KR20200066572A - A 2-subtituted fluorene-based compound, a hole transport material including the same, and an organic eletronic device including the same in a hoke transport layer - Google Patents

Abstract

The present invention provides a compound which can be used as a hole transport material having excellent hole injection/transport properties, electron blocking properties, photostability, electrical stability and thermal stability, a hole transport material including the compound, and an organic electronic device, including an organic electroluminescence (EL) device or organic photoelectric conversion device, provided with a hole transport layer including the compound, particularly an organic electronic device including an organic EL device having long life and high light-emitting efficiency. The compound is represented by the following Chemical Formula 3, wherein R_1 to R_6 and Ar_a to Ar_c are the same as defined in the specification.

Description

A 2-subtituted fluorene-based compound, a hole transport material including the same, and an organic eletronic, a 2-substituted fluorene-based compound, a hole transport material containing the compound, and an organic electronic device including the compound in a hole transport layer device including the same in a hoke transport layer}

The present invention relates to the provision of a new 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.

As an organic electronic device for mutually converting electrical energy and optical energy, it is known to include an organic electroluminescent element (organic EL element) or an organic photoelectric conversion element.

Among them, the organic EL device has a structure in which a light emitting material that emits light by an electric field is sandwiched between a cathode and an anode. The organic EL device is a device that emits a light emitting material by recombining holes and electrons injected from an electrode in a light emitting layer.

The organic EL device is self-luminous and has a wide viewing angle and excellent visibility. Therefore, the organic EL element is used as a display element such as a display. Further, the organic EL element is a thin solid element, can be reduced in weight, and has excellent strength. Therefore, a display using an organic EL element is useful not only for a stationary type such as a television, but also for mobile applications. In addition, a display element using an organic EL element can be easily changed in size, and is useful for lighting as it emits light from the entire surface.

The problems of the organic EL device include improvement in luminous efficiency (external quantum efficiency) and longevity. Various studies have been made so far to solve the above problems.

For example, in many cases, a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer are provided in the organic EL device in addition to the electrode and the light emitting layer. Usually, these layers are laminated in the order of 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, the probability of recombination of holes and electrons in the light emitting layer can be increased, and the light emission efficiency of the organic EL device can be improved.

The light emitting layer of the organic EL device is generally produced by doping a charge transporting compound called a host material with a fluorescent compound or a phosphorescent compound called a guest material. The holes and electrons injected from the electrode recombine in the light emitting layer formed of the host material and the guest material, so that the energy of the excited host material moves to the guest material, and the guest material is excited by the energy to be emitted as light energy, thereby efficiently emitting light Can get

In order to improve the probability of recombination of holes and electrons, it is important to efficiently transfer positive charges to the light-emitting layer, so it is necessary to adjust the transport balance of holes and electrons.

In order to adjust the transport balance of holes and electrons, there are a number of hole injection materials, hole mobility of hole transport materials, electron injection materials, electron mobility of electron transport materials, charge injection barriers at the layer interface, and the thickness of each film. You need to adjust the balance in consideration of factors.

However, since the transportability of holes and electrons of the material itself varies depending on the material, and a charge injection barrier occurs at the interface of the layer formed of another material, it is not easy to recombine the holes and electrons in the light-emitting layer in balance. Examples of a poor balance between charge injection and transport include a case in which either a hole or an electron is small, or a case in which one exits without recombining extremely much. In the case where the charge flows to the counter electrode, there is also a method of providing a layer to block the charge to trap the charge in the light emitting layer and to increase the recombination efficiency. In addition, high light emission efficiency can be obtained by the effect of trapping the excitation energy generated in the light emitting layer. Usually, the hole transport layer and the electron transport layer are often responsible for trapping the discharged charge and excitation energy in the light emitting layer, so the role of the hole transport material is very important.

The characteristics required for the hole transport material used to increase the recombination efficiency of the organic EL device are high hole transport properties and low electron transport properties, and the values of the band gap, ionization potential (IP), and electron affinity (Ea) are appropriate values. It is important to have 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, whereby the hole injection barrier into the light emitting layer can be made small. It is preferable that the electron affinity of the hole transport material is greater than the electron affinity of the light-emitting material, whereby an electron block effect can be obtained. On the other hand, the HOMO level is used in almost the same meaning as the ionization potential (IP), which is one of the charge injection characteristic indices, and the LUMO level is sometimes used in the same sense as the electron affinity (Ea).

Regarding the life of the organic EL device, the light stability and electrical stability of the material are important (for example, see Non-Patent Document 1 and Non-Patent Document 2). In a material having low light stability, the material is deteriorated by excitation energy in the light emitting layer. In addition, when the excitation energy of the hole transport layer is smaller than the excitation energy of the light emitting layer, the excitation energy generated in the light emitting layer moves to the hole transport layer, promotes deterioration of the hole transport material, and also leads to lower efficiency of the element, so that the excitation of the hole transport layer It is preferable that the energy is higher than the excitation energy of the light emitting layer. On the other hand, in materials with low electrical stability, the material is deteriorated by holes and electrons, resulting in low efficiency and short life.

Heat resistance and amorphous properties are also important for longevity of the device. In a material having low heat resistance, thermal decomposition occurs due to heat during device driving, and the material is deteriorated. Crystallinity is likely to occur in a material having low amorphous property, and the device is deteriorated. Therefore, the material used for the element is required to have high heat resistance and good amorphous properties.

The glass transition temperature (Tg) is used as a measure of the amorphous property, and when the Tg of the material is low, the Tg of the organic EL material is considered to be better as it is crystallized and changed into a non-uniform film even after a long time under room temperature conditions. It is preferable that Tg is at least 135°C or more in consideration of the device usage environment.

The same problem can also occur in an organic photoelectric conversion element.

For example, in patent document 1, the compound (1) represented by the following general formula (1) as a hole transport material used for a hole transport layer is formally described. However, Patent Document 1 does not show a production example of Compound (1), and there is no description or suggestion regarding the excellent effect exerted by the compound.

[Formula 1]

Further, Patent Document 2 reports compound (2) represented by the following formula (2) as a hole transport material used in the hole transport layer. Since the 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, it is considered that electrical stability and thermal stability are low. On the other hand, in the synthetic technique described in Patent Document 2, it is impossible to obtain a compound containing the 2-substituted fluorene skeleton of the present invention, and even a clue to predict the excellent effect of the compound is not found.

[Formula 2]

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

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

The present invention aims to provide a compound that can be used as a hole transport material having excellent hole injection or transport performance, electron block performance, light stability, electrical stability, and thermal stability.

Further, the present invention provides a hole transporting material containing the above-mentioned compound, and an organic electronic device comprising an organic EL element or an organic photoelectric conversion element having a hole-transporting layer containing the above-mentioned compound, in particular, a lifetime. An object of the present invention is to provide an organic electronic device comprising an organic EL element having a long and high luminous efficiency.

As a result of various studies, the inventors succeeded in synthesizing a new compound represented by Chemical Formula 3 shown below, and also, a hole transport material of an organic EL device or an organic photoelectric conversion device in which the same compound is included in an organic electronic device. As a result, the present invention has been completed by finding out that it is extremely useful, and in particular, it is possible to achieve high efficiency, long life, and low voltage driving of an organic EL device.

The present inventors estimate the reason why the organic EL device or the organic photoelectric conversion device included in the organic electronic device can be highly efficient and have a long life by using the compound represented by the following formula (3) as the hole transport layer material. .

That is, the compound represented by the following Chemical Formula 3 contains a 2-substituted fluorene skeleton defined by the same general formula, so that the material is bulky and rigid, and stacking between molecules is achieved. Is suppressed. As a result, it is estimated that the transfer energy from the light-emitting layer is suppressed because the compound exhibits high excitation energy, and the device is highly efficient. In addition, it is estimated that electrical stability, light stability and thermal stability increase by increasing the stiffness of the compound, and it also contributes to the long life of the organic EL element or the organic photoelectric conversion element included in the organic electronic device.

The gist of the present invention is as follows.

[1] Compound represented by the following formula (3):

[Formula 3]

In Chemical Formula 3,

R ¹ to R ⁶ are each independently of each other hydrogen, deuterium, halogen group, a linear, branched or cyclic alkyl group which may have a substituent, or a linear, branched or cyclic alkoxy group which may have a substituent. , Where R ¹ to R ⁴ Two adjacent ones may combine with each other to form a ring;

Ar ^a is each independently an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a condensed polycyclic aromatic group which may have a substituent;

Ar ^b is an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a condensed polycyclic aromatic group which may have a substituent;

Ar ^c is each independently a straight-chain, branched or cyclic alkyl group which may have a substituent, a straight-chain, branched or cyclic alkoxy group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent, An aromatic heterocyclic group which may have a substituent, or a condensed polycyclic aromatic group which may have a substituent, wherein two Ar ^c are bonded to each other through a single bond, a methylene group which may have a substituent, an oxygen atom or a sulfur atom. It may form a ring.

[2] The compound according to the above [1], wherein Ar ^b is a phenyl group which may have a substituent.

[3] Two Ar ^c are each independently selected from a methyl group which may have a substituent, a phenyl group which may have a substituent, or a naphthyl group which may have a substituent, wherein the two phenyl groups or a naphthyl group The compound described in [1] or [2] above, which may also be formed by bonding through a single bond to form a ring.

[4] A hole transport material containing the compound of any of [1] to [3] above.

[5] An organic electronic device comprising an organic electroluminescent element or an organic photoelectric conversion element having a hole transport layer between the cathode and the anode,

The hole transport layer is an organic electronic device, characterized in that it comprises a compound of any one of [1] to [3].

[6] The organic electronic device according to [5], wherein the organic electroluminescent element has 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 composed of the light emitting material,

The organic electronic device according to [6], wherein the host material is an electron transporting material or a positive charge transporting material having hole transporting property and electron transporting property.

The compound of the present invention can be used as a hole transport material capable of obtaining a hole transport layer having excellent light stability and electrical stability and thermal stability.

In particular, an organic electronic device comprising an organic EL element having a hole transporting layer containing the compound of the present invention has high luminous efficiency and a low voltage driving with long life.

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.

Hereinafter, the present invention will be described in more detail.

The present invention relates to compounds represented by the following formula (3):

[Formula 3]

In Chemical Formula 3,

R ¹ to R ⁶ are each independently of each other hydrogen, deuterium, halogen group, a linear, branched or cyclic alkyl group which may have a substituent, or a linear, branched or cyclic alkoxy group which may have a substituent. , Wherein two adjacent R ¹ to R ⁴ may combine with each other to form a ring;

Ar ^a is each independently an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a condensed polycyclic aromatic group which may have a substituent;

Ar ^b is an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a condensed polycyclic aromatic group which may have a substituent;

Ar ^c is each independently a straight-chain, branched or cyclic alkyl group which may have a substituent, a straight-chain, branched or cyclic alkoxy group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent, An aromatic heterocyclic group which may have a substituent, or a condensed polycyclic aromatic group which may have a substituent, wherein the two arcs are a single bond, a methylene group that may have a substituent, an oxygen atom, or a sulfur atom to bond to each other It may form.

In R ³ to R ⁶ and Ar ^c in the general formula (3), for example, a linear alkyl group is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group is mentioned.

In Formula 3, R ¹ to R ⁶ and Ar ^c are branched alkyl groups, for example, 1-methylethyl group, 1-methylpropyl group, 1-ethylpropyl group, 1-n-propylpropyl group, 1-methyl Butyl 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, 1-n-pentylheptyl group.

As the cyclic alkyl group in R ¹ to R ⁶ and Ar ^c in the formula (3), for example, a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or And polycyclic alkyl groups such as bicycloalkyl groups and tricycloalkyl groups.

Examples of the linear, branched or cyclic alkoxy group in R ¹ to R ⁶ and Ar ^c in the formula (3) include, for example, an alkoxy group in which an oxygen atom is located at the position of the linear, branched or cyclic alkyl group 1 above. .

The straight chain, branched chain, or cyclic alkyl group or alkoxy group preferably has 1 to 25 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 8 carbon atoms from the viewpoint of glass transition temperature and steric hindrance. Do.

As a ring formed by two adjacent R ¹ to R ⁴ in Formula 3 bonded to each other, for example, the adjacent two are bonded to each other and may have a propylene group, butylene group, pentylene group, or hex, which may have a substituent. And a ring formed as a silane group.

In R ³ to R ⁶ and Ar ^c in the formula (3), a linear, branched or cyclic alkyl group, or a substituent which the linear, branched or cyclic alkyl group or alkoxy group may have, for example, an alkoxy group and a halogen Flag.

Two or more substituents may be present, and when two or more are present, each may be different.

When R ¹ to R ⁶ are comprehensively determined, such as electrical stability, thermal stability, film-forming properties, and ease of synthesis and purification, the compounds represented by Chemical Formula 3 are most preferably hydrogen or methyl groups, respectively.

Examples of aromatic hydrocarbon groups, aromatic heterocyclic groups, and condensed polycyclic aromatic groups in Ar ^a and Ar ^c in Chemical Formula 3 are, for example, phenyl groups, biphenyl groups, terphenyl groups, naphthyl groups, anthracenyl groups, phenanthrenyl groups, fluorenyl groups, and the like. Neil group, pyrenyl group, perenyl group, fluoranthenyl group, triphenylenyl group, pyridyl group, pyrimidyl group, triazinyl group, furyl group, pyrrolyl group, thienyl group, quinolyl group, isoquinolyl group, benzofura Nyl group, benzothienyl group, indolyl group, carbazolyl group, benzooxazolyl group, benzothiazolyl group, quinoxalinyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, naphthylidi group And a nil group, a phenanthrolinyl group, an acridinyl group, and a carbonyl group. The aromatic hydrocarbon group, the aromatic heterocyclic group and the condensed polycyclic aromatic group in Ar ^a and Ar ^c preferably have a total of 6 to 25 carbon atoms and a hetero atom forming a ring, more preferably 6 to 20, and 6 to 18 It is more preferable.

Here, the two Ar ^c may be bonded to each other through a single bond, a methylene group that may have a substituent, an oxygen atom or a sulfur atom to form a ring.

Among them, two Ar ^c are each independently selected from 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, wherein the two phenyl groups or a naphthyl group It is preferable that a ring may be formed by bonding through a single bond.

Examples of the ring formed by bonding two Ar ^c to each other include a cyclopentane ring, a cyclohexane ring, an adamantane ring, and a fluorene ring, which form a five-membered ring and a spiro bond in the fluorene skeleton of Formula (3).

The aromatic hydrocarbon group, the aromatic heterocyclic group and the condensed polycyclic aromatic group in Ar ^b in the formula (3), for example, phenyl group, biphenyl group, terphenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, fluorenyl group, indenyl group, pyrene Neil 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, benzo Thienyl group, indolyl group, carbazolyl group, benzooxazolyl group, benzothiazolyl group, quinoxalinyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, naphthylinyl group, phenane Trolley group, acridinyl group, and carbonyl group.

As the aromatic hydrocarbon group, the aromatic heterocyclic group, and the condensed polycyclic aromatic group in Ar ^b , the total of carbon and hetero atoms forming a ring is preferably 6 to 25, more preferably 6 to 20, and further preferably 6 to 18 desirable.

When Ar ^b is present at the 2-position of the fluorene skeleton of Chemical Formula 3, the compound becomes a bulky and rigid molecular structure, and stacking between molecules is suppressed. Thereby, it is estimated that the electronic device including the organic EL element is highly efficient because the compound exhibits high excitation energy and the transfer energy from the light emitting layer to the hole transport layer containing the compound is suppressed.

In addition, since the rigidity of the compound increases by the presence of Ar ^b at the 2-position of the fluorene skeleton of Formula 3, the electrical stability, light stability and thermal stability increase, and the organic EL device comprising the compound in the hole transport layer or It is estimated that it also contributes to long life of the organic electronic device including the organic photoelectric conversion element.

In addition, the presence of Ar ^b at the 2-position of the fluorene skeleton of Chemical Formula 3 prevents the attack of the nucleophilic compound or the former electron compound of the N atom substituting at the adjacent 3-position to be sterically suppressed, thereby improving electrical stability, light stability and thermal stability. It is presumed that the stability is increased and it also contributes to the long life of the organic EL device containing the compound in the hole transport layer or the organic electronic device including the organic photoelectric conversion element.

The high excitation energy exhibited by the compound represented by the formula (3) is particularly advantageous for use as an electronic device including a blue light emitting organic EL element.

In the general formula (3), as Ar ^b , electrical stability, thermal stability, film-forming properties, and ease of synthesis and purification are comprehensively determined. A phenyl group, a biphenyl group, or a terphenyl group, which may have a substituent, is preferable, and may have a substituent. A phenyl group or a biphenyl group is more preferable, a phenyl group which may have a substituent is more preferable, and a phenyl group having no substituent is most preferred.

Substituents which may be included in the aromatic hydrocarbon group, the aromatic heterocyclic group and the condensed polycyclic aromatic group in Ar ^a to Ar ^c in the formula (3) include, for example, deuterium atoms; Cyano group; Nitro group; Halogen group; Linear or branched alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, and tert-butyl group; Alkyloxy groups such as methyloxy group, ethyloxy group, and propyloxy group; Alkenyl groups such as vinyl groups and allyl groups; Aryloxy groups such as phenyloxy group and phenyltrioxy group; Arylalkyloxy groups such as benzyloxy groups; Aromatic hydrocarbon groups such as phenyl group, biphenyl group, terphenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, fluorenyl group, indenyl group, pyrenyl group, perylene group, fluoranthenyl group, triphenylenyl group, or condensed polycyclic Aromatic groups; Pyridyl group, pyrimidyl group, triazinyl group, furyl group, pyrrolyl group, thienyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzooxazolyl group, benzo Aromatic heterocyclic groups such as thiazolyl group, quinoxalinyl group, benzoimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, naphthyridinyl group, phenanthrolinyl group, acridinyl group, and carbonyl group Or a condensed polycyclic aromatic group; Aryl vinyl groups such as styryl groups and naphthyl vinyl groups; And acyl groups such as acetyl groups.

Two or more substituents may be present, and when two or more are present, each may be different.

In addition, the substituents described for Ar ^a and Ar ^c in Formula 3 may be bonded to each other through a single bond, a methylene group that may have a substituent, an oxygen atom or a sulfur atom to form a ring.

In the general formula (3), in Ar ^a to Ar ^c , the aromatic hydrocarbon group, the aromatic heterocyclic group, and the condensed polycyclic aromatic group may have electrical stability, thermal stability, film-forming properties, and ease of synthesis and purification. Among the above examples, a phenyl group, a biphenyl group, a terphenyl group, or a naphthyl group, which may be substituted with one or two or more straight-chain alkyl groups having 1 to 10 carbon atoms or straight-chain alkyl groups having 1 to 5 carbon atoms, is preferably a methyl group, ethyl group, and propyl A group or a butyl group, or a phenyl group or a biphenyl group, in which one or two or more straight-chain alkyl groups having 1 to 3 carbon atoms may be substituted, is more preferable, and a methyl group or a phenyl group is most preferred.

Below, specific examples of the compound represented by the formula (3) are shown, but are not particularly limited to:

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Among the compounds represented by the above specific examples, examples of particularly preferred compounds, from the viewpoints of charge injection properties, charge transport properties, electrical stability, and thermal stability, include compounds (1a) to (16p) represented by the following formulas. have.

[Compound 1a]

[Compound 2b]

[Compound 3c]

[Compound 4d]

[Compound 5e]

[Compound 6f]

[Compound 7g]

[Compound 8h]

[Compound 9i]

[Compound 10j]

[Compound 11k]

[Compound 12l]

[Compound 13m]

[Compound 14n]

[Compound 15o]

[Compound 16p]

Since the compound represented by the formula (3) has the above properties, it can be used as a material for an organic EL element or a material for an organic photoelectric conversion element included in an organic electronic device, in particular, a hole transport layer of an organic EL element, preferably blue light emission It can be preferably used for the hole transport layer of an organic EL device. In particular, the compound enables high efficiency and long life of the organic EL element included in the organic electronic device.

The present invention also relates to a hole transport material containing a compound represented by the formula (3).

The purity of the compound represented by the formula (3) can be measured by high performance liquid chromatography (HPLC). High-speed liquid chromatography measures the purity of a sample by applying pressure to the mobile phase into which the sample is introduced, passing the solvent through the mobile phase at a high velocity to separate the sample (mixture) from the column, and detecting the separated sample in a detector. It is a way.

The molecular weight of the compound represented by the formula (3) can be measured by mass spectrometry (MS). Mass spectrometry is performed by ionizing a sample by applying a high voltage in a vacuum to a sample introduced from the sample introduction section, separating ions according to the mass charge ratio, and detecting the detection section.

The sample introduction section may be directly connected to gas chromatography (GC/MS), high-speed liquid chromatography (LC/MS), capillary electrophoresis (CE/MS), and may measure molecular weight while also measuring purity. On the other hand, a direct injection method (DI/MS) in which a sample is directly ionized may also be employed.

Various ionization methods are employed as the ion generating source. Examples include electron ionization (EI), high-speed atomic collision (FAB), electrospray ionization (ESI), and dielectric-coupled plasma (ICP).

Nuclear magnetic resonance spectrum (NMR) can be used to identify the compound represented by Formula 3. In the NMR measurement, since chemical shift and coupling information can be obtained according to the bonding state of the atom, a compound-specific spectrum can be obtained, and the compound can be identified. Measurement is made by dissolving a small amount of sample in various medium solvents.

Evaluation of the temperature stability of the compound represented by Chemical Formula 3 may be performed by differential scanning calorimetry (DSC). DSC measurement is performed by detecting a difference in heat amount from a standard sample when the sample undergoes a thermal change such as phase change or melting. DSC measurement shows the melting point of the compound and the glass transition temperature.

By measuring the ultraviolet visible absorption spectrum (UV/VIS), the fluorescence spectrum (PL), and the phosphorescence spectrum of the compound represented by the formula (3), not only can the UV absorption wavelength, fluorescent wavelength, and phosphorescence wavelength specific to the compound be known, but also Information such as bandgap, fluorescence quantum yield, and triplet energy can be obtained.

The HOMO level and LUMO level of the compound represented by Chemical Formula 3 can be measured by cyclic voltammetry (CV). In addition, ionization potential (IP) can also be used as the same index as the HOMO level.

In addition, a technique of obtaining an optical bandgap from the UV absorption wavelength and calculating the LUMO level (or Ea) from the HOMO level (or IP) can also be used.

One aspect of the organic electronic device of the present invention includes an organic EL device including a light emitting layer between a cathode and an anode, a hole transport layer disposed on the anode side of the light emitting layer, and the hole transport layer comprising a compound represented by Formula 3 And preferably includes a blue light emitting organic EL element.

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 device 1 shown in FIG. 1 has a first electrode 9 (anode) on the substrate 2, a hole injection layer 8, a hole transport layer 7, a light emitting layer 6, and electrons. The transport layer 5, the electron injection layer 4, and the second electrode 3 (cathode) have a stacked structure formed in this order.

The organic EL element included in the organic electronic device of the present invention may have a hole transport layer in which one or two or more layers are stacked. Similarly, another layer (for example, a light emitting layer and an electron transporting layer) of the organic EL device of the present invention may also be an aspect in which one or more layers are stacked.

In the organic EL device 1 shown in Fig. 1, the entire stacked structure constituting the organic EL device formed on the substrate 2 is made of an organic compound.

On the other hand, the organic EL element 1 shown in FIG. 1 is a hybrid organic-inorganic electroluminescent element (HOILED) in which a layer composed of an inorganic compound is included in a stacked structure constituting the organic EL element 1 formed on the substrate 2 Device). In this case, for example, in the organic EL device 1 shown in Fig. 1, an electron injection layer 4 made of an inorganic oxide as a layer made of an inorganic compound, and a hole injection layer 8 made of an inorganic oxide ) Can be provided. Since the inorganic compound is stable compared to the organic compound, the HOILED device is preferable because it has high resistance to oxygen or water compared to an organic EL device that does not include a layer made of an inorganic compound.

In addition, the case where the electron injection layer 4 and the hole injection layer 8 are provided in the organic EL element 1 shown in FIG. 1 is described as an example, for example, the electron injection layer 4 and/or Alternatively, the hole injection layer 8 may not be provided. In the organic EL device 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, or a hole injection layer 8 made of an organic 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 extracts light to the side opposite to the substrate 2 side, or a bottom emission type that extracts light to the substrate 2 side.

In addition, the organic EL element 1 shown in FIG. 1 is a net structure in which a first electrode 9 serving as an anode is disposed between the substrate 2 and the light emitting layer 6.

As the material of the substrate 2, resin materials such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, cycloolefin polymer, polyamide, polyethersulfone, polymethyl methacrylate, polycarbonate, polyarylate, and quartz Glass materials, such as glass and soda glass, etc. are mentioned, These 1 type(s) or 2 or more types can be used.

When the organic EL element 1 is of the bottom emission type, a transparent material is used for the substrate 2.

When the organic EL element 1 is a top emission type, a transparent or 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, an oxide film (insulating film) formed on the surface of a metal substrate such as stainless steel, and a substrate made of a resin material.

In the organic EL element 1 shown in Fig. 1, the first electrode 9 functions as an anode. Materials of the first electrode 9 include, for example, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), FTO (Fluorine Oxide), In ₃ O ₃ , SnO ₂ , Sb-containing SnO ₂ , Al And oxides such as ZnO. Among them, it is preferable to use ITO, IZO, and FTO as the first electrode 9 material.

The material that can be used for the hole injection layer 8 is selected from the viewpoints of the work function of the anode, the IP relationship of the hole transport layer, and charge transport characteristics. For example, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (abbreviation:PEDOT:PSS), a phthalocyanine compound represented by copper phthalocyanine (abbreviation:CuPc), molybdenum oxide (MoO _x ), Billions such as vanadium oxide (V ₂ O ₅ ), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN) Scepter heterocyclic compounds can be used. As long as it is a compound having appropriate IP and charge transport properties, various organic compounds and inorganic compounds can be selected regardless of the small molecule or the polymer. Moreover, you may use these materials in combination of 2 or more type.

The hole transport layer 7 includes a compound represented by Chemical Formula 3. The compound has an appropriate HOMO level and LUMO level by having a 2-substituted fluorene skeleton defined by the above general formula, and is excellent in light stability, electrical stability and thermal stability. Therefore, the efficiency of recombination of charges in the light emitting layer can be increased, and an organic EL device having a long life can be realized with higher light emission efficiency.

The compound represented by Chemical Formula 3 may be used alone as a hole transport material, or may be used by mixing an existing hole transport material with one or two or more types. Existing hole transport 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 -Aromatic amine compounds such as di(p-tolyl)amino]phenyl]cyclohexane (abbreviation: TAPC), or 4,4',4'-tri-9-carbazolyl triphenylamine (abbreviation: TCTA), 1, Carbazole derivatives such as 3-bis (carbazole-9-yl) benzene (abbreviation: mCP) can be used.

A fluorescent material or a phosphorescent material can be used for the light emitting layer 6. The luminescent material can also be used by containing a luminescent material (guest material) in a host material for charge transport and charge recombination.

As the host material, a material of positive charge transport having hole transport property and electron transport property may be used. Further, since the hole transport material of the present invention also has excellent electron blocking performance, an electron transport material can also be used for the host material.

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

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

Materials used for the electron transport layer 5 include, for example, metal complexes of quinolinol derivatives including Alq3 and BAlq, anthracene derivatives, pyridine derivatives, pyrimidine derivatives, benzoimidazole derivatives, quinoxaline derivatives, and phenanthroline Derivatives, triazine derivatives, carbazole derivatives, and triazole derivatives can be used.

When an electron transport layer including a material having an appropriate LUMO level is provided between the light emitting layer and the cathode or electron injection layer, the electron injection barrier from the cathode or electron injection layer to the electron transport layer is relaxed, and electron injection from the electron transport layer to the light emitting layer is also provided. Barriers can be relaxed. In addition, if the material has an appropriate HOMO level, it is possible to block holes flowing out to the counter electrode without recombination in the light emitting layer, trap holes in the light emitting layer, and increase the recombination efficiency in the light emitting layer.

The material used for the electron injection layer 4 is selected from the viewpoints of the work function of the cathode and the LUMO level of the electron transport layer. When the 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 later. 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, an alkali metal or an alkaline earth metal, lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride or cesium carbonate can be used.

The cathode of the organic EL device serves to inject electrons into the electron injection layer or electron transport layer. As the negative electrode, materials that act as a negative electrode are used, such as various metal materials and various alloys having 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 the bottom emission method is employed, an opaque electrode made of metal can be used as the cathode. Further, the cathode may also be used as a reflective electrode.

When employing the top emission method, transparent electrodes such as ITO and IZO can be used as the cathode. Here, since ITO has a large work function, in addition to making electron injection difficult, a sputtering method or an ion beam deposition method can be used to form an ITO film, but there is a possibility of damage to an electron transport layer or the like during film formation. Accordingly, a magnesium layer or a copper phthalocyanine layer may be provided between the electron transport layer and the ITO to improve electron injection and reduce damage to the electron transport layer during film formation.

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

[Example]

Hereinafter, with reference to Examples of the present invention will be described in more detail, but it shows a specific embodiment of the present invention, the present invention is not limited thereto.

[Synthesis of compounds]

Example 1

Compound (1a) was synthesized by the synthetic route shown below.

[Scheme 1]

[Scheme 2]

Compound (A1) was synthesized by the method shown below.

1,4-dibromo-2,5-diiodobenzene (25.0 g, 51 mmol), phenylboronic acid (13.1 g, 107 mmol), tetrakistriphenyl in a 300 mL shrink tube equipped with a stirrer Phosphine palladium (8.95g, 7.7mmol), toluene (200mL), water (80mL), and potassium carbonate (35.7g, 258mmol) were added, sealed and stirred at 100°C for 16 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature for 4 hours, and the precipitate was collected. Then, the desired compound (A1) was obtained by washing with water and washing with methanol (amount 15.6 g, yield 78.4%).

Compound (A2) was synthesized by the method shown below.

A 500 mL four-necked flask, argon-substituted with a stirrer, was added with compound (A1) (3.88 g, 10 mmol) and tetrahydrofuran (200 mL), stirred and cooled to -78°C. To this, 1.6 M-n-butyl lithium·hexane solution (7.64 mL, 12 mmol) was added dropwise. After stirring for 1 hour, benzophenone (2.16 g, 12 mmol) was added, and after stirring for an additional hour, the cooling bus was separated and heated to room temperature at -78°C, followed by stirring for 1 hour. Distilled water (50 mL) was added little by little to stop the reaction. The contents were transferred to a separatory funnel, dichloromethane was added, the organic phase and the aqueous phase were separated to remove the aqueous phase, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was purified by washing with cyclohexane to obtain the desired compound (A2) (amount 4.23 g, yield 86.1%).

Compound (A3) was synthesized by the method shown below.

A compound (A2) (4.20 g, 8.54 mmol), chloroform (100 mL), and trifluoromethanesulfonic acid (100 μl, 1.1 mmol) was added to a 100 mL shrink tube equipped with a stirrer, and sealed. Stir at room temperature for 2 hours. Then, saturated aqueous sodium hydrogen carbonate solution (30 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was purified by washing with hexane to obtain the target compound (A3) (amount 3.94 g, yield 97%).

Compound (B1) was synthesized by the method shown below.

4-amino-p-terphenyl (3.15g, 12.8mmol), 4-bromobiphenyl (2.5g, 10.7mmol), tris(dibenzylideneacetone)dipa in a 300mL shrink tube equipped with a stirrer Radium (0) (196 mg, 0.21 mmol), toluene (80 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (176 mg, 0.43 mmol), and t-butoxy sodium (1.55 g) , 16mmol), and sealed and stirred at 100°C for 5 hours. Thereafter, the reaction vessel was allowed to cool to room temperature, the precipitate was collected, and washed with water and ethyl acetate to obtain the desired compound (B1) (yield 4.11 g, yield 96%).

Compound (1a) was synthesized by the method shown below.

Compound (A3) (2.5g, 5.23mmol), compound (B1) (1.5g, 3.77mmol), bis(tri-t-butylphosphine)paradium ( 0) (77 mg, 0.15 mmol), xylene (60 mL), and t-butoxy sodium (543 mg, 5.66 mmol) were added, and the mixture was stirred at 130° C. for 16 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 2/1), and then washed with cyclohexane to obtain the desired compound (1a) (yield 1.01 g, yield 34). %). MS: [M+H] ⁺ = 790

Example 2

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

[Scheme 3]

[Reaction Scheme 4]

Compound (A4) was synthesized by the method shown below.

A 500 mL four-necked flask, argon-substituted with a stirrer, was added with compound (A1) (3.88 g, 10 mmol) and tetrahydrofuran (200 mL), stirred and cooled to -78°C. To this, 1.6 M-n-butyl lithium·hexane solution (7.64 mL, 12 mmol) was added dropwise. After stirring for 1 hour, fluorenone (2.16 g, 12 mmol) was added, and after stirring for an additional hour, the cooling bus was separated and heated to room temperature at -78°C, followed by stirring for 1 hour. Distilled water (50 mL) was added little by little to stop the reaction. The contents were transferred to a separatory funnel, dichloromethane was added, the organic phase and the aqueous phase were separated to remove the aqueous phase, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was purified by washing with cyclohexane to obtain the target compound (A4) (amount 2.85 g, yield 58.2%).

Compound (A5) was synthesized by the method shown below.

A compound (A4) (2.85 g, 5.82 mmol), chloroform (100 mL), and trifluoromethanesulfonic acid (100 μl, 1.1 mmol) was added to a 100 mL shrink tube equipped with a stirrer, and sealed. Stir at room temperature for 2 hours. Then, saturated aqueous sodium hydrogen carbonate solution (30 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was purified by washing with hexane to obtain the target compound (A5) (amount 2.66 g, yield 89.8%).

Compound (B2) was synthesized by the method shown below.

4-amino-p-terphenyl (1.78g, 7.23mmol), 4-(4-bromophenyl)dibenzofuran (1.95g, 5.78mmol), Tris (Dibenzylideneacetone)diparadium (0) (110 mg, 0.12 mmol), toluene (60 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (99 mg, 0.24 mmol), and t -Sodium butoxy (0.73g, 7.23mmol) was added, and the mixture was stirred at 100°C for 5 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, the precipitate was collected, and washed with water and ethyl acetate to obtain the desired compound (B2) (yield 2.88 g, yield 98%).

Compound (2b) was synthesized by the method shown below.

Compound (A5) (2.12g, 4.50mmol), compound (B2)(1.46g, 2.99mmol), bis(tri-t-butylphosphine)paradium ( 0) (76.7 mg, 0.15 mmol), xylene (60 mL), and t-butoxy sodium (432 mg, 4.50 mmol) were added, and the mixture was stirred at 130° C. for 16 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 2/1), and then recrystallized with 2-propanol to obtain the desired compound (2b) (yield: 861 mg, yield) 33%). MS: [M+H] ⁺ =878

Example 3

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

[Scheme 5]

Compound (B3) was synthesized by the method shown below.

4-amino-p-terphenyl (0.72g, 2.94mmol), 4-(4-bromophenyl)dibenzothiophene (1.00g, 2.94mmol) in a 50mL shrink tube equipped with a stirrer, Tris(dibenzylideneacetone)diparadium(0) (27mg, 0.03mmol), toluene (20mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (24mg, 0.06mmol), and Sodium t-butoxy (0.35 g, 3.68 mmol) was added and sealed, and then stirred at 100° C. for 5 hours. Thereafter, the reaction vessel was allowed to cool to around room temperature, the precipitate was collected, and washed with water and ethyl acetate to obtain the desired compound (B3) (yield 1.30 g, yield 88%).

Compound (3c) was synthesized by the method shown below.

Compound (A5) (1.89g, 4.00mmol), compound (B3)(1.30g, 2.85mmol), bis(tri-t-butylphosphine)paradium ( 0) (53mg, 0.11mmol), xylene (30mL), and t-butoxy sodium (0.37g, 4.27mmol) were added, and the mixture was stirred at 130°C for 16 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained 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 desired compound (3c) (amount 572 mg) , Yield 23%). MS:m/z=893

Example 4

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

[Scheme 6]

Compound (A6) was synthesized by the method shown below.

Compound (A5) (4.00g, 8.48mmol), 4-amino-p-terphenyl (2.08g, 8.48mmol), tris(dibenzylideneacetone)diparadium in a 100mL shrink tube equipped with a stirrer (0) (80 mg, 0.085 mmol), toluene (40 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (72 mg, 0.17 mmol), and t-butoxy sodium (1.04 g, 10.6 mmol) was added, and the mixture was stirred at 100° C. for 2 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane=1/2) to obtain the desired compound (A6) (yield 3.6 g, yield 90%).

Compound (4d) was synthesized by the method shown below.

Compound (A6) (1.72g, 2.70mmol), 4-bromo-p-terphenyl (0.84g, 2.70mmol), bis(tri-t-butylphosphine) in a 100mL shrink tube equipped with a stirrer Fin) Palladium (0) (41 mg, 0.081 mmol), xylene (18 mL), and t-butoxy sodium (0.37 g, 4.05 mmol) were added, and the mixture was stirred at 130° C. for 16 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, and the precipitate was collected and washed with toluene, methanol, and water. Then, 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 desired compound (4d) (amount) 1.53 g, yield 66%). MS:m/z=863

Example 5

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

[Scheme 7]

Compound (B4) was synthesized by the method shown below.

4-chlorophenylboronic acid (1.43g, 9.15mmol), 2-bromo-9,9-dimethylfluorene (2.50g, 9.15mmol), tetrakistry in a 100mL arbor-substituted shrink tube equipped with a stirrer Phenylphosphine palladium (211 mg, 0.183 mmol), toluene (33 mL), water (11 mL), and potassium phosphate (3.88 g, 18.3 mmol) were added, and the mixture was stirred at 100° C. for 2 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane=7/1), and washed with hexane to obtain the desired compound (B4) (yield 2.53 g, yield 91%).

Compound (5e) was synthesized by the method shown below.

Compound (A6)(1.37g, 2.16mmol), compound (B4)(0.99g, 3.24mmol), bis(tri-t-butylphosphine)paradium ( 0) (66 mg, 0.13 mmol), xylene (20 mL), and t-butoxy sodium (0.39 g, 4.32 mmol) were added, and the mixture was stirred at 130° C. for 5 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (40 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained mixture was purified by silica gel column chromatography (developing solvent: cyclohexane/toluene=3/2). Thereafter, the mixture was dissolved in toluene, and methanol was vapor-diffused and recrystallized to obtain the target compound (5e) (amount 0.58 g, yield 27%). MS:m/z=903

Example 6

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

[Scheme 8]

Compound (6f) was synthesized by the method shown below.

Compound (A6) (1.14g, 1.79mmol), 1-(4-bromophenyl)naphthalene (0.59g, 1.97mmol), bis(tri-t-butyl) in a 50mL shrink tube equipped with a stirrer Phosphine) Palladium (0) (27mg, 0.054mmol), xylene (12mL), and t-butoxy sodium (0.26g, 2.69mmol) were added, and the mixture was stirred at 130°C for 16 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (10 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained mixture was purified by silica gel column chromatography (developing solvent: THF). Thereafter, recrystallization with toluene and washing with THF gave the desired compound (6f) (yield 0.70 g, yield 47%). MS:m/z=837

Example 7

Compound (7 g) was synthesized by the synthetic route shown below.

[Scheme 9]

1-(4-aminophenyl)naphthalene was synthesized by the method shown below.

4-bromoaniline (4.00 g, 23.3 mmol), 1-naphthylboronic acid (4.40 g, 25.6 mmol), tetrakistriphenylphosphine palladium (808 mg, in a 200 mL shrink tube equipped with a stirrer) 0.70 mmol), toluene (90 mL), water (30 mL), and tribasic potassium phosphate (14.8 g, 69.9 mmol) were added, and the mixture was stirred at 100° C. for 2 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained 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.

Compound (A5) (2.50 g, 5.28 mmol), 1-(4-aminophenyl) naphthalene (1.16 g, 5.28 mmol), tris (dibenzylidene acetone) dipa in a 100 mL shrink tube equipped with a stirrer Radium (0) (72 mg, 0.079 mmol), toluene (31 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (65 mg, 0.16 mmol), and t-butoxy sodium (0.63 g) , 6.59mmol), sealed and stirred at 100°C for 2 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane=2/1) to obtain the desired compound (A7) (yield 3.0 g, yield 93%).

Compound (7 g) was synthesized by the method shown below.

Compound (A7) (3.00g, 4.91mmol), 1-(4-bromophenyl)naphthalene (2.00g, 7.06mmol), bis(tri-t-butyl) in a 100mL shrink tube equipped with a stirrer Phosphine) Palladium (0) (120mg, 0.24mmol), xylene (48mL), and t-butoxy sodium (0.79g, 8.25mmol) were added, and the mixture was stirred at 130°C for 3 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (40 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane=2/1). Thereafter, the mixture was recrystallized from acetone and methanol, and washed with ethyl acetate to obtain the target compound (7 g) (amount 1.61 g, yield 40%). MS:m/z=811

Example 8

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

[Scheme 10]

Compound (8h) was synthesized by the method shown below.

Compound (A6) (2.42g, 3.81mmol), 2-(4-bromophenyl)naphthalene (1.19g, 4.19mmol), bis(tri-t-butyl) in a 100 mL shrink tube equipped with a stirrer Phosphine) Palladium (0) (58.4mg, 0.11mmol), toluene (38mL), and t-butoxy sodium (0.51g, 5.33mmol) were added, and the mixture was stirred at 100°C for 5 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (20 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane=2/1). Then, the mixture was recrystallized with a mixed solvent of toluene and methanol, and washed with THF to obtain the desired compound (8h) (yield 2.00 g, yield 63%). MS:m/z=837

Example 9

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

[Scheme 11]

2-(4-aminophenyl)naphthalene was synthesized by the method shown below.

4-bromoaniline (2.70g, 15.7mmol), 2-naphthylboronic acid (2.99g, 17.4mmol), tetrakistriphenylphosphine palladium (543mg, 0.47 mmol), toluene (30 mL), water (6 mL), and tribasic potassium phosphate (3.81 g, 31.4 mmol) were added, and the mixture was stirred at 100° C. for 2 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane=1/3) to obtain the desired 2-(4-aminophenyl)naphthalene (amount 3.33 g, yield 96%).

Compound (A8) was synthesized by the method shown below.

Compound (A5) (2.12g, 4.50mmol), 2-(4-aminophenyl)naphthalene (1.04g, 4.73mmol), tris(dibenzylideneacetone)dipa in a 100mL shrink tube equipped with a stirrer Radium (0) (21 mg, 0.023 mmol), toluene (23 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (19 mg, 0.045 mmol), and t-butoxy sodium (0.65 g) , 6.75mmol), and sealed and stirred at 100°C for 2 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (40 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained mixture was purified by silica gel column chromatography (developing solvent: cyclohexane/toluene=2/1), and washed with methanol to obtain the desired compound (A8) (yield 2.7 g, yield 98%).

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

Compound (A8) (2.70g, 4.47mmol), 2-(4-bromophenyl)naphthalene (2.21g, 4.69mmol), bis(tri-t-butyl) in a 100mL shrink tube equipped with a stirrer Phosphine) Palladium (0) (22.8mg, 0.045mmol), toluene (33mL), and t-butoxy sodium (0.65g, 6.71mmol) were added, and the mixture was stirred at 100°C for 2 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (40 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained mixture was purified by silica gel column chromatography (developing solvent: cyclohexane/toluene=3/1). Then, the mixture was recrystallized with toluene, and the desired compound (9i) was obtained by washing with toluene and methanol (amount 1.89 g, yield 52%). MS:m/z=811

Example 10

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

[Scheme 12]

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

Compound (A8) (6.70g, 1.79mmol), 1-(4-bromophenyl)naphthalene (2.13g, 7.53mmol), bis(tri-t-butyl) in a 100mL shrink tube equipped with a stirrer Phosphine) Palladium (0) (35mg, 0.068mmol), toluene (35mL), and t-butoxy sodium (0.82g, 8.55mmol) were added, and the mixture was stirred at 100°C for 2 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (20 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane=2/1). Thereafter, the mixture was recrystallized with a mixed solvent of dichloromethane, acetone and methanol, and washed with isopropanol to obtain the desired compound (10j) (yield 2.00 g, yield 36%). MS:m/z=811

Example 11

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

[Scheme 13]

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) 0.1 mmol), toluene (30 mL), water (6 mL), and tribasic potassium phosphate (4.25 g, 20.0 mmol) were added, and the mixture was stirred at 100°C for 3 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained mixture was purified by silica gel column chromatography (developing solvent: toluene), and washed with methanol to obtain the desired 9-(4-chlorophenyl)phenanthrene (yield 2.63 g, yield 91%).

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

Compound (A6) (2.57g, 4.04mmol), 9-(4-chlorophenyl)phenanthrene (1.43g, 4.95mmol), bis(tri-t-butyl) in a 100mL shrink tube equipped with a stirrer Phosphine) Palladium (0) (35mg, 0.068mmol), toluene (23mL), and t-butoxy sodium (0.65g, 6.75mmol) were added, sealed and stirred at 100°C for 3 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (40 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over 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, recrystallization with methylcyclohexane and washing with 2-methoxy-2-methylpropane gave the desired compound (11k) (amount 1.84 g, yield 38%). MS:m/z=887

Example 12

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

[Scheme 14]

[Scheme 15]

Compound (A9) was synthesized by the method shown below.

A compound (A1) (2.50 g, 6.44 mmol) and tetrahydrofuran (128 mL) were added to an argon-substituted 300 mL four-necked flask equipped with a stirrer, stirred, and cooled to -78°C. To this, 1.6 M-n-butyl lithium·hexane solution (4.51 mL, 7.09 mmol) was added dropwise. After stirring for 1 hour, 4-phenylbenzophenone (2.00g, 7.73mmol) was added, and after stirring for an additional hour, the cooling bus was separated and heated to room temperature at -78°C, followed by stirring for 1 hour. Distilled water (50 mL) was added little by little to stop the reaction. The contents were transferred to a separatory funnel, ethyl acetate was added, the organic phase and the aqueous phase were separated to remove the aqueous phase, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was purified by washing with hexane to obtain the desired compound (A9) (amount 2.45 g, yield 67%).

Compound (A10) was synthesized by the method shown below.

A compound (A9) (2.45 g, 4.31 mmol), dichloromethane (130 mL), and trifluoromethanesulfonic acid (120 μl, 1.3 mmol) was added to a 300 mL two-necked eggplant-shaped flask equipped with a stirrer, After sealing, the mixture was stirred at room temperature for 1 hour. Then, saturated aqueous sodium hydrogen carbonate solution (30 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over 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) (2.12g, 3.85mmol), 4-amino-p-terphenyl (0.94g, 3.85mmol), tris(dibenzylideneacetone)diparadium in a 100mL shrink tube equipped with a stirrer (0) (18 mg, 0.019 mmol), toluene (40 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (16 mg, 0.039 mmol), and t-butoxy sodium (0.46 g, 4.81 mmol) was added and the mixture was stirred at 100° C. for 1 hour. Then, 1-(4-bromophenyl)naphthalene (1.20g, 4.23mmol), bis(tri-t-butylphosphine)paradium(0)(20mg, 0.039mmol), toluene (20mL) in the reaction vessel And t-butoxy sodium (0.46g, 4.81mmol) was added and sealed, and then stirred at 100°C for 16 hours. The reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained 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 desired compound (12l). (Yield 1.30 g, yield 37%). MS:m/z=915

Example 13

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

[Scheme 16]

[Scheme 17]

Compound (A12) was synthesized by the method shown below.

A compound (A1) (3.0 g, 7.7 mmol) and tetrahydrofuran (150 mL) were added to a 300 mL four-necked flask equipped with a stirrer, and stirred and cooled to -78°C. To this, 1.6 M-n-butyl lithium·hexane solution (5.39 mL, 8.50 mmol) was added dropwise. After stirring for 1 hour, 2-phenyl-9-fluorenone (2.38g, 9.24mmol) was added, followed by stirring for an additional hour, the cooling bus was removed, heated to room temperature at -78°C, and stirred for 1 hour. Did. Distilled water (50 mL) was added little by little to stop the reaction. The contents were transferred to a separatory funnel, ethyl acetate was added, the organic phase and the aqueous phase were separated to remove the aqueous phase, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was purified by washing with hexane to obtain the target compound (A12) (amount 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 added to a 100 mL two-necked eggplant flask equipped with a stirrer and argon-substituted, After sealing, the mixture was stirred at room temperature for 1 hour. Thereafter, saturated aqueous sodium hydrogen carbonate solution (20 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over 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) (amount 3.07 g, yield 88%).

Compound (A14) was synthesized by the method shown below.

Compound (A13) (3.0g, 5.48mmol), 4-amino-p-terphenyl (1.34g, 5.46mmol), tris(dibenzylideneacetone)diparadium in a 100mL shrink tube equipped with a stirrer (0) (50 mg, 0.055 mmol), toluene (30 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (45 mg, 0.109 mmol), and t-butoxy sodium (0.66 g, 6.85 mmol) was added, and the mixture was stirred at 100° C. for 2 hours. Thereafter, the reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (40 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The desired compound (A14) was obtained by recrystallizing the concentrated obtained mixture with toluene (amount 2.65 g, yield 68%).

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

Compound (A14) (2.65g, 3.72mmol), 1-(4-bromophenyl)naphthalene (1.15g, 4.09mmol), toluene (20mL), bis() Tri-t-butylphosphine) palladium (0) (29mg, 0.056mmol), and t-butoxy sodium (0.45g, 4.65mmol) were added, and the mixture was stirred at 100°C for 2 hours. The reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (20 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane=1/1), and then recrystallized from cyclohexane. Further, recrystallization was performed with a mixed solvent of dichloromethane, acetone, and methanol, and the desired compound (13m) was obtained by washing with isopropanol (amount 2.36 g, yield 69%). MS:m/z=913

Example 14

Compound (14n) was synthesized by the method shown below.

[Reaction Scheme 18]

[Scheme 19]

Compound (A15) was synthesized by the method shown below.

A compound (A1) (2.60 g, 6.7 mmol) and tetrahydrofuran (140 mL) were added to an argon-substituted 300 mL four-necked flask equipped with a stirrer, stirred, and cooled to -78°C. To this, 1.6M-n-butyl lithium·hexane solution (5.12 mL, 8.04 mmol) was added dropwise. After stirring for 1 hour, 11H-benzo[b]fluorenone-11-one (1.70g, 7.37mmol) was added, and after stirring for an additional hour, the cooling bus was removed and the temperature was raised from -78°C to room temperature. , And stirred for 1 hour. Distilled water (50 mL) was added little by little to stop the reaction. The contents were transferred to a separatory funnel, ethyl acetate was added, the organic phase and the aqueous phase were separated to remove the aqueous phase, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The obtained mixture was purified by washing with hexane to obtain the target compound (A15) (amount 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 added to a 100 mL two-necked eggplant-shaped flask equipped with a stirrer, 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 to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over 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) (amount 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), tris (dibenzylidene acetone) diparadium in a 100 mL shrink tube equipped with a stirrer (0) (15 mg, 0.02 mmol), toluene (35 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (14 mg, 0.03 mmol), and t-butoxy sodium (0.39 g, 4.10 mmol) was added, and the mixture was stirred at 100° C. for 1 hour. The reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (40 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained mixture was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane=1/2) to obtain the desired compound (A17) (yield 2.08 g, yield 92%).

Compound (14n) was synthesized by the method shown below.

Compound (A17) (2.2g, 3.28mmol), 1-(4-bromophenyl)naphthalene (1.02g, 3.61mmol), toluene (35mL), bis( Tri-t-butylphosphine)paradium(0) (17mg, 0.03mmol), and t-butoxy sodium (0.39g, 4.10mmol) were added, and the mixture was stirred at 100°C for 2 hours. The reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (40 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained 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 desired compound (14n) (yield 1.61 g, yield 55). %). MS:m/z=887

Example 15

Compound (15o) was synthesized by the method shown below.

[Scheme 20]

Compound (15o) was synthesized by the method shown below.

Compound (A13) (2.00g, 3.65mmol), 2-(4-aminophenyl)naphthalene (0.80g, 3.65mmol), tris(dibenzylideneacetone)dipa in a 100mL shrink tube equipped with a stirrer Radium (0) (33 mg, 0.037 mmol), toluene (25 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (30 mg, 0.037 mmol), and t-butoxy sodium (0.53 g) , 5.48mmol), and sealed and stirred at 100°C for 1 hour. Then, 2-(4-bromophenyl)naphthalene (1.24 g, 4.39 mmol), bis (tri-t-butylphosphine) palladium (0) (28 mg, 0.055 mmol), toluene (25 mL) in the reaction vessel. And t-butoxy sodium (0.53g, 5.48mmol), sealed and stirred for 2 hours at 100°C. The reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (30mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained 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 desired compound (15o) ( Quantity 1.30 g, yield 41%). MS:m/z=887

Example 16

Compound (16p) was synthesized by the method shown below.

[Scheme 21]

Compound (16p) was synthesized by the method shown below.

Compound (A16) (0.78g, 1.50mmol), 2-(4-aminophenyl)naphthalene (0.33g, 1.50mmol), tris(dibenzylideneacetone)dipa in a 100mL Shrink tube equipped with a stirrer Radium (0) (6.9 mg, 0.008 mmol), toluene (8 mL), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (6.2 mg, 0.015 mmol), and t-butoxy sodium ( 0.18 g, 1.88 mmol) was added, and after being sealed, the mixture was stirred at 100°C for 1 hour. Then, 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 and sealed, followed by stirring at 100°C for 4 hours. The reaction vessel was allowed to cool to near room temperature, the lid was opened, and water (30 mL) was added thereto. After the contents were transferred to a separatory funnel to separate the organic phase from the aqueous phase, the aqueous phase was removed, and the organic phase was further washed with water. The organic phase was dried over sodium sulfate. Thereafter, sodium sulfate was removed by filtration, and the organic phase was concentrated. The concentrated obtained 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 desired compound (16p) (amount 0.69) g, yield 53%). MS:m/z=861

Example 17

DSC measurements were made for the compounds (1a) to (16p) synthesized in Examples 1 to 16, and Comparative Compounds 1 to 3 shown below.

[Scheme 22]

Table 1 shows the Tg and decomposition temperatures.

As shown in Table 1, it can be seen that the compound of the present invention is a material having a Tg of 135°C or higher and a high decomposition temperature, which is excellent in temperature stability. It is believed that Arb at the 2-position of the fluorene skeleton of Formula 3 acts as one factor leading to desirable temperature stability.

In addition, since it is considered to have higher temperature stability in that it exhibits a high Tg of 10°C or more even when compared with a comparative compound, application to a vehicle type organic EL device or the like can be expected.

[Preparation of organic EL element]

Example 18

A compound HAT-CN of Formula 4 below was vacuum-deposited to a thickness of 10 nm on a glass substrate on which ITO (indium tin oxide) having a thickness of 110 nm was formed, and a hole injection layer was formed. Compound HT1 of Chemical Formula 4 below was vacuum-deposited to a thickness of 80 nm on the hole injection layer to form a first hole transport layer. Subsequently, the above 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. Subsequently, on the second hole transport layer, the compound BD1 of the following formula 4 is used as the guest material, the compound BH1 of the following structural formula is used as the host material, and a light emitting layer with a thickness of 25 nm is formed with the content of the guest material in the light emitting layer as 4% by weight. Did. Subsequently, an electron transport layer was formed by sequentially vacuum-depositing Compound HB1 (25 nm) of Formula 4 and Compound ET1 (10 nm) of Formula 4 on the emission layer. Thereafter, 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.

[Formula 4]

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 for the second hole transport layer was changed to compound (3c).

Example 21

An organic EL device was formed in the same manner as in Example 18, except that the material for the second hole transport layer was changed to compound (4d).

Example 22

An organic EL element 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 for the second hole transport layer was changed to compound (6f).

Example 24

An organic EL device was formed in the same manner as in Example 18, except that the material for the second hole transport layer was changed to 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 for 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 for 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 changed to 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 changed to 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 changed to compound (16p).

Comparative Example 1

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

The obtained organic EL devices of Examples 18 to 33 and Comparative Examples 1 to 3 were measured for voltage at a luminance of 1000 cd and external quantum efficiency. In addition, the device life was measured and the results are shown in Table 2 below.

The device life was measured by measuring the constant current of 100 mA/cm 2 as the time until the light emission luminance (initial luminance) of the device decayed to 50%.

On the hole transport layer
Compound used Voltage
(V) External quantum efficiency
(%) Device life (h) Chromaticity coordinate (x,y) x y Example 18 Compound (1a) 4.18 8.96 126 0.138 0.116 Example 19 Compound (2b) 4.19 8.69 177 0.138 0.117 Example 20 Compound (3c) 4.14 8.05 153 0.136 0.115 Example 21 Compound (4d) 4.53 7.27 176 0.135 0.126 Example 22 Compound (5e) 4.15 7.68 206 0.137 0.118 Example 23 Compound (6f) 4.50 7.45 260 0.135 0.127 Example 24 Compound (7 g) 4.35 7.86 294 0.138 0.115 Example 25 Compound (8h) 4.34 7.52 328 0.138 0.113 Example 26 Compound (9i) 4.12 8.73 302 0.135 0.117 Example 27 Compound (10j) 4.17 8.37 228 0.137 0.112 Example 28 Compound (11k) 4.13 8.38 260 0.137 0.113 Example 29 Compound (12l) 4.30 7.34 186 0.138 0.117 Example 30 Compound (13m) 4.22 7.09 317 0.138 0.120 Example 31 Compound (14n) 4.13 8.38 260 0.137 0.112 Example 32 Compound (15o) 4.20 8.09 315 0.138 0.117 Example 33 Compound (16p) 4.19 8.10 305 0.137 0.112 Comparative Example 1 Comparative Compound 1 5.67 5.06 84 0.137 0.137 Comparative Example 2 Comparative Compound 2 7.20 3.23 2 0.138 0.116 Comparative Example 3 Comparative Compound 3 4.33 7.55 109 0.136 0.119

The organic EL devices of Examples 18 to 33 and Comparative Examples 1 to 3 all emit blue light. As shown in Table 2, the organic EL devices of Examples 18 to 33 having the hole transport layer containing the compound of the present invention exhibited high external quantum efficiency and long device life while being capable of low voltage driving. The compound represented by the formula (3) has a bulky group Arb at the 2-position of the fluorene skeleton, and thus becomes a material having excellent thermal stability, and the N atom is directly bonded to the 3-position of the fluorene skeleton, thereby the nucleophilic compound of the N reactor It is believed that the attack of the ora electron-electron compound is suppressed in three dimensions, and becomes a material having excellent light stability and electrical stability, and it is possible to achieve low voltage, high efficiency and long life of the organic EL device containing the compound in the hole transport layer. .

On the other hand, the organic EL devices of Comparative Examples 1 to 3 having a hole transport layer containing a comparative compound are not necessarily said to have good driving voltage, external quantum efficiency, and device life, and further, the organic EL devices of Comparative Example 1 The light emission is light blue, and a sufficient color tone for use as three primary colors, such as a display or lighting, cannot be obtained.

1: Organic EL device
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)

Compound represented by the formula (3):
[Formula 3]

In Chemical Formula 3,
R ¹ to R ⁶ are each independently of each other hydrogen, deuterium, halogen group, a linear, branched or cyclic alkyl group which may have a substituent, or a linear, branched or cyclic alkoxy group which may have a substituent. , Wherein two adjacent R ¹ to R ⁴ may combine with each other to form a ring;
Ar ^a is each independently an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a condensed polycyclic aromatic group which may have a substituent;
Ar ^b is an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a condensed polycyclic aromatic group which may have a substituent;
Ar ^c is a straight-chain, branched or cyclic alkyl group which may have a substituent each independently of each other, a straight-chain, branched or cyclic alkoxy group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, An aromatic heterocyclic group which may have a substituent, or a condensed polycyclic aromatic group which may have a substituent, wherein two Ar ^c are bonded to each other through a single bond, a methylene group which may have a substituent, an oxygen atom or a sulfur atom. It may form a ring.
According to claim 1,
A compound in which Ar ^b is a phenyl group which may have a substituent.
The method according to claim 1 or 2,
Two Ar ^c are each independently selected from a methyl group which may have a substituent, a phenyl group which may have a substituent, or a naphthyl group which may have a substituent, wherein the two phenyl groups or the naphthyl group are single bonds. Compounds, which may be joined through to form a ring.
A hole transport material containing the compound of 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 the cathode and the anode,
The organic electronic device, characterized in that the hole transport layer contains the compound of any one of claims 1 to 3.
The method of claim 5,
And an organic electroluminescent element having a light emitting layer between the hole transport layer and the cathode.
The method of claim 6,
The light emitting layer includes a host material and a guest material made of a light emitting material,
The organic electronic device, characterized in that the host material is an electron transporting material, or a positive charge transporting material having hole transporting property and electron transporting property.

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