Amine compound and organic electroluminescent device thereof

Abstract

The present invention provides an amine compound and an organic electroluminescent device thereof, and relates to the technical field of organic electroluminescent materials. The amine compound of the present invention has good hole transport performance and high luminous efficiency, and has relatively excellent stability, can effectively transport holes, and balance carrier injection. In addition, when used as a covering layer, it can prevent the light emitted to the outside from being totally reflected and lost, improve the light extraction efficiency, and thus extend the service life of the device.

Description

Technical Field

[0001] The invention relates to the technical field of organic electroluminescent materials, and in particular to an amine compound and an organic electroluminescent device thereof. Background Art

[0002] Compared with liquid crystal displays (LCDs), organic light-emitting diodes (OLEDs) are self-luminous elements with many excellent properties such as wide viewing angle, excellent contrast, low voltage, fast response, high efficiency, and long life. Therefore, they are widely used in the fields of lighting and display and have broad development prospects.

[0003] Under the action of the electric field, the holes generated by the anode and the electrons generated by the cathode move and are injected into the hole transport layer and the electron transport layer, and migrate to the light-emitting layer. The two meet to generate energy excitons, which activate the luminescent material in the light-emitting layer of the device. The electrons in the molecules of the luminescent material transition from the ground state to the excited state. Since the electrons in the excited state are extremely unstable, the electrons migrate back to the stable ground state. During the transition, energy is released in the form of light, thereby achieving the luminescence of the device. In 1987, Tang et al. of Eastman Kodak Company achieved the development of practical OLEDs by sharing the various functions of luminescence in a laminated structure of different materials. With the continuous improvement of subsequent research work, various well-known functional layers have been formed, namely, hole injection layer, hole transport layer, electron blocking layer, light-emitting layer, hole blocking layer, electron transport layer, electron injection layer and covering layer. The existence of these functional layers has better improved the performance of the device.

[0004] The efficiency of organic light-emitting devices can be divided into external and internal. The internal luminous efficiency is related to the hole transport layer, the light-emitting layer, the electron transport layer, etc. Whether excitons can be effectively generated for light conversion, the effective transport of carriers is very important. The fast hole transfer rate causes them to diffuse to the electron transport region, causing the recombination of excitons to occur in the electron transport layer, and the energy is mainly released in the form of heat, which reduces the service life of the device. It can be seen that by balancing the injection of carriers and blocking the diffusion of holes toward the cathode, the luminescence performance can be improved. Therefore, the research on new hole transport materials cannot be ignored.

[0005] External luminous efficiency is the efficiency of extracting light generated in the light-emitting layer to the outside of the organic light-emitting device, that is, light extraction efficiency. In order to prevent the light emitted to the outside from being totally reflected and lost, an organic compound is used as a cover layer to improve the performance of the organic light-emitting device.

[0006] To this end, developing an organic material that can balance carrier injection, improve light extraction efficiency, and extend device life remains a research and development focus. Summary of the invention

[0007] In order to effectively improve the luminous efficiency of the device and prolong the service life, the present invention provides an amine compound and an organic electroluminescent device thereof.

[0008]

[0009] In formula 1,

[0010] The L is selected from one of the following groups:

[0011]

[0012] The R1 and R2 are independently selected from any one of substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C20 heteroaryl;

[0013] R3 and R4 are independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl;

[0014] The R is independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl;

[0015] The a and b are independently selected from 0, 1, 2 or 3. When a and b are greater than 1, multiple R3 and R4 are the same or different.

[0016] The n is independently selected from 0, 1, 2, 3 or 4, and the g is independently selected from 0, 1, 2 or 3. When n and g are greater than 1, multiple R are the same or different;

[0017] The Ar1-Ar4 are independently selected from any one of the structures shown in Formula 2, substituted or unsubstituted C6-C25 aryl groups, and substituted or unsubstituted C2-C20 heteroaryl groups, and the heteroaryl group is not a carbazolyl group; wherein at least one of the Ar1-Ar4 is a structure shown in Formula 2;

[0018] In formula 2,

[0019] The X is selected from O or S;

[0020] The Y is independently selected from CR a or N;

[0021] The R aAny one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl is independently selected; when multiple R a When it exists, the adjacent R a They can be bonded to form substituted or unsubstituted: benzene ring, naphthalene ring, pyridine ring, pyrimidine ring;

[0022] The R5 is independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl;

[0023] The c is selected from 0 or 1;

[0024] The L1-L6 are independently selected from a single bond or one of the following structures:

[0025]

[0026] Wherein, the R6 is independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl;

[0027] The a0 is selected from 0, 1, 2, 3 or 4;

[0028] The b0 is selected from 0, 1, 2 or 3;

[0029] The c0 is selected from 0, 1 or 2;

[0030] The d0 is selected from 0 or 1;

[0031] When a0, b0, and c0 are greater than 1, multiple R6s are the same or different, and adjacent R6s may be bonded to form a substituted or unsubstituted ring.

[0032] In addition, the present invention also provides an organic electroluminescent device, which comprises the amine compound.

[0033] Beneficial effects: The amine compounds involved in the present invention have good hole transport performance and high luminous efficiency, have relatively excellent stability, can effectively transport holes, and effectively recombine carriers in the light-emitting layer. In addition, as a covering layer, it can prevent the light emitted to the outside from being totally reflected and lost, effectively improve the light extraction efficiency, and thus extend the service life of the device. DETAILED DESCRIPTION

[0034] The present invention will be further described in detail below in conjunction with specific embodiments, and it should be understood that the embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention. Based on the embodiments in the present invention, other embodiments obtained by those skilled in the art without making creative work are all within the scope of protection required by this application.

[0035] The substituent groups of the present invention Indicates the connection site.

[0036] The "halogen" mentioned in the present invention includes fluorine, chlorine, bromine and iodine.

[0037] The "C1-C6" in the "substituted or unsubstituted C1-C6 alkyl" described in the present invention represents the number of carbon atoms in the unsubstituted "alkyl", excluding the number of carbon atoms in the substituent. The "C3-C10" in the "substituted or unsubstituted C3-C10 cycloalkyl" described in the present invention represents the number of carbon atoms in the unsubstituted "cycloalkyl", excluding the number of carbon atoms in the substituent. The "C6-C25" in the "substituted or unsubstituted C6-C25 aryl" described in the present invention represents the number of carbon atoms in the unsubstituted "aryl", excluding the number of carbon atoms in the substituent. The "C2-C20" in the "substituted or unsubstituted C2-C20 heteroaryl" described in the present invention represents the number of carbon atoms in the "heteroaryl", excluding the number of carbon atoms in the substituent.

[0038] The alkyl group described in the present invention refers to a monovalent group formed by removing a hydrogen atom from an alkane molecule. It can be straight-chain or branched, and the chain alkyl group with C3 or more in the present invention includes its isomers. Specific examples may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, pentyl, and hexyl, but are not limited thereto.

[0039] The cycloalkyl group described in the present invention refers to a monovalent group formed by removing a hydrogen atom from a cycloalkane molecule. Specific examples may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, and adamantyl, but are not limited thereto.

[0040] The aryl group described in the present invention refers to a monovalent group obtained by removing a hydrogen atom from the parent nucleus of an aromatic hydrocarbon molecule. It can be a monocyclic aryl group, a polycyclic aryl group or a condensed aryl group. The monocyclic aryl group refers to an aryl group having only one aromatic ring in the molecule, such as phenyl, etc., but not limited thereto; the polycyclic aryl group refers to an aryl group having two or more independent aromatic rings in the molecule, and specific examples may include biphenyl and terphenyl, but not limited thereto; the condensed aryl group refers to an aryl group having two or more aromatic rings in the molecule and fused to each other by sharing two adjacent carbon atoms, and specific examples may include naphthyl, anthracenyl, phenanthrenyl, fluorenyl, benzofluorenyl, pyrenyl, triphenylene, fluoranthenyl, spirobifluorenyl, but not limited thereto.

[0041] The heteroaryl group described in the present invention refers to a monovalent group obtained by removing a hydrogen atom from the parent nucleus of a heterocyclic aromatic hydrocarbon molecule. It may contain one or more of N, O, P, S, Si, and Se as heteroatoms, and may be a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a condensed ring heteroaryl group. Specific examples of the monocyclic heteroaryl group may include pyridyl, pyrimidyl, triazine, furanyl, thienyl, and pyrrolyl, but are not limited thereto; specific examples of the polycyclic heteroaryl group may include bipyridyl, bipyrimidyl, and phenylpyridyl, but are not limited thereto; specific examples of the condensed ring heteroaryl group may include quinolyl, isoquinolyl, indolyl, dibenzofuranyl, benzodibenzofuranyl, dibenzothienyl, benzodibenzothienyl, etc., except for carbazolyl.

[0042] The "unsubstituted" in the "substituted or unsubstituted" of the present invention means that the hydrogen atom on the group is not replaced by any substituent.

[0043] When no additional definition is provided, the "substituted" in the "substituted or unsubstituted" of the present invention refers to the substitution of at least one hydrogen in the compound by the following substituents: deuterium, halogen, cyano, C1-C6 alkyl, C6-C25 aryl, C2-C20 heteroaryl or a combination thereof. Specific examples may include deuterium, fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, peryl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9,9-spirobifluorenyl, pyrrolyl, furanyl, thienyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothienyl, biphenyl, terphenyl, etc., except carbazolyl.

[0044] The bonding to form a substituted or unsubstituted ring described in the present invention means that two groups are connected to each other by a chemical bond and are optionally aromatized. For example:

[0045]

[0046] The bonded substituted or unsubstituted ring described in the present invention may be a five-membered ring, a six-membered ring or a condensed ring, such as phenyl, naphthyl, cyclopentane, cyclohexane, cyclopentene, cyclohexene, but is not limited thereto.

[0047] The present invention provides an amine compound, which is represented by Formula 1:

[0048]

[0049] In formula 1,

[0050] The L is selected from one of the following groups:

[0051]

[0052] The R1 and R2 are independently selected from any one of substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C20 heteroaryl;

[0053] R3 and R4 are independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl;

[0054] The R is independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl;

[0055] The a and b are independently selected from 0, 1, 2 or 3. When a and b are greater than 1, multiple R3 and R4 are the same or different.

[0056] The n is independently selected from 0, 1, 2, 3 or 4, the g is independently selected from 0, 1, 2 or 3, when n and g are greater than 1, multiple R are the same or different;

[0057] The Ar1-Ar4 are independently selected from any one of the structures shown in Formula 2, substituted or unsubstituted C6-C25 aryl groups, and substituted or unsubstituted C2-C20 heteroaryl groups, and the heteroaryl group is not a carbazolyl group; wherein at least one of the Ar1-Ar4 is a structure shown in Formula 2;

[0058] In formula 2,

[0059] The X is selected from O or S;

[0060] The Y is independently selected from CR a or N;

[0061] The R a independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl, and multiple R a When it exists, the adjacent R a They can be bonded to form substituted or unsubstituted: benzene ring, naphthalene ring, pyridine ring, pyrimidine ring;

[0062] The R5 is independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl;

[0063] The c is selected from 0 or 1;

[0064] The L1-L6 are independently selected from a single bond or one of the following structures:

[0065]

[0066] Wherein, the R6 is independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl;

[0067] The a0 is independently selected from 0, 1, 2, 3 or 4;

[0068] The b0 is independently selected from 0, 1, 2 or 3;

[0069] The c0 is independently selected from 0, 1 or 2;

[0070] The d0 is independently selected from 0 or 1;

[0071] When a0, b0, and c0 are greater than 1, multiple R6s are the same or different, and adjacent R6s may be bonded to form a substituted or unsubstituted ring.

[0072] Preferably, L1-L6 are independently selected from a single bond or one of the following structures:

[0073]

[0074] Preferably, L is selected from one of the following structures:

[0075]

[0076] The h is independently selected from 0, 1, 2, 3, 4 or 5;

[0077] The k is independently selected from 0, 1, 2, 3 or 4;

[0078] The m is independently selected from 0, 1, 2 or 3.

[0079] More preferably, L is selected from one of the following structures:

[0080]

[0081] Preferably, at least one of Ar1, Ar2, Ar3, and Ar4 is selected from the structure shown in Formula 2, including one, two, three or four of Ar1, Ar2, Ar3, and Ar4 are selected from the structure shown in Formula 2; when one of Ar1, Ar2, Ar3, and Ar4 is selected from the structure shown in Formula 2, Ar1, Ar2, Ar3, or Ar4 is selected from the structure shown in Formula 2; when two of Ar1, Ar2, Ar3, and Ar4 are selected from the structure shown in Formula 2, Ar1 and Ar2, or Ar1 and Ar3 are selected from the structure shown in Formula 2; when three of Ar1, Ar2, Ar3, and Ar4 are selected from the structure shown in Formula 2, Ar1, Ar2, and Ar3 are selected from the structure shown in Formula 2; when four of Ar1, Ar2, Ar3, and Ar4 are selected from the structure shown in Formula 2, Ar1, Ar2, Ar3, and Ar4 are selected from the structure shown in Formula 2.

[0082] Preferably, Ar1, Ar2, Ar3, Ar4 are substituted or unsubstituted structures represented by Formula 2:

[0083]

[0084] Preferably, the "substituted" in the "substituted or unsubstituted" refers to at least one hydrogen being replaced by the following substituents: deuterium, methyl, isopropyl, tert-butyl, cyano, trifluoromethyl, adamantyl, phenyl.

[0085] Preferably, the formula 2 is selected from one of the following groups:

[0086]

[0087]

[0088] The c is selected from 0 or 1;

[0089] Said p is independently selected from 0, 1, 2, 3 or 4;

[0090] The q is independently selected from 0, 1, 2 or 3;

[0091] The s is independently selected from 0, 1 or 2;

[0092] Preferably, R a , R5 is independently selected from: deuterium, methyl, ethyl, isopropyl, tert-butyl, cyano, fluoro, trifluoromethyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, phenyl, deuterated phenyl;

[0093] When p, q, s are greater than 1, multiple R a Same or different, and adjacent R a They can be bonded to form substituted or unsubstituted benzene ring, naphthalene ring, pyridine ring, and pyrimidine ring.

[0094] More preferably, the formula 2 is selected from one of the following groups:

[0095]

[0096]

[0097] The d is independently selected from 0, 1, 2, 3, 4 or 5;

[0098] The e is independently selected from 0, 1, 2, 3 or 4.

[0099] More preferably, the formula 2 is selected from one of the following groups:

[0100]

[0101] Most preferably, the amine compound is selected from one of the following compounds:

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114] The present invention also provides an organic electroluminescent device, which comprises one or more of the amine compounds.

[0115] Preferably, the organic electroluminescent device comprises an anode, a cathode, and an organic layer disposed between the anode and the cathode, and the organic layer comprises one or more of the amine compounds.

[0116] Preferably, the organic electroluminescent device comprises an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer comprises a hole transport region, a light-emitting layer, and an electron transport region, and the hole transport region comprises one or more of the amine compounds.

[0117] The hole transport region of the present invention includes at least one of a hole injection layer, a hole transport layer and a light-emitting auxiliary layer. Preferably, the hole transport region includes at least two of the hole injection layer, the hole transport layer and the light-emitting auxiliary layer; further preferably, the hole transport region includes a hole injection layer and a hole transport layer. More preferably, the hole transport region includes a hole injection layer, a hole transport layer and a light-emitting auxiliary layer. At least one of the hole injection layer, the hole transport layer and the light-emitting auxiliary layer includes one or more of the amine compounds.

[0118] Preferably, the organic layer includes at least one 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 at least one of the hole injection layer and the hole transport layer includes one or more of the amine compounds.

[0119] Preferably, the organic layer comprises a hole transport layer, the hole transport layer is located between the anode and the light-emitting layer, and the hole transport layer comprises one or more of the amine compounds.

[0120] Preferably, the organic electroluminescent device further comprises a covering layer, the covering layer is located on a side of the cathode away from the anode, and the covering layer comprises one or more of the amine compounds.

[0121] The anode material of the present invention is generally a material with a higher work function, so as to improve the hole injection efficiency. Specific examples include, but are not limited to: metals and alloys, such as silver (Ag), aluminum (Al), gold (Au), copper (Cu), nickel (Ni), molybdenum (Mo), titanium (Ti), zinc (Zn), palladium (Pd), platinum (Pt), vanadium (V), chromium (Cr), or their alloys; metal oxides, such as indium zinc oxide (IZO), indium tin oxide (ITO), indium oxide (InO), zinc oxide (ZnO), etc.; combinations of metals and oxides, such as tin oxide: antimony (SnO2:Sb) and zinc oxide: aluminum (ZnO:Al); laminated materials, such as aluminum / gold (Al / Au), aluminum / silver (Al / Ag), etc.

[0122] The cathode material of the present invention is generally a material with a small work function, so as to promote the efficiency of electron injection. Specific examples include, but are not limited to: metals, such as silver (Ag), magnesium (Mg), aluminum (Al), indium (In), etc.; metal alloys, such as lithium aluminum alloy (Li:Al), magnesium silver alloy (Mg:Ag), etc.; laminated materials, such as magnesium / aluminum (Mg / Al), magnesium / silver (Mg / Ag), aluminum / silver (Al / Ag), etc.

[0123] The hole injection material of the present invention is generally a material with good hole capacity and suitable HOMO energy level. Specific examples include, but are not limited to: phthalocyanine compounds, such as copper phthalocyanine, oxytitanium phthalocyanine, etc.; aromatic amine derivatives, such as N4,N4,N4",N4"-tetrakis([1,1'-biphenyl]-4-yl)-[1,1':4',1"-terphenyl]-4,4"-diamine, 4,4',4"-tris(N-(naphthalene-1-yl)-N-phenyl-amino)triphenylamine (1T-NATA), 4,4',4"-tris[2-naphthylphenylamino]triphenylamine (2T-NATA), N,N'-di(naphthalene-1-yl)-N,N'-diphenyl-benzidine (NPB), etc.; polymer materials, such as poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDT:PSS), etc.

[0124] The hole transport material of the present invention is generally a material with a high hole mobility, so as to transfer the received holes to the light-emitting layer. Specific examples include, but are not limited to: fluorene derivatives N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD); triphenylamine derivatives, such as 4,4',4"-tri(carbazole-9-yl)triphenylamine), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), 4-[1-[4-[di(4-methylphenyl)amino]phenyl]cyclohexyl]-N-(3-methylphenyl)-N-(4-methylphenyl)aniline (TAPC), etc.; polymer materials polyvinylcarbazole (PVC), etc. Preferably, the hole transport material is selected from an amine compound described in the present invention.

[0125] The luminescent material of the present invention is usually a fluorescent material and a phosphorescent material. In order to avoid the problem of concentration quenching of the phosphorescent material, the phosphorescent material is usually used as a doping material. The luminescent layer is prepared by co-deposition with other matrix materials (main materials). The amount of the phosphorescent material is preferably 0.1-70wt%, more preferably 0.1-30wt%, further preferably 1-30wt%, further preferably 1-20wt%, and particularly preferably 1-10wt%.

[0126] Specific examples of fluorescent materials that can be used in the present invention include, but are not limited to, indole derivatives, carbazole derivatives, boron-containing compounds, pyrrole derivatives, fused polycyclic aromatic derivatives, styrylamine derivatives, fused ring amine derivatives, etc. Specific examples of phosphorescent materials that can be used include, but are not limited to, rare earth metal complexes, such as terbium complexes, europium complexes, etc.; heavy metal complexes, such as iridium complexes, platinum complexes, osmium complexes, etc.

[0127] Specific examples of the host materials that can be used in the present invention include but are not limited to: fused aromatic ring derivatives, such as naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, fluoranthene derivatives, etc.; compounds containing heterocyclic rings, such as pyrimidine derivatives, carbazole derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, etc.

[0128] The hole blocking material of the present invention generally has good hole blocking ability so as to block holes in the light-emitting layer. Specific examples include, but are not limited to, imidazole derivatives, azabenzene derivatives, anthraquinone derivatives, anthrone derivatives, quinoline derivatives, and the like.

[0129] The electron transport material of the present invention is generally a material having excellent electron mobility, and specific examples include but are not limited to metal complexes, thiazole derivatives, azabenzene derivatives, pyridine derivatives, quinoline derivatives, phenanthroline derivatives, imidazole derivatives, triazole derivatives, and the like.

[0130] The electron injection material of the present invention is generally a material with good electron injection ability so as to reduce the potential barrier between the cathode and the electron transport layer. Specific examples include but are not limited to: alkali metal salts, alkaline earth metal salts, metal oxides, etc.

[0131] The cover layer of the present invention has the function of light extraction, and specific examples include but are not limited to: metal compounds, aromatic amine derivatives, carbazole derivatives, etc. Preferably, the cover layer of the present invention is selected from an amine compound of the present invention.

[0132] The manufacturing method of each layer of the organic electroluminescent device described in the present invention can be a known method such as a dry film forming method or a wet film forming method. Specific examples include but are not limited to: vacuum evaporation method, plasma method, spin coating method, dipping method, spray film method, etc.

[0133] The organic electroluminescent device described in the present invention is mainly used in the field of display technology, such as flexible OLED, organic solar cell, lighting source, panel display, etc.

[0134] Synthesis Example

[0135] The present invention has no particular limitation on the method for preparing the amine compound, and conventional methods known to those skilled in the art may be used.

[0136] For example:

[0137]

[0138] Wherein, X0 is independently selected from Cl, Br or I.

[0139] The present invention has no particular limitation on the sources of the raw materials involved in the examples, and the raw materials can be commercially available products or obtained by preparation methods well known to those skilled in the art.

[0140] The instrument used for mass spectrometry was a G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer from Waters, UK; the instrument used for elemental analysis was a Vario EL cube organic element analyzer from Elementar, Germany.

[0141] [Synthesis Example 1] Synthesis of Compound 13

[0142]

[0143] Preparation of intermediate A-13:

[0144] Under nitrogen protection, a-13 (80.00mmol, 18.29g), b-13 (82.00mmol, 7.64g), sodium tert-butoxide (160.00mmol, 15.38g) were added to 300ml toluene, and Pd(OAc)2 (1.60mmol, 0.36g) and P(t-Bu)3 (3.20mmol, 6.40ml of 0.5M toluene solution) were added under stirring, and the mixed solution of the above reactants was heated to reflux for 7h. After the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, and the liquid was separated by standing. The organic layer was collected and dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation, cooled and crystallized, and filtered by suction. The obtained solid was recrystallized with toluene / methanol (volume ratio 10:1) to obtain intermediate A-13 (18.03g, yield 79%), and the solid purity was ≥99.71% by HPLC. Mass spectrum m / z: 285.1140 (theoretical value: 285.1154).

[0145] Preparation of intermediate M-13:

[0146] Under nitrogen protection, m-13 (80.00mmol, 34.54g), n-13 (82.00mmol, 13.88g), sodium tert-butoxide (160.00mmol, 15.38g) were added to 300ml toluene, and Pd(dppf)Cl2 (1.60mmol, 1.17g) was added under stirring, and the mixed solution of the above reactants was heated to reflux for 6h. After the reaction was completed, it was cooled to room temperature, and dichloromethane and distilled water were added to the mixture for extraction, and the mixture was allowed to stand for separation. The organic phase was collected and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. It was purified by silica gel column chromatography with n-hexane / dichloromethane (volume ratio 10:1) to obtain intermediate M-13 (35.36g, 85%). The solid purity was ≥99.85% by HPLC. Mass spectrum m / z: 519.1768 (theoretical value: 519.1754).

[0147] Preparation of compound 13:

[0148] Under nitrogen protection, intermediate M-13 (30.00mmol, 15.60g), intermediate A-13 (32.00mmol, 9.13g), sodium tert-butoxide (60.00mmol, 5.77g) were added to 200ml toluene, and Pd(OAc)2 (0.60mmol, 0.13g) and P(t-Bu)3 (1.20mmol, 2.40ml of 0.5M toluene solution) were added under stirring, and the mixed solution of the above reactants was heated to reflux for 5.5h. After the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, and the liquid was separated by standing. The organic layer was collected and dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation, cooled and crystallized, and filtered by suction. The obtained solid was recrystallized with toluene / methanol (volume ratio 10:1) to obtain compound 13 (17.30g, yield 75%), and the solid purity was ≥99.98% detected by HPLC. Mass spectrum m / z: 768.3133 (theoretical value: 768.3141). Theoretical element content (%) C 57 H 40 N2O: C, 89.03; H, 5.24; N, 3.64. Measured element content (%): C, 89.02; H, 5.23; N, 3.68.

[0149] [Synthesis Example 2] Synthesis of Compound 27

[0150]

[0151] Preparation of intermediate A-13:

[0152] Under nitrogen protection, a-13 (100.00mmol, 22.87g), b-13 (102.00mmol, 9.50g), sodium tert-butoxide (200.00mmol, 19.22g) were added to 300ml toluene, and Pd(OAc)2 (2.00mmol, 0.45g) and P(t-Bu)3 (4.00mmol, 8.00ml of 0.5M toluene solution) were added under stirring, and the mixed solution of the above reactants was heated to reflux for 7.5h. After the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, and the liquid was separated by standing. The organic layer was collected and dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure, cooled and crystallized, and filtered by suction. The obtained solid was recrystallized with toluene / methanol (volume ratio 10:1) to obtain intermediate A-13 (23.68g, yield 83%), and the solid purity was ≥99.74% by HPLC. Mass spectrum m / z: 362.1428 (theoretical value: 362.1419).

[0153] Preparation of compound 27:

[0154] Under nitrogen protection, m-27 (30.00mmol, 14.29g), intermediate A-13 (62.00mmol, 17.69g), sodium tert-butoxide (60.00mmol, 5.77g) were added to 250ml toluene, and Pd(OAc)2 (0.60mmol, 0.13g) and P(t-Bu)3 (1.20mmol, 2.40ml of 0.5M toluene solution) were added under stirring, and the mixed solution of the above reactants was heated to reflux for 6h. After the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, and the liquid was separated by standing. The organic layer was collected and dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure, cooled and crystallized, and filtered by suction. The obtained solid was recrystallized with toluene to obtain compound 27 (20.71g, yield 78%), and the solid purity was ≥99.97% by HPLC. Mass spectrum m / z: 884.3416 (theoretical value: 884.3403). Theoretical element content (%) C 65 H 44 N2O2: C, 88.21; H, 5.01; N, 3.17. Measured element content (%): C, 88.23; H, 5.02; N, 3.16.

[0155] [Synthesis Example 3] Synthesis of Compound 46

[0156]

[0157] According to the preparation method of Synthesis Example 1, a-13 was replaced by an equal mole of a-46, b-13 was replaced by an equal mole of b-46, and m-13 was replaced by an equal mole of m-46 to obtain compound 46 (20.73 g). The solid purity was ≥ 99.97% by HPLC. Mass spectrum m / z: 920.3528 (theoretical value: 920.3515). Theoretical element content (%) C 67 H 44 N4O: C, 87.37; H, 4.82; N, 6.08. Measured element content (%): C, 87.38; H, 4.85; N, 6.06.

[0158] [Synthesis Example 4] Synthesis of Compound 56

[0159]

[0160] According to the preparation method of Synthesis Example 2, a-13 was replaced by an equal mole of a-46, b-13 was replaced by an equal mole of b-56, and m-27 was replaced by an equal mole of m-56 to obtain compound 56 (27.00 g). The solid purity was ≥ 99.96% by HPLC. Mass spectrum m / z: 1267.5166 (theoretical value: 1267.5158). Theoretical element content (%) C 95 H 66 N2O2: C, 90.02; H, 5.25; N, 2.21. Measured element content (%): C, 90.03; H, 5.28; N, 2.18.

[0161] [Synthesis Example 5] Synthesis of Compound 66

[0162]

[0163] According to the preparation method of Synthesis Example 1, a-13 was replaced by an equal mole of a-66, b-13 was replaced by an equal mole of b-66, m-13 was replaced by an equal mole of m-66, and n-13 was replaced by an equal mole of n-66 to obtain compound 66 (17.95 g). The solid purity was ≥ 99.96% by HPLC. Mass spectrum m / z: 830.2923 (theoretical value: 830.2933). Theoretical element content (%) C 61 H 38 N2O2: C, 88.17; H, 4.61; N, 3.37. Measured element content (%): C, 88.18; H, 4.60; N, 3.38.

[0164] [Synthesis Example 6] Synthesis of Compound 69

[0165]

[0166] According to the preparation method of Synthesis Example 1, a-13 was replaced by an equal molar amount of a-66, b-13 was replaced by an equal molar amount of b-69, and m-13 was replaced by an equal molar amount of m-69 to obtain compound 69 (16.89 g). The solid purity was ≥ 99.98% as determined by HPLC. Mass spectrum m / z: 740.2838 (theoretical value: 740.2828). Theoretical element content (%) C 55 H 36 N2O: C, 89.16; H, 4.90; N, 3.78. Measured element content (%): C, 89.18; H, 4.88; N, 3.77.

[0167] [Synthesis Example 7] Synthesis of Compound 82

[0168]

[0169] According to the preparation method of Synthesis Example 2, a-13 was replaced by an equal mole of a-82, b-13 was replaced by an equal mole of b-82, and m-27 was replaced by an equal mole of m-82 to obtain compound 82 (26.53 g). The solid purity was ≥ 99.95% by HPLC. Mass spectrum m / z: 1262.3585 (theoretical value: 1262.3576). Theoretical element content (%) C 89 H 54 N2O3S2: C, 84.60; H, 4.31; N, 2.22. Measured element content (%): C, 84.62; H, 4.33; N, 2.21.

[0170] [Synthesis Example 8] Synthesis of Compound 90

[0171]

[0172] Preparation of intermediate A-66:

[0173] Under nitrogen protection, a-66 (120.00 mmol, 18.31 g), b-66 (122.00 mmol, 16.24 g) and sodium tert-butoxide (240.00 mmol, 23.06 g) were added to 300 ml of toluene, and Pd(OAc)2 (2.40 mmol, 0.54 g) and P(t-Bu)3 (4.80 mmol, 9.60 ml of 0.5 M toluene solution) were added under stirring, and the mixed solution of the above reactants was heated to reflux for 7.5 h. After the reaction, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The mixture was allowed to stand for separation, and the organic layer was collected and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure. The temperature was lowered for crystallization, and suction was filtered. The obtained solid was recrystallized from toluene / methanol (volume ratio 10:1) to obtain intermediate A-66 (24.53 g, yield 82%). The solid purity was ≥99.74% by HPLC. Mass spectrum m / z: 249.0798 (theoretical value: 249.0790).

[0174] Preparation of intermediate C-90:

[0175] Under nitrogen protection, c-90 (70.00mmol, 16.08g), d-90 (72.00mmol, 15.79g), sodium tert-butoxide (140.00mmol, 13.45g) were added to 300ml toluene, and Pd(OAc)2 (1.40mmol, 0.31g) and P(t-Bu)3 (2.80mmol, 5.60ml of 0.5M toluene solution) were added under stirring, and the mixed solution of the above reactants was heated to reflux for 7h. After the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, and the liquid was separated by standing. The organic layer was collected and dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The temperature was lowered for crystallization, and suction was filtered. The obtained solid was recrystallized with toluene / methanol (volume ratio 10:1) to obtain intermediate C-90 (22.81g, yield 79%). The solid purity was ≥99.78% by HPLC. Mass spectrum m / z: 412.1585 (theoretical value: 412.1576).

[0176] Preparation of intermediate M-90:

[0177] Under nitrogen protection, m-90 (80.00mmol, 35.66g), A-66 (82.00mmol, 20.44g), sodium tert-butoxide (160.00mmol, 15.38g) were added to 300ml toluene, and Pd(OAc)2 (1.60mmol, 0.36g) and P(t-Bu)3 (3.20mmol, 6.40ml of 0.5M toluene solution) were added under stirring, and the mixed solution of the above reactants was heated to reflux for 6.5h. After the reaction was completed, it was cooled to room temperature, and dichloromethane and distilled water were added to the mixture for extraction, and the mixture was allowed to stand for separation. The organic phase was collected and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure. It was purified by silica gel column chromatography with n-hexane / dichloromethane (volume ratio 10:1) to obtain intermediate M-90 (34.39g, yield 70%), and the solid purity was ≥99.88% by HPLC. Mass spectrum m / z: 613.1458 (theoretical value: 613.1445).

[0178] Preparation of compound 90:

[0179] Under nitrogen protection, intermediate M-90 (30.00mmol, 18.42g), intermediate C-90 (32.00mmol, 13.20g), sodium tert-butoxide (60.00mmol, 5.77g) were added to 200ml toluene, and Pd(OAc)2 (0.60mmol, 0.13g) and P(t-Bu)3 (1.20mmol, 2.40ml of 0.5M toluene solution) were added under stirring, and the mixed solution of the above reactants was heated to reflux for 6h. After the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, and the liquid was separated by standing. The organic layer was collected and dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The temperature was lowered for crystallization, and suction was filtered. The obtained solid was recrystallized from toluene to obtain compound 90 (22.87g, yield 77%). The solid purity was ≥99.97% detected by HPLC. Mass spectrum m / z: 989.3263 (theoretical value: 989.3254). Theoretical element content (%) C 70 H 43 N3O4: C, 84.92; H, 4.38; N, 4.24. Measured element content (%): C, 84.95; H, 4.33; N, 4.23.

[0180] [Synthesis Example 9] Synthesis of Compound 102

[0181]

[0182] According to the preparation method of Synthesis Example 1, a-13 was replaced by an equal mole of a-102, b-13 was replaced by an equal mole of b-66, m-13 was replaced by an equal mole of m-102, and n-13 was replaced by an equal mole of n-102 to obtain compound 102 (21.65 g). The solid purity was ≥ 99.98% by HPLC. Mass spectrum m / z: 974.3885 (theoretical value: 974.3872). Theoretical element content (%) C 72 H 50 N2O2: C, 88.68; H, 5.17; N, 2.87. Measured element content (%): C, 88.70; H, 5.18; N, 2.86.

[0183] [Synthesis Example 10] Synthesis of Compound 107

[0184]

[0185] According to the preparation method of Synthesis Example 2, a-13 was replaced by an equal mole of a-107, b-13 was replaced by an equal mole of b-107, and m-27 was replaced by an equal mole of m-107 to obtain compound 107 (24.01 g). The solid purity was ≥ 99.97% by HPLC. Mass spectrum m / z: 1052.3738 (theoretical value: 1052.3726). Theoretical element content (%) C 75 H 48 N4O3: C, 85.53; H, 4.59; N, 5.32. Measured element content (%): C, 85.51; H, 4.58; N, 5.33.

[0186] [Synthesis Example 11] Synthesis of Compound 116

[0187]

[0188] According to the preparation method of Synthesis Example 2, b-13 was replaced by an equal mole of b-116, and m-27 was replaced by an equal mole of m-1116 to obtain compound 116 (24.44 g). The solid purity was ≥ 99.98% as determined by HPLC. Mass spectrum m / z: 1130.3708 (theoretical value: 1130.3720). Theoretical element content (%) C 81 H 50 N2O5: C, 86.00; H, 4.46; N, 2.48. Measured element content (%): C, 86.01; H, 4.47; N, 2.47.

[0189] [Synthesis Example 12] Synthesis of Compound 119

[0190]

[0191] According to the preparation method of Synthesis Example 1, a-13 was replaced by an equal mole of a-119, b-13 was replaced by an equal mole of b-119, and m-13 was replaced by an equal mole of m-119 to obtain compound 119 (20.43 g). The solid purity was ≥ 99.95% by HPLC. Mass spectrum m / z: 907.3185 (theoretical value: 907.3199). Theoretical element content (%) C 66 H 41 N3O2: C, 87.30; H, 4.55; N, 4.63. Measured element content (%): C, 87.28; H, 4.51; N, 4.67.

[0192] [Synthesis Example 13] Synthesis of Compound 135

[0193]

[0194] According to the preparation method of Synthesis Example 8, a-66 was replaced by an equal mole of a-135, b-66 was replaced by an equal mole of b-135, c-90 was replaced by an equal mole of c-135, d-90 was replaced by an equal mole of b-13, and m-90 was replaced by an equal mole of m-135 to obtain compound 135 (20.59 g). The solid purity was ≥ 99.97% by HPLC. Mass spectrum m / z: 890.2797 (theoretical value: 890.2789). Theoretical element content (%) C 63 H 42 N2S2: C, 84.91; H, 4.75; N, 3.14. Measured element content (%): C, 84.95; H, 4.72; N, 3.15.

[0195] [Synthesis Example 14] Synthesis of Compound 143

[0196]

[0197] Preparation of intermediate E-143:

[0198] Under nitrogen protection, e-143 (110.00mmol, 26.57g), f-143 (112.00mmol, 29.25g), Pd(dppf)Cl2 (2.20mmol, 1.61g), Na2CO3 (220.00mmol, 23.32g) and 300mL toluene, 100mL ethanol, 100mL water were stirred, and the above reactant system was heated to reflux for 8h; after the reaction was completed, it was cooled to room temperature, filtered to obtain a filter cake, and the filter cake was washed with ethanol, and finally the filter cake was recrystallized with toluene / ethanol = 10:1 to obtain intermediate E-143 (26.35g, yield 81%); HPLC purity ≥99.73%. Mass spectrum m / z: 295.0238 (theoretical value: 295.0222).

[0199] Preparation of compound 143:

[0200] According to the preparation method of Synthesis Example 1, a-13 was replaced by an equal mole of E-143, and n-13 was replaced by an equal mole of n-143 to obtain compound 143 (19.36 g). The solid purity was ≥ 99.96% as determined by HPLC. Mass spectrum m / z: 837.2918 (theoretical value: 837.2926). Theoretical element content (%) C 58 H 39 N5S: C, 83.13; H, 4.69; N, 8.36. Measured element content (%): C, 83.18; H, 4.68; N, 8.33.

[0201] [Synthesis Example 15] Synthesis of Compound 155

[0202]

[0203] According to the preparation method of Synthesis Example 2, a-13 was replaced by an equal mole of a-155, and b-13 was replaced by an equal mole of b-155 to obtain compound 155 (23.42 g). The solid purity was ≥ 99.96% as determined by HPLC. Mass spectrum m / z: 1068.3585 (theoretical value: 1068.3572). Theoretical element content (%) C 77 H 52 N2S2: C, 86.48; H, 4.90; N, 2.62. Measured element content (%): C, 86.47; H, 4.91; N, 2.61.

[0204] [Synthesis Example 16] Synthesis of Compound 165

[0205]

[0206] According to the preparation method of Synthesis Example 2, a-13 was replaced by an equal molar amount of a-135, b-13 was replaced by an equal molar amount of b-165, and m-27 was replaced by an equal molar amount of m-56 to obtain compound 165 (21.93 g). The solid purity was ≥ 99.97% by HPLC. Mass spectrum m / z: 1014.3118 (theoretical value: 1014.3102). Theoretical element content (%) C 73 H 46 N2S2: C, 86.36; H, 4.57; N, 2.76. Measured element content (%): C, 86.33; H, 4.56; N, 2.78.

[0207] [Synthesis Example 17] Synthesis of Compound 181

[0208]

[0209] According to the preparation method of Synthesis Example 2, a-13 was replaced by an equal mole of a-135, b-13 was replaced by an equal mole of b-135, and m-27 was replaced by an equal mole of m-181 to obtain compound 181 (21.42 g). The solid purity was ≥ 99.96% by HPLC. Mass spectrum m / z: 914.2797 (theoretical value: 914.2789). Theoretical element content (%) C 65 H 42 N2S2: C, 85.31; H, 4.63; N, 3.06. Measured element content (%): C, 85.33; H, 4.65; N, 3.03.

[0210] [Synthesis Example 18] Synthesis of Compound 187

[0211]

[0212] According to the preparation method of Synthesis Example 8, a-66 was replaced by an equal mole of a-187, b-66 was replaced by an equal mole of b-187, c-90 was replaced by an equal mole of a-187, d-90 was replaced by an equal mole of d-187, and m-90 was replaced by an equal mole of m-66 to obtain compound 187 (24.23 g). The solid purity was ≥ 99.96% by HPLC. Mass spectrum m / z: 1136.2918 (theoretical value: 1136.2929). Theoretical element content (%) C 79 H 48 N2OS3: C, 83.42; H, 4.25; N, 2.46. Measured element content (%): C, 83.43; H, 4.23; N, 2.28.

[0213] [Synthesis Example 19] Synthesis of Compound 192

[0214]

[0215] According to the preparation method of Synthesis Example 14, e-143 was replaced by an equal mole of e-192, f-143 was replaced by an equal mole of f-192, b-13 was replaced by an equal mole of b-107, m-13 was replaced by an equal mole of m-90, and n-143 was replaced by an equal mole of n-192 to obtain Compound 192 (25.16 g). The solid purity was ≥ 99.95% by HPLC. Mass spectrum m / z: 1102.3968 (theoretical value: 1102.3957). Theoretical element content (%) C 81 H 54 N2OS: C, 88.17; H, 4.93; N, 2.54. Measured element content (%): C, 88.18; H, 4.95; N, 2.52.

[0216] [Synthesis Example 20] Synthesis of Compound 199

[0217]

[0218] According to the preparation method of Synthesis Example 2, a-13 was replaced by an equal molar amount of a-155, b-13 was replaced by an equal molar amount of b-107, and m-27 was replaced by an equal molar amount of m-199 to obtain compound 199 (24.05 g). The solid purity was ≥ 99.95% by HPLC. Mass spectrum m / z: 1082.3377 (theoretical value: 1082.3365). Theoretical element content (%) C 77 H 50 N2OS2: C, 85.37; H, 4.65; N, 2.59. Measured element content (%): C, 85.38; H, 4.66; N, 2.58.

[0219] [Synthesis Example 21] Synthesis of Compound 219

[0220]

[0221] According to the preparation method of Synthesis Example 2, a-13 was replaced by an equal mole of a-219, b-13 was replaced by an equal mole of b-219, and m-27 was replaced by an equal mole of m-107 to obtain compound 219 (25.21 g). The solid purity was ≥ 99.95% by HPLC. Mass spectrum m / z: 1182.3688 (theoretical value: 1182.3678). Theoretical element content (%) C 85 H 54 N2OS2: C, 86.26; H, 4.60; N, 2.37. Measured element content (%): C, 86.28; H, 4.61; N, 2.33.

[0222] [Synthesis Example 22] Synthesis of Compound 240

[0223]

[0224] According to the preparation method of Synthesis Example 2, a-13 was replaced by an equal molar amount of a-135, b-13 was replaced by an equal molar amount of b-240, and m-27 was replaced by an equal molar amount of m-240 to obtain compound 240 (20.59 g). The solid purity was ≥ 99.96% as determined by HPLC. Mass spectrum m / z: 890.1547 (theoretical value: 890.1554). Theoretical element content (%) C 57 H 34 N2OS4: C, 76.82; H, 3.85; N, 3.14. Measured element content (%): C, 76.85; H, 3.87; N, 3.11.

[0225] [Synthesis Example 23] Synthesis of Compound 247

[0226]

[0227] Preparation of intermediate G-247:

[0228] Under nitrogen protection, a-66 (200.00 mmol, 30.52 g), b-13 (202.00 mmol, 18.81 g) and sodium tert-butoxide (400.00 mmol, 38.44 g) were added to 350 ml of toluene, and Pd(OAc)2 (4.00 mmol, 0.90 g) and P(t-Bu)3 (8.00 mmol, 16.00 ml of 0.5 M toluene solution) were added under stirring, and the mixed solution of the above reactants was heated to reflux for 8 h. After the reaction, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The mixture was allowed to stand for separation, and the organic layer was collected and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure. The mixture was cooled and crystallized, and filtered by suction. The obtained solid was recrystallized from toluene / methanol (volume ratio 10:1) to obtain intermediate G-247 (33.90 g, yield 81%). The solid purity was ≥99.80% by HPLC. Mass spectrum m / z: 209.0855 (theoretical value: 209.0841).

[0229] Preparation of intermediate H-247:

[0230] Under nitrogen protection, h-247 (70.00mmol, 20.20g), G-247 (72.00mmol, 15.07g), Pd(dppf)Cl2 (1.40mmol, 1.02g), Na2CO3 (140.00mmol, 14.84g) and 300mL toluene, 100mL ethanol, 100mL water were stirred, and the above reactant system was heated to reflux for 7h; after the reaction was completed, it was cooled to room temperature, filtered to obtain a filter cake, and the filter cake was washed with ethanol, and finally the filter cake was recrystallized with toluene / ethanol = 10:1 to obtain intermediate H-247 (27.45g, yield 85%); HPLC purity ≥99.69%. Mass spectrum m / z: 461.2172 (theoretical value: 461.2162).

[0231] Preparation of compound 247:

[0232] Under nitrogen protection, M-247 (30.00mmol, 16.80g), H-247 (32.00mmol, 14.76g), Pd(dppf)Cl2 (0.60mmol, 0.44g), Na2CO3 (60.00mmol, 6.36g) and 240mL toluene, 80mL ethanol, 80mL water were stirred, and the above reaction system was heated to reflux for 5h; after the reaction was completed, it was cooled to room temperature, filtered to obtain a filter cake, and the filter cake was rinsed with ethanol, and finally the filter cake was recrystallized with toluene / ethanol = 10:1 to obtain compound 247 (19.84g), and the solid purity was ≥99.98% by HPLC. Mass spectrum m / z: 858.3238 (theoretical value: 858.3246). Theoretical element content (%) C 63 H 42 N2O2: C, 88.09; H, 4.93; N, 3.26. Measured element content (%): C, 88.08; H, 4.95; N, 3.23.

[0233] [Synthesis Example 24] Synthesis of Compound 262

[0234]

[0235] According to the preparation method of Synthesis Example 23, a-66 was replaced by an equal molar amount of a-135, b-13 was replaced by an equal molar amount of b-262, h-247 was replaced by an equal molar amount of h-262, G-247 was replaced by an equal molar amount of n-13, and m-13 was replaced by an equal molar amount of m-46 to obtain compound 262 (20.16 g). The solid purity was ≥ 99.95% by HPLC. Mass spectrum m / z: 932.3218 (theoretical value: 932.3225). Theoretical element content (%) C 69 H44 N2S: C, 88.81; H, 4.75; N, 3.00. Measured element content (%): C, 88.85; H, 4.72; N, 2.98.

[0236] [Synthesis Example 25] Synthesis of Compound 270

[0237]

[0238] Preparation of intermediate A-270:

[0239] Under nitrogen protection, a-270 (120.00 mmol, 27.56 g), b-13 (122.00 mmol, 11.36 g) and sodium tert-butoxide (240.00 mmol, 23.06 g) were added to 300 ml of toluene, and Pd(OAc)2 (2.40 mmol, 0.54 g) and P(t-Bu)3 (4.80 mmol, 9.60 ml of 0.5 M toluene solution) were added under stirring, and the mixed solution of the above reactants was heated to reflux for 7.5 h. After the reaction, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The mixture was allowed to stand for separation, and the organic layer was collected and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure. The temperature was lowered for crystallization, and suction was filtered. The obtained solid was recrystallized from toluene / methanol (volume ratio 10:1) to obtain intermediate A-270 (28.86 g, yield 84%). The solid purity was ≥99.83% by HPLC. Mass spectrum m / z: 249.0798 (theoretical value: 249.0790).

[0240] Preparation of intermediate E-270:

[0241] Under nitrogen protection, e-270 (120.00mmol, 22.97g), f-270 (122.00mmol, 31.86g), Pd(dppf)Cl2 (2.40mmol, 1.76g), Na2CO3 (240.00mmol, 25.44g) and 300mL toluene, 100mL ethanol, 100mL water were stirred, and the above reactant system was heated to reflux for 8h; after the reaction was completed, it was cooled to room temperature, filtered to obtain a filter cake, and the filter cake was washed with ethanol, and finally the filter cake was recrystallized with toluene / ethanol = 10:1 to obtain intermediate E-270 (25.06g, yield 85%); HPLC purity ≥99.79%. Mass spectrum m / z: 245.0055 (theoretical value: 245.0066).

[0242] Preparation of intermediate C-270:

[0243] Under nitrogen protection, E-270 (70.00mmol, 17.20g), b-13 (72.00mmol, 6.71g), sodium tert-butoxide (140.00mmol, 13.45g) were added to 300ml toluene, and Pd(OAc)2 (1.40mmol, 0.31g) and P(t-Bu)3 (2.80mmol, 5.60ml of 0.5M toluene solution) were added under stirring, and the mixed solution of the above reactants was heated to reflux for 7h. After the reaction was completed, it was cooled to room temperature, distilled water was added, extracted with dichloromethane, and the liquid was separated by standing. The organic layer was collected and dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The temperature was lowered for crystallization, and suction was filtered. The obtained solid was recrystallized with toluene / methanol (volume ratio 10:1) to obtain intermediate C-270 (16.72g, yield 79%). The solid purity was ≥99.69% by HPLC. Mass spectrum m / z: 302.0885 (theoretical value: 302.0878).

[0244] Preparation of compound 270:

[0245] According to the preparation method of Synthesis Example 1, n-13 was replaced by an equal mole of A-270, and A-13 was replaced by an equal mole of C-270 to obtain Compound 270 (21.67 g). The solid purity was ≥ 99.97% as determined by HPLC. Mass spectrum m / z: 902.3088 (theoretical value: 902.3079). Theoretical element content (%) C 63 H 42 N4OS: C, 83.79; H, 4.69; N, 6.20. Measured element content (%): C, 83.77; H, 4.68; N, 6.21.

[0246] [Synthesis Example 26] Synthesis of Compound 281

[0247]

[0248] According to the preparation method of Synthesis Example 25, a-270 was replaced with an equal mole of a-281, b-13 was replaced with an equal mole of b-281, e-270 was replaced with an equal mole of e-281, and f-270 was replaced with an equal mole of f-281 to obtain Compound 281 (19.27 g). The solid purity was ≥ 99.98% by HPLC. Mass spectrum m / z: 879.4045 (theoretical value: 879.4034). Theoretical element content (%) C 64 H 33 D 10 N3O: C, 87.34; H, 6.07; N, 4.77. Measured element content (%): C, 87.33; H, 6.08; N, 4.79.

[0249] [Synthesis Example 27] Synthesis of Compound 285

[0250]

[0251] Preparation of intermediate E-285:

[0252] Under nitrogen protection, e-285 (140.00mmol, 34.17g), f-285 (142.00mmol, 25.80g), Pd(dppf)Cl2 (2.80mmol, 2.05g), Na2CO3 (280.00mmol, 29.68g) and 300mL toluene, 100mL ethanol, 100mL water were stirred, and the above reaction system was heated to reflux for 8h; after the reaction was completed, it was cooled to room temperature, filtered to obtain a filter cake, and the filter cake was washed with ethanol, and finally the filter cake was recrystallized with toluene / ethanol = 10:1 to obtain intermediate E-285 (29.49g, yield 80%); HPLC purity ≥99.78%. Mass spectrum m / z: 263.1323 (theoretical value: 263.1310).

[0253] Preparation of compound 285:

[0254] According to the preparation method of Synthesis Example 2, a-13 was replaced by an equal mole of E-285, and b-13 was replaced by an equal mole of b-285 to obtain Compound 285 (27.25 g). The solid purity was ≥ 99.97% as determined by HPLC. Mass spectrum m / z: 1297.5618 (theoretical value: 1297.5627). Theoretical element content (%) C 97 H 72 N2O2: C, 89.78; H, 5.59; N, 2.16. Measured element content (%): C, 89.77; H, 5.60; N, 2.17.

[0255] [Synthesis Example 28] Synthesis of Compound 290

[0256]

[0257] According to the preparation method of Synthesis Example 2, a-13 was replaced by an equal mole of a-290, and b-13 was replaced by an equal mole of b-290 to obtain Compound 290 (25.65 g). The solid purity was ≥ 99.95% as determined by HPLC. Mass spectrum m / z: 1154.5491 (theoretical value: 1154.5499). Theoretical element content (%) C 83 H 70 N4O2: C, 86.28; H, 6.11; N, 4.85. Measured element content (%): C, 86.27; H, 6.10; N, 4.88.

[0258] [Synthesis Example 29] Synthesis of Compound 298

[0259]

[0260] Preparation of intermediate A-66:

[0261] The same preparation method as A-66 in Synthesis Example 8.

[0262] Preparation of intermediate I-298:

[0263] Under nitrogen protection, i-298 (100.00mmol, 24.41g), j-298 (102.00mmol, 13.42g), Pd(dppf)Cl2 (2.00mmol, 1.46g), Na2CO3 (200.00mmol, 21.20g) and 300mL toluene, 100mL ethanol, 100mL water were stirred, and the above reactant system was heated to reflux for 7.5h; after the reaction was completed, it was cooled to room temperature, filtered to obtain a filter cake, and the filter cake was washed with ethanol, and finally the filter cake was recrystallized with toluene / ethanol = 10:1 to obtain intermediate I-298 (17.06g, yield 80%); HPLC purity ≥99.63%. Mass spectrum m / z: 213.1085 (theoretical value: 213.1092).

[0264] Preparation of compound 298:

[0265] According to the preparation method of Synthesis Example 14, e-143 was replaced by an equal mole of e-298, f-143 was replaced by an equal mole of f-298, b-13 was replaced by an equal mole of I-298, m-13 was replaced by an equal mole of m-90, and n-143 was replaced by an equal mole of A-66 to obtain Compound 298 (23.40 g). The solid purity was ≥ 99.96% by HPLC. Mass spectrum m / z: 986.3588 (theoretical value: 986.3596). Theoretical element content (%) C 69 H 34 D8N2O5: C, 83.95; H, 5.10; N, 2.84. Measured element content (%): C, 83.91; H, 5.53; N, 2.83.

[0266] [Synthesis Example 30] Synthesis of Compound 306

[0267]

[0268] Preparation of intermediate J-306:

[0269] Under nitrogen protection, e-298 (130.00mmol, 25.41g), f-192 (132.00mmol, 34.34g), Pd(dppf)Cl2 (2.60mmol, 1.90g), Na2CO3 (260.00mmol, 27.56g) and 300mL toluene, 100mL ethanol, 100mL water were stirred, and the above reactant system was heated to reflux for 8h; after the reaction was completed, it was cooled to room temperature, filtered to obtain a filter cake, and the filter cake was rinsed with ethanol, and finally the filter cake was recrystallized with toluene / ethanol = 10:1 to obtain intermediate J-306 (27.16g, yield 84%); HPLC purity ≥99.82%. Mass spectrum m / z: 248.0355 (theoretical value: 248.0365).

[0270] Preparation of intermediate K-306:

[0271] Under nitrogen protection, f-192 (130.00mmol, 33.82g), j-306 (132.00mmol, 17.37g), Pd(dppf)Cl2 (2.60mmol, 1.90g), Na2CO3 (260.00mmol, 27.56g) and 300mL toluene, 100mL ethanol, 100mL water were stirred, and the above reactant system was heated to reflux for 8h; after the reaction was completed, it was cooled to room temperature, filtered to obtain a filter cake, and the filter cake was washed with ethanol, and finally the filter cake was recrystallized with toluene / ethanol = 10:1 to obtain intermediate K-306 (24.15g, yield 81%); HPLC purity ≥99.79%. Mass spectrum m / z: 229.0851 (theoretical value: 229.0863).

[0272] Synthesis of compound 306:

[0273] According to the preparation method of Synthesis Example 2, a-13 was replaced by an equal molar amount of J-306, b-13 was replaced by an equal molar amount of K-306, and m-27 was replaced by an equal molar amount of m-56 to obtain compound 306 (25.11 g). The solid purity was ≥ 99.96% by HPLC. Mass spectrum m / z: 1194.3852 (theoretical value: 1194.3861). Theoretical element content (%) C 81 H 34 D 16 N2S4: C, 81.37; H, 5.56; N, 2.34. Measured element content (%): C, 81.38; H, 5.55; N, 2.33.

[0274] [Synthesis Example 31] Synthesis of Compound 308

[0275]

[0276] Preparation of intermediate P-308:

[0277] According to the preparation method of K-306 in Synthesis Example 30, f-192 was replaced by an equal molar amount of p-308, and j-306 was replaced by an equal molar amount of q-308 to obtain intermediate P-308 (23.43 g, yield 80%); HPLC purity ≥ 99.89%. Mass spectrum m / z: 225.1528 (theoretical value: 225.1517).

[0278] Preparation of compound 308:

[0279] According to the preparation method of Synthesis Example 2, a-13 was replaced by an equal molar amount of a-135, b-13 was replaced by an equal molar amount of P-308, and m-27 was replaced by an equal molar amount of m-82 to obtain compound 308 (22.54 g). The solid purity was ≥ 99.96% by HPLC. Mass spectrum m / z: 1042.3981 (theoretical value: 1042.3991). Theoretical element content (%) C 73 H 58 N2OS2: C, 84.03; H, 5.60; N, 2.68. Measured element content (%): C, 84.05; H, 5.61; N, 2.66.

[0280] [Synthesis Example 32] Synthesis of Compound 315

[0281]

[0282]

[0283] According to the preparation method of Synthesis Example 25, a-270 was replaced by an equal mole of a-315, b-13 was replaced by an equal mole of b315, e-270 was replaced by an equal mole of e-315, f-270 was replaced by an equal mole of f-315, b-13 was replaced by an equal mole of b-69, and m-13 was replaced by an equal mole of m-90 to obtain compound 315 (23.97 g). The solid purity was ≥99.98% by HPLC. Mass spectrum m / z: 1093.4347 (theoretical value: 1093.4356). Theoretical element content (%) C 78 H 55 N5O2: C, 85.61; H, 5.07; N, 6.40. Measured element content (%): C, 85.62; H, 5.08; N, 6.36.

[0284] Device Embodiment

[0285] The ITO glass substrate was ultrasonically cleaned twice with 5% glass cleaning solution for 200 minutes each time, and then ultrasonically cleaned twice with deionized water for 10 minutes each time. Then, it was ultrasonically cleaned with acetone and isopropyl ketone for 20 minutes, dried at 120°C, and transferred to a vacuum deposition device. The purity of the organic material used was above 99.99%.

[0286] Device Example 1: Preparation of Organic Electroluminescent Device 13

[0287] First, the treated transparent ITO glass substrate is placed on a substrate holder of a vacuum evaporation device, and then hexanitrile hexaazatriphenylene (HAT-CN) is evaporated on the surface of the substrate to form The film with a thickness of The compound 13 of the present invention's synthesis example 1 was used as a hole transport layer; then BH1:BD1=95:5 was evaporated on the hole transport layer as a light-emitting layer with a thickness of The thickness of the evaporation on the light-emitting layer is TPBi is used as a hole blocking layer; on this basis, TmPyPB is evaporated as an electron transport layer with a thickness of The thickness of the evaporated layer on the electron transport layer is Lithium fluoride (LiF) is used as the electron injection layer, and then evaporated to a thickness of of aluminum as cathode.

[0288]

[0289] Device Examples 2-16: Compound 46, Compound 66, Compound 69, Compound 90, Compound 102, Compound 119, Compound 135, Compound 143, Compound 187, Compound 192, Compound 247, Compound 262, Compound 270, Compound 281, and Compound 315 are used respectively to replace Compound 13 in Device Example 1 as a hole transport layer. Except for this, an organic electroluminescent device is prepared using the same synthesis method as Device Example 1.

[0290] Comparative Example 1:

[0291] The organic electroluminescent device was prepared by the same synthesis method as in Device Example 1 except that Comparative Compound 1 was used instead of Compound 13 in Device Example 1 as the hole transport layer.

[0292]

[0293] Table 1: Light-emitting characteristics test of organic electroluminescent devices

[0294]

[0295] Device Example 17: Preparation of Organic Electroluminescent Device 17

[0296] The treated ITO-Ag-ITO glass substrate is placed on a substrate holder of a vacuum evaporation device, and then hexanitrile hexaazatriphenylene (HAT-CN) is evaporated on the surface of the substrate to form The film with a thickness of NPB was used as the hole transport layer; then BH2:BD2=95:5 was evaporated on the hole transport layer as the light-emitting layer with a thickness of The thickness of the evaporation on the light-emitting layer is TPBi is used as the hole blocking layer; on this basis, ET is evaporated as the electron transport layer with a thickness of The thickness of the evaporated layer on the electron transport layer is Lithium fluoride (LiF) is used as the electron injection layer, and then evaporated to a thickness of The magnesium / silver (1:9) was used as the cathode. Finally, the compound 27 of Synthesis Example 2 of the present invention was thermally evaporated on the cathode as a covering layer with a thickness of

[0297]

[0298] Device Examples 18-32: Compound 56, Compound 82, Compound 107, Compound 116, Compound 155, Compound 165, Compound 181, Compound 199, Compound 219, Compound 240, Compound 285, Compound 290, Compound 298, Compound 306, and Compound 308 are used as covering layers to replace Compound 27 in Device Example 17. In addition, the organic electroluminescent device is prepared using the same synthesis method as Device Example 17.

[0299] Comparative Example 2:

[0300] An organic electroluminescent device was prepared by the same synthesis method as in Device Example 17, except that Comparative Compound 2 was used instead of Compound 27 in Device Example 17 as the covering layer.

[0301]

[0302] Table 2: Light-emitting characteristics test of organic electroluminescent devices

[0303]

[0304]

[0305] According to the data in the table, when the amine compounds described in the present invention are used as hole transport materials or covering materials of organic electroluminescent devices, the performance in terms of luminous efficiency, driving voltage, service life, etc. is greatly improved.

[0306] It should be noted that the present invention is particularly described using individual embodiments. However, without departing from the principles of the present invention, a person skilled in the art may make various improvements in form or detail to the present invention, and these improvements also fall within the scope of protection of the present invention.

Claims

1. An amine compound, characterized in that The amine compound is represented by Formula 1: In Formula 1, the L is selected from one of the following structures: The h is independently selected from 0, 1, 2, 3, 4 or 5, and the h is not 0 at the same time; The k is independently selected from 0, 1, 2, 3 or 4, and the k is not 0 at the same time; The m is independently selected from 0, 1, 2 or 3, and the m is not 0 at the same time; Ar1, Ar2, Ar3, Ar4 are substituted or unsubstituted structures represented by Formula 2: The "substituted" in the "substituted or unsubstituted" means that at least one hydrogen is replaced by the following substituents: deuterium, methyl, isopropyl, tert-butyl, cyano, trifluoromethyl, adamantyl, phenyl; Wherein, at least one of Ar1-Ar4 is a structure shown in Formula 2; Said One selected from the following groups: The c is selected from 0 or 1; Said p is independently selected from 0, 1, 2, 3 or 4; The q is independently selected from 0, 1, 2 or 3; The s is independently selected from 0, 1 or 2, and multiple R a Same or different; The R a Independently selected from hydrogen, deuterium, fluorine, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted phenyl; the "substituted" in the "substituted or unsubstituted C1-C6 alkyl" refers to the replacement of at least one hydrogen in the substituent with the following substituents: deuterium, fluorine; the "substituted" in the "substituted or unsubstituted phenyl" refers to the replacement of at least one hydrogen in the substituent with the following substituents: deuterium; The R5 is independently selected from hydrogen, deuterium, fluorine, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted phenyl; the "substituted" in the "substituted or unsubstituted C1-C6 alkyl" means replacing at least one hydrogen in the substituent with the following substituents: deuterium, fluorine; the "substituted" in the "substituted or unsubstituted phenyl" means replacing at least one hydrogen in the substituent with the following substituents: deuterium; The L1-L2 are independently selected from a single bond or one of the following structures: Wherein, the R6 is independently selected from any one of hydrogen and deuterium; The a0 is independently selected from 0, 1, 2, 3 or 4; The b0 is independently selected from 0, 1, 2 or 3; When a0 and b0 are greater than 1, multiple R6 are the same or different; The L3-L6 are independently selected from a single bond or one of the following structures: Wherein, the R6, R 6a Independently selected from any one of hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl; the "substituted" in the "substituted or unsubstituted methyl" and "substituted or unsubstituted ethyl" refers to the substitution of at least one hydrogen in the substituent with the following substituents: deuterium; The a0 is independently selected from 0, 1, 2, 3 or 4; The b0 is independently selected from 0, 1, 2 or 3; The c0 is independently selected from 0, 1 or 2; When a0 and b0 are greater than 1, multiple R6 are the same or different, and multiple R 6a Same or different, and adjacent R 6a They may be bonded to form a substituted or unsubstituted cyclopentane or substituted or unsubstituted cyclohexane ring, and the "substitution" in the "substituted or unsubstituted cyclopentane" or "substituted or unsubstituted cyclohexane ring" refers to replacing at least one hydrogen in the substituent with the following substituent: deuterium.

2. An amine compound according to claim 1, characterized in that: The L is selected from one of the following structures:

3. An amine compound according to claim 1, characterized in that: The L is selected from one of the structures shown below:

4. An amine compound according to claim 1, characterized in that: The formula 2 is selected from one of the following groups: The d is independently selected from 0, 1, 2, 3, 4 or 5; The e is independently selected from 0, 1, 2, 3 or 4.

5. An amine compound according to claim 1, characterized in that: The formula 2 is selected from one of the following groups:

6. An amine compound, characterized in that The amine compound is selected from one of the following compounds:

7. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises one or more of the amine compounds described in any one of claims 1 to 6.

8. The organic electroluminescent device according to claim 7, comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a hole transport region, a light emitting layer, and an electron transport region, wherein: The hole transport region comprises one or more of the amine compounds described in any one of claims 1-6.

9. The organic electroluminescent device according to claim 7, characterized in that: The organic electroluminescent device further comprises a covering layer, which is located on a side of the cathode away from the anode, and the covering layer comprises at least one of the amine compounds described in any one of claims 1 to 6.

Images