JP2015205831A - Benzofuropyrimidine compound, method for producing the same, and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electron injection material or an electron transport material driving an element under low voltage by excellent electron injection properties and electron transport properties under low pressure and further driving the element for a long time with high luminous efficiency.SOLUTION: Provided is an electron injection material or an electron transport material including a benzofuropyrimidine compound, for example, represented by formula (C-1).

Description

  The present invention relates to a benzofuropyrimidine compound useful as a component of an organic electroluminescent device, a method for producing the same, and an electron injection material or an electron transport material comprising the compound.

  An organic electroluminescent element has a basic structure in which a light-emitting layer containing a light-emitting material is sandwiched between a hole transport layer and an electron transport layer, and an anode and a cathode are attached to the outside of the light-emitting layer. This element utilizes light emission (fluorescence or phosphorescence) accompanying exciton deactivation caused by recombination of holes and electrons, and is applied to displays and the like. The hole transport layer is divided into a hole transport layer and a hole injection layer, the light emitting layer is divided into an electron blocking layer, a light emitting layer and a hole blocking layer, and the electron transport layer is divided into an electron transport layer and an electron injection layer. May be configured.

  In recent years, many organic electroluminescent devices using triazine and pyrimidine compounds in the light emitting layer and the electron transporting layer have been reported, but they completely satisfy the market requirements in terms of luminous efficiency characteristics, driving voltage characteristics, and long life characteristics. However, there is a need for better materials.

  As electron transport materials, dibenzofuran compounds (for example, Patent Document 1) and nitrogen-substituted dibenzothiophene compounds have been disclosed (for example, refer to Patent Document 2-3), and proposals for improving the lifetime of the device using these compounds have been made. However, improvement is desired in that the device has a higher drive voltage and a longer life expectancy.

  In addition, the use of nitrogen-substituted dibenzofuran compounds has been proposed for many applications, not limited to organic electroluminescent devices, but production methods of these compounds have hardly been reported, and a simple synthesis method is required. .

International Publication No. 2007/069569 Pamphlet JP 2011-84531 A International Publication No. 2013/038650 Pamphlet

  Organic electroluminescence devices have begun to be used in various display devices, but there is a demand for further enhancement of device performance such as longer life, higher luminous efficiency, and lower drive voltage. More specifically, there is a demand for the development of a carrier transport material that achieves a long life, high luminous efficiency, low driving voltage, and suppression of voltage rise during driving.

  Among the carrier transport materials, for the electron injection material and the electron transport material, there are new materials that drive the device at a low voltage due to excellent electron injection properties and electron transport properties, and have high luminous efficiency and drive the device for a long time. It is desired.

  In addition, simple synthesis of benzofuropyrimidine compounds, which are useful compounds, is desired.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the benzofuropyrimidine compound represented by the general formula (1) of the present invention has an electron durability and It has been found that the hole durability is remarkably improved. From such knowledge, when the benzofuropyrimidine compound is used as an electron transport layer in an organic electroluminescent device, the organic electroluminescent device has a longer life than when a known or general-purpose electron transport material is used. The inventors have found that the voltage rise during driving is suppressed, and have completed the present invention.

  That is, the present invention relates to a benzofuropyrimidine compound (hereinafter also referred to as “compound (1)”) represented by the following general formula (1) of the present invention, a production method thereof, and an electron injection material or electron transport containing the compound. It relates to materials.

（式中、Ｒ^１〜Ｒ^４は、各々独立して、炭素数４〜６６の芳香族基（各々独立して、フッ素原子、メチル基、エチル基、炭素数３〜１０のアルキル基、メトキシ基、エトキシ基、炭素数３〜１０のアルコキシ基、炭素数１〜３のハロゲン化アルキル基、炭素数１〜３のハロゲン化アルコキシ基、又は炭素数１０〜３６のジアリールアミノ基を置換基として有していてもよい）、水素原子、重水素原子、フッ素原子、メチル基、エチル基、炭素数３〜１０のアルキル基、メトキシ基、エトキシ基、炭素数３〜１０のアルコキシ基、メチルチオ基、エチルチオ基、炭素数３〜１０のスルフィド基、又は炭素数１０〜３６のジアリールアミノ基を表す。
Ａｒ^１及びＡｒ^２は、各々独立して、炭素数４〜６６の芳香族基（各々独立して、フッ素原子、メチル基、エチル基、炭素数３〜１０のアルキル基、メトキシ基、エトキシ基、炭素数３〜１０のアルコキシ基、炭素数１〜３のハロゲン化アルキル基、炭素数１〜３のハロゲン化アルコキシ基、又は炭素数１０〜３６のジアリールアミノ基を置換基として有していてもよい）を表す。）
また、本発明は、前記化合物（１）を工業的に製造するために極めて有用な製造中間体を提供することができる。

(In the formula, R ^{1 to} R ⁴ are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, methoxy Group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, halogenated alkyl group having 1 to 3 carbon atoms, halogenated alkoxy group having 1 to 3 carbon atoms, or diarylamino group having 10 to 36 carbon atoms as a substituent Which may have), hydrogen atom, deuterium atom, fluorine atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, methylthio group , An ethylthio group, a C3-C10 sulfide group, or a C10-C36 diarylamino group.
Ar ¹ and Ar ² are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group). , Having an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. May be). )
Moreover, this invention can provide a very useful manufacturing intermediate in order to manufacture the said compound (1) industrially.

  Hereinafter, the present invention will be described in detail.

  The present invention relates to the above compound (1), a production method thereof, and an electron injection material or an electron transport material containing the compound.

  The present invention also relates to a production intermediate for producing the above compound (1).

  The substituents in the compound (1) of the present application are defined as follows.

  The aromatic group having 4 to 66 carbon atoms defines only a ring skeleton that may be condensed or linked, and the carbon number of the aromatic group does not include the carbon number of the substituent. In the aromatic group having 4 to 66 carbon atoms, the aromatic group is not particularly limited as long as it is an aromatic hydrocarbon group, a heteroaromatic group, or a group in which these are condensed or linked.

  That is, the aromatic group having 4 to 66 carbon atoms represents an aromatic group having 4 to 66 carbon atoms in the ring skeleton and may be condensed or linked. The aromatic group having 4 to 66 carbon atoms does not include the carbon number of a substituent that may be separately provided. The aromatic group having 4 to 66 carbon atoms is not particularly limited as long as it is an aromatic hydrocarbon group, a heteroaromatic group, or a group in which these are condensed or linked.

  The aromatic group having 4 to 66 carbon atoms is not particularly limited, and examples thereof include a phenyl group, a biphenylyl group, a terphenyl group, a naphthyl group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylbiphenyl group, and a biphenylnaphthyl group. Group, diphenylnaphthyl group, phenylnaphthylphenyl group, anthryl group, anthrylphenyl group, phenylanthryl group, phenylanthrylphenyl group, phenanthrylphenyl group, phenanthrylphenyl group, phenylphenanthryl group, pyrenyl group, phenylpyrene group Nyl, pyrenylphenyl, fluorenyl, fluorenylphenyl, phenylfluorenyl, fluoranthenyl, phenylfluoranthenyl, fluoranthenylphenyl, perylenyl, phenylperenylenyl, perylenylphenyl Group, triphenylenyl group, phenyltriphenylenyl group, triphenylenylphenyl group, tetracenyl group, phenyltoteracenyl group, tetracenylphenyl group, chrysenyl group, phenylchrysenyl group, chrysenylphenyl group Or an aromatic hydrocarbon group which may be condensed), pyridyl group, phenylpyridyl group, pyridylphenyl group, bipyridyl group, biphenylpyridyl group, pyridylbiphenyl group, diphenylpyridyl group, pyrimidyl group, phenylpyrimidyl group, pyridyl group Midylphenyl, pyrazyl, phenylpyrazyl, pyrazylphenyl, triazinyl, phenyltriazyl, triazylphenyl, quinolyl, phenylquinolyl, quinolylphenyl, pyridylquinolyl, isoquinolyl, Phenylisoquinolyl , Isoquinolylphenyl group, pyridylisoquinolyl group, quinoxalinyl group, phenylquinoxalinyl group, quinoxalinylphenyl group, acridinyl group, phenylacridinyl group, acridinylphenyl group, phenanthridinyl group , Phenylphenanthridinyl group, phenanthridinylphenyl group, phenanthrolinyl group, phenylphenanthrolinyl group, phenanthrolinylphenyl group, pyrrolyl group, phenylpyrrolyl group, pyrrolylphenyl group, pyridylpyrrole Group, furanyl group, phenylfuranyl group, furanylphenyl group, pyridylfuranyl group, thienyl group, phenylthienyl group, thienylphenyl group, imidazolyl group, phenylimidazolyl group, imidazolylphenyl group, oxazolyl group, phenyloxazolyl group Group, oxazolylpheny Group, isoxazolyl group, phenylisoxazolyl group, isoxazolylphenyl group, oxadiazolyl group, phenyloxadiazolyl group, oxadiazolylphenyl group, thiazolyl group, phenylthiazolyl group, thiazolylphenyl group, Indolyl group, phenylindolyl group, indolylphenyl group, benzofuranyl group, phenylbenzofuranyl group, benzofuranylphenyl group, benzothiazolyl group, phenylbenzothiazolyl group, benzothiazolylphenyl group, benzoimidazolyl group, phenylbenzoimidazolyl Group, benzimidazolylphenyl group, benzoxazolyl group, phenylbenzoxazolyl group, benzoxazolylphenyl group, benzothiazolyl group, phenylbenzothiazolyl group, benzothiazolylphenyl group, dibenzofura Group, phenyldibenzofuranyl group, dibenzofuranylphenyl group, dibenzothienyl group, phenyldibenzothienyl group, dibenzothienylphenyl group, carbazolyl group, phenylcarbazolyl group, carbazolylphenyl group, pyridylcarbazolyl group, Pyridylphenylcarbazolyl group, carbolinyl group, phenylcarbolinyl group, carbolinylphenyl group, indolocarbazolyl group, phenylindolocarbazolyl group, phenylindolocarbazolylphenyl group, indolocarbazolyl And a ruphenyl group, an indolobenzothienyl group, a phenylindolobenzothienyl group, or an indolobenzothienylphenyl group (above, a heteroaromatic group which may be linked or condensed).

  Although it does not specifically limit as a C3-C10 alkyl group, For example, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec -Pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, benzyl group, or phenethyl group.

  Although it does not specifically limit as a C3-C10 alkoxy group, For example, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group , Sec-pentyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, benzyloxy group, or phenethyloxy Groups and the like.

  Although it does not specifically limit as a C1-C3 halogenated alkyl group, For example, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloroethyl group, dichloro Examples include an ethyl group, trichloroethyl group, pentachloroethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, pentafluoroethyl group, chloropropyl group, or fluoropropyl group.

  Although it does not specifically limit as a C1-C3 halogenated alkoxy group, For example, a chloromethyloxy group, a dichloromethyloxy group, a trichloromethyloxy group, a fluoromethyloxy group, a difluoromethyloxy group, tri Fluoromethyloxy group, chloroethyloxy group, dichloroethyloxy group, trichloroethyloxy group, pentachloroethyloxy group, fluoroethyloxy group, difluoroethyloxy group, trifluoroethyloxy group, pentafluoroethyloxy group, chloro A propyloxy group, a fluoropropyloxy group, etc. are mentioned.

  The diarylamino group having 10 to 36 carbon atoms represents an amino group in which two kinds of aryl groups which may be different from each other are bonded, and means a group having 10 to 36 carbon atoms as a whole.

  The diarylamino group having 10 to 36 carbon atoms is not particularly limited. For example, N, N-diphenylamino group, N-tolyl-N-phenylamino group, N, N-ditolylamino group, N, N -Dibiphenylamino group, N, N-di (terphenyl) amino group, N-phenyl-N-naphthylamino group, N-phenyl-N-biphenylamino group, N-phenyl-N-terphenylamino group, or N-biphenyl-N-terphenylamino group etc. are mentioned. Of these, N, N-diphenylamino group, N-tolyl-N-phenylamino group, N, N-ditolylamino group, or N, N-dibiphenyl is preferable in that the compound (1) has excellent electron transport material properties. An amino group is preferred.

  Although it does not specifically limit as a C3-C10 sulfide group, For example, n-propyl sulfide group, isopropyl sulfide group, n-butyl sulfide group, sec-butyl sulfide group, tert-butyl sulfide group, n -Pentyl sulfide group, sec-pentyl sulfide group, cyclopentyl sulfide group, n-hexyl sulfide group, cyclohexyl sulfide group, n-heptyl sulfide group, n-octyl sulfide group, n-nonyl sulfide group, n-decyl sulfide group, benzyl Examples thereof include a sulfide group or a phenethyl sulfide group.

In R ^{1 to} R ⁴ , Ar ¹ , and Ar ² , the aromatic group having 4 to 66 carbon atoms is each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, or a methoxy group. , An ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, and a diarylamino group having 10 to 36 carbon atoms. And may have a plurality of substituents. When there are a plurality of substituents, each substituent may be the same or different.

^As the R ¹ ~R 4, Ar ^1, and an aromatic substituent which group may have, for 4-66 carbon atoms in Ar ^2, from the viewpoint of excellent electron transporting material properties, a methyl group or a carbon number 10-36 diarylamino groups are preferred.

R ^{1 to} R ⁴ are each independently an aromatic group having 4 to 30 carbon atoms in terms of excellent electron transport material properties (these substituents are each independently a fluorine atom, a methyl group, or an ethyl group). A substituent having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogenated alkoxy group having 1 to 3 carbon atoms May be a hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, an ethyl group, or an alkyl group having 3 to 10 carbon atoms, preferably a phenyl group, a biphenyl group, a phenanthryl group, a pyrenyl group. Group, fluoranthenyl group, pyridyl group, pyrimidyl group, quinolyl group, isoquinolyl group, pyridylphenyl group, pyrimidylphenyl group, carbazolyl group, pyridylcarbazolyl group, young A dipyridylcarbazolyl group (these substituents may each independently have a fluorine atom, a methyl group, an ethyl group, a methoxy group or an ethoxy group as a substituent), a hydrogen atom, a deuterium atom , A fluorine atom, a methyl group, an ethyl group, or an alkyl group having 3 to 10 carbon atoms, each independently a phenyl group, a biphenylyl group, an anthracenyl group, a phenanthryl group, a pyrimidylphenyl group, or It is more preferably a pyridylphenyl group (these substituents may have a methyl group), a hydrogen atom, a deuterium atom, or a methyl group, and more preferably a hydrogen atom or a deuterium atom.

  The aromatic group having 4 to 30 carbon atoms is not particularly limited, but among the substituents exemplified in the aromatic group having 4 to 66 carbon atoms, the total number of carbon atoms is 30 or less. Things can be illustrated.

  That is, the aromatic group having 4 to 30 carbon atoms defines only a ring skeleton that may be condensed or linked, and the carbon number of the aromatic group does not include the carbon number of the substituent. The aromatic group in the aromatic group having 4 to 30 carbon atoms is not particularly limited as long as it is an aromatic hydrocarbon group, a heteroaromatic group, or a group in which these are condensed or linked.

  Although it does not specifically limit as the said C4-C30 aromatic group, For example, a phenyl group, a biphenylyl group, a terphenyl group, a naphthyl group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylbiphenyl group, biphenylnaphthyl Group, diphenylnaphthyl group, phenylnaphthylphenyl group, anthryl group, anthrylphenyl group, phenylanthryl group, phenylanthrylphenyl group, phenanthrylphenyl group, phenanthrylphenyl group, phenylphenanthryl group, pyrenyl group, phenylpyrene group Nyl, pyrenylphenyl, fluorenyl, fluorenylphenyl, phenylfluorenyl, fluoranthenyl, phenylfluoranthenyl, fluoranthenylphenyl, perylenyl, phenylperenylenyl, perylenylphenyl Group, triphenylenyl group, phenyltriphenylenyl group, triphenylenylphenyl group, tetracenyl group, phenyltoteracenyl group, tetracenylphenyl group, chrysenyl group, phenylchrysenyl group, chrysenylphenyl group Or an aromatic hydrocarbon group which may be condensed), pyridyl group, phenylpyridyl group, pyridylphenyl group, bipyridyl group, biphenylpyridyl group, pyridylbiphenyl group, diphenylpyridyl group, pyrimidyl group, phenylpyrimidyl group, pyridyl group Midylphenyl, pyrazyl, phenylpyrazyl, pyrazylphenyl, triazinyl, phenyltriazyl, triazylphenyl, quinolyl, phenylquinolyl, quinolylphenyl, pyridylquinolyl, isoquinolyl, Phenylisoquinolyl , Isoquinolylphenyl group, pyridylisoquinolyl group, quinoxalinyl group, phenylquinoxalinyl group, quinoxalinylphenyl group, acridinyl group, phenylacridinyl group, acridinylphenyl group, phenanthridinyl group , Phenylphenanthridinyl group, phenanthridinylphenyl group, phenanthrolinyl group, phenylphenanthrolinyl group, phenanthrolinylphenyl group, pyrrolyl group, phenylpyrrolyl group, pyrrolylphenyl group, pyridylpyrrole Group, furanyl group, phenylfuranyl group, furanylphenyl group, pyridylfuranyl group, thienyl group, phenylthienyl group, thienylphenyl group, imidazolyl group, phenylimidazolyl group, imidazolylphenyl group, oxazolyl group, phenyloxazolyl group Group, oxazolylpheny Group, isoxazolyl group, phenylisoxazolyl group, isoxazolylphenyl group, oxadiazolyl group, phenyloxadiazolyl group, oxadiazolylphenyl group, thiazolyl group, phenylthiazolyl group, thiazolylphenyl group, Indolyl group, phenylindolyl group, indolylphenyl group, benzofuranyl group, phenylbenzofuranyl group, benzofuranylphenyl group, benzothiazolyl group, phenylbenzothiazolyl group, benzothiazolylphenyl group, benzoimidazolyl group, phenylbenzoimidazolyl Group, benzimidazolylphenyl group, benzoxazolyl group, phenylbenzoxazolyl group, benzoxazolylphenyl group, benzothiazolyl group, phenylbenzothiazolyl group, benzothiazolylphenyl group, dibenzofura Group, phenyldibenzofuranyl group, dibenzofuranylphenyl group, dibenzothienyl group, phenyldibenzothienyl group, dibenzothienylphenyl group, carbazolyl group, phenylcarbazolyl group, carbazolylphenyl group, pyridylcarbazolyl group, Pyridylphenylcarbazolyl group, dipyridylcarbazolyl group, carbolinyl group, phenylcarbolinyl group, carbolinylphenyl group, indolocarbazolyl group, phenylindolocarbazolyl group, indolocarbazolylphenyl group , Phenylindolocarbazolylphenyl group, indolobenzothienyl group, phenylindolobenzothienyl group, or indolobenzothienylphenyl group (above, heteroaromatic group which may be linked or condensed), etc. .

As for Ar ¹ and Ar ² , any one of them is a condensed ring aromatic group having 7 to 18 carbon atoms, or any one of the following general formulas (2) to (9), because of excellent electron transport material characteristics. The substituents represented by these groups are each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, A halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. Either of these is a condensed aromatic group having 7 to 18 carbon atoms or a substituent represented by any one of the following general formulas (2) to (9) (these substituents are each independently methyl Group or diary having 10 to 36 carbon atoms And more preferably substituted also be) at arylamino group.

That is, as for Ar ¹ and Ar ² , one of them is a condensed ring aromatic group having 7 to 18 carbon atoms (fluorine atom, methyl group, ethyl group, 3 to 10 carbon atoms, because it is excellent in electron transport material properties. Alkyl group, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, halogenated alkyl group having 1 to 3 carbon atoms, halogenated alkoxy group having 1 to 3 carbon atoms, or diarylamino having 10 to 36 carbon atoms Or a substituent represented by any one of the following general formulas (2) to (9), preferably one of which has 7 to 18 carbon atoms. A condensed aromatic group (which may be substituted with a methyl group or a C10-C36 diarylamino group) or a substituent represented by any one of the following general formulas (2) to (9): More preferably.

Further, Ar ¹ and Ar ² are each independently a phenyl group, a condensed ring aromatic group having 7 to 18 carbon atoms, and the following general formulas (2) to (2), because they are excellent in electron transport material properties. A substituent represented by any one of the general formula (9) (these substituents are each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, Even if it has a C3-C10 alkoxy group, a C1-C3 halogenated alkyl group, a C1-C3 halogenated alkoxy group, or a C10-C36 diarylamino group as a substituent, It is preferable that each of Ar ¹ and Ar ² is independently a phenyl group, a condensed aromatic group having 7 to 18 carbon atoms, and the following general formula ( 2) One of general formula (9) (These substituents may each independently be a substituent selected from the group consisting of a methyl group or a C10-C36 diarylamino group). More preferred.

That is, with respect to Ar ¹ and Ar ² , both are independently a condensed ring aromatic group having 7 to 18 carbon atoms (fluorine atom, methyl group, ethyl group, An alkyl group having 3 to 10 carbon atoms, an methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or 10 to 36 carbon atoms Or a substituent represented by any one of the following general formulas (2) to (9), preferably both Ar ¹ and Ar ² Are each independently a condensed aromatic group having 7 to 18 carbon atoms (which may be substituted with a methyl group or a diarylamino group having 10 to 36 carbon atoms) or the following general formula (2) to general formula ( 9) A position represented by any of More preferred is a substituent.

（一般式（２）〜（９）中、Ａｒ^３は、各々独立して、炭素数４〜３０の芳香族基（各々独立して、フッ素原子、メチル基、エチル基、炭素数３〜１０のアルキル基、メトキシ基、エトキシ基、炭素数３〜１０のアルコキシ基、炭素数１〜３のハロゲン化アルキル基、炭素数１〜３のハロゲン化アルコキシ基、又は炭素数１０〜３６のジアリールアミノ基を置換基として有していてもよい）、メチル基、エチル基、メトキシ基、エトキシ基、炭素数１０〜３６のジアリールアミノ基又は水素原子を表わす。）
なお、炭素数７〜１８の縮環芳香族基は、縮環骨格のみを規定するものであり、当該縮環芳香族基の炭素数に置換基の炭素数は含まれない。当該炭素数７〜１８の縮環芳香族基は、炭素数７〜１８の縮環芳香族炭化水素及び炭素数７〜１８の縮環ヘテロ芳香族基からなり、特に限定するものではないが、例えば、ナフチル基、フルオレニル基、アントリル基、フェナントリル基、ピレニル基、クリセニル基、トリフェニレニル基、ペリレニル基、キノリル基、イソキノリル基、アクリジニル基、フェナントリジニル基、フェナントロリル基、インドリル基、インドリジニル基、ベンゾイミダゾリル基、アザインドリジニル基、ベンゾチアゾリル基、ベンゾフラニル基、ベンゾチエニル基、カルバゾリル基、カルボリニル基、ジアザカルバゾリル基、ジベンゾフラニル基、ジベンゾチエニル基、インドロカルバゾリル基、又はインドロジベンゾチエニル基が挙げられる。

(In General Formulas (2) to (9), Ar ³ is each independently an aromatic group having 4 to 30 carbon atoms (each independently being a fluorine atom, a methyl group, an ethyl group, or 3 to 10 carbon atoms). Alkyl group, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, halogenated alkyl group having 1 to 3 carbon atoms, halogenated alkoxy group having 1 to 3 carbon atoms, or diarylamino having 10 to 36 carbon atoms A methyl group, an ethyl group, a methoxy group, an ethoxy group, a C10-C36 diarylamino group, or a hydrogen atom.
The condensed aromatic group having 7 to 18 carbon atoms defines only a condensed ring skeleton, and the number of carbon atoms of the substituent is not included in the number of carbon atoms of the condensed aromatic group. The said C7-18 condensed ring aromatic group consists of a C7-18 condensed ring aromatic hydrocarbon and a C7-18 condensed ring heteroaromatic group, although it does not specifically limit, For example, naphthyl group, fluorenyl group, anthryl group, phenanthryl group, pyrenyl group, chrysenyl group, triphenylenyl group, perylenyl group, quinolyl group, isoquinolyl group, acridinyl group, phenanthridinyl group, phenanthryl group, indolyl group, indolizinyl group, Benzimidazolyl group, azaindolidinyl group, benzothiazolyl group, benzofuranyl group, benzothienyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group, dibenzofuranyl group, dibenzothienyl group, indolocarbazolyl group, or India Examples include a lodibenzothienyl group.

Further, the aromatic group of the general formula (2) - 4 to 30 carbon atoms in the (9) ^is the same definition as the aromatic group of 4 to 30 carbon atoms indicated by R 1 to R ^4, particularly limited not, but it can be exemplified the same substituents as the substituents exemplified in R ¹ to R ^4.

  Further, the diarylamino group having 10 to 36 carbon atoms in the general formulas (2) to (9) is not particularly limited, but the same ones as exemplified in the aforementioned diarylamino group having 10 to 36 carbon atoms are used. It can be illustrated.

  The diarylamino group having 10 to 36 carbon atoms is not particularly limited. For example, N, N-diphenylamino group, N-tolyl-N-phenylamino group, N, N-ditolylamino group, N, N -Dibiphenylamino group, N, N-di (terphenyl) amino group, N-phenyl-N-naphthylamino group, N-phenyl-N-biphenylamino group, N-phenyl-N-terphenylamino group, or N-biphenyl-N-terphenylamino group etc. are mentioned.

Preferred examples of the condensed aromatic group of 7 to 18 or the general formula (2) to the general formula (9) in Ar ¹ and Ar ² are each independently a fluorine atom, Methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, halogenated alkyl group having 1 to 3 carbon atoms, alkoxy halide having 1 to 3 carbon atoms And a substituent selected from the group consisting of a C10-C36 diarylamino group, and the substituent may be plural. When there are a plurality of substituents, each substituent may be the same or different.

  Of the substituents represented by the general formulas (2) to (9), the general formula (2), (3), (5), (7), or (9) The substituent represented by these is preferable.

In the substituents represented by the general formulas (2) to (9), Ar ³ is each independently an aromatic group having 4 to 30 carbon atoms (independently, in terms of excellent electron transport properties). , Fluorine atom, methyl group, methoxy group, or diarylamino group having 10 to 36 carbon atoms as a substituent), methyl group, ethyl group, diarylamino group having 10 to 36 carbon atoms, or hydrogen atom It is preferably each independently an aromatic group having 4 to 18 carbon atoms (each independently having a fluorine atom, a methyl group, a methoxy group, or a diarylamino group having 10 to 36 carbon atoms as a substituent). More preferably a methyl group, an ethyl group, a C10-C36 diarylamino group or a hydrogen atom, each independently a phenyl group, a pyridylphenyl group, a phenylpyridyl group, Enylpyridyl group, pyrimidylphenyl group, quinolylphenyl group, isoquinolylphenyl group, naphthyl group, biphenylyl group, fluorenyl group, benzofluorenyl group, dibenzofluorenyl group, terphenyl group, anthryl group, phenanthryl group , Pyrenyl group, chrysenyl group, triphenylenyl group, pyridyl group, bipyridyl group, terpyridyl group, quinolyl group, isoquinolyl group, indolyl group, imidazolyl group, benzoimidazolyl group, thiazole group, carbazolyl group, phenylcarbazolyl group, pyridylcarbazolyl Group, dipyridylcarbazolyl group, carbolinyl group, phenylcarbolinyl group, pyridylcarbolinyl group, or dibenzothiophenyl group (these substituents are each independently a fluorine atom, a methyl group, a methoxy group, or Carbon number A diarylamino group having 0 to 36 as a substituent), a methyl group, an ethyl group, a diarylamino group having 10 to 36 carbon atoms, or a hydrogen atom, and each independently, Phenyl group, pyridylphenyl group, phenylpyridyl group, diphenylpyridyl group, pyrimidylphenyl group, quinolylphenyl group, isoquinolylphenyl group, naphthyl group, biphenylyl group, fluorenyl group, benzofluorenyl group, terphenyl group , Anthryl group, phenanthryl group, pyrenyl group, chrysenyl group, triphenylenyl group, pyridyl group, bipyridyl group, terpyridyl group, quinolyl group, isoquinolyl group, indolyl group, benzoimidazolyl group, carbazolyl group, phenylcarbazolyl group, pyridylcarbazolyl Group, dipyridylcarbazolyl Group, carbolinyl group, phenylcarbolinyl group, pyridylcarbolinyl group, or dibenzothiophenyl group (these substituents are each independently a fluorine atom, a methyl group, a methoxy group, or a carbon number of 10 to 36). A diarylamino group (which may have a diarylamino group as a substituent), a methyl group, an ethyl group, a C10-C36 diarylamino group, or a hydrogen atom, and each independently a phenyl group, pyridylphenyl. Group, phenylpyridyl group, diphenylpyridyl group, pyrimidylphenyl group, quinolylphenyl group, isoquinolylphenyl group, naphthyl group, biphenylyl group, fluorenyl group, benzofluorenyl group, terphenyl group, anthryl group, phenanthryl Group, pyrenyl group, chrysenyl group, triphenylenyl group, pyridyl group, bipyri group Zyl group, terpyridyl group, quinolyl group, isoquinolyl group, indolyl group, benzimidazolyl group, carbazolyl group, phenylcarbazolyl group, pyridylcarbazolyl group, dipyridylcarbazolyl group, carbolinyl group, phenylcarbolinyl group, pyridylcarbo group More preferably, they are a linyl group, a dibenzothiophenyl group (these substituents may each independently have a methyl group as a substituent), or a hydrogen atom.

  In addition, the said C4-C18 aromatic group shows the aromatic group whose total carbon number of a ring skeleton is 4-18, and may be condensed or connected. In addition, the carbon number of the substituent which you may have separately is not contained in the said C4-C18 aromatic group. The aromatic group in the aromatic group having 4 to 18 carbon atoms is not particularly limited as long as it is an aromatic hydrocarbon group, a heteroaromatic group, or a group in which these are condensed or linked.

  Although it does not specifically limit as the said C4-C18 aromatic group, For example, a phenyl group, a pyridylphenyl group, a pyrimidylphenyl group, a quinolylphenyl group, an isoquinolylphenyl group, a naphthyl group, Biphenylyl group, fluorenyl group, benzofluorenyl group, dibenzofluorenyl group, terphenyl group, anthryl group, phenanthryl group, pyrenyl group, chrysenyl group, triphenylenyl group, pyridyl group, bipyridyl group, terpyridyl group, quinolyl group, isoquinolyl group Group, indolyl group, imidazolyl group, benzimidazolyl group, thiazole group, carbazolyl group, phenylcarbazolyl group, pyridylcarbazolyl group, dipyridylcarbazolyl group, carbolinyl group, phenylcarbolinyl group, pyridylcarbolinyl group, Or dibenzothiofe Le group.

  The benzofuropyrimidine compound of the present application is preferably a benzofuropyrimidine compound represented by the following general formula (1 ′) from the viewpoint of excellent electron transport properties, and the benzofuropyrimidine compound represented by the following general formula (1 ″). More preferred is a furopyrimidine compound.

（式中、Ａｒ^３は、前記一般式（２）〜（９）におけるＡｒ^３と同じ定義を表わす。）
なお、一般式（１’）におけるＡｒ^３の好ましい範囲については、一般式（２）〜（９）において示したＡｒ^３の好ましい範囲と同じである。

(In the formula, Ar ³ represents the same definition as Ar ³ in the general formulas (2) to (9).)
Note that the preferable range of Ar ³ in the general formula (1 '), the same as the preferable range of Ar ³ shown in the general formula (2) to (9).

Furthermore, in the general formula (1 ′), each Ar ³ independently represents a phenyl group, a pyridylphenyl group, a phenylpyridyl group, a diphenylpyridyl group, a pyrimidylphenyl group, a quinolylphenyl group, or an isoquinolylphenyl group. Group, naphthyl group, biphenylyl group, terphenyl group, anthryl group, phenanthryl group, pyrenyl group, chrysenyl group, triphenylenyl group, pyridyl group, bipyridyl group, quinolyl group, isoquinolyl group, carbazolyl group, phenylcarbazolyl group, pyridylcarbamate Zolyl group, dipyridylcarbazolyl group, carbolinyl group, phenylcarbolinyl group, pyridylcarbolinyl group, or dibenzothiophenyl group (these substituents each independently have a methyl group as a substituent) Or a hydrogen atom. Furthermore, in the general formula (1 ′), at least one of Ar ³ is a pyridylphenyl group, a phenylpyridyl group, a pyrimidylphenyl group, a pyridyl group, a bipyridyl group (these substituents are each independently methyl Group may be present as a substituent).

  Specific examples of the benzofuropyrimidine compound represented by the general formula (1) include the following compounds 1 to 140, but the present invention is not limited thereto.

次に、本発明の製造方法について説明する。

Next, the manufacturing method of this invention is demonstrated.

  The benzofuropyrimidine compound (1) of the present invention is prepared by the following reaction formula (1) or reaction formula (2) in the presence of a base, in the presence of a metal catalyst, or in the presence of a base and a metal catalyst. Can be manufactured.

  Hereinafter, the compound represented by the general formula (10) is generally referred to as the compound (10). In addition, it is synonymous also about other compounds including a compound (11).

（一般式中、
Ｒ^１〜Ｒ^４は、各々独立して、炭素数４〜６６の芳香族基（各々独立して、フッ素原子、メチル基、エチル基、炭素数３〜１０のアルキル基、メトキシ基、エトキシ基、炭素数３〜１０のアルコキシ基、炭素数１〜３のハロゲン化アルキル基、炭素数１〜３のハロゲン化アルコキシ基、又は炭素数１０〜３６のジアリールアミノ基を置換基として有していてもよい）、水素原子、重水素原子、フッ素原子、メチル基、エチル基、炭素数３〜１０のアルキル基、メトキシ基、エトキシ基、炭素数３〜１０のアルコキシ基、メチルチオ基、エチルチオ基、炭素数３〜１０のスルフィド基、又は炭素数１０〜３６のジアリールアミノ基を表す。
Ａｒ^１及びＡｒ^２は、各々独立して、炭素数４〜６６の芳香族基（各々独立して、フッ素原子、メチル基、エチル基、炭素数３〜１０のアルキル基、メトキシ基、エトキシ基、炭素数３〜１０のアルコキシ基、炭素数１〜３のハロゲン化アルキル基、炭素数１〜３のハロゲン化アルコキシ基、又は炭素数１０〜３６のジアリールアミノ基を置換基として有していてもよい）を表す。
Ａｒ^１１、Ａｒ^１２及びＡｒ^１３は、各々独立して、炭素数４〜６６の芳香族基（各々独立して、フッ素原子、メチル基、エチル基、炭素数３〜１０のアルキル基、メトキシ基、エトキシ基、炭素数３〜１０のアルコキシ基、炭素数１〜３のハロゲン化アルキル基、炭素数１〜３のハロゲン化アルコキシ基、又は炭素数１０〜３６のジアリールアミノ基を置換基として有していてもよい）を表す。
Ｘ^１〜Ｘ^４は、各々独立して、炭素数４〜６６の芳香族基（各々独立して、フッ素原子、メチル基、エチル基、炭素数３〜１０のアルキル基、メトキシ基、エトキシ基、炭素数３〜１０のアルコキシ基、炭素数１〜３のハロゲン化アルキル基、炭素数１〜３のハロゲン化アルコキシ基、又は炭素数１０〜３６のジアリールアミノ基を置換基として有していてもよい）、水素原子、重水素原子、フッ素原子、メチル基、エチル基、炭素数３〜１０のアルキル基、メトキシ基、エトキシ基、炭素数３〜１０のアルコキシ基、メチルチオ基、エチルチオ基、炭素数３〜１０のスルフィド基、炭素数１０〜３６のジアリールアミノ基、又は脱離基を表す。
Ｘ^５〜Ｘ^６及びＹは、各々独立して、水素原子、重水素原子、フッ素原子、メチル基、エチル基、炭素数３〜１０のアルキル基、メトキシ基、エトキシ基、炭素数３〜１０のアルコキシ基、メチルチオ基、エチルチオ基、炭素数３〜１０のスルフィド基、炭素数１０〜３６のジアリールアミノ基又は脱離基を表す。
Ｘ^７、Ｘ^８は脱離基を表す。
なお、一般式（１０）におてい、Ｘ^１〜Ｘ^６のうち少なくとも一つは脱離基である。）
また、反応式（１）で用いる化合物（１０）は、塩基又は酸の存在下に、次の反応式（３）で示される方法により製造することができる。同様に、化合物（１１）は、塩基又は酸の存在下に、次の反応式（４）で示される方法又は反応式（５）で示される方法により製造することができる。

(In the general formula,
R ^{1 to} R ⁴ are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group). , Having an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. A hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a methylthio group, an ethylthio group, A C3-C10 sulfide group or a C10-C36 diarylamino group is represented.
Ar ¹ and Ar ² are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group). , Having an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. May be).
Ar ¹¹ , Ar ¹² and Ar ¹³ are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group). , An ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. May be used).
X ^{1 to} X ⁴ are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group). , Having an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. A hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a methylthio group, an ethylthio group, A sulfide group having 3 to 10 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, or a leaving group is represented.
X ^{5 to} X ⁶ and Y are each independently a hydrogen atom, deuterium atom, fluorine atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, or 3 to 10 carbon atoms. Represents an alkoxy group, a methylthio group, an ethylthio group, a sulfide group having 3 to 10 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, or a leaving group.
X ⁷ and X ⁸ represent a leaving group.
In general formula (10), at least one of X ^{1 to} X ⁶ is a leaving group. )
Moreover, the compound (10) used by Reaction formula (1) can be manufactured by the method shown by following Reaction formula (3) in presence of a base or an acid. Similarly, compound (11) can be produced by the method shown by the following reaction formula (4) or the method shown by reaction formula (5) in the presence of a base or acid.

（一般式中、
Ａｒ^１１及びＡｒ^１２は、各々独立して、炭素数４〜６６の芳香族基（各々独立して、フッ素原子、メチル基、エチル基、炭素数３〜１０のアルキル基、メトキシ基、エトキシ基、炭素数３〜１０のアルコキシ基、炭素数１〜３のハロゲン化アルキル基、炭素数１〜３のハロゲン化アルコキシ基、又は炭素数１０〜３６のジアリールアミノ基を置換基として有していてもよい）を表す。
Ｒ^５はメチル基、エチル基、炭素数３〜１０のアルキル基、又は炭素数５〜１０の芳香族基を表す。
Ｘ^１〜Ｘ^４は各々独立して、炭素数４〜６６の芳香族基（各々独立して、フッ素原子、メチル基、エチル基、炭素数３〜１０のアルキル基、メトキシ基、エトキシ基、炭素数３〜１０のアルコキシ基、炭素数１〜３のハロゲン化アルキル基、炭素数１〜３のハロゲン化アルコキシ基、又は炭素数１０〜３６のジアリールアミノ基を置換基として有していてもよい）、水素原子、重水素原子、フッ素原子、メチル基、エチル基、炭素数３〜１０のアルキル基、メトキシ基、エトキシ基、炭素数３〜１０のアルコキシ基、メチルチオ基、エチルチオ基、炭素数３〜１０のスルフィド基、炭素数１０〜３６のジアリールアミノ基、又は脱離基を表す。
Ｘ^５〜Ｘ^６は、各々独立して、水素原子、重水素原子、フッ素原子、メチル基、エチル基、炭素数３〜１０のアルキル基、メトキシ基、エトキシ基、炭素数３〜１０のアルコキシ基、メチルチオ基、エチルチオ基、炭素数３〜１０のスルフィド基、炭素数１０〜３６のジアリールアミノ基、又は脱離基を表す。
Ｘ^７〜Ｘ^９は脱離基を表す。
なお、一般式（１０）及びそれに準ずる一般式（１５）、（１６）及び（１７）において、Ｘ^１〜Ｘ^６の少なくとも一つは脱離基である。）
Ｒ^５は、メチル基、エチル基、炭素数３〜１０のアルキル基、又は炭素数５〜１０の芳香族基を表す。炭素数３〜１０のアルキル基は、前記と同じ定義を表す。炭素数５〜１０の芳香族基としては、特に限定するものではないが、例えば、ピリジル基、フェニル基、トリル基、ｔｅｒｔ−ブチルフェニル基、ナフチル基、キノリル基、イソキノリル基等が挙げられる。

(In the general formula,
Ar ¹¹ and Ar ¹² are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group). , Having an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. May be).
R ⁵ represents a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, or an aromatic group having 5 to 10 carbon atoms.
X ^{1 to} X ⁴ are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, Even if it has a C3-C10 alkoxy group, a C1-C3 halogenated alkyl group, a C1-C3 halogenated alkoxy group, or a C10-C36 diarylamino group as a substituent, Good), hydrogen atom, deuterium atom, fluorine atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, methylthio group, ethylthio group, carbon It represents a sulfide group having 3 to 10 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, or a leaving group.
X ^{5 to} X ⁶ each independently represent a hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, or an alkoxy having 3 to 10 carbon atoms. A group, a methylthio group, an ethylthio group, a C3-C10 sulfide group, a C10-C36 diarylamino group, or a leaving group;
X < ⁷ > -X < ⁹ > represents a leaving group.
In general formula (10) and general formulas (15), (16), and (17) corresponding thereto, at least one of X ^{1 to} X ⁶ is a leaving group. )
R ⁵ represents a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, or an aromatic group having 5 to 10 carbon atoms. A C3-C10 alkyl group represents the same definition as the above. The aromatic group having 5 to 10 carbon atoms is not particularly limited, and examples thereof include a pyridyl group, a phenyl group, a tolyl group, a tert-butylphenyl group, a naphthyl group, a quinolyl group, and an isoquinolyl group.

  Z represents a chlorine atom, a bromine atom, a triflate or an iodine atom. Among these, a chlorine atom or a bromine atom is preferable in terms of good reaction yield and easy availability.

The leaving group represented by X ^{1 to} X ⁹ and Y is not particularly limited. For example, a hydrogen atom, a chlorine atom, a bromine atom, a triflate, an iodine atom, a metal-containing group (for example, Li, Na MgCl, MgBr, MgI, CuCl, CuBr, CuI, AlCl ₂ , AlBr ₂ , Al (Me) ₂ , Al (Et) ₂ , Al ( ⁱ Bu) ₂ , Sn (Me) ₃ , Sn (Bu) ₃ , SnF ₃ , ZnR ²⁴ (R ²⁴ represents a halogen atom. Examples of ZnR ²⁴ include ZnCl, ZnBr, ZnI, etc.), Si (R ²¹ ) ₃ (for example, SiMe ₃ , SiPh ₃ , SiMePh ₂ , SiCl _{3, SiF 3, Si (OMe} ) 3, Si (OEt) 3, Si (OMe) 2 OH , ^{_{etc.), BF 3 K, B (}} OR 22) 2 ( e.g., B _{^{OH) 2, B (OMe)}} 2, B (O i Pr) 2, B (OBu) 2, B (OPh) 2 or the _like), ^{B (OR} 23) _3, etc.) and the like.

Ligands such as ethers and amines may be coordinated with the metal-containing groups represented by X ^{1 to} X ⁹ and Y, and the reaction formula (1) is inhibited as the type of ligand. There is no limit as long as it does not.

Moreover, as B (OR < ²² >) ₂ , what is shown by following (I) to (VII) can be illustrated, and what is shown by (II) is a point with a sufficient yield.

前記Ｂ（ＯＲ^２３）_３としては次の（Ｉ）から（ＩＩＩ）で示されるものが例示できる。

Examples of B (OR ²³ ) ₃ include those represented by the following (I) to (III).

これらの脱離基のうち、反応後処理の容易性、原料調達の容易さの点で、塩素原子、臭素原子、トリフラート、ヨウ素原子、Ｂ（ＯＲ^２２）_２、又はＢ（ＯＲ^２３）_３が好ましい。

Among these leaving groups, chlorine atom, bromine atom, triflate, iodine atom, B (OR ²² ) ₂ , or B (OR ²³ ) ₃ is selected from the viewpoint of ease of post-reaction treatment and raw material procurement. preferable.

  Next, reaction formula (1) will be described.

  As shown in the reaction of the reaction formula (1), the compound (1) of the present invention is obtained by reacting the compound (10) or the compound (11) with the compound (21) in the presence of a metal catalyst or in the presence of a base and a metal catalyst. And can be synthesized by performing a coupling reaction.

  In addition, it is preferable that a metal catalyst is a palladium catalyst, a nickel catalyst, or a copper catalyst in reaction of Reaction formula (1) at the point which the efficiency etc. of a coupling reaction are excellent.

In the reaction of reaction formula (1), it is also possible to carry out the reaction by adding a base, and it is preferable to add a base from the viewpoint of improving the reaction yield. However, when X ^{1 to} X ⁷ and Y are a hydrogen atom, a chlorine atom, a bromine atom, a triflate, an iodine atom, B (OR ²² ) ₂ , or Si (R ²¹ ) ₃ , it is essential to add a base. .

  In addition, a phase transfer catalyst can be added in the reaction of the reaction formula (1). Although it does not specifically limit as a phase transfer catalyst, For example, 18-crown-6 ether etc. can be used. The amount added is an arbitrary amount within a range that does not significantly inhibit the reaction.

  Although it does not specifically limit as a metal catalyst used for reaction of Reaction formula (1), For example, a palladium catalyst, a copper catalyst, and a nickel catalyst are mention | raise | lifted.

  Although it does not specifically limit as a palladium catalyst, For example, salts, such as palladium chloride, palladium acetate, trifluoroacetate palladium, palladium nitrate, can be illustrated. Further, π-allyl palladium chloride dimer, palladium acetylacetonate, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, tri (tert -Butyl) phosphine palladium and dichloro (1,1'-bis (diphenylphosphino) ferrocene) palladium and the like. Among them, a palladium complex having a tertiary phosphine as a ligand such as dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, tri (tert-butyl) phosphinepalladium is preferable in terms of a good yield, and is available. In terms of ease, tri (tert-butyl) phosphine palladium is more preferable.

  The copper catalyst is not particularly limited, and examples thereof include copper chloride, copper bromide, copper iodide, copper oxide, and copper triflate. Among these, copper oxide and copper iodide are preferable from the viewpoint of excellent coupling reaction results, and copper oxide is more preferable from the viewpoint of easy availability.

  The nickel catalyst is not particularly limited. For example, nickel chloride, nickel bromide, nickel chloride hydrate, dichloro (dimethoxyethane) nickel, dichloro [1,2-bis (diphenylphosphino) ethane] nickel Dichloro [1,3-bis (diphenylphosphino) propane] nickel, dichloro [1,4-bis (diphenylphosphino) butane] nickel, dichloro [1,1′-bis (diphenylphosphino) ferrocene] nickel ( Examples of the four include nickel complex having tertiary phosphine as a ligand and dichloro (N, N, N ′, N′-tetramethylethylenediamine) nickel. Among them, dichloro (dimethoxyethane) nickel, dichloro [1,4-bis (diphenylphosphino) butane] nickel, and dichloro (N, N, N ′, N′-tetramethylethylenediamine) nickel have excellent coupling reaction results. In terms of this point, dichloro (dimethoxyethane) nickel and dichloro [1,4-bis (diphenylphosphino) butane] nickel are more preferable in that they are easily available.

  For palladium complexes having the above tertiary phosphine as a ligand and nickel complexes having a tertiary phosphine as a ligand, a tertiary phosphine is added to a palladium salt, nickel salt or complex thereof. Can be adjusted. The adjustment can be performed separately from the reaction and then added to the reaction system, or can be performed in the reaction system.

  The tertiary phosphine is not particularly limited, and examples thereof include triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, and 9,9-dimethyl. -4,5-bis (diphenylphosphino) xanthene, 2- (diphenylphosphino) -2 '-(N, N-dimethylamino) biphenyl, 2- (di-tert-butylphosphino) biphenyl, 2- ( Dicyclohexylphosphino) biphenyl, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenyl Sufino) ferrocene, tri (2-furyl) phosphine, tri (o-tolyl) phosphine, tris (2,5-xylyl) phosphine, (±) -2,2′-bis (diphenylphosphino) -1,1 ′ -Binaphthyl, 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl and the like can be exemplified. Of these, (tert-butyl) phosphine or 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl is preferred because it is readily available and yields are good.

  When a tertiary phosphine is added to a palladium salt, nickel salt or complex thereof, the addition amount of the tertiary phosphine is 1 mol of palladium salt, nickel salt or complex thereof (in terms of palladium or nickel atom). It is preferable that it is 0.1-10 times mole with respect to it, and it is further more preferable that it is 0.3-5 times mole from a point with a sufficient yield.

  In addition, it is also possible to add a ligand separately to said copper catalyst. The ligand to be added to the copper catalyst is not particularly limited. For example, 2,2′-bipyridine, 1,10-phenanthroline, N, N, N ′, N′-tetramethylethylenediamine, triphenyl Examples include phosphine, 2- (dicyclohexylphosphino) biphenyl, and the like. Of these, 1,10-phenanthroline is preferred because it is readily available and yields are good.

  In the reaction formula (1), the base that can be used is not particularly limited. For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, potassium acetate, sodium acetate , Potassium phosphate, sodium phosphate, sodium fluoride, potassium fluoride, cesium fluoride and the like. Among these, potassium carbonate, potassium phosphate, or sodium hydroxide is preferable in terms of a good yield.

  The reaction of reaction formula (1) is preferably carried out in a solvent. The solvent is not particularly limited, and examples thereof include water, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), tetrahydrofuran (THF), toluene, benzene, diethyl ether, 1,4-dioxane, ethanol, butanol, and xylene. These may be exemplified, and these may be used in appropriate combination. Among these, a mixed solvent of 1,4-dioxane, xylene, toluene and butanol or a mixed solvent of xylene and butanol is preferable in terms of a good yield.

  Although it does not specifically limit as a compound (21) in Reaction formula (1), For example, the compound represented by the following 4-1 to 4-63 can be illustrated.

（これらの置換基は、各々独立して、フッ素原子、メチル基、エチル基、炭素数３〜１０のアルキル基、メトキシ基、エトキシ基、炭素数３〜１０のアルコキシ基、炭素数１〜３のハロゲン化メチル基、炭素数１〜３のハロゲン化メトキシ基、又は炭素数１０〜３６のジアリールアミノ基を置換基として有してもよい。
また、Ｙは、上記一般式（２１）におけるＹと同じ定義である。）

(These substituents are each independently a fluorine atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, or 1 to 3 carbon atoms. A halogenated methyl group, a halogenated methoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms may be used as a substituent.
Y is the same definition as Y in the general formula (21). )

（これらの置換基は、各々独立して、フッ素原子、メチル基、エチル基、炭素数３〜１０のアルキル基、メトキシ基、エトキシ基、炭素数３〜１０のアルコキシ基、炭素数１〜３のハロゲン化メチル基、炭素数１〜３のハロゲン化メトキシ基、又は炭素数１０〜３６のジアリールアミノ基を置換基として有してもよい。
また、Ｙは、上記一般式（２１）におけるＹと同じ定義である。）
化合物（２１）は、例えば、Ｊ．Ｔｓｕｊｉ著、「Ｐａｌｌａｄｉｕｍ Ｒｅａｇｅｎｔｓ ａｎｄ Ｃａｔａｌｙｓｔｓ」，Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ，２００４年、Ｊｏｕｒｎａｌ ｏｆ Ｏｒｇａｎｉｃ Ｃｈｅｍｉｓｔｒｙ，６０巻，７５０８−７５１０，１９９５年、Ｊｏｕｒｎａｌ ｏｆ Ｏｒｇａｎｉｃ Ｃｈｅｍｉｓｔｒｙ，６５巻，１６４−１６８，２０００年、Ｏｒｇａｎｉｃ Ｌｅｔｔｅｒｓ，１０巻，９４１−９４４，２００８年、又はＣｈｅｍｉｓｔｒｙ ｏｆ Ｍａｔｅｒｉａｌｓ，２０巻，５９５１−５９５３，２００８年に開示されている方法を用いて製造することができる。また化合物（２１）中の任意の水素原子は重水素原子に置換されていてもよい。

(These substituents are each independently a fluorine atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, or 1 to 3 carbon atoms. A halogenated methyl group, a halogenated methoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms may be used as a substituent.
Y is the same definition as Y in the general formula (21). )
Compound (21) is described, for example, in J. Org. Tsuji, “Palladium Reagents and Catalysts”, John Wiley & Sons, 2004, Journal of Organic Chemistry, 60, 7508-7510, 1995, Journal of Organics, 16: Journal of Organics. 10, 941-944, 2008, or Chemistry of Materials, 20, 5951-5953, 2008. In addition, any hydrogen atom in compound (21) may be substituted with a deuterium atom.

  In the reaction formula (1), the compound (10) or (11) is reacted with the compound (21) in the presence or absence of a base in the presence of a metal catalyst to produce the compound (1) of the present invention. By applying the reaction conditions of the Suzuki-Miyaura reaction, the target product can be obtained with good yield.

  The amount of the metal catalyst used in the reaction formula (1) is not particularly limited as long as it is a so-called catalyst amount, but is 0.1% with respect to 1 mol of the compound (10) or (11) in terms of good yield. It is preferable that it is -0.01 times mole (in metal atom conversion).

  Although there is no restriction | limiting in particular in the usage-amount of a base, It is preferable that it is 0.5-10 times mole with respect to 1 mol of a compound (21), and is a 1-4 times mole by a point with a sufficient yield. Is more preferable.

  There is no particular limitation on the molar ratio of the compound (10) or (11) and the compound (21) used in the reaction formula (1), but 1 mole per 1 mole of the leaving group of the compound (10) or (11). It is preferable to use 10 to 10 moles of the compound (21), and it is more preferable to use 1 to 3 moles of the compound (21) in terms of good yield.

  In addition, the compound (10) and the compound (11) industrially supply a compound such as the compound (1) that is remarkably excellent in low driving voltage property, high light emission efficiency, and long life of the organic electroluminescence device. Therefore, it is an excellent material and is very valuable industrially.

  Next, reaction formulas (2), (3) and (4) will be described.

  The reactions of the reaction formulas (2), (3) and (4) can be carried out by subjecting the compounds described in the respective reaction formulas to a ring condensation reaction in the presence of a base or an acid, respectively.

The base that can be used in the reactions of the reaction formulas (2), (3), and (4) is not particularly limited, and examples thereof include potassium tert-butoxide, sodium hydroxide, potassium hydroxide, and sodium carbonate. And potassium carbonate, lithium carbonate, cesium carbonate, potassium acetate, sodium acetate, potassium phosphate, sodium phosphate, sodium fluoride, potassium fluoride, cesium fluoride, and the like. Of these, potassium tert-butoxide is preferred because of its good yield. In addition, the acid that can be used in the reaction is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, carbonic acid, phosphoric acid, acetic acid, benzoic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and p-toluenesulfone. Examples include acids and various Lewis acids. Lewis acids include AlCl ₃ , Al (OTf) ₃ , ZnCl ₂ , ZnBr ₂ , ZnI ₂ , Zn (OTf) ₂ , FeCl ₂ , FeCl ₃ , BF ₃ , GaCl ₃ , InCl ₃ , InBr ₃ , InI ₃ , In (OTf) ₃ , Yb (OTf) ₃ , SiMe ₃ Cl, SiMe ₃ I, SiMe ₃ OTf, and the like. Of these, sulfuric acid is preferred because of its good yield.

  The reactions of reaction formulas (2), (3) and (4) are preferably carried out in a solvent. The solvent is not particularly limited, and examples thereof include water, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), tetrahydrofuran (THF), toluene, benzene, diethyl ether, 1,4-dioxane, ethanol, butanol, and xylene. These may be exemplified, and these may be used in appropriate combination. Of these, THF, DMF, and xylene are preferable in terms of good yield.

  Although there is no restriction | limiting in particular in the usage-amount of a base, It is preferable that it is 0.5-10 times mole with respect to 1 mol of compounds (13), (16), and (19), and a point with a sufficient yield, It is more preferable that it is 1.1-4.0 times mole.

  Next, the reaction of the reaction formula (2) will be described.

  The reaction formula (2) can be performed in one pot, but can also be performed stepwise as shown in the following reaction formulas (6) and (7).

（一般式中、Ａｒ^１、Ａｒ^２、Ｒ^１〜Ｒ^４、Ｚについては、反応式（２）と同じ定義を示す。）
反応式（２）の反応に用いる化合物（１２）〜（１４）は、公知の製造方法を用いて製造することもできるし、市販品を用いることもできる。

(In the general formula, Ar ¹ , Ar ² , R ^{1 to} R ⁴ , and Z have the same definition as reaction formula (2).)
The compounds (12) to (14) used in the reaction of the reaction formula (2) can be produced using a known production method, or commercially available products can be used.

  Although it does not specifically limit as a compound (12), For example, the compound represented by the following 5-1 to 5-38 can be illustrated.

化合物（１３）としては、特に限定するものではないが、例えば、次の６−１〜６−１５で表される化合物を例示することができる。

Although it does not specifically limit as a compound (13), For example, the compound represented by the following 6-1 to 6-15 can be illustrated.

化合物（１４）としては、特に限定するものではないが、例えば、次の７−１〜７−３９で表される化合物を例示することができる。

Although it does not specifically limit as a compound (14), For example, the compound represented by the following 7-1 to 7-39 can be illustrated.

反応式（２）は反応式（６）及び（７）に分解できる。即ち、本反応は化合物（１２）が塩基存在下、化合物（１３）と反応することにより化合物（２１）が生成される。この化合物（２１）が反応式（７）で表される様に化合物（１４）と反応することで本発明の化合物（１）が得られる。

Reaction formula (2) can be decomposed into reaction formulas (6) and (7). That is, in this reaction, compound (21) is produced by reacting compound (12) with compound (13) in the presence of a base. The compound (21) of the present invention is obtained by reacting the compound (21) with the compound (14) as represented by the reaction formula (7).

  Although the amount of the base used is not particularly limited, it is preferably 0.5 to 10 times by mole with respect to 1 mole of compound (13), and 1.1 to 4.0 times in terms of good yield. More preferably, it is a mole.

  Although there is no restriction | limiting in particular in the molar ratio of the compound (12) and compound (13) used by Reaction formula (6), Compound (12) is 0.1-10 times mole with respect to 1 mol of compound (13). In terms of good yield of compound (21), it is preferably 1.1 to 2.0 moles.

  Although there is no restriction | limiting in particular in the molar ratio of the compound (21) and compound (14) used by Reaction formula (7), Compound (14) is 0.1-20 times mole with respect to 1 mol of compound (21). In terms of good yield of the benzofuropyrimidine compound (1) of the present invention, 1.0 to 5 times is preferable.

  Next, the reaction of the reaction formula (3) will be described.

  Reaction formula (3) can be performed in one pot, but can also be performed stepwise as shown in the following reaction formulas (8) and (9).

（一般式中、Ａｒ^１１、Ａｒ^１２、Ｘ^１〜Ｘ^６、Ｚについては、反応式（３）と同じ定義を示す。）
化合物（１５）〜（１７）は、公知の方法を用いて製造することもできるし、市販品を用いることもできる。

(In the general formula, Ar ¹¹ , Ar ¹² , X ^{1 to} X ⁶ , and Z have the same definition as reaction formula (3).)
Compounds (15) to (17) can be produced using known methods, or commercially available products can also be used.

  Although it does not specifically limit as a compound (15), For example, the compound represented by the following 8-1 to 8-10 can be illustrated.

化合物（１６）としては、特に限定するものではないが、例えば、次の９−１〜９−５で表される化合物を例示することができる。

Although it does not specifically limit as a compound (16), For example, the compound represented by the following 9-1 to 9-5 can be illustrated.

化合物（１７）としては、特に限定するものではないが、例えば、次の１０−１〜１０−１２で表される化合物を例示することができる。

Although it does not specifically limit as a compound (17), For example, the compound represented by the following 10-1 to 10-12 can be illustrated.

反応式（３）は塩基又は酸存在下に、化合物（１５）と化合物（１６）と化合物（１７）を反応させ、本発明の化合物（１０）を製造する方法である。

Reaction formula (3) is a method for producing compound (10) of the present invention by reacting compound (15), compound (16) and compound (17) in the presence of a base or acid.

  Reaction formula (3) can be decomposed into reaction formulas (8) and (9). That is, in this reaction, compound (15) is produced by reacting compound (15) with compound (16) in the presence of a base. By reacting compound (22) with compound (17) as represented by reaction formula (9), compound (10) of the present invention is obtained.

  Although the compound (22) may be isolated, it may be used for the reaction (9) which is the next step in one pot without isolation.

  Although the usage-amount of a base does not have a restriction | limiting in particular, it is preferable that it is 0.5-10 times mole with respect to 1 mol of a compound (16), and 1.1-4.0 times by the point with a good yield. More preferably, it is a mole.

  Although there is no restriction | limiting in particular in the molar ratio of the compound (15) and compound (16) used by Reaction formula (8), Compound (15) is 0.1-10 times mole with respect to 1 mol of compound (16). In terms of good yield of compound (22), it is preferably 1.1 to 2.0 moles.

  Although there is no restriction | limiting in particular in the molar ratio of the compound (22) and compound (17) used by Reaction formula (9), Compound (17) is 0.1-20 times mole with respect to 1 mol of compound (22). In terms of good yield of the compound (10) of the present invention, 1.0 to 5 times is preferable.

  Next, reaction formula (4) will be described.

  The reaction formula (4) can be performed in one pot, but can also be performed stepwise as shown in the following reaction formulas (10) and (11).

（一般式中、Ａｒ^１２、Ｘ^１〜Ｘ^５、Ｘ^７、Ｚ、Ｒ^５については、反応式（４）と同じ定義を示す。）
反応式（４）は塩基又は酸存在下に、化合物（１８）と化合物（１９）と化合物（１７）を反応させ、化合物（２０）を製造する方法である。

(In the general formula, Ar ¹² , X ^{1 to} X ⁵ , X ⁷ , Z, and R ⁵ have the same definitions as those in Reaction Formula (4).)
Reaction formula (4) is a method for producing compound (20) by reacting compound (18), compound (19) and compound (17) in the presence of a base or acid.

  Reaction formula (4) can be decomposed into reaction formulas (10) and (11). That is, in this reaction, compound (23) is produced by reacting compound (18) with compound (19) in the presence of a base. By reacting compound (23) with compound (17) as represented by reaction formula (11), compound (20) of the present invention is obtained.

  Although the compound (23) may be isolated, it may be used for the reaction (11) which is the next step in one pot without isolation.

  Although the usage-amount of a base does not have a restriction | limiting in particular, it is preferable that it is 0.5-10 times mole with respect to 1 mol of a compound (18), and 1.1-4.0 times by the point with a good yield. More preferably, it is a mole.

  Although there is no restriction | limiting in particular in the molar ratio of the compound (18) and compound (19) used by Reaction formula (10), Compound (18) is 0.1-10 times mole with respect to 1 mol of compound (19). In terms of good yield of compound (23), it is preferably 1.1 to 2.0 moles.

  Although there is no restriction | limiting in particular in the molar ratio of the compound (23) and compound (17) used by Reaction formula (11), Compound (17) is 0.1-20 times mole with respect to 1 mol of compound (23). Is preferable, and 1.0-5 times is preferable at the point with the good yield of a compound (20).

  Next, reaction formula (5) will be described.

  Reaction formula (5) is a method for producing compound (11) by reacting compound (20) with a halogenating agent or sulfonylating agent in the presence or absence of a base. The halogenating agent is not particularly limited, and examples thereof include thienyl chloride, thienyl bromide, thienyl iodide, phosphoryl chloride, phosphoryl bromide, and phosphoryl iodide. The sulfonylating agent is not particularly limited, and examples thereof include trifluoromethanesulfonic acid anhydride, toluenesulfonic acid anhydride, toluenesulfonic acid chloride, methanesulfonic acid chloride, and nitrobenzenesulfonic acid chloride.

  Although it does not specifically limit as a base used by Reaction formula (5), The same thing as the base shown by Reaction formula (2), (3) and (4) can be used.

  Although there is no restriction | limiting in particular in the molar ratio of the compound (20) used by reaction of Reaction formula (5), and a reactive agent, 0.1-20 times mole of a reactive agent is preferable with respect to 1 mol of a compound (20). From the viewpoint of good yield of the benzofuropyrimidine compound (11) of the present invention, 1.0 to 5 times is preferable.

  About compound (1), (10) and (11) of this invention, purity can be raised by performing processes, such as reprecipitation, concentration, filtration, and refinement | purification after completion | finish of each reaction. In order to further increase the purity, purification may be performed by recrystallization, silica gel column chromatography, sublimation, or the like, if necessary.

  This invention is an organic electroluminescent element containing the benzofuropyrimidine compound represented by General formula (1), The said benzofuropyrimidine compound is preferably used for an electron carrying layer, an electron injection layer, or a light emitting layer.

  That is, the benzofuropyrimidine compound is preferably used as an electron transport material or an electron injection material.

  The benzofuropyrimidine compound represented by the general formula (1) can be preferably used as an electron transport material (electron transport material, electron injection material, etc.) of an organic electroluminescence device. At this time, for the anode, the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the light emitting layer dopant, the light emitting layer host, the cathode, and the like used in combination, generally known materials are selected by those skilled in the art. Can be used.

  About the structure of the said organic electroluminescent element, what is necessary is just a conventionally well-known thing, and it does not specifically limit.

Although there is no limitation in particular in the manufacturing method of the thin film for organic electroluminescent elements containing the compound (1) of this invention, The film-forming by a vacuum evaporation method can be mentioned as a preferable example. Film formation by the vacuum evaporation method can be performed by using a general-purpose vacuum evaporation apparatus. The vacuum degree of the vacuum chamber when forming a film by the vacuum evaporation method is such that the production tact time for producing the organic electroluminescent element is short and the production cost is superior, so that commonly used diffusion pumps, turbo molecular pumps, cryogenic pumps are used. It is preferably about 1 × 10 ⁻² to 1 × 10 ⁻⁶ Pa that can be reached by a pump or the like, and the deposition rate is preferably 0.005 to 10 nm / second, although it depends on the thickness of the film to be formed. Moreover, the thin film for organic electroluminescent elements which consists of a compound (1) can also be manufactured by the solution coating method. For example, the compound (1) is dissolved in an organic solvent such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate or tetrahydrofuran, and a spin coating method, ink jet method, casting method or Film formation by a dip method or the like is also possible.

It is a cross-sectional schematic diagram of the organic electroluminescent element produced in Evaluation Example 1-1 grade | etc.,. It is a cross-sectional schematic diagram of the organic electroluminescent element produced in Evaluation Example 2-1.

1. 1. Glass substrate with ITO transparent electrode 2. hole injection layer First hole transport layer 4. Second hole transport layer 5. Light emitting layer 6. 6. Electron transport layer Electron injection layer 8. Cathode layer 11. 11. Glass substrate with ITO transparent electrode Hole injection layer 13. First hole transport layer 14. Second hole transport layer 15. Light emitting layer 16. Electron transport layer 17. Cathode layer

  EXAMPLES Hereinafter, although a synthesis example, an Example, a comparative example, and a reference example are given and this invention is demonstrated further in detail, this invention is limited to these and is not interpreted.

  Example-1

アルゴン気流下、化合物 Ａ−１（４．１ｇ）、及び３−ブロモ−５−クロロベンゾニトリル（４．７６ｇ）をＴＨＦ（２０ｍＬ）に加え、そこにカリウムｔｅｒｔ−ブトキシド（２．４７ｇ）のＴＨＦ溶液（１００ｍＬ）を加え、２．０時間加熱還流した。次いで、反応混合物にヘキサン（１２０ｍＬ）を加え室温まで放冷した。析出した固体をヘキサンで洗浄することで目的の２−（３−ブロモ−５−クロロフェニル）−［１］ベンゾフロ［３，２−ｄ］ピリミジン−４（３Ｈ）−オン（Ｂ−１）の薄褐色粉末（収量６．８３ｇ、収率９１％）を得た。

Under a stream of argon, Compound A-1 (4.1 g) and 3-bromo-5-chlorobenzonitrile (4.76 g) were added to THF (20 mL), and potassium tert-butoxide (2.47 g) in THF was added thereto. The solution (100 mL) was added and heated to reflux for 2.0 hours. Then, hexane (120 mL) was added to the reaction mixture and allowed to cool to room temperature. The precipitated solid was washed with hexane, so that the desired 2- (3-bromo-5-chlorophenyl)-[1] benzofuro [3,2-d] pyrimidin-4 (3H) -one (B-1) was diluted. A brown powder (yield 6.83 g, yield 91%) was obtained.

¹ H-NMR (DMSO-d ₆ ), δ (ppm): 7.37 (t, J = 7.2 Hz, 1H), 7.52 (dd, J = 8.3, 7.2 Hz, 1H), 7.66 (d, J = 8.3 Hz, 1H), 7.70 (s, 1H), 8.04 (d, J = 7.2 Hz, 1H), 8.39 (s, 1H), 8. 50 (s, 1H).
Under an argon stream, phosphoryl chloride (2.6 g) was added to compound B-1 (1.50 g), and the mixture was heated and stirred at 80 ° C. for 2.5 hours. After allowing to cool, chloroform and 4N-NaOH aqueous solution were added to make the aqueous layer basic. Insoluble components were filtered, and the organic layer of the filtrate was extracted. The organic layer was concentrated to give the desired 2- (3-bromo-5-chlorophenyl) -4-chloro- [1] benzofuro [3,2-d] pyrimidine (B-2) yellow powder (yield 384 mg, Yield 24%).

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.59 (dd, J = 7.8, 6.7 Hz, 1H), 7.66 (s, 1H), 7.77 (d, J = 8.4 Hz, 1H), 7.80 (dd, J = 8.4, 6.7 Hz, 1H), 8.35 (d, J = 7.7 Hz, 1H), 8.55 (s, 1H), 8.66 (s, 1H).
Under an argon stream, THF (10 mL) was added to compound B-2 (394 mg) and phenylmagnesium bromide in 1M-THF (4.0 mL), and the mixture was heated to reflux for 72 hours. After allowing to cool, water and chloroform were added, and the organic layer was extracted. Toluene was added to the organic layer, followed by concentration and purification by column chromatography (developing solvent: hexane) to purify the desired 2- (3-bromo-5-chlorophenyl) -4-phenyl- [1] benzofuro [3, A white powder (yield 72 mg, yield 16%) of 2-d] pyrimidine (B-3) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.55-7.59 (m, 1H), 7.61-7.70 (m, 4H), 7.76-7.78 (m, 2H), 8.38 (d, J = 7.7 Hz, 1H), 8.67 (s, 1H), 8.73 (d, J = 8.3 Hz, 2H), 8.78 (s, 1H) .
Example-2

アルゴン気流下、２−シアノフェノール（５９６ｍｇ）、臭化フェナシル（１．０９ｇ）、及び炭酸ナトリウム（１．０６ｇ）をＤＭＦ（１０ｍＬ）に加え、８０℃で１時間撹拌した。次いで、反応混合物に水（１０ｍＬ）を加え室温まで放冷した。析出した固体を水及びヘキサンで洗浄することで目的の３−アミノ−２−ベンゾイルベンゾフラン（Ａ−２）の黄色粉末（収量１．１４ｇ、収率９６％）を得た。

Under an argon stream, 2-cyanophenol (596 mg), phenacyl bromide (1.09 g), and sodium carbonate (1.06 g) were added to DMF (10 mL), and the mixture was stirred at 80 ° C. for 1 hour. Next, water (10 mL) was added to the reaction mixture, and the mixture was allowed to cool to room temperature. The precipitated solid was washed with water and hexane to obtain the desired 3-amino-2-benzoylbenzofuran (A-2) yellow powder (yield 1.14 g, yield 96%).

¹ H-NMR (DMSO-d ₆ ), δ (ppm): 7.31 (dd, J = 8.0, 6.5 Hz, 1H), 7.47 (s, 2H), 7.53-7. 63 (m, 5H), 8.06 (d, J = 7.8 Hz, 1H), 8.11 (d, J = 8.0 Hz, 2H).
Under a stream of argon, Compound A-2 (1.10 g) and 3-bromo-5-chlorobenzonitrile (1.5 g) were added to THF (4.6 mL), and potassium tert-butoxide (573 mg) in THF was added thereto. The solution (18.5 mL) was added and stirred at 30 ° C. for 100 hours. Then water (23 mL) and methanol (12 mL) were added to the reaction mixture. The precipitated solid was washed with water, methanol and hexane to give the desired 2- (3-bromo-5-chlorophenyl) -4-phenyl- [1] benzofuro [3,2-d] pyrimidine (B-3). White powder (yield 1.43 g, yield 71%) was obtained.

  Example-3

アルゴン気流下、化合物 Ｂ−３（７１ｍｇ）、４−（２−ピリジル）フェニルボロン酸（７１ｍｇ）、酢酸パラジウム（１．８ｍｇ）、及び２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（７．８ｍｇ）をＴＨＦ（３．３ｍＬ）に加え、さらに３Ｍ−炭酸カリウム水溶液（０．２５ｍＬ）を添加し、次いで２０時間加熱還流した。反応混合物を室温まで放冷後、水を加えた。析出した固体を水で洗浄し、メタノールで洗浄し、さらにヘキサンで洗浄することで、目的の２−［４，４’’−ビス（２−ピリジル）−［１，１’：３’，１’’］−テルフェニル−５’−イル］−４−フェニル−［１］ベンゾフロ［３，２−ｄ］ピリミジン（Ｃ−１）の灰色粉末（収量１００ｍｇ，収率９８％）を得た。

Under an argon stream, Compound B-3 (71 mg), 4- (2-pyridyl) phenylboronic acid (71 mg), palladium acetate (1.8 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′- Triisopropylbiphenyl (7.8 mg) was added to THF (3.3 mL), 3M aqueous potassium carbonate solution (0.25 mL) was further added, and the mixture was heated to reflux for 20 hours. The reaction mixture was allowed to cool to room temperature, and water was added. The precipitated solid is washed with water, washed with methanol, and further washed with hexane, so that the desired 2- [4,4 ″ -bis (2-pyridyl)-[1,1 ′: 3 ′, 1 ”] -Terphenyl-5′-yl] -4-phenyl- [1] benzofuro [3,2-d] pyrimidine (C-1) was obtained as a gray powder (yield 100 mg, yield 98%).

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.29 (dd, J = 7.2, 4.8 Hz, 2H), 7.57 (dd, J = 7.7, 6.5 Hz, 1H) ), 7.63 (t, J = 7.2 Hz, 1H), 7.65-7.71 (m, 2H), 7.74-7.79 (m, 2H), 7.82 (dd, J = 7.9, 7.2 Hz, 2H), 7.87 (d, J = 7.9 Hz, 2H), 7.99 (d, J = 8.4 Hz, 4H), 8.09 (s, 1H) , 8.22 (d, J = 8.4 Hz, 4H), 8.47 (d, J = 7.7 Hz, 1H), 8.78 (d, J = 4.8 Hz, 2H), 8.80 ( d, J = 8.4 Hz, 2H), 9.05 (s, 2H).
Example-4

アルゴン気流下、化合物 Ｂ−２（３８０ｍｇ）、４−（２−ピリジル）フェニルボロン酸（６３４ｍｇ）、酢酸パラジウム（４．３ｍｇ）、及び２−ジシクロヘキシルホスフィノ−２’，４’，６’−トリイソプロピルビフェニル（１８．３ｍｇ）をＴＨＦ（１９ｍＬ）に加え、さらに３Ｍ−炭酸カリウム水溶液（２．１ｍＬ）を添加し、次いで７２時間加熱還流した。反応混合物を室温まで放冷後、水を加えた。析出した固体を水で洗浄し、メタノールで洗浄し、さらにヘキサンで洗浄することで、目的の２−［４，４’’−ビス（２−ピリジル）−［１，１’：３’，１’’］−テルフェニル−５’−イル］−４−［４−（２−ピリジル）フェニル］−［１］ベンゾフロ［３，２−ｄ］ピリミジン（Ｃ−２）の灰色粉末（収量５４７ｍｇ，収率８１％）を得た。

Under an argon stream, Compound B-2 (380 mg), 4- (2-pyridyl) phenylboronic acid (634 mg), palladium acetate (4.3 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′- Triisopropylbiphenyl (18.3 mg) was added to THF (19 mL), 3M-potassium carbonate aqueous solution (2.1 mL) was further added, and then the mixture was heated to reflux for 72 hours. The reaction mixture was allowed to cool to room temperature, and water was added. The precipitated solid is washed with water, washed with methanol, and further washed with hexane, so that the desired 2- [4,4 ″ -bis (2-pyridyl)-[1,1 ′: 3 ′, 1 ''] -Terphenyl-5'-yl] -4- [4- (2-pyridyl) phenyl]-[1] benzofuro [3,2-d] pyrimidine (C-2) gray powder (yield 547 mg, Yield 81%) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.30 (dd, J = 7.2, 4.8 Hz, 2H), 7.33 (dd, J = 7.3, 4.8 Hz, 1H) ), 7.58 (t, J = 7.3 Hz, 1H), 7.76-7.88 (m, 8H), 8.00 (d, J = 8.4 Hz, 4H), 8.10 (s) , 1H), 8.22 (d, J = 8.4 Hz, 4H), 8.33 (d, J = 8.6 Hz, 2H), 8.47 (d, J = 7.6 Hz, 1H), 8 .78 (d, J = 4.8 Hz, 2H), 8.80 (d, J = 4.8 Hz, 1H), 8.93 (d, J = 8.6 Hz, 2H), 9.06 (s, 2H).
Example-5

アルゴン気流下、化合物 Ａ−１（２．０５ｇ）、３，５−ジクロロベンゾニトリル（１．８９ｇ）をＴＨＦ（１０ｍＬ）に加え、そこにカリウムｔｅｒｔ−ブトキシド（１．２３ｇ）のＴＨＦ溶液（５０ｍＬ）を加え、２．０時間加熱還流した。次いで反応混合物にヘキサン（６０ｍＬ）を加え室温まで放冷した。析出した固体をヘキサンで洗浄することで目的の２−（３，５−ジクロロフェニル）−［１］ベンゾフロ［３，２−ｄ］ピリミジン−４（３Ｈ）−オン（Ｂ−４）の薄黄色粉末（収量３．１ｇ、収率９３％）を得た。

Under a stream of argon, Compound A-1 (2.05 g) and 3,5-dichlorobenzonitrile (1.89 g) were added to THF (10 mL), and potassium tert-butoxide (1.23 g) in THF (50 mL) was added thereto. ) And heated to reflux for 2.0 hours. Next, hexane (60 mL) was added to the reaction mixture, and the mixture was allowed to cool to room temperature. The precipitated solid was washed with hexane to give the desired 2- (3,5-dichlorophenyl)-[1] benzofuro [3,2-d] pyrimidin-4 (3H) -one (B-4) as a pale yellow powder (Yield 3.1 g, yield 93%) was obtained.

¹ H-NMR (DMSO-d ₆ ), δ (ppm): 7.35 (dd, J = 7.7, 7.3 Hz, 1H), 7.51 (dd, J = 8.2, 7.3 Hz) , 1H), 7.57 (s, 1H), 7.65 (d, J = 8.2 Hz, 1H), 8.02 (d, J = 7.7 Hz, 1H), 8.33 (s, 2H) ).
Under an argon stream, compound B-4 (3.10 g) was added to DMF (94 mL), thionyl chloride (8.91 g) was added thereto, and the mixture was heated and stirred at 85 ° C. for 2.5 hours. After allowing to cool, water (94 mL), 4N-NaOH aqueous solution (72 mL) and saturated aqueous sodium hydrogen carbonate solution (4 mL) were added to make the aqueous layer basic. The insoluble component is filtered, and the solid is washed with water, washed with methanol, and further washed with hexane to give the desired 2- (3,5-dichlorophenyl) -4-chloro- [1] benzofuro [3,2- d] A white powder (yield 2.5 g, yield 77%) of pyrimidine (B-5) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.50 (s, 1H), 7.59 (dd, J = 7.8, 6.7 Hz, 1H), 7.76 (d, J = 8.4 Hz, 1H), 7.80 (dd, J = 8.4, 6.7 Hz, 1H), 8.34 (d, J = 7.8 Hz, 1H), 8.49 (s, 2H).
Under an argon stream, THF (10 mL) was added to compound B-2 (394 mg) and phenylmagnesium bromide in 1M-THF (4.0 mL), and the mixture was heated to reflux for 72 hours. After allowing to cool, water and chloroform were added, and the organic layer was extracted. Toluene was added to the organic layer, followed by concentration and purification by column chromatography (developing solvent: hexane) to purify the desired 2- (3,5-dichlorophenyl) -4-phenyl- [1] benzofuro [3,2- d] A white powder (yield 72 mg, yield 16%) of pyrimidine (B-6) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.55-7.59 (m, 1H), 7.61-7.70 (m, 4H), 7.76-7.78 (m, 2H), 8.38 (d, J = 7.7 Hz, 1H), 8.67 (s, 1H), 8.73 (d, J = 8.3 Hz, 2H), 8.78 (s, 1H) .
Example-6

アルゴン気流下、化合物 Ｂ−３（２．１８ｇ）、９−フェナントレンボロン酸（１．２２ｇ）、及びビス（トリフェニルホスフィン）パラジウムジクロリド（７０．２ｍｇ）をＴＨＦ（５０ｍＬ）に加え、さらに３Ｍ−炭酸カリウム水溶液（３．７ｍＬ）を添加し、次いで５時間加熱還流した。反応混合物を室温まで放冷後、水を加えた。析出した固体を水で洗浄し、メタノールで洗浄し、さらにヘキサンで洗浄することで、目的の２−［３−クロロ−５−（９−フェナントリル）フェニル］−４−フェニル−［１］ベンゾフロ［３，２−ｄ］ピリミジン（Ｂ−７）の灰色粉末（収量２．６０ｇ，収率９７％）を得た。

Under an argon stream, Compound B-3 (2.18 g), 9-phenanthreneboronic acid (1.22 g), and bis (triphenylphosphine) palladium dichloride (70.2 mg) were added to THF (50 mL), and 3M- Aqueous potassium carbonate (3.7 mL) was added and then heated to reflux for 5 hours. The reaction mixture was allowed to cool to room temperature, and water was added. The precipitated solid was washed with water, washed with methanol, and further washed with hexane, whereby the desired 2- [3-chloro-5- (9-phenanthryl) phenyl] -4-phenyl- [1] benzofuro [ A gray powder (yield 2.60 g, 97% yield) of 3,2-d] pyrimidine (B-7) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.53 (dd, J = 7.9, 6.3 Hz, 1H), 7.57-7.78 (m, 10H), 7.84 ( s, 1H), 7.98 (dd, 9.9, 8.5 Hz, 2H), 8.35 (d, J = 7.7 Hz, 1H), 8.73 (d, J = 8.2 Hz, 2H) ), 8.78 (d, J = 8.3 Hz, 1H), 8.81 (s, 1H), 8.82-8.84 (m, 2H).
Under an argon stream, compound B-7 (1.17 g), 4- (2-pyridyl) phenylboronic acid (482 mg), palladium acetate (9.9 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6 '-Triisopropylbiphenyl (62.9 g) was added to THF (22 mL), 3M aqueous potassium carbonate solution (1.6 mL) was further added, and the mixture was heated to reflux for 19 hours. The reaction mixture was allowed to cool to room temperature, and water was added. The precipitated solid was washed with water, washed with methanol, and further washed with hexane to obtain a gray solid. The obtained gray solid was dissolved in toluene, insoluble components were filtered off, and methanol was added to the filtrate to precipitate a white solid. The precipitated solid was filtered off to obtain the desired 2- [5- (9-phenanthryl) -4 ′-(2-pyridyl) biphenyl-3-yl] -4-phenyl- [1] benzofuro [3,2 -D] A gray powder (yield 1.24 g, yield 87%) of pyrimidine (C-3) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.27-7.30 (m, 1H), 7.54 (dd, J = 7.7, 6.8 Hz, 1H), 7.57- 7.83 (m, 10H), 7.85 (d, J = 7.8 Hz, 1H), 7.94 (s, 1H), 7.99-8.01 (m, 4H), 8.13 ( d, J = 8.3 Hz, 1H), 8.19 (d, J = 8.4 Hz, 2H), 8.40 (d, J = 7.6 Hz, 1H), 8.75-8.78 (m 3H), 8.81 (d, J = 8.2 Hz, 1H), 8.86 (d, J = 8.2 Hz, 1H), 8.93 (s, 1H), 9.15 (s, 1H) ).
Production and Performance Evaluation of Organic Electroluminescent Device Containing Component of Benzofuropyrimidine Compound of the Present Invention The present invention will be explained by the following test examples, but the present invention is not limited to these. In addition, structural formulas and abbreviations of the compounds used are shown below.

評価実施例１−１
基板には、２ｍｍ幅の酸化インジウム−スズ（ＩＴＯ）膜がストライプ状にパターンされたＩＴＯ透明電極付きガラス基板を用いた。この基板をイソプロピルアルコールで洗浄した後、酸素プラズマ洗浄にて表面処理を行った。洗浄後の基板に、真空蒸着法で各層の真空蒸着を行い、断面図を図１に示すような発光面積４ｍｍ^２有機電界発光素子を作製した。

Evaluation Example 1-1
As the substrate, a glass substrate with an ITO transparent electrode in which an indium-tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used. The substrate was cleaned with isopropyl alcohol and then surface-treated by oxygen plasma cleaning. Each layer was vacuum-deposited on the cleaned substrate by a vacuum deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm ² as shown in FIG.

First, the said glass substrate was introduce | transduced in the vacuum evaporation tank and it pressure-reduced to 1.0 * 10 <^-4> Pa.
Thereafter, a hole injection layer 2, a first hole transport layer 3, a second hole transport layer 4, a light emitting layer 5, an electron transport layer are formed as an organic compound layer on the glass substrate with an ITO transparent electrode shown by 1 in FIG. 6 and the electron injection layer 7 were sequentially formed, and then the cathode layer 8 was formed.

  In addition, all the materials which comprise each layer of an organic electroluminescent element were vacuum-deposited by the resistance heating system.

  As the hole injection layer 2, HTL-1 was vacuum-deposited with a film thickness of 0.15 nm / second and a film thickness of 65 nm.

  As the first hole transport layer 3, HAT-CN was vacuum-deposited with a film thickness of 0.025 nm / second and a film thickness of 5 nm.

  As the second hole transport layer 4, HTL-2 was vacuum-deposited with a film thickness of 10 nm at a film formation rate of 0.15 nm / second.

  As the light emitting layer 5, EML-1 and EML-2 were mixed at a film formation rate of 0.18 nm / second and a film thickness of 25 nm (EML-1 / EML-2 = 95.4 / 4.6 (weight ratio)). Vacuum deposition was performed.

  As the electron transport layer 6, C-1 synthesized in Example-3 of the present invention was vacuum-deposited with a film thickness of 30 nm at a film formation rate of 0.15 nm / second.

  As the electron injection layer 7, Liq was vacuum-deposited with a film thickness of 0.005 nm / second and a film thickness of 0.5 nm.

  Finally, a metal mask was disposed so as to be orthogonal to the ITO stripe, and the cathode layer 8 was formed. The cathode layer 8 is formed by vacuum-depositing magnesium / silver (weight ratio 80/20) and silver in this order at film thicknesses of 80 nm and 20 nm at a film formation rate of 0.5 nm / second and 0.2 nm / second, respectively. A two-layer structure was adopted.

  Each film thickness was measured with a stylus type film thickness meter (DEKTAK, manufactured by Veeco). Furthermore, this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less. Sealing was performed using a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation).

Evaluation Example 1-2
In the electron transport layer 6 of Evaluation Example 1-1, an organic electroluminescent element was produced in the same manner as in Evaluation Example 1-1 except that C-3 synthesized in Example-6 was used instead of C-1. Was made.

Reference Example 1-1
In the electron transport layer 6 of Evaluation Example 1-1, an organic electroluminescent element was produced in the same manner as in Evaluation Example 1-1 except that ETL-1 which is a known electron transport material was used instead of C-1. Was made.

A direct current was applied to the produced organic electroluminescence device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. As the lifetime characteristic (h), the luminance decay time during continuous lighting when a current density of 10 mA / cm ² was passed was measured. Further, the time when the luminance (cd / m ² ) was reduced by 20% and the drive voltage increase when the device was driven for 20 hours were measured. In addition, the measurement results are shown in the table below together with the initial voltage (V) and the initial current efficiency (cd / A) when a current density of 10 mA / cm ² was passed. In addition, about the element lifetime (h) of each evaluation example, time (h) when the brightness | luminance (cd / m < ² >) of the element in the reference example 1-1 reduced 5% from the initial stage was set to 100, and it was a relative value. Indicated.

参考例１−１に比べて、本発明のベンゾフロピリミジン化合物を使用した有機電界発光素子は寿命特性に優れていることが分かった。

As compared with Reference Example 1-1, it was found that the organic electroluminescent device using the benzofuropyrimidine compound of the present invention was superior in life characteristics.

Evaluation Example 2-1
As the substrate, a glass substrate with an ITO transparent electrode in which an indium-tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used. The substrate was cleaned with isopropyl alcohol and then surface-treated by oxygen plasma cleaning. Each layer was vacuum-deposited on the cleaned substrate by a vacuum deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm ² as shown in FIG.

First, the said glass substrate was introduce | transduced in the vacuum evaporation tank and it pressure-reduced to 1.0 * 10 <^-4> Pa.
Thereafter, a hole injection layer 12, a first hole transport layer 13, a second hole transport layer 14, a light emitting layer 15 and an electron transport layer are formed as an organic compound layer on the glass substrate with an ITO transparent electrode indicated by 11 in FIG. 16 were sequentially formed, and then the cathode layer 17 was formed.

  In addition, all the materials which comprise each layer of an organic electroluminescent element were vacuum-deposited by the resistance heating system.

  As the hole injection layer 12, HTL-1 was vacuum-deposited with a film thickness of 65 nm at a film formation rate of 0.15 nm / second.

  As the first hole transport layer 13, HAT-CN was vacuum-deposited with a film thickness of 5 nm at a film formation rate of 0.025 nm / second.

  As the second hole transport layer 14, HTL-2 was vacuum-deposited with a film thickness of 10 nm at a film formation rate of 0.15 nm / second.

  As the light emitting layer 15, EML-1 and EML-2 are formed at a film formation rate of 0.18 nm / second and a film thickness of 25 nm (EML-1 / EML-2 = 95.4 / 4.6 (weight ratio)). Vacuum deposition was performed.

  As the electron transport layer 16, C-1 and Liq synthesized in Example-3 of the present invention were formed with a film thickness of 0.15 nm / second and a film thickness of 30 nm (C-1 / Liq = 50/50 (weight ratio). ) Co-evaporation).

  Finally, a metal mask was arranged so as to be orthogonal to the ITO stripe, and the cathode layer 17 was formed. The cathode layer 17 is formed by vacuum-depositing magnesium / silver (weight ratio 80/20) and silver in this order at film thicknesses of 80 nm and 20 nm at a film formation rate of 0.5 nm / second and 0.2 nm / second, respectively. A two-layer structure was adopted.

Each film thickness was measured with a stylus type film thickness meter (DEKTAK, manufactured by Veeco).
Furthermore, this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less. For the sealing, a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation) were used.

Evaluation Example 2-2
In the electron transport layer 16 of Evaluation Example 2-2, an organic electroluminescent element was produced in the same manner as in Evaluation Example 2-1, except that C-3 synthesized in Example-6 was used instead of C-1. Was made.

Reference Example 2-1
In the electron transport layer 16 of Evaluation Example 2-1, an organic electroluminescent element was produced in the same manner as in Evaluation Example 2-1, except that ETL-1 which is a known electron transport material was used instead of C-1. Was made.

A direct current was applied to the produced organic electroluminescence device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. As the lifetime characteristic (h), the luminance decay time during continuous lighting when a current density of 10 mA / cm ² was passed was measured. Further, the time when the luminance (cd / m ² ) was reduced by 10% and the drive voltage increase when the device was driven for 50 hours were measured. In addition, the measurement results are shown in the table below together with the initial voltage (V) and the initial current efficiency (cd / A) when a current density of 10 mA / cm ² was passed. In addition, about the drive voltage (V) and current efficiency (cd / A) of each evaluation example, it showed with the relative value when the measured value of Reference Example 2-1 (ETL-1) was set to 100. The element lifetime (h) of each evaluation example is expressed as a relative value with the time (h) when the luminance (cd / m ² ) of the element in Reference Example 2-1 was reduced by 5% from the initial value being 100. .

参考例２−１に比べて、本発明のベンゾフロピリミジン化合物を使用した有機電界発光素子は寿命特性に顕著に優れていることが分かった。

Compared to Reference Example 2-1, it was found that the organic electroluminescent device using the benzofuropyrimidine compound of the present invention was remarkably excellent in lifetime characteristics.

  The organic electroluminescent device using the benzofuropyrimidine compound of the present invention can be driven for a longer time than the organic electroluminescent device using the existing material. Further, the benzofuropyrimidine compound of the present invention can be applied to a light emitting host layer and the like in addition to the electron transport layer of this example. Thus, the benzofuropyrimidine compound of the present invention is useful as an electron injection material or an electron transport material. Furthermore, the present invention can be applied not only to an element using a fluorescent light emitting material but also to various organic electroluminescent elements using a phosphorescent light emitting material. Further, the benzofuropyrimidine compound of the present invention has high solubility, and it is possible to produce an element using not only a vacuum deposition method but also a coating method. Furthermore, it is useful not only for applications such as flat panel displays but also for illumination applications that require low power consumption.

Claims (12)

General formula (1)

(In the formula, R ^{1 to} R ⁴ are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, methoxy Group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, halogenated alkyl group having 1 to 3 carbon atoms, halogenated alkoxy group having 1 to 3 carbon atoms, or diarylamino group having 10 to 36 carbon atoms as a substituent Which may have), hydrogen atom, deuterium atom, fluorine atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, methylthio group , An ethylthio group, a C3-C10 sulfide group, or a C10-C36 diarylamino group.
Ar ¹ and Ar ² are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group). , Having an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. May be). )
A benzofuropyrimidine compound represented by the formula: R ^{1 to} R ⁴ are each independently an aromatic group having 4 to 30 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group). , An optionally substituted alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, or a halogenated alkoxy group having 1 to 3 carbon atoms), a hydrogen atom, a deuterium atom The benzofuropyrimidine compound of Claim 1 which is a fluorine atom, a methyl group, an ethyl group, or a C3-C10 alkyl group. Either Ar ¹ or Ar ² is a condensed aromatic group having 7 to 18 carbon atoms (fluorine atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, carbon number 3 Or an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms). The substituent represented by any one of the following general formulas (2) to (9) is represented, and the other is an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group). An alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a carbon number 10-36 diaryl a Roh represents also may) have as a substituent group, benzo furopyrimidine compound according to claim 1 or claim 2.

(In General Formulas (2) to (9), Ar ³ is each independently an aromatic group having 4 to 30 carbon atoms (each independently being a fluorine atom, a methyl group, an ethyl group, or 3 to 10 carbon atoms). Alkyl group, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, halogenated alkyl group having 1 to 3 carbon atoms, halogenated alkoxy group having 1 to 3 carbon atoms, or diarylamino having 10 to 36 carbon atoms A methyl group, an ethyl group, a methoxy group, an ethoxy group, a C10-C36 diarylamino group, or a hydrogen atom. Ar ³ each independently has an aromatic group having 4 to 30 carbon atoms (each independently has a fluorine atom, a methyl group, a methoxy group, or a diarylamino group having 10 to 36 carbon atoms as a substituent). The benzofuropyrimidine compound of Claim 3 which is a methyl group, an ethyl group, a C10-C36 diarylamino group, or a hydrogen atom. In the presence of a metal catalyst or in the presence of a base and a metal catalyst, a compound represented by the general formula (10) or a compound represented by the general formula (11) and a compound represented by the general formula (21) A method for producing a benzofuropyrimidine compound represented by the general formula (1), wherein a coupling reaction is performed.

(In the general formula,
R ^{1 to} R ⁴ are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group). , Having an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. A hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a methylthio group, an ethylthio group, A C3-C10 sulfide group or a C10-C36 diarylamino group is represented.
Ar ¹ and Ar ² are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group). , Having an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. May be).
Ar ¹¹ , Ar ¹² and Ar ¹³ are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group). , An ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. May be used).
X ^{1 to} X ⁴ are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group). , Having an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. A hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a methylthio group, an ethylthio group, A sulfide group having 3 to 10 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, or a leaving group is represented.
X ^{5 to} X ⁶ and Y are each independently a hydrogen atom, deuterium atom, fluorine atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, or 3 to 10 carbon atoms. An alkoxy group, a methylthio group, an ethylthio group, a sulfide group having 3 to 10 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, or a leaving group.
X ⁷ represents a leaving group.
In general formula (10), at least one of X ^{1 to} X ⁶ is a leaving group. ) A benzofuro represented by the general formula (1), wherein the compound represented by the general formula (12), the general formula (13) and the general formula (14) is subjected to a ring condensation reaction in the presence of a base or an acid. A method for producing a pyrimidine compound.

(In the general formula,
R ^{1 to} R ⁴ are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group). , Having an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. A hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a methylthio group, an ethylthio group, A C3-C10 sulfide group or a C10-C36 diarylamino group is represented.
Ar ¹ and Ar ² are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group). , Having an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. May be).
X ⁸ represents a leaving group. ) A benzofuro represented by the general formula (10), wherein the compound represented by the general formula (15), the general formula (16) and the general formula (17) is subjected to a ring condensation reaction in the presence of a base or an acid. A method for producing a pyrimidine compound.

(In the general formula,
Ar ¹¹ and Ar ¹² are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group). , Having an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. May be).
X ^{1 to} X ⁴ are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group). , Having an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. A hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a methylthio group, an ethylthio group, A sulfide group having 3 to 10 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, or a leaving group is represented.
X ⁵ and X ⁶ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, or an alkoxy having 3 to 10 carbon atoms. A group, a methylthio group, an ethylthio group, a C3-C10 sulfide group, a C10-C36 diarylamino group, or a leaving group;
X ⁸ represents a leaving group. ) A benzofuropyrimidine represented by the general formula (11), wherein the compound represented by the general formula (20) is reacted with a halogenating agent or a sulfonylating agent in the presence or absence of a base. Compound production method.

(In the general formula,
Ar ¹² is each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, or a carbon number). 3-10 alkoxy group, C1-C3 halogenated alkyl group, C1-C3 halogenated alkoxy group, or C10-C36 diarylamino group may be substituted. Represents.
X ^{1 to} X ⁴ are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group). , Having an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. A hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a methylthio group, an ethylthio group, A sulfide group having 3 to 10 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, or a leaving group is represented.
X ⁶ is a hydrogen atom, deuterium atom, fluorine atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, methylthio group, ethylthio group, A sulfide group having 3 to 10 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, or a leaving group is represented.
X ⁷ represents a leaving group. ) A benzofuropyrimidine compound represented by the general formula (10).

(In the general formula,
Ar ¹¹ and Ar ¹² are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group). , Having an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. May be).
X ^{1 to} X ⁴ are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group). , Having an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. A hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a methylthio group, an ethylthio group, A sulfide group having 3 to 10 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, or a leaving group is represented.
X ⁵ and X ⁶ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, or an alkoxy having 3 to 10 carbon atoms. A group, a methylthio group, an ethylthio group, a C3-C10 sulfide group, a C10-C36 diarylamino group, or a leaving group;
At least one of X ^{1 to} X ⁶ is a leaving group. ) A benzofuropyrimidine compound represented by the general formula (11).

(In the general formula,
Ar ¹² is each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, or a carbon number). 3-10 alkoxy group, C1-C3 halogenated alkyl group, C1-C3 halogenated alkoxy group, or C10-C36 diarylamino group may be substituted. Represents.
X ^{1 to} X ⁴ are each independently an aromatic group having 4 to 66 carbon atoms (each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group). , Having an alkoxy group having 3 to 10 carbon atoms, a halogenated alkyl group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. A hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a methylthio group, an ethylthio group, A sulfide group having 3 to 10 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, or a leaving group is represented.
X ⁶ is a hydrogen atom, deuterium atom, fluorine atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group having 3 to 10 carbon atoms, methylthio group, ethylthio group, A sulfide group having 3 to 10 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, or a leaving group is represented.
X ⁷ represents a leaving group. ) An electron injection or electron transport material comprising the benzofuropyrimidine compound according to claim 1. An electron injection or electron transport material for an organic electroluminescent device comprising the benzofuropyrimidine compound according to claim 1.

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