JPH08104672A - Fulgimide compound and its use - Google Patents

Abstract

PURPOSE: To obtain the subject new compound suppressed in color development in the initial color undeveloped state, convertible from colorless to color- developed form on being irradiated with ultraviolet light with the color change reversible, and having high durability, thus useful as a photochromic material. CONSTITUTION: This compound is expressed by formula I [X-ring is a (substituted) divalent aromatic hydrocarbon group or (substituted) divalent unsaturated heterocyclic group; Z-ring is a (substituted) norbornylidene group, bicyclo[3,3,1]nonylidene group or adamanthylidene group; R1 is a (substituted) monovalent hydrocarbon group or (substituted) monovalent heterocyclic group; R2 is a perhalogenoalkyl, CN, (substituted)alkoxycarbonyl, etc.], e.g. N-cyano-4- cyclopropyl-6,7-dihydrospirobenzothiophenedicarboxyimido-7,2'- tricyclo[3,3,1,13,7]decane. The compound of formula I is obtained by reaction of a compound of formula II with the corresponding amine to form a compound which is then cyclized e.g. by heating at 160-220 deg.C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel fulgimide compound having a photochromic action, and its use. More specifically, a novel fulgimide compound which changes from colorless to a colored form by the action of light including ultraviolet rays such as sunlight or light of a mercury lamp, the change is reversible, and has excellent durability, and its Regarding use.

[0002]

2. Description of the Related Art Photochromism is a phenomenon that has been attracting attention for several years, and when a compound is irradiated with light including ultraviolet rays such as sunlight or light from a mercury lamp, the color of the compound is rapidly changed and the light irradiation is performed. It is a reversible action that returns to the original color when you leave it in the dark. A compound having this property is called a photochromic compound, and compounds having various structures have been conventionally synthesized and proposed, but no special common skeleton is recognized in the structure.

Against this background, Japanese Patent Laid-Open No. 2-281
The following general formula shown in Japanese Patent No. 54

[0004]

[Chemical 4]

The fulgide compound or fulgimide compound represented by the formula (1) is stable and colorless in a general state,
When exposed to sunlight or ultraviolet rays, the color develops immediately,
It is a compound having excellent photochromic properties because it returns to colorless when the irradiation is stopped and these discolorations are repeated with good durability. Here, in the fulgide compound or the fulgimide compound,

[0006]

Embedded image

An aromatic hydrocarbon group or an unsaturated heterocyclic group is shown as R ₁ , and a hydrocarbon group or a heterocyclic group is shown as R ₁ '. As Y ′, an oxygen atom, an imide group, a hydrogen atom of the imide group, an electron donating group of an alkyl group or an aryl group, a cyano group, an alkoxycarbonyl group or the like via an alkylene group, an alkylidene group or the like. The group substituted with a group to which the electron-withdrawing group of is bonded. And

[0008]

[Chemical 6]

Are each a norbornylidene group or an adamantylidene group which may have a substituent.

[0010]

Since the above-mentioned fulgimide compound has a rigid and strain-free cage-like adamantylidene group or norbornylidene group, it weakens a single bond forming a part of the 6-membered ring, It is believed that irradiation with light, including ultraviolet light, facilitates electron-cyclic ring opening, resulting in a colored form. However, these compounds have a drawback that they are already yellowish in the state before being irradiated with ultraviolet rays (hereinafter, also referred to as initial coloring) with the increase in the maximum absorption wavelength, which is used for photochromic lenses and the like. If it does, the lens will turn yellow at the beginning.

From the above background, there has been a demand for the development of a photochromic compound without initial coloring.

[0012]

Means for Solving the Problems As a result of intensive studies for suppressing the initial coloration of the above photochromic compound, the present inventors have found that light containing ultraviolet rays such as sunlight or the light of a mercury lamp changes from colorless to colorless. The present invention has been completed by successfully synthesizing a fulgimide compound that changes to a colored or darkened state and the change is reversible and does not cause initial coloring.

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

[0014]

[Chemical 7]

{Wherein the following formula (a)

[0016]

Embedded image

Is a divalent aromatic hydrocarbon or divalent unsaturated heterocyclic group, each of which may have a substituent, and R
₁ is a monovalent hydrocarbon group or a monovalent heterocyclic group which may each have a substituent, and has the following formula (b)

[0018]

[Chemical 9]

Is a norbornylidene group which may have a substituent, a bicyclo [3,3,1] nonylidene group or an adamantylidene group, and R ₂ is a perhalogenoalkyl group, a cyano group or a substituent. Alkoxycarbonyl group which may have, alkylcarbonyl group which may have a substituent, arylcarbonyl group which may have a substituent,
A nitro group, a sulfonyl group, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, or an aryloxycarbonyl group which may have a substituent. } The fulgimide compound represented by these.

In the general formula (I) of the present invention, the group of the above formula (a) is an aromatic hydrocarbon group or an unsaturated heterocyclic group which may have a substituent. These groups may have up to 5 and preferably up to 3 substituents. The aromatic hydrocarbon group has 6 to 6 carbon atoms.
It has 20 and preferably 6 to 14 carbon atoms, and examples of the ring forming the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring and a phenanthrene ring.

The unsaturated heterocyclic group is a 5-membered or 6-membered mono-heterocyclic group containing 1 to 3 at least one kind of hetero atom such as nitrogen atom, oxygen atom and sulfur atom, or A fused heterocyclic group in the form of a fused benzene ring or cyclohexene ring is shown. Examples of the ring forming such a heterocyclic group include nitrogen-containing heterocycles such as pyrrole ring, pyridine ring, quinoline ring, isoquinoline ring and indole ring; furan ring, benzofuran ring, pyran ring, tetrahydrobenzofuran ring and the like. Oxygen heterocycle;
Examples thereof include sulfur-containing heterocycles such as a thiophene ring, a benzothiophene ring, and a tetrahydrobenzothiophene ring.

Examples of the substituent which the aromatic hydrocarbon group or unsaturated heterocyclic group represented by the above formula (a) may have are halogen atoms such as fluorine, chlorine, bromine and iodine; and a hydroxyl group. Cyano group; nitro group; amino group;
Carboxyl group; alkylamino group having 1 to 4 carbon atoms such as methylamino group and diethylamino group; alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group and t-butyl group; trifluoromethyl group; A halogenalkyl group having 1 to 3 halogen atoms such as 2-chloroethyl group; a lower alkoxy group having 1 to 4 carbon atoms such as methoxy group, ethoxy group, t-butoxy group; phenyl group, naphthyl group, toluyl group An aryl group having 6 to 10 carbon atoms;
6 to 14 carbon atoms such as phenoxy group and 1-naphthoxy group
Aryloxy group of benzyl group, phenylethyl group,
Examples include aralkyl groups having 7 to 15 carbon atoms such as phenylpropyl group; aralkoxy groups having 7 to 15 carbon atoms such as benzyloxy group and phenylpropoxy group, and alkylthio groups having 1 to 4 carbon atoms. These substituents may be the same or different and the position is not particularly limited.

The group represented by the above formula (a) includes a halogen atom, a nitro group, an alkylthio group having 1 to 4 carbon atoms,
An aromatic hydrocarbon group or unsaturated, which may be substituted in each case by at least one atom or group selected from the group consisting of an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. It is preferably a heterocyclic group.

The group represented by the above formula (a) is an aryl group having 6 to 14 carbon atoms which may be substituted by 1 to 3 of each of the above-mentioned substituents in each case, or nitrogen. Having atoms, oxygen atoms and sulfur atoms 5
A monocyclic heterocyclic group having a six-membered ring or a six-membered ring or a condensed heterocyclic group in which a benzene ring or a cyclohexene ring is condensed with the heterocyclic group is more preferable.

Further, as the group represented by the above formula (a), a benzene ring, a 5-membered or 6-membered monocyclic heterocycle containing 1 to 3 heteroatoms, or a benzene ring or cyclohexene on the heterocycle. Those that are fused heterocycles in which the rings are fused are preferred. The benzene ring, monocyclic heterocycle or condensed heterocycle containing one or two of the above-mentioned substituents is also a preferred embodiment.

R ₁ in the general formula (1) is a monovalent hydrocarbon group or a monovalent heterocyclic group which may have a substituent. Here, as the hydrocarbon group or the heterocyclic group, known ones can be used without any limitation. Specific examples of the hydrocarbon group may be an aliphatic, alicyclic or aromatic hydrocarbon, and specific examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. Carbon number 1
To 20, preferably 1 to 6 alkyl groups; phenyl groups,
6 to 6 carbon atoms such as toluyl group, xylyl group and naphthyl group
14 aryl groups; a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group, which has 3 to 7 carbon atoms, and is preferably a cyclopropyl group.

The heterocyclic group is not particularly limited, but is, for example, a 5-membered ring containing 1 to 3 at least one kind of hetero atom such as nitrogen atom, oxygen atom and sulfur atom, or A 6-membered mono-heterocyclic group and the like are preferable. Examples of the ring forming this heterocyclic group include nitrogen-containing unsaturated heterocycles such as pyrrole ring and pyridine ring; oxygen-containing unsaturated heterocycles such as furan ring and pyran ring; nitrogen-containing unsaturated heterocycles such as thiophene ring. Saturated heterocycles are preferred. On the other hand, saturated heterocyclic groups such as saturated piperidine ring, piperazine ring, morpholine ring, pyrrolidine ring, indoline ring and chroman ring can also be used.

Specific examples of the substituents of the above R ₁ groups include the same substituents as described in the above formula (a), the number of which is 1 or more. It may be.

In the above general formula (I) of the present invention, the group of the above formula (b) is a norbornylidene group, a bicyclo [3,3,1] nonylidene group or an adamantylidene group, each of which may have a substituent. Means The norbornylidene group has the following formula (c)

[0030]

[Chemical 10]

A 7-norbornylidene group represented by the following formula is preferred, and a bicyclo [3,3,1] nonylidene group is represented by the following formula (d):

[0032]

[Chemical 11]

A bicyclo [3,3,1] 9-nonylidene group represented by the following is preferred, and an adamantylidene group is represented by the following formula (e):

[0034]

[Chemical 12]

A 2-adamantylidene group represented by: is preferred.

In the above formula, 7-
1 shows a skeleton structure of a norbornylidene group, a bicyclo [3,3,1] 9-nonylidene group or a 2-adamantylidene group.

In these 7-norbornylidene group, bicyclo [3,3,1] 9-nonylidene group or 2-adamantylidene group, the hydrogen atom in the above formula may be substituted by a substituent, and the number thereof is 1 It may be individual or more. When it has a substituent, its type, number and position are arbitrarily selected depending on the purpose and application. When it has a plurality of substituents, it may be the same or different.

Examples of the substituent of the above 7-norbornylidene group, bicyclo [3.3.1] 9-nonylidene group or 2-adamantylidene group include a hydroxy group; a methylamino group, a diethylamino group and the like having 1 carbon atom. ~ 4 alkylamino group; methoxy group, ethoxy group, tert-butoxy group, etc., C1-4 alkoxy group; benzyloxy group, etc., C7-15 aralkoxy group; phenoxy group, 1-naphthoxy group, etc. An aryloxy group having 6 to 14 carbon atoms; an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group and a t-butyl group; a halogen atom such as fluorine, chlorine and bromine; a cyano group; a carboxyl group; ethoxycarbonyl An alkoxycarbonyl group having 2 to 10 carbon atoms such as; a halogen-substituted alkyl group having 1 or 2 carbon atoms such as a trifluoromethyl group; a nitro group; Examples thereof include aryl groups having 6 to 10 carbon atoms such as phenyl group and toluyl group, and aralkyl groups having 7 to 9 carbon atoms such as phenylethyl group and phenylpropyl group.

Of these substituents, particularly preferable examples are a halogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

In the above general formula (I) of the present invention, R ₂ is a perhalogenoalkyl group, a cyano group, an alkoxycarbonyl group which may have a substituent, an alkylcarbonyl group which may have a substituent, or a substituent. An arylcarbonyl group which may have a group, a nitro group, a sulfonyl group, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, or an aryl which may have a substituent Indicates an oxycarbonyl group. All of these groups are electron-withdrawing groups, and in the present invention, such a specific electron-withdrawing group has a structure in which it is directly bonded to an imide group that constitutes a fulgimide compound, and thus the initial coloration of the fulgimide compound is obtained. Is significantly reduced.

In the above R ₂ , the perhalogenoalkyl group has 1 to 4 carbon atoms such as trichloromethyl group, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group and nonafluorobutyl group. Perhalogenoalkyl group; as the alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group,
Propoxycarbonyl group, butoxycarbonyl group, t-
An alkoxycarbonyl group having 2 to 5 carbon atoms such as butoxycarbonyl group; an alkylcarbonyl group having 2 to 5 carbon atoms such as methylcarbonyl group, ethylcarbonyl group, propylcarbonyl group, butylcarbonyl group, t-butylcarbonyl group An alkylcarbonyl group; an arylcarbonyl group, a benzoyl group, an arylcarbonyl group having 7 to 11 carbon atoms such as a 1-naphthylcarbonyl group; an alkylsulfonyl group, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, t-
An alkylsulfonyl group having 1 to 4 carbon atoms such as butylsulfonyl group; an arylsulfonyl group having 6 to 1 carbon atoms such as phenylsulfonyl group and naphthylsulfonyl group
0 arylsulfonyl group; Examples of the aryloxycarbonyl group include arylsulfonyl groups having 7 to 11 carbon atoms such as phenoxycarbonyl group and naphthoxycarbonyl group.

Further, as the substituents of the alkoxycarbonyl group, the alkylcarbonyl group, the arylcarbonyl group, the alkylsulfonyl group, the arylsulfonyl group and the aryloxycarbonyl group among the respective groups of R ₂ , specifically, The same substituents as those described in the formula (a) can be exemplified. And the number may be one or more. In particular, the group having this substituent is preferably a group substituted with a halogen atom or a cyano group. Further, the group substituted with the halogen atom is preferably one in which all of the alkoxy group, alkyl group or aryl group thereof is substituted with the halogen atom. Examples of such a substituent include a perhalogenoalkoxycarbonyl group having 2 to 5 carbon atoms such as a trichloromethoxycarbonyl group, a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a heptafluoropropoxycarbonyl group and a nonafluorobutoxycarbonyl group; trichloromethyl A perhalogenoalkylcarbonyl group having 2 to 5 carbon atoms such as a carbonyl group, a trifluoromethylcarbonyl group, a pentafluoroethylcarbonyl group, a heptafluoropropylcarbonyl group, and a nonafluorobutylcarbonyl group; and a 7 to 7 carbon atoms such as a pentafluorobenzoyl group And 11 perhalogenoarylcarbonyl groups.

In the general formula (I), the group represented by the above formula (b) is an optionally substituted 7-norbornylidene group, bicyclo [3.3.1] 9-nonylidene group or 2 An adamantylidene group, and R ₂ is a cyano group, a perhalogenoalkylcarbonyl group, an alkylcarbonyl group which may have a substituent, an arylcarbonyl group which may have a substituent, particularly a cyano group, a substituent The arylcarbonyl group which may have a group is more preferable from the viewpoint of suppressing the initial coloration of the obtained compound. Further, when a cyano group is used as R ₂ , the obtained fulgimide compound is a photochromic compound having durability that reversibly repeats coloring and decoloring, and is similar to other fulgimide compounds having the same maximum absorption wavelength at the time of color development. Compared with this, it is preferable since the effect of becoming more excellent is exhibited.

In the present invention, the flugimide compound represented by the general formula (I) which can be preferably used is exemplified by the following compounds.

(1) N-cyano-4-cyclopropyl-
6,7-Dihydrospirobenzothiophenedicarboximide-7,2'-tricyclo [3.3.1.13,7]
Decane (2) N-acetyl-4-cyclopropyl-6,7-dihydrospirobenzothiophenedicarboximide-
7,2'-Tricyclo [3.3.1.13,7] decane (3) N-benzoyl-4-cyclopropyl-6,7-
Dihydrospirobenzothiophene dicarboximide-
7,2′-Tricyclo [3.3.1.13,7] decane (4) N-acetyl-4-cyclopropyl-6,7-dihydro-2-methylspirobenzothiophenedicarboximide-7,2 ′ -Tricyclo [3.3.1.13,
7] decane (5) N-cyano-6,7-dihydro-4-methyl-2
-Phenylspirobenzothiophenedicarboximide-7,2'-tricyclo [3.3.1.13,7] decane (6) 5'-chloro-6,7-dihydro-N-methyl-
N'-Methylsulfonyl-4-isopropylspiroindole dicarboximide-7,2'-tricyclo [3.3.1.13,7] decane (7) 3 ', 5'-dichloro-3,4-dihydro- 1-
Ethyl-7-methoxy-N-trichloromethylcarbonylspirodibenzo [5,6-b: d] thiophenedicarboximide-4,2′-tricyclo [3.3.1.1]
3,7] decane (8) N-benzoyl-3,4-dihydro-5′-methyl-1- (p-methoxyphenyl) spirobenzo [5
6-b: d] furandicarboximido-4,2'-tricyclo [3.3.1.13,7] decane (9) 4-cyclopropyl-5'-methoxy-N'-phenyl-N-trichloromethyl Carbonyl spirobenzo [b] indole dicarboximide-4,2'-tricyclo [3.3.1.13,7] decane (10) 1-cyclopropyl-3,4-dihydro-N-
Phenylsulfonyl (6,7,8,9-tetrahydrodibenzo [5,6-b: d] thiophenedicarboximide-4,2'-tricyclo [3.3.1.13,7] decane The invention has been described above. The fulgimide compound represented by the general formula (I) generally exists as a light yellow solid at room temperature, and is generally represented by the following general formula (I) by the following means (a) to (c).
It can be confirmed that the compound is.

(A) Proton nuclear magnetic resonance spectrum ( ¹
The type and number of protons existing in the molecule can be known by measuring (1 H-NMR). That is, a peak due to an aromatic proton near δ 7 to 8 ppm, a group in the case where R ₁ is a cycloalkyl group near δ 1.2 to 2.5 ppm, a norbornylidene group, and a bicyclo [3.3.1] nonylidene group. Alternatively, a broad peak based on protons derived from the adamantylidene group appears. In addition, the relative number of δ peak intensities can be compared to determine the number of protons in each bonding group.

(B) By elemental analysis, each weight% of carbon, hydrogen, nitrogen, sulfur and halogen can be determined. Furthermore, the weight% of oxygen can be calculated by subtracting the total weight% of the recognized elements from 100. Therefore, the composition of the corresponding product can be determined.

(C) ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C
-NMR) makes it possible to know the type of carbon present in the molecule. R ₁ around δ27-52ppm
When is a cycloalkyl group, a peak derived from the carbon of the group and a norbornylidene group, a bicyclo [3.3.1] nonylidene group or an adamantylidene group, δ
Peak of carbon of aromatic hydrocarbon group or unsaturated heterocyclic group around 110-150ppm, δ160-170ppm
A peak based on carbon with> C = 0 appears in the vicinity.

The fulgimide compound of the general formula (I) of the present invention may be produced by any method,
The type of manufacturing method does not matter. However, although preferred and representative methods are described below, the present invention is not limited to these methods.

For example, it can be manufactured by the method of the following process A.

Process A: This process A comprises the following general formula (II)

[0052]

[Chemical 13]

(In the formula

[0054]

Embedded image

[0055]

[Chemical 15]

And R ₁ are the same as defined in the above general formula (I)) and the corresponding amines are reacted with each other, and then cyclized, and the fulgimide represented by the above general formula (I). It is a method for producing a compound.

The reaction in Process A is preferably carried out in a solvent, and examples of the solvent include aprotic polar solvents such as N-methylpyrrolidone, dimethylformamide, tetrahydrofuran and 1,4-dioxane.

A method of reacting the acid anhydride of the general formula (II) with the amine compound and then cyclizing the acid anhydride is, for example, 16
A method of heating to a temperature of 0 to 220 ° C., a combination of this heating and ultraviolet irradiation, or a method of contacting with a Lewis acid catalyst is suitably adopted. As the Lewis acid catalyst, known compounds such as SnCl ₄ , TiCl ₄ , SbCl ₅ ,
AlCl ₃ etc. can be used without any limitation. The amount of the Lewis acid catalyst used is not particularly limited, but it is usually preferably used in the range of 0.001 to 1 mol with respect to 1 mol of the compound to be cyclized.

In the process A, the general formula (I
When the acid anhydride of I) is reacted with an amine compound, the reaction ratio is adopted from a wide range, but generally, the molar ratio is 1:10 to 10: 1, preferably 1: 5 to 5: 1. Ranges are preferred.

The above reaction is usually carried out at a temperature of 25 to 160.
It is carried out under conditions of a temperature of 1 to 24 hours. After completion of the reaction, the solvent is removed, dehydration is carried out with a dehydrating agent such as acetyl chloride or acetic anhydride, and the cyclization reaction of the obtained compound is carried out under the above-mentioned conditions, whereby the fulgimide compound of the present invention can be obtained. .

In the above process A, the acid anhydride of the general formula (II) used as a starting material can be produced, for example, by the following method.

That is, the following general formula (IIa)

[0063]

Embedded image

(In the formula

[0065]

[Chemical 17]

And R ₁ are the same as defined in the above general formula (I)), and a carbonyl compound represented by the following general formula (IIb)

[0067]

Embedded image

(In the formula

[0069]

[Chemical 19]

Is the same as defined in the above general formula (I), and R ₃ and R ₄ are the same or different and have 1 to 6 carbon atoms.
Is an alkyl group. The acid anhydride of the general formula (II) can be obtained by subjecting the succinic acid diester derivative represented by) to a condensation reaction and performing the treatment described below.

In the condensation reaction, the compound of the general formula (IIa)
The reaction ratio of the carbonyl compound of (4) and the succinic acid diester derivative of the general formula (IIb) may be in a wide range,
Generally, the molar ratio is in the range of 1:10 to 10: 1, preferably 1: 5 to 5: 1. The reaction is usually 0 ° C to 110 ° C.
C., preferably in the range of 10.degree. C. to 100.degree.
The reaction is suitably carried out using a solvent, and the solvent is preferably an aprotic solvent, examples of which include benzene, diethyl ether, toluene,
Tetrahydrofuran etc. are mentioned.

This condensation reaction is generally carried out in the presence of a condensing agent such as sodium hydride, t-butoxide and sodium ethylate. Such a condensing agent is usually 0.1 per mol of the carbonyl compound of the general formula (IIa).
It is used in the range of 10 to 10 mol.

After completion of the reaction, the obtained dicarboxylic acid diester is converted into a free dicarboxylic acid. For this reaction, the conditions for the hydrolysis reaction in the presence of a base which are generally known per se are used. For example, it is carried out at a temperature of 0 to 80 ° C. using a 10% ethanolic sodium hydroxide solution.

The dicarboxylic acid thus obtained is converted into an acid anhydride according to a method known per se and represented by the general formula (II)
The acid anhydride of The reaction to obtain an acid anhydride is carried out by using a well-known reagent such as acetic anhydride and acetyl chloride.

Process B: This process B is represented by the following general formula (III)

[0076]

Embedded image

(In the formula

[0078]

[Chemical 21]

[0079]

[Chemical formula 22]

R ₁ and R ₁ are the same as defined in the above general formula (I)), wherein an imide compound represented by the general formula (I) is reacted with an alkali metal and then a corresponding halogen compound is reacted. ) Is a method for producing a fulgimide compound.

As the alkali metal used in this process B, metal sodium, metal potassium, metal lithium and the like are used. The reaction ratio of the alkali metal is generally 1. with respect to 1 mol of the compound represented by the general formula (III).
It is selected from the range of 0 to 10 mol. The reaction ratio of the halogen compound is generally 0.5 with respect to 1 mol of the compound corresponding to (III) obtained by reacting an alkali metal.
It is preferably selected from the range of 10 to 10 mol.

The solvent used in this reaction is the same as that described in the above process A. The reaction temperature is usually preferably in the range of 0 to 100 ° C.

The fulgimide compound of the general formula (I) of the present invention can be obtained by any of the above-mentioned Process A and Process B, or by modification thereof.

The fulgimide compound of the general formula (I) in the present invention has a photochromic action itself and is excellent in durability. However, by combining it with an ultraviolet stabilizer, durability of the photochromic action is improved. The sex is further improved. Therefore, the fulgimide compound of the present invention may be used in combination with a known ultraviolet stabilizer when it is put to practical use.

The fulgimide compound represented by the above general formula (I) of the present invention is well soluble in general organic solvents such as toluene, chloroform and tetrahydrofuran. When the fulgimide compound represented by the general formula (I) is dissolved in such a solvent, the solution is almost colorless and transparent with almost no initial coloration, and when it is irradiated with ultraviolet rays, it develops a color, and even when the light is blocked, the temperature is around room temperature. Its color development hardly changes, and even if it is heated to around 80 ° C, the state of color development is stable and does not return to the original colorless system, but when it is irradiated with white light containing no ultraviolet rays, it quickly returns to the original colorless state. It exhibits a reversible photochromic action. The photochromic action in the fulgimide compound of the general formula (I) also occurs in the polymer solid matrix, and the reversible speed is on the order of seconds.
As the high-molecular polymer forming the high-molecular matrix to be the object, any polymer in which the fulgimide compound represented by the general formula (I) of the present invention is uniformly dispersed may be used. Methyl acid, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polystyrene, polyacrylonitrile,
Polyvinyl alcohol, polyacrylamide, poly (2
-Hydroxyethylmethacrylate), polydimethylsiloxane, polycarbonate, poly (allyldiglycolcarbonate), or other polymers, or monomers that are the raw materials for these polymers, or polymers obtained by copolymerizing these monomers with other monomers. It is preferably used.

The photochromic composition of the present invention is dispersed in a thermoplastic resin by synthesizing the thermoplastic resin, that is, by carrying out polymerization in the presence of the photochromic composition, or by heating the thermoplastic resin and the photochromic composition. A method of melt-kneading at a temperature not lower than the melting temperature of the plastic resin can be mentioned.

Next, as the thermosetting resin, ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2
-Poly (acrylic acid) and poly (methacrylic acid) ester compounds such as bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane; diallyl phthalate,
Polyallyl compounds such as diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol carbonate, trimethylolpropane triallyl carbonate; Polyvalent thioacrylic acid and polyvalent thiomethacrylic acid ester such as 2-bis (methacryloylthio) ethane, bis (2-acryloylthioethyl) ether, 1,4-bis (methacryloylthiomethyl) benzene; glycidyl acrylate, glycidyl methacrylate , Β-methylglycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyloxymethacrylate, 3
-(Glycidyl-2-oxyethoxy) -2-hydroxypropyl methacrylate, 3- (glycidyloxy-
Methacrylate compounds or acrylate compounds such as 1-isopropyloxy) -2-hydroxypropyl acrylate and 3- (glycidyloxy-2-hydroxypropyloxy) -2-hydroxypropyl acrylate; radically polymerizable polyfunctional monomers such as divinylbenzene Polymers of

Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride and the like of each of these monomers; methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, etc. Acrylic acid and methacrylic acid ester compounds; diethyl fumarate, diphenyl fumarate, and other fumaric acid ester compounds; thioacrylic acid and thiomethacrylic acid ester compounds, such as methylthioacrylate, benzylthioacrylate, and benzylthiomethacrylate; styrene, chlorostyrene, Examples thereof include copolymers with radically polymerizable monofunctional monomers such as vinyl compounds such as methylstyrene, vinylnaphthalene, α-methylstyrene dimer and bromostyrene.

Further, addition of a polyvalent thiol compound such as ethanedithiol, propanetriol, hexanedithiol, pentaerythritol tetrakisthioglycolate, di (2-mercaptoethyl) ether and the above radical-polymerizable polyfunctional monomer. Copolymer; diphenylethane diisocyanate, xylylene diisocyanate, p
An addition polymer of a polyvalent isocyanate compound such as phenylene diisocyanate and a polyhydric alcohol compound such as ethylene glycol, trimethylolpropane, pentaerythritol and bisphenol A, or the above-mentioned polyvalent thiol compound can be used. These raw material monomers can be used alone or in combination of two or more.

For dispersion of the photochromic composition in the thermosetting resin, a method of mixing the raw material monomer of the thermosetting resin and the photochromic composition and then polymerizing the mixture is generally adopted.

The addition amount of the fulgimide compound of the general formula (I) of the present invention dispersed in the above-mentioned polymer is generally 0.001 to 7 per 100 parts by weight of the polymer.
The range is 0 parts by weight, preferably 0.005 to 30 parts by weight, and particularly preferably 0.1 to 15 parts by weight.

The photochromic action of the fulgimide compound of the general formula (I) of the present invention is remarkably improved in durability as compared with the conventionally known fulgimide compound.

Therefore, the compound of the present invention can be widely used as a photochromic material. For example, various storage materials replacing silver salt photosensitive materials, copying materials, photoconductors for printing, recording materials for cathode ray tubes, photosensitive materials for lasers, It can be used as various recording materials such as holographic photosensitive materials. Other,
The photochromic material using the compound of the present invention can also be used as a material for photochromic lens materials, optical filter materials, display materials, photometers, decorations and the like.

[0094]

INDUSTRIAL APPLICABILITY The fulgimide compound of the general formula (I) of the present invention has a specific electron-withdrawing group directly introduced into the imide portion thereof, so that the coloring in the initial undeveloped state is improved. It is suppressed, and the effect of lengthening the wavelength can be obtained.

Further, when R ₂ is a cyano group, the durability as a photochromic compound that reversibly repeats coloring and decoloring is higher than that of other fulgimide compounds having the same maximum absorption wavelength during color development. Excellent and especially good.

[0096]

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 10.0 g of 3-cyclopropyl thienyl ketone (0.
066 mol) and 20.0 g (0.065 mol) of diethyl 2-adamantylidene succinate of the following formula.

[0098]

[Chemical formula 23]

A solution of and was dissolved in 200 cc of toluene was prepared. Then, the above-mentioned toluene solution was vigorously stirred for 10 hours while maintaining the liquid temperature at 0 ° C. or lower in a solution in which 5.6 g of sodium hydride was dispersed in 200 cc of toluene. After hydrolysis with an excess of 10% alcoholic potassium hydroxide solution, the dicarboxylic acid obtained by acidification with hydrochloric acid was treated with 100 cc of acetyl chloride and purified by chromatography on silica gel to give fulgide of the formula 11.5 g of compound was obtained.

[0100]

[Chemical formula 24]

The obtained compound was dissolved in 100 cc of acetone, 5.5 g (0.131 mol) of cyanamide was added dropwise, and the mixture was stirred for 2 hours. After the reaction, the solvent was removed, the residue was dissolved in acetyl chloride, refluxed for 1 hour, and cyclized. The obtained compound was refluxed in O-dichlorobenzene for 1 hour to be rearranged to the following fulgimide compound (1). This compound was purified by chromatography on silica gel using chloroform and hexane as eluents,
Recrystallization from toluene and isopropyl alcohol gave pale yellow needle crystals in a yield of 15%. The elemental analysis values of this compound are C 70.79%, H 5.7
2%, N 7.15%, O 8.20%, S 8.23%, which is a calculated value for C ₂₃ H ₂₂ N ₂ O ₂ S.
0.74%, H 5.68%, N 7.17%, O 8.
It was in very good agreement with 19% and S 8.21%.

Further, the proton nuclear magnetic resonance spectrum was measured to find that the peak of 2H due to the proton of the thiophene ring was around δ 7.0 to 7.5 ppm, and the peak of 1H due to the proton rearranged at around δ 3.7 ppm was 1H. , Δ1.3
A peak at 19H of a proton based on a cyclopropyl group and a 2-adamantylidene group was shown at about 2.5 ppm.

Furthermore, ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C
-NMR), a peak based on the carbon of the 2-adamantylidene group at δ27-70 ppm, δ1
A peak due to the carbon of the cyclopropyl group appears at around 0.2 ppm, a peak due to the carbon of the thiophene ring near δ110 to 160 ppm, and a peak due to the carbon of> C = O bond near δ160 to 170 ppm.

From the above results, it was confirmed that the isolated product was the fulgimide compound (1) represented by the following structural formula.

[0105]

[Chemical 25]

Example 2 A fulgimide compound having the following structural formula was obtained in the same manner as in Example 1 except that NH ₃ was used in place of the cyanamide of Example 1.

[0107]

[Chemical formula 26]

6.5 g (0.015 mol) of this compound
Was dissolved in tetrahydrofuran and metal potassium was reacted at room temperature to obtain 5.4 g of potassium imide of the following formula.

[0109]

[Chemical 27]

This and acetyl chloride 0.79 g (0.01
mol) was reacted in dimethylformamide to obtain the following fulgimide compound (2). This compound was purified by chromatography on silica gel using chloroform and hexane as eluents and was obtained as yellow needle crystals from toluene and isopropyl alcohol in 42% yield. The elemental analysis values of this compound are C 71.61%, H 6.02%, N 3.36.
%, O 11.47%, S 7.70%, and C ₂₅ H
₂₅ NO ₃ S calculated value, C 71.57%, H 6.
01%, N 3.34%, O 11.44%, S 7.6
It was very close to 4%. When the proton nuclear magnetic resonance spectrum was measured, a peak of 2H due to an aromatic proton, δ, was found around δ 7.0 to 8.0 ppm.
1H based on 1-5 rearranged protons around 3.7ppm
, A peak of 22H based on a cyclopropyl group and a 2-adamantylidene group was shown at δ 1.0 to 2.2 ppm.

Furthermore, ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C
-NMR), a peak based on the carbon of the 2-adamantylidene group at δ 27 to 52 ppm, δ 9.
A peak due to the carbon of the cyclopropyl group at around 7 ppm,
A peak due to the carbon of the methyl group of the acetyl group appears at about δ25 to 35 ppm, a peak due to the carbon of the thiophene ring at about δ110 to 160 ppm, and a peak due to the carbon of the> C═O bond at about δ160 to 170 ppm.

From the above results, it was confirmed that the isolated product was the fulgimide compound (2) represented by the following structural formula.

[0113]

[Chemical 28]

Example 3 3.3 g (0.01 mol) of a fulgimide compound of the following formula

[0115]

[Chemical 29]

[0116] was dissolved in tetrahydrofuran, and 1 g of metallic potassium was reacted with this at room temperature to obtain 3.0 g of imide potassium having the following formula.

[0117]

Embedded image

This and benzoyl chloride (1.41 g, 0.01)
(mol) was reacted in dimethylformamide to obtain the following fulgimide compound (3). This compound was purified by chromatography on silica gel using chloroform and hexane as eluents and was obtained in 55% yield as pale yellow crystals from toluene and isopropyl alcohol. The elemental analysis values of this compound are C 72.40%, H 5.88%, N 3.27.
%, O 7.15%, S 7.45%, and C ₂₆ H ₂₅
Calculated value for NO ₃ S C 72.36%, H
5.84%, N 3.25%, O 11.12%, S
Very good agreement with 7.43%. The proton nuclear magnetic resonance spectrum was measured and found to be δ 7.0-7.5 pp.
7H peak due to the proton of the thiophene ring and the benzene ring near m, 1H peak due to the 1.5 rearranged proton near δ 3.7 ppm, cyclopropyl group and 2-adamantyl around δ 1.3 to 2.5 ppm. A 19 H peak of the proton based on the den group was shown.

Furthermore, ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C
-NMR), a peak based on the carbon of the 2-adamantylidene group at δ27-70 ppm, δ1
A peak due to the carbon of the cyclopropyl group appears at around 0.2 ppm, a peak due to the carbon of the thiophene ring and the benzene ring near δ110 to 160 ppm, and a peak due to the carbon of the> C = O bond near δ160 to 170 ppm.

From the above results, it was confirmed that the isolated product was a fulgimide compound (3) represented by the following structural formula.

[0121]

[Chemical 31]

Example 4 Various fulgimide compounds were synthesized from the raw materials shown in Table 1 in the same manner as in Examples 1 to 3.

The obtained compounds were subjected to elemental analysis, proton nuclear magnetic resonance spectrum and ¹³ C-nuclear magnetic resonance spectrum in the same manner as in Examples 1 to 3, respectively, and the results of structural formula (4) to The compound represented by (33) was identified. In addition, Table 2 shows the elemental analysis values of this compound,
The calculated values obtained from the structural formula of each compound and the characteristic spectrum of the proton nuclear magnetic resonance spectrum are shown.

[0124]

[Table 1]

[0125]

[Table 2]

[0126]

[Table 3]

[0127]

[Table 4]

[0128]

[Table 5]

[0129]

[Table 6]

[0130]

[Table 7]

[0131]

[Table 8]

[0132]

[Table 9]

[0133]

[Table 10]

[0134]

[Table 11]

[0135]

[Table 12]

Example 5 0.04 part of the fulgimide compound was added to 70 parts of tetraethylene glycol dimethacrylate, 15 parts of triethylene glycol dimethacrylate, and 10 parts of glycidyl methacrylate.
Parts, 5 parts of 2-hydroethylmethacrylate and 1 part of perbutyl ND as a polymerization catalyst were added and mixed sufficiently until completely dissolved. This mixed solution was poured into a mold composed of a glass plate and a gasket composed of an ethylene-vinyl acetate copolymer, and the mixture was heated at 35 ° C to 90 ° C at 20 ° C in an air oven.
Polymerization was carried out by raising the temperature over time. After completion of the polymerization, the polymer was removed from the glass mold of the mold.

On the obtained polymerized plate, a xenon long life fade meter FAL-25 manufactured by Suga Test Instruments Co., Ltd.
AX-HC (output: 2.5 kW, light source: xenon
Long-life arc lamp) was used to irradiate with xenon light, and the maximum absorption wavelength in the colored state was measured. In addition, the initial color tone is visually observed and a color difference meter (S
M-4 type) was used to measure the YI of the sample.

[0138] In addition, JIS L0843, JISB 7
Fatigue life (T1 / 2) was measured according to 754. T1
/ 2 is defined as the time required for the color density to decay to half the initial value when the film is illuminated on the fade meter.

The results are shown in Table 3.

For comparison, with respect to the compounds represented by the following (A) to (I), a polymer plate was prepared in the same manner, and its physical properties were measured in the same manner as above.

[0141]

Embedded image

[0142]

[Chemical 33]

[0143]

Embedded image

[0144]

Embedded image

[0145]

Embedded image

[0146]

Embedded image

[0147]

[Chemical 38]

[0148]

[Chemical Formula 39]

[0149]

[Chemical 40]

[0150]

[Table 13]

[Brief description of drawings]

FIG. 1 shows ¹ H—N of the compound obtained in Example 1.
It is a chart of MR.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C09K 9/02 B G03C 1/73 503

Claims (2)

[Claims] 1. A compound represented by the following general formula (I): {In the formula, the following formula (a): Is a divalent aromatic hydrocarbon or divalent unsaturated heterocyclic group which may each have a substituent, and R ₁ is a monovalent hydrocarbon group which may have a substituent, or It is a monovalent heterocyclic group and has the following formula (b): Is a norbornylidene group, a bicyclo [3,3,1] nonylidene group or an adamantylidene group, each of which may have a substituent, and R ₂ has a perhalogenoalkyl group, a cyano group or a substituent. Good alkoxycarbonyl group, optionally substituted alkylcarbonyl group, optionally substituted arylcarbonyl group, nitro group, sulfonyl group, optionally substituted alkylsulfonyl group, substituent Is an arylsulfonyl group which may have or an aryloxycarbonyl group which may have a substituent. } The fulgimide compound represented by these. 2. A photochromic material comprising the fulgimide compound according to claim 1.