JP2011026317A - Quinacridone derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide quinacridone soluble in general-purpose organic solvents, excellent in robustness and processability, emitting white-colored light by itself, or able to be brought to white-colored light-emitting compositions by combining with other light emitting compounds. <P>SOLUTION: Quinacridone derivatives expressed by structural formula (1) are provided. Light-emitting devices using the quinacridone derivatives can be easily produced. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a quinacridone derivative. More specifically, the present invention is soluble in a general-purpose organic solvent, has excellent fastness and processability, emits white light by itself, or emits other light when it does not emit white light by itself. The present invention relates to a quinacridone derivative that can be made into a composition capable of emitting white light when combined with a functional compound.

  Quinacridone was developed in Germany about 100 years ago and later redeveloped by DuPont in the United States. In 1952, a quinacridone pigment that was robust and excellent in weather resistance was developed and used as an exterior paint for automobiles.

  Ordinary organic light emitters have a light emission ability of about 1 Lm / W, but quinacridone has excellent performance as an organic light emitter, and in recent years, quinacridone having a light emission ability of about 20 Lm / W has been developed (Non-Patent Documents). 1).

  Referring to Non-Patent Document 1, a basic skeleton structure of linear-trans-quinacridone (IV) is described. The position numbers of carbon atoms and nitrogen atoms on the ring forming the skeleton of the linear-trans-quinacridone (IV) are as shown in the structural formula (IV) described in Non-Patent Document 1.

Non-Patent Document 1 includes
(a) As a derivative of linear-trans-quinacridone (IV), a compound in which a bromine atom is bonded to the 2-position carbon atom and a hydrogen atom is bonded to the 5-position and 12-position nitrogen atoms in the quinacridone skeleton (a ),
(b) As a derivative of linear-trans-quinacridone (IV), an iodine atom is bonded to each of the 2nd and 9th carbon atoms in the quinacridone skeleton, and a hydrogen atom is bonded to the 5th and 12th nitrogen atoms. A compound (b),
(c) As a derivative of linear-trans-quinacridone (IV), a methyl group is present at the 2-position carbon atom in the quinacridone skeleton, or the 2-position and 9-position carbon atoms, respectively, and the 5- and 12-position nitrogen atoms. Discloses a compound (c) formed by bonding a hydrogen atom.

  According to this Non-Patent Document 1, linear-trans-quinacridone (IV) including these compounds (a) to (c) is extremely poorly soluble in ordinary organic solvents, and therefore visible light of these substances is visible. It has been reported that these substances had to be dissolved in sulfuric acid to obtain an absorption spectrum (see Non-Patent Document 1, page 8, right column, lines 8 to 12). Further, Non-Patent Document 1 summarizes the ultraviolet spectrum of quinacridone derivatives such as 2,9-dimethylquinacridone dissolved in concentrated sulfuric acid in Table III.

  However, it is difficult to find industrial uses for substances that are both deleterious and must be dissolved in concentrated sulfuric acid, which is a strong acid.

  On the other hand, in Patent Document 1, in the quinacridone skeleton represented by the formula (IV) in Non-Patent Document 1, hydrogen atoms are bonded to the nitrogen atoms at the 5th and 12th positions, and the number of carbon atoms is 1 to 2 and 9th. Although a quinacridone derivative to which 10 alkyl groups are bonded is suggested, a hydrogen atom is bonded to the 5th and 12th nitrogen atoms, and an alkyl group having 5 carbon atoms at the 2nd and 9th positions, or an alkyl having 7 carbon atoms. Examples include two quinacridone derivatives to which groups are bonded, and one quinacridone derivative in which a hydrogen atom is bonded to the nitrogen atoms at the 5th and 12th positions and an alkyl group having 4 carbon atoms is bonded to the 4th and 8th positions. It has only been done.

  In Patent Document 2, in the quinacridone skeleton represented by the formula (IV) in Non-Patent Document 1, hydrogen atoms are bonded to the nitrogen atoms at the 5th and 12th positions, and —COOH is bonded to the 3rd and 10th positions. Examples of quinacridone derivatives and quinacridone derivatives in which a methyl group is bonded to the nitrogen atoms at the 5th and 12th positions and —COOH is bonded to the 3rd and 10th positions are shown as examples.

  In Patent Document 3, in the quinacridone skeleton represented by the formula (IV) in Non-Patent Document 1, an alkyl group having 1 to 10 carbon atoms is bonded to the nitrogen atoms at the 5th and 12th positions, and at the 3rd and 9th positions. Quinacridone derivatives to which —COOH is bound are described (see claim 2).

  However, the quinacridone derivatives described as examples in Patent Document 3 are examples in which quinacridone derivatives in which hydrogen atoms are bonded to the nitrogen atoms at the 5th and 12th positions and —COOH is bonded to the 3rd and 10th positions. Is shown as

Patent Document 4 discloses a quinacridone derivative in which R ₁ is a hydrogen atom, R ₂ is an alkyl group, R ₃ is a hydrogen atom, and R ₄ is an alkylene group to which an aryl group is bonded. Referring to a synthesis example in Patent Document 4, a quinacridone derivative that emits green light in Synthesis Example 1 is disclosed (see Example 1), and a quinacridone derivative that emits green light in Synthesis Example 6 is disclosed (see Example 2). In Patent Document 4, a quinacridone derivative that emits white light is not disclosed as a synthesis example. Further, it is impossible to predict a substance capable of emitting white light from the descriptions of Synthesis Examples 1 and 6 in Patent Document 4.

JP 2005-35965 A JP 2007-99723 A International Publication No. 2006/115131 International Publication No. 2004/067674

S.S.Labana and L.L.Labana, Chem.Rev. 67,1 (1967)

  An object of the present invention is to provide a device that is soluble in a general-purpose organic solvent, has excellent fastness and processability, emits white light by itself, or can be combined with other light-emitting compounds to emit white light. It is to provide a quinacridone derivative that can be produced.

Means for solving the problems are as follows:
(1) A quinacridone derivative represented by the following structural formula 1.

(However, in Structural Formula 1, X is —COOR ₁ (where R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), a bromine atom, an iodine atom, or an aromatic hydrocarbon group. An alkyl group having 1 to 10 carbon atoms (excluding the carbon number of the aromatic hydrocarbon group when the aromatic hydrocarbon group is substituted), a structural formula of —O—CH ₂ CH ₂ —O— ( 1A), one oxygen atom in the structural formula (1A) is bonded to the benzene ring in the structural formula 1, and the other oxygen atom is bonded to the carbon on the 4-position benzene ring in the structural formula 1. A dioxane-forming group, a group represented by —CH ₂ —Ar (wherein Ar represents an aromatic hydrocarbon group), an aromatic hydrocarbon group-substituted oxadiazole group represented by the structural formula (1B) (provided that the structure Ar in the formula (1B) is an aromatic charcoal It represents hydrogen radical.), Or structural formula of -CH = CH-Ar (1C) (where, Ar represents a represents an aromatic hydrocarbon group.)

Y is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms that may be substituted with an aromatic hydrocarbon group (excluding the carbon number of the aromatic hydrocarbon group when the aromatic hydrocarbon group is substituted). And when X is a bromine atom or an iodine atom, Y is an optionally substituted aromatic hydrocarbon group having 1 to 20 carbon atoms (when an aromatic hydrocarbon group is substituted, the carbon number of the aromatic hydrocarbon group is Is an alkyl group. )
(2) Y is an alkyl group having 1 to 20 carbon atoms that may be substituted for an aromatic hydrocarbon group (excluding the number of carbon atoms in the aromatic hydrocarbon group when the aromatic hydrocarbon group is substituted). In some cases, X is —COOR _1a (wherein R _1a represents an alkyl group having 2 to 10 carbon atoms), and may have an aromatic hydrocarbon group having 1 to 10 carbon atoms (an aromatic hydrocarbon group When substituted, the alkyl group of the aromatic hydrocarbon group is excluded.) The aromatic hydrocarbon group-substituted oxadiazole group represented by the structural formula (1B) (provided that the aromatic hydrocarbon group is a pyrenyl group) Or a quinacridone derivative according to (1) above, which is an aromatic-substituted vinyl group represented by the structural formula (1C),
(3) Y represents an alkyl group having 1 to 20 carbon atoms which may be substituted for the aromatic hydrocarbon group (excluding the carbon number of the aromatic hydrocarbon group when the aromatic hydrocarbon group is substituted). In this case, the aromatic hydrocarbon group that may be bonded to the alkyl group is a phenyl group, the quinacridone derivative according to (1) or (2),
(4) The quinacridone derivative according to (1), wherein Y is a hydrogen atom, and X is the dioxane-forming group.
(5) Y is an alkyl group having 1 to 20 carbon atoms, and X is a group represented by —CH ₂ —Ar (wherein Ar represents an aromatic hydrocarbon group) or a structural formula (1B). The quinacridone derivative according to the above (1), which is an aromatic hydrocarbon group-substituted oxadiazole group shown.

  According to the present invention, a quinacridone derivative that emits white light by itself, or a device that emits light in a color tone from yellow to orange without emitting white light by itself, for example, by combining with a blue light emitting compound. The quinacridone derivatives can be provided, and the quinacridone derivatives dissolve in an organic solvent, so that the processability is good. Therefore, a light-emitting device using these quinacridone derivatives can be easily produced.

FIG. 1 is a process explanatory diagram illustrating a process of synthesizing a quinacridone derivative. FIG. 2 is a schematic explanatory diagram illustrating an example of an organic EL element. FIG. 3 is an IR chart of the cyclohexadiene compound (1A) represented by Structural Formula 10. FIG. 4 is an IR chart of the fragrance (1B) represented by Structural Formula 11. FIG. 5 is an IR chart of the quinacridone derivative represented by Structural Formula 12. FIG. 6 is an IR chart of the quinacridone derivative represented by Structural Formula 13. FIG. 7 is an IR chart of the quinacridone derivative represented by Structural Formula 19. FIG. 8 is an IR chart of the quinacridone derivative represented by Structural Formula 21. FIG. 9 is an IR chart of the quinacridone derivative represented by Structural Formula 22. FIG. 10 is an IR chart of the quinacridone derivative represented by Structural Formula 26. FIG. 11 is an IR chart of the quinacridone derivative represented by Structural Formula 27. FIG. 12 is an IR chart of the quinacridone derivative represented by Structural Formula 28. FIG. 13 is an IR chart of the compound represented by Structural Formula 15. FIG. 14 is an IR chart of the compound represented by Structural Formula 29. FIG. 15 is an IR chart of the compound represented by Structural Formula 30. FIG. 16 is a fluorescence emission spectrum of the compound represented by Structural Formula 31. FIG. 17 is an IR chart of the compound represented by Structural Formula 31. FIG. 18 is an IR chart of the compound represented by Structural Formula 32. FIG. 19 is a fluorescence emission spectrum of the compound represented by Structural Formula 32. FIG. 20 is an IR chart of the compound represented by Structural Formula 33. FIG. 21 is an IR chart of the compound represented by Structural Formula 34. FIG. 22 is a fluorescence emission spectrum diagram of the compound represented by the structural formula 34. FIG. 23 is an IR chart of the compound represented by Structural Formula 35. FIG. 24 is an IR chart of the compound represented by Structural Formula 36. FIG. 25 is an IR chart of the compound represented by Structural Formula 37. FIG. 26 is an IR chart of the compound represented by Structural Formula 38. FIG. 27 is an IR chart of the compound represented by Structural Formula 39. FIG. 28 is an IR chart of the compound represented by Structural Formula 41. FIG. 29 is an IR chart of the compound represented by Structural Formula 42. FIG. 30 is an IR chart of the compound represented by Structural Formula 43.

  The quinacridone derivative according to the present invention has the structural formula 1.

In Structural Formula 1, X is —COOR ₁ (where R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), a bromine atom, an iodine atom, an aromatic hydrocarbon group such as a pyrenyl group, An alkyl group having 1 to 10 carbon atoms which may be substituted with an anthryl group or the like (excluding the carbon number of the aromatic hydrocarbon group when the aromatic hydrocarbon group is substituted), -O-CH ₂ CH ₂ -O A structural formula (1A) of the formula, wherein one oxygen atom in the structural formula (1A) is bonded to the benzene ring in the structural formula of the structural formula 1 and the other oxygen atom is at the 4-position in the structural formula 1 A dioxane-forming group bonded to carbon on the benzene ring, a group represented by —CH ₂ —Ar (wherein Ar represents an aromatic hydrocarbon group such as a pyrenyl group or an anthryl group), and a structural formula (1B) Aromatic hydrocarbon group An oxadiazole group (wherein Ar in the structural formula (1B) represents an aromatic hydrocarbon group), or a structural formula (1C) of —CH═CH—Ar (wherein Ar represents an aromatic hydrocarbon group) .) Is an aromatic group-substituted vinyl group.

  In Structural Formula 1, Y is a hydrogen atom or an aromatic hydrocarbon group that may be substituted with an alkyl group such as a methyl group, such as an anthryl group, a pyrenyl group, etc. An alkyl group, preferably an alkyl group having 1 to 15 carbon atoms, and particularly preferably an alkyl group having 1 to 10 carbon atoms and a benzyl group (when the aromatic hydrocarbon group is substituted, the carbon number of the aromatic hydrocarbon group is excluded). , When X is a bromine atom or an iodine atom, Y is an optionally substituted aromatic hydrocarbon group having 1 to 10 carbon atoms (when an aromatic hydrocarbon group is substituted, the carbon number of the aromatic hydrocarbon group is And an alkyl group having 1 to 5 carbon atoms and a benzyl group.

  In the quinacridone derivative according to the present invention, when X is a bromine atom or an iodine atom, Y is not a hydrogen atom.

A preferred quinacridone derivative according to the present invention is the structural formula 1, wherein Y is an optionally substituted aromatic hydrocarbon group having 1 to 10 carbon atoms (when the aromatic hydrocarbon group is substituted, X is —COOR _1a (wherein R _1a represents an alkyl group having 1 to 10 carbon atoms) or an aromatic hydrocarbon group. An alkyl group having 1 to 10 carbon atoms (excluding the carbon number of the aromatic hydrocarbon group when the aromatic hydrocarbon group is substituted), or an aromatic hydrocarbon group substitution represented by the structural formula (1B) Represents an oxadiazole group, and Y represents an optionally substituted aromatic hydrocarbon group having 1 to 10 carbon atoms (when an aromatic hydrocarbon group is substituted, the carbon number of the aromatic hydrocarbon group is excluded. ) In the case of an alkyl group The aromatic hydrocarbon group is a phenyl group.

  These quinacridone derivatives are soluble in a hydrophobic organic solvent by having an alkyl group, an alkyl group replacing an aromatic hydrocarbon group, or a carboxylic acid group or an ester group.

  Furthermore, in the quinacridone derivative according to the present invention, the quinacridone derivative in which Y is a hydrogen atom and X is the dioxane-forming group becomes soluble in a polar solvent due to having an ether group in the molecule, and is oxidized. Excellent thermal stability and robustness because it is difficult to be applied. Therefore, the quinacridone derivative having a dioxane-forming group can be derived into a useful compound, particularly a white light-emitting polymer, by further organic reaction by dissolving in a solvent.

  The quinacridone derivative according to the present invention can be synthesized, for example, through the process shown in FIG.

  One raw material for synthesizing the quinacridone derivative is a 1,4-cyclohexanedione 2,5-dicarboxylic acid alkyl ester or 1,4-cyclohexanediol 2,5-dicarboxylic acid alkyl ester represented by Structural Formula 2 (Chemical Formula 5) 4-X-substituted-aniline represented by Structural Formula 3 (Chemical Formula 6).

_{R 2} in the structural formula 2, of 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms.

X in the structural formula 3 is —COOR ₁ (where R ₁ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms), a bromine atom, an iodine atom, or an aromatic group. An alkyl group having 1 to 10 carbon atoms that may be substituted with a hydrocarbon group (excluding the number of carbon atoms in the aromatic hydrocarbon group when the aromatic hydrocarbon group is substituted), or —O—CH ₂ CH ₂ -O- has the structural formula (1A), and one oxygen atom in the structural formula (1A) is bonded to the 3-position or 5-position of the benzene ring in the structural formula 3 with the amino group as the 1-position. And the other oxygen atom represents a dioxane-forming group bonded to carbon on the 4-position benzene ring in Chemical Formula 3 above. The group or atom selected as X is selected according to the structure of the target quinacridone derivative.

  1,4-cyclohexanedione 2,5-dicarboxylic acid alkyl ester represented by structural formula 2 or 1,4-cyclohexanediol 2,5-dicarboxylic acid alkyl ester and 4-X-substituted-aniline represented by structural formula 3 A cyclohexadiene compound represented by the structural formula 4 is obtained by dehydration reaction. 4-X-substituted-aniline represented by Structural Formula 3 is cheaper and more readily available than X-substituted aniline, has an effective resonance effect, is highly reactive, and therefore increases the yield. Can do.

  The dehydration reaction is carried out by reacting the 4-X substituted-aniline amino group and the 1,4-cyclohexanedione 2,5-dicarboxylic acid alkyl ester carbonyl group, or the 4-X substituted-aniline amino group and 1,4. -Proceed by dehydration with the hydroxyl group of cyclohexanediol 2,5-dicarboxylic acid alkyl ester. As the solvent, for example, alcohols such as methanol, ethanol and isopropanol, acidic solvents such as acetic anhydride, phthalic acid and phthalic anhydride can be raised.

  The reflux temperature is sufficient as the reaction temperature for the dehydration reaction.

  A dehydration catalyst can be used for this dehydration reaction. The dehydration catalyst is added to the dehydration reaction system. Usually, a mixed solution of the solvent and the dehydration catalyst is used.

  Examples of the dehydration catalyst include known catalysts, such as aluminum oxide, calcium oxide, and copper oxide.

In the structural formula represented by Structural Formula 4, R ₁ and X in this cyclohexadiene isomer are the same as described above.

  Next, the cyclohexadiene compound represented by the structural formula 4 is dehydrogenated to dehydrogenate the cyclohexadiene compound to obtain an aromatized product having the structure represented by the structural formula 5. This dehydrogenation reaction is preferably performed by so-called iodo oxidation in which iodine is added to a solution in which the cyclohexadiene compound represented by the structural formula 4 is dissolved and refluxed. In FIG. 1, the step of aromatizing by dehydrogenation is indicated as iodo-oxidation.

In the structure represented by this structural formula 5, R ₁ and X have the same meaning as described above.

  The dehydrogenation reaction can be carried out by heating a mixture having the cyclohexadiene compound represented by the structural formula 4 and a dehydrogenation catalyst and a solvent as required.

  Examples of the solvent include alcohols such as ethanol and propanol, polar solvents such as orthodichlorobenzene, metadichlorobenzene, pyridine, dioxane, and N, N-dimethylformamide.

  The reaction temperature by heating is usually the reflux temperature of the solvent or 140 to 180 ° C.

  As the dehydrogenation catalyst, a known dehydrogenation catalyst can be used, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, iron, zinc, aluminum oxide, aluminum chloride and the like. In some cases, a dehydrogenation catalyst may not be used.

The aromatic product represented by the structural formula 5 obtained by the dehydrogenation reaction can be continuously subjected to an N-alkylation reaction and a ring closure reaction by reacting with a dialkyl sulfuric acid. 1, a quinacridone derivative (Structural Formula 6) in which Y is an alkyl group having 1 to 10 carbon atoms is synthesized. In addition, in FIG. 1, the synthesis example using the dimethyl sulfate which is an example of a dialkyl sulfuric acid is shown. In the structure represented by the following structural formula 6, R ₃ represents an alkyl group having 1 to 10 carbon atoms, which may be substituted with an aromatic hydrocarbon group. R ₃ bonded to two nitrogen atoms in the structure represented by Structural Formula 6 may be the same or different.

  The N-alkylation reaction and the ring closure reaction are carried out by heating a mixture containing a solvent, an aromatic compound represented by the structural formula 5 and a dialkyl sulfuric acid, for example, to the reflux temperature of the solvent or 140 to 180 ° C. proceed.

  Examples of the solvent include alcohols such as ethanol and propanol, polar solvents such as orthodichlorobenzene, metadichlorobenzene, pyridine, dioxane, and N, N-dimethylformamide.

When X is an alkyl ester group represented by -COOR ₁ in the quinacridone derivative represented by Structural Formula 6, hydrolysis of the quinacridone derivative represented by Structural Formula 6 yields a quinacridone derivative represented by Structural Formula 7. It is done.

  The hydrolysis can be easily carried out by refluxing a mixture containing a quinacridone derivative represented by the structural formula 6 and a solvent and made acidic with caustic soda or the like or acidic with hydrochloric acid or the like.

  On the other hand, the aromatized product represented by the structural formula 5 obtained by the dehydrogenation reaction can be subjected to a ring-closing reaction with an acid catalyst such as sulfuric acid. As a result of the ring closure reaction, a quinacridone derivative represented by Structural Formula 8 is synthesized. In the structure of the quinacridone derivative represented by Structural Formula 8, X has the same meaning as described above.

In the quinacridone derivative represented by the structural formula 8, when X is —COOR ₁ and R ₁ is an alkyl group having 1 to 10 carbon atoms, the quinacridone derivative represented by the chemical formula 8 and the aromatic carbonization Reacting with a halogenated hydrocarbon having an alkyl group of 1 to 10 carbon atoms that may be substituted with a hydrogen group (excluding the number of carbon atoms of the aromatic hydrocarbon group when the aromatic hydrocarbon group is substituted). Thus, a quinacridone derivative represented by the structural formula 9 is synthesized, in which an alkyl group which may be substituted with an aromatic hydrocarbon group is bonded to a nitrogen atom.

In the quinacridone derivative represented by the structural formula 9, R ₃ may have 1 to 10 carbon atoms which may be substituted with an aromatic hydrocarbon group (when the aromatic hydrocarbon group is substituted, the carbon number of the aromatic hydrocarbon group is The alkyl group derived from a halogenated hydrocarbon having an alkyl group.

Examples of the aromatic hydrocarbon that may be substituted with the halogenated hydrocarbon include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, a pyrenyl group, and a dibenzophenanthryl group. Preferable examples of R ₃ include a benzyl group.

In the quinacridone derivative represented by the structural formula 9, when X is —COOR ₁ and R ₁ is an alkyl group, the quinacridone derivative represented by the structural formula 9 is hydrolyzed with an alkali or an acid, whereby X is − A quinacridone derivative that is COOH can be synthesized.

  In addition, a quinacridone derivative according to the present invention can be synthesized using a commercially available quinacridone.

  In Structural Formula 1 represented by Structural Formula 1, X is an alkyl group having 1 to 10 carbon atoms (excluding the carbon number of the aromatic hydrocarbon group) substituting the aromatic hydrocarbon group, and Y is aromatic A quinacridone derivative which is an alkyl group having 1 to 20 carbon atoms which may be substituted with an aromatic hydrocarbon group (excluding the carbon number of the aromatic hydrocarbon group when the aromatic hydrocarbon group is substituted) is a commercially available quinacridone And halogenated alkyl (provided that the alkyl group in the halogenated alkyl has 1 to 20 carbon atoms which may be substituted for the aromatic hydrocarbon group (when the aromatic hydrocarbon group is substituted, the number of carbon atoms in the aromatic hydrocarbon group is When the aromatic hydrocarbon group is substituted with an aromatic hydrocarbon group, the nitrogen atom in quinacridone may be substituted with an aromatic hydrocarbon group. Quinacridone derivative A substituted with an alkyl group of the aromatic hydrocarbon group is synthesized, and then the quinacridone derivative B is synthesized by alkylating the 2nd and 9th carbons of this quinacridone derivative A. The quinacridone derivative C was synthesized by substituting the hydrogen bonded to the terminal carbon in the alkyl group bonded to the 2-position carbon and the 9-position carbon in the quinacridone derivative B with a halogen, and then reacting the quinacridone derivative C with an aromatic hydrocarbon. When dehydrohalogenated, X is an alkyl group having 1 to 10 carbon atoms (excluding the carbon number of the aromatic hydrocarbon group) substituting the aromatic hydrocarbon group, and Y is an aromatic hydrocarbon group An alkyl group having 1 to 20 carbon atoms which may be substituted (excluding the carbon number of the aromatic hydrocarbon group when the aromatic hydrocarbon group is substituted) It can be synthesized certain quinacridone derivatives.

  In addition, 2,9-dialkylquinacridone having an alkyl group having 1 to 10 carbon atoms at the 2-position and 9-position in Structural Formula 1 and an alkyl halide (provided that the alkyl group in the halogenated alkyl represents an aromatic hydrocarbon group). A nitrogen atom in quinacridone by reacting with an optionally substituted alkyl group having 1 to 20 carbon atoms (excluding the carbon number of the aromatic hydrocarbon group when the aromatic hydrocarbon group is substituted). In addition, a quinacridone derivative D substituted with an alkyl group having 1 to 10 carbon atoms that may be substituted with an aromatic hydrocarbon group (excluding the number of carbon atoms of the aromatic hydrocarbon group when the aromatic hydrocarbon group is substituted) In this quinacridone derivative D, the hydrogen bonded to the terminal carbon in the alkyl group bonded to the 2-position carbon and the 9-position carbon is replaced with a halogen, When a cridon derivative C is synthesized and then dehydrohalogenated by reacting the quinacridone derivative C with an aromatic hydrocarbon, X is substituted with an aromatic hydrocarbon group having 1 to 10 carbon atoms (aromatic hydrocarbon group). And the carbon number of the aromatic hydrocarbon group when Y is substituted with the aromatic hydrocarbon group, Y may be substituted with the aromatic hydrocarbon group. The quinacridone derivative which is an alkyl group can be synthesized.

  The quinacridone derivative that substitutes the aromatic hydrocarbon group-substituted oxadiazole group represented by the structural formula (1B) at the 2nd and 9th positions in the structural formula 1 can be synthesized, for example, as follows.

  In the structural formula 1, the 2nd and 9th positions are halogenated, for example, iodinated, then the halogen atom bonded to the 2nd and 9th positions is substituted with a CN group (cyano group), and the cyano group substituted at the 2nd and 9th positions is carboxylated. An acid chloride derivative (1B1) is obtained by converting a carboxylic acid group derived from an acid and substituting at the 2-position and 9-position into an acid chloride group (—COCl).

On the other hand, by introducing a carboxylic acid group into an aromatic hydrocarbon such as benzene, naphthalene, anthracene, pyrene, etc., converting the introduced carboxylic acid group into an acid chloride, and reacting the acid chloride with hydrazine, the hydrazide group To synthesize hydrazide-introduced aromatic hydrocarbon (H ₂ NNHOC-Ar).

The quinacridone derivative (1B1) and hydrazide-introduced aromatic hydrocarbon (H ₂ NNHOC-Ar) are coupled to synthesize a coupling body (1B2). When this coupling body (1B2) is heated together with phosphoryl chloride, a quinacridone derivative substituting the aromatic hydrocarbon group-substituted oxadiazole group can be synthesized.

  The quinacridone derivative that substitutes the aromatic hydrocarbon group-substituted vinyl group represented by the structural formula (1C) at the 2nd and 9th positions in the structural formula 1 can be synthesized, for example, as follows.

  A quinacridone derivative having a halogenated methyl group at the 2nd and 9th positions is synthesized by introducing methyl groups at the 2nd and 9th positions in the quinacridone skeleton, and substituting hydrogen in the methyl group with halogen at the 2nd and 9th positions. By the so-called Wittig reaction in which methyl halide in this quinacridone derivative is reacted with triphenylphosphine, the structural formula (1C) in which X in the structural formula 1 is —CH═CH—Ar (where Ar represents an aromatic hydrocarbon group) A quinacridone derivative which is an aromatic hydrocarbon group-substituted vinyl group represented by

  The quinacridone derivative according to the present invention is soluble in a general-purpose organic solvent when X is an alkyl group or the dioxane-forming group and Y is an alkyl group. Therefore, when this quinacridone derivative is dissolved in an organic solvent and reacted with a monomer capable of polycondensation with this quinacridone derivative, a white light-emitting polymer can be formed.

  The quinacridone derivative according to the present invention emits light in the region of 400 to 700 nm and can be used for an organic EL device capable of emitting white light.

  An organic EL device using a quinacridone derivative according to the present invention includes an ITO anode, for example, polyvinylcarbazole (PVK), 2- (4-tert-butylphenyl) 5- (4-biphenyl) -1,3,4-oxazodiazole. In addition, a structure including a light emitting layer containing the quinacridone derivative of the present invention and a cathode formed on the surface of the light emitting layer may be used. In light emission, when an electric field is applied between the cathode and the anode, electrons are injected from the cathode side, holes are injected from the anode, and electrons are recombined with holes in the light-emitting layer, and energy levels are reduced. This is a phenomenon in which energy is released as light when the position returns from the conduction band to the valence band.

  This organic EL element can employ various types of structures as long as it has a light emitting layer containing a quinacridone derivative according to the present invention between an anode and a cathode. As this organic EL element, for example, as shown in FIG. 2, the transparent electrode 3 formed on the surface of the transparent substrate 2 and the quinacridone derivative according to the present invention formed on the surface of the transparent electrode 3 A single-layer organic light emitting device comprising the light emitting layer 4 contained and a cathode 5 formed on the surface of the light emitting layer 4 can be mentioned.

  In this single layer type organic light emitting device, the light emitting layer can be a deposited layer formed by depositing a quinacridone derivative represented by the structural formula 1, and the light emitting layer is represented by the structural formula 1. The quinacridone derivative can be dissolved in an organic solvent together with a polymer compound such as polyvinylcarbazole, and the resulting polymer solution can be applied and dried to obtain a light emitting layer.

  As another type of organic EL device, an electron transporting substance that transports electrons, a quinacridone derivative according to the present invention, and a hole transporting polymer that transports holes are provided between an anode and a cathode. Single layer type organic light emitting device having a light emitting layer, a hole transport layer containing a hole transporting material between an anode and a cathode formed on a substrate, and an electron transporting light emission containing the quinacridone derivative according to the present invention A two-layer organic low-molecular light-emitting device formed by laminating layers (for example, a hole transport layer between an anode and a cathode, and a light-emitting layer containing the quinacridone derivative and host dye according to the present invention as a guest dye) A two-layer dye-doped light-emitting device formed by laminating), a hole transport layer containing a hole transport material between the anode and the cathode, and the quinacridone derivative and electron transport material according to the present invention A two-layer organic light-emitting device in which an electron-transporting light-emitting layer is laminated (for example, a hole transport layer between an anode and a cathode, and the quinacridone derivative according to the present invention as a guest dye and A two-layer dye-doped organic light-emitting device formed by laminating an electron transport light-emitting layer containing a host dye), a hole transport layer between the anode and the cathode, a light-emitting layer containing the quinacridone derivative according to the present invention, and A three-layer type organic light emitting device formed by laminating an electron transport layer can be exemplified. In the various organic EL elements described above, a single light emitting layer and a laminate composed of two layers and three layers may be referred to as an organic layer.

The organic EL element can be usually formed on a substrate. Examples of the substrate include transparent substrates such as glass and plastic. As the anode, various materials can be adopted as long as the work function is large and transparent, and holes can be injected into the film by applying a voltage. Specifically, the anode can be formed of an inorganic transparent conductive material such as ITO, In ₂ O ₃ , SnO ₂ , ZnO, CdO, or the like, or a compound thereof, or a conductive polymer material such as polyaniline. . This anode is formed on the substrate by chemical vapor deposition, spray pyrolysis, vacuum deposition, electron beam deposition, sputtering, ion beam sputtering, ion plating, ion assisted deposition, or other methods. Can be formed.

  The cathode employs a material having a small work function, and may be formed of a single metal or a metal alloy such as MgAg, an aluminum alloy, and metal calcium. The preferred cathode is an alloy electrode of aluminum and a small amount of lithium. The cathode can be easily formed on the surface of the organic layer including the light emitting layer formed on the substrate, for example, by a vapor deposition technique.

  Examples of the electron transporting substance include oxadiazole derivatives such as 2- (4-tert-butylphenyl) -5- (4-biphenyl) -1,3,4-oxadiazole and 2,5-bis (1-naphthyl) -1,3,4-oxadiazole, 2,5-bis (5′-tert-butyl-2′-benzoxazolyl) thiophene, and the like can be given. As the electron transporting substance, for example, a metal complex material such as a quinolinol aluminum complex (Alq3) or a benzoquinolinol beryllium complex (Bebq2) can be preferably used.

  Examples of the hole transport material include triphenylamine compounds such as N, N′-diphenyl-N, N′-di (m-tolyl) -benzidine (TPD) and α-NPD, hydrazone compounds, and stilbene compounds. , Heterocyclic compounds, π-electron starburst hole transport materials, and the like.

  The organic layer in the organic EL element can be formed by any of a coating method such as a spin casting method, a coating method, a dipping method, and a vapor deposition method. Whichever of the coating method and the vapor deposition method is adopted, it is preferable to interpose a buffer layer between the electrode and the organic layer. Examples of materials that can form the buffer layer formed between the cathode and the organic layer include alkali metal compounds such as lithium fluoride, alkaline earth metal compounds such as magnesium fluoride, and aluminum oxide. And 4,4′-biscarbazole biphenyl (Cz-TPD). Further, as a material for forming a buffer layer formed between an anode such as ITO and an organic layer, for example, m-MTDATA (4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenyl Amine), phthalocyanine, polyaniline, polythiophene derivatives, inorganic oxides such as molybdenum oxide, ruthenium oxide, vanadium oxide, and lithium fluoride. By appropriately selecting the material of these buffer layers, the driving voltage of the organic EL element can be lowered, the quantum efficiency of light emission can be improved, and the emission luminance can be improved. .

  The organic EL element using the quinacridone derivative according to the present invention can be generally used as, for example, a DC drive type element, and can also be used as a pulse drive type element and an AC drive type element.

  The quinacridone derivative according to the present invention is further used in display fields such as monochrome displays and color displays, and lighting fields such as light signs, direct-view signs, indirect lighting, and backlights for LCDs.

  As described above, the quinacridone derivative according to the present invention can be obtained by, for example, reacting an aromatic dicarboxylic acid and hydrazine to obtain a copolymer linked by an oxadiazole ring, or linked by an oxadithiazole. A copolymer or the like can be obtained. These copolymers are soluble in an organic solvent and emit white light by having a quinacridone derivative skeleton in the main chain.

  These copolymers are also useful substances capable of forming an organic EL device.

Example 1
In this example, in the quinacridone derivative represented by the structural formula 1, a quinacridone derivative in which X is —COOCH ₃ and —COOH and Y is a methyl group was synthesized according to the following procedure.

<Dehydration reaction>
A 500 mL flask was charged with 11.4 g of dimethyl 1,4-cyclohexanedione 2,5-dicarboxylate, 13.2 g of methyl 4-amino-benzoate, 150 mL of ethanol and 150 mL of acetic acid. The contents of the flask were refluxed for 3 hours with stirring. After stopping the reaction, the contents of the flask were cooled to room temperature. The contents of the flask were subjected to suction filtration, and the solid filtrate was recrystallized from toluene and washed with methanol. As a result, 8 g of a cyclohexadiene compound (1A) represented by the structural formula 10 was synthesized. An IR chart of the cyclohexanediene body (1A) represented by Structural Formula 10 is shown in FIG.

<Iodo oxidation (dehydrogenation reaction)>
200 mL of ethanol was put into a 500 mL flask, and this ethanol was boiled. Next, 4 g of the cyclohexanediene (1A) and 5 g of iodine were added to the boiling ethanol. The contents of the flask were refluxed with stirring for 5 hours. After stopping the reaction, it was left overnight at room temperature. Thereafter, the contents of the flask were subjected to suction filtration, and the solid filtrate was washed with ethanol to synthesize 2.4 g of an aromatized product (1B) represented by Structural Formula 11 as orange crystals. An IR chart of the fragrance (1B) shown in Structural Formula 11 is shown in FIG. 4, and its melting point was 160 ° C.

<N-methylation and ring closure reaction>
In a 50 mL flask, 1 g of the aromatized product (1B) represented by the structural formula 11 was placed, and then 50 mL of 1,2-dichlorobenzene and 3 mL of dimethyl sulfate were successively added. The contents of the flask were heated to 160 ° C. with stirring for 1.5 hours. Subsequently, it reacted by heating at 170-180 degreeC for 0.5 hour. After completion of the reaction, ice water and the contents in the flask were put into a conical beaker, and the contents of the conical beaker were shaken and mixed. Thereafter, 10% caustic soda was added to the contents of the conical beaker to make the pH of the contents weakly alkaline. The contents of the conical beaker were transferred to a separatory funnel and chloroform extraction was performed three times, and the chloroform extract was washed once with water. After adding 3 tablespoon of sodium sulfate to the chloroform extract, it was left overnight. On the next day, the chloroform extract was concentrated to dryness with an evaporator, and the obtained concentrate was subjected to suction filtration to obtain a solid as a filtrate. By washing the solid with methanol, 0.6 g of a quinacridone derivative (1C) represented by the structural formula 12 was synthesized. An IR chart of the quinacridone derivative (1C) represented by Structural Formula 12 is shown in FIG. 5, and its melting point was 280 ° C. or higher.

<Hydrolysis>
In a 50 mL three-necked flask, 0.1 g of the quinacridone derivative (1C) represented by the structural formula 12 was placed. Furthermore, 20 mL of ethanol and 20 mL of dioxane were added to this three-necked flask, and 1 g of caustic potash and boiling stone were added. The contents of this three-necked flask were refluxed for 3 hours. After the reaction was stopped, ice water and the contents of the three-necked flask were placed in a conical beaker, and the conical beaker was shaken. The pH of the contents of the conical beaker was made weakly acidic with hydrochloric acid. The contents of the conical beaker were suction filtered, and the filtrate was washed with methanol to synthesize 0.06 g of the quinacridone derivative (1D) represented by the structural formula 13. An IR chart of the quinacridone derivative (1D) represented by Structural Formula 13 is shown in FIG. The melting point of this quinacridone derivative was 280 ° C. or higher.

(Example 2)
In this example, in the quinacridone derivative represented by the structural formula 1, a quinacridone derivative in which X is —COOC ₂ H ₅ or —COOH and Y is a methyl group was synthesized according to the following procedure.

<Dehydration reaction>
A 500 mL flask was charged with 13.8 g dimethyl 1,4-cyclohexanedione 2,5-dicarboxylate, 25 g ethyl 4-amino-benzoate, 200 mL ethanol and 200 mL acetic acid. The contents of the flask were refluxed with stirring for 12 hours. After stopping the reaction, the contents of the flask were cooled to room temperature. The contents of the flask were subjected to suction filtration, and the solid filtrate was recrystallized from toluene and washed with ethanol to synthesize an orange crystal and 11 g of cyclohexadiene (A) represented by Structural Formula 14.

<Iodo oxidation (dehydrogenation reaction)>
200 mL of ethanol, 11 g of the cyclohexadiene compound (A) represented by the structural formula 14 and 7 g of iodine were placed in a 500 mL flask, and the contents of the flask were refluxed for 5 hours with stirring. After stopping the reaction, it was left overnight at room temperature. Thereafter, the contents of the flask were subjected to suction filtration, and the solid filtrate was washed with ethanol and recrystallized with DMF to synthesize 7 g of an aromatized product (B) represented by Structural Formula 15 as orange crystals. An IR chart of this aromatic body (B) is shown in FIG.

<N-methylation and ring closure reaction>
In a 50 mL flask, 3 g of the aromatized product (B) represented by the structural formula 15 was placed, and then 30 mL of 1,2-dichlorobenzene and 3 mL of dimethyl sulfate were successively added. The reaction was conducted by heating the contents of the flask to 160 ° C. for 5 hours under stirring. After completion of the reaction, ice water and the contents in the flask were put into a conical beaker, and the contents of the conical beaker were shaken and mixed. Thereafter, 10% caustic soda was added to the contents of the conical beaker to make the pH of the contents weakly alkaline. The contents of the conical beaker were transferred to a separatory funnel and chloroform extraction was performed three times, and the chloroform extract was washed once with water. After adding 3 tablespoon of sodium sulfate to the chloroform extract, it was left overnight. On the next day, the chloroform extract was concentrated to dryness with an evaporator, and the obtained concentrate was subjected to suction filtration to obtain a solid as a filtrate. By washing the solid with methanol, 2 g of the quinacridone derivative (C) represented by the structural formula 16 was synthesized.

<Hydrolysis>
In a 50 mL three-necked flask, 0.1 g of the quinacridone derivative (C) represented by the structural formula 16 was placed. Furthermore, 100 mL of ethanol and 20 mL of dioxane were added to this three-necked flask, and 1 g of caustic potash and boiling stone were added. The contents of this three-necked flask were refluxed for 3 hours. After the reaction was stopped, ice water and the contents of the three-necked flask were placed in a conical beaker, and the conical beaker was shaken. The pH of the contents of the conical beaker was made weakly acidic with hydrochloric acid. The contents of the conical beaker were suction filtered, and the filtrate was washed with methanol to synthesize 0.06 g of the quinacridone derivative (1D) represented by the structural formula 13.

(Example 3)
In this example, a quinacridone derivative represented by Structural Formula 1 in which X is —Br and Y is a methyl group was synthesized according to the following procedure.

<Dehydration reaction>
A 1000 mL flask was charged with 11.4 g of dimethyl 1,4-cyclohexanedione 2,5-dicarboxylate, 20.64 g of 4-bromoaniline, 200 mL of ethanol and 200 mL of acetic acid. The contents of the flask were refluxed with stirring for 5 hours. After stopping the reaction, the contents of the flask were cooled to room temperature. The contents of the flask were subjected to suction filtration, and the solid filtrate was recrystallized with DNF and washed with ethanol to synthesize 13 g of a cyclohexadiene compound (3A) represented by Structural Formula 17 as orange crystals. The melting point of the cyclohexanediene compound (3A) represented by Structural Formula 17 was 240 ° C.

<Iodo oxidation (dehydrogenation reaction)>
A 500 mL flask was charged with 12 g of the cyclohexadiene compound (3A) represented by the structural formula 17 above, 6 g of iodine, 50 mL of 1,4-dichlorobenzene, and 250 mL of ethanol. The contents of the flask were refluxed with stirring for 6 hours. After stopping the reaction, it was left overnight at room temperature. Thereafter, the contents of the flask were suction filtered, and the solid filtrate was washed with ethanol and recrystallized with THF. 3.6 g of the aromatized product (3B) represented by the structural formula 18 of the obtained orange crystals was synthesized. The melting point of the fragrance (3B) represented by Structural Formula 18 was 220 ° C.

<N-methylation and ring closure reaction>
In a 50 mL flask, 1.2 g of the aromatic product (3B) represented by the structural formula 18 was placed, and then 15 mL of 1,2-dichlorobenzene and 2 mL of dimethyl sulfate were successively added. The reaction was conducted by heating the contents of the flask to 160 ° C. for 4 hours with stirring. After completion of the reaction, ice water and the contents in the flask were put into a conical beaker, and the contents of the conical beaker were shaken and mixed. Thereafter, 10% caustic soda was added to the contents of the conical beaker to make the pH of the contents weakly alkaline. The contents of the conical beaker were transferred to a separatory funnel and chloroform extraction was performed three times, and the chloroform extract was washed once with water. After adding 3 tablespoon of sodium sulfate to the chloroform extract, it was left overnight. On the next day, the chloroform extract was concentrated to dryness with an evaporator, and the obtained concentrate was subjected to suction filtration to obtain a solid as a filtrate. By washing the solid with methanol, 0.8 g of a quinacridone derivative (3C) represented by the structural formula 19 was synthesized. An IR chart of this quinacridone derivative is shown in FIG. The melting point was 280 ° C. or higher.

Example 4
In this example, a quinacridone derivative represented by Structural Formula 1 in which X is —C ₈ H ₁₇ and Y is a methyl group or a hydrogen atom was synthesized according to the following procedure.

<Dehydration reaction>
A 1000 mL flask was charged with 11.4 g of dimethyl 1,4-cyclohexanedione 2,5-dicarboxylate, 24.64 g of 4-n-octylaniline, 300 mL of ethanol and 300 mL of acetic acid. The contents of the flask were refluxed with stirring for 5 hours. After stopping the reaction, the contents of the flask were cooled to room temperature. The contents of the flask were subjected to suction filtration, and the solid filtrate was washed with methanol to synthesize 14 g of a cyclohexadiene compound (4A) represented by Structural Formula 20 as orange crystals.

<Iodo oxidation (dehydrogenation reaction)>
A 500 mL flask was charged with 12 g of the cyclohexadiene compound (4A) represented by the structural formula 20, 6 g of iodine, and 200 mL of ethanol. The contents of the flask were refluxed with stirring for 5 hours. After stopping the reaction, it was left overnight at room temperature. Thereafter, the contents of the flask were suction filtered, and the solid filtrate was washed with ethanol. 10 g of the aromatized product (4B) represented by the structural formula 21 of the obtained red crystal was synthesized. An IR chart of the fragrance (4B) represented by Structural Formula 21 is shown in FIG. The aromatized product (4B) represented by the structural formula 21 is more soluble in an organic solvent such as isobutanol than the aromatized product (3B) represented by the structural formula 18, and is irradiated with UV light of about 365 nm. Then, it was observed by visual appearance that the emission wavelength was shifted to the longer wavelength side. This is presumably because the molecular polarization is large due to the induced effect of the long-chain alkyl group.

<N-methylation and ring closure reaction>
In a 100 mL flask, 6.0 g of the aromatic product (4B) represented by the structural formula 21 was placed, and then 60 mL of 1,2-dichlorobenzene and 10.0 g of dimethyl sulfate were successively added. The reaction was conducted by heating the contents of the flask to 160 ° C. for 5 hours under stirring. After completion of the reaction, ice water and the contents in the flask were put into a conical beaker, and the contents of the conical beaker were shaken and mixed. Thereafter, 10% caustic soda was added to the contents of the conical beaker to make the pH of the contents weakly alkaline. The contents of the conical beaker were transferred to a separatory funnel, and chloroform extraction was performed once, and the chloroform extract was washed three times with water. After adding sodium sulfate to the chloroform extract, it was left overnight. On the next day, the chloroform extract was concentrated to dryness with an evaporator, and the obtained concentrate was subjected to suction filtration to obtain a solid as a filtrate. This solid was washed with methanol to obtain 4.7 g of a quinacridone derivative (4C) represented by the structural formula 22. An IR chart of this quinacridone derivative is shown in FIG.

<Ring ring reaction>
A 500 mL four-necked flask was charged with 6.0 g of the aromatic product (4B) represented by the structural formula 21, 150 mL of 1,2-dichlorobenzene, and 4.25 g of p-toluenesulfonic acid. The contents of the four-necked flask were reacted at 160 ° C. for 5 hours with stirring. After completion of the reaction, the contents of the four-necked flask were filtered with suction, and the filtrate was washed with methanol to obtain 4 g of a quinacridone derivative (4D) represented by the structural formula 23.

(Example 5)
In this example, in the quinacridone derivative represented by Structural Formula 1, a quinacridone derivative in which X is a dioxane forming group and Y is a hydrogen atom was synthesized according to the following procedure.

<Dehydration reaction>
A 500 mL flask was charged with 5.55 g of dimethyl 1,4-cyclohexanedione 2,5-dicarboxylate, 7.55 g of 3,4-ethylenedioxyaniline, 125 mL of ethanol and 125 mL of acetic acid. The contents of the flask were heated to 115 ° C. with stirring for 5 hours. After stopping the reaction, the contents of the flask were cooled to room temperature. The contents of the flask were subjected to suction filtration, and the solid filtrate was washed with methanol and petroleum ether to obtain 10.5 g of a cyclohexadiene compound (5A) represented by structural formula 24 as pink crystals. The melting point of this cyclohexadiene compound (5A) was 218.0-219.5 ° C.

<Iodo oxidation (dehydrogenation reaction)>
In a 500 mL flask, cyclohexadiene compound (5A) represented by the structural formula 24 (dimethyl 1,4-cyclohexadiene-2,5-di (3,4-ethylenedioxyaniline) -1,4-dicarboxylate) 2.80 g, 80.0 mL of o-dichlorobenzene was added. To the contents of this flask, 0.160 g of sulfuric acid was gradually added dropwise and stirred for 30 minutes, and then stirred for 2 hours while heating to 160 ° C. After stopping the reaction, it was left overnight at room temperature. Thereafter, the contents of the flask were suction filtered, the solid filtrate was washed with methanol and petroleum ether and recrystallized with xylene. The refined powder is red, and 2.10 g of an aromatic product (5B) (dimethyl 1,2-dicarboxylate-2,5-di (3,4-ethylenedioxyaniline) benzene represented by the structural formula 25 is obtained. The melting point of this aromatized product (5A) was 225.0 to 226.7 ° C.

<Ring ring reaction>
A 500 mL four-necked flask is charged with 2.10 g of the aromatic product (5B) represented by the structural formula 25, 3.33 g of p-toluenesulfonic acid, 0.02 g of sulfuric acid, and 60.0 mL of o-dichlorobenzene. It was. The contents of the four-necked flask were reacted at 160 ° C. for 20 hours with stirring. After completion of the reaction, the solvent was removed under reduced pressure. The obtained solid was washed with pure water and methanol, and then recrystallized with DMF. The black powder 1.50 g obtained by purification had a melting point of 300 ° C. or higher, and was a quinacridone derivative represented by the structural formula 26. The IR chart is shown in FIG.

(Example 6)
In this example, in the quinacridone derivative represented by the structural formula 1, a quinacridone derivative in which X is —C ₈ H ₁₇ and Y is a benzyl group was synthesized according to the following procedure.

<Benzylation reaction>
In a 500 mL four-necked flask, 0.752 g of quinacridone derivative (4D) represented by Structural Formula 23, 0.282 g of sodium hydride, 1.4 mL of benzyl bromide, and 100 mL of DMF were placed. The contents of this four-necked flask were heated to 120 ° C. with stirring for 3 hours. The contents of the four-necked flask were put into ion-exchanged water and stopped. A mixture of the reaction product solution, which is a DMF mixture, and water was separated, and the pH of the separated DMF mixture was neutralized with hydrochloric acid, followed by suction filtration to obtain a residue. This residue was washed with methanol. The washed solid was dried under reduced pressure to obtain 0.18 g of red crystals. According to FIG. 11 obtained by IR analysis, this red crystal was a quinacridone derivative represented by the structural formula 27.

(Example 7)
In this example, in the quinacridone derivative represented by the structural formula 1, a quinacridone derivative in which X is —C ₈ H ₁₇ and Y is —C ₄ H ₉ was synthesized according to the following procedure.

<Benzylation reaction>
In a 50 mL four-necked flask, 0.741 g of the quinacridone derivative (4D) represented by the structural formula 23, 0.267 g of sodium hydride, 1.5 mL of bromobutane, and 30 mL of DMF were placed. The contents of this four-necked flask were heated to 120 ° C. with stirring for 3 hours. The contents of the four-necked flask were put into ion-exchanged water and stopped. A mixture of the reaction product solution, which is a DMF mixture, and water was separated, and the pH of the separated DMF mixture was neutralized with hydrochloric acid, followed by suction filtration to obtain a residue. This residue was washed with methanol. The washed solid was dried under reduced pressure to obtain 0.17 g of red crystals. According to FIG. 12 obtained by IR analysis, this red crystal was a quinacridone derivative represented by the structural formula 28.

(Example 8)
In a four-necked separable flask, 20.4 g of 2,9-di-methylquinacridone and 300 mL of dimethylformamide (DMF) were placed, and the contents of the separable flask were stirred for 30 minutes while heating to 120 ° C. After 30 minutes, the contents of the separable flask are allowed to cool to 60 ° C., and then 7.2 g of 60% sodium hydride is added to the contents of the separable flask to bring the contents of the separable flask to 120 ° C. The mixture was stirred for 30 minutes while being heated to ° C. Then, the contents of the separable flask changed from reddish purple to blue. Next, the contents of the separable flask were allowed to cool to 60 ° C., after which 53.2 g of bromodecane was added to the contents of the separable flask, and the contents of the separable flask were heated to reflux for 6 hours. The color of the contents of the separable flask changed from blue to magenta. After refluxing, water was put into the separable flask and the contents of the separable flask were suction filtered to obtain a reddish purple residue.

  The residue was washed with methanol and suction filtered to obtain a reddish purple residue. This residue was recrystallized from chloroform and suction filtered to obtain vermilion crystals. The melting point of this crystal was 135 ° C. An IR chart of this crystal is shown in FIG. This crystal was N, N′-didecyl-2,9-dimethylquinacridone having a structure represented by Structural Formula 29.

  Next, 2.48 g of this N, N′-didecyl-2,9-dimethylquinacridone, 2.85 g of N-bromosuccinimide (NBS), 0.065 g of 25% water-wet product of benzoyl peroxide and 100 mL of tetrachloroethane were mixed. The flask was placed in a one-neck flask and the contents of the flask were heated at 110 ° C. for 7 hours with stirring. As a result, the color of the contents of the flask changed from red to brown.

  After stopping the heating, the contents of the flask were concentrated to dryness using an evaporator, washed with methanol, and suction filtered to obtain a brown residue. The brown residue was recrystallized from ethyl acetate and suction filtered to obtain brown crystals. The melting point of this brown crystal is 170 ° C., and the IR chart of this crystal is shown in FIG. This crystal was N, N′-didecyl-2,9-dibromomethylquinacridone represented by the structural formula 30.

  The N, N′-didecyl-2,9-dibromomethylquinacridone 0.78 g, 9-methylanthracene 0.77 g, potassium carbonate 0.69 g, copper powder 0.064 g and DMF 100 mL were placed in a three-necked flask, The contents of the flask were refluxed for 3 hours.

  After stopping the reflux, the contents of the flask were filtered while heating to collect the filtrate. The filtrate and water were mixed, decanted, and suction filtered to obtain a residue. The melting point of this crystal is 200 ° C., the IR chart of this crystal is shown in FIG. 17, and the emission spectrum of this crystal is shown in FIG. The fluorescence spectrum was measured with a fluorescence spectrometer (Fluorolog R-3, manufactured by Horiba, Ltd.). This crystal was N, N′-didecyl-2,9-di (9-methylanthryl) methylquinacridone represented by the structural formula 31.

  In the quinacridone derivative represented by the structural formula 31, an anthryl group is bonded to the 2nd and 9th positions (p position) of the quinacridone skeleton via a methylene group. The anthryl group is an atomic group that emits blue light. Therefore, the quinacridone derivative represented by Structural Formula 31 emits greenish white light as shown in FIG.

Example 9
A four-necked flask was charged with 1.56 g of 2,9-dimethylquinacridone and 300 mL of dehydrated dimethylformamide (DMF), and the contents of the four-necked flask were stirred for 30 minutes while heating to 120 ° C. After 30 minutes, the contents of the four-necked flask are allowed to cool to 60 ° C., and then 0.80 g of 60% sodium hydride is added to the contents of the four-necked flask to add the contents of the four-necked flask. The product was stirred for 30 minutes while heating to 120 ° C. As a result, the contents of the four-necked flask changed from magenta to blue. Next, the contents of the separable flask were allowed to cool to 60 ° C., after which 4.54 g of 9-chloromethylanthracene was added to the contents of the separable flask, and the contents of the four-necked flask were heated to reflux for 5 hours. . The color of the contents of the four-necked flask changed from blue to brown. After refluxing, the contents of the four-necked flask were poured into water and suction filtered to obtain a reddish residue.

  The residue was washed with acetone and suction filtered to obtain a reddish purple residue. The residue was recrystallized from chloroform and suction filtered to obtain red crystals. The melting point of this crystal was 400 ° C. or higher. The IR chart of this crystal is shown in FIG. 18, and the fluorescence spectrum is shown in FIG. This crystal was N, N′-di (9-anthryl) dimethyl-2,9-dimethylquinacridone having a structure represented by Structural Formula 32.

  In the quinacridone derivative represented by the structural formula 32, an anthryl group is bonded to a nitrogen atom in the quinacridone skeleton through a methylene group. This anthryl group is an atomic group emitting blue light. Therefore, the quinacridone derivative represented by the structural formula 32 emits light in bluish white as shown by the fluorescence spectrum shown in FIG.

(Example 10)
In a three-necked flask, 0.78 g of N, N′-didecyl-2,9-dibromomethylquinacridone represented by the structural formula 30 in Example 8, 1.05 g of triphenylphosphine, and 50 mL of xylene were placed. The contents of the neck flask were refluxed for 2 hours. After 2 hours had passed, the contents of the three-necked flask were allowed to cool and then suction filtered, and the residue was collected by filtration.

  In a three-necked flask, 50 mL of dehydrated ethanol and 1.39 g of lithium were stored to dissolve lithium, and 0.65 g of the residue (N-decyl-ylidoquinacridone) and 0.20 g of p-methoxybenzaldehyde were stored. The contents of the three neck flask were stirred at room temperature for 24 hours.

  Thereafter, the contents of the three-necked flask were concentrated and dried with an evaporator, and the resulting solid was washed with water and suction filtered. The obtained residue was washed with methanol to obtain crystals. An IR chart of this crystal is shown in FIG. This crystal was a quinacridone derivative represented by the structural formula 33.

(Example 11)
In a four-necked flask, 0.31 g of 2,9-dimethylquinacridone and 50 mL of dehydrated dimethylformamide (DMF) were placed, and the contents of the four-necked flask were stirred for 30 minutes while heating to 120 ° C. After 30 minutes, the contents of the four-necked flask are allowed to cool to 60 ° C., and 0.24 g of 60% sodium hydride is added to the four-necked flask to bring the contents of the four-necked flask to 120 ° C. Stir for 30 minutes while heating. As a result, the contents of the four-necked flask changed from purple to blue. The contents of the four-necked flask are then allowed to cool to 60 ° C., after which 1.00 g of 1-chloromethylpyrene is added to the contents of the four-necked flask and the contents of the four-necked flask are heated for 5 hours. Refluxed. The color of the contents of the four-necked flask changed from blue to brown. After refluxing, the contents of the four-necked flask were poured into water and suction filtered to obtain a reddish residue.

  The residue was washed with methanol and suction filtered to obtain a reddish residue. This residue was extracted with acetone, and the extract was concentrated with an evaporator. The obtained concentrate was washed with diethyl ether and suction filtered again to obtain reddish brown crystals. An IR chart of this crystal is shown in FIG. This crystal was N, N′-di (1-pyrenylmethyl) quinacridone having a structure represented by Structural Formula 34. The fluorescence spectrum of N, N′-di (1-pyrenylmethyl) quinacridone represented by this structural formula 34 is shown in FIG.

  In the quinacridone derivative represented by the structural formula 34, a pyrenyl group is bonded to a nitrogen atom in the quinacridone skeleton via a methylene group, and this pyrenyl group is an atomic group that emits blue light, and the quinacridone skeleton itself is an atomic group that emits red light. Therefore, this quinacridone derivative is a reddish white light-emitting compound. In order to emit light in bluish white, the quinacridone derivative represented by the structural formula 34 is preferably substituted with a pyrenyl group at the 2-position and the 9-position (ie, p-position).

(Example 12)
<Synthesis of quinacridone unit>
Quinacridone (25 g) was placed in a 1 L four-necked flask, and DMF (500 mL) was placed in the four-necked flask, heated to 110 ° C. with stirring, and stirred at that temperature for 20 minutes.

  The contents of the four-necked flask are air-cooled to 60 ° C., 60% sodium hydride is added, taking care not to generate hydrogen, and the contents of the four-necked flask are again heated to 110 ° C. at that temperature. Stir for 30 minutes.

  The contents of the four-necked flask were air-cooled to 60 ° C., and then 71 g of 1-bromodecane was charged into the four-necked flask and then heated to reflux for 5 hours.

  After the contents of the four-necked flask were air-cooled, the contents were poured into ice water made with ion-exchanged water to stop the reaction.

  The contents put into ice water were neutralized with dilute hydrochloric acid, filtered, and the resulting residue was washed with water and methanol. The residue after washing was dissolved in chloroform, dehydrated with sodium sulfate, and filtered. The residue obtained by concentrating the resulting filtrate was recrystallized from tetrahydrofuran and filtered. The obtained crystals were purified by silica gel chromatography. An IR chart of 2.31 g of the crystals obtained by purification is shown in FIG. This crystal was N, N′-didecylquinacridone represented by the structural formula 35.

  A 200 mL three-necked flask contains 1.83 g of N, N′-didecylquinacridone represented by the structural formula 35, 3.08 g of potassium iodide, and 2.65 g of potassium iodate, and further 100 mL of acetic acid. Housed. The contents of the three-necked flask were refluxed for 4 hours with stirring. When 4 hours had elapsed, the contents of the three-necked flask were concentrated under reduced pressure using an evaporator and dried. A large amount of water was added to the concentrated dried product, and the mixture was subjected to dispersion treatment with an ultrasonic cleaner, followed by suction filtration.

  The obtained crystals were washed with methanol and dried. The dried crystals were further dissolved in chloroform and purified by silica gel chromatography to obtain crystals. The IR chart of this crystal is shown in FIG. From this IR chart, this crystal was identified as N, N'-didecyl-2,9-diiodoquinacridone represented by the structural formula 36.

  A 200 mL three-necked flask was charged with 2.99 g of the quinacridone compound represented by the structural formula 36, 850 mg of copper cyanide and 100 mL of DMF. The contents of the three-necked flask were refluxed for 4 hours while stirring. When 4 hours had elapsed, the contents of the three-necked flask were concentrated under reduced pressure using an evaporator. The concentrate was put into 250 mL of chloroform, heated until the chloroform boiled, and then naturally filtered. Crystals deposited by cooling the obtained filtrate were collected by suction filtration.

  The IR chart of this crystal is shown in FIG. This crystal was N, N′-didecyl-2,9-dicyanoquinacridone represented by the structural formula 37.

  A 100 mL three-necked flask was charged with 450 mg of the quinacridone compound represented by the structural formula 37 and 50 mL of acetic acid, and the contents of the three-necked flask were stirred while being heated to 80 ° C. After heating and stirring for 30 minutes, the contents of the three-necked flask are cooled to 30 ° C., and 30 mL of sulfuric acid aqueous solution in which 40 mL of sulfuric acid and 10 mL of water are mixed is put into the three-necked flask, and then To the contents of the three-necked flask, 80 mg of sodium nitrite was added 5 times at intervals of 10 minutes. Sodium nitrite adhering to the inner wall of the three-necked flask was washed away with 20 mL of sulfuric acid aqueous solution.

  The contents of the three-necked flask were heated to 80 ° C. and stirred for 4 hours. Thereafter, the contents of the three-necked flask were cooled, and the cooled contents were put into 500 mL of ice water.

  The ice water charged with the contents was subjected to suction filtration, and the obtained crystals were washed successively with water, methanol and a small amount of chloroform.

  After the washed crystals were dried under reduced pressure, the crystals were dissolved by heating in 10 mL of DMF, and the filtrate obtained by filtration was cooled to room temperature and recrystallized. The obtained crystals were washed with methanol and dried. An IR chart of the obtained crystal is shown in FIG. The crystal was N, N′-didecylquinacridone-2,9-dicarboxylic acid represented by the structural formula 38.

  In a 30 mL eggplant-shaped flask, 880 mg of N, N'-didecylquinacridone-2,9-dicarboxylic acid represented by Structural Formula 38 and boiling stone were added, and 3 mL of thionyl chloride was further added. The contents of the eggplant-shaped flask were heated to reflux for 4 hours and then air-cooled. Thereafter, the contents of the eggplant-shaped flask were distilled to discharge excess thionyl chloride, and the contents after distillation were further distilled under reduced pressure for 1 hour to completely remove thionyl chloride. FIG. 27 shows an IR chart of the product in the eggplant-shaped flask. This product is shown in Structural Formula 39.

<Synthesis of pyrene unit>
A 20 mL eggplant type flask was charged with 2.0 g of 1-pyrenecarboxylic acid, boiling stone and 10 mL of thionyl chloride, and the contents of the eggplant type flask were heated to reflux for 4 hours.

  Reflux was stopped and distilled for 2 hours to discharge excess thionyl chloride by distillation. After distillation, the contents of the eggplant-shaped flask were distilled under reduced pressure for 1 hour to further discharge and remove thionyl chloride. The residue after distillation under reduced pressure was an acid chloride represented by Structural Formula 40.

  In a 500 mL four-necked flask, 170 mL of tetrahydrofuran, 2.4 mL of pyridine, and 4.06 g of hydrazide monohydrate were placed. A solution prepared by dissolving 2.0 g of the acid chloride represented by the structural formula 40 in 80 mL of tetrahydrofuran was added dropwise to the contents of the four-necked flask while cooling the contents with ice. After dripping, the contents of the four-necked flask were heated to 40-50 ° C. for 1 hour in an oil bath. After the lapse of 1 hour, the contents of the four-necked flask were air-cooled, and then the contents of the four-necked flask were put into 800 mL of ice water, and the precipitated crystals were suction filtered. The resulting filtered solid was washed with methanol to remove water and dried under reduced pressure. An IR chart of the obtained crystal is shown in FIG. This crystal was pyrene hydrazide represented by the structural formula 41.

<Coupling>
A 300 mL three-necked flask was charged with 1.09 g (4.18 mmol) of pyrene hydrazide represented by the above structural formula 41, 120 ml of tetrahydrofuran, and 2.4 ml of pyridine. While cooling the contents of the three-necked flask with ice water, 60 mL of a tetrahydrofuran solution in which 1.29 mmol of didecylquinacridone chloride represented by the structural formula 39 was dissolved was gradually added dropwise to the three-necked flask. After completion of dropping, the contents of the three-necked flask were stirred for 1 hour 30 minutes while heating to 50 ° C. in an oil bath, and then refluxed with stirring for 30 minutes.

  Thereafter, the mixture was air-cooled, and the contents of the three-necked flask were concentrated to a half volume under reduced pressure, and the concentrated solution was poured into ice water. Crystals precipitated by throwing them into ice water were filtered off by suction filtration, and the filtered crystals were dissolved in 150 mL of chloroform and dehydrated with sodium sulfate. The filtrate obtained by suction filtration was concentrated to dryness. An IR chart of this crystal is shown in FIG. This crystal was a compound having a structure represented by Structural Formula 42.

  A 10 mL eggplant-shaped flask was charged with 0.5 g of the compound represented by the structural formula 42 and 5 mL of phosphoryl chloride. The contents of the eggplant-shaped flask were stirred for 6 hours while heating to 120 ° C. Thereafter, the contents of the eggplant-shaped flask were put into ice water, neutralized with a 10% sodium hydroxide solution, and suction filtered. The crystals obtained by filtration were washed 3 times with water and finally with a small amount of methanol. The washed crystals were further purified by extraction with a Soxhlet extractor 20 times with methanol, 5 times with toluene and 50 times with acetone. An IR chart of the purified crystals obtained is shown in FIG. This purified crystal was a compound represented by Structural Formula 43.

  As shown in Example 9, since the pyrenyl group is an atomic group that emits blue light and the quinacridone skeleton is an atomic group that emits red light, the quinacridone derivative represented by Structural Formula 43 is considered to emit white light. It is done. In addition, since the decyl group is bonded to the nitrogen atom in the quinacridone skeleton, it becomes soluble in an organic solvent.

Claims (5)

A quinacridone derivative represented by the following structural formula (1):

(However, in the structural formula (1), X is -COOR ₁ (wherein, _{R 1} is hydrogen atom, or an alkyl group having 1 to 5 carbon atoms.), A bromine atom, an iodine atom, aromatic hydrocarbon group (excluding the number of carbon atoms of the aromatic hydrocarbon group when substituted aromatic hydrocarbon group.) substituted to carbon atoms which may 1-10 alkyl group, _-O-CH 2 CH 2 _-O- structure Benzene having the formula (1A), wherein one oxygen atom in the structural formula (1A) is bonded to the benzene ring in the structural formula (1) and the other oxygen atom is 4-position benzene in the structural formula (1) A dioxane-forming group bonded to carbon on the ring, a group represented by —CH ₂ —Ar (wherein Ar represents an aromatic hydrocarbon group), and an aromatic hydrocarbon group-substituted oxadi represented by the structural formula (1B) An azole group (provided that A in the structural formula (1B) Represents an aromatic hydrocarbon group), or an aromatic hydrocarbon group-substituted vinyl group represented by the structural formula (1C) of —CH═CH—Ar (wherein Ar represents an aromatic hydrocarbon group). Show

Y is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms that may be substituted with an aromatic hydrocarbon group (excluding the carbon number of the aromatic hydrocarbon group when the aromatic hydrocarbon group is substituted). And when X is a bromine atom or an iodine atom, Y is an optionally substituted aromatic hydrocarbon group having 1 to 20 carbon atoms (when an aromatic hydrocarbon group is substituted, the carbon number of the aromatic hydrocarbon group is Is an alkyl group. ) When the Y is an alkyl group having 1 to 20 carbon atoms which may be substituted for the aromatic hydrocarbon group (excluding the carbon number of the aromatic hydrocarbon group when the aromatic hydrocarbon group is substituted), When X is —COOR _1a (wherein R _1a represents an alkyl group having 2 to 10 carbon atoms), an aromatic hydrocarbon group may have 1 to 10 carbon atoms (when the aromatic hydrocarbon group is substituted) An alkyl group of the aromatic hydrocarbon group (excluding the number of carbon atoms of the aromatic hydrocarbon group), an aromatic hydrocarbon group-substituted oxadiazole group represented by the structural formula (2A) (provided that the aromatic hydrocarbon group is a pyrenyl group), Alternatively, the quinacridone derivative according to claim 1, wherein the quinacridone derivative is an aromatic-substituted vinyl group represented by the structural formula (1C).   When Y represents an alkyl group having 1 to 20 carbon atoms that may be substituted with an aromatic hydrocarbon group (excluding the carbon number of the aromatic hydrocarbon group when the aromatic hydrocarbon group is substituted), The quinacridone derivative according to claim 1 or 2, wherein the aromatic hydrocarbon group that may be bonded to the alkyl group is a phenyl group, an anthryl group, or a pyrenyl group.   The quinacridone derivative according to claim 1, wherein Y is a hydrogen atom, and X is the dioxane-forming group. Y is an alkyl group having 1 to 20 carbon atoms, X is a group represented by —CH ₂ —Ar (wherein Ar represents an aromatic hydrocarbon group), an aromatic represented by the structural formula (1A) The quinacridone derivative according to claim 1, which is a hydrocarbon group-substituted oxadiazole group.

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