JP4479656B2 - Alkynyl group-substituted fused heterocyclic compound, process for producing the same, and organic electroluminescence device using the same - Google Patents

Description

式中、ｎ^１は１〜３の整数を表わし、ｎ^１が１の場合、Ａは水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、アルキルシリル基、又はヘテロ環基を表わし、ｎ^１が２又は３の場合、Ａは２価又は３価のアリール基又はヘテロ環基を表わし、Ｘ及びＹはそれぞれＣＨ又はＮを表わす、
で示されるアルキニル基置換縮合ヘテロ環化合物を含有する有機エレクトロルミネッセンス素子、この素子に使用される前記式（１）で示されるアルキニル基置換縮合ヘテロ環化合物及びその製法に関する。The present invention is useful for a blue light emitting material for an electroluminescent element (organic electroluminescent element), etc. (1):

In the formula, n ¹ represents an integer of ¹ to 3, and when n ¹ is 1, A represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkylsilyl group, or a heterocyclic group, when n ¹ is 2 or 3, A represents a divalent or trivalent aryl group or heterocyclic group, and X and Y represent CH or N, respectively.
The present invention relates to an organic electroluminescence device containing an alkynyl group-substituted fused heterocyclic compound represented by formula (1), an alkynyl group-substituted fused heterocyclic compound represented by the formula (1) used in this device, and a method for producing the same.

  Examples of the alkynyl group-substituted condensed heterocyclic compound represented by the formula (1) and a method for producing the same include, for example, Chemische Berichte (1960, 93, p. 593), 8-acetylquinoline and phosphorus pentachloride. Although the manufacturing method of 8-ethynyl quinoline by making it react is described, the yield was as low as 14%. Also, the Australian Journal of Chemistry (Australian Journal of Chemistry, 1989, 42, p. 279) has 8-phenyl by reacting 8-trifluoromethanesulfonyloxyquinoline with tributylstannylphenylacetylene. Although a method for producing ethynylquinoline is described, the yield was as low as 43%.

  Furthermore, about these compounds, it was not known at all about the use as an organic electroluminescent element material.

  The present invention relates to an organic electroluminescence device containing an alkynyl group-substituted condensed heterocyclic compound represented by the above formula (1) that exhibits strong blue light emission under ultraviolet irradiation, and an alkynyl group substituted fused heterocycle represented by the above formula (1). Provided are novel alkynyl group-substituted fused heterocyclic compounds included in the ring compounds.

  The present invention also provides a method for synthesizing an alkynyl group-substituted fused heterocyclic compound represented by the formula (1), which exhibits strong blue light emission under ultraviolet irradiation and is useful as a material for an organic electroluminescence device, in a high yield. provide.

  As a result of intensive studies, the present inventors have found that an organic electroluminescence device containing an alkynyl group-substituted condensed heterocyclic compound represented by the above formula (1) exhibits bluish white light emission when a voltage is applied, and The present inventors have found that the alkynyl group-substituted condensed heterocyclic compound represented by (1) exhibits strong blue light emission upon irradiation with ultraviolet rays in a chloroform solution, and has been found to be extremely useful as an organic electroluminescence element material, leading to the present invention.

  In addition, the present inventors derived a hydroxy group-substituted condensed heterocyclic compound into a corresponding trifluoromethanesulfonic acid ester (formula (5) shown below), and then reacted with various terminal acetylene compounds using a zerovalent palladium catalyst. By this, it discovered that the alkynyl group substituted condensed heterocyclic compound shown by said Formula (1) can be manufactured with a sufficient yield.

式中、ｎ^１は１〜３の整数を表わし、ｎ^１が１の場合、Ａは水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、アルキルシリル基、又はヘテロ環基を表わし、ｎ^１が２又は３の場合、Ａは２価又は３価のアリール基又はヘテロ環基を表わし、Ｘ及びＹはそれぞれＣＨ又はＮを表わす、
で示されるアルキニル基置換縮合ヘテロ環化合物を含有することを特徴とする有機エレクトロルミネッセンス素子に関するものである。That is, the present invention is as follows.
1st invention is an organic electroluminescent element which has an organic compound thin layer between one pair of electrodes, Comprising: This organic compound layer is following Formula (1):

In the formula, n ¹ represents an integer of ¹ to 3, and when n ¹ is 1, A represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkylsilyl group, or a heterocyclic group, when n ¹ is 2 or 3, A represents a divalent or trivalent aryl group or heterocyclic group, and X and Y represent CH or N, respectively.
The organic electroluminescent element characterized by containing the alkynyl group substituted condensed heterocyclic compound shown by these.

式中、ｎ^１は前記と同義であり、ｎ^１が１の場合、Ｒ^１は、アルキル基、シクロアルキル基、無置換のフェニル基以外のアリール基、アラルキル基、アルキルシリル基、又はヘテロ環基を表わし、ｎ^１が２又は３の場合、Ｒ^１は２価又は３価のアリール基又はヘテロ環基を表わし、Ｘ及びＹは前記と同義である、
で示されるアルキニル基置換縮合ヘテロ環化合物に関するものである。The second invention is the following formula (1 ′):

In the formula, n ¹ is as defined above, and when n ¹ is 1, R ¹ is an alkyl group, a cycloalkyl group, an aryl group other than an unsubstituted phenyl group, an aralkyl group, an alkylsilyl group, or a heterocyclic ring And when n ¹ is 2 or 3, R ¹ represents a divalent or trivalent aryl group or heterocyclic group, and X and Y are as defined above.
It is related with the alkynyl group substituted condensed heterocyclic compound shown by these.

式中、Ｘ及びＹは前記と同義である、
で示されるトリフルオロメタンスルホニルオキシ基置換縮合ヘテロ環化合物と、次式（６）：

式中、Ａ及びｎ^１は前記と同義である、
で示される末端アセチレン化合物とを、塩基性溶媒中で反応させることを特徴とする前記式（１）で示されるアルキニル基置換縮合ヘテロ環化合物の製造法に関するものである。The third invention uses a zerovalent palladium compound as a catalyst, and uses the following formula (5):

In the formula, X and Y are as defined above.
A trifluoromethanesulfonyloxy group-substituted condensed heterocyclic compound represented by the following formula (6):

In the formula, A and n ¹ are as defined above.
The terminal acetylene compound shown by these is made to react in a basic solvent, It is related with the manufacturing method of the alkynyl group substituted condensed heterocyclic compound shown by said Formula (1) characterized by the above-mentioned.

式中、Ｘ及びＹは前記と同義である、
で示されるエチニル基置換縮合ヘテロ環化合物（前記式（１）においてｎ^１が１、Ａが水素原子である化合物）の製造法に関するものである。In a fourth invention, a zero-valent palladium compound is used as a catalyst, and a trifluoromethanesulfonyloxy group-substituted condensed heterocyclic compound represented by the above formula (5) is reacted with an alkylsilylacetylene compound in a basic solvent to produce an alkyl. A silylethynyl group-substituted condensed heterocyclic compound (a compound in which n ¹ is 1 and A is an alkylsilyl group in the above formula (1)), followed by hydrolysis, is represented by the following formula (7):

In the formula, X and Y are as defined above.
In the formula (1), wherein n ¹ is 1 and A is a hydrogen atom.

式中、Ｘ’はハロゲン原子を表し、Ｒはハロゲン原子、ジアルキルアミノ基、アリールオキシ基、アルコキシ基、アルケニル基、アシル基、ニトロ基、シアノ基、アルキル基、シクロアルキル基、又はアリール基を表し、複数のＲは、それぞれ同一でも異なっていてもよく、ｎ^３は１〜５の整数を表す、
で示されるハロゲン化芳香族環化合物とを、触媒として０価パラジウム化合物を用いて、塩基性溶媒中で反応させることにより、前記式（１）において、Ａがアリール基であり、ｎ^１が１である次式（８）：

式中、Ｘ、Ｙ、Ｒ及びｎ^３は前記と同義である、
で示されるフェニルエチニル基置換縮合ヘテロ環化合物の製造法に関するものである。The fifth invention relates to an ethynyl group-substituted fused heterocyclic compound represented by the formula (7) and the following formula (9):

In the formula, X ′ represents a halogen atom, and R represents a halogen atom, a dialkylamino group, an aryloxy group, an alkoxy group, an alkenyl group, an acyl group, a nitro group, a cyano group, an alkyl group, a cycloalkyl group, or an aryl group. A plurality of R may be the same or different, and n ³ represents an integer of 1 to 5,
In the formula (1), A is an aryl group, and n ¹ is 1 by reacting a halogenated aromatic ring compound represented by the formula (1) with a zero-valent palladium compound as a catalyst. The following formula (8):

In the formula, X, Y, R, and n ³ are as defined above.
The present invention relates to a process for producing a phenylethynyl group-substituted condensed heterocyclic compound represented by

1 is a cross-sectional view of an organic EL device in Example 16, in which reference numeral 1 indicates a glass substrate, 2 indicates ITO, 3 indicates a hole injection layer, 4 indicates a light emitting layer, and 5 indicates an electron. An injection layer or a hole block layer, and 6 an Al electrode.

In the alkynyl group-substituted condensed heterocyclic compound (formula (1)) used in the organic electroluminescence device of the first invention, n ¹ represents an integer of ¹ to 3, and when n ¹ is 1, A is hydrogen. Represents an atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkylsilyl group, or a heterocyclic group, and when n ¹ is 2 or 3, A represents a divalent or trivalent aryl group or heterocyclic group. X and Y represent CH or N, respectively.

  Examples of the alkyl group include alkyl groups having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. These substituents include isomers thereof.

  Examples of the cycloalkyl group include cycloalkyl groups having 3 to 7 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

  Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a dimethylnaphthyl group. These substituents include isomers thereof.

  Examples of the aralkyl group include benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, naphthylmethyl group, naphthylethyl group, naphthylpropyl group, naphthylmethyl group, diphenylmethyl group and the like.

  Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tributylsilyl group, a methyldiisopropylsilyl group, a t-butyldimethylsilyl group, and a methyldit-butylsilyl group.

  Examples of the heterocyclic group include quinolyl group, quinazolinyl group, quinoxalinyl group, imidazolyl group, imidazolidinyl group, imidazolinyl group, pyrazolyl group, pyridyl group, piperidyl group and the like.

When n ¹ is 2, A is a divalent aryl group or a divalent heterocyclic group, and when n ¹ is 3, A is a trivalent aryl group or a trivalent heterocyclic group. Examples of these groups include divalent or trivalent aryl groups or heterocyclic groups described above.

  In the above-mentioned substituents exemplified as A, the hydrogen atom bonded to the carbon atom is further a halogen atom, preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a dialkylamino group, preferably dimethylamino A dialkylamino group having 2 to 10 carbon atoms such as a group, a diethylamino group, or a dipropylamino group; an aryloxy group, preferably 6 to 6 carbon atoms such as a phenoxy group, a triloxy group, a xylyloxy group, a naphthoxy group, or a dimethylnaphthoxy group 14 aryloxy groups; alkoxy groups, preferably methoxy groups, ethoxy groups, propoxy groups, butoxy groups, pentanoxy groups, hexanoxy groups, heptanoxy groups, octanoxy groups, nonanoxy groups, decanoxy groups, etc. Group; alkenyl group, preferably vinyl group, propenyl , Butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, etc. Group, acetyl group, propionyl group, butyryl group, valeryl group, pivaloyl group and the like, an aromatic acyl group such as an acyl group or benzoyl group of an aliphatic acid having 1 to 7 carbon atoms; a nitro group, a cyano group, or the above It may be substituted with an alkyl group, a cycloalkyl group, or an aryl group that has the same meaning. These substituents include isomers thereof.

  Specific examples of the alkynyl group-substituted condensed heterocyclic compound (formula (1)) include 8-phenylethynylquinoline, 1,4-bis (8′-quinolylethynyl) benzene, 1,3-bis. (8′-quinolylethynyl) benzene, 1,3,5-tris (8′-quinolylethynyl) benzene, 8-ethynylquinoline, 8- (1′-propynyl) quinoline, 8- (2′-cyclohexylethynyl) ) Quinoline, 8- (3′-phenyl-1′-propynyl) quinoline, 8-trimethylsilylethynylquinoline, bis (8′-quinolyl) acetylene, 8- (4′-fluorophenylethynyl) quinoline, 8- (3 ′ -Fluorophenylethynyl) quinoline, 8- (2′-fluorophenylethynyl) quinoline, 8- (4′-methoxyphenylethynyl) Norin, 8- (3′-methoxyphenylethynyl) quinoline, 8- (4′-phenylphenylethynyl) quinoline, 8- (2′-pyridylethynyl) quinoline, 8- (3′-pyridylethynyl) quinoline, 8- Alkynyl group-substituted quinoline compounds such as (2′-methyl-2′-H-imidazolylethynyl) quinoline and 8- (4′-benzoylphenylethynyl) quinoline, 8-phenylethynylquinazoline, 1,4-bis (8′- Quinazolinylethynyl) benzene, 1,3-bis (8′-quinazolinylethynyl) benzene, 1,3,5-tris (8′-quinazolinylethynyl) benzene, 8-ethynylquinazoline, 8- (1 '-Propynyl) quinazoline, 8- (2'-cyclohexylethynyl) quinazoline, 8- (3'-phenyl-1'-propyl) Pinyl) quinazoline, 8-trimethylsilylethynylquinazoline, bis (8′-quinazolinyl) acetylene, 8- (4′-fluorophenylethynyl) quinazoline, 8- (3′-fluorophenylethynyl) quinazoline, 8- (2′-fluoro) Phenylethynyl) quinazoline, 8- (4′-methoxyphenylethynyl) quinazoline, 8- (3′-methoxyphenylethynyl) quinazoline, 8- (4′-phenylphenylethynyl) quinazoline, 8- (2′-pyridylethynyl) Alkynyl group-substituted quinazoline compounds such as quinazoline, 8- (3′-pyridylethynyl) quinazoline, 8- (2′-methyl-2′-H-imidazolylethynyl) quinazoline, 8- (4′-benzoylphenylethynyl) quinazoline, 8-Phenylethynylquinoxari 1,4-bis (8′-quinoxalinylethynyl) benzene, 1,3-bis (8′-quinoxalinylethynyl) benzene, 1,3,5-tris (8′-quinoxali) Nylethynyl) benzene, 8-ethynylquinoxaline, 8- (1′-propynyl) quinoxaline, 8- (2′-cyclohexylethynyl) quinoxaline, 8- (3′-phenyl-1′-propynyl) quinoxaline, 8-trimethylsilylethynyl Quinoxaline, bis (8′-quinoxalinyl) acetylene, 8- (4′-fluorophenylethynyl) quinoxaline, 8- (3′-fluorophenylethynyl) quinoxaline, 8- (2′-fluorophenylethynyl) quinoxaline, 8- ( 4'-methoxyphenylethynyl) quinoxaline, 8- (3'-methoxyphenylethynyl) Quinoxaline, 8- (4′-phenylphenylethynyl) quinoxaline, 8- (2′-pyridylethynyl) quinoxaline, 8- (3′-pyridylethynyl) quinoxaline, 8- (2′-methyl-2′-H-imidazolyl) And alkynyl group-substituted 8-quinoxaline compounds such as ethynyl) quinoxaline and 8- (4′-benzoylphenylethynyl) quinoxaline.

式中、Ｒ^１は、アルキル基、シクロアルキル基、無置換のフェニル基以外のアリール基、アラルキル基、アルキルシリル基、又はヘテロ環を表わす。

式中、ｎ^２は２〜３の整数を表す。

Among the alkynyl group-substituted condensed heterocyclic compounds represented by the formula (1) of the present invention, alkynyl group-substituted condensed heterocyclic compounds represented by the following formulas (2) to (4) are preferably used in the present invention.

In the formula, R ¹ represents an alkyl group, a cycloalkyl group, an aryl group other than an unsubstituted phenyl group, an aralkyl group, an alkylsilyl group, or a heterocyclic ring.

Wherein, ^{n 2} represents an integer of 2-3.

In the alkynyl group-substituted condensed heterocyclic compound represented by the formula (2), R ¹ represents an alkyl group, a cycloalkyl group, an aryl group other than an unsubstituted phenyl group, an aralkyl group, an alkylsilyl group, or a heterocyclic group. Represent. In addition, the specific aspect of these substituents is the same as that of what was mentioned as A in the said Formula (1).

  Specific examples of the alkynyl group-substituted condensed heterocyclic compound (formula (2)) include 8- (1-propynyl) quinoline, 8- (2-cyclopropylethynyl) quinoline, 8- (4′- Methylphenylethynyl) quinoline, 8-trimethylsilylethynylquinoline, 8- (4′-fluorophenylethynyl) quinoline, 8- (3′-fluorophenylethynyl) quinoline, 8- (2′-fluorophenylethynyl) quinoline, 8- (4′-methoxyphenylethynyl) quinoline, 8- (3′-methoxyphenylethynyl) quinoline, 8- (4′-phenylphenylethynyl) quinoline, 8- (2′-pyridylethynyl) quinoline, 8- (3 ′ -Pyridylethynyl) quinoline, 8- (2'-methyl-2'-H-imidazolylethynyl) quinori 8- (4'-benzoylphenyl ethynyl) quinoline, and the like.

In the alkynyl group-substituted fused heterocyclic compound represented by the formula (3), n ² represents an integer of ² to 3.
Specific examples include 1,4-bis (8′-quinolylethynyl) benzene, 1,3-bis (8′-quinolylethynyl) benzene, 1,3,5-tris (8′-quinolyl). Ethynyl) benzene and the like.

The compound represented by the formula (4) is bis (8′-quinolyl) acetylene in which A is a quinolyl group, X and Y are both CH, and n ¹ is 1 in the formula (1).

  The second invention relates to an alkynyl group-substituted fused heterocyclic compound represented by the formula (1 ') except that in the formula (1), A is a hydrogen atom.

In the formula (1 ′), n ¹ , X and Y are as defined in the formula (1), and when n ¹ is 1, R ¹ is an aryl other than an alkyl group, a cycloalkyl group or an unsubstituted phenyl group. Represents a group, an aralkyl group, an alkylsilyl group, or a heterocyclic group, and when n ¹ is 2 or 3, R ¹ represents a divalent or trivalent aryl group or heterocyclic group. Examples of R ¹ include those having the same meaning as the alkyl group, cycloalkyl group, aryl group other than the unsubstituted phenyl group, aralkyl group, alkylsilyl group, or heterocyclic group described in A of the formula (1). Specific examples of the compound include compounds other than 8-phenylethynylquinoline described in the above formula (1).

  Preferable examples of the alkynyl group-substituted condensed heterocyclic compound represented by the formula (1 ') include compounds represented by the above formulas (2) to (4).

  In the production method of the third invention, a zero-valent palladium compound is used as a catalyst, and a trifluoromethanesulfonyloxy-substituted condensed heterocyclic compound (formula (5)) and a terminal acetylene compound (formula (6)) are made basic. An alkynyl group-substituted condensed heterocyclic compound (formula (1)) is produced by reacting in a solvent.

  Here, the trifluoromethanesulfonyloxy group-substituted condensed heterocyclic compound is synthesized, for example, according to the synthesis method described in Journal of the American Chemical Society, 1987, 109, p. 5478. By reacting trifluoromethanesulfonic anhydride with a hydroxy group-substituted condensed heterocyclic compound corresponding to the desired trifluoromethanesulfonyloxy-substituted condensed heterocyclic compound in a solvent such as methylene chloride in the presence of an organic base such as triethylamine. Manufactured.

  Examples of zero-valent palladium compounds used as catalysts include zero-valent palladium phosphine complexes (palladium tetrakistriphenylphosphine complex, bisdiphenylphosphinoethane palladium complex, bistricyclohexylphosphine palladium complex, etc.), zero-valent palladium olefin complexes (Trisdi). Benzylideneacetone dipalladium complex) and the like. Of these compounds, zero-valent palladium phosphine complexes are preferable, and tetrakis (triphenylphosphine) palladium is more preferable.

  The usage-amount of these zerovalent palladium compounds is 0.1-10 mol% with respect to a trifluoromethanesulfonyloxy group substituted condensed heterocyclic compound, Preferably it is 0.5-5 mol%.

In the terminal acetylene compound represented by the formula (6), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkylsilyl group, or a heterocyclic group, and n ¹ is an integer of ¹ to 3. Represents.
These substituents represented by A have the same meaning as A in the formula (1).

  Specific examples of the terminal acetylene compound (formula (6)) include phenylacetylene, 4-fluorophenylacetylene, 3-fluorophenylacetylene, 2-fluorophenylacetylene, 4-methoxyphenylacetylene, and 3-methoxyphenyl. Ethenyl group-substituted aryl compounds such as acetylene, 4-phenylphenylacetylene, 4-benzoylphenylacetylene, 1,4-diethynylbenzene, 1,3-diethynylbenzene, 1,3,5-triethynylbenzene, 8-ethynyl Quinoline, 8-ethynylquinazoline, 8-ethynylquinoxaline, 2′-pyridylacetylene, 3′-pyridylacetylene, ethynyl group-substituted heterocyclic compounds such as 5-ethynyl-1-methyl-1-H-imidazole, trimethylsilylacetylene, etc. Le Kill silyl acetylene compound 1- propyne, 1-alkyl-substituted acetylene compound of butyne, etc., a cycloalkyl group substituted acetylene compound such as cyclohexyl acetylene, aralkyl group substituted acetylene compound such as 3-phenyl-1-propyne and the like.

  The amount of the terminal acetylene compound (the above formula (6)) used is 1.0 to 2.0 mol, preferably 1 mol relative to 1 mol of the trifluoromethanesulfonyloxy group-substituted condensed heterocyclic compound (the above formula (5)). Is 1.0 to 1.3 mol.

  Examples of the basic solvent used in the production method of the third invention include piperidine and pyrrolidine.

The usage-amount of a basic solvent is 1-20L (liter) with respect to 1 mol of trifluoromethanesulfonyloxy group substituted condensed heterocyclic compounds (Formula (5)), Preferably it is 1.5-5L.
Moreover, reaction temperature is 80-100 degreeC, Preferably it is 80-90 degreeC.
The reaction time varies depending on the kind of the terminal acetylene compound, the amount of solvent used, the reaction temperature, and the like, but is 1 to 5 hours.

  This reaction is usually performed in an inert gas atmosphere such as argon or nitrogen, or in a gas stream of these gases. The reaction pressure used is usually atmospheric pressure.

  After completion of the reaction, the alkynyl group-substituted condensed heterocyclic compound produced according to the above production method is subjected to usual post-treatments such as extraction, concentration, filtration, etc., and distillation, recrystallization, various chromatography, etc. It can be appropriately purified by known means.

  The obtained alkynyl group-substituted fused heterocyclic compound is suitably used for an organic electroluminescence device.

The ethynyl group-substituted condensed heterocyclic compound represented by the following formula (7) in which A is a hydrogen atom and n ¹ is 1 in the above formula (1) is produced by the following production method separately from the above production method. Can do.

式中、Ｘ及びＹは前記と同義である、
を製造することができる。That is, according to the fourth aspect of the present invention, a trifluoromethanesulfonyloxy group-substituted condensed heterocyclic compound (formula (5)) and a terminal acetylene compound (above-mentioned) are used in a basic solvent using a zero-valent palladium compound as a catalyst according to the above production method. After reacting with the above alkylsilylacetylene compound as the formula (6) to form an alkylsilylethynyl group-substituted condensed heterocyclic compound, the alkylsilylethynyl group-substituted condensed heterocyclic compound is hydrolyzed to replace the ethynyl group. Fused heterocyclic compound (following formula (7)):

In the formula, X and Y are as defined above.
Can be manufactured.

For this hydrolysis, for example, an aqueous solution of an alkali metal hydroxide is used.
Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide.

  In the aqueous solution of the alkali metal hydroxide, the concentration of the alkali metal hydroxide is 0.1 to 12.5 mol / L, preferably 0.5 to 5 mol / L. Moreover, the usage-amount is 1-5 mol with respect to 1 mol of alkyl silyl ethynyl group substituted condensed heterocyclic compounds, Preferably it is 1-2 mol.

  The temperature used in this hydrolysis is 5 to 50 ° C, preferably 15 to 25 ° C. Moreover, although reaction time changes with the said density | concentration and temperature, it is 0.1 to 2 hours.

  This hydrolysis is usually performed in an inert gas atmosphere such as argon or nitrogen, or in a gas stream of these gases. The reaction pressure used is usually atmospheric pressure.

  The ethynyl group-substituted condensed heterocyclic compound (formula (7)) produced according to the above production method is subjected to usual post-treatments such as extraction, concentration and filtration after the completion of the reaction, followed by distillation and recrystallization as necessary. It can be appropriately purified by known means such as various chromatographies.

  In the method for producing the alkynyl group-substituted condensed heterocyclic compound of the fourth invention, a purified ethynyl group-substituted condensed heterocyclic compound (formula (7)) can be used as the terminal acetylene compound. After the production of the condensed heterocyclic compound (formula (7)), a crude product obtained only by the above-described post-treatment such as filtration and concentration can be used as it is.

式中、Ｒはハロゲン原子、ジアルキルアミノ基、アリールオキシ基、アルコキシ基、アルケニル基、アシル基、ニトロ基、シアノ基、アルキル基、シクロアルキル基、又はアリール基を表し、複数のＲは、それぞれ同一でも異なっていてもよく、ｎ^３は１〜５の整数を表し、Ｘ及びＹは前記と同義である、
で示されるフェニルエチニル基置換縮合ヘテロ環化合物も、上記の製法とは別に下記の製法で製造することができる。In the formula (1), A is an aryl group, and n ¹ is 1, the following formula (8):

In the formula, R represents a halogen atom, a dialkylamino group, an aryloxy group, an alkoxy group, an alkenyl group, an acyl group, a nitro group, a cyano group, an alkyl group, a cycloalkyl group, or an aryl group. They may be the same or different, n ³ represents an integer of 1 to 5, and X and Y are as defined above.
The phenylethynyl group-substituted condensed heterocyclic compound represented by the above can also be produced by the following production method separately from the above production method.

式中、Ｘ’はハロゲン原子を表し、Ｒ及びｎ^３は前記と同義である、
で示されるハロゲン化芳香族環化合物とを、触媒として０価パラジウム化合物を用いて、塩基性溶媒中で反応させることによりフェニルエチニル基置換縮合ヘテロ環化合物（前記式（８））を製造することができる。That is, the fifth invention relates to an ethynyl group-substituted condensed heterocyclic compound represented by the above formula (7) and the following formula (9):

In the formula, X ′ represents a halogen atom, and R and n ³ are as defined above.
A phenylethynyl group-substituted condensed heterocyclic compound (formula (8)) is reacted with a halogenated aromatic ring compound represented by the formula (8) using a zerovalent palladium compound as a catalyst in a basic solvent. Can do.

  Here, the ethynyl group-substituted condensed heterocyclic compound (formula (7)) is produced according to any one of the above production methods.

In the halogenated aromatic ring compound represented by the formula (9), R is a halogen atom, dialkylamino group, aryloxy group, alkoxy group, alkenyl group, acyl group, nitro group, cyano group, alkyl group, cycloalkyl group. Or an aryl group, and the plurality of R may be the same or different, and n ³ is an integer of 1 to 5.

Examples of the zero-valent palladium compound used as the catalyst include the aforementioned zero-valent palladium compounds.
The amount of these zerovalent palladium compounds used is 0.1 to 10 mol%, preferably 0.5 to 5 mol%, based on the halogenated aromatic ring compound (formula (9)).

  Examples of the basic solvent used in this reaction include piperidine or pyrrolidine.

The usage-amount of a basic solvent is 1-20L (liter) with respect to 1 mol of ethynyl group substituted condensed heterocyclic compounds (Formula (7)), Preferably it is 1.5-5L.
Moreover, reaction temperature is 80-100 degreeC, Preferably it is 80-90 degreeC.
While the reaction time varies depending on the kind of the halogenated aromatic ring compound (formula (9)), the amount of solvent used, the reaction temperature, etc., it is 1 to 5 hours.
This reaction is usually performed in an inert gas atmosphere such as argon or nitrogen, or in a gas stream of these gases. The reaction pressure used is usually atmospheric pressure.

  The phenylethynyl group-substituted condensed heterocyclic compound (formula (9)) produced according to the above production method is subjected to usual post-treatments such as extraction, concentration, filtration, etc. after completion of the reaction, and if necessary, distillation, It can be appropriately purified by known means such as recrystallization and various chromatography.

  The obtained phenylethynyl group-substituted condensed heterocyclic compound (formula (9)) is suitably used for an organic electroluminescence device.

  Hereinafter, the embodiment is shown about the organic electroluminescent element which is 1st invention.

  An organic electroluminescent element of a first invention is an organic electroluminescent element having an organic compound layer between a pair of electrodes, wherein the organic compound layer is an alkynyl group-substituted condensed heterocyclic compound represented by the formula (1). Among them, it contains at least one kind. Here, the organic compound layer is preferably a light emitting layer, an electron injection layer (or a hole block layer), or a hole transport layer.

  Further, this organic electroluminescence element is an element in which a single layer or a multilayer organic compound layer is formed between an anode and a cathode.

  A single layer type organic electroluminescent element has a light emitting layer between an anode and a cathode. The light emitting layer contains a light emitting material, and further contains a hole injecting material or an electron injecting material (or hole blocking material) for transporting holes injected from the anode or electrons injected from the cathode to the light emitting material. May be.

  Multi-layer type organic electroluminescence devices include, for example, (anode / hole injection layer / light emitting layer / cathode), (anode / light emitting layer / electron injection layer (or hole block layer) / cathode), (anode / hole injection). And a multilayer structure such as layer / light emitting layer / electron injection layer (or hole block layer) / cathode).

  In addition to the alkynyl group-substituted condensed heterocyclic compound (formula (1)), the light-emitting layer includes a known light-emitting material, doping material, hole injection material (phthalocyanine derivative, naphthalocyanine derivative, porphyrin derivative, oxazole, oxadi Azole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acylhydrazone, polyarylalkane, stilbene, butadiene, benzidine type triphenylamine, styrylamine type triphenylamine, Diamine-type triphenylamine and the like, derivatives thereof, and polymer materials such as polyvinyl carbazole, polysilane, and conductive polymers) and electron injection materials (or hole block materials) ( Luolenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone and their derivatives) May be.

  The alkynyl group-substituted fused heterocyclic compound (formula (1)) has a concentration of 0.5 to 100 wt. % Is added.

  This organic electroluminescent element can also be used in combination with a light emitting material, other doping materials, a hole injection material or an electron injection material (or hole block material). Furthermore, each of the hole injection layer, the light emitting layer, and the electron injection layer (or hole block layer) may be formed of two or more layers. In that case, in the case of a hole injection layer, the layer that injects holes from the electrode is a hole injection layer, and the layer that receives holes from the hole injection layer and transports holes to the light emitting layer is a hole transport layer. Call. Similarly, in the case of an electron injection layer, the layer that injects electrons from the electrode is the electron injection layer, the layer that receives electrons from the electron injection layer and transports the electrons to the light emitting layer is the electron transport layer, and the inflow of holes from the light emitting layer is The layer to be prevented is called a hole block layer. Each of these layers is selected and used depending on factors such as the energy level of the material, heat resistance, adhesion with the organic compound layer or the metal electrode.

  As the light emitting material or host material that can be used in the organic compound layer together with the alkynyl group-substituted condensed heterocyclic compound (formula (1)), condensed polycyclic aromatics (anthracene, naphthalene, phenanthrene, pyrene, tetracene, pentacene, coronene, chrysene) Fluorescein, perylene, rubrene and derivatives thereof), phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, Quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran Polymethine, merocyanine, imidazole chelated oxinoid compounds, quinacridone, rubrene, stilbene derivatives and fluorescent dyes.

  Of the known hole injection materials that can be used in the organic electroluminescence device of the present invention, more effective hole injection materials are aromatic tertiary amine derivatives or phthalocyanine derivatives. Specific examples of the aromatic tertiary amine derivative are triphenylamine, tolylamine, tolyldiphenylamine, N, N′-diphenyl-N, N ′-(3-methylphenyl) -1,1′-biphenyl-4,4 '-Diamine (hereinafter referred to as TPD), N, N, N', N '-(4-methylphenyl) -1,1'-phenyl-4,4'-diamine, N, N, N', N '-(4-Methylphenyl) -1,1'-biphenyl-4,4'-diamine, N, N'-diphenyl-N, N'-dinaphthyl-1,1'-biphenyl-4,4'-diamine N, N '-(methylphenyl) -N, N'-(4-n-butylphenyl) -phenanthrene-9,10-diamine, N, N-bis (4-di-4-tolylaminophenyl)- 4-phenyl-cyclohexane or the like, or An oligomer or polymer having a these aromatic tertiary amine skeletons, though not particularly limited thereto.

Specific examples of phthalocyanine (Pc) derivatives are H ₂ Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl ₂ SiPc, (HO) AlPc, (HO) GaPc, Although it is a phthalocyanine derivative and a naphthalocyanine derivative such as VOPc, TiOPc, MoOPc, and GaPc-O-GaPc, it is not limited thereto.

In the organic electroluminescence device of the present invention, a more effective known electron injection material or hole block material is a metal complex compound or a nitrogen-containing five-membered ring derivative. Specific examples of the metal complex compound include 8-hydroxyquinolinate lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, tris ( 8-hydroxyquinolinato) aluminum (hereinafter referred to as Alq _3), tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [ h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (o-cresolate) gallium, bis (2-Methyl-8-quinolinato) (1-naphtholato) aluminum , Bis (2-methyl-8-quinolinato) (2-naphtholate) gallium and the like, but are not limited thereto.

  The nitrogen-containing five-membered derivative is preferably an oxazole, thiazole, oxadiazole, thiadiazole or triazole derivative. Specifically, 2,5-bis (1-phenyl) -1,3,4-oxazole, dimethyl-1,4-bis (5′-phenyloxazolyl) benzene, 2,5-bis (1- Phenyl) -1,3,4-thiazole, 2,5-bis (1-phenyl) -1,3,4-oxadiazole, 2- (4′-tert-butylphenyl) -5- (4 ″- Biphenyl) -1,3,4-oxadiazole, 2,5-bis (1-naphthyl) -1,3,4-oxadiazole, 1,4-bis [2- (5-phenyloxadiazolyl) Benzene, 1,4-bis [2- (5-phenyloxadiazolyl) -4-tert-butylbenzene], 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1 , 3,4-thiadiazole, 2,5-bis (1-naphthyl) -1,3,4-thiadiazole, 1,4-bis [2- (5-phenylthiadiazolyl)] benzene, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1 , 3,4-triazole, 2,5-bis (1-naphthyl) -1,3,4-triazole, 1,4-bis [2- (5-phenyltriazolyl)] benzene, 3- (4- Biphenylyl) -4-phenyl-5-t-butylphenyl-1,2,4-triazole and the like are exemplified, but not limited thereto.

  In the organic electroluminescence device of the present invention, an inorganic compound layer may be provided between the light emitting layer and the electrode in order to improve the charge injection property.

Examples of the inorganic compound layer include fluorides and oxides of alkali metals or alkaline earth metals such as LiF, Li ₂ O, RaO, SrO, BaF ₂ , and SrF ₂ .

  As the conductive material used for the anode of the organic electroluminescence device of the present invention, a material having a work function larger than 4 eV is suitable, and carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, Platinum, palladium and their alloys, ITO (substance with 5-10% tin oxide added to indium oxide) substrate, tin oxide used for NESA substrate, metal oxide such as indium oxide, and organic conductivity such as polythiophene and polypyrrole Can be used.

As the conductive material used for the cathode, those having a work function smaller than 4 eV are suitable, and magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum and the like and alloys thereof are used. It is done. Here, examples of the alloy include magnesium / silver, magnesium / indium, lithium / aluminum, and the like. The ratio of the alloy is not particularly limited and is controlled by the temperature of the vapor deposition source, the atmosphere, the degree of vacuum, and the like.
If necessary, the anode and the cathode may be formed of two or more layers.

  As for the organic electroluminescent element of this invention, it is desirable for at least one surface to be transparent in the light emission wavelength range of an element. The substrate is also preferably transparent.

  The transparent electrode is obtained by using the above-described conductive material and setting so as to ensure a predetermined translucency by a method such as vapor deposition or sputtering.

The electrode on the light emitting surface preferably has a light transmittance of 10% or more.
The substrate is not particularly limited as long as it has mechanical and thermal strength and has transparency, and examples thereof include a glass substrate and a transparent resin film.

  Transparent resin films include polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone. , Polysulfone, polyethersulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, Polyvinylidene fluoride, polyester, polycarbonate, polyurethane, polyimide, polyetherimide, polyimide, polypropylene, etc. It is.

  The organic electroluminescence device of the present invention can be provided with a protective layer on the surface of the device or can be protected by silicon oil, resin, etc., in order to improve stability against temperature, humidity, atmosphere, etc. .

  In addition, the formation of each layer of the organic electroluminescence element should be performed by any one of dry film formation methods such as vacuum deposition, sputtering, plasma, and ion plating, or wet film formation methods such as spin coating, dipping, and flow coating. Can do. The film thickness is not particularly limited, but the normal film thickness is in the range of 5 nm to 10 μm, and more preferably in the range of 10 nm to 0.2 μm.

  In the case of a wet film-forming method, a thin film is prepared by dissolving or dispersing materials such as alkynyl group-substituted condensed heterocyclic compounds (formula (1)) forming each layer in a solvent such as ethanol, chloroform, tetrahydrofuran, dioxane and the like. be able to.

As the dry film formation method, vacuum deposition is preferable, and the 8-alkynylquinoline derivative of the present invention is placed in an alumina deposition cell using a vacuum deposition apparatus, with a vacuum degree of 2 × 10 ⁻³ Pa or less and a substrate temperature of room temperature. A thin film can be prepared by heating a material such as a tungsten filament and evaporating the material.

  Co-evaporation of TPD and bis (8'-quinolyl) acetylene or the like can be performed by using an evaporation source for each and controlling the temperature independently.

  Here, any organic thin film layer is made of polystyrene, polycarbonate, polyacrylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, etc. Insulating resins and copolymers thereof, photoconductive resins such as poly-N-vinylcarbazole and polysilane, resins such as conductive resins such as polythiophene and polypyrrole, antioxidants, ultraviolet absorbers, plasticizers, etc. Additives can be used.

  The organic electroluminescence device of the present invention can be used for a flat light emitter such as a flat panel display of a wall-mounted television, a light source such as a copying machine, a printer, a backlight of a liquid crystal display or instruments, a display board, a marker lamp, and the like.

  The ultraviolet absorption maximum and the fluorescence maximum wavelength of the alkynyl group-substituted condensed heterocyclic compound of the present invention were measured by the following methods.

  The ultraviolet absorption maximum wavelength was measured by dissolving an alkynyl group-substituted condensed heterocyclic compound in chloroform (concentration 0.01 mg / ml) and using an ultraviolet spectrophotometer at room temperature (20 ° C.).

  The fluorescence maximum wavelength was measured at room temperature (20 ° C.) using the above-mentioned chloroform solution and a fluorescence spectrophotometer.

  The alkynyl group-substituted condensed heterocyclic compound of the present invention exhibited blue fluorescence with a fluorescence maximum of 380 to 400 nm when irradiated with ultraviolet light having a wavelength of about 240 nm in a chloroform solution. Moreover, the organic electroluminescent element containing this implement | achieved blue fluorescence (refer the following Examples 16-22).

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

Reference Example 1 Synthesis of 8-trifluoromethanesulfoxyquinoline A yellow solution of 7.26 g (50 mmol) of 8-quinolinol, 50 ml of methylene chloride and 9.1 ml (65 mmol) of triethylamine was brought to 0 ° C. in an ice bath, and then trifluoromethanesulfonic acid. 9.3 ml (55 mmol) of anhydride was added dropwise. After dripping, the reaction solution changed to almost black was stirred for 1 hour while maintaining the reaction temperature at 0 ° C. After completion of the reaction, 200 ml of water and 250 ml of diethyl ether were added to the reaction solution for liquid separation, and the resulting organic layer was washed with hydrochloric acid (125 ml × 2 times) at a concentration of 1 mol / L and water (125 ml × 1 time) in this order. After drying over anhydrous magnesium sulfate and filtering, diethyl ether is distilled off, the residue is dissolved in 250 ml of hexane at a temperature of 70 ° C., insoluble matter is filtered, and the filtrate is cooled to give brown white crystals. The target compound was obtained. (12.6 g, 91% yield)
The physical properties are shown below.

¹ H-NMR (300 MHz, CDCl ₃ ) δ: 9.11-9.03 (m, 1H), 8.30-8.19 (m, 1H), 7.89-7.81 (m, 1H) 7.65-7.50 (m, 3H)
EI-MS (m / e): 277 (M ^<+> ), CI-MS (m / z): 278 (MH ^<+> )

２０ｍｌシュレンクに８−トリフルオロメタンスルホキシキノリン５５４ｍｇ（２．０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム２７ｍｇ（２．４×１０^−５ｍｏｌ）、ピペリジン６ｍｌを加えて攪拌した。この黄色溶液に１，４−ジエチニルベンゼン１２０ｍｇ（０．９５ｍｍｏｌ）を加えて、８０℃で３時間攪拌した。反応終了後、反応混合物に塩化メチレンを加えて希釈して、飽和塩化アンモニウム水溶液で洗浄し、次いで無水硫酸マグネシウムで乾燥して、ろ過後、得られたろ液を減圧乾固した。得られた反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をヘキサン／酢酸エチル＝１００／０から１／１に徐々に変えて展開した。）によって精製することにより黄橙色粉末である目的化合物を得た。（３１０ｍｇ、収率８６％）
以下に、その物性を示す。
^１Ｈ−ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ_３）δ：９．０９−９．０５（ｍ、２Ｈ）、８．２５−８．１４（ｍ、２Ｈ）、８．０６−８．００（ｍ、２Ｈ）、７．８７−７．８０（ｍ、２Ｈ）、７．６９（ｓ，４Ｈ）、７．６０−７．４０（ｍ，４Ｈ）
ＥＩ−ＭＳ（ｍ／ｅ）：３８０（Ｍ^＋）、ＣＩ−ＭＳ（ｍ／ｚ）：３８１（ＭＨ^＋）
［吸収極大：クロロホルム溶液］２４２ｎｍ
［蛍光極大波長：クロロホルム溶液］３９３ｎｍExample 1
Synthesis of 1,4-bis (8′-quinolylethynyl) benzene (Formula 10)

To 20 ml Schlenk, 554 mg (2.0 mmol) of 8-trifluoromethanesulfoxyquinoline, 27 mg (2.4 × 10 ⁻⁵ mol) of tetrakis (triphenylphosphine) palladium and 6 ml of piperidine were added and stirred. To this yellow solution, 120 mg (0.95 mmol) of 1,4-diethynylbenzene was added and stirred at 80 ° C. for 3 hours. After completion of the reaction, the reaction mixture was diluted with methylene chloride, washed with a saturated aqueous ammonium chloride solution, then dried over anhydrous magnesium sulfate, filtered, and the filtrate obtained was dried under reduced pressure. The obtained reaction crude product is purified by column chromatography using silica gel (development solvent is gradually changed from hexane / ethyl acetate = 100/0 to 1/1) to obtain a yellow-orange powder. The target compound was obtained. (310 mg, 86% yield)
The physical properties are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 9.09-9.05 (m, 2H), 8.25-8.14 (m, 2H), 8.06-8.00 (m, 2H) 7.87-7.80 (m, 2H), 7.69 (s, 4H), 7.60-7.40 (m, 4H)
EI-MS (m / e): 380 (M ^<+> ), CI-MS (m / z): 381 (MH ^<+> )
[Absorption maximum: chloroform solution] 242 nm
[Fluorescence maximum wavelength: chloroform solution] 393 nm

２０ｍｌシュレンクに８−トリフルオロメタンスルホキシキノリン５５４ｍｇ（２．０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム２７ｍｇ（２．４×１０^−５ｍｏｌ）、ピペリジン６ｍｌを加え攪拌した。この黄色溶液に１，３−ジエチニルベンゼン１２０ｍｇ（０．９５ｍｍｏｌ）を加えて、８０℃で４時間攪拌した。反応終了後、反応混合物に塩化メチレンを加えて希釈した後、飽和塩化アンモニウム水溶液で洗浄し、次いで無水硫酸マグネシウムで乾燥し、ろ過後、ろ液を減圧乾固した。得られた橙色の反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をヘキサン／酢酸エチル＝１００／０から１／１に徐々に変えて展開した。）によって精製することで黄橙色粉末である目的化合物を得た。（３００ｍｇ、収率８３％）
以下に、その物性を示す。
^１Ｈ−ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ_３）δ：９．０９−９．０６（ｍ，２Ｈ），８．２３−８．１５（ｍ，２Ｈ），８．０６−７．９８（ｍ、３Ｈ）、７．８６−７．７８（ｍ、２Ｈ）、７．７０−７．６５（ｍ、２Ｈ）、７．５９−７．３５（ｍ、５Ｈ）
ＥＩ−ＭＳ（ｍ／ｅ）：３８０（Ｍ^＋）、ＣＩ−ＭＳ（ｍ／ｚ）：３８１（ＭＨ^＋）
［吸収極大：クロロホルム溶液］２４２ｎｍ
［蛍光極大波長：クロロホルム溶液］３８６ｎｍExample 2
Synthesis of 1,3-bis (8′-quinolylethynyl) benzene (Formula 11)

To 20 ml Schlenk, 554 mg (2.0 mmol) of 8-trifluoromethanesulfoxyquinoline, 27 mg (2.4 × 10 ⁻⁵ mol) of tetrakis (triphenylphosphine) palladium and 6 ml of piperidine were added and stirred. To this yellow solution, 120 mg (0.95 mmol) of 1,3-diethynylbenzene was added and stirred at 80 ° C. for 4 hours. After completion of the reaction, the reaction mixture was diluted with methylene chloride, washed with a saturated aqueous ammonium chloride solution, then dried over anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to dryness under reduced pressure. The resulting orange reaction crude product was purified by column chromatography using silica gel (developed by gradually changing the developing solvent from hexane / ethyl acetate = 100/0 to 1/1). The target compound was obtained. (300 mg, 83% yield)
The physical properties are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 9.09-9.06 (m, 2H), 8.23-8.15 (m, 2H), 8.06-7.98 (m, 3H) 7.86-7.78 (m, 2H), 7.70-7.65 (m, 2H), 7.59-7.35 (m, 5H)
EI-MS (m / e): 380 (M ^<+> ), CI-MS (m / z): 381 (MH ^<+> )
[Absorption maximum: chloroform solution] 242 nm
[Fluorescence maximum wavelength: chloroform solution] 386 nm

２０ｍｌシュレンクに８−トリフルオロメタンスルホキシキノリン８００ｍｇ（２．９ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム２３ｍｇ（２．０×１０^−５ｍｏｌ）、ピペリジン６ｍｌを加え攪拌した。この黄色溶液に１，３，５−トリエチニルベンゼン９１ｍｇ（０．６１ｍｍｏｌ）を加え、８０℃で３時間攪拌した。反応終了後、反応混合物に塩化メチレンを加えて希釈した後、飽和塩化アンモニウム水溶液で洗浄し、次いで無水硫酸マグネシウムで乾燥、減圧乾固した。得られた橙色の反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をヘキサン／酢酸エチル＝１００／０から１／１に徐々に変えて展開した。）によって精製することで黄橙色粉末である目的化合物を得た。（２８０ｍｇ、収率８６％）
以下に、その物性を示す。
^１Ｈ−ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ_３）δ：９．１０−９．０５（ｍ、３Ｈ）、８．２１−８．１７（ｍ、３Ｈ）、８．０８−８．０１（ｍ、６Ｈ）、７．８６−７．８２（ｍ，３Ｈ）、７．６０−７．５３（ｍ，３Ｈ）、７．５０−７．４５（ｍ、３Ｈ）
ＥＩ−ＭＳ（ｍ／ｅ）：４０３（Ｍ−Ｃ_９Ｈ_６Ｎ）
［吸収極大：クロロホルム溶液］２４２ｎｍ
［蛍光極大波長：クロロホルム溶液］３８６ｎｍExample 3
Synthesis of 1,3,5-tris (8′-quinolylethynyl) benzene (Formula 12)

To 20 ml Schlenk, 800 mg (2.9 mmol) of 8-trifluoromethanesulfoxyquinoline, 23 mg (2.0 × 10 ⁻⁵ mol) of tetrakis (triphenylphosphine) palladium and 6 ml of piperidine were added and stirred. To this yellow solution, 91 mg (0.61 mmol) of 1,3,5-triethynylbenzene was added and stirred at 80 ° C. for 3 hours. After completion of the reaction, the reaction mixture was diluted with methylene chloride, washed with a saturated aqueous ammonium chloride solution, then dried over anhydrous magnesium sulfate and dried under reduced pressure. The resulting orange reaction crude product was purified by column chromatography using silica gel (developed by gradually changing the developing solvent from hexane / ethyl acetate = 100/0 to 1/1). The target compound was obtained. (280 mg, 86% yield)
The physical properties are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 9.10-9.05 (m, 3H), 8.21-8.17 (m, 3H), 8.08-8.01 (m, 6H) 7.86-7.82 (m, 3H), 7.60-7.53 (m, 3H), 7.50-7.45 (m, 3H)
EI-MS (m / e) : 403 (M-C 9 H 6 N)
[Absorption maximum: chloroform solution] 242 nm
[Fluorescence maximum wavelength: chloroform solution] 386 nm

Example 4
Synthesis of bis (8′-quinolyl) acetylene (Formula 4)

(First step)
To 20 ml Schlenk, 554 mg (2.0 mmol) of 8-trifluoromethanesulfoxyquinoline, 11.6 mg (1.0 × 10 ⁻⁵ mol) of tetrakis (triphenylphosphine) palladium and 6 ml of piperidine were added and stirred. To this yellow solution, 290 μl (2.1 mmol) of trimethylsilylacetylene was added and stirred at 90 ° C. for 3 hours. After completion of the reaction, the reaction mixture was diluted with methylene chloride, washed with a saturated aqueous ammonium chloride solution, and dried under reduced pressure to obtain 8-trimethylsilylethynylquinoline. (360 mg, 80% yield of this step)

(Second step)
8-Trimethylsilylethynylquinoline obtained by the above reaction was dissolved in 6 ml of methanol, an aqueous NaOH solution (concentration 1 mol / 1.3 ml) was added dropwise, and the mixture was stirred at room temperature for 15 minutes. 20 ml of water was added to the reaction mixture, followed by extraction with methylene chloride (10 ml × 3 times), and the obtained organic layer was evaporated under reduced pressure to obtain 8-ethynylquinoline. (245 mg, 99% yield of this step)

(Third step)
To 8-ethynylquinoline obtained by the above reaction, add 527 mg (1.9 mmol) of 8-trifluoromethanesulfoxyquinoline, 11.6 mg (1.0 × 10 ⁻⁵ mol) of tetrakis (triphenylphosphine) palladium, and 6 ml of piperidine. And stirred at 90 ° C. for 2 hours. After completion of the reaction, the yellow solid precipitated in the reaction system is collected by filtration, and the resulting solid is washed with water (5 ml) and hexane (5 ml) in this order, and then dried to obtain a target compound which is a pale yellow powder. Got. (400 mg, 90% yield of this step)
The total yield of the first to third steps is 71%.
The physical properties are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 9.11-9.05 (m, 2H), 8.22-8.15 (m, 4H), 7.84-7.80 (m, 2H) 7.60-7.51 (m, 2H), 7.49-7.39 (m, 2H)
EI-MS (m / e): 280 (M ^<+> ), CI-MS (m / z): 281 (MH ^<+> )
[Absorption maximum: chloroform solution] 240 nm
[Fluorescence maximum wavelength: chloroform solution] 397 nm

２０ｍｌシュレンクに８−トリフルオロメタンスルホキシキノリン５５４ｍｇ（２．０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム２３ｍｇ（２×１０^−５ｍｏｌ）、ピペリジン６ｍｌを加え攪拌した。この黄色反応溶液にフェニルアセチレン２３１μｌ（２．１ｍｍｏｌ）を加えて、８０℃で２．５時間攪拌した。反応終了後、反応混合液に飽和塩化アンモニウム水溶液を加えた後、塩化メチレンで抽出し、有機層を無水硫酸マグネシウムで乾燥し、減圧乾固した。得られた反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をヘキサン／酢酸エチル＝１００／０から５／１に徐々に変えて展開した。）によって精製することで、黄色固体である目的化合物を得た。（４２２ｍｇ、収率９２％）
以下に、その物性を示す。
^１Ｈ−ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ_３）δ：９．０８−９．０５（ｍ、１Ｈ）、８．２２−８．１７（ｍ，１Ｈ）、８．３０−７．９０（ｍ、１Ｈ）、７．８３−７．７９（ｍ、１Ｈ）、７．７１−７．６７（ｍ、２Ｈ）、７．５６−７．５０（ｍ，１Ｈ）、７．４８−７．４３（ｍ，１Ｈ）、７．４０−７．３０（ｍ，３Ｈ）
ＥＩ−ＭＳ（ｍ／ｅ）：２２９（Ｍ^＋）、ＣＩ−ＭＳ（ｍ／ｚ）：２３０（ＭＨ^＋）
［吸収極大：クロロホルム溶液］２４２ｎｍ
［蛍光極大波長：クロロホルム溶液］３９１ｎｍExample 5
Synthesis of 8-phenylethynylquinoline (Formula 13)

To 20 ml Schlenk, 554 mg (2.0 mmol) of 8-trifluoromethanesulfoxyquinoline, 23 mg (2 × 10 ⁻⁵ mol) of tetrakis (triphenylphosphine) palladium and 6 ml of piperidine were added and stirred. To this yellow reaction solution, 231 μl (2.1 mmol) of phenylacetylene was added and stirred at 80 ° C. for 2.5 hours. After completion of the reaction, a saturated aqueous ammonium chloride solution was added to the reaction mixture, followed by extraction with methylene chloride. The organic layer was dried over anhydrous magnesium sulfate and evaporated to dryness. The obtained reaction crude product is purified by column chromatography using silica gel (development solvent is gradually changed from hexane / ethyl acetate = 100/0 to 5/1), and is a yellow solid. The target compound was obtained. (422 mg, 92% yield)
The physical properties are shown below.
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 9.08-9.05 (m, 1H), 8.22-8.17 (m, 1H), 8.30-7.90 (m, 1H) 7.83-7.79 (m, 1H), 7.71-7.67 (m, 2H), 7.56-7.50 (m, 1H), 7.48-7.43 (m, 1H), 7.40-7.30 (m, 3H)
EI-MS (m / e): 229 (M ^<+> ), CI-MS (m / z): 230 (MH ^<+> )
[Absorption maximum: chloroform solution] 242 nm
[Fluorescence maximum wavelength: chloroform solution] 391 nm

２０ｍｌシュレンクに８−トリフルオロメタンスルホキシキノリン５５４ｍｇ（２．０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム２３ｍｇ（２×１０^−５ｍｏｌ）、ピペリジン６ｍｌを加え攪拌した。この黄色溶液に４−フルオロフェニルアセチレン２４１μｌ（２．１ｍｍｏｌ）を加え、８０℃で２時間攪拌した。反応混合液に飽和塩化アンモニウム水溶液を加えた後、有機物は塩化メチレンで抽出、無水硫酸マグネシウムで乾燥、減圧乾固した。得られた反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をヘキサン／酢酸エチル＝１００／０から５／１に徐々に変えて展開した。）によって精製することで黄色固体である目的化合物を得た。（４０３ｍｇ、収率８２％）
^１Ｈ−ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ_３）δ：９．０６−９．０４（ｍ、１Ｈ）、８．２０−８．１７（ｍ，１Ｈ）、８．０１−７．９８（ｍ、１Ｈ）、７．８４−７．８１（ｍ、１Ｈ）、７．７０−７．６３（ｍ、２Ｈ）、７．５６−７．５１（ｍ，１Ｈ）、７．４８−７．４４（ｍ，１Ｈ）、７．２２−７．０２（ｍ、２Ｈ）
ＣＩ−ＭＳ（ｍ／ｚ）：２４８（ＭＨ＋）
［吸収極大：クロロホルム溶液］２４２ｎｍ
［蛍光極大波長：クロロホルム溶液］３９２ｎｍExample 6
Synthesis of 8- (4′-fluorophenylethynyl) quinoline (Formula 14)

To 20 ml Schlenk, 554 mg (2.0 mmol) of 8-trifluoromethanesulfoxyquinoline, 23 mg (2 × 10 ⁻⁵ mol) of tetrakis (triphenylphosphine) palladium and 6 ml of piperidine were added and stirred. To this yellow solution, 241 μl (2.1 mmol) of 4-fluorophenylacetylene was added and stirred at 80 ° C. for 2 hours. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. The resulting reaction crude product was purified by column chromatography using silica gel (development solvent was gradually changed from hexane / ethyl acetate = 100/0 to 5/1), and was purified as a yellow solid. A compound was obtained. (403 mg, 82% yield)
^{1 H-NMR (300MHz, CDCl} 3) δ: 9.06-9.04 (m, 1H), 8.20-8.17 (m, 1H), 8.01-7.98 (m, 1H) 7.84-7.81 (m, 1H), 7.70-7.63 (m, 2H), 7.56-7.51 (m, 1H), 7.48-7.44 (m, 1H), 7.22-7.02 (m, 2H)
CI-MS (m / z): 248 (MH +)
[Absorption maximum: chloroform solution] 242 nm
[Fluorescence maximum wavelength: chloroform solution] 392 nm

２０ｍｌシュレンクに８−トリフルオロメタンスルホキシキノリン５５４ｍｇ（２．０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム２３ｍｇ（２×１０^−５ｍｏｌ）、ピペリジン６ｍｌを加え攪拌した。この黄色溶液に３−フルオロフェニルアセチレン２４３μｌ（２．１ｍｍｏｌ）を加え、８０℃で２時間攪拌した。反応混合液に飽和塩化アンモニウム水溶液を加えた後、有機物は塩化メチレンで抽出、無水硫酸マグネシウムで乾燥、減圧乾固した。得られた反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をヘキサン／酢酸エチル＝１００／０から５／１に徐々に変えて展開した。）によって精製することで黄色固体である目的化合物を得た。（３５３ｍｇ、収率７１％）
^１Ｈ−ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ_３）：δ９．０７−９．０５（ｍ、１Ｈ）、８．２１−８．１８（ｍ，１Ｈ）、８．０２−７．９９（ｍ，１Ｈ）、７．８６−７．８２（ｍ，１Ｈ）、７．５７−７．５２（ｍ，１Ｈ）、７．５０−７．４４（ｍ，２Ｈ）、７．３９−７．２８（ｍ，２Ｈ）、７．０９−７．０４（ｍ，１Ｈ）
ＣＩ−ＭＳ（ｍ／ｚ）：２４８（ＭＨ＋）
［吸収極大：クロロホルム溶液］２４１ｎｍ
［蛍光極大波長：クロロホルム溶液］３８６ｎｍExample 7
Synthesis of 8- (3′-fluorophenylethynyl) quinoline (Formula 15)

To 20 ml Schlenk, 554 mg (2.0 mmol) of 8-trifluoromethanesulfoxyquinoline, 23 mg (2 × 10 ⁻⁵ mol) of tetrakis (triphenylphosphine) palladium and 6 ml of piperidine were added and stirred. To this yellow solution, 243 μl (2.1 mmol) of 3-fluorophenylacetylene was added and stirred at 80 ° C. for 2 hours. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. The resulting reaction crude product was purified by column chromatography using silica gel (development solvent was gradually changed from hexane / ethyl acetate = 100/0 to 5/1), and was purified as a yellow solid. A compound was obtained. (353 mg, 71% yield)
¹ H-NMR (300 MHz, CDCl ₃ ): δ 9.07-9.05 (m, 1H), 8.21-8.18 (m, 1H), 8.02-7.99 (m, 1H), 7.86-7.82 (m, 1H), 7.57-7.52 (m, 1H), 7.50-7.44 (m, 2H), 7.39-7.28 (m, 2H) ), 7.09-7.04 (m, 1H)
CI-MS (m / z): 248 (MH +)
[Absorption maximum: chloroform solution] 241 nm
[Fluorescence maximum wavelength: chloroform solution] 386 nm

２０ｍｌシュレンクに８−トリフルオロメタンスルホキシキノリン５５４ｍｇ（２．０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム２３ｍｇ（２×１０^−５ｍｏｌ）、ピペリジン６ｍｌを加え攪拌した。この黄色溶液に２−フルオロフェニルアセチレン２３８μｌ（２．１ｍｍｏｌ）を加え、８０℃で２時間攪拌した。反応混合液に飽和塩化アンモニウム水溶液を加えた後、有機物は塩化メチレンで抽出、無水硫酸マグネシウムで乾燥、減圧乾固した。得られた反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をヘキサン／酢酸エチル＝１００／０から５／１に徐々に変えて展開した。）によって精製することで黄色固体である目的化合物を得た。（３５７ｍｇ、収率７２％）
^１Ｈ−ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ_３）δ：９．０８−９．０６（ｍ、１Ｈ）、８．２０−８．１７（ｍ，１Ｈ）、８．０６−８．０３（ｍ，１Ｈ）、７．８５−７．８２（ｍ，１Ｈ）、７．７２−７．６７（ｍ，１Ｈ）、７．５７−７．５２（ｍ，１Ｈ）、７．４９−７．４４（ｍ，１Ｈ）、７．３５−７．３０（ｍ，１Ｈ）、７．１８−７．０９（ｍ，２Ｈ）
ＣＩ−ＭＳ（ｍ／ｚ）：２４８（ＭＨ＋）
［吸収極大：クロロホルム溶液］２４２ｎｍ
［蛍光極大波長：クロロホルム溶液］３８７ｎｍExample 8
Synthesis of 8- (2′-fluorophenylethynyl) quinoline (Formula 16)

To 20 ml Schlenk, 554 mg (2.0 mmol) of 8-trifluoromethanesulfoxyquinoline, 23 mg (2 × 10 ⁻⁵ mol) of tetrakis (triphenylphosphine) palladium and 6 ml of piperidine were added and stirred. To this yellow solution, 238 μl (2.1 mmol) of 2-fluorophenylacetylene was added and stirred at 80 ° C. for 2 hours. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. The resulting reaction crude product was purified by column chromatography using silica gel (development solvent was gradually changed from hexane / ethyl acetate = 100/0 to 5/1), and was purified as a yellow solid. A compound was obtained. (357 mg, 72% yield)
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 9.08-9.06 (m, 1H), 8.20-8.17 (m, 1H), 8.06-8.03 (m, 1H) 7.85-7.82 (m, 1H), 7.72-7.67 (m, 1H), 7.57-7.52 (m, 1H), 7.49-7.44 (m, 1H), 7.35-7.30 (m, 1H), 7.18-7.09 (m, 2H)
CI-MS (m / z): 248 (MH +)
[Absorption maximum: chloroform solution] 242 nm
[Fluorescence maximum wavelength: chloroform solution] 387 nm

２０ｍｌシュレンクに８−トリフルオロメタンスルホキシキノリン５５４ｍｇ（２．０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム２３ｍｇ（２×１０^−５ｍｏｌ）、ピペリジン６ｍｌを加え攪拌した。この黄色溶液に４−メトキシフェニルアセチレン２７２μｌ（２．１ｍｍｏｌ）を加え、８０℃で２時間攪拌した。反応混合液に飽和塩化アンモニウム水溶液を加えた後、有機物は塩化メチレンで抽出、無水硫酸マグネシウムで乾燥、減圧乾固した。反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をヘキサン／酢酸エチル＝１００／０から４／１に徐々に変えて展開した。）によって精製することで黄色油状物である目的化合物を得た。（２５３ｍｇ、収率４９％）
^１Ｈ−ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ_３）δ：９．０４−９．０２（ｍ，１Ｈ）、８．１８−８．１５（ｍ，１Ｈ）、８．００−７．９７（ｍ，１Ｈ）、７．８０−７．７７（ｍ，１Ｈ）、７．７３−７．５８（ｍ，２Ｈ）、７．５５−７．５２（ｍ，１Ｈ）、７．４９−７．４３（ｍ，１Ｈ）、６．９０−６．８６（ｍ，２Ｈ）、３．８６（ｓ，３Ｈ）
ＣＩ−ＭＳ（ｍ／ｚ）：２６０（ＭＨ＋）
［吸収極大：クロロホルム溶液］２４７ｎｍ
［蛍光極大波長：クロロホルム溶液］４２０ｎｍExample 9
Synthesis of 8- (4′-methoxyphenylethynyl) quinoline (Formula 17)

To 20 ml Schlenk, 554 mg (2.0 mmol) of 8-trifluoromethanesulfoxyquinoline, 23 mg (2 × 10 ⁻⁵ mol) of tetrakis (triphenylphosphine) palladium and 6 ml of piperidine were added and stirred. To this yellow solution, 272 μl (2.1 mmol) of 4-methoxyphenylacetylene was added and stirred at 80 ° C. for 2 hours. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. The reaction crude product was purified by column chromatography using silica gel (developed by gradually changing the developing solvent from hexane / ethyl acetate = 100/0 to 4/1) to give the target compound as a yellow oil. Obtained. (253 mg, 49% yield)
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 9.04-9.02 (m, 1H), 8.18-8.15 (m, 1H), 8.00-7.97 (m, 1H) 7.80-7.77 (m, 1H), 7.73-7.58 (m, 2H), 7.55-7.52 (m, 1H), 7.49-7.43 (m, 1H), 6.90-6.86 (m, 2H), 3.86 (s, 3H)
CI-MS (m / z): 260 (MH +)
[Absorption maximum: chloroform solution] 247 nm
[Fluorescence maximum wavelength: chloroform solution] 420 nm

２０ｍｌシュレンクに８−トリフルオロメタンスルホキシキノリン５５４ｍｇ（２．０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム２３ｍｇ（２×１０^−５ｍｏｌ）、ピペリジン６ｍｌを加え攪拌した。この黄色溶液に３−メトキシフェニルアセチレン２６７μｌ（２．１ｍｍｏｌ）を加え、８０℃で２時間攪拌した。反応混合液に飽和塩化アンモニウム水溶液を加えた後、有機物は塩化メチレンで抽出、無水硫酸マグネシウムで乾燥、減圧乾固した。反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をヘキサン／酢酸エチル＝１００／０から３／１に徐々に変えて展開した。）によって精製することで黄色油状物である目的化合物を得た。（３６４ｍｇ、収率７０％）
^１Ｈ−ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ_３）δ：９．０７−９．０５（ｍ、１Ｈ）、８．２０−８．１７（ｍ，１Ｈ）、８．０３−８．００（ｍ，１Ｈ）、７．８４−７．８１（ｍ，１Ｈ）、７．５７−７．５２（ｍ，１Ｈ）、７．４８−７．４４（ｍ，１Ｈ）、７．３６−７．２２（ｍ，３Ｈ）、６．９５−６．８９（ｍ，１Ｈ）、３．８４（ｓ，３Ｈ）
ＣＩ−ＭＳ（ｍ／ｚ）：２６０（ＭＨ＋）
［吸収極大：クロロホルム溶液］２４２ｎｍ
［蛍光極大波長：クロロホルム溶液］３９８ｎｍExample 10
Synthesis of 8- (3′-methoxyphenylethynyl) quinoline (Formula 18)

To 20 ml Schlenk, 554 mg (2.0 mmol) of 8-trifluoromethanesulfoxyquinoline, 23 mg (2 × 10 ⁻⁵ mol) of tetrakis (triphenylphosphine) palladium and 6 ml of piperidine were added and stirred. To this yellow solution, 267 μl (2.1 mmol) of 3-methoxyphenylacetylene was added and stirred at 80 ° C. for 2 hours. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. By purifying the reaction crude product by column chromatography using silica gel (development solvent was gradually changed from hexane / ethyl acetate = 100/0 to 3/1), the target compound as a yellow oily substance was obtained. Obtained. (364 mg, 70% yield)
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 9.07-9.05 (m, 1H), 8.20-8.17 (m, 1H), 8.03-8.00 (m, 1H) , 7.84-7.81 (m, 1H), 7.57-7.52 (m, 1H), 7.48-7.44 (m, 1H), 7.36-7.22 (m, 3H), 6.95-6.89 (m, 1H), 3.84 (s, 3H)
CI-MS (m / z): 260 (MH +)
[Absorption maximum: chloroform solution] 242 nm
[Fluorescence maximum wavelength: chloroform solution] 398 nm

２０ｍｌシュレンクに８−トリフルオロメタンスルホキシキノリン５５４ｍｇ（２．０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム２３ｍｇ（２×１０^−５ｍｏｌ）、ピペリジン６ｍｌを加え攪拌した。この黄色溶液に４−フェニルフェニルアセチレン３７４ｍｇ（２．１ｍｍｏｌ）を加え、８０℃で２時間攪拌した。反応混合液に飽和塩化アンモニウム水溶液を加えた後、有機物は塩化メチレンで抽出、無水硫酸マグネシウムで乾燥、減圧乾固した。反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をヘキサン／酢酸エチル＝１００／０から４／１に徐々に変えて展開した。）によって精製することで黄色固体である目的化合物を得た。（２９７ｍｇ、収率４９％）
^１Ｈ−ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ_３）δ：９．０７−９．０５（ｍ，１Ｈ）、８．１９−８．１５（ｍ，１Ｈ）、８．０３−８．００（ｍ，１Ｈ）、７．８２−７．７３（ｍ，３Ｈ）、７．６４−７．５９（ｍ，４Ｈ）、７．５６−７．５１（ｍ，１Ｈ）、７．４８−７．４２（ｍ，３Ｈ）、７．３８−７．２５（ｍ，１Ｈ）
ＣＩ−ＭＳ（ｍ／ｚ）：３０６（ＭＨ＋）
［吸収極大：クロロホルム溶液］２４２ｎｍ
［蛍光極大波長：クロロホルム溶液］４０２ｎｍExample 11
Synthesis of 8- (4′-phenylphenylethynyl) quinoline (Formula 19)

To 20 ml Schlenk, 554 mg (2.0 mmol) of 8-trifluoromethanesulfoxyquinoline, 23 mg (2 × 10 ⁻⁵ mol) of tetrakis (triphenylphosphine) palladium and 6 ml of piperidine were added and stirred. To this yellow solution was added 374 mg (2.1 mmol) of 4-phenylphenylacetylene, and the mixture was stirred at 80 ° C. for 2 hours. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. The reaction crude product was purified by column chromatography using silica gel (development solvent was gradually changed from hexane / ethyl acetate = 100/0 to 4/1) to obtain the target compound as a yellow solid. It was. (297 mg, 49% yield)
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 9.07-9.05 (m, 1H), 8.19-8.15 (m, 1H), 8.03-8.00 (m, 1H) 7.82-7.73 (m, 3H), 7.64-7.59 (m, 4H), 7.56-7.51 (m, 1H), 7.48-7.42 (m, 3H), 7.38-7.25 (m, 1H)
CI-MS (m / z): 306 (MH +)
[Absorption maximum: chloroform solution] 242 nm
[Fluorescence maximum wavelength: chloroform solution] 402 nm

２０ｍｌシュレンクに８−トリフルオロメタンスルホキシキノリン５５４ｍｇ（２．０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム２３ｍｇ（２×１０^−５ｍｏｌ）、ピペリジン６ｍｌを加え攪拌した。この黄色溶液に２’−ピリジルアセチレン２６２μｌ（２．６ｍｍｏｌ）を加え、８０℃で２時間攪拌した。反応混合液に飽和塩化アンモニウム水溶液を加えた後、有機物は塩化メチレンで抽出、無水硫酸マグネシウムで乾燥、減圧乾固した。反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をヘキサン／酢酸エチル＝１００／０から０／１００に徐々に変えて展開した。）によって精製することで黄色油状物である目的化合物を得た。（１８８ｍｇ、収率４１％）
^１Ｈ−ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ_３）δ：９．０８−９．０６（ｍ，１Ｈ）、８．６８−８．６５（ｍ，１Ｈ）、８．２１−８．１８（ｍ，１Ｈ）、８．１０−８．０７（ｍ，１Ｈ）、７．８７−７．８４（ｍ，１Ｈ）、７．７４−７．７０（ｍ，２Ｈ）、７．５８−７．５５（ｍ，１Ｈ）、７．５３−７．４７（ｍ，１Ｈ）、７．２８−７．２４（ｍ，１Ｈ）
ＣＩ−ＭＳ（ｍ／ｚ）：２３１（ＭＨ＋）
［吸収極大：クロロホルム溶液］２４１ｎｍ
［蛍光極大波長：クロロホルム溶液］３７７ｎｍExample 12
Synthesis of 8- (2′-pyridylethynyl) quinoline (Formula 20)

To 20 ml Schlenk, 554 mg (2.0 mmol) of 8-trifluoromethanesulfoxyquinoline, 23 mg (2 × 10 ⁻⁵ mol) of tetrakis (triphenylphosphine) palladium and 6 ml of piperidine were added and stirred. To this yellow solution was added 262 μl (2.6 mmol) of 2′-pyridylacetylene, and the mixture was stirred at 80 ° C. for 2 hours. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. The reaction crude product was purified by column chromatography using silica gel (development solvent was gradually changed from hexane / ethyl acetate = 100/0 to 0/100), and the target compound as a yellow oil was obtained. Obtained. (188 mg, 41% yield)
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 9.08-9.06 (m, 1H), 8.68-8.65 (m, 1H), 8.21-8.18 (m, 1H) , 8.10-8.07 (m, 1H), 7.87-7.84 (m, 1H), 7.74-7.70 (m, 2H), 7.58-7.55 (m, 1H), 7.53-7.47 (m, 1H), 7.28-7.24 (m, 1H)
CI-MS (m / z): 231 (MH +)
[Absorption maximum: chloroform solution] 241 nm
[Fluorescence maximum wavelength: chloroform solution] 377 nm

２０ｍｌシュレンクに８−トリフルオロメタンスルホキシキノリン５５４ｍｇ（２．０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム２３ｍｇ（２×１０^−５ｍｏｌ）、ピペリジン６ｍｌを加え攪拌した。この黄色溶液に３’−ピリジルアセチレン２４４ｍｇ（２．３７ｍｍｏｌ）を加え、８０℃で２時間攪拌した。反応混合液に飽和塩化アンモニウム水溶液を加えた後、有機物は塩化メチレンで抽出、無水硫酸マグネシウムで乾燥、減圧乾固した。反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をヘキサン／酢酸エチル＝１００／０から０／１００に徐々に変えて展開した。）によって精製することで黄色油状物である目的化合物を得た。（３７５ｍｇ、収率８１％）
^１Ｈ−ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ_３）δ：９．０８−９．０６（ｍ，１Ｈ）、８．９２−８．９１（ｍ，１Ｈ）、８．５８−８．５６（ｍ，１Ｈ）、８．２２−８．１９（ｍ，１Ｈ）、８．０４−８．０２（ｍ，１Ｈ）、７．９９−７．９５（ｍ，１Ｈ）、７．８７−７．８４（ｍ，１Ｈ）、７．５６−７．５３（ｍ，１Ｈ）、７．５０−７．４６（ｍ，１Ｈ）、７．３３−７．２９（ｍ，１Ｈ）
ＣＩ−ＭＳ（ｍ／ｚ）：２３１（ＭＨ＋）
［吸収極大：クロロホルム溶液］２４１ｎｍ
［蛍光極大波長：クロロホルム溶液］３７８ｎｍExample 13
Synthesis of 8- (3′-pyridylethynyl) quinoline (Formula 21)

To 20 ml Schlenk, 554 mg (2.0 mmol) of 8-trifluoromethanesulfoxyquinoline, 23 mg (2 × 10 ⁻⁵ mol) of tetrakis (triphenylphosphine) palladium and 6 ml of piperidine were added and stirred. To this yellow solution, 244 mg (2.37 mmol) of 3′-pyridylacetylene was added and stirred at 80 ° C. for 2 hours. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. The reaction crude product was purified by column chromatography using silica gel (development solvent was gradually changed from hexane / ethyl acetate = 100/0 to 0/100), and the target compound as a yellow oil was obtained. Obtained. (375 mg, 81% yield)
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 9.08-9.06 (m, 1H), 8.92-8.91 (m, 1H), 8.58-8.56 (m, 1H) , 8.22-8.19 (m, 1H), 8.04-8.02 (m, 1H), 7.99-7.95 (m, 1H), 7.87-7.84 (m, 1H), 7.56-7.53 (m, 1H), 7.50-7.46 (m, 1H), 7.33-7.29 (m, 1H)
CI-MS (m / z): 231 (MH +)
[Absorption maximum: chloroform solution] 241 nm
[Fluorescence maximum wavelength: chloroform solution] 378 nm

２０ｍｌシュレンクに８−トリフルオロメタンスルホキシキノリン５５４ｍｇ（２．０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム２３ｍｇ（２×１０^−５ｍｏｌ）、ピペリジン６ｍｌを加え攪拌した。この黄色溶液に５−エチニル−１−メチル−１−Ｈ−イミダゾール２４４μｌ（２．４ｍｍｏｌ）を加え、８０℃で２時間攪拌した。反応混合液に飽和塩化アンモニウム水溶液を加えた後、有機物は塩化メチレンで抽出、無水硫酸マグネシウムで乾燥、減圧乾固した。反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をヘキサン／酢酸エチル＝１００／０から０／１００に徐々に変えて展開し、更に、メタノール／酢酸エチル＝１／１０で展開した。）によって精製することで黄色固体である目的化合物を得た。（４１８ｍｇ、収率９０％）
^１Ｈ−ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ_３）δ：９．０５−９．０３（ｍ，１Ｈ）、８．２１−８．１８（ｍ，１Ｈ）、７．９８−７．９５（ｍ，１Ｈ）、７．８５−７．８２（ｍ，１Ｈ）、７．５７−７．４４（ｍ，４Ｈ）、３．８８（ｓ，３Ｈ）
ＣＩ−ＭＳ（ｍ／ｚ）：２３４（ＭＨ＋）
［吸収極大：クロロホルム溶液］２４６ｎｍ
［蛍光極大波長：クロロホルム溶液］４１６ｎｍExample 14
Synthesis of 8- (2′-methyl-2′-H-imidazolylethynyl) quinoline (Formula 22)

To 20 ml Schlenk, 554 mg (2.0 mmol) of 8-trifluoromethanesulfoxyquinoline, 23 mg (2 × 10 ⁻⁵ mol) of tetrakis (triphenylphosphine) palladium and 6 ml of piperidine were added and stirred. To this yellow solution, 244 μl (2.4 mmol) of 5-ethynyl-1-methyl-1-H-imidazole was added and stirred at 80 ° C. for 2 hours. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. The reaction crude product was developed by column chromatography using silica gel (developing solvent was gradually changed from hexane / ethyl acetate = 100/0 to 0/100, and further developed with methanol / ethyl acetate = 1/10). To obtain the target compound as a yellow solid. (418 mg, 90% yield)
^{1 H-NMR (300MHz, CDCl} 3) δ: 9.05-9.03 (m, 1H), 8.21-8.18 (m, 1H), 7.98-7.95 (m, 1H) 7.85-7.82 (m, 1H), 7.57-7.44 (m, 4H), 3.88 (s, 3H)
CI-MS (m / z): 234 (MH +)
[Absorption maximum: chloroform solution] 246 nm
[Fluorescence maximum wavelength: chloroform solution] 416 nm

２０ｍｌシュレンクに８−エチニルキノリン４６０ｍｇ（３．０ｍｍｏｌ）、テトラキス（トリフェニルホスフィン）パラジウム６９ｍｇ（６×１０^−５ｍｏｌ）、ピペリジン９ｍｌを加え攪拌した。この黄色溶液に４−ブロモベンゾフェノン７８３ｍｇ（３．０ｍｍｏｌ）を加え、８０℃で３２時間攪拌した。反応混合液に飽和塩化アンモニウム水溶液を加えた後、有機物は塩化メチレンで抽出、無水硫酸マグネシウムで乾燥、減圧乾固した。反応粗生成物をシリカゲルを用いたカラムクロマトグラフィー（展開溶媒をヘキサン／酢酸エチル＝１００／０から３／１に徐々に変えて展開した。）によって精製することで黄色固体である目的化合物を得た。（６０５ｍｇ、収率６０％）
^１Ｈ−ＮＭＲ（３００ＭＨｚ、ＣＤＣｌ_３）δ：９．０９−９．０７（ｍ，１Ｈ）、８．２２−８．１９（ｍ，１Ｈ）８．０６−８．０３（ｍ，１Ｈ）、７．８８−７．７９（ｍ，７Ｈ）、７．６４−７．４７（ｍ，５Ｈ）
ＣＩ−ＭＳ（ｍ／ｚ）：３３４（ＭＨ＋）
［吸収極大：クロロホルム溶液］２４２ｎｍ
［蛍光極大波長：クロロホルム溶液］４７３ｎｍExample 15
Synthesis of 8- (4′-benzoylphenylethynyl) quinoline (Formula 23)

To 20 ml Schlenk, 460 mg (3.0 mmol) of 8-ethynylquinoline, 69 mg (6 × 10 ⁻⁵ mol) of tetrakis (triphenylphosphine) palladium and 9 ml of piperidine were added and stirred. To this yellow solution, 783 mg (3.0 mmol) of 4-bromobenzophenone was added and stirred at 80 ° C. for 32 hours. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the organic matter was extracted with methylene chloride, dried over anhydrous magnesium sulfate, and evaporated to dryness under reduced pressure. The reaction crude product was purified by column chromatography using silica gel (development solvent was gradually changed from hexane / ethyl acetate = 100/0 to 3/1) to obtain the target compound as a yellow solid. It was. (605 mg, 60% yield)
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 9.09-9.07 (m, 1H), 8.22-8.19 (m, 1H) 8.06-8.03 (m, 1H), 7.88-7.79 (m, 7H), 7.64-7.47 (m, 5H)
CI-MS (m / z): 334 (MH +)
[Absorption maximum: chloroform solution] 242 nm
[Fluorescence maximum wavelength: chloroform solution] 473 nm

Example 16
Preparation of the organic electroluminescent element which contains bis (8'- quinolyl) acetylene (the compound of said Formula (4)) in an organic light emitting layer.
Using a vacuum deposition apparatus (manufactured by ULVAC-KIKO), using a vacuum-deposited ITO as a transparent electrode on soda glass as a substrate, and from a TPD at a vacuum degree of 2 × 10 ⁻³ Pa or less on the same substrate A hole transport layer 3 having a thickness of 40 nm, a light emitting layer 4 containing 1.4% by weight of bis (8′-quinolyl) acetylene in TPD having a thickness of 40 nm, an electron transport layer 5 made of Alq ₃ having a thickness of 20 nm, an electrode 6 was formed by sequentially depositing aluminum (Al) with a film thickness of 100 nm to produce an organic electroluminescence element.
In addition, the temperature of the vapor deposition source of bis (8′-quinolyl) acetylene was controlled within a range not exceeding 280 ° C.
The device emitted light at 16 cd / m ² when +30 V was applied between the electrodes using the ITO electrode 2 as the positive electrode and the Al electrode 6 as the negative electrode. The emission spectrum had a shoulder at 435 nm and a peak at 497 nm, and the chromaticity coordinates of the emission color according to JIS Z8701 were (0.25, 0.36).

Example 17
Preparation of an organic electroluminescence device containing 8- (4′-phenylphenylethynyl) quinoline (the compound of the formula (19)) in an organic light emitting layer.
Using glass with an indium tin oxide (hereinafter abbreviated as ITO) film manufactured by ECH as a transparent electrode substrate, a vacuum deposition apparatus (manufactured by ULVAC Kiko) is used, and 2 × 10 ⁻³ Pa or less is formed on the substrate. The hole transport layer 3 made of N, N′-bis (3-methylphenyl) -N, N′-bis (phenyl) -benzidine (hereinafter abbreviated as TPD) is formed with a film thickness of 40 nm and 4,4 ′ under vacuum. The light-emitting layer 4 containing 9% by weight of 8- (4′-phenylphenylethynyl) quinoline in bis (carbazol-9-yl) biphenyl (hereinafter abbreviated as CBP) has a thickness of 20 nm, and 3- (4-biphenylyl ) A hole blocking layer (electron transporting layer) 5 made of -4-phenyl-5-t-butylphenyl-1,2,4-triazole (hereinafter abbreviated as TAZ) having a film thickness of 20 nm and an electrode 6 made of aluminum. Al) film thickness 100 nm, to produce an organic electroluminescent device formed by sequentially depositing.
When the ITO electrode 2 of the device was energized with the Al electrode 6 as the negative electrode and the voltage between the electrodes was increased, light was emitted at 4 cd / m ² at + 22V. The emission spectrum had a peak at 418 nm, and the chromaticity coordinates of the emission color were (0.18, 0.14).

Example 18
Preparation of an organic electroluminescent device containing 8- (2′-methyl-2′-H-imidazolylethynyl) quinoline (the compound of the formula (22)) in an organic light emitting layer.
An organic electroluminescence device was produced in the same manner as in Example 17 except that the light-emitting layer 4 containing 9% by weight of 8- (2′-methyl-2′-H-imidazolylethynyl) quinoline in CBP was used.
When the ITO electrode 2 of the element was used as a positive electrode and the Al electrode 6 was used as a negative electrode and the voltage between the electrodes was increased, light was emitted at 14 cd / m ² at + 21V. The maximum current efficiency at this time was 0.10 cd / A. The emission spectrum had a peak at 427 nm, and the chromaticity coordinates of the emission color were (0.17, 0.12).

Example 19
Preparation of an organic electroluminescence device containing 8- (4′-fluorophenylethynyl) quinoline (the compound of the formula (14)) in an organic light emitting layer.
An organic electroluminescence device was produced in the same manner as in Example 17 except that the light-emitting layer 4 containing 9% by weight of 8- (4′-fluorophenylethynyl) quinoline in CBP was used.
When the ITO electrode 2 of the element was used as a positive electrode and the Al electrode 6 was used as a negative electrode and the voltage between the electrodes was increased, light was emitted at 5 cd / m ² at + 21V. The maximum current efficiency at this time was 0.059 cd / A. The emission spectrum had a peak at 420 nm, and the chromaticity coordinates of the emission color were (0.21, 0.19).

Example 20
Preparation of an organic electroluminescent element containing 8-phenylethynylquinoline (the compound of the formula (13)) in an organic light emitting layer.
An organic electroluminescence device was produced in the same manner as in Example 17 except that the light emitting layer 4 containing 9% by weight of 8-phenylethynylquinoline in CBP was used.
When the ITO electrode 2 of the element was used as a positive electrode and the Al electrode 6 was used as a negative electrode and the voltage between the electrodes was increased, light was emitted at 4 cd / m ² at + 21V. The maximum current efficiency at this time was 0.052 cd / A. The emission spectrum had a peak at 415 nm, and the chromaticity coordinates of the emission color were (0.17, 0.11).

Example 21
Fabrication of an organic electroluminescence device comprising 1,3-bis (8′-quinolylethynyl) benzene (the compound of the formula (11)) in an organic light emitting layer.
An organic electroluminescence device was produced in the same manner as in Example 17 except that the light emitting layer 4 containing 9% by weight of 1,3-bis (8′-quinolylethynyl) benzene in CBP was used.
When the ITO electrode 2 of the device was used as a positive electrode and the Al electrode 6 was used as a negative electrode and the voltage between the electrodes was increased, light was emitted at 0.4 cd / m ² at + 20V. The maximum current efficiency at this time was 0.032 cd / A. The emission spectrum had a peak at 451 nm, and the chromaticity coordinates of the emission color were (0.18, 0.17).

Example 22
Preparation of an organic electroluminescent device containing 8- (2′-fluorophenylethynyl) quinoline (the compound of the formula (16)) in an organic light emitting layer.
An organic electroluminescence device was produced in the same manner as in Example 17 except that the light-emitting layer 4 containing 9% by weight of 8- (2′-fluorophenylethynyl) quinoline in CBP was used.
When the ITO electrode 2 of the device was energized with the Al electrode 6 as the negative electrode and the voltage between the electrodes was increased, light was emitted at ³ cd / m ² at + 18V. The maximum current efficiency at this time was 0.018 cd / A. The emission spectrum had a peak at 421 nm, and the chromaticity coordinates of the emission color were (0.19, 0.18).

  ADVANTAGE OF THE INVENTION According to this invention, the organic electroluminescent element which contains the alkynyl group substituted condensed heterocyclic compound shown by said Formula (1) which shows strong blue light emission under ultraviolet irradiation in an organic compound layer can be provided.

  According to the present invention, the alkynyl group-substituted condensed heterocyclic compound represented by the above formula (1 ′), which exhibits strong blue light emission by ultraviolet irradiation in a chloroform solution and is extremely useful as an organic electroluminescence device material, is included. Thus, novel alkynyl group-substituted fused heterocyclic compounds represented by the above formulas (2) to (4) can be provided.

  According to the present invention, a novel alkynyl group-substituted condensed heterocyclic compound represented by the above formula (1), which exhibits strong blue light emission under ultraviolet irradiation and is useful as a material for an organic electroluminescence device, is further obtained with high yield. A method of synthesis can be provided.

Claims (4)

An organic electroluminescence device having an organic compound thin layer between a pair of electrodes, wherein the organic compound layer is represented by the following formula (1):

In the formula, n ¹ represents an integer of ¹ to 3, and when n ¹ is 1, A represents an aryl group or a heterocyclic group, and when n ¹ is 2 or 3, A is a divalent or trivalent aryl. Represents a group or a heterocyclic group, X and Y each represent CH;
The organic electroluminescent element characterized by containing the alkynyl group substituted condensed heterocyclic compound shown by these. The compound represented by formula (1) is represented by the following formula (2):

In the formula, R ¹ represents an aryl group or a heterocyclic group other than an unsubstituted phenyl group,
The organic electroluminescence device according to claim 1, which is represented by: The compound represented by the formula (1) is represented by the following formula (3):

Wherein, ^{n 2} represents an integer of 2-3.
The organic electroluminescence device according to claim 1, which is represented by: The compound represented by formula (1) is represented by the following formula (4):

The organic electroluminescence device according to claim 1, which is represented by:

Images