JPWO2011078030A1 - Chromene compounds - Google Patents

Abstract

Disclosed is a novel photochromic compound having a color tone at the time of color development, a low initial coloration, a high color density, a high color fading speed, and good durability. The photochromic compound is a chromene compound having an indeno (2,1-f) naphtho (1,2-b) pyran structure represented by the structural formula (1) as a basic skeleton, and is a carbon at the 5th to 12th positions of the pyran structure. 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 in which one of the atoms has a bonding site with a carbon atom of a pyran structure; And an aliphatic heterocyclic ring having a bonding site with a carbon atom of the pyran structure, an alicyclic ring, an aliphatic heterocyclic ring, an aromatic ring or a condensed polycyclic group in which an aromatic heterocyclic ring is condensed. It has the substituent selected through a carbon-carbon bond. [Chemical 1]

Description

  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.

In photochromic compounds used for such applications,
(I) 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.

のインデノ(２,１-ｆ)ナフト（１,２-ｂ）ピラン構造を基本骨格として有するクロメン化合物が知られている（例えば、特許文献１及び２参照）。As a photochromic compound that can satisfy such requirements, structural formula (1)

A chromene compound having an indeno (2,1-f) naphtho (1,2-b) pyran structure as a basic skeleton is known (see, for example, Patent Documents 1 and 2).

  Photochromic plastic lenses using a photochromic compound are preferably colored in intermediate 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 and a purple to blue photochromic compound (blue compound) having a maximum absorption at 550 to 650 nm are mixed. Yes.

  However, when the color tone is adjusted by such a method, various problems occur due to the difference in the photochromic properties of the mixed compounds. For example, when the repetition durability of the yellow compound is lower than that of the blue compound, there has been a problem that the color tone changes gradually to a strong blue tone when used over a long period of time.

  Further, when the color development sensitivity and color fading speed of the yellow compound are lower than those of the blue compound, the color tone during color development has a strong blue tint, and the color tone during the color fade has a strong yellow tint.

  It is considered that such a problem can be solved by using a compound (double peak compound) that has two or more absorption maxima at the time of light irradiation and develops a single compound in an intermediate color. In general, it is known that a yellow compound is inferior in durability to a blue compound. Therefore, in the double peak compound, there is a compound in which the color density of yellow (having the maximum absorption wavelength at 430 to 530 nm) is higher than the color density of blue (having the maximum absorption wavelength at 550 to 650 nm). (Hereinafter, in the case of a double peak compound, the ratio of the yellow color density to the blue color density may be double peaked).

  So far, compounds as shown in the following formulas (A) to (C) are known as photochromic compounds (double peak compounds) having two or more absorption maximums upon light irradiation.

を有するクロメン化合物（特許文献３参照）は、ダブルピーク性は高いものの、退色速度が遅い上、繰り返し耐久性が低いという問題があった。However, these compounds have room for improvement in the following respects:
That is, structural formula (A)

The chromene compound (see Patent Document 3) having a high double peak property has a problem that the fading speed is slow and the repetition durability is low.

を有するクロメン化合物（特許文献４参照）は、430〜530 nmの吸収が、550〜650 nmの吸収に比べて小さく、ダブルピーク性が低いという問題があった。Structural formula (B)

The chromene compound (see Patent Document 4) has a problem that the absorption at 430 to 530 nm is smaller than the absorption at 550 to 650 nm, and the double peak property is low.

を有するクロメン化合物（特許文献５参照）は、ダブルピーク性に優れ、実用的な発色濃度及び退色速度を有しているが、吸収スペクトルの末端部分（以下、吸収端という）が420nmを超えて可視域に到達しているため、初期着色がやや大きいという点で改善の余地があった。Furthermore, structural formula (C)

The chromene compound (see Patent Document 5) having an excellent double peak property and a practical color density and fading speed, but the terminal portion of the absorption spectrum (hereinafter referred to as the absorption edge) exceeds 420 nm. Since it reached the visible range, there was room for improvement in that the initial coloring was slightly large.

International Publication WO 99/15518 Brochure International Publication WO 01/60811 Pamphlet International Publication WO 01/19813 Pamphlet International Publication WO 03/44022 Pamphlet International Publication WO 05/28465 Brochure

  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.

  To date, 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 (hereinafter simply referred to as “pyran skeleton”) However, it is known to exhibit a high double peak property. The substituent having a high electron donating property here is specifically a substituent bonded to the 6-position and the 7-position with an oxygen atom or a nitrogen atom. However, although the above compound has a high double peak property, the fading rate is basically slow, and the color development due to heat at room temperature without light irradiation (hereinafter, this color development is referred to as thermochromism initial coloration) is large. It has the disadvantage of low durability. In particular, when 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 intensively studied 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) 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.

  Such an electron-donating property is not so high, and 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.

  Although 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. By introducing a substituent which is not so high and sterically bulky to at least one carbon atom of the carbon atom at the 12th position, the introduced substituent group at the 5th to 12th position and pyran are introduced. It is inferred that an unpredictable effect is achieved by some steric interaction with the skeleton.

  Thus, 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. A fused 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 in which a bonding site with a carbon atom is present, and the indeno (2,1 -F) 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. A chromene compound having a substituent selected from the group consisting of the condensed polycyclic groups via a carbon-carbon bond.

  The second object of the present invention is to produce the chromene compound.

  The 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.

  Furthermore, 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. .

  Furthermore, the 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.

  Therefore, for example, 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. Thus, 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 represented by the above structural formula (1) as a basic skeleton, and has 5 to 12-position carbon atoms in 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.

  In the substituent having an aliphatic heterocycle, when the carbon atom of the pyran skeleton is bonded to a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom of the aliphatic heterocycle, the valence of the heteroatom is Since it is 2-3, compared with the carbon whose valence is 4, the atom on the side couple | bonded with a carbon atom becomes three-dimensionally small. Although this is considered to be the cause, the obtained chromene compound tends to have a large initial coloration.

  In addition, in the substituent having an aromatic ring, when the carbon atom of the pyran skeleton and the carbon atom of the aromatic ring are bonded, it is presumed that the cause is that the conjugation of the pyran skeleton is extended. The chromene compound tends to increase the initial coloration and tends not to have a higher double peak property.

These substituents will be described in detail.
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.

  Although it does not restrict | limit especially as a condensed polycyclic group which the aliphatic heterocyclic ring condensed to the alicyclic ring, The condensed polycyclic group which is C3-C20 which comprises a ring is preferable, and C6-C20 The condensed polycyclic group is particularly preferred. Preferable examples of the 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 [2,2,2] octane ring, thiabicyclo [3,2,1] octane ring, Bicyclo ring groups such as thiabicyclo [3,3,1] nonane ring and tricyclo such as 1-azaadamantane ring, 2-azaadamantane ring, 1-oxaadamantane ring, 1-thiaadamantane ring, etc. And a ring group.

  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 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 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. [3,2,1] octane ring, diazabicyclo [3,3,1] nonane ring, diazabicyclo [4,3,0] nonane ring, dioxabicyclo [2,2,1] heptane ring, dioxabicyclo [2 , 2,2] octane ring, dioxabicyclo [3,2,1] octane ring, dioxabicyclo [3,3,1] nonane ring, dioxabicyclo [4,3,0] nonane ring, dithiabicyclo [2 , 2,1] heptane ring, dithiabicyclo [2,2,2] octane ring, dithiabicyclo [3,2,1] octane ring, bicyclo ring group such as dithiabicyclo [3,3,1] nonane ring, and for example Examples include tricyclo ring groups such as 2,4,10-triazatricyclo [3,3,1,13,7] decane It is.

  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.

  An alicyclic ring, an alicyclic ring, an aliphatic heterocyclic ring, an aromatic ring or a condensed polycyclic group condensed with an aromatic heterocyclic ring, or an aliphatic heterocyclic ring having an alicyclic ring or an aliphatic heterocyclic ring The condensed polycyclic group condensed with an aromatic ring or an aromatic heterocyclic ring may itself be substituted.

  An alicyclic ring, an aliphatic heterocyclic ring, an aromatic ring, or a condensed polycyclic group in which an aromatic heterocyclic ring is condensed, or an aliphatic heterocyclic ring, an alicyclic ring, an aliphatic heterocyclic ring, an aromatic ring 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.

Here, the alkyl group is not particularly limited, but an alkyl group having 1 to 8 carbon atoms is preferable.
Examples of 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. Examples of 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. Examples of 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. Examples of 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. Examples of the 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. C4-C12 heteroaryl groups such as aryl groups having 6 to 14 carbon atoms such as, thienyl groups, furyl groups, pyrrolinyl groups, pyridyl groups, etc. (specific examples of alkyl groups, alkoxy groups, and cycloalkyl groups) Are the same as those described above for the substituent). Examples of 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, and examples thereof are morpholino group, piperidino group, pyrrolidinyl group, piperazino group, N-methylpiperazino group, An indolinyl group etc. can be mentioned. Furthermore, 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. Examples of 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. Specific examples of 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. Examples of suitable aryloxy groups include phenoxy group, 1-naphthoxy group, 2-naphthoxy group and the like.

  In the chromene compound of the present invention, among the substituents that the 5-12 position carbon atoms of the pyran skeleton may have, a group that is preferable in terms of obtaining a compound having a small initial coloration and a high double peak property, 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.

In the chromene compound of the present invention, 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. Among such sterically bulky substituents, the chromene compound of the present invention preferably has a substituent in which the resulting chromene compound has the following form.
The chromene compound in the case where there is no substituent at positions 5-8 of the pyran skeleton has a benzene ring containing a carbon atom at positions 5-8 of the pyran skeleton in a plane in the molecular orbital calculation by MOPACPM3. The dihedral angle formed by the carbon atoms is 0 °. On the other hand, in the chromene compound of the present invention, when 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. Further, when the 6-position or 7-position carbon atom of the pyran skeleton has the above-mentioned condensed polycyclic group as a substituent, among the condensed polycyclic groups, 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. Further, when 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.

  In the chromene compound of the present invention, when the substituent is present on the carbon atoms at the 5th to 8th positions of the pyran skeleton, in order to further enhance the double peak property, the above substituent is the 6th or 7th position of the pyran skeleton. Bonding to a carbon atom is preferred.

  Further, 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 in a plane in the molecular orbital calculation by MOPACPM3. The dihedral angle formed by the 12th carbon atom is 0 °. On the other hand, in the chromene compound of the present invention, when 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. In addition, when the carbon atom at the 10th or 11th position of the pyran skeleton has the above condensed polycyclic group as a substituent, among the condensed polycyclic groups, 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 °. Further, when 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 °.

  In the chromene compound of the present invention, 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.

  Specific examples of 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. Furthermore, 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. Specific examples of particularly preferred groups include a bicyclo [2,2,2] octane ring group, a 1-adamantane ring group, and a 2-adamantane ring group.

  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. There are three main methods. In recent years, with the development of computers, semi-empirical methods and non-empirical methods have become main methods. 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., Chemistry Dojin, 1983), "Computational Chemistry Guidebook" (Eiji Osawa et al., Tim Clark, Maruzen, 1985)].

  More specifically, the chromene compound according to the present invention is represented by the following general formula (2).

〔式中、
Ｒ¹及びＲ²は、インデノ(２,１‐ｆ)ナフト(１,２‐ｂ)ピラン骨格の炭素原子との結合部位が存在する脂環式環に、脂環式環、脂肪族複素環、芳香族環又は芳香族複素環が縮環した縮合多環基、及びピラン骨格の炭素原子との結合部位が存在する脂肪族複素環に、脂環式環、脂肪族複素環、芳香族環又は芳香族複素環が縮環した縮合多環基からなる群から選ばれる基であって、炭素‐炭素結合を介してインデノ(２,１‐ｆ)ナフト(１,２‐ｂ)ピラン骨格に結合する基であり、
Ｒ^1'及びＲ^2'は、水素原子；ヒドロキシル基；アルキル基；ハロアルキル基；シクロアルキル基；アルコキシ基；アミノ基；窒素原子を含み、該窒素原子がピラン骨格の炭素原子と直接結合する複素環基；シアノ基；ニトロ基；ホルミル基；ヒドロキシカルボニル基；アルキルカルボニル基；アルコキシカルボニル基；ハロゲン原子；アラルキル基；アリール基；アラルコキシ基；又はアリールオキシ基であり、
Ｒ⁴及びＲ⁵は、それぞれ独立に、一般式（３）

（式中、Ｒ⁸は、アリール基、又はヘテロアリール基であり；Ｒ⁹は、水素原子、アルキル基、又はハロゲン原子であり；ｍは１〜３の整数である）で表される基、一般式（４）

（式中、Ｒ¹⁰は、アリール基、又はヘテロアリール基であり；ｎは１〜３の整数である）で表される基、アリール基、ヘテロアリール基、又はアルキル基であるか、又はＲ⁴及びＲ⁵は、互いに結合して、脂環式環を形成し、
Ｒ⁶及びＲ⁷は、それぞれ独立して、水素原子；ヒドロキシル基；アルキル基；ハロアルキル基；シクロアルキル基；アルコキシ基；アミノ基；窒素原子を含み、該窒素原子が１３位の炭素原子と直接結合する複素環基；シアノ基；ニトロ基；ホルミル基；ヒドロキシカルボニル基；アルキルカルボニル基；アルコキシカルボニル基；ハロゲン原子；アラルキル基；アリール基；アラルコキシ基；又はアリールオキシ基であるか、又はＲ⁶及びＲ⁷は、インデノ(２,１‐ｆ)ナフト(１,２‐ｂ)ピラン骨格の１３位の炭素原子と共に、互いに一緒になって、炭素数が３〜２０である、脂環式環基又は脂環式環に芳香族環又は芳香族複素環が縮環した縮合多環、又は炭素数が３〜２０である、複素環基又は複素環に芳香族環又は芳香族複素環が縮環した縮合多環を形成し、
ａ、ｂ、ｃ及びｄは、それぞれ、０〜４の整数であり、ただし、ａ＋ｂ＝１〜８、ａ＋ｃ＝４、ｂ＋ｄ＝４であり、
ａが２以上である場合、Ｒ¹は、互いに、同一又は異なる基であり、
ｂが２以上である場合、Ｒ²は、互いに、同一又は異なる基であり、
ｃが２以上である場合、Ｒ^1'は、互いに、同一又は異なる基であり、
ｄが２以上である場合、Ｒ^2'は、互いに、同一又は異なる基であり、
ａ及びｂが共に０ではない場合、Ｒ¹及びＲ²は、互いに、同一又は異なる基であり、
ｃ及びｄが共に０ではない場合、Ｒ^1'及びＲ^2'は、互いに、同一又は異なる基である。］ General formula (2)

[Where,
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. A fused 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, an alicyclic ring, an aliphatic heterocyclic ring, an aromatic ring Or a group selected from the group consisting of condensed polycyclic groups condensed with an aromatic heterocycle, which is linked to an indeno (2,1-f) naphtho (1,2-b) pyran skeleton via a carbon-carbon bond. A bonding group,
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. Cyano group; nitro group; formyl group; hydroxycarbonyl group; alkylcarbonyl group; alkoxycarbonyl group; halogen atom; aralkyl group; aryl group; aralkoxy group; or aryloxy group,
R ⁴ and R ⁵ are each independently represented by the general formula (3)

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 cycloalkyl group; an alkoxy group; an amino group; a nitrogen atom, and the nitrogen atom is directly connected to the carbon atom at the 13th position. Cyano group; nitro group; formyl group; hydroxycarbonyl group; alkylcarbonyl group; alkoxycarbonyl group; halogen atom; aralkyl group; aryl group; aralkoxy group; or aryloxy group, or R ⁶ And R ⁷ together with a carbon atom at position 13 of the indeno (2,1-f) naphtho (1,2-b) pyran skeleton, together with each other, an alicyclic ring having 3 to 20 carbon atoms A condensed polycyclic ring condensed with an aromatic ring or aromatic heterocyclic ring on a group or alicyclic ring, or a heterocyclic group or heterocyclic ring having 3 to 20 carbon atoms, condensed with an aromatic ring or aromatic heterocyclic ring Ring Condensed polycyclic was formed,
a, b, c and d are each an integer of 0 to 4, provided that a + b = 1 to 8, a + c = 4, b + d = 4,
when a is 2 or more, R ¹ are the same or different from each other;
when b is 2 or more, R ² are the same or different from each other;
when c is 2 or more, R ^{1 ′} is the same or different from each other;
when d is 2 or more, R ^{2 ′} is the same or different from each other;
when both a and b are not 0, R ¹ and R ² are the same or different from each other;
When c and d are not 0, R ^{1 ′} and R ^{2 ′} are the same or different from each other. ]

  The group in the general formula (2) will be described.

An alicyclic ring, an aliphatic heterocyclic ring, an alicyclic ring in which a bonding site to the carbon atom of the indeno (2,1-f) naphtho (1,2-b) pyran skeleton of R ¹ and R ² exists; 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 either bound to the carbon atoms of R ¹ is 6-position and / or 7-position, by binding to the carbon atom of R ² is 9-position and / or 12-position, particularly high double peak property It can be a chromene compound. Therefore, it is preferable that a is an integer of 0 to 2 and b is an integer of 0 to 2 (however, (a + b) ≠ 0). Among such preferable chromene compounds, a chromene compound in which R ¹ is bonded to a carbon atom at the 6-position or 7-position and b = 0 exhibits particularly excellent physical properties.

In addition to R ^{1 and} R ² , R ^{1 ′} and R ^{2 ′} are bonded to the carbon atoms at the 5th to 12th positions of the pyran skeleton. Therefore, c and d representing the numbers of R ^{1 ′} and R ^{2 ′} are integers of 0 to 4, respectively, and are integers satisfying a + c = 4 and b + d = 4.

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. A carbonyl group; a hydroxycarbonyl group; an alkylcarbonyl group; an alkoxycarbonyl group; a halogen atom; an aralkyl group; an aryl group; an aralkoxy group; or an aryloxy group.

Each group of R ^{1 ′} and R ^{2 ′} will be described in detail.

  The alkyl group is not particularly limited, but an alkyl group having 1 to 8 carbon atoms is preferable. Examples of 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. Examples of 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. Examples of 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. Examples of 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. Examples of the substituent that the amino group has 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. And heteroaryl groups having 4 to 12 carbon atoms such as aryl groups having 6 to 14 carbon atoms, thienyl groups, furyl groups, pyrrolinyl groups, and pyridyl groups, etc. (specific examples of alkyl groups, alkoxy groups, and cycloalkyl groups are listed below). And the same groups as those described above for the substituent). Examples of 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. For example, a morpholino group, piperidino group, pyrrolidinyl group, piperazino group, N-methylpiperazino group, An indolinyl group etc. can be mentioned. Furthermore, 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. Examples of 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. Specific examples of 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. 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. Examples of 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.

In addition, R ^{1 ′} particularly includes 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, and the nitrogen atom is pyran. 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. That is, 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. When 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. A suitable electron-withdrawing group is a cyano group or a C 1-8 haloalkyl group, and specific examples include a cyano group and a trifluoromethyl group.

Although be balance with R ^1, if R ¹ is present one or more (a ≧ 1), in particular, when at least one R ¹ that bind to position 6 or 7 carbon atoms, especially excellent In order to obtain a chromene compound exhibiting physical properties, 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. Here, the same group as the aryl group already ^demonstrated regarding R1 ^' and R2 ^' is applied to an aryl 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. Also, R ⁹ of the general formula (3) is a hydrogen atom, an alkyl group or a halogen atom. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. m is an integer of 1 to 3, and 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 group, 2-benzothienyl-ethenyl group, 2-benzofuranyl-ethenyl group, 2- (N-methyl) indolyl-ethenyl group and the like can be mentioned.

In General formula (4), R < ¹⁰ > is the same aryl group or heteroaryl group as said R < ⁸ >. Moreover, n is an integer of 1 to 3, but 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. Group, (4-piperidinophenyl) -ethynyl group, (4-methoxyphenyl) -ethynyl group, (4-methylphenyl) -ethynyl group, (2-methoxyphenyl) -ethynyl group, 2-thienyl-ethynyl group Names include 2-furyl-ethynyl group, 2- (N-methyl) pyrrolinyl-ethynyl group, 2-benzothienyl-ethyl group, 2-benzofuranyl-ethynyl group, 2- (N-methyl) indolyl-ethynyl group, etc. Can do.

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 a heteroaryl group having 6 to 14 carbon atoms is preferable. Examples of suitable heteroaryl groups include thienyl group, furyl group, pyrrolinyl group, pyridyl group, benzothienyl group, benzofuranyl group, benzopyrrolinyl group and the like. Further, 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.

In particular, in order to exhibit excellent photochromic properties, it is preferable that 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.

  In the aryl groups in the above (i) to (iii), the position of the substituent is not particularly limited, and the total number is not particularly limited. However, in order to exhibit excellent photochromic properties, the substitution position is preferably the 3- or 4-position when the aryl group is a phenyl group. Moreover, it is preferable that the number of the substituents in that case is 1-2. Examples of such suitable aryl groups are 4-methylphenyl group, 4-methoxyphenyl group, 3,4-dimethoxyphenyl group, 4-n-propoxyphenyl group, 4- (N, N-dimethylamino) phenyl. Group, 4- (N, N-diethylamino) phenyl group, 4- (N, N-diphenylamino) phenyl group, 4-morpholinophenyl group, 4-piperidinophenyl group, 3- (N, N-dimethylamino) ) Phenyl group, 4- (2,6-dimethylpiperidino) phenyl group and the like.

  Moreover, in the heteroaryl group in the above (i) to (iii), the position of the substituent is not particularly limited, and the total number is not particularly limited, but the number is preferably 1. Specific examples of 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. 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 aryl group; an aralkoxy group; or an aryloxy group.

An alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a nitrogen atom in R ⁶ and R ⁷ , a heterocyclic group in which the nitrogen atom is directly bonded to the 13th carbon atom of the pyran skeleton, an alkylcarbonyl group, Details of the alkoxycarbonyl group, halogen atom, aralkyl group, aryl group, aralkoxy group, and aryloxy group are the same as those described for R ^{1 ′} and R ^{2 ′} above.

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. Or a condensed polycyclic ring in which an aromatic ring or an aromatic heterocyclic ring is condensed to the alicyclic ring, a heterocyclic ring 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 polycycle in which an aromatic ring or an aromatic heterocycle is condensed to an alicyclic ring include a benzocyclohexane ring.

  Examples of the heterocyclic ring having 3 to 20 atoms including the carbon atom at the 13-position include a dihydrothiophene ring, a dihydrofuran ring, a tetrahydrofuran ring, and a dihydropyridine ring.

  Examples of the condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to a heterocycle include a dihydrobenzofuran ring and a dihydrobenzothiophene ring.

In the present invention, it is preferable that R ⁶ and R ⁷ together with the carbon atom at the 13th position of the pyran structure form a ring together. Among these, from the viewpoint that initial coloring due to thermochromism is reduced and the fading speed is increased, in particular, 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. Among these, it is preferable that the alicyclic ring is formed from the viewpoint of reducing the initial coloring due to thermochromism and increasing the fading speed.

Particularly preferred as the alicyclic ring formed by R ⁶ and R ⁷ is an alicyclic ring (alkyl group, haloalkyl) having 3 to 20 carbon atoms to form a ring including the 13-position carbon atom. 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 ′} .

  Examples of 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 preferable from the viewpoint that initial coloring due to thermochromism is reduced and fading speed is increased. In particular, a single ring is preferable from the viewpoint that initial coloration due to thermochromism is reduced and a fading speed is increased. Specific examples of the single ring include a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, and 3,3. , 5,5-tetramethylcyclohexane ring, and the like. In particular, from the viewpoint of reducing initial coloration due to thermochromism and increasing the fading speed, a cyclooctane ring, 3,3,5,5-tetramethylcyclo A hexane ring or the like is preferable.

In the present invention, 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.

Among the chromene compounds of the present invention, 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. An alicyclic ring, an aliphatic heterocyclic ring, an aromatic ring or an aromatic heterocyclic ring fused to an aromatic heterocyclic ring, an aromatic ring or a condensed polycyclic group condensed with an aromatic heterocyclic ring, or an aliphatic heterocyclic ring Particularly preferred is a chromene compound which is a substituent selected from a condensed polycyclic group. For the same reason, lomen compounds represented by the following general formula (5) or general formula (6) are also particularly suitable.

［式中、
Ｒ¹、Ｒ²、Ｒ^2'、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、ｂ及びｄは、それぞれ、上記一般式（２）に記載ものと同意義であり、
Ｒ³及びＲ¹¹は、水素原子；ヒドロキシル基；アルキル基；ハロアルキル基；シクロアルキル基；アルコキシ基；アミノ基；窒素原子を含み、該窒素原子がピラン骨格の５位の炭素原子と直接結合する複素環基；シアノ基；ニトロ基；ホルミル基；ヒドロキシカルボニル基；アルキルカルボニル基；アルコキシカルボニル基；ハロゲン原子；アラルキル基；アリール基；アラルコキシ基；又はアリールオキシ基であり、
Ｒ¹²は、上記一般式（２）におけるＲ^1'及びＲ^2'の中で、Hammett数σ_pが−０.１以下の電子供与性の置換基である。］ General formula (5)

[Where:
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. A heterocyclic group, 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 aryl group, an aralkoxy group, or an aryloxy group,
R ¹² is an electron-donating substituent having a Hammett number σ _p of −0.1 or less among R ^{1 ′} and R ^{2 ′} in the general formula (2). ]

［式中、
Ｒ¹、Ｒ²、Ｒ^2'、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、ｂ及びｄは、それぞれ、上記一般式（２）に記載のものと同意義であり、
Ｒ³及びＲ¹¹は、上記一般式（２）に記載のものと同意義であり、
Ｒ¹³は、上記一般式（２）におけるＲ^1'及びＲ^2'の中で、Hammett数σ_pが−０.１以下の電子供与性の置換基である。］ General formula (6)

[Where:
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 the same as those described in the general formula (2),
R ¹³ is an electron-donating substituent having a Hammett number σ _p of −0.1 or less among R ^{1 ′} and R ^{2 ′} in the general formula (2). ]

Here, 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. A heterocyclic group, 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 aryl group, an aralkoxy group, or an aryloxy group. Specific examples of these groups include the same groups as those exemplified for R ^{1 ′} and R ^{2 ′} above. As a matter of course, preferable groups include those exemplified for R ^{1 ′} and R ^{2 ′} above.

R ¹² and R ¹³ in the above general formulas (5) and (6) are the electron donating properties in which the Hammett number σ _p is −0.1 or less in R ^{1 ′} and R ^{2 ′} of 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 σ _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 π-electron system. is there. The substituent whose Hammett number σ _p is 0 is a hydrogen atom.

R ¹² and R ¹³ in the general formulas (5) and (6) are particularly preferably an electron donating group having a Hammett number σ _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.

R ¹² and R ¹³ which are electron donating substituents having Hammett number σ _p of −0.1 or less include hydroxyl group (σ _p = −0.37), alkyl group, cycloalkyl group, alkoxy group, aryloxy group , An amino group, or a heterocyclic group containing a nitrogen atom, in which the nitrogen atom is directly bonded to the 6th and 7th carbon atoms of the pyran skeleton.

Hereinafter, the electron-donating substituent having a Hammett number σ _p of −0.1 or less will be described in detail.

The alkyl group is usually a group having a Hammett number σ _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. Specific examples of suitable alkyl groups include methyl group (σ _p = −0.14), ethyl group (σ _p = −0.13), n-propyl group (σ _p = −0.12), isopropyl group, and n-butyl. Group, sec-butyl group, tert-butyl group (σ _p = −0.15) and the like.

The cycloalkyl group is usually a group having a Hammett number σ _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. Specific examples of suitable cycloalkyl groups include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group (σ _p = −0.16), and the like.

The alkoxy group is usually a group having a Hammett number σ _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. Specific examples of suitable alkoxy groups include methoxy group (σ _p = −0.28), ethoxy group (σ _p = −0.21), n-propoxy group (σ _p = −0.26), isopropoxy group, n- A butoxy group, a sec-butoxy group, a tert-butoxy group, and the like can be given.

The aryloxy group is usually a group having a Hammett number σ _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. Specific examples of suitable aryloxy groups include phenoxy group (σ _p = −0.32), 1-naphthoxy group, and the like. In 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 σ _p is −0.1 or less.

The amino group is usually a group having a Hammett number σ _p of −1.0 or more and −0.5 or less. If a suitable amino group is illustrated, it will not be limited to an unsubstituted amino group ((sigma) _p = -0.66), The amino group which has a substituent may be sufficient. Examples of the substituent that the amino group has 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 4 carbon atoms. ˜12 heteroaryl groups and the like. Preferable examples of such a substituted amino group include methylamino groups (σ _p = −0.77), alkylamino groups such as ethylamino groups; dimethylamino groups (σ _p = −0.83), dialkylamino groups such as diethylamino groups Groups; arylamino groups such as phenylamino group (σ _p = −0.11), diarylamino groups such as diphenylamino group, 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 σ _p of −1.0 or more and −0.4 or less. is there. Examples of suitable heterocyclic groups include morpholino group (σ _p = −0.50), piperidino group (σ _p = −0.83), pyrrolidinyl group, piperazino group, N-methylpiperazino group, indolinyl group and the like. Furthermore, 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.

Among these, a group having a Hammett number σ _p of −0.90 to −0.20 is more preferable, and a group having −0.60 to −0.20 is more preferable in that the balance between initial coloring and double peak property is excellent. For example, 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.

Specific examples of the particularly preferred chromene compound in the present invention include the following compounds.

Identification of chromene compound The 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 the following means (a) to (c) are used. I can confirm.

(A) By measuring a proton nuclear magnetic resonance spectrum ( ¹ H-NMR), a peak based on an aromatic proton and an alkene proton in the vicinity of δ: 5.0 to 9.0 ppm, δ: 1.0 to 4 A peak based on protons of an alkyl group and an alkoxy group appears around 0.0 ppm. Moreover, the number of protons of each linking group can be known by relatively comparing the respective spectrum intensities.

  (B) The composition of the corresponding product can be determined by elemental analysis.

(C) ¹³ by measuring the C- nuclear magnetic resonance spectrum ^{(13 C-NMR), δ} : 110~160 ppm around the peak based on the carbons of an aromatic hydrocarbon group, [delta]: 80 to 140 ppm alkene near And a peak based on carbon of alkyne, and δ: a peak based on carbon of alkyl group and alkoxy group appears in the vicinity of 20 to 80 ppm.

Production of chromene compound The production method of the chromene compound of the present invention is not particularly limited, and is carried out according to various synthetic methods. For example, the chromene compound represented by the general formula (2) is preferably produced by the following method. In the following description, symbols in the respective formulas have the same meanings as described in the above-described formulas unless otherwise specified.

（式中、Ｒ¹、Ｒ²、Ｒ^1'、Ｒ^2'、Ｒ⁶、Ｒ⁷、ａ、ｂ、ｃ及びｄは、上述のとおりである）で表わされるナフトール誘導体と、一般式（８）

（式中、Ｒ⁴及びＲ⁵は、上述のとおりである）で表されるプロパルギルアルコール誘導体とを、酸触媒存在下で反応させることにより、好適に製造することができる。ナフトール誘導体とプロパルギルアルコール誘導体との反応比率は、広い範囲から採用されるが、一般には、１：１０〜１０：１（モル比）の範囲から選択される。また、酸触媒としては、硫酸、ベンゼンスルホン酸、ｐ‐トルエンスルホン酸、酸性アルミナ等が用いられ、ナフトール誘導体とプロパルギルアルコール誘導体との総和100重量部当り０.１〜１０重量部の範囲で用いられる。反応温度は、通常、０〜200℃が好ましく、溶媒としては、非プロトン性有機溶媒、例えば、Ｎ‐メチルピロリドン、ジメチルホルムアミド、テトラヒドロフラン、ベンゼン、トルエン等が使用される。かかる反応により得られる生成物の精製方法は特に限定されない。例えば、シリカゲルカラム精製を行い、さらに再結晶により、精製を行なうことができる。General formula (7)

(Wherein R ¹ , R ² , R ^{1 ′} , R ^{2 ′} , R ⁶ , R ⁷ , a, b, c and d are as described above) and a general formula (8 )

(Wherein R ⁴ and R ⁵ are as described above) can be suitably produced by reacting with a propargyl alcohol derivative in the presence of an acid catalyst. Although the reaction ratio of a naphthol derivative and a propargyl alcohol derivative is adopted from a wide range, it is generally selected from a range of 1:10 to 10: 1 (molar ratio). As the acid catalyst, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acidic alumina and the like are used, and used in the range of 0.1 to 10 parts by weight per 100 parts by weight of the total of the naphthol derivative and the propargyl alcohol derivative. It is done. The reaction temperature is usually preferably from 0 to 200 ° C., and as the solvent, 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.

As a naphthol derivative by this invention, Preferably, 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.

（式中、Ｒ¹及びａは、一般式（２）と同意義である）で表わされるベンゼン誘導体を、マグネシウムと反応させてGrignard試薬とし、ついで、酸クロリドと反応させて、一般式（１０）

で表わされる化合物（Ｒ¹、Ｒ²、Ｒ^1'、Ｒ^2'、ａ、ｂ、ｃ及びｄは一般式（２）と同意義である）を調製する。 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)).

で表わされる化合物を調製する。なお、一般式（１１）の化合物において、ＲはStobbe反応で使用したジエステル化合物由来の基である。 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. In the compound of the general formula (11), R is a group derived from the diester compound used in the Stobbe reaction.

で表わされるカルボン酸を調製する。 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.

で表されるベンジル保護されたカルボン酸誘導体を調製する。 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)

The benzyl protected carboxylic acid derivative represented by

（式中、Ｒ⁶及びＲ⁷は、一般式（２）と同意義である）で表わされるケトンと、−８０〜７０℃、１０分〜４時間、有機溶媒中で反応させ、次いで水素とパラジウム炭素等で、脱ベンジル化反応を行うことで、一般式（１４）

（式中、Ｒ¹、Ｒ²、Ｒ^1'、Ｒ^2'、Ｒ⁶、Ｒ⁷、ａ、ｂ、ｃ及びｄは、一般式（２）と同意義である）で表わされるアルコール体を調製する。
かかる反応において、前記有機金属試薬と前記一般式（１５）で表わされるケトンとの反応比率は、広い範囲から採用されるが、一般には１：１０〜１０：１（モル比）の範囲から選択される。反応温度は通常−８０〜７０℃が好ましく、溶媒としては、非プロトン性有機溶媒、例えば、ジエチルエーテル、テトラヒドロフラン、ベンゼン、トルエン等が使用される。 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. Next, 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 are the same as those 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)). Prepare.
In such a reaction, 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) For the alcohol represented by the general formula (14) obtained in the step e), 10 minutes to 2 hours at 10 to 120 ° C. under neutral to acidic conditions. 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 suitable to use in the range of -10 weight part. In this reaction, a solvent such as tetrahydrofuran, benzene, or toluene is used.

  In addition, the following compound is mentioned as a specific example of the benzene derivative represented by General formula (9) of the raw material used in the synthesis | combination of the naphthol derivative represented by General formula (7).

構造式（１６）のベンゼン誘導体は、例えば、Journal of Organic Cemistry, 729-733; 1998に記載の方法に従って合成される。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.

構造式（１７）のベンゼン誘導体は、例えば、Journal of Medicinal Chemistry, 4993-5006; 1995に記載の方法に従って合成される。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.

構造式（１８）のベンゼン誘導体は、例えば、Journal of the American Chemical Society, 5654-5655; 1990に記載の方法に従って合成される。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.

構造式（１９）のベンゼン誘導体は、例えば、Journal of Chemical Society, Perkin Transactions 2, 662-668; 1976に記載の方法に従って合成される。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.

Benzene derivative of structural formula (20)

  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 is well dissolved in general organic solvents such as toluene, chloroform, and tetrahydrofuran. When 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.

Combination with other photochromic compounds 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. As the photochromic compound to be combined, known compounds can be used without any limitation. For example, fulgide, fulgimide, spirooxazine, chromene and the like can be mentioned. Among these, 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.

  That is, it 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. In addition, a photochromic composition that provides high transparency can be obtained.

  In order to give high transparency, the other chromene compound to be combined is preferably one having a transmittance by thermochromism of 75% or more and an absorption edge of an 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 380-410 nm. In addition, the transmittance | 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.

  Specific examples of these other suitable chromene compounds include chromene compounds represented by the following general formulas (21) and (22).

一般式（２１）において、Ｒ^2'、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、一般式（２）で示したものと同意義であり、Ｒ¹²は、水素原子、ヒドロキシル基、アルキル基、ハロアルキル基、シクロアルキル基、アルコキシ基、アミノ基、環員窒素原子を含み且つその窒素原子でそれが結合しているベンゼン環に結合する複素環基、シアノ基、ニトロ基、ホルミル基、ヒドロキシカルボニル基、アルキルカルボニル基、アルコキシカルボニル基、ハロゲン原子、アラルキル基、アラルコキシ基、アリールオキシ基又はアリール基であり、ｍは０〜４の整数であり、ｎは０〜２の整数である。具体例としては、例えば、国際公開WO2001／60811パンフレットに記載の化合物が挙げられる。 Formula (21)

In the general formula (21), 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.

General formula (22)

In the general formula (22), 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. 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.

  Moreover, what is necessary is just to determine suitably the mixture ratio of each chromene compound according to the desired color tone, when setting it as the photochromic composition containing the chromene compound of this invention and another chromene compound. In that case, 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. Specifically, more preferably, in the case of a thin film such as a coating (for example, in the case of a thin film of about 100 μm), 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 It is preferable to adjust the color tone in the range of 0.001 to 5.0 parts by mass and other chromene compounds 0.001 to 5.0 parts by mass. Alternatively, in the case of a thick cured body (for example, 1 mm or more), 0.001 to 0.5 parts by mass of the chromene compound of the present invention with respect to 100 parts by mass of the polymerizable monomer that gives the thick cured body or the thick cured body. The color tone is preferably adjusted in the range of 0.001 to 0.5 part by mass of other chromene compounds.

Stabilizer to be combined Although 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. As 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 said ultraviolet absorber exhibits an effect by using in the range of 0.001-5 mass parts with respect to 100 mass parts of polymerization monomers containing the chromene compound of this invention. Moreover, a known hindered amine can be used as the light stabilizer, and a known hindered phenol can be used as the antioxidant. Said light stabilizer and antioxidant exhibit an effect by using in the range of 0.01-10 mass parts with respect to 100 mass parts of polymerization monomers containing the chromene compound of this invention.

Use of chromene compound 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.

  In addition, 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 | polymerizing and hardening this to a photochromic curable composition by mixing. That is, a cured product in which the photochromic composition is uniformly dispersed can be obtained by polymerizing and curing the photochromic curable composition containing the photochromic composition of the present invention and various polymerizable monomers.

Among them, from the viewpoint of obtaining excellent base properties such as high color density and high photochromic properties such as high fading speed, and excellent base properties such as high hardness and heat resistance, the structural formula (1), 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. Specific examples of each component include, for example, (A1) component such as glycidyl acrylate, glycidyl methacrylate, β-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 Polyalkylene glycol compounds such as acid ester compounds and methacrylic acid ester compounds and polyethylene glycol diacrylate; (A2) component includes trimethylolpropane trimeta Polyester acrylates such as polyacrylic acid and polymethacrylic acid ester compounds such as relate, urethane acrylates such as urethane oligomer tetramethacrylate and polyester oligomer hexaacrylate; (A3) components include ethylene glycol diacrylate, diethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (3,5-dibromo- 4-methacryloyloxyethoxyphenyl) propane and other polyacrylic acid and polymethacrylic acid ester compounds, etc., international publication WO2001 / 0 Examples thereof include polymerizable monomers described in 5854 pamphlet. The L scale Rockwell hardness means a hardness measured in accordance with JIS-B 7726, and it is easily judged whether or not the above hardness condition is satisfied by performing the measurement on a homopolymer of each monomer. be able to.

  A copolymer obtained by copolymerizing the polymerizable monomer described above with a polymerizable monofunctional monomer can also be used as the polymer matrix. Examples of such 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 ester compounds; methyl acrylate, methyl methacrylate, benzyl methacrylate, methacrylic acid Acrylic acid and methacrylic acid ester compounds such as 2-hydroxyethyl methacrylate; fumaric acid ester compounds such as diethyl fumarate and diphenyl fumarate; thioacrylic acid and thiomethacrylic acid such as methylthioacrylate, benzylthioacrylate, and benzylthiomethacrylate Ester compounds; vinyl compounds such as styrene, chlorostyrene, methylstyrene, vinylnaphthalene, α-methylstyrene dimer, bromostyrene, and the like. These can be used singly or in combination of two or more, and the blending amount is appropriately determined according to the intended use.

  There is no restriction | limiting in particular as a method to disperse | distribute the chromene compound of this invention in the said polymer solid matrix, A general method can be used. For example, a method in which the thermoplastic resin and chromene compound are kneaded in a molten state and dispersed in the resin, or after dissolving the chromene compound in the polymerizable monomer, a polymerization catalyst is added, and heat or light is applied. 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. In addition, 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.

  For example, 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 comprising 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. At this time, 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 (in combination 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.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
[Example 1]

のナフトール誘導体1.20ｇ（２.３ミリモル）と、構造式（２４）

のプロパルギルアルコール誘導体0.80ｇ（３.０ミリモル）とを、トルエン７０mlに溶解し、さらに、ｐ‐トルエンスルホン酸0.022ｇを添加し、加熱還流下、１時間攪拌した。
反応後、溶媒を除去し、シリカゲル上でのクロマトグラフィーにより精製して、白色粉末状の生成物1.33を得た。収率は７５％であった。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 О 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 δ 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 δ5.6-9.0 ppm.

Further, when the ¹³ C-nuclear magnetic resonance spectrum was measured, a peak based on carbon of an aromatic ring was observed in the vicinity of δ110 to 160 ppm, and a peak based on alkyl carbon was observed in δ20 to 60 ppm.

[実施例２〜１２]From the above results, it was confirmed that the product was a compound represented by the following structural formula (25).

[Examples 2 to 12]

  In the same manner as in Example 1, 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.

[実施例１３〜２４]

[Examples 13 to 24]

Evaluation of physical properties of photochromic plastic lens produced by coating method The chromene compound obtained in the above example was mixed with a photopolymerization initiator and a polymerizable monomer, and then applied to the surface of the lens substrate and irradiated with ultraviolet rays. Polymerization was performed to form a coating film on the surface of the lens substrate.

  As a 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. Hexaacrylate (Daicel UCB Co., Ltd., EB-1830) / glycidyl methacrylate mixture (mixing ratio: 50 parts by mass / 10 parts by mass / 10 parts by mass / 10 parts by mass) was used. To 90 parts by mass of this radical polymerizable monomer mixture, 1 part by mass of the chromene compound obtained in Example 1 was added and mixed well, and then CGI 1800 [1-hydroxycyclohexyl as a photopolymerization initiator was used. Mixture of phenyl ketone and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide (weight ratio 3: 1)] 0.3 parts by mass, stabilizer bis (1,2, 2,6,6-pentamethyl-4-piperidyl) sebacate 5 parts by mass, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] 3 parts by mass, silane cup Add 7 parts by mass of γ-methacryloyloxypropyltrimethoxysilane as a ring agent and 3 parts by mass of N-methyldiethanolamine. The resulting cured composition.

Subsequently, about 2 g of the photochromic curable composition obtained by the above method was spin-coated on the surface of a lens substrate (CR39: allyl resin plastic lens; refractive index = 1.50) using a MIKASA spin coater 1H-DX2. did. Optics coated with a cured polymer film (dispersed chromene compound) by irradiating the surface-coated lens with a metal halide lamp with an output of 120 mW / cm ² in a nitrogen gas atmosphere for 3 minutes. An article (photochromic plastic lens) was produced (polymer film thickness: 40 μm).

  The following photochromic characteristics were evaluated for the obtained photochromic plastic lens.

  [1] Maximum absorption wavelength (λmax): The maximum absorption wavelength after color development determined by a spectrophotometer (instant multi-channel photodetector MCPD3000) manufactured by Otsuka Electronics Co., Ltd., which was 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.

[2] Color density (A ₀ ): the difference between the absorbance ε (120) after 120 seconds of light irradiation at the maximum absorption wavelength and the absorbance ε (0) in the non-light-irradiated state. did. It can be said that the higher this value, the better the photochromic properties.

[3] 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 λ _max ) and blue (maximum from 550 nm to 650 nm) The ratio of the absorption wavelength) to the color density (A _B : value of λ _max ), and used as an index of double peak property.

  [4] Fading half-life (τ1 / 2 (second)): When light irradiation is stopped after 120 seconds of light irradiation, the absorbance at the maximum absorption wavelength of the sample is {ε (120) −ε (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.

[5] Absorption edge (λ 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 (absorption edge of the ultraviolet light spectrum) 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.

[6] 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.

[7] 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.

  [8] Color sensitivity [ε (10) / ε (120)]: Using the photochromic plastic lens obtained under the above conditions as a sample, the color density {ε (120)} after light irradiation for 120 seconds and light irradiation for 10 seconds The ratio with the subsequent color density {ε (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.

  The results of photochromic properties obtained for the photochromic plastic lens using the chromene compound of Example 1 are summarized in Table 3.

  Further, as the photochromic compound, the chromene compound obtained in Examples 2 to 12 was used, and a photochromic plastic lens was produced in the same manner as the photochromic lens production method using the chromene compound of Example 1 above. Characteristics were evaluated. The results are shown in Table 3. In Table 3, “Compound No.” corresponds to the number of the Example in which the compound was prepared (for example, “Compound No. 1” is the lomene compound prepared in Example 1).

、構造式（Ｅ）

、構造式（Ｆ）

の各フォトクロミック化合物を用いて、実施例と同様にして、フォトクロミックプラスチックレンズを作製し、各レンズのフォトクロミック特性を評価した。得られた結果を表４に示す（表４において、使用したフォクロミック化合物を、化合物No. Ａ〜Ｆで示す）。 Comparative Examples 1-6
For comparison, the photochromic compounds of the structural formulas (A) to (C) and the structural formula (D) described in Patent Documents 3 to 5 described above.

Structural formula (E)

Structural formula (F)

Using each photochromic compound, a photochromic plastic lens was produced in the same manner as in the example, and the photochromic characteristics of each lens were evaluated. The obtained results are shown in Table 4 (in Table 4, the used chromic compounds are indicated by Compound Nos. A to F).

  From the comparison of Tables 3 and 4, the following matters can be understood.

  Examples 13 to 24 (compounds 1 to 12) using the chromene compound of the present invention show high color density, high color fading speed, small initial coloration, and high repetition durability. It turns out that a high double peak property is shown.

Among the chromene compounds of the present invention, those having a high double peak property (A _Y / A _B ) can reduce the amount of yellow compounds generally having low durability when adjusting to a gray or brown color tone. This is preferable. For example, A _Y / A _B includes preferably at least 1.00 and more preferably 1.10 or more, still more preferably 1.20 or more, especially preferably 1.30 or higher.

  The fading half-life τ1 / 2 is preferably from 40 seconds to less than 130 seconds, more preferably from 40 seconds to less than 100 seconds, and particularly preferably from 40 seconds to less than 80 seconds.

  The transmittance by 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, and particularly preferably from 405 nm to 415 nm from the viewpoint of initial coloring and color development sensitivity.

  On the other hand, Comparative Example 1 (Compound A) has a problem that the double peak property is high, but the fading speed is very slow, the initial transmittance is low (colored brown), and the repetition durability is slightly low. On the other hand, it can be seen that 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 gray), and the repeated durability is also low. In contrast, 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). Have On the other hand, 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 (Compound D) has a methoxy group at the 6-position, but in any of the 5-position, 7-position, and 9-12-position, the alicyclic ring has an alicyclic ring, an aliphatic heterocyclic ring, and 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 (Compound E) 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. Alternatively, 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.

In Comparative Example 6 (Compound F), the bond with the 7-position carbon of the pyran skeleton is an aromatic ring. In this case, the initial coloring by the absorption edge becomes large (it is colored yellow because the absorption edge is in the visible region), and high double peak property cannot be obtained. On the other hand, it can be seen that 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.
[Examples 25 to 38]

  The chromene compounds shown in Table 5 were synthesized in the same manner as in Example 1. The structure of the resulting chromene compound was analyzed in the same manner as in Example 1. As a result, it was confirmed that it was a compound represented by the structural formula shown in Table 5. Table 6 shows the elemental analysis values and 1H-NMR spectrum values of the chromene compounds obtained in each Example. In Table 6, compound Nos. 25 to 38 are chromene compounds obtained in Examples 25 to 38, respectively.

［実施例３９〜５２］

[Examples 39 to 52]

  A photochromic plastic lens was produced by the same method 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.

Examples of the naphthol compound represented by the structural formula (7) are illustrated below.
[Example 53]

のベンゾフェノン誘導体42.3ｇ（122.2ミリモル）を白色固体として得た（収率：６５％）。 Preparation of Naphthol Derivative of Structural Formula (23) Used in Example 1 5.2 g (214.0 mmol) of magnesium was added to 230 ml of tetrahydrofuran, and the temperature was raised to 55 ° C. A solution of 65 g (188.0 mmol) of the benzene derivative of the above structural formula (17) in tetrahydrofuran (230 ml) was added dropwise to the previous solution to prepare a Grignard reagent. The obtained Grignard reagent was cooled to −78 ° C., and a solution of 29.8 g (214.0 mmol) of benzoyl chloride in tetrahydrofuran (230 ml) was added dropwise. After completion of the dropwise addition, the temperature was raised to room temperature and stirred for 3 hours. After the reaction, the product is washed with water, the solvent is removed, and the product is purified by recrystallization with methanol.

Of benzophenone was obtained as a white solid (yield: 65%).

の化合物58.0ｇ（122.2ミリモル）をオレンジ色オイルとして得た（収率：100％）。42.3 g (122.2 mmol) of the benzophenone derivative of the structural formula (26) and 24.5 g (140.5 mmol) of diethyl succinate were dissolved in 200 ml of tetrahydrofuran, and the temperature was raised to 55 ° C. To this solution, a solution of potassium tert-butoxide 15.7 g (140.5 mmol) in tetrahydrofuran (400 ml) was added dropwise and stirred for 1 hour. After the reaction, 200 ml of toluene was added, concentrated hydrochloric acid and then 200 ml of ethyl acetate were added, washed with water, the solvent was removed, and the following structural formula (27)

58.0 g (122.2 mmol) of was obtained as an orange oil (yield: 100%).

の化合物14.0ｇ（28.1ミリモル）を、黄色固体として得た（収率：２３％）。58.0 g (122.2 mmol) of the compound of the structural formula (27), 10.1 g (122.2 mmol) of sodium acetate and 62.4 g (608.5 mmol) of acetic anhydride were dissolved in 200 ml of toluene and refluxed for 3 hours. After the reaction, it is washed with water, the solvent is removed, and the product is purified by recrystallization with ethyl acetate and acetonitrile to obtain the following structural formula (28).

14.0 g (28.1 mmol) of was obtained as a yellow solid (yield: 23%).

のカルボン酸誘導体11.4ｇ（26.7ミリモル）を黄色固体として得た（収率：９５％）。14.0 g (28.1 mmol) of the compound of the structural formula (28) was dispersed in 75 ml of methanol. To this solution, 80 ml of an aqueous solution of 6.7 g (168.6 mmol) of sodium hydroxide was added and refluxed for 3 hours. After the reaction, the mixture is washed with concentrated hydrochloric acid and then with water, the solvent is removed, and the residue is purified again by suspending in toluene. The following structural formula (29)

11.4 g (26.7 mmol) of the carboxylic acid derivative was obtained as a yellow solid (yield: 95%).

の化合物15.9ｇ（26.2ミリモル）を黄色固体として得た（収率：９８％）。11.4 g (26.7 mmol) of the carboxylic acid derivative of the structural formula (29) and 7.4 g (58.7 mmol) of benzyl chloride were dissolved in 150 ml of N, N-dimethylformamide. To this solution, 9.2 g (66.8 mmol) of potassium carbonate was added, and the temperature was raised to 60 ° C. and stirred for 3 hours. After the reaction, 200 ml of toluene was added, washed with water, the solvent was removed, and the following structural formula (30)

15.9 g (26.2 mmol) of the above compound was obtained as a yellow solid (yield: 98%).

のカルボン酸誘導体13.3ｇ（25.7ミリモル）を黄色固体として得た（収率：９８％）。15.9 g (26.2 mmol) of the compound of the structural formula (30) was dispersed in 200 ml of isopropyl alcohol. To this solution, 180 ml of an aqueous solution of 31.4 g (786.0 mmol) of sodium hydroxide was added and refluxed for 3 hours. After the reaction, 200 ml of toluene was added, concentrated hydrochloric acid and then 200 ml of tetrahydrofuran were added, washed with water, the solvent was removed, and the residue was purified again by suspending in toluene. The following structural formula (31)

13.3 g (25.7 mmol) of the carboxylic acid derivative was obtained as a yellow solid (yield: 98%).

の化合物11.6ｇ（23.6ミリモル）を黄色固体として得た（収率：９２％）。13.3 g (25.7 mmol) of the carboxylic acid derivative of the structural formula (31) was dispersed in 180 ml of toluene. To this solution, 7.8 g (77.1 mmol) of triethylamine and 9.2 g (33.4 mmol) of diphenylphosphoryl azide were added and stirred at room temperature for 2 hours. To this solution, 5.9 g (128.5 mmol) of ethanol was added and reacted at 70 ° C. for 2 hours. To this solution, 75 ml of ethanol was added, and then 14.4 g (257.0 mmol) of potassium hydroxide was added and refluxed for 3 hours. After the reaction, ethanol was distilled off at normal pressure, 200 ml of tetrahydrofuran was added, washed with water, the solvent was removed, and the following structural formula (32)

11.6 g (23.6 mmol) of the compound was obtained as a yellow solid (yield: 92%).

の化合物10.6ｇ（17.7ミリモル）を黄色固体として得た（収率：７５％）。11.6 g (23.6 mmol) of the compound of the structural formula (32) was dispersed in 150 ml of acetonitrile, 101.3 g (116.8 mmol) of 6% hydrochloric acid aqueous solution was added, and the mixture was cooled to 0 to 5 ° C. To this solution, 7.3 g (35.4 mmol) of 33% sodium nitrite aqueous solution was added and stirred for 30 minutes. To this solution was added 19.6 g (118.0 mmol) of a 50% aqueous potassium iodide solution, and the mixture was stirred at room temperature for 6 hours. After the reaction, toluene is added, washed with water, the solvent is removed, and purified by column chromatography to obtain the following structural formula (33)

Of the compound as a yellow solid (yield: 75%).

の化合物６.７ｇ（10.6ミリモル）を黄色固体として得た（収率：６０％）。10.6 g (17.7 mmol) of the compound of the structural formula (32) was dispersed in 370 ml of toluene and cooled to −50 ° C. To this solution, 12.2 ml (19.5 mmol) of n-butyllithium (1.6M hexane solution) was added dropwise and stirred for 30 minutes. To this solution, 7.0 g of a toluene solution of 3.4 g (22.2 mmol) of 3,3,5,5-tetramethylcyclohexanone was added dropwise and stirred at 0 ° C. for 3 hours. After the reaction, toluene was added, washed with water, the solvent was removed, and the residue was purified again by suspending in methanol to obtain the following structural formula (34).

6.7 g (10.6 mmol) of the above compound was obtained as a yellow solid (yield: 60%).

の化合物５.４ｇ（10.0ミリモル）を黄色固体として得た（収率：９４％）。6.7 g (10.6 mmol) of the compound of the structural formula (34) was dissolved in 150 ml of tetrahydrofuran, 2.7 g (42.4 mmol) of ammonium formate, and 2.2 g of 5% palladium carbide were added, and the mixture was stirred at room temperature for 8 hours. . After the reaction, 50 ml of toluene was added, washed with water, the solvent was distilled off, and then purified by suspending again with toluene to obtain the following structural formula (35).

5.4 g (10.0 mmol) of the compound was obtained as a yellow solid (yield: 94%).

5.4 g (10.0 mmol) of the compound of the structural formula (35) was dissolved in 120 ml of toluene and heated to 90 ° C. To this solution, 57.6 g (303.0 mmol) of p-toluenesulfonic acid monohydrate was added and refluxed for 4 hours. After the reaction, it was washed with water, the solvent was removed, and the residue was purified again by suspending in toluene to obtain 3.9 g (7.5 mmol) of the naphthol compound of the above structural formula (23) as a white solid. (Yield: 75%).
The elemental analysis values of this product were C: 85.42%, H: 8.55%, O: 6.03%, and C ₃₇ H ₄₄

The calculated values of O ₂ agreed well with C: 85.34%, H: 8.52%, and O: 6.14%.

  When the proton nuclear magnetic resonance spectrum was measured, a peak of 36H based on an alkyl group was observed around δ 0.5 to 4.5 ppm, and a peak of 8H based on a hydroxyl group and an aromatic ring proton was observed around δ 5.0 to 9.0 ppm. Indicated.

Furthermore, when the ¹³ C-nuclear magnetic resonance spectrum was measured, a peak based on carbon of an aromatic ring was observed around δ110 to 160 ppm, and a peak based on carbon of an alkyl group and an alkoxy group was observed at δ20 to 80 ppm.

From the above results, it was confirmed that the isolated product was a naphthol compound of the structural formula (23).
[Examples 54 to 78]

In the same manner as in Example 53, naphthol compounds shown in Table 8 below were synthesized. As a result of structural analysis using the same structure identification means as in Example 53, the obtained product was a naphthol derivative used in the synthesis of the chromene compounds of Examples 2-12 and Examples 25-38. confirmed. Table 8 shows elemental analysis values of these naphthol compounds, calculated values obtained from the structural formulas of the respective compounds, and characteristic spectra of ¹ H-NMR spectra.

Claims (17)

Structural formula (1)

A chromene compound having an indeno (2,1-f) naphtho (1,2-b) pyran skeleton as a basic skeleton, wherein the indeno (2,1-f) naphtho (1,2-b) pyran skeleton In the alicyclic ring in which at least one of the carbon atoms at positions 5 to 12 has a bonding site with the carbon atom of the indeno (2,1-f) naphtho (1,2-b) pyran skeleton, A ring, an aliphatic heterocycle, an aromatic ring or a condensed polycyclic group condensed with an aromatic heterocycle, and a bond to a carbon atom of the indeno (2,1-f) naphtho (1,2-b) pyran skeleton A substituent selected from the group consisting of an alicyclic ring, an aliphatic heterocyclic ring, an aromatic ring, or a condensed polycyclic group condensed with an aromatic heterocyclic ring is bonded to a carbon-carbon bond to the aliphatic heterocyclic ring in which the moiety is present. A chromene compound characterized by comprising General formula (2)

[Where,
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. A fused 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, an alicyclic ring, an aliphatic heterocyclic ring, an aromatic ring Or a group selected from the group consisting of condensed polycyclic groups condensed with an aromatic heterocycle, which is linked to an indeno (2,1-f) naphtho (1,2-b) pyran skeleton via a carbon-carbon bond. A bonding group,
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; Cyano group; nitro group; formyl group; hydroxycarbonyl group; alkylcarbonyl group; alkoxycarbonyl group; halogen atom; aralkyl group; aryl group; aralkoxy group; or aryloxy group,
R ⁴ and R ⁵ are each independently represented by the general formula (3)

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 cycloalkyl group; an alkoxy group; an amino group; a nitrogen atom, and the nitrogen atom is directly connected to the carbon atom at the 13th position. Cyano group; nitro group; formyl group; hydroxycarbonyl group; alkylcarbonyl group; alkoxycarbonyl group; halogen atom; aralkyl group; aryl group; aralkoxy group; or aryloxy group, or R ⁶ And R ⁷ together with a carbon atom at position 13 of the indeno (2,1-f) naphtho (1,2-b) pyran skeleton, together with each other, an alicyclic ring having 3 to 20 carbon atoms A condensed polycyclic ring condensed with an aromatic ring or aromatic heterocyclic ring on a group or alicyclic ring, or a heterocyclic group or heterocyclic ring having 3 to 20 carbon atoms, condensed with an aromatic ring or aromatic heterocyclic ring Ring Condensed polycyclic was formed,
a, b, c and d are each an integer of 0 to 4, provided that a + b = 1 to 8, a + c = 4, b + d = 4,
when a is 2 or more, R ¹ are the same or different from each other;
when b is 2 or more, R ² are the same or different from each other;
when c is 2 or more, R ^{1 ′} is the same or different from each other;
when d is 2 or more, R ^{2 ′} is the same or different from each other;
when both a and b are not 0, R ¹ and R ² are the same or different from each other;
When c and d are not 0, R ^{1 ′} and R ^{2 ′} are the same or different from each other.]
The chromene compound of Claim 1 represented by these.   A condensed polycyclic group in which an alicyclic ring is condensed to an alicyclic ring having a bonding site with a carbon atom of an indeno (2,1-f) naphtho (1,2-b) pyran skeleton is formed by bicyclo [2 , 2,1] heptane ring, bicyclo [2,2,2] octane ring, bicyclo [3,2,1] octane ring, bicyclo [3,3,1] nonane ring, and bicyclo [4,3,0] A group having 4 to 20 carbon atoms constituting a ring selected from the group consisting of nonane ring or a group having 4 to 20 carbon atoms constituting a ring selected from 1-adamantane ring and 2-adamantane ring The chromene compound according to claim 1 or 2.   A condensed polycyclic group in which an aliphatic heterocycle is condensed to an alicyclic ring in which an attachment site to a carbon atom of an indeno (2,1-f) naphtho (1,2-b) pyran skeleton exists is an azabicyclo [2 , 2,1] heptane ring, azabicyclo [2,2,2] octane ring, 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, A C3-C20 bicyclo ring group constituting a ring selected from a thiabicyclo [2,2,2] octane ring, a thiabicyclo [3,2,1] octane ring, and a thiabicyclo [3,3,1] nonane ring Or 1-azaadamantane ring, 2-azaadamantane ring, 1-oxaadamantane ring, and 1-thiaadada Is a group of the tricyclo ring having 3 to 20 carbon atoms constituting the ring selected from pentane ring, according to claim 1 or 2 chromene compound according.   A condensed polycyclic group in which an aromatic ring is condensed to an alicyclic ring in which an indeno (2,1-f) naphtho (1,2-b) pyran skeleton is bonded to a carbon atom is a benzocyclopropane ring. A condensed polycycle having 7 to 30 carbon atoms constituting a ring selected from the group consisting of a group, a benzocyclobutane ring group, a benzocyclopentane ring group, a benzocyclohexane ring group, a benzocycloheptane ring group, and a benzocyclooctane ring group The chromene compound according to claim 1 or 2, which is a group.   A condensed polycyclic group in which an aromatic heterocycle is condensed to an alicyclic ring in which an attachment site to a carbon atom of an indeno (2,1-f) naphtho (1,2-b) pyran skeleton exists is 3,4 A condensed polycyclic ring having 6 to 30 carbon atoms constituting a ring selected from the group consisting of a 3-cyclopentenopyridine ring group, a 3,4-cycloheptenopyridine ring group, and a 3,4-cyclooctenopyridine ring group The chromene compound according to claim 1 or 2.   A condensed polycyclic group in which an alicyclic ring is condensed to an aliphatic heterocycle having a bonding site with a carbon atom of an indeno (2,1-f) naphtho (1,2-b) pyran skeleton is represented by an azabicyclo [4 , 3,0] nonane ring group, oxabicyclo [4,3,0] nonane ring group, heptahydrocyclohexa [c] thiophene ring group The chromene compound according to claim 1 or 2, which is a ring.   A condensed polycyclic group in which an aliphatic heterocycle is condensed to an aliphatic heterocycle having a bonding site with a carbon atom of an indeno (2,1-f) naphtho (1,2-b) pyran skeleton is represented by diazabicyclo [2 , 2,1] heptane ring, diazabicyclo [2,2,2] octane ring, diazabicyclo [3,2,1] octane ring, diazabicyclo [3,3,1] nonane ring, diazabicyclo [4,3,0] nonane Ring, dioxabicyclo [2,2,1] heptane ring, dioxabicyclo [2,2,2] octane ring, dioxabicyclo [3,2,1] octane ring, dioxabicyclo [3,3,1 ] Nonane ring, dioxabicyclo [4,3,0] nonane ring, dithiabicyclo [2,2,1] heptane ring, dithiabicyclo [2,2,2] octane ring, dithiabicyclo [3,2,1] octane ring, From the dithiabicyclo [3,3,1] nonane ring, 2,4,10-triazatricyclo [3,3,1,13,7] decane group That condensation of 3 to 20 carbon atoms constituting the ring selected from the group Hajime Tamaki, according to claim 1 or 2 chromene compound according.   A fused polycyclic group in which an aromatic ring is condensed to an aliphatic heterocyclic ring in which an indeno (2,1-f) naphtho (1,2-b) pyran skeleton is bonded to a carbon atom is a 2-indoline ring The chromene according to claim 1 or 2, which is a condensed polycycle having 7 to 30 carbon atoms constituting a ring selected from the group consisting of a group, a 2-coumaran ring group, and a 2,3-dihydrobenzo [c] thiophene ring group. Compound.   A condensed polycyclic group in which an aromatic heterocycle is condensed to an aliphatic heterocycle having a binding site to a carbon atom of an indeno (2,1-f) naphtho (1,2-b) pyran skeleton is -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- A condensed polycyclic group having 6 to 30 carbon atoms constituting a ring selected from the group consisting of a dihydrofuro [3,4-b] furan group and a 4,6-dihydrothieno [3,4-b] thiophene group. The chromene compound according to 1 or 2. General formula (5)

[Where:
R ¹ , R ² , R ^{2 ′} , R ⁴ , R ⁵ , R ⁶ , R ⁷ , b and d are respectively the same as defined in claim 2,
R ³ and R ¹¹ are 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 heterocyclic group in which the nitrogen atom is directly bonded to a carbon atom of a pyran skeleton. Cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, halogen atom, aralkyl group, aryl group, aralkoxy group, or aryloxy group,
R ¹² is an electron donating group having a Hammett number σ _p of −0.1 or less among R ^{1 ′} and R ^{2 ′} defined in claim 2]
The chromene compound of Claim 2 represented by these. General formula (6)

[Where:
R ¹ , R ² , R ^{2 ′} , R ⁴ , R ⁵ , R ⁶ , R ⁷ , b and d are each as defined in claim 2;
R ³ and R ¹¹ are as defined in claim 10;
R ¹³ is an electron donating group having a Hammett number σ _p of −0.1 or less among R ^{1 ′} and R ^{2 ′} defined in claim 2]
The chromene compound of Claim 2 represented by these. A method for producing the chromene compound according to claim 2, wherein the chromene compound has the general formula (7).

Wherein R ¹ , R ² , R ^{1 ′} , R ^{2 ′} , R ⁶ , R ⁷ , a, b, c and d are as defined in claim 2, respectively. The naphthol derivative obtained is represented by the general formula (8) in the presence of an acid catalyst.

(Wherein R ⁴ and R ⁵ are the same as defined in claim 2), and a reaction with a propargyl alcohol derivative.   A photochromic curable composition comprising the chromene compound according to any one of claims 1 to 11 and a polymerizable monomer.   A photochromic optical article having, as a constituent member, a polymer molded body in which the chromene compound according to any one of claims 1 to 11 is dispersed.   The optical article which has the optical base material coat | covered with the polymer film in which all or a part of at least 1 surface has disperse | distributed the chromene compound in any one of Claims 1-11 as a structural member. General formula (7)

(Wherein R ¹ , R ² , R ^{1 ′} , R ^{2 ′} , R ⁶ , R ⁷ , a, b, c and d are the same as defined in claim 2). Naphthol derivative.