JP2020105104A - Photochromic compound - Google Patents

Abstract

To provide a photochromic compound that has an excellent solubility.SOLUTION: Provided is a compound in which a 4-alkoxyphenyl group is substituted on one pyran ring of a naphthopyran skeleton having a structure in which two pyran rings are fused on both sides of a naphthalene skeleton, as exemplified by a compound synthesized by reacting 1,1-bis(4-isopropoxyphenyl)-2-propyn-1-ol with 2,6-dihydroxynaphthalene and trimethyl orthoformate.SELECTED DRAWING: None

Description

The present invention relates to photochromic compounds.

Photochromic compounds are colored by changing their chemical bond mode without changing the molecular weight when they receive light of a specific wavelength, and then return to their original chemical bond mode by light of another wavelength or thermal reaction and disappear. It is a reversible compound.

Among the photochromic compounds, the naphthopyran compound has been attracting attention as a T-type photochromic compound that is rapidly decolorized by a thermal reaction.

For example, Patent Document 1 describes a specific naphthopyran compound having an appropriate decolorization rate.
Further, for example, Non-Patent Document 1 describes a one-pot method that can obtain a naphthopyran compound in an excellent yield.

US Pat. No. 5,464,567

Weili, Z. Erick, M, C.; Org. Lett. 2003, 5(22), 4153-4154.

Generally, the photochromic compound is dissolved in an organic solvent or the like and applied. Therefore, the property of being excellent in solubility in various organic solvents is required.
In Patent Document 1 and Non-Patent Document 1, the solubility in an organic solvent is not examined,
There was room for improvement.

An object of the present invention is to provide a photochromic compound having excellent solubility.

The present inventors have conducted extensive studies to solve the above problems and found that the naphthopyran compound represented by the following general formula (1) has excellent solubility. The present inventors have further researched on the basis of this finding and completed the present invention.

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

(In the general formula (1), X ¹ and X ² represent oxygen atoms, Y ¹ and Y ² represent CH, R ^{1 to} R ⁴ represent general formula (2), and R ^{11 to} R ^{11 14} represents a hydrogen atom, a halogen atom, a hydroxyl group, a nitrile group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R ¹⁵ has 3 or more carbon atoms. Represents an alkyl group of the formula: * represents a bonding site with the pyran skeleton, and X ¹ and Y ¹ and X ² and Y ² respectively bond to adjacent carbon atoms among the carbon atoms constituting the naphthalene skeleton. .)

In the present invention, the general formula (1) is preferably any of the following general formulas (3) to (9).

In the compound of the present invention, the general formula (1) is more preferably any of the general formulas (5) to (9).

In the compound of the present invention, R ¹⁵ in the general formula (2) is preferably an alkyl group having 3 to 8 carbon atoms.
In the compound of the present invention, R ¹⁵ in the general formula (2) is preferably an alkyl group having 3 or 4 carbon atoms.

The compound of the present invention preferably has a solubility in toluene at 20° C. of 3 g/L or more, and a solubility in ethyl acetate at 20° C. of 0.5 g/L or more.

According to the present invention, a photochromic compound having excellent solubility can be provided.

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

(In the general formula (1), X ¹ and X ² represent oxygen atoms, Y ¹ and Y ² represent CH, R ^{1 to} R ⁴ represent general formula (2), and R ^{11 to} R ^{11 14} represents a hydrogen atom, a halogen atom, a hydroxyl group, a nitrile group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R ¹⁵ has 3 or more carbon atoms. Represents an alkyl group of the formula: * represents a bonding site with the pyran skeleton, and X ¹ and Y ¹ and X ² and Y ² respectively bond to adjacent carbon atoms among the carbon atoms constituting the naphthalene skeleton. .)

If X ¹ and Y ¹ and X ² and Y ² in the general formula (1) are respectively bonded to adjacent carbon atoms among the carbon atoms constituting the naphthalene skeleton, they are from the 1-position of the naphthalene skeleton to 8 It may be bonded to any of the positions.
Among them, the general formula (1) is preferably any of the following general formulas (3) to (9), more preferably any of the following general formulas (5) to (9), It is particularly preferable that it is one of the following general formulas (7) to (9).
The compound represented by the general formula (1) is colored by ultraviolet rays and exhibits orange to red color, and therefore can be appropriately selected from the compounds represented by the following general formula (1) according to a desired color. ..

R ^{11 to} R ¹⁴ in the general formula (2) are each a hydrogen atom, a halogen atom, a hydroxyl group, a nitrile group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. Represent
R ^{11 to} R ¹⁴ in the general formula (2) are preferably hydrogen atoms.

Examples of the halogen atom in R ^{11 to} R ¹⁴ include fluorine, chlorine, bromine, iodine and the like.

Examples of the alkyl group for R ^{11 to} R ¹⁴ include linear, branched or cyclic alkyl groups.
Examples of the linear, branched or cyclic alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group and an n-octyl group. A linear alkyl group such as an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group and an n-pentadecyl group;
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 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-dimethyl Hexyl 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 A branched alkyl group such as 5-tetramethylhexyl group;
Cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, 1-cyclopentyl-2,2-dimethylpropyl group, 1-cyclopentyl-2,2-dimethylpropyl group, 1-cyclohexyl-2,2-dimethylpropyl group (cycloalkyl Group); and examples of the alkyl group having a substituent include a fluoromethyl group, a chloromethyl group, a methoxymethyl group, a methoxyethyl group, a hydroxyethyl group and a benzyl group.

Examples of the aryl group for R ^{11 to} R ¹⁴ include a phenyl group, a nitrophenyl group, a cyanophenyl group, a hydroxyphenyl group, a carboxyphenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, a fluorophenyl group, and a chlorophenyl group. , Bromophenyl group, methoxyphenyl group, ethoxyphenyl group, trifluoromethylphenyl group, N,N-dimethylaminophenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, fluoronaphthyl group And aryl groups such as chloronaphthyl group, bromonaphthyl group and trifluoromethylnaphthyl group.

Examples of the alkoxy group for R ^{11 to} R ¹⁴ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and an n-pentyloxy group. Group, isopentyloxy group, neopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-dodecyloxy group.
Examples of the alkoxy group in which some or all of the hydrogen atoms are substituted with halogen include, for example, fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, 1,1,2,2,2-pentafluoroethoxy group. , 1,1,2,2-tetrafluoroethoxy group, 1,1,2-trifluoroethoxy group, 1,2,2-trifluoroethoxy group, 2,2,2-trifluoroethoxy group, 2,2 -Difluoroethoxy group, 1,2-difluoroethoxy group, 1,1-difluoroethoxy group, 2-fluoroethoxy group, 1-fluoroethoxy group, 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, 3,3,4,4,5,5,5 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-pentadeca Fluoro-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 , 9,9,10,10,11,11,12,12,13,13,14,14,14-heptadecafluoro-1 -Tetradecyloxy group, 1H,1H,2,5-bis(trifluoromethyl)-3,6-dioxaundecafluoro-1-nonyloxy group, 6-(perfluoro-1-methylethyl)-1-hexyl Oxy group, 2-(perfluoro-1-methylbutyl)-1-ethoxy group, 2-(perfluoro-3-methylbutyl)ethoxy group, 2-(perfluoro-7-methyloctyl)ethoxy group, 2H-hexafluoro-2- Examples include propoxy group and 2,2-bis(trifluoromethyl)-1-propoxy group.

Examples of the aryloxy group for R ^{11 to} R ¹⁴ include a phenoxy group, a 1-naphthoxy group, a 2-naphthoxy group, a 2-methylphenoxy group, a 4-methylphenoxy group, a 4-tert-butylphenoxy group, and a 2-methoxy group. Examples thereof include a phenoxy group and a 4-isopropylphenoxy group.
As the aryloxy group having a substituent, for example, 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, mono- or An aryloxy group having a di-alkylamino group (the carbon number of the alkyl group is 1 to 8), a halogen atom, a cyano group, a hydroxy group, a nitro group and the like can be mentioned.

Examples of the acyl group in R ^{11 to} R ¹⁴ include 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. Can be mentioned.

Examples of the alkoxycarbonyl group for R ^{11 to} R ¹⁴ include an alkoxycarbonyl group having 2 to 8 carbon atoms.
Specifically, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentyl. Oxycarbonyl group, isopentyloxycarbonyl group, neopentyloxycarbonyl group, 1,2-dimethyl-propyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, 1,3-dimethyl-butyloxycarbonyl group, 1-isopropylpropyloxycarbonyl group, 1,2-dimethylbutyloxycarbonyl group, n-heptyloxycarbonyl group, 1,4-dimethylpentyloxycarbonyl group, 2-methyl-1-isopropylpropyloxycarbonyl group, 1-ethyl -3-methylbutyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, 3-methyl-1-isopropylbutyloxycarbonyl group, 2-methyl-1-isopropyloxycarbonyl group, 1-tert- Butyl-2-methylpropyloxycarbonyl group, n-nonyloxycarbonyl group, methoxymethoxycarbonyl group, methoxyethoxycarbonyl group, ethoxyethoxycarbonyl group, propoxyethoxycarbonyl group, butoxyethoxycarbonyl group, diethylaminoethoxycarbonyl group, methylthioethoxycarbonyl Group, methoxypropyloxycarbonyl group, γ-methoxypropoxycarbonyl group, γ-ethoxypropoxycarbonyl group, methoxyethoxyethoxycarbonyl group, ethoxyethoxyethoxycarbonyl group, dimethoxymethoxycarbonyl group, diethoxymethoxycarbonyl group, dimethoxyethoxycarbonyl group, Diethoxyethoxycarbonyl group, (3,6,9-oxa)decyloxycarbonyl group, tetrahydrofurfuryloxycarbonyl group, pyranoxycarbonyl group, piperidinooxycarbonyl group, piperidinoethoxycarbonyl group, tetrahydropyrroleoxycarbonyl group Group, tetrahydropyran methoxycarbonyl group, tetrahydrothiopheneoxycarbonyl group, cyclohexyloxycarbonyl group and the like.

Examples of the aryloxycarbonyl group for R ^{11 to} R ¹⁴ include a phenoxycarbonyl group, a 4-dimethylaminophenyloxycarbonyl group, a 4-diethylaminophenyloxycarbonyl group, a 2-chlorophenyloxycarbonyl group, and a 2-methylphenyloxycarbonyl group. , 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, Substituted or unsubstituted phenyloxycarbonyl group such as 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group; 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, etc. Examples thereof include a substituted or unsubstituted naphthyloxycarbonyl group and the like.

R ¹⁵ in the general formula (2) represents an alkyl group having 3 or more carbon atoms.
Examples of the alkyl group having 3 or more carbon atoms include linear, branched or cyclic alkyl groups similar to the alkyl groups in R ^{11 to} R ¹⁴ .
Among these, an alkyl group having 3 to 8 carbon atoms is preferable from the viewpoint of imparting excellent solubility, and a propyl group, an isopropyl group, and n- which are alkyl groups having 3 or 4 carbon atoms from the viewpoint of gram extinction coefficient. A butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group are preferable, a propyl group and a sec-butyl group are more preferable, and a sec-butyl group is still more preferable.

The compound of the present invention is preferably a compound that is soluble in an organic solvent.
Examples of the organic solvent include aromatic hydrocarbons (eg, toluene, xylene, etc.), ketones (methyl ethyl ketone, acetone, cyclohexanone, 2-heptanone, 3-heptanone, etc.), ethers (eg, propylene glycol monomethyl ether acetate). , Methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, etc.), esters (for example, 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 method for producing the compound of the present invention will be described below with reference to an example of the synthetic method, but the method for producing the compound of the present invention is not limited to the following method. Further, when carrying out the reaction described below, functional groups other than the site may be protected with an appropriate protecting group in advance, if necessary, and deprotected at an appropriate stage.

The compound of the present invention can be produced, for example, by reacting the following general formula (10) with the general formulas (11) and (11′).

In the general formula (10), the hydroxyl group may be bonded to any of positions 1 to 8 of the naphthalene skeleton.
As the compound represented by the general formula (10), commercially available compounds can be appropriately used.

^{R 1,} R 2, ^{R 3} and ^{R 4} in the general formula (11) and (11 ') are respectively synonymous with ^{R 1,} R 2, ^{R 3} and ^{R 4} in the general formula (1), respectively It represents the general formula (2).

The method for producing the compounds represented by the general formulas (11) and (11′) is not particularly limited. For example, it can be manufactured by the method described in JP 2012-501326 A, CN103936793A, or the like.

The conditions for reacting the compound represented by the general formula (10) with the compounds represented by the general formulas (11) and (11′) are not particularly limited. The reaction is usually carried out in a solvent under acid catalysis.

The acid catalyst is not particularly limited. For example, 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 can be used. Can be mentioned.

The solvent is not particularly limited as long as it is an inert solvent for the reaction. For example, dichloroethane, toluene, xylene, ethanol, isopropyl alcohol, acetonitrile and the like can be mentioned.
The temperature at the time of reaction can be 20-100 degreeC, and 30-70 degreeC is preferable. The reaction time can be 1 to 24 hours, preferably 1.5 to 5 hours.
The reaction efficiency can be improved by adding a dehydrating agent such as trimethyl orthoformate into the reaction system.

Isolation and purification of the product in the above production method can be carried out by appropriately combining methods used in ordinary organic synthesis, for example, filtration, extraction, washing, drying, concentration, crystallization, various chromatography and the like.

The solubility of the compound of the present invention in toluene at 20° C. is preferably 3 g/L or more, more preferably 5 g/L or more, further preferably 8 g/L or more, and 10 g/L or more. It is particularly preferable that The compound of the present invention has a solubility in ethyl acetate at 20° C. of preferably 0.5 g/L or more, more preferably 1 g/L or more, further preferably 2 g/L or more, It is particularly preferably 3 g/L or more.
If the compound of the present invention has a solubility in toluene and ethyl acetate in the above range, it also has excellent solubility in the above-mentioned organic solvent, and it is suitable for use as will be described later. You can
The above-mentioned solubility is obtained by, for example, adding a solvent (toluene or ethyl acetate) at 20°C to a glass test tube in which 50 mg of the compound of the present invention is weighed, and visually observing the state of the solution to completely dissolve it. The concentration can be obtained by a method such as measuring the concentration.

The compound of the present invention can be made into a dye composition by mixing with, for example, a resin. The coloring composition is preferably used as a coloring composition.
The resin is not particularly limited, and a thermoplastic resin, a photocurable resin, a thermosetting resin, or the like may be appropriately selected according to the application of the coloring composition and the like. For example, 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. Examples include resins such as polysulfone resin, polyether sulfone resin, fluororesin, silicone resin, polyester resin, epoxy resin, phenol resin, and melamine resin. These may be used alone or in combination of two or more.

The compounding amount of the compound of the present invention in the dye composition is, for example, preferably 0.001 to 50% by mass, and 0.01 to 40% by mass of the compound with respect to the total solid content of the dye composition. Is more preferable.

The dye composition may contain an optional component other than the compound of the present invention and the resin, depending on its application. Examples of optional components include antioxidants, defoamers, other dyes (dyes, pigments, etc.), infrared absorbers, ultraviolet absorbers, polymerizable monomers, polymerization initiators, sensitizers, and the like.
The method for producing the dye composition is not particularly limited, and for example, the compound and resin of the present invention, and optional components to be blended may be mixed.

The dye composition containing the compound of the present invention has an appropriate decoloring rate and is also excellent in solubility, and therefore, for example, dyes for optical filters, textile products such as print shirts, printing inks, and decorative materials. It is preferably used for manufacturing toys, display materials, window materials, agricultural films, packaging materials, stationery and the like. The present invention also includes optical filters containing the compound of the present invention, pigments for optical filters, textile products such as print shirts, printing inks, decorative materials, toys, display materials, window materials, agricultural films, packaging materials, stationery and the like. To be done. Dyes for optical filters, textile products such as print shirts, printing inks, decorative materials, toys, display materials, window materials, agricultural films, packaging materials, and stationery may be those containing the compound of the present invention. The configuration is not particularly limited.
The pigment compound containing the compound of the present invention is particularly suitable as a pigment composition for spectacle lenses including sunglasses and eyesight-correcting lenses. Eyeglass lenses containing the compounds of the invention are an example of a preferred embodiment of the invention.

Any optical filter may be used as long as it contains the compound of the present invention. For example, it may have a support and, if necessary, an optical functional layer and the like, as in the conventional filter. In the optical filter, the compound of the present invention is preferably contained in the support or the optical functional layer.

The configurations of the support and the optical functional layer are not particularly limited. For example, the support is usually formed by using a transparent resin. Examples of the transparent resin include cyclic olefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide (aramid) resin, polyarylate resin, polysulfone. Resins, polyether sulfone resins, polyparaphenylene resins, polyamideimide resins, polyurethane resins, polythiourethane resins, polyethylene naphthalate (PEN) resins, fluorinated aromatic polymer resins, (modified) acrylics Examples of the resin include epoxy resins and epoxy resins.

The manufacturing method of 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 in a solvent, dip coating method, air knife coating method, curtain Examples of the method include forming a coating film on the support by a coating method such as a coating method, a roller coating method, a wire bar coating method, a gravure coating method, a spin coating method and an extrusion coating method. The solvent is not particularly limited, and examples thereof include the above-mentioned organic solvents.

Further, as a method for producing an optical functional layer or a support containing the compound of the present invention, a compound of the present invention, a photocurable resin and / or a thermosetting resin and a photopolymerization initiator and / or a thermal polymerization initiator After mixing, a cured film may be formed by light irradiation and/or heat treatment, and this may be used as an optical functional layer or a support.

As a method for producing a lens which is an example of an optical filter, for example, a method of kneading a compound of the present invention in a transparent resin and molding by injection molding method, compression molding method, extrusion molding method, or the like on the support Various methods such as a method of forming an optical functional layer containing the compound of the present invention can be adopted.

Examples that more specifically describe the present invention will be shown below, but the present invention is not limited to these examples.

The equipment used for measuring the physical properties of the obtained compound is as follows.
(LC/MS)
Shimadzu Corporation High Performance Liquid Chromatograph Mass Spectrometer LCMS-2010EV (ESI method)
(NMR)
JEOL Ltd. nuclear magnetic resonance system JNM-ECZ400S

<Example 1>
Compound 1 was obtained by the following method.
Synthesis of 4,4′-diisopropoxybenzophenone 4,4′-Diisopropoxybenzophenone was obtained in the same manner as the method described in JP 2012-501326 A.

Synthesis of 1,1-bis(4-isopropoxyphenyl)-2-propyn-1-ol In the synthesis of 1,1-bis(2-methoxyphenyl)-2-propyn-1-ol described in CN103936793, 2 1,1-bis(4-isopropoxyphenyl)-2-propyn-1-ol was obtained in the same manner except that 2,2′-dimethoxybenzophenone was changed to 4,4′-diisopropoxybenzophenone.

Synthesis of Compound 1 In a 200 ml reaction flask equipped with a thermometer, 1,1-bis(4-isopropoxyphenyl)-2-propyn-1-ol 11.7 g, dichloroethane 90 ml, 2,6-dihydroxynaphthalene (Tokyo 2.4 g of Kasei Co., Ltd.) and 6.4 g of trimethyl orthoformate (Tokyo Kasei Co., Ltd.) (Tokyo Kasei Co.) were added. With stirring, 0.38 g of pyridinium p-toluenesulfonate (manufactured by Tokyo Kasei Co., Ltd.) was added, and the mixture was reacted at room temperature for 2 hours. The crystals taken out were washed with methanol to obtain 3.5 g of compound 1.
LC-MS: m/z=773 [M+H] ^+
1 H-NMR (400 MHz, CDCl ₃ ): δ1.30 (d, 24H), 4.50 (sep, 4H), 6.19 (d, 2H), 6.80 (d, 8H), 7.15. -7.20 (m, 4H), 7.34 (d, 8H), 7.78 (d, 2H)

<Example 2>
Compound 2 was obtained by the following method.
Synthesis of 4,4′-dipropoxybenzophenone In the synthesis of 4,4′-diisopropoxybenzophenone described in JP 2012-501326 A, 4 was similarly prepared except that isopropyl bromide was changed to propyl bromide. , 4'-dipropoxybenzophenone was obtained.

Synthesis of 1,1-bis(4-propoxyphenyl)-2-propyn-1-ol In the synthesis of 1,1-bis(2-methoxyphenyl)-2-propyn-1-ol described in CN103936793, 2, 1,1-Bis(4-propoxyphenyl)-2-propyn-1-ol was obtained in the same manner except that 2′-dimethoxybenzophenone was changed to 4,4′-dipropoxybenzophenone.

Synthesis of Compound 2 In the synthesis of Compound 1, 1,1-bis(4-isopropoxyphenyl)-2-propyn-1-ol was replaced with 1,1-bis(4-propoxyphenyl)-2-propyn-1-ol. Compound 2 was obtained in the same manner as in the synthesis of compound 1, except that the above was changed to.
LC-MS: m/z=773 [M+H] ^+
1 H-NMR (400 MHz, CDCl ₃ ): δ1.01 (t, 12H), 1.78 (sext, 8H), 3.88 (t, 8H), 6.19 (d, 2H), 6.82. (D, 8H), 7.14-7.20 (m, 4H), 7.36 (d, 8H), 7.77 (d, 2H)

<Example 3>
Compound 3 was obtained by the following method.
Synthesis of 4,4′-dibutoxybenzophenone In the synthesis of 4,4′-diisopropoxybenzophenone described in JP 2012-501326 A, 4 was similarly prepared except that isopropyl bromide was changed to butyl bromide. , 4'-Dibutoxybenzophenone was obtained.

Synthesis of 1,1-bis(4-butoxyphenyl)-2-propyn-1-ol In the synthesis of 1,1-bis(2-methoxyphenyl)-2-propyn-1-ol described in CN103936973, 2, 1,1-Bis(4-butoxyphenyl)-2-propyn-1-ol was obtained in the same manner except that 2′-dimethoxybenzophenone was changed to 4,4′-dibutoxybenzophenone.

Synthesis of compound 3 1,1-bis(4-isopropoxyphenyl)-2-propyn-1-ol in the synthesis of compound 1 was replaced with 1,1-bis(4-butoxyphenyl)-2-propyn-1-ol. Compound 3 was obtained in the same manner as in the synthesis of compound 1, except that the compound was changed to.
LC-MS: m/z=829 [M+H] ^+
1 H-NMR (400 MHz, CDCl ₃ ): δ 0.96 (t, 12H), 1.46 (sext, 8H), 1.70-1.75 (m, 8H), 3.92 (t, 8H). , 6.19 (d, 2H), 6.81 (d, 8H), 7.14-7.19 (m, 4H), 7.35 (d, 8H), 7.77 (d, 2H).

<Example 4>
Compound 4 was obtained by the following method.
Synthesis of 4,4′-diisobutoxybenzophenone In the synthesis of 4,4′-diisopropoxybenzophenone described in JP 2012-501326 A, 4 was similarly prepared except that isopropyl bromide was changed to isobutyl bromide. , 4'-Diisobutoxybenzophenone was obtained.

Synthesis of 1,1-bis(4-isobutoxyphenyl)-2-propyn-1-ol In the synthesis of 1,1-bis(2-methoxyphenyl)-2-propyn-1-ol described in CN103936973, 2 1,1-bis(4-isobutoxyphenyl)-2-propyn-1-ol was obtained in the same manner except that 2,2′-dimethoxybenzophenone was changed to 4,4′-diisobutoxybenzophenone.

Synthesis of Compound 4 1,1-Bis(4-isopropoxyphenyl)-2-propyn-1-ol in the synthesis of Compound 1 was converted to 1,1-bis(4-isobutoxyphenyl)-2-propyne-1- Compound 4 was obtained in the same manner as the synthesis of compound 1 except that all was changed.
LC-MS: m/z=829 [M+H] ^+
1 H-NMR (400 MHz, CDCl ₃ ): δ 1.00 (d, 24H), 2.05 (sep, 4H), 3.68 (d, 8H), 6.19 (d, 2H), 6.82. (D, 8H), 7.14-7.20 (m, 4H), 7.35 (d, 8H), 7.77 (d, 2H)

<Example 5>
Compound 5 was obtained by the following method.
Synthesis of 4,4'-di-sec-butoxybenzophenone In the synthesis of 4,4'-diisopropoxybenzophenone described in JP 2012-501326 A, except that isopropyl bromide is changed to -sec-butyl bromide. In the same manner, 4,4'-di(sec-butoxy)benzophenone was obtained.

Synthesis of 1,1-bis(4-sec-butoxyphenyl)-2-propyn-1-ol In the synthesis of 1,1-bis(2-methoxyphenyl)-2-propyn-1-ol described in CN103393679, 1,1-bis(4-sec-butoxyphenyl)-2-propyn-1-ol was similarly prepared except that 2,2′-dimethoxybenzophenone was changed to 4,4′-di-sec-butoxyphenylbenzophenone. Got

Synthesis of Compound 5 1,1-Bis(4-isopropoxyphenyl)-2-propyn-1-ol in the synthesis of Compound 1 was converted to 1,1-bis(4-sec-butoxyphenyl)-2-propyne-1. Compound 5 was obtained in the same manner as the synthesis of compound 1 except that the compound was changed to -ol.
LC-MS: m/z=829 [M+H] ^+
1 H-NMR (400 MHz, CDCl ₃ ): δ0.95 (t, 12H), 1.27 (d, 12H), 1.54-1.74 (m, 8H), 4.25 (sext, 4H). , 6.20 (d, 2H), 6.81 (d, 8H), 7.15-7.20 (m, 4H), 7.34 (d, 8H), 7.78 (d, 2H).

<Example 6>
Compound 6 was obtained by the following method.
Synthesis of 4,4'-di-n-hexylbenzophenone In the synthesis of 4,4'-diisopropoxybenzophenone described in JP 2012-501326 A, except that isopropyl bromide is changed to -n-hexyl bromide. In the same manner, 4,4'-di-n-hexylbenzophenone was obtained.

Synthesis of 1,1-bis(4-n-hexyloxyphenyl)-2-propyn-1-ol In the synthesis of 1,1-bis(2-methoxyphenyl)-2-propyn-1-ol described in CN103936793. ,2,2'-Dimethoxybenzophenone was changed to 4,4'-di-n-hexylbenzophenone in the same manner as described above, 1,1-bis(4-n-hexyloxyphenyl)-2-propyne-1- Got all.

Synthesis of Compound 6 1,1-Bis(4-isopropoxyphenyl)-2-propyn-1-ol in the synthesis of Compound 1 was converted to 1,1-bis(4-n-hexyloxyphenyl)-2-propyne- Compound 6 was obtained in the same manner as the synthesis of compound 1 except that it was changed to 1-ol.
LC-MS: m/z=942 [M+H] ^+
1 H-NMR (400 MHz, CDCl ₃ ): δ 0.90 (t, 12H), 1.28-1.47 (m, 24H), 1.71-1.78 (m, 8H), 3.91 ( t, 8H), 6.19 (d, 2H), 6.81 (d, 8H), 7.14-7.20 (m, 4H), 7.35 (d, 8H), 7.77 (d. , 2H)

<Example 7>
Compound 7 was obtained by the following method.
Synthesis of 4,4'-di-n-octylbenzophenone In the synthesis of 4,4'-diisopropoxybenzophenone described in JP 2012-501326 A, except that isopropyl bromide is changed to -n-octyl bromide. In the same manner, 4,4'-di-n-octylbenzophenone was obtained.

Synthesis of 1,1-bis(4-n-octyloxyphenyl)-2-propyn-1-ol In the synthesis of 1,1-bis(2-methoxyphenyl)-2-propyn-1-ol described in CN103936793. , 2,2'-Dimethoxybenzophenone was changed to 4,4'-di-n-octylbenzophenone in the same manner as described above, 1,1-bis(4-n-octyloxyphenyl)-2-propyne-1- Got all.

Synthesis of Compound 7 In the synthesis of Compound 1, 1,1-bis(4-isopropoxyphenyl)-2-propyn-1-ol was replaced with 1,1-bis(4-n-octyloxyphenyl)-2-propyne- Compound 7 was obtained in the same manner as the synthesis of compound 1 except that it was changed to 1-ol.
LC-MS: m/z=1054 [M+H] ^+
1 H-NMR (400 MHz, CDCl ₃ ): δ0.89 (t, 12H), 1.24-1.46 (m, 40H), 1.71-1.78 (m, 8H), 3.90( t, 8H), 6.18 (d, 2H), 6.81 (d, 8H), 7.14-7.19 (m, 4H), 7.34 (d, 8H), 7.77 (d , 2H)

<Comparative Example 1>
Compound A was obtained by the following method.
Synthesis of 1,1-bis(4-methoxyphenyl)-2-propyn-1-ol 1,1-bis(4-methoxyphenyl)-2-propyn-1-ol was prepared in the same manner as the method described in CN103936793. Got

Synthesis of Compound A 1,1-bis(4-isopropoxyphenyl)-2-propyn-1-ol in the synthesis of Compound 1 was replaced with 1,1-bis(4-methoxyphenyl)-2-propyn-1-ol. Compound A was obtained in the same manner as in the synthesis of Compound 1, except that the above was changed to.

In compounds 1 to 6, in the general formula (8), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ in the general formula (2) each represent a hydrogen atom, and R ¹⁵ represents a substituent shown in Table 1. It is a compound. In the substituents shown in Table 1, * represents a binding site with the general formula (2).

<Example 8>
Synthesis of compound 8 In the same manner as in Example 5, 1,1-bis(4-sec-butoxyphenyl)-2-propyn-1-ol was obtained.
Changed 1,1-bis(4-isopropoxyphenyl)-2-propyn-1-ol in the synthesis of Compound 1 to 1,1-bis(4-sec-butoxyphenyl)-2-propyn-1-ol Then, Compound 8 was obtained in the same manner as in the synthesis of Compound 1, except that 2,6-dihydroxynaphthalene was changed to 2,7-dihydroxynaphthalene.
LC-MS: m/z=829 [M+H] ^+
1 H-NMR (400 MHz, CDCl ₃ ): δ 0.96 (t, 12H), 1.27 (d, 12H), 1.57-1.75 (m, 8H), 4.26 (sext, 4H). , 6.02 (d, 2H), 6.81 (d, 8H), 7.02 (d, 2H), 7.12 (d, 2H), 7.38 (d, 8H), 7.50 ( d, 2H)

<Example 9>
Synthesis of compound 9 In the same manner as in Example 5, 1,1-bis(4-sec-butoxyphenyl)-2-propyn-1-ol was obtained.
Changed 1,1-bis(4-isopropoxyphenyl)-2-propyn-1-ol in the synthesis of Compound 1 to 1,1-bis(4-sec-butoxyphenyl)-2-propyn-1-ol Then, Compound 9 was obtained in the same manner as in the synthesis of Compound 1, except that 2,6-dihydroxynaphthalene was changed to 2,3-dihydroxynaphthalene.
LC-MS: m/z=829 [M+H] ^+
1 H-NMR (400 MHz, CDCl ₃ ): δ0.97 (t, 12H), 1.29 (d, 12H), 1.57-1.76 (m, 8H), 4.27 (sext, 4H). , 6.23 (d, 2H), 6.80 (d, 8H), 7.20-7.32 (m, 4H), 7.42 (d, 8H), 7.86 (d, 2H).

Compound 8 is a compound in which R ¹ , R ² , R ³ and R ⁴ in the general formula (9) below are each a substituent represented by the following general formula (2′), and compound 9 is the following general formula (9) In 7), R ¹ , R ² , R ³ and R ⁴ are each a compound represented by the following general formula (2′).

The following evaluations were performed for each compound obtained in Examples and Comparative Examples. The results are shown in Table 2.
<Solubility test>
The solubility (g/L) in toluene and ethyl acetate at 20° C. of each of the compounds obtained in Examples and Comparative Examples was measured by the following method.
To a glass test tube in which 50 mg of each compound obtained in Examples and Comparative Examples was weighed, toluene at 20° C. or ethyl acetate was added, and the state of the solution was visually observed and completely dissolved. The density was measured and evaluated.

From the above results, when the compounds 1 to 9 obtained in Examples 1 to 9 and the compound A obtained in Comparative Example 1 were compared, it was confirmed that the compounds 1 to 9 had better solubility.
Further, in Examples 2 and 5 in which R ¹⁵ is a propyl group or a sec-butyl group, the solubility in toluene is more excellent, and in Example 5 in which R ¹⁵ is a sec-butyl group, the solubility in ethyl acetate is better. It was confirmed to be excellent.
Further, Examples 8 and 9 in which R ¹⁵ is a sec-butyl group and have the skeleton of the general formulas (7) and (9) are particularly excellent in both solubility in toluene and solubility in ethyl acetate. Was confirmed.
In Examples 6 and 7, the solubility in toluene was excellent, but it is considered that the gram extinction coefficient is reduced as compared with other Examples having an alkyl group having 3 or 4 carbon atoms.

Claims (6)

A compound represented by the following general formula (1).

(In the general formula (1), X ¹ and X ² represent oxygen atoms, Y ¹ and Y ² represent CH, R ^{1 to} R ⁴ represent general formula (2), and R ^{11 to} R ^{11 14} represents a hydrogen atom, a halogen atom, a hydroxyl group, a nitrile group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R ¹⁵ has 3 or more carbon atoms. Represents an alkyl group of the formula: * represents a bonding site with the pyran skeleton, and X ¹ and Y ¹ and X ² and Y ² respectively bond to adjacent carbon atoms among the carbon atoms constituting the naphthalene skeleton. .) The compound according to claim 1, wherein the general formula (1) is any one of the following general formulas (3) to (9).

The compound according to claim 2, wherein the general formula (1) is any one of the general formulas (5) to (9). The compound according to claim 1, wherein R ¹⁵ is an alkyl group having 3 to 8 carbon atoms. The compound according to claim 1, wherein R ¹⁵ is an alkyl group having 3 or 4 carbon atoms. The compound according to claim 1, which has a solubility in toluene at 20° C. of 3 g/L or more and a solubility in ethyl acetate at 20° C. of 0.5 g/L or more.