JP2015193555A - Method for producing carbazole compound having tertiary amino group, and the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method which can provide a carbazole compound having a tertiary amino group in high yield with suppressed formation of by-products, and which can simplify the production process.SOLUTION: The carbazole compound having a tertiary amino group is produced by using: a step of introducing a tertiary amino group into a compound comprising a 9-butoxycarbonylcarbazole structure; and a step of eliminating the butoxycarbonyl group from the compound.

Description

  The present invention relates to a method and a compound for producing a carbazole compound having a tertiary amino group useful as an organic semiconductor material.

A carbazole compound having a tertiary amino group is useful as an organic semiconductor material, and can be widely used as a light-emitting material, an electron transport material, a hole transport material and the like constituting an organic light-emitting element. Various methods for producing such a carbazole compound having a tertiary amino group have been made to suppress the production of by-products to increase the yield and simplify the process.
Non-Patent Document 1 discloses a method for producing a carbazole compound, in which a tertiary amino group is introduced into a carbazole ring by directly reacting a secondary amine with a carbazole compound in which an iodine atom is substituted on the carbazole ring, as shown in the following formula: Is disclosed. However, this production method has a problem in that the NH group at the 9-position of the carbazole ring reacts with other compounds in the reaction system, and impurities that are difficult to separate from the target product are by-produced.

On the other hand, in Patent Document 1, as shown in the following formula, the NH group of a carbazole compound having a carbazole ring substituted with a bromine atom is protected with a benzoyl group, and then reacted with a secondary amine to introduce a tertiary amino group. A method for producing a carbazole compound is described. According to this production method, since the NH group of the carbazole ring is protected with a benzoyl group, it is possible to suppress the formation of a by-product that becomes a problem in the method of Non-Patent Document 1. However, if the reaction used in the amination step is a reaction using a weak base such as the Ullmann reaction, the benzoyl group is retained without leaving the carbazole ring, but the Backwald-Hartwig reaction (Buchwald- In a reaction using a strong base (for example, sodium tert-butoxide) such as Hartwig reaction, the benzoyl group is eliminated from the carbazole ring. For this reason, in the method using a benzoyl group as a protecting group, the amination method is limited to a method using a weak base with poor reactivity, and it is difficult to increase the yield to an industrial level.

Non-Patent Document 2 discloses a method for producing a carbazole compound in which the NH group of a carbazole ring is protected with a benzyl group when a carbazole compound having a carbazole ring substituted with a bromine atom is aminated. The benzyl group is a protective group having a strong bond, and is hardly detached even when the compound is exposed to a strong acid or base. For this reason, according to this method, even when a relatively strong base is used in the amination step, the benzyl group is retained on the carbazole ring, and the formation of by-products can be suppressed.

US2006 / 051690A1 Specification

Journal of Photochemistry and Photobiology, A: Chemistry (2005), 174 (2), 125-129 Advanced Functional Materials (2003), 13 (6), 445-452

  When producing a carbazole compound having a tertiary amino group as described above, by protecting the amino group of the carbazole ring with a benzyl group, generation of by-products in the amination step can be suppressed. However, when the present inventors actually evaluated a method for producing a carbazole compound using a benzyl group as a protecting group, the inventors found for the first time that there were the following problems.

That is, in this production method, since the bond between the nitrogen atom of the carbazole ring and the benzyl group is strong, the elimination reaction hardly proceeds when the benzyl group is eliminated using an acid after amination. It was found that the target carbazole compound could not be obtained in a sufficient yield. In particular, when a plurality of amino groups were introduced into the carbazole ring in the amination step, it was also found that the benzyl group was more difficult to remove and the yield of the target product was lowered. Further investigations have shown that in the method for producing a carbazole compound using a benzyl group as a protecting group, the yield is lowered even when a ditolylamino group is introduced into the carbazole ring. This is because AlCl ₃ used for elimination of the benzyl group is a Lewis acid, so the reactivity of the benzyl group increases during the elimination process, and the polymer is produced by the reaction of the benzyl group with the tolyl group of the amino group. It was thought to be due to this. Furthermore, in the method for producing a carbazole compound using a benzyl group as a protecting group, an unreacted product (mainly secondary amine) remaining in the amination step and the benzyl group are prevented from side-reacting in the elimination step. It is essential to purify the target product later. For this reason, the purification cost and time are increased, and the deprotection of the benzyl group cannot be performed while amination is performed, thereby simplifying the process.
Therefore, in order to solve the problems of the prior art, the present inventors can suppress the production of by-products and can obtain a high yield of a carbazole compound having a tertiary amino group. The present invention has been studied for the purpose of providing a method for producing a carbazole compound having a tertiary amino group that can simplify the process, and a compound used as an intermediate of the production method.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a butoxycarbonyl group as a protecting group for protecting the NH group at the 9-position of the carbazole ring, thereby producing a by-product in the amination step. It was found that the production of the product can be suppressed and at the same time, the protecting group can be easily removed, and a carbazole compound having a tertiary amino group can be obtained in high yield. Furthermore, it has been found that this method can simplify the production process as compared with the case where a benzyl group is used as a protecting group. Specifically, the present invention has the following configuration.
[1] A carbazole having a tertiary amino group, which comprises a step of introducing a tertiary amino group into a compound having a 9-butoxycarbonylcarbazole structure and a step of removing the butoxycarbonyl group from the compound. Compound production method.
[2] The production method according to [1], wherein the compound containing the 9-butoxycarbonylcarbazole structure has a reactive group in at least one of positions 1 to 8 of the carbazole ring.
[3] The production method according to [2], wherein the reactive group is a halogen atom.
[4] Any one of [1] to [3], wherein the tertiary amino group is introduced by reacting the compound containing the 9-butoxycarbonylcarbazole structure with a secondary amine. Manufacturing method.
[5] The production method according to [4], wherein a palladium catalyst is used when the compound containing the 9-butoxycarbonylcarbazole structure is reacted with the secondary amine.
[6] The [4] or [5], wherein the secondary amine is diarylamine, dialkylamine, alkylarylamine, carbazole, acridan, phenoxazine, phenothiazine or 5,10-dihydrophenazine. (However, the aryl group and the alkyl group present in the diarylamine, the dialkylamine, and the alkylarylamine may each be substituted, and the 1- to 8-positions of the carbazole, 1- 9 position, 1-4 and 6-9 position of the phenoxazine, 1-4 and 6-9 position of the phenothiazine, and 1-9 position of the 5,10-dihydrophenazine may be substituted.) .
[7] The production method according to [4] or [5], wherein the secondary amine is a diarylamine (however, the aryl group present in the diarylamine may be substituted). .
[8] The removal of a butoxycarbonyl group is performed by bringing a compound containing a 9-butoxycarbonylcarbazole structure into which a tertiary amino group has been introduced into contact with an acidic compound, according to [1] to [7] The manufacturing method of any one of Claims.
[9] The method according to any one of [1] to [8], wherein the step of removing the butoxycarbonyl group is performed without performing purification in the step of introducing the tertiary amino group. Manufacturing method.
[10] The production according to any one of [1] to [9], wherein the step of removing the butoxycarbonyl group is also performed while the step of introducing the tertiary amino group is performed. Method.

［一般式（１）において、Ｒ¹〜Ｒ⁸は各々独立に水素原子または置換基を表すが、Ｒ¹〜Ｒ⁸の少なくとも１つは３級アミノ基を表す。Ｒ¹とＲ²、Ｒ²とＲ³、Ｒ³とＲ⁴、Ｒ⁴とＲ⁵、Ｒ⁵とＲ⁶、Ｒ⁶とＲ⁷、Ｒ⁷とＲ⁸はそれぞれ互いに結合して環状構造を形成していてもよい。］
［１２］ 前記一般式（１）のＲ³およびＲ⁶の少なくとも一方が３級アミノ基であることを特徴とする［１１］に記載の化合物。
［１３］ 前記３級アミノ基がジアリールアミノ基、ジアルキルアミノ基、アルキルアリールアミノ基、カルバゾール−９−イル基、アクリダン−１０−イル基、フェノキサジン−１０−イル基、フェノチアジン−１０−イル基または５，１０−ジヒドロフェナジン−１０−イル基であることを特徴とする［１１］または［１２］に記載の化合物（ただし、前記ジアリールアミノ基、前記ジアルキルアミノ基および前記アルキルアリールアミノ基に存在するアリール基およびアルキル基はそれぞれ置換されていてもよく、また、前記カルバゾール−９−イル基の１〜８位、アクリダン−１０−イル基の１〜９位、フェノキサジン−１０−イル基の１〜４および６〜９位、フェノチアジン−１０−イル基の１〜４および６〜９位、並びに５，１０−ジヒドロフェナジン−１０−イル基の１〜９位は置換されていてもよい。）。
［１４］ 前記３級アミノ基がジアリールアミノ基であることを特徴とする［１１］または［１２］に記載の化合物（ただし、前記ジアリールアミノ基に存在するアリール基は置換されていてもよい。）。
［１５］ 下記一般式（５）で表される化合物。

［一般式（５）において、Ｒ¹¹〜Ｒ¹⁸は各々独立に水素原子または置換基を表すが、Ｒ¹³およびＲ¹⁶の少なくとも一方は下記一般式（６）〜（９）のいずれかで表される構造を有する。Ｒ¹¹とＲ¹²、Ｒ¹²とＲ¹³、Ｒ¹³とＲ¹⁴、Ｒ¹⁴とＲ¹⁵、Ｒ¹⁵とＲ¹⁶、Ｒ¹⁶とＲ¹⁷、Ｒ¹⁷とＲ¹⁸はそれぞれ互いに結合して環状構造を形成していてもよい。］

［一般式（６）〜（９）において、Ｒ³¹〜Ｒ³⁸、Ｒ⁴¹〜Ｒ⁴⁸、Ｒ⁵¹〜Ｒ⁵⁸、Ｒ⁶¹〜Ｒ⁶⁵、Ｒ⁷¹〜Ｒ⁸⁰は、各々独立に水素原子または置換基を表す。Ｒ³¹とＲ³²、Ｒ³²とＲ³³、Ｒ³³とＲ³⁴、Ｒ³⁵とＲ³⁶、Ｒ³⁶とＲ³⁷、Ｒ³⁷とＲ³⁸、Ｒ⁴¹とＲ⁴²、Ｒ⁴²とＲ⁴³、Ｒ⁴³とＲ⁴⁴、Ｒ⁴⁵とＲ⁴⁶、Ｒ⁴⁶とＲ⁴⁷、Ｒ⁴⁷とＲ⁴⁸、Ｒ⁵¹とＲ⁵²、Ｒ⁵²とＲ⁵³、Ｒ⁵³とＲ⁵⁴、Ｒ⁵⁵とＲ⁵⁶、Ｒ⁵⁶とＲ⁵⁷、Ｒ⁵⁷とＲ⁵⁸、Ｒ⁶¹とＲ⁶²、Ｒ⁶²とＲ⁶³、Ｒ⁶³とＲ⁶⁴、Ｒ⁶⁴とＲ⁶⁵、Ｒ⁵⁴とＲ⁶¹、Ｒ⁵⁵とＲ⁶⁵、Ｒ⁷¹とＲ⁷²、Ｒ⁷²とＲ⁷³、Ｒ⁷³とＲ⁷⁴、Ｒ⁷⁵とＲ⁷⁶、Ｒ⁷⁶とＲ⁷⁷、Ｒ⁷⁷とＲ⁷⁸、Ｒ⁷⁹とＲ⁸⁰は互いに結合して環状構造を形成していてもよい。＊は結合位置を表す。］
［１６］ 一般式（５）で表される化合物からなるドナー材料。
［１７］ 遅延蛍光体用であることを特徴とする［１６］に記載のドナー材料。
［１８］ 一般式（５）で表される化合物のカルバゾール環の９位をアクセプターで置換することを特徴とする蛍光体の製造方法。
［１９］ 一般式（５）で表される化合物と下記一般式（１０）で表される化合物とを反応させることにより、下記一般式（１１）で表される遅延蛍光体を製造することを特徴とする［１８］に記載の蛍光体の製造方法。
一般式（１０）
Ｘ−Ａ
［一般式（１０）において、Ｘはハロゲン原子を表し、Ａはアクセプターを表す。］

［一般式（１１）において、Ｒ¹¹〜Ｒ¹⁸は各々独立に水素原子または置換基を表すが、Ｒ¹³およびＲ¹⁶の少なくとも一方は一般式（６）〜（９）のいずれかで表される構造を有する。Ａはアクセプターを表す。Ｒ¹¹とＲ¹²、Ｒ¹²とＲ¹³、Ｒ¹³とＲ¹⁴、Ｒ¹⁴とＲ¹⁵、Ｒ¹⁵とＲ¹⁶、Ｒ¹⁶とＲ¹⁷、Ｒ¹⁷とＲ¹⁸はそれぞれ互いに結合して環状構造を形成していてもよい。］
［２０］ 前記蛍光体が遅延蛍光体であることを特徴とする［１８］または［１９］に記載の蛍光体の製造方法。 [11] A compound represented by the following general formula (1).

[In General Formula (1), R ^{1 to} R ⁸ each independently represents a hydrogen atom or a substituent, but at least one of R ^{1 to} R ⁸ represents a tertiary amino group. R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ are bonded to each other to form a cyclic structure. It may be formed. ]
[12] The compound according to [11], wherein at least one of R ³ and R ^{6 in} the general formula (1) is a tertiary amino group.
[13] The tertiary amino group is a diarylamino group, a dialkylamino group, an alkylarylamino group, a carbazol-9-yl group, an acridan-10-yl group, a phenoxazin-10-yl group, or a phenothiazin-10-yl group. Or a compound according to [11] or [12], wherein the compound is a 5,10-dihydrophenazin-10-yl group (provided in the diarylamino group, the dialkylamino group and the alkylarylamino group) The aryl group and the alkyl group may be substituted, respectively, 1 to 8 position of the carbazol-9-yl group, 1 to 9 position of the acridan-10-yl group, phenoxazin-10-yl group 1-4 and 6-9 positions, 1-4 and 6-9 positions of the phenothiazin-10-yl group, and 5,10 -Positions 1-9 of the dihydrophenazin-10-yl group may be substituted.
[14] The compound according to [11] or [12], wherein the tertiary amino group is a diarylamino group (provided that the aryl group present in the diarylamino group may be substituted). ).
[15] A compound represented by the following general formula (5).

[In General Formula (5), R ^{11 to} R ¹⁸ each independently represents a hydrogen atom or a substituent, and at least one of R ¹³ and R ¹⁶ is represented by any one of the following General Formulas (6) to (9). Has a structure. R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ are bonded to each other to form a cyclic structure. It may be formed. ]

[In General Formulas (6) to (9), R ^{31 to} R ³⁸ , R ^{41 to} R ⁴⁸ , R ^{51 to} R ⁵⁸ , R ^{61 to} R ⁶⁵ , and R ^{71 to} R ⁸⁰ are each independently a hydrogen atom or a substituent. Represents a group. R ³¹ and R ³² , R ³² and R ³³ , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R ⁴³ And R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , R ⁴⁶ and R ⁴⁷ , R ⁴⁷ and R ⁴⁸ , R ⁵¹ and R ⁵² , R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁴ , R ⁵⁵ and R ⁵⁶ , R ⁵⁶ and R ⁵⁷ , ^R57 and ^R58 , ^R61 and ^R62 , ^R62 and ^R63 , ^R63 and ^R64 , ^R64 and ^R65 , ^R54 and ^R61 , ^R55 and ^R65 , ^R71 and ^R72 , R ⁷² and R ⁷³ , R ⁷³ and R ⁷⁴ , R ⁷⁵ and R ⁷⁶ , R ⁷⁶ and R ⁷⁷ , R ⁷⁷ and R ⁷⁸ , and R ⁷⁹ and R ⁸⁰ may be bonded to each other to form a cyclic structure. * Represents a bonding position. ]
[16] A donor material comprising a compound represented by the general formula (5).
[17] The donor material according to [16], which is used for a delayed phosphor.
[18] A method for producing a phosphor, comprising substituting the 9-position of the carbazole ring of the compound represented by the general formula (5) with an acceptor.
[19] Producing a delayed phosphor represented by the following general formula (11) by reacting a compound represented by the general formula (5) with a compound represented by the following general formula (10): [18] The method for producing a phosphor according to [18].
General formula (10)
X-A
[In General Formula (10), X represents a halogen atom, and A represents an acceptor. ]

[In General Formula (11), R ^{11 to} R ¹⁸ each independently represents a hydrogen atom or a substituent, and at least one of R ¹³ and R ¹⁶ is represented by any one of General Formulas (6) to (9). It has a structure. A represents an acceptor. R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ are bonded to each other to form a cyclic structure. It may be formed. ]
[20] The method for producing a phosphor according to [18] or [19], wherein the phosphor is a delayed phosphor.

  According to the production method of the present invention, a carbazole compound having a tertiary amino group can be produced in a high yield while suppressing the formation of by-products. Moreover, the manufacturing process of the carbazole compound having a tertiary amino group can be simplified.

Was determined from the molecular orbital calculation, a Delta] E _ST various donors is a graph showing each donor. It is a schematic sectional drawing which shows the layer structural example of an organic electroluminescent element.

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 and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value. In addition, the isotope species of the hydrogen atom present in the molecule of the compound used in the present invention is not particularly limited. For example, all the hydrogen atoms in the molecule may be ¹ H, or a part or all of them are ² H. (Deuterium D) may be used.

<Method for producing carbazole compound having tertiary amino group>
The method for producing a carbazole compound having a tertiary amino group according to the present invention includes a step of introducing a tertiary amino group into a compound containing a 9-butoxycarbonylcarbazole structure (amination step), and removing the butoxycarbonyl group from the compound. Including a step (desorption step). Hereinafter, each step will be described. Here, a step (protection step) of introducing a butoxycarbonyl group at the 9-position of a carbazole ring of a compound containing a carbazole structure, which is performed prior to the amination step, will be described first. In addition, the manufacturing method of this invention is not limited to the following processes.

[1] Protection Step In the protection step, a butoxycarbonyl group is introduced as a protecting group at the 9-position of the carbazole ring of the compound having a carbazole structure to obtain a compound containing a 9-butoxycarbonylcarbazole structure.
In this protection step, specifically, a compound having a carbazole structure and a compound having a butoxycarbonyl group are reacted in a reaction solvent to generate a compound having a 9-butoxycarbonylcarbazole structure.

  The compound having a carbazole structure as a starting material may be a compound having a carbazole ring, and substituents may be introduced into the carbazole ring, or the substituents introduced into the carbazole ring may be bonded to each other to form a ring. A structure may be formed. In addition, the cyclic structure formed by bonding of substituents may be a cyclic structure connected to a constituent atom of a carbazole ring or a condensed ring condensed with a carbazole ring. In the following description, a compound including this carbazole structure is referred to as a “carbazole compound”, and a compound having a butoxycarbonyl group bonded to the 9-position of a carbazole ring of the compound including this carbazole structure (including a 9-butoxycarbonylcarbazole structure). Compound) is sometimes referred to as “butoxycarbonylcarbazole compound”.

The compound having a carbazole structure (carbazole compound) has at least one reactive group. Thereby, a tertiary amino group can be selectively introduced at a position having a reactive group in a subsequent amination step. The reactive group may be present in the carbazole ring, may be present in a substituent substituted on the carbazole ring, or may be present in a cyclic structure formed by combining the substituents. Is preferably present in at least one of positions 1 to 8 of the carbazole ring.
The position of the reactive group in the carbazole ring can be appropriately selected according to the target carbazole compound. For example, when synthesizing a carbazole compound useful as an organic semiconductor material, the starting carbazole compound preferably has a reactive group at any of the 2-position, 3-position, 6-position, and 7-position of the carbazole ring. It is more preferable to have a reactive group in at least one of the 3-position and the 6-position.

  The reactive group is not particularly limited as long as it can be eliminated in the amination step and converted to a tertiary amino group, such as p-toluenesulfonate group, trifluoromethanesulfonate group, binacolatoboryl group, boric acid group, fluorine. A pseudo-halogen group such as an atom, a chlorine atom, a bromine atom, and an iodine atom, a boric acid group, and a halogen atom can be exemplified, and a chlorine atom, a bromine atom, and an iodine atom are preferable, and a bromine atom is more preferable. .

一般式（２）、（３）において、Ｒ¹’〜Ｒ⁸’は各々独立に水素原子または置換基を表すが、Ｒ¹’〜Ｒ⁸’の少なくとも１つは反応性基を表す。Ｒ¹’とＲ²’、Ｒ²’とＲ³’、Ｒ³’とＲ⁴’、Ｒ⁴’とＲ⁵’、Ｒ⁵’とＲ⁶’、Ｒ⁶’とＲ⁷’、Ｒ⁷’とＲ⁸’はそれぞれ互いに結合して環状構造を形成していてもよい。Ｒ¹’〜Ｒ⁸’がとりうる置換基の説明と好ましい範囲、置換基同士が結合して形成する環状構造については後述する。 As the compound having a carbazole structure, for example, a compound represented by the following general formula (2) is preferably used. By the reaction of the compound represented by the general formula (2) and the compound having a butoxycarbonyl group, a compound represented by the following general formula (3), that is, a butoxycarbonylcarbazole compound can be obtained.

In the general formulas (2) and (3), R ¹ ′ to R ⁸ ′ each independently represents a hydrogen atom or a substituent, and at least one of R ¹ ′ to R ⁸ ′ represents a reactive group. R ¹ 'and R ^2', R ² 'and R ^3', R ³ 'and R ^4', R ⁴ 'and R ^5', R ⁵ 'and R ^6', R ⁶ 'and R ^7', R ⁷ 'And R ⁸ ' may be bonded to each other to form a cyclic structure. Description and preferred ranges of the substituents that R ¹ ′ to R ⁸ ′ can take, and a cyclic structure formed by combining the substituents will be described later.

Examples of the compound having a butoxycarbonyl group include di-tert-butyl dicarbonate,
tert-Butoxycarbonylamide, tert-butoxycarbonyl azide and the like can be used.
The ratio of the compound having a butoxycarbonyl group to be subjected to the reaction is preferably 10 to 1 mol, more preferably 3 to 1 mol, relative to 1 mol of the carbazole compound.

  The reaction solvent for reacting the carbazole compound and the compound having a butoxycarbonyl group is not particularly limited as long as it is inert to the reaction. For example, aromatics such as benzene, toluene, xylene and chlorobenzene, diethyl Ethers such as ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, diethylene glycol dimethyl ether, esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl propionate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketones, hydrocarbons such as hexane, heptane, octane and nonane, halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, organic acids such as formic acid, acetic acid and propionic acid N, N- dimethylformamide, N, N- dimethylacetamide, include polar solvents and water, such as N- methylpyrrolidone, a mixed solvent thereof can be used. The amount of the reaction solvent is preferably 1000 to 3 times, and more preferably 100 to 5 times the amount of the carbazole compound.

  The reaction conditions can be appropriately set according to the raw materials used, the type of solvent, and the like. For example, the reaction temperature is preferably 200 to -100 ° C, and more preferably 100 to 0 ° C. The reaction time is preferably 24 to 1 hour, and more preferably 12 to 1 hour. The reaction is preferably performed with stirring.

[2] Amination step In the amination step, a tertiary amino group is introduced into the compound containing the 9-butoxycarbonylcarbazole structure obtained in the protection step.
Here, the butoxycarbonyl group of a compound having a 9-butoxycarbonylcarbazole structure (butoxycarbonylcarbazole compound) functions as a protecting group for protecting the NH group at the 9-position of the carbazole ring from the reaction in the amination step. The butoxycarbonyl group is hardly removed even when the amination step is performed in the presence of a relatively strong base, and the NH group of the carbazole ring can be reliably protected. Thereby, it is possible to suppress the formation of by-products while promoting the reaction using a strong base, and to obtain the target product in this step, a butoxycarbonylcarbazole compound having a tertiary amino group in a high yield. .

The amination step is preferably performed using a coupling reaction between a butoxycarbonylcarbazole compound and a secondary amine. The coupling reaction is not particularly limited, and any known coupling reaction for bonding an aromatic compound and an amine can be used. Among them, a so-called back reaction is performed in the presence of a palladium catalyst and a base. It is preferable to use the Wald-Hartwig reaction. Thereby, the target carbazole compound having a tertiary amino group can be obtained in high yield.
Specifically, in the amination step by the coupling reaction, the butoxycarbonylcarbazole compound obtained in the protection step and the secondary amine are reacted in the presence of a metal catalyst and a base. As a result, the reactive amine of the 9-butoxycarbonylcarbazole compound is eliminated and the secondary amine is bonded to the position where the reactive group was bonded. As a result, a butoxycarbonylcarbazole compound having a tertiary amino group is produced.

一般式（１）において、Ｒ¹〜Ｒ⁸は各々独立に水素原子または置換基を表すが、Ｒ¹〜Ｒ⁸の少なくとも１つは３級アミノ基を表す。Ｒ¹とＲ²、Ｒ²とＲ³、Ｒ³とＲ⁴、Ｒ⁴とＲ⁵、Ｒ⁵とＲ⁶、Ｒ⁶とＲ⁷、Ｒ⁷とＲ⁸はそれぞれ互いに結合して環状構造を形成していてもよい。
Ｒ¹〜Ｒ⁸の少なくとも１つが表す３級アミノ基は、一般式（３）で表される化合物の反応性基が脱離した位置に２級アミンが結合することで形成されたものである。したがって、一般式（１）で表される化合物のカルバゾール環における３級アミノ基の位置は、一般式（３）で表される化合物のカルバゾール環における反応性基の位置に対応する。Ｒ¹〜Ｒ⁸がとりうる３級アミノ基、３級アミノ基以外の置換基および置換基同士が結合して形成する環状構造については後述する。 When the butoxycarbonylcarbazole compound obtained in the protection step is a compound represented by the above general formula (3), butoxycarbonyl having a tertiary amino group represented by the following general formula (1) is obtained by this amination step. A carbazole compound can be obtained.

In the general formula (1), R ^{1 to} R ⁸ each independently represent a hydrogen atom or a substituent, and at least one of R ^{1 to} R ⁸ represents a tertiary amino group. R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ are bonded to each other to form a cyclic structure. It may be formed.
The tertiary amino group represented by at least one of R ^{1 to} R ⁸ is formed by binding of a secondary amine to the position where the reactive group of the compound represented by the general formula (3) is eliminated. . Therefore, the position of the tertiary amino group in the carbazole ring of the compound represented by the general formula (1) corresponds to the position of the reactive group in the carbazole ring of the compound represented by the general formula (3). A tertiary amino group that can be taken by R ^{1 to} R ⁸ , a substituent other than the tertiary amino group, and a cyclic structure formed by combining the substituents will be described later.

The secondary amine is not particularly limited and may be appropriately selected depending on the target carbazole compound, but may be a diarylamine, dialkylamine, alkylarylamine, carbazole, acridan, phenoxazine, phenothiazine or 5,10- Dihydrophenazine is preferable, and diarylamine is more preferable. Thereby, a carbazole compound suitable as an organic semiconductor material can be obtained. In addition, the aryl group and alkyl group present in diarylamine, dialkylamine and alkylarylamine may be substituted, respectively, 1 to 8 position of carbazole, 1 to 9 position of acridan, 1 to 4 and 6 of phenoxazine. The 9th position, the 1-4th and 6th-9th positions of the phenothiazine, the 1st-9th position of the 5,10-dihydrophenazine may be substituted. For descriptions and preferred ranges of substituents that can be substituted on the aryl group, alkyl group, and carbazole, reference can be made to the descriptions and preferred ranges of substituents that can be taken by R ^{1 to} R ⁸ described later.
The ratio of the secondary amine used for the reaction is preferably 10 to 1 mol, more preferably 3 to 1 mol, per 1 mol of the butoxycarbonylcarbazole compound.

As the metal catalyst, a copper catalyst or a palladium catalyst can be used, and a palladium catalyst is preferably used. As a result, the target product in this step, butoxycarbonylcarbazole compound having a tertiary amino group, can be obtained in high yield.
Examples of the palladium catalyst include palladium acetate, palladium chloride, dichlorobis (triphenylphosphine) palladium, dichlorobis (triphenylphosphine) nickel, dichlorobis (tricyclohexylphosphine) palladium, and trisdibenzylideneacetonedipalladium. Or trisdibenzylideneacetone dipalladium is preferably used.
The addition amount of the palladium catalyst in the reaction solvent is preferably 100 to 0.5 mol%, more preferably 30 to 1 mol%, based on the butoxycarbonylcarbazole compound.
In addition, a ligand that forms a complex with the palladium catalyst may be added to the reaction solvent. Examples of the ligand include tri (tert-butyl) phosphonium tetrafluoroborate, 2-di-tert-butylphosphino-2 ′-(N, N-dimethylamino) biphenyl, and the like.

As the base, general bases such as sodium carbonate, potassium carbonate, potassium hydroxide and the like can be used. Alkali metal alkoxides such as sodium tert-butoxide and potassium tert-butoxide, strong bis (trimethylsilyl) sodium amide and the like. It is preferable to use a base. Thereby, a butoxycarbonylcarbazole compound having a tertiary amino group can be obtained in high yield. Further, the butoxycarbonyl group of the butoxycarbonylcarbazole compound is reliably retained as a protective group even when these bases are used, and the generation of by-products can be suppressed.
The amount of the base used is preferably 10 to 1 equivalent, more preferably 3 to 1 equivalent, with respect to the butoxycarbonylcarbazole compound.

The reaction solvent for performing the coupling reaction is not particularly limited as long as it is inert to the reaction, and can be appropriately selected from the reaction solvents exemplified in the protection step. The amount of the solvent used is preferably 1000 to 10 times the amount of the compound having a 9-butoxycarbonylcarbazole structure,
More preferably, the amount is 100 to 10 times.
The reaction conditions can be appropriately set according to the raw materials used, the type of solvent, and the like. For example, the reaction temperature is preferably 300 to -100 ° C, and more preferably 200 to 0 ° C. The reaction time is preferably 100 to 1 hour, and more preferably 24 to 1 hour. The reaction is preferably performed with stirring.

[3] Desorption step In the desorption step, the butoxycarbonyl group is desorbed from the butoxycarbonylcarbazole compound having a tertiary amino group to obtain the target carbazole compound having a tertiary amino group.
The elimination step can be performed, for example, by bringing a butoxycarbonylcarbazole compound having a tertiary amino group into contact with an acidic compound.
In the butoxycarbonylcarbazole compound, the butoxycarbonyl group is relatively easily eliminated by contact with an acidic compound even if the number of substitutions of the tertiary amino group is relatively large. In addition, since this elimination step does not use a compound that promotes the reaction between the protecting group and the amine, such as a Lewis acid in the benzyl group, generation of by-products can be suppressed. For this reason, in this elimination step, a carbazole compound having a tertiary amino group can be obtained in a high yield regardless of the type and number of substituents of the tertiary amino group.

As the acidic compound used for elimination of the butoxycarbonyl group, strong acids such as hydrochloric acid, trifluoroacetic acid, hydrochloric acid-ethyl acetate solution, hydrochloric acid-methanol solution, trifluoromethanesulfonic acid, p-toluenesulfonic acid and the like can be preferably used.
The amount of the acidic compound used is preferably 100 to 0.1 equivalent, more preferably 10 to 0.1 equivalent, relative to the butoxycarbonylcarbazole compound.

The reaction solvent for performing the coupling reaction is not particularly limited as long as it is inert to the reaction, and can be appropriately selected from the reaction solvents exemplified in the protection step. As a usage-amount of a solvent, it is preferable that it is 1000-5 times amount with respect to the compound which has a 9-butoxycarbonylcarbazole structure which has a tertiary amino group, and it is more preferable that it is 100-10 times amount.
The reaction conditions can be appropriately set according to the raw materials used, the type of solvent, and the like. For example, the reaction temperature is preferably 300 to -100 ° C, and more preferably 200 to -80 ° C. The reaction time is preferably 100 to 1 hour, and more preferably 24 to 1 hour. The reaction is preferably performed with stirring.

  This elimination step may be performed by purifying the butoxycarbonylcarbazole compound having a tertiary amino group obtained in the amination step and adding an acidic compound to the solution of the purified product, or performing the amination step. Further, the reaction may be performed by directly adding an acidic compound to the reaction solution. By using the latter method, the purification process before the desorption process can be omitted, and thus the manufacturing process can be simplified. Here, although the unreacted secondary amine remains in the reaction solution after the amination step, the acidic compound used in the elimination step is a reaction between the butoxycarbonyl group and the secondary amine as described above. Therefore, even when a method of adding an acidic compound directly to the reaction solution is used, a high yield can be obtained.

一般式（４）において、Ｒ¹〜Ｒ⁸は各々独立に水素原子または置換基を表すが、Ｒ¹〜Ｒ⁸の少なくとも１つは３級アミノ基を表す。Ｒ¹とＲ²、Ｒ²とＲ³、Ｒ³とＲ⁴、Ｒ⁴とＲ⁵、Ｒ⁵とＲ⁶、Ｒ⁶とＲ⁷、Ｒ⁷とＲ⁸はそれぞれ互いに結合して環状構造を形成していてもよい。 Through the above steps, a carbazole compound having a tertiary amino group is produced. For example, when the butoxycarbonylcarbazole compound having a tertiary amino group obtained in the amination step is a compound represented by the general formula (1), a carbazole compound represented by the following general formula (4) is obtained. Can do.

In the general formula (4), R ^{1 to} R ⁸ each independently represents a hydrogen atom or a substituent, and at least one of R ^{1 to} R ⁸ represents a tertiary amino group. R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ are bonded to each other to form a cyclic structure. It may be formed.

In the general formula (4) and the above general formula (1), the tertiary amino group may be only one of R ^{1 to} R ⁸ , or may be two or more.
When the tertiary amino group is only one of R ^{1 to} R ⁸ , R ³ or R ⁶ is preferably a tertiary amino group, and R ³ is represented by the general formula (2). More preferably, it is a group.
On the other hand, when two or more of R ^{1 to} R ⁸ are tertiary amino groups, the tertiary amino group is at least one of R ^{1 to} R ⁴ and at least one of R ^{5 to} R ^8. It is preferable. At this time, the tertiary amino group is preferably ^{1 to} 3 of R ^{1 to} R ⁴ and 1 to 3 of R ^{5 to} R ⁸ , and one of R ^{1 to} R ⁴ or More preferably, it is one or two of R ^{5 to} R ⁸ . The number of tertiary amino groups in R ^{1 to} R ⁴ and the number of tertiary amino groups in R ^{5 to} R ⁸ may be the same or different, but are preferably the same. Among R ^{1 to} R ⁴ , R ² or R ³ is preferably a tertiary amino group, and at least R ³ is more preferably a tertiary amino group. Of R ^{5 to} R ⁸ , R ⁶ or R ⁷ is preferably a tertiary amino group, and at least R ⁶ is more preferably a tertiary amino group. A preferred compound is a compound in which R ³ and R ^{6 in} the general formula (1) are tertiary amino groups. The tertiary amino groups present in the general formulas (1) and (4) may be the same or different, but are preferably the same. Moreover, it is also preferable that the group represented by the general formula (1) has a symmetrical structure. That is, R ¹ and R ⁸ , R ² and R ⁷ , R ³ and R ⁶ , and R ⁴ and R ⁵ are preferably the same.
In addition, the preferable substituted position of the reactive group in said general formula (2), (3) is the same as the preferable substituted position of the tertiary amino group in general formula (1), (4), and said amino group The description of the preferred substitution position can be referred to corresponding to R ¹ ′ to R ⁸ ′.

As the tertiary amino group that R ^{1 to} R ⁸ can take, a diarylamino group, a dialkylamino group, an alkylarylamino group, a carbazol-9-yl group, an acridan-10-yl group, a phenoxazin-10-yl group, A phenothiazin-10-yl group or a 5,10-dihydrophenazin-10-yl group is preferable, and a diarylamino group is more preferable. Thereby, a carbazole compound suitable as an organic semiconductor material can be obtained. In addition, the aryl group and alkyl group present in the diarylamino group, dialkylamino group and alkylarylamino group may each be substituted, and the 1- to 8-position of the carbazol-9-yl group, acridan-10-yl. 1-9 position of group, 1-4 and 6-9 position of phenoxazin-10-yl group, 1-4 and 6-9 position of phenothiazin-10-yl group, and 5,10-dihydrophenazine-10- Positions 1-9 of the yl group may be substituted. For the explanation and preferred range of the substituent that can be substituted on the aryl group, alkyl group, and carbazol-9-yl group, the explanation and preferred range of the substituent that can be taken by the following R ^{1 to} R ⁸ can be referred to.

The substituents that R ^{1 to} R ⁸ can take include the above-mentioned tertiary amino groups, and R ¹ ′ to R ⁸ ′ include the above-mentioned reactive groups. In addition to these, R ^{1 to} R ⁸ and Examples of the substituent that R ¹ ′ to R ⁸ ′ can take include, for example, a hydroxy group, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an alkylthio group having 1 to 20 carbon atoms. , An alkyl-substituted amino group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, carbon An alkynyl group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an alkylsulfonyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an amide group, an alkylamide group having 2 to 10 carbon atoms, Trialkyl having 3 to 20 carbon atoms Lil group, trialkylsilyl group having 4 to 20 carbon atoms, trialkylsilyl alkenyl group having 5 to 20 carbon atoms and an trialkylsilyl alkynyl group and a nitro group having 5 to 20 carbon atoms. Among these specific examples, those that can be substituted with a substituent may be further substituted. More preferred substituents are a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, carbon It is a substituted or unsubstituted heteroaryl group of 3 to 40. More preferable substituents are a fluorine atom, a chlorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, and a substituted group having 6 to 15 carbon atoms. Or it is an unsubstituted aryl group, a C3-C12 substituted or unsubstituted heteroaryl group.

R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ are bonded to each other to form a cyclic structure. to time, the above R ¹ 'and R ^2', R ² 'and R ^3', R ³ 'and R ^4', R ⁴ 'and R ^5', 'and R ^6' R ^5, and R ⁶ 'R ^{When 7} ′, R ⁷ ′ and R ⁸ ′ are bonded to each other to form a cyclic structure, the cyclic structure may be an aromatic ring or an aliphatic ring, and may contain a heteroatom. Further, the cyclic structure may be a condensed ring having two or more rings. The hetero atom here is preferably selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. Examples of cyclic structures formed include benzene ring, naphthalene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, imidazoline ring, oxazole ring, isoxazole ring, thiazole And a ring, an isothiazole ring, a cyclohexadiene ring, a cyclohexene ring, a cyclopentaene ring, a cycloheptatriene ring, a cycloheptadiene ring, and a cycloheptaene ring.

Hereinafter, specific examples of the compound produced by the method for producing a carbazole compound having a tertiary amino group of the present invention will be exemplified. In the following compounds, Ph represents a phenyl group, and p-Tolyl represents a p-tolyl group. However, the carbazole compound produced in the present invention should not be limitedly interpreted by these specific examples.

一般式（１）において、Ｒ¹〜Ｒ⁸は各々独立に水素原子または置換基を表すが、Ｒ¹〜Ｒ⁸の少なくとも１つは３級アミノ基を表す。Ｒ¹とＲ²、Ｒ²とＲ³、Ｒ³とＲ⁴、Ｒ⁴とＲ⁵、Ｒ⁵とＲ⁶、Ｒ⁶とＲ⁷、Ｒ⁷とＲ⁸はそれぞれ互いに結合して環状構造を形成していてもよい。Ｒ¹〜Ｒ⁸の説明と好ましい範囲については上記した通りである。
一般式（１）で表される化合物は、本発明の３級アミノ基を有するカルバゾール化合物の製造方法において上記のアミノ化工程で得られる中間体であり、この一般式（１）で表される化合物に上記の脱離工程行うことにより、３級アミノ基を有するカルバゾール化合物を製造することができる。 [Compound represented by general formula (1)]
The compound represented by the general formula (1) is a novel compound.

In the general formula (1), R ^{1 to} R ⁸ each independently represent a hydrogen atom or a substituent, and at least one of R ^{1 to} R ⁸ represents a tertiary amino group. R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ are bonded to each other to form a cyclic structure. It may be formed. The description and preferred range of R ^{1 to} R ⁸ are as described above.
The compound represented by the general formula (1) is an intermediate obtained in the above-mentioned amination step in the method for producing a carbazole compound having a tertiary amino group of the present invention, and is represented by the general formula (1). Carbazole compounds having a tertiary amino group can be produced by subjecting the compound to the above elimination step.

[Application examples of carbazole compounds having a tertiary amino group]
For example, like the carbazole compound represented by the general formula (4), the deprotected carbazole compound having a tertiary amino group produced by the production method of the present invention is useful as an organic semiconductor material. The carbazole structure having a tertiary amino group functions as a donor that supplies energy to the acceptor by being combined with an acceptor atomic group. Therefore, the deprotected carbazole compound having a tertiary amino group produced by the production method of the present invention is used as a raw material for supplying a donor site, that is, a donor material when producing a compound having a donor site and an acceptor site. Is also useful. A compound having a carbazole structure having a tertiary amino group as a donor site exhibits excellent characteristics as a light-emitting material, a host material, an electron transport material, a hole transport material, and the like of an organic electroluminescence element, and is extremely useful.

Among the carbazole compounds represented by the above general formula (4), the compound represented by the following general formula (5) is a novel compound and is useful as a raw material (donor material) for supplying a donor site of a phosphor. Is expensive. In particular, the compound represented by the following general formula (5) is useful as a raw material (donor material for delayed phosphor) that supplies the donor site of the delayed phosphor.

In the general formula (5), R ^{11 to} R ¹⁸ each independently represent a hydrogen atom or a substituent, and at least one of R ¹³ and R ¹⁶ is represented by any one of the following general formulas (6) to (9). It has a structure. R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ are bonded to each other to form a cyclic structure. It may be formed. For the explanation and preferred range of R ^{11 to} R ¹⁸ in the general formula (5), the explanation and preferred range of R ^{1 to} R ⁸ in the general formula (1) can be referred to.

In the general formulas (6) to (9), R ^{31 to} R ³⁸ , R ^{41 to} R ⁴⁸ , R ^{51 to} R ⁵⁸ , R ^{61 to} R ⁶⁵ , and R ^{71 to} R ⁸⁰ are each independently a hydrogen atom or a substituent. Represents. For the explanation and preferred range of the substituent, reference can be made to the explanation and preferred range of the substituent that can be taken by the above R ^{1 to} R ⁸ . R ³¹ and R ³² , R ³² and R ³³ , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R ⁴³ And R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , R ⁴⁶ and R ⁴⁷ , R ⁴⁷ and R ⁴⁸ , R ⁵¹ and R ⁵² , R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁴ , R ⁵⁵ and R ⁵⁶ , R ⁵⁶ and R ⁵⁷ , ^R57 and ^R58 , ^R61 and ^R62 , ^R62 and ^R63 , ^R63 and ^R64 , ^R64 and ^R65 , ^R54 and ^R61 , ^R55 and ^R65 , ^R71 and ^R72 , R ⁷² and R ⁷³ , R ⁷³ and R ⁷⁴ , R ⁷⁵ and R ⁷⁶ , R ⁷⁶ and R ⁷⁷ , R ⁷⁷ and R ⁷⁸ , and R ⁷⁹ and R ⁸⁰ may be bonded to each other to form a cyclic structure. For the explanation and preferred range of the cyclic structure, reference can be made to the explanation and preferred range when R ¹ and R ^{2 and the} like are bonded to each other to form a cyclic structure. * Represents a bonding position to the benzene ring constituting the carbazole of the general formula (5).

  In order to produce a delayed phosphor from the compound represented by the general formula (5), the 9-position of the carbazole ring of the compound represented by the general formula (5) may be substituted with an acceptor. Specifically, by reacting a compound represented by the general formula (5) with, for example, a compound represented by the following general formula (10), a delayed phosphor represented by the following general formula (11) is obtained. Can be manufactured.

General formula (10)
X-A
In the general formula (10), X represents a halogen atom, and specific examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a bromine atom and an iodine atom can be preferably used. A represents an acceptor. The acceptor here refers to an atom or an atomic group that exhibits an electron withdrawing ability when substituted at the 9-position of the carbazole ring of the compound represented by the general formula (5). Preferably, it is an aromatic substituent having electron withdrawing ability. That is, the acceptor represented by A preferably has at least one aromatic ring or heteroaromatic ring having electron withdrawing ability, and is bonded to X by the aromatic ring or heteroaromatic ring. The aromatic ring or heteroaromatic ring may have a condensed ring structure, and the heteroaromatic ring is preferably a heteroaromatic ring containing a nitrogen atom. Specific examples of the aromatic ring and heteroaromatic ring include benzene ring, biphenylene ring, naphthalene ring, fluorene ring, triphenylene ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, triazole ring, thiazole ring, pyrrole ring. it can. The bonding site to the carbazole ring in the aromatic ring or heteroaromatic ring is not particularly limited, but it is preferable to bond to the carbazole ring at a carbon atom among atoms constituting the aromatic ring or heteroaromatic ring. The acceptor represented by A is preferably an aromatic substituent having an electron withdrawing group. The electron withdrawing group here means a substituent having a positive Hammett σ _p value. For example, a cyano group can be mentioned as a preferred example.

一般式（１１）において、Ｒ¹¹〜Ｒ¹⁸は各々独立に水素原子または置換基を表すが、Ｒ¹³およびＲ¹⁶の少なくとも一方は上記一般式（６）〜（９）のいずれかで表される構造を有する。Ａはアクセプターを表す。Ｒ¹¹とＲ¹²、Ｒ¹²とＲ¹³、Ｒ¹³とＲ¹⁴、Ｒ¹⁴とＲ¹⁵、Ｒ¹⁵とＲ¹⁶、Ｒ¹⁶とＲ¹⁷、Ｒ¹⁷とＲ¹⁸はそれぞれ互いに結合して環状構造を形成していてもよい。Ｒ¹¹〜Ｒ¹⁸およびＡの説明と好ましい範囲については、一般式（５）および一般式（１０）の対応する記載を参照することができる。

In the general formula (11), R ^{11 to} R ¹⁸ each independently represent a hydrogen atom or a substituent, and at least one of R ¹³ and R ¹⁶ is represented by any one of the above general formulas (6) to (9). It has a structure. A represents an acceptor. R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ are bonded to each other to form a cyclic structure. It may be formed. For the explanation and preferred ranges of R ^{11 to} R ¹⁸ and A, the corresponding descriptions of general formula (5) and general formula (10) can be referred to.

The compound represented by the general formula (5), as compared to a donor material that has been used conventionally, has a feature that the donor itself Delta] E _ST is small. Delta] E _ST is determined from the difference between the excited triplet energy and the excited singlet energy obtained from theoretical calculations. Figure 1 is a Delta] E _ST various donors is a graph showing each donor. Generally the delay phosphor express its function is involved greatly Delta] E _ST. Conventional delayed phosphors are designed with a combination of a donor and an acceptor. Then, when selecting an acceptor material, the smaller the Delta] E _ST with donor material, Delta] E _ST of the delayed fluorescent material can be in combination of smaller are common. According to FIG. 1, when diphenylamine (ΔE _ST = 1.1) or carbazole (ΔE _ST = 0.96) is selected as the donor material, ΔE _ST becomes very large. Many conventional delayed phosphors have used donor material in the range indicated by region “a” in FIG. These Delta] E _ST is smaller than the diphenylamine or carbazole, but still high region. On the other hand, the compound represented by the general formula (5) is a donor material in a new region represented by the region “b” in FIG. Since the compound represented by the general formula (5) is Delta] E _ST is sufficiently small, it is possible to provide a smaller delay phosphor Delta] E _ST by using as a donor material. According to the production method of the present invention, the compound represented by the general formula (5) can be easily produced, and therefore the present invention is extremely useful.

[Organic electroluminescence device]
Hereinafter, an organic electroluminescence element will be described as an example of an organic device to which a carbazole compound having a tertiary amino group produced by the production method of the present invention is applied.
The organic electroluminescence element has a structure in which at least an anode, a cathode, and an organic layer are formed between the anode and the cathode. The organic layer includes at least a light emitting layer, and may consist of only the light emitting layer, or may have one or more organic layers in addition to the light emitting layer. Examples of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer. The hole transport layer may be a hole injection / transport layer having a hole injection function, and the electron transport layer may be an electron injection / transport layer having an electron injection function. A specific structural example of the organic electroluminescence element is shown in FIG. In FIG. 2, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light emitting layer, 6 is an electron transport layer, and 7 is a cathode.
Below, each member and each layer of an organic electroluminescent element are demonstrated.

(substrate)
The organic electroluminescence device of the present invention is preferably supported on a substrate. The substrate is not particularly limited and may be any substrate conventionally used for organic electroluminescence elements. For example, a substrate made of glass, transparent plastic, quartz, silicon, or the like can be used.

(anode)
As the anode in the organic electroluminescence element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used. For the anode, a thin film may be formed by vapor deposition or sputtering of these electrode materials, and a pattern of a desired shape may be formed by photolithography, or when pattern accuracy is not so high (about 100 μm or more) ), A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material. Or when using the material which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.

(cathode)
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, Suitable are a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, a lithium / aluminum mixture, aluminum and the like. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic electroluminescence element is transparent or translucent, the emission luminance is advantageously improved.
In addition, by using the conductive transparent material mentioned in the description of the anode as a cathode, a transparent or semi-transparent cathode can be produced. By applying this, an element in which both the anode and the cathode are transparent is used. Can be produced.

(Light emitting layer)
The light emitting layer is a layer that emits light after excitons are generated by recombination of holes and electrons injected from each of the anode and the cathode, and the light emitting material may be used alone for the light emitting layer. , Preferably including a luminescent material and a host material. In order for the organic electroluminescent device and the organic photoluminescent device of the present invention to exhibit high luminous efficiency, it is important to confine singlet excitons and triplet excitons generated in the light emitting material in the light emitting material. Therefore, it is preferable to use a host material in addition to the light emitting material in the light emitting layer. As the host material, an organic compound in which at least one of excited singlet energy and excited triplet energy has a value higher than that of the light-emitting material can be used. As a result, singlet excitons and triplet excitons generated in the light emitting material can be confined in the molecule of the light emitting material, and the light emission efficiency can be sufficiently extracted. However, even if singlet excitons and triplet excitons cannot be sufficiently confined, there are cases where high luminous efficiency can be obtained, so that host materials that can achieve high luminous efficiency are particularly limited. And can be used in the present invention. In the organic light-emitting device or organic electroluminescence device of the present invention, light emission is generated from the light-emitting material contained in the light-emitting layer. This emission includes both fluorescence and delayed fluorescence. However, light emission from the host material may be partly or partly emitted.
When the host material is used, the amount of the light emitting material contained in the light emitting layer is preferably 0.1% by weight or more, more preferably 1% by weight or more, and 50% by weight or less. It is preferably 20% by weight or less, more preferably 10% by weight or less.
The host material in the light-emitting layer is preferably an organic compound that has a hole transporting ability and an electron transporting ability, prevents the emission of longer wavelengths, and has a high glass transition temperature.
The deprotected carbazole compound produced by the production method of the present invention may function as a light emitting material or may function as a host material in the organic electroluminescent device and the light emitting layer of the organic photoluminescent device.

(Injection layer)
The injection layer is a layer provided between the electrode and the organic layer for lowering the driving voltage and improving the luminance of light emission, and there are a hole injection layer and an electron injection layer, Further, it may be present between the cathode and the light emitting layer or the electron transport layer. The injection layer can be provided as necessary.

(Blocking layer)
The blocking layer is a layer that can prevent diffusion of charges (electrons or holes) and / or excitons existing in the light emitting layer to the outside of the light emitting layer. The electron blocking layer can be disposed between the light emitting layer and the hole transport layer and blocks electrons from passing through the light emitting layer toward the hole transport layer. Similarly, a hole blocking layer can be disposed between the light emitting layer and the electron transporting layer to prevent holes from passing through the light emitting layer toward the electron transporting layer. The blocking layer can also be used to block excitons from diffusing outside the light emitting layer. That is, each of the electron blocking layer and the hole blocking layer can also function as an exciton blocking layer. The term “electron blocking layer” or “exciton blocking layer” as used herein is used in the sense of including a layer having the functions of an electron blocking layer and an exciton blocking layer in one layer.

(Hole blocking layer)
The hole blocking layer has a function of an electron transport layer in a broad sense. The hole blocking layer has a role of blocking holes from reaching the electron transport layer while transporting electrons, thereby improving the recombination probability of electrons and holes in the light emitting layer. As the material for the hole blocking layer, the material for the electron transport layer described later can be used as necessary.

(Electron blocking layer)
The electron blocking layer has a function of transporting holes in a broad sense. The electron blocking layer has a role to block electrons from reaching the hole transport layer while transporting holes, thereby improving the probability of recombination of electrons and holes in the light emitting layer. .

(Exciton blocking layer)
The exciton blocking layer is a layer for preventing excitons generated by recombination of holes and electrons in the light emitting layer from diffusing into the charge transport layer. It becomes possible to efficiently confine in the light emitting layer, and the light emission efficiency of the device can be improved. The exciton blocking layer can be inserted on either the anode side or the cathode side adjacent to the light emitting layer, or both can be inserted simultaneously. That is, when the exciton blocking layer is provided on the anode side, the layer can be inserted adjacent to the light emitting layer between the hole transport layer and the light emitting layer, and when inserted on the cathode side, the light emitting layer and the cathode Between the luminescent layer and the light-emitting layer. Further, a hole injection layer, an electron blocking layer, or the like can be provided between the anode and the exciton blocking layer adjacent to the anode side of the light emitting layer, and the excitation adjacent to the cathode and the cathode side of the light emitting layer can be provided. Between the child blocking layer, an electron injection layer, an electron transport layer, a hole blocking layer, and the like can be provided. When the blocking layer is disposed, at least one of the excited singlet energy and the excited triplet energy of the material used as the blocking layer is preferably higher than the excited singlet energy and the excited triplet energy of the light emitting material.

(Hole transport layer)
The hole transport layer is made of a hole transport material having a function of transporting holes, and the hole transport layer can be provided as a single layer or a plurality of layers.
The hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic. Known hole transport materials that can be used include, for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indolocarbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, Examples include amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers. An aromatic tertiary amine compound and an styrylamine compound are preferably used, and an aromatic tertiary amine compound is more preferably used.

(Electron transport layer)
The electron transport layer is made of a material having a function of transporting electrons, and the electron transport layer can be provided as a single layer or a plurality of layers.
The electron transport material (which may also serve as a hole blocking material) may have a function of transmitting electrons injected from the cathode to the light emitting layer. Examples of the electron transport layer that can be used include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide oxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

This organic electroluminescent element emits light by applying an electric field between the anode and the cathode of the obtained element. At this time, if the light is emitted by excited singlet energy, light having a wavelength corresponding to the energy level is confirmed as fluorescence emission and delayed fluorescence emission. In addition, in the case of light emission by excited triplet energy, a wavelength corresponding to the energy level is confirmed as phosphorescence. Since normal fluorescence has a shorter fluorescence lifetime than delayed fluorescence, the emission lifetime can be distinguished from fluorescence and delayed fluorescence.
On the other hand, with respect to phosphorescence, in ordinary organic compounds such as the compounds of the present invention, the excited triplet energy is unstable and is converted into heat and the like, and the lifetime is short and it is immediately deactivated. In order to measure the excited triplet energy of a normal organic compound, it can be measured by observing light emission under extremely low temperature conditions.
The carbazole compound having a tertiary amino group produced by the production method of the present invention can be suitably used as a material for each organic layer constituting the organic electroluminescence device as described above. The use of the carbazole compound having a tertiary amino group is not limited to this. The carbazole compound produced in the present invention can be suitably used as an organic semiconductor material for other various organic devices.

  The features of the present invention will be described more specifically with reference to synthesis examples and examples. The following materials, processing details, processing procedures, and the like can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

３−ブロモカルバゾール（１０．０ｇ, ４０．６ｍｍｏｌ）と４−Ｎ，Ｎ−ジメチルアミノピリジン（０．５０ｇ,０．４１ｍｍｏｌ）をテトラヒドロフラン１００ｍｌに加え撹拌した。この混合物に、ジ−ｔｅｒｔ−ブチルジカーボネート（（ＢＯＣ）₂Ｏ：１１．５ｇ,５２．８ｍｍｏｌ）をゆっくりと滴下し、３５℃で終夜撹拌した。その後、反応液をエバポレーターで濃縮し、得られた濃縮物にメタノール１００ｍｌを加え、結晶を析出させた。得られた結晶を濾別した後、メタノールで洗浄し、乾燥した。これにより、中間体２ａを収量１２．０ｇ、収率８５％で得た。
¹Ｈ ＮＭＲ（６００ＭＨｚ，ＣＤＣｌ₃）δ８．６−８．４（１Ｈ），８．２−８．０（２Ｈ）、７．５−７．１（４Ｈ）、１．８−１．６（９Ｈ）；ＭＳ（７０ｅＶ，ＥＩ）ｍ／ｚ＝３４６（Ｍ＋）、３４８（Ｍ＋） Example 1 Synthesis of Compound 1 [1-1] Protection Step

3-Bromocarbazole (10.0 g, 40.6 mmol) and 4-N, N-dimethylaminopyridine (0.50 g, 0.41 mmol) were added to 100 ml of tetrahydrofuran and stirred. To this mixture, di-tert-butyl dicarbonate ((BOC) ₂ O: 11.5 g, 52.8 mmol) was slowly added dropwise and stirred at 35 ° C. overnight. Thereafter, the reaction solution was concentrated with an evaporator, and 100 ml of methanol was added to the obtained concentrate to precipitate crystals. The obtained crystals were filtered off, washed with methanol and dried. As a result, Intermediate 2a was obtained in a yield of 12.0 g and a yield of 85%.
¹ H NMR (600 MHz, CDCl ₃ ) δ 8.6-8.4 (1H), 8.2-8.0 (2H), 7.5-7.1 (4H), 1.8-1.6 ( 9H); MS (70 eV, EI) m / z = 346 (M +), 348 (M +)

中間体２ａ（１０．４ｇ，３０ｍｍｏｌ）、ジフェニルアミン（５．５８ｇ，３３ｍｍｏｌ）、酢酸パラジウム（Ｐｄ（ＯＡｃ）₂：０．５４ｇ,２．４ｍｍｏｌ）、およびナトリウムｔｅｒｔ−ブトキシド（ＮａＯｔ−Ｂｕ：６．９２ｇ，７２ｍｍｏｌ）を脱水トルエン１６０ｍｌに加え、撹拌した。この反応液にトリ（ｔｅｒｔ−ブチル）ホスホニウム テトラフルオロボレート（ｔＢｕ₃Ｐ・ＨＢＦ₄：０．３５ｇ，１．２ｍｍｏｌ）を加え１００℃で終夜撹拌した。その後、水２００ｍｌを加えた反応液をセライトでろ過した後濃縮し、メタノールを加えて結晶を析出させた。得られた結晶をろ別し、水とメタノールで洗浄した。これにより、中間体３ａを収量１０．０ｇ、収率７７％で得た。
¹Ｈ ＮＭＲ（６００ＭＨｚ，ＣＤＣｌ₃）δ８．６−８．１（２Ｈ），７．４−６．８（９Ｈ）、６．８−６．５（ｍ，６Ｈ），１．８−１．６（９Ｈ）；ＭＳ（７０ｅＶ，ＥＩ）ｍ／ｚ＝４３４（Ｍ＋） [1-2] Amination process

Intermediate 2a (10.4 g, 30 mmol), diphenylamine (5.58 g, 33 mmol), palladium acetate (Pd (OAc) ₂ : 0.54 g, 2.4 mmol), and sodium tert-butoxide (NaOt-Bu: 6. 92 g, 72 mmol) was added to 160 ml of dehydrated toluene and stirred. Tri (tert-butyl) phosphonium tetrafluoroborate (tBu ₃ P · HBF ₄ : 0.35 g, 1.2 mmol) was added to the reaction solution, and the mixture was stirred at 100 ° C. overnight. Thereafter, the reaction solution to which 200 ml of water was added was filtered through celite and concentrated, and methanol was added to precipitate crystals. The obtained crystals were separated by filtration and washed with water and methanol. As a result, Intermediate 3a was obtained in a yield of 10.0 g and a yield of 77%.
¹ H NMR (600 MHz, CDCl ₃ ) δ 8.6-8.1 (2H), 7.4-6.8 (9H), 6.8-6.5 (m, 6H), 1.8-1. 6 (9H); MS (70 eV, EI) m / z = 434 (M +)

中間体３ａ（８．６９ｇ，２０ｍｍｏｌ）を１，４−ジオキサン１００ｍｌに加え、濃塩酸１０ｍｌを滴下した後、８０℃で２時間撹拌した。この反応液を濃縮してトルエン３００ｍｌを加え、飽和炭酸水素ナトリウムで中和した後、分液した。このうち有機層を濃縮し、この濃縮物を、ＳｉＯ₂カラムクロマトグラフィーにより、クロロホルム：ヘキサン＝１：１の混合溶媒を展開溶媒に用いて精製した。これにより、化合物１を収量５．７ｇ、収率８５％で得た。
¹Ｈ ＮＭＲ（６００ＭＨｚ，ＣＤＣｌ₃）δ１１．０−１２．０（１Ｈ）、８．６−８．１（２Ｈ），７．４−６．８（９Ｈ）、６．８−６．５（ｍ，６Ｈ）；ＭＳ（７０ｅＶ，ＥＩ）ｍ／ｚ＝３３４（Ｍ＋） [1-3] Desorption step

Intermediate 3a (8.69 g, 20 mmol) was added to 100 ml of 1,4-dioxane, 10 ml of concentrated hydrochloric acid was added dropwise, and the mixture was stirred at 80 ° C. for 2 hours. The reaction solution was concentrated, added with 300 ml of toluene, neutralized with saturated sodium hydrogen carbonate, and then separated. Among these, the organic layer was concentrated, and this concentrate was purified by SiO ₂ column chromatography using a mixed solvent of chloroform: hexane = 1: 1 as a developing solvent. As a result, Compound 1 was obtained in a yield of 5.7 g and a yield of 85%.
¹ H NMR (600 MHz, CDCl ₃ ) δ 11.0-12.0 (1H), 8.6-8.1 (2H), 7.4-6.8 (9H), 6.8-6.5 ( m, 6H); MS (70 eV, EI) m / z = 334 (M +)

３−ブロモカルバゾール（１０．０ｇ, ４０．６ｍｍｏｌ）の代わりに ３，６−ジブロモカルバゾール（１３．２ｇ, ４０．６ｍｍｏｌ）を出発物質として用いること以外は、実施例１と同様の保護工程を行い、中間体２ｂを収量１５．０ｇ、収率８７％で得た。
¹Ｈ ＮＭＲ（６００ＭＨｚ，ＣＤＣｌ₃）δ８．６−８．４（２Ｈ），８．３−７．８（４Ｈ），１．８−１．６（９Ｈ）；ＭＳ（７０ｅＶ，ＥＩ）ｍ／ｚ＝４２３（Ｍ＋）、４２５（Ｍ＋）、４２８（Ｍ＋） Example 2 Synthesis of Compound 2 [2-1] Protection Step

The same protection step as in Example 1 was performed except that 3,6-dibromocarbazole (13.2 g, 40.6 mmol) was used as a starting material instead of 3-bromocarbazole (10.0 g, 40.6 mmol). Intermediate 2b was obtained in a yield of 15.0 g and a yield of 87%.
¹ H NMR (600 MHz, CDCl ₃ ) δ 8.6-8.4 (2H), 8.3-7.8 (4H), 1.8-1.6 (9H); MS (70 eV, EI) m / z = 423 (M +), 425 (M +), 428 (M +)

中間体２ｂ（８．４９ｇ，３０ｍｍｏｌ）、ジフェニルアミン（１１．１６ｇ，６６ｍｍｏｌ）、パラジウム触媒（シグマ−アルドリッチ社製、商品名ＰＥＰＰＳＩ−Ｉｐｒ：１．０２ｇ,１．５ｍｍｏｌ）、およびＮａＯｔ−Ｂｕ（７．２１ｇ，７５ｍｍｏｌ）を脱水トルエン１６０ｍｌに加え、１００℃で終夜撹拌した。その後、水２００ｍｌを加えた反応液を、セライトでろ過した後濃縮し、メタノールを加えて結晶を析出させた。得られた結晶をろ別し、水とメタノールで洗浄した。これにより、中間体３ｂを収量１５．９ｇ、収率８８％で得た。
¹Ｈ ＮＭＲ（６００ＭＨｚ，ＣＤＣｌ₃）δ８．４−７．８（８Ｈ），７．７−６．８（１８Ｈ），１．８−１．６（９Ｈ）；ＭＳ（７０ｅＶ，ＥＩ）ｍ／ｚ＝６０１（Ｍ＋） [2-2] Amination step

Intermediate 2b (8.49 g, 30 mmol), diphenylamine (11.16 g, 66 mmol), palladium catalyst (manufactured by Sigma-Aldrich, trade name PEPPSI-Ipr: 1.02 g, 1.5 mmol), and NaOt-Bu (7 .21 g, 75 mmol) was added to 160 ml of dehydrated toluene and stirred at 100 ° C. overnight. Thereafter, the reaction solution to which 200 ml of water was added was filtered through celite and concentrated, and methanol was added to precipitate crystals. The obtained crystals were separated by filtration and washed with water and methanol. As a result, Intermediate 3b was obtained in a yield of 15.9 g and a yield of 88%.
¹ H NMR (600 MHz, CDCl ₃ ) δ 8.4-7.8 (8H), 7.7-6.8 (18H), 1.8-1.6 (9H); MS (70 eV, EI) m / z = 601 (M +)

中間体３ａ（８．６９ｇ，２０ｍｍｏｌ）の代わりに中間体３ｂ（１２．０３ｇ，２０ｍｍｏｌ）を用いること以外は、実施例１と同様の脱離工程を行い、化合物２を収量９．１３ｇ、収率９１％で得た。
^１Ｈ ＮＭＲ（６００ＭＨｚ，ＣＤＣｌ_３）δ１１．０−１２．０（１Ｈ）、８．２−８．０（ｍ，２Ｈ），７．９−７．７（２Ｈ）、７．３−６．９（ｍ，１０Ｈ）、６．９−６．５（４Ｈ）；ＭＳ（７０ｅＶ，ＥＩ）ｍ／ｚ＝５０１（Ｍ＋） [2-3] Desorption step

Except for using Intermediate 3b (12.03 g, 20 mmol) instead of Intermediate 3a (8.69 g, 20 mmol), the same elimination step as in Example 1 was performed, and Compound 2 was obtained in a yield of 9.13 g. Obtained at a rate of 91%.
¹ H NMR (600 MHz, CDCl ₃ ) δ 11.0-12.0 (1H), 8.2-8.0 (m, 2H), 7.9-7.7 (2H), 7.3-6. 9 (m, 10H), 6.9-6.5 (4H); MS (70 eV, EI) m / z = 501 (M +)

中間体２ｂ（８．５０ｇ，２０ｍｍｏｌ）、ジ（ｐ−トリル）アミン（１１．８４ｇ，６０ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（Ｐｄ₂（ｄｂａ）₃：０．９１６ｇ,１．０ｍｍｏｌ）、ＮａＯｔ−Ｂｕ（４．６１ｇ，４８ｍｍｏｌ）、および２−ジ−ｔｅｒｔ−ブチルホスフィノ−２′−（Ｎ，Ｎ−ジメチルアミノ）ビフェニル（１．３７ｇ，４ｍｍｏｌ）を脱水トルエン１００ｍｌに加え、１００℃で終夜撹拌した。その後、水２００ｍｌを加えた反応液を、セライトでろ過した後濃縮し、メタノールを加えて結晶を析出させた。得られた結晶をろ別し、水とメタノールで洗浄した。これにより、中間体３ｃを収量１１．８４ｇ、収率９０％で得た。
¹Ｈ ＮＭＲ（６００ＭＨｚ，ＣＤＣｌ₃）δ８．４−７．８（４Ｈ），７．７−６．８（１８Ｈ），２．５−２．３（１２Ｈ），１．８−１．６（９Ｈ）；ＭＳ（７０ｅＶ，ＥＩ）ｍ／ｚ＝６５７（Ｍ＋） Example 3 Synthesis of Compound 4 [3-1] Protection Step Intermediate 2b was obtained using the same starting material and protection step as in Example 2.
[3-2] Amination step

Intermediate 2b (8.50 g, 20 mmol), di (p-tolyl) amine (11.84 g, 60 mmol), tris (dibenzylideneacetone) dipalladium (Pd ₂ (dba) ₃ : 0.916 g, 1.0 mmol) , NaOt-Bu (4.61 g, 48 mmol), and 2-di-tert-butylphosphino-2 ′-(N, N-dimethylamino) biphenyl (1.37 g, 4 mmol) were added to 100 ml of dehydrated toluene. Stir overnight at ° C. Thereafter, the reaction solution to which 200 ml of water was added was filtered through celite and concentrated, and methanol was added to precipitate crystals. The obtained crystals were separated by filtration and washed with water and methanol. As a result, Intermediate 3c was obtained in a yield of 11.84 g and a yield of 90%.
¹ H NMR (600 MHz, CDCl ₃ ) δ 8.4-7.8 (4H), 7.7-6.8 (18H), 2.5-2.3 (12H), 1.8-1.6 ( 9H); MS (70 eV, EI) m / z = 657 (M +)

中間体３ａ（８．６９ｇ，２０ｍｍｏｌ）の代わりに中間体３ｃ（１３．１６ｇ，２０ｍｍｏｌ）を用いること以外は、実施例１と同様の脱離工程を行い、化合物４を収量１０．３７ｇ、収率９３％で得た。
¹Ｈ ＮＭＲ（６００ＭＨｚ，ＣＤＣｌ₃）δ１１．０−１２．０（１Ｈ），８．４−７．８（４Ｈ），７．７−６．８（１８Ｈ），２．５−２．３（１２Ｈ）；ＭＳ（７０ｅＶ，ＥＩ）ｍ／ｚ＝５５７（Ｍ＋） [3-3] Desorption step

Except for using Intermediate 3c (13.16 g, 20 mmol) instead of Intermediate 3a (8.69 g, 20 mmol), the elimination step was performed in the same manner as in Example 1, yielding 10.37 g of Compound 4 in a yield of 10.37 g. Obtained at a rate of 93%.
¹ H NMR (600 MHz, CDCl ₃ ) δ 11.0-12.0 (1H), 8.4-7.8 (4H), 7.7-6.8 (18H), 2.5-2.3 ( 12H); MS (70 eV, EI) m / z = 557 (M +)

中間体２ａ（６．２３ｇ，１８ｍｍｏｌ）とフェノキサジン（３．６３ｇ，２０ｍｍｏｌ）および、Ｐｄ（ＯＡｃ）₂（０．３２ｇ,１．４ｍｍｏｌ）、ＮａＯｔ−Ｂｕ（２．２５ｇ，２３．４ｍｍｏｌ）を脱水トルエン１００ｍｌに加え、撹拌した。この反応液にｔＢｕ₃Ｐ・ＨＢＦ₄（０．２１ｇ，０．７ｍｍｏｌ）を加え８０℃で終夜撹拌した。反応液に水２００ｍｌを加え、セライトろ過し、濃縮してメタノールを加え結晶化させ、ろ別して、水とメタノールで洗浄して中間体３ｄ（５．２５ｇ,収率６５％）を得た。必要に応じてカラムクロマトグラフィー（ＳｉＯ₂,クロロホルム：ヘキサン＝１：１）により精製を行った。
ＭＳ（７０ｅＶ，ＥＩ）ｍ／ｚ＝４４８（Ｍ＋） Synthesis Example 4 Synthesis of Compound 5 [4-1] Protection Step Intermediate 2a was obtained using the same starting material and protection step as in Example 1.
[4-2] Amination step

Intermediate 2a (6.23 g, 18 mmol), phenoxazine (3.63 g, 20 mmol), Pd (OAc) ₂ (0.32 g, 1.4 mmol), NaOt-Bu (2.25 g, 23.4 mmol) The mixture was added to 100 ml of dehydrated toluene and stirred. TBu ₃ P · HBF ₄ (0.21 g, 0.7 mmol) was added to the reaction solution, and the mixture was stirred at 80 ° C. overnight. To the reaction solution was added 200 ml of water, filtered through Celite, concentrated, crystallized by adding methanol, filtered and washed with water and methanol to obtain Intermediate 3d (5.25 g, yield 65%). If necessary, purification was performed by column chromatography (SiO ₂ , chloroform: hexane = 1: 1).
MS (70 eV, EI) m / z = 448 (M +)

中間体３ａ（８．６９ｇ，２０ｍｍｏｌ）の代わりに中間体３ｄ（４．４９ｇ，１０ｍｍｏｌ）を用いること以外は、実施例１と同様の脱離工程を行い、化合物５を収量２．９６ｇ、収率８５％で得た。
¹Ｈ ＮＭＲ（６００ＭＨｚ，ＣＤＣｌ₃）δ１０．０−１１．０（１Ｈ)、８．４−８．１（１Ｈ），７．８．−７．５（３Ｈ），７．４−７．３（２Ｈ），７．２−６．９（９Ｈ）；ＭＳ（７０ｅＶ，ＥＩ）ｍ／ｚ＝３４８（Ｍ＋） [4-3] Desorption step

Except for using Intermediate 3d (4.49 g, 10 mmol) instead of Intermediate 3a (8.69 g, 20 mmol), the same elimination step as in Example 1 was performed, yielding 2.96 g of Compound 5 in a yield of 2.96 g. Obtained at a rate of 85%.
¹ H NMR (600 MHz, CDCl ₃ ) δ 10.0-11.0 (1H), 8.4-8.1 (1H), 7.8. -7.5 (3H), 7.4-7.3 (2H), 7.2-6.9 (9H); MS (70 eV, EI) m / z = 348 (M +)

中間体２ａ（５．１９ｇ，１５ｍｍｏｌ）と９，９−ジメチルアクリダン（３．４５ｇ，１６．５ｍｍｏｌ）および、Ｐｄ（ＯＡｃ）₂（０．２７ｇ,１．２ｍｍｏｌ）、ＮａＯｔ−Ｂｕ（１．８７ｇ，１９．５ｍｍｏｌ）を脱水トルエン８０ｍｌに加え、撹拌した。この反応液にｔＢｕ₃Ｐ・ＨＢＦ₄（０．１７ｇ，０．６ｍｍｏｌ）を加え８０℃で終夜撹拌した。反応液に水１５０ｍｌを加え、セライトろ過し、濃縮してメタノールを加え結晶化させ、ろ別して、水とメタノールで洗浄して中間体３ｅ（３．９２ｇ,収率５５％）を得た。必要に応じてカラムクロマトグラフィー（ＳｉＯ₂,クロロホルム：ヘキサン＝１：１）により精製を行った
ＭＳ（７０ｅＶ，ＥＩ）ｍ／ｚ＝４５９（Ｍ⁺ − Ｍｅ） Synthesis Example 5 Synthesis of Compound 6 [5-1] Protection Step Intermediate 2a was obtained using the same starting material and protection step as in Example 1.
[5-2] Amination step

Intermediate 2a (5.19 g, 15 mmol), 9,9-dimethylacridan (3.45 g, 16.5 mmol) and Pd (OAc) ₂ (0.27 g, 1.2 mmol), NaOt-Bu (1. 87 g, 19.5 mmol) was added to 80 ml of dehydrated toluene and stirred. TBu ₃ P · HBF ₄ (0.17 g, 0.6 mmol) was added to the reaction solution, and the mixture was stirred at 80 ° C. overnight. 150 ml of water was added to the reaction solution, filtered through Celite, concentrated, crystallized by adding methanol, filtered and washed with water and methanol to obtain Intermediate 3e (3.92 g, yield 55%). MS (70 eV, EI) m / z = 459 (M ⁺ -Me) purified by column chromatography (SiO ₂ , chloroform: hexane = 1: 1) as necessary.

中間体３ａ（８．６９ｇ，２０ｍｍｏｌ）の代わりに中間体３ｅ（２．３７ｇ，５ｍｍｏｌ）を用いること以外は、実施例１と同様の脱離工程を行い、化合物６を収量１．８７ｇ、収率９２％で得た。
¹Ｈ ＮＭＲ（６００ＭＨｚ，ＣＤＣｌ₃）δ１０．０−１１．０（１Ｈ)、８．４−８．１（１Ｈ），７．７．−７．４（３Ｈ），７．３−７．１（９Ｈ），７．０−６．８（２Ｈ），１．７−１．４（６Ｈ）；ＭＳ（７０ｅＶ，ＥＩ）ｍ／ｚ＝３５９（Ｍ⁺−Ｍｅ） [5-3] Desorption step

Except for using Intermediate 3e (2.37 g, 5 mmol) instead of Intermediate 3a (8.69 g, 20 mmol), the same elimination step as in Example 1 was performed to obtain Compound 6 in a yield of 1.87 g. Obtained at a rate of 92%.
¹ H NMR (600 MHz, CDCl ₃ ) δ 10.0-11.0 (1H), 8.4-8.1 (1H), 7.7. -7.4 (3H), 7.3-7.1 (9H), 7.0-6.8 (2H), 1.7-1.4 (6H); MS (70 eV, EI) m / z = 359 (M ⁺ -Me)

(Comparative Example 1)
According to the method described in Non-Patent Document 2, a benzyl group was introduced at the 9-position of 3-bromocarbazole. Thereafter, the same amination step and elimination step as in Example 1 were carried out except that 3-bromocarbazole into which a benzyl group was introduced instead of intermediate 2a, and a carbazole compound in which a diphenylamino group was introduced at the 3-position (Compound 1) was synthesized.

中間体５（５．１８ｇ，８ｍｍｏｌ）と塩化アルミニウム（１０．６７ｇ，８０ｍｍｏｌ）をアニソール４７ｍｌに加え、８０℃で終夜撹拌した。この反応液を氷水５００ｍｌに添加し、さらにトルエン３００ｍｌに加え、水酸化ナトリウムでｐＨ＝１０以上になるまで調製した。調製した反応液をセライトでろ過し、分液した。このうち有機層を濃縮し、この濃縮物をＳｉＯ₂カラムクロマトグラフィーにより、クロロホルムを展開溶媒に用いて精製した。得られたフラクションにメタノールを加えて、目的物４の結晶を析出させた。これにより、化合物４を収量１．０７ｇ、収率２４％で得た。 (Comparative Example 2)
According to the method described in Non-Patent Document 2, a benzyl group was introduced at the 9-position of 3,6-dibromocarbazole. Then, the same amination process as Example 3 was performed except having used the 3, 6- dibromo carbazole which introduce | transduced the benzyl group instead of the intermediate 2b, and the following intermediate 5 was obtained.

Intermediate 5 (5.18 g, 8 mmol) and aluminum chloride (10.67 g, 80 mmol) were added to 47 ml of anisole and stirred at 80 ° C. overnight. This reaction solution was added to 500 ml of ice water, further added to 300 ml of toluene, and prepared with sodium hydroxide until pH = 10 or more. The prepared reaction solution was filtered through celite and separated. Among these, the organic layer was concentrated, and this concentrate was purified by SiO ₂ column chromatography using chloroform as a developing solvent. Methanol was added to the obtained fraction to precipitate crystals of the target product 4. As a result, Compound 4 was obtained in a yield of 1.07 g and a yield of 24%.

(Comparative Example 3)
According to the method described in the literature (Organic Letters, 15 (5), 1120-1123; 2013), using 3-bromocarbazole and p-tolylsulfonyl chloride, a p-tolylsulfonyl group at the 9-position of 3-bromocarbazole ( MeC ₆ H ₄ SO ₂ -) was introduced. Thereafter, the same amination step and elimination step as in Example 1 were carried out except that 3-bromocarbazole having a p-tolylsulfonyl group introduced was used instead of the intermediate 2a, and a diphenylamino group was introduced at the 3-position. A carbazole compound (Compound 1) was synthesized.

(Comparative Example 4)
In the same manner as in the method described in Comparative Example 3, an acetyl group (CH ₃ CO—) was introduced into the 9-position of 3-bromocarbazole using 3-bromocarbazole and acetyl chloride. Thereafter, the same amination step and elimination step as in Example 1 were performed except that 3-bromocarbazole having an acetyl group introduced therein was used instead of intermediate 2a, and a carbazole compound having a diphenylamino group introduced at the 3-position (Compound 1) was synthesized.

(Comparative Example 5)
According to the method described in Patent Document 1, a benzoyl group was introduced at the 9-position of 3-bromocarbazole. Thereafter, the same amination step and elimination step as in Example 1 were carried out except that 3-bromocarbazole having a benzoyl group introduced therein was used instead of intermediate 2a, and a carbazole compound having a diphenylamino group introduced at the 3-position (Compound 1) was synthesized.

(Comparative Example 6)
Similarly to the method described in Comparative Example 3, a benzyloxycarbonyl group (PhCH ₂ OCO-) was introduced into the 9-position of 3-bromocarbazole using 3-bromocarbazole and benzyloxycarbonyl chloride (PhCH ₂ OCOCl). . Thereafter, the same amination step and elimination step as in Example 1 were performed except that 3-bromocarbazole into which a benzyloxycarbonyl group was introduced instead of the intermediate 2a, and a diphenylamino group was introduced at the 3-position. A carbazole compound (Compound 1) was synthesized.

[Evaluation]
About Examples 1-3 and Comparative Examples 1-6, the degree of elimination of the protecting group in the amination step was evaluated according to the following criteria. Here, the degree of elimination of the protecting group in the amination step was examined by thin layer silica gel chromatography. Moreover, this evaluation result is shown in Table 1 together with the yield in the desorption process.
A: No removal of the protecting group is observed B: No elimination of the protecting group is observed

As shown in Table 1, in Examples 1 to 3, in which a butoxycarbonyl group was introduced as a protecting group, the elimination of the protecting group was not observed in the amination step, and the yield in the elimination step was as high as 85% or more. It was a thing. In particular, in Examples 2 and 3 in which tertiary amino groups were introduced at two positions of the carbazole ring, a very high yield of 90% or more could be obtained.
On the other hand, in Comparative Examples 1 and 2 in which a benzyl group was introduced as a protecting group, although removal of the protecting group was not observed in the amination step, the production of Examples 1 and 3 in which similar carbazole compounds were synthesized. Compared with the method, the yield in the desorption process was low. In particular, the yield of Comparative Example 2 in which a ditolylamino group was introduced as a tertiary amino group was significantly inferior to that of Example 3. This is presumed to be due to the polymerization of the ditolylamino group in which the aryl moiety is electron-rich due to the influence of the methyl group in the presence of AlCl ₃ which is a Lewis acid, reacting with the benzyl group.
Further, in Comparative Example 3 in which a p-tolylsulfonyl group was introduced as a protecting group, Comparative Example 4 in which an acetyl group was introduced, and Comparative Example 5 in which a benzoyl group was introduced, elimination of the protecting group was observed in the amination step.
Furthermore, in Comparative Example 6 in which a benzyloxycarbonyl group was introduced as a protecting group, the yield in the elimination step was as low as 5% or less.

In the method for producing a carbazole compound having a tertiary amino group of the present invention, a carbazole compound having a tertiary amino group useful as an organic semiconductor material can be obtained in a high yield by a simple process.
For this reason, this invention has high industrial applicability.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Hole injection layer 4 Hole transport layer 5 Light emitting layer 6 Electron transport layer 7 Cathode

Claims (20)

  Production of a carbazole compound having a tertiary amino group, comprising a step of introducing a tertiary amino group into a compound having a 9-butoxycarbonylcarbazole structure and a step of removing the butoxycarbonyl group from the compound Method.   The method according to claim 1, wherein the compound containing a 9-butoxycarbonylcarbazole structure has a reactive group at at least one of positions 1 to 8 of the carbazole ring.   The production method according to claim 2, wherein the reactive group is a halogen atom.   The production method according to any one of claims 1 to 3, wherein the tertiary amino group is introduced by reacting the compound containing the 9-butoxycarbonylcarbazole structure with a secondary amine.   The production method according to claim 4, wherein a palladium catalyst is used when the compound containing the 9-butoxycarbonylcarbazole structure is reacted with the secondary amine.   6. The process according to claim 4 or 5, wherein the secondary amine is diarylamine, dialkylamine, alkylarylamine, carbazole, acridan, phenoxazine, phenothiazine or 5,10-dihydrophenazine. The aryl group and the alkyl group present in the diarylamine, the dialkylamine and the alkylarylamine may be substituted, respectively, and the carbazole 1 to 8 position, the acridan 1 to 9 position, the phenoxy 1 to 4 and 6 to 9 positions of sadin, 1 to 4 and 6 to 9 positions of the phenothiazine, and 1 to 9 positions of the 5,10-dihydrophenazine may be substituted).   6. The production method according to claim 4 or 5, wherein the secondary amine is a diarylamine (however, the aryl group present in the diarylamine may be substituted).   8. The butoxycarbonyl group is eliminated by bringing a compound containing a 9-butoxycarbonylcarbazole structure into which a tertiary amino group has been introduced into contact with an acidic compound. The manufacturing method as described.   The method according to any one of claims 1 to 8, wherein the step of removing the butoxycarbonyl group is performed without performing purification in the step of introducing the tertiary amino group.   The method according to any one of claims 1 to 9, wherein the step of removing the butoxycarbonyl group is also performed while the step of introducing the tertiary amino group is performed. A compound represented by the following general formula (1).

[In General Formula (1), R ^{1 to} R ⁸ each independently represents a hydrogen atom or a substituent, but at least one of R ^{1 to} R ⁸ represents a tertiary amino group. R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁶ and R ⁷ , R ⁷ and R ⁸ are bonded to each other to form a cyclic structure. It may be formed. ] The compound according to claim 11, wherein at least one of R ³ and R ^{6 in} the general formula (1) is a tertiary amino group.   The tertiary amino group is a diarylamino group, a dialkylamino group, an alkylarylamino group, a carbazol-9-yl group, an acridan-10-yl group, a phenoxazin-10-yl group, a phenothiazin-10-yl group, or 5, The compound according to claim 11 or 12, which is a 10-dihydrophenazin-10-yl group (provided that the aryl group and the alkyl present in the diarylamino group, the dialkylamino group and the alkylarylamino group) Each group may be substituted, and the 1 to 8 position of the carbazol-9-yl group, the 1 to 9 position of the acridan-10-yl group, and 1 to 4 and 6 of the phenoxazin-10-yl group. -9 position, positions 1-4 and 6-9 of the phenothiazin-10-yl group, and 5,10-dihydro 1-9 position Enajin-10-yl group may be substituted.).   The compound according to claim 11 or 12, wherein the tertiary amino group is a diarylamino group (however, the aryl group present in the diarylamino group may be substituted). A compound represented by the following general formula (5).

[In General Formula (5), R ^{11 to} R ¹⁸ each independently represents a hydrogen atom or a substituent, and at least one of R ¹³ and R ¹⁶ is represented by any one of the following General Formulas (6) to (9). Has a structure. R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ are bonded to each other to form a cyclic structure. It may be formed. ]

[In General Formulas (6) to (9), R ^{31 to} R ³⁸ , R ^{41 to} R ⁴⁸ , R ^{51 to} R ⁵⁸ , R ^{61 to} R ⁶⁵ , and R ^{71 to} R ⁸⁰ are each independently a hydrogen atom or a substituent. Represents a group. R ³¹ and R ³² , R ³² and R ³³ , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R ⁴³ And R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , R ⁴⁶ and R ⁴⁷ , R ⁴⁷ and R ⁴⁸ , R ⁵¹ and R ⁵² , R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁴ , R ⁵⁵ and R ⁵⁶ , R ⁵⁶ and R ⁵⁷ , ^R57 and ^R58 , ^R61 and ^R62 , ^R62 and ^R63 , ^R63 and ^R64 , ^R64 and ^R65 , ^R54 and ^R61 , ^R55 and ^R65 , ^R71 and ^R72 , R ⁷² and R ⁷³ , R ⁷³ and R ⁷⁴ , R ⁷⁵ and R ⁷⁶ , R ⁷⁶ and R ⁷⁷ , R ⁷⁷ and R ⁷⁸ , and R ⁷⁹ and R ⁸⁰ may be bonded to each other to form a cyclic structure. * Represents a bonding position. ] The donor material which consists of a compound represented by following General formula (5).

[In General Formula (5), R ^{11 to} R ¹⁸ each independently represents a hydrogen atom or a substituent, and at least one of R ¹³ and R ¹⁶ is represented by any one of the following General Formulas (6) to (9). Has a structure. R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ are bonded to each other to form a cyclic structure. It may be formed. ]

[In General Formulas (6) to (9), R ^{31 to} R ³⁸ , R ^{41 to} R ⁴⁸ , R ^{51 to} R ⁵⁸ , R ^{61 to} R ⁶⁵ , and R ^{71 to} R ⁸⁰ are each independently a hydrogen atom or a substituent. Represents a group. R ³¹ and R ³² , R ³² and R ³³ , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R ⁴³ And R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , R ⁴⁶ and R ⁴⁷ , R ⁴⁷ and R ⁴⁸ , R ⁵¹ and R ⁵² , R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁴ , R ⁵⁵ and R ⁵⁶ , R ⁵⁶ and R ⁵⁷ , ^R57 and ^R58 , ^R61 and ^R62 , ^R62 and ^R63 , ^R63 and ^R64 , ^R64 and ^R65 , ^R54 and ^R61 , ^R55 and ^R65 , ^R71 and ^R72 , R ⁷² and R ⁷³ , R ⁷³ and R ⁷⁴ , R ⁷⁵ and R ⁷⁶ , R ⁷⁶ and R ⁷⁷ , R ⁷⁷ and R ⁷⁸ , and R ⁷⁹ and R ⁸⁰ may be bonded to each other to form a cyclic structure. * Represents a bonding position. ]   The donor material according to claim 16, which is used for a delayed phosphor. A method for producing a phosphor, comprising substituting the 9-position of a carbazole ring of a compound represented by the following general formula (5) with an acceptor.

[In General Formula (5), R ^{11 to} R ¹⁸ each independently represents a hydrogen atom or a substituent, and at least one of R ¹³ and R ¹⁶ is represented by any one of the following General Formulas (6) to (9). Has a structure. R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ are bonded to each other to form a cyclic structure. It may be formed. ]

[In General Formulas (6) to (9), R ^{31 to} R ³⁸ , R ^{41 to} R ⁴⁸ , R ^{51 to} R ⁵⁸ , R ^{61 to} R ⁶⁵ , and R ^{71 to} R ⁸⁰ are each independently a hydrogen atom or a substituent. Represents a group. R ³¹ and R ³² , R ³² and R ³³ , R ³³ and R ³⁴ , R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , R ⁴¹ and R ⁴² , R ⁴² and R ⁴³ , R ⁴³ And R ⁴⁴ , R ⁴⁵ and R ⁴⁶ , R ⁴⁶ and R ⁴⁷ , R ⁴⁷ and R ⁴⁸ , R ⁵¹ and R ⁵² , R ⁵² and R ⁵³ , R ⁵³ and R ⁵⁴ , R ⁵⁵ and R ⁵⁶ , R ⁵⁶ and R ⁵⁷ , ^R57 and ^R58 , ^R61 and ^R62 , ^R62 and ^R63 , ^R63 and ^R64 , ^R64 and ^R65 , ^R54 and ^R61 , ^R55 and ^R65 , ^R71 and ^R72 , R ⁷² and R ⁷³ , R ⁷³ and R ⁷⁴ , R ⁷⁵ and R ⁷⁶ , R ⁷⁶ and R ⁷⁷ , R ⁷⁷ and R ⁷⁸ , and R ⁷⁹ and R ⁸⁰ may be bonded to each other to form a cyclic structure. * Represents a bonding position. ] A delayed phosphor represented by the following general formula (11) is produced by reacting a compound represented by the general formula (5) with a compound represented by the following general formula (10): The method for producing a phosphor according to claim 18.
General formula (10)
X-A
[In General Formula (10), X represents a halogen atom, and A represents an acceptor. ]

[In General Formula (11), R ^{11 to} R ¹⁸ each independently represents a hydrogen atom or a substituent, and at least one of R ¹³ and R ¹⁶ is represented by any one of General Formulas (6) to (9). Has a structure. A represents an acceptor. R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ are bonded to each other to form a cyclic structure. It may be formed. ]   The method for producing a phosphor according to claim 18 or 19, wherein the phosphor is a delayed phosphor.

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