JP2017200905A - Organic compound, and electrochromic element, optical filter, lens unit, imaging apparatus, and window material including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic compound having an absorption peak in a wavelength region of 540 nm or more in a colored state.SOLUTION: The organic compound is represented by formula (1). [R-Rand R-Rare each independently H, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an acyl group, or a halogen atom; Rand Rare each independently an alkyl group, an aryl group, or an aralkyl group; and substituents may be bonded to each other to form a ring structure.]SELECTED DRAWING: Figure 1

Description

  The present invention relates to an electrochromic organic compound, and an electrochromic element, an optical filter, a lens unit, an imaging device, and a window material having the same.

  Various materials have electrochromic (hereinafter sometimes abbreviated as “EC”) properties that change the optical absorption properties (colored state and light transmittance) of substances due to electrochemical redox reactions. Has been reported.

  Examples of the organic low molecular compound having EC properties (organic low molecular EC compound) include a viologen derivative which is a cathodic EC compound colored by reduction, and a phenazine derivative which is an anodic EC compound colored by oxidation.

  These low-molecular EC compounds have a shorter π-conjugate length than the conductive polymer and have absorption in the ultraviolet region. In the case of anodic EC compounds, they are oxidized, and in the case of cathodic EC compounds, they are reduced. The conjugate length becomes longer than the conjugate length of the compound before oxidation or reduction. Therefore, the wavelength region that absorbs light becomes a visible light region, and the organic low-molecular EC compound is colored by oxidation or reduction.

  Conventionally, application of EC elements to light control mirrors for automobiles, electronic paper, and the like has been proposed. These EC elements utilize the characteristic that various color tones can be displayed by selecting materials. In utilizing EC elements, the development of materials of various colors suggests the possibility for a wide range of applications. For example, when considering application to a full-color display or the like, materials for coloring cyan, magenta, and yellow are required. Further, considering application to a wide range of uses, EC materials having various absorption wavelengths are required at the time of coloring.

  Patent Document 1 describes a plurality of phenazine derivatives and viologen derivatives having different absorption wavelengths during coloring, and discloses a plurality of phenazine derivatives having different maximum absorption wavelengths in the range of 460 nm to 532 nm.

Japanese Patent No. 4384730

  However, the phenazine derivative described in Patent Document 1 does not have an absorption peak in a wavelength region of 540 nm or more in a colored state.

  The present invention has been made in view of the above problems, and an object thereof is to provide an electrochromic organic compound having an absorption peak in a wavelength region of 540 nm or more in a colored state.

  In one aspect of the present invention, the organic compound is represented by the following general formula (1).

一般式（１）において、Ｒ_１１〜Ｒ_１５は、それぞれ独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアリール基、置換基を有していてもよいアリールオキシ基、置換基を有していてもよいアラルキル基、アシル基、又はハロゲン原子を表す。ただし、Ｒ_１１、Ｒ_１３及びＲ_１５のうち少なくとも１つは、置換基を有していてもよいアルコキシ基又は置換基を有していてもよいアリールオキシ基である。また、Ｒ_１１〜Ｒ_１５は、置換基同士で結合して環構造を形成してもよい。

In General Formula (1), R _{11 to} R ₁₅ each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. An aryl group which may have a substituent, an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom; However, at least one of R ₁₁ , R ₁₃ and R ₁₅ is an alkoxy group which may have a substituent or an aryloxy group which may have a substituent. R _{11 to} R ₁₅ may combine with each other to form a ring structure.

R ₅ and R ₆ each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.

R ₂₁ to R ₂₄ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, It represents an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom, and may be bonded together to form a ring structure.

  According to the organic compound as one aspect of the present invention, an organic compound having an absorption peak in a wavelength region of 540 nm or more in a colored state can be provided.

The figure which shows an example of the organic EC compound which concerns on 1st Embodiment with a molecular model. The cross-sectional schematic diagram of an example of the electrochromic element which concerns on 2nd Embodiment. The block diagram explaining the structure of the electrochromic apparatus which concerns on 3rd Embodiment. FIG. 10 is a schematic diagram illustrating a configuration of an example of an imaging apparatus according to a third embodiment. The figure which shows the ultraviolet visible absorption spectrum in each neutral state of the exemplary compound of Example 3. The figure which shows the transmittance | permeability spectrum at the time of the coloring / decoloring of the electrochromic element of Example 5. The figure explaining the structure of the window material of 4th Embodiment. The figure which shows the ultraviolet visible absorption spectrum in the neutral state of the exemplary compound of Example 13. The figure which shows the transmittance | permeability spectrum at the time of the coloring / decoloring of the electrochromic element of Example 15.

  The organic compound of this embodiment is an organic compound having electrochromic properties (EC properties), and is an organic compound represented by the general formula (1).

一般式（１）において、Ｒ_１１〜Ｒ_１５は、それぞれ独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアリール基、置換基を有していてもよいアリールオキシ基、置換基を有していてもよいアラルキル基、アシル基、又はハロゲン原子を表す。ただし、Ｒ_１１、Ｒ_１３及びＲ_１５のうち少なくとも１つは、置換基を有していてもよいアルコキシ基又は置換基を有していてもよいアリールオキシ基である。Ｒ_１１〜Ｒ_１５は、置換基同士で結合して環構造を形成してもよい。

In General Formula (1), R _{11 to} R ₁₅ each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. An aryl group which may have a substituent, an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom; However, at least one of R ₁₁ , R ₁₃ and R ₁₅ is an alkoxy group which may have a substituent or an aryloxy group which may have a substituent. R _{11 to} R ₁₅ may combine with each other to form a ring structure.

R ₅ and R ₆ each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.

R ₂₁ to R ₂₄ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, It represents an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom, and may be bonded together to form a ring structure.

The organic compound represented by the general formula (1) includes an organic compound represented by the following general formula (2). This is an organic compound in which R ₁₁ is an alkoxy group which may have a substituent or an aryloxy group which may have a substituent in the compound represented by the general formula (1).

一般式（２）において、Ｒ_１は、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基を表す。

In General Formula (2), R ₁ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.

R ₁₂ to R ₁₅ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, The aryloxy group which may have a substituent, the aralkyl group which may have a substituent, an acyl group, or a halogen atom is represented. However, R ₁₂ to R ₁₅ may combine with each other to form a ring structure.

R ₅ and R ₆ each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.

R ₂₁ to R ₂₄ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, It represents an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom, and may be bonded together to form a ring structure.

The organic compound represented by the general formula (1) includes an organic compound having EC properties represented by the following general formula (3). This is an organic compound represented by the general formula (1), and each of R ₁₁ and R ₁₅ is an alkoxy group which may have a substituent or an aryloxy group which may have a substituent. It is an organic compound.

一般式（３）において、Ｒ１およびＲ２は、それぞれ独立に、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基を表す。

In General Formula (3), R 1 and R 2 may each independently have an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. Represents an aralkyl group.

R ₁₂ to R ₁₄ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, The aryloxy group which may have a substituent, the aralkyl group which may have a substituent, an acyl group, or a halogen atom is represented. However, R ₁₂ to R ₁₄ may combine with each other to form a ring structure.

R ₅ and R ₆ each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.

R ₂₁ to R ₂₄ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, It represents an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom, and may be bonded together to form a ring structure.

Moreover, the organic compound represented by General formula (1) contains the organic compound which has EC property shown by following General formula (4). This is an organic compound in which R ₁₁ is an alkoxy group which may have a substituent or an aryloxy group which may have a substituent in the organic compound represented by the general formula (1). In addition, R ₂₃ is a phenyl group having a substituent, and at least one of the ortho positions of the phenyl group is an organic compound substituted with an alkoxy group or an aryloxy group.

一般式（４）において、Ｒ_１およびＲ_７は、それぞれ独立に、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基を表す。

In General Formula (4), R ₁ and R ₇ each independently have an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. Represents a good aralkyl group.

R _{12 to} R ₁₅ and R _{31 to} R ₃₄ each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. An aryl group that may have a substituent, an aryloxy group that may have a substituent, an aralkyl group that may have a substituent, an acyl group, or a halogen atom; However, R _{12 to} R ₁₅ may be bonded to each other to form a ring structure.

R ₅ and R ₆ each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.

R ₂₁ , R ₂₂ and R ₂₄ each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An aryl group, an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom, which is bonded to each other to form a ring structure Also good.

Furthermore, the organic compound represented by the general formula (1) includes an organic compound having EC properties represented by the following general formula (5). This is an alkoxy group that may have a substituent or an aryloxy group that may have a substituent in each of R ₁₁ and R _{15 in} the organic compound represented by the general formula (1). It is an organic compound. R ₂₃ is a phenyl group having a substituent, and each of the two ortho positions of the phenyl group is an organic compound substituted with an alkoxy group or an aryloxy group.

一般式（５）において、Ｒ１、Ｒ２、Ｒ７およびＲ８は、それぞれ独立に、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基を表す。

In General Formula (5), R1, R2, R7, and R8 each independently have an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. Represents an aralkyl group which may be present.

R _{12 to} R ₁₄ and R _{32 to} R ₃₄ each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. Represents an aryl group which may have a substituent, an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom; It may be formed.

R ₅ and R ₆ each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.

R ₂₁ , R ₂₂ , and R ₂₄ each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. An aryl group, an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom, which is bonded to each other to form a ring structure Also good.

The organic compound represented by the general formula (1) includes an organic compound having EC property represented by the general formula (6). This is because in the compound represented by the general formula (1), the substituent at the para position of the phenyl group represented by R ₁₃ has an alkoxy group or a substituent which may have a substituent. It is also an organic compound that is an aryloxy group.

一般式（６）において、Ｒ_３は、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基を表す。
Ｒ_１１、Ｒ_１２、Ｒ_１４およびＲ_１５は、それぞれ独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアリール基、置換基を有していてもよいアリールオキシ基、置換基を有していてもよいアラルキル基、アシル基、又はハロゲン原子を表し、置換基同士で結合して環構造を形成してもよい。

In General Formula (6), R ₃ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
R ₁₁ , R ₁₂ , R ₁₄ and R ₁₅ each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. Represents an aryl group which may have a substituent, an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom; It may be formed.

R ₅ and R ₆ each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.

R ₂₁ to R ₂₄ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, It represents an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom, and may be bonded together to form a ring structure.

In the organic compound represented by the general formula (6), at least one of R ₁₁ and R ₁₅ may have an alkyl group which may have a substituent, or an aryl group or substituent which may have a substituent. It is preferable that it is an aralkyl group which may have. In such a compound, the phenazine ring and the phenyl group are twisted due to the steric hindrance of the substituents (R ₁₁ and R ₁₅ ) arranged at the ortho position of the phenyl group. Therefore, among the organic compounds represented by the general formula (6), high transparency is exhibited in a neutral state (decolored state).

Moreover, the organic compound represented by General formula (1) contains the organic compound which has EC property shown by following General formula (7). This is an organic compound represented by the general formula (1), with substituents which may substituted alkoxy group or an optionally substituted aryl group represented by R ₁₃ It is an organic compound. In addition, the substituent represented by R ₂₃ is an organic compound in which the para position is a phenyl group substituted with an alkoxy group or an aryloxy group.

一般式（７）において、Ｒ_３およびＲ_９は、それぞれ独立に、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアラルキル基を表す。

In General Formula (7), R ₃ and R ₉ each independently have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents a good aralkyl group.

R ₁₁ , R ₁₂ , R ₁₄ , R ₁₅ , R ₃₁ , R ₃₂ , R ₃₄ and R ₃₅ each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. An optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted aralkyl group, an acyl group, or a halogen atom. And a substituent may be bonded to each other to form a ring structure.

R ₅ and R ₆ each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.

R ₂₁ , R ₂₂ and R ₂₄ each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An aryl group, an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom, which is bonded to each other to form a ring structure Also good.

In the organic compound represented by the general formula (7), at least one of R ₁₁ , R ₁₅ , R ₃₁ and R ₃₅ may have an alkyl group which may have a substituent, or a substituent. A preferable aryl group and an aralkyl group which may have a substituent are preferable. In such a compound, the phenazine ring and the phenyl group are twisted due to the steric hindrance of the substituents (R ₁₁ , R ₁₅ , R ₃₁ , R ₃₅ ) arranged at the ortho position of the phenyl group. Therefore, among organic compounds represented by the general formula (7), high transparency is exhibited in a neutral state (decolored state).

  Specific examples of the substituents in the general formulas (1) to (7) are shown below. However, these are merely representative examples of organic compounds, and the present invention is not limited thereto.

The alkyl group which may have a substituent represented by R _{1 to} R ₃ and R _{7 to} R ₉ may be linear, branched or cyclic. Further, a hydrogen atom may be replaced with a fluorine atom or an ester group. _{Further, R 1 ~R 3, R 7} ~R 9 alkyl group which may have a substituent represented by is preferably 1 to 20 carbon atoms. Specific examples of the alkyl group represented by R _{1 to} R ₃ and R _{7 to} R ₉ include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, an isobutyl group, and a cyclohexyl group. And a trifluoromethyl group. Preferably, they are a methyl group, isopropyl group, and isobutyl group.

The aryl group which may have a substituent represented by R _{1 to} R ₃ and R _{7 to} R ₉ is, for example, a phenyl group, a tolyl group, a biphenyl group, a fluorenyl group, a naphthyl group, a fluoranthenyl group, an anthryl. Group, pyrenyl group and the like. A phenyl group is preferred. The aryl group represented by R _{1 to} R ₃ and R _{7 to} R ₉ is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, an aralkyl group, an acyl group. You may have group as a substituent.

Examples of the aralkyl group which may have a substituent represented by R _{1 to} R ₃ and R _{7 to} R ₉ include a benzyl group and a phenethyl group. Aralkyl groups represented by R _{1 to} R ₃ and R _{7 to} R ₉ are substituted with halogen atoms, alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, aryl groups, and acyl groups. You may have as a group.

The alkyl group which may have a substituent represented by R _{11 to} R ₁₅ and R _{31 to} R ₃₅ may be linear, branched or cyclic. Further, a hydrogen atom may be replaced with a fluorine atom or an ester group. The alkyl group represented by R _{11 to} R ₁₅ and R _{31 to} R ₃₅ preferably has 1 to 20 carbon atoms. Specific examples of the alkyl group represented by R _{11 to} R ₁₅ and R _{31 to} R ₃₅ include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, a cyclohexyl group, and trifluoromethyl. Group, isobutyl group and the like.

Examples of the alkoxy group optionally having a substituent represented by R _{11 to} R ₁₅ and R _{31 to} R ₃₅ include a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, and an ethylhexyl group. An oxy group, 2-methoxyethoxy group, benzyloxy group, etc. are mentioned. _{Incidentally,} an alkoxy group represented by _{R 11 ~R 15, R 31 ~R} 35 is preferably 1 to 20 carbon atoms.

Examples of the aryl group which may have a substituent represented by R _{11 to} R ₁₅ and R _{31 to} R ₃₅ include a phenyl group, a biphenyl group, a fluorenyl group, and a naphthyl group. The aryl group represented by R ₃ and R ₉ may have a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an acyl group as a substituent.

Examples of the aryloxy group which may have a substituent represented by R _{11 to} R ₁₅ and R _{31 to} R ₃₅ include a phenoxy group and a naphthyloxy group. The aromatic ring of the aryloxy group which may have a substituent represented by R _{11 to} R ₁₅ and R _{31 to} R ₃₅ is a halogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 or more carbon atoms. You may have 4 or less alkoxy groups as a substituent.

Examples of the aralkyl group optionally having a substituent represented by R _{11 to} R ₁₅ and R _{31 to} R ₃₅ include a benzyl group and a phenethyl group. Aralkyl groups represented by R _{11 to} R ₁₅ and R _{31 to} R ₃₅ are substituted with halogen atoms, alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, aryl groups, and acyl groups. You may have as a group.

Examples of the acyl group represented by R _{11 to} R ₁₅ and R _{31 to} R ₃₅ include an acetyl group and a benzoyl group.

R _{11 to} R ₁₅ and R _{31 to} R ₃₅ may be bonded to each other at adjacent substituents to form a ring structure. Examples of the ring structure formed at this time include a benzene ring, a naphthalene ring, a fluorene ring, and a pyridine ring.

The alkyl group represented by R ₅ and R ₆ may be linear, branched or cyclic. Further, a hydrogen atom may be replaced with a fluorine atom or an ester group. Examples of the alkyl group represented by R5 and R6 include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, and an isobutyl group.

Examples of the aryl group which may have a substituent represented by R ₅ and R ₆ include a phenyl group, a biphenyl group, a fluorenyl group, and a naphthyl group. The aryl group represented by R5 and R6 may have a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an acyl group as a substituent.

Examples of the aralkyl group optionally having a substituent represented by R ₅ and R ₆ include a benzyl group and a phenylethyl group. The aralkyl group represented by R5 and R6 may have a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an acyl group as a substituent.

The alkyl group which may have a substituent represented by R _{21 to} R ₂₄ may be linear, branched or cyclic. Further, a hydrogen atom may be replaced with a fluorine atom or an ester group. The alkyl group represented by R _{21 to} R ₂₄ preferably has 1 to 20 carbon atoms. Specific examples of the alkyl group represented by R _{21 to} R ₂₄ include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, a cyclohexyl group, a trifluoromethyl group, and an isobutyl group. Can be mentioned.

Examples of the alkoxy group optionally having a substituent represented by R _{21 to} R ₂₄ include a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, an ethylhexyloxy group, and 2-methoxy. An ethoxy group, a benzyloxy group, etc. are mentioned. The alkoxy group represented by R _{21 to} R ₂₄ preferably has 1 to 20 carbon atoms.

Examples of the aryl group which may have a substituent represented by R _{21 to} R ₂₄ include a phenyl group, a biphenyl group, a fluorenyl group, and a naphthyl group. The aryl group represented by R _{21 to} R ₂₄ may have a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an acyl group as a substituent.

Examples of the aryloxy group optionally having a substituent represented by R _{21 to} R ₂₄ include a phenoxy group and a naphthyloxy group. The aromatic ring of the aryloxy group which may have a substituent represented by R _{21 to} R ₂₄ is a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. You may have as a substituent.

Examples of the aralkyl group which may have a substituent represented by R _{21 to} R ₂₄ include a benzyl group and a phenethyl group. The aralkyl group represented by R _{21 to} R ₂₄ may have a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an acyl group as a substituent. .

Examples of the acyl group represented by R _{21 to} R ₂₄ include an acetyl group and a benzoyl group.

R _{21 to} R ₂₄ may be bonded to each other at adjacent substituents to form a ring structure. Examples of the ring structure formed at this time include a benzene ring, a naphthalene ring, a fluorene ring, and a pyridine ring.

  Next, characteristics based on the structure of the phenazine derivative which is an organic compound having EC property represented by the general formula (1) will be described. FIG. 1 is a diagram showing an organic compound represented by the following chemical structural formula (8), which is an example of the organic compound according to the present embodiment, as a molecular model.

図１は、一般式（５）において、Ｒ_１とＲ_２の一方がイソプロピル基で、他方がメチル基であり、Ｒ_７とＲ_８の一方がイソプロピル基で、他方がメチル基の場合の分子の立体構造を示している。すなわち、化学構造式（８）で表される有機化合物は、フェナジン環に結合した２つのフェニル基のそれぞれのオルト位の一方がイソプロポキシ基であり、他方がメトキシ基である。化学構造式（８）で表わされる有機化合物は、後述の例示化合物Ａ−２１に該当する。そのため、以降の説明では、化学構造式（８）で表わされる有機化合物を「例示化合物Ａ−２１」と呼ぶ。

FIG. 1 shows a molecule in the general formula (5) in which _one of R ₁ and R ₂ is an isopropyl group, the other is a methyl group, one of R ₇ and R ₈ is an isopropyl group, and the other is a methyl group. The three-dimensional structure is shown. That is, in the organic compound represented by the chemical structural formula (8), one of the ortho positions of two phenyl groups bonded to the phenazine ring is an isopropoxy group and the other is a methoxy group. The organic compound represented by the chemical structural formula (8) corresponds to Exemplified Compound A-21 described later. Therefore, in the following description, the organic compound represented by the chemical structural formula (8) is referred to as “Exemplary Compound A-21”.

The three-dimensional structure shown in FIG. 1 is Gaussian 09 * Revision C., which is electronic state calculation software. The structure optimization calculation of the ground state was performed using 01. At that time, as a quantum chemical calculation method, a density functional theory was adopted, and LC-BLYP was used as a functional. The basis functions are Gaussian 09, Revision C. In 01, 6-31 + G ** was used.
Gaussian 09, Revision C. 01,
M.M. J. et al. Frisch, G.M. W. Trucks, H.C. B. Schlegel, G.M. E. Scuseria,
M.M. A. Robb, J .; R. Cheeseman, G.M. Scalmani, V.M. Barone, B.M. Mennucci,
G. A. Petersson, H.C. Nakatsuji, M .; Caricato, X. et al. Li, H .; P. Hratchian,
A. F. Izmaylov, J. et al. Bloino, G.M. Zheng, J. et al. L. Sonnenberg, M .; Hada,
M.M. Ehara, K .; Toyota, R.A. Fukuda, J. et al. Hasegawa, M .; Ishida, T .; Nakajima,
Y. Honda, O .; Kitao, H .; Nakai, T .; Vreven, J.M. A. Montgomery, Jr. ,
J. et al. E. Peralta, F.A. Ogliaro, M .; Bearpark, J.A. J. et al. Heyd, E .; Brothers,
K. N. Kudin, V .; N. Staroverov, T .; Keith, R.A. Kobayashi, J. et al. Normand,
K. Raghavachari, A .; Rendell, J. et al. C. Burant, S.M. S. Iyengar, J. et al. Tomasi,
M.M. Cossi, N .; Rega, J .; M.M. Millam, M.M. Klene, J .; E. Knox, J .; B. Cross,
V. Bakken, C.I. Adamo, J .; Jaramillo, R.A. Gomperts, R.M. E. Stratmann,
O. Yazyev, A .; J. et al. Austin, R.A. Cammi, C.I. Pomeri, J .; W. Ochterski,
R. L. Martin, K.M. Morokuma, V.M. G. Zakrzewski, G.M. A. Voth,
P. Salvador, J .; J. et al. Dannenberg, S.M. Dapprich, A.D. D. Daniels,
O. Farkas, J .; B. Foresman, J.M. V. Ortiz, J. et al. Cioslowski,
and D.D. J. et al. Fox, Gaussian, Inc. , Wallingford CT, 2010.
In FIG. 1, exemplary compound A-21 has a phenazine ring 20 and a phenyl group 21 bonded to the phenazine ring 20, and has an isopropoxy group and a methoxy group at the ortho position of the phenyl group 21. ing.

  Considering the phenazine ring 20 exhibiting electrochromic characteristics as a plane, the plane of the phenyl group 21 having an alkoxy group at the ortho position intersects the plane of the phenazine ring 20, and the plane of the phenazine ring 20 and the plane of the phenyl group 21 The angle between the two is large. In a phenazine derivative, in the molecular structure in which the angle formed by the plane of the phenazine ring and the plane of the phenyl group is close to 90 °, the orbits of the π electrons of the phenazine ring and the phenyl group are orthogonal and resonance is reduced. Therefore, by localizing HOMO (the highest occupied molecular orbital) in the phenazine ring 20, the absorption in the neutral state can be shortened.

  Here, the difference between the organic compound of the present embodiment and a known phenazine derivative will be described. Patent Document 1 discloses compounds Ref-1 and Ref-2 represented by the following chemical structural formulas.

公知の化合物Ｒｅｆ−１は、フェナジン環に結合したフェニル基のオルト位に置換基が存在しない。そのため、分子の平面性が高く、分子全体に電子的な共鳴構造が拡がることにより、その中性状態における吸収は長波長化する。実際、発明者らが追試した結果、化合物Ｒｅｆ−１の中性状態における吸収端は４６０ｎｍ付近の可視波長域まで存在し、固体状態および溶液状態で淡赤茶色を呈する。

The known compound Ref-1 has no substituent at the ortho position of the phenyl group bonded to the phenazine ring. Therefore, the planarity of the molecule is high, and the electronic resonance structure spreads throughout the molecule, so that the absorption in the neutral state becomes longer. In fact, as a result of further trials by the inventors, the absorption edge in the neutral state of the compound Ref-1 exists up to a visible wavelength region near 460 nm, and exhibits a light reddish brown color in a solid state and a solution state.

  Further, in Patent Document 1, as shown in the compound Ref-2 as an example, neutral state coloration is reduced by introducing an alkyl group such as a methyl group into the ortho position of the phenyl group bonded to the phenazine ring. It is described. This is thought to mean that neutral absorption shortens the wavelength by twisting the phenazine ring and the phenyl group due to steric hindrance of an alkyl group such as a methyl group.

  However, according to Patent Document 1, the wavelength (absorption wavelength) of the absorption peak in the colored state is 532 nm for compound Ref-1, whereas 512 nm for compound Ref-2, and Ref-2 absorbs more. The wavelength is short. This indicates that the molecular twist in the neutral state described above remains in the molecular structure of the colored radical cation, and as a result, the absorption in the oxidized state is also shortened.

  That is, in the conventional phenazine derivative, the neutral state transparency improvement (shortening the absorption wavelength) and the long wavelength absorption in the oxidative coloring state are not compatible.

  On the other hand, the organic compound of the present embodiment has a short wavelength and high transparency in the neutral state due to the twisting of the phenazine ring 20 and the phenyl group 21, and in the oxidized state (colored state), from the compound Ref-1. Also has an absorption peak in the long wavelength region of 540 nm or more. This is caused by having an alkoxy group as a substituent, and is caused by an effect specific to an alkoxy group or an aryloxy group, which could not be expected from known knowledge.

  In the present specification, in the absorption spectrum, a light absorption amount having a maximum value in a certain wavelength band and a half width of 20 nm or more is called an absorption peak. Here, the half-value width means the width of the wavelength at which the absorbance in the absorption spectrum becomes a half value (half value) of the absorbance at the maximum value.

  The organic compound according to the present embodiment only needs to have at least one absorption peak in the wavelength region of 540 nm or more in the oxidized state (colored state). Not limited to this, the organic compound according to the present embodiment has a plurality of absorption peaks in the wavelength region of 540 nm or more in the oxidation state (colored state), or is absorbed in a wavelength region of 540 nm or more and a wavelength region shorter than 540 nm. It may have a peak.

  The effect peculiar to this alkoxy group or aryloxy group will be described. By the above-described quantum chemical calculation, the molecular structures of the exemplary compound A-21 and the known compound Ref-2 in the neutral state and the oxidized (radical cation) state were predicted. Table 1 shows the dihedral angles of the phenazine ring and the phenyl group obtained by calculation.

例示化合物Ａ−２１では、酸化状態における二面角の角度が４５．０°であったのに対して、化合物Ｒｅｆ−２では４９．３°となった。また、フェナジン環２０とフェニル基２１との結合の電子密度を表わす結合次数は、例示化合物Ａ−２１では０．９８２８、化合物Ｒｅｆ−２では０．４８７０であった。

In Illustrative Compound A-21, the dihedral angle in the oxidized state was 45.0 °, whereas in Compound Ref-2, it was 49.3 °. Further, the bond order representing the electron density of the bond between the phenazine ring 20 and the phenyl group 21 was 0.9828 for the exemplary compound A-21 and 0.4870 for the compound Ref-2.

  These results show that in the neutral state, Exemplified Compound A-21 and Compound Ref-2 have substantially the same dihedral angle, whereas in the radical cation state, which is an oxidized state, Exemplified Compound A- 21 indicates that the planarity is higher than that of the compound Ref-2. That is, it is suggested that Exemplified Compound A-21 promotes mixing of the phenazine ring and the orbital of the phenyl group in the oxidized state as compared with Compound Ref-2. As a result, Exemplified Compound A-21 has a longer absorption peak in the oxidized state.

  This is an effect that was not obtained with the methyl group substituent on the phenyl group of the compound Ref-2, and this embodiment represented by the general formula (1) in which the phenyl group has an alkoxy group or an aryloxy group as a substituent. This is an effect peculiar to organic compounds. That is, when the dihedral angle in the oxidized state is smaller than that in the neutral state in the oxidized state, the organic compound of the present embodiment, as shown below, is used as a substituent of the hydrogen atom and phenyl group of the phenazine ring. A hydrogen bond with an oxygen atom contained in the alkoxy group occurs. Therefore, it is easy to form a stable six-membered ring. As a result, in the oxidized state, the dihedral angle between the phenazine ring and the phenyl group becomes small and the planarity becomes high, so that mixing of orbits is promoted more than before.

一方、化合物Ｒｅｆ−２のようなアルキル置換基は、弱い電子供与性基であり酸素原子も含まれないため、酸化状態の二面角は比較的大きく、吸収ピークの長波長化が起こらない。

On the other hand, an alkyl substituent such as compound Ref-2 is a weak electron-donating group and does not contain an oxygen atom. Therefore, the dihedral angle in the oxidation state is relatively large, and the absorption peak does not increase in wavelength.

  As described above, the organic compound according to the present embodiment has a strong electron donating property of the alkoxy group and an electronic mutual relationship between a lone pair of oxygen atoms (law pair) contained in the alkoxy group and a hydrogen atom on the phenazine ring. Due to the contribution of the action, twisting occurs in the decolored state. Therefore, planarity is improved in the colored state.

  Therefore, the organic compound according to the present embodiment has a high transparency by shortening the wavelength by twisting the phenazine ring and the phenyl group in the decolored state. Further, in the organic compound according to this embodiment, in the colored state, mixing of the orbital of the phenazine ring and the phenyl group is promoted by an electronic effect peculiar to the alkoxy group, and the absorption becomes longer. That is, according to the organic compound according to the present embodiment, it is possible to provide an organic compound that has an absorption peak in a long wavelength region of 540 nm or longer in a colored state and has higher transparency in a decolored state than before. it can.

  The EC characteristics of another organic compound represented by the general formula (1) will be described. The organic compound represented by the following chemical structural formula (9) is an example of the organic compound according to the present embodiment represented by the general formula (1). In addition, since the organic compound represented by Chemical Structural Formula (9) corresponds to Exemplified Compound C-6 described later, it will be referred to as Exemplified Compound C-6 in the following description.

化学構造式（９）で表わされる例示化合物Ｃ−６は、一般式（１）において、Ｒ_１３がアルコキシ基であり、アルコキシ基のＲ_３で表される置換基がイソプロピル基である化合物である。すなわち、例示化合物Ｃ−６は、フェナジン環と、フェナジン環と結合しているフェニル基とを有し、フェニル基のパラ位にはイソプロポキシ基を有している。

Exemplary compound C-6 represented by chemical structural formula (9) is a compound in which R ₁₃ is an alkoxy group and the substituent represented by R ₃ of the alkoxy group is an isopropyl group in general formula (1). . That is, exemplary compound C-6 has a phenazine ring and a phenyl group bonded to the phenazine ring, and has an isopropoxy group at the para position of the phenyl group.

  Here, the difference between Example Compound C-6 and a known phenazine derivative will be described. Patent Document 1 discloses a compound Ref-3 represented by the following chemical structural formula.

公知の化合物Ｒｅｆ−３は、フェナジン環に結合したフェニル基のパラ位にアルコキシ基が存在しない。特許文献１によると、化合物Ｒｅｆ−３の着色状態における吸収ピークの波長（吸収波長）は４９６ｎｍである。

The known compound Ref-3 has no alkoxy group at the para position of the phenyl group bonded to the phenazine ring. According to Patent Document 1, the wavelength (absorption wavelength) of the absorption peak in the colored state of compound Ref-3 is 496 nm.

  On the other hand, Exemplified Compound C-6 has an absorption peak in the wavelength region of 540 nm or longer, which is longer than that of Compound Ref-3, in the oxidized state (colored state). This is caused by having an alkoxy group as a substituent at the para position of the phenyl group.

  Illustrative compound C-6 has at least one absorption peak in the wavelength region of 540 nm or more in the oxidized state (colored state). Not limited to this, the organic compound according to the present embodiment has a plurality of absorption peaks in the wavelength region of 540 nm or more in the oxidation state (colored state), or is absorbed in a wavelength region of 540 nm or more and a wavelength region shorter than 540 nm. It may have a peak.

  Illustrative compound C-6 has a strong electron-donating alkoxy group at the para-position of the phenyl group. Due to the influence of this strong electron donating group, the electron density of the phenazine ring showing EC properties is increased, the HOMO (highest occupied molecular orbital) energy of the phenazine ring becomes a shallow level, and HOMO-LUMO (lowest unoccupied molecular orbital). The energy gap is narrowed. If this energy gap is narrow, the absorption becomes longer.

  In addition, phenazine in the molecular structure of radical cations in the oxidized state is due to the contribution of electronic interaction between the lone pair of oxygen atoms contained in the alkoxy group (lone pair) and the π-electron conjugated system on the phenazine and phenyl rings. Mixing of rings and phenyl orbitals is promoted. As a result, the absorption becomes longer. Such a longer wavelength is considered to occur due to the contribution of electronic interaction between the lone pair of oxygen atoms contained in the alkoxy group or aryloxy group and the π-electron conjugated system on the phenazine ring and phenyl ring. It is done.

  As described above, the organic compound according to the present embodiment has a longer wavelength in the oxidation state than in the known compound Ref-3 due to an electronic effect peculiar to the alkoxy group or the aryloxy group in the oxidation state. That is, the organic compound according to this embodiment has an absorption peak in a long wavelength region of 540 nm or more in a colored state.

  Regarding neutral absorption in the decolored state, the known compound Ref-3 and exemplified compound C-6 have high molecular flatness even in the neutral state, and the electronic resonance structure spreads throughout the molecule. The absorption wavelength is also longer. In fact, the absorption edge in the neutral state of Compound Ref-3 is around 450 nm, and the absorption edge in the neutral state of Exemplified Compound C-6 exists up to the visible wavelength region of 445 nm.

  Furthermore, an organic compound represented by the following chemical structural formula (10) will be described as an example of a phenazine derivative of an organic compound having EC properties represented by the general formula (1) according to the present embodiment. Since this compound corresponds to Exemplified Compound D-2 which will be described later, it will be referred to as Exemplified Compound D-2 in the following description.

化学構造式（１０）で表わされる例示化合物Ｄ−２は、一般式（１）において、Ｒ_１３がメチル基を置換基として有するメトキシ基であり、Ｒ_１１がメチル基である化合物である。すなわち、例示化合物Ｄ−２は、フェナジン環と、フェナジン環と結合しているフェニル基とを有し、フェナジン環と結合したフェニル基のパラ位にはメトキシ基を、オルト位にはメチル基を有している。

Exemplary compound D-2 represented by chemical structural formula (10) is a compound in which, in general formula (1), R ₁₃ is a methoxy group having a methyl group as a substituent, and R ₁₁ is a methyl group. That is, Exemplified Compound D-2 has a phenazine ring and a phenyl group bonded to the phenazine ring, a methoxy group at the para position of the phenyl group bonded to the phenazine ring, and a methyl group at the ortho position. Have.

  In Illustrative Compound D-2, since the methyl group is introduced at the ortho position of the phenyl group bonded to the phenazine ring, the phenazine ring and the phenyl group are twisted due to the steric hindrance of the methyl group. That is, because the molecular structure has a large angle formed by the plane of the phenazine ring and the plane of the phenyl group, the orbits of the π electrons of the phenazine ring and the phenyl group are orthogonal, and resonance is reduced. Therefore, by localizing HOMO in the phenazine ring, the absorption in the neutral state can be shortened.

  The same tendency is described in Patent Document 1, for example, in the improvement of transparency using the twist of molecules. However, in the conventional phenazine derivative, the neutral state transparency improvement (shortening the absorption wavelength) and the long wavelength absorption in the oxidative coloring state are not compatible. This is because the molecular twist in the neutral state described above remains in the molecular structure of the colored radical cation, and as a result, the absorption in the oxidized state is also shortened.

However, the exemplary compound D-2 represented by the chemical structural formula (10) according to the present invention has an absorption edge of 410 nm when neutral, greatly improves neutral transparency, and has an absorption wavelength peak when colored. It has an absorption peak in a long wavelength region of 540 nm or more in a colored state of 553 nm. That is, the organic compound according to this embodiment is twisted in a neutral state. In addition, due to the contribution of the strong electron donating property of the alkoxy group and the electronic interaction between the lone pair of oxygen atoms contained in the alkoxy group and the hydrogen atom on the phenyl ring, it is planar in the oxidized state. Will improve. This is not limited to the case where R ₁₃ is an alkoxy group, and it is considered that the same effect can be obtained even if it is an aryloxy group.

  The organic compound according to this embodiment has a strong electron donating property of an alkoxy group or an aryloxy group, and an electronic interaction between a lone pair of an oxygen atom contained in the alkoxy group or the aryloxy group and a hydrogen atom on the phenyl ring. The contribution of the action causes twisting in the neutral state. Therefore, planarity is improved in the oxidized state.

  Therefore, in the neutral state, the organic compound according to the present embodiment has a short wavelength and high transparency due to the twist of the phenazine ring and the phenyl group. Specifically, as described above, in the organic compound of the present embodiment, since the angle of the angle formed by the plane of the phenazine ring and the plane of the phenyl group is large, the absorption in the decolored state is shortened, which is conventionally Transparency is also improved.

  Further, in the organic compound according to the present embodiment, in the oxidized state, mixing of the phenazine ring and the orbital of the phenyl group is promoted by the electronic effect peculiar to the alkoxy group or aryloxy group, and the absorption becomes longer. That is, according to the organic compound according to the present embodiment, an organic compound having an absorption peak in a long wavelength region of 540 nm or longer in a colored state can be provided. Moreover, the organic compound whose transparency in a decoloring state is higher than before can be provided.

  In addition, it is more preferable that the organic compound of this embodiment does not have an absorption edge in a wavelength region of 430 nm or more in a decolored state and is transparent in a wavelength region of 430 nm or more.

  Specific structural formulas of the organic compound according to this embodiment are exemplified below. However, the organic compound which concerns on this embodiment is not limited to these.

例示化合物のうちＡ群に示す有機化合物は、一般式（４）または一般式（５）で示される化合物例であり、１つのフェナジン環に２つのフェニル基が置換した化合物例である。Ｂ群に示す有機化合物は、一般式（２）又は一般式（３）で示される化合物例である。また、例示化合物のうちＣ群に示す有機化合物は、一般式（６）で示される化合物であり、１つのフェナジン環に１つのフェニル基が置換した化合物例である。Ｄ群に示す有機化合物は一般式（６）で示される化合物のうち、フェニル基の少なくとも１つのオルト位に少なくとも１つの置換基を有している化合物例である。Ｅ群に示す有機化合物は一般式（７）で示される化合物であり、１つのフェナジン環に２つのフェニル基が置換した化合物例である。Ｆ群に示す有機化合物は一般式（７）で示される化合物のうち、２つのフェニル基のそれぞれの少なくとも１つのオルト位にすくなくとも１つの置換基を有している化合物例である。

Among the exemplified compounds, the organic compound shown in Group A is a compound example represented by General Formula (4) or General Formula (5), and is a compound example in which two phenyl groups are substituted on one phenazine ring. The organic compound shown in Group B is a compound example represented by General Formula (2) or General Formula (3). Moreover, the organic compound shown to C group among exemplary compounds is a compound shown by General formula (6), and is a compound example which substituted one phenyl group to one phenazine ring. The organic compound shown in Group D is an example of a compound having at least one substituent in at least one ortho position of the phenyl group among the compounds represented by the general formula (6). The organic compound shown in Group E is a compound represented by the general formula (7), and is an example of a compound in which two phenyl groups are substituted on one phenazine ring. The organic compound shown in Group F is an example of a compound having at least one substituent in at least one ortho position of each of two phenyl groups among the compounds represented by the general formula (7).

  In all the organic compounds described above, the phenazine ring, which is an EC site, is substituted with a phenyl group into which an alkoxy group or an aryloxy group is introduced in at least one of the ortho and para positions. Therefore, due to the electronic effect of the ortho or para alkoxy group or aryloxy group of the phenyl group, a molecular structure in which orbitals are easily mixed with the phenazine ring forming the radical cation during oxidative coloring.

  Therefore, the organic compound having EC property in the present embodiment has characteristics with longer wavelength region absorption than before when colored.

  In addition, the phenazine ring, which is an EC site, is substituted with a phenyl group in which an alkoxy group or an aryloxy group is introduced in at least one of the ortho-position and the para-position. Can be expected to do. In order to improve transparency in the decolored state, the ortho position of the phenyl group is substituted with an alkoxy group or an aryloxy group, or the ortho position of the phenyl group is substituted with an alkyl group, an aryl group, or an aralkyl group. It is preferable that

(Method for synthesizing organic compound according to this embodiment)
Among the organic compounds according to this embodiment, the organic compounds represented by the general formulas (2) to (5) can be synthesized using a reaction represented by the following formula (11). In the formula (11), Y is a halogen atom. A precursor can be synthesized by a known Pd-catalyzed coupling reaction using a combination of a halogenated phenazine and a phenylboronic acid or boronic ester compound having an alkoxy group at the ortho position. Furthermore, the organic compound according to this embodiment can be synthesized by reduction and alkylation of the phenazine ring. As an example, a synthesis scheme of the organic compound represented by the general formula (3) is shown in the following formula (11).

  Here, if the number of halogen atoms substituted by the starting material halogenated phenazine is two, the compounds represented by the general formulas (4) and (5) can be similarly synthesized.

また、本実施形態に係る有機化合物のうち、一般式（６）、（７）で表される有機化合物は、下記式（１２）で示される反応を用いて合成できる。式（１２）において、Ｙはハロゲン原子である。フェナジンのハロゲン体と、オルト位にアルコキシ基を有するフェニルボロン酸もしくはボロン酸エステル化合物の組み合わせで、公知のＰｄ触媒によるカップリング反応で前駆体を合成することができる。さらに、フェナジン環の還元とアルキル化により、本実施形態に係る有機化合物を合成することができる。一例として、一般式（６）で表わされる有機化合物の合成スキームを下記式（１２）に示す。

Moreover, among the organic compounds according to this embodiment, the organic compounds represented by the general formulas (6) and (7) can be synthesized using a reaction represented by the following formula (12). In the formula (12), Y is a halogen atom. A precursor can be synthesized by a known Pd-catalyzed coupling reaction using a combination of a halogenated phenazine and a phenylboronic acid or boronic ester compound having an alkoxy group at the ortho position. Furthermore, the organic compound according to this embodiment can be synthesized by reduction and alkylation of the phenazine ring. As an example, a synthesis scheme of the organic compound represented by the general formula (6) is shown in the following formula (12).

  Here, if the number of halogen atoms substituted by the halogenated phenazine of the starting material is two, the compound represented by the general formula (7) can be synthesized in the same manner.

（第２の実施形態）
第１の実施形態に係るＥＣ性を有する有機化合物は、エレクトロクロミック素子（ＥＣ素子）のエレクトロクロミック層（ＥＣ層）として用いることができる。

(Second Embodiment)
The organic compound having EC property according to the first embodiment can be used as an electrochromic layer (EC layer) of an electrochromic device (EC device).

  Hereinafter, the EC element 15 according to the present embodiment will be described with reference to FIG. FIG. 2 is a diagram for explaining the configuration of the EC element 15 of the present embodiment.

  The EC element 15 is an EC element having a pair of substrates 10, a pair of electrodes 11, an electrochromic layer (EC layer) 12 disposed between the pair of electrodes 11, and a sealing material 13. The EC layer 12 has an electrolyte and an organic compound represented by the general formula (1). The pair of electrodes 11 has a constant distance between the electrodes 11 by a sealing material 13 such as a spacer. In the EC element 15, a pair of electrodes 11 are disposed between a pair of substrates 10. The EC element 15 only needs to include the pair of electrodes 11 and the EC layer 12 disposed between the pair of electrodes 11, and does not necessarily include the pair of substrates 10 and the sealing material 13. Also good.

  The EC layer 12 includes an organic compound represented by the general formula (1) according to this embodiment and an electrolyte. The EC layer 12 may include a layer made of an EC compound and a layer made of an electrolyte. Further, the EC layer 12 may be provided as a solution having an EC compound and an electrolyte. The EC element according to this embodiment is preferably an EC element in which the EC layer 12 is a solution.

  Next, members constituting the EC element according to this embodiment will be described.

  The electrolyte is not limited as long as it is an ion dissociable salt and has good solubility in a solvent and high compatibility in a solid electrolyte. Among them, an electrolyte having an electron donating property is preferable. These electrolytes can also be called supporting electrolytes.

  Examples of the electrolyte include inorganic ion salts such as various alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, and cyclic quaternary ammonium salts.

Specifically, _{LiClO 4, LiSCN, LiBF 4,} LiAsF 6, LiCF 3 SO 3, LiPF 6, LiI, NaI, NaSCN, NaClO 4, NaBF 4, NaAsF 6, KSCN, the KCl like Li, Na, K alkaline metal salts _{and, (CH 3) 4 NBF 4} , (C 2 H 5) 4 NBF 4, (n-C 4 H 9) 4 NBF 4, (n-C 4 H 9) 4 NPF 6, (C 2 Quaternary ammonium salts and cyclic quaternary ammonium salts such as H ₅ ) ₄ NBr, (C ₂ H ₅ ) ₄ NClO ₄ , (nC ₄ H ₉ ) ₄ NClO _4, and the like can be given.

  The solvent for dissolving the EC organic compound and the electrolyte is not particularly limited as long as it can dissolve the EC organic compound and the electrolyte, but a solvent having polarity is particularly preferable.

  Specifically, water, methanol, ethanol, propylene carbonate, ethylene carbonate, dimethyl sulfoxide, dimethoxyethane, γ-butyrolactone, γ-valerolactone, sulfolane, dimethylformamide, dimethoxyethane, tetrahydrofuran, acetonitrile, propionitrile, 3- Examples include organic polar solvents such as methoxypropiononitrile, benzonitrile, dimethylacetamide, methylpyrrolidinone, and dioxolane.

  A polymer or gelling agent may be further added to the EC medium described above to make it highly viscous or gelled.

  The polymer is not particularly limited, and examples thereof include polyacrylonitrile, carboxymethylcellulose, polyvinyl chloride, polyethylene oxide, polypropylene oxide, polyurethane, polyacrylate, polymethacrylate, polyamide, polyacrylamide, polyester, and Nafion (registered trademark). It is done.

  Next, the substrate 10 and the electrode 11 will be described. The substrate 10 is preferably transparent. As the substrate 10, for example, colorless or colored glass, tempered glass, or the like is used. As these glass materials, optical glass substrates such as Corning # 7059 and BK-7 can be preferably used. Even a material such as plastic or ceramic can be used as appropriate as long as it has sufficient transparency. The substrate 10 is preferably made of a material that is rigid and causes little distortion. In the present embodiment, “transparent” indicates that the visible light transmittance is a transmittance of 50% or more.

  Specific examples of the material used for the substrate 10 include polyethylene terephthalate, polyethylene naphthalate, polynorbornene, polyamide, polysulfone, polyethersulfone, polyetheretherketone, polyphenylene sulfide, polycarbonate, polyimide, and polymethyl methacrylate. .

  The electrode 11 is preferably a transparent electrode. Examples of the material of the electrode 11 include indium tin oxide alloy (ITO), fluorine-doped tin oxide (FTO), tin oxide (NESA), indium zinc oxide (IZO (registered trademark)), silver oxide, vanadium oxide, and molybdenum oxide. And metal materials such as gold, silver, platinum, copper, indium and chromium, silicon-based materials such as polycrystalline silicon and amorphous silicon, and carbon materials such as carbon black, graphite and glassy carbon. In addition, a conductive polymer whose conductivity is improved by doping treatment, for example, a polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, polyethylenedioxythiophene (PEDOT) and polystyrene sulfonic acid complex is also preferably used.

  In the EC element 15 of this embodiment, since it is preferable to have a high transmittance in a decolored state, for example, ITO, IZO, NESA, PEDOT: PSS, graphene, or the like is preferably used as the electrode 11. These can be used in various forms such as bulk and fine particles. These materials for the electrodes 11 may be used alone or in combination.

  In the present embodiment, both of the pair of electrodes 11 are transparent electrodes. However, the present invention is not limited to this. For example, only one of the pair of electrodes 11 may be a transparent electrode. preferable.

  The sealing material 13 is preferably a material that is chemically stable, does not transmit gas and liquid, and does not inhibit the redox reaction of the EC material. For example, an inorganic material such as glass frit, an organic material such as an epoxy resin, a metal material, or the like can be used. The sealing material 13 may have a function of maintaining the distance between the two electrodes 11. On the other hand, when the sealing material 13 is not provided with a function as a spacer for defining the distance between the two electrodes 11, a separate spacer (not shown) is disposed between the electrodes 11, and the spacers provide a space between the electrodes 11. The distance may be maintained. As the material of the spacer, inorganic materials such as silica beads and glass fibers, and organic materials such as polydivinylbenzene, polyimide, polytetrafluoroethylene, fluororubber, and epoxy resin can be used. By this spacer, it is possible to provide a space for accommodating the EC layer 12 having the solution containing the EC organic compound of this embodiment, and to maintain the distance between the electrodes.

  The EC element 15 according to the present embodiment may have a liquid inlet for injecting a liquid containing an EC compound into a space formed by the pair of electrodes 11 and the sealing material 13. After a solution containing an EC organic compound is sealed from the liquid inlet, the inlet is covered with a sealing member, and further sealed with an adhesive or the like, thereby obtaining an element. The sealing member may also serve to isolate the adhesive from the EC organic compound so as not to contact. The shape of the sealing member is not particularly limited, but a tapered shape such as a wedge shape is preferable.

  The method for forming the EC element 15 according to this embodiment is not particularly limited. For example, a method in which a liquid containing an EC organic compound prepared in advance by a vacuum injection method, an atmospheric injection method, a meniscus method, or the like is injected into the gap provided between the pair of electrodes 11 to form the EC layer 12 is used. Can do.

  The EC element 15 according to the present embodiment may include the organic compound according to the present embodiment represented by the general formula (1) and another EC compound different from the organic compound according to the present embodiment. Good. The other EC compound may be one type or a plurality of types, and may be a compound colored in an oxidized state, a compound colored in a reduced state, or both. Particularly preferred are compounds that color in the reduced state.

  The compound colored in the oxidized state is a compound having a visible light transmittance in the oxidized state lower than the visible light transmittance in the reduced state. The compound colored in the reduced state is a compound whose visible light transmittance in the reduced state is lower than the visible light transmittance in the oxidized state.

  The absorption wavelength region of other EC compounds is preferably 400 nm or less when decolored. This is because an EC element having high transparency at the time of decoloring can be provided. On the other hand, the absorption wavelength region during coloring is preferably in the range of 400 nm to 800 nm, more preferably 420 nm to 700 nm.

  By combining with other EC compounds that absorb different wavelength regions during coloring, an EC element that uniformly absorbs light in the visible light region at each wavelength can also be obtained. In addition, as another type of EC compound, another type of organic compound represented by the general formula (1) may be included. That is, the EC element may have two or more different organic compounds each represented by the general formula (1).

  Examples of other EC compounds according to this embodiment include the following compounds.

  Other compounds colored in the oxidized state include oligothiophenes such as 3,3′4,4′5,5′-hexamethylbithiophene and 3,4-ethylenedioxy-2,5-dimethylthiophene, 5 , 10-dihydro-5,10-dimethylphenazine, phenazine compounds such as 5,10-dihydro-5,10-diethylphenazine, metallocene compounds such as ferrocene, tetra-t-butylferrocene and titanocene, N, N ′ , N, N′-tetramethyl-p-phenylenediamine and other phenylenediamine compounds, and 1-phenyl-2-pyrazoline and other pyrazoline compounds.

  Examples of compounds colored in the reduced state include N, N′-diheptylbipyridinium diperchlorate, N, N′-diheptylbipyridinium ditetrafluoroborate, N, N′-diheptylbipyridinium dihexafluorophosphate, N, N '-Diethylbipyridinium diperchlorate, N, N'-diethylbipyridinium ditetrafluoroborate, N, N'-diethylbipyridinium dihexafluorophosphate, N, N'-dibenzylbipyridinium diperchlorate, N, N'-di Benzylbipyridinium ditetrafluoroborate, N, N′-dibenzylbipyridinium dihexafluorophosphate, N, N′-diphenylbipyridinium diperchlorate, N, N′-diphenylbipyridinium ditetrafluoroborate, , N'-diphenylbipyridinium dihexafluorophosphate, viologen compounds, 2-ethylanthraquinone, 2-t-butylanthraquinone, anthraquinone compounds such as octamethylanthraquinone, ferrocenium tetrafluoroborate, ferrocenium hexafluorophosphate And ferrocenium salt compounds, styryl compounds, and the like.

  The compound contained in the EC layer 12 of the EC element 15 according to the present embodiment can be confirmed to be contained in the EC element 15 by extracting and analyzing by a known method. For example, extraction by chromatography and analysis by each magnetic resonance spectrum (NMR) can be mentioned. Moreover, when EC layer 12 is solid, it can analyze by TOF-SIMS etc.

  The organic compound represented by the general formula (1) has an absorption peak in a long wavelength region of 540 nm or longer in a colored state, and has improved transparency in a neutral state (decolored state) than before. .

  Since the organic compound according to the present embodiment has an absorption peak in a longer wavelength range than before in a colored state, the organic compound represented by the general formula (1) alone or combined with an EC compound having colored absorption in another wavelength band Thus, EC elements having various absorption colors can be provided. Moreover, according to the EC element of this embodiment, the transparency in the decolored state can be improved. In addition, the EC element 15 of the present embodiment can be suitably used for reducing the amount of incident light on an imaging element such as a camera.

(Third embodiment)
The EC element 15 according to the above-described embodiment can be used for an optical filter, a lens unit, an imaging device, and the like. In the present embodiment, an optical filter, a lens unit, and an imaging device that use the EC element 15 will be described.

  The optical filter includes an EC device 30 having an EC element 15 and a driving device (active element) connected to the EC element 15. FIG. 3 is a block diagram for explaining the configuration of the EC device 30. The drive device connected to the EC element 15 includes a drive power supply 8, a resistance switch 9, and a controller 7.

  The drive power supply 8 applies a voltage necessary for the EC material included in the EC layer 12 to cause an electrochemical reaction to the EC element 15.

  More preferably, the driving voltage is a constant voltage. This is because when the EC material is composed of a plurality of types of materials, the absorption spectrum may change due to the difference in redox potential or molar extinction coefficient of the material, so it is preferable to apply a constant voltage. Because.

  The voltage application start of the drive power supply 8 or the application state is held by a signal from the controller 7, and a constant voltage application state is held during the period in which the light transmittance of the EC element 15 is controlled.

  The resistance switch 9 switches between a resistor R1 and a resistor R2 larger than the resistor R1 in a closed circuit including the drive power supply 8 and the EC element 15 and connects them in series. The resistance value of the resistor R1 is preferably at least smaller than the largest impedance of the element closed circuit, and is preferably 10Ω or less. The resistance value of the resistor R2 is preferably larger than the largest impedance of the element closed circuit, and is preferably 1 MΩ or more. The resistor R2 may be air. In this case, strictly speaking, the closed circuit is an open circuit, but it can be considered as a closed circuit by regarding air as the resistance R2.

  The controller 7 sends a switching signal to the resistance switch 9 to control switching of the resistors R1 and R2.

  The lens unit according to the present embodiment includes a plurality of lenses and an optical filter having an EC element 15. The optical filter may be provided either between the plurality of lenses or outside the lenses. The optical filter is preferably provided on the optical axis of the lens.

  The imaging device of the present embodiment includes an optical filter and a light receiving element that receives light that has passed through the optical filter.

  Specific examples of the imaging device include a camera, a video camera, a camera-equipped mobile phone, and the like. The imaging device may have a form in which a main body having a light receiving element and a lens unit having a lens can be separated.

  Here, when the imaging device can be separated between the main body and the lens unit, an embodiment using an optical filter separate from the imaging device during imaging is also included in the present invention. In this case, examples of the arrangement position of the optical filter include the outside of the lens unit, between the lens unit and the light receiving element, between a plurality of lenses (when the lens unit has a plurality of lenses), and the like.

  FIG. 4 is a schematic diagram illustrating an example of the configuration of the imaging apparatus 100 using the optical filter of the present embodiment.

  The imaging device 100 is an imaging device that includes a lens unit 102 and an imaging unit 103.

  The lens unit 102 includes an optical filter 101 and an imaging optical system having a plurality of lenses or lens groups. The optical filter 101 is the optical filter of the present embodiment described above.

  For example, in FIG. 4A, the lens unit represents a rear focus type zoom lens that performs focusing after the stop. A first lens group 104 having a positive refractive power, a second lens group 105 having a negative refractive power, a third lens group 106 having a positive refractive power, and a fourth lens group having a positive refractive power in order from the object side. There are four lens groups 107. Zooming is performed by changing the distance between the second lens group 105 and the third lens group 106, and focusing is performed by moving a part of the fourth lens group 107.

  The lens unit 102 has, for example, an aperture stop 108 between the second lens group 105 and the third lens group 106, and between the third lens group 106 and the fourth lens group 107. An optical filter 101 is provided. Light passing through the lens unit is disposed so as to pass through the lens groups 104 to 107, the diaphragm 108, and the optical filter 101, and the amount of light using the aperture diaphragm 108 and the optical filter 101 can be adjusted.

  The lens unit 102 is detachably connected to the imaging unit 103 via a mount member (not shown).

  In the present embodiment, the optical filter 101 is disposed between the third lens group 106 and the fourth lens group 107 in the lens unit 102, but the imaging device 100 is not limited to this configuration. For example, the optical filter 101 may be either in front of the aperture stop 108 (subject side) or behind (in the imaging unit 103 side), or any group of the first to fourth lens groups 104 to 107. It may be before or after, or between any two lens groups. If the optical filter 101 is arranged at a position where light converges, there is an advantage that the area of the optical filter 101 can be reduced.

  The configuration of the lens unit 102 is not limited to the above-described configuration, and can be selected as appropriate. For example, in addition to the rear focus method, an inner focus method in which focusing is performed before the stop may be used, or other methods may be used. In addition to the zoom lens, a special lens such as a fisheye lens or a macro lens can be selected as appropriate.

  The imaging unit 103 includes a glass block 109 and a light receiving element 110.

  The glass block 109 is a glass block such as a low-pass filter, a face plate, or a color filter.

  The light receiving element 110 is a sensor unit that receives light that has passed through the lens unit, and an imaging element such as a CCD or CMOS can be used. In addition, an optical sensor such as a photodiode may be used, and an optical sensor that acquires and outputs light intensity or wavelength information can be used as appropriate.

  As shown in FIG. 4A, when the optical filter 101 is incorporated in the lens unit 102, the driving device may be disposed inside the lens unit 102 or may be disposed outside the lens unit 102. In the case of being arranged outside the lens unit 102, the EC element 15 in the lens unit 102 and the driving device are connected through wiring to control driving.

  In the configuration of the imaging apparatus 100 described above, the optical filter 101 is disposed inside the lens unit 102. However, the present invention is not limited to this embodiment, and the optical filter 101 may be disposed at an appropriate location inside the imaging apparatus 100, and the light receiving element 110 may be disposed so as to receive light that has passed through the optical filter 101.

  For example, as illustrated in FIG. 4B, the imaging unit 103 may include an optical filter 101. FIG. 4B is a diagram illustrating the configuration of another example of the imaging apparatus according to the present embodiment, and is a schematic diagram of the configuration of the imaging apparatus having an optical filter in the imaging unit 103. In FIG. 4B, for example, the optical filter 101 is disposed immediately before the light receiving element 110. When the imaging unit itself incorporates the optical filter 101, the connected lens unit 102 does not need to have the optical filter 101, so that a dimmable imaging apparatus using an existing lens unit can be configured. It becomes.

  The imaging apparatus 100 of this embodiment can be applied to a product having a combination of light amount adjustment and a light receiving element. For example, it can be used for a camera, a digital camera, a video camera, a digital video camera, and can also be applied to a product incorporating an imaging device such as a mobile phone, a smartphone, a PC, or a tablet.

(Fourth embodiment)
The EC element 15 according to the above-described embodiment can also be used for a window material. In the present embodiment, a window material 111 using the EC element 15 will be described. FIG. 7A is a schematic diagram for explaining the configuration of the window member 111, and FIG. 7B is a schematic view of a section VIIB-BIIB in FIG. 7A.

  The window member 111 of the present embodiment includes an EC element 15 that can be used as an optical filter, a transparent plate 113 that sandwiches the EC element 15, and a frame 112 that surrounds and integrates the whole. The EC element 15 is connected to a driving device (not shown). The driving device (not shown) may be integrated in the frame 112, or may be disposed outside the frame 112 and connected to the EC element 15 through wiring.

  The transparent plate 113 is not particularly limited as long as it is a material having high light transmittance, and is preferably a glass material in consideration of use as a window.

  The frame 112 may be made of any material but may be regarded as a frame that covers at least a part of the optical filter and has an integrated form.

  The EC element 15 is a constituent member independent of the transparent plate 113. For example, the substrate 10 of the EC element 15 may be regarded as the transparent plate 113.

  The window material 111 of the present embodiment can be applied to, for example, an application for adjusting the amount of sunlight entering the room during the daytime. Since it can be applied to the adjustment of the amount of heat in addition to the amount of sunlight, it can be used to control the brightness and temperature of the room. In addition, the present invention can also be applied as a shutter for blocking the view from the outside to the room.

  Such a dimming window can be applied to a glass window for a building or a window of a vehicle such as an automobile, an airplane, and a ship.

  As described above, the EC element including the organic compound represented by the general formula (1) in the EC layer can be used for an optical filter, a lens unit, an imaging device, a window material, and the like. Each of the optical filter, the lens unit, the imaging device, and the window material of the present embodiment can be variously combined with an organic compound represented by the general formula (1) alone or an EC compound having colored absorption in other wavelength bands. It is possible to provide an absorption color. Moreover, since each of the optical filter, the lens unit, the imaging device, and the window material of the above-described embodiment includes the organic compound represented by the general formula (1), the transparency in the decolored state can be improved.

  Further, according to the imaging apparatus 100 of the present embodiment, by using the optical filter 101 as a dimming member, the dimming amount can be appropriately changed by one filter, which reduces the number of members and saves space. There are advantages.

  Hereinafter, although an example is described, the present invention is not limited to these.

[Example 1]
<Synthesis of Exemplary Compound A-21>

例示化合物Ａ−２１は、例えば以下の手順で合成できる。まず、化合物ＸＸ−２を合成する。５０ｍｌ反応容器に、化合物ＸＸ−１を６７６ｍｇ（２．０ｍｍｏｌ）、２−イソプロポキシ−６−メトキシフェニルボロン酸を１．２６ｇ（６．０ｍｍｏｌ）、トルエン／１，４−ジオキサン（７ｍｌ／７ｍｌ）混合溶媒中で混合し、窒素で溶存酸素を除去した。なお、化合物ＸＸ−１は、Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔｅｒｓ，５２，６４８４（２０１１）に従って合成した化合物である。

Illustrative compound A-21 can be synthesized, for example, by the following procedure. First, compound XX-2 is synthesized. In a 50 ml reaction vessel, compound XX-1 676 mg (2.0 mmol), 2-isopropoxy-6-methoxyphenylboronic acid 1.26 g (6.0 mmol), toluene / 1,4-dioxane (7 ml / 7 ml) The mixture was mixed in a mixed solvent, and dissolved oxygen was removed with nitrogen. Compound XX-1 is a compound synthesized according to Tetrahedron Letters, 52, 6484 (2011).

Next, 18.0 mg (0.08 mmol) of Pd (OAc) ₂ , 82.1 mg (0.10 mmol) of 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (S-Phos), tripotassium phosphate 2.30 g (10.0 mmol) was added in a nitrogen atmosphere, and the mixture was heated to reflux at 110 ° C. for 8 hours.

  The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / chloroform) to obtain Compound XX-2 as a yellow solid (770 mg, yield 75%).

  Subsequently, Example Compound A-21 is synthesized. In a 50 ml reaction vessel, 350 mg (0.69 mmol) of compound XX-2, 3.51 g (20.6 mmol) of 2-iodopropane and acetonitrile / water (10 ml / 1 ml) mixed solvent were mixed, and dissolved oxygen with nitrogen Was removed. Next, 600 mg (3.44 mmol) of hydrosulfite sodium and 599 mg (4.13 mmol) of potassium carbonate were added in a nitrogen atmosphere, and the mixture was heated to reflux at 90 ° C. for 9 hours.

  The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / toluene) to obtain a solid exemplified compound A-21 (110 mg, yield 26%).

  The structure of the obtained compound was confirmed by nuclear magnetic resonance spectrum (NMR) measurement. As a result, the ratio of peak integral values was in good agreement with the structure, and it was confirmed that the obtained compound was Exemplified Compound A-21. The measurement results of the NMR spectrum are shown below.

¹ H-NMR (heavy acetone) δ (ppm): 7.19 (t, 2H), 6.8-6.65 (m, 10H), 4.45 (sep, 2H), 4.11 (sep, 2H), 3.62 (s, 6H), 1.52 (d, 12H), 1.24 (d, 12H).
[Example 2]
<Synthesis of Exemplified Compound B-18>

例示化合物Ｂ−１８は、例えば以下の手順で合成できる。

Illustrative compound B-18 can be synthesized, for example, by the following procedure.

  First, compound XX-3 is synthesized. In a 100 ml reaction vessel, 500 mg (1.48 mmol) of compound XX-1, 278 mg (2.96 mmol) of phenol and DMSO (5 ml) were mixed, and dissolved oxygen was removed with nitrogen. Next, 62.8 mg (0.074 mmol) of CuI / Sparteine complex and 409 mg (2.96 mmol) of potassium carbonate and nitrogen atmosphere were added, and the mixture was heated to reflux at 110 ° C. for 8 hours.

  The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: toluene / chloroform) to obtain Compound XX-3 (160 mg, yield 32%) as a yellow solid.

  Next, Compound XX-4 is synthesized. In a 50 ml reaction vessel, 160 mg (0.46 mmol) of compound XX-3, 144 mg (0.69 mmol) of 2-isopropoxy-6-methoxyphenylboronic acid, toluene / 1,4-dioxane (4 ml / 4 ml) mixed solvent Mix in and remove dissolved oxygen with nitrogen.

Next, 4.1 mg (0.018 mmol) of Pd (OAc) ₂ , 19 mg (0.046 mmol) of 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (S-Phos), and tripotassium phosphate 526 mg (2.29 mmol) was added under a nitrogen atmosphere, and the mixture was heated to reflux at 110 ° C. and reacted for 15 hours.

  The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / chloroform) to obtain Compound XX-4 as a yellow solid (170 mg, 85% yield).

  Subsequently, Example Compound B-18 is synthesized. In a 50 ml reaction vessel, 170 mg (0.39 mmol) of compound XX-4, 1.99 g (11.7 mmol) of 2-iodopropane, and acetonitrile / water (10 ml / 1 ml) mixed solvent were mixed, and dissolved oxygen with nitrogen Was removed. Next, 340 mg (1.95 mmol) of hydrosulfite sodium and 323 mg (2.34 mmol) of potassium carbonate were added in a nitrogen atmosphere, and the mixture was heated to reflux at 90 ° C. for 10 hours.

  The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / toluene) to obtain solid exemplified compound B-18 (120 mg, yield 59%).

As a result of NMR measurement, since the ratio of peak integration values was in good agreement with the structure, it was confirmed that the obtained compound was Exemplified Compound B-18. The measurement results of the NMR spectrum are shown below.
¹ H-NMR (heavy acetone) δ (ppm): 7.35 (m, 2H), 7.19 (t, 1H), 7.06 (t, 1H), 6.99 (d, 2H), 6 8-6.65 (m, 6H), 6.49 (d, 1H), 6.42 (dd, 1H), 4.47 (sep, 1H), 4.17 (sep, 1H), 3. 97 (sep, 1H), 3.71 (s, 3H), 1.51 (d, 6H), 1.46 (d, 6H), 1.18 (d, 6H).
[Comparative Example 1]
As Comparative Example 1, a comparative compound Ref-1 which is a known EC compound is used. The molecular structure of the comparative compound Ref-1 is as described above. Comparative compound Ref-1 is a phenazine derivative substituted with a phenyl group having no alkoxy substituent at the ortho position.

[Example 3]
<Neutral transparency>
In this example, see FIG. 5 for the transparency in the neutral state of Example Compound A-21 of Example 1, Example Compound B-18 of Example 2, and Comparative Compound Ref-1 of Comparative Example 1. To say. FIG. 5 shows the measurement results of the absorption spectrum of each compound. Absorption spectra were obtained by dissolving each of Exemplified Compound A-21 of Example 1, Exemplified Compound B-18 of Example 2 and Comparative Compound Ref-1 of Comparative Example 1 in acetonitrile. (Measured using JASCO Corporation V-560).

  Corresponding to the fact that each of Exemplified Compound A-21 and Exemplified Compound B-18 are visually colorless solids, the absorption spectrum has an absorption peak in the ultraviolet region, and the absorption edge is about 420 nm. there were. Each of Exemplified Compound A-21 and Exemplified Compound B-18 are materials that do not have absorption over the entire visible light region and have improved transparency as compared with the conventional compounds. On the other hand, the comparative compound Ref-1 was visually a light reddish brown solid, and the absorption edge of the absorption peak was about 460 nm.

  As a result, each of Exemplified Compound A-21 and Exemplified Compound B-18 having an alkoxy group as a substituent at the ortho position of each phenyl group has higher transparency in the neutral state than Comparative Compound Ref-1. It shows that.

[Example 4]
<Evaluation of electrochromic characteristics>
For each of Exemplified Compound A-21 in Example 1, Exemplified Compound B-18 in Example 2, and Comparative Compound Ref-1 in Comparative Example 1, absorption spectra in an oxidized (colored) state were measured.

The absorption spectrum was measured by dissolving (5.0 × 10 ⁻⁴ mol / L) each of the above compounds in a propylene carbonate solution (0.1 mol / L) of tetrabutylammonium perchlorate as a supporting electrolyte. It was performed using. The obtained solution is put in a glass cell having an optical path length of 1 mm, a mesh-like platinum electrode (working electrode) and a wire-like platinum electrode (counter electrode) are arranged by a predetermined method, and a reference electrode RE (Ag / Ag ⁺ ) Was measured. This solution was subjected to constant-potential oxidation at or above the oxidation potential of the compound, using transmitted light that passed through the mesh electrode. A potentiostat (Cell Test 1470E) manufactured by Solartron was used for applying the driving voltage, and a spectroscope manufactured by Ocean Optics (USB2000-UV-VIS) was used for the spectroscopic measurement.

  Table 2 shows the wavelength of the absorption peak (colored absorption wavelength) λmax in the colored state (oxidized state) and the absorption edge wavelength in the decolored state (neutral state) of Example 3 described above.

酸化により生成する着色種は、いずれも可視域波長の帯域に吸収を示す。しかし、例示化合物Ａ−２１、Ｂ−１７のそれぞれは、酸化状態において、比較化合物Ｒｅｆ−１に比べて長波長に吸収ピークを有する。この酸化着色状態は、還元により再度無色透明に戻り、酸化還元に伴う可逆的なエレクトロクロミック特性が確認された。

Any colored species produced by oxidation exhibits absorption in the visible wavelength range. However, Exemplified Compounds A-21 and B-17 each have an absorption peak at a long wavelength in the oxidized state as compared with Comparative Compound Ref-1. This oxidation-colored state returned to colorless and transparent again by reduction, and reversible electrochromic characteristics associated with oxidation-reduction were confirmed.

  From Examples 3 and 4, each of Exemplified Compound A-21 and Exemplified Compound B-17 has a shorter neutral absorption wavelength and improved transparency as compared with Comparative Compound Ref-1, and is further oxidized and colored. Occasionally, absorption was observed in a band of 540 nm or longer, which was longer than that of Compound Ref-1.

[Example 5]
<Preparation of electrochromic element and element driving>
Next, EC example compound A-21 as an anodic EC material and cathodic EC compound W-1 having the following structure as a cathodic EC material are each dissolved in propylene carbonate at a concentration of 100.0 mM to prepare an EC solution. did.

次いで、図２に示されるＥＣ素子を以下に説明する方法により作製した。電極１１としての透明導電膜（ＩＴＯ）付きの基板１０を２枚準備し、２枚の基板１０を導電面（電極１１が設けられている面）が向かい合い、かつ基板１０間に一定の間隔が生じるように配置する。基板１０は、ガラス基板を用いた。続いて、充填してＥＣ層１２を形成する溶液の注入口を残すように、２枚の基板１０をエポキシ系接着剤により素子周辺部を封止し、注入口付き空セルを作製した。この時、厚さの異なるフィルム又は直系の異なるビーズをスペーサーとして用いてシール材１３を形成することで、電極１１間の距離を調整した。

Next, the EC element shown in FIG. 2 was produced by the method described below. Two substrates 10 with a transparent conductive film (ITO) as electrodes 11 are prepared, and the two substrates 10 face each other with conductive surfaces (surfaces on which the electrodes 11 are provided), and there is a constant interval between the substrates 10. Arrange to occur. As the substrate 10, a glass substrate was used. Subsequently, the peripheral portion of the element was sealed with an epoxy adhesive so as to leave an injection port for a solution that was filled to form the EC layer 12, and an empty cell with an injection port was manufactured. At this time, the distance between the electrodes 11 was adjusted by forming the sealing material 13 using a film having a different thickness or a different type of direct bead as a spacer.

  The EC layer 12 was formed by filling the EC element cell thus fabricated with an EC solution from the opening of the cell by vacuum injection. Further, an EC element was produced by sealing the opening of the cell with an epoxy resin.

  When a voltage of 0.7 V is applied to this EC element, absorption derived from oxidized species of exemplary compound A-21 (λ to 560 nm) and absorption derived from reduced species of cathodic EC compound W-1 (λ to 615 nm) The organic EC element was colored. The organic EC element disappeared when 0 V was applied, and showed reversible color disappearance. FIG. 6 shows the change in the transmittance spectrum of the EC element of this example accompanying this voltage application.

  As shown in FIG. 6, it was confirmed that the organic EC device using the exemplary compound A-21 of Example 1 showed a change in transmittance in a long wavelength region when colored with application of voltage.

    As described above, to provide an EC organic compound having an absorption peak in a long wavelength region of 540 nm or more in a colored state and having higher transparency in a neutral state (decolored state) than before. Can do.

[Example 6]
<Synthesis of Exemplary Compound A-3>

Illustrative compound A-3 can be synthesized, for example, by the following procedure. First, compound XX-5 is synthesized. In a 50 ml reaction vessel, 507 mg (1.5 mmol) of compound XX-1, 638 mg (4.5 mmol) of 2-methoxyphenylboronic acid, and a mixed solvent of toluene / 1,4-dioxane (6 ml / 6 ml) were mixed. The dissolved oxygen was removed with nitrogen. Next, 13.5 mg (0.06 mmol) of Pd (OAc) ₂ , 61.6 mg (0.15 mmol) of 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (S-Phos), tripotassium phosphate 1.72 g (7.5 mmol) was added under a nitrogen atmosphere, and the mixture was heated to reflux at 100 ° C. for 6 hours.

  After cooling the reaction solution to room temperature, the powder precipitated during concentration under reduced pressure was purified by recrystallization to obtain Compound XX-5 (265 mg, yield 45%) as a yellow solid.

  Subsequently, Example Compound A-3 is synthesized. In a 50 ml reaction vessel, 155 mg (0.40 mmol) of compound XX-5, 1.34 g (7.9 mmol) of 2-iodopropane and acetonitrile (5 ml) were mixed, and dissolved oxygen was removed with nitrogen. Next, an aqueous solution (1.6 ml) of sodium hydrosulfite (344 mg, 1.98 mmol) and an aqueous solution (0.7 ml) of potassium carbonate (327 mg, 2.37 mmol) were added, and the mixture was heated to reflux at 90 ° C. for 9 hours. Went.

  The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / toluene) to obtain solid exemplified compound A-3 (175 mg, yield 92%).

  The structure of the obtained compound was confirmed by NMR measurement. As a result, the ratio of peak integral values was in good agreement with the structure, and it was confirmed that the obtained compound was Exemplified Compound A-3. The measurement results of the NMR spectrum are shown below.

¹ H-NMR (heavy acetone) δ (ppm): 7.35-7.25 (m, 4H), 7.09-7.01 (m, 4H), 6.99 (t, 2H), 6. 91 (dd, 2H), 6.80 (d, 2H), 4.18 (sep, 2H), 3.82 (s, 6H), 1.53 (d, 12H).
[Example 7]
<Synthesis of Exemplified Compound A-25>

例示化合物Ａ−２５は、例えば以下の手順で合成できる。まず、化合物ＸＸ−６を合成する。５０ｍｌ反応容器に、化合物ＸＸ−１を５０７ｍｇ（１．５ｍｍｏｌ）、２，６−ジフェノキシフェニルボロン酸を１．３８ｇ（４．５ｍｍｏｌ）、トルエン／１，４−ジオキサン（６ｍｌ／６ｍｌ）混合溶媒中で混合し、窒素で溶存酸素を除去した。次にＰｄ（ＯＡｃ）_２を１３．５ｍｇ（０．０６ｍｍｏｌ）、２−ジシクロヘキシルフォスフィノ−２’，６’−ジメトキシビフェニル（Ｓ−Ｐｈｏｓ）を６１．６ｍｇ（０．１５ｍｍｏｌ）、リン酸三カリウムを１．７２ｇ（７．５ｍｍｏｌ）、窒素雰囲気下で添加し、１００℃にて加熱還流し４時間反応を行った。

Illustrative compound A-25 can be synthesized, for example, by the following procedure. First, compound XX-6 is synthesized. In a 50 ml reaction vessel, compound XX-1 (507 mg, 1.5 mmol), 2,6-diphenoxyphenylboronic acid (1.38 g, 4.5 mmol), toluene / 1,4-dioxane (6 ml / 6 ml) mixed solvent Mix in and remove dissolved oxygen with nitrogen. Next, 13.5 mg (0.06 mmol) of Pd (OAc) ₂ , 61.6 mg (0.15 mmol) of 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (S-Phos), tripotassium phosphate 1.72 g (7.5 mmol) was added under a nitrogen atmosphere, and the mixture was heated to reflux at 100 ° C. for 4 hours.

  After cooling the reaction solution to room temperature, the powder precipitated during concentration under reduced pressure was purified by recrystallization to obtain Compound XX-6 (650 mg, yield 62%) as a yellow solid.

  Subsequently, Example Compound A-25 is synthesized. In a 50 ml reaction vessel, 350 mg (0.50 mmol) of compound XX-6, 2.55 g (15.0 mmol) of 2-iodopropane and acetonitrile / water (10 ml / 1 ml) mixed solvent were mixed, and dissolved oxygen with nitrogen Was removed. Next, 435 mg (2.5 mmol) of hydrosulfite sodium and 415 mg (3.0 mmol) of potassium carbonate and a nitrogen atmosphere were added, and the mixture was heated to reflux at 90 ° C. for 10 hours.

  The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / toluene) to obtain solid exemplified compound A-25 (80 mg, yield 20%).

  The structure of the obtained compound was confirmed by NMR measurement. As a result, the ratio of peak integral values was in good agreement with the structure, and it was confirmed that the obtained compound was Exemplified Compound A-25. The measurement results of the NMR spectrum are shown below.

¹ H-NMR (heavy acetone) δ (ppm): 7.41-7.32 (m, 10H), 7.29 (t, 2H), 7.08 (t, 4H), 6.98 (d, 8H), 6.87 (t, 4H), 6.83 (dd, 2H), 6.72 (d, 2H), 6.61 (d, 2H), 3.78 (sep, 2H), 1. 28 (d, 12H).
[Example 8]
<Synthesis of Exemplified Compound B-9>

例示化合物Ｂ−９は、例えば以下の手順で合成できる。まず、化合物ＸＸ−８を合成する。５０ｍｌ反応容器に、化合物ＸＸ−７を５１８ｍｇ（２．０ｍｍｏｌ）、２−イソプロポキシ−６−メトキシフェニルボロン酸を４６２ｍｇ（２．２ｍｍｏｌ）、トルエン／１，４−ジオキサン（７ｍｌ／７ｍｌ）混合溶媒中で混合し、窒素で溶存酸素を除去した。次にＰｄ（ＯＡｃ）_２を１８．０ｍｇ（０．０８ｍｍｏｌ）、２−ジシクロヘキシルフォスフィノ−２’，６’−ジメトキシビフェニル（Ｓ−Ｐｈｏｓ）を８２．１ｍｇ（０．２ｍｍｏｌ）、リン酸三カリウムを２．３０ｇ（１０．０ｍｍｏｌ）、窒素雰囲気下で添加し、１００℃にて加熱還流し９時間反応を行った。

Illustrative compound B-9 can be synthesized, for example, by the following procedure. First, Compound XX-8 is synthesized. In a 50 ml reaction vessel, 518 mg (2.0 mmol) of compound XX-7, 462 mg (2.2 mmol) of 2-isopropoxy-6-methoxyphenylboronic acid, mixed solvent of toluene / 1,4-dioxane (7 ml / 7 ml) Mix in and remove dissolved oxygen with nitrogen. Next, 18.0 mg (0.08 mmol) of Pd (OAc) ₂ , 82.1 mg (0.2 mmol) of 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (S-Phos), tripotassium phosphate 2.30 g (10.0 mmol) was added in a nitrogen atmosphere, and the mixture was heated to reflux at 100 ° C. for 9 hours.

  The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / chloroform) to obtain Compound XX-8 (654 mg, yield 95%) as a yellow solid.

  Subsequently, Example Compound B-9 is synthesized. In a 50 ml reaction vessel, 516 mg (1.5 mmol) of compound XX-8, 5.10 g (30 mmol) of 2-iodopropane and acetonitrile / water (10 ml / 1 ml) mixed solvent are mixed, and dissolved oxygen is removed with nitrogen. did. Next, 1.30 g (7.5 mmol) of hydrosulfite sodium and 1.24 g (9.0 mmol) of potassium carbonate and nitrogen atmosphere were added, and the mixture was heated to reflux at 90 ° C. for 9 hours. The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / toluene) to obtain solid exemplified compound B-9 (226 mg, yield 35%).

  The structure of the obtained compound was confirmed by nuclear magnetic resonance spectrum (NMR) measurement. As a result, the ratio of peak integral values was in good agreement with the structure, and it was confirmed that the obtained compound was Exemplified Compound B-9. The measurement results of the NMR spectrum are shown below.

¹ H-NMR (heavy acetone) δ (ppm): 7.19 (t, 1H), 6.86-6.66 (m, 9H), 4.42 (sep, 1H), 4.10 (sep, 1H), 4.01 (sep, 1H), 3.65 (s, 3H), 1.52 (d, 6H), 1.43 (d, 6H), 1.17 (d, 6H).
[Example 9]
<Evaluation of neutral transparency and electrochromic properties>
Example Compound A-3 in Example 6, Example Compound A-25 in Example 7, and Example Compound B-9 in Example 8 were each in a decolored state (neutral state) in the same manner as in Examples 3 and 4. And the absorption spectrum in the colored state (oxidized state) was measured. Table 3 shows the absorption edge wavelength in the decolored state (neutral state) and the wavelength (colored absorption wavelength) λmax of the absorption peak in the colored state (oxidized state).

例示化合物Ａ−３、Ａ−２５、Ｂ−９のそれぞれは、酸化状態において、表２に示した比較化合物Ｒｅｆ−１に比べて長波長に吸収ピークを有する。この酸化着色状態は、還元により再び無色透明に戻り、酸化還元に伴う可逆的なエレクトロクロミック特性が確認された。

Each of the exemplary compounds A-3, A-25, and B-9 has an absorption peak at a longer wavelength in the oxidized state as compared with the comparative compound Ref-1 shown in Table 2. This oxidative coloring state returned to colorless and transparent again upon reduction, and reversible electrochromic properties associated with the oxidation reduction were confirmed.

  From Example 9, each of Exemplified Compounds A-3, A-25 and Exemplified Compound B-9 has a shorter neutral absorption wavelength and improved transparency as compared with Comparative Compound Ref-1, At the time of oxidative coloring, absorption was shown in a band of 540 nm or longer, which is longer than that of the compound Ref-1.

[Example 10]
<Synthesis of Exemplified Compound C-6>

例示化合物Ｃ−６は、例えば以下の手順で合成できる。まず、化合物ＸＸ−１５を合成する。５０ｍｌ反応容器に、化合物ＸＸ−７を５１８ｍｇ（２．０ｍｍｏｌ）、４−イソプロポキシフェニルボロン酸を４５０ｍｇ（２．５ｍｍｏｌ）、トルエン／１，４−ジオキサン（７ｍｌ／７ｍｌ）混合溶媒中で混合し、窒素で溶存酸素を除去した。なお、化合物ＸＸ−５は、Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔｅｒｓ，５２，６４８４（２０１１）に従って合成した化合物である。

Illustrative compound C-6 can be synthesized, for example, by the following procedure. First, compound XX-15 is synthesized. In a 50 ml reaction vessel, 518 mg (2.0 mmol) of compound XX-7 and 450 mg (2.5 mmol) of 4-isopropoxyphenylboronic acid were mixed in a mixed solvent of toluene / 1,4-dioxane (7 ml / 7 ml). The dissolved oxygen was removed with nitrogen. Compound XX-5 is a compound synthesized according to Tetrahedron Letters, 52, 6484 (2011).

Next, 18.0 mg (0.08 mmol) of Pd (OAc) ₂ , 82.1 mg (0.20 mmol) of 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (S-Phos), tripotassium phosphate 2.30 g (10.0 mmol) was added under a nitrogen atmosphere, and the mixture was heated to reflux at 100 ° C. for 3 hours.

  The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / chloroform) to obtain Compound XX-15 as a yellow solid (565 mg, yield 90%).

  Subsequently, Example Compound C-6 is synthesized. In a 50 ml reaction vessel, 384 mg (1.22 mmol) of compound XX-15, 4.15 g (24.4 mmol) of 2-iodopropane, and acetonitrile / water (18 ml / 8 ml) mixed solvent were mixed, and dissolved oxygen with nitrogen. Was removed. Next, 1.25 g (6.1 mmol) of hydrosulfite sodium and 1.01 g (7.3 mmol) of potassium carbonate were added under a nitrogen atmosphere, and the mixture was heated to reflux at 90 ° C. for 9 hours.

  The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / toluene) to obtain a solid exemplified compound C-6 (390 mg, yield 80%).

  The structure of the obtained compound was confirmed by nuclear magnetic resonance spectrum (NMR) measurement. As a result, the ratio of peak integral values was in good agreement with the structure, and it was confirmed that the obtained compound was Exemplified Compound C-6. The measurement results of the NMR spectrum are shown below.

¹ H-NMR (heavy acetone) δ (ppm): 7.49 (d, 2H), 7.04-6.91 (m, 4H), 6.86-6.72 (m, 5H), 4. 65 (sep, 1H), 4.12 (sep, 2H), 1.56 (d, 12H), 1.32 (d, 6H).
[Example 11]
<Synthesis of Exemplified Compound D-2>

例示化合物Ｄ−２は、例えば以下の手順で合成できる。まず、化合物ＸＸ−１６を合成する。５０ｍｌの反応容器で、化合物ＸＸ−７を５１８ｍｇ（２．００ｍｍｏｌ）、４−メトキシ−２−メチルフェニルボロン酸を４９８ｍｇ（３．０ｍｍｏｌ）、トルエン／１，４−ジオキサン（７ｍｌ／７ｍｌ）混合溶媒中で混合し、窒素で溶存酸素を除去した。次にＰｄ（ＯＡｃ）_２を１８．０ｍｇ（０．０８ｍｍｏｌ）、２−ジシクロヘキシルフォスフィノ−２’，６’−ジメトキシビフェニル（Ｓ−Ｐｈｏｓ）を８２．１ｍｇ（０．２０ｍｍｏｌ）、リン酸三カリウムを２．３０ｇ（１０．０ｍｍｏｌ）、窒素雰囲気下で添加し、１００℃にて加熱還流し５時間反応を行った。

Illustrative compound D-2 can be synthesized, for example, by the following procedure. First, compound XX-16 is synthesized. In a 50 ml reaction vessel, 518 mg (2.00 mmol) of compound XX-7, 498 mg (3.0 mmol) of 4-methoxy-2-methylphenylboronic acid, mixed solvent of toluene / 1,4-dioxane (7 ml / 7 ml) Mix in and remove dissolved oxygen with nitrogen. Next, 18.0 mg (0.08 mmol) of Pd (OAc) ₂ , 82.1 mg (0.20 mmol) of 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (S-Phos), tripotassium phosphate 2.30 g (10.0 mmol) was added in a nitrogen atmosphere, and the mixture was heated to reflux at 100 ° C. for 5 hours.

  The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / chloroform) to obtain Compound XX-16 as a yellow solid (550 mg, yield 91%).

  Subsequently, Example Compound D-2 is synthesized. In a 50 ml reaction vessel, 550 mg (1.83 mmol) of compound XX-16, 6.23 g (36.6 mmol) of 2-iodopropane and acetonitrile / water (20 ml / 10 ml) mixed solvent were mixed, and dissolved oxygen with nitrogen Was removed. Next, 1.59 g (9.15 mmol) of hydrosulfite sodium and 1.52 g (11.0 mmol) of potassium carbonate were added under a nitrogen atmosphere, and the mixture was heated to reflux at 90 ° C. and reacted for 10 hours.

  The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / toluene) to obtain a solid exemplified compound D-2 (665 mg, yield 94%).

  As a result of NMR measurement, since the ratio of peak integration values was in good agreement with the structure, it was confirmed that the obtained compound was Exemplified Compound D-2. The measurement results of the NMR spectrum are shown below.

¹ H-NMR (heavy acetone) δ (ppm): 7.12 (t, 1H), 6.84-6.74 (m, 7H), 6.70 (dd, 1H), 6.66 (d, 1H), 4.09 (sep, 2H), 3.79 (s, 3H), 2.26 (s, 3H), 1.50 (d, 6H), 1.46 (d, 6H).
[Example 12]
<Synthesis of Exemplified Compound F-2>

例示化合物Ｆ−２は、例えば以下の手順で合成できる。まず、化合物ＸＸ−９を合成する。５０ｍｌの反応容器で、化合物ＸＸ−１を５０７ｍｇ（１．５０ｍｍｏｌ）、４−メトキシ−２−メチルフェニルボロン酸を７４７ｍｇ（４．５ｍｍｏｌ）、トルエン／１，４−ジオキサン（７ｍｌ／７ｍｌ）混合溶媒中で混合し、窒素で溶存酸素を除去した。次にＰｄ（ＯＡｃ）_２を１３．５ｍｇ（０．０６ｍｍｏｌ）、２−ジシクロヘキシルフォスフィノ−２’，６’−ジメトキシビフェニル（Ｓ−Ｐｈｏｓ）を６１．６ｍｇ（０．１５ｍｍｏｌ）、リン酸三カリウムを１．７２ｇ（７．５ｍｍｏｌ）、窒素雰囲気下で添加し、１００℃にて加熱還流し６時間反応を行った。

Illustrative compound F-2 can be synthesized, for example, by the following procedure. First, compound XX-9 is synthesized. In a 50 ml reaction vessel, compound XX-1 507 mg (1.50 mmol), 4-methoxy-2-methylphenylboronic acid 747 mg (4.5 mmol), toluene / 1,4-dioxane (7 ml / 7 ml) mixed solvent Mix in and remove dissolved oxygen with nitrogen. Next, 13.5 mg (0.06 mmol) of Pd (OAc) ₂ , 61.6 mg (0.15 mmol) of 2-dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl (S-Phos), tripotassium phosphate 1.72 g (7.5 mmol) was added under a nitrogen atmosphere, and the mixture was heated to reflux at 100 ° C. for 6 hours.

  The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / chloroform) to obtain Compound XX-9 (478 mg, yield 76%) as a yellow solid.

  Subsequently, Example Compound F-2 is synthesized. In a 50 ml reaction vessel, 255 mg (0.61 mmol) of compound XX-9, 2.06 g (12.1 mmol) of 2-iodopropane and acetonitrile / water (10 ml / 4 ml) mixed solvent were mixed, and dissolved oxygen with nitrogen Was removed. Next, 528 mg (3.03 mmol) of hydrosulfite sodium and 503 mg (3.64 mmol) of potassium carbonate and nitrogen atmosphere were added, and the mixture was heated to reflux at 90 ° C. for 9 hours.

  The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / toluene) to obtain a solid exemplified compound F-2 (130 mg, yield 42%).

  As a result of NMR measurement, the ratio of peak integrated values was in good agreement with the structure, and it was confirmed that the obtained compound was Exemplified Compound F-2. The measurement results of the NMR spectrum are shown below.

¹ H-NMR (heavy acetone) δ (ppm): 7.12 (d, 2H), 6.86-6.81 (m, 4H), 6.79 (dd, 2H), 6.73-6. 67 (m, 4H), 4.16 (sep, 2H), 3.79 (s, 6H), 2.28 (s, 6H), 1.52 (d, 12H).
[Comparative Example 2]
As Comparative Example 2, Comparative Compound Ref-3, which is the above-mentioned known EC compound, is used. Comparative compound Ref-3 is a phenazine derivative substituted with a phenyl group having no alkoxy substituent at the para position.

[Example 13]
<Neutral transparency>
In this example, the transparency in the neutral state of each of Exemplified Compound C-6 of Example 10, Exemplified Compound D-2 of Example 11 and Comparative Compound Ref-3 of Comparative Example 2 is described with reference to FIG. To say. FIG. 8 shows the measurement results of the absorption spectrum of each compound. The absorption spectrum was measured by the same method as in Example 3.

  Comparative compound Ref-3 and exemplary compound C-6 were visually dark yellow solids, and the absorption edge of the absorption peak was about 450 nm. On the other hand, as shown in FIG. 8, the absorption of the compound D-2 is shorter than that of the comparative compound Ref-3 and the exemplary compound C-6. The absorption edge was about 410 nm. Illustrative compound D-2 is a material that has no absorption over the entire visible light region and has improved transparency as compared with the conventional compound. Exemplified Compound F-2 also has an absorption edge of 420 nm, and does not absorb the entire visible light region like Exemplified Compound D-2, and is a material with improved transparency compared to the conventional compound F-2.

  Table 4 shows the absorption edge wavelength in the decolored state (neutral state).

この結果は、フェニル基のオルト位に置換基を有する例示化合物Ｄ−２及び例示化合物Ｆ−２のそれぞれが、比較化合物Ｒｅｆ−３に比べて、中性状態における透明性が高いことを示すものである。

This result indicates that each of Exemplified Compound D-2 and Exemplified Compound F-2 having a substituent at the ortho position of the phenyl group has higher transparency in the neutral state than Comparative Compound Ref-3. It is.

[Example 14]
<Evaluation of electrochromic characteristics>
Absorption in the oxidized (colored) state of Example Compound C-6 of Example 10, Example Compound D-2 of Example 11, Example Compound F-2 of Example 12, and Comparative Compound Ref-3 of Comparative Example 2 The spectrum was measured. The absorption spectrum was measured in the same manner as in Example 4.

  Table 5 shows the wavelength (colored absorption wavelength) λmax of the absorption peak in the colored state (oxidized state).

酸化により生成する着色種は、いずれも可視域波長の帯域に吸収を示す。しかし、分子外側部位のフェニル基のパラ位にアルコキシ基を有する例示化合物Ｃ−６、Ｄ−２、Ｆ−２のそれぞれは、分子外側部位のフェニル基のパラ位にアルコキシ基を有さない比較化合物Ｒｅｆ−３に比べて、酸化状態において長波長に吸収ピークを有する。この酸化着色状態は、還元により再度無色透明に戻り、酸化還元に伴う可逆的なエレクトロクロミック特性が確認された。

Any colored species produced by oxidation exhibits absorption in the visible wavelength range. However, each of Exemplified Compounds C-6, D-2, and F-2 having an alkoxy group at the para position of the phenyl group at the outer molecular site has no alkoxy group at the para position of the phenyl group at the outer molecular site. Compared with compound Ref-3, it has an absorption peak at a long wavelength in the oxidation state. This oxidation-colored state returned to colorless and transparent again by reduction, and reversible electrochromic characteristics associated with oxidation-reduction were confirmed.

  From Examples 13 and 14, Exemplified Compound C-6, Exemplified Compound D-2 and Exemplified Compound F-2 each having an alkoxy group at the para position of the phenyl group at the outer side of the molecule were compared with each other in Comparative Compound Ref-3 during oxidative coloring. Absorption is exhibited in a longer wavelength band of 540 nm or more. In particular, with respect to Exemplified Compound D-2 and Exemplified Compound F-2 having a substituent at the ortho position of the phenyl group, the neutral absorption of each of them is shortened, and both transparency at the time of decolorization and long wavelength absorption at the time of coloring are compatible. It was shown that

[Example 15]
<Preparation of electrochromic element and element driving>
An EC element 15 including Example Compound D-2 in the EC layer 12 was produced. First, an EC example compound D-2 as an anodic EC material and a cathodic EC compound W-2 having the following structure as a cathodic EC material were each dissolved in propylene carbonate at a concentration of 100.0 mM to prepare an EC solution. .

次いで、実施例５と同様の方法で空セルを作製し、作製した空セルに、真空注入法によりセルの開口部から本実施例のＥＣ溶液を充填することでＥＣ層１２を形成した。さらにセルの開口部をエポキシ樹脂により封止することにより、ＥＣ素子１５を作製した。

Next, an empty cell was produced in the same manner as in Example 5, and the produced empty cell was filled with the EC solution of this example from the opening of the cell by vacuum injection to form an EC layer 12. Further, the EC element 15 was fabricated by sealing the opening of the cell with an epoxy resin.

  When a voltage of 0.7 V is applied to the EC element 15, absorption derived from the oxidized species of the exemplary compound D-2 (λ to 550 nm) and absorption derived from the reduced species of the cathodic EC compound W-2 (λ to 615 nm) The EC element 15 is colored. The EC element 15 was decolored when 0 V was applied, and showed reversible color erasing. FIG. 9 shows the change in the transmittance spectrum of the EC element of this example accompanying this voltage application.

  As shown in FIG. 9, it was confirmed that the EC element 15 using the exemplary compound D-2 exhibits a change in transmittance in a long wavelength region when colored with application of voltage.

[Example 16]
<Synthesis of Exemplified Compound F-14>

まず、化合物ＸＸ−１１を合成した。５０ｍｌ反応容器に、化合物ＸＸ−１を３４２ｍｇ（０．９７ｍｍｏｌ）、４−メトキシ−２−メチルフェニルボロン酸を４８４ｍｇ（２．９１ｍｍｏｌ）、トルエン／１，４−ジオキサン（５ｍｌ／５ｍｌ）混合溶媒中で混合し、窒素で溶存酸素を除去した。なお、化合物ＸＸ−１は、Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔｅｒｓ，５２，６４８４（２０１１）に従って合成した。

First, Compound XX-11 was synthesized. In a 50 ml reaction vessel, compound XX-1 342 mg (0.97 mmol), 4-methoxy-2-methylphenylboronic acid 484 mg (2.91 mmol), toluene / 1,4-dioxane (5 ml / 5 ml) in a mixed solvent And dissolved oxygen was removed with nitrogen. Compound XX-1 was synthesized according to Tetrahedron Letters, 52, 6484 (2011).

Next, 8.8 mg (0.04 mmol) of Pd (OAc) ₂ , 40.0 mg (0.097 mmol) of S-Phos, 1.12 g (4.9 mmol) of tripotassium phosphate were added under a nitrogen atmosphere. The mixture was heated to reflux at 100 ° C. and reacted for 3 hours. The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / chloroform) to obtain Compound XX-11 as a yellow solid (410 mg, yield 96%).

  Subsequently, Example Compound F-14 is synthesized. In a 50 ml reaction vessel, 391 mg (0.90 mmol) of compound XX-11, 3.06 g (18.0 mmol) of 2-iodopropane, and a mixed solvent of acetonitrile / water (20 ml / 10 ml) were mixed, and dissolved oxygen with nitrogen Was removed. Next, 920 mg (4.5 mmol) of hydrosulfite sodium and 750 mg (5.4 mmol) of potassium carbonate were added in a nitrogen atmosphere, and the mixture was heated to reflux at 90 ° C. and reacted for 8 hours. The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / toluene) to obtain a solid exemplified compound F-14 (111 mg, 24% yield).

As a result of NMR measurement, since the ratio of peak integration values was in good agreement with the structure, it was confirmed that the obtained compound was Exemplified Compound F-14. The measurement results of the NMR spectrum are shown below.
¹ H-NMR (heavy acetone) δ (ppm): 7.15-7.05 (m, 3H), 6.98 (dd, 1H), 6.90-6.70 (m, 7H), 4. 48 (sep, 1H), 3.81 (s, 6H), 3.33 (sep, 1H), 2.35 (s, 3H), 2.28 (s, 6H), 1.62 (d, 6H) ), 1.23 (d, 6H).
[Example 17]
<Synthesis of Exemplified Compound B-30>

まず、化合物ＸＸ−１３を合成する。５０ｍｌ反応容器に、化合物ＸＸ−１２を３９５ｍｇ（１．４５ｍｍｏｌ）、２−イソプロポキシ−６−メトキシフェニルボロン酸を４５６ｍｇ（２．１７ｍｍｏｌ）、トルエン／１，４−ジオキサン（５ｍｌ／５ｍｌ）混合溶媒中で混合し、窒素で溶存酸素を除去した。

First, compound XX-13 is synthesized. In a 50 ml reaction vessel, compound XX-12 (395 mg, 1.45 mmol), 2-isopropoxy-6-methoxyphenylboronic acid (456 mg, 2.17 mmol), toluene / 1,4-dioxane (5 ml / 5 ml) mixed solvent Mix in and remove dissolved oxygen with nitrogen.

Next, 13.0 mg (0.06 mmol) of Pd (OAc) ₂ , 59.0 mg (0.15 mmol) of S-Phos, 1.66 g (7.2 mmol) of tripotassium phosphate were added under a nitrogen atmosphere. The mixture was heated to reflux at 100 ° C. and reacted for 4 hours. The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / chloroform) to obtain Compound XX-13 (510 mg, yield 98%) as a yellow solid.

  Subsequently, Example Compound B-30 is synthesized. In a 50 ml reaction vessel, 510 mg (1.42 mmol) of compound XX-13, 5.07 g (29.8 mmol) of 2-iodopropane, and acetonitrile / water (20 ml / 8 ml) mixed solvent were mixed, and dissolved oxygen with nitrogen. Was removed. Next, 1.53 g (7.45 mmol) of sodium hydrosulfite and 1.24 g (8.94 mmol) of potassium carbonate were added under a nitrogen atmosphere, and the mixture was heated to reflux at 90 ° C. for 9 hours. The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / toluene) to obtain solid exemplified compound B-30 (350 mg, yield 54%).

As a result of NMR measurement, since the ratio of peak integration values was in good agreement with the structure, it was confirmed that the obtained compound was Exemplified Compound B-30. The measurement results of the NMR spectrum are shown below.
¹ H-NMR (heavy acetone) δ (ppm): 7.20 (t, 1H), 699-6.83 (m, 5H), 6.74 (d, 1H), 6.72-6. 65 (m, 2H), 4.45 (sep, 2H), 3.69 (s, 3H), 3.25 (sep, 1H), 2.28 (s, 3H), 1.62 (d, 6H) ), 1.42-1.02 (d, br, 12H).
[Example 18]
<Synthesis of Exemplified Compound A-40>

まず、化合物ＸＸ−１４を合成する。５０ｍｌ反応容器に、化合物ＸＸ−２０を７０４ｍｇ（２．０ｍｍｏｌ）、２−イソプロポキシ−６−メトキシフェニルボロン酸を１．２６ｇ（６．０ｍｍｏｌ）、トルエン／１，４−ジオキサン（８ｍｌ／８ｍｌ）混合溶媒中で混合し、窒素で溶存酸素を除去した。

First, compound XX-14 is synthesized. In a 50 ml reaction vessel, 704 mg (2.0 mmol) of compound XX-20, 1.26 g (6.0 mmol) of 2-isopropoxy-6-methoxyphenylboronic acid, toluene / 1,4-dioxane (8 ml / 8 ml) The mixture was mixed in a mixed solvent, and dissolved oxygen was removed with nitrogen.

Next, 18.0 mg (0.08 mmol) of Pd (OAc) ₂ , 82.1 mg (0.20 mmol) of S-Phos, 2.30 g (10.0 mmol) of tripotassium phosphate were added under a nitrogen atmosphere. The mixture was heated to reflux at 110 ° C. and reacted for 6 hours. The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / chloroform) to obtain Compound XX-14 as a yellow solid (760 mg, yield 73%).

  Subsequently, Example Compound A-40 is synthesized. In a 50 ml reaction vessel, 750 mg (1.44 mmol) of compound XX-14, 4.88 g (28.8 mmol) of 2-iodopropane and acetonitrile / water (20 ml / 8 ml) mixed solvent were mixed, and dissolved oxygen with nitrogen Was removed. Next, 1.47 g (7.18 mmol) of hydrosulfite sodium and 1.19 g (8.61 mmol) of potassium carbonate were added in a nitrogen atmosphere, and the mixture was heated to reflux at 90 ° C. and reacted for 10 hours. The reaction solution was cooled to room temperature, concentrated under reduced pressure, and separated and purified by silica gel chromatography (mobile phase: hexane / toluene) to obtain a solid exemplified compound A-40 (580 mg, 66% yield).

As a result of NMR measurement, since the ratio of peak integration values was in good agreement with the structure, it was confirmed that the obtained compound was Exemplified Compound A-40. The measurement results of the NMR spectrum are shown below.
¹ H-NMR (heavy acetone) δ (ppm): 7.21 (t, 1H), 7.19 (t, 1H), 6.97 (s, 2H), 6.89 (s, 1H), 6 .83 (s, 1H), 6.75-6.66 (m, 5H), 4.45 (sep, 1H), 4.42 (sep, 1H), 3.72 (s, 3H), 3. 69 (s, 3H), 3.33 (sep, 1H), 2.30 (s, 3H), 1.64 (br, 6H), 1.38 (br, 6H), 1.17 (d, 12H) ).
[Example 19]
<Evaluation of neutral transparency and electrochromic properties>
Example Compound F-14 in Example 16, Example Compound B-30 in Example 17, and Example Compound A-40 in Example 18 are each in a decolored state (neutral state) in the same manner as in Examples 3 and 4. And the absorption spectrum in the colored state (oxidized state) was measured. Table 6 shows the absorption edge wavelength in the decolored state (neutral state) and the wavelength (colored absorption wavelength) λmax of the absorption peak in the colored state (oxidized state) for each compound.

例示化合物Ｆ−１４、Ｂ−３０、Ａ−４０のそれぞれは、着色状態において、表６に示すように、５４０ｎｍ以上の長波長域に吸収ピークを有する。この酸化着色状態は、還元により再び無色透明に戻り、酸化還元に伴う可逆的なエレクトロクロミック特性が確認された。

Each of the exemplary compounds F-14, B-30, and A-40 has an absorption peak in a long wavelength region of 540 nm or more in the colored state, as shown in Table 6. This oxidative coloring state returned to colorless and transparent again upon reduction, and reversible electrochromic properties associated with the oxidation reduction were confirmed.

  In addition, each of Exemplified Compounds F-14, B-30, and A-40 having a methyl group at the 1-position of the phenazine ring has a neutral absorption edge of 400 nm, particularly in transparency during decoloring. Excellent. The neutral absorption of each of the exemplary compounds F-14, B-30, and A-40 is significantly shorter than that of the comparative compound Ref-1. Further, the wavelength is further shortened than the neutral absorption ends (all 420 nm) of the exemplary compounds F-2, B-9, and A-21 having no methyl group at the 1-position of the phenazine ring.

  This shortening of the wavelength of neutral absorption improves the transparency and also improves the light resistance to UV light. In particular, when an EC material or an EC element according to the present invention is used in combination with a UV cut filter in an imaging apparatus, even if a UV cut filter that cuts light in a shorter wavelength region is used, deterioration to light may be reduced. I can do it.

  As described above, according to each of the above-described embodiments and examples, an EC organic compound having an absorption peak in a long wavelength region of 540 nm or more in a colored state can be provided. Further, the transparency in the decolored state can be improved as compared with the conventional case.

10 Substrate 11 Electrode 12 EC layer 15 EC element

Claims (20)

An organic compound represented by the following general formula (1):

In General Formula (1), R _{11 to} R ₁₅ each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. An aryl group which may have a substituent, an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom; However, at least one of R ₁₁ , R ₁₃ and R ₁₅ is an alkoxy group which may have a substituent or an aryloxy group which may have a substituent. R _{11 to} R ₁₅ may combine with each other to form a ring structure.
R ₅ and R ₆ each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
R ₂₁ to R ₂₄ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, It represents an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom, and may be bonded together to form a ring structure. It is shown by following General formula (2), The organic compound of Claim 1 characterized by the above-mentioned.

In General Formula (2), R ₁ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
R ₁₂ to R ₁₅ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl which may have a substituent. Represents a group, an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom, and may be bonded together to form a ring structure. Good.
R ₅ and R ₆ each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
R ₂₁ to R ₂₄ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, It represents an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom, and may be bonded together to form a ring structure. It is shown by following General formula (3), The organic compound of Claim 1 characterized by the above-mentioned.

In General Formula (3), R ₁ and R ₂ each independently have an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. Represents a good aralkyl group.
R ₁₂ to R ₁₄ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl which may have a substituent. Represents a group, an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom, and may be bonded together to form a ring structure. Good.
R ₅ and R ₆ each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
R ₂₁ to R ₂₄ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, It represents an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom, and may be bonded together to form a ring structure. It is shown by following General formula (4), The organic compound of Claim 1 characterized by the above-mentioned.

In General Formula (4), R ₁ and R ₇ each independently have an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. Represents a good aralkyl group.
R _{12 to} R ₁₅ and R _{31 to} R ₃₄ each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. Represents an optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted aralkyl group, an acyl group, or a halogen atom, and is bonded to each other to form a ring structure. May be. R ₅ and R ₆ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
R ₂₁ , R ₂₂ , and R ₂₄ each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. An aryl group, an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom, which is bonded to each other to form a ring structure Also good. It is shown by following General formula (5), The organic compound of Claim 1 characterized by the above-mentioned.

In General Formula (5), R ₁ , R ₂ , R ₇ and R ₈ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. An aralkyl group which may have a group; R _{12 to} R ₁₄ and R _{32 to} R ₃₄ each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. Represents an aryl group which may have a substituent, an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom; It may be formed. R ₅ and R ₆ each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
R ₂₁ , R ₂₂ , and R ₂₄ each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. An aryl group, an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom, which is bonded to each other to form a ring structure Also good. It is shown by following General formula (6), The organic compound of Claim 1 characterized by the above-mentioned.

In General Formula (6), R ₃ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
R ₁₁ , R ₁₂ , R ₁₄ and R ₁₅ each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. Represents an aryl group which may have a substituent, an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom; It may be formed.
R ₅ and R ₆ each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
R ₂₁ to R ₂₄ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, It represents an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom, and may be bonded together to form a ring structure. At least one of R ₁₁ and R ₁₅ is an alkyl group that may have a substituent, an aryl group that may have a substituent, or an aralkyl group that may have a substituent. The organic compound according to claim 6. It is shown by following General formula (7), The organic compound of Claim 6 characterized by the above-mentioned.

In General Formula (7), R ₃ and R ₉ each independently have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents a good aralkyl group.
R ₁₁ , R ₁₂ , R ₁₄ , R ₁₅ , R ₃₁ , R ₃₂ , R ₃₄ and R ₃₅ each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. An optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted aralkyl group, an acyl group, or a halogen atom. And a substituent may be bonded to each other to form a ring structure.
R ₅ and R ₆ each independently represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
R ₂₁ , R ₂₂ and R ₂₄ each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An aryl group, an aryloxy group which may have a substituent, an aralkyl group which may have a substituent, an acyl group, or a halogen atom, which is bonded to each other to form a ring structure Also good. At least one of R ₁₁ , R ₁₅ , R ₃₁ and R ₃₅ may have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. The organic compound according to claim 8, which is a good aralkyl group. The organic compound according to any one of claims 1 to 9, wherein at least one of R ₂₁ and R ₂₄ is a methyl group.   The organic compound according to any one of claims 1 to 10, which has an absorption peak in a wavelength region of 540 nm or more in a colored state.   The organic compound according to any one of claims 1 to 11, which is transparent in a wavelength region of 430 nm or more in a decolored state. A pair of electrodes;
An electrochromic layer disposed between the pair of electrodes,
The said electrochromic layer contains the organic compound as described in any one of Claim 1 to 12, The electrochromic element characterized by the above-mentioned.   The electrochromic device according to claim 13, wherein the electrochromic layer further includes an organic compound different from the organic compound.   The electrochromic device according to claim 14, wherein the different kind of organic compound is transparent in a visible wavelength region of 430 nm or more in a decolored state.   The electrochromic element according to claim 13, wherein the electrochromic layer is a liquid having an electrolyte and the organic compound. The electrochromic device according to any one of claims 13 to 16,
And an active element connected to the electrochromic element. An optical filter according to claim 17,
An imaging optical system having a plurality of lenses. An optical filter according to claim 7;
An image pickup apparatus comprising: an image pickup element that receives light transmitted through the optical filter. A pair of substrates;
The electrochromic device according to any one of claims 13 to 16, which is disposed between the pair of substrates,
An active element connected to the electrochromic element,
A window material characterized in that the amount of light transmitted through the pair of substrates is adjusted by the electrochromic element.

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