JP6798851B2 - A chromene compound and a curable composition containing the chromene compound. - Google Patents

Description

The present invention relates to a novel chromene compound useful as a photochromic compound.

Photochromism is a reversible reaction in which when a compound is irradiated with light containing ultraviolet rays such as sunlight or mercury lamp light, the color changes rapidly, and when the light is stopped and placed in a dark place, the color returns to the original color due to heat. Is. Compounds having this property are called photochromic compounds and are used as materials for photochromic plastic lenses.

Generally, in photochromic compounds used for such applications.
(I) The degree of coloration in the visible light region (hereinafter referred to as initial coloration) before irradiation with ultraviolet rays is small.
(II) The speed from the start of irradiation with ultraviolet rays until the color development density (hereinafter referred to as the color development density) reaches saturation is fast.
(III) The speed from the start of irradiation with ultraviolet rays until the color development density reaches saturation is fast (hereinafter, also referred to as high color development sensitivity).
(IV) The speed from stopping the irradiation of ultraviolet rays to returning to the original state (hereinafter referred to as the fading speed) is fast,
(V) The reversible action has good repeated durability, and
(VI) In order to increase the dispersibility in the host material used, it is required to have a property of being dissolved in a monomer composition as a host material after curing at a high concentration.

Among such photochromic compounds, many compounds having an indenonaphthopyrane skeleton (hereinafter, may be referred to as chromene compounds) have been developed as compounds satisfying the above characteristics.

For example, a chromene compound represented by the following formula (A) (see Patent Document 1), a chromene compound represented by the following formula (B) (see Patent Document 2), and a chromene compound represented by the following formula (C) (Patent Document). 3) is known. These compounds exert excellent effects as compared with other photochromic compounds.

In recent years, the properties required for chromene compounds have become even higher. Therefore, there is room for improvement in the above-mentioned chromium compound in the following points. Specifically, the chromene compounds represented by the formulas (A), (B) and (C) are colored in a state of not being irradiated with light (also referred to as coloring at the time of deterioration) when used as a photochromic plastic lens for a long period of time, for example. There was a problem that (.) Became large and the color density at the time of light irradiation decreased.

On the other hand, as a chromene compound exhibiting excellent properties of low coloring at the time of deterioration and a high fading rate, the chromene compound represented by the following formula (D) (Patent Document 3) and the following formula (E) are shown. Chromen compounds (Patent Document 4) are known.

International Publication WO 1996/04576 Pamphlet International Publication WO2004 / 085568 Pamphlet International Patent Publication WO2001 / 060811 Pamphlet Japanese Patent No. 3522189

The demand for photochromic compounds has become more sophisticated and rapidly expanding in recent years. Therefore, it is also desired that the photochromic compound satisfies the properties that have not been required so far. For example, it has become important to use it in the summer when the sunlight is strong and in high temperature. Specifically, the development of a photochromic compound having a high color-developing density even under a high temperature such as in summer while maintaining the above-mentioned characteristics (I) to (VI) to some extent is particularly required (hereinafter, under high temperature). However, the characteristic having a high color density may be referred to as "small temperature dependence").

However, in general, the color fading of the chromene compound is promoted by heat, so that an effective chromene compound that sufficiently satisfies such a requirement is not generally known at present. For example, the compounds represented by the formulas (D) and (E) having a high fading rate have a large temperature dependence. Further, also in other compounds represented by the above formulas (A), (B), and (C), compounds that highly satisfy both the conventionally desired properties and the "property with low temperature dependence". Did not exist.

Therefore, an object of the present invention is to provide a chromene compound having a small temperature dependence while maintaining some conventional characteristics.

Various developments of chromene compounds are underway because various photochromic properties can be exhibited according to each application by giving various substituents to the indenonaphthopyrane skeleton. Therefore, the present inventors have examined various substituents, the positions of the substituents, and the combinations of the substituents. Among the innumerable combinations, the ring group that spiro-bonds with the carbon atom at the 13-position (hereinafter referred to as “)”. By using the substituents at the 6-position, 7-position, and 11-position as specific substituents (sometimes simply referred to as "ring X group"), a chromene compound having excellent color development at high temperature and low temperature dependence. We have found that this can be obtained, and have completed the present invention.

That is, the first invention has the following equation (1).

(During the ceremony,
R ¹ and R ² are independently an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an amino. A group, a substituted amino group, or a heterocyclic group,
R ³ is a hydrogen atom
R ⁴ and R ⁵ are independently hydroxy groups, alkyl groups having 1 to 6 carbon atoms, haloalkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms. Group, amino group, substituted amino group, heterocyclic group, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, halogen atom, carbon Aralkyl group having 7 to 11 carbon atoms, aralkylthio group having 7 to 11 carbon atoms, aryl group having 6 to 12 carbon atoms, thiol group, alkylthio group having 1 to 6 carbon atoms, alkoxyalkylthio group having 2 to 9 carbon atoms, carbon number of carbon atoms A haloalkylthio group having 1 to 6, a cycloalkylthio group having 3 to 8 carbon atoms, or an arylthio group having 6 to 10 carbon atoms.
a is an integer of 0 to 3, and when a is 2 or more, R ⁴ may be the same or different groups from each other. When b is an integer of 0 to 2, and b is 2. R ⁵ may be the same or different groups from each other
R ⁶ and R ⁷ independently have an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an amino. A group, a substituted amino group, a heterocyclic group, a halogen atom, or an aryl group having 6 to 12 carbon atoms.
c is an integer from 0 to 5, and when c is 2 or more, R ⁶ may be the same or different groups from each other.
d is an integer from 0 to 5, and when d is 2 or more, R ⁶ may be the same or different groups from each other.
The following formula

The ring group spirobonded with the carbon atom at the 13-position represented by is an aliphatic hydrocarbon ring group consisting of a single ring having 4 to 20 carbon atoms, and the aliphatic hydrocarbon ring group has 1 to 6 carbon atoms. Alkyl group, haloalkyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 8 carbon atoms, alkoxy group having 1 to 6 carbon atoms, amino group, substituted amino group, and at least 1 selected from the group consisting of halogen atoms. It may have a type of substituent. ) Is a chromium compound.

The chromium compound of the present invention exerts an excellent effect by using the substituents at the ring X group, the 6-position, the 7-position, and the 11-position as specific substituents. Of these, if even one substituent does not satisfy the requirements of the present invention, excellent properties cannot be exhibited. In the conventional compound, there is no compound that simultaneously satisfies these four substituents.

Therefore, for example, when a photochromic lens is produced using the chromen compound of the present invention, it is possible to produce a photochromic lens having a high color density and a small temperature dependence even at a high temperature such as in summer.

The chromium compound of the present invention has the following formula (1).

It has an indenonaphthopyran structure represented by (1) as a basic skeleton. It is known that a chromene compound having an indenonaphthopyrane structure exhibits excellent photochromic properties. In the present invention, among the chromene compounds having the basic skeleton, by using the substituents at the ring X, 6, 7, and 11 positions as specific substituents, the excellent photochromic properties are maintained and the temperature is high. It is possible to obtain a chromene compound having excellent color development and low temperature dependence. Hereinafter, specific substituents will be described step by step.

<R ¹ and R ² >
R ¹ is a substituent that binds to the carbon atom at the 6-position of the pyran skeleton, and R ² is a substituent that binds to the carbon atom at the 11-position of the pyran skeleton. In the present invention, R ¹ and R ² are independently an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and 1 to 6 carbon atoms, respectively. It is selected from an alkoxy group, an amino group, a substituted amino group, or a heterocyclic group.

The alkyl group having 1 to 6 carbon atoms is not particularly limited, and examples of suitable alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and t. -Butyl group, n-hexyl group and the like can be mentioned.

The haloalkyl group having 1 to 6 carbon atoms is not particularly limited, but a haloalkyl group having 1 to 6 carbon atoms substituted with a fluorine atom, a chlorine atom or a bromine atom is preferable. Examples of suitable haloalkyl groups include trifluoromethyl group, tetrafluoroethyl group, chloromethyl group, 2-chloroethyl group, bromomethyl group and the like.

The cycloalkyl group having 3 to 8 carbon atoms is not particularly limited, and examples of suitable cycloalkyl groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like. be able to.

The alkoxy group having 1 to 6 carbon atoms is not particularly limited, and examples of suitable alkoxy groups include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an s-butoxy group, and a t-butoxy group. And so on.

The substituted amino group is not particularly limited, and is, for example, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and carbon. Examples thereof include a secondary amino group and a tertiary amino group having an aryl group of numbers 6 to 12. Examples of suitable substituted amino groups include methylamino group, dimethylamino group, ethylamino group, diethylamino group, phenylamino group, diphenylamino group and the like.

The heterocyclic group is not particularly limited, and examples of suitable heterocyclic groups include a morpholino group, a piperidino group, a pyrrolidinyl group, a piperazino group, an N-methylpiperadino group, and the like.

Among the above, although it depends on the combination with other groups, R ¹ and R ² have an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a substituted amino group, or a heterocyclic group. Preferably, an alkoxy group having 1 to 6 carbon atoms, a substituted amino group having an alkyl group having 1 to 6 carbon atoms, or a heterocyclic group is particularly preferable. Examples of particularly suitable ones include a methoxy group, a dimethylamino group, a morpholino group and the like.

<R ³ >
In the chromene compound of the present invention, R ³ must be a hydrogen atom.

<R ⁴ and R ⁵ >
R ⁴ and R ⁵ are independently hydroxy groups, alkyl groups having 1 to 6 carbon atoms, haloalkyl groups having 1 to 6 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms. Group, amino group, substituted amino group, heterocyclic group, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, halogen atom, carbon Aralkyl group having 7 to 11 carbon atoms, aralkylthio group having 7 to 11 carbon atoms, aryl group having 6 to 12 carbon atoms, thiol group, alkylthio group having 1 to 6 carbon atoms, alkoxyalkylthio group having 2 to 9 carbon atoms, carbon number of carbon atoms It is a haloalkylthio group having 1 to 6, a cycloalkylthio group having 3 to 8 carbon atoms, or an arylthio group having 6 to 10 carbon atoms.

In R ⁴ and ^{R 5,} the alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, amino group, substituted amino Examples of the group and the heterocyclic group include the same groups as those already described in <R ¹ and R ² >, and examples of suitable groups include the same groups.

The alkylcarbonyl group having 2 to 7 carbon atoms is not particularly limited, and examples of suitable alkylcarbonyl groups include an acetyl group and an ethylcarbonyl group.

The alkoxycarbonyl group having 2 to 7 carbon atoms is not particularly limited, and examples of suitable alkoxycarbonyl groups 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 having 7 to 11 carbon atoms is not particularly limited, and examples of suitable aralkyl groups include a benzyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group.

The aralkyl group having 7 to 11 carbon atoms is not particularly limited, and examples of suitable aralkyl groups include a benzyloxy group and a naphthylmethoxy group.

The aryl group having 6 to 12 carbon atoms is not particularly limited, and examples of suitable aryl groups include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.

The Alkoxy group having 7 to 11 carbon atoms, the Alkoxy group having 7 to 11 carbon atoms, and the aryl group having 6 to 12 carbon atoms contain hydrogen atoms, preferably 1 to 4 hydrogen atoms contained in the group. , The above-mentioned hydroxyl group, alkyl group having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbon atoms, cycloalkyl group having 3 to 8 carbon atoms, alkoxy group having 1 to 6 carbon atoms, amino group, substituted amino group, It may be substituted with a heterocyclic group, a cyano group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group having 2 to 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, or a halogen atom.

The alkylthio group having 1 to 6 carbon atoms is not particularly limited, and examples of suitable alkylthio groups include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, and t. -Butylthio group, n-hexylthio group and the like can be mentioned.

The alkoxyalkylthio group having 2 to 9 carbon atoms is not particularly limited, and examples of suitable alkoxyalkylthio groups include a methoxymethylthio group, a methoxyethylthio group, a methoxyn-propylthio group, a methoxyn-butylthio group, and an ethoxyethylthio group. Groups, n-propoxy n-propyl group and the like can be mentioned.

The haloalkylthio group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include an alkylthio group having 1 to 6 carbon atoms substituted with a fluorine atom, a chlorine atom, and a bromine atom. Examples of suitable haloalkylthio groups include trifluoromethylthio group, tetrafluoroethylthio group, chloromethylthio group, 2-chloroethylthio group and bromomethylthio group.

The cycloalkylthio group having 3 to 8 carbon atoms is not particularly limited, and examples of suitable cycloalkylthio groups include a cyclopropylthio group, a cyclobutylthio group, a cyclopentylthio group, a cyclohexylthio group, a cycloheptylthio group, and a cyclo. An octylthio group and the like can be mentioned.

The arylthio group having 6 to 10 carbon atoms is not particularly limited, and examples of suitable arylthio groups include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and the like.

Of the above, R ⁴ and R ^5, alkyl groups having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, amino group, substituted amino group is preferably a heterocyclic group, an alkyl having 1 to 6 carbon atoms A group, an alkoxy group having 1 to 6 carbon atoms, a substituted amino group having an alkyl group having 1 to 6 carbon atoms, and a heterocyclic group are preferable. Examples of particularly suitable ones include a methyl group, a methoxy group, a dimethylamino group, a morpholino group and the like.

a is an integer of 0 to 3, refers to the number of substituents ^{R 4.} When a is 2 or more, R ⁴ may be the same or different groups from each other. b is an integer of 0 to 2, refers to the number of substituents ^{R 5.} When b is 2, R ⁵ may be the same or different groups from each other. Even when a plurality of R ⁴ and R ⁵ are present, the preferred group is the group shown in the above description.

Although the preferable groups of R ⁴ and R ⁵ have been exemplified above, a = 0, b = 0, that is, R, in consideration of the productivity of the chromene compound, ease of handling, etc. while maintaining excellent properties. ^4, and it is most preferable that both of R ⁵ is a hydrogen atom.

<R ⁶ and R ⁷ >
R ⁶ and R ⁷ independently have an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an amino. A group, a substituted amino group, a heterocyclic group, a halogen atom, or an aryl group having 6 to 12 carbon atoms. Here, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a substituted amino group, a heterocyclic group, and a halogen atom. , an aryl group having 6 to 12 carbon ^{atoms, R 1, R 2, R} 4, and include the same groups as previously described with ^{R 5,} is the same preferable groups.

Among the above, R ⁶ and R ⁷ are preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, a substituted amino group, a heterocyclic group, or a halogen atom. Alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, substituted amino groups having alkyl groups having 1 to 6 carbon atoms, and heterocyclic groups are preferable. Examples of particularly suitable ones include a methyl group, a methoxy group, a dimethylamino group, a morpholino group, a piperidino group, a fluoro group and the like.

c is an integer from 0 to 5, refers to the number of substituents ^{R 6.} When c is 2 or more, R ⁶ may be the same or different groups from each other. d is an integer from 0 to 5 and refers to the number of substituents on R ⁷ . When d is 2, R ⁵ may be the same or different groups from each other. Even when a plurality of R ⁶ and R ⁷ are present, the preferred group is the group shown in the above description.

Further, in order to exhibit excellent photochromic characteristics, c and d are preferably 0 or 1. When c = 1 and d = 1, the position of the substituent is preferably the 3-position or 4-position of the phenyl group.

<Ring X group>
The following formula

The ring group spiro-bonded to the carbon atom at the 13-position represented by (1) is an aliphatic hydrocarbon ring group (ring X group) composed of a single ring having 4 to 20 carbon atoms. A monocycle having 4 to 20 carbon atoms is a group having a plurality of rings such as a bicyclo ring or a tricyclo ring, and a group in which one ring group is fused with another ring (ring group). Means not.

As the monocycle (ring X) having 4 to 20 carbon atoms, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring are particularly preferable.

The aliphatic hydrocarbon ring group (ring X group) composed of a single ring having 4 to 20 carbon atoms is an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, and a cyclo having 3 to 8 carbon atoms. It may have at least one substituent selected from the group consisting of an alkyl group, an alkoxy group having 1 to 6 carbon atoms, an amino group, a substituted amino group and a halogen atom. The alkyl group having 1 to 6 carbon atoms, the haloalkyl group having 1 to 6 carbon atoms, the cycloalkyl group having 3 to 8 carbon atoms, the alkoxy group having 1 to 6 carbon atoms, the amino group, the substituted amino group and the halogen atom are Examples include groups similar to those already described in R ¹ , R ² , R ⁴ , and R ⁵ . Among the substituents of the ring X group, the chromene compound of the present invention exerts a particularly excellent effect as an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, and 1 to 1 carbon atoms. An alkoxy group of 6 is preferable, and an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms are particularly preferable.

Among the above ring X groups, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, or a ring group in which an alkyl group having 1 to 6 carbon atoms (preferably an alkyl group having 1 to 3 carbon atoms) is bonded to these rings. Preferably, particularly preferably, it is an unsubstituted cyclohexane ring group, a cycloheptane ring group, or a cyclooctane ring group having no substituent. A typical example of a suitable ring X is represented by, for example, the following formula. In the following formula, the carbon atom represented by 13 is the 13-position carbon atom of the indenonaphthopyran structure.

<Especially suitable chromene compound>
Specific examples of particularly suitable chromium compounds in the present invention include

<Identification of chromene compounds>
The chromene compound of the present invention generally exists as a colorless, pale yellow, pale green solid or viscous liquid at normal temperature and pressure, and can be confirmed by the following means (a) to (c).

(A) By measuring the proton nuclear magnetic resonance spectrum ( ¹ H-NMR), peaks based on aromatic protons and alkene protons around δ: 5.0 to 9.0 ppm, δ: 1.0 to 4 Proton-based peaks of alkyl and alkylene groups appear near 0.0 ppm. In addition, the number of protons of each bonding group can be known by comparing the spectral intensities of each.

(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} : a peak based on the carbons of the aromatic hydrocarbon group near 110~160ppm, δ: 80~140ppm alkenes and alkynes in the vicinity Carbon-based peaks of alkyl and alkylene groups appear in the vicinity of δ: 20 to 80 ppm.

<Manufacturing of chromene compounds>
The chromene compound of the present invention may be produced by any synthetic method. To give an example thereof, the chromene compound represented by the above formula (1) can be suitably produced by the following method. In the following description, the reference numerals in the respective formulas have the same meanings as described in the above-mentioned formulas unless otherwise specified.
The following formula (5):

With the naphthol compound indicated by
The following formula (6):

It can be suitably produced by a method of reacting with the propargyl alcohol compound represented by (1) in the presence of an acid catalyst. The reaction ratio of the naphthol compound and the propargyl alcohol compound is preferably selected from the range of 1:10 to 10: 1 (molar ratio). Further, as the acid catalyst, for example, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acidic alumina and the like are used. The acid catalyst is used in the range of 0.1 to 10 parts by weight per 100 parts by weight of the total of the naphthol compound and the propargyl alcohol compound. The reaction temperature is preferably 0 to 200 ° C. As the solvent, an aprotic organic solvent, for example, N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, benzene, toluene and the like is preferably used. The method for purifying the product obtained by such a reaction is not particularly limited. For example, the product can be purified by performing silica gel column purification and further recrystallization.

Among the naphthol compounds represented by the formula (5), a preferable compound has a structure capable of producing a suitable chromene compound represented by the formula (1). For example, a compound represented by the following formula can be mentioned as particularly preferable.

The naphthol compound represented by the formula (5) can be synthesized, for example, as follows. The naphthol compound can be synthesized based on the reaction method described in the papers such as International Publication No. WO2001 / 60881 Pamphlet and International Publication No. WO2005 / 028465 Pamphlet.

First, the following equation (7):

By carrying out a stove reaction and a cyclization reaction on the benzophenone compound represented by

To obtain the compound of. In the compound of the formula (8), R is a group derived from the diester compound used in the Stobbe reaction, and Ac is an acetyl group. Then, the compound (8) is hydrolyzed with an alkali or an acid to form the following formula (9).

To obtain the carboxylic acid of. The carboxylic acid is benzylated by using a base such as potassium carbonate and benzyl chloride, and then hydrolyzed by using an alkali or an acid, and the following formula (10)

To obtain the benzyl-protected carboxylic acid represented by. The benzyl-protected carboxylic acid (Bn in formula (10) is a benzyl group) is converted to an amine by a method such as Curtius rearrangement, Hofmann rearrangement, Lossen rearrangement, etc., from which a diazonium salt is prepared by a method known per se. To do. This diazonium salt is converted into bromide by a Sandmeyer reaction or the like, and the obtained bromide is reacted with magnesium, lithium or the like to prepare an organometallic compound. This organometallic compound is expressed by the following formula (11):

By reacting with the ketone represented by the above in an organic solvent at -80 to 70 ° C. for 10 minutes to 4 hours, and then debenzylation reaction with hydrogen and palladium carbon or the like, the following formula (12):

Obtain the alcohol indicated by. The Friedel-Crafts reaction of this alcohol at 10 to 120 ° C. for 10 minutes to 2 hours under neutral to acidic conditions can be used to synthesize the desired naphthol compound of the formula (5). In such a reaction, the reaction ratio of the organometallic compound to the ketone represented by the formula (11) is preferably selected from the range of 1:10 to 10: 1 (molar ratio). The reaction temperature is preferably −80 to 70 ° C. As the solvent, an aprotic organic solvent such as diethyl ether, tetrahydrofuran, benzene, toluene and the like are preferably used. The Friedel-Crafts reaction of the alcohol of the above formula (12) under neutral to acidic conditions uses, for example, an acid catalyst such as acetic acid, hydrochloric acid, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, or acidic alumina. It is preferable to do so. Such an acid catalyst is preferably used in the range of 0.1 to 10 parts by weight per 100 parts by weight of the alcohol of the above formula (12). In this reaction, for example, an aprotic organic solvent such as tetrahydrofuran, benzene, or toluene is used.

On the other hand, the propargyl alcohol compound represented by the formula (6) can be easily synthesized, for example, by reacting the ketone compound corresponding to the formula (6) with a metal acetylene compound such as lithium acetylide.

The chromium compound of the present invention synthesized as described above is well soluble in general organic solvents such as toluene, chloroform and tetrahydrofuran. When the chromene compound represented by the above formula (1) is dissolved in such a solvent, the solution is generally almost colorless and transparent, and when irradiated with sunlight or ultraviolet rays, it develops color rapidly, and when light is blocked, it reversibly and quickly develops color. It exhibits a good photochromic effect that returns to the original colorlessness.

<Combination with other photochromic compounds (chromen composition)>
The chromen compound of the present invention can also be used in combination with other photochromic compounds in order to obtain various color tones required for a photochromic lens. As the photochromic compound to be combined, a known compound can be used without any limitation. For example, flugide, flugimid, spirooxazine, chromium and the like can be mentioned. Of these, the chromene compound is particularly preferable because it can maintain a uniform color tone during color development, suppress color shift during color development due to deterioration of photochromic properties, and can reduce initial coloring.

That is, by combining the chromene compound of the present invention with another chromene compound having good color development sensitivity and fading speed and small initial coloring like the chromene compound, the color tone at the time of color development is uniform. Moreover, a photochromic composition (chromen composition) having a high color-developing density and a small temperature dependence can be obtained even at a high temperature such as in summer.

In the present invention, when the chromene compound is used for plastic lens applications, other photochromic compounds, particularly other chromene compounds (chromene compounds other than the chromene compound of the present invention) are combined with the chromene compound of the present invention, and gray or It is preferable to use a chromene composition that develops a brown color. As a matter of course, it can also be used in combination with a chromene compound as exemplified in the comparative example. However, when used in combination with other chromene compounds, the other chromene compounds have a first absorption peak in the range of 430 to 530 nm and a second absorption peak in the range of 550 to 650 nm at the time of color development. It is preferable to use a chromium compound having a ratio of the intensity of the first absorption peak to the intensity of the second absorption peak (first absorption peak intensity / second absorption peak intensity) of 0.8 or more and 2.0 or less. By using a chromene compound having such characteristics, it is possible to easily adjust the color tone at the time of color development to gray or brown, and to obtain a highly durable plastic lens.

Specific examples of these suitable other chromene compounds include the following chromene compounds (2), (3) and (4).

The following formula (2)

Chromen compound, indicated by
The following formula (3)

Chlomen compound represented by, and the following formula (4)

It is preferable to use at least one compound selected from the group consisting of the chromium compounds shown in (1) in combination.

<Chromene compound represented by the above formula (2)>
<R ⁴⁰⁰ and R ⁵⁰⁰ >
R ⁴⁰⁰ and R ⁵⁰⁰ independently have a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an alkoxy having 1 to 6 carbon atoms. Group, amino group, substituted amino group, heterocyclic group, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, halogen atom, carbon Aralkyl group having 7 to 11 carbon atoms, aralkylthio group having 7 to 11 carbon atoms, aryl group having 6 to 12 carbon atoms, thiol group, alkylthio group having 1 to 6 carbon atoms, alkoxyalkylthio group having 2 to 9 carbon atoms, carbon number of carbon atoms It is a haloalkylthio group having 1 to 6, a cycloalkylthio group having 3 to 8 carbon atoms, or an arylthio group having 6 to 10 carbon atoms. These groups exemplified, the <R ^4, and R ^5> include the same groups as described in, the preferred groups are also the <R ^4, and R ^5> include the same groups as described in Be done.

a1 is an integer of 0 to ^3, refers to the number of substituents ^{R 400.} When a1 is 2 or more, R ⁴⁰⁰ may be the same or different groups from each other. b1 is an integer of 0 to ^2, refers to the number of substituents ^{R 500.} If b1 is 2, R ⁵⁰⁰ may be a different group identical to one another. Even when a plurality of R ⁴⁰⁰ and R ⁵⁰⁰ are present, the preferred group is the group shown in the above description.

Although the preferable groups of R ⁴⁰⁰ and R ⁵⁰⁰ have been exemplified above, a1 = 0, b1 = 0, that is, in consideration of the productivity, ease of handling, etc. of the chromene composition while maintaining excellent properties. , R ⁴⁰⁰ , and R ⁵⁰⁰ are both hydrogen atoms most preferably.

<R ⁶⁰⁰ and R ⁷⁰⁰ >
R ⁶⁰⁰ and R ⁷⁰⁰ independently have an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an amino group. A group, a substituted amino group, a heterocyclic group, a halogen atom, or an aryl group having 6 to 12 carbon atoms. These groups exemplified, the <R ^6, and R ^7> include the same groups as described in, the preferred groups are also the <R ^6, and R ^7> include the same groups as described in Be done.

c1 is an integer from 0 to 5 and refers to the number of substituents on R ⁶⁰⁰ . When c1 is 2 or more, R ⁶⁰⁰ may be the same or different groups from each other. d1 is an integer from 0 to 5 and refers to the number of substituents on R ⁷⁰⁰ . If d1 is 2, R ⁵ may be also different groups the same as each other. Even when a plurality of R ⁶⁰⁰ and R ⁷⁰⁰ are present, the preferred group is the group shown in the above description.

Further, in order to exhibit excellent photochromic characteristics, c1 and d1 are preferably 0 or 1. When c1 = 1 and d1 = 1, the position of the substituent is preferably the 3-position or 4-position of the phenyl group.

^<R 8>
R ⁸ is an alkoxy group having 1 to 6 carbon atoms, an amino group, a substituted amino group, a heterocyclic group, or an aryl group having 6 to 12 carbon atoms, and these groups are the above-mentioned <R ¹ and R ² >, wherein <R ^4, and R ^5> include the same groups as previously described, it is the same preferable groups.

<R ⁹ >
R ⁹ is an aryl group having 6 to 12 carbon atoms, and examples of the aryl group include groups similar to those already described in <R ⁴ and R ⁵ >. Among them, suitable aryl groups are exemplified by phenyl group, 1-naphthyl group, 2-naphthyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 2,4. Examples thereof include −dimethoxyphenyl group, 2,4,6-trimethoxyphenyl group and 4-morpholinophenyl group.

<R ¹⁰⁰ and R ¹¹⁰ >
R ¹⁰⁰ and R ¹¹⁰ are a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. , An aryl group having 6 to 12 carbon atoms. Examples of the group having a specific carbon number include the same groups as those already described in <R ¹ and R ² >, <R ⁴ and R ⁵ >, and the preferred groups are also the same.

<Ring group formed by R ¹⁰⁰ and R ¹¹⁰ >
Further, R ¹⁰⁰ and R ¹¹⁰ are an aliphatic ring having 3 to 20 ring member carbon atoms together with a carbon atom at the 13-position to which they are bonded, and an aromatic ring or an aromatic heterocycle condensed in the aliphatic ring. A fused polycycle, a heterocycle having 3 to 20 ring member atoms, or a fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to the heterocycle may be formed, and these ring groups are carbon. From the group consisting of an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, a substituted amino group, and a halogen atom. It may have at least one substituent of choice. Note that in the substituent groups of the cyclic group, for certain groups having the number of carbon and substituted amino group, the <R ^1, and R ^2> in include the same groups as previously described, the preferred group The same is true.

Specific examples include the compounds described in Pamphlet of International Patent Publication WO2005 / 028465.

<Chromene compound represented by the above formula (3)>
In the chromene compound represented by the formula (3), R ¹¹ and R ¹² are selected from the following combinations of (i), (ii), and (iii).

(I) R ¹¹ and R ¹² both have the following formulas.

(In the formula, the following formula

Ring Y represented by is an aryl group having 6 to 12 carbon atoms.
R ¹³ and R ¹⁴ independently have an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, a substituted amino group, and a heterocyclic group. It is a halogen atom or an aryl group having 6 to 12 carbon atoms.
e is an integer from 0 to 4, and when e is 2 or more, R ¹⁴ may be the same or different from each other. ) Is a sulfur-containing substituent.

Aryl group having 6 to 12 carbon atoms in the ring Y is a specific group, the <R ^4, and R ^5> in include the same groups as previously described, is the same preferable groups.

Further, in the groups described in R ¹³ and R ¹⁴ , the group having a specific carbon number, the substituted amino group, and the heterocyclic group are specific groups such as <R ¹ and R ² >, the above. <R ^4, and R ^5> in include the same groups as previously described, is the same preferable groups.

(Ii) R ¹¹ is the above-mentioned sulfur-containing substituent, and is
R ¹² is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, and a substituent. Amino group, heterocyclic group, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, halogen atom, aralkyl with 7 to 11 carbon atoms. A group, an alkyloxy group having 7 to 11 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

Further, in the group described in R ¹² , the group having a specific carbon number, the substituted amino group, and the heterocyclic group are specific groups such as <R ¹ , and R ² >, and <R ⁴ , ⁴ . And groups similar to those already described in R ⁵ >, and preferred groups as well.

(Iii) R ¹² is the above-mentioned sulfur-containing substituent, and is
R ¹¹ is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, and a substituent. Amino group, heterocyclic group, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, halogen atom, aralkyl with 7 to 11 carbon atoms. A group, an alkyloxy group having 7 to 11 carbon atoms, and an aryl group having 6 to 12 carbon atoms.

Further, in the group described for R ^11, the particular group having a number of carbon atoms, a substituted amino group, and heterocyclic group, as a specific group, the <R ^1, and R ^2>, the <R ^4, And the same groups as those already described in R ⁵ >, and the preferred groups are also the same.

<R ⁴⁰¹ and R ⁵⁰¹ >
R ⁴⁰¹ and R ⁵⁰¹ independently have a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an alkoxy having 1 to 6 carbon atoms. Group, amino group, substituted amino group, heterocyclic group, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, halogen atom, carbon Aralkyl group having 7 to 11 carbon atoms, aralkylthio group having 7 to 11 carbon atoms, aryl group having 6 to 12 carbon atoms, thiol group, alkylthio group having 1 to 6 carbon atoms, alkoxyalkylthio group having 2 to 9 carbon atoms, carbon number of carbon atoms It is a haloalkylthio group having 1 to 6, a cycloalkylthio group having 3 to 8 carbon atoms, or an arylthio group having 6 to 10 carbon atoms. These groups exemplified, the <R ^4, and R ^5> include the same groups as described in, the preferred groups are also the <R ^4, and R ^5> include the same groups as described in Be done.

a2 is an integer from 0 to 3 and indicates the number of substituents of R ⁴⁰¹ . When a2 is 2 or more, R ⁴⁰¹ may be the same or different groups from each other. b2 is an integer from 0 to 2 and refers to the number of substituents on R ⁵⁰¹ . When b2 is 2, R ⁵⁰¹ may be the same or different groups from each other. Even when a plurality of R ⁴⁰¹ and R ⁵⁰¹ are present, the preferred group is the group shown in the above description.

Although the preferred groups of R ⁴⁰¹ and R ⁵⁰¹ have been exemplified above, a2 = 0, b2 = 0, that is, considering the productivity, ease of handling, etc. of the chromene composition while maintaining excellent properties. , R ⁴⁰¹ , and R ⁵⁰¹ are both hydrogen atoms most preferably.

<R ⁶⁰¹ and R ⁷⁰¹ >
R ⁶⁰¹ and R ⁷⁰¹ independently have an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an amino group. A group, a substituted amino group, a heterocyclic group, a halogen atom, or an aryl group having 6 to 12 carbon atoms. These groups exemplified, the <R ^6, and R ^7> include the same groups as described in, the preferred groups are also the <R ^6, and R ^7> include the same groups as described in Be done.

c2 is an integer from 0 to ^5, refers to the number of substituents ^{R 601.} When c2 is 2 or more, ^R601 may be the same or different groups from each other. d2 is an integer from 0 to 5 and refers to the number of substituents on R ⁷⁰¹ . When d2 is 2, R ⁷⁰¹ may be the same or different groups from each other. Even when a plurality of R ⁶⁰¹ and R ⁷⁰¹ are present, the preferred group is the group shown in the above description.

Further, in order to exhibit excellent photochromic characteristics, c2 and d2 are preferably 0 or 1. When c2 = 1 and d2 = 1, the position of the substituent is preferably the 3-position or 4-position of the phenyl group.

<R ¹⁰¹ and R ¹¹¹ >
R ¹⁰¹ and R ¹¹¹ are an aliphatic ring having 3 to 20 ring member carbon atoms, and a condensation in which an aromatic ring or an aromatic heterocycle is fused to the aliphatic ring together with the carbon atom at the 13-position to which they are bonded. A polycycle, a heterocycle having 3 to 20 ring member atoms, or a fused polycycle in which an aromatic ring or an aromatic heterocycle is fused to the heterocycle may be formed, and these ring groups have 1 carbon number. Selected from the group consisting of an alkyl group of ~ 6; a haloalkyl group of 1-6 carbon atoms, a cycloalkyl group of 3-8 carbon atoms, an alkoxy group of 1-6 carbon atoms, an amino group, a substituted amino group, and a halogen atom. It may have at least one type of substituent.

These ring group, said ^{<R 100,} and ring ^{group R 110} forms> include the same groups as previously described, a preferred group, the group described for ^{<R 100,} and ^{R 110>} Similar groups can be mentioned.

Specific examples include the compounds described in Pamphlet of International Patent Publication WO 2013/042800.

<Chromene compound represented by the above formula (4)>
<R ⁴⁰² and R ⁵⁰² >
R ⁴⁰² and R ⁵⁰² independently have a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an alkoxy having 1 to 6 carbon atoms. Group, amino group, substituted amino group, heterocyclic group, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group with 2 to 7 carbon atoms, alkoxycarbonyl group with 2 to 7 carbon atoms, halogen atom, carbon Aralkyl group having 7 to 11 carbon atoms, aralkylthio group having 7 to 11 carbon atoms, aryl group having 6 to 12 carbon atoms, thiol group, alkylthio group having 1 to 6 carbon atoms, alkoxyalkylthio group having 2 to 9 carbon atoms, carbon number of carbon atoms It is a haloalkylthio group having 1 to 6, a cycloalkylthio group having 3 to 8 carbon atoms, or an arylthio group having 6 to 10 carbon atoms. These groups exemplified, the <R ^4, and R ^5> include the same groups as described in, the preferred groups are also the <R ^4, and R ^5> include the same groups as described in Be done.

a3 is an integer from 0 to 3 and indicates the number of substituents of R ⁴⁰² . When a3 is 2 or more, R ⁴⁰² may be the same or different groups from each other. b3 is an integer from 0 to 2 and refers to the number of substituents on R ⁵⁰² . When b3 is 2, R ⁵⁰³ may be the same or different groups from each other. Even when a plurality of R ⁴⁰² and R ⁵⁰² are present, the preferred group is the group shown in the above description.

Although the preferred groups of R ⁴⁰² and R ⁵⁰² have been exemplified above, a3 = 0, b3 = 0, that is, considering the productivity, ease of handling, etc. of the chromane composition while maintaining excellent properties. , R ⁴⁰¹ , and R ⁵⁰¹ are both hydrogen atoms most preferably.

<R ⁶⁰² and R ⁷⁰² >
R ⁶⁰² and R ⁷⁰² independently have an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an amino group. A group, a substituted amino group, a heterocyclic group, a halogen atom, or an aryl group having 6 to 12 carbon atoms. These groups exemplified, the <R ^6, and R ^7> include the same groups as described in, the preferred groups are also the <R ^6, and R ^7> include the same groups as described in Be done.

c3 is an integer from 0 to 5 and refers to the number of substituents on R ⁶⁰² . When c3 is 2 or more, R ⁶⁰² may be the same or different groups from each other. d3 is an integer from 0 to 5 and refers to the number of substituents on R ⁷⁰² . When d3 is 2, R ⁷⁰² may be the same or different groups from each other. Even when a plurality of R ⁶⁰² and R ⁷⁰² are present, the preferred group is the group shown in the above description.

Further, in order to exhibit excellent photochromic characteristics, c3 and d3 are preferably 0 or 1. When c3 = 1 and d3 = 1, the position of the substituent is preferably the 3-position or 4-position of the phenyl group.

<R ¹⁰² and R ¹¹² >
In R ¹⁰² and R ¹¹² , an aliphatic ring having 3 to 20 ring-membered carbon atoms, and an aromatic ring or an aromatic heterocycle fused to the aliphatic ring, together with a carbon atom at the 13-position to which they are bonded. A fused polycycle, a heterocycle having 3 to 20 ring member atoms, or a fused polycycle obtained by condensing an aromatic ring or an aromatic heterocycle on the heterocycle may be formed, and these ring groups have carbon atoms. Selected from the group consisting of an alkyl group of 1 to 6, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, a substituted amino group, and a halogen atom. It may have at least one type of substituent.

These ring group, said ^{<R 100,} and ring ^{group R 110} forms> include the same groups as previously described, a preferred group, the group described for ^{<R 100,} and ^{R 110>} Similar groups can be mentioned.

<M and M'>
M and M'are one or both sulfur atoms, and when one is a sulfur atom, the other is an oxygen atom.

<R ¹⁵ and R ¹⁶ >
R ¹⁵ and R ¹⁶ independently have a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and 1 to 6 carbon atoms, respectively. Alkoxy group, amino group, substituted amino group, heterocyclic group, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group having 2 to 7 carbon atoms, alkoxycarbonyl group having 2 to 7 carbon atoms, halogen atom. , An aralkyl group having 7 to 11 carbon atoms, an alkyloxy group having 7 to 11 carbon atoms, and an aryl group having 6 to 12 carbon atoms. In these groups, the group having a specific carbon number, the substituted amino group, and the heterocyclic group are already described as specific groups in the above <R ¹ , and R ² >, the above <R ⁴ , and R ⁵ >. The same group as the above-mentioned group is mentioned, and the preferable group is also the same.

Further, f is an integer of 1 to 3.

Specific examples include the compounds described in Pamphlet of International Patent Publication WO2012 / 121414.

<Chromen composition>
In the case of a photochromic composition containing the chromene compound of the present invention and another chromene compound, the blending ratio of each chromene compound is appropriately determined according to a desired color tone.

<Photochromic curable composition>
When the chromene compound of the present invention or the chromene composition containing the chromene compound of the present invention and another chromene compound is combined with a polymerizable monomer to obtain a photochromic curable composition, the following blending ratios are used. Is preferable. Specifically, the amount of the chromene compound or chromene composition of the present invention is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the polymerized monomer.

Specifically, more preferably, in the case of a thin film such as a coating film, for example, a thin film having a thickness of about 100 μm, the chromium compound of the present invention is 0.001 with respect to 100 parts by mass of the coating film or the polymerizable monomer that gives the coating film. It is preferable to adjust the color tone with ~ 5.0 parts by mass and 0.001 to 5.0 parts by mass of other monomer compounds. Alternatively, in the case of a thick cured product, for example, a cured product having a thickness of 1 mm or more, the chromium compound of the present invention 0.001 to 0.5 is based on 100 parts by mass of the polymerizable monomer that gives the thick cured product or the thick cured product. It is preferable to adjust the color tone by the mass part and 0.001 to 0.5 parts by mass of the other monomer compound.

<Stabilizer to combine>
The chromene compound of the present invention has high durability as it is, but the durability can be further increased by using the following ultraviolet absorbers, light stabilizers, antioxidants and the like. As the ultraviolet absorber, known ultraviolet absorbers such as benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds and benzoate compounds can be used, and in particular, cyanoacrylate compounds and benzophenone compounds can be used. Compounds are preferred. The ultraviolet stabilizer is preferably used in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the polymerized monomer containing the chromene compound of the present invention. Further, a known hindered amine can be used as the light stabilizer, and a known hindered phenol can be used as the antioxidant. The above-mentioned light stabilizer and antioxidant are preferably used in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerized monomer containing the chromium compound of the present invention.

<Use of chromene compounds; polymer molded products; optical articles>
In addition, the chromen compound of the present invention exhibits similar photochromic properties even in the host material. The host material to be the target may be one in which the chromene compound of the present invention is uniformly dispersed. Among them, optically preferable ones are, for example, methyl polyacrylate, ethyl polyacrylate, methyl polymethacrylate, ethyl polymethacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, and poly (2-hydroxyethyl methacrylate). , Polydimethylsiloxane, polycarbonate and other thermoplastic resins.
Further, a thermosetting resin obtained by polymerizing a radically polymerizable polyfunctional monomer can also be used as the polymer matrix. Examples of such radically polymerizable polyfunctional monomers include ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, and bisphenol A dimethacrylate, 2,2. Polyvalent acrylic or polyvalent acrylates such as −bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane; diallyl phthalate, diallyl Polyvalent allyl compounds such as terephthalate, diallyl isophthalate, diallylate tartrate, diallyl epoxy succinate, diallyl fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyldiglycol carbonate, trimethylpropantriallyl carbonate; 1,2 -Polyvalent thioacrylic acid ester or polyvalent thiomethacrylic acid ester such as bis (methacryloylthio) ethane, bis (2-acryloylthioethyl) ether, 1,4-bis (methacryloylthiomethyl) benzene; glycidyl acrylate, glycidyl methacrylate , Β-Methylglycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyloxy methacrylate, 3- (glycidyl-2-oxyethoxy) -2-hydroxypropyl methacrylate, 3- (glycidyloxy-1-isopropyloxy) -2-Hydroxypropyl acrylate, 3-glycidyloxy-2-hydroxypropyloxy) Acrylate ester or methacrylic acid ester such as -2-hydroxypropyl acrylate; divinylbenzene and the like can be mentioned.
Further, a copolymer obtained by copolymerizing the above-mentioned radically polymerizable polyfunctional monomer with a radically polymerizable monofunctional monomer can also be used as the polymer matrix. Examples of such radically polymerizable monofunctional monomers include unsaturated carboxylic acids such as acrylate, methacrylic acid, and maleic anhydride; methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, and 2-hydroxy. Acrylic acid ester or methacrylic acid ester such as ethyl methacrylate; Fumaric acid ester such as diethyl fumarate, diphenyl fumarate; thioacrylic acid ester and thiomethacrylic acid ester such as methyl thioacrylate, benzyl thioacrylate, benzyl thiomethacrylate; styrene, chloro Examples thereof include vinyl compounds such as styrene, methylstyrene, vinylnaphthalene, α-methylstyrene dimer and bromostyrene.

As a method for dispersing the chromene compound of the present invention in the host material, a method known per se can be used. For example, a method of kneading the thermoplastic resin and the chromene compound in a molten state to disperse the chromene compound in the resin, or a method of dissolving the chromene compound in the polymerizable monomer and then adding a polymerization catalyst to heat or light. A method of dispersing the monomer compound in the resin by polymerizing in the above method, or a method of dispersing the monomer compound in the resin by dyeing the surface of the thermoplastic resin and the thermosetting resin with the monomer compound can be mentioned. ..

The chromene compound of the present invention can be widely used as a photochromic material, and for example, various storage materials, copying materials, printing photoconductors, cathode line tube storage materials, laser photosensitive materials, and holographic photosensitive materials that replace silver salt photosensitive materials. It can be used as various storage materials such as. In addition, the photochromic material using the chromen compound of the present invention can also be used as a material for a photochromic lens material, an optical filter material, a display material, a photometer, a decoration, and the like. For example, when used for a photochromic lens, there is no particular limitation as long as the method can obtain uniform dimming performance. For example, a method of sandwiching a polymer film obtained by uniformly dispersing the photochromic material of the present invention in a lens. Alternatively, a method in which the photochromic compound of the present invention is dispersed in the above-mentioned polymerizable monomer and polymerized by a predetermined method, or this compound is dissolved in, for example, silicone oil and 10 to 60 at 150 to 200 ° C. Examples thereof include a method of impregnating the lens surface over a minute and then coating the surface with a curable substance to make a photochromic lens. Further, a method of applying the polymer film to the lens surface and coating the surface with a curable substance to form a photochromic lens is also used.

Further, a coating agent composed of a photochromic curable composition containing the chromene compound of the present invention may be applied to the surface of the lens base material to cure the coating film. At this time, the lens base material may be subjected to surface treatment such as surface treatment with an alkaline solution or plasma treatment in advance, and further, the base material and the coating film may be subjected to surface treatment together with or without these surface treatments. Primers can also be applied to improve the adhesion of the. By doing so, it is possible to produce an optical article coated with a polymer film in which a chromene compound or a chromene composition is dispersed. Further, an optical article having the shape can be produced by arranging a lens base material in a cavity in advance, pouring the photochromic curable composition into the cavity, and curing the curable composition.

The chromene compound of the present invention has a small temperature dependence. Specifically, the ratio (A ₃₅ / A ₂₃ ) of the color development density (A ₃₅ ) at 35 ° C. to the color development density (A ₂₃ ) at 23 ° C. can be 0.65 or more, and more preferably 0. It can be 70 or more, and more preferably 0.75 or more. The higher this ratio (A ₃₅ / A ₂₃ ), the smaller the temperature dependence. When the chromium compound is a double peak compound having a first absorption peak in the range of 430 to 530 nm and a second absorption peak in the range of 550 to 650 nm, both the first and second absorption peaks are used. The ratio (A ₃₅ / A ₂₃ ) is preferably 0.70 or more, and more preferably 0.75 or more. The upper limit of the ratio (A ₃₅ / A ₂₃ ) is most preferably 1.0, but in consideration of industrially producible chromene compounds (including double peak compounds), the ratio (including double peak compounds) The upper limit of A ₃₅ / A ₂₃ ) is 0.90.

Further, the chromene composition using the chromene compound of the present invention (including a combination of double peak compounds) can also maintain the ratio (A ₃₅ / A ₂₃ ) high. Therefore, the color tone can be easily adjusted. For example, when used for sunglasses, it is easy to match the color tone with gray or brown, and a chromene composition having a small temperature dependence can be obtained. Also in the chromen composition, the ratio (A ₃₅ / A ₂₃ ) can be 0.70 or more, and further can be 0.75 or more. The upper limit of the ratio (A ₃₅ / A ₂₃ ) of the chromene composition is most preferably 1.0, but considering the chromene composition (including the double peak compound) that can be industrially produced, the chromene composition is said to be The upper limit of the ratio (A ₃₅ / A ₂₃ ) is 0.90.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Example 1
(Preparation of naphthol compound; synthesis of naphthol compound represented by formula (13))
The following formula (13)

The naphthol compound shown in (1) was synthesized by the following procedure.

21.0 g (86.7 mmol) of 4,4'-dimethylbenzophenone and 17.3 g (99.4 mmol) of diethyl succinate were dissolved in 200 ml of tetrahydrofuran and the temperature was raised to 55 ° C. A solution of 9.7 g (86.7 mmol) of potassium-t-butoxide in tetrahydrofuran (200 ml) was added dropwise to this solution, and the mixture was stirred for 1 hour. After the reaction, the mixture was washed with concentrated hydrochloric acid and then with water to remove the solvent, and the following formula (14) was used.

The compound represented by (1) was obtained as 29.3 g (86.3 mmol, yield: 100%) of an orange oil.

The compound represented by the formula (14), 7.1 g (86.6 mmol) of sodium acetate and 35.8 g (350.7 mmol) of acetic anhydride were dissolved in 100 ml of toluene and refluxed for 4 hours. After the reaction, the mixture was washed with water, the solvent was removed, and recrystallization was performed with methanol for purification. The following formula (15)

The compound represented by (2) was obtained as an orange solid (22.6 g (62.4 mmol, yield: 72%)).

The compound represented by the formula (15) was dispersed in 100 ml of methanol. 125 ml of an aqueous solution of 12.5 g (312 mmol) of sodium hydroxide was added to this solution, and the mixture was refluxed for 3 hours. After the reaction, the mixture was washed with concentrated hydrochloric acid and then with water to remove the solvent, and purified by performing reslurry with toluene according to the following formula (16).

The carboxylic acid derivative represented by (1) was obtained as 16.4 g (56.1 mmol, yield: 90%) of a yellow solid.

The carboxylic acid derivative represented by the formula (16) and 15.7 g (123.6 mmol) of benzyl chloride were dissolved in 120 ml of N, N-dimethylformamide. 19.4 g (140.6 mmol) of potassium carbonate was added to this solution, the temperature was raised to 60 ° C., and the mixture was stirred for 3 hours. After the reaction, wash with water to remove the solvent, and the following formula (17)

The compound represented by (1) was obtained as 26.5 g (56.1 mmol, yield: 100%) of yellow oil.

The compound represented by the formula (17) was dispersed in 200 ml of isopropyl alcohol. To this solution was added 220 ml of an aqueous solution of 22.4 g (561.0 mmol) of sodium hydroxide, and the mixture was refluxed for 4 hours. After the reaction, the mixture was washed with concentrated hydrochloric acid and then with water to remove the solvent, and purified by performing reslurry with toluene according to the following formula (18).

The carboxylic acid derivative represented by (1) was obtained as a yellow solid of 18.9 g (49.4 mmol, yield: 88%).

The carboxylic acid derivative represented by the formula (18) was dispersed in 400 ml of toluene. To this solution was added 24.9 g (247.0 mmol) of triethylamine and 17.7 g (64.6 mmol) of diphenylphosphoryl azide, and the mixture was stirred at room temperature for 2 hours. To this solution was added 20.0 g (435.3 mmol) of ethanol and reacted at 70 ° C. for 2 hours. To this solution, 500 ml of ethanol was added, then 30.0 g (535.7 mmol) of potassium hydroxide was added, and the mixture was refluxed for 4 hours. After the reaction, ethanol was distilled off at normal pressure, tetrahydrofuran was added, the mixture was washed with water, and the solvent was removed to obtain the following formula (19).

The compound represented by (1) was obtained as 17.5 g (49.4 mmol, yield: 100%) of a yellow solid.

The compound represented by the formula (19) was dispersed in 600 ml of acetonitrile, 150.0 g (247.0 mmol) of a 6% aqueous hydrochloric acid solution was added, and the mixture was cooled to 0 ° C to 5 ° C. To this solution was added 15.3 g (74.1 mmol) of a 33% aqueous sodium nitrite solution, and the mixture was stirred for 30 minutes. To this solution was added 41.2 g (247.0 mmol) of a 50% aqueous potassium iodide solution, and the mixture was stirred at room temperature for 4 hours. After the reaction, toluene is added, the mixture is washed with water, the solvent is removed, and purification is performed by column chromatography. The following formula (20)

The compound represented by (1) was obtained as 16.1 g (34.7 mmol, yield: 70%) of a yellow solid.

The compound represented by the formula (20) was dispersed in 400 ml of toluene and cooled to −30 ° C. To this solution, 26.0 ml (41.6 mmol) of n-butyllithium (1.6 M hexane solution) was added dropwise, and the mixture was stirred for 30 minutes. To this solution, 22.8 g of a toluene solution of 6.7 g (43.4 mmol) of cyclooctanone was added dropwise, and the mixture was stirred at 0 ° C. for 1 hour. After the reaction, toluene is added, the mixture is washed with water, the solvent is removed, and the slurry is purified with methanol according to the following formula (21).

The compound represented by (1) was obtained as a yellow solid in an amount of 7.2 g (15.5 mmol, yield: 45%).

The compound represented by the formula (21) and 190.4 mg (0.78 mmol) of (±) -10-camphorsulfonic acid were dissolved in 150 ml of toluene and refluxed for 30 minutes. After allowing to cool to room temperature, this solution was added to 60 ml of a toluene solution of 2.5 g (15.5 mmol) of p-toluenesulfonic acid heated to 90 ° C., and the mixture was refluxed for 6 hours. After the reaction, the naphthol compound represented by the above formula (13) was obtained by 3.3 g (9.5 mmol, yield: 61) of the yellow solid by washing with water, removing the solvent, and purifying by the column chromatography method. %) Obtained as.

(Synthesis of chromene compound)
1.0 g (2.8 mmol) of the naphthol compound represented by the above formula (13) obtained by the above method and the following formula (22)

The propargyl alcohol compound (1.0 g (3.6 mmol)) shown in (1) was dissolved in 50 ml of toluene, 0.02 g of p-toluenesulfonic acid was further added, and the mixture was stirred under heating under reflux for 1 hour. After the reaction, the solvent was removed. Then, the product was purified by chromatography on silica gel to obtain 1.3 g of a white powdery product. The yield was 74%.

Elemental analysis of the product, C85.05%, a _{H6.93%, C 43 H 42 О} 3 C85.11% a calculated value of (the chromene compound represented by the following formula (23)), H6 Very well matched to .98%.

When the proton nuclear magnetic resonance spectrum was measured, a peak of 20H based on the methylene proton of the cyclooctane ring and the methyl proton of the methyl group was measured around 1.0 to 3.0 ppm, and a methoxy group was measured around δ2.3 to 4.0 ppm. The peak of 6H based on the methyl proton of δ, and the peak of 16H based on the proton of aromatic and alkene were shown in the vicinity of δ5.6 to 9.0 ppm.

Further, when the ¹³ C-nuclear magnetic resonance spectrum was measured, a carbon-based peak of the aromatic ring was shown near δ110-160 ppm, an alkene carbon-based peak was shown near δ80-140 ppm, and an alkyl carbon-based peak was shown at δ20-60 ppm. It was.

From the above results, it was confirmed that the isolated product was a chromene compound represented by the following formula (23).

Examples 2-10
In the same manner as in Example 1, the naphthol compounds and propargyl alcohol compounds shown in Table 1 (Examples 2 to 5), Table 2 (Examples 6 to 9), and Table 3 (Example 10) were prepared. A chromene compound was synthesized by reacting both. In each example, the naphthol compound was synthesized according to the method described in Example 1, except that the raw materials, the reactants, etc. were replaced with those used in Example 1 so as to obtain the desired product.

As a result of structural analysis of the obtained chromene compound using the same structural confirmation means as in Example 1, it was confirmed that the chromene compound was a compound represented by the structural formulas shown in Tables 1 to 3. In addition, Table 4 shows the elemental analysis values of these compounds, the calculated values obtained from the structural formulas of each compound, and the characteristic spectra of the ¹ H-NMR spectrum.

As a matter of course, in the present specification, Me in the chemical formula refers to a methyl group.

Examples 11-20
(Evaluation of physical properties of photochromic plastic lenses produced by the coating method)
Chlomen compound No. obtained in Example 1 above. 1 was mixed with a photopolymerization initiator and a polymerizable monomer, then applied to the surface of the lens substrate, and further irradiated with ultraviolet rays to polymerize the 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 hexagon as radically polymerizable monomers An acrylate (manufactured by Daicel UCB Co., Ltd., EB-1830) / glycidyl methacrylate was blended in a blending ratio of 50 parts by mass / 10 parts by mass / 10 parts by mass / 10 parts by mass / 10 parts by mass, respectively. With respect to 90 parts by mass of the mixture of the radically polymerizable monomer, the chromene compound No. 1 obtained in Example 1 was obtained. After adding 11 parts by mass and mixing thoroughly, CGI1800 {1-hydroxycyclohexylphenyl ketone and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, which are photopolymerization initiators, 0.3 parts by mass of the mixture (weight ratio 3: 1)}, 5 parts by mass of the stabilizer bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and ethylene bis (oxyethylene). ) Bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] in 3 parts by mass, γ-methacryloyloxypropyltrimethoxysilane as a silane coupling agent in 7 parts by mass, and N-methyl. 3 parts by mass of diethanolamine was added and mixed thoroughly to prepare a photochromic curable composition.

Subsequently, about 2 g of the photochromic curable composition obtained by the above method is spun on the surface of a lens base material (CR39: allyl resin plastic lens; refractive index = 1.50) using a spin coater 1H-DX2 manufactured by MIKASA. I coated it. This surface-coated lens was irradiated for 3 minutes using a metal halide lamp having an output of 120 mW / cm ^{2 in} a nitrogen gas atmosphere and cured (an optical article (photochromic) coated with a polymer film in which a chromium compound was dispersed. A plastic lens) was produced (thickness of polymer film: 40 μm).

The following photochromic characteristics were evaluated for the obtained photochromic plastic lens. The results of the following evaluation using the chromene compound of Example 1 are summarized in Table 5.

[1] Maximum absorption wavelength (λmax): The maximum absorption wavelength after color development obtained by a spectrophotometer (instantaneous multi-channel photodetector MCPD3000) manufactured by Otsuka Electronics Co., Ltd., which is an index of color tone at the time of color development. And said.

[2] 23 ° C. color development density (A ₂₃ ): The difference between the absorbance {ε (120)} after light irradiation at 23 ° C. for 120 seconds at the maximum absorption wavelength and the absorbance ε (0) when no light is irradiated. Yes, it was used as an index of color density. It can be said that the higher this value is, the better the photochromic property is.

[3] 35 ° C. color development concentration (A ₃₅ ): The difference between the absorbance {ε (120)} after light irradiation at 35 ° C. for 120 seconds at the maximum absorption wavelength and the absorbance ε (0) when no light is irradiated. Yes, it was used as an index of color density. It can be said that the higher this value is, the better the photochromic property is.

[4] Temperature dependence (A ₃₅ / A ₂₃ ): The ratio of the 35 ° C. color development density (A ₃₅ ) to the 23 ° C. color development density (A ₂₃ ). It can be said that the higher this value is, the smaller the temperature dependence is and the better.

[5] 23 ° C. fading half-life [τ1 / 2 (sec.)]: When the irradiation of light is stopped after irradiation with light for 120 seconds at 23 ° C., the absorbance of the sample at the maximum absorption wavelength is {ε (120). ) -Ε (0)}, which is the time required to decrease to 1/2, and was used as an index of the fading rate. The shorter this time, the faster the fading speed.

[7] Residual rate (A ₅₀ / A ₀ × 100): The obtained photochromic plastic lens was accelerated and deteriorated for 50 hours by a xenon weather meter X25 manufactured by Suga Test Instruments Co., Ltd. After that, the color development density is evaluated before and after the test, the color development density before the test (A ₀ ) and the color development density after the test (A ₅₀ ) are measured, and the ratio (A ₅₀ / A ₀ ) is used as the residual rate. , Used as an index of color development durability. The higher the residual rate, the higher the durability of color development.

Further, a photochromic plastic lens was obtained in the same manner as described above except that the compounds obtained in Examples 2 to 10 (Nos. 2 to 10 respectively) were used as the chromene compound, and their characteristics were evaluated. The results are summarized in Table 5.

Comparative Examples 1-5
For comparison, a photochromic plastic lens was obtained in the same manner as in Examples using the compounds represented by the following formulas (A) to (E), and their characteristics were evaluated. The results are shown in Table 6.

The photochromic plastic lenses in Examples 11 to 20 using the chromene compound of the present invention are Comparative Example 1 (chromen compound represented by the formula (A)) and Comparative Example 2 (chromen compound represented by the formula (B)). , Photochromic of Comparative Example 3 (chromen compound represented by the formula (C)), Comparative Example 4 (chromen compound represented by the formula (D)), Comparative Example 5 (chromen compound represented by the formula (E)). It can be seen that the lens has higher durability, higher color density even at high temperatures, and less temperature dependence than the plastic lens.

Examples 21 and 22
The composition of the chromene compounds of Examples 5 and 9 of the present invention and the chromene compound represented by the following formula (24) as shown in Table 7 (Example 21: 1.0 mass of chromene compound produced in Example 5). 30 parts by mass of the chromene compound represented by the formula (24). Example 22: 1.0 part by mass of the chromene compound produced in Example 9, 3.0 parts by mass of the chromene compound represented by the formula (24). ), A photochromic plastic lens was produced by the same method as in Example 11, and its characteristics were evaluated. The results are summarized in Table 8.

The chromene compound represented by the following formula (24) has a first absorption peak (intensity 0.68) at 468 nm and a second absorption peak (intensity 0.68) at 578 nm, and has a second absorption peak with respect to the second absorption peak intensity. It is a compound in which the intensity ratio of one absorption peak (first absorption peak intensity / second absorption peak intensity) is 1.00.

As shown in Table 8, the photochromic plastic lens obtained by curing the chromen composition of the present invention has high durability, high color density even at high temperature, and low temperature dependence.

Claims (1)

The following formula (1)
(During the ceremony,
R ¹ and R ² are independently methyl group, cyclohexyl group, methoxy group, or morpholino group , respectively .
R ⁶ is a methoxy group, a morpholino group, or a piperidino group .
R ⁷ is a hydrogen atom, a methyl group, or a methoxy group.
The following formula
The ring group spiro-bonded to the carbon atom at the 13-position represented by is a cyclooctane ring or a 4,4-dimethylcyclohexane ring . )
Chromen compound indicated by.