CN114133366A - Organic compound and organic electroluminescent element comprising same - Google Patents

Organic compound and organic electroluminescent element comprising same Download PDF

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CN114133366A
CN114133366A CN202111019285.XA CN202111019285A CN114133366A CN 114133366 A CN114133366 A CN 114133366A CN 202111019285 A CN202111019285 A CN 202111019285A CN 114133366 A CN114133366 A CN 114133366A
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substituted
carbon atoms
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李泰烷
俞智雄
都光石
郭兑虎
金相大
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Material Science Co Ltd
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Abstract

The present invention relates to a novel organic compound and an organic light-emitting device including the same, and more particularly, to an organic electroluminescent device having a low driving voltage and remarkably improved luminous efficiency and life.

Description

Organic compound and organic electroluminescent element comprising same
Technical Field
The present invention relates to an organic compound and an organic electroluminescent element including the organic compound.
Background
Organic electroluminescent devices (OLEDs) have a simple structure, various advantages in manufacturing processes, high luminance, excellent viewing angle characteristics, high response speed, and low driving voltage, compared to other flat panel display devices such as conventional Liquid Crystal Displays (LCDs), Plasma Display Panels (PDPs), and Field Emission Displays (FEDs), and are actively developed and commercialized to be used as light sources for flat panel displays such as wall-mounted televisions, backlights for displays, lighting, and advertising boards.
As for the organic electroluminescent element, the original organic EL element was reported by down (c.w.tang) et al of eastman kodak company, (c.w.tang, s.a.vansylke, Applied Physics Letters, vol. 51, page 913, 1987), the light emission principle of which is generally based on that, when a voltage is Applied, holes injected from an anode and electrons injected from a cathode recombine to form excitons, i.e., electron-hole pairs, by transferring the energy of the excitons to a light emitting material to convert into light.
More specifically, the organic electroluminescent element has a structure including a cathode (electron injection electrode) and an anode (hole injection electrode) and one or more organic layers between the two electrodes. At this time, the organic electroluminescent element is stacked in order of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), a light emitting layer (EML), an Electron Transport Layer (ETL), or an Electron Injection Layer (EIL) from the anode, and a hole transport auxiliary layer or a Hole Blocking Layer (HBL) may be further included before and after the light emitting layer, respectively, in order to improve the efficiency of the light emitting layer.
Materials used as an organic layer in an organic electronic element may be classified into a light emitting material and a charge transport material, for example, a hole injection material, a hole transport material, an electron input material, and the like, according to functions.
Lifetime and efficiency are the biggest problems of organic electronic light emitting elements, and as displays become larger, these efficiency and lifetime problems must be solved.
Efficiency, lifetime, driving voltage, and the like are correlated with each other, and when efficiency is improved, driving voltage is relatively lowered, and as driving voltage is lowered, crystallization of organic substances due to Joule heat (Joule heating) generated during driving is reduced, and as a result, lifetime tends to be increased.
However, simply improving the organic layer does not maximize efficiency. This is because both long life and high efficiency can be achieved when the energy levels between the respective organic layers and the T1 value, intrinsic properties of the substance (mobility, interfacial properties, etc.), and the like are optimally combined.
In recent years, in order to solve the problem of light emission in the hole transport layer, an emission assistance layer must be present between the hole transport layer and the light emitting layer, and different emission assistance layers must be developed for each of the light emitting layers (red (R), green (G), and blue (B)).
Generally, electrons (electrons) are transferred from the electron transport layer to the light emitting layer, holes (holes) are transferred from the hole transport layer to the light emitting layer, and excitons (exitons) are generated by recombination (recombination).
However, as for the substance used for the hole transport layer, since it is required to have a low HOMO value, most of them have a low T1 value, and thus excitons (exitons) generated in the light emitting layer are transferred to the hole transport layer, resulting in charge imbalance (charge imbalance) in the light emitting layer, which results in light emission at the hole transport layer interface.
When the hole transport layer interface emits light, there occurs a problem that the color purity and efficiency of the organic electronic element are lowered and the lifetime is shortened. Therefore, an emission assist layer having a high T1 value and having a HOMO level between the HOMO level of the hole transport layer and the HOMO level of the emission layer is urgently required.
Documents of the prior art
Patent document
(non-patent document 1) Krebs, fredrik.c et al (Krebs, Frederik C., et al), "Synthesis, Structure and Properties of a Molecular thermoelectric substance, 4,8,12-Trioxa-12C-phospha-4,8,12,12C-tetrahydrodibenzo [ cd, mn ] pyrene, (Synthesis, Structure, and Properties of 4,8,12-Trioxa-12C-phospha-4,8,12,12C-tetrahydrodibenzo [ cd, mn ] pyrene, a Molecular pyro ctric ], American Chemical Society (Journal of the American Chemical Society), 119.6 (1997): 1208 and 1216.
Disclosure of Invention
Problems to be solved by the invention
An object of the present invention is to provide a novel organic compound and an organic electroluminescent element including the same.
Another object of the present invention is to provide a novel compound which has a HOMO level that facilitates hole transport and has excellent hole transport properties to a light-emitting layer, and which can be used as a hole transport assist layer material for an organic electroluminescent device.
Another object of the present invention is to provide an organic electroluminescent device having a high T1 value and a deep HOMO level and a charge balance (charge balance) between holes and electrons by using a hole transport auxiliary layer containing a novel organic compound, and capable of remarkably improving luminous efficiency and life characteristics by realizing light emission inside a light emitting layer rather than at a hole transport layer interface.
It is another object of the present invention to provide an organic electroluminescent device having a low driving voltage and excellent emission efficiency and External Quantum Efficiency (EQE) characteristics, by including the novel organic compound.
Means for solving the problems
In order to accomplish the above objects of the present invention, there is provided a compound represented by the following chemical formula 1:
[ chemical formula 1]
Figure BDA0003241184090000031
Wherein the content of the first and second substances,
m and n, which are the same or different from each other, are each independently an integer of 0 or 1,
m+n≥0，
o is an integer of 0 to 4,
p is an integer of 0 to 3,
ad is a substituted or unsubstituted adamantyl group,
X1selected from the group consisting of C (R)3)(R4)、N(R5) O, S and Si (R)6)(R7) A group of components selected from the group consisting of,
X2selected from the group consisting of single bond, C (R)8)(R9) A group consisting of O and S,
L1to L3The same or different from each other, each independently selected from the group consisting of a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkenylene group having 3 to 10 carbon atoms, a substituted or unsubstituted heteroalkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 2 to 10 carbon atoms, and a substituted or unsubstituted heterocycloalkenylene group having 2 to 10 carbon atoms,
Ar1and Ar2The same or different from each other, each is independently selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 20 carbon atom1 to 20 heteroalkyl group, a substituted or unsubstituted heterocycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted heteroalkenyl group having 1 to 20 carbon atoms,
R1to R9The same or different from each other, each is independently selected from the group consisting of hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxyl group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, A substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaralmino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and may be bonded to each other with an adjacent group to form a substituted or unsubstituted ring.
Further, the present invention relates to an organic electroluminescence element including: a first electrode; a second electrode; and at least one organic film interposed between the first electrode and the second electrode. In the organic electroluminescent element, the organic film includes a light-emitting layer, and an organic film including a compound represented by the following chemical formula 1 and an organic film including a compound represented by the following chemical formula 6 are included between the first electrode and the light-emitting layer:
[ chemical formula 1]
Figure BDA0003241184090000051
[ chemical formula 6]
Figure BDA0003241184090000052
Wherein the content of the first and second substances,
n、m、Ad、X1、X2、Ar1、Ar2、L1、L2、L3、R1and R2As defined in the above-mentioned context,
w and x are the same as or different from each other and each independently an integer of 0 to 4,
Y1and Y2Are the same or different from each other and are each independently selected from the group consisting of O, S, C (R)21)(R22) And N (R)23) A group of components selected from the group consisting of,
L4to L6The same or different from each other, each independently selected from the group consisting of a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkenylene group having 3 to 10 carbon atoms, a substituted or unsubstituted heteroalkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 2 to 10 carbon atoms, and a substituted or unsubstituted heterocycloalkenylene group having 2 to 10 carbon atoms,
Ar3selected from the group consisting of substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, and substituted or unsubstituted heteroalkyl havingA heterocycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted heteroalkenyl group having 1 to 20 carbon atoms,
R19to R23The same or different from each other, each is independently selected from the group consisting of hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxyl group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, A substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaralmino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and may be bonded to each other with adjacent groups to form a substituted or unsubstituted ring.
In the present invention, unless otherwise specifically limited, "hydrogen" is hydrogen, protium, deuterium, or tritium.
In the present invention, "halo" is fluoro, chloro, bromo or iodo.
In the present invention, "alkyl group" means a monovalent substituent derived from a straight-chain or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, and hexyl.
In the present invention, "alkenyl" means a monovalent substituent derived from a straight-chain or branched unsaturated hydrocarbon having 2 to 40 carbon atoms having one or more carbon-carbon double bonds. Examples thereof include, but are not limited to, vinyl (vinyl), allyl (allyl), isopropenyl (isopropenyl), and 2-butenyl (2-butenyl).
In the present invention, "alkynyl" refers to a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms with one or more carbon-carbon triple bonds. Examples thereof include, but are not limited to, ethynyl (ethyl) and 2-propynyl (2-propyl).
In the present invention, "alkylthio" refers to an alkyl group described above bonded through a sulfur bond (-S-).
In the present invention, "aryl" refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms bonded to a single ring or two or more rings. Also, more than two ring-pendant (pendant) or fused forms may be included. Examples of such aryl groups include, but are not limited to, phenyl, naphthyl, phenanthryl, anthracyl, fluorenyl, and dimethylfluorenyl groups.
In the present invention, "heteroaryl" means a monovalent substituent derived from a mono-or poly-heterocyclic aromatic hydrocarbon having 6 to 30 carbon atoms. In this case, more than one carbon, preferably 1 to 3 carbons, in the ring is substituted with a heteroatom such as N, O, S or Se. Also, more than two rings may be included in a pendant or fused form to each other, and also in a fused form with an aryl group. Examples of such heteroaryl groups include, but are not limited to, 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl and triazinyl, polycyclic rings such as phenylthienyl (phenoxathienyl), indolizinyl (indolizinyl), indolyl (indolinyl), purinyl (purinyl), quinolinyl (quinolyl), benzothiazole (benzothiazolyl) and carbazolyl (carbazolyl), and 2-furyl, N-imidazolyl, 2-isoxazolyl, 2-pyridyl and 2-pyrimidinyl.
In the present invention, the "aryloxy group" is a monovalent substituent represented by RO-, and R mentioned above means an aryl group having 6 to 60 carbon atoms. Examples of such aryloxy groups include, but are not limited to, phenoxy, naphthoxy, and diphenoxy.
In the present invention, the "alkyloxy group" is a monovalent substituent represented by R 'O-, wherein R' is an alkyl group having 1 to 40 carbon atoms and may have a linear (linear), branched (branched) or cyclic (cyclic) structure. Examples of the alkyloxy group include, but are not limited to, methoxy group, ethoxy group, n-propoxy group, 1-propoxy group, t-butoxy group, n-butoxy group, and pentyloxy group.
In the present invention, "alkoxy" may be a straight chain, a branched chain or a cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited, and is preferably 1 to 20. Specifically, there may be mentioned methoxy, ethoxy, n-propoxy, isopropoxy (isopropoxy), isopropoxy (i-propyloxy), n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexoxy, 3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonoxy, n-decoxy, benzyloxy, p-methylbenzyloxy and the like, but not limited thereto.
In the present invention, "aralkyl" refers to aryl groups and alkyl groups are aryl-alkyl groups as described above. Preferred aralkyl groups include lower alkyl groups. Non-limiting examples of preferred aralkyl groups include benzyl, 2-phenylethyl and naphthylmethyl. The bond to the parent residue is through the alkyl group.
In the present invention, "arylamino" refers to an amine substituted with an aryl group having 6 to 30 carbon atoms.
In the present invention, "alkylamino" refers to an amine substituted with an alkyl group having 1 to 30 carbon atoms.
In the present invention, "aralkylamino" refers to an amine substituted with aryl-alkyl having 6 to 30 carbon atoms.
In the present invention, "heteroarylamino group" means an amino group substituted with an aryl group having 6 to 30 carbon atoms and a heterocyclic group.
In the present invention, "heteroaralkyl" refers to an aryl-alkyl group substituted with a heterocyclyl group.
In the present invention, "cycloalkyl" refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of the cycloalkyl group include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl (norbonyl), and adamantane (adamantine).
In the present invention, "heterocycloalkyl" means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 carbon atoms, in which one or more carbons, preferably 1 to 3 carbons, are substituted with a heteroatom such as N, O, S or Se. Examples of such a heterocycloalkyl group include, but are not limited to, morpholine and piperazine.
In the present invention, "alkylsilyl group" means a silyl group substituted with an alkyl group having 1 to 40 carbon atoms, and "arylsilyl group" means a silyl group substituted with an aryl group having 6 to 60 carbon atoms.
In the present invention, "fused ring" means a form of fused aliphatic ring, fused aromatic ring, fused heteroaliphatic ring, fused heteroaromatic ring, or a combination thereof.
In the present invention, "form a ring by bonding to each other with an adjacent group" means that a substituted or unsubstituted aliphatic hydrocarbon ring is formed by bonding to each other with an adjacent group; a substituted or unsubstituted aromatic hydrocarbon ring; a substituted or unsubstituted aliphatic heterocycle; substituted or unsubstituted aromatic heterocycle; or a fused ring thereof.
In the present invention, examples of the "aromatic hydrocarbon ring" include, but are not limited to, phenyl, naphthyl, anthryl and the like.
In the present invention, "aliphatic heterocyclic ring" means an aliphatic ring containing one or more heteroatoms.
In the present invention, "aromatic heterocycle" refers to an aromatic ring containing one or more heteroatoms.
In the present invention, "substituted" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position of the substituted position is not limited as long as the position of the hydrogen atom can be substituted, that is, the position at which the substituent can be substituted, and when two or more are substituted, the two or more substituents are the same as or different from each other. The above substituents may be substituted with one or more substituents selected from the group consisting of hydrogen, cyano, nitro, halogen, hydroxyl, alkyl having 1 to 30 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkynyl having 2 to 24 carbon atoms, heteroalkyl having 2 to 30 carbon atoms, alkyl having 6 to 30 carbon atoms, aryl having 5 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, heteroaralkyl having 3 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, alkylamino having 1 to 30 carbon atoms, arylamino having 6 to 30 carbon atoms, aralkylamino having 6 to 30 carbon atoms and heteroaralmino having 2 to 24 carbon atoms, but are not limited to the above examples.
ADVANTAGEOUS EFFECTS OF INVENTION
The invention has the following effects: the compound of the present invention has an excellent hole transport property to a light emitting layer due to its HOMO level that facilitates hole transport, and in particular, by using a hole transport auxiliary layer comprising a novel organic compound, holes and electrons maintain a charge balance (charge balance) while having a high T1 value and a deep HOMO level, and light emission is achieved inside the light emitting layer instead of at the hole transport layer interface, thereby significantly improving light emission efficiency and life characteristics.
Further, by including a novel compound as a material for the hole transport assist layer and/or the hole transport layer, an organic electroluminescent element having a low driving voltage and excellent emission efficiency, External Quantum Efficiency (EQE), and long-life characteristics can be provided
Detailed Description
Hereinafter, examples of the present invention will be described in detail so that those skilled in the art to which the present invention pertains can easily carry out the present invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described in the present specification.
The compound containing an adamantyl group according to the present invention is characterized by having an adamantyl group and a tri-substituted amine structure in the entire compound structure. The novel organic compound according to the present invention has a hole transporting property, and can exhibit suitably low crystallinity and high heat resistance when used as an organic electroluminescent element material or the like because of containing an adamantyl group.
In the above-mentioned characteristics of the adamantane structure, the molecule is a non-planar structure as compared with a simple molecular structure such as a cycloalkyl group or an aryl group, and in general, a non-planar structure such as an alkyl group having a long chain may cause energy loss due to mobility caused by characteristics such as rotational motion or vibrational motion of the molecule, but on the contrary, even if the adamantane structure has characteristics such that crystallinity is decreased, since the structures form a rigid condensed ring structure with each other, the mobility of the molecule can be decreased, and due to such characteristics, it has high heat resistance and can reduce energy loss due to mobility.
Further, the adamantane structure does not affect the energy level according to delocalization, and the number of carbon atoms is larger than that of phenyl groups, so that the molecular weight is increased, and the melting point or the glass transition temperature is increased, thereby improving the stability of the thin film.
Specifically, the compound represented by the following chemical formula 1 is as follows:
[ chemical formula 1]
Figure BDA0003241184090000101
Wherein the content of the first and second substances,
m and n, which are the same or different from each other, are each independently an integer of 0 or 1,
m+n≥0，
o is an integer of 0 to 4,
p is an integer of 0 to 3,
ad is a substituted or unsubstituted adamantyl group,
X1selected from the group consisting of C (R)3)(R4)、N(R5) O, S and Si (R)6)(R7) A group of components selected from the group consisting of,
X2selected from the group consisting of single bond, C (R)8)(R9) A group consisting of O and S,
L1to L3The same or different from each other, each independently selected from the group consisting of a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, and a substituted or unsubstituted heteroarylene groupA substituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkenylene group having 3 to 10 carbon atoms, a substituted or unsubstituted heteroalkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 2 to 10 carbon atoms, and a substituted or unsubstituted heterocycloalkenylene group having 2 to 10 carbon atoms,
Ar1and Ar2The same or different from each other, each independently selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted heteroalkenyl group having 1 to 20 carbon atoms,
R1to R9The same or different from each other, each is independently selected from the group consisting of hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxyl group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, A substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted carbon atomA heteroarylamino group having a number of 2 to 24, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and may be bonded to each other with adjacent groups to form a substituted or unsubstituted ring.
X is above1May be0 or S, the above X2May be a single bond.
L above1To L3The same or different from each other, and may be each independently selected from the group consisting of a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms.
Ar above1And Ar2The same or different from each other, may be each independently selected from the group consisting of the following chemical formulae 2 to 5:
[ chemical formula 2]
Figure BDA0003241184090000121
[ chemical formula 3]
Figure BDA0003241184090000122
[ chemical formula 4]
Figure BDA0003241184090000123
[ chemical formula 5]
Figure BDA0003241184090000124
Wherein the content of the first and second substances,
the symbol indicates a bonding portion which is,
q and s are the same or different from each other and each independently an integer of 0 to 5,
r is an integer of 0 to 7,
t and v, which are the same or different from each other, are each independently an integer of 0 to 4,
u is an integer of 0 to 3,
X3selected from the group consisting of C (R)16)(R17)、N(R18) A group consisting of O and S,
R10to R18The same or different from each other, each is independently selected from the group consisting of hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxyl group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, A substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaralmino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and may be bonded to each other with an adjacent group to form a substituted or unsubstituted ring.
The compound represented by chemical formula 1 according to the present invention is selected from the group consisting of, but not limited to:
Figure BDA0003241184090000141
Figure BDA0003241184090000151
Figure BDA0003241184090000161
Figure BDA0003241184090000171
Figure BDA0003241184090000181
Figure BDA0003241184090000191
Figure BDA0003241184090000201
Figure BDA0003241184090000211
Figure BDA0003241184090000221
Figure BDA0003241184090000231
Figure BDA0003241184090000241
Figure BDA0003241184090000251
Figure BDA0003241184090000261
Figure BDA0003241184090000271
Figure BDA0003241184090000281
Figure BDA0003241184090000291
Figure BDA0003241184090000301
Figure BDA0003241184090000311
Figure BDA0003241184090000321
Figure BDA0003241184090000331
Figure BDA0003241184090000341
Figure BDA0003241184090000351
Figure BDA0003241184090000361
Figure BDA0003241184090000371
Figure BDA0003241184090000381
Figure BDA0003241184090000391
Figure BDA0003241184090000401
Figure BDA0003241184090000411
Figure BDA0003241184090000421
Figure BDA0003241184090000431
Figure BDA0003241184090000441
Figure BDA0003241184090000451
Figure BDA0003241184090000461
Figure BDA0003241184090000471
Figure BDA0003241184090000481
Figure BDA0003241184090000491
Figure BDA0003241184090000501
Figure BDA0003241184090000511
Figure BDA0003241184090000521
Figure BDA0003241184090000531
Figure BDA0003241184090000541
Figure BDA0003241184090000551
the compound of the present invention represented by the above chemical formula 1 can be effectively used as a hole transport auxiliary layer.
When the compound of the present invention is used as a hole transport assist layer material in an organic electroluminescent element, it contains a substituent that increases the HOMO in the above compound and can be finely adjusted, so that the hole mobility can be adjusted to be optimum according to the electron mobility input to the light-emitting layer.
Due to these characteristics, when the above organic compound is used as a material of an organic electroluminescent element, equivalent or excellent characteristics can be exhibited in most of element characteristics such as luminous efficiency, lifetime, and the like.
The present invention provides an organic electroluminescent device comprising the compound represented by the above chemical formula 1.
The organic compound of the present invention can be effectively used as a material for a hole transport assist layer.
In the organic electroluminescent element according to the present invention, the organic thin film layer is formed by one or more layers including at least a light-emitting layer, and the organic thin film layer is a hole transport layer and a hole transport auxiliary layer between the first electrode and the light-emitting layer.
The hole transport auxiliary layer is a compound represented by the following chemical formula 1, and the hole transport layer may be a compound represented by the following chemical formula 6:
[ chemical formula 1]
Figure BDA0003241184090000552
[ chemical formula 6]
Figure BDA0003241184090000561
Wherein the content of the first and second substances,
n、m、Ad、X1、X2、Ar1、Ar2、L1、L2、L3、R1and R2As defined in the above-mentioned context,
w and x are the same as or different from each other and each independently an integer of 0 to 4,
Y1and Y2Are the same or different from each other and are each independently selected from the group consisting of O, S, C (R)21)(R22) And N (R)23) A group of components selected from the group consisting of,
L4to L6The same or different from each other, each independently selected from the group consisting of a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylene groupA heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkenylene group having 3 to 10 carbon atoms, a substituted or unsubstituted heteroalkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 2 to 10 carbon atoms, and a substituted or unsubstituted heterocycloalkenylene group having 2 to 10 carbon atoms,
Ar3selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted heteroalkenyl group having 1 to 20 carbon atoms,
R19to R23The same or different from each other, each is independently selected from the group consisting of hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxyl group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, A substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted carbon atomIs a group consisting of a heteroarylamino group of 2 to 24, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and may be bonded to each other with adjacent groups to form a substituted or unsubstituted ring.
The compound represented by the above chemical formula 6 may be a compound represented by the following chemical formula 7 or a compound represented by the chemical formula 8:
[ chemical formula 7]
Figure BDA0003241184090000571
[ chemical formula 8]
Figure BDA0003241184090000572
Wherein the content of the first and second substances,
L4、L5、L6、Ar3and Y2As defined in the above chemical formula 6,
a. b, c, d, e and f, which are the same or different from each other, are each independently an integer of 0 to 4,
z is selected from the group consisting of a single bond, C (R)32)(R33)、C-C(R34)(R35) A group consisting of O and S,
R24to R35The same or different from each other, each is independently selected from the group consisting of hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxyl group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaryl group having 6 to 60 carbon atoms30, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and may be bonded to each other with adjacent groups to form a substituted or unsubstituted ring.
The compound represented by the above chemical formula 6 may be selected from the group consisting of:
Figure BDA0003241184090000581
Figure BDA0003241184090000591
Figure BDA0003241184090000601
Figure BDA0003241184090000611
Figure BDA0003241184090000621
Figure BDA0003241184090000631
Figure BDA0003241184090000641
Figure BDA0003241184090000651
the organic electroluminescent element may have a structure in which an anode, a hole injection layer, a hole transport auxiliary layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode are stacked, and an electron transport auxiliary layer may be further stacked as necessary.
The organic electroluminescent element of the present invention will be described below by way of example. However, the contents of the following examples do not limit the organic electroluminescent element of the present invention.
The organic electroluminescent element of the present invention may have a structure in which an anode (hole injection electrode), a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), a hole transport auxiliary layer, an emission layer (EML), and a cathode (electron injection electrode) are sequentially stacked, and preferably, may further include a hole transport auxiliary layer between the anode and the emission layer, and an Electron Transport Layer (ETL), an Electron Injection Layer (EIL) between the cathode and the emission layer. And, an electron transport auxiliary layer may be further included between the cathode and the light emitting layer.
As a method for manufacturing an organic electroluminescent element according to the present invention, an anode is first formed by coating an anode substance on a substrate surface in a conventional manner. In this case, the substrate used is preferably a glass substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling, and water resistance. As the anode material, transparent and highly conductive Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), or tin oxide (SnO) can be used2) Zinc oxide (ZnO), and the like.
Next, a Hole Injection Layer (HIL) material is vacuum-thermally evaporated or spin-coated on the surface of the anode in a conventional manner to form a hole injection layer. Examples of such a hole injection layer material include copper phthalocyanine (CuPc), 4',4 ″ -tris (3-methylphenylamino) triphenylamine (m-MTDATA), 4',4 ″ -tris (3-methylphenylamino) phenoxybenzene (m-MTDAPB), 4',4 ″ -tris (N-carbazolyl) triphenylamine (TCTA) as a starburst (starburst) type amine, 4',4 ″ -tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine (2-TNATA), and IDE406 available from Idemitsu corporation.
The compound represented by the above chemical formula 6 according to the present invention is vacuum-thermally evaporated or spin-coated on the surface of the above hole injection layer in a conventional method to form a hole transport layer.
The compound represented by the above chemical formula 1 according to the present invention is vacuum-thermally evaporated or spin-coated on the surface of the above hole transport layer to form a hole transport auxiliary layer.
The light-emitting layer is formed on the surface of the hole transport auxiliary layer by vacuum thermal evaporation or spin coating of a light-emitting layer (EML) material by a conventional method. In this case, tris (8-hydroxyquinolyl) aluminum (Alq) can be used as a single light-emitting substance or a light-emitting host substance among light-emitting layer substances used in the case of green3) Etc., in the case of blue, Alq may be used34,4' -N, N ' -dicarbazole-biphenyl (4,4' -N, N ' -dicarbazole-biphenol, CBP), poly (N-vinylcarbazole), PVK, 9, 10-bis (naphthalene-2-yl) anthracene (9,10-di (naphthalene-2-yl) anthrylene, ADN), 4' -tris (carbazol-9-yl) triphenylamine (TCTA), 1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene (1,3,5-tris (N-phenylbenzimidazole-2-yl) benzene, TPBI), 3-tert-butyl-9, 10-bis (naphthalene-2-yl) anthracene (3-tert-butyl-butyldi-9, 10-naphthalene-2-yl) anthracene, TBADN), E3, Distyrylarylene (DSA), or a mixture of two or more thereof, but is not limited thereto.
As the Dopant (Dopant) which can be used together with the light-emitting host in the light-emitting layer material, IDE102 and IDE105 which are commercially available from Idemitsu (Idemitsu) can be used, and as the phosphorescent Dopant (Dopant) (here, tris (2-phenylpyridine)) iridium (III) (ir (ppy)3), bis [ (4, 6-difluorophenyl) pyridyl-N, C-2' ] picolinoyl iridium (III) (chirp) (reference [ haya Adachi et al, appl. phys. lett., 2001, 79, 3082-3084]), octaethylporphyrin platinum (II) (PtOEP), TBE002 (cobine corporation) and the like can be used.
An Electron Transport Layer (ETL) material is vacuum-thermally evaporated or spin-coated on the surface of the light-emitting layer by a conventional method to form the ETL. At this time, the electron transport layer material used is not particularly limited, and preferably,tris (8-hydroxyquinoline) aluminum (Alq) can be used3)。
Alternatively, a Hole Blocking Layer (HBL) is further formed between the light emitting layer and the electron transport layer, and a phosphorescent Dopant (Dopant) is used in the light emitting layer, so that a phenomenon in which triplet excitons or holes are diffused into the electron transport layer can be prevented.
The formation of the hole blocking layer can be carried out by vacuum thermal evaporation or spin coating of a hole blocking layer material by a conventional method, and the hole blocking layer material is not particularly limited, but lithium (8-hydroxyquinolyl) lithium (Liq), bis (8-hydroxy-2-methylquinolyl) -diphenoxyaluminum (BAlq), Bathocuproine (BCP), lithium fluoride (LiF), and the like can be preferably used.
An Electron Injection Layer (EIL) material is vacuum-thermally evaporated or spin-coated on the surface of the electron transport layer by a conventional method to form an electron injection layer. In this case, as the electron injection layer material, materials such as LiF, Liq, Li2O, BaO, NaCl, and CsF can be used.
The cathode is formed by vacuum thermal deposition of a cathode material on the surface of the electron injection layer by a conventional method.
In this case, examples of the cathode material to be used include lithium (Li), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium (Mg), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and the like. Also, the front light emitting organic electroluminescent element may use Indium Tin Oxide (ITO) or Indium Zinc Oxide (IZO) to form a transparent cathode capable of transmitting light.
A coating layer (CPL) can be formed on the surface of the cathode using the coating layer-forming composition.
Hereinafter, the synthesis method of the above compound will be described by representative examples. However, the synthetic method of the compound of the present invention is not limited to the following exemplified method, and the compound of the present invention can be prepared by the following exemplified method and methods known in the art.
[ Synthesis examples ]
< Synthesis examples 1-1: synthesis of Compound 337 >
1-A) Synthesis of intermediate 1-A
Figure BDA0003241184090000681
1- (4'-bromo- [1,1' -biphenyl) was added to the round bottom flask under a nitrogen stream]-4-yl) adamantane (1- (4'-bromo- [1,1' -biphenyl)]-4-yl) adamantane, 100.0g, 272.2mmol) [1,1' -biphenyl ]]-4-amine ([1,1' -biphenyl)]-4-amine，50.68g，299.5mmol)、Pd2(dba)3(4.99g, 5.44mmol), t-BuONa (52.33g, 544.5mmol), 50% t-Bu3The reaction was carried out by stirring the P solution (5.12mL, 21.78mmol) and toluene (1500mL) at 100 ℃. After completion of the reaction, methanol was added to precipitate the reaction product, and the resulting solid was filtered and purified by silica gel column chromatography (silica gel column) and recrystallization to prepare 100.5g of compound 1-A (yield: 81%).
1-B) Synthesis of Compound 337
Figure BDA0003241184090000691
To a round-bottomed flask, under a nitrogen stream, were added compound 1-A (10g, 21.95mmol), 3-bromodibenzofuran (3-bromodibenzofuran) (5.97g, 24.14mmol), Pd2(dba)3(0.40g, 0.44mmol), t-BuONa (4.22g, 43.89mmol), 50% t-Bu3The reaction was carried out by stirring the P solution (0.41mL, 1.76mmol) and toluene (150mL) at 100 ℃. After completion of the reaction, methanol was added to precipitate, and the resulting solid was filtered and purified by silica gel column chromatography (silica gel column) and recrystallization to prepare 8.87g of compound 337 (yield: 65%).
< Synthesis examples 1 to 2: synthesis of Compound 340 >
Figure BDA0003241184090000692
8.46g of Compound 340 (yield: 62%) was prepared by synthesis and purification in the same manner as the synthesis of Compound 337, except that 2-bromodibenzofuran (2-bromodibenzofuran) (5.97g, 24.14mmol) was used instead of 3-bromodibenzofuran.
< Synthesis examples 1 to 3: synthesis of Compound 974
Figure BDA0003241184090000701
By synthesizing and purifying in the same manner as the synthesis method of the compound 337 except that 3-bromodibenzothiophene (3-bromodibenzothiophene, 6.35g, 24.14mmol) was used in place of 3-bromodibenzofuran, 9.24g of the compound 974 was prepared (yield: 66%).
< Synthesis examples 1 to 4: synthesis of Compound 977
Figure BDA0003241184090000702
By synthesizing and purifying in the same manner as in the synthesis of the compound 337 except for using 2-bromodibenzothiophene (2-bromodibenzothiophene) (6.35g, 24.14mmol) in place of 3-bromodibenzofuran, 8.40g of the compound 977 was prepared (yield: 60%).
< Synthesis examples 1 to 5: synthesis of Compound 424
5-A) Synthesis of intermediate 5-A
Figure BDA0003241184090000703
To a round bottom flask was added 3-bromodibenzofuran (100g, 404.7mmol) (4-chlorophenyl) boronic acid (75.94g, 485.7mmol), K under a stream of nitrogen2CO3(111.9g，809.4mmol)、Pd(PPh3)4(18.71g, 16.19mmol), toluene (900mL), ethanol (300mL) and water (300mL) and refluxed with stirring. After the reaction was completed, the organic layer was extracted with toluene and water. With MgSO4The extracted organic layer was treated to remove residual water and concentrated under reduced pressure, followed by purification by silica gel column chromatography (silica gel column) and recrystallization to prepare 94.49g of compound 5-A (collected)Rate: 83%).
5-B) Synthesis of Compound 424
Figure BDA0003241184090000711
Under a nitrogen stream, compound 1-A (10g, 21.95mmol), compound 5-A (6.73g, 24.14mmol), Pd were added to a round-bottom flask2(dba)3(0.40g, 0.44mmol), t-BuONa (4.22g, 43.89mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (sphos) (0.36g, 0.88mmol) and toluene (150mL), followed by stirring at 100 ℃ to effect a reaction. After completion of the reaction, methanol was added to precipitate the reaction product, and the resulting solid was filtered and purified by silica gel column chromatography (silica gel column) and recrystallization to obtain 10.42g of compound 424 (yield: 68%).
< Synthesis examples 1 to 6: synthesis of Compound 427 >
6-A) Synthesis of intermediate 6-A
Figure BDA0003241184090000712
By conducting synthesis and purification in the same manner as in the synthesis of the compound 5-A except for using 2-bromodibenzofuran (2-bromodibenzofuran) (100g, 404.7mmol) in place of 3-bromodibenzofuran, 92.22g of the compound 6-A was produced (yield: 81%).
6-B) Synthesis of Compound 427
Figure BDA0003241184090000721
Synthesis and purification were carried out in the same manner as the synthesis of compound 424 except that compound 6-A (6.73g, 24.14mmol) was used instead of compound 5-A, whereby 10.1g of compound 427 was prepared (yield: 66%).
< Synthesis examples 1 to 7: synthesis of Compound 1058
7-A) Synthesis of intermediate 7-A
Figure BDA0003241184090000722
Synthesis and purification were carried out in the same manner as in the synthesis of the compound 5-A except that 3-bromodibenzothiophene (3-bromodibenzothiophene) (100g, 380.0mmol) was used in place of 3-bromodibenzofuran, to give 87.66g of the compound 7-A (yield: 82%).
7-B) Synthesis of Compound 1058
Figure BDA0003241184090000723
Synthesis and purification were carried out in the same manner as the synthesis of compound 424 except that compound 7-A (7.12g, 24.14mmol) was used instead of compound 5-A, to give 9.96g of compound 1058 (yield: 65%).
< Synthesis examples 1 to 8: synthesis of Compound 1061
8-A) Synthesis of intermediate 8-A
Figure BDA0003241184090000731
89.80g of compound 8-A was prepared (yield: 84%) by conducting synthesis and purification in the same manner as the synthesis of compound 5-A except that 2-bromodibenzothiophene (2-bromodibenzothiophene) (100g, 380.0mmol) was used in place of 3-bromodibenzofuran.
8-B) Synthesis of Compound 1061
Figure BDA0003241184090000732
Synthesis and purification were carried out in the same manner as the synthesis of compound 424 except that compound 8-A (7.12g, 24.14mmol) was used instead of compound 5-A, whereby 10.42g of compound 1061 was prepared (yield: 68%).
< Synthesis examples 1 to 9: synthesis of Compound 346 >
9-A) Synthesis of intermediate 9-A
Figure BDA0003241184090000733
Synthesis and purification were carried out in the same manner as the synthetic method of the compound 1-A except that 4- (naphthalen-1-yl) aniline (65.67g, 299.5mmol) was used in place of [1,1' -biphenyl ] -4-amine, to prepare 96.75g of the compound 9-A (yield: 78%).
9-B) Synthesis of Compound 346
Figure BDA0003241184090000741
Synthesis and purification were carried out in the same manner as the synthesis of compound 337 except that compound 9-A (11.1g, 21.95mmol) was used instead of compound 1-A, to give 9.00g of compound 346 (yield: 61%).
< Synthesis examples 1 to 10: synthesis of Compound 983
Figure BDA0003241184090000742
Synthesis and purification were carried out in the same manner as the synthesis of compound 337 except that compound 9-A (11.1g, 21.95mmol) and 3-bromodibenzothiophene (6.35g, 24.14mmol) were used, to give 9.51g of compound 983 (yield: 63%).
< Synthesis examples 1 to 11: synthesis of Compound 436 >
Figure BDA0003241184090000751
Synthesis and purification were carried out in the same manner as the synthesis of the compound 424 except for using the compound 9-A (11.1g, 21.95mmol) and the compound 6-A (6.73g, 24.14mmol), to give 10.84g of the compound 436 (yield: 66%).
< Synthesis examples 1 to 12: synthesis of Compound 1070 >
Figure BDA0003241184090000752
Synthesis and purification were carried out in the same manner as the synthesis of compound 424 except for using compound 9-A (11.1g, 21.95mmol) and compound 8-A (7.12g, 24.14mmol), to give 10.06g of compound 1070 (yield: 60%).
< Synthesis examples 1 to 13: synthesis of Compound 1067
Figure BDA0003241184090000753
Synthesis and purification were carried out in the same manner as the synthesis of the compound 424 except that the compound 9-A (11.1g, 21.95mmol) and the compound 7-A (7.12g, 24.14mmol) were used, to give 10.9g of the compound 1067 (yield: 65%).
< Synthesis examples 1 to 14: synthesis of Compound 355
14-A) Synthesis of intermediate 14-A
Figure BDA0003241184090000761
Synthesis and purification were carried out in the same manner as the synthesis of the compound 1-A except that 4- (naphthalen-2-yl) aniline (65.67g, 299.5mmol) was used in place of [1,1' -biphenyl ] -4-amine, to give 99.24g of the compound 14-A (yield: 80%).
14-B) Synthesis of Compound 355
Figure BDA0003241184090000762
Synthesis and purification were carried out in the same manner as the synthesis of compound 337 except that compound 14-A (11.1g, 21.95mmol) was used instead of compound 1-A, to give 9.88g of compound 355 (yield: 67%).
< Synthesis examples 1 to 15: synthesis of Compound 992
Figure BDA0003241184090000763
Synthesis and purification were carried out in the same manner as the synthesis of compound 337 except that compound 14-A (11.1g, 21.95mmol) and 3-bromodibenzothiophene (6.35g, 24.14mmol) were used, to give 9.21g of compound 992 (yield: 65%).
< Synthesis examples 1 to 16: synthesis of Compound 442
Figure BDA0003241184090000771
Synthesis and purification were carried out in the same manner as the synthesis of compound 424 except that compound 14-A (11.1g, 21.95mmol) and compound 5-A (6.73g, 24.14mmol) were used, to give 11.16g of compound 442 (yield: 68%).
< Synthesis examples 1 to 17: synthesis of Compound 445 >
Figure BDA0003241184090000772
Synthesis and purification were carried out in the same manner as the synthesis of the compound 424 except for using the compound 14-A (11.1g, 21.95mmol) and the compound 6-A (6.73g, 24.14mmol), to prepare 10.18g of a compound 445 (yield: 62%).
< Synthesis examples 1 to 18: synthesis of Compound 1079
Figure BDA0003241184090000781
Synthesis and purification were carried out in the same manner as the synthesis of compound 424 except for using compound 14-A (11.1g, 21.95mmol) and compound 8-A (7.12g, 24.14mmol), to give 10.57g of compound 1079 (yield: 63%).
< Synthesis examples 1 to 19: synthesis of Compound 364 >
19-A) Synthesis of intermediate 19-A
Figure BDA0003241184090000782
Synthesis and purification were carried out in the same manner as the synthetic method of the compound 1-A except that 4- (phenanthren-9-yl) aniline (4- (phenylanthren-9-yl) aniline) (80.66g, 299.5mmol) was used in place of [1,1' -biphenyl ] -4-amine, to prepare 116.5g of the compound 19-A (yield: 77%).
19-B) Synthesis of Compound 364
Figure BDA0003241184090000783
Synthesis and purification were carried out in the same manner as the synthesis of compound 337 except that compound 19-A (12.2g, 21.95mmol) was used instead of compound 1-A, to give 9.51g of compound 364 (yield: 60%).
< Synthesis examples 1 to 20: synthesis of Compound 1001
Figure BDA0003241184090000791
By conducting synthesis and purification in the same manner as in the synthesis of compound 337 except for using 19-A (12.2g, 21.95mmol) and 3-bromodibenzothiophene (6.35g, 24.14mmol), compound 1001 (yield: 61%) was prepared in 9.88 g.
< Synthesis examples 1 to 21: synthesis of Compound 395
21-A) Synthesis of intermediate 21-A
Figure BDA0003241184090000792
122.6g of Compound 21-A (yield: 81%) was prepared by synthesis and purification in the same manner as the synthesis of Compound 1-A except that 9,9-dimethyl-9H-fluoren-2-amine (62.67g, 299.5mmol) was used in place of [1,1' -biphenyl ] -4-amine.
21-B) Synthesis of Compound 395
Figure BDA0003241184090000793
Synthesis and purification were carried out in the same manner as the synthesis of compound 337 except that compound 21-A (11.0g, 22.19mmol) was used instead of compound 1-A, to give 9.69g of compound 395 (yield: 66%).
< Synthesis examples 1 to 22: synthesis of Compound 1029
Figure BDA0003241184090000801
Synthesis and purification were carried out in the same manner as the synthesis of compound 337 except that compound 21-A (11.0g, 22.19mmol) and 3-bromodibenzothiophene (6.42g, 24.41mmol) were used, to give 9.40g of compound 1029 (yield: 64%).
< Synthesis examples 1 to 23: synthesis of Compound 471 >
Figure BDA0003241184090000802
Synthesis and purification were carried out in the same manner as the synthesis of the compound 424 except for the compound 21-A (11.0g, 22.19mmol) and the compound 6-A (6.80g, 24.41mmol), to give 10.97g of a compound 471 (yield: 67%).
< Synthesis examples 1 to 24: synthesis of Compound 1113 >
Figure BDA0003241184090000803
Synthesis and purification were carried out in the same manner as the synthesis of the compound 424 except for the compound 21-A (11.0g, 22.19mmol) and the compound 6-A (7.20g, 24.41mmol), to give 10.04g of the compound 1113 (yield: 60%).
< Synthesis examples 1 to 25: synthesis of Compound 339 >
25-A) Synthesis of intermediate 25-A
Figure BDA0003241184090000811
Synthesis and purification were carried out in the same manner as the synthesis of the compound 1-A except that [1,1' -biphenyl ] -2-amine ([1,1' -biphenyl ] -2-amine) (50.68g, 299.5mmol) was used instead of [1,1' -biphenyl ] -4-amine, to prepare 90.55g of the compound 25-A (yield: 73%).
25-B) Synthesis of Compound 339
Figure BDA0003241184090000812
Synthesis and purification were carried out in the same manner as the synthesis of compound 337 except that compound 25-A (10.0g, 21.95mmol) was used instead of compound 1-A, to give 7.92g of compound 339 (yield: 58%).
Synthesis examples 1 to 26 Synthesis of Compound 1011
26-A) Synthesis of intermediate 26-A
Figure BDA0003241184090000821
Synthesis and purification were carried out in the same manner as the synthesis of the compound 1-A except that [1,1':3',1 "-terphenyl ] -4' -amine ([1,1':3', 1" -terphenyl ] -4' -amine) (73.47g, 299.5mmol) was used instead of [1,1' -biphenyl ] -4-amine, to prepare 108.6g of the compound 26-A (yield: 75%).
26-B) Synthesis of Compound 1011
Figure BDA0003241184090000822
Synthesis and purification were carried out in the same manner as the synthesis of compound 337 except that compound 26-A (11.0g, 20.69mmol) and compound 9-A (5.99g, 22.76mmol) were used, to give 9.01g of compound 1011 (yield: 61%).
Synthesis examples 1 to 27 Synthesis of Compound 748
27-A) Synthesis of intermediate 27-A
Figure BDA0003241184090000823
75.07g of compound 27-A (yield: 72%) was prepared by conducting synthesis and purification in the same manner as the synthesis of compound 1-A except that 1- (4-bromophenyl) adamantane (1- (4-bromophenyl) adamantane) (80.0g, 274.7mmol) was used in place of 1- (4'-bromo- [1,1' -biphenyl ] -4-yl) adamantane.
27-B) Synthesis of Compound 748
Figure BDA0003241184090000831
Synthesis and purification were carried out in the same manner as the synthesis of compound 424 except for using compound 27-A (10.0g, 26.35mmol) and compound 8-A (8.54g, 28.98mmol), to give 9.92g of compound 748 (yield: 59%).
< Synthesis examples 1 to 28: synthesis of Compound 695 >
28-A) Synthesis of intermediate 28-A
Figure BDA0003241184090000832
72.98g of compound 28-A (yield: 70%) was prepared by conducting synthesis and purification in the same manner as the synthesis of compound 1-A except for using 1- (4-bromophenyl) adamantane (80.0g, 274.7mmol) and [1,1':4',1 "-terphenyl ] -4-amine ([1,1':4', 1" -tert-phenyl ] -4-amine) (74.13g, 302.2 mmol).
Synthesis of 28-B) Compound 695
Figure BDA0003241184090000833
Synthesis and purification were carried out in the same manner as the synthesis of compound 337 except that compound 28-A (10.0g, 21.95mmol) and 3-bromodibenzothiophene (6.35g, 24.14mmol) were used, to give 8.96g of compound 695 (yield: 64%).
< Synthesis examples 1 to 29: synthesis of Compound 104
29-A) Synthesis of intermediate 29-A
Figure BDA0003241184090000841
Synthesis and purification were carried out in the same manner as in the synthesis of the compound 5-A except that 4-bromodibenzofuran (100g, 404.7mmol) was used in place of 3-bromodibenzofuran, to obtain 87.99g of the compound 29-A (yield: 78%).
29-B) Synthesis of Compound 104
Figure BDA0003241184090000842
Synthesis and purification were carried out in the same manner as the synthesis of compound 424 except for using compound 28-A (10.0g, 21.95mmol) and compound 29-A (6.73g, 24.14mmol), to give 8.42g of compound 104 (yield: 55%).
< Synthesis examples 1 to 30: synthesis of Compound 867
30-A) Synthesis of intermediate 30-A
Figure BDA0003241184090000843
66.38g of compound 30-A (yield: 75%) was prepared by conducting synthesis and purification in the same manner as the synthesis of compound 1-A except for using 1- (4-bromophenyl) adamantane (60.0g, 206.0mmol) and 4- (naphthalen-2-yl) aniline (4- (naphthalen-2-yl) aniline) (49.70g, 226.6 mmol).
30-B) Synthesis of intermediate 30-B
Figure BDA0003241184090000851
Synthesis and purification were carried out in the same manner as in the synthesis of the compound 5-A except that 2-bromodibenzothiophene (50.0g, 190.0mmol) and (3-chlorophenyl) boronic acid (35.65g, 228.0mmol) were used, to obtain 37.07g of the compound 30-B (yield: 70%).
30-C) Synthesis of Compound 867
Figure BDA0003241184090000852
Synthesis and purification were carried out in the same manner as the synthesis of compound 424 except for compound 30-A (10.0g, 23.28mmol) and compound 30-B (7.55g, 25.60mmol) to give 8.33g of compound 867 (yield: 52%).
< Synthesis examples 1 to 31: synthesis of Compound 385 >
31-A) Synthesis of intermediate 31-A
Figure BDA0003241184090000853
Synthesis and purification were carried out in the same manner as the Synthesis of the Compound 1-A except that dibenzofuran-3-amine (38.4g, 209.6mmol) was used in place of [1,1' -biphenyl ] -4-amine, to give 72.49g of the Compound 31-A (yield: 81%).
31-B) Synthesis of Compound 385
Figure BDA0003241184090000861
Synthesis and purification were carried out in the same manner as the synthesis of compound 337 except that compound 31-A (10.0g, 21.29mmol) was used instead of compound 1-A, to give 8.94g of compound 385 (yield: 66%).
< Synthesis examples 1 to 32: synthesis of Compound 398
Figure BDA0003241184090000862
Synthesis and purification were carried out in the same manner as the synthesis of compound 337 except for using compound 31-A (10.0g, 21.29mmol) and 2-bromo-9-phenyl-9H-carbazole (7.55g, 23.42mmol), to prepare 8.63g of compound 398 (yield: 57%).
< Synthesis examples 1 to 33: synthesis of Compound 476 >
Figure BDA0003241184090000863
Synthesis and purification were carried out in the same manner as the synthesis of the compound 424 except for using the compound 31-A (10.0g, 21.29mmol) and the compound 5-A (6.53g, 23.42mmol), to prepare 9.55g of a compound 476 (yield: 63%).
Synthesis examples 1-34 Synthesis of Compound 485
34-A) Synthesis of intermediate 34-A
Figure BDA0003241184090000871
76.82g of compound 9-A (yield: 83%) was prepared by conducting synthesis and purification in the same manner as in the synthesis of compound 1-A except that dibenzothiophene-3-amine (41.77g, 209.6mmol) was used in place of [1,1' -biphenyl ] -4-amine.
34-B) Synthesis of Compound 485
Figure BDA0003241184090000872
Synthesis and purification were carried out in the same manner as the synthesis of compound 424 except for using compound 34-A (10.0g, 20.59mmol) and compound 5-A (6.31g, 22.65mmol), to give 8.99g of compound 485 (yield: 60%).
Synthesis examples 1 to 35-Synthesis of Compound 1120 >
Figure BDA0003241184090000873
Synthesis and purification were carried out in the same manner as the synthesis of compound 424 except for using compound 34-A (10.0g, 20.59mmol) and compound 8-A (6.67g, 22.65mmol), to give 8.89g of compound 1120 (yield: 58%).
Synthesis examples 1 to 36 Synthesis of Compound 158
36-A) Synthesis of intermediate 36-A
Figure BDA0003241184090000881
60.29g of compound 36-A was prepared by the same synthesis and purification as that of compound 5-A except that 4-bromoaniline (50.0g, 290.6mmol) and dibenzofuran-2-ylboronic acid (73.94g, 348.8mmol) were used (yield: 80%).
36-B) Synthesis of intermediate 36-B
Figure BDA0003241184090000882
72.57g of compound 36-B (yield: 75%) was prepared by conducting synthesis and purification in the same manner as in the synthesis of compound 1-A except that 1- (4-bromophenyl) adamantane (60.0g, 206.0mmol) and compound 36-A (58.77g, 226.6mmol) were used.
36-C) Synthesis of Compound 158
Figure BDA0003241184090000883
Synthesis and purification were carried out in the same manner as the synthesis of compound 337 except for using compound 36-B (10.0g, 21.29mmol) and 3-bromodibenzothiophene (6.16g, 23.42mmol), to give 8.47g of compound 158 (yield: 61%).
< Synthesis examples 1 to 37: synthesis of Compound 159
Figure BDA0003241184090000891
Synthesis and purification were carried out in the same manner as the synthesis of compound 424 except for using compound 36-B (10.0g, 21.29mmol) and compound 5-A (6.53g, 23.42mmol), to give 9.55g of compound 159 (yield: 63%).
< Synthesis examples 1 to 38: synthesis of Compound 167
Figure BDA0003241184090000892
Synthesis and purification were carried out in the same manner as the synthesis of compound 424 except for using compound 36-B (10.0g, 21.29mmol) and compound 7-A (6.91g, 23.42mmol), to give 9.10g of compound 167 (yield: 60%).
< Synthesis examples 1 to 39: synthesis of Compound 189 >
Figure BDA0003241184090000893
Synthesis and purification were carried out in the same manner as the synthesis of compound 337 except for using compound 36-B (10.0g, 21.29mmol) and 2-bromo-9-phenyl-9H-carbazole (7.55g, 23.42mmol), to prepare 8.78g of compound 189 (yield: 58%).
< Synthesis examples 1 to 40: synthesis of Compound 192
40-A) Synthesis of intermediate 40-A
Figure BDA0003241184090000901
52.71g of compound 40-A (yield: 80%) was prepared by synthesis and purification in the same manner as the synthesis of compound 5-A except that 3-bromo-9-phenyl-9H-carbazole (60.0g, 186.2mmol) was used instead of 3-bromo dibenzofuran.
40-B) Synthesis of Compound 192
Figure BDA0003241184090000902
Synthesis and purification were carried out in the same manner as the synthesis of compound 424 except for using compound 36-B (10.0g, 21.29mmol) and compound 40-A (8.29g, 23.42mmol), to give 9.39g of compound 192 (yield: 62%).
< Synthesis example 2-1: preparation of Compound 1-1 >
Figure BDA0003241184090000911
To a 250mL flask was added 2-bromo-9, 9' -spirobifluorene under a stream of nitrogen gas](6.01g, 15.21mmol), N- ([1,1' -Biphenyl)]-4-yl) -9, 9-dimethyl-9H-fluoren-2-amine (5.00g, 13.83mmol), sodium tert-butoxide (3.99g, 41.49mmol), tris (dibenzylideneacetone) dipalladium (0) (0.25g, 0.28mmol), 50% by weight of tri-tert-butylphosphine dissolved in toluene (2.55g, 1.11mmol) and 100mL of toluene are refluxed with stirring. After the reaction was completed, the organic layer was extracted with 100mL of water. With MgSO4The extracted organic layer was treated to remove residual moisture and concentrated under reduced pressure, followed by purification by column chromatography and recrystallization from dichloromethane/heptane to obtain 7.07g of compound 1-1 in a yield of 75.6%.
< Synthesis examples 2-2: preparation of Compound 1-2 >
Figure BDA0003241184090000912
The synthesis and purification were carried out in the same manner as for the preparation of compound 1-1 except that N- ([1,1'-biphenyl ] -2-yl) -9, 9-dimethyl-9H-fluoren-2-amine (5.00g, 13.83mmol) was used instead of N- ([1,1' -biphenyl ] -4-yl) -9, 9-dimethyl-9H-fluoren-2-amine, whereby 6.15g of compound 1-2 was obtained in a yield of 65.8%.
< Synthesis examples 2 to 3: preparation of Compounds 1 to 19 >
Figure BDA0003241184090000913
Synthesis and purification were carried out in the same manner as for the preparation of compound 1-1 except that 2-bromo-9, 9-diphenyl-9H-fluorene (6.05g, 15.21mmol) was used in place of 2-bromo-9, 9' -spirobifluorene, to obtain 6.59g of compounds 1-19 in a yield of 70.3%.
< Synthesis examples 2 to 4: preparation of Compounds 1 to 20 >
Figure BDA0003241184090000921
Synthesis and purification were carried out in the same manner as for the preparation of compound 1-1 except that 2-bromo-9, 9-diphenyl-9H-fluorene (6.05g, 15.21mmol) and N- ([1,1' -biphenyl ] -2-yl) -9, 9-dimethyl-9H-fluoren-2-amine (5.00g, 13.83mmol) were used, to obtain 6.29g of compound 1-20 in a yield of 67.1%.
< Synthesis examples 2 to 5: preparation of Compounds 1 to 110 >
Figure BDA0003241184090000922
Synthesis and purification were carried out in the same manner as for the preparation of compound 1-1 except that 2' -bromo-10, 11-dihydrospiro [ dibenzo [ a, d ] [7] annulene-5, 9' -fluorene ] (6.44g, 15.21mmol) was used in place of 2-bromo-9, 9' -spirobifluorene [ fluorene ], whereby 6.22g of compound 1-110 was obtained in a yield of 63.9%.
< Synthesis examples 2 to 6: preparation of Compounds 1 to 111 >
Figure BDA0003241184090000923
Synthesis and purification were carried out in the same manner as for the preparation of compound 1-1 except that 2' -bromo-10, 11-dihydrospiro [ dibenzo [ a, d ] [7] annulene-5, 9' -fluorene ] (6.44g, 15.21mmol) and N- ([1,1' -biphenyl ] -2-yl) -9, 9-dimethyl-9H-fluoren-2-amine (5.00g, 13.83mmol) were used, to obtain 5.82g of compound 1-111 in a yield of 59.8%.
< Synthesis examples 2 to 7: preparation of Compounds 1 to 37 >
Figure BDA0003241184090000931
Synthesis and purification were carried out in the same manner as for the preparation of compound 1-1 except that 2-bromospiro [ fluorene-9, 9 '-xanthene ] (6.26g, 15.21mmol) was used in place of 2-bromo-9, 9' -spirobifluorene, whereby 6.07g of compound 1-37 was obtained in a yield of 63.4%.
< Synthesis examples 2 to 8: preparation of Compounds 1 to 38
Figure BDA0003241184090000932
Synthesis and purification were carried out in the same manner as for the preparation of compound 1-1 except that 2-bromospiro [ fluorene-9, 9 '-xanthene ] (6.26g, 15.21mmol) and N- ([1,1' -biphenyl ] -2-yl) -9, 9-dimethyl-9H-fluoren-2-amine (5.00g, 13.83mmol) were used to obtain 5.62g of compound 1-38 in a yield of 58.7%.
< Synthesis examples 2 to 9: preparation of Compounds 1 to 74
Figure BDA0003241184090000933
Synthesis and purification were carried out in the same manner as for the preparation of compound 1-1 except that 2' -bromo-10, 10-dimethyl-10H-spiro [ anthracene-9, 9' -fluorene ] (6.65g, 15.21mmol) was used in place of 2-bromo-9, 9' -spirobifluorene, whereby 6.01g of compounds 1-74 were obtained in a yield of 60.5%.
< Synthesis examples 2 to 10: preparation of Compounds 1 to 75 >
Figure BDA0003241184090000941
Synthesis and purification were carried out in the same manner as in the preparation of compound 1-1 except for using 2' -bromo-10, 10-dimethyl-10H-spiro [ anthracene-9, 9' -fluorene ] (6.65g, 15.21mmol) and N- ([1,1' -biphenyl ] -2-yl) -9, 9-dimethyl-9H-fluoren-2-amine (5.00g, 13.83mmol), to obtain 5.69g of compound 1-75 in a yield of 57.3%.
< Synthesis examples 2 to 11: preparation of Compounds 1 to 147 >
Figure BDA0003241184090000942
Synthesis and purification were carried out in the same manner as for the preparation of compound 1-1 except for using 4- ((3r,5r,7r) -adamantan-1-yl) - [1,1':3',1 "-terphenyl ] -4' -amine (5.00g, 13.17mmol) and 2-bromo-9, 9-dimethyl-9H-fluorene (7.92g, 28.98mmol), to obtain 5.60g of compound 1-147 in a yield of 55.7%.
< Synthesis examples 2 to 12: preparation of Compounds 1 to 134 >
Figure BDA0003241184090000943
Synthesis and purification were carried out in the same manner as in the preparation of the compound 1-1 except for using 4'- ((3r,5r,7r) -adamantan-1-yl) -3, 5-diphenyl- [1,1' -biphenyl ] -4-amine (5.00g, 15.08mmol) and 2-bromo-9, 9-diphenyl-9H-fluorene (9.06g, 33.18mmol), to obtain 6.29g of the compound 1-134 in a yield of 58.2%.
< Synthesis examples 2 to 13: preparation of Compounds 1 to 161 >
Figure BDA0003241184090000951
Synthesis and purification were carried out in the same manner as for the preparation of compound 1-1 except that 1,1':3',1 "-terphenyl-4 ' -amine (7.0g, 28.53mmol) and 2-bromo-9, 9-dimethyl-9H-fluorene (18.71g, 68.48mmol) were used, to obtain 9.02g of compound 1-161 in a yield of 50.2%.
< Synthesis examples 2 to 14: preparation of Compounds 1 to 185
Figure BDA0003241184090000952
The synthesis and purification were carried out in the same manner as in the preparation of compound 1-1 except for using 5-naphthalen-1-yl-1, 1' -biphenyl-2-amine (6.0g, 20.31mmol) and 2-bromo-9, 9-dimethyl-9H-fluorene (18.71g, 68.48mmol), to obtain 6.60g of compound 185 in a yield of 47.8%.
< Synthesis examples 2 to 15: preparation of Compounds 1 to 211 >
Figure BDA0003241184090000961
Synthesis and purification were carried out in the same manner as in the preparation of compound 1-1 except that 2' -bromo-2, 7-di-tert-butyl-9, 9' -spirobifluorene (7.72g, 15.21mmol) was used in place of 2-bromo-9, 9' -spirobifluorene, whereby 7.49g of compound 1-211 was obtained in a yield of 68.7%.
< Synthesis examples 2 to 16: preparation of Compounds 1 to 212 >
Figure BDA0003241184090000962
Synthesis and purification were carried out in the same manner as in the preparation of compound 1-1 except for using 2' -bromo-2, 7-di-tert-butyl-9, 9' -spirobifluorene (7.72g, 15.21mmol) and N- ([1,1' -biphenyl ] -2-yl) -9, 9-dimethyl-9H-fluoren-2-amine (5.00g, 13.83mmol), to obtain 7.10g of compound 1-212 in a yield of 65.1%.
< Synthesis examples 2 to 17: preparation of Compounds 1 to 221 >
Figure BDA0003241184090000963
Synthesis and purification were carried out in the same manner as for the preparation of compound 1-1 except that 3- (4-bromophenyl) -9-phenyl-9H-carbazole (6.06g, 15.21mmol) was used instead of 2-bromo-9, 9' -spirobifluorene, and 6.81g of compound 1-221 was obtained in a yield of 72.5%.
< Synthesis examples 2 to 18: preparation of Compounds 1 to 234 >
Figure BDA0003241184090000971
Synthesis and purification were carried out in the same manner as in the preparation of compound 1-1 except for using 2-bromo-9-phenyl-9H-carbazole (4.90g, 15.21mmol) and N,9, 9-triphenyl-9H-fluoren-2-amine (5.66g, 13.83mmol), to obtain 5.84g of compound 1-234 in a yield of 64.9%.
Example 1: organic electroluminescent element production (Green)
Forming an anode on the substrate with the reflective layer using ITO, and using N2Plasma or Ultraviolet (UV) -ozone. HAT-CN was deposited on the substrate as a Hole Injection Layer (HIL) to a thickness of 10 nm. Next, a Hole Transport Layer (HTL) was formed by depositing compound 1-1 of the present invention in a thickness of 110 nm.
A compound 337 is vacuum-deposited on the hole transport layer to a thickness of 85nm to form a hole transport auxiliary layer, and 4,4'-N, N' -dicarbazole-biphenyl (4,4'-N, N' -dicarbazole-biphenyl, CBP) is deposited on the hole transport auxiliary layer to a thickness of 35nm as a light emitting layer (EML), and about 3% or so of bis (1-phenylisoquinoline) (acetylacetone) iridium (III) (bis- (1-phenylisoquinoline) iridium (III) acetate, (piq)2ir (acac)) is doped as a dopant (dopant).
Further, as an Electron Transport Layer (ETL), a layer having a thickness of 30nm was deposited thereon, and a thickness of 1: 1, and LiQ, and depositing LiQ as an Electron Injection Layer (EIL) thereon at a thickness of 1 nm. Subsequently, a film was evaporated at a thickness of 16nm in a ratio of 1: 4 a mixture of magnesium and silver (Ag) was mixed as a cathode, and N4, N4' -bis [4- [ bis (3-methylphenyl) amino group ] was vapor-deposited on the cathode at a thickness of 60nm]Phenyl radical]-N4, N4 '-diphenyl- [1,1' -biphenyl]-4,4' -diamine (DNTPD) as a capping layer. A seal cap (seal cap) containing a moisture absorbent is bonded thereon with an ultraviolet ray curing type adhesive to protect the organic electroluminescent element from O in the atmosphere2Or moisture, thereby producing an organic electroluminescent element.
[ examples 2 to 40]
As shown in table 1 below, organic electroluminescent elements of examples 2 to 40 and organic electroluminescent elements of comparative examples 1 to 4 were manufactured in the same manner as in example 1, except that the hole transport layer compound and the hole transport auxiliary layer compound were used.
Figure BDA0003241184090000981
[ Table 1]
Figure BDA0003241184090000982
Figure BDA0003241184090000991
[ Experimental example 1: analysis of element Properties
In the above, the measurement was made at 10mA/cm for the organic electroluminescent elements manufactured according to the examples and comparative examples2Electro-optical characteristics at the time of current driving and at 20mA/cm2The lifetime was reduced by 95% at the time of constant current driving, and is shown in table 2.
[ Table 2]
Figure BDA0003241184090001001
Figure BDA0003241184090001011
Figure BDA0003241184090001021
From table 2 above, it was confirmed that comparative example 1 is an organic electroluminescent element in which the compound of the present invention is used for a hole transport layer and a hole transport auxiliary layer is not formed, and the organic electroluminescent element of comparative example 2 and comparative example 4 has low efficiency and short lifetime, while the organic electroluminescent element of comparative example 2 and comparative example 4 has high driving voltage and short lifetime. Comparative example 3, which contains the compound of the present invention as a hole transport auxiliary layer, shows characteristics of low efficiency and short lifetime, although the compound of the comparative example is used in the hole transport layer, and the driving voltage is at the same level as that of the examples of the present invention.
On the contrary, it was confirmed that the organic electroluminescent elements of the examples exhibited low driving voltage, high efficiency, excellent color purity, and long life.
Example 41: organic electroluminescent element production (Red)
Forming an anode on the substrate on which the reflective layer is formed using ITO, and using N2Plasma or ultraviolet-ozone is subjected to surface treatment. HAT-CN was deposited on the substrate as a Hole Injection Layer (HIL) to a thickness of 10 nm. Next, a Hole Transport Layer (HTL) was formed by depositing compound 1-1 in a thickness of 110 nm.
The compound 337 of the present invention was vacuum-deposited on the hole transport layer to a thickness of 40nm to form a hole transport auxiliary layer, and 4,4'-N, N' -dicarbazole-biphenyl (4,4'-N, N' -dicarbazole-biphenol, CBP) was deposited on the hole transport auxiliary layer to a thickness of 35nm to form an emission layer (EML), and about 5% or so of tris (2-phenylpyridine) -iridium (III) (tris (2-phenylpyridine) -iridium, ir (ppy)3) was doped as a dopant (dopant).
As an Electron Transport Layer (ETL), a layer of 1: 1, and LiQ, and depositing LiQ as an Electron Injection Layer (EIL) thereon at a thickness of 1 nm. Subsequently, a film was evaporated at a thickness of 16nm in a ratio of 1: 4 a mixture of magnesium and silver (Ag) was mixed as a cathode, and N4, N4' -bis [4- [ bis (3-methylphenyl) amino group ] was vapor-deposited on the cathode at a thickness of 60nm]Phenyl radical]-N4, N4 '-diphenyl- [1,1' -biphenyl]-4,4' -diamine (DNTPD) as a capping layer. A seal cap (seal cap) containing a moisture absorbent is bonded thereon with an ultraviolet ray curing type adhesive to protect the organic electroluminescent element from O in the atmosphere2Or moisture, thereby producing an organic electroluminescent element.
[ examples 42 to 54]
As shown in table 3 below, organic electroluminescent elements of examples 42 to 54 and organic electroluminescent elements of comparative examples 5 to 8 were produced in the same manner as in example 41, except that the hole transport layer compound and the hole transport auxiliary layer compound were used.
[ Table 3]
Figure BDA0003241184090001031
[ Experimental example 2: analysis of element Properties
In the above, for the organic electroluminescent elements manufactured according to examples 41 to 54 and comparative examples 5 to 8, the measurement was performed at 10mA/cm2Electro-optical characteristics at the time of current driving and at 20mA/cm2The lifetime was reduced by 95% at the time of constant current driving, and is shown in table 4.
[ Table 4]
Figure BDA0003241184090001041
While comparative example 5, which is an organic electroluminescent element using the compound of the present invention for the hole transport layer and not forming the hole transport auxiliary layer, was confirmed to have a high driving voltage, a low efficiency and a short lifetime, comparative example 6 showed a high driving voltage, a low efficiency and a short lifetime, and comparative examples 7 and 8 showed a low efficiency and a short lifetime, although the driving voltages were at the same level.
In contrast, it was confirmed that the organic electroluminescent element according to the example of the present invention exhibited low driving voltage, high efficiency, excellent color purity, and long life.
Although the preferred embodiments of the present invention have been described in detail, the scope of the invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention defined in the scope of the claims are also included in the scope of the invention.

Claims (10)

1. A compound represented by the following chemical formula 1, wherein,
[ chemical formula 1]
Figure FDA0003241184080000011
Wherein the content of the first and second substances,
m and n, which are the same or different from each other, are each independently an integer of 0 or 1,
m+n≥0，
o is an integer of 0 to 4,
p is an integer of 0 to 3,
ad is a substituted or unsubstituted adamantyl group,
X1selected from the group consisting of C (R)3)(R4)、N(R5) O, S and Si (R)6)(R7) A group of components selected from the group consisting of,
X2selected from the group consisting of single bond, C (R)8)(R9) A group consisting of O and S,
L1to L3The same or different from each other, each independently selected from the group consisting of a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroarylene group,A substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkenylene group having 3 to 10 carbon atoms, a substituted or unsubstituted heteroalkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 2 to 10 carbon atoms, and a substituted or unsubstituted heterocycloalkenylene group having 2 to 10 carbon atoms,
Ar1and Ar2The same or different from each other, each independently selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted heteroalkenyl group having 1 to 20 carbon atoms,
R1to R9The same or different from each other, each is independently selected from the group consisting of hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxyl group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, A substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaralmino group having 2 to 24 carbon atoms, a substituted or unsubstitutedAn alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and can be bonded to each other with adjacent groups to form a substituted or unsubstituted ring.
2. The compound of claim 1, wherein,
said X1Is 0 or S.
3. The compound of claim 1, wherein,
said X2Is a single bond.
4. The compound of claim 1, wherein,
said L1To L3The same or different from each other, and each is independently selected from the group consisting of a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms.
5. The compound of claim 1, wherein,
ar is1And Ar2The same or different from each other, each independently selected from the group consisting of the following chemical formulas 2 to 5, wherein:
[ chemical formula 2]
Figure FDA0003241184080000031
[ chemical formula 3]
Figure FDA0003241184080000032
[ chemical formula 4]
Figure FDA0003241184080000033
[ chemical formula 5]
Figure FDA0003241184080000034
Wherein the content of the first and second substances,
the symbol indicates the part of the bond,
q and s are the same or different from each other and each independently an integer of 0 to 5,
r is an integer of 0 to 7,
t and v, which are the same or different from each other, are each independently an integer of 0 to 4,
u is an integer of 0 to 3,
X3selected from the group consisting of C (R)16)(R17)、N(R18) A group consisting of O and S,
R10to R18The same or different from each other, each is independently selected from the group consisting of hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxyl group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, A substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaralmino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and may be adjacent to each otherThe groups are bonded to each other to form a substituted or unsubstituted ring.
6. An organic electroluminescent element, wherein,
the method comprises the following steps:
a first electrode for forming a first electrode layer on a substrate,
a second electrode, and
at least one or more organic films between the first electrode and the second electrode;
wherein the organic film includes a light emitting layer,
an organic film including a compound represented by the following chemical formula 1 and an organic film including a compound represented by the following chemical formula 6 are included between the first electrode and the light emitting layer,
[ chemical formula 1]
Figure FDA0003241184080000041
[ chemical formula 6]
Figure FDA0003241184080000042
Wherein the content of the first and second substances,
n、m、Ad、X1、X2、Ar1、Ar2、L1、L2、L3、R1and R2As defined in claim 1, in the same way,
w and x are the same as or different from each other and each independently an integer of 0 to 4,
Y1and Y2Are the same or different from each other and are each independently selected from the group consisting of O, S, C (R)21)(R22) And N (R)23) A group of components selected from the group consisting of,
L4to L6The same or different from each other, each independently selected from the group consisting of a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms10 alkylene group, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkenylene group having 3 to 10 carbon atoms, a substituted or unsubstituted heteroalkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 2 to 10 carbon atoms, and a substituted or unsubstituted heterocycloalkenylene group having 2 to 10 carbon atoms,
Ar3selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted heteroalkenyl group having 1 to 20 carbon atoms,
R19to R23The same or different from each other, each is independently selected from the group consisting of hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxyl group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, A substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaralmino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilane having 1 to 30 carbon atomsA group consisting of a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and can be bonded to each other with adjacent groups to form a substituted or unsubstituted ring.
7. The organic electroluminescent element according to claim 6, wherein,
the compound represented by chemical formula 6 is a compound represented by chemical formula 7 below or a compound represented by chemical formula 8,
[ chemical formula 7]
Figure FDA0003241184080000061
[ chemical formula 8]
Figure FDA0003241184080000062
Wherein the content of the first and second substances,
L4、L5、L6、Ar3and Y2As defined in claim 6, in the same way,
a. b, c, d, e and f, which are the same or different from each other, are each independently an integer of 0 to 4,
z is selected from the group consisting of a single bond, C (R)32)(R33)、C-C(R34)(R35) A group consisting of O and S,
R24to R35The same or different from each other, each is independently selected from the group consisting of hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxyl group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted alkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 2 to 4 carbon atoms, a substituted or unsubstituted aryl group having a substituted or unsubstituted aryl groupA heteroaryl group having 5 to 60 atoms, a substituted or unsubstituted heteroaralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaralmino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and may be bonded to each other with adjacent groups to form a substituted or unsubstituted ring.
8. The organic electroluminescent element according to claim 6, wherein,
the organic film including the compound represented by the chemical formula 1 is a hole transport auxiliary layer.
9. The organic electroluminescent element according to claim 6, wherein,
the organic film including the compound represented by chemical formula 6 is a hole transport layer.
10. The organic electroluminescent element according to claim 6, wherein,
the organic film includes at least one layer selected from the group consisting of a hole injection layer, a hole transport auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer.
CN202111019285.XA 2020-09-03 2021-09-01 Organic compound and organic electroluminescent element comprising same Pending CN114133366A (en)

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