JP7351713B2 - 2-substituted fluorene compound, hole transport material containing the compound, and organic electronic device containing the compound in the hole transport layer - Google Patents

Description

The present invention relates to the provision of a novel compound, the use of the compound as a hole transport material or a material for an organic electronic device, and the provision of an organic electronic device using the compound.

BACKGROUND ART Organic electronic devices that mutually convert electrical energy and light energy include organic electroluminescent elements (organic EL elements) or organic photoelectric conversion elements.

Among these, organic EL elements have a structure in which a luminescent material that emits light by an electric field is sandwiched between a cathode and an anode. An organic EL element is an element that causes a light emitting material to emit light by recombining holes and electrons injected from an electrode within a light emitting layer.

Organic EL elements are self-luminous, have a wide viewing angle, and have excellent visibility. For this reason, organic EL elements are used as display elements such as displays. Further, organic EL elements are thin solid elements, can be lightweight, and have excellent strength. Therefore, displays using organic EL elements are useful not only for stationary displays such as televisions, but also for mobile applications. Furthermore, a display element using an organic EL element can be easily changed in size and emits light from its entire surface, so it is also useful for illumination purposes.

Challenges for organic EL devices include improving luminous efficiency (external quantum efficiency) and extending their lifetime. Various efforts have been made to solve the above problems.
For example, organic EL devices are often provided with a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer in addition to an electrode and a light emitting layer. Usually, these layers are laminated in the following order: an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode. By providing these layers in addition to the electrode and the light-emitting layer, it is possible to increase the probability that holes and electrons recombine within the light-emitting layer, and it is possible to improve the light-emitting efficiency of the organic EL element.

The light-emitting layer of an organic EL device is generally produced by doping a charge-transporting compound called a host material with a fluorescent compound or phosphorescent compound called a guest material. The holes and electrons injected from the electrode recombine in the light-emitting layer formed by the host material and the guest material, and the energy of the excited host material is transferred to the guest material, and the guest material is excited by that energy. Efficient light emission can be obtained by being released as light energy.

In order to improve the recombination probability of holes and electrons, it is important to efficiently transfer both charges to the light emitting layer, so it is necessary to adjust the transport balance of holes and electrons.
To adjust the transport balance of holes and electrons, the hole mobility of the hole injection material and hole transport material, the electron mobility of the electron injection material and electron transport material, the charge injection barrier at the layer interface, and the The balance must be adjusted after considering many factors, such as the thickness of each film.
However, the hole and electron transport properties of the materials themselves vary depending on the material, and a charge injection barrier occurs at the interface between layers made of different materials, so holes and electrons are recombined in a well-balanced manner within the light-emitting layer. It is not easy to do so. Examples of poor balance between charge injection and transport include a case where either holes or electrons are small, or an extremely large number of either hole or electron passes through without recombining. If the charges flow out to the opposite electrode, there is a method to improve recombination efficiency by providing a charge blocking layer to confine the charges within the light emitting layer. Furthermore, high luminous efficiency can be obtained due to the effect of confining the excitation energy generated within the luminescent layer. Normally, the hole transport layer and the electron transport layer often play the role of confining outflowing charges and excitation energy within the light emitting layer, so the role played by the hole transport material is very important.

The properties required for hole transport materials used to increase the recombination efficiency of organic EL devices include high hole transport properties and low electron transport properties, as well as band gap, ionization potential (IP), and electron affinity. It is important that the value of (Ea) has an appropriate value. The ionization potential of the hole transport material is preferably a value between the work function of the anode or the ionization potential of the hole injection material and the ionization potential of the light emitting material, thereby reducing the hole injection barrier to the light emitting layer. can. It is desirable that the electron affinity of the hole transporting material be greater than that of the light emitting material, so that an electron blocking effect can be obtained. It should be noted that the HOMO level is used, which is almost synonymous with ionization potential (IP), which is one of the indicators of charge injection characteristics, and the LUMO level is sometimes used, which is almost synonymous with electron affinity (Ea).

Regarding the lifespan of an organic EL element, the photostability and electrical stability of the material are important (see, for example, Non-Patent Document 1 and Non-Patent Document 2). If the material has low photostability, the excitation energy within the light emitting layer will degrade the material. In addition, if the excitation energy of the hole transport layer is lower than the excitation energy of the light emitting layer, the excitation energy generated in the light emitting layer will move to the hole transport layer, promoting deterioration of the hole transport material and reducing the efficiency of the device. Therefore, it is desirable that the excitation energy of the hole transport layer is higher than the excitation energy of the light emitting layer. On the other hand, materials with low electrical stability deteriorate due to holes and electrons, resulting in low efficiency and short life.

Heat resistance and amorphous property are also important for extending the life of the device. If a material has low heat resistance, thermal decomposition occurs due to the heat generated when the element is driven, and the material deteriorates. Materials with low amorphous properties tend to crystallize, resulting in device deterioration. Therefore, the material used for the element is required to have high heat resistance and good amorphous properties.
Glass transition temperature (Tg) is used as a measure of amorphousness, and if the Tg of a material is low, it will crystallize and turn into an uneven film even under room temperature conditions over a long period of time, so organic EL materials It is said that the higher the Tg, the better. Considering the environment in which the device is used, it is preferable that Tg is at least 135° C. or higher.

A similar problem may also occur in organic photoelectric conversion elements.

For example, Patent Document 1 formally describes a compound (1) represented by the following formula as a hole transport material used in a hole transport layer. However, Patent Document 1 does not show any production example of compound (1), and there is no description or suggestion regarding the excellent effects exhibited by the compound.

Further, Patent Document 2 reports a compound (2) represented by the following formula as a hole transport material used in a hole transport layer. Compound (2) has a 3-phenylfluorene skeleton with a shorter conjugated system than the 2-phenylfluorene skeleton of the corresponding compound of the present invention, and therefore has low electrical stability and thermal stability. It is possible that On the other hand, it is impossible to obtain the compound containing the 2-substituted fluorene skeleton of the present invention using the synthetic method described in Patent Document 2, and there is no clue to predict the excellent effects of the compound.

International Publication No. 2018/074881 Korean Publication Patent No. 10-2017-0092097

Adv. Mater. , 24, 3212 (2012) Adv. Mater. , 22, 2468 (2010)

An object of the present invention is to provide a compound that can be used as a hole transport material that has excellent hole injection or transport performance, electron blocking performance, photostability, electrical stability, and thermal stability.
The present invention also provides a hole transport material containing the above compound, and an organic electronic device including an organic EL element or an organic photoelectric conversion element having a hole transport layer containing the above compound. An object of the present invention is to provide an organic electronic device including an organic EL element having a long life and high luminous efficiency.

As a result of various studies, the inventors succeeded in synthesizing a new compound represented by the general formula (1-1) shown below. The present invention was completed based on the discovery that the material is extremely useful as a hole transport material for devices, and in particular can achieve high efficiency, long life, and low voltage driving of organic EL devices.

The inventors have achieved higher efficiency and longer life of organic EL elements or organic photoelectric conversion elements included in organic electronic devices by using a compound represented by the following general formula (1-1) as a hole transport layer material. The reason why this is possible is estimated as shown below.
That is, the compound represented by the following general formula (1-1) contains a 2-substituted fluorene skeleton defined in the general formula, so that the material has a bulky and rigid structure, and stacking of molecules is suppressed. . It is presumed that the compound exhibits high excitation energy, thereby suppressing energy transfer from the light-emitting layer, thereby increasing the efficiency of the device. In addition, increasing the rigidity of the compound increases electrical stability, photostability, and thermal stability, contributing to longer lifespans of organic EL elements or organic photoelectric conversion elements included in organic electronic devices. It is estimated to be.

The gist of the present invention is as follows.
[1] General formula (1-1)

During the ceremony,
R ₁ to R ₆ are each independently hydrogen, deuterium, a halogen group, a linear, branched or cyclic alkyl group which may have a substituent, or a substituent a straight-chain, branched-chain or cyclic alkoxy group which may _be conjugated with _each other to form a ring;
Ara each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. is a fused polycyclic aromatic group,
Arb is an aromatic hydrocarbon group that may have a substituent, an aromatic heterocyclic group that may have a substituent, or a fused polycyclic aromatic group that may have a substituent. can be,
Arc each independently represents a linear, branched, or cyclic alkyl group that may have a substituent; a linear, branched, or cyclic alkyl group that may have a substituent; Cyclic alkoxy group, aromatic hydrocarbon group that may have a substituent, aromatic heterocyclic group that may have a substituent, or fused polycyclic aromatic group that may have a substituent is a group group, where two Arcs may be bonded to each other via a single bond, a methylene group which may have a substituent, an oxygen atom or a sulfur atom to form a ring.
A compound represented by

[2] The compound according to [1] above, wherein Arb is a phenyl group which may have a substituent.
[3] Two Arcs each independently represent a methyl group that may have a substituent, a phenyl group that may have a substituent, or a naphthyl group that may have a substituent. The group according to [1] or [2], wherein the two phenyl groups or naphthyl groups may be bonded via a single bond to form a ring. Compound.
[4] A hole transport material containing the compound according to any one of [1] to [3] above.

[5] An organic electronic device comprising an organic electroluminescent element or an organic photoelectric conversion element provided with a hole transport layer between a cathode and an anode,
An organic electronic device characterized in that the hole transport layer contains the compound described in any one of [1] to [3] above.

[6] The organic electronic device according to [5] above, comprising an organic electroluminescent element having a light emitting layer between the hole transport layer and the cathode.
[7] The light-emitting layer includes a host material and a guest material made of a light-emitting material,
The organic electronic device according to [6] above, wherein the host material is an electron transporting material or a dual charge transporting material having hole transporting properties and electron transporting properties.

The compound of the present invention can be used as a hole-transporting material that provides a hole-transporting layer with excellent photostability, electrical stability, and thermal stability.
In particular, an organic electronic device including an organic EL element equipped with a hole transport layer containing the compound of the present invention has a long life, high luminous efficiency, and can be driven at low voltage.

FIG. 1 is a schematic cross-sectional view for explaining an example of an organic EL element included in the organic electronic device of the present invention.

The present invention will be explained in more detail below.
The present invention provides general formula (1-1)

During the ceremony,
R ₁ to R ₆ are each independently hydrogen, deuterium, a halogen group, a linear, branched or cyclic alkyl group which may have a substituent, or a substituent a straight-chain, branched-chain or cyclic alkoxy group which may _be conjugated with _each other to form a ring;
Ara each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. is a fused polycyclic aromatic group,
Arb is an aromatic hydrocarbon group that may have a substituent, an aromatic heterocyclic group that may have a substituent, or a fused polycyclic aromatic group that may have a substituent. can be,
Arc each independently represents a linear, branched, or cyclic alkyl group that may have a substituent; a linear, branched, or cyclic alkyl group that may have a substituent; Cyclic alkoxy group, aromatic hydrocarbon group that may have a substituent, aromatic heterocyclic group that may have a substituent, or fused polycyclic aromatic group that may have a substituent is a group group, where two Arcs may be bonded to each other via a single bond, a methylene group which may have a substituent, an oxygen atom or a sulfur atom to form a ring.
Regarding the compound represented by.

Examples of the linear alkyl group in R ₁ to R ₆ and Arc in general formula (1-1) include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group.
Examples of the branched alkyl group in R ₁ to R ₆ and Arc in general formula (1-1) include 1-methylethyl group, 1-methylpropyl group, 1-ethylpropyl group, 1-n -Propylpropyl group, 1-methylbutyl group, 1-ethylbutyl group, 1-propylbutyl group, 1-n-butylbutyl group, 1-methylpentyl group, 1-ethylpentyl group, 1-n-propylpentyl group, 1- n-pentylpentyl group, 1-methylhexyl group, 1-ethylhexyl group, 1-n-propylhexyl group, 1-n-butylhexyl group, 1-n-pentylhexyl group, 1-n-hexylhexyl group, 1 -methylheptyl group, 1-ethylheptyl group, 1-n-propylheptyl group, 1-n-butylheptyl group, and 1-n-pentylheptyl group.

Examples of the cyclic alkyl group in R ₁ to R ₆ and Arc in general formula (1-1) include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group. group, or polycyclic alkyl groups such as a bicycloalkyl group and a tricycloalkyl group.
Examples of the linear, branched or cyclic alkoxy group in R ₁ to R ₆ and Arc in general formula (1-1) include the above-mentioned linear, branched or cyclic alkyl groups. An example is an alkoxy group in which an oxygen atom is located at the 1-position.
The linear, branched or cyclic alkyl group or alkoxy group preferably has 1 to 25 carbon atoms, more preferably 1 to 15 carbon atoms, from the viewpoint of glass transition temperature and steric hindrance. More preferably, it has 1 to 8 carbon atoms.
The ring formed by two adjacent ones of R ₁ to R ₄ in general formula (1-1) bonding to each other is, for example, a ring formed by bonding two adjacent ones to each other and having a substituent. Examples include rings formed by a propylene group, a butylene group, a pentylene group, or a hexylene group.

A linear, branched or cyclic alkyl group, or a linear, branched or cyclic alkyl group or alkoxy group in R ₁ to R ₆ and Arc in general formula (1-1) is Examples of the substituents that may be present include an alkoxy group and a halogen group.
Two or more of the above-mentioned substituents may be present, and when there are two or more, each substituent may be different.

R ₁ to R ₆ are determined by comprehensively considering the electrical stability, thermal stability, film formability, and ease of synthesis and purification of the compound represented by the general formula (1-1). , each independently of the other, are most preferably hydrogen or a methyl group.

Examples of the aromatic hydrocarbon group, aromatic heterocyclic group, and fused polycyclic aromatic group in Ara and Arc in general formula (1-1) include phenyl group, biphenyl group, terphenyl group, naphthyl group, anthracenyl group. group, phenanthrenyl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, pyridyl group, pyrimidyl group, triazinyl group, furyl group, pyrrolyl group, thienyl group, quinolyl group, isoquinolyl group, benzofuranyl group group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalinyl group, benzimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, naphthyldinyl group, phenanthrolinyl group, acridinyl group , and carbolinyl group. The aromatic hydrocarbon group, aromatic heterocyclic group, and fused polycyclic aromatic group in Ara and Arc preferably have a total of 6 to 25 carbon atoms and heteroatoms forming a ring, and preferably 6 to 20 carbon atoms in total. More preferably, those with a number of 6 to 18 are even more preferred.
Here, the two Arcs may be bonded to each other to form a ring via a single bond, a methylene group that may have a substituent, an oxygen atom, or a sulfur atom.
Among these, two Arcs may each independently have a methyl group that may have a substituent, a phenyl group that may have a substituent, or a substituent. It is preferably selected from naphthyl groups, where the two phenyl groups or naphthyl groups may be bonded via a single bond to form a ring.
Examples of rings formed by two Arcs bonding to each other include a cyclopentane ring, a cyclohexane ring, an adamantane ring, and a fluorene ring that form a spiro bond with the five-membered ring in the fluorene skeleton of general formula (1-1). Can be mentioned.

Examples of the aromatic hydrocarbon group, aromatic heterocyclic group, and fused polycyclic aromatic group in Arb in general formula (1-1) include phenyl group, biphenyl group, terphenyl group, naphthyl group, anthracenyl group, Phenanthrenyl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, pyridyl group, pyrimidyl group, triazinyl group, furyl group, pyrrolyl group, thienyl group, quinolyl group, isoquinolyl group, benzofuranyl group, Benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalinyl group, benzimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, naphthyldinyl group, phenanthrolinyl group, acridinyl group, and A carbolinyl group is mentioned.
The aromatic hydrocarbon group, aromatic heterocyclic group and fused polycyclic aromatic group in Arb preferably have a total of 6 to 25 carbon atoms and heteroatoms forming a ring, more preferably 6 to 20. , 6 to 18 are more preferred.

The presence of Arb at the 2-position of the fluorene skeleton in general formula (1-1) gives the compound a bulky and rigid molecular structure, and stacking of molecules is suppressed. As a result, the compound exhibits high excitation energy and energy transfer from the light-emitting layer to the hole transport layer containing the compound is suppressed, so it is presumed that electronic devices including organic EL elements become highly efficient.
In addition, the presence of Arb at the 2-position of the fluorene skeleton in general formula (1-1) increases the rigidity of the compound, thereby increasing the electrical stability, photostability, and thermal stability. It is estimated that this also contributes to extending the life of an organic electronic device including an organic EL element or an organic photoelectric conversion element containing in the hole transport layer.
Furthermore, the presence of Arb at the 2-position of the fluorene skeleton in general formula (1-1) sterically suppresses the attack of nucleophilic compounds and electrophilic compounds on the N atom substituted at the adjacent 3-position. Therefore, it is estimated that the electrical stability, photostability and thermal stability will increase, contributing to the longevity of organic electronic devices including organic EL elements or organic photoelectric conversion elements containing the compound in the hole transport layer. be done.
The high excitation energy exhibited by the compound represented by general formula (1-1) is particularly advantageous for use in electronic devices including blue-emitting organic EL elements.

Arb in general formula (1-1) has a substituent group, judging from electrical stability, thermal stability, film formability, ease of synthesis and purification, etc. A phenyl group, a biphenyl group, or a terphenyl group which may have a substituent is preferable, a phenyl group or a biphenyl group which may have a substituent is more preferable, a phenyl group which may have a substituent is still more preferable, and a phenyl group which may have a substituent is more preferable. A phenyl group having no is most preferred.

Examples of substituents that the aromatic hydrocarbon group, aromatic heterocyclic group, and fused polycyclic aromatic group in Ara to Arc in general formula (1-1) may include include deuterium atom; Group; Nitro group; Halogen group; Straight or branched alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group; Methyloxy group, ethyloxy group, propyl group Alkyloxy groups such as oxy groups; alkenyl groups such as vinyl groups and allyl groups; aryloxy groups such as phenyloxy groups and phenyltrioxy groups; arylalkyloxy groups such as benzyloxy groups; phenyl groups, biphenyl groups, and terphenyl Aromatic hydrocarbon groups or fused polycyclic aromatic groups such as naphthyl group, anthracenyl group, phenanthrenyl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group; pyridyl group, pyrimidyl group , triazinyl group, furyl group, pyrrolyl group, thienyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalinyl group, benzimidazolyl group, pyrazolyl group, Aromatic heterocyclic groups or fused polycyclic aromatic groups such as dibenzofuranyl group, dibenzothienyl group, naphthyldinyl group, phenanthrolinyl group, acridinyl group, and carbolinyl group; arylvinyl group such as styryl group and naphthylvinyl group ; Examples include acyl groups such as acetyl groups.
Two or more of the above-mentioned substituents may be present, and when there are two or more, each substituent may be different.
Furthermore, the above substituents mentioned for Ara and Arc in general formula (1-1) are bonded to each other via a single bond, a methylene group which may have a substituent, an oxygen atom or a sulfur atom, and the may be formed.

The substituents that the aromatic hydrocarbon group, aromatic heterocyclic group, and condensed polycyclic aromatic group in Ara to Arc in general formula (1-1) may have include electrical stability, thermal Judging from the viewpoint of stability, film formability, and ease of synthesis and purification, among the above examples, straight chain alkyl groups having 1 to 10 carbon atoms or straight chain alkyl groups having 1 to 5 carbon atoms A phenyl group, a biphenyl group, a terphenyl group, or a naphthyl group which may be substituted with one or more chain alkyl groups is preferred, and a methyl group, ethyl group, propyl group or butyl group, or a carbon number of 1 to 3 A phenyl group or a biphenyl group which may be substituted with one or more linear alkyl groups is more preferred, and a methyl group or a phenyl group is most preferred.

Specific examples of the compound represented by the general formula (1-1) are shown below, but the invention is not particularly limited thereto.

Among the compounds shown as the above specific examples, a compound represented by the following chemical formula (1a ) to (16p) are listed.

Since the compound represented by the general formula (1-1) has the above-mentioned properties, it can be used as a material for organic EL elements or organic photoelectric conversion elements included in organic electronic devices, and in particular, for organic EL elements. It can be suitably used for a hole transport layer, preferably a hole transport layer of a blue light emitting organic EL device. In particular, the compound enables higher efficiency and longer life of organic EL elements included in organic electronic devices.
The present invention also relates to a hole transport material containing a compound represented by general formula (1-1).

The purity of the compound represented by general formula (1-1) can be measured by high performance liquid chromatography (HPLC). High performance liquid chromatography applies pressure to the mobile phase into which the sample has been introduced, passes the solvent through the mobile phase at a high flow rate, separates the sample (mixture) in a column, and detects the separated sample with a detector. This is a method to measure the purity of a sample.

The molecular weight of the compound represented by general formula (1-1) can be measured by mass spectrometry (MS). Mass spectrometry is performed by applying a high voltage in vacuum to a sample introduced through the sample introduction section, ionizing the sample, separating the ions according to their mass-to-charge ratio, and detecting them at the detection section. .
The sample introduction section can be directly connected to gas chromatography (GC/MS), high performance liquid chromatography (LC/MS), and capillary electrophoresis (CE/MS), and can measure molecular weight as well as purity. be able to. Note that a direct injection method (DI/MS) in which the sample is directly ionized may also be employed.
Various ionization methods are employed in ion sources. Examples include electron ionization (EI), fast atom bombardment (FAB), electrospray ionization (ESI), and inductively coupled plasma (ICP).

Nuclear magnetic resonance spectroscopy (NMR) can be used to identify the compound represented by general formula (1-1). In NMR measurement, information on chemical shifts and coupling can be obtained from the bonding state of atoms, etc., so a spectrum unique to a compound can be obtained, and the compound can be identified. Measurements are performed by dissolving a small amount of sample in various heavy solvents.
The thermal stability of the compound represented by general formula (1-1) can be evaluated by differential scanning calorimetry (DSC). DSC measurement is performed by detecting the difference in calorific value from a standard sample when a thermal change such as a phase transition or melting occurs in the sample. DSC measurement allows the melting point and glass transition temperature of a compound to be determined.

By measuring the ultraviolet-visible absorption spectrum (UV/VIS), fluorescence spectrum (PL), and phosphorescence spectrum of the compound represented by general formula (1-1), the UV absorption wavelength, fluorescence wavelength, and phosphorescence wavelength unique to the compound can be determined. Not only can you know, but you can also know information such as a compound's band gap, fluorescence quantum yield, and triplet energy.
The HOMO level and LUMO level of the compound represented by general formula (1-1) can be measured by cyclic voltammetry (CV). Ionization potential (IP) is also used as an index similar to the HOMO level.
Furthermore, a method is also used in which the optical band gap is determined from the UV absorption wavelength and the LUMO level (or Ea) is calculated from the HOMO level (or IP).

One embodiment of the organic electronic device of the present invention includes a light emitting layer between a cathode and an anode, and a hole transport layer disposed on the anode side of the light emitting layer, and the hole transport layer is generally It includes an organic EL device containing a compound represented by formula (1-1), preferably a blue-emitting organic EL device.
FIG. 1 is a schematic cross-sectional view for explaining an example of an organic EL element included in the organic electronic device of the present invention. The organic EL element 1 shown in FIG. It has a laminated structure in which the layer 4 and the second electrode 3 (cathode) are formed in this order.
The organic EL element included in the organic electronic device of the present invention may have a hole transport layer formed by laminating one layer or two or more layers. Similarly, other layers (for example, a light emitting layer and an electron transport layer) of the organic EL device of the present invention may also be in the form of one layer or a stack of two or more layers.

In an organic EL device 1 shown in FIG. 1, all of the laminated structure forming the organic EL device formed on a substrate 2 is made of an organic compound.
Note that the organic EL device 1 shown in FIG. ). In this case, for example, in the organic EL element 1 shown in FIG. 1, an electron injection layer 4 made of an inorganic oxide and a hole injection layer 8 made of an inorganic oxide are provided as layers made of an inorganic compound. It can be assumed that there is Since inorganic compounds are more stable than organic compounds, HOILED elements are preferred because they have higher resistance to oxygen and water than organic EL elements that do not include a layer made of an inorganic compound.

Further, in the organic EL element 1 shown in FIG. 1, a case will be described in which an electron injection layer 4 and a hole injection layer 8 are provided. The injection layer 8 may be omitted. Further, in the organic EL element 1 shown in FIG. 1, an electron injection layer made of an inorganic compound may be provided in place of the electron injection layer 4 made of an organic compound, and an electron injection layer 8 made of an organic compound may be replaced with an electron injection layer made of an inorganic compound. A hole injection layer made of an inorganic compound may be provided.

The organic EL element 1 shown in FIG. 1 may be of a top emission type that takes out light to the side opposite to the substrate 2 side, or may be of a bottom emission type that takes out light to the side of the substrate 2.
Further, the organic EL element 1 shown in FIG. 1 has a forward structure in which a first electrode 9 functioning as an anode is disposed between a substrate 2 and a light emitting layer 6.

Materials for the substrate 2 include resin materials such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, cycloolefin polymer, polyamide, polyether sulfone, polymethyl methacrylate, polycarbonate, and polyarylate, and quartz glass and soda glass. Examples include glass materials, and one or more of these can be used.

When the organic EL element 1 is of a bottom emission type, a transparent material is used as the material for the substrate 2.
When the organic EL element 1 is of a top emission type, not only a transparent material but also an opaque material can be used as the material for the substrate 2. Examples of the opaque substrate include a substrate made of a ceramic material such as alumina, a metal substrate such as stainless steel with an oxide film (insulating film) formed on the surface, and a substrate made of a resin material. .

The first electrode 9 in the organic EL element 1 shown in FIG. 1 functions as an anode. Examples of the material for the first electrode 9 include ITO (indium tin oxide), IZO (indium zinc oxide), FTO (fluorine tin oxide), In ₃ O ₃ , SnO ₂ , Sb-containing SnO ₂ , Al-containing ZnO, etc. Examples include oxides. Among these, it is preferable to use ITO, IZO, and FTO as the material for the first electrode 9.

The material used for the hole injection layer 8 is selected from the viewpoints of the relationship between the work function of the anode and the IP of the hole transport layer, charge transport characteristics, and the like. For example, phthalocyanine compounds such as poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (abbreviation: PEDOT:PSS), copper phthalocyanine (abbreviation: CuPc), molybdenum oxide (MoO _x ), oxidation Acceptor heterocycles such as vanadium (V ₂ O ₅ ), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN) Compounds can be used. Various organic and inorganic compounds can be selected, regardless of whether they are low molecules or polymers, as long as they have appropriate IP and charge transport properties. Moreover, two or more of these materials can also be used in combination.

The hole transport layer 7 contains a compound represented by the general formula (1-1). Since the compound has a 2-substituted fluorene skeleton defined by the general formula, it has appropriate HOMO and LUMO levels and is excellent in photostability, electrical stability, and thermal stability. Therefore, the recombination efficiency of charges within the light emitting layer can be increased, and an organic EL element with higher luminous efficiency and longer life can be realized.

The compound represented by the general formula (1-1) can be used alone as a hole transporting material, but it can also be used in combination with one or more existing hole transporting materials. Existing hole-transporting materials include, for example, N,N-dibiphenyl-N'-terphenyl-N'-phenylbenzidine (abbreviation: HT1), N,N'-diphenyl-N,N'-di( α-naphthyl)benzidine (abbreviation: NPD), N,N'-diphenyl-N,N'-di(m-tolyl)benzidine (abbreviation: TPD), 1,1-bis[4-[N,N-di Aromatic amine compounds such as (p-tolyl)amino]phenyl]cyclohexane (abbreviation: TAPC), or 4,4',4''-tri-9-carbazolyltriphenylamine (abbreviation: TCTA), 1, Carbazole derivatives such as 3-bis(carbazol-9-yl)benzene (abbreviation: mCP) can be used.

For the light emitting layer 6, a fluorescent material or a phosphorescent material can be used. The luminescent material can also be used by incorporating a luminescent material (guest material) into a host material that performs charge transport and charge recombination.
As the host material, a material having both charge-transporting properties and hole-transporting properties and electron-transporting properties can be used. Further, since the hole transporting material of the present invention has excellent electron blocking performance, an electron transporting material can also be used as the host material.

As the host material, for example, metal complexes such as aluminum complexes and beryllium complexes, anthracene derivatives, oxadiazole derivatives, benzimidazole derivatives, and phenanthrene derivatives can be used.

The luminescent material is not particularly limited, but as the fluorescent material, for example, quinacridone, coumarin, rubrene, perylene and its derivatives, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives, pyrene derivatives, aromatic amine derivatives, and tetracene derivatives can be used. can. Further, as the phosphorescent material, for example, a metal complex such as iridium or platinum can be used. A green luminescent material such as Ir(ppy) ₃ , a blue luminescent material such as FIrpic, and a red luminescent material such as (Btp) ₂ Ir(acac) are used.

Examples of materials used for the electron transport layer 5 include metal complexes of quinolinol derivatives such as Alq3 and BAlq, anthracene derivatives, pyridine derivatives, pyrimidine derivatives, benzimidazole derivatives, quinoxaline derivatives, phenanthroline derivatives, triazine derivatives, carbazole derivatives, Triazole derivatives can be used.
Providing an electron transport layer containing a material with an appropriate LUMO level between the emissive layer and the cathode or electron injection layer relaxes the electron injection barrier from the cathode or electron injection layer to the electron transport layer, and furthermore, the electron transport layer It is possible to alleviate the barrier for electron injection into the light-emitting layer. In addition, when the material has an appropriate HOMO level, it prevents holes from flowing out to the counter electrode without recombining in the light-emitting layer, confines the holes within the light-emitting layer, and increases recombination efficiency within the light-emitting layer. be able to.

The material used for the electron injection layer 4 is selected from the viewpoints of the work function of the cathode, the LUMO level of the electron transport layer, etc. When an electron transport layer is not provided, it is selected in consideration of the LUMO level of the light emitting material or the host material described below. The electron injection material may be an organic compound or an inorganic compound.
When the electron injection layer is made of an inorganic compound, for example, in addition to alkali metals and alkaline earth metals, lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, and cesium carbonate may be used. I can do it.

The cathode of an organic EL element plays the role of injecting electrons into an electron injection layer or an electron transport layer. For the cathode, materials that act as a cathode are used, such as various metal materials and various alloys with relatively small work functions. Examples include aluminum, silver, magnesium, calcium, gold, indium tin oxide (ITO), indium zinc oxide (IZO), magnesium indium alloy (MgIn), and silver alloy.
When employing the bottom emission method, an opaque electrode made of metal can be used as the cathode. Further, the cathode can also be a reflective electrode.
When employing the top emission method, a transparent electrode such as ITO or IZO can be used as the cathode. Here, since ITO has a large work function, it is difficult to inject electrons, and sputtering and ion beam evaporation are used to form ITO films. May cause damage. Therefore, in order to improve electron injection and reduce damage to the electron transport layer during film formation, a magnesium layer or a copper phthalocyanine layer may be provided between the electron transport layer and ITO.

The organic photoelectric conversion element included in the organic electronic device of the present invention can also be produced in accordance with the above organic EL element.

Hereinafter, the present invention will be described in more detail with reference to Examples, which are intended to illustrate specific examples of the present invention, and the present invention is not limited thereto.

[Synthesis of compounds]
Example 1
Compound (1a) was synthesized by the synthetic route shown below.

Compound (A1) was synthesized by the method shown below.
In a 300 mL Schlenk tube equipped with a stirrer and purged with argon, 1,4-dibromo-2,5-diiodobenzene (25.0 g, 51 mmol), phenylboronic acid (13.1 g, 107 mmol), and tetrakistriphenylphosphine were added. Palladium (8.95 g, 7.7 mmol), toluene (200 mL), water (80 mL), and potassium carbonate (35.7 g, 258 mmol) were added and the mixture was sealed, followed by stirring at 100° C. for 16 hours. Thereafter, the reaction vessel was allowed to cool to around room temperature for 4 hours, and the precipitate was collected by filtration. Thereafter, the target compound (A1) was obtained by washing with water and methanol (yield: 15.6 g, yield: 78.4%).

Compound (A2) was synthesized by the method shown below.
Compound (A1) (3.88 g, 10 mmol) and tetrahydrofuran (200 mL) were placed in a 500 mL four-necked flask equipped with a stirrer and purged with argon, stirred, and cooled to -78°C. A 1.6M n-butyllithium hexane solution (7.64 mL, 12 mmol) was added dropwise thereto. After stirring for 1 hour, benzophenone (2.16 g, 12 mmol) was added, and after further stirring for 1 hour, the cooling bath was removed, the temperature was raised from -78°C to room temperature, and the mixture was stirred for 1 hour. The reaction was stopped by adding distilled water (50 mL) in portions. The contents were transferred to a separatory funnel, dichloromethane was added to separate the organic and aqueous phases, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The resulting mixture was purified by washing with cyclohexane to obtain the target compound (A2) (yield: 4.23 g, yield: 86.1%).

Compound (A3) was synthesized by the method shown below.
Compound (A2) (4.20 g, 8.54 mmol), chloroform (100 mL), and trifluoromethanesulfonic acid (100 μl, 1.1 mmol) were placed in a 100 mL Schlenk tube equipped with a stirrer and replaced with argon, and the tube was sealed. and stirred at room temperature for 2 hours. Then, a saturated aqueous sodium hydrogen carbonate solution (30 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The resulting mixture was purified by washing with hexane to obtain the target compound (A3) (yield: 3.94 g, yield: 97%).

Compound (B1) was synthesized by the method shown below.
4-amino-p-terphenyl (3.15 g, 12.8 mmol), 4-bromobiphenyl (2.5 g, 10.7 mmol), tris(dibenzylidene) were placed in a 300 mL Schlenk tube equipped with a stirrer and purged with argon. acetone) dipalladium(0) (196 mg, 0.21 mmol), toluene (80 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (176 mg, 0.43 mmol), and sodium t-butoxy (1. After the mixture was sealed, the mixture was stirred at 100°C for 5 hours. Thereafter, the reaction container was allowed to cool to around room temperature, and the precipitate was collected by filtration and washed with water and ethyl acetate to obtain the target compound (B1) (yield: 4.11 g, yield: 96%). .

Compound (1a) was synthesized by the method shown below.
Compound (A3) (2.5 g, 5.23 mmol), compound (B1) (1.5 g, 3.77 mmol), and bis(tri-t-butylphosphine) were placed in a 100 mL Schlenk tube equipped with a stirrer and replaced with argon. Palladium (0) (77 mg, 0.15 mmol), xylene (60 mL), and sodium t-butoxy (543 mg, 5.66 mmol) were added and the mixture was sealed, followed by stirring at 130° C. for 16 hours. Thereafter, the reaction container was allowed to cool to around room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The concentrated mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 2/1), and then washed with cyclohexane to obtain the target compound (1a) (yield: 1. 01g, yield 34%). MS: [M+H] ⁺ =790

Example 2
Compound (2b) was synthesized by the synthetic route shown below.

Compound (A4) was synthesized by the method shown below.
Compound (A1) (3.88 g, 10 mmol) and tetrahydrofuran (200 mL) were placed in a 500 mL four-necked flask equipped with a stirrer and purged with argon, stirred, and cooled to -78°C. A 1.6M n-butyllithium hexane solution (7.64 mL, 12 mmol) was added dropwise thereto. After stirring for 1 hour, fluorenone (2.16 g, 12 mmol) was added, and after further stirring for 1 hour, the cooling bath was removed, the temperature was raised from -78°C to room temperature, and the mixture was stirred for 1 hour. The reaction was stopped by adding distilled water (50 mL) in portions. The contents were transferred to a separatory funnel, dichloromethane was added to separate the organic and aqueous phases, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The resulting mixture was purified by washing with cyclohexane to obtain the target compound (A4) (yield: 2.85 g, yield: 58.2%).

Compound (A5) was synthesized by the method shown below.
Compound (A4) (2.85 g, 5.82 mmol), chloroform (100 mL), and trifluoromethanesulfonic acid (100 μl, 1.1 mmol) were placed in a 100 mL Schlenk tube equipped with a stirrer and replaced with argon, and the tube was sealed. and stirred at room temperature for 2 hours. Then, a saturated aqueous sodium hydrogen carbonate solution (30 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The resulting mixture was purified by washing with hexane to obtain the target compound (A5) (yield: 2.66 g, yield: 89.8%).

Compound (B2) was synthesized by the method shown below.
4-Amino-p-terphenyl (1.78 g, 7.23 mmol), 4-(4-bromophenyl)dibenzofuran (1.95 g, 5.78 mmol) were placed in a 300 mL Schlenk tube equipped with a stirrer and purged with argon. , tris(dibenzylideneacetone)dipalladium(0) (110 mg, 0.12 mmol), toluene (60 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (99 mg, 0.24 mmol), and t- Butoxysodium (0.73 g, 7.23 mmol) was added and the mixture was sealed, followed by stirring at 100° C. for 5 hours. Thereafter, the reaction container was allowed to cool to around room temperature, and the precipitate was collected by filtration and washed with water and ethyl acetate to obtain the target compound (B2) (yield 2.88 g, yield 98%). .

Compound (2b) was synthesized by the method shown below.
Compound (A5) (2.12 g, 4.50 mmol), compound (B2) (1.46 g, 2.99 mmol), and bis(tri-t-butylphosphine) were placed in a 200 mL Schlenk tube equipped with a stirrer and replaced with argon. Palladium (0) (76.7 mg, 0.15 mmol), xylene (60 mL), and sodium t-butoxy (432 mg, 4.50 mmol) were added and the mixture was sealed, followed by stirring at 130° C. for 16 hours. Thereafter, the reaction container was allowed to cool to around room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The concentrated mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 2/1), and then recrystallized from 2-propanol to obtain the target compound (2b) ( Yield: 861 mg, yield: 33%). MS: [M+H] ⁺ =878

Example 3
Compound (3c) was synthesized by the synthetic route shown below.

Compound (B3) was synthesized by the method shown below.
4-Amino-p-terphenyl (0.72 g, 2.94 mmol) and 4-(4-bromophenyl)dibenzothiophene (1.00 g, 2.94 mmol) were placed in a 50 mL Schlenk tube equipped with a stirrer and replaced with argon. ), tris(dibenzylideneacetone)dipalladium(0) (27 mg, 0.03 mmol), toluene (20 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (24 mg, 0.06 mmol), and t -Butoxysodium (0.35 g, 3.68 mmol) was added, the mixture was sealed, and the mixture was stirred at 100° C. for 5 hours. Thereafter, the reaction container was allowed to cool to around room temperature, and the precipitate was collected by filtration and washed with water and ethyl acetate to obtain the target compound (B3) (yield: 1.30 g, yield: 88%). .

Compound (3c) was synthesized by the method shown below.
Compound (A5) (1.89 g, 4.00 mmol), compound (B3) (1.30 g, 2.85 mmol), and bis(tri-t-butylphosphine) were placed in a 100 mL Schlenk tube equipped with a stirrer and replaced with argon. Palladium (0) (53 mg, 0.11 mmol), xylene (30 mL), and sodium t-butoxy (0.37 g, 4.27 mmol) were added and the mixture was sealed, followed by stirring at 130° C. for 16 hours. Thereafter, the reaction container was allowed to cool to around room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The concentrated mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 2/1), and then recrystallized with a mixed solvent of toluene and methanol to obtain the target compound (3c). (yield 572 mg, yield 23%). MS: m/z=893

Example 4
Compound (4d) was synthesized by the synthetic route shown below.

Compound (A6) was synthesized by the method shown below.
Compound (A5) (4.00 g, 8.48 mmol), 4-amino-p-terphenyl (2.08 g, 8.48 mmol), and tris(dibenzylidene) were placed in a 100 mL Schlenk tube equipped with a stirrer and purged with argon. acetone) dipalladium(0) (80 mg, 0.085 mmol), toluene (40 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (72 mg, 0.17 mmol), and sodium t-butoxy (1. After the mixture was sealed, the mixture was stirred at 100°C for 2 hours. Thereafter, the reaction container was allowed to cool to around room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The concentrated mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 1/2) to obtain the target compound (A6) (yield: 3.6 g, yield: 90%). .

Compound (4d) was synthesized by the method shown below.
Compound (A6) (1.72 g, 2.70 mmol), 4-bromo-p-terphenyl (0.84 g, 2.70 mmol), bis(tri-t) were placed in a 100 mL Schlenk tube equipped with a stirrer and purged with argon. -butylphosphine)palladium(0) (41 mg, 0.081 mmol), xylene (18 mL), and t-butoxysodium (0.37 g, 4.05 mmol) were added, and after sealing, the mixture was stirred at 130°C for 16 hours. . Thereafter, the reaction vessel was allowed to cool to around room temperature, and the precipitate was collected by filtration and washed with toluene, methanol, and water. Thereafter, the obtained mixture was purified by silica gel column chromatography (developing solvent: hexane/ethyl acetate = 4/1), and then recrystallized with a mixed solvent of toluene and THF to obtain the target compound (4d). (yield: 1.53 g, yield: 66%). MS: m/z=863

Example 5
Compound (5e) was synthesized by the synthetic route shown below.

Compound (B4) was synthesized by the method shown below.
In a 100 mL Schlenk tube equipped with a stirrer and purged with argon, 4-chlorophenylboronic acid (1.43 g, 9.15 mmol), 2-bromo-9,9-dimethylfluorene (2.50 g, 9.15 mmol), and tetrakis were placed. Add triphenylphosphine palladium (211 mg, 0.183 mmol), toluene (33 mL), water (11 mL), and tripotassium phosphate (3.88 g, 18.3 mmol), and after sealing, stir at 100°C for 2 hours. did. Thereafter, the reaction container was allowed to cool to around room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The concentrated mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 7/1) and washed with hexane to obtain the target compound (B4) (yield: 2.53 g, Yield 91%).

Compound (5e) was synthesized by the method shown below.
Compound (A6) (1.37 g, 2.16 mmol), compound (B4) (0.99 g, 3.24 mmol), and bis(tri-t-butylphosphine) were placed in a 100 mL Schlenk tube equipped with a stirrer and replaced with argon. Palladium (0) (66 mg, 0.13 mmol), xylene (20 mL), and sodium t-butoxy (0.39 g, 4.32 mmol) were added and the mixture was sealed, followed by stirring at 130° C. for 5 hours. Thereafter, the reaction container was allowed to cool to around room temperature, the lid was opened, and water (40 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The resulting concentrated mixture was purified by silica gel column chromatography (developing solvent: cyclohexane/toluene = 3/2). Thereafter, the mixture was dissolved in toluene and recrystallized by vapor diffusion of methanol to obtain the target compound (5e) (yield: 0.58 g, yield: 27%). MS: m/z=903

Example 6
Compound (6f) was synthesized by the synthetic route shown below.

Compound (6f) was synthesized by the method shown below.
Compound (A6) (1.14 g, 1.79 mmol), 1-(4-bromophenyl)naphthalene (0.59 g, 1.97 mmol), bis(tri- Add t-butylphosphine) palladium (0) (27 mg, 0.054 mmol), xylene (12 mL), and t-butoxysodium (0.26 g, 2.69 mmol), and after sealing, stir at 130°C for 16 hours. did. Thereafter, the reaction container was allowed to cool to around room temperature, the lid was opened, and water (10 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The resulting concentrated mixture was purified by silica gel column chromatography (developing solvent: THF). Thereafter, the target compound (6f) was obtained by recrystallizing with toluene and washing with THF (yield: 0.70 g, yield: 47%). MS: m/z=837

Example 7
A compound (7g) was synthesized by the synthetic route shown below.

1-(4-aminophenyl)naphthalene was synthesized by the method shown below.
In a 200 mL Schlenk tube equipped with a stirrer and purged with argon, 4-bromoaniline (4.00 g, 23.3 mmol), 1-naphthylboronic acid (4.40 g, 25.6 mmol), and tetrakistriphenylphosphine palladium (808 mg) were added. , 0.70 mmol), toluene (90 mL), water (30 mL), and tripotassium phosphate (14.8 g, 69.9 mmol), and after sealing, the mixture was stirred at 100° C. for 2 hours. Thereafter, the reaction container was allowed to cool to around room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The concentrated mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 1/2) to obtain the desired 1-(4-aminophenyl)naphthalene (yield: 4.50 g, yield 88%).

Compound (A7) was synthesized by the method shown below.
In a 100 mL Schlenk tube equipped with a stirrer and purged with argon, compound (A5) (2.50 g, 5.28 mmol), 1-(4-aminophenyl)naphthalene (1.16 g, 5.28 mmol), tris(di benzylideneacetone) dipalladium (0) (72 mg, 0.079 mmol), toluene (31 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (65 mg, 0.16 mmol), and t-butoxysodium (0 After the mixture was sealed, the mixture was stirred at 100°C for 2 hours. Thereafter, the reaction container was allowed to cool to around room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The concentrated mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 2/1) to obtain the target compound (A7) (yield: 3.0 g, yield: 93%). .

A compound (7g) was synthesized by the method shown below.
Compound (A7) (3.00 g, 4.91 mmol), 1-(4-bromophenyl)naphthalene (2.00 g, 7.06 mmol), bis(tri- Add t-butylphosphine) palladium (0) (120 mg, 0.24 mmol), xylene (48 mL), and t-butoxysodium (0.79 g, 8.25 mmol), and after sealing, stir at 130°C for 3 hours. did. Thereafter, the reaction container was allowed to cool to around room temperature, the lid was opened, and water (40 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The resulting concentrated mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 2/1). Thereafter, the mixture was recrystallized with acetone and methanol and washed with ethyl acetate to obtain the target compound (7 g) (yield: 1.61 g, yield: 40%). MS: m/z=811

Example 8
Compound (8h) was synthesized by the synthetic route shown below.

Compound (8h) was synthesized by the method shown below.
Compound (A6) (2.42 g, 3.81 mmol), 2-(4-bromophenyl)naphthalene (1.19 g, 4.19 mmol), bis(tri- t-Butylphosphine) palladium (0) (58.4 mg, 0.11 mmol), toluene (38 mL), and t-butoxysodium (0.51 g, 5.33 mmol) were added, and after sealing, the mixture was heated at 100°C for 5 hours. , stirred. Thereafter, the reaction container was allowed to cool to around room temperature, the lid was opened, and water (20 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The resulting concentrated mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 2/1). Thereafter, the target compound (8h) was obtained by recrystallizing with a mixed solvent of toluene and methanol and washing with THF (yield: 2.00 g, yield: 63%). MS: m/z=837

Example 9
Compound (9i) was synthesized by the method shown below.

2-(4-aminophenyl)naphthalene was synthesized by the method shown below.
In a 100 mL Schlenk tube equipped with a stirrer and purged with argon, 4-bromoaniline (2.70 g, 15.7 mmol), 2-naphthylboronic acid (2.99 g, 17.4 mmol), and tetrakistriphenylphosphine palladium (543 mg) were added. , 0.47 mmol), toluene (30 mL), water (6 mL), and tripotassium phosphate (3.81 g, 31.4 mmol), and after sealing the mixture, the mixture was stirred at 100° C. for 2 hours. Thereafter, the reaction container was allowed to cool to around room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The concentrated mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 1/3) to obtain the desired 2-(4-aminophenyl)naphthalene (yield: 3.33 g, yield 96%).

Compound (A8) was synthesized by the method shown below.
In a 100 mL Schlenk tube equipped with a stirrer and purged with argon, compound (A5) (2.12 g, 4.50 mmol), 2-(4-aminophenyl)naphthalene (1.04 g, 4.73 mmol), and tris(di benzylideneacetone) dipalladium(0) (21 mg, 0.023 mmol), toluene (23 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (19 mg, 0.045 mmol), and t-butoxysodium (0 After the mixture was sealed, the mixture was stirred at 100°C for 2 hours. Thereafter, the reaction container was allowed to cool to around room temperature, the lid was opened, and water (40 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The concentrated mixture was purified by silica gel column chromatography (developing solvent: cyclohexane/toluene = 2/1) and washed with methanol to obtain the target compound (A8) (yield: 2.7 g, yield 98%).

Compound (9i) was synthesized by the method shown below.
Compound (A8) (2.70 g, 4.47 mmol), 2-(4-bromophenyl)naphthalene (2.21 g, 4.69 mmol), bis(tri- t-Butylphosphine) palladium (0) (22.8 mg, 0.045 mmol), toluene (33 mL), and t-butoxysodium (0.65 g, 6.71 mmol) were added, and after sealing, the mixture was heated at 100°C for 2 hours. , stirred. Thereafter, the reaction container was allowed to cool to around room temperature, the lid was opened, and water (40 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The resulting concentrated mixture was purified by silica gel column chromatography (developing solvent: cyclohexane/toluene = 3/1). Thereafter, the mixture was recrystallized with toluene and washed with toluene and methanol to obtain the target compound (9i) (yield: 1.89 g, yield: 52%). MS: m/z=811

Example 10
Compound (10j) was synthesized by the method shown below.

Compound (10j) was synthesized by the method shown below.
Compound (A8) (6.70 g, 1.79 mmol), 1-(4-bromophenyl)naphthalene (2.13 g, 7.53 mmol), bis(tri- Add t-butylphosphine) palladium (0) (35 mg, 0.068 mmol), toluene (35 mL), and t-butoxysodium (0.82 g, 8.55 mmol), and after sealing, stir at 100°C for 2 hours. did. Thereafter, the reaction container was allowed to cool to around room temperature, the lid was opened, and water (20 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The resulting concentrated mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 2/1). Thereafter, the target compound (10j) was obtained by recrystallizing with a mixed solvent of dichloromethane, acetone, and methanol and washing with isopropanol (yield: 2.00 g, yield: 36%). MS: m/z=811

Example 11
Compound (11k) was synthesized by the method shown below.

9-(4-chlorophenyl)phenanthrene was synthesized by the method shown below.
4-chloroboronic acid (1.72 g, 11.0 mmol), 9-bromophenanthrene (2.57 g, 10.0 mmol), tetrakistriphenylphosphine palladium (115 mg, After the mixture was sealed, the mixture was stirred at 100°C for 3 hours. Thereafter, the reaction container was allowed to cool to around room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The concentrated mixture was purified by silica gel column chromatography (developing solvent: toluene) and washed with methanol to obtain the target 9-(4-chlorophenyl)phenanthrene (yield 2.63 g, yield 91%).

Compound (11k) was synthesized by the method shown below.
Compound (A6) (2.57 g, 4.04 mmol), 9-(4-chlorophenyl)phenanthrene (1.43 g, 4.95 mmol), bis(tri- Add t-butylphosphine) palladium (0) (35 mg, 0.068 mmol), toluene (23 mL), and t-butoxysodium (0.65 g, 6.75 mmol), and after sealing, stir at 100°C for 3 hours. did. Thereafter, the reaction container was allowed to cool to around room temperature, the lid was opened, and water (40 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The mixture obtained by concentration was purified by silica gel column chromatography (developing solvent: cyclohexane/toluene = 1/1). Thereafter, the target compound (11k) was obtained by recrystallizing with methylcyclohexane and washing with 2-methoxy-2-methylpropane (yield: 1.84 g, yield: 38%). MS: m/z=887

Example 12
Compound (12l) was synthesized by the method shown below.

Compound (A9) was synthesized by the method shown below.
Compound (A1) (2.50 g, 6.44 mmol) and tetrahydrofuran (128 mL) were placed in a 300 mL four-necked flask equipped with a stirrer and purged with argon, stirred, and cooled to -78°C. A 1.6M n-butyllithium hexane solution (4.51 mL, 7.09 mmol) was added dropwise thereto. After stirring for 1 hour, 4-phenylbenzophenone (2.00 g, 7.73 mmol) was added, and after further stirring for 1 hour, the cooling bath was removed, the temperature was raised from -78°C to room temperature, and the mixture was stirred for 1 hour. The reaction was stopped by adding distilled water (50 mL) in portions. The contents were transferred to a separatory funnel, ethyl acetate was added to separate the organic and aqueous phases, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The resulting mixture was purified by washing with hexane to obtain the target compound (A9) (yield: 2.45 g, yield: 67%).

Compound (A10) was synthesized by the method shown below.
Compound (A9) (2.45 g, 4.31 mmol), dichloromethane (130 mL), and trifluoromethanesulfonic acid (120 μl, 1.3 mmol) were placed in a 300 mL two-necked eggplant flask equipped with a stirrer and purged with argon, and the flask was sealed. After that, the mixture was stirred at room temperature for 1 hour. Then, a saturated aqueous sodium hydrogen carbonate solution (30 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The mixture obtained by concentration was purified by silica gel column chromatography (developing solvent: hexane/ethyl acetate = 5/1) to obtain the target compound (A10) (yield 2.11 g, yield 90 %).

Compound (12l) was synthesized by the method shown below.
Compound (A10) (2.12 g, 3.85 mmol), 4-amino-p-terphenyl (0.94 g, 3.85 mmol), and tris(dibenzylidene) were placed in a 100 mL Schlenk tube equipped with a stirrer and purged with argon. acetone) dipalladium(0) (18 mg, 0.019 mmol), toluene (40 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (16 mg, 0.039 mmol), and sodium t-butoxy (0. 46 g, 4.81 mmol) was added thereto, the mixture was sealed, and the mixture was stirred at 100° C. for 1 hour. Thereafter, 1-(4-bromophenyl)naphthalene (1.20 g, 4.23 mmol), bis(tri-t-butylphosphine) palladium(0) (20 mg, 0.039 mmol), toluene (20 mL) and Sodium t-butoxy (0.46 g, 4.81 mmol) was added and the mixture was sealed, followed by stirring at 100° C. for 16 hours. The reaction container was allowed to cool to around room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The concentrated mixture was purified by silica gel column chromatography (developing solvent: cyclohexane/toluene = 5/1), and then recrystallized with a mixed solvent of cyclohexane, toluene, and hexane to obtain the target compound (12 l ) was obtained (yield: 1.30 g, yield: 37%). MS: m/z=915

Example 13
Compound (13m) was synthesized by the method shown below.

Compound (A12) was synthesized by the method shown below.
Compound (A1) (3.0 g, 7.7 mmol) and tetrahydrofuran (150 mL) were placed in a 300 mL four-necked flask equipped with a stirrer and purged with argon, stirred, and cooled to -78°C. A 1.6M n-butyllithium hexane solution (5.39 mL, 8.50 mmol) was added dropwise thereto. After stirring for 1 hour, 2-phenyl-9-fluorenone (2.38 g, 9.24 mmol) was added, and after further stirring for 1 hour, the cooling bath was removed, the temperature was raised from -78°C to room temperature, and the mixture was stirred for 1 hour. did. The reaction was stopped by adding distilled water (50 mL) in portions. The contents were transferred to a separatory funnel, ethyl acetate was added to separate the organic and aqueous phases, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The resulting mixture was purified by washing with hexane to obtain the target compound (A12) (yield: 3.68 g, yield: 84%).

Compound (A13) was synthesized by the method shown below.
Compound (A12) (3.60 g, 6.37 mmol), dichloromethane (40 mL), and trifluoromethanesulfonic acid (168 μl, 1.82 mmol) were placed in a 100 mL two-neck eggplant flask equipped with a stirrer and purged with argon, and the flask was sealed. After that, the mixture was stirred at room temperature for 1 hour. Then, saturated aqueous sodium hydrogen carbonate solution (20 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The mixture obtained by concentration was washed with hexane to obtain the target compound (A13) (yield: 3.07 g, yield: 88%).

Compound (A14) was synthesized by the method shown below.
Compound (A13) (3.0 g, 5.48 mmol), 4-amino-p-terphenyl (1.34 g, 5.46 mmol), and tris(dibenzylidene) were placed in a 100 mL Schlenk tube equipped with a stirrer and purged with argon. acetone) dipalladium(0) (50 mg, 0.055 mmol), toluene (30 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (45 mg, 0.109 mmol), and sodium t-butoxy (0. 66 g, 6.85 mmol) and the mixture was sealed, followed by stirring at 100° C. for 2 hours. Thereafter, the reaction container was allowed to cool to around room temperature, the lid was opened, and water (40 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The concentrated mixture was recrystallized from toluene to obtain the target compound (A14) (yield: 2.65 g, yield: 68%).

Compound (13m) was synthesized by the method shown below.
Compound (A14) (2.65 g, 3.72 mmol), 1-(4-bromophenyl)naphthalene (1.15 g, 4.09 mmol), and toluene (20 mL) were placed in a 100 mL Schlenk tube equipped with a stirrer and replaced with argon. ), bis(tri-t-butylphosphine)palladium(0) (29 mg, 0.056 mmol), and sodium t-butoxy (0.45 g, 4.65 mmol), and after sealing, at 100 ° C. for 2 hours. Stirred. The reaction container was allowed to cool to around room temperature, the lid was opened, and water (20 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The resulting concentrated mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 1/1), and then recrystallized from cyclohexane. Furthermore, the target compound (13m) was obtained by recrystallizing with a mixed solvent of dichloromethane, acetone, and methanol and washing with isopropanol (yield: 2.36 g, yield: 69%). MS: m/z=913
Example 14
Compound (14n) was synthesized by the method shown below.

Compound (A15) was synthesized by the method shown below.
Compound (A1) (2.60 g, 6.7 mmol) and tetrahydrofuran (140 mL) were placed in a 300 mL four-necked flask equipped with a stirrer and purged with argon, stirred, and cooled to -78°C. A 1.6M n-butyllithium hexane solution (5.12 mL, 8.04 mmol) was added dropwise thereto. After stirring for 1 hour, 11H-benzo[b]fluorenon-11-one (1.70 g, 7.37 mmol) was added, and after further stirring for 1 hour, the cooling bath was removed and the temperature was raised from -78 °C to room temperature. , and stirred for 1 hour. The reaction was stopped by adding distilled water (50 mL) in portions. The contents were transferred to a separatory funnel, ethyl acetate was added to separate the organic and aqueous phases, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The resulting mixture was purified by washing with hexane to obtain the target compound (A15) (yield: 3.21 g, yield: 89%).

Compound (A16) was synthesized by the method shown below.
Compound (A15) (2.71 g, 5.02 mmol), dichloromethane (30 mL), and trifluoromethanesulfonic acid (1.91 mL, 7.54 mmol) were placed in a 100 mL two-necked eggplant flask equipped with a stirrer and purged with argon. After sealing, the mixture was stirred at room temperature for 1 hour. Then, saturated aqueous sodium hydrogen carbonate solution (20 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The mixture obtained by concentration was washed with methanol and cyclohexane to obtain the target compound (A16) (yield: 1.90 g, yield: 72%).

Compound (A17) was synthesized by the method shown below.
Compound (A16) (1.71 g, 3.28 mmol), 4-amino-p-terphenyl (0.80 g, 3.28 mmol), and tris(dibenzylidene) were placed in a 100 mL Schlenk tube equipped with a stirrer and purged with argon. acetone) dipalladium(0) (15 mg, 0.02 mmol), toluene (35 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (14 mg, 0.03 mmol), and sodium t-butoxy (0. After the mixture was sealed, the mixture was stirred at 100°C for 1 hour. The reaction container was allowed to cool to around room temperature, the lid was opened, and water (40 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The concentrated mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 1/2) to obtain the target compound (A17) (yield 2.08 g, yield 92%). .

Compound (14n) was synthesized by the method shown below.
Compound (A17) (2.2 g, 3.28 mmol), 1-(4-bromophenyl)naphthalene (1.02 g, 3.61 mmol), and toluene (35 mL) were placed in a 100 mL Schlenk tube equipped with a stirrer and replaced with argon. ), bis(tri-t-butylphosphine)palladium(0) (17 mg, 0.03 mmol), and sodium t-butoxy (0.39 g, 4.10 mmol), and after sealing, at 100 ° C. for 2 hours. Stirred. The reaction container was allowed to cool to around room temperature, the lid was opened, and water (40 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The concentrated mixture was purified by silica gel column chromatography (developing solvent: hexane/toluene = 1/1) and recrystallized with a mixed solvent of toluene and methanol to obtain the target compound (14n). (Yield: 1.61 g, yield: 55%). MS: m/z=887
Example 15
Compound (15o) was synthesized by the method shown below.

Compound (15o) was synthesized by the method shown below.
In a 100 mL Schlenk tube equipped with a stirrer and purged with argon, compound (A13) (2.00 g, 3.65 mmol), 2-(4-aminophenyl)naphthalene (0.80 g, 3.65 mmol), and tris(di benzylideneacetone)dipalladium(0) (33 mg, 0.037 mmol), toluene (25 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (30 mg, 0.037 mmol), and t-butoxysodium (0 .53 g, 5.48 mmol) and the mixture was sealed, followed by stirring at 100° C. for 1 hour. Thereafter, 2-(4-bromophenyl)naphthalene (1.24 g, 4.39 mmol), bis(tri-t-butylphosphine) palladium(0) (28 mg, 0.055 mmol), toluene (25 mL) and Sodium t-butoxy (0.53 g, 5.48 mmol) was added and the mixture was sealed, followed by stirring at 100° C. for 2 hours. The reaction container was allowed to cool to around room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The concentrated mixture was purified by silica gel column chromatography (developing solvent: cyclohexane/toluene = 2/1), and then recrystallized with a mixed solvent of dichloromethane and methanol to obtain the target compound (15o). was obtained (yield: 1.30 g, yield: 41%). MS: m/z=887
Example 16
Compound (16p) was synthesized by the method shown below.

Compound (16p) was synthesized by the method shown below.
In a 100 mL Schlenk tube equipped with a stirrer and purged with argon, compound (A16) (0.78 g, 1.50 mmol), 2-(4-aminophenyl)naphthalene (0.33 g, 1.50 mmol), and tris(distillate) were placed. benzylideneacetone) dipalladium(0) (6.9 mg, 0.008 mmol), toluene (8 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (6.2 mg, 0.015 mmol), and t- Butoxysodium (0.18 g, 1.88 mmol) was added and the mixture was sealed, followed by stirring at 100° C. for 1 hour. Thereafter, 2-(4-bromophenyl)naphthalene (0.47 g, 1.65 mmol), bis(tri-t-butylphosphine) palladium(0) (7.7 mg, 0.015 mmol), toluene (3 .8 mL) and t-butoxy sodium (0.18 g, 1.88 mmol) were added, the mixture was sealed, and the mixture was stirred at 100° C. for 4 hours. The reaction container was allowed to cool to around room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel and the organic phase and aqueous phase were separated, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried with sodium sulfate. Thereafter, sodium sulfate was removed by filtration and the organic phase was concentrated. The concentrated mixture was purified by silica gel column chromatography (developing solvent: cyclohexane/toluene = 2/1), and then recrystallized with a mixed solvent of THF and methanol to obtain the target compound (16p). was obtained (yield: 0.69 g, yield: 53%). MS: m/z=861
Example 17
Compounds (1a) to (16p) synthesized in Examples 1 to 16 above and Comparative Compounds 1 to 3 shown below were subjected to DSC measurement.

Tg and decomposition temperature are shown in Table 1.

As shown in Table 1, it can be seen that the compound of the present invention has a Tg of 135° C. or higher, a high decomposition temperature, and is a material with excellent thermal stability. It is thought that Arb present at the 2-position of the fluorene skeleton in general formula (1-1) acted as one factor that brought about suitable thermal stability.
Furthermore, since it exhibits a Tg that is 10° C. higher than the comparative compound, it is considered to have higher thermal stability, so it can be expected to be applied to vehicle-mounted organic EL devices, etc.

[Creation of organic EL element]
Example 18
A hole injection layer was formed by vacuum evaporating a compound HAT-CN having the following structural formula to a thickness of 10 nm on a glass substrate on which ITO (indium tin oxide) had been formed to a thickness of 110 nm. On the hole injection layer, a compound HT1 having the following structural formula was vacuum deposited to a thickness of 80 nm to form a first hole transport layer. Next, the prepared compound (1a) was vacuum deposited on the first hole transport layer to a thickness of 10 nm to form a second hole transport layer. Next, a compound BD1 having the following structural formula was used as a guest material on the second hole transport layer, a compound BH1 having the following structural formula was used as a host material, and the content of the guest material in the light emitting layer was 4% by weight. A light emitting layer with a thickness of 25 nm was formed. Next, a compound HB1 (25 nm) having the following structural formula and a compound ET1 (10 nm) having the following structural formula were sequentially vacuum-deposited on the light emitting layer to form an electron transport layer. Next, lithium fluoride (LiF) (1 nm) and aluminum (80 nm) were sequentially vacuum-deposited on the electron transport layer to form an electron injection layer and a cathode.

Example 19
An organic EL device was formed in the same manner as in Example 18, except that the material of the second hole transport layer was replaced with compound (2b).
Example 20
An organic EL device was formed in the same manner as in Example 18, except that the material of the second hole transport layer was replaced with compound (3c).
Example 21
An organic EL device was formed in the same manner as in Example 18, except that the material of the second hole transport layer was replaced with compound (4d).
Example 22
An organic EL device was formed in the same manner as in Example 18, except that the material of the second hole transport layer was replaced with compound (5e).
Example 23
An organic EL device was formed in the same manner as in Example 18, except that the material of the second hole transport layer was replaced with compound (6f).
Example 24
An organic EL device was formed in the same manner as in Example 18, except that the material of the second hole transport layer was replaced with a compound (7 g).
Example 25
An organic EL device was formed in the same manner as in Example 18, except that the material of the second hole transport layer was replaced with compound (8h).
Example 26
An organic EL device was formed in the same manner as in Example 18 except that the material of the second hole transport layer was replaced with compound (9i).
Example 27
An organic EL device was formed in the same manner as in Example 18, except that the material of the second hole transport layer was replaced with compound (10j).
Example 28
An organic EL device was formed in the same manner as in Example 18, except that the material of the second hole transport layer was replaced with compound (11k).
Example 29
An organic EL device was formed in the same manner as in Example 18, except that the material of the second hole transport layer was replaced with compound (12l).
Example 30
An organic EL device was formed in the same manner as in Example 18, except that the material of the second hole transport layer was replaced with compound (13m).
Example 31
An organic EL device was formed in the same manner as in Example 18, except that the material of the second hole transport layer was replaced with compound (14n).
Example 32
An organic EL device was formed in the same manner as in Example 18, except that the material of the second hole transport layer was replaced with compound (15o).
Example 33
An organic EL device was formed in the same manner as in Example 18, except that the material of the second hole transport layer was replaced with compound (16p).

Comparative example 1
An organic EL device was formed in the same manner as in Example 18, except that the material of the second hole transport layer was replaced with Comparative Compound 1.

Comparative example 2
An organic EL device was formed in the same manner as in Example 18, except that the material of the second hole transport layer was replaced with Comparative Compound 2.

Comparative example 3
An organic EL device was formed in the same manner as in Example 18, except that the material of the second hole transport layer was replaced with Comparative Compound 3.

For the obtained organic EL devices of Examples 18 to 33 and Comparative Examples 1 to 3, the voltage and external quantum efficiency at a brightness of 1000 cd were measured. In addition, the element life was measured and the results are shown in Table 2 below.
The device life was measured as the time required for the device's luminance (initial brightness) to decay to 50% in constant current measurement at 100 mA/cm ² .

The organic EL devices of Examples 18 to 33 and Comparative Examples 1 to 3 all emitted blue light.
As shown in Table 2, the organic EL devices of Examples 18 to 33 having hole transport layers containing the compound of the present invention can be driven at low voltage and have high external quantum efficiency and long device life. Indicated. The compound represented by formula (1-1) has a bulky group Arb at the 2-position of the fluorene skeleton, making it a material with excellent thermal stability, and the N atom is directly bonded to the 3-position of the fluorene skeleton. As a result, the attack of nucleophilic and electrophilic compounds on the N atom is sterically suppressed, resulting in a material with excellent photostability and electrical stability. It is thought that this enabled us to achieve lower voltage, higher efficiency, and longer life.
On the other hand, the organic EL devices of Comparative Examples 1 to 3, which have hole transport layers containing comparative compounds, cannot necessarily be said to have good driving voltage, external quantum efficiency, and device life. The emitted light was a pale blue color, and it was not possible to obtain a sufficient color tone for use as a primary color for displays or lighting.

1 Organic EL element 2 Substrate 3 Second electrode (cathode)
4 Electron injection layer 5 Electron transport layer 6 Light emitting layer 7 Hole transport layer 8 Hole injection layer 9 First electrode (anode)

Claims (7)

General formula (1-1)
During the ceremony,
R ₁ to R ₆ are each independently hydrogen, deuterium, a halogen group, a linear, branched or cyclic alkyl group which may have a substituent, or a substituent a straight-chain, branched-chain or cyclic alkoxy group which may _be conjugated with _each other to form a ring;
Ara each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. is a fused polycyclic aromatic group,
Arb is an aromatic hydrocarbon group that may have a substituent, an aromatic heterocyclic group that may have a substituent, or a fused polycyclic aromatic group that may have a substituent. can be,
Arc each independently represents an aromatic hydrocarbon group that may have a substituent, an aromatic heterocyclic group that may have a substituent, or an aromatic heterocyclic group that may have a substituent. A good fused polycyclic aromatic group, where two Arcs are bonded to each other via a single bond to form a ring.
A compound represented by 2. The compound according to claim 1, wherein Arb is a phenyl group which may have a substituent. The two Arcs are each independently selected from a phenyl group which may have a substituent , or a naphthyl group which may have a substituent, where the two phenyl groups, or The compound according to claim 1 or 2, wherein the naphthyl group is bonded via a single bond to form a ring. A hole transport material containing the compound according to any one of claims 1 to 3. An organic electronic device comprising an organic electroluminescent element or an organic photoelectric conversion element having a hole transport layer between a cathode and an anode,
An organic electronic device characterized in that the hole transport layer contains the compound according to any one of claims 1 to 3. 6. The organic electronic device according to claim 5, comprising an organic electroluminescent element having a light emitting layer between the hole transport layer and the cathode. The light-emitting layer includes a host material and a guest material made of a light-emitting material,
7. The organic electronic device according to claim 6, wherein the host material is an electron transporting material or a dual charge transporting material having hole transporting properties and electron transporting properties.