JP6580613B2 - Lighting for plant cultivation using a novel triazine compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to lighting for plant cultivation using an organic electroluminescent element produced using a novel triazine compound that is excellent in heat resistance and can realize high efficiency, low voltage and long life of the element.

A liquid crystal display (LCD) is used for a small and medium-sized display device. However, since it is basically a light emitting / receiving type from a backlight, the configuration of the display for extracting light is complicated.
In contrast, organic electroluminescence displays (OLEDs) are self-luminous, do not require a backlight like LCDs, are simple in structure, can be made thinner and lighter, and are therefore portable display means. Suitable as
Furthermore, organic electroluminescence has been attracting attention as a light source element for several years, and research related to lighting using organic electroluminescence emission has been made for practical application throughout the country and abroad. Recently, it has become possible to produce a curved light source by depositing or applying an organic electroluminescent material on a plastic substrate. The use of display lighting using OLED is also being promoted in museums and the like, because light emission by organic electroluminescence does not emit ultraviolet rays that affect the exhibits.

When organic electroluminescence is used as a display, a material suitable for extracting the three primary colors (blue, green, red) of light is important. For example, 4,4′-bis [2,2-bis] is used as a blue material. (4-Methylphenyl) ethenyl] -1,1′-biphenyl (DTVBi) is a green fluorescent material such as tris (8-hydroxyquinolinolato) aluminum (Alq ₃ ) or tris [2-phenylpyridinate. -C ^2, N] iridium (III) is, as the red fluorescent material, 4- (dicyanomethylene) -2-t-butyl-6- (1,1,7,7-tetramethyljulolidyl-9 A pyran compound such as ethenyl) -4H-pyran (DCJTB) is 2,3,7,8,12,13,17,18-octaethyl-21H, 2 as a red phosphorescent material. 3H-porphyrin platinum complex [Pt (OEP)] and the like are known.

Recently, attention has been focused on light sources for plant cultivation. Open-air cultivation is generally used for plant cultivation, but indoor cultivation is promoted as a means of avoiding salt damage and radioactive contamination due to the tsunami of the Great East Japan Earthquake with the assistance of the relevant ministries and agencies. Under such circumstances, construction of a plant factory for producing plants indoors has been promoted by entry from different industries. Some plant factories use sunlight and others use artificial light. As light sources of artificial light, fluorescent lamps, HID lamps, and LED lamps are generally used.
However, fluorescent lamps are in a direction to be deceived by national measures and emit light in a wide range from ultraviolet to infrared together with HID lamps, so they are not efficient for plant cultivation. Moreover, although the LED lamp can take out single light required for cultivation, since it is a point light source, in order to illuminate the whole cultivation area | region, it is necessary to arrange | position many light sources, and wiring and a drive device become complicated. For this reason, the equipment becomes larger than necessary, and installation is restricted.
On the other hand, since the organic electroluminescence light source is a planar light emitter, it can be easily configured to illuminate a required area by singly or connecting a plurality of them, and even for a larger area, Roll to Roll It can be manufactured by applying a printing technique based on the method (Non-Patent Document 1).

  Plants grow by photosynthesis, but the wavelength regions that can be absorbed by chlorophylls possessed by plants are blue of 430 nm to 460 nm and red of 645 nm to 665 nm. Therefore, blue and red light is necessary for plant cultivation. Plants also absorb near-infrared light of 680 nm or more, but a phenomenon called let drop occurs, and the efficiency of photosynthesis decreases rapidly. In order to suppress this, when light of about 650 nm is irradiated at the same time, the light absorption effect of chlorophyll contained in the plant becomes very high as compared with the case where each is irradiated alone. This is generally called the Emerson effect (Non-Patent Document 2). Therefore, it is necessary to develop a red light emitting element that emits light at around 650 nm in organic electroluminescence.

As an example of an organic electroluminescence device emitting light at 600 nm or more in the red or near infrared region, a bis (2,3-diphenylquinoxaline) iridium (acetylacetonato) complex [(QH) ₂ having an emission maximum at 680 nm. There is an element using Ir (acac)] having an external quantum efficiency of 10.2% at 600 cd / m ² (Non-patent Document 3).
In addition, an element using a 5,10,15,20-tetraphenyl-21H, 23H-tetrabenzoporphyrin platinum complex [Pt (tpbp)] having an emission maximum at 765 nm, an external quantum at 0.1 mA / cm ² . Some have an efficiency of 6.3% (Non-Patent Document 4).
In addition, an element using a 2,3-dicyanopyrazinophenanthrene compound (TPA-DCPP) showing an emission maximum at 708 nm, the external quantum efficiency when the doping amount is set to 20% is 9.8%. There is a thing (nonpatent literature 5).
In addition, an element using 2,3-bis [4 ′-(diphenylamino)-(1,1′-biphenyl) -4-yl] fumaronitrile (TPATCN), which exhibits an emission maximum at 670 nm, has an external quantum efficiency of There is 2.58% (Non-Patent Document 6).
However, although all of the above compounds have emission maxima at 600 nm or more, they are insufficient for practical use in terms of efficiency, characteristics and effects, and further development of compounds and optimization for device application are necessary. It is.

Konica Minolta Holdings, Inc. website, http: // www. konicaminolta. jp / about / release / 2010 / 0412_01_01. html Japanese Society of Plant Physiology, http: // jspp. org / H. Fujita, H .; Sakurai, K .; Tani, K .; Wakisaka and T.W. Hirao, IEICE Electronics Express, 2005, 2 (8), 260-266. C. Borek, et al. , Angew. Chem. 2007, 119, 1277-1130 S. Wang et al. , Angew. Chem. Int. Ed. 2015, 54, 13068-13072 X. Han et al. , Adv. Funct. Mater. DOI: 10.1002 / adfm. 2015503344.

The present invention relates to an organic electroluminescence produced by a novel triazine compound having a high triplet energy level and excellent heat resistance and capable of realizing high efficiency, low voltage and long life of the element when used as an organic electronic element material. and an object thereof is to provide a luminescence (EL) lighting plant cultivation using element.

The above problems are solved by the following inventions 1) to 2).
1) Illumination for plant cultivation using an organic electroluminescence device produced by using a triazine compound represented by the following general formula [1] in which a triazine skeleton part and a dibenzofuran or dibenzothiophene skeleton part are connected via a biphenyl skeleton part .
[Wherein, X represents an oxygen atom or a sulfur atom, and R ¹ and R ³ , R ⁴ each independently represents a group consisting of hydrogen, fluorine, and a linear or branched alkyl group having 1 to 6 carbon atoms. Represents a selected group, R ² represents hydrogen, fluorine, or a linear or branched alkyl group having 1 to 6 carbon atoms; Ar represents a phenyl group represented by the following formulas (I) to (VIII); Represents a group selected from the group consisting of 1-naphthyl group, 2-naphthyl group, 1-phenanthrenyl group, 2-phenanthrenyl group, 3-phenanthrenyl group, 4-phenanthrenyl group and 9-phenanthrenyl group, and R ^{10 to} R ^73. Represents a group independently selected from the group consisting of hydrogen, fluorine, and a linear or branched alkyl group having 1 to 6 carbon atoms. ]
2) The plant cultivation illumination according to 1), wherein the triazine compound is a triazine compound represented by the following general formula [2] in which a triazine skeleton portion and a dibenzofuran or dibenzothiophene skeleton portion are linked via a biphenyl skeleton portion.
[Wherein, X represents an oxygen atom or a sulfur atom, and R ¹ and R ³ , R ⁴ each independently represents a group consisting of hydrogen, fluorine, and a linear or branched alkyl group having 1 to 6 carbon atoms. Represents a selected group, R ² represents hydrogen, fluorine, or a linear or branched alkyl group having 1 to 6 carbon atoms; Ar represents a phenyl group represented by the following formulas (I) to (VIII); Represents a group selected from the group consisting of 1-naphthyl group, 2-naphthyl group, 1-phenanthrenyl group, 2-phenanthrenyl group, 3-phenanthrenyl group, 4-phenanthrenyl group and 9-phenanthrenyl group, and R ^{10 to} R ^73. Represents a group independently selected from the group consisting of hydrogen, fluorine, and a linear or branched alkyl group having 1 to 6 carbon atoms. ]

According to the present invention, a novel triazine compound having a high triplet energy level and excellent heat resistance and capable of realizing high efficiency, low voltage, and long life of an element when used as an organic electronic element material is used. the organic EL element manufactured Te can provide illumination for plant cultivation using.
Furthermore, the organic EL element used in the present invention starts emitting light at a very low voltage of about 2.4 V as a rising voltage, and exhibits a very high light extraction effect as a red element having a maximum external quantum efficiency of about 18%. In addition, it is possible to achieve a long life of about 1500 hours of 10% decay time of emission intensity, which is sufficiently practical. Therefore, when this is applied to lighting for plant cultivation, it is possible to produce red lighting suitable for indoor cultivation of plants.

FIG. 5 shows a nuclear magnetic resonance spectrum ( ¹ H-NMR) of the compound of Example 1. The figure which shows the result of the mass spectrometry (Mass) of the compound of Example 1. FIG. The figure which shows the ultraviolet-visible (UV-vis) absorption spectrum and photoluminescence (PL) spectrum of the compound of Example 1. The figure which shows the measurement result of the ionization potential of the compound of Example 1. The figure which shows the ultraviolet-visible (UV-vis) absorption spectrum of (alpha) -NPD and DBT (4) -HH-PhTRZ. The figure which shows the photo-luminescence (PL) spectrum of (alpha) -NPD and DBT (4) -HH-PhTRZ. The figure which shows the nuclear magnetic resonance spectrum (< ¹ > H-NMR) of the compound of Example 2. FIG. The figure which shows the energy diagram of the element of Examples 3-6. The figure which shows the voltage-current density characteristic of the element of Examples 3-5. The figure which shows the voltage-luminance characteristic of the element of Examples 3-5. The figure which shows the current density-external quantum efficiency characteristic of the element of Examples 3-5. The figure which shows the luminance-external quantum efficiency characteristic of Examples 3-5. The figure which shows the EL spectrum of Examples 3-5. The figure which shows the measurement result of the element lifetime of Examples 3-5. The figure which shows the energy diagram of the element of Examples 7-9. The figure which shows the voltage-current density characteristic of Examples 6-7. The figure which shows the voltage-luminance characteristic of Examples 6-7. The figure which shows the current density-external quantum efficiency characteristic of Examples 6-7. The figure which shows the brightness | luminance-external quantum efficiency characteristic of Examples 6-7. The figure which shows the EL spectrum of Examples 6-7. The figure which shows the measurement result of the element lifetime of Examples 6-7. The figure which shows the voltage-current density characteristic of Examples 8-9. The figure which shows the voltage-luminance characteristic of Examples 8-9. The figure which shows the current density-external quantum efficiency characteristic of Examples 8-9. The figure which shows the brightness | luminance-external quantum efficiency characteristic of Examples 8-9. The figure which shows the EL spectrum of Examples 8-9. The figure which shows the measurement result of the element lifetime of Examples 8-9. The figure which shows the energy diagram of the element of Example 10. FIG. FIG. 10 shows voltage-current density characteristics of Example 10. FIG. 10 shows voltage-luminance characteristics of Example 10. FIG. 10 shows luminance-current efficiency characteristics of Example 10. FIG. 10 shows luminance-power efficiency characteristics of Example 10. FIG. 10 shows current density-external quantum efficiency characteristics of Example 10. FIG. 10 shows luminance-external quantum efficiency characteristics of Example 10. FIG. 11 shows an EL spectrum of Example 10. It shows a ¹ H-NMR spectrum of the compound of Example 11 (total area). The figure which shows the < ¹ > H-NMR spectrum of the compound of Example 11 (enlarged view). It shows a ¹ H-NMR spectrum of the compound of Example 12 (total area). The figure which shows the < ¹ > H-NMR spectrum of the compound of Example 12 (enlarged view). It shows a ¹ H-NMR spectrum of the compound of Example 13 (total area). The figure which shows the < ¹ > H-NMR spectrum of the compound of Example 13 (enlarged view). The figure which shows the result of the thermal decomposition temperature of the compound of Example 13. It shows a ¹ H-NMR spectrum of the compound of Example 14 (total area). The figure which shows the < ¹ > H-NMR spectrum of the compound of Example 14 (enlarged view). It shows a ¹ H-NMR spectrum of the compound of Example 15 (total area). The figure which shows the < ¹ > H-NMR spectrum of the compound of Example 15 (enlarged view). The figure which shows the result of the thermal decomposition temperature of the compound of Example 15. FIG. FIG. 18 shows the ¹ H-NMR spectrum of the compound of Example 16 (all regions). FIG. 16 is a diagram (enlarged view) showing the ¹ H-NMR spectrum of the compound of Example 16. It shows a ¹ H-NMR spectrum of the compound of Example 17 (total area). The figure which shows the < ¹ > H-NMR spectrum of the compound of Example 17 (enlarged view). The figure which shows the result of the thermal decomposition temperature of the compound of Example 17. FIG. It shows a ¹ H-NMR spectrum of the compound of Example 18 (total area). The figure which shows the < ¹ > H-NMR spectrum of the compound of Example 18 (enlarged view). FIG. 18 shows the ¹ H-NMR spectrum of the compound of Example 19 (all regions). The figure which shows the < ¹ > H-NMR spectrum of the compound of Example 19 (enlarged view). The figure which shows the result of the thermal decomposition temperature of the compound of Example 19. FIG. It shows a ¹ H-NMR spectrum of the compound of Example 20 (total area). Figure shows the ¹ H-NMR spectrum of the compound of Example 20 (enlarged view). It shows a ¹ H-NMR spectrum of the compound of Example 21 (total area). The figure which shows the < ¹ > H-NMR spectrum of the compound of Example 21 (enlarged view). It shows a ¹ H-NMR spectrum of the compound of Example 22 (total area). Figure shows the ¹ H-NMR spectrum of the compound of Example 22 (enlarged view). FIG. 18 shows the ¹ H-NMR spectrum of the compound of Example 35 (all regions). The figure which shows the < ¹ > H-NMR spectrum of the compound of Example 35 (enlarged view). FIG. 18 shows a ¹ H-NMR spectrum of the compound of Example 36 (all regions). FIG. 19 shows a ¹ H-NMR spectrum of the compound of Example 36 (enlarged view). It shows a ¹ H-NMR spectrum of the compound of Example 37 (total area). The figure which shows the < ¹ > H-NMR spectrum of the compound of Example 37 (enlarged view). It shows a ¹ H-NMR spectrum of the compound of Example 38 (total area). Figure shows the ¹ H-NMR spectrum of the compound of Example 38 (enlarged view). Sectional drawing which shows an example of the organic EL element used by this invention. Sectional drawing which shows an example of the organic EL element used by this invention. Sectional drawing which shows an example of the organic EL element used by this invention. Sectional drawing which shows an example of the organic EL element used by this invention. Sectional drawing which shows an example of the organic EL element used by this invention. Sectional drawing which shows an example of the organic EL element used by this invention. Sectional drawing which shows an example of the organic EL element used by this invention. Sectional drawing which shows an example of the organic EL element used by this invention.

Hereinafter, the present invention will be described in detail.
In general, a compound having a structure in which partial skeletons are connected by a benzene ring has high crystallinity. When a film is formed using this compound, it is easily recrystallized over time. Since the recrystallized portion does not participate in light emission, it is necessary to lower the crystallinity of the compound in order to use it as a light emitting material.
Therefore, the present inventors examined a compound having a molecular structure that is difficult to recrystallize, and considered reducing the crystallinity by imparting a twist to the molecule. Then, in the triazine compound in which the triazine skeleton part and the dibenzofuran or dibenzothiophene skeleton part used in the present invention are connected via the biphenyl skeleton part, the triazine skeleton part and the dibenzofuran or dibenzothiophene skeleton part are combined with a meta of a benzene ring having a biphenyl structure. It has been found that the crystallinity is lowered by bonding to the position, and the present invention has been achieved. In addition, when the bond of the skeleton part is in the para position, the crystallinity is not sufficiently lowered. In addition, the triplet energy level of the compound in which the bond of the skeleton part is in the para position is approximately 2.5 eV, but the triplet energy level of the triazine compound used in the present invention is higher than 2.5 eV.
Furthermore, the relationship between the substituent Ar in the general formula [1] and the general formula [2] and the twist of the molecule was examined. When Ar is a phenyl group, a naphthyl group, or a phenanthrenyl group, However, it was found that the crystallinity increases when Ar is an anthranyl group or a group in which four or more benzene rings are condensed.

Of ^{R 1 ~R 4, R 10 ~R} 73 in the triazine compound used in the present invention, a linear or branched alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n- propyl group, iso -Propyl group, n-butyl group, sec-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 5-methyl Pentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 1,4-dimethylbutyl group, 2,3-dimethylbutyl Group, 2,4-dimethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 4-ethylbutyl group and the like.

The triazine compounds of general formula [1] and general formula [2] used in the present invention were synthesized by the method as shown below, but are not limited thereto. X, R ¹ , R ² , R ³ , R ⁴ , and Ar in the reaction formulas shown in [Chemical Formula 5] to [Chemical Formula 14] are the same as those in the general formula [1] and the general formula [2]. is there. Y represents a bromine atom or an iodine atom, and Z represents a boronic acid or a boronic acid ester.
First, the synthesis of an intermediate containing a dibenzofuran ring or a dibenzothiophene ring will be described. Regarding the addition position of the biphenyl skeleton to the dibenzofuran ring or dibenzothiophene ring, an intermediate in which a highly reactive halogen such as bromine or iodine is introduced into the corresponding position and then converted to boronic acid or its ester by an appropriate method. Can be synthesized.

For example, when synthesizing an intermediate in which the addition position is 1-position, halogen cannot be directly introduced into the 1-position of a dibenzofuran ring or dibenzothiophene ring. Examples include a method of introducing bromine by a method described in JP-A-2006-135775 after ring closure using pivalic acid by a method described in JP-A-520508.
The starting material 2'-phenoxyacetanilide or 2'-thiophenoxyacetanilide was synthesized by acetylating the corresponding aniline by known methods.

As another method, as shown in the following [Chemical Formula 6], a compound having a nitro group is synthesized by the method described in JP 2012-049518 A, and after cyclization, the nitro group is reduced to an amino group, and the Sandmeyer reaction is performed. The method of brominating or iodizing using is mentioned.
The starting diphenyl ether or diphenyl thioether may be synthesized by Williamson's ether synthesis method (for example, Liebigs Ann. Chem. 1851, 77, 37) using the corresponding phenol or thiophenol and halobenzene. The ring closure reaction may be performed by applying the method of Sanz, Roberto et al. (Journal of Organic Chemistry, 71 (16), 6291-6294; 2006). For the reduction of the nitro group and the Sandmeyer reaction, methods well known among those skilled in the art may be employed.

In the case of synthesizing the dibenzofuran or dibenzothiophene having a substituent R ^2, R ³ are as phenol or thiophenol and a halobenzene in the ether synthesis, using those having a substituent R ^2, R ^3, the chemical formula 6 ] May be synthesized according to the procedure shown in the following [Chemical Formula 7].

When synthesizing an intermediate in which the addition position is the 2-position, dibenzofuran or dibenzothiophene can be directly brominated. As the method, for example, Hand, Elli S. et al. And the like (Journal of Organic Chemistry, 62 (5), 1348-1355; 1997), Kudo et al. (Journal of Heterocyclic Chemistry, 22 (1), 215-18; 1985) and the like may be applied.
Further, when an intermediate at the 2-position having the substituents R ² and R ³ is required, the position of the nitro group of the starting material in the above [Chemical 7] can be changed to change the following [Chemical 8 It can also be synthesized by the procedure shown in FIG.

When synthesizing an intermediate at the 3-position, the method of Wei, Ye et al. (Organic Letters, 13 (20), 5504-5507; 2011) or the method of Illuminati, Gabriello et al. (Journal of the American Chemical Chemical). (1951), 73, 5887-5888.) May be applied. If an intermediate having substituents R ² and R ³ is required, the starting material in the above [Chemical Formula 7] may be changed to one having a nitro group at the 5-position.

When synthesizing the intermediate at the 4-position, the necessary boronic acid can be synthesized directly from dibenzofuran or dibenzothiophene depending on its reactivity, unlike the one at the 1- to 3-position. For the synthesis, for example, the pamphlet of International Publication No. 2009/110360 can be referred to. If an intermediate having substituents R ² and R ³ is required, the starting material in the above [Chemical Formula 7] may be changed to the one in which the position of the nitro group is 6-position.

An intermediate in which halogen is introduced at the 1st to 3rd positions of the dibenzofuran ring or dibenzothiophene ring synthesized as described above is reacted with, for example, magnesium to form a Grignard reagent, and then trimethyl borate or boric acid at low temperature. Boronic acid can be obtained by reacting with a boronic acid ester such as triisopropyl or by reacting with normal butyllithium at a low temperature to form a lithiated product, then reacting with the boronic acid ester and treating with diluted acid water. .
The desired boronic acid ester can also be obtained by reacting with a boronic acid ester such as 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and adding water to stop the reaction. can get. Recently, a method in which bis (triphenylphosphine) dichloropalladium is added in the presence of potassium acetate in a polar solvent such as DMF using bispinacolatodiborane and a boronic acid ester is synthesized under heating can also be used.

When it is desired to introduce an alkyl group such as a methyl group or fluorine as the substituent R ¹ of the biphenyl skeleton, the corresponding amine compound is converted to a halogen compound by a Sandmeyer reaction, and then the boronic acid of the dibenzofuran ring or dibenzothiophene ring is used. Alternatively, it may be reacted with a boronic acid ester. Further, the obtained halogen compound can be used for the subsequent reaction if it is converted into boronic acid or boronic acid ester by an appropriate method. The following [9] shows the Sandmeyer reaction. For details, refer to International Publication No. 2005/094882 pamphlet and Japanese Patent No. 6012889.

If the boronic acid or boronic acid ester having the dibenzofuran ring or dibenzothiophene ring obtained as described above and the halogen compound obtained by the Sandmeyer reaction are Suzuki coupled as shown in the following [Chemical Formula 10] , An intermediate having a dibenzofuran ring or a dibenzothiophene ring is obtained. These intermediates can be converted into a boronic acid compound by the same method as when the dibenzofuran ring or dibenzothiophene ring compound intermediate as described above is converted into a boronic acid or boronic acid ester via a halogen compound.

Details of the Suzuki coupling can be found in Miyaura, N .; Suzuki, A .; Chem. Rev. Reference may be made to 1995, 95, 2457, etc., but this will be briefly described.
The reaction solvent is an aromatic hydrocarbon solvent, a mixture of an aromatic hydrocarbon solvent and an alcohol solvent, an ether solvent, or the like. Aromatic hydrocarbon solvents include toluene, xylene, ethylbenzene, mesitylene and the like. Examples of alcohol solvents include methanol, ethanol, propanol, butanol and the like. Examples of ether solvents include cyclic ethers such as tetrahydrofuran and 1,4-dioxane, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethoxy ether, and ethylene glycol diethoxy ether.
In the present invention, it is preferable to use an aromatic hydrocarbon solvent since the solubility of the raw material in the solvent is the key to the progress of the reaction. A mixture of toluene and an alcohol solvent can also be used.
Examples of bases used for the reaction include inorganic or organic bases. Preference is given to alkali metal carbonates or bicarbonates, more preferably potassium carbonate.
As for palladium used in the reaction, since any reaction is a coupling reaction between a halogen compound such as bromide and a boric acid compound, generally Pd (0) is used. Tetrakis (triphenylphosphine) palladium or tris (dibenzylideneacetone) dipalladium is preferable, and tetrakis (triphenylphosphine) palladium is more preferable.

Next, as for the intermediate of the triazine skeleton part, a method described in International Publication 2011/132684, which is synthesized from an amidine compound and a Schiff base, or a method described in JP 2013-256490 A in which ring closure is performed using antimony pentachloride. Etc. can be referred to.
The method described in the pamphlet of International Publication No. 2011-132684 is as shown in the following [Chemical Formula 11]. In the formula, Ar of the Schiff base and Ar of amidine hydrochloride are the same aryl group.

As the solvent 1 in the synthesis of the Schiff base, a solvent immiscible with water is used in order to condense the corresponding aldehyde and amine compound by a dehydration reaction. For example, hydrocarbon solvents such as toluene, xylene, ethylbenzene, and mesitylene are preferable, but toluene is more preferable in view of recovery after the reaction. As the reaction conditions, it is necessary to azeotrope the generated water with a solvent and trap it with a Dean-Stark tube.
In the reaction between the Schiff base and amidine hydrochloride, the reaction does not proceed unless the solvent is soluble in amidine hydrochloride. Therefore, a highly polar solvent is used. In general, alcohols, nitrogen-containing solvents such as dimethylformamide, dimethyl sulfoxide, and the like are used, but alcohols, particularly ethyl alcohol, are preferable in terms of post-treatment. Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, alcohol salts such as sodium methylate and potassium methylate, etc. alone or in combination. And use. Preferred for the progress of the reaction is a mixture of sodium hydroxide and sodium tertiary butyrate.

The method described in JP2013-256490A is as shown in the following [Chemical Formula 12]. This method can be applied to cases where it is difficult to obtain amidine hydrochloride.
A solvent that does not react with antimony pentachloride is used. Generally, an aliphatic halide solvent such as methylene chloride or dichloroethane is used, but methylene chloride is preferred in the present invention.

Using the boronic acid compound and bromide obtained as described above, the triazine compound of the general formula [1] and the general formula [2] used in the present invention by the reaction shown in the following [Chemical Formula 13] or [Chemical Formula 14] Can be synthesized.

<Reaction Formula of Compound of General Formula [1]>
<Reaction Formula of Compound of General Formula [2]>

Although the specific example of the triazine compound used by this invention is shown in Table 1-Table 556, it is not limited to these. The meanings of the abbreviations in the table are as follows.
“Position” represents a bonding position of a dibenzofuranyl group or a dibenzothiophenyl group.
However, R ³ is not bonded to the same position.
-In the case of an alkyl group having 3 or more carbon atoms, both linear and branched are included.
· "Ph" represents a phenyl group - represents a _(C 6 _{H 5).}
· "Tol" is tolyl - represents a _{(CH 3 C 6 H 5)} .
· "Phen" is phenethyl group - represents a _{(C 2 H 5 C 6 H} 5).
-About a phenyl group, a tolyl group, and a phenethyl group, it can also replace with what has a C3-C6 linear or branched alkyl group as a substituent.

The compounds represented by the following formulas are shown in Tables 1 to 38. X, R ^{1 to} R ⁴ and R ^{10 to} R ¹⁴ in the formula are the same as those in the general formula [1].

The compounds represented by the following formulas are shown in Table 39 to Table 97. X, R ^{1 to} R ⁴ and R ^{15 to} R ²¹ in the formula are the same as those in the general formula [1].

The compounds represented by the following formulas are shown in Table 98 to Table 156. X, R ^{1 to} R ⁴ and R ^{22 to} R ²⁸ in the formula are the same as those in the general formula [1].

The compounds represented by the following formulas are shown in Tables 157 to 236. X, R ^{1 to} R ⁴ and R ^{29 to} R ³⁷ in the formula are the same as those in the general formula [1].

Compounds represented by the following formulas are shown in Tables 237 to 316. X, R ^{1 to} R ⁴ and R ^{38 to} R ⁴⁶ in the formula are the same as those in the general formula [1].

Compounds represented by the following formulas are shown in Tables 317 to 396. X, R ^{1 to} R ⁴ and R ^{47 to} R ⁵⁵ in the formula are the same as those in the general formula [1].

Compounds represented by the following formulas are shown in Tables 397 to 476. X, R ^{1 to} R ⁴ and R ^{56 to} R ⁶⁴ in the formula are the same as those in the general formula [1].

Compounds represented by the following formulas are shown in Tables 477 to 556. X, R ^{1 to} R ⁴ and R ^{65 to} R ⁷³ in the formula are the same as those in the general formula [1].

The triazine compound used in the present invention has a large energy given to the light-emitting material because the lowest empty orbit (LUMO) is shallow and the highest occupied orbit (HOMO) is deep. Moreover, since each value is larger than the work function values of the anode and the cathode, the hole or electron injection property is high. Therefore, the light emitting material can be efficiently illuminated by combining with a light emitting material, particularly a red light emitting material having a long wavelength. In use, it is desirable to form a layer by vapor deposition.
Further, it is possible to produce an organic EL device by using the triazine compound, in which case it can be used as a host material for the emission layer. Furthermore, since the hole or electron injection property is high, it can be mixed with the hole transport layer or the electron transport layer.

Next , the organic EL element used in the present invention will be described.
The organic EL device used in the present invention is a device in which a plurality of organic compounds are laminated between an anode and a cathode, and the triazine compound used in the present invention is preferably used as the host material of the light emitting layer. It may be contained in the transport layer.
The light emitting layer is generally composed of a light emitting material and a host material. Examples of the configuration of the multilayer organic EL device include, for example, an anode (for example, ITO) / hole transport layer / light emitting layer / electron transport layer / cathode, ITO / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode. ITO / hole transport layer / light-emitting layer / hole block layer / electron transport layer / cathode, ITO / hole transport layer / light-emitting layer / hole block layer / electron transport layer / electron injection layer / cathode, ITO / hole injection layer (positive And a layer in which a large number of layers such as hole injection layer) / hole transport layer / light emitting layer / hole block layer / electron transport layer / electron injection layer / cathode are laminated. Moreover, you may provide a sealing layer on a cathode as needed.
Each of the light emitting layer, the hole transport layer, and the electron transport layer preferably has a multilayer structure in which the respective functions are separated. In addition, the hole transport layer and the electron transport layer can be provided separately with a layer responsible for the injection function (hole injection layer and electron injection layer) and a layer responsible for the transport function (hole transport layer and electron transport layer).

Hereinafter, the constituent elements of the organic EL element used in the present invention will be described by taking as an example an element structure composed of an anode / hole transport layer / light emitting layer / electron transport layer / cathode.
The organic EL element used in the present invention is preferably supported by a substrate. There is no restriction | limiting in particular in the raw material of a board | substrate, For example, what consists of glass, quartz glass, a transparent plastic etc. which are commonly used for the conventional organic EL element is mentioned.
As the anode, the electrode material is preferably a single metal having a high work function (4 eV or more), an alloy of metals having a high work function (4 eV or more), a conductive substance, or a mixture thereof. Specific examples thereof include conductive transparent materials such as metals such as gold, silver and copper, ITO (indium-tin oxide), tin oxide (SnO ₂ ) and zinc oxide (ZnO), and high conductivity such as polypyrrole and polythiophene. Examples include molecular materials.
The anode can be formed by a method such as vapor deposition, sputtering or coating using these electrode materials. Sheet resistance of the anode is preferably several hundreds Omega / cm ² or less. Although the film thickness of the anode depends on the material, it is generally about 5 to 1000 nm, preferably 10 to 500 nm.

The cathode is preferably made of a single metal having a low work function (4 eV or less), an alloy of metals having a low work function (4 eV or less), a conductive substance, or a mixture thereof as an electrode material. Specific examples thereof include lithium, lithium-indium alloy, sodium, sodium-potassium alloy, magnesium, magnesium-silver alloy, magnesium-indium alloy, aluminum, aluminum-lithium alloy, and aluminum-magnesium alloy.
The cathode can be produced by a method such as vapor deposition or sputtering using these electrode materials. The sheet electrical resistance of the cathode is preferably several hundred Ω / cm ² or less. The thickness of the cathode depends on the material, but is generally about 5 to 1000 nm, preferably 10 to 500 nm.
In order to efficiently extract light emitted from the organic EL element used in the present invention , at least one of the anode and the cathode is preferably transparent or translucent.

The hole transport layer is made of a hole transfer compound and has a function of transmitting holes injected from the anode to the light emitting layer. When a hole transfer compound is disposed between two electrodes to which an electric field is applied and holes are injected from the anode, a hole transfer material having a hole mobility of at least 10 ⁻⁶ cm ² / V · sec or more is preferable. As such a hole-transmitting substance, an arbitrary material is selected from materials conventionally used as a charge injection material for holes in a photoconductive material and known materials used for a hole transport layer of an organic EL element. Can be used.
Examples of hole transfer materials include phthalocyanine derivatives such as copper phthalocyanine, N, N, N ′, N′-tetraphenyl-1,4-phenylenediamine, N, N′-di (m-tolyl) -N, N Triarylamine derivatives such as' -diphenyl-4,4-diaminophenyl (TPD), N, N'-di (1-naphthyl) -N, N'-diphenyl-4,4-diaminophenyl (α-NPD) , Polyphenylenediamine derivatives, polythiophene derivatives, and water-soluble PEDOT-PSS (polyethylenedioxathiophene-polystyrenesulfonic acid).
The hole transport layer may be a single layer made of one or more of these hole transfer materials, but may be a laminate of hole transport layers made of materials other than those described above.

Examples of the hole injection material include PEDOT-PSS (polymer mixture) and DNTPD represented by the following formula.

Examples of the hole transport material include TPD, DTASi, α-NPD represented by the following formula.

The electron transport layer is made of an electron transport material and has a function of transmitting electrons injected from the cathode to the light emitting layer. When an electron transport material is arranged between two electrodes to which an electric field is applied and electrons are injected from the cathode, an electron transport material having an electron mobility of at least 10 ⁻⁶ cm ² / V · sec or more is preferable.
As such an electron transport material, a material that is conventionally used as an electron charge injection material in a photoconductive material or a known material that is used in an electron transport layer of an organic EL element may be appropriately selected and used. it can.
Examples of electron transport materials include quinoline complexes such as tris (8-hydroxyquinolinolato) aluminum complex (Alq ₃ ), 1-N-phenyl-2- (p-biphenylyl) -5- (p-tert -Triazine derivatives such as butylphenyl) -1,3,5-triazine (TAZ), phenanthroline derivatives such as 1,4-di (1,10-phenanthroline-2-yl) benzene (DPB), lithium fluoride And alkali metal halides.
The electron transport layer may be a single layer composed of one or more of these electron transport materials, but may be a stack of electron transport layers composed of materials other than those described above.

Examples of the electron injection material include lithium fluoride (LiF), 8-hydroxyquinolinolato lithium complex (Liq) represented by the following formula, lithium complex of phenanthroline derivative (LiPB) described in JP-A-2008-106015, Examples thereof include a phenoxypyridine lithium complex (LiPP) described in JP-A-2008-195623.

Examples of the electron transport material include Alq ₃ , TAZ, and DPB represented by the following formula.
In addition, “TmPyPhTAZ” described in Japanese Patent Application Laid-Open No. 2007-137829 and “tetra-pPyPhBP” described in Japanese Patent Application Laid-Open No. 2008-066322 (both described below) are electron transport materials according to the applicant's application. Etc.) can also be used.

For the light emitting layer, a commonly used light emitting material can be used without any particular limitation. Examples thereof include pyran derivatives represented by the following formula. However, these are fluorescent materials and are not necessarily efficient materials because the internal quantum efficiency is 25% at the maximum.
Therefore, as the light emitting material used in combination with the triazine compound used in the present invention , a phosphorescent material [Ir (DPQ) ₂ (dpm)] of the following formula having an internal quantum efficiency of 100% at maximum by triplet excitons is preferable .
As phosphorescent materials, the following [Chemical 30] compounds described in JP-A-2009-132688, the following [Chemical 31] compounds described in JP-A-2009-149607, and JP-A-2009-164614 are described. The following [Chemical Formula 32] compound and the following [Chemical Formula 33] compound described in JP2013-155153A may be used. In addition, “Bu” in [Chemical Formula 33] means a butyl group.

The light emitting layer is formed of a host material and a light emitting material (dopant) [Appl. Phys. Lett. 65 3610 (1989)]. A luminescent material is used in combination with a host material in order to avoid concentration quenching and to efficiently transfer luminescent energy to the luminescent material. The amount of the light emitting material used is preferably 0.01 to 40% by weight, more preferably 0.1 to 20% by weight, based on the host material.
Although it is preferable to use the triazine compound according to the present invention as the host material, it may be used in combination with other host materials, for example, a compound represented by the following formula described in JP 2012-167046 A related to the applicant's application. it can.

In the organic EL device used in the present invention , a hole injection layer made of an organic conductor may be provided between the anode and the organic compound layer for the purpose of further improving the hole injection property. Examples of the hole injection material include phthalocyanine derivatives such as copper phthalocyanine, polyphenylenediamine derivatives, polythiophene derivatives, and PEDOT-PSS (polyethylenedioxythiophene-polystyrenesulfonic acid).

The formation method of the hole injection layer and the hole transport layer is not particularly limited. For example, a dry film forming method (vacuum vapor deposition method, ionization vapor deposition method, etc.), a wet film forming method [solvent coating method (spin coating method, casting method, ink jet method) Etc.)].
The film formation of the electron transport layer is limited to dry film formation methods (vacuum vapor deposition method, ionization vapor deposition method, etc.) because the lower layer may be eluted when the wet film formation method is used.
You may use together said film forming method as needed.
The vacuum deposition conditions for producing a hole transport layer, a light emitting layer, an electron transport layer, etc. by vacuum deposition are not particularly limited, but usually a boat temperature (deposition source of about 50 to 500 ° C. under a vacuum of about 10 ⁻⁵ Torr or less. Temperature), at a substrate temperature of about −50 to 300 ° C., 0.01 to 50 nm / sec. Vapor deposition is preferred. Moreover, when each layer of a positive hole transport layer, a light emitting layer, and an electron carrying layer is produced using a some compound, it is preferable to co-evaporate, carrying out temperature control of the boat which put the compound, respectively.

  When producing a hole injection layer or a hole transport layer by a solvent coating method, the components constituting each layer are dissolved or dispersed in a solvent to obtain a coating solution. Solvents include hydrocarbon solvents (eg, heptane, toluene, xylene, cyclohexane, etc.), ketone solvents (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), halogen solvents (eg, dichloromethane, chloroform, chlorobenzene, dichlorobenzene, etc.) Ester solvents (eg, ethyl acetate, butyl acetate, etc.), alcohol solvents (eg, methanol, ethanol, propanol, butanol, methyl cellosolve, ethyl cellosolve, etc.), ether solvents (eg, dibutyl ether, tetrahydrofuran, 1,4-dioxane) 1,2-dimethoxyethane, etc.), aprotic solvents (for example, N, N'-dimethylacetamide, dimethyl sulfoxide, etc.), water and the like. The solvent may be used alone or a plurality of solvents may be used in combination.

The thickness of each layer such as the hole transport layer, the light emitting layer, and the electron transport layer is not particularly limited, but is usually 5 to 5000 nm.
The organic EL device used in the present invention may be protected by providing a protective layer (sealing layer) for the purpose of blocking contact with oxygen, moisture, etc., or encapsulating the device in an inert substance. Examples of the inert substance include paraffin, silicon oil, and fluorocarbon. Examples of the material used for the protective layer include fluorine resin, epoxy resin, silicone resin, polyester, polycarbonate, and photocurable resin.

The organic EL element used in the present invention can be used as a DC-driven element. When a DC voltage is applied, light emission is observed when a voltage of about 1.5 to 20 V is applied with the positive polarity of the anode and the negative polarity of the cathode. The organic EL element used in the present invention can also be used as an AC drive element. When an AC voltage is applied, light is emitted when the anode is in a positive state and the cathode is in a negative state.
The organic EL element used in the present invention can be used for various illuminations such as a copying machine, a printer, and a backlight of a liquid crystal display. The red light source is indispensable and is very suitable for use in such applications.

72 to 79 are sectional views of preferred examples of the organic EL element used in the present invention.
FIG. 72 is an example in which an anode 2, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6 and a cathode 4 are sequentially provided on the substrate 1. This separates the functions of carrier transport and light emission, and the degree of freedom in material selection increases, so that the efficiency of light emission and the degree of freedom in light emission color increase.
FIG. 73 shows an example in which an anode 2, a hole injection layer 7, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6 and a cathode 4 are sequentially provided on the substrate 1. In this case, the provision of the hole injection layer 7 improves the adhesion between the anode 2 and the hole transport layer 5, improves the injection of holes from the anode, and is effective in lowering the voltage of the light emitting element.
FIG. 74 shows an example in which an anode 2, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6, an electron injection layer 8 and a cathode 4 are sequentially provided on the substrate 1. In this case, injection of electrons from the cathode 4 is improved, which is effective for lowering the voltage of the light emitting element.
FIG. 75 shows an example in which an anode 2, a hole injection layer 7, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6, an electron injection layer 8 and a cathode 4 are sequentially provided on the substrate 1. In this case, hole injection from the anode 2 is improved and electron injection from the cathode 4 is improved, which is the most effective for driving at a low voltage.

76 to 79 are cross-sectional views of a device in which a hole block layer is inserted. The hole blocking layer has an effect of preventing holes injected from the anode or excitons generated by recombination in the light emitting layer 3 from escaping to the cathode 4, and is effective in improving the light emission efficiency of the organic EL element. The hole blocking layer 9 can be inserted between the light emitting layer 3 and the cathode 4, between the light emitting layer 3 and the electron transport layer 6, or between the light emitting layer 3 and the electron injection layer 8. More preferred is between the light emitting layer 3 and the electron transport layer 6.
76 to 79, each of the hole transport layer 5, the hole injection layer 7, the electron transport layer 6, the electron injection layer 8, the light emitting layer 3, and the hole block layer 9 may have a single layer structure or a multilayer structure.
72 to 79 are basic device configurations to the last, and the configuration of the organic EL device using the triazine compound of the present invention is not limited to these.

EXAMPLES Hereinafter, although an Example and a reference example are shown and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples.
First, synthesis examples 1 to 27 of intermediates necessary for synthesizing the triazine compounds represented by the general formula [1] and the general formula [2] will be shown, and then the synthesis of the triazine compounds using the intermediates. It shows the example.
Moreover, the description of (DSC) after melting | fusing point in an example means melting | fusing point measured with the differential scanning calorimeter (DSC).
Further, “DBT-TRZ” in FIGS. 3 to 6, 8, 15, and 28 is “DBT (4) -HH-PhTRZ” synthesized in Example 1.

Synthesis example 1
Synthesis of 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine

<1> Synthesis of N-[(3-bromophenyl) methylene] benzenamine
This compound was synthesized by the following procedure with reference to International Publication No. 2013/172835.
To a 1 L four-necked round bottom flask equipped with a stirrer, a Dean-Stark tube with an Erlin condenser tube, a nitrogen inlet tube and a thermometer, 500 mL of toluene, 50.0 g (0.27 mol) of m-bromobenzaldehyde, aniline 25 0.0 g (0.268 mol) was added, and the mixture was reacted at a reflux temperature of toluene under a nitrogen stream for 8 hours. The water generated at that time was azeotroped with toluene and collected in a Dean-Stark tube.
The obtained reaction liquid was returned to room temperature, and toluene was distilled off under reduced pressure to obtain 74.8 g (yield 106.5%) of an oily substance. The obtained oil was used in the next reaction without purification.

<2> Synthesis of 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine
This compound was synthesized according to the following procedure using, for example, the method described in JP-A-2015-526887.
In a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a nitrogen inlet, and a thermometer, 74.8 g (0.268 mol) of the benzeneamine obtained in the above <1> and 84.6 g of benzamidine hydrochloride (0.54 mol), 22.7 g (0.57 mol) of sodium hydroxide, and 500 mL of ethanol were added, and the mixture was allowed to react at a reflux temperature of ethanol for 18 hours under a nitrogen stream. Next, the mixture was once cooled to room temperature, 10.8 g (0.112 mol) of sodium tertiary butyrate was added, and the mixture was reacted again at an ethanol reflux temperature for 16 hours under a nitrogen stream.
The obtained reaction liquid was cooled to room temperature, and the precipitated crystals were suction filtered. Next, the crystals remaining in Nutsche were thoroughly washed with ethanol and water to obtain 28.0 g (yield 26.7%) of the white target compound. The melting point was 231.47 ° C. (DSC).

Synthesis example 2
Synthesis of 2- (3-bromo-4-methylphenyl) -4,6-diphenyl-1,3,5-triazine

<1> Synthesis of N-[(3-bromo-4-methylphenyl) methylene] benzenamine
This compound was synthesized by the following procedure using 3-bromo-4-tolualdehyde instead of m-bromobenzaldehyde in <1> of Synthesis Example 1.
To a 1 L four-necked round bottom flask equipped with a stirrer, a Dean-Stark tube with an Erlin condenser tube, a nitrogen inlet tube and a thermometer, 420 mL of toluene, 44.5 g of 3-bromo-4-tolualdehyde (0.22 mol) ), 20.8 g (0.22 mol) of aniline was added, and the mixture was reacted at a reflux temperature of toluene under a nitrogen stream for 8 hours. The water generated at that time was azeotroped with toluene and collected in a Dean-Stark tube.
The obtained reaction liquid was returned to room temperature, and toluene was distilled off under reduced pressure to obtain 64.4 g (yield: 105.3%) of an oily substance. The obtained oil was used in the next reaction without purification.

<2> 2- (3-Bromo-4-methylphenyl) -4,6-diphenyl-1,3,5-
Synthesis of triazine
This compound was also synthesized according to the following procedure with the aid of the method <2> of Synthesis Example 1.
In a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser tube, a nitrogen inlet tube and a thermometer, 64.2 g (0.22 mol) of the benzeneamine obtained in the above <1> and 69.8 g of benzamidine hydrochloride (0.45 mol), sodium hydroxide 19.0 g (0.48 mol), and ethanol 420 mL were added, and the mixture was reacted at ethanol reflux temperature for 18 hours under a nitrogen stream. Next, the mixture was once cooled to room temperature, 9.1 g (0.094 mol) of sodium tertiary butyrate was added, and the mixture was reacted again at an ethanol reflux temperature for 16 hours under a nitrogen stream.
The obtained reaction liquid was cooled to room temperature, and the precipitated crystals were suction filtered. Next, the crystals remaining in Nutsche were sufficiently washed with ethanol and water to obtain 30.3 g (yield 33.8%) of the white target compound. The melting point was 176.82 ° C. (DSC).

Synthesis example 3
Synthesis of 2- (3-bromo-4-fluorophenyl) -4,6-diphenyl-1,3,5-triazine

<1> Synthesis of N-[(3-bromo-4-fluorophenyl) methylene] benzenamine
This compound was synthesized according to the following procedure using 3-bromo-4-fluorobenzaldehyde instead of m-bromobenzaldehyde in <1> of Synthesis Example 1.
To a 1 L four-necked round bottom flask equipped with a stirrer, a Dean-Stark tube with an Erlin condenser tube, a nitrogen inlet tube and a thermometer, 460 mL of toluene, 50.0 g of 3-bromo-4-fluorobenzaldehyde (0.25 mol) ), 23.0 g (0.25 mol) of aniline was added and allowed to react for 8 hours at a toluene reflux temperature under a nitrogen stream. The water generated at that time was azeotroped with toluene and collected in a Dean-Stark tube.
The obtained reaction liquid was returned to room temperature, and toluene was distilled off under reduced pressure to obtain 73.6 g of oil (yield 107.5%). The obtained oil was used in the next reaction without purification.

<2> 2- (3-Bromo-4-fluorophenyl) -4,6-diphenyl-1,3,5
-Synthesis of triazine
This compound was also synthesized according to the following procedure with the aid of the method <2> of Synthesis Example 1.
In a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser tube, a nitrogen inlet tube and a thermometer, 64.2 g (0.22 mol) of the benzeneamine obtained in the above <1> and 69.8 g of benzamidine hydrochloride (0.45 mol), sodium hydroxide 19.0 g (0.48 mol), and ethanol 420 mL were added, and the mixture was reacted at ethanol reflux temperature for 18 hours under a nitrogen stream. Next, the mixture was once cooled to room temperature, 9.1 g (0.094 mol) of sodium tertiary butyrate was added, and the mixture was reacted again at an ethanol reflux temperature for 16 hours under a nitrogen stream.
The obtained reaction liquid was cooled to room temperature, and the precipitated crystals were suction filtered. Next, the crystals remaining in Nutsche were thoroughly washed with ethanol and water to obtain 22.2 g (yield 22.2%) of the white target compound. The melting point was 202.67 ° C. (DSC).

Synthesis example 4
Synthesis of 2- (3-bromophenyl) -4,6-di (p-tolyl) -1,3,5-triazine
This compound was synthesized by the following procedure with reference to JP2013-256490A.
To a 500 mL four-necked round bottom flask equipped with a stirrer, a Dimroth condenser, a nitrogen inlet tube, a 25 mL dropping funnel and a thermometer, dichloromethane (DCM) 150 mL, 3-bromobenzoyl chloride 24.1 g (0.103 mol), 22.7 g (0.218 mol) of p-tolunitrile was added and cooled to about −10 ° C. with an ice water bath. Subsequently, 33.0 g (0.11 mol) of antimony pentachloride (SbCl ₅ ) was added dropwise at 0 ° C. or lower while paying attention to heat generation under a nitrogen stream. Then, after 30 minutes of ice bathing, the temperature was returned to room temperature, and the reaction was carried out for 12 hours at a temperature at which DCM was gently refluxed. Next, the mixture was cooled to room temperature, and the crystals were suction filtered, washed with about 200 mL of DCM, and dried overnight in a dryer at 40 ° C.
Next, 750 mL of 28% ammonia water was placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (which may be omitted) and a thermometer, and cooled to about −5 ° C. in an ice water bath. Next, after the whole amount of the dried crystals was slowly added, the mixture was stirred in an ice-water bath for 15 minutes, and then returned to room temperature and stirred for 3 hours. The crystals were then suction filtered and washed with water until the ammonia odor disappeared. The obtained crystals were dried for one day in a vacuum dryer at 60 ° C.
Next, in a 500 mL four-necked round bottom flask equipped with a stirrer, a Liebig condenser and a thermometer, 300 mL of dimethylformamide (DMF) and the crystals dried by the vacuum dryer were placed, and the DMF reflux temperature was set. After stirring for 1 hour, the filtrate was recovered by hot filtration. The crystals remaining on Nutsche were further dissolved with 300 mL of DMF at reflux temperature and filtered hot. This operation is repeated once more, and all the recovered DMF solution is transferred to a 2 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser and a thermometer, and the precipitated crystals are heated once. After dissolving, it was cooled to room temperature to obtain crystals. The crystals were suction filtered, washed with 200 mL of ethanol, and dried with a dryer at 60 ° C. to obtain 19.4 g (42.7%) of the target compound. The melting point was 189.65 ° C. (DSC).

Synthesis example 5
Synthesis of 2- (3-bromophenyl) -4,6-di (p-fluorophenyl) -1,3,5-triazine
This compound was synthesized according to the following procedure using p-fluorobenzonitrile instead of p-tolunitrile in Synthesis Example 4.
In a 500 mL four-necked round bottom flask equipped with a stirrer, a Dimroth condenser, a nitrogen inlet tube, a 25 mL dropping funnel and a thermometer, DCM 150 mL, 3-bromobenzoyl chloride 24.1 g (0.103 mol), p-fluorobenzo 26.4 g (0.218 mol) of nitrile was added and cooled to about −10 ° C. in an ice water bath. Next, under nitrogen flow, 33.0 g (0.11 mol) of SbCl _{5 was} added dropwise at 0 ° C. or less while paying attention to heat generation. After 30 minutes of ice bathing, the temperature was returned to room temperature, and DCM was refluxed gently for 12 hours. Reacted. Next, the mixture was cooled to room temperature, and the crystals were suction filtered, washed with about 200 mL of DCM, and dried overnight in a dryer at 40 ° C.
Next, 750 mL of 28% ammonia water was placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (which may be omitted) and a thermometer, and cooled to about −5 ° C. in an ice water bath. Next, the entire amount of the dried crystals was slowly added, and then the reaction solution was stirred in an ice-water bath for 15 minutes, further returned to room temperature, and stirred for 3 hours. Next, the crystals were suction filtered, washed with water until the ammonia odor disappeared, and dried for one day in a vacuum dryer at 60 ° C.
Next, to a 500 mL four-necked round bottom flask equipped with a stirrer, a Liebig condenser and a thermometer, 300 mL of DMF and crystals dried by the vacuum dryer were added and stirred at the DMF reflux temperature for 1 hour. . The DMF solution was then filtered hot and the filtrate was collected. The crystals remaining on Nutsche were further dissolved with 300 mL of DMF at reflux temperature and filtered hot. This operation is repeated once more, and all the recovered DMF solution is transferred to a 2 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser and a thermometer, and the precipitated crystals are heated once. After dissolution, the crystals were precipitated by cooling to room temperature. The crystals were suction filtered, washed with 200 mL of ethanol, and dried with a dryer at 60 ° C. to obtain 29.5 g (yield: 63.3%) of the target compound. The melting point was 225.98 ° C. (DSC).

Synthesis Example 6
Synthesis of 2- (3-bromophenyl) -4,6-di (1-naphthyl) -1,3,5-triazine
This compound was synthesized by the following procedure using 1-naphthonitrile instead of p-tolunitrile in Synthesis Example 4.
A 500 mL four-necked round bottom flask equipped with a stirrer, a Dimroth condenser, a nitrogen inlet tube, a 25 mL dropping funnel and a thermometer was added to DCM 150 mL, 3-bromobenzoyl chloride 24.1 g (0.103 mol), 1-naphthonitrile. 33.4 g (0.218 mol) was added and cooled to about −10 ° C. in an ice water bath. Then, 33.0 g (0.11 mol) of SbCl _{5 was} added dropwise at 0 ° C. or less while paying attention to heat generation under a nitrogen stream. Next, after 30 minutes of ice bathing, the temperature was returned to room temperature, and the reaction was allowed to proceed for 12 hours at a temperature at which DCM was gently refluxed. Next, the mixture was cooled to room temperature, and the crystals were suction filtered, washed with about 200 mL of DCM, and dried overnight in a dryer at 40 ° C.
Next, 750 mL of 28% ammonia water was placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (which may be omitted) and a thermometer, and cooled to about −5 ° C. in an ice water bath. Next, after the whole amount of the dried crystals was slowly added, the mixture was stirred for 15 minutes in an ice-water bath, further returned to room temperature, and stirred for 3 hours. Next, the crystals were suction filtered, washed with water until the ammonia odor disappeared, and dried for one day in a vacuum dryer at 60 ° C.
Next, 300 mL of DMF and crystals dried by the vacuum dryer were added to a 500 mL four-necked round bottom flask equipped with a stirrer, a Liebig condenser, and a thermometer, and stirred at the DMF reflux temperature for 1 hour. Next, the DMF solution was subjected to hot filtration, and the filtrate was recovered. The crystals remaining on Nutsche were further dissolved with 300 mL of DMF at reflux temperature and filtered hot. This operation is repeated once more, and all the recovered DMF solution is transferred to a 2 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser and a thermometer, and the precipitated crystals are heated once. After dissolution, the crystals were precipitated by cooling to room temperature. The crystals were suction filtered, washed with 200 mL of ethanol, and dried with a dryer at 60 ° C. to obtain 20.6 g (yield 38.7%) of the target compound. The melting point was 110.5-111.3 ° C.

Synthesis example 7
Synthesis of 2- (3-bromophenyl) -4,6-di (9-phenanthro) -1,3,5-triazine
This compound was synthesized according to the following procedure using 9-pheninantonitrile instead of p-tolunitrile in Synthesis Example 4.
A 200 mL four-necked round bottom flask equipped with a stirrer, a Dimroth condenser tube, a nitrogen inlet tube, a 10 mL dropping funnel and a thermometer was added to DCM 63 mL, 3-bromobenzoyl chloride 10.0 g (45.5 mmol), 9-pheninant. 18.5 g (91.1 mol) of nitrile was added and cooled to about −10 ° C. in an ice water bath. Next, 13.8 g (45.9 mmol) of SbCl _{5 was} added dropwise at 0 ° C. or lower while paying attention to heat generation under a nitrogen stream. Then, after 30 minutes of ice bathing, the temperature was returned to room temperature, and DCM was allowed to react gently at reflux temperature for 12 hours. Next, the mixture was cooled to room temperature, and the crystals were suction filtered, washed with about 80 mL of DCM, and dried overnight in a dryer at 40 ° C.
Next, 380 mL of 28% ammonia water was placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (which may be omitted) and a thermometer, and cooled to about −5 ° C. in an ice water bath. Next, after the whole amount of the dried crystals was slowly added, the mixture was stirred in an ice-water bath for 15 minutes, and then returned to room temperature and stirred for 3 hours. Next, the crystals were suction filtered, washed with water until the ammonia odor disappeared, and dried for one day in a vacuum dryer at 60 ° C.
Next, 130 mL of DMF and crystals dried by the vacuum dryer were added to a 300 mL four-necked round bottom flask equipped with a stirrer, a Liebig condenser, and a thermometer, and stirred at the DMF reflux temperature for 1 hour. Next, the mixture was cooled to room temperature and collected by suction filtration. The same operation was repeated once more, and the undissolved crystals were collected by suction filtration and washed with 60 mL of ethanol. Thereafter, the crystals were dried with a dryer at 60 ° C. to obtain 20.6 g (yield 38.7%) of the target compound.

Synthesis example 8
Synthesis of 3- (dibenzofuran-4-yl) phenylboronic acid

<1> Synthesis of 4-dibenzofuranboronic acid
This compound was synthesized by the following procedure.
Dibenzofuran 75.0 g (0.445 mol) and dehydration were added to a 2 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 500 mL isobaric dropping funnel and a thermometer. Tetrahydrofuran (THF) 900 mL was added, and cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 310 mL (0.498 mol) of n-butyllithium n-hexane solution (concentration: 1.6 M) (hereinafter abbreviated as n-BuLi) was dropped at −50 ° C. or lower, and then the isobaric dropping funnel was washed with 150 mL of THF. Added to the reaction solution. Then, after post-reaction at -50 ° C. or lower for 1 hour, the mixture was returned to room temperature and stirred for 4 hours. Next, after cooling again to −60 ° C. or lower with an acetone-dry ice bath, 60 mL (0.538 mol) of trimethyl boronate [B (OMe) ₃ ] was dropped at −45 ° C. or lower, and then the isobaric dropping funnel was washed with 150 mL of THF. Added to the reaction solution. Next, after stirring at −45 ° C. or lower for 30 minutes, the acetone-dry ice bath was removed, and the mixture was returned to room temperature and post-reacted for 15 hours to obtain a boron reaction solution.
Next, 340 mL of concentrated hydrochloric acid and 860 mL of water are placed in a 3 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (may be omitted), a 2000 mL dropping funnel, and a thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, returning to room temperature, and stirring for 3 hours.
The obtained reaction solution was transferred to a 3 L separatory funnel to separate the organic layer, and the aqueous layer was extracted three times with 400 mL of diethyl ether. Next, the organic layers were combined into one, washed with 400 mL of saturated saline, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, 350 mL of n-heptane was added to the obtained crude crystals, stirred for 1 hour at 50 ° C., returned to room temperature, and suction filtered to obtain 64.8 g (yield 93.8%) of the target compound.

<2> Synthesis of 4- (3-bromophenyl) dibenzofuran
This compound was synthesized by the following procedure with reference to JP2011-051936A.
In a 2 L four-necked round bottom flask equipped with a stirrer, Erlin condenser, nitrogen inlet, and thermometer, 57.5 g (271.8 mmol) of boronic acid obtained in <1> above, 3-iodobromobenzene 84.7 g (298.7 mmol), toluene 900 mL, ethanol 450 mL, potassium carbonate 75.0 g (542.0 mmol) and water 270 mL were added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. Next, 0.31 g (1.34 mmol) of palladium acetate and 0.82 g (2.71 mmol) of tri (o-tolyl) phosphine were added and heated, followed by stirring at reflux temperature for 2 hours.
The resulting reaction solution was cooled to room temperature, the aqueous layer was separated, and extracted with 200 mL of ethyl acetate. Next, the organic layers were combined into one, washed with 200 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained oil was separated by silica gel column chromatography using a mixed solvent of n-hexane and toluene to obtain 69.0 g (yield 78.8%) of the target compound.

<3> Synthesis of 3- (dibenzofuran-4-yl) phenylboronic acid
This compound was also synthesized by the following procedure with reference to JP 2011-051936 A.
Into a 2 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 200 mL isobaric dropping funnel and a thermometer, 57.5 g of dibenzofuran obtained in the above <2> (177.9 mmol) and 900 mL of dehydrated THF were added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 135 mL (205.3 mmol) of n-BuLi was dropped at −50 ° C. or lower, and then the isobaric dropping funnel was washed with 150 mL of THF and added to the reaction solution. Next, after post-reaction at −50 ° C. or less for 1 hour, 24.1 g (231.3 mmol) of B (OMe) ₃ was dropped at a temperature not exceeding −45 ° C., and the isobaric dropping funnel was washed with 200 mL of THF. Added to the reaction. Subsequently, it was post-reacted in an acetone-dry ice bath for 30 minutes, returned to room temperature, and further post-reacted for 20 hours to obtain a boron reaction solution.
Next, 190 mL of concentrated hydrochloric acid and 480 mL of water are placed in a 2 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (which may be omitted), a 2000 mL dropping funnel and a thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, and then returning to room temperature and stirring for 3 hours.
The obtained reaction solution was transferred to a 2 L separatory funnel to separate the organic layer, and the aqueous layer was extracted three times with 400 mL of diethyl ether. Next, the organic layers were combined into one, washed with 400 mL of saturated saline, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, a mixed solution of 175 mL of n-heptane and 75 mL of toluene was added to the obtained crude crystals, stirred at 50 ° C. for 1 hour, returned to room temperature, and suction filtered to 26.5 g (yield 51.7%). To give the desired compound.

Synthesis Example 9
Synthesis of 3- (dibenzothiophen-4-yl) phenylboronic acid

<1> Synthesis of 4-dibenzothiopheneboronic acid
This compound was synthesized according to the following procedure in the same manner as in <1> of Synthesis Example 8.
To a 2 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 300 mL isobaric dropping funnel and a thermometer, 60.0 g (0.326 mol) of dibenzothiophene and 900 mL of dehydrated THF was added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 230 mL (0.385 mol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 150 mL of THF and added to the reaction solution. Next, after post-reaction at -50 ° C. or lower for 1 hour, the mixture was returned to room temperature and stirred for 4 hours. Next, after cooling again to −60 ° C. or lower with an acetone-dry ice bath and dropping 45 mL (0.404 mol) of B (OMe) ₃ at −45 ° C. or lower, the isobaric dropping funnel was washed with 150 mL of THF to obtain a reaction solution. added. Next, after stirring at −45 ° C. or lower for 30 minutes, the acetone-dry ice bath was removed, and the mixture was returned to room temperature and reacted for 20 hours to obtain a boron reaction solution.
Next, 340 mL of concentrated hydrochloric acid and 860 mL of water are placed in a 3 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (may be omitted), a 2000 mL dropping funnel, and a thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, and then returning to room temperature and stirring for 3 hours.
The resulting reaction solution was transferred to a 5 L separatory funnel to separate the organic layer, and the aqueous layer was extracted three times with 600 mL of diethyl ether. The organic layers were then combined into one and extracted three times with 400 mL of a 10% aqueous sodium hydroxide solution, and then placed in a 3 L four-necked round bottom flask equipped with a stirrer, Liebig condenser, 1000 mL dropping funnel and thermometer. The mixture was acidified with 600 mL of glacial acetic acid, and the precipitated crystals were suction filtered. Next, the obtained crystals were washed with water until the odor of acetic acid disappeared and dried in a dryer at 60 ° C. to obtain 62.5 g (yield 83.5%) of the target compound.

<2> Synthesis of 4- (3-bromophenyl) dibenzothiophene
This compound was synthesized according to the following procedure in the same manner as in <2> of Synthesis Example 8.
In a 2 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a nitrogen inlet, and a thermometer, 62.0 g (271.8 mmol) of boronic acid obtained in the above <1>, 3-iodobromobenzene 84.7 g (298.7 mmol), toluene 900 mL, ethanol 450 mL, potassium carbonate 75.0 g (542.0 mmol) and water 270 mL were added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. Next, 0.31 g (1.34 mmol) of palladium acetate and 0.82 g (2.71 mmol) of tri (o-tolyl) phosphine were added and heated, followed by stirring at reflux temperature for 2 hours.
The resulting reaction solution was cooled to room temperature, the aqueous layer was separated, and extracted with 200 mL of ethyl acetate. Next, the organic layers were combined into one, washed with 200 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained oil was separated by silica gel column chromatography using a mixed solvent of n-hexane and toluene to obtain 87.8 g (yield 95.2%) of the target compound.

<3> Synthesis of 3- (dibenzothiophen-4-yl) phenylboronic acid
This compound was synthesized according to the following procedure in the same manner as in <3> of Synthesis Example 8.
87.5 g of the bromide obtained in <2> above was placed in a 2 L 4-neck round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 200 mL isobaric dropping funnel and a thermometer. (258.2 mmol) and 1350 mL of dehydrated THF were added and cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 200 mL (320.0 mmol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 150 mL of THF and added to the reaction solution. Next, after post-reaction at -50 ° C. or lower for 1 hour, 35.2 g (336.8 mmol) of B (OMe) ₃ was added dropwise at a temperature not exceeding −45 ° C. Next, the isobaric dropping funnel was washed with 150 mL of THF and added to the reaction solution, followed by 30 minutes of post-reaction in an acetone-dry ice bath, then returned to room temperature, and further reacted for 20 hours to obtain a boron reaction solution.
Next, 285 mL of concentrated hydrochloric acid and 715 mL of water are placed in a 3 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (which may be omitted), a 2000 mL dropping funnel and a thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, and then returning to room temperature and stirring for 3 hours.
The resulting reaction solution was transferred to a 3 L separatory funnel to separate the organic layer, and the aqueous layer was extracted three times with 500 mL of diethyl ether. Next, the organic layers were combined into one, washed with 500 mL of saturated saline and dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, a mixed solution of 350 mL of n-heptane and 150 mL of toluene was added to the obtained crude crystals, and the mixture was stirred at 50 ° C. for 1 hour, returned to room temperature, filtered with suction, and 49.5 g (yield 63.1%). The target compound was obtained.

Synthesis Example 10
Synthesis of 3- (dibenzofuran-2-yl) phenylboronic acid ester

<1> Synthesis of 2-bromodibenzofuran
This compound was synthesized by the following procedure with reference to International Publication No. 2013/118507 pamphlet.
A 2L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 500 mL isobaric dropping funnel and a thermometer, 136.8 g (0.813 mol) dibenzofuran and 900 mL DCM And cooled to −5 ° C. or lower with an ice-water bath under a nitrogen stream. Then, under a nitrogen stream, a solution obtained by diluting 131.3 g (1.62 mol) of bromine with 210 mL of DCM was added dropwise at −5 ° C. or less over 1.5 hours. Next, the mixture was stirred for 0.5 hours in an ice-water bath, then removed from the ice-water bath and stirred at room temperature for 20 hours.
The obtained reaction solution was transferred to a 2 L separatory funnel, and the DCM layer was washed with 690 mL of water, 210 mL of 20% aqueous sodium thiosulfate and 300 mL of water in this order, dried over magnesium sulfate, and then suction filtered with magnesium sulfate. The solvent was distilled off under reduced pressure. Next, the obtained crude crystals were recrystallized from methanol to obtain 145.0 g (yield: 72.1%) of the desired bromide. The melting point was 109.3-110.5 ° C.

<2> Synthesis of 2-dibenzofuranboronic acid
This compound was also synthesized by the following procedure with reference to International Publication No. 2013/118507 pamphlet.
110.4 g of the bromide obtained in <1> above was placed in a 2 L 4-neck round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 500 mL isobaric dropping funnel and a thermometer. (0.446 mol) and 1000 mL of dehydrated THF were added and cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 420 mL (0.672 mol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 200 mL of THF and added to the reaction solution. Next, after post-reaction at -50 ° C. or lower for 1 hour, 210 mL (0.915 mol) of isopropyl borate [B (i-PrO) ₃ ] was added dropwise at −45 ° C. or lower. Next, the isobaric dropping funnel was washed with 140 mL of THF and added to the reaction solution, and stirred at −45 ° C. or lower for 30 minutes. Then, the acetone-dry ice bath was removed, and the reaction solution was returned to room temperature for 20 hours. Got.
Next, 76 mL of concentrated hydrochloric acid and 764 mL of water were placed in a 3 L four-necked round bottom flask equipped with a stirrer, Liebig condenser (not necessary), a 2000 mL dropping funnel and a thermometer at −5 ° C. in an ice bath. Until cooled. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, returning to room temperature, and stirring for 3 hours.
The obtained reaction solution was transferred to a 3 L separatory funnel to separate the organic layer, and the aqueous layer was extracted with 840 mL of ethyl acetate. Subsequently, the organic layers were combined into one, washed with 560 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, 530 mL of n-heptane was added to the obtained crude crystals, rinsed at 50 ° C. for 1 hour, cooled to room temperature, and suction filtered to obtain 58.2 g (yield 61.4%) of the desired boronic acid.

<3> Synthesis of 2- (3-bromophenyl) dibenzofuran
This compound was synthesized by the following procedure with reference to <2> of Synthesis Example 8.
In a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser tube, a nitrogen inlet tube, and a thermometer, 21.7 g (102.4 mmol) of boronic acid obtained in the above <2>, 3-iodobromobenzene 31.8 g (112.4 mmol), toluene 340 mL, ethanol 170 mL, potassium carbonate 28.2 g (203.9 mmol) and water 102 mL were added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. Next, 0.11 g (0.47 mmol) of palladium acetate and 0.31 g (1.02 mmol) of tri (o-tolyl) phosphine were added and heated, followed by stirring at reflux temperature for 2 hours.
The resulting reaction solution was cooled to room temperature, the aqueous layer was separated, and extracted with 100 mL of ethyl acetate. Subsequently, the organic layers were combined into one, washed with 100 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, the obtained oil was separated by silica gel column chromatography using a mixed solvent of n-hexane and toluene to obtain 24.8 g (yield 75.8) of the desired bromide.

<4> Synthesis of 3- (dibenzofuran-2-yl) phenylboronic acid ester
This compound was synthesized by the following procedure with reference to <3> of Synthesis Example 8.
Into a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer, 24.8 g of the bromide obtained in <3> above. (76.7 mmol) and 160 mL of dehydrated THF were added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 59 mL (92.0 mmol) of n-BuLi was dropped at −50 ° C. or lower, and then the isobaric dropping funnel was washed with 50 mL of THF and added to the reaction solution. Further, after post-reaction at -50 ° C or lower for 1 hour, 2-isopropoxy-4,4,5,5, -tetramethyl-1,3,2-dioxaborolane at a temperature not exceeding -45 ° C. 6 g (92.0 mmol) was added dropwise. Next, the isotonic dropping funnel was washed with 50 mL of THF and added to the reaction solution, and after post-reaction in an acetone-dry ice bath for 30 minutes, the mixture was returned to room temperature and further reacted for 20 hours.
70 mL of water and 50 mL of ethyl acetate were added to the resulting reaction solution, stirred for 30 minutes, allowed to stand, and then separated. The organic layer was further washed with 75 mL of saturated brine, dried over magnesium sulfate, magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, the obtained crude oil was purified by silica gel column chromatography (developing solvent: toluene) and then recrystallized from n-octane to obtain 14.1 g (yield 67.5%) of the target compound. The melting point was 165.7-166.7 ° C.

Synthesis Example 11
Synthesis of 3- (dibenzothiophen-2-yl) phenylboronic acid ester

<1> Synthesis of 2-bromodibenzothiophene
This compound was synthesized according to the following procedure in the same manner as in <1> of Synthesis Example 10.
To a 2 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 500 mL isobaric dropping funnel and a thermometer, 150.0 g (0.813 mol) of dibenzothiophene and DCM 900mL was put, and it cooled to -5 degrees C or less with an ice water bath under nitrogen stream. Next, a solution obtained by diluting 131.3 g (1.62 mol) of bromine with 210 mL of DCM was added dropwise at −5 ° C. or lower over 1.5 hours under a nitrogen stream, followed by stirring for 0.5 hours in an ice water bath, and further with ice water. The bath was removed and the mixture was stirred at room temperature for 20 hours.
The obtained reaction solution was transferred to a 2 L separatory funnel, and the DCM layer was washed with 690 mL of water, 210 mL of 20% aqueous sodium thiosulfate and 300 mL of water in this order, dried over magnesium sulfate, and then magnesium sulfate was suction filtered. And the solvent was distilled off under reduced pressure. Subsequently, the obtained crude crystals were recrystallized from acetonitrile to obtain 162.8 g (yield: 76.0%) of the target bromide. The melting point was 118.5-120.1 ° C.

<2> Synthesis of 2-dibenzothiopheneboronic acid
This compound was synthesized according to the following procedure in the same manner as in <2> of Synthesis Example 10.
91.3 g of the bromide obtained in <1> above was placed in a 2 L 4-neck round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 500 mL isobaric dropping funnel and a thermometer. (0.347 mol) and 800 mL of dehydrated THF were added and cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 330 mL (0.528 mol) of n-BuLi was dropped at −50 ° C. or lower, and then the isobaric dropping funnel was washed with 200 mL of THF and added to the reaction solution. Next, after post-reaction at -50 ° C. or lower for 1 hour, 160 mL (0.697 mol) of [B (i-PrO) ₃ ] was added dropwise at −45 ° C. or lower. Next, the isotonic dropping funnel is washed with 130 mL of THF and added to the reaction solution, and stirred at −45 ° C. or lower for 30 minutes. Then, the acetone-dry ice bath is removed and the temperature is returned to room temperature. It was.
Next, 59 mL of concentrated hydrochloric acid and 591 mL of water were placed in a 3 L four-necked round bottom flask equipped with a stirrer, Liebig condenser (may be omitted), 2000 mL dropping funnel and thermometer. Until cooled. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, and then returning to room temperature and stirring for 3 hours.
The obtained reaction solution was transferred to a 3 L separatory funnel to separate the organic layer, and the aqueous layer was extracted with 810 mL of DCM. Subsequently, the organic layers were combined into one, washed with 540 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, 450 mL of n-heptane was added to the obtained crude crystals, rinsed at 50 ° C. for 1 hour, cooled to room temperature, and suction filtered to obtain 63.6 g of the desired boronic acid (yield 80.6%). .

<3> Synthesis of 2- (3-bromophenyl) dibenzothiophene
This compound was synthesized by the following procedure in the same manner as in <3> of Synthesis Example 10.
In a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a nitrogen inlet, and a thermometer, 24.0 g (105.2 mmol) of boronic acid obtained in the above <2>, 3-iodobromobenzene 32.8 g (115.6 mmol), 350 mL of toluene, 175 mL of ethanol, 29.0 g (209.8 mmol) of potassium carbonate and 105 mL of water were added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. Subsequently, 0.12 g (0.51 mmol) of palladium acetate and 0.32 g (1.05 mmol) of tri (o-tolyl) phosphine were added and heated, followed by stirring at reflux temperature for 2 hours.
The resulting reaction solution was cooled to room temperature, the aqueous layer was separated, and extracted with 100 mL of ethyl acetate. Subsequently, the organic layers were combined into one, washed with 100 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, the obtained oil was separated by silica gel column chromatography using a mixed solvent of n-hexane and toluene to obtain 26.7 g (yield 74.8%) of the desired bromide.

<4> Synthesis of 3- (dibenzothiophen-2-yl) phenylboronic acid ester
This compound was synthesized according to the following procedure in the same manner as in <4> of Synthesis Example 10.
35.6 g of the bromide obtained in <3> above was added to a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer. (105.2 mmol) and 230 mL of dehydrated THF were added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 80 mL (128.0 mmol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 50 mL of THF and added to the reaction solution. Next, after post-reaction at -50 ° C. or less for 1 hour, 21.4 g (126.2 mmol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added to −45. The solution was added dropwise at a temperature not exceeding ℃. Subsequently, the isobaric dropping funnel was washed with 50 mL of THF and added to the reaction solution, followed by post-reaction in an acetone-dry ice bath for 30 minutes, and then returned to room temperature for further 20 hours.
100 mL of water and 85 mL of ethyl acetate were added to the resulting reaction solution, stirred for 30 minutes, allowed to stand, and then separated. Next, the organic layer was washed with 125 mL of saturated brine and dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, the obtained crude oil was purified by silica gel column chromatography (developing solvent: toluene) and then recrystallized from n-octane to obtain 26.7 g (yield 71.2%) of the target compound. Melting point was 147.2-148.0 ° C.

Synthesis Example 12
Synthesis of 3- (dibenzofuran-3-yl) phenylboronic acid

<1> Synthesis of 3-nitrodibenzofuran
This compound was synthesized by the following procedure with reference to Journal of Chemical Society of Japan, Vol. 55, No. 2, page 629 (1982).
Into a 1 L four-necked round bottom flask equipped with a stirrer, Liebig condenser (optional), thermometer, nitrogen inlet tube and 200 mL dropping funnel, 40.0 g (0.24 mol) benzofuran and 500 mL trifluoroacetic acid And cooled to 0 ° C. or lower with an ice-water bath. Next, under a nitrogen stream, 100 mL of trifluoroacetic acid in which 18.2 g (0.29 mol) of nitric acid (d = 1.52) was dissolved was dropped so that the reaction solution did not exceed 0 ° C., and then at 0 ° C. or less for 1 hour. After reaction, a reaction solution was obtained.
Next, 3 kg of crushed ice was added to a 5 L four-necked round bottom flask equipped with a stirrer, Liebig condenser (optional), thermometer, and 200 mL dropping funnel, and the above reaction was performed while stirring slowly. The liquid was slowly added, and the precipitated crystals were suction filtered. The crystals on Nutsche were washed with 600 mL of water, 500 mL of 5% aqueous potassium carbonate solution and 1000 mL of water in this order, and dried in a vacuum dryer at 60 ° C. to obtain crude crystals. Then, recrystallization was performed with 350 mL of acetic acid to obtain 38.7 g (yield: 76.0%) of the target nitro compound. The melting point was 181.7 ° C. to 182.8 ° C.

<2> Synthesis of 3-aminodibenzofuran
This compound was synthesized by the following procedure with reference to Journal of Medicinal Chemistry, 46 (12), 2436-2445; 2003.
In a 2 L 4-neck round bottom flask equipped with a stirrer, an Erlin condenser and a thermometer, 36.0 g (0.167 mol) of the nitro compound obtained in the above <1>, 600 mL of isopropyl alcohol, 90 m of water and chloride 26.9 g (0.501 mol) of ammonium was added and stirred at room temperature. Next, after 93.3 g (1.67 mol) of iron powder was added in portions, the mixture was gently heated to reflux temperature and reacted for 11 hours.
The obtained reaction liquid was cooled to room temperature, iron powder was removed using celite, and the solvent was distilled off under reduced pressure. Subsequently, the obtained crude crystals were purified by silica gel column chromatography using a mixed solvent of n-hexane and ethyl acetate to obtain 19.5 g (yield 62.7%) of the target amine compound. The melting point was 82.7-83.4 ° C.

<3> Synthesis of 3-bromodibenzofuran
This compound was synthesized by the following procedure with reference to International Publication No. 2002/078693 pamphlet.
In a 500 mL four-necked round bottom flask equipped with a stirrer, Liebig condenser (optional), thermometer, and 200 mL dropping funnel, 19.0 g (102.6 mmol) of the amino compound obtained in the above <2> , 190 mL of water and 57 mL of 48% hydrobromic acid were added and stirred overnight. Next, the solution was cooled to −10 ° C. in an ice water bath, and a solution obtained by dissolving 8.1 g (117.4 mmol) of sodium nitrite in 150 mL of water was added dropwise under conditions such that the temperature did not rise above 5 ° C. The reaction solution was stirred at 5 ° C. or lower for 1 hour to obtain a diazonium solution.
Next, to a 1 L four-necked round bottom flask equipped with a stirrer, Erlin condenser, thermometer, and 500 mL dropping funnel, cuprous bromide 16.2 g (116.9 mmol), 48% hydrobromic acid 38 mL and 90 mL of water were added, and the mixture was cooled to 0 ° C. and stirred. Next, the diazonium liquid was added dropwise at a temperature not exceeding 5 ° C., stirred at the same temperature for 30 minutes, then heated to 40 ° C., and stirred at the same temperature for 18 hours.
To the resulting reaction solution, 200 mL of water was added, cooled to room temperature, and extracted twice with 200 mL of DCM. Next, the organic layer was washed with 100 mL of a 5% aqueous sodium sulfite solution, then washed with 100 mL of saturated brine and dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained crude product was purified by silica gel column chromatography using n-heptane as a developing solution to obtain 17.2 g (yield 68.0%) of the desired bromide. Melting point is 118.3-119.5 ° C

<4> Synthesis of 3-dibenzofuranboronic acid
This compound was also synthesized by the following procedure with reference to International Publication No. 2013/118507 pamphlet.
15.0 g of the bromide obtained in <3> above was placed in a 500 mL four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer. (68.8 mmol) and 160 mL of dehydrated THF were added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Subsequently, 52 mL (82.6 mmol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 50 mL of THF and added to the reaction solution. Subsequently, after post-reaction at -50 ° C. or lower for 1 hour, 21 mL (89.5 mmol) of [B (i-PrO) ₃ ] was added dropwise at −45 ° C. or lower. Next, the isotonic dropping funnel was washed with 40 mL of THF and added to the reaction solution, and stirred at −45 ° C. or lower for 30 minutes. Then, the acetone-dry ice bath was removed and the temperature was returned to room temperature. It was.
Next, 12 mL of concentrated hydrochloric acid and 119 mL of water are placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (not necessary), a 500 mL dropping funnel and a thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, returning to room temperature, and stirring for 3 hours.
The obtained reaction solution was transferred to a 1 L separatory funnel to separate the organic layer, and the aqueous layer was extracted with 170 mL of ethyl acetate. Next, the organic layers were combined into one, washed with 120 mL of saturated saline, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, 110 mL of n-heptane was added to the resulting crude crystals, rinsed at 50 ° C. for 1 hour, cooled to room temperature, and suction filtered to obtain 10.7 g of the desired boronic acid (yield 73.2%). .

<5> Synthesis of 3- (3-bromophenyl) dibenzofuran
This compound was synthesized by the following procedure with reference to <2> of Synthesis Example 8.
In a 1 L four-necked round bottom flask equipped with a stirrer, Erlin condenser, nitrogen inlet, and thermometer, 10.5 g (49.5 mmol) of boronic acid obtained in the above <4>, 3-iodobromobenzene 15.4 g (54.4 mmol), 170 mL of toluene, 85 mL of ethanol, 13.6 g (98.7 mmol) of potassium carbonate and 50 mL of water were added and stirred at room temperature for 30 minutes under a nitrogen stream. Next, 53.2 mg (0.22 mmol) of palladium acetate and 0.15 g (0.49 mmol) of tri (o-tolyl) phosphine were added and heated, followed by stirring at reflux temperature for 2 hours.
The resulting reaction solution was cooled to room temperature, the aqueous layer was separated, and extracted with 50 mL of ethyl acetate. Next, the organic layers were combined, washed with 50 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Then, the obtained oil was separated by silica gel column chromatography using a mixed solvent of n-hexane and toluene to obtain 14.4 g (yield 91.0%) of the desired bromide.

<6> Synthesis of 3- (dibenzofuran-3-yl) phenylboronic acid
This compound was synthesized according to the following procedure in the same manner as in <3> of Synthesis Example 8.
In a 500 mL four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer, 14.4 g of the bromide obtained in <5> above. (44.5 mmol) and 225 mL of dehydrated THF were added and cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Subsequently, 34 mL (54.0 mmol) of n-BuLi was dropped at −50 ° C. or lower, and then the isobaric dropping funnel was washed with 40 mL of THF and added to the reaction solution. Then, after post-reaction at -50 ° C or lower for 1 hour, 6.0 g (57.8 mmol) of B (OMe) _{3 was} added dropwise at a temperature not exceeding -45 ° C. Next, the isobaric dropping funnel was washed with 50 mL of THF and added to the reaction solution, followed by 30 minutes of post-reaction in an acetone-dry ice bath, then returned to room temperature and further reacted for 20 hours to obtain a boron reaction solution.
Next, 48 mL of concentrated hydrochloric acid and 120 mL of water are placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (which may be omitted), a 500 mL dropping funnel, and a thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, returning to room temperature, and stirring for 3 hours.
The obtained reaction solution was transferred to a 1 L separatory funnel to separate the organic layer, and the aqueous layer was extracted three times with 100 mL of diethyl ether. Subsequently, the organic layers were combined into one, washed with 100 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, a mixed solution of 45 mL of n-heptane and 18 mL of toluene was added to the obtained crude crystals, and the mixture was stirred at 50 ° C. for 1 hour, returned to room temperature, and suction filtered to obtain 7.1 g (yield: 54.3%). A compound was obtained.

Synthesis Example 13
Synthesis of 3- (dibenzothiophen-3-yl) phenylboronic acid

<1> Synthesis of dibenzosulfoxide
This compound was synthesized by the following procedure with reference to International Publication No. 2011/106344 pamphlet.
To a 2 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 1000 mL isobaric dropping funnel and a thermometer, 64.4 g (0.35 mol) of dibenzothiophene and Chloroform 700mL was put, and it cooled to -40 degreeC with the acetonitrile dry ice bath under nitrogen stream. Next, after adding 700 mL of a chloroform solution of 78.3 g (0.35 mol) of metachloroperbenzoic acid (mCPBA) from an isobaric dropping funnel at a temperature not exceeding −30 ° C., the mixture was stirred at the same temperature for 1 hour and further brought to room temperature. The mixture was returned and stirred for 1 hour.
The crystals produced as a by-product from the obtained reaction solution were filtered, transferred to a 2 L separatory funnel, and 300 mL of water was added to neutralize with a 10% aqueous sodium carbonate solution. Further, the neutralized organic layer was washed twice with 200 mL of water and dried over sodium sulfate, and then sodium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained reaction product was purified by silica gel column chromatography using a mixed solvent of DCM and n-hexane, and further recrystallized with ethanol to obtain 50.5 g (yield: 73.7%) of the desired dibenzosulfoxide. . Melting point was 187.2-188.4 ° C.

<2> Synthesis of 3-nitrodibenzosulfoxide
This compound was also synthesized by the following procedure with reference to International Publication No. 2011/106344 pamphlet.
A 500 mL four-necked round bottom flask equipped with a stirrer, Liebig condenser (optional), 200 mL dropping funnel and thermometer is charged with 110 mL of acetic acid and concentrated sulfuric acid at 0 ° C or lower in an ice-water bath. Then, 50.0 g (0.25 mol) of dibenzosulfoxide obtained in the above <1> was slowly added while stirring. Next, 120 mL of fuming nitric acid was added dropwise at a temperature not exceeding 0 ° C., and the mixture was further vigorously stirred at 0 ° C. or lower for 30 minutes.
The obtained reaction solution was slowly poured into 2 Kg of ice water placed in a 3 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (optional) and a thermometer, and the precipitated crystals were suction filtered. Washed with 2 L of salt water. Further, the crystals were dissolved in 500 mL of DCM and dried over magnesium sulfate, and then the magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained crude crystals were recrystallized with ethanol to obtain 44.3 g (yield 69.0%) of the target nitro compound. The melting point was 208.3-209.4 ° C.

<3> Synthesis of 3-aminodibenzothiophene
This compound was synthesized by the following procedure.
A 1 L autoclave was charged with 44.0 g (0.18 mol) of the nitro compound obtained in the above <2>, 20 g of 10% palladium carbon, and 800 mL of ethyl acetate, and the mixture was covered and stirred. Hydrogen gas was then added at a pressure of 0.35 Mpa and fed until the absorption was completed. When the absorption disappeared, the reaction was stopped and the bag was opened. The reaction solution was filtered using Celite, and the solvent was distilled off under reduced pressure. Next, the obtained crude crystals were purified by silica gel column chromatography using a mixed solvent of DCM and n-hexane to obtain 27.1 g (yield: 75.6%) of the target amine compound. The melting point was 120.6-121.4 ° C.

<4> Synthesis of 3-bromodibenzothiophene
This compound was synthesized by the following procedure with reference to <3> of Synthesis Example 12.
In a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (optional), a thermometer, and a 300 mL dropping funnel, 27.0 g (135.5 mmol) of the amino compound obtained in <3> above. Then, 250 mL of water and 75 mL of 48% hydrobromic acid were added and stirred overnight. Next, the solution was cooled to −10 ° C. in an ice water bath, and a solution obtained by dissolving 10.7 g (155.0 mmol) of sodium nitrite in 200 mL of water was added dropwise so that the temperature did not rise above 5 ° C. Next, the diazotized reaction liquid was stirred at 5 ° C. or lower for 1 hour to obtain a diazonium liquid.
Next, 21.4 g of cuprous bromide (154.4 mmol), 48% hydrobromic acid was added to a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a thermometer, and a 1 L dropping funnel. 50 mL and 120 mL of water were added, and the mixture was cooled to 0 ° C. and stirred. Next, the diazonium liquid was added dropwise at a temperature not exceeding 5 ° C., followed by stirring at the same temperature for 30 minutes, further raising the temperature to 40 ° C. and stirring for 18 hours.
The obtained reaction solution was charged with 260 mL of water, cooled to room temperature, and extracted twice with 260 mL of DCM. Next, the organic layer was washed with 130 mL of a 5% aqueous sodium sulfite solution, further washed with 130 mL of saturated brine, and then dried over magnesium sulfate. Subsequently, magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, the obtained crude product was purified by silica gel column chromatography using n-heptane as a developing solution to obtain 28.9 g (yield: 81.1%) of the desired bromide. The melting point was 97.3-98.3 ° C.

<5> Synthesis of 3-dibenzothiopheneboronic acid
This compound was synthesized by the following procedure with reference to <4> of Synthesis Example 12.
28.5 g of the bromide obtained in <4> above was placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer. (108.3 mmol) and 250 mL of dehydrated THF were added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Subsequently, 82 mL (130.0 mmol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 80 mL of THF and added to the reaction solution. Next, after post-reaction at −50 ° C. or lower for 1 hour, [B (i-PrO) ₃ ] 33 mL (140.9 mmol) was added dropwise at −45 ° C. or lower. Next, the isobaric dropping funnel was washed with 63 mL of THF and added to the reaction liquid, and stirred at −45 ° C. or lower for 30 minutes. Then, the acetone-dry ice bath was removed and the temperature was returned to room temperature. Obtained.
Next, 19 mL of concentrated hydrochloric acid and 187 mL of water are placed in a 1 L four-necked round bottom flask equipped with a stirrer, Liebig condenser (may be omitted), 1 L dropping funnel, and thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, returning to room temperature, and stirring for 3 hours.
The obtained reaction solution was transferred to a 1 L separatory funnel to separate the organic layer, and the aqueous layer was extracted with 270 mL of ethyl acetate. Next, the organic layers were combined, washed with 190 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, 170 mL of n-heptane was added to the obtained crude crystals, rinsed at 50 ° C. for 1 hour, cooled to room temperature, and suction filtered to obtain 17.7 g of the desired boronic acid (yield 71.6%). It was.

<6> Synthesis of 3- (3-bromophenyl) dibenzothiophene
This compound was synthesized according to the following procedure with reference to <5> of Synthesis Example 12.
In a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser tube, a nitrogen inlet tube, and a thermometer, 17.5 g (76.7 mmol) of boronic acid obtained in the above <5>, 3-iodobromobenzene 23.9 g (84.3 mmol), 260 mL of toluene, 130 mL of ethanol, 21.1 g (153.0 mmol) of potassium carbonate and 76 mL of water were added and stirred at room temperature for 30 minutes under a nitrogen stream. Next, 82.5 mg (0.34 mmol) of palladium acetate and 0.23 g (0.76 mmol) of tri (o-tolyl) phosphine were added and heated, followed by stirring at reflux temperature for 2 hours.
The resulting reaction solution was cooled to room temperature, the aqueous layer was separated, and extracted with 80 mL of ethyl acetate. Next, the organic layers were combined, washed with 80 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, the obtained oil was separated by silica gel column chromatography using a mixed solvent of n-hexane and toluene to obtain 22.2 g (yield: 85.5%) of the desired bromide.

<7> Synthesis of 3- (dibenzothiophen-3-yl) phenylboronic acid
This compound was synthesized by the following procedure in the same manner as in <6> of Synthesis Example 12.
22.0 g of the bromide obtained in the above <6> was placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 50 mL isobaric dropping funnel and a thermometer. (64.8 mmol) and 330 mL of dehydrated THF were added and cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 50 mL (80.0 mmol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 60 mL of THF and added to the reaction solution. Subsequently, after post-reaction at -50 ° C or lower for 1 hour, 8.7 g (84.1 mmol) of B (OMe) _{3 was} added dropwise at a temperature not exceeding -45 ° C. Next, the isobaric dropping funnel was washed with 75 mL of THF and added to the reaction solution, and after post-reaction in an acetone-dry ice bath for 30 minutes, the reaction solution was returned to room temperature and further reacted for 20 hours to obtain a boron reaction solution.
Next, 70 mL of concentrated hydrochloric acid and 175 mL of water are placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (not necessary), a 1 L dropping funnel and a thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, returning to room temperature, and stirring for 3 hours.
The obtained reaction solution was transferred to a 1 L separatory funnel to separate the organic layer, and the aqueous layer was extracted three times with 150 mL of diethyl ether. Next, the organic layers were combined into one, washed with 150 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, a mixed solution of 66 mL of n-heptane and 26 mL of toluene was added to the obtained crude crystals, and the mixture was stirred at 50 ° C. for 1 hour, then returned to room temperature, suction filtered, and 11.5 g (yield 58.4%). To give the desired compound.

Synthesis Example 14
Synthesis of 3- (dibenzofuran-1-yl) phenylboronic acid

<1> Synthesis of 2'-phenoxyacetanilide
This compound was synthesized according to the following procedure with reference to Chemical Communications (Cambridge, United Kingdom) (2011), 47, (27), 7845-7847.
To a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 50 mL isobaric dropping funnel, and a thermometer, 50.0 g of 2′-phenoxyaniline (0. 27 mol) and 500 mL of DCM were added and stirred at room temperature under a nitrogen stream. Next, 42.8 g (0.41 mol) of triethylamine was added and cooled to −10 ° C. in an ice-water bath, and 30.3 g (0.38 mol) of acetyl chloride was added dropwise at 0 ° C. or less while paying attention to heat generation from the dropping funnel. . Further, the mixture was stirred at the same temperature for 30 minutes, returned to room temperature and post-reacted for 5 hours to obtain a reaction solution.
Next, 250 g of crushed ice was added to a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a 1 L dropping funnel and a thermometer, and the reaction solution was stirred while stirring. The whole amount was dropped. Next, the dropping funnel was washed with 100 mL of DCM and added to the reaction solution, and then stirred at room temperature for one day.
The obtained reaction solution was transferred to a 1 L separatory funnel, and the organic layer was separated. The organic layer was washed three times with 250 mL of water, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration. The solvent was distilled off to obtain 73.2 g (yield 119.8%) of the target compound. The obtained compound was used for the next reaction as it was.

<2> Synthesis of N-4-dibenzofuranylacetamide
This compound was synthesized by the following procedure with reference to JP-T-2013-520508.
In a 1 L 4-neck round bottom flask equipped with a stirrer, a Liebig condenser and a thermometer, 73.0 g (0.321 mol) of the acetanilide obtained in the above <1>, 328.0 g (3.21 mol) of pivalic acid, 7.2 g (32.1 mmol) of palladium acetate and 4.4 g (32.1 mmol) of potassium carbonate were added and reacted at 105 ° C. for 48 hours, and further reacted at 115 ° C. for 24 hours.
The resulting reaction solution was cooled to room temperature and fed into 1825 mL of water, and then 256 g of sodium carbonate was added in several portions while paying attention to foaming. Next, the organic layer extracted three times with 560 mL of ethyl acetate was washed with water 360 mL, water: saturated saline = 1: 1 360 mL, saturated brine 360 mL in this order, dried over magnesium sulfate, and then magnesium sulfate was suction filtered. And the solvent was distilled off under reduced pressure. Subsequently, the obtained crude product was purified by silica gel column chromatography using chloroform as a developing solvent to obtain 61.8 g (yield: 85.5%) of the target compound.

<3> Synthesis of 1-bromo-N-4-dibenzofuranylacetamide
This compound was synthesized according to the following procedure with reference to JP-A-2006-135775.
In a 1 L four-necked round bottom flask equipped with a stirrer, Liebig condenser (optional), 200 mL dropping funnel and thermometer, 60.1 g (0.267 mol) of the acetamide obtained in the above <2> 720 mL of acetic acid was added and stirred at 35 ° C. Next, 44.0 g (0.555 mol) of bromine diluted with 135 mL of acetic acid was added dropwise, and the dropping funnel was washed with 45 mL of acetic acid and added to the reaction solution. Subsequently, after stirring at 35-40 degreeC for 4 hours, the reaction liquid was poured into 5.4L of water, and also stirred for one day and night. The precipitated crystals were suction filtered to obtain 68.0 g (yield 83.9%) of the target bromide.

<4> Synthesis of 1-bromo-4-dibenzofuranamine (hydrochloride)
This compound was also synthesized according to the following procedure with reference to JP-A-2006-135775.
In a 2 L 4-neck round bottom flask equipped with a stirrer, an Erlin condenser, a nitrogen inlet, and a thermometer, 68.0 g (0.224 mol) of the bromide obtained in the above <3>, ethanol 580 mL, tetrahydrofuran 240 mL, 101.0 g (1.8 mol) of potassium hydroxide and 240 mL of water were added and reacted at reflux temperature for 18 hours.
The solvent was distilled off from the resulting reaction solution under reduced pressure, and the crude product was extracted with 650 mL of diethyl ether. Further, the aqueous layer was separated and extracted with 220 mL of diethyl ether, and then the diethyl ether layers were combined and dried with potassium carbonate. Next, after potassium carbonate was filtered, the diethyl ether layer was transferred to a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser, a 200 mL dropping funnel and a thermometer, and 200 mL of 2N hydrochloric acid diethyl ether solution was added dropwise. did. At the same time as the dropwise addition, the hydrochloride of the target compound was precipitated. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour, and then suction filtered to obtain 53.6 g (yield 80.5%) of the hydrochloride of the target compound. The obtained hydrochloride salt was used for the next reaction as it was.

<5> Synthesis of 1-bromodibenzofuran
This compound was also synthesized according to the following procedure with reference to JP-A-2006-135775.
Into a 1 L 4-neck round bottom flask equipped with a stirrer, Liebig condenser (optional), 200 mL dropping funnel and thermometer, 52.5 g (0.176 mol) of amine hydrochloride obtained in <4> above. ), 270 mL of acetic acid, 62 mL of concentrated hydrochloric acid, and 161 mL of water were added, and the mixture was cooled to −5 ° C. or lower in an ice-water bath. Next, an aqueous solution in which 13.5 g (0.195 mol) of sodium nitrite was dissolved in 75 mL of water was dropped from the dropping funnel at a temperature not exceeding 5 ° C., and then stirred at 5 ° C. or lower for 1 hour to obtain a diazo solution.
Next, the diazo solution was transferred to a 500 mL dropping funnel and set in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (may be omitted) and a thermometer. Next, 200 mL of 50% diphosphorous acid and 100 mL of water were added, and the mixture was cooled to −5 ° C. or lower in an ice water bath. Next, the diazo solution was added dropwise at a temperature not exceeding 5 ° C., stirred for 1 hour in an ice-water bath, returned to room temperature, and further stirred for 48 hours.
The obtained reaction solution was extracted twice with 350 mL of ethyl acetate, and then the ethyl acetate layer was washed twice with 350 mL of water and dried over magnesium sulfate. Then, magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained crude oil was purified by a silica gel column using n-heptane as a developing solution to obtain 34.7 g (yield 78.3%) of the desired bromide.

<6> Synthesis of 1-dibenzofuranboronic acid
This compound was synthesized by the following procedure with reference to International Publication No. 2013/118507 pamphlet.
The bromide obtained in the above <5> was placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 200 mL isobaric dropping funnel and a thermometer. (139.6 mmol) and dehydrated THF (325 mL) were added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Subsequently, 106 mL (167.6 mmol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 100 mL of THF and added to the reaction solution. Subsequently, after post-reaction at -50 ° C. or lower for 1 hour, 43 mL (181.6 mmol) of [B (i-PrO) ₃ ] was added dropwise at −45 ° C. or lower. Subsequently, the isobaric dropping funnel was washed with 80 mL of THF and added to the reaction solution, and then stirred at −45 ° C. or lower for 30 minutes, the acetone-dry ice bath was removed, the temperature was returned to room temperature, and the reaction was further continued for 20 hours. A reaction solution was obtained.
Next, 24 mL of concentrated hydrochloric acid and 241 mL of water are placed in a 1 L four-necked round bottom flask equipped with a stirrer, Liebig condenser (not necessary), 1 L dropping funnel and thermometer, and -5 in an ice bath. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, returning to room temperature, and stirring for 3 hours.
The obtained reaction solution was transferred to a 1 L separatory funnel to separate the organic layer, and the aqueous layer was extracted with 340 mL of ethyl acetate. Next, the organic layers were combined, washed with 240 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration. The solvent was distilled off under reduced pressure. Next, 220 mL of n-heptane was added to the resulting crude crystals, rinsed at 50 ° C. for 1 hour, cooled to room temperature, and suction filtered to obtain 21.6 g (yield 72.8%) of the desired boronic acid. .

<7> Synthesis of 1- (3-bromophenyl) dibenzofuran
This compound was synthesized by the following procedure with reference to <2> of Synthesis Example 8.
In a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a nitrogen inlet, and a thermometer, 21.5 g (101.3 mmol) of boronic acid obtained in the above <6>, 3-iodobromobenzene 31.5 g (111.4 mmol), toluene 350 mL, ethanol 175 mL, potassium carbonate 27.8 g (202.1 mmol) and water 100 mL were added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. Next, 108.9 mg (0.45 mmol) of palladium acetate and 0.31 g (1.0 mmol) of tri (o-tolyl) phosphine were added and heated, followed by stirring at reflux temperature for 2 hours.
The resulting reaction solution was cooled to room temperature, the aqueous layer was separated, and extracted with 100 mL of ethyl acetate. Subsequently, the organic layers were combined into one, washed with 100 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, the obtained oil was separated by silica gel column chromatography using a mixed solvent of n-hexane and toluene to obtain 28.7 g (yield: 88.5%) of the desired bromide.

<8> Synthesis of 3- (dibenzofuran-1-yl) phenylboronic acid
This compound was synthesized according to the following procedure in the same manner as in <3> of Synthesis Example 8.
28.5 g of the bromide obtained in <7> above was added to a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer. (88.0 mmol) and 445 mL of dehydrated THF were added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 67 mL (106.9 mmol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 80 mL of THF and added to the reaction solution. Then 1 hour at -50 ° C. or less, allowed to _after-react, B a (OMe) 3 11.9g (114.4mmol) , was added dropwise at a temperature below -45 ° C.. Next, the isobaric dropping funnel was washed with 100 mL of THF and added to the reaction solution, followed by 30 minutes of post-reaction in an acetone-dry ice bath, then returned to room temperature and further reacted for 20 hours to obtain a boron reaction solution.
Next, 95 mL of concentrated hydrochloric acid and 238 mL of water are placed in a 2 L four-necked round bottom flask equipped with a stirrer, Liebig condenser (may be omitted), 1 L dropping funnel and thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, returning to room temperature, and stirring for 3 hours.
The obtained reaction solution was transferred to a 2 L separatory funnel to separate the organic layer, and the aqueous layer was extracted three times with 200 mL of diethyl ether. Next, the organic layers were combined into one, washed with 200 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, a mixed solution of 89 mL of n-heptane and 35 mL of toluene was added to the obtained crude crystals, and the mixture was stirred at 50 ° C. for 1 hour, then returned to room temperature, filtered with suction, and 15.4 g (yield 59.4%). To give the desired compound.

Synthesis Example 15
Synthesis of 3- (dibenzothiophen-1-yl) phenylboronic acid

<1> Synthesis of 2'-phenylthioacetanilide
This compound was synthesized according to the following procedure with reference to A European Journal, 22 (30), 10607-10613; 2016.
Into a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 50 mL isobaric dropping funnel and a thermometer, 51.2 g of 2′-phenylthioaniline (0 .254 mol) and 470 mL of DCM were added and stirred at room temperature under a nitrogen stream. Next, 40.3 g (0.39 mol) of triethylamine was added, and after cooling to −10 ° C. in an ice water bath, 28.5 g (0.35 mol) of acetyl chloride was added dropwise at 0 ° C. or less while paying attention to heat generation. Next, the mixture was stirred at the same temperature for 30 minutes, returned to room temperature and post-reacted for 5 hours to obtain a reaction solution.
Next, 200 g of crushed ice was placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride pipe, a 1 L dropping funnel, and a thermometer, and the reaction liquid was stirred. The whole amount was dropped. Next, the dropping funnel was washed with 80 mL of DCM and added to the reaction solution, and then stirred at room temperature for one day.
The obtained reaction solution was transferred to a 1 L separatory funnel, and the organic layer was separated, then washed three times with 200 mL of water, and dried over magnesium sulfate. Then, magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained crude product was purified by silica gel column chromatography using ethyl acetate and toluene as eluents to obtain 59.1 g (yield 95.6%) of the target compound. The melting point was 96.3-97.1 ° C.

<2> Synthesis of N-4-dibenzothiophenylacetamide
This compound was synthesized by the following procedure with reference to JP-T-2013-520508.
In a 1 L 4-neck round bottom flask equipped with a stirrer, a Liebig condenser and a thermometer, 59.0 g (0.242 mol) of acetanilide obtained in the above <1>, 250.0 g (2.34 mol) of pivalic acid, Palladium acetate 5.5 g (23.4 mmol) and potassium carbonate 3.4 g (24.3 mmol) were added and reacted at 105 ° C. for 48 hours, and further reacted at 115 ° C. for 24 hours.
The resulting reaction solution was cooled to room temperature, fed into 1390 mL of water, 185 g of sodium carbonate was added in several portions while paying attention to foaming, and then extracted three times with 420 mL of ethyl acetate. Next, the organic layers are combined, washed with 280 mL of water, water: saturated saline = 1: 1 280 mL, saturated saline 280 mL in this order, dried over magnesium sulfate, and then magnesium sulfate is removed by suction filtration. The solvent was distilled off under reduced pressure. Subsequently, the obtained crude product was purified by silica gel column chromatography using chloroform as a developing solvent to obtain 55.4 g (yield 94.3%) of the target compound.

<3> Synthesis of 1-bromo-N-4-dibenzofuranylacetamide
This compound was synthesized according to the following procedure with reference to JP-A-2006-135775.
Into a 1 L 4-neck round bottom flask equipped with a stirrer, Liebig condenser (optional), 200 mL dropping funnel and thermometer, 55.4 g (0.230 mol) of acetamide obtained in <2> above. After adding 620 mL of acetic acid and stirring at 35 ° C., 37.8 g (0.477 mol) of bromine diluted with 116 mL of acetic acid was added dropwise. Next, the dropping funnel was washed with 40 mL of acetic acid and added to the reaction solution, followed by stirring at 35 to 40 ° C. for 4 hours.
The obtained reaction solution was poured into 5.6 L of water, stirred for one day and night, and the precipitated crystals were suction filtered to obtain 58.6 g (yield: 84.1%) of the desired bromide.

<4> Synthesis of 1-bromo-4-dibenzothiophenamine (hydrochloride)
This compound was also synthesized according to the following procedure with reference to JP-A-2006-135775.
In a 2 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser tube, a nitrogen inlet tube and a thermometer, 58.5 g (0.183 mol) of the bromide obtained in the above <3>, ethanol 470 mL, tetrahydrofuran 200 mL, water 82.4 g (1.5 mol) of potassium oxide and 195 mL of water were added and reacted at reflux temperature for 18 hours.
The solvent was distilled off from the resulting reaction solution under reduced pressure, and the crude product was extracted with 530 mL of diethyl ether. Next, the aqueous layer was separated and extracted with 180 mL of diethyl ether, and then the diethyl ether layers were combined and dried over potassium carbonate. Then, potassium carbonate was removed by filtration, and the diethyl ether layer was transferred to a 1 L four-necked round bottom flask equipped with a stirrer, Liebig condenser, 200 mL dropping funnel and thermometer, and 160 mL of 2N-diethyl ether hydrochloride solution 160 mL. Was dripped. At the same time as the dropwise addition, the hydrochloride of the target compound was precipitated. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour and suction filtered to obtain 44.0 g (yield: 81.2%) of the hydrochloride of the target compound. The obtained hydrochloride salt was used for the next reaction as it was.

<5> Synthesis of 1-bromodibenzothiophene
This compound was also synthesized according to the following procedure with reference to JP-A-2006-135775.
In a 1 L four-necked round bottom flask equipped with a stirrer, Liebig condenser (optional), 100 mL dropping funnel and thermometer, 43.5 g (0.156 mol) of amine hydrochloride obtained in <4> above. ), 240 mL of acetic acid, 55 mL of concentrated hydrochloric acid and 143 mL of water were added, and the mixture was cooled to −5 ° C. or lower in an ice-water bath. Next, an aqueous solution in which 12.0 g (0.173 mol) of sodium nitrite was dissolved in 67 mL of water was dropped from the dropping funnel at a temperature not exceeding 5 ° C., and then stirred at 5 ° C. or lower for 1 hour.
The obtained diazo solution was transferred to a 1 L dropping funnel and set in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (optional) and a thermometer, and then added to the round bottom flask. % Diphosphorous acid 180mL and water 90mL were added, and it cooled to -5 degrees C or less with the ice water bath. Next, the diazo solution was added dropwise at a temperature not exceeding 5 ° C., stirred for 1 hour in an ice-water bath, returned to room temperature, and stirred for 48 hours at room temperature.
The obtained reaction solution was extracted twice with 310 mL of ethyl acetate, washed twice with 310 mL of water, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration. The solvent was distilled off under reduced pressure. Subsequently, the obtained crude oil was purified with a silica gel column using n-heptane as a developing solution, to obtain 33.8 g (yield: 82.5%) of the desired bromide.

<6> Synthesis of 1-dibenzothiopheneboronic acid
This compound was synthesized by the following procedure with reference to International Publication No. 2013/118507 pamphlet.
Into a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer, 33.5 g of the bromide obtained in <5> above (127.3 mmol) and 300 mL of dehydrated THF were added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 97 mL (152.8 mmol) of n-BuLi was dropped at −50 ° C. or lower, and then the isobaric dropping funnel was washed with 90 mL of THF and added to the reaction solution. Next, after post-reaction at −50 ° C. or lower for 1 hour, B (i-PrO) ₃ 39 mL (165.6 mmol) was added dropwise at −45 ° C. or lower. Next, the isobaric dropping funnel was washed with 75 mL of THF and added to the reaction solution. After stirring at −45 ° C. or lower for 30 minutes, the acetone-dry ice bath was removed and the temperature was returned to room temperature. Obtained.
Next, 22 mL of concentrated hydrochloric acid and 220 mL of water are placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (may be omitted), a 1 L dropping funnel and a thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, returning to room temperature, and stirring for 3 hours.
The obtained reaction solution was transferred to a 1 L separatory funnel to separate the organic layer, and the aqueous layer was extracted with 310 mL of ethyl acetate. Next, the organic layers were combined into one, washed with 220 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, 200 mL of n-heptane was added to the obtained crude crystals, rinsed at 50 ° C. for 1 hour, cooled to room temperature, and suction filtered to obtain 19.8 g of the desired boronic acid (yield 68.1%). .

<7> Synthesis of 1- (3-bromophenyl) dibenzothiophene
This compound was synthesized by the following procedure with reference to <2> of Synthesis Example 9.
Into a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a nitrogen inlet, and a thermometer, 19.7 g (86.3 mmol) of boronic acid obtained in the above <6>, 3-iodobromobenzene 26.9 g (95.0 mmol), 300 mL of toluene, 150 mL of ethanol, 23.7 g (172.3 mmol) of potassium carbonate, and 85 mL of water were added, and the mixture was stirred at room temperature for 30 minutes in a nitrogen stream. Subsequently, 92.9 mg (0.38 mmol) of palladium acetate and 0.26 g (0.85 mmol) of tri (o-tolyl) phosphine were added and heated, followed by stirring at reflux temperature for 2 hours.
The resulting reaction solution was cooled to room temperature, the aqueous layer was separated, and extracted with 85 mL of ethyl acetate. Next, the organic layers were combined into one, washed with 85 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, the obtained oil was separated by silica gel column chromatography using a mixed solvent of n-hexane and toluene to obtain 26.7 g (yield 91.4%) of the desired bromide.

<8> Synthesis of 3- (dibenzothiophen-1-yl) phenylboronic acid
This compound was synthesized according to the following procedure in the same manner as in <3> of Synthesis Example 9.
28.5 g of the bromide obtained in <7> above was added to a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer. (88.0 mmol) and 445 mL of dehydrated THF were added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 67 mL (106.9 mmol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 80 mL of THF and added to the reaction solution. Then 1 hour at -50 ° C. or less, allowed to _after-react, B a (OMe) 3 11.9g (114.4mmol) , was added dropwise at a temperature below -45 ° C.. Next, the isobaric dropping funnel was washed with 100 mL of THF and added to the reaction solution. After the reaction was performed in an acetone-dry ice bath for 30 minutes, the reaction solution was returned to room temperature and further reacted for 20 hours to obtain a boron reaction solution.
Next, 95 mL of concentrated hydrochloric acid and 238 mL of water are placed in a 2 L 4-neck round bottom flask equipped with a stirrer, Liebig condenser (may be omitted), 1 L dropping funnel and thermometer, and -5 ° C in an ice bath. Until cooled. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, and then returning to room temperature and stirring for 3 hours.
The obtained reaction solution was transferred to a 2 L separatory funnel to separate the organic layer, and the aqueous layer was extracted three times with 200 mL of diethyl ether. Next, the organic layers were combined into one, washed with 200 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, a mixed solution of 89 mL of n-heptane and 35 mL of toluene was added to the obtained crude crystals, stirred for 1 hour at 50 ° C., returned to room temperature, and suction filtered to 15.4 g (yield 59.4%). To give the desired compound.

Synthesis Example 16
Synthesis of 3- (7-methyldibenzofuran-4-yl) phenylboronic acid

<1> Synthesis of 1- (4-methylphenoxy) -2-nitrobenzene
This compound was synthesized by the following procedure.
Into a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser tube fitted with a calcium chloride tube, a nitrogen inlet tube, a 200 mL isobaric dropping funnel and a thermometer, dimethyl sulfoxide (DMSO) 250 mL and potassium hydroxide 56 0.0 g (1.0 mol) was added and stirred under a nitrogen stream. Next, a solution obtained by diluting 108.1 g (1.0 mol) of p-cresol with 50 mL of DMSO was added dropwise while paying attention to heat generation, and then stirred at 40 ° C. for 30 minutes. Next, the solution was cooled to 25 ° C., a solution obtained by diluting 157.5 g (1.0 mol) of o-chloronitrobenzene with 100 mL of DMSO was dropped, and then heated to 90 ° C. and reacted at the same temperature for 5 hours.
The obtained reaction solution was cooled to room temperature, poured into a 3 L Erlenmeyer flask containing 2 L of water, and extracted five times with 300 mL of diethyl ether. The extracted ether layer was washed with 500 mL of water three times and dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration. The solvent was distilled off under reduced pressure to obtain 215.9 g (yield 94.5). %) Of the desired compound. The obtained compound was used in the next reaction without purification.

<2> Synthesis of 1- (4-methylphenoxy) -2-aniline
This compound was synthesized by the following procedure.
In a 3 L four-necked round bottom flask equipped with a stirrer, Erling condenser, 300 mL dropping funnel and thermometer, ethanol 1410 mL, 214.0 g (0.93 mol) of the nitro compound obtained in <1> above, zinc dust 305.7 g (4.67 mol) was added, and the mixture was cooled to 0 ° C. in an ice-water bath with good stirring. Next, 270 mL of acetic acid was added dropwise at a temperature not exceeding 20 ° C., and then the dropping funnel was washed with 465 mL of ethanol, added to the reaction solution, stirred for 1 hour in an ice-water bath, and further stirred overnight at room temperature.
The zinc dust in the obtained reaction solution was filtered, the filter cake was washed with 300 mL of ethanol, and the solvent was distilled off under reduced pressure. Next, the obtained crude product was diluted with 1500 mL of toluene, and this was put into a 2 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser and a thermometer, heated to 60 ° C., and then silica gel (BW −80S) 100 g was added and stirred at the same temperature for 1 hour. Subsequently, the silica gel was removed by suction filtration at the same temperature, and the solvent was distilled off under reduced pressure to obtain 104.8 g (yield 56.5%) of the target compound. The melting point was 47.6-48.5 ° C.

<3> Synthesis of N- [2- (4-methylphenoxy) phenyl] acetamide
This compound was synthesized by the following procedure.
Into a 1 L 4-neck round bottom flask equipped with a stirrer, Liebig condenser (optional), 100 mL dropping funnel and thermometer, 104.0 g (0.52 mol) of the amino compound obtained in <2> above. , 820 mL of DCM and 82.7 g (0.79 mol) of triethylamine (TEA) were added and cooled to −10 ° C. in an ice water bath. Subsequently, 58.6 g (0.73 mol) of acetyl chloride was dropped at a temperature not exceeding 0 ° C., and then the dropping funnel was washed with 150 mL of DCM and added to the reaction solution. Subsequently, after stirring at the same temperature for 30 minutes, it returned to room temperature and stirred for 4 hours.
The obtained reaction liquid was transferred to a 1 L dropping funnel and dropped with stirring into a 2 L four-necked round bottom flask containing 480 g of crushed ice, then transferred to a 2 L separatory funnel to separate the aqueous layer, Extracted with 200 mL DCM and washed 3 times with 480 mL water with the original DCM layer. Subsequently, after drying with magnesium sulfate, the magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained crude product was purified by silica gel column chromatography using toluene and ethyl acetate as developing solvents to obtain 99.8 g (yield 79.5%) of the target compound. The melting point was 92.4-93.3 ° C.

<4> Synthesis of 7-methyl-4-dibenzofuranacetamide
This compound was synthesized according to the following procedure with reference to JP 2013-520508 A.
In a 1 L 4-neck round bottom flask equipped with a stirrer, a Liebig condenser and a thermometer, 99.0 g (0.410 mol) of acetamide obtained in the above <3>, 420 g (4.10 mol) of pivalic acid, potassium carbonate 5.66 g (41.0 mmol) and palladium acetate 9.20 g (41.0 mmol) were added and reacted at 105 ° C. for 48 hours and further at 115 ° C. for 24 hours.
The resulting reaction was cooled to room temperature and charged into 2330 mL of water in a 5 L 4-neck round bottom flask equipped with a stirrer, Liebig condenser (optional) and thermometer. Next, with stirring, 326.7 g of sodium carbonate was added in several portions while paying attention to foaming, and then stirred for 30 minutes, 700 mL of ethyl acetate was added, and the mixture was separated with a 5 L separatory funnel. The aqueous layer was further extracted twice with 700 mL of ethyl acetate. The ethyl acetate layer was washed twice with 460 mL of water and 460 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration. The solvent was distilled off under. Subsequently, the obtained crude product was purified by silica gel column chromatography using chloroform as a developing solvent to obtain 94.8 g (yield 96.6%) of the target compound. The melting point was 74.2-75.1 ° C.

<5> Synthesis of 7-methyl-4-dibenzofuranamine
This compound was also synthesized by the following procedure with reference to JP 2013-520508 A.
In a 3 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser and a thermometer, 94.8 g (0.396 mol) of acetamide obtained in the above <4>, 1020 mL of ethanol, 179.2 g of potassium hydroxide (3 .18 mol), 430 mL of THF, and 430 mL of water were added and reacted at reflux temperature for 18 hours.
The obtained reaction solution was cooled to room temperature, insolubles were filtered, and the solvent was distilled off under reduced pressure. Next, 1160 mL of diethyl ether was added to the obtained crude product for extraction, and the separated aqueous layer was further extracted with 380 mL of diethyl ether. The diethyl ether layers were combined into one, washed with 240 mL of water three times and dried over magnesium sulfate, and then the magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained crude product was purified by silica gel column chromatography using dichloromethane as a developing solvent to obtain 45.2 g (yield 57.8%) of the target compound.

<6> Synthesis of 7-methyl-4-iododibenzofuran
This compound was synthesized by the following procedure.
In a 1 L 4-neck round bottom flask equipped with a stirrer, Erlin condenser, 200 mL dropping funnel and thermometer, 45.0 g (0.228 mol) of amino compound obtained in <5> above, 480 mL of water, concentrated hydrochloric acid 110 mL and 145 mL of dioxane were added and stirred at reflux temperature for 1 hour, then cooled to room temperature, and further cooled to −10 ° C. in an ice water bath. Next, a solution obtained by dissolving 22.0 g (0.319 mol) of sodium nitrite in 150 mL of water at a temperature not exceeding 5 ° C. was dropped, and the mixture was stirred for 30 minutes in an ice water bath at 5 ° C. Then, using a filter aid. The aqueous solution of diazonium salt was filtered.
Next, 51.5 g (0.31 mol) of potassium iodide and 150 mL of water are placed in a 2 L four-necked round bottom flask equipped with a stirrer, an Erling condenser, a 1 L dropping funnel and a thermometer, and 10 ° C. or less. Kept. Subsequently, the diazonium salt aqueous solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at the same temperature for 30 minutes and further stirring at 40 ° C. for 4 hours.
The resulting reaction solution was cooled to room temperature, DCM was added in 480 mL, and then transferred to a 2 L separatory funnel to separate the aqueous layer. The aqueous layer was extracted again with 480 mL DCM. Next, the DCM layers were combined and washed with 400 mL of a 20% aqueous sodium thiosulfate solution, further washed twice with 400 mL of water, and then dried over magnesium sulfate. Next, magnesium sulfate was removed by suction filtration, and the crude product obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography using n-heptane as a developing solvent to obtain 41.2 g of the desired iodide. (Yield 58.7%) was obtained.

<7> Synthesis of 7-methyl-4-dibenzofuranboronic acid
This compound was synthesized by the following procedure.
The iodide obtained in the above <6> was placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer. 0 g (133.0 mmol) and 310 mL of dehydrated THF were added and cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 100 mL (160.0 mmol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 95 mL of THF and added to the reaction solution. Next, after post-reaction at -50 ° C or lower for 1 hour, 18.0 g (173.1 mmol) of B (OMe) _{3 was} added dropwise at -45 ° C or lower. Next, the isobaric dropping funnel was washed with 80 mL of THF and added to the reaction solution, and stirred at −45 ° C. or lower for 30 minutes. Then, the acetone-dry ice bath was removed and the temperature was returned to room temperature. Obtained.
Next, 23 mL of concentrated hydrochloric acid and 230 mL of water are placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (may be omitted), a 1 L dropping funnel and a thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, returning to room temperature, and stirring for 3 hours.
The obtained reaction solution was transferred to a 1 L separatory funnel to separate the organic layer, and the aqueous layer was extracted with 325 mL of ethyl acetate. Next, the organic layers were combined into one, washed with 230 mL of saturated saline, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, 210 mL of n-heptane was added to the obtained crude crystals, rinsed at 50 ° C. for 1 hour, cooled to room temperature and suction filtered to obtain 22.9 g of the desired boronic acid (yield 76.3%). .

<8> Synthesis of 7-methyl-4- (3-bromophenyl) dibenzofuran
This compound was synthesized by the following procedure with reference to <7> of Synthesis Example 14.
In a 1 L four-necked round bottom flask equipped with a stirrer, Erlin condenser, nitrogen inlet, and thermometer, 22.6 g (100.0 mmol) of boronic acid obtained in the above <7>, 3-iodobromobenzene 31.0 g (109.6 mmol), 350 mL of toluene, 175 mL of ethanol, 27.3 g (198.9 mmol) of potassium carbonate and 100 mL of water were added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. Next, 107.1 mg (0.44 mmol) of palladium acetate and 0.31 g (1.0 mmol) of tri (o-tolyl) phosphine were added and heated, followed by stirring at reflux temperature for 2 hours.
The resulting reaction solution was cooled to room temperature, the aqueous layer was separated, and extracted with 100 mL of ethyl acetate. Subsequently, the organic layers were combined into one, washed with 100 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, the obtained oil was separated by silica gel column chromatography using a mixed solvent of n-hexane and toluene to obtain 29.4 g (yield: 87.1%) of the desired bromide.

<9> Synthesis of 3- (7-methyldibenzofuran-4-yl) phenylboronic acid
This compound was synthesized by the following procedure in the same manner as in <8> of Synthesis Example 14.
Into a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer, 29.0 g of the bromide obtained in <8> above. (86.0 mmol) and 430 mL of dehydrated THF were added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 65 mL (104.8 mmol) of n-BuLi was dropped at −50 ° C. or lower, and then the isobaric dropping funnel was washed with 80 mL of THF and added to the reaction solution. Then, after post-reaction at -50 ° C or lower for 1 hour, 11.6 g (111.8 mmol) of B (OMe) _{3 was} added dropwise at a temperature not exceeding -45 ° C. Next, the isobaric dropping funnel was washed with 100 mL of THF and added to the reaction solution. After the reaction was performed in an acetone-dry ice bath for 30 minutes, the reaction solution was returned to room temperature and further reacted for 20 hours to obtain a boron reaction solution.
Next, 95 mL of concentrated hydrochloric acid and 238 mL of water are placed in a 2 L four-necked round bottom flask equipped with a stirrer, Liebig condenser (may be omitted), 1 L dropping funnel and thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, returning to room temperature, and stirring for 3 hours.
The obtained reaction solution was transferred to a 2 L separatory funnel to separate the organic layer, and the aqueous layer was extracted three times with 200 mL of diethyl ether. Next, the organic layers were combined into one, washed with 200 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, a mixed solution of 89 mL of n-heptane and 35 mL of toluene was added to the obtained crude crystals, and the mixture was stirred at 50 ° C. for 1 hour, then returned to room temperature, suction filtered, and 16.4 g (yield 63.3%). To give the desired compound.

Synthesis Example 17
Synthesis of 3- (7-methyldibenzothiophen-4-yl) phenylboronic acid

<1> Synthesis of 1-[(4-methylphenyl) thio] -2-nitrobenzene
This compound was synthesized by the following procedure.
Into a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 200 mL isobaric dropping funnel and a thermometer, 250 mL DMSO and 56.0 g potassium hydroxide (1. 0 mol) was added and stirred under a nitrogen stream. Next, a solution of 124.2 g (1.0 mol) of p-tolyl mercaptan diluted with 50 mL of DMSO was added dropwise while paying attention to heat generation, and then stirred at 40 ° C. for 30 minutes. Subsequently, after cooling to 25 ° C., a solution of 157.5 g (1.0 mol) of o-chloronitrobenzene diluted with 100 mL of DMSO was added dropwise, heated to 90 ° C., and reacted at the same temperature for 5 hours.
The obtained reaction solution was cooled to room temperature, poured into a 3 L Erlenmeyer flask containing 2 L of water, and extracted five times with 300 mL of diethyl ether. Further, the diethyl ether layer was washed with 500 mL of water three times and dried with magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained crude crystals were recrystallized with n-heptane to obtain 196.1 g (yield 78.9%) of the target compound. The melting point was 88.5-89.8 ° C.

<2> Synthesis of 1- (4-methylphenylthio) -2-aniline
This compound was synthesized by the following procedure.
In a 3 L 4-neck round bottom flask equipped with a stirrer, Erlin condenser, 300 mL dropping funnel and thermometer, ethanol 1700 mL, 195.9 g (0.81 mol) of the nitro compound obtained in <1> above, zinc dust 262.0 g (4.00 mol) was added, and the mixture was cooled to 0 ° C. in an ice-water bath with good stirring. Next, 233 mL (4.00 mol) of acetic acid was added dropwise at a temperature not exceeding 20 ° C., and then the dropping funnel was washed with 140 mL of ethanol, added to the reaction solution, stirred for 1 hour in an ice-water bath, and further stirred overnight at room temperature.
The zinc powder in the obtained reaction solution was filtered, the filter cake was washed with 400 mL of ethanol, and the solvent was distilled off under reduced pressure. Next, the obtained crude product was diluted with 800 mL of ethyl acetate, washed with 250 mL of water three times, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration. The solvent was distilled off under reduced pressure. This gave 131.7 g (yield 76.6%) of the target compound. The melting point was 47.8-49.1 ° C.

<3> Synthesis of N- [2- (4-methylphenylthio) phenyl] acetamide
This compound was synthesized by the following procedure.
131.5 g (0.61 mol) of the amino compound obtained in the above <2> was added to a 2 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (optional), a 100 mL dropping funnel and a thermometer. , DCM 1 L, TEA 72.1 g (0.94 mol) was added, and cooled to −10 ° C. in an ice water bath. Next, 51.1 g (0.86 mol) of acetyl chloride was added dropwise at a temperature not exceeding 0 ° C., then the dropping funnel was washed with 130 mL of DCM and added to the reaction solution, stirred at the same temperature for 30 minutes, and then returned to room temperature. Stir for 4 hours.
The resulting reaction solution was transferred to a 1 L dropping funnel and dropped into a 2 L 4-neck round bottom flask containing 540 g of crushed ice with stirring. It was then transferred to a 2 L separatory funnel and the aqueous layer was separated, extracted with 200 mL DCM, combined with the original DCM layer, washed 3 times with 540 mL water and dried over magnesium sulfate. Next, magnesium sulfate was removed by suction filtration, and the crude product obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography using toluene and ethyl acetate as developing solvents, and 152.0 g (yield). The target compound was obtained at a rate of 96.5%.

<4> Synthesis of 7-methyl-4-dibenzothiophenacetamide
This compound was synthesized according to the following procedure with reference to JP 2013-520508 A.
In a 1 L four-necked round bottom flask equipped with a stirrer, Liebig condenser and thermometer, 105.5 g (0.410 mol) of acetamide obtained in the above <3>, 420 g (4.10 mol) of pivalic acid, potassium carbonate 5.66 g (41.0 mmol) and palladium acetate 9.20 g (41.0 mmol) were added and reacted at 105 ° C. for 48 hours and further at 115 ° C. for 24 hours.
The resulting reaction was cooled to room temperature and charged into 2330 mL of water in a 5 L 4-neck round bottom flask equipped with a stirrer, Liebig condenser (optional) and thermometer. Next, with stirring, 326.7 g of sodium carbonate was added in several portions while paying attention to foaming, and then stirred for 30 minutes. Next, 700 mL of ethyl acetate was added, transferred to a 5 L separatory funnel and separated, and the aqueous layer was extracted twice more with 700 mL of ethyl acetate. Next, the ethyl acetate layer was washed twice with 460 mL of water and 460 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained crude product was purified by silica gel column chromatography using chloroform as a developing solvent to obtain 95.1 g (yield 90.8%) of the target compound.

<5> Synthesis of 7-methyl-4-dibenzothiophenamine
This compound was also synthesized by the following procedure with reference to JP 2013-520508 A.
In a 3 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser and a thermometer, 90.1 g (0.212 mol) of the acetamide obtained in the above <4>, 920 mL of ethanol, 160.0 g of potassium hydroxide (2 .83 mol), 380 mL of THF, and 380 mL of water were added and reacted at reflux temperature for 18 hours.
The obtained reaction solution was cooled to room temperature, insolubles were filtered, and the solvent was distilled off under reduced pressure. Next, 1030 mL of diethyl ether was added to the obtained crude product for extraction, and the separated aqueous layer was further extracted with 340 mL of diethyl ether, then washed with 220 mL of water three times and dried over magnesium sulfate. Then, magnesium sulfate was removed by suction filtration, and the crude product obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography using dichloromethane as a developing solvent to obtain 60.3 g (yield 80.3). %) Of the desired compound.

<6> Synthesis of 7-methyl-4-iododibenzothiophene
This compound was synthesized by the following procedure.
In a 1 L four-necked round bottom flask equipped with a stirrer, Erling condenser, 200 mL dropping funnel and thermometer, 60.0 g (0.281 mol) of amino compound obtained in the above <5>, water 450 mL, concentrated hydrochloric acid 100 mL and 135 mL dioxane were added and stirred at reflux temperature for 1 hour, then cooled to room temperature, and further cooled to −10 ° C. in an ice water bath. Next, at a temperature not exceeding 5 ° C., a solution obtained by dissolving 20.4 g (0.295 mol) of sodium nitrite in 140 mL of water was added dropwise, stirred for 30 minutes in an ice water bath at 5 ° C., and then using a filter aid. The aqueous solution of diazonium salt was filtered.
Next, 47.5 g (0.286 mol) of potassium iodide and 140 mL of water are placed in a 2 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a 1 L dropping funnel and a thermometer and brought to 10 ° C. or lower. Kept. Subsequently, the diazonium salt aqueous solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at the same temperature for 30 minutes and further stirring at 40 ° C. for 4 hours.
The obtained reaction solution was cooled to room temperature, 450 mL of DCM was added, transferred to a 2 L separatory funnel, the aqueous layer was separated, and the aqueous layer was extracted again with 450 mL of DCM. Next, the DCM layers were combined, washed with 370 mL of a 20% aqueous sodium thiosulfate solution, further washed twice with 370 mL of water, and then dried over magnesium sulfate. Then, magnesium sulfate was removed by suction filtration, and the crude product obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography using n-heptane as a developing solvent to obtain 52.3 g of the desired iodide. (Yield 57.4%) was obtained.

<7> Synthesis of 7-methyl-4-dibenzothiopheneboronic acid
This compound was synthesized by the following procedure.
The iodide obtained in the above <6> was placed in a 2 L 4-neck round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 200 mL isobaric dropping funnel and a thermometer. 0 g (214.8 mmol) and 500 mL of dehydrated THF were added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 160 mL (256.0 mmol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 150 mL of THF and added to the reaction solution. Next, after post-reaction at -50 ° C or lower for 1 hour, 29.0 g (279.5 mmol) of B (OMe) ₃ was added dropwise at -45 ° C or lower. Next, the isobaric dropping funnel was washed with 130 mL of THF and added to the reaction solution, and stirred at −45 ° C. or lower for 30 minutes. Then, the acetone-dry ice bath was removed and the temperature was returned to room temperature. Obtained.
Next, 37 mL of concentrated hydrochloric acid and 370 mL of water are placed in a 2 L four-necked round bottom flask equipped with a stirrer, Liebig condenser (may be omitted), 1 L dropping funnel and thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, returning to room temperature, and stirring for 3 hours.
The obtained reaction solution was transferred to a 1 L separatory funnel to separate the organic layer, and the aqueous layer was extracted with 525 mL of ethyl acetate. The organic layers were then combined into one, washed with 370 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, 340 mL of n-heptane was added to the obtained crude crystals, rinsed at 50 ° C. for 1 hour, cooled to room temperature, and suction filtered to obtain 48.6 g of the desired boronic acid (yield 75.0%). .

<8> Synthesis of 7-methyl-4- (3-bromophenyl) dibenzothiophene
This compound was synthesized by the following procedure with reference to <7> of Synthesis Example 15.
In a 3 L four-necked round bottom flask equipped with a stirrer, Erlin condenser, nitrogen inlet, and thermometer, 48.5 g (200.3 mmol) of boronic acid obtained in the above <7>, 3-iodobromobenzene 96.0 g (317.6 mmol), 1 L of toluene, 500 mL of ethanol, 79.0 g (576.6 mmol) of potassium carbonate, and 290 mL of water were added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream, and then 310.4 mg (1 .28 mmol) and 0.9 g (2.8 mmol) of tri (o-tolyl) phosphine were added and heated, followed by stirring at reflux temperature for 2 hours.
The resulting reaction solution was cooled to room temperature, the aqueous layer was separated, and extracted with 300 mL of ethyl acetate. Next, the organic layers were combined, washed with 300 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, the obtained oil was separated by silica gel column chromatography using a mixed solvent of n-hexane and toluene to obtain 59.7 g (yield: 84.5%) of the desired bromide.

<9> Synthesis of 3- (7-methyldibenzothiophen-4-yl) phenylboronic acid
This compound was synthesized according to the following procedure in the same manner as in <8> of Synthesis Example 15.
The bromide obtained in <8> above was placed in a 2L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 200 mL isobaric dropping funnel and a thermometer. (0.167 mol) and 830 mL of dehydrated THF were added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 126 mL (203.5 mmol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 150 mL of THF and added to the reaction solution. Next, after post-reaction at -50 ° C. or lower for 1 hour, 22.5 g (217.1 mmol) of B (OMe) _{3 was} added dropwise at a temperature not exceeding −45 ° C. Next, the isobaric dropping funnel was washed with 200 mL of THF and added to the reaction solution. After the reaction was performed in an acetone-dry ice bath for 30 minutes, the reaction solution was returned to room temperature and further reacted for 20 hours to obtain a boron reaction solution.
Next, 185 mL of concentrated hydrochloric acid and 460 mL of water are placed in a 3 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (may be omitted), a 2 L dropping funnel, and a thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, and then returning to room temperature and stirring for 3 hours.
The obtained reaction solution was transferred to a 3 L separatory funnel to separate the organic layer, and the aqueous layer was extracted three times with 380 mL of diethyl ether. Next, the organic layers were combined into one, washed with 380 mL of saturated brine, and dried over magnesium sulfate. Magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, a mixed solution of 170 mL of n-heptane and 68 mL of toluene was added to the obtained crude crystals, and the mixture was stirred at 50 ° C. for 1 hour, then returned to room temperature, suction filtered, and 35.0 g (yield 65.8%). The target compound was obtained.

Synthesis Example 18
Synthesis of 3- (7-fluorodibenzofuran-4-yl) phenylboronic acid

<1> Synthesis of 1- (4-fluorophenoxy) -2-nitrobenzene
This compound was synthesized by the following procedure.
To a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser tube fitted with a calcium chloride tube, a nitrogen inlet tube, a 200 mL isobaric dropping funnel and a thermometer, 100 mL DMSO and 28.0 g potassium hydroxide (0. 5 mol) was added and stirred under a nitrogen stream. Next, a solution prepared by diluting 56.0 g (0.5 mol) of p-fluorophenol with 50 mL of DMSO was added dropwise while paying attention to heat generation, and then stirred at 40 ° C. for 30 minutes. Next, the solution was cooled to 25 ° C., a solution obtained by diluting 78.5 g (0.5 mol) of o-chloronitrobenzene with 50 mL of DMSO was dropped, and then heated to 90 ° C. and reacted at the same temperature for 5 hours.
The resulting reaction solution was cooled to room temperature, poured into a 2 L Erlenmeyer flask containing 1 L of water, and extracted three times with 300 mL of diethyl ether. Next, the diethyl ether layer was washed twice with 50 mL of water and dried over magnesium sulfate. Magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure to obtain 120.8 g (yield 103.1%). ) Was obtained. The obtained compound was used in the next reaction without purification.

<2> Synthesis of 1- (4-fluorophenoxy) -2-aniline
This compound was synthesized by the following procedure.
Concentrated hydrochloric acid 510 mL and tin chloride dihydrate 510 g (2.26 mol) were placed in a 2 L four-necked round bottom flask equipped with a stirrer, Erlin condenser, 1 L dropping funnel and thermometer, and stirred at room temperature. Next, a solution obtained by dissolving 120.0 g (0.51 mol) of the nitro compound obtained in the above <1> in 510 mL of THF was added dropwise with good stirring. Since heat generation started almost simultaneously with the start of dropping, the solution was cooled in a water bath when the temperature exceeded 40 ° C. After completion of the dropping, the dropping funnel was washed with 50 mL of THF and added to the reaction solution, followed by a reaction at 40 ° C. for 2 hours, and then cooled to room temperature.
The obtained reaction solution was transferred to a 3 L four-necked round bottom flask equipped with a stirrer, Liebig condenser, 500 mL dropping funnel and thermometer, cooled to 5 ° C. with an ice-water bath, and 40% aqueous sodium hydroxide solution 285 mL was dropped to make it alkaline while paying attention to heat generation. The precipitated inorganic salt was removed by suction filtration, and the filter cake was further washed with 1 L of ethyl acetate. The filtrate was then transferred to a 3 L separatory funnel and the aqueous layer was separated and extracted with 500 mL of ethyl acetate. Next, the ethyl acetate layers were combined and washed with 500 mL of water and dried over potassium carbonate, and then potassium carbonate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained crude oil was purified by silica gel column chromatography using toluene as a developing solvent to obtain 78.6 g (yield 75.9%) of the target compound.

<3> Synthesis of N- [2- (4-fluorophenoxy) phenyl] acetamide
This compound was synthesized by the following procedure.
78.4 g (0.386 mol) of the amino compound obtained in the above <2> was added to a 2 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (optional), a 100 mL dropping funnel and a thermometer. , 620 mL of DCM and 61.4 g (0.58 mol) of TEA were cooled to −10 ° C. in an ice-water bath, and then 43.5 g (0.542 mol) of acetyl chloride was added dropwise at a temperature not exceeding 0 ° C. Next, the dropping funnel was washed with 100 mL of DCM and added to the reaction solution, stirred at the same temperature for 30 minutes, then returned to room temperature and further stirred for 4 hours.
The obtained reaction liquid was transferred to a 1 L dropping funnel and dropped with stirring into a 2 L four-necked round bottom flask containing 340 g of crushed ice, and then transferred to a 2 L separating funnel to separate the aqueous layer. The aqueous layer was extracted with 340 mL of DCM, washed with 340 mL of water three times with the original DCM layer, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. . Subsequently, the obtained crude crystals were purified by recrystallization using toluene and n-heptane as solvents to obtain 67.8 g (yield 71.6%) of the target compound. The melting point was 77.3-78.2 ° C.

<4> Synthesis of 7-fluoro-4-dibenzofuranacetamide
This compound was synthesized according to the following procedure with reference to JP 2013-520508 A.
In a 1 L 4-neck round bottom flask equipped with a stirrer, a Liebig condenser and a thermometer, 67.5 g (0.275 mol) of acetamide obtained in the above <3>, 282.0 g (2.75 mol) of pivalic acid, 3.80 g (27.5 mmol) of potassium carbonate and 6.20 g (27.5 mmol) of palladium acetate were added and reacted at 105 ° C. for 48 hours and further at 115 ° C. for 24 hours.
The resulting reaction was cooled to room temperature and charged into 1200 mL of water placed in a 3 L 4-neck round bottom flask equipped with a stirrer, Liebig condenser (optional) and thermometer. Next, while stirring, 219.3 g of sodium carbonate was added in several portions while paying attention to foaming, then stirred for 30 minutes, 470 mL of ethyl acetate was added, and the mixture was transferred to a 3 L separatory funnel and separated. The aqueous layer was further extracted twice with 470 mL of ethyl acetate, and then the ethyl acetate layer was washed twice with 300 mL of water and 300 mL of saturated brine and dried over magnesium sulfate. Subsequently, magnesium sulfate was removed by suction filtration, and the crude product obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography using chloroform as a developing solvent, and 58.8 g (yield 87.9). %) Of the desired compound.

<5> Synthesis of 7-fluoro-4-dibenzofuranamine
This compound was synthesized according to the following procedure with reference to JP 2013-520508 A.
In a 3 L 4-neck round bottom flask equipped with a stirrer, a Liebig condenser and a thermometer, 58.5 g (0.241 mol) of the acetamide obtained in <4> above, 620 mL of ethanol, 108.8 g of potassium hydroxide (1 .93 mol), 260 mL of THF, and 260 mL of water were added and reacted at reflux temperature for 18 hours.
The obtained reaction solution was cooled to room temperature and insoluble matters were filtered off, and then the solvent was distilled off under reduced pressure. Next, 1160 mL of diethyl ether was added to the obtained crude product for extraction, and the separated aqueous layer was further extracted with 380 mL of diethyl ether. Next, the diethyl ether layer was washed with 240 mL of water three times and dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained crude product was purified by silica gel column chromatography using dichloromethane as a developing solvent to obtain 27.0 g (yield 55.7%) of the target compound.

<6> Synthesis of 7-fluoro-4-iododibenzofuran
This compound was synthesized by the following procedure.
In a 1 L 4-neck round bottom flask equipped with a stirrer, Erlin condenser, 200 mL dropping funnel and thermometer, 27.0 g (0.134 mol) of the amino compound obtained in <5> above, 280 mL of water, concentrated hydrochloric acid 65 mL and dioxane 85 mL were added, stirred at reflux temperature for 1 hour, then cooled to room temperature, and further cooled to −10 ° C. in an ice water bath. Next, at a temperature not exceeding 5 ° C., a solution obtained by dissolving 13.0 g (0.188 mol) of sodium nitrite in 90 mL of water was added dropwise, stirred for 30 minutes in an ice water bath at 5 ° C., and then using a filter aid. The aqueous solution of diazonium salt was filtered.
Next, in a 1 L four-necked round bottom flask equipped with a stirrer, Erling condenser, 1 L dropping funnel and thermometer, 30.2 g (0.182 mol) of potassium iodide and 90 mL of water were added and kept at 10 ° C. or less. Kept. Subsequently, the diazonium salt aqueous solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at the same temperature for 30 minutes and further stirring at 40 ° C. for 4 hours.
The resulting reaction solution was cooled to room temperature, 280 mL of DCM was added, and then transferred to a 2 L separatory funnel to separate the aqueous layer. The aqueous layer was extracted again with 280 mL DCM. Next, the DCM layers were combined and washed with 240 mL of a 20% aqueous sodium thiosulfate solution, and further washed twice with 240 mL of water, and then dried over magnesium sulfate. Subsequently, magnesium sulfate was removed by suction filtration, and the crude product obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography using n-heptane as a developing solvent to obtain 26.5 g of the desired iodide. (Yield 63.4%) was obtained.

<7> Synthesis of 7-fluoro-4-dibenzofuranboronic acid
This compound was synthesized according to the following procedure in the same manner as in <7> of Synthesis Example 16.
The iodide obtained in <6> above was placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer. 5 g (85.0 mmol) and 200 mL of dehydrated THF were added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 64 mL (102.2 mmol) of n-BuLi was dropped at −50 ° C. or lower, and then the isobaric dropping funnel was washed with 60 mL of THF and added to the reaction solution. Next, after post-reaction at −50 ° C. or lower for 1 hour, 11.5 g (110.6 mmol) of B (OMe) _{3 was} added dropwise at −45 ° C. or lower. Next, the isobaric dropping funnel was washed with 50 mL of THF and added to the reaction solution, and stirred at −45 ° C. or lower for 30 minutes. Then, the acetone-dry ice bath was removed and the temperature was returned to room temperature. Obtained.
Next, 15 mL of concentrated hydrochloric acid and 150 mL of water are placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (may be omitted), a 1 L dropping funnel and a thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, returning to room temperature, and stirring for 3 hours.
The obtained reaction solution was transferred to a 1 L separatory funnel to separate the organic layer, and the aqueous layer was extracted with 210 mL of ethyl acetate. Next, the organic layers were combined into one, washed with 150 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, 135 mL of n-heptane was added to the obtained crude crystals, rinsed at 50 ° C. for 1 hour, cooled to room temperature, and suction filtered to obtain 15.5 g of the desired boronic acid (yield 79.5%). It was.

<8> Synthesis of 7-fluoro-4- (3-bromophenyl) dibenzofuran
This compound was synthesized by the following procedure with reference to <8> of Synthesis Example 16.
In a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a nitrogen inlet, and a thermometer, 15.5 g (67.4 mmol) of boronic acid obtained in the above <7>, 3-iodobromobenzene 20.9 g (73.94 mmol), toluene 235 mL, ethanol 118 mL, potassium carbonate 18.4 g (134.0 mmol) and water 68 mL were added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. Subsequently, 72.2 mg (0.30 mmol) of palladium acetate and 0.21 g (0.67 mmol) of tri (o-tolyl) phosphine were added and heated, followed by stirring at reflux temperature for 2 hours.
The resulting reaction solution was cooled to room temperature, the aqueous layer was separated, and extracted with 70 mL of ethyl acetate. Next, the organic layers were combined into one, washed with 70 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained oil was separated by silica gel column chromatography using a mixed solvent of n-hexane and toluene to obtain 20.2 g (yield 87.8%) of the target compound.

<9> Synthesis of 3- (7-fluorodibenzofuran-4-yl) phenylboronic acid
This compound was synthesized by the following procedure in the same manner as in <9> of Synthesis Example 16.
20.0 g of the bromide obtained in <8> above was added to a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 50 mL isobaric dropping funnel and a thermometer. (58.6 mmol) and 300 mL of dehydrated THF were added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 45 mL (70.9 mmol) of n-BuLi was dropped at −50 ° C. or lower, and then the isobaric dropping funnel was washed with 55 mL of THF and added to the reaction solution. Next, after post-reaction at -50 ° C. or lower for 1 hour, 8.0 g (76.2 mmol) of B (OMe) _{3 was} added dropwise at a temperature not exceeding −45 ° C. Next, the isobaric dropping funnel was washed with 70 mL of THF and added to the reaction solution, followed by post-reaction in an acetone-dry ice bath for 30 minutes, and then returned to room temperature for an additional 20 hours to obtain a boron reaction solution.
Next, 65 mL of concentrated hydrochloric acid and 162 mL of water are placed in an L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (optional), a 500 mL dropping funnel and a thermometer, and -5 in an ice bath. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, returning to room temperature, and stirring for 3 hours.
The resulting reaction solution was transferred to a 1 L separatory funnel to separate the organic layer, and the aqueous layer was extracted three times with 140 mL of diethyl ether. Next, the organic layers were combined into one, washed with 140 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, a mixed solution of 60 mL of n-heptane and 24 mL of toluene was added to the obtained crude crystals, and the mixture was stirred at 50 ° C. for 1 hour, then returned to room temperature and suction filtered to obtain 11.8 g (yield 65.6%). The target compound was obtained.

Synthesis Example 19
Synthesis of 3- (7-fluorodibenzothiophen-4-yl) phenylboronic acid

<1> Synthesis of 1-[(4-fluorophenyl) thio] -2-nitrobenzene
This compound was synthesized by the following procedure.
To a 500 mL four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer, 70 mL DMSO and 23.1 g potassium hydroxide (0.1. 41 mol) was added and stirred under a nitrogen stream. Next, a solution obtained by diluting 50.0 g (0.39 mol) of p-fluorothiophenol with 50 mL of DMSO was added dropwise while paying attention to heat generation, and then stirred at 40 ° C. for 30 minutes. Next, the solution was cooled to 25 ° C., a solution obtained by diluting 61.5 g (0.39 mol) of o-chloronitrobenzene with 40 mL of DMSO was dropped, and then heated to 90 ° C. and reacted at the same temperature for 5 hours.
The resulting reaction solution was cooled to room temperature, poured into a 2 L Erlenmeyer flask containing 1 L of water, and extracted three times with 300 mL of diethyl ether and twice with 300 mL of ethyl acetate. Subsequently, the organic layers were combined into one, washed with 500 mL of water three times and dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained crude crystals were recrystallized with 95% ethanol to obtain 84.5 g (yield: 86.9%) of the target nitro compound. The melting point was 110.3-111.4 ° C.

<2> Synthesis of 1- (4-fluorophenylthio) -2-aniline
This compound was synthesized by the following procedure.
Concentrated hydrochloric acid (340 mL) and tin chloride dihydrate (340 g, 1.53 mol) were placed in a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a 1 L dropping funnel and a thermometer, and stirred at room temperature. Next, a solution obtained by dissolving 84.5 g (0.34 mol) of the nitro compound obtained in <1> above in 340 mL of THF was added dropwise with good stirring. Since heat generation started almost simultaneously with the start of the dropwise addition, the mixture was cooled in a water bath when the temperature exceeded 40 ° C. After completion of dropping, the dropping funnel was washed with 50 mL of THF and added to the reaction solution. Further, after post-reaction at 40 ° C. for 2 hours, it was cooled to room temperature. Since the hydrochloride precipitated with cooling, it was cooled to 10 ° C. in an ice-water bath, and the hydrochloride crystals were collected by suction filtration.
Next, 600 mL of hydrochloride and ethyl acetate were placed in a 1 L four-necked round bottom flask equipped with a stirrer, Liebig condenser, 500 mL dropping funnel and thermometer, and 300 mL of 10% aqueous sodium hydroxide solution was generated in an exothermic manner. The reaction solution was made alkaline by adding dropwise. Next, the reaction solution was transferred to a 1 L separatory funnel, the aqueous layer was separated, and the ethyl acetate layer was washed 3 times with 200 mL of water and then dried over potassium carbonate. Subsequently, potassium carbonate was removed by suction filtration, and the solvent was distilled off under reduced pressure to obtain 49.0 g (yield 65.7%) of the target compound. The obtained compound was used in the next reaction without purification.

<3> Synthesis of N- [2- (4-fluorophenylthio) phenyl] acetamide
This compound was synthesized by the following procedure.
In a 1 L four-necked round bottom flask equipped with a stirrer, Liebig condenser (optional), 100 mL dropping funnel and thermometer, 48.9 g (0.223 mol) of the amino compound obtained in <2> above. , 420 mL of DCM and 35.5 g (0.335 mol) of TEA were added and cooled to −10 ° C. in an ice water bath. Next, 25.1 g (0.313 mol) of acetyl chloride was added dropwise at a temperature not exceeding 0 ° C., then the dropping funnel was washed with 40 mL of DCM and added to the reaction solution, stirred at the same temperature for 30 minutes, and then returned to room temperature. Stir for 4 hours.
The obtained reaction liquid was transferred to a 1 L dropping funnel and dropped into a 1 L 4-neck round bottom flask containing 200 g of crushed ice with stirring. It was then transferred to a 1 L separatory funnel and the aqueous layer was separated, extracted with 100 mL DCM, combined with the original DCM layer, washed 3 times with 200 mL water, and then dried over magnesium sulfate. Next, magnesium sulfate was removed by suction filtration, and the crude product obtained by distilling off the solvent under reduced pressure was purified by recrystallization using toluene and n-heptane to yield 44.6 g (yield 76). 0.5%) of the target compound. The melting point was 93.5-94.4 ° C.

<4> Synthesis of 7-fluoro-4-dibenzothiophenacetamide
This compound was synthesized according to the following procedure with reference to JP 2013-520508 A.
In a 1 L 4-neck round bottom flask equipped with a stirrer, a Liebig condenser and a thermometer, 44.5 g (0.17 mol) of the acetamide obtained in the above <3>, 175 g (1.70 mol) of pivalic acid, potassium carbonate 2.35 g (17.0 mmol) and 3.83 g (17.0 mmol) of palladium acetate were added and reacted at 105 ° C. for 48 hours and further at 115 ° C. for 24 hours.
The resulting reaction was cooled to room temperature and charged into 970 mL of water in a 3 L 4-neck round bottom flask equipped with a stirrer, Liebig condenser (optional) and thermometer. Next, with stirring, 135.5 g of sodium carbonate was added in several portions while paying attention to foaming, and then stirred for 30 minutes, 700 mL of ethyl acetate was added, and the mixture was transferred to a 3 L separatory funnel and separated. Next, the aqueous layer was further extracted twice with 290 mL of ethyl acetate, and then the ethyl acetate layer was washed twice with 290 mL of water and 290 mL of saturated brine and dried over magnesium sulfate. Then, magnesium sulfate was removed by suction filtration, and the crude product obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography using chloroform as a developing solvent, and 40.1 g (yield 91.1). %) Of the desired compound.

<5> Synthesis of 7-fluoro-4-dibenzothiophenamine
This compound was also synthesized by the following procedure with reference to JP 2013-520508 A.
In a 2 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser and a thermometer, 40.1 g (0.155 mol) of the acetamide obtained in the above <4>, 670 mL of ethanol, 117.0 g of potassium hydroxide (2 0.07 mol), 280 mL of THF, and 280 mL of water were added and reacted at reflux temperature for 18 hours.
The obtained reaction solution was cooled to room temperature, insolubles were filtered, the solvent was distilled off under reduced pressure, and 750 mL of diethyl ether was added to the resulting crude product for extraction. The separated aqueous layer was further diluted with diethyl ether. Extracted with 250 mL. Next, the diethyl ether layer was washed with 160 mL of water three times and dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained crude product was purified by silica gel column chromatography using dichloromethane as a developing solvent to obtain 27.5 g (yield 81.7%) of the target compound.

<6> Synthesis of 7-fluoro-4-iododibenzothiophene
This compound was synthesized by the following procedure.
In a 500 mL four-necked round bottom flask equipped with a stirrer, Erling condenser, 100 mL dropping funnel and thermometer, 27.5 g (0.126 mol) of the amino compound obtained in <5> above, water 200 mL, concentrated hydrochloric acid After 45 mL and 60 mL of dioxane were added and stirred at reflux temperature for 1 hour, the mixture was cooled to room temperature and further cooled to −10 ° C. in an ice water bath. Next, a solution obtained by dissolving 9.2 g (0.133 mol) of sodium nitrite in 63 mL of water at a temperature not exceeding 5 ° C. was dropped, and the mixture was stirred in an ice water bath at 5 ° C. for 30 minutes, and then diazonium using a filter aid. The aqueous salt solution was filtered.
Next, 21.2 g (0.128 mol) of potassium iodide and 63 mL of water are placed in a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a 500 mL dropping funnel and a thermometer. Kept. Subsequently, the diazonium salt aqueous solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at the same temperature for 30 minutes and further stirring at 40 ° C. for 4 hours.
The resulting reaction solution was cooled to room temperature, and 200 mL of DCM was added, and then transferred to a 2 L separatory funnel to separate the aqueous layer. The aqueous layer was extracted again with 200 mL DCM. Next, the DCM layers were combined and washed with 170 mL of a 20% aqueous sodium thiosulfate solution, further washed twice with 170 mL of water, and then dried over magnesium sulfate. Subsequently, magnesium sulfate was removed by suction filtration, and the crude product obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography using n-heptane as a developing solvent to obtain 25.0 g of the desired iodide. (Yield 60.7%) was obtained.

<7> Synthesis of 7-fluoro-4-dibenzothiopheneboronic acid
This compound was synthesized by the following procedure in the same manner as in <4> of Synthesis Example 17.
The iodide obtained in the above <6> was placed in a 500 mL four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel, and a thermometer. 0 g (76.2 mmol) and 180 mL of dehydrated THF were added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Subsequently, 56 mL (90.8 mmol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 50 mL of THF and added to the reaction solution. Next, after post-reaction at -50 ° C or lower for 1 hour, 10.3 g (99.1 mmol) of B (OMe) ₃ was dropped at -45 ° C or lower. Next, the isobaric dropping funnel was washed with 46 mL of THF and added to the reaction solution, and stirred at −45 ° C. or lower for 30 minutes, then the acetone-dry ice bath was removed and the temperature was returned to room temperature. Obtained.
Next, 37 mL of concentrated hydrochloric acid and 370 mL of water are placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (not necessary), a 500 mL dropping funnel and a thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, and then returning to room temperature and stirring for 3 hours.
The obtained reaction solution was transferred to a 1 L separatory funnel to separate the organic layer, and the aqueous layer was extracted with 190 mL of ethyl acetate. Next, the organic layers were combined into one, washed with 130 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, the obtained crude crystals were added to 120 mL of n-heptane, rinsed at 50 ° C. for 1 hour, cooled to room temperature, and suction filtered to obtain 14.0 g of the desired boronic acid (yield 74.7%). It was.

<8> Synthesis of 7-fluoro-4- (3-bromophenyl) dibenzothiophene
This compound was synthesized by the following procedure with reference to <8> of Synthesis Example 17.
In a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a nitrogen inlet, and a thermometer, 14.0 g (56.9 mmol) of boronic acid obtained in the above <7>, 3-iodobromobenzene 27.3 g (90.3 mmol), 285 mL of toluene, 142 mL of ethanol, 22.4 g (164.0 mmol) of potassium carbonate and 83 mL of water were added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. Subsequently, 88.3 mg (0.36 mmol) of palladium acetate and 0.26 g (0.8 mmol) of tri (o-tolyl) phosphine were added and heated, followed by stirring at reflux temperature for 2 hours.
The resulting reaction solution was cooled to room temperature, the aqueous layer was separated, and extracted with 85 mL of ethyl acetate. Next, the organic layers were combined into one, washed with 85 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, the obtained oil was separated by silica gel column chromatography using a mixed solvent of n-hexane and toluene to obtain 16.8 g of the desired bromide (yield 82.8%).

<9> Synthesis of 3- (7-fluorodibenzothiophen-4-yl) phenylboronic acid
This compound was synthesized in the same manner as in <9> of Synthesis Example 17 by the following procedure.
The bromide obtained in <8> above was added to a 500 mL four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 50 mL isobaric dropping funnel and a thermometer. 8 g (47.0 mmol) and 230 mL of dehydrated THF were added and cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 35 mL (56.4 mmol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 40 mL of THF and added to the reaction solution. Then, after post-reaction at -50 ° C or lower for 1 hour, 6.3 g (60.8 mmol) of B (OMe) _{3 was} added dropwise at a temperature not exceeding -45 ° C. Next, the isobaric dropping funnel was washed with 50 mL of THF and added to the reaction solution. After the reaction was performed in an acetone-dry ice bath for 30 minutes, the reaction solution was returned to room temperature and further reacted for 20 hours to obtain a boron reaction solution.
Next, 51 mL of concentrated hydrochloric acid and 130 mL of water are placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (not necessary), a 500 mL dropping funnel and a thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, and then returning to room temperature and stirring for 3 hours.
The obtained reaction solution was transferred to a 1 L separatory funnel to separate the organic layer, and the aqueous layer was extracted three times with 100 mL of diethyl ether. Subsequently, the organic layers were combined into one, washed with 100 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, a mixed solution of 50 mL of n-heptane and 20 mL of toluene was added to the obtained crude crystals, and the mixture was stirred at 50 ° C. for 1 hour, then returned to room temperature, filtered with suction, and 10.4 g (yield 68.8%). To give the desired compound.

Synthesis Example 20
Synthesis of 3- (7-phenyldibenzofuran-4-yl) phenylboronic acid

<1> Synthesis of 4- (2-nitrophenoxy) -1,1′-biphenyl
This compound was synthesized by the following procedure.
To a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser tube fitted with a calcium chloride tube, a nitrogen inlet tube, a 200 mL isobaric dropping funnel and a thermometer, 100 mL DMSO and 28.0 g potassium hydroxide (0. 5 mol) was added and stirred under a nitrogen stream. Next, a solution obtained by diluting 85.0 g (0.5 mol) of p-phenylphenol with 50 mL of DMSO was added dropwise while paying attention to heat generation, and then stirred at 40 ° C. for 30 minutes. Next, the solution was cooled to 25 ° C., a solution obtained by diluting 78.5 g (0.5 mol) of o-chloronitrobenzene with 50 mL of DMSO was added dropwise, heated to 90 ° C., and reacted at the same temperature for 5 hours.
The obtained reaction solution was cooled to room temperature, poured into a 2 L Erlenmeyer flask containing 1 L of water, and extracted three times with 300 mL of diethyl ether. Next, after washing twice with 50 mL of water and drying with magnesium sulfate, magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure to obtain 139.8 g (yield 96.0%). A compound was obtained. The obtained compound was used in the next reaction without purification.

<2> Synthesis of 2-([1,1′-biphenyl] -4-yloxy) benzenamine
This compound was synthesized by the following procedure.
Concentrated hydrochloric acid 510 mL and tin chloride dihydrate 510 g (2.26 mol) were placed in a 2 L four-necked round bottom flask equipped with a stirrer, Erlin condenser, 1 L dropping funnel and thermometer, and stirred at room temperature. Next, a solution obtained by dissolving 139.5 g (0.48 mol) of the nitro compound obtained in <1> above in 510 mL of THF was added dropwise with good stirring. Since heat generation started almost simultaneously with the start of dropping, the solution was cooled in a water bath when the temperature exceeded 40 ° C. After completion of the dropping, the dropping funnel was washed with 50 mL of THF and added to the reaction solution. After further reaction at 40 ° C. for 2 hours, the mixture was cooled to room temperature.
The obtained reaction solution was transferred to a 3 L four-necked round bottom flask equipped with a stirrer, Liebig condenser, 500 mL dropping funnel and thermometer, cooled to 5 ° C. with an ice-water bath, and 40% aqueous sodium hydroxide solution 285 mL was dropped to make it alkaline while paying attention to heat generation. The precipitated inorganic salt was suction filtered, and the filter cake was further washed with 1 L of ethyl acetate. The filtrate was then transferred to a 3 L separatory funnel, the aqueous layer was separated, extracted with 500 mL of ethyl acetate, washed with 500 mL of water, and dried over potassium carbonate. Next, potassium carbonate was removed by suction filtration, and the crude oil obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography using toluene as a developing solvent to obtain 100.7 g (yield 80 .3%) of the target compound.

<3> Synthesis of N- [2-([1,1′-biphenyl] -4-yloxy) phenyl] acetamide
This compound was synthesized by the following procedure.
In a 2 L four-necked round bottom flask equipped with a stirrer, Liebig condenser (optional), 100 mL dropping funnel and thermometer, 100.5 g (0.384 mol) of amino compound obtained in <2> above. , 620 mL of DCM and 61.4 g (0.58 mol) of TEA were cooled to −10 ° C. in an ice-water bath, and then 43.5 g (0.542 mol) of acetyl chloride was added dropwise at a temperature not exceeding 0 ° C. Next, the dropping funnel was washed with 100 mL of DCM and added to the reaction solution, stirred at the same temperature for 30 minutes, then returned to room temperature and further stirred for 4 hours.
The obtained reaction liquid was transferred to a 1 L dropping funnel and dropped with stirring into a 2 L four-necked round bottom flask containing 340 g of crushed ice, then transferred to a 2 L separatory funnel, and the aqueous layer was separated. Extracted with 340 mL DCM. Then, after washing with 340 mL of water three times together with the original DCM layer and drying with magnesium sulfate, the magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained crude crystals were purified by recrystallization using toluene and n-heptane as solvents to obtain 100.0 g (yield 85.7%) of the target compound.

<4> Synthesis of 7-phenyl-4-dibenzofuranacetamide
This compound was synthesized according to the following procedure with reference to JP 2013-520508 A.
In a 1 L 4-neck round bottom flask equipped with a stirrer, a Liebig condenser and a thermometer, 95.0 g (0.313 mol) of acetamide obtained in the above <3>, 321.1 g (3.13 mol) of pivalic acid, 4.33 g (31.3 mmol) of potassium carbonate and 7.06 g (31.3 mmol) of palladium acetate were added and reacted at 105 ° C. for 48 hours and further at 115 ° C. for 24 hours.
The resulting reaction was cooled to room temperature and charged into 1370 mL of water in a 3 L 4-neck round bottom flask equipped with a stirrer, Liebig condenser (optional) and thermometer. Next, while stirring, 250.0 g of sodium carbonate was added in several portions while paying attention to foaming. After stirring for 30 minutes, 535 mL of ethyl acetate was added, and the mixture was transferred to a 3 L separatory funnel and separated. The aqueous layer was further extracted twice with 535 mL of ethyl acetate. Next, the ethyl acetate layer was washed twice with 340 mL of water and 340 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained crude product was purified by silica gel column chromatography using chloroform as a developing solvent to obtain 80.4 g (yield 85.3%) of the target compound.

<5> Synthesis of 7-phenyl-4-dibenzofuranamine
This compound was also synthesized by the following procedure with reference to JP 2013-520508 A.
In a 2 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser and a thermometer, 80.4 g (0.268 mol) of the acetamide obtained in the above <4>, 690 mL of ethanol, 120.5 g of potassium hydroxide (2 .14 mol), 290 mL of THF, and 290 mL of water were added and reacted at reflux temperature for 18 hours.
After cooling the obtained reaction liquid to room temperature and filtering insolubles, the solvent was distilled off under reduced pressure, and the crude product obtained was extracted by adding 1280 mL of diethyl ether. Extracted with 420 mL of ether. Next, the diethyl ether layer was washed with 265 mL of water three times and dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained crude product was purified by silica gel column chromatography using dichloromethane as a developing solvent to obtain 41.3 g (yield 59.4%) of the target compound.

<6> Synthesis of 7-phenyl-4-iododibenzofuran
This compound was synthesized by the following procedure.
In a 1 L 4-neck round bottom flask equipped with a stirrer, Erlin condenser, 200 mL dropping funnel and thermometer, 41.2 g (0.159 mol) of amino compound obtained in <5> above, 330 mL of water, concentrated hydrochloric acid 77 mL and dioxane 100 mL were added, and the mixture was stirred at reflux temperature for 1 hour, then cooled to room temperature, and further cooled to −10 ° C. in an ice water bath. Next, at a temperature not exceeding 5 ° C., a solution obtained by dissolving 15.4 g (0.223 mol) of sodium nitrite in 106 mL of water was added dropwise, stirred for 30 minutes in an ice water bath at 5 ° C., and then diazonium using a filter aid. The aqueous salt solution was filtered.
Next, 35.8 g (0.216 mol) of potassium iodide and 107 mL of water are placed in a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a 1 L dropping funnel and a thermometer, and kept at 10 ° C. or lower. Kept. Subsequently, the diazonium salt aqueous solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at the same temperature for 30 minutes and further stirring at 40 ° C. for 4 hours.
The resulting reaction solution was cooled to room temperature, and 330 mL of DCM was added, and then transferred to a 2 L separatory funnel to separate the aqueous layer. The aqueous layer was extracted again with 330 mL DCM. Next, the DCM layers were combined and washed with 280 mL of a 20% aqueous sodium thiosulfate solution, and further washed twice with 280 mL of water, and then dried over magnesium sulfate. Then, magnesium sulfate was removed by suction filtration, and the crude product obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography using n-heptane as a developing solvent to obtain 40.6 g of the desired iodide. (Yield 69.0%) was obtained.

<7> Synthesis of 7-phenyl-4-dibenzofuranboronic acid
This compound was synthesized according to the following procedure in the same manner as in <7> of Synthesis Example 16.
The iodide obtained in <6> above was placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer. 5 g (109.7 mmol) and 260 mL of dehydrated THF were added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Next, 83 mL (131.9 mmol) of n-BuLi was dropped at −50 ° C. or lower, and then the isobaric dropping funnel was washed with 77 mL of THF and added to the reaction solution. Next, after post-reaction at -50 ° C or lower for 1 hour, 14.8 g (142.7 mmol) of B (OMe) ₃ was dropped at -45 ° C or lower. Next, the isobaric dropping funnel was washed with 65 mL of THF and added to the reaction solution, and stirred at −45 ° C. or lower for 30 minutes. Then, the acetone-dry ice bath was removed and the temperature was returned to room temperature. Obtained.
Next, 20 mL of concentrated hydrochloric acid and 190 mL of water are placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (may be omitted), a 1 L dropping funnel and a thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, returning to room temperature, and stirring for 3 hours.
The obtained reaction solution was transferred to a 1 L separatory funnel to separate the organic layer, and the aqueous layer was extracted with 270 mL of ethyl acetate. Subsequently, the organic layers were combined into one, washed with 200 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, 175 mL of n-heptane was added to the obtained crude crystals, rinsed at 50 ° C. for 1 hour, cooled to room temperature, and suction filtered to obtain 23.5 g of the desired boronic acid (yield 74.5%). .

<8> Synthesis of 7-phenyl-4- (3-bromophenyl) dibenzofuran
This compound was synthesized by the following procedure with reference to <8> of Synthesis Example 16.
In a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a nitrogen inlet, and a thermometer, 23.5 g (81.7 mmol) of boronic acid obtained in the above <7>, 3-iodobromobenzene 25.5 g (90.2 mmol), toluene 286 mL, ethanol 143 mL, potassium carbonate 22.4 g (163.5 mmol) and water 83 mL were added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. Next, 88.1 mg (0.37 mmol) of palladium acetate and 0.26 g (0.82 mmol) of tri (o-tolyl) phosphine were added and heated, followed by stirring at reflux temperature for 2 hours.
The resulting reaction solution was cooled to room temperature, the aqueous layer was separated, and extracted with 85 mL of ethyl acetate. Next, the organic layers were combined into one, washed with 85 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, the obtained oil was separated by silica gel column chromatography using a mixed solvent of n-hexane and toluene to obtain 23.1 g of the desired bromide (yield 83.5%).

<9> Synthesis of 3- (7-phenyldibenzofuran-4-yl) phenylboronic acid
This compound was synthesized by the following procedure in the same manner as in <9> of Synthesis Example 16.
Into a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer, 23.1 g of the bromide obtained in <8> above. (68.1 mmol) and 350 mL of dehydrated THF were added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Subsequently, 52 mL (82.4 mmol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 64 mL of THF and added to the reaction solution. Subsequently, after post-reaction at -50 ° C. or lower for 1 hour, 9.3 g (88.5 mmol) of B (OMe) _{3 was} added dropwise at a temperature not exceeding −45 ° C. Next, the isobaric dropping funnel was washed with 81 mL of THF and added to the reaction solution, followed by post-reaction in an acetone-dry ice bath for 30 minutes, and then returned to room temperature for an additional 20 hours to obtain a boron reaction solution.
Next, 75 mL of concentrated hydrochloric acid and 188 mL of water are placed in an L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (may be omitted), a 1 L dropping funnel and a thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, and then returning to room temperature and stirring for 3 hours.
The resulting reaction solution was transferred to a 1 L separatory funnel to separate the organic layer, and the aqueous layer was extracted three times with 165 mL of diethyl ether. Next, the organic layers were combined into one, washed with 165 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, a mixed solution of 70 mL of n-heptane and 28 mL of toluene was added to the obtained crude crystals, and the mixture was stirred at 50 ° C. for 1 hour, then returned to room temperature and suction filtered to obtain 17.0 g (yield 68.9%). The target compound was obtained.

Synthesis Example 21
Synthesis of 3- (7-phenyldibenzothiophen-4-yl) phenylboronic acid

<1> Synthesis of 4- (2-nitrothiophenoxy) -1,1′-biphenyl
This compound was synthesized by the following procedure.
To a 500 mL four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer, 70 mL DMSO and 23.1 g potassium hydroxide (0.1. 41 mol) was added and stirred under a nitrogen stream. Next, a solution obtained by diluting 72.6 g (0.39 mol) of p-phenylthiophenol with 50 mL of DMSO was added dropwise while paying attention to heat generation, followed by stirring at 40 ° C. for 30 minutes. Next, the solution was cooled to 25 ° C., a solution obtained by diluting 61.5 g (0.39 mol) of o-chloronitrobenzene with 40 mL of DMSO was dropped, and then heated to 90 ° C. and reacted at the same temperature for 5 hours.
The obtained reaction solution was cooled to room temperature, poured into a 2 L Erlenmeyer flask containing 1 L of water, and extracted three times with 300 mL of diethyl ether and twice with 300 mL of ethyl acetate. The organic layers were then combined into one, washed with 500 mL of water three times and dried over magnesium sulfate, and then the magnesium sulfate was removed by suction filtration. The solvent was distilled off under reduced pressure to yield 107.8 g (yield). The desired compound was obtained at a rate of 89.9%.

<2> Synthesis of 2-([1,1′-biphenyl] -4-ylthio) benzenamine
This compound was synthesized by the following procedure.
Concentrated hydrochloric acid 350 mL and tin chloride dihydrate 350 g (1.57 mol) were placed in a 2 L 4-neck round bottom flask equipped with a stirrer, an Erlin condenser, a 1 L dropping funnel and a thermometer, and stirred at room temperature. Next, a solution obtained by dissolving 107.5 g (0.35 mol) of the nitro compound obtained in the above <1> in 350 mL of THF was added dropwise with good stirring. Since heat generation started almost simultaneously with the start of dropping, the mixture was cooled in a water bath when the temperature exceeded 40 ° C. After completion of the dropping, the dropping funnel was washed with 50 mL of THF and added to the reaction solution. After further reaction at 40 ° C. for 2 hours, the mixture was cooled to room temperature. Since the hydrochloride precipitated with cooling, it was cooled to −10 ° C. in an ice water bath, and the hydrochloride crystals were collected by suction filtration.
Next, 600 mL of the hydrochloride and ethyl acetate were placed in a 2 L four-necked round bottom flask equipped with a stirrer, Liebig condenser, 500 mL dropping funnel and thermometer, and 310 mL of 10% aqueous sodium hydroxide solution was generated in an exothermic manner. The solution was made alkaline by adding dropwise.
The obtained solution was transferred to a 2 L separatory funnel, and the aqueous layer was separated. The ethyl acetate layer was washed with 210 mL of water three times and then dried over potassium carbonate. Next, potassium carbonate was filtered off, and the solvent was distilled off under reduced pressure to obtain 69.1 g (yield 71.2%) of the oily target compound. The obtained oil was used in the next reaction without purification.

<3> Synthesis of N- [2-([1,1′-biphenyl] -4-ylthio) phenyl] acetamide
This compound was synthesized by the following procedure.
In a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (optional), a 100 mL dropping funnel and a thermometer, 69.0 g (0.249 mol) of the amino compound obtained in <2> above. Then, 470 mL of DCM and 40.0 g (0.374 mol) of TEA were added and cooled to −10 ° C. in an ice water bath, and then 28.0 g (0.349 mol) of acetyl chloride was added dropwise at a temperature not exceeding 0 ° C. Next, the dropping funnel was washed with 50 mL of DCM and added to the reaction solution, stirred at the same temperature for 30 minutes, then returned to room temperature and further stirred for 4 hours.
The obtained reaction liquid was transferred to a 1 L dropping funnel and dropped with stirring into a 1 L four-necked round bottom flask containing 230 g of crushed ice, and then transferred to a 1 L separating funnel to separate the aqueous layer. Extracted with 110 mL DCM and combined with the original DCM layer and washed 3 times with 230 mL water. Next, after drying with magnesium sulfate, magnesium sulfate was removed by suction filtration, and the crude product obtained by distilling off the solvent under reduced pressure was purified by recrystallization using toluene and n-heptane, 57.2 g (yield 71.9%) of the target compound was obtained.

<4> Synthesis of 7-phenyl-4-dibenzothiophenacetamide
This compound was synthesized according to the following procedure with reference to JP 2013-520508 A.
In a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser and a thermometer, 57.0 g (0.178 mol) of acetamide obtained in <3> above, 184 g (1.78 mol) of pivalic acid, potassium carbonate 2.47 g (17.8 mmol) and 4.01 g (17.8 mmol) of palladium acetate were added and reacted at 105 ° C. for 48 hours and further at 115 ° C. for 24 hours.
The resulting reaction was cooled to room temperature and poured into 1020 mL of water in a 3 L 4-neck round bottom flask equipped with a stirrer, Liebig condenser (optional) and thermometer, then stirred While being careful of foaming, 142.2 g of sodium carbonate was added in several portions. Next, the mixture was stirred for 30 minutes, 740 mL of ethyl acetate was added, transferred to a 3 L separatory funnel and separated, and the aqueous layer was further extracted twice with 300 mL of ethyl acetate. Next, the ethyl acetate layer was washed twice with 290 mL of water and 300 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained crude product was purified by silica gel column chromatography using chloroform as a developing solvent to obtain 48.6 g (yield: 86.1%) of the target compound.

<5> Synthesis of 7-phenyl-4-dibenzothiophenamine
This compound was also synthesized by the following procedure with reference to JP 2013-520508 A.
In a 2 L 4-neck round bottom flask equipped with a stirrer, a Liebig condenser and a thermometer, 48.5 g (0.152 mol) of the acetamide obtained in the above <4>, 660 mL of ethanol, 114.7 g of potassium hydroxide (2 0.02 mol), 275 mL of THF, and 275 mL of water were added and reacted at reflux temperature for 18 hours.
The obtained reaction solution was cooled to room temperature, insolubles were filtered, the solvent was distilled off under reduced pressure, and the crude product obtained was extracted by adding 735 mL of diethyl ether, and the separated aqueous layer was further separated. Extracted with 245 mL of diethyl ether. Next, the diethyl ether layer was washed with 160 mL of water three times and dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained crude product was purified by silica gel column chromatography using dichloromethane as a developing solvent to obtain 35.0 g (yield 83.7%) of the target compound.

<6> Synthesis of 7-phenyl-4-iododibenzothiophene
This compound was synthesized by the following procedure.
In a 500 mL four-necked round bottom flask equipped with a stirrer, Erling condenser, 100 mL dropping funnel and thermometer, 35.0 g (0.127 mol) of the amino compound obtained in the above <5>, water 200 mL, concentrated hydrochloric acid After 45 mL and 60 mL of dioxane were added and stirred at reflux temperature for 1 hour, the mixture was cooled to room temperature and further cooled to −10 ° C. in an ice water bath. Next, at a temperature not exceeding 5 ° C., a solution obtained by dissolving 9.2 g (0.133 mol) of sodium nitrite in 63 mL of water was added dropwise, stirred for 30 minutes in an ice water bath at 5 ° C., and then using a filter aid. The aqueous solution of diazonium salt was filtered.
Next, 21.2 g (0.128 mol) of potassium iodide and 63 mL of water are placed in a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a 500 mL dropping funnel and a thermometer. Then, the diazonium salt aqueous solution was added dropwise at a temperature not exceeding 10 ° C., stirred at the same temperature for 30 minutes, and further stirred at 40 ° C. for 4 hours.
The obtained reaction solution was cooled to room temperature, and 200 mL of DCM was added, and then transferred to a 2 L separatory funnel, the aqueous layer was separated, and extracted again with 200 mL of DCM. The DCM layers are then combined together, washed with 170 mL of a 20% aqueous sodium thiosulfate solution, and further washed twice with 170 mL of water, dried over magnesium sulfate, and the magnesium sulfate is removed by suction filtration, and the solvent is removed under reduced pressure. Was distilled off. Next, the obtained crude product was purified by silica gel column chromatography using n-heptane as a developing solvent to obtain 28.6 g (yield 58.4%) of the desired iodide.

<7> Synthesis of 7-phenyl-4-dibenzothiopheneboronic acid
This compound was synthesized according to the following procedure in the same manner as in <7> of Synthesis Example 17.
The iodide obtained in the above <6> was placed in a 500 mL four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer. 5 g (73.8 mmol) and 175 mL of dehydrated THF were added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Subsequently, 54 mL (87.9 mmol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 50 mL of THF and added to the reaction solution. Next, after post-reaction at -50 ° C or lower for 1 hour, 10.0 g (95.9 mmol) of B (OMe) ₃ was dropped at -45 ° C or lower. Next, the isobaric dropping funnel was washed with 45 mL of THF and added to the reaction solution, and stirred at −45 ° C. or lower for 30 minutes. Then, the acetone-dry ice bath was removed and the temperature was returned to room temperature. Obtained.
Next, 36 mL of concentrated hydrochloric acid and 360 mL of water were placed in a 1 L four-necked round bottom flask equipped with a stirrer, Liebig condenser (optional), 500 mL dropping funnel and thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, and then returning to room temperature and stirring for 3 hours.
The obtained reaction solution was transferred to a 1 L separatory funnel to separate the organic layer, and the aqueous layer was extracted with 190 mL of ethyl acetate. Next, the organic layers were combined into one, washed with 130 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, 115 mL of n-heptane was added to the obtained crude crystals, rinsed at 50 ° C. for 1 hour, cooled to room temperature, and suction filtered to obtain 15.6 g (yield 69.8%) of the desired boronic acid. .

<8> Synthesis of 7-phenyl-4- (3-bromophenyl) dibenzothiophene
This compound was synthesized by the following procedure with reference to <8> of Synthesis Example 17.
In a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a nitrogen inlet, and a thermometer, 15.5 g (51.0 mmol) of boronic acid obtained in the above <7>, 3-iodobromobenzene 24.4 g (80.8 mmol), 260 mL of toluene, 130 mL of ethanol, 20.0 g (146.8 mmol) of potassium carbonate and 74 mL of water were added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream, and then 79.0 mg (0 .32 mmol) and 0.23 g (0.71 mmol) of tri (o-tolyl) phosphine were added and heated, followed by stirring at reflux temperature for 2 hours.
The resulting reaction solution was cooled to room temperature, the aqueous layer was separated, and extracted with 80 mL of ethyl acetate. Next, the organic layers were combined, washed with 80 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, the obtained oil was separated by silica gel column chromatography using a mixed solvent of n-hexane and toluene to obtain 17.9 g (yield 84.7%) of the desired bromide.

<9> Synthesis of 3- (7-phenyldibenzothiophen-4-yl) phenylboronic acid
This compound was synthesized in the same manner as in <9> of Synthesis Example 17 by the following procedure.
Into a 500 mL four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 50 mL isobaric dropping funnel and a thermometer, 17.8 g of the bromide obtained in <8> above. (42.8 mmol) and 210 mL of dehydrated THF were added and cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Subsequently, 32 mL (51.4 mmol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 40 mL of THF and added to the reaction solution. Then, after post-reaction at -50 ° C or lower for 1 hour, 5.7 g (55.4 mmol) of B (OMe) _{3 was} added dropwise at a temperature not exceeding -45 ° C. Next, the isobaric dropping funnel was washed with 50 mL of THF and added to the reaction solution, followed by post-reaction in an acetone-dry ice bath for 30 minutes, and then returned to room temperature for further 20 hours to obtain a boron reaction solution.
Next, 47 mL of concentrated hydrochloric acid and 118 mL of water are placed in a 500 mL four-necked round bottom flask equipped with a stirrer, a Liebig condenser (which may be omitted), a 300 mL dropping funnel and a thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, returning to room temperature, and stirring for 3 hours.
The obtained reaction solution was transferred to a 1 L separatory funnel to separate the organic layer, and the aqueous layer was extracted three times with 100 mL of diethyl ether. Subsequently, the organic layers were combined into one, washed with 100 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, a mixed solution of 45 mL of n-heptane and 18 mL of toluene was added to the obtained crude crystals, and the mixture was stirred at 50 ° C. for 1 hour, then returned to room temperature, filtered with suction, and 10.4 g (yield 64.1%). To give the desired compound.

Synthesis Example 22
Synthesis of 2-bromo-4-iodotoluene

This compound was synthesized by the following procedure.
To a 1 L 4-neck round bottom flask equipped with a stirrer, Erlin condenser, 100 mL dropping funnel and thermometer, water 450 mL, 2-bromo-p-toluidine 50.0 g (0.268 mol), concentrated hydrochloric acid 100 mL ( 1.102 mol) was added and heated to 90 ° C. with stirring. Subsequently, after stirring at the same temperature for 1 hour, it cooled to room temperature, and also cooled to -10 degreeC with the ice-water bath. Subsequently, an aqueous solution obtained by dissolving 22.3 g (0.323 mol) of sodium nitrite in 70 mL of water at a temperature not exceeding 5 ° C. was added dropwise, stirred at 5 ° C. or lower for 30 minutes, filtered using an auxiliary agent, and diazonium. An aqueous salt solution was obtained.
Next, in a 1 L 4-neck round bottom flask equipped with a stirrer, Erling condenser, 1 L dropping funnel and thermometer, 67.0 g (0.403 mol) potassium iodide (Wako Pure Chemical) and 230 mL water were added. Put in water bath and stir at 10 ° C. Subsequently, after the aqueous solution of the diazonium salt was dropped, the water bath was removed, the temperature was returned to room temperature, the temperature was further raised to 40 ° C., and the mixture was stirred for 4 hours.
The obtained reaction solution was returned to room temperature again, and 300 mL of DCM was added and transferred to a 2 L separatory funnel, and then the aqueous layer was separated, followed by extraction with 250 mL of DCM. Next, the DCM layers are combined into one, washed with 250 mL of 20% sodium thiosulfate aqueous solution, 250 mL of saturated multistory water, and 250 mL of water, dried over magnesium sulfate, and then magnesium sulfate is removed by suction filtration. The solvent was distilled off under. Subsequently, the obtained crude oil was purified by silica gel column chromatography using n-heptane as a developing solvent to obtain 73.5 g (yield: 92.2%) of the desired iodide.

Synthesis Example 23
Synthesis of 3-bromo-4-iodo-1-fluorobenzene

<1> Synthesis of 3-bromo-4-fluoronitrobenzene
This compound was synthesized by the following procedure.
In a 1 L four-necked round bottom flask equipped with a stirrer, Liebig condenser, 50 mL dropping funnel and thermometer, 100 g (0.57 mol) of 1-bromo-2-fluorobenzene and 570 mL of concentrated sulfuric acid were placed in an ice-water bath. After cooling to 0 ° C., 47 mL of 68% nitric acid was added dropwise at a temperature not exceeding 40 ° C. Subsequently, it cooled to 20 degreeC and post-reacted at the same temperature for 3 hours.
The obtained reaction solution was poured onto 3150 g of crushed ice, and the precipitated crystals were collected by filtration, further washed well with 1.5 L of water, and dried for one day in a vacuum dryer at 40 ° C. Subsequently, the obtained crude crystals were further recrystallized with petroleum ether to obtain 103.1 g (yield: 82.2%) of the target compound. The melting point was 57.5-58.9 ° C.

<2> Synthesis of 3-bromo-4-fluoroaniline
This compound was synthesized by the following procedure.
Into a 2 L 4-neck round bottom flask equipped with a stirrer, Erling condenser, 1 L dropping funnel and thermometer, put 466.9 g (2.07 mol) of tin chloride dihydrate and 760 mL of ethanol and stir at room temperature. did. Next, a solution of 3-bromo-4-fluoronitrobenzene (102.7 g, 0.466 mol) in THF (760 mL) was added dropwise with the tin chloride completely dissolved, and the mixture was stirred at 60 ° C. for 2 hours.
The obtained reaction solution was once returned to room temperature, the solvent was distilled off under reduced pressure, 440 g of ice was added to the obtained residue, and the mixture was made alkaline with 1580 mL of a 7% aqueous sodium hydroxide solution. The obtained slurry was separated by suction filtration, and the residue on Nutsche was washed with 600 mL of DCM. The organic layer of the collected filtrate was then separated and the aqueous layer was extracted with 600 mL DCM. Next, the DCM layers were combined and washed with 600 mL of water, and then dried using potassium carbonate. The potassium carbonate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained crude product was purified by silica gel column chromatography using toluene as a developing solvent to obtain 54.7 g (yield 61.7%) of the target compound.

<3> Synthesis of 2-bromo-4-iodo-1-fluorobenzene
This compound was synthesized by the following procedure.
To a 1 L four-necked round bottom flask equipped with a stirrer, Liebig condenser, 100 mL dropping funnel and thermometer, water 630 mL, concentrated hydrochloric acid 84 mL (0.926 mol) and 3-bromo-4-fluoroaniline 54.7 g (0.241 mol) was added and stirred at room temperature for one day. Next, the solution was cooled to −10 ° C. in an ice water bath, and an aqueous solution (63 mL) of 19.0 g (0.270 mol) of sodium nitrite was added dropwise at a temperature not exceeding 5 ° C., followed by stirring at 5 ° C. or lower for 30 minutes. Filtration was performed using a filter aid to obtain an aqueous solution of a diazonium salt.
Next, 42.0 g (0.251 mol) of potassium iodide and 125 mL of water were placed in a 2 L four-necked round bottom flask equipped with a stirrer, an Erling condenser, a 1 L dropping funnel and a thermometer. Stir at 10 ° C. Subsequently, the aqueous solution of the diazonium salt was added dropwise, the water bath was removed, the temperature was returned to room temperature, the temperature was raised to 40 ° C., and the mixture was stirred at the same temperature for 4 hours.
The obtained reaction solution was returned to room temperature again, 270 mL of DCM was added and transferred to a 2 L separatory funnel, the aqueous layer was separated, and 220 mL of DCM was further added for extraction. Next, the DCM layers were combined into one, washed with 220 mL of 20% aqueous sodium thiosulfate solution, saturated aqueous 220 mL and 220 mL of water three times, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration. The solvent was distilled off under reduced pressure. Subsequently, the obtained crude oil was purified by silica gel column chromatography using n-heptane as a developing solvent to obtain 62.5 g (yield: 86.0%) of the target compound.

Synthesis Example 24
Synthesis of 2-methyl-5- (dibenzofuran-4-yl) phenylboronic acid

<1> Synthesis of 4- (3-bromo-4-methylphenyl) dibenzofuran
This compound was synthesized by the following procedure with reference to <2> of Synthesis Example 8.
Into a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a nitrogen inlet, and a thermometer, 19.3 g (91.0 mmol) of 4-dibenzofuranboronic acid of Synthesis Example 8 and 2 of Synthesis Example 22 -26.9 g (100.0 mmol) of bromo-4-iodotoluene, 300 mL of toluene, 150 mL of ethanol, 25.1 g (181.5 mmol) of potassium carbonate and 90 mL of water were added and stirred at room temperature for 30 minutes under a nitrogen stream. Next, 0.10 g (0.45 mmol) of palladium acetate and 0.27 g (0.91 mmol) of tri (o-tolyl) phosphine were added and heated, followed by stirring at reflux temperature for 2 hours.
The resulting reaction solution was cooled to room temperature, the aqueous layer was separated, and extracted twice with 100 mL of ethyl acetate. Subsequently, the organic layers were combined into one, washed with 100 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, the obtained oil was separated by silica gel column chromatography using a mixed solvent of n-heptane and toluene to obtain 23.3 g of the desired bromide (yield 75.9%).

<2> Synthesis of 2-methyl-5- (dibenzofuran-4-yl) phenylboronic acid
This compound was synthesized by the following procedure with reference to <3> of Synthesis Example 8.
The bromide obtained in the above <1> was placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer. (71.2 mmol) and 400 mL of dehydrated THF were added and cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Subsequently, 55 mL (85.4 mmol) of n-BuLi was dropped at −50 ° C. or lower, and then the isobaric dropping funnel was washed with 50 mL of THF and added to the reaction solution. Subsequently, after post-reaction at -50 ° C or lower for 1 hour, 9.7 g (92.6 mmol) of B (OMe) _{3 was} added dropwise at a temperature not exceeding -45 ° C. Next, the isobaric dropping funnel was washed with 100 mL of THF and added to the reaction solution. After the reaction was performed in an acetone-dry ice bath for 30 minutes, the reaction solution was returned to room temperature and further reacted for 20 hours to obtain a boron reaction solution.
Next, 80 mL of concentrated hydrochloric acid and 200 mL of water are placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser (may be omitted), a 1 L dropping funnel and a thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, returning to room temperature, and stirring for 3 hours.
The resulting reaction solution was transferred to a 1 L separatory funnel to separate the organic layer, and the aqueous layer was extracted three times with 140 mL of diethyl ether. Next, the organic layers were combined into one, washed with 140 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, a mixed solution of 70 mL of n-heptane and 30 mL of toluene was added to the obtained crude crystals, and the mixture was stirred at 50 ° C. for 1 hour, then returned to room temperature, suction filtered, and 12.8 g (yield 62.4%). The target compound was obtained.

Synthesis Example 25
Synthesis of 2-methyl-5- (dibenzothiophen-4-yl) phenylboronic acid

<1> Synthesis of 4- (3-bromo-4-methylphenyl) dibenzothiophene
This compound was synthesized according to the following procedure in the same manner as in <2> of Synthesis Example 9.
In a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a nitrogen inlet, and a thermometer, 20.8 g (91.0 mmol) of 4-dibenzothiopheneboronic acid of Synthesis Example 9 and of Synthesis Example 22 26.9 g (100.0 mmol) of 2-bromo-4-iodotoluene, 300 mL of toluene, 150 mL of ethanol, 25.1 g (181.5 mmol) of potassium carbonate, and 90 mL of water were added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. Next, 0.10 g (0.45 mmol) of palladium acetate and 0.27 g (0.91 mmol) of tri (o-tolyl) phosphine were added and heated, followed by stirring at reflux temperature for 2 hours.
The resulting reaction solution was cooled to room temperature, the aqueous layer was separated, and extracted twice with 100 mL of ethyl acetate. Next, the organic layers were combined into one, washed with 100 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained oil was purified by recrystallization using a mixed solvent of n-heptane and toluene to obtain 19.9 g of the desired bromide (yield 61.8%). The melting point was 132.0-133.0 ° C.

<2> Synthesis of 2-methyl-5- (dibenzothiophen-4-yl) phenylboronic acid
This compound was synthesized according to the following procedure in the same manner as in <3> of Synthesis Example 9.
19.5 g of the bromide obtained in the above <1> was placed in a 2 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer. (55.2 mmol) and 300 mL of dehydrated THF were added and cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Subsequently, 43 mL (68.8 mmol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 50 mL of THF and added to the reaction solution. Subsequently, after post-reaction at -50 ° C. or lower for 1 hour, 7.5 g (71.7 mmol) of B (OMe) _{3 was} added dropwise at a temperature not exceeding −45 ° C. Next, the isobaric dropping funnel was washed with 100 mL of THF and added to the reaction solution. After the reaction was performed in an acetone-dry ice bath for 30 minutes, the reaction solution was returned to room temperature and further reacted for 20 hours to obtain a boron reaction solution.
Next, 63 mL of concentrated hydrochloric acid and 157 mL of water are placed in a 1 L four-necked round bottom flask equipped with a stirrer, Liebig condenser (optional), 500 mL dropping funnel, and thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, and then returning to room temperature and stirring for 3 hours.
The obtained reaction solution was transferred to a 3 L separatory funnel to separate the organic layer, and the aqueous layer was extracted three times with 110 mL of diethyl ether. Next, the organic layers were combined into one, washed with 110 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, a mixed solution of 75 mL of n-heptane and 32 mL of toluene was added to the obtained crude crystals, and the mixture was stirred at 50 ° C. for 1 hour, then returned to room temperature, suction filtered, and 12.5 g (yield 71.2%). To give the desired compound.

Synthesis Example 26
Synthesis of 2-fluoro-5- (dibenzofuran-4-yl) -phenylboronic acid

<1> Synthesis of 4- (3-bromo-4-fluorophenyl) dibenzofuran
This compound was synthesized by the following procedure with reference to <2> of Synthesis Example 8.
Into a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a nitrogen inlet, and a thermometer, 22.3 g (105.2 mmol) of 4-dibenzofuranboronic acid of Synthesis Example 8 and 3 of Synthesis Example 23 -34.7 g (115.6 mmol) of bromo-4-iodo-1-fluorobenzene, 350 mL of toluene, 175 mL of ethanol, 29.0 g (209.8 mmol) of potassium carbonate and 105 mL of water, and 30 minutes at room temperature under a nitrogen stream Stir. Subsequently, 0.12 g (0.54 mmol) of palladium acetate and 0.32 g (1.07 mmol) of tri (o-tolyl) phosphine were added and heated, followed by stirring at reflux temperature for 2 hours.
The resulting reaction solution was cooled to room temperature, the aqueous layer was separated, and extracted twice with 150 mL of ethyl acetate. The organic layers were combined into one, washed with 150 mL of saturated brine, and dried over magnesium sulfate. Magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, the obtained oil was separated by silica gel column chromatography using a mixed solvent of n-heptane and toluene to obtain 32.4 g (yield 90.3%) of the desired bromide.

<2> Synthesis of 2-fluoro-5- (dibenzofuran-4-yl) -phenylboronic acid
This compound was also synthesized according to the following procedure with reference to <3> of Synthesis Example 8.
Into a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer, 32.4 g of the bromide obtained in <1> above. (95.0 mmol) and 480 mL of dehydrated THF were added and cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Subsequently, 76 mL (121.6 mmol) of n-BuLi was dropped at −50 ° C. or lower, and then the isobaric dropping funnel was washed with 50 mL of THF and added to the reaction solution. Subsequently, after post-reaction at -50 ° C. or lower for 1 hour, 12.9 g (123.5 mmol) of B (OMe) _{3 was} added dropwise at a temperature not exceeding −45 ° C. Next, the isobaric dropping funnel was washed with 100 mL of THF and added to the reaction solution. After the reaction was performed in an acetone-dry ice bath for 30 minutes, the reaction solution was returned to room temperature and further reacted for 20 hours to obtain a boron reaction solution.
Next, 105 mL of concentrated hydrochloric acid and 265 mL of water are placed in a 2 L four-necked round bottom flask equipped with a stirrer, Liebig condenser (may be omitted), 1 L dropping funnel and thermometer. Cooled to ° C. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, returning to room temperature, and stirring for 3 hours.
The obtained reaction solution was transferred to a 2 L separatory funnel to separate the organic layer, and the aqueous layer was extracted three times with 170 mL of diethyl ether. Subsequently, the organic layers were combined into one, washed with 170 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, a mixed solution of 95 mL of n-heptane and 40 mL of toluene was added to the obtained crude crystals, and the mixture was stirred at 50 ° C. for 1 hour, then returned to room temperature, suction filtered, and 12.8 g (yield 62.4%). The target compound was obtained.

Synthesis Example 27
Synthesis of 2-fluoro-5- (dibenzothiophen-4-yl) -phenylboronic acid

<1> Synthesis of 4- (3-bromo-4-fluorophenyl) dibenzothiophene
This compound was synthesized according to the following procedure in the same manner as in <2> of Synthesis Example 9.
To a 1 L four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a nitrogen inlet, and a thermometer, 23.2 g (101.8 mmol) of 4-dibenzothiopheneboronic acid of Synthesis Example 9 and 3-Bromo-4-iodo-1-fluorobenzene (33.6 g, 111.9 mmol), toluene (340 mL), ethanol (170 mL), potassium carbonate (28.0 g, 202.6 mmol) and water (90 mL) were added, and the mixture was stirred at room temperature under a nitrogen stream at room temperature. Stir for minutes. Subsequently, 0.11 g (0.50 mmol) of palladium acetate and 0.30 g (0.98 mmol) of tri (o-tolyl) phosphine were added and heated, followed by stirring at reflux temperature for 2 hours.
The resulting reaction solution was cooled to room temperature, the aqueous layer was separated, and extracted with 150 mL of ethyl acetate. Next, the organic layers were combined into one, washed with 150 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Subsequently, the obtained oil was purified by recrystallization using a mixed solvent of n-heptane and toluene to obtain 18.4 g (yield 53.0%) of the target compound.

<2> Synthesis of 2-fluoro-5- (dibenzothiophen-4-yl) phenylboronic acid
This compound was synthesized according to the following procedure in the same manner as in <3> of Synthesis Example 9.
19.3 g of the bromide obtained in the above <1> was placed in a 1 L four-necked round bottom flask equipped with a stirrer, a Liebig condenser equipped with a calcium chloride tube, a nitrogen inlet tube, a 100 mL isobaric dropping funnel and a thermometer. (54.0 mmol) and 400 mL of dehydrated THF were added, and the mixture was cooled to −60 ° C. or lower in an acetone-dry ice bath under a nitrogen stream. Subsequently, 42 mL (66.9 mmol) of n-BuLi was dropped at −50 ° C. or less, and then the isobaric dropping funnel was washed with 50 mL of THF and added to the reaction solution. Subsequently, after post-reaction at -50 ° C or lower for 1 hour, 7.3 g (70.5 mmol) of B (OMe) _{3 was} added dropwise at a temperature not exceeding -45 ° C. Next, the isobaric dropping funnel was washed with 75 mL of THF, added to the reaction solution, post-reacted in an acetone-dry ice bath for 30 minutes, returned to room temperature, and further reacted for 20 hours to obtain a boron reaction solution.
A 1 L four-necked round bottom flask equipped with a stirrer, Liebig condenser (may be omitted), 1 L dropping funnel and thermometer is charged with 62 mL of concentrated hydrochloric acid and 154 mL of water, and cooled to −5 ° C. in an ice bath. did. Next, the boron reaction solution was added dropwise at a temperature not exceeding 10 ° C., followed by stirring at 10 ° C. or lower for 1 hour, returning to room temperature, and stirring for 3 hours.
The obtained reaction solution was transferred to a 3 L separatory funnel to separate the organic layer, and the aqueous layer was extracted three times with 100 mL of diethyl ether. Next, the organic layers were combined into one, washed with 110 mL of saturated brine, dried over magnesium sulfate, and then magnesium sulfate was removed by suction filtration, and the solvent was distilled off under reduced pressure. Next, a mixed solution of 75 mL of n-heptane and 22 mL of toluene was added to the obtained crude crystals, and the mixture was stirred at 50 ° C. for 1 hour, then returned to room temperature and suction filtered to obtain 11.8 g (yield 68.1%). The target compound was obtained.

Example 1
2- {3- [3- (Dibenzothiophen-4-yl) phenyl] phenyl} -4,6-diphenyl-1,3,5-triazine [DBT (4) -HH-PhTRZ: (I)- 1233 Compound]
The compound according to the above reaction formula was synthesized as follows.
3- (Dibenzo [b, d] thiophen-4-yl) phenylboronic acid of Synthesis Example 9 was added to a 100 mL four-necked round bottom flask equipped with a stirrer, an Erlin condenser, a nitrogen inlet, and a thermometer. 60 g (5.26 mmol), 1.70 g (4.39 mmol) of 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine of Synthesis Example 1, 1.35 M aqueous tripotassium phosphate solution (K ₃ PO ₄ : 2.78 g + H ₂ O: 9.7 mL) and THF 29.1 mL were added and nitrogen bubbling was performed for 1 hour. Next, 0.081 g of tris (dibenzylideneacetone) dipalladium (0) [Pd ₂ (dba) ₃ ] and 0.075 g of 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl [SPhos] were added, and a nitrogen stream was added. Under heating to 80 ° C., the mixture was refluxed and stirred. After 15 hours, disappearance of 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine by thin layer chromatography (SiO ₂ , developing solvent: dichloromethane / hexane = 1 / 3.5) The reaction mixture was cooled to room temperature.
Ethyl acetate was added to the obtained reaction mixture, transferred to a separatory funnel, washed with saturated brine, and further ethyl acetate was added to extract an organic layer. Since a large amount of precipitate was confirmed in the liquid separation, the solution was suction filtered, and the resulting off-white solid was washed with methanol / water and then dried under reduced pressure. Subsequently, toluene was added and heated to reflux, followed by hot filtration using silica gel. When confirmed by thin layer chromatography (SiO ₂ , developing solvent: dichloromethane / hexane = 1 / 3.5), all the spots derived from the raw material disappeared at this point. Subsequently, the obtained liquid was concentrated and dried under reduced pressure, and then purified by recrystallization (solvent: toluene), further washed with hexane, and dried under reduced pressure to obtain a white solid (yield 2.02 g / yield 81.81). 5%). Subsequently, the obtained white solid was purified by sublimation by a conventional method. The purification conditions, yield, and yield are shown in Table 557. The high temperature side temperature and the low temperature side temperature are sublimation working temperatures in a conventional method.
FIG. 1 shows a nuclear magnetic resonance spectrum ( ¹ H-NMR) of a crystal obtained by sublimation purification, and FIG. 2 shows the result of mass spectrometry (Mass).
The results of elemental analysis are as follows, and the numbers in parentheses are theoretical values.
Carbon: 82.50 (82.51), Hydrogen: 4.36 (4.44)
Nitrogen: 7.31 (7.40), Sulfur: 5.43 (5.65)
From these data, it was confirmed that the obtained compound was DBT (4) -HH-PhTRZ.

Table 558 shows evaluation results of thermophysical properties of the obtained DBT (4) -HH-PhTRZ.
Next, in order to measure various characteristics of the obtained DBT (4) -HH-PhTRZ, a DBT (4) -HH-PhTRZ single film ( A thickness of 40 nm) was produced.
Next, an ultraviolet-visible (UV-vis) absorption spectrum of the above single film was measured using an ultraviolet-visible (UV-vis) spectrophotometer UV-3150 manufactured by Shimadzu Corporation, and Fluoro Max- manufactured by HORIBA, Ltd. 4 was used to measure the photoluminescence (PL) spectrum. The results are shown in FIG.
Further, the ionization potential (Ip) of the single film was measured in a vacuum using a photoelectron yield (PYS) apparatus manufactured by Sumitomo Heavy Industries, Ltd. The results are shown in FIG. Ip is data necessary for producing an organic electroluminescence element.
Furthermore, since the organic EL element is an all-solid-state light-emitting element, optical characteristics in the solid state are important, but the energy gap (Eg) can be estimated from the absorption edge of the UV-vis absorption spectrum, and the electron affinity ( Ea) can be calculated by subtracting Eg from Ip.
Table 559 shows the ionization potential (Ip), electron affinity (Ea), and energy gap (Eg) results for DBT (4) -HH-PhTRZ.

Next, in order to measure the characteristics of DBT (4) -H-H-PhTRZ and α-NPD represented by the following formula, an α-NPD single film (thickness) was formed by resistance heating vapor deposition using a vacuum integrated vapor deposition apparatus. 40 nm), DBT-TRZ single film (thickness 40 nm), and α-NPD: DBT (4) -H—H—PhTRZ (1: 1) co-deposited film (thickness 30 nm).
Next, an ultraviolet-visible (UV-vis) absorption spectrum of each film was measured using an ultraviolet-visible (UV-vis) spectrophotometer UV-3150 manufactured by Shimadzu Corporation. The measurement results are shown in FIG.
Moreover, about each said film | membrane, the photo-luminescence (PL) spectrum was measured using Fluoro Max-4 by Horiba. The measurement results are shown in FIG. Since the α-NPD: DBT (4) -H—H—PhTRZ (1: 1) co-deposited film gave different results from the respective photoluminescence regions, both formed an exciplex. It is considered that photoluminescence was observed.

Example 2
2- {3- [3- (Dibenzofuran-4-yl) phenyl] phenyl} -4,6-diphenyl-1,3,5-triazine [DBF (4) -HH-PhTRZ: (I) -1 Compound of
The compound according to the above reaction formula was synthesized as follows.
To a 100 mL 4-neck round bottom flask equipped with a stirrer, an Erlin condenser, a nitrogen inlet, and a thermometer, 1.69 g (5.55 mmol) of 3- (dibenzofuran-4-yl) phenylboronic acid of Synthesis Example 8 ), 1.04 g (2.68 mmol) of 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine of Synthesis Example 1 and 1M aqueous tripotassium phosphate solution (K ₃ PO ₄ : 1.52 g + H ₂ O: 5.32 mL), toluene 10.64 mL, and ethanol 5.32 mL were added, and nitrogen bubbling was performed for 1 hour. Subsequently, tris (dibenzylideneacetone) dipalladium (0) [Pd ₂ (dba) ₃ ] 3.2 mg, 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl [SPhos] 29.8 mg were added, and 80 ° C. The mixture was heated to reflux and stirred. After 2 hours, disappearance of 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine was confirmed by thin layer chromatography (SiO ₂ , developing solvent: dichloromethane / hexane = 1/2). And the reaction mixture was cooled to room temperature.
The resulting reaction mixture was dispersed and washed overnight with water and methanol, and then suction filtered. Subsequently, the filtrate was filtered hot with 300 mL of toluene, and the filtrate was concentrated and dried under reduced pressure to obtain a white solid (yield 1.63 g / yield 81.5%).
The obtained white solid was purified by sublimation by a conventional method. The purification conditions, yield, and yield are shown in Table 560. The high temperature side temperature and the low temperature side temperature are sublimation working temperatures in a conventional method.
A nuclear magnetic resonance spectrum ( ¹ H-NMR) of a crystal obtained by sublimation purification is shown in FIG. Moreover, as a result of mass spectrometry, it was found that a molecular ion peak was shown at 552 representing the target compound. The results of elemental analysis are as follows, and the numbers in parentheses are theoretical values. In addition, since the elemental analysis includes a combustion operation, the value of oxygen in the compound cannot be measured.
Carbon: 84.89 (84.91), Hydrogen: 4.54 (4.57)
Nitrogen: 7.54 (7.62)
From these data, it was confirmed that the obtained compound was DBF (4) -HH-PhTRZ.

Examples 3-5
Photoluminescence of α-NPD: DBT (4) -H-H-PhTRZ (1: 1) co-deposited film (thickness 30 nm) using DBT (4) -H-H-PhTRZ synthesized in Example 1 When an exciplex was formed on the long wavelength side, the overlap of the deep red phosphorescent material Ir (DPQ) ₂ (dpm) with the triplet exciplex ( ³ MLCT) was large, and the exciplex Efficient energy transfer to the luminescent material can be expected. Accordingly, an organic EL device having a light emitting layer in which the mixing ratio of the exciplex host (α-NPD: DBT (4) -HH-PhTRZ) was changed as in Examples 3 to 5 below was prepared, and the optimum mixing ratio was obtained. investigated.

Example 3
α-NPD: DBT (4) -HH-PhTRZ = 8: 2 (thickness 20 nm) / 7: 3 (thickness 20 nm)
Example 4
α-NPD: DBT (4) -HH-PhTRZ = 5: 5 (thickness 40 nm)
Example 5
α-NPD: DBT (4) -HH-PhTRZ = 3: 7 (thickness 20 nm) / 2: 8 (thickness 20 nm)

In Example 3, the layer with a mixing ratio of 8: 2 and the layer with 7: 3 are stacked.
Moreover, the said Example 5 laminates | stacks the layer whose mixing ratio is 3: 7, and the layer of 2: 8.

The layer structure of the organic EL element is as follows, and x: y of the light emitting layer corresponds to the changed mixing ratio. Note that the light emitting layer was doped with 1 wt% of Ir (DPQ) ₂ (dpm). The number in parentheses is the film thickness.

DNTPD: PPBI (20 nm) (hole injection layer) / α-NPD (20 nm) (hole transport layer) / α-NPD: DBT (4) -H—H—PhTRZ = x: y [1 wt% Ir (DPQ) ₂ (Dpm) dope] (40 nm) (light emitting layer) / DBT (4) -H—H—PhTRZ (20 nm) (light emitting layer) / DPB (30 nm) (electron transport layer) / DPB: 20 wt% Liq (20 nm) ( Electron injection layer) / Liq (1 nm) (electron injection layer) / Al (cathode)

The chemical structure of the main materials used is as follows. (DNTPD is described above.)

An energy diagram of the above element configuration is shown in FIG.
Moreover, of the produced element,
The voltage-current density characteristics are shown in FIG.
The voltage-luminance characteristics are shown in FIG.
The current density vs. external quantum efficiency characteristics are shown in FIG.
The luminance vs. external quantum efficiency characteristics are shown in FIG.
The EL spectrum is shown in FIG.
The device lifetime is shown in FIG.
Tables 561 to 563 show the relationship among the host mixing ratios and the voltage, power efficiency, current efficiency, external quantum efficiency, and chromaticity coordinate values at 1 cd / m ² , 100 cd / m ^2, and 1000 cd / m ² . .

Examples 6-7
The lithium doped region was examined for the purpose of improving the lifetime of the organic EL element.
That is, an organic EL element having the following layer structure was produced. The number in parentheses is the layer thickness.

Device 1 (Example 6)
DNTPD: PPBI (20 nm) (hole injection layer) / α-NPD (20 nm) (hole transport layer) / α-NPD: DBT (4) -H—H—PhTRZ = 50: 50: [1 wt% Ir (DPQ) ₂ (dpm) dope] (40 nm) (light emitting layer) / DBT (4) -H—H—PhTRZ (20 nm) (light emitting layer) / DPB (30 nm) (electron transport layer) / DPB: 20 wt% Liq (20 nm) (Electron injection layer) / Liq (1 nm) (electron injection layer) / Al (cathode)

Device 2 (Example 7)
DNTPD: PPBI (20 nm) (hole injection layer) / α-NPD (20 nm) (hole transport layer) / α-NPD: DBT (4) -H—H—PhTRZ = 50: 50: [1 wt% Ir (DPQ) ₂ (dpm) dope] (40 nm) (light emitting layer) / DBT-TRZ (20 nm) (light emitting layer) / DPB: 20 wt% Liq (50 nm) (electron injection layer) / Liq (1 nm) (electron injection layer) / Al

An energy diagram of the device configuration of Device 1 is shown in FIG. 8, and an energy diagram of the device configuration of Device 2 is shown in FIG.
Moreover, of the produced element,
The voltage-current density characteristics are shown in FIG.
The voltage-luminance characteristics are shown in FIG.
The current density vs. external quantum efficiency characteristics are shown in FIG.
Luminance vs. external quantum efficiency characteristics are shown in FIG.
The EL spectrum is shown in FIG.
The device lifetime is shown in FIG.
Tables 564 to 566 show relationships among voltage, power efficiency, current efficiency, external quantum efficiency, and chromaticity coordinate values of Device 1 and Device 2 at 1 cd / m ² , 100 cd / m ² , and 1000 cd / m ² . .

Examples 8-9
The effect of the Ir (DPQ) ₂ (dpm) used in the light-emitting layer on the lifetime of the device was examined with the addition amount of 1 wt% (Example 8) and 2 wt% (Example 9).
The layer structure of the produced organic EL element is as follows.

Example 8
DNTPD: PPBI (20 nm) (hole injection layer) / α-NPD (20 nm) (hole transport layer) / α-NPD: DBT (4) -H—H—PhTRZ = 50: 50: [1 wt% Ir (DPQ) ₂ (dpm) dope] (40 nm) (light emitting layer) / DBT (4) -H—H—PhTRZ (20 nm) (light emitting layer) / DPB: 20 wt% Liq (50 nm) (electron injection layer) / Liq (1 nm) (Electron injection layer) / Al

Example 9
DNTPD: PPBI (20 nm) (hole injection layer) / α-NPD (20 nm) (hole transport layer) / α-NPD: DBT (4) -H—H—PhTRZ = 50: 50: [2 wt% Ir (DPQ) ₂ (dpm) dope] (40 nm) (light emitting layer) / DBT (4) -H—H—PhTRZ (20 nm) (light emitting layer) / DPB: 20 wt% Liq (50 nm) (electron injection layer) / Liq (1 nm) (Electron injection layer) / Al

The energy diagram of the element structure of Examples 8-9 is shown in FIG.
Moreover, of the produced element,
The voltage-current density characteristics are shown in FIG.
The voltage-luminance characteristics are shown in FIG.
FIG. 24 shows the current density vs. external quantum efficiency characteristics.
The luminance-external quantum efficiency characteristics are shown in FIG.
The EL spectrum is shown in FIG.
The device lifetime is shown in FIG.
As can be seen from FIG. 27, in Example 9 in which the addition amount is 2 wt%, the 10% decay time of the emission intensity is about 1500 hours, which is sufficiently practical.
Tables 567 to 569 show the relationship among the voltage, power efficiency, current efficiency, external quantum efficiency, and chromaticity coordinate values at 1 cd / m ² , 100 cd / m ^2, and 1000 cd / m ² of each element of Examples 8 to 9. Shown in

Example 10
An element having the following layer structure in which DBF (4) -H—H—PhTRZ synthesized in Example 2 was incorporated by vacuum deposition was prepared and evaluated. The chemical structure of main materials other than DBF (4) -H-H-PhTRZ is the same as in Examples 3-5.

ITO / DNTPD: PPBI (20 nm) (hole injection layer) / α-NPD (20 nm) (hole transport layer) / α-NPD: DBF (4) -HH-PhTRZ: Ir (DPQ) ₂ (dpm) = 50: 50: 1 wt% (40 nm) (light emitting layer) / DBF (4) -H—H—PhTRZ (20 nm) (light emitting layer) / DPB (30 nm) / DPB: 20 wt% Liq (20 nm) (electron transport layer) / Liq (1 nm) (electron injection layer) / Al (80 nm)

FIG. 28 shows an energy diagram of the element configuration.
Moreover, of the produced element,
The voltage-current density characteristics are shown in FIG.
The voltage-luminance characteristics are shown in FIG.
Luminance-current efficiency characteristics are shown in FIG. 31. Luminance-power efficiency characteristics are shown in FIG. 32. Current density-external quantum efficiency characteristics are shown in FIG.
Luminance-external quantum efficiency characteristics are shown in FIG.
The EL spectra are shown in FIG.
Table 570 to Table 572 show the relationship among the voltage, power efficiency, current efficiency, and external quantum efficiency at 1 cd / m ² , 100 cd / m ^2, and 1000 cd / m ² for the element of Example 10, and the excitation light is 340 nm. Table 573 shows the photoluminescence quantum yield of each of.

Example 11
2- {3- [3- (Dibenzofuran-2-yl) phenyl] phenyl} -4,6-diphenyl-1,3,5-triazine [DBF (2) -H-H-PhTRZ: (I) -353 Compound of
The compound according to the above reaction formula was synthesized as follows.
To a 100 mL four-necked round bottom flask equipped with a stirrer, an Erlin condenser tube, a nitrogen inlet tube, and a thermometer, 1.95 g of 5- (dibenzofuran-2-yl) phenylboronic acid ester of Synthesis Example 10 (5. 27 mmol), 1.70 g (4.39 mmol) of 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine of Synthesis Example 1, 1.35 M tripotassium phosphate aqueous solution (K ₃ PO) ₄ : 2.78 g + H ₂ O: 9.7 mL) and THF 29.1 mL were added, and nitrogen bubbling was performed for 1 hour. Next, 0.081 g of tris (dibenzylideneacetone) dipalladium (0) [Pd ₂ (dba) ₃ ] and 0.075 g of 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl [SPhos] were added, and a nitrogen stream was added. Under heating to 80 ° C., the mixture was refluxed and stirred. After 15 hours, disappearance of 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine by thin layer chromatography (SiO ₂ , developing solvent: dichloromethane / hexane = 1 / 3.5) The reaction mixture was cooled to room temperature.
Ethyl acetate was added to the obtained reaction mixture, transferred to a separatory funnel, washed with saturated brine, and further ethyl acetate was added to extract an organic layer. Since a large amount of precipitate was confirmed in the liquid separation, the solution was suction filtered, and the resulting off-white solid was washed with methanol / water and then dried under reduced pressure. Next, toluene was added and heated to reflux, followed by hot filtration using silica gel, and confirmation by thin layer chromatography (SiO ₂ , developing solvent: dichloromethane / hexane = 1 / 3.5). Were all gone. The obtained liquid was concentrated and dried under reduced pressure, and then purified by recrystallization (solvent: toluene). Then, it was washed with hexane and dried under reduced pressure to obtain a white solid (yield 2.00 g / yield 83.0%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The nuclear magnetic resonance spectrum ( ¹ H-NMR) of this crystal is shown in FIG. 36 (entire region) and FIG. 37 (enlarged view). Assignment of ¹ H-NMR spectrum is as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 9.08 (t, J = 1.8 Hz, 1H), 8.81 (dd, J = 7.9, 1.6 Hz, 5H), 8.27 ( d, J = 1.8 Hz, 1H), 8.03 (q, J = 2.1 Hz, 2H), 7.96-7.91 (m, 1H), 7.84-7.56 (m, 14H) ), 7.54-7.46 (m, 1H), 7.38 (t, J = 7.5 Hz, 1H) ppm;
The results of elemental analysis are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 84.95 (84.91), Hydrogen: 4.60 (4.57)
Nitrogen: 7.59 (7.62)
Moreover, the result of mass spectrometry was m / z 551 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBF (2) -HH-PhTRZ.

Example 12
2- {3- [3- (Dibenzothiophen-2-yl) phenyl] phenyl} -4,6-diphenyl-1,3,5-triazine [DBT (2) -HH-PhTRZ: (I)- Compound 529)
The starting materials in Example 11 were prepared by using 2.03 g (5.27 mmol) of 3- (dibenzothiophen-2-yl) phenylboronic acid ester of Synthesis Example 11 and 2- (3-bromophenyl) -4 of Synthesis Example 1. 2- (3-bromophenyl) -4,6-diphenyl after reacting in exactly the same manner except that it was changed to 1.70 g (4.39 mmol) of 1,6-diphenyl-1,3,5-triazine. After confirming disappearance of -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.92 g / yield 77.1%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The nuclear magnetic resonance spectrum ( ¹ H-NMR) of this crystal is shown in FIG. 38 (entire region) and FIG. 39 (enlarged view). Assignment of ¹ H-NMR spectrum is as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 9.08 (d, J = 1.4 Hz, 1H), 8.81 (dt, J = 8.2, 2.0 Hz, 5H), 8.47 ( d, J = 1.4 Hz, 1H), 8.29-8.22 (m, 1H), 8.06 (s, 1H), 8.00-7.86 (m, 3H), 7.80 ( ddd, J = 15.1, 8.0, 1.5 Hz, 3H), 7.74-7.55 (m, 8H), 7.53-7.43 (m, 2H) ppm;
The results of elemental analysis are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.47 (82.51), Hydrogen: 4.51 (4.44)
Nitrogen: 7.29 (7.40), Sulfur: 5.73 (5.65)
Moreover, the result of mass spectrometry was m / z 567 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBT (2) -HH-PhTRZ.

Example 13
2- {3- [3- (Dibenzofuran-4-yl) phenyl] -4-methylphenyl} -4,6-diphenyl-1,3,5-triazine [DBF (4) -H-Me-PhTRZ: ( 1) Compound of -1061]
Starting materials in Synthesis Example 11 were 1.51 g (5.27 mmol) of 3- (dibenzofuran-4-yl) phenylboronic acid in Synthesis Example 8 and 2- (3-bromo-4-methylphenyl) in Synthesis Example 2. 2- (3-Bromo-4-methylphenyl) was reacted in the same manner except that it was changed to 1.76 g (4.39 mmol) of -4,6-diphenyl-1,3,5-triazine. After confirming the disappearance of -4,6-diphenyl-1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.63 g / yield 65.6%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The nuclear magnetic resonance spectrum ( ¹ H-NMR) of this crystal is shown in FIG. 40 (entire region) and FIG. 41 (enlarged view). Assignment of ¹ H-NMR spectrum is as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.81-8.75 (m, 4H), 8.74-8.69 (m, 2H), 8.24 (d, J = 1.8 Hz, 1H), 8.00 (d, J = 7.8 Hz, 1H), 7.81-7.73 (m, 3H), 7.68-7.43 (m, 12H), 7.39-7. 32 (m, 1H), 2.46 (s, 3H) ppm;
Moreover, the result of thermal decomposition temperature (TG-DTA) is shown in FIG.
The results of elemental analysis are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 84.95 (84.93), Hydrogen: 4.60 (4.81)
Nitrogen: 7.39 (7.43)
Moreover, the result of mass spectrometry was m / z 566 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBF (4) -H-Me-PhTRZ.

Example 14
2- {3- [3- (Dibenzothiophen-4-yl) phenyl] -4-methylphenyl} -4,6-diphenyl-1,3,5-triazine [DBT (4) -H-Me-PhTRZ: (1) Compound of 1237]
The starting materials in Example 11 were synthesized from 1.60 g (5.27 mmol) of 3- (dibenzothiophen-4-yl) phenylboronic acid of Synthesis Example 9 and 2- (3-bromo-4-methylphenyl) of Synthesis Example 2. ) -4,6-diphenyl-1,3,5-triazine was reacted in the same manner except that it was changed to 1.76 g (4.39 mmol), and then 2- (3-bromo-4-methylphenyl) was reacted. ) -4,6-diphenyl-1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.65 g / yield 64.7%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The nuclear magnetic resonance spectrum ( ¹ H-NMR) of this crystal is shown in FIG. 43 (entire region) and FIG. 44 (enlarged view).
Assignment of ¹ H-NMR spectrum is as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.79 (dd, J = 8.0, 1.1 Hz, 4H), 8.75 (d, J = 1.8 Hz, 1H), 8.70 ( dd, J = 8.2, 1.8 Hz, 1H), 8.25-8.13 (m, 2H), 7.86 (s, 1H), 7.83-7.77 (m, 2H), 7.67 (t, J = 7.6 Hz, 1H), 7.63-7.40 (m, 12H), 2.49 (d, J = 13.3 Hz, 3H) ppm;
The results of elemental analysis are as follows, and the numbers in parentheses are theoretical values.
Carbon: 82.61 (82.59), Hydrogen: 4.60 (4.68)
Nitrogen: 7.31 (7.22), Sulfur: 5.48 (5.51)
Moreover, the result of mass spectrometry was m / z 581 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBT (4) -H-Me-PhTRZ.

Example 15
2- {3- [3- (dibenzofuran-4-yl) phenyl] -4-fluorophenyl} -4,6-diphenyl-1,3,5-triazine [DBF (4) -HF-PhTRZ: ( 1) Compound 1206]
The starting materials in Example 11 are 1.51 g (5.27 mmol) of 3- (dibenzofuran-4-yl) phenylboronic acid of Synthesis Example 8 and 2- (3-bromo-4-fluorophenyl) of Synthesis Example 3. 2- (3-bromo-4-fluorophenyl) was reacted in exactly the same manner except that it was changed to 1.78 g (4.39 mmol) of -4,6-diphenyl-1,3,5-triazine. After confirming the disappearance of -4,6-diphenyl-1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.74 g / yield 69.5%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The nuclear magnetic resonance spectrum ( ¹ H-NMR) of this crystal is shown in FIG. 45 (entire region) and FIG. 46 (enlarged view). Assignment of ¹ H-NMR spectrum is as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.96 (dd, J = 7.8, 2.3 Hz, 1H), 8.85-8.75 (m, 5H), 8.24 (d, J = 1.8 Hz, 1H), 8.05-7.95 (m, 2H), 7.85-7.74 (m, 2H), 7.73-7.55 (m, 10H), 7. 54-7.44 (m, 1H), 7.45-7.33 (m, 2H) ppm;
Moreover, the result of thermal decomposition temperature (TG-DTA) is shown in FIG.
The results of elemental analysis are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.14 (82.23), Hydrogen: 4.12 (4.25)
Nitrogen: 7.35 (7.38), Fluorine: 3.39 (3.34)
Moreover, the result of mass spectrometry was m / z 570 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBF (4) -HF-PhTRZ.

Example 16
2- {3- [3- (Dibenzothiophen-4-yl) phenyl] -4-fluorophenyl} -4,6-diphenyl-1,3,5-triazine [DBT (4) -HF-PhTRZ: (I) -1382 Compound]
The starting materials in Example 11 were synthesized from 1.60 g (5.27 mmol) of 3- (dibenzothiophen-4-yl) phenylboronic acid of Synthesis Example 9 and 2- (3-bromo-4-fluorophenyl of Synthesis Example 3 ) -4,6-diphenyl-1,3,5-triazine The reaction was carried out in the same manner except that it was changed to 1.78 g (4.39 mmol), and then 2- (3-bromo-4-fluorophenyl) was obtained. ) -4,6-diphenyl-1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.01 g / yield 78.8%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The nuclear magnetic resonance spectrum ( ¹ H-NMR) of this crystal is shown in FIG. 48 (entire region) and FIG. 49 (enlarged view).
Assignment of ¹ H-NMR spectrum is as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 9.00 (dd, J = 7.8, 2.3 Hz, 1H), 8.84-8.72 (m, 5H), 8.20 (q, J = 4.1 Hz, 2H), 8.10 (s, 1H), 7.88-7.74 (m, 3H), 7.70 (t, J = 7.8 Hz, 1H), 7.65- 7.51 (m, 8H), 7.51-7.34 (m, 3H) ppm;
The results of elemental analysis are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 80.10 (79.98), Hydrogen: 4.22 (4.13)
Nitrogen: 7.04 (7.17), Sulfur: 5.40 (5.47)
Fluorine: 3.24 (3.24)
Moreover, the result of mass spectrometry was m / z 581 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBT (4) -HF-PhTRZ.

Example 17
2- {3- [3- (Dibenzofuran-4-yl) phenyl] phenyl} -4,6-di (p-tolyl) -1,3,5-triazine [DBF (4) -H-H-DiMeTRZ: Compound (I) -1064]
The starting materials in Example 11 are 1.51 g (5.27 mmol) of 3- (dibenzofuran-4-yl) phenylboronic acid of Synthesis Example 8 and 2- (3-bromophenyl) -4,6 of Synthesis Example 4. -After reacting in exactly the same manner except for changing to 1.82 g (4.39 mmol) of di (p-tolyl) -1,3,5-triazine, 2- (3-bromophenyl) -4, After confirming disappearance of 6-di (p-tolyl) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.61 g / yield 63.1%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The nuclear magnetic resonance spectrum ( ¹ H-NMR) of this crystal is shown in FIG. 50 (entire region) and FIG. 51 (enlarged view). Assignment of ¹ H-NMR spectrum is as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 9.06 (s, 1H), 8.79 (d, J = 7.8 Hz, 1H), 8.68 (d, J = 8.2 Hz, 4H) , 8.26 (d, J = 1.8 Hz, 1H), 8.04 (d, J = 3.2 Hz, 2H), 7.91 (d, J = 7.8 Hz, 1H), 7.83− 7.59 (m, 7H), 7.54-7.46 (m, 1H), 7.37 (d, J = 7.8 Hz, 5H), 2.48 (s, 6H) ppm;
Moreover, the result of thermal decomposition temperature (TG-DTA) is shown in FIG.
The results of elemental analysis are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 84.80 (84.95), Hydrogen: 4.98 (5.04)
Nitrogen: 7.21 (7.25)
Moreover, the result of mass spectrometry was m / z 580 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBF (4) -HH-DiMeTRZ.

Example 18
2- {3- [3- (Dibenzothiophen-4-yl) phenyl] phenyl} -4,6-di (p-tolyl) -1,3,5-triazine [DBT (4) -H-H-DiMeTRZ : (I) -1240 Compound]
The starting materials in Example 11 were synthesized from 1.60 g (5.27 mmol) of 3- (dibenzothiophen-4-yl) phenylboronic acid in Synthesis Example 9 and 2- (3-bromophenyl) -4, After reacting in exactly the same manner except that the amount was changed to 1.82 g (4.39 mmol) of 6-di (p-tolyl) -1,3,5-triazine, 2- (3-bromophenyl) -4 The disappearance of, 6-di (p-tolyl) -1,3,5-triazine was confirmed and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.04 g / yield 78.1%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The nuclear magnetic resonance spectrum ( ¹ H-NMR) of this crystal is shown in FIG. 53 (entire region) and FIG. 54 (enlarged view).
Assignment of ¹ H-NMR spectrum is as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 9.10 (d, J = 1.4 Hz, 1H), 8.78 (d, J = 7.8 Hz, 1H), 8.68 (d, J = 8.2 Hz, 4H), 8.28-8.11 (m, 3H), 7.93 (d, J = 7.8 Hz, 1H), 7.88-7.74 (m, 3H), 7. 74-7.55 (m, 4H), 7.55-7.41 (m, 2H), 7.40-7.28 (m, 4H), 2.48 (d, J = 14.2 Hz, 6H) ) Ppm;
The results of elemental analysis are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.59 (82.66), Hydrogen: 5.02 (4.91)
Nitrogen: 7.04 (7.05), Sulfur: 5.35 (5.38)
Moreover, the result of mass spectrometry was m / z 595 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBT (4) -HH-DiMeTRZ.

Example 19
2- {3- [3- (Dibenzofuran-4-yl) phenyl] phenyl} -4,6-di (p-fluorophenyl) -1,3,5-triazine [DBF (4) -HH-DiFTRZ : Compound of (I) -1209]
The starting materials in Example 11 are 1.51 g (5.27 mmol) of 3- (dibenzofuran-4-yl) phenylboronic acid of Synthesis Example 8 and 2- (3-bromophenyl) -4,6 of Synthesis Example 5. -After reacting in exactly the same manner except that it was changed to 1.78 g (4.39 mmol) of di (p-fluorophenyl) -1,3,5-triazine, 2- (3-bromophenyl) -4 After confirming disappearance of 1,6-di (p-fluorophenyl) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.70 g / yield 66.2%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The nuclear magnetic resonance spectrum ( ¹ H-NMR) of this crystal is shown in FIG. 55 (entire region) and FIG. 56 (enlarged view). Assignment of ¹ H-NMR spectrum is as follows.
¹ H-NMR (400 MHz, DMSO-d6): δ 9.01 (s, 1H), 8.84 (dd, J = 8.7, 5.5 Hz, 4H), 8.78 (d, J = 7) .8 Hz, 1H), 8.65 (d, J = 1.8 Hz, 1H), 8.26 (d, J = 7.6 Hz, 1H), 8.16 (d, J = 6.9 Hz, 2H) 7.97 (dd, J = 8.7, 1.8 Hz, 1H), 7.89-7.77 (m, 4H), 7.76-7.67 (m, 2H), 7.56 ( t, J = 7.8 Hz, 1H), 7.52-7.40 (m, 4H) ppm;
Moreover, the result of thermal decomposition temperature (TG-DTA) is shown in FIG.
The results of elemental analysis are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 79.66 (79.71), Hydrogen: 3.70 (3.95)
Nitrogen: 7.11 (7.15), Fluorine: 7.32 (7.15)
Moreover, the result of mass spectrometry was m / z 588 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBF (4) -HH-DiFTRZ.

Example 20
2- {3- [3- (Dibenzothiophen-4-yl) phenyl] phenyl} -4,6-di (p-fluorophenyl) -1,3,5-triazine [DBT (4) -HH- DiFTRZ: (I) -1385 Compound]
The starting materials in Example 11 were synthesized from 1.60 g (5.27 mmol) of 3- (dibenzothiophen-4-yl) phenylboronic acid in Synthesis Example 9 and 2- (3-bromophenyl) -4, After reacting in exactly the same manner except that it was changed to 1.78 g (4.39 mmol) of 6-di (p-fluorophenyl) -1,3,5-triazine, 2- (3-bromophenyl)- The disappearance of 4,6-di (p-fluorophenyl) -1,3,5-triazine was confirmed, and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.10 g / yield 79.6%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The nuclear magnetic resonance spectrum ( ¹ H-NMR) of this crystal is shown in FIG. 58 (entire region) and FIG. 59 (enlarged view).
Assignment of ¹ H-NMR spectrum is as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 9.21-8.97 (m, 1H), 8.79 (d, J = 5.4 Hz, 5H), 8.30-8.13 (m, 3H), 7.99-7.90 (m, 1H), 7.90-7.75 (m, 3H), 7.65 (d, J = 35.8 Hz, 4H), 7.56-7. 39 (m, 2H), 7.21 (d, J = 8.6 Hz, 4H) ppm;
The results of elemental analysis are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 77.41 (77.59), Hydrogen: 3.75 (3.84)
Nitrogen: 7.03 (6.96), Sulfur: 5.25 (5.31)
Moreover, the result of mass spectrometry is m / z 603 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBT (4) -HH-DiFTRZ.

Example 21
2- {3- [3- (Dibenzofuran-4-yl) phenyl] phenyl} -4,6-di (1-naphthyl) -1,3,5-triazine [DBF (4) -HH-DiNapTRZ: Compound of (II) -733]
The starting materials in Example 11 are 1.51 g (5.27 mmol) of 3- (dibenzofuran-4-yl) phenylboronic acid of Synthesis Example 8 and 2- (3-bromophenyl) -4,6 of Synthesis Example 6. -After reacting in exactly the same manner except for changing to 2.13 g (4.39 mmol) of di (1-naphthyl) -1,3,5-triazine, 2- (3-bromophenyl) -4, After confirming the disappearance of 6-di (1-naphthyl) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
Ethyl acetate was added to the obtained reaction mixture, transferred to a separatory funnel, washed with saturated brine, and further ethyl acetate was added to extract an organic layer. Since a large amount of precipitate was confirmed in the liquid separation, the solution was suction filtered, and the resulting off-white solid was washed with methanol / water and then dried under reduced pressure. Next, toluene was added and heated to reflux, followed by hot filtration using silica gel, and confirmation by thin layer chromatography (SiO ₂ , developing solvent: dichloromethane / hexane = 1 / 3.5). Were all gone. The obtained liquid was concentrated and dried under reduced pressure, and then purified by recrystallization (solvent: chlorobenzene). Then, it was washed with hexane and dried under reduced pressure to obtain a white solid (yield 2.27 g / yield 75.6%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The nuclear magnetic resonance spectrum ( ¹ H-NMR) of this crystal is shown in FIG. 60 (entire region) and FIG. 61 (enlarged view). Assignment of ¹ H-NMR spectrum is as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 9.27 (d, J = 8.7 Hz, 2H 9.27 (d, J = 8.7 Hz, 2H), 9.15 (s, 1H), 8 .81 (d, J = 8.2 Hz, 1H), 8.61 (d, J = 7.3 Hz, 2H), 8.22 (d, J = 1.4 Hz, 1H), 8.09 (d, J = 7.8 Hz, 2H), 8.04 (s, 1H), 7.97 (t, J = 4.1 Hz, 4H), 7.84-7.57 (m, 11H), 7.56- 7.44 (m, 3H), 7.42-7.27 (m, 1H) ppm;
The results of elemental analysis are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 86.59 (86.61), Hydrogen: 4.52 (4.48)
Nitrogen: 6.41 (6.45)
Moreover, the result of mass spectrometry was m / z 651 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBF (4) -HH-DiNapTRZ.

Example 22
2- {3- [3- (Dibenzothiophen-4-yl) phenyl] phenyl} -4,6-di (1-naphthyl) -1,3,5-triazine [DBT (4) -HH-DiNapTRZ : (II) -855 compound]
The starting materials in Example 11 were synthesized from 1.60 g (5.27 mmol) of 3- (dibenzothiophen-4-yl) phenylboronic acid of Synthesis Example 9 and 2- (3-bromophenyl) -4, After reacting in exactly the same manner except that the amount was changed to 2.13 g (4.39 mmol) of 6-di (1-naphthyl) -1,3,5-triazine, 2- (3-bromophenyl) -4 After confirming disappearance of 1,6-di (1-naphthyl) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.05 g / yield 56.8%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The nuclear magnetic resonance spectrum ( ¹ H-NMR) of this crystal is shown in FIG. 62 (overall view) and FIG. 63 (enlarged view).
Assignment of ¹ H-NMR spectrum is as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 9.25 (d, J = 8.2 Hz, 2H), 9.17 (s, 1H), 8.80 (d, J = 7.8 Hz, 1H) , 8.60 (d, J = 6.9 Hz, 2H), 8.25-8.18 (m, 2H), 8.16 (s, 1H), 8.08 (d, J = 8.2 Hz, 2H), 7.97 (t, J = 9.2 Hz, 3H), 7.80 (dd, J = 19.5, 7.6 Hz, 2H), 7.74-7.39 (m, 13H) ppm ;
The results of elemental analysis are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 84.48 (84.53), Hydrogen: 4.46 (4.38)
Nitrogen: 6.38 (6.29), Sulfur: 4.68 (4.80)
Moreover, the result of mass spectrometry was m / z 667 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBT (4) -HH-DiNapTRZ.

Example 23
2- {3- [3- (dibenzofuran-4-yl) phenyl] phenyl} -4,6-di (9-phenanthro) -1,3,5-triazine [DBF (4) -HH-DiPhenTRZ: Compound of (VIII) -3565]
The starting materials in Example 11 are 1.51 g (5.27 mmol) of 3- (dibenzofuran-4-yl) phenylboronic acid of Synthesis Example 8 and 2- (3-bromophenyl) -4,6 of Synthesis Example 7. -After reacting in exactly the same manner except that it was changed to 2.58 g (4.39 mmol) of di (9-phenanthro) -1,3,5-triazine, 2- (3-bromophenyl) -4, After confirming the disappearance of 6-di (9-phenanthro) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.01 g / yield 61.2%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals.
The results of elemental analysis of this crystal are as follows, and the numbers in parentheses are theoretical values.
Carbon: 87.81 (87.86), Hydrogen: 4.49 (4.42)
Nitrogen: 5.63 (5.59)
Moreover, the result of mass spectrometry was m / z 751 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBF (4) -HH-DiPhenTRZ.

Example 24
2- {3- [3- (Dibenzothiophen-4-yl) phenyl] phenyl} -4,6-di (9-phenanthro) -1,3,5-triazine [DBT (4) -HH-DiPhenTRZ : (VIII) -4159 compound]
The starting materials in Example 11 were synthesized from 1.60 g (5.27 mmol) of 3- (dibenzothiophen-4-yl) phenylboronic acid in Synthesis Example 9 and 2- (3-bromophenyl) -4, After reacting in exactly the same manner except that the amount was changed to 2.58 g (4.39 mmol) of 6-di (9-phenanthro) -1,3,5-triazine, 2- (3-bromophenyl) -4 The disappearance of, 6-di (9-phenanthro) -1,3,5-triazine was confirmed and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.05 g / yield 69.9%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 84.87 (84.91), Hydrogen: 4.49 (4.57)
Nitrogen: 7.63 (7.62)
Moreover, the result of mass spectrometry was m / z 667 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBT (4) -HH-DiPhenTRZ.

Example 25
2- {3- [3- (Dibenzofuran-3-yl) phenyl] phenyl} -4,6-diphenyl-1,3,5-triazine [DBF (3) -HH-PhTRZ: (I) -705 Compound of
The starting materials in Example 11 are 1.51 g (5.26 mmol) of 3- (dibenzofuran-3-yl) phenylboronic acid of Synthesis Example 12 and 2- (3-bromophenyl) -4,6 of Synthesis Example 1. -After reacting in exactly the same manner except that it was changed to 1.70 g (4.39 mmol) of diphenyl-1,3,5-triazine, 2- (3-bromophenyl) -4,6-diphenyl-1 After confirming disappearance of 1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.84 g / yield 76.3%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 84.87 (84.91), Hydrogen: 4.49 (4.57)
Nitrogen: 7.63 (7.62)
Moreover, the result of mass spectrometry was m / z 551 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBF (3) -HH-PhTRZ.

Example 26
2- {3- [3- (Dibenzothiophen-3-yl) phenyl] phenyl} -4,6-diphenyl-1,3,5-triazine [DBT (3) -HH-PhTRZ: (I)- Compound 881]
The starting materials in Example 11 were synthesized from 1.60 g (5.27 mmol) of 3- (dibenzothiophen-3-yl) phenylboronic acid of Synthesis Example 13 and 2- (3-bromophenyl) -4, of Synthesis Example 1. The reaction was conducted in the same manner except that it was changed to 1.70 g (4.39 mmol) of 6-diphenyl-1,3,5-triazine, and then 2- (3-bromophenyl) -4,6-diphenyl- After confirming disappearance of 1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.07 g / yield 83.4%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.57 (82.51), Hydrogen: 4.49 (4.44)
Nitrogen: 7.42 (7.40), Sulfur: 5.52 (5.65)
Moreover, the result of mass spectrometry was m / z 567 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBT (3) -HH-PhTRZ.

Example 27
2- {3- [3- (dibenzofuran-1-yl) phenyl] phenyl} -4,6-diphenyl-1,3,5-triazine [DBF (1) -HH-PhTRZ: (I) -1 Compound of
The starting materials in Example 11 are 1.51 g (5.26 mmol) of 3- (dibenzofuran-1-yl) phenylboronic acid of Synthesis Example 14 and 2- (3-bromophenyl) -4,6 of Synthesis Example 1. -After reacting in exactly the same manner except that it was changed to 1.70 g (4.39 mmol) of diphenyl-1,3,5-triazine, 2- (3-bromophenyl) -4,6-diphenyl-1 After confirming disappearance of 1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.03 g / yield 84.1%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 84.84 (84.91), Hydrogen: 4.61 (4.57)
Nitrogen: 7.66 (7.62)
Moreover, the result of mass spectrometry was m / z 551 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBF (1) -HH-PhTRZ.

Example 28
2- {3- [3- (Dibenzothiophen-1-yl) phenyl] phenyl} -4,6-diphenyl-1,3,5-triazine [DBT (1) -HH-PhTRZ: (I)- 177 compounds]
The starting materials in Example 11 were synthesized from 1.60 g (5.27 mmol) of 3- (dibenzothiophen-3-yl) phenylboronic acid of Synthesis Example 15 and 2- (3-bromophenyl) -4, Synthesis Example 1. The reaction was conducted in the same manner except that it was changed to 1.70 g (4.39 mmol) of 6-diphenyl-1,3,5-triazine, and then 2- (3-bromophenyl) -4,6-diphenyl- After confirming disappearance of 1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.03 g / yield 81.6%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.55 (82.51), Hydrogen: 4.41 (4.44)
Nitrogen: 7.53 (7.40), Sulfur: 5.41 (5.65)
Moreover, the result of mass spectrometry was m / z 567 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBT (1) -HH-PhTRZ.

Example 29
2- {3- [3- (7-Methyldibenzofuran-4-yl) phenyl] phenyl} -4,6-diphenyl-1,3,5-triazine [(7) MeDBF (4) -H-H-PhTRZ : (I) -1059 compound]
The starting materials in Example 11 were synthesized from 1.58 g (5.26 mmol) of 3- (7-methyldibenzofuran-4-yl) phenylboronic acid of Synthesis Example 16 and 2- (3-bromophenyl)-of Synthesis Example 1. The reaction was conducted in the same manner except that it was changed to 1.70 g (4.39 mmol) of 4,6-diphenyl-1,3,5-triazine, and then 2- (3-bromophenyl) -4,6- After confirming the disappearance of diphenyl-1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.00 g / yield 80.4%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 84.89 (84.93), Hydrogen: 4.76 (4.81)
Nitrogen: 7.46 (7.43)
Moreover, the result of mass spectrometry was m / z 565 [M] ⁺ , and from these data, it was confirmed that the obtained compound was (7) MeDBF (4) -HH-PhTRZ.

Example 30
2- {3- [3- (7-Methyldibenzothiophen-4-yl) phenyl] phenyl} -4,6-diphenyl-1,3,5-triazine [(7) MeDBT (4) -HH- PhTRZ: Compound of (I) -1235]
The starting material in Example 11 is 1.60 g (5.27 mmol) of 3- (7-methyldibenzothiophen-4-yl) phenylboronic acid of Synthesis Example 17 and 2- (3-bromophenyl) of Synthesis Example 1 After reacting in exactly the same manner except that it was changed to 1.70 g (4.39 mmol) of -4,6-diphenyl-1,3,5-triazine, 2- (3-bromophenyl) -4,6 -The disappearance of diphenyl-1,3,5-triazine was confirmed and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.13 g / yield 83.5%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.55 (82.59), Hydrogen: 4.61 (4.68)
Nitrogen: 7.23 (7.22), Sulfur: 5.61 (5.51)
Moreover, the result of mass spectrometry was m / z 581 [M] ⁺ , and from these data, it was confirmed that the obtained compound was (7) MeDBT (4) -HH-PhTRZ.

Example 31
2- {3- [3- (7-Fluorodibenzofuran-4-yl) phenyl] phenyl} -4,6-diphenyl-1,3,5-triazine [(7) FDBF (4) -H-H-PhTRZ : Compound of (I) -1204]
The starting materials in Example 11 were synthesized from 1.61 g (5.26 mmol) of 3- (7-fluorodibenzofuran-4-yl) phenylboronic acid of Synthesis Example 18 and 2- (3-bromophenyl)-of Synthesis Example 1. The reaction was conducted in the same manner except that it was changed to 1.70 g (4.39 mmol) of 4,6-diphenyl-1,3,5-triazine, and then 2- (3-bromophenyl) -4,6- After confirming the disappearance of diphenyl-1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.00 g / yield 80.4%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.31 (82.23), Hydrogen: 4.26 (4.25)
Nitrogen: 7.33 (7.28), Fluorine: 3.31 (3.34)
Moreover, the result of mass spectrometry was m / z 569 [M] ⁺ , and from these data, it was confirmed that the obtained compound was (7) FDBF (4) -HH-PhTRZ.

Example 32
2- {3- [3- (7-fluorodibenzothiophen-4-yl) phenyl] phenyl} -4,6-diphenyl-1,3,5-triazine [(7) FDBT (4) -HH- PhTRZ: Compound of (I) -1380]
The starting materials in Example 11 are 1.69 g (5.27 mmol) of 3- (7-fluorodibenzothiophen-4-yl) phenylboronic acid of Synthesis Example 19 and 2- (3-bromophenyl) of Synthesis Example 1 After reacting in exactly the same manner except that it was changed to 1.70 g (4.39 mmol) of -4,6-diphenyl-1,3,5-triazine, 2- (3-bromophenyl) -4,6 -The disappearance of diphenyl-1,3,5-triazine was confirmed and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.04 g / yield 79.6%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 79.90 (79.98), Hydrogen: 4.11 (4.13)
Nitrogen: 7.15 (7.17), Sulfur: 5.54 (5.47)
Fluorine: 3.30 (3.24)
Moreover, the result of mass spectrometry was m / z 586 [M] ⁺ , and from these data, it was confirmed that the obtained compound was (7) FDBT (4) -HH-PhTRZ 3.

Reference Example 33
2- {3- [3- (7-phenyldibenzofuran-4-yl) phenyl] phenyl} -4,6-diphenyl-1,3,5-triazine [(7) PhDBF (4) -H-H-PhTRZ : Compounds not listed in the table]
The starting materials in Example 11 were prepared by using 1.91 g (5.26 mmol) of 3- (7-phenyldibenzofuran-4-yl) phenylboronic acid of Synthesis Example 20 and 2- (3-bromophenyl)-of Synthesis Example 1. The reaction was conducted in the same manner except that it was changed to 1.70 g (4.39 mmol) of 4,6-diphenyl-1,3,5-triazine, and then 2- (3-bromophenyl) -4,6- After confirming the disappearance of diphenyl-1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.25 g / yield 81.8%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 86.14 (86.10), Hydrogen: 4.63 (4.66)
Nitrogen: 7.63 (7.69)
Moreover, the result of mass spectrometry was m / z 627 [M] ⁺ , and from these data, it was confirmed that the obtained compound was (7) PhDBF (4) -HH-PhTRZ.

Reference Example 34
2- {3- [3- (7-phenyldibenzothiophen-4-yl) phenyl] phenyl} -4,6-diphenyl-1,3,5-triazine [(7) PhDBT (4) -HH- PhTRZ: Compound not listed in the table]
The starting materials in Example 11 are 2.00 g (5.27 mmol) of 3- (7-fluorodibenzothiophen-4-yl) phenylboronic acid of Synthesis Example 21 and 2- (3-bromophenyl) of Synthesis Example 1 After reacting in exactly the same manner except that it was changed to 1.70 g (4.39 mmol) of -4,6-diphenyl-1,3,5-triazine, 2- (3-bromophenyl) -4,6 -The disappearance of diphenyl-1,3,5-triazine was confirmed and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.34 g / yield 82.7%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 83.89 (83.95), Hydrogen: 4.51 (4.54)
Nitrogen: 6.55 (6.53), Sulfur: 5.05 (4.98)
Moreover, the result of mass spectrometry was m / z 643 [M] ⁺ , and from these data, it was confirmed that the obtained compound was (7) PhDBT (4) -HH-PhTRZ.

Example 35
2- {3- [3- (Dibenzofuran-4-yl) -6-methylphenyl] phenyl} -4,6-diphenyl-1,3,5-triazine [DBF (4) -Me-H-PhTRZ: ( I) -1058 Compound]
The starting materials in Example 11 are 1.59 g (5.26 mmol) of 2-methyl-5- (dibenzofuran-4-yl) phenylboronic acid of Synthesis Example 24 and 2- (3-bromophenyl) of Synthesis Example 1. After reacting in exactly the same manner except that it was changed to 1.70 g (4.39 mmol) of -4,6-diphenyl-1,3,5-triazine, 2- (3-bromophenyl) -4,6 -The disappearance of diphenyl-1,3,5-triazine was confirmed and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.12 g / yield 85.7%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The nuclear magnetic resonance spectrum ( ¹ H-NMR) of this crystal is shown in FIG. 64 (entire region) and FIG. 65 (enlarged view). Assignment of ¹ H-NMR spectrum is as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.86 (s, 1H), 8.84-8.75 (m, 5H), 8.06-7.85 (m, 4H), 7.72 −7.64 (m, 3H), 7.64-7.50 (m, 8H), 7.43 (td, J = 7.3, 3.2 Hz, 2H), 7.35 (t, J = 7.3 Hz, 1 H), 2.45 (s, 3 H) ppm;
The results of elemental analysis are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 84.88 (84.93), Hydrogen: 4.83 (4.81)
Nitrogen: 7.63 (7.67)
Moreover, the result of mass spectrometry was m / z 565 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBF (4) -Me-H-PhTRZ.

Example 36
2- {3- [3- (Dibenzothiophen-4-yl) -6-methylphenyl] phenyl} -4,6-diphenyl-1,3,5-triazine [(DBT (4) -Me-H-PhTRZ : Compound of (I) -1234]
The starting material in Example 11 is 1.68 g (5.27 mmol) of 2-methyl-5- (dibenzothiophen-4-yl) phenylboronic acid of Synthesis Example 25 and 2- (3-bromophenyl of Synthesis Example 1 ) -4,6-diphenyl-1,3,5-triazine Except for the change to 1.70 g (4.39 mmol), the reaction was conducted in the same manner, and then 2- (3-bromophenyl) -4, After confirming the disappearance of 6-diphenyl-1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.07 g / yield 81.4%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The nuclear magnetic resonance spectrum ( ¹ H-NMR) of this crystal is shown in FIG. 66 (entire region) and FIG. 67 (enlarged view).
Assignment of ¹ H-NMR spectrum is as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.87 (s, 1H), 8.79 (dd, J = 7.9, 1.6 Hz, 5H), 8.23-8.12 (m, 2H), 7.83-7.39 (m, 17H), 2.44 (d, J = 15.0 Hz, 3H) ppm;
The results of elemental analysis are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.71 (82.59), Hydrogen: 4.61 (4.68)
Nitrogen: 7.17 (7.22), Sulfur: 5.51 (5.51)
Moreover, the result of mass spectrometry was m / z 581 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBT (4) -Me-H-PhTRZ.

Example 37
2- {3- [3- (Dibenzofuran-4-yl) -6-fluorophenyl] phenyl} -4,6-diphenyl-1,3,5-triazine [DBF (4) -FH-PhTRZ: ( I) Compound of 1203]
The starting materials in Example 11 were mixed with 1.61 g (5.26 mmol) of 2-fluoro-5- (dibenzofuran-4-yl) phenylboronic acid of Synthesis Example 26 and 2- (3-bromophenyl) of Synthesis Example 1 After reacting in exactly the same manner except that it was changed to 1.70 g (4.39 mmol) of -4,6-diphenyl-1,3,5-triazine, 2- (3-bromophenyl) -4,6 -The disappearance of diphenyl-1,3,5-triazine was confirmed and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.14 g / yield 85.7%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The nuclear magnetic resonance spectrum ( ¹ H-NMR) of this crystal is shown in FIG. 68 (entire region) and FIG. 69 (enlarged view).
Assignment of ¹ H-NMR spectrum is as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 9.04 (s, 1H), 8.86-8.76 (m, 5H), 8.11 (dd, J = 7.8, 2.3 Hz, 1H), 8.04-7.85 (m, 4H), 7.75-7.52 (m, 9H), 7.51-7.28 (m, 4H) ppm;
The results of elemental analysis are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.04 (82.23), Hydrogen: 4.83 (4.81)
Nitrogen: 7.63 (7.67), Fluorine: 3.20 (3.34)
Moreover, the result of mass spectrometry was m / z 569 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBF (4) -FH-PhTRZ.

Example 38
2- {3- [3- (Dibenzothiophen-4-yl) -6-fluorophenyl] phenyl} -4,6-diphenyl-1,3,5-triazine [(DBT (4) -FH-PhTRZ : Compound of (I) -1379]
The starting materials in Example 11 were prepared by using 1.68 g (5.27 mmol) of 2-fluoro-5- (dibenzothiophen-4-yl) phenylboronic acid of Synthesis Example 27 and 2- (3-bromophenyl) of Synthesis Example 1. ) -4,6-diphenyl-1,3,5-triazine Except for the change to 1.70 g (4.39 mmol), the reaction was conducted in the same manner, and then 2- (3-bromophenyl) -4, After confirming the disappearance of 6-diphenyl-1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.09 g / yield 81.4%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The nuclear magnetic resonance spectrum ( ¹ H-NMR) of this crystal is shown in FIG. 70 (entire region) and FIG. 71 (enlarged view).
Assignment of ¹ H-NMR spectrum is as follows.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 9.06 (d, J = 1.4 Hz, 1H), 8.86-8.74 (m, 6H), 8.20 (td, J = 6. 9, 1.4 Hz, 2H), 8.01 (dd, J = 7.6, 2.5 Hz, 1H), 7.91 (dd, J = 7.6, 1.1 Hz, 1H), 7.82 −7.67 (m, 3H), 7.66-7.36 (m, 13H) ppm;
The results of elemental analysis are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 80.03 (79.98), Hydrogen: 4.05 (4.13)
Nitrogen: 7.16 (7.17), Sulfur: 5.51 (5.47)
Fluorine: 3.25 (3.24)
Moreover, the result of mass spectrometry was m / z 585 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBT (4) -FH-PhTRZ.

Example 39
2- {3- [3- (dibenzofuran-2-yl) phenyl] -4-methylphenyl} -4,6-diphenyl-1,3,5-triazine [DBF (2) -H-Me-PhTRZ: ( I) -753 Compound]
The starting materials in Synthesis Example 11 were 1.95 g (5.27 mmol) of 3- (dibenzofuran-2-yl) phenylboronic acid ester of Synthesis Example 10 and 2- (3-bromo-4-methylphenyl) of Synthesis Example 2. ) -4,6-diphenyl-1,3,5-triazine was reacted in the same manner except that it was changed to 1.76 g (4.39 mmol), and then 2- (3-bromo-4-methylphenyl) was reacted. ) -4,6-diphenyl-1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.09 g / yield 84.2%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 85.02 (84.93), Hydrogen: 4.84 (4.81)
Nitrogen: 7.41 (7.43)
Moreover, the result of mass spectrometry was m / z 565 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBF (2) -H-Me-PhTRZ.

Example 40
2- {3- [3- (Dibenzothiophen-2-yl) phenyl] -4-methylphenyl} -4,6-diphenyl-1,3,5-triazine [DBT (2) -H-Me-PhTRZ: Compound (I) -533]
The starting materials in Synthesis Example 11 were prepared by using 2.03 g (5.27 mmol) of 3- (dibenzothiophen-2-yl) phenylboronic acid ester of Synthesis Example 11 and 2- (3-bromo-4-methyl of Synthesis Example 2). Phenyl) -4,6-diphenyl-1,3,5-triazine was reacted in exactly the same manner except that it was changed to 1.76 g (4.39 mmol), and then 2- (3-bromo-4-methyl After confirming disappearance of (phenyl) -4,6-diphenyl-1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.65 g / yield 64.7%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.67 (82.59), Hydrogen: 4.76 (4.68)
Nitrogen: 7.30 (7.22), Sulfur: 5.27 (5.51)
Moreover, the result of mass spectrometry was m / z 581 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBT (2) -H-Me-PhTRZ.

Example 41
2- {3- [3- (dibenzofuran-2-yl) phenyl] -4-fluorophenyl} -4,6-diphenyl-1,3,5-triazine [DBF (2) -HF-PhTRZ: ( I) -502 Compound]
The starting materials in Example 11 were prepared from 1.95 g (5.27 mmol) of 3- (dibenzofuran-2-yl) phenylboronic acid ester of Synthesis Example 10 and 2- (3-bromo-4-fluorophenyl of Synthesis Example 3 ) -4,6-diphenyl-1,3,5-triazine The reaction was carried out in the same manner except that it was changed to 1.78 g (4.39 mmol), and then 2- (3-bromo-4-fluorophenyl) was obtained. ) -4,6-diphenyl-1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.12 g / yield 82.8%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.19 (82.23), Hydrogen: 4.24 (4.25)
Nitrogen: 7.40 (7.38), Fluorine: 3.41 (3.34)
Moreover, the result of mass spectrometry was m / z 569 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBF (2) -HF-PhTRZ.

Example 42
2- {3- [3- (Dibenzothiophen-2-yl) phenyl] -4-fluorophenyl} -4,6-diphenyl-1,3,5-triazine [DBT (2) -HF-PhTRZ: Compound (I) -678]
The starting material in Example 11 was prepared by using 2.03 g (5.27 mmol) of 3- (dibenzothiophen-2-yl) phenylboronic acid ester of Synthesis Example 11 and 2- (3-bromo-4-fluoro of Synthesis Example 3). Phenyl) -4,6-diphenyl-1,3,5-triazine was reacted in exactly the same manner except that it was changed to 1.78 g (4.39 mmol), and then 2- (3-bromo-4-fluoro After confirming the disappearance of (phenyl) -4,6-diphenyl-1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.06 g / yield 82.8%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 79.92 (79.98), Hydrogen: 4.10 (4.13)
Nitrogen: 7.14 (7.17), Sulfur: 5.41 (5.47)
Fluorine: 3.43 (3.24)
Moreover, the result of mass spectrometry was m / z 585 [M] ⁺ , and from these data, it was confirmed that the obtained compound was DBT (2) -HF-PhTRZ.

Example 43
2- {3- [3- (Dibenzofuran-2-yl) phenyl] phenyl} -4,6-di (p-tolyl) -1,3,5-triazine [DBF (2) -HH-DiMeTRZ: Compound of (I) -360]
The starting materials in Example 11 were prepared from 1.95 g (5.27 mmol) of 3- (dibenzofuran-2-yl) phenylboronic acid ester of Synthesis Example 10 and 2- (3-bromophenyl) -4, Synthesis Example 4 After reacting in exactly the same manner except that the amount was changed to 1.82 g (4.39 mmol) of 6-di (p-tolyl) -1,3,5-triazine, 2- (3-bromophenyl) -4 The disappearance of, 6-di (p-tolyl) -1,3,5-triazine was confirmed and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.74 g / yield 68.4%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 84.82 (84.95), Hydrogen: 4.94 (5.04)
Nitrogen: 7.21 (7.25)
Mass spectrometry results from these data ^{m / z 580 [M] +} , that the compound obtained is DBF (2) -H-H- DiMeTRZ was confirmed.

Example 44
2- {3- [3- (Dibenzothiophen-2-yl) phenyl] phenyl} -4,6-di (p-tolyl) -1,3,5-triazine [DBT (2) -H-H-DiMeTRZ : Compound of (I) -536]
The starting materials in Example 11 are 2.03 g (5.27 mmol) of 3- (dibenzothiophen-2-yl) phenylboronic acid ester of Synthesis Example 11 and 2- (3-bromophenyl) -4 of Synthesis Example 4. , 6-di (p-tolyl) -1,3,5-triazine except that it was changed to 1.82 g (4.39 mmol), the reaction was conducted in exactly the same manner, and then 2- (3-bromophenyl)- After confirming disappearance of 4,6-di (p-tolyl) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.04 g / yield 78.1%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.78 (82.66), Hydrogen: 4.94 (4.91)
Nitrogen: 7.11 (7.05), Sulfur: 5.17 (5.38)
As a result of mass spectrometry, m / z 595 [M] ⁺ was used, and from this data, it was confirmed that the obtained compound was DBT (2) -HH-DiMeTRZ.

Example 45
2- {3- [3- (Dibenzofuran-2-yl) phenyl] phenyl} -4,6-di (p-fluorophenyl) -1,3,5-triazine [DBF (2) -HH-DiFTRZ : Compound of (I) -505]
The starting materials in Example 11 were 1.95 g (5.27 mmol) of 3- (dibenzofuran-2-yl) phenylboronic acid ester of Synthesis Example 10 and 2- (3-bromophenyl) -4, Synthesis Example 5 After reacting in exactly the same manner except that it was changed to 1.78 g (4.39 mmol) of 6-di (p-fluorophenyl) -1,3,5-triazine, 2- (3-bromophenyl)- The disappearance of 4,6-di (p-fluorophenyl) -1,3,5-triazine was confirmed, and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.70 g / yield 66.2%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 79.68 (79.71), Hydrogen: 3.82 (3.95)
Nitrogen: 7.04 (7.15), Fluorine: 7.22 (7.15)
As a result of mass spectrometry, m / z 588 [M] ⁺ was used, and from these data, it was confirmed that the obtained compound was DBF (2) -HH-DiFTRZ.

Example 46
2- {3- [3- (Dibenzothiophen-2-yl) phenyl] phenyl} -4,6-di (p-fluorophenyl) -1,3,5-triazine [DBT (2) -HH- Of DiFTRZ: (I) -681 Compound]
The starting materials in Example 11 are 2.03 g (5.27 mmol) of 3- (dibenzothiophen-2-yl) phenylboronic acid ester of Synthesis Example 11 and 2- (3-bromophenyl) -4 of Synthesis Example 5. , 6-di (p-fluorophenyl) -1,3,5-triazine except that it was changed to 1.78 g (4.39 mmol), the reaction was conducted in the same manner, and then 2- (3-bromophenyl) After confirming disappearance of -4,6-di (p-fluorophenyl) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.11 g / yield 79.6%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 77.52 (77.59), Hydrogen: 3.76 (3.84)
Nitrogen: 6.88 (6.96), Sulfur: 5.27 (5.31)
Fluorine: 6.57 (6.29)
The result of mass spectrometry was m / z 604 [M] ⁺ , and from this data, it was confirmed that the obtained compound was DBT (2) -H—H-DiFTRZ.

Example 47
2- {3- [3- (Dibenzofuran-2-yl) phenyl] phenyl} -4,6-di (1-naphthyl) -1,3,5-triazine [DBF (2) -HH-DiNapTRZ: Synthesis of (II) -245 Compound]
The starting materials in Example 11 were prepared from 1.95 g (5.27 mmol) of 3- (dibenzofuran-2-yl) phenylboronic acid ester of Synthesis Example 10 and 2- (3-bromophenyl) -4, Synthesis Example 6. After reacting in exactly the same manner except that the amount was changed to 2.13 g (4.39 mmol) of 6-di (1-naphthyl) -1,3,5-triazine, 2- (3-bromophenyl) -4 After confirming disappearance of 1,6-di (1-naphthyl) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.24 g / yield 78.3%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 86.59 (86.61), Hydrogen: 4.52 (4.48)
Nitrogen: 6.41 (6.45)
As a result of mass spectrometry, m / z 651 [M] ⁺ and these data confirmed that the obtained compound was DBF (2) -H—H-DiNapTRZ.

Example 48
2- {3- [3- (Dibenzothiophen-2-yl) phenyl] phenyl} -4,6-di (1-naphthyl) -1,3,5-triazine [DBT (2) -H-H-DiNapTRZ : Compound of (II) -367]
The starting materials in Example 11 are 2.03 g (5.27 mmol) of 3- (dibenzothiophen-2-yl) phenylboronic acid ester of Synthesis Example 11 and 2- (3-bromophenyl) -4 of Synthesis Example 6. , 6-di (1-naphthyl) -1,3,5-triazine except that it was changed to 2.13 g (4.39 mmol), the reaction was conducted in the same manner, and then 2- (3-bromophenyl)- The disappearance of 4,6-di (1-naphthyl) -1,3,5-triazine was confirmed, and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.67 g / yield 56.8%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 84.48 (84.53), Hydrogen: 4.46 (4.38)
Nitrogen: 6.33 (6.29), Sulfur: 4.73 (4.80)
The result of mass spectrometry was m / z 668 [M] ⁺ , and from this data, it was confirmed that the obtained compound was DBT (2) -HH-DiNapTRZ.

Example 49
2- {3- [3- (Dibenzofuran-2-yl) phenyl] phenyl} -4,6-di (9-phenanthro) -1,3,5-triazine [DBF (2) -H-H-DiPhenTRZ: Compound of (VIII) -1189]
The starting materials in Example 11 were 1.95 g (5.27 mmol) of 3- (dibenzofuran-2-yl) phenylboronic acid ester of Synthesis Example 10 and 2- (3-bromophenyl) -4, Synthesis Example 7 After reacting in exactly the same manner except that the amount was changed to 2.58 g (4.39 mmol) of 6-di (9-phenanthro) -1,3,5-triazine, 2- (3-bromophenyl) -4 The disappearance of, 6-di (9-phenanthro) -1,3,5-triazine was confirmed and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.02 g / yield 61.2%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 87.77 (87.86), Hydrogen: 4.35 (4.42)
Nitrogen: 5.52 (5.59)
As a result of mass spectrometry, m / z 752 [M] ⁺ and these data confirmed that the obtained compound was DBF (2) -HH-DiPhenTRZ.

Example 50
2- {3- [3- (Dibenzothiophen-2-yl) phenyl] phenyl} -4,6-di (9-phenanthro) -1,3,5-triazine [DBT (2) -H-H-DiPhenTRZ : Compound of (VIII) -1783]
The starting materials in Example 11 are 2.03 g (5.27 mmol) of 3- (dibenzothiophen-2-yl) phenylboronic acid ester of Synthesis Example 11 and 2- (3-bromophenyl) -4 of Synthesis Example 7. , 6-di (9-phenanthro) -1,3,5-triazine, except that it was changed to 2.58 g (4.39 mmol), the reaction was conducted in the same manner, and then 2- (3-bromophenyl)- After confirming the disappearance of 4,6-di (9-phenanthro) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 1.92 g / yield 56.8%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
). The obtained white solid was washed with hexane and then dried under reduced pressure to obtain a white solid (yield 1.92 g / yield 56.8%). Thereafter, the obtained white solid was purified by sublimation by a conventional method. The results of elemental analysis of crystals obtained by sublimation purification are as follows, and the numbers in parentheses are theoretical values.
Carbon: 86.11 (86.02), Hydrogen: 4.25 (4.33)
Nitrogen: 5.55 (5.47), Sulfur: 4.09 (4.18)
The result of mass spectrometry was m / z 768 [M] ⁺ , and from this data, it was confirmed that the obtained compound was DBT (2) -HH-DiPhenTRZ.

Example 51
2- {3- [3- (dibenzofuran-3-yl) phenyl] -4-methylphenyl} -4,6-diphenyl-1,3,5-triazine [DBF (3) -H-Me-PhTRZ: ( I) -709 Compound]
Starting materials in Synthesis Example 11 were 1.51 g (5.27 mmol) of 3- (dibenzofuran-3-yl) phenylboronic acid of Synthesis Example 12 and 2- (3-bromo-4-methylphenyl) of Synthesis Example 2. 2- (3-Bromo-4-methylphenyl) was reacted in the same manner except that it was changed to 1.76 g (4.39 mmol) of -4,6-diphenyl-1,3,5-triazine. After confirming the disappearance of -4,6-diphenyl-1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.08 g / yield 83.3%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 85.11 (84.93), Hydrogen: 4.79 (4.81)
Nitrogen: 7.54 (7.43)
As a result of mass spectrometry, m / z 565 [M] ⁺ and these data confirmed that the obtained compound was DBF (3) -H-Me-PhTRZ.

Example 52
2- {3- [3- (Dibenzothiophen-3-yl) phenyl] -4-methylphenyl} -4,6-diphenyl-1,3,5-triazine [DBT (3) -H-Me-PhTRZ: Compound of (I) -885]
The starting materials in Synthesis Example 11 are 1.60 g (5.27 mmol) of 3- (dibenzothiophen-3-yl) phenylboronic acid of Synthesis Example 13 and 2- (3-bromo-4-methylphenyl) of Synthesis Example 2. ) -4,6-diphenyl-1,3,5-triazine was reacted in the same manner except that it was changed to 1.76 g (4.39 mmol), and then 2- (3-bromo-4-methylphenyl) was reacted. ) -4,6-diphenyl-1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.65 g / yield 64.7%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.41 (82.59), Hydrogen: 4.55 (4.68)
Nitrogen: 7.34 (7.22), Sulfur: 5.70 (5.51)
The result of mass spectrometry was m / z 580 [M] ⁺ , and from this data, it was confirmed that the obtained compound was DBT (3) -H-Me-PhTRZ.

Example 53
2- {3- [3- (dibenzofuran-3-yl) phenyl] -4-fluorophenyl} -4,6-diphenyl-1,3,5-triazine [DBF (3) -HF-PhTRZ: ( I) -854 Compound]
The starting materials in Example 11 are 1.51 g (5.27 mmol) of 3- (dibenzofuran-3-yl) phenylboronic acid of Synthesis Example 12 and 2- (3-bromo-4-fluorophenyl) of Synthesis Example 3. 2- (3-bromo-4-fluorophenyl) was reacted in exactly the same manner except that it was changed to 1.78 g (4.39 mmol) of -4,6-diphenyl-1,3,5-triazine. After confirming the disappearance of -4,6-diphenyl-1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.98 g / yield 79.4%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.14 (82.23), Hydrogen: 4.34 (4.25)
Nitrogen: 7.33 (7.38), Fluorine: 3.39 (3.34)
As a result of mass spectrometry, m / z 570 [M] ⁺ and these data confirmed that the obtained compound was DBF (3) -HF-PhTRZ.

Example 54
2- {3- [3- (Dibenzothiophen-3-yl) phenyl] -4-fluorophenyl} -4,6-diphenyl-1,3,5-triazine [DBT (3) -HF-PhTRZ: Synthesis of (I) -1030 Compound]
The starting materials in Example 11 were synthesized from 1.60 g (5.27 mmol) of 3- (dibenzothiophen-3-yl) phenylboronic acid of Synthesis Example 13 and 2- (3-bromo-4-fluorophenyl of Synthesis Example 3 ) -4,6-diphenyl-1,3,5-triazine The reaction was carried out in the same manner except that it was changed to 1.78 g (4.39 mmol), and then 2- (3-bromo-4-fluorophenyl) was obtained. ) -4,6-diphenyl-1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.09 g / yield 81.5%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 79.78 (79.98), Hydrogen: 4.06 (4.13)
Nitrogen: 7.22 (7.17), Sulfur: 5.49 (5.47)
Fluorine: 3.45 (3.24)
As a result of mass spectrometry, m / z 586 [M] ⁺ and from these data, it was confirmed that the obtained compound was DBT (3) -HF-PhTRZ.

Example 55
2- {3- [3- (Dibenzofuran-3-yl) phenyl] phenyl} -4,6-di (p-tolyl) -1,3,5-triazine [DBF (3) -H-H-DiMeTRZ: Synthesis of (I) -712 Compound]
The starting materials in Example 11 are 1.51 g (5.27 mmol) of 3- (dibenzofuran-3-yl) phenylboronic acid of Synthesis Example 12 and 2- (3-bromophenyl) -4,6 of Synthesis Example 4. -After reacting in exactly the same manner except for changing to 1.82 g (4.39 mmol) of di (p-tolyl) -1,3,5-triazine, 2- (3-bromophenyl) -4, After confirming disappearance of 6-di (p-tolyl) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.86 g / yield 73.0%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 84.80 (84.95), Hydrogen: 5.11 (5.04)
Nitrogen: 7.27 (7.25)
As a result of mass spectrometry, m / z 579 [M] ⁺ and these data confirmed that the obtained compound was DBF (3) -H—H—DiMeTRZ.

Example 56
2- {3- [3- (Dibenzothiophen-3-yl) phenyl] phenyl} -4,6-di (p-tolyl) -1,3,5-triazine [DBT (3) -H-H-DiMeTRZ : Compound of (I) -888]
The starting materials in Example 11 were synthesized from 1.60 g (5.27 mmol) of 3- (dibenzothiophen-3-yl) phenylboronic acid in Synthesis Example 13 and 2- (3-bromophenyl) -4, After reacting in exactly the same manner except that the amount was changed to 1.82 g (4.39 mmol) of 6-di (p-tolyl) -1,3,5-triazine, 2- (3-bromophenyl) -4 The disappearance of, 6-di (p-tolyl) -1,3,5-triazine was confirmed and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.17 g / yield 83.3%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.78 (82.66), Hydrogen: 5.02 (4.91)
Nitrogen: 7.16 (7.05), Sulfur: 5.04 (5.38)
As a result of mass spectrometry, m / z 595 [M] ⁺ was used, and from this data, it was confirmed that the obtained compound was DBT (3) -HH-DiMeTRZ.

Example 57
2- {3- [3- (Dibenzofuran-3-yl) phenyl] phenyl} -4,6-di (p-fluorophenyl) -1,3,5-triazine [DBF (3) -HH-DiFTRZ : Compound of (I) -857]
The starting materials in Example 11 are 1.51 g (5.27 mmol) of 3- (dibenzofuran-3-yl) phenylboronic acid of Synthesis Example 12 and 2- (3-bromophenyl) -4,6 of Synthesis Example 5. -After reacting in exactly the same manner except that it was changed to 1.78 g (4.39 mmol) of di (p-fluorophenyl) -1,3,5-triazine, 2- (3-bromophenyl) -4 After confirming disappearance of 1,6-di (p-fluorophenyl) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.95 g / yield 75.4%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 79.63 (79.71), Hydrogen: 4.01 (3.95)
Nitrogen: 7.14 (7.15), Fluorine: 6.40 (6.47)
As a result of mass spectrometry, m / z 588 [M] ⁺ and these data confirmed that the obtained compound was DBF (3) -HH-DiFTRZ.

Example 58
2- {3- [3- (Dibenzothiophen-3-yl) phenyl] phenyl} -4,6-di (p-fluorophenyl) -1,3,5-triazine [DBT (3) -HH- Of DiFTRZ: (I) -1033 Compound]
The starting materials in Example 11 were synthesized from 1.60 g (5.27 mmol) of 3- (dibenzothiophen-3-yl) phenylboronic acid in Synthesis Example 13 and 2- (3-bromophenyl) -4, After reacting in exactly the same manner except that it was changed to 1.78 g (4.39 mmol) of 6-di (p-fluorophenyl) -1,3,5-triazine, 2- (3-bromophenyl)- The disappearance of 4,6-di (p-fluorophenyl) -1,3,5-triazine was confirmed, and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.13 g / yield 80.3%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 77.63 (77.59), Hydrogen: 3.92 (3.84)
Nitrogen: 6.04 (6.29), Sulfur: 5.26 (5.31)
Fluorine: 7.15 (6.96)
Mass spectrometry results from this data in ^{m / z 604 [M] +} , that the compound obtained is DBT (3) -H-H- DiFTRZ was confirmed.

Example 59
2- {3- [3- (dibenzofuran-3-yl) phenyl] phenyl} -4,6-di (1-naphthyl) -1,3,5-triazine [DBF (3) -HH-DiNapTRZ: Compound of (II) -489]
The starting materials in Example 11 are 1.51 g (5.27 mmol) of 3- (dibenzofuran-3-yl) phenylboronic acid of Synthesis Example 12 and 2- (3-bromophenyl) -4,6 of Synthesis Example 6. -After reacting in exactly the same manner except for changing to 2.13 g (4.39 mmol) of di (1-naphthyl) -1,3,5-triazine, 2- (3-bromophenyl) -4, After confirming the disappearance of 6-di (1-naphthyl) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.30 g / yield 80.4%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 86.72 (86.61), Hydrogen: 4.44 (4.48)
Nitrogen: 6.29 (6.45)
As a result of mass spectrometry, m / z 651 [M] ⁺ and these data confirmed that the obtained compound was DBF (3) -HH-DiNapTRZ.

Example 60
2- {3- [3- (Dibenzothiophen-3-yl) phenyl] phenyl} -4,6-di (1-naphthyl) -1,3,5-triazine [DBT (3) -HH-DiNapTRZ : Compound of (II) -611]
The starting materials in Example 11 were synthesized from 1.60 g (5.27 mmol) of 3- (dibenzothiophen-3-yl) phenylboronic acid of Synthesis Example 13 and 2- (3-bromophenyl) -4, of Synthesis Example 6. After reacting in exactly the same manner except that the amount was changed to 2.13 g (4.39 mmol) of 6-di (1-naphthyl) -1,3,5-triazine, 2- (3-bromophenyl) -4 After confirming disappearance of 1,6-di (1-naphthyl) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.73 g / yield 59.2%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 84.61 (84.53), Hydrogen: 4.40 (4.38)
Nitrogen: 6.37 (6.29), Sulfur: 4.62 (4.80)
The result of mass spectrometry was m / z 668 [M] ⁺ , and from this data, it was confirmed that the obtained compound was DBT (3) -HH-DiNapTRZ.

Example 61
2- {3- [3- (dibenzofuran-3-yl) phenyl] phenyl} -4,6-di (9-phenanthro) -1,3,5-triazine [DBF (3) -HH-DiPhenTRZ: Compound of (VIII) -2377]
The starting materials in Example 11 are 1.51 g (5.27 mmol) of 3- (dibenzofuran-3-yl) phenylboronic acid of Synthesis Example 12 and 2- (3-bromophenyl) -4,6 of Synthesis Example 7. -After reacting in exactly the same manner except that it was changed to 2.58 g (4.39 mmol) of di (9-phenanthro) -1,3,5-triazine, 2- (3-bromophenyl) -4, After confirming the disappearance of 6-di (9-phenanthro) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.00 g / yield 60.7%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 87.89 (87.86), Hydrogen: 4.31 (4.42)
Nitrogen: 5.63 (5.59)
As a result of mass spectrometry, m / z 752 [M] ⁺ and these data confirmed that the obtained compound was DBF (3) -HH-DiPhenTRZ.

Example 62
2- {3- [3- (Dibenzothiophen-3-yl) phenyl] phenyl} -4,6-di (9-phenanthro) -1,3,5-triazine [DBT (3) -H-H-DiPhenTRZ : (VIII) -2971 compound]
The starting materials in Example 11 were synthesized from 1.60 g (5.27 mmol) of 3- (dibenzothiophen-3-yl) phenylboronic acid of Synthesis Example 13 and 2- (3-bromophenyl) -4, Synthesis Example 7. After reacting in exactly the same manner except that the amount was changed to 2.58 g (4.39 mmol) of 6-di (9-phenanthro) -1,3,5-triazine, 2- (3-bromophenyl) -4 The disappearance of, 6-di (9-phenanthro) -1,3,5-triazine was confirmed and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.08 g / yield 61.8%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 86.07 (86.02), Hydrogen: 4.39 (4.33)
Nitrogen: 5.49 (5.47), Sulfur: 4.05 (4.18)
The result of mass spectrometry was m / z 768 [M] ⁺ , and from this data, it was confirmed that the obtained compound was DBT (3) -HH-DiPhenTRZ.

Example 63
2- {3- [3- (Dibenzofuran-1-yl) phenyl] -4-methylphenyl} -4,6-diphenyl-1,3,5-triazine [DBF (1) -H-Me-PhTRZ: ( I) -5 Compound]
Starting materials in Synthesis Example 11 were 1.51 g (5.27 mmol) of 3- (dibenzofuran-1-yl) phenylboronic acid of Synthesis Example 14 and 2- (3-bromo-4-methylphenyl) of Synthesis Example 2. 2- (3-Bromo-4-methylphenyl) was reacted in the same manner except that it was changed to 1.76 g (4.39 mmol) of -4,6-diphenyl-1,3,5-triazine. After confirming the disappearance of -4,6-diphenyl-1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.98 g / yield 80.2%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 84.82 (84.93), Hydrogen: 4.79 (4.89)
Nitrogen: 7.54 (7.62)
As a result of mass spectrometry, m / z 565 [M] ⁺ and from these data, it was confirmed that the obtained compound was DBF (1) -H-Me-PhTRZ.

Example 64
2- {3- [3- (Dibenzothiophen-1-yl) phenyl] -4-methylphenyl} -4,6-diphenyl-1,3,5-triazine [DBT (1) -H-Me-PhTRZ: Synthesis of (I) -181 Compound]
The starting materials in Synthesis Example 11 are 1.60 g (5.27 mmol) of 3- (dibenzothiophen-3-yl) phenylboronic acid of Synthesis Example 15 and 2- (3-bromo-4-methylphenyl) of Synthesis Example 2. ) -4,6-diphenyl-1,3,5-triazine was reacted in the same manner except that it was changed to 1.76 g (4.39 mmol), and then 2- (3-bromo-4-methylphenyl) was reacted. ) -4,6-diphenyl-1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.99 g / yield 78.2%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.68 (82.59), Hydrogen: 4.51 (4.68)
Nitrogen: 7.30 (7.22), Sulfur: 5.51 (5.51)
The result of mass spectrometry was m / z 580 [M] ⁺ , and from this data, it was confirmed that the obtained compound was DBT (1) -H-Me-PhTRZ.

Example 65
2- {3- [3- (dibenzofuran-1-yl) phenyl] -4-fluorophenyl} -4,6-diphenyl-1,3,5-triazine [DBF (1) -HF-PhTRZ: ( I) -150 Compound]
The starting materials in Example 11 are 1.51 g (5.27 mmol) of 3- (dibenzofuran-1-yl) phenylboronic acid of Synthesis Example 14 and 2- (3-bromo-4-fluorophenyl) of Synthesis Example 3. 2- (3-bromo-4-fluorophenyl) was reacted in exactly the same manner except that it was changed to 1.78 g (4.39 mmol) of -4,6-diphenyl-1,3,5-triazine. After confirming the disappearance of -4,6-diphenyl-1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.94 g / yield 77.6%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.33 (82.23), Hydrogen: 4.10 (4.25)
Nitrogen: 7.33 (7.38), Fluorine: 3.29 (3.34)
As a result of mass spectrometry, m / z 570 [M] ⁺ and these data confirmed that the obtained compound was DBF (1) -HF-PhTRZ.

Example 66
2- {3- [3- (Dibenzothiophen-1-yl) phenyl] -4-fluorophenyl} -4,6-diphenyl-1,3,5-triazine [DBT (1) -HF-PhTRZ: Synthesis of (I) -326 Compound]
The starting materials in Example 11 were synthesized from 1.60 g (5.27 mmol) of 3- (dibenzothiophen-1-yl) phenylboronic acid of Synthesis Example 15 and 2- (3-bromo-4-fluorophenyl of Synthesis Example 3 ) -4,6-diphenyl-1,3,5-triazine The reaction was carried out in the same manner except that it was changed to 1.78 g (4.39 mmol), and then 2- (3-bromo-4-fluorophenyl) was obtained. ) -4,6-diphenyl-1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.02 g / yield 78.9%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 79.83 (79.98), Hydrogen: 4.17 (4.13)
Nitrogen: 7.30 (7.17), Sulfur: 5.40 (5.47)
Fluorine: 3.30 (3.24)
As a result of mass spectrometry, m / z 586 [M] ⁺ and these data confirmed that the obtained compound was DBT (1) -HF-PhTRZ.

Example 67
2- {3- [3- (Dibenzofuran-1-yl) phenyl] phenyl} -4,6-di (p-tolyl) -1,3,5-triazine [DBF (1) -H-H-DiMeTRZ: Synthesis of (I) -8 Compound]
The starting materials in Example 11 are 1.51 g (5.27 mmol) of 3- (dibenzofuran-1-yl) phenylboronic acid of Synthesis Example 14 and 2- (3-bromophenyl) -4,6 of Synthesis Example 4. -After reacting in exactly the same manner except for changing to 1.82 g (4.39 mmol) of di (p-tolyl) -1,3,5-triazine, 2- (3-bromophenyl) -4, After confirming disappearance of 6-di (p-tolyl) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.99 g / yield 78.5%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 85.04 (84.95), Hydrogen: 4.99 (5.04)
Nitrogen: 7.34 (7.25)
As a result of mass spectrometry, m / z 579 [M] ⁺ and these data confirmed that the obtained compound was DBF (1) -H—H—DiMeTRZ.

Example 68
2- {3- [3- (Dibenzothiophen-1-yl) phenyl] phenyl} -4,6-di (p-tolyl) -1,3,5-triazine [DBT (1) -HH-DiMeTRZ : Compound of (I) -181]
The starting materials in Example 11 were synthesized from 1.60 g (5.27 mmol) of 3- (dibenzothiophen-1-yl) phenylboronic acid of Synthesis Example 15 and 2- (3-bromophenyl) -4, Synthesis Example 4. After reacting in exactly the same manner except that the amount was changed to 1.82 g (4.39 mmol) of 6-di (p-tolyl) -1,3,5-triazine, 2- (3-bromophenyl) -4 The disappearance of, 6-di (p-tolyl) -1,3,5-triazine was confirmed and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.17 g / yield 83.3%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.78 (82.66), Hydrogen: 5.02 (4.91)
Nitrogen: 7.16 (7.05), Sulfur: 5.04 (5.38)
The result of mass spectrometry was m / z 596 [M] ⁺ , and from this data, it was confirmed that the obtained compound was DBT (1) -HH-DiMeTRZ.

Example 69
2- {3- [3- (Dibenzofuran-1-yl) phenyl] phenyl} -4,6-di (p-fluorophenyl) -1,3,5-triazine [DBF (1) -HH-DiFTRZ : Compound of (I) -153]
The starting materials in Example 11 are 1.51 g (5.27 mmol) of 3- (dibenzofuran-1-yl) phenylboronic acid of Synthesis Example 14 and 2- (3-bromophenyl) -4,6 of Synthesis Example 5. -After reacting in exactly the same manner except that it was changed to 1.78 g (4.39 mmol) of di (p-fluorophenyl) -1,3,5-triazine, 2- (3-bromophenyl) -4 After confirming disappearance of 1,6-di (p-fluorophenyl) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.99 g / yield 77.1%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 79.83 (79.71), Hydrogen: 4.09 (3.95)
Nitrogen: 7.22 (7.15), Fluorine: 6.44 (6.47)
As a result of mass spectrometry, m / z 588 [M] ⁺ and from these data, it was confirmed that the obtained compound was DBF (1) -HH-DiFTRZ.

Example 70
2- {3- [3- (Dibenzothiophen-1-yl) phenyl] phenyl} -4,6-di (p-fluorophenyl) -1,3,5-triazine [DBT (1) -HH- DiFTRZ: Compound of (I) -329]
The starting materials in Example 11 were synthesized from 1.60 g (5.27 mmol) of 3- (dibenzothiophen-1-yl) phenylboronic acid of Synthesis Example 15 and 2- (3-bromophenyl) -4, Synthesis Example 5. After reacting in exactly the same manner except that it was changed to 1.78 g (4.39 mmol) of 6-di (p-fluorophenyl) -1,3,5-triazine, 2- (3-bromophenyl)- The disappearance of 4,6-di (p-fluorophenyl) -1,3,5-triazine was confirmed, and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.07 g / yield 78.2%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 77.63 (77.59), Hydrogen: 3.92 (3.84)
Nitrogen: 6.84 (6.96), Sulfur: 5.27 (5.31)
Fluorine: 6.34 (6.29)
The result of mass spectrometry was m / z 603 [M] ⁺ , and from this data, it was confirmed that the obtained compound was DBT (1) -H—H-DiFTRZ.

Example 71
2- {3- [3- (Dibenzofuran-1-yl) phenyl] phenyl} -4,6-di (1-naphthyl) -1,3,5-triazine [DBF (1) -H-H-DiNapTRZ: (II) -1 Compound]
The starting materials in Example 11 are 1.51 g (5.27 mmol) of 3- (dibenzofuran-1-yl) phenylboronic acid of Synthesis Example 14 and 2- (3-bromophenyl) -4,6 of Synthesis Example 6. -After reacting in exactly the same manner except for changing to 2.13 g (4.39 mmol) of di (1-naphthyl) -1,3,5-triazine, 2- (3-bromophenyl) -4, After confirming the disappearance of 6-di (1-naphthyl) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.24 g / yield 78.4%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 86.54 (86.61), Hydrogen: 4.35 (4.48)
Nitrogen: 6.33 (6.45)
As a result of mass spectrometry, m / z 651 [M] ⁺ and these data confirmed that the obtained compound was DBF (1) -H—H-DiNapTRZ.

Example 72
2- {3- [3- (dibenzothiophen-1-yl) phenyl] phenyl} -4,6-di (1-naphthyl) -1,3,5-triazine [DBT (1) -HH-DiNapTRZ : Compound of (II) -123]
The starting materials in Example 11 were synthesized from 1.60 g (5.27 mmol) of 3- (dibenzothiophen-1-yl) phenylboronic acid in Synthesis Example 15 and 2- (3-bromophenyl) -4, After reacting in exactly the same manner except that the amount was changed to 2.13 g (4.39 mmol) of 6-di (1-naphthyl) -1,3,5-triazine, 2- (3-bromophenyl) -4 After confirming disappearance of 1,6-di (1-naphthyl) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 1.90 g / yield 64.8%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 84.44 (84.53), Hydrogen: 4.31 (4.38)
Nitrogen: 6.19 (6.29), Sulfur: 5.06 (4.80)
As a result of mass spectrometry, m / z 668 [M] ⁺ was used, and from this data, it was confirmed that the obtained compound was DBT (1) -HH-DiNapTRZ.

Example 73
2- {3- [3- (Dibenzofuran-1-yl) phenyl] phenyl} -4,6-di (9-phenanthro) -1,3,5-triazine [DBF (1) -HH-DiPhenTRZ: (VIII) -1 Compound]
The starting materials in Example 11 are 1.51 g (5.27 mmol) of 3- (dibenzofuran-1-yl) phenylboronic acid of Synthesis Example 14 and 2- (3-bromophenyl) -4,6 of Synthesis Example 7. -After reacting in exactly the same manner except that it was changed to 2.58 g (4.39 mmol) of di (9-phenanthro) -1,3,5-triazine, 2- (3-bromophenyl) -4, After confirming the disappearance of 6-di (9-phenanthro) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.14 g / yield 65.1%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 87.98 (87.86), Hydrogen: 4.47 (4.42)
Nitrogen: 5.52 (5.59)
As a result of mass spectrometry, m / z 752 [M] ⁺ and these data confirmed that the obtained compound was DBF (1) -HH-DiPhenTRZ.

Example 74
2- {3- [3- (Dibenzothiophen-1-yl) phenyl] phenyl} -4,6-di (9-phenanthro) -1,3,5-triazine [DBT (1) -HH-DiPhenTRZ : Compound of (VIII) -595]
The starting materials in Example 11 were synthesized from 1.60 g (5.27 mmol) of 3- (dibenzothiophen-1-yl) phenylboronic acid of Synthesis Example 15 and 2- (3-bromophenyl) -4, After reacting in exactly the same manner except that the amount was changed to 2.58 g (4.39 mmol) of 6-di (9-phenanthro) -1,3,5-triazine, 2- (3-bromophenyl) -4 The disappearance of, 6-di (9-phenanthro) -1,3,5-triazine was confirmed and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.04 g / yield 60.6%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 86.14 (86.02), Hydrogen: 4.27 (4.33)
Nitrogen: 5.58 (5.47), Sulfur: 4.01 (4.18)
The result of mass spectrometry was m / z 768 [M] ⁺ , and from this data, it was confirmed that the obtained compound was DBT (1) -HH-DiPhenTRZ.

Example 75
2- {3- [3- (7-methyldibenzofuran-4-yl) phenyl] -4-methylphenyl} -4,6-diphenyl-1,3,5-triazine [(7) MeDBF (4) -H -Me-PhTRZ: Compound of (I) -1145]
The starting materials in Synthesis Example 11 were mixed with 1.58 g (5.26 mmol) of 3- (7-methyldibenzofuran-4-yl) phenylboronic acid of Synthesis Example 16 and 2- (3-bromo-4- of Synthesis Example 2). Methylphenyl) -4,6-diphenyl-1,3,5-triazine was reacted in the same manner except that it was changed to 1.76 g (4.39 mmol), and then 2- (3-bromo-4- After confirming disappearance of (methylphenyl) -4,6-diphenyl-1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.09 g / yield 82.3%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 84.89 (84.95), Hydrogen: 5.09 (5.04)
Nitrogen: 7.26 (7.25)
As a result of mass spectrometry, m / z 579 [M] ⁺ and these data confirmed that the obtained compound was (7) MeDBF (4) -H-Me-PhTRZ.

Example 76
2- {3- [3- (7-methyldibenzothiophen-4-yl) phenyl] -4-methylphenyl} -4,6-diphenyl-1,3,5-triazine [(7) MeDBT (4)- H-Me-PhTRZ: Compound of (I) -1321]
The starting materials in Synthesis Example 11 were combined with 1.60 g (5.27 mmol) of 3- (7-methyldibenzothiophen-4-yl) phenylboronic acid of Synthesis Example 17 and 2- (3-bromo-4 of Synthesis Example 2). -Methylphenyl) -4,6-diphenyl-1,3,5-triazine was reacted in exactly the same manner except that it was changed to 1.76 g (4.39 mmol), and then 2- (3-bromo-4 -Methylphenyl) -4,6-diphenyl-1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.18 g / yield 83.5%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.58 (82.66), Hydrogen: 4.87 (4.91)
Nitrogen: 6.98 (7.05), Sulfur: 5.57 (5.38)
As a result of mass spectrometry, m / z 596 [M] ⁺ and these data confirmed that the obtained compound was (7) MeDBT (4) -H-Me-PhTRZ.

Example 77
2- {3- [3- (7-fluorodibenzofuran-4-yl) phenyl] -4-methylphenyl} -4,6-diphenyl-1,3,5-triazine [(7) FDBF (4) -H -Me-PhTRZ: Compound not in Table]
The starting materials in Synthesis Example 11 were prepared by using 1.61 g (5.26 mmol) of 3- (7-fluorodibenzofuran-4-yl) phenylboronic acid of Synthesis Example 18 and 2- (3-bromo-4- of Synthesis Example 2). Methylphenyl) -4,6-diphenyl-1,3,5-triazine was reacted in the same manner except that it was changed to 1.76 g (4.39 mmol), and then 2- (3-bromo-4- After confirming disappearance of (methylphenyl) -4,6-diphenyl-1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.12 g / yield 82.9%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.31 (82.31), Hydrogen: 4.36 (4.49)
Nitrogen: 7.33 (7.20), Fluorine: 3.20 (3.26)
As a result of mass spectrometry, m / z 583 [M] ⁺ and these data confirmed that the obtained compound was (7) FDBF (4) -H-Me-PhTRZ.

Example 78
2- {3- [3- (7-fluorodibenzothiophen-4-yl) phenyl] -4-methylphenyl} -4,6-diphenyl-1,3,5-triazine [(7) FDBT (4)- H-Me-PhTRZ: Compound not listed in the table]
The starting materials in Synthesis Example 11 were combined with 1.69 g (5.27 mmol) of 3- (7-fluorodibenzothiophen-4-yl) phenylboronic acid of Synthesis Example 19 and 2- (3-bromo-4 of Synthesis Example 2). -Methylphenyl) -4,6-diphenyl-1,3,5-triazine was reacted in exactly the same manner except that it was changed to 1.76 g (4.39 mmol), and then 2- (3-bromo-4 -Methylphenyl) -4,6-diphenyl-1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.14 g / yield 81.4%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 79.95 (80.11), Hydrogen: 4.30 (4.37)
Nitrogen: 7.03 (7.01), Sulfur: 5.31 (5.35)
Fluorine: 3.41 (3.17)
As a result of mass spectrometry, m / z 599 [M] ⁺ and these data confirmed that the obtained compound was (7) FDBT (4) -H-Me-PhTRZ.

Reference Example 79
2- {3- [3- (7-phenyldibenzofuran-4-yl) phenyl] -4-methylphenyl} -4,6-diphenyl-1,3,5-triazine [(7) PhDBF (4) -H -Me-PhTRZ: (I) -2065 Compound]
The starting materials in Synthesis Example 11 were prepared by using 1.91 g (5.26 mmol) of 3- (7-phenyldibenzofuran-4-yl) phenylboronic acid of Synthesis Example 20 and 2- (3-bromo-4- of Synthesis Example 2). Methylphenyl) -4,6-diphenyl-1,3,5-triazine was reacted in the same manner except that it was changed to 1.76 g (4.39 mmol), and then 2- (3-bromo-4- After confirming disappearance of (methylphenyl) -4,6-diphenyl-1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.23 g / yield 79.5%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 86.11 (86.09), Hydrogen: 4.85 (4.87)
Nitrogen: 6.61 (6.55)
As a result of mass spectrometry, m / z 640 [M] ⁺ and from these data, it was confirmed that the obtained compound was (7) PhDBF (4) -H-Me-PhTRZ.

Reference Example 80
2- {3- [3- (7-phenyldibenzothiophen-4-yl) phenyl] -4-methylphenyl} -4,6-diphenyl-1,3,5-triazine [(7) PhDBT (4)- H-Me-PhTRZ: Compound of (I) -2147]
The starting materials in Synthesis Example 11 were synthesized from 2.00 g (5.27 mmol) of 3- (7-phenyldibenzothiophen-4-yl) phenylboronic acid of Synthesis Example 21 and 2- (3-bromo-4 of Synthesis Example 2). -Methylphenyl) -4,6-diphenyl-1,3,5-triazine was reacted in exactly the same manner except that it was changed to 1.76 g (4.39 mmol), and then 2- (3-bromo-4 -Methylphenyl) -4,6-diphenyl-1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.33 g / yield 81.1%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 83.96 (83.99), Hydrogen: 4.71 (4.75)
Nitrogen: 6.35 (6.39), Sulfur: 4.98 (4.87)
As a result of mass spectrometry, m / z 657 [M] ⁺ and these data confirmed that the obtained compound was (7) PhDBT (4) -H-Me-PhTRZ.

Example 81
2- {3- [3- (7-Methyldibenzofuran-4-yl) phenyl] -4-fluorophenyl} -4,6-diphenyl-1,3,5-triazine [(7) MeDBF (4) -H -F-PhTRZ: Compound not in Table]
The starting material in Example 11 was prepared by using 1.58 g (5.26 mmol) of 3- (7-methyldibenzofuran-4-yl) phenylboronic acid of Synthesis Example 16 and 2- (3-bromo-4- of Synthesis Example 3). Fluorophenyl) -4,6-diphenyl-1,3,5-triazine was reacted in exactly the same manner except that it was changed to 1.78 g (4.39 mmol), and then 2- (3-bromo-4- The disappearance of (fluorophenyl) -4,6-diphenyl-1,3,5-triazine was confirmed, and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.10 g / yield 82.4%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.29 (82.31), Hydrogen: 4.52 (4.49)
Nitrogen: 7.26 (7.20), Fluorine: 3.19 (3.26)
As a result of mass spectrometry, m / z 583 [M] ⁺ and from these data, it was confirmed that the obtained compound was (7) MeDBF (4) -HF-PhTRZ.

Example 82
2- {3- [3- (7-Methyldibenzothiophen-4-yl) phenyl] -4-fluorophenyl} -4,6-diphenyl-1,3,5-triazine [(7) MeDBT (4)- H-F-PhTRZ: Compound not in Table]
The starting materials in Example 11 were synthesized from 1.60 g (5.27 mmol) of 3- (7-methyldibenzothiophen-4-yl) phenylboronic acid of Synthesis Example 17 and 2- (3-bromo-4 of Synthesis Example 3). -Fluorophenyl) -4,6-diphenyl-1,3,5-triazine was reacted in exactly the same manner except that it was changed to 1.78 g (4.39 mmol), and then 2- (3-bromo-4 -Fluorophenyl) -4,6-diphenyl-1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.21 g / yield 84.2%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 80.08 (80.11), Hydrogen: 4.30 (4.37)
Nitrogen: 6.98 (7.01), Sulfur: 5.37 (5.35)
Fluorine: 3.27 (3.17)
As a result of mass spectrometry, m / z 599 [M] ⁺ and these data confirmed that the obtained compound was (7) MeDBT (4) -HF-PhTRZ.

Example 83
2- {3- [3- (7-fluorodibenzofuran-4-yl) phenyl] -4-fluorophenyl} -4,6-diphenyl-1,3,5-triazine [(7) FDBF (4) -H -F-PhTRZ: (I) -1218 Compound]
The starting material in Example 11 was prepared by using 1.61 g (5.26 mmol) of 3- (7-fluorodibenzofuran-4-yl) phenylboronic acid of Synthesis Example 18 and 2- (3-bromo-4- of Synthesis Example 3). Fluorophenyl) -4,6-diphenyl-1,3,5-triazine was reacted in exactly the same manner except that it was changed to 1.78 g (4.39 mmol), and then 2- (3-bromo-4- The disappearance of (fluorophenyl) -4,6-diphenyl-1,3,5-triazine was confirmed, and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.16 g / yield 84.1%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 79.74 (79.71), Hydrogen: 3.91 (3.95)
Nitrogen: 7.11 (7.15), Fluorine: 6.54 (6.47)
As a result of mass spectrometry, m / z 587 [M] ⁺ and these data confirmed that the obtained compound was (7) FDBF (4) -HF-PhTRZ.

Example 84
2- {3- [3- (7-fluorodibenzothiophen-4-yl) phenyl] -4-fluorophenyl} -4,6-diphenyl-1,3,5-triazine [(7) FDBT (4)- Of HF-PhTRZ: (I) -1394 Compound]
The starting materials in Example 11 were synthesized from 1.69 g (5.26 mmol) of 3- (7-fluorodibenzothiophen-4-yl) phenylboronic acid of Synthesis Example 19 and 2- (3-bromo-4 of Synthesis Example 3). -Fluorophenyl) -4,6-diphenyl-1,3,5-triazine was reacted in exactly the same manner except that it was changed to 1.78 g (4.39 mmol), and then 2- (3-bromo-4 -Fluorophenyl) -4,6-diphenyl-1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.15 g / yield 82.0%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 80.13 (80.11), Hydrogen: 4.41 (4.37)
Nitrogen: 6.95 (7.01), Sulfur: 5.33 (5.35)
Fluorine: 3.18 (3.17)
As a result of mass spectrometry, m / z 599 [M] ⁺ and these data confirmed that the obtained compound was (7) FDBT (4) -HF-PhTRZ.

Reference Example 85
2- {3- [3- (7-phenyldibenzofuran-4-yl) phenyl] -4-fluorophenyl} -4,6-diphenyl-1,3,5-triazine [(7) PhDBF (4) -H -F-PhTRZ: (I) -2100 Compound]
The starting material in Example 11 was prepared by using 1.91 g (5.26 mmol) of 3- (7-phenyldibenzofuran-4-yl) phenylboronic acid of Synthesis Example 20 and 2- (3-bromo-4- of Synthesis Example 3). Fluorophenyl) -4,6-diphenyl-1,3,5-triazine was reacted in exactly the same manner except that it was changed to 1.78 g (4.39 mmol), and then 2- (3-bromo-4- The disappearance of (fluorophenyl) -4,6-diphenyl-1,3,5-triazine was confirmed, and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.17 g / yield 76.9%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 83.73 (83.70), Hydrogen: 4.29 (4.37)
Nitrogen: 6.56 (6.51), Fluorine: 2.95 (2.94)
The result of mass spectrometry was m / z 645 [M] ⁺ , and from these data, it was confirmed that the obtained compound was (7) PhDBF (4) -HF-PhTRZ.

Reference Example 86
2- {3- [3- (7-phenyldibenzothiophen-4-yl) phenyl] -4-fluorophenyl} -4,6-diphenyl-1,3,5-triazine [(7) PhDBT (4)- Of HF-PhTRZ: (I) -2224 Compound]
The starting materials in Example 11 were synthesized from 2.00 g (5.27 mmol) of 3- (7-phenyldibenzothiophen-4-yl) phenylboronic acid of Synthesis Example 21 and 2- (3-bromo-4 of Synthesis Example 3). -Fluorophenyl) -4,6-diphenyl-1,3,5-triazine was reacted in exactly the same manner except that it was changed to 1.78 g (4.39 mmol), and then 2- (3-bromo-4 -Fluorophenyl) -4,6-diphenyl-1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.39 g / yield 82.6%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 81.61 (81.67), Hydrogen: 4.31 (4.26)
Nitrogen: 6.25 (6.35), Sulfur: 4.79 (4.85)
Fluorine: 3.04 (2.87)
As a result of mass spectrometry, m / z 660 [M] ⁺ and these data confirmed that the obtained compound was (7) PhDBT (4) -HF-PhTRZ.

Example 87
2- {3- [3- (7-Methyldibenzofuran-4-yl) phenyl] -phenyl} -4,6-di (p-tolyl) -1,3,5-triazine [(7) MeDBF (4) -HH-DiMeTRZ: Compound of (I) -1148]
The starting materials in Example 11 were synthesized from 1.58 g (5.26 mmol) of 3- (7-methyldibenzofuran-4-yl) phenylboronic acid of Synthesis Example 16 and 2- (3-bromophenyl)-of Synthesis Example 4 After reacting in exactly the same manner except that the amount was changed to 1.82 g (4.39 mmol) of 4,6-di (p-tolyl) -1,3,5-triazine, 2- (3-bromophenyl) After confirming disappearance of -4,6-di (p-tolyl) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.10 g / yield 80.8%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 85.03 (84.96), Hydrogen: 5.22 (5.26)
Nitrogen: 7.12 (7.08)
As a result of mass spectrometry, m / z 593 [M] ⁺ and these data confirmed that the obtained compound was (7) MeDBF (4) -HH-DiMeTRZ.

Example 88
2- {3- [3- (7-methyldibenzothiophen-4-yl) phenyl] -phenyl} -4,6-di (p-tolyl) -1,3,5-triazine [(7) MeDBT (4 ) -HH-DiMeTRZ: Compound of (I) -1324]
The starting materials in Example 11 are 1.60 g (5.26 mmol) of 3- (7-methyldibenzothiophen-4-yl) phenylboronic acid of Synthesis Example 17 and 2- (3-bromophenyl) of Synthesis Example 4 After reacting in exactly the same manner except that it was changed to 1.82 g (4.39 mmol) of -4,6-di (p-tolyl) -1,3,5-triazine, 2- (3-bromophenyl) ) -4,6-di (p-tolyl) -1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.25 g / yield 84.5%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.77 (82.73), Hydrogen: 5.08 (5.12)
Nitrogen: 6.88 (6.89), Sulfur: 5.27 (5.26)
As a result of mass spectrometry, m / z 609 [M] ⁺ was used, and from these data, it was confirmed that the obtained compound was (7) MeDBT (4) -HH-DiMeTRZ.

Example 89
2- {3- [3- (7-fluorodibenzofuran-4-yl) phenyl] phenyl} -4,6-di (p-tolyl) -1,3,5-triazine [(7) FDBF (4)- H-H-DiMeTRZ: Compound not in the table]
The starting materials in Example 11 were synthesized from 1.61 g (5.26 mmol) of 3- (7-fluorodibenzofuran-4-yl) phenylboronic acid of Synthesis Example 18 and 2- (3-bromophenyl)-of Synthesis Example 4 After reacting in exactly the same manner except that the amount was changed to 1.82 g (4.39 mmol) of 4,6-di (p-tolyl) -1,3,5-triazine, 2- (3-bromophenyl) After confirming disappearance of -4,6-di (p-tolyl) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.22 g / yield 85.3%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 82.35 (82.39), Hydrogen: 4.68 (4.72)
Nitrogen: 7.10 (7.03), Fluorine: 3.16 (3.18)
As a result of mass spectrometry, m / z 597 [M] ⁺ and these data confirmed that the obtained compound was (7) FDBF (4) -HH-DiMeTRZ.

Example 90
2- {3- [3- (7-fluorodibenzothiophen-4-yl) phenyl] phenyl} -4,6-di (p-tolyl) -1,3,5-triazine [(7) FDBT (4) -HH-DiMePhTRZ: Compound not in Table]
The starting materials in Example 11 are 1.69 g (5.26 mmol) of 3- (7-fluorodibenzothiophen-4-yl) phenylboronic acid of Synthesis Example 19 and 2- (3-bromophenyl) of Synthesis Example 4 After reacting in exactly the same manner except that it was changed to 1.82 g (4.39 mmol) of -4,6-di (p-tolyl) -1,3,5-triazine, 2- (3-bromophenyl) ) -4,6-di (p-tolyl) -1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.29 g / yield 85.3%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 80.20 (80.24), Hydrogen: 4.68 (4.60)
Nitrogen: 6.88 (6.85), Sulfur: 5.14 (5.22)
Fluorine: 3.10 (3.10)
As a result of mass spectrometry, m / z 613 [M] ⁺ and from these data, it was confirmed that the obtained compound was (7) FDBT (4) -H—H—DiMeTRZ.

Reference Example 91
2- {3- [3- (7-phenyldibenzofuran-4-yl) phenyl] phenyl} -4,6-di (p-tolyl) -1,3,5-triazine [(7) PhDBF (4)- H-H-DiMeTRZ: (I) -2068 Compound]
The starting materials in Example 11 were prepared from 1.91 g (5.26 mmol) of 3- (7-phenyldibenzofuran-4-yl) phenylboronic acid of Synthesis Example 20 and 2- (3-bromophenyl)-of Synthesis Example 4 After reacting in exactly the same manner except that the amount was changed to 1.82 g (4.39 mmol) of 4,6-di (p-tolyl) -1,3,5-triazine, 2- (3-bromophenyl) After confirming disappearance of -4,6-di (p-tolyl) -1,3,5-triazine, the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.26 g / yield 78.8%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 86.12 (86.08), Hydrogen: 5.01 (5.07)
Nitrogen: 6.45 (6.41),
As a result of mass spectrometry, m / z 655 [M] ⁺ and these data confirmed that the obtained compound was (7) PhDBF (4) -H—H—DiMeTRZ.

Reference Example 92
2- {3- [3- (7-phenyldibenzothiophen-4-yl) phenyl] phenyl} -4,6-di (p-tolyl) -1,3,5-triazine [(7) PhDBT (4) -H-H-DiMeTRZ: (I) -2177 Compound]
The starting materials in Example 11 were 2.00 g (5.27 mmol) of 3- (7-phenyldibenzothiophen-4-yl) phenylboronic acid of Synthesis Example 21 and 2- (3-bromophenyl) of Synthesis Example 4 After reacting in exactly the same manner except that it was changed to 1.82 g (4.39 mmol) of -4,6-di (p-tolyl) -1,3,5-triazine, 2- (3-bromophenyl) ) -4,6-di (p-tolyl) -1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.22 g / yield 75.4%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 83.95 (84.02), Hydrogen: 5.01 (4.95)
Nitrogen: 6.45 (6.41), Sulfur: 4.59 (4.77)
As a result of mass spectrometry, m / z 671 [M] ⁺ and these data confirmed that the obtained compound was (7) PhDBF (4) -HH-DiMeTRZ.

Example 93
2- {3- [3- (7-methyldibenzofuran-4-yl) phenyl] phenyl} -4,6-di (p-fluorophenyl) -1,3,5-triazine [(7) MeDBF (4) -HH-DiFTRZ: Compound not in the table]
The starting materials in Example 11 were prepared by using 1.58 g (5.26 mmol) of 3- (7-methyldibenzofuran-4-yl) phenylboronic acid of Synthesis Example 16 and 2- (3-bromophenyl)-of Synthesis Example 5 After reacting in the same manner except that it was changed to 1.78 g (4.39 mmol) of 4,6-di (p-fluorophenyl) -1,3,5-triazine, 2- (3-bromophenyl) ) -4,6-di (p-fluorophenyl) -1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.03 g / yield 77.1%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 79.80 (79.85), Hydrogen: 4.20 (4.19)
Nitrogen: 6.95 (6.98), Fluorine: 6.25 (6.32)
As a result of mass spectrometry, m / z 600 [M] ⁺ and from these data, it was confirmed that the obtained compound was (7) MeDBF (4) -HH-DiFTRZ.

Example 94
2- {3- [3- (7-methyldibenzothiophen-4-yl) phenyl] phenyl} -4,6-di (p-fluorophenyl) -1,3,5-triazine [(7) MeDBT (4 ) -H-H-DiFTRZ: a compound not listed in the table]
The starting materials in Example 11 were synthesized from 1.60 g (5.26 mmol) of 3- (7-methyldibenzofuran-4-yl) phenylboronic acid of Synthesis Example 17 and 2- (3-bromophenyl)-of Synthesis Example 5. After reacting in the same manner except that it was changed to 1.78 g (4.39 mmol) of 4,6-di (p-fluorophenyl) -1,3,5-triazine, 2- (3-bromophenyl) ) -4,6-di (p-fluorophenyl) -1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.12 g / yield 78.4%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 77.70 (77.78), Hydrogen: 4.06 (4.08)
Nitrogen: 6.75 (6.80), Sulfur: 5.21 (5.19)
Fluorine: 6.28 (6.15)
The result of mass spectrometry was m / z 617 [M] ⁺ , and from these data, it was confirmed that the obtained compound was (7) MeDBT (4) -H—H—DiFTRZ.

Example 95
2- {3- [3- (7-fluorodibenzofuran-4-yl) phenyl] phenyl} -4,6-di (p-fluorophenyl) -1,3,5-triazine [(7) FDBF (4) -HH-DiFTRZ: (I) -1221 Compound]
The starting material in Example 11 was prepared by using 1.61 g (5.26 mmol) of 3- (7-fluorodibenzofuran-4-yl) phenylboronic acid of Synthesis Example 18 and 2- (3-bromophenyl)-of Synthesis Example 5 After reacting in the same manner except that it was changed to 1.78 g (4.39 mmol) of 4,6-di (p-fluorophenyl) -1,3,5-triazine, 2- (3-bromophenyl) ) -4,6-di (p-fluorophenyl) -1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.14 g / yield 80.4%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 77.35 (77.35), Hydrogen: 3.68 (3.66)
Nitrogen: 7.00 (6.94), Fluorine: 9.45 (9.41)
As a result of mass spectrometry, m / z 605 [M] ⁺ and these data confirmed that the obtained compound was (7) FDBF (4) -HH-DiFTRZ.

Example 96
2- {3- [3- (7-fluorodibenzothiophen-4-yl) phenyl] phenyl} -4,6-di (p-fluorophenyl) -1,3,5-triazine [(7) FDBT (4 ) -HH-DiFTRZ: (I) -1397 Compound]
The starting materials in Example 11 are 1.69 g (5.26 mmol) of 3- (7-fluorodibenzothiophen-4-yl) phenylboronic acid of Synthesis Example 19 and 2- (3-bromophenyl) of Synthesis Example 5. After reacting in the same manner except that it was changed to 1.78 g (4.39 mmol) of -4,6-di (p-fluorophenyl) -1,3,5-triazine, 2- (3-bromo The disappearance of (phenyl) -4,6-di (p-fluorophenyl) -1,3,5-triazine was confirmed, and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 11 to obtain a white solid (yield 2.18 g / yield 79.8%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 75.22 (75.35), Hydrogen: 3.55 (3.57)
Nitrogen: 6.88 (6.76), Sulfur: 5.14 (5.16)
Fluorine: 9.21 (9.17)
As a result of mass spectrometry, m / z 621 [M] ⁺ was used, and from these data, it was confirmed that the obtained compound was (7) FDBT (4) -HH-DiFTRZ.

Reference Example 97
2- {3- [3- (7-phenyldibenzofuran-4-yl) phenyl] phenyl} -4,6-di (p-fluorophenyl) -1,3,5-triazine [(7) PhDBF (4) -H-H-DiFTRZ: (I) -2124 Compound]
The starting materials in Example 11 were prepared from 1.91 g (5.26 mmol) of 3- (7-phenyldibenzofuran-4-yl) phenylboronic acid of Synthesis Example 20 and 2- (3-bromophenyl)-of Synthesis Example 5 After reacting in the same manner except that it was changed to 1.78 g (4.39 mmol) of 4,6-di (p-fluorophenyl) -1,3,5-triazine, 2- (3-bromophenyl) ) -4,6-di (p-fluorophenyl) -1,3,5-triazine disappeared and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.26 g / yield 77.5%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 81.38 (81.43), Hydrogen: 4.15 (4.10)
Nitrogen: 6.40 (6.33), Fluorine: 5.69 (5.72)
As a result of mass spectrometry, m / z 663 [M] ⁺ and from these data, it was confirmed that the obtained compound was (7) PhDBF (4) -HH-DiFTRZ.

Reference Example 98
2- {3- [3- (7-phenyldibenzothiophen-4-yl) phenyl] phenyl} -4,6-di (p-fluorophenyl) -1,3,5-triazine [(7) PhDBT (4 ) -HH-DiFTRZ: Compound of (I) -2217]
The starting materials in Example 11 are 2.00 g (5.26 mmol) of 3- (7-phenyldibenzothiophen-4-yl) phenylboronic acid of Synthesis Example 21 and 2- (3-bromophenyl) of Synthesis Example 5. After reacting in the same manner except that it was changed to 1.78 g (4.39 mmol) of -4,6-di (p-fluorophenyl) -1,3,5-triazine, 2- (3-bromo The disappearance of (phenyl) -4,6-di (p-fluorophenyl) -1,3,5-triazine was confirmed, and the reaction mixture was cooled to room temperature.
The obtained reaction mixture was treated in the same manner as in Example 21 to obtain a white solid (yield 2.36 g / yield 79.1%). Further, the white solid was purified by sublimation by a conventional method to obtain crystals. The results of elemental analysis of this crystal are as follows, and the numerical values in parentheses are theoretical values.
Carbon: 79.48 (79.51), Hydrogen: 4.05 (4.00)
Nitrogen: 6.21 (6.18), Sulfur: 4.57 (4.72)
Fluorine: 5.69 (5.59)
As a result of mass spectrometry, m / z 679 [M] ⁺ and these data confirmed that the obtained compound was (7) PhDBT (4) -HH-DiFTRZ.

1 Substrate 2 Anode (ITO)
DESCRIPTION OF SYMBOLS 3 Light emitting layer 4 Cathode 5 Hole (hole) transport layer 6 Electron transport layer 7 Hole (hole) injection layer 8 Electron injection layer 9 Hole block layer

Claims (2)

Illumination for plant cultivation using an organic electroluminescence element produced using a triazine compound represented by the following general formula [1] in which a triazine skeleton part and a dibenzofuran or dibenzothiophene skeleton part are linked via a biphenyl skeleton part.
[Wherein, X represents an oxygen atom or a sulfur atom, and R ¹ and R ³ , R ⁴ each independently represents a group consisting of hydrogen, fluorine, and a linear or branched alkyl group having 1 to 6 carbon atoms. Represents a selected group, R ² represents hydrogen, fluorine, or a linear or branched alkyl group having 1 to 6 carbon atoms; Ar represents a phenyl group represented by the following formulas (I) to (VIII); Represents a group selected from the group consisting of 1-naphthyl group, 2-naphthyl group, 1-phenanthrenyl group, 2-phenanthrenyl group, 3-phenanthrenyl group, 4-phenanthrenyl group and 9-phenanthrenyl group, and R ^{10 to} R ^73. Represents a group independently selected from the group consisting of hydrogen, fluorine, and a linear or branched alkyl group having 1 to 6 carbon atoms. ]
The lighting for plant cultivation according to claim 1, wherein the triazine compound is a triazine compound represented by the following general formula [2] in which a triazine skeleton portion and a dibenzofuran or dibenzothiophene skeleton portion are connected via a biphenyl skeleton portion.
[Wherein, X represents an oxygen atom or a sulfur atom, and R ¹ and R ³ , R ⁴ each independently represents a group consisting of hydrogen, fluorine, and a linear or branched alkyl group having 1 to 6 carbon atoms. Represents a selected group, R ² represents hydrogen, fluorine, or a linear or branched alkyl group having 1 to 6 carbon atoms; Ar represents a phenyl group represented by the following formulas (I) to (VIII); Represents a group selected from the group consisting of 1-naphthyl group, 2-naphthyl group, 1-phenanthrenyl group, 2-phenanthrenyl group, 3-phenanthrenyl group, 4-phenanthrenyl group and 9-phenanthrenyl group, and R ^{10 to} R ^73. Represents a group independently selected from the group consisting of hydrogen, fluorine, and a linear or branched alkyl group having 1 to 6 carbon atoms. ]