JP2001031670A - Chromene compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a specific new chromene compound having high color developing rate and, in a solution or a polymer solid matrix, moderately low discoloring rate. SOLUTION: This compound is represented by formula I (R1 is a substituted amino, a heterocycle or the like; R2 to R4 are each H, a substituted amino or the like; R7 is H, trifluoromethyl or the like; R6 and R8 are each H, cyano or the like; R5 and R9 are each H, cyano or the like; R10 is an alkyl, an alkoxy or the like; a is 0-3) e.g. the compound of formula II. The compound of formula I is obtained by reacting a naphthol derivative of formula III with a propargyl alcohol derivative of formula IV in the presence of an acid catalyst. The mole ratio of the compound of formula III to the compound of formula IV in the reaction is preferably 1:10 to 10:1. The acid catalyst may be sulfuric acid, benzenesulfonic acid or the like and preferably 0.1-10 pts.wt. per total amount of the compound of formula III and IV. The reaction temperature is preferably 0-200 deg.C and the solvent is preferably N-methylpyrrolidone or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of changing the color of a light to a yellow to red color tone by irradiation of light including ultraviolet rays such as sunlight or light of a mercury lamp, and the change is reversible.
The present invention relates to a chromene compound having a high coloring speed and a moderate fading speed.

[0002]

2. Description of the Related Art Photochromism is a phenomenon that has been attracting attention for several years. When a compound is irradiated with light including ultraviolet rays such as sunlight or light from a mercury lamp, the color changes rapidly, and the light irradiation is stopped. It is a reversible action that returns to the original color when stopped and put in a dark place. A compound having such properties is called a photochromic compound, and various compounds have been conventionally synthesized, and are used in various fields such as optical materials such as a photochromic lens for spectacles.

[0003] In applications such as photochromic spectacle lenses, intermediate colors such as gray and brown are preferred. Such intermediate colors are photochromic compounds which exhibit yellow to red when colored (hereinafter, also referred to as yellow to red compounds). And a photochromic compound that exhibits a blue color at the time of color development (hereinafter, also simply referred to as a blue compound). At this time, the color tone in the color development process, the color tone in the saturated color development, and the color tone in the fading process are uniform. Is more preferred.

A chromene compound is known as a yellow-red compound, and a spirooxazine compound or a fulgide compound is known as a blue compound. Generally, blue is more human than yellow to red. Since the sensitivity to the eyes is high, to obtain a uniform color tone as described above, yellow ~
It is preferable that the red compound has a higher color developing speed than the blue compound and conversely, the fading speed is appropriately lower. The coloring speed of the blue compound is relatively fast, so that the coloring speed of the yellow to red compounds is not so significant as long as it is at the same level. When a yellow to red compound having a high speed is used, there is a problem that the color tone at the time of fading becomes uneven.

For example, PCT Patent Application WO 98/452
No. 81 describes the following formula (A) that develops an orange color

[0006]

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A chromene compound represented by the formula (1) is disclosed. However, since the chromene compound has a high color-forming speed and a fading speed, when a composition having an intermediate color is formed by combining with a known blue compound, the color tone in the fading process is reduced. There is a problem that it turns blue.

Japanese Patent Application Laid-Open No. 10-298176 discloses the following formula (B):

[0009]

Embedded image Is disclosed, and the discoloration rate of the compound is lower than that of the compound (A),
Not enough yet.

US Pat. No. 4,989,089 discloses the following formula (C):

[0011]

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A chromene compound represented by the formula: This compound, contrary to the above two chromene compounds, is too slow in both the color development rate and the color fading rate, so that no uniformity in the color development-discoloration process can be obtained.

As described above, a known chromene compound which develops a color from yellow to red, when an attempt is made to obtain an intermediate color such as gray or brown by combining with a blue compound,
The color tone of the fading process was not uniform, and was not satisfactory.

[0014]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a chromene compound which, when used in combination with a blue compound, has a uniform color tone when discolored, in other words, a chromene compound. It is an object of the present invention to provide a chromene compound having substantially the same coloring speed and a moderately fading speed.

[0015]

DISCLOSURE OF THE INVENTION The present invention has been proposed to achieve the above object, and a novel chromene compound discovered by the present inventors has a high color-forming speed and a high fading speed. It was completed based on the finding that it was moderately slow.

That is, the present invention provides the following general formula (1)

[0017]

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In the formula, R ¹ is a substituted amino group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and bonding the nitrogen atom to a naphthopyran ring, or an aromatic group in the heterocyclic group. A condensed heterocyclic group in which a hydrocarbon ring or an aromatic heterocyclic ring is condensed, wherein R ² , R ³ and R ⁴ each have a hydrogen atom, a substituted amino group, a nitrogen atom as a hetero atom and the nitrogen atom and a benzene ring Is a substituted or unsubstituted heterocyclic group, or a fused heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the heterocyclic group,
R ² , R ³ and R ⁴ are not hydrogen atoms at the same time,
R ⁷ represents a hydrogen atom, a trifluoromethyl group, a cyano group,
A sulfonyl group, an alkylsulfonyl group, an arylsulfonyl group or a nitro group, and R ⁶ and R ⁸ are each a hydrogen atom, an aliphatic hydrocarbon group having 3 or more carbon atoms, a fluorine atom, when R ⁷ is not a hydrogen atom, Trifluoromethyl group, cyano group, sulfonyl group, alkylsulfonyl group,
An arylsulfonyl group or a nitro group, and when R ⁷ is a hydrogen atom, a hydrogen atom and an aliphatic hydrocarbon group having 3 or more carbon atoms, respectively, and R ⁵ and R ⁹ are a hydrogen atom and a cyano group, respectively. An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom or a chlorine atom, and R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are not simultaneously hydrogen atoms. , R ¹⁰ represents an alkyl group, an alkoxy group, an aralkoxy group, an aralkyl group, a substituted amino group, a cyano group, a substituted or unsubstituted aryl group, a halogen atom,
A substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and bonding the nitrogen atom to a naphthopyran ring, or a fused heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to the heterocyclic group And a is an integer of 0 to 3. It is a chromene compound represented by｝.

Another aspect of the present invention is a photochromic material comprising a chromene compound represented by the above general formula (1),
And a photochromic optical material containing the chromene compound.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula (1), R ¹
Is a substituted amino group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and a nitrogen atom bonded to a naphthopyran ring, or an aromatic hydrocarbon ring or an aromatic heterocyclic ring fused to the heterocyclic group A fused heterocyclic group.

In the above-mentioned substituted or unsubstituted heterocyclic group, "having a nitrogen atom as a hetero atom and bonding the nitrogen atom to a naphthopyran ring" means that "-" of -R ¹ is not bonded. When it is called a hand, it means that an unbonded hand is present in a nitrogen atom included as a hetero atom, and the nitrogen atom is bonded to a naphthopyran ring.

The above-mentioned substituted amino group is not particularly limited, but is preferably an alkylamino group, a dialkylamino group, an arylamino group, or a diarylamino group substituted with an alkyl group or an aryl group. Specific examples of suitable substituted amino groups include a methylamino group, an ethylamino group, a phenylamino group, a dimethylamino group, a diethylamino group, and a diphenylamino group.

A substituted or unsubstituted heterocyclic group having the above-mentioned nitrogen atom as a heteroatom and bonding the nitrogen atom to a naphthopyran ring, or an aromatic hydrocarbon ring or an aromatic heterocyclic ring fused to the heterocyclic group As the fused heterocyclic group,
Although not particularly limited, the number of carbon atoms constituting the heterocyclic group is generally 2 to 10, preferably 2 to 6. Further, a hetero atom may be present in the ring in addition to the nitrogen atom bonded to the naphthopyran ring, and the hetero atom is not particularly limited, but an oxygen atom, a sulfur atom, a nitrogen atom and the like are preferable. is there.

A substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and linking the nitrogen atom to a naphthopyran ring, or a condensation wherein an aromatic hydrocarbon ring or an aromatic heterocycle is fused to the heterocyclic group Specific examples of suitable heterocyclic groups include morpholino, piperidino, pyrrolidinyl, piperazino, N-methylpiperazino, and indolinyl groups.

In the above general formula (1), R ² , R ³ and R ⁴ each represent a hydrogen atom, a substituted amino group or a nitrogen atom as a heteroatom, and the nitrogen atom and the benzene ring are bonded to each other. It is an unsubstituted heterocyclic group or a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is condensed to the heterocyclic group. However, R ² , R ³ , and R ⁴ are not simultaneously hydrogen atoms. When these groups are hydrogen atoms at the same time, the effect of the present invention cannot be obtained because the fading speed is significantly reduced.

Here, the substituted amino group has the same meaning as the substituted amino group in R ¹ , and the same is exemplified as a suitable substituted amino group. Also, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a hetero atom and bonding the nitrogen atom to a benzene ring, or a condensation in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the heterocyclic group Heterocyclic group "
Is the same as the substituted or unsubstituted heterocyclic group and the condensed heterocyclic group bonded to the naphthopyran ring at R ¹ except that the ring to which the nitrogen atom is bonded is a benzene ring. In the general formula (1), R ⁷ is a hydrogen atom,
A trifluoromethyl group, a cyano group, a sulfonyl group, an alkylsulfonyl group, an arylsulfonyl group, or a nitro group.

Here, the alkylsulfonyl group includes
Although not particularly limited, an alkylsulfonyl group having 1 to 4 carbon atoms such as a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, and a t-butylsulfonyl group is preferable.

The arylsulfonyl group is not particularly limited, but is preferably an arylsulfonyl group having 6 to 10 carbon atoms such as a phenylsulfonyl group and a naphthylsulfonyl group.

In the general formula (1), R ⁶ and R
⁸ has different structures depending on R ⁷ . That is, R
⁷ is a trifluoromethyl group other than a hydrogen atom, a cyano group,
When it is a sulfonyl group, an alkylsulfonyl group, an arylsulfonyl group or a nitro group, a hydrogen atom, an aliphatic hydrocarbon group having 3 or more carbon atoms, a fluorine atom, a trifluoromethyl group, a cyano group, a sulfonyl group, an alkylsulfonyl group, It is an arylsulfonyl group or a nitro group. When R ⁷ is a hydrogen atom, R ⁶ and R 7
⁸ is a hydrogen atom or an aliphatic hydrocarbon group having 3 or more carbon atoms.

Here, the aliphatic hydrocarbon group having 3 or more carbon atoms is not particularly limited, but may be, for example, an n-propyl group, an isopropyl group, an n-butyl group or a t-butyl group.
As described above, particularly, an alkyl group having 3 to 6 carbon atoms: a cycloalkyl group having 3 or more carbon atoms, particularly 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclohexyl group, an adamantylidene group, and a norbornylidene group is preferred. Here, the aliphatic hydrocarbon group is
If the number of carbon atoms is smaller than 3, an appropriately slow fading speed, which is an effect of the present invention, cannot be obtained.

Further, an alkylsulfonyl group and arylsulfonyl group include the same groups as those exemplified in R ^7.

In the general formula (1), R ⁵ and R
⁹ is a hydrogen atom, a cyano group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom or a chlorine atom, respectively.

Here, the alkyl group has 1 to 1 carbon atoms.
The number is not particularly limited as long as it is 5, but a linear alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl is preferable.

The alkoxy group has 1 to 1 carbon atoms.
If it is 5, there is no particular limitation, but a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group are preferred.

However, R ⁵ , R ⁶ , R ⁷ , R ^{8 described above}
And R ⁹ are not hydrogen atoms at the same time, and at least one of them must be a substituent other than hydrogen. When all of these groups are hydrogen atoms, the effects of the present invention cannot be obtained.

In view of the effects of the present invention, a suitable mode of the substitution position of R ⁵ , R ⁶ , R ⁷ , R ^8, and R ⁹ is as follows because of the appropriate slow fading speed and the ease of synthesis. (However, in the following embodiments, when each of these substituents is a hydrogen atom, each substituent is omitted and represented.
When R ⁵ , R ^{6 and the} like are specified, it means that these specified groups are other than a hydrogen atom).

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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In the general formula (1), R ¹⁰ represents an alkyl group, an alkoxy group, an aralkoxy group, an aralkyl group, a substituted amino group, a cyano group, a substituted or unsubstituted aryl group, a halogen atom, and a nitrogen atom as a hetero atom. A substituted or unsubstituted heterocyclic group in which the nitrogen atom is bonded to a naphthopyran ring, or a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the heterocyclic group.

Hereinafter, each of these groups will be described.

The alkyl group is not particularly limited, but is generally preferably an alkyl group having 1 to 4 carbon atoms.
Examples of suitable alkyl groups include a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, se
Examples thereof include a c-butyl group and a t-butyl group.

The alkoxy group is not particularly limited, but is generally preferably an alkoxy group having 1 to 5 carbon atoms. Specific examples of suitable alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and t-butoxy groups.

The aralkoxy group is not particularly limited, but is preferably an aralkoxy group having 6 to 10 carbon atoms. Specific examples of suitable aralkoxy groups include a phenoxy group and a naphthoxy group.

The aralkyl group is not particularly limited, but is generally preferably an aralkyl group having 7 to 11 carbon atoms. Examples of suitable aralkyl groups include a benzyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group.

The substituted amino group is not particularly limited, but is preferably an alkylamino group, a dialkylamino group, an arylamino group, or a diarylamino group. Specific examples of suitable substituted amino groups include a methylamino group, an ethylamino group, a phenylamino group, a dimethylamino group, a diethylamino group, and a diphenylamino group.

The unsubstituted aryl group is not particularly limited, but is generally preferably an unsubstituted aryl group having 6 to 10 carbon atoms. Examples of suitable unsubstituted aryl groups include a phenyl group and a naphthyl group.

As the substituted aryl group, one or more hydrogen atoms of the unsubstituted aryl group is the same alkyl group, alkoxy group, aryl group, aralkyl group, substituted amino group as described for R2. A substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and having a dangling bond at the nitrogen atom, or a fused heterocyclic ring in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the heterocyclic group Examples include those substituted with a group or the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

A substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and linking the nitrogen atom to a naphthopyran ring, or a condensation of an aromatic hydrocarbon ring or an aromatic heterocycle fused to the heterocyclic group The heterocyclic group is not particularly limited, but the number of carbon atoms constituting the heterocyclic group is generally 2 to 10, particularly preferably 2 to 6.
Further, a hetero atom may be present in the ring in addition to the nitrogen atom bonded to the naphthopyran ring, and the hetero atom is not particularly limited, but an oxygen atom, a sulfur atom, a nitrogen atom and the like are preferable. is there. A substituted or unsubstituted heterocyclic group having a suitable nitrogen atom as a heteroatom and the nitrogen atom bonded to a naphthopyran ring, or a condensation in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to the heterocyclic group Specific examples of the heterocyclic group include a morpholino group, a piperidino group,
Examples include a pyrrolidinyl group, a piperazino group, an N-methylpiperazino group, an indolinyl group, and the like.

[0055] a shown a number of substitutions in the above R ¹⁰ is an integer of 0 to 3. When a is 2 or 3, each R ¹⁰ may be different from each other. The position to which these substituents are bonded is not particularly limited as long as it is at the 7-, 8-, 9- or 10-position of the naphthopyran ring, and the total number thereof is not particularly limited, but the total number of the substituents present at these positions is It is preferable that the number is 2 or less.

Among the chromene compounds of the present invention, from the viewpoint of the effect, the following formula (2)

[0057]

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[Wherein, R¹¹Is a substituted amino group, a nitrogen atom
Having a nitrogen atom and a naphthopyran ring
Is a substituted or unsubstituted heterocyclic group,
An aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the ring group
Is a fused heterocyclic group,¹²And R¹³Is hydrogen
Atom, substituted amino group, nitrogen atom as hetero atom
Substitution wherein the nitrogen atom and the benzene ring are bonded or
An unsubstituted heterocyclic group, or an aromatic hydrocarbon ring
Or a fused heterocyclic group in which an aromatic heterocycle is fused,
R¹²And R¹³Are not simultaneously hydrogen atoms, and R
¹⁴Is a hydrogen atom, a cyano group, an alkyl having 1 to 5 carbon atoms
Group, alkoxy group having 1 to 5 carbon atoms, fluorine atom or chlorine
An atom, R^FifteenIs a hydrogen atom or a fat with 3 or more carbon atoms
A group hydrocarbon group;¹⁶Is a hydrogen atom, trifluoro
Methyl group, cyano group, sulfonyl group, alkylsulfonyl
, An arylsulfonyl group or a nitro group,
R¹⁴, R^FifteenAnd R ¹⁶Are two hydrogen atoms. 〕so
The chromene compounds shown are particularly preferred.

Specific examples of such compounds are as follows.
-Morpholino-3- (4'-morpholinophenyl) -3
-(4'-trifluorophenyl) -3H-benzo (f) chromene; 6-morpholino-3- (4'-morpholinophenyl) -3- (3'-t-butylphenyl)-
3H-benzo (f) chromene; 6-morpholino-3-
(3′-morpholinophenyl) -3- (2′-fluorophenyl) -3H-benzo (f) chromene; 6-indolino-3- (4′-morpholinophenyl) -3- (4 ′
-Cyanophenyl) -3H-benzo (f) chromene; 6
-Morpholino-3- (3'-N, N-diphenylaminophenyl) -3- (3'-isopropylphenyl) -3
H-benzo (f) chromene and the like can be mentioned. The chromene compound of the present invention represented by the general formula (1) is
Generally, it exists as a colorless or pale yellow solid or viscous liquid at normal temperature and normal pressure, and can be confirmed by the following means (a) to (c).

(A) Proton nuclear magnetic resonance spectrum (
By measuring the ¹ H-NMR), ^δ5.9~9.
A peak based on an aromatic proton and an alkene proton appears at about 0 ppm, and a peak based on an alkyl group and an alkylene group proton appears at about δ 1.0 to 4.0 ppm. Further, by comparing the respective spectral intensities relatively, the number of protons of each bonding group can be known.

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

(C) ¹³ C-nuclear magnetic resonance spectrum ( ¹³
C-NMR), δ110-160
a peak based on carbon of an aromatic hydrocarbon group around ppm,
A peak based on the carbon of the alkene appears around δ80 to 140 ppm, and a peak based on the carbon of the alkyl group and the alkylene group appears around δ20 to 80 ppm.

The method for producing the chromene compound represented by the general formula (1) of the present invention is not particularly limited, and may be obtained by any synthetic method. A typical method that is generally preferably used will be described below.

The following general formula (3)

[0065]

Embedded image {However, R ¹ , R ¹⁰ and a have the same meanings as defined in the general formula (1). A naphthol derivative represented by｝ and the following general formula (4)

[0066]

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{Provided that R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ,
R ⁸ and R ⁹ have the same meaning as defined in the general formula (1). This is a method of reacting a propargyl alcohol derivative represented by｝ in the presence of an acid catalyst. The method for synthesizing the naphthol derivative represented by the general formula (3) is not particularly limited. For example, the naphthol derivative can be suitably synthesized by the following method.

That is, 1,1-dichloro-2-naphthalenone is synthesized by reacting 2-naphthol with chlorine.
Next, a 1-chloro-2-naphthol derivative is synthesized by reacting with a secondary or primary amine corresponding to the substituent R ¹ in the above general formula (1) in the presence of a base such as triethylamine, and a reducing agent such as Raney nickel. And can be suitably synthesized. At this time, when 2-naphthol having substituents at the 5-, 6-, 7-, and 8-positions of 2-naphthol is used, the 7-position of the naphthopyran ring,
Chromene compounds having substituents at the 8-, 9-, and 10-positions can be synthesized.

The propargyl alcohol derivative represented by the general formula (4) can be synthesized, for example, by reacting a ketone derivative corresponding to the general formula (4) with a metal acetylene compound such as lithium acetylide.

The reaction conditions for reacting the naphthol derivative represented by the general formula (3) with the propargyl alcohol represented by the general formula (4) in the presence of an acid are not particularly limited. It is preferred to employ reaction conditions.

That is, the reaction ratio of these two compounds can be adopted from a wide range, but is generally 1:10 to 1
It is preferable to select from the range of 0: 1 (molar ratio).
Sulfuric acid, benzenesulfonic acid, p-
Toluenesulfonic acid, acidic alumina and the like are used, and it is preferable to use 0.1 to 10 parts by weight with respect to the total amount of the naphthol derivative and propargyl alcohol. Further, the reaction temperature is generally preferably from 0 to 200 ° C., and the solvent is an aprotic organic solvent such as N 2
-Methylpyrrolidone, dimethylformamide, tetrahydrofuran, benzene, toluene and the like are preferably used.

The method for purifying the reaction product is not particularly limited. For example, a purification method using a silica gel column, and a purification method such as recrystallization thereof can be employed.

The chromene compound represented by the general formula (1) of the present invention is well soluble in general organic solvents such as toluene, chloroform and tetrahydrofuran. When the chromene compound represented by the general formula (1) is dissolved in such a solvent, the solution is generally almost colorless and transparent, and rapidly develops color when irradiated with sunlight or ultraviolet light, and rapidly recovers its original colorlessness when light is blocked. A good reversible photochromic action is exhibited. Such a photochromic action is similarly exhibited in a polymer solid matrix. The target polymer solid matrix may be any one in which the chromene compound represented by the general formula (1) of the present invention is uniformly dispersed, and optically preferable, for example, polymethyl acrylate, polyacrylic acid Ethyl, polymethyl methacrylate, polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethyl methacrylate), polydimethylsiloxane,
A thermoplastic resin such as polycarbonate can be used.

Further, ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) Polyhydric acrylic acid and polyhydric methacrylate compounds such as propane and 2,2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane; diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, epoxy amber Diallyl acid, diallyl fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl jig Call carbonate, polyvalent allyl compounds such as trimethylolpropane triallyl carbonate; 1,2-bis (methacryloyl thio) ethane, bis (2-acryloylthioethyl) ether, 1,4
Polyvalent thioacrylic acid and polyvalent thiomethacrylate compounds such as 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)
Acrylic ester compounds such as -2-hydroxypropyl acrylate and methacrylic ester compounds; and thermosetting resins obtained by polymerizing radically polymerizable polyfunctional monomers such as divinylbenzene.

Further, each of these monomers and an unsaturated carboxylic acid such as acrylic acid, methacrylic acid and maleic anhydride; methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, etc. Acrylic acid and methacrylic acid ester compounds; fumaric acid ester compounds such as diethyl fumarate and diphenyl fumarate; thioacrylic acid and thiomethacrylic acid ester compounds such as methylthioacrylate, benzylthioacrylate and benzylthiomethacrylate; styrene, chlorostyrene, Copolymers with radically polymerizable monofunctional monomers such as vinyl compounds such as methylstyrene, vinylnaphthalene, α-methylstyrene dimer, and bromostyrene are exemplified.

The method for dispersing the chromene compound represented by the general formula (1) of the present invention in the polymer solid matrix is not particularly limited, and a general method can be used. For example, kneading the thermoplastic resin and the chromene compound in a molten state and dispersing the resin in the resin, or dissolving the chromene compound in the polymerizable monomer,
A method in which a polymerization catalyst is added and polymerized by heat or light to be dispersed in the resin, or a method in which the surface of the thermoplastic resin and the thermosetting resin is dispersed in the resin by dyeing a chromene compound on the surface can be exemplified. .

The chromene compound of the present invention can be widely used as a photochromic material. For example, various storage materials in place of silver salt photosensitive materials, copying materials, photosensitive materials for printing, storage materials for cathode ray tubes, photosensitive materials for lasers, holography. It can be used as various storage materials such as photosensitive materials for use. In addition, the photochromic material using the chromene compound of the present invention can be used as a material for a photochromic lens material, an optical filter material, a display material, a light meter, a decoration, and the like.

For example, when used for a photochromic lens, a method of sandwiching a polymer film formed by uniformly dispersing the chromene compound of the present invention into a lens; covering the lens surface with the polymer film, A method of coating with a curable substance; a method of dispersing the chromene compound of the present invention in the polymerizable monomer and polymerizing it by a predetermined method; 1 at 200 ° C
A method of impregnating the lens surface for 0 to 60 minutes and further covering the surface with a curable substance; and the like can be employed to obtain a photochromic lens having uniform light control performance.

[0079]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 The following naphthalene derivatives

[0081]

Embedded image 3.2 g (0.014 mol) of the following propargyl alcohol derivative

[0082]

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5.0 g (0.014 mol) was dissolved in 200 ml of toluene, and 0.05 g of p-toluenesulfonic acid was added, followed by refluxing for 1 hour. After the reaction, the solvent was removed, and a mixed solvent of chloroform and ethyl acetate (9: 1)
Was purified by chromatography on silica gel as eluent, to obtain 0.2 g of an orange powdery product. The yield was 2.5%.

The elemental analysis value of this product was C71.43.
%, H 5.36%, F 9.88%, N 4.79%, O
A 8.44%, C71.32% calculated values of _{C 34 H 31 F 3 NO 3} , H5.46%, F9.95%, N4.
89% and O 8.38% corresponded very well.

When the proton nuclear magnetic resonance spectrum was measured, as shown in FIG.
A peak of 16H based on a methylene proton of a morpholino group around δ 3.8 to 4.0 ppm, δ 6.0 to 8.1 p
A peak around 15 pm based on an aromatic proton and an alkene proton was shown. Further ¹³ C-
When a nuclear magnetic resonance spectrum was measured, δ110-1
A peak at around 60 ppm based on carbon of the aromatic ring, δ80
A peak based on the carbon of the alkene around ~ 140 ppm,
The peak based on alkyl carbon was shown in δ20 to 60 ppm.

From the above results, it was confirmed that the isolated product was a compound represented by the following structural formula (5).

[0087]

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Examples 2 to 9 In the same manner as in Example 1, the chromene compounds shown in Tables 1 and 2 were synthesized. The obtained product was subjected to structural analysis using the same means for structure confirmation as in Example 1, and as a result, Tables 1 and 2 were obtained.
Was confirmed to be a compound represented by the structural formula shown in Table 1.
Table 3 shows the elemental analysis values of these compounds, the calculated values obtained from the structural formulas of the respective compounds, and characteristic ¹ H-NMR spectra.

[0089]

[Table 1]

[0090]

[Table 2]

[0091]

[Table 3]

Example 10 0.05 part of the chromene compound obtained in Example 1 was added to 70 parts of tetraethylene glycol dimethacrylate, 15 parts of triethylene glycol dimethacrylate, 10 parts of glycidyl methacrylate and 5 parts of 2-hydroethyl methacrylate. And mixed well. This mixture was poured into a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer, and cast polymerization was performed. In the polymerization, the temperature was gradually increased from 30 ° C. to 90 ° C. over 18 hours using an air furnace, and the temperature was maintained at 90 ° C. for 2 hours. After the completion of the polymerization, the polymer was removed from the glass mold of the mold.

A xenon lamp L-2480 (300 W) manufactured by Hamamatsu Photonics was added to the obtained polymer (thickness: 2 mm).
SHL-100 was passed through an aeromass filter (manufactured by Corning) at 20 ° C. ± 1 ° C., and the beam intensity at the polymer surface was 365 nm = 2.4 mW / cm ² , 245 nm = 24 μ.
The color was developed by irradiation at 120 W / cm ² for 120 seconds, and the photochromic properties were measured. The photochromic properties were evaluated as follows.

Maximum absorption wavelength (λmax): Co., Ltd.
It is the maximum absorption wavelength after color development determined by a spectrophotometer (Instant Multi-Channel Photo Detector MCPD1000) manufactured by Otsuka Electronics Co., Ltd. The maximum absorption wavelength is related to the color tone at the time of color development.

Color density ｛ε (120) −ε
(0)｝: difference between the absorbance at the maximum absorption wavelength after light irradiation for 120 seconds {ε (120)} and the absorbance ε (0) at the age absorption wavelength without light irradiation. It can be said that the higher this value is, the better the photochromic property is.

Fading speed [t1 / 2 (min.)]: 12
After the light irradiation for 0 second, when the light irradiation is stopped, the absorbance at the maximum length of the sample is {ε (120) −ε (0)}.
The time it takes to drop to half of Since the fading speed of the blue compound is usually about 3 minutes, the fading speed of the chromene compound is 5 to 10 in order to perform fading while maintaining the uniformity of the color tone.
It can be said that it is better to be on the order of minutes. Coloring speed (min. ^-1 ): The rate of increase in color density per unit time until the color density reaches saturation when irradiated with a xenon lamp.

Table 4 shows the above results.

[0098]

[Table 4]

Examples 11 to 18 and Comparative Examples 1 to 3 A photochromic polymer was obtained in the same manner as in Example 10 except that the compounds obtained in Examples 2 to 9 were used as the chromene compound, and the characteristics were evaluated. did. The results are shown in Table 4.

Further, for comparison, the following formula (A):
(B) and (C)

[0101]

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[0102]

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[0103]

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A photochromic polymer was obtained in the same manner as described above, using the compound represented by the formula (1).

[0105]

[Table 5]

The photochromic polymers of Comparative Examples 1 and 2 have too high a fading speed. In addition, the photochromic polymer of Comparative Example 3 has too low a coloring speed and a fading speed. In contrast, Examples 10 to 18 using the chromene compound of the present invention.
Thus, the photochromic polymer has a moderately slow fade rate and a fast color development rate (similar to a blue compound).

[0107]

The chromene compound of the present invention exhibits a moderately slow fading rate and a high color developing rate in a solution or in a solid polymer matrix. Therefore, for example, when a chromene compound of the present invention is combined with a blue compound to obtain a photochromic lens exhibiting an intermediate color, the lens can develop and fade while maintaining uniformity of color tone.

[Brief description of the drawings]

FIG. 1 is a proton nuclear magnetic resonance spectrum of the compound of Example 1.

Claims (3)

[Claims] [Claim 1] The following general formula (1) In the formula, R ¹ is a substituted amino group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and bonding the nitrogen atom to a naphthopyran ring, or an aromatic hydrocarbon ring in the heterocyclic group. Or a condensed heterocyclic group in which an aromatic heterocyclic ring is condensed, wherein R ² , R ³ and R ⁴ each have a hydrogen atom, a substituted amino group or a nitrogen atom as a hetero atom, and the nitrogen atom is bonded to a benzene ring; A substituted or unsubstituted heterocyclic group, or a fused heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the heterocyclic group, wherein R ² , R ³ and R ⁴ are simultaneously hydrogen atoms. R ⁷ is a hydrogen atom, a trifluoromethyl group, a cyano group,
A sulfonyl group, an alkylsulfonyl group, an arylsulfonyl group or a nitro group, and R ⁶ and R ⁸ are each a hydrogen atom, an aliphatic hydrocarbon group having 3 or more carbon atoms, a fluorine atom, when R ⁷ is not a hydrogen atom, Trifluoromethyl group, cyano group, sulfonyl group,
An alkylsulfonyl group, an arylsulfonyl group, or a nitro group, when R ⁷ is a hydrogen atom, a hydrogen atom or an aliphatic hydrocarbon group having 3 or more carbon atoms, and R ⁵ and R ⁹ are each a hydrogen atom Atom, cyano group, carbon number 1
R ⁵ , R ⁶ , R ⁷ , R ^8, and R ⁹ are not hydrogen atoms at the same time, and R ¹⁰ is , An alkyl group, an alkoxy group, an aralkoxy group,
An aralkyl group, a substituted amino group, a cyano group, a substituted or unsubstituted aryl group, a halogen atom, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and bonding the nitrogen atom to a naphthopyran ring, or A condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is condensed to a heterocyclic group, and a is an integer of 0 to 3. Chromene compound represented by｝. 2. A photochromic material comprising the chromene compound according to claim 1. 3. A photochromic optical material comprising the chromene compound according to claim 1.