JP2000327675A - Chromene compounds - Google Patents

Abstract

(57) [Problem] To provide a photochromic compound having good photochromic durability having high color fading speed and little coloration upon deterioration. A novel chromene compound represented by the following general formula (1). Embedded image In the above formula, R ¹ and R ² are a hydrogen atom, an alkyl group, an aryl group and the like, and R ³ and R ⁴ are an aryl group and a heteroaryl group which may be different from each other.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is directed to a colored form which is changed by irradiation with light containing ultraviolet rays such as sunlight or light from a mercury lamp, the change being reversible and exhibiting excellent fading speed,
Further, the present invention relates to a novel chromene compound which is less colored upon deterioration and has excellent photochromic durability.

[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 containing ultraviolet rays such as sunlight or light from a mercury lamp, the color changes rapidly, and the irradiation of light is stopped. It is a reversible action that returns to the original color when placed in a dark place. A compound having this property is called a photochromic compound, and various compounds have been conventionally synthesized, but no special commonality is recognized in its structure.

[0003] PCT Patent Application Publication WO 96/14
No. 596 discloses a chromene compound represented by the following formula (A).

[0004]

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However, this chromene compound has a low color fading speed and is greatly colored when further deteriorated, and the durability of repetition has not been satisfactory. PCT
Patent application publication WO 97/48762 discloses a compound represented by the following formula (B).

[0006]

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However, this chromene compound has a low fading speed and lacks practicality.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to further improve the photochromic properties as compared with the above-mentioned conventional compounds, to increase the fading speed, to reduce the coloration at the time of deterioration, and to improve the photochromic durability. A chromene compound is provided.

[0009]

DISCLOSURE OF THE INVENTION The present invention has been proposed to achieve the above object, and the novel chromene compound has a high fading speed, has little coloration upon deterioration, and has excellent photochromic durability. It has been completed based on the knowledge obtained by the present inventors. That is, the present invention provides the following general formula (1)

[0010]

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Wherein R ¹ and R ² represent a hydrogen atom, an alkyl group, an alkoxy group, an aralkoxy group, an amino group, a substituted amino group, a cyano group, a substituted or unsubstituted aryl group, a halogen atom, an aralkyl group; A substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and the nitrogen atom bonded to an indene ring, or a fused heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the heterocyclic group Is a cyclic group, p and q are each an integer of 0 to 3 representing the number of substituents R ¹ and R ² , and R ³ and R ⁴ may be different from each other in the following formula (2)

[0012]

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Wherein R ⁵ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, R ⁶ is a hydrogen atom, an alkyl group or a halogen atom, and n is 1 to 3 A group represented by the formula:
The following equation (3)

[0014]

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Wherein R ⁷ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and m is an integer of 1 to 3. Or a substituted or unsubstituted heteroaryl group, an alkyl group, or an aliphatic or aromatic hydrocarbon ring group formed by combining R ³ and R ⁴ . It is a chromene compound represented by｝.

Another invention is a photochromic material comprising a chromene compound represented by the above general formula (1). Still another invention is a photochromic optical material containing the chromene compound represented by the general formula (1).

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula (1), the substituents R ¹ and R ² are a hydrogen atom, an alkyl group, an alkoxy group, an aralkoxy group, an amino group, a substituted amino group, a cyano group, a substituted or unsubstituted group. An aryl group, a halogen atom, an aralkyl group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and the nitrogen atom bonded to an indene ring, or an aromatic hydrocarbon ring or aromatic It is a condensed heterocyclic group in which a group heterocyclic ring is condensed.

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 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 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 aryl group is not particularly limited, but is generally an aryl group having 6 to 10 carbon atoms. Examples of suitable aryl groups include a phenyl group and a naphthyl group. Further, as a substituent of the aryl group,
The same alkyl group, alkoxy group, aryl group, substituted amino group as R ¹ and R ² , a substituted or unsubstituted heterocyclic group having a nitrogen atom as a hetero atom and bonding the nitrogen atom to the aryl group, or Examples of the heterocyclic group include a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is condensed.

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

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.

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

The position at which the substituents R ¹ and R ² are bonded to the ring is not particularly limited as long as it is a bondable position in each ring.

P and q each represent the number of substituents R ¹ and R ² and are integers from 0 to 3, preferably 2 or less. p,
When q is 2 or more, each group may be different from each other.

In the general formula (1), R ³ and R ⁴ may be different from each other.

[0029]

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Wherein R ⁵ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, R ⁶ is a hydrogen atom, an alkyl group or a halogen atom, and n is 1 to 3 A group represented by the formula:
The following equation (3)

[0031]

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Wherein R ⁷ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and m is an integer of 1 to 3. Or a substituted or unsubstituted heteroaryl group, an alkyl group, or an aliphatic or aromatic hydrocarbon ring group formed by combining R ³ and R ⁴ .

R ⁵ in the above formula (2) is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

The aryl group is not particularly limited.
An aryl group having 6 to 10 carbon atoms is preferred. Specific examples include a phenyl group and a naphthyl group.

As the substituent for the aryl group, groups having the same meanings as those described above for R ¹ and R ² are applied. Preferably, a substituted amino group, an alkoxy group, an alkyl group,
A substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and the nitrogen atom being bonded to an aryl group, or a fused heterocyclic ring in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the heterocyclic group Groups.

The position where the substituent is bonded is not particularly limited.
The total number of the substituents is not particularly limited, either, but when the aryl group is a phenyl group, the 3- or 4-position is preferable. When the aryl group is a naphthyl group, the 4- or 6-position is preferable.

The heteroaryl group is not particularly limited, but is preferably a heteroaryl group having 4 to 12 carbon atoms.
Specific examples include a thienyl group, a furyl group, a pyrrolinyl group, a pyridyl group, a benzothienyl group, a benzofuranyl group, and a benzopyrrolyl group.

As the substituent for the heteroaryl group, the same groups as those described above for R ¹ and R ² are applied.
Preferably, a substituted or unsubstituted heterocyclic group having a substituted amino group, an alkoxy group, an alkyl group, a nitrogen atom as a hetero atom and the nitrogen atom and a heteroaryl group bonded thereto, or an aromatic group having an aromatic group Examples thereof include a condensed heterocyclic group in which a hydrocarbon ring or an aromatic heterocyclic ring is condensed. The position where the substituent is bonded is not particularly limited, and the total number of the substituent is not particularly limited.

R ⁶ in the above formula (2) is a hydrogen atom, an alkyl group or a halogen atom. Specific examples of suitable alkyl groups include a methyl group, an ethyl group, and a propyl group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In the above formula (2), n represents a repeating unit and is an integer of 1 to 3. From the viewpoint of raw material acquisition, n is 1
It is preferred that

Specific examples of preferred groups of the above formula (2) include a phenyl-ethylenyl group, a (4- (N, N-dimethylamino) phenyl) -ethenyl group and a (4- (N, N
-Diethylamino) phenyl) -ethenyl group, (4-morpholinophenyl) -ethenyl group, (4-piperidinophenyl) -ethenyl group, (4-eurolidinophenyl)
-Ethenyl group, (4-methoxyphenyl) -ethenyl group, (4-methylphenyl) -ethenyl group, (2-
(N, N-dimethylamino) phenyl) -ethenyl group,
(2-methoxyphenyl) -ethenyl group, phenyl-1
-Methylethenyl group, (4- (N, N-dimethylamino) phenyl) -1-methylethenyl group, (4-methoxyphenyl) -1-methylethenyl group, phenyl-1-
Fluoroethenyl group, (4- (N, N-dimethylamino) phenyl) -1-fluoroethenyl group, 2-thienyl-ethenyl group, 2-furyl-ethenyl group, 2- (N-
Methyl) pyrrolinyl-ethenyl group, 2-benzothienyl-ethenyl group, 2-benzofuranyl-ethenyl group, 2-
And (N-methyl) indolyl-ethenyl groups.

R ⁷ in the above formula (3) is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. Here, a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl groups are groups as defined for group described as R ⁵ above.

In the above formula (3), m represents a repeating unit, m is an integer of 1 to 3, and 1 is preferable from the viewpoint of easy availability of raw materials.

Specific examples of preferred groups of the above formula (3) include a phenyl-ethynyl group, a (4- (N, N-dimethylamino) phenyl) -ethynyl group and a (4- (N, N
-Diethylamino) phenyl) -ethynyl group, (4-morpholinophenyl) -ethynyl group, (4-piperidinophenyl) -ethynyl group, (4-eurolidinophenyl)
-Ethynyl group, (4-methoxyphenyl) -ethynyl group, (4-methylphenyl) -ethynyl group, (2-
(N, N-dimethylamino) phenyl) -ethynyl group,
(2-methoxyphenyl) -ethynyl group, 2-thienyl-ethynyl group, 2-furyl-ethynyl group, 2- (N-methyl) pyrrolinyl-ethynyl group, 2-benzothienyl-
Ethyl group, 2-benzofuranyl-ethynyl group, 2- (N
-Methyl) indolyl-ethynyl group and the like. Further, the substituted or unsubstituted aryl group or the substituted or unsubstituted heteroaryl group as R ³ and R ⁴ is not particularly limited, and has the same meaning as the group described as R ⁵ above.

The alkyl group as R ³ and R ⁴ is not particularly limited, but has the same meaning as the group described as R ¹ . The aliphatic hydrocarbon ring group formed by R ³ and R ⁴ together is not particularly limited, but specific examples include an adamantylidene group,
Examples include a bicyclononylidene group and a norbornylidene group.

The aromatic hydrocarbon ring group formed by R ³ and R ⁴ together is not particularly limited,
Specific examples include a fluorene group and the like.

It is preferable that at least one of R ³ and R ⁴ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

Further, at least one of R ³ and R ⁴ is a substituted or unsubstituted heterocyclic group having a substituted amino group and a nitrogen atom as a hetero atom and having the nitrogen atom bonded to an aryl group or a heteroaryl group. An aryl group or a heteroaryl group having, as a substituent, a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is condensed to a ring group or the heterocyclic group, R ⁵ is a substituted amino group, and a nitrogen atom is a hetero atom. A substituted or unsubstituted heterocyclic group in which the nitrogen atom is bonded to an aryl group or a heteroaryl group, or a fused heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to the heterocyclic group. group represented by the formula (2) is an aryl or heteroaryl group having a substituent, or R ⁷ is nitrogen atom and ants have a substituted amino group, a nitrogen atom as a hetero atom Or a substituted or unsubstituted heterocyclic group bonded to a heteroaryl group or a heteroaryl group, or an aryl group having as a substituent a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to the heterocyclic group Alternatively, it is preferably a group represented by the formula (3) which is a heteroaryl group.

A substituted or unsubstituted heterocyclic group having a substituted amino group or a nitrogen atom as a heteroatom and having the nitrogen atom and an aryl group bonded thereto, or an aromatic hydrocarbon ring or aromatic group The aryl group having a condensed heterocyclic group to which a group heterocyclic ring is condensed as a substituent is not particularly limited in the position where the substituent is substituted, and the total number of the substituents is not particularly limited, but the substitution position is such that the aryl group is a phenyl group. In some cases, substitution at the 3- or 4-position is preferred, and the number is preferably 1.

Specific examples of preferred aryl groups having the above-mentioned heterocyclic group or fused heterocyclic group as a substituent include 4
-(N, N-dimethylamino) phenyl group, 4- (N,
An N-diethylamino) phenyl group, a 4- (N, N-diphenylamino) phenyl group, a 4-morpholinophenyl group, a 4-piperidinophenyl group, a 3- (N, N-dimethylamino) phenyl group and the like can be mentioned. it can.

A substituted or unsubstituted heterocyclic group having the above-mentioned substituted amino group or nitrogen atom as a heteroatom and having the nitrogen atom and a heteroaryl group bonded thereto, or an aromatic hydrocarbon ring or In the heteroaryl group having, as a substituent, a condensed heterocyclic group in which an aromatic heterocycle is condensed, the position at which the substituent is substituted is not particularly limited, and the total number of substituents is not particularly limited, but the number is one. Is preferred.

Specific examples of the preferred heteroaryl group having the heterocyclic group or the fused heterocyclic group as a substituent include a 4- (N, N-dimethylamino) thienyl group and a 4- (N, N-dimethylamino) thienyl group.
(N, N-diethylamino) furyl group, 4- (N, N-
Diphenylamino) thienyl group, 4-morpholinopyrrolinyl group, 6-piperidinobenzothienyl group, 6- (N,
And N-dimethylamino) benzofuranyl group.

R ⁵ is a substituted amino group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a hetero atom and the nitrogen atom bonded to an aryl group or a heteroaryl group, or In the case of a group represented by the formula (2), which is an aryl group or a heteroaryl group having, as a substituent, a condensed heterocyclic group in which a hydrocarbon ring or an aromatic heterocyclic ring is condensed, R ⁵ is the above-mentioned R ³ , R ⁴ A substituted or unsubstituted heterocyclic group having a substituted amino group, a nitrogen atom as a hetero atom, and the nitrogen atom being bonded to an aryl group or a heteroaryl group, or an aromatic hydrocarbon ring or It is a group having the same meaning as the group described as the aryl group or the heteroaryl group having, as a substituent, a condensed heterocyclic group in which an aromatic heterocyclic ring is condensed.

As an example of a preferable group represented by the formula (2) wherein R ⁵ is an aryl group or a heteroaryl group having the substituent, (4- (N, N-dimethylamino) phenyl) -ethenyl Group, (4- (N, N-diethylamino) phenyl) -ethenyl group, (4-morpholinophenyl) -ethenyl group, (4-piperidinophenyl)
-Ethenyl group, (4-eurolidinophenyl) -ethenyl group, (2- (N, N-dimethylamino) phenyl)-
An ethenyl group, (4- (N, N-dimethylamino) phenyl) -1-methylethenyl group, (4- (N, N-dimethylamino) phenyl) -1-fluoroethenyl group and the like can be mentioned.

R ⁷ is a substituted amino group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and the nitrogen atom bonded to an aryl group or a heteroaryl group, or an aromatic group in the heterocyclic group. In the case of a group represented by the formula (3), which is an aryl group or a heteroaryl group having, as a substituent, a condensed heterocyclic group in which a hydrocarbon ring or an aromatic heterocyclic ring is condensed, R ⁷ represents R ³ , R ⁴ described above. A substituted or unsubstituted heterocyclic group having a substituted amino group, a nitrogen atom as a hetero atom, and the nitrogen atom being bonded to an aryl group or a heteroaryl group, or an aromatic hydrocarbon ring or It is a group having the same meaning as the group described as the aryl group or the heteroaryl group having, as a substituent, a condensed heterocyclic group in which an aromatic heterocycle is condensed.

A preferable example of the group represented by the formula (3) wherein R ⁷ is a substituted aryl group or a heteroaryl group is (4- (N, N-dimethylamino) phenyl) -ethynyl group. , (4- (N, N-diethylamino) phenyl) -ethynyl group, (4-morpholinophenyl) -ethynyl group, (4-piperidinophenyl) -ethynyl group, (4-eurolidinophenyl) -ethynyl group ,
(2- (N, N-dimethylamino) phenyl) -ethynyl group, 2- (N-methyl) indolyl-ethynyl group,
(4- (N-methylpiperazino) phenyl) -ethynyl and the like.

The chromene compound suitable in the present invention is
The following equation (4)

[0058]

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(Wherein R ⁸ and R ⁹ represent a hydrogen atom, an alkyl group, an alkoxy group, an aralkoxy group, a substituted amino group, a cyano group, a substituted or unsubstituted aryl group, a halogen atom, an aralkyl group nitrogen atom) A substituted or unsubstituted heterocyclic group in which the nitrogen atom and the naphthalene ring are bonded as an atom or a fused heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to the heterocyclic group,
R ¹⁰ and R ¹¹ are a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group which may be different from each other. ).

More preferably, R ¹⁰ is a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted heterocyclic group having a substituted amino group, a nitrogen atom as a heteroatom, and the nitrogen atom bonded to an aryl group or a heteroaryl group. A chromene compound represented by the above formula (4), which is an aryl group or a heteroaryl group having, as a substituent, a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is condensed to a ring group.

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

[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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The compound represented by the general formula (1) of the present invention generally exists as a colorless or pale yellow solid or viscous liquid at normal temperature and normal pressure, and is represented by the following (a) to (c). Can be confirmed by various means.

(A) Proton nuclear magnetic resonance spectrum (
By measuring ¹ H-NMR), δ 5.0 to 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 carbons of alkenes and alkynes appears around δ80 to 140 ppm, and a peak based on carbons of alkyl groups and alkylene groups 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.

Process A: The following general formula (5)

[0073]

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(Wherein R ¹ , R ² , p and q have the same meanings as defined in the general formula (1)) and a hydroxy-fluorene derivative represented by the general formula (6)

[0075]

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(However, R ³ and R ⁴ have the same meanings as defined in the general formula (1).) A method of reacting a propargyl alcohol derivative represented by the formula (1) in the presence of an acid catalyst.

The method for synthesizing the compounds represented by the general formulas (5) and (6) is not particularly limited. The hydroxy-fluorene derivative represented by the general formula (5) is obtained, for example, by reacting a hydroxy-fluorenone derivative with a Grignard reagent at -10 to 70 ° C for 10 minutes to 4 hours to obtain a hydroxy-fluorenol derivative, It can be synthesized by reacting under acidic conditions at 10 to 120 ° C. for 10 minutes to 2 hours, and spiroting fluorenol. The propargyl alcohol derivative represented by the general formula (6) can be synthesized, for example, by reacting a ketone derivative corresponding to the general formula (6) with a metal acetylene compound such as lithium acetylide.

The reaction between the compound represented by the general formula (5) and the compound represented by the general formula (6) is carried out as follows. That is, the reaction ratio of these two compounds is adopted from a wide range, but is generally 1:10 to 10.
It is selected from the range of 10: 1 (molar ratio). Further, as the acid catalyst, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acidic alumina or the like is used.
It is used in the range of 1 to 10 parts by weight. The reaction temperature is usually preferably from 0 to 200 ° C., and as the solvent, an aprotic organic solvent such as N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, benzene, and toluene are used.

Process B: The following general formula (7)

[0080]

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(Wherein R ¹ , R ² , p and q have the same meanings as defined in formula (1)) and a hydroxy-fluorenone derivative represented by formula (6)

[0082]

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(Provided that R ³ and R ⁴ have the same meanings as defined in the general formula (1)) by reacting the propargyl alcohol derivative represented by the following formula (8)

[0084]

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(However, R ¹ , R ² , R ³ , R ⁴ , p and q
Has the same meaning as defined in general formula (1). ) (Hereinafter abbreviated as precursor chromene compound 1).
And then reacting the compound of general formula (8) with the Grignard reagent at -10 to 70 ° C for 10 minutes to 4 hours to obtain a fluorenol-chromene derivative as described in the synthesis method of the compound of general formula (5). (Hereinafter abbreviated as precursor chromene compound 2), and then, under neutral to acidic conditions, 10
This is a method of obtaining a chromene compound of the above general formula (1) by reacting at ク ロ 120 ° C. for 10 minutes to 2 hours to spiro-form the fluorenol moiety of the precursor chromene compound 2.

The reaction between the compound represented by the general formula (7) and the compound represented by the general formula (6) is carried out as follows. That is, the reaction ratio of these two compounds is adopted from a wide range, but is generally 1:10 to 10.
It is selected from the range of 10: 1 (molar ratio). Further, as the acid catalyst, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acidic alumina or the like is used.
It is used in the range of 1 to 10 parts by weight. The reaction temperature is usually preferably from 0 to 200 ° C., and as the solvent, an aprotic organic solvent such as N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, benzene, and toluene are used.

The reaction from the general formula (8) to the general formula (1) is carried out as follows. That is, the compound of general formula (8) is reacted with a Grignard reagent to obtain a precursor chromene compound 2. This reaction ratio is employed from a wide range, but is generally 1:10 to 10: 1 (molar ratio).
Is selected from the range. The reaction temperature is usually -10 to 70
° C. is preferred, as the solvent, an aprotic organic solvent,
For example, diethyl ether, tetrahydrofuran, benzene, toluene and the like are used. Then, benzo (a)
The fluorene 9-position of the fluoren-9-ol-chromene derivative is spiroylated under neutral to acidic conditions. Acetic acid, hydrochloric acid, sulfuric acid, benzenesulfonic acid, p
-Toluenesulfonic acid, acidic alumina and the like are used, and used in a range of 0.1 to 10 parts by weight based on the total amount of the precursor chromene compound 2. The reaction temperature is usually 0 to 120 ° C.
Preferably, acetic acid, tetrahydrofuran, benzene, toluene and the like are used as the solvent.

The method for purifying the product is not particularly limited. For example, the product can be purified by silica gel column purification and further recrystallization.

The chromene compound represented by the general formula (1) of the present invention is well soluble in common 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. The photochromic action of such a compound of the general formula (1) shows similar properties even 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,
Examples include thermoplastic resins such as polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethyl methacrylate), polydimethylsiloxane, and polycarbonate.

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.

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 in a photochromic lens, there is no particular limitation as long as uniform light control performance can be obtained, and specifically, a polymer film obtained by uniformly dispersing the photochromic material of the present invention. Or a method of sandwiching the chromene compound of the present invention in the polymerizable monomer and polymerizing it by a predetermined method, or dissolving this compound in, for example, silicone oil. 150-2
There is a method in which the surface of the lens is impregnated at 00 ° C. for 10 to 60 minutes, and the surface is further coated with a curable substance to form a photochromic lens. Further, there is a method in which the polymer film is coated on the lens surface, and the surface is coated with a curable substance to form a photochromic lens.

[0094]

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 3-hydroxy-benzo (a) fluorene derivative

[0096]

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1.0 g (0.0026 mol) of the following propargyl alcohol derivative

[0098]

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0.77 g (0.0026 mol) was dissolved in 50 ml of toluene, and 0.05 g of p-toluenesulfonic acid was added, followed by stirring at room temperature for 1 hour. After the reaction,
Removal of the solvent and purification by chromatography on silica gel gives the product 0.4 as a pale yellow powder.
g was obtained. The yield was 24%. The elemental analysis value of this product was 88.05% for C, 5.15% for H, and N2.09.
%, O 4.70%, calculated values of C ₄₈ H ₃₅ NO ₂ , C 87.64%, H 5.36%, N 2.13%, O
This was in very good agreement with 4.86%.

Further, when the proton nuclear magnetic resonance spectrum was measured, the peak of 8H based on the methylene proton of the morpholino group was found around δ 3.0 to 4.0 ppm, and δ 5.
A peak of 27H based on an aromatic proton and an alkene proton was shown at around 6 to 9.0 ppm.
Further measurement of ¹³ C-nuclear magnetic resonance spectrum,
A peak based on the carbon of the aromatic ring was found at around δ 110 to 160 ppm, a peak based on the carbon of the alkene around δ 80 to 140 ppm, and a peak based on the carbon of the alkyl at δ 20 to 60 ppm. From the above results, it was confirmed that the isolated product was a compound represented by the following structural formula.

[0101]

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Examples 2 to 5 In the same manner as in Example 1, chromene compounds shown in Table 1 were synthesized. The obtained product was subjected to structure analysis using the same means for structure confirmation as in Example 1, and as a result, it was confirmed that the product was a compound represented by the structural formula shown in Table 1. Table 2 shows the elemental analysis values of these compounds, the calculated values obtained from the structural formulas of the compounds, and the characteristic spectra of the ¹ H-NMR spectrum.

Example 6 The following Grignard reagent

[0104]

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The following precursor chromene compound 1 was prepared by dissolving 0.55 g (0.0019 mol) in 20 ml of tetrahydrofuran and dissolving in 30 ml of tetrahydrofuran.

[0106]

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1.0 g (0.0018 mol) at 25 ° C.
And reacted for 1 hour. After the reaction, the solvent was removed, and the product was purified by chromatography on silica gel to obtain 0.2 g of a product as a pale yellow powder. The yield was 16%. Elemental analysis of this product gave C90.
56%, H5.13%, N2.01% , a O2.30%, C90.54% calculated values of C ₅₂ H ₃₅ NO,
H 5.11%, N 2.03% and O 2.32% corresponded very well.

Further, when the proton nuclear magnetic resonance spectrum was measured, a peak of 4H based on the methylene proton of the indolino group, δ5.
A peak of 31H based on an aromatic proton and a proton of an alkene was shown around 6 to 9.0 ppm.

Further measurement of ¹³ C-nuclear magnetic resonance spectrum revealed that a peak based on the carbon of the aromatic ring was found at about δ 110 to 160 ppm, a peak based on the carbon of the alkene was found at about δ 80 to 140 ppm, and a peak based on the carbon of the alkyl was found at δ 20 to 60 ppm. Showed a peak.

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

[0111]

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Examples 7 and 8 In the same manner as in Example 6, chromene compounds shown in Table 1 were synthesized. The obtained product was subjected to structure analysis using the same means for structure confirmation as in Example 1, and as a result, it was confirmed that the product was a compound represented by the structural formula shown in Table 1. Table 2 shows the elemental analysis values of these compounds, the calculated values obtained from the structural formulas of the compounds, and the characteristic spectra of the ¹ H-NMR spectrum.

[0113]

[Table 1]

[0114]

[Table 2]

[0115]

[Table 3]

[0116]

[Table 4]

Examples 9 to 16, Comparative Examples 1 and 2 0.05 part of the chromene compound obtained in Example 1 was used in 70 parts of tetraethylene glycol dimethacrylate, 15 parts of triethylene glycol dimethacrylate, 10 parts of glycidyl methacrylate, -Added to 5 parts of hydroethyl methacrylate and mixed well. This mixed solution 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.
Irradiation was performed at W / cm 2 for 120 seconds to develop color, and various photochromic properties were measured according to the methods described below.

Maximum absorption wavelength (λmax): λmax after color development of this polymer was determined by a spectrophotometer (Instant Multi-Channel Photo Detector MCPD1000) manufactured by Otsuka Electronics Co., Ltd.

Initial coloring (−) = ε (0) · ε (0): Absorbance of the polymer in the unirradiated state at the same wavelength as the maximum absorption wavelength when irradiated with light.

Color density (−) = ε (120) −ε
(0) · ε (120): Absorbance of the polymer at the maximum absorption wavelength after irradiation for 120 seconds under the above conditions.

Fading speed [t1 / 2 (min.)] = 120
After irradiation for 2 seconds, the absorbance of this polymer is [ε (120) −ε
(0)].

The following test was conducted as a method of accelerating the deterioration.
The obtained polymer was acceleratedly degraded for 200 hours using a xenon weather meter X25 manufactured by Suga Test Instruments Co., Ltd. The evaluation method of the photochromic stability before and after degradation, evaluates the color density before orders before and after degradation, by measuring the initial color density (A ₀₎ and the color density after accelerated experiment 200 hours (A _{2 00)} , And durability are shown below.

Durability (%) = (A ₀ / A ₂₀₀ ) × 10
Further, the color difference before and after the deterioration was measured by a color difference meter (SM-4) manufactured by Suga Test Instruments Co., Ltd. before and after the deterioration. The degree is YI (20
0), and the degree of color change due to deterioration is represented by ΔYI,
It was colored at the time of deterioration.

The degree of change in color (ΔYI) = YI (20
0) -YI (0) Table 3 shows the results.

A photochromic polymer was obtained in the same manner as described above, except that the compounds obtained in Examples 2 to 8 were used as the chromene compound. The characteristics are shown in Table 3.

For comparison, the following formula (A):
(B)

[0128]

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[0129]

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After a photochromic polymer was obtained in the same manner using the conventional compound represented by the formula (1), the photochromic properties were measured.

[0131]

[Table 5]

Example 9 using the chromene compound of the present invention
In No. 16 to No. 16, the photochromic polymers were Comparative Examples 1 and 2.
As compared with the above, all three effects of the fading speed, coloring at the time of deterioration and durability of photochromic property are excellent.

[0133]

The chromene compound of the present invention exhibits a high fading rate in a solution or a solid polymer matrix, has little coloration upon deterioration, and has good photochromic durability. For example, a photochromic lens using the chromene compound of the present invention quickly returns to the original color tone when returned from indoors to indoors, and shows good durability with little coloring due to deterioration even when used for a long time.

Claims (3)

[Claims] [Claim 1] The following general formula (1) In the formula, the substituents R ¹ and R ² are a hydrogen atom, an alkyl group, an alkoxy group, an aralkoxy group, an amino group, a substituted amino group,
A cyano group, a substituted or unsubstituted aryl group, a halogen atom, an aralkyl group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and bonding the nitrogen atom to an indene ring, or the heterocyclic group Is a fused heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused,
p and q are each an integer of 0 to 3 representing the number of substituents R ¹ and R ² , and the substituents R ³ and R ⁴ may be different from each other. (Wherein, R ⁵ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group,, R ⁶
Is a hydrogen atom, an alkyl group or a halogen atom, and n
Is an integer of 1 to 3. ), A group represented by the following formula (3): (Wherein, R ⁷ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and m is an integer of 1 to 3), or a substituted or unsubstituted aryl group A substituted or unsubstituted heteroaryl group, an alkyl group, or an aliphatic hydrocarbon ring group or an aromatic hydrocarbon ring group formed by combining R ³ and R ⁴ . 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.