JP2001114775A - Chromene compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new photochromic compound causing slight initial discoloration. SOLUTION: This new chromene compound has a phenyl group at the 2-position of the pyran ring substituted by amino group having a substituent group as a basic structure, e.g. the one represented by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of changing the color of a liquid to a yellow to light blue color by irradiation with light including ultraviolet rays such as sunlight or light from a mercury lamp, the change being reversible and in a colorless state. It relates to a chromene compound with little initial coloring.

[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 98/45
No. 281, the following formula (A)

[0004]

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[0005] A chromene compound represented by the following formula is disclosed. When dissolving in a solution or dispersing in a polymer matrix, this chromene compound develops a light orange color to a dark orange color when exposed to light including ultraviolet light, and blocks the original light orange color when the ultraviolet light is blocked. Shows the reversibility of the photochromic action of returning to. However, since it is lightly colored even in a colorless state, that is, a state in which light including ultraviolet rays is not applied, there is a problem that it cannot be suitably used in a field such as a photochromic eyeglass lens where transparency is required.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a chromene compound having less initial coloring and exhibiting good photochromic properties as compared with the above-mentioned compounds.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been proposed to achieve the above object, and has been made based on the knowledge obtained by the present inventors that the novel chromene compound of the present invention has little initial coloring. It was completed.

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

[0009]

Embedded image [Wherein, R ¹ represents the following formula (2)

[0010]

Embedded image

Wherein R ⁵ and R ⁶ are each independently
Hydrogen atom, a trifluoromethyl group, a cyano group, a cyanomethyl group, a sulfonyl group, an arylsulfonyl group, an alkylsulfonyl group, a sulfamoyl group, a nitro group, Karubokishiriru group, carboxamide group, an alkoxycarbonyl group, or a carbamoyl group, R ⁵ And R ⁶ are not hydrogen atoms at the same time. A group represented by｝, or the following formula (3)

[0012]

Embedded image

Wherein R ⁷ and R ⁸ are each independently
A hydrogen atom, an alkyl group, a trifluoromethyl group, a cyano group, a cyanomethyl group, an arylsulfonyl group, an alkylsulfonyl group, an alkylcarbonyl group, or an arylcarbonyl group, and R ⁷ and R ⁸ are simultaneously a hydrogen atom or an alkyl group Never.基 is a group represented by R
² , R ³ and R ⁴ are each independently a hydrogen atom, an alkoxy group, a halogen atom, a trifluoromethyl group or a trifluoromethoxy group, and are represented by the following formula (4)

[0014]

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The divalent group represented by the general formula (1)
It is a divalent condensed polycyclic organic group which may have a substituent having a benzene ring condensed with a 2H-pyran ring therein as a constituent element. ] Is a chromene compound represented by the formula:

In the chromene compound, the following formula (4) in the above general formula (1)

[0017]

Embedded image The divalent fused polycyclic organic group which may have a substituent represented by the following formulas (5) to (8)

[0018]

Embedded image

In each formula, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² ,
R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aralkoxy group, an aralkyl group, a substituted amino group, a cyano group, an aryl group, a halogen atom, and a nitrogen atom. A heterocyclic group in which the nitrogen atom and the ring of the condensed polycyclic organic group are bonded as an atom, or a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocycle is condensed to the heterocyclic group, These groups may have a substituent, and a, b, c, d, e, and f representing the number of bonds of R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are are each independently an integer of 0 to 3, R ^10, and l and m represent the number of bonds R ¹¹ are each independently an integer of 0 to 2, a to f, l, and m is 2 or more each ^{R 9, R 1 0, R} 11, R 12, R 13, R 14, R 15 coupled to one another when,
Or R ¹⁶ may be different from each other, and the group represented by -Y- in the formula (8) is represented by the following formula:

[0020]

Embedded image

(Where Z is¹And Z^TwoIs oxygen independently
Atom or sulfur atom, and R¹⁷, R ¹⁸, R¹⁹, And R
²⁰Is an alkylene group, and g, h, i, and j are
Each is an integer of 1 to 4. ) Any group represented by｝
Chromene compound has good photochromic properties
It has the characteristic of showing.

Further, another invention is a photochromic material comprising the chromene compound of the present invention and a photochromic optical material comprising the chromene compound.

[0023]

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

[0024]

Embedded image

Wherein R ⁵ and R ⁶ are each independently
Hydrogen atom, a trifluoromethyl group, a cyano group, a cyanomethyl group, a sulfonyl group, an arylsulfonyl group, an alkylsulfonyl group, a sulfamoyl group, a nitro group, Karubokishiriru group, carboxamide group, an alkoxycarbonyl group, or a carbamoyl group, R ⁵ And R ⁶ are not hydrogen atoms at the same time. A group represented by｝, or the following formula (3)

[0026]

Embedded image

Wherein R ⁷ and R ⁸ are each independently
A hydrogen atom, an alkyl group, a trifluoromethyl group, a cyano group, a cyanomethyl group, an arylsulfonyl group, an alkylsulfonyl group, an alkylcarbonyl group, or an arylcarbonyl group, and R ⁷ and R ⁸ are simultaneously a hydrogen atom or an alkyl group Never. It is a group represented by｝.

The arylsulfonyl group of R ⁵ and R ^{6 in} the general formula (2) is not particularly limited, but is generally an arylsulfonyl group having 6 to 11 carbon atoms. Examples of suitable arylsulfonyl groups include a phenylsulfonyl group, a p-toluylsulfonyl group, and a naphthylsulfonyl group.

The alkylsulfonyl group of R ⁵ and R ⁶ is not particularly limited, but generally has 1 to carbon atoms.
An alkylsulfonyl group of 4 is preferred. Examples of suitable alkylsulfonyl groups include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, and a butylsulfonyl group.

The carboxamide group of R ⁵ and R ⁶ is not particularly limited, but generally has 2 to 9 carbon atoms.
Is preferred. Illustrative examples of suitable carboxamide groups include N-methylcarboxamide groups,
N, N-dimethylcarboxamide group, N, N-diethylcarboxamide group, N, N-dipropylcarboxamide group, N, N-di-n-butylcarboxamide group and the like can be mentioned.

The alkoxycarbonyl group for R ⁵ and R ⁶ is not particularly limited, but generally has 2 carbon atoms.
~ 5 alkoxycarbonyl groups are preferred. Examples of suitable alkoxycarbonyl groups include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group,
Examples thereof include an n-butoxycarbonyl group, a sec-butoxycarbonyl group, and a t-butoxycarbonyl group.

The above R^FiveAnd R⁶In the effect of the present invention
To reduce certain initial coloration, R^FiveAnd R⁶Nozomi
One or two of them are trifluoromethyl, cyano
Group, cyanomethyl group, sulfonyl group, arylsulfonyl group
Group, alkylsulfonyl group, sulfamoyl group, nitro
B, carboxylyl, carboxamide, alkoxy
Electron withdrawal such as carbonyl or carbamoyl
Preferably it is a group. In that case, the other substituent
As a hydrogen atom reduces initial coloration
Preferred for In particular, the solubility and durability of chromene compounds
From the viewpoint of sex, R ^FiveAnd R⁶Any one of the trif
Fluoromethyl group, cyano group, cyanomethyl group, alkoxy
Particularly preferred is a carbonyl group and the other is a hydrogen atom.
Suitable.

The alkyl group of R ⁷ and R ^{8 in} the general formula (3) is not particularly limited, but generally has 1 to 4 carbon atoms such as a methyl group, an ethyl group and an n-propyl group. , Isopropyl group, n-butyl group, sec-butyl group, t-
A butyl group and the like can be mentioned.

The arylsulfonyl group and alkylsulfonyl group for R ⁷ and R ⁸ include the same substituents as those exemplified for R ⁵ and R ⁶ .

The alkylcarbonyl group for R ⁷ and R ⁸ is not particularly limited, but generally has 2 to 2 carbon atoms.
5 alkylcarbonyl groups are preferred. Examples of suitable alkylcarbonyl groups include a methylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, and a butylcarbonyl group.

The arylcarbonyl group of R ⁷ and R ⁸ is not particularly limited, but generally has 7 to 7 carbon atoms.
Twelve arylcarbonyl groups are preferred. Examples of suitable arylcarbonyl groups include a phenylcarbonyl group,
Examples thereof include a p-toluylcarbonyl group and a naphthylcarbonyl group.

In R ⁷ and R ⁸ , one of R ⁷ and R ⁸ is selected from the group consisting of the trifluoromethyl group, cyano group, cyanomethyl group, An electron withdrawing group such as an arylsulfonyl group, an alkylsulfonyl group, an alkylcarbonyl group, or an arylcarbonyl group is preferred.
In particular, from the viewpoint of the solubility of the chromene compound, R ⁷ and R ⁸
It is particularly preferred that one or two of the above are a trifluoromethyl group, a cyano group, a cyanomethyl group, an alkylcarbonyl group, and an arylcarbonyl group. When one of R ⁷ and R ⁸ is a group as described above, the other group is preferably a hydrogen atom or an alkyl group to reduce initial coloring.

In the above formula (1), R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkoxy group, a halogen atom, a trifluoromethyl group or a trifluoromethoxy group.

Here, the halogen atom is not particularly limited, but is preferably a fluorine atom, a chlorine atom, or a bromine atom. Among them, a fluorine atom is particularly preferred.

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

In R ² , R ³ and R ⁴ , even if R ² , R ³ and R ⁴ are all a hydrogen atom or an alkoxy group, the effect of reducing the initial coloring, which is the effect of the present invention, is exhibited. If at least one of R ² , R ³ and R ⁴ is a halogen atom, a trifluoromethyl group or a trifluoromethoxy group, it is preferable since the initial coloring is further reduced. When R ³ is an alkoxy group, it is effective for increasing the fading speed among the photochromic characteristics.

In R ² , R ³ and R ⁴ , particularly preferred forms of the substituents are those of R ² , R ³ and R ⁴ from the viewpoint of reducing the initial coloring which is the effect of the present invention. One is a fluorine atom, a trifluoromethyl group, or a trifluoromethoxy group and the other is a hydrogen atom, or R ³ is an alkoxy group, and one of R ^{2 and} R ⁴ is a fluorine atom, The form in which it is a fluoromethyl group or a trifluoromethoxy group and the other is a hydrogen atom is particularly preferable.

In the general formula (1), the following formula (4)

[0044]

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The divalent group represented by the general formula (1)
It is a divalent condensed polycyclic organic group which may have a substituent having a benzene ring condensed with a 2H-pyran ring therein as a constituent element.

The divalent condensed polycyclic organic group is not particularly limited as long as it has a benzene ring condensable with the 2H-pyran ring in the general formula (1), and any known condensed polycyclic organic group can be used. It may be a polycyclic organic group.
The number of rings constituting the condensed polycyclic organic group is not particularly limited, but is preferably 2 to 10 among known condensed polycyclic organic groups.

The structure of the ring may be a condensed polycyclic organic group which may have a substituent, the ring is constituted only by unsaturated carbon atoms, or may have a substituent. A condensed polycyclic organic group containing 1 to 2 saturated carbon atoms other than unsaturated carbon atoms as ring constituent elements and 0 to 2 nitrogen, oxygen or sulfur atoms as hetero atoms;
Alternatively, a condensed polycyclic organic group containing one or two nitrogen, oxygen, or sulfur atoms as hetero atoms in addition to unsaturated carbon as a constituent element of a ring is preferable.

Examples of the condensed polycyclic organic group which may have a substituent and which is composed only of unsaturated carbon atoms include naphthalene, phenanthrene, anthracene, acenaphthylene, biphenylene, naphthacene, pyrene, triphenylene, chrysene and phenalene. , Picene, fluoranthene,
Examples include perylene, acephenanthrylene, pentaphen, pentacene, trinaphthylene, tetraphenylene, hexaphen, heptafen, hexacene, rubicene, pyranthrene, coronene, and ovalene. The position at which these are fused to the 2H-pyran ring in the general formula (1) is not particularly limited at any position of the benzene ring in the fused polycyclic organic group which can be fused to the 2H-pyran ring.

The substituent of the condensed polycyclic organic group composed only of unsaturated carbon atoms is not particularly limited, and may be any known substituent. In consideration of photochromic properties, the following substituents are considered. Groups are preferred. Preferred substituents include an alkyl group, an alkoxy group, an aralkoxy group, an aralkyl group, a substituted amino group, a cyano group, an aryl group, a halogen atom, and a condensed polycyclic organic group having a nitrogen atom as a hetero atom. And a fused heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is fused to the heterocyclic group.

Among the substituents, the alkyl group is not particularly limited, but is generally an alkyl group having 1 to 4 carbon atoms. Examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n
-Butyl group, sec-butyl group, t-butyl group and the like.

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

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

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

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

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

Examples of the substituted aryl group include an alkyl group, an alkoxy group, an aryl group, an aralkyl group, and a substituted amino group in which one or more hydrogen atoms of the unsubstituted aryl group are substituted.

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

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

The number of these substituents is not particularly limited and may be appropriately determined depending on the number of substitutable substitution positions. Generally, the number of substituents is preferably 0 to 5.

In the above general formula (1), the following formula (4)

[0061]

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The divalent group represented by the formula (1) contains one to two saturated carbon atoms other than unsaturated carbon atoms as an element constituting a ring, and contains zero nitrogen, oxygen or sulfur atoms as hetero atoms. When it is a fused polycyclic organic group containing 2 to 2,
Such groups include indene, fluorene, acenaphthene, indane, 7H-benzo [c] fluorene,
1H-benzo [a] fluorene, 7H-dibenzo [c,
g] fluorene, 7H-dibenzo [b, g] fluorene, and 13H-dibenzo [a, g] fluorene. The position at which each of these groups is fused to the 2H-pyran ring in the general formula (1) is the 2H-pyran ring.
There is no particular limitation on any position of the benzene ring in the condensed polycyclic organic group which can be condensed with the pyran ring.

The group may have a substituent, and when the position of the substituent is on an unsaturated carbon atom, a condensation composed of only the unsaturated carbon atom Substituents similar to the substituents exemplified for the polycyclic organic group can be exemplified. The number of the substituents is not particularly limited and may be appropriately determined based on the number of substitutable substitution positions. Generally, the number of the substituents is preferably 0 to 5.

The substituent may be on a saturated carbon atom without any problem. Examples of the substituent at this time include substituents such as a hydroxyl group, an alkoxy group, and an alkyl group. As another form of the substituent, a saturated carbon atom may form a spiro ring with another ring.

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

In the case where the saturated carbon atom forms a spiro ring with another ring, the other ring is not particularly limited as long as it can form a spiro ring, and the following rings are exemplified. Can be. "C" in the ring means a spiro carbon.

That is, as such a ring,

[0069]

Embedded image Or, the following general formula (9),

[0070]

Embedded image ｛However, the group represented by -Y- in the following formula

[0071]

Embedded image

(Where Z is¹And Z^TwoIs oxygen independently
Atom or sulfur atom, and R¹⁷, R ¹⁸, R¹⁹, And R
²⁰Is an alkylene group, and g, h, i, and j are
Each is an integer of 1 to 4. Any group represented by)
It is. ｝.

Where Z¹And Z^TwoIs an oxygen atom or a sulfur atom
I am a child. In the formula, R¹⁷, R¹⁸, R ¹⁹, And R²⁰Is
It is a alkylene group. The alkylene group is not particularly limited.
Is not performed, but an alkylene group having 1 to 6 carbon atoms is preferable.
No. Suitable alkylene groups include methylene, ethylene
Group, propylene group, butylene group, pentylene group,
Examples thereof include a silene group. G, h,
i and j indicate the respective number of repetitions
However, these are all integers of 1 to 4,
Are all 1 or 2 in that
Is preferred.

In the general formula (1), the following formula (4)

[0075]

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Is a condensed polycyclic organic group containing one or two nitrogen, oxygen or sulfur atoms as hetero atoms in addition to the unsaturated carbon atoms as ring constituent elements. Include such groups as indole, isoindole, benzo [b] furan, benzo [b] thiophene, indolizine, 4H-chromene, quinoline, isoquinoline, 4H-quinolidine, 1H-indazole, quinazoline, cinnoline, quinoxaline Phthalazine, carbazole, acridine, phenanthridine, phenazine, phenothiazine, phenoxatiin, phenoxazine, and thianthrene. The position at which each of these groups is fused to the 2H-pyran ring in the general formula (1) is not particularly limited at any position of the benzene ring in the condensed polycyclic organic group which can be fused to the 2H-pyran ring.

The condensed polycyclic organic group containing one or two nitrogen, oxygen or sulfur atoms as a hetero atom as described above may have a substituent. And the same substituents as those exemplified for the condensed polycyclic organic group composed only of the unsaturated carbon atoms. The number of the substituents is not particularly limited and may be appropriately determined based on the number of substitutable substitution positions. In general, the number of the substituents is preferably 0 to 5.

In the general formula (1), the following formula (4)

[0079]

Embedded image The divalent fused polycyclic organic group which may have a substituent represented by the following formulas (5) to (8)

[0080]

Embedded image

In the formulas, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² ,
R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aralkoxy group, an aralkyl group, a substituted amino group, a cyano group, an aryl group, a halogen atom, and a nitrogen atom. A heterocyclic group in which the nitrogen atom and the ring of the condensed polycyclic organic group are bonded as an atom, or a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocycle is condensed to the heterocyclic group, These groups may have a substituent, and represent a, b, c, d, e, and f representing the number of bonds of R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ^16. Are each independently an integer of 0 to 3, l and m representing the number of bonds of R ¹⁰ and R ¹¹ are each independently an integer of 0 to 2, and a to f, l, and m are 2 or more and R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ ,
Or R ¹⁶ may be different from each other, and the group represented by -Y- in the formula (8) is represented by the following formula:

[0082]

Embedded image

(Where Z is¹And Z^TwoIs oxygen independently
Atom or sulfur atom, and R¹⁷, R ¹⁸, R¹⁹, And R
²⁰Is an alkylene group, and g, h, i, and j are
Each is an integer of 1 to 4. ) Any group represented by｝
Chromene compound is one of the photochromic properties
It is preferable to consider the fading speed.

Here, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ ,
R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom,
An alkyl group, an alkoxy group, an aralkoxy group, an aralkyl group, a substituted amino group, a cyano group, an aryl group, a halogen atom, a heteroatom having a nitrogen atom as a heteroatom, wherein the nitrogen atom is bonded to a ring of a condensed polycyclic organic group. A condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocycle is condensed to the cyclic group or the heterocyclic group, and the substituent of each of these groups is the condensed polycyclic organic group, Substituents similar to the substituents exemplified in the case of a condensed polycyclic organic group which may have a substituent composed only of atoms can be exemplified. These groups may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, an aralkoxy group, an aralkyl group, a substituted amino group, a cyano group, an aryl group, a halogen atom, and a nitrogen atom. Examples of the heterocyclic group include a heteroatom in which the nitrogen atom is bonded to the ring of the condensed polycyclic organic group as a hetero atom, and each of these substituents can be the same as the above-mentioned substituent.

Further, a, b, c, d, e and f representing the number of bonds of R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently an integer of 0 to 3. , R ¹⁰ and R ¹¹ each independently represent an integer of 0 to 2, and each of R ⁹ , R ^{9 to be} bonded when a to f, l, and m is 2 or more, ^{10, R 11, R 12,} R 13, R 14, R 15,
Alternatively, R ¹⁶ may be different from each other, but a to f, l, and m are preferably integers of 0 to 1 from the viewpoint of ease of synthesis.

The group represented by -Y- in the above formula (8) is represented by the following formula:

[0087]

Embedded image

(Where Z is¹And Z^TwoIs oxygen independently
Atom or sulfur atom, and R¹⁷, R ¹⁸, R¹⁹, And R
²⁰Is an alkylene group, and g, h, i, and j are
Each is an integer of 1 to 4. )
is there. R in the formula¹⁷, R¹⁸, R ¹⁹, And R²⁰Archille
And the groups g, h, i, and j are described in the general formula (9).
The same form as described can be shown.

Among the chromene compounds of the present invention, the following formulas (10), (11),
(12) and (13)

[0090]

Embedded image (Wherein, R ²² , R ²⁶ , R ³¹ and R ³⁶ are represented by the following formula (1)
4)

[0091]

Embedded image

In the formula, R ³⁹ and R ⁴⁰ are each independently a hydrogen atom, a trifluoromethyl group, a cyano group, a cyanomethyl group or an alkoxycarbonyl group, and R ³⁹ and R ⁴⁰ are simultaneously a hydrogen atom. There is no. A group represented by｝, or the following formula (15)

[0093]

Embedded image

[0094] {wherein, R ⁴¹ and R ⁴² each independently represent a hydrogen atom, an alkyl group, a trifluoromethyl group, a cyano group, a cyanomethyl group, an alkylcarbonyl group, or an arylcarbonyl group, R ⁴¹ and R ⁴² cannot be a hydrogen atom or an alkyl group at the same time.基, R ²³ , R ²⁴ , R ²⁷ , R ²⁸ , R ³² , R ³³ ,
R ³⁷ and R ³⁸ are each independently a hydrogen atom, an alkoxy group, a fluorine atom, a trifluoromethyl group, or a trifluoromethoxy group, and R ²¹ has a hydrogen atom or a nitrogen atom as a hetero atom. a nitrogen atom and the naphthopyran ring are bonded to are substituted or unsubstituted heterocyclic group or plurality aromatic to heterocyclic group hydrocarbon ring or fused heterocyclic group which aromatic heterocyclic rings are fused, R ²⁵ is a carbon the number is 1-5 alkyl group, R ²⁹ and R ³⁰ are each independently a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, R ^34,
R ³⁵ is particularly preferably a chromene compound independently represented by a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms.

Specific examples of such compounds are as follows.
-Morpholino-3- (4'-N, N-bis [4 "-carboxyethylphenyl] aminophenyl) -3-phenyl-3H-benzo (f) chromene; 6-morpholino-3
-(4'-N, N-bis [4 "-cyanophenyl] aminophenyl) -3-phenyl-3H-benzo (f) chromene; 6-indolino-3- (4'-N, N-bis [4
"-Trifluorophenyl] aminophenyl) -3-phenyl-3H-benzo (f) chromene; 6-morpholino-3- (4'-acetylaminophenyl) -3-phenyl-3H-benzo (f) chromene; 6 -Morpholino-3
-(4'-dicyanomethylaminophenyl) -3- (3
'-Fluoro, 4'-methoxyphenyl) -3H-benzo (f) chromene; 5-isopropyl-2- (4'-phenylsulfonylaminophenyl) -2-phenyl-2Hbenzo (h) chromene; 2- (4' -Bistrifluoromethylaminophenyl) -2-phenyl-2H-1
-Oxatriphenylene and the following compounds

[0096]

Embedded image

And the like. The compound of the present invention represented by the general formula (1) generally exists as a colorless or pale yellow solid or viscous liquid at normal temperature and normal pressure, and is prepared by the following means (a) to (c). You can check.

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

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

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

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 (16)

[0103]

Embedded image (However, the following equation (17)

[0104]

Embedded image

The monovalent group represented by the general formula (4)
Is a condensed polycyclic organic group which may have a substituent corresponding to the group represented by ) And a general formula (18)

[0106]

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(Wherein R ¹ , R ² , R ³ and R ⁴ have the same meanings as defined in the general formula (1)) in the presence of an acid catalyst. It is.

As the hydroxyl derivative represented by the general formula (16), for example, a 1-naphthol derivative, a 2-naphthol derivative and the like are commercially available. Also, if not commercially available, for example,
Examples of the method include a method in which a halogen derivative which is a precursor of a target vidroxyl derivative is lithiated with an organolithium such as n-butyllithium, and is derivatized to a hydroxyl derivative using a known hydroxylating reagent.

The propargyl alcohol derivative represented by the general formula (18) is, for example, a compound represented by the general formula (1)
It can be synthesized by reacting the ketone derivative corresponding to 8) with a metal acetylene compound such as lithium acetylide.

The reaction conditions for reacting the hydroxyl derivative represented by the general formula (16) with the propargyl alcohol represented by the general formula (18) in the presence of an acid are not particularly limited. It is preferred to employ reaction conditions.

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

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

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

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

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

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

[0119]

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 1,1-Dichloronaphthalenone was synthesized from 2-naphthol and chlorine, reacted with morpholine, and then reduced with Raney nickel to obtain the following hydroxyl derivative:

[0121]

Embedded image 1.3 g (5.6 mmol) and the following propargyl alcohol derivative

[0122]

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2.9 g (5.6 mmol) was dissolved in 80 ml of toluene, and 0.02 g of p-toluenesulfonic acid was added, followed by refluxing for 1 hour. After the reaction, the solvent was removed and the residue was purified by chromatography on silica gel using a mixed solvent of hexane and ethyl acetate (7: 3) as an eluent to obtain 1.6 g of an orange oily product. Was. The obtained product was recrystallized with 50 ml of a mixed solvent of isopropyl alcohol and toluene (9/1) to obtain 1.2 g of a powdery product. The yield was 29%. Elemental analysis of this product gave C7
7.33%, H 5.66%, N 3.77%, O13.2
A 3%, a calculated value of _{C 47 H 4 N 2 O 6} C77.
24%, H 5.79%, N 3.83%, O 13.13%
Very well matched.

Further, when the proton nuclear magnetic resonance spectrum was measured, as shown in FIG.
4.4 ppm based on the ethyl proton of the ester group
0H peak, 8H peak based on methylene proton of morpholino group at δ3.1, δ4.0 ppm, δ6.2
A peak of 24H based on an aromatic proton and a proton of an alkene was shown at about 8.1 ppm. Further measurement of ¹³ C-nuclear magnetic resonance spectrum revealed that δ
A peak based on carbon of an aromatic ring and an alkene was shown at around 100 to 160 ppm, a peak based on carbonyl carbon at δ 170 ppm, and a peak based on alkyl and alkylene carbons at δ 10 to 70 ppm. From the above results, it was confirmed that the isolated product was a compound represented by the following structural formula.

[0125]

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Examples 2 to 9 In the same manner as in Example 1, chromene compounds shown in Table 1 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 and 2
Was confirmed to be a compound represented by the structural formula shown in Table 1.
Table 3 shows the elemental analysis values of these compounds, the calculated values obtained from the structural formulas of the respective compounds, and characteristic ¹ H-NMR spectra.

[0127]

[Table 1]

[0128]

[Table 2]

[0129]

[Table 3]

Examples 10 to 18 and 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, It was added to 5 parts of 2-hydroethyl methacrylate and mixed well. This mixture was poured into a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer, and cast polymerization was performed. In the polymerization, the temperature was gradually increased from 30 ° C. to 90 ° C. over 18 hours using an air furnace, and the temperature was maintained at 90 ° C. for 2 hours. After the completion of the polymerization, the polymer was removed from the glass mold of the mold.

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

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

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

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

A photochromic polymer was obtained in the same manner as described above, except that the compounds obtained in Examples 2 to 9 were used as the chromene compound. The properties are shown in Table 4.

[0136]

[Table 4] Further, for comparison, the following formulas (A) and (B)

[0137]

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[0138]

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A photochromic polymer was obtained in the same manner as described above using the compound represented by the formula (1), and the characteristics are shown in Table 5.

[0140]

[Table 5]

The photochromic polymers of Comparative Examples 1 and 2 have large initial coloring. In contrast, in Examples 10 to 18 using the chromene compound of the present invention, the photochromic polymer has little initial coloring.

[0142]

The chromene compound of the present invention has little initial coloring in a solution or in a solid polymer matrix. For example, a photochromic lens using the chromene compound of the present invention has a good dimming function such that it has little initial coloring and is almost colorless indoors, but is colored outdoors.

[Brief description of the drawings]

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

Claims (4)

[Claims] [Claim 1] The following general formula (1) [Wherein, R ¹ represents the following formula (2): Wherein R ⁵ and R ⁶ are each independently a hydrogen atom, a trifluoromethyl group, a cyano group, a cyanomethyl group, a sulfonyl group, an arylsulfonyl group, an alkylsulfonyl group, a sulfamoyl group, a nitro group, a carboxylyl group,
It is a carboxamide group, an alkoxycarbonyl group, or a carbamoyl group, and R ⁵ and R ⁶ are not hydrogen atoms at the same time. Or a group represented by the following formula (3): In the formula, R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group, a trifluoromethyl group, a cyano group, a cyanomethyl group, an arylsulfonyl group, an alkylsulfonyl group, an alkylcarbonyl group, or an arylcarbonyl group. , R ⁷ and R ⁸ are not simultaneously a hydrogen atom or an alkyl group. R ² , R ³ , and R ⁴ are each independently a hydrogen atom, an alkoxy group, a halogen atom, a trifluoromethyl group, or a trifluoromethoxy group; Embedded image Is a divalent condensed polycyclic organic group which may have a substituent having a benzene ring condensed to the 2H-pyran ring in the general formula (1) as an element. is there. A chromene compound represented by the formula: 2. The odor of the general formula (1) according to claim 1.
And the following formula (4)A divalent condensed polycyclic ring which may have a substituent represented by
The organic group is represented by the following formulas (5) to (8):中 In each formula, R⁹, R^Ten, R¹¹, R¹², R¹³, R¹⁴,
R^Fifteen, And R¹⁶Are each independently a hydrogen atom,
, An alkoxy group, an aralkoxy group, an aralkyl group,
Substituted amino group, cyano group, aryl group, halogen atom,
Having a nitrogen atom as a hetero atom and a condensed polycyclic ring
A heterocyclic group bonded to the ring of the formula organic group, or
Condensation of aromatic hydrocarbon ring or aromatic heterocyclic ring
Heterocyclic groups, and these groups may have a substituent.
K, R⁹, R¹², R¹³, R¹⁴, R^Fifteen, And R¹⁶Number of connections
A, b, c, d, e, and f each independently represent 0
An integer of from 1 to 3;^Ten, And R¹¹L and
And m are each independently an integer of 0 to 2, a to f,
each of the Rs that combine when l and m are 2 or more⁹,
R^{1 0}, R¹¹, R¹², R¹³, R¹⁴, R^FifteenOr R¹⁶Are each other
And represented by -Y- in the formula (8).
Is a group of the following formula:(Where Z¹And Z^TwoAre independently oxygen atoms or sulfur
A yellow atom, R¹⁷, R ¹⁸, R¹⁹, And R²⁰Is an archi
G, h, i, and j are each 1 to 4
Is an integer. A) any group represented by 基
Item 7. The chromene compound according to Item 1. 3. A photochromic material comprising the chromene compound according to claim 1 or 2. 4. A photochromic optical material comprising the chromene compound according to claim 1 or 2.