyl, etc., but are not limited thereto.

[0034] The cycloalkyl group described in the present invention refers to the general term for monovalent groups obtained by removing one hydrogen atom from a cyclic alkane molecule, preferably having 3 to 18 carbon atoms, more preferably 3 to 12 carbon atoms, and particularly preferably 3 to 6 carbon atoms. The cycloalkyl group may be substituted or unsubstituted. Specific examples may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, etc., but are not limited thereto.

[0035] The aryl group described in the present invention refers to the general term for monovalent groups obtained by removing one hydrogen atom from the aromatic nucleus carbon of an aromatic compound molecule, which may be a monocyclic aryl group, a polycyclic aryl group or a fused-ring aryl group, preferably having 6 to 60 carbon atoms, more preferably 6 to 30 carbon atoms, particularly preferably 6 to 18 carbon atoms, and most preferably 6 to 12 carbon atoms. The aryl group may be substituted or unsubstituted. The monocyclic aryl group refers to an aryl group having only one aromatic ring in the molecule, such as phenyl, etc., but is not limited thereto; the polycyclic aryl group refers to an aryl group having two or more independent aromatic rings in the molecule, such as biphenyl, terphenyl, etc., but is not limited thereto; the fused-ring aryl group refers to an aryl group having two or more aromatic rings and fused to each other by sharing two adjacent carbon atoms, such as naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluorenyl, benzofluorenyl, triphenylenyl, fluoranthenyl, 9,9'-spirobifluorenyl, etc., but is not limited thereto.

[0036] The heteroaryl group described in the present invention refers to the general term for monovalent groups obtained by replacing one or more aromatic nucleus carbon atoms in the aryl group with heteroatoms, and the heteroatoms include but are not limited to oxygen, sulfur, nitrogen, silicon or phosphorus atoms, preferably having 2 to 60 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably 2 to 18 carbon atoms, also preferably 2 to 12 carbon atoms, and most preferably 2 to 7 carbon atoms. The heteroaryl group may be substituted or unsubstituted. The connection site of the heteroaryl group may be located on the ring-forming carbon atoms or on the ring-forming heteroatoms, and the heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group or a fused-ring heteroaryl group, etc. The monocyclic heteroaryl group includes pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, etc., but is not limited thereto; the polycyclic heteroaryl group includes bipyridyl, bipyrimidinyl, phenylpyridyl, phenylpyrimidinyl, etc., but is not limited thereto; the fused-ring heteroaryl group includes quinolinyl, isoquinolinyl, indolyl, benzothienyl, benzofuryl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuryl, benzodibenzofuryl, dibenzothienyl, benzodibenzothienyl, carbazolyl, benzocarbazolyl, acridinyl, 9,10-dihydroacridinyl, phenoxazinyl, phenothiazinyl, phenoxathiinyl, spirofluoreneoxanthenyl, spirofluorenesulfuranthenyl, etc., but is not limited thereto.

[0037] The arylene group described in the present invention refers to the general term of divalent groups obtained by removing two hydrogen atoms from the aromatic nucleus carbon of an aromatic compound molecule. It can be a monocyclic arylene group, a polycyclic arylene group or a fused-ring arylene group, preferably having 6 to 60 carbon atoms, more preferably 6 to 30 carbon atoms, particularly preferably 6 to 18 carbon atoms, and most preferably 6 to 12 carbon atoms. The arylene group can be substituted or unsubstituted. The monocyclic arylene group includes, but is not limited to, phenylene, etc.; the polycyclic arylene group includes, but is not limited to, biphenylene, terphenyl, etc.; the fused-ring arylene group includes, but is not limited to, naphthylene, anthrylene, phenanthrylene, pyrenylene, perylenylene, fluorenylene, benzo[a]fluorenylene, triphenylene, fluoranthenylene, 9,9'-spirobifluorenylene, etc.

[0038] The heteroarylene group described in the present invention refers to the general term of divalent groups obtained by removing two hydrogen atoms from the nuclear carbon of an aromatic heterocycle composed of carbon and heteroatoms in the arylene group. The heteroatoms include, but are not limited to, oxygen, sulfur, nitrogen or phosphorus atoms. It preferably has 2 to 60 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably 2 to 18 carbon atoms, also preferably 2 to 12 carbon atoms, and most preferably 2 to 7 carbon atoms. The heteroarylene group can be substituted or unsubstituted. The connecting site of the heteroarylene group can be located on the ring-forming carbon atoms or on the ring-forming heteroatoms. The heteroarylene group can be a monocyclic heteroarylene group, a polycyclic heteroarylene group or a fused-ring heteroarylene group. The monocyclic heteroarylene group includes, but is not limited to, pyridylene, pyrimidinylene, pyrazinylene, pyridazinylene, triazinylene, furanylene, thienylene, pyrrolylene, oxazolylene, thiazolylene, imidazolylene, etc.; the polycyclic heteroarylene group includes, but is not limited to, bipyridylene, bipyrimidinylene, phenylpyridylene, phenylpyrimidine, etc.; the fused-ring heteroarylene group includes, but is not limited to, quinolinylene, isoquinolinylene, indolylene, benzothienylene, benzofuranylene, benzoxazolylene, benzimidazolylene, benzothiazolylene, dibenzofuranylene, benzo[d]dibenzofuranylene, dibenzothienylene, benzo[d]dibenzothienylene, carbazolylene, benzocarbazolylene, acridinylene, 9,10-dihydroacridinylene, phenoxazinylene, phenothiazinylene, phenoxathiinylene, spirofluoreneoxanthene, spirofluorenesulfuranthene, etc.

[0039] "Substituted" as used in the present invention means that a hydrogen atom in a compound group is replaced by other atoms or groups, and the substitution position is not restricted.

[0040] As used herein, "substituted or unsubstituted" means unsubstituted or mono- or poly-substituted by the following groups: deuterium, cyano, nitro, halogen atom, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 alkylthio, substituted or unsubstituted C1-C12 alkylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C30 arylamino, etc., but not limited thereto; or when there are multiple substituents, adjacent substituents may be bonded to form a ring; when there are multiple substituents, the multiple substituents may be the same or different from each other.

[0041] Preferably mono- or poly-substituted by the following groups: deuterium, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclopentadienyl, cyclohexadienyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, perylenyl, pyrenyl, benzyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, 9,9'-spirobifluorenyl, pyridyl, pyrimidinyl, triazinyl, carbazolyl, acridinyl, furyl, thienyl, benzofuranyl, benzothienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothienyl, phenothiazinyl, phenoxazinyl, indolyl, etc., but not limited thereto.

[0042] As used herein, "bonded to form a ring" means that two groups are connected to each other by a chemical bond and optionally aromatized. Examples are as follows:

[0043]

[0044] In the present invention, the ring formed by connection may be an aromatic ring system, an aliphatic ring system or a ring system formed by the fusion of both, and the ring formed by connection may be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring or a fused ring, such as benzene, naphthalene, indene, cyclopentene, cyclopentane, cyclopentane-fused benzene, cyclohexene, cyclohexane, cyclohexane-fused benzene, fluorene, pyridine, quinoline, isoquinoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, phenanthrene or pyrene, but not limited thereto.

[0045] The present invention provides a heterocyclic compound having a structure shown in Formula 1:

[0046] A-L-B Formula 1

[0047] In Formula 1, A is selected from any one of the structures represented by Formulas 2 to 4:

[0048]

[0049] Ry is independently selected from any one of substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted C2-C30 heteroaryl groups; or Ry can be directly bonded to L;

[0050] Z is independently selected from CH or N, and in the structures represented by Formulas 2 to 4, at least one Z in each structure is N; the Z at the connection with Lx and L is selected from CH;

[0051] The R 1 is independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl groups, substituted or unsubstituted C3-C12 cycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted C2-C30 heteroaryl groups;

[0052] a is independently selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8, b is selected from 0, 1, 2, 3, 4, or 5, c is selected from 0, 1, 2, 3, 4, 5, 6, or 7. When a, b, or c is greater than 1, two or more Rs 1 are the same or different from each other, or two adjacent Rs 1 can be bonded to form a substituted or unsubstituted ring;

[0053] The X 1 is selected from any one of a single bond, O, S, C(R 2 )(R 3 ), and N(R 4 );

[0054] The R 2 , R 3 are independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl groups, substituted or unsubstituted C3-C12 cycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted C2-C30 heteroaryl groups;

[0055] The R 4 is independently selected from any one of substituted or unsubstituted C1-C12 alkyl groups, substituted or unsubstituted C3-C12 cycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted C2-C30 heteroaryl groups;

[0056] B is the structure represented by Formula 5:

[0057]

[0058] The said X 2 is selected from O or S;

[0059] The said ring E is selected from any one of the following groups:

[0060]

[0061] The said Y is independently selected from CH or N, and "*" represents the fusion site;

[0062] The said R 5 and R 7 are independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C2-C30 heteroaryl;

[0063] The said d 1 is independently selected from 0, 1, 2, 3, 4, 5 or 6, and the said d 2 is independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, and the said d 3 is independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; when the said d 1 , d 2 or d 3 is 1, two or more Rs 7 are the same as or different from each other, or two adjacent Rs 7 are bonded to form a substituted or unsubstituted ring;

[0064] The said L and Lx are independently selected from any one of a single bond, substituted or unsubstituted C6-C30 arylene, and substituted or unsubstituted C2-C30 heteroarylene;

[0065] When there are multiple substituents in the said "substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene", the multiple substituents are the same as or different from each other, or two adjacent substituents can be bonded to form a substituted or unsubstituted ring.

[0066] Preferably, in the said formula 2 is selected from any one of formula 2-1 to formula 2-6, and in the said formula 3 is selected from any one of formula 3-1 to formula 3-8:

[0067]

[0068] The said R 1Any one selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C2-C18 heteroaryl;

[0069] The b 1 Selected from 0, 1, 2, 3, 4 or 5, the b 2 Selected from 0, 1, 2, 3 or 4, the b 3 Independently selected from 0, 1, 2 or 3, the b 4 Selected from 0, 1, or 2, the c 1 Selected from 0, 1, 2, 3, 4, 5, 6 or 7, the c 2 Independently selected from 0, 1, 2, 3, 4, 5 or 6, the c 3 Independently selected from 0, 1, 2, 3, 4 or 5, when the b 1 , b 2 , b 3 , b 4 , c 1 , c 2 Or c 3 When greater than 1, two or more Rs 1 Are the same as or different from each other, or two adjacent Rs 1 Can be bonded to form a substituted or unsubstituted ring;

[0070] The Lx is independently selected from any one of a single bond, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted triphenylene, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted cinnolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl;

[0071] Preferably, the "substituted" group in the Lx is selected from any one or more of deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C2-C18 heteroaryl. When there are multiple substituents, the multiple substituents are the same as or different from each other.

[0072] Preferably, the A is selected from any one of the following groups:

[0073]

[0074]

[0075]

[0076]

[0077] The said m 1 is independently selected from 0, 1, 2, 3, 4, 5 or 6, and the said m 2 is independently selected from 0, 1, 2, 3, 4 or 5, and the said m 3 is independently selected from 0, 1, 2, 3 or 4, and the said m 4 is independently selected from 0, 1, 2 or 3, and the said m 5 is independently selected from 0, 1, 2, 3, 4, 5, 6 or 7, and the said m 6 is independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; when the said m 1 , m 2 , m 3 , m 4 , m 5 or m 6 is greater than 1, two or more Rs 1 are the same as or different from each other, or two adjacent Rs 1 bond to form a substituted or unsubstituted ring.

[0078] Preferably, the said R 1 is independently selected from hydrogen, deuterium, halogen, cyano, or any one of the following substituted or unsubstituted groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, triphenylene, benzocyclopropyl, benzocyclobutyl, benzocyclopentyl, benzocyclohexyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, pyridyl, pyrimidinyl, triazinyl, pyrazinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl; or two adjacent Rs 1 can combine with each other to form any one of a substituted or unsubstituted benzene ring, naphthalene ring, or C3-C7 aliphatic ring.

[0079] Preferably, Ry is independently selected from the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, triphenylene, perylenyl, pyrenyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, pyridyl, bipyridyl, pyrimidinyl, pyrazinyl, triazinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, or Ry can be directly bonded to L;

[0080] The "substituted" group is selected from any one or more of deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C18 aryl, and substituted or unsubstituted C2-C18 heteroaryl. When there are multiple substituents, the multiple substituents are the same or different from each other.

[0081] Preferably, B is selected from any one of the following groups:

[0082]

[0083] More preferably, B is selected from any one of the following groups:

[0084]

[0085] The R 5 、R 7 are independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C18 aryl, and substituted or unsubstituted C2-C18 heteroaryl;

[0086] The n 1 is independently selected from 0, 1, 2, 3, 4 or 5, and the n 2 is independently selected from 0, 1, 2, 3, 4, 5, 6 or 7; n 3 is independently selected from 0, 1, 2, 3, 4, 5 or 6, and the n 4 is independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; when the n 1 、n 2 、n 3 or n 4 is greater than 1, two or more Rs 7 are the same or different from each other, or two adjacent Rs 7 are bonded to form a substituted or unsubstituted ring.

[0087] Even more preferably, B is selected from any one of the following groups:

[0088]

[0089]

[0090]

[0091] Preferably, L is independently selected from a single bond or any one of the following groups:

[0092]

[0093]

[0094] The X 3 is independently selected from any one of O, S, C(R 9 ) 2 , N(R 10 );

[0095] The R 8 , R 9 are independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C2-C18 heteroaryl; or two R 9 can be bonded to form a substituted or unsubstituted ring;

[0096] The R 10 is independently selected from any one of substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C2-C18 heteroaryl;

[0097] The f 1 is independently selected from 0, 1, 2, 3 or 4, the f 2 is independently selected from 0, 1, 2, 3, 4, 5 or 6, the f 3 is independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, the f 4 is independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, the f 5 is independently selected from 0, 1, 2 or 3, the f 6 is independently selected from 0, 1 or 2, the f 7 is independently selected from 0, 1, 2, 3, 4 or 5; when the f 1 , f 2 , f 3 , f 4 , f 5 , f 6 or f 7 is greater than 1, two or more R8 Two adjacent Rs, which may be the same or different from each other 8 are bonded to form a substituted or unsubstituted ring.

[0098] Preferably, each of said Rs 8 is independently selected from hydrogen, deuterium, halogen, cyano, or a substituted or unsubstituted group selected from the following: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, benzocyclopropyl, benzocyclobutyl, benzocyclopentyl, benzocyclohexyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, pyridyl, pyrimidinyl, triazinyl, pyrazinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl.

[0099] Most preferably, the heterocyclic compound is selected from any one of the following structures:

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113] Some specific structural forms of the compound of Formula 1 according to the present invention are listed above, but the present invention is not limited to these listed chemical structures. Any structure based on the structure shown in Formula 1 with substituents as defined above should be included.

[0114] The present invention also provides an organic electroluminescent device, comprising an anode, a cathode, and one or more organic layers, wherein the organic layer is located between the anode and the cathode or outside at least one of the anode and the cathode, and the organic layer comprises at least one heterocyclic compound of the present invention.

[0115] Specifically, the organic electroluminescent device of the present invention may comprise one or more organic layers, and the organic layer may comprise a light-emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, a covering layer, etc.

[0116] The organic layer may be located between the anode and the cathode, or outside one or more of the anode and the cathode. Specifically, the organic layer located between the anode and the cathode may comprise a light-emitting layer, a hole transport layer, a hole injection layer, an electron blocking layer, a light-emitting auxiliary layer, an electron transport layer, an electron injection layer, a hole blocking layer, etc., and the organic layer located outside one or more of the anode and the cathode may comprise a covering layer, etc.

[0117] Preferably, the organic layer comprises at least one of an electron transport layer, a hole blocking layer, and a covering layer, and at least one of the electron transport layer, the hole blocking layer, and the covering layer comprises at least one heterocyclic compound of the present invention.

[0118] Preferably, the organic layer is located between the anode and the cathode, the organic layer comprises an electron transport layer, and the electron transport layer comprises at least one heterocyclic compound of the present invention.

[0119] Preferably, the organic layer is located between the anode and the cathode, the organic layer comprises a hole blocking layer, and the hole blocking layer comprises at least one heterocyclic compound of the present invention.

[0120] Preferably, the organic layer is located outside one or more of the anode and the cathode, the organic layer comprises a covering layer, and the covering layer comprises at least one heterocyclic compound of the present invention.

[0121] Preferably, the organic layer may be a single-layer structure, a double-layer structure, or a multi-layer structure. At the same time, each of the organic layers may also comprise a single-layer or multi-layer structure, and the single-layer structure may be composed of a single substance or two or more substances. However, the structure of the organic electroluminescent device is not limited thereto, and it may comprise fewer or more organic layers. For example, the hole transport layer comprises a first hole transport layer and a second hole transport layer; the electron transport layer comprises a first electron transport layer and a second electron transport layer.

[0122] Preferably, the organic electroluminescent device of the present invention has the following structure, but is not limited thereto:

[0123] (1) Substrate / Anode / Hole Transport Layer / Light Emitting Layer / Electron Transport Layer / Cathode;

[0124] (2) Substrate / Anode / Hole Injection Layer / Hole Transport Layer / Light Emitting Layer / Electron Transport Layer / Electron Injection Layer / Cathode;

[0125] (3) Substrate / Anode / Hole Injection Layer / Hole Transport Layer / Light Emitting Layer / Electron Transport Layer / Electron Injection Layer / Cathode / Covering Layer;

[0126] (4) Substrate / Anode / Hole Injection Layer / Hole Transport Layer / Light Emitting Layer / Hole Blocking Layer / Electron Transport Layer / Electron Injection Layer / Cathode;

[0127] (5) Substrate / Anode / Hole Injection Layer / Hole Transport Layer / Electron Blocking Layer / Light Emitting Layer / Electron Transport Layer / Electron Injection Layer / Cathode;

[0128] (6) Substrate / Anode / Hole Injection Layer / Hole Transport Layer / Electron Blocking Layer / Light Emitting Layer / Electron Transport Layer / Electron Injection Layer / Cathode / Covering Layer;

[0129] (7) Substrate / Anode / Hole Injection Layer / Hole Transport Layer / Electron Blocking Layer / Light Emitting Layer / Hole Blocking Layer / Electron Transport Layer / Electron Injection Layer / Cathode;

[0130] (8) Substrate / Anode / Hole Injection Layer / Hole Transport Layer / Light Emitting Layer / Hole Blocking Layer / Electron Transport Layer / Electron Injection Layer / Cathode / Covering Layer;

[0131] (9) Substrate / Anode / Hole Injection Layer / First Hole Transport Layer / Second Hole Transport Layer / Light Emitting Layer / Electron Transport Layer / Electron Injection Layer / Cathode;

[0132] (10) Substrate / Anode / Hole Injection Layer / First Hole Transport Layer / Second Hole Transport Layer / Light Emitting Layer / Electron Transport Layer / Electron Injection Layer / Cathode / Covering Layer;

[0133] In the organic electroluminescent device of the present invention, for each functional layer, except for the heterocyclic compound materials described in the present invention, materials known in the art can be used. However, these materials are for illustrative purposes only and are not intended to limit the scope of the present application. The following separately introduces each organic functional layer of the above-mentioned organic electroluminescent device and the electrodes on both sides of the device:

[0134] The organic electroluminescent device of the present invention is usually formed on a substrate. The above-mentioned substrate only needs to remain unchanged when forming the electrodes and forming the organic layers. For example, substrates such as glass, plastic, polymer film, and silicon can be used.

[0135] As the anode material of the present invention, a material with a high work function is preferably used. The anode can be a transmissive electrode, a reflective electrode, or a semi-transmissive electrode. When the anode is a transmissive electrode, the material used to form the anode can be selected from indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2 ), zinc oxide (ZnO), or any combination thereof; when the anode is a semi-transmissive electrode or a reflective electrode, the material used to form the anode can be selected from magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof. The anode can have a single-layer structure or a multi-layer structure including two or more layers. For example, the anode can have a single-layer structure of Al or a three-layer structure of ITO / Ag / ITO, but the structure of the anode is not limited thereto.

[0136] The hole transport region of the present invention is provided on the anode, and the hole transport region can be selected from at least one of a hole injection layer, a hole transport layer, a light-emitting auxiliary layer, and an electron blocking layer. The hole transport region can have: 1) a single-layer structure, which includes a single layer containing a single material; or includes a single layer containing multiple materials; 2) a multi-layer structure, which includes multiple layers containing multiple materials.

[0137] As the hole injection layer material of the present invention, a material with a high work function is preferably used, and can be selected from any one or more of the following structures: metal porphyrin, oligothiophene, arylamine derivative, perylene derivative, hexanitrile hexaazatriphenylene compound, quinacridone compound, anthraquinone compound, and conductive polymers based on polyaniline and polythiophene, etc., but not limited thereto.

[0138] As the hole transport layer material of the present invention, a material with a high hole mobility is preferably used, and can be selected from any one or more of the following structures: carbazole derivative, triarylamine derivative, biphenyl diamine derivative, fluorene derivative, stilbene derivative, phthalocyanine compound, hexanitrile hexaazatriphenylene compound, quinacridone compound, anthraquinone compound, polyaniline, polythiophene, polyvinyl carbazole, etc., but not limited thereto.

[0139] As described above, the hole transport region can further include any one of a light-emitting auxiliary layer and an electron blocking layer. As the light-emitting auxiliary layer material or electron blocking layer material, other known materials suitable for this layer can be selected. Preferably, it is a compound capable of effectively blocking the migration of electrons to the hole transport region, and can be selected from any one or more of the following structures: triarylamine derivative, carbazole derivative, stilbene derivative, fluorene derivative, etc., but not limited thereto.

[0140] The light-emitting layer described in the present invention is provided on the hole transport region. The light-emitting layer can have a single-layer structure formed of a single material, a single-layer structure formed of multiple materials, or a multilayer structure having multiple layers formed of multiple materials.

[0141] As the light-emitting layer material described in the present invention, red, green, or blue light-emitting materials can be used. Generally, it contains a guest (doped) material and a host material. The guest material can be a simple fluorescent material or a phosphorescent material, or a combination of fluorescent and phosphorescent materials. The host material of the light-emitting layer not only needs to have bipolar charge transport properties but also appropriate energy levels to effectively transfer the excitation energy to the guest light-emitting material. The host material can be selected from any one or more of the following structures: stilbenyl aryl derivatives, stilbene derivatives, carbazole derivatives, triarylamine derivatives, anthracene derivatives, pyrene derivatives, etc., but not limited thereto. The guest material can be selected from any one or several of the following structures: metal complexes (such as iridium complexes, platinum complexes, osmium complexes, rhodium complexes, etc.), anthracene derivatives, pyrene derivatives, perylene derivatives, etc., but not limited thereto.

[0142] As the doping ratio of the host material and the guest material of the light-emitting layer, the optimum can vary depending on the materials used. Generally, the doping ratio of the guest material in the light-emitting layer is 0.01% to 20%, preferably 0.1% to 15%, and more preferably 1% to 10%.

[0143] The electron transport region described in the present invention is provided on the light-emitting layer. The electron transport region can be selected from at least one of an electron injection layer, an electron transport layer, and a hole blocking layer. The electron transport region can have: 1) a single-layer structure, which includes a single layer containing a single material; or includes a single layer containing multiple materials; 2) a multilayer structure, which includes multiple layers containing multiple materials.

[0144] As the hole blocking layer material described in the present invention, it is preferably capable of effectively blocking hole materials. In addition to the heterocyclic compounds provided by the present invention, it can also be selected from any one or more of the following structures: phenanthroline derivatives, rare earth derivatives, oxazole derivatives, triazole derivatives, triazine derivatives, etc., but not limited thereto.

[0145] As the electron transport layer material described in the present invention, a material with high electron mobility is preferred. In addition to the heterocyclic compounds provided by the present invention, it can also be selected from any one or more of the following structures: metal chelates, oxazolooxazole derivatives, thiazole derivatives, diazole derivatives, azobenzene derivatives, phenazine derivatives, silicon-containing heterocyclic compounds, boron-containing heterocyclic compounds, cyano compounds, quinoline derivatives, phenanthroline derivatives, benzimidazole derivatives, etc., but not limited thereto.

[0146] As the electron injection layer material described in the present invention, a material with a low work function is preferably selected, and it can be any one or more of the following structures: metals, alkali metals, alkaline earth metals, halides of alkali metals, halides of alkaline earth metals, oxides of alkali metals, oxides of alkaline earth metals, alkali metal salts, alkaline earth metal salts, metal complexes, and other substances with high electron injection properties. Examples include Li, Ca, Sr, LiF, CsF, CaF 2 、BaO、Li 2 CO 3 、CaCO 3 、Li 2 C 2 O 4 、Cs 2 C 2 O 4 、CsAlF 4 、LiOx, Yb, Tb, cesium 8-hydroxyquinoline, tris(8-hydroxyquinoline)aluminum, etc., but not limited thereto.

[0147] The cathode described in the present invention is provided on the electron transport region. As the cathode material described in the present invention, a material with a low work function is preferably selected. The cathode can be selected from a transmissive electrode, a semi-reflective electrode, or a reflective electrode. When the cathode is a transmissive electrode, the material used to form the cathode can be selected from transparent metal oxides (e.g., ITO, IZO, etc.); when the cathode is a semi-reflective electrode or a reflective electrode, the material used to form the cathode can be selected from Ag, Mg, Cu, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti, compounds including them, or mixtures thereof (e.g., a mixture of Ag and Mg), but not limited thereto.

[0148] As the cover layer described in the present invention, in addition to the heterocyclic compounds provided by the present invention, it can be selected from any one or more of the following structures: inorganic compounds (e.g., metal oxides, metal nitrides, metal fluorides, etc.), organic compounds (arylamine derivatives, carbazole derivatives, benzimidazole derivatives, benzoxazole derivatives, benzothiazole derivatives, triazole derivatives, etc.), or can be formed by mixing inorganic compounds and organic compounds, but not limited thereto.

[0149] The present invention also provides a preparation method of the compound of formula 1, but the preparation method of the present invention is not limited thereto.

[0150] [Synthesis route of the compound of formula 1]

[0151]

[0152] The above raw materials a to c can be commercially available products or prepared by preparation methods well-known to those skilled in the art. Taking raw materials a and c as examples, they can be prepared by the following preparation methods:

[0153] Preparation of raw material a:

[0154]

[0155]

[0156] Preparation of raw material c:

[0157]

[0158] Xa, Xb, Xc, Xd, Xe, and Xf are independently selected from any one of I, Br, and Cl.

[0159] The present invention does not impose any special restrictions on the thickness of each organic layer of the organic electroluminescent device, and the commonly used thicknesses in the art can be adopted.

[0160] The organic electroluminescent device described in the present invention can be manufactured by successively laminating the above structures. Manufacturing methods can use well-known methods such as wet film formation methods and dry film formation methods. As specific examples of wet film formation methods, various coating methods such as spin coating method, dipping method, casting method, and inkjet method can be cited. As specific examples of dry film formation methods, vacuum evaporation method, sputtering method, plasma method, ion plating method, etc. can be cited, but are not limited thereto.

[0161] The organic electroluminescent device described in the present invention can be widely applied to fields such as panel display, lighting source, flexible OLED, electronic paper, organic solar cell, organic photoreceptor or organic thin film transistor, sign board, signal lamp, etc.

[0162] Through the following examples, the present invention will be more elaborately explained, but it is not intended to limit the present invention thereby. Based on this description, those of ordinary skill in the art will be able to implement the present invention and prepare other compounds and devices according to the present invention without creative efforts within the entire disclosed scope.

[0163] Description of raw materials, reagents, and characterization equipment:

[0164] The present invention does not have any special restrictions on the sources of raw materials and reagents used in the following examples, and they can be commercially available products or prepared by preparation methods well-known to those skilled in the art.

[0165] Mass spectrometry was performed using a Waters G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer from the UK, with chloroform as the solvent;

[0166] Elemental analysis was performed using a Vario EL cube organic elemental analyzer from Elementar, Germany, with a sample mass of 5 - 10 mg.

[0167] [Synthesis Example 1] Preparation of Compound 1

[0168]

[0169] Preparation of Intermediate A-1:

[0170] Under nitrogen protection, a-1 (100.00 mmol, 35.38 g), B 2 Pin 2 (110.00 mmol, 27.93 g), Pd(PPh 3 ) 4 (1.10 mmol, 1.16 g), Na 2 CO 3 (150.00 mmol, 15.90 g), and DMF (600 mL) were added to the reaction flask, and the mixture was heated for reaction for 2 h. After the reaction was completed, it was cooled to room temperature, 700 mL of distilled water was added, and then it was extracted with ethyl acetate. The organic phase was dried over anhydrous MgSO 4 , the solvent was removed by rotary evaporation, and then recrystallized with toluene:ethanol = 10:3 to obtain Intermediate A-1 (36.97 g, yield 83%); HPLC purity ≥ 99.62%. Mass spectrometry m / z: 445.2224 (theoretical value: 445.2213).

[0171] Preparation of Intermediate B-1:

[0172] Under nitrogen protection, Intermediate A-1 (72.00 mmol, 32.07 g), b-1 (70.00 mmol, 13.40 g), Pd(PPh 3 ) 4 (0.70 mmol, 0.81 g), K 2 CO 3 (105.00 mmol, 14.51 g), and 140 mL of toluene, 70 mL of ethanol, and 70 mL of water were added to the reaction flask, and the mixture was stirred. The reaction was carried out under reflux for 3 h. After the reaction was completed, it was cooled to room temperature, and then filtered to obtain a filter cake, which was rinsed with ethanol. Finally, the filter cake was recrystallized with toluene / ethanol = 5:1 to obtain Intermediate B-1 (24.08 g, yield 80%); HPLC purity ≥ 99.71%. Mass spectrometry m / z: 429.1293 (theoretical value: 429.1284).

[0173] Preparation of Intermediate C-1:

[0174] Under nitrogen protection, intermediate B-1 (45.00 mmol, 19.35 g), B 2 Pin 2 (50.00 mmol, 12.70 g), Pd(dppf)Cl 2 (0.45 mmol, 0.33 g), Na 2 CO 3 (67.50 mmol, 7.15 g) and DMF (270 mL) were added to the reaction flask, and the mixture was heated and reacted for 4 h. After the reaction was completed, it was cooled to room temperature, 350 mL of distilled water was added, and then it was extracted with ethyl acetate. The organic phase was dried over anhydrous MgSO 4 , the solvent was removed by rotary evaporation, and then recrystallized with toluene:ethanol = 10:1, and dried to obtain intermediate C-1 (18.30 g, yield 78%); HPLC purity ≥ 99.83%. Mass spectrometry m / z: 521.2539 (theoretical value: 521.2526).

[0175] Preparation of Compound 1:

[0176] Under nitrogen protection, intermediate C-1 (25.50 mmol, 13.30 g), c-1 (25.00 mmol, 6.20 g), Pd 2 (dba) 3 (0.25 mmol, 0.23 g), P(t-Bu) 3 (0.75 mmol, 0.15 g), K 2 CO 3 (37.50 mmol, 5.18 g), THF (100 mL) were added to the reaction flask, and the mixture was stirred. The mixture was heated under reflux for 6 hours. After the reaction was completed, it was cooled to room temperature, and the filter cake was obtained by suction filtration. The filter cake was rinsed with ethanol, and finally the filter cake was recrystallized with toluene to obtain Compound 1 (10.55 g, yield 75%); HPLC purity ≥ 99.99%. Mass spectrometry m / z: 562.2060 (theoretical value: 562.2045). Theoretical elemental content (%) C 41 H 26 N 2 O: C, 87.52; H, 4.66; N, 4.98. Measured elemental content (%): C, 87.49; H, 4.71; N, 5.01.

[0177] [Synthesis Example 2] Preparation of Compound 77

[0178]

[0179] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-77, b-1 with an equimolar amount of b-77, and c-1 with an equimolar amount of c-77. According to the same preparation method as in Synthesis Example 1, Compound 77 (12.54 g) was obtained; HPLC purity ≥ 99.94%. Mass spectrometry m / z: 716.2588 (theoretical value: 716.2576). Theoretical elemental content (%) C 51 H 32 N 4 O: C, 85.45; H, 4.50; N, 7.82. Measured elemental content (%): C, 85.51; H, 4.46; N, 7.78.

[0180] [Synthesis Example 3] Preparation of Compound 92

[0181]

[0182] Preparation of Intermediate b-92:

[0183] Under nitrogen protection, d-92 (100.00 mmol, 33.49 g), e-92 (102.00 mmol, 15.95 g), Pd(PPh 3 ) 4 (1.00 mmol, 1.16 g) and Na 2 CO 3 (150.00 mmol, 15.90 g) and 200 mL of toluene, 100 mL of ethanol, 100 mL of water were added to the reaction flask, and the mixture was stirred. The reaction was carried out under reflux for 2 h. After the reaction was completed, it was cooled to room temperature, and then filtered to obtain a filter cake, which was washed with ethanol. Finally, the filter cake was recrystallized from toluene to obtain Intermediate b-92 (28.44 g, yield 89%); HPLC purity ≥ 99.62%. Mass spectrometry m / z: 317.9571 (theoretical value: 317.9559).

[0184] Preparation of Intermediate a-92:

[0185] Dissolve f-92 (200.00 mmol, 53.71 g) in 400 ml of THF. At -78 °C, slowly add 100 ml of a 15% hexane solution of n-butyllithium (170 mmol) (about 1 hour). Stir at -78 °C for 1 hour. Subsequently, while maintaining the temperature at -78 °C, add a solution of g-92 (170.00 mmol, 30.98 g) dissolved in 140 ml of THF. After addition, the reaction mixture was gradually warmed to room temperature, and then treated with NH 4Quench with Cl, and then concentrate on a rotary evaporator. Add 720 ml of acetic acid to the concentrated solution, and then add 140 ml of HCl. Heat the mixture to 75 °C and maintain for 4 hours. After the reaction is completed, cool to room temperature, filter by suction to obtain a filter cake, and rinse the filter cake with methanol, then dry under reduced pressure at 40 °C to obtain intermediate a-92 (42.11 g, yield 70%); HPLC purity ≥ 99.64%. Mass spectrometry m / z: 353.0981 (theoretical value: 353.0971).

[0186] Preparation of Compound 92:

[0187] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-92, b-1 with an equimolar amount of b-92, and c-1 with an equimolar amount of c-77. According to the same preparation method as in Synthesis Example 1, Compound 92 (13.23 g) is obtained; HPLC purity ≥ 99.93%. Mass spectrometry m / z: 766.2721 (theoretical value: 766.2733). Theoretical elemental content (%) C 55 H 34 N 4 O: C, 86.14; H, 4.47; N, 7.31. Measured elemental content (%): C, 86.09; H, 4.52; N, 7.27.

[0188] [Synthesis Example 4] Preparation of Compound 111

[0189]

[0190] Replace intermediate A-1 in Synthesis Example 1 with an equimolar amount of intermediate A-77, and c-1 with an equimolar amount of c-111. According to the same preparation method as in Synthesis Example 1, Compound 111 (12.40 g) is obtained; HPLC purity ≥ 99.96%. Mass spectrometry m / z: 688.2529 (theoretical value: 688.2515). Theoretical elemental content (%) C 51 H 32 N 2 O: C, 88.93; H, 4.68; N, 4.07. Measured elemental content (%): C, 88.89; H, 4.71; N, 4.11.

[0191] [Synthesis Example 5] Preparation of Compound 126

[0192]

[0193] Preparation of Intermediate a-126:

[0194] Replace f-92 in Synthesis Example 3 with an equimolar amount of f-126 and g-92 with an equimolar amount of g-126. According to the same preparation method as Intermediate a-92 in Synthesis Example 3, Intermediate a-126 (49.70 g) was obtained; HPLC purity ≥ 99.59%. Mass spectrometry m / z: 766.2721 (theoretical value: 766.2733).

[0195] Preparation of Compound 126:

[0196] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-126, b-1 with an equimolar amount of b-126, and c-1 with an equimolar amount of c-111. According to the same preparation method as in Synthesis Example 1, Compound 126 (13.43 g) was obtained; HPLC purity ≥ 99.92%. Mass spectrometry m / z: 789.2765 (theoretical value: 789.2780). Theoretical elemental content (%) C 58 H 35 N 3 O: C, 88.19; H, 4.47; N, 5.32. Measured elemental content (%): C, 88.22; H, 4.51; N, 5.27.

[0197] [Synthesis Example 6] Preparation of Compound 157

[0198]

[0199] Preparation of Intermediate f-157:

[0200] Under nitrogen protection, d-157 (230.00 mmol, 65.07 g), e-157 (235.00 mmol, 36.98 g), Pd(PPh 3 ) 4 (2.30 mmol, 2.66 g) and Na 2 CO 3 (350.00 mmol, 37.10 g) as well as 400 mL of toluene, 200 mL of ethanol, and 200 mL of water were added to the reaction flask. The mixture was stirred and reacted under heating and reflux for 2 h. After the reaction was completed, it was cooled to room temperature, and then filtered to obtain a filter cake, which was rinsed with ethanol. Finally, the filter cake was recrystallized with toluene to obtain Intermediate f-157 (55.59 g, yield 90%); HPLC purity ≥ 99.67%. Mass spectrometry m / z: 266.9466 (theoretical value: 266.9450).

[0201] Preparation of Intermediate a-157:

[0202] Replace f-92 in Synthesis Example 3 with an equimolar amount of f-157, and replace g-92 with an equimolar amount of g-157. According to the same preparation method as Intermediate a-92 in Synthesis Example 3, Intermediate a-157 (45.77 g) was obtained; HPLC purity ≥ 99.59%. Mass spectrometry m / z: 407.1449 (theoretical value: 407.1441).

[0203] Preparation of Compound 157:

[0204] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-157, and replace c-1 with an equimolar amount of c-111. According to the same preparation method as in Synthesis Example 1, Compound 157 (12.82 g) was obtained; HPLC purity ≥ 99.93%. Mass spectrometry m / z: 742.2997 (theoretical value: 742.2984). Theoretical elemental content (%) C 55 H 38 N 2 O: C, 88.92; H, 5.16; N, 3.77. Measured elemental content (%): C, 88.87; H, 5.20; N, 3.81.

[0205] [Synthesis Example 7] Preparation of Compound 175

[0206]

[0207] Preparation of Intermediate c-175:

[0208] Add j-175 (50 mmol, 10.96 g) and 50 mL of DMF solution to a reaction flask to dissolve it completely. Then add CBr 4 (55 mmol, 18.24 g) and sodium tert-butoxide (200 mmol, 19.22 g). Stir the mixture at room temperature for 30 minutes. After the reaction is completed, pour the solution into distilled water, then extract with dichloromethane. Wash the organic phase with distilled water and dry it with anhydrous MgSO 4 Dry, filter and concentrate under reduced pressure. The crude product was purified by flash chromatography (petroleum ether: ethyl acetate = 30:1) to obtain Intermediate c-175 (13.57 g, yield 91%). HPLC purity ≥ 99.78%. Mass spectrometry m / z: 296.9775 (theoretical value: 296.9789).

[0209] Preparation of Compound 157:

[0210] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-175, b-1 with an equimolar amount of b-175, and c-1 with an equimolar amount of c-175. According to the same preparation method as in Synthesis Example 1, Compound 175 (12.93 g) was obtained; HPLC purity ≥ 99.94%. Mass spectrometry m / z: 738.2688 (theoretical value: 738.2671). Theoretical elemental content (%) C 55 H 34 N 2 O: C, 89.41; H, 4.64; N, 3.79. Measured elemental content (%): C, 89.36; H, 4.67; N, 3.83.

[0211] [Synthesis Example 8] Preparation of Compound 209

[0212]

[0213] Preparation of Intermediate c-209:

[0214] Replace j-175 in Synthesis Example 7 with an equimolar amount of j-209. According to the same preparation method as Intermediate c-175 in Synthesis Example 7, Intermediate c-209 (13.41 g) was obtained. HPLC purity ≥ 99.75%. Mass spectrometry m / z: 296.9775 (theoretical value: 296.9789).

[0215] Preparation of Compound 209:

[0216] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-209 and c-1 with an equimolar amount of c-209. According to the same preparation method as in Synthesis Example 1, Compound 209 (11.34 g) was obtained; HPLC purity ≥ 99.98%. Mass spectrometry m / z: 612.2219 (theoretical value: 612.2202). Theoretical elemental content (%) C 45 H 28 N 2 O: C, 88.21; H, 4.61; N, 4.57. Measured elemental content (%): C, 88.17; H, 4.59; N, 4.61.

[0217] [Synthesis Example 9] Preparation of Compound 253

[0218]

[0219] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-253, b-1 with an equimolar amount of b-253, and c-1 with an equimolar amount of c-209. According to the same preparation method as in Synthesis Example 1, compound 253 (13.22 g) was obtained; HPLC purity ≥ 99.92%. Mass spectrometry m / z: 777.2796 (theoretical value: 777.2780). Theoretical elemental content (%) C 57 H 35 N 3 O: C, 88.01; H, 4.54; N, 5.40. Measured elemental content (%): C, 87.98; H, 4.57; N, 5.36.

[0220] [Synthesis Example 10] Preparation of Compound 293

[0221]

[0222] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-293, b-1 with an equimolar amount of b-293, and c-1 with an equimolar amount of c-175. According to the same preparation method as in Synthesis Example 1, compound 293 (13.14 g) was obtained; HPLC purity ≥ 99.93%. Mass spectrometry m / z: 772.3442 (theoretical value: 772.3454). Theoretical elemental content (%) C 57 H 44 N 2 O: C, 88.57; H, 5.74; N, 3.62. Measured elemental content (%): C, 88.61; H, 5.69; N, 3.65.

[0223] [Synthesis Example 11] Preparation of Compound 296

[0224]

[0225] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-296, b-1 with an equimolar amount of b-296, and c-1 with an equimolar amount of c-111. According to the same preparation method as in Synthesis Example 1, compound 296 (13.63 g) was obtained; HPLC purity ≥ 99.91%. Mass spectrometry m / z: 813.2789 (theoretical value: 813.2780). Theoretical elemental content (%) C 60 H 35 N 3 O: C, 88.54; H, 4.33; N, 5.16. Measured elemental content (%): C, 88.51; H, 4.29; N, 5.21.

[0226] [Synthesis Example 12] Preparation of Compound 302

[0227]

[0228] Replace intermediate A-1 in Synthesis Example 1 with an equimolar amount of intermediate A-92, b-1 with an equimolar amount of b-302, and c-1 with an equimolar amount of c-111. According to the same preparation method as in Synthesis Example 1, compound 302 (13.41 g) was obtained; HPLC purity ≥ 99.92%. Mass spectrometry m / z: 788.2838 (theoretical value: 788.2828). Theoretical elemental content (%) C 59 H 36 N 2 O: C, 89.82; H, 4.60; N, 3.55. Measured elemental content (%): C, 89.77; H, 4.56; N, 3.60.

[0229] [Synthesis Example 13] Preparation of Compound 326

[0230]

[0231] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-326, b-1 with an equimolar amount of b-326, and c-1 with an equimolar amount of c-111. According to the same preparation method as in Synthesis Example 1, compound 326 (12.83 g) was obtained; HPLC purity ≥ 99.93%. Mass spectrometry m / z: 743.2953 (theoretical value: 743.2937). Theoretical elemental content (%) C 54 H 37 N 3 O: C, 87.19; H, 5.01; N, 5.65. Measured elemental content (%): C, 87.22; H, 4.97; N, 5.63.

[0232] [Synthesis Example 14] Preparation of Compound 330

[0233]

[0234] Preparation of intermediate b-330:

[0235] Replace d-92 in Synthesis Example 3 with an equimolar amount of d-330. According to the same preparation method as intermediate b-92 in Synthesis Example 3, intermediate b-330 (27.98 g) was obtained; HPLC purity ≥ 99.62%. Mass spectrometry m / z: 319.9953 (theoretical value: 319.9967).

[0236] Preparation of compound 330:

[0237] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-330, b-1 with an equimolar amount of b-330, and c-1 with an equimolar amount of c-209. According to the same preparation method as in Synthesis Example 1, compound 330 (13.06 g) was obtained; HPLC purity ≥ 99.92%. Mass spectrometry m / z: 756.2760 (theoretical value: 756.2777). Theoretical elemental content (%) C 55 H 36 N 2 O 2 : C, 87.28; H, 4.79; N, 3.70. Measured elemental content (%): C, 87.33; H, 4.81; N, 3.65.

[0238] [Synthesis Example 15] Preparation of Compound 337

[0239]

[0240] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-337, b-1 with an equimolar amount of b-337, and c-1 with an equimolar amount of c-175. According to the same preparation method as in Synthesis Example 1, compound 337 (11.37 g) was obtained; HPLC purity ≥ 99.97%. Mass spectrometry m / z: 614.2116 (theoretical value: 614.2107). Theoretical elemental content (%) C 43 H 26 N 4 O: C, 84.02; H, 4.26; N, 9.11. Measured elemental content (%): C, 83.98; H, 4.30; N, 9.08.

[0241] [Synthesis Example 16] Preparation of Compound 343

[0242]

[0243] Preparation of Intermediate b-343:

[0244] Replace d-92 in Synthesis Example 3 with an equimolar amount of d-343 and e-92 with an equimolar amount of e-343. According to the same preparation method as Intermediate b-92 in Synthesis Example 3, intermediate b-343 (24.53 g) was obtained; HPLC purity ≥ 99.67%. Mass spectrometry m / z: 270.9718 (theoretical value: 270.9701).

[0245] Preparation of Compound 343:

[0246] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-343, b-1 with an equimolar amount of b-343, and c-1 with an equimolar amount of c-111. According to the same preparation method as in Synthesis Example 1, compound 343 (13.11 g) was obtained; HPLC purity ≥ 99.92%. Mass spectrometry m / z: 770.2969 (theoretical value: 770.2984). Theoretical elemental content (%) C 55 H 30 D 4 N 4 O: C, 85.69; H, 4.97; N, 7.27. Measured elemental content (%): C, 85.73; H, 5.02; N, 7.22.

[0247] [Synthesis Example 17] Preparation of Compound 405

[0248]

[0249] Preparation of Intermediate c-405:

[0250] Replace j-175 in Synthesis Example 7 with an equimolar amount of j-405. According to the same preparation method as Intermediate c-175 in Synthesis Example 7, Intermediate c-405 (13.27 g) was obtained. HPLC purity ≥ 99.73%. Mass spectrometry m / z: 296.9777 (theoretical value: 296.9789).

[0251] Preparation of Compound 405:

[0252] Replace Intermediate A-1 in Synthesis Example 1 with an equimolar amount of Intermediate A-92, b-1 with an equimolar amount of b-405, and c-1 with an equimolar amount of c-405. According to the same preparation method as in Synthesis Example 1, compound 405 (11.37 g) was obtained; HPLC purity ≥ 99.98%. Mass spectrometry m / z: 614.2118 (theoretical value: 614.2107). Theoretical elemental content (%) C 43 H 26 N 4 O: C, 84.02; H, 4.26; N, 9.11. Measured elemental content (%): C, 83.99; H, 4.31; N, 9.07.

[0253] [Synthesis Example 18] Preparation of Compound 408

[0254]

[0255] Preparation of Intermediate c-408:

[0256] Replace j-175 in Synthesis Example 7 with an equimolar amount of j-408, and according to the same preparation method as Intermediate c-175 in Synthesis Example 7, Intermediate c-408 (13.42 g) was obtained. HPLC purity ≥ 99.76%. Mass spectrometry m / z: 296.9777 (theoretical value: 296.9789).

[0257] Preparation of Intermediate a-408:

[0258] Replace f-92 in Synthesis Example 3 with an equimolar amount of f-408 and g-92 with an equimolar amount of g-408, and according to the same preparation method as Intermediate a-92 in Synthesis Example 3, Intermediate a-408 (42.83 g) was obtained; HPLC purity ≥ 99.64%. Mass spectrometry m / z: 354.0937 (theoretical value: 354.0924).

[0259] Preparation of Compound 408:

[0260] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-408, b-1 with an equimolar amount of b-408, and c-1 with an equimolar amount of c-408, and according to the same preparation method as in Synthesis Example 1, Compound 408 (12.30 g) was obtained; HPLC purity ≥ 99.95%. Mass spectrometry m / z: 692.2340 (theoretical value: 692.2325). Theoretical elemental content (%) C 47 H 28 N 6 O: C, 81.49; H, 4.07; N, 12.13. Measured elemental content (%): C, 81.53; H, 4.12; N, 12.09.

[0261] [Synthesis Example 19] Preparation of Compound 431

[0262]

[0263] Preparation of Intermediate c-431:

[0264] Replace j-175 in Synthesis Example 7 with an equimolar amount of j-431, and according to the same preparation method as Intermediate c-175 in Synthesis Example 7, Intermediate c-431 (13.12 g) was obtained. HPLC purity ≥ 99.73%. Mass spectrometry m / z: 296.9779 (theoretical value: 296.9789).

[0265] Preparation of Intermediate a-408:

[0266] Replace f-92 in Synthesis Example 3 with an equimolar amount of f-431, and replace g-92 with an equimolar amount of g-431. According to the same preparation method as Intermediate a-92 in Synthesis Example 3, Intermediate a-431 (51.71 g) was obtained; HPLC purity ≥ 99.61%. Mass spectrometry m / z: 453.1297 (theoretical value: 453.1284).

[0267] Preparation of Compound 431:

[0268] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-431, b-1 with an equimolar amount of b-431, and c-1 with an equimolar amount of c-431. According to the same preparation method as in Synthesis Example 1, Compound 431 (13.43 g) was obtained; HPLC purity ≥ 99.93%. Mass spectrometry m / z: 789.2797 (theoretical value: 789.2780). Theoretical elemental content (%) C 58 H 35 N 3 O: C, 88.19; H, 4.47; N, 5.32. Measured elemental content (%): C, 88.23; H, 4.52; N, 5.27.

[0269] [Synthesis Example 20] Preparation of Compound 444

[0270]

[0271] Preparation of Intermediate c-444:

[0272] Replace j-175 in Synthesis Example 7 with an equimolar amount of j-444. According to the same preparation method as Intermediate c-175 in Synthesis Example 7, Intermediate c-444 (13.27 g) was obtained. HPLC purity ≥ 99.75%. Mass spectrometry m / z: 296.9776 (theoretical value: 296.9789).

[0273] Preparation of Compound 444:

[0274] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-444, b-1 with an equimolar amount of b-444, and c-1 with an equimolar amount of c-444. According to the same preparation method as in Synthesis Example 1, Compound 444 (12.49 g) was obtained; HPLC purity ≥ 99.95%. Mass spectrometry m / z: 703.2278 (theoretical value: 703.2260). Theoretical elemental content (%) C 50 H 29 N 3 O 2: C, 85.33; H, 4.15; N, 5.97. Measured elemental content (%): C, 85.29; H, 4.11; N, 6.03.

[0275] [Synthesis Example 21] Preparation of Compound 459

[0276]

[0277] Preparation of Intermediate c-459:

[0278] Replace j-175 in Synthesis Example 7 with an equimolar amount of j-459, and according to the same preparation method as Intermediate c-175 in Synthesis Example 7, Intermediate c-459 (15.15 g) was obtained. HPLC purity ≥ 99.69%. Mass spectrometry m / z: 346.9961 (theoretical value: 346.9946).

[0279] Preparation of Compound 459:

[0280] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-459, b-1 with an equimolar amount of b-459, and c-1 with an equimolar amount of c-459, and according to the same preparation method as in Synthesis Example 1, Compound 459 (11.97 g) was obtained; HPLC purity ≥ 99.96%. Mass spectrometry m / z: 664.2249 (theoretical value: 664.2263). Theoretical elemental content (%) C 47 H 28 N 4 O: C, 84.92; H, 4.25; N, 8.43;. Measured elemental content (%): C, 84.87; H, 4.30; N, 8.39;.

[0281] [Synthesis Example 22] Preparation of Compound 466

[0282]

[0283] Preparation of Intermediate c-466:

[0284] Replace j-175 in Synthesis Example 7 with an equimolar amount of j-466, and according to the same preparation method as Intermediate c-175 in Synthesis Example 7, Intermediate c-466 (14.97 g) was obtained. HPLC purity ≥ 99.67%. Mass spectrometry m / z: 346.9959 (theoretical value: 346.9946).

[0285] Preparation of Intermediate a-466:

[0286] Replace f-92 in Synthesis Example 3 with an equimolar amount of f-466, and replace g-92 with an equimolar amount of g-466. According to the same preparation method as Intermediate a-92 in Synthesis Example 3, Intermediate a-466 (41.62 g) was obtained; HPLC purity ≥ 99.66%. Mass spectrometry m / z: 354.0907 (theoretical value: 354.0924).

[0287] Preparation of Compound 466:

[0288] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-466, replace b-1 with an equimolar amount of b-466, and replace c-1 with an equimolar amount of c-466. According to the same preparation method as in Synthesis Example 1, Compound 466 (12.51 g) was obtained; HPLC purity ≥ 99.94%. Mass spectrometry m / z: 714.2440 (theoretical value: 714.2420). Theoretical elemental content (%) C 51 H 30 N 4 O: C, 85.69; H, 4.23; N, 7.84. Measured elemental content (%): C, 85.72; H, 4.19; N, 7.87.

[0289] [Synthesis Example 23] Preparation of Compound 496

[0290]

[0291] Preparation of Intermediate f-496:

[0292] Replace d-157 in Synthesis Example 6 with an equimolar amount of d-496, and replace e-157 with an equimolar amount of e-92. According to the same preparation method as Intermediate f-157 in Synthesis Example 3, Intermediate f-496 (55.59 g) was obtained; HPLC purity ≥ 99.69%. Mass spectrometry m / z: 269.9763 (theoretical value: 269.9749).

[0293] Preparation of Intermediate a-496:

[0294] Replace f-92 in Synthesis Example 3 with an equimolar amount of f-496, and replace g-92 with an equimolar amount of g-496. According to the same preparation method as Intermediate a-92 in Synthesis Example 3, Intermediate a-496 (41.98 g) was obtained; HPLC purity ≥ 99.67%. Mass spectrometry m / z: 357.1211 (theoretical value: 357.1222).

[0295] Preparation of Compound 496:

[0296] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-496, b-1 with an equimolar amount of b-496, and c-1 with an equimolar amount of c-496. According to the same preparation method as in Synthesis Example 1, Compound 496 (12.12 g) was obtained; HPLC purity ≥ 99.95%. Mass spectrometry m / z: 682.2397 (theoretical value: 682.2381). Theoretical elemental content (%) C 49 H 26 D 4 N 2 S: C, 86.19; H, 5.02; N, 4.10. Measured elemental content (%): C, 86.25; H, 4.97; N, 4.07.

[0297] [Synthesis Example 24] Preparation of Compound 506

[0298]

[0299] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-506, b-1 with an equimolar amount of b-506, and c-1 with an equimolar amount of c-506. According to the same preparation method as in Synthesis Example 1, Compound 506 (13.06 g) was obtained; HPLC purity ≥ 99.94%. Mass spectrometry m / z: 756.2334 (theoretical value: 756.2348). Theoretical elemental content (%) C 53 H 32 N 4 S: C, 84.10; H, 4.26; N, 7.40. Measured elemental content (%): C, 84.06; H, 4.31; N, 7.37.

[0300] [Synthesis Example 25] Preparation of Compound 529

[0301]

[0302] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-529, b-1 with an equimolar amount of b-529, and c-1 with an equimolar amount of c-529. According to the same preparation method as in Synthesis Example 1, Compound 529 (12.91 g) was obtained; HPLC purity ≥ 99.94%. Mass spectrometry m / z: 737.1716 (theoretical value: 737.1708). Theoretical elemental content (%) C 48 H 27 N 5 S 2 : C, 78.13; H, 3.69; N, 9.49. Measured elemental content (%): C, 78.09; H, 3.74; N, 9.52.

[0303] [Synthesis Example 26] Preparation of Compound 536

[0304]

[0305] Replace intermediate A-1 in Synthesis Example 1 with an equimolar amount of intermediate A-92, b-1 with an equimolar amount of b-536, and c-1 with an equimolar amount of c-536. According to the same preparation method as in Synthesis Example 1, compound 536 (13.67 g) was obtained; HPLC purity ≥ 99.93%. Mass spectrometry m / z: 780.2585 (theoretical value: 780.2599). Theoretical elemental content (%) C 57 H 36 N 2 S: C, 87.66; H, 4.65; N, 3.59. Measured elemental content (%): C, 87.70; H, 4.62; N, 3.62.

[0306] [Synthesis Example 27] Preparation of Compound 547

[0307]

[0308] Preparation of intermediate a-547:

[0309] Replace f-92 in Synthesis Example 3 with an equimolar amount of f-547 and g-92 with an equimolar amount of g-547. According to the same preparation method as intermediate a-92 in Synthesis Example 3, intermediate a-547 (49.70 g) was obtained; HPLC purity ≥ 99.62%. Mass spectrometry m / z: 429.1271 (theoretical value: 429.1284).

[0310] Preparation of compound 547:

[0311] Replace a-1 in Synthesis Example 1 with an equimolar amount of a-547, b-1 with an equimolar amount of b-547, and c-1 with an equimolar amount of c-547. According to the same preparation method as in Synthesis Example 1, compound 547 (12.79 g) was obtained; HPLC purity ≥ 99.95%. Mass spectrometry m / z: 730.2455 (theoretical value: 730.2443). Theoretical elemental content (%) C 53 H 34 N 2 S: C, 87.09; H, 4.69; N, 3.83. Measured elemental content (%): C, 87.13; H, 4.74; N, 3.78.

[0312] [Synthesis Example 28] Preparation of Compound 551

[0313]

[0314] Preparation of Intermediate a-547:

[0315] Replace f-92 in Synthesis Example 3 with an equimolar amount of f-551 and g-92 with an equimolar amount of g-551. According to the same preparation method as Intermediate a-92 in Synthesis Example 3, Intermediate a-551 (53.86 g) was obtained; HPLC purity ≥ 99.59%. Mass spectrometry m / z: 479.1429 (theoretical value: 479.1441).

[0316] Preparation of Intermediate A-551:

[0317] Under nitrogen protection, a-551 (45.00 mmol, 35.38 g), B 2 Pin 2 (50.00 mmol, 27.93 g), Pd(PPh 3 ) 4 (0.45 mmol, 0.52 g), Na 2 CO 3 (67.50 mmol, 7.15 g) and DMF (270 mL) were added to the reaction flask, and the mixture was heated and reacted for 2 h. After the reaction was completed, it was cooled to room temperature, 350 mL of distilled water was added, and then extracted with ethyl acetate. The organic phase was dried with anhydrous MgSO 4 After drying, the solvent was removed by rotary evaporation, and then recrystallized with toluene:ethanol = 10:3, and dried to obtain Intermediate A-551 (20.83 g, yield 81%); HPLC purity ≥ 99.77%. Mass spectrometry m / z: 571.2671 (theoretical value: 571.2683).

[0318] Preparation of Compound 551:

[0319] Under nitrogen protection, Intermediate A-551 (25.50 mmol, 14.57 g), c-547 (25.00 mmol, 6.60 g), Pd 2 (dba) 3 (0.25 mmol, 0.23 g), P(t-Bu) 3 (0.75 mmol, 0.15 g), K 2 CO 3(37.5 mmol, 5.18 g) and THF (100 mL) were added to a reaction flask, and the mixture was stirred. The reaction was heated under reflux for 6 hours. After the reaction was completed, it was cooled to room temperature, and the filter cake was obtained by suction filtration. The filter cake was rinsed with ethanol, and finally the filter cake was recrystallized with toluene to obtain Compound 551 (11.48 g, yield 73%); HPLC purity ≥ 99.97%. Mass spectrometry m / z: 628.1982 (theoretical value: 628.1973). Theoretical elemental content (%) C 45 H 28 N 2 S: C, 85.96; H, 4.49; N, 4.46. Measured elemental content (%): C, 86.01; H, 4.52; N, 4.41.

[0320] [Synthesis Example 29] Preparation of Compound 567

[0321]

[0322] In Synthesis Example 1, Intermediate A-1 was replaced with an equimolar amount of Intermediate A-77, b-1 was replaced with an equimolar amount of b-567, and c-1 was replaced with an equimolar amount of c-567. According to the same preparation method as in Synthesis Example 1, Compound 567 (13.13 g) was obtained; HPLC purity ≥ 99.93%. Mass spectrometry m / z: 760.2924 (theoretical value: 760.2912). Theoretical elemental content (%) C 55 H 40 N 2 S: C, 86.81; H, 5.30; N, 3.68. Measured elemental content (%): C, 86.77; H, 5.28; N, 3.72.

[0323] [Synthesis Example 30] Preparation of Compound 587

[0324]

[0325] Preparation of Intermediate c-587:

[0326] In Synthesis Example 7, j-175 was replaced with an equimolar amount of j-587. According to the same preparation method as Intermediate c-175 in Synthesis Example 7, Intermediate c-587 (11.33 g) was obtained. HPLC purity ≥ 99.78%. Mass spectrometry m / z: 247.9596 (theoretical value: 247.9585).

[0327] Preparation of Compound 587:

[0328] Replace c-1 in Synthesis Example 1 with an equimolar amount of c-587, and according to the same preparation method as in Synthesis Example 1, compound 587 (10.57 g) was obtained; HPLC purity ≥ 99.98%. Mass spectrometry m / z: 563.2012 (theoretical value: 563.1998). Theoretical elemental content (%) C 40 H 25 N 3 O: C, 85.24; H, 4.47; N, 7.46. Measured elemental content (%): C, 85.19; H, 4.51; N, 7.42.

[0329] [Synthesis Example 31] Preparation of Compound 593

[0330]

[0331] Preparation of Intermediate c-593:

[0332] Replace j-175 in Synthesis Example 7 with an equimolar amount of j-593, and according to the same preparation method as Intermediate c-175 in Synthesis Example 7, Intermediate c-593 (13.36 g) was obtained. HPLC purity ≥ 99.73%. Mass spectrometry m / z: 298.9680 (theoretical value: 298.9694).

[0333] Preparation of Compound 593:

[0334] Replace Intermediate A-1 in Synthesis Example 1 with an equimolar amount of Intermediate A-459, b-1 with an equimolar amount of b-593, and c-1 with an equimolar amount of c-593, and according to the same preparation method as in Synthesis Example 1, compound 593 (11.97 g) was obtained; HPLC purity ≥ 99.97%. Mass spectrometry m / z: 664.2274 (theoretical value: 664.2263). Theoretical elemental content (%) C 47 H 28 N 4 O: C, 84.92; H, 4.25; N, 8.43. Measured elemental content (%): C, 84.89; H, 4.30; N, 8.38.

[0335] [Synthesis Example 32] Preparation of Compound 607

[0336]

[0337] Replace intermediate A-1 in Synthesis Example 1 with an equimolar amount of intermediate A-77, b-1 with an equimolar amount of b-607, and c-1 with an equimolar amount of c-209. According to the same preparation method as in Synthesis Example 1, compound 607 (12.76 g) was obtained; HPLC purity ≥ 99.94%. Mass spectrometry m / z: 728.2839 (theoretical value: 728.2828). Theoretical elemental content (%) C 54 H 36 N 2 O: C, 88.98; H, 4.98; N, 3.84. Measured elemental content (%): C, 89.02; H, 5.03; N, 3.79.

[0338] [Synthesis Example 33] Preparation of Compound 612

[0339]

[0340] Preparation of intermediate c-612:

[0341] Replace j-175 in Synthesis Example 7 with an equimolar amount of j-612. According to the same preparation method as intermediate c-175 in Synthesis Example 7, intermediate c-612 (13.82 g) was obtained. HPLC purity ≥ 99.76%. Mass spectrometry m / z: 312.9552 (theoretical value: 312.9561).

[0342] Preparation of compound 612:

[0343] Replace intermediate A-1 in Synthesis Example 1 with an equimolar amount of intermediate A-343, b-1 with an equimolar amount of b-612, and c-1 with an equimolar amount of c-612. According to the same preparation method as in Synthesis Example 1, compound 612 (12.60 g) was obtained; HPLC purity ≥ 99.95%. Mass spectrometry m / z: 719.2018 (theoretical value: 719.2031). Theoretical elemental content (%) C 50 H 29 N 3 OS: C, 83.43; H, 4.06; N, 5.84. Measured elemental content (%): C, 83.39; H, 4.09; N, 5.87.

[0344] [Device Example 1]

[0345] First, place the glass substrate coated with ITO / Ag / ITO in distilled water and wash it twice, perform ultrasonic washing for 30 minutes, then wash it repeatedly with distilled water twice and perform ultrasonic washing for 10 minutes. After the distilled water washing is completed, perform ultrasonic washing in sequence with isopropyl alcohol, acetone, and methanol solvents, and then dry it on a hot plate heated to 120 °C. Transfer the dried substrate to a plasma cleaner, wash it for 5 minutes, and then transfer the substrate to an evaporation machine.

[0346] Then, deposit HI-1 as a hole injection layer on the already cleaned ITO / Ag / ITO substrate, with a deposition thickness of 10 nm. Deposit HT-1 as a hole transport layer on this hole injection layer, with a deposition thickness of 60 nm. Then, vacuum deposit a mixture of GH-1, GH-2, and GD-1 (mass ratio GH-1:GH-2:GD-1 = 46:46:8) on the hole transport layer to form a light-emitting layer, with a deposition thickness of 30 nm. Deposit the compound 1 of the present invention and Liq (mass ratio 1:1) as an electron transport layer on the light-emitting layer, with a deposition thickness of 40 nm. Deposit LiF as an electron injection layer on this electron transport layer, with a deposition thickness of 1 nm. Then, deposit Mg:Ag (mass ratio Mg:Ag = 1:9) as a cathode on this electron injection layer, with a deposition thickness of 15 nm. Then, vacuum deposit CP-1 as a cover layer on the cathode, with a deposition thickness of 70 nm, thereby preparing an organic electroluminescent device (the material structures of each functional layer in the process of preparing the organic electroluminescent device are as follows).

[0347]

[0348] [Device Examples 2 - 18]

[0349] Use compound 111, compound 175, compound 209, compound 253, compound 293, compound 337, compound 343, compound 405, compound 431, compound 444, compound 506, compound 547, compound 567, compound 587, compound 593, compound 607, compound 612 of the present invention to replace compound 1 in Device Example 1 as the electron transport layer, and the other preparation steps are the same as those in Device Example 1 to prepare organic electroluminescent devices 2 - 18.

[0350] [Comparative Device Examples 1 - 7]

[0351] Use comparative compound 1, comparative compound 2, comparative compound 3, comparative compound 4, comparative compound 5, comparative compound 6, comparative compound 7 to replace compound 1 in Device Example 1 as the electron transport layer, and the other preparation steps are the same as those in Device Example 1 to prepare comparative devices 1 - 7.

[0352] [Device Example 19]

[0353] On the already cleaned ITO / Ag / ITO substrate, HI-1 is evaporated as the hole injection layer with an evaporation thickness of 10 nm. On this hole injection layer, HT-1 is evaporated as the hole transport layer with an evaporation thickness of 60 nm. Then, a mixture of GH-1, GH-2 and GD-1 (mass ratio GH-1:GH-2:GD-1 = 46:46:8) is vacuum-evaporated on the hole transport layer to form the light-emitting layer with an evaporation thickness of 30 nm. On the light-emitting layer, Compound 1 of the present invention is evaporated as the hole blocking layer with an evaporation thickness of 30 nm. Then, ET-1 and Liq (mass ratio 1:1) are evaporated on the hole blocking layer as the electron transport layer with an evaporation thickness of 40 nm. LiF is evaporated on this electron transport layer as the electron injection layer with an evaporation thickness of 1 nm. Then, Mg:Ag (mass ratio Mg:Ag = 1:9) is evaporated on this electron injection layer as the cathode with an evaporation thickness of 15 nm. Then, CP-1 is vacuum-evaporated on the cathode as the covering layer with an evaporation thickness of 70 nm, thereby preparing the organic electroluminescent device 19.

[0354] [Device Examples 20 - 51]

[0355] Compound 77, Compound 92, Compound 111, Compound 126, Compound 157, Compound 175, Compound 209, Compound 253, Compound 293, Compound 296, Compound 302, Compound 326, Compound 330, Compound 337, Compound 343, Compound 405, Compound 408, Compound 431, Compound 444, Compound 459, Compound 466, Compound 496, Compound 506, Compound 529, Compound 536, Compound 547, Compound 551, Compound 567, Compound 587, Compound 593, Compound 607, Compound 612 of the present invention are used to replace Compound 1 in Device Example 19 as the hole blocking layer, and the other preparation steps are the same as those in Device Example 19 to prepare the organic electroluminescent devices 20 - 51.

[0356] [Comparative Device Examples 8 - 14]

[0357] Comparative Compound 1, Comparative Compound 2, Comparative Compound 3, Comparative Compound 4, Comparative Compound 5, Comparative Compound 6, Comparative Compound 7 are used to replace Compound 1 in Device Example 19 as the hole blocking layer, and the other preparation steps are the same as those in Device Example 19 to prepare the comparative devices 8 - 14.

[0358] A combined IVL test system is composed of a test software, a computer, a K2400 digital source meter produced by Keithley Corporation in the United States, and a PR788 spectral scanning luminance meter produced by PhotoResearch Corporation in the United States to test the driving voltage and luminous efficiency of organic electroluminescent devices. The life test is carried out using an M6000 OLED life test system of McScience Company. The test environment is the atmospheric environment, and the temperature is room temperature. The test results of the luminous characteristics of the organic electroluminescent devices obtained from Examples 1 to 51 of the inventive device and Comparative Device Examples 1 to 14 are shown in Table 1 below.

[0359] Table 1:

[0360]

[0361]

[0362]

[0363] From the results in Table 1, it can be seen that when the heterocyclic compounds provided by the present invention are used in the electron transport layer or hole blocking layer of organic electroluminescent devices, the driving voltage of the organic electroluminescent devices can be reduced, the luminous efficiency of the organic electroluminescent devices can be improved, and the service life of the organic electroluminescent devices can be extended.

[0364] [Device Example 52]

[0365] HI-1 is evaporated as a hole injection layer on the already cleaned ITO / Ag / ITO substrate with an evaporation thickness of 10 nm. HT-1 is evaporated as a hole transport layer on this hole injection layer with an evaporation thickness of 60 nm. Then, a mixture of GH-1, GH-2, and GD-1 (mass ratio GH-1:GH-2:GD-1 = 46:46:8) is vacuum-evaporated on the hole transport layer to form a light-emitting layer with an evaporation thickness of 30 nm. HB-1 is evaporated as a hole blocking layer on the light-emitting layer with an evaporation thickness of 30 nm. Then, a mixture of ET-1 and Liq (mass ratio 1:1) is evaporated as an electron transport layer on the hole blocking layer with an evaporation thickness of 40 nm. LiF is evaporated as an electron injection layer on this electron transport layer with an evaporation thickness of 1 nm. Then, Mg:Ag (mass ratio Mg:Ag = 1:9) is evaporated as a cathode on this electron injection layer with an evaporation thickness of 15 nm. Then, Compound 111 is vacuum-evaporated as a covering layer on the cathode with an evaporation thickness of 70 nm, thereby preparing Organic Electroluminescent Device 52.

[0366] [Device Examples 53 to 62]

[0367] Use Compound 175, Compound 209, Compound 253, Compound 296, Compound 337, Compound 408, Compound 431, Compound 536, and Compound 612 of the present invention to replace Compound 111 in Device Example 52 as the cover layer, and the other preparation steps are the same as those in Device Example 52 to prepare organic electroluminescent devices 53 - 62.

[0368] [Comparative Device Example 15]

[0369] Use Comparative Compound 8 to replace Compound 111 in Device Example 52 as the cover layer, and the other preparation steps are the same as those in Device Example 52 to prepare Comparative Device 15.

[0370] Table 2:

[0371]

[0372] As can be seen from Table 2, when the compounds of the present invention are applied to the cover layer of organic electroluminescent devices, due to the high refractive index of the compounds of the present invention, the light extraction efficiency of the devices can be effectively improved compared with Comparative Compound 8, thereby improving the luminous efficiency of the organic electroluminescent devices and extending the service life of the devices.

[0373] It should be noted that the present invention has been specifically described with individual embodiments. For those of ordinary skill in the art in the technical field, without departing from the principle of the present invention, several improvements and modifications can still be made to the present invention, and these improvements and modifications also fall within the protection scope of the present invention.

Claims

1. A heterocyclic compound, characterized in that the heterocyclic compound has a structure shown in Formula 1: A-L-B Formula 1 In Formula 1, A is selected from any one of the following groups: The said R 1 is independently selected from hydrogen and deuterium; Said R 1a Independently selected from any one of hydrogen, deuterium, or the following substituted or unsubstituted groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; or two adjacent Rs 1a can combine with each other to form any one of substituted or unsubstituted C3-C7 aliphatic rings; The R 1b is independently selected from any one of hydrogen, deuterium, or a substituted or unsubstituted phenyl group; or two adjacent Rs 1b may combine with each other to form any one of a substituted or unsubstituted benzene ring; wherein b1 is selected from 0, 1, 2, 3, 4 or 5, b2 is selected from 0, 1, 2, 3 or 4, b3 is independently selected from 0, 1, 2 or 3, c1 is selected from 0, 1, 2, 3, 4, 5, 6 or 7, c2 is independently selected from 0, 1, 2, 3, 4, 5 or 6, and when b1, b2, b3, c1 or c2 is greater than 1, two or more Rs 1 are the same as or different from each other, and two or more Rs 1a are the same as or different from each other; The m 1 is independently selected from 0, 1, 2, 3, 4, 5 or 6, and the m 2 is independently selected from 0, 1, 2, 3, 4 or 5, and the m 5 is independently selected from 0, 1, 2, 3, 4, 5, 6 or 7, and the m 6 is independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; when the m 1 , m 2 , m 5 or m 6 is greater than 1, two or more R 1 are the same as or different from each other, and two or more R 1b are the same as or different from each other; Ry is independently selected from the following substituted or unsubstituted groups: phenyl, biphenyl, naphthyl, pyridyl; Lxa is independently selected from any one of a single bond, a substituted or unsubstituted phenylene group; Lx is selected from a single bond; The said X 1 is selected from any one of a single bond, O, S, N(R 4 )); Said R 4 Independently selected from any one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, and substituted or unsubstituted naphthyl; B is selected from any one of the following groups: Said X 2 is selected from O or S; L is selected from a single bond, a phenyl group substituted or unsubstituted with deuterium, a substituted or unsubstituted s-triazine group or any one of the following groups: Said X 3 is selected from any one of O, S, C(R 9 ) 2 ; The R 8a independently selected from any one of hydrogen, deuterium, cyano, or a substituted or unsubstituted one of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; The R 8 is independently any one selected from hydrogen and deuterium; Said R 9 Independently selected from any one of substituted or unsubstituted C1-C6 alkyl groups; The f 1 is independently selected from 0, 1, 2, 3 or 4, and the f 2 is independently selected from 0, 1, 2, 3, 4, 5 or 6, and the f 3 is independently selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, and the f 4 is independently selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, and the f 5 is independently selected from 0, 1, 2 or 3, and the f 6 is independently selected from 0, 1 or 2, and the f 7 is independently selected from 0, 1, 2, 3, 4 or 5; when the f 1 , f 2 , f 3 , f 4 , f 5 , f 6 or f 7 is greater than 1, two or more Rs 8a are the same as or different from each other, and two or more Rs 8 are the same as or different from each other; The "substituted" group is selected from deuterium.

2. The heterocyclic compound according to claim 1, characterized in that A is selected from any one of the following groups:

3. The heterocyclic compound according to claim 1, characterized in that Ry is independently selected from the following substituted or unsubstituted groups: phenyl, pyridyl.

4. The heterocyclic compound according to claim 1, characterized in that B is selected from any one of the following groups:

5. The heterocyclic compound according to claim 1, characterized in that L is selected from a single bond or any one of the following groups:

6. A heterocyclic compound, characterized in that the heterocyclic compound is selected from any one of the following compounds:

7. An organic electroluminescent device comprising an anode, a cathode and one or more organic layers, the organic layer being located between the anode and the cathode or outside at least one of the anode and the cathode, characterized in that the organic layer comprises at least one heterocyclic compound according to any one of claims 1 to 6.

8. The organic electroluminescent device according to claim 7, characterized in that the organic layer comprises at least one of an electron transport layer, a hole blocking layer or a capping layer, and at least one of the electron transport layer, the hole blocking layer or the capping layer comprises at least one heterocyclic compound according to any one of claims 1 to 6.

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