JP2000229975A - Chromene compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel chromene compound that has high color-fading rate, show reduced discoloration on its deterioration with high photochromic durability and is useful in photochromic lenses and the like. SOLUTION: This compound is represented by formula I R1 and R2 are each an alkyl, an alkoxy, an aralkoxy, a (substituted) amino, a (substituted) aryl or the like; (a) and (b) are each 0-3; R3 and R4 are each a group of formula II [R6 is a (substituted) aryl, a (substituted) hetero aryl; R7 is H, a halogen, an alkyl or the like; (n) is 1-3], a group of formula III (R8 is R6; (m) is (n), a (substituted) aryl, a (substituted) hetero aryl; and R5 is H, an alkyl}, typically the compound of formula IV. The compound of formula I is prepared, for example, by allowing a hydroxycarbazole derivative of formula V to react with a propargyl alcohol derivative of formula VI in a solvent, for example, tetrahydrofuran or the like in the presence of acid catalyst, for example, sulfuric acid or the like.

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 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 98/42
No. 693 discloses a chromene compound represented by the following formula (A).

[0004]

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[0005] However, this chromene compound has a low color fading rate and is greatly colored when further deteriorated.

[0006]

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.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been proposed in order to achieve the above object, and the novel chromene compound has a high fading speed, has little coloring 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)

[0009]

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[Wherein each of R ¹ and R ² may be different from each other and has an alkyl group, an alkoxy group, an aralkoxy group, an amino group, a substituted amino group, a nitrogen atom as a hetero atom, and the nitrogen atom Or a substituted or unsubstituted heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is condensed to the heterocyclic group, a cyano group, a substituted or unsubstituted substituted aryl group, a halogen atom or an aralkyl radical, a indicating the number of substituents of R ¹ is an integer of 0 to 3, R ²
B represents an integer of 0 to ³ , and each of R ³ and R ⁴ may be different from each other in the following formula (2)

[0011]

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(Wherein, R ⁶ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, R ⁷ is a hydrogen atom, an alkyl group or a halogen atom, and n is an integer of 1 to 3) And a group represented by the following formula (3):

[0013]

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Wherein R ⁸ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and m is an integer of 1 to 3; R ⁵ is a hydrogen atom or an alkyl group. ] Is a chromene compound represented by the formula:

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

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula (1), R ¹ ,
R ² may be different from each other, and may have an alkyl group, an alkoxy group, an aralkoxy group, a substituted amino group, or a substituted group having a nitrogen atom as a heteroatom and the nitrogen atom being bonded to a carbazole ring or a naphthalene ring. Or an unsubstituted heterocyclic group, a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the heterocyclic group, a cyano group, a substituted or unsubstituted aryl group, a halogen atom or an aralkyl 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,
Examples include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a t-butyl group. The alkoxy group is not particularly limited, but is generally preferably an alkoxy group having 1 to 5 carbon atoms. Specific examples of suitable alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and t-butoxy groups. The aralkoxy group is not particularly limited, but is preferably an aralkoxy group having 6 to 10 carbon atoms. Specific examples of suitable aralkoxy groups include a phenoxy group and a naphthoxy group. The 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,
Examples thereof include a phenylamino group, a dimethylamino group, a diethylamino group, and a diphenylamino group. A substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and the nitrogen atom bonded to a carbazole ring or a naphthalene 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. In the ring, a hetero atom may be present in addition to the nitrogen atom bonded to the carbazole ring or the naphthalene ring, and the hetero atom is not particularly limited, but an oxygen atom, a sulfur atom, a nitrogen atom and the like are preferable. It is. A substituted or unsubstituted heterocyclic group having a suitable nitrogen atom as a heteroatom and the nitrogen atom bonded to a carbazole ring or a naphthalene ring, or an aromatic hydrocarbon ring or an aromatic heterocyclic ring in the heterocyclic group. Specific examples of the condensed condensed heterocyclic group include a morpholino group, a piperidino group, a pyrrolidinyl group, a piperazino group, an N-methylpiperazino group, an indolinyl group, and the like. 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. Examples of the substituent of the aryl group include the same alkyl group, alkoxy group, aryl group, substituted amino group as the groups described as R ¹ and R ² , a nitrogen atom as a hetero atom and a carbazole ring or naphthalene. Examples thereof include a substituted or unsubstituted heterocyclic group bonded to a ring, a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is condensed 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 representing the number of substitutions of R ¹ is 0
-3. The position where R ¹ is bonded is not particularly limited, and the total number thereof is not particularly limited, but the total number of R ¹ is preferably 2 or less. B representing the number of substitutions of R ² is 0 to 3;
Is an integer. The position where R ² is bonded is not particularly limited,
Although the total number is not particularly limited, the total number of R ² is preferably 2 or less.

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

[0018]

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Wherein R ⁷ is a hydrogen atom, an alkyl group or a halogen atom, R ⁶ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and n is an integer of 1-3 And a group represented by the following formula (3):

[0020]

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Wherein R ⁸ 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.

R ⁷ 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.

R ⁶ 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, but is preferably an aryl group having 6 to 10 carbon atoms. Specific examples include a phenyl group and a naphthyl group. Examples of the substituent of the aryl group include the above-described R ¹ and R ²
The groups having the same meanings as those described above are applied. Preferably, a substituted amino group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a hetero atom and the nitrogen atom being bonded to an aryl group, or an aromatic hydrocarbon ring or an aromatic heterocyclic group as the heterocyclic group. Examples include a fused heterocyclic group in which rings are fused, an alkoxy group, and an alkyl group. The position at which the substituent is bonded is not particularly limited, and the total number thereof is not particularly limited, but when the aryl group is a phenyl group, the 3-position or the 4-position is used.
Position or naphthyl group, the 4-position or 6-position is preferred.
The heteroaryl group described above is not particularly limited,
A heteroaryl group having 4 to 12 carbon atoms is preferred. Illustrative examples include a thienyl group, a furyl group, a pyrrolinyl group,
Examples include 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 amino group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a hetero atom and a bond between the nitrogen atom and the heteroaryl group, or an aromatic hydrocarbon ring or an aromatic group as the heterocyclic group. Examples include a fused heterocyclic group in which a heterocyclic ring is fused, an alkoxy group, and an alkyl group. The position where the substituent is bonded is not particularly limited, and the total number is not particularly limited.

In the above formula (2), n is an integer of 1 to 3. From the viewpoint of obtaining raw materials, it is preferable that n is 1.

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 ⁸ 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 or a substituted or unsubstituted heteroaryl group In a group as defined for group described as R ⁶ above.

In the above formula (3), m is an integer of 1 to 3, and m is preferably 1 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 that of R ⁶ described above.

At least one of R ³ and R ⁴ is preferably 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 heteroatom, wherein the nitrogen atom is 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 the ring group or the heterocyclic group; R ⁶ 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. groups represented by formula (2) is an aryl or heteroaryl group having a substituent group; or R ⁸ is a substituted amino group, the nitrogen atom and ants have 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, a nitrogen atom as a hetero atom and the nitrogen atom being bonded to an aryl group, or an aromatic hydrocarbon ring or an aromatic heterocyclic group; The aryl group having a condensed heterocyclic group in which a ring is condensed as a substituent is not particularly limited at the position where the substituent is substituted, and the total number thereof is not particularly limited, but the substitution position is 3 when the aryl group is a phenyl group. It is preferably substituted at the 4- or 4-position, and the number is preferably 1. Suitable substituted amino group, substituted or unsubstituted heterocyclic group having a nitrogen atom as a hetero atom and bonding the nitrogen atom to an aryl group, or an aromatic hydrocarbon ring or an aromatic heterocyclic ring as the heterocyclic group Specific examples of an aryl group having as a substituent a condensed heterocyclic group fused with a 4- (N, N-dimethylamino) phenyl group,
4- (N, N-diethylamino) phenyl group, 4-
(N, N-diphenylamino) phenyl group, 4-morpholinophenyl group, 4-piperidinophenyl group, 3-
(N, N-dimethylamino) phenyl group and the like.

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 a heteroaryl group, or an aromatic hydrocarbon ring or an aromatic In the heteroaryl group having a condensed heterocyclic group in which a heterocyclic ring is condensed as a substituent, the position where the substituent is substituted is not particularly limited, and the total number thereof is not particularly limited, but the number is preferably 1. A substituted amino group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and a nitrogen atom bonded to a heteroaryl group, or an aromatic hydrocarbon ring or an aromatic heterocyclic group as the heterocyclic group. Specific examples of a heteroaryl group having a fused heterocyclic group in which a ring is fused as a substituent include 4-
(N, N-dimethylamino) thienyl group, 4- (N, N
-Diethylamino) furyl group, 4- (N, N-diphenylamino) thienyl group, 4-morpholinopyrrolinyl group,
Examples include a 6-piperidinobenzothienyl group and a 6- (N, N-dimethylamino) benzofuranyl group.

R ⁶ is a substituted or unsubstituted heterocyclic group in which R ⁶ is a substituted amino group or a nitrogen atom as a heteroatom and the nitrogen atom is bonded to an aryl group or a heteroaryl group; In the 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 heterocycle is condensed, R ⁶ is the same as R ³ and R ⁴ described above. A substituted or unsubstituted heterocyclic group having at least one substituted amino group, 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; 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 a hydrocarbon ring or an aromatic heterocycle is condensed.

R ⁶ is a substituted amino group or 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; Examples of a suitable group represented by the formula (2), which is an aryl group or a heteroaryl group having a condensed heterocyclic group in which a hydrocarbon ring or an aromatic heterocyclic ring is condensed as a substituent, include (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) -ethenyl group, (4- (N, N-dimethylamino)
Phenyl) -1-methylethenyl group, (4- (N, N-
Dimethylamino) phenyl) -1-fluoroethenyl group and the like.

R ⁸ 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 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 heterocycle is condensed, R ⁸ is the same as R ³ and R ⁴ described above. A substituted or unsubstituted heterocyclic group having at least one substituted amino group, 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; 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 a hydrocarbon ring or an aromatic heterocycle is condensed.

R ⁸ is a substituted or unsubstituted heterocyclic group in which R ⁸ is a substituted amino group or a nitrogen atom as a heteroatom and the nitrogen atom is bonded to an aryl group or a heteroaryl group; Examples of a suitable 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, include (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.

In the general formula (1), R ⁵ is a hydrogen atom or an alkyl group. The alkyl group is not particularly limited, but is preferably an alkyl group having 1 to 5 carbon atoms. Specific examples of suitable groups include a methyl group, an ethyl group, a propyl group, and a butyl group.

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

[0039]

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Wherein R ⁹ is an alkyl group having 1 to 5 carbon atoms, and R ¹⁰ has an alkyl group, an alkoxy group, an aralkoxy group, a substituted amino group, and a nitrogen atom as a hetero atom. A substituted or unsubstituted heterocyclic group bonded to a naphthalene ring, or a fused heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to the heterocyclic group, a cyano group, a substituted or unsubstituted aryl group , A halogen atom or an aralkyl group, b is an integer of 0 to 3,
R ¹¹ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and R ¹² is represented by the following formula (5)

[0041]

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Wherein R ⁷ is a hydrogen atom, an alkyl group or a halogen atom, and R ⁶ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. Equation (6)

[0043]

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Wherein R ⁸ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl And R ¹³ is a hydrogen atom or an alkyl group. ] Is a chromene compound represented by the formula:

More preferably, R ¹¹ 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 or 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 heterocycle is condensed to a ring group, or R ¹² has a substituted amino group or a nitrogen atom as 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. groups represented by the formula (5) having an aryl group or a heteroaryl group having a group as R ^6; substituted amino group, the nitrogen atom and the arylene having a nitrogen atom as a hetero atom A substituted or unsubstituted heterocyclic group bonded to a 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 heterocyclic ring is fused to the heterocyclic group; or A group represented by the formula (6) having a heteroaryl group as R ⁸ ;
Or 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 an aromatic group on the heterocyclic 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 a group heterocyclic ring is condensed.

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

[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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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 ( ¹
H-NMR), δ11-12pp
a peak based on the proton of the NH group of the carbazole group near m, a peak based on an aromatic proton and an alkene proton near δ 5.0 to 9.0 ppm, δ
A peak based on the protons of the alkyl group and the alkylene group appears around 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), δ110-160p
pm, a peak based on the carbon of the aromatic hydrocarbon group, δ
A peak based on the carbon of the alkene and alkyne appears around 80 to 140 ppm, and a peak based on the carbon of the alkyl group and the alkylene group appears around δ 20 to 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.

The following general formula (7)

[0058]

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(Wherein R ¹ , R ² , R ⁵ , a and b have the same meanings as defined in the general formula (1)) and a hydroxycarbazole derivative represented by the general formula (8)

[0060]

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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 (7) and (8) is not particularly limited. The hydroxycarbazole derivative represented by the general formula (7) is obtained, for example, by reacting 3-bromo-9Hbenzo (1,2-a) carbazole with lithium at -78 to 10 ° C for 10 minutes to 2 hours, It can be synthesized by adding n-butylmagnesium bromide at ５０50 ° C., expanding sales for 10 minutes to 5 hours, and further blowing oxygen to react for 10 minutes to 5 hours. At this time, 3-bromo-9H benzo (1,2-
a) When 3-bromo-9H benzo (1,2-a) carbazole having substituents at the 5-, 6-, 7-, and 8-positions of carbazole is used, 5
Chromene compounds having substituents at the 6-, 6-, 7-, and 8-positions can be synthesized. The propargyl alcohol derivative represented by the general formula (8) can be synthesized, for example, by reacting a ketone derivative corresponding to the general formula (8) with a metal acetylene compound such as lithium acetylide.

The reaction between the compound represented by the general formula (7) and the compound represented by the general formula (8) 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). 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 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 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 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, 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, maleic anhydride, etc .; 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.

[0071]

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.

[0072]

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 hydroxycarbazole derivatives

[0074]

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1.0 g (0.0040 mol) of the following propargyl alcohol derivative

[0076]

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1.1 g (0.0053 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, the solvent was removed, and the product was purified by chromatography on silica gel.
I got The yield was 11%.

The product had an elemental analysis of C87.85.
%, H 5.32%, N 3.16%, O 3.67%, which is C87.84% calculated as C32H31NO,
Very good agreements were found for H 5.3%, N 3.2% and O 3.66%.

Further, when the proton nuclear magnetic resonance spectrum was measured, it was found that δ 3.8 to 4.5 p as shown in FIG.
The peak of 3H based on the proton of the N-methyl group of the carbazole ring was shown near pm, and the peak of 20H based on the aromatic proton and the alkene proton was shown near δ 5.6 to 8.4 ppm.

Further, when 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 near δ 80 to 140 ppm, and a peak based on the alkyl carbon 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.

[0082]

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

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

[Table 4]

Examples 11 to 20, Comparative Example 1 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, It was added to 5 parts of ethyl 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 / cm2 for 120 seconds to develop color, and photochromic properties were measured. The photochromic properties were expressed 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.

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.

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

After irradiating for 120 seconds at a fade rate [t1 / 2 (min.)] = 120 seconds, the absorbance of this polymer was changed to [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 ) × 100 Further, the degree of coloring before and after color development before and after deterioration was measured by a color difference meter (SM-4) manufactured by Suga Test Instruments Co., Ltd. The coloring degree before deterioration is YI (0), and the coloring degree after deterioration 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 (200) −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 10 were used as the chromene compound. The characteristics are shown in Table 3.

Further, for comparison, the following formula (A)

[0099]

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A photochromic polymer was obtained in the same manner using the compound represented by the formula (1), and the characteristics are shown in Table 3.

[0101]

[Table 5]

Example 1 using the chromene compound of the present invention
In Nos. 1 to 20, the photochromic polymer is superior to Comparative Example 1 in all three effects of the fading speed, the coloring at the time of deterioration, and the photochromic durability.

[Brief description of the drawings]

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

Claims (3)

[Claims] [Claim 1] The following general formula (1) [In the formula, each of R ¹ and R ² may be different from each other, and has an alkyl group, an alkoxy group, an aralkoxy group, an amino group, a substituted amino group, a nitrogen atom as a hetero atom, and the nitrogen atom and a carbazole ring. Or a substituted or unsubstituted heterocyclic group bonded to a naphthalene ring, or a fused heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to the heterocyclic group, a cyano group, a substituted or unsubstituted aryl group, a halogen atom or aralkyl group, R ¹
A which represents the number of substitutions of a is an integer of 0 to 3; b which represents the number of substitutions of R ² is an integer of 0 to 3; R ³ and R ⁴ may be different from each other; (2) (In the formula, R ⁶ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, R ⁷ 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 ⁸ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and m is 1
A substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, and R ⁵ is a hydrogen atom or an alkyl group. A chromene compound represented by the formula: 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.