JP2000327676A - Chromene compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound having a high fading rate, causing slight discoloration at the time of deterioration, excellent in durability of photochromism and useful for a photochromic lens, etc., by further improving the photochromism as compared with that of a conventional compound. SOLUTION: This compound is represented by formula I [R1 and R2 are each H, an alkyl or the like; p and q are each 0-3; R3 and R4 together may compose a (substituted)aromatic hydrocarbon ring or the like; X is O or the like], e.g. a compound represented by formula II. The compound represented by formula I is obtained by reacting a naphthol derivative represented by formula III with a propargyl alcohol derivative represented by formula IV, preferably in (1:10) to (10:1) molar ratio in the presence of an acidic catalyst (e.g. sulfuric acid) in an amount of preferably 0.1-10 pts.wt. based on the sum total of the reactional substrates, etc. The above compound is easily soluble in an organic solvent, assumes good reversible photochromic actions and exhibits similar characteristics even in a polymer. The above compound can be utilized for various kinds of memory materials, copying materials, etc., in place of silver salt photosensitive materials.

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, and its use.

[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 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.

Also, PCT Patent Application Publication WO 97
/ 48762 discloses a chromene compound represented by the following formula (B).

[0007]

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

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a chromene compound which further improves the photochromic properties as compared with the above-mentioned compounds, has a high fading speed, has little coloring upon deterioration, and has excellent photochromic durability. Is to provide.

[0010]

DISCLOSURE OF THE INVENTION The present invention has been proposed to achieve the above-mentioned object, and provides a novel chromene compound which has a high fading speed, has little coloring upon deterioration, and has excellent photochromic durability. It is a suggestion.

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

[0012]

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[Wherein R ¹ and R ² each independently 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, Atoms, aralkyl groups,
A substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and bonding the nitrogen atom to a benzene ring, or a fused heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to the heterocyclic group And p and q are integers of 0 to ³ , and R ³ and R ⁴ are each independently the following formula (2)

[0014]

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(Wherein, R ⁷ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, R ⁸ is a hydrogen atom, an alkyl group, or a halogen atom; Which is an integer of from 3 to 3),
The following equation (3)

[0016]

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(Wherein R ⁹ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and m is an integer of 1 to 3). An aryl group, a substituted or unsubstituted heteroaryl group, or an alkyl group, or R ³ and R ⁴ together form a substituted or unsubstituted aliphatic hydrocarbon ring, or a substituted or unsubstituted aromatic group; R ⁵ and R ⁶ may each independently form a group hydrocarbon ring.
Hydrogen atom, hydroxyl group, substituted or unsubstituted alkyl group,
Substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl group, allyl group, cyano group, halogen atom, alkoxy group, aralkoxy group, alkoxycarbonyl group, hydroxycarbonyl group, substituted or unsubstituted aminocarbonyl group, or An aralkyl group, or R
⁵ and R ⁶ may together form an oxo group, a substituted or unsubstituted aliphatic hydrocarbon ring, or a substituted or unsubstituted heterocyclic ring, and X represents an oxygen atom, a sulfur atom,
Ethylidene group, the following formula (4)

[0018]

Embedded image (Wherein R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, an allyl group, a cyano group, Group, a halogen atom, an alkoxy group, an aralkoxy group, an alkoxycarbonyl group, a hydroxycarbonyl group, a substituted or unsubstituted aminocarbonyl group, or an aralkyl group, or R ¹⁰ and R ¹¹ together form an oxo group, A substituted or unsubstituted aliphatic hydrocarbon ring or a substituted or unsubstituted heterocyclic ring) or the following formula (5)

[0019]

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(In the formula, R ¹² is a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, an allyl group, or a cyano group.) ] Is a chromene compound represented by the formula:

Further, another invention is a photochromic material comprising the chromene compound represented by the above general formula (1), and a photochromic optical material comprising the chromene compound.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1),
R ¹ and R ^{2 each} have 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, or a nitrogen atom as a hetero atom. A substituted or unsubstituted heterocyclic group in which a nitrogen atom and an aromatic ring are bonded, or a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the heterocyclic group.

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 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.

The unsubstituted 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.

As the substituted aryl group, one or more hydrogen atoms of the unsubstituted aryl group may be the same alkyl group, alkoxy group, aryl group or substituted amino group as described above for R ¹ and R ^2. A substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and bonding the nitrogen atom 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 And the like.

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 a benzene ring, or a condensation in which an aromatic hydrocarbon ring or an aromatic heterocycle is 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. In the heterocycle, a hetero atom may be present in addition to the nitrogen atom bonded to the benzene ring. The hetero atom is not particularly limited, but an oxygen atom, a sulfur atom, a nitrogen atom and the like are preferable.

A substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and the nitrogen atom being bonded to a benzene ring, or a condensation in which an aromatic hydrocarbon ring or an aromatic heterocycle is condensed to the heterocyclic group Specific examples of suitable heterocyclic groups include morpholino, piperidino, pyrrolidinyl, piperazino, N-methylpiperazino,
An indolinyl group and the like can be mentioned.

R¹And R^TwoP and q indicating the number of substitutions of
Is an integer of 0 to 3. R¹And R^TwoEach of which binds
The position is not particularly limited, and the total number is not particularly limited.
Is preferably 2 or less. p or q
Is 2 or 3, each R ¹Or R^TwoAre different from each other
May be.

In the general formula (1), R ³ and R ⁴ are each independently the following formula (2)

[0035]

Embedded image (Wherein, R ⁷ is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, R ⁸
Is a hydrogen atom, an alkyl group, or a halogen atom,
n is an integer of 1 to 3), a group represented by the following formula (3)

[0036]

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Wherein R ⁹ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and m is an integer of 1 to 3; , A substituted or unsubstituted heteroaryl group, or an alkyl group. R ³ ,
And R ⁴ are not limited to these groups, and R ³ and R ⁴ may be combined to form an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring.

R ⁷ in the above formula (2) is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. The substituted or unsubstituted aryl group is not particularly limited, but the same group as the above-mentioned substituted or unsubstituted aryl group for R ¹ and R ² is applied.

In the substituted aryl group, the position to which the substituent is bonded is not particularly limited, and the total number thereof is not particularly limited. However, when the aryl group is a phenyl group, the aryl group is a 3- or 4-position, and when the aryl group is a naphthyl group, Position 4 or 6 is preferred.

The unsubstituted heteroaryl group is not particularly limited, but is preferably a heteroaryl group having 4 to 12 carbon atoms. Specific examples include a thienyl group,
Examples thereof include a furyl group, a pyrrolyl group, a pyridinyl group, a benzothienyl group, a benzofuranyl group, and a benzopyrolinyl group. Examples of the substituted heteroaryl group include those in which one or more hydrogen atoms of the unsubstituted heteroaryl group are substituted with the same substituents as those in the above-described substituted aryl groups of R ¹ and R ^2. . The position where these substituents are bonded is not particularly limited, and the total number is not particularly limited.

R ⁸ 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 is an integer of 1 to 3. From the viewpoint of obtaining raw materials, n is preferably 1.

Among the groups represented by the above formula (2), preferred examples include a phenyl-ethylenyl group,
(4- (N, N-dimethylamino) phenyl) -ethenyl group, (4- (N, N-diethylamino) phenyl)-
Ethenyl group, (4-morpholinophenyl) -ethenyl group, (4-piperidinophenyl) -ethenyl group, (4-
(Euroridinophenyl) -ethenyl group, (4-methoxyphenyl) -ethenyl group, (4-methylphenyl) -ethenyl group, (2- (N, N-dimethylamino) phenyl) -ethenyl group, (2-methoxyphenyl) Phenyl) -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) pyrrolyl-ethenyl group, 2
-Benzothienyl-ethenyl group, 2-benzofuranyl-
Examples include an ethenyl group and a 2- (N-methyl) indolyl-ethenyl group.

R ⁹ in the above formula (3) is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. These groups are the same meaning as the group which was described as R ⁷ above.

In the above formula (3), m is not particularly limited as long as it is an integer of 1 to 3, but from the viewpoint of easy availability of raw materials, m
Is preferably 1.

Among the groups represented by the above formula (3), preferred examples include a phenyl-ethylynyl group,
(4- (N, N-dimethylamino) phenyl) -ethynyl group, (4- (N, N-diethylamino) phenyl)-
Ethynyl group, (4-morpholinophenyl) -ethynyl group, (4-piperidinophenyl) -ethynyl group, (4-
(Euroridinophenyl) -ethynyl group, (4-methoxyphenyl) -ethynyl group, (4-methylphenyl) -ethynyl group, (2- (N, N-dimethylamino) phenyl) -ethynyl group, (2-methoxyphenyl) Phenyl) -ethynyl group, 2-thienyl-ethynyl group, 2-furyl-ethynyl group, 2- (N-methyl) pyrrolyl-ethynyl group, 2
-Benzothienyl-ethyl group, 2-benzofuranyl-ethynyl group, 2- (N-methyl) indolyl-ethynyl group and the like.

The substituted or unsubstituted aryl group or substituted or unsubstituted heteroaryl group as R ³ and R ⁴ has the same meaning as the group described as R ⁷ .

The alkyl group as R ³ and R ⁴ is
It is synonymous with the groups described as R ¹ described above.

When R ³ and R ⁴ are taken together to form an aliphatic hydrocarbon ring, the aliphatic hydrocarbon ring is not particularly limited, but may be an aliphatic hydrocarbon ring having 5 to 12 carbon atoms. Hydrocarbon rings are preferred. Specific examples of suitable rings include an adamantylidene ring, a bicyclononylidene ring, and a norbornylidene ring.

Further, as the substituted aliphatic hydrocarbon ring in which these are substituted, one or more hydrogen atoms are
It is substituted by a substituent such as an alkyl group, an alkoxy group, an aryl group, a hydroxyl 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 suitable alkoxy groups include a methoxy group, an ethoxy group, and a propoxy group. Specific examples of suitable aryl groups include a phenyl group and a naphthyl group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

When R ³ and R ⁴ are taken together to form an aromatic hydrocarbon ring, the aromatic hydrocarbon ring is not particularly limited, but may be an aromatic ring having 6 to 12 carbon atoms. Hydrocarbon rings are preferred. Specific examples of suitable rings include a fluorene ring.

Further, as the substituted aromatic hydrocarbon ring in which these are substituted, one or more hydrogen atoms are
Examples include those substituted with the same substituents as in the case of the substituted aliphatic hydrocarbon ring formed by combining R ³ and R ⁴ .

In addition, at least one of R ³ and R ⁴ is
It is preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, or a group having these groups.

Further, at least one of R ³ and R ⁴ is particularly preferably any one of the following groups (i) to (ix).

(I) a substituted aryl or substituted heteroaryl group having a substituted amino group as a substituent; (ii) a substituted or heteroaryl group having a nitrogen atom as a heteroatom and bonding the nitrogen atom to the aryl or heteroaryl group. A substituted aryl group or a substituted heteroaryl group having an unsubstituted heterocyclic group as a substituent; (iii) an aromatic hydrocarbon ring or an aromatic heterocyclic ring fused to the substituted or unsubstituted heterocyclic group in the above (ii). A substituted aryl group or a substituted heteroaryl group having a condensed heterocyclic group as a substituent; (iv) Formula (2) wherein R ⁷ is a substituted aryl group or a substituted heteroaryl group having a substituted amino group as a substituent. (V) a substituted or unsubstituted group in which R ⁷ has a nitrogen atom as a heteroatom and the nitrogen atom is bonded to an aryl group or a heteroaryl group; A group represented by the formula (2) that is a substituted aryl group or a substituted heteroaryl group having a heterocyclic group as a substituent; (vi) R ⁷ is an aromatic group substituted or unsubstituted in the above (v). A group represented by the formula (2), which is a substituted aryl group or a substituted heteroaryl group having, as a substituent, a condensed heterocyclic group in which a hydrocarbon ring or an aromatic heterocycle is condensed; (vii) R ⁹ substitutes a substituted amino group A group represented by the formula (3), which is a substituted aryl group or a substituted heteroaryl group as a group; (viii) R ⁹ has a nitrogen atom as a hetero atom, and the nitrogen atom is bonded to an aryl group or a heteroaryl group; Formula (4) which is a substituted aryl group or a substituted heteroaryl group having a substituted or unsubstituted heterocyclic group as a substituent
In group represented; (ix) R ⁹ is a substituted aryl having a fused heterocyclic group in which the aromatic hydrocarbon ring or aromatic heterocycle substituted or unsubstituted heterocyclic group in the (viii) condensed as a substituent A group represented by the formula (4), which is a group or a substituted heteroaryl group; among them, the groups (i) to (iii) are particularly preferable.

In the substituted aryl groups in the above (i) to (iii), the position where the substituent is substituted is not particularly limited, and the total number thereof is not particularly limited, but the substitution position is that the aryl group is a phenyl group. In such a case, substitution at the 3- or 4-position is preferred, and the number is preferably 1. Specific examples of suitable substituted aryl groups include a 4- (N, N-dimethylamino) phenyl group, a 4- (N, N-diethylamino) phenyl group,
4- (N, N-diphenylamino) phenyl group, 4-morpholinophenyl group, 4-piperidinophenyl group, 3-
(N, N-dimethylamino) phenyl group and the like can be mentioned.

In the substituted heteroaryl groups in the above (i) to (iii), the position at which the substituent is substituted is not particularly limited, and the total number thereof is not particularly limited, but the number is preferably 1. Specific examples of preferable examples of the substituted heteroaryl group include 4- (N,
N-dimethylamino) thienyl group, 4- (N, N-diethylamino) furyl group, 4- (N, N-diphenylamino) thienyl group, 4-morpholinopyrrolinyl group, 6-piperidinobenzothienyl group, 6 -(N, N-dimethylamino) benzofuranyl group and the like.

Further, the above formulas (iv) to (vi) are represented by the formula (2).
In the group to be obtained, R in the formula (2) ⁷Are the above (i) to
(Iii) a substituted aryl group or a substituted heteroaryl group;
It is synonymous. Suitable as the group represented by the formula (2)
For example, (4- (N, N-dimethylamino) phenyl
Enyl) -ethenyl group, (4- (N, N-diethylamido)
No) phenyl) -ethenyl group, (4-morpholinophenyl)
L) -ethenyl group, (4-piperidinophenyl) -ethe
A nyl group, a (4-eurolidinophenyl) -ethenyl group,
(2- (N, N-dimethylamino) phenyl) -etheni
Group, (4- (N, N-dimethylamino) phenyl)-
1-methylethenyl group, (4- (N, N-dimethylamido)
No) phenyl) -1-fluoroethenyl group and the like
Can be.

In the groups represented by the formula (3) in the above (vii) to (ix), R ⁹ in the formula (3) is the same as the above (i) to ( ⁹ ).
It has the same meaning as the substituted aryl group or substituted heteroaryl group in (iii). Preferred examples of the group represented by the formula (3) include a (4- (N, N-dimethylamino) phenyl) -ethynyl group, a (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.

R ⁵ and R in the above general formula (1)
⁶ each independently represent a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, an allyl group, a cyano group, a halogen atom, an alkoxy group, an aralkoxy group; Group, alkoxycarbonyl group, hydroxycarbonyl group, substituted or unsubstituted aminocarbonyl group, or aralkyl group. R ⁵ and R ⁶ are, in addition to these groups, R ⁵ and R ^{6 taken} together to form an oxo group, a substituted or unsubstituted aliphatic hydrocarbon ring, or a substituted or unsubstituted heterocyclic ring. It may constitute a group.

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

As the substituted alkyl group, an alkoxy group,
It is substituted with an aryl group, a hydroxyl group or a halogen atom. Specific examples of suitable alkoxy groups include a methoxy group, an ethoxy group, and a propoxy group.
Specific examples of suitable aryl groups include a phenyl group and a naphthyl group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The unsubstituted cycloalkyl group is not particularly limited, but is generally preferably an unsubstituted cycloalkyl group having 5 to 12 carbon atoms. Specific examples of suitable unsubstituted cycloalkyl groups include an adamantylidene group, a bicyclononylidene group, and a norbornylidene group.

Examples of the substituted cycloalkyl group include those in which one or more hydrogen atoms of the unsubstituted cycloalkyl group are substituted with the same substituents as in the case of the alkyl group and the substituted alkyl group.

The alkoxycarbonyl group is not particularly limited, but is generally preferably an alkoxycarbonyl group having 2 to 15 carbon atoms. Specific examples of suitable alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, and phenoxycarbonyl.

The substituted aminocarbonyl group is not particularly limited, but is preferably an alkylaminocarbonyl group, a dialkylaminocarbonyl group, an arylaminocarbonyl group or a diarylaminocarbonyl group. Specific examples of suitable substituted aminocarbonyl groups include methylaminocarbonyl, ethylaminocarbonyl, phenylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, and diphenylaminocarbonyl.

Incidentally, a substituted or unsubstituted aryl group,
Halogen atom, an alkoxy group, the aralkoxy group and aralkyl group, the same meanings as the groups described as R ¹ described above.

When R ⁵ and R ⁶ together form an unsubstituted aliphatic hydrocarbon ring, the unsubstituted aliphatic hydrocarbon ring is not particularly limited, but may be a 3- to 7-membered ring. Or a ring obtained by condensing an aromatic hydrocarbon ring such as a benzene ring or a naphthalene ring or a heterocyclic ring such as a pyridine ring with the aliphatic hydrocarbon ring. Specific examples of suitable unsubstituted aliphatic hydrocarbon rings include cyclopropylidene, cyclopennylidene, cyclohexanylidene, cycloheptanylidene, adamantylidene,
Bicyclononylidene, norbornylidene, indenylidene, fluorenylidene, benzofluorenylidene and the like can be mentioned.

Further, as the substituted aliphatic hydrocarbon ring substituted with one or more of these, one or more hydrogen atoms are
It is substituted with an alkyl group, an alkoxy group, an aryl group, a hydroxyl 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 suitable alkoxy groups include a methoxy group, an ethoxy group, and a propoxy group. Specific examples of suitable aryl groups include a phenyl group and a naphthyl group. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

When R ⁵ and R ⁶ together form an unsubstituted heterocyclic ring, the unsubstituted heterocyclic ring includes:
Although not particularly limited, a 5- to 7-membered heterocyclic ring containing 1 to 5 oxygen atoms, sulfur atoms or nitrogen atoms, or an aromatic hydrocarbon ring such as a benzene ring or a naphthalene ring or a pyridine ring in the heterocyclic ring Are preferably condensed with a heterocyclic ring. Specific examples of suitable unsubstituted heterocycles include oxolane, pyrrolidine, piperazine, pyran, thiolysine and the like.

Further, the substituted heterocyclic ring substituted with one or more of the above-mentioned substituted heterocyclic rings has the above-mentioned R
Those substituted with the same substituent as in the case of the substituted aliphatic hydrocarbon ring formed by combining ⁵ and R ⁶ can be mentioned.

The above R ⁵ and R ⁶ together form an aliphatic hydrocarbon ring in which aromatic hydrocarbon rings such as an indenylidene group, a fluorenylidene group and a benzofluorenylidene group are condensed. Particularly preferred.

In the general formula (1), X is an oxygen atom,
Sulfur atom, ethylidene group, general formula (4)

[0074]

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(Wherein R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, Group, a cyano group, a halogen atom, an alkoxy group, an aralkoxy group, an alkoxycarbonyl group, a hydroxycarbonyl group, a substituted or unsubstituted aminocarbonyl group, or an aralkyl group, or R ¹⁰ and R ¹¹ together , An oxo group, a substituted or unsubstituted aliphatic hydrocarbon ring which may be condensed with an aromatic hydrocarbon ring or a heterocyclic ring, or a substituted or unsubstituted which may be condensed with an aromatic hydrocarbon ring or a heterocyclic ring Or a heterocyclic ring of the following formula (5):

[0076]

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(In the formula, R ¹² is a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, an allyl group, or a cyano group.) It is.

In the general formula (4), R ¹⁰ and R ¹¹ are
The same meaning as R ⁵ and R ⁶ described above.

In R ¹² in the general formula (5), a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstituted aryl group are the same as R ⁵ and R ⁶ described above. Synonymous with the groups described.

The chromene compound suitable in the present invention is
In the formula (1), X is a chromene compound represented by the general formula (4).

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

[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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The chromene compound represented by the above 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.
It can be confirmed by such means as (c).

(A) Proton nuclear magnetic resonance spectrum ( ¹
H-NMR), δ 5.0 to 9.0.
A peak based on an aromatic proton and an alkene proton appears at around ppm, and a peak based on an alkyl group and an alkylene group proton appears around 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) by measuring the ¹³ C- nuclear magnetic resonance spectrum ⁽¹³ C-NMR), the peak based on the carbons of an aromatic hydrocarbon group near δ110~160ppm, δ80~140
A peak based on carbon of alkene and alkyne appears around ppm, and a peak based on carbon of alkyl group and alkylene group appears around δ20-80.

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 (6)

[0091]

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(However, R ¹ , R ² , R ³ , R ⁴ , X, p, q
Has the same meaning as defined in general formula (1). ) And a naphthol derivative represented by the general formula (7)

[0093]

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

The method for synthesizing the compounds represented by the general formulas (6) and (7) is not particularly limited. The reaction between the compound represented by the general formula (6) and the compound represented by the general formula (7) in the presence of an acid catalyst is performed as follows. That is, the reaction ratio of these two compounds is
Adopted from a wide range, but generally from 1:10 to 10:
It is selected from the range of 1 (molar ratio). As the acid catalyst, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acidic alumina and the like are used, and the compound represented by the general formula (6) and the compound represented by the general formula (7) (reaction substrate) Is used in the range of 0.1 to 10 parts by weight based on the total of 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 (8)

[0097]

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(Wherein R ¹ , R ² , X, p and q have the same meanings as defined in formula (1)) and a hydroxyfluorenone derivative represented by formula (7)

[0099]

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(Wherein R ³ and R ⁴ have the same meanings as defined in the general formula (1)). A propargyl alcohol derivative represented by the following formula (9) is reacted in the presence of an acid catalyst.

[0101]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , p, q and X have the same meanings as defined in the general formula (1)). Equation (9)
A compound represented by the following formula was added to a Grignard reagent at -30 to 70 ° C.
For 10 minutes to 4 hours to obtain a chromene derivative represented by the general formula (1).

The reaction between the compound represented by the general formula (8) and the compound represented by the general formula (7) in the presence of an acid catalyst is carried out as follows. That is, these two
The reaction ratio of the species compounds is adopted from a wide range,
Generally, it is selected from the range of 1:10 to 10: 1 (molar ratio). As the acid catalyst, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acidic alumina and the like are used, and the compound represented by the general formula (6) and the compound represented by the general formula (7) (reaction substrate) Is used in the range of 0.1 to 10 parts by weight based on the total of The reaction temperature is
Usually, the temperature is preferably from 0 to 200 ° C. As the solvent, an aprotic organic solvent such as N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, benzene, toluene and the like are used.

The reaction between the compound represented by the general formula (9) and the Grignard reagent obtained by the above reaction is carried out as follows. That is, the reaction ratio of these two compounds is adopted from a wide range, but is generally 1: 1.
It is selected from the range of 0 to 10: 1 (molar ratio). The reaction temperature is usually preferably −20 to 60 ° C., and as the solvent,
An anhydrous aprotic organic solvent such as tetrahydrofuran, ether, toluene and the like is used.

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.

Further, chromene derivatives of the general formula (1) having various structures can be obtained by using other known organic chemical reactions.

The chromene compound represented by the above 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.

The photochromic action of the compound of the general formula (1) shows the same 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, polyethyl methacrylate, polystyrene, polyacrylonitrile,
Polyvinyl alcohol, polyacrylamide, poly (2
-Hydroxyethyl methacrylate), thermoplastic resins such as 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 them in the resin, or dissolving the chromene compound in the polymerizable monomer, then adding a polymerization catalyst and polymerizing with heat or light. And dispersing the resin in the resin by dyeing the surface of the thermoplastic resin and the thermosetting resin with a chromene compound.

The chromene compound of the present invention can be widely used as a photochromic material. For example, various memory materials in place of silver salt photosensitive materials, copying materials, photosensitive materials for printing, storage materials for cathode ray tubes, photosensitive materials for lasers, holographic materials. 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.

[0113]

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.

[0114]

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 naphthol derivatives

[0116]

Embedded image 1.0 g (2.5 mmol) and the following propargyl alcohol derivative

[0117]

Embedded image

0.81 g (2.8 mmol) was dissolved in 50 ml of toluene, and 0.03 g of p-toluenesulfonic acid was added, followed by stirring at room temperature for 1 hour. After the reaction, the solvent was removed, and the product was purified by chromatography on silica gel to give a pale yellow powdery product (0.83 g).
I got Yield was 49%.

The product had an elemental analysis of C87.68.
%, H 5.26%, N 2.13%, C ₄₉ H ₃₅ N
Is a calculated value of _{O 2 C87.86%, H5.27%,} N
This was in very good agreement with 2.09%.

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 3.
2 originated from methylene proton at benzyl position near 7 ppm
H peak, 25H based on an aromatic proton and an alkene proton near δ 5.6 to 9.0 ppm
Was shown.

Further, when the ¹³ C-nuclear magnetic resonance spectrum was measured, 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 alkyl carbon was found at about 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.

[0123]

Embedded image Example 2 The following naphthol derivative

[0124]

Embedded image The following acetylene derivatives

[0125]

Embedded image The following chromene compound obtained in the same manner as in Example 1 from

[0126]

Embedded image

1.0 g (1.8 mmol) was dissolved in 50 ml of anhydrous tetrahydrofuran, and 2-biphenylmagnesium bromide (5.4 mmol) prepared in advance was dissolved.
l) An anhydrous tetrahydrofuran solution was added dropwise at room temperature, and 5
The mixture was heated and stirred at 0 ° C. for 1 hour. The reaction solution was poured into water (10 ml) and extracted with toluene. After washing with water, the solvent was distilled off, and the product was separated and purified by silica column chromatography to obtain 0.90 g of the following yellow chromene compound. The yield was 58%.

[0128]

Embedded image The elemental analysis value of this product was 85.70% for C and 5.1 for H.
1% and N 2.13%, which corresponded very well to the calculated values of C ₆₁ H ₄₅ NO ₄ , C 85.59%, H 5.30%, and N 1.64%.

Further, when the proton nuclear magnetic resonance spectrum was measured, the peak of 8H based on the methylene proton of the morpholino group, δ2.
A peak of 2H based on a hydroxyl group around 6 ppm, δ5.6 to
A peak around 35 ppm based on an aromatic proton and an alkene proton was observed at around 9.0 ppm.

Example 3 0.50 g (0.5 mm) of the chromene compound obtained in Example 2
ol) in 50 ml of toluene, add 1 drop of sulfuric acid,
The mixture was refluxed for 1 hour. After washing with water, toluene was distilled off, and the product was separated and purified by silica column chromatography to obtain 0.31 g of the following white chromene compound. The yield was 76%.

[0131]

Embedded image

The elemental analysis value of this product was C89.07.
%, H 5.14%, N 1.89%, and C ₆₁ H ₄₁ N
89.35% of calculated values of O ₂ , 5.04% of H, N
This was in very good agreement with 1.71%.

Further, when the proton nuclear magnetic resonance spectrum was measured, an 8H peak 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 33H based on an aromatic proton and a proton of an alkene was shown around 6 to 9.0 ppm.
The structure of the product was confirmed by NMR and elemental analysis.

Examples 4 to 10 The chromene compounds shown in Table 1 were synthesized in the same manner as in Example 1 or Example 2. 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.

[0135]

[Table 1]

[0136]

[Table 2]

[0137]

[Table 3]

Examples 11 to 20, Comparative Examples 1 and 2 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, -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 and 245 nm = 24 μm.
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): λmax after color development of this polymer was determined with 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.

Initial coloring {ε (0)}: Absorbance at the maximum absorption wavelength in a state where light is not irradiated. For example, in an optical material such as an eyeglass lens, it can be said that the lower this value is, the more excellent the photochromic property is.

Color density {ε (120) −ε (0)}:
Difference between absorbance {ε (120)} after irradiation with light for 120 seconds and the above {ε (0)} at the maximum absorption wavelength.
It can be said that the higher this value is, the better the photochromic property is.

Fading speed [t1 / 2 (min.)]: 120
After irradiating the light for 2 seconds, when the light irradiation is stopped, the absorbance of the sample at the maximum absorption wavelength becomes Δε (120) −ε.
(0) Time required to decrease to 1/2 of｝. It can be said that the shorter this time is, the better the photochromic property is.

Residual rate (%) = ｛(A ₀ / A ₂₀₀ ) × 10
0 °: The following deterioration promotion test was performed to evaluate the durability of color development by light irradiation. That is, the obtained polymer (sample) was accelerated and degraded for 200 hours using a xenon weather meter X25 manufactured by Suga Test Instruments Co., Ltd. Thereafter, the color density was evaluated before and after the test, and the color density (A ₀ ) before the test and the color density (A ₂₀₀ ) after the test were measured.
The value of {(A ₀ / A ₂₀₀ ) × 100} is defined as the residual rate (%),
This was used as an index of color development durability. The higher the residual ratio, the higher the durability of coloring.

Degree of color change (ΔYI) = YI (200)
-YI (0): In order to evaluate the durability of the color tone without light irradiation, the color difference of the sample before and after the above-mentioned deterioration promotion test was measured using a color difference meter (SM-4) manufactured by Suga Test Instruments Co., Ltd. It was measured. The degree of change in coloring due to deterioration is calculated as the value of degree of coloring ΔY
The value of the degree of coloration before the test {YI (0)} from I (200)}
, And the difference {YI} was determined, and the durability was evaluated. △ Y
The smaller the value of I, the higher the durability of the color tone without light irradiation.

Examples 2 to 1 were used as chromene compounds.
A photochromic polymer was obtained in the same manner as described above, except that the compound obtained in Step No. 0 was used, and the properties were evaluated. The results are summarized in Table 3.

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

[0148]

Embedded image

[0149]

Embedded image

A photochromic polymer was obtained in the same manner using the compound represented by the formula (1), and the characteristics were evaluated. Table 4 shows the results.

[0151]

[Table 4]

[0152]

[Table 5]

Example 1 using the chromene compound of the present invention
In 1 to 20, the photochromic polymer is Comparative Example 1,
As compared with No. 2, all three effects of the fading speed, the coloring at the time of deterioration and the durability of the photochromic property are excellent.

Claims (3)

[Claims] [Claim 1] The following general formula (1) Wherein R ¹ and R ² are each independently 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 A substituted or unsubstituted heterocyclic group having a nitrogen atom as a hetero atom and a nitrogen atom bonded to a benzene ring, or a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the heterocyclic group A cyclic group, p and q are integers of 0 to 3,
R ³ and R ⁴ are each independently the following formula (2): (Wherein, R ⁷ is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, R ⁸
Is a hydrogen atom, an alkyl group, or a halogen atom,
n is an integer of 1 to 3), a group represented by the following formula (3): (Wherein, R ⁹ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and m is an integer of 1 to 3), a substituted or unsubstituted aryl group Or a substituted or unsubstituted heteroaryl group, or an alkyl group, or R ³ and R ⁴ together form a substituted or unsubstituted aliphatic hydrocarbon ring, or a substituted or unsubstituted aromatic hydrocarbon R ⁵ and R ⁶ may each independently represent a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group , Allyl group, cyano group, halogen atom, alkoxy group, aralkoxy group, alkoxycarbonyl group, hydroxycarbonyl group, substituted or unsubstituted aminocarbonyl group, or Or an aralkyl group, taken together with R ⁵ and R ^6, oxo group may also be constituted substituted or unsubstituted aliphatic hydrocarbon ring, or a substituted or unsubstituted heterocyclic ring, X is , An oxygen atom, a sulfur atom, an ethylidene group, a compound represented by the following formula (4): (Wherein, R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, an allyl group, a cyano group, Group, a halogen atom, an alkoxy group, an aralkoxy group, an alkoxycarbonyl group, a hydroxycarbonyl group, a substituted or unsubstituted aminocarbonyl group, or an aralkyl group, or R ¹⁰ and R ¹¹ together form an oxo group, Which may constitute a substituted or unsubstituted aliphatic hydrocarbon ring or a substituted or unsubstituted heterocyclic ring), or the following formula (5): (Wherein, R ¹² is a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, an allyl group, or a cyano group)] Chromene compounds. 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.