JP6507534B2 - Benzothienopyrimidine compound, method for producing the same, and organic electroluminescent device containing the same - Google Patents

Description

  The present invention relates to a benzothienopyrimidine compound useful as a component of an organic electroluminescent device, a method for producing the same, and an organic electroluminescent device containing 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 dibenzothiophene compound (for example, patent documents 1) and a nitrogen substitution dibenzothiophene compound are indicated (for example, refer to patent documents 2-3), and the proposal which improves the life of an element using these is proposed. However, improvement is desired in terms of increasing the driving voltage of the element and in the point of further prolonging the life.

  In addition, the use of nitrogen-substituted dibenzothiophene compounds has been proposed for many applications, not limited to organic electroluminescent devices, but methods for producing these compounds have hardly been reported, and simple synthetic methods have been sought. There is.

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.

  Moreover, it is general to heat at high temperature in vacuum at the time of sublimation refinement | purification and vapor deposition for organic electroluminescent element preparation, and the material for organic electroluminescent elements is requested | required of a material with higher heat resistance.

  There is also a need for a convenient synthesis of benzothienopyrimidine 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 benzothienopyrimidine compounds represented by the general formula (1) of the present invention have higher electron durability and greater durability than conventionally known compounds. It has been found that the hole durability is significantly improved. From such findings, when the benzothienopyrimidine compound is used as an electron transport layer in an organic electroluminescent device, the lifetime of the organic electroluminescent device is extended compared to when a known or general electron transport material is used, and It has been found that the voltage rise during driving is suppressed, and the present invention has been completed.

  The present inventors have also found that substitution of the 2- and 4-positions of benzothienopyrimidine with an aromatic group improves the heat resistance of the compound and suppresses the thermal deterioration of the material, and completes the present invention. It came to

  That is, the present invention relates to a benzothienopyrimidine 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 organic electroluminescent device containing the same It is.

(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 compound (1), a method for producing the same, and an organic electroluminescent device 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, diphenyl pyridyl phenyl group, pyrimidyl group, phenyl pyri group Midyl group, pyrimidyl 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, isoki Ryl group, phenyl isoquinolyl group, 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 pyrrolyl 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 oxy Sazolyl group, oxazolyl phenyl 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, benzothiazolyl phenyl group , Benzoimidazolyl group, phenylbenzoimidazolyl group, benzoimidazolylphenyl group, benzoxazolyl group, phenylbenzoxazolyl group, benzoxazolylphenyl group, benzothiazolyl group, phenylbenzothiazolyl group, benzothia Rylphenyl group, dibenzofuranyl group, phenyldibenzofuranyl group, dibenzofuranylphenyl group, dibenzothienyl group, phenyldibenzothienyl group, dibenzothienylphenyl group, carbazolyl group, phenylcarbazolyl group, carbazolylphenyl group, pyridyl Carbazolyl group, pyridylphenyl carbazolyl group, carborinyl group, phenylcarbolinyl group, carborinyl phenyl group, indolocarbazolyl group, phenyl indolocarbazolyl group, phenyl indolocarbazolyl phenyl group And an indolocarbazolylphenyl group, an indolodibenzothienyl group, a phenylindorhodibenzothienyl group, an indolodibenzothienylphenyl group (a heteroaromatic group which may be linked or condensed, or the like).

  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, Pyridyl phenyl group (these substituents may have a methyl group), a hydrogen atom, a deuterium atom, a phenyl group or a methyl group is more preferable, and a hydrogen atom, a phenyl group or a deuterium atom It is further preferred that

  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, diphenyl pyridyl phenyl group, pyrimidyl group, phenyl pyri group Midyl group, pyrimidyl 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, isoki Ryl group, phenyl isoquinolyl group, 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 pyrrolyl 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 oxy Sazolyl group, oxazolyl phenyl 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, benzothiazolyl phenyl group , Benzoimidazolyl group, phenylbenzoimidazolyl group, benzoimidazolylphenyl group, benzoxazolyl group, phenylbenzoxazolyl group, benzoxazolylphenyl group, benzothiazolyl group, phenylbenzothiazolyl group, benzothia Rylphenyl group, dibenzofuranyl group, phenyldibenzofuranyl group, dibenzofuranylphenyl group, dibenzothienyl group, phenyldibenzothienyl group, dibenzothienylphenyl group, carbazolyl group, phenylcarbazolyl group, carbazolylphenyl group, pyridyl Carbazolyl group, pyridylphenylcarbazolyl group, dipyridylcarbazolyl group, carborinyl group, phenylcarbolinyl group, carborinylphenyl group, indolocarbazolyl group, phenyl indolocarbazolyl group, indolo A carbazolyl phenyl group, a phenyl indolocarbazolyl phenyl group, an indolodibenzothienyl group, a phenylindorhodibenzothienyl group, or an indolodibenzothienylphenyl group (a heteroaromatic group which may be linked or condensed, or more) ) Etc. It is.

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 phenyl group or a fused aromatic group having 7 to 18 carbon atoms (a fluorine atom, a methyl group, 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, a halogenated alkoxy group having 1 to 3 carbon atoms, or 10 to 36 diarylamino group may be included as a substituent) or a substituent represented by any one of the following general formulas (2) to (9), Ar ¹ and Ar Both of ^two groups each independently have a condensed aromatic group having 7 to 18 carbon atoms (which may be substituted with a methyl group or a diarylamino group having 10 to 36 carbon atoms) or the following general formula (2) Any of general formula (9) It is more preferable that it is a substituent represented by

  Below, the substituent represented by General formula (2)-(9) is shown.

(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 group 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, phenanthrizinyl group, phenanthrolyl group, indolyl group, indolizinyl group , Benzoimidazolyl group, azaindolidinyl group, benzothiazolyl group, benzofuranyl group, benzothienyl group, carbazolyl group, carborinyl group, diazacarbazolyl group, dibenzofuranyl group, dibenzothienyl group, indolocarbazolyl group, or And indologibenzothienyl 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 24 carbon atoms (each independently having a fluorine atom, a methyl group, a methoxy group, or a diarylamino group having 10 to 36 carbon atoms as a substituent). More preferably a methyl group, an ethyl group, a diarylamino group having 10 to 36 carbon atoms, or a hydrogen atom.

Among these, each Ar ³ independently represents a phenyl group, a pyridylphenyl group, a phenyl pyridyl group, a diphenyl pyridyl group, a diphenyl pyridyl phenyl group, a pyrimidyl phenyl group, a quinolyl phenyl group, an isoquinolyl phenyl group, Naphthyl, biphenylyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, terphenyl, anthryl, phenanthryl, pyrenyl, chrysenyl, triphenylenyl, pyridyl, bipyridyl, terpyridyl, quinolyl Group, isoquinolyl group, indolyl group, imidazolyl group, benzimidazolyl group, thiazole group, carbazolyl group, phenylcarbazolyl group, pyridylcarbazolyl group, dipyridylcarbazolyl group, carborinyl group, phenylcarborinyl group, pyridyl A carborinyl group or a dibenzothiophenyl group (these substituents may each independently have a fluorine atom, a methyl group, a methoxy group, or a diarylamino group having 10 to 36 carbon atoms as a substituent) And more preferably a methyl group, an ethyl group, a diarylamino group having 10 to 36 carbon atoms, or a hydrogen atom.

Furthermore, among these, Ar ³ each independently represents a phenyl group, pyridylphenyl group, phenyl pyridyl group, diphenyl pyridyl group, diphenyl pyridyl phenyl 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, bipyridyl group, terpyridyl group, quinolyl group, isoquinolyl group , Indolyl group, benzimidazolyl group, carbazolyl group, phenyl carbazolyl group, pyridylcarbazolyl group, dipyridylcarbazolyl group, carborinyl group, phenylcarborinyl group, pyridylcarborinyl group, or dibenzothiophenyl group (These substituents may each independently have a fluorine atom, a methyl group, a methoxy group, or a C 10-C 36 diarylamino group as a substituent), a methyl group, an ethyl group, a carbon number It is more preferable that it is a 10-36 diarylamino group or a hydrogen atom.

Furthermore, among these, Ar ³ each independently represents a phenyl group, pyridylphenyl group, phenyl pyridyl group, diphenyl pyridyl group, diphenyl pyridyl phenyl 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, bipyridyl group, terpyridyl group, quinolyl group, isoquinolyl group , Indolyl group, benzimidazolyl group, carbazolyl group, phenyl carbazolyl group, pyridylcarbazolyl group, dipyridylcarbazolyl group, carborinyl group, phenylcarborinyl group, pyridylcarborinyl group, or dibenzothiophenyl group (These substituents may each independently have a methyl group as a substituent) or a hydrogen atom is more preferable.

  The aromatic group having 4 to 24 carbon atoms is an aromatic group which has 4 to 24 carbon atoms in the ring skeleton and may be fused or linked. In addition, carbon number of the substituent which may have separately is not contained in the said C4-C24 aromatic group. The aromatic group in the said C4-C24 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 24 carbon atoms is not particularly limited, but among the substituents exemplified for the aromatic group having 4 to 66 carbon atoms, those having a total number of carbon atoms of 24 or less It can be exemplified, for example, phenyl group, pyridylphenyl group, phenyl pyridyl group, diphenyl pyridyl group, diphenyl pyridyl phenyl group, pyrimidyl phenyl group, pyrimidyl phenyl group, quinolyl phenyl group, isoquinolyl phenyl group , Naphthyl group, biphenylyl group, fluorenyl group, benzofluorenyl group, dibenzofluorenyl group, terphenyl group, anthryl group, phenanthryl group, pyrenyl group, chrysenyl group, triphenylenyl group, pyridyl group, bipyridyl group, terpyridyl group, Quinolyl group, isoquinolyl group, indolyl group, imidazolyl group, benzo Midazolyl group, thiazole group, carbazolyl group, phenylcarbazolyl group, pyridylcarbazolyl group, dipyridylcarbazolyl group, carborinyl group, phenylcarbolinyl group, pyridylcarbolinyl group, or dibenzothiophenyl group. .

  Although the following compounds 1 to 140 can be illustrated as specific examples of the benzothienopyrimidine compound represented by the general formula (1), the present invention is not limited thereto.

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

  The benzothienopyrimidine compound (1) of the present invention can be obtained by the following reaction formula (1), reaction formula (2), or reaction formula 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 manufacture by the method shown by (12).

  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 represents a leaving group.
Z represents a chlorine atom, a bromine atom, a triflate or an iodine atom.
In 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) or reaction formula (13) in the presence of a base or an acid. Similarly, in the presence of a base or an acid, compound (11) can be represented by the following reaction formula (4) and the method shown by reaction formula (5), or reaction formula (14) and reaction formula (15) It can be manufactured by the method shown.

(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 represents a leaving group.
Z represents a chlorine atom, a bromine atom, a triflate or an iodine atom.
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 ⁷ 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 ⁷ 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.

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

(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 form compound (22). The compound (22) 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 at the point with a favorable yield of compound (22).

  The molar ratio of the compound (22) 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 (22) Is preferable, and 1.0 to 5 times is preferable in that the yield of the benzothienopyrimidine compound (1) of the present invention is good.

  Next, the reaction of reaction formula (12) will be described.

  In addition, about said Reaction Formula (12), although it is also possible to go by one pot, it can also be carried out stepwise like following Reaction Formula (16) and (17), 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 (25), For example, the compound represented by the following 25-1-25-38 can be illustrated.

Although it does not specifically limit as a compound (26), For example, the compound represented by the following 26-1 to 26-15 can be illustrated.

As a compound (14), although it does not specifically limit, the compound similar to Reaction formula (2) can be illustrated.

  Reaction formula (2) can be decomposed into reaction formulas (16) and (17). That is, in this reaction, compound (25) reacts with compound (26) in the presence of a base to produce compound (22). The compound (22) is reacted with the compound (14) as shown in the reaction formula (17) 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 (26), and 1.1 to 4.0 times in terms of a good yield. More preferably, it is molar.

  The molar ratio of the compound (25) to the compound (26) used in reaction formula (16) is not particularly limited, but 0.1 to 10 times the molar amount of the compound (25) relative to 1 mol of the compound (26) 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 (14) used in reaction formula (17) is not particularly limited, but 0.1 to 20 times the molar amount of the compound (14) relative to 1 mol of the compound (22) Is preferable, and 1.0 to 5 times is preferable in that the yield of the benzothienopyrimidine compound (1) of the present invention is good.

  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 form compound (23). The compound (23) is reacted with the compound (17) as shown in the reaction formula (9) to obtain the compound (10) of the present invention.

  The compound (23) 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 a compound (23).

  The molar ratio of the compound (23) to the compound (17) used in the 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 (23) 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, the reaction of reaction formula (13) will be described.

  About reaction formula (13), although it is also possible to go by one pot, it can also carry out stepwise like following reaction formula (18) and (19), 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 (27) to (28) can be produced using known methods, or commercially available products can be used.

  Although it does not specifically limit as a compound (27), For example, the compound represented by the following 27-1 to 27-10 can be illustrated.

As a compound (28), although it does not specifically limit, the compound represented by the following 28-1 to 28-5 can be illustrated, for example.

As a compound (17), although it does not specifically limit, the compound similar to Reaction formula (3) can be illustrated.

  The reaction formula (13) is a method of producing a compound (10) of the present invention by reacting the compound (27), the compound (28) and the compound (17) in the presence of a base or an acid.

  Reaction formula (13) can be decomposed into reaction formulas (18) and (19). That is, in this reaction, compound (27) reacts with compound (28) in the presence of a base to form compound (23). The compound (23) is reacted with the compound (17) as shown in the reaction formula (9) to obtain the compound (10) of the present invention.

  The compound (23) 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 to be used is not particularly limited, but it is preferably 0.5 to 10 times the mol of 1 mol of the compound (28), and 1.1 to 4.0 times in terms of a good yield. More preferably, it is molar.

  The molar ratio of the compound (27) to the compound (28) used in reaction formula (18) is not particularly limited, but 0.1 to 10 times the molar amount of the compound (27) relative to 1 mol of the compound (28) 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 reaction formula (19) is not particularly limited, but 0.1 to 20 times the molar amount of the compound (17) relative to 1 mol of the compound (23) 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 ⁴ , X ⁶ , 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.

  The compound (18) is not particularly limited, and examples thereof include compounds represented by methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, benzyl acetate, phenyl acetate and naphthyl acetate. can do.

  Reaction formula (4) can be decomposed into reaction formulas (10) and (11). That is, in this reaction, compound (18) reacts with compound (19) in the presence of a base to form compound (24). The compound (24) is reacted with the compound (17) as shown in the reaction formula (11) to obtain the compound (20) of the present invention.

  The compound (24) may be isolated but may not be isolated and may be used in the next step, reaction (11), in one pot.

  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 compound (24).

  The molar ratio of the compound (24) 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 (24) 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 benzothienopyrimidine compound (11) of the present invention.

  Next, reaction formula (14) will be described.

  The reaction formula (14) can be performed in one pot, but can also be performed stepwise as in the following reaction formulas (20) and (11).

(In the general formula, Ar ¹² , X ^{1 to} X ⁴ , X ⁶ , X ⁷ , Z, and R ⁵ have the same definitions as in the reaction formula (4).)
The reaction scheme (14) is a method of producing a compound (20) by reacting the compound (29), the compound (28) and the compound (17) in the presence of a base or an acid.

  The compound (29) is not particularly limited, and, for example, methylthio glycolate, ethyl thio glycolate, propyl thio glycolate, butyl thio glycolate, pentyl thio glycolate, hexyl thio glycolate, phenyl thio glycolate And compounds represented by benzylthio glycolate and naphthylthio glycolate.

  Reaction equation (14) can be decomposed into reaction equations (20) and (11). That is, in this reaction, compound (29) reacts with compound (28) in the presence of a base to form compound (24). The compound (24) is reacted with the compound (17) as shown in the reaction formula (11) to obtain the compound (20) of the present invention.

  The compound (24) may be isolated but may not be isolated and may be used in the next step, reaction (11), in one pot.

  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 (28), and 1.1 to 4.0 times in terms of a good yield. More preferably, it is molar.

  The molar ratio of the compound (29) to the compound (28) used in the reaction formula (20) is not particularly limited, but 0.1 to 10 times the molar amount of the compound (29) relative to 1 mol of the compound (28) It is preferable that it is 1.1-2.0 times mole at the point with a favorable yield of compound (24).

  The molar ratio of the compound (24) 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 (24) Is preferable, and 1.0 to 5 times is preferable in that the yield of the compound (20) is good.

  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 benzothienopyrimidine compound represented by the general formula (1), and the benzothienopyrimidine compound is preferably used for an electron transport layer, an electron injection layer, or a light emitting layer.

  The benzothieno pyrimidine compound represented by General formula (1) can be preferably used as an electron transport material (an electron transport material, an 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.

  The benzothienopyrimidine compound represented by the general formula (1) of the present invention has a high solubility in chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate, tetrahydrofuran and the like, and thus a general-purpose device is used. Film formation by a spin coat method, an ink jet method, a cast method, a dip method or the like is also possible.

  Typical structures of the organic electroluminescent device from which the effects of the present invention can be obtained include a substrate, an anode, a hole injection layer, a light emitting layer of a hole transport layer, an electron transport layer, and a cathode.

  The anode and the cathode of the organic electroluminescent element are connected to a power source via an electrical conductor. The organic electroluminescent device operates by applying a potential between the anode and the cathode. Holes are injected from the anode into the organic electroluminescent device, and electrons are injected into the organic electroluminescent device at the cathode.

  The organic electroluminescent device is typically placed on a substrate, and the anode or the cathode can be in contact with the substrate. The electrode in contact with the substrate is conveniently referred to as the lower electrode. In general, the lower electrode is an anode, but the organic electroluminescent device of the present invention is not limited to such a form.

  The substrate may be light transmissive or opaque depending on the intended light emission direction. The light transmission properties can be confirmed by electroluminescence through the substrate. In general, transparent glass or plastic is employed as the substrate. The substrate may be a composite structure comprising multiple material layers.

  If the electroluminescent emission is confirmed through the anode, the anode is formed to either pass or substantially transmit the emission.

  Common transparent anode (anode) materials used in the present invention include indium-tin oxide (ITO), indium-zinc oxide (IZO), or tin oxide. Furthermore, other metal oxides such as aluminum or indium-doped tin oxide, magnesium-indium oxide, or nickel-tungsten oxide are also preferably used. In addition to these oxides, metal nitrides, such as gallium nitride, metal selenides, such as zinc selenide, or metal sulfides, such as zinc sulfide, can be used as the anode. The anode can be modified with plasma deposited fluorocarbons.

  If the electroluminescent emission is confirmed only through the cathode, the transmission properties of the anode are not important and any conductive material transparent, opaque or reflective can be used. Examples of conductors for this application include gold, iridium, molybdenum, palladium, platinum and the like.

  The hole injection layer can be provided between the anode and the hole transport layer. The material of the hole injection layer improves the film forming properties of the organic material layer, such as the hole transport layer and the hole injection layer, and serves to facilitate the injection of holes into the hole transport layer. Examples of materials suitable for use in the hole injection layer include porphyrin compounds, plasma deposited fluorocarbon polymers, and amines having an aromatic ring such as biphenyl or carbazole, such as m-MTDATA (4,4 ') , 4 ''-tris [(3-methylphenyl) phenylamino] triphenylamine), 2T-NATA (4,4 ', 4' '-tris [(N-naphthalen-2-yl) -N-phenylamino] Triphenylamine), triphenylamine, tolylamine, tolyldiphenylamine, N, N′-diphenyl-N, N′-bis (3-methylphenyl) -1,1′-biphenyl-4,4′-diamine, N, N, N'N'-tetrakis (4-methylphenyl) -1,1'-biphenyl-4,4'-diamine, MeO-TPD N, N, N'N'-tetrakis (4-methoxyphenyl) -1,1'-biphenyl-4,4'-diamine), N, N'-diphenyl-N, N'-dinaphthyl-1,1 ' -Biphenyl-4,4'-diamine, N, N'-bis (methylphenyl) -N, N'-bis (4-normalbutylphenyl) phenanthrene-9,10-diamine, N, N'-diphenyl-N , N′-bis (9-phenylcarbazol-3-yl) -1,1′-biphenyl-4,4′-diamine and the like.

  The hole transport layer of the organic electroluminescent device preferably contains one or more hole transport compounds (hole transport materials), for example, an aromatic tertiary amine. An aromatic tertiary amine is a compound containing one or more trivalent nitrogen atoms, and the trivalent nitrogen atoms are bonded only to carbon atoms, and one or more of these carbon atoms are aromatic rings. It is formed. In particular, the aromatic tertiary amines may be arylamines, such as monoarylamines, diarylamines, triarylamines or polymeric arylamines.

  As the hole transport material, benzothienopyrimidine compounds represented by the general formula (1) can be used, and as other materials, aromatic tertiary amines having one or more amino groups are used. Can. In addition, polymeric hole transport materials can be used. For example, poly (N-vinylcarbazole) (PVK), polythiophene, polypyrrole, polyaniline and the like can be used.

  Specifically, NPD (N, N'-bis (naphthalen-1-yl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine), α-NPD (N, N) '-Di (1-naphthyl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine), TPBi (1,3,5-tris (1-phenyl-1H-benzimidazole) 2-yl) benzene), TPD (N, N'-bis (3-methylphenyl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine) and the like.

Between the hole injection layer and the hole transport layer, dipyrazino [2,3-f: 2 ', 3'-h] quinoxaline-2,3,6,7,10,11-hexacarbonitrile as a charge generation layer (HAT-CN), 7,7 ', 8,8'-tetracyanoquinodimethane (TCNQ), 2,3,5,6-tetrafluoro-7,7', 8,8'-tetracyanoquinodi A layer containing methane (F ₄ -TCNQ) or the like may be provided, or the hole transport layer may be doped with these compounds.

  The light emitting layer of the organic electroluminescent device contains a phosphorescent material or a fluorescent material, and in this case, light emission occurs as a result of recombination of electron-hole pairs in this region. The light emitting layer may be formed of a single material containing both a small molecule and a polymer, but more generally is formed of a host material doped with a guest compound, and the emission mainly originates from the dopant, It can emit any color.

  As the host material of the light emitting layer, benzothienopyrimidine compounds represented by the general formula (1) can be used. Other materials include, for example, biphenyl group, fluorenyl group, triphenylsilyl group, carbazole group, The compound which has a pyrenyl group or an anthranil group is mentioned, These materials can also be used independently and can also be mixed and used with the benzothieno pyrimidine compound represented by General formula (1).

  Specifically, DPVBi (4,4'-bis (2,2-diphenylvinyl) -1,1'-biphenyl), BCzVBi (4,4'-bis (9-ethyl-3-carbazovinylene) 1,1 are used. '-Biphenyl), TBADN (2-tertiary butyl-9,10-di (2-naphthyl) anthracene), ADN (9,10-di (2-naphthyl) anthracene), CBP (4,4'-bis (4) Carbazol-9-yl) biphenyl), CDBP (4,4'-bis (carbazol-9-yl) -2,2'-dimethylbiphenyl), 9,10-bis (biphenyl) anthracene and the like.

  The host material in the light emitting layer may be an electron transporting material as defined below, a hole transporting material as defined above, another material supporting hole-electron recombination, or a combination of these materials.

  Examples of fluorescent dopants include pyrene, anthracene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine and quinacridone, dicyanomethylene pyran compound, thiopyran compound, polymethine compound, pyrilium or thiapyrilium compound, fluorene derivative, periflanthene derivative, indeno Examples thereof include perylene derivatives, bis (azinyl) amine boron compounds, bis (azinyl) methane compounds, carbostyril compounds, and compounds that exhibit heat activation delayed fluorescence.

  Examples of useful phosphorescent dopants include organometallic complexes of transition metals such as iridium, platinum, palladium, osmium and the like.

Examples of dopants include Alq ₃ (tris (8-hydroxyquinoline) aluminum), DPAVBi (4,4′-bis [4- (di-para-tolylamino) styryl] biphenyl), perylene, Ir (PPy) ₃ ( Examples include tris (2-phenylpyridine) iridium (III), FlrPic (bis (3,5-difluoro-2- (2-pyridyl) phenyl- (2-carboxypyridyl) iridium (III), and the like.

  As the thin film forming material used to form the electron transport layer of the organic electroluminescent device of the present invention, the benzothienopyrimidine compound represented by the general formula (1) of the present invention can be used. Note that the electron transporting layer may contain other electron transporting materials. Other electron transporting materials include alkali metal complexes, alkaline earth metal complexes, earth metal complexes and the like.

  Desirable alkali metal complexes, alkaline earth metal complexes or earth metal complexes include, for example, lithium 8-hydroxyquinolinate (Liq), zinc bis (8-hydroxyquinolinate), bis (8-hydroxyquinolinate) ) Copper, bis (8-hydroxyquinolinate) manganese, tris (8-hydroxyquinolinate) aluminum, tris (2-methyl-8-hydroxyquinolinate) aluminum, tris (8-hydroxyquinolinate) gallium Bis (10-hydroxybenzo [h] quinolinate) beryllium, bis (10-hydroxybenzo [h] quinolinate) zinc, bis (2-methyl-8-quinolinate) chlorogallium, bis (2-methyl-8-quinolinate) (O-cresolato) gallium, bis (2-methyl-8-quino) Inert) -1-naphthoquinone Trad aluminum, bis (2-methyl-8-quinolinato) -2-naphthoquinone Trad gallium, and the like.

  A hole blocking layer may be provided between the light emitting layer and the electron transporting layer for the purpose of improving carrier balance. Preferred compounds for the hole blocking layer are BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis (2 -Methyl-8-quinolinolato) -4- (phenylphenolate) aluminum), bis (10-hydroxybenzo [h] quinolinate) beryllium) and the like.

  In the organic electroluminescent device of the present invention, an electron injection layer may be provided for the purpose of improving the electron injection property and improving the device characteristics (for example, light emission efficiency, low voltage drive, or high durability).

As a compound desirable as an electron injection layer, benzothienopyrimidine compounds represented by the general formula (1), fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarbonide An acid, a fluorenylidene methane, anthraquinodimethane, or anthrone etc. are mentioned. Also, the above-mentioned metal complexes, alkali metal oxides, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth halides, SiO _x , AlO _x , SiN _x , SiON, _{AlON, GeO X, LiO X,} LiON, TiO X, TiON, TaO X, TaON, TaN X, various oxides of C, etc. may be used an inorganic compound such as a nitride, and oxynitride.

When light emission is only seen through the anode, the cathode used in the present invention can be formed from almost any conductive material. Preferred cathode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, indium , Lithium / aluminum mixtures, rare earth metals and the like.

It is sectional drawing of the organic electroluminescent element produced by evaluation example 1 grade | etc.,. It is sectional drawing of the organic electroluminescent element produced by evaluation example-10 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

Under an argon stream, acetophenone (2.64 g) and 3-chloro-1,2-benzisothiazole (3.39 g) are added to DMF (20 mL), and a potassium tert-butoxide solution in DMF (50 mL) is added thereto. Was then added dropwise and then stirred at 100.degree. C. for 20 hours. The reaction mixture was allowed to cool to room temperature and water was added. The precipitated solid is washed with water and then with hexane to give a yellow powder (yield 4.3 g, 86%) of the desired 3-amino-2-benzoylbenzo [b] thiophene (A-1). The

¹ H-NMR (DMSO-d ₆ ), δ (ppm): 7.38 (t, J = 7.2 Hz, 1 H), 7.45 to 7.54 (m, 4 H), 7.74 (d, J = 8.1 Hz, 2 H), 7.78 (d, J = 8.1 Hz, 1 H), 8. 20 (d, J = 8.1 Hz, 1 H), 8. 27 (s, 2 H).
Under argon flow, compound A-1 (1.27 g), 3-bromo-5-chlorobenzonitrile (2.16 g), and potassium tert-butoxide (842 mg) were added to xylene (25 mL), Stir for 5 hours. The reaction mixture was allowed to cool to room temperature and then methanol was added. The precipitated solid was washed with water, washed with methanol, and further washed with hexane to obtain a pale brown solid. A light brown powder of 2- (3-bromo-5-chlorophenyl) -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (B-1) is obtained by recrystallization from o-xylene. (Yield 1.42 g, yield 63%) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.61-7.70 (m, 5 H), 7.73 (t, J = 7.6 Hz, 1 H), 7.96 (d, J = 8.0 Hz, 1 H), 8.36 (d, J = 8.0 Hz, 2 H), 8.72-8.75 (m, 2 H), 8.83 (s, 1 H).
Example 2

Compound B-1 (1.36 g), 4- (2-pyridyl) phenylboronic acid (1.43 g), palladium acetate (13.5 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′ under a stream of argon , 6'-Triisopropylbiphenyl (85. 8 mg) is added to toluene (30 mL), then 3 M aqueous potassium carbonate solution (4.8 mL) and 1-butanol (4.8 mL) are added, followed by heating for 2.5 hours Refluxed. The reaction mixture was allowed to cool to room temperature and then water and methanol were added. The precipitated solid was washed with water, washed with methanol and further washed with hexane to obtain a gray solid. The gray solid is recrystallized with o-xylene, and the desired 2- [4,4 ′ ′-bis (2-pyridyl)-[1,1 ′: 3 ′, 1 ′ ′]-terphenyl-5′- is obtained. A yellow powder (yield 1.59 g, 82%) of yl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (C-1) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.30 (dd, J = 7.5, 4.8 Hz, 2 H), 7.62-7.71 (m, 4 H), 7.74 ( t, J = 7.5 Hz, 1 H, 7.834 (t, J = 7.5 Hz, 2 H), 7.87 (d, J = 7.9 Hz, 2 H), 7.98 (d, J = 7) .9 Hz, 1 H), 7.99 (d, J = 8.4 Hz, 4 H), 8. 10 (s, 1 H), 8.22 (d, J = 8.4 Hz, 4 H), 8.44 (d , J = 8.2 Hz, 2 H), 8.78 (d, J = 4.8 Hz, 2 H), 8.81 (d, J = 7.8 Hz, 1 H), 9. 10 (s, 2 H).
Example 3

Compound B-1 (1.12 g), 9-phenanthreneboronic acid (581 mg), and tetrakis (triphenylphosphine) palladium (57.8 mg) were added to THF (24 mL) under argon stream, and 4N sodium hydroxide was added The aqueous solution (1.9 mL) was added and then heated to reflux for 16 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 gray solid is recrystallized with toluene, and the yellow color of 2- [3-chloro-5- (9-phenanthryl) phenyl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (B-2) A powder (yield 1.16 g, yield 85%) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.59-7.76 (m, 10 H), 7.84 (s, 1 H), 7.95 (m, 3 H), 8.37 (d , J = 8.0 Hz, 2 H), 8.71 (d, J = 7.8 Hz, 1 H), 8.79 (d, J = 8.2 Hz, 1 H), 8.83-8.86 (m, 2H), 8.89 (s, 1H).
Compound B-2 (1.14 g), 4- (2-pyridyl) phenylboronic acid (497 mg), palladium acetate (9.4 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6 under an argon stream '-Triisopropylbiphenyl (59.5 mg) was added to toluene (21 mL), and further 3 M aqueous potassium carbonate solution (2.1 mL) and 1-butanol (2.1 mL) were added, and then heated to reflux for 3 hours. After the reaction mixture was allowed to cool, water and methanol were added. The precipitated solid was washed with water, washed with methanol and further washed with hexane to obtain a gray solid. The gray solid is recrystallized with toluene, and the desired 2- [5- (9-phenanthryl) -4 '-(2-pyridyl) biphenyl-3-yl] 4-phenyl- [1] benzothieno [3,2- is obtained. A yellow powder (yield 1.23 g, 89%) of d] pyrimidine (C-2) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.26 to 7.30 (m, 1 H), 7.58 to 7.66 (m, 5 H), 7.68 to 7.76 (m, 5) 4H), 7.80 (t, J = 7.5 Hz, 1 H), 7.84 (d, J = 7.7 Hz, 1 H), 7.94 (s, 1 H), 7.96 (d, J = 8.0 Hz, 1 H), 7.99-8.02 (m, 4 H), 8.12 (d, J = 8.3 Hz, 1 H), 8. 19 (d, J = 8.6 Hz, 2 H), 8.41 (d, J = 8.1 Hz, 2 H), 8.74 (d, J = 8.2 Hz, 1 H), 8.76 (d, J = 4.9 Hz, 1 H), 8.81 (d , J = 8.4 Hz, 1 H), 8.86 (d, J = 8.0 Hz, 1 H), 8.99 (s, 1 H), 9.21 (s, 1 H).
Example 4

Compound B-1 (2.50 g), 4- (2-pyridyl) phenylboronic acid (1.32 g), and tetrakis (triphenylphosphine) palladium (128 mg) were added to THF (55 mL) under argon stream, and further added. Aqueous 3 M potassium carbonate solution (4.4 mL) was added and then heated to reflux for 23 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 gray solid is recrystallized with xylene and 2- [3-chloro-4 '-(2-pyridyl) biphenyl-5-yl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (B -3) yellow powder (yield 2.66 g, 91% yield) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.28-7.32 (m, 1 H), 7.62-7. 70 (m, 4 H), 7.34 (t, J = 7. 5 Hz, 1 H), 7.80 (s, 1 H), 7.82-7. 87 (m, 2 H), 7.89 (d, J = 8.4 Hz, 2 H), 7.97 (d, J = 7.9 Hz, 1 H), 8. 19 (d, J = 8.4 Hz, 2 H), 8. 40 (d, J = 8.1 Hz, 2 H), 8.76-8.79 (m, 3 H), 8.97 (s, 1 H).
Compound B-3 (1.32 g), 1-pyreneboronic acid (738 mg), palladium acetate (11.2 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (argon flow) under an argon stream 47.7 mg) was added to THF (50 mL), and further 3 M aqueous potassium carbonate solution (5.0 mL) was added, and then heated to reflux for 2 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. This gray solid is purified by silica gel column chromatography (developing solvent: mixed solvent of toluene: chloroform = 50: 50 (volume ratio)) to obtain the desired 2- [5- (1-pyrenyl) -4 ′-(2 There was obtained a yellow powder (yield 1.72 g, 99%) of -pyridyl) biphenyl-3-yl] 4-phenyl- [1] benzothieno [3,2-d] pyrimidine (C-3).

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.30-7.34 (m, 1 H), 7.57-7. 65 (m, 4 H), 7.70 (dd, J = 8. 1, 7.1 Hz, 1 H), 7.82-7. 87 (m, 2 H), 7. 95 (d, J = 8.0 Hz, 1 H), 8.03 (d, J = 8.4 Hz, 2 H ), 8.06 (d, J = 7.6 Hz, 1 H), 8.09 (s, 1 H), 8.09 (d, J = 9.2 Hz, 1 H), 8.16 (d, J = 3) .1 H, 2 H), 8.18-8.23 (m, 4 H), 8. 25 (d, J = 7.7 Hz, 1 H), 8.33 (d, J = 7.9 Hz, 1 H), 8 .37 (d, J = 9.2 Hz, 1 H), 8. 40 (d, J = 8.0 Hz, 2 H), 8.74 (d, J = 7.5 Hz, 1 H), 8.78 (d, J = 4.8 Hz, 1 H), 9.07 s, 1H), 9,22 (s, 1H).
Example 5

Compound B-3 (1.32 g), 3-fluorantheneboronic acid (738 mg), palladium acetate (11.2 mg), and 2-dicyclohexylphosphino-2 ', 4', 6'-tri under argon flow Isopropylbiphenyl (47.7 mg) was added to THF (50 mL), and further 3 M aqueous potassium carbonate solution (5.0 mL) was added, and then heated to reflux for 6 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 gray solid is recrystallized with xylene to give the desired 2- [5- (3-fluorantenyl) -4 '-(2-pyridyl) biphenyl-3-yl] 4-phenyl- [1] benzothieno [3 There was obtained a yellow powder (yield 1.31 g, 76%) of [2-d] pyrimidine (C-4).

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.28 to 7.31 (m, 1 H), 7.43 to 7.46 (m, 2 H), 7.61 to 7.73 (m, 5) 6H), 7.80-7.85 (m, 2H), 7.87 (d, J = 7.1 Hz, 1H), 7.95-8.01 (m, 3H), 8.01 (d, 7H) J = 8.4 Hz, 2 H), 8.03 (d, J = 6.8 Hz, 1 H), 8.06 (s, 1 H), 8. 10 (d, J = 7.1 Hz, 1 H), 8. 12 (d, J = 8.4 Hz, 1 H), 8. 20 (d, J = 8.4 Hz, 2 H), 8.41 (d, J = 8.1 Hz, 2 H), 8.75-8.78 (M, 2H), 9.04 (s, 1 H), 9.18 (s, 1 H).
Example 6

Compound B-1 (1.32 g), 3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) carbazole (897 mg), and tetrakistriphenylphosphine under argon gas flow Palladium (40.9 mg) was added to THF (29 mL), and further 3 M aqueous potassium carbonate solution (6.1 mL) was added, and then heated to reflux for 24 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 gray solid is recrystallized with xylene and 2- [3-chloro-5- (carbazol-3-yl) phenyl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (B-4) A brown powder (yield 1.44 mg, 92%) was obtained.

¹ H-NMR (DMSO-d ₆ ), δ (ppm): 7.22 (t, J = 7.1 Hz, 1 H), 7.44 (t, J = 7.6 Hz, 1 H), 7.54 ( d, J = 8.1 Hz, 1H), 7.66 (d, J = 8.4 Hz, 1H), 7.70-7.78 (m, 4H), 7.84-7.90 (m, 2H) ), 8.05 (s, 1 H), 8. 28 (d, J = 8.0 Hz, 1 H), 8.32 (d, J = 7.8 Hz, 1 H), 8.37 (d, J = 8) 11.0 Hz, 2H), 8.62 (s, 1 H), 8.66 (s, 1 H), 8.79 (d, J = 7.8 Hz, 1 H), 8.98 (s, 1 H), 11. 44 (s, 1 H).
Compound B-4 (1.44 g), 4- (2-pyridyl) phenylboronic acid (640 mg), palladium acetate (12.0 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6 under an argon stream '-Triisopropylbiphenyl (76.6 mg) was added to THF (27 mL), and further 3 M aqueous potassium carbonate solution (2.1 mL) was added, and then heated to reflux for 17 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. This gray solid is purified by silica gel column chromatography (developing solvent: mixed solvent of toluene: chloroform = 50: 50 (volume ratio)) to obtain the desired 2- [5- (carbazol-3-yl) -4′- A yellow powder (yield 1.71 g, 97%) of (2-pyridyl) biphenyl-3-yl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (B-5) was obtained .

¹ H-NMR (DMSO-d ₆ ), δ (ppm): 7.22 (t, J = 7.4 Hz, 1 H), 7.41 (dd, J = 7.4, 4.8 Hz, 1 H), 7.44 (t, J = 7.6 Hz, 1 H), 7.55 (d, J = 8.1 Hz, 1 H), 7.68 (d, J = 8.4 Hz, 1 H), 7. 70-7 .79 (m, 4 H), 7.86 (t, J = 7.6 Hz, 1 H), 7.93-7.99 (m, 2 H), 8.08-8.12 (m, 3 H), 8 .27-8.35 (m, 5 H), 8.39 (d, J = 8.0 Hz, 2 H), 8. 73 (s, 1 H), 8. 74 (d, J = 4.8 Hz, 1 H) , 8.81 (d, J = 7.8 Hz, 1 H), 8.98 (s, 1 H), 9.05 (s, 1 H), 11.42 (s, 1 H).
Compound B-5 (1.71 g), 2-bromopyridine (493 mg), copper (I) oxide (18.6 mg), 1,10-phenanthroline (46.9 mg), potassium carbonate (719 mg) in an argon stream And 18-crown-6-ether (137 mg) were added to xylene and heated to reflux for 17 hours. The reaction was allowed to cool to room temperature and then water and methanol were added. The precipitated solid was washed with water, washed with methanol, and further washed with hexane to give a brown solid. The resulting solid is recrystallized with xylene to give the desired 2- [5- [9- (2-pyridyl) carbazol-3-yl] -4 '-(2-pyridyl) biphenyl-3-yl] -4 A white powder (yield 1.34 g, 70%) of -phenyl- [1] benzothieno [3,2-d] pyrimidine (C-5) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.28-7.31 (m, 1H), 7.36-7.41 (m, 2H), 7.51 (t, J = 7.7 Hz , 1H), 7.61-7.68 (m, 4H), 7. 70-7. 76 (m, 2H), 7, 82 (t, J = 7.6 Hz, 1 H), 7.87 (d , J = 7.8 Hz, 1 H), 7.92-8.04 (m, 7 H), 8. 17 (s, 1 H), 8.22 (d, J = 8.3 Hz, 2 H), 8.28 (D, J = 7.7 Hz, 1 H), 8.85 (d, J = 8.2 Hz, 2 H), 8.57 (s, 1 H), 8.77-8.81 (m, 2 H), 8 .82 (d, J = 8.4 Hz, 1 H), 9.09 (s, 1 H), 9. 14 (s, 1 H).
Example 7

Compound A-1 (1.52 g) and 5-bromo-2-chlorobenzonitrile (1.95 g) are dissolved in THF (12 mL) under an argon stream, and a solution of potassium tert-butoxide (741 mg) in THF is dissolved therein. The suspension (18 mL) was added dropwise and then stirred at 30 ° C. for 16 hours. Water and methanol were then added to the reaction mixture. The precipitated solid is washed with water, washed with methanol, and further washed with hexane to give the desired 2- (5-bromo-2-chlorophenyl) -4-phenyl- [1] benzothieno [3,2-d]. A pale yellow solid (yield 2.00 g, 74%) of pyrimidine (B-6) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.47 (d, J = 8.5 Hz, 1 H), 8.56 (dd, J = 8.5, 2.4 Hz, 1 H), 7.59 − 7.68 (m, 4 H), 7. 74 (dd, J = 8.0, 7.6 Hz, 1 H), 7.79 (d, J = 8.0 Hz, 1 H), 8.21 (d, J = 2.4 Hz, 1 H), 8. 36 (d, J = 8.1 Hz, 2 H), 8. 71 (d, J = 8.0 Hz, 1 H).
Example 8

Compound B-6 (1.75 g), 4- (2-pyridyl) phenylboronic acid (1.85 g), palladium acetate (17.4 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′ under an argon stream 6'-triisopropylbiphenyl (73.8 mg) was added to THF (39 mL), to which 3 M aqueous potassium carbonate solution (6.2 mL) was added, and then heated to reflux for 16 hours. After the reaction mixture was allowed to cool, water and methanol were added. The precipitated solid is washed with water, washed with methanol, further washed with hexane, and the desired 2- [4,4 ′ ′-bis (2-pyridyl)-[1,1 ′: 4 ′, 1 ′ ′ A brown solid (yield 2.40 g, 96%) of [] -terphenyl-5'-yl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (C-6) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.23 (dd, J = 6.6, 4.7 Hz, 1 H), 7.26-7.29 (m, 1 H), 7.36-7 .44 (m, 3 H), 7.50 (d, J = 8.4 Hz, 2 H), 7.57 (t, J = 7.5 Hz, 1 H), 7.66-7.84 (m, 8 H) , 7.88-7.94 (m, 4H), 8.00 (d, J = 6.6 Hz, 2 H), 8. 17 (d, J = 8.4 Hz, 2 H), 8.57 (d, J) J = 1.9 Hz, 1 H), 8.57 (d, J = 7.5 Hz, 1 H), 8.71 (d, J = 4.7 Hz, 1 H), 8.76 (d, J = 4.7 Hz) , 1 H).
Example 9

Under an argon stream, 3'-bromoacetophenone (1.39 mL) and 3-chloro-1,2-benzisothiazole (1.70 g) are added to DMF (5.0 mL), and potassium tert-butoxide (1 A suspension of .68 g of DMF (15.0 mL) was added dropwise and then stirred at 100 ° C. for 4 hours. The reaction mixture was allowed to cool to room temperature and water was added. The precipitated solid was washed with water and further washed with hexane. The obtained solid is purified by silica gel column chromatography (developing solvent; chloroform) to obtain a yellow powder (yield) of the desired 3-amino-2- (3'-bromobenzoyl) benzo [b] thiophene (A-2). 3.04 g (yield 91%) was obtained.

¹ H-NMR (DMSO-d ₆ ) δ (ppm): 7.38 (dd, J = 8.1, 7.1 Hz, 1 H), 7.53 (t, J = 7.8 Hz, 1 H), 7 .59 (dd, J = 8.0, 7.1 Hz, 1 H), 7.78-7.81 (m, 2 H), 7.87 (d, J = 8.1 Hz, 1 H), 7.92 (m. s, 1 H), 8. 29 (d, J = 8.0 Hz, 1 H), 8.41 (s, 2 H).
Compound A-2 (3.02 g), 3-bromobenzonitrile (2.48 g), and sodium sulfate (3.87 g) were added to DMF (18 mL) under an argon stream, and potassium tert-butoxide (1. A suspension of 12 g of DMF (27 mL) was added dropwise and then stirred at 30 ° C. for 21 hours. Methanol was then added to the reaction mixture. The precipitated solid was washed with water, washed with methanol, and further washed with hexane to obtain a pale brown solid. This is subjected to recrystallization with o-xylene to thin the desired 2- (3-bromophenyl) -4- (3-bromophenyl)-[1] benzothieno [3,2-d] pyrimidine (B-7) A brown powder (yield 3.68 g, 82% yield) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.46 (t, J = 7.9 Hz, 1 H),
7.54 (t, J = 7.9 Hz, 1 H), 7.64-7.69 (m, 2 H), 7.72-7.77 (m, 2 H), 7.97 (d, J = 8) .0 Hz, 1 H), 8. 29 (d, J = 7.8 Hz, 1 H), 8. 50 (s, 1 H), 8. 72 (d, J = 7.8 Hz, 1 H), 8. 75 (d , J = 7.9 Hz, 1 H), 8.92 (s, 1 H).
Example 10

Compound B-7 (1.99 g), 4- (2-pyridyl) phenylboronic acid (1.91 g), and bis (triphenylphosphino) palladium dichloride (56 mg) in THF (40 mL) under an argon stream In addition, 3 M aqueous potassium carbonate solution (6.4 mL) was added thereto and then heated to reflux for 16 hours. The reaction mixture was allowed to cool to room temperature and then water and methanol were added. The precipitated solid is washed with water, washed with methanol, further washed with hexane, and the desired 2- [4 '-(2-pyridyl) biphenyl-3-yl] 4- [4'-(2-pyridyl) A brown solid (yield 2.05 g, 80%) of biphenyl-3-yl]-[1] benzothieno [3,2-d] pyrimidine (C-7) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.29-7.32 (m, 2 H), 7.66 (dd, J = 7.9, 7.1 Hz, 1 H), 7.68 (t , J = 7.7 Hz, 1 H), 7.73 (dd, J = 8.0, 7.1 Hz, 1 H), 7.77 (t, J = 7.8 Hz, 1 H), 7.80-7. 87 (m, 5 H), 7.90-7.92 (m, 1 H), 7. 91 (d, J = 8.5 Hz, 2 H), 7.94 (d, J = 8.5 Hz, 2 H), 7.99 (d, J = 7.9 Hz, 1 H), 8. 19 (d, J = 8.5 Hz, 2 H), 8. 20 (d, J = 8.5 Hz, 2 H), 8.41 (d , J = 7.8 Hz, 1 H), 8.71 (s, 1 H), 8.75-8.80 (m, 3 H), 8.82 (d, J = 7.9 Hz, 1 H), 9.13 (S, 1 H).
Example 11

Compound A-1 (253 mg), 3'-cyano-4- (2-pyridyl) biphenyl (103 mg), and sodium sulfate (426 mg) were added to THF (2 mL) under an argon stream, and potassium tert-butoxide ( A THF suspension (3.0 mL) of 123 mg) was added dropwise and then stirred at 30.degree. Thereafter, 3'-cyano-4- (2-pyridyl) biphenyl (103 mg each, a total of 309 mg) was added in three divided portions every one hour, and then stirred for 21 hours. Then, it heated and refluxed for 21 hours. The reaction mixture was allowed to cool to room temperature and then water and methanol were added. The precipitated solid is washed with water, washed with methanol, and further washed with hexane to obtain the desired 2- [4 '-(2-pyridyl) biphenyl-3-yl] -4-phenyl- [1] benzothieno [ The white solid (yield 58 mg, 12% of yield) of 3, 2- d] pyrimidine (C-8) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.40-7.43 (m, 1 H), 7.61-7.75 (m, 6 H), 7.83 (d, J = 8.2 Hz) , 1H), 7.92-7.98 (m, 5H), 8.23 (d, J = 8.2 Hz, 2 H), 8.41 (d, J = 8.2 Hz, 2 H), 8.78 (D, J = 7.8 Hz, 1 H), 8.81-8.84 (m, 2 H), 9.10 (s, 1 H).
Example 12

Compound A-1 (1.01 g), 4-bromobenzonitrile (801 mg), and sodium sulfate (1.70 g) are added to THF (8.0 mL) under an argon stream, and potassium tert-butoxide (494 mg) is added thereto. The THF suspension (12.0 mL) was added dropwise and then stirred at 30.degree. C. for 17 hours. Then, 4-bromobenzonitrile (364 mg) was further added, and the mixture was further heated to reflux for 2 hours. The reaction mixture was allowed to cool to room temperature and then water and methanol were added. The precipitated solid is washed with water, washed with methanol, and further washed with hexane to give the desired 2- (4-bromophenyl) -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (B A pale yellow solid (yield 684 mg, 41%) of -8) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.61-7.75 (m, 5 H), 7.71 (d, J = 8.7 Hz, 2 H), 7.97 (d, J = 8 .0 Hz, 1 H), 8. 38 (d, J = 8.1 Hz, 2 H), 8. 68 (d, J = 8.7 Hz, 2 H), 8. 75 (d, J = 7.8 Hz, 1 H) .
Example 13

Compound B-8 (682 mg), bis (4-biphenylyl) amine (576 mg), potassium carbonate (496 mg), and 18-crown-6-ether (86.2 mg) in xylene (6.6 mL) in an argon stream In addition, it was heated to 100 ° C. Then, a mixture of palladium acetate (7.3 mg) and tri- (tert-butyl) phosphine in 1 M-toluene solution (98 μL) in xylene (1.6 mL) is added to the solution heated to 100 ° C. It was then heated to reflux for 17 hours. The reaction mixture was allowed to cool to room temperature and then water and methanol were added. The precipitated solid is washed with water, washed with methanol, and further washed with hexane to obtain the desired 2- [4-bis (4-biphenylyl) aminophenyl] -4-phenyl- [1] benzothieno [3,2- A gray solid (yield 901 mg, 84%) of d] pyrimidine (C-9) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.31 to 7.38 (m, 8 H), 7.45 to 7.49 (m, 4 H), 7.59 (d, J = 8.6 Hz) , 4H), 7.61-7.68 (m, 8H), 7.72 (t, J = 7.8 Hz, 1 H), 7.96 (d, J = 8.0 Hz, 1 H), 8.39 (D, J = 8.0 Hz, 2 H), 8.70 (d, J = 8.7 Hz, 2 H), 8.77-8.78 (m, 1).
Example 14

Under argon flow, compound A-1 (1.01 g), 3,5-dibromobenzonitrile (1.15 g), and sodium sulfate (1.70 g) are added to THF (8.0 mL), and potassium tert- A THF suspension (12 mL) of butoxide (494 mg) was added dropwise and then stirred at 30 ° C. for 17 hours. Then, 3,5-dibromobenzonitrile (522 mg) was further added, and the mixture was heated to reflux for 5 hours. The reaction mixture was allowed to cool to room temperature and then water and methanol were added. The precipitated solid is washed with water, washed with methanol, and further washed with hexane to give the desired 2- (3,5-dibromophenyl) -4-phenyl- [1] benzothieno [3,2-d] pyrimidine. A white solid of (B-9) (yield 1.36 g, 69%) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.64-7. 70 (m, 4 H), 7.73 (dd, J = 8.0, 7.1 Hz, 1 H), 7.82 (s) , 1H), 7.96 (d, J = 8.0 Hz, 1 H), 8.36 (d, J = 8.1 Hz, 2 H), 8.73 (d. J = 7.9 Hz, 1 H), 8 .87 (s, 2H).
Example 15

Compound B-9 (496 mg), 9-phenanthreneboronic acid (533 mg), and tetrakis (triphenylphosphine) palladium (23.1 mg) were added to THF (20 mL) under an argon stream, and a 3 M aqueous potassium carbonate solution was added thereto. (1.6 mL) was added and then heated to reflux for 19 hours. The reaction mixture was allowed to cool to room temperature and then water and methanol were added. The precipitated solid is washed with water, washed with methanol, and further washed with hexane to obtain the desired 2- [3,5-di (9-phenanthryl) phenyl] -4-phenyl- [1] benzothieno [3,2]. A brown solid (yield 647 g, 94%) of -d] pyrimidine (C-10) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.54-7.75 (m, 13 H), 7.92 (s, 1 H), 7.95 (d, J = 8.0 Hz, 1 H), 7.99 (s, 2 H), 8.00 (d, J = 8.0 Hz, 2 H), 8.23 (d, J = 8.0 Hz, 2 H), 8. 38 (d, J = 7.9 Hz , 2H), 8.70 (d, J = 7.7 Hz, 1 H), 8.79 (d, J = 8.3 Hz, 2 H), 8.85 (d, J = 8.0 Hz, 2 H), 9 .07 (s, 2H).
Example 16

Compound B-1 (2.45 g), phenylboronic acid (727 mg), and bis (triphenylphosphine) palladium dichloride (38.0 mg) were added to THF (22 mL) under an argon stream, and 3 M aqueous potassium carbonate solution ( 4.0 mL) was added and then heated to reflux for 24 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- [5-chlorobiphenyl-3-yl] -4-phenyl- [1] benzothieno [3,2-d]. A brown powder of pyrimidine (B-10) (yield 2.33 g, 96%) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.45 (t, J = 7.4 Hz, 1 H), 7.54 (t, J = 7.5 Hz, 2 H), 7.61-7. 77 (m, 8 H), 7.96 (d, J = 8.0 Hz, 1 H), 8. 38 (d, J = 8.1 Hz, 2 H), 8.74-8.76 (m, 2 H), 8.90 (s, 1 H).
Compound B-10 (2.30 g), bispinacolato diboron (1.43 g), tris (dibenzylideneacetone) dipalladium (141 mg), 2-dicyclohexylphosphino-2 ′, 4 ′, 6 in an argon stream. '-Triisopropylbiphenyl (220 mg) and potassium acetate (1.11 g) were added to 1,4-dioxane (25.6 mL) and heated to reflux for 19 hours. The reaction mixture was allowed to cool, and then the insolubles were filtered. The filtrate is purified by silica gel column chromatography (developing solvent; chloroform) to obtain the desired 2- [5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -biphenyl White powder (yield 2.25 g, yield 81%) of -3-yl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (B-11) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 1.45 (s, 12 H), 7.42 (t, J = 7.4 Hz, 1 H), 7.53 (t, J = 7.4 Hz, 2H), 7.61-7. 70 (m, 4H), 7.72 (dd, J = 7.9, 7.1 Hz, 1 H), 7.83 (d, J = 8.2 Hz, 2 H), 7.97 (d, J = 7.9 Hz, 1 H), 8.23 (s, 1 H), 8.41 (d, J = 8.2 Hz, 2 H), 8.83 (d, J = 7.8 Hz , 1 H), 9.13 (s, 1 H), 9. 16 (s, 1 H).
Compound B-11 (1.20 g), 3-bromo-6,9-di (2-pyridyl) carbazole (978 mg), bis (triphenylphosphine) palladium dichloride (31.2 mg) in THF (22 mL) in an argon stream ) And 3M aqueous potassium carbonate solution (1.5 mL) was further added, and then heated to reflux for 22 hours. The reaction mixture was allowed to cool to room temperature and water was added. The organic layer was extracted, the solvent was distilled off under reduced pressure, and then methanol was added to precipitate a white-brown solid. The white-brown solid is collected by filtration to give the desired 2- [5- [6,9-di (2-pyridyl) carbazol-3-yl] biphenyl-3-yl] -4-phenyl- [1] benzothieno. A brown powder (yield 1.14 g, 70%) of [3,2-d] pyrimidine (C-11) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.26 (dd, J = 7.4, 4.9 Hz, 1 H), 7.39 (dd, J = 7.4, 4.9 Hz, 1 H) ), 7.47 (t, J = 7.4 Hz, 1 H), 7.56-7.74 (m, 7 H), 7.76 (d, J = 8.1 Hz, 1 H), 7.82 (d , J = 7.5 Hz, 1 H), 7.90-8.04 (m, 8 H), 8.12 (s, 1 H), 8. 18 (d, J = 8.7 Hz, 1 H), 8.43 (D, J = 8.2 Hz, 2 H), 8.65 (s, 1 H), 8. 76 (d, J = 4.9 Hz, 1 H), 8.80-8.83 (m, 2 H), 8 93 (s, 1 H), 9.03 (s, 1 H), 9. 13 (s, 1 H).
Example 17

Compound B-2 (1.00 g), 3-pyridylboronic acid (291 mg), palladium acetate (8.2 mg), and 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl under an argon stream (34.7 mg) was added to THF (18 mL), and further 3 M aqueous potassium carbonate solution (2.4 mL) was added, and then heated to reflux for 24 hours. Then palladium acetate (8.2 mg) and 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (34.7 mg) in THF (5 mL) are added to the reaction mixture, then for 24 hours Heated to reflux. The reaction mixture was allowed to cool to room temperature and water was added. After THF was distilled off under reduced pressure, methanol was added to precipitate a white-brown solid. By filtering this white-brown solid, the desired 2- [5- (9-phenanthryl) -3- (3-pyridyl) phenyl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine is obtained. A white-brown powder (yield 1.08 g, 100%) of (C-12) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.47 (t, J = 7.9, 4.8 Hz, 1 H), 7.58-7.76 (m, 9 H), 7. 91 ( s, 1 H), 7.93 (s, 1 H), 7.96 (d, J = 8.0 Hz, 1 H), 7.99 (d, J = 7.9 Hz, 1 H), 8.07 (d, J = 8.3 Hz, 1 H), 8. 15 (d, J = 7.9 Hz, 1 H), 8. 38 (d, J = 8.1 Hz, 2 H), 8.68 (d, J = 4.8 Hz) , 1H), 8.73 (d, J = 7.9 Hz, 1 H), 8.80 (d, J = 8.1 Hz, 1 H), 8.85 (d, J = 8.2 Hz, 1 H), 9 .02 (s, 1 H), 9. 13 (s, 1 H), 9. 14 (s, 1 H).
Example 18

Compound B-1 (500 mg), 4-diphenylboronic acid (482 mg), palladium acetate (5.0 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (21. 0 mg) was suspended in a mixed solvent of toluene (30.0 mL) and 1-butanol (7 mL), 3M aqueous potassium carbonate solution (0.74 mL) was further added, and the mixture was heated and stirred at 100 ° C. for 21 hours. The reaction mixture was allowed to cool, methanol was added, and the precipitated solid was collected by filtration. The obtained solid is washed with water, methanol and hexane, and recrystallized with a mixed solvent of 180 mL of toluene and 80 mL of methanol to obtain the desired 4-phenyl-2- (1,1 ′: 4 ′, 1 ′ ′: 3 ′ ′, 1 ′ ′ ′: 4 ′ ′ ′, 1 ′ ′ ′ ′-Queenquephenyl-5 ′ ′-yl)-[1] benzothieno [3,2-d] pyrimidine (C-13) White A powder (yield 706 mg, 99% yield) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.39 (t, J = 7.6 Hz, 2 H), 7.50 (t, J = 7.7 Hz, 4 H), 7.61-7.74 (M, 9 H), 7.78 (d, J = 8.3 Hz, 4 H), 7.93 (d, J = 8.3 Hz, 4 H), 7.96 (d, J = 8.0 Hz, 1 H) , 8.06 (s, 1 H), 8.41 (d, J = 6.8 Hz, 2 H), 8.79 (d, J = 8.0 Hz, 1 H), 9.06 (d, J = 1. 5 Hz, 2 H).
Example 19

Compound B-1 (500 mg), 9-anthraceneboronic acid (270 mg), palladium acetate (5.0 mg), and 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (21. 0 mg) was suspended in 1,4-dioxane (11.0 mL), 3M aqueous potassium carbonate solution (0.74 mL) was further added, and the mixture was heated and stirred at 80 ° C. for 16 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The obtained solid is washed with water, methanol and hexane, and further recrystallized with 38 mL of toluene to obtain the desired 2- [3- (9-anthracyl) -5-chlorophenyl] -4-phenyl- [1] benzothieno. A white powder (yield 584 mg, 96%) of [3,2-d] pyrimidine (B-12) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.40 (t, J = 7.8 Hz, 2H), 7.50 (t, J = 7.0 Hz, 2H), 5.53-7.61 (M, 5 H), 7.67 (t, J = 7.2 Hz, 1 H), 7. 76 (d, J = 9.2 Hz, 2 H), 7. 91 (d, J = 8.5 Hz, 1 H) , 8.08 (d, J = 8.3 Hz, 2 H), 8.32 (d, J = 8.2 Hz, 2 H), 8.56 (s, 1 H), 8.64 (d, J = 7. 6). 8 Hz, 1 H), 8.76 (s, 1 H), 8.95 (s, 1 H).
Compound B-12 (536 mg), 4- (2-pyridyl) phenylboronic acid (233 mg), palladium acetate (4.4 mg) and 2-dicyclohexylphosphino-2 ', 4', 6'-tri under argon flow Isopropyl biphenyl (18.6 mg) was suspended in 1,4-dioxane (10.0 mL), 3M aqueous potassium carbonate solution (0.65 mL) was added, and the mixture was heated and stirred at 80 ° C. for 16 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The obtained solid is washed with water, methanol and hexane, and further recrystallized with a mixed solvent of 180 mL of toluene and 80 mL of methanol to obtain the desired 2- [5- (9-anthracyl) -4 ′-(2-pyridyl) A white powder (yield 578 mg, 89%) of (biphenyl-3-yl) -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (C-14) was obtained.

¹ H-NMR (DMSO-d ₆ ) δ (ppm): 7.39 (dd, J = 7.9 Hz, 4.5 Hz, 1 H), 7. 50 (t, J = 7.6 Hz, 2 H), 7 .59 (t, J = 7.0 Hz, 2 H), 7.63-7.72 (m, 4 H), 7. 76 (d, J = 8.5 Hz, 2 H), 7.83 (t, J = 7.2 Hz, 1 H), 7.92 (t, J = 7.9 Hz, 1 H), 8.02 (s, 1 H), 8.06 (d, J = 7.3 Hz, 1 H), 8.08 ( d, J = 8.6 Hz, 2 H), 8.22-8.33 (m, 7 H), 8. 68-8.72 (m, 3 H), 8. 80 (s, 1 H), 9. 28 ( s, 1 H).
Example 20

Compound B-3 (450 mg), 4-diphenylboronic acid (203 mg), palladium acetate (3.8 mg) and 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (16. under a stream of argon). 3 mg) was suspended in a mixed solvent of toluene (23.0 mL) and 1-butanol (5 mL), 3 M aqueous potassium carbonate solution (0.57 mL) was further added, and the mixture was heated and stirred at 100 ° C. for 16 hours. The reaction mixture was allowed to cool, methanol was added, and the precipitated solid was collected by filtration. The obtained solid is washed with water, methanol and hexane, and further recrystallized with a mixed solvent of 80 mL of toluene and 100 mL of methanol to obtain the desired 4-phenyl-2- [4- (2-pyridyl) -1, 1 ′: 3 ′, 1 ′ ′: 4 ′ ′, 1 ′ ′ ′-quaterphenyl-5′-yl]-[1] benzothieno [3,2-d] pyrimidine (C-15) as a white powder ( A yield of 398 mg (72% yield) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.26-7.29 (m, 1 H), 7.40 (t, J = 7.0 Hz, 1 H), 7.49 (t, J = 7) .8 Hz, 2 H), 7.61-7. 74 (m, 7 H), 8. 78-7. 86 (m, 4 H), 7. 93 (d, J = 8.2 Hz, 2 H), 7.96 (D, J = 8.2 Hz, 3 H), 8.07 (s, 1 H), 8. 19 (d, J = 8.2 Hz, 2 H), 8.41 (d, J = 8.1 Hz, 2 H) , 8.75 (d, J = 4.7 Hz, 1 H), 8.79 (d, J = 7.3 Hz, 1 H), 9.07 (s, 2 H).
Example 21

Compound B-3 (470 mg), bispinacolato diboron (295 mg), tris (dibenzylideneacetone) dipalladium (16.0 mg), 2-dicyclohexylphosphino-2 ', 4', 6'- under an argon stream. Triisopropylbiphenyl (17.0 mg) and potassium acetate (175 mg) were suspended in 1,4-dioxane (30.0 mL), and heated and stirred at 80 ° C. for 16 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The resulting solid is purified by silica gel chromatography (developing solvent: chloroform) to obtain the desired 2- [5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -4 '-(2-Pyridyl) biphenyl-3-yl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (B-13) as a white powder (yield 241 mg, 44%) Obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.44 (s, 12 H), 7.60-7.68 (m, 5 H), 7.71 (t, J = 7.2 Hz, 1 H), 7.78-7.84 (m, 2H), 7.92-7.96 (m, 3H), 8.14 (d, J = 8.3 Hz, 2H), 8.26 (s, 1H), 8.40 (d, J = 7.0 Hz, 2 H), 8.74 (d, J = 5.9 Hz, 1 H), 8.81 (d, J = 7.0 Hz, 1 H), 9. 16 (dd , J = 2.0 Hz, 1.9 Hz, 2 H).
Compound B-13 (240 mg), 5-bromo-2,2'-bipyridine (110 mg), palladium acetate (1.8 mg) and 2-dicyclohexylphosphino-2 ', 4', 6'-tri under argon flow Isopropyl biphenyl (7.4 mg) was suspended in 1,4-dioxane (13.0 mL), 3M aqueous potassium carbonate solution (0.26 mL) was further added, and the mixture was heated and stirred at 100 ° C. for 24 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The obtained solid is washed with water, methanol and hexane and further recrystallized with 15 mL of toluene to obtain the desired 2- [5- (2,2'-bipyridin-5-yl) -4 '-(2-) A white powder (yield 170 mg, 68%) of pyridyl) biphenyl-3-yl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (C-16) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.26 to 7.29 (m, 1 H), 7.35 (t, J = 6.4 Hz, 1 H), 7.62 to 7.74 (m) , 5 H), 7.79-7.89 (m, 3 H), 7.96 (d, J = 8.0 Hz, 3 H), 8.07 (s, 1 H), 8. 20 (d, J = 8) .3 Hz, 2 H), 8.28 (dd, J = 8.0 Hz, 2.0 Hz, 1 H), 8.41 (d, J = 7.3 Hz, 2 H), 8.51 (d, J = 8). 0 Hz, 1 H), 8.58 (d, J = 8.3 Hz, 1 H), 8. 75 (t, J = 4.8 Hz, 2 H), 8.79 (d, J = 8.0 Hz, 1 H), 9.10 (s, 1 H), 9. 14 (s, 1 H), 9. 19 (s, 1 H).
Example 22

Under an argon stream, 4-acetylbiphenyl (2.00 g) and 3-chloro-1,2-benzisothiazole (2.43 g) are added to DMF (4.0 mL), and a solution of potassium tert-butoxide in DMF ( 1.98 g / 20.0 mL) was added dropwise, and then heated and stirred at 100 ° C. for 16 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The resulting solid is washed with water and purified by silica gel chromatography (developing solvent: chloroform) to obtain the desired 3-amino-2- (4-phenylbenzoyl) benzo [b] thiophene (A-3). A yellow powder (yield 1.23 g, 32% yield) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.03 (s, 2 H), 7.38 to 7.43 (m, 2 H), 7.47 to 7.54 (m, 3 H), 7. 66 (d, J = 7.4 Hz, 2 H), 7. 70-7. 76 (m, 4 H), 7.99 (d, J = 8.2 Hz, 2 H).
Compound A-3 (1.23 g), 3-bromo-5-chlorobenzonitrile (889 mg) and sodium sulfate (1.59 g) were added to THF (3.0 mL) under an argon stream, and potassium tert-butoxide was added thereto. The THF solution (461 mg / 16.0 mL) of H 2 O was added dropwise, and then heated and stirred at 30 ° C. for 16 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The resulting solid is washed with methanol to give the desired 2- (3-bromo-5-chlorophenyl) -4- (4-biphenyl)-[1] benzothieno [3,2-d] pyrimidine (B-14) A pale yellow powder (yield 1.13 g, 57%) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.43 (t, J = 7.4 Hz, 1 H), 7. 50 (t, J = 7.5 Hz, 2 H), 7.64-7.66 (M, 2H), 7.72 (d, J = 7.7 Hz, 2 H), 7.73 (t, J = 8.1 Hz, 1 H), 7.88 (d, J = 8.5 Hz, 2 H) , 7.97 (d, J = 8.2 Hz, 1 H), 8.45 (d, J = 8.5 Hz, 2 H), 8.73 (s, 1 H), 8.74 (d, J = 8. 2 Hz, 1 H), 8.84 (s, 1 H).
Example 23

Compound B-14 (700 mg), 4- (2-pyridyl) phenylboronic acid (581 mg), palladium acetate (18.0 mg) and 2-dicyclohexylphosphino-2 ', 4', 6'-tri under an argon stream Isopropyl biphenyl (76.0 mg) was suspended in 1,4-dioxane (44.0 mL), 3M aqueous potassium carbonate solution (0.89 mL) was further added, and the mixture was heated and stirred at 100 ° C. for 5 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The obtained solid is washed with water, methanol and hexane, and further recrystallized with 100 mL of toluene to obtain the desired 4- (4-biphenyl) -2- [4,4 ′ ′-di (2-pyridyl)- White powder of 1,1 ': 3', 1 ''-terphenyl-5'-yl]-[1] benzothieno [3,2-d] pyrimidine (C-17) (yield 950 mg, 99%) I got

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.28 (d, J = 7.2 Hz, 2 H), 7.43 (t, J = 7.4 Hz, 1 H), 7.52 (t, J = 7.53 Hz, 2 H), 7. 65 (t, J = 6.9 Hz, 1 H), 7.72 (t, J = 8.5 Hz, 1 H), 7.73 (d, J = 7.5 Hz, 2H), 7.78-7.86 (m, 4H), 7.89 (d, J = 8.5 Hz, 2 H), 7.97 (d, J = 8.4 Hz, 5 H), 8.08 (d s, 1 H), 8. 19 (d, J = 8.4 Hz, 4 H), 8.5 1 (d, J = 8.5 Hz, 2 H) 8. 75 (d, J = 5.0 Hz, 2 H) 8. 79 (d, J = 7.7 Hz, 1 H), 9. 10 (d, J = 1.8 Hz, 2 H).
Example 24

Under an argon stream, 2-acetonaphthalene (2.00 g) and 3-chloro-1,2-benzisothiazole (2.11 g) are added to DMF (4.0 mL), and a solution of potassium tert-butoxide in DMF is added thereto. (1.98 g / 20.0 mL) was added dropwise and then heated and stirred at 100 ° C. for 16 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The resulting solid is washed with water and purified by silica gel chromatography (developing solvent: chloroform) to obtain the desired yellow of 3-amino-2- (2-naphthoyl) benzo [b] thiophene (A-4). A powder (yield 1.51 g, 42%) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.05 (s, 2 H), 7.42 (t, J = 7.6 Hz, 1 H), 7. 50 (t, J = 7.6 Hz, 1 H) ), 7.56-7.61 (m, 2H), 7.72 (d, J = 8.1 Hz, 1 H), 7.76 (d, J = 8.1 Hz, 1 H), 7.91 (d , J = 6.8 Hz, 1 H), 7.95- 7.99 (m, 3 H), 8. 47 (s, 1 H).
Compound A-4 (1.51 g), 3-bromo-5-chlorobenzonitrile (1.19 g) and sodium sulfate (2.12 g) were added to THF (5.0 mL) under an argon stream, and potassium tert was added thereto. -A solution of butoxide in THF (614 mg / 25.0 mL) was added dropwise, and then heated and stirred at 30 ° C for 16 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The obtained solid is washed with methanol, and the desired 2- (3-bromo-5-chlorophenyl) -4- (2-naphthyl)-[1] benzothieno [3,2-d] pyrimidine (B-15) is obtained. A pale yellow powder (yield 1.74 g, 69%) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.62-7.64 (m, 2H), 7.66-7.68 (m, 2H), 7.73 (t, J = 7.6 Hz) , 1 H), 7.97 (d, J = 8.1 Hz, 2 H), 8.08-8.12 (m, 2 H), 8. 46 (dd, J = 8.5 Hz, 2.3 Hz, 1 H) , 8.74-8.76 (m, 2H), 8.82 (s, 1 H), 8.85 (t, J = 1.8 Hz, 1 H).
Example 25

Compound B-15 (500 mg), 4- (2-pyridyl) phenylboronic acid (436 mg), palladium acetate (11.0 mg) and 2-dicyclohexylphosphino-2 ', 4', 6'-tri under an argon stream Isopropyl biphenyl (47.5 mg) was suspended in 1,4-dioxane (33.0 mL), 3M aqueous potassium carbonate solution (0.66 mL) was added, and the mixture was heated and stirred at 100 ° C. for 16 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The obtained solid is washed with water, methanol and hexane and further recrystallized with 100 mL of toluene to obtain the desired 4- (2-naphthyl) -2- [4,4 ′ ′-di (2-pyridyl)- White powder of 1,1 ': 3', 1 ''-terphenyl-5'-yl]-[1] benzothieno [3,2-d] pyrimidine (C-18) (yield: 530 mg, 77%) I got

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.27 (d, J = 7.2 Hz, 2H), 7.61-7.68 (m, 3H), 7.71 (t, J = 7) .9 Hz, 1 H), 7.78-7.86 (m, 4 H), 7.97 (d, J = 8.4 Hz, 6 H), 8.07-8.12 (m, 3 H), 8.19 (D, J = 8.4 Hz, 4 H), 8.54 (dd, J = 8.4 Hz, 2.0 Hz, 1 H), 8. 76 (d, J = 5.1 Hz, 2 H), 8.80 ( d, J = 7.6 Hz, 1 H), 8.88 (s, 1 H), 9. 11 (d, J = 1.5 Hz, 2 H).
Example 26

Under an argon stream, 8-acetylquinoline (1.90 g) and 3-chloro-1,2-benzisothiazole (1.79 g) are added to DMF (6.5 mL), and potassium tert-butoxide (1. A DMF suspension (20.0 mL) of 43 g) was added dropwise and then stirred at 80 ° C. for 17 hours. The reaction mixture was allowed to cool to room temperature and water was added. The precipitated solid is washed with water and then with hexane to obtain a yellow powder (yield 2.00 g, yield of the desired 8-quinolyl- (3-aminobenzo [b] thiophen-2-yl) ketone (A-5). Rate of 62%).

¹ H-NMR (DMSO-d ₆ ), δ (ppm): 7.41 (dd, J = 8.0, 7.1 Hz, 1 H), 7.50 (dd, J = 8.0, 7.1 Hz) , 1H), 7.59 (dd, J = 8.3, 4.2 Hz, 1 H), 7.66 (d, J = 8.0 Hz, 1 H), 7.71 (dd, J = 8.1, 7.1 Hz, 1 H), 7. 80 (d, J = 7.1 Hz, 1 H), 8. 13 (d, J = 8.1 Hz, 1 H), 8. 18 (s, 2 H), 8. 25 ( d, J = 8.0 Hz, 1 H), 8.46 (d, J = 8.3 Hz, 1 H), 8.85 (d, J = 4.2 Hz, 1 H).
Compound A-5 (1.98 g) and 3-bromo-5-chlorobenzonitrile (2.11 g) were added to THF (33 mL) under an argon stream, and potassium tert-butoxide (802 mg) in THF solution (32) was added thereto. .5 mL) was added dropwise and stirred at 30.degree. C. for 27 hours. The reaction mixture was allowed to cool to room temperature and then water and methanol were added. The precipitated solid is washed with water, washed with methanol and further washed with hexane to give the desired 2- (3-bromo-5-chlorophenyl) -4- (8-quinolyl)-[1] benzothieno [3, A light brown powder (yield 1.60 g, 49%) of 2-d] pyrimidine (B-16) was obtained.

¹ H-NMR (CDCl ₃ ), δ (ppm): 7.55 (dd, J = 8.3, 4.2 Hz, 1 H), 7.61-7.70 (m, 3 H), 7.80- 7.84 (m, 2 H), 8. 11 (d, J = 8.2 Hz, 1 H), 8. 15 (d, J = 7.1 Hz, 1 H), 8. 36 (d, J = 8.3 Hz , 1H), 8.71 (s, 1H), 8.76 (d, J = 7.4 Hz, 1 H), 8.82 (s, 1 H), 8.95 (d, J = 5, 2 Hz, 1 H) ).
Example 27

Compound B-16 (1.01 g), 4- (2-pyridyl) phenylboronic acid (876 mg), palladium acetate (9.0 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6 in an argon stream '-Triisopropylbiphenyl (57.2 mg) was suspended in THF (40.0 mL), and 3 M aqueous potassium carbonate solution (2.9 mL) was added, and the mixture was heated to reflux for 60 hours. The reaction mixture was allowed to cool, water and methanol were added, and the precipitated solid was collected by filtration. The resulting solid is washed with water, methanol and hexane, and further recrystallized with toluene to give the desired 2- [4,4′-di (2-pyridyl) -1,1 ′: 3 ′, 1 White powder (yield 1.00 g, 79%) of ''-terphenyl-5'-yl] -4- (8-quinolyl)-[1] benzothieno [3,2-d] pyrimidine (C-19) Got).

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.26 to 7.29 (m, 2H), 7.55 (dd, J = 8.3, 4.2 Hz, 1 H), 7.63 (dd , J = 7.5, 7.2, 1 H), 7.67 (dd, J = 7.5, 7.2, 1 H), 7.78-7.85 (m, 6 H), 7.97 ( d, J = 8.4 Hz, 4 H), 8.08 (s, 1 H), 8.1 1 (d, J = 8.2 Hz, 1 H), 8. 18 (d, J = 8.4 Hz, 4 H), 8.23 (d, J = 7.1 Hz, 1 H), 8.36 (d, J = 8.3 Hz, 1 H), 8.76 (d, J = 4.7 Hz, 2 H), 8.81 (d , J = 7.2 Hz, 1 H), 8.99 (d, J = 4.2 Hz, 1 H), 9.08 (s, 2 H).
Example 28

Compound B-2 (1.50 mg), 4-biphenylboronic acid (650 mg), palladium acetate (12.3 mg), and 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl under argon stream (78.1 mg) was suspended in 1,4-dioxane (55.0 mL), 3M aqueous potassium carbonate solution (1.82 mL) was added, and the mixture was heated and stirred at 90 ° C. for 22 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The resulting solid is washed with water, methanol and hexane, and recrystallized with 30 mL of toluene to give the desired 2- [5- (9-phenanthryl) -1,1 ′: 4 ′, 1 ′ ′-terphenyl. A white powder (yield 1.66 g, 91%) of 3-yl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (C-20) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.38 (t, J = 7.4 Hz, 1 H), 7.46-7.50 (m, 2 H), 7.57-7.74 (m , 11 H), 7.77 (d, J = 8.4 Hz, 2 H), 7, 92-7.99 (m, 6 H), 8. 10 (d, J = 8.3 Hz, 1 H), 8. 38 (D, J = 8.1 Hz, 2 H), 8. 73 (d, J = 7.8 Hz, 1 H), 8. 79 (d, J = 8.2 Hz, 1 H), 8. 84 (d, J = 8.1 Hz, 1 H), 8.95 (s, 1 H), 9. 17 (s, 1 H).
Example 29

Compound B-2 (1.50 g), 4- (3-pyridyl) phenylboronic acid (652 mg), palladium acetate (12.3 mg), and 2-dicyclohexylphosphino-2 ', 4', 6 under an argon stream '-Triisopropylbiphenyl (78.1 mg) was suspended in 1,4-dioxane (55.0 mL), 3M aqueous potassium carbonate solution (1.82 mL) was further added, and the mixture was heated and stirred at 90 ° C for 24 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The obtained solid is washed with water, methanol and hexane, and recrystallized with 50 mL of toluene to obtain the desired 2- [5- (9-phenanthryl) -4 '-(3-pyridyl) biphenyl-3-yl]. A white powder (yield 1.32 g, 73%) of -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (C-21) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.57-7.75 (m, ¹⁰ H), 7.77 (d, J = 8.4 Hz, 2 H), 7.91 (s, 1 H), 7.94-7.98 (m, 3H), 8.02 (d, J = 8.4 Hz, 2 H), 8.07 (d, J = 8.2 Hz, 1 H), 8.33 (d, J = 8.1 Hz, 1 H), 8. 37 (d, J = 8.0 Hz, 2 H), 8. 67 (d, J = 5.2 Hz, 1 H), 8. 72 (d, J = 7.7 Hz, 1H), 8.79 (d, J = 8.3 Hz, 1 H), 8. 85 (s, J = 8.2 Hz, 1 H), 8.99 (s, 1 H), 9.01 (s, 1 H) , 9.16 (s, 1 H).
Example 30

Compound B-2 (10.0 g), bis (binacolato) diboron (5.95 g), tris (dibenzylideneacetone) bispalladium (286 mg), 2-dicyclohexylphosphino-2 ′, 4 ′, 6 in an argon stream '-Triisopropylbiphenyl (297 mg) and potassium acetate (3.06 g) were suspended in 1,4-dioxane (310 mL) and stirred with heating at 80 ° C. for 24 hours. The reaction mixture was allowed to cool, and the solvent was evaporated under reduced pressure. The solid is dispersed in water and collected by filtration, and the obtained solid is washed with water, methanol and hexane to obtain the desired 2- [3- (4,4,5,5-tetramethyl-1,3,2 -Dioxaborolane-2-yl) -5- (9-phenanthryl) phenyl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (B-17) as white powder (yield 11.7 g, yield) 100%).

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.43 (s, 12 H), 7.54-7.71 (m, 9 H), 7.84 (s, 1 H), 7.97-7. 95 (m, 2 H), 7.99 (d, J = 8.3 Hz, 1 H), 8. 15 (s, 1 H), 8. 36 (d, J = 8.1 Hz, 2 H), 8.73 8.77 (m, 2H), 8.81 (d, J = 8.1 Hz, 1 H), 9.03 (s, 1 H), 9.25 (s, 1 H).
Example 31

Compound B-17 (1.75 g), 3-chloro-6-phenylpyridine (622 mg), palladium acetate (12.3 mg), and 2-dicyclohexylphosphino-2 ', 4', 6'- under an argon stream Triisopropylbiphenyl (78.1 mg) was suspended in 1,4-dioxane (55.0 mL), 3M aqueous potassium carbonate solution (1.82 mL) was added, and the mixture was heated and stirred at 95 ° C. for 24 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The resulting solid is washed with water, methanol and hexane, and recrystallized with 30 mL of toluene to give the desired 2- [3- (9-phenanthryl) -5- (6-phenylpyridin-3-yl) phenyl]. A white powder (yield 1.48 g, 81%) of -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (C-22) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.46 (t, J = 7.3 Hz, 1 H), 7.51-7.74 (m, 11 H), 7.89-7.99 (m) , 5H), 8.07-8.11 (m, 3H), 8.22 (d, J = 8.3 Hz, 1 H), 8.38 (d, J = 8.8 Hz, 2 H), 8.728 d , J = 7.8 Hz, 1 H), 8.79 (d, J = 8.2 Hz, 1 H), 8.85 (d, J = 8.2 Hz, 1 H), 9.01 (s, 1 H), 9 19 (s, 1 H), 9.23 (s, 1 H).
Example 32

Compound B-17 (1.75 g), 5-bromo-2,2′-bipyridine (771 mg), and tetrakis (triphenylphosphino) palladium (63.0 mg) in an argon stream, in 1,4-dioxane The mixture was suspended in 55.0 mL), 3M aqueous potassium carbonate solution (1.82 mL) was further added, and the mixture was heated and stirred at 95 ° C. for 18 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The resulting solid is washed with water, methanol and hexane, and recrystallized with 40 mL of toluene to give the desired 2- [3- (9-phenanthryl) -5- (2,2'-bipyridin-5-yl) White powder (yield 1.33 g, 73%) of phenyl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (C-23) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.33 (dd, J = 7.4, 4.8 Hz, 1 H), 7.57-7.73 (m, 9 H), 7.86 (t , J = 7.7 Hz, 1 H), 7.91 (s, 1 H), 7.93 (d, J = 8.0 Hz, 1 H), 7.96-7.98 (m, 2 H), 8.07 (D, J = 8.2 Hz, 1 H), 8. 27 (d, J = 8.3 Hz, 1 H), 8. 37 (d, J = 8.0 Hz, 2 H), 8. 49 (d, J = 8.0 Hz, 1 H), 8.55 (d, J = 8.3 Hz, 1 H), 8. 70-8. 74 (m, 2 H), 8. 78 (dm J = 8.2 Hz, 1 H), 8. 84 (d, J = 8.1 Hz, 1 H), 9.01 (s, 1 H), 9.19 (s, 1 H), 9.21 (s, 1 H).
Example 33

Compound B-1 (22.6 g), bispinacolate diboron (14.0 g), potassium acetate (10.8 g), and bis (triphenylphosphine) palladium dichloride (702 mg) in an argon stream under 1,4- It was suspended in dioxane (250 mL) and stirred with heating at 100 ° C. for 21 hours. The reaction mixture was allowed to cool, and the solvent was evaporated under reduced pressure. The resulting solid was suspended in chloroform and then filtered. Water was added to the filtrate, and the separated and extracted organic layer was dried over anhydrous magnesium sulfate. The solvent is distilled off under reduced pressure from the obtained organic layer, and the desired 2- [3-chloro-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] is obtained. A white powder (17.5 g, 70% yield) of -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (B-18) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 1.44 (s, 12 H), 7.61 to 7.74 (m, 5 H), 7.94 to 7, 96 (m, 2 H), 8. 38 (d, J = 8.1 Hz, 2 H), 8.79 (d, J = 7.2 Hz, 1 H), 8.87 (s, 1 H), 9.04 (s, 1 H).
Example 34

Compound B-2 (1.50 g), 4-isoquinolylboronic acid (567 mg), palladium acetate (12.3 mg), and 2-dicyclohexylphosphino-2 ', 4', 6'-tri under argon flow Isopropyl biphenyl (78.1 mg) was suspended in 1,4-dioxane (55.0 mL), 3M aqueous potassium carbonate solution (1.8 mL) was further added, and the mixture was heated and stirred at 90 ° C. for 20 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The resulting solid is washed with water, methanol and hexane, and recrystallized with 15 mL of toluene to give the desired 2- [3- (4-isoquinolyl) -5- (9-phenanthryl) phenyl] -4-phenyl. A white powder (yield 1.22 g, 70%) of-[1] benzothieno [3,2-d] pyrimidine (C-24) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.56-7.78 (m, 9 H), 7.83 (s, 1 H), 7.93-8.16 (m, 6 H), 8.33 (d, 5) J = 8.0 Hz, 2 H), 8.42 (d, J = 8.9, 2 H), 8.68 (d, J = 7.5 Hz, 1 H), 8.77-8.79 (m, 2 H) ), 8.85 (d, J = 8.2 Hz, 1 H), 9.03 (s, 1 H), 9.20 (s, 1 H), 9.56 (s, 1 H).
Example 35

Compound B-2 (1.50 g), 8-quinolylboronic acid (567 mg), palladium acetate (12.3 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (argon flow of argon) 78.1 mg) was suspended in 1,4-dioxane (55.0 mL), 3M aqueous potassium carbonate solution (1.82 mL) was further added, and the mixture was heated and stirred at 90 ° C. for 20 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The obtained solid is washed with water, methanol and hexane, and recrystallized with 20 mL of toluene to obtain the desired 2- [3- (9-phenanthryl) -5- (8-quinolyl) phenyl] -4-phenyl. A white powder (yield 1.37 g, 78%) of-[1] benzothieno [3,2-d] pyrimidine (C-25) was obtained.
¹ H-NMR (CDCl ₃ ): δ 7.48 (dd, J = 8.2, 4.1 Hz, 1 H), 7.52 to 7.73 (m, 10 H), 7.90 to 7.94 (m) , 2H), 7.97-8.00 (m, 2H), 8.03 (d, J = 7.2 Hz, 1 H), 8.08 (s, 1 H), 8.29 (d, J = 8) .5 Hz, 1 H), 8.36-8. 38 (m, 3 H), 8. 68 (d, J = 7.5 Hz, 1 H), 8, 77 (d, J = 7.9 Hz, 1 H), 8 82 (d, J = 8.0 Hz, 1 H), 9.03 (s, 1 H), 9.07 (d, J = 4.1 Hz, 1 H), 9.20 (s, 1 H).
Example 36

Compound B-1 (1.81 g), phenylboronic acid (1.17 g), palladium acetate (18.0 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl under argon stream 114 mg) was suspended in THF (40 mL), and 3 M aqueous potassium carbonate solution (6.4 mL) was further added, and the mixture was heated to reflux for 26 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The obtained solid is washed with water, methanol and hexane, and the desired 4-phenyl-2- [1,1 ′: 3 ′, 1 ′ ′-terphenyl-5′-yl]-[1] benzothieno [3] Obtained a gray powder (yield 1.89 g, 96%) of [2-d] pyrimidine (C-26).

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.46 (t, J = 7.4 Hz, 2 H), 7.56 (dd, 8.2, 7.4 Hz, 4 H), 7.60-7 .73 (m, 5 H), 7.85 (d, J = 8.2 Hz, 4 H), 7.96 (d, J = 7.9 Hz, 1 H), 7.98 (s, 1 H), 8.41 (D, J = 8.1 Hz, 2 H), 8.78 (d, J = 7.9 Hz, 1 H), 9.01 (s, 2 H).
Example-37

Compound B-10 (1.23 g), 4- (4,6-diphenylpyridin-2-yl) phenylboronic acid (1.15 g), palladium acetate (12.3 mg), and 2-dicyclohexylphospha under argon stream Fino-2 ', 4', 6'-triisopropylbiphenyl (78.1 mg) is suspended in 1,4-dioxane (55.0 mL), and 3 M aqueous potassium carbonate solution (1.82 mL) is further added, 90 The mixture was heated and stirred at ° C for 7 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The resulting solid is washed with water, methanol and hexane, and recrystallized with 50 mL of toluene to obtain the desired 2- [4- (4,6-diphenylpyridin-2-yl) -1,1 ': 3' , 1 ′ ′-Terphenyl-5′-yl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (C-27) as a white powder (yield 1.75 g, 89% yield) Obtained.
¹ H-NMR (CDCl ₃ ): δ 7.43 to 7.49 (m, 3 H), 7.52 to 7.58 (m, 6 H), 7.62 to 7.69 (m, 4 H), 7. 72 (dd, J = 8.0, 7.1 Hz, 1 H), 7.85 (d, J = 8.2 Hz, 2 H), 7.93 (d, J = 8.4 Hz, 2 H), 7.96 (D, J = 8.0 Hz, 1 H), 7.99 (s, 2 H), 8.00 (d, J = 8.4 Hz, 2 H), 8.03 (s, 1 H), 8. 28 (d , J = 8.5 Hz, 4 H), 8.41 (d, J = 8.2 Hz, 2 H), 8.78 (d, J = 7.3 Hz, 1 H), 9.04 (s, 1 H), 9 .07 (s, 1 H).
Example 38

Compound B-10 (1.23 g), 4- (2,6-diphenylpyridin-4-yl) phenylboronic acid (1.15 g), palladium acetate (12.3 mg), and 2-dicyclohexylphospha under argon stream Fino-2 ', 4', 6'-triisopropylbiphenyl (78.1 mg) is suspended in 1,4-dioxane (55.0 mL), and 3 M aqueous potassium carbonate solution (1.82 mL) is further added, 90 The mixture was heated and stirred at ° C for 7 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The resulting solid is washed with water, methanol and hexane, and recrystallized with 50 mL of toluene to obtain the desired 2- [4- (2,6-diphenylpyridin-4-yl) -1,1 ': 3 White powder of ', 1''-terphenyl-5'-yl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (C-28) (yield 1.86 g, 95%) I got
¹ H-NMR (CDCl ₃ ): δ 7.43 to 7.69 (m, 13 H), 7.71 (dd, J = 8.0, 7.1 Hz, 1 H), 7.80 (d, J = 8) .2 Hz, 2 H), 7.86 (d, J = 8.2 Hz, 2 H), 7.93 (s, 1 H), 7.96 (d, J = 7.9 Hz, 1 H), 7.98-8 .00 (m, 3 H), 8.05 (s, 1 H), 8. 26 (d, J = 8.3 Hz, 2 H), 8. 38-8. 43 (m, 4 H), 8. 79 (d , J = 7.8 Hz, 1 H), 9.03 (s, 1 H), 9.09 (s, 1 H).
Example 39

Compound B-17 (1.75 g), 2-bromopyridine (518 mg), and tetrakis (triphenylphosphino) palladium (63.0 mg) were suspended in 1,4-dioxane (55.0 mL) under an argon stream. It became turbid, and further 3M potassium carbonate aqueous solution (1.82 mL) was added, and it heat-stirred at 95 degreeC for 123 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The obtained solid is washed with water, methanol and hexane, and recrystallized with a mixed solvent of 15 mL of toluene and 20 mL of methanol to obtain the desired 2- [3- (9-phenanthryl) -5- (2-pyridyl) A white powder (yield 974 mg, 60%) of phenyl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (C-29) was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.31 (dd, J = 7.4, 4.8 Hz, 1 H), 7.55-7.73 (m, 9 H), 7.85 (t, J = 7) .7 Hz, 1 H), 7.92-7.96 (m, 3 H), 8.01 (d, J = 8.0 Hz, 1 H), 8.07 (d, J = 8.2 Hz, 1 H), 8 .38 (m, 3H), 8.74 (d, J = 7.6 Hz, 1 H), 8.77-8.80 (m, 2 H), 8.83 (d, J = 7.8 Hz, 1 H) , 9.01 (s, 1 H), 9. 47 (s, 1 H).
Example 40

Under an argon stream, mercaptoacetophenone (1.52 g) and 3-chloro-2-fluorobenzonitrile (15.6 g) were suspended in DMF (15 mL) and stirred at 0 ° C. Subsequently, 4N potassium hydroxide aqueous solution was dripped, Then, it heat-stirred at 50 degreeC for 30 minutes. Thereafter, 30 mL of water is added, and the mixture is allowed to cool, and then the precipitate is separated by filtration to obtain a yellow powder (yield 1 of the desired 3-amino-2-benzoyl-7-chlorobenzo [b] thiophene (A-6). .73 g (yield 60%) were obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.47 (t, J = 7.9 Hz, 1 H), 7.51-7.60 (m, 3 H), 7.68 (dd, J = 7) .9, 0.8 Hz, 1 H), 7.77 (d, J = 8.0 Hz, 2 H), 8. 25 (dd, J = 7.9, 0.8 Hz, 1 H), 8. 35 (s, s, s, 2H).
Compound A-6 (1.50 g), 3,5-dibromobenzonitrile (1.50 g), and potassium phosphate (2.21 g) are suspended in DMF (10.4 mL) under argon atmosphere, Stir for hours. After that, water is added, and the precipitate is separated by filtration to obtain the desired 2- (3,5-dibromophenyl) -6-chloro-4-phenyl [1] benzothieno [3,2-d] pyrimidine (B -19) gray powder (yield 2.33 g, 84% yield) was obtained. )
¹ H-NMR (CDCl ₃ ) δ (ppm): 7.62 (t, J = 7.8 Hz, 1 H), 7.66-7.71 (m, 3 H), 7.73 (d, J = 7) .8 Hz, 1 H), 7.83 (s, 1 H), 8. 35 (d, J = 7.8 Hz, 2 H), 8.63 (d, J = 7.7 Hz, 1 H), 8. 84 (s , 2H).
Example-41

Compound B-19 (1.59 g), 4- (2-pyridyl) phenylboronic acid (1.43 g), and tetrakis (triphenyl phosphino) palladium (69.3 mg) under an argon atmosphere with THF (60 mL) The mixture was further suspended in 3 M aqueous potassium carbonate solution (4.8 mL) and heated to reflux for 24 hours. The reaction mixture was allowed to cool to room temperature and then water and methanol were added. The precipitated solid is purified by column chromatography (developing solvent: chloroform) to give 6-chloro-2- [4,4 ′ ′-bis (2-pyridyl)-[1,1 ′: 3 ′, 1 ′ Yellow powder (yield 1.57 g, 77%) of 6 ']-terphenyl-5'-yl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (B-20), and 6 -Chloro-2- [5-bromo-4 '-(2-pyridyl) biphenyl-3-yl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (B-21) as a yellow powder ( The yield was 0.153 g (8.5%).

¹ H-NMR (CDCl ₃ ) δ (ppm) of compound B-20: 7.29 (dd, J = 7.1, 4.8 Hz, 2H), 7.61-7.74 (m, 5H), 7.82 (dd, J = 7.8, 7.1 Hz, 2 H), 7.86 (d, J = 7.8 Hz, 2 H), 7.97 (d, J = 8.4 Hz, 4 H), 8 .09 (s, 1 H), 8.20 (d, J = 8.4 Hz, 4 H), 8.43 (d, J = 7.9 Hz, 2 H), 8.71 (d, J = 7.8 Hz, 1H), 8.77 (d, J = 4.8 Hz, 2H), 9.07 (s, 2H).
¹ H-NMR (CDCl ₃ ) δ (ppm) of compound B-21: 7.28-7.31 (m, 1H), 7, 63 (t, J = 7.8 Hz, 1H), 7.66 ( m, 3H), 7.73 (d, J = 7.8 Hz, 1 H), 7.80-7.85 (m, 2 H), 7.87 (d, J = 8.4 Hz, 2 H), 7. 96 (s, 1 H), 8. 18 (d, J = 8.4 Hz, 2 H), 8. 40 (d, J = 8.1 Hz, 2 H), 8.68 (d, J = 7.8 Hz, 1 H ), 8.76 (d, = 4.8 Hz, 1 H), 8.92 (s, 1 H), 9.00 (s, 1 H).
Example 42

Compound B-20 (1.57 g), phenylboronic acid (338 mg), palladium acetate (10.4 mg), and 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl (66) under an argon stream .0 mg) was suspended in THF (60 mL), and 3 M aqueous potassium carbonate solution (1.8 mL) was added, and the mixture was heated to reflux for 5 hours. After allowing to cool, water and methanol are added, and the precipitated solid is collected by filtration to obtain the desired 2- [4,4 ′ ′-bis (2-pyridyl)-[1,1 ′: 3 ′, 1 ′ ′ ] -Terphenyl-5'-yl] -4,6-diphenyl- [1] benzothieno [3,2-d] pyrimidine (C-30) as white powder (yield 1.63 g, 98%) The

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.29 (dd, J = 7.1, 4.8 Hz, 2 H), 7.52 (t, J = 7.4 Hz, 1 H), 7.58 −7.67 (m, 5 H), 7.72− 7.80 (m, 4 H), 7.82 (dd, J = 7.9, 7.1 Hz, 2 H), 7.86 (d, J = 7.9 Hz, 2H), 7.99 (d, J = 8.4 Hz, 4H), 8.10 (s, J = 1 H), 8.21 (d, J = 8.4 Hz, 4 H), 8. 39 (d, J = 8.1 Hz, 2 H), 8.78 (d, J = 4.8 Hz, 2 H), 8.81 (d, J = 6.6 Hz, 1 H), 9. 11 (s, 2 H) ).
Example 43

Compound A-1 (1.00 g), 3,4-dichlorobenzonitrile (747 mg), and sodium sulfate (1.68 g) are suspended in tetrahydrofuran (5.0 mL) under argon stream, and tetrahydrofuran (15.0 mL) is further added. After dropwise addition of potassium tert-butoxide (487 mg) dissolved in (iii), the reaction system was heated and stirred at 50 ° C. for 18 hours. After cooling, water and methanol were added, and the precipitated solid was collected by filtration. The resulting solid is washed with water and methanol to give a white powder (yield) of the desired 2- (3,4-dichlorophenyl) -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (B-22) 1.21 g, yield 75%) was obtained.

¹ H-NMR (DMSO-d ₆ ) δ (ppm): 7.59-7.67 (m, 5 H), 7.71 (dd, J = 8.0, 7.2 Hz, 1 H), 7.95 (D, J = 7.9 Hz, 1 H), 8. 35 (d, J = 8.1 Hz, 2 H), 8.62 (d, J = 8.4 Hz, 1 H), 8. 71 (d, J = 7.9 Hz, 1 H), 8.87 (s, 1 H).
Compound B-22 (800 mg), 4- (2-pyridyl) phenylboronic acid (860 mg), palladium acetate (8.8 mg), and 2-dicyclohexylphosphino-2 ', 4', 6'- under an argon stream Triisopropylbiphenyl (56.0 mg) was suspended in 1,4-dioxane (40.0 mL), 3M aqueous potassium carbonate solution (2.6 mL) was added, and the mixture was heated and stirred at 90 ° C. for 23 hours. After allowing to cool, water was added, and the precipitated solid was collected by filtration. The obtained solid is washed with water, methanol and hexane, and recrystallized with 20 mL of toluene to obtain the desired 4-phenyl-2- [4,4 ′ ′-bis (2-pyridyl) -1,1 ′: A white powder (yield 883 mg, 70%) of 2 ′, 1 ′ ′-terphenyl-4′-yl]-[1] benzothieno [3,2-d] pyrimidine (C-31) was obtained.

¹ H-NMR (DMSO-d ₆ ) δ (ppm): 7.19-7.24 (m, 2H), 7.40 (d, J = 8.4 Hz, 2H), 7.47 (d, J = 8.5 Hz, 2H), 7.58-7.75 (m, 10H), 7.91 (d, J = 8.5 Hz, 2H), 7.95 (m, 3H), 8.40 (d) , J = 8.2 Hz, 2 H), 8.67-8. 70 (m, 2 H), 8. 75 (d, J = 7.9 Hz, 1 H), 8.86 (d, J = 8.1 Hz, 1H), 8.91 (s, 1H).
Example 44

Under an argon stream, mercaptoacetophenone (1.82 g) and 3-bromo-6-fluorobenzonitrile (2.4 g) were suspended in DMF (10 mL) and stirred at 0 ° C. After adding 4 N potassium hydroxide aqueous solution (6.0 mL) dropwise to this, it heat-stirred at 65 degreeC for 50 minutes. Next, water is added, and the mixture is allowed to cool, and then the precipitate is separated by filtration to obtain a yellow powder (yield 2.56 g, the desired 3-amino-2-benzoyl-5-bromobenzo [b] thiophene (A-7). Yield 66%).

¹ H-NMR (DMSO-d ₆ ) δ (ppm): 7.49-7.58 (m, 3 H), 7.67 (d, J = 8.6 Hz, 1 H), 7.75 (d, J = 8.1 Hz, 2 H), 7. 80 (d, J = 8.6 Hz, 1 H), 8. 25 (s, 2 H), 8.5 4 (s, 1 H).
Under an argon atmosphere, Compound A-7 (1.67 g), benzonitrile (1.60 g), and potassium phosphate (2.20 g) were suspended in DMF (10 mL), and heated and stirred at 80 ° C. for 18 hours. After that, water and methanol were added and stirred in an ice bath. The precipitated solid is separated by filtration and washed with water and methanol to give a yellow powder (yield) of the desired 8-bromo-2,4-diphenyl [1] benzothieno [3,2-d] pyrimidine (B-23). 459 mg (yield 21%) were obtained.

¹ H-NMR (DMSO-d ₆ ) δ (ppm): 7.53-7.69 (m, 6 H), 7.80 (d, J = 8.5 Hz, 1 H), 7.83 (d, J = 8.5 Hz, 1 H), 8. 38 (d, J = 8.1 Hz, 2 H), 8. 79 (d, J = 8.2 Hz, 2 H), 8.88 (s, 1 H).
Example 45

Compound B-1 (904 mg), carbazole (702 mg), palladium acetate (9.0 mg), potassium carbonate (1.16 g), and 18-crown-6 ether (106 mg) in xylene (20 mL) in an argon stream The suspension was further added, and a 1 M-toluene solution (120 μL) of tri (tert-butyl) phosphine was added, and the mixture was heated to reflux for 5 hours. The reaction mixture is allowed to cool, water and methanol are added, and the precipitated solid is collected by filtration to obtain the desired 2- (3,5-dicarbazolylphenyl) -4-phenyl- [1] benzothieno [3, Gray powder (yield 1.22 g, 91%) of 2-d] pyrimidine (C-32) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.37 (d, J = 7.3 Hz, 4 H), 7. 50 (dd, J = 8.2, 7.3 Hz, 4 H), 7.58 -7.64 (m, 4 H), 7.68 (d, J = 8.2 Hz, 4 H), 7.72 (t, J = 7.2 Hz, 1 H), 7.96-7.98 (m, 2H), 8.22 (d, J = 7.8 Hz, 4 H), 8.37 (d, J = 7.7 Hz, 2 H), 8.66 (d, J = 7.8 Hz, 1 H), 9. 13 (s, 2 H).
Example-46

Compound B-17 (1.75 g), 1-chloroisoquinoline (537 mg), palladium acetate (12.3 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (under argon flow) 78.1 mg) was suspended in 1,4-dioxane (55.0 mL), 3M aqueous potassium carbonate solution (1.82 mL) was further added, and the mixture was heated and stirred at 90 ° C. for 5 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The resulting solid is washed with water, methanol and hexane and then purified by column chromatography (developing solvent: chloroform) to obtain the desired 2- [3- (1-isoquinolyl) -5- (9-phenanthryl) White powder (yield 290 mg, 17%) of phenyl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (C-33) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.52-7.75 (m, 12H), 7.92-7.95 (m, 3H), 7.97 (d, J = 7.8 Hz) , 1H), 8.04 (s, 1H), 8.17 (d, J = 8.2 Hz, 1 H), 8.35-8.37 (m, 3 H), 8.67 (d, J = 7) .5 Hz, 1 H), 8.72 (d, J = 5.8 Hz, 1 H), 8.77 (d, J = 8.0 Hz, 1 H), 8.83 (d, J = 7.9 Hz, 1 H) , 9.10 (s, 1 H), 9.23 (s, 1 H).
Example 47

Compound B-1 (243 mg), 4- (4,6-dimethylpyrimidin-2-yl) phenylboronic acid (400 mg), palladium acetate (2.40 mg), and 2-dicyclohexylphosphino-2 'in an argon stream 1,4 ', 6'-triisopropylbiphenyl (15.0 mg) is suspended in 1,4-dioxane (11.0 mL), 3M aqueous potassium carbonate solution (720 μL) is added, and the mixture is heated and stirred at 70 ° C for 20 hours did. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The obtained solid is washed with water, methanol and hexane, and recrystallized with 10 mL of toluene to obtain the desired 4-phenyl-2- [4,4 ′ ′-bis (4,6-dimethylpyrimidin-2-yl White powder (yield 289 mg, yield 76) of -1,1 ′: 3 ′, 1 ′ ′-terphenyl-5′-yl]-[1] benzothieno [3,2-d] pyrimidine (C-34) %) Got.

¹ H-NMR (CDCl ₃ ) δ (ppm): 2.58 (s, 12 H), 6.96 (s, 2 H), 7.60-7.73 (m, 5 H), 7.95-7. 97 (m, 5 H), 8.09 (s, 1 H), 8.42 (d, J = 8.2 Hz, 2 H), 8.62 (d, J = 8.5 Hz, 4 H), 8.78 ( d, J = 7.7 Hz, 1 H), 9.09 (s, 2 H).
Example-48

Compound B-17 (1.75 g), 2-chloro-4,6-diphenylpyridine (872 mg), palladium acetate (12.3 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6 in an argon stream '-Triisopropylbiphenyl (78.9 mg) was suspended in 1,4-dioxane (55.0 mL), 3M aqueous potassium carbonate solution (1.82 mL) was further added, and the mixture was heated and stirred at 85 ° C. for 16 hours. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The resulting solid is washed with water, methanol and hexane, and recrystallized with 50 mL of toluene to give the desired 2- [3- (9-phenanthryl) -5- (4,6-diphenylpyridin-2-yl) A white powder (yield 1.56 g, 77%) of phenyl] -4-phenyl- [1] benzothieno [3,2-d] pyrimidine (C-35) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.23 to 7.74 (m, 15 H), 7.82 (d, J = 8.2 Hz, 2 H), 7.93 to 7.95 (m) , 2H), 7.98 (s, 1 H), 7.99 (d, J = 7.7 Hz, 1 H), 8.1 1 (d, J = 8.3 Hz, 1 H), 8. 15 (s, 1 H) ), 8.30 (d, J = 8.2 Hz, 2 H), 8.43 (d, J = 8.1 Hz, 2 H), 8.55 (s, 1 H), 8.74 (d, J = 7) .9 Hz, 1 H), 8.79 (d, J = 8.3 Hz, 1 H), 8. 85 (d, J = 8.1 Hz, 1 H), 9.03 (s, 1 H), 9.73 (s) , 1 H).
Example 49

Under an argon stream, 1-acetylnaphthalene (3.57 g) and 3-chloro-1,2-benzisothiazole (3.39 g) are added to DMF (10 mL), and potassium tert-butoxide in DMF is suspended therein. (30 mL) was added dropwise and then stirred at 80 ° C. for 5 hours. The reaction mixture was allowed to cool to room temperature and water and chloroform were added. The organic layer was extracted by liquid separation operation and dried over anhydrous magnesium sulfate. This is purified by column chromatography (developing solvent: hexane / chloroform) to obtain a yellow liquid (yield 3.56 g) of the desired 3-amino-2- (1-naphthoyl) benzo [b] thiophene (A-8). , Yield 59%).

¹ H-NMR (DMSO-d ₆ ), δ (ppm): 7.44 (dd, J = 8.0, 7.1 Hz, 1 H), 7.52-7.64 (m, 4 H), 7. 71-7.75 (m, 2H), 7.93 (d, J = 8.5 Hz, 1 H), 8.04 (d, J = 8.7 Hz, 1 H), 8.09 (d, J = 8 2 Hz, 1 H), 8. 30 (d, J = 8.0 Hz, 1 H), 8. 40 (s, 2 H).
Compound A-8 (3.50 g), 3-bromo-5-chlorobenzonitrile (2.75 g), and potassium phosphate (4.88 g) were added to DMF (23 mL) under an argon stream, and the reaction was allowed to proceed for 17 hours at room temperature. It stirred. Thereafter, 3-bromo-5-chlorobenzonitrile (2.75 g) was further added, and the mixture was heated and stirred at 100 ° C. for 30 minutes. The reaction mixture was allowed to cool to room temperature and then methanol was added. The precipitated solid is washed with water and methanol to give the desired 2- (3-bromo-5-chlorophenyl) -4- (1-naphthyl)-[1] benzothieno [3,2-d] pyrimidine (B- The pale brown powder (yield 1.34 g, 23%) of 24) was obtained.

¹ H-NMR (DMSO-d ₆ ), δ (ppm): 7.54 (dd, J = 8.5, 6.8 Hz, 1 H), 7.61 (dd, J = 8.1, 6.8 Hz) , 1H), 7.66-7.74 (m, 4H), 7.89 (d, J = 7.7 Hz, 1 H), 7.96 (d, J = 7.1 Hz, 1 H), 8.03 (D, J = 8.1 Hz, 1 H), 8.06 (d, J = 8.8 Hz, 1 H), 8.1 1 (d, J = 8.3 Hz, 1 H), 8.69 (s, 1 H) , 8.77-8.81 (m, 2H).
Example 50

Compound B-24 (1.34 g), 4- (2-pyridyl) phenylboronic acid (1.24 g), palladium acetate (12.0 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′ under an argon stream 6,6'-triisopropylbiphenyl (76.3 mg) was suspended in THF (53.0 mL), and 3M aqueous potassium carbonate solution (5.3 mL) was further added, and the mixture was heated to reflux for 22 hours. The reaction mixture is allowed to cool, water and methanol are added, and the precipitated solid is collected by filtration to obtain the desired 2- [4,4 ′ ′-bis (2-pyridyl)-[1,1 ′: 3 ′, 1 ''-Terphenyl-5'-yl] -4- (1-naphthyl)-[1] benzothieno [3,2-d] pyrimidine (C-36) gray powder (yield 1.86 g, 99 %) Got.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.26-7.29 (m, 2H), 7.54 (dd, J = 8.5, 6.9 Hz, 1H), 7.61 (dd) , J = 7.6, 7.4 Hz, 1 H), 7.65-7.73 (m, 3 H), 7.78 (m, 4 H), 7.89 (d, J = 7.0 Hz, 1 H) , 7.95 (d, J = 8.4 Hz, 4 H), 8.03 (d, J = 8.0 Hz, 1 H), 8.04 (d, J = 7.0 Hz, 1 H), 8.10- 8.12 (m, 2 H), 8. 17 (d, J = 8.4 Hz, 4 H), 8. 25 (d, J = 8.5 Hz, 1 H), 8. 76 (d, J = 4.6 z , 2H), 8.84 (d, J = 7.3 Hz, 1 H), 9.07 (s, 2 H).
Example 51

Compound B-17 (1.28 g), 8- (4-chlorophenyl) quinoline (527 mg), palladium acetate (9.0 mg), and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′- under an argon stream Triisopropylbiphenyl (57.2 mg) was suspended in THF (22.0 mL), and 3 M aqueous potassium carbonate solution (1.33 mL) was added, and the mixture was heated to reflux for 17 hours. The reaction mixture was allowed to cool, water and methanol were added, and the precipitated solid was collected by filtration. This is purified by column chromatography (developing solvent: hexane / chloroform) to give the desired 2- [5- (9-phenanthryl) -4 '-(8-quinolyl) biphenyl-3-yl] -4-phenyl. A white powder (yield 98 mg, 14%) of-[1] benzothieno [3,2-d] pyrimidine (C-37) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.45 (dd, J = 8.3, 4.1 Hz, 1 H), 7.49-7.53 (m, 1 H), 7.58-7 .74 (m, 10 H), 7.82-7.87 (m, 1 H), 7.88 (d, J = 8.3 Hz, 2 H), 7.94 (s, 1 H), 7.96-8 .00 (m, 1 H), 7.99 (d, J = 8.3 Hz, 2 H), 8.03 (s, 1 H), 8.13 (d, J = 8.4 Hz, 1 H), 8.24 (D, J = 8.3 Hz, 1 H), 8.32-8.34 (m, 1 H), 8.41 (d, J = 8.1 Hz, 2 H), 8.75 (d, J = 7. 8 Hz, 1 H), 8.79 (d, J = 7.6 Hz, 1 H), 8.85 (d, J = 8.0 Hz, 1 H), 8.95 (s, 1 H), 9.02 (d, J) J = 4.1 Hz, 1 H), 9.2 (S, 1H).
Synthesis example-1

The compound A-7 (1.29 g) was suspended in formamide (16 mL) under an argon atmosphere and stirred at room temperature. Concentrated sulfuric acid was added dropwise thereto, and the mixture was heated and stirred at 180 ° C. for 22 hours. After allowing the reaction to cool, water was added. The precipitate was separated by filtration to obtain a gray powder (yield 1.16 g, 95%) of the desired 8-bromo-4-phenyl- [1] benzothieno [3,2-d] pyrimidine.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.60-7.67 (m, 3H), 7.79-7.84 (m, 2H), 8.24 (d, J = 7.6 Hz) , 2H), 8.76 (s, 1 H), 9.42 (s, 1 H).
Under an argon stream, 8-bromo-4-phenyl- [1] benzothieno [3,2-d] pyrimidine (1.10 g), 5'-m-terphenylboronic acid (972 mg), palladium acetate (14.5 mg) And 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (92.1 mg) are suspended in THF (32 mL), and 3M aqueous potassium carbonate solution (2.4 mL) is further added, 66 Heated to reflux for time. The reaction mixture was allowed to cool, water was added, and the precipitated solid was collected by filtration. The obtained solid is washed with water, methanol and hexane, and the desired 8- [1,1 ′: 3 ′, 1 ′ ′-terphenyl-5′-yl] -4-phenyl- [1] benzothieno [3] A gray powder (yield 1.54 g, 98%) of 2, 2-d] pyrimidine (ETL-3) was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm): 7.44 (t, J = 7.3 Hz, 2 H), 7.53 (dd, J = 7.8, 7.3 Hz, 4 H), 7.60 −7.67 (m, 3 H), 7.77 (d, J = 7.8 Hz, 4 H), 7.87 (s, 1 H), 7.97 (s, 2 H), 8.04 (d, J = 8.4 Hz, 1 H), 8.08 (d, J = 8.4 Hz, 1 H), 8. 28 (d, J = 7.9 Hz, 2 H), 8. 95 (s, 1 H), 9. 45 (S, 1 H).
Synthesis example-2

Under an argon stream, mercaptoacetophenone (3.04 g) and 3-cyano-2-fluoropyridine (2.44 g) were suspended in DMF (20 mL) and stirred at 0 ° C. After adding 4 N potassium hydroxide aqueous solution (10 mL) dropwise to this, it stirred at room temperature for 14 hours. After that, water is added, and the reaction product is allowed to cool, and then the precipitate is separated by filtration to obtain a yellow powder of 3-amino-2-benzoyl-5-thieno [5,4-b] pyridine (yield 2. 92 g (yield 57%) were obtained.

¹ H-NMR (DMSO-d ₆ ): δ 7.51 (dd, J = 8.2, 4.6 Hz, 1 H), 7.53-7.62 (m, 3 H), 7.80 (d, J = 8.0 Hz, 2 H), 8.44 (s, 2 H), 8. 68 (d, J = 8.2 Hz, 1 H), 8. 74 (d, J = 4.6 Hz, 1 H).
Under an argon atmosphere, 3-amino-2-benzoyl-5-thieno [5,4-b] pyridine (2.54 g) and 3 ', 5'-dichloroacetophenone (3.12 g) are suspended in acetic acid (20 mL). It became turbid and stirred at room temperature. Concentrated sulfuric acid was added dropwise thereto, and the mixture was refluxed for 42 hours. After allowing the reaction to cool, water was added. The precipitate is purified by column chromatography (developing solvent: chloroform) to give the desired 2- (3,5-dichlorophenyl) -4-phenylthieno [3,2-b: 5,4-b '] dipyridine A white powder (yield 1.54 g, 38%) was obtained.

¹ H-NMR (CDCl ₃ ) δ 7.48 (s, 1 H), 7.55 (dd, J = 7.9, 4.7 Hz, 1 H), 7.57-7.66 (m, 3 H), 7 .85 (d, J = 8.2 Hz, 2 H), 7.88 (s, 1 H), 8. 15 (s, 2 H), 8. 80 (d, J = 4.7 Hz, 1 H), 8.89 (D, J = 7.9 Hz, 1 H).
In an argon stream, 2- (3,5-dichlorophenyl) -4-phenylthieno [3,2-b: 5,4-b '] dipyridine (1.00 g), phenylboronic acid (718 mg), palladium acetate (27) .6 mg) and 2-di-tert-butylphosphino-2 ', 4', 6'-triisopropylbiphenyl (173 mg) are suspended in 1,4-dioxane (12 mL), and 3M aqueous potassium carbonate solution (4. Add 0 mL) and heat to reflux for 15 h. After allowing the reaction mixture to cool, water was added and the aqueous layer was removed by decantation. The resulting solid is purified by column chromatography (developing solvent: chloroform) to give the desired 2- [1,1 ': 3', 1 ''-terphenyl-5'-yl] -4-phenyl- Gray powder (yield 417 mg, 35%) of thieno [3,2-b: 5,4-b '] dipyridine (ETL-4) was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.45 (t, J = 7.4 Hz, 2 H), 7.51 (dd, J = 7.9, 4.7 Hz, 1 H), 7.52-7.65 (M, 7 H), 7.79 (d, J = 8.2 Hz, 4 H), 7.87 (d, J = 8.2 Hz, 2 H), 7.93 (s, 1 H), 8.02 (s , 1 H), 8.42 (s, 2 H), 8.78 (d, J = 4.7 Hz, 1 H), 8.89 (d, J = 7.9 Hz, 1 H).
Purification Example 1 (Example)
A yellow powder of compound C-1 (1.58 g, purity before sublimation 99.7%) is heated to a vaporization portion temperature of 330 ° C. and a collection portion temperature of 280 ° C. under vacuum conditions of 1.0 × 10 ⁻³ Pa to sublime Purification gave a white powder of compound C-1 (yield 1.20 g, 76%, purity 99.8%).

Purification Example 2 (Example)
The yellow powder (1.68 g, purity 99.7% before sublimation) of compound C-26 is heated to a vaporization unit temperature of 240 ° C. and a collection unit temperature of 220 ° C. under a vacuum of 5.0 × 10 ⁻⁴ Pa for sublimation Purification gave a white powder of compound C-26 (yield 1.53 g, 91%, purity 99.9%).

Comparative purification example 1 (comparative example)
Compound ETL-3 gray powder (1.54 g, purity before sublimation 99.7%) is heated to a vaporization temperature of 240 ° C. and a collection temperature of 220 ° C. under a vacuum of 5.0 × 10 ⁻⁴ Pa for sublimation Purification gave a white powder of compound ETL-3 (yield 1.20 g, 78%, purity 99.4%).

  It was found that the purity of the benzothienopyrimidine compound of the present invention after sublimation was improved and the heat resistance was excellent as compared with Comparative Purification Example-1.

Production and Performance Evaluation of an Organic Electroluminescent Device Comprising the Benzothienopyrimidine 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
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 2 of the present invention was vacuum deposited at a film deposition rate 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 2
An organic electroluminescent device was manufactured in the same manner as in Evaluation Example 1 except that C-2 synthesized in Example 3 was used instead of C-1 in the electron transport layer 6 of Evaluation Example 1. did.

Evaluation Example 3
An organic electroluminescent device was produced in the same manner as in Evaluation Example 1 except that C-3 synthesized in Example 4 was used instead of C-1 in the electron transport layer 6 of Evaluation Example 1. did.

Evaluation Example 4
An organic electroluminescent device was produced in the same manner as in Evaluation Example 1 except that C-4 synthesized in Example 5 was used instead of C-1 in the electron transport layer 6 of Evaluation Example 1. did.

Evaluation Example 5
An organic electroluminescent device was manufactured in the same manner as in Evaluation Example 1 except that C-5 synthesized in Example 6 was used instead of C-1 in the electron transport layer 6 of Evaluation Example 1. did.

Evaluation Example 6
An organic electroluminescent device was manufactured in the same manner as in Evaluation Example 1 except that C-14 synthesized in Example 19 was used instead of C-1 in the electron transport layer 6 of Evaluation Example 1. did.

Evaluation Example 7
An organic electroluminescent device was manufactured in the same manner as in Evaluation Example 1 except that C-15 synthesized in Example 20 was used instead of C-1 in the electron transport layer 6 of Evaluation Example 1. did.

Evaluation Example 8
An organic electroluminescent device was manufactured in the same manner as in Evaluation Example 1 except that C-18 synthesized in Example 25 was used instead of C-1 in the electron transport layer 6 of Evaluation Example 1. did.

Evaluation Example 9
An organic electroluminescent device was manufactured in the same manner as in Evaluation Example 1 except that C-23 synthesized in Example 32 was used instead of C-1 in the electron transport layer 6 of Evaluation Example 1. did.

Reference Example 1
An organic electroluminescent device was manufactured in the same manner as in Evaluation Example 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. did.

A direct current was applied to the organic electroluminescent elements produced in Evaluation Examples 1 to 9 and Reference Example 1, and light emission 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 is reduced by 20% from the initial value is shown as a relative value as 100. The

It was found that the organic electroluminescent device using the benzothienopyrimidine compound of the present invention is superior to the life characteristics and the voltage rise suppression effect as compared to Reference Example 1.

Evaluation Example 10
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 2 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 11
An organic electroluminescent device was produced in the same manner as in Evaluation Example 10, except that C-2 synthesized in Example 3 was used instead of C-1 in the electron transport layer 16 of Evaluation Example 10. did.

Evaluation Example 12
An organic electroluminescent device was produced in the same manner as in Evaluation Example 10, except that C-3 synthesized in Example 4 was used instead of C-1 in the electron transport layer 16 of Evaluation Example 10. did.

Evaluation Example 13
An organic electroluminescent device was produced in the same manner as in Evaluation Example 10, except that C-4 synthesized in Example 5 was used instead of C-1 in the electron transport layer 16 of Evaluation Example 10. did.

Evaluation Example 14
An organic electroluminescent device was produced in the same manner as in Evaluation Example 10, except that C-10 synthesized in Example 15 was used instead of C-1 in the electron transport layer 16 of Evaluation Example 10. did.

Evaluation Example 15
An organic electroluminescent device was produced in the same manner as in Evaluation Example 10, except that C-12 synthesized in Example 17 was used instead of C-1 in the electron transport layer 16 of Evaluation Example 10. did.

Evaluation Example 16
An organic electroluminescent device was produced in the same manner as in Evaluation Example 10, except that C-13 synthesized in Example 18 was used instead of C-1 in the electron transport layer 16 of Evaluation Example 10. did.

Evaluation Example 17
An organic electroluminescent device was produced in the same manner as in Evaluation Example 10 except that C-15 synthesized in Example 20 was used instead of C-1 in the electron transport layer 16 of Evaluation Example 10. did.

Evaluation Example 18
An organic electroluminescent device was manufactured in the same manner as in Evaluation Example 10, except that C-17 synthesized in Example 23 was used instead of C-1 in the electron transport layer 16 of Evaluation Example 10. did.

Evaluation Example 19
An organic electroluminescent device was produced in the same manner as in Evaluation Example 10, except that C-20 synthesized in Example 28 was used instead of C-1 in the electron transport layer 16 of Evaluation Example 10. did.

Evaluation example 20
An organic electroluminescent device was produced in the same manner as in Evaluation Example 10 except that C-21 synthesized in Example 29 was used instead of C-1 in the electron transport layer 16 of Evaluation Example 10. did.

Evaluation example-21
An organic electroluminescent device was produced in the same manner as in Evaluation Example 10, except that C-22 synthesized in Example 31 was used instead of C-1 in the electron transport layer 16 of Evaluation Example 10. did.

Evaluation Example-22
An organic electroluminescent device was produced in the same manner as in Evaluation Example 10, except that C-23 synthesized in Example 32 was used instead of C-1 in the electron transport layer 16 of Evaluation Example 10. did.

Evaluation Example 23
An organic electroluminescent device was produced in the same manner as in Evaluation Example 10, except that C-24 synthesized in Example 34 was used instead of C-1 in the electron transport layer 16 of Evaluation Example 10. did.

Evaluation Example 24
An organic electroluminescent device was produced in the same manner as in Evaluation Example 10, except that C-25 synthesized in Example 35 was used instead of C-1 in the electron transport layer 16 of Evaluation Example 10. did.

Reference Example 2
An organic electroluminescent device was manufactured in the same manner as in Evaluation Example 6 except that ETL-1, which is a known electron transport material, was used instead of C-1 in the electron transport layer 16 of Evaluation Example 6. did.

Reference Example 3
An organic electroluminescent device was manufactured in the same manner as in Evaluation Example 6 except that ETL-2, which is a known electron transport material, was used in place of C-1 in the electron transport layer 16 of Evaluation Example 6. did.

A direct current is applied to the organic electroluminescent elements produced in Evaluation Examples 10 to 24, Reference Example 2 and Reference Example 3, and light emission characteristics are measured using a luminance meter made by TOPCON, LUMINANCE METER (BM-9). Was evaluated. 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, the measured value of reference example 2 (ETL-1) was shown as a relative value when set to 100. The device life (h) of each evaluation example is shown as a relative value with the time (h) when the luminance (cd / m ² ) of the device in Reference Example 2 is reduced by 10% from the initial value as 100.

It was found that the organic electroluminescent device using the benzothienopyrimidine compound of the present invention was remarkably superior in life characteristics as compared with Reference Example 2 and also superior in the voltage rise suppressing effect. It was found that the organic electroluminescent device using the benzothienopyrimidine compound of the present invention is superior in current efficiency to Reference Example-3.

Evaluation Example 25
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-26 / Liq = 50/50 (weight ratio) at a deposition rate of 0.15 nm / sec for C-26 synthesized in Example 36 of the present invention and Liq. 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 Comparative Example 1
An organic electroluminescent device was produced in the same manner as in Evaluation Example 25 except that ETL-3 synthesized in Synthesis Example 1 was used instead of C-26 in the electron transport layer 16 of Evaluation Example 25. did.

Evaluation Comparative Example-2
An organic electroluminescent device was produced in the same manner as in Evaluation Example 25 except that ETL-4 synthesized in Synthesis Example 2 was used instead of C-26 in the electron transport layer 16 of Evaluation Example 25. did.

A direct current is applied to the organic electroluminescent devices manufactured in Evaluation Example 25 and Evaluation Comparative Example 1 and Evaluation Comparative Example 2, and light emission characteristics are measured using a luminance meter manufactured by TOPCON, LUMINANCE METER (BM-9). Was evaluated. The initial voltage (V) and the initial current efficiency (cd / A) at a current density of 5 mA / cm ² were measured. In addition, when the current density was 40 mA / cm ² and the device was continuously lit, the drive voltage rise when the device was driven for 50 hours was measured. The results are shown in the table below. 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 evaluation comparative example 2 (ETL-4) is set to 100.

The organic electroluminescent device using the benzothienopyrimidine compound of the present invention is lower in drive voltage, excellent in current efficiency, and excellent in drive voltage rise suppression effect as compared with Comparative Comparative Examples 1 and 2. I understood.

  The organic electroluminescent device using the benzothienopyrimidine compound of the present invention can be driven for a long time as compared with the organic electroluminescent device using the existing material. The benzothienopyrimidine 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. 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 benzothienopyrimidine compound of the present invention has high solubility, and it is possible to produce not only a vacuum deposition 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 (22)

Benzothienopyrimidine compounds represented by the general formula (1):
During the ceremony
R ^{1 to} R ⁴ each independently represent an aromatic group having 5 to 17 carbon atoms, a hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, An ethoxy group, an alkoxy group having 3 to 10 carbon atoms, a methylthio group, an ethylthio group, or an alkylthio group having 3 to 10 carbon atoms;
Ar ¹ is an aromatic group having 5 to 25 carbon atoms (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, 1 carbon atom A halogenated alkyl group of -3, a halogenated alkoxy group of 1 to 3 carbon atoms, or a diarylamino group of 10 to 36 carbon atoms as a substituent);
Ar ² is an aromatic group having 5 to 56 carbon atoms (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, 1 carbon atom A halogenated alkyl group of -3, a halogenated alkoxy group of 1 to 3 carbon atoms, or a diarylamino group of 10 to 36 carbon atoms as a substituent);
However, those in which Ar ¹ or Ar ² has at least a part of the structures represented by General Formulas (1-1) to (1-3) are excluded:
During the ceremony
R ¹¹ represents a phenyl group, 4- biphenylyl group , 2-triphenylenyl group, 2-dibenzofuranyl group, 4-dibenzofuranyl group, 2-dibenzothienyl group, 4-dibenzothienyl group, 2-dibenzoselenophenyl group, Represents a group selected from the group consisting of 4-dibenzoselenophenyl group, 9-phenylcarbazol-3-yl group;
R ¹² represents a hydrogen atom or a phenyl group. R ^{1 to} R ⁴ each independently represent a phenyl group, 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 The benzothieno pyrimidine compound of Claim 1 which represents the alkoxy group of this, the methylthio group, the ethylthio group, or the C3-C10 alkylthio group . The benzothieno pyrimidine compound of Claim ^{1 to which} R < ¹ > -R < ⁴ > represents a hydrogen atom. The benzothieno pyrimidine compound of Claim 1 or 2 which Ar ² represents the substituent represented by General formula (2)-(9):
In the general formulas (2) to (9),
Ar ³ each independently represents a C 5-25 aromatic group. Ar ¹ represents an aromatic group having 5 to 25 carbon atoms;
5. The benzothienopyrimidine compound according to claim 4, wherein Ar ² represents a substituent represented by the general formula (5), (7) or (9):
Formula (5), (7), in (9), Ar ³ each independently represent an aromatic group of 5 to 25 carbon atoms. Ar ¹ is an aromatic group having 5 to 17 carbon atoms;
The benzothienopyrimidine compound according to claim 5, wherein each Ar ³ independently represents an aromatic group having 5 to 17 carbon atoms. R ^{1 to} R ^{4 each} represent a phenyl group or a hydrogen atom,
7. The benzothienopyrimidine compound according to claim 6, wherein Ar ¹ represents a phenyl group, a biphenylyl group , a quinolyl group, a pyridyl biphenylyl group or a naphthyl group. Benzothienopyrimidine compounds represented by the general formula (1):
In general formula (1),
R ^{1 to} R ^{4 each} represents a hydrogen atom;
Ar ¹ represents a phenyl group, a biphenylyl group or a naphthyl group;
Ar ² represents a substituent represented by the general formula (5):
In general formula (5),
Ar ³ each independently represents an aromatic group having 5 to 17 carbon atoms. Benzothienopyrimidine compounds represented by the general formula (1):
During the ceremony
R ^{1 to} R ^{4 each} 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 group having 3 to 10 carbon atoms, a methylthio group, Represents an ethylthio group or an alkylthio group having 3 to 10 carbon atoms;
Ar ¹ is an aromatic group having 5 to 25 carbon atoms (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, 1 carbon atom A halogenated alkyl group of -3, a halogenated alkoxy group of 1 to 3 carbon atoms, or a diarylamino group of 10 to 36 carbon atoms as a substituent),
Ar ² is an aromatic group having 5 to 56 carbon atoms (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, 1 carbon atom And C.sup.3 halogenated alkyl groups, C.sub.1 -C.sub.3 halogenated alkoxy groups, or C.sub.10-C.sub.36 diarylamino groups may be included as a substituent).
However, those in which Ar ¹ or Ar ² has at least a part of the structures represented by General Formulas (1-1) to (1-3) are excluded:
During the ceremony
R ¹¹ represents a phenyl group, 4- biphenylyl group , 2-triphenylenyl group, 2-dibenzofuranyl group, 4-dibenzofuranyl group, 2-dibenzothienyl group, 4-dibenzothienyl group, 2-dibenzoselenophenyl group, Represents a group selected from the group consisting of 4-dibenzoselenophenyl group, 9-phenylcarbazol-3-yl group;
R ¹² represents a hydrogen atom or a phenyl group. A process for producing a benzothienopyrimidine compound represented by the general formula (1) according to claim 1, wherein
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 general formulas (10) and (11),
Ar ¹¹ is an aromatic group having 5 to 25 carbon atoms (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, 1 carbon atom And at least a part of the halogenated alkyl group of -3, the halogenated alkoxy group of 1 to 3 carbon atoms, or the diarylamino group of 10 to 36 carbon atoms which may have as a substituent;
Ar ¹² and Ar ¹³ each independently represent an aromatic group having 5 to 56 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 Represents at least a part of
X ^{1 to} X ⁴ are each independently
An aromatic group having 5 to 17 carbon atoms, a hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, A leaving group selected from the group consisting of a methylthio group, an ethylthio group, an alkylthio group having 3 to 10 carbon atoms, or a chlorine atom, a bromine atom, a triflate, an iodine atom, and a metal-containing group;
X ^{5 to} X ⁶ and Y are each independently
Hydrogen or a leaving group selected from the group consisting of chlorine, bromine, triflate, iodine and metal-containing groups;
X ⁷ represents a leaving group selected from the group consisting of chlorine atom, bromine atom, triflate, iodine atom, and metal-containing group.
In General Formula (10), at least one of X ^{1 to} X ⁶ is the leaving group.
However, those in which Ar ¹¹ or Ar ¹² at least partially have the structures represented by General Formulas (1-1) to (1-3) are excluded:
During the ceremony
R ¹¹ represents a phenyl group, 4- biphenylyl group , 2-triphenylenyl group, 2-dibenzofuranyl group, 4-dibenzofuranyl group, 2-dibenzothienyl group, 4-dibenzothienyl group, 2-dibenzoselenophenyl group, Represents a group selected from the group consisting of 4-dibenzoselenophenyl group, 9-phenylcarbazol-3-yl group;
R ¹² represents a hydrogen atom or a phenyl group. A process for producing a benzothienopyrimidine compound represented by the general formula (1) according to claim 1, wherein
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 the general formulas (12) to (14),
R ^{1 to} R ⁴ , Ar ¹ and Ar ² are the same as in the general formula (1);
Z represents a leaving group selected from the group consisting of chlorine atom, bromine atom, triflate, iodine atom, and metal-containing group. A process for producing a benzothienopyrimidine compound represented by the general formula (1) according to claim 1, wherein
A method for producing, characterized in that the compounds represented by the general formula (25), the general formula (26) and the general formula (14) are condensed in the presence of a base or an acid:
In the general formulas (14), (25) and (26),
R ^{1 to} R ⁴ , Ar ¹ and Ar ² are the same as in the general formula (1);
Z represents a leaving group selected from the group consisting of chlorine atom, bromine atom, triflate, iodine atom, and metal-containing group. A process for producing a benzothienopyrimidine compound represented by the general formula (1) according to claim 1, wherein
A method for producing, characterized in that the compounds represented by the general formula (22) and the general formula (14) are condensed in the presence of a base or an acid:
In the general formulas (14) and (22), R ^{1 to} R ⁴ , Ar ¹ and Ar ² are the same as the general formula (1). A method for producing a benzothienopyrimidine compound represented by the general formula (10) according to claim 10, wherein
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 the general formulas (15) to (17),
Ar ¹¹ , Ar ¹² and X ^{1 to} X ⁶ are the same as in the general formula (10);
Z represents a leaving group selected from the group consisting of chlorine atom, bromine atom, triflate, iodine atom, and metal-containing group. A method for producing a benzothienopyrimidine compound represented by the general formula (10) according to claim 10, wherein
A method of producing, characterized in that the compounds represented by the general formula (27), the general formula (28) and the general formula (17) are condensed in the presence of a base or an acid:
In the general formulas (17), (27) to (28),
Ar ¹¹ , Ar ¹² and X ^{1 to} X ⁶ are the same as in the general formula (10);
Z represents a leaving group selected from the group consisting of chlorine atom, bromine atom, triflate, iodine atom, and metal-containing group. A method for producing a benzothienopyrimidine compound represented by the general formula (10) according to claim 10, wherein
A process for producing, characterized in that the compounds represented by the general formula (23) and the general formula (17) are condensed in the presence of a base or an acid:
In the general formulas (17) and (23), Ar ¹¹ , Ar ¹² and X ^{1 to} X ⁶ are the same as the general formula (10). A method for producing a benzothienopyrimidine compound represented by the general formula (11) according to claim 10, wherein
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 the general formula (20), Ar ¹² , X ^{1 to} X ⁴ and X ⁶ are the same as the general formula (11). Benzothienopyrimidine compounds represented by the general formula (10):
During the ceremony
Ar ¹¹ is
Aromatic group having 5 to 25 carbon atoms (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, halogen having 1 to 3 carbon atoms (Optionally substituted alkyl group, halogenated alkoxy group having 1 to 3 carbon atoms, or diarylamino group having 10 to 36 carbon atoms as a substituent), or
Represents some of these;
Ar ¹² is
Aromatic group having 5 to 56 carbon atoms (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, halogen having 1 to 3 carbon atoms (Optionally substituted alkyl group, halogenated alkoxy group having 1 to 3 carbon atoms, or diarylamino group having 10 to 36 carbon atoms as a substituent), or
Represents some of these;
X ^{1 to} X ⁴ are each independently
An aromatic group having 5 to 17 carbon atoms, a hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, A methylthio group, an ethylthio group, an alkylthio group having 3 to 10 carbon atoms, or a group selected from the group consisting of a chlorine atom, a bromine atom, a triflate, an iodine atom, and a metal-containing group;
X ⁵ and X ⁶ are each independently
A hydrogen atom, or a group selected from the group consisting of a chlorine atom, a bromine atom, a triflate, an iodine atom, and a metal-containing group;
At least one of X ^{1 to} X ⁶ is a group selected from the group consisting of a chlorine atom, a bromine atom, a triflate, an iodine atom, and a metal-containing group.
However, those in which Ar ¹¹ or Ar ¹² at least partially have the structures represented by General Formulas (1-1) to (1-3) are excluded:
During the ceremony
R ¹¹ represents a phenyl group, 4- biphenylyl group , 2-triphenylenyl group, 2-dibenzofuranyl group, 4-dibenzofuranyl group, 2-dibenzothienyl group, 4-dibenzothienyl group, 2-dibenzoselenophenyl group, Represents a group selected from the group consisting of 4-dibenzoselenophenyl group, 9-phenylcarbazol-3-yl group,
R ¹² represents a hydrogen atom or a phenyl group. Benzothienopyrimidine compounds represented by the general formula (11):
During the ceremony
Ar ¹² is
Aromatic group having 5 to 56 carbon atoms (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, halogen having 1 to 3 carbon atoms (Optionally substituted alkyl group, halogenated alkoxy group having 1 to 3 carbon atoms, or diarylamino group having 10 to 36 carbon atoms as a substituent), or
Represents some of these;
X ^{1 to} X ⁴ are each independently
An aromatic group having 5 to 17 carbon atoms, a hydrogen atom, a deuterium atom, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, A methylthio group, an ethylthio group, an alkylthio group having 3 to 10 carbon atoms, or a group selected from the group consisting of a chlorine atom, a bromine atom, a triflate, an iodine atom, and a metal-containing group;
X ⁶
A hydrogen atom, or a group selected from the group consisting of a chlorine atom, a bromine atom, a triflate, an iodine atom, and a metal-containing group;
X ⁷ represents a group selected from the group consisting of bromine atom, triflate, iodine atom, and metal-containing group;
However, those having at least a part of the structures represented by the general formulas (1-1) to (1-3) are excluded in Ar ¹² :
During the ceremony
R ¹¹ represents a phenyl group, 4- biphenylyl group , 2-triphenylenyl group, 2-dibenzofuranyl group, 4-dibenzofuranyl group, 2-dibenzothienyl group, 4-dibenzothienyl group, 2-dibenzoselenophenyl group, Represents a group selected from the group consisting of 4-dibenzoselenophenyl group, 9-phenylcarbazol-3-yl group,
R ¹² represents a hydrogen atom or a phenyl group.   An organic electroluminescent device comprising the benzothienopyrimidine compound according to any one of claims 1 to 9.   The organic electroluminescent device according to claim 20, comprising the benzothienopyrimidine compound in an electron injection layer, an electron transport layer, or a light emitting layer.   The material for organic electroluminescent elements which comprises the benzothieno pyrimidine compound of any one of Claims 1-9.