JP6500340B2 - Benzofuropyrimidine compound, method for producing the same, and use thereof - Google Patents

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 injecting material or an electron transporting material comprising the same.

  An organic electroluminescent device has a basic structure in which a light emitting layer containing a light emitting material is sandwiched between a hole transporting layer and an electron transporting layer, and further, an anode and a cathode are attached to the outer side thereof. It is an element utilizing 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 block layer, a light emitting layer and a hole block layer, and the electron transport layer is divided into an electron transport layer and an electron injection layer. It may be configured.

  In recent years, a large number of organic electroluminescent devices using triazine and pyrimidine compounds for the light emitting layer, electron transporting layer, etc. have been reported, but the light emitting efficiency characteristics, driving voltage characteristics and long life characteristics completely satisfy the market requirements. However, even better materials are required.

  As an electron transport material etc., a dibenzofuran compound (for example, patent document 1) and a nitrogen-substituted dibenzothiophene compound are disclosed (for example, refer to patent documents 2-3), and it is proposed to improve the lifetime of the device using these However, improvement is desired in terms of increasing the driving voltage of the element and in the point of further prolonging the life.

  Also, the use of nitrogen-substituted dibenzofuran compounds has been proposed for many applications, not limited to organic electroluminescent devices, but methods for producing these compounds have been hardly reported, and simple synthetic methods are required. .

WO 2007/069569 pamphlet JP, 2011-84531, A WO 2013/038650 pamphlet

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

  Among the carrier transport materials, as for the electron injection material and the electron transport material, a new material which drives the device at a low voltage due to the excellent electron injection property and electron transport characteristics, has a high luminous efficiency, and drives the device for a long time It is desired.

  There is also a need for a convenient synthesis of benzofuropyrimidine compounds that are useful compounds.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have found that the benzofuropyrimidine compounds represented by the general formula (1) of the present invention have an electron durability and an electron durability higher than those of conventionally known compounds. It has been found that the hole durability is significantly improved. From these findings, when the benzofuropyrimidine compound is used as an electron transport layer in an organic electroluminescent device, the lifetime of the organic electroluminescent device is extended as compared with the case where a known or general electron transport material is used. It has been found that the voltage rise during driving is suppressed, and the present invention has been completed.

  That is, according to the present invention, a benzofuropyrimidine compound (hereinafter, also referred to as "compound (1)") represented by the following general formula (1) of the present invention, a method for producing the same, and an electron injecting material or electron transport containing it It relates to the material.

(Wherein, R ^{1 to} R ⁴ each independently represent 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, 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 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 And an ethylthio group, a sulfide group having 3 to 10 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms.
Ar ¹ and Ar ² each independently represent 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 And having, as a substituent, 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 Also represent). )
In addition, the present invention can provide a very useful production intermediate for industrially producing the compound (1).

  Hereinafter, the present invention will be described in detail.

  The present invention relates to the above-mentioned compound (1), a method for producing the same, and an electron injecting material or an electron transporting material containing the same.

  The present invention also relates to production intermediates for producing the above-mentioned 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 which may be fused or linked, and the carbon number of the aromatic group does not include the carbon number of the substituent. In the said C4-C66 aromatic group, an aromatic group will not be specifically limited if it is an aromatic hydrocarbon group, a hetero aromatic group, or what these condensed or connected.

  That is, the aromatic group having 4 to 66 carbon atoms represents an aromatic group in which the total carbon number of the ring skeleton is 4 to 66 and which may be fused or linked. In addition, carbon number of the substituent which may have separately is not contained in the said C4-C66 aromatic group. The said C4-C66 aromatic group will not be specifically limited if it is an aromatic hydrocarbon group, a hetero aromatic group, or what these condensed or connected.

  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 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, anthryl phenyl group, phenyl anthryl group, phenyl anthryl phenyl group, phenanthryl group, phenanthryl phenyl group, phenyl phenanthryl group, pyrenyl group, phenyl pyre Group, pyrenyl phenyl group, fluorenyl group, fluorenyl phenyl group, phenyl fluorenyl group, fluoranthenyl group, phenyl fluoranthenyl group, fluoranthenyl phenyl group, perylenyl group, phenyl perylenyl group, perylenyl pheny Group, triphenylenyl group, phenyltriphenylenyl group, triphenylenyl phenyl group, tetracenyl group, phenyl to terracenyl group, tetracenyl phenyl group, chrysenyl group, phenyl chrysenyl group, chrysenyl phenyl group Or an aromatic hydrocarbon group which may be fused), pyridyl group, phenyl pyridyl group, pyridyl phenyl group, bipyridyl group, biphenyl pyridyl group, pyridyl biphenyl group, diphenyl pyridyl group, pyrimidyl group, phenyl pyrimidyl group, pyri Mysyl phenyl group, pyrazyl group, phenyl pyrazyl group, pyrazyl phenyl group, triazinyl group, phenyl triazyl group, triazyl phenyl group, quinolyl group, phenyl quinolyl group, quinolyl phenyl group, pyridyl quinolyl group, isoquinolyl group, Phenyl isoquinolyl , Isoquinolyl phenyl group, pyridyl isoquinolyl group, quinoxalinyl group, phenyl quinoxalinyl group, quinoxalinyl phenyl group, acridinyl group, phenyl acridinyl group, acridinyl phenyl group, phenanthridinyl group , Phenyl phenanthridinyl group, phenanthridinyl phenyl group, phenanthrolinyl group, phenyl phenanthrolinyl group, phenanthrolinyl phenyl group, pyrrolyl group, phenyl pyrrolyl group, pyrrolyl phenyl group, pyridyl pylori Group, furanyl group, phenyl furanyl group, furanyl phenyl group, pyridyl furanyl group, thienyl group, phenyl thienyl group, thienyl phenyl group, imidazolyl group, phenyl imidazolyl group, imidazolyl phenyl group, oxazolyl group, phenyl oxazolyl Group, oxazolylphene Group, isoxazolyl group, phenyl isoxazolyl group, isoxazolyl phenyl group, oxadiazolyl group, phenyl oxadiazolyl group, oxadiazolyl phenyl group, thiazolyl group, phenyl thiazolyl group, thiazolyl phenyl group, Indolyl group, phenyl indolyl group, indolyl phenyl group, benzofuranyl group, phenylbenzofuranyl group, benzofuranyl phenyl group, benzothiazolyl group, phenylbenzothiazolyl group, benzothiazolylphenyl group, benzoimidazolyl group, phenylbenzoimidazolyl group Group, benzoimidazolylphenyl group, benzoxazolyl group, phenylbenzoxazolyl group, benzoxazolylphenyl group, benzothiazolyl group, phenylbenzothiazolyl group, benzothiazolylphenyl group, dibenzofuran Group, phenyldibenzofuranyl group, dibenzofuranylphenyl group, dibenzothienyl group, phenyldibenzothienyl group, dibenzothienylphenyl group, carbazolyl group, phenylcarbazolyl group, carbazolylphenyl group, pyridylcarbazolyl group, Pyridyl phenyl carbazolyl group, carborinyl group, phenyl carborinyl group, carborinyl phenyl group, indolocarbazolyl group, phenyl indolocarbazolyl group, phenyl indolocarbazolyl phenyl group, indolocarbazolyl group And the like. Examples thereof include a phenyl group, an indolodibenzothienyl group, a phenylindorhodibenzothienyl group, and an indolodibenzothienylphenyl 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, phenethyl group and the like.

  The alkoxy group having 3 to 10 carbon atoms is not particularly limited. For example, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentyloxy group , Sec-pentyloxy, cyclopentyloxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy or phenethyloxy And the like.

  The halogenated alkyl group having 1 to 3 carbon atoms is not particularly limited, and, for example, chloromethyl group, dichloromethyl group, trichloromethyl group, fluoromethyl group, trifluoromethyl group, trifluoromethyl group, chloroethyl group, dichloroethyl group Ethyl group, trichloroethyl group, pentachloroethyl group, fluoroethyl group, difluoroethyl group, trifluoroethyl group, pentafluoroethyl group, chloropropyl group, fluoropropyl group and the like can be mentioned.

  The halogenated alkoxy group having 1 to 3 carbon atoms is not particularly limited, and examples thereof include a chloromethyloxy group, a dichloromethyloxy group, a trichloromethyloxy group, a fluoromethyloxy group, a trifluoromethyloxy group, tri Chloromethyloxy group, chloroethyloxy group, dichloroethyloxy group, trichloroethyloxy group, pentachloroethyloxy group, fluoroethyloxy group, difluoroethyloxy group, trifluoroethyloxy group, pentafluoroethyloxy group, chloro A propyloxy group or a fluoropropyloxy group etc. are mentioned.

  The C10-C36 diarylamino group represents an amino group to which two types of optionally different aryl groups are bonded, and means that the total carbon number is 10-36.

  Although it does not specifically limit as a C10-C36 diarylamino group, For example, N, N- diphenylamino group, N- tolyl-N- phenylamino group, N, N- di tolyl amino 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. Among these, an N, N-diphenylamino group, an N-tolyl-N-phenylamino group, an N, N-ditolylamino group, or an N, N-dibiphenyl is preferred in that the electron transporting material properties of the compound (1) are excellent. 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 A sulfide group or a phenethyl sulfide group etc. are mentioned.

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 Selected from the group consisting of ethoxy, alkoxy having 3 to 10 carbons, halogenated alkyl having 1 to 3 carbons, halogenated alkoxy having 1 to 3 carbons, and diarylamino having 10 to 36 carbons The substituent may have one or more 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 to 36 diarylamino groups are preferred.

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

  In addition, although it does not specifically limit as said C4-C30 aromatic group, The total number of carbon number is 30 or less among the substituents illustrated in the above-mentioned C4-C66 aromatic group The thing can be illustrated.

  That is, an aromatic group having 4 to 30 carbon atoms defines only a ring skeleton which may be fused or linked, and the number of carbons of the substituent is not included in the number of carbons of the aromatic group. The aromatic group in the said C4-C30 aromatic group will not be specifically limited if it is an aromatic hydrocarbon group, a hetero aromatic group, or what these condensed or connected.

  Although it does not specifically limit as said C4-C30 aromatic group, For example, a phenyl group, biphenylyl group, terphenyl group, a naphthyl group, a naphthylphenyl group, a phenyl naphthyl group, a naphthyl biphenyl group, a biphenyl naphthyl is mentioned. Group, diphenylnaphthyl group, phenylnaphthylphenyl group, anthryl group, anthryl phenyl group, phenyl anthryl group, phenyl anthryl phenyl group, phenanthryl group, phenanthryl phenyl group, phenyl phenanthryl group, pyrenyl group, phenyl pyre Group, pyrenyl phenyl group, fluorenyl group, fluorenyl phenyl group, phenyl fluorenyl group, fluoranthenyl group, phenyl fluoranthenyl group, fluoranthenyl phenyl group, perylenyl group, phenyl perylenyl group, perylenyl pheny Group, triphenylenyl group, phenyltriphenylenyl group, triphenylenyl phenyl group, tetracenyl group, phenyl to terracenyl group, tetracenyl phenyl group, chrysenyl group, phenyl chrysenyl group, chrysenyl phenyl group Or an aromatic hydrocarbon group which may be fused), pyridyl group, phenyl pyridyl group, pyridyl phenyl group, bipyridyl group, biphenyl pyridyl group, pyridyl biphenyl group, diphenyl pyridyl group, pyrimidyl group, phenyl pyrimidyl group, pyri Mysyl phenyl group, pyrazyl group, phenyl pyrazyl group, pyrazyl phenyl group, triazinyl group, phenyl triazyl group, triazyl phenyl group, quinolyl group, phenyl quinolyl group, quinolyl phenyl group, pyridyl quinolyl group, isoquinolyl group, Phenyl isoquinolyl , Isoquinolyl phenyl group, pyridyl isoquinolyl group, quinoxalinyl group, phenyl quinoxalinyl group, quinoxalinyl phenyl group, acridinyl group, phenyl acridinyl group, acridinyl phenyl group, phenanthridinyl group , Phenyl phenanthridinyl group, phenanthridinyl phenyl group, phenanthrolinyl group, phenyl phenanthrolinyl group, phenanthrolinyl phenyl group, pyrrolyl group, phenyl pyrrolyl group, pyrrolyl phenyl group, pyridyl pylori Group, furanyl group, phenyl furanyl group, furanyl phenyl group, pyridyl furanyl group, thienyl group, phenyl thienyl group, thienyl phenyl group, imidazolyl group, phenyl imidazolyl group, imidazolyl phenyl group, oxazolyl group, phenyl oxazolyl Group, oxazolylphene Group, isoxazolyl group, phenyl isoxazolyl group, isoxazolyl phenyl group, oxadiazolyl group, phenyl oxadiazolyl group, oxadiazolyl phenyl group, thiazolyl group, phenyl thiazolyl group, thiazolyl phenyl group, Indolyl group, phenyl indolyl group, indolyl phenyl group, benzofuranyl group, phenylbenzofuranyl group, benzofuranyl phenyl group, benzothiazolyl group, phenylbenzothiazolyl group, benzothiazolylphenyl group, benzoimidazolyl group, phenylbenzoimidazolyl group Group, benzoimidazolylphenyl group, benzoxazolyl group, phenylbenzoxazolyl group, benzoxazolylphenyl group, benzothiazolyl group, phenylbenzothiazolyl group, benzothiazolylphenyl group, dibenzofuran Group, phenyldibenzofuranyl group, dibenzofuranylphenyl group, dibenzothienyl group, phenyldibenzothienyl group, dibenzothienylphenyl group, carbazolyl group, phenylcarbazolyl group, carbazolylphenyl group, pyridylcarbazolyl group, Pyridyl phenyl carbazolyl group, dipyridyl carbazolyl group, carborinyl group, phenyl carbolinyl group, carborinyl phenyl group, indolocarbazolyl group, phenyl indolocarbazolyl group, indolocarbazolyl phenyl group And phenyl indolocarbazolylphenyl group, indolodibenzothienyl group, phenylindorhodibenzothienyl group, or indolodibenzothienylphenyl group (above, heteroaromatic group which may be linked or condensed), etc. .

Ar ¹ and Ar ² each have a condensed aromatic group having 7 to 18 carbon atoms or any of the following general formulas (2) to (9) in that they have excellent electron transport material properties. Substituents which are represented (these substituents each independently represent 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, It is preferable that it is a C1-C3 halogenated alkyl group, a C1-C3 halogenated alkoxy group, or a C10-C36 diarylamino group which may have as a substituent), Or one of them is a fused 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 each independently represent methyl Group or 10 to 36 carbon atoms And more preferably substituted also be) at arylamino group.

That is, with regard to Ar ¹ and Ar ² , one of them is a condensed aromatic group having 7 to 18 carbon atoms (a fluorine atom, a methyl group, an ethyl group, 3 to 10 carbon atoms) in terms of excellent 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 It is preferable that it is a substituent represented by either of following General formula (2) thru | or General formula (9), and any one of them may have 7 to 18 carbon atoms. A substituted aromatic group (which may be substituted with a methyl group or a diarylamino group having 10 to 36 carbon atoms) or a substituent represented by any one of the following general formulas (2) to (9): It is more preferable that

Furthermore, Ar ¹ and Ar ² are each independently a phenyl group, a fused aromatic group having 7 to 18 carbon atoms, and the following general formula (2): The substituent represented by any one of the general formula (9) (these substituents each independently represent 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 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 And Ar ¹ and Ar ² are each independently a phenyl group, a fused aromatic group having 7 to 18 carbon atoms, and a compound represented by the general formula 2) to any one of the general formula (9) Wherein the substituent is a substituent selected from the group consisting of (wherein each of the substituents may be independently substituted with a methyl group or a diarylamino group having 10 to 36 carbon atoms) More preferable.

That is, Ar ¹ and Ar ² are each independently a condensed aromatic group having 7 to 18 carbon atoms (a fluorine atom, a methyl group, an ethyl group, a carbon number) in terms of excellent electron transport material properties. 3-10 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 10 to 36 carbon atoms Is preferably a substituent represented by either of the following general formula (2) to general formula (9), and both of Ar ¹ and Ar ² are preferred. Each independently represents a fused 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 (2) 9) either It is more preferable that it is a substituent.

(In the general formulas (2) to (9), each Ar ³ is independently an aromatic group having 4 to 30 carbon atoms (each independently, a fluorine atom, a methyl group, an ethyl group, 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 Group may have a substituent as a substituent), methyl group, ethyl group, methoxy group, ethoxy group, diarylamino group having 10 to 36 carbon atoms or hydrogen atom)
The condensed aromatic group having 7 to 18 carbon atoms defines only a condensed ring skeleton, and the carbon number of the substituent is not included in the carbon number of the condensed aromatic group. The fused aromatic group having 7 to 18 carbon atoms is composed of a fused aromatic hydrocarbon having 7 to 18 carbon atoms and a fused heteroaromatic group having 7 to 18 carbon atoms, and is not particularly limited. For example, naphthyl group, fluorenyl group, anthryl group, phenanthryl group, pyrenyl group, chrysenyl group, triphenylenyl group, perylenyl group, quinolyl group, isoquinolyl group, acridinyl group, phenanthrizyl group, phenanthrolyl group, indolyl group, indolidolizinyl group, Benzoimidazolyl group, azaindolizinyl group, benzothiazolyl group, benzofuranyl group, benzothienyl group, carbazolyl group, carborinyl group, diazacarbazolyl group, dibenzofuranyl group, dibenzothienyl group, indolocarbazolyl group, or And lodibenzothienyl groups.

Further, the aromatic group having 4 to 30 carbon atoms in the general formulas (2) to (9) has the same definition as the aromatic group having 4 to 30 carbon atoms represented by R ^{1 to} R ⁴ , and is particularly limited The same substituents as those exemplified for R ^{1 to} R ⁴ can be exemplified although they are not.

  Moreover, although the C10-C36 diarylamino group in General Formula (2)-(9) is not specifically limited, The same thing as having illustrated in the above-mentioned C10-C36 diarylamino group is mentioned. It can be illustrated.

  Although it does not specifically limit as a C10-C36 diarylamino group, For example, N, N- diphenylamino group, N- tolyl-N- phenylamino group, N, N- di tolyl amino 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.

The substituted aromatic group of 7 to 18 which is preferable in Ar ¹ and Ar ² , or the substituent represented by any one of the general formulas (2) to (9) is 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, halogenated alkoxy having 1 to 3 carbon atoms The substituent may be selected from the group consisting of a group and a diarylamino group having 10 to 36 carbon atoms, and the number of the substituents 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) is preferred in that the electron transport property is excellent. The substituent represented by is preferable.

In the substituents represented by the general formulas (2) to (9), Ar ³ is independently an aromatic group having 4 to 30 carbon atoms (each independently, in that it is excellent in electron transport properties. , A fluorine atom, a methyl group, a methoxy group, or a diarylamino group having 10 to 36 carbon atoms as a substituent), a methyl group, an ethyl group, a diarylamino group having 10 to 36 carbon atoms, or a hydrogen atom It is preferable that each independently be 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). Is more preferably a methyl group, an ethyl group, a diarylamino group having a carbon number of 10 to 36, or a hydrogen atom, and each of them is independently preferably a phenyl group, a pyridylphenyl group, a phenylpyridyl group, Phenyl pyridyl, pyrimidyl phenyl, quinolyl phenyl, isoquinolyl phenyl, naphthyl, biphenylyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, terphenyl, anthryl, phenanthryl , Pyrenyl group, chrysenyl group, triphenylenyl group, pyridyl group, bipyridyl group, terpyridyl group, quinolyl group, isoquinolyl group, indolyl group, imidazolyl group, benzimidazolyl group, thiazole group, carbazolyl group, phenylcarbazolyl group, pyridylcarbazolyl Group, dipyridylcarbazolyl group, carborinyl 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 0 to 36 diarylamino group may be substituted as a substituent), methyl group, ethyl group, C10-C36 diarylamino group, or a hydrogen atom is more preferable, and each of them is independently Phenyl group, pyridyl phenyl group, phenyl pyridyl group, diphenyl pyridyl group, pyrimidyl phenyl group, quinolyl phenyl group, isoquinolyl phenyl group, naphthyl group, biphenylyl group, fluorenyl group, benzofluorenyl group, terphenyl group , Anthryl, phenanthryl, pyrenyl, chrysenyl, triphenylenyl, pyridyl, bipyridyl, terpyridyl, quinolyl, isoquinolyl, indolyl, benzimidazolyl, carbazolyl, phenylcarbazolyl, pyridylcarbazolyl Group, dipyridylcarbazoli Group, carborinyl group, phenylcarbolinyl group, pyridylcarbolinyl group, or dibenzothiophenyl group (these substituents each independently represent a fluorine atom, a methyl group, a methoxy group, or a carbon number of 10 to 36) More preferably, it is a diarylamino group 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 a phenyl group or pyridylphenyl Group, phenyl pyridyl group, diphenyl pyridyl group, pyrimidyl phenyl group, quinolyl phenyl group, isoquinolyl phenyl group, naphthyl group, biphenylyl group, fluorenyl group, benzofluorenyl group, terphenyl group, anthryl group, phenanthryl Group, pyrenyl group, chrysenyl group, triphenylenyl group, pyridyl group, bipyri Azyl group, terpyridyl group, quinolyl group, isoquinolyl group, indolyl group, benzimidazolyl group, carbazolyl group, phenylcarbazolyl group, pyridylcarbazolyl group, dipyridylcarbazolyl group, carborinyl group, phenylcarborinyl group, pyridylcarbo More preferably, it is a linyl group or 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 is 4-18 in total carbon number of ring structure, and shows the aromatic group which may be condensing or connecting. In addition, carbon number of the substituent which may have separately may not be contained in the said C4-C18 aromatic group. The aromatic group in the said C4-C18 aromatic group will not be specifically limited if it is an aromatic hydrocarbon group, a hetero aromatic group, or what these condensed or connected.

  The aromatic group having 4 to 18 carbon atoms is not particularly limited, and examples thereof include phenyl group, pyridylphenyl group, pyrimidylphenyl group, quinolylphenyl group, isoquinolylphenyl group and naphthyl group, Biphenylyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, terphenyl, anthryl, phenanthryl, pyrenyl, chrysenyl, triphenylenyl, pyridyl, bipyridyl, terpyridyl, quinolyl, isoquinolyl Group, indolyl group, imidazolyl group, benzimidazolyl group, thiazole group, carbazolyl group, phenylcarbazolyl group, pyridylcarbazolyl group, dipyridylcarbazolyl group, carborinyl 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 ′) in terms of excellent electron transport properties, and a benzo represented by the following general formula (1 ′ ′) It is more preferable that it is a furopyrimidine compound.

(Wherein, 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 General Formula (1 ′), Ar ³ each independently represents a phenyl group, a pyridylphenyl group, a phenyl pyridyl group, a diphenyl pyridyl group, a pyrimidyl phenyl group, a quinolyl phenyl group, isoquinolyl phenyl , Naphthyl, biphenylyl, terphenyl, anthryl, phenanthryl, pyrenyl, chrysenyl, triphenylenyl, pyridyl, bipyridyl, quinolyl, isoquinolyl, carbazolyl, phenylcarbazolyl, pyridylcarbayl Zoryl group, dipyridylcarbazolyl group, carborinyl group, phenylcarbolinyl group, pyridylcarbolinyl group, or dibenzothiophenyl group (these substituents each independently have a methyl group as a substituent) Or a hydrogen atom is preferable. Furthermore, in 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 It is preferable that it may have a group as a substituent.

  As specific examples of the benzofuropyrimidine compounds represented by the general formula (1), the following compounds 1 to 140 can be exemplified, but the present invention is not limited thereto.

Next, the manufacturing method of the present invention will be described.

  The benzofuropyrimidine compound (1) of the present invention can be obtained by the method represented 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 It can be manufactured.

  Further, hereinafter, the compound represented by the general formula (10) is referred to as a compound (10) roughly. The same applies to other compounds including the compound (11).

(In the general formula,
R ^{1 to} R ⁴ each independently represent 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 And having, as a substituent, 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 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, It represents a C3-C10 sulfide group or a C10-C36 diarylamino group.
Ar ¹ and Ar ² each independently represent 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 And having, as a substituent, 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 Also represent).
Ar ¹¹ , Ar ¹² and Ar ¹³ each independently represent 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, 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, or a diarylamino group having 10 to 36 carbon atoms as a substituent May be represented by
X ^{1 to} X ⁴ each independently represents 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 And having, as a substituent, 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 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, It represents a sulfide group of 3 to 10 carbon atoms, a diarylamino group of 10 to 36 carbon atoms, or a leaving group.
X ^{5 to} X ⁶ and Y 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 3 to 10 carbon atoms And 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 the general formula (10), at least one of X ^{1 to} X ⁶ is a leaving group. )
Further, the compound (10) used in the reaction formula (1) can be produced by the method shown by the following reaction formula (3) in the 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 an acid.

(In the general formula,
Ar ¹¹ and Ar ¹² each independently represent 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 And having, as a substituent, 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 Also represent).
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 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 Hydrogen, deuterium, fluorine, methyl, ethyl, alkyl having 3 to 10 carbons, methoxy, ethoxy, alkoxy having 3 to 10 carbons, methylthio, ethylthio, carbon It represents a sulfide group of the number 3 to 10, a diarylamino group having a carbon number of 10 to 36, or a leaving group.
Each of X ^{5 to} X ⁶ independently represents 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 having 3 to 10 carbon atoms And 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 to X ⁹ represents a leaving group.
In the general formula (10) and the general formulas (15), (16) and (17) according 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. The C3-C10 alkyl group has the same definition as described above. Although it does not specifically limit as a C5-C10 aromatic group, For example, a pyridyl group, a phenyl group, a tolyl group, a tert- butylphenyl group, a naphthyl group, a quinolyl group, an isoquinolyl group etc. are mentioned.

  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, and examples thereof include a hydrogen atom, a chlorine atom, a bromine atom, a triflate, an iodine atom, and 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 (eg, 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.

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

Further, as B (OR ²² ) ₂ , those shown by the following (I) to (VII) can be exemplified, and from the viewpoint of a good yield, those shown by (II) are preferable.

As said B (OR < ²³ >) ₃ , what is shown by following (I) to (III) can be illustrated.

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

  Next, reaction formula (1) will be described.

  As shown in the reaction of Reaction formula (1), the compound (1) of the present invention comprises the compound (10) or the compound (11) and the compound (21) in the presence of a metal catalyst or in the presence of a base and a metal catalyst. It can be synthesized by performing a coupling reaction.

  In the reaction of the reaction formula (1), the metal catalyst is preferably a palladium catalyst, a nickel catalyst or a copper catalyst in that the efficiency of the coupling reaction is excellent.

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

  In addition, in the reaction of reaction formula (1), a phase transfer catalyst can also be added. The phase transfer catalyst is not particularly limited, and, for example, 18-crown-6-ether can be used. In addition, as the addition amount, it is arbitrary quantity of the range which does not inhibit reaction remarkably.

  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, a nickel catalyst is mention | raise | lifted.

  Although it does not specifically limit as a palladium catalyst, For example, salts, such as palladium chloride, palladium acetate, palladium trifluoroacetate, palladium nitrate, etc. can be illustrated. Furthermore, π-allylpalladium chloride dimer, palladium acetylacetonato, 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 etc. can be exemplified. Among them, palladium complexes having tertiary phosphines such as dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, tri (tert-butyl) phosphinepalladium as a ligand are preferable in terms of a good yield, Tri (tert-butyl) phosphine palladium is further preferred in that it is easy.

  The copper catalyst is not particularly limited, and examples thereof include copper chloride, copper bromide, copper iodide, copper oxide, and copper triflate. Among them, copper oxide and copper iodide are preferable in that they are excellent in coupling reaction results, and copper oxide is more preferable in that they are easily available.

  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 ( The above four are examples of nickel complexes having a tertiary phosphine as a ligand), 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 are excellent in coupling reaction results. In terms of point, preferred and easy to obtain, dichloro (dimethoxyethane) nickel and dichloro [1,4-bis (diphenylphosphino) butane] nickel are more preferable.

  In addition, about the palladium complex which has said tertiary phosphine as a ligand, and the nickel complex which has a tertiary phosphine as a ligand, a tertiary phosphine is added to palladium salt, nickel salt, or those complex compounds. 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. For example, triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl -4,5-bis (diphenylphosphino) xanthene, 2- (diphenylphosphino) -2 '-(N, N-dimethylamino) biphenyl, 2- (di-tert-butylphosphino) biphenyl, 2- (di-tert-butylphosphino) biphenyl Dicyclohexylphosphino) biphenyl, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1'-bis (diphenyl Sphino) 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 etc. can be illustrated. Among these, (tert-butyl) phosphine or 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl is preferable in view of easy availability and good yield.

  When a tertiary phosphine is added to a palladium salt, a nickel salt or their complex compound, the addition amount of the tertiary phosphine is 1 mole (palladium or nickel atom equivalent) of the palladium salt, the nickel salt or their complex compound The amount is preferably 0.1 to 10 times by mole, and more preferably 0.3 to 5 times by mole in terms of a good yield.

  In addition, it is also possible to add a ligand separately to said copper catalyst. The ligand added to the copper catalyst is not particularly limited, and, for example, 2,2'-bipyridine, 1,10-phenanthroline, N, N, N ', N'-tetramethylethylenediamine, triphenyl A phosphine, 2- (dicyclohexyl phosphino) biphenyl etc. can be illustrated. Among these, 1,10-phenanthroline is preferable in terms of easy availability and good yield.

  Examples of the base that can be used in the reaction formula (1) include, but are not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, potassium acetate, sodium acetate And 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. For example, water, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), tetrahydrofuran (THF), toluene, benzene, diethyl ether, 1,4-dioxane, ethanol, butanol or xylene Can be exemplified, and these may be used in combination as appropriate. Among these, 1,4-dioxane, xylene, a mixed solvent of 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.

(These substituents each independently represent 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, or 1 to 3 carbon atoms Or a halogenated methyl group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent.
Moreover, Y is the same definition as Y in the said General formula (21). )

(These substituents each independently represent 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, or 1 to 3 carbon atoms Or a halogenated methyl group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent.
Moreover, Y is the same definition as Y in the said General formula (21). )
The compound (21) is described, for example, in J. Tsuji, "Palladium Reagents and Catalysts", John Wiley & Sons, 2004, Journal of Organic Chemistry, 60, 7508-7510, 1995, Journal of Organic Chemistry, 65, 164-168, 2000, Organic Letters 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 reaction formula (1), compound (10) or (11) is reacted with compound (21) in the presence or absence of a base in the presence of a metal catalyst to produce compound (1) of the present invention The target product can be obtained in good yield by applying the reaction conditions of the Suzuki-Miyaura reaction.

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

  The amount of the base used is not particularly limited, but it is preferably 0.5 to 10 times the mol of 1 mol of the compound (21), and is 1 to 4 times the mol in terms of a good yield. Is more preferred.

  The molar ratio of the compound (10) or (11) to the compound (21) used in the reaction formula (1) is not particularly limited, but it is preferably 1 to 1 mol of the leaving group of the compound (10) or (11). It is preferable to use 10 times mol of the compound (21), and it is more preferable to use 1 to 3 times mol of the compound (21) in terms of a good yield.

  The compound (10) and the compound (11) industrially supply a compound such as the compound (1) which is remarkably excellent in low driving voltage property, high luminous efficiency, and long life of the organic electroluminescent device. It is an excellent material and very valuable industrially.

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

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

The base which can be used in the reactions of the reaction formulas (2), (3) and (4) is not particularly limited, and, for example, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, 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. Among these, potassium tert-butoxide is preferred in terms of a good yield. Also, the acid that can be used for the reaction is not particularly limited, but, for example, hydrochloric acid, sulfuric acid, carbonic acid, phosphoric acid, acetic acid, benzoic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluene sulfone Examples include acids and various Lewis acids. As a Lewis acid, 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 1 (OTf) ₃ , Yb (OTf) ₃ , SiMe ₃ Cl, SiMe ₃ I, SiMe ₃ OTf, and the like. Among these, sulfuric acid is preferable in terms of a good yield.

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

  The amount of the base used is not particularly limited, but it is preferably 0.5 to 10 times the mol of 1 mol of the compounds (13), (16) and (19), and in terms of a good yield, More preferably, it is 1.1 to 4.0 times the molar amount.

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

  In addition, about said Reaction Formula (2), although it is also possible to go by one pot, it can also carry out stepwise like following Reaction Formula (6) and (7), respectively.

(In the general formula, Ar ¹ , Ar ² , R ^{1 to} R ⁴ and Z have the same definitions as in the 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.

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.

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.

Reaction formula (2) can be decomposed into reaction formulas (6) and (7). That is, in this reaction, compound (12) is reacted with compound (13) in the presence of a base to produce compound (21). The compound (21) is reacted with the compound (14) as shown in the reaction formula (7) to obtain the compound (1) of the present invention.

  The amount of the base to be used is not particularly limited, but it is preferably 0.5 to 10 times the mol of 1 mol of the compound (13), and 1.1 to 4.0 times in terms of a good yield More preferably, it is molar.

  The molar ratio of the compound (12) to the compound (13) used in reaction formula (6) is not particularly limited, but 0.1 to 10 times the molar amount of the compound (12) relative to 1 mol of the compound (13) It is preferable that it is 1.1-2.0 times mole from the point which the yield of a compound (21) is good.

  The molar ratio of the compound (21) to the compound (14) used in the reaction formula (7) is not particularly limited, but 0.1 to 20 times the molar amount of the compound (14) relative to 1 mol of the compound (21) Is preferably 1.0 to 5 times in terms of a good yield of the benzofuropyrimidine compound (1) of the present invention.

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

  About reaction formula (3), although it is also possible to go by one pot, it can also be performed stepwise like following reaction formula (8) and (9), respectively.

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

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.

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.

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

  Reaction formula (3) can be decomposed into reaction formulas (8) and (9). That is, in this reaction, compound (15) reacts with compound (16) in the presence of a base to produce compound (22). The compound (22) is reacted with the compound (17) as shown in the reaction formula (9) to obtain the compound (10) of the present invention.

  The compound (22) may be isolated but may not be isolated and may be used in the next step, reaction (9), in one pot.

  The amount of the base used is not particularly limited, but it is preferably 0.5 to 10 times the mol of 1 mol of the compound (16), and it is 1.1 to 4.0 times in terms of a good yield. More preferably, it is molar.

  The molar ratio of the compound (15) to the compound (16) used in the reaction formula (8) is not particularly limited, but 0.1 to 10 times the molar amount of the compound (15) relative to 1 mol of the compound (16) It is preferable that it is 1.1-2.0 times mole at the point with a favorable yield of compound (22).

  The molar ratio of the compound (22) to the compound (17) used in reaction formula (9) is not particularly limited, but 0.1 to 20 times the molar amount of the compound (17) relative to 1 mol of the compound (22) Is preferable, and 1.0 to 5 times is preferable in that the yield of the compound (10) of the present invention is good.

  Next, reaction formula (4) will be described.

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

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

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

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

  The amount of the base to be used is not particularly limited, but it is preferably 0.5 to 10 times the mol of 1 mol of the compound (18), and 1.1 to 4.0 times in terms of a good yield. More preferably, it is molar.

  The molar ratio of the compound (18) to the compound (19) used in the reaction formula (10) is not particularly limited, but 0.1 to 10 times the molar amount of the compound (18) with respect to 1 mol of the compound (19) It is preferable that it is 1.1-2.0 times mole at the point with a favorable yield of a compound (23).

  The molar ratio of the compound (23) to the compound (17) used in the reaction formula (11) is not particularly limited, but 0.1 to 20 times the molar amount of the compound (17) with respect to 1 mol of the compound (23) Is preferable, and 1.0 to 5 times is preferable in that the yield of the compound (20) is good.

  Next, reaction formula (5) will be described.

  The reaction scheme (5) is a method of producing a compound (11) by reacting the compound (20) with a halogenating agent or a sulfonylating agent in the presence or absence of a base. Examples of the halogenating agent include, but not particularly limited to, 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.

  The base used in the reaction formula (5) is not particularly limited, but the same bases as those shown in the reaction formulas (2), (3) and (4) can be used.

  The molar ratio of the compound (20) to the reactant used in the reaction of the reaction formula (5) is not particularly limited, but 0.1 to 20 moles of the reactant is preferable to 1 mole of the compound (20). And 1.0 to 5 times is preferable in terms of a good yield of the benzofuropyrimidine compound (11) of the present invention.

  The purity of the compounds (1), (10) and (11) of the present invention can be increased by performing treatments such as reprecipitation, concentration, filtration and purification after completion of each reaction. For further purification, purification may be carried out by recrystallization, silica gel column chromatography, sublimation or the like, if necessary.

  The present invention is an organic electroluminescent device containing a benzofuropyrimidine compound represented by the general formula (1), and the benzofuropyrimidine compound is preferably used for an electron transport layer, an electron injection layer, or a light emitting layer.

  That is, the said benzo furo pyrimidine compound is preferably used as an electron transport material or an electron injection material.

  The benzofuropyrimidine compound represented by General formula (1) can be preferably used as an electron transport material (electron transport material, electron injection material, etc.) of an organic electroluminescent element. At this time, as 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, Can be used in

  The configuration of the organic electroluminescent device may be any conventionally known one, and is not particularly limited.

Although there is no limitation in particular in the manufacturing method of the thin film for organic electroluminescent elements which contains the compound (1) of this invention, The film-forming by a vacuum evaporation method can be mentioned as a preferable example. The film formation by the vacuum evaporation method can be performed by using a general-purpose vacuum evaporation apparatus. The degree of vacuum of the vacuum chamber at the time of forming a film by a vacuum evaporation method is a diffusion pump, a turbo molecular pump, a cryo which is generally used in that the manufacturing tact time for manufacturing an organic electroluminescent device is short and the manufacturing cost is superior. It is preferably about 1 × 10 ⁻² to 1 × 10 ⁻⁶ Pa which can be reached by a pump or the like, and the deposition rate is preferably 0.005 to 10 nm / second depending on the thickness of the film to be formed. Moreover, the thin film for organic electroluminescent elements which consists of a compound (1) can be manufactured also by the solution apply | 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 coat method, an ink jet method, a cast method or the like using a general-purpose device 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 by evaluation example 1-1 grade | etc.,. It is a cross-sectional schematic diagram of the organic electroluminescent element produced by evaluation example 2-1 grade | etc.,.

1. Glass substrate with ITO transparent electrode Hole injection layer 3. First hole transport layer 4. Second hole transport layer 5. Light emitting layer 6. Electron transport layer 7. Electron injection layer 8. Cathode layer 11. Glass substrate with ITO transparent electrode 12. Hole injection layer 13. First hole transport layer 14. Second hole transport layer 15. Light emitting layer 16. Electron transport layer 17. Cathode layer

  The present invention will be described in more detail by way of synthesis examples, examples, comparative examples and reference examples, but the present invention is not construed as being limited thereto.

  Example 1

Compound A-1 (4.1 g) and 3-bromo-5-chlorobenzonitrile (4.76 g) are added to THF (20 mL) under an argon stream, and potassium tert-butoxide (2.47 g) in THF is 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 the mixture was allowed to cool to room temperature. The precipitated solid is washed with hexane to thin the desired 2- (3-bromo-5-chlorophenyl)-[1] benzofuro [3,2-d] pyrimidin-4 (3H) -one (B-1) A brown powder (yield 6.83 g, 91%) was obtained.

¹ H-NMR (DMSO-d ₆ ), δ (ppm): 7.37 (t, J = 7.2 Hz, 1 H), 7.52 (dd, J = 8.3, 7.2 Hz, 1 H), 7.66 (d, J = 8.3 Hz, 1 H), 7.70 (s, 1 H), 8.04 (d, J = 7.2 Hz, 1 H), 8.39 (s, 1 H), 8. 50 (s, 1 H).
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 an aqueous 4N NaOH solution were added to make the aqueous layer basic. Insoluble components were filtered off and the organic layer of the filtrate was extracted. By concentrating the organic layer, a yellow powder (yield: 384 mg, of a target 2- (3-bromo-5-chlorophenyl) -4-chloro- [1] benzofuro [3,2-d] pyrimidine (B-2) is obtained. 24% yield was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.59 (dd, J = 7.8, 6.7 Hz, 1 H), 7.66 (s, 1 H), 7.77 (d, J = 8.4 Hz, 1 H), 7. 80 (dd, J = 8.4, 6.7 Hz, 1 H), 8. 35 (d, J = 7.7 Hz, 1 H), 8. 55 (s, 1 H), 8.66 (s, 1 H).
Under an argon stream, compound B-2 (394 mg) and a 1 M solution of phenylmagnesium bromide in THF (4.0 mL) were added to THF (10 mL), and the mixture was heated to reflux for 72 hours. After cooling, water and chloroform were added to extract the organic layer. After adding toluene to the organic layer, it is concentrated and purified by column chromatography (developing solvent: hexane) to thereby obtain the desired 2- (3-bromo-5-chlorophenyl) -4-phenyl- [1] benzofuro [3, A white powder (yield 72 mg, 16%) of 2-d] pyrimidine (B-3) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.55 to 7.59 (m, 1 H), 7.61 to 7.70 (m, 4 H), 7.76 to 7.78 (m, 5) 2H), 8.38 (d, J = 7.7 Hz, 1 H), 8.67 (s, 1 H), 8. 73 (d, J = 8.3 Hz, 2 H), 8.78 (s, 1 H) .
Example 2

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 stirred at 80 ° C. for 1 hour. Then, water (10 mL) was added to the reaction mixture, and allowed to cool to room temperature. The precipitated solid was washed with water and hexane to obtain a target yellow powder (yield 1.14 g, 96%) of 3-amino-2-benzoylbenzofuran (A-2).

¹ H-NMR (DMSO-d ₆ ), δ (ppm): 7.31 (dd, J = 8.0, 6.5 Hz, 1 H), 7.47 (s, 2 H), 7.53-7. 63 (m, 5 H), 8.06 (d, J = 7.8 Hz, 1 H), 8.1 1 (d, J = 8.0 Hz, 2 H).
Compound A-2 (1.10 g) and 3-bromo-5-chlorobenzonitrile (1.5 g) are added to THF (4.6 mL) under an argon stream, and potassium tert-butoxide (573 mg) in THF is added thereto. The solution (18.5 mL) was added and stirred at 30 ° C. for 100 hours. To the reaction mixture was then added water (23 mL) and methanol (12 mL). The precipitated solid is 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, 71%) was obtained.

  Example 3

Compound B-3 (71 mg), 4- (2-pyridyl) phenylboronic acid (71 mg), palladium acetate (1.8 mg), and 2-dicyclohexylphosphino-2 ', 4', 6'- under an argon stream Triisopropylbiphenyl (7.8 mg) was added to THF (3.3 mL), and further 3 M aqueous potassium carbonate solution (0.25 mL) was added, and then 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 to obtain the desired 2- [4,4 ′ ′-bis (2-pyridyl)-[1,1 ′: 3 ′, 1 Gray powder (yield 100 mg, yield 98%) of '] -terphenyl-5'-yl] -4-phenyl- [1] benzofuro [3,2-d] pyrimidine (C-1) was obtained.

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, 1 H), 7.65-7.71 (m, 2 H), 7.74-7.79 (m, 2 H), 7.82 (dd, J) = 7.9, 7.2 Hz, 2 H), 7. 87 (d, J = 7.9 Hz, 2 H), 7.99 (d, J = 8.4 Hz, 4 H), 8.09 (s, 1 H) , 8.22 (d, J = 8.4 Hz, 4 H), 8. 47 (d, J = 7.7 Hz, 1 H), 8.78 (d, J = 4.8 Hz, 2 H), 8.80 ( d, J = 8.4 Hz, 2 H), 9.05 (s, 2 H).
Example 4

Compound B-2 (380 mg), 4- (2-pyridyl) phenylboronic acid (634 mg), palladium acetate (4.3 mg), and 2-dicyclohexylphosphino-2 ', 4', 6'- under an argon stream Triisopropylbiphenyl (18.3 mg) was added to THF (19 mL), and 3 M aqueous potassium carbonate solution (2.1 mL) was further added, and then 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 to obtain 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, A yield of 81% was obtained.

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

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

¹ H-NMR (DMSO-d ₆ ), δ (ppm): 7.35 (dd, J = 7.7, 7.3 Hz, 1 H), 7.51 (dd, J = 8.2, 7.3 Hz , 1H), 7.57 (s, 1 H), 7.65 (d, J = 8.2 Hz, 1 H), 8.02 (d, J = 7.7 Hz, 1 H), 8.33 (s, 2 H) ).
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), 4 N aqueous NaOH solution (72 mL) and saturated aqueous sodium bicarbonate solution (4 mL) were added to make the aqueous layer basic. The insoluble component is filtered, the solid is washed with water, washed with methanol and further washed with hexane to obtain the desired 2- (3,5-dichlorophenyl) -4-chloro- [1] benzofuro [3,2- d] White powder (yield 2.5 g, 77%) of pyrimidine (B-5) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.50 (s, 1 H), 7.59 (dd, J = 7.8, 6.7 Hz, 1 H), 7.76 (d, J = 8.4 Hz, 1 H), 7.80 (dd, J = 8.4, 6.7 Hz, 1 H), 8.34 (d, J = 7.8 Hz, 1 H), 8.49 (s, 2 H).
Under an argon stream, compound B-2 (394 mg) and a 1 M solution of phenylmagnesium bromide in THF (4.0 mL) were added to THF (10 mL), and the mixture was heated to reflux for 72 hours. After cooling, water and chloroform were added to extract the organic layer. After adding toluene to the organic layer, it is concentrated and purified by column chromatography (developing solvent: hexane) to obtain the desired 2- (3,5-dichlorophenyl) -4-phenyl- [1] benzofuro [3,2- d] White powder (yield 72 mg, 16% yield) of pyrimidine (B-6) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.55 to 7.59 (m, 1 H), 7.61 to 7.70 (m, 4 H), 7.76 to 7.78 (m, 5) 2H), 8.38 (d, J = 7.7 Hz, 1 H), 8.67 (s, 1 H), 8. 73 (d, J = 8.3 Hz, 2 H), 8.78 (s, 1 H) .
Example 6

Under argon flow, compound B-3 (2.18 g), 9-phenanthreneboronic acid (1.22 g), and bis (triphenylphosphine) palladium dichloride (70.2 mg) are added to THF (50 mL), and 3 M- Aqueous potassium carbonate solution (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 is washed with water, washed with methanol, and further washed with hexane to give the desired 2- [3-chloro-5- (9-phenanthryl) phenyl] -4-phenyl- [1] benzofuro [. 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, 1 H), 7.57-7.78 (m, 10 H), 7.84 (m s, 1 H), 7.98 (dd, 9.9, 8.5 Hz, 2 H), 8. 35 (d, J = 7.7 Hz, 1 H), 8. 73 (d, J = 8.2 Hz, 2 H) ), 8.78 (d, J = 8.3 Hz, 1 H), 8.81 (s, 1 H), 8.82-8.84 (m, 2 H).
Compound B-7 (1.17 g), 4- (2-pyridyl) phenylboronic acid (482 mg), palladium acetate (9.9 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6 in an argon stream '-Triisopropylbiphenyl (62.9 g) was added to THF (22 mL), and further 3 M aqueous potassium carbonate solution (1.6 mL) was added, and then 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 resulting gray solid was dissolved in toluene, and the insoluble component was separated by filtration, and then methanol was added to the filtrate to precipitate a white solid. The precipitated solid is separated by filtration to obtain the desired 2- [5- (9-phenanthryl) -4 '-(2-pyridyl) biphenyl-3-yl] -4-phenyl- [1] benzofuro [3,2]. A gray powder (yield 1.24 g, 87%) of -d] pyrimidine (C-3) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.27-7.30 (m, 1 H), 7.54 (dd, J = 7.7, 6.8 Hz, 1 H), 7.57- 7.83 (m, 10H), 7.85 (d, J = 7.8 Hz, 1 H), 7.94 (s, 1 H), 7.99-8.01 (m, 4 H), 8.13 ( d, J = 8.3 Hz, 1 H), 8. 19 (d, J = 8.4 Hz, 2 H), 8. 40 (d, J = 7.6 Hz, 1 H), 8.75-8.78 (m , 3H), 8.81 (d, J = 8.2 Hz, 1 H), 8.86 (d, J = 8.2 Hz, 1 H), 8.93 (s, 1 H), 9.15 (s, 1 H) ).
Production and Performance Evaluation of an Organic Electroluminescent Device Comprising the Benzofuropyrimidine Compound of the Present Invention as a Component The present invention will be explained by the following test examples, but the present invention is not limited thereto. In addition, structural formulas of the compounds to be used and their abbreviations are shown below.

Evaluation Example 1-1
As a 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 washed with isopropyl alcohol and then surface-treated by oxygen plasma washing. Each layer was vacuum-deposited on the cleaned substrate by a vacuum deposition method to produce an organic electroluminescent device having a light-emitting area of 4 mm ² as shown in FIG.

First, the glass substrate was introduced into a vacuum deposition tank, and the pressure was 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, and an electron transport layer are formed as an organic compound layer on a glass substrate with an ITO transparent electrode shown in FIG. 6 and the electron injection layer 7 were sequentially formed, and then the cathode layer 8 was formed.

  The materials forming each layer of the organic electroluminescent device were vacuum deposited by resistance heating.

  As the hole injection layer 2, HTL-1 was vacuum deposited at a deposition rate of 0.15 nm / sec.

  As the first hole transport layer 3, HAT-CN was vacuum deposited at a deposition rate of 0.025 nm / sec to a thickness of 5 nm.

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

  As the light emitting layer 5, a film thickness of 25 nm (EML-1 / EML-2 = 95.4 / 4.6 (weight ratio)) of EML-1 and EML-2 at a film forming speed of 0.18 nm / sec. Vacuum deposition).

  As the electron transport layer 6, C-1 synthesized in Example 3 of the present invention was vacuum deposited at a film forming speed of 0.15 nm / sec.

  As the electron injection layer 7, Liq was vacuum deposited at a deposition rate of 0.005 nm / sec.

  Finally, a metal mask was disposed to be orthogonal to the ITO stripes, 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 0.5 nm / sec and 0.2 nm / sec, respectively, to a film thickness of 80 nm and 20 nm , 2 layer structure.

  Each film thickness was measured with a stylus type film thickness measurement meter (DEKTAK, manufactured by Veeco). Furthermore, this element was sealed in a nitrogen atmosphere glove box with an oxygen and water concentration of 1 ppm or less. Sealing used the sealing cap made from glass, and the said film-forming board | substrate epoxy-type ultraviolet-ray cured resin (made by Nagase ChemteX Corp.).

Evaluation Example 1-2
An organic electroluminescent device was manufactured by the same method as Evaluation Example 1-1 except that C-3 synthesized in Example 6 was used instead of C-1 in the electron transport layer 6 of Evaluation Example 1-1. Was produced.

Reference Example 1-1
An organic electroluminescent device was manufactured 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 in the electron transport layer 6 of Evaluation Example 1-1. Was produced.

A direct current was applied to the produced organic electroluminescent device, and the luminescence characteristics were evaluated using a luminance meter manufactured by TOPCON, LUMINANCE METER (BM-9). As a lifetime characteristic (h), the luminance decay time at the time of continuous lighting when current density 10 mA / cm ² was passed was measured. In addition, the time when the luminance (cd / m ² ) decreased by 20% and the increase in driving voltage when the element 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) at a current density of 10 mA / cm ² . In addition, about the element life (h) of each evaluation example, the time (h) when the luminance (cd / m ² ) of the element in Reference Example 1-1 is reduced by 5% from the initial value is 100, and it is a relative value. Indicated.

It was found that the organic electroluminescent device using the benzofuropyrimidine compound of the present invention was superior in life characteristics as compared to Reference Example 1-1.

Evaluation Example 2-1
As a 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 washed with isopropyl alcohol and then surface-treated by oxygen plasma washing. Each layer was vacuum deposited on the cleaned substrate by a vacuum deposition method, and an organic electroluminescent device having a light emitting area of 4 mm ² as shown in FIG. 2 was produced.

First, the glass substrate was introduced into a vacuum deposition tank, and the pressure was 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 a glass substrate with an ITO transparent electrode shown by 11 in FIG. The film 16 was sequentially formed, and then the cathode layer 17 was formed.

  The materials forming each layer of the organic electroluminescent device were vacuum deposited by resistance heating.

  As the hole injection layer 12, HTL-1 was vacuum deposited at a deposition rate of 0.15 nm / sec.

  As the first hole transport layer 13, HAT-CN was vacuum deposited at a deposition rate of 0.025 nm / sec to a thickness of 5 nm.

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

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

  The electron transport layer 16 has a thickness of 30 nm (C-1 / Liq = 50/50 (weight ratio) at a deposition rate of 0.15 nm / sec for C-1 and Liq synthesized in Example 3 of the present invention. Vacuum evaporation).

  Finally, a metal mask was disposed to be orthogonal to the ITO stripes, and the cathode layer 17 was formed. The cathode layer 17 is formed by vacuum deposition of magnesium / silver (weight ratio 80/20) and silver in this order with film thicknesses of 0.5 nm / sec and 0.2 nm / sec to a film thickness of 80 nm and 20 nm, respectively. , 2 layer structure.

Each film thickness was measured with a stylus type film thickness measurement meter (DEKTAK, manufactured by Veeco).
Furthermore, this element was sealed in a nitrogen atmosphere glove box with an oxygen and water concentration of 1 ppm or less. Sealing used the sealing cap made from glass, and the said film-forming board | substrate epoxy-type ultraviolet-ray cured resin (made by Nagase ChemteX Corp.).

Evaluation Example 2-2
In the electron transport layer 16 of the Evaluation Example 2-1, instead of the C-1, except for using C-3 synthesized in Example -6, the organic electroluminescent device in the same manner as Evaluation Example 2-1 Was produced.

Reference Example 2-1
An organic electroluminescent device was manufactured by the same method as Evaluation Example 2-1 except that ETL-1 which is a known electron transport material was used in place of C-1 in the electron transport layer 16 of Evaluation Example 2-1. Was produced.

A direct current was applied to the produced organic electroluminescent device, and the luminescence characteristics were evaluated using a luminance meter manufactured by TOPCON, LUMINANCE METER (BM-9). As a lifetime characteristic (h), the luminance decay time at the time of continuous lighting when current density 10 mA / cm ² was passed was measured. In addition, the time when the luminance (cd / m ² ) was reduced by 10% and the increase in driving voltage 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) at a current density of 10 mA / cm ² . 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) is set to 100. Regarding the device life (h) of each evaluation example, the time (h) when the luminance (cd / m ² ) of the device in Reference Example 2-1 is reduced by 5% from the initial time is shown as a relative value as 100. .

It was found that the organic electroluminescent device using the benzofuropyrimidine compound of the present invention was remarkably excellent in the life characteristics as compared to Reference Example 2-1.

  The organic electroluminescent device using the benzofuropyrimidine compound of the present invention can be driven for a long time as compared with the organic electroluminescent device using the existing material. The benzofuropyrimidine compound of the present invention is also applicable to a light emitting host layer and the like in addition to the electron transport layer of this example. Thus, the benzofuropyrimidine compounds of the present invention are useful as electron injecting materials or electron transporting materials. Furthermore, application to various organic electroluminescent devices using phosphorescent light emitting materials as well as devices using fluorescent light emitting materials is also possible. In addition, the benzofuropyrimidine compound of the present invention has high solubility, and it is possible to produce not only a vacuum evaporation method but also a device using a coating method. Furthermore, it is useful not only for applications such as flat panel displays, but also for lighting applications that require low power consumption.

Claims (9)

Benzofuropyrimidine compounds represented by the general formula (1 ′ ′):
During the ceremony
[1] Ar ³ on the benzene ring at the 2-position of the benzofuro [3,2-d] pyrimidine ring is each independently a phenyl group, a pyridylphenyl group, a phenyl pyridyl group, a diphenyl pyridyl group, a pyrimidyl phenyl group , Quinolyl phenyl, isoquinolyl phenyl, naphthyl, biphenylyl, terphenyl, anthryl, phenanthryl, pyrenyl, chrysenyl, triphenylenyl, pyridyl, bipyridyl, quinolyl, isoquinolyl, carbazolyl Group, a phenylcarbazolyl group, a pyridylcarbazolyl group, a dipyridylcarbazolyl group, a carbolinyl group, a phenylcarbolinyl group, a pyridylcarbolinyl group or a dibenzothiophenyl group (these substituents are each independently Methyl group as a substituent),
[1] Ar ³ on the benzene ring at position 4 of the benzofuro [3,2-d] pyrimidine ring is each independently a phenyl group, a pyridylphenyl group, a phenyl pyridyl group, a diphenyl pyridyl group, a pyrimidyl phenyl group , Quinolyl phenyl, isoquinolyl phenyl, naphthyl, biphenylyl, terphenyl, anthryl, phenanthryl, pyrenyl, chrysenyl, triphenylenyl, pyridyl, bipyridyl, quinolyl, isoquinolyl, carbazolyl Group, phenylcarbazolyl group, pyridylcarbazolyl group, dipyridylcarbazolyl group, carborinyl group, phenylcarbolinyl group, pyridylcarbolinyl group, or dibenzothiophenyl group (these groups are each independently A methyl group may have as a substituent) or a hydrogen atom It is. A process for producing a benzofuropyrimidine compound represented by the general formula (1 ′ ′) according to claim 1,
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) Production method characterized by coupling reaction:
In formulas (10) and (11),
Ar ¹¹ is,
Off Eniru group, or,
One or two hydrogen atoms of the phenyl group are each independently a phenyl group, pyridylphenyl group, phenylpyridyl group, diphenyl pyridyl group, pyrimidyl phenyl group, quinolyl phenyl group, isoquinolyl phenyl group, naphthyl group , Biphenylyl, terphenyl, anthryl, phenanthryl, pyrenyl, chrysenyl, triphenylenyl, pyridyl, bipyridyl, quinolyl, isoquinolyl, carbazolyl, phenylcarbazolyl, pyridylcarbazolyl, Selected from dipyridylcarbazolyl group, carborinyl group, phenylcarbolinyl group, pyridylcarbolinyl group, and dibenzothiophenyl group (these groups may each independently have a methyl group as a substituent) It is representative of the substituted group group;
Ar ¹² represents a phenyl group having a leaving group at each of two m positions;
Ar ¹³ is
(A): a group corresponding to a group substituted at the 4-position of a [1] benzofuro [3, 2-d] pyrimidine ring represented by the formula (1 ′ ′),
Phenyl group or
One or two hydrogen atoms of the phenyl group are each independently a phenyl group, pyridylphenyl group, phenylpyridyl group, diphenyl pyridyl group, pyrimidyl phenyl group, quinolyl phenyl group, isoquinolyl phenyl group, naphthyl group , Biphenylyl, terphenyl, anthryl, phenanthryl, pyrenyl, chrysenyl, triphenylenyl, pyridyl, bipyridyl, quinolyl, isoquinolyl, carbazolyl, phenylcarbazolyl, pyridylcarbazolyl, Selected from dipyridylcarbazolyl group, carborinyl group, phenylcarbolinyl group, pyridylcarbolinyl group, and dibenzothiophenyl group (these groups may each independently have a methyl group as a substituent) Or a group substituted with
(B): a group corresponding to Ar ³ on the benzene ring substituted at the 2-position of the [1] benzofuro [3, 2-d] pyrimidine ring represented by the formula (1 ′ ′) , each of which is independently And phenyl, pyridylphenyl, phenylpyridyl, diphenylpyridyl, pyrimidylphenyl, quinolylphenyl, isoquinolylphenyl, naphthyl, biphenylyl, terphenyl, anthryl, phenanthryl, Pyrenyl group, chrysenyl group, triphenylenyl group, pyridyl group, bipyridyl group, quinolyl group, isoquinolyl group, carbazolyl group, phenylcarbazolyl group, pyridylcarbazolyl group, dipyridylcarbazolyl group, carborinyl group, phenylcarbolinyl group , pyridylcarbonitrile Li sulfonyl group or dibenzothiophenyl group (these groups are each independently It represents a chill group which may have a substituent);
X ^{1 to} X ⁴ represent a hydrogen atom.
Y and X ⁷ represent a leaving group;
The leaving group is a group selected from the group consisting of chlorine atom, bromine atom, triflate, iodine atom, and metal-containing group ;
The metal-containing group includes 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, ZnCl, ZnBr, ZnI, SiMe 3, SiPh 3, SiMePh 2, SiCl 3, SiF 3, Si (OMe) 3, Si (OEt) 3, Si (OMe) 2 OH, BF ₃ K, B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , B (OBu) ₂ , B (OPh) ₂ , and any one of the following formulas .
A process for producing a benzofuropyrimidine compound represented by the general formula (1 ′ ′) according to claim 1,
A method for producing, characterized in that the compounds represented by the general formula (12), the general formula (13) and the general formula (14) are condensed in the presence of a base or an acid:
In formulas (12) to (14),
R ^{1 to} R ⁴ represent a hydrogen atom;
Ar ³ is as defined in the general formula (1 ′ ′);
X ⁸ represents a leaving group;
The leaving group is a group selected from the group consisting of chlorine atom, bromine atom, triflate, iodine atom, and metal-containing group ;
The metal-containing group includes 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, ZnCl, ZnBr, ZnI, SiMe 3, SiPh 3, SiMePh 2, SiCl 3, SiF 3, Si (OMe) 3, Si (OEt) 3, Si (OMe) 2 OH, BF ₃ K, B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , B (OBu) ₂ , B (OPh) ₂ , and any one of the following formulas .
A method for producing a benzofuropyrimidine compound represented by the general formula (10), which comprises
A method for producing, characterized in that the compounds represented by the general formula (15), the general formula (16) and the general formula (17) are condensed in the presence of a base or an acid:
In formulas (10), (15) to (17),
Ar ¹¹ is
Phenyl group or
One or two hydrogen atoms of the phenyl group are each independently a phenyl group, pyridylphenyl group, phenylpyridyl group, diphenyl pyridyl group, pyrimidyl phenyl group, quinolyl phenyl group, isoquinolyl phenyl group, naphthyl group , Biphenylyl, terphenyl, anthryl, phenanthryl, pyrenyl, chrysenyl, triphenylenyl, pyridyl, bipyridyl, quinolyl, isoquinolyl, carbazolyl, phenylcarbazolyl, pyridylcarbazolyl, Selected from dipyridylcarbazolyl group, carborinyl group, phenylcarbolinyl group, pyridylcarbolinyl group, and dibenzothiophenyl group (these groups may each independently have a methyl group as a substituent) It is representative of the substituted group group;
Ar ¹² represents a phenyl group having a leaving group at each of two m positions;
X ^{1 to} X ⁴ represent a hydrogen atom.
X ⁸ represents a leaving group;
The leaving group is a group selected from the group consisting of chlorine atom, bromine atom, triflate, iodine atom, and metal-containing group ;
The metal-containing group includes 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, ZnCl, ZnBr, ZnI, SiMe 3, SiPh 3, SiMePh 2, SiCl 3, SiF 3, Si (OMe) 3, Si (OEt) 3, Si (OMe) 2 OH, BF ₃ K, B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , B (OBu) ₂ , B (OPh) ₂ , and any one of the following formulas .
A method for producing a benzofuropyrimidine compound represented by the general formula (11), which comprises
A method of production comprising reacting the compound represented by the general formula (20) with a halogenating agent or a sulfonylating agent in the presence or absence of a base:
In formulas (11) and (20),
Ar ¹² represents a phenyl group having a leaving group at each of two m positions;
X ^{1 to} X ⁴ represent a hydrogen atom;
X ⁷ represents a leaving group;
The leaving group is a chlorine atom, a bromine atom, a group selected triflate, and iodine MotoHara child or Ranaru group. Benzofuropyrimidine compounds represented by the general formula (10):
In formula (10),
Ar ¹¹ is
Phenyl group or
One or two hydrogen atoms of the phenyl group are each independently a phenyl group, pyridylphenyl group, phenylpyridyl group, diphenyl pyridyl group, pyrimidyl phenyl group, quinolyl phenyl group, isoquinolyl phenyl group, naphthyl group , Biphenylyl, terphenyl, anthryl, phenanthryl, pyrenyl, chrysenyl, triphenylenyl, pyridyl, bipyridyl, quinolyl, isoquinolyl, carbazolyl, phenylcarbazolyl, pyridylcarbazolyl, Selected from dipyridylcarbazolyl group, carborinyl group, phenylcarbolinyl group, pyridylcarbolinyl group, and dibenzothiophenyl group (these groups may each independently have a methyl group as a substituent) It is representative of the substituted group group;
Ar ¹² represents a phenyl group having a leaving group at each of two m positions;
X ^{1 to} X ⁴ represent a hydrogen atom.
The leaving group is a group selected from the group consisting of chlorine atom, bromine atom, triflate, iodine atom, and metal-containing group ;
The metal-containing group includes 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, ZnCl, ZnBr, ZnI, SiMe 3, SiPh 3, SiMePh 2, SiCl 3, SiF 3, Si (OMe) 3, Si (OEt) 3, Si (OMe) 2 OH, BF ₃ K, B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , B (OBu) ₂ , B (OPh) ₂ , and any one of the following formulas .
Benzofuropyrimidine compounds represented by the general formula (11):
In formula (11),
Ar ¹² represents a phenyl group having a leaving group at each of two m positions;
X ^{1 to} X ⁴ represent a hydrogen atom;
X ⁷ represents a leaving group;
The leaving group is a group selected from the group consisting of chlorine atom, bromine atom, triflate, iodine atom, and metal-containing group ;
The metal-containing group includes 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, ZnCl, ZnBr, ZnI, SiMe 3, SiPh 3, SiMePh 2, SiCl 3, SiF 3, Si (OMe) 3, Si (OEt) 3, Si (OMe) 2 OH, BF ₃ K, B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , B (OBu) ₂ , B (OPh) ₂ , and any one of the following formulas .
  An electron injecting or electron transporting material comprising the benzofuropyrimidine compound according to claim 1.   An electron injecting or electron transporting material for an organic electroluminescent device comprising the benzofuropyrimidine compound according to claim 1.