JP5760323B2 - 1,2,4,5-Substituted phenyl derivatives, process for producing the same, and organic electroluminescent device comprising them as constituents - Google Patents

Description

  The present invention relates to a 1,2,4,5-substituted phenyl derivative and a method for producing the same. The 1,2,4,5-substituted phenyl derivative of the present invention has good charge transport properties and forms a stable thin film, and thus is useful as a component of a fluorescent or phosphorescent organic electroluminescent device.

  The present invention also relates to a high-efficiency organic electroluminescence device excellent in driving performance and luminescence, using a 1,2,4,5-substituted phenyl derivative in at least one organic compound layer of the organic electroluminescence device. .

  An organic electroluminescent element is formed by sandwiching a light-emitting layer containing a light-emitting material between a hole transport layer and an electron transport layer, and further attaching an anode and a cathode to the outside, and recombination of holes and electrons injected into the light-emitting layer. It is an element that utilizes light emission (fluorescence or phosphorescence) when the generated excitons are deactivated, and is applied to displays and the like.

  The 1,2,4,5-substituted phenyl derivative of the present invention is novel and is characterized by having a pyridyl-substituted phenylene group or a phenyl-substituted pyridylene group on the 1,2,4,5-position phenyl group.

  Recently, as a 1,2,4,5-substituted phenyl derivative, an example in which a compound into which a bipyridyl group is introduced is used for an organic electroluminescence device (for example, see Patent Document 1), the bond of the bipyridyl group is It is not limited to the 1, 2, 4 and 5 positions of the phenyl group, and the substitution of the bipyridyl group is not limited to the phenyl group. Moreover, it is limited to a bipyridyl group and does not include the derivative of the present invention.

  Furthermore, examples in which 1,2,4,5-substituted phenyl derivatives are used in organic electroluminescent devices are disclosed (for example, see Patent Document 2), but these are only discussed for improving luminous efficiency. However, the low power consumption and long life required for the organic electroluminescence device are not shown, and the effect is limited. Furthermore, the 1,2,4,5-substituted phenyl derivatives of the present invention are not included.

  Furthermore, there is an example (for example, see Patent Documents 3 to 7) in which a derivative in which a phenyl group and a pyridyl group are combined is used in an organic electroluminescent element, but the effect of improving the element performance is insufficient. It is different from 2,4,5-substituted phenyl derivatives.

WO2009-151039 WO2009-081873 JP 2008-63232 A JP 2003-336043 A JP 2007-015993 A JP 2005-255986 A JP 2008-127326 A

  Although organic electroluminescent elements are used in various display devices, the use of organic electroluminescent elements in portable devices with limited power supply is required to achieve lower power consumption. At the same time, when the organic electroluminescence device is used commercially, how to extend the device lifetime in order to obtain stable performance becomes a problem.

  Especially for electron transport materials, materials that combine excellent charge injection and transport characteristics to drive devices at low voltage and reduce power consumption, and durability that enables longer device lifetimes, are the conventional compounds. New materials are desired because they cannot be found in any of the above.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have excellent derivatives in which a pyridyl-substituted phenylene group or a phenyl-substituted pyridylene group is bonded to phenyl groups at 1, 2, 4, and 5 positions. It has been found to have charge injection and transport properties. The 1,2,4,5-substituted phenyl derivatives (1) to (4) can be formed into a thin film by a general method such as vacuum deposition, and an organic electroluminescence device using these as an electron transport layer However, it has been found that a reduction in power consumption and a longer life can be achieved as compared with a general-purpose organic electroluminescence device, and the present invention has been completed.

  That is, the present invention relates to the general formula (1)

(Wherein R ^{1 to} R ³⁴ each independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms), 1,2,4,5-substituted phenyl derivatives It is about.

  In addition, the general formula (2)

(In the formula, R ^{1 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X ^{1 to} X ⁸ represent a carbon atom or a nitrogen atom. , X ¹ and X ² , X ³ and X ⁴ , X ⁵ and X ⁶ , X ⁷ and X ⁸ cannot simultaneously be nitrogen atoms or carbon atoms. It relates to phenyl derivatives.

  In addition, the general formula (3)

(Wherein R ^{1 to} R ³⁴ each independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms), 1,2,4,5-substituted phenyl derivatives It is about.

  Further, the general formula (4)

(In the formula, R ^{1 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X ^{1 to} X ¹⁶ represent a nitrogen atom or a carbon atom. , X ^{1 to} X ⁴ , X ^{5 to} X ⁸ , X ^{9 to} X ¹² , X ^{13 to} X ¹⁶ , one atom is a nitrogen atom, and the other three atoms are carbon atoms And 1,2,4,5-substituted phenyl derivatives.

  Further, the present invention provides a general formula (5)

(In the formula, R ¹ and R ² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ¹ to Y ⁴ each independently represent a leaving group. And a compound represented by formula (6-1)

(In the formula, R ^{3 to} R ⁶ and R ^{19 to} R ²² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. M represents a metal group or a heteroatom group. And a compound represented by the general formula (6-2):

(Wherein R ^{7 to} R ¹⁰ and R ^{23 to} R ²⁶ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. M represents a metal group or a heteroatom group. And a compound represented by formula (6-3):

(Wherein R ^{11 to} R ¹⁴ and R ^{27 to} R ³⁰ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. M represents a metal group or a heteroatom group. And a compound represented by formula (6-4):

(Wherein R ^{15 to} R ¹⁸ and R ^{31 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. M represents a metal group or a heteroatom group. And a compound represented by the general formula (1), which is subjected to a coupling reaction in the presence of a base and a metal catalyst.

(Wherein R ^{1 to} R ³⁴ each independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms), 1,2,4,5-substituted phenyl derivatives It is related with the manufacturing method.

  Further, the general formula (5)

(In the formula, R ¹ and R ² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ¹ to Y ⁴ each independently represent a leaving group. And a compound represented by formula (7-1)

(In the formula, R ^{3 to} R ⁵ and R ^{15 to} R ¹⁹ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. M is a metal group or a heteroatom group. X ¹ and X ² represent a carbon atom or a nitrogen atom, provided that X ¹ and X ² cannot simultaneously be a nitrogen atom or a carbon atom) and a general formula (7-2) )

(Wherein R ^{6 to} R ⁸ and R ^{20 to} R ²⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. M is a metal group or a heteroatom group. X ³ and X ⁴ represent a carbon atom or a nitrogen atom, provided that X ³ and X ⁴ cannot simultaneously be a nitrogen atom or a carbon atom.) And a compound represented by the general formula (7-3 )

(Wherein R ^{9 to} R ¹¹ and R ^{25 to} R ²⁹ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. M represents a metal group or a heteroatom group. X ⁵ and X ⁶ represent a carbon atom or a nitrogen atom, provided that X ⁵ and X ⁶ cannot simultaneously be a nitrogen atom or a carbon atom.) And a compound represented by the general formula (7-4 )

(Wherein R ^{12 to} R ¹⁴ and R ^{30 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. M represents a metal group or a heteroatom group. X ⁷ and X ⁸ represent a carbon atom or a nitrogen atom, provided that X ⁷ and X ⁸ cannot simultaneously be a nitrogen atom or a carbon atom.) The compound shown is present in the presence of a base and a metal catalyst. A general formula (2) characterized in that a coupling reaction is carried out below

(In the formula, R ^{1 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X ^{1 to} X ⁸ represent a carbon atom or a nitrogen atom. , X ¹ and X ² , X ³ and X ⁴ , X ⁵ and X ⁶ , X ⁷ and X ⁸ cannot simultaneously be nitrogen atoms or carbon atoms. The present invention relates to a method for producing a phenyl derivative.

  Further, the general formula (5)

(In the formula, R ¹ and R ² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ¹ to Y ⁴ each independently represent a leaving group. And a compound represented by formula (8-1)

(In the formula, R ^{3 to} R ⁶ and R ^{19 to} R ²² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. M represents a metal group or a heteroatom group. And a compound represented by the general formula (8-2):

(In formula, R < ⁷ > -R < ¹⁰ >, R < ²³ > -R < ²⁶ > respectively independently represents hydrogen, a C1-C6 alkyl group, or a C1-C6 alkoxy group. M is a metal group or And a compound represented by formula (8-3):

(Wherein, R ^{11 to} R ¹⁴ and R ^{27 to} R ³⁰ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. M represents a metal group or And a compound represented by formula (8-4):

(Wherein, R ^{15 to} R ¹⁸ and R ^{31 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. M represents a metal group or And a compound represented by the general formula (3), wherein the compound is represented by a coupling reaction in the presence of a base and a metal catalyst.

(Wherein R ^{1 to} R ³⁴ each independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms), 1,2,4,5-substituted phenyl derivatives It is related with the manufacturing method.

  Further, the general formula (5)

(In the formula, R ¹ and R ² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ¹ to Y ⁴ each independently represent a leaving group. And a compound represented by formula (9-1)

(In the formula, R ^{3 to} R ⁵ and R ^{15 to} R ¹⁹ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. M is a metal group or a heteroatom group. X ^{1 to} X ⁴ represent a nitrogen atom or a carbon atom, provided that one of the four atoms of X ^{1 to} X ⁴ is a nitrogen atom, and the other three atoms represent a carbon atom. And a compound represented by the general formula (9-2)

(Wherein R ^{6 to} R ⁸ and R ^{20 to} R ²⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. M is a metal group or a heteroatom group. .X ⁵ to X ⁸ representing a represents a nitrogen atom or a carbon atom. However, of each of the four atoms of X ⁵ to X ^8, one atom and a nitrogen atom, the other three atoms represent carbon atoms And a compound represented by the general formula (9-3)

(Wherein R ^{9 to} R ¹¹ and R ^{25 to} R ²⁹ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. M represents a metal group or a heteroatom group. X ^{13 to} X ¹⁶ represent a nitrogen atom or a carbon atom, provided that one of four atoms of X ^{13 to} X ¹⁶ is a nitrogen atom, and the other three atoms represent a carbon atom. And a compound represented by the general formula (9-4)

(Wherein R ^{12 to} R ¹⁴ and R ^{30 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. M represents a metal group or a heteroatom group. .X ⁹ to X ¹² representing a represents a nitrogen atom or a carbon atom. However, of each of the four atoms of X ⁹ to X ^12, a single atom and a nitrogen atom, the other three atoms represent carbon atoms And a compound represented by the general formula (4), wherein a coupling reaction is carried out in the presence of a base and a metal catalyst.

(In the formula, R ^{1 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X ^{1 to} X ¹⁶ represent a nitrogen atom or a carbon atom. , X ^{1 to} X ⁴ , X ^{5 to} X ⁸ , X ^{9 to} X ¹² , X ^{13 to} X ¹⁶ , one atom is a nitrogen atom, and the other three atoms are carbon atoms )), A process for producing a 1,2,4,5-substituted phenyl derivative.

  Further, the general formula (10)

(In the formula, R ¹ and R ² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Z ^{1 to} Z ⁴ each independently represent a metal group or a hetero atom. And a compound represented by formula (11-1):

(Wherein R ^{3 to} R ⁶ and R ^{19 to} R ²² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ⁵ represents a leaving group. ) And the general formula (11-2)

(Wherein R ^{7 to} R ¹⁰ and R ^{23 to} R ²⁶ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ⁵ represents a leaving group. ) And the general formula (11-3)

(In the formula, R ^{11 to} R ¹⁴ and R ^{27 to} R ³⁰ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ⁵ represents a leaving group. ) And the general formula (11-4)

(Wherein R ^{15 to} R ¹⁸ and R ^{31 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ⁵ represents a leaving group. The compound represented by formula (1) is subjected to a coupling reaction in the presence of a base and a metal catalyst.

(Wherein R ^{1 to} R ³⁴ each independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms), 1,2,4,5-substituted phenyl derivatives It is related with the manufacturing method.

  Further, the general formula (10)

(In the formula, R ¹ and R ² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Z ^{1 to} Z ⁴ each independently represent a metal group or a hetero atom. And a compound represented by formula (12-1):

(Wherein R ^{3 to} R ⁵ and R ^{15 to} R ¹⁹ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ⁵ represents a leaving group. X ¹ and X ² represent a carbon atom or a nitrogen atom, provided that X ¹ and X ² cannot simultaneously be a nitrogen atom or a carbon atom.) And a compound represented by the general formula (12-2)

(Wherein R ^{6 to} R ⁸ and R ^{20 to} R ²⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ⁵ represents a leaving group. X ³ and X ⁴ represent a carbon atom or a nitrogen atom, provided that X ³ and X ⁴ cannot simultaneously be a nitrogen atom or a carbon atom.) And a compound represented by the general formula (12-3)

(Wherein R ^{9 to} R ¹¹ and R ^{25 to} R ²⁹ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ⁵ represents a leaving group. X ⁵ and X ⁶ represent a carbon atom or a nitrogen atom, provided that X ⁵ and X ⁶ cannot simultaneously be a nitrogen atom or a carbon atom.) And a compound represented by the general formula (12-4)

(Wherein R ^{12 to} R ¹⁴ and R ³⁰ to ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ⁵ represents a leaving group. X ³ and X ^{4 each} represent a carbon atom or a nitrogen atom (provided that X ⁷ and X ⁸ cannot simultaneously be a nitrogen atom or a carbon atom)) in the presence of a base and a metal catalyst. General formula (2), characterized by ring reaction

(In the formula, R ^{1 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X ^{1 to} X ⁸ represent a carbon atom or a nitrogen atom. , X ¹ and X ² , X ³ and X ⁴ , X ⁵ and X ⁶ , X ⁷ and X ⁸ cannot simultaneously be nitrogen atoms or carbon atoms. The present invention relates to a method for producing a phenyl derivative.

  Further, the general formula (10)

(In the formula, R ¹ and R ² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Z ^{1 to} Z ⁴ each independently represent a metal group or a hetero atom. And a compound represented by formula (13-1):

(Wherein R ^{3 to} R ⁶ and R ^{19 to} R ²² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ⁵ represents a leaving group. ) And the general formula (13-2)

(Wherein R ^{7 to} R ¹⁰ and R ^{23 to} R ²⁶ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ⁵ represents a leaving group. And a compound represented by formula (13-3)

(In the formula, R ^{11 to} R ¹⁴ and R ^{27 to} R ³⁰ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ⁵ represents a leaving group. ) And the general formula (13-4)

(Wherein R ^{15 to} R ¹⁸ and R ^{31 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ⁵ represents a leaving group. The compound represented by formula (3) is subjected to a coupling reaction in the presence of a base and a metal catalyst.

(Wherein R ^{1 to} R ³⁴ each independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms), 1,2,4,5-substituted phenyl derivatives It is related with the manufacturing method.

  Further, the general formula (10)

(In the formula, R ¹ and R ² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Z ^{1 to} Z ⁴ each independently represent a metal group or a hetero atom. And a compound represented by the general formula (14-1):

(Wherein R ^{3 to} R ⁵ and R ^{15 to} R ¹⁹ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ⁵ represents a leaving group. X ^{1 to} X ⁴ represent a nitrogen atom or a carbon atom, provided that one of the four atoms of X ^{1 to} X ⁴ is a nitrogen atom, and the other three atoms represent a carbon atom. The compound shown and general formula (14-2)

(Wherein R ^{6 to} R ⁸ and R ^{20 to} R ²⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ⁵ represents a leaving group. X ^{5 to} X ⁸ represent a nitrogen atom or a carbon atom, provided that one of the four atoms of X ^{5 to} X ⁸ is a nitrogen atom, and the other three atoms represent a carbon atom. The compound shown and general formula (14-3)

(Wherein R ^{9 to} R ¹¹ and R ^{25 to} R ²⁹ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, Y ⁵ represents a leaving group. X ^{13 to} X ¹⁶ represent a nitrogen atom or a carbon atom, provided that one of the four atoms of X ^{13 to} X ¹⁶ is a nitrogen atom, and the other three atoms are carbon atoms. And the general formula (14-4)

(Wherein R ^{12 to} R ¹⁴ and R ^{30 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ⁵ represents a leaving group. X ^{9 to} X ¹² each represent a nitrogen atom or a carbon atom, provided that one of the four atoms X ^{9 to} X ¹² is a nitrogen atom, and the other three atoms represent a carbon atom. And a compound represented by the general formula (4), wherein a coupling reaction is carried out in the presence of a base and a metal catalyst.

(Wherein R ^{1 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X ^{1 to} X ¹⁶ represent a nitrogen atom or a carbon atom. However, one of four atoms X ^{1 to} X ⁴ , X ^{5 to} X ⁸ , X ^{9 to} X ¹² , and X ^{13 to} X ¹⁶ is a nitrogen atom, and the other three atoms are carbon atoms. It is related with the manufacturing method of the 1,2,4,5- substituted phenyl derivative shown by this.

  Furthermore, the present invention relates to a general formula (1)

(Wherein R ^{1 to} R ³⁴ each independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms), 1,2,4,5-substituted phenyl derivatives It is related with the organic electroluminescent element which uses as a structural component.

  Further, the present invention provides a general formula (2)

(In the formula, R ^{1 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X ^{1 to} X ⁸ represent a carbon atom or a nitrogen atom. , X ¹ and X ² , X ³ and X ⁴ , X ⁵ and X ⁶ , X ⁷ and X ⁸ cannot simultaneously be nitrogen atoms or carbon atoms. The present invention relates to an organic electroluminescent device comprising a phenyl derivative as a constituent component.

  Further, the present invention provides a general formula (3)

(Wherein R ^{1 to} R ³⁴ each independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms), 1,2,4,5-substituted phenyl derivatives It is related with the organic electroluminescent element which uses as a structural component.

  Further, the present invention provides a general formula (4)

(In the formula, R ^{1 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X ^{1 to} X ¹⁶ represent a nitrogen atom or a carbon atom. , X ^{1 to} X ⁴ , X ^{5 to} X ⁸ , X ^{9 to} X ¹² , X ^{13 to} X ¹⁶ , one atom is a nitrogen atom, and the other three atoms are carbon atoms )), And an organic electroluminescent device having a 1,2,4,5-substituted phenyl derivative as a constituent component.

  Hereinafter, the present invention will be described in detail.

In the compounds represented by the general formulas (1) to (4), R ¹ to R ³⁴ are preferably hydrogen atoms or methyl groups, and more preferably all are hydrogen atoms.

As the alkyl group having 1 to 6 carbon atoms in R ^{1 to} R ³⁴ described in the general formulas (1) to (4), methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, 1-methyl A propyl group, t-butyl group, pentan-1-yl group, 3-methylbutyl, 2,2-dimethylpropyl group, hexane-1-yl group and the like can be mentioned. Examples of the alkoxy group having 1 to 6 carbon atoms in R ¹ to R ³⁴ described in the general formulas (1) to (4) include a methoxy group, an ethoxy group, a group, a propoxy group, a butoxy group, a pentanoxy group, and a hexanoxy group. Can be mentioned. Any of the substituents listed above can be selected at any position from R ¹ to R ³⁴ .

  In the compounds represented by the general formulas (1) to (4), when the same pyridyl-substituted phenylene group or phenyl-substituted pyridylene group is bonded to all 1, 2, 4, and 5 positions of the benzene ring, It is preferable in that the performance of the light emitting element is good.

  Specific examples of the 1,2,4,5-substituted phenyl derivative represented by the general formula (1) include the following (A1) to (A29), but the compound of the present invention is not limited thereto. .

  Specific examples of the 1,2,4,5-substituted phenyl derivative represented by the general formula (2) include the following (B1) to (B20), but the compound of the present invention is not limited thereto. .

  Specific examples of the 1,2,4,5-substituted phenyl derivative represented by the general formula (3) include the following (C1) to (C29), but the compound of the present invention is not limited thereto. .

  Specific examples of the 1,2,4,5-substituted phenyl derivative represented by the general formula (4) include the following (D1) to (D32), but the compounds of the present invention are limited to these. is not.

  Next, the manufacturing method of this invention is demonstrated.

  The 1,2,4,5-substituted phenyl derivative (1) of the present invention can be produced by the method shown by the following reaction formula.

(In the formula, R ^{1 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ¹ to Y ⁴ each independently represent a leaving group. M represents a metal group or a heteroatom group.)
Hereinafter, this reaction will be described with specific examples, but the present invention is not limited thereto.

Examples of M in the compounds (6-1) to (6-4) include ZnR ³⁵ , MgR ³⁶ , Sn (R ³⁷ ) ₃ , B (OR ³⁸ ) _{2 and the} like. However, R ³⁵ and R ³⁶ each independently represent a chlorine atom, a bromine atom or an iodine atom, R ³⁷ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ³⁸ represents a hydrogen atom or carbon number 1 To R 4, and two R ³⁸ of B (OR ³⁸ ) ₂ may be the same or different. Further, the two R ³⁸ can be combined to form a ring containing an oxygen atom and a boron atom.

As B (OR ³⁸ ) ₂ in the compounds (6-1) to (6-4), B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , B (OBu) ₂ , B ( OPh) ₂ etc. can be illustrated. Examples of B (OR ³⁸ ) ₂ in the case where two R ³⁸ are united to form a ring containing an oxygen atom and a boron atom include groups represented by the following (I) to (VI): The group represented by (II) is preferable because it can be exemplified and the yield is good.

Examples of the leaving group represented by Y ^{1 to} Y ⁴ in the compound (5) include a chlorine group, a bromine group, an iodine group, a trifluoromethylsulfonyloxy (OTf) group, a methanesulfonyloxy (OMs) group, and a chloromethanesulfonyl. An oxy group, p-toluenesulfonyloxy (OTs) group, etc. can be mentioned. Since these leaving groups have reaction selectivity, it is possible to appropriately select different substituents at different positions of Y ¹ to Y ⁴ .

As examples of the compound (5), the following E1 to E289 (wherein R ¹ and R ² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms). .), But the present invention is not limited to these examples.

  In “Step 1”, the compounds (6-1) to (6-4) are reacted with the compound (5) in the presence of a palladium catalyst or a nickel catalyst, optionally in the presence of a base. This is a method for obtaining a 2,4,5-substituted phenyl derivative (1) and applying reaction conditions for general coupling reactions such as Suzuki-Miyaura reaction, Negishi reaction, Tamao-Kumada reaction, Stille reaction, etc. Thus, the target product can be obtained with good yield.

  Examples of the palladium catalyst that can be used in “Step 1” include salts of palladium chloride, palladium acetate, palladium trifluoroacetate, palladium nitrate, and the like. Further, π-allyl palladium chloride dimer, palladium acetylacetonate, tris (dibenzylideneacetone) dipalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium and dichloro (1,1′-bis (diphenylphosphine). Examples include complex compounds such as fino) ferrocene) palladium. Among these, a palladium complex having a tertiary phosphine as a ligand is preferable in terms of a good reaction yield.

  A palladium complex having a tertiary phosphine as a ligand can also be prepared in a reaction system by adding a tertiary phosphine to a palladium salt or a complex compound. The tertiary phosphine that can be used at this time is triphenylphosphine, trimethylphosphine, tributylphosphine, tri (tert-butyl) phosphine, tricyclohexylphosphine, tert-butyldiphenylphosphine, 9,9-dimethyl-4,5. -Bis (diphenylphosphino) xanthene, 2- (diphenylphosphino) -2 '-(N, N-dimethylamino) biphenyl, 2- (di-tert-butylphosphino) biphenyl, 2- (dicyclohexylphosphino) Biphenyl, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,1 ′ -Bis (diphenylphosphino) Erocene, tri (2-furyl) phosphine, tri (o-tolyl) phosphine, tris (2,5-xylyl) phosphine, (±) -2,2′-bis (diphenylphosphino) -1,1′-binaphthyl 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl, 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl, and the like. 2-dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl is preferred because it is easily available and the reaction yield is good.

The molar ratio between the tertiary phosphine and the palladium salt or complex compound is preferably 1:10 to 10: 1, and more preferably 1: 2 to 5: 1 in terms of good reaction yield. In addition, as the nickel catalyst, [1,1′bis (diphenylphosphino) ferrocene] nickel (II) dichloride, [1,2-bis (diphenylphosphino) ethane] nickel (II) dichloride, [1,3-bis (Diphenylphosphino) propane] nickel (II) dichloride, [1,1′bis (diphenylphosphino) propane] nickel (II) dichloride, 1,2-bis (diphenylphosphino) ethane] nickel (II) dichloride, [1,3-bis (diphenylphosphino) propane] nickel (II) dichloride and the like Examples of the base that can be used in "Step 1" include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, carbonate Lithium, cesium carbonate, tripotassium phosphate, sodium phosphate, fluoride Thorium, potassium fluoride, can be exemplified cesium fluoride, etc., tripotassium phosphate is preferable in view good yield. The molar ratio of the base to the compound (6-1), (6-2), (6-3) or (6-4) is preferably 1: 2 to 10: 1, and is 1: 1 to 3: 1 is more desirable.

  The molar ratio of compound (5) used in “Step 1” to compound (6-1), (6-2), (6-3) or (6-4) is preferably 1: 5 to 2: 1. From the viewpoint of good yield, 1: 2 to 2: 1 is more desirable. In addition, the compounds (6-1), (6-2), (6-3) or (6-4) may be the same or different. In some cases, the intermediates are isolated and sequentially reacted. Or may be added sequentially without isolation.

  Examples of the solvent that can be used in “Step 1” include water, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, dioxane, toluene, benzene, diethyl ether, ethanol, methanol, and xylene, and these may be used in appropriate combination. . It is desirable to use a mixed solvent of toluene and ethanol in terms of good yield.

  “Step 1” can be performed at a temperature appropriately selected from 0 ° C. to 150 ° C., and is more preferably performed at 60 ° C. to 100 ° C. in terms of a good yield.

  Compound (1) can be obtained by carrying out a normal treatment after completion of “Step 1”. If necessary, it may be purified by recrystallization, column chromatography or sublimation.

  Further, the 1,2,4,5-substituted phenyl derivatives (2) to (4) of the present invention can also be produced by the reaction formulas represented by the following “Step 2” to “Step 4”. is there.

(In the formula, R ^{1 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X ^{1 to} X ⁸ represent a carbon atom or a nitrogen atom. , X ¹ and X ² , X ³ and X ⁴ , X ⁵ and X ⁶ , X ⁷ and X ⁸ cannot simultaneously be a nitrogen atom or a carbon atom, and Y ^{1 to} Y ⁴ each independently represents a leaving group. M represents a metal group or a heteroatom group.)

(In the formula, R ^{1 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ¹ to Y ⁴ each independently represent a leaving group. M represents a metal group or a heteroatom group.)

(Wherein R ^{1 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X ^{1 to} X ¹⁶ represent a nitrogen atom or a carbon atom. However, one of four atoms X ^{1 to} X ⁴ , X ^{5 to} X ⁸ , X ^{9 to} X ¹² , and X ^{13 to} X ¹⁶ is a nitrogen atom, and the other three atoms are carbon atoms. Y ^{1 to} Y ⁴ each independently represents a leaving group, and M represents a metal group or a heteroatom group.)
These reactions in Steps 2 to 4 can be synthesized using a method similar to “Step 1”, which is a method for synthesizing the 1,2,4,5-substituted phenyl derivative (1).

  Furthermore, the 1,2,4,5-substituted phenyl derivatives (1) to (4) of the present invention can also be produced by the methods shown in the following “Step 5” to “Step 8”.

(In the formula, R ^{1 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Z ^{1 to} Z ⁴ each independently represent a metal group or a hetero atom. Y ⁵ represents a leaving group.

(In the formula, R ^{1 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X ^{1 to} X ⁸ represent a carbon atom or a nitrogen atom. However, X ¹ and X ² , X ³ and X ⁴ , X ⁵ and X ⁶ , X ⁷ and X ⁸ cannot be a nitrogen atom or a carbon atom at the same time Z ^{1 to} Z ⁴ are each independently a metal group Or represents a heteroatom group, and Y ⁵ represents a leaving group.)

(Wherein R ^{1 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Z ^{1 to} Z ⁴ each independently represent a metal group or hetero Represents an atomic group, Y ⁵ represents a leaving group.)

(Wherein R ^{1 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X ^{1 to} X ¹⁶ represent a nitrogen atom or a carbon atom. However, one of four atoms X ^{1 to} X ⁴ , X ^{5 to} X ⁸ , X ^{9 to} X ¹² , and X ^{13 to} X ¹⁶ is a nitrogen atom, and the other three atoms are carbon atoms. Z ^{1 to} Z ⁴ each independently represents a metal group or a heteroatom group, and Y ⁵ represents a leaving group.)
Examples of the metal group or heteroatom group represented by Z ^{1 to} Z ⁴ in the compound (10) include Sn (R ³⁷ ) ₃ , B (OR ³⁸ ) _{2 and the} like. ^{However, R 37} represents an alkyl group or phenyl group having 1 to 4 carbon ^{atoms, R 38} is a hydrogen atom, an alkyl group or a phenyl group having a carbon number of 1 to 4, ^{B (OR} _{38) 2} the two R ³⁸ may be the same or different. Further, the two R ³⁸ can be combined to form a ring containing an oxygen atom and a boron atom.

Examples of B (OR ³⁸ ) ₂ in the compound (10) include B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , B (OBu) ₂ , B (OPh) _{2 and the} like. Examples of B (OR ³⁸ ) ₂ in the case where two R ³⁸ are united to form a ring containing an oxygen atom and a boron atom include groups represented by the following (I) to (VI): The group represented by (II) is preferable because it can be exemplified and the yield is good.

Examples of the leaving group represented by Y ⁵ in the compounds (11) to (14) include a chlorine group, a bromine group, an iodine group, a trifluoromethylsulfonyloxy group, a methanesulfonyloxy group, a chloromethanesulfonyloxy group, and p-. And toluenesulfonyloxy.

  In “Step 5” to “Step 8”, the same reaction conditions as in “Step 1” can be used. In addition, the compounds (1) to (4) can be obtained by performing ordinary treatment after the completion of “Step 5” to “Step 8”. If necessary, it may be purified by recrystallization, column chromatography or sublimation.

Although there is no particular limitation on the method for producing an organic electroluminescent device comprising the 1,2,4,5-substituted phenyl derivative (1) to (4) of the present invention as a constituent component, film formation by vacuum vapor deposition is possible. . Film formation by the vacuum evaporation method can be performed by using a general-purpose vacuum evaporation apparatus. The vacuum degree of the vacuum chamber when forming a film by the vacuum evaporation method is reached by a diffusion pump, a turbo molecular pump, a cryopump, etc. that are generally used in consideration of the manufacturing tact time and manufacturing cost of manufacturing the organic electroluminescence device. It is preferably about 1 × 10 ⁻² to 1 × 10 ⁻⁵ Pa. The deposition rate is preferably 0.005 to 1.0 nm / second, depending on the thickness of the film to be formed.

  Further, the 1,2,4,5-substituted phenyl derivatives (1) to (4) of the present invention can be formed by a spin coat method, an ink jet method, a cast method, a dip method or the like using a general-purpose apparatus. is there.

  The 1,2,4,5-substituted phenyl derivatives (1) to (4) of the present invention are useful as materials for fluorescent or phosphorescent organic electroluminescent devices because they have good charge injection and transport properties. It can be used as a host material or an electron transport material.

  The band gap of the 1,2,4,5-substituted phenyl derivatives (1) to (4) of the present invention is 3.2 eV or more, and the three primary colors (red: 1.9 eV, green: 2) constituting the panel. .4 eV, blue: 2.8 eV) wide band gap material sufficient to confine energy of each color. Therefore, it can be applied to various elements such as a single color display element, a three primary color display element, and a white element for illumination use. Furthermore, since the solubility can be controlled by changing the substituent, it can be applied not only to a vapor deposition element but also to a coating element. The fluorescent or phosphorescent organic electroluminescent device can be driven at a low voltage to reduce the power consumption, and the lifetime of each device can be extended.

It is sectional drawing of the organic electroluminescent element produced in Test Example-1.

  Hereinafter, although an example of an experiment and a test example are given and the present invention is explained still in detail, the present invention is not limited to these.

  Example-1

  Under a stream of argon, 1.00 g (2.5 mmol) of 1,2,4,5-tetrabromobenzene, 4.04 g (20 mmol) of 4- (2-pyridyl) phenylboronic acid, 28.5 mg (0.13 mmol) of palladium acetate ), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl 121 mg (0.25 mmol) and tripotassium phosphate 5.39 g (25 mmol) were dissolved in 10 mL toluene, 1 mL water and heated. The mixture was stirred for 44 hours under reflux. After cooling to room temperature, it was diluted with methanol and the solid was filtered off. The obtained crude product was purified by silica gel column chromatography (developing solvent: chloroform: hexane = 2: 1 to 1: 0) to obtain the desired 4,4 ″ -di (2-pyridyl) -4 ′, 5 ′. A white solid (yield 1.38 g, 79% yield) of -bis [4- (2-pyridyl) phenyl] -1,1 ′; 2 ′, 1 ″ -terphenyl was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.21-7.53 (m, 4H), 7.44 (d, J = 8.44 Hz, 8H), 7.69 (s, 2H), 7.53- 7.79 (m, 8H), 7.94 (d, J = 8.48 Hz, 8H), 8.70 (d, J = 4.56 Hz, 4H).
Example-2

  Under argon stream, 1,2,4,5-tetrabromobenzene 1.00 g (2.5 mmol), 4- (pyridin-3-yl) phenylboronic acid 4.04 g (20 mmol), palladium acetate 28.5 mg (0 .13 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl 121 mg (0.25 mmol) and tripotassium phosphate 5.39 g (25 mmol) were dissolved in 20 mL dioxane, 6 ml water. The mixture was stirred for 21 hours under heating and reflux. After cooling to room temperature, it was diluted with water and the solid was filtered off. The obtained crude product was purified by silica gel column chromatography (developing solvent: chloroform) to obtain the desired 4,4 ″ -di (3-pyridyl)-[4- (3-pyridyl) phenyl] -1,1 ′. 2 ′, 1 ″ -terphenyl white solid was obtained (yield 1.35 g, yield 77%).

¹ H-NMR (CDCl ₃ ): δ 7.46 (d, J = 8.28 Hz, 8H), 7.48-7.56 (m, 4H), 7.57 (d, J = 8.32 Hz, 8H) ), 7.69 (s, 2H), 8.07 (d, J = 7.12 Hz, 4H), 8.63 (dd, J = 1.48, 4.96 Hz, 4H), 8.92 (d , J = 1.96 Hz, 4H).
Example-3

  Under an argon stream, 1,2,4,5-tetrabromobenzene 65.9 mg (0.17 mmol), 4- (4-pyridyl) phenylboronic acid 200 mg (1.01 mmol), palladium acetate 1.88 mg (0.0084 mmol) ), 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl 8.60 mg (0.021 mmol) and tripotassium phosphate 640 mg (3.02 mmol) are dissolved in 100 mL of toluene and heated under reflux for 48 hours. Stir. After cooling to room temperature, it was diluted with 300 mL of chloroform, and the solid was filtered off. The organic layer is concentrated, and the resulting crude product is purified by silica gel chromatography (developing solvent: chloroform: methanol = 99: 1 to 20: 1) to obtain the desired 4,4 ″ -di (4-pyridyl)- A white solid (yield 20 mg, 17%) of 4 ′, 5′-bis [4- (4-pyridyl) phenyl] -1,1 ′; 2 ′, 1 ″ -terphenyl was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.52 (s, 2H), 7.54 (d, J = 6.21 Hz, 8H), 7.65 (d, J = 8.28 Hz, 8H), 7. 85 (d, J = 8.28 Hz, 8H), 8.68 (d, J = 6.21 Hz, 8H).
Example-4

  Under an argon stream, 1,2,4,5-tetrabromobenzene 0.50 g (1.3 mmol), 3- (2-pyridyl) phenylboronic acid 2.02 g (10 mmol), palladium acetate 14.3 mg (0.06 mmol) ), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl 60.5 mg (0.13 mmol) and tripotassium phosphate 2.70 g (13 mmol) were dissolved in 10 mL of toluene and 2 mL of water. The mixture was stirred for 48 hours with heating under reflux. After cooling to room temperature, it was diluted with methanol and the solid was filtered off. The obtained crude product was purified by silica gel column chromatography (developing solvent: chloroform), and the desired 3,3 ″ -di (2-pyridyl) -4 ′, 5′-bis [3- (2-pyridyl) was obtained. A white solid (yield 0.83 g, yield 95%) of phenyl] -1,1 ′; 2 ′, 1 ″ -terphenyl was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.17-7.25 (m, 4H), 7.30 (d, J = 7.76 Hz, 4H), 7.36 (t, J = 7.62 Hz, 4H) ), 7.55 (d, J = 8.00 Hz, 4H), 7.69 (t, J = 7.72 Hz, 4H), 7.79 (s, 2H), 7.93 (d, J = 7) .92 Hz, 4H), 8.02 (s, 4H).
Example-5

  Under an argon stream, 1,2,4,5-tetrabromobenzene 0.50 g (1.3 mmol), 2- (4-methylphenyl) pyridin-5-ylboronic acid 2.16 g (10.2 mmol), palladium acetate 14 .3 mg (0.06 mmol), 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl 60.5 mg (0.13 mmol), tripotassium phosphate 2.70 g (13 mmol) in 20 mL of toluene, It melt | dissolved in 2 ml of water, and stirred for 72 hours under heating-refluxing. Then, water was added, and the solvent was removed under reduced pressure after extraction with chloroform. The precipitated solid was recrystallized from 25 ml of o-xylene, and the desired 1,2,4,5-tetrakis [2- (4-methylphenyl) pyridin-5-yl] benzene white solid (yield 901 mg, yield) 95%).

¹ H-NMR (CDCl ₃ ): δ 2.44 (s, 12H), 7.30 (d, J = 8.28 Hz, 8H), 7.63 (d, J = 8.24 Hz, 4H), 7. 68 (d, J = 8.40 Hz, 4H), 7.69 (s, 2H), 7.91 (d, J = 8.20 Hz, 8H), 8.67 (s, 4H).
Test Example-1
As the substrate, a glass substrate with an ITO transparent electrode in which an indium-tin oxide (ITO) film having a width of 2 mm was patterned in a stripe shape was used. The substrate was cleaned with isopropyl alcohol and then surface treated by ozone ultraviolet cleaning. Each layer was vacuum-deposited on the cleaned substrate by a vacuum deposition method, and an organic electroluminescence device having a light-emitting area of 4 mm ² as shown in FIG.

First, the said glass substrate was introduce | transduced in the vacuum evaporation tank and it pressure-reduced to 1.0 * 10 <^-4> Pa. Thereafter, a hole injection layer 2, a hole transport layer 3, a light emitting layer 4 and an electron transport layer 5 are sequentially formed as an organic compound layer on the glass substrate indicated by 1 in FIG. Filmed. As the hole injection layer 2, sublimation-purified phthalocyanine copper (II) was vacuum-deposited with a film thickness of 25 nm. As the hole transport layer 3, N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (NPD) was vacuum-deposited with a film thickness of 45 nm. As the light emitting layer 4, 2-t-butyl-9,10-di (2-naphthyl) anthracene (TBADN) and 4,4′-bis [4- (di-p-tolylamino) phenylethen-1-yl] Biphenyl (DPAVBi) was vacuum-deposited at a film thickness of 40 nm at a ratio of 97: 3 (% by mass). As the electron transport layer 5, 4,4 ″ -di (2-pyridyl) -4 ′, 5′-bis [4- (2-pyridyl) phenyl] 1,1 synthesized in Example-1 of the present invention was used. ';2', 1 ''-Terphenyl was vacuum deposited with a film thickness of 20 nm.

  Each organic material was formed into a film by a resistance heating method, and the heated compound was vacuum-deposited at a film formation rate of 0.3 to 0.5 nm / second. Finally, a metal mask is disposed so as to be orthogonal to the ITO stripe, and the cathode layer 6 is formed. The cathode layer 6 was made into a two-layer structure by vacuum deposition of lithium fluoride and aluminum with a thickness of 1.0 nm and 100 nm, respectively. Each film thickness was measured with a stylus type film thickness meter (DEKTAK). Furthermore, this element was sealed in a nitrogen atmosphere glove box having an oxygen and moisture concentration of 1 ppm or less. Sealing was performed using a glass sealing cap and the above-described film-forming substrate epoxy type ultraviolet curable resin (manufactured by Nagase ChemteX Corporation).

A direct current was applied to the produced organic electroluminescence device, and the light emission characteristics were evaluated using a luminance meter of LUMINANCE METER (BM-9) manufactured by TOPCON. As light emission characteristics, voltage (V), luminance (cd / m ² ), current efficiency (cd / A), and power efficiency (lm / W) when a current density of 20 mA / cm ² is passed are measured, and when continuously lit The luminance half time of was measured.

The measured values of the fabricated element were 3.8 V, 2070 cd / m ² , 10.4 cd / A, and 8.5 lm / W. The luminance half time of this device was 1550 hours.

Comparative Example-1
In place of the electron transport layer 5 of Test Example 1, an organic electroluminescent element obtained by vacuum-depositing tris (8-quinolinolato) aluminum (III) (Alq), which is an existing material, with a film thickness of 20 nm was used in the same manner as Test Example 1. Produced.

The measured values of the manufactured element were 6.4 V, 1664 cd / m ² , 8.3 cd / A, and 4.1 lm / W. The luminance half time of this device was 1500 hours.

  The fluorescent or phosphorescent organic electroluminescent device using the 1,2,4,5-substituted phenyl derivatives (1) to (4) of the present invention has lower power consumption and longer length than the devices using existing materials. It was confirmed that the lifetime could be achieved. In addition, the 1,2,4,5-substituted phenyl derivatives (1) to (4) of the present invention are organic electroluminescent using other fluorescent light emitting materials and phosphorescent materials in addition to the electron transport layer of this example. Application to an element is also possible. In addition to applications such as flat panel displays, the present invention is useful for lighting applications that require both low power consumption and long life.

1. 1. Glass substrate with ITO transparent electrode 2. hole injection layer Hole transport layer 4. 4. Light emitting layer Electron transport layer 6. Cathode layer

Claims (3)

1,2,4,5-substituted phenyl derivatives represented by the following (A1) to (A3), (A5) to (A6), and (A8) to (A29).

General formula (5)

(In the formula, R ¹ and R ² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ¹ to Y ⁴ each independently represent a leaving group. And a compound represented by formula (6-1)

(In the formula, R ^{3 to} R ⁶ and R ^{19 to} R ²² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. M represents a metal group or a heteroatom group. And a compound represented by the general formula (6-2):

(Wherein R ^{7 to} R ¹⁰ and R ^{23 to} R ²⁶ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. M represents a metal group or a heteroatom group. And a compound represented by formula (6-3):

(Wherein R ^{11 to} R ¹⁴ and R ^{27 to} R ³⁰ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. M represents a metal group or a heteroatom group. And a compound represented by formula (6-4):

(Wherein R ^{15 to} R ¹⁸ and R ^{31 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. M represents a metal group or a heteroatom group. The method for producing a 1,2,4,5-substituted phenyl derivative according to claim 1, wherein the compound is represented by a coupling reaction in the presence of a base and a metal catalyst. General formula (10)

(In the formula, R ¹ and R ² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Z ^{1 to} Z ⁴ each independently represent a metal group or a hetero atom. And a compound represented by formula (11-1):

(Wherein R ^{3 to} R ⁶ and R ^{19 to} R ²² each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ⁵ represents a leaving group. ) And the general formula (11-2)

(Wherein R ^{7 to} R ¹⁰ and R ^{23 to} R ²⁶ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ⁵ represents a leaving group. ) And the general formula (11-3)

(In the formula, R ^{11 to} R ¹⁴ and R ^{27 to} R ³⁰ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ⁵ represents a leaving group. ) And the general formula (11-4)

(Wherein R ^{15 to} R ¹⁸ and R ^{31 to} R ³⁴ each independently represent hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Y ⁵ represents a leaving group. The method for producing a 1,2,4,5-substituted phenyl derivative according to claim 1, wherein a coupling reaction is carried out in the presence of a base and a metal catalyst.

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