Photochromic compound

Abstract

To provide a photochromic compound that exhibits superior thermal resistance.SOLUTION: There is provided a compound represented by the following general formula (1) (R11A and R11B each independently represent a substituted or unsubstituted alkyl group or an aryl group which may have a substituent; R12A and R12B each independently represent a hydrogen atom, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group; R13A to R15A and R13B to R15B each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a cyano group, or -CO2R21; R21 represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group; and XA and XB each independently represent an oxygen atom or a sulfur atom).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to compounds, more particularly to photochromic compounds. [Background technology]

[0002] A photochromic compound is a compound that has the reversibility of changing its chemical bonding pattern and becoming colored by irradiation with light of a specific wavelength without changing its molecular weight, and then returning to its original chemical bonding pattern and losing its color (fading) when not irradiated, heated, or irradiated with light of a different wavelength. For example, Patent Document 1 describes a naphthopyran compound that exhibits photochromic properties. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] U.S. Patent No. 5,464,567 Summary of the Invention [Problem to be solved by the invention]

[0004] The naphthopyran compound described in Patent Document 1 is useful as a photochromic compound, but there is room for improvement in terms of heat resistance.

[0005] An object of the present invention is to provide a photochromic compound having good heat resistance. [Means for solving the problem]

[0006] The present inventors have conducted extensive research to solve the above problems and have found that a naphthopyran compound represented by the following general formula (1) exhibits photochromic properties and has good heat resistance. Based on this finding, the present inventors have conducted further research and completed the present invention.

[0007] That is, the present invention relates to the following compounds, etc., but is not limited thereto. <1> A compound represented by the following general formula (1):

[0008] [ka]

[0009] (In general formula (1), R 11A and R 11B each independently represents a linear, branched, or cyclic alkyl group which may have a substituent, or an aryl group which may have a substituent; R 12A and R 12B each independently represents a hydrogen atom, an optionally substituted linear, branched or cyclic alkoxy group, or an optionally substituted aryloxy group, R 13A , R 14A , R 15A , R 13B , R 14B and R 15B are each independently a hydrogen atom, a halogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted linear, branched or cyclic alkoxy group, an optionally substituted aryloxy group, a cyano group, or -COR 21 represents R 21 represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group, X A and X B represent, independently of each other, an oxygen atom or a sulfur atom. <2> R 12A and R 12B are each independently a hydrogen atom or a linear or branched alkoxy group having 1 to 8 carbon atoms which may have a substituent, <1> The compound described in <3> R 12A and R 12Bis a hydrogen atom, <1> or <2> The compound described in <4> R 11A and R 11B are each independently a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, <1> ~ <3> The compound according to any one of the preceding claims. <5> R 13A , R 14A , R 15A , R 13B , R 14B and R 15B are each independently a hydrogen atom, a halogen atom, or a linear, branched, or cyclic alkoxy group which may have a substituent, <1> ~ <4> The compound according to any one of the preceding claims. <6> X A and X B is an oxygen atom, <1> ~ <5> The compound described in

[0010] This specification is as follows: <7> The present invention also discloses the following. <7> A compound represented by the following general formula (2):

[0011] [ka]

[0012] (In general formula (2), R 11 , R 12 , R 13 , R 14 , R 15 and X satisfies any of the following (a), (b) and (c). (stomach): R 11 represents an optionally substituted branched alkyl group, R 12 represents a hydrogen atom, an optionally substituted linear, branched or cyclic alkoxy group, or an optionally substituted aryloxy group, R 13 , R 14 and R 15are each independently a hydrogen atom, a halogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted linear, branched or cyclic alkoxy group, an optionally substituted aryloxy group, a cyano group, or -COR 21 represents R 21 represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group, X represents an oxygen atom or a sulfur atom. (B): R 11 represents a linear or cyclic alkyl group having 2 or more carbon atoms, which may have a substituent; R 12 represents an optionally substituted linear, branched or cyclic alkoxy group or an optionally substituted aryloxy group, R 13 , R 14 and R 15 are each independently a hydrogen atom, a halogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted linear, branched or cyclic alkoxy group, an optionally substituted aryloxy group, a cyano group, or -COR 21 represents R 21 represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group, X represents an oxygen atom or a sulfur atom. (C): R 11 represents a methyl group, R 12 represents an optionally substituted branched or cyclic alkoxy group or an optionally substituted aryloxy group, R 13 , R 14 and R 15are each independently a hydrogen atom, a halogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted linear, branched or cyclic alkoxy group, an optionally substituted aryloxy group, a cyano group, or -COR 21 represents R 21 represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group, X represents an oxygen atom or a sulfur atom. [Effects of the Invention]

[0013] According to the present invention, a photochromic compound having good heat resistance can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0014] The compound of the present invention is a compound represented by the following general formula (1).

[0015] [ka]

[0016] (In general formula (1), R 11A and R 11B each independently represents a linear, branched, or cyclic alkyl group which may have a substituent, or an aryl group which may have a substituent; R 12A and R 12B each independently represents a hydrogen atom, an optionally substituted linear, branched or cyclic alkoxy group, or an optionally substituted aryloxy group, R 13A , R 14A , R 15A , R 13B , R 14B and R 15Bare each independently a hydrogen atom, a halogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted linear, branched or cyclic alkoxy group, an optionally substituted aryloxy group, a cyano group, or -COR 21 represents R 21 represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group, X A and X B represent, independently of each other, an oxygen atom or a sulfur atom.

[0017] In general formula (1), R 11A and R 11B each independently represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group. In the present invention, examples of the linear, branched, or cyclic alkyl group which may have a substituent include linear, branched, or cyclic alkyl groups which may have a substituent and have 1 to 20 carbon atoms. In this specification, the number of carbon atoms in a group which may have a substituent refers to the number of carbon atoms in the entire group including the substituent.

[0018] Examples of linear, branched, or cyclic alkyl groups include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, and n-pentadecyl groups; Isopropyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, 1-methylbutyl, neopentyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 1,2-dimethylbutyl, 1,1-dimethylbutyl, 3-ethylbutyl, 2-ethylbutyl, 1-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-2-methylpropyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl branched-chain alkyl groups such as 1-ethylpentyl, 2,4-dimethylpentyl, 2-ethylhexyl, 2,5-dimethylhexyl, 2,5,5-trimethylpentyl, 2,4-dimethylhexyl, 2,2,4-trimethylpentyl, 1,1-dimethylhexyl, 1,1,3,3-tetramethylbutyl, 3,5,5-trimethylhexyl, 4-ethyloctyl, 4-ethyl-4,5-dimethylhexyl, 1,3,5,7-tetramethyloctyl, 4-butyloctyl, 6,6-diethyloctyl, 6-methyl-4-butyloctyl, 3,5-dimethylheptadecyl, 2,6-dimethylheptadecyl, 2,4-dimethylheptadecyl, and 2,2,5,5-tetramethylhexyl; Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an adamantyl group.

[0019] The substituent in the linear, branched or cyclic alkyl group which may have a substituent is not particularly limited, and examples thereof include a monocyclic or polycyclic aromatic ring group having 6 to 10 carbon atoms (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 number of carbon atoms in the alkyl is 1 to 8), a halogen atom, a cyano group, a hydroxy group, a nitro group, a carboxy group, an alkoxy group having 1 to 8 carbon atoms ... Examples of such alkyl groups include a carboxyl group, an acyl group having 2 to 10 carbon atoms (e.g., 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, and a naphthoyl group), an acyloxy group having 2 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms (e.g., a vinyl group, a 1-propenyl group, an allyl group, a butenyl group, and a styryl group). Examples of the substituent in the cyclic alkyl group which may have a substituent include linear or branched alkyl groups having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2-methylbutyl group, 1-methylbutyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, etc.). When the alkyl group has two or more substituents, the substituents may be the same or different. In one embodiment, the substituent in the alkyl group is preferably a halogen atom, a linear, branched or cyclic alkoxy group having 1 to 8 carbon atoms, a hydroxy group, a monocyclic or polycyclic aromatic group having 6 to 10 carbon atoms, or the like. Examples of the substituted linear, branched or cyclic alkyl group include a fluoromethyl group, a chloromethyl group, a bromobutyl group, a methoxymethyl group, a methoxyethyl group, a hydroxyethyl group, and a benzyl group.

[0020] In the present invention, the aryl group which may have a substituent includes an aryl group having 6 to 20 carbon atoms which may have a substituent. The aryl group is not particularly limited, and examples thereof include monocyclic aromatic hydrocarbon groups such as a phenyl group, and polycyclic aromatic hydrocarbon groups such as a naphthyl group, an anthracenyl group, a naphthacenyl group, a pentacenyl group, a phenanthrenyl group, and a pyrenyl group.

[0021] The substituent in the aryl 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 (wherein 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 a monocyclic or polycyclic aryl group having 6 to 14 carbon atoms. A linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms and a halogen atom are preferred. When the aryl group has a substituent, and there are two or more substituents, the respective substituents may be the same or different. Examples of the aryl group having a substituent include a nitrophenyl group, a cyanophenyl group, a hydroxyphenyl group, a carboxyphenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, a fluorophenyl group, a chlorophenyl group, a bromophenyl group, a methoxyphenyl group, an ethoxyphenyl group, a trifluoromethylphenyl group, an N,N-dimethylaminophenyl group, a nitronaphthyl group, a cyanonaphthyl group, a hydroxynaphthyl group, a methylnaphthyl group, a fluoronaphthyl group, a chloronaphthyl group, a bromonaphthyl group, a trifluoromethylnaphthyl group, a phenoxyphenyl group, and a biphenyl group.

[0022] In general formula (1), R 11A and R 11Bare each independently preferably a linear or branched alkyl group of 1 to 8 carbon atoms which may have a substituent, more preferably a linear or branched alkyl group of 1 to 6 carbon atoms which may have a substituent, even more preferably a linear or branched alkyl group of 1 to 5 carbon atoms which may have a substituent, even more preferably a linear or branched alkyl group of 1 to 4 carbon atoms which may have a substituent, even more preferably a methyl group, ethyl group, isopropyl group, isobutyl group, sec-butyl group, or tert-butyl group, particularly preferably a methyl group, ethyl group, or sec-butyl group, and most preferably an ethyl group or sec-butyl group. 11A and R 11B are preferably the same.

[0023] In general formula (1), R 12A and R 12B represent, independently of each other, a hydrogen atom, an optionally substituted linear, branched or cyclic alkoxy group, or an optionally substituted aryloxy group.

[0024] In the present invention, the linear, branched, or cyclic alkoxy group which may have a substituent includes a linear, branched, or cyclic alkoxy group having 1 to 20 carbon atoms which may have a substituent. Examples of linear, branched, or cyclic alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isopentyloxy, neopentyloxy, n-hexyloxy, 2-ethylhexyloxy, cyclohexyloxy, and n-dodecyloxy groups.

[0025] The substituent in the optionally substituted linear, branched, or cyclic alkoxy group is not particularly limited, and examples thereof include a halogen atom, a hydroxy group, a linear, branched, or cyclic alkoxy group having 1 to 18 carbon atoms, a monocyclic or polycyclic aryl group having 6 to 16 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, an amino group, and a mono- or di-alkylamino group (wherein the alkyl group has 1 to 8 carbon atoms). Examples of alkoxy groups in which some or all of the hydrogen atoms are substituted with halogen include a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a 1,1,2,2,2-pentafluoroethoxy group, a 1,1,2,2-tetrafluoroethoxy group, a 1,1,2-trifluoroethoxy group, a 1,2,2-trifluoroethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2-difluoroethoxy group, a 1,2-difluoroethoxy group, a 1,1-difluoroethoxy group, a 2-fluoroethoxy group, a 1-fluoroethoxy group, a 2,2, 3,3-tetrafluoro-1-propoxy group, 2,2,3,3,3-pentafluoro-1-propoxy group, 2,2,3,3,4,4,4-heptafluoro-1-butoxy group, 2,2,3,4,4,4-hexafluoro-1-butoxy group, 2,2,3,3,4,4,5,5-octafluoro-1-pentyloxy group, 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexyloxy group, 4,4,5,5,6,6,7,7,7-nonafluoro-1-heptyloxy group, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1- Heptyloxy group, 7,7,8,8,8-pentafluoro-1-octyloxy group, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octyloxy group, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1-nonyloxy group, 4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-1-nonyloxy group, 7,7,8,8,9,9,10,10,10-nonafluoro-1-decyloxy group, 3,3,4,4,5,5,6,6,7,7,8,8,9,9 ,10,10,10-heptadecafluoro-1-decyloxy group, 4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-pentadecafluoro-1-decyloxy group, 7,7,8,8,9,9,10,10,11,11,12,12,12-tridecafluoro-1-dodecyloxy group, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-henicosafluoro-1-dodecyloxy group, 7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,Examples include a 14-heptadecafluoro-1-tetradecyloxy group, a 1H,1H,2,5-bis(trifluoromethyl)-3,6-dioxaundecafluoro-1-nonyloxy group, a 6-(perfluoro-1-methylethyl)-1-hexyloxy group, a 2-(perfluoro-1-methylbutyl)-1-ethoxy group, a 2-(perfluoro-3-methylbutyl)ethoxy group, a 2-(perfluoro-7-methyloctyl)ethoxy group, a 2H-hexafluoro-2-propoxy group, and a 2,2-bis(trifluoromethyl)-1-propoxy group.

[0026] In the present invention, the aryloxy group which may have a substituent includes a monocyclic or polycyclic aryloxy group having 6 to 20 carbon atoms which may have a substituent. Examples of the monocyclic or polycyclic aryloxy group include a phenoxy group, a 1-naphthoxy group, a 2-naphthoxy group, and an anthracenyloxy group. The substituent in the optionally substituted aryloxy group is not particularly limited, and examples thereof include a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, a linear, branched, or cyclic alkoxy group having 1 to 8 carbon atoms, an amino group, a mono- or di-alkylamino group (the alkyl group has 1 to 8 carbon atoms), a halogen atom, a cyano group, a hydroxy group, a nitro group, an aryloxy group having 6 to 14 carbon atoms, etc. Preferred are a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, and a halogen atom. Examples of the aryloxy group having a substituent include a 2-methylphenoxy group, a 4-methylphenoxy group, a 4-tert-butylphenoxy group, a 2-methoxyphenoxy group, a 4-isopropylphenoxy group, and a phenoxyphenoxy group.

[0027] In general formula (1), R 12A and R 12Bare each independently preferably a hydrogen atom or a linear or branched alkoxy group having 1 to 8 carbon atoms which may have a substituent, more preferably a hydrogen atom or a linear or branched alkoxy group having 1 to 5 carbon atoms which may have a substituent, further preferably a hydrogen atom, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group or a tert-butoxy group, particularly preferably a hydrogen atom or a sec-butoxy group, and most preferably a hydrogen atom. 12A and R 12B are preferably the same.

[0028] In general formula (1), R 13A , R 14A , R 15A , R 13B , R 14B and R 15B are each independently a hydrogen atom, a halogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted linear, branched or cyclic alkoxy group, an optionally substituted aryloxy group, a cyano group, or -COR 21 Represents. R 21 R represents a linear, branched or cyclic alkyl group which may have a substituent, or an aryl group which may have a substituent. 21 As the alkyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms is preferred.

[0029] In the present invention, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0030] R 13A , R 14A , R 15A , R 13B , R 14B and R 15BIn the above, the optionally substituted linear, branched or cyclic alkyl group is preferably an optionally substituted linear or branched alkyl group having 1 to 8 carbon atoms. The optionally substituted aryl group is preferably an optionally substituted aryl group having 6 to 12 carbon atoms. The optionally substituted linear, branched or cyclic alkoxy group is preferably an optionally substituted linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms. The optionally substituted aryloxy group is preferably an optionally substituted aryloxy group having 6 to 12 carbon atoms. In one aspect, R 13A and R 13B are preferably the same. 14A and R 14B are preferably the same. 15A and R 15B are preferably the same.

[0031] In general formula (1), R 13A , R 14A , R 15A , R 13B , R 14B and R 15B are each independently preferably a hydrogen atom, a halogen atom, or a linear, branched, or cyclic alkoxy group which may have a substituent, more preferably a hydrogen atom, a halogen atom, or a linear or branched alkoxy group of 1 to 12 carbon atoms which may have a substituent, still more preferably a hydrogen atom, a halogen atom, or a linear or branched alkoxy group of 1 to 12 carbon atoms, and particularly preferably a hydrogen atom. As the halogen atom, a fluorine atom or a chlorine atom is preferred.

[0032] In general formula (1), X A and X B represent each independently an oxygen atom or a sulfur atom. X A and X B is preferably an oxygen atom.

[0033] As an example of a preferred embodiment of the compound of the present invention, in general formula (1), R 11Aand R 11B are each independently a methyl group, an ethyl group, or a sec-butyl group, and R 12A and R 12B are each independently a hydrogen atom or a sec-butoxy group, and R 13A , R 14A , R 15A , R 13B , R 14B and R 15B is a hydrogen atom, and X A and X B is an oxygen atom.

[0034] In one aspect, the compound of the present invention is preferably a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), a compound represented by the following formula (1-3), a compound represented by the following formula (1-4), or the like. In the formulas, Me represents a methyl group. In one aspect, the compound represented by formula (1-2), the compound represented by formula (1-3), or the compound represented by formula (1-4) is more preferred because of its better heat resistance, and the compound represented by formula (1-2) is even more preferred. In another aspect, the compound represented by formula (1-1) or the compound represented by formula (1-2) is preferred because of its fast decolorization speed.

[0035] [ka]

[0036] The method for producing the compound of the present invention will be described below by way of an example of a synthesis method, but the method for producing the compound of the present invention is not limited to the method described below. Furthermore, when carrying out the reaction described below, functional groups other than those at the relevant sites may be protected in advance with appropriate protecting groups as necessary, and these may be deprotected at an appropriate stage.

[0037] The compound represented by general formula (1) can be produced, for example, by reacting 2,7-dihydroxynaphthalene (2,7-naphthalenediol), a compound represented by the following general formula (2A) (hereinafter, also referred to as compound (2A)), and a compound represented by the following general formula (2B) (hereinafter, also referred to as compound (2B)).

[0038] [ka]

[0039] R in the above general formula (2A) 11A , R 12A , R 13A , R 14A , R 15A and X A are R in general formula (1), respectively. 11A , R 12A , R 13A , R 14A , R 15A and X A R in general formula (2A) 11A , R 12A , R 13A , R 14A , R 15A and X A The preferred embodiments of are the same as those of general formula (1).

[0040] R in the above general formula (2B) 11B , R 12B , R 13B , R 14B , R 15B and X B are R in general formula (1), respectively. 11B , R 12B , R 13B , R 14B , R 15B and X B R in general formula (2B) 11B , R 12B , R 13B , R 14B , R 15B and X BThe preferred embodiments of are the same as those of general formula (1). Compound (2A) and compound (2B) may be the same compound or different compounds, but are preferably the same compound.

[0041] The conditions for reacting 2,7-dihydroxynaphthalene with compound (2A) and compound (2B) are not particularly limited, and the reaction is usually carried out in a solvent in the presence of an acid catalyst.

[0042] The acid catalyst is not particularly limited, and examples thereof include organic acids such as p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, and pyridinium p-toluenesulfonate.

[0043] The solvent is not particularly limited as long as it is inert to the reaction, and examples thereof include dichloroethane, toluene, xylene, ethanol, isopropyl alcohol, and acetonitrile. The reaction temperature can be set to 20 to 100° C., and preferably 30 to 70° C. The reaction time can be set to 1 to 24 hours, and preferably 1.5 to 5 hours. The reaction efficiency can be improved by adding a dehydrating agent such as trimethyl orthoformate to the reaction system.

[0044] The method for producing compound (2A) and compound (2B) is not particularly limited, and they can be produced by the methods described in, for example, JP-A No. 2012-501326 and CN103936793A.

[0045] Compound (2A) and compound (2B) can be obtained, for example, by reacting a benzophenone derivative represented by the following general formula (4A) (hereinafter, also referred to as benzophenone derivative (4)) with a metal acetylene compound such as a lithio form of an acetylene derivative represented by the following general formula (5) (hereinafter, also referred to as acetylene derivative (5)), followed by deprotection.

[0046] [ka]

[0047] In the general formula (3A) and the general formula (5), L represents a protecting group (for example, a trimethylsilyl group, etc.). R in general formula (3A) and general formula (4A) 11A , R 12A , R 13A , R 14A , R 15A and X A are R in general formula (1), respectively. 11A , R 12A , R 13A , R 14A , R 15A and X A R in general formula (3A) and general formula (4A) 11A , R 12A , R 13A , R 14A , R 15A and X A The preferred embodiments of are the same as those of general formula (1).

[0048] The conditions for reacting the benzophenone derivative (4) with the acetylene derivative (5) are not particularly limited, and the reaction is usually carried out in a solvent in the presence of a deprotonating agent.

[0049] The deprotonating agent is not particularly limited, and examples thereof include butyllithium. The solvent is not particularly limited as long as it is inert to the reaction, and examples thereof include diethyl ether, tetrahydrofuran (THF), dioxane, and cyclopentyl methyl ether.

[0050] The temperature at which the benzophenone derivative (4) and the acetylene derivative (5) are reacted can be −90 to 20° C., and preferably −78 to 10° C. The reaction time can be 0.5 to 24 hours, and preferably 0.5 to 5 hours.

[0051] The conditions for synthesizing the compound represented by the general formula (2A) (hereinafter referred to as the propargyl alcohol derivative (2)) from the compound represented by the general formula (3A) (hereinafter referred to as the propargyl alcohol derivative (3)) are not particularly limited. The reaction is usually carried out in a solvent in the presence of a base. The base is not particularly limited, and examples thereof include potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, and tetrabutylammonium fluoride. The solvent is not particularly limited as long as it is inert to the reaction. Examples include alcohol solvents such as methanol, ethanol, isopropyl alcohol (IPA), and butanol, as well as THF. The reaction temperature for obtaining the propargyl alcohol derivative (2) from the propargyl alcohol derivative (3) can be 0 to 100°C, preferably 10 to 80°C. The reaction time can be 0.5 to 24 hours, preferably 0.5 to 10 hours.

[0052] Isolation and purification of each product in the above production method can be carried out by an appropriate combination of methods commonly used in organic synthesis, such as filtration, extraction, washing, drying, concentration, crystallization, various types of chromatography, etc. In addition, intermediates can also be subjected to the next reaction without any particular purification.

[0053] When the compound of the present invention has geometric isomerism, the present invention includes all of the geometric isomers. When the compound of the present invention has one or more asymmetric carbon atoms, the present invention includes compounds in which each asymmetric carbon atom is in the R configuration, the S configuration, and any combination thereof. Furthermore, the present invention includes all of their racemates, racemic mixtures, single enantiomers, and diastereomeric mixtures.

[0054] The compound of the present invention is a photochromic compound. The photochromic compound undergoes structural transformation into a colored substance upon irradiation with light such as ultraviolet light. The compound represented by general formula (1) is usually colorless, but undergoes structural transformation upon irradiation with light such as ultraviolet light, resulting in color development and exhibiting a yellow to orange color. In addition, the compound of the present invention has good heat resistance. The compound of the present invention also has the effect of exhibiting a fast decolorization speed.

[0055] The compound of the present invention preferably has a 1% weight loss temperature of 240°C or higher. Compounds having a 1% weight loss temperature of 240°C or higher are preferred because they have good heat resistance. The compound of the present invention preferably has a 1% weight loss temperature of 240 to 500°C, more preferably 250 to 500°C. The 1% weight loss temperature refers to the 1% weight loss temperature measured by thermogravimetric analysis (TGA). The measurement conditions can be those described in the Examples.

[0056] The compound of the present invention preferably has a maximum absorption wavelength of 420 to 460 nm when colored. The maximum absorption wavelength of a compound can be determined, for example, as the wavelength of the maximum absorption peak obtained by measuring the absorption spectrum of a thin film containing the compound using an ultraviolet-visible spectrophotometer. The maximum absorption wavelength of a compound can be measured by the method described in the Examples.

[0057] The compound of the present invention is preferably a compound that is soluble in an organic solvent. Examples of organic solvents 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 compound of the present invention is preferably soluble in at least one of the above organic solvents at a concentration of 0.1% by weight or more, for example, preferably 0.1% by weight to 50% by weight, more preferably 1% by weight to 40% by weight, and even more preferably 3% by weight to 30% by weight. More preferably, the solubility in the organic solvent at 20°C is within this range. When the solubility in the organic solvent is within this range, the compound of the present invention can be suitably used, for example, in the applications described below.

[0058] The compound of the present invention can be suitably used in various applications where it is required to turn yellow to orange upon irradiation with ultraviolet light, and then to become colorless upon heating, irradiation with visible light, or blocking ultraviolet light at room temperature.

[0059] The compound of the present invention can be used as a photochromic compound. The compound of the present invention may be used alone or in combination of two or more. The compound of the present invention can be mixed with, for example, a resin to form a photochromic composition such as a photochromic resin composition. The resin is not particularly limited, and may be appropriately selected from thermoplastic resins, photocurable resins, thermosetting resins, etc. depending on the intended use of the coloring composition. Examples of the resin include acrylic resins, polycarbonate resins, polystyrene resins, low-density polyethylene resins, polypropylene resins, polyurethane resins, polythiourethane resins, polyamide resins, polyacetal resins, polyphenylene sulfide resins, polyethylene terephthalate resins, polybutylene terephthalate resins, polycycloolefin resins, polysulfone resins, polyethersulfone resins, fluororesins, silicone resins, polyester resins, epoxy resins, phenolic resins, and melamine resins. These may be used alone or in combination of two or more.

[0060] The amount of the compound of the present invention blended in the photochromic resin composition is, for example, preferably 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.

[0061] The photochromic resin composition may contain optional components other than the compound of the present invention and the resin, depending on its application, etc. Examples of optional components include antioxidants, antifoaming agents, other dyes (photochromic dyes, dyes, pigments, etc. other than the compound of the present invention), infrared absorbers, ultraviolet absorbers, polymerizable monomers, polymerization initiators, sensitizers, etc. There are no particular limitations on the method for producing the photochromic resin composition, and for example, the compound of the present invention, the resin, and optional components that are added as desired may be mixed together.

[0062] Photochromic compositions containing the compounds of the present invention color upon exposure to ultraviolet light and decolorize upon cessation of ultraviolet irradiation, exposure to visible light, or heating. Therefore, photochromic compositions containing the compounds of the present invention are suitable for use in the manufacture of, for example, display materials, optical filters for eyewear such as eyeglasses and sunglasses, dyes for optical filters, textile products such as printed shirts, printing inks, decorative materials, toys, display materials, eyewear, window materials, agricultural films, packaging materials, stationery, recording materials, cosmetics for nail polish and makeup, indicators, and the like. Optical filters, dyes for optical filters, textile products such as printed shirts, printing inks, decorative materials, toys, display materials, eyewear, window materials, agricultural films, packaging materials, stationery, recording materials, cosmetics, and the like, containing the compounds of the present invention are also encompassed by the present invention. The dyes for optical filters, textile products such as printed shirts, printing inks, decorative materials, toys, display materials, eyewear, window materials, agricultural films, packaging materials, stationery, recording materials, cosmetics, and the like may contain the compounds of the present invention, and their composition is not particularly limited. The photochromic composition containing the compound of the present invention is particularly suitable as a photochromic composition for use in printing inks, display materials, toys, eyewear, recording materials, cosmetics, and the like.

[0063] The optical filter may be any optical filter as long as it contains the compound of the present invention, and may, for example, have a support similar to conventional optical filters and, if necessary, an optically functional layer, etc. In the optical filter, the compound of the present invention is preferably contained in the support or the optically functional layer.

[0064] The configurations of the support and the optical functional layer are not particularly limited. For example, the support is usually formed using a transparent resin. Examples of transparent resins 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, polyparaphenylene resins, polyamideimide resins, polyurethane resins, polythiourethane resins, polyethylene naphthalate (PEN) resins, fluorinated aromatic polymer resins, (modified) acrylic resins, and epoxy resins.

[0065] The method for producing an 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, the compound of the present invention and a binder resin, etc. are dissolved or dispersed in a solvent, and then a coating film is formed on the support by a coating method such as dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, spin coating, or extrusion coating. The solvent is not particularly limited, and examples thereof include the above-mentioned organic solvents.

[0066] Furthermore, as a method for producing an optical functional layer or a support containing the compound of the present invention, the compound of the present invention may be mixed with a photocurable resin and / or a thermosetting resin, and a photopolymerization initiator and / or a thermopolymerization initiator, and then a cured film is formed by light irradiation and / or heat treatment, and this may be used as the optical functional layer or the support.

[0067] As a method for producing a lens, which is an example of an optical filter, various methods can be used, such as a method in which the compound of the present invention is kneaded into a transparent resin and molded by injection molding, compression molding, extrusion molding, or the like, or a method in which an optical functional layer containing the compound of the present invention is formed on the above-mentioned support.

[0068] The present specification also discloses a compound represented by the following general formula (2). The compound of the present disclosure represented by the following general formula (2) is an example of a compound represented by the above general formula (2A). The compound represented by the following general formula (2) can be used, for example, to produce a compound represented by the above general formula (1). According to the present disclosure, a compound that can be used to produce a photochromic compound can be provided.

[0069] A compound represented by the following general formula (2):

[0070] [ka]

[0071] (In general formula (2), R 11 , R 12 , R 13 , R 14 , R 15 and X satisfies any of the following (a), (b) and (c). (stomach): R 11 represents an optionally substituted branched alkyl group, R 12 represents a hydrogen atom, an optionally substituted linear, branched or cyclic alkoxy group, or an optionally substituted aryloxy group, R 13 , R 14 and R 15 are each independently a hydrogen atom, a halogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted linear, branched or cyclic alkoxy group, an optionally substituted aryloxy group, a cyano group, or -COR 21 represents R 21 represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group, X represents an oxygen atom or a sulfur atom. (B): R 11 represents a linear or cyclic alkyl group having 2 or more carbon atoms, which may have a substituent; R 12 represents an optionally substituted linear, branched or cyclic alkoxy group or an optionally substituted aryloxy group, R 13 , R 14 and R 15 are each independently a hydrogen atom, a halogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted linear, branched or cyclic alkoxy group, an optionally substituted aryloxy group, a cyano group, or -COR 21 represents R 21 represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group, X represents an oxygen atom or a sulfur atom. (C): R 11 represents a methyl group, R 12 represents an optionally substituted branched or cyclic alkoxy group or an optionally substituted aryloxy group, R 13 , R 14 and R 15 are each independently a hydrogen atom, a halogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted linear, branched or cyclic alkoxy group, an optionally substituted aryloxy group, a cyano group, or -COR 21 represents R 21 represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group, X represents an oxygen atom or a sulfur atom.

[0072] In the compounds of the present disclosure, examples of the optionally substituted linear, branched, or cyclic alkyl group, the optionally substituted aryl group, the optionally substituted linear, branched, or cyclic alkoxy group, the optionally substituted aryloxy group, and the halogen atom are the same as those in the compounds of the present invention described above.

[0073] When the compound of the present disclosure satisfies the above (A), R 11 represents preferably a branched-chain alkyl group having 3 to 20 carbon atoms which may have a substituent, more preferably a branched-chain alkyl group having 3 to 6 carbon atoms which may have a substituent, further preferably an isopropyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group, and particularly preferably a sec-butyl group. In the above (A) of the present disclosure, R 12 is preferably a hydrogen atom or a linear or branched alkoxy group having 1 to 8 carbon atoms which may have a substituent, more preferably a hydrogen atom or a linear or branched alkoxy group having 1 to 8 carbon atoms, even more preferably a hydrogen atom or a linear or branched alkoxy group having 1 to 5 carbon atoms which may have a substituent, even more preferably a hydrogen atom, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group or a tert-butoxy group, and particularly preferably a hydrogen atom or a sec-butoxy group.

[0074] When the compound of the present disclosure satisfies the above (b), R 11 is preferably a linear or cyclic alkyl group having 2 to 20 carbon atoms, which may have a substituent, more preferably a linear or cyclic alkyl group having 2 to 6 carbon atoms, even more preferably a linear or cyclic alkyl group having 2 to 4 carbon atoms, and particularly preferably an ethyl group. In the above (b) of the present disclosure, R 12is preferably a linear or branched alkoxy group having 1 to 8 carbon atoms which may have a substituent, more preferably a linear or branched alkoxy group having 1 to 8 carbon atoms, even more preferably a linear or branched alkoxy group having 1 to 5 carbon atoms which may have a substituent, even more preferably a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group or tert-butoxy group, and particularly preferably a sec-butoxy group.

[0075] When the compound of the present disclosure satisfies the above (c), R 12 is preferably a branched or cyclic alkoxy group having 3 to 8 carbon atoms which may have a substituent, more preferably a branched or cyclic alkoxy group having 3 to 8 carbon atoms, even more preferably a branched alkoxy group having 3 to 5 carbon atoms which may have a substituent, even more preferably an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group or a tert-butoxy group, and particularly preferably a sec-butoxy group.

[0076] In the above (a), (b), and (c) of the present disclosure, R 13 , R 14 and R 15 are each preferably a hydrogen atom, a halogen atom, or a linear, branched, or cyclic alkoxy group which may have a substituent, more preferably a hydrogen atom, a halogen atom, or a linear or branched alkoxy group having 1 to 8 carbon atoms which may have a substituent, and even more preferably a hydrogen atom or a halogen atom. 21 As the alkyl group, an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms are preferred. In the above (a), (b) and (c) of the present disclosure, X is preferably an oxygen atom.

[0077] The method for producing the compound of the present disclosure is not particularly limited, and for example, it can be produced by the same method as that for the compound (2A) described above.

[0078] All scientific and patent literature cited herein is hereby incorporated by reference. [Example]

[0079] Examples will be given below to explain the present invention more specifically, but the present invention is not limited to these examples.

[0080] The following instruments were used to measure the physical properties of the compounds obtained. (LC / MS) Shimadzu Corporation High Performance Liquid Chromatograph Mass Spectrometer LCMS-2010EV (ESI method) (GC / MS) Shimadzu Corporation Gas Chromatograph Mass Spectrometer GCMS-QP2010Plus (EI method) (NMR) Nuclear magnetic resonance device JNM-ECZ400S manufactured by JEOL Ltd.

[0081] Example 1 A compound represented by the following formula (1-1) was obtained by the following method: The compound represented by the following formula (1-1) is referred to as compound (1-1).

[0082] [ka]

[0083] 4-sec-butoxybenzophenone 4-sec-butoxybenzophenone was synthesized in the same manner as in the synthesis of 4-n-butoxybenzophenone described in Polymer Journal, 1990, 22(8), 705, except that n-butyl bromide was changed to sec-butyl bromide.

[0084] 1-(4-sec-butoxyphenyl)-3-(trimethylsilyl)-1-phenylprop-2-yn-1-ol A 300 mL four-neck flask equipped with a thermometer was charged with trimethylsilylacetylene (14 g) and THF (85 mL). Under a nitrogen atmosphere, n-butyllithium (1.6 M, 61 g) was added dropwise while maintaining the temperature below 0°C, and the mixture was stirred for 30 minutes. A solution of 4-sec-butoxybenzophenone (30 g) in THF (200 mL) was added dropwise while maintaining the temperature below 0°C, and the mixture was allowed to warm to room temperature. The reaction mixture was poured into water, extracted with toluene, and concentrated under reduced pressure to obtain 40 g of 1-(4-sec-butoxyphenyl)-3-(trimethylsilyl)-1-phenylprop-2-yn-1-ol.

[0085] 1-(4-sec-butoxyphenyl)-1-phenylprop-2-yn-1-ol A 200 mL four-neck flask equipped with a thermometer was charged with 1-(4-sec-butoxyphenyl)-3-(trimethylsilyl)-1-phenylprop-2-yn-1-ol (40 g), methanol (85 mL), and potassium carbonate (7 g), and the mixture was stirred at room temperature for 3 hours. The mixture was then poured into water. The mixture was extracted with toluene and concentrated under reduced pressure to obtain 26 g of 1-(4-sec-butoxyphenyl)-1-phenylprop-2-yn-1-ol. GC / MS: m / z = 280.05 ([M] + )

[0086] Compound (1-1) 2,7-Dihydroxynaphthalene (1.2 g), 1-(4-sec-butoxyphenyl)-1-phenylprop-2-yn-1-ol (4.2 g), toluene (30 mL), and p-toluenesulfonic acid monohydrate (90 mg) were charged into four 50 mL flasks equipped with thermometers and condensers and stirred at 40°C for 2 hours. After cooling, water (22 mL) was added and the mixture was separated. The organic layer was washed with water. The crude product obtained by concentration under reduced pressure was purified by silica gel column chromatography, and the resulting solid was dried at 40°C to obtain 3 g of compound (1-1). Compound (1-1) LC / MS: m / z = 685.35 ([M+H] + ) 1H NMR(400MHz,DMSO-d6):δ7.68(d,J=8.8Hz,2H),δ7.49(d,J=7.6Hz,2H),δ7.37-7.32(m,4H),δ7.27-7.23(m,2H),δ7.13(d,J=8.8Hz,2H),δ7.05( d,J=10.4Hz,2H),δ6.88-6.84(m,4H),δ6.32(d,J=10.0Hz,2H),δ4.35-4 .27(m,2H),δ1.66-1.46(m,4H),δ1.18-1.16(m,6H),δ0.89-0.85(m,6H)

[0087] <Example 2> A compound represented by the following formula (1-2) was obtained by the following method: The compound represented by the following formula (1-2) is referred to as compound (1-2).

[0088] [ka]

[0089] 4-ethoxybenzophenone 4-Ethoxybenzophenone was synthesized in the same manner as in the synthesis of 4-n-butoxybenzophenone described in Polymer Journal, 1990, 22(8), 705, except that n-butyl bromide was changed to ethyl iodide. GC / MS: m / z = 225.95 ([M] + )

[0090] 1-(4-ethoxyphenyl)-3-(trimethylsilyl)-1-phenylprop-2-yn-1-ol 1-(4-Ethoxyphenyl)-3-(trimethylsilyl)-1-phenylprop-2-yn-1-ol was synthesized in the same manner as in the synthesis of 1-(4-sec-butoxyphenyl)-3-(trimethylsilyl)-1-phenylprop-2-yn-1-ol in Example 1, except that 4-sec-butoxybenzophenone was changed to 4-ethoxybenzophenone. GC / MS: m / z = 324.05 ([M] + ) 1 H NMR(400MHz,DMSO-d6):δ7.50(d,2H),δ7.40(d,2H),δ7.30(t,2H),δ7.20(t ,1H),δ6.84(d,2H),δ6.67(s,1H),δ3.97(q,2H),δ1.29(t,3H),δ0.21(s,9H)

[0091] 1-(4-ethoxyphenyl)-1-phenylprop-2-yn-1-ol 1-(4-Ethoxyphenyl)-1-phenylprop-2-yn-1-ol was synthesized in the same manner as in the synthesis of 1-(4-sec-butoxyphenyl)-1-phenylprop-2-yn-1-ol in Example 1, except that 1-(4-sec-butoxyphenyl)-3-(trimethylsilyl)-1-phenylprop-2-yn-1-ol was changed to 1-(4-ethoxyphenyl)-3-(trimethylsilyl)-1-phenylprop-2-yn-1-ol. GC / MS: m / z = 251.95 ([M] + ) 1 H NMR(400MHz,DMSO-d6):δ7.50(d,2H),δ7.38(d,2H),δ7.30(t,2H),δ7.21(t,1H),δ6.84(d,2H),δ6.68(s,1H),δ3.97(q,2H),δ1.29(t,3H)

[0092] Compound (1-2) Compound (1-2) was obtained in the same manner as in the synthesis of compound (1-1), except that 1-(4-sec-butoxyphenyl)-1-phenylprop-2-yn-1-ol was changed to 1-(4-ethoxyphenyl)-1-phenylprop-2-yn-1-ol. Compound (1-2) LC / MS: m / z = 629.45 ([M+H] + ) 1H NMR(400MHz,DMSO-d6):δ7.67(d,J=9.2Hz,2H),δ7.50-7.47(m,4H),δ7.40-7.32(m,8H),δ7.27-7.23(m,2H),δ7.13(d,J=9 .2Hz,2H),δ7.06(dd,J=10.0Hz,2H),δ6.88-6.85(m,4H),δ6.31(dd,J=9.6Hz,2H),δ3.99-3.92(m,4H),δ1.29-1.25(m,6H)

[0093] Example 3 A compound represented by the following formula (1-3) was obtained by the following method: The compound represented by the following formula (1-3) is referred to as compound (1-3).

[0094] [ka]

[0095] 2,4-Di-sec-butoxybenzophenone 2,4-Di-sec-butoxybenzophenone was synthesized in the same manner as in the synthesis of 4-n-butoxybenzophenone described in Polymer Journal, 1990, 22(8), 705, except that n-butyl bromide was changed to sec-butyl bromide and 4-hydroxybenzophenone was changed to 2,4-dihydroxybenzophenone.

[0096] 1-(2,4-di-sec-butoxyphenyl)-3-(trimethylsilyl)-1-phenylprop-2-yn-1-ol 1-(2,4-Di-sec-butoxyphenyl)-3-(trimethylsilyl)-1-phenylprop-2-yn-1-ol was synthesized in the same manner as in the synthesis of 1-(4-sec-butoxyphenyl)-3-(trimethylsilyl)-1-phenylprop-2-yn-1-ol in Example 1, except that 4-sec-butoxybenzophenone was changed to 2,4-di-sec-butoxybenzophenone.

[0097] 1-(2,4-di-sec-butoxyphenyl)-1-phenylprop-2-yn-1-ol 1-(2,4-Di-sec-butoxyphenyl)-1-phenylprop-2-yn-1-ol was synthesized in the same manner as in the synthesis of 1-(4-sec-butoxyphenyl)-1-phenylprop-2-yn-1-ol in Example 1, except that 1-(4-sec-butoxyphenyl)-3-(trimethylsilyl)-1-phenylprop-2-yn-1-ol was changed to 1-(2,4-di-sec-butoxyphenyl)-3-(trimethylsilyl)-1-phenylprop-2-yn-1-ol.

[0098] Compound (1-3) Compound (1-3) was obtained in the same manner as in the synthesis of compound (1-1), except that 1-(4-sec-butoxyphenyl)-1-phenylprop-2-yn-1-ol was replaced with 1-(2,4-di-sec-butoxyphenyl)-1-phenylprop-2-yn-1-ol. LC / MS: m / z = 829.75 ([M+H] + ) 1 H NMR (400MHz, DMSO-d6): δ7.63-7.55(m,4H), δ7.46-7.43(m,4H), δ7.29-7.00(m,10H), δ6.49-6.43(m,4H), δ6.29- 6.26(m,2H),δ4.38-4.30(m,4H),δ1.67-1.03(m,17H),δ0.92-0.81(m,9H),δ0.73-0.66(m,3H),δ0.60-0.52(m,3H)

[0099] Example 4 A compound represented by the following formula (1-4) was obtained by the following method: The compound represented by the following formula (1-4) is referred to as compound (1-4), where Me represents a methyl group.

[0100] [ka]

[0101] 2-sec-butoxy-4-methoxybenzophenone 2-sec-butoxy-4-methoxybenzophenone was synthesized in the same manner as in the synthesis of 4-n-butoxybenzophenone described in Polymer Journal, 1990, 22(8), 705, except that n-butyl bromide was changed to sec-butyl bromide and 4-hydroxybenzophenone was changed to 2-hydroxy-4-methoxybenzophenone.

[0102] 1-(2-sec-butoxy-4-methoxyphenyl)-3-(trimethylsilyl)-1-phenylprop-2-yn-1-ol 1-(2-sec-butoxy-4-methoxyphenyl)-3-(trimethylsilyl)-1-phenylprop-2-yn-1-ol was synthesized in the same manner as in the synthesis of 1-(4-sec-butoxyphenyl)-3-(trimethylsilyl)-1-phenylprop-2-yn-1-ol in Example 1, except that 4-sec-butoxybenzophenone was changed to 2-sec-butoxy-4-methoxybenzophenone.

[0103] 1-(2-sec-butoxy-4-methoxyphenyl)-1-phenylprop-2-yn-1-ol 1-(2-sec-butoxy-4-methoxyphenyl)-1-phenylprop-2-yn-1-ol was synthesized in the same manner as in the synthesis of 1-(4-sec-butoxyphenyl)-1-phenylprop-2-yn-1-ol in Example 1, except that 1-(4-sec-butoxyphenyl)-3-(trimethylsilyl)-1-phenylprop-2-yn-1-ol was changed to 1-(2-sec-butoxy-4-methoxyphenyl)-3-(trimethylsilyl)-1-phenylprop-2-yn-1-ol.

[0104] Compound (1-4) Compound (1-4) was obtained in the same manner as in the synthesis of compound (1-1), except that 1-(4-sec-butoxyphenyl)-1-phenylprop-2-yn-1-ol was changed to 1-(2-sec-butoxy-4-methoxyphenyl)-1-phenylprop-2-yn-1-ol. Compound (1-4) LC / MS: m / z = 745.50 ([M+H] + ) 1 H NMR(400MHz,DMSO-d6):δ7.64-7.59(m,4H),δ7.43(d,J=7.2Hz,4H),δ7.29-7.00(m,10H),δ6.51-6.46(m,4H),δ6.30-6.26(m,2H),δ4 .39-4.28(m,2H),δ3.70(s,6H),δ1.57-1.15(m,4H),δ1.11-1.04(m,3H),δ0.87-0.81(m,3H),δ0.73-0.68(m,3H),δ0.60-0.53(m,3H)

[0105] <Comparative Example 1> A compound represented by the following formula (1'-1) was obtained by the method of Example 2 of US Pat. No. 5,464,567. The compound represented by the following formula (1'-1) is referred to as compound (1'-1).

[0106] [ka]

[0107] The compounds obtained in the examples and comparative examples were evaluated as follows. <Heat resistance test> The weight loss due to thermal decomposition of the compounds obtained in the examples and comparative examples was measured under the following measurement conditions using a thermogravimetric analyzer TGA-50 manufactured by Shimadzu Corporation, and the temperature at which a weight loss of 1% of the initial weight was observed was defined as the 1% weight loss temperature. (Measurement conditions) Measurements were performed under the following conditions: sample weight 10 mg, temperature rise rate 10°C / min (maximum temperature reached 500°C), nitrogen atmosphere, flow rate 20 mL / min. The heat resistance was evaluated based on the 1% weight loss temperature according to the following criteria. The results are shown in Table 1. A: 1% weight loss temperature is 250℃ or higher B: 1% weight loss temperature is 240℃ or higher and less than 250℃ C: 1% weight loss temperature is less than 240℃

[0108] [Table 1]

[0109] The compounds (1-1) to (1-4) produced in the examples were superior in heat resistance to the compound (1'-1) of Comparative Example 1.

[0110] <Spectral characteristics test> The compounds obtained in the examples and comparative examples were irradiated with ultraviolet light to cause coloration, and then the decolorization (fading) rate was evaluated. 10 mg of the compounds obtained in the examples and comparative examples was dissolved in 5 mL of an 8 wt % toluene solution of polymethacrylate, and the solution was applied to a glass substrate by spin coating and dried to form a thin film with a thickness of 1.5 μm. The transmittance of the obtained thin film was measured in the wavelength range of 350 to 500 nm using a UV-visible-near-infrared spectrophotometer V-570 (JASCO Corporation) (transmittance before irradiation). The thin film was colorless and transparent before UV irradiation.

[0111] The thin film was then irradiated with ultraviolet light (365 nm) for 10 minutes to color the thin film. Immediately after ultraviolet irradiation, the transmittance of the thin film was measured in the wavelength range of 350 to 500 nm using a V-570 ultraviolet-visible-near-infrared spectrophotometer (JASCO Corporation) (transmittance immediately after irradiation). The maximum absorption wavelength of the thin film immediately after ultraviolet irradiation (λmax (nm) when colored) is shown in Table 2. Table 2 also shows the transmittance of the thin film before ultraviolet irradiation and the transmittance of the thin film immediately after ultraviolet irradiation at λmax (nm) when colored.

[0112] After UV irradiation, the thin film was left standing at room temperature for 20 hours in the dark, and then left standing at 100°C for 30 minutes in the dark. Thereafter, the transmittance of the thin film was measured in the wavelength range of 350 to 500 nm using the method described above (transmittance after standing in the dark). The transmittance of the thin film at λmax when colored after standing in the dark is shown in Table 2 as "transmittance after standing in the dark."

[0113] The color retention rate (%) was calculated from the transmittance of the thin film before irradiation, the transmittance immediately after irradiation, and the transmittance after standing in the dark at λmax (nm) during coloring, using the following formula. Color retention rate (%) = 100 × (transmittance before irradiation - transmittance after standing in the dark) / (transmittance before irradiation - transmittance immediately after irradiation) Table 2 shows the color retention rate (%).

[0114] [Table 2]

[0115] When the compound becomes colored, the transmittance of the thin film decreases. The recovery of transmittance at λmax during coloration indicates that the colored compound has faded. The smaller the color retention rate (%), the faster the compound fades. The compounds (1-1) to (1-4) prepared in the examples were colored by ultraviolet irradiation. After coloring, they were decolorized under light-shielded conditions, demonstrating photochromic properties. The compounds prepared in the examples had a faster decolorization rate than the compound (1'-1) prepared in the comparative example.

Claims

1. A compound represented by the following general formula (1): 【Chemical 1】 (In general formula (1), R １１Ａ and R １１Ｂ each independently represents a linear, branched, or cyclic alkyl group which may have a substituent, or an aryl group which may have a substituent; R １２Ａ and R １２Ｂ each independently represents a hydrogen atom, an optionally substituted linear, branched or cyclic alkoxy group, or an optionally substituted aryloxy group, R １３Ａ , R １４Ａ , R １５Ａ , R １３Ｂ , R １４Ｂ and R １５Ｂ are each independently a hydrogen atom, a halogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted linear, branched or cyclic alkoxy group, an optionally substituted aryloxy group, a cyano group, or —CO ２ R ２１ represents R ２１ represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group, X Ａ and X Ｂ each independently represents an oxygen atom or a sulfur atom.

2. R １２Ａ and R １２Ｂ and each independently represent a hydrogen atom or a linear or branched alkoxy group having 1 to 8 carbon atoms which may have a substituent.

3. R １２Ａ and R １２Ｂ The compound according to claim 1 or 2, wherein is a hydrogen atom.

4. R １１Ａ and R １１Ｂ and each independently represent a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent.

5. R １３Ａ , R １４Ａ , R １５Ａ , R １３Ｂ , R １４Ｂ and R １５Ｂ and each independently represent a hydrogen atom, a halogen atom, or a linear, branched, or cyclic alkoxy group which may have a substituent.

6. X Ａ and X Ｂ The compound according to claim 1 or 2, wherein is an oxygen atom.

7. A compound represented by the following general formula (2): 【Chemistry 2】 (In general formula (2), R １１ , R １２ , R １３ , R １４ , R １５ and X satisfies any of the following (a), (b), and (c). (stomach): R １１ represents an optionally substituted branched alkyl group, R １２ represents a hydrogen atom, an optionally substituted linear, branched or cyclic alkoxy group, or an optionally substituted aryloxy group, R １３ , R １４ and R １５ are each independently a hydrogen atom, a halogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted linear, branched or cyclic alkoxy group, an optionally substituted aryloxy group, a cyano group, or —CO ２ R ２１ represents R ２１ represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group, X represents an oxygen atom or a sulfur atom. (B): R １１ represents a linear or cyclic alkyl group having 2 or more carbon atoms, which may have a substituent; R １２ represents an optionally substituted linear, branched or cyclic alkoxy group or an optionally substituted aryloxy group, R １３ , R １４ and R １５ are each independently a hydrogen atom, a halogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted linear, branched or cyclic alkoxy group, an optionally substituted aryloxy group, a cyano group, or —CO ２ R ２１ represents R ２１ represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group, X represents an oxygen atom or a sulfur atom. (C): R １１ represents a methyl group, R １２ represents an optionally substituted branched or cyclic alkoxy group or an optionally substituted aryloxy group, R １３ , R １４ and R １５ are each independently a hydrogen atom, a halogen atom, an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, an optionally substituted linear, branched or cyclic alkoxy group, an optionally substituted aryloxy group, a cyano group, or —CO ２ R ２１ represents R ２１ represents an optionally substituted linear, branched or cyclic alkyl group or an optionally substituted aryl group, X represents an oxygen atom or a sulfur atom.

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