JP2013147481A - Synthesis method, compound synthesized using the same, and organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a simple synthesis method of indolocarbazole (indolo[3,2,1-jk]carbazole) and analogs thereof for achieving high yield, tens of gram scale synthesis, and a small number of processes.SOLUTION: A synthesis method of a compound represented by general formula (4) is provided. In the synthesis method, when a compound represented by general formula (1) is reacted with a compound represented by general formula (2), the compound represented by general formula (4) is synthesized via a compound represented by general formula (3) as an intermediate. In the formulas: X-Xand X-Xare each independently CRor N; Rare each independently a hydrogen atom or a substituent; Y is a single bond, O, S, Se, CRR, NR, SiRRor BR; R-Rare each independently a hydrogen atom or a substituent; Z is Cl, Br, I, or OTf; and Tf is a trifluoromethanesulfonyl group (a tri-furyl group).

Description

  The present invention relates to a synthesis method, a compound thereof, and an organic electroluminescent device. More specifically, the present invention relates to a method for synthesizing indolocarbazole and its analogs and compounds thereof, and an organic electroluminescent device using indolocarbazole and its analogs synthesized by the synthesis method.

  Organic electroluminescent elements (hereinafter also referred to as “elements” and “organic EL elements”) are actively researched and developed because they emit light with high luminance when driven at a low voltage. An organic electroluminescent element has an organic layer between a pair of electrodes, and electrons injected from the cathode and holes injected from the anode recombine in the organic layer, and the generated exciton energy is used for light emission. To do.

In recent years, the efficiency of organic electroluminescent elements has been increased by using phosphorescent materials. However, in practical use, improvements are required from the viewpoints of lowering drive voltage and durability. In particular, from the viewpoint of durability, it is necessary that the compound used for the organic electroluminescence device has high purity.
On the other hand, an organic electroluminescent element using a compound having a structure in which phenyl groups of triphenylamine are connected to each other to form a condensed ring to form a carbazole ring as a host material of a light emitting layer is known. As a method for synthesizing such a carbazole derivative or indolocarbazole (indoro [3,2,1-jk] carbazole) in which the phenyl groups of triphenylamine are linked to each other and condensed, for example, Patent Document 1 2 and non-patent documents 1 to 3 are known.

Non-Patent Document 1 describes a method of synthesizing indolocarbazole on a gram scale by FVP (flash vacuum pyrolysis).
In addition, in the synthesis example of Patent Document 1, an intermediate obtained by heating carbazole and 1-fluoro-2-nitrobenzene in the presence of potassium carbonate is reduced and converted to another intermediate having an amino group, Furthermore, a method is described in which indolocarbazole is obtained by condensing by thermal decomposition after reacting with sodium nitrite in sulfuric acid or acetic acid solvent at 0 ° C. In addition, a method is described in which the obtained indolocarbazole is brominated in chloroform to obtain a brominated product, and a substituent is introduced into indolocarbazole.
Patent Document 2 describes a method of synthesizing a hetero condensed ring by a reaction in which a carbazole derivative having a hydroxyl group is cyclized in a molecule.
Non-Patent Document 2 describes a reaction in which carbazole is reacted with 1-fluoro-4-nitrobenzene to synthesize an intermediate having a nitro group and reduced to synthesize a carbazole derivative having an amino group. Yes. Non-Patent Document 3 describes a method of synthesizing a hetero condensed ring by a reaction in which a compound having a halogen as a substituent is cyclized in a molecule using a palladium salt.

JP 2010-087496 A International publication WO2011 / 088887

Chem. Eur. J. et al. 2009, 15, 5482-5490 Journal of Materials Chemistry, 2006, 16, 1831-1842 J. et al. AM. CHEM. SOC. 2006, 128, 581-590

  However, the methods described in Patent Documents 1 and 2 are synthesis methods that remain unsatisfactory from the viewpoints of synthesis scale, yield, and by-product control, and the method described in Patent Document 1 has many steps and remains unsatisfactory. It was a thing. Further, the FVP device described in Non-Patent Document 1 is a special device and has a problem from the viewpoint of simplicity. Therefore, there has been a demand for a synthesis method for obtaining the desired indolocarbazole and its analogs selectively with high purity by a further simple method.

  The problem to be solved by the present invention is that indolocarbazole (indoro [3,2,1-jk] has a high yield, can be used for synthesis on the scale of several tens of grams, and is easy to control by-products. Carbazole) and analogs thereof.

  As a result of intensive studies by the present inventor, a desired organic compound is synthesized using a normal organic synthesis that does not require a special apparatus in a short process (sometimes one-pot) by a synthesis method through an intermediate having a specific structure. It was found that carbazole (indoro [3,2,1-jk] carbazole) and its analogs can be selectively synthesized with high purity.

（一般式（１）〜（４）中、Ｘ¹¹〜Ｘ¹⁷およびＸ²¹〜Ｘ²⁴はそれぞれ独立にＣＲ⁰またはＮを表し、Ｒ⁰はそれぞれ独立に水素原子または置換基を表す。Ｙは単結合、Ｏ、Ｓ、Ｓｅ、ＣＲ¹Ｒ²、ＮＲ³、ＳｉＲ⁴Ｒ⁵またはＢＲ⁶を表し、Ｒ¹〜Ｒ⁶はそれぞれ独立に水素原子または置換基を表す。ＺはＣｌ、Ｂｒ、Ｉ、ＯＴｆを表す。なお、Ｔｆはトリフルオロメタンスルホニル基（トリフリル基）を表す。）
［２］ ［１］に記載の合成法は、前記一般式（４）で表される化合物が、下記一般式（Ａ）〜（Ｃ）のいずれかで表される化合物であることが好ましい。

（一般式（Ａ）〜（Ｃ）中、Ｘ¹¹〜Ｘ¹⁷およびＸ²¹〜Ｘ²⁴はそれぞれ独立にＣＲ⁰またはＮを表し、Ｒ⁰はそれぞれ独立に水素原子または置換基を表す。Ｙは単結合、Ｏ、Ｓ、Ｓｅ、ＣＲ¹Ｒ²、ＮＲ³、ＳｉＲ⁴Ｒ⁵またはＢＲ⁶を表し、Ｒ¹〜Ｒ⁶はそれぞれ独立に水素原子または置換基を表す。ただし、一般式（Ａ）、（Ｂ）および（Ｃ）において共通する名称の置換基は、互いに同一であっても異なっていてもよい。）
［３］ ［１］または［２］に記載の合成法は、前記一般式（４）で表される化合物が、下記一般式（８）で表される化合物であり、下記一般式（５）で表される化合物と下記一般式（６）で表される化合物を反応させて、下記一般式（７）で表される化合物を中間体として経て、前記一般式（８）で表される化合物を合成することが好ましい。

（一般式（５）〜（８）中、Ｒ⁵¹〜Ｒ⁵⁷およびＲ⁶¹〜Ｒ⁶⁴はそれぞれ独立に水素原子または置換基を表す。Ｙは単結合、Ｏ、Ｓ、Ｓｅ、ＣＲ¹Ｒ²、ＮＲ³、ＳｉＲ⁴Ｒ⁵またはＢＲ⁶を表し、Ｒ¹〜Ｒ⁶はそれぞれ独立に水素原子または置換基を表す。ＺはＣｌ、Ｂｒ、Ｉ、ＯＴｆを表す。なお、Ｔｆはトリフルオロメタンスルホニル基（トリフリル基）を表す。）
［４］ ［３］に記載の合成法は、前記一般式（８）で表される化合物が、下記一般式（Ｇ）〜（Ｉ）のいずれかで表される化合物であることが好ましい。

（一般式（Ｇ）、（Ｈ）および（Ｉ）中、Ｒ⁵¹〜Ｒ⁵⁷およびＲ⁶¹〜Ｒ⁶⁴はそれぞれ独立に水素原子または置換基を表す。Ｙは単結合、Ｏ、Ｓ、Ｓｅ、ＣＲ¹Ｒ²、ＮＲ³、ＳｉＲ⁴Ｒ⁵またはＢＲ⁶を表し、Ｒ¹〜Ｒ⁶はそれぞれ独立に水素原子または置換基を表す。ただし、一般式（Ｇ）、（Ｈ）および（Ｉ）において共通する名称の置換基は、互いに同一であっても異なっていてもよい。）
［５］ 下記一般式（１１）〜（１６）のいずれかで表されることを特徴とする化合物。

（一般式（１１）〜（１６）中、Ｘ¹¹〜Ｘ¹⁷およびＸ²¹〜Ｘ²⁴はそれぞれ独立にＣＲ⁰またはＮを表し、Ｒ⁰はそれぞれ独立に水素原子または置換基を表す。Ｙは単結合、Ｏ、Ｓ、Ｓｅ、ＣＲ¹Ｒ²、ＮＲ³、ＳｉＲ⁴Ｒ⁵またはＢＲ⁶を表し、Ｒ¹〜Ｒ⁶はそれぞれ独立に水素原子または置換基を表す。ただし、一般式（１１）〜（１６）において共通する名称の置換基は、互いに同一であっても異なっていてもよい。）
［６］ 下記一般式（２１）〜（２６）のいずれかで表されることを特徴とする［５］に記載の化合物。

（一般式（２１）〜（２６）中、Ｒ⁵¹〜Ｒ⁵⁷およびＲ⁶¹〜Ｒ⁶⁴はそれぞれ独立に水素原子または置換基を表す。Ｙは単結合、Ｏ、Ｓ、Ｓｅ、ＣＲ¹Ｒ²、ＮＲ³、ＳｉＲ⁴Ｒ⁵またはＢＲ⁶を表し、Ｒ¹〜Ｒ⁶はそれぞれ独立に水素原子または置換基を表す。ただし、一般式（２１）〜（２６）において共通する名称の置換基は、互いに同一であっても異なっていてもよい。）
［７］ 基板と、該基板上に配置され、陽極及び陰極からなる一対の電極と、該電極間に配置され、発光層を含む少なくとも一層の有機層とを有し、前記発光層に［１］〜［６］のいずれか一項に記載の合成法を経て合成された化合物を含むことを特徴とする有機電界発光素子。 That is, the present invention which is a specific means for solving the above-described problems is as follows.
[1] A compound represented by the following general formula (1) and a compound represented by the following general formula (2) are reacted, and a compound represented by the following general formula (3) is used as an intermediate, followed by A synthesis method comprising synthesizing a compound represented by formula (4).

(In the general formulas (1) to (4), X ^{11 to} X ¹⁷ and X ^{21 to} X ²⁴ each independently represent CR ⁰ or N, and R ⁰ each independently represents a hydrogen atom or a substituent. Represents a single bond, O, S, Se, CR ¹ R ² , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent, Z represents Cl, Br, I represents OTf, and Tf represents a trifluoromethanesulfonyl group (a trifuryl group).
[2] In the synthesis method according to [1], the compound represented by the general formula (4) is preferably a compound represented by any one of the following general formulas (A) to (C).

(In the general formulas (A) to (C), X ^{11 to} X ¹⁷ and X ^{21 to} X ²⁴ each independently represent CR ⁰ or N, and R ⁰ each independently represents a hydrogen atom or a substituent. Represents a single bond, O, S, Se, CR ¹ R ² , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , and R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent, provided that the general formula (A ), (B) and (C) may have the same or different substituents having the same name.
[3] In the synthesis method described in [1] or [2], the compound represented by the general formula (4) is a compound represented by the following general formula (8), and the following general formula (5) And a compound represented by the following general formula (6), a compound represented by the following general formula (7) as an intermediate, and a compound represented by the above general formula (8) Is preferably synthesized.

(In the general formulas (5) to (8), R ^{51 to} R ⁵⁷ and R ^{61 to} R ⁶⁴ each independently represent a hydrogen atom or a substituent. Y represents a single bond, O, S, Se, CR ¹ R ^2. , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent, Z represents Cl, Br, I or OTf, where Tf is trifluoromethanesulfonyl. Represents a group (trifuryl group).)
[4] In the synthesis method according to [3], the compound represented by the general formula (8) is preferably a compound represented by any one of the following general formulas (G) to (I).

(In the general formulas (G), (H) and (I), R ^{51 to} R ⁵⁷ and R ^{61 to} R ⁶⁴ each independently represents a hydrogen atom or a substituent. Y represents a single bond, O, S, Se, CR ¹ R ² , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , each of R ^{1 to} R ⁶ independently represents a hydrogen atom or a substituent, provided that the general formulas (G), (H) and (I) The substituents having the same name in the above may be the same or different.
[5] A compound represented by any one of the following general formulas (11) to (16).

(In the general formulas (11) to (16), X ^{11 to} X ¹⁷ and X ^{21 to} X ²⁴ each independently represent CR ⁰ or N, and R ⁰ each independently represents a hydrogen atom or a substituent. Represents a single bond, O, S, Se, CR ¹ R ² , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , and R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent, provided that the general formula (11 ) To (16) may have the same or different substituents having the same name.
[6] The compound according to [5], which is represented by any one of the following general formulas (21) to (26).

(In the general formulas (21) to (26), R ^{51 to} R ⁵⁷ and R ^{61 to} R ⁶⁴ each independently represent a hydrogen atom or a substituent. Y represents a single bond, O, S, Se, CR ¹ R ^2. , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent, provided that the substituents having the same names in the general formulas (21) to (26) are They may be the same or different.)
[7] A substrate, a pair of electrodes including an anode and a cathode disposed on the substrate, and at least one organic layer including a light-emitting layer disposed between the electrodes. ] The organic electroluminescent element characterized by including the compound synthesize | combined through the synthesis method as described in any one of [6].

  According to the present invention, indolocarbazole (indoro [3,2,1-jk] carbazole), which has a high yield, can be used for synthesis on the scale of several tens of grams, and has a simple by-product control. And methods for synthesizing analogs thereof.

It is the schematic which shows an example of a structure of the organic electroluminescent element which concerns on this invention. It is a NMR chart of indolocarbazole (indoro [3,2,1-jk] carbazole). It is a NMR chart of an indolocarbazole derivative having a nitro group. It is a NMR chart of an indolocarbazole derivative having an iodo group. It is a NMR chart of compound 25-a having a nitro group.

  Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

（一般式（１）〜（４）中、Ｘ¹¹〜Ｘ¹⁷およびＸ²¹〜Ｘ²⁴はそれぞれ独立にＣＲ⁰またはＮを表し、Ｒ⁰はそれぞれ独立に水素原子または置換基を表す。Ｙは単結合、Ｏ、Ｓ、Ｓｅ、ＣＲ¹Ｒ²、ＮＲ³、ＳｉＲ⁴Ｒ⁵またはＢＲ⁶を表し、Ｒ¹〜Ｒ⁶はそれぞれ独立に水素原子または置換基を表す。ＺはＣｌ、Ｂｒ、Ｉ、ＯＴｆを表す。なお、Ｔｆはトリフルオロメタンスルホニル基（トリフリル基）を表す。）
以下、本発明の合成法について、説明する。なお、好ましい代表例であるインドロカルバゾール（ｉｎｄｏｒｏ ［３，２，１−ｊｋ］ｃａｒｂａｚｏｌｅ）およびその類縁体の合成法について説明することがあるが、本発明はこのような態様に限定されるものではない。 [Synthesis method]
(Method for synthesizing compound represented by formula (4))
In the synthesis method of the present invention, a compound represented by the following general formula (1) and a compound represented by the following general formula (2) are reacted, and the compound represented by the following general formula (3) is used as an intermediate. Then, the compound represented by the following general formula (4) is synthesized.

(In the general formulas (1) to (4), X ^{11 to} X ¹⁷ and X ^{21 to} X ²⁴ each independently represent CR ⁰ or N, and R ⁰ each independently represents a hydrogen atom or a substituent. Represents a single bond, O, S, Se, CR ¹ R ² , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent, Z represents Cl, Br, I represents OTf, and Tf represents a trifluoromethanesulfonyl group (a trifuryl group).
Hereinafter, the synthesis method of the present invention will be described. In addition, although there may be described a method for synthesizing indolocarbazole (indoro [3,2,1-jk] carbazole), which is a preferred representative example, and its analogs, the present invention is limited to such an embodiment. is not.

In the present invention, the hydrogen atom in the description of each general formula includes an isotope (deuterium atom and the like), and the atoms constituting the substituent further include the isotope.
In the present invention, when referred to as “substituent”, the substituent may be substituted. For example, the term “alkyl group” in the present invention includes an alkyl group substituted with a fluorine atom (for example, trifluoromethyl group) and an alkyl group substituted with an aryl group (for example, triphenylmethyl group). When the term “alkyl group having 1 to 6 carbon atoms” is used, it means that the number of carbon atoms is 1 to 6 as all groups including those substituted.

First, the reaction when the compound represented by the general formula (1) and the compound represented by the general formula (2) are reacted to synthesize the compound represented by the general formula (3) as an intermediate. Conditions are not particularly limited, and known conditions can be used. For example, the conditions described in [0302] and [0303] of JP 2010-087496 A can be used. Specifically, the following conditions are preferable.
The ratio of the compound represented by the general formula (1) and the compound represented by the general formula (2) is preferably in the following range in terms of equivalent ratio (molar ratio).
The addition amount of the general formula (2) is preferably 3.0 to 1.0 equivalent, more preferably 2.0 to 1.0 equivalent with respect to the general formula (1). It is particularly preferably 1.0 to 1.5 equivalents.
The solvent used when reacting the compound represented by the general formula (1) and the compound represented by the general formula (2) can include the following, among which N, N-dimethylacetamide is preferable. .
Examples include polar solvents such as dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone.
As an additive used when the compound represented by the general formula (1) and the compound represented by the general formula (2) are reacted, it is preferable to use potassium carbonate. The amount of potassium carbonate added is preferably 2.0 to 5.0 equivalents, more preferably 2.0 to 3.0 equivalents, more preferably 2.5 to 3 with respect to the general formula (1). It is particularly preferable that the amount is equivalent. Further, the following additives may be used simultaneously with potassium carbonate or in place of potassium carbonate.
In addition to inorganic bases such as sodium carbonate, cesium carbonate, tertiary butoxy potassium, tertiary butoxy sodium, potassium phosphate, potassium acetate, sodium acetate, sodium hydride, triethylamine, diazabicycloundecene (DBU), N, And organic bases such as N-diisopropylethylamine.
As reaction conditions for reacting the compound represented by the general formula (1) and the compound represented by the general formula (2), the heating temperature is preferably 100 to 200 ° C, and 110 to 190 ° C. It is more preferable that it is 120-180 degreeC. The reaction time is preferably 0.5 to 12 hours, more preferably 0.5 to 5 hours, and particularly preferably 0.5 to 2 hours. These heating temperature and reaction time vary depending on the compound used, and the heating temperature and reaction time are appropriately selected until the compound represented by the general formula (1) disappears. In general, when the compound represented by the general formula (2) has an electron withdrawing group, the heating temperature is lower and the reaction time is often shorter than when the compound has no electron withdrawing group.

Next, the reaction conditions for synthesizing the compound represented by the general formula (4) from the compound represented by the general formula (3) are not particularly limited, and known conditions can be used. For example, J. et al. AM. CHEM. SOC. The conditions described in 2006, 128, 581-590 can be used. Specifically, the following conditions are preferable.
Examples of the catalyst for synthesizing the compound represented by the general formula (4) from the compound represented by the general formula (3) include the following, among which palladium acetate is preferable.
Palladium acetate, palladium chloride, dichlorobis (triphenylphosphine) palladium, dichlorobis (triphenylphosphine) nickel, dichlorobis (tricyclohexylphosphine) palladium, trisdibenzylideneacetonedipalladium and the like can be mentioned.
The amount of palladium acetate added is preferably 1 to 200 mol%, more preferably 3 to 50 mol%, and particularly preferably 3 to 25 mol% with respect to the general formula (1). .
The ligands used when synthesizing the compound represented by the general formula (4) from the compound represented by the general formula (3) can include the following, among which tricyclohexylphosphonium tetra Fluoroborate is preferred.
Examples include tricyclohexylphosphonium tetrafluoroborate, tricyclohexylphosphine, tritertiary butylphosphine, (2-biphenyl) ditertiarybutylphosphine, and various imidazolium salts. The addition amount of tricyclohexylphosphonium tetrafluoroborate is preferably 1.0 to 4.0 equivalents, more preferably 1.5 to 3.0 equivalents, more preferably 2 to the previous group of palladium acetate. It is especially preferable that it is 0.0-2.4 equivalent.
As reaction conditions for synthesizing the compound represented by the general formula (4) from the compound represented by the general formula (3), the heating temperature is preferably 100 to 200 ° C, and 110 to 190. More preferably, it is 120 degreeC, and it is especially preferable that it is 120-185 degreeC. The reaction time is preferably 0.5 to 12 hours, more preferably 0.5 to 5 hours, and particularly preferably 0.5 to 3 hours.

In the general formulas (1) to (4), X ^{11 to} X ¹⁷ and X ^{21 to} X ²⁴ each independently represent CR ⁰ or N, and R ⁰ each independently represents a hydrogen atom or a substituent.

In the general formula (1), examples of the substituent represented by R ⁰ include the following substituent group A, and the substituent may further have a substituent. Examples of the further substituent include a group selected from the substituent group A.

<< Substituent group A >>
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, n-propyl, isopropyl, t-butyl, n-hexyl, 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 carbon number). 2-10, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group (preferably having 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably carbon number). 2 to 10 such as propargyl and 3-pentynyl), aryl group (preferably having 6 to 3 carbon atoms) , More preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, anthranyl, etc.), an amino group (preferably 0 to 30 carbon atoms, More preferably, it has 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, dibenzylamino, phenylamino, diphenylamino, ditolylamino and the like. Group (preferably having 1 to 30 carbon atoms, 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), aryl An oxy group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably Or having 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy and the like, and a heterocyclic oxy group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 30 carbon atoms). 20, particularly preferably 1 to 12 carbon atoms, such as pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.), acyl groups (preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, especially Preferably it is C2-C12, for example, acetyl, benzoyl, formyl, pivaloyl etc.), alkoxycarbonyl group (preferably C2-C30, more preferably C2-C20, particularly preferably carbon 2 to 12, for example, methoxycarbonyl, ethoxycarbonyl, etc.) An aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonyl and the like. ), An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as acetoxy and benzoyloxy), an acylamino group (preferably 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably 2-10 carbon atoms, and examples thereof include acetylamino, benzoylamino, and the like, and an alkoxycarbonylamino group (preferably having 2-2 carbon atoms). 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, etc.), aryloxycarbonylamino group (preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl And sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino). ), A sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenyl Sulfamoyl, etc.), a carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, Phenylcarbamoyl etc.), alkylthio group ( Preferably, it has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methylthio, ethylthio and the like, and an arylthio group (preferably 6 to 30 carbon atoms). , More preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.), a heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably 1 to carbon atoms). 20, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazolylthio and the like, and a sulfonyl group (preferably having a carbon number). 1 to 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl). Rufinyl 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 methanesulfinyl and benzenesulfinyl. ), A ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylureido, etc.), phosphoric acid. An amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenylphosphoric acid amide), a hydroxy group , Mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (aromatic hetero A ring group is also included, preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms. Nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom, selenium atom, tellurium atom, specifically pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, pyrrolyl, pyrazolyl, triazolyl, imidazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl Quinolyl, furyl, thienyl, selenophenyl, tellurophenyl, piperidyl, piperidino, morpholino, pyrrolidyl, pyrrolidino, benzoxazolyl, benzimidazolyl, benzothiazolyl, carbazolyl group, azepinyl group, silylyl group, etc.), silyl group ( Preferably it has 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl, triphenylsilyl, and the like. A group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, such as trimethylsilyloxy, triphenylsilyloxy, etc.), phosphoryl group (for example, diphenyl) A phosphoryl group, a dimethylphosphoryl group, etc.). These substituents may be further substituted, and examples of the further substituent include a group selected from the substituent group A described above.

As said R < ⁰ > contained in X < ¹¹ > -X < ¹⁷ >, a hydrogen atom, an aryl group, or heteroaryl group is preferable among the said substituent group A each independently.
As said R < ⁰ > contained in X < ²¹ > -X < ²⁴ >, among the said substituent group A, a hydrogen atom, an aryl group or heteroaryl group, an acylamino group, and an electron withdrawing group (for example, nitro group) are respectively preferable.

The aryl group represented by R ⁰ preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 18 carbon atoms. For example, a phenyl group, a xylyl group, a biphenyl group, a terphenyl group, A naphthyl group, an anthranyl group, a triphenylenyl group, a pyrenyl group, etc. are mentioned.
The heteroaryl group represented by R ⁰ preferably has 5 to 30 ring members, more preferably 5 to 20 ring members, and particularly preferably 5 to 15 ring members. For example, pyridyl group, pyrimidyl group, triazyl group, pyrazyl group, Examples include a pyridazyl group, a carbazolyl group, a dibenzothiophenyl group, a dibenzofuranyl group.

R ⁰ contained in X ^{11 to} X ¹⁷ and X ^{21 to} X ²⁴ may further have a substituent represented by the substituent group A as described above.
However, the further substituents that R ⁰ may have may be connected to each other to form a condensed ring.
The further substituent that R ⁰ may have may be further substituted.

Of X ^{11 to} X ¹⁷ and X ^{21 to} X ²⁴ , the number of CR ⁰ is preferably 1 to 11, more preferably 5 to 11, and particularly preferably 8 to 11. 9 to 11 is more particularly preferable, 10 or 11 is even more particularly preferable, and 11 is even more particularly preferable.
Moreover, the number of CR ⁰ in which R ⁰ is a substituent among X ^{11 to} X ¹⁷ and X ^{21 to} X ²⁴ is 0 to 11, more preferably 0 to 8, and preferably 1 to 3 It is particularly preferable that the number is one.

The position of CR ⁰ in which R ⁰ is a substituent among X ^{21 to} X ²³ depends on the position of the ring formed by condensing two CR ^0, but at least of X ²¹ , X ²² and X ²³ One is preferable, and X ²² is more preferable.

In general formulas (1) to (4), Y represents a single bond, O, S, Se, CR ¹ R ² , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , and R ^{1 to} R ⁶ are each independently hydrogen. Represents an atom or substituent. Y is preferably a single bond, O, S, CR ¹ R ² , NR ³ , or SiR ⁴ R ⁵ , more preferably a single bond, O, S, CR ¹ R ² , or NR ³ , Particularly preferred is a bond, CR ¹ R ² or NR ³ .

  Here, the synthesis method of the present invention also provides a yield even when Y represents a single bond, that is, the compound represented by the general formula (4) is an indolocarbazole skeleton having two 5-membered rings. In addition, it can handle synthesis of a scale of several tens of grams and is simple with a small number of steps. Such an indolocarbazole skeleton having two five-membered rings has a large intramolecular strain, so the yield is high and it can be used for synthesis on the scale of several tens of grams. The ability to synthesize was unexpected for those skilled in the art. This is because the above-mentioned Chem. Eur. J. et al. 2009, 15, 5482-5490 is supported by the synthesis using a special FVP device.

Examples of the substituent represented by the substituents R ¹ and R ² on the carbon atom include the substituent group A described above, and the substituent on the carbon atom is preferably an alkyl group, a perfluoroalkyl group, an aryl group, A heteroaryl group, a dialkylamino group, a diarylamino group, an alkoxy group, a cyano group, and a fluorine atom, an alkyl group or an aryl group is more preferable, and a methyl group or a phenyl group is particularly preferable.

Examples of the substituent represented by the substituent R ³ on the nitrogen atom include the following substituent group B.
<< 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, isopropyl, 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 groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as propargyl , 3-pentynyl, etc.), an aryl group (preferably having 6 to 30 carbon atoms, more preferably carbon 6 to 20, particularly preferably 6 to 12 carbon atoms, including, for example, phenyl, p-methylphenyl, naphthyl, anthranyl, etc.), cyano group, heterocyclic group (including aromatic heterocyclic group, Has 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a silicon atom, a selenium atom, and a tellurium atom. Is pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, pyrrolyl, pyrazolyl, triazolyl, imidazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, quinolyl, furyl, thienyl, selenophenyl, tellurophenyl, piperidyl, piperidino, morpholino, pyrrolidyl, pyrrolidino, benzoxazolid Le, benzimidazo , Benzothiazolyl, carbazolyl, azepinyl group, etc. Shiroriru group.), And the like. These substituents may be further substituted, and examples of the further substituent include a group selected from the substituent group B described above.
The substituent on the nitrogen atom represented by R ³ is preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, more preferably an aryl group, and a phenyl group or a phenyl group (biphenyl group) substituted with a phenyl group. Particularly preferred.

Preferred ranges of the substituents represented by the substituents R ⁴ and R ⁵ on the silicon atom are the same as the preferred ranges of the substituents represented by the substituents R ¹ and R ² on the carbon atom.

The preferred range of the substituent represented by the substituent R ⁶ on the boron atom is the same as the preferred range of the substituent represented by the substituent R ³ on the nitrogen atom.

  In general formulas (1) to (4), Z represents Cl, Br, I, or OTf. Tf represents a trifluoromethanesulfonyl group (trifuryl group). Among them, Z is preferably Cl.

一般式（Ａ）〜（Ｃ）中、Ｘ¹¹〜Ｘ¹⁷およびＸ²¹〜Ｘ²⁴はそれぞれ独立にＣＲ⁰またはＮを表し、Ｒ⁰はそれぞれ独立に水素原子または置換基を表す。Ｙは単結合、Ｏ、Ｓ、Ｓｅ、ＣＲ¹Ｒ²、ＮＲ³、ＳｉＲ⁴Ｒ⁵またはＢＲ⁶を表し、Ｒ¹〜Ｒ⁶はそれぞれ独立に水素原子または置換基を表す。
一般式（Ａ）〜（Ｃ）におけるＸ¹¹〜Ｘ¹⁷およびＸ²¹〜Ｘ²⁴の好ましい範囲は、前記一般式（４）で表される化合物におけるＸ¹¹〜Ｘ¹⁷およびＸ²¹〜Ｘ²⁴の好ましい範囲と同様である。
一般式（Ａ）〜（Ｃ）におけるＹの好ましい範囲は、前記一般式（４）で表される化合物におけるＹの好ましい範囲と同様である。
前記一般式（４）で表される化合物が、前記一般式（Ｂ）で表される化合物であることがより好ましい。 In the synthesis method of the present invention, the compound represented by the general formula (4) is preferably a compound represented by any one of the following general formulas (A) to (C).

In the general formulas (A) to (C), X ^{11 to} X ¹⁷ and X ^{21 to} X ²⁴ each independently represent CR ⁰ or N, and R ⁰ each independently represents a hydrogen atom or a substituent. Y represents a single bond, O, S, Se, CR ¹ R ² , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , and R ^{1 to} R ⁶ each independently represent a hydrogen atom or a substituent.
A preferred range of X ¹¹ to X ¹⁷ and X ²¹ to X ²⁴ in the general formula (A) ~ (C) is a X ¹¹ to X ¹⁷ and X ²¹ to X ²⁴ in the compound represented by the general formula (4) This is the same as the preferred range.
The preferable range of Y in the general formulas (A) to (C) is the same as the preferable range of Y in the compound represented by the general formula (4).
The compound represented by the general formula (4) is more preferably a compound represented by the general formula (B).

一般式（５）〜（８）中、Ｒ⁵¹〜Ｒ⁵⁷およびＲ⁶¹〜Ｒ⁶⁴はそれぞれ独立に水素原子または置換基を表す。Ｙは単結合、Ｏ、Ｓ、Ｓｅ、ＣＲ¹Ｒ²、ＮＲ³、ＳｉＲ⁴Ｒ⁵またはＢＲ⁶を表し、Ｒ¹〜Ｒ⁶はそれぞれ独立に水素原子または置換基を表す。ＺはＣｌ、Ｂｒ、Ｉ、ＯＴｆを表す。なお、Ｔｆはトリフルオロメタンスルホニル基（トリフリル基）を表す。
一般式（５）〜（８）におけるＲ⁵¹〜Ｒ⁵⁷およびＲ⁶¹〜Ｒ⁶⁴の好ましい範囲は、前記一般式（１）〜（４）で表される化合物におけるＸ¹¹〜Ｘ¹⁷およびＸ²¹〜Ｘ²⁴が有するＲ⁰の好ましい範囲と同様である。
一般式（５）〜（８）におけるＹの好ましい範囲は、前記一般式（１）〜（４）で表される化合物におけるＹの好ましい範囲と同様である。
一般式（５）〜（８）におけるＺの好ましい範囲は、前記一般式（１）〜（４）で表される化合物におけるＺの好ましい範囲と同様である。 In the synthesis method of the present invention, the compound represented by the general formula (4) is a compound represented by the following general formula (8), and the compound represented by the following general formula (5) and the following general formula ( It is preferable to react the compound represented by 6) and synthesize the compound represented by the general formula (8) through the compound represented by the following general formula (7) as an intermediate.

In general formulas (5) to (8), R ^{51 to} R ⁵⁷ and R ^{61 to} R ⁶⁴ each independently represent a hydrogen atom or a substituent. Y represents a single bond, O, S, Se, CR ¹ R ² , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , and R ^{1 to} R ⁶ each independently represent a hydrogen atom or a substituent. Z represents Cl, Br, I, or OTf. Tf represents a trifluoromethanesulfonyl group (trifuryl group).
The preferred ranges of R ^{51 to} R ⁵⁷ and R ^{61 to} R ^{64 in} the general formulas (5) to (8) are X ^{11 to} X ¹⁷ and X ²¹ in the compounds represented by the general formulas (1) to (4). it is the same as the preferred ranges of R ⁰ where to X ²⁴ has.
The preferable range of Y in the general formulas (5) to (8) is the same as the preferable range of Y in the compounds represented by the general formulas (1) to (4).
The preferable range of Z in the general formulas (5) to (8) is the same as the preferable range of Z in the compounds represented by the general formulas (1) to (4).

一般式（Ｇ）、（Ｈ）および（Ｉ）中、Ｒ⁵¹〜Ｒ⁵⁷およびＲ⁶¹〜Ｒ⁶⁴はそれぞれ独立に水素原子または置換基を表す。Ｙは単結合、Ｏ、Ｓ、Ｓｅ、ＣＲ¹Ｒ²、ＮＲ³、ＳｉＲ⁴Ｒ⁵またはＢＲ⁶を表し、Ｒ¹〜Ｒ⁶はそれぞれ独立に水素原子または置換基を表す。
一般式（Ｇ）〜（Ｉ）におけるＲ⁵¹〜Ｒ⁵⁷およびＲ⁶¹〜Ｒ⁶⁴の好ましい範囲は、前記一般式（８）で表される化合物におけるＲ⁵¹〜Ｒ⁵⁷およびＲ⁶¹〜Ｒ⁶⁴の好ましい範囲と同様である。
一般式（Ｇ）〜（Ｉ）におけるＹの好ましい範囲は、前記一般式（８）で表される化合物におけるＹの好ましい範囲と同様である。
前記一般式（８）で表される化合物が、前記一般式（Ｈ）で表される化合物であることがより好ましい。 In the synthesis method of the present invention, the compound represented by the general formula (8) is preferably a compound represented by any one of the following general formulas (G) to (I).

In the general formulas (G), (H) and (I), R ^{51 to} R ⁵⁷ and R ^{61 to} R ⁶⁴ each independently represent a hydrogen atom or a substituent. Y represents a single bond, O, S, Se, CR ¹ R ² , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , and R ^{1 to} R ⁶ each independently represent a hydrogen atom or a substituent.
A preferred range of R ⁵¹ to R ⁵⁷ and R ⁶¹ to R ⁶⁴ in the general formula (G) ~ (I) are, of R ⁵¹ to R ⁵⁷ and R ⁶¹ to R ⁶⁴ in the compound represented by the general formula (8) This is the same as the preferred range.
The preferable range of Y in the general formulas (G) to (I) is the same as the preferable range of Y in the compound represented by the general formula (8).
The compound represented by the general formula (8) is more preferably a compound represented by the general formula (H).

Specific examples of compounds in which Y is a single bond among the compounds represented by the general formula (1) are listed below, but the present invention is not limited thereto. Further, when Y in the general formula (1) is O, S, Se, CR ¹ R ² , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , it can be considered in the same manner as when Y is a single bond.

  Specific examples of the compound represented by the general formula (2) are listed below, but the present invention is not limited thereto.

Specific examples of the compound represented by the general formula (3) in which Y is a single bond and Z is Cl are listed below, but the present invention is not limited thereto. Further, when Y in the general formula (1) is O, S, Se, CR ¹ R ² , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , it can be considered in the same manner as when Y is a single bond. Further, when Z is Br, I, or OTf, these combinations can be considered.

（一般式（Ｄ）、（Ｅ）および（Ｆ）中、Ｘ¹¹〜Ｘ¹⁷およびＸ²¹〜Ｘ²⁴はそれぞれ独立にＣＲ⁰またはＮを表し、Ｒ⁰はそれぞれ独立に水素原子または置換基を表す。Ｙは単結合、Ｏ、Ｓ、Ｓｅ、ＣＲ¹Ｒ²、ＮＲ³、ＳｉＲ⁴Ｒ⁵またはＢＲ⁶を表し、Ｒ¹〜Ｒ⁶はそれぞれ独立に水素原子または置換基を表す。Ｐ、ＱおよびＲはそれぞれ独立にＩ、Ｂｒ、ＣｌまたはＯＨを表す。）
このような一般式（Ｄ）、（Ｅ）および（Ｆ）で表される化合物は、置換基を導入することができる位置Ｐ、Ｑ、Ｒをあらかじめ決定できているために、前記一般式（４）で表される化合物に置換基を導入した化合物を合成するときにこれらの一般式（Ｄ）、（Ｅ）および（Ｆ）で表される化合物を中間体として経て合成することで、副生成物の生成を抑制することができる。 (Method for synthesizing compounds represented by formulas (D) to (F))
Furthermore, this invention is represented by the following general formula (D)-(F) characterized by using the compound represented by the said general formula (A)-(C) manufactured with the synthesis method of this invention. The present invention also relates to a method for synthesizing a compound.

(In the general formulas (D), (E) and (F), X ^{11 to} X ¹⁷ and X ^{21 to} X ²⁴ each independently represent CR ⁰ or N, and R ⁰ each independently represents a hydrogen atom or a substituent. Y represents a single bond, O, S, Se, CR ¹ R ² , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , and R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent. Q and R each independently represents I, Br, Cl or OH.)
Such compounds represented by the general formulas (D), (E), and (F) have previously determined positions P, Q, and R at which substituents can be introduced. 4) By synthesizing the compounds represented by the general formulas (D), (E) and (F) as intermediates when synthesizing a compound in which a substituent is introduced into the compound represented by 4), Product formation can be suppressed.

A preferred range of the general formula (D), X ¹¹ ~X ¹⁷ and X ²¹ to X ²⁴ in (E) and (F), X ¹¹ to X in the general formula (1) to the compound represented by (4) ^This is the same as the preferred range of ¹⁷ and X ^{21 to} X ²⁴ .
The preferable range of Y in the general formulas (D), (E) and (F) is the same as the preferable range of Y in the compounds represented by the general formulas (1) to (4).
In the general formulas (D), (E) and (F), P, Q and R each independently represent I, Br, Cl or OH, preferably I, Br or OH, more preferably I. preferable.
Among the compounds represented by the general formulas (D), (E), and (F), the compound represented by the general formula (E) is more preferable.

（一般式（Ｊ）、（Ｋ）および（Ｌ）中、Ｒ⁵¹〜Ｒ⁵⁷およびＲ⁶¹〜Ｒ⁶⁴はそれぞれ独立に水素原子または置換基を表す。Ｙは単結合、Ｏ、Ｓ、Ｓｅ、ＣＲ¹Ｒ²、ＮＲ³、ＳｉＲ⁴Ｒ⁵またはＢＲ⁶を表し、Ｒ¹〜Ｒ⁶はそれぞれ独立に水素原子または置換基を表す。Ｓ、ＴおよびＵはそれぞれ独立にＩ、Ｂｒ、ＣｌまたはＯＨを表す。
一般式（Ｊ）、（Ｋ）および（Ｌ）におけるＲ⁵¹〜Ｒ⁵⁷およびＲ⁶¹〜Ｒ⁶⁴の好ましい範囲は、前記一般式（Ｇ）〜（Ｉ）で表される化合物におけるＲ⁵¹〜Ｒ⁵⁷およびＲ⁶¹〜Ｒ⁶⁴の好ましい範囲と同様である。
一般式（Ｊ）、（Ｋ）および（Ｌ）におけるＹの好ましい範囲は、前記一般式（Ｇ）〜（Ｉ）で表される化合物におけるＹの好ましい範囲と同様である。
一般式（Ｊ）、（Ｋ）および（Ｌ）におけるＳ、ＴおよびＵの好ましい範囲は、前記一般式（Ｄ）〜（Ｆ）で表される化合物におけるＰ、Ｑ、Ｒの好ましい範囲と同様である。
一般式（Ｊ）、（Ｋ）および（Ｌ）で表される化合物の中でも、前記一般式（Ｋ）で表される化合物であることがより好ましい。 The method for synthesizing the compounds represented by the general formulas (D) to (F) is preferably a method for synthesizing the compounds represented by the following general formulas (J) to (L).
That is, this invention uses the compound represented by the said general formula (G)-(I) manufactured with the synthesis method of this invention, It represents with following general formula (J)-(L) characterized by the above-mentioned. The present invention also relates to a method for synthesizing the compound.

(In the general formulas (J), (K) and (L), R ^{51 to} R ⁵⁷ and R ^{61 to} R ⁶⁴ each independently represents a hydrogen atom or a substituent. Y represents a single bond, O, S, Se, CR ¹ R ² , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent, S, T and U each independently represent I, Br, Cl or Represents OH.
Formula (J), the preferred range of R ⁵¹ to R ⁵⁷ and R ⁶¹ to R ⁶⁴ in (K) and (L) is, R ⁵¹ in the compound represented by the general formula (G) ~ (I) ~R ^This is the same as the preferred range of ⁵⁷ and R ^{61 to} R ⁶⁴ .
The preferable range of Y in the general formulas (J), (K) and (L) is the same as the preferable range of Y in the compounds represented by the general formulas (G) to (I).
Preferred ranges of S, T and U in the general formulas (J), (K) and (L) are the same as the preferred ranges of P, Q and R in the compounds represented by the general formulas (D) to (F). It is.
Among the compounds represented by the general formulas (J), (K), and (L), the compound represented by the general formula (K) is more preferable.

There are no particular limitations on the conditions for the reduction reaction from the compound having a nitro group represented by the general formulas (A) to (C) and the general formulas (G) to (I) to a compound having an NH ₂ group. The following conditions can be used. For example, catalytic reduction using hydrogen and a metal catalyst (for example, Pd / C), reduction reaction using a metal (for example, iron, tin, zinc) under acidic conditions, metal hydride reagent (for example, lithium aluminum hydride) Examples include the reduction reaction used.

Compounds having an NH ₂ group derived from compounds having a nitro group represented by the general formulas (A) to (C) and the general formulas (G) to (I) are represented by the general formulas (D) to (F). ) And the compounds represented by the general formulas (J) to (L) can be converted by diazotization followed by Sandmeyer reaction or hydrolysis. These reaction conditions are not particularly limited, and known conditions can be used. For example, the conditions described in Experimental Science Course 5th edition Volume 13 (Maruzen) can be mentioned. Among these, P to R are preferably I from the viewpoint of yield.

  The compound represented by the general formula (4) obtained by the synthesis method of the present invention and the compound having an amino group derived therefrom, the general formulas (D) to (F) or the general formulas (J) to (L) ) To synthesize a compound for an organic electroluminescent element from the viewpoint of controlling by-products.

  The compound represented by the general formula (4) obtained by the synthesis method of the present invention, the compound having an amino group derived therefrom, the general formulas (D) to (F) or the general formulas (J) to (L) The molecular weight of the compound for organic electroluminescent element synthesized using (hereinafter collectively referred to as the compound synthesized through the synthesis method of the present invention) is usually 400 or more and 1500 or less, and 450 or more and 1200 or less. It is preferably 500 to 1100, more preferably 550 to 1000. When the molecular weight is 450 or more, it is advantageous for forming a high-quality amorphous thin film, and when the molecular weight is 1200 or less, the solubility and sublimation property are improved, which is advantageous for improving the purity of the compound. From the viewpoint of the glass transition temperature, the molecular weight of the compound synthesized through the synthesis method of the present invention is preferably 550 or more. On the other hand, from the viewpoint of laminating a composition containing a compound synthesized through the synthesis method of the present invention by vapor deposition, the compound synthesized through the synthesis method of the present invention preferably has a molecular weight of 1200 or less.

When the compound synthesized through the synthesis method of the present invention is used as a host material of a light emitting layer of an organic electroluminescent device or a charge transport material of a layer adjacent to the light emitting layer, an energy gap in a thin film state than a light emitting material described later. (When the light emitting material described later is a phosphorescent light emitting material, a large minimum triplet (T ₁ ) energy in a thin film state) is advantageous in improving efficiency by preventing quenching of light emission. On the other hand, from the viewpoint of chemical stability of the compound, it is preferable that the energy gap and T ₁ energy are not too large.

The T ₁ energy in the film state of the compound synthesized through the synthesis method of the present invention is preferably 1.77 eV (40 kcal / mol) or more and 3.51 eV (81 kcal / mol) or less, preferably 2.39 eV (55 kcal). / Mol) and more preferably 3.25 eV (75 kcal / mol) or less. In the organic electroluminescent device of the present invention, it is preferable from the viewpoint of luminous efficiency that the T ₁ energy of the compound synthesized through the synthesis method of the present invention is higher than the T ₁ energy of the phosphorescent material described later. In particular, when the emission color from the organic electroluminescence device is green (emission peak wavelength is 490 to 580 nm), from the viewpoint of light emission efficiency, the T ₁ energy is 2.39 eV (55 kcal / mol) or more and 2.82 eV (65 kcal / mol). mol) or less.

The T ₁ energy can be obtained from the short wavelength end of a phosphorescence emission spectrum of a thin film of material. For example, a material is deposited on a cleaned quartz glass substrate to a film thickness of about 50 nm by a vacuum deposition method, and the phosphorescence emission spectrum of the thin film is F-7000 Hitachi Spectrofluorimeter (Hitachi High-Technologies) under liquid nitrogen temperature. Use to measure. T ₁ energy can be obtained by converting the rising wavelength on the short wavelength side of the obtained emission spectrum into energy units.

  From the viewpoint of stably operating the organic electroluminescent element against heat generated during high temperature driving or driving the element, and from the viewpoint of reducing the chromaticity deviation during high temperature storage, the organic electroluminescent element of the present invention is not limited to the above-described one. The compound synthesized through the synthesis method is preferably a compound having a glass transition temperature of 100 ° C. or higher. The glass transition temperature (Tg) of the compound synthesized through the synthesis method of the present invention is more preferably 100 ° C. or higher and 400 ° C. or lower, particularly preferably 120 ° C. or higher and 400 ° C. or lower, and 140 ° C. or higher and 400 ° C. or lower. More preferably, it is not higher than ° C.

  When the purity of the compound synthesized through the synthesis method of the present invention is low, impurities work as a trap for charge transport or promote deterioration of the device. Therefore, the compound synthesized by the synthesis method of the present invention The higher the purity, the better. Purity can be measured by, for example, high performance liquid chromatography (HPLC), and the area ratio of the compound synthesized by the synthesis method of the present invention when detected with a light absorption intensity of 254 nm is preferably 95.0% or more, and more It is preferably 97.0% or more, particularly preferably 99.0% or more, and most preferably 99.9% or more. Examples of the method for increasing the purity of the compound synthesized through the synthesis method of the present invention include recrystallization and sublimation purification.

  Although the specific example of the compound synthesize | combined using the synthesis method of this invention is enumerated below, this invention is not limited to these.

（一般式（１１）〜（１６）中、Ｘ¹¹〜Ｘ¹⁷およびＸ²¹〜Ｘ²⁴はそれぞれ独立にＣＲ⁰またはＮを表し、Ｒ⁰はそれぞれ独立に水素原子または置換基を表す。Ｙは単結合、Ｏ、Ｓ、Ｓｅ、ＣＲ¹Ｒ²、ＮＲ³、ＳｉＲ⁴Ｒ⁵またはＢＲ⁶を表し、Ｒ¹〜Ｒ⁶はそれぞれ独立に水素原子または置換基を表す。）
前記一般式（１１）〜（１６）における各置換基の好ましい範囲は、前記一般式（Ｄ）〜（Ｆ）における各置換基の好ましい範囲と同様である。 [Compound of the present invention]
The present invention also relates to a novel compound represented by any one of the following general formulas (11) to (16).

(In the general formulas (11) to (16), X ^{11 to} X ¹⁷ and X ^{21 to} X ²⁴ each independently represent CR ⁰ or N, and R ⁰ each independently represents a hydrogen atom or a substituent. A single bond, O, S, Se, CR ¹ R ² , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , and R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent.)
The preferable range of each substituent in the general formulas (11) to (16) is the same as the preferable range of each substituent in the general formulas (D) to (F).

（一般式（２１）〜（２６）中、Ｒ⁵¹〜Ｒ⁵⁷およびＲ⁶¹〜Ｒ⁶⁴はそれぞれ独立に水素原子または置換基を表す。Ｙは単結合、Ｏ、Ｓ、Ｓｅ、ＣＲ¹Ｒ²、ＮＲ³、ＳｉＲ⁴Ｒ⁵またはＢＲ⁶を表し、Ｒ¹〜Ｒ⁶はそれぞれ独立に水素原子または置換基を表す。）
前記一般式（２１）〜（２６）における各置換基の好ましい範囲は、前記一般式（Ｇ）〜（Ｉ）における各置換基の好ましい範囲と同様である。 The compound of the present invention is more preferably represented by any one of the following general formulas (21) to (26).

(In the general formulas (21) to (26), R ^{51 to} R ⁵⁷ and R ^{61 to} R ⁶⁴ each independently represent a hydrogen atom or a substituent. Y represents a single bond, O, S, Se, CR ¹ R ^2. , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , and R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent.)
The preferable range of each substituent in the general formulas (21) to (26) is the same as the preferable range of each substituent in the general formulas (G) to (I).

Specific examples of particularly preferable compounds for an organic electroluminescence device synthesized through a compound synthesized using the synthesis method of the present invention are listed below, but the present invention is not limited thereto.

  Three general synthesis methods for synthesizing a compound for an organic electroluminescence device through a compound synthesized using the synthesis method of the present invention will be described, but the present invention is not limited thereto.

Part 1

R ^{101 and} R ¹⁰² each independently represents a substituent. As the substituent, an aryl group and a heteroaryl group are preferable. R ^{201 and} R ²⁰² each independently represent a leaving group. Examples of the leaving group include Cl, Br, and I. Known conditions can be used for the coupling reaction. For example, it can be synthesized using a metal catalyst such as a Cu catalyst or a Pd catalyst, using a known appropriate ligand, a base, and a solvent.

Part 2

P to Q in the general formulas (D) to (F) each independently represent Cl, Br, or I. R ¹⁰³ represents a substituent. As the substituent, an aryl group and a heteroaryl group are preferable. R ²⁰³ represents a leaving group. Examples of the leaving group include Cl, Br, I, boronic acid (B (OH) ₂ ), boronic acid ester derivatives, and boronic acid ester salts. Known conditions can be used for the coupling reaction. For example, when P to Q are represented by I and R ²⁰³ is represented by B (OH) ₂ , they can be synthesized by Suzuki coupling using a Pd catalyst.
Moreover, after converting PQ into a boronic acid or a boronic acid ester derivative by a well-known method, coupling reaction can also be performed.

Part 3

P to Q in the general formulas (D) to (F) each independently represent Cl, Br, or I. R ¹⁰⁴ or R ¹⁰⁵ each independently represents a substituent. As the substituent, an aryl group and a heteroaryl group are preferable. Further, R ¹⁰⁴ and R ¹⁰⁵ may be connected to each other. Known conditions can be used for the coupling reaction. For example, it can be synthesized using a metal catalyst such as a Cu catalyst or a Pd catalyst, using a known appropriate ligand, a base, and a solvent.

  When P to Q in the general formulas (D) to (F) are OH, the reaction is performed with trifluoromethanesulfonic anhydride, and the OH group is converted to the OTf group, thereby being the same as Cl, Br, and I described above. A coupling reaction can be performed. Tf represents a trifluoromethanesulfonyl group (trifuryl group).

[Organic electroluminescence device]
The organic electroluminescent element of the present invention comprises a substrate, a pair of electrodes arranged on the substrate and consisting of an anode and a cathode, and at least one organic layer disposed between the electrodes and including a light emitting layer, The light emitting layer includes a compound synthesized by the synthesis method of the present invention or a compound derived from the compound.
When an indolocarbazole analogue having a heterocyclic group as a substituent synthesized by the synthesis method described in International Publication WO2011 / 088887 is used as a host material for a light emitting layer of an organic electroluminescent device, I found out that there was dissatisfaction. On the other hand, the organic electroluminescent device obtained when the compound synthesized by the synthesis method of the present invention is used as the organic layer of the organic electroluminescent device was synthesized by the synthesis method described in International Publication No. WO2011 / 088887. It has been found that the durability is remarkably improved as compared with the organic electroluminescent device obtained when the compound is used as the organic layer of the organic electroluminescent device. Without being bound by any theory, when a substituent is introduced into indolocarbazole, a compound synthesized by a known synthesis method may be, for example, two or two, regardless of whether it is desired to be halogenated (for example, bromination). Even if the reaction is carried out using three monohalogens, selectivity may not be obtained in the subsequent reaction and a by-product different from the desired one may be produced. On the other hand, in the synthesis method of the present invention, the position where a substituent can be introduced can be determined in advance, so that by-products can be suppressed, and this is because the desired compound is selectively obtained with high purity. Conceivable.

The structure of the organic electroluminescent element of the present invention is not particularly limited. In FIG. 1, an example of a structure of the organic electroluminescent element of this invention is shown. 1 has an organic layer on a substrate 2 between a pair of electrodes (anode 3 and cathode 9).
The element configuration, the substrate, the cathode, and the anode of the organic electroluminescence element are described in detail in, for example, Japanese Patent Application Laid-Open No. 2008-270736, and the matters described in the publication can be applied to the present invention.
Hereinafter, the preferable aspect of the organic electroluminescent element of this invention is demonstrated in detail in order of a board | substrate, an electrode, an organic layer, a protective layer, a sealing container, a drive method, light emission wavelength, and a use.

<Board>
The organic electroluminescent element of the present invention has a substrate.
The substrate used in the present invention is preferably a substrate that does not scatter or attenuate light emitted from the organic layer. 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.

<Electrode>
The organic electroluminescent element of the present invention is disposed on the substrate and has a pair of electrodes including an anode and a cathode.
In view of the properties of the light-emitting element, at least one of the pair of electrodes, the anode and the cathode, is preferably transparent or translucent.

(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.

(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.

<Organic layer>
The organic electroluminescent element of the present invention has an organic layer disposed between the electrodes.
There is no restriction | limiting in particular in the said organic layer, Although it can select suitably according to the use and objective of an organic electroluminescent element, It is preferable to form on the said transparent electrode or the said semi-transparent electrode. In this case, the organic layer is formed on the entire surface or one surface of the transparent electrode or the semitransparent electrode.
There is no restriction | limiting in particular about the shape of a organic layer, a magnitude | size, thickness, etc., According to the objective, it can select suitably.
Hereinafter, in the organic electroluminescent element of the present invention, the configuration of the organic layer, the method for forming the organic layer, preferred embodiments of the layers constituting the organic layer, and materials used for the layers will be described in order.

(Organic layer structure)
In the organic electroluminescent element of the present invention, the organic layer preferably includes a charge transport layer. The charge transport layer refers to a layer in which charge transfer occurs when a voltage is applied to the organic electroluminescent element. Specific examples include a hole injection layer, a hole transport layer, an electron block layer, a light emitting layer, a hole block layer, an electron transport layer, and an electron injection layer.
The organic electroluminescent element of the present invention has a light emitting layer containing the phosphorescent material and another organic layer, and the light emitting layer contains a compound synthesized by the synthesis method of the present invention or a compound derived from the compound. . At this time, the compound synthesized by the synthesis method of the present invention or a compound derived from the compound is preferably used as the host compound of the light emitting layer. Furthermore, in the organic electroluminescent element of the present invention, it is more preferable that the organic layer has a light emitting layer containing the phosphorescent material and another organic layer. However, in the organic electroluminescent element of the present invention, even when the organic layer has a light emitting layer and other organic layers, the layers do not necessarily have to be clearly distinguished.

Further, the charge transport material for an organic electroluminescence device of the present invention has an electron transport layer adjacent to the cathode between a pair of electrodes, and further, a hole blocking layer adjacent to the opposite side of the electron transport layer to the cathode In the organic electroluminescent element having any of the above, it is also preferable that the electron transporting layer or the hole blocking layer is contained.
A plurality of these organic layers may be provided, and when a plurality of layers are provided, they may be formed of the same material, or may be formed of different materials for each layer.

(Formation method of organic layer)
In the organic electroluminescence device of the present invention, each organic layer is formed by a dry film forming method such as a vapor deposition method or a sputtering method, a wet film forming method such as a transfer method, a printing method, a spin coating method, or a bar coating method (solution coating method). Any of these can be suitably formed.
In the organic electroluminescent element of the present invention, the light emitting layer is preferably formed by a vacuum deposition process. In the organic electroluminescent element of the present invention, the light emitting layer is preferably formed by a wet process.

(Light emitting layer)
The light emitting layer receives holes from an anode, a hole injection layer, or a hole transport layer, and receives electrons from a cathode, an electron injection layer, or an electron transport layer when an electric field is applied. It is a layer having a function of providing and emitting light. However, the light emitting layer in the present invention is not necessarily limited to light emission by such a mechanism. The light emitting layer in the organic electroluminescence device of the present invention preferably contains at least one phosphorescent material in addition to the compound synthesized by the synthesis method of the present invention or a compound derived from the compound.

  The light emitting layer in the organic electroluminescence device of the present invention may be composed of only a compound synthesized by the synthesis method of the present invention or a compound derived from the compound and a phosphorescent material. The synthesized compound or a compound derived from the compound may be used as a host material to form a mixed layer of the phosphorescent material. The phosphorescent material may be one kind or two or more kinds. 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. Furthermore, the light emitting layer may include a material that does not have charge transporting properties and does not emit light.

  Further, the light emitting layer may be a single layer or a multilayer of two or more layers, and each layer may contain the same light emitting material or host material, or each layer may contain a different material. When there are a plurality of light emitting layers, each of the light emitting layers may emit light with different emission colors.

  Although the thickness of the light emitting layer is not particularly limited, it is usually preferably 2 nm to 500 nm, more preferably 3 nm to 200 nm, and more preferably 5 nm to 100 nm from the viewpoint of external quantum efficiency. More preferably.

The organic electroluminescence device of the present invention is characterized in that the light emitting layer contains a compound synthesized by the synthesis method of the present invention or a compound derived from the compound, and the synthesis of the present invention as a host material of the light emitting layer It is a preferred embodiment to use a compound synthesized by the method or a compound derived from the compound. Here, in this specification, the host material is a compound mainly responsible for charge injection and transport in the light emitting layer, and is a compound that itself does not substantially emit light. Here, “substantially does not emit light” means that the amount of light emitted from the compound that does not substantially emit light is preferably 5% or less, more preferably 3% or less of the total amount of light emitted from the entire device. Preferably it says 1% or less.
Hereinafter, as the material of the light emitting layer, the compound synthesized by the synthesis method of the present invention or a compound derived from the compound, the phosphorescent material, the compound synthesized by the synthesis method of the present invention or derived from the compound thereof. Other host materials other than the compounds will be described in order. In addition, the compound represented by the compound synthesize | combined by the synthesis method of this invention or the compound induced | guided | derived from the compound may be used other than the said light emitting layer in the organic electroluminescent element of this invention.

In the present invention, the compound represented by the compound synthesized by the synthesis method of the present invention or a compound derived from the compound is not limited in its use, and is contained in any layer in the organic layer. Also good. As the introduction layer of the compound synthesized by the synthesis method of the present invention or a compound derived from the compound, the light emitting layer, a layer between the light emitting layer and the cathode (in particular, adjacent to the light emitting layer). Of the light emitting layer, the electron transport layer, the electron injection layer, the exciton block layer, the hole block layer, and the electron block layer. More preferably contained in any one or more, more preferably contained in any of the light emitting layer, the electron transport layer, the hole blocking layer, the hole transport layer, the light emitting layer, the hole transport layer, Or it is especially preferable to contain in an electron carrying layer. In addition, the compound synthesized by the synthesis method of the present invention or a compound derived from the compound may be used in the plurality of layers described above. For example, you may use for both a light emitting layer and an electron carrying layer, or a light emitting layer and a positive hole transport layer.
When the compound represented by the light emitting layer and the electron transport layer is contained in the light emitting layer, the compound represented by the light emitting layer and the electron transport layer is contained in an amount of 0.1 to 99% by mass with respect to the total mass of the light emitting layer. It is preferable to include 1 to 97 mass%, and it is more preferable to include 10 to 96 mass%. When the compound represented by the light emitting layer and the electron transport layer is further contained in a layer other than the light emitting layer, it is preferably contained in an amount of 50 to 100% by mass with respect to the total mass of the layer other than the light emitting layer. More preferably, it is contained by mass%.

(II) Phosphorescent material In the present invention, it is preferable that the light emitting layer has at least one phosphorescent material. In the present invention, in addition to the phosphorescent light emitting material, a fluorescent light emitting material or a phosphorescent light emitting material different from the phosphorescent light emitting material contained in the light emitting layer can be used as the light emitting material.
Details of these fluorescent light-emitting materials and phosphorescent light-emitting materials are described in, for example, paragraph numbers [0100] to [0164] of JP-A-2008-270736 and paragraph numbers [0088] to [0090] of JP-A-2007-266458. The matters described in these publications can be applied to the present invention.

Examples of phosphorescent light-emitting materials that can be used in the present invention include US Pat. / 19373A2, JP 2001-247859, JP 2002-302671, JP 2002-117978, JP 2003-133074, JP 2002-235076, JP 2003-123982, JP 2002-170684, EP 121157, JP -226495, JP 2002-234894, JP 2001-247859, JP 2001-298470, JP 2002-17367. , JP 2002-203678, JP 2002-203679, JP 2004-357799, JP 2006-256999, JP 2007-19462, JP 2007-84635, JP 2007-96259, and the like. Examples of such a light emitting material include Ir complex, Pt complex, Cu complex, Re complex, W complex, Rh complex, Ru complex, Pd complex, Os complex, Eu complex, Tb complex, Gd. Examples include phosphorescent metal complex compounds such as complexes, Dy complexes, and Ce complexes. 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 Re complexes are preferred. Furthermore, from the viewpoints of luminous efficiency, driving durability, chromaticity, etc., Ir complexes and Pt complexes are particularly preferable, and Ir complexes are most preferable.
These phosphorescent metal complex compounds are preferably contained in the light emitting layer together with the compound represented by the general formula (1).

  As the phosphorescent material contained in the light emitting layer, it is preferable to use an iridium complex represented by the following general formula (T-1). Hereinafter, the iridium complex represented by the general formula (T-1) will be described.

  The compound represented by formula (T-1) will be described.

(In the general formula (T-1), R _T3 ′, R _T3 , R _T4 , R _T5 and R _T6 are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, —CN, perfluoro. An alkyl group, a trifluorovinyl group, —CO ₂ R _T , —C (O) R _T , —N (R _T ) ₂ , —NO ₂ , —OR _T , a halogen atom, an aryl group or a heteroaryl group; Further, it may have a substituent Z ^T.
Q is a 5-membered or 6-membered aromatic heterocyclic ring or condensed aromatic heterocyclic ring containing one or more nitrogen atoms.
R _T3 , R _T4 , R _T5 and R _T6 may be any two adjacent to each other to form a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring is cycloalkyl, aryl or hetero It is aryl, and the condensed 4- to 7-membered ring may further have a substituent Z ^T.
R _T3 ′ and R _T6 are —C (R _T ) ₂ —C (R _T ) ₂ —, —CR _T = CR _T —, —C (R _T ) ₂ —, —O—, —NR _T —, A ring may be formed by linking with a linking group selected from —O—C (R _T ) ₂ —, —NR _T —C (R _T ) ₂ —, and —N═CR _T —.
R _T each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group, or a heteroaryl group, and may further have a substituent Z ^T.
Z ^T is independently a halogen atom, —R ′, —OR ′, —N (R ′) ₂ , —SR ′, —C (O) R ′, —C (O) OR ′, —C (O ) N (R ′) ₂ , —CN, —NO ₂ , —SO ₂ , —SOR ′, —SO ₂ R ′, or —SO ₃ R ′, each independently representing a hydrogen atom or an alkyl group. Represents a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
(X—Y) represents an auxiliary ligand. m _T represents an integer of 1 to 3, and n _T represents an integer of 0 to 2. m _T + n _T is 3. )

  General formula (T-1) is a complex having iridium (Ir) as a metal, and in combination with the charge transporting material of the present invention, facilitates the transport of charges in the light emitting layer and increases the luminous efficiency. Can do.

The alkyl group may have a substituent, may be saturated or unsaturated and, as a group which may be substituted, may be exemplified by the substituents Z ^T described above. The alkyl group represented by R ₃ ′, R ₃ , R ₄ , R ₅ and R ₆ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Group, for example, methyl group, ethyl group, i-propyl group, t-butyl group and the like.
The cycloalkyl group may have a substituent, may be saturated or unsaturated and, as a group which may be substituted, may be exemplified by the substituents Z ^T described above. The cycloalkyl group represented by R ₃ ′, R ₃ , R ₄ , R ₅ , R ₆ is preferably a cycloalkyl group having 4 to 7 ring members, more preferably a cycloalkyl group having 5 to 6 carbon atoms in total. Examples of the alkyl group include a cyclopentyl group and a cyclohexyl group.
The alkenyl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 and R _T6 preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms. And vinyl, allyl, 1-propenyl, 1-isopropenyl, 1-butenyl, 2-butenyl, 3-pentenyl and the like.
The alkynyl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 , R _T6 is preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms. Yes, for example, ethynyl, propargyl, 1-propynyl, 3-pentynyl and the like.

Examples of the perfluoroalkyl group represented by R ₃ ′, R ₃ , R ₄ , R ₅ , and R ₆ include those in which all the hydrogen atoms of the aforementioned alkyl group are replaced with fluorine atoms.
The halogen atom represented by R ₃ ′, R ₃ , R ₄ , R ₅ , R ₆ is preferably a fluorine atom.
The aryl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 , R _T6 is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group. Groups and the like.

The heteroaryl group represented by R _T3 ′, R _T3 , R _T4 , R _T5 , R _T6 is preferably a heteroaryl group having 5 to 8 carbon atoms, more preferably a 5- or 6-membered substitution. Or an unsubstituted heteroaryl group, for example, pyridyl group, pyrazinyl group, pyridazinyl group, pyrimidinyl group, triazinyl group, quinolinyl group, isoquinolinyl group, quinazolinyl group, cinnolinyl group, phthalazinyl group, quinoxalinyl group, pyrrolyl group, indolyl group , Furyl group, benzofuryl group, thienyl group, benzothienyl group, pyrazolyl group, imidazolyl group, benzimidazolyl group, triazolyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, isothiazolyl group, benzisothiazolyl group , Thiadiazolyl group, isoxazolyl Group, a benzisoxazolyl group, a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, an imidazolidinyl group, a thiazolinyl group, a sulfolanyl group, a carbazolyl group, a dibenzofuryl group, dibenzothienyl group, such as 7 pyrido-indolyl group. Preferred examples include pyridyl group, pyrimidinyl group, imidazolyl group, and thienyl group, and more preferred are pyridyl group and pyrimidinyl group.

R _T3 ′, R _T3 , R _T4 , R _T5 and R _T6 are preferably a hydrogen atom, an alkyl group, a cyano group, a perfluoroalkyl group, a dialkylamino group, a fluorine atom, an aryl group, a heteroaryl group, or a halogen atom. More preferably a hydrogen atom, an alkyl group, a cyano group, a trifluoromethyl group, a fluorine atom, an aryl group, or a halogen atom, still more preferably a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, Particularly preferred are a hydrogen atom, a methyl group, an isobutyl group, a phenyl group, or a fluorine atom. As the substituent Z ^T , an alkyl group, an alkoxy group, a fluorine atom, a cyano group, and a dialkylamino group are preferable, and a hydrogen atom is more preferable.

R _T3 , R _T4 , R _T5 and R _T6 may be any two adjacent to each other to form a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring is cycloalkyl, aryl or hetero It is aryl, and the condensed 4- to 7-membered ring may further have a substituent Z ^T. The definition and preferred range of cycloalkyl, aryl and heteroaryl formed are the same as the cycloalkyl group, aryl group and heteroaryl group defined by R _T3 ′, R _T3 , R _T4 , R _T5 and R _T6 .

  Examples of the aromatic heterocyclic ring represented by ring Q include a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, an oxadiazole ring, a thiazole ring, and a thiadiazole ring. A pyridine ring and a pyrazine ring are preferable, and a pyridine ring is more preferable.

  Examples of the condensed aromatic heterocyclic ring represented by ring Q include a quinoline ring, an isoquinoline ring, and a quinoxaline ring. Preferred are a quinoline ring and an isoquinoline ring, and more preferred is a quinoline ring.

m _T is preferably 1 to 3, and more preferably 2 or 3. That is, n _T is preferably 0 or 1. It is preferable that the kind of ligand in a complex is comprised from 1 or 2 types, More preferably, it is 1 type. When introducing a reactive group into the complex molecule, it is also preferred that the ligand consists of two types from the viewpoint of ease of synthesis.

  The metal complex represented by the general formula (T-1) is composed of a main ligand or a tautomer thereof and a combination of a ligand different from the main ligand or a tautomer thereof, All of the ligands of the metal complex may be composed of only a partial structure represented by the main ligand or a tautomer thereof.

Further, as a so-called ligand used in forming a conventionally known metal complex, the trader may have a known ligand (also referred to as a coordination compound) as a secondary ligand that does not contribute to light emission as necessary. Good.

  As the sub-ligands used in the conventionally known metal complexes, there are various known ligands. For example, “Photochemistry and Photophysics of Coordination Compounds” Springer-Verlag H. Published by Yersin, 1987, “Organometallic Chemistry-Fundamentals and Applications-” Liu Huabosha, Akio Yamamoto, published by 1982, etc. (for example, halogen ligands (preferably chlorine ligands), Examples thereof include nitrogen heteroaryl ligands (for example, bipyridyl, phenanthroline, etc.), diketone ligands (for example, acetylacetone, etc.) The secondary ligand is preferably a diketone or a picolinic acid derivative.

  Although the example of a subligand is specifically mentioned below, this invention is not limited to these.

In the example of the subligand, * represents a coordination position to iridium in the general formula (T-1). Rx, Ry and Rz each independently represents a hydrogen atom or a substituent. Examples of the substituent include a substituent selected from the substituent group A. Preferably, Rx and Rz are each independently an alkyl group, a perfluoroalkyl group, a halogen atom or an aryl group, more preferably an alkyl group having 1 to 4 carbon atoms, a perfluoroalkyl group having 1 to 4 carbon atoms, A fluorine atom and an optionally substituted phenyl group are most preferred, and a methyl group, an ethyl group, a trifluoromethyl group, a fluorine atom and a phenyl group are most preferred. Ry is preferably a hydrogen atom, an alkyl group, a perfluoroalkyl group, a halogen atom, or an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an optionally substituted phenyl group. And most preferably a hydrogen atom or a methyl group. Since these sub-ligands are not considered to be sites where charge is transported in the device or electrons are concentrated by excitation, Rx, Ry, and Rz may be any chemically stable substituent, and the effects of the present invention Will not be affected.
Since the complex synthesizing method is generally known and is easy, the secondary ligand is preferably (I-1), (I-4), or (I-5), and most preferably (I-1 ).

  In the present invention, the secondary ligand is most preferably acetylacetonate (acac) from the viewpoint of obtaining stability of the complex and high luminous efficiency. * Represents a coordination position to iridium in the general formula (T-1).

  Complexes having these subligands can be synthesized in the same manner as in known synthesis examples by using corresponding ligand precursors. For example, it can synthesize | combine by the method shown below using commercially available difluoroacetylacetone similarly to the method of the 46th page of international publication 2009-073245.

  In addition, a monoanionic bidentate ligand having a phenylpyridine skeleton can be further used as the ligand, and specific examples include a monoanionic bidentate ligand represented by the general formula (I-15). It is done.

R _T7 ′ and R _{T7 to} R _T10 in General Formula (I-15) have the same _{meanings as} R _T3 ′ and R _{T3 to} R _T6 in General Formula (T-1), and preferred ones are also the same. R _T8 ′ to R _T10 ′ are synonymous with R _T3 ′.
R _T8 ′ is preferably a hydrogen atom, an alkyl group, an aryl group or a fluorine atom, more preferably a hydrogen atom.
R _T9 ′ and R _T10 ′ each represent a hydrogen atom or are preferably bonded to each other to form a condensed 4- to 7-membered cyclic group, and the condensed 4- to 7-membered cyclic group includes a cycloalkyl group, a cyclo A heteroalkyl group, an aryl group, or a heteroaryl group is more preferable, and an aryl group is still more preferable.
R _T9 '~R _T10' may further have a substituent Z ^T, the alkyl group as the substituent Z ^T, an alkoxy group, a fluorine atom, a cyano group, an alkylamino group, a diarylamino group is preferably an alkyl Groups are more preferred.

  The compound represented by the general formula (T-1) is preferably a compound represented by the following general formula (T-2).

(In the general formula (T-2), R _T3 ′ to R _T6 ′ and R _{T3 to} R _T6 are each independently a hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, —CN, perfluoroalkyl group. , A trifluorovinyl group, —CO ₂ R _T , —C (O) R _T , —N (R _T ) ₂ , —NO ₂ , —OR _T , a halogen atom, an aryl group or a heteroaryl group, and further substituted It may have the group Z ^T.
R _T3 , R _T4 , R _T5 and R _T6 may be bonded to each other to form a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring further has a substituent Z ^T. You may do it.
R _T3 ′ and R _T6 are —C (R _T ) ₂ —C (R _T ) ₂ —, —CR _T = CR _T —, —C (R _T ) ₂ —, —O—, —NR _T —, A ring may be formed by linking with a linking group selected from —O—C (R _T ) ₂ —, —NR _T —C (R _T ) ₂ —, and —N═CR _T —.
R _T each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group, or a heteroaryl group, and may further have a substituent Z ^T.
Z ^T is independently a halogen atom, —R ′, —OR ′, —N (R ′) ₂ , —SR ′, —C (O) R ′, —C (O) OR ′, —C (O ) N (R ′) ₂ , —CN, —NO ₂ , —SO ₂ , —SOR ′, —SO ₂ R ′, or —SO ₃ R ′, each independently representing a hydrogen atom or an alkyl group. Represents a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
(X—Y) represents an auxiliary ligand. m _T represents an integer of 1 to 3, and n _T represents an integer of 0 to 2. m _T + n _T is 3. )
In the general formula (T-2), R _T3 ′, R _{T3 to} R _T6 , (XY), m _T, and n _T are preferably ranges of R _T3 ′, R _{T3 to} R in the general formula (T-1). _T6, is the same as the preferred range of (X-Y), m _T and n _T.
R _T4 ′ is preferably a hydrogen atom, an alkyl group, an aryl group or a fluorine atom, more preferably a hydrogen atom.
R _T5 ′ and R _T6 ′ each represent a hydrogen atom or preferably bonded to each other to form a condensed 4- to 7-membered cyclic group, and the condensed 4- to 7-membered cyclic group includes a cycloalkyl group, a cyclo A heteroalkyl group, an aryl group, or a heteroaryl group is more preferable, and an aryl group is still more preferable.
R _T4 '~R _T6' may further have a substituent Z ^T, the alkyl group as the substituent Z ^T, an alkoxy group, a fluorine atom, a cyano group, an alkylamino group, a diarylamino group is preferably an alkyl Groups are more preferred.

  One of the preferable forms of the compound represented by the general formula (T-2) is a compound represented by the following general formula (T-3).

In the general formula (T-3), R _T3 ′, R _T4 ′, R _T5 ′, R _T6 ′, R _T3 , R _T4 , R _T5 and R _T6 are a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group. , An alkynyl group, —CN, a perfluoroalkyl group, —N (R _T ) ₂ , a halogen atom, an aryl group or a heteroaryl group, and may further have a substituent Z ^T. The R _T the same meaning as R _T in the above-described general formula (T-1).
R _T3 ′, R _T4 ′, R _T5 ′, R _T6 ′, R _T3 , R _T4 , R _T5, and R _T6 are not bonded to each other to form a condensed ring.
Z ^T each independently represents a halogen atom, —R ′, —OR ′, —N (R ′) ₂ , —SR ′, or —CN, and each R ′ independently represents a hydrogen atom, an alkyl group, or a perhaloalkyl. Represents a group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
(X-Y), m _T and n _T is in the general formula (T-2) (X- Y), has the same meaning as m _T and n _T, preferable ones are also same.

  The compound represented by the general formula (T-3) is preferably a compound represented by the following general formula (T-3-1).

R _T3 in the general formula _{(T-3-1) '~R T6} ', R T3 ~R T6, and m _T is, R _T3 in the general formula _{(T3) '~R T6',} R T3 ~R T6 , And m _T , and preferable examples are also the same.
R _{T7 to} R _T10 are synonymous with R _{T3 to} R _T6 . R _T7 ′ to R _T10 ′ are synonymous with R _T3 ′ to R _T6 ′.

  Another preferable form of the compound represented by the general formula (T-2) is a compound represented by the following general formula (T-4).

R _T3 ′ to R _T6 ′, R _{T3 to} R _T6 , (XY), m _T and n _T in the general formula (T-4) are R _T3 ′ to R _T6 ′ in the general formula (T-2). , R _{T3 to} R _T6 , (XY), m _T, and n _T , and preferable examples are also the same. R _T7 ′ is synonymous with R _T3 ′, and preferred ones are also the same.

  Another preferred embodiment of the compound represented by the general formula (T-2) is a compound represented by the following general formula (T-5).

R _T3 ′ to R _T7 ′, R _{T3 to} R _T6 , (XY), m _T and n _T in the general formula (T-5) are R _T3 ′ to R _T6 ′ in the general formula (T-2). , R _{T3 to} R _T6 , (XY), m _T, and n _T , and preferable examples are also the same.

  Although the specific example of a compound represented by general formula (T-1) is enumerated below, it is not limited to the following.

The compound illustrated as a compound represented by the said general formula (T-1) is compoundable by the method of Unexamined-Japanese-Patent No. 2009-99783, the various method as described in US Patent 7279232, etc. After synthesis, it is preferable to purify by sublimation purification after purification by column chromatography, recrystallization or the like. By sublimation purification, not only can organic impurities be separated, but inorganic salts and residual solvents can be effectively removed. Ir complexes have structural isomers such as facial and meridional isomers depending on the coordination direction of the ligand. Any structural isomer may be used as a luminescent material, and a mixture of several structural isomers. May be used.

  The phosphorescent light emitting material is preferably contained in the light emitting layer, but its use is not limited and may be further contained in any layer in the organic layer.

  The phosphorescent light-emitting material in the light-emitting layer is preferably contained in the light-emitting layer in an amount of 0.1% by mass to 50% by mass with respect to the total compound mass that generally forms the light-emitting layer. From the viewpoint of external quantum efficiency, the content is more preferably 1% by mass to 50% by mass, and particularly preferably 2% by mass to 40% by mass.

(III) Other host materials Examples of other host materials that can be used for the light emitting layer other than the compound represented by the general formula (1) include compounds having the following structure as a partial structure. it can.
Aromatic hydrocarbon, pyrrole, indole, carbazole, azaindole, azacarbazole, triazole, oxazole, oxadiazole, pyrazole, imidazole, thiophene, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styryl Conductivity of anthracene, hydrazone, stilbene, silazane, aromatic tertiary amine compound, styrylamine compound, porphyrin compound, polysilane compound, poly (N-vinylcarbazole), aniline copolymer, thiophene oligomer, polythiophene, etc. Polymer oligomer, organic silane, carbon film, pyridine, pyrimidine, triazine, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyra Dioxide, carbodiimide, fluorenylidenemethane, distyrylpyrazine, fluorine-substituted aromatic compounds, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, phthalocyanine, metal complexes of 8-quinolinol derivatives, metal phthalocyanine, benzoxazole, Examples thereof include various metal complexes represented by metal complexes having benzothiazol as a ligand and derivatives thereof (which may have a substituent or a condensed ring).

(Other layers)
The organic electroluminescent element of the present invention may have other layers other than the light emitting layer.
As an organic layer other than the light emitting layer that the organic layer may have, a hole injection layer, a hole transport layer, a block layer (a hole block layer, an electron block layer, an exciton block layer, etc.), Examples thereof include an electron transport layer. Examples of the specific layer configuration include the following, but the present invention is not limited to these configurations.
Anode / hole transport layer / light emitting layer / electron transport layer / cathode,
Anode / hole transport layer / light emitting layer / block layer / electron transport layer / cathode,
Anode / hole transport layer / light emitting layer / block layer / electron transport layer / electron injection layer / cathode,
Anode / hole injection layer / hole transport layer / light emitting layer / block layer / electron transport layer / cathode,
Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode,
Anode / hole injection layer / hole transport layer / light emitting layer / block layer / electron transport layer / electron injection layer / cathode,
Anode / hole injection layer / hole transport layer / block layer / light emitting layer / block layer / electron transport layer / electron injection layer / cathode.
The organic electroluminescent element of the present invention preferably comprises (A) at least one organic layer preferably disposed between the anode and the light emitting layer. Examples of the organic layer (A) preferably disposed between the anode and the light emitting layer include a hole injection layer, a hole transport layer, and an electron block layer from the anode side.
The organic electroluminescent element of the present invention preferably includes (B) at least one organic layer preferably disposed between the cathode and the light emitting layer. Examples of the organic layer (B) preferably disposed between the cathode and the light emitting layer include an electron injection layer, an electron transport layer, and a hole blocking layer from the cathode side.
Specifically, an example of a preferred embodiment of the organic electroluminescent element of the present invention is the embodiment described in FIG. 1, and as the organic layer, a hole injection layer 4, a hole transport layer 5, from the anode side 3, In this embodiment, the light emitting layer 6, the hole blocking layer 7, and the electron transport layer 8 are laminated in this order.
Hereinafter, other layers other than the light emitting layer which may be included in the organic electroluminescent element of the present invention will be described.

(A) Organic layer preferably disposed between the anode and the light emitting layer First, (A) the organic layer preferably disposed between the anode and the light emitting layer will be described.

(A-1) 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. The hole injecting material and hole transporting material used for these layers may be a low molecular compound or a high molecular compound.
Regarding the hole injection layer and the hole transport layer, the matters described in paragraph numbers [0165] to [0167] of JP-A-2008-270736 can be applied to the present invention.

The hole injection layer preferably contains an electron accepting dopant. By containing an electron-accepting dopant in the hole injection layer, hole injection properties are improved, driving voltage is lowered, and efficiency is improved. The electron-accepting dopant may be any organic material or inorganic material as long as it can extract electrons from the doped material and generate radical cations. For example, tetracyanoquinodimethane ( TCNQ compounds such as TCNQ) and tetrafluorotetracyanoquinodimethane (F ₄ -TCNQ), hexaazatriphenylene compounds such as hexacyanohexaazatriphenylene (HAT-CN), and molybdenum oxide. Further, the same effect can be obtained by sandwiching only the electron accepting dopant as a thin film between the anode and the hole transport layer. In this case, this layer is called a hole injection layer. Furthermore, the same effect can be obtained by sandwiching an electron-accepting dopant as a thin film in the hole transport layer. In this case, the hole injection layer sandwiched between the hole transport layers may be a single layer or multiple layers.

  The electron-accepting dopant in the hole injection layer is preferably contained in an amount of 0.01% by mass to 50% by mass, and 0.1% by mass to 40% by mass with respect to the total compound mass forming the hole injection layer. % Content is more preferable, and 0.2% by mass to 30% by mass is more preferable. When used as a thin film, the thickness of the hole injection layer is preferably 1 nm to 50 nm, more preferably 3 nm to 30 nm, and even more preferably 5 nm to 20 nm.

(A-2) Electron Blocking Layer The electron blocking layer is a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side. In the present invention, an electron blocking layer can be provided as an organic layer adjacent to the light emitting layer on the anode side.
As an example of the organic compound constituting the electron blocking layer, for example, those mentioned as the hole transport material described above can be applied.
The thickness of the electron blocking layer is preferably 1 nm to 500 nm, more preferably 3 nm to 200 nm, and even more preferably 5 nm to 100 nm.
The electron 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.
The T ₁ energy in the film state of the organic compound composing the electron blocking layer must be higher than the T ₁ energy of the light emitting material in order to prevent energy transfer of excitons generated in the light emitting layer and not to reduce the light emission efficiency. Is preferred.

(A-3) Material [compound represented by general formula (M-1)] particularly preferably used for the organic layer preferably disposed between the anode and the light emitting layer
The organic electroluminescent device of the present invention is represented by at least one of the following general formula (M-1) as a material particularly preferably used for the organic layer preferably disposed between the (A) anode and the light emitting layer. Can be mentioned.

The compound represented by the general formula (M-1) is more preferably contained in an organic layer adjacent to the light emitting layer between the light emitting layer and the anode, but its use is not limited, and the organic layer It may be further contained in any of the layers. As the introduction layer of the compound represented by the general formula (M-1), any of a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, a charge blocking layer, or a plurality of layers can be used. Can be contained.
The organic layer adjacent to the light emitting layer between the light emitting layer and the anode, containing the compound represented by the general formula (M-1), is more preferably an electron block layer or a hole transport layer.

In the general formula (M-1), Ar ¹ and Ar ² are each independently one or more selected from alkyl, aryl, heteroaryl, arylamino, alkylamino, morpholino, thiomorpholino, N, O, and S Represents a 5- or 6-membered heterocycloalkyl or cycloalkyl containing a heteroatom, and may further have a substituent Z ^T. Ar ¹ and Ar ² may be bonded to each other by a single bond, alkylene, or alkenylene (with or without a condensed ring) to form a condensed 5- to 9-membered ring.
Ar ³ represents P-valent alkyl, aryl, heteroaryl, or arylamino, and may further have a substituent Z.
Z ^T is independently a halogen atom, —R ″, —OR ″, —N (R ″) ₂ , —SR ″, —C (O) R ″, —C (O) OR ″, —C (O ) N (R ″) ₂ , —CN, —NO ₂ , —SO ₂ , —SOR ″, —SO ₂ R ″, or —SO ₃ R ″, each R ″ independently represents a hydrogen atom or an alkyl group Represents a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
p is an integer of 1 to 4, and when p is 2 or more, Ar ¹ and Ar ² may be the same or different.

  Another preferable embodiment of the compound represented by the general formula (M-1) is a case represented by the following general formula (M-2).

In the general formula (M-2), R ^M1 represents an alkyl group, an aryl group, or a heteroaryl group.
R ^{M2 to} R ^M23 each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, an amino group, a silyl group, a cyano group, a nitro group, or a fluorine atom.

In the general formula (M-2), R ^M1 represents an alkyl group (preferably having 1 to 8 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms), or a heteroaryl group (preferably having 4 to 12 carbon atoms). Which may have the aforementioned substituent Z ^T. R ^M1 is preferably an aryl group or a heteroaryl group, more preferably an aryl group. Preferred substituents when the aryl group of R ^M1 has a substituent include an alkyl group, a halogen atom, a cyano group, an aryl group, and an alkoxy group, and an alkyl group, a halogen atom, a cyano group, and an aryl group are more preferable. An alkyl group, a cyano group, or an aryl group is more preferable. The aryl group of R ^M1 is preferably a phenyl group that may have a substituent Z ^T , and more preferably a phenyl group that may have an alkyl group or a cyano group.

R ^{M2 to} R ^M23 are each independently a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms), a heteroaryl group (preferably having 4 to 12 carbon atoms), Alkoxy group (preferably having 1 to 8 carbon atoms), aryloxy group (preferably having 6 to 30 carbon atoms), amino group (preferably having 0 to 24 carbon atoms), silyl group (preferably having 0 to 18 carbon atoms), cyano Represents a group, a nitro group, or a fluorine atom, and these may have the aforementioned substituent Z ^T.

R ^M2 , R ^M7 , R ^M8 , R ^M15 , R ^M16 and R ^M23 are preferably a hydrogen atom or an alkyl group or an aryl group which may have a substituent Z ^T , more preferably a hydrogen atom. is there.
R ^M4 , R ^M5 , R ^M11 , R ^M12 , R ^M19 and R ^M20 are preferably a hydrogen atom, an alkyl or aryl group which may have a substituent Z ^T , or a fluorine atom, more preferably It is a hydrogen atom.
R ^M3 , R ^M6 , R ^M9 , R ^M14 , R ^M17 and R ^M22 are preferably a hydrogen atom, an alkyl or aryl group optionally having a substituent Z ^T , a fluorine atom, or a cyano group, A hydrogen atom or an alkyl group which may have a substituent Z ^T is more preferable, and a hydrogen atom is still more preferable.
R ^M10 , R ^M13 , R ^M18 and R ^M21 are preferably a hydrogen atom, an alkyl group optionally having a substituent Z ^T , an aryl group, a heteroaryl group or an amino group, a nitro group, a fluorine atom, or cyano. More preferably a hydrogen atom, an alkyl group or aryl group optionally having a substituent Z ^T , a nitro group, a fluorine atom, or a cyano group, still more preferably a hydrogen atom or a substituent Z ^T. It is the alkyl group which may have. When the alkyl group has a substituent, the substituent is preferably a fluorine atom, and the alkyl group which may have a substituent Z ^T preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. It is.

  Another preferable embodiment of the compound represented by the general formula (M-1) is a case represented by the following general formula (M-3).

In the general formula (M-3), R ^{S1 to} R ^S5 are each independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, —CN, a perfluoroalkyl group, a trifluorovinyl group, —CO ₂ R, — C (O) R, —NR ₂ , —NO ₂ , —OR, a halogen atom, an aryl group or a heteroaryl group may be represented, and may further have a substituent Z ^T. Each R independently represents a hydrogen atom, an alkyl group, a perhaloalkyl group, an alkenyl group, an alkynyl group, a heteroalkyl group, an aryl group or a heteroaryl group. When a plurality of R ^{S1 to} R ^S5 are present, they may be bonded to each other to form a ring, and may further have a substituent Z ^T.
a represents an integer of 0 to 4, and when a plurality of R ^S1 are present, they may be the same or different and may be bonded to each other to form a ring. b to e each independently represent an integer of 0 to 5, and when there are a plurality of R ^{S2 to} R ^S5 , they may be the same or different, and any two may be bonded to form a ring. Good.
q is an integer of 1 to 5, and when q is 2 or more, a plurality of R ^S1 may be the same or different, and may be bonded to each other to form a ring.

The alkyl group may have a substituent, may be saturated or unsaturated and, as a group which may be substituted, may be exemplified by the substituents Z ^T described above. The alkyl group represented by R ^{S1 to} R ^S5 is preferably an alkyl group having 1 to 8 carbon atoms in total, more preferably an alkyl group having 1 to 6 carbon atoms in total, such as a methyl group or an ethyl group. I-propyl group, cyclohexyl group, t-butyl group and the like.
The cycloalkyl group may have a substituent, may be saturated or unsaturated and, as a group which may be substituted, may be exemplified by the substituents Z ^T described above. The cycloalkyl group represented by R ^{S1 to} R ^S5 is preferably a cycloalkyl group having 4 to 7 ring members, more preferably a cycloalkyl group having 5 to 6 carbon atoms in total, such as a cyclopentyl group or cyclohexyl group. Groups and the like.
The alkenyl group represented by R ^{S1 to} R ^S5 preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms. For example, vinyl, allyl, 1-propenyl, 1-isopropenyl, 1-butenyl, 2-butenyl, 3-pentenyl and the like can be mentioned.
The alkynyl group represented by R ^{S1 to} R ^S5 preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms. For example, ethynyl, propargyl, 1-propynyl , 3-pentynyl and the like.

Examples of the perfluoroalkyl group represented by R ^{S1 to} R ^S5 include those in which all the hydrogen atoms of the aforementioned alkyl group are replaced with fluorine atoms.

The aryl group represented by R ^{S1 to} R ^S5 is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a tolyl group, a biphenyl group, and a terphenyl group.

The heteroaryl group represented by R ^{S1 to} R ^S5 is preferably a heteroaryl group having 5 to 8 carbon atoms, more preferably a 5- or 6-membered substituted or unsubstituted heteroaryl group, For example, pyridyl group, pyrazinyl group, pyridazinyl group, pyrimidinyl group, triazinyl group, quinolinyl group, isoquinolinyl group, quinazolinyl group, cinnolinyl group, phthalazinyl group, quinoxalinyl group, pyrrolyl group, indolyl group, furyl group, benzofuryl group, thienyl group, Benzothienyl, pyrazolyl, imidazolyl, benzimidazolyl, triazolyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, isothiazolyl, benzisothiazolyl, thiadiazolyl, isoxazolyl, benzisoxa Examples include zolyl group, pyrrolidinyl group, piperidinyl group, piperazinyl group, imidazolidinyl group, thiazolinyl group, sulfolanyl group, carbazolyl group, dibenzofuryl group, dibenzothienyl group, pyridoindolyl group and the like. Preferred examples include pyridyl group, pyrimidinyl group, imidazolyl group, and thienyl group, and more preferred are pyridyl group and pyrimidinyl group.

R ^{S1 to} R ^S5 are preferably a hydrogen atom, an alkyl group, a cyano group, a trifluoromethyl group, a perfluoroalkyl group, a dialkylamino group, a fluoro group, an aryl group, or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. Group, cyano group, trifluoromethyl group, fluoro group and aryl group, more preferably a hydrogen atom, an alkyl group and an aryl group. As the substituent Z ^T , an alkyl group, an alkoxy group, a fluoro group, a cyano group, and a dialkylamino group are preferable, and a hydrogen atom and an alkyl group are more preferable.

Any two of R ^{S1 to} R ^S5 may be bonded to each other to form a condensed 4- to 7-membered ring, and the condensed 4- to 7-membered ring is cycloalkyl, aryl, or heteroaryl; The 7-membered ring may further have a substituent Z ^T. The definition and preferred range of cycloalkyl, aryl and heteroaryl formed are the same as the cycloalkyl group, aryl group and heteroaryl group defined by R ^{S1 to} R ^S5 .

When the compound represented by the general formula (M-1) is used in the hole transport layer, the compound represented by the general formula (M-1) is preferably contained in an amount of 50 to 100% by mass, It is preferable that 80-100 mass% is contained, and it is especially preferable that 95-100 mass% is contained.
Moreover, when using the compound represented by the said general formula (M-1) for a some organic layer, it is preferable to contain in said range in each layer.

  The compound represented by the general formula (M-1) may contain only one kind in any of the organic layers, and the compound represented by the plurality of general formulas (M-1) may be arbitrarily selected. You may contain combining in a ratio.

  The thickness of the hole transport layer containing the compound represented by the general formula (M-1) is preferably 1 nm to 500 nm, more preferably 3 nm to 200 nm, and 5 nm to 100 nm. Is more preferable. The hole transport layer is preferably provided in contact with the light emitting layer.

The lowest excited triplet (T ₁ ) energy in the film state of the compound represented by the general formula (M-1) is 1.77 eV (40 kcal / mol) or more and 3.51 eV (81 kcal / mol) or less. Is preferably 2.39 eV (55 kcal / mol) or more and 3.25 eV (75 kcal / mol) or less. In the organic electroluminescent element of the present invention, it is preferable from the viewpoint of luminous efficiency that the T ₁ energy of the compound represented by the general formula (M-1) is higher than the T ₁ energy of the phosphorescent material. . In particular, when the emission color from the organic electroluminescence device is green (emission peak wavelength is 490 to 580 nm), from the viewpoint of light emission efficiency, the T ₁ energy is 2.39 eV (55 kcal / mol) or more and 2.82 eV (65 kcal / mol). mol) or less.

  The hydrogen atoms constituting the general formula (M-1) include hydrogen isotopes (deuterium atoms and the like). In this case, all hydrogen atoms in the compound may be replaced with hydrogen isotopes, or a mixture in which a part is a compound containing hydrogen isotopes may be used.

  The compound represented by the general formula (M-1) can be synthesized by combining various known synthesis methods. Most commonly, carbazole compounds are synthesized by dehydroaromatization after the Athercorp rearrangement reaction of a condensate of an aryl hydrazine and a cyclohexane derivative (LF Tieze, by Th. Eicher, translated by Takano, Ogasawara, Precision organic synthesis, page 339 (published by Nankodo). Regarding the coupling reaction of the obtained carbazole compound and halogenated aryl compound using a palladium catalyst, Tetrahedron Letters 39: 617 (1998), 39: 2367 (1998) and 40: 6393 (1999) and the like. The reaction temperature and reaction time are not particularly limited, and the conditions described in the above literature can be applied.

  The compound represented by the general formula (M-1) preferably forms a thin layer by a vacuum deposition process, but a wet process such as solution coating can also be suitably used. The molecular weight of the compound is preferably 2000 or less, more preferably 1200 or less, and particularly preferably 800 or less from the viewpoints of deposition suitability and solubility. Also, from the viewpoint of vapor deposition suitability, if the molecular weight is too small, the vapor pressure becomes small, the change from the gas phase to the solid phase does not occur, and it is difficult to form an organic layer. Particularly preferred.

  Specific examples of the compound represented by the general formula (M-1) are shown below, but the present invention is not limited thereto.

(B) Organic layer preferably disposed between the cathode and the light emitting layer Next, the (B) organic layer preferably disposed between the cathode and the light emitting layer will be described.

(B-1) Electron injection layer and 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. The electron injection material and the electron transport material used for these layers may be a low molecular compound or a high molecular compound.
As the electron transport material, the compound represented by the general formula (1) can be used. Other electron transport materials include pyridine derivatives, quinoline derivatives, pyrimidine derivatives, pyrazine derivatives, phthalazine derivatives, phenanthroline derivatives, triazine derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, benzimidazole derivatives, imidazopyridine 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, Metal complexes of phthalocyanine derivatives and 8-quinolinol derivatives, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands Various metal complexes typified by metal complexes, organosilane derivatives typified by siloles, condensed hydrocarbon compounds such as naphthalene, anthracene, phenanthrene, triphenylene, pyrene, etc., are preferred, pyridine derivatives, benzimidazole derivatives , An imidazopyridine derivative, a metal complex, or a condensed ring hydrocarbon compound is more 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 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.

  The electron injection layer can contain an electron donating dopant. By including an electron donating dopant in the electron injection layer, the electron injection property is improved, the driving voltage is lowered, and the efficiency is improved. The electron donating dopant may be any organic material or inorganic material as long as it can give electrons to the doped material and generate radical anions. For example, tetrathiafulvalene (TTF) , Tetrathianaphthacene (TTT), dihydroimidazole compounds such as bis- [1,3 diethyl-2-methyl-1,2-dihydrobenzimidazolyl], lithium, cesium and the like.

  The electron donating dopant in the electron injection layer is preferably contained in an amount of 0.01% by mass to 50% by mass, and 0.1% by mass to 40% by mass, based on the total mass of the compound forming the electron injection layer. It is more preferable that 0.5% by mass to 30% by mass is contained.

(B-2) 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.
The T ₁ energy in the film state of the organic compound constituting the hole blocking layer is higher than the T ₁ energy of the light emitting material in order to prevent energy transfer of excitons generated in the light emitting layer and not to reduce the light emission efficiency. It is preferable.
As an example of the organic compound constituting the hole blocking layer, the compound represented by the general formula (1) can be used.
Examples of other organic compounds constituting the hole blocking layer other than the compound represented by the general formula (1) include aluminum (III) / tris-8-hydroxyquinoline (abbreviated as Alq), aluminum ( III) Aluminum complexes such as bis (2-methyl-8-quinolinato) 4-phenylphenolate (Aluminum (III) bis (2-methyl-8-quinolinato) 4-phenylphenolate (abbreviated as Balq)), triazole derivatives, And phenanthroline derivatives such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline (abbreviated as BCP)), and the like. It is done. In the present invention, the hole blocking layer is not limited to the function of actually blocking holes, and may have a function of preventing the excitons of the light emitting layer from diffusing into the electron transport layer or blocking energy transfer quenching. . The compound of the present invention can also be preferably applied as a hole blocking layer.
The thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 3 nm to 100 nm, and still more preferably 5 nm to 50 nm.
The hole blocking layer may have a single layer structure made of one or more of the materials described above, or may have a multilayer structure made of a plurality of layers having the same composition or different compositions.
The material used for the hole blocking layer is preferably higher than the T ₁ energy of the phosphorescent light emitting material in terms of color purity, light emission efficiency, and driving durability.

(B-3) Material particularly preferably used for the organic layer preferably disposed between the cathode and the light emitting layer The organic electroluminescent element of the present invention is preferably disposed between the (B) cathode and the light emitting layer. As a material particularly preferably used for the material of the organic layer, the compound represented by the general formula (1), the aromatic hydrocarbon compound (particularly, the following general formula (Tp-1)) and the following general formula (O— The compound represented by 1) can be mentioned.
Hereinafter, the aromatic hydrocarbon compound and the compound represented by the general formula (O-1) will be described.

[Aromatic hydrocarbon compounds]
The aromatic hydrocarbon compound is more preferably contained in an organic layer adjacent to the light emitting layer between the light emitting layer and the cathode, but its use is not limited, and any layer in the organic layer may be included. Further, it may be contained. The introduction layer of the aromatic hydrocarbon compound is contained in one or more of a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an exciton block layer, and a charge block layer. be able to.
The organic layer adjacent to the light emitting layer between the light emitting layer and the cathode and containing the aromatic hydrocarbon compound is preferably a block layer (hole blocking layer, exciton blocking layer) or an electron transporting layer. More preferably, it is a transport layer.

When the aromatic hydrocarbon compound is contained in a layer other than the light emitting layer, it is preferably contained in an amount of 70 to 100% by mass, more preferably 85 to 100% by mass. When the aromatic hydrocarbon compound is contained in the light emitting layer, it is preferably included in an amount of 0.1 to 99% by mass, more preferably 1 to 95% by mass, and more preferably 10 to 95%, based on the total mass of the light emitting layer. It is more preferable to include the mass%.
As the aromatic hydrocarbon compound, it is preferable to use a hydrocarbon compound having a molecular weight of 400 to 1200 and a condensed polycyclic skeleton having a total carbon number of 13 to 22. Examples of the condensed polycyclic skeleton carbon atoms in total 13 to 22, fluorene fluorene, anthracene, phenanthrene, tetracene, chrysene, pentacene, pyrene, perylene, is preferably one of triphenylene, in view of T _1, triphenylene, phenanthrene Is more preferable, and triphenylene is more preferable from the viewpoint of stability of the compound and charge injection / transport properties, and a compound represented by the following general formula (Tp-1) is particularly preferable.

  The hydrocarbon compound represented by the general formula (Tp-1) preferably has a molecular weight in the range of 400 to 1200, more preferably 400 to 1100, and still more preferably 400 to 000. If the molecular weight is 400 or more, a high-quality amorphous thin film can be formed, and if the molecular weight is 1200 or less, it is preferable in terms of solubility in a solvent, sublimation, and appropriate deposition.

  The application of the hydrocarbon compound represented by the general formula (Tp-1) is not limited, and may be further contained in any layer within the organic layer as well as the organic layer adjacent to the light emitting layer. .

In the general formula (Tp-1), R ^{12 to} R ²³ are each independently a hydrogen atom, an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group (these are further an alkyl group, a phenyl group, a fluorenyl group, A naphthyl group or a triphenylenyl group). However, R ^{12 to} R ²³ are not all hydrogen atoms.

Examples of the alkyl group represented by R ^{12 to} R ²³ include a substituted or unsubstituted, for example, methyl group, ethyl group, isopropyl group, n-butyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like can be mentioned, preferably methyl group, ethyl group, isopropyl group, tert-butyl group, cyclohexyl group, more preferably methyl group, ethyl group, or A tert-butyl group.

R ^{12 to} R ²³ are preferably an alkyl group having 1 to 4 carbon atoms, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group (these are further an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group). It is more preferably a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group, which may be substituted with (which may be substituted).
A benzene ring that may be substituted with a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group (which may be further substituted with an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group); It is particularly preferred.

  The total number of aryl rings in the general formula (Tp-1) is preferably 2 to 8, and preferably 3 to 5. By setting it as this range, a high-quality amorphous thin film can be formed, and solubility in a solvent, sublimation, and deposition suitability are improved.

R ^{12 to} R ²³ each independently preferably has a total carbon number of 20 to 50, and more preferably a total carbon number of 20 to 36. By setting it as this range, a high-quality amorphous thin film can be formed, and solubility in a solvent, sublimation, and deposition suitability are improved.

  The hydrocarbon compound represented by the general formula (Tp-1) is preferably a hydrocarbon compound represented by the following general formula (Tp-2).

In General Formula (Tp-2), a plurality of Ar ¹¹ are the same, and an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group (these are an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or Which may be substituted with a triphenylenyl group).

As a hydrogen atom represented by Ar ¹¹ , an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group (these may be further substituted with an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group) Are synonymous with those described for R ^{12 to} R ²³ , and preferred ones are also the same.

  The hydrocarbon compound represented by the general formula (Tp-1) is also preferably a hydrocarbon compound represented by the following general formula (Tp-3).

  In general formula (Tp-3), L is an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group (these are further substituted with an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group). Or an n-valent linking group formed by combining these. n represents an integer of 2 to 6.

The alkyl group, phenyl group, fluorenyl group, naphthyl group, or triphenylenyl group that forms the n-valent linking group represented by L has the same meaning as that described for R ^{12 to} R ²³ .
L is preferably an alkyl group or a benzene ring, a fluorene ring optionally substituted with a benzene ring, or an n-valent linking group formed by combining these.
Although the preferable specific example of L is given to the following, it is not limited to these. In the specific examples, it is bonded to the triphenylene ring by *.

  n is preferably 2 to 5, and more preferably 2 to 4.

  The compound represented by the general formula (Tp-1) is preferably a compound represented by the following general formula (Tp-4).

（一般式（Ｔｐ−４）において、Ａ^A1〜Ａ^A12はそれぞれ独立にＣＲ⁴⁰⁰または窒素原子を表す。ｎ⁴⁰¹は０〜８の整数を表す。ｎ⁴⁰¹が０である場合、Ａ^A1〜Ａ^A6で表される環は、トリフェニレン環とＡ^A7〜Ａ^A12で表される環との間の単結合を表す。ｎ⁴⁰¹が２〜６の場合、複数存在するＡ^A1〜Ａ^A6で表される環は出現ごとに異なってもよく、複数存在する環同士の連結様式も出現ごとに異なっていてもよい。）
なお、本発明において、前記一般式（Ｔｐ−４）の説明における水素原子は同位体（重水素原子等）も含み、また更に置換基を構成する原子は、その同位体も含んでいることを表す。
前記一般式（Ｔｐ−４）において、Ｒ⁴¹¹〜Ｒ⁴²¹はそれぞれ独立に水素原子、アルキル基、フェニル基、フルオレニル基、ナフチル基、またはトリフェニレニル基（これらは更にアルキル基、フェニル基、フルオレニル基、ナフチル基、若しくはトリフェニレニル基で置換されていてもよい）を表す。
Ｒ⁴¹¹〜Ｒ⁴²¹として好ましくは、水素原子、炭素数１〜４のアルキル基、フェニル基、フルオレニル基、ナフチル基、若しくはトリフェニレニル基（これらは更にアルキル基、フェニル基、フルオレニル基、ナフチル基、若しくはトリフェニレニル基で置換されていてもよい）であることが好ましく、水素原子、フェニル基（該フェニル基はアルキル基、フェニル基、フルオレニル基、ナフチル基、若しくはトリフェニレニル基で置換されていてもよい）であることが更に好ましく、水素原子であることが特に好ましい。
Ａ^A1〜Ａ^A12として好ましくはＣＲ⁴⁰⁰である。
前記一般式（Ｔｐ−４）中、Ｒ⁴⁰⁰が表す置換基としては、水素原子、炭素数１〜４のアルキル基、フェニル基、フルオレニル基、ナフチル基、若しくはトリフェニレニル基（これらは更にアルキル基、フェニル基、フルオレニル基、ナフチル基、若しくはトリフェニレニル基で置換されていてもよい）を表す。複数存在するＲ⁴⁰⁰はそれぞれ異なっていてもよい。
Ｒ⁴⁰⁰として好ましくは、水素原子、炭素数１〜４のアルキル基、フェニル基、フルオレニル基、ナフチル基、若しくはトリフェニレニル基（これらは更にアルキル基、フェニル基、フルオレニル基、ナフチル基、若しくはトリフェニレニル基で置換されていてもよい）であることが好ましく、水素原子、炭素数１〜４のアルキル基、フェニル基（該フェニル基はアルキル基、フェニル基、フルオレニル基、ナフチル基、若しくはトリフェニレニル基で置換されていてもよい）であることが更に好ましく、水素原子、炭素数１〜４のアルキル基、フェニル基（該フェニル基はアルキル基、フェニル基、フルオレニル基、ナフチル基、若しくはトリフェニレニル基で置換されていてもよい）であることが特に好ましい。
ｎ⁴⁰¹として好ましくは０〜５の整数であり、１〜５の整数であることがさらに好ましく、２〜４であることが特に好ましい。
ｎ⁴⁰¹は１以上の整数であり、Ａ^A7〜Ａ^A12で表される環と連結する位置がＡ^A3である場合、発光効率の観点からＡ^A4またはＡ^A5で表される置換基はＣＲ⁴⁰⁰であり、Ｒ⁴⁰⁰は炭素数１〜４のアルキル基、フェニル基が好ましく、炭素数１〜４のアルキル基が更に好ましく、メチル基であることが特に好ましい。
前記一般式（Ｔｐ−４）中、Ａ^A1〜Ａ^A12によって構成される各６員環の芳香環のうち、窒素原子を含む環が１個以下であることが好ましく、０個であることがより好ましい。前記一般式（Ｔｐ−４）中、Ａ^A1〜Ａ^A12によって構成される各６員環の芳香環の連結に制限はないが、メタ位またはパラ位で連結していることが好ましい。よりさらに、前記一般式（Ｔｐ−４）で表される化合物は、トリフェニレン環を構成する縮環の部分構造であるフェニル環を含め、パラ位で連続して連結している芳香環の個数が３個以下であることが好ましい。

(In the general formula (Tp-4), if .n ⁴⁰¹ .n ⁴⁰¹ is an integer from 0 to 8 representing the CR ⁴⁰⁰ or a nitrogen atom A ^A1 to A ^A12 are each independently is 0, A ^A1 to A ^The ring represented by ^A6 represents a single bond between the triphenylene ring and the ring represented by A ^{A7 to} A ^{A12. When} n ⁴⁰¹ is 2 to 6, it is represented by a plurality of A ^{A1 to} A ^A6. The ring may be different for each occurrence, and the manner in which multiple rings are present may be different for each occurrence.)
In the present invention, the hydrogen atom in the description of the general formula (Tp-4) includes an isotope (deuterium atom, etc.), and the atoms constituting the substituent further include the isotope. Represent.
In the general formula (Tp-4), R ^{411 to} R ⁴²¹ are each independently a hydrogen atom, an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group (these are further an alkyl group, a phenyl group, a fluorenyl group, A naphthyl group or a triphenylenyl group).
Preferred as R ⁴¹¹ to R ^421, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group (these may be further alkyl groups, a phenyl group, a fluorenyl group, a naphthyl group, or And may be substituted with a triphenylenyl group), and may be a hydrogen atom or a phenyl group (the phenyl group may be substituted with an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group). More preferably, it is particularly preferably a hydrogen atom.
A ^{A1 to} A ^A12 are preferably CR ⁴⁰⁰ .
In the general formula (Tp-4), examples of the substituent represented by R ⁴⁰⁰ include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group (these are further an alkyl group, A phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group). A plurality of R ⁴⁰⁰ may be different from each other.
R ⁴⁰⁰ is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group (these are an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group). It may be substituted, and is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group (the phenyl group is substituted with an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group). More preferably, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group (the phenyl group is substituted with an alkyl group, a phenyl group, a fluorenyl group, a naphthyl group, or a triphenylenyl group). It may be particularly preferable.
n ⁴⁰¹ is preferably an integer of 0 to 5, more preferably an integer of 1 to 5, and particularly preferably 2 to 4.
n ⁴⁰¹ is an integer of 1 or more, and when the position connected to the ring represented by A ^{A7 to} A ^A12 is A ^A3 , the substituent represented by A ^A4 or A ^A5 is CR ⁴⁰⁰ from the viewpoint of luminous efficiency. R ⁴⁰⁰ is preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group.
In the general formula (Tp-4), among the six-membered aromatic rings constituted by A ^{A1 to} A ^A12 , the number of nitrogen-containing rings is preferably 1 or less, and 0. More preferred. In the general formula (Tp-4), although there is no limitation on the connection of each 6-membered aromatic ring constituted by A ^{A1 to} A ^A12 , it is preferable to connect at the meta position or the para position. Furthermore, the compound represented by the general formula (Tp-4) includes a phenyl ring which is a partial structure of a condensed ring constituting a triphenylene ring, and the number of aromatic rings continuously connected at the para position. The number is preferably 3 or less.

When the hydrocarbon compound represented by the general formula (Tp-1) is used as a host material of a light emitting layer of an organic electroluminescent element or a charge transport material of a layer adjacent to the light emitting layer, it is in a thin film state than the light emitting material When the energy gap (low emission triplet (T ₁ ) energy in a thin film state when the light emitting material is a phosphorescent light emitting material) is large, the light emission is prevented from quenching, which is advantageous in improving efficiency. On the other hand, from the viewpoint of chemical stability of the compound, it is preferable that the energy gap and T ₁ energy are not too large. The T ₁ energy in the film state of the hydrocarbon compound represented by the general formula (Tp-1) is preferably 1.77 eV (40 kcal / mol) or more and 3.51 eV (81 kcal / mol) or less. It is more preferable that it is 39 eV (55 kcal / mol) or more and 3.25 eV (75 kcal / mol) or less. In the organic electroluminescent element of the present invention, it is preferable from the viewpoint of luminous efficiency that the T ₁ energy of the compound represented by the general formula (Tp-1) is higher than the T ₁ energy of the phosphorescent material. . In particular, when the emission color from the organic electroluminescence device is green (emission peak wavelength is 490 to 580 nm), from the viewpoint of light emission efficiency, the T ₁ energy is 2.39 eV (55 kcal / mol) or more and 2.82 eV (65 kcal / mol). mol) or less.

The T ₁ energy of the hydrocarbon compound represented by the general formula (Tp-1) can be obtained by a method similar to the method in the description of the general formula (1).

  The glass transition temperature (Tg) of the hydrocarbon compound according to the present invention is 80 ° C. or more and 400 ° C. or less from the viewpoint of stably operating the organic electroluminescence device against heat generation during high temperature driving or during device driving. The temperature is preferably 100 ° C. or higher and 400 ° C. or lower, more preferably 120 ° C. or higher and 400 ° C. or lower.

  Hereinafter, specific examples of the hydrocarbon compound represented by the general formula (Tp-1)) will be exemplified, but the hydrocarbon compound used in the present invention is not limited thereto. Absent.

The compounds exemplified as the hydrocarbon compound represented by the general formula (Tp-1) include WO05 / 013388 pamphlet, WO06 / 130598 pamphlet, WO09 / 021107 pamphlet, US2009 / 0009065, WO09 / 008311 pamphlet and WO04 / 018587 pamphlet.
After synthesis, it is preferable to purify by sublimation purification after purification by column chromatography, recrystallization or the like. By sublimation purification, not only can organic impurities be separated, but inorganic salts and residual solvents can be effectively removed.

[Compound represented by formula (O-1)]
As a material particularly preferably used for the material of the organic layer that is preferably arranged between the (B) cathode and the light emitting layer, it is possible to use a compound represented by the following general formula (O-1) as an organic electroluminescence. It is preferable from the viewpoint of element efficiency and driving voltage. Below, general formula (O-1) is demonstrated.

In general formula (O-1), R ^O1 represents an alkyl group, an aryl group, or a heteroaryl group. A ^{O1 to} A ^O4 each independently represent C—R ^A or a nitrogen atom. R ^A represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and a plurality of R ^A may be the same or different. L ^O1 represents a divalent to hexavalent linking group composed of an aryl ring or a heteroaryl ring. n ^O1 represents an integer of 2 to 6.

R ^O1 represents an alkyl group (preferably having 1 to 8 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms), or a heteroaryl group (preferably having 4 to 12 carbon atoms), and these are the aforementioned substituents. Group A may be included. R ^O1 is preferably an aryl group or a heteroaryl group, more preferably an aryl group. A preferable substituent when the aryl group of R ^O1 has a substituent includes an alkyl group, an aryl group or a cyano group, more preferably an alkyl group or an aryl group, and still more preferably an aryl group. When the aryl group of R ^O1 has a plurality of substituents, the plurality of substituents may be bonded to each other to form a 5- or 6-membered ring. The aryl group of R ^O1 is preferably a phenyl group which may have a substituent A, more preferably a phenyl group which an alkyl group or an aryl group may be substituted, and still more preferably an unsubstituted group. A phenyl group or a 2-phenylphenyl group.

A ^{O1 to} A ^O4 each independently represent C—R ^A or a nitrogen atom. Of A ^{O1 to} A ^O4 , 0 to 2 are preferably nitrogen atoms, and 0 or 1 is more preferably a nitrogen atom. It is preferred that all of A ^{O1 to} A ^O4 are C—R ^A , or A ^O1 is a nitrogen atom and A ^{O2 to} A ^O4 are C—R ^A , A ^O1 is a nitrogen atom, and A ^O2 to More preferably, A ^O4 is C—R ^A , A ^O1 is a nitrogen atom, A ^{O2 to} A ^O4 are C—R ^A , and all R ^A are hydrogen atoms.

R ^A represents a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms), or a heteroaryl group (preferably having 4 to 12 carbon atoms). It may have a substituent Z ^T. The plurality of R ^A may be the same or different. R ^A is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

L ^O1 represents a divalent to hexavalent linking group composed of an aryl ring (preferably having 6 to 30 carbon atoms) or a heteroaryl ring (preferably having 4 to 12 carbon atoms). L ^O1 is preferably an arylene group, heteroarylene group, aryltriyl group, or heteroaryltriyl group, more preferably a phenylene group, a biphenylene group, or a benzenetriyl group, still more preferably a biphenylene group, Or it is a benzenetriyl group. L ^O1 may have the above-described substituent Z ^T , and when it has a substituent, the substituent is preferably an alkyl group, an aryl group, or a cyano group. Specific examples of L ^O1 include the following.

n ^O1 represents an integer of 2 to 6, preferably an integer of 2 to 4, more preferably 2 or 3. n ^O1 is most preferably 3 from the viewpoint of the efficiency of the organic electroluminescent element, and most preferably 2 from the viewpoint of the durability of the organic electroluminescent element.
The compound represented by the general formula (O-1) is more preferably a compound represented by the following general formula (O-2).

In general formula (O-2), R ^O1 independently represents an alkyl group, an aryl group, or a heteroaryl group. R ^{O2 to} R ^O4 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. A ^{O1 to} A ^O4 each independently represent C—R ^A or a nitrogen atom. R ^A represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and a plurality of R ^A may be the same or different.

R ^O1 and A ^O1 to A ^O4, the general formula (O1) in the same meaning as R ^O1 and A ^O1 to A ^O4 of, also the same preferable ranges thereof.
R ^{02 to} R ⁰⁴ are each independently a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms), or a heteroaryl group (preferably having 4 to 12 carbon atoms). Which may have the substituent group A described above. R ^{02 to} R ⁰⁴ are preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an aryl group, and most preferably a hydrogen atom.

  The compound represented by the general formula (O-1) has a glass transition temperature (Tg) of 100 ° C. from the viewpoint of stability at high temperature storage, stable operation against high temperature driving, and heat generation during driving. It is preferably ˜400 ° C., more preferably 120 ° C. to 400 ° C., and still more preferably 140 ° C. to 400 ° C.

  Specific examples of the compound represented by the general formula (O-1) are shown below, but the compound used in the present invention is not limited thereto.

  The compound represented by the general formula (O-1) can be synthesized by the method described in JP-A No. 2001-335776. After synthesis, purification by column chromatography, recrystallization, reprecipitation, etc., followed by purification by sublimation is preferred. Not only can organic impurities be separated by sublimation purification, but inorganic salts, residual solvents, moisture, and the like can be effectively removed.

  In the organic electroluminescent device of the present invention, the compound represented by the general formula (O-1) is preferably contained in the organic layer between the light emitting layer and the cathode, but the layer on the cathode side adjacent to the light emitting layer. It is more preferable that it is contained.

<Protective layer>
In the present invention, the entire organic electroluminescent element may be protected by a protective layer.
Regarding the protective layer, the matters described in paragraph numbers [0169] to [0170] of JP-A-2008-270736 can be applied to the present invention. The material for the protective layer may be inorganic or organic.

<Sealing container>
The organic electroluminescent element of the present invention may be sealed entirely using a sealing container.
Regarding the sealing container, the matters described in paragraph No. [0171] of JP-A-2008-270736 can be applied to the present invention.

<Driving method>
The organic electroluminescence device of the present invention emits light by applying a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. Can be obtained.
The driving method of the organic electroluminescence device of the present invention is described in JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234658, and JP-A-8-2441047. The driving methods described in each publication, Japanese Patent No. 2784615, US Pat. Nos. 5,828,429 and 6,023,308 can be applied.

The external quantum efficiency of the organic electroluminescent device of the present invention is preferably 7% or more, and more preferably 10% or more. The value of the external quantum efficiency should be the maximum value of the external quantum efficiency when the device is driven at 20 ° C., or the value of the external quantum efficiency around 300 to 400 cd / m ² when the device is driven at 20 ° C. Can do.

  The internal quantum efficiency of the organic electroluminescence device of the present invention is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more. The internal quantum efficiency of the device is calculated by dividing the external quantum efficiency by the light extraction efficiency. In a normal organic EL element, the light extraction efficiency is about 20%, but the shape of the substrate, the shape of the electrode, the thickness of the organic layer, the thickness of the inorganic layer, the refractive index of the organic layer, the refractive index of the inorganic layer, etc. By devising it, it is possible to increase the light extraction efficiency to 20% or more.

<Emission wavelength>
There is no restriction | limiting in the light emission wavelength of the organic electroluminescent element of this invention. For example, among the three primary colors of light, it may be used for red light emission, green light emission, or blue light emission. Among them, the organic electroluminescence device of the present invention has an emission peak wavelength of 400 to 700 nm, considering the lowest excited triplet (T ₁ ) energy of the compound represented by the general formula (1). From the viewpoint of
Specifically, in the organic electroluminescence device of the present invention, when the compound represented by the general formula (1) is used as a host material of the light emitting layer, an electron transport layer or an electron transport material of the hole blocking layer, the guest The emission peak wavelength of the material is preferably 400 to 700 nm, more preferably 450 to 650 nm, and particularly preferably 480 to 550 nm.

<Use of the organic electroluminescent device of the present invention>
The organic electroluminescent element of the present invention can be suitably used for a display element, a display, a backlight, an electrophotography, an illumination light source, a recording light source, an exposure light source, a reading light source, a sign, a signboard, an interior, or optical communication. In particular, it is preferably used for a device that is driven in a region where light emission luminance is high, such as a light emitting device, a lighting device, and a display device.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[Comparative Example 1]
Chem. Eur. J. et al. In the method described in 2009, 15, 5482-5490, the following indolocarbazole (indoro [3,2,1-jk] carbazole) is synthesized by using the FVP (Flash Vacuum Pyrolysis) method by the following synthesis route. Was 71%.

[Comparative Example 2]
According to the method described in JP 2010-87496 A, the following indolocarbazole (indoro [3,2,1-jk] carbazole) was synthesized by the following synthesis route through a diazonium salt. The total yield at that time was 55%.

[Example 1]
Indolocarbazole (indoro [3,2,1-jk] carbazole) was synthesized according to the following scheme.

Carbazole (29.4 g, 176 mmol, 1.0 eq), o-chlorofluorobenzene (46.0 g, 352 mmol, 2.0 eq), potassium carbonate (73.0 g, 528 mmol, 3.0 eq) N, N -Mixed in 350 mL of dimethylacetamide and heated at 185 ° C. for 5 hours under nitrogen atmosphere. After allowing to cool, the reaction mixture was extracted with ethyl acetate, and the organic layer was dried over sodium sulfate and filtered. The resulting solution was concentrated under reduced pressure and then reslurried in a small amount of acetonitrile. The resulting precipitate yielded 44.0 g of intermediate (yield 90%).
Intermediate (15.0 g, 54 mmol, 1.0 eq), potassium carbonate (14.9 g, 108 mmol, 2.0 eq), palladium acetate (606 mg, 2.7 mmol, 0.05 eq) tricyclohexylphosphonium tetrafluoro Borate (2.00 g, 5.4 mmol, 0.10 equivalent) was mixed with 110 mL of N, N-dimethylacetamide and heated at 185 ° C. for 5 hours under a nitrogen atmosphere. Thereafter, the reaction solution was poured into water. The resulting precipitate was collected by filtration and recrystallized from acetonitrile to obtain 11.1 g (yield 85%) of indolocarbazole (indoro [3,2,1-jk] carbazole). The total yield at this time was 77%.
A ¹ H-NMR chart of the synthesized compound is shown in FIG.

[Example 2]
According to the following scheme, the synthesis method of the indolocarbazole derivative was implemented.

9H-carbazole (23.8 g, 142 mmol, 1.0 eq), 3-chloro-4-fluoronitrobenzene (25.0 g, 142 mmol, 1.0 eq), potassium carbonate (59.1 g, 427 mmol, 3.0 eq) Was mixed with N, N-dimethylacetamide (450 mL) and heated at 150 ° C. for 3 and a half hours under a nitrogen atmosphere. After allowing to cool, palladium acetate (1.60 g, 7.1 mmol, 0.05 equivalents) and tricyclohexylphosphine tetrafluoroborate (5.24 g, 14.2 mmol, 0.10 equivalents) were added to the reaction solution at 170 ° C. Heated for 1 hour. Water (3 L) was added to the reaction solution allowed to cool and stirred, and the resulting precipitate was filtered off. The solid collected by filtration was dissolved in toluene, dried and concentrated, and the solid reprecipitated with methanol was collected by filtration to obtain 33.2 g of an intermediate having a nitro group (yield 81%).
Ammonium chloride (1.01 g, 18.9 mmol, 0.2 eq), reduced iron (21.07 g, 377 mmol, 4.0 eq) and water (94.5 mL) were heated at 160 ° C. for 1 h. The reaction solution was lowered to 90 ° C., and then isopropyl alcohol (855 mL), acetic acid (13.5 mL), and N, N′-dimethylimidazolidinone (40.5 mL) were added. An intermediate having a nitro group (27.0 g, 94.3 mmol, 1.0 equivalent) was added to the reaction solution, and the mixture was heated at 90 ° C. for 1.5 hours. After allowing to cool, the reaction solution was filtered through Celite, and extracted and dried with ethyl acetate. The intermediate body which has an amino group was obtained by concentrating a solution. Acetonitrile (270 mL) and hydrochloric acid (1.5 M aqueous solution, 136 mL) were added to the amino group-containing intermediate obtained in the above reaction, and the mixture was cooled to −5 ° C. with ice, and then sodium nitrite (7.8 g, 113 mmol, 1 .2 equivalents) aqueous solution (34 mL) was added dropwise. After stirring with ice cooling for 1 hour, an aqueous solution (54 mL) of potassium iodide (39.12 g, 236 mmol, 2.5 equivalents) was added dropwise, and the mixture was stirred for 4 hours while gradually warming to 80 ° C. To the reaction solution allowed to cool, 900 mL of toluene was added, and the extracted organic layer was washed with an aqueous sodium sulfite solution. The concentrated residue was subjected to column purification (eluent hexane: toluene = 2: 1) to obtain 35 g of iodoindolocarbazole as white crystals (2-step yield 49%).
The ¹ H-NMR charts of the synthesized indolocarbazole derivative having a nitro group and indolocarbazole derivative having an iodo group are shown in FIGS. 3 and 4, respectively.

  From the comparison between Examples 1 and 2 and Comparative Examples 1 and 2, the synthesis method of the present invention has a higher yield than known synthesis methods, and can be used for synthesis on a scale of several tens of grams and is simple. all right.

[Example 3]
Indolocarbazole derivative H9, which is a compound described in International Publication No. WO2011 / 088887, was synthesized according to the following scheme.

9,9′-dimethyl-9,10-dihydroacridine (30.0 g, 143 mmol, 1.0 equiv), 3-chloro-4-fluoronitrobenzene (25.2 g, 143 mmol, 1.0 equiv), potassium carbonate (59. 4 g, 430 mmol, 3.0 eq) were mixed with N, N-dimethylacetamide (450 mL) and heated at 170 ° C. for 4 hours under nitrogen atmosphere. After allowing to cool, palladium acetate (1.61 g, 7.2 mmol, 0.05 eq) and tricyclohexylphosphine tetrafluoroborate (5.28 g, 14.3 mmol, 0.10 eq) were added to the reaction solution at 170 ° C. Heated for 2 hours. After allowing to cool, the reaction solution was extracted with ethyl acetate, and the concentrated residue was subjected to column purification (eluent hexane: ethyl acetate = 10: 1) to obtain 39.1 g of an intermediate having a nitro group (yield 83). %)Obtained.
Ammonium chloride (978 mg, 18.3 mmol, 0.2 eq), reduced iron (20.4 g, 365 mmol, 4.0 eq) and water (90 mL) were heated at 160 ° C. for 1 h. The reaction solution was lowered to 90 ° C., and isopropyl alcohol (210 mL), acetic acid (14.0 mL), and N, N′-dimethylimidazolidinone (30 mL) were added. An intermediate having a nitro group (30.0 g, 91.4 mmol, 1.0 equivalent) was suspended in isopropyl alcohol (600 mL), added dropwise, and heated at 90 ° C. for 1.5 hours. After allowing to cool, the reaction solution was filtered through Celite, and extracted and dried with ethyl acetate. The solution was concentrated to obtain 24.5 g (yield 90%) of an intermediate having an amino group.
Acetonitrile (190 mL) and hydrochloric acid (1.5 M aqueous solution, 96 mL) were added to an amino group-containing intermediate (20.0 g, 67.0 mmol, 1.0 equivalent), and the mixture was ice-cooled to −5 ° C. and then sodium nitrite. An aqueous solution (24 mL) of (5.55 g, 80.4 mmol, 1.2 eq) was added dropwise. After stirring with ice cooling for 1 hour, an aqueous solution (38 mL) of potassium iodide (27.8 g, 167 mmol, 2.5 equivalents) was added dropwise, and the mixture was stirred for 4 hours while gradually warming to 80 ° C. To the reaction solution allowed to cool was added 500 mL of toluene, and the extracted organic layer was washed with an aqueous sodium sulfite solution. The residue after concentration was subjected to column purification (eluent hexane: toluene = 2: 1) to obtain 21.9 g (yield 80%) of an intermediate having an iodo group.
Intermediate having an iodo group (20.0 g, 48.9 mmol, 1.0 equivalent), 9H-carbazole (8.6 g, 51.3 mmol, 1.05 equivalent), copper iodide (931 mg, 4.89 mmol, 0 equivalent) 0.1 equivalent), copper (621 mg, 9.77 mmol, 0.2 equivalent), potassium carbonate (13.5 g, 97.7 mmol, 2 equivalents), and diphenyl ether (50 mL) were added, and at 190 ° C. for 24 hours under a nitrogen atmosphere. Heated. After completion of the reaction, diphenyl ether was removed by heating under reduced pressure, reslurried in toluene, and filtered through celite. The concentrated residue was subjected to column purification (eluent: hexane to hexane: toluene = 4: 1) to obtain 19.1 g (yield 87%) of H9. The total yield at this time was 52%.
A ¹ H-NMR chart of the synthesized compound 25-a having a nitro group is shown in FIG.

[Comparative Example 3]
Indolocarbazole derivative H9 was synthesized by a method according to the following scheme described in International Publication WO2011 / 088887. The total yield at this time was 49%.

  From the comparison between Example 3 and Comparative Example 3, the synthesis method of the present invention has a higher yield than the known synthesis method, and can cope with the synthesis on the scale of several tens of grams, so that the desired compound can be selectively purified with high purity. It was found that it could be synthesized. .

[Examples 4 and 5 and Comparative Examples 4 and 5]
<Production and evaluation of organic electroluminescence device>
Using the indolocarbazole derivative H9 synthesized by the synthesis method of Example 3 and Comparative Example 3 as the host material of the light emitting layer, the organic electroluminescent elements of Examples 4 and 5 and Comparative Examples 4 and 5 having the following configurations Were fabricated, and the fabricated devices were evaluated.
In addition, all the materials used for preparation of the organic electroluminescence device are subjected to sublimation purification, and the purity (254 nm absorption intensity area ratio) is 99.9% or more by high performance liquid chromatography (Tosoh TSKgel ODS-100Z). confirmed.

(Production of organic EL elements (vapor deposition))
A glass substrate having a thickness of 0.5 mm and a 2.5 cm square ITO film (manufactured by Geomat Co., Ltd., surface resistance 10 Ω / □) is placed in a cleaning container, subjected to ultrasonic cleaning in 2-propanol, and then subjected to UV-ozone treatment for 30 minutes. Went. The following organic compound layers were sequentially deposited on the transparent anode (ITO film) by vacuum deposition.

First layer: HAT-CN: film thickness 10 nm

Second layer: NPD: film thickness 30 nm

Third layer: the following luminescent material 1 and host material (mass ratio = 85: 15): film thickness 30 nm

Host material of third layer (light emitting layer) Example 4: Indolocarbazole derivative H9 synthesized by the synthesis method of Example 3
Comparative Example 4: Indolocarbazole derivative H9 synthesized by the synthesis method of Comparative Example 3

Fourth layer: TpH-18: film thickness 10 nm

Fifth layer: Alq: film thickness 40 nm

On this, 1 nm of lithium fluoride and 100 nm of metal aluminum were vapor-deposited in this order, and it was set as the cathode. A patterned mask (a mask having a light emitting area of 2 mm × 2 mm) was placed on the lithium fluoride layer, and metal aluminum was deposited.
This laminated body is put in a glove box substituted with nitrogen gas without being exposed to the atmosphere, and sealed with a glass sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.). The organic electroluminescent elements of Example 4 and Comparative Example 4 were obtained.

The element of Example 5 was produced in the same manner except that the light emitting material 1 used in the element of Example 4 was changed to the light emitting material 2. The element of Comparative Example 5 was produced in the same manner except that the light emitting material 1 used for the element of Comparative Example 4 was changed to the light emitting material 2.

  As a result of emitting light from the organic electroluminescent elements of each Example and Comparative Example, light emission derived from the light emitting material was obtained for each of the organic electroluminescent elements.

<Element evaluation>
The time required for the luminance to decrease to 80% when each element was made to emit light at 5000 cd / m ² was measured.

From the obtained results, the indolocarbazole derivative H9 synthesized by the synthetic route of Comparative Example 3 was compared with the organic electroluminescent element of Example 4 using the indolocarbazole derivative H9 synthesized by the synthetic route of Example 3. The time required for the luminance of the organic electroluminescent device of Comparative Example 4 using the above to decrease to 80% was 1/5.
Similarly, in Comparative Example 5, the time for the luminance of the organic electroluminescent element to be reduced to 80% was 1/3 as compared with Example 5.
Although not limited to any reason, in the synthesis route of Comparative Example 3, dibromination proceeds in addition to monobromination, and it is difficult to control by-products, and in the ring closure reaction, other than the desired cyclized product. It is also considered that the generation of by-products significantly reduced the time for the luminance to decrease to 80%.

DESCRIPTION OF SYMBOLS 2 ... Substrate 3 ... Anode 4 ... Hole injection layer 5 ... Hole transport layer 6 ... Light emitting layer 7 ... Hole block layer 8 ... Electron transport layer 9 ...・ Cathode 10: Organic electroluminescent device (organic EL device)

Claims (7)

A compound represented by the following general formula (1) and a compound represented by the following general formula (2) are reacted, and a compound represented by the following general formula (3) is used as an intermediate, followed by the following general formula (4) A synthesis method comprising synthesizing a compound represented by:

(In the general formulas (1) to (4), X ^{11 to} X ¹⁷ and X ^{21 to} X ²⁴ each independently represent CR ⁰ or N, and R ⁰ each independently represents a hydrogen atom or a substituent. Represents a single bond, O, S, Se, CR ¹ R ² , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent, Z represents Cl, Br, I represents OTf, and Tf represents a trifluoromethanesulfonyl group (a trifuryl group). 2. The synthesis method according to claim 1, wherein the compound represented by the general formula (4) is a compound represented by any one of the following general formulas (A) to (C).

(In the general formulas (A) to (C), X ^{11 to} X ¹⁷ and X ^{21 to} X ²⁴ each independently represent CR ⁰ or N, and R ⁰ each independently represents a hydrogen atom or a substituent. A single bond, O, S, Se, CR ¹ R ² , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , and R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent.) The compound represented by the general formula (4) is a compound represented by the following general formula (8),
A compound represented by the following general formula (5) and a compound represented by the following general formula (6) are reacted, and a compound represented by the following general formula (7) is used as an intermediate, and then the above general formula (8) 3. The synthesis method according to claim 1, wherein the compound represented by formula (1) is synthesized.

(In the general formulas (5) to (8), R ^{51 to} R ⁵⁷ and R ^{61 to} R ⁶⁴ each independently represent a hydrogen atom or a substituent. Y represents a single bond, O, S, Se, CR ¹ R ^2. , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent, Z represents Cl, Br, I or OTf, where Tf is trifluoromethanesulfonyl. Represents a group (trifuryl group).) 4. The synthesis method according to claim 3, wherein the compound represented by the general formula (8) is a compound represented by any one of the following general formulas (G) to (I).

(In the general formulas (G), (H) and (I), R ^{51 to} R ⁵⁷ and R ^{61 to} R ⁶⁴ each independently represents a hydrogen atom or a substituent. Y represents a single bond, O, S, Se, CR ¹ R ² , NR ³ , SiR ⁴ R ⁵ or BR ⁶ is represented, and R ^{1 to} R ⁶ each independently represent a hydrogen atom or a substituent.) A compound represented by any one of the following general formulas (11) to (16).

(In the general formulas (11) to (16), X ^{11 to} X ¹⁷ and X ^{21 to} X ²⁴ each independently represent CR ⁰ or N, and R ⁰ each independently represents a hydrogen atom or a substituent. A single bond, O, S, Se, CR ¹ R ² , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , and R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent.) The compound according to claim 5, which is represented by any one of the following general formulas (21) to (26).

(In the general formulas (21) to (26), R ^{51 to} R ⁵⁷ and R ^{61 to} R ⁶⁴ each independently represent a hydrogen atom or a substituent. Y represents a single bond, O, S, Se, CR ¹ R ^2. , NR ³ , SiR ⁴ R ⁵ or BR ⁶ , and R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent.) A substrate,
A pair of electrodes arranged on the substrate and comprising an anode and a cathode;
And at least one organic layer including a light emitting layer disposed between the electrodes,
The organic electroluminescent element characterized by including in the said light emitting layer the compound synthesize | combined through the synthesis method as described in any one of Claims 1-4, and the compound of Claim 5 or 6.

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