JP7456076B2 - Compound, method for producing compound, and organic light emitting device - Google Patents

Description

The present disclosure relates to a novel compound, a method for producing the compound, a blue light-emitting material, and an organic light-emitting device.

With the increasing demand for high efficiency, energy saving, and low environmental impact, devices using organic electroluminescence (hereinafter sometimes referred to as organic EL), which has many advantages over conventional inorganic light emitting materials, have attracted attention in recent years. As a result, even in general lighting, there is a shift from fluorescent lamps to white light emitting diodes (LEDs). This is due to the demand for switching from fluorescent lamps to white organic EL lighting as a substitute for mercury products.
It is important that the light-emitting materials used for the light-emitting layer of an organic EL light-emitting device, white LED lighting, etc. have a well-balanced combination of light-emitting materials that are the three primary colors of light: red light-emitting material, green light-emitting material, and blue light-emitting material. Especially in the case of white LED lighting, it is important that the luminescent materials of the three primary colors of light have a good balance, and if the balance of the fluorescent luminescent materials of the three primary colors of light is not good, it is difficult to obtain good white light. The problem is that it is difficult.

Of the three primary colors of light, many organic compounds are known to emit red and green light, which have relatively long wavelengths.
However, among light-emitting materials, compounds that emit blue light are limited. For example, materials that emit blue light in a solvent are known, but there are few materials that emit blue light in solid state, and Organic aromatic compounds that emit blue energy are not well known.
As a blue light-emitting material, a novel aromatic organic amine derivative that is useful for organic EL has been proposed (see Patent Document 1).
With the aim of obtaining blue light emission with good color purity, oligonaphthalene derivatives, which are compounds in which three or more naphthalene skeletons are bonded consecutively, and light-emitting devices using the same have been proposed, and are capable of emitting light at short wavelengths. is described (see Patent Document 2).
In addition, the present inventor previously synthesized a boron diketone complex useful as a blue solid-state luminescent material, and produced an OLED device (Organic Lighting Emitting Diode Device) using the boron diketone complex (Patent Document 3 and Non-Patent Document 3). (See Reference 1).

Chem. Asian J. 2017, Vol. 12, P2299-2303.

JP 2016-147855 A Japanese Patent Application Publication No. 2006-151966 Re-publication No. 2017-065219

With the blue light emitting material described in Patent Document 1, pale blue light emission with a relatively long wavelength of about 450 nm to 480 nm can be obtained. However, in order to obtain well-balanced white light, there is a need for a material that emits deep blue light with a maximum absorption wavelength in the relatively short wavelength range of 380 nm to 460 nm. The blue light-emitting material described in Document 1 still required improvement in terms of emission wavelength.
Cited Document 2 describes a compound in which three or four naphthalene skeletons are bonded consecutively, and although it has been confirmed that short wavelength light emission is possible, the synthesis route is complicated; There is a problem that the yield of the intermediate is low. Furthermore, although blue light emission has been confirmed, the luminous efficiency has not been evaluated.
The boron diketone complex compounds described in Patent Document 3 and Non-Patent Document 1 can emit deep blue light in solid state, have a molecular weight of 300 or more, and can form stable films by vacuum evaporation, so they are suitable for devices. It is suitable for manufacturing. However, there is still room for improvement in terms of producing efficient light-emitting materials, such as the availability of raw materials and the complexity of the synthesis route.

The problem to be solved by an embodiment of the present invention is to provide a new compound and a blue light-emitting material that can realize deep blue light emission with a maximum absorption wavelength of 380 nm to 460 nm and can be manufactured efficiently. It is.
The problem to be solved by other embodiments of the present invention is to develop a method for producing a compound that can easily obtain a compound capable of emitting deep blue light with a maximum absorption wavelength of 380 nm to 460 nm in high yield. It is to provide.
A problem to be solved by another embodiment of the present invention is to provide an organic light emitting device using a compound that emits deep blue light with a maximum absorption wavelength of 380 nm to 460 nm.

Means for solving the problem include the following aspects.

<1> A compound represented by the following formula (I).

In formula (I), n represents 0 or 1.
<2> The compound represented by the formula (I) is the compound according to <1>, which is a compound represented by the following formula (I-2).

<3> The compound according to <1> or <2>, having a molecular weight of 300 or more.
<4> A blue light-emitting material represented by the following formula (I):

In formula (I), n represents 0 or 1.
<5> 2,6-dibromonaphthalene (a1) or 2,6-dibromonaphthalene (a2) and 1-bromonaphthaleneboronic acid (b) are combined with potassium carbonate and tetra(triphenylphosphorus)palladium (0). The method for producing the compound according to <2>, comprising a step of reacting in the presence of the compound.

<6> An organic light emitting device comprising the compound according to any one of <1> to <3> or the blue light emitting material according to <4>.

According to one embodiment of the present invention, it is possible to provide a novel compound and a blue light-emitting material that can be efficiently produced and that can realize deep blue light emission with a maximum absorption wavelength of 380 nm to 460 nm.
According to another embodiment of the present invention, it is possible to provide a method for producing a compound that can easily obtain a compound capable of realizing deep blue light emission having a maximum absorption wavelength of 380 nm to 460 nm in high yield.
According to another embodiment of the present invention, it is possible to provide an organic light-emitting device using a compound that realizes deep blue light emission with a maximum absorption wavelength of 380 nm to 460 nm.

1 is a graph showing absorption spectra in chloroform solvent, emission spectra in chloroform solvent, and solid emission spectra of exemplary compounds 2611, 2612, 2711, and 2712 obtained in Examples 1 to 4. 1 is a ¹ H NMR spectrum of Exemplary Compound 2611 obtained in Example 1. 13 is a ¹³ C NMR spectrum of Exemplified Compound 2611 obtained in Example 1. 1 is a ¹ H NMR spectrum of 2-bromo-6-(1-naphthyl)naphthalene (26B1), which is an intermediate of Exemplified Compound 2612 obtained in Example 2. ^13C NMR spectrum of 2-bromo-6-(1-naphthyl)naphthalene (26B1), which is an intermediate of Exemplified Compound 2612 obtained in Example 2. 1 is a ¹ H NMR spectrum of Exemplified Compound 2612 obtained in Example 2. 13 is a ¹³ C NMR spectrum of Exemplary Compound 2612 obtained in Example 2. This is a ¹ H NMR spectrum of 2-bromo-7-(1-naphthyl)naphthalene (27B1), which is an intermediate of Exemplified Compound 2712, obtained together with Exemplified Compound 2711 in Example 3. This is a ¹³ C NMR spectrum of 2-bromo-7-(1-naphthyl)naphthalene (27B1), which is an intermediate of Exemplified Compound 2712, obtained together with Exemplified Compound 2711 in Example 3. 1 is a ¹ H NMR spectrum of Exemplified Compound 2711 obtained in Example 3. 1 is a ¹³ C NMR spectrum of the exemplary compound 2711 obtained in Example 3. 1 is a ¹ H NMR spectrum of Exemplified Compound 2712 obtained in Example 4. 1 is a ¹³ C NMR spectrum of the exemplary compound 2712 obtained in Example 4.

Hereinafter, the compound, the method for producing the compound, and the organic light-emitting device of the present disclosure will be described in detail.
In the present disclosure, a numerical range indicated using "~" means a range that includes the numerical values listed before and after "~" as the minimum and maximum values, respectively.
The term "solid content" in the present disclosure refers to components excluding the solvent, and liquid components such as low molecular weight components other than the solvent are also included in the "solid content" herein.
In the present disclosure, "solvent" means water, an organic solvent, and a mixed solvent of water and an organic solvent.
In this disclosure, the term "step" is used not only to refer to an independent process, but also to include a process that is not clearly distinguishable from other processes, as long as the intended purpose of the process is achieved. .
In the present disclosure, unless otherwise specified, the expression "substituent" is used to include unsubstituted groups and those that further have a substituent. For example, when expressed as "alkyl group", unsubstituted alkyl It is used in a meaning that includes both a group and an alkyl group further having a substituent. The same applies to other substituents.
In the numerical ranges described step by step in this disclosure, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step. Moreover, in the numerical ranges described in this disclosure, the upper limit or lower limit described in a certain numerical range may be replaced with the value shown in the Examples.
Furthermore, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.

≪Compound≫
The compound of the present disclosure is a compound represented by the following formula (I).
The compound represented by the following formula (I) is a compound with a novel structure, and is useful as a blue light-emitting material, as described below.

In the formula (I), n represents 0 or 1, and from the viewpoint of suitability for synthesis, n is preferably 0.
That is, the compound represented by formula (I) is preferably a compound represented by the following formula (I-2).

It is considered important that the bonding positions of the two naphthalenes in formula (I) and formula (I-2) have the partial structure shown below.

In the naphthalene skeleton of the above partial structure, the bonding position of the third naphthalene skeleton may be any of 1, 3, 4, 5, 6, 7, and 8, but depending on synthesis suitability and maximum absorption of the resulting compound. From the viewpoint of wavelength, the bonding position is preferably 5, 6, or 7, more preferably 6 or 7.

The compound of the present disclosure is a compound that can realize deep blue light emission with a maximum absorption wavelength of 380 nm to 460 nm, and is suitably used as a blue light emitting material.
The emission wavelength of the compound of the present disclosure in a solvent and in a solid state are both preferably in the range of 380 nm to 460 nm, more preferably in the range of 380 nm or more and less than 450 nm, and 390 nm to 430 nm. More preferably, the range is within the range of .

Naphthalene emits fluorescence with a quantum yield of 0.23 in organic solvents, but does not emit light in the solid state. The present inventors have discovered that by dimerizing naphthalene with carbon-carbon bonds, solid-state luminescence can be produced with high efficiency in a longer wavelength region than in a solution state. In the present disclosure, we aimed to produce a compound that has a molecular weight of 300 or more and has naphthalene as a luminescent atomic group (chromophore) and emits blue light. As a result, we focused on the dimer structure of the above structure from the bond position when naphthalene was dimerized with a carbon-carbon bond, and by introducing one or two more naphthalene skeletons into the dimer, We have found a compound that has a preferable maximum absorption wavelength in an organic solvent and in a solid state.

The maximum emission wavelength of a compound in a solvent can be measured using, for example, an absolute PL photon yield measuring device (C9920-02, manufactured by Hamamatsu Photonics Co., Ltd.).
In addition, the maximum emission wavelength of a compound in a solid state can be measured using a powdered material of a solid state luminescent material, for example, using an absolute PL photon yield measuring device (C9920-02, manufactured by Hamamatsu Photonics Co., Ltd.). It can be done using By using the absolute PL photon yield measurement device, more reliable maximum emission wavelength and fluorescence yield values can be obtained than with conventional relative measurement methods.

In addition, the luminescence lifetime and rate constant, which are one of the important physical properties when using a compound as a blue-emitting material, can be measured using a compact fluorescence lifetime measuring device (TAU, manufactured by Hamamatsu Photonics Co., Ltd.). It can be measured by photon counting. As described above, the sample to be measured is a powdered luminescent material. A pulsed LED lamp can be used as an excitation light source in the single photon measurement method.

Note that when the compound is used as a blue light-emitting material, for example, in producing an organic EL or the like, the light-emitting layer is often formed by a vacuum evaporation method. From the viewpoint of durability of the light emitting layer, the molecular weight of the compound of the present disclosure as a blue light emitting material is preferably 300 or more, more preferably 350 or more.

Exemplary compounds of the compounds of the present disclosure are listed below, but the present disclosure is not limited to the following exemplary compounds.
Examples of the compound represented by the above formula (I) and the compound represented by the formula (I-2) include the following exemplified compounds 2611, 2612, 2711, and 2712.
The following exemplified compounds are all compounds containing three naphthalene skeletons and have a molecular weight of 380.49.

Among the above exemplary compounds, exemplary compound 2612 and exemplary compound 2612 are preferable, and exemplary compound 2611 is more preferable, from the viewpoint of emission wavelength, stability, and ease of synthesis.
Therefore, the blue light-emitting material preferably contains the exemplified compound 2612 and the exemplified compound 2612, and more preferably contains the exemplified compound 2611.

Next, exemplary compounds that are represented by formula (1) but are not included in formula (I-2), i.e., compounds in which n in formula (I) is 1 and which have four naphthalene skeletons in the molecule, are listed below. Exemplary compounds having four naphthalene skeletons in the molecule include the following exemplary compounds 126261, 126262, 126271, 126272, 127271, 127272, etc.
The following exemplary compounds all contain four naphthalene skeletons and have a molecular weight of 506.65.

Each of the above-mentioned exemplified compounds represented by formula (I) has at least three naphthalene skeletons, so all have a molecular weight of 300 or more, and when used as a solid blue light-emitting material, they are suitable for forming a light-emitting layer with good durability. It is a compound that has the advantage that it can be formed.
Therefore, when the compound of the present disclosure is applied as a blue light-emitting material to an organic light-emitting device described below, etc., a solid-state thin film can be produced. When the resulting solid-state thin film is used as an electrode in, for example, electronic devices, it has good durability and can efficiently convert photons into wavelengths to emit blue light. be effective.

≪Method for producing compound≫
The compound represented by formula (I) can be synthesized using readily available compounds as raw materials. There are no particular limitations on the method for producing the compound of the present disclosure, and the compound can be obtained by any known production method.
Among these, from the viewpoint of better yield, it is preferable to produce by the production method of the present disclosure below, which applies "Suzuki coupling".
The method for producing the compound of the present disclosure includes combining 2,6-dibromonaphthalene (a1) or 2,7-dibromonaphthalene (a2) and 1-bromonaphthaleneboronic acid (b) with potassium carbonate [K ₂ CO ₃ ]. and tetra(triphenylphosphorus)palladium(0) [Pd(PPh ₃ ) ₄ ]. Here, Ph represents a phenyl group.

A synthetic scheme for Exemplified Compound 2611, which is an example of the production method of the present disclosure, is shown below. Note that details of the method for producing the compound will be explained in Examples by giving synthetic examples.

According to the method for producing a compound of the present disclosure, easily available dibromonaphthalene, such as 2,6-dibromonaphthalene (a1) or 2,7-dibromonaphthalene (a2), and 1-bromonaphthaleneboronic acid are used as starting materials. (b) can be used to synthesize the compounds of the present disclosure. Specifically, for example, the desired exemplary compound 2611 can be obtained through a one-step reaction as shown in the above scheme.
Furthermore, in the above scheme, by controlling either the reaction temperature or reaction time, it is possible to obtain 26B1, which is an intermediate for synthesizing exemplified compound 2611 and exemplified compound 2612, as shown in the synthesis scheme below. can.
Thereafter, by further reacting intermediate 26B1 with 2-bromonaphthaleneboronic acid (b2), exemplified compound 2612 can be obtained in high yield through a two-step reaction process using the same solvent, catalyst, etc. .

Next, a synthesis scheme of a compound having four naphthalene skeletons will be explained. The following synthesis of a compound having four naphthalene skeletons can also be performed in the same manner as the synthesis of a compound having three naphthalene skeletons by applying "Suzuki coupling."

First, an intermediate NNB1 having two naphthalene skeletons is obtained using dibromonaphthalene (a) such as 2,6-dibromonaphthalene or 2,7-dibromonaphthalene and 1-bromonaphthaleneboronic acid (b). The above reaction is carried out in the presence of potassium carbonate [K ₂ CO ₃ ] and tetra(triphenylphosphorus)palladium(0) [Pd(PPh ₃ ) ₄ ], similar to the synthesis of compounds having three naphthalene skeletons. It is.

Next, dibromonaphthalene (a) and bromonaphthaleneboronic acid (b3), such as 1-bromonaphthaleneboronic acid or 2-bromonaphthaleneboronic acid, are used to obtain intermediate NNB2, which has two naphthalene skeletons.

Next, the intermediate NNB2 obtained above was added in the presence of n-butyllithium [n-BuLi] and triisopropyl borate [B(OiPr) ₃ ] in a tetrahydrofuran (THF) solvent at -78°C. An intermediate NNB3 in which -B(OH) ₂ is introduced into a compound having two naphthalene skeletons can be obtained by the reaction.

Furthermore, the intermediate NNB1 and NNB3 obtained above are reacted in the presence of potassium carbonate [K ₂ CO ₃ ] and tetra(triphenylphosphorus)palladium(0) [Pd(PPh ₃ ) ₄ ]. In this way, a compound NNNN1 having four naphthalene skeletons can be obtained.
In the above reaction, the bonding position of boron in dibromonaphthalene (a), the bonding position of -B(OH) ₂ in bromonaphthaleneboronic acid (b3), etc. can be determined by selecting raw materials according to the purpose. By selecting the raw materials, the bonding positions of the third naphthalene skeleton and the fourth naphthalene skeleton in the naphthalene skeleton can be controlled.
In this way, the compound of the present disclosure having three or four naphthalene skeletons can be produced by a simple method using easily available raw materials.

In the above synthesis scheme, the reaction is carried out for 2 hours to 10 hours depending on the purpose under a temperature condition of 50°C to 100°C, preferably 60°C to 90°C, the solvent is distilled off, and the compound of the present disclosure is purified. can be obtained.
Examples of the reaction solvent include organic solvents selected from water, 1,2-dimethoxyethane, and toluene.
Only one type of solvent may be used, or two or more types may be used in combination. When two or more types are used together, water and at least one type of organic solvent may be used together, or two or more types of mutually different organic solvents may be used together. Among these, a mixed solvent of water and 1,2-dimethoxyethane and a mixed solvent of water and toluene are preferable, and from the viewpoint of better yield, the mixing ratio of 1,2-dimethoxyethane and water is preferable. [Volume ratio] A mixed solvent of 15:1 to 5:1 is more preferable.

The amount of the solvent to be used is, for example, 0.5 parts by mass to 20 parts by mass per 1 part by mass of the starting materials (a1) or (a2), (b) and potassium carbonate. It is preferably 1 part by mass to 15 parts by mass.

The reaction may be performed in air or under an atmosphere or flow of an inert gas (helium, nitrogen, argon, etc.). Among these, from the viewpoint of further improving the yield, it is preferable to carry out under a nitrogen atmosphere.
Additionally, when performing a reaction in an inert gas atmosphere, bubbling the inert gas into the mixed solution of raw materials before the reaction can further reduce the effects of oxygen in the air on the reaction. It is preferable from the viewpoint of
The reaction may be carried out under normal pressure, increased pressure, or reduced pressure.
The reaction may be performed while stirring or under reflux. From the viewpoint of further improving the yield, it is preferable to carry out the reaction under reflux.

Purification can be carried out by conventional methods. For example, a crude product obtained by distilling off the solvent can be purified by silica gel chromatography using a mixed solvent of hexane and chloroform at a volume ratio of 3:1 as a developing solvent.

The method for producing a compound of the present disclosure can further include any steps other than the steps described above.
For example, the method may include a step of purifying the obtained crude product of the compound by silica gel chromatography or the like, as described above.

According to the method for producing the compound of the present disclosure, the compound of the present disclosure useful as a blue-emitting material can be obtained in high yield by a simple method using easily available starting materials. Therefore, it is possible to easily obtain a compound useful as a blue-emitting material, which is useful when applying blue-emitting materials to a wide range of fields.
Note that high yield in the present disclosure refers to a theoretical yield of 10% or more, preferably 30% or more.

≪Blue luminescent material≫
The blue light-emitting material of the present disclosure is represented by the following formula (I).

In formula (I), n represents 0 or 1.
The blue-blue luminescent material represented by the above formula (I) can emit deep blue light with a maximum absorption wavelength in the range of 380 nm to 460 nm even in a solvent such as chloroform solvent or in a solid state.
The blue light-emitting material represented by formula (I) is the same compound as the novel compound of the present disclosure, and its preferred examples are also the same.

The blue light-emitting material of the present disclosure has at least three naphthalene skeletons and has a molecular weight of 300 or more. Therefore, as a blue solid-state light-emitting material, the light-emitting layer of an organic light-emitting device can be formed by a vapor phase method such as a vacuum evaporation method. Since it can be suitably used when forming a light emitting layer and the durability of the formed light emitting layer is good, its application range is wide.

≪Organic light emitting device≫
The organic light-emitting device of the present disclosure includes the compound of the present disclosure described above or the blue light-emitting material of the present disclosure.
The organic light emitting device in the present disclosure is, for example, a display device, a component of a lighting device, an exposure light source of an electrophotographic image forming device, a backlight of a liquid crystal display device, a light emitting device such as a light emitting device having a color filter in a white light source, etc. It is suitably used as
As a display device, for example, an organic light-emitting element is used as a display part, and the organic light-emitting element is connected to the drain electrode or source electrode of a transistor to control the luminance of the light emitted, thereby displaying images on an organic EL television, a personal computer display, etc. Examples include display devices. The organic light emitting device of the present disclosure can be applied to the above display device, furthermore, a white LED light source and the like.

The compound of the present disclosure can emit deep blue light with an emission wavelength of 380 nm to 460 nm in a solid state. Therefore, when the organic light emitting device of the present disclosure is combined with an organic light emitting device containing red and green organic light emitting materials and applied to an image display device, for example, the organic light emitting device of the present disclosure has good white display performance and has good contrast. Excellent images can be obtained. It is also suitable as a white LED light source. Therefore, the organic light-emitting device of the present disclosure containing the compound of the present disclosure can be applied to various fields.

Hereinafter, the compound of the present disclosure and the method for producing the same will be described in more detail with reference to Examples. However, the present disclosure is not limited to the following examples unless the scope thereof is exceeded. In addition, in the following examples, "%" is in terms of mass unless otherwise specified.
The "%" yield in the examples is the ratio (by weight) of the amount of product actually obtained if all of the raw material were theoretically converted to the desired product.

(Reagent and compound identification method)
All reagents used in the preparation were commercially available. Furthermore, the synthesized product was confirmed by NMR (Nuclear Magnetic Resonance) and high-resolution mass spectrometry (HRMS) measurements.
For NMR measurement, NMR System 600 MHz manufactured by Varian was used. For high-resolution mass spectrometry, a high-performance dual convergence mass spectrometer (GC-MS) JMS-700 manufactured by JEOL Ltd. (JEOL) was used. The following HRMS (FAB) refers to a numerical value measured by an apparatus that performs ionization during mass spectrometry using fast atom bombardment (FAB).

[Example 1: Synthesis of bis(1-naphthyl)-2,6-naphthalene (exemplified compound 2611)]
Exemplary compound (2611) was synthesized according to the scheme below.
2,6-dibromonaphthalene (compound (a1)) 290 mg (1.0 mmol [mmol]), 1-bromonaphthalene boronic acid (compound (b)) 395 mg (2.3 mmol) and potassium carbonate 690 mg, 5.0 mmol After bubbling the solution obtained by dissolving the above in a mixed solvent of 1,2-dimethoxyethane (10 ml) and water (1 ml) with nitrogen gas for 10 minutes, tetra(triphenylphosphorus) palladium (0) ( 116 mg, 0.1 mmol) was added thereto, and the mixture was refluxed at 85° C. for 7 hours under a nitrogen atmosphere.
After returning the solution to room temperature, 100 ml of benzene was added, and after washing twice with 100 ml of saturated brine, the organic layer was separated, dried over sodium sulfate, and then the solvent was distilled off.
The product was separated by silica gel column chromatography using hexane:chloroform (volume ratio 3:1) as a developing solvent to obtain 217 mg of Exemplified Compound 2611 in a yield of 57%.

NMR measurement was carried out by the method already described, and the following results were obtained: ^{The 1} H NMR chart of Exemplary Compound 2611 is shown in Figure 2A, and ^{the 13} C NMR chart is shown in Figure 2B.
^1H NMR (600 MHz, _CDCl3 ) _δH = 8.06 (m, 1H), 8.02 (d, 1H, J = 8.2 Hz), 7.99 (d, 1H, J = 8.4 Hz), 7.96 (d, 1H, J = 7.8 Hz), 7.30 (d, 1H, J = 7.7 Hz), 7.71 (dd, 1H, J = 8.2, 1.5 Hz), 7.62-7.56 (m, 2H), 7.54 (ddd, 1H, J = 8.0, 6.8, 1.2 Hz), 7.47 (ddd, 1H, J = 8.4, 6.8, 1.5 Hz).
^13CNMR (600MHz, _CDCl3 ) _δC = 140.26, 138.70, 133.98, 132.67, 131.89, 129.09, 128.72, 128.49, 127.98, 127.96, 127.39, 126.29, 126.22, 125.99, 125.59.
HRMS (FAB) m/z calcd. for _{C30H20 380.1565} , found 380.1563.

[Example 2: Synthesis of 2-(1-naphthyl)-6-(2-naphthyl)naphthalene (exemplified compound 2612)]
1. Synthesis of Intermediate (26B1) First, Intermediate (26B1) was synthesized according to the scheme below.
858 mg (3.0 mmol) of 2,6-dibromonaphthalene (compound (a1)), 620 mg (3.6 mmol) of 1-bromonaphthaleneboronic acid (compound (b)) and 2 g (14 mmol) of potassium carbonate were added to 1,2- After bubbling the solution obtained by dissolving in a mixed solvent of 40 ml of dimethoxyethane and 4 ml of water with nitrogen gas for 10 minutes, 346 mg (0.3 mmol) of tetra(triphenylphosphorus) palladium (0) was added, and nitrogen gas was added. The mixture was refluxed at 85° C. for 2 hours in an atmosphere.
After returning the solution to room temperature, 200 ml of benzene was added, and after washing twice with 100 ml of saturated brine, the organic layer was separated, dried over sodium sulfate, and the solvent was distilled off.
The product was separated by silica gel column chromatography using hexane:chloroform (mixed solvent at a volume ratio of 3:1) as a developing solvent, and 408 mg of intermediate 26B1 was obtained in a yield of 41%.

NMR measurement was performed using the method described above, and the results shown below were obtained. ^{A 1} H NMR chart and a ¹³ CNMR chart of intermediate 26B1 are shown in FIG. 3A and FIG. 3B, respectively.
¹ HNMR (600MHz, CDCl ₃ ) 8.11 (d, 1H, J = 1.6Hz), 7.97-7.89 (m, 4H), 7.87 (d, 1H, J = 8.4Hz) , 7.76 (d, 1H, J = 8.6Hz), 7.68 (dd, 1H, J = 8.4, 1.6Hz), 7.62 (dd, 1H, J = 8.7, 1 .9Hz), 7.57 (dd, 1H, J = 7.9, 7.1Hz), 7.55-7.50 (m, 2H), 7.45 (ddd, 1H, J = 8.2, 6.9, 1.2Hz).
¹³ CNMR (600 MHz, CDCl ₃ ) δ _C =139.81, 138.96, 133.96, 133.74, 131.97, 131.73, 129.92, 129.86, 129.82, 129.66 , 128.78, 128.52, 128.11, 127.37, 126.91, 126.38, 126.05, 126.00, 125.55, 120.09.
HRMS (FAB) m/z calcd. for C ₂₀ H ₁₃ Br 332.0201, found 332.0185.

2. Synthesis of Exemplified Compound 2612 Exemplified Compound 2612 was synthesized according to the scheme below.
Above 1. 335 mg (1.0 mmol) of intermediate 26B1 obtained in step 2, 230 mg (1.3 mmol) of 2-bromonaphthaleneboronic acid (compound (b2)), and 690 mg (5 mmol) of potassium carbonate in 10 ml of 1,2-dimethoxyethane and 1 ml of water. After bubbling the solution obtained by dissolving it in a mixed solvent of Refluxed for an hour.
After returning the solution to room temperature, 200 ml of benzene was added, and after washing twice with 100 ml of saturated brine, the organic layer was separated, dried over sodium sulfate, and the solvent was distilled off.
The product was separated by silica gel column chromatography using hexane:chloroform (3:1 volume ratio mixed solvent) as a developing solvent to obtain 326 mg of Exemplary Compound 2612 in a yield of 86%.

NMR measurement was carried out by the method already described, and the following results were obtained: ^{The 1} H NMR chart of Exemplary Compound 2612 is shown in Figure 4A, and ^{the 13} C NMR chart is shown in Figure 4B.
^1H NMR (600MHz, _CDCl3 ) _δH = 8.27 (brd, 1H, J = 1.1 Hz), 8.22 (brd, 1H, J = 1.2 Hz), 8.06 (d, 1H, J = 8.2 Hz), 7.90-8.07 (m, 10H), 7.70 (dd, 1H, J = 8.2, 1.6 Hz), 7.50-7.61 (m, 5H), 7.56 (ddd, 1H, J = 8.2, 6.6, 1.2 Hz).
^13C NMR (600MHz, _CDCl3 ) _δC = 140.26, 138.81, 138.67, 138.53, 134.01, 133.92, 133.05, 132.86, 132.79, 131.90, 129.17, 128.86, 128.73, 128.68, 128.50, 128.41, 128.16, 127.97, 127.85, 127.40, 126.56, 126.35, 126.31, 126.28, 126.21, 126.10, 126.01, 125.88, 125.60.
HRMS (FAB) m/z calcd. for _{C30H20 380.1565} , found 380.1565.

[Example 3: Synthesis of bis(1-naphthyl)-2,7-naphthalene (exemplified compound 2711) and 2-bromo-7-(1-naphthyl)naphthalene (intermediate 27B1)]
Exemplary compound 2711 and intermediate 27B1 were synthesized according to the scheme below.
1,2 of 2,7-dibromonaphthalene (compound (a2)) 600 mg (2.1 mmol), 1-bromonaphthalene boronic acid (compound (b)) 654 mg (3.8 mmol) and potassium carbonate 1.4 g (10 mmol) - A solution obtained by dissolving in a mixed solvent of 25 ml of dimethoxyethane and 3 ml of water was bubbled with nitrogen gas for 10 minutes, and then 242 mg (0.2 mmol) of tetra(triphenylphosphorus) palladium (0) was added. The mixture was refluxed at 85° C. for 16 hours under a nitrogen atmosphere.
After returning the solution to room temperature, 150 ml of benzene was added, and after washing twice with 100 ml of saturated brine, the organic layer was separated, dried over sodium sulfate, and then the solvent was distilled off.
The product was separated by silica gel column chromatography using hexane:chloroform (mixed solvent at a volume ratio of 3:1) as a developing solvent, and 570 mg of Exemplified Compound 2711 was obtained in a yield of 71%, and 170 mg of Intermediate 27B1 was obtained. Obtained with a yield of 24%.

Intermediate 27B1 was subjected to NMR measurement using the method described above, and the results shown below were obtained. ^{A 1} H NMR chart and a ¹³ CNMR chart of intermediate 27B1 are shown in FIG. 5A and FIG. 5B, respectively.
¹ H NMR (400 MHz, CDCl ₃ ) δ _H = ¹ H NMR δ _H = 8.06 (d, 1 H, J = 1.7 Hz), 7.96-7.86 (m, 5 H), 7.81 ( d, 1H, J=8.8Hz), 7.66 (dd, 1H, J=8.2, 1,6Hz), 7.61 (dd, 1H, J=8.7, 1.9Hz), 7 .57 (dd, 1H, J=8.1, 7.0Hz), 7.54-7.49 (2H, two ddd signals overlap), 7.44 (ddd, 1H, J=8.7, 6. 7,1.3Hz).
^13C NMR (600MHz, _CDCl3 ) _δC = 139.74, 139.59, 134.63, 133.94, 131.73, 131.08, 130.19, 129.55, 129.06, 128. 51,128.14,127.90,127.78,127.38,126.38,126.05,125.98,125.54,120.44.
HRMS (FAB) m/z calcd. for C ₃₀ H ₂₀ 380.1565, found 380.1564.

NMR measurement of Exemplary Compound 2711 was carried out by the method already described, and the following results were obtained: ^{The 1} H NMR chart of Exemplary Compound 2711 is shown in Figure 6A, and ^{the 13} C NMR chart is shown in Figure 6B.
^1H NMR (400MHz, _CDCl3 ) _δH = 8.06 (d, 2H, J = 8.3 Hz), 8.02 (s, 2H), 8.00 (d, 2H, J = 8.2 Hz), 7.96 (d, 2H, J = 8.2 Hz), 7.92 (d, 2H, J = 7.8 Hz), 7.71 (d, 2H, J = 8.2 Hz), 7.61-7.55 (m, 4H), 7.53 (t, 2H, J = 7.3 Hz), 7.46 (t, 2H, J = 7.7 Hz).
^13C NMR (600MHz, _CDCl3 ) _δC = 140.26, 139.00, 133.98, 133.95, 133.57, 131.89, 131.85, 129.03, 128.86, 128.49, 127.97, 127.67, 127.40, 126.30, 126.22, 126.00, 125.59.
HRMS (FAB) m/z calcd. for _{C30H20 380.1565} , found 380.1564.

[Example 4: Synthesis of 2-(1-naphthyl)-7-(2-naphthyl)naphthalene (exemplified compound 2712)]
Exemplary compound 2712 was synthesized according to the scheme below.
100 mg (0.30 mmol) of the intermediate (27B1) obtained in Example 3, 67 mg (0.39 mmol) of 2-bromonaphthaleneboronic acid (compound (b2)), and 207 mg (1.5 mmol) of potassium carbonate were mixed with 1, A solution obtained by dissolving in a mixed solvent of 5 ml of 2-dimethoxyethane and 1 ml of water was bubbled with nitrogen gas for 10 minutes, and then 35 mg (0.03 mmol) of tetra(triphenylphosphorus) palladium (0) was added. The mixture was refluxed at 85° C. for 3 hours under a nitrogen atmosphere.
After returning the solution to room temperature, 100 ml of benzene was added, and after washing twice with 100 ml of saturated brine, the organic layer was separated, dried over sodium sulfate, and then the solvent was distilled off.
The product was separated by silica gel column chromatography using hexane:chloroform (mixed solvent at a volume ratio of 3:1) as a developing solvent to obtain 91 mg of Exemplary Compound 2712 in a yield of 80%.

NMR measurement of Exemplary Compound 2712 was performed by the method described above, and the results shown below were obtained. A ¹ H NMR chart and a ¹³ C NMR chart of Exemplary Compound 2712 are shown in FIG. 7A and FIG. 7B, respectively.
¹ H NMR δ _{H =} 8.23 (s, 1H), 8.21 (s, 1H), 8.08-8.04 (m, 2H), 8.03-7.88 (m, 9H), 7.67 (d, 1H, J=8.5Hz), 7.62-7.48 (m, 5H), 7.45 (m, 1H).
^13C NMR (600MHz, _CDCl3 ) _δC = 140.27, 139.09, 139.02, 138.53, 134.00, 133.89, 132.86, 131.95, 131.90, 129. 22, 128.83, 128.72, 128.54, 128.49, 128.41, 127.98, 127.84, 127.62, 127.39, 126.53, 126.43, 126.31, 126.23, 126.20, 126.12, 126.01, 125.87, 125.60.
HRMS (FAB) m/z calcd. for C ₂₀ H ₂₀ 380.1565,found. 380.1563

≪Evaluation≫
Emission wavelength, photophysical properties (in solid state (powder)) and solution containing the compound (chloroform) of Exemplified Compound 2611, Exemplified Compound 2612, Exemplified Compound 2711, and Exemplified Compound 2712 synthesized in Examples 1 to 4 Fluorescence yield, fluorescence lifetime and rate constant) were measured.

<Measurement method of each physical property>
(Measurement of fluorescence yield, etc.)
Using an absolute PL photon yield measurement device (C9920-02, manufactured by Hamamatsu Photonics Co., Ltd.), the maximum absorption wavelength (λabs/nm) and fluorescence number rate of the above compound in chloroform solvent were measured. By using an absolute PL photon yield measurement device, highly reliable fluorescence yield values can be obtained.
(Measurement of absorption spectrum)
Absorption spectra were measured using a UV-visible spectrophotometer (Ubest-50, manufactured by JASCO), and fluorescence emission spectra were measured using an absolute PL photon yield measuring device (C9920-02, manufactured by Hamamatsu Photonics Co., Ltd.). Measured using

To measure the solid state, each compound is prepared as a solid powder sample, each of the obtained samples is placed in a glass Petri dish attached to the absolute PL photon yield measurement device described above, and the quartz Petri dish containing the sample is placed in the absolute PL photon yield measurement device described above. The maximum fluorescence wavelength and fluorescence yield were measured under the same conditions as those used to measure the maximum fluorescence wavelength and fluorescence yield for a solution of each of the above compounds dissolved in chloroform, except that it was installed in a photon yield measuring device. .

The absorption spectrum in chloroform solvent, the fluorescence spectrum in chloroform solvent, and the solid fluorescence spectrum of the above exemplary compound are shown in FIG. In FIG. 1, the absorption spectrum is shown by a solid line, the emission spectrum in chloroform solvent is shown by a broken line, and the fluorescence spectrum in a solid state is shown by a dotted line.

In addition, in order to evaluate the basic physical properties of each exemplified compound, the emission maximum wavelength (λf) of the exemplified compound in chloroform solvent, the emission maximum wavelength in the solid state (λf ^solid ), the emission quantum yield (Φf) in chloroform solvent, and The solid state luminescence quantum yield (Φf ^solid ) was measured and is also listed in Table 1.

1 and Table 1, all of the exemplary compounds 2611, 2612, 2711, and 2712 had a maximum emission wavelength in the range of 380 nm to 410 nm in the solid state, and had an emission quantum yield at a level that was practically problem-free. Of these, the exemplary compound 2611 exhibited an emission quantum yield of more than 0.9, which is an extremely excellent value.
Furthermore, when each of the compounds obtained in the Examples was in a solid powder state, vivid blue fluorescence was confirmed when observed with the naked eye.

From the results of the above examples, it was shown that the compound of the present disclosure is a blue-emitting material that exhibits a blue color at a level useful as an organic light-emitting device, etc., and has good luminous efficiency.

Claims (6)

When the third naphthalene skeleton is bonded to the partial structure (A) below and n is 1, it is a compound represented by the following formula (I) that further has a fourth naphthalene skeleton, and the third naphthalene skeleton is An organic light-emitting device containing a compound represented by the following formula (I) in which the bonding position is the 6th or 7th position of the partial structure (A) in the following formula (I).


In formula (I), n represents 0 or 1. This is a compound in which a third naphthalene skeleton is bonded to the following partial structure (A) , and the bonding position of the third naphthalene skeleton is the 6th or 7th position of the partial structure (A) in the following formula (I-2). A compound represented by the following formula (I-2).


The compound according to claim 2, which is at least one selected from the following compound (1), compound (2), compound (3), and compound (4).

4. The compound according to claim 2 or 3, which has a molecular weight of 300 or more. The compound according to any one of claims 2 to 4, which is a blue-emitting material. 2,6-dibromonaphthalene (a1) or 2,7-dibromonaphthalene (a2) and 1-bromonaphthaleneboronic acid (b) in the presence of potassium carbonate and tetra(triphenylphosphorus)palladium (0) A method for producing the compound according to any one of claims 2 to 4, which comprises a step of reacting.