WO2007105699A1

WO2007105699A1 - Dithienylcyclopentene compound, styrene polymer having dithienylcyclopentene, photochromic material, and photonic element

Info

Publication number: WO2007105699A1
Application number: PCT/JP2007/054868
Authority: WO
Inventors: Seiya Kobatake
Original assignee: Osaka Industrial Promotion Organization
Priority date: 2006-03-11
Filing date: 2007-03-12
Publication date: 2007-09-20
Also published as: JPWO2007105699A1

Abstract

A display material which, upon light irradiation, generates two isomers each relatively stable to heat and which in a colored state can be easily returned to a colorless state; a photochromic material which reacts irreversibly by the action of ultraviolet; a novel photochromic material which assumes a red color; a novel photochromic material which reacts irreversibly by the action of ultraviolet to show photochromism and is irreversibly decolored by heating; and a polymer which in a solid state shows photochromism and which can contain a photochromic ingredient evenly at a high density. The display material is a dithienylcyclopentene compound represented by the following general formula (I). The polymer is a styrene polymer having a dithienylcyclopentene represented by the following general formula (II).

Description

Specification

Dicenylcyclopentene compound, styrene polymer having diphenylcyclopentene, photochromic material, and optical functional device

Technical field

The present invention relates to a novel diphenylcyclopentene compound, a styrene polymer having a novel diacetylcyclopentene, a photochromic material including these compounds, and an optical functional device including the material.

Background art

[0002] (1) A photochromic compound is a compound that reversibly generates two structural isomers having different colors by light irradiation. Such photochromic compounds are broadly classified into those that are thermally stable at room temperature (P-type photochromism) and those that are thermally unstable at room temperature (T-type photochromism). Is done. For example, diarylmethene compounds and fulgide compounds exhibit P-type photochromism, and spiropyran azobenzene exhibits T-type photochromism.

[0003] A diarylethene compound or a fulgide compound is a compound in which both two kinds of heterogeneous substances generated by light irradiation are relatively thermally stable. For this reason, application in fields such as optical recording is expected (see, for example, Patent Documents 1 and 2).

[0004] (2) A photochromic compound is a substance that reversibly generates two structural isomers having different colors by light irradiation. Among such photochromic compounds, diarylethene compounds are expected to be applied to optical memories and display materials that are thermally stable and have high repeated durability. However, for example, a diaryruthene compound represented by the following chemical formula (ΠΙ) fades with visible light. For this reason, this compound has a problem that it cannot be used in the presence of room light.

In order to solve the above problem, a diallethene is synthesized in which a colored body does not fade even under room light and returns to an original colorless body by heating. For example, a diallethene compound represented by the following chemical formula (IV) developed by the present inventors does not fade with visible light (see, for example, Non-Patent Document 1, Patent Documents 3 and 4).

[Chemical 2]

(In the formula (IV), R represents a cyclohexyloxy group.) Patent Document 1: Japanese Patent Laid-Open No. 10-45732

Patent Document 2: JP-A-9 71585 Patent Document 3: Japanese Patent Laid-Open No. 2003-255489

Patent Document 4: Japanese Patent Laid-Open No. 2003-255490

Non-patent literature l: Morimitsu, Shibata, Kobatake, Irie, J. Org. Chem. 2002, 67, p. 4574-4578

Disclosure of the invention

Problems to be solved by the invention

(1) However, the compounds described in Patent Documents 1 and 2 are not easy to return from a colored state to an uncolored state. Therefore, it is necessary to provide a compound that can be easily rewritten when used as a display material.

[0007] That is, the present invention has been made in view of the above-mentioned problems, and the object thereof is that both of the two isomers generated by light irradiation are thermally relatively stable and have no color state. An object of the present invention is to provide a display material that can be easily returned to a colored state.

[0008] Another object of the present invention is to provide a dicenylcyclopentene-based material that reacts irreversibly with ultraviolet light.

[0009] Many of the currently known irreversibly reacting di-cyclopentene materials are colored blue. Still another object of the present invention is to provide a novel di-cyclopentene-based material that is colored red.

[0010] Another object of the present invention is to provide a novel photochromic material that reversibly shows photochromism by light and that irreversibly loses its colored state by heating.

[0011] (2) Further, when a photochromic compound is used as a display material, it is necessary to exhibit photochromism in a solid state. However, low-molecular photochromic compounds cannot be contained in polymers at high concentrations. Also, since molecular diffusion occurs in the polymer during heating, it cannot be dispersed uniformly and densely in the polymer.

[0012] In actual implementation, a polymer having high heat resistance is preferable.

[0013] That is, the present invention has been made in view of the above problems, and an object of the present invention is to provide a polymer, photochromic, which exhibits photochromism in a solid state and can contain a photochromic component uniformly and in a high density in the polymer. It is to provide a material and an optical functional element. Another object of the present invention is to obtain a polymer having high heat resistance. Means for solving the problem

[0014] (1) As a result of intensive studies to solve the above problems, the present inventors have found that the above-described problems can be solved by a diphenyl cyclopentene having a specific substituent. That is, the present invention is as follows.

[0015] The present invention is a diacetylcyclopentene compound represented by the following general formula (I).

[Chemical 3]

(Wherein R ¹ represents a hydrogen (H) or fluorine (F) atom, R ² represents a hydrogen (H) or methyl group, R ³ represents a methyl group, a methoxy group, a trimethylsilyl group, R ⁴ and R ⁵ may be the same or different and each represents hydrogen (H) or an amino group capable of protonation.

[0016] Further, the present invention is a photochromic material containing the above-mentioned dichelcyclopentene compound.

[0017] Further, the present invention may be an optical functional device including the photochromic material.

[0018] (2) As a result of intensive studies to solve the above-mentioned problem, the present inventor has found that the above-mentioned problem can be solved by introducing a diphenylcyclopentene compound represented by the chemical formula (Π) into the polymer. I found it. That is, the present invention is as follows.

[0019] The present invention is a styrene polymer having a repeating unit represented by the following general formula (Π).

(In the formula (Π), R represents a cyclohexyloxy group.)

[0020] The present invention is also a photochromic material containing the styrene polymer.

[0021] Further, the present invention may be an optical functional device including the photochromic material.

The invention's effect

[0022] (1) The present invention provides a display material in which both of the two isomers generated by light irradiation are thermally relatively stable and can be easily returned to a non-colored state. be able to.

[0023] Further, according to the present invention, it is possible to provide a dicenylcyclopentene-based material that reacts irreversibly with ultraviolet light. Furthermore, it is possible to provide a novel dichelcyclopentene material that is colored red.

[0024] According to the present invention, it is possible to provide a novel photochromic material that reversibly shows photochromism by light and that irreversibly discolors by heating.

[0025] (2) In addition, the present invention exhibits photochromism in a solid state, It is possible to provide a display material that is uniform and highly dense.

Brief Description of Drawings

[FIG. 1] FIG. 1 is a diagram showing the state of spectrum change of a coloring reaction and a decoloring reaction by light irradiation of a compound (la-H) in acetonitrile.

[FIG. 2] FIG. 2 is a diagram showing a change in spectrum when trifluoromethanesulfonic acid is added to (a) compound (la—H) and (b) compound (lb—H) in acetonitrile. is there.

FIG. 3 is a graph showing the protonation rate of amino groups when an acid is added to compound (la—H) and compound (lb—H).

FIG. 4 is a diagram showing the thermal fading reaction of compound (lb—H) and compound (2b—H) at 60 ° C.

FIG. 5 is a graph showing the progress of thermal fading at 30 ° C., 50 ° C. and 60 ° C., although 3 equivalents of trifluoromethanesulfonic acid is added to the compound (lb-H).

[Figure 6] Figure 6 is a logarithmic plot of the change in absorption spectrum from the data in Figure 5.

[FIG. 7] FIG. 7 is a graph showing the temperature dependence of the velocity coefficient obtained for the slope force of the primary plot of FIG.

[FIG. 8] FIG. 8 is a diagram showing the state of spectrum change of the coloring reaction and decoloring reaction of compound (la-F) by light irradiation in acetonitrile.

[FIG. 9] FIG. 9 is a graph showing a change in spectrum when trifluoromethanesulfonic acid is added to a compound (la-F) in acetonitrile.

FIG. 10 is a diagram showing the protonation rate of amino groups when acid is added to compound (la-F) in acetonitrile.

FIG. 11 is a diagram showing the thermal fading reaction of compound (lb-F) and compound (2b-F) at 80 ° C.

[FIG. 12] FIG. 12 is a logarithmic plot of the change in absorption spectrum from the data in FIG.

FIG. 13 is a graph showing the temperature dependence of the thermal fading reaction rate coefficient of the compound (lb-F) and the compound (2b-F). FIG. 14 is a diagram showing a state of spectrum change of a coloring reaction and a decoloring reaction due to light irradiation of a compound (la′-H) in acetonitrile.

[FIG. 15] FIG. 15 is a diagram comparing the photostability of the diphenylcyclopentene compounds (lb′—H) and (1 b—H) and the dithiylberberfluorocyclopentene compounds of this example. is there.

FIG. 16 is a diagram showing a change in spectrum when trifluoromethanesulfonic acid is added to a compound (la′—H) and a compound (lb′—H) in acetonitrile.

FIG. 17 is a diagram showing a fading reaction at 25 ° C. under a certain place of compound (lb′—H).

[FIG. 18] FIG. 18 is a view showing a state of spectrum change of a coloring reaction and a decoloring reaction due to light irradiation of a compound (la′-F) in acetonitrile.

FIG. 19 is a view showing a change in spectrum when trifluoromethanesulfonic acid is added to the compound (la′-F) and the compound (lb′-F) in acetonitrile.

[FIG. 20] FIG. 20 shows the results when the compound (la′-F) of this example was added with trifluoromethanesulfonic acid and then irradiated with ultraviolet light and left at 40 ° C. and 60 ° C. under some conditions. Absorption spectrum change

FIG. 21 is a diagram showing a state of spectrum change of a coloring reaction and a decoloring reaction due to light irradiation of a compound (la′′F) in hexane.

FIG. 22 is a diagram showing a thermal fading reaction of compound (lb ′ ,, 1 F) at 50 ° C. in hexane.

[FIG. 23] FIG. 23 is a graph showing the attenuation of absorbance of compound (lb ′, 1F) in hexane at 30-60 ° C.

[FIG. 24] FIG. 24 is a logarithmic plot of the change in absorption spectrum from the data in FIG.

[FIG. 25] FIG. 25 is a graph showing the temperature dependence of the thermal fading reaction rate coefficient obtained from the gradient force of the primary plot of FIG.

[FIG. 26] FIG. 26 is a diagram showing an outline of synthesizing a styrene monomer having the di-cyclopentene of the present invention.

[FIG. 27] FIG. 27 shows a DSC curve obtained by measuring the differential scanning calorimetry of the polymer (poly (la-M)). It is a figure.

FIG. 28 is a diagram showing a change in ultraviolet-visible absorption spectrum when ultraviolet light is irradiated in a toluene solution of a polymer (poly (la-M)) and in a film.

[FIG. 29] FIG. 29 is a graph showing a change in reaction rate when ultraviolet light is irradiated in a toluene solution of a polymer (poly (la-M)) and in a film.

FIG. 30 shows 110 ° C., 120 ° C., 130 in a polymer (poly (lb-M)) film. It is a figure which shows progress of thermal fading in C, 140 degreeC, and 150 degreeC.

[FIG. 31] FIG. 31 is a plot of the change in absorption spectrum logarithmically from the data in FIG.

[FIG. 32] FIG. 32 is a graph showing the temperature dependence of the thermal fading reaction rate coefficient obtained from the gradient force of the primary plot of FIG.

FIG. 33 is a graph showing changes in Tg when 1-adamantyl methacrylate is prepared as a copolymer.

FIG. 34 is a view showing a DSC curve of a copolymer Poly ((la-M) -co- (1-adamantyl methacrylate)).

FIG. 35 is a view showing a thermogravimetric analysis curve of a copolymer Poly ((la-M) -co- (1-adamantyl methacrylate)).

[Fig.36] Fig.36 shows the thermal fading coefficient of polymer (Poly (lb-M)) (○) and copolymer (Poly ((la-M) -co- (1-adamantyl methacrylate)) (參) FIG.

BEST MODE FOR CARRYING OUT THE INVENTION

A. Dicercyclopentene compounds

[Dice-cyclopentene compound]

The diphenylcyclopentene compound of the present invention is represented by the following general formula a).

[Chemical 5]

[0028] The amino group is not particularly limited as long as it can be protonated in the presence of an acid. Specific examples include an amino group substituted with an alkyl group. Preferred alkyl groups are those having 1 to 10 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, tert-butyl group, pentyl group. Group, octyl group and the like.

[0029] The di-cyclopentene compound represented by the general formula (I) is! By changing ^ ~, (1) a compound that can switch between P-type photochromism and T-type photochromism in the presence of acid, (2) a compound that can be heated and decolored by adding acid, (3) Different compounds can be obtained from blue to red.

[0030] (1) In the diphenylcyclopentene compound represented by the general formula (I), when R ³ is a methyl group and R ⁴ is an amino group capable of protonation, the light is removed under neutral conditions. Irradiation generates two isomers reversibly as shown in the following reaction formula. It has the property of reversibly changing optical properties such as light absorption coefficient, refractive index, optical rotation, and dielectric constant in response to the change in molecular structure due to photochemical reaction. These two isomers (la-H, lb-H) exhibit P-type photochromism that is thermally stable at room temperature. When the compound represented by the general formula (lb—H) is placed in the presence of an acid, the amino group is protonated to produce the compound (2b—H). Compound (2b-H) differs from the optical properties of compound (lb-H). In the compound (2b—H), the amino group is deprotonated in the presence of alkali to produce the compound (lb—H). Compound (2b-H) is unstable at room temperature, and is heated to produce compound (2a-H). In addition, compound (2a-H) and compound (2b-H) reversibly generate two structural isomers with different colors upon irradiation with light. In addition, the compound (2b-H) is a compound that exhibits a T-type photochromium whose state caused by light irradiation is thermally unstable at room temperature. Compound (2a-H) can also be obtained by placing compound (la-H) in the presence of an acid and protonating the amino group. In the compound (2a-H), the amino group is deprotonated in the presence of an alkyl group to produce the compound (la-H). That is, the di-cyclocyclopentene compound of the present invention undergoes a series of reactions by light irradiation, heat treatment, and acid / alkali treatment, as shown in the following chemical formula.

[Chemical 6]

[0032] As described above, the dichelcyclopentene compound of the present invention has P-type photochromism and T The type photochromism can be switched by having an amino group capable of protonation in the molecule. That is, in the present invention, the role of an amino group capable of protonation is important.

(2) In the dicyclocyclopentene compound represented by the general formula (I), when R ³ is a methoxy group and R ⁴ is an amino group capable of protonation, ultraviolet light is used under neutral conditions. As shown in the following reaction formula, the reaction proceeds irreversibly. The molecular structure changes due to the photochemical reaction, and in accordance with this change, it has the property of reversibly changing optical characteristics such as the light absorption coefficient, refractive index, optical rotation or dielectric constant. The isomer (lb ') is stable to visible light.

When the compound represented by the general formula (lb ′) is placed in the presence of an acid, the amino group is protonated to produce the compound (2b ′). Compound (2b ′) differs from the optical properties of compound (lb ′). In the compound (2b ′), the amino group is deprotonated in the presence of alkali to produce the compound (lb ′). The compound (2b ′) becomes a separate compound by heating and is almost colorless. In addition, when the compound (2a ′) is irradiated with ultraviolet rays, the compound (2b ′) is irreversibly generated. Compound (2a ′) can also be obtained by placing compound (la ′) in the presence of an acid and protonating the amino group. In the compound (2a ′), the amino group is deprotonated in the presence of alkali to produce the compound (la ′). That is, the diphenylcyclopentene compound of the present invention undergoes a series of reactions by light irradiation, heat treatment, acid and alkali treatment as shown in the following chemical formula. Such an irreversible photochromic material can be used for a temperature sensor, for example.

[Chemical 7]

Heat erase

(3) In the diphenylcyclopentene compound represented by the general formula (I), when R ² is a methyl group, R ³ catoxy group, and R ⁴ is an amino group capable of protonation, neutral conditions Thus, a compound (lb '') that develops a red color is generated upon irradiation with ultraviolet rays.

[Chemical 8]

(1 a (1 (4) In the diphenylcyclopentene compound represented by the general formula (I), when R ³ is a trimethylsilyl group, the following reaction formula is obtained by irradiation with light under neutral conditions. As shown in The two isomers are reversibly produced. The molecular structure changes due to photochemical reaction, and according to this change, it has the property of reversibly changing optical properties such as light absorption coefficient, refractive index, optical rotation or dielectric constant. These two isomers (la ''',lb''') show photochromism. In addition, the compound (la ′,) was thermally stable. The compound (lb ',,) becomes a separate compound when heated and loses its color.

[Chemical 9]

Heat erase

[0037] [Synthesis of Dicenylcyclopentene Compound]

The diphenylcyclopentene compound represented by the general formula (I) can be produced by a known method as shown in Examples.

[0038] Since the diphenylcyclopentene compound of the present invention causes a photoreaction and exhibits photochromism, a material containing the compound can be used as a photochromic material useful for various optical functional elements, for example. In the case of (1) above, in particular, by using an acid, the dichelcyclopentene compound of the present invention can switch between P-type photochromism and T-type photochromism, so that recording and erasing of information can be easily repeated. Can do.

An optical functional element such as an optical memory element or an optical switching element can be produced by using such a mechanism and a change in optical characteristics accompanying the mechanism.

[0040] When used for an optical switching element, for example, a thin film is formed using a photochromic material containing the di-cyclopentene-based compound of the present invention, and an optical switching element is manufactured using the thin film. By utilizing the large refractive index change of the photochromic material Therefore, the element can be miniaturized, which is preferable.

When used in an optical memory element, for example, a thin film is formed using a photochromic material containing a diphenylcyclopentene compound of the present invention, and an optical memory element is produced using this as a recording layer. The photon mode recording on the recording layer makes it possible to significantly improve the recording density, which is preferable. By using a multiphoton absorption reaction, three-dimensional recording is also possible, so the recording capacity can be improved. It is possible and more preferable.

[0042] Further, in the case of the dichelcyclopentene compound of the above (2), since it is not decolored by visible light, it can be used as an irreversible optical recording element. The dichelcyclopentene compound (2) can be decolorized by heating, and can be used as a heating sensor.

[0043] Further, in the case of the dichelic cyclopentene compound of (3) above, since it is not decolorized by visible light, it can be used as an irreversible optical recording element, and a photochromic material colored in red, which has not been obtained conventionally, is obtained. be able to. It can be used as a radiation checker.

[0044] Further, in the case of the above-mentioned (4) di-cyclocyclopentene compound, it can be decolored by heating, so that it can be used as a heating sensor.

[0045] The presence of the dicenylcyclopentene compound of the present invention can be confirmed by a general organic analysis technique such as nuclear magnetic resonance sputtering, mass spectrometry, and high performance liquid chromatography.

[0046] In the present invention, when an acid is used, the amount of the acid used is 1 molar equivalent or more, preferably 1 to 5 molar equivalents, more preferably, with respect to the di-cyclopentapentene compound of the present invention. Or 2 to 4 molar equivalents.

[0047] As the acid to be used, trifluoromethanesulfonic acid, acetic acid, hydrochloric acid and the like are used.

Further, as the base to be used, triethylamine or the like is used.

[0048] The acid may be used in the state of being dissolved in a solvent such as acetonitrile, or the solvent may not be used. In addition, when protonation is performed using an acid, heating from room temperature to about 150 ° C. is preferable because the reaction is accelerated. When no solvent is used, two isomers are reversibly produced when irradiated with light in the state where the diphenylcyclopentene compound of the present invention and an acid coexist. The presence of acid does not have a significant effect on this reaction. In the case of conducting a protonic reaction using an acid, heating may be performed. By heating, the acid is Surrounds the periphery of the otochromic material and protonates the amino group. Upon cooling, the acid leaves the photochromic material. Thereby, a photochromic material can be decolored.

B. Styrene polymer with di-cyclopentene

The styrene polymer having dicenylcyclopentene of the present invention has a repeating unit represented by the following general formula (II), and is obtained by radical polymerization of a compound represented by the following general formula (V). It is done.

[Chemical 5]

(In the formula (Π), R represents a cyclohexyloxy group.)

[Chemical 6]

(In the formula (V), R represents a cyclohexyloxy group.)

[0050] The styrene polymer having di-cyclocyclopentene of the present invention comprises a compound represented by the general formula (V) in the presence of 2, 2'-azobisisobutyl nitrile (AIB N) as a radical polymerization initiator. Obtained by radical polymerization under pressure. Examples of the solvent used for the polymerization include cyclohexane and toluene. The number average molecular weight of the polymer photochromic material of the present invention is preferably 1,000 to 100,000, more preferably 10,000 to 40,000, and polydispersity (weight average molecular weight and number average). The ratio to the molecular weight is about 1.6 to 2.1, and the glass transition temperature (Tg) is 104 ° C.

[0051] The styrene polymer having the dicyclocyclopentene of the present invention is obtained by irradiating light with two polymers (Poly (la-M) and Poly (lb-M)) as shown in the following reaction formula (VI). Generate reversibly. It has the property of reversibly changing optical properties such as light absorption coefficient, refractive index, optical rotation or dielectric constant according to this change due to the change in molecular structure due to photochemical reaction. In addition, by heating Poly (lb— M) at a temperature higher than 100 ° C, Poly (la— M) Is generated. That is, the styrene polymer having the dicyclocyclopentene of the present invention undergoes a reversible reaction by light irradiation and heat treatment.

[Chemical 7]

(In the formula (VI), R represents a cyclohexyloxy group.)

[0052] The polymer photochromic material of the present invention may contain other copolymerization components as long as the photochromism is not inhibited. By including other copolymerization components in this way, a polymer having a high Tg can be obtained. Usually, when other copolymerization monomers are included, the photochromism of the photochromic material of the present invention tends to decrease, and therefore the content of other copolymerization components may be appropriately adjusted depending on the balance between photochromism and Tg.

[0053] For example, a copolymer having a high Tg can be obtained by copolymerizing the dicyclocyclopentene of the present invention with 1-adamantyl methacrylate, N-1-adamantyl maleimide, or the like.

[0054] The optical recording medium of the present invention can be obtained by forming a recording layer containing a polymer photochromic material having a repeating unit represented by the general formula (式) of the present invention on a substrate. . The substrate is appropriately selected from those usually used which may be transparent or opaque to the light used. Specific materials for the substrate include power such as glass, plastic, paper, plate-like or foil-like metal such as aluminum. Among these, plastic is preferred from various points of view. Examples of plastics include acrylic resin, methallyl resin, vinyl acetate resin, vinyl chloride resin, nitrocellulose, polyethylene resin, polypropylene resin, polycarbonate resin, polyimide resin, and polysulfone resin. . [0055] The recording layer is formed on the substrate by dissolving the polymer photochromic material of the present invention in a suitable solvent together with a nonder resin if necessary, and using a doctor blade method, a casting method, a spinner method, an immersion method. By such means, it is applied so as to form a thin film having a film thickness of 2 nm to 50 μm, preferably 10 nm to 30 μm. Examples of the binder resin used include phenol resin, polycarbonate resin, polystyrene resin, and (meth) acrylic resin such as methyl poly (meth) acrylate. In general, it leads to a decrease in the concentration of the galleureten structure.

It is most desirable to use noinder resin but not more than the same amount as that of the polymer photochromic material of the present invention, more preferably less than half. Examples of the solvent include toluene, xylene, black benzene, methyl ethyl ketone, and ethyl acetate.

[0056] The content of the polymer photochromic material of the present invention in the formed recording layer is not particularly limited, but can be appropriately determined in consideration of the absorbance of the substance, the intensity of light emission, and the like. The recording layer may be provided on only one side of the substrate or on both sides. Further, a protective film such as an ultraviolet curable resin can be provided on the recording layer for the purpose of improving the weather resistance. Recording on the optical recording medium of the present invention is performed by irradiating the converged light on the recording layer provided on the substrate.

Example 1

[Example 1]

1— (2—Methyl—5—Ferre 3—Chel) —2— (2—Methyl—5— p— Ν, Ν— Jetylaminophenol—3—Chel) cyclopentene is They can be synthesized by the methods of Synthesis Example 1 and Synthesis Example 2.

[Synthesis Example 1]

Under an argon atmosphere, 0.50 g (l. 5 mmol) of 1,2-bis (2-methyl-5-chloro-3-cyl) cyclopentene was dissolved in 4 mL of anhydrous tetrahydrofuran (THF). Thereto, 3.0 mL (4.8 mmol) of a 1.6 mol / L n-butyllithium hexane solution was slowly added dropwise. After stirring at room temperature for 30 minutes, 1.3 mL (l.lg; 4.8 mmol) of tri-n-butyl borate was added all at once. The reaction was completed by stirring at room temperature for 1 hour. To this solution, 0.84 g (3. Ommol) of p-dodo N, N-jetinorea-phosphorus and 3.5 mL of THF are added, and then added to the solution. 0.10 g (0. 83 mmol) of trakis (triphenylphosphine) palladium (0) was added, and 2 drops of 2 mol ZL sodium carbonate aqueous solution and 3 drops of ethylene glycol were added and stirred. After refluxing for 3 hours and returning to room temperature, the organic layer was taken out by adding water and jetyl ether, and further extracted with jetyl ether. The organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off. Using silica gel column chromatography, a mixed solution of hexane: ethyl acetate (95: 5 (volume ratio)) has a 1- (2-methyl-5-phenol--containing a dethylamino group at one end of the molecule. (Lu 3—Chel) —2— (2—Methyl—5— p— Ν, Ν— Jetylaminophenol—3-Chel) cyclopentene (1 a——) was separated and purified. The yield was 0.083 g, and the yield was 10%.

1H-NMR (400 MHz, CDC1 TMS) δ = 1.16 (t, J = 7.2Hz, 6H), 1.95 (

3,

s, 3H), 1.98 (s, 3H), 2.05 (quintet, J = 7.6Hz, 2H), 2.83 (t, J = 7.6H z, 4H), 3.35 (q, J = 7.2Hz, 4H), 6.62 (d, J = 8.8Hz 2H), 6.85 (s, 1H), 7.05 (s, 1H), 7.2-7.6 (m, 7H)

[0058] [Yi 8]

[0059] Under an argon atmosphere, 1.0 g (3. Ommol) of 1,2-bis (2-methyl-5-chloro-3-chel) cyclopentene was dissolved in 20 mL of anhydrous tetrahydrofuran (THF). Then, 1.9 mL (3. Ommol) of a 1.6 mol / L n-butyllithium hexane solution was slowly dropped. After stirring at room temperature for 30 minutes, 1.3 mL (l. Lg; 4.8 mmol) of tri-n-butyl borate was added all at once. The reaction was completed by stirring at room temperature for 1 hour. To this solution, add 0.62 g (3. Ommol) of Eodobenzene and 15 mL of THF, and add tetrakis (triphenylphosphine). In) Palladium (0) (0.10 g, 0.083 mmol) was added, and 12 mL of 2 mol ZL aqueous sodium carbonate solution and 3 drops of ethylene glycol were added and stirred. After refluxing for 3 hours and returning to room temperature, the organic layer was taken out with water and jetyl ether and extracted with jetyl ether. The organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off. Using silica gel column chromatography, a mixed solution of hexane: ethyl acetate (95: 5 (volume ratio)) was used to make a 1- (2-methyl-5-ferrule 3 cha) 2-2 (2 —Methyl 5 chloro-3 chale) cyclopentene was separated and purified. The yield was 0.73 g and the yield was 65%.

'H-NMR (400MHz, CDC1, TMS) δ = 1. 88 (s, 3Η), 1. 99 (s, 3H), 2. 05

Three

(quintet, J = 7.6Hz, 2H), 2.75 (t, J = 7.6Hz, 2H), 2.81 (t, J = 7.6Hz, 2H), 6.62 (s, 1H) , 6. 99 (s, 1H), 7. 2— 7. 6 (m, 5H)

Under an argon atmosphere, 1 (2-methyl-5 ferrule 3 chas) -2- (2-methyl-5 cyclotane 3 chas) cyclopentene 0.35 g (0.994 mmol) in anhydrous tetrahydrofuran (THF) was dissolved in 6 mL. Thereto, 0.66 mL (0.96 mmol) of a 1.46 mol / L t-butyllithium pentane solution was slowly added dropwise. After stirring at 0 ° C. for 1 hour, 0.38 mL (0.32 g; l. 4 mmol) of tri-n-butyl borate was added all at once. The reaction was terminated by stirring for 1 hour at room temperature. In this solution, p 6-N, N jetylline 0.26 g (0.94 mmol) and THF 15 mL were added, and tetrakis (triphenylphosphine) paradium (0) 0.032 g (0.026 mmol) ) Was added, and 4 mL of a 2 mol ZL aqueous sodium carbonate solution and a few drops of ethylene glycol were added and stirred. After refluxing for 2 hours and returning to room temperature, the organic layer was removed by adding water and jetyl ether, and further extracted with jetyl ether.

. The organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off. Using silica gel column chromatography, a mixed solution of hexane: ethyl acetate (95: 5 (volume ratio)) was used to determine 1— (2-methyl-5-ferro 3 chas) —2— (2 —Methyl-5—p—Ν, Ν Jetylaminophenol 3 chalcole) cyclopentene (1 a- Η) was isolated and purified. The yield was 0.030 g and the yield was 6.6%. H-NMR (400MHz, CDC1 TMS) δ = 1.16 (t, J = 7.2Hz, 6H), 1.95 (s

3,

3H), 1.98 (s, 3H), 2.05 (quintet, J = 7.6Hz, 2H), 2.83 (t, J = 7.6Hz, 4H), 3.35 (q, J = 7.2Hz, 4H), 6.62 (d, J = 8.8Hz, 2H), 6.85 (s, 1H), 7.05 (s, 1H), 7.2-7.6 (m, 7H)

[Chemical 9]

1— (2-Methyl-5-ferro-3 chael) —2— (2-methyl-5-ρ-Ν, Ν-jetylaminophenol having a jetylamino group at one end of the synthesized molecule -Lu-Chenyl) cyclopentene (la-Η) reacts as shown in the following chemical formula. Hereinafter, experimental examples will be described based on the following chemical formula.

[Chemical 10]

[0063] [Change in absorption spectrum associated with photochromism]

Diceryl cyclopentene (la-H) having a jetylamino group at one end of the synthesized molecule showed a thermally stable photochromism in a neutral acetonitrile solution. When the colorless (la-H) solution was irradiated with ultraviolet light, the solution turned purple (lb-Pi) and changed to a spectrum having an absorption maximum at 540 nm.

[0064] FIG. 1 is a diagram showing a state of spectrum change between a coloring reaction and a decoloring reaction. From this result, it was found that the diphenylcyclopentene compound of the present invention exhibits a normal photochromism that causes a coloring reaction by ultraviolet irradiation and a fading reaction by visible light irradiation.

[0065] [Spectrum change due to acid addition]

Fig. 2 is a diagram showing the change in spectrum when trifluoromethanesulfonic acid is added in acetonitrile. From this figure, it can be seen that if about 3 equivalents of trifluoromethanesulfonic acid is added to the compound (la-H), the spectral change is eliminated.

FIG. 3 is a diagram showing the proton ratio of an amino group when an acid is added. From this figure, it was found that in the acetonitrile, the amino group was almost protonated when about 3 equivalents of trifluoromethanesulfonic acid was added.

FIG. 4 is a diagram showing a thermal fading reaction at 60 ° C. In the figure, the lb graph is for trifluoromethanesulfonic acid without addition, and 2b is 10 equivalents of trifluoromethanesulfonic acid. It is added. From this figure, the compound (lb-H) obtained by irradiating the compound (la-H) with ultraviolet light, which contains 10 equivalents of trifluoromethanesulfonic acid, was heated at 60 ° C for 2 hours. On standing, the solution returned to almost colorless, and its absorption spectrum coincided with the absorption spectrum of (2a-H) having an absorption maximum at 281 nm. In addition, the solution of 2b returned to colorless even after being left at room temperature for 3 days. That is, (2b-H) was found to show a heat return reaction at room temperature. On the other hand, under neutral conditions, the compound (lb—H) did not show a heat return reaction at 60 ° C. as well as at room temperature. From this result, it became clear that the diphenylcyclopentene compound of the present invention can switch between P-type photochromism and T-type photochromism by adding acid.

[0068] [Fade rate coefficient]

Figure 5 shows the compound (lb—H) with 3 equivalents of trifluoromethanesulfonic acid. It is a figure which shows progress of thermal fading in C, 50 degreeC, and 60 degreeC. From this figure, it can be seen that the progression of thermal fading is promoted by heating. Figure 6 is a logarithmic plot of the change in absorption spectrum from the data in Figure 5. FIG. 7 is a graph showing the temperature dependence of the thermal fading reaction rate coefficient obtained from the slope of the primary plot of FIG. From this figure, it was estimated that the thermal fading speed increased due to heating, and fading occurred at several seconds (about 6 seconds) at 120 ° C.

[0069] (Example 2)

[Synthesis example]

To a mixed solution of 230 mL of acetic acid and 10 mL of water, 27 g (0.27 mol) of 2-methylthiophene was added. Bromine 28mL (0.55mol) was slowly added dropwise at room temperature and stirred for 8 hours. The mixture was neutralized with an aqueous sodium hydroxide solution and extracted with ether. The organic layer was washed with an aqueous sodium thiosulfate solution and dried over magnesium sulfate. Magnesium sulfate was removed by filtration, and the solvent was distilled off with an evaporator. 2,4 Jib mouth moe 5-methylthiophene was isolated as a fraction at 75 ° C / 0.5 KPa by vacuum distillation.

Yield 56g, Yield 80%

'H-NMR (400MHz, CDC1, TMS): δ = 2.33 (s, 3H), 6. 85 (s, 1H) [Chemical 11]

[0070] Next, in an argon atmosphere, 5.0 g (19.6 mmol) of 2,4-dib-mouthed 5-methylthiophene was dissolved in 50 mL of tetrahydrofuran (THF) at -78 ° C to obtain 1.6 M n-butyllithiate. The hexane solution 12.8 mL (20.5 mmol) was slowly added dropwise and stirred for 2 hours. To this, 7.9 mL (20.4 mmol) of tributyl borate was slowly added dropwise and stirred at −78 ° C. for 2 hours. The mixture was diluted with water to obtain tetrakistriphenylphosphine palladium (0) 0.64 g (0.56 mmol), odobenzene 4. Og (19.6 mmol), 2 mol ZL aqueous sodium carbonate solution 5 mL, and tetrahydrofuran 150 mL. Refluxed at 80 ° C for 7.5 hours. Thereafter, the mixture was neutralized with hydrochloric acid and extracted with ether. The organic layer was dried over magnesium sulfate, filtered, and concentrated 3-bromo-2-methyl-5-phenolthiophene was isolated using a silica gel column with hexane as a developing solvent (R = 0 53).

f

Yield 3. Og, Yield 56.3%

'H-NMR (400MHz, CDC1, TMS) δ = 2. 42 (s, 3Η), 7. l l (s, 1H), 7.2

Three

5- 7. 52 (m, 5H)

[Chemical 12]

[0071] Next, 3-bromo-2-methyl-5-phenol-off at −78 ° C. in an argon atmosphere. 1.0 g (4. Ommol) of ethylene was dissolved in lOOmL of tetrahydrofuran, and 2.7mL (4.4 mmol) of 1.6molZL n-butyllithium hexane solution was slowly added dropwise. The mixture was cooled to 95 ° C, and 0.6 mL (4.3 mmol) of octafluorocyclopentene was added all at once. 1. After stirring for 5 hours, the mixture was returned to room temperature and taented with water. Extraction with ether, drying over magnesium sulfate, filtration and concentration of the organic layer. 1- (2-Methyl-5 felt 3 cell) heptafluorocyclopentene was purified on a silica gel column using hexane as a developing solvent (R = 0.58). Further purification by high performance liquid chromatography (HPLC) f

Went.

Yield 0.76g, Yield 52%

'H-NMR (400MHz, CDC1, TMS) δ = 2. 48 (s, 3Η), 7. 24— 7. 56 (m,

Three

6H)

[Chemical 13]

Under argon atmosphere, 2, 4 dib-mouthed mortar 5-methylthiophene 2.8g (ll mmol) was dissolved in tetrahydrofuran lOOmL, and 1.6molZL n-butynole lithium hexane solution 7.lmL (l lmmol) was slowly added dropwise and stirred for 1 hour. Thereto, tributyl borate 5. OmL (13 mmol) was slowly added dropwise and stirred at 78 ° C. for 1 hour. Quench with water, tetrakistriphenylphosphine palladium (0) 0.35 g (0.56 mmol), p — ododo N, N Jetylaminobenzene 3. Og (l lmmol), 2 mol ZL sodium carbonate aqueous solution 2. 5mL and tetrahydrofuran lOOmL were added. Refluxed at 80 ° C for 3 hours. Thereafter, the mixture was neutralized with hydrochloric acid and extracted with ether. Dry organic layer with magnesium sulfate After drying, filtration and concentration of 3 bromo-2-methyl-5- (pN, N-jetylaminophenol) thiophene was purified by recrystallization of hexane force.

Yield 1.3g, Yield 37%

'H-NMR (400MHz, CDC1, TMS) δ = 1.18 (t, J = 7.2Hz, 6H), 2.38 (s

Three

, 3H), 3.37 (d, J = 7.2Hz, 4H), 6.65 (d, J = 8.8Hz, 2H), 6.90 (s, 1H), 7.35 (d, J = 8.8Hz, 2H)

[Chemical 14]

In an argon atmosphere, dissolve 0.50 g (l.5 mmol) of 3 bromo-2-methyl-5- (p-N, N-deethylaminophenol) thiophene in 10 mL of tetrahydrofuran at 78 ° C and add 1.6 mol / L n-butyllithium hexane. Solution 1. 1 mL (l.8 mmol) was slowly added dropwise and stirred for 1 hour. 1- (2-Methyl 5-Ferru 3 Cha) heptafluorocyclopentene 0.56g (l.5mmol) and tetrahydrofuran 5ml mixed solution was slowly added dropwise at -78 ° C. And stirred for 3 hours. Taentied with water and extracted with ether. The organic layer was dried over magnesium sulfate, removed by filtration, and the organic layer was concentrated. 1- (2-Methyl-5-p-N, N Jetylaminophenol 3 chael) — 2— (2 Methyl-5 phenyl 3 cheryl) octafluorocyclopentene is hexane as developing solvent Separation and purification by silica gel column chromatography (R = 0.2).

f Further purified by high performance liquid chromatography (HPLC).

Yield 0.43g, Yield 49%

'H-NMR (400MHz, CDC1, TMS) δ = 1.18 (t, J = 7.2Hz, 6H), 1.92 (s

Three

, 3H), 1.95 (s, 3H), 3.37 (q, J = 7.2Hz, 4H), 6.65 (d, 8.8Hz, 2H), 7.08 (s, 1H), 7.29-7.40 (m, 6H) , 7.54 (d, J = 7.2Hz, 2H) FAB -MS m / z = 591 (M ⁺ ) [Chemical 15]

Diacetylcyclopentene (la-F) having a jetylamino group at one end of the synthesized molecule reacts as shown in the following chemical formula. Hereinafter, experimental examples will be described based on the following chemical formula.

[Chemical 16]

(2 a (2 b- [Change in absorption spectrum associated with photochromism] Diceryl cyclopentene (la-F) having a jetylamino group at one end of the synthesized molecule showed a thermally stable photochromism in a neutral acetonitrile solution. When the colorless (la-F) solution was irradiated with ultraviolet light, the solution was colored purple (lb-F) and changed to a spectrum having an absorption maximum at 630 nm.

FIG. 8 is a diagram showing the state of spectrum change between the coloring reaction and the decoloring reaction. From this result, it was found that the diphenylcyclopentene compound of the present invention exhibits a normal photochromism that causes a coloring reaction by ultraviolet irradiation and a fading reaction by visible light irradiation.

[0077] [Spectrum change due to acid addition]

FIG. 9 is a diagram showing a change in spectrum when trifluoromethanesulfonic acid is added in acetonitrile. From this figure, it can be seen that if about 3 equivalents of compound (la-F) and about 6 equivalents of trifluoromethanesulfonic acid are added to compound (lb-F), the spectral change is eliminated.

FIG. 10 is a diagram showing the proton ratio of an amino group when an acid is added. From this figure, it can be seen that in diphenylcyclopentene, if about 6 equivalents of trifluoromethanesulfonic acid is added, the amino groups of both compounds (la-F) and (lb-F) are almost protonated. Wakatsuta o

FIG. 11 is a diagram showing a thermal fading reaction at 80 ° C. The white circles in the figure are those without trifluoromethanesulfonic acid (lb-F), and the black circles are those with 10 equivalents of trifluoromethanesulfonic acid (2b-F). From this figure, the compound (lb-F) obtained by irradiating the compound (la-F) with ultraviolet light, which is obtained by adding 10 equivalents of trifluoromethanesulfonic acid (2b-F), When the solution was allowed to stand at 80 ° C for 10 hours, the solution returned to almost colorless, and the absorption spectrum coincided with the absorption spectrum of (la-F) having an absorption maximum at 293 nm. On the other hand, under neutral conditions, the compound (lb-F) did not show a heat return reaction at 60 ° C as well as at room temperature. From this result, it has been clarified that the diphenylcyclopentene compound of the present invention has a heat regeneration function by adding an acid.

[0080] [Fade rate coefficient]

FIG. 12 is a logarithmic plot of the change in absorption spectrum from the data in FIG. Figure 13 shows the logarithm of the rate coefficient obtained at various temperatures for the compound (lb-F) and trifluoromethanesulfonic acid 10 equivalents (2b-F). From this figure, the compound (lb-F) is stable at 30 ° C for several years, and when 10 equivalents of trifluoromethanesulfonic acid is added, the thermal fading rate increases with heating, and at 160 ° C, it takes several tens of seconds. It was estimated that the color would fade.

[Example 3]

[Synthesis Example 3]

The flask was charged with 12 g of 2-methoxy-4-methylthiophene (0. 92 mol), 200 mL of hexane and 20 mL of acetic acid, and cooled to 0 ° C. with an ice-water bath. N-chlorosuccinimide (13.5 g, 0.1 mol) was added little by little, and the mixture was stirred for 3 hours in an ice-water bath. After completion of the reaction, the reaction mixture was neutralized with an aqueous sodium hydroxide solution, then extracted with ether, and the organic layer was washed with an aqueous sodium chloride solution. It was dried over anhydrous magnesium sulfate, filtered and concentrated to synthesize 2-chloro-3-methyl 5-methoxythiophene. NMR showed almost no impurities and was used in the next reaction without further purification. The yield was 12 g and the yield was 82%.

'H-NMR (400MHz, CDC1, TMS) δ = 2.08 (s, 3Η, CH), 3.82 (s, 1H,

3 3

OCH), 5. 87 (s, 1H, thienyl H).

[Chemical 17]

[0082] 1.6 g (12 mmol) of aluminum chloride was added to 10 mL of dry carbon disulfide and cooled in an ice-water bath. To this was added dropwise a solution of 2-chloromethyl 3-methyl 5-methoxythiophene 1.0 g (6. Ommol), pentadioic acid chloride 0.52 g (3. l mmol), and carbon disulfide 2 mL at 0 ° C. Then, the mixture was stirred at room temperature for 1 hour to synthesize 1,5 bis (2-capped 3-methyl-5-methoxy-4 cell) pentane-1,5 dione. After the reaction, water was added, extracted with ether, dried over anhydrous magnesium sulfate, filtered and concentrated. 1, 5 screws (2— 1-methyl-1,5-methoxy-1,4-cell) pentane-1,5-dione was purified by recrystallization from acetone. The yield was 39 mg and the yield was 3.0%.

'H-NMR (400MHz, CDC1, TMS) δ = 2.01 (quintet, J = 7.2 Hz, 2H, CH

Three

), 2.27 (s, 6H, CH), 2.87 (t, J = 7.2Hz, 4H, CH), 3.99 (s, 6H, OCH

2 3 2 3

)

[Chemical 18]

Under argon atmosphere, 1,5-bis (2-chloro-1,3-methyl-4-methoxy-4) pentane-1,5-dione 96 mg (0.23 mmol), zinc powder 50 mg (0.76 mmol) , TiCl (THF) 180 mg (0.49 mmol), dry THF 5 mL in a flask, 40

3 3

The mixture was stirred at ° C. for 1 hour to synthesize 1,2-bis (2-black-mouth-3-methyl-5-methoxy-4-cell) cyclopentene. The obtained 1,2-bis (2-chloro-1,3-methyl-1,5-methoxy-4,1) cyclopentene was purified by silica gel column chromatography (eluent: hexane) and further HPLC ( Purification was performed using hexane: ethyl acetate = 99: 1) to obtain a colorless amorphous solid. The yield was 37 mg and the yield was 42%.

'H-NMR (400MHz, CDC1, TMS) δ = 1. 84 (s, 6Η, CH), 2.02 (quintet

3 3

, J = 7.2 Hz, 2H, CH), 2.68 (t, J = 7.2 Hz, 4H, CH), 3.64 (s, 6H, OCH

twenty two

)

Three

MS m / z = 388 (M ⁺ )

[Chemical 19]

Under an argon atmosphere, add 37 mg (0.095 mmol) of cyclopentene and 2 mL of dry THF to a flask and add 1.6 M n-BuLi hexane solution. (0.17 mL, 0.29 mmol) was added dropwise at 0 ° C, followed by stirring at room temperature for 2 hours. B (OBu) (0. ImL, 0.38 mmol) was added and stirred at room temperature for 2 hours.

Three

P-Nodo-N, N Jetylline (57 mg, 0.19 mmol), THF 2 mL, Pd (P Ph) (0.7 mg), 2M NaCO aqueous solution (0.5 mL), 2 drops of ethylene glycol

3 4 2 3

And refluxed for 3.5 hours. It returned to room temperature, water and ether were added and the organic layer was taken out. The extract was dried over magnesium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (eluent: hexane: ethyl acetate = 9: 1). Furthermore, separation and purification were performed by HPLC (eluent: hexane: ethyl acetate = 95: 5), and 1 (2-methoxy 4 methyl 5-p- Ν, ジェ jetylaminophenol- (Lu 3 -Cenyl) -2- (2-Methoxy-4-methyl-5-ferro 3 -Chel) cyclopentene (la, —H) was obtained. The yield was 3.6 mg and the yield was 7.0%.

'H-NMR (400MHz, CDC1, TMS) δ = 1.17 (t, J = 7.2Hz, 6H, CH CH)

3 2 1 3

, 1.93 (s, 3H, CH), 1.96 (s, 3H, CH), 2.07 (quintet, J = 7.6Hz, 2H, C

3 3

H), 2.80 (t, J = 7.6Hz, 4H, CH), 3.36 (quartet, J = 7.2Hz, 4H, CH C

2 2 1 2

H), 3.68 (s, 3H, OCH), 3.70 (s, 3H, OCH), 6.65 (d, J = 7.2 Hz, 2H,

3 3 3

Ar), 7.19-7.35 (m, 7H, Ar) .MSm / z = 543 (M ⁺ )

[Chemical 20]

[Change in absorption spectrum due to photochromism]

The above synthesized 1- (2-methoxy-4-methyl-5-p-N, N-jetylaminophen (Lu 3 chanel) —2— (2-Methoxy-4-methyl-5-feru lu 3 chanel) Cyclopentene hexane solution is irradiated with 313 nm UV light and colored red, 524η m An absorption band showing an absorption maximum appeared in Fig. 14 (a). Figure 14 shows the change in absorption spectrum. The colored state is very stable with visible light equivalent to normal room light, but when it was irradiated with visible light with a strong light intensity, it gradually faded and returned to the original ring-opened form (Fig. 14 (b)). Thus, photochromism that is reversibly isomerized by ultraviolet light and visible light was observed.

[0086] [1— (2-Methoxy-1-4-methyl 5--p-N, N-deethylaminophenol 3-cell) 2 -— (2-Methoxy-4-methyl-5-ferro-3-cell -Lu) Photostability of cyclopentene ring closures]

It has been reported that the introduction of a methoxy group at the 2-position of dithiylbelfluorocyclopentene makes the ring-closed compound stable to visible light [(1) K. Shibata, S. Kobatake, M. I rie, Chem. Lett., 618-619 (2001), (2) JP 2005-82507, Japanese Patent Application 2003-3 13990].

FIG. 15 is a comparison of the photostability of the dichelcyclopentene compound (lb ′, 1 H) of this example and the dicherel perfluorocyclopentene compound. Whereas the conventional diphenylperfluorocyclopentene system is colored blue (Δ in the figure), the dichelcyclopentene compound of this example is colored in red (◯ in the figure). The 參 in the figure is the dicenyl cyclopentene compound (1b-H) of Example 1 that reacts reversibly with visible light. In addition, the photostability of the dicenylcyclopentene compound of this example is about 10 times higher than that of the conventional dithiylberylfluorocyclopentene compound.

[0088] [Change in absorption spectrum by acid addition]

FIG. 16 is a diagram showing a change in spectrum when trifluoromethanesulfonic acid is added in acetonitrile. From this figure, 1— (2-methoxy-4-methyl-5-p-N, N—jetylaminophenol 3 chael) 2— (2-methoxy-1-methyl-5-phenyl 5-phenyl 3 ) Addition of 2 to 3 equivalents of trifluoromethanesulfonic acid to cyclopentene (Fig. 16 (a)) and this UV-irradiated product (Fig. 16 (b)) reveals that the spectral change is eliminated. . [0089] [Fade reaction]

Figure 17 shows 1— (2-methoxy-4-methyl-5-p-N, N-deethylaminophenol-3 chael)-2- (2-methoxy-4-methyl-5-phenol This is the change in absorption spectrum when trifluoromethanesulfonic acid is added to (Cheel) cyclopentene and then irradiated with ultraviolet light, and then left at 25 ° C under certain conditions. The gradually fading force spectrum has shifted to a long wavelength and has not returned to the open ring. The solution after fading is light stable. With increasing temperature, the fading response increased.

[0090] From the above, it can be seen that the di-cyclopentene compound of this example has light stability after color development. In addition, since it fades due to heat, it was found that application to a heating sensor is possible.

[0091] (Example 4)

[Synthesis Example 4]

Under an argon atmosphere, 1.2 g (4.2 mmol) of 2,4 jib-mouthed 3-methyl-5-methoxythiophene was dissolved in 30 mL of dry THF and cooled to 78 ° C. Thereto, 2.9 mL (4.6 mmol) of n-BuLi hexane solution (1.6 M) was also added dropwise with stirring and stirred for 1 hour. B (OBu) 1. 8 mL (6.6 mmol) was added dropwise with a syringe and stirred for 1.5 hours.

Three

It was warmed and taented with water. Pd (PPh) 180 mg (0.15 mmol), 20% — Na CO

3 4 2 aq 8mL, P odode N, N jetinorea-phosphorus 1.2g (4.2 mmol) is added, 70 ° C

Three

At reflux for 2 hours.

Extracted with ether, combined organic layers, washed with saturated brine, dried over MgS04, filtered, concentrated, purified with adsorption column (hexane: acetate = 9: 1), 3 bromo — as pale yellow solid 2-Methoxy-4-methyl-5- (ρ-N, N-detylaminophenol) thiophene was obtained.

The yield was 0.64 g, and the yield was 43%.

'H-NMR (400MHz, CDC1, TMS) δ = 1.17 (t, J = 7.2 Hz, 6H, CH CH)

3 2 1 3

, 2.21 (s, 3H, CH), 3.36 (q, J = 7.2 Hz, 4H, CH CH), 3.96 (s, 3H, OC

3 1 2 3

H), 6.67 (d, J = 8.8Hz, 2H, Ar), 7.22 (d, J = 8.8Hz, 2H, Ar).

Three

[Chemical 21] 1) n-BuLi

2) B (OBu) ₃

In an argon atmosphere, 360 mg (l. Ommol) of 3 bromo-2-methoxy-4-methyl-5- (p-N, N dimethylaminophenol) thiophene was dissolved in 8 mL of dry THF and cooled to 78 ° C. did. A 1.6M n-BuLi hexane solution (0.70 mL, 1. I mmol) was also added dropwise with syringe, and the mixture was stirred for 1 hour. 1- (2-Methoxy-1-4-methyl-5-phenol 3-Chell) Octafluorocyclopentene 400mg (l. Ommol) dissolved in 5mL dryTHF was also added dropwise to the syringe, and 78 ° Stir at C for 2 h. After that, the temperature was returned to room temperature and the force was entangled with water. Extraction was performed with ether, and the organic layers were combined, washed with an aqueous sodium chloride solution, and separated and purified by silica gel column chromatography (eluent, hexane: ethyl acetate = 8: 2). Further, the product was purified by HPLC (hexane: ethyl acetate = 9: 1) to produce a light yellow amorphous solid. (Aminophenol 3 chanel) -2- (2-methoxy-4-methyl-5-phenol 3-chael) perfluorocyclopentene was obtained.

The yield was 210 mg and the yield was 32%.

'H-NMR (400MHz, CDC1, TMS) δ = 1.18 (t, J = 7.2Hz, 6H, CH CH)

3 2 1 3

, 2.06 (s, 3H, CH), 2.08 (s, 3H, CH), 3.36 (q, J = 7.2Hz, 4H, CH CH

3 3 1 2

), 3.74 (s, 3H, OCH), 3.77 (s, 3H, OCH), 6.66 (d, J = 8.8Hz, 2H, A

3 3 3

r), 7. 19-7.38 (m, 7H, Ar) .MS m / z = 651.1705 (M ⁺ )

[Chemical 22]

[0093] [Change in absorption spectrum associated with photochromism]

1- (2-Methoxy-4-methyl-5-p-N, N-jetylaminophenol-3 chanels) -2- (2-methoxy-4-methyl-5-phenol- (Lu 3 chanel) When the acetonitrile and hexane solution of perfluorocyclopentene was irradiated with 313 nm ultraviolet light, it was colored blue-green, and absorption bands with absorption maxima at 666 nm and 644 nm, respectively, appeared. Figure 18 shows the change in absorption spectrum. The colored state is very stable with visible light that is about the same level as normal room light, but when it was exposed to strong visible light, it gradually faded and returned to its original ring-opened form. In this way, photochromism that is reversibly different by ultraviolet light and visible light was observed.

[0094] [Change in absorption spectrum by acid addition]

FIG. 19 is a diagram showing a change in spectrum when trifluoromethanesulfonic acid is added in acetonitrile. From this figure, 1— (2-methoxy—4-methyl-5—p—N, N—jetylaminophenol 3 chas) 2— (2-methoxy-1-methyl-5-methyl 5-ferol 3 che -L) It can be seen that the addition of 2 to 3 equivalents of trifluoromethanesulfonic acid to perfluorocyclopentene eliminates the spectral change.

[0095] [Fade reaction]

FIG. 20 shows the change in absorption spectrum when dichloromethane sulfonic acid is added to the dicyclocyclopentene of this example and then irradiated with ultraviolet light and left at 60 ° C. in the dark. The force of fading reaction has not progressed to the open ring. The solution after fading is light stable As described above, Examples 3 and 4 show that these diphenyl cyclopentene compounds do not cause a reversible reaction with visible light under neutral and acidic conditions. It can also be seen that when the material is heat faded under acidic conditions, it changes to a different substance.

[0097] (Example 5)

[Synthesis Example 5]

Diarylethene having a trimethylsilyl group was synthesized according to the following scheme.

[Chemical 23]

[0098] Under an argon atmosphere, 150 mL of anhydrous tetrahydrofuran (THF) and 2.3 g (27 mmol) of diisobromine were placed in a flask, and 13 mL (21 mmol) of 1.6 M n-butyllithium hexane solution at −30 ° C. The solution was slowly added dropwise and stirred for 1 hour. 4.0 g (17 mmol) of 2 bromo-5-phenolthiophene dissolved in 30 mL of anhydrous THF at 78 ° C. was dripped and stirred for 2 hours. Furthermore, 2.6 mL (21 mmol) of trimethylsilyl chloride dissolved in 30 mL of anhydrous THF was added and stirred for 30 minutes. The reaction solution was returned to room temperature, extracted with ether, washed with brine, and dried over magnesium sulfate. Magnesium sulfate was filtered off, the solvent was distilled off, and the residue was purified by column chromatography using hexane Z ethyl acetate (95: 5) as a developing solvent to obtain 3 bromo-5-fluoro-2 trimethylsilylthiophene. (Rf = 0.71). Yield The amount was 3.9 g, and the yield was 75%.

Yeah! NMR (400 MHz, CDC1, TMS) δ = 0.42 (s, 9H, TMS), 7.28 (s, 1H

Three

, Ar), 7. 3- 7. 6 (m, 5H, Ar) .MS m / z = 310 (M ⁺ )

[0099] 3-Bromo-5-phenyl-2-trimethylsilylthiophene was placed in a flask under an argon atmosphere.

0.9 g (2.9 mmol) and 1 mL of anhydrous ether were added, and 1.6 mL (3.2 mmol) of 1.6 M n-butyllithium hexane solution was slowly added dropwise at 80 ° C. After stirring for 1 hour at 80 ° C, 0.20 mL (l.5 mmol) of octafluorocyclopentene was slowly added dropwise and stirred for 4 hours. The mixture was washed with water, returned to room temperature, extracted with ether, washed with brine, and dried over magnesium sulfate. Magnesium sulfate is filtered off, the solvent is distilled off, and the residue is purified by column chromatography using hexane as an eluent to obtain 1,2-bis (2 trimethylsilyl-1,5,3,3) perfluor. Rocyclopentene was obtained (Rf = 0.20). Yield ί Also, 0. 46 g, were yield ί or 49 ^_0/0.

'H-NMR (400MHz, CDC1, TMS) δ = 0.10 (s, 18H, TMS), 7. 3— 7. 6 (

Three

m, 12H, Ar) .MS m / z = 636 (M +).

[0100] [Change of absorption spectrum with photochromism]

When the hexane solution of 1,2-bis (2 trimethylsilyl-5-phenol 3 chael) perfluorocyclopentene synthesized above is irradiated with 313 nm UV light, the solution turns blue and is shown in Figure 21 Thus, an absorption peak having an absorption maximum at 615 nm appeared. After 2 minutes of irradiation, no spectral change was observed, and the light was in a steady state. The blue color is due to the formation of a closed ring. When it was irradiated with visible light of 460 nm or more, the solution gradually faded and became colorless when irradiated for about 3 minutes. As shown in the figure, it was confirmed that the absorption spectrum of the bleached solution coincided with the spectrum of the ring-opened product and returned to the ring-opened product. In this way, a photoreversible photochromic reaction by irradiation with ultraviolet light and visible light was confirmed.

[0101] [Thermal stability]

Heat stability of the hexane solution of 1,2-bis (2 trimethylsilyl 5 phenol 3 chalc) perfluorocyclopentene (la '''-F) in this example for 8 hours at 60 ° C I investigated. The absorption spectrum shows no change before and after heating, and the ring-opened product is thermally stable. It was confirmed that there was.

[0102] On the other hand, when the solution after irradiation with ultraviolet light was heated at 60 ° C, it became a colorless solution after 1 hour. The reaction was followed by an absorption spectrum in order to investigate the force of thermal return to the ring-opened body and whether it changed to another compound. Figure 22 shows the spectral change at 50 ° C. The absorption peak at 615 nm decreased with the progress of heating, and the peak disappeared completely in about 2 hours. The absorption spectrum after fading was different from that of the ring-opened product, indicating that it reacted with different substances. No coloration was observed even when the colorless substance was irradiated with ultraviolet light, and no photochromism was observed. When the thermal fading product was fractionated by HPLC and the mass spectrum was measured, mZz = 564, and it was apparent that it was 72 smaller than mZz = 636 of the ring-opened ring and the ring-closed ring. This suggests the elimination of the trimethylsilyl group, which was considered to have changed to a photostable compound with the elimination.

[0103] [Fade temperature coefficient]

In order to obtain the thermal fading reaction constant from the colored state, the reaction rate was measured at various temperatures and the reaction rate constant was determined. Figure 23 shows the absorbance decay at 30-60 ° C. When a primary plot was made from these data, a linear relationship was recognized as shown in FIG. This means that the reaction proceeds in the first order. In these experiments, no significant difference was observed in the presence or absence of air (oxygen). The slope force of the first-order plot in Fig. 24 The reaction rate constant at each temperature was determined. Furthermore, as shown in Fig. 25, the Arrhenius plot of the reaction rate constant shows a linear relationship, and the activation energy

(E) and frequency factor (A) were found to be 101 kj / mol and 1.7 X 10 ¹³ s— ¹ .

a

[0104] Using these values to calculate the half-life at various temperatures, Table 1 shows. In other words, at temperatures below 10 ° C, it will not fade safely for several months, and at temperatures above 30 ° C it will fade in several hours. A material having such a property can be used as a temperature sensor for temperature management in a place where a temperature change may occur. For example, when long-term frozen storage (1 month) is required, color is irradiated with ultraviolet light at a low temperature. If it is kept frozen, it will not fade, but it will fade if it is above 30 ° C for several hours. In this way, frozen storage is maintained for a long time Can be used as a temperature sensor.

[table 1]

Table 1. Half-life time of thermal bleaching reaction of 1 b "'-F in hexane ^a>

a) Half-life times were determined from Arrhenius parameters: E _a = 111 kJ / mol, A = 1.7 x 10 ¹³ s

[0105] (Example 6)

FIG. 26 shows an outline for synthesizing the styrene polymer having dicenylcyclopentene of the present invention shown below.

[Synthesis Example 6]

2—Synthesis of ododthiophene

[Chemical 24]

To 350 ml of acetic acid, 75 ml of sulfuric acid, and 350 ml of water, 66 g (0. 78 mol) of thiophene, 25 g (0. l mol) of noreperiodic acid and 85 g (0.33 mol) of I were added and stirred. Reaction solution in ice bath

2

While cooling, the solution was neutralized with an aqueous sodium hydroxide solution. The mixture was extracted with jetyl ether, washed with brine and aqueous sodium thiosulfate solution, and dried over magnesium sulfate. Magnesium sulfate was filtered off and the solvent was distilled off, followed by distillation under reduced pressure to isolate a fraction at 47 ° C / 0.7 KPa. did.

Yield 120g, Yield 75%

1H—NMR (400MHz, CDC1, TMS) δ = 6.80 (dd, J = 4 and 6Hz, 1H, A

Three

romatic H), 7.25 (d, J = 4Hz, 1H, Aromatic H), 7.36 (d, J = 6Hz, 1H, Aromatic H)

Synthesis of 2-cyclohexyloxythiophene

[Chemical 25]

To the flask in an argon atmosphere, 120 ml of cyclohexanol and 4 g of sodium were added and heated to 120 ° C. to completely dissolve the sodium. 35 g (0.095 mol) of CuBrO. Was added, 20 g (0.095 mol) of 2-odothiophene was slowly added dropwise, and the mixture was stirred at 125 ° C. for 4 hours. The reaction solution was returned to room temperature, and solids were removed by suction filtration. After extraction with jetyl ether, it was washed with brine and dried over magnesium sulfate. Magnesium sulfate was filtered off, and the solvent was distilled off under reduced pressure (35 ° C Zl. 4 KPa). Hexane was added to the remainder, and hexane-soluble components were collected by suction filtration. After the solvent in the filtrate was distilled off, the residue was purified by column chromatography using hexane as a developing solvent (R = 0.25).

f

Yield 1.08 g, 6.2% yield

'H -NMR (400MHz, CDC1, TMS) δ = 1. 3— 2. 1 (m, 10H, cyclohexylH

Three

), 4.06 (sep, J = 4Hz, 1H, OCH), 6.24 (d, J = 4Hz, 1H, Aromatic H), 6.56 (d, J = 6Hz, 1H, Aromatic H), 6 70 (dd, J = 4 and 6Hz, 1H, Aroma tic H)

Synthesis of 3,5-Dibu-Mouth Mo 2-cyclohexyloxythiophene

[Chemical 26]

Into a flask, add 1.58 g (8.66 mmol) of 2-cyclohexenoleoxythiophene and 25.Oml of dichloromethane. While stirring on an ice bath, 浴 bromosuccinimide 3.14 g (17.6 mmol) ) Was added slowly. Thereafter, the ice bath was removed and the mixture was stirred overnight. The reaction solution was cooled in an ice bath and solids were removed by filtration. Extract the filtrate with CHC1 and wash with heavy water and brine.

Three

And dried over magnesium sulfate. Magnesium sulfate was filtered off, the solvent was distilled off, and the residue was purified by column chromatography using hexane as a developing solvent (Rf = 0.59).

Yield 2.37g, Yield 80.3%

'H-NMR (400MHz, CDC1, TMS) δ = 1. 3— 2. 1 (m, 10Η, cyclohexyl

Three

H), 4. 05 (sep, J =

4Hz, 1H, OCH), 6. 73 (s, 1H, Aromatic H)

Synthesis of 4- (4-bromo-5-cyclohexyloxythiophene-2-yl) benzaldehyde

[Chemical 27]

a ₂ C0 ₃ ia S. THF In a flask under an argon atmosphere, 45 ml of anhydrous tetrahydrofuran (THF) and 3, 5 dibromo-2 cyclohexoxythiophene (2.37 g, 6.97 mmol) were added at 78 ° C. 4.5 ml (7.5 mmol) of 1.6M n butyl lithium hexane solution was slowly added dropwise. 78 After stirring at ° C for 1 hour, 2.74 ml (10.3 mmol) of tributyl boronate was slowly added dropwise and stirred for 1.5 hours. After entrapping with water, the temperature was returned to room temperature, and 4 bromobenzaldehyde 1.29 g (6.97 mmol), tetrakistriphenylphosphine palladium 0.34 g (0.29 mmol), 20% aqueous sodium hydrogen carbonate solution (16 ml) were added. Refluxed at 62 ° C for 7.5 hours. The mixture was neutralized with hydrochloric acid, extracted with jetyl ether, washed with brine, and dried over magnesium sulfate. Magnesium sulfate was filtered off, the solvent was distilled off, and the residue was purified by column chromatography using hexane: ethyl acetate = 9: 1 as a developing solvent (Rf = 0.33).

Yield 1.50g, Yield 58.8%

'H-NMR (400MHz, CDC1, TMS) δ = 1. 3— 2. 1 (m, 10Η, cyclohexyl

Three

H), 4.2 (sep, J = 4Hz, 1H, OCH), 7. 15 (s, 1H, Aromatic H), 7. 6—7.9 (m, 4H, Aromatic H), 10. 0 ( s, 1H, CHO) 2- [4- (4 Bromo-5 cyclohexylthiophene 2-yl) fur

Synthesis of dioxolane

[Chemical 28]

p Toluenesulfonic acid monohydrate 3. 15 mg (l. 10 X 10 mmol) is dissolved in 46 ml of toluene, and 4- (4 bromo-5 cyclohexyloxythiophene 2-yl) benzaldehyde is 0.46 g ( l. 26 mmol) and 0.85 g (13.7 mmol) of ethylene glycol were added, and the mixture was refluxed with a Dean-Stark condenser for 2.5 hours using an oil bath at 150 ° C. The mixture was neutralized with an aqueous sodium bicarbonate solution, extracted with jetyl ether, washed with brine, and dried over magnesium sulfate. Filter off magnesium sulfate, distill off the solvent, and recrystallize with hexane.

Yield 0.40 g, Yield 77.5% H-NMR (400MHz, CDC1, TMS) δ = 1. 3— 2. 1 (m, 10H, cyclohexyl

Three

H), 4. 0-4. 2 (m, 5H, OCH and CH2), 5. 81 (s, 1H, CH), 6. 98 (s, 1 H, Aromatic H), 7. 45— 7. 47 (m, 4H, Aromatic H)

Synthesis of 3-bromo-2-cyclohexyloxy-5-phenolthiophene

[Chemical 29]

Na ₂ C0 ₃ (aq) / THF

Add 50 ml of anhydrous THF, 2.3 g (6.8 mmol) of cyclohexoxythiophene in anhydrous argon, and add 1.6 M n-butyllithium hexane at 78 ° C. 4.5 ml (7.2 mmol) of the solution was slowly added dropwise. After stirring at 78 ° C for 1 hour, 2.3 ml (8.6 mmol) of tributyl boronate was slowly added dropwise and stirred for 1.5 hours. After quenching with water, the temperature was returned to room temperature, and 1.4 g (6.9 mmol) of odobenzene, 0.32 g (0.28 mmol) of tetrakistriphenylphosphine palladium, and 20% aqueous sodium hydrogen carbonate solution (27 ml) were added. And refluxed at 62 ° C. for 7.5 hours. Hydrochloric acid was added to neutralize, extracted with jetyl ether, washed with brine, and dried over magnesium sulfate. Magnesium sulfate was filtered off, the solvent was distilled off, and the residue was purified by column chromatography using hexane as a developing solvent (Rf = 0.28).

Yield 1.36 g, 59% yield

'H-NMR (400MHz, CDC1, TMS) δ = 1. 3— 2. 1 (m, 10Η, cyclohexyl

Three

H), 4. 15 (sep, J = 4Hz, 1H, OCH), 6. 96 (s, 1H, Aromatic H), 7.2-7.5 (m, 5H, Aromatic H)

1— (2 Cyclohexyloxy 5—Ferell 3 Chael) Heptafluoro Mouth pentene synthesis

[Chemical 30]

To a flask under an argon atmosphere, 0.39 g (l. 16 mmol) of 3 bromo 2 cyclohexyloxy 5 phenol thiophene and 25 ml of anhydrous THF were added 78. In C, 1.87 ml (1.38 mmol) of 1.6 M n-butyllithium hexane solution was slowly added dropwise. After stirring at −78 ° C. for 1 hour and a half, 0.27 ml (1.9 mmol) of octafluorocyclopentene was added all at once and stirred for 1.5 hours. After entrapping with water and returning to room temperature, the mixture was neutralized with an aqueous sodium hydrogen carbonate solution, extracted with jetyl ether, washed with brine, and dried over magnesium sulfate. Magnesium sulfate was filtered off, the solvent was distilled off, and the residue was purified by column chromatography using hexane as a developing solvent (Rf = 0.47).

Yield 0.42 g, Yield 80.5%

'H-NMR (400MHz, CDC1, TMS) δ = 1. 3— 2. 1 (m, 10Η, cyclohexyl

Three

H), 4. 28 (sep, J = 4 Hz, 1H, OCH), 7. 15 (s, 1H, Aromatic H), 7. 25-7. 50 (m, 5H, Aromatic H); MS (FAB ) m / z (M ⁺ ) 450 Di-Cyclocyclopentene 1,3 Synthesis of dioxolan

[Chemical 31]

Add 2— [4— (4 Bromo-5 cyclohexylthiophene —2—yl) phenol] — 1,3 Dioxolane 1.5 g (3.66 mmol) and anhydrous tetrahydrofuran 5 ml to an argon atmosphere flask. Then, 2.5 ml (3.95 mmol) of 1.6 M n-butyllithium hexane solution was slowly added dropwise at -78 ° C. After stirring at 78 ° C for 1 hour and a half, 1.0 g (2.22 mmol) of 1- (2 cyclohexyloxy 5 phenol 3 chalc) heptafluoric mouth pentene dissolved in 5 ml of anhydrous THF was slowly added dropwise. And stirred for 6 and a half hours. After entrapping with water and returning to room temperature, the mixture was neutralized with an aqueous sodium hydrogen carbonate solution, extracted with jetyl ether, washed with brine, and dried over magnesium sulfate. Magnesium sulfate was filtered off, the solvent was distilled off, and the residue was purified by column chromatography using hexane: ethyl acetate = 8: 2 as a developing solvent (Rf = 0.38).

Yield 0.84 g, Yield 50.0%

'H-NMR (400MHz, CDC1, TMS) δ = 1.0— 2. 1 (m, 20Η, cyclohexyl

Three

H), 4. 0-4. 2 (m, 6H, OCH and CH), 5. 81 (s, 1H, CH), 7.1-7.5 (m

2

, 11H, Aromatic H) Synthesis of di-cyclopentene formyl

[Chemical 32]

To the flask, add 5 ml of acetone, 0.18 g (0.7 mmol) of p-toluenesulfonic acid pyridinium (p-TAPS), 0.13 g (0.21 mmo 1) of di-cyclohexane, 1,3 dioxolane, and 2 Reflux for hours. The reaction solution is returned to room temperature, extracted with jetyl ether, and edible. Washed with brine and dried over magnesium sulfate. Magnesium sulfate was filtered off and the solvent was distilled off.

Yield 0.15g, Yield 100%

'H-NMR (400MHz, CDC1, TMS) δ = 1.0— 2.1 (m, 20Η, cyclohexyl

Three

H), 4.05 (sep, J = 4 Hz, 2H, OCH), 7.1— 7.9 (m, 11H, Aromatic H), 10.0 (s, 1H, CHO) Synthesis of di-cyclopentene-hydroxymethyl

[Chemical 33]

The flask was charged with 0.154 g (0.215 mmol) of di-cyclopentene monoformyl and 7 ml of ethanol. Potassium borohydride 1.16X10 " ² g (0.215 mmol) was dissolved in a mixed solvent of ethanol lml and water lml, slowly added dropwise with a syringe, and stirred for 1 hour. After extraction with jetyl ether, it was washed with brine. The magnesium sulfate was filtered off and the solvent was distilled off.

Yield 0.151 g, Yield 98.1%

'H-NMR (400MHz, CDC1, TMS) δ = 1.0-2.1 (m, 21H, cyclohexyl

Three

H and OH), 4.03 (sep, J = 4Hz, 2H, OCH), 4.7 (s, 2H, HOCH), 7.1

1 2

-7.5 (m, 11H, Aromatic H) Synthesis of di-cyclopentene monomer (la-M)

[Chemical 34]

In a flask under argon atmosphere, 0.15 g (0.21 mmol) of di-cyclopentene-hydroxymethyl, 62.3 mg (0.42 mmol) of p-butylbenzoic acid, 94.3 mg (0.46 mmol) of dicyclohexylcarbodiimide, 4-dimethylaminopyridine 27.6 mg (0.23 mmol) was dissolved in anhydrous THF 4.6 ml and stirred at room temperature for 24 hours. The mixture was neutralized with an aqueous sodium hydrogen carbonate solution, extracted with jetyl ether, washed with brine, and dried over magnesium sulfate. Magnesium sulfate was filtered off, 4-tert-butyl catechol (1 piece) was added, and the solvent was distilled off. Purification by column chromatography using hexane: ethyl acetate = 8: 2 as a developing solvent (Rf = 0.68). Since impurities remained, it was purified again by HPLC. Yield 0.151 g, Yield 84.8%

'H-NMR (400MHz, CDC1, TMS) δ = 1.0— 2.1 (m, 20Η, cyclohexyl

Three

H), 4.03 (sep, J = 4Hz, 2H, OCH), 5.36 (s, 2H, CH), 5.39 (d, 1H, J = 11Hz, Vinyl H), 5.86 (d, 1H, J = 18Hz, Vinyl H), 6.74 (dd, 1H, J = ll, 18Hz, Vinyl H), 7.1—7.5 (m, 13H, Aromatic H), 8.0—8.05 (m, 2H, Aromatic H);

HR-MS (FAB) m / z = 848.2438, Calculated for C H F O S m / z

47 42 6 4 2

= 848.2429 (M ⁺ ) Monomer la— M homopolymerization [Chemical 35]

Monomer la- M 0.151g (. 0 178mmol) , Azobisuisobuchi port - tolyl ^{(AIBN) 1. 57mg (9.68X10 _3} mmol), toluene (0.50 ml) placed in a glass tube, after Datsukifu tube, at 60 ° C Polymerized for 10 hours. The polymerization mixture was precipitated in methanol to isolate the polymer. It refine | purified by melt | dissolving in a small amount of black mouth form, and reprecipitating.

Yield 79 mg, Yield 52.3%

Number average molecular weight Mn = 21,000, polydispersity MwZMn = l.85

'H-NMR (400MHz, CDC1, TMS) δ = 1.0—1.8 (br, 23H, Vinyl H

Three

and cyclohexyl H), 4.0 (br, 2H, CH), 5. 18 (br, 2H, CH), 6.35 (br, 2

2

H, Aromatic H), 7.0—7.7 (br, 15H, Aromatic H)

[0118] [Glass transition point]

Using a differential scanning calorie (DSC) meter, the glass transition point (Tg) was determined from the change in the differential scanning calorific value of the polymer obtained above. The results are shown in FIG. From this measurement, it was found that the Tg of the polymer obtained was 104 ° C.

[0119] [Change in absorption spectrum associated with photochromism] Irradiation of ultraviolet light onto a film prepared by using the above synthesized polymer in a toluene solution and using the above synthesized polymer (the polymer dissolved in toluene and cast on a quartz substrate) has an absorption maximum at 650 nm. It changed to the spectrum it has. FIG. 28 is a diagram showing the state of spectrum change of the coloring reaction in the toluene solution and in the film. From this result, it was proved that the styrene polymer having diceryl cyclopentene of the present invention causes a coloring reaction by ultraviolet irradiation.

[0120] Next, when the polymer in the toluene solution and in the film was irradiated with ultraviolet light and allowed to react to the light steady state, it reacted up to 90% in the solution and up to 60% in the film. The results are shown in FIG.

[0121] [Fade reaction]

Next, the polymer irradiated with ultraviolet light (Poly (lb-M)) faded when heated to a high temperature of 100 ° C or higher, which was relatively stable in room light. In addition, it was confirmed that the photochromism of photocoloring and heating regeneration can be repeated when the faded film is irradiated with ultraviolet light.

[0122] [Fade rate coefficient]

Figure 30 shows the polymer 110 (Poly (lb-M)). C, 120. C, 130. C, 140. C, 150. FIG. 4 is a diagram showing the progress of thermal fading in C. From this figure, it can be seen that the process of thermal fading is promoted by heating. From this figure, it can be seen that at 150 ° C, the color faded completely within 10 minutes. Fig. 31 is a logarithmic plot of the change in absorption spectrum from the data in Fig. 30. FIG. 32 is a graph in which the speed coefficient is obtained from the slope of the primary plot of FIG. From this figure, using the formula lnk = —EaZRX lZT + lnA, the activation energy is calculated from the Arrhenius plot of the speed constant at each temperature, and Ea = 125 kjZmol. The value was almost the same as that dispersed in the. From the above, it was possible to introduce a diphenylcyclopentene dye having a photocoloring / heating regeneration function into a polymer at a high density without losing the properties of a low molecule.

[0123] [Synthesis Example 13]

Copolymerization of la—M and 1-adamantyl methacrylate

[Chemical 36]

The copolymerization of monomer la-M and 1-adamantyl methacrylate was carried out under the conditions shown in Table 2 below. As an example, we describe the experimental method for entry 2 in Table 2.

[0124] Diethylcyclopentene monomer (la—M) 99.7 mg (0.12 mmol), 1-adamantyl methacrylate 26. lmg (0.12 mmol), azobisisobutyoxy-tolyl (AIBN) 2.03 mg (12. 5 X 10 ^_3 mmol) and 0.67 ml of toluene were placed in a glass tube, and after degassed and sealed, polymerization was performed at 60 ° C for 5 hours. The polymerization mixture was precipitated in methanol and the polymer was isolated. The product was purified by dissolving in a small amount of black mouth form and reprecipitating.

[0125] From FIG. 33, it was found that the addition of 1-adamantyl methacrylate increased Tg.

Yield 81.6 mg, Yield 64.9%

Number average molecular weight Mn = 29000, polydispersity MwZMn = l. 94

The amount of la- M in the copolymer = 61 mole ^_0/0

[Table 2]

Copolymerization of diche-norecyclopentene monomer (la-M) and adamantyl methacrylate (AdMA) in toluene at 60 ° C

entry [1a-] [AIBN] Time Yield Content of 1 aM M _w / M _n

(mol / L) (mol / L) (h) (%) (mol%)

1 0.36 0 0.019 10 57.6 100 21000 1.85

2 0.18 0.17 0.019 5 64.9 61 29000 1.94

3 0.11 0.49 0.005 9 56.5 49 58000 2.98

4 0.24 0.12 0.019 4 56.1 42 24000 2.04

5 0 0.41 0.019 4 58.9 0 15000 2.26

Copolymerization of di-cyclopentene monomer (la-M) and N-1-adamantylmaleimide AdMI)

[Chemical 37]

Diethylcyclopentene monomer (la-M) 76. 3mg (0.090mmol), N-1-adadamantylmaleimide (AdMI) 20.9mg (0.090mmol), azobisisobutyoxy-tolyl (AIBN) 0.83mg (5.0 X 10 ^_3 mmol) and 0.5 ml of toluene were placed in a glass tube, and after degassing and sealing, polymerization was performed at 60 ° C for 10 hours. The polymerization mixture was precipitated in methanol and the polymer was isolated by filtration. Dissolve it in a small amount of black mouth form and reprecipitate it. Made.

Yield 71.5 mg, Yield 73.6%

Number average molecular weight Mn = 36000, polydispersity MwZMn = 2. 39

The amount of la- M in the copolymer = 49 mole ^_0/0

[0127] [Glass transition point]

Using a differential scanning calorie (DSC) meter, the glass transition point (Tg) was determined from the change in the differential scanning calorific value of the polymer obtained above. The results are shown in FIG. From this measurement, it was found that the Tg of the polymer obtained above had no glass transition point below 230 ° C.

[0128] [Pyrolysis]

From the thermogravimetric analysis of the obtained polymer (Poly ((la-M) -co-14)), the thermal decomposition initiation temperature was examined. The results are shown in FIG. From this measurement, it was found that the decomposition start temperature was around 240 ° C.

[0129] [Thermal fading speed]

FIG. 36 is a graph showing the temperature dependence of the thermal fading reaction coefficient of the polymer (Poly (lb-M)) and the copolymer (Poly ((lb-M) -co-14)). This figure shows that the thermal fading rates of Poly (lb—M) and Poly ((1 b-M) co-14) are almost equal. Based on the above, it was possible to synthesize a polymer having a glass transition point of 200 ° C. or higher with a high density introduction of a di-cyclopentene dye having photo-coloring and heating regeneration functions.

Industrial applicability

[0130] (1) The present invention provides a display material in which both of the two isomers generated by light irradiation are thermally relatively stable and can be easily returned to a non-colored state. Is possible.

[0131] Further, according to the present invention, it is possible to provide a photochromic material that reacts in addition and reverse with ultraviolet light. Furthermore, a novel photochromic material that develops red color can be provided.

[0132] According to the present invention, it is possible to provide a novel photochromic material that reacts in addition and reverse with ultraviolet light, exhibits photochromism, and decolors in addition and reverse by heating. In addition, the present invention can provide a display material that exhibits photochromism in a solid state and contains a photochromic component that is uniform in poly and high density.

Claims

(Wherein R ¹ represents a hydrogen (H) or fluorine (F) atom, R ² represents a hydrogen (H) or methyl group, R ³ represents a hydrogen (H) or methyl group, R ⁴ and R ⁵ may be the same or different and each represents hydrogen (H) or an amino group capable of protonation.

[2] A photochromic material comprising the dichelcyclopentene compound according to claim 1.

[3] An optical functional device comprising the photochromic material according to claim 2.

[4] A styrene polymer having a repeating unit represented by the following general formula (Π).

[Chemical 2]

(In the formula (Π), R represents a cyclohexyloxy group.) A photochromic material containing the styrene polymer according to claim 4, an optical functional element _n containing the photochromic material according to claim ^5.