JP2009167162A - Organic electroluminescent device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new pyridylpyridine platinum complex. <P>SOLUTION: The platinum complex represented by general formula (1) (wherein, R represents H or a substituent; L<SP>1</SP>represents a single bond or a linking group; and X represents a halogen) is obtained by reacting compounds represented by general formulas (B-2) and (B-2') with a compound represented by general formula (A-O), to obtain a compound represented by general formula (C-O), and reacting the resultant compound with a platinum salt. The platinum complex is useful as a light-emitting material for organic EL devices. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a platinum complex compound useful as a light emitting material and an organic electroluminescent device (hereinafter also referred to as “organic EL device”) using the same.

  In recent years, organic electroluminescence devices have been actively researched and developed because they can emit light with high luminance when driven at a low voltage. In general, an organic EL element is composed of an organic layer including a light emitting layer and a pair of electrodes sandwiching the layer, and the electrons injected from the cathode and the holes injected from the anode are recombined in the light emitting layer. The energy of the excitons is used for light emission.

  By using a phosphorescent material, the efficiency of the device is increasing. Known phosphorescent materials include iridium complexes and platinum complexes (Patent Document 1).

  The use of a platinum complex having a tetradentate ligand has already been reported to improve the luminous efficiency and durability of the organic EL device (Patent Document 2). Among these platinum complexes, complexes having a pyridylpyridine skeleton can shorten the emission wavelength compared to complexes having a phenylpyridine skeleton, and are promising as light blue to blue light emitting materials. However, since it is difficult to suppress by-products in complexation, it has been necessary to establish a practical production method.

In addition, a blue light emitting material having a pyridylpyrazole skeleton and an organic EL element using the same have been reported (Patent Document 3), but the development of an element that achieves both high efficiency and durability, particularly in use at high luminance. Not in. Considering the development of organic EL elements in lighting equipment, it is necessary to use high-luminance, so the development of a blue light-emitting material with excellent durability at high luminance is desired.
JP 2005-220136 A International Publication No. 04-108857 Pamphlet JP 2007-19462

  An object of the present invention is to provide a method for producing a pyridylpyridine platinum complex having a specific structure capable of improving the yield of the complexing step, a platinum complex produced by the production method, and a pyridylpyridine platinum having a specific structure. An object of the present invention is to provide an organic electroluminescent device which is excellent in durability when used in a complex and at high luminance.

  As a result of investigations to solve the above problems, the inventors of the present invention have a low yield in the complexing step with a pyridylpyridine ligand and a platinum (II) salt. Suppression of coordination to the nitrogen atom to platinum by introducing an electron-withdrawing substituent at the α-position of the nitrogen atom of the pyridine ring (effect of steric hindrance and reduction of electron density on the nitrogen atom) ), The pyridylpyridine complex can be synthesized with good yield, and the pyridylpyridine complex has improved durability in use of the organic EL device at high luminance as compared with a known blue light emitting material. As a result, the present invention has been completed. That is, the present invention has been achieved by the following means.

(1) A compound represented by general formula (B-2) and general formula (B-2 ′) is reacted with a compound represented by general formula (A-0) to give a general formula (C-0). A process for obtaining a compound represented by formula (1) and a step for reacting a compound represented by formula (C-0) with a platinum salt, Method.
General formula (B-2)

(In the general formula (B-2), R ¹⁷ and R ¹⁸ each independently represents a hydrogen atom or a substituent, provided that at least one of R ¹⁷ and R ¹⁸ represents an electron-withdrawing substituent. R ^A represents a hydrogen atom or a substituent.)
General formula (B-2 ′)

(In the general formula (B-2 ′), R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or a substituent, provided that at least one of R ¹⁹ and R ²⁰ represents an electron-attracting substituent. R ^B represents a hydrogen atom or a substituent.)
General formula (A-0)

(In the general formula (A-0), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represents a hydrogen atom or a substituent. L ¹ represents a single bond or a divalent group. X represents a halogen atom.)
General formula (C-0)

(In the general formula (C-0), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ^A and R ^B each independently represents a hydrogen atom or a substituent. R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or a substituent, provided that at least one of R ¹⁷ and R ¹⁸ represents an electron withdrawing substituent, and at least one of R ¹⁹ and R ²⁰ One represents an electron-withdrawing substituent, and L ¹ represents a single bond or a divalent linking group.)
General formula (1)

(In the general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ^A and R ^B each independently represents a hydrogen atom or a substituent. R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or a substituent, provided that at least one of R ¹⁷ and R ¹⁸ represents an electron withdrawing substituent, and at least one of R ¹⁹ and R ²⁰ represents Represents an electron-attracting substituent, L ¹ represents a single bond or a divalent linking group.)

(2) A platinum complex represented by the general formula (1).
General formula (1)

(In the general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ^A and R ^B each independently represents a hydrogen atom or a substituent. R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or a substituent, provided that at least one of R ¹⁷ and R ¹⁸ represents an electron withdrawing substituent, and at least one of R ¹⁹ and R ²⁰ represents Represents an electron-attracting substituent, L ¹ represents a single bond or a divalent linking group.)

(3) The platinum complex according to (2), wherein the general formula (1) is represented by the following general formula (2).
General formula (2)

(In the general formula (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ^A and R ^B are the same as those in the general formula (1). R ²¹ and R ²² each independently represents a hydrogen atom or a substituent.

  (4) A platinum complex produced by the method according to (1).

(5) An organic electroluminescent device having at least one organic layer between a pair of electrodes, wherein the organic layer contains at least one platinum complex described in (2), (3) and (4) An organic electroluminescent element characterized by comprising:
(6) An organic electroluminescent device having at least one organic layer between a pair of electrodes, wherein the light emitting layer contains at least one kind of platinum complex according to (2), (3) and (4) An organic electroluminescent element characterized by comprising:

  By this invention, the platinum complex represented by General formula (1) and General formula (2) can be manufactured with a sufficient yield. In addition, by including these platinum complexes in the organic layer, an organic electroluminescence device having excellent durability particularly in use at high luminance can be provided.

  In the present invention, the substituent group B is defined as follows.

(Substituent group B)
An alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n- Decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, For example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, For example, propargyl, 3-pentynyl, etc.), aryl groups (preferably having 6 to 30 carbon atoms, more preferably A prime number of 6 to 20, particularly preferably a carbon number of 6 to 12, such as phenyl, p-methylphenyl, naphthyl, anthranyl, etc., an amino group (preferably a carbon number of 0 to 30, more preferably a carbon number). 0 to 20, particularly preferably 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino, etc.), an alkoxy group (preferably 1 to 1 carbon atoms). 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy, 2-ethylhexyloxy and the like, and aryloxy groups (preferably 6 carbon atoms). -30, more preferably 6-20 carbons, particularly preferably 6-12 carbons, Phenyloxy, 1-naphthyloxy, 2-naphthyloxy, etc.), a heterocyclic oxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms). For example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.)

  An acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group ( Preferably it has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl and the like, and an aryloxycarbonyl group (preferably having a carbon number). 7 to 30, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl, and acyloxy groups (preferably 2 to 30 carbon atoms, more preferably carbon atoms). 2 to 20, particularly preferably 2 to 10 carbon atoms, for example, acetoxy, benzoyloxy An acylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino). An alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms such as methoxycarbonylamino), aryloxycarbonylamino group (Preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino).

  A sulfonylamino group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino), a sulfamoyl group ( Preferably it is C0-30, More preferably, it is C0-20, Most preferably, it is C0-12, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl etc. are mentioned. ), A carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like.) An alkylthio group (preferably having 1 to 30 carbon atoms) Preferably it is C1-C20, Most preferably, it is C1-C12, for example, methylthio, ethylthio etc. are mentioned, for example, An arylthio group (Preferably C6-C30, More preferably C6-C20, Particularly preferably, it has 6 to 12 carbon atoms, and examples thereof include phenylthio.), A heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms). For example, pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like, and a sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 carbon atom). To 20, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl).

  A sulfinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.), ureido group (preferably carbon 1 to 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid amide group (preferably having 1 carbon atom) To 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphate amide and phenyl phosphate amide), hydroxy group, mercapto group, halogen atom (for example, Fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group Hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic (heteroaryl) group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms. Examples of the hetero atom include nitrogen atom, oxygen Atom, sulfur atom, and specifically imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group and the like. (Preferably 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, for example, trimethylsilyl, triphenylsilyl, etc.), silyloxy group (preferably 3 carbon atoms) To 40, more preferably 3 to 30 carbon atoms, particularly preferably carbon 3 to 24, for example trimethylsilyloxy, etc. triphenylsilyl oxy and the like.) And the like. These substituents may be further substituted.

  Hereinafter, a platinum complex having a tetradentate ligand represented by the general formula (1) will be described.

In the description of the general formula (1) and the general formula (2), the hydrogen atom includes an isotope (deuterium atom and the like), and the atoms constituting the substituent further include the isotope.
General formula (1)

In general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ each independently represent a hydrogen atom or a substituent. The substituents represented by R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are as defined in Substituent Group B. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ may be bonded to each other to form a ring, if possible.

R ¹¹ and R ¹⁶ are preferably hydrogen atoms, alkyl groups, aryl groups, amino groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, alkylthio groups, sulfonyl groups, hydroxy groups, halogen atoms, cyano groups. , A nitro group, a heterocyclic group, more preferably a hydrogen atom, an alkyl group, an aryl group, a halogen atom, a cyano group, or a heterocyclic group, still more preferably a hydrogen atom, a methyl group, a t-butyl group, A trifluoromethyl group, a phenyl group, a fluorine atom, a cyano group, and a pyridyl group are more preferable, and a hydrogen atom, a methyl group, and a fluorine atom are more preferable, and a hydrogen atom is particularly preferable.

R ¹³ and R ¹⁴ are preferably synonymous with the preferred ranges of R ¹¹ and R ¹⁶ .

R ¹² and R ¹⁵ are preferably a hydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, a cyano group, or a heterocyclic group, more preferably A hydrogen atom, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a halogen atom, and a heterocyclic group, and more preferably a hydrogen atom, an alkyl group, an amino group, an alkoxy group, a halogen atom, and a heterocyclic ring. More preferably a hydrogen atom, a methyl group, a t-butyl group, a dialkylamino group, a diphenylamino group, a methoxy group, a phenoxy group, a fluorine atom, an imidazolyl group, a pyrrolyl group or a carbazolyl group, particularly preferably Hydrogen atom, methyl group, fluorine atom, methoxy group, and phenoxy group. Properly is hydrogen atom, a methyl group.

R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or a substituent. The substituents represented by R ¹⁷ , R ¹⁸ , R ¹⁹ , and R ^{20 have the same} meanings as the substituent group B. However, at least one of R ¹⁷ and R ¹⁸ represents an electron withdrawing substituent, and at least one of R ¹⁹ and R ²⁰ represents an electron withdrawing substituent.

A preferred embodiment is an embodiment in which R ¹⁷ and R ²⁰ are electron-withdrawing substituents, an embodiment in which R ¹⁸ and R ¹⁹ are electron-withdrawing substituents, or all of R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are It is an embodiment that is an electron withdrawing substituent, and a more preferred embodiment is an embodiment in which all of R ¹⁷ , R ¹⁸ , R ¹⁹ , and R ²⁰ are electron withdrawing substituents. Here, the plurality of electron withdrawing substituents may be the same or different.

  The electron withdrawing substituent is a substituent having a σ value (σm or σp) larger than 0 in Hammett's rule. In the present specification, a substituent in which at least one of σm and σp is greater than 0 is defined as an electron withdrawing group. Definitions and values of σ values are reported in the literature (for example, Chem. Rev., 1991, 91, 165-195).

Examples of R ¹⁷ , R ¹⁸ , R ¹⁹ , and R ²⁰ include a hydrogen atom, a halogen atom, a phenyl group substituted with a fluorine atom, an alkoxy group substituted with fluorine, a perfluoroalkyl group, a cyano group, a nitro group, Examples thereof include an aryloxy group, an alkyl group, an aryl group, a silyl group, a trialkylsilyl group, and a triarylsilyl group.
R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are preferably a hydrogen atom, a halogen atom, a phenyl group substituted with a fluorine atom, an alkoxy group substituted with fluorine, a perfluoroalkyl group, a cyano group, a nitro group, An aryloxy group, more preferably a hydrogen atom, a fluorine atom, a phenyl group substituted with a fluorine atom, a trifluoromethoxy group, a trifluoromethyl group, a cyano group, or a phenoxy group, and more preferably a hydrogen atom, A phenoxy group substituted with a fluorine atom, a perfluorophenyl group, a trifluoromethyl group, a cyano group or an electron withdrawing substituent, and particularly preferably a hydrogen atom, a fluorine atom or an electron withdrawing substituent. A phenoxy group, most preferably a hydrogen atom or a fluorine atom.

  Among the phenoxy groups substituted with an electron withdrawing substituent, the electron withdrawing substituent is preferably a fluorine atom, a trifluoromethyl group or a cyano group, preferably a fluorine atom or a trifluoromethyl group. More preferred are phenoxy groups. The number of electron withdrawing substituents is preferably 1 to 5, more preferably 1 to 3, and most preferably 1 or 2.

R ^A and R ^B represent a hydrogen atom or a substituent. R ^A and R ^B may be linked to each other.

R ^A and R ^B are preferably a hydrogen atom, alkyl group, aryl group, amino group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, alkylthio group, sulfonyl group, hydroxy group, halogen atom, cyano group, A nitro group and a heterocyclic group, more preferably a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, a halogen atom, and a cyano group, still more preferably a hydrogen atom, an alkyl group, A perfluoroalkyl group, an aryl group, a halogen atom, and a cyano group, more preferably a hydrogen atom, a methyl group, a trifluoromethyl group, and a cyano group, and particularly preferably a hydrogen atom, a trifluoromethyl group, a fluorine atom, A cyano group, most preferably a hydrogen atom.

L ¹ represents a single bond or a divalent linking group. Although it does not specifically limit as a bivalent coupling group, The coupling group which consists of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a silicon atom is preferable. Specific examples of the divalent linking group are shown below, but the present invention is not limited thereto.

  Ro represents a substituent selected from the substituent group B. Ro is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms. m represents an integer of 0 to 5. m is preferably 0 to 4, more preferably 0 to 3.

L ¹ is preferably a dialkylmethylene group, a diarylmethylene group or a diheteroarylmethylene group, more preferably a dimethylmethylene group, a methylphenylmethylene group or a diphenylmethylene group, still more preferably a dimethylmethylene group.

  These linking groups may be substituted with hydrogen atoms. In this case, examples of the substituent include substituent group B. In the case of having a plurality of substituents, the substituents may be linked to form a ring.

  General formula (B-2) and general formula (B-2 ') are demonstrated.

In the general formula (B-2) and the general formula (B-2 ′), R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ^A and R ^B are as defined in the general formula (1). The preferred range is also the same.

  General formula (A-0) is demonstrated.

In the general formula (A-0), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and L ¹ have the same meaning as in the general formula (1). The preferred range is also the same. X represents a halogen atom.
The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom, a bromine atom or an iodine atom, still more preferably a chlorine atom or a bromine atom.

  General formula (C-0) is demonstrated.

In the general formula (C-0), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ^A , R ^B and L ¹ are general It is synonymous with Formula (1). The preferred range is also the same.

  The platinum complex represented by the general formula (1) is more preferably a complex represented by the general formula (2).

In the general formula (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ^A and R ^B are as defined in the general formula (1). It is. The preferred range is also the same. R ²¹ and R ²² each independently represents a hydrogen atom or a substituent.
The substituents represented by R ²¹ and R ²² have the same meanings as in the substituent group B. R ²¹ and R ²² may be connected to each other to form a cyclic structure such as a cyclohexane ring or a cyclopentane ring.

R ²¹ and R ²² are preferably a hydrogen atom, an alkyl group, an aryl group, a halogen atom, or a heterocyclic group, more preferably a hydrogen atom, a methyl group, a phenyl group, a fluorine atom, or a pyridyl group, still more preferably. A methyl group, a phenyl group, and a fluorine atom, and most preferably a methyl group and a phenyl group

  The platinum complex represented by the general formula (1) or (2) may be a low molecular weight compound, or a high molecular weight compound in which a residue is connected to a polymer main chain (preferably a mass average molecular weight of 1000 to 5000000, Preferably 5,000 to 2,000,000, more preferably 10,000 to 1,000,000) or a high molecular weight compound having a main chain structure of the platinum complex of the present invention (preferably a mass average molecular weight of 1,000 to 5,000,000, more preferably 5,000 to 2,000,000, more preferably 10,000 to 1000000). In the case of a high molecular weight compound, it may be a homopolymer, may be a copolymer with another polymer, and if it is a copolymer, it may be a random copolymer or a block copolymer. There may be. Further, in the case of a copolymer, a compound having a light emitting function and / or a compound having a charge transport function may be included in the polymer.

  Specific examples of the complex represented by the general formula (1) in the present invention are illustrated below, but the present invention is not limited thereto.

  The production method of the present invention will be described.

  A compound represented by formula (A-0) is reacted with compounds (B-2) and (B-2 ′) having a substituent at a specific position of the pyridine ring (α-position of the nitrogen atom of pyridine). And a step of obtaining a compound represented by the general formula (C-0), and a step of reacting the compound represented by the general formula (C-0) with a platinum salt. It is a manufacturing method of the platinum complex represented by these.

In the above formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ^A , R ^B and L ¹ are the same as those in the general formula (1). It is synonymous with them. X represents a halogen atom.

  The compound (B-2) having a substituent at a specific position of the pyridine ring (α position of the nitrogen atom of pyridine) can be obtained from (B-3) or (B-4) via a lithiated compound (Org. Lett., 6, 277 (2004)). (B-2 ′) can also be synthesized by the same method.

In said formula, R <^17> , R <^18> and ^RA are synonymous with those in General formula (1).

  The compound represented by the general formula (C-0) includes a compound represented by the general formula (B-2) and the general formula (B-2 ′) and a compound represented by the general formula (A-0). It can be synthesized by reacting in a solvent in the presence of a palladium catalyst, (optionally a ligand) and a base.

  The compound represented by the general formula (B-2) and the general formula (B-2 ′) is used in an amount of 1.0 to 10 moles, respectively, with respect to the compound represented by the general formula (A-0). However, it is preferable to use 1.0-6 mol times amount, and it is more preferable to use 1.0-3 mol times amount.

  The reaction is usually performed under normal pressure, but may be performed under pressure or under reduced pressure as necessary. Furthermore, the reaction may be carried out in air, but it is preferably carried out in an inert atmosphere such as nitrogen or argon in order to prevent the deactivation of the palladium catalyst.

  Although it does not specifically limit as a solvent used for the said reaction, Water; Aromatic hydrocarbons, such as benzene, toluene, xylene; Halogenated hydrocarbons, such as dichloroethane and chloroform; Tetrahydrofuran, 1,2- dimethoxyethane, 1 Ethers such as 1,4-dioxane and diethyl ether; alcohols such as methanol, ethanol and isopropyl alcohol; esters such as ethyl acetate and butyl acetate. Of these, water, aromatic hydrocarbons, and ethers are preferable. These solvents may be used as a mixture of two or more.

  The amount of the solvent used may be a stirrable amount, and is usually used in an amount of 1 to 200 times by weight, preferably 2 to 100 times by weight of the compound (A-0).

  As the palladium catalyst used in the above reaction, a divalent palladium salt or a zero-valent palladium salt is used. Examples of the divalent palladium include palladium acetate and dichlorobistoluphenylphosphine palladium, and examples of the zero-valent palladium include tetrakistriphenylphosphine palladium and bis (dibenzylideneacetone) palladium.

  The amount of the palladium catalyst is usually 0.0001 to 0.5 mol times the amount of the compound (A-0), preferably 0.001 to 0.2 mol times, Preferably it is 0.005-0.1 mol times amount.

  The above reaction may be performed by further adding a ligand as necessary. Examples of the ligand include a phosphine ligand and a carbene ligand. Of these, phosphine ligands are preferred.

  The amount of the ligand used is usually 0.5 to 20 mole times, preferably 1 to 10 mole times, more preferably 1 to 5 times moles of the palladium catalyst used. Amount.

  Although it does not specifically limit as a base used for the said reaction, Specifically, alkaline-earth metal, such as alkali metal hydroxides, such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, calcium hydroxide, barium hydroxide Alkali metal bicarbonates such as hydroxide, sodium bicarbonate and potassium bicarbonate, alkaline earth metal bicarbonates such as calcium bicarbonate and barium bicarbonate, alkali metal carbonates such as sodium carbonate and calcium carbonate, calcium carbonate And alkaline earth metal carbonates such as barium carbonate, and phosphates such as sodium phosphate and potassium phosphate. Among these, alkali metal bicarbonate, alkali metal carbonate, and phosphate are preferable.

  As a usage-amount of a base, 0.1-50 mol times amount is normally used with respect to a compound (A-0), Preferably, it is 1-20 mol times amount, More preferably, 2-10 mol times Amount.

  The temperature of the above reaction is not particularly limited, and is usually performed between 0 ° C. and the boiling point of the solvent. However, when the decomposition of the product does not occur, the temperature near the boiling point of the solvent is used to improve the reaction rate. It is preferable to make it react with.

  The platinum complex represented by the general formula (1) can be obtained by reacting a compound represented by the general formula (C-0) (hereinafter also referred to as a ligand) with a platinum salt in the presence of a solvent. it can.

In the production method of the present invention, the platinum salt used in the complex formation reaction between the platinum salt and the ligand includes divalent platinum, platinum chloride (PtCl ₂ ), platinum bromide, platinum iodide, Platinum acetylacetonate, bis (benzonitrile) dichloroplatinum, bis (acetonitrile) dichloroplatinum, dichloro (1,5-cyclooctadiene) platinum, dibromobis (triphenylphosphine) platinum, dichloro (1,10-phenanthroline) platinum, Dichlorobis (triphenylphosphine) platinum, ammonium tetrachloroparadate, diammine dibromopalladium, diammine dichloroplatinum, diammine diiodoplatinum, potassium tetrabromoplatinate, potassium tetrachloroplatinate, sodium Tora chloro platinum over preparative like. Of these, platinum chloride, bis (benzonitrile) dichloroplatinum, and bis (acetonitrile) dichloroplatinum are preferable.

  These metal compounds may contain crystal water, a crystal solvent, and a coordination solvent. The valence of the metal is not particularly limited, but the metal is preferably divalent or zero-valent, more preferably divalent.

  In the production method of the present invention, the amount of platinum salt used in the complex formation reaction between the platinum salt and the ligand is usually the ligand when one platinum atom forming the complex is contained in the platinum salt. It is 0.1-10 mol with respect to 1 mol, Preferably it is 0.5-5 mol, More preferably, it is 1-3 mol. When n platinum atoms forming a complex are contained in the platinum salt, the amount used may be 1 / n times.

  In the production method of the present invention, examples of the solvent used in the complex formation reaction between the platinum salt and the ligand include amides such as N, N-dimethylformamide, formamide, N, N-dimethylacetamide, acetonitrile, Nitriles such as pionitrile, butyronitrile, benzonitrile, halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, o-dichlorobenzene, fats such as pentane, hexane, octane, decane Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, diethyl ether, diisopropyl ether, butyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, 1,4-dioxane, etc. Ete Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, tert-butyl alcohol, 2-methoxyethanol, 2-ethoxyethanol, ethylene glycol, glycerin, Examples thereof include carboxylic acids such as acetic acid and propionic acid, water and the like. Of these, nitriles such as acetonitrile, propionitrile, butyronitrile, and benzonitrile, and aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene are particularly preferable. These solvents may be used alone or in combination of two or more.

  In the production method of the present invention, the amount of the solvent used in the complex formation reaction between the platinum salt and the ligand is not particularly limited as long as the reaction can proceed sufficiently. The volume amount is preferably 1 to 200 times, and more preferably 5 to 100 times.

  In the production method of the present invention, when an acidic substance such as hydrogen halide is produced during the complex formation reaction between the platinum salt and the ligand, the reaction may be performed in the presence of a basic substance. Basic substances include tertiary amines such as triethylamine, diisopropylethylamine and pyridine, metal alkoxides such as sodium methoxide and sodium ethoxide, inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate and sodium bicarbonate Kind. Also, acidic substances such as hydrogen halide generated during complex formation can be removed or reduced in amount from the reaction solution by blowing an inert gas such as nitrogen or argon into the reaction solution.

  In the production method of the present invention, the complex formation reaction between the platinum salt and the ligand is preferably performed in an inert gas atmosphere. Examples of the inert gas include nitrogen and argon.

  In the production method of the present invention, the reaction temperature, reaction time, and reaction pressure during the complex formation reaction between the platinum salt and the ligand vary depending on the raw materials, the solvent, etc., but are usually 20 ° C to 300 ° C, preferably 50 ° C to It is 250 degreeC, More preferably, it is the range of 80 to 220 degreeC. The reaction time is usually 30 minutes to 24 hours, preferably 1 to 12 hours, more preferably 2 to 10 hours, and the reaction pressure is usually atmospheric pressure, but under pressure as necessary. But it can be under reduced pressure.

  In the production method of the present invention, the heating means during the complex formation reaction between the platinum salt and the ligand is not particularly limited. Specifically, heating by an oil bath or a mantle heater or heating by microwave irradiation can be used.

  In the complex of the present invention, a method for producing a compound represented by the following general formula (D-1) will be specifically described.

In the above formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ²¹ , R ²² and R ^A are the same as those in the general formula (2).

The complex of the present invention is the method described in Journal of Organic Chemistry 53, 786, (1988), GR Newkome et al., Page 789, left line 53 to right line 7, page 790, left line 18 to 38. It can be obtained by the method described in the row, page 790, the method described in the right column, line 19-30, and a combination thereof. Starting from compound (A-1), a base such as lithium diisopropylamide, potassium t-butoxide, sodium hydride or the like is added to the N, N-dimethylformamide solution of (A-1) at 0 ° C. to room temperature. 1.2 equivalents were added and reacted at 0 ° C. to room temperature for about 30 minutes. On the other hand, alkyl halide R ²¹ X (R ²¹ is as defined in the general formula (2), and X represents a halogen atom). 1.5 to 4 equivalents of an alkyl halide represented by the formula, and the reaction was allowed to react for about 30 minutes at room temperature to monoalkylate. Halide R ²² X (R ²² is as defined in the general formula (2) and X represents a halogen atom) is reacted to obtain a dialkyl-substituted product (B-1) in a yield of 70 to 99%. Can do. Further, as the alkyl halide, 1,4-dibromobutane or the like is used to have a cyclopentane ring (B-1), and 1,5-dibromopentane or the like is used to have a cyclohexane ring (B-1). ) Can be synthesized.

  As a step of obtaining (C-1) from (B-1), the target compound can be synthesized by using the method described in Synth. Commun., 11, 513 (1981).

  The step of obtaining the compound (D-1) of the present invention from (C-1) comprises dissolving the compound (C-1) and 1 to 1.5 equivalents of platinum chloride in benzonitrile, and heating at 130 ° C. to It can be synthesized by heating to reflux temperature (boiling point of benzonitrile: 191 ° C.) and stirring for 30 minutes to 4 hours. Compound (D-1) can be purified by recrystallization using chloroform or ethyl acetate, silica gel column chromatography, sublimation purification or the like.

  Moreover, in the platinum complex of this invention, the complex represented by the following general formula (H-1) is compoundable also with the following manufacturing methods.

In the above formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ^A have the same meanings as those in the general formula (2). Ro represents a substituent selected from the substituent group B, and m represents an integer of 0 to 5.

  As the step of obtaining (F-1) from (E-1) and the step of obtaining (F-2) from (E-2), the method described in Synth. Commun., 11, 513 (1981) is used. Thus, the target compound can be synthesized.

  By using the method described in Angew. Chem. Int. Ed., 42, 2051-2053 (2003) as a step of obtaining (G-1) from (F-1), (F-2), The target compound can be synthesized.

  As a step of obtaining the compound (H-1) of the present invention from (G-1), the compound (G-1) and 1 to 1.5 equivalents of platinum chloride are dissolved in benzonitrile and heated at 130 ° C. The target compound can be synthesized by heating to the reflux temperature (boiling point of benzonitrile: 191 ° C.) and stirring for 30 minutes to 4 hours. Compound (H-1) can be purified by recrystallization using chloroform or ethyl acetate, silica gel column chromatography, sublimation purification or the like.

  In the production methods shown above, when the defined substituents change under the conditions of a certain synthesis method or are inappropriate for carrying out the method, the functional groups are protected and deprotected (for example, Protective Groups in Organic Synthesis, by TW Greene, John Wiley & Sons Inc. (198) ) Etc.) and the like can be easily manufactured. Moreover, it is also possible to change the order of reaction steps such as introduction of substituents as necessary.

  The device of the present invention will be described in detail.

  The element of the present invention is an organic electroluminescent element having at least one organic layer between a pair of electrodes, and is characterized by containing at least one kind of the platinum complex of the present invention in an organic layer. When the organic layer is a single layer, the organic layer has a light emitting layer. From the property of the element, at least one of the anode and the cathode is preferably transparent or translucent.

  The element of the present invention is characterized in that the organic layer contains a complex having a tetradentate ligand having a specific structure. Although it does not specifically limit as an organic layer, In addition to a light emitting layer, a positive hole injection layer, a positive hole transport layer, an electron injection layer, an electron transport layer, a positive hole block layer, an electron block layer, an exciton block layer, a protective layer, etc. You may have. Each of these layers may have other functions.

  As an aspect of lamination of the organic layer in the present invention, an aspect in which a hole transport layer, a light emitting layer, and an electron transport layer are laminated in this order from the anode side is preferable. Further, a charge blocking layer or the like may be provided between the hole transport layer and the light-emitting layer, or between the light-emitting layer and the electron transport layer. A hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer. Each layer may be divided into a plurality of secondary layers.

  The complex of the present invention can be contained in any layer when the organic layer is composed of a plurality of layers. The complex of the present invention is preferably contained in the light emitting layer, more preferably contained in the light emitting layer as the light emitting material or host material, further preferably contained in the light emitting layer as the light emitting material, and at least one kind It is particularly preferable that it is contained in the light emitting layer together with the host material.

  When the complex of the present invention is introduced into a layer other than the light emitting layer (for example, a charge transport layer), it is preferably contained in the layer in an amount of 10% by mass to 100% by mass, more preferably 30% by mass to 100% by mass. % Is preferably included.

  Each element constituting the element of the present invention will be described in detail.

<Board>
The substrate used in the present invention is preferably a substrate that does not scatter or attenuate light emitted from the organic layer. Specific examples include yttria-stabilized zirconia (YSZ), inorganic materials such as glass, polyesters such as polyethylene terephthalate, polybutylene phthalate, and polyethylene naphthalate, polystyrene, polycarbonate, polyethersulfone, polyarylate, polyimide, and polycycloolefin. , Organic materials such as norbornene resin and poly (chlorotrifluoroethylene).

  For example, when glass is used as the substrate, alkali-free glass is preferably used as the material in order to reduce ions eluted from the glass. Moreover, when using soda-lime glass, it is preferable to use what gave barrier coatings, such as a silica. In the case of an organic material, it is preferable that it is excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, and workability.

  There is no restriction | limiting in particular about the shape of a board | substrate, a structure, a magnitude | size, It can select suitably according to the use, purpose, etc. of a light emitting element. In general, the shape of the substrate is preferably a plate shape. The substrate structure may be a single layer structure, a laminated structure, may be formed of a single member, or may be formed of two or more members.

  The substrate may be colorless and transparent or colored and transparent, but is preferably colorless and transparent in that it does not scatter or attenuate light emitted from the organic light emitting layer.

  The substrate can be provided with a moisture permeation preventing layer (gas barrier layer) on the front surface or the back surface.

  As a material for the moisture permeation preventive layer (gas barrier layer), inorganic materials such as silicon nitride and silicon oxide are preferably used. The moisture permeation preventing layer (gas barrier layer) can be formed by, for example, a high frequency sputtering method. When a thermoplastic substrate is used, a hard coat layer, an undercoat layer, or the like may be further provided as necessary.

<Anode>
The anode usually only needs to have a function as an electrode for supplying holes to the organic layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials. As described above, the anode is usually provided as a transparent anode.

  Suitable examples of the material for the anode include metals, alloys, metal oxides, conductive compounds, and mixtures thereof. Specific examples of the anode material include conductive metals such as tin oxide doped with antimony and fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Metals such as oxides, gold, silver, chromium, nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, polyaniline, polythiophene, polypyrrole, etc. Organic conductive materials, and a laminate of these and ITO. Among these, conductive metal oxides are preferable, and ITO is particularly preferable from the viewpoints of productivity, high conductivity, transparency, and the like.

  The anode is composed of, for example, a wet method such as a printing method and a coating method, a physical method such as a vacuum deposition method, a sputtering method, and an ion plating method, and a chemical method such as a CVD and a plasma CVD method. It can be formed on the substrate according to a method appropriately selected in consideration of suitability with the material to be processed. For example, when ITO is selected as the anode material, the anode can be formed according to a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like.

  In the organic electroluminescent element of the present invention, the formation position of the anode is not particularly limited and can be appropriately selected according to the use and purpose of the light emitting element. Is preferably formed on the substrate. In this case, the anode may be formed on the entire one surface of the substrate, or may be formed on a part thereof.

  The patterning for forming the anode may be performed by chemical etching such as photolithography, or may be performed by physical etching such as laser, or vacuum deposition or sputtering with a mask overlapped. It may be performed by a lift-off method or a printing method.

  The thickness of the anode can be appropriately selected depending on the material constituting the anode and cannot be generally defined, but is usually about 10 nm to 50 μm, and preferably 50 nm to 20 μm.

The resistance value of the anode is preferably 10 ³ Ω / □ or less, and more preferably 10 ² Ω / □ or less. When the anode is transparent, it may be colorless and transparent or colored and transparent. In order to take out light emission from the transparent anode side, the transmittance is preferably 60% or more, and more preferably 70% or more.

  The transparent anode is detailed in Yutaka Sawada's “New Development of Transparent Conductive Film” published by CMC (1999), and the matters described here can be applied to the present invention. In the case of using a plastic substrate having low heat resistance, a transparent anode formed using ITO or IZO at a low temperature of 150 ° C. or lower is preferable.

<Cathode>
The cathode usually has a function as an electrode for injecting electrons into the organic layer, and there is no particular limitation on the shape, structure, size, etc., and it is known depending on the use and purpose of the light-emitting element. The electrode material can be selected as appropriate.

  Examples of the material constituting the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specific examples include alkali metals (eg, Li, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloys, lithium-aluminum alloys, magnesium. -Rare earth metals such as silver alloys, indium, ytterbium, and the like. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection.

Among these, as a material constituting the cathode, an alkali metal or an alkaline earth metal is preferable from the viewpoint of electron injecting property, and a material mainly composed of aluminum is preferable from the viewpoint of excellent storage stability.
The material mainly composed of aluminum is aluminum alone, an alloy of aluminum and 0.01 to 10% by mass of alkali metal or alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum alloy, etc.) Say.

  The materials for the cathode are described in detail in JP-A-2-15595 and JP-A-5-121172, and the materials described in these public relations can also be applied in the present invention.

  There is no restriction | limiting in particular about the formation method of a cathode, According to a well-known method, it can carry out. For example, the cathode described above is configured from a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method. It can be formed according to a method appropriately selected in consideration of suitability with the material. For example, when a metal or the like is selected as the cathode material, one or more of them can be simultaneously or sequentially performed according to a sputtering method or the like.

  Patterning when forming the cathode may be performed by chemical etching such as photolithography, physical etching by laser, or the like, or by vacuum deposition or sputtering with the mask overlaid. It may be performed by a lift-off method or a printing method.

In the present invention, the cathode forming position is not particularly limited, and may be formed on the entire organic layer or a part thereof.
Further, a dielectric layer made of an alkali metal or alkaline earth metal fluoride or oxide may be inserted between the cathode and the organic layer with a thickness of 0.1 to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer. The dielectric layer can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like.

The thickness of the cathode can be appropriately selected depending on the material constituting the cathode and cannot be generally defined, but is usually about 10 nm to 5 μm, and preferably 50 nm to 1 μm.
Further, the cathode may be transparent or opaque. The transparent cathode can be formed by depositing a thin cathode material to a thickness of 1 to 10 nm and further laminating a transparent conductive material such as ITO or IZO.

<Organic layer>
The organic layer in the present invention will be described. The element of the present invention has at least one organic layer including a light emitting layer, and the organic layer other than the organic light emitting layer includes a hole transport layer, an electron transport layer, and a hole block layer as described above. , Electron blocking layer, hole injection layer, electron injection layer and the like.

-Formation of organic layer-
In the organic electroluminescent element of the present invention, each layer constituting the organic layer can be suitably formed by any of a dry film forming method such as a vapor deposition method and a sputtering method, a transfer method, and a printing method.

-Light emitting layer-
The light-emitting layer receives holes from the anode, the hole injection layer, or the hole transport layer when an electric field is applied, receives electrons from the cathode, the electron injection layer, or the electron transport layer, and recombines holes and electrons. It is a layer which has the function to provide and to emit light.
The light emitting layer in the present invention may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material. The light emitting layer is preferably a light emitting material and a host material using the complex of the present invention. In addition, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.

  Although the thickness of a light emitting layer is not specifically limited, Usually, it is preferable that they are 1 nm-500 nm, it is more preferable that they are 5 nm-200 nm, and it is still more preferable that they are 10 nm-100 nm.

<Light emitting material>
The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material. Moreover, only 1 type may be used and 2 or more types may be used.
The light emitting layer in the present invention can contain two or more kinds of light emitting materials in order to improve the color purity and widen the light emission wavelength region.

(Fluorescent material)
Examples of fluorescent light-emitting materials that can be used in the present invention include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives. , Condensed aromatic compounds, perinone derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styryl Complexes of amine derivatives, diketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, 8-quinolinol derivatives and pyromethene derivatives Various complexes represented, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

(Phosphorescent material)
Examples of phosphorescent materials that can be used in the present invention include US Pat. No. 6,303,238 B1, US Pat. No. 6,097,147, International Publication No. 00/57676, International Publication No. 00/70655, International Publication No. 01/08230, International Publication No. 01/39234. Pamphlet, WO 01/41512 pamphlet, WO 02/02714 pamphlet, WO 02/15645 pamphlet, WO 02/44189 pamphlet, WO 05/19373 pamphlet, JP 2001-247859, JP2002-302671, JP2002-117978, JP2003-133074, JP2002-235076, JP2003-123982, JP2002-170684, P121212, JP2002-226495, JP2002-234894, JP2001-247659, JP2001-298470, JP2002-173675, JP2002-203678, JP2002-203679, JP2004-357771, Examples include phosphorescent compounds described in JP-A-2006-256999, JP-A-2007-19462, JP-A-2007-84635, JP-A-2007-96259, etc. Among them, more preferable luminescent dopants include Ir complexes. , Pt complex, Cu complex, Re complex, W complex, Rh complex, Ru complex, Pd complex, Os complex, Eu complex, Tb complex, Gd complex, Dy complex, and Ce complex. Particularly preferred is an Ir complex, a Pt complex, or a Re complex, among which an Ir complex or a Pt complex containing at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond. Or a Re complex. Furthermore, from the viewpoints of luminous efficiency, driving durability, chromaticity, etc., an Ir complex, a Pt complex, or a Re complex containing a tridentate or higher polydentate ligand is particularly preferable.

The content of the phosphorescent material (the complex of the present invention and / or the phosphorescent material used together) that can be used in the present invention is in the range of 0.1% by mass to 60% by mass with respect to the total mass of the light emitting layer. Is preferable, a range of 0.2% by mass to 50% by mass is more preferable, a range of 0.3% by mass to 40% by mass is further preferable, and a range of 0.5% by mass to 30% by mass is most preferable. .
When another phosphorescent material is used in combination with the complex of the present invention, the content of the complex of the present invention is preferably in the range of 0.1% by mass to 60% by mass with respect to the total mass of the phosphorescent light emitting material. The range of 0.2% to 50% by mass is more preferable, the range of 0.3% to 40% by mass is more preferable, and the range of 0.5% to 35% by mass is most preferable.

<Host material>
The host material is preferably a charge transport material. The host material may be one kind or two or more kinds, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Further, the light emitting layer may include a material that does not have charge transporting properties and does not emit light.

  The host material is a compound mainly responsible for charge injection and transport in the light emitting layer, and itself is a compound that does not substantially emit light. In this specification, “substantially no light emission” means that the light emission amount from the substantially non-light emitting compound is preferably 5% or less, more preferably 3% or less of the total light emission amount of the entire device. More preferably, it means 1% or less.

  The concentration of the host material in the light emitting layer is not particularly limited, but is preferably the main component (the component having the largest content) in the light emitting layer, more preferably 50% by mass or more and 99.9% by mass or less, 70 mass% or more and 99.8 mass% or less are more preferable, 80 mass% or more and 99.7 mass% or less are especially preferable, and 90 mass% or more and 99.5 mass% or less are the most preferable.

  The glass transition point of the host material is preferably 100 ° C. or higher and 500 ° C. or lower, more preferably 110 ° C. or higher and 300 ° C. or lower, and further preferably 120 ° C. or higher and 250 ° C. or lower.

  In the present invention, the fluorescence wavelength in the film state of the host material contained in the light emitting layer is preferably in the range of 400 nm to 650 nm, more preferably in the range of 420 nm to 600 nm, and in the range of 440 nm to 550 nm. More preferably.

  As the host material used in the present invention, the compounds described in paragraphs 0113 to 0161 of JP-A No. 2002-1000047 and the compounds described in paragraphs of 0087 to 0098 of JP-A No. 2004-214179 can be suitably used. It is not limited to.

  Examples of the host material contained in the light emitting layer in the present invention include those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, and aryl. Examples thereof include materials having a silane skeleton and materials exemplified in the sections of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer described later. Among them, a material including a tertiary amine skeleton, a carbazole skeleton, or an indole skeleton is preferable, a material including a carbazole skeleton or an indole skeleton is more preferable, and a material including a carbazole skeleton is particularly preferable.

-Hole injection layer, hole transport layer-
The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side. Specifically, the hole injection layer and the hole transport layer are carbazole derivatives, azacarbazole derivatives, indole derivatives, azaindole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamines. Derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, organosilane derivatives, carbon In addition, a layer containing various metal complexes represented by an Ir complex having phenylazole or phenylazine as a ligand is preferable.
An electron-accepting dopant can be contained in the hole injection layer or the hole transport layer of the organic EL device of the present invention. As the electron-accepting dopant introduced into the hole-injecting layer or the hole-transporting layer, any inorganic compound or organic compound can be used as long as it has an electron-accepting property and oxidizes an organic compound.

  Specifically, examples of the inorganic compound include metal halides such as ferric chloride, aluminum chloride, gallium chloride, indium chloride, and antimony pentachloride, metal oxides such as vanadium pentoxide, and molybdenum trioxide.

As the organic compound, a compound having a nitro group, halogen, cyano group, trifluoromethyl group or the like as a substituent, a quinone compound, an acid anhydride compound, fullerene, or the like can be preferably used.
In addition, JP-A-6-212153, JP-A-11-111463, JP-A-11-251067, JP-A-2000-196140, JP-A-2000-286054, JP-A-2000-315580, JP-A-2001-102175, JP-A-2001-2001. -160493, JP2002-252085, JP2002-56985, JP2003-157981, JP2003-217862, JP2003-229278, JP2004-342614, JP2005-72012, JP20051666667 The compounds described in JP-A-2005-209643 and the like can be preferably used.
Among these, hexacyanobutadiene, hexacyanobenzene, tetracyanoethylene, tetracyanoquinodimethane, tetrafluorotetracyanoquinodimethane, p-fluoranyl, p-chloranil, p-bromanyl, p-benzoquinone, 2,6-dichlorobenzoquinone, 2 , 5-dichlorobenzoquinone, 1,2,4,5-tetracyanobenzene, 1,4-dicyanotetrafluorobenzene, 2,3-dichloro-5,6-dicyanobenzoquinone, p-dinitrobenzene, m-dinitrobenzene, o-dinitrobenzene, 1,4-naphthoquinone, 2,3-dichloronaphthoquinone, 1,3-dinitronaphthalene, 1,5-dinitronaphthalene, 9,10-anthraquinone, 1,3,6,8-tetranitrocarbazole, 2,4,7-trinitro-9- Luenone, 2,3,5,6-tetracyanopyridine or fullerene C60 is preferred, and hexacyanobutadiene, hexacyanobenzene, tetracyanoethylene, tetracyanoquinodimethane, tetrafluorotetracyanoquinodimethane, p-fluoranyl, p- Chloranil, p-bromanyl, 2,6-dichlorobenzoquinone, 2,5-dichlorobenzoquinone, 2,3-dichloronaphthoquinone, 1,2,4,5-tetracyanobenzene, 2,3-dichloro-5,6-dicyano Benzoquinone or 2,3,5,6-tetracyanopyridine is more preferred, and tetrafluorotetracyanoquinodimethane is particularly preferred.

  These electron-accepting dopants may be used alone or in combination of two or more. Although the usage-amount of an electron-accepting dopant changes with kinds of material, it is preferable that it is 0.01 mass%-50 mass% with respect to hole transport layer material, and it is 0.05 mass%-20 mass%. It is further more preferable and it is especially preferable that it is 0.1 mass%-10 mass%.

  The thicknesses of the hole injection layer and the hole transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.

  The thickness of the hole transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. In addition, the thickness of the hole injection layer is preferably 0.1 nm to 200 nm, more preferably 0.5 nm to 100 nm, and still more preferably 1 nm to 100 nm.

  The hole injection layer and the hole transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

-Electron injection layer, electron transport layer-
The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. Specifically, the electron injection layer and the electron transport layer are triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, Carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, 8-quinolinol derivative complexes, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands It is preferably a layer containing various complexes typified by the complex to be prepared, an organosilane derivative, and the like.

The electron injection layer or the electron transport layer of the organic EL device of the present invention can contain an electron donating dopant. The electron donating dopant introduced into the electron injecting layer or the electron transporting layer only needs to have an electron donating property and a property of reducing an organic compound, such as an alkali metal such as Li or an alkaline earth metal such as Mg. Transition metals including rare earth metals and reducing organic compounds are preferably used. As the metal, a metal having a work function of 4.2 eV or less can be preferably used. Specifically, Li, Na, K, Be, Mg, Ca, Sr, Ba, Y, Cs, La, Sm, Gd , And Yb. Examples of the reducing organic compound include nitrogen-containing compounds, sulfur-containing compounds, and phosphorus-containing compounds.
In addition, materials described in JP-A-6-212153, JP-A-2000-196140, JP-A-2003-68468, JP-A-2003-229278, JP-A-2004-342614, and the like can be used.

  These electron donating dopants may be used alone or in combination of two or more. The amount of the electron donating dopant varies depending on the type of material, but is preferably 0.1% by mass to 99% by mass, and 1.0% by mass to 80% by mass with respect to the electron transport layer material. Is more preferable, and 2.0 mass% to 70 mass% is particularly preferable.

The thicknesses of the electron injection layer and the electron transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.
The thickness of the electron transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. In addition, the thickness of the electron injection layer is preferably 0.1 nm to 200 nm, more preferably 0.2 nm to 100 nm, and still more preferably 0.5 nm to 50 nm.
The electron injection layer and the electron transport layer may have a single-layer structure made of one or more of the materials described above, or may have a multilayer structure made up of a plurality of layers having the same composition or different compositions.

-Hole blocking layer-
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. In the present invention, a hole blocking layer can be provided as an organic layer adjacent to the light emitting layer on the cathode side.
Examples of organic compounds constituting the hole blocking layer include aluminum (III) bis (2-methyl-8-quinolinato) 4-phenylphenolate (Aluminum (III) bis (2-methyl-8-quinolinato) 4- aluminum complexes such as phenylphenolate (abbreviated as BAlq), triazole derivatives, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (2,9-Dimethyl-4,7-diphenyl-1,10-) phenanthroline derivatives such as phenanthroline (abbreviated as BCP)) and the like.
The thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm.
The hole blocking layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

<Protective layer>
In the present invention, the entire organic EL element may be protected by a protective layer.
As a material contained in the protective layer, any material may be used as long as it has a function of preventing materials that promote device deterioration such as moisture and oxygen from entering the device.
Specific examples thereof include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni, MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, and Fe ₂ O. ₃ , metal oxides such as Y ₂ O ₃ and TiO ₂ , metal nitrides such as SiN _x and SiN _x O _y , metal fluorides such as MgF ₂ , LiF, AlF ₃ and CaF ₂ , polyethylene, polypropylene, polymethyl Monomer mixture containing methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene and at least one comonomer A copolymer obtained by copolymerization of a copolymer having a cyclic structure in the copolymer main chain. Copolymer, 1% by weight of the water absorbing water absorption material, water absorption of 0.1% or less of moisture-proof material, and the like.

  The method for forming the protective layer is not particularly limited. For example, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency) Excited ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, transfer method can be applied.

<Sealing container>
The element of this invention may seal the whole element using a sealing container. You may enclose a water | moisture-content absorber or an inert liquid in the space between a sealing container and an element. Although it does not specifically limit as a moisture absorber, For example, barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, calcium chloride, magnesium chloride, copper chloride Cesium fluoride, niobium fluoride, calcium bromide, vanadium bromide, molecular sieve, zeolite, magnesium oxide and the like. The inert liquid is not particularly limited, and examples thereof include fluorinated solvents such as paraffins, liquid paraffins, perfluoroalkanes, perfluoroamines, perfluoroethers, chlorinated solvents, and silicone oils. It is done.

<Drive>
The element of the present invention can obtain light emission by applying a direct current (which may include an alternating current component if necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. it can.

  Regarding the driving method of the element of the present invention, JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234665, and JP-A-8-214447, The driving methods described in Japanese Patent No. 2784615, US Pat. Nos. 5,828,429 and 6023308, etc. can be applied.

<Charge generation layer>
The organic EL device of the present invention can have a configuration in which a charge generation layer is provided between a plurality of light emitting layers in order to improve luminous efficiency.
The charge generation layer is a layer having a function of generating charges (holes and electrons) when an electric field is applied and a function of injecting the generated charges into a layer adjacent to the charge generation layer.

The material for forming the charge generation layer may be any material having the above functions, and may be formed of a single compound or a plurality of compounds.
Specifically, it may be a conductive material, a semiconductive material such as a doped organic layer, or an electrically insulating material. 11-329748, Unexamined-Japanese-Patent No. 2003-272860, and the material of Unexamined-Japanese-Patent No. 2004-39617 are mentioned.
More specifically, transparent conductive materials such as ITO and IZO (indium zinc oxide), fullerenes such as C60, conductive organic materials such as oligothiophene, metal phthalocyanines, metal-free phthalocyanines, metal porphyrins, metal-free Conductive organic materials such as porphyrins, metal materials such as Ca, Ag, Al, Mg: Ag alloy, Al: Li alloy, Mg: Li alloy, hole conductive material, electron conductive material, and a mixture thereof May be used.
The hole conductive material is, for example, a material in which a hole transporting organic material such as 2-TNATA or NPD is doped with an oxidant having an electron withdrawing property such as F4-TCNQ, TCNQ, or FeCl _3. The electron conductive material includes an electron transporting organic material doped with a metal or a metal compound having a work function of less than 4.0 eV, an N type conductive polymer, N type Type semiconductors. Examples of the N-type semiconductor include N-type Si, N-type CdS, and N-type ZnS. Examples of the P-type semiconductor include P-type Si, P-type CdTe, and P-type CuO.
In addition, an electrically insulating material such as V ₂ O ₅ can be used for the charge generation layer.

  The charge generation layer may be a single layer or a stack of a plurality of layers. A structure in which a plurality of layers are stacked includes a conductive material such as a transparent conductive material and a metal material and a hole conductive material, or a structure in which an electron conductive material is stacked, and the above hole conductive material and electron conductive And a layer having a structure in which a functional material is laminated.

In general, it is preferable to select a film thickness and a material for the charge generation layer so that the visible light transmittance is 50% or more. The film thickness is not particularly limited, but is preferably 0.5 to 200 nm, more preferably 1 to 100 nm, still more preferably 3 to 50 nm, and particularly preferably 5 to 30 nm.
The method for forming the charge generation layer is not particularly limited, and the above-described method for forming the organic compound layer can be used.

The charge generation layer is formed between the two or more light emitting layers. The charge generation layer may include a material having a function of injecting charges into adjacent layers on the anode side and the cathode side. In order to improve the electron injection property to the layer adjacent to the anode side, for example, an electron injection compound such as BaO, SrO, Li ₂ O, LiCl, LiF, MgF ₂ , MgO, and CaF _{2 is} added to the anode side of the charge generation layer. May be laminated.
In addition to the contents mentioned above, the material for the charge generation layer should be selected based on the descriptions in JP-A-2003-45676, US Pat. Nos. 6,337,492, 6,107,734, 6,872,472, and the like. Can do.

  The element of the present invention can be suitably used for display elements, displays, backlights, electrophotography, illumination light sources, recording light sources, exposure light sources, reading light sources, signs, signboards, interiors, optical communications, and the like.

[Example 1]
<Synthesis of Exemplified Compound 1>

Synthesis of Compound J2
A1 (3.56 g, 10.0 mmol), 2-fluoropyridyl-3-boric acid (4.23 g, 30.0 mmol), palladium acetate (0.11 g, 0.5 mmol), triphenylphosphine (0.52 g, 2 0.0 mmol), sodium carbonate (10.6 g, 0.1 mol), 1,2-dimethoxyethane (100 mL) and water (100 mL) were stirred at 80 ° C. for 5 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, filtered, and extracted with chloroform. The organic layers were combined, dried and concentrated, and the resulting residue was purified with a column. Thereafter, recrystallization using ethanol gave 1.90 g of J2 as white crystals. The yield was 49%.

¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.93 (s, 6H), 7.21 (d, J = 9.0 Hz, 2H), 7.30 (m, 2H), 7.69 (t , J = 9 Hz, 2H), 7.78 (d, J = 6.0 Hz, 2H), 8.23 (m, 2H), 8.64 (m, 2H).

Synthesis of Exemplary Compound 1 Platinum chloride (2.2 g, 5.0 mmol) and J2 (2.2 g, 5.0 mmol) were stirred in benzonitrile (50 mL) for 4 hours under heating and reflux conditions in a nitrogen atmosphere. The solvent was distilled off from the reaction solution, and the obtained residue was purified by column and recrystallization to obtain 2.6 g of Exemplified Compound 1 as a yellow powder. Yield 76%.

¹ H-NMR (300 MHz, CDCl ₃ ) δ: 2.11 (s, 6H), 7.57 (d, J = 8.4 Hz, 2H), 7.93 (t, J = 8.1 Hz, 2H) , 8.00 (dd, J = 5.1, 3.0 Hz, 2H), 8.06 (dd, J = 5.7, 5.1 Hz, 2H), 8.20 (d, J = 8.4 Hz) , 2H).

[Example 2]
<Synthesis of Exemplary Compound 2>
Synthesis of compound S2

  A1 (0.83 g, 2.3 mmol), 6-fluoropyridyl-3-boric acid (1.0 g, 7.0 mmol), palladium acetate (26 mg, 0.12 mmol), triphenylphosphine (121 mg, 0.46 mmol), A mixture of sodium carbonate (2.4 g, 23 mmol), 1,2-dimethoxyethane (25.0 mL) and water (25.0 mL) was stirred at 85 ° C. for 1.5 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, filtered through celite, and extracted with ethyl acetate. The organic layers were combined, dried and concentrated, and the resulting residue was purified by a column to obtain 0.76 g (yield 85%) of S2 as a white solid.

Synthesis of Exemplified Compound 2

  Platinum chloride (137 mg, 0.52 mmol) and S2 (200 mg, 0.52 mmol) were stirred in benzonitrile (5 mL) for 6 hours and a half under heating and refluxing conditions in a nitrogen atmosphere. The reaction solution was allowed to cool to room temperature, and the solid precipitated by adding methanol was filtered and washed with methanol to obtain Illustrative Compound 2 as a yellow solid.

Example 3

<Synthesis of Exemplified Compound 3>

Synthesis of Compound A2 In a nitrogen atmosphere, compound A1 (2.0 g, 5.62 mmol), 2,6-difluoropyridyl-3-boric acid (2.14 g, 11.24 mmol), palladium acetate (63 mg, 0.281 mmol), Triphenylphosphine (294 mg, 1.12 mmol), sodium carbonate (5.96 g, 56.2 mmol), 1,2-dimethoxyethane (40 mL) and water (40 mL) were added, and the mixture was heated to reflux with stirring for 6 hours 30 minutes. After cooling to room temperature, the mixture was extracted with ethyl acetate, and the resulting organic layer was dried over sodium sulfate, filtered and concentrated. The obtained residue was purified by silica gel column chromatography (chloroform) to obtain 1.81 g (yield 76%) of compound A2 as white crystals.

¹ H-NMR (CD ₂ Cl ₂ , 300 MHz) δ: 1.95 (s, 6H), 7.00 (ddd, J = 0.9, 3.0, 8.1 Hz, 2H), 7.30 (dd, J = 2.4, 6.6 Hz, 2H) , 7.74-7.80 (m, 4H), 8.72 (dt, J = 8.1, 9.6Hz, 2H)

Synthesis of Exemplified Compound 3 To a 100 mL eggplant flask under nitrogen atmosphere, add Compound A2 (1.5 g, 3.53 mmol), platinum chloride (0.94 g, 3.53 mmol), and benzonitrile (50 mL), and then at 180 ° C. for 6 hours. Stir. After cooling to room temperature, 150 mL of methanol was added, and the precipitated solid was filtered and dried under reduced pressure to obtain 1.75 g (yield 80%) of Exemplary Compound 3 as yellow crystals. λmax = 461 nm (dichloromethane solution).

¹ H-NMR (CD ₂ Cl ₂ ) 300 MHz δ: 1.94 (s, 6H), 7.34 (tt, J = 1.8 Hz, J (Pt-H) = 56.4 Hz, 2H), 7.48 (dd, J = 0.9, 7.8Hz, 2H), 7.84 (t, J = 8.1Hz, 2H), 7.96 (d, J = 8.4Hz)

Example 4

<Synthesis of Exemplified Compound 25>

Synthesis of Compound B2 Compound B1 (2.2 g, 5.0 mmol), 2,6-difluoropyridyl-3-boric acid (2.4 g, 15.0 mmol), palladium acetate (56.1 mg, 0.25 mmol), triphenylphosphine (262.0 mg, 1.0 mmol), sodium carbonate (5.3 g, 50.0 mmol), 1,2-dimethoxyethane (50 mL) and water (50 mL) were stirred at 80 ° C. for 5 hours under nitrogen atmosphere. The reaction solution was cooled to room temperature, filtered, and extracted with chloroform. The organic layers were combined, dried and concentrated, and the resulting residue was purified by a column to obtain 2.61 g of Compound B2 as a yellow oily substance. The yield was quantitative.

¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.61 (d, J = 6.6 Hz, 12H), 1.63 (quint, J = 6.0 Hz, 2H), 2.45 (d, J = 5.4 Hz, 4H), 6.96 ( d, J = 9.0Hz, 2H), 7.78 (dd, J = 7.5, 0.3Hz, 2H), 7.64 (t, J = 7.8Hz, 2H), 7.69 (t, J = 7.5Hz, 2H), 8.69 ( dd, J = 8.7, 8.4Hz, 2H)

Synthesis of Exemplary Compound 25 Platinum chloride (2.2 g, 5.0 mmol) and compound B2 (2.2 g, 5.0 mmol) were stirred in benzonitrile (50 mL) for 4 hours under heating and reflux conditions in a nitrogen atmosphere. The solvent was distilled off from the reaction solution, and the resulting residue was purified by column and recrystallization to obtain 2.6 g of Exemplified Compound 25 as a yellow powder. Yield 76%.

¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.51 (d, J = 6.6 Hz, 12H), 1.17 (quint, J = 6.3 Hz, 2H), 2.44 (d, J = 6.4 Hz, 4H), 7.58 ( s, 2H), 7.78 (d, J = 8.7Hz, 2H), 8.06 (t, J = 8.1Hz, 2H), 8.22 (d, J = 8.1Hz, 2H).

Example 5

<Synthesis of Exemplified Compound 26>
Synthesis of compound K2

  K1 (2.3 g, 6.0 mmol), 2,6-difluoropyridyl-3-boric acid (2.86 g, 18.0 mmol), palladium acetate (0.07 g, 0.3 mmol), triphenylphosphine (0.32 g) 1.2 mmol), sodium carbonate (6.38 g, 60.0 mmol), 1,2-dimethoxyethane (60 mL) and water (60 mL) were stirred at 80 ° C. for 5 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, filtered, and extracted with chloroform. The organic layers were combined, dried and concentrated, and the resulting residue was purified with a column to obtain 2.10 g of K2 as white crystals. The yield was 77%.

¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.78 (m, 4H), 2.67 (m, 2H), 6.99 (d, J = 9.0 Hz, 2H), 7.24 (d , J = 6.0 Hz, 2H), 7.66 (t, J = 6.0 Hz, 2H), 7.69 (d, J = 6.0 Hz, 2H), 6.78 (dd, J = 9. 8, 9.8, 2H).

Synthesis of Exemplified Compound 26

  Platinum chloride (1.90 g, 4.2 mmol, 1.0 equivalent) and K2 (1.12 g, 4.2 mmol, 1.0 equivalent) in benzonitrile (80 mL) under heating and reflux conditions in a nitrogen atmosphere. Stir for 6 hours. The solvent was distilled off from the reaction solution, and purification by recrystallization gave 2.05 g of Exemplified Compound 26 as yellow crystals. Yield 75%.

¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.77 (m, 4H), 2.76 (m, 4H), 7.49 (m, 4H), 7.92 (t, J = 8.7 Hz) , 2H), 8.08 (d, J = 9.5 Hz, 2H)

Example 6
<Synthesis of Exemplified Compound 27>
Synthesis of compound M2

  Compound M1 (3.4 g, 8.6 mmol), 2,6-difluoropyridyl-3-boric acid (4.2 g, 26.4 mmol), palladium acetate (96.2 mg, 0.43 mmol), triphenylphosphine (445. 5 mg, 1.7 mmol), sodium carbonate (9.2 g, 86 mmol, 5.0 eq), 1,2-dimethoxyethane (80.0 mL) and water (80.0 mL) were mixed at 80 ° C. under a nitrogen atmosphere. For one and a half hours. The reaction solution was cooled to room temperature, filtered, and extracted with ethyl acetate. The organic layers were combined, dried and concentrated, and the resulting residue was purified by a column to obtain 3.4 g (yield 84%) of Compound M2 as a white solid.

¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.61-1.52 (m, 6H), 2.62-2.58 (m, 4H), 6.97 (dd, J = 8.1) 2.7 Hz, 2H), 7.30-7.26 (m, 2H), 7.69-7.67 (m, 4H), 8.76 (q, J = 9.3 Hz, 2H).

Synthesis of Exemplified Compound 27

  First platinum chloride (2.66 g, 10.0 mmol) and compound M2 (3.4 g, 7.3 mmol) were stirred in benzonitrile (70 mL) for 2 and a half hours under heating and reflux conditions in a nitrogen atmosphere. The reaction solution was allowed to cool to room temperature, and the precipitated solid was filtered and washed with methanol to obtain 3.2 g of Exemplified Compound 27 as a yellow powder. Yield 75%.

¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.22 (br, 2H), 1.47 (br, 2H), 1.92 (br, 2H), 2.61 (br, 2H), 2. 99 (br, 2H), 7.48 (m, J (Pt-H) = 60.0 Hz, 2H), 7.56-7.53 (m, 2H), 7.95 (t, J = 9. 0 Hz, 2H), 8.08 (d, J = 9.0 Hz, 2H).

Example 7
<Synthesis of Exemplified Compound 31>

Synthesis of Compound N2 In a nitrogen atmosphere, compound N1 (3.0 g, 6.24 mmol), 2,6-difluoropyridyl-3-boric acid (2.38 g, 15 mmol), palladium acetate (70 mg, 0.31 mmol), Tri Phenylphosphine (327 mg, 1.24 mmol), sodium carbonate (6.61 g, 62.4 mmol), 1,2-dimethoxyethane (50 mL) and water (50 mL) were added, and the mixture was heated to reflux with stirring for 6 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate, and the resulting organic layer was dried over sodium sulfate, filtered and concentrated. The obtained residue was purified by silica gel column chromatography (chloroform) to give compound N2 as a beige solid.

Synthesis of Exemplary Compound 31 Under a nitrogen atmosphere, Compound N2 (1 g, 1.82 mmol), platinum chloride (484 mg, 1.82 mmol), and benzonitrile (30 mL) were added to a 100 mL eggplant flask and stirred at 180 ° C. for 6 hours. . After cooling to room temperature, 50 mL of ethanol was added, and the precipitated solid was filtered and dried under reduced pressure to obtain 600 mg (yield 44%) of Exemplary Compound 31 as yellow crystals.

¹ H-NMR (CD ₂ Cl ₂ ) 300 MHz δ: 6.63-6.70 (m, 4H), 7.08-7.19 (m, 2H), 7.32-7.42 (m, 8H), 7.91 (t, J = 8.1Hz, 2H ), 8.25 (d, J = 8.4Hz, 2H)

Example 8
<Synthesis of Exemplified Compound 37>

Synthesis of Compound E2 Under nitrogen atmosphere, compound E1 (700 mg, 1.35 mmol), 2,6-difluoropyridyl-3-boric acid (2.1 g, 13.5 mmol), palladium acetate (30.3 mg, 0.14 mmol), A mixture of triphenylphosphine (142.0 mg, 0.54 mmol), potassium carbonate (1.9 g, 13.5 mmol), 1,2-dimethoxyethane (7.0 mL) and water (7.0 mL) was added at 80 ° C. For 8 and a half hours. The reaction solution was cooled to room temperature, filtered, and extracted with ethyl acetate. The organic layers were combined, dried and concentrated, and the resulting residue was purified by a column to obtain 501.1 mg (yield 63%) of Compound E2 as a yellow oily substance.

¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.30 (s, 18H), 6.78 (dd, J = 8.1, 3.0 Hz, 2H), 7.12-7.07 (m, 4H), 7.38 (t, J = 1.8 Hz, 1H), 7.56 (dd, J = 7.5, 1.8 Hz, 2H), 7.67 (t, J = 7.8 Hz, 2H) ), 8.35 (t, J = 8.1 Hz, 1H), 8.39 (t, J = 8.1 Hz, 1H).

Synthesis of Exemplary Compound 37 Platinum chloride (300 mg, 0.86 mmol) and compound E2 (501.1 mg, 0.86 mmol) were stirred in benzonitrile (10 mL) for 7 hours under heating and refluxing conditions in a nitrogen atmosphere. The solvent was distilled off from the reaction solution, and the resulting residue was filtered and washed with methanol to obtain 490 mg of a platinum complex as a yellow powder. Yield 73%.

¹ H-NMR (300 MHz, CD ₂ Cl ₂ ) δ: 1.31 (s, 18H), 6.58 (d, J = 8.7 Hz, 2H), 7.19 (d, J = 1.8 Hz, 2H), 7.43 (tt, J = 1.5 Hz, J (Pt−H) = 55.8 Hz, 2H), 7.52 (m, 1H), 7.76 (t, J = 8.7 Hz, 2H), 7.88 (d, J = 8.1 Hz, 2H).

Example 9
<Synthesis of Exemplary Compound 43>

Synthesis of Compound O2 Compound O1 (1.25 g, 3.2 mmol), 2,6-difluoropyridyl-3-boric acid (1.22 g, 7.68 mmol), palladium acetate (71.7 mg, 0.32 mmol) in a three-necked flask under nitrogen atmosphere , Triphenylphosphine (340 mg, 1.28 mmol), potassium carbonate (5.91 g, 42.2 mmol), tetrahydrofuran (30 mL) and water (30 mL) were added, and the mixture was heated to reflux with stirring for 6 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate, and the resulting organic layer was dried over sodium sulfate, filtered and concentrated. The obtained residue was purified by silica gel column chromatography to obtain 0.94 g of compound O2 as a white solid.

Synthesis of Exemplary Compound 43 Under a nitrogen atmosphere, Compound O2 (450 mg, 0.98 mmol), platinum chloride (260 mg, 0.98 mmol), and benzonitrile (10 mL) were added to a 100 mL eggplant flask and stirred at 180 ° C. for 2 hours. . After cooling to room temperature, 50 mL of methanol was added, and the precipitated solid was filtered and dried under reduced pressure to obtain 270 mg of Exemplified Compound 43 as yellow crystals.

¹ H-NMR (CD ₂ Cl ₂ ) 300 MHz δ: 2.08 (s, 6H), 7.41 (dd, J = 2.4,9.3Hz, 2H), 7.51 (s, J (H-Pt) = 57.6Hz, 2H) , 7.89 (dt, J = 1.8,9.0Hz, 2H)

Example 10
<Synthesis of Exemplified Compound 46>

Synthesis of Compound F2 In a nitrogen atmosphere, compound F1 (0.8 g, 2.25 mmol), 2,6-difluoropyridyl-3-borate (858 mg, 5.4 mmol), palladium acetate (25 mg, 0.11 mmol), tri Phenylphosphine (118 mg, 0.45 mmol), sodium carbonate (2.38 g, 22.5 mmol), 1,2-dimethoxyethane (20 mL) and water (20 mL) were added, and the mixture was heated to reflux with stirring for 6 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate, and the resulting organic layer was dried over sodium sulfate, filtered and concentrated. The obtained residue was purified by silica gel column chromatography (chloroform) to obtain 0.86 g (yield 79%) of compound F2 as a beige solid.

¹ H-NMR (CDCl ₃ ) 300 MHz δ: 1.86 (s, 6H), 3.84 (s, 6H), 6.73 (d, J = 2.1 Hz, 2H), 6.94 (ddd, J = 0.6, 3.0, 8.4 Hz, 2H), 7.26-7.29 (m, 2H), 8.74 (dt, J = 8.1, 12.8Hz, 2H)

Synthesis of Exemplified Compound 46 Under a nitrogen atmosphere, Compound F2 (700 mg, 1.44 mmol), platinum chloride (383 mg, 1.44 mmol), and benzonitrile (35 mL) were added to a 100 mL eggplant flask and stirred at 180 ° C. for 2 hours. . After cooling to room temperature, 50 mL of methanol was added, and the precipitated solid was filtered and dried under reduced pressure to obtain 457 mg (yield 48%) of Exemplary Compound 46 as yellow crystals.

¹ H-NMR (CD ₂ Cl ₂ , 300 MHz) δ: 2.03 (s, 6H), 4.05 (s, 6H), 7.14 (d, J = 2.4Hz, 2H), 7.50 (brs, J (H-Pt) = 57.0Hz, 2H), 7.62 (t, J = 2.1Hz, 2H)

Ｐ１（１．０ｇ、２．９ｍｍｏｌ）、２，６−ジフルオロピリジル−３−ほう酸（１．４ｇ、８．５ｍｍｏｌ）、ジクロロビス（トリフェニルホスフィン）パラジウム（２００ｍｇ、０．９４ｍｍｏｌ）、炭酸カリウム（２．４ｇ、６．０ｍｍｏｌ）、水（１０２ｍｇ、５．７ｍｍｏｌ）、１，４−ジオキサン（３０．０ｍL）からなる混合物を、窒素雰囲気下、４時間半加熱還流した。反応液を室温にまで冷却、濾過した後に、水を加え、酢酸エチルで抽出を行った。有機層をまとめて乾燥、濃縮し、得られた残渣をカラムにて精製することで、P2を白色固体として７３０ｍｇ（収率５０％）得た。 Example 11
<Synthesis of Exemplified Compound 47>
Synthesis of compound P2

P1 (1.0 g, 2.9 mmol), 2,6-difluoropyridyl-3-boric acid (1.4 g, 8.5 mmol), dichlorobis (triphenylphosphine) palladium (200 mg, 0.94 mmol), potassium carbonate (2 .4 g, 6.0 mmol), water (102 mg, 5.7 mmol) and 1,4-dioxane (30.0 mL) were heated to reflux for 4 and a half hours under a nitrogen atmosphere. The reaction mixture was cooled to room temperature and filtered, water was added, and the mixture was extracted with ethyl acetate. The organic layers were combined, dried and concentrated, and the resulting residue was purified by a column to obtain 730 mg (yield 50%) of P2 as a white solid.

¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.86 (s, 6H), 3.01 (s, 12H), 6.43 (s, 2H), 6.93 (dd, J = 3.0 , 8.4 Hz, 2H), 7.02 (s, 2H), 8.79 (dt, J = 8.1, 9.6 Hz, 2H).

Synthesis of Exemplified Compound 47

  Platinum chloride (193 mg, 0.72 mmol) and P2 (370 mg, 0.72 mmol) were stirred in benzonitrile (7.0 mL) for 3 hours under heating and reflux conditions in a nitrogen atmosphere. The reaction solution was allowed to cool to room temperature, and the solid precipitated by adding methanol was filtered and washed with methanol to obtain 370 mg of Exemplified Compound 47 as a light yellow powder. Yield 73%.

¹ H-NMR (300 MHz, CD ₂ Cl ₂ ) δ: 2.02 (s, 6H), 3.20 (s, 12H), 6.75 (d, J = 2.4 Hz, 2H), 7.30 (T, J = 2.4 Hz, 2H), 7.48 (t, J (HH) = 2.1 Hz, J (Pt−H) = 54.6 Hz, 2H).

Example 12
<Synthesis of Exemplary Compound 54>

Synthesis of Compound I2 In a nitrogen atmosphere, compound I1 (0.95 g, 2.03 mmol), 2,6-difluoropyridyl-3-boric acid (1.28 g, 8.12 mmol), palladium acetate (23 mg, 0.11 mmol), Triphenylphosphine (106 mg, 0.41 mmol), potassium carbonate (2.80 g, 20.3 mmol), tetrahydrofuran (20 mL) and water (10 mL) were added, and the mixture was heated to reflux with stirring for 5 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate, and the resulting organic layer was dried over sodium sulfate, filtered and concentrated. The obtained residue was purified by silica gel column chromatography (hexane / ethyl acetate = 20/1) to obtain 1.04 g (yield 95%) of Compound I2 as a white solid.

¹ H-NMR (CD ₂ Cl ₂ , 300 MHz) δ: 1.21 (s, 9H), 1.81 (s, 6H), 7.00 (ddd, J = 0.6, 3.0, 8.4 Hz, 2H), 7.15 (d, J = 1.8Hz, 2H), 7.63 (t, J = 1.8Hz, 2H), 8.59 (dt, J = 8.1, 9.6Hz, 2H)

Synthesis of Exemplified Compound 54 In a nitrogen atmosphere, Compound I2 (830 mg, 1.55 mmol), platinum chloride (411 mg, 1.55 mmol), and benzonitrile (40 mL) were added to a 100 mL eggplant flask and stirred at 180 ° C. for 2 hours. . After cooling to room temperature, 50 mL of methanol was added, and the precipitated solid was filtered and dried under reduced pressure to obtain 736 mg (yield 65%) of Exemplary Compound 54 as yellow crystals.

¹ H-NMR (CD ₂ Cl ₂ , 300 MHz) δ: 1.44 (s, 9H), 2.12 (s, 6H), 7.51 (tt, J = 1.5Hz, J (Pt-H) = 56.4Hz, 2H), 7.63 (d, J = 1.5Hz, 2H), 8.14 (t, J = 1.5Hz, 2H)

Example 13
<Synthesis of Exemplary Compound 55>
Synthesis of compound G2

  G1 (2.16 g, 4.0 mmol), 2,6-difluoropyridyl-3-boric acid (1.90 g, 12.0 mmol), palladium acetate (45 mg, 0.2 mmol), triphenylphosphine (0.21 g, 0 0.8 mmol), sodium carbonate (4.24 g, 40.0 mmol), 1,2-dimethoxyethane (40 mL) and water (40 mL) were stirred at 80 ° C. for 5 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, filtered, and extracted with chloroform. The organic layers were combined, dried and concentrated, and the resulting residue was purified with a column to obtain 2.26 g of G2 as white crystals. Yield 93%.

¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.85 (s, 6H), 6.85 (s, 2H), 6.92 (dd, J = 5.1, 3.0 Hz, 2H), 7 .06 (d, J = 6
. 3 Hz, 4H), 7.23 (t, J = 7.2 Hz, 2H), 7.34-7.44 (m,
6H), 8.66 (dt, J = 9.3, 7.8 Hz, 2H).

Synthesis of exemplary compound 55

  First platinum chloride (0.79 g, 3.0 mmol) and G2 (1.82 g, 3.0 mmol, 1.0 equivalent) were stirred in benzonitrile (30 mL) for 4 hours under heating and reflux conditions in a nitrogen atmosphere. The solvent was distilled off from the reaction solution, and the obtained residue was purified by column and recrystallization to obtain 1.8 g of Exemplified Compound 55 as a yellow powder. Yield 76%.

¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.94 (s, 6H), 7.11 (t, J = 4.8 Hz, 4H), 7.16 (s, 2H), 7.33 (t , J = 7.5 Hz, 2H), 7.45 (d, J = 7.2 Hz, 4H), 7.50 (s, 2H), 7.53 (t, J = 2.1 Hz, 2H).

Example 14
<Synthesis of Exemplary Compound 86>
Synthesis of compound H2

  H1 (3.0 g, 5.0 mmol), 2,6-difluoropyridyl-3-boric acid (2.4 g, 15.0 mmol), palladium acetate (56.1 mg, 0.25 mmol), triphenylphosphine (262.0 mg) 1.0 mmol), sodium carbonate (5.3 g, 50.0 mmol), 1,2-dimethoxyethane (50 mL) and water (50 mL) were stirred at 80 ° C. for 5 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, filtered, and extracted with chloroform. The organic layers were combined, dried and concentrated, and the resulting residue was purified with a column to obtain 3.3 g of H2 as white crystals. The yield is 98%.

¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.78 (s, 6H), 2.02 (s, 12H), 6.53 (s, 2H), 6.90 (dd, J = 5.4) , 3.0 Hz, 2H), 7.04 (s, 4H), 7.09 (s, 2H), 8.63 (dt, J = 9.6, 8.1 Hz, 2H).

Synthesis of Exemplified Compound 86

  Platinum chloride (1.12 g, 4.2 mmol) and H2 (2.80 g, 4.2 mmol, 1.0 equivalent) were stirred in benzonitrile (42 mL) for 4 hours under heating and reflux conditions in a nitrogen atmosphere. The solvent was distilled off from the reaction solution, and the obtained residue was purified by column and recrystallization to obtain 2.4 g of Exemplified Compound 86 as a yellow powder. Yield 66%.

¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.97 (s, 6H), 2.15 (s, 12H), 7.06 (s, 2H), 7.18 (s, 4H), 7. 31 (s, 2H), 7.54 (t, J = 28.2 Hz, 2H).

Example 15
<Synthesis of Exemplified Compound 87>

Synthesis of Compound Q2 In a nitrogen atmosphere, compound Q1 (1.77 g, 4.23 mmol), 2,6-difluoropyridyl-3-boric acid (1.6 g, 10 mmol), palladium acetate (48 mg, 0.22 mmol), Tri Phenylphosphine (221 mg, 0.846 mmol), sodium carbonate (4.48 g, 42.3 mmol), 1,2-dimethoxyethane (25 mL) and water (25 mL) were added, and the mixture was refluxed with stirring for 6 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate, and the resulting organic layer was dried over sodium sulfate, filtered and concentrated. The obtained residue was purified by silica gel column chromatography to obtain 2.1 g of Compound Q2 as a beige solid.

Synthesis of Exemplified Compound 87 In a nitrogen atmosphere, add compound Q2 (2.1 g, 4.31 mmol), platinum platinum (1.148 g, 4.31 mmol), and benzonitrile (30 mL) to a 100 mL eggplant-shaped flask at 180 ° C. for 2 hours. Stir. After cooling to room temperature, 50 mL of methanol was added, and the precipitated solid was filtered and dried under reduced pressure to obtain 1.52 g (yield 52%) of Exemplary Compound 87 as yellow crystals.

¹ H-NMR (CD ₂ Cl ₂ ) 300 MHz δ: 2.20 (s, 3H), 6.60-6.66 (m, 2H), 7.22-7.33 (m, 3H), 7.39 (t, J = 1.8Hz, J (Pt -H) = 55.8Hz, 2H), 7.58-7.61 (m, 2H), 8.05 (t, J = 8.1Hz, 2H), 8.20 (d, J = 8.1Hz, 2H)

Example 16
<Synthesis of Exemplary Compound 96>

  Synthesis was performed in the same manner as Exemplified Compound 43 using Compound R1 as a raw material instead of Compound O1, and Exemplified Compound 96 was obtained as yellow crystals.

¹ H-NMR (CD ₂ Cl ₂ ) 300 MHz δ: 2.15 (s, 3H), 3.61 (s, 3H), 7.51 (s, J (Pt-H) = 57Hz, 2H), 7.70 (dd, J = 2.4 , 6.3Hz, 2H), 7.94 (dt, J = 2.4,6,3Hz, 2H)

Example 17
<Synthesis of Exemplified Compound 97>

Synthesis of Compound S2 In a nitrogen atmosphere, compound A1 (2.0 g, 5.62 mmol), 2,6-dimethoxypyridyl-3-boric acid (2.47 g, 13.5 mmol), palladium acetate (63 mg, 0.28 mmol), Triphenylphosphine (294 mg, 1.12 mmol), sodium carbonate (5.96 g, 56.2 mmol), 1,2-dimethoxyethane (40 mL) and water (40 mL) were added, and the mixture was heated to reflux with stirring for 4 hours. After cooling to room temperature, the mixture was extracted with ethyl acetate, and the resulting organic layer was dried over sodium sulfate, filtered and concentrated. The obtained residue was purified by silica gel column chromatography to obtain 2.25 g of compound S2 as a beige solid.

Synthesis of Exemplified Compound 97 To a 100 mL eggplant flask under nitrogen atmosphere, add Compound S2 (2.05 g, 4.34 mmol), K ₂ PtCl ₄ (1.8 g, 4.34 mmol), acetic acid (50 mL), and stir at 100 ° C. for 8 hours. did. After cooling to room temperature, water was added and the mixture was extracted with chloroform. The resulting organic layer was dried over sodium sulfate, filtered and concentrated. The obtained residue was purified by silica gel column chromatography to obtain 0.38 g of Exemplified Compound 97 as yellow crystals.

¹ H-NMR (CDCl ₃ ) 300 MHz δ: 2.04 (s, 3H), 4.00 (s, 6H), 4.08 (s, 6H), 7.23 (s, 2H), 7.31 (dd, J = 0.8, 8.1 Hz, 2H), 7.75 (t, J = 8.1Hz, 2H), 8.35 (dd, J = 0.6,8.1Hz, 2H)

[Comparative Example 1]
The ligand C2 and the ligand D2 of the compound (55) described in International Publication No. 2004-108857 pamphlet (both α-positions of the pyridine ring forming a platinum-carbon bond are unsubstituted) are synthesized, Complexation was carried out in the same manner as in Examples 1 and 2. In all cases, a large amount of by-products were produced, and the yield of the target complex was 1% or less.

Example 18
The cleaned ITO substrate was put into a vapor deposition apparatus, and copper phthalocyanine was vapor-deposited by 10 nm, and NPD ((N, N′-di-α-naphthyl-N, N′-diphenyl) -benzidine) was vapor-deposited thereon by 40 nm. On top of this, mCP (host material) and exemplary compound 3 of the present invention were vapor-deposited at a ratio of 85:15 (mass ratio) of 67 nm, and BAlq was vapor-deposited thereon at 40 nm. On top of this, lithium fluoride was deposited to 3 nm, and then 60 nm of aluminum was deposited to produce a device. As a result of emitting light by applying a DC constant voltage to the EL element using Toyo Technica source measure unit 2400 type, blue light emission derived from compound 3 was obtained, and 360 cd / m ² (light emission area 4 mm ² ) The luminance half-life of the driven element (the time until the luminance decreases to 50% of the initial luminance) was 1.05 times that of the element of Comparative Example 2. On the other hand, the luminance half-life of the device driven at 1000 cd / m ² (light emitting area 4 mm ² ), which is a higher luminance condition, was 1.8 times that of the device of Comparative Example 2.

[Example 19] to [Example 27]
Luminance half-life of an element manufactured and driven at 360 cd / m ² (light emitting area 4 mm ² ) as in Example 18 except that the materials shown in Table 1 were used for the host material and the light emitting material of the light emitting layer. The luminance half-life of the element driven at 1000 cd / m ² (light emitting area 4 mm ² ) was measured. The results are shown in Table 1.

[Comparative Example 2]
The cleaned ITO substrate was put into a vapor deposition apparatus, and copper phthalocyanine was vapor-deposited by 10 nm, and NPD ((N, N′-di-α-naphthyl-N, N′-diphenyl) -benzidine) was vapor-deposited thereon by 40 nm. On top of this, mCP and compound 2 described in JP-A-2007-19462 were deposited at a ratio of 85:15 (mass ratio) of 67 nm, and BAlq was deposited thereon by 40 nm. On top of this, lithium fluoride was deposited to 3 nm, and then 60 nm of aluminum was deposited to produce a device. As a result of applying a constant DC voltage to the EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue light emission derived from the compound 2 was obtained. The luminance half life of the element driven at 360 cd / m ² (light emitting area 4 mm ² ) was 100 hours. Furthermore, the luminance half-life of the element driven at 1000 cd / m ² (light emitting area 4 mm ² ), which is a high luminance condition, was 35 hours.

  The chemical structure of the compound 2, mCP, Host1, and BAlq described in the above copper phthalocyanine, NPD, and JP-A No. 2007-19462 is shown below.

  Even when other platinum complexes of the present invention are used, an organic electroluminescent element excellent in durability at high luminance can be obtained as described above.

Claims (6)

A compound represented by the general formula (B-2) and the general formula (B-2 ′) is reacted with a compound represented by the general formula (A-0), and is represented by the general formula (C-0). A method for producing a platinum complex represented by the general formula (1), comprising: a step of obtaining a compound comprising: a step of reacting a compound represented by the general formula (C-0) with a platinum salt.
General formula (B-2)

(In the general formula (B-2), R ¹⁷ and R ¹⁸ each independently represents a hydrogen atom or a substituent, provided that at least one of R ¹⁷ and R ¹⁸ represents an electron-withdrawing substituent. R ^A represents a hydrogen atom or a substituent.)
General formula (B-2 ′)

(In the general formula (B-2 ′), R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or a substituent, provided that at least one of R ¹⁹ and R ²⁰ represents an electron-attracting substituent. R ^B represents a hydrogen atom or a substituent.)
General formula (A-0)

(In the general formula (A-0), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represents a hydrogen atom or a substituent. L ¹ represents a single bond or a divalent group. X represents a halogen atom.)
General formula (C-0)

(In the general formula (C-0), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ^A and R ^B each independently represents a hydrogen atom or a substituent. R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or a substituent, provided that at least one of R ¹⁷ and R ¹⁸ represents an electron withdrawing substituent, and at least one of R ¹⁹ and R ²⁰ One represents an electron-withdrawing substituent, and L ¹ represents a single bond or a divalent linking group.)
General formula (1)

(In the general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ^A and R ^B each independently represents a hydrogen atom or a substituent. R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or a substituent, provided that at least one of R ¹⁷ and R ¹⁸ represents an electron withdrawing substituent, and at least one of R ¹⁹ and R ²⁰ represents Represents an electron-attracting substituent, L ¹ represents a single bond or a divalent linking group.) A platinum complex represented by the general formula (1).
General formula (1)

(In the general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ^A and R ^B each independently represents a hydrogen atom or a substituent. R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or a substituent, provided that at least one of R ¹⁷ and R ¹⁸ represents an electron withdrawing substituent, and at least one of R ¹⁹ and R ²⁰ represents Represents an electron-attracting substituent, L ¹ represents a single bond or a divalent linking group.) The platinum complex according to claim 2, wherein the general formula (1) is represented by the following general formula (2).
General formula (2)

(In the general formula (2), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ^A and R ^B are the same as those in the general formula (1). R ²¹ and R ²² each independently represents a hydrogen atom or a substituent.   A platinum complex produced by the method according to claim 1.   An organic electroluminescent device having at least one organic layer between a pair of electrodes, wherein the organic layer contains at least one platinum complex according to claim 2, 3 and 4 in the organic layer. Electroluminescent device.   An organic electroluminescence device having at least one organic layer between a pair of electrodes, wherein the light emitting layer contains at least one kind of platinum complex according to claim 2, 3 and 4. Electroluminescent device.