JPH0742248B2 - Diaryl maleic acid derivative and process for producing diaryl ethene - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel diarylmaleic acid derivative having photochromic properties, and a method for producing diarylethenes.

[Conventional technology]

Conventionally, various compounds having a photochromic property that develops or discolors upon irradiation with light have been known, and recording / memory materials, copying materials, light control materials, masking materials, photometers, or displays using these compounds. Various materials for use have been proposed. Examples of such photochromic compounds include compounds such as benzospiropyrans, naphthoxazines, fulgides, diazo compounds, and diarylethenes.

In recent years, many studies have been conducted to use such a photochromic compound as a reversible optical recording material, but the following performance is required for using it as an optical recording material. That is, (1) recording stability, (2) repetitive durability, (3) high sensitivity, (4) semiconductor laser sensitivity, etc.

However, currently known photochromic compounds are generally thermally unstable in either a colored state or a decolored state and return to a stable state within a few hours even at room temperature. It has the drawback that stability cannot be ensured. Fulgides and diarylethenes have been proposed as photochromic compounds whose two states are relatively stable when exposed to light, but their stability is insufficient for application to optical recording materials, and their repeated durability. Has the disadvantage of being inferior to.

Therefore, none of the conventional photochromic compounds has sufficiently satisfactory performance as an optical recording material.

Further, as a conventional method for producing diarylethenes, a dimerization reaction of an acetylated product with low-valent titanium (Japanese Patent Application Laid-Open No. S60-12069).
61-263935), a dimerization reaction of a cyanomethylated compound with a phase transfer catalyst (JP-A-63-24245), a method by Wittig reaction (JP-A-63-77876), and the like. However, these methods have problems in that the number of substituents is limited, the desired product cannot be obtained selectively, and the synthesis requires multiple steps.

Therefore, even in the production of diarylethene to solve the above-mentioned drawbacks, the conventional production method has a limit.

[Problems to be Solved by the Invention]

The present invention has been made in view of such circumstances, and an object thereof is to provide a diaryl maleic acid derivative having excellent properties in thermal stability in a colored state, repeated durability, and sensitivity. There is.

Still another object is to obtain diarylethenes having a wide range of structures such that diarylethenes can be easily obtained in high yield and asymmetric diarylethenes can be selectively produced. A method for producing diarylethenes is provided.

[Means for Solving the Problems]

The above-mentioned objects are represented by the general formula (I) (In the formula, R ¹ and R ² represent a hydrogen atom or an aliphatic hydrocarbon group, and A ¹ and A ² are The stands, R ^3, R ⁷ is a methyl group or a fluorine atom, R ^8, R ¹¹
Represents a methyl group, R ^{4 to} R ⁶ , R ⁹ , R ¹⁰ and R ^{12 to} R ¹⁵ represent a hydrogen atom, a fluorine atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or a cyano group, and R ¹ And R ² , or A ¹ and A ² may be the same or different. ) Is achieved by a diaryl maleic acid derivative represented by

Further, an aromatic compound derivative represented by the general formula (II) AX ... (II) (wherein A represents an aryl group or a heterocyclic group, and X represents a chlorine atom, a bromine atom or an iodine atom) or The halogen of the heterocyclic compound derivative is represented by the general formula (II ′) ▲ R ¹⁶ _m ▼ ML _n (II ′) (wherein R ¹⁶ is a hydrocarbon group or a disubstituted amino group, M is Mg,
Cu, Zn, Sn, B, Al, Si or Zr, L is an anion residue, m, n is 1
Represents an integer of 3 ) A general formula (I
I ″) ▲ AMR ¹⁶ _p ▼ L _q X _r ... (II ″) (In the formula, A, M, R ¹⁶ , L and X are the same as above, p and q are integers of 0 to 3, r is 0 or Represents 1, but any of p, q, and r is 0
Not. ) Is an organic metal compound represented by the general formula (III) RC≡CR ′… (III) (wherein R and R ′ are hydrogen atoms, aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbons). Represents a hydrogen group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a cyano group, R,
R'may be the same or different. Further, R and R ′ may form a ring structure in cooperation with the triple bond. ) Is reacted with the acetylene derivative represented by the formula (1), and the reaction product is subsequently represented by the general formula (IV) A′X ... (IV) (wherein A ′ represents an aryl group or a heterocyclic group, X
Indicates the same as above. ) An aromatic compound derivative or a heterocyclic compound derivative represented by (Wherein R, R ′, A and A ′ are the same as those described above, and A and A ′ may be the same or different).

Next, the present invention will be described in detail.

The diarylmaleic acid derivative of the present invention is represented by the general formula (I), and is a maleic acid derivative in which R ¹ and R ² are hydrogen atoms, or both R ¹ and R ² or R ¹ and R ¹ . ²
A maleic acid diester or maleic acid monoester derivative in which either one of them is an aliphatic hydrocarbon group is included. As the maleic acid ester derivative, R ¹ and R ² are preferably a methyl ester having 1 to 3 carbon atoms, an ethyl ester, or a propyl ester.

A ¹ and A ² are a phenyl group, a thienyl group, or a benzothienyl group, and in particular, ^one in which at least one of A ^{1 and} A ² is a benzothienyl group has excellent thermal stability of coloring and excellent repeated durability. And is preferred.

R ³ and R ⁷ are methyl groups or fluorine atoms, and R ⁸ and R ¹¹ are methyl groups.

Next, the method for producing a diarylethene compound of the present invention, including the diarylmaleic acid derivative of the present invention, comprises: a) synthesis of an organometallic compound from an aromatic compound derivative or a heterocyclic compound derivative; b) an organometallic compound and acetylene. It can be divided into three steps: reaction with a derivative and reaction of (c) a product obtained from an organometallic compound and an acetylene derivative with an aromatic compound derivative or a heterocyclic compound derivative. However, the reactions a) to c) can be carried out continuously, and in order to simplify the process, it is not necessary to isolate the product until the intended diarylethene is obtained.

First, in the reaction of a), an organometallic compound is synthesized from an aromatic compound derivative or a heterocyclic compound derivative represented by the general formula (III). As a method for synthesizing this organometallic compound, for example, a method of reacting an aromatic compound derivative or a heterocyclic compound derivative with metallic magnesium, a method of reacting metallic magnesium and then reacting with zinc halide or copper halide, Examples thereof include a method of reacting metal magnesium and then a copper bromide-dimethyl sulfide complex, a method of reacting organolithium and then reacting with copper dicyclohexylamide, and the like.

Further, as the metal of the organometallic compound of the present invention, magnesium, copper, zinc, tin, boron, aluminum, silicon, zirconium and the like are preferably used.

The aromatic compound derivative or the heterocyclic compound derivative represented by the general formula (I) used in the present invention may have a low reactivity with an organometallic compound obtained by reacting with a metal compound, As A of, for example, (Here, R ^{3 to} R ²³ are a hydrogen atom, a fluorine atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a halogen-substituted alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, Represents a cyano group, Y is an oxygen atom,
Represents a sulfur atom or an alkyl-substituted nitrogen atom, Z ^{1 to} Z ⁶ represent a nitrogen atom or a monosubstituted carbon atom, and at least one of Z ^{1 to} Z ³ and at least one of Z ^{4 to} Z ⁶ are nitrogen. Is an atom. ) And the like. Specific examples of the heterocyclic compound derivative include a thiophene derivative, a furan derivative, a pyrrole derivative, a benzothiophene derivative, a benzofuran derivative, an indole derivative, an isoxazole derivative, a thiadiazole derivative, a thiazole derivative, a pyrazole derivative or a triazole derivative. To be Further, X in the general formula (II) may be any one of a chlorine atom, a bromine atom and an iodine atom, but is particularly preferably a bromine atom or an iodine atom which is highly reactive and has a good yield. .

The amount of the metal compound used is preferably 0.7 to 1.3 times mol, more preferably 0.8 to 1.2 times mol, of the aromatic compound derivative or the heterocyclic compound derivative.

The reaction temperature varies depending on the aromatic compound derivative or the heterocyclic compound derivative used, and a suitable temperature may be set appropriately. The reaction time is preferably 1 to 24 hours, more preferably 2 to 5 hours.

Next, in the reaction of b), the acetylene derivative represented by the general formula (III) is added to the organometallic compound obtained in a) to obtain an adduct to the acetylene derivative. Here, the acetylene derivative represented by the general formula (III) has a substituent
It is necessary that R and R ′ have low reactivity with the above-mentioned organometallic compound, and R and R ′ are a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group. , An alkoxycarbonyl group, an acyl group, and a cyano group can be used as a substituent. Further, R and R ′ may be the same or different, and both may form a ring structure.

The addition amount of the acetylene derivative is preferably 0.7 to 1.3 times mol, and more preferably 0.8 to 1.2 times mol, of the aromatic compound derivative or the heterocyclic compound derivative used at the beginning.

The reaction temperature varies depending on the compound to be used as described above, and thus a suitable temperature may be appropriately set. The reaction time is preferably 0.5 to 24 hours, more preferably 1 to 5
It's time.

Without isolation of the addition product obtained from the acetylene derivative and the organometallic compound, the reaction of c), that is, by adding the aromatic compound derivative or the heterocyclic compound represented by the general formula (IV), the desired product is obtained. A diarylethene represented by the general formula (V) can be obtained. The aromatic compound derivative or the heterocyclic compound to be added may be the same as or different from the aromatic compound derivative or the heterocyclic compound derivative used at the beginning. Particularly with different derivatives, it is possible to obtain selectively single asymmetric diarylethenes. This is a great feature of the present invention, which cannot be obtained by the conventional method for producing diarylethenes.

The amount of aromatic derivative or heterocyclic derivative to be added is
The aromatic or heterocyclic derivative used at the beginning is preferably 0.8 to 3 times mol, more preferably 1 to 3 times mol.
It is twice the mole.

The reaction temperature of c) is preferably −80 to 100 ° C., more preferably −80 to 25 ° C. Also, start the reaction at low temperature,
A method of raising the temperature on the way can also be adopted. The reaction time is preferably 2 to 24 hours, more preferably 5 to 15 hours.

The reaction of c) is possible without a catalyst, but a transition metal complex catalyst such as tetrakistriphenylphosphine palladium, dichlorobis (triphenylphosphine) palladium or dichloro [1,4-bis (diphenylphosphinobutane)] palladium is used. It is preferable to use it because the yield is high.

The production method of the present invention is preferably carried out in a sufficiently dehydrated organic solvent, for example, diethyl ether, tetrahydrofuran (THF) or the like, and in a container replaced with an inert gas such as nitrogen or argon.

Since the products obtained in the reactions a) to c) are a mixture, they must be separated in order to obtain the diarethanes, but the separation is carried out by a commonly used extraction method, distillation method,
It can be easily performed by appropriately selecting a recrystallization method, a chromatography method, or the like.

Taking the dithienylmaleic acid derivative as an example, the diarylmaleic acid derivative of the present invention changes from a ring-opened body to a ring-closed body upon irradiation with ultraviolet light and changes from colorless to yellow as shown in the following formula (VI).

When the closed ring is irradiated with visible light, it returns to the original open ring and disappears. The diarylmaleic acid derivative-based photochromic compound of the present invention has high thermal stability in both the colored state and the decolored state, does not change for a long period of time, and is well retained.
Further, it has excellent durability against repeated coloring and decoloring, and can be advantageously used for reversible optical information recording materials.

The optical recording material using the recording layer containing the novel diarylmaleic acid derivative of the present invention can be obtained, for example, by the following known method. That is, (1) a method of depositing the diarylmaleic acid derivative of the present invention on a suitable substrate by a known vapor deposition method, (2) a polyester resin, polystyrene resin, or polyvinyl chloride of the diarylmaleic acid derivative of the present invention Resin, polyvinyl acetate resin, polyvinyl butyral resin,
Polymethylmethacrylate resin, Polycarbonate resin,
Benzene, toluene, hexane, cyclohexane, with resin binders such as phenol resin and epoxy resin
A method of dispersing or dissolving in a solvent such as methyl ethyl ketone, acetone, methanol, ethanol, terrahydrofuran, dioxane, carbon tetrachloride, chloroform and coating on a suitable substrate, (3) The diarylmaleic acid derivative of the present invention The optical recording material of the present invention can be produced by forming a recording layer by a method of dissolving in a solvent such as the above and enclosing in a glass cell or the like.

〔The invention's effect〕

INDUSTRIAL APPLICABILITY As described above, the diaryl maleic acid derivative of the present invention is excellent in thermal stability, has good photochromic property of repeated durability of coloring and decoloring, and is a recording / memory material, copying material, light control material, masking material. It can be suitably used for various applications such as materials and display materials. Further, when the diarylmaleic acid derivative of the present invention is used as a recording layer and a suitable light source is used for color development and erasing, and a difference in hue thereof is read out as a signal, a highly reliable reversible optical recording material is obtained. be able to.

Further, according to the production method of the present invention, diarylethenes can be easily obtained in high yield. The production method of the present invention can not only selectively obtain asymmetric diarylethenes, but can also produce diarylethenes having a wide range of structures.

Many of the diarylethenes are useful as wotochromic compounds, and the production method of the present invention can be used for producing excellent photochromic compounds such as the diarylmaleic acid derivative of the present invention.

Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

[Example 1] (1) Production of dimethyl 2,3-di (2-methylbenzothienyl) -maleate In a three-necked flask having a capacity of 100 ml, 0.229 g (1.01 mmol) of 3-bromo-2-methylbenzothiophene was added. After adding 5 ml of diethyl ether and cooling to -70 ° C under a nitrogen stream, 1 mmol of n-butyllithium hexane solution was added dropwise and stirred for 30 minutes. Next, copper dicyclohexylamide 1.1m prepared separately from dicyclohexylamine, methyllithium and copper iodide
10 ml of a diethyl ether solution was added dropwise and reacted for 40 minutes. Next, 5 ml of a diethyl ether solution of 126 μ (1.0 mmol) of dimethyl acetylenedicarboxylate was added dropwise and reacted for 1 hour. Further, 329 ml of a THF solution of 0.229 g (1.01 mmol) of 3-bromo-2-methylbenzothiophene and tetrakis were added. Triphenylphosphine palladium 0.058 g (0.
(05mmol) was added, and the reaction was performed for 12 hours while returning to room temperature. After completion of the reaction, 10 ml of 3N hydrochloric acid was added, and the mixture was extracted with 100 ml of diethyl ether. The obtained reaction product was separated and purified by silica gel preparative plate chromatography, and as a result, 210 mg (yield 48%) of a diaryl maleic acid derivative having the following structural formula was obtained.

(2) Analytical value (i) ¹ H-NMR (CDCl ₃ ) δ = 3.55 ppm (s, 6H) 2.7 ppm (s, 6H) 7.2 to 7.8 ppm (m, 8
H) (ii) MS (m / e) 436 (M ⁺ ) (3) Photochromic property The compound synthesized in (1) above was added to benzene at 10 ^-3 mol /
The pale yellow solution obtained by dissolving so as to have the above composition was enclosed in a quartz glass cell and irradiated with ultraviolet light for 30 seconds by a 100 W mercury lamp (manufactured by Osram) equipped with a glass filter (manufactured by U-330HOYA). However, it was colored deep yellow. The absorption spectrum changed from that shown by the solid line in FIG. 1 to that shown by the dotted line. That is, the right fragrance of the following formula was changed by ultraviolet light, and it was colored deep yellow.

This colored state was very stable thermally, and even when left at 37 ° C. for 2 weeks or longer, no decrease in absorption of the colored state was observed as shown in FIG. Next, a cut filter (manufactured by Nippon Vacuum Optical Co., Ltd.) was attached to the solution colored deep yellow.
When it was irradiated with visible light of 400 nm or more by a 0 W mercury lamp for 2 minutes, the color was erased and the original color state was changed. This change could be reversibly repeated.

(4) Repeated durability (reversible color fading cycle resistance) 40 mg of the compound synthesized in (1) above was dissolved together with 300 mg of polymethylmethacrylate, and this was applied onto a 1 × 3 cm square quartz glass plate by spin coating, A recording layer was prepared by drying. 460nm of absorption spectrum of this recording layer
The transmittance was 87%. U-330 is used for this recording layer
Ultraviolet light was irradiated for 30 seconds with a 100 W mercury lamp equipped with a filter to make the entire surface colored. The transmittance of the obtained absorption spectrum in the colored state at 460 nm was 77%. Then, the colored recording layer was irradiated with visible light of 400 nm or more for 2 minutes by a 100 W mercury lamp equipped with a cut filter, and the color was erased, and the transmittance of the absorption spectrum of the recording layer returned to 87%. By alternately irradiating this ultraviolet light and visible light, coloring and decoloring were set as one cycle, and the durability test was repeated. The results are shown in FIG.

As shown in FIG. 3, the transmittance of the absorption spectrum at 460 nm after repeating 1000 times was 86% in the decolored state and 77% in the colored state. When it was repeated 2000 times, the decolored state was 82% and the colored state was 72%.

Example 2 By the method according to Example 1, R ¹ and R 2 in the general formula (I) were used.
Diaryl maleic acid derivatives in which ² , A ¹ and A ² are shown in Table 1 were synthesized. An ultraviolet irradiation test was conducted on the obtained benzene solution of the diarylmaleic acid derivative in the same manner as in Example 1. As a result, each was colored in the color tone shown in Table 1. Further, each colored state was thermally very stable. Next, when this landing state was irradiated with visible light, the original light yellow state could be erased. Furthermore, this change could be reversibly repeated.

[Example 3] 0.073 g of metallic magnesium in a three-necked flask having a capacity of 100 ml
Charge (3mmol), add 1ml of THF under nitrogen atmosphere,
The mixture was kept at ℃ and stirred. Iodobenzene 336μ (3m
5 ml of THF solution of (mol) was added dropwise, and the mixture was stirred at 0 ° C. for 1 hour and further at room temperature for 1 hour. The solution was then cooled to -78 ° C, copper iodide (3 mmol) was added, then the temperature was raised to -40 ° C and stirred for 1 hour. The solution was cooled again to -78 ° C and the dimethyl acetylenedicarboxylate 367μ (3mmol) T was added.
5 ml of the HF solution was gradually added dropwise. After the completion of the dropping, the mixture was stirred for 1 hour while being kept at -78 ° C. After adding tetrakistriphenylphosphine palladium 0.173g (5mol%) to this, 2-iodothiophene 331μ (3mmol) in THF
5 ml was gradually added dropwise. After the dropping, the temperature was gradually raised from −78 ° C. to room temperature and stirred at room temperature for 10 hours. After the reaction was completed, 60 ml of 2N hydrochloric acid was added. Then 2 with 50 ml of diethyl ether
The extract was extracted twice, the ether layers were collected, washed and dried, and then the ether was distilled off. The reaction product was separated and purified using a silica gel preparative plate, and as a result, 760 mg (yield 84%) of diarylethenes having the following structural formula was obtained. The product was identified by nuclear magnetic resonance spectrum, infrared absorption spectrum, and mass spectrometry spectrum. (Hereinafter, the product was identified in the same manner.) Example 4 An aromatic compound derivative or a heterocyclic compound derivative shown in Table 2 was used, and other conditions were the same as in Example 3,
The diarylethenes shown in Table 2 were obtained. All the obtained diarylethenes exhibited reversible color change upon irradiation with light.

[Example 5] 0.073 g of magnesium metal in a three-necked flask having a capacity of 100 ml
Charge (3mmol), add 5ml of THF under nitrogen atmosphere, and 0 ℃
And stirred. Add mesityl bromide 459μ (3
15 ml of THF solution of (mol mol) was added dropwise, and the mixture was stirred at 0 ° C. for 1 hour and further at room temperature for 1 hour. Next, this solution was cooled to −78 ° C., 0.617 g (3 mmol) of copper bromide-dimethyl sulfide complex was added, and then the temperature was raised to −40 ° C. and stirred for 1 hour. The solution was cooled again to −78 ° C., and 5 ml of a THF solution containing 367 μ (3 mmol) of dimethylacetylene dicarboxylate was gradually added dropwise. After the completion of the dropping, the mixture was stirred for 1 hour while being kept at -78 ° C. After adding tetrakistriphenylphosphine palladium 0.173g (5mol%) to this, 3-iodo-2,5
-Dimethylthiophene 409μ (3m mol) in THF solution 5ml
Was gradually added dropwise. After the dropping, the temperature was gradually returned to room temperature from −78 ° C., and the mixture was stirred at room temperature for 10 hours. 2N hydrochloric acid after reaction
60 ml was added. Then, the mixture was extracted twice with 50 ml of diethyl ether, the ether layers were collected, washed and dried, and then the ether was distilled off. The reaction product was separated and purified using a silica gel preparative plate, and as a result, 650 mg (yield 58%) of diarylethenes having the following structural formula was obtained.

[Example 6] Diarylethenes shown in Table 3 were obtained in the same manner as in Example 5 except that the aromatic compound or heterocyclic compound shown in Table 3 and the acetylene derivative were used. All the obtained diarylethenes exhibited reversible color change upon irradiation with light.

[Example 7] 0.073 g of metal magnesium in a three-necked flask having a capacity of 100 ml
Add (3mmol), add 1ml of THF under nitrogen atmosphere, 0 ℃
And stirred. To this, 5 ml of a THF solution of 409 μ (3 mmol) of 3-iodo-2,5-dimethylthiophene was added dropwise,
The mixture was stirred at 0 ° C for 1 hour and further at room temperature for 1 hour. The solution was then cooled to -78 ° C and copper bromide-dimethyl sulfide complex 0.617 g
(3 mmol) was added, then the temperature was raised to -40 ° C and the mixture was stirred for 1 hour. The solution was cooled again to -78 ℃, and dimethylacetylene dicarboxylate 367μ (3mmol) in THF was added.
5 ml was gradually added dropwise. After the completion of the dropping, the mixture was stirred for 1 hour while being kept at -78 ° C. To this, anhydrous zinc chloride 0.409g (3m
mol) was added, and then the temperature was raised to room temperature and stirred for 1 hour. Tetrakistriphenylphosphine palladium (0.173 g, 5 mol%) was added thereto, and 4-iodinated-2,5-
517 ml of a THF solution containing 0.717 g (3 mmol) of dimethylthiazole was gradually added dropwise. After the dropping, 10 hours at room temperature, then 40 ℃
And stirred for 3 hours.

After the reaction was completed, 50 ml of 2N hydrochloric acid was added. Then, the mixture was extracted twice with diethyl ether, the ether layers were collected, dried over anhydrous magnesium sulfate, and the ether was distilled off. The reaction product was separated and purified using a silica gel preparative plate. As a result, 360 mg of diarylethenes having the following structural formula (yield 33
%) Was obtained.

Also, reversible changes due to light irradiation were observed.

[Brief description of drawings]

FIG. 1 is a graph showing the optical change in absorption spectrum of the compound synthesized in (1) of Example 1 in a benzene solution.
FIG. 3 is a graph showing the time-dependent change in the absorbance reduction rate of the colored cyclized product of the compound synthesized in (1) of Example 1, and FIG. 3 is the ultraviolet light of the optical recording layer prepared in (4) of Example 1. 5 is a graph showing a change in transmittance at 460 nm with alternating irradiation with visible light.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area C07C 253/30 255/57 C07D 333/24 333/38 333/60

Claims (3)

[Claims] 1. A general formula (I) (In the formula, R ¹ and R ² represent a hydrogen atom or an aliphatic hydrocarbon group, and A ¹ and A ² are The stands, R ^3, R ⁷ is a methyl group or a fluorine atom, R ^8, R ¹¹
Represents a methyl group, R ^{4 to} R ⁶ , R ⁹ , R ¹⁰ and R ^{12 to} R ¹⁵ represent a hydrogen atom, a fluorine atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or a cyano group, and R ¹ And R ² , or A ¹ and A ² may be the same or different. ) A diaryl maleic acid derivative represented by: 2. An aromatic compound represented by the general formula (II) AX (II) (wherein A represents an aryl group or a heterocyclic group, and X represents a chlorine atom, a bromine atom or an iodine atom). The halogen of the derivative or the heterocyclic compound derivative is represented by the general formula (II ′) ▲ R ¹⁶ _m ▼ ML _n (II ′) (wherein R ¹⁶ is a hydrocarbon group or a disubstituted amino group, M is Mg,
Cu, Zn, Sn, B, Al, Si or Zr, L is an anion residue, m, n is 1
Represents an integer of 3 ) A general formula (I
I ″) ▲ AMR ¹⁶ _p ▼ L _q X _r ... (II ″) (In the formula, A, M, R ¹⁶ , L and X are the same as above, p and q are integers of 0 to 3, r is 0 or Represents 1, but any of p, q, and r is 0
Not. ) Is an organic metal compound represented by the general formula (III) RC≡CR ′… (III) (wherein R and R ′ are hydrogen atoms, aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbons). Represents a hydrogen group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a cyano group, R,
R'may be the same or different. Further, R and R ′ may form a ring structure in cooperation with the triple bond. ) Is reacted with the acetylene derivative represented by the formula (1), and the reaction product is subsequently represented by the general formula (IV) A′X ... (IV)
Indicates the same as above. ) An aromatic compound derivative or a heterocyclic compound derivative represented by (In the formula, R, R ', A and A'represent the same as those described above, and A and A'may be the same or different.) A method for producing a diarylethene. 3. A general formula (II) A ³ X (II) (wherein A ³ is X represents a chlorine atom, a bromine atom, or an iodine atom, and R ^{3 to} R ²³ represent a hydrogen atom, a fluorine atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a halogen-substituted alkyl group. Represents a group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a cyano group, Y represents an oxygen atom, a sulfur atom, an alkyl-substituted nitrogen atom, Z ^{1 to} Z ⁶ represent a nitrogen atom or a monosubstituted carbon atom, and Z 1 ^At least one of ^{1 to} Z ³ and at least one of Z ^{4 to} Z ⁶ are nitrogen atoms. ) The halogen of the aromatic compound derivative or heterocyclic compound derivative represented by the general formula (II ′) ▲ R ¹⁶ _m ▼ ML _n (II ′) (wherein R ¹⁶ , M, L and m, n are The same as the above), a general formula (II
) A ³ ▲ MR ¹⁶ _p ▼ L _q X _r … (II) (wherein A, M, R ¹⁶ , L, X, p, q and r are the same as above) Formula (III) RC≡CR ′ (III) (In the formula, R and R ′ are a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, an alkoxy group, an alkoxycarbonyl group, Represents an acyl group or a cyano group, R,
R'may be the same or different. Further, R and R ′ may form a ring structure in cooperation with the triple bond. ) Is reacted with the acetylene derivative represented by the formula (1), and the reaction product is subsequently represented by the general formula (IV ′) A ⁴ X (IV ′) (in the formula, A ⁴ is the same as the above A ³ , Represents the same as above.) The general formula (V) characterized by reacting an aromatic compound derivative or a heterocyclic compound derivative represented by (In the formula, R, R ', A ³ and A ⁴ are the same as those described above, and A ³ and A ⁴ may be the same or different.).