JP2000344762A - Chromene compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject novel chromene compound that has high color- fading rate and shows excellent photochromic duration with reduced discoloration, while it is deteriorated and has a chemical structure where the 1 position of the indene ring is substituted with a spiro carbon. SOLUTION: This novel compound is represented by formula I the ring including X and Y is an aromatic hydrocarbon ring or an unsaturated heterocyclic ring; one of R1 and R2 is a condensed heterocyclic ring group and the other is H, hydroxy or the like; R3 and R4 are each a group of formula II [R7 is a (substituted) aryl or the like; R8 is H, an alkyl, a halogen; n is 1-3] or the like; R5 and R6 are each hydroxyl, alkyl or the like; p and q are each 0-3}, typically the compound of formula III. The compound of formula I is prepared, for example, by allowing a carbonyl-chromene derivative of formula IV to react with an organometallic reagent of formula V [the C and D rings are each an aromatic hydrocarbon group, a (substituted) aromatic heterocyclic ring group; Z is lithium or the like; L is chlorine or the like; W is -O-, -S-, -CO- or the like] to form a hydroxychromene derivative, followed by dehydrative ring-closure reaction under an acidic condition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel chromene compound and a use of the chromene compound.

[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] For example, PCT Patent Application Publication WO9
No. 6,14,596 discloses a chromene compound represented by the following formula (A).

[0004]

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However, this chromene compound has a low fading rate, and when used as a photochromic material for a long period of time, for example, the coloration in a state not irradiated with light (also referred to as coloring at the time of deterioration) becomes large, or the coloration during light irradiation is increased. There is a problem that the color density is reduced.

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

[0007]

Embedded image However, this chromene compound has a problem that the fading speed is slow.

[0008]

Accordingly, an object of the present invention is to further improve the photochromic properties as compared with the above-mentioned compounds, to increase the fading speed, to reduce the coloration at the time of deterioration, and to represent the above-mentioned reduction in color density. It is an object of the present invention to provide a chromene compound which hardly causes a decrease in photochromic property as described above, that is, has excellent photochromic durability.

[0009]

DISCLOSURE OF THE INVENTION The present invention has been proposed to achieve the above object, and a novel chromene compound obtained by the present inventors has a high fading speed,
Further, it has been completed based on the finding that coloring during degradation is small and that the durability of photochromic properties is excellent.

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

[0011]

Embedded image 中 In the formula, the following formula (2)

[0012]

Embedded image And a group represented by the following formula (3)

[0013]

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The groups represented by are each independently an aromatic hydrocarbon group or an unsaturated heterocyclic group, and R ¹ and R
² is, when at least one of the groups represented by the formula (2) or the formula (3) is an unsaturated heterocyclic group,
When the group satisfies the condition shown in the following (i) or (ii), and both groups represented by the formulas (2) and (3) are aromatic hydrocarbon groups, the following ( i) or (iii)
Wherein R ³ and R ⁴ are
Formula (4) below independently

[0015]

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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; A group represented by the following formula (5):

[0017]

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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 aryl group, a substituted or unsubstituted heteroaryl group, or an alkyl group;
³ and R ⁴ may together form an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring, and R ⁵ is a hydroxyl group, an alkyl group, a trifluoromethyl group, an alkoxy group, an aralkoxy group. Having an amino group, a substituted amino group, a cyano group, a nitro group, a halogen atom, an aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and a nitrogen atom as a heteroatom. A substituted or unsubstituted heterocyclic group bonded to the ring of the group represented by the formula (2), or a condensed heterocyclic group obtained by condensing an aromatic hydrocarbon ring or an aromatic heterocycle with the heterocyclic group; Is an integer of 0 to 3, and R ⁶ is a hydroxyl group, an alkyl group, a trifluoromethyl group, an alkoxy group, an aralkoxy group, an amino group, a substituted amino group, a cyano group, a nitro group, A halogen atom, an aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and a nitrogen atom as a hetero atom, and the nitrogen atom is bonded to the ring of the group represented by the formula (3). A substituted or unsubstituted heterocyclic group, or a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is condensed to the heterocyclic group, and q is an integer of 0 to 3. Chromene compound represented by｝.

Here, the [conditions of R ¹ and R ² ] in (i) to (iii) are as follows. (i) R ^1, or a substituted or unsubstituted heterocyclic group either one of R ² is the nitrogen atom a nitrogen atom as a hetero atom bonded to the carbon atom to which R ¹ and R ² are bonded, or complex- A condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is condensed to a ring group, and the other is a hydrogen atom, a hydroxyl acid group, an alkyl group, an alkoxy group, an aralkoxy group,
It is an amino group, a substituted amino group, a cyano group, a halogen atom, an aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. (ii) R ¹ and R ² are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, or R ¹ and R ² are
A substituted or unsubstituted divalent aromatic hydrocarbon group or a substituted or unsubstituted divalent unsaturated heterocyclic group and a substituted or unsubstituted divalent aromatic hydrocarbon group or a substituted or unsubstituted divalent An unsaturated heterocyclic group represented by the following formula:

[0020]

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(Wherein R ¹⁰ is a hydrogen atom or a compound having 1 to 1 carbon atoms)
An alkyl group of 10; d is an integer of 0 to 2;
Is 0, a mere bond, r is an integer of 1 to 4, and s is an integer of 2 to 6. ) To form a ring bonded through any one group selected from the groups represented by (iii) The condition (ii) is the same as the condition (ii) except that one or both of R ^{1 and} R ² are a substituted or unsubstituted heteroaryl group.

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.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula (1), the following formula (2)

[0024]

Embedded image And a group represented by the following formula (3)

[0025]

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The groups represented by are each independently an aromatic hydrocarbon group or an unsaturated heterocyclic group.

The aromatic hydrocarbon group is not particularly limited, but is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms. Examples of suitable aromatic hydrocarbon groups include one benzene ring such as a phenylene group, a naphthylene group, a phenanthrylene group, a tolylene group, a xylylene group,
And an aromatic hydrocarbon group having from 4 to 4 condensed rings.

The unsaturated heterocyclic group is not particularly limited, but may be a 5- or 6-membered ring containing oxygen, sulfur and nitrogen atoms or an unsaturated heterocyclic group in which a benzene ring is condensed. preferable. Examples of suitable unsaturated heterocyclic groups include a pyridylene group, a quinolylene group, a pyrrolylene group, a nitrogen-containing heterocyclic group such as an indolylene group, a furylene group, an oxygen-containing heterocyclic group such as a benzofurylene group, a thienylene group, and a benzothienylene group. Examples thereof include a sulfur-containing heterocyclic group.

In the general formula (1), R ¹ and R ²
Is different depending on the combination of the group represented by the formula (2) and the group represented by the formula (3).

That is, when at least one of the groups represented by the formulas (2) and (3) is an unsaturated heterocyclic group, R ¹ and R ² may be the same as the above (i) or (ii) ), And when both groups represented by the formulas (2) and (3) are aromatic hydrocarbon groups, the group represented by the formula (i) or (iii) It is a group that satisfies the conditions of If these conditions are not satisfied, one or more of the photochromic physical properties such as the color density, the fading speed, and the durability are reduced, and the effects of the present invention cannot be obtained.

[0031] Here, the condition (i), a substituted or nitrogen atom has either one of R ¹ or R ² a nitrogen atom as a hetero atom is attached to the carbon atom to which R ¹ and R ² are bonded When an unsubstituted heterocyclic group (that is, for example, “-” of “—R ¹ ” is referred to as a dangling bond, a dangling bond is present at the nitrogen atom, and “the nitrogen atom” and “R ¹ and R ¹ Or a substituted or unsubstituted heterocyclic group which is bonded to a carbon atom to which ² is bonded.), Or a fused heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the heterocyclic group And the other is a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an aralkoxy group, an amino group, a substituted amino group,
It is a cyano group, a halogen atom, an aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

A substituted or unsubstituted heterocyclic group having one of the above-mentioned groups, having a nitrogen atom as a hetero atom and bonding the nitrogen atom to a “carbon atom to which R ¹ and R ² are bonded”. Or a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocycle is condensed to the heterocyclic group, is not particularly limited, but is a 5-, 6-, or 7-membered ring having 4 to 7 carbon atoms. And / or a structure in which some carbon atoms in the ring are substituted with sulfur atoms or oxygen atoms, and 0 to 2 benzene rings are condensed in the cyclic amine structure. Are preferred.

When any of these groups has a substituent, the substituent may be a hydroxyl group, an alkyl group, an alkoxy group, an aralkoxy group, an amino group, a substituted amino group (wherein the substituent is an alkyl group). Or an aryl group), a cyano group, a halogen atom, an aralkyl group, a substituted or unsubstituted aryl group (where the substituent of the aryl group is a hydroxyl group, an alkyl group, a trifluoromethyl group,
Alkoxy group, aralkoxy group, amino group, substituted amino group, cyano group, nitro group, halogen atom, aryl group,
It is a heteroaryl group or an aralkyl group. ) Or a substituted or unsubstituted aromatic heterocyclic group (where the substituent of the aromatic heterocyclic group is a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, an aralkoxy group, an amino group,
A substituted amino group, a cyano group, a nitro group, a halogen atom, an aryl group, a heteroaryl group, or an aralkyl group. ) And the like.

A substituted or unsubstituted heterocyclic group having a nitrogen atom as a hetero atom and bonding to the "carbon atom to which R ¹ and R ² are bonded" or an aromatic hydrocarbon ring or Specific examples of suitable condensed heterocyclic groups in which an aromatic heterocyclic ring is condensed include pyrrolidinyl, piperidinyl, hexamethyleneimino, morpholino, thiomorpholino, pyrrolyl, indole, indolyl, indolyl. Group, tetrahydroquinolyl group, carbazole group and the like.

In the above condition (i), the other ^one of R ¹ and R ² is a hydrogen atom, a hydroxyl group, an alkyl group,
It is an alkoxy group, an aralkoxy group, an amino group, a substituted amino group, a cyano group, a halogen atom, an aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl 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, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a t-butyl group.

The above 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 above-mentioned substituted amino group is an alkylamino group, a dialkylamino group, an arylamino group or a diarylamino group substituted by an alkyl group or an aryl group. Groups, an ethylamino group, a phenylamino group, a dimethylamino group, a diethylamino group, a diphenylamino group, and the like.

The halogen atom is a fluorine atom,
Examples include a chlorine atom, a bromine atom or an iodine atom.

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

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

As the substituted aryl group, one or more hydrogen atoms of the unsubstituted aryl group are a hydroxyl group, an alkyl group, a trifluoromethyl group, an alkoxy group, an aralkoxy group, an amino group, a substituted amino group, In addition to a cyano group, a nitro group, a halogen atom, an aryl group, a heteroaryl group, or an aralkyl group, the compound has a nitrogen atom as a hetero atom as described above and has a dangling bond (that is, the nitrogen atom And an aryl group), or a substituted or unsubstituted heterocyclic group or a heterocyclic group substituted by a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocycle is condensed.

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 pyridyl group, a benzothienyl group, a benzofuranyl group, and a benzopyrrolinyl group. Further, as the substituent of the substituted heteroaryl group, a hydroxyl group, an alkyl group, a trifluoromethyl group, an alkoxy group, an aralkoxy group, an amino group, a substituted amino group, a cyano group, a nitro group, a halogen atom, an aryl group, A heteroaryl group or an aralkyl group, and a substituted or unsubstituted heterocyclic group having a nitrogen atom as a hetero atom and having an unbonded bond at the nitrogen atom (ie, the nitrogen atom and the heteroaryl group are bonded) Or a fused heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to the heterocyclic group.

The condition (ii) is that R ¹ and R ² are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, or
¹ and R ² together represent a substituted or unsubstituted divalent aromatic hydrocarbon group or a substituted or unsubstituted divalent unsaturated heterocyclic group and a substituted or unsubstituted divalent aromatic hydrocarbon A group or a substituted or unsubstituted divalent unsaturated heterocyclic group is represented by the following formula:

[0046]

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(Wherein, R ¹⁰ is a hydrogen atom or a group having 1 to 1 carbon atoms)
An alkyl group of 10; d is an integer of 0 to 2;
Is 0, a mere bond, r is an integer of 1 to 4, and s is an integer of 2 to 6. ) To form a ring bonded via any one group selected from the groups shown in the above.

The above-mentioned substituted or unsubstituted aryl group,
And the substituted or unsubstituted heteroaryl group is a substituted or unsubstituted heteroaryl group as defined in the above (i), wherein the “nitrogen atom is a heteroatom and the nitrogen atom is bonded to a“ carbon atom to which R ¹ and R ² are bonded ”. A substituted or unsubstituted aryl group as a group other than an unsubstituted heterocyclic group or a fused heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to the heterocyclic group, and substituted or unsubstituted Synonymous with heteroaryl group.

When R ¹ and R ^{2 in} the above condition (ii) together form a ring, a substituted or unsubstituted divalent aromatic hydrocarbon group and a substituted or unsubstituted divalent aromatic hydrocarbon group may be used. The above unsaturated heterocyclic group is one in which one hydrogen atom of the above-mentioned substituted or unsubstituted aryl group and substituted or unsubstituted heteroaryl group is changed to a bond to become divalent. R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group; t-butyl group,
A t-amyl group, a pentyl group and an n-hexyl group are preferred. Further, d is an integer of 0 to 2. When d is 0, it represents a simple bond, which means that the divalent group is directly bonded. Further, r is an integer of 1 to 4, and s is an integer of 2 to 6. In this case, a specific example of a suitable ring to be formed is as follows.

[0050]

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And one or two of the aromatic rings which are part of the ring skeleton are a 5- or 6-membered ring containing an oxygen, sulfur or nitrogen atom, or a benzene ring is condensed with these. Cyclic unsaturated heterocycles, for example, nitrogen-containing heterocycles such as pyridine, quinoline, pyrrole and indole rings;
Oxygen-containing heterocyclic groups such as a furan ring and a benzofuran ring; and structures substituted with a heterocyclic ring such as a sulfur-containing heterocyclic ring such as a thiophene ring and a benzothiophene ring.

The condition (iii) is the same as the condition (ii) except that one or both of R ^{1 and} R ² is a substituted or unsubstituted heteroaryl group.
Is the same as

R ³ and R ⁴ in the general formula (1) each independently represent the following formula (4)

[0054]

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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; A group represented by the following formula (5):

[0056]

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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).
It is a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or an alkyl group. Also, 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 (4) is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

As the substituted or unsubstituted aryl group and the substituted or unsubstituted heteroaryl group, the same groups as those described above for R ¹ and R ² in (ii) are applied. When these groups have a substituent, the position to which the substituent is bonded is not particularly limited, and the total number thereof is not particularly limited, but in the case of the substituted aryl group, when the aryl group is a phenyl group. Preferably has a substituent at the 3- or 4-position or, if it is a naphthyl group, at the 4- or 6-position.

R ⁸ in the above formula (4) 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 (4), n is an integer of 1 to 3. From the viewpoint of obtaining raw materials, n is preferably 1.

Specific examples of preferred groups among the groups represented by the above formula (4) include a phenyl-ethylenyl group and (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, (4-methoxyphenyl) -ethenyl group, (4-methylphenyl) -ethenyl group, (2- (N, N-dimethylamino) phenyl)-
An ethenyl group, a (2-methoxyphenyl) -ethenyl group,
A phenyl-1-methylethenyl group, a (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,
Examples thereof include a 2- (N-methyl) pyrrolyl-ethenyl group, a 2-benzothienyl-ethenyl group, a 2-benzofuranyl-ethenyl group, and a 2- (N-methyl) indolyl-ethenyl group.

R ⁹ in the formula (5) 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 explained as R ⁷ above.

In the above formula (5), 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.

Specific examples of preferred groups among the groups represented by the above formula (5) include a phenyl-ethynyl group and (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, (4-methoxyphenyl) -ethynyl group, (4-methylphenyl) -ethynyl group, (2- (N, N-dimethylamino) phenyl)-
An ethynyl group, a (2-methoxyphenyl) -ethynyl group,
2-thienyl-ethynyl group, 2-furyl-ethynyl group,
Examples thereof include a 2- (N-methyl) pyrrolinyl-ethynyl group, a 2-benzothienyl-ethyl group, a 2-benzofuranyl-ethynyl group, and a 2- (N-methyl) indolyl-ethynyl group.

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 has the same meaning as the group described as R ¹ in the above (ii).

When R ³ and R ⁴ are taken together to form an aliphatic hydrocarbon ring, the aliphatic hydrocarbon ring is not particularly limited. For example, an adamantylidene ring, a bicyclononylidene ring, a norbornylidene ring and the like can be mentioned.

When R ³ and R ⁴ are taken together to form an aromatic hydrocarbon ring, the aromatic hydrocarbon ring is not particularly limited, but a preferred ring is fluorene. And the like.

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

Further, at least one of R ³ and R ⁴ is particularly preferably any of the following groups.

A substituted aryl or substituted heteroaryl group having a substituted amino group as a substituent; a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and bonding the nitrogen atom to an aryl or heteroaryl group A substituted aryl group or a substituted heteroaryl group having, as a substituent, a substituted aryl group having, as a substituent, a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocycle is condensed to the substituted or unsubstituted heterocyclic group described above. or substituted heteroaryl group; the nitrogen atom has R ⁷ is a nitrogen atom as a hetero atom; R ⁷ is a group represented by the formula (4) is a substituted aryl group or a substituted heteroaryl group having as a substituent a substituted amino group And a substituted or unsubstituted heterocyclic group to which an aryl group or a heteroaryl group is bonded as a substituent. The R ⁷ is condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to a substituted or unsubstituted heterocyclic group in the; aryl group or a substituted heteroaryl group in which the formula (4) a group represented by A group represented by the formula (4), which is a substituted aryl group or a substituted heteroaryl group having a substituent; a formula (5), wherein R ⁹ is a substituted aryl group or a substituted heteroaryl group having a substituted amino group as a substituent. A substituted aryl group or a substituted heteroaryl group, wherein R ⁹ has a nitrogen atom as a hetero atom, and the nitrogen atom and an aryl group or a heteroaryl group have a substituted or unsubstituted heterocyclic group as a substituent. condensation of or R ⁹ is engaged aromatic hydrocarbon ring or aromatic heterocyclic ring fused to a substituted or unsubstituted heterocyclic group in the; group represented by an expression (5) Group represented by the formula (5) is a substituted aryl group or a substituted heteroaryl group having a heterocyclic group as a substituent.

In the above-mentioned substituted aryl group, the position of the substituent is not particularly limited.
Although the total number is not particularly limited, the substitution position is preferably substituted at the 3- or 4-position when the aryl group is a phenyl group, and the number is preferably 1. Specific examples of suitable substituted aryl groups include 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 can be mentioned.

In the above-mentioned substituted heteroaryl group, 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 preferred substituted heteroaryl groups include a 4- (N, N-dimethylamino) thienyl group and a 4- (N, N-diethylamino) group.
Examples thereof include a furyl group, a 4- (N, N-diphenylamino) thienyl group, a 4-morpholinopyrrolinyl group, a 6-piperidinobenzothienyl group, and a 6- (N, N-dimethylamino) benzofuranyl group.

In the group represented by the above formula (4), R ⁷ in the formula (4) has the same meaning as the above substituted aryl group or substituted heteroaryl group. As an example of a preferred group represented by the formula (4), (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.

In the group represented by the above formula (5), R ⁹ in the formula (5) has the same meaning as the above substituted aryl group or substituted heteroaryl group. As an example of a preferable group represented by the formula (5), (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- An ethynyl group, (4- (N-methylpiperazino) phenyl) -ethynyl and the like can be mentioned.

In the general formula (1), R ⁵ and R ⁶
Is independently a hydroxyl group, an alkyl group, a trifluoromethyl group, an alkoxy group, an aralkoxy group,
An amino group, a substituted amino group, a cyano group, a nitro group, a halogen atom, an aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, having a nitrogen atom as a hetero atom and not bonded to the nitrogen atom When a hand is present (that is, in the case of R ⁵ , the nitrogen atom and the above formula (2)
And in the case of R ⁶ , the nitrogen atom is bonded to the ring of the group represented by the formula (3). A) a substituted or unsubstituted heterocyclic group, or a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the heterocyclic group.

Here, an alkyl group, an alkoxy group, an aralkoxy group, a substituted amino group, a halogen atom, an aralkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroallyl group are represented by R ¹ and R ² about
a substituted or unsubstituted heterocyclic group or a heterocyclic group having a nitrogen atom as a hetero atom, wherein the nitrogen atom and the “carbon atom to which R ¹ and R ² are bonded” in (i), It is the same as that described as a group other than the "condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is condensed".

Further, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a hetero atom and having a dangling bond at the nitrogen atom, or an aromatic hydrocarbon ring or an aromatic heterocyclic ring fused to the heterocyclic group The fused heterocyclic groups described above are also the same as those described for R ¹ and R ² except for the ring to which the nitrogen atom is bonded.

Each R^FiveAnd R⁶The number of substitutions
And q are both integers from 0 to 3. These groups combine
Position is not particularly limited, and the total number is not particularly limited.
Is preferably 2 or less. Note that p is
When 2 or 3, each R ^FiveAre different from each other
You may. The same applies when q is 2 or 3.

The chromene compounds suitable in the present invention include the following chromene compounds (I) to (III).

(I) The following formula (6)

[0083]

Embedded image 中 In the formula, the following formula (3)

[0084]

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The group represented by is an unsaturated heterocyclic group,
R ¹ and R ² are the same as R ¹ and R ² in the general formula (1), R ³ and R ⁴ each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl R ⁵ represents a hydroxyl group, an alkyl group, a trifluoromethyl group, an alkoxy group, an aralkoxy group, a substituted amino group, a cyano group, a nitro group, a halogen atom, an aralkyl group, a substituted or unsubstituted aryl group, Or an unsubstituted heteroaryl group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and bonding the nitrogen atom to a naphthalene ring, or an aromatic hydrocarbon ring or an aromatic heterocyclic group as the heterocyclic group. A condensed heterocyclic group in which a ring is condensed, R ⁶ is a hydroxyl group, an alkyl group, a trifluoromethyl group, an alkoxy group, an aralkoxy group, a substituted amino Group, a cyano group, a nitro group, a halogen atom, an aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and a nitrogen atom as a heteroatom and represented by the nitrogen atom and the formula (3). A substituted or unsubstituted heterocyclic group bonded to the ring of the group to be bonded, or a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the heterocyclic group. Chromene compound represented by｝.

(II) The following formula (7)

[0087]

Embedded image 中 In the formula, the following formula (2)

[0088]

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The group represented by is an unsaturated heterocyclic group,
R ¹ and R ² are the same as R ¹ and R ² in the general formula (1), R ³ and R ⁴ each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl R ⁵ represents a hydroxyl group, an alkyl group, a trifluoromethyl group, an alkoxy group, an aralkoxy group, a substituted amino group, a cyano group, a nitro group, a halogen atom, an aralkyl group, a substituted or unsubstituted aryl group, Or an unsubstituted heteroaryl group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and bonding the nitrogen atom to the ring of the group represented by the formula (2), or A condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocycle is condensed, and R ⁶ is a hydroxyl group, an alkyl group, a trifluoromethyl group, an alkoxy group, an aralkoxy group; A diamino group, a substituted amino group, a cyano group, a nitro group, a halogen atom, an aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group; A substituted or unsubstituted heterocyclic group bonded to
Or a fused heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to the heterocyclic group. Chromene compound represented by｝.

(III) The following formula (8)

[0091]

Embedded image 中 In the formula, the following formula (2)

[0092]

Embedded image And a group represented by the following formula (3)

[0093]

Embedded image

The group represented by the general formula (1) has the same meaning as in the general formula (1). Ring A and ring B are an aromatic hydrocarbon group or an aromatic heterocyclic ring which may have a substituent, and at least A One of the ring and the ring B is an aromatic heterocyclic group,
Is the following formula

[0095]

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(Wherein R ¹⁰ is a hydrogen atom or a group having 1 to 1 carbon atoms)
An alkyl group of 10; d is an integer of 0 to 2;
Is a simple bond when r is 0, r is an integer of 2 to 4, and s is an integer of 2 to 4. ) Is any one group selected from groups represented by, R ³ and R ⁴ are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, R ⁵ Is a hydroxyl group, an alkyl group, a trifluoromethyl group, an alkoxy group, an aralkoxy group, a substituted amino group, a cyano group, a nitro group, a halogen atom, an aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl A substituted or unsubstituted heterocyclic group having a group, a nitrogen atom as a heteroatom, and bonding the nitrogen atom to the ring of the group represented by the formula (2), or an aromatic hydrocarbon ring or a fused heterocyclic group in which an aromatic heterocyclic ring is fused, R ⁶ is hydroxyl group, an alkyl group, a trifluoromethyl group, an alkoxy group, aralkoxy group, substituted A amino group, a cyano group, a nitro group, a halogen atom, an aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and a nitrogen atom as a heteroatom; It is a substituted or unsubstituted heterocyclic group bonded to the ring of the group shown, or a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the heterocyclic group. Chromene compound represented by｝.

The most preferred chromene compounds include R ³
Is (a) an aryl group or a heteroaryl group having an amino group as a substituent, (b) a substituted or unsubstituted nitrogen atom having a heteroatom as a heteroatom and an aryl group or a heteroaryl group bonded to the nitrogen atom. Aryl group or heteroaryl group having a heterocyclic group as a substituent, or (c)
The above formula (6), which is a substituted aryl group or a substituted heteroaryl group having as a substituent a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is condensed with the substituted or unsubstituted heterocyclic group in the above (b). Is a chromene compound represented by

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

[0099]

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[0100]

Embedded image

[0101]

Embedded image

[0102]

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The chromene 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.
It can be confirmed by such means as (c).

(A) Proton nuclear magnetic resonance spectrum (
By measuring ¹ H-NMR), δ 5.0 to 9.
A peak based on an aromatic proton and an alkene proton appears at about 0 ppm, and a peak based on an alkyl group and an alkylene group proton appears at about δ 1.0 to 4.0 ppm. Further, by comparing the respective spectral intensities relatively, the number of protons of each bonding group can be known.

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

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

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

In this method, the following general formula (9)

[0109]

Embedded image (However, the following equation (2)

[0110]

Embedded image A group represented by the following formula (3)

[0111]

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The groups represented by R ³ , R ⁴ , R ⁵ , R ⁶ , p and q have the same meanings as defined in the general formula (1). And a carbonyl-chromene derivative represented by the following general formula (10)

[0113]

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In the formula, the ring C and the ring D are each independently
A substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group, wherein Z is a lithium atom,
A sodium atom, a potassium atom, or a magnesium atom, L is a chlorine atom, a bromine atom, or an iodine atom; and when Z is other than a magnesium atom, L is not present;
W is the following formula

[0115]

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(Wherein R ¹⁰ is a hydrogen atom or a group having 1 to 1 carbon atoms)
An alkyl group of 10; d is an integer of 0 to 2;
Is a simple bond when r is 0, r is an integer of 2 to 4, and s is an integer of 2 to 4. Any one indicated by)
There are two groups. By reacting with an organometallic reagent represented by｝, the following general formula (11)

[0117]

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(Wherein all the substituents and rings are the same as the substituents represented by the same symbols in the general formulas (9) and (10)), and a hydroxychromene derivative represented by the formula: This is a method for obtaining a chromene compound represented by the general formula (1) by dehydration and ring closure under acidic conditions. The method for synthesizing the carbonyl-chromene derivative represented by the general formula (9) is not particularly limited, and can be synthesized by a known method. For example, the following general formula (12)

[0119]

Embedded image (However, the following equation (2)

[0120]

Embedded image And a group represented by the following formula (3)

[0121]

Embedded image

The groups represented by R ⁵ , R ⁶ , p and q are as defined in the general formula (1). ) And a phenol derivative represented by the following general formula (13)

[0123]

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(Wherein R ³ and R ⁴ have the same meanings as defined in formula (1)) by reacting a propargyl alcohol derivative represented by the formula (9) under acidic conditions. A carbonyl-chromene derivative can be synthesized. At this time, the formula (2) and / or
Alternatively, when a group having a substituent is used as the group represented by the formula (3), a group represented by the formula (2) and / or (3) is used as the carbonyl-chromene derivative represented by the general formula (9). Those having a substituent can be synthesized.

The carbonyl represented by the general formula (9)
The reaction conditions at the time of synthesis of the chromene derivative are not particularly limited. For example, the reaction can be suitably performed under the following conditions.

That is, the reaction ratio of the phenol derivative and propargyl alcohol as the reaction substrate is adopted from a wide range, but is generally selected from the range of 1:10 to 10: 1 (molar ratio). Further, as the acid catalyst, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid, acidic alumina or the like is used.
It is used in the range of 1 to 10 parts by weight. The reaction temperature is usually preferably from 0 to 200 ° C., and as the solvent, an aprotic organic solvent such as N-methylpyrrolidone, dimethylformamide, tetrahydrofuran, benzene, and toluene are used.

The 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 synthesis of the hydroxychromene derivative represented by the general formula (11) is performed, for example, as follows.

That is, first, the raw material represented by the following formula

[0130]

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(Wherein L is chlorine, bromine or iodine) and an alkali metal or alkaline earth metal such as magnesium metal or lithium metal in the range of 1: 1 to 1: 3. Reaction in an inert solvent such as dry ether or dry THF is performed at -70 ° C.
The reaction is carried out at a reflux temperature for 10 to 6 hours to obtain an organometallic reagent represented by the above formula (10). Then, the thus obtained organometallic reagent and the carbonyl-chromene compound represented by the general formula (9) are mixed with an organic solvent such as dry THF or dry ether under a nitrogen atmosphere at a ratio of 2: 1 to 1: 5. The hydroxychromene derivative represented by the general formula (11) can be obtained by mixing and stirring at room temperature to reflux temperature for 10 minutes to 10 hours. In the reaction, the organometallic reagent does not need to be isolated and purified, and the reagent obtained from the synthesis can be used as it is.

After completion of the reaction, the reaction solution was poured into ice water, neutralized with an acid such as hydrochloric acid, acetic acid, sulfuric acid, and the like, and the organic matter was extracted with an organic solvent such as toluene and ether.
The desired hydroxychromene derivative can be obtained by evaporating the solvent from the organic layer. Further, depending on the case, the precipitated hydroxychromene derivative can be obtained by filtration. Thereafter, purification is performed using a silica gel column or the like, and further, the product can be purified by recrystallization, but the crude product may be used as it is in the next reaction.

The method for obtaining the chromene compound represented by the above general formula (1) by dehydrating and cyclizing the hydroxychromene derivative thus obtained is not particularly limited. 10 minutes to 10 at room temperature to reflux temperature in an acidic solvent such as a mixed solvent of hydrochloric acid.
It can be suitably performed by stirring for a time. After the completion of the ring closure reaction, the reaction product was transferred to water, neutralized with alkali, and the organic substance was extracted with an organic solvent such as toluene and ether.After washing with water, the solvent was distilled off. And / or purification by recrystallization to obtain the target chromene compound represented by the general formula (1).

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 reversibly quickly when light is blocked. It exhibits good photochromic action returning to its original colorless state. The photochromic action of such a compound of the general formula (1) shows similar properties even in a polymer solid matrix. The target polymer solid matrix may be any one in which the chromene compound represented by the general formula (1) of the present invention is uniformly dispersed, and optically preferable, for example, polymethyl acrylate, polyacrylic acid Ethyl, polymethyl methacrylate,
Examples include thermoplastic resins such as polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethyl methacrylate), polydimethylsiloxane, and polycarbonate.

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

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

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

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

For example, when the photochromic material is used for a photochromic lens, the method is not particularly limited as long as uniform light control performance can be obtained. For example, the photochromic material of the present invention can be uniformly dispersed. A method of sandwiching a polymer film in a lens, or a method of dispersing the chromene compound of the present invention in the polymerizable monomer and polymerizing it by a predetermined method, or a method of dispersing the compound in, for example, silicone oil Dissolve 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.

[0140]

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 structure

[0142]

Embedded image

A carbonyl chromene compound represented by the following formula:
0 g (0.0019 mol) of dry THF solution 10 ml
And the following equation

[0144]

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0.76 g (0.0029 g) of the organometallic reagent
mol) is reacted under a nitrogen atmosphere at 35 ° C. for 2 hours, and then ice water 1
Then, the mixture was neutralized with diluted hydrochloric acid, extracted with ether, washed with water, dried over magnesium sulfate, and the solvent was distilled off.

[0146]

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1.5 g of an oil containing 10 ml of acetic acid and 0.5 ml of concentrated hydrochloric acid were added to the oil,
After 2 hours of reaction, the reaction mixture was poured into 100 ml of water, neutralized with a 10% aqueous sodium hydroxide solution, and the organic matter precipitated with toluene was extracted, washed with water, dried over magnesium sulfate, and evaporated, and the resulting oil was subjected to silica gel chromatography. By purification, 0.3 g of a product as a pale yellow powder was obtained. The yield was 24%. Elemental analysis of this product gave C 78.87%, H 4.66%, N 2.06%, O
4.77%, a _{S9.63%, C 44 H 31 NO} 2 S
C. 78.89%, H 4.66%, N2.
The values agreed very well with the results, namely, 09%, O4.78% and S9.57%.

When the proton nuclear magnetic resonance spectrum was measured, an 8H peak based on the methylene proton of the morpholino group, δ5.
A peak of 23H based on an aromatic proton and an alkene proton was shown around 5 to 9.0 ppm.
Further measurement of ¹³ C-nuclear magnetic resonance spectrum,
A peak based on the carbon of the aromatic ring was found at around δ 110 to 160 ppm, a peak based on the carbon of the alkene around δ 80 to 140 ppm, and a peak based on the carbon of the alkyl at δ 20 to 60 ppm. From the above results, it was confirmed that the isolated product was a compound represented by the following structural formula.

[0149]

Embedded image

Examples 2 to 16 In the same manner as in Example 1, chromene compounds shown in Tables 1 to 4 were synthesized. As a result of structural analysis of the obtained product using the same means for structure confirmation as in Example 1, Tables 1 to 4
Was confirmed to be a compound represented by the structural formula shown in Table 1.
Tables 5 and 6 show the elemental analysis values of these compounds, the calculated values obtained from the structural formulas of the respective compounds, and characteristic ¹ H-NMR spectra.

[0151]

[Table 1]

[0152]

[Table 2]

[0153]

[Table 3]

[0154]

[Table 4]

[0155]

[Table 5]

[0156]

[Table 6]

Examples 17 to 32, 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. The obtained polymer (thickness: 2 mm) was used as a sample, and a xenon lamp L-2480 (300 W) SH manufactured by Hamamatsu Photonics was added to the sample.
L-100 aeromass filter (Corning)
20 ° C. ± 1 ° C., beam intensity 36 on the polymer surface
5 nm = 2.4 mW / cm ² , 245 nm = 24 μW /
The sample was irradiated for 120 seconds at cm ² to develop a color, and the photochromic properties of the sample were measured. The photochromic properties were evaluated as follows.

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

Initial coloring {ε (0)}: Absorbance at the maximum absorption wavelength in the light non-irradiated state. 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.

Coloring density Δε (120) −ε
(0)｝: difference between the absorbance {ε (120)} after the light irradiation 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.)]: 12
After the light irradiation for 0 second, when the light irradiation is stopped, the absorbance at the maximum length of the sample is {ε (120) −ε (0)}.
The time it takes to drop to half of It can be said that the shorter this time is, the better the photochromic property is.

Residual rate (%) = ｛(A ₀ / A ₂₀₀ ) × 1
00｝: 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.

The degree of change in coloring (ΔYI) = YI (20
0) -YI (0): In order to evaluate the durability of the color tone without light irradiation, the color difference meter (SM-4) manufactured by Suga Test Instruments Co., Ltd. was used for the samples before and after the deterioration promotion test. The color difference was measured. The degree of change in coloring due to deterioration is calculated from the value of the degree of coloring {YI (200)} after the test to the value of the degree of coloring {YI before the test}
(0)} was subtracted to obtain a difference {YI}, and the durability was evaluated. The smaller the ΔYI, the higher the durability of the color tone without light irradiation.

Further, a photochromic polymer was obtained in the same manner as described above except that the compounds obtained in Examples 2 to 16 were used as the chromene compound, and the characteristics were evaluated. Table 7 summarizes the results.

[0165]

[Table 7] Further, for comparison, the following formulas (A) and (B)

[0166]

Embedded image

[0167]

Embedded image

A photochromic polymer was obtained in the same manner using the compound represented by the formula (1), and the characteristics are shown in Table 8.

[0169]

[Table 8]

Example 1 using the chromene compound of the present invention
In 7 to 32, the photochromic polymer was 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.

[0171]

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.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C09K 9/02 C09K 9/02 BF Term (Reference) 4C062 HH69 4C071 AA04 AA08 BB01 BB02 BB03 BB08 CC01 CC11 CC12 CC21 CC22 EE05 EE13 FF17 FF23 GG01 GG05 HH05 JJ01 JJ07 JJ08 LL05

Claims (3)

[Claims] [Claim 1] The following general formula (1) 中 wherein the following formula (2) And a group represented by the following formula (3): Are each independently an aromatic hydrocarbon group or an unsaturated heterocyclic group, and R ¹ and R ² are at least one of the groups represented by the above formula (2) or the above formula (3) When one of the groups is an unsaturated heterocyclic group, the group satisfies the following condition (i) or (ii), and both groups represented by the formulas (2) and (3) are When it is an aromatic hydrocarbon group, it is a group that satisfies the following condition (i) or (iii), and R ³ and R ⁴ are each independently the following formula (4): (Wherein R ⁷ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group;
⁸ 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 (5): (Wherein, R ⁹ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group;
Is an integer of 1 to 3. ), A substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or an alkyl group, or R ³ and R ⁴ together form an aliphatic hydrocarbon ring or an aromatic group. R ⁵ may be a hydroxyl group, an alkyl group, a trifluoromethyl group, an alkoxy group, an aralkoxy group, an amino group, a substituted amino group, a cyano group, a nitro group, a halogen atom, an aralkyl group. Group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted having a nitrogen atom as a heteroatom and bonding the nitrogen atom to the ring of the group represented by the formula (2) Or a fused heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocycle is fused to the heterocyclic group, p is an integer of 0 to 3, and R ⁶ is Sil group, alkyl group, trifluoromethyl group, alkoxy group, aralkoxy group, amino group, substituted amino group, cyano group, nitro group, halogen atom, aralkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted hetero An aryl group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a hetero atom and bonding the nitrogen atom to the ring of the group represented by the formula (3), or an aromatic hydrocarbon ring as the heterocyclic group Alternatively, it is a condensed heterocyclic group in which an aromatic heterocyclic ring is condensed, and q is an integer of 0 to 3. ｝
A chromene compound represented by the formula: [Condition of R ¹ and R ^2] (i) unsubstituted or one of R ¹ or R ² has the nitrogen atom is a nitrogen atom as a hetero atom bonded to the carbon atom to which R ¹ and R ² are bonded A substituted heterocyclic group, or a fused heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the heterocyclic group, and the other is a hydrogen atom, a hydroxyl acid group, an alkyl group, an alkoxy group, an aralkoxy group,
It is an amino group, a substituted amino group, a cyano group, a halogen atom, an aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. (ii) R ¹ and R ² are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, or R ¹ and R ² are
A substituted or unsubstituted divalent aromatic hydrocarbon group or a substituted or unsubstituted divalent unsaturated heterocyclic group and a substituted or unsubstituted divalent aromatic hydrocarbon group or a substituted or unsubstituted divalent An unsaturated heterocyclic group is represented by the following formula: (Wherein, R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, d is an integer of 0 to 2, and when d is 0, it represents a mere bond; Is an integer and s is 2
6 to an integer. ) To form a ring bonded through any one group selected from the groups represented by (iii) The condition (ii) is the same as the condition (ii) except that one or both of R ^{1 and} R ² are a substituted or unsubstituted heteroaryl group. 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.