JP2005225819A - Azole compound having pyrrole ring and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an azole compound being a new oxadiazole derivative, a new azole compound usable as the raw material of the oxadiazole derivative, a method for producing these azole compounds, and a charge transport material and a luminescent material, both containing the azole compound. <P>SOLUTION: The azole compound is an oxadiazole derivative having a pyrrole ring and represented by formula (I-1) (wherein Ar<SP>1</SP>and Ar<SP>2</SP>are each an optionally substituted aromatic or heterocyclic aromatic ring; R<SP>1</SP>to R<SP>3</SP>are each hydrogen, a halogen, or an alkyl, aryl, aralkyl, halogens, cyano, aliphatic or aromatic amino, aliphatic or aromatic acyl, or aliphatic or aromatic alkoxy group; and n is 1-6). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a novel azole compound used in various organic thin film elements, a novel compound as a raw material for producing the azole compound, a method for producing the compound, a charge transport material containing the azole compound as a component, and a light emitting material It is about.

  In recent years, there have been active attempts to realize new functional elements through thinning of organic molecules. For example, research on organic electroluminescence elements using other organic thin films formed by vapor deposition or coating methods, and other optical elements has been actively conducted.

  Among organic molecules used in such an organic thin film element, an oxadiazole derivative emits strong fluorescence even in a solid state, and has excellent electron transporting ability and hole transporting ability. It is evaluated by. For example, an oxadiazole derivative having the following structure has been reported as a light emitting material of an organic electroluminescence device.

  As R in the formula, a tert-butyl group, a diethylamino group, a phenyl group, and other groups are shown.

｛Ａは、（置換）アルキル基、（置換）アリール基、（置換）複素環式芳香環基｝
が記載されている。 Further, Patent Document 1 discloses an oxadiazole having the following structure as an oxadiazole derivative that is excellent in light emission luminance, electron transport property, and film forming property, is useful as an organic electroluminescence device, and is also useful as a fluorescent brightening agent. Derivative

{A is a (substituted) alkyl group, (substituted) aryl group, (substituted) heterocyclic aromatic ring group}
Is described.

（式中、Ａは芳香族炭化水素基もしくは芳香族複素環基を表し；Ｒは水素原子、ハロゲン原子、アルキル基、アルコキシ基、ヒドロキシ基を表す）が提案されており、有機ＥＬ素子用材料、特に電子輸送材料として有用であることが記載されている。 Patent Document 2 discloses an oxadiazole derivative having the following structure.

(Wherein, A represents an aromatic hydrocarbon group or an aromatic heterocyclic group; R represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a hydroxy group) has been proposed, and a material for an organic EL device In particular, it is described that it is useful as an electron transport material.

（式中、Ｒ_１〜Ｒ_３は同じであっても異なっていてもよく、それぞれ水素原子、ハロゲン原子または一価の基を表す。）が提案されている。 Patent Document 3 discloses a novel oxadiazole derivative having the following structure that provides an amorphous organic thin film that is stable and excellent in heat resistance.

(Wherein R _{1 to} R ₃ may be the same or different and each represents a hydrogen atom, a halogen atom or a monovalent group).

  Non-Patent Document 2 describes that an oxadiazole derivative is obtained from a tetrazole compound via a ring-closing reaction. On the other hand, Non-Patent Document 3 shows that a tetrazole compound can be obtained by a reaction between a nitrile compound and an azide.

JP-A-9-104679 JP-A-8-3150 JP-A-5-202011 Hamada et al., Journal of Chemical Society of Japan 1991, (11), 1540-1548 J. Sauer, R. Huisgen, and H. J. Sturm Tetrahedron, 1960, 11, PP. 241-251 Koguro & etc .: SYNTHESIS 1998, No6 June p910-914

  The inventors of the present invention have intensively studied to develop a novel compound that exhibits excellent characteristics as a charge transport material or a light emitting material. As a result, it was found that the oxadiazole derivative having a pyrrole ring has fluorescence in the visible part. The present invention made under such knowledge provides an azole compound comprising a novel oxadiazole derivative useful as a charge transport material or a light-emitting material, and a novel azole compound as a raw material for the oxadiazole derivative. It is an object of the present invention to provide a method for producing an azole compound, and further to provide an electron transport material and a light emitting material containing the azole compound as components.

または下記式(I-2)

（式(I-1)または(I-2)中、Ａｒ^１およびＡｒ^２は、同一または異なり、置換基を有してもよい芳香族環またはヘテロ環式芳香族環、Ｒ^１〜Ｒ^３は、それぞれ独立して、水素原子、アルキル基、アリール基、アラルキル基、ハロゲン原子、シアノ基、脂肪族または芳香族アミノ基、脂肪族または芳香族アシル基、脂肪族または芳香族アルコキシ基、ｎは１〜６）で表される。 The azole compound described in claim 1 for achieving the above object is an oxadiazole derivative having a pyrrole ring, which is represented by the following formula (I-1):

Or the following formula (I-2)

(In formula (I-1) or (I-2), Ar ¹ and Ar ² are the same or different and may have a substituent, an aromatic ring or a heterocyclic aromatic ring, R ^{1 to} R ^3. Each independently represents a hydrogen atom, alkyl group, aryl group, aralkyl group, halogen atom, cyano group, aliphatic or aromatic amino group, aliphatic or aromatic acyl group, aliphatic or aromatic alkoxy group, n Are represented by 1-6).

Examples of the aromatic ring or heterocyclic aromatic ring (Ar ¹ and Ar ² ) which may have a substituent include aromatic rings such as a benzene ring and a naphthalene ring, or heterocyclic rings such as a pyridine ring and a quinoline ring And a formula aromatic ring. Preferred examples of the substituent for the aromatic ring include an alkyl group, an alkoxy group, a halogen atom, and a cyano group.

R ⁴ and R ⁵ of an aliphatic amino group (—NR ⁴ R ⁵ ) which is an example of R ¹ , R ² and R ³ are a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an amyl group, Examples thereof include an alkyl group which may have 1 to 6 carbon atoms such as an isoamyl group, a hexyl group and a cyclohexyl group, or an aliphatic group such as a cyclic alkyl group, and one of R ⁴ and R ⁵ is a hydrogen atom. May be. Specific examples of the aliphatic amino group include N, N-dimethylamino group, N, N-diethylamino group, N, N-diisopropylamino group, N-methylamino group, N-ethylamino group, and N-propylamino group. Is mentioned.

R ⁶ and R ⁷ of the aromatic amino group (—NR ⁶ R ⁷ ) may have a substituent such as a phenyl group, a tolyl group, a methoxyphenyl group, a cyanophenyl group, a chlorophenyl group, and a biphenyl group. Groups. Specific examples of the aromatic amino group include N-phenylamino group, N, N-diphenylamino group, N-tolylamino group, N-methoxyphenylamino group, N-cyanophenylamino group, and N-chlorophenylamino group. It is done.

Examples of R ⁸ of the aliphatic or aromatic acyl group (—COR ⁸ ) include a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a phenyl group. Specific examples of the acyl group include aliphatic acyl groups such as formyl group, acetyl group, propionyl group, butyryl group and valeryl group, and aromatic acyl groups such as benzoyl group and toluoyl group.

  Examples of the aliphatic or aromatic alkoxy group include aliphatic alkoxy groups such as methoxy group, ethoxy group, isopropoxy group and butoxy group, and aromatic alkoxy groups such as phenoxy group and benzyloxy group.

  Examples of the alkyl group may be branched such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, nonyl group, dodecyl group, etc. Examples thereof include an alkyl group, a cyclic alkyl group such as a cyclohexyl group, and a haloalkyl group such as a trifluoromethyl group.

  Examples of the aryl group include a phenyl group, a tolyl group, a biphenyl group, and a naphthyl group. Examples of the aralkyl group include benzyl group and phenethyl group. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.

Similarly, the azole compound described in claim 2 is the oxadiazole derivative according to claim 1, wherein Ar ¹ and / or Ar ² is a benzene ring which may have a substituent.

The azole compound according to claim 3, wherein R ¹ , R ² and / or R ³ are alkyl groups having 1 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl having 7 to 20 carbon atoms. The azole compound according to claim 1, which is a group selected from the group.

または下記式(II-2)

（式(II-1)または(II-2)中、Ｒ^１、Ｒ^２、Ｒ^３およびＡｒ^１は前記式(I-1)および(I-2)と同じ）で表される。 An azole compound described in claim 4 for achieving the above object is a 5-substituted tetrazole compound having a pyrrole ring, which is represented by the formula (II-1):

Or the following formula (II-2)

(In the formula (II-1) or (II-2), R ¹ , R ² , R ³ and Ar ¹ are the same as those in the above formulas (I-1) and (I-2)).

（式(III)中、Ａｒ^２は前記式(I-1)および(I-2)と同じ、Ｘはハロゲン原子、ｎは１から６）で表される置換アリール酸ハロゲン化物との間で閉環反応させることを特徴とする前記式(I-1)または(I-2)で表されるアゾール化合物の製造方法である。 In order to achieve the above object, a method for producing an azole compound according to claim 5 includes a 5-substituted tetrazole compound represented by the formula (II-1) or (II-2). The following formula (III)

(In the formula (III), Ar ² is the same as in the above formulas (I-1) and (I-2), X is a halogen atom, and n is 1 to 6). A method for producing an azole compound represented by the above formula (I-1) or (I-2), wherein the cyclization reaction is performed.

Examples of the substituted aryl acid halide represented by the formula (III) include acid chlorides having the following structure. In addition, as a substituent (R) in a formula, the same atom or group as said R < ¹ > -R < ² > may be sufficient, and a hydrogen atom, a C1-C12 alkyl group, carbon number is preferable. It is a 6-20 aryl group, a C7-20 aralkyl group, or a halogen atom.

  Specific examples include benzoyl chloride, p-tert-butylbenzoyl chloride, 2,3-dicarboxynaphthalene chloride, 1,2,3-benzenetricarboxylic acid chloride, 1,3,5-benzenetricarboxylic acid chloride. Products, pyromellitic acid chlorides, or bromides of these organic acids.

または下記式(IV-2)

（式(VI-1)または(VI-2)中、Ｒ^１、Ｒ^２、Ｒ^３およびＡｒ^１は前記式(I-1)および(I-2)と同じ）で表されるニトリル化合物と、式（Ｖ）
ＭＮ_３ （Ｖ）
（式(Ｖ)中、Ｍはアルカリ金属、アルカリ土類金属、アンモニウム、またはアルキルアンモニウムで多種混合してもよい）で表されるアジド化合物を反応させることを特徴とする(II-1)または(II-2)で表されるテトラゾール化合物の製造方法である。 The production method described in claim 6 has the following formula (IV-1)

Or the following formula (IV-2)

(In the formula (VI-1) or (VI-2), R ¹ , R ² , R ³ and Ar ¹ are the same as those in the above formulas (I-1) and (I-2)) , Formula (V)
MN ₃ (V)
(In formula (V), M may be mixed with alkali metal, alkaline earth metal, ammonium, or alkylammonium) and is reacted (II-1) or This is a method for producing a tetrazole compound represented by (II-2).

  Examples of the nitrile compound represented by the formula (IV-1) or the formula (IV-2) include those having the following structures. Me in the following formula represents a methyl group.

Examples of the azide compound represented by the formula (V) include sodium azide (NaN ₃ ), calcium azide (Ca (N ₃ ) ₂ ), and ammonium azide (NH ₄ N ₃ ).

  The charge transport material according to claim 7 of the claims for achieving the above object comprises the azole compound according to any one of claims 1 to 3 as a component.

  Similarly, the light-emitting material described in claim 8 contains the azole compound according to any one of claims 1 to 3 as a component.

  The azole compound having pyrrole of the present invention has charge transport performance, an absorption maximum wavelength in the ultraviolet region, and a maximum emission wavelength in the range of 400 to 550 nm. For this reason, the derivative | guide_body of this invention can anticipate a wide application as a charge transport material in an organic electroluminescent element, a luminescent material, or a luminescent material for lasers.

Preferred form for carrying out the invention

  The 5-substituted tetrazole compound represented by the formula (II-1) of the present invention is obtained by a reaction of the following formula with a nitrile compound corresponding to the formula (IV-1) and an azide represented by the formula (V). can get.

  Specific examples of the tetrazole compound of formula (II-1) include, but are not limited to, the following compounds (II-1-1), (II-1-2), and (II-1-3): . In the following formulae, Me represents a methyl group.

  A pyrrole ring represented by the formula (I-1) of the present invention by a ring-closing reaction of the 5-substituted tetrazole compound of the formula (II-1) and the aromatic acid halide represented by the formula (III) according to the following formula An oxadiazole derivative containing is obtained.

Specifically, a pyridine solution of an aromatic acid halide or an inert solvent solution is dropped into a pyridine solution of a 5-substituted tetrazole compound at room temperature to 100 ° C., followed by stirring at the boiling point for several hours. After the generation of N ₂ gas is finished, it is cooled to room temperature, and a large amount of water is added to obtain a precipitated product by recrystallization or the like.

As the inert solvent, THF; glymes; aromatic compounds such as toluene and xylene can be used. Among these, THF; water-soluble solvents such as glymes are preferable. The reaction time is until the generation of N ₂ gas is completed, but is generally 3 to 5 hours.

  Specific examples of the oxadiazole derivative containing a pyrrole ring represented by the formula (I-1) include the following compounds (I-1-1) to (I-1-11) ”. However, the present invention is not limited to these. In the following formulae, Me represents a methyl group.

  The 5-substituted tetrazole compound represented by the formula (II-2) of the present invention is obtained by the reaction of the following formula using a nitrile compound corresponding to the formula (IV-2) and an azide represented by the formula (V). can get.

  Specific examples of the tetrazole compound of the formula (II-2) include the following compound (II-2-1).

  A pyrrole ring represented by the formula (I-2) of the present invention by a ring-closing reaction of the 5-substituted tetrazole compound of the formula (II-2) and the aromatic acid halide represented by the formula (III) according to the following formula: An oxadiazole derivative containing is obtained.

  Specific reaction conditions are the same as in the ring-closing reaction of the oxadiazole derivative of the formula (I-1).

  Specific examples of the oxadiazole derivative of the present invention include, but are not limited to, the following oxadiazole derivative (I-2-1). In the following formula, + represents a tert-butyl group, and Me represents a methyl group.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1 (tetrazole compound (II-1-1): synthesis of 5- [3- (2,5-dimethylpyrrol-1-yl) phenyl] tetrazole)
A mixture of 3- (2,5-dimethylpyrrol-1-yl) benzonitrile (3.74 g), sodium azide (1.61 g), triethylammonium chloride (3.41 g) and toluene (20 ml) was heated for 8 h. Circulated. After extraction with water, 36% aqueous HCl was added to precipitate the product, which was collected by filtration and dried to obtain 3.26 g of the desired tetrazole compound (II-1-1) in a yield of 72%. It was.

^{According to 1} H-NMR (300 MHz, DMSO) analysis, δ value is 8.877 (s, 1H), 8.134 (d, 1H), 7.765 (dd, 1H), 7.532 (d, 1H). , 5.856 (s, 2H), 2.019 (s, 6H).

Moreover, (delta) value by ¹³ C-NMR (DMSO) analysis is 139.666, 130.694, 130.628, 127.644, 126.317, 126.153, 125.221, 106.356, 100.084. , 12.838 was obtained.

  As a result of performing mass spectrometry (MS), m / e was 238 (M-1). Table 1 shows the molecular formula of the tetrazole compound (II-1-1).

Example 2 (Synthesis of tetrazole compound (II-1-2))
In the same manner as in Example 1, the tetrazole compound (II-1-2) was obtained from the nitrile compound (IV-1-1).

Example 3 (Synthesis of tetrazole compound (II-2-1))
In the same manner as in Example 1, the tetrazole compound (II-2-1) was obtained from the nitrile compound (IV-2-1).

  Table 1 shows the molecular formulas of the tetrazole compounds obtained in Examples 1 to 3 and the results of mass spectrometry (MS).

Table 2 shows the measurement results of ¹ H-NMR and ¹³ C-NMR of the tetrazole compounds obtained in Examples 1 to 3.

Example 4 (Oxadiazole derivative containing pyrrole ring (I-2-1): 2- (1-phenyl-5-methylpyrrol-2-yl) phenyl-5-p-tert-butylphenyloxadiazole Composition)
A solution of 0.25 g of the tetrazole compound (II-2-1) obtained in Example 3 and 0.18 g of pt-butylbenzoyl chloride in pyridine (6 ml) was stirred and refluxed for 3 hours, and then cooled to room temperature. 20 ml of water was added. The precipitated solid was filtered and washed with water and methanol. 0.31 g (85% yield) of the oxadiazole derivative (I-2-1) was obtained.

Table 3 shows the molecular formula and mass spectrometry (MS) result of the oxadiazole derivative (I-2-1) obtained. Table 4 shows the ¹ H-NMR measurement results of Compound 4.

Example 5 (Oxadiazole derivative containing pyrrole ring (I-1-6): 1,3,5-tris [2- (3- (2,5-dimethylpyrrol-1-yl) phenyl) oxazole- Synthesis of 5-yl] benzene
To a solution of 1.51 g of the tetrazole compound (II-1-1) obtained in Example 1 in 3 ml of pyridine, 30 g of a diglyme (5 ml) solution of 0.54 g of 1,3,5-benzenetricarbonyltrichloride was added. After dropwise addition in minutes, the mixture was heated to reflux for 3 hours. Water was added at the point where generation of N ₂ was completed to cause precipitation, and the precipitate was filtered and purified by column chromatography (silica gel). 1.14 g (69% yield) of the oxadiazole derivative (I-1-6) was obtained.

Table 3 shows the molecular formula and mass spectrometry (MS) results of the oxadiazole derivative (I-1-6) obtained. Table 4 shows the ¹ H-NMR measurement results.

Example 6 (Oxadiazole derivative containing pyrrole ring (I-1-5): 1,4-bis [2- (2- (2,5-dimethylpyrrol-1-yl) phenyl) oxadiazole Synthesis of -5-yl] benzene
A tetrazole compound obtained by using 2- (2,5-dimethylpyrrol-1-yl) benzonitrile instead of 3- (2,5-dimethylpyrrol-1-yl) benzonitrile used in Example 1 The reaction and post-treatment were performed in the same manner as in Example 1 except that 2.39 g of (II-1-4) and 1.32 g of terephthaloyl chloride were used. 0.84 g (30% yield) of the oxadiazole derivative (I-1-5) was obtained.

Table 3 shows the molecular formula and mass spectrometry (MS) result of the oxadiazole derivative (I-1-5) obtained. Table 4 shows the measurement results of ¹ H-NMR and ¹³ C-NMR.

Examples 7, 8, 9, 10, 11
By the same reaction, in Example 7, the oxadiazole derivative (I-1-1) containing a pyrrole ring, in Example 8, the oxadiazole derivative (I-1-2) containing a pyrrole ring, Example 9 In Example 10, an oxadiazole derivative (I-1-3) containing a pyrrole ring, in Example 10, an oxadiazole derivative (I-1-4) containing a pyrrole ring, and in Example 11, an oxadiazole derivative containing a pyrrole ring. A diazole derivative (I-1-7) was obtained.

Table 3 shows the molecular formulas and mass spectrometry (MS) results of the oxadiazole derivatives obtained in Examples 7, 8, 9, 10, and 11. Table 4 shows the measurement results of ¹ H-NMR and ¹³ C-NMR.

Excitation and fluorescence spectra of the oxadiazole derivatives containing the pyrrole ring obtained in Examples 4 to 11 were measured at a concentration of 1 × 10 ⁻⁴ mol using chloroform as a solvent. The measurement results of the excitation spectrum and fluorescence spectrum of the oxadiazole derivative of the formula (I-2-1) obtained in Example 4 are shown in FIG. The measurement results of the excitation spectrum and fluorescence spectrum of the oxadiazole derivative of the formula (I-1-6) obtained in Example 5 are shown in FIG. FIG. 3 shows the measurement results of the excitation spectrum and fluorescence spectrum of the oxadiazole derivative of the formula (I-1-5) obtained in Example 6.

  As is clear from FIGS. 1, 2 and 3, these oxadiazole derivatives exhibited a maximum emission wavelength at 400 to 500 nm. Furthermore, the emission maximum wavelength of the oxadiazole derivatives obtained in Examples 7 to 11 was in the range of 400 to 500 nm.

2 is an excitation and fluorescence spectrum of an oxadiazole derivative containing a pyrrole ring represented by formula (I-2-1) to which the present invention is applied. 3 is an excitation and fluorescence spectrum of an oxadiazole derivative containing a pyrrole ring represented by formula (I-1-6) to which the present invention is applied. 3 is an excitation and fluorescence spectrum of an oxadiazole derivative containing a pyrrole ring represented by formula (I-1-5) to which the present invention is applied.

Claims (8)

An oxadiazole derivative having a pyrrole ring, which has the following formula (I-1)

Or the following formula (I-2)

(In formula (I-1) or (I-2), Ar ¹ and Ar ² are the same or different and may have a substituent, an aromatic ring or a heterocyclic aromatic ring, R ^{1 to} R ^3. Each independently represents a hydrogen atom, alkyl group, aryl group, aralkyl group, halogen atom, cyano group, aliphatic or aromatic amino group, aliphatic or aromatic acyl group, aliphatic or aromatic alkoxy group, n Are azole compounds represented by 1-6). The azole compound according to claim ^1, wherein Ar ¹ and / or Ar ² is a benzene ring which may have a substituent. 2. The group according to claim ¹ , wherein R ¹ , R ² and / or R ³ are a group selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. An azole compound. A 5-substituted tetrazole compound having a pyrrole ring, which has the formula (II-1)

Or the following formula (II-2)

(In the formula (II-1) or (II-2), R ¹ , R ² , R ³ and Ar ¹ are the same as those in the above formulas (I-1) and (I-2)). A 5-substituted tetrazole compound represented by the formula (II-1) or the formula (II-2) and the following formula (III):

(In the formula (III), Ar ² is the same as in the above formulas (I-1) and (I-2), X is a halogen atom, and n is 1 to 6). A method for producing an azole compound represented by the formula (I-1) or (I-2), wherein the cyclization reaction is performed. The following formula (IV-1)

Or the following formula (IV-2)

(In the formula (VI-1) or (VI-2), R ¹ , R ² , R ³ and Ar ¹ are the same as those in the above formulas (I-1) and (I-2)) , Formula (V)
MN ₃ (V)
(In formula (V), M may be mixed with alkali metal, alkaline earth metal, ammonium, or alkylammonium) and is reacted (II-1) or A method for producing a tetrazole compound represented by (II-2). The charge transport material which uses the azole compound in any one of Claims 1-3 as a component. The luminescent material which uses the azole compound in any one of Claims 1-3 as a component.

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