JP2018035129A - Pyrimidine derivative, luminescent material consisting of the same and organic el element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel pyrimidine derivative as a heat activation delayed fluorescence (TADF) material capable of efficiently up-conversion of triplet exciton to singlet exciton, a luminescent material and an organic EL element using the same.SOLUTION: There is provided a pyrimidine derivative represented by the following general formula (1) and having energy difference (ΔE) between excited singlet energy (E) and triplet excitation energy (ΔE) of 0.25 eV or less. (1), where Rrepresents a hydrogen atom, an alkyl group, an alkoxy group, a thioalkoxy group or an amino group as an electron-donating group, or an aryl group, a cyano group, a carbonyl group or a sulfonyl group as an electron-attracting group, Rrepresents a methyl group, an aryl group, an alkoxy group, an acyl group or a cyano group, n represents an integer of 1 to 3, a substituents D each independently represents a hydrogen atom or an electron-donating group, and a phenyl group having the substituents D has a symmetric structure or an asymmetric structure when n is 2 or 3.SELECTED DRAWING: None

Description

  The present invention relates to a novel pyrimidine derivative having high luminous efficiency, a light emitting material using the same, and an organic EL device.

  In an organic electronics (EL) element, by applying a voltage between a pair of electrodes, holes from the anode, electrons from the cathode, and a light emitting layer containing an organic compound as a light emitting material are injected, and the injected electrons and When holes recombine, excitons are formed in the light-emitting organic compound, and light emission can be obtained from the excited organic compound.

One means for improving the practicality of such an organic EL element is to increase the luminous efficiency. Excitons formed by organic compounds include singlet excitons (E _S1 ) and triplet excitons (E _T1 ). Fluorescence emission from singlet excitons (E _S1 ) and triplet excitons (E Although there are a phosphorescence from _T1), these statistical generation ratio in _{elements, E S1: E T1 = 1} : 3, and limit the internal quantum efficiency of 25% on an organic EL element using the fluorescent emission It was said. Therefore, in recent years, development of a light-emitting element using a phosphorescent compound capable of converting a triplet excited state into light emission has been actively performed in order to improve the conversion efficiency (internal quantum efficiency) from electrons to photons. It was. However, most of the phosphorescent compounds are complexes having a noble metal such as iridium or platinum as a central metal, and there are problems in terms of cost and supply stability.

Recently, materials that emit delayed fluorescence have been studied as materials that can convert part of the triplet excited state into light emission without using such a phosphorescent compound. Specifically, an organic EL device using a thermally activated delayed fluorescence (TADF) material that upconverts triplet excitons (E _T1 ) to singlet excitons (E _S1 ) has been developed. ing. Using this TADF material, singlet excitons (E _S1 ) emit fluorescence, while triplet excitons (E _T1 ) absorb the heat of the element and surroundings and cross back to the excited singlet. In order to emit fluorescence, all excitons generated by current excitation can be extracted as light energy, and at the same time, an internal quantum efficiency of 100% can be realized.

For example, in Non-Patent Document 1, a carbazolyl dicyanobenzene (CDCB) derivative is reported as a phosphorescent compound containing no metal, and the CDCB derivative has an energy between a singlet excited state and a triplet excited state. It has been reported that the difference (ΔE _ST ) is small and promotes highly efficient up-conversion from the excited triplet state to the excited singlet exciton while maintaining a high emission quantum yield.

  Furthermore, the TADF material can be expected to improve not only a high internal quantum yield but also an external quantum yield because of the above-described light emission mechanism. Regarding the external quantum efficiency, it was about 7.5% with the conventional fluorescent material, but with the green TADF material, the external quantum efficiency approaching 30%, which is comparable to the phosphorescent material, has been realized.

  Non-Patent Document 2 shows one of the design rules for blue-emitting organic molecules exhibiting TADF, and organic molecules based on the design rules are HOMO (Highest Occupied Molecular Orbital) with a wide range of delocalized electrons Orbital) and LUMO (Lowest Unoccupied Molecular Orbital), and even when the overlap of the two wave functions is small, high oscillator strength is induced and the emission quantum yield is reported to increase. . The organic molecule exhibits high emission quantum yield and efficient up-conversion from triplet excitons to singlet excitons, and realizes that the emission efficiency and internal quantum efficiency are close to 100%. There is disclosure.

An organic EL device using a delayed fluorescent material for the light emitting layer is considered to exhibit high external quantum efficiency. In order to obtain delayed fluorescence with high efficiency, it is necessary not only to cross back from the triplet level to the excited singlet level but also to efficiently emit light from the excited singlet. In order to obtain such a light-emitting material, for example, in order to reduce an energy difference (ΔE _ST ) between a singlet and a triplet, in an organic compound, an electron-donating group having a donor property and an electron request having an acceptor property are obtained. Precise molecular design is necessary, such as appropriately selecting and combining the pulling group.

  In Patent Document 1, it is reported that a triazine compound containing a carbazole structure or a pyrimidine compound containing a carbazole structure can be a TADF material as a light-emitting material used for an organic EL element.

  Furthermore, Non-Patent Document 3 describes a blue organic EL device using a 9,10-dihydroacridine / diphenylsulfone derivative as a TADF material, and has performance comparable to that of an existing phosphorescent organic EL device. It has been reported that a device including a material exhibits an external quantum efficiency of 19.5% and suppresses a decrease in light emission efficiency at high luminance.

  All of the above documents perform molecular design of TADF materials. However, at present, for example, with a blue TADF material that requires higher light emission energy, the required light emission efficiency is not sufficiently achieved, and the value remains low. Therefore, further studies on TADF materials are desired.

Japanese Patent No. 5679496

H. Uoyama, K. Goushi, K. Shizu, H. Nomura, C. Adachi, Nature 2012,492, 234. S. Hirata, Y. Sakai, K. Masui, H. Tanaka, SY Lee, H. Nomura, N. Nakamura, M. Yasumatsu, H. Nakanotani, Q. Zhang, K. Shizu, H. Miyazaki, C. Adachi , Nature Materials 2015, 14, 330. Q. Zhang, B. Li, S. P. Huang, H. Nomura, H. Tanaka, C. Adachi, Nature Photonics 2014, 8, 326.

In the present invention, focusing on the energy difference between HOMO-LUMO (ΔE _HL ) and the energy difference between the singlet excited state and the triplet excited state (ΔE _ST ), the triplet exciton (E _T1 ) is calculated. It is an object to provide a novel pyrimidine derivative as a thermally activated delayed fluorescence (TADF) material capable of efficiently up-converting to singlet excitons (E _S1 ), and a light emitting material and an organic EL device using the same. Yes.

The present inventors have found that a specific pyrimidine derivative in which a specific electron donating site is introduced into a pyrimidine skeleton, which is a light emitting site, is effective as a thermally activated delayed fluorescence (TADF) material, and completed the present invention. It was.
That is, this invention consists of the following matters.

（一般式（１）中、Ｒ¹は、水素原子、電子供与性基として、アルキル基、アルコキシ基、チオアルコキシ基若しくはアミノ基、又は、電子求引性基として、アリール基、シアノ基、カルボニル基若しくはスルホニル基を表し、Ｒ⁸は、メチル基、アリール基、アルコキシ基、アシル基又はシアノ基を表し、ｎは１〜３の整数を表し、置換基Ｄは、それぞれ独立に、水素原子又は電子供与性基を表し、ｎが２又は３の場合、該置換基Ｄを有するフェニル基は、互いに対称構造又は非対称構造を有する。） The pyrimidine derivative of the present invention is represented by the following general formula (1), and an energy difference (ΔE _ST ) between excited singlet energy (E _S1 ) and triplet excited energy (E _T1 ) is 0.25 eV or less. It is characterized by being.

(In the general formula (1), R ¹ is a hydrogen atom, an electron donating group, an alkyl group, an alkoxy group, a thioalkoxy group or an amino group, or an electron withdrawing group, an aryl group, a cyano group, or a carbonyl group. R ⁸ represents a methyl group, an aryl group, an alkoxy group, an acyl group or a cyano group, n represents an integer of 1 to 3, and each substituent D independently represents a hydrogen atom or Represents an electron-donating group, and when n is 2 or 3, the phenyl groups having the substituent D have a symmetric structure or an asymmetric structure.

（一般式（１）中、Ｒ¹は、水素原子、電子供与性基として、アルキル基、アルコキシ基、チオアルコキシ基若しくはアミノ基、又は、電子求引性基として、アリール基、シアノ基、カルボニル基若しくはスルホニル基を表し、Ｒ⁸は、メチル基、アリール基、アルコキシ基、アシル基又はシアノ基を表し、ｎは２を表し、置換基Ｄを有するフェニル基は、互いに対称構造又は非対称構造を有する。） The pyrimidine derivative of the present invention is represented by the following general formula (1), and an energy difference (ΔE _ST ) between excited singlet energy (E _S1 ) and triplet excited energy (E _T1 ) is 0.25 eV or less. It is characterized by being.

(In the general formula (1), R ¹ is a hydrogen atom, an electron donating group, an alkyl group, an alkoxy group, a thioalkoxy group or an amino group, or an electron withdrawing group, an aryl group, a cyano group, or a carbonyl group. R ⁸ represents a methyl group, an aryl group, an alkoxy group, an acyl group or a cyano group, n represents 2, and the phenyl group having the substituent D has a symmetric structure or an asymmetric structure. Have)

（一般式（２）中、Ｒ¹は、水素原子、電子供与性基として、アルキル基、アルコキシ基、チオアルコキシ基若しくはアミノ基、又は、電子求引性基として、アリール基、シアノ基、カルボニル基若しくはスルホニル基を表し、Ｒ⁸は、メチル基、アリール基、アルコキシ基、アシル基又はシアノ基を表し、置換基Ｄは、それぞれ独立に下記構造式で表される置換基のいずれかを表す。）

（一般式（３）中、Ｒ²〜Ｒ⁷はそれぞれ独立に、水素原子、アルキル基又はアリール基を表し、Ｘは、メチレン基、−ＣＲ^aＲ^b−、−Ｏ−、−Ｓ−、又は−Ｓ（＝Ｏ）₂−を表し、Ｒ^a及びＲ^bは、それぞれ独立にアルキル基又はアリール基であり、また互いに連結して環を形成してもよい。）。 The pyrimidine derivative of the present invention is represented by the following general formula (2), and an energy difference (ΔE _ST ) between excited singlet energy (E _S1 ) and triplet excited energy (E _T1 ) is 0.25 eV or less. It is characterized by being.

(In the general formula (2), R ¹ represents a hydrogen atom, an electron donating group as an alkyl group, an alkoxy group, a thioalkoxy group or an amino group, or an electron withdrawing group as an aryl group, a cyano group, or a carbonyl group. Represents a group or a sulfonyl group, R ⁸ represents a methyl group, an aryl group, an alkoxy group, an acyl group, or a cyano group, and each substituent D independently represents any of the substituents represented by the following structural formulae. .)

(In General Formula (3), R ^{2 to} R ⁷ each independently represents a hydrogen atom, an alkyl group or an aryl group, and X represents a methylene group, —CR ^a R ^b —, —O—, —S—, Or -S (= O) _2- , wherein R ^a and R ^b are each independently an alkyl group or an aryl group, and may be linked to each other to form a ring).

The pyrimidine derivative is preferably represented by the following structural formula.

The light emitting material of the present invention comprises the above pyrimidine derivative.
The organic EL device of the present invention uses the above pyrimidine derivative.

According to the pyrimidine derivative of the present invention, the energy difference (ΔE _ST ) between the singlet and the triplet is reduced by introducing a specific electron donating site into the pyrimidine skeleton that is the light-emitting site, and the triplet exciton Efficient up-conversion is realized through reverse intersystem crossing to singlet excitons. Specifically, in the pyrimidine derivative represented by the general formula (1) or (2), an electron donating moiety such as a carbazole moiety, an acridine moiety, or a dimethylacridine derivative as a substituent D on the pyrimidine skeleton that is a light emitting moiety. Upconversion emission can be observed by introducing. Therefore, the pyrimidine derivative is suitable as a thermally activated delayed fluorescence (TADF) material.

Furthermore, in the pyrimidine derivative, the pyrimidine skeleton and the carbazole moiety, the dimethylacridine moiety, and the dimethylacridine derivative moiety, which are the substituent D, each have high triplet energy (E _T1 ). Therefore, the pyrimidine derivative can be expected to be blue TADF.

As a result of quantum chemical calculation, the pyrimidine derivative has a large energy difference (ΔE _HL ) between HOMO (highest occupied orbital) and LUMO (lowest empty orbital) of 3.3 eV or more, and a blue emission color is expected.

From the results of quantum chemical calculations, the pyrimidine derivative has an energy difference (ΔE _ST ) between excited singlet energy (E _S1 ) and triplet energy (E _T1 ) of 0.25 eV or less, specifically 0.2 eV or less. It has a small and high emission quantum efficiency.

  The pyrimidine derivative can be synthesized in a good yield by a relatively simple method. In addition, since no precious metal such as Ir or Pt is included, the cost of the light emitting material can be reduced.

  The organic EL device of the present invention achieves an external quantum efficiency of 20% by using the pyrimidine derivative. Such external quantum efficiency is more than twice that of conventional fluorescent materials.

FIG. 1 is a diagram showing a ¹ H-NMR spectrum of Ac-PPM. FIG. 2 is a diagram showing a ¹ H-NMR spectrum of BAc-MPM. FIG. 3 is a diagram showing a ¹ H-NMR spectrum of BCz-MPM. 4A shows the UV-vis and PL spectra of a single film of Ac-PPM and a 10 ⁻⁵ M toluene solution, and FIG. 4B shows a single film of Ac-PPM and 10 wt% DPEPO-doped co-evaporation. It is a figure showing UV-vis and PL spectrum of a film | membrane. FIG. 5 is a diagram showing transient PL spectra at 300K and 5K in a 10 wt% DPEPO-doped co-deposited film of Ac-PPM. 6A shows the PL spectrum at 5K of the 10 wt% DPEPO-doped co-deposited film of Ac-PPM, and FIG. 6B shows the PL spectrum at room temperature (RT) of the 10 wt% DPEPO-doped co-deposited film of Ac-PPM. FIG. FIG. 7 is a diagram showing the PYS measurement results of the Ac-PPM single film. FIG. 8 is a diagram showing UV-vis and PL spectra of a BCz-MPM single film and a 10 wt% DPEPO-doped co-deposited film. The “―― ● ――” line represents the PL spectrum, and the “―― ○ ――” line represents the UV-vis spectrum. FIG. 9 is a diagram showing a transient PL spectrum of a BCz-MPM 10 wt% DPEPO-doped co-deposited film. FIG. 10A shows a PL spectrum at 5K of a 10 wt% DPEPO-doped co-deposited film of BCz-MePyM — 2-1, and FIG. 10B shows a room temperature (RT) of the 10 wt% DPEPO-doped co-deposited film of BCz-MePyM — 2-1. It is a figure showing PL spectrum in). FIG. 11 is a diagram showing a PYS measurement result of a BCz-MPM single film. FIG. 12 is a diagram showing a ¹ H-NMR spectrum of AC-SPM. FIG. 13 is a diagram showing a ¹ H-NMR spectrum of PXZ-PPM. FIG. 14 is a diagram showing a ¹ H-NMR spectrum of Ac-MMPM. FIG. 15 is a diagram showing a ¹ H-NMR spectrum of Ac-46DPPM. FIG. 16 is a diagram showing a ¹ H-NMR spectrum of Ac-26DPPM. FIG. 17A shows the UV-vis spectrum and PL spectrum of a 10 wt% DPEPO-doped co-deposited film of Ac-SPM, and FIG. 17B shows the room temperature (10 wt% DPEPO-doped co-deposited film of Ac-SPM). (RT) and 2K represent a transient PL spectrum at 5K, and FIG. 17 (c) shows a PL spectrum at 300K and 5K in a 10 wt% DPEPO-doped co-deposited film of Ac-SPM. 18A shows a UV-vis spectrum and a PL spectrum of a 10 wt% DPEPO-doped co-deposited film of Ac-NPM, and FIG. 18B shows a room temperature (10 wt% DPEPO-doped co-deposited film of Ac-NPM). (RT) and 5K represent 5 hour-resolved transient PL spectra, and FIG. 18 (c) is a diagram illustrating PL spectra at 300K and 5K in a 10 wt% DPEPO-doped co-deposited film of Ac-NPM. FIG. 19A shows a UV-vis spectrum and a PL spectrum of a 10 wt% DPEPO-doped co-deposited film of PXZ-PPM, and FIG. 19B shows a room temperature (10 wt% DPEPO-doped co-deposited film of PXZ-PPM). RT) and an 8 hour-resolved transient PL spectrum at 5K, and FIG. 19C shows a PL spectrum at 300K and 5K in a 10 wt% DPEPO-doped co-deposited film of PXZ-PPM. 20A shows the UV-vis spectrum and PL spectrum of the AC-MMPM 10 wt% DPEPO-doped co-deposited film, and FIG. 20B shows the room temperature of the AC-MMPM 10 wt% DPEPO-doped co-deposited film. RT) and an 11-hour resolved transient PL spectrum at 5K, and FIG. 20C is a diagram showing a PL spectrum in a 10 wt% DPEPO-doped co-deposited film of AC-MMPM. FIG. 21 is a diagram showing a ¹ H-NMR spectrum of AC-1MHPM. FIG. 22 is a diagram showing a ¹ H-NMR spectrum of AC-2MHPM. FIG. 23 is a diagram showing a ¹ H-NMR spectrum of AC-3MHPM. FIG. 24 (a) represents a UV-vis spectrum of a toluene solution (10 ⁻⁵ M) of AC-1MHPM, AC-2MHPM, and AC-3MHPM, and FIG. 24 (b) shows AC-1MHPM, AC-2MHPM. , and it represents a PL spectrum of the toluene solution of ^{AC-3MHPM (10 -5 M)} , FIG. 24 (c) is, AC-1MHPM, AC-2MHPM , and PL of 20wt% DPEPO doped co-deposited film of AC-3MHPM It is a figure showing a spectrum. FIG. 25 is a diagram showing transient PL spectra at 300 K and 5 K in 20 wt% DPEPO-doped co-deposited films of AC-1 MHPM, AC-2 MHPM, and AC-3 MHPM. FIG. 26 (a) shows the fluorescence and low temperature phosphorescence (5K) spectrum in the AC-1MHPM 20 wt% DPEPO-doped co-deposited film, and FIG. 26 (b) shows the AC-2MHPM in the 20 wt% DPEPO-doped co-deposited film. Fluorescence and low temperature phosphorescence (5K) spectra are shown, and FIG. 26C is a diagram showing fluorescence and low temperature phosphorescence (5K) spectra in a 20 wt% DPEPO-doped co-deposited film of AC-3MHPM. FIG. 27 is a diagram showing an EL spectrum of an organic EL element in which the light emitting layer is Ac-PPM: DPEPO (10 wt% DPEPO co-deposited film). FIG. 28A shows the relationship between current density-voltage-luminance characteristics of an organic EL element in which the light-emitting layer is Ac-PPM: DPEPO (10 wt% DPEPO co-deposited film), and FIG. 28 represents the relationship between the power efficiency and the luminance characteristics of the organic EL element in which Ac-PPM: DPEPO (10 wt% DPEPO co-deposited film) is used, and FIG. It is a figure showing the relationship of the external quantum efficiency-luminance characteristic of the organic EL element made into the vapor deposition film. FIG. 29 is an energy diagram of the hole transport layer, the light emitting layer, and the electron transport layer when the light emitting layer is Ac-PPM: DPEPO (10 wt% DPEPO co-deposited film) in the organic EL device. FIG. 30 is a diagram illustrating an EL spectrum of an organic EL element in which the light emitting layer is BCz-MPM: DPEPO (10 wt% DPEPO co-deposited film). FIG. 31A shows the relationship between current density-voltage-luminance characteristics of an organic EL element in which the light emitting layer is BCz-MPM: DPEPO (10 wt% DPEPO co-deposited film), and FIG. FIG. 31C shows the relationship between the power efficiency and the luminance characteristics of an organic EL element in which BCz-MPM: DPEPO (10 wt% DPEPO co-deposited film) is used, and FIG. It is a figure showing the relationship of the external quantum efficiency-luminance characteristic of the organic EL element made into the vapor deposition film. FIG. 32 is an energy diagram of a hole transport layer, a light emitting layer, and an electron transport layer when the light emitting layer is BCz-MPM: DPEPO (10 wt% DPEPO co-deposited film) in the organic EL device. FIG. 33 is a diagram showing an EL spectrum of an organic EL element in which the light emitting layer is Ac-PPM: PO9 (10 wt% PO9 co-deposited film). FIG. 34 (a) shows the relationship between the current density-voltage-luminance characteristics of an organic EL element in which the light emitting layer is Ac-PPM: PO9 (10 wt% PO9 co-deposited film), and FIG. -PPM: PO9 (10 wt% PO9 co-deposited film) represents the relationship between the power efficiency and luminance characteristics of the organic EL element, and FIG. 34 (c) shows the light emitting layer as Ac-PPM: PO9 (10 wt% PO9 co-deposited film). It is a figure showing the relationship between the external quantum efficiency-luminance characteristic of the organic EL element made into. For comparison, FIGS. 28 (a) to 28 (c) are shown in an overlapping manner in FIGS. 34 (a) to 34 (c). FIG. 35 is an energy diagram of a hole transport layer, a light-emitting layer, and an electron transport layer when the light-emitting layer is Ac-PPM: PO9 (10 wt% PO9 co-deposited film). FIG. 36 shows a hole transport layer, a light emitting layer, and an electron transport when the light emitting layer is Ac-HPM, Ac-MPM, Ac-PPM, Ac-SPM, or Ac-NPM (each 10 wt% DPEPO co-deposited film). It is an energy diagram of a layer. FIG. 37 is a diagram showing an EL spectrum of an organic EL element in which the light emitting layer is Ac-SPM, Ac-HPM, Ac-PPM, Ac-MPM, or Ac-NPM (each 10 wt% DPEPO co-deposited film). FIG. 38A shows current density-voltage- of an organic EL element in which the light emitting layer is Ac-SPM, Ac-HPM, Ac-PPM, Ac-MPM, or Ac-NPM (each 10 wt% DPEPO co-deposited film). FIG. 38B shows a relationship of luminance characteristics, and the light emitting layer is Ac-SPM, Ac-HPM, Ac-PPM, Ac-MPM, or Ac-NPM (each 10 wt% DPEPO co-deposited film). FIG. 38C shows the relationship between the external quantum efficiency and luminance characteristics of the organic EL element. FIG. 38C shows that the light emitting layer is Ac-SPM, Ac-HPM, Ac-PPM, Ac-MPM, or Ac-NPM (each 10 wt% DPEPO). It is a figure showing the relationship of the power efficiency-luminance characteristic of the organic EL element made into the co-deposition film | membrane. FIG. 39 shows the hole transport layer, light-emitting layer, and electron transport layer when the light-emitting layer is Ac-HPM: mCP (10 wt% mCP co-deposited film) and Ac-HPM: DPEPO (10 wt% DPEPO co-deposited film). It is an energy diagram. FIG. 40 is a diagram illustrating an EL spectrum of an organic EL element in which the light emitting layer is Ac-HPM: DPEPO (10 wt% DPEPO co-deposited film). FIG. 41A shows the relationship between current density-voltage-luminance characteristics of an organic EL element in which the light-emitting layer is Ac-MPM: DPEPO (10 wt% DPEPO co-deposited film), and FIG. FIG. 41C shows the relationship between the power efficiency and the luminance characteristics of the organic EL element in which Ac-MPM: DPEPO (10 wt% DPEPO co-deposited film) is used, and FIG. 41C shows the light emitting layer as Ac-MPM: DPEPO (10 wt%). It is a figure showing the relationship of the external quantum efficiency-luminance characteristic of the organic EL element made into DPEPO co-deposition film | membrane. FIG. 42 is an energy diagram of the hole transport layer, the light emitting layer, and the electron transport layer when the light emitting layer is PXZ-PPM: CBP (10 wt% CBP co-evaporated film). FIG. 43 is a diagram illustrating an EL spectrum of an organic EL element in which the light emitting layer is PXZ-PPM: CBP and the concentration of PXZ-PPM is 5 wt%, 10 wt%, 15 wt%, 20 wt%, or 50 wt%. FIG. 44A shows the relationship between the luminance characteristics and voltage of an organic EL element in which the light emitting layer is PXZ-PPM: CBP and the concentration of PXZ-PPM is 5 wt%, 10 wt%, 15 wt%, 20 wt%, or 50 wt%. FIG. 44B shows the external quantum efficiency of the organic EL element in which the light emitting layer is PXZ-PPM: CBP and the concentration of PXZ-PPM is 5 wt%, 10 wt%, 15 wt%, 20 wt%, or 50 wt%. FIG. 44 (c) shows the relationship between luminance characteristics, and the light emitting layer is PXZ-PPM: CBP, and the concentration of PXZ-PPM is 5 wt%, 10 wt%, 15 wt%, 20 wt%, or 50 wt%. It is a figure showing the relationship of the power efficiency-luminance characteristic of an organic EL element. FIG. 45 shows the hole transport layer, the light-emitting layer, and the electron transport layer when the light-emitting layer is Ac-MMPM: mCP (10 wt% mCP co-deposited film) and Ac-MMPM: DPEPO (10 wt% DPEPO co-deposited film). It is an energy diagram. FIG. 46 is a diagram showing an EL spectrum of an organic EL element in which the light emitting layer is Ac-MMPM: mCP (10 wt% mCP co-deposited film). FIG. 47A shows the relationship between the current density-voltage-luminance characteristics of an organic EL element in which the light emitting layer is Ac-MMPM: mCP (10 wt% mCP co-deposited film), and FIG. 47 represents the relationship between the power efficiency and the luminance characteristics of the organic EL device in which Ac-MMPM: mCP (10 wt% mCP co-deposited film) is used. FIG. It is a figure showing the relationship of the external quantum efficiency-luminance characteristic of the organic EL element made into the vapor deposition film. In FIG. 48, one of the light emitting layers is Ac-46DPPM, Ac-26DPPM, or CzAc-26DPPM (each 10 wt% mCP co-deposited film), and the other is Ac-46DPPM, Ac-26DPPM, or CzAc-26DPPM (each 10 wt%). It is an energy diagram of a positive hole transport layer, a light emitting layer, and an electron carrying layer when it is set as a DPEPO co-deposition film | membrane. FIG. 49 is a diagram showing an EL spectrum of an organic EL element in which the light emitting layer is Ac-46DPPM: mCP (10 wt% mCP co-deposited film) and Ac-46DPPM: DPEPO (10 wt% DPEPO co-deposited film). FIG. 50A shows current density-voltage-luminance characteristics of an organic EL element in which the light emitting layer is Ac-46DPPM: mCP (10 wt% mCP co-deposited film) and Ac-46DPPM: DPEPO (10 wt% DPEPO co-deposited film). A relationship of current density-voltage-luminance characteristics of an organic EL device in which the light emitting layer is Ac-26DPPM: mCP (10 wt% mCP co-deposited film) and Ac-26DPPM: DPEPO (10 wt% DPEPO co-deposited film); The relationship of the current density-voltage-luminance characteristic of the organic EL element which made the light emitting layer CzAc-26DPPM: mCP (10 wt% mCP co-deposited film) and CzAc-26DPPM: DPEPO (10 wt% DPEPO co-deposited film) is represented. FIG. 50B shows the relationship between the power efficiency and the luminance characteristics of the organic EL element in which the light emitting layer is Ac-46DPPM: mCP (10 wt% mCP co-deposited film) and Ac-46DPPM: DPEPO (10 wt% DPEPO co-deposited film). The relationship between the power efficiency and the luminance characteristics of the organic EL element in which the light emitting layer is Ac-26DPPM: mCP (10 wt% mCP co-deposited film) and Ac-26DPPM: DPEPO (10 wt% DPEPO co-deposited film); and the light emitting layer is CzAc It represents the relationship between the power efficiency and the luminance characteristics of organic EL elements of −26 DPPM: mCP (10 wt% mCP co-deposited film) and CzAc-26DPPM: DPEPO (10 wt% DPEPO co-deposited film). FIG. 50C shows the external quantum efficiency-luminance of the organic EL device in which the light emitting layer is Ac-46DPPM: mCP (10 wt% mCP co-deposited film) and Ac-46DPPM: DPEPO (10 wt% DPEPO co-deposited film). Relationship of characteristics; Relationship between external quantum efficiency and luminance characteristics of organic EL elements in which the light emitting layer is Ac-26DPPM: mCP (10 wt% mCP co-deposited film) and Ac-26DPPM: DPEPO (10 wt% DPEPO co-deposited film); The relationship of the external quantum efficiency of the organic EL element which made the light emitting layer CzAc-26DPPM: mCP (10 wt% mCP co-deposited film) and CzAc-26DPPM: DPEPO (10 wt% DPEPO co-deposited film) is represented. FIG. 51 is an energy diagram of the hole transport layer, the light-emitting layer, and the electron-transport layer when the light-emitting layer is AC-1MHPM, AC-2MHPM, or AC-3MHPM (each 20 wt% DPEPO co-deposited film). FIG. 52 is a diagram illustrating an EL spectrum of an organic EL element in which the light-emitting layer is AC-1MHPM, AC-2MHPM, or AC-3MHPM (each 20 wt% DPEPO co-deposited film). FIG. 53A shows the relationship between the current density-voltage-luminance characteristics of an organic EL element in which the light emitting layer is AC-1 MHPM, AC-2 MHPM, or AC-3 MHPM (each 20 wt% DPEPO co-deposited film). 53 (b) shows the relationship between the external quantum efficiency and the luminance characteristics of an organic EL element in which the light emitting layer is AC-1MHPM, AC-2MHPM, or AC-3MHPM (each 20 wt% DPEPO co-deposited film). c) represents the relationship between the power efficiency and the luminance characteristics of the organic EL element in which the light emitting layer is AC-1 MHPM, AC-2 MHPM, or AC-3 MHPM (each 20 wt% DPEPO co-deposited film). FIG. 54 is a diagram showing a typical configuration of an organic EL element.

Hereinafter, the present invention will be described in detail.
[Pyrimidine derivatives]
The pyrimidine derivative of the present invention is represented by the following general formula (1), and the energy difference (ΔE _ST ) between the excited singlet energy (E _S1 ) and the triplet excited energy (E _T1 ) is 0.25 eV. It is as follows.

In the general formula (1), R ¹ represents a hydrogen atom, an aryl group, an alkyl group, an alkoxy group, a thioalkoxy group, an amino group, a cyano group, a carbonyl group, or a sulfonyl group. Specifically, the aryl group includes a phenyl group, a biphenyl group, a terphenyl group, a pyridyl group, a terpyridyl group, and a naphthyl group, and the alkyl group includes a methyl group, an ethyl group, a 1-propyl group, and a 2-propyl group. The alkoxy group includes a methoxy group and an ethoxy group, the thioalkoxy group includes a thiomethyl group and a thioethyl group, and the amino group includes a dimethylamino group, a diethylamino group, and a cyclic piperidyl group. The carbonyl group includes an acetyl group and a benzophenone group, and the sulfonyl group includes a methylsulfonyl group and a phenylsulfonyl group.
R ⁸ represents a methyl group, an aryl group, an alkoxy group, an acyl group or a cyano group. Specifically, the aryl group and the alkoxy group include the same groups as those in R ¹ , and the acyl group includes an acetyl group.

  The substituent D represents a hydrogen atom or an electron donating group. Examples of the electron donating group include an acridinyl group, a 9,10-dihydro-9,9-dimethylacridinyl group, a phenazacillinyl group, and a triarylamine group.

n is an integer of 1 to 3. By having 1 to 3 phenyl groups having the substituent D in the general formula (1), in the pyrimidine derivative represented by the general formula (1), electrons are appropriately supplied to the pyrimidine skeleton that is a light emitting site. The energy difference (ΔE _ST ) between the singlet and the triplet can be reduced.

  When n is 2 or 3, the phenyl groups having the substituent D have a symmetric structure or an asymmetric structure with respect to each other. In addition, these groups may have substituents, such as an alkoxy group, a thioalkoxy group, and an alkyl group, in the range which does not impair the effect of this invention.

上記一般式（２）中、Ｒ¹及びＲ⁸は、一般式（１）におけるＲ¹について上記したとおりである。
置換基Ｄはそれぞれ独立に、下記一般式（３）で表される置換基のいずれかを表す。すなわち、置換基Ｄは、アクリジン骨格、カルバゾール骨格、又はこれらの誘導体骨格（例えば、ジメチルアクリジン誘導体、フェナザシリン誘導体、スピロアクリジンフルオレン誘導体、又はスピロアクリジンキサンテン誘導体等）を含む置換基である。

More specifically, the pyrimidine derivative represented by the general formula (1) is represented by the following general formula (2).

In the general formula (2), R ¹ and R ⁸ are as described above for R ¹ in the general formula (1).
The substituents D each independently represent any of the substituents represented by the following general formula (3). That is, the substituent D is a substituent including an acridine skeleton, a carbazole skeleton, or a derivative skeleton thereof (for example, a dimethylacridine derivative, a phenazacillin derivative, a spiroacridine fluorene derivative, or a spiroacridine xanthene derivative).

In the general formula (3), R ^{2 to} R ⁷ each independently represents a hydrogen atom, an alkyl group or an aryl group, and X represents a methylene group, —CR ^a R ^b —, —O— (ether bond), —S— (sulfide bond) or —S (═O) ₂ — (sulfonyl group) is represented, and R ^a and R ^b may be linked to each other to form a ring.

In R ^{2 to} R ⁷ , specifically, an aryl group includes a phenyl group, a biphenyl group, a terphenyl group, a pyridyl group, a terpyridyl group, and a naphthyl group, and an alkyl group includes a methyl group, an ethyl group, 1- Propyl group and 2-propyl group are included, alkoxy group is methoxy group and ethoxy group, thioalkoxy group is thiomethyl group and thioethyl group, amino group is dimethylamino group, diethylamino group, and Examples include cyclic piperidyl groups, carbonyl groups include acetyl groups and benzophenone groups, and sulfonyl groups include methylsulfonyl groups and phenylsulfonyl groups. Of these, the aryl group is preferably a phenyl group and a naphthyl group, the alkyl group is preferably a methyl group, an ethyl group, a 1-propyl group and a 2-propyl group, and the alkoxy group is a methoxy group and an ethoxy group. The thioalkoxy group is preferably a thiomethoxy group and a thioethoxy group, the amino group is preferably a dimethylamino group and a piperidyl group, the carbonyl group is preferably a ketone group and a benzophenone group, and the sulfonyl group is a methyl group. A sulfonyl group and a phenylsulfonyl group are preferred.

Specific examples of —CR ^a R ^b — in X include a dimethylmethylene group, a diphenylmethylene group, a ditolylmethylene group, and a dipyridylmethylene group. R ^a and R ^b may be linked to each other to form, for example, a 5- to 7-membered ring such as cyclopentene, cyclohexane, and cycloheptane, and these rings do not impair the effects of the present invention. For example, it may have a substituent such as an alkoxy group, a thioalkoxy group, a carbonyl group, and an ester group.

The substituent D in the general formula (2) is a dimethylacridine derivative (R ^a and R ^b are methyl groups) or a substituent containing a carbazole skeleton from the viewpoint that both have high triplet energy. preferable.

The pyrimidine derivative represented by the general formula (1) or (2) is more preferably represented by the following structural formula.

The pyrimidine derivative represented by the general formula (1) or (2) is particularly preferably represented by the following structural formula.

The pyrimidine derivative represented by the general formula (1) or (2) can be produced by various known methods. For example, Ac-PPM can be produced using a Suzuki-Miyaura coupling reaction.

  That is, by putting DMAC-Bpin and 4,6-dichloro-2-phenylpyrimidine in a four-necked flask and heating and refluxing with a base such as potassium carbonate in the presence of a Pd (0) catalyst and a ligand, It can be synthesized with a yield of 67%.

  However, the pyrimidine derivative represented by the general formula (1) or (2) is not limited to the above method and can be produced by combining various known methods.

The pyrimidine derivative represented by the general formula (1) of the present invention obtained as described above has an energy difference (ΔE _ST ) between the excited singlet energy (E _S1 ) and the triplet excited energy (E _T1 ). Is 0.25 eV or less and has high emission quantum efficiency. The energy difference (ΔE _ST ) between such excited singlet energy (E _S1 ) and triplet excitation energy (E _T1 ) is measured, for example, at a low temperature (5 K) and a normal temperature (300 K), The excitation singlet energy (E _S1 ) and triplet excitation energy (E _T1 ) are estimated from the rise of the phosphorescence spectrum observed at low temperature (5K) and the rise of the fluorescence emission spectrum observed at room temperature (300K), respectively. The excitation singlet energy (E _S1 ) is subtracted from the triplet excitation energy (E _T1 ). In the pyrimidine derivative, a pyrimidine skeleton that is a light emitting site has a phenyl group having a substituent D, specifically, an electron donating site having a carbazole site, an acridine site, a dimethylacridine derivative, or the like as the substituent D. By introducing it, a reverse intersystem crossing from a triplet exciton to a singlet exciton occurs, and upconversion emission can be observed. Therefore, the pyrimidine derivative is suitable as a thermally activated delayed fluorescence (TADF) material.
Further, in the pyrimidine derivative, the pyrimidine skeleton and the carbazole moiety, the dimethylacridine moiety, and the dimethylacridine derivative moiety, which are the substituent D, each have a high triplet energy (E _T1 ), and the energy of HOMO and LUMO. The difference (ΔE _HL ) gap tends to increase. For this reason, the pyrimidine derivative can be expected to emit blue light, which is an emission color in a short wavelength region.

[Light emitting material / organic EL element]
The light emitting material of the present invention comprises the above pyrimidine derivative.
The organic EL device of the present invention uses the above pyrimidine derivative.
Here, FIG. 45 shows a typical layer structure of the organic EL element.
The organic EL element typically has, for example, an ITO film formed on the substrate 1 as the anode 2, and a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer formed thereon. A layer and a cathode are laminated in this order.

  The substrate 1 is transparent and smooth and has a total light transmittance of at least 70%. Specifically, the substrate 1 is a flexible transparent substrate such as a glass substrate having a thickness of several μm or a special transparent substrate. Plastic or the like is used.

Thin films such as the anode 2, the hole injection layer 3, the hole transport layer 4, the light emitting layer 5, the electron transport layer 6, the electron injection layer 7 and the cathode 8 formed on the substrate are laminated by a vacuum deposition method or a coating method. Is done. When using a vacuum vapor deposition method, the deposited material is usually heated in an atmosphere reduced to 10 ⁻³ Pa or lower. The thickness of each layer varies depending on the type of layer and the material used, but usually the anode 2 and the cathode 8 are about 100 nm, and the other layers including the light emitting layer 5 are less than 50 nm. The electron injection layer 7 or the like may be formed with a thickness of 1 nm or less, for example.

  The anode 2 has a large work function and a total light transmittance of usually 80% or more. Specifically, in order to transmit light emitted from the anode 2, transparent conductive ceramics such as ITO and ZnO, transparent conductive polymers such as PEDOT / PSS and polyaniline, and other transparent conductive materials are used. The film thickness of the anode 2 is usually 10 to 200 nm.

  In the light emitting layer 5, like the other light emitting layers used in the organic EL device, it is preferable to use a host compound together with the pyrimidine derivative which is the light emitting material of the present invention. The host compound is not particularly limited as long as it does not impair the emission characteristics based on fluorescence and TADF. For example, DPEPO, PO9, 4,4′-bis (N-carbazolyl) -1,1′-biphenyl ( CBP), 2,8-bis (diphenylphosphoryl) dibenzothiophene (PPT), adamantane anthracene (Ad-Ant), rubrene, and 2,2′-bi (9,10-diphenylanthracene) (TPBA). It is done. In the components constituting the light emitting layer 5, the content of the light emitting material (pyrimidine derivative) and the host compound of the present invention is usually 1 to 50 wt%, preferably 5 to 10 wt%.

  In order to efficiently transport holes from the anode 2 to the light emitting layer, a hole transport layer 4 is provided between the anode 2 and the light emitting layer 5. Examples of the hole transport material forming the hole transport layer 4 include TAPC, N, N′-diphenyl-N, N′-di (m-tolyl) benzidine (TPD), N, N′-di (1 -Naphthyl) -N, N′-diphenylbenzidine (α-NPD), 4,4 ′, 4 ″ tri-9-carbazolyltriphenylamine (TCTA) and 4,4 ′, 4 ″ tris [phenyl ( m-tolyl) amino] triphenylamine and the like.

An electron transport layer 6 is provided between the cathode 8 and the light emitting layer 5 in order to efficiently transport electrons from the cathode to the light emitting layer. Examples of the electron transport material forming the electron transport layer 6 include B3PymPm, 2- (4-biphenylyl) -5- (pt-butylphenyl) -1,3,4-oxadiazole (tBu-PBD). 1,3-bis [5- (4-t-butylphenyl) -2- [1,3,4] oxadiazolyl] benzene (OXD-7), 3- (biphenyl-4-yl) -5- (4 -T-butylphenyl) -4-phenyl-4H-1,2,4-triazole (TAZ), bathocuproine (BCP), 1,3,5-tris (1-phenyl-1H-benzimidazol-2-yl) Examples include benzene (TPBi).
In addition to the above layers, a hole injection layer 3 and an electron injection layer 7, and a layer such as a hole blocking layer, an electron blocking layer, and an exciton blocking layer are formed as necessary.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not restrict | limited by the following Example.

[Synthesis of Pyrimidine Derivatives Represented by General Formula (1)]
The equipment and measurement conditions used for the identification of the composites are as follows.
(1) ¹ H nuclear magnetic resonance (NMR) apparatus JEOL Ltd. (400 MHz) JNM-EX270FT-NMR type (2) mass spectrometry (MS) apparatus JEOL Ltd. JMS-K9 [desktop GCQMS] and Waters Co., Ltd. Zspray (SQ detector 2))
(3) Sublimation purification equipment (i) Temperature gradient electric furnace, model: NPF80-500 type, company name: Cosmo Tech Co., Ltd.
(Ii) Thermal constant flow rate device, model: MC-1A, company name: Coflock Co., Ltd.
(Iii) Rotary pump, model: GLD-136C, company name: ULVAC Kiko Co., Ltd.
(4) Elemental analyzer Perkin Elmer 2400II CHNS / O analyzer Measurement mode: CHN mode

[Example 1] Synthesis of Ac-PPM To a 50 ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a reflux tube, DMAC-Bpin (1.42 g, 3.45 mmol), 4,6-dichloro-2- Phenylpyrimidine (0.39 g, 1.73 mmol), 1.35 M tripotassium phosphate (K ₃ PO ₄ ) solution (6.4 ml, 8.63 mmol), and dehydrated dioxane (30 ml) were added and nitrogen bubbling for 1 hour. Went. Tris (dibenzylideneacetone) dipalladium (0) (Pb ₂ (dba) ₃ ) (160 mg, 0.17 mmol) and 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (Sphos) (70 mg, 0 .17 mmol) was added and the reaction was carried out under reflux. The reaction solution changed from a reddish brown clear solution to a yellow clear solution. After 2 hours, the reaction was complete. The reaction crude product was dissolved in tetrahydrofuran (THF), filtered with suction, evaporated to remove THF, and redissolved in 200 ml of chloroform. Separation washing was performed 3 times with 200 ml of saline. Purification was performed by silica gel column chromatography. Chloroform was used for each of the injection solvent and the developing solvent. After purification, it was confirmed by thin layer chromatography (TLC) that only the target product spot was observed. After evaporation to remove chloroform, washing with methanol and suction filtration gave a yellow white solid. The yield was 0.82 g, and the yield was 67%. After vacuum drying, ¹ H-NMR and MS were measured.

The results of ¹ H-NMR and MS of Ac-PPM are shown below.
¹ H-NMR (CDCl 3, δ in ppm): 8.80 (dd, 2H), 8.60 (d, 4H, J = 8.8 Hz), 8.20 (s, 1H), 7.59-7 .56 (m, 7H), 7.49 (dd, 4H, J = 9.6 Hz), 7.02-6.94 (m, 8H), 6.38 (dd, 4H, J = 9.6 Hz)
EIMS: m / z = 724 [M ⁺ ]

  0.72 g of the obtained product was purified by sublimation under conditions of nitrogen gas 70 ml / min, high temperature part 370 ° C., low temperature part 185 ° C. to obtain yellow acicular crystals. The yield was 0.39 g, and the yield was 54%.

Elemental analysis of the target product after purification was performed.
Anal. _{Calcd for C 52 H 42 N 4} ; C, 86.39%; H, 5.86%; N, 7.75%. Found: C, 86.19%; H, 5.81%; N, 7.78%
The error between the theoretical value and the measured value was within 0.3% for all elements, and it was confirmed that the target product could be sufficiently purified.

[Example 2] Synthesis of BAc-MPM In a 25 mL four-necked flask equipped with a thermometer, a nitrogen inlet tube and a reflux tube, 4,6-bis (3,5-dichlorophenyl) -2-methylpyrimidine (BDCPMPM) 0 .77 g (2.0 mmol), 1.67 g (8.0 mmol) of dimethylacetamide (DMAC), 1.73 g (18 mmol) of sodium t-butoxide (NatBuO), and 25 mL of xylene were added, and nitrogen bubbling was performed for 45 minutes. Thereafter, 90 mg (0.40 mmol) of palladium (II) acetate (Pd (OAc) ₂ ) and 0.28 ml (1.2 mmol) of tri-t-butylphosphine ((tBu) ₃ P) were added and heated to 140 ° C. Reflux for 1 hour. The disappearance of the raw materials and the production of the target product were confirmed by TLC, and the reaction was terminated (brown transparent solution). After returning to room temperature, suction filtration was performed, followed by separation and washing twice with 50 mL of water and once with 50 mL of brine, dehydrated using anhydrous sodium sulfate, and then concentrated. The product was purified by silica gel chromatography (silica gel; 600 cc, developing solvent; hexane: dichloromethane = 1: 1), and the fraction of interest was collected and concentrated. The yield was 1.66 g, and the yield was 76.9%.

The results of ¹ H-NMR and MS of BAc-MPM are shown below.
¹ H-NMR (CDCl ₃ , δ in ppm): 8.33 (s, 4H, J = 1.0), 7.95 (s, 1H), 7.46 (m, 10H), 6.95 ( m, 16H), 6.44 (d, 8H, J = 4.4), 2.80 (s, 3H), 1.671 (s, 24H)
EIMS: 1075 [M ⁺ ]

Example 3 Synthesis of BCz-MPM 4,6-bis (3,5-dichlorophenyl) -2-methylpyrimidine (BDCPMPM) 0 was added to a 25 mL four-necked flask equipped with a thermometer, a nitrogen inlet tube and a reflux tube. .84 g (2.2 mmol), carbazole (Cz) 1.47 g (8.8 mmol), potassium carbonate (K ₂ CO ₃ ) 2.74 g (19.8 mmol), and xylene 25 mL were added, and nitrogen was bubbled for 40 minutes. Thereafter, 99 mg (0.44 mmol) of palladium (II) acetate (Pd (OAc) ₂ ) and 310 μL (1.32 mmol) of tri-t-butylphosphine ((tBu) ₃ P) were added and heated to 140 ° C. Reflux for hours. The purification of the target product was confirmed by TLC, and the reaction was terminated. After returning to room temperature (dark brown solution), suction filtration was performed, followed by separation and washing twice with 100 mL of water and once with 100 mL of brine, dehydrated using anhydrous sodium sulfate, and then concentrated. Since Cz as a raw material was also confirmed on TLC, it was purified by silica gel chromatography (silica gel; 400 cc, developing solvent; hexane: dichloromethane = 1: 1), and a fraction containing only the target product was collected, concentrated, and orange. A white powder was obtained.

The results of ¹ H-NMR and MS of BCz-MPM are shown below.
¹ H-NMR (DMSO-d ₆ , δ in ppm): 8.84 (s, 5H), 8.26 (d, 8H, J = 4.0), 8.04 (s, 2H), 7. 60 (d, 8H, J = 4.2), 7.47 (t, 8H, J = 7.6), 7.30 (t, 8H, J = 5.8), 2.74 (s, 3H )
EIMS: m / z = 907 [M ⁺ ]

  0.65 g of the obtained product was purified by sublimation under conditions of nitrogen gas 70 ml / min, high temperature part 380 ° C., low temperature part 190 ° C. to obtain yellow needle crystals. The yield was 0.136 g, and the yield was 26%.

[Example 4] Synthesis of Ac-MPM Ac-MPM was synthesized in the same manner as in Example 1 as a pyrimidine derivative represented by the general formula (1).

[Example 5] Synthesis of Ac-HPM As a pyrimidine derivative represented by the general formula (1), Ac-HPM was synthesized in the same manner as in Example 1.

[Example 6] Synthesis of Ac-SPM

(I) Synthesis of SMPMPhCl In a 500 ml four-necked flask equipped with a reflux tube and a thermometer, SMPMCl (4.86 g, 25 mmol), 4-chlorophenylboronic acid (8.6 g, 55 mmol), 1M Na ₂ CO ₃ aqueous solution ( 13.3 ml, 125 mmol), 350 ml of acetonitrile, and 125 ml of water were added, and nitrogen bubbling was performed for 1 hour. Thereafter, PdCl ₂ (PPh ₃ ) ₂ (700 mg, 1.25 mmol) was added, and the reaction was performed under reflux. The reaction solution was a yellow transparent solution. After 1 hour, an orange solid had precipitated, and it was confirmed by TLC that the raw material SMPMCl had disappeared, and the reaction was completed. Suction filtration was performed, and after washing with methanol, the filtrate was dissolved in 200 ml of chloroform. Washing was performed with water (100 ml × 3 times) and brine (150 ml × 1 time), followed by evaporation. In order to remove the catalyst, silica gel column chromatography was performed. Using a column with a diameter of 7 cm, 400 cc of silica gel (height 7 cm) was used. Chloroform was used for each of the injection solvent and the developing solvent. After purification, 7.3 g of a white solid was obtained, and the yield was 84%. The formation of SMPMPhCl (molecular weight 347) was confirmed by ¹ H-NMR and MS.

(Ii) Synthesis of Ac-SPM In a 25 ml four-necked flask equipped with a reflux tube and a thermometer, SMPMPhCl (1.04 g, 3 mmol), acridine (1.32 g, 6.3 mmol), and tBuONa (1.44 g, 15 mmol) ) Was added and a nitrogen flow for 15 minutes was performed. Thereafter, 50 ml of dehydrated xylene was added and nitrogen bubbling was performed for 1 hour. Pd (OAc) ₂ (34 mg, 0.15 mmol) and P (tBu) ₃ (0.11 ml, 0.45 mmol) were added, and then the reaction was performed under reflux conditions (140 ° C.). After the start of reflux, the reaction solution changed from an orange transparent solution to brown. After about 30 minutes, a green solid was deposited, and after 2 hours, it turned to brown. The disappearance of the raw material was confirmed by TLC. Suction filtration was performed with toluene washing, and the filtrate was dissolved in chloroform to recover the target product. Liquid separation washing was performed with 150 ml of water twice and 150 ml of brine once, and the mixture was concentrated by evaporation. After drying under reduced pressure, 0.75 g (yield 36%) of a yellow solid was obtained. Generation of Ac-SPM (molecular weight 693) was confirmed by ¹ H-NMR and MS.
The results of ¹ H-NMR of Ac-SPM are shown in FIG. 12, and the results of elemental analysis are shown below.

表１に示すとおり、実測値は許容誤差範囲（±０．３％以内）に収まっていることが確認された。

As shown in Table 1, it was confirmed that the measured values were within the allowable error range (within ± 0.3%).

[Example 7] Synthesis of Ac-NPM

(I) Synthesis of SOPMPhCl After placing 50 ml of methylene chloride in a 100 ml four-necked flask equipped with a reflux tube and a thermometer, the reaction vessel was cooled to 0 ° C. with ice water, and m-chloroperbenzoic acid (mCPBA) (5 .84 g, 22 mmol) was added. Thereafter, SPMPhCl (3.47 g, 10 mmol) dissolved in 50 ml of methylene chloride (CH ₂ Cl ₂ ) was slowly dropped with a dropping funnel and stirred at room temperature. After 1 hour, it was confirmed by TLC that the raw material SPMPhCl had disappeared, and the reaction was completed. The mixture was neutralized by adding 36 ml of an aqueous sodium hydrogen carbonate (NaHCO ₃ ) solution, washed with a separatory funnel with water 100 ml × 3 times and brine 150 ml × 1 time, and concentrated by evaporation. After being dispersed and washed with ethanol, drying under reduced pressure was performed to obtain 3.3 g (yield 87%) of a white solid. Generation of SOPMPhCl (molecular weight 379) was confirmed by ¹ H-NMR and MS.

(Ii) Synthesis of NPMPhCl 100 ml of SOPMPhCl (0.76 g, 2 mmol) and 1,4-dioxane were placed in a 100 ml four-necked flask equipped with a reflux tube and a thermometer. Then, piperidine (1.0 ml, 10 mmol) was added and stirred at 50 ° C. After 5 hours, the raw material SOPMPhCl had disappeared by TLC, so the reaction was terminated. Quenched by adding 100 ml of water. The mixture was extracted with ethyl acetate in a separatory funnel, washed with water (100 ml × 3 times) and brine (150 ml × 1 time), and evaporated. After being dispersed and washed with ethanol, drying under reduced pressure was performed to obtain 0.61 g of a yellow solid, and the yield was 79%. ^{From 1} H-NMR and MS, production of NPMPhCl (molecular weight 384) was confirmed.

(Iii) Synthesis of Ac-NPM In a 25 ml four-necked flask equipped with a reflux tube and a thermometer, NPMPhCl (1.04 g, 3 mmol), acridine (1.32 g, 6.3 mmol) and tBuONa (1.44 g, 15 mmol) Then, a nitrogen flow for 15 minutes was performed. Thereafter, dehydrated xylene (50 ml) was added and nitrogen bubbling was performed for 1 hour. After adding Pd (OAc) ₂ (34 mg, 0.15 mmol) and P (tBu) ₃ (0.11 ml, 0.45 mmol), the reaction was carried out at 140 ° C. under reflux conditions. After 2 hours, the solution turned brownish, and disappearance of the raw material was confirmed by TLC. After suction filtration, the object was caught on the filter paper. The filtrate was dissolved in chloroform and the target product was recovered. Liquid separation washing was performed with 150 ml of water twice and 150 ml of brine once, and the mixture was concentrated by evaporation. A column was extracted with a toluene solution. Then, after concentrating by evaporation, it was dispersed and washed with methanol and hexane and dried under reduced pressure to obtain 1.77 g of a yellow solid with a yield of 81%. Ac-NPM (molecular weight: 730) was identified as the target product from ¹ H-NMR and MS.
The results of elemental analysis of Ac-NPM are shown below.

表２に示すとおり、実測値は許容誤差範囲（±０．３％以内）に収まっていることが確認された。

As shown in Table 2, it was confirmed that the measured values were within the allowable error range (within ± 0.3%).

[Example 8] Synthesis of PXZ-PPM

(I) Synthesis of PPMPhCl In a 500 ml four-necked flask equipped with a reflux tube and a thermometer, PPMCl (5.63 g, 25 mmol), 4-chlorophenylboronic acid (8.6 g, 55 mmol), 1M sodium carbonate (Na ₂ CO ₃₎ ) Aqueous solution (13.3 ml, 125 mmol), 350 ml of acetonitrile, and 125 ml of water were added, and nitrogen bubbling was performed for 1 hour. Thereafter, PdCl ₂ (PPh ₃ ) ₂ (700 mg, 1.25 mmol) was added, and the reaction was performed under reflux. The reaction solution was a yellow transparent solution. After 2 hours, it was confirmed by TLC that the raw material SMPMCl had disappeared, and the reaction was completed. Suction filtration was performed, and after washing with methanol, the filtrate was dissolved in 200 ml of chloroform. The extract was washed with water (100 ml × 3 times) and brine (150 ml × 1 time) and concentrated by evaporation. Further, the catalyst was removed by silica gel column chromatography (silica gel; 400 cc (packed to a height of 7 cm)) using a column tube having a diameter of 8 cm. Chloroform was used as the injection solvent and the developing solvent. After purification, 8.3 g (yield 88%) of white solid was obtained. ^The product was identified by ¹ H-NMR and MS.

(Ii) Synthesis of PXZ-PPM In a 25 ml four-necked flask equipped with a reflux tube and a thermometer, PPPMPhCl (1.77 g, 4.6 mmol), phenoxazine (1.72 g, 9.4 mmol), and t-butoxy were added. Sodium (tBuONa) (2.4 g, 25 mmol) was added and a nitrogen flow for 15 minutes was performed. Thereafter, 80 ml of dehydrated xylene was added, and nitrogen bubbling was further performed for 1 hour. Pd (OAc) ₂ (56 mg, 0.25 mmol) and P (tBu) ₃ (0.18 ml, 0.75 mmol) were added thereto, and then reacted at 140 ° C. under reflux conditions. After the reaction for 9 hours, disappearance of the raw material was confirmed by TLC. Suction filtration was performed with toluene washing, and the filtrate was dissolved in chloroform to recover the target product. Liquid separation washing was performed with 150 ml of water twice and 150 ml of brine once, and the mixture was concentrated by evaporation. Subsequently, the catalyst was removed by silica gel column chromatography (silica gel; 400 cc (packed to a height of 7 cm)) using a column tube having a diameter of 8 cm. Chloroform was used as the injection solvent and the developing solvent. After evaporation, 1.5 g of a yellow solid was obtained. ^The product was identified by ¹ H-NMR and MS.

表３に示すとおり、実測値は許容誤差範囲（±０．３％以内）に収まっていることが確認された。 The result of ¹ H-NMR of PXZ-PPM is shown in FIG. 13, and the result of elemental analysis is shown below.

As shown in Table 3, it was confirmed that the measured values were within the allowable error range (within ± 0.3%).

[Example 9] Synthesis of Ac-MMPM

(I) Synthesis of MMPM-Cl In a 300 ml four-necked flask equipped with a reflux tube and a thermometer, MPM-Cl (1.63 g, 10 mmol), 4-chloro-2-methylphenylboronic acid (3.49 g, 20 0.5 mmol), 160 ml of acetonitrile, and 50 ml of 1M Na ₂ CO ₃ aqueous solution were added, and nitrogen bubbling was performed for 1 hour. Thereafter, PdCl ₂ (PPh ₃ ) ₂ (700 mg, 1.25 mmol) was added, and the reaction was performed under reflux. The reaction solution was a yellow transparent solution. After 2 hours, disappearance of the raw material was confirmed by TLC. After a while, an orange solid precipitated, and thus suction filtration was performed. After washing with methanol, the filtrate was dissolved in chloroform. The extract was washed with water (150 ml × 3 times) and brine (150 ml × 1 time), and concentrated by evaporation. Further, the catalyst was removed by silica gel column chromatography (silica gel; 150 cc) using a glass filter 17G-4. The injection solvent was toluene, and the developing solvent was hexane: ethyl acetate = 1: 1. After evaporation, 3.0 g of a white solid was obtained, and the yield was 84%. ^{From 1} H-NMR and MS, production of MMPM-Cl (molecular weight 343) was confirmed.

(Ii) Synthesis of Ac-MMPM In a 25 ml four-necked flask equipped with a reflux tube and a thermometer, MMPM-Cl (1.03 g, 3 mmol), acridine (1.32 g, 6.3 mmol), and tBuONa (1 .44 g, 15 mmol) was added followed by a 15 minute nitrogen flow. Thereafter, dehydrated xylene (50 ml) was added and nitrogen bubbling was performed for 1 hour. Pd (OAc) ₂ (34 mg, 0.15 mmol) and P (tBu) ₃ (0.11 ml, 0.45 mmol) were added, and the reaction was carried out under reflux conditions (140 ° C.). After 16 hours, disappearance of the raw material was confirmed by TLC. After suction filtration with toluene washing, 200 ml of toluene was added, followed by liquid separation washing with water 150 ml × 2 times and brine 150 ml × 2 times, and concentrated by evaporation. Subsequently, silica gel column chromatography (silica gel; 500 cc (packed up to a height of 10 cm)) was performed using a column having a diameter of 8 cm. Toluene was used as the injection solvent, and hexane: ethyl acetate = 1: 1 was used as the developing solvent. After evaporation, 1.35 g (65% yield) of a white pink solid was obtained. The production of Ac-MMPM (molecular weight 689) was confirmed by ¹ H-NMR and MS.

表４に示すとおり、実測値は許容誤差範囲（±０．３％以内）に収まっていることが確認された。 The results of ¹ H-NMR of Ac-MMPM are shown in FIG. 14, and the results of elemental analysis are shown below.

As shown in Table 4, it was confirmed that the measured values were within the allowable error range (within ± 0.3%).

[Example 10] Synthesis of Ac-46DPPM

(I) Synthesis of C46DPPM In a 100 mL four-necked flask, 2.13 g (8.0 mmol) of 2-chloro-4,6-diphenylpyrimidine (CDPPM), 1.25 g (8.0 mmol) of 4-chlorophenylboronic acid (CPB) Then, 1M sodium carbonate aqueous solution in which 2.54 g (24 mmol) of sodium carbonate was dissolved in 24 mL of water and 70 mL of acetonitrile were added, and nitrogen bubbling was performed for 35 minutes. Thereafter, 281 mg (0.40 mmol) of bis (triphenylphosphine) palladium dichloride (PdCl ₂ (PPh ₃ ) ₂ ) was added, and the mixture was heated to reflux at 80 ° C. for 1 hour. After confirming the formation of the target product and disappearance of the raw materials by TLC, the reaction was terminated and the temperature was returned to room temperature. The black solid was separated by suction filtration and purified by silica gel chromatography (silica gel; 500 cc, developing solvent; hexane: ethyl acetate = 10: 1 (vol / vol)), and 2.45 g of white crystalline powder ( Yield 90.1%). Generation of C46DPPM (molecular weight 343) was confirmed by ¹ H-NMR and MS.

(Ii) Synthesis of Ac-46DPPM In a 25 mL four-necked flask, 1.37 g (4.0 mmol) of 2- (4-chlorophenyl) -4,6-diphenylpyrimidine (C46DPPM), 0.84 g of dimethylacridine (DMAC) (4 0.0 mmol), 1.66 g (12 mmol) of anhydrous sodium carbonate, and 25 mL of dehydrated xylene were added, and nitrogen bubbling was performed for 60 minutes. Thereafter, 45 mg (0.20 mmol) of palladium acetate and 174 mg (0.60 mmol) of tri-t-butylphosphonium tetrafluoroborate ([(t-Bu) ₃ PH] BF ₄ ) were added and heated to 140 ° C., 18 Heated to reflux for hours. The disappearance of the raw materials and the production of the target product were confirmed by TLC, and the reaction was terminated and returned to room temperature. The catalyst was removed by suction filtration, and the filtrate was washed with water and saturated brine, dehydrated with magnesium sulfate, and concentrated through a filter paper. Recrystallization from toluene gave 1.67 g (yield: 81.5%) of a pale yellow crystalline solid. Generation of Ac-46DPPM (molecular weight 513) was confirmed by ¹ H-NMR and MS.

表５に示すとおり、実測値は許容誤差範囲（±０．３％以内）に収まっていることが確認された。 The results of ¹ H-NMR of Ac-46DPPM are shown in FIG. 15, and the results of elemental analysis are shown below.

As shown in Table 5, it was confirmed that the measured values were within the allowable error range (within ± 0.3%).

温度計、窒素導入管及び還流管を付けた２５ｍＬ四口フラスコに、４−（４−ブロモフェニル）−２，６−ジフェニルピリミジン（Ｂ２６ＤＰＰＭ）１．５５ｇ（４．０ｍｍｏｌ）、ジメチルアクリジン（ＤＭＡＣ）０．８４ｇ（４．０ｍｍｏｏｌ）、炭酸カリウム（Ｋ₂ＣＯ₃）１．６６ｇ（１２ｍｍｏｌ）、及びキシレン２５ｍＬ加え、４０分間窒素バブリングした。次いで、Ｐｄ（ＯＡｃ）₂ ４５ｍｇ（０．２０ｍｍｏｌ）及び［（^tＢｕ）_３ＰＨ］ＢＦ₄ １７４ｍｇ（０．６０ｍｍｏｌ）加え、１６時間加熱還流した。ＴＬＣにて原料の消費及び目的物の生成を確認し、反応を終了し、室温に戻した（濃茶色透明溶液）。室温に戻した後、吸引ろ過を行い、ろ液を分液（水１００ｍＬ×２、食塩水１００ｍＬ）し、Ｎａ₂ＳＯ₄脱水、濃縮した。その後、触媒を除去するため、シリカゲルクロマトグラフィー（シリカゲル；４００ｃｃ、展開溶媒；ヘキサン：ジクロロメタン＝２：１（ｖｏｌ／ｖｏｌ））にて精製、目的物のみのフラクションを回収、濃縮した。その後、メタノールにて分散洗浄を行い、純度の高い薄黄色固体を１．９８ｇ得、収率は９６．６％となった。¹Ｈ−ＮＭＲ及びＭＳより、Ａｃ−２６ＤＰＰＭ（分子量５１３）の生成を確認した。 [Example 11] Synthesis of Ac-26DPPM

In a 25 mL four-necked flask equipped with a thermometer, a nitrogen inlet tube and a reflux tube, 1.55 g (4.0 mmol) of 4- (4-bromophenyl) -2,6-diphenylpyrimidine (B26DPPM), dimethylacridine (DMAC) 0.84 g (4.0 mmol), 1.66 g (12 mmol) of potassium carbonate (K ₂ CO ₃ ), and 25 mL of xylene were added, and nitrogen was bubbled for 40 minutes. Then added _{Pd (OAc) 2 45mg (0.20mmol} ) and _{^{[(t Bu) 3 PH]}} BF 4 174mg (0.60mmol), was heated at reflux for 16 hours. The consumption of the raw materials and the production of the target product were confirmed by TLC, and the reaction was terminated and the temperature was returned to room temperature (dark brown transparent solution). After returning to room temperature, suction filtration was performed, and the filtrate was separated (water 100 mL × 2, brine 100 mL), dried over Na ₂ SO ₄ and concentrated. Thereafter, in order to remove the catalyst, purification was performed by silica gel chromatography (silica gel; 400 cc, developing solvent; hexane: dichloromethane = 2: 1 (vol / vol)), and a fraction containing only the target product was collected and concentrated. Thereafter, dispersion washing was performed with methanol to obtain 1.98 g of a light yellow solid with high purity, and the yield was 96.6%. Formation of Ac-26DPPM (molecular weight 513) was confirmed by ¹ H-NMR and MS.

表６に示すとおり、実測値は許容誤差範囲（±０．３％以内）に収まっていることが確認された。 The elemental analysis results of Ac-26DPPM are shown below.

As shown in Table 6, it was confirmed that the measured values were within the allowable error range (within ± 0.3%).

[Example 12] Synthesis of CzAc-26DPPM

(I) Synthesis of Ac-Cl To a 100 mL four-necked flask equipped with a nitrogen introduction tube, a thermometer and a reflux tube, 2.87 g (15 mmol) of DMAC, 3.14 g (15 mmol) of 1-bromo-4-chlorobenzene, K ₂ 4.15 g (30 mmol) of CO ₃ and 100 mL of xylene were added, and nitrogen bubbling was performed for 60 minutes. Then placed _{Pd (OAc) 2 168mg (0.75mmol} ) and _{^{[(t Bu) 3 PH]}} BF 4 653mg (2.25mmol), was heated under reflux for 32 hours. The formation of the target product was confirmed by TLC, and the reaction was completed (dark brown solution). After returning to room temperature, the reaction solution was separated into a filtrate and a filtrate by suction filtration, and the filtrate was separated (water 100 mL × 2, brine 100 mL), Na ₂ SO ₄ dehydrated and concentrated. Thereafter, the catalyst and the like were removed by silica gel chromatography, concentrated, subjected to methanol dispersion washing, and dried under reduced pressure to obtain 2.88 g (yield 60%) of a pale yellow solid. Formation of Ac-Cl (molecular weight 320) was confirmed by ¹ H-NMR and MS.

(Ii) Synthesis of DBAc-Cl In a 100 mL three-necked flask equipped with a 100 mL dropping funnel, a nitrogen introduction tube and a thermometer, 2.88 g (9.0 mmol) of Ac-Cl and 25 mL of methylene chloride (CH ₂ Cl ₂ ) were added, and nitrogen was used for a while. Flowed. Next, a solution obtained by dissolving 3.20 g (18 mmol) of N-bromosuccinimide (NBS) in 75 mL of methylene chloride was placed in a 100 mL dropping funnel. The N-bromosuccinimide solution was added dropwise over 1 hour and 25 minutes while cooling the three-necked flask in a 0 ° C. water bath. The reaction solution after the dropping was a golden transparent solution. As confirmed by TLC, the raw material was consumed and the target product was produced, but there were spots that were thought to be due to the mono-substituted product. Therefore, in order to consume the mono-substituted product, when a solution in which 1.0 g of NBS was dissolved in 30 mL of methylene chloride was added using a dropping funnel, the spot of the mono-substituted product was slightly thinned. Here, the reaction was once stopped and liquid separation was performed. Thereafter, the concentrated mucus was used again for the reaction. A 100 mL four-necked flask was charged with 35 mL of mucilage and methylene chloride, and a 100 mL dropping funnel was charged with a solution of 2.0 g of NBS dissolved in 65 mL of methylene chloride. Thereafter, a methylene chloride solution of NBS was added dropwise over 50 minutes while cooling with a 0 ° C. water bath. After confirming the disappearance of the mono-substituted product and the formation of the target product by TLC, the reaction was completed (golden transparent solution). Next, the solution was separated (water 200 mL × 5), dried over Na ₂ SO ₄ and concentrated. Then, after purification and concentration by silica gel chromatography (silica gel; 600 cc, developing solvent; hexane: toluene = 10: 1), recrystallization was performed with a mixed solvent of hexane: toluene = 1: 1. 1.76 g of a springy crystalline solid was obtained. Further, the filtrate was concentrated and washed with methanol to obtain 1.75 g of a crystalline solid. A total of 3.51 g was obtained, and the yield was 81.6%. Formation of DBAc-Cl (molecular weight 478) was confirmed by ¹ H-NMR and MS.

(Iii) Synthesis of CzAc-Cl In a 100 mL four-necked flask equipped with a nitrogen introduction tube, a thermometer and a reflux tube, 3.34 g (7.0 mmol) of DBAc-Cl, 2.34 g (14 mmol) of carbazole (Cz), K ₂ CO ₃ 3.84 g (28 mmol) and xylene 100 mL were added and nitrogen bubbling was performed for 60 minutes. After bubbling, placed _{Pd (OAc) 2 79mg (0.35mmol} ) and _{^{[(t Bu) 3 PH]}} BF 4 305mg (1.05mmol), was heated to 110 ° C., refluxed for 89 hours. Although the disappearance of carbazole was not confirmed by TLC, the formation of the target product was confirmed and the reaction was completed (dark red brown solution). After returning to room temperature, suction filtration was performed, and the filtrate was separated (water 100 mL × 2, brine 100 mL), Na ₂ SO ₄ dehydrated and concentrated. Thereafter, the product was purified and concentrated by silica gel chromatography (silica gel; 800 cc, developing solvent; hexane: ethyl acetate = 20: 1), and then dispersed and washed with methanol to remove spots other than the target product. 3.52 g (yield 74.4%) of a pale yellow solid after drying under reduced pressure was obtained. Formation of CzAc-Cl (molecular weight: 650) was confirmed by ¹ H-NMR and MS.

(Iv) Synthesis of CzAc-Bpin To a 50 mL four-necked flask equipped with a nitrogen introduction tube, a thermometer and a reflux tube, 3.90 g (6.0 mmol) of CzAc-Cl, 1.83 g of bis (pinacolato) diboron (Bpin) ( 7.2 mmol) and 1.77 g (18 mmol) of potassium acetate (KOAc) were added, followed by nitrogen flow. Thereafter, 50 mL of dioxane was added, and nitrogen bubbling was performed for 90 minutes. After bubbling, 67 mg (0.30 mmol) of Pd (OAc) ₂ and 123 mg (0.30 mmol) of S-phos were added and heated to reflux for 1 hour. The formation of the target product was confirmed by TLC, and the reaction was completed (dark red brown transparent solution). After returning to room temperature, suction filtration was performed, and the filtrate was separated (water 100 mL × 2, brine 100 mL), Na ₂ SO ₄ dehydrated and concentrated. The residue of the raw material was removed with a glass filter (17G4, silica gel: 150 cc), the filtrate was concentrated, then dispersed and washed with methanol, and the filtrate was dried under reduced pressure. 3.47 g of a pale yellow solid after drying under reduced pressure was obtained, and the yield was 78.0%. Formation of CzAc-Bpin (molecular weight 742) was confirmed by ¹ H-NMR and MS.

(V) Synthesis of CzAc-26DPPM To a 25 mL four-necked flask equipped with a thermometer, a nitrogen introduction tube and a reflux tube, 0.53 g (2.0 mmol) of CzAc-Bpin, 4-chloro-2,6-diphenyl-pyrimidine ( C26PM) 1.48 g (2.0 mmol), 1.27 g (6.0 mmol) of K ₃ PO ₄ dissolved in 4.4 mL of water and 20 mL of dioxane were added, and nitrogen was bubbled for 40 minutes. Next, 183 mg (0.20 mmol) of Pd ₂ (dba) ₃ and 82 mg (0.20 mmol) of S-phos were added and heated to reflux for 2 hours. Since the consumption of the raw materials and the production of the target product were confirmed by TLC, the reaction was terminated and the temperature was returned to room temperature (a red-black transparent solution). After returning to room temperature, suction filtration was performed, and the filtrate was separated (water 100 mL × 2, brine 100 mL), dried over Na ₂ SO ₄ and concentrated. Thereafter, in order to remove the catalyst, purification was performed by silica gel chromatography (silica gel; 400 cc, developing solvent; hexane: dichloromethane = 2: 1 (vol / vol)), and a fraction containing only the target product was collected and concentrated. After concentration, dispersion washing was performed with methanol. Thereafter, reprecipitation and recrystallization were performed to finally obtain 0.765 g (yield 45.3%) of a yellow solid. Formation of CzAc-26DPPM (molecular weight 846) was confirmed by ¹ H-NMR and MS.

表７に示すように、実測値は許容誤差範囲（±０．３％以内）に収まっていることが確認された。
［実施例１３］Ａｃ−１ＭＨＰＭの合成

（ｉ）１ＭＨＰＭ−Ｃｌの合成
還流管及び温度計を付けた２００ｍｌの四口フラスコに４，６−ジクロロ−５−メチルピリミジン（１．４７ｇ、９ｍｍｏｌ）、４−クロロフェニルボロン酸（２．８１ｇ、１８ｍｍｏｌ）、アセトニトリル（１５０ｍｌ）、１Ｍ炭酸ナトリウム（Ｋ₂ＣＯ₃）水溶液（４５ｍｌ）を入れ、１時間の窒素バブリングを行った。その後、ＰｄＣｌ₂（ＰＰｈ₃）₂（３２０ｍｇ、０．４５ｍｍｏｌ）を入れ、還流下で反応を行った。４時間後、ＴＬＣにより原料の消失が確認された。吸引濾過を行い、水で洗浄後、ろ物をクロロホルムに溶解させ、水１５０ｍｌ×３回、塩水１５０ｍｌ×３回で洗浄し、エバポレーションを行った。また、触媒を抜くために、ガラスフィルター１７Ｇ−４を使用し抜きカラムを行った。シリカゲルを１５０ｃｃ使用し、インジェクション溶媒はトルエン、展開溶媒はヘキサン：酢酸エチル＝１０：３（ｖｏｌ／ｖｏｌ）を使用した。エバポレーション後、白色固体が１．２７ｇ得られ、収率は３２％であった。¹Ｈ−ＮＭＲ及びＭＳより、１ＭＨＰＭ−Ｃｌ（分子量３１５）の生成を確認した。
（ii）Ａｃ−１ＭＨＰＭの合成
還流管及び温度計を付けた５０ｍｌの四口フラスコに１ＭＨＰＭ−Ｃｌ（０．８８ｇ、２．８ｍｍｏｌ）、９,１０−ジヒドロ−９，９−ジメチルアクリジン（１．２３ｇ、５．９ｍｍｏｌ）、ｔＢｕＯＮａ（１．３４ｇ、１４ｍｍｏｌ）を入れた後、１５分間の窒素フローを行った。その後、脱水キシレン（５０ｍｌ）を入れ、窒素バブリングを１時間行った。Ｐｄ（ＯＡｃ）₂（３２ｍｇ、０．１４ｍｍｏｌ）、Ｐ（ｔＢｕ）₃（０．１ｍｌ、０．４２ｍｍｏｌ）を入れた後、還流条件下（１４０℃）で反応を行った。６時間反応後、ＴＬＣにより原料の消失が確認された。トルエン洗浄にて吸引濾過した後、トルエン１５０ｍｌを加え、水１５０ｍｌ×３回、塩水１５０ｍｌ×３回にて分液洗浄を行い、エバポレーションにて濃縮した。次いで、シリカゲルカラムクロマトグラフィーを行った。直径８ｃｍのカラムを用い、シリカゲルを５００ｃｃ（高さ１０ｃｍ）使用した。インジェクション溶媒はジクロロメタン、展開溶媒はヘキサン：酢酸エチル＝１０：２（ｖｏｌ／ｖｏｌ）を使用した。エバポレーション後、白色固体が１．４４ｇ得られ、収率は７８％であった。¹Ｈ−ＮＭＲ（図２１）及びＭＳより、Ａｃ−ＭＨＰＭ（分子量６６１）の生成を確認した。
Ａｃ−１ＭＨＰＭの元素分析結果を以下に示す。

表８に示すように、実測値は許容誤差範囲（±０．３％以内）に収まっていることが確認された。
［実施例１４］Ａｃ−２ＭＨＰＭの合成

（ｉ）２ＭＨＰＭ−Ｃｌの合成
還流管及び温度計を付けた３００ｍｌの四口フラスコに４，６−ジクロロピリミジン（１．３３ｇ、９ｍｍｏｌ）、４−クロロ―２−メチルフェニルボロン酸（３．０６ｇ、１８ｍｍｏｌ）、アセトニトリル（１５０ｍｌ）、１Ｍ炭酸ナトリウム（Ｎａ₂ＣＯ₃）水溶液（５０ｍｌ）を入れ、１時間の窒素バブリングを行った。その後、ＰｄＣｌ₂（ＰＰｈ₃）₂（３２０ｍｇ、０．４５ｍｍｏｌ）を入れ、還流下で反応を行った。反応溶液は黄色透明溶液であった。２時間後、ＴＬＣにより原料の消失が確認された。しばらくすると、オレンジ色固体が析出したため、吸引濾過を行い、メタノールで洗浄後、ろ物をクロロホルムに溶解させた。水１５０ｍｌ×３回、塩水１５０ｍｌ×１回で洗浄し、エバポレーションを行った。また、触媒を抜くために、シリカゲルカラムクロマトグラフィーを行った。ガラスフィルター１７Ｇ−４を使用し、シリカゲルを１５０ｃｃ使用した。インジェクション溶媒はトルエン、展開溶媒はヘキサン：酢酸エチル＝１：１（ｖｏｌ／ｖｏｌ）を使用した。エバポレーション後、白色固体が１．２７ｇ得られ、収率は４３％であった。¹Ｈ−ＮＭＲ及びＭＳより、２ＭＨＰＭ−Ｃｌ（分子量３２９）の生成を確認した。
（ii）Ａｃ−２ＭＨＰＭの合成
還流管及び温度計を付けた２５ｍｌの四口フラスコに２ＭＨＰＭ−Ｃｌ（０．９９ｇ、３ｍｍｏｌ）、９，１０−ジヒドロ−９，９−ジメチルアクリジン（１．３２ｇ、６．３ｍｍｏｌ）、ｔＢｕＯＮａ（１．４４ｇ、１５ｍｍｏｌ）を入れた後、１５分間の窒素フローを行った。その後、脱水キシレン（５０ｍｌ）を入れ、窒素バブリングを１時間行った。Ｐｄ（ＯＡｃ）₂（３４ｍｇ、０．１５ｍｍｏｌ）、Ｐ（ｔＢｕ）₃（０．１１ｍｌ、０．４５ｍｍｏｌ）を入れた後、還流条件下（１４０℃）で反応を行った。１１時間反応後、ＴＬＣにより原料の消失が確認された。トルエン洗浄にて吸引濾過した後、トルエン１５０ｍｌを加え、水１５０ｍｌ×３回、塩水１５０ｍｌ×３回にて分液洗浄を行い、エバポレーションにて濃縮した。次いで、シリカゲルカラムクロマトグラフィーを行った。直径８ｃｍのカラムを用い、シリカゲルを５００ｃｃ（高さ１０ｃｍ）使用した。インジェクション溶媒はジクロロメタン、展開溶媒はヘキサン：酢酸エチル＝１０：１（ｖｏｌ／ｖｏｌ）を使用した。エバポレーション後、黄白色固体が１．０１ｇ得られ、収率は５０％であった。¹Ｈ−ＮＭＲ（図２２）及びＭＳより、Ａｃ−２ＭＨＰＭ（分子量６７５）の生成を確認した。
Ａｃ−２ＭＨＰＭの元素分析結果を以下に示す。

表９に示すように、実測値は許容誤差範囲（±０．３％以内）に収まっていることが確認された。
［実施例１５］Ａｃ−３ＭＨＰＭの合成

（ｉ）３ＭＨＰＭ−Ｃｌの合成
還流管及び温度計を付けた３００ｍｌの四口フラスコに４，６−ジクロロ−５−メチルピリミジン（０．９８ｇ、６．０ｍｍｏｌ）、４−クロロ−２−メチルフェニルボロン酸（２．２４ｇ、１３．２ｍｍｏｌ）、アセトニトリル（１００ｍｌ）、１Ｍ炭酸ナトリウム（Ｎａ₂ＣＯ₃）（３０ｍｌ）を入れ、１時間の窒素バブリングを行った。その後、ＰｄＣｌ₂（ＰＰｈ₃）₂２１０ｍｇ、０．３ｍｍｏｌ）を入れ、還流下で反応を行った。反応溶液は黄色透明溶液であった。３時間後、ＴＬＣにより原料の消失が確認された。しばらくすると、オレンジ色固体が析出したため、吸引濾過を行い、メタノールで洗浄後、ろ物をクロロホルムに溶解させた。水１５０ｍｌ×３回、塩水１５０ｍｌ×１回で洗浄し、エバポレーションを行なった。また、触媒を抜くために、シリカゲルカラムクロマトグラフィーを行なった。ガラスフィルター１７Ｇ−４を使用し、シリカゲルを１５０ｃｃ使用した。インジェクション溶媒はトルエン、展開溶媒はヘキサン：酢酸エチル＝１０：３（ｖｏｌ／ｖｏｌ）を使用した。エバポレーション後、白色固体が１．０ｇ得られ、収率は４９％であった。¹Ｈ−ＮＭＲ及びＭＳより、３ＭＨＰＭ−Ｃｌ（分子量３４３）の生成を確認した。
（ii）Ａｃ−３ＭＨＰＭの合成
還流管及び温度計を付けた２５ｍｌの四口フラスコに３ＭＨＰＭ−Ｃｌ（１．０３ｇ、３ｍｍｏｌ）、９,１０−ジヒドロ−９,９−ジメチルアクリジン（１．３２ｇ、６．３ｍｍｏｌ）、ｔＢｕＯＮａ（１．４４ｇ、１５ｍｍｏｌ）を入れた後、１５分間の窒素フローを行った。その後、脱水キシレン（５０ｍｌ）を入れ、窒素バブリングを１時間行った。Ｐｄ（ＯＡｃ）₂（３４ｍｇ、０．１５ｍｍｏｌ）、Ｐ（ｔＢｕ）₃（０．１１ｍｌ、０．４５ｍｍｏｌ）を入れた後、還流条件下（１４０℃）で反応を行った。４時間反応後、ＴＬＣにより原料の消失が確認された。トルエン洗浄にて吸引濾過した後、トルエン１５０ｍｌを加え、水１５０ｍｌ×３回、塩水１５０ｍｌ×３回にて分液洗浄を行い、エバポレーションにて濃縮した。次いで、シリカゲルカラムクロマトグラフィーを行った。直径８ｃｍのカラムを用い、シリカゲルを５００ｃｃ（高さ１０ｃｍ）使用した。インジェクション溶媒はジクロロメタン、展開溶媒はヘキサン：酢酸エチル＝１０：１（ｖｏｌ／ｖｏｌ）を使用した。エバポレーション後、黄白色固体が１．２８ｇ得られ、収率は６２％であった。¹Ｈ−ＮＭＲ（図２３）及びＭＳより、Ａｃ−３ＭＨＰＭ（分子量６８９）の生成を確認した。
Ａｃ−３ＭＨＰＭの元素分析結果を以下に示す。

表１０に示すように、実測値は許容誤差範囲（±０．３％以内）に収まっていることが確認された。 The elemental analysis results of CzAc-26DPPM are shown below.

As shown in Table 7, it was confirmed that the measured values were within the allowable error range (within ± 0.3%).
[Example 13] Synthesis of Ac-1MHPM

(I) Synthesis of 1MHPM-Cl In a 200 ml four-necked flask equipped with a reflux tube and a thermometer, 4,6-dichloro-5-methylpyrimidine (1.47 g, 9 mmol), 4-chlorophenylboronic acid (2.81 g, 18 mmol), acetonitrile (150 ml), and 1M sodium carbonate (K ₂ CO ₃ ) aqueous solution (45 ml) were added, and nitrogen bubbling was performed for 1 hour. Thereafter, PdCl ₂ (PPh ₃ ) ₂ (320 mg, 0.45 mmol) was added, and the reaction was performed under reflux. After 4 hours, the disappearance of the raw material was confirmed by TLC. After suction filtration and washing with water, the filtrate was dissolved in chloroform, washed with water 150 ml × 3 times and brine 150 ml × 3 times, and evaporated. In order to remove the catalyst, a glass filter 17G-4 was used and a column was removed. 150 cc of silica gel was used, toluene was used as the injection solvent, and hexane: ethyl acetate = 10: 3 (vol / vol) was used as the developing solvent. After evaporation, 1.27 g of a white solid was obtained, and the yield was 32%. ^{From 1} H-NMR and MS, production of ¹ MHPM-Cl (molecular weight 315) was confirmed.
(Ii) Synthesis of Ac-1MHPM In a 50 ml four-necked flask equipped with a reflux tube and a thermometer, 1 MHPM-Cl (0.88 g, 2.8 mmol), 9,10-dihydro-9,9-dimethylacridine (1. 23 g, 5.9 mmol) and tBuONa (1.34 g, 14 mmol) were added, followed by a nitrogen flow for 15 minutes. Thereafter, dehydrated xylene (50 ml) was added and nitrogen bubbling was performed for 1 hour. After adding Pd (OAc) ₂ (32 mg, 0.14 mmol) and P (tBu) ₃ (0.1 ml, 0.42 mmol), the reaction was carried out under reflux conditions (140 ° C.). After the reaction for 6 hours, disappearance of the raw material was confirmed by TLC. After suction filtration with toluene washing, 150 ml of toluene was added, followed by liquid separation washing with water 150 ml × 3 times and brine 150 ml × 3 times, and concentrated by evaporation. Subsequently, silica gel column chromatography was performed. A column of 8 cm in diameter was used, and 500 cc of silica gel (height 10 cm) was used. The injection solvent was dichloromethane, and the developing solvent was hexane: ethyl acetate = 10: 2 (vol / vol). After evaporation, 1.44 g of a white solid was obtained, and the yield was 78%. Formation of Ac-MHPM (molecular weight 661) was confirmed by ¹ H-NMR (FIG. 21) and MS.
The elemental analysis results of Ac-1MHPM are shown below.

As shown in Table 8, it was confirmed that the measured values were within the allowable error range (within ± 0.3%).
[Example 14] Synthesis of Ac-2MHPM

(I) Synthesis of 2MHPM-Cl In a 300 ml four-necked flask equipped with a reflux tube and a thermometer, 4,6-dichloropyrimidine (1.33 g, 9 mmol), 4-chloro-2-methylphenylboronic acid (3.06 g) 18 mmol), acetonitrile (150 ml), and 1M aqueous sodium carbonate (Na ₂ CO ₃ ) solution (50 ml) were added, and nitrogen bubbling was performed for 1 hour. Thereafter, PdCl ₂ (PPh ₃ ) ₂ (320 mg, 0.45 mmol) was added, and the reaction was performed under reflux. The reaction solution was a yellow transparent solution. After 2 hours, the disappearance of the raw material was confirmed by TLC. After a while, an orange solid precipitated, and thus suction filtration was performed. After washing with methanol, the filtrate was dissolved in chloroform. Washing was performed with water (150 ml × 3 times) and brine (150 ml × 1 time), followed by evaporation. In order to remove the catalyst, silica gel column chromatography was performed. A glass filter 17G-4 was used and 150 cc of silica gel was used. The injection solvent was toluene, and the developing solvent was hexane: ethyl acetate = 1: 1 (vol / vol). After evaporation, 1.27 g of a white solid was obtained, and the yield was 43%. ^{From 1} H-NMR and MS, it was confirmed that 2MHPM-Cl (molecular weight: 329) was produced.
(Ii) Synthesis of Ac-2MHPM In a 25 ml four-necked flask equipped with a reflux tube and a thermometer, 2MHPM-Cl (0.99 g, 3 mmol), 9,10-dihydro-9,9-dimethylacridine (1.32 g, 6.3 mmol) and tBuONa (1.44 g, 15 mmol) were added followed by 15 minutes of nitrogen flow. Thereafter, dehydrated xylene (50 ml) was added and nitrogen bubbling was performed for 1 hour. Pd (OAc) ₂ (34 mg, 0.15 mmol) and P (tBu) ₃ (0.11 ml, 0.45 mmol) were added, and then the reaction was performed under reflux conditions (140 ° C.). After the reaction for 11 hours, disappearance of the raw material was confirmed by TLC. After suction filtration with toluene washing, 150 ml of toluene was added, followed by liquid separation washing with water 150 ml × 3 times and brine 150 ml × 3 times, and concentrated by evaporation. Subsequently, silica gel column chromatography was performed. A column of 8 cm in diameter was used, and 500 cc of silica gel (height 10 cm) was used. The injection solvent was dichloromethane, and the developing solvent was hexane: ethyl acetate = 10: 1 (vol / vol). After the evaporation, 1.01 g of a yellowish white solid was obtained, and the yield was 50%. A result of ¹ H-NMR (Fig. 22) and MS, to confirm the production of Ac-2MHPM (molecular weight 675).
The elemental analysis results of Ac-2MHPM are shown below.

As shown in Table 9, it was confirmed that the measured values were within the allowable error range (within ± 0.3%).
Example 15 Synthesis of Ac-3MHPM

(I) Synthesis of 3MHPM-Cl In a 300 ml four-necked flask equipped with a reflux tube and a thermometer, 4,6-dichloro-5-methylpyrimidine (0.98 g, 6.0 mmol), 4-chloro-2-methylphenyl Boronic acid (2.24 g, 13.2 mmol), acetonitrile (100 ml), 1M sodium carbonate (Na ₂ CO ₃ ) (30 ml) were added, and nitrogen bubbling was performed for 1 hour. _{Then, PdCl 2 (PPh 3) 2} 210mg, 0.3mmol) were charged, and the reaction was carried out under reflux. The reaction solution was a yellow transparent solution. After 3 hours, disappearance of the raw material was confirmed by TLC. After a while, an orange solid precipitated, and thus suction filtration was performed. After washing with methanol, the filtrate was dissolved in chloroform. Washing was performed with water (150 ml × 3 times) and brine (150 ml × 1 time), followed by evaporation. In order to remove the catalyst, silica gel column chromatography was performed. A glass filter 17G-4 was used and 150 cc of silica gel was used. The injection solvent was toluene, and the developing solvent was hexane: ethyl acetate = 10: 3 (vol / vol). After evaporation, 1.0 g of a white solid was obtained and the yield was 49%. ^{From 1} H-NMR and MS, production of 3MHPM-Cl (molecular weight 343) was confirmed.
(Ii) Synthesis of Ac-3MHPM In a 25 ml four-necked flask equipped with a reflux tube and a thermometer, 3MHPM-Cl (1.03 g, 3 mmol), 9,10-dihydro-9,9-dimethylacridine (1.32 g, 6.3 mmol) and tBuONa (1.44 g, 15 mmol) were added followed by 15 minutes of nitrogen flow. Thereafter, dehydrated xylene (50 ml) was added and nitrogen bubbling was performed for 1 hour. Pd (OAc) ₂ (34 mg, 0.15 mmol) and P (tBu) ₃ (0.11 ml, 0.45 mmol) were added, and then the reaction was performed under reflux conditions (140 ° C.). After the reaction for 4 hours, disappearance of the raw material was confirmed by TLC. After suction filtration with toluene washing, 150 ml of toluene was added, followed by liquid separation washing with water 150 ml × 3 times and brine 150 ml × 3 times, and concentrated by evaporation. Subsequently, silica gel column chromatography was performed. A column of 8 cm in diameter was used, and 500 cc of silica gel (height 10 cm) was used. The injection solvent was dichloromethane, and the developing solvent was hexane: ethyl acetate = 10: 1 (vol / vol). After evaporation, 1.28 g of a yellowish white solid was obtained, and the yield was 62%. Formation of Ac-3MHPM (molecular weight 689) was confirmed by ¹ H-NMR (FIG. 23) and MS.
The elemental analysis results of Ac-3MHPM are shown below.

As shown in Table 10, it was confirmed that the measured values were within the allowable error range (within ± 0.3%).

[Optical characteristics evaluation]
The equipment and measurement conditions used for the optical property evaluation are as follows.
(1) Ultraviolet / visible (UV-vis) spectrophotometer UV-3150 manufactured by Shimadzu Corporation
Measurement conditions: medium scan speed, measurement range 200 to 800 nm, sampling pitch 0.5 nm, slit width 0.5 nm
(2) Photoluminescence (PL) measuring device Fluoro MAX-2 manufactured by HORIBA, Ltd.
At normal temperature and low temperature, PL spectrum and time-resolved PL spectrum (transient PL spectrum) using a streak camera (C4334 manufactured by Hamamatsu Photonics Co., Ltd.) were measured.
(3) Photoelectron Yield Spectroscopy (PYS) Device Ionization Potential Measurement Device manufactured by Sumitomo Heavy Industries, Ltd. Ionization potential (Ip) was measured in vacuum using an ionization potential measurement device.
The electron affinity (Ea) was calculated by estimating the energy gap (Eg) from the absorption edge of the UV-vis absorption spectrum.

(Optical property evaluation-1)
Using Ac-PPM obtained in Example 1, a single film of Ac-PPM, a 10 ⁻⁵ M toluene solution, and a dope film (10 wt% DPEPO co-deposited film) were prepared, and UV-vis absorption spectrum, PL Spectrum and PYS measurements were taken. Note that DPEPO is bis (2- (diphenylphosphino) phenyl) ether oxide.
The results are shown in FIGS.

From FIG. 4B, the PL spectra of the single film and the doped film almost overlapped. This is considered to be because aggregation was suppressed by the dimethyl group of acridine.
In the time-resolved PL spectrum (transient PL spectrum) in FIG. 5, the intensity of the delay component at normal temperature (300K) is higher than that of the delay component at low temperature (5K). From this result, it was found that Ac-PPM exhibits TADF characteristics.
In the PL spectrum of FIG. 6, a phosphorescence spectrum could be observed at a low temperature (5K) (FIG. 6 (a)), and a fluorescence emission spectrum could be observed at room temperature (300K) (FIG. 6 (b)). From the rise of the fluorescence emission spectrum at normal temperature (300 K) and the rise of the phosphorescence spectrum at low temperature (5 K), the excited singlet energy (E _S1 ) and the triplet energy (E _T1 ) are E _s = 2.86 eV and E _T = 2.67 eV could be estimated. From these results, the difference (ΔE _ST ) between the excited singlet energy (E _S1 ) and the triplet energy (E _T1 ) was 0.19 eV, which was a considerably small value.
Moreover, in Ac-PPM, even when doped with PO9 instead of DPEPO, a delay component based on TADF characteristics could be confirmed from the transient PL spectrum as in the case of doping with DPEPO.
From the above results, it is suggested that the pyrimidine skeleton and the dimethylacridine derivative site each have a high triplet energy (E _T1 ) and can be blue TADF.

(Optical property evaluation ・ 2)
A BCz-MPM single film and a doped film (10 wt% DPEPO co-deposited film) were prepared using the BCz-MPM obtained in Example 3, and UV-vis absorption spectrum, PL spectrum, and PYS were measured. It was.
The results are shown in Table 2 and Figs.

From FIG. 8, the doped film was shifted to the long wavelength side by λ _max of about 20 nm as compared with the single film. The reason for this is thought to be concentration quenching due to aggregation.
From the time-resolved PL spectrum (transient PL spectrum) in FIG. 9, the intensity of the delayed component at room temperature of 300 K was clearly increased from that at low temperature of 5 K. From this result, it was found that BCz-MPM exhibits TADF characteristics.
From FIG. 10A, a phosphorescence spectrum could be observed at a low temperature of 5K. From the rise of the fluorescence emission spectrum at normal temperature (300K) shown in FIG. 10B and the rise of the phosphorescence spectrum at low temperature 5K shown in FIG. 10A, the excited singlet energy (E _S1 ) and triplet The energy (E _T1 ) was estimated as E _S = 2.84 eV and E _T = 3.16 eV, respectively. From these results, the energy difference (ΔE _ST ) between the excited singlet energy (E _S1 ) and the triplet energy (E _T1 ) was as low as 0.32 eV.

(Optical property evaluation-3)
For the HOMO and LUMO of the pyrimidine derivatives of Examples 1, 3, 4, and 5, molecular orbital calculation was performed by density functional theory (DFT), and the energy difference (ΔE _HL) between HOMO, LUMO, and HOMO-LUMO. ), Singlet energy (E _Sl ), triplet energy (E _T1 ), and energy difference (ΔE _ST ) of the lowest singlet energy (E _S1 ) and triplet energy (E _T1 ).
Table 13 shows the results.

Any of a pyrimidine derivative of Examples 1, 3, 4 and 5 also, Delta] E _ST is as small as 0.01~0.12eV, TADF is expected. Moreover, the energy difference (ΔE _HL ) between HOMO and LUMO is as large as 3.31 eV or more, and a blue emission color is expected.

(Optical characteristics evaluation-4)
Using Ac-SPM, Ac-NPM, PXZ-PPM and Ac-MMPM obtained in Examples 6 to 9, single films and doped films (10 wt% DPEPO co-deposited films) were prepared, and UV-vis absorption was performed. A spectrum, PYS, and a PL spectrum and a time-resolved PL spectrum (transient PL spectrum) using a streak camera were measured at room temperature and low temperature.
The results are shown in FIGS.
Table 14 shows the emission wavelength (λ _em ), PL emission quantum yield (PLQE), excited singlet energy (S ₁ ), excited triplet energy for the pyrimidine derivatives obtained in Examples 1 and 4-9. (T ₁ ), energy difference (ΔE _ST ) and light emission lifetime (τ _d ) between S ₁ and T ₁ are shown.

表１４より、低温リン光スペクトルにより、すべての材料においてＴ₁が２．６５〜２．７０ｅＶと同等のエネルギーと見積もられた。
（光学特性評価・５）
実施例１３〜１５で得られたＡｃ−１ＭＨＰＭ、Ａｃ−２ＭＨＰＭ、及びＡｃ−３ＭＨＰＭを用いてトルエン溶液（１０^-5Ｍ）を調製し、ＵＶ−ｖｉｓ吸収スペクトル及びＰＬスペクトルを測定し、ドープ膜（２０ｗｔ％ＤＰＥＰＯ共蒸着膜）を作製し、ＰＬスペクトルを測定した。
結果を図２４（ａ）〜（ｃ）に示す。
Ａｃ−１ＭＨＰＭ、Ａｃ−２ＭＨＰＭ、及びＡｃ−３ＭＨＰＭのトルエン溶液（１０^-5Ｍ）のＵＶ−ｖｉｓスペクトルより（図２４（ａ））、これら全ての材料でＴＡＤＦを示唆するＩＣＴ（分子内電荷移動）による吸収が見られた。また、図２４（ｂ）より、２０ｗｔ％ Ａｃ−１ＭＨＰＭ：ＤＰＥＰＯ共蒸着膜はλ_em＝４８１ｎｍと青色発光を示し、ＰＬＱＥは７５％と高い値を示した。一方、２０ｗｔ％ Ａｃ−３ＭＨＰＭ：ＤＰＥＰＯ共蒸着膜はλ_em＝４５４ｎｍと純青色発光を達成し、ＰＬＱＥは４７％を示した。
次に、実施例１３〜１５で得られたＡｃ−１ＭＨＰＭ、Ａｃ−２ＭＨＰＭ、及びＡｃ−３ＭＨＰＭを用いて、単膜、及びドープ膜（２０ｗｔ％ＤＰＥＰＯ共蒸着膜）を調製し、ストリークカメラを用いた時間分解ＰＬスペクトル（過渡ＰＬスペクトル）の測定を行った。
結果を図２５に示す。
図２５より、すべての材料において遅延蛍光の発光強度が３００Ｋにおいて５Ｋよりも強くなっておりＴＡＤＦ特性を示唆している。また、図２６（ａ）及び（ｂ）より、Ａｃ−１ＭＨＰＭ及びＡｃ−２ＭＨＰＭのＴ₁はそれぞれ約２．８ｅＶ、図２６（ｃ）より、Ａｃ−３ＭＨＰＭのＴ₁は２．９５ｅＶと見積もられた。ΔＥ_STはどれも約０．２Ｖと、比較的小さく、発光寿命も比較的小さく（t_d＝４５〜５０ms）、高効率なＴＡＤＦを示唆する。
光学特性結果を表１５に示す。

From Table 14, T ₁ was estimated to be equivalent to 2.65 to 2.70 eV in all materials from the low temperature phosphorescence spectrum.
(Optical characteristics evaluation ・ 5)
A toluene solution (10 ⁻⁵ M) was prepared using Ac-1 MHPM, Ac-2 MHPM, and Ac-3 MHPM obtained in Examples 13 to 15, UV-vis absorption spectrum and PL spectrum were measured, and a dope film (20 wt% DPEPO co-deposited film) was prepared and the PL spectrum was measured.
The results are shown in FIGS.
From the UV-vis spectrum of toluene solutions (10 ^-5 M) of Ac-1 MHPM, Ac-2 MHPM, and Ac-3 MHPM (FIG. 24 (a)), ICT (intramolecular charge transfer) suggesting TADF in all these materials ) Was observed. Further, from FIG. 24B, the 20 wt% Ac-1 MHPM: DPEPO co-deposited film showed blue emission with λ _em = 481 nm, and PLQE showed a high value of 75%. On the other hand, the 20 wt% Ac-3MHPM: DPEPO co-deposited film achieved pure blue emission with λ _em = 454 nm, and PLQE showed 47%.
Next, using Ac-1 MHPM, Ac-2 MHPM, and Ac-3 MHPM obtained in Examples 13 to 15, a single film and a doped film (20 wt% DPEPO co-deposited film) were prepared, and a streak camera was used. The time-resolved PL spectrum (transient PL spectrum) was measured.
The results are shown in FIG.
FIG. 25 shows that the emission intensity of delayed fluorescence is stronger than 5K at 300K in all materials, suggesting TADF characteristics. In addition, from FIGS. 26 (a) and (b), T- ₁ of Ac-1MHPM and Ac-2MHPM is estimated to be about 2.8 eV, respectively, and from FIG. 26 (c), T _{1 of} Ac-3MHPM is estimated to be 2.95 eV. It was. ΔE _ST is about 0.2V, which is relatively small, and the light emission lifetime is relatively small (t _d = 45 to 50 ms), suggesting highly efficient TADF.
Table 15 shows the optical characteristic results.

[Production and Evaluation of Organic EL Element]
The equipment used for the evaluation of the organic EL element is as follows.
EL (electroluminescence) spectrum apparatus; HOTONIC MULTI-CHANNEL ANALYZER PMA-1 manufactured by Hamamatsu Photonics Co., Ltd.

[Example 16]
Using the Ac-PPM obtained in Example 1, the device structure [ITO anode / TAPC (30 nm thickness) / 10 wt% Ac-PPM: DPEPO (10 nm thickness) / B3PyPB (50 nm thickness) / LiF (0.5 nm thickness) ) / Al cathode (100 nm thickness)], an organic EL device was produced. Note that TAPC (4,4′-cyclohexylidenebis [N, N-bis (4-methylphenyl) benzeneamine]) represents a hole transport layer as B3PyPB (3,3 ″, 5,5 ″ −). Tetra (pyridin-3-yl) -1,1 ′, 3 ′, 1 ″ -terphenyl) is a material for forming an electron transport layer, and LiF is a material for forming an electron injection layer. “10 wt% Ac-PPM: DPEPO “(10 wt% DPEPO co-deposited film)” is a material for forming a light emitting layer.

From the EL spectrum shown in FIG. 27, light emission derived from Ac-PPM was observed. The peak wavelength was 496 nm, and light emission from the doped film showed a slight long wavelength shift compared to the Ac-PPM single film.
FIG. 28A shows the relationship between current density-voltage-luminance characteristics, FIG. 28B shows the relationship between power efficiency-luminance characteristics, and FIG. 28C shows the relationship between external quantum efficiency-luminance characteristics. . From these results, the driving power (D.V.) at 1 cd / m ² is 2.92 V, the power efficiency (PE) is 49.6 lm / W, and the external quantum efficiency (EQE) Is 17.9%, the driving power (D.V.) at 100 cd / m ² is 3.93 V, the power efficiency (PE) is 33.1 lm / W, and the external quantum efficiency (E.Q. E.) is 16.1%, the driving power (D.V.) at 1000 cd / m ² is 4.99 V, the power efficiency (PE) is 17.8 lm / W, and the external quantum efficiency (E .Q.E.) Was 11.0%. The CIE at 100 cd / m ² was 0.21 and 0.45, indicating light emission in the green region.

[Example 17]
In Example 16, instead of “10 wt% Ac-PPM: DPEPO”, a 10 wt% DPEPO doped film of BCz-MPM obtained in Example 3 (“10 wt% BCz-MPM”) was used instead of “10 wt% Ac-PPM: DPEPO”. : DPEPO ") was used to produce an organic EL device in the same manner as in Example 16.
That is, the element structure is [ITO anode / TAPC (30 nm thickness) / 10 wt% BCz-MPM: DPEPO (10 nm thickness) / B3PyPB (50 nm thickness) / LiF (0.5 nm thickness) / Al cathode (100 nm thickness)]. is there.
From the EL spectrum shown in FIG. 30, luminescence derived from BCz-MPM was observed.
31A shows the relationship between current density-voltage-luminance characteristics, FIG. 31B shows the relationship between power efficiency-luminance characteristics, and FIG. 31C shows the relationship between external quantum efficiency-luminance characteristics. .
From these results, the peak wavelength was 450 nm, and the CIE at 100 cdm ⁻² was 0.18 and 0.19, indicating pure blue light emission. The maximum external quantum efficiency is EQE _max = 8.5%, which exceeds the theoretical limit of 7.5% of the fluorescent organic EL device, and strongly suggests light emission derived from TADF.

[Example 18]
In Example 16, an organic EL device was produced in the same manner as in Example 16 except that PO9 was used instead of DPEPO as the host material for forming the light emitting layer.

That is, the element structure is [ITO anode / TAPC (30 nm thickness) / 10 wt% Ac-PPM: PO9 (10 nm thickness) / B3PyPB (50 nm thickness) / LiF (0.5 nm thickness) / Al cathode (100 nm thickness)]. is there.
From FIG. 33, it was found that EL spectra almost overlap in the element using PO9 as the host material for forming the light emitting layer and the element of Example 16.
34A shows the relationship between current density-voltage-luminance characteristics, FIG. 34B shows the relationship between power efficiency-luminance characteristics, and FIG. 34C shows the relationship between external quantum efficiency-luminance characteristics. . In FIGS. 34A to 34C, these characteristics of the element of Example 16 are also shown.
From these results, it was found that the element using PO9 as the host material is slightly more efficient at low luminance than when DPEPO is used. In the case of an element using PO9 as a host material, the driving power (D.V.) at 1 cd / m ² is 2.91 V, the luminance (PE) is 51.7 m / W, and the external quantum efficiency (E .Q.E.) Is 19.2%, drive power (D.V.) at 100 cd / m ² is 3.91 V, luminance (PE) is 32.0 lm / W, external quantum efficiency (EQE) is 16.0%, driving power (DV) at 1000 cd / m ² is 5.00 V, luminance (PE) is 17.0 lm / W, external The quantum efficiency (EQE) was 10.9%. The CIE at 100 cd / m ² was 0.21 and 0.43, indicating light emission in the green region.
In particular, in an element using PO9 for Ac-PPM, the maximum external quantum efficiency (EQE) was 19.2%, which was as high as 20%. It can also be seen that the driving voltage is low at 50 lm / W in the low luminance region.
Table 16 shows the results of Examples 16-18.

In Examples 16 and 18, even when either DPEPO or PO9 was used as the host material (dopant), a delayed component derived from TADF could be confirmed from the transient PL spectrum.
When the host material is DPEPO (Example 16), the CIE at 100 cdm ⁻² is 0.21 and 0.45, indicating light emission in the green region, and when the host material is PO9 (Example 18), 100 cdm ⁻² The CIE at the time was 0.21 and 0.43, indicating light emission in the green region. In the device of Example 8, the maximum external quantum efficiency was 19.2%, which was as high as 20%. The drive voltage was also low, and a high power efficiency of 50 lm / W was achieved in the low luminance region.

[Example 19]
Using the Ac-PPM, Ac-MPM, Ac-HPM, Ac-SPM, and Ac-NPM obtained in Examples 1 and 4 to 7, the device structure [ITO anode / TAPC (30 nm thickness) / 10 wt% Ac- RPM: DPEPO (20 nm thickness) / B3PyPB (50 nm thickness) / LiF (0.5 nm thickness) / Al cathode (100 nm thickness)] was prepared. Note that Ac-RPM represents any of Ac-PPM, Ac-MPM, Ac-HPM, Ac-SPM, and Ac-NPM.
FIG. 36 shows an energy diagram.
The results are shown in FIGS. 37 (a) to 37 (c) and Table 17.
From the EL spectrum shown in FIG. 37, light emission derived from Ac-RPM was observed in all devices. Moreover, as shown in FIG.38 (b), high efficiency of 10% or more of maximum external quantum efficiency (EQE) was achieved in all the elements. In particular, as shown in Table 17, the Ac-SPM and devices using Ac-NPM, respectively 100Cdm ^-1 at green emission CIE (0.24,0.49), blue light emission CIE (0.17,0. 29).

[Example 20]
Using the Ac-MPM obtained in Example 4, the device structure [ITO anode / TAPC (30 nm thickness) / 10 wt% Ac-MPM: mCP (10 nm thickness) / 10 wt% Ac-MPM: DPEPO (10 nm thickness) / B3PyPB (50 nm thickness) / LiF (0.5 nm thickness) / Al cathode (100 nm thickness)] was produced. That is, a double light emitting layer device was manufactured using Ac-MPM that achieved 80% PLQY.
An energy diagram is shown in FIG.

図４０に示すＥＬスペクトルより、Ａｃ−ＭＰＭに由来する発光が観測された。
図４１（ａ）は、電流密度−電圧−輝度特性の関係を示し、図４１（ｂ）は電力効率−輝度特性の関係を示し、図４１（ｃ）は外部量子効率−輝度特性の関係を示す。
結果を表１８に示す。

From the EL spectrum shown in FIG. 40, light emission derived from Ac-MPM was observed.
41A shows the relationship between current density-voltage-luminance characteristics, FIG. 41B shows the relationship between power efficiency-luminance characteristics, and FIG. 41C shows the relationship between external quantum efficiency-luminance characteristics. Show.
The results are shown in Table 18.

ホスト材料にｍＣＰ及びＤＰＥＰＯを使用したデバイスは、最大外部量子効率（Ｅ．Ｑ．Ｅ．）２４．５％（図４１（Ｃ））、駆動電圧（Ｄ．Ｖ．）２．８Ｖ（図４１（ａ））、最大電力効率（Ｅ．Ｑ．Ｅ．）６１．６％（図４１（Ｂ））、かつ、表１８に示すように、水色発光（ＣＩＥ（０．１９、０．３７））を達成した。

A device using mCP and DPEPO as a host material has a maximum external quantum efficiency (EQE) of 24.5% (FIG. 41C), a driving voltage (DV) of 2.8 V (FIG. 41). (A)), maximum power efficiency (EQE) 61.6% (FIG. 41 (B)), and as shown in Table 18, light blue emission (CIE (0.19, 0.37)) ) Was achieved.

[Example 21]
Using the PXZ-PPM obtained in Example 8, devices having a PXZ-PPM doping concentration of 5 to 50 wt% were prepared.
Device D: [ITO / KLHIP: PPBi (20 nm) / TAPC (25 nm) / TCTA (5 nm) / 5 wt% PXZ-PPM : CBP (10 nm) / B4PyPPM (50 nm) / LiF (0.5 nm) / Al (100 nm) ]
Device E: [ITO / KLHIP: PPBi (20 nm) / TAPC (25 nm) / TCTA (5 nm) / 10 wt% PXZ-PPM : CBP (10 nm) / B4PyPPM (50 nm) / LiF (0.5 nm) / Al (100 nm) ]
Device F: [ITO / KLHIP: PPBi (20 nm) / TAPC (25 nm) / TCTA (5 nm) / 15 wt% PXZ-PPM : CBP (10 nm) / B4PyPPM (50 nm) / LiF (0.5 nm) / Al (100 nm) ]
Device G: [ITO / KLHIP: PPBi (20 nm) / TAPC (25 nm) / TCTA (5 nm) / 20 wt% PXZ-PPM : CBP (10 nm) / B4PyPPM (50 nm) / LiF (0.5 nm) / Al (100 nm) ]
Device H: [ITO / KLHIP: PPBi (20 nm) / TAPC (25 nm) / TCTA (5 nm) / 50 wt% PXZ-PPM : CBP (10 nm) / B4PyPPM (50 nm) / LiF (0.5 nm) / Al (100 nm) ]
An energy diagram of devices D to H is shown in FIG.
The results of EL spectra of devices D to H are shown in FIG. 44A shows the relationship between voltage and luminance characteristics, FIG. 44B shows the relationship between external quantum efficiency and luminance characteristics, and FIG. 44C shows the relationship between power efficiency and luminance characteristics.

結果を表１９に示す。

The results are shown in Table 19.

図４３に示すＥＬスペクトルより、発光材料由来のピークが観測された（λ_EL＝５２４〜５４０ｎｍ）。図４４（ｂ）、（ｃ）及び表１９に示すように、ドープ濃度が２０ｗｔ％のデバイスにおいて、最大外部量子効率が２５．１％、最大電力効率が１１１ ｌｍ／ＷとこれまでのＴＡＤＦ素子のなかで世界最高効率を示した。また、１００ｃｄ／ｍ²時においても外部量子効率が２５．１％、電力効率が１０３ ｌｍ／Ｗと高い値を維持した。

From the EL spectrum shown in FIG. 43, a peak derived from the light emitting material was observed (λ _EL = 524 to 540 nm). As shown in FIGS. 44 (b) and 44 (c) and Table 19, in a device having a doping concentration of 20 wt%, the maximum external quantum efficiency is 25.1% and the maximum power efficiency is 111 lm / W, so far the TADF element. Among them, it showed the highest efficiency in the world. Even at 100 cd / m ² , the external quantum efficiency was 25.1% and the power efficiency was maintained at a high value of 103 lm / W.

[Example 22]
Using the Ac-MMPM obtained in Example 9, the device structure [ITO anode / TAPC (30 nm thickness) / 10 wt% Ac-MMPM: mCP (10 nm thickness) / 10 wt% Ac-MMPM: DPEPO (10 nm thickness) / B3PyPB (50 nm thickness) / LiF (0.5 nm thickness) / Al cathode (100 nm thickness)] was produced.
An energy diagram is shown in FIG.
From the EL spectrum shown in FIG. 46, light emission derived from Ac-MMPM was observed.
47A shows the relationship between current density-voltage-luminance characteristics, FIG. 47B shows the relationship between power efficiency-luminance characteristics, and FIG. 47C shows the relationship between external quantum efficiency-luminance characteristics. Show.
The results are shown in Table 20.

表２０に示すように、ＣＩＥ（０．１６、０．２０）と純青色発光を示した。また、図４７（ｃ）に示すように、最大外部量子効率が１３．５％、１００ｃｄｍ^-2時においても８．２％と、従来の蛍光発光材料の理論限界（７．５％）を凌駕している。

As shown in Table 20, CIE (0.16, 0.20) and pure blue light emission were exhibited. Further, as shown in FIG. 47 (c), the maximum external quantum efficiency is 13.5%, and it is 8.2% even at 100 cdm ⁻² , exceeding the theoretical limit (7.5%) of the conventional fluorescent light emitting material. doing.

[Example 23]
Devices were prepared using Ac-46DPPM, Ac-26DPPM and CzAc-26DPPM obtained in Examples 10-12. The element structure is shown below.
[ITO / TAPC (20 nm) / Ac-46DPPM or Ac-26DPPM or CzAc-26DPPM: mCP (10 nm) / Ac-46DPPM or Ac-26DPPM or CzAc-26DPPM: DPEPO (10 nm) / B3PyPB (50 nm) / LiF (0 .5 nm) / Al (100 nm)]
FIG. 48 shows an energy diagram of materials constituting the device using Ac-46DPPM, Ac-26DPPM, and CzAc-26DPPM for the light emitting layer.
FIG. 49 shows the results of measuring the EL spectrum for each device.
50A shows the relationship between current density-voltage-luminance characteristics, FIG. 50B shows the relationship between power efficiency-luminance characteristics, and FIG. 50C shows the relationship between external quantum efficiency-luminance characteristics. Show.
The results are shown in Table 21.

表２１に示すように、Ａｃ−４６ＤＰＰＭを用いた場合、最も青色発光（０．１６、０．２１）を示し、ＣｚＡｃ−２６ＤＰＰＭにかけて水色発光（０．２１、０．３８）に長波長シフトすることがわかった。また、同時に、Ａｃ−４６ＤＰＰＭを用いた場合、外部量子効率が１００ｃｄ／ｍ²時、１４．９％、１０００ｃｄ／ｍ²時、９．２８％と、蛍光発光材料の理論限界外部量子効率７．５％を凌駕したデバイス特性を示した。

As shown in Table 21, when Ac-46DPPM is used, blue light emission (0.16, 0.21) is shown, and CzAc-26DPPM is shifted to light blue light emission (0.21, 0.38) by a long wavelength. I understood it. At the same time, Ac-46DPPM case of using, at the external quantum efficiency of 100cd / m ^2, 14.9%, at 1000cd / m ^2, 9.28% and, fluorescent material of the theoretical limit external quantum efficiency 7. The device characteristics surpassed 5%.

[Example 24]
Devices were prepared using Ac-1 MHPM, Ac-2 MHPM, and Ac-3 MHPM obtained in Examples 13 to 15, respectively. The host material used was DPEPO, the hole-side exciton block layer was mCP, the host DPEPO, and the electron-side exciton block layer was DPEPO.
The element structure is shown below.
Device 1: [ITO / KLHIP: PPBi (20 nm) / TAPC (20 nm) / mCP (10 nm) / 20 wt% Ac-1MHPM : DPEPO (20 nm) / DPEPO (10 nm) / B3PyPB (30 nm) / LiF (0.5 nm) / Al (100 nm)]
Device 2: [ITO / KLHIP: PPBi (20 nm) / TAPC (20 nm) / mCP (10 nm) / 20 wt% Ac-2MHPM : DPEPO (20 nm) / DPEPO (10 nm) / B3PyPB (30 nm) / LiF (0.5 nm) / Al (100 nm)]
Device 3: [ITO / KLHIP: PPBi (20 nm) / TAPC (20 nm) / mCP (10 nm) / 20 wt% Ac-3MHPM : DPEPO (20 nm) / DPEPO (10 nm) / B3PyPB (30 nm) / LiF (0.5 nm) / Al (100 nm)]

FIG. 51 shows an energy diagram of materials constituting the devices 1 to 3 using Ac-1 MHPM, Ac-2 MHPM, and Ac-3 MHPM for the light emitting layer.
In FIG. 52, the result of having measured EL spectrum about the devices 1-3 is shown.
53A shows the relationship between current density-voltage-luminance characteristics, FIG. 53B shows the relationship between external quantum efficiency-luminance characteristics, and FIG. 53C shows the relationship between power efficiency-luminance characteristics. Show.
The results are shown in Table 22.

ＥＬスペクトルより、どちらも発光材料由来のピークが観測された。図５２より、発光波長は、Ａｃ−１ＭＨＰＭでは、λ_EL＝４７７ｎｍ（ＣＩＥ（０．１７，０．２８））、Ａｃ−２ＭＨＰＭでは、λ_EL＝４７７ｎｍ（ＣＩＥ（０．１７，０．２７））と青色発光を示し、Ａｃ−３ＭＨＰＭでは、λ_EL＝４５０ｎｍ（ＣＩＥ（０．１６，０．１５））と純青色発光を示した。Ａｃ−１ＭＨＰＭでは、最大外部量子効率（Ｅ．Ｑ．Ｅ_max）が２４．０％、１００ｃｄｍ^-2時においても高い外部量子効率が１９．０％という非常に高い効率を達成した。一方、Ａｃ−３ＭＨＰＭは最大外部量子効率が１７．８％、１００ ｃｄｍ^-2時においても高い外部量子効率が１０．４％という純青色ＴＡＤＦ素子においては高い効率を達成した（図５３（ｂ））。

From the EL spectrum, peaks derived from the light emitting material were observed in both cases. From FIG. 52, the emission wavelength is λ _EL = 477 nm (CIE (0.17, 0.28)) for Ac-1 MHPM, and λ _EL = 477 nm (CIE (0.17, 0.27) for Ac-2 MHPM. ) And blue light emission, and Ac-3MHPM showed pure blue light emission at λ _EL = 450 nm (CIE (0.16, 0.15)). In Ac-1 MHPM, the maximum external quantum efficiency (EQE _max ) was 24.0%, and a high external quantum efficiency of 19.0% was achieved even at 100 cdm ⁻² . On the other hand, Ac-3MHPM achieved high efficiency in a pure blue TADF device having a maximum external quantum efficiency of 17.8% and a high external quantum efficiency of 10.4% even at 100 cdm ⁻² (FIG. 53B). ).

DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Hole injection layer 4 Hole transport layer 5 Light emitting layer 6 Electron transport layer 7 Electron injection layer 8 Cathode

Claims (6)

It is represented by the following general formula (1), and
A pyrimidine derivative characterized in that an energy difference (ΔE _ST ) between excited singlet energy (E _S1 ) and triplet excited energy (E _T1 ) is 0.25 eV or less.

(In general formula (1),
R ¹ represents a hydrogen atom, an electron donating group, an alkyl group, an alkoxy group, a thioalkoxy group or an amino group, or an electron withdrawing group, an aryl group, a cyano group, a carbonyl group or a sulfonyl group,
R ⁸ represents a methyl group, an aryl group, an alkoxy group, an acyl group or a cyano group,
n represents an integer of 1 to 3,
Each of the substituents D independently represents a hydrogen atom or an electron-donating group,
When n is 2 or 3, the phenyl groups having the substituent D have a symmetric structure or an asymmetric structure with respect to each other. ) It is represented by the following general formula (1), and
A pyrimidine derivative characterized in that an energy difference (ΔE _ST ) between excited singlet energy (E _S1 ) and triplet excited energy (E _T1 ) is 0.25 eV or less.

(In general formula (1),
R ¹ represents a hydrogen atom, an electron donating group, an alkyl group, an alkoxy group, a thioalkoxy group or an amino group, or an electron withdrawing group, an aryl group, a cyano group, a carbonyl group or a sulfonyl group,
R ⁸ represents a methyl group, an aryl group, an alkoxy group, an acyl group or a cyano group,
n represents 2,
Each of the substituents D independently represents a hydrogen atom or an electron-donating group, and
The phenyl groups having the substituent D have a symmetric structure or an asymmetric structure. ) It is represented by the following general formula (2),
A pyrimidine derivative characterized in that an energy difference (ΔE _ST ) between excited singlet energy (E _S1 ) and triplet excited energy (E _T1 ) is 0.25 eV or less.

(In general formula (2),
R ¹ represents a hydrogen atom, an electron donating group, an alkyl group, an alkoxy group, a thioalkoxy group or an amino group, or an electron withdrawing group, an aryl group, a cyano group, a carbonyl group or a sulfonyl group,
R ⁸ represents a methyl group, an aryl group, an alkoxy group, an acyl group or a cyano group,
D represents each independently the substituent represented by the following structural formula. )

(In General Formula (3), R ^{2 to} R ⁷ each independently represents a hydrogen atom, an alkyl group or an aryl group, and X represents a methylene group, —CR ^a R ^b —, —O—, —S—, Or -S (= O) _2- , wherein R ^a and R ^b are each independently an alkyl group or an aryl group, and may be linked to each other to form a ring). The pyrimidine derivative according to any one of claims 1 to 3, which is represented by the following structural formula.

  The luminescent material which consists of a pyrimidine derivative as described in any one of Claims 1-4.   The organic EL element using the pyrimidine derivative as described in any one of Claims 1-4.

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