阅读说明：本技术 一种有机电致发光化合物及其应用 (Organic electroluminescent compound and application thereof ) 是由 陈志宽 李祥智 蔡烨 魏定纬 丁欢达 于 2020-07-29 设计创作，主要内容包括：本发明涉及一种有机电致发光化合物及其应用,所述有机电致发光化合物具有式I所示的结构。本发明提供了一种新型的有机电致发光化合物,以一种特殊的稠环结构为母核,该结构具有一定角度的扭转,一定程度上降低空穴传输速率,有利于空穴与电子传输速率平衡,将其应用于有机电致发光器件时,特别是作为发光层主体材料时,能够使器件具有较高的发光效率、较低的驱动电压和较长的使用寿命。(The invention relates to an organic electroluminescent compound and application thereof, wherein the organic electroluminescent compound has a structure shown in a formula I. The invention provides a novel organic electroluminescent compound, which takes a special condensed ring structure as a mother core, the structure has a certain angle of torsion, the hole transmission rate is reduced to a certain extent, the hole and electron transmission rate balance is facilitated, and when the novel organic electroluminescent compound is applied to an organic electroluminescent device, particularly when the novel organic electroluminescent compound is used as a main body material of a light-emitting layer, the device can have higher luminous efficiency, lower driving voltage and longer service life.)

1. An organic electroluminescent compound, characterized in that the organic electroluminescent compound has a structure represented by formula I;

in the formula I, the Y¹And Y²Each independently selected from N-L-Ar, O, S or CR_aR_bSaid R is_aAnd R_bAre not connected or are connected through a single bond;

ar is selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl orAny one of the above; the bond at the wavy line mark represents a group;

ar is¹And Ar²Each independently selected from any one of substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;

the R is_aAnd R_bEach independently selected from hydrogen, deuterium, tritium, cyano, nitro, halogen, substituted or unsubstituted C1-C30 straight chain alkyl, substituted or unsubstituted C3-C30 branched alkylAny one of a group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C60 aryl group, and a substituted or unsubstituted C3-C60 heteroaryl group;

in the formula I, R is¹、R²、R³、R⁴And R⁵Each independently selected from hydrogen, deuterium, tritium, cyano, nitro, halogen, substituted or unsubstituted C1-C30 linear alkyl, substituted or unsubstituted C3-C30 branched alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 thioalkoxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C6-C60 thioaryloxy, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C3-C60 heteroaryloxy, substituted or unsubstituted C3-C60 thioheteroaryloxy,

the R is⁶、R⁷、R⁸、R⁹And R¹⁰Each independently selected from any one or at least two of hydrogen, deuterium, tritium, cyano, nitro, halogen, substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C3-C30 branched-chain alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl;

the L, L¹And L²Each independently selected from a single bond, a substituted or unsubstituted C6-C60 aryl, or a substituted or unsubstituted C3-C60 heteroaryl;

in the formula I, m and k are respectively independent integers from 0 to 3, and n, p and q are respectively independent integers from 0 to 4;

Ar、Ar¹、Ar²、R¹-R¹⁰、R_a、R_b、L、L¹and L²Wherein the substituted groups are each independently selected from deuterium, tritium, halogen, cyano, C1-C20 linear alkyl, deuterium substituted C1-C20 linear alkyl, halogen substituted C1-C20 linear alkyl, C3-C20 branched alkyl, deuterium substituted C3-C20 branched alkyl, halogen substituted C3-C20 branched alkyl, C3-C20 cycloalkyl, deuterium substituted C3-C20 cycloalkyl, halogen substituted C3-C20 cycloalkyl, C6-C30 aryl, deuterium substituted C30-C30 aryl, halogen substituted C30-C30 aryl, cyano substituted C30-C30 aryl, C30-C30 heteroaryl, deuterium substituted C30-C30 heteroaryl, halogen substituted C30-C30 heteroaryl, cyano substituted C30 heteroaryl, C30-C30 alkoxy, C30-C30 aryloxy, Any one or at least two of C6-C30 aryl amino, C3-C30 heteroaryl amino and C3-C30 aryl heteroaryl amino.

2. The organic electroluminescent compound according to claim 1, wherein the organic electroluminescent compound has a structure represented by formula II or formula III;

said X¹And X²Each independently is a single bond, N-L-Ar, O, S or C (L-Ar)₂Any one of the above;

r and s are each independently an integer of 0-4;

r 'and R' are respectively and independently selected from any one or at least two of hydrogen, deuterium, tritium, cyano, nitro, halogen, C1-C10 straight-chain alkyl, C3-C10 branched-chain alkyl, C3-C10 cycloalkyl, C2-C10 alkenyl, C1-C10 alkoxy, C6-C30 aryl, C3-C30 heteroaryl, C6-C30 arylamino, C3-C30 heteroarylamino and C3-C30 arylheteroarylamino;

ar, L and Y¹、Y²、R¹-R⁴、m、n, p and q all have the same limits as in claim 1.

3. The organic electroluminescent compound according to claim 2, wherein in formula II, X is¹And X²At least one of which is a single bond, preferably one and only one of which is a single bond;

preferably, in formula II, Y is¹、Y²、X¹And X²At least one of them is N-L-Ar, preferably one or two of them are N-L-Ar, and more preferably two of them are N-L-Ar.

4. The organic electroluminescent compound according to claim 2, wherein in formula III, Y is¹And Y²At least one of them is N-L-Ar, preferably one or two of them are N-L-Ar, and more preferably two of them are N-L-Ar.

5. The organic electroluminescent compound according to any one of claims 1 to 4, wherein Ar has any one of the following structures:

z is¹-Z²²Each independently selected from N or CR¹¹；

The R is¹¹Each independently selected from hydrogen, deuterium, tritium, cyano, nitro, halogen, C1-C10 straight chain alkyl, C3-C10 branched chain alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C6-C30 aryl, C6-C30 aryloxy, C3-C30 heteroaryl,Any one or at least two groups connected together;

said L³Selected from single bonds or C6-C30 aryl;

the R is¹²And R¹³Each independently selected from C6-C30 aryl, C3-C30 heteroarylAny one of them;

x is selected from NR¹⁴、CR¹⁵R¹⁶Any one of O or S;

the R is¹⁴、R¹⁵And R¹⁶Each independently selected from any one or at least two of hydrogen, deuterium, tritium, cyano, nitro, halogen, C1-C10 straight-chain alkyl, C3-C10 branched-chain alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C6-C30 aryl, C6-C30 aryloxy and C3-C30 heteroaryl.

6. The organic electroluminescent compound according to claim 5, wherein Z is¹-Z⁶1-3 in the formula are N;

preferably, Z is⁷-Z¹⁴1-3 in the formula are N;

preferably, Z is¹⁵-Z²²Wherein 0-2 is N.

7. The organic electroluminescent compound according to any one of claims 1 to 4, wherein Ar is selected from any one of the following substituted or unsubstituted groups:

the R is¹⁴、R¹⁵And R¹⁶Each independently selected from any one of hydrogen, deuterium, tritium, cyano, nitro, halogen, C1-C10 alkyl, C1-C10 alkoxy, C6-C30 aryl, C6-C30 aryloxy and C3-C30 heteroaryl.

8. The organic electroluminescent compound according to claim 1, wherein the organic electroluminescent compound has any one of the following compounds 1 to 80:

9. an organic electroluminescent device comprising a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode, the organic layer comprising any one or a combination of at least two of the organic electroluminescent compounds according to any one of claims 1 to 8;

preferably, the organic layer includes a light emitting layer containing the organic electroluminescent compound according to any one of claims 1 to 8;

preferably, the light emitting layer includes a host material including the organic electroluminescent compound according to any one of claims 1 to 8 and a guest material;

preferably, the light-emitting layer contains at least two host materials;

preferably, the guest material comprises a fluorescent dopant, preferably any one or a combination of at least two of Ir, Pt, Ni, Au, Os, Re, Rh, Zn, Ag, Fe or W;

preferably, the organic layer further comprises any one or at least two of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer or an electron injection layer;

preferably, the organic electroluminescent compound according to any one of claims 1 to 8 is contained in the electron blocking layer.

10. A display device or a lighting device comprising the organic electroluminescent device according to claim 9.

Technical Field

The invention relates to the technical field of organic electroluminescence, in particular to an organic electroluminescent compound and application thereof.

Background

In 1987, the first organic light-emitting diode (OLED) device (hereinafter referred to as OLED device) was first fabricated by danqing cloud doctor in the Eastman Kodak laboratory (Eastman Kodak) of the united states by vacuum evaporation (appl. phys. lett.,1987,51,913), which uses transparent and conductive Indium Tin Oxide (ITO) as the cathode, and on which diamine derivatives and tris (8-hydroxyquinoline) aluminum are sequentially evaporated, and the anode material uses mg-ag alloy, and this multilayer structure can reduce the driving voltage of the OLED device, and effectively improve the charge injection problem between the material molecules and the electrode interface, and thus the device performance and lifetime are improved.

Compared with the traditional light-emitting technology, the OLED device has the advantages of low driving voltage, high light-emitting efficiency, high contrast, high color saturation, wide visual angle, quick response time and the like, has great potential to replace the mainstream liquid crystal display, and becomes the star technology in the display field. The increasing demand in the display field also drives the rapid development of OLED device structures and organic photoelectric materials, which are embodied as compounds and materials with new structures, functional groups and substituents, and simultaneously, the OLED device structures are continuously optimized and gradually developed from the initial sandwich structure into complex structures composed of multiple functional layers. The current OLED device comprises a plurality of layers of a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and suitable electrodes, and these layers are respectively composed of the following materials: hole injection materials, hole transport materials, light emitting materials, hole blocking materials, electron transport materials, and electron injection materials. The OLED light-emitting layer manufactured in a doping mode has advantages in the light-emitting efficiency of the device, so that the light-emitting layer material is usually formed by doping a host material with a guest material, and the host material is an important factor influencing the light-emitting efficiency and performance of the OLED device.

At present, the number of the current day,

the CBP is a widely applied main body material and has good hole transport property, but when the CBP is used as the main body material, the CBP is easy to recrystallize due to low glass transition temperature, so that the service performance and the luminous efficiency of an OLED device are reduced. On the other hand, CBP is a hole-type host material, the transport of electrons and holes is unbalanced, the recombination efficiency of excitons is low, the light emitting region is not ideal, and the roll-off phenomenon is severe during the operation of the device, which results in low efficiency of energy transfer from the host material to the guest material and reduces the efficiency of the device.

Therefore, it is a technical problem in the art to improve the thermal stability and energy transfer efficiency of the host material, thereby further optimizing the light emitting efficiency and driving voltage of the organic electroluminescent device.

Disclosure of Invention

An object of the present invention is to provide an organic electroluminescent compound, and more particularly, to provide a host material of a light-emitting layer, which has high thermal stability and energy transfer efficiency, and has high light-emitting efficiency, low driving voltage and long service life when applied to an organic electroluminescent device.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides an organic electroluminescent compound, which has a structure shown in a formula I;

in the formula I, the Y¹And Y²Each independently selected from N-L-Ar, O, S or CR_aR_bSaid R is_aAnd R_bAre not connected or are connected through a single bond;

ar is selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl or

Any one of the above; the bond at the wavy line mark represents a group;

ar is¹And Ar²Each independently selected from any one of substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;

the R is_aAnd R_bEach independently selected from any one of hydrogen, deuterium, tritium, cyano, nitro, halogen, substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C3-C30 branched-chain alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl;

in the formula I, R is¹、R²、R³、R⁴And R⁵Each independently selected from hydrogen, deuterium, tritium, cyano, nitro, halogen, substituted or unsubstituted C1-C30 linear alkyl, substituted or unsubstituted C3-C30 branched alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 thioalkoxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C6-C60 thioaryloxy, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C3-C60 heteroaryloxy, substituted or unsubstituted C3-C60 thioheteroaryloxy,Any one or at least two groups connected to each otherOr, said R is¹、R²、R³、R⁴And R⁵Wherein adjacent groups on the same phenyl ring are linked to form a substituted or unsubstituted C6-C60 aromatic ring or a substituted or unsubstituted C3-C60 heteroaromatic ring; the "C6-C30 aromatic ring" and "C3-C30 heteroaromatic ring" are linked to the benzene ring on the parent nucleus in formula I in a manner that they share two carbon atoms, i.e., are fused to the parent nucleus; the "adjacent groups" refer to two groups adjacent to each other on the same benzene ring, for example, when two adjacent R's are substituted on the benzene ring⁵Two of these R⁵May be linked to form a substituted or unsubstituted C6-C30 aromatic ring or a substituted or unsubstituted C3-C30 heteroaromatic ring;

the R is⁶、R⁷、R⁸、R⁹And R¹⁰Each independently selected from any one or at least two of hydrogen, deuterium, tritium, cyano, nitro, halogen, substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C3-C30 branched-chain alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl;

the L, L¹And L²Each independently selected from a single bond or a substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C60 heteroaryl, preferably a single bond or phenylene;

in formula I, m and k are each independently an integer from 0 to 3, such as 1 or 2, and n, p, q are each independently an integer from 0 to 4, such as 1, 2 or 3;

Ar、Ar¹、Ar²、R¹-R¹⁰、R_a、R_b、L、L¹and L²Wherein the substituted groups are each independently selected from deuterium, tritium, halogen, cyano, C1-C20 straight chain alkyl, deuterium substituted C1-C20 straight chain alkyl, halogen substituted C1-C20 straight chain alkyl, C3-C20 branched alkyl, deuterium substituted C3-C20 branched alkyl, halogen substituted C3-C20 branched alkyl, C3-C20 cycloalkyl, deuterium substituted C3-C20 cycloalkyl, halogen substituted C3-C20 cycloalkyl, C6-C30 aryl, deuterium substituted C6-C30 aryl, halogen substituted C5634-CAny one or at least two combinations of C6-C30 aryl, cyano-substituted C6-C30 aryl, C3-C30 heteroaryl, deuterium-substituted C3-C30 heteroaryl, halogen-substituted C3-C30 heteroaryl, cyano-substituted C3-C30 heteroaryl, C1-C20 alkoxy, C2-C20 alkenyl, C6-C30 aryloxy, C6-C30 arylamino, C3-C30 heteroarylamino and C3-C30 arylheteroarylamino. The substituted group may be selected from any one or at least two of the above groups, or may be selected from groups in which the above groups are bonded by chemical bond.

In the present invention, the wavy line marks represent the bond of the group.

In the present invention, the expression that a single bond crosses a ring means that a group can be attached at any attachable site of the ring.

In the present invention, halogen includes, but is not limited to, fluorine, chlorine, bromine, iodine, and the like.

The invention provides a novel organic electroluminescent compound with a special condensed ring structureThe structure is a mother core, the structure has torsion at a certain angle, the hole transmission rate is reduced to a certain extent, the hole and electron transmission rate balance is facilitated, and when the structure is applied to an organic electroluminescent device, particularly when the structure is used as a main body material of a light-emitting layer, the device can have high luminous efficiency, low driving voltage and long service life.

Preferably, in formula I, Y is¹And Y²At least one of them is N-L-Ar.

Preferably, in formula I, R¹、R²、R³、R⁴And R⁵Are all hydrogen.

Preferably, in formula I, R is_aAnd R_bEach independently selected from C1-C10 alkyl or C6-C30 aryl, preferably methyl or phenyl.

Preferably, the organic electroluminescent compound has a structure represented by formula II or formula III;

said X¹And X²Each independently is a single bond, N-L-Ar, O, S or C (L-Ar)₂Any one of the above;

r and s are each independently an integer of 0 to 4, such as 1, 2, or 3;

r 'and R' are respectively and independently selected from any one or at least two of hydrogen, deuterium, tritium, cyano, nitro, halogen, C1-C10 straight-chain alkyl, C3-C10 branched-chain alkyl, C3-C10 cycloalkyl, C2-C10 alkenyl, C1-C10 alkoxy, C6-C30 aryl, C3-C30 heteroaryl, C6-C30 arylamino, C3-C30 heteroarylamino and C3-C30 arylheteroarylamino;

ar, L¹、L²、Y¹、Y²、R¹-R⁴M, n, p and q all have the same selection ranges as before.

Preferably, in formula II, R is¹-R⁴And R' are both hydrogen.

Preferably, in formula III, R is¹-R⁴And R "are both hydrogen.

Preferably, in formula II, X is¹And X²At least one of which is a single bond, preferably, only one of which is a single bond.

Preferably, in formula II, Y is¹、Y²、X¹And X²At least one of them is N-L-Ar, preferably one or two of them are N-L-Ar, and more preferably two of them are N-L-Ar.

Preferably, in formula III, Y is¹And Y²At least one of them is N-L-Ar, preferably one or two of them are N-L-Ar, and more preferably two of them are N-L-Ar.

The preferable compound contains N-L-Ar groups, the N-L-Ar groups are matched with the mother nucleus and can promote carrier transmission, so that the luminous efficiency of the device is further improved, the driving voltage is reduced, the service life is prolonged, the number of the N-L-Ar groups is preferably one or two, and the excessive number of the N-L-Ar groups can cause the unbalance of electron and hole transmission, thereby reducing the current efficiency.

Preferably, the organic electroluminescent compound has any one of the following structures:

the Ar 'has the same selection range as the Ar, and the L' has the same selection range as the L.

Preferably, the Ar has any one of the following structures:

z is¹-Z²²Each independently selected from N or CR¹¹；

The R is¹¹Each independently selected from hydrogen, deuterium, tritium, cyano, nitro, halogen, C1-C10 straight chain alkyl, C3-C10 branched chain alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C6-C30 aryl, C6-C30 aryloxy, C3-C30 heteroaryl,

Any one or at least two groups connected together; when substituted with at least two R¹¹When these are at least two R¹¹May be the same or different;

said L³Selected from single bonds or C6-C30 aryl;

the R is¹²And R¹³Each independently selected from any one of C6-C30 aryl and C3-C30 heteroaryl;

x is selected from NR¹⁴、CR¹⁵R¹⁶Any one of O or S;

the R is¹⁴、R¹⁵And R¹⁶Each independently selected from hydrogen, deuterium, tritium, cyano, nitro, halogen, C1-C10 straight chain alkyl, C3-C10 branched chain alkylThe group is formed by connecting any one or at least two of C3-C10 naphthenic base, C1-C10 alkoxy, C6-C30 aryl, C6-C30 aryloxy and C3-C30 heteroaryl.

Preferably, Z is¹-Z⁶Wherein 1-3 (e.g., 2) are N.

Preferably, Z is⁷-Z¹⁴Wherein 1-3 (e.g., 2) are N.

Preferably, Z is¹⁵-Z²²Wherein 0-2 (e.g., 1) are N.

Preferably, Ar is selected from any one of the following substituted or unsubstituted groups:

the R is¹⁴、R¹⁵And R¹⁶Each independently selected from any one of hydrogen, deuterium, tritium, cyano, nitro, halogen, C1-C10 alkyl, C1-C10 alkoxy, C6-C30 aryl, C6-C30 aryloxy and C3-C30 heteroaryl.

Preferably, said R is¹³、R¹⁴And R¹⁵Each independently selected from any one of methyl, phenyl or pyridyl.

Preferably, in Ar, the substituted group is selected from C1-C10 alkyl or C6-C30 aryl, preferably any one or at least two of methyl, phenyl, naphthyl and biphenyl.

In the present invention, the number of carbons of the aryl group (or aromatic ring) includes C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, etc., and the aryl group includes monocyclic, polycyclic, fused ring, and specifically is selected from phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthryl, anthryl, indenyl, triphenylene, pyrenyl, tetracenyl, perylenyl, chrysenyl, fused tetraphenyl, fluoranthenyl, or spiro dibenzofluorenyl.

In the present invention, the aryloxy group means a group in which an aryl group is bonded to an oxygen atom, wherein the aryl group is as described above.

In the present invention, arylamino means a group in which an aryl group is bonded to an oxygen atom, wherein the aryl group is as described above.

In the present invention, the number of carbons of the heteroaryl group (or heteroaryl ring) includes C4, C5, C6, C7, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28 and the like, and the heteroaryl group includes monocyclic, polycyclic and condensed rings, and the rings may be connected to each other by a short non-aromatic group (e.g., methylene, oxygen, sulfur, and nitrogen) or may be connected by a single bond, and is selected from the group consisting of furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, and the like, Indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, derivatives thereof, and the like.

In the present invention, the number of carbons of the alkyl group includes C2, C3, C4, C5, C6, C7, C8, C9, etc., and the alkyl group may be any of a straight chain and a branched chain, and examples thereof include: methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, tert-butyl.

In the present invention, the alkoxy group means a group in which an alkyl group is bonded to an oxygen atom, wherein the alkyl group is as described in the above paragraph.

In the present invention, the number of carbons of the alkenyl group includes C2, C3, C4, C5, C6, C7, C8, C9 and the like, and the alkenyl group means a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having one or more carbon-carbon double bonds and having 2 to 10 carbon atoms. Examples include, but are not limited to, vinyl, allyl, isopropenyl, 2-butenyl, and the like.

Preferably, the organic electroluminescent compound has any one of the following compounds 1 to 80:

in the above compounds, D represents deuterium.

It is a second object of the present invention to provide an organic electroluminescent device comprising a first electrode, a second electrode and an organic layer between the first electrode and the second electrode, the organic layer comprising any one or a combination of at least two of the organic electroluminescent compounds described in the first object.

Preferably, the organic layer includes a light-emitting layer containing the organic electroluminescent compound described as one of the objects.

Preferably, the light emitting layer includes a host material and a guest material, and the host material includes the organic electroluminescent compound according to one of the objects.

Preferably, the light-emitting layer contains at least two host materials.

Preferably, the guest material comprises a fluorescent dopant, preferably any one or a combination of at least two of Ir, Pt, Ni, Au, Os, Re, Rh, Zn, Ag, Fe or W.

Preferably, the organic layer further comprises any one or at least two of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, or an electron injection layer.

Preferably, the electron blocking layer contains an organic electroluminescent compound according to one of the objects.

It is a third object of the present invention to provide a display device or a lighting device including the organic electroluminescent device of the second object.

Compared with the prior art, the invention has the following beneficial effects:

the invention provides a novel organic electroluminescent compound, which takes a special condensed ring structure as a mother core, the structure has a certain angle of torsion, the hole transmission rate is reduced to a certain extent, the hole and electron transmission rate balance is facilitated, and when the novel organic electroluminescent compound is applied to an organic electroluminescent device, particularly when the novel organic electroluminescent compound is used as a main body material of a light-emitting layer, the device can have higher luminous efficiency, lower driving voltage and longer service life.

Drawings

Fig. 1 is a schematic structural view of an organic electroluminescent device provided in embodiment 1 of the present invention;

the material comprises a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 7 and a cathode 8.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

A representative synthetic route for the compounds of formula I of the present invention is as follows (coupling reaction):

wherein X represents a halogen such as fluorine, chlorine, bromine, iodine, etc., and Z₁Represents Bpin or B (OH)₂，Z₂Represents OH, SH or NO₂。

The following synthetic examples exemplify the synthetic methods of several specific compounds:

synthesis example 1 Synthesis of Compound 20

Synthesis of intermediates 1 to 20: in a 100 ml three-necked flask, raw material 9(2.75 g, 0.01mol), raw material 10(1.84 g, 0.01mol), potassium carbonate (1.66 g, 0.012mol), toluene (30 ml), water (6 ml), tetrakis (triphenylphosphine) palladium (5.8 g, 0.5mmol) were added under nitrogen protection, stirred at 100 ℃ for 10 hours, and cooled to room temperature after reaction. Adding water into a reaction system, extracting by dichloromethane, and sequentially adding magnesium sulfate into the obtained extract liquor for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to afford intermediates 1-20(0.93 g, 28% yield).

Synthesis of intermediates 2 to 20: the same synthesis as intermediates 1-20 was performed except that intermediates 1-20(2.87 g, 0.01mol) were used instead of starting material 9 and starting material 8(2.18 g, 0.01mol) was used instead of starting material 10 to give intermediates 2-20(1.27 g, 31% yield).

Synthesis of intermediates 3 to 20: in a 100 ml three-necked flask, intermediate 2-20(4.09 g, 0.01mol), trifluoromethanesulfonic acid (0.02mol) were added and stirred at 5 ℃ for 2 days, then 20 ml of a mixture of water and pyridine (volume ratio 5: 1) was added, refluxed for half an hour, cooled to room temperature after completion, 50 ml of water was added, extracted with dichloromethane 3 times, the organic layer was dried over anhydrous magnesium sulfate, the organic solvent was removed, and the product was recrystallized from ethanol to give intermediate 3-20(1.62 g, 43% yield).

Synthesis of intermediates 4 to 20: in a 100 ml three-necked flask, intermediate 3-20(3.77 g, 0.01mol), BOC anhydride (0.012mol), tetrahydrofuran (35 ml) were added, nitrogen gas was introduced, and after stirring uniformly, 4-dimethylaminopyridine (0.002mol) was added, the temperature was raised to 70 ℃, reaction was carried out for 2 hours, after cooling to room temperature, the solvent was distilled off under reduced pressure, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) to give intermediate 4-20(4.44 g, 93% yield).

Synthesis of intermediates 5 to 20: in a 100 ml three-necked flask, 4-20(4.77 g, 0.01mol) of the starting material, anhydrous THF (30 ml) was added under nitrogen, and the reaction was cooled to-78 ℃. N-butyllithium (4.4ml,0.025mol) was added with stirring and reacted at this temperature for 1 hour. 9-fluorenone (1.8g,1mmol) was dissolved in 10ml of anhydrous tetrahydrofuran and added dropwise to the reaction flask. Reacting for 1h at room temperature, adding water into the reaction system, extracting by dichloromethane, and sequentially adding magnesium sulfate into the obtained extract liquid for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to afford intermediate 5-20(4.40 g, 76% yield).

Synthesis of intermediates 6 to 20: in a 100 ml three-necked flask, intermediate 5-20(5.79 g, 0.01mol) was added, 20 ml acetic acid was added, refluxed for 4 hours, washed with saturated sodium bicarbonate, the organic layer was dried over anhydrous magnesium sulfate, the organic solvent was removed, and the crude product was purified by tetrahydrofuran: recrystallization from 1:4 ethanol gave intermediates 6-20(3.96 g, 86% yield).

Synthesis of compound 20: taking a 100 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, drying, introducing nitrogen, and respectively adding an intermediate 6-20(4.61 g, 0.01mol), a raw material 5(2.40 g, 0.01mol), cesium carbonate (0.012mol), and tris (dibenzylideneacetone) dipalladium (Pd)₂(dba)₃0.5mmol) and 2-dicyclohexylphosphonium-2 ',4',6' -triisopropylbiphenyl (xphos, 0.55mmol), followed by addition of toluene, refluxing of the mixture for 24 hours, cooling to room temperature after the reaction, filtration of the reaction system and concentration, and chromatography purification of the crude product (ethyl acetate/n-hexane, 1/10 (vol.%)) to give compound 20(5.32 g, 80% yield).

Elemental analysis: c₄₇H₂₇N₃Theoretical value of S: c, 84.79, H, 4.09, N, 6.31, S, 4.82, found: c, 84.83, H, 4.08, N, 6.29, S, 4.80, HRMS (ESI) M/z (M +): theoretical value: 665.1926, found: 665.1933.

synthesis example 2 Synthesis of Compound 25

Synthesis of intermediates 1 to 25: in a 100 ml three-necked flask, under the protection of nitrogen, raw material 9(2.75 g, 0.01mol), raw material 13(1.80 g, 0.01mol), potassium carbonate (1.66 g, 0.012mol), toluene (30 ml), water (6 ml), tetrakis (triphenylphosphine) palladium (5.8 g, 0.5mmol) were added, stirred at 100 ℃ for 10 hours, and cooled to room temperature after reaction. Adding water into a reaction system, extracting by dichloromethane, and sequentially adding magnesium sulfate into the obtained extract liquor for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to afford intermediates 1-25(1.02 g, 31% yield).

Synthesis of intermediates 2 to 25: the same synthesis as intermediates 1-25 was performed except that intermediates 1-25(3.29 g, 0.01mol) were used instead of starting material 9 and starting material 8(2.0 g, 0.01mol) was used instead of starting material 13 to give intermediates 2-25(1.22 g, 30% yield).

Synthesis of intermediates 3 to 25: intermediate 2-25(4.05 g, 0.01mol), dichloromethane (30 ml) were added in a 100 ml three-necked flask under nitrogen protection, cooled to 0 ℃, a diethyl ether solution (10 ml) of boron trifluoride (0.01mol) was added dropwise, followed by stirring at room temperature for 12 hours, an aqueous sodium bicarbonate solution was added after the reaction was completed, dichloromethane was extracted, the organic solution was dried over anhydrous magnesium sulfate, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to give intermediate 3-25(1.47 g, 38% yield).

Synthesis of intermediates 4 to 25: in a 100 ml three-necked flask, intermediate 3 to 25(3.87 g, 0.01mol), BOC anhydride (0.012mol), tetrahydrofuran (35 ml) were added, nitrogen gas was introduced, and after stirring uniformly, 4-dimethylaminopyridine (0.002mol) was added, the temperature was raised to 70 ℃, reaction was carried out for 2 hours, after cooling to room temperature, the solvent was distilled off under reduced pressure, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) to give intermediate 4 to 25(4.53 g, 93% yield).

Synthesis of intermediates 5 to 25: in a 100 ml three-necked flask, 4-25(4.87 g, 0.01mol) of the starting material, dry THF (30 ml) was added under nitrogen and the reaction was cooled to-78 ℃. N-butyllithium (4.4ml,0.025mol) was added with stirring and reacted at this temperature for 1 hour. 9-fluorenone (1.8g,1mmol) was dissolved in 10ml of anhydrous tetrahydrofuran and added dropwise to the reaction flask. Reacting for 1h at room temperature, adding water into the reaction system, extracting by dichloromethane, and sequentially adding magnesium sulfate into the obtained extract liquid for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to afford intermediate 5-25(4.18 g, 71% yield).

Synthesis of intermediates 6 to 25: in a 100 ml three-necked flask, intermediate 5-25(5.89 g, 0.01mol) was added, 20 ml acetic acid was added, refluxed for 4 hours, washed with saturated sodium bicarbonate, the organic layer was dried over anhydrous magnesium sulfate, the organic solvent was removed, and the crude product was purified by tetrahydrofuran: recrystallization from 1:4 ethanol gave intermediates 6-25(4.05 g, 86% yield).

Synthesis of compound 25: taking a 100 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, drying, introducing nitrogen, and respectively adding an intermediate 6-25(4.71 g, 0.01mol), a raw material 5(2.40 g, 0.01mol), cesium carbonate (0.012mol), and tris (dibenzylideneacetone) dipalladium (Pd)₂(dba)₃0.5mmol) and 2-dicyclohexylphosphonium-2 ',4',6' -triisopropylbiphenyl (xphos, 0.55mmol), followed by addition of toluene, refluxing of the mixture for 24 hours, cooling to room temperature after the reaction, filtration of the reaction system and concentration, and chromatography purification of the crude product (ethyl acetate/n-hexane, 1/10 (vol.%)) to give compound 25(5.13 g, 76% yield).

Elemental analysis: c₅₀H₃₃N₃Theoretical value: c, 88.86, H, 4.92, N, 6.22, found: c, 88.90, H, 4.90, N, 6.20, HRMS (ESI) M/z (M +): theoretical value: 675.2674, found: 675.2680.

synthesis example 3 Synthesis of Compound 28

Synthesis of intermediates 1 to 28: in a 100 ml three-necked flask, raw material 1(2.75 g, 0.01mol), raw material 2(1.38 g, 0.01mol), potassium carbonate (1.66 g, 0.012mol), toluene (30 ml), water (6 ml), tetrakis (triphenylphosphine) palladium (5.8 g, 0.5mmol) were added under nitrogen protection, stirred at 100 ℃ for 10 hours, and cooled to room temperature after reaction. Adding water into a reaction system, extracting by dichloromethane, and sequentially adding magnesium sulfate into the obtained extract liquor for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to afford intermediates 1-28(0.89 g, 31% yield).

Synthesis of intermediates 2 to 28: the same synthesis as intermediates 1-28 was performed except that intermediates 1-28(2.87 g, 0.01mol) were used instead of starting material 1 and starting material 3(2.18 g, 0.01mol) was used instead of starting material 2, to give intermediates 2-28(1.30 g, 34% yield).

Synthesis of intermediates 3 to 28: in a 100 ml three-neck bottle, the raw materials 2-28(3.81 g, 0.01mol), potassium carbonate (3.45 g, 0.025mol) and DMF (30 ml) were added under nitrogen protection, stirred at 100 ℃ for 6 hours, reacted and cooled to room temperature. Adding water into a reaction system, extracting by dichloromethane, and sequentially adding magnesium sulfate into the obtained extract liquor for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to afford intermediate 3-28(2.89 g, 80% yield).

Synthesis of intermediates 4 to 28: in a 100 ml three-necked flask, intermediate 3 to 28(3.61 g, 0.01mol), BOC anhydride (0.012mol), tetrahydrofuran (35 ml) were added, nitrogen gas was introduced, and after stirring uniformly, 4-dimethylaminopyridine (0.002mol) was added, the temperature was raised to 70 ℃, reaction was carried out for 2 hours, after cooling to room temperature, the solvent was distilled off under reduced pressure, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) to give intermediate 4 to 28(4.15 g, yield 90%).

Synthesis of intermediates 5 to 28: in a 100 ml three-necked flask, starting material 4-28(4.61 g, 0.01mol), dry THF (30 ml) was added under nitrogen and the reaction was cooled to-78 ℃. N-butyllithium (4.4ml,0.025mol) was added with stirring and reacted at this temperature for 1 hour. 9-fluorenone (1.8g,1mmol) was dissolved in 10ml of anhydrous tetrahydrofuran and added dropwise to the reaction flask. Reacting for 1h at room temperature, adding water into the reaction system, extracting by dichloromethane, and sequentially adding magnesium sulfate into the obtained extract liquid for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to afford intermediate 5-28(4.50 g, 80% yield).

Synthesis of intermediates 6 to 28: in a 100 ml three-necked flask, intermediate 5-28(5.63 g, 0.01mol) was added, 20 ml acetic acid was added, refluxed for 4 hours, washed with saturated sodium bicarbonate, the organic layer was dried over anhydrous magnesium sulfate, the organic solvent was removed, and the crude product was purified by tetrahydrofuran: recrystallization from 1:4 ethanol gave intermediates 6-28(4.0 g, 90% yield).

Synthesis of compound 28: taking a 100 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, drying, introducing nitrogen, and respectively adding an intermediate 6-28(4.45 g, 0.01mol), a raw material 5(2.40 g, 0.01mol), cesium carbonate (0.012mol), and tris (dibenzylideneacetone) dipalladium (Pd)₂(dba)₃0.5mmol) and 2-dicyclohexylphosphonium-2 ',4',6' -triisopropylbiphenyl (xphos, 0.55mmol), followed by addition of toluene, refluxing of the mixture for 24 hours, cooling to room temperature after the reaction, filtration of the reaction system and concentration, and chromatography purification of the crude product (ethyl acetate/n-hexane, 1/10 (vol.%)) to give compound 28(5.45 g, 84% yield).

Elemental analysis: c₄₇H₂₇N₃Theoretical value of O: c, 86.88, H, 4.19, N, 6.47, found: c, 86.93, H, 4.17, N, 6.45, HRMS (ESI) M/z (M +): theoretical value: 649.2154, found: 649.2159.

synthesis example 4 Synthesis of Compound 34

Synthesis of intermediates 1 to 34: the synthesis of intermediates 1-28 was identical except starting material 6(2.92 g, 0.01mol) was used instead of starting material 1 and starting material 7(1.67 g, 0.01mol) was used instead of starting material 2 to give intermediates 1-34(1.40 g, 42% yield).

Synthesis of intermediates 2 to 34: the same synthesis as intermediates 1-28 was performed except that intermediate 1-34(3.33 g, 0.01mol) was used instead of starting material 1 and starting material 8(2.00 g, 0.01mol) was used instead of starting material 2 to give intermediates 2-34(1.43 g, 35% yield).

Synthesis of intermediates 3 to 34: taking a 100 ml double-neck round-bottom bottle, putting a stirrer and an upper reflux pipe, drying, introducing nitrogen, respectively adding an intermediate 2-34(4.09 g, 0.01mol), triphenylphosphine (0.02mol) and 1, 2-dichlorobenzene (40 ml), heating at 180 ℃ for reaction for 12 hours, cooling to room temperature after the reaction is finished, concentrating a reaction system, and carrying out chromatographic purification on a crude product (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain an intermediate 3-34(2.79 g, yield 74%).

Synthesis of intermediates 4 to 34: the synthesis was identical to that of intermediate 3-28, except that intermediate 3-34(3.77 g, 0.01mol) was used instead of intermediate 3-28, giving intermediate 4-34(4.58 g, 96% yield).

Synthesis of intermediates 5 to 34: the same synthesis as intermediate 4-28 was performed except that intermediate 4-34(4.77 g, 0.01mol) was used instead of intermediate 4-28 to give intermediate 5-34(4.57 g, 79% yield).

Synthesis of intermediates 6 to 34: the same synthesis as intermediate 5-28 was performed except that intermediate 5-34(5.79 g, 0.01mol) was used instead of intermediate 5-28 to give intermediate 6-34(4.33 g, 94% yield).

Synthesis of compound 34: synthesis of Compound 28 was performed except that intermediates 6-34(4.61 g, 0.01mol) were used instead of intermediates 6-28 to give Compound 34(5.79 g, 87% yield).

Elemental analysis: c₄₇H₂₇N₃Theoretical value of S: c, 84.79, H, 4.09, N, 6.31, S, 4.82, found: c, 84.84, H, 4.08, N, 6.28, S, 4.80, HRMS (ESI) M/z (M +): theoretical value: 665.1926, found: 665.1932.

synthesis example 5 Synthesis of Compound 54

Synthesis of intermediates 1 to 54: synthesis of compound 28 except that 6-28(4.45 g, 0.01mol) was used instead of intermediates 7-28 and starting material 11(2.04 g, 0.01mol) was used instead of starting material 5 gave intermediates 1-54(4.64 g, 89% yield).

Synthesis of intermediates 2 to 54: a100 ml double-neck round-bottom bottle is taken, a stirrer and an upper reflux pipe are placed in the bottle, nitrogen is filled after drying, intermediates 1 to 54(5.21 g, 0.01mol), N-bromosuccinimide (0.011mol) and 40 ml tetrahydrofuran are respectively added, and stirring is carried out for 10 hours at room temperature. After the reaction was complete, 5 ml of water were added. Extracting the reaction system for three times by using dichloromethane, and sequentially adding magnesium sulfate into the obtained extract liquor for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/hexane, 1/10) to afford intermediates 2-54(4.07 g, 68% yield).

Synthesis of intermediates 3 to 54: in a 100 ml three-necked flask, the intermediates 2 to 54(5.99 g, 0.01mol), the raw material 7(1.67 g, 0.01mol), potassium carbonate (1.66 g, 0.012mol), toluene (30 ml), water (6 ml), tetrakis (triphenylphosphine) palladium (5.8 g, 0.5mmol) were added under nitrogen protection, stirred at 100 ℃ for 10 hours, and cooled to room temperature after reaction. Adding water into a reaction system, extracting by dichloromethane, and sequentially adding magnesium sulfate into the obtained extract liquor for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to afford intermediate 3-54(4.94 g, 77% yield).

Synthesis of intermediates 4 to 54: taking a 100 ml double-neck round-bottom bottle, putting a stirrer and an upper reflux pipe, drying, introducing nitrogen, respectively adding the intermediates 3-54(6.42 g, 0.01mol), triphenylphosphine (0.02mol) and 1, 2-dichlorobenzene (40 ml), heating at 180 ℃ for reaction for 12 hours, cooling to room temperature after the reaction is finished, concentrating the reaction system, and purifying the crude product by chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain the intermediates 4-54(5.12 g, 84% yield).

Synthesis of compound 54: synthesis of compound 28 except that intermediate 7-28 was replaced with 4-54(6.10 g, 0.01mol) and starting material 5 was replaced with starting material 11(2.04 g, 0.01mol) gave compound 54(5.90 g, 86% yield).

Elemental analysis: c₅₁H₃₀N₂Theoretical value of O: c, 89.19, H, 4.40, N, 4.08, found: c, 89.23, H, 4.38, N, 4.07, HRMS (ESI) M/z (M +): theoretical value: 686.2358, found: 686.2364.

synthesis example 6 Synthesis of Compound 72

Synthesis of intermediates 1 to 72: synthesis of intermediates 1-28 starting material 7(1.67 g, 0.01mol) was substituted for starting material 2 to give intermediates 1-72(1.01 g, 32% yield).

Synthesis of intermediates 2 to 72: the same synthesis as intermediates 1-28 was performed except that intermediate 1-72(3.16 g, 0.01mol) was used instead of starting material 1 and starting material 8(2.00 g, 0.01mol) was used instead of starting material 2 to give intermediates 2-72(1.29 g, 33% yield).

Synthesis of intermediates 3 to 72: taking a 100 ml double-neck round-bottom bottle, putting a stirrer and an upper reflux pipe, drying, introducing nitrogen, respectively adding an intermediate 2-72(3.92 g, 0.01mol), triphenylphosphine (0.02mol) and 1, 2-dichlorobenzene (40 ml), heating at 180 ℃ for reaction for 12 hours, cooling to room temperature after the reaction is finished, concentrating a reaction system, and carrying out chromatographic purification on a crude product (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain an intermediate 3-72(2.56 g, yield 71%).

Synthesis of intermediates 4 to 72: the synthesis was identical to that of intermediate 3-28, except that intermediate 3-72(3.60 g, 0.01mol) was used instead of intermediate 3-28, giving intermediate 4-72(5.38 g, 96% yield).

Synthesis of intermediates 5 to 72: the same synthesis as intermediate 4-28 was performed except that intermediate 4-72(5.60 g, 0.01mol) was used instead of intermediate 4-28 to give intermediate 5-72(4.90 g, 74% yield).

Synthesis of intermediates 6 to 72: the synthesis was identical to that of intermediate 5-28, except that intermediate 5-72(6.62 g, 0.01mol) was used instead of intermediate 5-28, giving intermediate 6-72(4.22 g, 95% yield).

Synthesis of compound 72: synthesis of compound 28 was performed except that intermediates 7-28 were replaced with intermediates 7-72(4.44 g, 0.01mol) and starting material 5 was replaced with starting material 11(1.12 g, 0.01mol) to give compound 72(5.24 g, 88% yield).

Elemental analysis: c₄₅H₂₈N₂Theoretical value: c, 90.58, H, 4.73, N, 4.69, found: c, 90.62, H, 4.71, N, 4.67, HRMS (ESI) M/z (M +): theoretical value: 596.2252, found: 596.2259.

synthesis example 7 Synthesis of Compound 5

Synthesis of intermediates 8 to 5: a100 ml two-necked round-bottomed flask was taken, and a stirrer and an upper reflux tube were placed, and after drying, nitrogen gas was introduced, and then, intermediates 7 to 72(4.44 g, 0.01mol), raw material 12(2.67 g, 0.01mol), cesium carbonate (0.012mol), tris (dibenzylideneacetone) dipalladium (Pd2(dba)3, 0.5mmol) and 2-dicyclohexylphosphorus-2 ',4',6' -triisopropylbiphenyl (xphos, 0.55mmol) were added, followed by toluene, the mixture was refluxed for 18 hours, after reaction, cooled to room temperature, the reaction system was filtered and concentrated, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain intermediates 8 to 5(3.17 g, yield 47%).

Synthesis of Compound 5: a100 ml two-neck round-bottom flask is taken and placed with a stirrer and an upper reflux pipe, nitrogen is filled after drying, intermediate 8-5(6.75 g, 0.01mol), raw material 11(1.12 g, 0.01mol), 1,1' -bis (diphenylphosphino) ferrocene) palladium (II) dichloride (0.5mmol), 10% palladium-carbon (0.5mmol), trimethylbenzene (50 ml), sodium tert-butoxide (0.01mol) are respectively added, the mixture is refluxed for 24 hours, cooled to room temperature after reaction, a reaction system is filtered and concentrated, and a crude product is purified by chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain compound 5(6.68 g, 89% yield).

Elemental analysis: c₅₄H₃₃N₅Theoretical value: c, 86.26, H, 4.42, N, 9.31, found: c, 86.21, H, 4.44, N, 9.35, HRMS (ESI) M/z (M +): theoretical value: 751.2736, found: 751.2745.

synthesis example 8 Synthesis of Compound 77

Synthesis of intermediates 1 to 77: the synthesis of intermediates 1-28 was identical except starting material 14(3.02 g, 0.01mol) was used instead of starting material 1 and starting material 7(1.67 g, 0.01mol) was used instead of starting material 2 to give intermediates 1-77(1.37 g, 40% yield).

Synthesis of intermediates 2 to 77: the synthesis was identical to intermediates 1-28 except that intermediate 1-77(3.43 g, 0.01mol) was used instead of starting material 1 and starting material 8(2.00 g, 0.01mol) was used instead of starting material 2 to give intermediates 2-77(1.42 g, 34% yield).

Synthesis of intermediates 3 to 77: taking a 100 ml double-neck round-bottom bottle, putting a stirrer and an upper reflux pipe, drying, introducing nitrogen, respectively adding an intermediate 2-77(4.19 g, 0.01mol), triphenylphosphine (0.02mol) and 1, 2-dichlorobenzene (40 ml), heating at 180 ℃ for reaction for 12 hours, cooling to room temperature after the reaction is finished, concentrating a reaction system, and carrying out chromatographic purification on a crude product (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain an intermediate 3-77(2.71 g, yield 70%).

Synthesis of intermediates 4 to 77: the synthesis was identical to that of intermediate 3-28, except that intermediate 3-77(3.87 g, 0.01mol) was used instead of intermediate 3-28, giving intermediate 4-77(4.63 g, 95% yield).

Synthesis of intermediates 5 to 77: the synthesis was identical to that of intermediates 4-28 except that intermediate 4-77(4.87 g, 0.01mol) was used instead of intermediate 4-28 to give intermediates 5-77(4.48 g, 76% yield).

Synthesis of intermediates 6 to 77: the synthesis was identical to that of intermediates 5-28, except that intermediate 5-77(5.89 g, 0.01mol) was used instead of intermediate 5-28, giving intermediate 6-77(4.33 g, 92% yield).

Synthesis of compound 77: synthesis of compound 28 was performed except that intermediate 6-77(4.71 g, 0.01mol) was used instead of intermediate 6-28 to give compound 77(5.98 g, 88% yield).

Elemental analysis: c₅₀H₂₈N₃D₅Theoretical value: c, 88.20, H, 5.62, N, 6.17, found: c, 88.17, H, 5.64, N, 6.19, HRMS (ESI) M/z (M +): theoretical value: 680.2988, found: 680.2995.