JP4780372B2 - Quinoxalinedione derivative, production method thereof and use thereof - Google Patents

Description

  The present invention relates to a novel quinoxalinedione derivative and a method for producing the same, and a luminescent material of the quinoxalinedione derivative, a solubilizer for a metal salt, or a trap for a metal element.

  Conventionally, research has been conducted on light-emitting materials composed of organic substances having various heterocyclic bone nuclei or metal complexes thereof. These heteronuclear bone nuclei often require multi-step synthetic reactions for production due to their complex chemical structures. In addition, since it is a condensed polycyclic structure having a rigid chemical structure, it often has a drawback that it has a high melting point and is not sufficiently soluble in a solvent. These disadvantages not only cause problems in synthesis reaction operations and separation and purification by liquid chromatography, but also cause difficulty in film formation by spin coating. Also, because of the high molecular weight and low vapor pressure, there is a disadvantage in film formation by vacuum deposition.

In order to solve these problems, new luminescent materials have been demanded. As a structure required for a new light-emitting material, the structure should be as simple as possible, assuming that it has a condensed polycyclic structure, and the chemical reaction process should be as simple as possible in its production. However, considering the ease of production of the target compound in terms of setting reaction conditions and yield, and considering usage, performance such as rich solubility in conventionally used organic solvents Needed. When the metal salt used as a synthesis reagent is used in a homogeneous solution, the aprotic polarity having an amide structure such as N, N-dimethylformamide, N, N-dimethylacetamide or N-methylpyrrolidone has been conventionally used as a solvent. Solvents have been used. In the molecules of these solvents, there is only one carbonyl group for solvating the metal cation, and the solvating ability may not be sufficient. For this reason, there has been a demand for metal salt solubilizing agents that are more excellent in solvating ability than conventional aprotic amide solvents.
As a countermeasure against the problems found in conventional solvents, it was expected that a plurality of carbonyl groups could be realized by solubilizers having adjacent chemical structures.

Under such a technical background, a novel solid light-emitting material satisfying the requirements from the above-mentioned structure, production, and solvent in a light-emitting material premised on having a condensed polycyclic structure In addition, a metal salt solubilizing agent and a metal scavenger excellent in solvating ability are desired.

  The problem to be solved by the present invention is a compound having a novel condensed polycyclic structure and a method for producing the same, and a light emitting material premised on having a condensed polycyclic structure. It is an object of the present invention to provide a novel solid-state light-emitting material that satisfies the requirements from a solvent, a metal salt solubilizer and a metal scavenger having excellent solvating ability.

  The present inventors have studied the above-mentioned problems, and have newly invented a novel quinoxalinedione derivative compound having a condensed polycyclic structure and a chemical structure in which a plurality of carbonyl groups are adjacent to each other, and a method for producing the compound. Has found that it becomes a new solid light-emitting material satisfying the requirements from the solvent in terms of structure, production, and at the same time, it becomes a metal salt solubilizer and metal scavenger excellent in solvating ability, The present invention has been completed.

（式中、R¹¹とR¹²は、脂肪族炭化水素基であり、不飽和結合と分岐鎖を含んでもよい。R^2１,R²²は、塩素、臭素及びヨウ素から選ばれるハロゲン原子、又は脂肪族炭化水素基R³及び脂肪族炭化水素オキシ基OR³から選ばれる基（式中、R³はアルキル基（CnH2n+1、nは1〜20の整数を表す。）から選ばれる原子又は基を表す。）
（２）下記一般式（２）で表されることを特徴とするキノキサリンジオン誘導体

（式中、Ｘは活性基、R¹³はＨを表す。
R¹⁴は、アルキレン基（CnH2n, n=1〜20の整数をあらわす。）又は芳香環を含むアルキレン基（CH2C6H4CH2）を表す。
R^2１,R²²は、塩素、臭素及びヨウ素から選ばれるハロゲン原子、又は脂肪族炭化水素基R³及び脂肪族炭化水素オキシ基OR³から選ばれる基（式中、R³はアルキル基（CnH2n+1、nは1〜20の整数を表す。）から選ばれる原子又は基を表す。mは2から1000の整数を表す。）
（３）下記一般式（３）で表されることを特徴とするキノキサリンジオン誘導体。

（式中、R³¹,R³²,R³³は、アルキル基（炭素数1から18）及びアラルキル基から選ばれる基を表す。
R^2１,R²²は、塩素、臭素及びヨウ素から選ばれるハロゲン原子、脂肪族炭化水素基R³及び脂肪族炭化水素オキシ基OR³から選ばれる基（式中、R³はアルキル基（CnH2n+1、nは1〜20の整数を表す。））から選ばれる原子又は基を表す。）。
（４）下記一般式（４）で表されることを特徴とするキノキサリンジオン誘導体。

（式中、R³¹,R³²,R³³は、アルキル基（炭素数1から18）及びアラルキル基から選ばれる基を表す。
R^2１,R²²は、塩素、臭素及びヨウ素から選ばれるハロゲン原子、脂肪族炭化水素基R³及び脂肪族炭化水素オキシ基OR³から選ばれる基（式中、R³はアルキル基（CnH2n+1, nは1〜20の整数を表す。）から選ばれる原子又は基を表す。）
（５）下記一般式（５）で表されることを特徴とするキノキサリンジオン誘導体。

（式中、R^2１,R²²は、塩素、臭素及びヨウ素から選ばれるハロゲン原子、脂肪族炭化水素基R³及び脂肪族炭化水素オキシ基OR³から選ばれる基（式中、R³ はアルキル基（CnH2n+1,nは1〜20の整数を表す。）から選ばれる原子又は基を表す。）
（６）下記一般式（６）で表されるキノキサリンジオン誘導体を熱転移反応により一般式（３）で表されるキノキサリンジオン誘導体を製造することを特徴とする一般式（３）で表されるキノキサリンジオン誘導体の製造方法。

（式中、R³¹,R³²,R³³は、アルキル基（炭素数1から18）及びアラルキル基から選ばれる基を表す。R^2１,R²²は、塩素、臭素及びヨウ素から選ばれるハロゲン原子、 脂肪族炭化水素基R³及び脂肪族炭化水素オキシ基OR³から選ばれる基（式中、R³はアルキル基（CnH2n+1,nは1〜20の整数を表す。）から選ばれる原子又は基を表す。）
（７）一般式（７）で表されるキノキサリンジオン誘導体を熱転移反応により一般式（４）で表されるキノキサリンジオン誘導体を製造することを特徴とする一般式（４）で表されるキノキサリンジオン誘導体の製造方法。

（式中、R³¹,R³²,R³³は、アルキル基（炭素数1から18）及びアラルキル基から選ばれる基を表す。R^2１,R²²は、塩素、臭素及びヨウ素から選ばれるハロゲン原子、脂肪族基R³及び脂肪族オキシ基OR³から選ばれる基（式中、R³はアルキル基（CnH2n+1, nは1〜20の整数を表す。）から選ばれる原子又は基を表す。））
（８）一般式（８）で表されるキノキサリンジオン誘導体を熱転移反応により一般式（５）で表されるキノキサリンジオン誘導体を製造することを特徴とする一般式（５）で表されるキノキサリンジオン誘導体の製造方法。

（式中、R^2１,R²²は、塩素、臭素及びヨウ素から選ばれるハロゲン原子、脂肪族炭化水素基R³及び脂肪族炭化水素オキシ基OR³から選ばれる基（式中、R³はアルキル基 （CnH2n+1, nは1〜20の整数を表す。）を表す。））
（９）前記（１）から（５）のいずれか記載のキノキサリンジオン誘導体からなる固体発光材料。
（１０）前記（１）から（５）のいずれか記載のキノキサリンジオン誘導体からなる金属塩可溶化剤。
（１１）前記（１）から（５）のいずれか記載のキノキサリンジオン誘導体からなる金属塩捕捉剤。 According to the present invention, the following inventions are provided.
(1) A quinoxalinedione derivative represented by the following general formula (1):

(In the formula, R ¹¹ and R ¹² are aliphatic hydrocarbon groups and may contain an unsaturated bond and a branched chain. R ²¹ and R ²² are halogen atoms selected from chlorine, bromine and iodine; An atom or group selected from an aromatic hydrocarbon group R ³ and an aliphatic hydrocarbon oxy group OR ³ (wherein R ³ is an alkyl group (CnH 2 n + 1, n represents an integer of 1 to 20)) Represents.)
(2) A quinoxalinedione derivative represented by the following general formula (2)

(In the formula, X represents an active group, and R ¹³ represents H.
R ¹⁴ represents an alkylene group (CnH2n, n represents an integer of 1 to 20) or an alkylene group containing an aromatic ring (CH2C6H4CH2).
R ²¹ and R ²² are a halogen atom selected from chlorine, bromine and iodine, or a group selected from an aliphatic hydrocarbon group R ³ and an aliphatic hydrocarbon oxy group OR ³ (wherein R ³ is an alkyl group (CnH 2n +1, n represents an integer of 1 to 20.) represents an atom or group selected from m. M represents an integer of 2 to 1000.)
(3) A quinoxalinedione derivative represented by the following general formula (3):

(Wherein R ³¹ , R ³² and R ³³ represent a group selected from an alkyl group (having 1 to 18 carbon atoms) and an aralkyl group.
R ²¹ and R ²² are a halogen atom selected from chlorine, bromine and iodine, a group selected from an aliphatic hydrocarbon group R ³ and an aliphatic hydrocarbon oxy group OR ³ (wherein R ³ is an alkyl group (CnH 2n + 1, n represents an integer of 1 to 20))) or an atom or group selected from. ).
(4) A quinoxalinedione derivative represented by the following general formula (4).

(Wherein R ³¹ , R ³² and R ³³ represent a group selected from an alkyl group (having 1 to 18 carbon atoms) and an aralkyl group.
R ²¹ and R ²² are a halogen atom selected from chlorine, bromine and iodine, a group selected from an aliphatic hydrocarbon group R ³ and an aliphatic hydrocarbon oxy group OR ³ (wherein R ³ is an alkyl group (CnH 2n + 1, n represents an integer of 1 to 20.) represents an atom or group selected from
(5) A quinoxalinedione derivative represented by the following general formula (5).

(Wherein R ²¹ and R ²² are a group selected from a halogen atom selected from chlorine, bromine and iodine, an aliphatic hydrocarbon group R ³ and an aliphatic hydrocarbon oxy group OR ³ (wherein R ³ is an alkyl group) An atom or group selected from a group (CnH2n + 1, n represents an integer of 1 to 20).)
(6) A quinoxalinedione derivative represented by the following general formula (6) is produced by a thermal transfer reaction to produce a quinoxalinedione derivative represented by the following general formula (3): A method for producing a quinoxalinedione derivative.

(In the formula, R ³¹ , R ³² and R ³³ represent a group selected from an alkyl group (having 1 to 18 carbon atoms) and an aralkyl group. R ²¹ and R ²² are halogen atoms selected from chlorine, bromine and iodine. A group selected from an aliphatic hydrocarbon group R ³ and an aliphatic hydrocarbon oxy group OR ³ (wherein R ³ represents an alkyl group (CnH 2 n + 1, n represents an integer of 1 to 20)); Or represents a group.)
(7) A quinoxaline represented by the general formula (4), wherein the quinoxaline dione derivative represented by the general formula (4) is produced by subjecting the quinoxaline dione derivative represented by the general formula (7) to a thermal transfer reaction. A method for producing a dione derivative.

(In the formula, R ³¹ , R ³² and R ³³ represent a group selected from an alkyl group (having 1 to 18 carbon atoms) and an aralkyl group. R ²¹ and R ²² are halogen atoms selected from chlorine, bromine and iodine. , A group selected from an aliphatic group R ³ and an aliphatic oxy group OR ³ (wherein R ³ represents an atom or group selected from an alkyl group (CnH 2 n + 1, n represents an integer of 1 to 20)) .))
(8) A quinoxaline represented by the general formula (5), wherein the quinoxaline dione derivative represented by the general formula (5) is produced by subjecting the quinoxaline dione derivative represented by the general formula (8) to a thermal transfer reaction. A method for producing a dione derivative.

(Wherein R ²¹ and R ²² are a group selected from a halogen atom selected from chlorine, bromine and iodine, an aliphatic hydrocarbon group R ³ and an aliphatic hydrocarbon oxy group OR ³ (wherein R ³ is an alkyl group) Group (CnH2n + 1, n represents an integer of 1 to 20).))
(9) A solid light-emitting material comprising the quinoxalinedione derivative according to any one of (1) to (5).
(10) A metal salt solubilizer comprising the quinoxalinedione derivative according to any one of (1) to (5).
(11) A metal salt scavenger comprising the quinoxalinedione derivative according to any one of (1) to (5).

  According to the present invention, a novel quinoxalinedione derivative having a chemical structure in which a plurality of carbonyl groups are adjacent to each other and a method for producing the same can be obtained. This novel compound can be used as a solid light-emitting material by ultraviolet excitation, a metal salt solubilizer capable of effectively dissolving a metal element as a metal salt, and a metal salt capable of effectively capturing the metal element as a metal salt It can be used as a scavenger.

式中、R¹¹とR¹²は、脂肪族炭化水素基を表す。これらの基は、飽和結合により形成されていてもよいし、不飽和結合（二重結合又は三重結合）を含んでいてもよい。また、これらの基は途中から枝分かれした分岐鎖により別れた基を有するものであってもよい。
R^2１、R²²は、塩素、臭素及びヨウ素から選ばれるハロゲン原子、脂肪族炭化水素基及び脂肪族炭化水素オキシ基（脂肪族炭化水素基の炭素数は1〜20の整数を表す。）から選ばれる基である。 The quinoxalinedione derivative obtained by the present invention is a compound represented by the following structural formula (1).

In the formula, R ¹¹ and R ¹² represent an aliphatic hydrocarbon group. These groups may be formed by a saturated bond or may contain an unsaturated bond (double bond or triple bond). Moreover, these groups may have groups separated by a branched chain branched from the middle.
R ²¹ and R ²² are from a halogen atom selected from chlorine, bromine and iodine, an aliphatic hydrocarbon group and an aliphatic hydrocarbon oxy group (the carbon number of the aliphatic hydrocarbon group represents an integer of 1 to 20). The group to be selected.

The aliphatic hydrocarbon groups of R ¹¹ and R ¹² include saturated and unsaturated chain hydrocarbon groups. The aliphatic hydrocarbon group includes those having an aliphatic hydrocarbon group, a chain hydrocarbon group, a cyclic hydrocarbon group, or an aromatic hydrocarbon group as a side chain. R ¹¹ and R ¹² may be the same group.
(1) A saturated aliphatic hydrocarbon group is a group represented by the general formula CnH2n + 1, and n represents an integer of 3 to 24.
Specific examples of the saturated aliphatic hydrocarbon having 3 to 24 carbon atoms include propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, isopentyl, t-pentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, nonyl , Isononyl, 3-ethyl-4-decanyl, undecanyl, nonadecanyl, tetradecanyl, pentadecanyl, hexadecanyl, dodecyl, heptadecanyl, eicosanyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
Further, the saturated aliphatic hydrocarbon preferably has 3 to 12 carbon atoms. Specifically, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, isopentyl, t-pentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, nonyl, isononyl, 3-ethyl-4-decanyl, undecanyl , Nonadecanyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
(2) The unsaturated aliphatic hydrocarbon group is an unsaturated aliphatic hydrocarbon group having 3 to 24 carbon atoms. The double bond may have not only one but also a plurality, or may have a triple bond. Specifically, groups such as propenyl, i-propenyl, allyl, butenyl, arylidene group, propargyl, pentenyl, i-pentenyl, hexenyl, i-hexenyl, octenyl, i-octenyl, decenyl, undecenyl, eicosenyl, dococenyl, tricosenyl, etc. Can give.
Furthermore, carbon number n of the said unsaturated aliphatic hydrocarbon becomes like this. Preferably it is 3-12. Specific examples include groups such as propenyl, i-propenyl, allyl, butenyl, arylidene, propargyl, pentenyl, i-pentenyl, hexenyl, i-hexenyl, octenyl, i-octenyl and decenyl.
(3) Aliphatic hydrocarbons having a cyclic hydrocarbon group or aromatic hydrocarbon group as a side chain include a cyclohexylmethyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, and the end of the aliphatic hydrocarbon is aromatic. Group substituted by a group hydrocarbon or cyclic hydrocarbon group. The aliphatic hydrocarbon has 1 to 24 carbon atoms.

R ²¹ and R ²² are groups selected from an aliphatic hydrocarbon group and an aliphatic hydrocarbon oxy group. The aliphatic hydrocarbon group is a saturated aliphatic hydrocarbon or unsaturated aliphatic hydrocarbon group.
(1) Specific examples of the saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, isopentyl, t-pentyl, hexyl, isohexyl, heptyl , Isoheptyl, octyl, isooctyl, nonyl, isononyl, 3-ethyl-4-decanyl, undecanyl, nonadecanyl, tetradecanyl, pentadecanyl, hexadecanyl, dodecyl, heptadecanyl, eicosanyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
The n is preferably 3-12.
Groups such as propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, isopentyl, t-pentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, nonyl, isononyl, 3-ethyl-4-decanyl, undecanyl, nonadecanyl, etc. Can be mentioned.
(2) The unsaturated aliphatic hydrocarbon group is an unsaturated aliphatic hydrocarbon group having 3 to 24 carbon atoms. The double bond may have not only one but also a plurality, or may have a triple bond. Specifically, groups such as propenyl, i-propenyl, allyl, butenyl, arylidene, propargyl, pentenyl, i-pentenyl, hexenyl, i-hexenyl, octenyl, i-octenyl, decenyl, undecenyl, eicosenyl, dococenyl, tricosenyl, etc. I can give you.
Furthermore, carbon number n of the said unsaturated aliphatic hydrocarbon becomes like this. Preferably it is 3-12. Specific examples include propenyl, i-propenyl, allyl, butenyl, arylidene, propargyl, pentenyl, i-pentenyl, hexenyl, i-hexenyl, octenyl, i-octenyl and decenyl groups.

  An aliphatic hydrocarbon oxy group is one in which an aliphatic hydrocarbon is bonded through oxygen. Same as above for aliphatic hydrocarbons.

合成は、活性基で置換された脂肪族炭化水素化合物をキノキサリンジオン誘導体とともに、不活性な溶媒中で反応させることにより行う。
脂肪族化合物の活性基としては、塩素、臭素、ヨウ素、p-トルエンスルホニルオキシ基などが用いられる。また、反応液中には副生する酸を補足するための塩基を添加するのが望ましい。
塩基としては、無水炭酸カリウム等の無機塩基や、トリエチルアミン、ピリジンなどの有機塩基が用いられ、溶媒としては、アセトン、Ｎ，Ｎ’−ジメチルイミダゾリジノン、ジメチルスルホキシド、Ｎ，Ｎ−ジメチルホルムアミドなどの溶媒が用いられる。反応温度は４０〜１５０℃である。
反応物の回収は、反応液を水中に注ぎ、析出物の濾過によるか、またはクロロホルムやトルエンなどで抽出することにより行う。また、反応物の回収は、反応液を減圧下に加熱して、溶媒を除き、残留物をクロロホルムやトルエンで抽出することによっても行うことができる。精製は、再結晶法またはシリカゲルカラムを用いて行うことができる。 The quinoxalinedione derivative represented by the general formula (1) is synthesized by substituting two unsubstituted nitrogens on the quinoxalinedione represented by the general formula (9) with an aliphatic hydrocarbon group.

The synthesis is carried out by reacting an aliphatic hydrocarbon compound substituted with an active group together with a quinoxalinedione derivative in an inert solvent.
As the active group of the aliphatic compound, chlorine, bromine, iodine, p-toluenesulfonyloxy group and the like are used. Further, it is desirable to add a base for supplementing the by-product acid to the reaction solution.
As the base, an inorganic base such as anhydrous potassium carbonate, or an organic base such as triethylamine or pyridine is used. As the solvent, acetone, N, N′-dimethylimidazolidinone, dimethyl sulfoxide, N, N-dimethylformamide or the like is used. These solvents are used. The reaction temperature is 40-150 ° C.
The reaction product is collected by pouring the reaction solution into water and filtering the precipitate, or extracting the product with chloroform or toluene. The reaction product can also be collected by heating the reaction solution under reduced pressure to remove the solvent and extracting the residue with chloroform or toluene. Purification can be performed using a recrystallization method or a silica gel column.

式中、Ｘは活性基、R¹³はＨを表す。R¹⁴はアルキレン基（CnH2n, n=1〜20の整数をあらわす。）、または芳香環を含むアルキレン基（CH2C6H4CH2）、R^2１,R²²は、塩素、臭素及びヨウ素から選ばれるハロゲン原子,脂肪族炭化水素基R³及び脂肪族炭化水素オキシ基OR³から選ばれる基（式中、R³はアルキル基（CnH2n+1,nは1〜20の整数を表す。）を表す。
前記一般式（２）はキノキサリンジオン骨核と脂肪族基が交互に結合した重合物で、ｍは2以上1000以下の整数であり、繰り返し数を表す。
R²¹, R²²は水素、ハロゲン、脂肪族炭化水素基、脂肪族炭化水素オキシ基を示す。（脂肪族炭化水素は一般式（１）で表される場合に同じ。）
該脂肪族炭化水素基において、その炭素数は1〜24、好ましくは1〜12である。該脂肪族炭化水素基においては、飽和及び不飽和の鎖状炭化水素基が包含される。脂肪族基は、側鎖として鎖状炭化水素基、環式炭化水素基、あるいは芳香族炭化水素基を有するものも含む。該アルキルオキシ基の鎖状炭化水素基の炭素数は1〜24、好ましくは1〜12である。アルキルオキシ基の炭素鎖には、飽和及び不飽和の鎖状炭化水素基が包含される。鎖状炭化水素基は、側鎖として鎖状炭化水素基、環式炭化水素基、あるいは芳香族炭化水素基を有するものも含む。R²¹,R²²は同一の基であってもよい。 The quinoxaline dione derivative obtained by the present invention is a quinoxaline dione derivative represented by the following general formula (2).

In the formula, X represents an active group, and R ¹³ represents H. R ¹⁴ is an alkylene group (CnH 2 n, n represents an integer of 1 to 20), or an alkylene group containing an aromatic ring (CH 2 C 6 H 4 CH 2), R ²¹ and R ²² are halogen atoms selected from chlorine, bromine and iodine, A group selected from an aromatic hydrocarbon group R ³ and an aliphatic hydrocarbon oxy group OR ³ (wherein R ³ represents an alkyl group (CnH 2 n + 1, n represents an integer of 1 to 20)).
The general formula (2) is a polymer in which a quinoxalinedione bone nucleus and an aliphatic group are alternately bonded, and m is an integer of 2 or more and 1000 or less, and represents the number of repetitions.
R ²¹ and R ²² represent hydrogen, halogen, an aliphatic hydrocarbon group, or an aliphatic hydrocarbon oxy group. (Aliphatic hydrocarbon is the same as represented by the general formula (1).)
In the aliphatic hydrocarbon group, the carbon number is 1 to 24, preferably 1 to 12. The aliphatic hydrocarbon group includes saturated and unsaturated chain hydrocarbon groups. The aliphatic group includes those having a chain hydrocarbon group, a cyclic hydrocarbon group, or an aromatic hydrocarbon group as a side chain. The chain hydrocarbon group of the alkyloxy group has 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms. The carbon chain of the alkyloxy group includes saturated and unsaturated chain hydrocarbon groups. The chain hydrocarbon group includes those having a chain hydrocarbon group, a cyclic hydrocarbon group, or an aromatic hydrocarbon group as a side chain. R ²¹ and R ²² may be the same group.

The quinoxalinedione polymer represented by the general formula (2) is synthesized by substituting two unsubstituted nitrogens on the quinoxalinedione represented by the general formula (9) with a divalent aliphatic group. The synthesis is obtained by reacting an aliphatic compound substituted with two active groups with a quinoxalinedione derivative in an inert solvent.
The number of m is a number determined by heat-treating the compound of the general formula (9) together with the aliphatic compound substituted with two active groups, and is usually 2 or more and up to about 1000. It has been confirmed. In addition, by adjusting reaction conditions such as temperature and time, it may be considered that the above number may be exceeded in some cases.

（式中、R³¹,R³²,R³³は、アルキル基（炭素数1〜18）及びフェニル基から選ばれる基を表す。R^2１,R²²は、水素原子,塩素、臭素及びヨウ素から選ばれるハロゲン原子、脂肪族炭化水素基R³及び脂肪族炭化水素オキシ基OR³から選ばれる基（式中、R³はアルキル基（CnH2n+1, nは1〜20の整数を表す。）を表す。）） The quinoxalinedione derivative obtained by the present invention is a compound represented by the following structural formula (3).

(In the formula, R ³¹ , R ³² and R ³³ represent a group selected from an alkyl group (having 1 to 18 carbon atoms) and a phenyl group. R ²¹ and R ²² are selected from a hydrogen atom, chlorine, bromine and iodine. A group selected from a halogen atom, an aliphatic hydrocarbon group R ³ and an aliphatic hydrocarbon oxy group OR ³ (wherein R ³ represents an alkyl group (CnH 2 n + 1, n represents an integer of 1 to 20)). To express.))

（式中、R³¹,R³²,R³³、R^2１,R²²は前記と同じ） The quinoxalinedione derivative represented by the general formula (3) is reacted with the 2,3-dichloroquinoxaline derivative represented by the general formula (10) with the allyl alcohol derivative represented by the general formula (11), It is produced by synthesizing the general formula (6) in which the chlorines at the 2nd and 3rd positions are substituted with allyl alcohol derivative residues, and then reacting them thermally.

(Wherein R ³¹ , R ³² , R ³³ , R ²¹ , R ²² are the same as above)

The reaction of the general formula (10) and the general formula (11) is performed by heating 2 equivalents or 2 equivalents or more of an allyl alcohol derivative in an inert solvent in a dry atmosphere with respect to the dichloroquinoxaline derivative. It is desirable to add a base for supplementing the by-product acid to the reaction solution. As the base, an inorganic base such as anhydrous potassium carbonate, or an organic base such as triethylamine or pyridine is used. As the solvent, acetone, N, N′-dimethylimidazolidinone, dimethyl sulfoxide, N, N-dimethylformamide or the like is used. These solvents are used. The reaction temperature is 100 to 180 ° C.
The reaction product is collected by pouring the reaction solution into water and filtering the precipitate, or extracting the product with chloroform or toluene. The reaction product can also be collected by heating the reaction solution under reduced pressure to remove the solvent and extracting the residue with chloroform or toluene. Purification can be performed using vacuum distillation or recrystallization.
The thermal reaction of the general formula (6) is a reaction in which an allyl group bonded to an oxygen atom is rearranged to an adjacent nitrogen atom. In this thermal rearrangement reaction, the reaction temperature is 120 to 300 ° C, preferably 180 to 220 ° C. In addition, this reaction is performed in an inert gas atmosphere such as nitrogen gas, in an inert solvent, or in the absence of a solvent. Examples of the organic solvent include high boiling point hydrocarbon solvents having a boiling point of 250 ° C. or higher, such as dodecane and diphenyl ether, and high boiling point ether solvents.

式中、R³¹,R³²,R³³は、アルキル基（炭素数1〜18）及びフェニル基から選ばれる基を表す。R^2１,R²²は、水素原子,塩素、臭素及びヨウ素から選ばれるハロゲン原子, 脂肪族炭化水素基R³及び脂肪族オキシ基OR³から選ばれる基（式、R³はアルキル基（CnH2n+1, nは1〜20の整数を表す。）を表す。
前記一般式(４)において、R³¹,R³²,R³³は水素、脂肪族炭化水素基または芳香族炭化水素基を示す。該脂肪族炭化水素基において炭素数は1〜18、好ましくは1〜4である。芳香族基の具体例としてフェニル基、ナフチル基などが挙げられる。
R^2１,R²²は、ハロゲン原子、脂肪族炭化水素基、アルキルオキシ基を示す。該脂肪族炭化水素基において、その炭素数は1〜２４、好ましくは1〜１２である。該脂肪族炭化水素基においては、飽和及び不飽和の鎖状炭化水素基が包含される。脂肪族炭化水素基は、側鎖として鎖状炭化水素基、環式炭化水素基、あるいは芳香族炭化水素基を有するものも含む。該アルキルオキシ基の鎖状炭化水素基の炭素数は1〜24、好ましくは1〜12である。アルキルオキシ基の炭素鎖には、飽和及び不飽和の鎖状炭化水素基が包含される。脂肪族基は、側鎖として鎖状炭化水素基、環式炭化水素基、あるいは芳香族炭化水素基を有するものも含む。R21,R22は同一の基であってもよい。 A quinoxalinedione derivative represented by the following general formula (4):

In the formula, R ³¹ , R ³² and R ³³ represent a group selected from an alkyl group (having 1 to 18 carbon atoms) and a phenyl group. R ²¹ and R ²² are a hydrogen atom, a halogen atom selected from chlorine, bromine and iodine, a group selected from an aliphatic hydrocarbon group R ³ and an aliphatic oxy group OR ³ (formula, R ³ is an alkyl group (CnH2n + 1, n represents an integer of 1 to 20).
In the general formula (4), R ³¹ , R ³² and R ³³ represent hydrogen, an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group has 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples of the aromatic group include a phenyl group and a naphthyl group.
R ²¹ and R ²² represent a halogen atom, an aliphatic hydrocarbon group, or an alkyloxy group. The aliphatic hydrocarbon group has 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms. The aliphatic hydrocarbon group includes saturated and unsaturated chain hydrocarbon groups. The aliphatic hydrocarbon group includes those having a chain hydrocarbon group, a cyclic hydrocarbon group, or an aromatic hydrocarbon group as a side chain. The chain hydrocarbon group of the alkyloxy group has 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms. The carbon chain of the alkyloxy group includes saturated and unsaturated chain hydrocarbon groups. The aliphatic group includes those having a chain hydrocarbon group, a cyclic hydrocarbon group, or an aromatic hydrocarbon group as a side chain. R21 and R22 may be the same group.

一般式（10）の化合物と式(12)の化合物の反応は一般式(６)の化合物の製造と同様であるが、反応温度は50〜100℃で行う。一般式(13)とアリルアルコール誘導体の反応は、一般式(６)の合成と同様で、一般式(13)に対して過剰のアリルアルコール誘導体を加え、反応温度100℃〜150℃で行う。 A 2,3-dichloroquinoxaline derivative represented by the general formula (10) is reacted with 0.5 equivalent of a diol (formula 12) to obtain the general formula (13), and then the remaining chlorine is converted to an allyl alcohol derivative. To synthesize a general formula (7). The general formula (4) is produced by rearranging the butenyl bone nucleus and the allyl group to the adjacent nitrogen on the quinoxaline bone nucleus by the thermal reaction of the general formula (7).

The reaction of the compound of general formula (10) and the compound of formula (12) is the same as the production of the compound of general formula (6), but the reaction temperature is 50-100 ° C. The reaction of the general formula (13) and the allyl alcohol derivative is the same as the synthesis of the general formula (6), and an excess of the allyl alcohol derivative is added to the general formula (13), and the reaction is performed at a reaction temperature of 100 ° C to 150 ° C.

式中、R^2１,R²²は、塩素、臭素及びヨウ素から選ばれるハロゲン原子、 脂肪族炭化水素基R³及び脂肪族炭化水素オキシ基OR³から選ばれる基（式中、R³はアルキル基 （CnH2n+1,nは1〜20の整数を表す。）から選ばれる原子又は基を表す。
前記一般式（５）はキノキサリンジオン骨核とイソブテン骨核 が、交互結合した重合物で、nは繰り返し単位を示し、ｎは2〜1000である。R^2１,R²²は、ハロゲン原子、脂肪族炭化水素基、アルキルオキシ基を示す。該脂肪族炭化水素基において、その炭素数は1〜24、好ましくは1〜12である。該脂肪族炭化水素基においては、飽和及び不飽和の鎖状炭化水素基が包含される。脂肪族基は、側鎖として鎖状炭化水素基、環式炭化水素基、あるいは芳香族炭化水素基を有するものも含む。該アルキルオキシ基の鎖状炭化水素基の炭素数は1〜24、好ましくは1〜12である。アルキルオキシ基の炭素鎖には、飽和及び不飽和の鎖状炭化水素基が包含される。脂肪族基は、側鎖として鎖状炭化水素基、環式炭化水素基、あるいは芳香族炭化水素基を有するものも含む。R^2１,R²²は同一の基であってもよい。 A quinoxalinedione derivative represented by the following general formula (5):

In the formula, R ²¹ and R ²² are a halogen atom selected from chlorine, bromine and iodine, a group selected from an aliphatic hydrocarbon group R ³ and an aliphatic hydrocarbon oxy group OR ³ (wherein R ³ is an alkyl group) (CnH2n + 1, n represents an integer of 1 to 20) represents an atom or group selected from
The general formula (5) is a polymer in which the quinoxalinedione bone nucleus and the isobutene bone nucleus are alternately bonded, n represents a repeating unit, and n is 2 to 1000. R ²¹ and R ²² represent a halogen atom, an aliphatic hydrocarbon group, or an alkyloxy group. In the aliphatic hydrocarbon group, the carbon number is 1 to 24, preferably 1 to 12. The aliphatic hydrocarbon group includes saturated and unsaturated chain hydrocarbon groups. The aliphatic group includes those having a chain hydrocarbon group, a cyclic hydrocarbon group, or an aromatic hydrocarbon group as a side chain. The chain hydrocarbon group of the alkyloxy group has 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms. The carbon chain of the alkyloxy group includes saturated and unsaturated chain hydrocarbon groups. The aliphatic group includes those having a chain hydrocarbon group, a cyclic hydrocarbon group, or an aromatic hydrocarbon group as a side chain. R ²¹ and R ²² may be the same group.

  The general formula (5) is obtained by reacting a 2,3-dichloroquinoxaline derivative represented by the general formula (10) with an equivalent amount of a diol (formula 12) to obtain the general formula (8). It is synthesized by the thermal rearrangement reaction of formula (8). The synthesis condition of the general formula (8) is performed according to the condition of the general formula (6). The thermal rearrangement reaction of the general formula (8) is performed according to the reaction of the general formula (7).

A compound represented by the general formula (1), (2), (3), (4), (5), in which two nitrogen atoms on the quinoxalinedione are substituted with an aliphatic residue, or a polymer, When irradiated with ultraviolet rays having a wavelength of 400 nm or less, light is emitted strongly even in the solid state.
The general formulas (1), (3), and (4) are all highly soluble in chloroform, toluene, tetrahydrofuran, ethyl acetate, acetone, etc., and there is no difficulty in synthesis reaction, purification, and solution coating.
In general formulas (2) and (5), when the quinoxaline bone nucleus does not have a substituent and the degree of polymerization is high, the solubility may be low. And easily soluble.

また、溶液の蛍光スペクトルでは、発光スペクトルの波長シフトとともに発光強度の増加としても確認された。
さらに金属元素との錯形成は、ESI-MSにより錯体由来の質量ピークとして確認された。 Two carbonyl groups on the compounds represented by the general formulas (1), (2), (3), (4), and (5) are strongly coordinated to a metal element and have a property of forming a complex.
Strong coordination ability to metal elements is confirmed by nuclear magnetic resonance spectrum (NMR), visible ultraviolet absorption spectroscopy, fluorescence spectroscopy and the like. Similar to quinoxalinedione, cyclohexane-1,2-dione with two adjacent carbonyl groups and 2,3-dihydroxynaphthalene (compound of structural formula (14)) with adjacent coordinating oxygen atoms, Even under conditions where almost no NMR peak shift was observed, a remarkable low magnetic field shift of each hydrogen atom peak was observed in the quinoxalinedione derivative of the present invention.

Moreover, in the fluorescence spectrum of the solution, it was confirmed that the emission intensity increased with the wavelength shift of the emission spectrum.
Furthermore, complex formation with metal elements was confirmed by ESI-MS as a mass peak derived from the complex.

The present invention will be described in more detail with reference to examples. The present invention is not limited by this example.

原料物質は、以下の化合物である。

前記原料物質0.81ｇ、臭化ドデシル3.0ｇ、水素化ナトリウム0.42ｇをN,N-ジメチルイミダゾリジノン20ml中、110℃で12時間、加熱攪拌を行った。
反応液を真空下に乾固し、トルエン可溶分をシリカゲルカラムで精製した(溶離液ヘキサン、1.19g)。目的性生物の確認値は以下の通りである。
¹H NMR (CDCl₃、内標準TMS) d=0 .87 (6H, t, CH3), 1.25-1.45 (36H, ｍ, CH2), 1.73-1.764(4H, m, CH2), 4.19 (4H, t, NCH2), 7.25 (2H, s, Ar-H), 7.25 (2H, s, Ar-H) Synthesis of a compound represented by the structural formula (15) (one of the compounds represented by the general formula (1)).

The raw material is the following compound.

0.81 g of the raw material, 3.0 g of dodecyl bromide, and 0.42 g of sodium hydride were heated and stirred at 110 ° C. for 12 hours in 20 ml of N, N-dimethylimidazolidinone.
The reaction solution was dried under vacuum, and the toluene-soluble component was purified with a silica gel column (eluent hexane, 1.19 g). Confirmation values of target organisms are as follows.
¹ H NMR (CDCl ₃ , internal standard TMS) d = 0.87 (6H, t, CH3), 1.25-1.45 (36H, m, CH2), 1.73-1.764 (4H, m, CH2), 4.19 (4H, t, NCH2), 7.25 (2H, s, Ar-H), 7.25 (2H, s, Ar-H)

原料物質は以下の化合物である。

原料物質1.11ｇ、臭化アリル4.8ｇ、無水炭酸カリウム1.52ｇをN,N-ジメチルイミダゾリジノン20ml中、120℃で5時間、加熱攪拌を行った。反応液より無機塩を濾別し、真空下に乾固した。シリカゲルカラムで精製した(溶離液アセトン-クロロホルム（4：96）、収率69%。
構造式１６の化合物の確認値
¹H NMR (CDCl₃、内標準TMS) d=3.89 (6H, s, OCH3), 4.87-4.88 (4H, m, NCH2), 5.25-5.335(4H, m, =CH2), 5.91-5.96 (2H, m, OCH2-), 6.79 (2H, s, Ar-H), 6.8 (2H, s, Ar-H) Synthesis of a compound represented by Structural Formula (16) (one of the compounds represented by Formula (1)).

The raw material is the following compound.

1.11 g of raw material, 4.8 g of allyl bromide and 1.52 g of anhydrous potassium carbonate were stirred in 20 ml of N, N-dimethylimidazolidinone at 120 ° C. for 5 hours. Inorganic salts were filtered off from the reaction solution and dried under vacuum. Purification by silica gel column (eluent acetone-chloroform (4:96), yield 69%).
Confirmation value of compound of structural formula 16
¹ H NMR (CDCl ₃ , internal standard TMS) d = 3.89 (6H, s, OCH3), 4.87-4.88 (4H, m, NCH2), 5.25-5.335 (4H, m, = CH2), 5.91-5.96 (2H , m, OCH2-), 6.79 (2H, s, Ar-H), 6.8 (2H, s, Ar-H)

原料物質は以下の化合物である。

原料物質4.97g、無視炭酸カリウム10.0ｇ、アリルアルコール4.6ｇをN,N-ジメチルアセトアミド30mlとともに、耐圧容器中150℃において加熱攪拌を行った。反応液より、無機塩を濾別後、真空蒸留により中間原料物質１８を得た（120℃/0.1mmHg、4.57g）
中間原料物質（構造式（１８）で表される化合物）は以下の構造式である。

¹H NMR (CDCl₃、内標準TMS) d=4.98-5.08 (4H, m, OCH2), 5.311-5.510(4H, t, =CH2), 6.146-6.224 (2H, m, -CH=), 7.456-7.488 (2H, m, Ar-H), 7.456-7.488 (2H, m, Ar-H)
前記中間原料物質1.0gをN,N-ジブチルアニリン10ml中、窒素雰囲気下に220℃で12時間加熱した。反応液を真空下に乾固させ、シリカゲルカラム （溶離液アセトン-クロロホルム15:85）で目的［化4］を得た（85％）。
¹H NMR (CDCl₃、内標準TMS) d=4.79-4.81 (4H, m, NCH2), 5.17-5.23(4H, m, =CH2), 5.94-6.01 (2H, m, -CH=), 7.21-7.24 (2H, m, Ar-H), 7.21-7.24(2H, m, Ar-H) Synthesis of a compound of the following structural formula (17) (one of the compounds represented by the general formula (1))

The raw material is the following compound.

4.97 g of raw material, 10.0 g of neglected potassium carbonate, and 4.6 g of allyl alcohol were heated and stirred at 150 ° C. in a pressure vessel together with 30 ml of N, N-dimethylacetamide. After the inorganic salt was filtered off from the reaction solution, intermediate raw material 18 was obtained by vacuum distillation (120 ° C./0.1 mmHg, 4.57 g).
The intermediate raw material (compound represented by the structural formula (18)) has the following structural formula.

¹ H NMR (CDCl ₃ , internal standard TMS) d = 4.98-5.08 (4H, m, OCH2), 5.311-5.510 (4H, t, = CH2), 6.146-6.224 (2H, m, -CH =), 7.456 -7.488 (2H, m, Ar-H), 7.456-7.488 (2H, m, Ar-H)
1.0 g of the intermediate raw material was heated in 10 ml of N, N-dibutylaniline at 220 ° C. for 12 hours in a nitrogen atmosphere. The reaction solution was dried under vacuum, and the target [Chemical Formula 4] was obtained (85%) using a silica gel column (eluent acetone-chloroform 15:85).
¹ H NMR (CDCl ₃ , internal standard TMS) d = 4.79-4.81 (4H, m, NCH2), 5.17-5.23 (4H, m, = CH2), 5.94-6.01 (2H, m, -CH =), 7.21 -7.24 (2H, m, Ar-H), 7.21-7.24 (2H, m, Ar-H)

原料物質は以下の構造式の化合物である。

原料物質1.98ｇ、2-メチレン-1,3-プロパンジオール0.45ｇ、無水炭酸カリウム2.07ｇをジメチルスルホキシド10ml中、100℃で3時間加熱攪拌した。反応混合物を水に注ぎ、析出物を濾過で回収した。粗製物をシリカゲルカラムで精製して化合物25を得た（溶離液トルエン、収率78％）。
中間原料は以下の構造式の化合物（２０）である

¹H NMR (CDCl₃、内標準TMS) d=5.15 (4H, s, OCH₂), 5.47 (2H, s, =CH₂), 7.37-7.64, 7.79-7.94 (8H, m, Ar-H) Synthesis of a compound having the following structural formula (structural formula (19)) (one of the compounds represented by the general formula (4))

The raw material is a compound having the following structural formula.

1.98 g of raw material, 0.45 g of 2-methylene-1,3-propanediol, and 2.07 g of anhydrous potassium carbonate were heated and stirred at 100 ° C. for 3 hours in 10 ml of dimethyl sulfoxide. The reaction mixture was poured into water and the precipitate was collected by filtration. The crude product was purified on a silica gel column to give compound 25 (eluent toluene, 78% yield).
The intermediate raw material is a compound (20) having the following structural formula

¹ H NMR (CDCl ₃ , internal standard TMS) d = 5.15 (4H, s, OCH ₂ ), 5.47 (2H, s, = CH ₂ ), 7.37-7.64, 7.79-7.94 (8H, m, Ar-H)

中間原料物質（２１）を用いて、実施例４の化合物２０の合成と同様に化合物の残存する塩素をアリル基で置換することにより合成した。化合物5の熱転位反応は実施例４の化合物２０の熱転位反応と同様に行うことができる。

1H-NMR(、内標準TMS): 4.88-4.89(2H, m, =CH2(Butenyl)), 4.91-4.99(8H, m, NCH2(Allyl, Butenyl)), 5.25-5.32 (4H, m, =CH2(Allyl)), 5.91-5.97(2H, m,-CH=), 5.91-5.97 (8H, m, Ar-H)
化合物２１の化合物２２への熱転位反応においては中間生成物（２３）及び（２４）が生成する。

¹H NMR (CDCl₃、内標準TMS) d= 4.88-4.904(2H, m, NCH2(Allyl)), 5.16-5.26 (8H, m, =CH2(Allyl), OCH2(Butenyl)), 5.57 (4H, bs, =CH2(Butenyl)), 5.88-5.955(2H, m, -CH=), 5.88-5.95 (2H, m, Ar-H), 7.23-7.26 (2H, m, Ar-H), 7.35-7.36 (2H, m, Ar-H), 7.28-7.60 (2H, m, Ar-H)

¹H NMR (CDCl₃、内標準TMS) d=4.82 (2H, s, =CH2(Butenyl)), 4.99-5.01(8H, m, NCH2, OCH2), 5.31-5.50 (4H, m, =CH2(Allyl)), 6.15-6.19(2H, m, -CH=), 6.15-6.19 (6H, m, Ar-H), 7.62-7.64 (2H, m, Ar-H)
Synthesis of the following target compound (22)

Using the intermediate raw material (21), synthesis was performed by substituting the remaining chlorine of the compound with an allyl group in the same manner as in the synthesis of Compound 20 of Example 4. The thermal rearrangement reaction of compound 5 can be carried out in the same manner as the thermal rearrangement reaction of compound 20 of Example 4.

1H-NMR (Internal standard TMS): 4.88-4.89 (2H, m, = CH2 (Butenyl)), 4.91-4.99 (8H, m, NCH2 (Allyl, Butenyl)), 5.25-5.32 (4H, m, = CH2 (Allyl)), 5.91-5.97 (2H, m, -CH =), 5.91-5.97 (8H, m, Ar-H)
In the thermal rearrangement reaction of compound 21 to compound 22, intermediate products (23) and (24) are formed.

¹ H NMR (CDCl ₃ , internal standard TMS) d = 4.88-4.904 (2H, m, NCH2 (Allyl)), 5.16-5.26 (8H, m, = CH2 (Allyl), OCH2 (Butenyl)), 5.57 (4H , bs, = CH2 (Butenyl)), 5.88-5.955 (2H, m, -CH =), 5.88-5.95 (2H, m, Ar-H), 7.23-7.26 (2H, m, Ar-H), 7.35 -7.36 (2H, m, Ar-H), 7.28-7.60 (2H, m, Ar-H)

¹ H NMR (CDCl ₃ , internal standard TMS) d = 4.82 (2H, s, = CH2 (Butenyl)), 4.99-5.01 (8H, m, NCH2, OCH2), 5.31-5.50 (4H, m, = CH2 ( Allyl)), 6.15-6.19 (2H, m, -CH =), 6.15-6.19 (6H, m, Ar-H), 7.62-7.64 (2H, m, Ar-H)

キノキサリンジオン（一般式9（R²¹=OCH3, R²²= OCH3））0.33ｇ、を無水炭酸カリウム0.56ｇ、3-クロロ-2-クロロメチル-1-プロパン0.19ｇ、ジメチルイミダゾリジノン4mlの混合液を110℃で2日間加熱攪拌した。無機塩を濾過により取り除き、液を乾固して、重合物を得た（0.52ｇ）。
1H-NMR(TMS): 4.84-5.16 (6H, b, =CH2, NCH2), 6.74-6.86 (2H, b, Ar-H) Synthesis of structural formula (25) (one of the compounds represented by general formula (5))

Mixing 0.33 g of quinoxalinedione (general formula 9 (R ²¹ = OCH3, R ²² = OCH3)) with 0.56 g of anhydrous potassium carbonate, 0.19 g of 3-chloro-2-chloromethyl-1-propane and 4 ml of dimethylimidazolidinone The solution was heated and stirred at 110 ° C. for 2 days. The inorganic salt was removed by filtration, and the liquid was dried to obtain a polymer (0.52 g).
1H-NMR (TMS): 4.84-5.16 (6H, b, = CH2, NCH2), 6.74-6.86 (2H, b, Ar-H)

Solid state emission spectrum (number is emission wavelength, (*) is the emission wavelength with the highest intensity, excitation wavelength is 310 nm)
Measurement values of structural formula 15 of Example 1: 397 nm (*), 416 nm
The measured value of the structural formula 17 in Example 3 (R ¹¹ = CH 2 CH = CH 2, R ¹² = CH 2 CH = CH 2, R ²¹ = H,
R ²² = H): 395 nm (*), 415 nm
Of formula ^{1 (R 11 = CH2C6H5, R} 12 = CH2C6H5, R 21 = H, R 22 = H) measured in the case of: 386nm, 400nm (*), 421nm
Measured value of structural formula 16 of Example 2 (R ¹¹ = CH 2 CH = CH 2, R ¹² = CH 2 CH = CH 2, R ²¹ = OCH 3, R ²² = OCH 3): 454 nm
Measured values of the compound of the general formula 3 (R ³¹ = R ³² = R ³³ = H, R ²¹ = H, R ²² = H): 367 nm, 385 nm (*), 402 nm

NMRのピークへの影響（低磁場シフト）。溶媒：重アセトニトリル、内部標準物質：TMS、化合物39の濃度：20mmol/l、添加塩濃度：20mmol/l

無添加： 4.793-4.811 (4H, m, NCH2), 5.174-5.234 (4H, m, =CH2),5.946-6.011 (2H, m, -CH=), 7.216-7.246 (2H, m, Ar-H), 7.286-7.315 (2H, m, Ar-H)
過塩素酸リチウム：4.804-4.817 (4H, bs, NCH2), 5.176-5.238 (4H, m, =CH2),5.946-6.013 (2H, m, -CH=), 7.229-7.256 (2H, m, Ar-H), 7.292-7.319 (2H, m, Ar-H)

過塩素酸マグネシウム：4.901-4.915(4H, m, NCH2), 5.274-5.315 (4H, m, =CH2), 5.962-6.029 (2H, m, -CH=), 7.417-7.443 (2H, m, Ar-H), 7.505-7.524 (2H, m, Ar-H)過塩素酸バリウム：4.845-4.856(4H, m, NCH2), 5.214-5.255 (4H, m, =CH2), 5.924-5.989 (2H, m, -CH=), 7.361-7.388 (2H, m, Ar-H), 7.432-7.459 (2H, m, Ar-H)

酢酸亜鉛：4.810-4.828(4H, m, NCH2), 5.185-5.248 (4H, m, =CH2), 5.939-6.014 (2H, m, -CH=), 7.248-7.275 (2H, m, Ar-H), 7.312-7.339 (2H, m, Ar-H)
酢酸ユーロピウム：5.52(4H, bs, NCH2), 5.37-5.438 (4H, m, =CH2), 6.109-6.173 (2H, m, -CH=), 7.422-7.448 (2H, m, Ar-H), 7.558-7.585 (2H, m, Ar-H) The compound of Example 3 (Structural Formula (17)) is used to show the metal scavenging ability.

Effect on NMR peak (low magnetic field shift). Solvent: deuterated acetonitrile, internal standard: TMS, concentration of compound 39: 20 mmol / l, added salt concentration: 20 mmol / l

No additive: 4.793-4.811 (4H, m, NCH2), 5.174-5.234 (4H, m, = CH2), 5.946-6.011 (2H, m, -CH =), 7.216-7.246 (2H, m, Ar-H ), 7.286-7.315 (2H, m, Ar-H)
Lithium perchlorate: 4.804-4.817 (4H, bs, NCH2), 5.176-5.238 (4H, m, = CH2), 5.946-6.013 (2H, m, -CH =), 7.229-7.256 (2H, m, Ar -H), 7.292-7.319 (2H, m, Ar-H)

Magnesium perchlorate: 4.901-4.915 (4H, m, NCH2), 5.274-5.315 (4H, m, = CH2), 5.962-6.029 (2H, m, -CH =), 7.417-7.443 (2H, m, Ar -H), 7.505-7.524 (2H, m, Ar-H) Barium perchlorate: 4.845-4.856 (4H, m, NCH2), 5.214-5.255 (4H, m, = CH2), 5.924-5.989 (2H, m, -CH =), 7.361-7.388 (2H, m, Ar-H), 7.432-7.459 (2H, m, Ar-H)

Zinc acetate: 4.810-4.828 (4H, m, NCH2), 5.185-5.248 (4H, m, = CH2), 5.939-6.014 (2H, m, -CH =), 7.248-7.275 (2H, m, Ar-H ), 7.312-7.339 (2H, m, Ar-H)
Europium acetate: 5.52 (4H, bs, NCH2), 5.37-5.438 (4H, m, = CH2), 6.109-6.173 (2H, m, -CH =), 7.422-7.448 (2H, m, Ar-H), 7.558-7.585 (2H, m, Ar-H)

Metal capture capacity of reference material 1 cyclohexane-1,2-dione: 20 mmol / l
No additive: 1.929-1.977 (4H, m, CH2), 2.323-2.359 (2H, m, CH2), 2.45-2.477 (2H, m, CH2)
Magnesium perchlorate: 1.928-1.979 (4H, m, CH2), 2.325-2.359 (2H, m, CH2), 2.453-2.480 (2H, m, CH2)
concentration

無添加：1H-NMR(TMS):3.766-3.837 (4H, m, Ar-CH2), 4.916-5.004 (4H, t, =CH2), 5.998-6.065 (2H, m,-CH=), 6.94 (2H, m, Ar-OH), 6.94 (2H, m, Ar-H), 7.835-7.854 (2H, m, Ar-H)
過塩素酸マグネシウム：3.783-3.802 (4H, m, Ar-CH2), 4.916-5.001 (4H, m, =CH2), 6.000-6.055(2H, m, -CH=), 6.94 (2H, m, Ar-OH), 6.94 (2H, m, Ar-H), 7.835-7.855 (2H, m, Ar-H) Metal capture capability of reference material 2

No addition: 1H-NMR (TMS): 3.766-3.837 (4H, m, Ar-CH2), 4.916-5.004 (4H, t, = CH2), 5.998-6.065 (2H, m, -CH =), 6.94 ( 2H, m, Ar-OH), 6.94 (2H, m, Ar-H), 7.835-7.854 (2H, m, Ar-H)
Magnesium perchlorate: 3.783-3.802 (4H, m, Ar-CH2), 4.916-5.001 (4H, m, = CH2), 6.000-6.055 (2H, m, -CH =), 6.94 (2H, m, Ar -OH), 6.94 (2H, m, Ar-H), 7.835-7.855 (2H, m, Ar-H)

ESI-MSによる錯体ピーク（Lは化合物41を、ANは溶媒を意味する）。
溶媒：アセトニトリル、
（１）化合物41：0.04mmol/l、過塩素酸マグネシウム：0.01mmol/l、ピーク質量507([2L+Mg-H]⁺),306([L+Mg+AN-H]⁺)
（２）化合物41：0.04mmol/l、過塩素酸リチウム：0.01mmol/l、ピーク質量：491[2L+Li]⁺,290[L+Ba+AN]⁺

The compound of Example 3 (Structural Formula (17)) is used to show the metal scavenging ability.

Complex peak by ESI-MS (L means compound 41, AN means solvent).
Solvent: acetonitrile,
(1) Compound 41: 0.04 mmol / l, magnesium perchlorate: 0.01 mmol / l, peak mass 507 ([2L + Mg-H] ⁺ ), 306 ([L + Mg + AN-H] ⁺ )
(2) Compound 41: 0.04 mmol / l, lithium perchlorate: 0.01 mmol / l, peak mass: 491 [2L + Li] ⁺ , 290 [L + Ba + AN] ⁺

Claims (10)

A quinoxalinedione compound represented by the following general formula (2):

(In the formula, X represents chlorine and bromine, and R ¹³ represents H.
R ¹⁴ represents a C1-C3 alkylene group substituted with CH = .
R ²¹ and R ²² are groups selected from an aliphatic hydrocarbon group R ³ and an aliphatic hydrocarbon oxy group OR ³ (wherein R ³ is an alkyl group (C _n H _{2n + 1} , n is 1 to 3). Represents an integer.) Represents an atom or group selected from: m represents an integer of 2 to 1000)) A quinoxalinedione compound represented by the following general formula (3):

(In the formula, R ³¹ , R ³² and R ³³ represent an alkyl group (having 1 to 3 carbon atoms).
R ²¹ and R ²² are groups selected from an aliphatic hydrocarbon group R ³ and an aliphatic hydrocarbon oxy group OR ³ (wherein R ³ is an alkyl group (C _n H _{2n + 1} , n is 1 to 3). Represents an integer.)) Represents an atom or group selected from. ) A quinoxalinedione compound represented by the following general formula (4):

(In the formula, R ³¹ , R ³² and R ³³ represent an alkyl group (having 1 to 3 carbon atoms).
R ²¹ and R ²² are groups selected from an aliphatic hydrocarbon group R ³ and an aliphatic hydrocarbon oxy group OR ³ (wherein R ³ is an alkyl group (C _n H _{2n + 1} , n is 1 to 3). Represents an integer.) Represents an atom or group selected from :)) A quinoxalinedione compound represented by the following general formula (5):

(In the formula, R ²¹ and R ²² are groups selected from an aliphatic hydrocarbon group R ³ and an aliphatic hydrocarbon oxy group OR ³ (wherein R ³ is an alkyl group (C _n H _{2n + 1} , n is Represents an integer of 1 to 3.) represents an atom or group selected from :)) A quinoxalinedione compound represented by the general formula (3), wherein a quinoxalinedione compound represented by the general formula (3) is produced by a thermal transfer reaction of the quinoxalinedione compound represented by the following general formula (6): Manufacturing method.

(In the formula, R ³¹ , R ³² and R ³³ represent an alkyl group (having 1 to 3 carbon atoms).
R ²¹ and R ²² are groups selected from an aliphatic hydrocarbon group R ³ and an aliphatic hydrocarbon oxy group OR ³ (wherein R ³ is an alkyl group (C _n H _{2n + 1} , n is 1 to 3). Represents an integer.) Represents an atom or group selected from :)) A quinoxalinedione compound represented by the general formula (4) is produced by a thermal transfer reaction of the quinoxalinedione compound represented by the general formula (7). Production method.

(In the formula, R ³¹ , R ³² and R ³³ represent an alkyl group (having 1 to 3 carbon atoms).
R ²¹ and R ²² are groups selected from an aliphatic group R ³ and an aliphatic oxy group OR ³ (wherein R ³ represents an alkyl group (C _n H _{2n + 1} , n represents an integer of 1 to 3). Represents an atom or group selected from A quinoxalinedione compound represented by the general formula (5) is produced by a thermal transfer reaction of the quinoxalinedione compound represented by the general formula (8). Production method.

(Wherein R ²¹ and R ²² are groups selected from an aliphatic hydrocarbon group R ³ and an aliphatic hydrocarbon oxy group OR ³ (wherein R ³ is an alkyl group (C _n H _{2n + 1} , n is Represents an integer of 1 to 3.))))   A solid light-emitting material comprising the quinoxalinedione compound according to any one of claims 1 to 4.   A metal salt solubilizer comprising the quinoxalinedione compound according to any one of claims 1 to 4. A metal salt scavenger comprising the quinoxalinedione compound according to any one of claims 1 to 4.