Diaryl ethene compound

Abstract

To provide a diarylethene compound which closes a ring upon ultraviolet irradiation to exhibit a yellowish color, and can also retain a colored state for a certain amount of time upon visible-light irradiation.SOLUTION: The invention provides a compound represented by general formula (1) in the figure. (In general formula (1), X1 represents general formula (2a) or general formula (2b); X2 to X7 each independently represent a hydrogen atom or halogen atom; and X8 represents general formula (3a), general formula (3b), general formula (4a) or general formula (4b).)SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to diarylethene compounds.

Background Art

[0002] A photochromic compound is a compound that, when irradiated with light of a specific wavelength, changes its chemical bonding mode without changing its molecular weight to become colored, and returns to its original chemical bonding mode by light of another wavelength or a thermal reaction to decolorize (fade), having reversibility.

[0003] As one of the photochromic compounds, diarylethene compounds are known. When the open-ring form of a diarylethene compound is irradiated with ultraviolet light (UV light), a ring-closing reaction occurs to form a closed-ring form. The open-ring form of a diarylethene compound is usually colorless, while the closed-ring form is colored. When the colored closed-ring form of a diarylethene compound is irradiated with visible light, it returns to the original colorless open-ring form by an open-ring reaction. For example, Patent Documents 1 and 2 describe fluorine-containing diarylethene compounds that are colored yellow by ultraviolet irradiation and decolorized by visible light irradiation.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] As described above, a diarylethene compound can reversibly convert between two states, an open-ring form and a closed-ring form, by light irradiation. Further, diarylethene compounds have the advantages of excellent thermal stability, chemical stability, and durability of repeated coloring / fading. Although some diarylethene compounds have a closed-ring form that exhibits a blue color or the like, diarylethene compounds in which the closed-ring form exhibits a yellowish color generally tend to have a faster conversion rate from the closed-ring form to the open-ring form compared to diarylethene compounds in which the closed-ring form exhibits other colors (for example, blue). Therefore, for example, when adjusting the color tone by mixing colors using a combination of a diarylethene compound that exhibits a yellowish color and a diarylethene compound that exhibits a blue color, when irradiated with visible light, the yellowish color disappears first and only the blue color tends to remain. When the fading rates are different when using a combination of photochromic compounds that exhibit different colors in this way, the color tone changes over time and it is not possible to maintain a colored state with a certain color. For this reason, depending on the application, there may be a need for a diarylethene compound that closes the ring upon ultraviolet irradiation to exhibit a yellowish color and does not have too fast a rate from the closed-ring form to the open-ring form upon visible light irradiation and can maintain a colored state for a certain period of time even after visible light irradiation.

[0006] An object of the present invention is to provide a diarylethene compound that closes the ring upon ultraviolet irradiation to exhibit a yellowish color and can maintain a colored state for a certain period of time even after visible light irradiation.

Means for Solving the Problems

[0007] As a result of intensive studies to solve the above problems, the present inventors have found that a diarylethene compound represented by the following general formula (1) closes the ring with ultraviolet light to exhibit a yellowish color and can maintain a colored state for a certain period of time even after visible light irradiation. Based on this finding, the present inventors have further conducted research and completed the present invention.

[0008] That is, the compound of the present invention is a compound represented by the following general formula (1).

[0009]

Chemical formula

[0010] (In general formula (1), X 1represents general formula (2a) or general formula (2b), X 2 ~X 7 each independently represents a hydrogen atom or a halogen atom, X 8 represents general formula (3a), general formula (3b), general formula (4a) or general formula (4b).

[0011] [Chemical formula]

[0012] (In general formula (2a) and general formula (2b), R 11 and R 16 each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group or OR 101 ; R 101 represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group, R 12 ~R 15 and R 17 ~R 20 each independently represents a hydrogen atom, a halogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, a nitro group, a cyano group, OR 102 NR 103 R 104 NR 105 COR 106 COR 107 CO2R 108 CONR 109 OCOR 110 SO3R 111 or SO2NR 112 ; R 102 ~R 112 each independently represents a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group. However, R 103 and R 104When each of them is a linear or branched alkyl group which may have a substituent, independently of one another, R 103 and R 104 and R 103 and the nitrogen atom to which R 104 is attached may form a nitrogen-containing heterocyclic group which may have a substituent. * indicates the bonding site with the general formula (1).)

[0013]

Chemical formula

[0014] (In the general formula (3a) and the general formula (3b), R 21 and R 24 each independently represents a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent or OR 201 , R 201 represents a linear, branched or cyclic alkyl group which may have a substituent or an aryl group which may have a substituent, R 22 , R 23 , R 25 and R 26 each independently represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group which may have a substituent, a nitro group, a cyano group, OR 202 , NR 203 R 204 , NR 205 COR 206 , COR 207 , CO2R 208 , CONR 209 , OCOR 210 , SO3R 211 or SO2NR 212 , R 202 ~R 212 each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent or an aryl group which may have a substituent. However, R 203 and R 204When each is independently a linear or branched alkyl group which may have a substituent, R 203 and R 204 and R 203 and the nitrogen atom to which R 204 is attached may form a nitrogen-containing heterocyclic group which may have a substituent. * indicates the bonding site with the general formula (1).)

[0015]

Chemical formula

[0016] (In the general formula (4a) and the general formula (4b), R 31 and R 36 each independently represent a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, or OR 301 , R 301 represents a linear, branched or cyclic alkyl group which may have a substituent or an aryl group which may have a substituent, R 32 ~R 35 and R 37 ~R 40 each independently represent a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, a nitro group, a cyano group, OR 302 , NR 303 R 304 , NR 305 COR 306 , COR 307 , CO2R 308 , CONR 309 , OCOR 310 , SO3R 311 or SO2NR 312 , R 302 ~R 312 each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent or an aryl group which may have a substituent. However, R 303 and R304 When each is independently a linear or branched alkyl group which may have a substituent, R 303 and R 304 and R 303 and the nitrogen atom to which R 304 is attached may form a nitrogen-containing heterocyclic group which may have a substituent. * indicates the bonding site with the general formula (1).))

[0017] In the compounds of the present invention, in general formulas (2a) and (2b), R 11 and R 16 are each independently a linear, branched or cyclic alkyl group which may have a substituent having 1 to 10 carbon atoms or OR 101 represents, R 101 is a linear, branched or cyclic alkyl group which may have a substituent having 1 to 10 carbon atoms, R 12 ~R 15 and R 17 ~R 20 are each independently preferably a hydrogen atom, a linear or branched alkyl group which may have a substituent having 1 to 6 carbon atoms or an aryl group which may have a substituent having 6 to 10 carbon atoms.

[0018] In the compounds of the present invention, in general formulas (3a) and (3b), R 21 and R 24 are each independently a linear, branched or cyclic alkyl group which may have a substituent having 1 to 10 carbon atoms or OR 201 represents, R 201 is a linear or branched alkyl group which may have a substituent having 1 to 10 carbon atoms, R 22 , R 23 , R 25 and R 26 are each independently a hydrogen atom or a linear, branched or cyclic alkyl group which may have a substituent having 1 to 6 carbon atoms, and in general formulas (4a) and (4b), R 31 and R 36 are each independently a linear, branched or cyclic alkyl group which may have a substituent having 1 to 10 carbon atoms or OR301 represents, and R 301 represents a linear, branched or cyclic alkyl group which may have a substituent having 1 to 10 carbon atoms, and R 32 ~R 35 and R 37 ~R 40 are each independently preferably a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent having 1 to 6 carbon atoms, or an aryl group which may have a substituent having 6 to 10 carbon atoms.

[0019] In the compound of the present invention, in general formula (1), X 1 preferably represents general formula (2a). In the compound of the present invention, in general formula (1), X 8 preferably represents general formula (4a) or general formula (4b).

Advantages of the Invention

[0020] According to the present invention, it is possible to provide a diarylethene compound which undergoes ring closure upon ultraviolet irradiation to exhibit a yellow color and can maintain a colored state for a certain period of time even after visible light irradiation.

Brief Description of the Drawings

[0021]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

BEST MODE FOR CARRYING OUT THE INVENTION

[0022] The compound of the present invention is a compound represented by the following general formula (1).

[0023]

Chemical formula

[0024] In general formula (1), X 1 represents general formula (2a) or general formula (2b), and X 2 ~X 7 each independently represents a hydrogen atom or a halogen atom, and X 8 represents general formula (3a), general formula (3b), general formula (4a) or general formula (4b).

[0025]

Chemical formula

[0026] (In general formula (2a) and general formula (2b), R 11 and R 16 each independently represents a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent or OR 101 represents R 101 is a linear, branched or cyclic alkyl group which may have a substituent or an aryl group which may have a substituent, and R 12 ~R 15 and R 17 ~R 20are, independently of each other, a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, a nitro group, a cyano group, OR 102 、NR 103 R 104 、NR 105 COR 106 、COR 107 、CO2R 108 、CONR 109 、OCOR 110 、SO3R 111 or SO2NR 112 represents, and R 102 ~R 112 each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, or an aryl group which may have a substituent. However, when R 103 and R 104 are each independently a linear or branched alkyl group which may have a substituent, R 103 and R 104 and R 103 and R 104 and the nitrogen atom to which they are attached may form a nitrogen-containing heterocyclic group which may have a substituent. * indicates the bonding site with the general formula (1).)

[0027]

Chemical formula

[0028] (In the general formula (3a) and the general formula (3b), R 21 and R 24 each independently represents a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent or OR 201 , R 201 represents a linear, branched or cyclic alkyl group which may have a substituent or an aryl group which may have a substituent, and R 22 , R 23 , R 25 and R 26are, independently of each other, a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group which may have a substituent, a nitro group, a cyano group, OR 202 , NR 203 R 204 , NR 205 COR 206 , COR 207 , CO2R 208 , CONR 209 , OCOR 210 , SO3R 211 or SO2NR 212 and R 202 ~R 212 each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, or an aryl group which may have a substituent. However, when R 203 and R 204 are each independently a linear or branched alkyl group which may have a substituent, R 203 and R 204 and R 203 and R 204 and the nitrogen atom to which they are attached may form a nitrogen-containing heterocyclic group which may have a substituent. * indicates the bonding site to the general formula (1).)

[0029]

Chemical formula

[0030] (In the general formula (4a) and the general formula (4b), R 31 and R 36 each independently represent a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, or OR 301 , R 301 represents a linear, branched or cyclic alkyl group which may have a substituent, or an aryl group which may have a substituent, and R 32 ~R 35 and R 37 ~R 40are, independently of each other, a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, a nitro group, a cyano group, OR 302 , NR 303 R 304 , NR 305 COR 306 , COR 307 , CO2R 308 , CONR 309 , OCOR 310 , SO3R 311 or SO2NR 312 and R 302 ~R 312 each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent, or an aryl group which may have a substituent. However, when R 303 and R 304 are each independently a linear or branched alkyl group which may have a substituent, R 303 and R 304 and R 303 and R 304 and the nitrogen atom to which they are attached may form a nitrogen-containing heterocyclic group which may have a substituent. * indicates the bonding site to the general formula (1).)

[0031] In this specification, the compound represented by the above general formula (1) is also referred to as compound (1). The same applies to compounds with other formula numbers. For example, the compound represented by the general formula (5) is also referred to as compound (5).

[0032] In the present invention, examples of the linear, branched or cyclic alkyl group which may have a substituent include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent. In this specification, the number of carbon atoms of a group which may have a substituent is the total number of carbon atoms of the group including the substituent. Examples of the linear, branched or cyclic alkyl group include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, etc.; branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-methylbutyl group, 1-methylbutyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1-ethyl-2-methylpropyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2,4-dimethylpentyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylpentyl group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, 1,1-dimethylhexyl group, 1,1,3,3-tetramethylbutyl group, 3,5,5-trimethylhexyl group, 4-ethyloctyl group, 4-ethyl-4,5-dimethylhexyl group, 1,3,5,7-tetramethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, 6-methyl-4-butyloctyl group, 3,5-dimethylheptadecyl group, 2,6-dimethylheptadecyl group, 2,4-dimethylheptadecyl group, 2,2,5,5-tetramethylhexyl group, etc.; cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group, etc. are included.

[0033] The substituents in a linear, branched or cyclic alkyl group which may have substituents are not particularly limited. For example, a monocyclic or polycyclic aromatic ring group having 6 to 10 carbon atoms (such as a phenyl group, a naphthyl group, etc.), a linear, branched or cyclic alkoxy group having 1 to 8 carbon atoms, an amino group, a mono- or di-alkylamino group (the alkyl has 1 to 8 carbon atoms), a halogen atom, a cyano group, a hydroxy group, a nitro group, a carboxy group, an alkoxycarbonyl group having 1 to 8 carbon atoms, an acyl group having 2 to 10 carbon atoms (for example, an acetyl group, a propionyl group, a butyryl group, a valeryl group, a pivaloyl group, an acryloyl group, a methacryloyl group, a benzoyl group, a toluoyl group, a cinnamoyl group, an anisoyl group, a naphthoyl group, etc.), an acyloxy group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms (for example, a vinyl group, a 1-propenyl group, an allyl group, a butenyl group, a styryl group, etc.) and the like can be mentioned. As the substituents in a cyclic alkyl group which may have substituents, for example, a linear or branched alkyl group having 1 to 10 carbon atoms (such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a 2-methylbutyl group, a 1-methylbutyl group, a neopentyl group, a 1,2-dimethylpropyl group, a 1,1-dimethylpropyl group, etc.) can also be mentioned. When the alkyl group has substituents and there are two or more substituents, each substituent may be the same or different.

[0034] In the present invention, examples of the aryl group which may have substituents include an aryl group having 6 to 20 carbon atoms which may have substituents. The aryl group is not particularly limited. For example, a monocyclic aromatic hydrocarbon group such as a phenyl group; polycyclic aromatic hydrocarbon groups such as a naphthyl group, an anthracenyl group, a naphthacenyl group, a pentacenyl group, a phenanthrenyl group, a pyrenyl group and the like can be mentioned. The substituents in the aryl group which may have substituents are not particularly limited. For example, they include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, amino groups, mono- or di-alkylamino groups (alkyl having 1 to 8 carbon atoms), halogen atoms, cyano groups, hydroxy groups, nitro groups, halogenated hydrocarbon groups having 1 to 8 carbon atoms, carboxy groups, alkoxycarbonyl groups having 1 to 8 carbon atoms, and the like. Preferably, they are linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms, or halogen atoms. As the aryl group having 6 to 20 carbon atoms which may have substituents, for example, a phenyl group which may be substituted with an alkyl group (for example, phenyl group, 3-methylphenyl group, 2,6-dimethylphenyl group, etc.) and the like are preferable. When the aryl group has substituents, if there are two or more substituents, each substituent may be the same or different.

[0035] In general formula (1), X 1 represents the above general formula (2a) or general formula (2b) (a group represented by general formula (2a) or general formula (2b)). In the present invention, X 1 preferably represents general formula (2a). In general formula (2a) and general formula (2b), R 11 and R 16 each independently represent a linear, branched or cyclic alkyl group which may have substituents, an aryl group which may have substituents, or OR 101 . R 101 represents a linear, branched or cyclic alkyl group which may have substituents, or an aryl group which may have substituents. R 11 and R 16 each independently preferably represent a linear, branched or cyclic alkyl group which may have substituents having 1 to 10 carbon atoms, or OR 101 , and more preferably a linear or branched alkyl group having 1 to 10 carbon atoms or OR 101It is more preferable to represent, and it is even more preferable to represent a linear or branched alkyl group having 1 to 6 carbon atoms, and it is particularly preferable to represent a methyl group, an ethyl group, an n-propyl group or an n-butyl group. R 101 preferably represents a linear, branched or cyclic alkyl group which may have a substituent having 1 to 10 carbon atoms, more preferably represents a linear or branched alkyl group having 1 to 3 carbon atoms, and even more preferably represents a methyl group.

[0036] In General Formulas (2a) and (2b), R 12 , R 13 , R 14 and R 15 and also R 17 , R 18 , R 19 and R 20 each independently represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, a nitro group, a cyano group, OR 102 , NR 103 R 104 , NR 105 COR 106 , COR 107 , CO2R 108 , CONR 109 , OCOR 110 , SO3R 111 or SO2NR 112 . R 102 , R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 , R 110 , R 111 and R 112 each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent or an aryl group which may have a substituent. However, when R 103 and R 104 each independently is a linear or branched alkyl group which may have a substituent, R 103and R 104 and R 103 and R 104 may form a nitrogen-containing heterocyclic group which may have a substituent, together with the nitrogen atom to which they are attached.

[0037] R 12 ~R 15 and R 17 ~R 20 are each independently preferably a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent, or an aryl group having 6 to 10 carbon atoms which may have a substituent, more preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and even more preferably a hydrogen atom. R 102 ~R 112 are each independently preferably a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aryl group having 6 to 10 carbon atoms which may have a substituent.

[0038] In the present invention, examples of the nitrogen-containing heterocyclic group include a 4- to 8-membered nitrogen-containing heterocycle. The nitrogen-containing heterocycle may be a nitrogen-containing heterocycle containing an oxygen atom. Examples of the nitrogen-containing heterocycle include non-aromatic nitrogen-containing heterocycles. Examples of the 4- to 8-membered nitrogen-containing heterocycle include non-aromatic nitrogen-containing heterocycles such as a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring. The substituent in the nitrogen-containing heterocyclic group which may have a substituent is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, a mono- or di-alkylamino group (the alkyl has 1 to 8 carbon atoms), a halogen atom, a cyano group, a hydroxy group, a nitro group, a halogenated hydrocarbon group having 1 to 8 carbon atoms, a carboxy group, an alkoxycarbonyl group having 1 to 8 carbon atoms, and the like. The substituent in the nitrogen-containing heterocyclic group which may have a substituent is preferably a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. As the nitrogen-containing heterocyclic group which may have a substituent, a piperidine ring or a pyrrolidine ring which may have a substituent is preferable. When the nitrogen-containing heterocycle has a substituent and there are two or more substituents, each substituent may be the same or different.

[0039] In general formula (1), X 2 , X 3 , X 4 , X 5 , X 6 and X 7 each independently represents a hydrogen atom or a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. In general formula (1), X 2 ~X 7 are preferably halogen atoms, more preferably fluorine atoms.

[0040] In general formula (1), X 8 represents the above general formula (3a), general formula (3b), general formula (4a) or general formula (4b) (a group represented by general formula (3a), general formula (3b), general formula (4a) or general formula (4b)). In one aspect of the present invention, it is preferable that X 8 represents general formula (4a) or general formula (4b).

[0041] In general formula (3a) and general formula (3b), R 21 and R 24 each independently represent an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group or OR 201 . R 201 represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group. R 21 and R 24 each independently preferably represent an optionally substituted linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or OR 201 , more preferably a linear or branched alkyl group having 1 to 10 carbon atoms or OR 201It is more preferable to represent, more preferably to represent a linear or branched alkyl group having 1 to 6 carbon atoms, and particularly preferably to represent a methyl group, an ethyl group, an n-propyl group or an n-butyl group. R 201 preferably represents a linear or branched alkyl group which may have a substituent having 1 to 10 carbon atoms, more preferably represents a linear or branched alkyl group having 1 to 3 carbon atoms, and even more preferably represents a methyl group.

[0042] In General Formulas (3a) and (3b), R 22 , R 23 , R 25 and R 26 each independently represents a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group which may have a substituent, a nitro group, a cyano group, OR 202 , NR 203 R 204 , NR 205 COR 206 , COR 207 , CO2R 208 , CONR 209 , OCOR 210 , SO3R 211 or SO2NR 212 . R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 , R 209 , R 210 , R 211 and R 212 each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent or an aryl group which may have a substituent. However, when R 203 and R 204 are each independently a linear or branched alkyl group which may have a substituent, R 203 and R 204 and R 203 and the nitrogen atom to which R 204 is bonded may form a nitrogen-containing heterocyclic group which may have a substituent.

[0043] R 22 、R 23 、R 25 and R 26 preferably each independently represents a linear, branched or cyclic alkyl group which may have a hydrogen atom or a substituent having 1 to 6 carbon atoms, more preferably represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and even more preferably represents a hydrogen atom. R 202 ~R 212 preferably each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent having 1 to 10 carbon atoms or an aryl group which may have a substituent having 6 to 10 carbon atoms.

[0044] In General Formulas (4a) and (4b), R 31 and R 36 each independently represents a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent or OR 301 . R 301 represents a linear, branched or cyclic alkyl group which may have a substituent or an aryl group which may have a substituent. R 31 and R 36 each independently preferably represents a linear, branched or cyclic alkyl group which may have a substituent having 1 to 10 carbon atoms or OR 301 , more preferably represents a linear or branched alkyl group having 1 to 10 carbon atoms or OR 301 , even more preferably represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group or OR 301 , still even more preferably represents a methyl group or OR 301 , and most preferably represents a methyl group. R 301 preferably represents a linear, branched or cyclic alkyl group which may have a substituent having 1 to 10 carbon atoms, more preferably represents a linear or branched alkyl group having 1 to 3 carbon atoms, and even more preferably represents a methyl group.

[0045] In General Formulas (4a) and (4b), R 32 , R 33 , R 34 and R 35 and R 37 , R 38 , R 39 and R 40 are, independently of one another, a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, a nitro group, a cyano group, OR 302 , NR 303 R 304 , NR 305 COR 306 , COR 307 , CO2R 308 , CONR 309 , OCOR 310 , SO3R 311 or SO2NR 312 . R 302 , R 303 , R 304 , R 305 , R 306 , R 307 , R 308 , R 309 , R 310 , R 311 and R 312 are, independently of one another, a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent or an aryl group which may have a substituent. However, when R 303 and R 304 are, independently of one another, a linear or branched alkyl group which may have a substituent, R 303 and R 304 and R 303 and R 304 may form a nitrogen-containing heterocyclic group which may have a substituent with the nitrogen atom to which they are attached.

[0046] R 32 ~R 35 and R 37 ~R 40represents, independently of one another, a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent having 1 to 6 carbon atoms, or an aryl group which may have a substituent having 6 to 10 carbon atoms, preferably represents a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and more preferably represents a hydrogen atom. R 302 ~R 312 represents, independently of one another, a hydrogen atom, a linear, branched or cyclic alkyl group which may have a substituent having 1 to 10 carbon atoms, or an aryl group which may have a substituent having 6 to 10 carbon atoms.

[0047] As an example of a preferred embodiment of the compound of the present invention, compounds represented by the following general formula (1A), compounds represented by general formula (1B), compounds represented by general formula (1C), and compounds represented by general formula (1D) can be mentioned.

[0048]

Chemical formula

[0049]

Chemical formula

[0050]

Chemical formula

[0051]

Chemical formula

[0052] The compound represented by general formula (1A) is a compound in which, in general formula (1), X 1 represents general formula (2a), and X 8 represents general formula (4a). The compound represented by general formula (1B) is a compound in which, in general formula (1), X 1 represents general formula (2a), and X 8is a compound represented by the general formula (4b). In the general formula (1C), the compound represented by the general formula (1), X 1 represents the general formula (2a), and X 8 is a compound represented by the general formula (3a). In the general formula (1D), the compound represented by the general formula (1), X 1 represents the general formula (2a), and X 8 is a compound represented by the general formula (3b). Among them, as the compound of the present invention, the compound represented by the general formula (1A) and the compound represented by the general formula (1B) are preferable. This is because these compounds can maintain the colored state for a certain period of time even when irradiated with visible light (the rate of conversion from the closed-ring form to the open-ring form is appropriate). Among them, the compound represented by the general formula (1A) is more preferable as the compound of the present invention. In the general formulas (1A) to (1D), X 2 to X 7 , R 11 to R 15 , R 21 to R 23 , R 24 to R 26 , R 31 to R 35 , R 36 to R 40 are the same as those in the general formula (1).

[0053] As an example of a preferred embodiment of the compound of the present invention, in the general formula (1), X 1 represents the general formula (2a), and in the general formula (2a), R 11 represents a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, R 12 to R 15 represent hydrogen atoms, X 2 to X 7 represent halogen atoms (preferably fluorine atoms), X 8 represents the general formula (4a) or the general formula (4b), and in the general formula (4a), R 31 represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or OR 301 , R 301 represents a methyl group, R 32 to R 35represents a hydrogen atom, and in general formula (4b), R 36 represents a methyl group, an ethyl group, an n-propyl group or an n-butyl group, and R 37 ~R 40 represent hydrogen atoms. Examples of the compound include those in which R

[0054] The compound (compound (1)) (ring-opened form) represented by general formula (1) is usually colorless, but is converted into a ring-closed form by ultraviolet irradiation. The ring-closed form of compound (1) usually has an absorption maximum wavelength (λmax) at 430 to 480 nm. The ring-closed form of compound (1) exhibits a yellowish color. The ring-closed form of the compound represented by general formula (1) is also included in the present invention. For example, the compound represented by the above general formula (1A) is cyclized by ultraviolet light to form a compound (compound (1A')) (ring-closed form) represented by the following general formula (1A').

[0055]

Chemical formula

[0056] X 2 , X 3 , X 4 , X 5 , X 6 and X 7 , R 11 , R 12 , R 13 , R 14 and R 15 and R 31 , R 32 , R 33 , R 34 and R 35 are the same as those in general formula (1). X 2 ~X 7 , R 11 ~R 15 and R 31 ~R35 The preferred embodiments are also the same as those of the general formula (1).

[0057] The absorption maximum wavelength of the compound can be determined, for example, as the wavelength of the absorption maximum peak obtained by measuring the absorption spectrum of an ethyl acetate solution of the compound with an ultraviolet-visible spectrophotometer.

[0058] The cyclic form of compound (1) is converted to compound (1) which is an open-ring form by irradiation with visible light (for example, light of 450 nm or more). Compound (1) can be suitably used for various applications which are required to be converted to a cyclic form by ultraviolet irradiation, colored in a yellow color, and decolorized to a colorless state by visible light irradiation after coloring. When the compound of the present invention is irradiated with visible light (preferably indoor light such as white LED or fluorescent lamp) in its cyclic form (colored state), it is preferable that the time from the colored state to decolorization is 0.5 to 3 hours, and more preferably 0.5 to 2 hours. In one embodiment, as the compound of the present invention, a compound capable of maintaining the colored state for the above time after visible light irradiation is preferable.

[0059] Regarding the method for producing the compound of the present invention, an example of the synthesis method will be given below and described, but the method for producing the compound of the present invention is not limited to the following method. Further, when performing the reactions described later, functional groups other than the relevant site may be protected in advance with appropriate protecting groups as necessary, and these may be deprotected at an appropriate stage.

[0060] The compound represented by the general formula (1A), which is an example of the compound represented by the general formula (1), can be obtained, for example, by the following method. First, a compound represented by the general formula (5) (compound (5)) and a compound represented by the general formula (6) (compound (6)) are reacted to obtain a compound represented by the general formula (7) (compound (7)). More specifically, compound (7) can be obtained by lithiating compound (6) with n-butyllithium or the like and reacting it with 1 equivalent or an excess amount of compound (5). The reaction conditions for lithiation are not particularly limited, and the conditions for ordinary halogen-lithium exchange reactions can be adopted.

[0061]

Chemical formula

[0062] X in general formula (5) 2 、X 3 、X 4 、X 5 、X 6 and X 7 are the same as in general formula (1). These preferred embodiments are also the same as in general formula (1). In general formula (5), Z 1 and Z 2 are the same or different and represent a halogen atom.

[0063]

Chemical formula

[0064] R in general formula (6) 11 、R 12 、R 13 、R 14 and R 15 are the same as in general formula (2a). Z 3 represents a halogen atom or a hydrogen atom, preferably a halogen atom.

[0065]

Chemical formula

[0066] R in general formula (7) 11 、R 12 、R 13 、R 14 and R 15 are the same as in general formula (2a). X 2 、X 3 、X4 and X 5 and X 6 and X 7 is the same as general formula (1). Z 2 is the same as general formula (5).

[0067] Next, compound (7) can be reacted with a compound represented by general formula (8) (compound (8)) to obtain a compound represented by general formula (9) (compound (9)). More specifically, compound (9) can be obtained by lithiating compound (8) in the same manner as described above and reacting it with compound (7).

[0068]

Chemical formula

[0069] R in general formula (8) 31 and R 32 and R 33 and R 34 and R 35 is the same as general formula (4a). Z 4 represents a halogen atom or a hydrogen atom, preferably a halogen atom. Z 1 and Z 2 and Z 3 and Z 4 Examples of the halogen atom in Z 1 and Z 2 are the same as those described above. Z 3 and Z 4 are preferably fluorine atoms, and Z

[0070]

Chemical formula

[0071] R in general formula (9) 11 and R 12 and R 13 and R 14 and R 15 is the same as general formula (2a). X 2 and X 3, X 4 , X 5 , X 6 and X 7 is the same as general formula (1). R 31 , R 32 , R 33 , R 34 and R 35 is the same as general formula (4a). By oxidizing compound (9), a compound represented by general formula (1A) can be obtained.

[0072] As another method different from the above, a compound represented by general formula (1A) can also be obtained by reacting compound (5) with compound (8) to form a compound represented by general formula (10) (compound (10)), then reacting compound (10) with compound (6) to form compound (9), and then oxidizing compound (9). More specifically, compound (10) can be obtained by lithiating compound (8) in the same manner as above and reacting it with compound (5). Compound (9) can be obtained by lithiating compound (6) in the same manner as above and reacting it with compound (10).

[0073]

Chemical formula

[0074] R in general formula (10) 31 , R 32 , R 33 , R 34 and R 35 is the same as general formula (4a). X 2 , X 3 , X 4 , X 5 , X 6 and X 7 is the same as general formula (1). Z 1 is the same as general formula (5).

[0075] The reaction conditions of compound (5) and compound (6), and compound (7) and compound (8) are not particularly limited. The reaction conditions of compound (5) and compound (8), and compound (10) and compound (6) are not particularly limited. The reaction is usually carried out in a solvent. The solvent may be any solvent that is inert to the reaction and is not particularly limited. For example, organic solvents such as diethyl ether, tetrahydrofuran (THF), dioxane, cyclopentyl methyl ether (CPME), and toluene can be mentioned. The temperature during the reaction for the reaction of compound (5) and compound (6), and compound (10) and compound (6) can be, for example, -100 to 0 °C, preferably -100 to -50 °C. The reaction of compound (7) and compound (8), and compound (5) and compound (8) can be, for example, -100 to 0 °C, preferably -100 to -20 °C. The reaction time can be, for example, 0.5 to 24 hours, preferably 1 to 12 hours.

[0076] The conditions for oxidizing compound (9) are not particularly limited. Oxidation can be carried out using an oxidizing agent. The oxidizing agent is not particularly limited. For example, meta-chloroperbenzoic acid (m-CPBA), hydrogen peroxide, etc. can be used. It is preferable to use 2 to 10 equivalents of the oxidizing agent, and more preferably 2 to 6 equivalents. As the solvent for the oxidation, dichloromethane, chloroform, acetic acid, etc. can be used. The reaction temperature can be, for example, 0 to 120 °C, preferably 20 to 100 °C. The reaction time can be, for example, 0.5 to 24 hours, preferably 1 to 12 hours. The reaction can be monitored by thin layer chromatography (TLC), etc., and if the remaining raw materials are observed, the oxidizing agent can be further added.

[0077] The isolation and purification of each product in the above production method can be carried out by appropriately combining methods commonly used in organic synthesis, such as filtration, extraction, washing, drying, concentration, crystallization, various chromatographies, etc. Also, in the case of intermediates, it is also possible to use them in the next reaction without particular purification.

[0078] When geometric isomers exist in the compounds of the present invention, the present invention includes any of the geometric isomers. Further, when one or more asymmetric carbon atoms exist in the compounds of the present invention, the present invention includes any of the compounds in which each asymmetric carbon atom has an R configuration, a compound having an S configuration, and any combination thereof. Also, any of their racemic compounds, racemic mixtures, single enantiomers, and diastereomer mixtures are included in the present invention.

[0079] The compounds of the present invention are preferably compounds that dissolve in an organic solvent. Examples of the organic solvent include aromatic hydrocarbons (e.g., toluene, xylene, etc.), ketones (methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, 3-heptanone, etc.), ethers (e.g., propylene glycol monomethyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, etc.), esters (e.g., methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lactate, ethyl acetate, butyl acetate, methyl 3-methoxypropionate, etc.), and mixed solvents of two or more of these. The compounds of the present invention preferably dissolve in at least one of the above organic solvents in an amount of 0.1% by weight or more, for example, preferably in an amount of 0.1% by weight or more and 50% by weight or less, more preferably 1% by weight or more and 40% by weight or less, and still more preferably 3% by weight or more and 30% by weight or less. More preferably, the solubility in the organic solvent at 20°C is within such a range. When the solubility in the organic solvent is within such a range, the compounds of the present invention can be suitably used, for example, in the applications described later.

[0080] The compounds of the present invention can be used as photochromic compounds. Only one kind of the compounds of the present invention may be used, or two or more kinds may be used in combination. The compounds of the present invention can be made into a photochromic composition such as a photochromic resin composition by mixing with, for example, a resin or the like. The above resin is not particularly limited, and a thermoplastic resin, a photocurable resin, a thermosetting resin, etc. may be appropriately selected according to the use of the coloring composition and the like. For example, resins such as acrylic resin, polycarbonate resin, polystyrene resin, low-density polyethylene resin, polypropylene resin, polyurethane resin, polythiourethane resin, polyamide resin, polyacetal resin, polyphenylene sulfide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycycloolefin resin, polysulfone resin, polyethersulfone resin, fluororesin, silicone resin, polyester resin, epoxy resin, phenol resin, melamine resin, etc. may be mentioned. These may be used alone or in combination of two or more.

[0081] The compounding amount of the compound of the present invention in the photochromic resin composition is preferably, for example, 0.001 to 50% by weight, more preferably 0.01 to 40% by weight, based on the total solid content of the photochromic resin composition.

[0082] The photochromic resin composition may contain optional components other than the compound and resin of the present invention according to its use and the like. Examples of the optional components include antioxidants, defoaming agents, other pigments (photochromic pigments, dyes, pigments, etc. other than the compound of the present invention), infrared absorbers, ultraviolet absorbers, polymerizable monomers, polymerization initiators, sensitizers, and the like. The method for producing the photochromic resin composition is not particularly limited. For example, the compound and resin of the present invention and, if desired, the optional components to be blended may be mixed.

[0083] The photochromic composition containing the compound of the present invention is colored by ultraviolet irradiation. Further, the photochromic composition containing the compound of the present invention is decolored by visible light irradiation. Therefore, the photochromic composition containing the compound of the present invention is suitably used, for example, for the production of dyes for optical filters such as display materials, eyewear such as glasses and sunglasses, textile products such as printed shirts, printing inks, decorative materials, toys, display materials, eyewear, window materials, agricultural films, packaging materials, stationery, recording materials, cosmetics such as nail polish and makeup. The optical filter containing the compound of the present invention, the dye for optical filter, textile products such as printed shirts, printing ink, decorative material, toy, display material, eyewear, window material, agricultural film, packaging material, stationery, recording material, cosmetics, etc. are also included in the present invention. The dye for optical filter, textile products such as printed shirts, printing ink, decorative material, toy, display material, eyewear, window material, agricultural film, packaging material, stationery, recording material, cosmetics, etc. may contain the compound of the present invention, and its configuration is not particularly limited. The photochromic composition containing the compound of the present invention is particularly suitable as a photochromic composition used for printing ink, display materials, toys, eyewear, recording materials, cosmetics, etc.

[0084] The optical filter may contain the compound of the present invention. For example, like the conventional ones, it may have a support and, if necessary, an optical functional layer or the like. In the optical filter, the compound of the present invention is preferably contained in the support or the optical functional layer.

[0085] The configurations of the support and the optical functional layer are not particularly limited either. For example, the support is usually formed using a transparent resin. Examples of the transparent resin include cyclic olefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide (aramid) resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyamideimide resins, polyurethane resins, polythiourethane resins, polyethylene naphthalate (PEN) resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, and the like.

[0086] The method for manufacturing the optical filter is not particularly limited. For example, as a method for forming an optical functional layer containing the compound of the present invention on a support, after dissolving or dispersing the compound of the present invention and a binder resin or the like in a solvent, a coating method such as a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, a spin coating method, an extrusion coating method, etc. is used to form a coating film on the support. The above solvent is not particularly limited, but examples include the organic solvents described above.

[0087] Further, as a method for manufacturing an optical functional layer or a support containing the compound of the present invention, after mixing the compound of the present invention with a photocurable resin and / or a thermosetting resin and a photoinitiator and / or a thermal initiator, a cured film is formed by light irradiation and / or heat treatment, and this can also be used as the optical functional layer or the support.

[0088] As a method for manufacturing a lens which is an example of the optical filter, for example, a method of kneading the compound of the present invention with a transparent resin and molding it by an injection molding method, a compression molding method, an extrusion molding method, etc., or a method of forming an optical functional layer containing the compound of the present invention on the above support, and various other methods can be adopted.

Examples

[0089] Examples for more specifically explaining the present invention are shown below, but the present invention is not limited to these examples.

[0090] Below, the equipment used when measuring the physical properties of the obtained compounds is as follows. (NMR) Nuclear magnetic resonance apparatus JNM-ECZ400S manufactured by JEOL Ltd.

[0091] <Example 1> (Synthesis of 3-bromo-2-n-propylbenzofuran) 3-Bromo-2-n-propylbenzofuran was obtained in the same manner as described in ARKIVOC, 2000, (iii), 240 from 2-n-propylbenzofuran obtained in the same manner as the method described in The Journal of Organic Chemistry, 2012, 77(15), 6473.

[0092] (Synthesis of 3-bromo-2-methylbenzothiophene) 3-Bromo-2-methylbenzothiophene was obtained in the same manner as described in Journal of the American Chemical Society, 1953, 75, 3278.

[0093] (Synthesis of 1-(2-methyl-3-benzothienyl)-2,3,3,4,4,5,5-heptafluorocyclopentene) 1-(2-Methyl-3-benzothienyl)-2,3,3,4,4,5,5-heptafluorocyclopentene was obtained from octafluorocyclopentene and 3-bromo-2-methylbenzothiophene by the method described in JP-A-05-222035.

[0094] (Synthesis of Compound (2-1)) A 100 mL reaction vessel equipped with a thermometer was charged with 3-bromo-2-n-propylbenzofuran (7.2 g) and THF (30 mL), and cooled to -100 °C. A 1.6 M n-butyllithium hexane solution (14 g) was added dropwise, and the mixture was stirred at low temperature for 30 minutes. Subsequently, a solution of 1-(2-methyl-3-benzothienyl)-2,3,3,4,4,5,5-heptafluorocyclopentene (10 g) dissolved in THF (30 mL) was added dropwise. The mixture was stirred for 1 hour while maintaining the temperature, and then warmed to room temperature. Water was added to stop the reaction, and the mixture was discharged into water and toluene. After neutralization, extraction was performed with toluene, and purification was carried out by silica gel column chromatography to obtain 4.8 g of the compound represented by the following formula (2-1) (Compound (2-1)). In the formula, Pr represents an n-propyl group.

[0095] [Chemical formula]

[0096] (Synthesis of Compound (1-1)) A 200 mL reaction vessel equipped with a thermometer and a condenser was charged with Compound (2-1) (4.8 g) and acetic acid (30 mL), and 30% hydrogen peroxide solution (3.5 g) was added dropwise at 100 °C. After stirring at 110 °C for 1 hour, the completion of the reaction was confirmed and the mixture was allowed to cool to room temperature, and the reaction solution was discharged into water. The precipitate was collected by suction filtration and washed with water to obtain 4.1 g of the compound represented by the following formula (1-1) (Compound (1-1)). 1 H-NMR (400 MHz, CDCl3): δ 7.71 (d, 1H), 7.54 (d, 1H), 7.42 (m, 3H), 7.27 (m, 2H), 7.19 (d, 1H), 2.49 (m, 1H), 2.34 (m, 1H), 2.06 (s, 3H), 1.69 (m, 1H), 1.52 (m, 1H), 0.77 (t, 3H)

[0097] [Chemical formula]

[0098] [Example 2] (Synthesis of 3-Bromo-2-n-butylbenzofuran) 3-Bromo-2-n-butylbenzofuran was obtained from 2-n-butylbenzofuran (Tokyo Chemical Industry) in the same manner as the method described in ARKIVOC, 2000, (iii), 240.

[0099] (Synthesis of 2-Bromo-3-methylbenzothiophene) 2-Bromo-3-methylbenzothiophene was obtained from 3-methylbenzothiophene (Tokyo Chemical Industry) by the method described in Journal of Heterocyclic Chemistry, 1966, 3(1), 45.

[0100] (Synthesis of 1-(3-Methyl-2-benzothienyl)-2,3,3,4,4,5,5-heptafluorocyclopentene) 1-(3-Methyl-2-benzothienyl)-2,3,3,4,4,5,5-heptafluorocyclopentene was obtained from 2-bromo-3-methylbenzothiophene and octafluorocyclopentene by the method described in CN1470512.

[0101] (Synthesis of Compound (2-2)) A compound represented by the following formula (2-2) (Compound (2-2)) was obtained in the same manner as in the synthesis of the compound (2-1) in Example 1, except that 3-bromo-2-n-propylbenzofuran was changed to 3-bromo-2-n-butylbenzofuran and 1-(2-methyl-3-benzothienyl)-2,3,3,4,4,5,5-heptafluorocyclopentene was changed to 1-(3-methyl-2-benzothienyl)-2,3,3,4,4,5,5-heptafluorocyclopentene. In the formula, Bu represents an n-butyl group.

[0102]

Chemical formula

[0103] (Synthesis of Compound (1-2)) Compound (2-1) in the synthesis of the compound (1-1) of Example 1 was changed to compound (2-2), and in the same manner, a compound represented by the following formula (1-2) (compound (1-2)) was obtained. 1 H-NMR (400 MHz, CDCl3): δ 7.71 (m, 1H), 7.57 (m, 3H), 7.42 (d, 1H), 7.25 (m, 3H), 2.72 (t, 2H), 1.89 (s, 3H), 1.61 (quin, 2H), 1.32 (quin, 2H), 0.83 (t, 3H)

[0104]

Chemical formula

[0105] <Example 3> (Synthesis of 3-bromo-2-methylbenzofuran) In the same manner as the method described in ARKIVOC, 2000, (iii), 240, 3-bromo-2-methylbenzofuran was obtained from 2-methylbenzofuran (FUJIFILM Wako Pure Chemical Corporation).

[0106] (Synthesis of compound (2-3)) Compound (2-1) in the synthesis of the compound (2-1) of Example 1 was changed to 3-bromo-2-methylbenzofuran, and in the same manner, a compound represented by the following formula (2-3) (compound (2-3)) was obtained.

[0107]

Chemical formula

[0108] (Synthesis of compound (1-3)) Compound (2-1) in the synthesis of the compound (1-1) of Example 1 was changed to compound (2-3), and in the same manner, a compound represented by the following formula (1-3) (compound (1-3)) was obtained. 1H-NMR(400MHz, CDCl3): δ 7.71 (d, 1H), 7.55 (d, 1H), 7.40 (m, 3H), 7.27 (m, 2H), 7.11 (d, 1H), 2.22 (s, 3H), 2.12 (s, 3H)

[0109]

Chem.

[0110] <Example 4> (Synthesis of Compound (2-4)) Except that 3-bromo-2-n-propylbenzofuran in the synthesis of Compound (2-1) in Example 1 was changed to 3-bromo-2-methylbenzofuran, and 1-(2-methyl-3-benzothienyl)-2,3,3,4,4,5,5-heptafluorocyclopentene was changed to 1-(3-methyl-2-benzothienyl)-2,3,3,4,4,5,5-heptafluorocyclopentene, the compound represented by the following formula (2-4) (Compound (2-4)) was obtained in the same manner.

[0111]

Chem.

[0112] (Synthesis of Compound (1-4)) Except that Compound (2-1) in the synthesis of Compound (1-1) in Example 1 was changed to Compound (2-4), the compound represented by the following formula (1-4) (Compound (1-4)) was obtained in the same manner. 1 H-NMR(400MHz, CDCl3): δ 7.70 (d, 1H), 7.52 (m, 3H), 7.42 (d, 1H), 7.27 (m, 3H), 2.44 (s, 3H), 1.91 (s, 3H)

[0113]

Chem.

[0114] <Example 5> (Synthesis of Compound (2-5)) Compound (2-5) represented by the following formula (2-5) was obtained in the same manner as in the synthesis of the compound (2-1) of Example 1, except that 3-bromo-2-n-propylbenzofuran was changed to 3-bromo-2-n-butylbenzofuran.

[0115] [Chemical formula]

[0116] (Synthesis of Compound (1-5)) Compound (1-5) represented by the following formula (1-5) was obtained in the same manner as in Example 1, except that compound (2-1) in the synthesis of compound (1-1) of Example 1 was changed to compound (2-5). 1 1H-NMR (400 MHz, CDCl3): δ 7.71 (d, 1H), 7.55 (d, 1H), 7.43 (m, 3H), 7.29 (m, 2H), 7.18 (d, 1H), 2.50 (m, 1H), 2.32 (m, 1H), 2.05 (s, 3H), 1.60 (m, 1H), 1.47 (m, 1H), 1.15 (m, 2H), 0.80 (t, 3H)

[0117] [Chemical formula]

[0118] [Example 6] (Synthesis of 3-Bromo-2-methoxybenzothiophene) 3-Bromo-2-methoxybenzothiophene was obtained from 2-bromobenzothiophene by the method described in Japanese Chemical Journal, 1968, 89(2), 192.

[0119] (Synthesis of 1-(2-Methoxy-3-benzothienyl)-2,3,3,4,4,5,5-heptafluorocyclopentene) 1-(2-Methoxy-3-benzothienyl)-2,3,3,4,4,5,5-heptafluorocyclopentene was obtained by the method described in JP-A-03-261782.

[0120] (Synthesis of Compound (2-6)) Compound (Compound (2-6)) represented by the following formula (2-6) was obtained in the same manner as in the synthesis of Compound (2-1) in Example 1, except that 3-bromo-2-n-propylbenzofuran was changed to 3-bromo-2-methylbenzofuran and 1-(2-methyl-3-benzothienyl)-2,3,3,4,4,5,5-heptafluorocyclopentene was changed to 1-(2-methoxy-3-benzothienyl)-2,3,3,4,4,5,5-heptafluorocyclopentene.

[0121] [Chemical Formula]

[0122] (Synthesis of Compound (1-6)) Compound (Compound (1-6)) represented by the following formula (1-6) was obtained in the same manner as in the synthesis of Compound (1-1) in Example 1, except that Compound (2-1) was changed to Compound (2-6). 1 H-NMR (400 MHz, CDCl3): δ 7.51 (m, 2H), 7.35 (d, 1H), 7.26 (m, 4H), 6.89 (d, 1H), 4.13 (s, 3H), 2.27 (s, 3H)

[0123] [Chemical Formula]

[0124] [Comparative Example 1] The compound represented by the following formula (I) (Compound of Comparative Example 1) was synthesized by the method described in JP-A-4-360886.

[0125] [Chemical Formula]

[0126] [Comparative Example 2] The compound represented by the following formula (II) (the compound of Comparative Example 2) was synthesized by the method described in JP-A-11-311813.

[0127] [Chemical formula]

[0128] (Measurement of absorption spectrum) Compounds (1-1), (1-3), (1-5), and (1-6) were each dissolved in ethyl acetate and placed in a cell with a lid. Light with a wavelength of 254 nm was irradiated as ultraviolet light to obtain a photo-steady state (PSS). At this time, the solution concentration was adjusted so that the absorbance at the absorption maximum in the visible light region of the cyclic form was 1.0 or less, and the absorption spectrum was measured with an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, Ultraviolet-Visible Spectrophotometer V-560) (0 minutes). As visible light, the cell was allowed to stand for 15 minutes under general daylight white LED illumination to irradiate light, and the absorption spectrum was measured. The cell was taken out of the spectrophotometer and allowed to stand for an additional 15 minutes under the same illumination to irradiate light (total irradiation for 30 minutes), and the absorption spectrum was measured. The same operation (light irradiation) was repeated until the color of the solution in the cell became visually colorless. Specifically, it was carried out for an additional 15 minutes, and the absorption spectrum when visible light was irradiated for a total of 45 minutes was measured. Further, the same operation (light irradiation) was carried out for 15 minutes, and the absorption spectrum when visible light was irradiated for a total of 60 minutes was measured. The same operation was performed on the compounds of Comparative Example 1 and Comparative Example 2, and the absorption spectra at the photo-steady state (PSS, 0 minutes), when visible light was irradiated for 1 minute, 2 minutes, and 3 minutes were measured, respectively. Each spectrum was normalized with the absorbance at the absorption maximum wavelength in the region of 400 nm to 600 nm in the photo-steady state being 1 and drawn.

[0129] The results are shown in FIGS. 1 to 6. Figure 1 shows the time-dependent change in the absorption spectrum of the ethyl acetate solution of the compound (1-1) obtained in Example 1 upon light irradiation. Figure 2 shows the time-dependent change in the absorption spectrum of the ethyl acetate solution of the compound (1-3) obtained in Example 3 upon light irradiation. Figure 3 shows the time-dependent change in the absorption spectrum of the ethyl acetate solution of the compound (1-5) obtained in Example 5 upon light irradiation. Figure 4 shows the time-dependent change in the absorption spectrum of the ethyl acetate solution of the compound (1-6) obtained in Example 6 upon light irradiation. In Figures 1 to 4, the solid line represents the spectrum of the photostationary state (PSS) (when continuously irradiated with a certain light, it is a state where the generation and disappearance of the product obtained as a result of photoisomerization are in equilibrium. Here, it refers to a state where the generation of the closed-ring form from the compound (1) (open-ring form) and the reverse reaction from the closed-ring form to the compound (1) are in equilibrium), the dotted line represents the absorption spectrum when irradiated with visible light for 15 minutes, the dashed line represents the absorption spectrum when irradiated with visible light for 30 minutes, the long dashed-dotted line represents the absorption spectrum when irradiated with visible light for 45 minutes, and the double dashed-dotted line represents the absorption spectrum when irradiated with visible light for 60 minutes.

[0130] Figure 5 shows the time-dependent change in the absorption spectrum of the ethyl acetate solution of the compound obtained in Comparative Example 1 upon light irradiation. Figure 6 shows the time-dependent change in the absorption spectrum of the ethyl acetate solution of the compound obtained in Comparative Example 2 upon light irradiation. In Figures 5 to 6, the solid line represents the photostationary state (PSS), the dotted line represents the absorption spectrum when irradiated with visible light for 1 minute, the dashed line represents the absorption spectrum when irradiated with visible light for 2 minutes, and the long dashed-dotted line represents the absorption spectrum when irradiated with visible light for 3 minutes.

[0131] The compounds (1-1) to (1-6) obtained in Examples 1 to 6 were colored yellow upon ultraviolet irradiation. The absorption maximum wavelengths of the colored substances (ring-closed substances) measured above were 462 nm for compound (1-1), 451 nm for compound (1-2), 452 nm for compound (1-3), 441 nm for compound (1-4), 463 nm for compound (1-5), and 476 nm for compound (1-6). The compound of Comparative Example 1 was also colored yellow upon ultraviolet irradiation. The absorption maximum wavelength of the colored substance of the compound of Comparative Example 1 was 443 nm, and the absorption maximum wavelength of the colored substance of the compound of Comparative Example 2 was 433 nm. When the solutions in the cells were irradiated with visible light for 3 minutes, the compounds of Comparative Example 1 and Comparative Example 2 became colorless to the naked eye.

Claims

1. A compound represented by the following general formula (1). 【Chemical 1】 (In general formula (1), X １ represents general formula (2a) or general formula (2b), X ２ ~X ７ represents a fluorine atom, X ８ represents the general formula (4a) or the general formula (4b). 【Chemical 2】 (In General Formula (2a) and General Formula (2b), R １１ and R １６ each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms or OR １０１ , and R １０１ represents a linear or branched alkyl group having 1 to 10 carbon atoms.) R １２ to R １５ and R １７ to R ２０ each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. * represents a bonding site with the general formula (1).) 【Chemical Formula 3】 (In General Formula (4a) and General Formula (4b), R ３１ and R ３６ each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms or OR ３０１ and represents R ３０１ represents a linear or branched alkyl group having 1 to 10 carbon atoms, R ３２ to R ３５ and R ３７ to R ４０ each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. * represents a bonding site with the general formula (1).))

2. In general formula (2a) and general formula (2b), R １１ and R １６ each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms or OR １０１ and R １０１ represents a linear or branched alkyl group having 1 to 3 carbon atoms. R １２ ~R １５ and R １７ ~R ２０ The compound according to claim 1, wherein R, ~R, and R, ~R each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.

3. In general formula (4a) and general formula (4b), R ３１ and R ３６ each independently represents a linear alkyl group having 1 to 10 carbon atoms or OR ３０１ wherein R ３０１ represents a linear or branched alkyl group having 1 to 3 carbon atoms, R ３２ to R ３５ and R ３７ to R ４０ The compound according to claim 1 or 2, wherein R, ３２ to R, ３５ , and R, ３７ to R, ４０ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.

4. In general formula (1), X １ is the compound according to any one of claims 1 to 3, which represents general formula (2a).

5. In the general formula (1), X1 represents the general formula (2a), In the general formula (2a), R11 represents a methyl group, an ethyl group, an n-propyl group or an n-butyl group, and R12 to R15 represent hydrogen atoms, In the general formulas (4a) and (4b), R31 and R36 each independently represent a methyl group, an ethyl group, an n-propyl group, an n-butyl group or OR301, R301 represents a methyl group, and R32 to R35 and R37 to R40 represent hydrogen atoms. The compound according to any one of Claims 1 to 4.

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