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WO2011078030A1 - Composé de chromène - Google Patents

Composé de chromène Download PDF

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Publication number
WO2011078030A1
WO2011078030A1 PCT/JP2010/072550 JP2010072550W WO2011078030A1 WO 2011078030 A1 WO2011078030 A1 WO 2011078030A1 JP 2010072550 W JP2010072550 W JP 2010072550W WO 2011078030 A1 WO2011078030 A1 WO 2011078030A1
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group
ring
condensed
carbon atoms
atom
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利彰 高橋
潤治 竹中
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Tokuyama Corp
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Tokuyama Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D455/00—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine
    • C07D455/02—Heterocyclic compounds containing quinolizine ring systems, e.g. emetine alkaloids, protoberberine; Alkylenedioxy derivatives of dibenzo [a, g] quinolizines, e.g. berberine containing not further condensed quinolizine ring systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom

Definitions

  • the present invention relates to a photochromic chromene compound, its use and an intermediate. More particularly, the present invention relates to a novel chromene compound useful as a photochromic compound for photochromic eyeglass lenses, its use, and an intermediate.
  • Photochromism is a reversible color that quickly changes when a compound is exposed to light containing ultraviolet light, such as sunlight or mercury lamp light, and stops when it is placed in a dark place. It is an action.
  • a compound having this property is called a photochromic compound and is used as a material for a photochromic plastic lens.
  • the degree of coloring in the visible light region before irradiation with ultraviolet rays (hereinafter referred to as “initial coloring”) is small; (II) The degree of coloration (hereinafter referred to as “color density”) when irradiated with ultraviolet rays is high, (III) The speed from the start of UV irradiation until the color density reaches saturation (hereinafter referred to as “color sensitivity”) (IV) A high speed (hereinafter referred to as “fading speed”) from when UV irradiation is stopped until it returns to its original state, (V) Curing so that the repetitive durability of the reversible action (hereinafter simply referred to as “repetitive durability” or “durability”) is good, and (VI) dispersibility in the host material used is high. There is a demand for the property of being dissolved at a high concentration in a monomer composition that later becomes a host material.
  • Photochromic plastic lenses using photochromic compounds are preferred to develop colors such as gray and brown.
  • Such an intermediate color can be obtained by mixing several kinds of photochromic compounds having different color tones during color development. Specifically, a yellow to red photochromic compound (yellow compound) having a maximum absorption at 430 to 530 nm is mixed with a purple to blue photochromic compound (blue compound) having a maximum absorption at 550 to 650 nm. Yes.
  • the color tone during the color development has a strong blue tint
  • the color tone during the color fading has a strong yellow tint
  • the present invention develops an intermediate color, has a small initial coloration, a high color density, a high color fading speed, a small color at the time of deterioration, and a small decrease in the color density when repeatedly used (for photochromic durability).
  • An object of the present invention is to provide a chromene compound that can be dissolved at a high concentration in a monomer composition that is an excellent base material for optical articles.
  • Another object of the present invention is to provide a process for producing the chromene compound of the present invention.
  • Another object of the present invention is to provide a photochromic curable composition comprising the chromene compound of the present invention and a polymerizable monomer.
  • Another object of the present invention is to provide a photochromic optical article having as a constituent member a polymer molded body in which the chromene compound of the present invention is dispersed.
  • Still another object of the present invention is to provide a novel naphthol derivative which is an intermediate in the production of the chromene compound of the present invention.
  • pyran skeleton compounds having highly electron-donating substituents bonded to the 6- and 7-positions of the indeno (2,1-f) naphtho (1,2-b) pyran skeleton
  • the substituent having a high electron donating property is specifically a substituent bonded to the 6-position and the 7-position with an oxygen atom or a nitrogen atom.
  • thermochromism initial coloration the color development due to heat at room temperature without light irradiation
  • thermochromism initial coloration is large. It has the disadvantage of low durability.
  • the electron-donating properties of the substituents at the 6-position and the 7-position are further increased, the degree of the above-described drawback increases.
  • the present inventors have conducted intensive studies to solve the above problems. As a result, the introduction of a sterically bulky substituent that does not have a high electron-donating property to at least one of the carbon atoms at positions 5 to 12 of the pyran skeleton of the above structural formula (1) results in color development.
  • the inventors have found that a chromene compound having a low initial coloration due to thermochromism and having a high double peak property can be obtained while maintaining various characteristics such as high density and fast fading speed.
  • a sterically bulky substituent includes an alicyclic ring, an aliphatic heterocyclic ring, an aromatic ring in an alicyclic ring in which a bonding site with a carbon atom of a pyran skeleton exists.
  • a condensed polycyclic group condensed with a ring or an aromatic heterocyclic ring, and an aliphatic heterocyclic ring having a bonding site with a carbon atom of a pyran skeleton, an alicyclic ring, an aliphatic heterocyclic ring, an aromatic ring or an aromatic ring It is selected from the group consisting of a condensed polycyclic group in which a heterocyclic ring is condensed.
  • the chromene compound according to the present invention maintains various characteristics such as high color density and fast fading speed, the initial coloration due to thermochromism is small, and the reason for the high double peak property is not clear.
  • a sterically bulky substituent into at least one carbon atom of the ⁇ 12-position carbon atom and a sterically bulky substituent, the introduced 5--12-position substituent and pyran It is inferred that an unpredictable effect is achieved by some steric interaction with the skeleton.
  • a first object of the present invention is a chromene compound having an indeno (2,1-f) naphtho (1,2-b) pyran skeleton of the structural formula (1) as a basic skeleton, Indeno (2,1-f) naphtho (1,2-b) pyran skeleton is such that at least one of the carbon atoms at positions 5 to 12 is the indeno (2,1-f) naphtho (1,2-b) pyran skeleton.
  • An alicyclic ring, an aliphatic heterocyclic ring, an aromatic ring or an aromatic heterocyclic ring is condensed to an aliphatic heterocyclic ring having a bonding site with a carbon atom of a naphtho (1,2-b) pyran skeleton.
  • the second object of the present invention is to produce the chromene compound.
  • a third object of the present invention is a photochromic curable composition containing the chromene compound and a polymerizable monomer.
  • a fourth object of the present invention is a photochromic optical article having as a constituent member a polymer molded body in which the chromene compound is dispersed.
  • a fifth object of the present invention is an optical article comprising, as a constituent member, an optical base material in which all or a part of at least one surface is coated with a polymer film in which the chromene compound is dispersed.
  • a sixth object of the present invention is a naphthol compound which is a raw material compound for producing the chromene compound of the present invention.
  • the chromene compound of the present invention exhibits an intermediate color tone, a small initial coloration, a high color density, and a fast fading speed even when dispersed in a solution or a polymer solid matrix. Excellent durability.
  • a photochromic lens using the chromene compound of the present invention when producing a photochromic lens using the chromene compound of the present invention, it is highly transparent indoors, and when it goes outdoors, it quickly develops a dark neutral color, and when it returns from the outdoors to the room, it fades quickly.
  • a highly durable photochromic lens that can be used for a long time can be manufactured.
  • the chromene compound of the present invention has an indeno (2,1-f) naphtho (1,2-b) pyran structure of the above structural formula (1) as a basic skeleton, and has a carbon atom at the 5- to 12-position of the pyran skeleton.
  • a condensed polycyclic ring in which at least one carbon atom is fused with an alicyclic ring, an aliphatic heterocyclic ring, an aromatic ring or an aromatic heterocyclic ring on an alicyclic ring in which a bonding site with a carbon atom of a pyran skeleton is present A group consisting of a condensed polycyclic group in which an alicyclic ring, an aliphatic heterocyclic ring, an aromatic ring, or an aromatic heterocyclic ring is condensed to an aliphatic heterocyclic ring in which a bonding site to a carbon atom of a pyran skeleton is present And having a substituent selected from the group consisting of a carbon-carbon bond, it is possible to develop a deep intermediate color with a single compound while maintaining excellent photochromic properties.
  • the valence of the heteroatom is Since it is 2 to 3, the atoms bonded to the carbon atom are sterically smaller than carbon having a valence of 4. Although this is considered to be the cause, the obtained chromene compound tends to have a large initial coloration.
  • the condensed polycyclic group in which the alicyclic ring is condensed to the alicyclic ring is not particularly limited, but is preferably a condensed polycyclic group having 4 to 20 carbon atoms constituting the ring, and having 7 to 20 carbon atoms.
  • the condensed polycyclic group is particularly preferred.
  • Preferred examples of the condensed polycyclic group in which an alicyclic ring is condensed to an alicyclic ring include, for example, a bicyclo [2,2,1] heptane ring, a bicyclo [2,2,2] octane ring, and a bicyclo Bicyclo ring groups such as [3,2,1] octane ring, bicyclo [3,3,1] nonane ring, bicyclo [4,3,0] nonane ring, and, for example, 1-adamantane ring, 2- And a tricyclo ring group such as an adamantane ring.
  • the condensed polycyclic group in which an aliphatic heterocyclic ring is condensed to an alicyclic ring is not particularly limited, but is preferably a condensed polycyclic group having 3 to 20 carbon atoms constituting the ring, and having 6 to 20 carbon atoms.
  • the condensed polycyclic group is particularly preferred.
  • condensed polycyclic group in which an aliphatic heterocycle is condensed to an alicyclic ring include an azabicyclo [2,2,1] heptane ring, an azabicyclo [2,2,2] octane ring, an azabicyclo [3 , 2,1] octane ring, azabicyclo [3,3,1] nonane ring, oxabicyclo [2,2,1] heptane ring, oxabicyclo [2,2,2] octane ring, oxabicyclo [3,2, 1] octane ring, oxabicyclo [3,3,1] nonane ring, thiabicyclo [2,2,1] heptane ring, thiabicyclo [2,2] octane ring, thiabicyclo [3,2,1] octane ring, Bicyclo ring groups such as thiabi
  • the condensed polycyclic group in which an aromatic ring is condensed to an alicyclic ring is not particularly limited, but a condensed polycyclic group having 7 to 30 carbon atoms constituting the ring is preferable.
  • Preferred examples of the condensed polycyclic group in which an aromatic ring is condensed to an alicyclic ring are as follows: benzocyclopropane ring group, benzocyclobutane ring group, benzocyclopentane ring group, benzocyclohexane ring group, benzocycloheptane A cyclic group, a benzocyclooctane cyclic group, etc. are mentioned.
  • the condensed polycyclic group in which an aromatic heterocyclic ring is condensed to an alicyclic ring is not particularly limited, but a condensed polycyclic group having 6 to 30 carbon atoms constituting the ring is preferable.
  • Preferred examples of the condensed polycyclic group in which an aromatic heterocyclic ring is condensed to an alicyclic ring are shown as 3,4-cyclopentenopyridine ring group, 3,4-cycloheptenopyridine ring group, 3,4 -Cyclooctenopyridine ring group and the like.
  • the condensed polycyclic group in which the alicyclic ring is condensed to the aliphatic heterocyclic ring is not particularly limited, but a condensed polycyclic group having 3 to 20 carbon atoms constituting the ring is preferable, and the carbon number is 6 to 20
  • the condensed polycyclic group is particularly preferred.
  • Preferred examples of the condensed polycyclic group in which an alicyclic ring is condensed to an aliphatic heterocyclic ring include an azabicyclo [4,3,0] nonane ring group, an oxabicyclo [4,3,0] nonane ring group, Examples include heptahydrocyclohexa [c] thiophene ring group.
  • the condensed polycyclic group in which the aliphatic heterocyclic ring is condensed to the aliphatic heterocyclic ring is not particularly limited, but is preferably a condensed polycyclic group having 3 to 20 carbon atoms constituting the ring, and having 6 to 20 carbon atoms.
  • the condensed polycyclic group is particularly preferred.
  • Preferred examples of the condensed polycyclic group in which an aliphatic heterocycle is condensed to an aliphatic heterocycle include, for example, a diazabicyclo [2,2,1] heptane ring, a diazabicyclo [2,2,2] octane ring, and a diazabicyclo.
  • the condensed polycyclic group in which an aromatic ring is condensed to an aliphatic heterocyclic ring is not particularly limited, but a condensed polycyclic group having 7 to 30 carbon atoms constituting the ring is preferable.
  • Preferred examples of the condensed polycyclic group in which an aromatic ring is condensed to an aliphatic heterocyclic ring include a 2-indoline ring group, a 2-coumaran ring group, a 2,3-dihydrobenzo [c] thiophene ring group, and the like. Can be mentioned.
  • the condensed polycyclic group in which an aromatic heterocyclic ring is condensed to an aliphatic heterocyclic ring is not particularly limited, but a condensed polycyclic group having 6 to 30 carbon atoms constituting the ring is preferable.
  • a preferred example of a condensed polycyclic group in which an aromatic heterocycle is condensed to an aliphatic heterocycle is 2,3-dihydropyrrolo [2,3-b] pyridine ring group, 2,3-dihydrofuro [2 ,, 3-b] pyridine ring group, 2,3-dihydrothieno [2,3-b] pyridine ring group, 4,6-dihydrofuro [3,4-b] furan group, 4,6-dihydrothieno [3,4-b ] A thiophene group etc. can be mentioned.
  • the condensed polycyclic group condensed with an aromatic ring or an aromatic heterocyclic ring may itself be substituted.
  • the substituent which the condensed polycyclic group condensed with the aromatic ring or the aromatic heterocyclic ring may be described in detail.
  • the substituent includes a hydroxyl group; an alkyl group; a haloalkyl group; a cycloalkyl group; an alkoxy group; A heterocyclic group in which a nitrogen atom is directly bonded to a carbon atom; a cyano group; a nitro group; a formyl group; a hydroxycarbonyl group; an alkylcarbonyl group; an alkoxycarbonyl group; a halogen atom; an aralkyl group; An aralkoxy group; or an aryloxy group.
  • the alkyl group is not particularly limited, but an alkyl group having 1 to 8 carbon atoms is preferable.
  • suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, etc. Can be mentioned.
  • the haloalkyl group is not particularly limited, but an alkyl group having 1 to 8 carbon atoms substituted with a fluorine atom, a chlorine atom or a bromine atom is preferable.
  • suitable haloalkyl groups include trifluoromethyl group, pentafluoroethyl group, chloromethyl group, 2-chloroethyl group, bromomethyl group and the like.
  • the cycloalkyl group is not particularly limited, but a cycloalkyl group having 3 to 8 carbon atoms is preferable.
  • suitable cycloalkyl groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
  • the alkoxy group is not particularly limited, but an alkoxy group having 1 to 8 carbon atoms is preferable.
  • suitable alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy and the like.
  • An amino group is an unsubstituted or substituted amino group.
  • substituent that the amino group may have include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • heteroaryl groups having 4 to 12 carbon atoms such as aryl groups having 6 to 14 carbon atoms, such as aryl groups, thienyl groups, furyl groups, pyrrolinyl groups, and pyridyl groups, etc.
  • alkyl groups specifically examples of alkyl groups, alkoxy groups, and cycloalkyl groups
  • suitable amino groups include amino groups, methylamino groups, dimethylamino groups, ethylamino groups, diethylamino groups, phenylamino groups, diphenylamino groups, and the like.
  • a heterocyclic group containing a nitrogen atom and in which the nitrogen atom is directly bonded to a carbon atom is not particularly limited, and examples thereof are morpholino group, piperidino group, pyrrolidinyl group, piperazino group, N-methylpiperazino group, An indolinyl group etc. can be mentioned.
  • the heterocyclic group may have an alkyl group having 1 to 8 carbon atoms as a substituent, and specific examples of the substituent include an alkyl group such as a methyl group.
  • Preferred examples of the heterocyclic group having a substituent include 2,6-dimethylmorpholino group, 2,6-dimethylpiperidino group, 2,2,6,6-tetramethylpiperidino group and the like. Is mentioned.
  • the alkylcarbonyl group is not particularly limited, and examples thereof include an acetyl group and an ethylcarbonyl group.
  • the alkoxycarbonyl group is not particularly limited, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group.
  • the halogen atom is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the aralkyl group is not particularly limited, but an aralkyl group having 7 to 11 carbon atoms is preferable.
  • suitable aralkyl groups include benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, naphthylmethyl group and the like.
  • the aryl group is not particularly limited, but an aryl group having 6 to 14 carbon atoms is preferable.
  • suitable aryl groups include phenyl group, 1-naphthyl group, 2-naphthyl group and the like.
  • the aralkoxy group is not particularly limited, but an aralkoxy group having 7 to 11 carbon atoms is preferable. Specific examples of suitable aralkoxy groups include benzyloxy groups and naphthylmethoxy groups.
  • the aryloxy group is not particularly limited, but an aryloxy group having 6 to 14 carbon atoms is preferable.
  • suitable aryloxy groups include phenoxy group, 1-naphthoxy group, 2-naphthoxy group and the like.
  • a group that is preferable in terms of obtaining a compound having small initial coloration and high double peak property can be exemplified.
  • Examples thereof include a condensed polycyclic group in which an alicyclic ring, an aliphatic heterocyclic ring or an aromatic ring is condensed to an alicyclic ring, or a condensed polycyclic group in which an alicyclic ring is condensed to an aliphatic heterocyclic ring.
  • the condensed polycyclic group that can be possessed by the carbon atoms at positions 5 to 12 of the pyran skeleton is a sterically bulky substituent having a lower electron donating property than the alkoxy group.
  • the chromene compound of the present invention preferably has a substituent in which the resulting chromene compound has the following form.
  • the benzene ring containing the carbon atom at the 5-8th position of the pyran skeleton is on the plane in the molecular orbital calculation by MOPACPM3.
  • the dihedral angle formed by the carbon atoms is 0 °.
  • the carbon atom at the 5-position of the pyran skeleton has the condensed polycyclic group as a substituent, among the condensed polycyclic groups, the 8-position, the 5-position of the pyran skeleton, It is preferable that the dihedral angle formed by the carbon atom at the 7-position and the carbon atoms at the 8-, 6- and 7-positions is 0.3 ° or more, and more preferably 0.5 ° or more. It is preferable that it is a substituent made into 1.0 degree or more especially.
  • the 6-position or 7-position carbon atom of the pyran skeleton has the above-mentioned condensed polycyclic group as a substituent
  • the carbon atoms at the 5-position, 6-position and 8-position of the pyran skeleton and 5 It is preferable that the dihedral angle formed by the carbon atoms at the position, 7-position, and 8-position is 0.3 ° or more, more preferably 0.5 ° or more.
  • the substituent is preferably 1.0 ° or more.
  • the carbon atom at the 8-position of the pyran skeleton has the above-mentioned condensed polycyclic group as a substituent, among the condensed polycyclic groups, the 6-position, 7-position, 5-position carbon atom and the 6-position, 8 It is preferable that the dihedral angle formed by the carbon atoms at the 5th and 5th positions is 0.3 ° or more, more preferably 0.5 ° or more, particularly 1.0 °. A substituent as described above is preferable.
  • the above substituent when the substituent is present on the carbon atoms at the 5th to 8th positions of the pyran skeleton, the above substituent is preferably located at the 6th or 7th position of the pyran skeleton in order to further enhance the double peak property. Bonding to a carbon atom is preferred.
  • the chromene compound in the case where there is no substituent at positions 9 to 12 of the pyran skeleton has a benzene ring containing a carbon atom at positions 9 to 12 of the pyran skeleton on a plane in the molecular orbital calculation by MOPACPM3.
  • the dihedral angle formed by the 12th carbon atom is 0 °.
  • the 9-position carbon atom of the pyran skeleton has the condensed polycyclic group as a substituent, among the condensed polycyclic groups, the 12-position, the 9-position, It is preferable that the dihedral angle formed by the carbon atom at the 11th position and the carbon atoms at the 12th, 10th and 11th positions is 1.0 ° or more, and more preferably 1.3 ° or more. In particular, the substituent is preferably 1.5 ° or more.
  • the carbon atom at the 10th or 11th position of the pyran skeleton has the above condensed polycyclic group as a substituent
  • the 9th, 10th, and 12th carbon atoms of the pyran skeleton and 9 It is preferable that the dihedral angle formed by the carbon atoms at the position, the 11th position, and the 12th position is 1.0 ° or more, more preferably 1.3 ° or more.
  • the substituent is preferably at least 1.5 °.
  • the 12-position carbon atom of the pyran skeleton has the above-mentioned condensed polycyclic group as a substituent, among the condensed polycyclic groups, the 10-position, 11-position, 9-position carbon atom and the 10-position, 12 It is preferable that the dihedral angle formed by the carbon atom at the position 9 and the 9-position is 1.0 ° or more, more preferably 1.3 ° or more, particularly 1.5. It is preferable that the substituent be at least 0 °.
  • the substituent when the substituent is present on the 9th to 12th carbon atoms of the pyran skeleton, the substituent is bonded to the 9th or 12th carbon atom in order to further enhance the double peak property. It is preferable.
  • preferable groups for satisfying the dihedral angle as described above include bicyclo [2,2,2] octane ring group, 1-adamantane ring group, 2-adamantane ring group, azabicyclo [2, 2,2] octane ring group, azabicyclo [4,3,0] nonane ring group, 1-azaadamantane ring group and the like.
  • a particularly preferable group in terms of high double peak property and small initial coloration includes a condensed polycyclic group in which an alicyclic ring is condensed to an alicyclic ring.
  • particularly preferred groups include a bicyclo [2,2,2] octane ring group, a 1-adamantane ring group, and a 2-adamantane ring group.
  • the molecular orbital calculation by MOPACPM3 is one of the molecular orbital methods (MO).
  • the molecular orbital method is one of the approximation methods for discussing the electronic state of molecules.
  • Empirical methods such as the Huckel method, semi-empirical methods that enhance the approximation of the Huckel method, and ab initio for obtaining molecular orbital functions strictly by calculation.
  • the molecular orbital method is one of the most powerful methods for relating a molecular structure to its chemical reactivity.
  • MOPACPM3 is a method that forms the core of the NDDO (Neglect of Diatomic Differential) Overlap) method, which is one of the semi-empirical methods. MOPACPM3 is used mainly for the purpose of considering the reaction and physical properties of organic compounds. Many documents and books [Molecular Orbital MOPAC Guidebook (Tsuneo Hirano, Kazutoshi Tanabe, Kaibundo, 1991), “Three “Introduction to Quantum Chemistry” (Sadajiro Yonezawa et al., Doujin Kagaku, 1983), “Computational Chemistry Guidebook” (Eiji Osawa et al., Tim Clark, Maruzen, 1985)].
  • chromene compound according to the present invention is represented by the following general formula (2).
  • R 1 and R 2 are an alicyclic ring or an aliphatic heterocyclic ring in the alicyclic ring in which the bonding site to the carbon atom of the indeno (2,1-f) naphtho (1,2-b) pyran skeleton exists.
  • R 1 ′ and R 2 ′ are each a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a nitrogen atom, and a heterocycle in which the nitrogen atom is directly bonded to a carbon atom of a pyran skeleton.
  • R 4 and R 5 are each independently represented by the general formula (3) A group represented by the formula: wherein R 8 is an aryl group or a heteroaryl group; R 9 is a hydrogen atom, an alkyl group, or a halogen atom; m is an integer of 1 to 3; General formula (4) (Wherein R 10 is an aryl group or a heteroaryl group; n is an integer of 1 to 3), an aryl group, a heteroaryl group, or an alkyl group, or R 4 and R 5 are bonded to each other to form an alicyclic ring; R 6 and R 7 are each independently a hydrogen atom; a hydroxyl group; an alkyl group; a haloalkyl group;
  • a condensed polycyclic group condensed with an aromatic ring or an aromatic heterocyclic ring, and an aliphatic heterocyclic ring having a bonding site with a carbon atom of a pyran skeleton include an alicyclic ring, an aliphatic heterocyclic ring, an aromatic ring or Details of the group selected from the group consisting of condensed polycyclic groups condensed with an aromatic heterocycle are as described above. At least one R 1 or R 2 must be present. That is, the sum (a + b) of a and b representing the number of R 1 and R 2 must be 1 or more and 8 or less.
  • R 1 ′ and R 2 ′ are each a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a nitrogen atom, and a heterocycle in which the nitrogen atom is directly bonded to a carbon atom of a pyran skeleton.
  • the alkyl group is not particularly limited, but an alkyl group having 1 to 8 carbon atoms is preferable.
  • suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, etc. Can be mentioned.
  • the haloalkyl group is not particularly limited, but an alkyl group having 1 to 8 carbon atoms substituted with a fluorine atom, a chlorine atom or a bromine atom is preferable.
  • suitable haloalkyl groups include trifluoromethyl group, pentafluoroethyl group, chloromethyl group, 2-chloroethyl group, bromomethyl group and the like.
  • the cycloalkyl group is not particularly limited, but a cycloalkyl group having 3 to 8 carbon atoms is preferable.
  • suitable cycloalkyl groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
  • the alkoxy group is not particularly limited, but an alkoxy group having 1 to 8 carbon atoms is preferable.
  • suitable alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy and the like.
  • An amino group is an amino group that is unsubstituted or optionally substituted.
  • substituent of the amino group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • a heteroaryl group having 4 to 12 carbon atoms such as an aryl group having 6 to 14 carbon atoms, a thienyl group, a furyl group, a pyrrolinyl group, and a pyridyl group (specific examples of an alkyl group, an alkoxy group, and a cycloalkyl group).
  • suitable amino groups include amino groups, methylamino groups, dimethylamino groups, ethylamino groups, diethylamino groups, phenylamino groups, diphenylamino groups, and the like.
  • the heterocyclic group containing a nitrogen atom and in which the nitrogen atom is directly bonded to a carbon atom is not particularly limited.
  • a morpholino group, piperidino group, pyrrolidinyl group, piperazino group, N-methylpiperazino group, An indolinyl group etc. can be mentioned.
  • the heterocyclic group may have an alkyl group having 1 to 8 carbon atoms as a substituent, and specific examples of the substituent include an alkyl group such as a methyl group.
  • Preferred examples of the heterocyclic group having a substituent include 2,6-dimethylmorpholino group, 2,6-dimethylpiperidino group, 2,2,6,6-tetramethylpiperidino group and the like. Is mentioned.
  • the alkylcarbonyl group is not particularly limited, and examples thereof include an acetyl group and an ethylcarbonyl group.
  • the alkoxycarbonyl group is not particularly limited, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group.
  • the halogen atom is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the aralkyl group is not particularly limited, but an aralkyl group having 7 to 11 carbon atoms is preferable.
  • suitable aralkyl groups include benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, naphthylmethyl group and the like.
  • the aryl group is not particularly limited, but an aryl group having 6 to 14 carbon atoms is preferable.
  • suitable aryl groups include phenyl group, 1-naphthyl group, 2-naphthyl group and the like.
  • the aralkoxy group is not particularly limited, but an aralkoxy group having 7 to 11 carbon atoms is preferable.
  • suitable aralkoxy groups include benzyloxy groups and naphthylmethoxy groups.
  • the aryloxy group is not particularly limited, but an aryloxy group having 6 to 14 carbon atoms is preferable.
  • suitable aryloxy groups include phenoxy group, 1-naphthoxy group, 2-naphthoxy group and the like.
  • R 1 ′ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; an alkoxy group having 1 to 8 carbon atoms; an amino group; or a nitrogen atom in that a high double peak property is obtained.
  • the nitrogen atom is preferably a heterocyclic group directly bonded to the carbon atom of the pyran skeleton.
  • Particularly suitable examples include a hydrogen atom, methyl group, methoxy group, N, N-dimethylamino group, morpholino group and the like.
  • R 1 ′ contains an alkyl group having 1 to 8 carbon atoms; an alkoxy group having 1 to 8 carbon atoms; an amino group; or a nitrogen atom, in order to enhance the double peak property.
  • a heterocyclic group that is directly bonded to a carbon atom of the skeleton is preferable. These groups are preferably bonded to the 6-position or 7-position carbon atom.
  • R 1 is bonded to either the 6-position or the 7-position carbon atom and contains an alkyl group having 1 to 8 carbon atoms; an alkoxy group having 1 to 8 carbon atoms; an amino group; or a nitrogen atom, R 1 ′ selected from a heterocyclic group in which the nitrogen atom is directly bonded to the carbon atom of the pyran skeleton is preferably bonded to the other carbon atom to which R 1 is not bonded.
  • R 2 ′ is preferably a hydrogen atom or an electron-withdrawing group in that a fast fading speed can be obtained.
  • R 2 ′ is an electron-withdrawing group
  • R 2 ′ is preferably bonded to a carbon atom at the 11-position in order to further increase the fading rate.
  • Suitable electron-withdrawing groups are a cyano group or a haloalkyl group having 1 to 8 carbon atoms, and specific examples include a cyano group and a trifluoromethyl group.
  • R 2 ′ is preferably a hydrogen atom.
  • R 4 and R 5 are each independently a group represented by the general formula (3), a group represented by the general formula (4), an aryl group, a heteroaryl group, or an alkyl group.
  • R 8 in the general formula (3) is an aryl group or a heteroaryl group.
  • the heteroaryl group is not particularly limited, but a heteroaryl group having 6 to 14 carbon atoms is preferable. Examples of suitable heteroaryl groups include thienyl, furyl, pyrrolinyl, pyridyl, benzothienyl, benzofuranyl, benzopyrrolinyl and the like.
  • R 9 of the general formula (3) is a hydrogen atom, an alkyl group or a halogen atom.
  • alkyl group examples include a methyl group, an ethyl group, and a propyl group.
  • halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • m is an integer of 1 to 3, but m is preferably 1 from the viewpoint of availability of raw materials.
  • Examples of suitable groups among the groups represented by the general formula (3) include phenyl-ethylenyl group, (4- (N, N-dimethylamino) phenyl) -ethenyl group, (4-morpholinophenyl)- Ethenyl group, (4-piperidinophenyl) -ethenyl group, (4-methoxyphenyl) -ethenyl group, (2-methoxyphenyl) -ethenyl group, phenyl-1-methylethenyl group, (4-methoxyphenyl) -1 -Methylethenyl group, phenyl-1-fluoroethenyl group, (4- (N, N-dimethylamino) phenyl) -1-fluoroethenyl group, 2-thienyl-ethenyl group, 2-furyl-ethenyl group, 2- (N-methyl) pyrrolinyl-ethenyl
  • R ⁇ 10 > is the same aryl group or heteroaryl group as said R ⁇ 8 >.
  • N is an integer of 1 to 3, and n is preferably 1 from the viewpoint of availability of raw materials.
  • Examples of suitable groups among the groups represented by the general formula (4) are phenyl-ethynyl group, (4- (N, N-dimethylamino) phenyl) -ethynyl group, (4-morpholinophenyl) -ethynyl.
  • Aryl group R 4 and R 5 the same group as the aryl group described above with reference to R 3 are applied.
  • the heteroaryl group for R 4 and R 5 is not particularly limited, but is preferably a heteroaryl group having 6 to 14 carbon atoms.
  • suitable heteroaryl groups include thienyl group, furyl group, pyrrolinyl group, pyridyl group, benzothienyl group, benzofuranyl group, benzopyrrolinyl group and the like.
  • alkyl groups the same groups as the alkyl group described for R 3 apply.
  • R 4 and R 5 can also be bonded to each other to form an alicyclic ring.
  • the alicyclic ring is not particularly limited, and specific examples of suitable rings include an adamantane ring, a bicyclononane ring, and a norbornane ring.
  • At least one of R 4 and R 5 is preferably an aryl group or a heteroaryl group. Furthermore, it is particularly preferable that at least one of R 4 and R 5 , preferably both, is any group shown in the following (i) to (iii). (I) an aryl group or heteroaryl group having an alkyl group or an alkoxy group as a substituent, (Ii) an aryl group or heteroaryl group having an amino group as a substituent, and (iii) a heterocyclic group having a nitrogen atom as a heteroatom, and the nitrogen atom and the aryl group or heteroaryl group are bonded. An aryl group or heteroaryl group as a group.
  • the position of the substituent is not particularly limited, and the total number is not particularly limited.
  • the substitution position is preferably the 3- or 4-position when the aryl group is a phenyl group.
  • the number of substituents is preferably 1 to 2.
  • suitable aryl groups are 4-methylphenyl group, 4-methoxyphenyl group, 3,4-dimethoxyphenyl group, 4-n-propoxyphenyl group, 4- (N, N-dimethylamino) phenyl.
  • the position of the substituent is not particularly limited, and the total number is not particularly limited, but the number is preferably 1.
  • suitable heteroaryl groups include 4-methoxythienyl group, 4- (N, N-dimethylamino) thienyl group, 4-methylfuryl group, 4- (N, N-diethylamino).
  • Examples include a furyl group, a 4- (N, N-diphenylamino) thienyl group, a 4-morpholinopyrrolinyl group, a 6-piperidinobenzothienyl group, and a 6- (N, N-dimethylamino) benzofuranyl group. .
  • R 6 and R 7 are each independently a hydrogen atom; a hydroxyl group; an alkyl group; a haloalkyl group; a cycloalkyl group; an alkoxy group; an amino group; a nitrogen atom, and the nitrogen atom is the carbon at the 13th position of the pyran skeleton.
  • R 6 and R 7 together with the carbon atom at the 13th position of the pyran skeleton, together with each other, the number of carbon atoms constituting the ring is 3 to 20 including the carbon atom at the 13th position.
  • a condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to the alicyclic ring a heterocycle having 3 to 20 atoms including the carbon atom at the 13-position, or You may form the condensed polycycle which the aromatic ring or the aromatic heterocycle condensed to the said heterocyclic ring.
  • Examples of the alicyclic ring having 3 to 20 carbon atoms including the carbon atom at the 13-position include, for example, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a norbornane ring, and a bicyclononane ring. And an adamantane ring.
  • examples of the condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed to an alicyclic ring include a benzocyclohexane ring.
  • heterocyclic ring having 3 to 20 atoms including the 13-position carbon atom examples include a dihydrothiophene ring, a dihydrofuran ring, a tetrahydrofuran ring, a dihydropyridine ring, and the like.
  • examples of the condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to a heterocyclic ring include a dihydrobenzofuran ring and a dihydrobenzothiophene ring.
  • R 6 and R 7 together with the carbon atom at the 13th position of the pyran structure form a ring together.
  • the alicyclic ring, or a condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed to the alicyclic ring Is preferably formed.
  • the alicyclic ring is formed from the viewpoint of reducing the initial coloring due to thermochromism and increasing the fading speed.
  • the alicyclic ring formed by R 6 and R 7 is an alicyclic ring (alkyl group, haloalkyl) containing 3 to 20 carbon atoms including the carbon atom at the 13-position.
  • Group, a cycloalkyl group, an alkoxy group, an amino group, an aralkyl group, an aryl group and a halogen atom which may have at least one substituent.
  • the alkyl group, haloalkyl group, cycloalkyl group, alkoxy group, amino group, aralkyl group, aryl group and halogen atom are the same as those described for R 1 ′ and R 2 ′ .
  • suitable groups include monocyclic rings such as cyclohexane ring, cycloheptane ring and cyclooctane ring, bicyclo rings such as norbornane ring and bicyclononane ring, and tricyclo rings such as adamantane ring. These may have at least one lower alkyl group having 4 or less carbon atoms such as a methyl group as a substituent.
  • a hydrocarbon ring having 3 to 20 carbon atoms is preferred from the viewpoint that the initial coloring due to thermochromism is reduced and the fading speed is increased.
  • a single ring is preferable from the viewpoint that initial coloration due to thermochromism is reduced and a fading speed is increased.
  • the single ring examples include a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, and 3,3. , 5,5-tetramethylcyclohexane ring, and the like.
  • a cyclooctane ring, 3,3,5,5-tetramethylcyclo A hexane ring or the like is preferable.
  • representative examples of the most preferable ring formed by combining R 6 and R 7 are represented by the following structural formulas, for example.
  • the carbon at the position indicated by the numeral “13” in the following formula corresponds to the 13th carbon of the pyran skeleton.
  • both R 1 and R 2 in the general formula (2) are an alicyclic ring, an alicyclic ring, a fatty acid, because the initial coloring is small and the double peak property is high.
  • Particularly preferred is a chromene compound which is a substituent selected from a condensed polycyclic group.
  • lomen compounds represented by the following general formula (5) or general formula (6) are also particularly suitable.
  • R 1 , R 2 , R 2 ′ , R 4 , R 5 , R 6 , R 7 , b and d are respectively the same as those described in the general formula (2)
  • R 3 and R 11 are each a hydrogen atom; a hydroxyl group; an alkyl group; a haloalkyl group; a cycloalkyl group; an alkoxy group; an amino group; a nitrogen atom, and the nitrogen atom is directly bonded to the 5-position carbon atom of the pyran skeleton.
  • R 12 is an electron-donating substituent having a Hammett number ⁇ p of ⁇ 0.1 or less among R 1 ′ and R 2 ′ in the general formula (2).
  • R 1 , R 2 , R 2 ′ , R 4 , R 5 , R 6 , R 7 , b, and d in the general formulas (5) and (6) are respectively represented by the general formula (2).
  • the groups exemplified in the general formula (2) are also included in the groups having the same meanings as those described above and preferable groups as these groups.
  • the number of groups and the position of the carbon atom to be bonded are also the same as those described in the general formula (2).
  • R 3 and R 11 are each a hydrogen atom; a hydroxyl group; an alkyl group; a haloalkyl group; a cycloalkyl group; an alkoxy group; an amino group; a nitrogen atom, and the nitrogen atom is directly bonded to the 5-position carbon atom of the pyran skeleton.
  • Specific examples of these groups include the same groups as those exemplified for R 1 ′ and R 2 ′ above.
  • preferable groups include those exemplified for R 1 ′ and R 2 ′ above.
  • R 12 and R 13 in the general formulas (5) and (6) are electron donating properties in which the Hammett number ⁇ p is ⁇ 0.1 or less in R 1 ′ and R 2 ′ in the general formula (2). It is a group. When R 12 and R 13 are the electron donating group, a particularly excellent effect is exhibited.
  • the Hammett number ⁇ p is defined based on the Hammett's rule, which uses the dissociation constant Ka of p-substituted benzoic acid as a reference, and quantifies the electrical effect of the substituent bonded to the ⁇ -electron system. is there.
  • the substituent whose Hammett number ⁇ p is 0 is a hydrogen atom.
  • R 12 and R 13 are particularly preferably electron donating groups having a Hammett number ⁇ p of ⁇ 0.1 or less. In the case of having an electron donating group that satisfies such a range, the double peak property can be enhanced while suppressing initial coloring.
  • the alkyl group is usually a group having a Hammett number ⁇ p of ⁇ 0.2 or more and ⁇ 0.1 or less, and in the present invention, an alkyl group having 1 to 8 carbon atoms is particularly preferable.
  • Group, sec-butyl group, tert-butyl group ( ⁇ p ⁇ 0.15) and the like.
  • the cycloalkyl group is usually a group having a Hammett number ⁇ p of ⁇ 0.2 or more and ⁇ 0.1 or less, and in the present invention, a cycloalkyl group having 3 to 8 carbon atoms is particularly preferable.
  • the alkoxy group is usually a group having a Hammett number ⁇ p of ⁇ 0.3 or more and ⁇ 0.2 or less, and in the present invention, an alkoxy group having 1 to 8 carbon atoms is particularly preferable.
  • the aryloxy group is usually a group having a Hammett number ⁇ p of ⁇ 0.5 or more and ⁇ 0.2 or less, and in the present invention, an aryloxy group having 6 to 14 carbon atoms is particularly preferable.
  • the aryloxy group one or more hydrogen atoms of the benzene ring are substituted with an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms. It may be a thing. Even with an aryloxy group substituted with these groups, the Hammett number ⁇ p is ⁇ 0.1 or less.
  • the amino group is usually a group having a Hammett number ⁇ p of ⁇ 1.0 or more and ⁇ 0.5 or less.
  • the substituent of the amino group include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, and a carbon number of 4 ⁇ 12 heteroaryl groups and the like.
  • a heterocyclic group containing a nitrogen atom and directly bonded to the 6th or 7th carbon atom of the pyran skeleton is usually a group having a Hammett number ⁇ p of ⁇ 1.0 or more and ⁇ 0.4 or less. is there.
  • the heterocyclic group may have an alkyl group having 1 to 8 carbon atoms as a substituent, and specific examples of the substituent include an alkyl group such as a methyl group.
  • Specific examples of the heterocyclic group having a substituent include 2,6-dimethylmorpholino group, 2,6-dimethylpiperidino group, 2,2,6,6-tetramethylpiperidino group and the like. It is done.
  • a group having a Hammett number ⁇ p of ⁇ 0.90 to ⁇ 0.20 is more preferable, and a group of ⁇ 0.60 to ⁇ 0.20 is more preferable in terms of excellent balance between initial coloring and double peak property.
  • a heterocyclic group containing a nitrogen atom such as an alkoxy group such as a methoxy group or an ethoxy group, a morpholino group, or the like, and the nitrogen atom is directly bonded to the 6th or 7th carbon atom of the pyran skeleton. Is particularly preferred.
  • chromene compounds in the present invention include the following compounds.
  • chromene compound of the present invention generally exists as a colorless, pale yellow or pale green solid or viscous liquid at room temperature and normal pressure, and is prepared by the following means (a) to (c). I can confirm.
  • composition of the corresponding product can be determined by elemental analysis.
  • chromene compound of the present invention is not particularly limited, and is carried out according to various synthetic methods.
  • the chromene compound represented by the general formula (2) is preferably produced by the following method.
  • symbols in the respective formulas have the same meanings as described in the above-described formulas unless otherwise specified.
  • the acid catalyst sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acidic alumina and the like are used, and the acid catalyst is used in the range of 0.1 to 10 parts by weight per 100 parts by weight of the total of naphthol derivative and propargyl alcohol derivative. It is done.
  • the reaction temperature is usually preferably from 0 to 200 ° C.
  • an aprotic organic solvent such as N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, benzene, toluene or the like is used.
  • the method for purifying the product obtained by such a reaction is not particularly limited. For example, purification can be performed by silica gel column purification and further by recrystallization.
  • the naphthol derivative represented by the general formula (7) is a novel compound and constitutes one embodiment of the present invention.
  • the compound represented by the following structural formula can be mentioned, for example.
  • the naphthol compound represented by the general formula (7) according to the present invention is synthesized according to the following reaction scheme.
  • Step a) Preparation of compound of general formula (10) from benzene derivative represented by general formula (9) (Wherein R 1 and a have the same meaning as in the general formula (2)) are reacted with magnesium to give a Grignard reagent, and then reacted with an acid chloride to give a general formula (10 ) (R 1 , R 2 , R 1 ′ , R 2 ′ , a, b, c and d are the same as those in the general formula (2)).
  • Step b) Preparation of the compound represented by the general formula (11)
  • the compound represented by the general formula (10) obtained in the step a) is subjected to the Stobbe reaction and then to the cyclization reaction to give the general formula (11)
  • the compound represented by is prepared.
  • R is a group derived from the diester compound used in the Stobbe reaction.
  • Step c) Preparation of the compound represented by the general formula (12)
  • the compound represented by the general formula (11) obtained in the preparation step b) is hydrolyzed with an alkali or an acid to obtain the general formula (12).
  • the carboxylic acid represented by is prepared.
  • Step d) Preparation of carboxylic acid compound represented by general formula (13)
  • the carboxylic acid represented by general formula (12) obtained in step c) is benzylated using a base such as potassium carbonate and benzyl chloride, Subsequently, it hydrolyzes with an alkali or an acid, General formula (13)
  • Step e) Preparation of the alcohol compound represented by the general formula (14)
  • the benzyl-protected carboxylic acid derivative represented by the general formula (13) obtained in the step d) is converted by a method such as Curtius rearrangement, Hofmann rearrangement or Lossen rearrangement. Convert to amine and prepare diazonium salt from this amine.
  • the diazonium salt is converted to bromide by Sandmeyer reaction or the like, and the resulting bromide is reacted with magnesium, lithium or the like to prepare an organometallic reagent.
  • This organometallic reagent is represented by the general formula (15) (Wherein R 6 and R 7 have the same meaning as in the general formula (2)), the reaction is carried out in an organic solvent at ⁇ 80 to 70 ° C. for 10 minutes to 4 hours, and then hydrogen and By carrying out debenzylation reaction with palladium carbon or the like, general formula (14) (Wherein R 1 , R 2 , R 1 ′ , R 2 ′ , R 6 , R 7 , a, b, c and d are the same as those in the general formula (2)).
  • the reaction ratio between the organometallic reagent and the ketone represented by the general formula (15) is selected from a wide range, but is generally selected from the range of 1:10 to 10: 1 (molar ratio). Is done.
  • the reaction temperature is usually preferably from ⁇ 80 to 70 ° C., and as the solvent, an aprotic organic solvent such as diethyl ether, tetrahydrofuran, benzene, toluene or the like is used.
  • Step f) Preparation of a naphthol derivative of the general formula (7)
  • the alcohol form represented by the general formula (14) obtained in the step e) is subjected to neutral to acidic conditions at 10 to 120 ° C. for 10 minutes to 2 hours.
  • a naphthol derivative represented by the general formula (7) is prepared by performing a Friedel-Crafts reaction.
  • Such a reaction is preferably carried out using an acid catalyst such as acetic acid, hydrochloric acid, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acidic alumina, etc., and such an acid catalyst is 0.1 per 100 parts by weight of alcohol. It is preferable to use in the range of ⁇ 10 parts by weight.
  • a solvent such as tetrahydrofuran, benzene, or toluene is used.
  • Benzene derivative of structural formula (16) The benzene derivative of the structural formula (16) is synthesized, for example, according to the method described in Journal of Organic Cemistry, 729-733; 1998.
  • Benzene derivative of structural formula (17) The benzene derivative of the structural formula (17) is synthesized, for example, according to the method described in Journal of Medicinal Chemistry, 4993-5006; 1995.
  • Benzene derivative of structural formula (18) The benzene derivative of the structural formula (18) is synthesized, for example, according to the method described in Journal of the American Chemical Society, 5654-5655; 1990.
  • Benzene derivative of structural formula (19) The benzene derivative of the structural formula (19) is synthesized, for example, according to the method described in Journal of Chemical Society, Perkin Transactions 2, 662-668; 1976.
  • the benzene derivative of the structural formula (20) is synthesized, for example, according to the method described in Australian Journal of Chemistry, 115-119; 1981, Journal, Journal of Organic Chemistry, 3129-3132;
  • the propargyl alcohol derivative represented by the general formula (8) can be synthesized by various methods. For example, by reacting a ketone derivative corresponding to the general formula (8) with a metal acetylene compound such as lithium acetylide. Easy to synthesize.
  • the chromene compound of the present invention synthesized as described above dissolves well in common organic solvents such as toluene, chloroform, and tetrahydrofuran.
  • a chromene compound is dissolved in such a solvent, generally, the solution is almost colorless and transparent, and rapidly develops color when irradiated with sunlight or ultraviolet rays, and reversibly and rapidly returns to the original colorless when light is blocked. It exhibits a good photochromic effect.
  • the chromene compound of the present invention exhibits an intermediate color by itself, but can also be used in combination with other photochromic compounds in order to obtain various color tones required as a photochromic lens.
  • known compounds can be used without any limitation.
  • fulgide, fulgimide, spirooxazine, chromene and the like can be mentioned.
  • a chromene compound is particularly preferable because it can maintain a uniform color tone at the time of color development and color, can suppress a color shift at the time of color development due to deterioration of photochromic properties, and can reduce initial coloring.
  • the chromene compound of the present invention contains the chromene compound of the present invention, and, like the chromene compound described above, by combining with other chromene compounds having good color development sensitivity and fading speed and small initial coloration, the color tone at the time of fading is uniform.
  • a photochromic composition that provides high transparency can be obtained.
  • chromene compounds to be combined are preferably those having a transmittance of 75% or more by thermochromism and an absorption edge of the ultraviolet absorption curve of 380 to 430 nm. Further, it is particularly preferable that the transmittance by thermochromism is 85% or more and the absorption edge of the ultraviolet absorption curve is 380 to 420 nm, the transmittance by thermochromism is 88% or more, and the absorption edge of the ultraviolet absorption curve. Is most preferably 380 to 410 nm.
  • permeability by this thermochromism and the absorption edge of an ultraviolet absorption curve are the values measured by the method described in the following Example.
  • R 2 ′ , R 3 , R 4 , R 5 , R 6 and R 7 are the same as those shown in the general formula (2), and R 12 is a hydrogen atom, hydroxyl Group, alkyl group, haloalkyl group, cycloalkyl group, alkoxy group, amino group, heterocyclic group containing a ring nitrogen atom and bonded to the benzene ring to which it is bonded, cyano group, nitro group, A formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group, an aralkoxy group, an aryloxy group or an aryl group, m is an integer of 0 to 4, and n is an integer of 0 to 2 It is. Specific examples include, for example, compounds described in International Publication WO2001 / 60811 Pamphlet.
  • R 3 , R 4 and R 5 are the same as those shown in the general formula (2), and R 13 is a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group.
  • alkoxy group alkoxy group, amino group, heterocyclic group containing a ring nitrogen atom and bonded to the benzene ring to which it is bonded, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group , An alkoxycarbonyl group, a halogen atom, an aralkyl group, an aralkoxy group, an aryloxy group or an aryl group, and o and p are each independently an integer of 0 to 4. Specific examples include compounds described in International Publication WO2009 / 136668 Pamphlet.
  • the blending ratio of each chromene compound may be appropriately determined according to the desired color tone.
  • the chromene compound or other chromene compound of the present invention is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the polymerization monomer.
  • the chromene compound of the present invention with respect to 100 parts by mass of the coating monomer or the polymerizable monomer that gives the coating film
  • the color tone is preferably adjusted in the range of 0.001 to 5.0 parts by mass and other chromene compounds 0.001 to 5.0 parts by mass.
  • a thick cured body for example, 1 mm or more
  • the color tone is preferably adjusted in the range of 0.001 to 0.5 parts by mass of the other chromene compounds.
  • the chromene compound of the present invention is highly durable as it is, the durability can be further enhanced by using the following ultraviolet absorber, light stabilizer, antioxidant and the like.
  • the ultraviolet absorber known ultraviolet absorbers such as a benzophenone compound, a benzotriazole compound, a cyanoacrylate compound, a triazine compound, and a benzoate compound can be used, and in particular, a cyanoacrylate compound and a benzophenone compound. Compounds are preferred.
  • the ultraviolet absorber is effective when used in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the polymerization monomer containing the chromene compound of the present invention.
  • a known hindered amine can be used as the light stabilizer
  • a known hindered phenol can be used as the antioxidant.
  • the above light stabilizer and antioxidant are effective when used in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerization monomer containing the chromene compound of the present invention.
  • the photochromic composition comprising the chromene compound of the present invention and the chromene compound represented by the structural formula (1), the general formula (21) or (22) has similar photochromic properties even in a polymer solid matrix. Indicates. As such a polymer solid matrix, any polymer can be used as long as the chromene compound of the present invention is uniformly dispersed.
  • Optically preferred polymer compounds for the polymer solid matrix include, for example, polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly Mention may be made of thermoplastic resins such as (2-hydroxyethyl methacrylate), polydimethylsiloxane and polycarbonate.
  • the photochromic composition containing the chromene compound of the present invention and the chromene compound represented by the structural formula (1), the general formula (21) or (22) is prepared by using various polymerizable monomers before forming a polymer. It can also be set as a photochromic composition by superposing
  • Photochromic composition containing a chromene compound represented by the general formula (21) or (22) and polymerizable monomers (A1), (A2) and (A3) shown below: (A1) a polymerizable monomer having an L-scale Rockwell hardness of 40 or less in a polymer obtained by homopolymerization, (A2) a tri- or higher functional radical polymerizable monomer having an L-scale Rockwell hardness of 60 or more of a polymer obtained by homopolymerization, (A3) A bifunctional radical polymerizable monomer having an L-scale Rockwell hardness of 60 or more of the polymer obtained by homopolymerization is mixed to form a cured product having an L-scale Rockwell hardness of 60 or more.
  • a photochromic curable composition is preferred.
  • each component include, for example, (A1) component such as glycidyl acrylate, glycidyl methacrylate, ⁇ -methyl glycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyloxy methacrylate, 3- (glycidyl-2 Acrylics such as 3-oxyethoxy) -2-hydroxypropyl methacrylate, 3- (glycidyloxy-1-isopropyloxy) -2-hydroxypropyl acrylate, 3- (glycidyloxy-2-hydroxypropyloxy) -2-hydroxypropyl acrylate;
  • (A2) component includes trimethylolpropane trimeta
  • Polyacrylates such as polyacrylates such as relate and polymethacrylate compounds, urethane acrylates such as urethan
  • a copolymer obtained by copolymerizing the polymerizable monomer described above with a polymerizable monofunctional monomer can be used as the polymer matrix.
  • polymerizable monofunctional monomers include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic anhydride; diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxy succinate, diallyl Polyvalent allyl compounds such as fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol carbonate, trimethylolpropane triallyl carbonate; 1,2-bis (methacryloylthio) ethane, bis (2-acryloylthioethyl) ) Ether, 1,4-bis (methacryloylthiomethyl) benzene and other polyvalent thioacrylic acid and polyvalent thiomethacrylic acid este
  • the method for dispersing the chromene compound of the present invention in the polymer solid matrix is not particularly limited, and a general method can be used.
  • Examples thereof include a method of polymerizing and dispersing in a resin, and a method of dispersing in a resin by dyeing a chromene compound on the surface of the thermoplastic resin and thermosetting resin.
  • the chromene compound of the present invention can be widely used as a photochromic material, for example, various kinds of storage materials, copy materials, printing photoreceptors, cathode ray tube storage materials, laser photosensitive materials, and holographic photosensitive materials in place of silver salt photosensitive materials. It can be used as various storage materials.
  • the photochromic material using the chromene compound of the present invention can also be used as a material for photochromic lens materials, optical filter materials, display materials, light quantity meters, decorations, and the like.
  • a photochromic lens when used for a photochromic lens, there is no particular limitation as long as it is a method capable of obtaining uniform light control performance. Specifically, a method of sandwiching a polymer film formed by uniformly dispersing the photochromic material of the present invention in a lens, a chromene compound of the present invention dispersed in the polymerizable monomer, A method of polymerizing by this method, or this compound is dissolved in, for example, silicone oil, impregnated on the lens surface over 10 to 60 minutes at 150 to 200 ° C., and further, the surface is coated with a curable substance, and photochromic There is a method of using a lens. Further, there is a method of applying the polymer film to the lens surface and coating the surface with a curable substance to form a photochromic lens.
  • a coating agent made of a polymerization curable composition containing the chromene compound of the present invention may be applied to the surface of the lens substrate to cure the coating film.
  • the lens substrate may be subjected to a surface treatment such as a surface treatment with an alkaline solution or a plasma treatment in advance, and further (with or without these surface treatments), the substrate and the coating film.
  • a primer can also be applied in order to improve the adhesion to the substrate.
  • Structural formula (23) Naphthol derivative of 1.20 g (2.3 mmol) and structural formula (24)
  • the propargyl alcohol derivative (0.80 g, 3.0 mmol) was dissolved in 70 ml of toluene, 0.022 g of p-toluenesulfonic acid was further added, and the mixture was stirred for 1 hour while heating under reflux. After the reaction, the solvent was removed and the residue was purified by chromatography on silica gel to obtain 1.33 as a white powder product. The yield was 75%.
  • the elemental analysis values of this product are C 84.01%, H 7.64%, O 8.35% (the analysis value of oxygen was calculated by subtracting the analysis value of other elements from 100%), and C 54 H The calculated values of 58 ⁇ 4 were in good agreement with C 84.12%, H 7.58% and O 8.30%.
  • the proton nuclear magnetic resonance spectrum was measured, and the peak of 33H based on the methyl proton of the tetramethylcyclohexane ring, the proton of the adamantane ring and the methylene proton was around 1.0 to 3.0 ppm, and the vicinity of ⁇ 2.3 to 4.5 ppm. Shows a peak of 9H based on the methyl proton of the methoxy group, and a peak of 16H based on the aromatic proton and the alkene proton in the vicinity of ⁇ 5.6-9.0 ppm.
  • Example 2 to 12 chromene compounds shown in Tables 1-1 to 1-3 (Examples 2 to 12) were synthesized.
  • the obtained product was subjected to structural analysis using the same structure confirmation means as in Example 1. As a result, it was confirmed that the product was a compound having the structural formula shown in Tables 1-1 to 1-3.
  • Table 2 shows elemental analysis values of these compounds, calculated values obtained from the structural formulas of the respective compounds, and characteristic spectra of 1 H-NMR spectra.
  • photochromic curable composition 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane / polyethylene glycol diacrylate (average molecular weight 532) / trimethylolpropane trimethacrylate / polyester oligomer is used as a radical polymerizable monomer.
  • Maximum absorption wavelength ( ⁇ max) The maximum absorption wavelength after color development determined with a spectrophotometer (instant multichannel photodetector MCPD3000) manufactured by Otsuka Electronics Co., Ltd., and used as an index of color tone during color development. The maximum absorption wavelength is related to the color tone at the time of color development.
  • Double peak property (A Y / A B ): yellow (having a maximum absorption wavelength from 430 nm to 530 nm) color density (A Y : value of ⁇ max ) and blue (maximum from 550 nm to 650 nm) The ratio of the absorption wavelength) to the color density (A B : value of ⁇ max ), and used as an index of double peak property.
  • Fading half-life ( ⁇ 1 / 2 (seconds): After light irradiation for 120 seconds, when the light irradiation is stopped, the absorbance at the maximum absorption wavelength of the sample is ⁇ (120) ⁇ (0) ⁇ This is the time required to decrease to 1/2 of this value, and was used as an index for fading speed. The shorter the time, the faster the fading speed.
  • Absorption edge ( ⁇ 0 ) The photochromic plastic lens obtained under the above conditions was used as a sample, and this was stored in a dark place all day and night, and then at room temperature, an ultraviolet-visible spectrophotometer (Shimadzu, UV-2550) ) To measure the transmittance (T%) of ultraviolet light from 300 nm to 800 nm. A tangent line is drawn with respect to the ultraviolet light absorption curve so that the transmittance (T%) of the obtained ultraviolet light absorption curve is 50%, and the transmittance (T%) of the tangential line becomes zero.
  • the absorption edge of the absorption wavelength was determined and used as an index for initial coloring. For example, in an optical article such as an eyeglass lens, the lower this value, the lower the initial coloration and the higher the transparency in the non-irradiated state.
  • Thermochromism (T 0 ) from 300 nm to 800 nm using a photochromic plastic lens obtained under the above conditions as a sample at room temperature using an ultraviolet-visible spectrophotometer (Shimadzu, UV-2550) Measure the transmittance (T%).
  • the transmittance at a wavelength where the transmittance in the range of 430 nm to 650 nm takes a minimum value was determined and used as an index for initial coloring. The larger this value, the smaller the initial coloration and the higher the transparency when not irradiated with light.
  • Residual rate (A 50 / A 0 ⁇ 100): The obtained photochromic plastic lens is accelerated and deteriorated by a xenon weather meter X25 manufactured by Suga Test Instruments Co., Ltd. for 50 hours. Thereafter, the color density was evaluated before and after the test, the color density (A 0 ) before the test and the color density (A 50 ) after the test were measured, and the ratio (A 50 / A 0 ) was defined as the residual rate. It was used as an index of color durability. The higher the remaining rate, the higher the durability of coloring.
  • Color development sensitivity [ ⁇ (10) / ⁇ (120)]: Using the photochromic plastic lens obtained under the above conditions as a sample, the color density ⁇ (120) ⁇ after light irradiation for 120 seconds and light irradiation for 10 seconds The ratio with the subsequent color density ⁇ (10) ⁇ was calculated and used as an index of color development sensitivity. The larger this value, the deeper the color developed in a shorter time for light irradiation.
  • Table 3 summarizes the results of the photochromic properties obtained for the photochromic plastic lens using the chromene compound of Example 1.
  • Examples 13 to 24 (compounds 1 to 12) using the chromene compound of the present invention showed high color density, high color fading speed, small initial coloration, high repetition durability, It turns out that a high double peak property is shown.
  • a Y / A B can reduce the amount of yellow compounds generally having low durability when adjusting to a gray or brown color tone.
  • a Y / A B is preferably at least 1.00, more preferably 1.10 or more, more preferably 1.20 or more, particularly preferably 1.30 or more.
  • the fading half-life ⁇ 1 / 2 is preferably 40 seconds or more and less than 130 seconds, more preferably 40 seconds or more and less than 100 seconds, and particularly preferably 40 seconds or more and less than 80 seconds.
  • thermochromism is preferably 85% or more, more preferably 87% or more, and particularly preferably 90% or more.
  • the absorption edge is preferably from 400 nm to 420 nm, more preferably from 405 nm to 420 nm, particularly preferably from 405 nm to 415 nm, from the viewpoint of initial coloring and color development sensitivity.
  • Comparative Example 1 (Compound A) has a high double peak property, it has a problem that the fading speed is very slow, the initial transmittance is low (colored brown), and the repetition durability is slightly low.
  • Example 20 (Compound 8) of the present invention maintains a double peak property, has a high fading speed, a high initial transmittance, and a high repetition durability.
  • Comparative Example 2 (Compound B) has problems that the double peak property is low, the initial transmittance is low (colored in gray), and the repeated durability is also low.
  • Example 21 (Compound 9) of the present invention has a high double peak property, a high initial transmittance, and a high durability.
  • Comparative Example 3 (Compound C) has a high double peak property and excellent repeatability, but has a large initial coloration due to the absorption edge (colored yellow because the absorption edge is in the visible region).
  • Example 22 (Compound 10) of the present invention shows that the initial coloring due to the absorption edge is small while maintaining the double peak property and the repeated durability.
  • Comparative Example 4 has a methoxy group at the 6-position, but in any of the 5-position, 7-position, and 9-12-position, the alicyclic ring is an alicyclic ring, an aliphatic heterocyclic ring, an aromatic ring A fused polycyclic group fused with a ring or an aromatic heterocycle, or a fused polycyclic group fused with an alicyclic ring, an aliphatic heterocycle, an aromatic ring or an aromatic heterocycle on an aliphatic heterocycle Does not have a substituent. In this case, a high double peak property cannot be obtained.
  • Comparative Example 5 is a condensed polycyclic group in which an alicyclic ring, an aliphatic heterocyclic ring, an aromatic ring or an aromatic heterocyclic ring is condensed to an alicyclic ring at any of positions 5 to 12.
  • the aliphatic heterocyclic ring does not have a substituent selected from an alicyclic ring, an aliphatic heterocyclic ring, an aromatic ring or a condensed polycyclic group in which an aromatic heterocyclic ring is condensed. In this case, a high double peak property cannot be obtained.
  • Example 24 Compound 12 of the present invention has a small initial coloring due to the absorption edge while maintaining the double peak property and the repeated durability.
  • a photochromic plastic lens was produced in the same manner as in Example 12 except that the compounds obtained in Examples 25 to 38 were used as the chromene compound, and the characteristics thereof were evaluated. The results are summarized in Table 7. Compound Nos. 25 to 38 in Table 7 are chromene compounds obtained in Examples 25 to 38, respectively.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Optical Filters (AREA)
  • Pyrane Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

La présente invention concerne un nouveau composé photochrome durable présentant un ton moyen lorsqu'il se trouve dans un état coloré, une faible coloration initiale, une densité élevée de couleur, et une grande vitesse de décoloration. Ledit composé photochrome est un composé de chromène, dont le squelette de base est une structure indéno(2,1-f)naphto(1,2-b)pyranne représentée par la formule structurelle (1). Un des atomes de carbone entre le cinquième atome de carbone et le douzième atome de carbone dans la structure pyranne, inclus, est lié via une liaison carbone-carbone à un substituant qui est un groupe polycyclique condensé dans lequel un noyau alicyclique, un noyau hétérocyclique aliphatique, un noyau aromatique, ou un noyau hétérocyclique aromatique est condensé avec un noyau alicyclique ou un noyau hétérocyclique aliphatique qui présente un site de liaison pour l'atome de carbone dans la structure pyranne.
PCT/JP2010/072550 2009-12-22 2010-12-15 Composé de chromène Ceased WO2011078030A1 (fr)

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WO2018235771A1 (fr) 2017-06-20 2018-12-27 株式会社トクヤマ Composé de polyrotaxane photochromique et composition durcissable contenant ledit composé de polyrotaxane photochromique
WO2020017610A1 (fr) 2018-07-20 2020-01-23 株式会社トクヤマ Composé photochromique et composition durcissable contenant ledit composé photochromique
WO2021075383A1 (fr) 2019-10-17 2021-04-22 株式会社トクヤマ Composé d'hydroxyuréthane photochromique
WO2022030557A1 (fr) 2020-08-06 2022-02-10 株式会社トクヤマ Composé photochromique, composition durcissable photochromique, corps durci, lentille et lunettes
WO2024128159A1 (fr) 2022-12-16 2024-06-20 株式会社トクヤマ Composition durcissable, corps durci, stratifié, lentille et lunettes
WO2024214740A1 (fr) 2023-04-12 2024-10-17 株式会社トクヤマ (méth)acrylate, composition durcissable, corps durci, stratifié, article optique, lentille et lunettes

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Publication number Priority date Publication date Assignee Title
WO2018235771A1 (fr) 2017-06-20 2018-12-27 株式会社トクヤマ Composé de polyrotaxane photochromique et composition durcissable contenant ledit composé de polyrotaxane photochromique
WO2020017610A1 (fr) 2018-07-20 2020-01-23 株式会社トクヤマ Composé photochromique et composition durcissable contenant ledit composé photochromique
WO2021075383A1 (fr) 2019-10-17 2021-04-22 株式会社トクヤマ Composé d'hydroxyuréthane photochromique
WO2022030557A1 (fr) 2020-08-06 2022-02-10 株式会社トクヤマ Composé photochromique, composition durcissable photochromique, corps durci, lentille et lunettes
WO2024128159A1 (fr) 2022-12-16 2024-06-20 株式会社トクヤマ Composition durcissable, corps durci, stratifié, lentille et lunettes
WO2024128160A1 (fr) 2022-12-16 2024-06-20 株式会社トクヤマ Composition durcissable, corps durci, stratifié, lentille et lunettes
WO2024128158A1 (fr) 2022-12-16 2024-06-20 株式会社トクヤマ Composition durcissable, corps durci, stratifié, lentille et lunettes
EP4636465A1 (fr) 2022-12-16 2025-10-22 Tokuyama Corporation Composition durcissable, corps durci, stratifié, lentille et lunettes
EP4636464A1 (fr) 2022-12-16 2025-10-22 Tokuyama Corporation Composition durcissable, corps durci, stratifié, lentille et lunettes
EP4636466A1 (fr) 2022-12-16 2025-10-22 Tokuyama Corporation Composition durcissable, corps durci, stratifié, lentille et lunettes
WO2024214740A1 (fr) 2023-04-12 2024-10-17 株式会社トクヤマ (méth)acrylate, composition durcissable, corps durci, stratifié, article optique, lentille et lunettes

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