JP2005035927A - Bis(aminostyryl)phenanthrene compound and intermediate for synthesizing the same, and methods for producing them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound suitable as an organic luminescent material with high luminance at an optimum wavelength and stability, especially giving red-color luminescence, using a compound improved in the fluorescence wavelength of an aminostyrylphenanthrene compound giving red-color luminescence in high fluorescence quantum yield, to provide an intermediate for synthesizing the compound, and to provide methods for producing them. <P>SOLUTION: The bis(aminostyryl)phenanthrene compound is represented by the general formula[I], [II] or [III]( wherein, R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>, R<SP>24</SP>, R<SP>25</SP>, R<SP>26</SP>, R<SP>27</SP>, R<SP>49</SP>, R<SP>50</SP>, R<SP>51</SP>and R<SP>52</SP>are each mutually the same or different phenyl or naphthyl; and R<SP>5</SP>, R<SP>6</SP>, R<SP>28</SP>, R<SP>29</SP>, R<SP>53</SP>and R<SP>54</SP>are each mutually the same or different electron-attracting group such as cyano group ). The intermediate for synthesizing the compound is also provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a bis (aminostyryl) phenanthrene compound suitable as an organic light-emitting material that emits red to green, particularly red light, a synthetic intermediate thereof, and a production method thereof.

  In recent years, organic electroluminescence elements (EL elements) have attracted attention as candidates for flat panel displays that are self-luminous, have a high response speed, and do not depend on viewing angles. There is growing interest. In particular, there are few materials that can form a stable red light-emitting layer, and finding such a material is an indispensable problem for realizing a full-color organic electroluminescence device.

  Aminostyryl compounds are used as electrophotographic photoreceptors, for example, JP-A-5-105645 (Patent Document 1), JP-A-2001-051433, JP-A-2002-131943, JP-A-2002-116560, JP-A-2002-099103, JP-A-2002-099103. 2002-072511, JP 2002-040677, JP 2002-040676, JP 2002-031901, JP 2001-337469, JP 2001-337649, JP 2000-214610, etc. These do not have an electron-withdrawing group in the molecule, and therefore cannot be used in applications such as red light-emitting materials for organic electroluminescent elements.

  As materials for organic electroluminescent elements, materials disclosed in JP-A-3-200889, JP-A-5-94943, and JP-A-2002-226722, and examples used for white organic electroluminescent elements, such as JP-A-6-207170, etc. The material disclosed in the publication is also not for red light emission. JP-A-5-320632, JP-A-6-100857, JP-A-9-268284, JP-A-11-040359, JP-A-11-102784, and JP-A-10-245549 disclose styryl groups and triphenylamino groups. Have been proposed, but these materials cannot be used for red light emission.

  Inorganic and Organic Electroluminescence '96 Berlin, p.101, 1996, Journal of the Korean Chemical Society (1999), 43 (3), 315-320, Bulletin as an aminostyryl compound as a red light emitting material for organic electroluminescent devices The aminostyryl compounds described in of the Korean Chemical Society (2001), 22 (2), 228-230, Journal of the Korean Chemical Society (1999), 43 (3), 315-320 -230132, JP-A-2002-22672, JP-A-2001-2883772, JP-A-2001-106657, JP-A-2001-106658. Examples of its use are reported in JP-A-11-329730, JP-A-11-329731, JP-A-2000-012225, JP-A-2000-012228, JP-A-2000-012227, and JP-A-2000-012226. . These materials may be positively mixed and used as described in JP-A-2002-134276, JP-A-2001-291591, JP-A-2001-307884, and JP-A-2001-307885.

  As the molecular structure of the materials shown above, there are many that have a symmetric structure with respect to the molecular long axis, but an organic electric field element that is often produced in order to set the light emission maximum to an optimum wavelength or by vacuum deposition. In order to improve the deposition property, each of JP 2002-226722 (Patent Document 2), JP 2001-288377, JP 2001-110570 (Patent Document 3), JP 2001-110571, and JP 2000-173773 is disclosed. As shown in the publication, an asymmetric structure may be effective.

  On the other hand, Japanese Patent Application Laid-Open No. 2002-208488 shows that such an asymmetric structure is also effective as a polymer constituent unit. Also, Sience (1998), 281 (11), 1653, WO2001-096409, NATO Science Series, 3: High Technology (2000), 79 (Multiphoton and Light Driven Multielectron Processes in Organics), 53-65, Journal of Chemical Physics. (2000), 113 (10), 3951-3959, Journal of Physical Chemistry A (2001), 105 (51), 11488-11495, Polymer Preprints (American Chemical Society, Division of Polymer Chemistry) (1998), 39 (2 ), 1116, Materials Research Society Symposium Proceedings (1998), 488 (Electrical, Optical, and Magnetic Properties of Organic Solid-State Materials IV), 217-226. Conceivable.

Development of a stable, high-brightness red light-emitting element is difficult, and what has been reported so far is tris (8-quinolinato) aluminum (hereinafter abbreviated as Alq ₃ ) and 4-dicyanomethylene-6- (p- Example of red light emission doped with dimethylaminostyryl) -2-methyl-4H-pyran (hereinafter abbreviated as DCM) (Chem. Funct. Dyes, Proc. Int. Symp., 2nd P. 536 (1993)) As an example of improving the high crystallinity of DCM, 4-dicyanomethylene-6- (p-dimethylaminostyryl) -2- (t--) described in Macromol. Synmpt., (1997), 125, 49 Butyl) -4H-pyran (hereinafter abbreviated as DCJTB), but reliability such as lifetime is not satisfactory as a display material.

Japanese Patent Laid-Open No. 5-105645 (page 5, right column, line 1 to page 10, bottom 6) JP-A-2002-226722 (page 10, right column, line 1 to page 11, left column, line 1 from the bottom, FIGS. 1 to 13) JP-A-2001-110570 (4th page, right column, 40th line to 4th line, from bottom to right of 5th page, 7th page, right column, 30th line to 8th page, left column, 17th line, FIGS. 1 to 8)

  In the development of an organic electroluminescent element, the selection of a light emitting material is the most important issue in securing the reliability of the element. However, since the material disclosed in Patent Document 1 does not have an electron-withdrawing group in the molecule, it cannot be used for red light emission. In addition, the aminostyrylphenanthrene compounds shown in Patent Documents 2 and 3 are excellent in color purity and have a high fluorescence quantum yield and can form a stable amorphous thin film. At present, it is desired to realize a red light emitting device having high color purity.

  An object of the present invention is a compound in which the fluorescence wavelength of an aminostyrylphenanthrene compound which exhibits red to green, particularly red emission with high fluorescence quantum yield, is improved and exhibits high luminance and stable red emission at an optimum wavelength. An object is to provide an aminostyrylphenanthrene compound suitable as a red organic light-emitting material, a synthetic intermediate thereof, and a method for producing them with high efficiency.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have shown that the bis (aminostyryl) phenanthrene compound represented by the following general formula [I], [II] or [III] exhibits strong luminescence, red to It has been found that the light-emitting material can be green, particularly red, and a general and highly efficient manufacturing method has been established, and the present invention has been achieved.

［但し、前記一般式［Ｉ］において、
Ｒ¹及びＲ³は、互いに同一の若しくは異なる下記一般式（１）で表わされるフェニル基であり

（但し、前記一般式（１）において、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰及びＲ¹¹は、互いに同一の又は異なる基であって、それらの少なくとも１つが水素原子、炭素数１以上の飽和又は不飽和の炭化水素基（隣接する炭化水素基同士が共同して環を形成してもよい。）、炭素数１以上の飽和又は不飽和の炭化水素オキシ基、炭素数１以上の飽和又は不飽和の炭化水素アミノ基、トリフルオロメチル基、シアノ基、又はＦ、Ｃｌ等のハロゲン原子である。）、
Ｒ²及びＲ⁴は、互いに同一の又は異なる基であって、下記一般式（２）で表されるフェニル基又は下記一般式（３）で表わされるナフチル基から選ばれた基であり

（但し、前記一般式（２）において、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵及びＲ¹⁶は、互いに同一の又は異なる基であって、それらの少なくとも１つが水素原子、炭素数１以上の飽和又は不飽和の炭化水素基（隣接する炭化水素基同士が共同して環を形成してもよい。）、炭素数１以上の飽和又は不飽和の炭化水素オキシ基、炭素数１以上の飽和又は不飽和の炭化水素アミノ基、トリフルオロメチル基、シアノ基、又はＦ、Ｃｌ等のハロゲン原子である。）、

（但し、前記一般式（３）において、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²及びＲ²³は、互いに同一の又は異なる基であって、それらの少なくとも１つが水素原子、炭素数１以上の飽和又は不飽和の炭化水素基（隣接する炭化水素基同士が共同して環を形成してもよい。）、炭素数１以上の飽和又は不飽和の炭化水素オキシ基、炭素数１以上の飽和又は不飽和の炭化水素アミノ基、トリフルオロメチル基、シアノ基、又はＦ、Ｃｌ等のハロゲン原子である。）、
Ｒ⁵及びＲ⁶は、互いに同一の又は異なる基であって、それらの少なくとも１つが水素原子、シアノ基、ニトロ基、トリフルオロメチル基、又はＦ、Ｃｌ等のハロゲン原子である。］

［但し、前記一般式［II］において、
Ｒ²⁴、Ｒ²⁵及びＲ²⁶は、互いに同一の又は異なる下記一般式（４）で表わされるナフチル基であり

（但し、前記一般式（４）において、Ｒ³⁰、Ｒ³¹、Ｒ³²、Ｒ³³、Ｒ³⁴、Ｒ³⁵及びＲ³⁶は、互いに同一の又は異なる基であって、少なくとも１つが水素原子、炭素数１以上の飽和又は不飽和の炭化水素基（隣接する炭化水素基同士が共同して環を形成してもよい。）、炭素数１以上の飽和又は不飽和の炭化水素オキシ基、炭素数１以上の飽和又は不飽和の炭化水素アミノ基、トリフルオロメチル基、シアノ基、又はＦ、Ｃｌ等のハロゲン原子である。）、
Ｒ²⁷は、下記一般式（５）で表わされるフェニル基又は下記一般式（６）で表わされるナフチル基であり

（但し、前記一般式（５）において、Ｒ³⁷、Ｒ³⁸、Ｒ³⁹、Ｒ⁴⁰、及びＲ⁴¹は、互いに同一の又は異なる基であって、少なくとも１つが水素原子、炭素数１以上の飽和又は不飽和の炭化水素基（隣接する炭化水素基同士が共同して環を形成してもよい。）、炭素数１以上の飽和又は不飽和の炭化水素オキシ基、炭素数１以上の飽和又は不飽和の炭化水素アミノ基、トリフルオロメチル基、シアノ基、又はＦ、Ｃｌ等のハロゲン原子である。）

（但し、前記一般式（６）において、Ｒ⁴²、Ｒ⁴³、Ｒ⁴⁴、Ｒ⁴⁵、Ｒ⁴⁶、Ｒ⁴⁷及びＲ⁴⁸は、互いに同一の又は異なる基であって、少なくとも１つが水素原子、炭素数１以上の飽和又は不飽和の炭化水素基（隣接する炭化水素基同士が共同して環を形成してもよい。）、炭素数１以上の飽和又は不飽和の炭化水素オキシ基、炭素数１以上の飽和又は不飽和の炭化水素アミノ基、トリフルオロメチル基、シアノ基、又はＦ、Ｃｌ等のハロゲン原子である。）、
Ｒ²⁸及びＲ²⁹は、互いに同一の又は異なる基であって、それらの少なくとも１つが水素原子、シアノ基、ニトロ基、トリフルオロメチル基、又はＦ、Ｃｌ等のハロゲン原子である。］

［但し、前記一般式［III］において、
Ｒ⁴⁹及びＲ⁵⁰は、互いに同一の又は異なる下記一般式（７）で表わされるフェニル基であり

（但し、前記一般式（７）において、Ｒ⁵⁵、Ｒ⁵⁶、Ｒ⁵⁷、Ｒ⁵⁸及びＲ⁵⁹は、互いに同一の又は異なる基であって、少なくとも１つが水素原子、炭素数１以上の飽和又は不飽和の炭化水素基（隣接する炭化水素基同士が共同して環を形成してもよい。）、炭素数１以上の飽和又は不飽和の炭化水素オキシ基、炭素数１以上の飽和又は不飽和の炭化水素アミノ基、トリフルオロメチル基、シアノ基、又はＦ、Ｃｌ等のハロゲン原子である。）、
Ｒ⁵¹及びＲ⁵²は、互いに同一の又は異なる下記一般式（８）で表わされるナフチル基であり

（但し、前記一般式（８）において、Ｒ⁶⁰、Ｒ⁶¹、Ｒ⁶²、Ｒ⁶³、Ｒ⁶⁴、Ｒ⁶⁵及びＲ⁶⁶は、互いに同一の又は異なる基であって、少なくとも１つが水素原子、炭素数１以上の飽和又は不飽和の炭化水素基（隣接する炭化水素基同士が共同して環を形成してもよい。）、炭素数１以上の飽和又は不飽和の炭化水素オキシ基、炭素数１以上の飽和又は不飽和の炭化水素アミノ基、トリフルオロメチル基、シアノ基、又はＦ、Ｃｌ等のハロゲン原子である。）、
Ｒ⁵³及びＲ⁵⁴は、互いに同一の又は異なる基であって、それらの少なくとも１つが水素原子、シアノ基、ニトロ基、トリフルオロメチル基、又はＦ、Ｃｌ等のハロゲン原子である。］ That is, the present invention first relates to a bis (aminostyryl) phenanthrene compound (hereinafter referred to as the compound of the present invention) represented by the following general formula [I], [II] or [III].

[However, in the general formula [I],
R ¹ and R ³ are the same or different phenyl groups represented by the following general formula (1)

(However, in the said General formula (1), R < ⁷ >, R < ⁸ >, R < ⁹ >, R < ¹⁰ > and R < ¹¹ > are mutually the same or different groups, Comprising: At least one of them is a hydrogen atom, C1 or more Saturated or unsaturated hydrocarbon group (adjacent hydrocarbon groups may form a ring together), saturated or unsaturated hydrocarbon oxy group having 1 or more carbon atoms, saturated having 1 or more carbon atoms Or an unsaturated hydrocarbon amino group, trifluoromethyl group, cyano group, or a halogen atom such as F or Cl).
R ² and R ⁴ are the same or different groups selected from a phenyl group represented by the following general formula (2) or a naphthyl group represented by the following general formula (3).

(However, in the said General formula (2), R < ¹² >, R < ¹³ >, R < ¹⁴ >, R < ¹⁵ > and R < ¹⁶ > are mutually the same or different groups, Comprising: At least one of them is a hydrogen atom, C1 or more Saturated or unsaturated hydrocarbon group (adjacent hydrocarbon groups may form a ring together), saturated or unsaturated hydrocarbon oxy group having 1 or more carbon atoms, saturated having 1 or more carbon atoms Or an unsaturated hydrocarbon amino group, trifluoromethyl group, cyano group, or a halogen atom such as F or Cl).

(In the general formula (3), R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are the same or different groups, and at least one of them is a hydrogen atom. A saturated or unsaturated hydrocarbon group having 1 or more carbon atoms (adjacent hydrocarbon groups may form a ring together), a saturated or unsaturated hydrocarbon oxy group having 1 or more carbon atoms, A saturated or unsaturated hydrocarbon amino group having 1 or more carbon atoms, a trifluoromethyl group, a cyano group, or a halogen atom such as F or Cl).
R ⁵ and R ⁶ are the same or different from each other, and at least one of them is a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group, or a halogen atom such as F or Cl. ]

[However, in the general formula [II],
R ²⁴ , R ²⁵ and R ²⁶ are the same or different naphthyl groups represented by the following general formula (4).

(In the general formula (4), R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ are the same or different groups, and at least one of them is a hydrogen atom, carbon 1 or more saturated or unsaturated hydrocarbon groups (adjacent hydrocarbon groups may form a ring together), 1 or more saturated or unsaturated hydrocarbon oxy group, carbon number One or more saturated or unsaturated hydrocarbon amino groups, trifluoromethyl groups, cyano groups, or halogen atoms such as F and Cl).
R ²⁷ is a phenyl group represented by the following general formula (5) or a naphthyl group represented by the following general formula (6).

(In the general formula (5), R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , and R ⁴¹ are the same or different groups, and at least one of them is a hydrogen atom, saturated with 1 or more carbon atoms) Or an unsaturated hydrocarbon group (adjacent hydrocarbon groups may form a ring together), a saturated or unsaturated hydrocarbon oxy group having 1 or more carbon atoms, saturated or having 1 or more carbon atoms, or An unsaturated hydrocarbon amino group, a trifluoromethyl group, a cyano group, or a halogen atom such as F or Cl.)

(In the general formula (6), R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ are the same or different groups, and at least one is a hydrogen atom, carbon 1 or more saturated or unsaturated hydrocarbon groups (adjacent hydrocarbon groups may form a ring together), 1 or more saturated or unsaturated hydrocarbon oxy group, carbon number One or more saturated or unsaturated hydrocarbon amino groups, trifluoromethyl groups, cyano groups, or halogen atoms such as F and Cl).
R ²⁸ and R ²⁹ are the same or different groups, and at least one of them is a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group, or a halogen atom such as F or Cl. ]

[However, in the general formula [III],
R ⁴⁹ and R ⁵⁰ are the same or different phenyl groups represented by the following general formula (7).

(However, in the general formula (7), R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ and R ⁵⁹ are the same or different groups, and at least one is a hydrogen atom, saturated or having 1 or more carbon atoms, or Unsaturated hydrocarbon group (adjacent hydrocarbon groups may form a ring together), saturated or unsaturated hydrocarbon oxy group having 1 or more carbon atoms, saturated or unsaturated group having 1 or more carbon atoms A saturated hydrocarbon amino group, a trifluoromethyl group, a cyano group, or a halogen atom such as F or Cl).
R ⁵¹ and R ⁵² are the same or different naphthyl groups represented by the following general formula (8).

(In the general formula (8), R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ are the same or different groups, and at least one of them is a hydrogen atom, carbon 1 or more saturated or unsaturated hydrocarbon groups (adjacent hydrocarbon groups may form a ring together), 1 or more saturated or unsaturated hydrocarbon oxy group, carbon number One or more saturated or unsaturated hydrocarbon amino groups, trifluoromethyl groups, cyano groups, or halogen atoms such as F and Cl).
R ⁵³ and R ⁵⁴ are the same or different from each other, and at least one of them is a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group, or a halogen atom such as F or Cl. ]

  The compound of the present invention can be effectively used as an organic light-emitting material that emits red to green, particularly red light, and has a high glass transition point and melting point, and is electrically, thermally, or chemically. In addition to being excellent in stability, it is amorphous and can easily form a glass state, so that vapor deposition or the like can also be performed. That is, the compound of the present invention represented by the above general formula [I], [II] or [III] is particularly excellent in red light emission because of its specific structure (in particular, an electron-withdrawing group such as a cyano group in a phenanthrene group). This is a material that exhibits an amorphous property that is advantageous for film-forming properties and durability such as vapor deposition. It is possible to provide an organic electroluminescence device that exhibits high luminance and stable red to green, particularly red light emission, at various wavelengths.

  According to the present invention, the bis (aminostyryl) phenanthrene compound represented by the above general formula [I], [II], or [III] is red to green having different emission maximum wavelengths depending on the substituent to be introduced. In particular, it can be effectively used as an organic light-emitting material that emits strong red light, has a high melting point, has excellent heat resistance, and has excellent electrical, thermal, or chemical stability. It is easy to form a crystalline and glassy state, has a sublimation property, and can form a uniform amorphous film by vacuum deposition or the like. In addition, this compound can be produced by a general and highly efficient method via the synthetic intermediate of the present invention.

［但し、前記一般式[IV]において、Ａｒ¹、Ａｒ²、Ａｒ³及びＡｒ⁴はそれぞれ、置換基を有してもよい互いに同一の又は異なるアリール基であって、置換基を有する場合には下記一般式（９）、（１０）、（１１）、（１２）、（１３）、（１４）、（１５）、（１６）又は（１７）で表わされるアリール基から選ばれた基である。

（但し、前記一般式（９）、（１０）、（１１）、（１２）、（１３）、（１４）、（１５）、（１６）及び（１７）において、Ｒ⁶⁷、Ｒ⁶⁸、Ｒ⁶⁹、Ｒ⁷⁰、Ｒ⁷¹、Ｒ⁷²、Ｒ⁷³、Ｒ⁷⁴、Ｒ⁷⁵、Ｒ⁷⁶、Ｒ⁷⁷、Ｒ⁷⁸、Ｒ⁷⁹、Ｒ⁸⁰及びＲ⁸¹は、互いに同一の又は異なる炭素数１以上の飽和又は不飽和の炭化水素基（隣接する炭化水素基同士が共同して環を形成してもよい。）であり、ｎは０〜５の整数であり、ｍは０〜３の整数であり、ｌは０〜３の整数である。）］ The compound of the present invention is preferably represented by the following general formula [IV].

[However, in the general formula [IV], Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each the same or different aryl group which may have a substituent, and each has a substituent. Is a group selected from aryl groups represented by the following general formula (9), (10), (11), (12), (13), (14), (15), (16) or (17) is there.

(However, in the general formulas (9), (10), (11), (12), (13), (14), (15), (16) and (17), R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ and R ⁸¹ are the same or different and have one or more saturated carbon atoms Or an unsaturated hydrocarbon group (adjacent hydrocarbon groups may form a ring together), n is an integer of 0 to 5, m is an integer of 0 to 3, l is an integer from 0 to 3)]]

Here, ^R67 , ^R68 , ^R69 , ^R70 , ^R71 , ^R72 , ^R73 , ^R74 , ^R75 , ^R76 , ^R77 , ^R78 , ^R79 , ^R80 and ^R81 are carbon. It is good that it is a hydrocarbon group of number 1-6.

（但し、前記一般式（１８）において、Ｒ⁸²は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（１９）において、Ｒ⁸³及びＲ⁸⁴は、互いに同一の又は異なる基であって、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（２０）において、Ｒ⁸⁵は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（２１）において、Ｒ⁸⁶及びＲ⁸⁷は、互いに同一の又は異なる基であって、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（２２）において、Ｒ⁸⁸は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（２３）において、Ｒ⁸⁹及びＲ⁹⁰は、互いに同一の又は異なる基であって炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（２４）において、Ｒ⁹¹は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（２５）において、Ｒ⁹²は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（２６）において、Ｒ⁹³は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（２７）において、Ｒ⁹⁴は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（２８）において、Ｒ⁹⁵及びＲ⁹⁶は、互いに同一の又は異なる基であって、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（２９）において、Ｒ⁹⁷は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（３０）において、Ｒ⁹⁸及びＲ⁹⁹は、互いに同一の又は異なる基であって、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（３１）において、Ｒ¹⁰⁰は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（３２）において、Ｒ¹⁰¹及びＲ¹⁰²は、互いに同一の又は異なる基であって、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（３３）において、Ｒ¹⁰³は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（３４）において、Ｒ¹⁰⁴及びＲ¹⁰⁵は、互いに同一の又は異なる基であって、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（３５）において、Ｒ¹⁰⁶は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（３６）において、Ｒ¹⁰⁷及びＲ¹⁰⁸は、互いに同一の又は異なる基であって、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（３７）において、Ｒ¹⁰⁹は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（３８）において、Ｒ¹¹⁰は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（３９）において、Ｒ¹¹¹は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（４０）において、Ｒ¹¹²は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（４１）において、Ｒ¹¹³及びＲ¹¹⁴は、互いに同一の又は異なる基であって、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（４２）において、Ｒ¹¹⁵は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（４３）において、Ｒ¹¹⁶及びＲ¹¹⁷は、互いに同一の又は異なる基であって、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（４４）において、Ｒ¹¹⁸は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（４５）において、Ｒ¹¹⁹及びＲ¹²⁰は、互いに同一の又は異なる基であって、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（４６）において、Ｒ¹²¹は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（４７）において、Ｒ¹²²及びＲ¹²³は互いに、同一の又は異なる基であって、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（４８）において、Ｒ¹²⁴は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（４９）において、Ｒ¹²⁵及びＲ¹²⁶は、互いに同一の又は異なる基であって、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（５０）において、Ｒ¹²⁷は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（５１）において、Ｒ¹²⁸は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（５２）において、Ｒ¹²⁹は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（５３）において、Ｒ¹³⁰は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（５４）において、Ｒ¹³¹及びＲ¹³²は、互いに同一の又は異なる基であって、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（５５）において、Ｒ¹³³は、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。）

（但し、前記一般式（５６）において、Ｒ¹³⁴及びＲ¹³⁵は、互いに同一の又は異なる基であって、炭素数１〜６の飽和又は不飽和のアルキル基、又は置換基を有してもよいアリール基である。） More specifically, the compounds of the present invention are represented by the following general formulas (18), (19), (20), (21), (22), (23), (24), (25), (26). , (27), (28), (29), (30), (31), (32), (33), (34), (35), (36), (37), (38), ( 39), (40), (41), (42), (43), (44), (45), (45), (46), (47), (48), (49), (50) , (51), (52), (53), (54), (55) or (56) is preferable.

(However, in the said General formula (18), ^R82 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (19), ^R83 and ^R84 are mutually the same or different groups, Comprising: It is a C1-C6 saturated or unsaturated alkyl group, or a substituent. A good aryl group.)

(However, in the said General formula (20), ^R85 is a C1-C6 saturated or unsaturated alkyl group or the aryl group which may have a substituent.)

(However, in the said General formula (21), ^R86 and ^R87 are mutually the same or different groups, Comprising: It is a C1-C6 saturated or unsaturated alkyl group, or a substituent. A good aryl group.)

(However, in the said General formula (22), ^R88 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (23), ^R89 and ^R90 are mutually the same or different groups, Comprising: You may have a C1-C6 saturated or unsaturated alkyl group, or a substituent. An aryl group.)

(However, in the said General formula (24), ^R91 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (25), ^R92 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (26), ^R93 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (27), ^R94 is a C1-C6 saturated or unsaturated alkyl group or the aryl group which may have a substituent.)

(However, in the general formula (28), R ⁹⁵ and R ⁹⁶ may be the same or different from each other, and may have a saturated or unsaturated alkyl group having 1 to 6 carbon atoms, or a substituent. A good aryl group.)

(However, in the said General formula (29), ^R97 is a C1-C6 saturated or unsaturated alkyl group or the aryl group which may have a substituent.)

(However, in the said General formula (30), ^R98 and ^R99 are mutually the same or different groups, Comprising: It is a C1-C6 saturated or unsaturated alkyl group, or a substituent. A good aryl group.)

(However, in the general formula (31), R ¹⁰⁰ is an alkyl group, or an aryl group which may have a substituent, saturated or unsaturated having 1 to 6 carbon atoms.)

(However, in the said General formula (32), ^R101 and ^R102 are mutually the same or different groups, Comprising: It is a C1-C6 saturated or unsaturated alkyl group, or a substituent. A good aryl group.)

(However, in the general formula (33), R ¹⁰³ is an alkyl group, or an aryl group which may have a substituent, saturated or unsaturated having 1 to 6 carbon atoms.)

(However, in the said General formula (34), ^R104 and ^R105 are mutually the same or different groups, Comprising: Even if it has a C1-C6 saturated or unsaturated alkyl group, or a substituent, A good aryl group.)

(However, in the said General formula (35), ^R106 is a C1-C6 saturated or unsaturated alkyl group or the aryl group which may have a substituent.)

(However, in the said General formula (36), ^R107 and ^R108 are mutually the same or different groups, Comprising: It is a C1-C6 saturated or unsaturated alkyl group, or a substituent. A good aryl group.)

(However, in the said General formula (37), ^R109 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (38), ^R110 is a C1-C6 saturated or unsaturated alkyl group or the aryl group which may have a substituent.)

(However, in the said General formula (39), ^R111 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (40), ^R112 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the general formula (41), R ¹¹³ and R ¹¹⁴ may be the same or different from each other, and may have a saturated or unsaturated alkyl group having 1 to 6 carbon atoms, or a substituent. A good aryl group.)

(However, in the said General formula (42), ^R115 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the general formula (43), R ¹¹⁶ and R ¹¹⁷ is an identical or different groups from each other, may have an alkyl group, or a substituent of the saturated or unsaturated having 1 to 6 carbon atoms A good aryl group.)

(However, in the said General formula (44), ^R118 is a C1-C6 saturated or unsaturated alkyl group or the aryl group which may have a substituent.)

(However, in the said General formula (45), ^R119 and ^R120 are mutually the same or different groups, Comprising: Even if it has a C1-C6 saturated or unsaturated alkyl group, or a substituent, A good aryl group.)

(However, in the said General formula (46), ^R121 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (47), ^R122 and ^R123 are mutually the same or different groups, Comprising: It is a C1-C6 saturated or unsaturated alkyl group, or a substituent. A good aryl group.)

(However, in the said General formula (48), ^R124 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (49), ^R125 and ^R126 are mutually the same or different groups, Comprising: It is a C1-C6 saturated or unsaturated alkyl group, or a substituent. A good aryl group.)

(However, in the said General formula (50), ^R127 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (51), ^R128 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (52), ^R129 is a C1-C6 saturated or unsaturated alkyl group or the aryl group which may have a substituent.)

(However, in the general formula (53), R ¹³⁰ is an alkyl group, or an aryl group which may have a substituent, saturated or unsaturated having 1 to 6 carbon atoms.)

(However, in the said General formula (54), ^R131 and ^R132 are mutually the same or different groups, Comprising: Even if it has a C1-C6 saturated or unsaturated alkyl group, or a substituent, A good aryl group.)

(However, in the said General formula (55), ^R133 is a C1-C6 saturated or unsaturated alkyl group or the aryl group which may have a substituent.)

(However, in the said General formula (56), ^R134 and ^R135 are mutually the same or different groups, Comprising: It is a C1-C6 saturated or unsaturated alkyl group, or a substituent. A good aryl group.)

The compounds of the present invention include the following structural formulas (60) -1 to (60) -16, (61) -1 to (61) -16, (62) -1 to (62) -16, (63)- 1 to (63) -16, (64) -1 to (64) -16, (65) -1 to (65) -16, and (66) -1 to (66) -16. Illustrated specifically. In the following exemplary compounds, as the number of cyano groups, trifluoromethyl groups, and halogen atoms introduced into the phenanthrene group increases, the emission wavelength tends to be longer.

In addition to these, the following compounds can also be exemplified.

（但し、前記一般式［Ｖ］において、Ｒ¹³⁶及びＲ¹³⁷はそれぞれ、前記Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ²⁴、Ｒ²⁵、Ｒ²⁶、Ｒ²⁷、Ｒ⁴⁹、Ｒ⁵⁰、Ｒ⁵¹又はＲ⁵²に相当するアリール基である。）

（但し、前記一般式［VI］及び［VII］において、Ｒ¹³⁸は炭化水素基であり、Ｒ¹³⁹及びＲ¹⁴⁰はそれぞれ、前記Ｒ⁵、Ｒ⁶、Ｒ²⁸、Ｒ²⁹、Ｒ⁵³又はＲ⁵⁴に相当する基であり、ＸはＦ、Ｃｌ等のハロゲン原子である。） The present invention also provides an aminobenzaldehyde represented by the following general formula [V]; a diphosphonic acid ester represented by the following general formula [VI] or a general formula [ And a diphosphonium represented by VII] to obtain a bis (aminostyryl) phenanthrene compound represented by the general formula [I], [II] or [III]. Is.

(However, in the general formula [V], R ¹³⁶ and R ¹³⁷ are respectively R ¹ , R ² , R ³ , R ⁴ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ⁴⁹ , R ⁵⁰ , An aryl group corresponding to R ⁵¹ or R ^52. )

(However, in the general formulas [VI] and [VII], R ¹³⁸ is a hydrocarbon group, and R ¹³⁹ and R ¹⁴⁰ are R ⁵ , R ⁶ , R ²⁸ , R ²⁹ , R ⁵³ or R ^{54, respectively.} X is a halogen atom such as F or Cl.)

  Specifically, in the production method of the present invention, the condensation is performed by a Wittig-Horner reaction or a Wittig reaction, and the diphosphonic acid ester and / or the diphosphonium is treated with a base in a solvent. Thus, a carbanion is generated, and this carbanion and the 4- (N, N-diarylamino) benzaldehyde are condensed to obtain the various bis (aminostyryl) phenanthrene compounds described above.

（但し、前記一般式[IV]において、Ａｒ¹、Ａｒ²、Ａｒ³及びＡｒ⁴はそれぞれ、前記したものと同じである。）、下記一般式（５７）で表わされる４−（Ｎ,Ｎ−ジアリールアミノ）ベンズアルデヒドと；下記一般式（５８）で表わされるジホスホン酸エステル又は下記一般式（５９）で表わされるジホスホニウムと；を縮合させるものである。

（但し、前記一般式（５７）、（５８）及び（５９）において、Ａｒ⁵及びＡｒ⁶はそれぞれ、前記Ａｒ¹、Ａｒ²、Ａｒ³又はＡｒ⁴と同じであり、Ｒ¹³⁸は炭化水素基（例えば炭素数１〜４の飽和炭化水素基）であり、ＸはＦ、Ｃｌ、Ｂｒ等のハロゲン原子である。） For example, in obtaining a bis (aminostyryl) phenanthrene compound compound represented by the following general formula [IV]:

(However, in the general formula ^{[IV], Ar 1, Ar} 2, respectively Ar ³ and Ar ⁴ are the same as those described above.), Represented by the following general formula (57) 4-(N, N -Diarylamino) benzaldehyde; and a diphosphonic acid ester represented by the following general formula (58) or a diphosphonium represented by the following general formula (59).

(However, in the general formulas (57), (58) and (59), Ar ⁵ and Ar ⁶ are the same as Ar ¹ , Ar ² , Ar ³ or Ar ⁴ , respectively, and R ¹³⁸ is a hydrocarbon group. (For example, a saturated hydrocarbon group having 1 to 4 carbon atoms), and X is a halogen atom such as F, Cl, or Br.)

This reaction is represented by a scheme, for example, as shown in Reaction Scheme 1.

  This reaction begins with the generation of a carbanion by treating the compound of general formula (58) or (59) with a base in a suitable solvent, and then the carbanion is converted to the general formula (57). Completed by condensation with an aldehyde. The following can be considered as a combination of a base and a solvent.

  Sodium hydroxide / water, sodium carbonate / water, potassium carbonate / water, sodium ethoxide / ethanol or dimethylformamide, sodium methoxide / methanol-diethyl ether mixed solvent or dimethylformamide, triethylamine / ethanol or diglyme or chloroform or nitromethane, pyridine / Methylene chloride or nitromethane, 1,5-disazabicyclo [4.3.0] non-5-ene / dimethyl sulfoxide, potassium t-butoxide / dimethyl sulfoxide or tetrahydrofuran or benzene or dimethylformamide, phenyl lithium / diethyl ether or tetrahydrofuran, t-Butyl lithium / diethyl ether or tetrahydrofuran, sodium amide / ammonia, sodium hydride / dimethyl phosphate Lumamide or tetrahydrofuran, triethyl sodium / diethyl ether, tetrahydrofuran or the like.

  Since this reaction proceeds at a relatively low temperature (−30 ° C. to 30 ° C.) and is selective, in addition to easy purification of the target product by chromatography, the compound of the present invention represented by the general formula [IV] Since the crystallinity is high, the purity can be improved by recrystallization. The recrystallization method is not particularly limited, but a method of dissolving in acetone and adding hexane, or a method of heating and dissolving in toluene, concentration and cooling is simple. This reaction may be carried out at normal pressure for 3 to 24 hours.

  Bis (aminostyryl) phenanthrene compounds represented by the general formulas (18) to (56) can be obtained by the method for producing a compound of the present invention. Specifically, the structural formulas (60) -1 to (60) ) -16, (61) -1 to (61) -16, (62) -1 to (62) -16, (63) -1 to (63) -16, (64) -1 to (64)- 16, bis (aminostyryl) phenanthrene compounds such as (65) -1 to (65) -16 and (66) -1 to (66) -16 can be obtained.

  The present invention also provides various compounds suitable as synthetic intermediates for the compounds of the present invention.

  That is, the diphosphonic acid ester represented by the general formula [VI] used as a synthesis intermediate of the bis (aminostyryl) phenanthrene compound represented by the general formula [I], [II] or [III] or the general formula Diphosphonium represented by the formula [VII].

（但し、前記一般式（５８）及び（５９）において、Ｒ¹³⁸及びＸはそれぞれ前記したものと同じである。） This synthetic intermediate (hereinafter referred to as the synthetic intermediate 1 of the present invention) is specifically represented by the following general formula (58) or (59).

(However, in the general formulas (58) and (59), R ¹³⁸ and X are the same as those described above.)

  The synthetic intermediate 1 of the present invention can be derived from the synthetic intermediate 2 as a precursor thereof as follows.

（但し、一般式［VIII］において、Ｒ¹³⁹及びＲ¹⁴⁰は、互いに同一の又は異なる基であって、それらの少なくとも１つが水素原子、シアノ基、ニトロ基、トリフルオロメチル基、又はＦ、Ｃｌ等のハロゲン原子であり、ＸはＦ、Ｃｌ等のハロゲン原子である。）

(但し、前記一般式[IX]において、Ｒ¹³⁸は炭化水素基、特に炭素数１〜４の飽和又は不飽和の炭化水素基である。) By reacting a dihalogenated aryl compound represented by the following general formula [VIII] (synthetic intermediate 2) with a trialkyl phosphite or triphenylphosphine (PPh ₃ ) represented by the following general formula [IX] The diphosphonic acid ester represented by the general formula [VI] or the diphosphonium represented by the general formula [VII] is obtained as the synthetic intermediate 1. This reaction can be carried out in a solvent such as xylene having a boiling point of 120 ° C. or higher, or in a large excess of trialkyl phosphite at a reaction temperature of 120 ° C. to 160 ° C. at normal pressure for a reaction time of 30 minutes to 24 hours. You can go.

(In the general formula [VIII], R ¹³⁹ and R ¹⁴⁰ are the same or different groups, and at least one of them is a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group, or F, Cl. X is a halogen atom such as F or Cl.)

(However, in the general formula [IX], R ¹³⁸ is a hydrocarbon group, particularly a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.)

  The present invention also provides a halogenated aryl compound represented by the above general formula [VIII] (the synthetic intermediate 2 of the present invention) as a synthetic intermediate for obtaining the synthetic intermediate 1.

  The synthetic intermediate 2 of the present invention is obtained by reacting a dimethylphenanthrene compound represented by the following general formula [X] with an N-halogenated succinimide represented by the following general formula [XI] under light irradiation. be able to. For example, in a solvent such as carbon tetrachloride, chloroform, benzene, chlorobenzene, using a light source such as a high pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, a halogen lamp, sunlight, or a fluorescent lamp, a temperature of 20 to 120 ° C. and a normal pressure of 30 to 30 React with a reaction time of 72 hours. If the reaction conditions are mild or the reaction time is short, a monohalogenated phenanthrene of the following general formula [XII], which is the synthetic intermediate 3, is formed.

（但し、一般式［Ｘ］において、Ｒ¹³⁹及びＲ¹⁴⁰は、互いに同一の又は異なる基であって、それらの少なくとも１つが水素原子、シアノ基、ニトロ基、トリフルオロメチル基又はＦ、Ｃｌ等のハロゲン原子である。）

(However, in the general formula [X], R ¹³⁹ and R ¹⁴⁰ is an identical or different groups from each other, at least one of them a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group, or F, Cl, etc. Of halogen atoms.)

（但し、前記一般式［XI］において、ＸはＦ、Ｃｌ、Ｂｒ等のハロゲン原子である。）

（但し、前記一般式［XII］において、Ｒ¹³⁹、Ｒ¹⁴⁰は前記したものと同じであり、ＸはＦ、Ｃｌ、Ｂｒ等のハロゲン原子である。）

(However, in the general formula [XI], X is a halogen atom such as F, Cl, or Br.)

(However, in the general formula [XII], R ¹³⁹ and R ¹⁴⁰ are the same as those described above, and X is a halogen atom such as F, Cl, or Br.)

  The reaction for obtaining each of the synthetic intermediates 1, 2 and 3 described above can be shown, for example, in the following reaction scheme 2.

  FIGS. 1-6 shows the example of the organic electroluminescent element (EL element) which uses the compound of this invention as an organic luminescent material, respectively.

  FIG. 1 shows a top emission type organic electroluminescent device A in which emitted light 20 is transmitted through a cathode 2, and the emitted light 20 can be observed from the protective layer 4 side. FIG. 2 shows a bottom emission type organic electroluminescent device B that also obtains reflected light from the cathode 3 as emitted light 20.

In the figure, reference numeral 1 denotes a substrate for forming an organic electroluminescent element. Glass, plastic and other suitable materials can be used. When the organic electroluminescent element is driven in an active matrix, it may be used as a substrate incorporating a TFT (thin film transistor). Moreover, when using an organic electroluminescent element in combination with another display element, a board | substrate can also be shared. Reference numeral 2 denotes a transparent or opaque electrode. In the bottom emission type organic electroluminescence element, ITO (Indium tin oxide), IZO (Indium zinc oxide), SnO ₂ or the like can be used. In the top emission type organic electroluminescence element, Cr, Fe, Co, Ni, Cu, Ta, W, Pt, Mo, Au, or alloys thereof can be used.

  Reference numeral 5 denotes an organic light emitting layer which contains the above-described bis (aminostyryl) phenanthrene compound as a light emitting material. About this light emitting layer, conventionally well-known various structures can be used as a layer structure from which the organic electroluminescence 20 is obtained.

  As will be described later, for example, when a material constituting either the hole transport layer or the electron transport layer has a light emitting property, a structure in which these thin films are stacked can be used. Furthermore, in order to improve the charge transport performance within the range of satisfying the object of the present invention, either or both of the hole transport layer and the electron transport layer have a structure in which thin films of plural kinds of materials are laminated, or plural kinds of materials. It does not prevent the use of a thin film having a composition mixed with

  Further, in order to improve the light emission performance, at least one kind of fluorescent material is used, and this thin film is sandwiched between the hole transport layer and the electron transport layer, and at least one kind of fluorescent material is properly used. You may use the structure included in the hole transport layer or the electron transport layer, or both. In these cases, in order to improve luminous efficiency, a thin film for controlling the transport of holes or electrons can be included in the layer structure.

  Since the bis (aminostyryl) phenanthrene compound represented by the above general formula [I] has both electron transport performance and hole transport performance, it can be used as a light emitting layer that also serves as an electron transport layer in the device structure, or a positive It can also be used as a light emitting layer also serving as a hole transport layer. In addition, the compound can be used as a light emitting material in a structure in which the light emitting layer is sandwiched between an electron transport layer and a hole transport layer.

  A mixed layer containing two or more different compounds among the phenanthrene compounds represented by the general formula [I] may be used as the light emitting layer. By selecting an appropriate combination of two or more types of compounds, it is possible to arbitrarily select the emission color without greatly changing the electrical characteristics of the device.

1 and 2, reference numeral 3 denotes a cathode. As an electrode material, a metal such as Ag, Au, Al, Cr, or In, or an alloy of this metal and an active metal such as Li, Mg, or Ca is used. Alternatively, a structure in which these layers are stacked can be used (hereinafter the same). The cathode may further have a structure in which an oxide of alkali metal or alkaline earth metal, fluoride (LiF, Li ₂ O, etc.) or the like is combined or laminated (hereinafter the same). In the top emission type organic electroluminescent device, the light transmittance suitable for the application can be obtained by adjusting the thickness of the cathode. And the light emission can be extracted to the cathode 3 side by configuring the anode 2 with a material having a high light reflectance. Further, in the figure, reference numeral 4 denotes a sealing / protecting layer, and the effect is enhanced by adopting a structure that covers the entire organic electroluminescent element. An appropriate material can be used as long as the airtightness is maintained.

  In the organic electroluminescent device according to the present invention, the organic layer has an organic laminated structure (single heterostructure) in which a hole transport layer and an electron transport layer are laminated, and the hole transport layer or the electron transport. The phenanthrene compound may be used as a layer forming material. Alternatively, the organic layer has an organic laminated structure (double heterostructure) in which a hole transport layer, a light emitting layer, and an electron transport layer are sequentially laminated, and the phenanthrene compound may be used as a material for forming the light emitting layer. .

  As an example of an organic electroluminescent device having such an organic laminated structure, FIG. 3 shows that a translucent anode 2, a hole transport layer 6 and an electron transport layer 7 are formed on a translucent substrate 1. 1 is a bottom-emitting organic electroluminescence device C having a single hetero structure, which has a laminated structure in which an organic layer 5a made of a cathode and a cathode 3 are sequentially laminated, and this laminated structure is sealed by a protective layer 4. .

  In an element having a single heterostructure, either or both of the hole transport layer 6 and the electron transport layer 7 are considered to serve as the light emitting layer, and organic electroluminescence is generated from the interface between the hole transport layer 6 and the electron transport layer 7. Obtained as light emission of a predetermined wavelength.

  In the case of a layer configuration in which the light emitting layer is omitted as shown in FIG. 3, light emission 20 having a predetermined wavelength is generated from the interface between the hole transport layer 6 and the electron transport layer 7. These luminescences are observed from the substrate 1 side.

  Further, FIG. 4 shows that a light-transmitting anode 2, an organic layer 5 b composed of a hole transport layer 10, a light emitting layer 11, and an electron transport layer 12, and a cathode 3 are sequentially formed on a light-transmitting substrate 1. This is a bottom emission organic electroluminescent element D having a double hetero structure, which has a laminated structure in which the laminated structure is sealed by a protective layer 4.

  In the organic electroluminescence device shown in FIG. 4, by applying a DC voltage between the anode 2 and the cathode 3, holes injected from the anode 2 are injected through the hole transport layer 10 and from the cathode 3. The emitted electrons reach the light emitting layer 11 through the electron transport layer 12. As a result, recombination of electrons / holes occurs in the light emitting layer 11 to generate excitons, and light having a predetermined wavelength is generated from the excitons.

  In each of the organic electroluminescent devices C and D described above, materials that can be used as a hole transporting material having charge transporting ability include benzidine or a derivative thereof, styrylamine or a derivative thereof, triphenylmethane or a derivative thereof, Porphyrin or derivative thereof, triazole or derivative thereof, imidazole or derivative thereof, oxadiazole or derivative thereof, polyarylalkane or derivative thereof, phenylenediamine or derivative thereof, arylamine or derivative thereof, oxazole or derivative thereof, anthracene or derivative thereof , Fluorenone or derivatives thereof, hydrazone or derivatives thereof, stilbene or derivatives thereof, or heterocyclic conjugated systems such as polysilane compounds, vinylcarbazole compounds, thiophene compounds, aniline compounds, etc. Nomar, oligomers, polymers, and the like (hereinafter, the same).

  Specifically, α-naphthylphenyldiamine, porphyrin, metal tetraphenylporphyrin, metal naphthalocyanine, 4,4 ′, 4 ″ -trimethyltriphenylamine, 4,4 ′, 4 ”-tris (3-methylphenylphenyl Amino) triphenylamine, N, N, N ′, N′-tetrakis (p-tolyl) p-phenylenediamine, N, N, N ′, N′-tetraphenyl-4,4′-diaminobiphenyl, N— Examples include, but are not limited to, phenylcarbazole, 4-di-p-tolylaminostilbene, poly (paraphenylene vinylene), poly (thiophene vinylene), poly (2,2′-thienylpyrrole), and the like. .

  Examples of a material that can be used as an electron transporting material having charge transporting ability include quinoline or a derivative thereof, perylene or a derivative thereof, bisstyryl or a derivative thereof, pyrazine or a derivative thereof (hereinafter the same).

Specific examples include 8-hydroxyquinoline aluminum (Alq ₃ ), anthracene, naphthalene, phenanthrene, pyrene, chrysene, perylene, butadiene, coumarin, acridine, stilbene, and derivatives thereof.

  For the substrate 1, for example, a light-transmitting material such as glass or plastic can be appropriately used. Further, this substrate may be shared when used in combination with other display elements or when the stacked structure shown in FIGS. 3 and 4 is arranged in a matrix.

  Each of the elements C and D can have a bottom emission type or a top emission type structure. Between the anode 2 and the hole transport layer 6 (or the hole transport layer 10), for the purpose of improving the charge injection efficiency, an inorganic substance, an organic substance or an organometallic compound such as 2-TNATA (4, 4 ′, 4) is used. A thin film made of “-tris (2-naphthylphenylamino) triphenylamine), a porphyrin compound described in US Pat. No. 4,720,432 or the like (hereinafter the same) may be provided. When formed of a conductive material, an insulating film may be provided on the side surface of the anode 2.

  Moreover, the organic layer 5a in the organic electroluminescent element C is an organic layer in which the hole transport layer 6 and the electron transport layer 7 are laminated, and the phenanthrene compound described above is contained in one or both of these layers, and the light emitting property. The hole transport layer 6 or the electron transport layer 7 may be formed. The organic layer 5b in the organic electroluminescent element D is an organic layer in which the hole transport layer 10, the light emitting layer 11 containing the phenanthrene compound, and the electron transport layer 12 are stacked. be able to. For example, either or both of the hole transport layer and the electron transport layer may have a light emitting property.

  In particular, the hole transport layer 6 or the electron transport layer 7 and the light emitting layer 11 are preferably made of the compound of the present invention, but these layers may be formed only of the compound of the present invention, or the present invention. It may be formed by co-evaporation of the above compound with another hole or electron transport material.

  In the hole transport layer, a hole transport layer in which a plurality of types of hole transport materials are stacked may be formed in order to improve hole transport performance.

  In the organic electroluminescent device C, the light emitting layer may be the electron transporting light emitting layer 7, but depending on the voltage applied from the power supply 8, light may be emitted from the hole transporting layer 6 or its interface. Similarly, in the organic electroluminescent element D, the light emitting layer may be the electron transport layer 12 or the hole transport layer 10 in addition to the layer 11. In order to improve the light emitting performance, it is preferable that the light emitting layer 11 using at least one fluorescent material is sandwiched between the hole transport layer and the electron transport layer. Or you may comprise the structure which contained this fluorescent material in the positive hole transport layer or the electron carrying layer, or these both layers. In such a case, in order to improve luminous efficiency, a thin film (such as a hole blocking layer or an exciton generation layer) for controlling the transport of holes or electrons can be included in the layer configuration.

  The material used for the cathode 3 may be an alloy of an active metal such as Li, Mg, or Ca and a metal such as Ag, Al, or In, and may have a structure in which these metal layers are laminated. It should be noted that an organic electroluminescent element suitable for the application can be produced by appropriately selecting the thickness and material of the cathode.

  Moreover, the protective layer 4 acts as a sealing film, and can improve the charge injection efficiency and the light emission efficiency by covering the entire organic electroluminescence device. If the airtightness is maintained, a material such as a single metal or alloy such as aluminum, gold, or chromium, a silicon compound such as silicon oxide or silicon nitride, or an organic material can be selected as appropriate.

  FIG. 5 has a laminated structure in which an anode 2, an organic layer 5 c composed of a hole transport layer 6 and an electron transport layer 7, and a transparent or translucent cathode 3 are sequentially laminated on the substrate 1. This is a top emission organic electroluminescent element E having a single hetero structure, in which this laminated structure is sealed by a protective layer 4. In this case, light emission 20 having a predetermined wavelength is generated from the interface between the hole transport layer 6 and the electron transport layer 7, and this light emission is observed from the cathode 3 or the protective layer 4 side.

  FIG. 6 shows that an anode 2, an organic layer 5 d composed of a hole injection layer 9, a hole transport layer 10, a light emitting layer 11 and an electron transport layer 12, and a transparent or translucent cathode 3 are formed on a substrate 1. This is a top emission organic electroluminescent element F having a laminated structure that is sequentially laminated, and the laminated structure is sealed by a protective layer 4. Also in this organic electroluminescent element, as in the organic electroluminescent element shown in FIG. 4, recombination of electrons / holes occurs in the light emitting layer 11 to generate excitons, and light emission of a predetermined wavelength is generated from the excitons. Will occur.

  In each of the organic electroluminescent elements E and F described above, the substrate 1 can be appropriately made of a light reflective material such as Ag, Au, Al, Cr, In, or an alloy thereof. This substrate may be shared when used in combination with other display elements or when the stacked structure shown in FIGS. 5 and 6 is arranged in a matrix.

  Further, the anode 2 on the substrate 1 is a reflective electrode, and Ag, Au, Al, Cr, In, or an alloy thereof can be used, and ITO or the like can be laminated and used, and the thickness thereof is a film formation. In view of the properties and reflectivity, the thickness is preferably 50 nm or more, and can be 200 nm or less. When such an anode is used, the substrate 1 is not limited to the light reflecting material described above, and may be made of a transparent or translucent material such as glass.

  Further, as shown in FIG. 6, between the anode 2 and the hole transport layer 10 (or the hole transport layer 6), a positive electrode made of an inorganic material, an organic material or an organometallic compound is used for the purpose of improving the charge injection efficiency. A hole injection layer 9 may be provided. When the protective layer 4 is formed of a conductive material such as metal, an insulating film may be provided on the side surface of the anode 2 for insulation separation.

  The organic layer 5c in the organic electroluminescent element E is an organic layer in which a hole transport layer 6 and an electron transport layer 7 are laminated, and as one of these layers, a mixed layer containing the above-described phenanthrene compound has a light emitting property. The hole transport layer 6 or the electron transport layer 7 may be formed. The organic layer 5d in the organic electroluminescent element F is an organic layer in which a hole transport layer 10, a light-emitting layer 11 made of the phenanthrene compound, and an electron transport layer 12 are stacked. Can be taken. For example, either or both of the hole transport layer and the electron transport layer may emit light.

  In the hole transport layer, a hole transport layer in which a plurality of types of hole transport materials are stacked may be formed in order to improve hole transport performance.

  In the organic electroluminescent element E, the light emitting layer may be the electron transporting light emitting layer 7, but depending on the voltage applied from the power supply 8, light may be emitted from the hole transporting layer 6 or its interface. Similarly, in the organic electroluminescent element F, the light emitting layer may be the electron transport layer 12 or the hole transport layer 10 in addition to the layer 11. In order to improve the light emitting performance, it is preferable that the light emitting layer 11 using at least one fluorescent material is sandwiched between the hole transport layer and the electron transport layer. Or you may comprise the structure which contained this fluorescent material in the positive hole transport layer or the electron carrying layer, or these both layers. In such a case, in order to improve luminous efficiency, a thin film (such as a hole blocking layer or an exciton generation layer) for controlling the transport of holes or electrons can be included in the layer configuration.

  The material used for the cathode 3 may be an alloy of an active metal such as Li, Mg, or Ca and a metal such as Ag, Al, or In, and may have a structure in which these metal layers are laminated. An organic electroluminescent element suitable for the application can be produced by appropriately selecting the thickness and material of the cathode, but the thickness of the cathode is preferably about 0.5 to 15 nm, more preferably about 0.5 to 5 nm.

  Moreover, the protective layer 4 acts as a sealing film, and can improve the charge injection efficiency and the light emission efficiency by covering the entire organic electroluminescence device. Note that, as long as the airtightness is maintained, a material such as a single metal such as aluminum, gold, chromium, silicon oxide, or silicon nitride, an alloy, or a compound can be appropriately selected.

  Each of the organic electroluminescent elements E and F described above has a structure in which the light emitting layer is sandwiched between the anode and the cathode, and the emitted light causes multiple interference between the anode and the cathode. By appropriately selecting the optical characteristics such as the reflectance and transmittance of the anode and the cathode and the film thickness of the organic layer sandwiched between them, the multiple interference effect can be positively utilized. , F can be used to control the emission wavelength. Thereby, it is also possible to improve the emission chromaticity. Regarding the mechanism of this multiple interference effect, reference can be made to AM-LCD Digest of Technical Papers, OD-2, P77-80 (2002) by J. Yamada et al.

  The current applied to each of the organic electroluminescent elements is usually a direct current, but a pulse current or an alternating current may be used. The current value and the voltage value are not particularly limited as long as they are within the range that does not destroy the element. However, considering the power consumption and life of the organic electroluminescence element, it is desirable to efficiently emit light with as little electrical energy as possible.

  Next, FIG. 7 is a configuration example of a flat display using the organic electroluminescent element of the present invention. As shown in the figure, for example, in the case of a full color display, the organic layer 5 (5a, 5b, 5c, 5d) capable of emitting three primary colors of red (R), green (G), and blue (B) is formed by the cathode 3 and the anode. Between the two. The cathode 3 and the anode 2 can be provided in stripes crossing each other, and are selected by the luminance signal circuit 14 and the control circuit 15 with a built-in shift register, and a signal voltage is applied to each, thereby the selected cathode 3 and the organic layer at the position (pixel) where the anode 2 intersects are configured to emit light.

  That is, FIG. 7 is an 8 × 3 RGB simple matrix, for example, in which a laminate 5 including at least one of a hole transport layer and a light emitting layer and an electron transport layer is disposed between the cathode 3 and the anode 2. (See FIG. 3 or FIG. 4, FIG. 5 or FIG. 6). Both the cathode and the anode are patterned in stripes, orthogonal to each other in a matrix, and a signal voltage is applied in time series by the control circuit 15 and the luminance signal circuit 14 with a built-in shift register so that light is emitted at the crossing position. It is composed of. The EL element having such a structure can be used not only as a display of characters and symbols but also as an image reproducing device. In addition, a striped pattern of the cathode 3 and the anode 2 can be arranged for each color of red (R), green (G), and blue (B) to constitute a multi-color or full-color all-solid-type flat panel display. It becomes. Further, not only the above simple matrix system but also an active matrix system can be driven.

  Examples of the present invention are shown below, but the present invention is not limited thereto.

Example 1
<Synthesis Example of Bis (aminostyryl) phenanthrene Compound (Structural Formula (60) -5)>

  Weigh 0.600 g (about 60 wt%, 15.4 mmol) of sodium hydride (with mineral oil) into the reaction vessel, wash twice with hexane, suspend in 80 mL of anhydrous tetrahydrofuran, wittig on an ice bath under nitrogen atmosphere -Horner reagent ((58) -1) 1.07 g (2.57 mmol) and 4- [N- (methylphenyl) -N-naphthyl] aminobenzaldehyde ((57) -1) 2.38 g (6.68 mmol) Of tetrahydrofuran: N, N-dimethylformamide = 1: 1 mixed solution was added dropwise over 15 minutes, and the mixture was stirred at 0 ° C. for 12 hours. The reaction mixture was quenched with a small amount of ice, extracted with toluene, washed with saturated brine, and dried over anhydrous sodium sulfate.

Purification by silica gel chromatography (Wako gel C-300, toluene: chloroform = 2: 1) and recrystallization from toluene-hexane four times gave 0.760 g of a red powder. This was identified as the desired product by ¹ H NMR and FAB-MS measurements (isolation yield: 34%). The identification data were as follows, and the ¹ H NMR spectrum was as shown in FIG.

^{1 H NMR (400 MHz, CDCl} 3) δ (ppm): 2.39 (s, 6H), 6.92 (d, 4H), 7.07 (s, 8H), 7.24 (d, 2H), 7.32-7.50 (m, 14H ), 7.80 (d, 2H), 7.89-7.95 (m, 4H), 8.00 (d, 2H), 8.27 (d, 2H), 8.64 (s, 2H)

  As a result of thermal analysis by DSC (differential scanning calorimetry), no melting point was observed by 450 ° C., and the glass transition point was 165 ° C., indicating that the material was a good amorphous material. Moreover, the visible absorption maximum of the dioxane solution was 454 nm, and the fluorescence maximum wavelength was 579 nm.

Example 2
<Synthesis Example of Diphosphonate (Structural Formula (58) -1)>

50 ml of xylene containing 0.920 g (1.74 mmol) of 3,6-bis (α-bromomethyl) phenanthrene-9,10-dicarbonitrile ([VIII] -1) and 0.867 g (5.52 mmol) of triethyl phosphite The product was suspended in the solution and gently refluxed for 48 hours to quantitatively obtain the desired product. This was identified as the target by ¹ H NMR and FAB-MS measurements. The identification data is as shown below, and its ¹ H NMR spectrum is as shown in FIG.

¹ H NMR (400 MHz, CDCl ₃ ) δ (ppm): 1.26 (t, 12H), 3.44 (s, 2H), 3.50 (s, 2H), 4.07 (m, 8H), 7.81 (d, 2H), 8.34 (D, 2H), 8.71 (s, 2H)

Example 3
<Synthesis Example of 3,6-bis (α-bromomethyl) phenanthrene-9,10-dicarbonitrile ([VIII] -1)>

  After dissolving 2.00 g (7.80 mmol) of 3,6-dimethylphenanthrene 9,10-dicarbonitrile ([X] -1) in 300 mL of chlorobenzene and performing oxygen deaeration through nitrogen, N-bromosuccinimide 1 .85 g (10.4 mmol) and a small amount of AIBN (azoisobutyronitrile) were added and refluxed for 10 hours, and the reaction solution was concentrated.

Purification by silica gel chromatography (Wako gel C-300, toluene) and recrystallization from toluene-hexane gave 0.920 g of a yellow powder. This was identified as the target product by ¹ H NMR and FAB-MS measurements (yield 22%). The identification data was as follows.

¹ H NMR (CDCl ₃ ) δ (ppm): 4.78 (t, 4H), 7.90 (d, 2H), 8.39 (d, 2H), 8.75 (s, 2H)

Example 4
In this example, a compound represented by the following structural formula (60) -5 was converted into an electron-transporting light-emitting layer, and 4,4′-bis [N, N′-di (1-naphthyl) -N, N′- This is an example in which a bottom-emitting organic electroluminescent element having a single heterostructure was fabricated using diphenyl] biphenyldiamine (α-NPD) as a hole transport layer.

First, a 30 mm × 30 mm glass substrate having an anode made of ITO having a thickness of 100 nm formed on one surface was set in a vacuum deposition apparatus. As a vapor deposition mask, a plurality of metal masks having 2.0 mm × 2.0 mm unit openings are arranged close to the substrate, and α−, which is a hole transport material, under a vacuum of 10 ⁻⁴ Pa or less by a vacuum vapor deposition method. NPD was deposited to a thickness of 140 nm. Further, the compound of the above structural formula (60) -5 was deposited as an electron transporting light-emitting material at 55 nm in contact with the hole transporting layer. The deposition rate was 0.2 nm / second.

  As the cathode material, a mixed film of Mg and Ag is adopted, and this is also formed by vapor deposition, for example, with a mixing ratio of Mg and Ag of 1: 3, and a thickness of 200 nm at a deposition rate of 1 nm / second. An organic electroluminescent device as shown in 3 was produced.

The organic electroluminescence device thus fabricated was evaluated for light emission characteristics by applying a forward bias DC voltage in a nitrogen atmosphere. The emission color was red, and as a result of spectroscopic measurement, a spectrum having an emission peak near 660 nm was obtained. This electroluminescence spectrum is shown in FIG. For the spectroscopic measurement, a spectroscope using a photodiode array manufactured by Otsuka Electronics Co., Ltd. as a detector was used. The voltage - was subjected to luminance measurement, as shown in FIG. 11, the luminance of 84cd / m ² was obtained at 10V.

After this organic electroluminescent device was fabricated, it was left in a nitrogen atmosphere for 1 month, but no device degradation was observed. In addition, when the current value was constantly supplied at an initial luminance of 100 cd / m ² to continuously emit light and forcibly deteriorated, it took 1000 hours until the luminance was reduced to half.

Example 5
In this example, a bottom-emission type organic electroluminescence device having a double hetero structure using α-NPD as a hole transport layer and the compound of the above structural formula (60) -5 as a light emitting layer was produced.

First, a 30 mm × 30 mm glass substrate having an anode made of ITO having a thickness of 100 nm formed on one surface was set in a vacuum deposition apparatus. As a vapor deposition mask, a plurality of metal masks having 2.0 mm × 2.0 mm unit openings are arranged close to the substrate, and α− which is a hole transport material under vacuum of 10 ⁻⁴ Pa or less by a vacuum vapor deposition method. NPD was deposited to a thickness of 140 nm. Further, the compound represented by the structural formula (60) -5 as a light emitting material was deposited in a thickness of 40 nm in contact with the hole transport layer. The deposition rate was 0.2 nm / second. Further, tris (8-quinolinol) aluminum (Alq ₃ ) having the following structural formula was deposited in contact with the light emitting layer as an electron transport layer. The electron transport layer made of Alq ₃ was 50nm deposited. The deposition rate was 0.2 nm / second.

As the cathode material, a mixed film of Mg and Ag is adopted, and this is also formed by vapor deposition, for example, with a mixing ratio of Mg and Ag of 1: 3, and a thickness of 200 nm at a deposition rate of 1 nm / second. An organic electroluminescent device as shown in 4 was produced.

The organic electroluminescence device thus fabricated was evaluated for light emission characteristics by applying a forward bias DC voltage in a nitrogen atmosphere. The emission color was red, and as a result of spectroscopic measurement, the same spectrum as in Example 4 was obtained. For the spectroscopic measurement, a spectroscope using a photodiode array manufactured by Otsuka Electronics Co., Ltd. as a detector was used. Further, when voltage-luminance measurement was performed, a luminance of 145 cd / m ² was obtained at 10 V as shown in FIG.

After this organic electroluminescent device was fabricated, it was left in a nitrogen atmosphere for 1 month, but no device degradation was observed. In addition, when the initial luminance was 100 cd / m ² , the current value was constantly supplied and continuous light emission was performed, and when it was forcibly deteriorated, it took 1500 hours until the luminance was reduced to half.

Example 6
In this example, a top emission organic electroluminescent element was manufactured using the phenanthrene compound of the above structural formula (60) -5 as the light emitting layer among the phenanthrene compounds of the general formula [I].

First, a 30 mm × 30 mm glass substrate having an anode made of a 100 nm thick silver alloy and a 10 nm thick ITO film formed thereon is formed on one surface in a vacuum deposition apparatus. did. As a deposition mask, a plurality of metal masks having 2.0 mm × 2.0 mm unit openings are arranged close to the substrate, and 2-TNATA of the following structural formula is applied under vacuum of 10 ⁻⁴ Pa or less by a vacuum deposition method. For example, a film having a thickness of 20 nm was formed, and then α-NPD was formed thereon to a thickness of 43 nm, for example. The deposition rate was 0.1 nm / second.

  Further, the phenanthrene compound of the above structural formula (60) -5 was deposited in contact with the hole transport layer to form a light emitting layer. The film thickness of the light emitting layer was, for example, 30 nm, and the vapor deposition rate was 0.2 nm / second.

Further thereon, Alq ₃ was deposited to a thickness of, for example, 36 nm as an electron transport layer.

  As the cathode material, a mixed film of Mg and Ag was adopted, and this was also formed by vapor deposition, for example, with a mixing ratio of Mg and Ag of 1: 3 and a deposition rate of 1 nm / second to a thickness of 12 nm, as shown in FIG. An organic electroluminescent device as described above was prepared.

The organic electroluminescence device of Example 6 produced in this manner was subjected to evaluation of luminescence characteristics by applying a forward bias DC voltage in a nitrogen atmosphere. The emission color was red, and as a result of performing spectroscopic measurement in the same manner as in Example 4, the same spectrum as in Example 4 was obtained. When voltage-luminance measurement was performed, a luminance of 172 cd / m ² was obtained at 10V.

After this organic electroluminescent device was produced, it was left in a nitrogen atmosphere for 1 month, but no device deterioration was observed. In addition, when the initial luminance was 100 cd / m ² and the current value was energized continuously to continuously emit light and forcibly deteriorated, it was 1400 hours until the luminance was reduced to half.

It is a principal part schematic sectional drawing of an example of the organic electroluminescent element based on this invention. It is a principal part schematic sectional drawing of the other example of an organic electroluminescent element equally. It is a principal part schematic sectional drawing of the other example of an organic electroluminescent element equally. It is a principal part schematic sectional drawing of the other example of an organic electroluminescent element equally. It is a principal part schematic sectional drawing of the other example of an organic electroluminescent element equally. It is a principal part schematic sectional drawing of the other example of an organic electroluminescent element equally. It is a block diagram of a full-color flat display using an organic electroluminescent element. ¹ is a ¹ H NMR spectrum diagram of a compound according to an example of the present invention. FIG. FIG. 3 is a ¹ H NMR spectrum diagram of a compound according to another example of the present invention. 1 is an emission spectrum diagram of an organic electroluminescent device according to an embodiment of the present invention. It is a voltage-luminance characteristic view of an organic electroluminescent element.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 2 ... Transparent electrode or anode, 3 ... Cathode, 4 ... Protective film 5, 5a, 5b ... Organic layer, 6 ... Hole transport layer, 7 ... Electron transport layer, 8 ... Power supply, 9 ... Hole Injection layer, 10 ... hole transport layer,
DESCRIPTION OF SYMBOLS 11 ... Light emitting layer, 12 ... Electron carrying layer, 14 ... Luminance signal circuit, 15 ... Control circuit,
20 ... emitted light, A, B, C, D, E, F ... organic electroluminescent element

Claims (18)

Bis (aminostyryl) phenanthrene compounds represented by the following general formula [I], [II] or [III].

[However, in the general formula [I],
R ¹ and R ³ are the same or different phenyl groups represented by the following general formula (1)

(However, in the said General formula (1), R < ⁷ >, R < ⁸ >, R < ⁹ >, R < ¹⁰ > and R < ¹¹ > are mutually the same or different groups, Comprising: At least one of them is a hydrogen atom, C1 or more Saturated or unsaturated hydrocarbon group (adjacent hydrocarbon groups may form a ring together), saturated or unsaturated hydrocarbon oxy group having 1 or more carbon atoms, saturated having 1 or more carbon atoms Or an unsaturated hydrocarbon amino group, trifluoromethyl group, cyano group, or halogen atom).
R ² and R ⁴ are the same or different groups selected from a phenyl group represented by the following general formula (2) or a naphthyl group represented by the following general formula (3).

(However, in the said General formula (2), R < ¹² >, R < ¹³ >, R < ¹⁴ >, R < ¹⁵ > and R < ¹⁶ > are mutually the same or different groups, Comprising: At least one of them is a hydrogen atom, C1 or more Saturated or unsaturated hydrocarbon group (adjacent hydrocarbon groups may form a ring together), saturated or unsaturated hydrocarbon oxy group having 1 or more carbon atoms, saturated having 1 or more carbon atoms Or an unsaturated hydrocarbon amino group, trifluoromethyl group, cyano group, or halogen atom).

(In the general formula (3), R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are the same or different groups, and at least one of them is a hydrogen atom. A saturated or unsaturated hydrocarbon group having 1 or more carbon atoms (adjacent hydrocarbon groups may form a ring together), a saturated or unsaturated hydrocarbon oxy group having 1 or more carbon atoms, A saturated or unsaturated hydrocarbon amino group having 1 or more carbon atoms, a trifluoromethyl group, a cyano group, or a halogen atom).
R ⁵ and R ⁶ are the same or different from each other, and at least one of them is a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group, or a halogen atom. ]

[However, in the general formula [II],
R ²⁴ , R ²⁵ and R ²⁶ are the same or different naphthyl groups represented by the following general formula (4).

(In the general formula (4), R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ are the same or different groups, and at least one of them is a hydrogen atom, carbon 1 or more saturated or unsaturated hydrocarbon groups (adjacent hydrocarbon groups may form a ring together), 1 or more saturated or unsaturated hydrocarbon oxy group, carbon number One or more saturated or unsaturated hydrocarbon amino groups, trifluoromethyl groups, cyano groups, or halogen atoms).
R ²⁷ is a phenyl group represented by the following general formula (5) or a naphthyl group represented by the following general formula (6).

(In the general formula (5), R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , and R ⁴¹ are the same or different groups, and at least one of them is a hydrogen atom, saturated with 1 or more carbon atoms) Or an unsaturated hydrocarbon group (adjacent hydrocarbon groups may form a ring together), a saturated or unsaturated hydrocarbon oxy group having 1 or more carbon atoms, saturated or having 1 or more carbon atoms, or It is an unsaturated hydrocarbon amino group, trifluoromethyl group, cyano group, or halogen atom.)

(In the general formula (6), R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ are the same or different groups, and at least one is a hydrogen atom, carbon 1 or more saturated or unsaturated hydrocarbon groups (adjacent hydrocarbon groups may form a ring together), 1 or more saturated or unsaturated hydrocarbon oxy group, carbon number One or more saturated or unsaturated hydrocarbon amino groups, trifluoromethyl groups, cyano groups, or halogen atoms).
R ²⁸ and R ²⁹ are the same or different from each other, and at least one of them is a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group, or a halogen atom. ]

[However, in the general formula [III],
R ⁴⁹ and R ⁵⁰ are the same or different phenyl groups represented by the following general formula (7).

(However, in the general formula (7), R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ and R ⁵⁹ are the same or different groups, and at least one is a hydrogen atom, saturated or having 1 or more carbon atoms, or Unsaturated hydrocarbon group (adjacent hydrocarbon groups may form a ring together), saturated or unsaturated hydrocarbon oxy group having 1 or more carbon atoms, saturated or unsaturated group having 1 or more carbon atoms A saturated hydrocarbon amino group, trifluoromethyl group, cyano group, or halogen atom).
R ⁵¹ and R ⁵² are the same or different naphthyl groups represented by the following general formula (8).

(In the general formula (8), R ⁶⁰ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ and R ⁶⁶ are the same or different groups, and at least one of them is a hydrogen atom, carbon 1 or more saturated or unsaturated hydrocarbon groups (adjacent hydrocarbon groups may form a ring together), 1 or more saturated or unsaturated hydrocarbon oxy group, carbon number One or more saturated or unsaturated hydrocarbon amino groups, trifluoromethyl groups, cyano groups, or halogen atoms).
R ⁵³ and R ⁵⁴ are the same or different from each other, and at least one of them is a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group, or a halogen atom. ] The bis (aminostyryl) phenanthrene compound according to claim 1, which is represented by the following general formula [IV].

[However, in the general formula [IV], Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are each the same or different aryl group which may have a substituent, and each has a substituent. Is a group selected from aryl groups represented by the following general formula (9), (10), (11), (12), (13), (14), (15), (16) or (17) is there.

(However, in the general formulas (9), (10), (11), (12), (13), (14), (15), (16) and (17), R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ and R ⁸¹ are the same or different and have one or more saturated carbon atoms Or an unsaturated hydrocarbon group (adjacent hydrocarbon groups may form a ring together), n is an integer of 0 to 5, m is an integer of 0 to 3, l is an integer from 0 to 3)]] R ⁶⁷ , R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R ⁷⁹ , R ⁸⁰ and R ⁸¹ have 1 to 1 carbon atoms. The bis (aminostyryl) phenanthrene compound according to claim 2, which is 6 hydrocarbon groups. The following general formula (18), (19), (20), (21), (22), (23), (24), (25), (26), (27), (28), (29) , (30), (31), (32), (33), (34), (35), (36), (37), (38), (39), (40), (41), ( 42), (43), (44), (45), (46), (47), (48), (49), (50), (51), (52), (53), (54) The bis (aminostyryl) phenanthrene compound according to claim 2, which is represented by formula (55) or (56).

(However, in the said General formula (18), ^R82 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (19), ^R83 and ^R84 are mutually the same or different groups, Comprising: It is a C1-C6 saturated or unsaturated alkyl group, or a substituent. A good aryl group.)

(However, in the said General formula (20), ^R85 is a C1-C6 saturated or unsaturated alkyl group or the aryl group which may have a substituent.)

(However, in the said General formula (21), ^R86 and ^R87 are mutually the same or different groups, Comprising: It is a C1-C6 saturated or unsaturated alkyl group, or a substituent. A good aryl group.)

(However, in the said General formula (22), ^R88 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (23), ^R89 and ^R90 are mutually the same or different groups, Comprising: You may have a C1-C6 saturated or unsaturated alkyl group, or a substituent. An aryl group.)

(However, in the said General formula (24), ^R91 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (25), ^R92 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the general formula (26), R ⁹³ is an alkyl group, or an aryl group which may have a substituent, saturated or unsaturated having 1 to 6 carbon atoms.)

(However, in the said General formula (27), ^R94 is a C1-C6 saturated or unsaturated alkyl group or the aryl group which may have a substituent.)

(However, in the general formula (28), R ⁹⁵ and R ⁹⁶ may be the same or different from each other, and may have a saturated or unsaturated alkyl group having 1 to 6 carbon atoms, or a substituent. A good aryl group.)

(However, in the said General formula (29), ^R97 is a C1-C6 saturated or unsaturated alkyl group or the aryl group which may have a substituent.)

(However, in the said General formula (30), ^R98 and ^R99 are mutually the same or different groups, Comprising: It is a C1-C6 saturated or unsaturated alkyl group, or a substituent. A good aryl group.)

(However, in the general formula (31), R ¹⁰⁰ is an alkyl group, or an aryl group which may have a substituent, saturated or unsaturated having 1 to 6 carbon atoms.)

(However, in the said General formula (32), ^R101 and ^R102 are mutually the same or different groups, Comprising: It is a C1-C6 saturated or unsaturated alkyl group, or a substituent. A good aryl group.)

(However, in the said General formula (33), ^R103 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (34), ^R104 and ^R105 are mutually the same or different groups, Comprising: Even if it has a C1-C6 saturated or unsaturated alkyl group, or a substituent, A good aryl group.)

(However, in the said General formula (35), ^R106 is a C1-C6 saturated or unsaturated alkyl group or the aryl group which may have a substituent.)

(However, in the general formula (36), R ¹⁰⁷ and R ¹⁰⁸ is an identical or different groups from each other, may have an alkyl group, or a substituent of the saturated or unsaturated having 1 to 6 carbon atoms A good aryl group.)

(However, in the said General formula (37), ^R109 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (38), ^R110 is a C1-C6 saturated or unsaturated alkyl group or the aryl group which may have a substituent.)

(However, in the said General formula (39), ^R111 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (40), ^R112 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the general formula (41), R ¹¹³ and R ¹¹⁴ may be the same or different from each other, and may have a saturated or unsaturated alkyl group having 1 to 6 carbon atoms, or a substituent. A good aryl group.)

(However, in the said General formula (42), ^R115 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (43), ^R116 and ^R117 are mutually the same or different groups, Comprising: It is a C1-C6 saturated or unsaturated alkyl group, or a substituent. A good aryl group.)

(However, in the said General formula (44), ^R118 is a C1-C6 saturated or unsaturated alkyl group or the aryl group which may have a substituent.)

(However, in the said General formula (45), ^R119 and ^R120 are mutually the same or different groups, Comprising: Even if it has a C1-C6 saturated or unsaturated alkyl group, or a substituent, A good aryl group.)

(However, in the general formula (46), R ¹²¹ is an alkyl group, or an aryl group which may have a substituent, saturated or unsaturated having 1 to 6 carbon atoms.)

(However, in the said General formula (47), ^R122 and ^R123 are mutually the same or different groups, Comprising: It is a C1-C6 saturated or unsaturated alkyl group, or a substituent. A good aryl group.)

(However, in the said General formula (48), ^R124 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (49), ^R125 and ^R126 are mutually the same or different groups, Comprising: It is a C1-C6 saturated or unsaturated alkyl group, or a substituent. A good aryl group.)

(However, in the said General formula (50), ^R127 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (51), ^R128 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (52), ^R129 is a C1-C6 saturated or unsaturated alkyl group or the aryl group which may have a substituent.)

(However, in the said General formula (53), ^R130 is a C1-C6 saturated or unsaturated alkyl group, or the aryl group which may have a substituent.)

(However, in the said General formula (54), ^R131 and ^R132 are mutually the same or different groups, Comprising: It is a C1-C6 saturated or unsaturated alkyl group, or a substituent. A good aryl group.)

(However, in the said General formula (55), ^R133 is a C1-C6 saturated or unsaturated alkyl group or the aryl group which may have a substituent.)

(However, in the general formula (56), R ¹³⁴ and R ¹³⁵ is an identical or different groups from each other, may have an alkyl group, or a substituent of the saturated or unsaturated having 1 to 6 carbon atoms A good aryl group.) 4- (N, N-diarylamino) benzaldehyde represented by the following general formula [V]; diphosphonic acid ester represented by the following general formula [VI] or diphosphonium represented by the following general formula [VII] A process for producing a bis (aminostyryl) phenanthrene compound, wherein the bis (aminostyryl) phenanthrene compound represented by [I], [II] or [III] described in claim 1 is obtained.

(However, in the general formula [V], R ¹³⁶ and R ¹³⁷ are respectively R ¹ , R ² , R ³ , R ⁴ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , An aryl group corresponding to R ⁴⁹ , R ⁵⁰ , R ⁵¹ or R ^52. )

(However, in the general formulas [VI] and [VII], R ¹³⁸ is a hydrocarbon group, and R ¹³⁹ and R ¹⁴⁰ are R ⁵ , R ⁶ , R ²⁸ , R ^{29, respectively.} , R ⁵³ or R ⁵⁴ and X is a halogen atom.)   The condensation is carried out by a Wittig-Horner reaction or a Wittig reaction, and a carbanion is produced by treating the diphosphonic acid ester and / or the diphosphonium with a base in a solvent to produce a carbanion. The method for producing a bis (aminostyryl) phenanthrene compound according to claim 5, wherein the 4- (N, N-diarylamino) benzaldehyde is condensed. In obtaining the bis (aminostyryl) phenanthrene compound represented by the general formula [IV] according to claim 2, 4- (N, N-diarylamino) benzaldehyde represented by the following general formula (57); A bis (aminostyryl) phenanthrene compound according to claim 2 is obtained by condensing a diphosphonic acid ester represented by the formula (58) or a diphosphonium represented by the following general formula (59): ) A method for producing a phenanthrene compound.

(However, in said general formula (57), (58) and (59), Ar < ⁵ > and Ar < ⁶ > are respectively the same as Ar < ¹ >, Ar < ² >, Ar < ³ > or Ar < ⁴ > described in Claim 2, and R ¹³⁸ is a hydrocarbon group, and X is a halogen atom.) The method for producing a bis (aminostyryl) phenanthrene compound according to claim 5 or 7, wherein R ¹³⁸ is a saturated hydrocarbon group having 1 to 4 carbon atoms.   The method for producing a bis (aminostyryl) phenanthrene compound according to claim 7, wherein the bis (aminostyryl) phenanthrene compound according to claim 3 is obtained.   The method for producing a bis (aminostyryl) phenanthrene compound according to claim 7, wherein the bis (aminostyryl) phenanthrene compound according to claim 4 is obtained. Diphosphonic acid ester or diphosphonium represented by the following general formula [VI] or [VII].

(However, in the general formula [VI] and [VII], R ¹³⁸ represents a hydrocarbon group, each R ¹³⁹ and R ¹⁴⁰ are said to claim ^{1 R 5, R 6, R} 28, R 29 , R ⁵³ or R ⁵⁴ and X is a halogen atom.) The diphosphonic acid ester or diphosphonium according to claim 11, wherein R ¹³⁸ is a saturated hydrocarbon group having 1 to 4 carbon atoms. The diphosphonic acid ester or diphosphonium according to claim 11, which is represented by the following general formula (58) or (59).

(However, in the general formulas (58) and (59), R ¹³⁸ and X are the same as those described above.) The dihalogenated aryl compound represented by the following general formula [VIII] is reacted with a trialkyl phosphite or triphenylphosphine (PPh ₃ ) represented by the following general formula [IX]. A method for producing a diphosphonic acid ester or diphosphonium, wherein the diphosphonic acid ester or diphosphonium represented by the general formula [VI] or [VII] is obtained.

(However, in the general formula [VIII], R ¹³⁹ and R ¹⁴⁰ are the same as those described above, and X is a halogen atom.)
General formula [IX]
P (OR ¹³⁸ ) ₃
(However, in the general formula [IX], R ¹³⁸ is the same as described above.) The method for producing a diphosphonic acid ester or diphosphonium according to claim 14, wherein R ¹³⁸ is a saturated hydrocarbon group having 1 to 4 carbon atoms.   The method for producing a diphosphonic acid ester or diphosphonium according to claim 14, wherein the diphosphonic acid ester or diphosphonium according to claim 13 is obtained. A dihalogenated aryl compound represented by the following general formula [VIII].

(In the general formula [VIII], R ¹³⁹ and R ¹⁴⁰ are the same or different groups, and at least one of them is a hydrogen atom, a cyano group, a nitro group, a trifluoromethyl group, or a halogen atom. And X is a halogen atom.) The dihalogenated aryl obtained by reacting the phenanthrene compound represented by the following general formula [X] with the N-halogenated succinimide represented by the general formula [XI] to obtain the dihalogenated aryl compound according to claim 17. Compound production method.

(However, in the general formula [X], R ¹³⁹ and R ¹⁴⁰ are the same as those described above.)

(In the general formula [XI], X is a halogen atom.)

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