JPH06293772A - New compound - Google Patents

Abstract

(57) [Abstract] [Purpose] To obtain a photochromic compound having excellent durability and having a further improved fading speed when light irradiation is stopped. [Structure] The following general formula [I]: (In the formula [Chemical formula 2] Is a divalent aromatic hydrocarbon group which may have a substituent or a divalent unsaturated heterocyclic group R ₁ may be a monovalent hydrocarbon group which may have a substituent, or Monovalent heterocyclic group Is a 7-norbornylidene group or a bicyclo [3.3.1] 9-nonylidene group X, each of which may have a substituent, is an imino in which an oxygen atom or a hydrogen atom may be substituted with a specific group. Group)

Description

Detailed Description of the Invention

[0001]

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

[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 5]

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 fulgimide compound,

[0006]

[Chemical 6]

Is an aromatic hydrocarbon group or an unsaturated heterocyclic group, R ₁ is a hydrocarbon group or a heterocyclic group, and X is a hydrogen atom substituted with a specific group. The optional imino group and oxygen atom are shown. Also,

[0008]

[Chemical 7]

Is a norbornylidene group or an adamantylidene group which may have a substituent, and the norbornylidene group is, specifically, 2
Only the norboridene group is shown.

[0010]

The above-mentioned fulgide compound or fulgimide compound is a photochromic compound excellent in terms of durability such as reversible repetition of coloring and decoloring, as described above, but it is further irradiated with light. It has been desired to develop a photochromic compound having a further improved fading speed after the color development.

[0011]

[Means for Solving the Problems] The present inventors succeeded in the creation of a new compound as a result of repeated research for the purpose of obtaining a photochromic compound having a higher fading rate when the irradiation of light is stopped. Moreover, they have found that the compound achieves the above-mentioned object, and completed the present invention.
That is, the present invention provides the following general formula [I]

[0012]

[Chemical 8]

{In the formula

[0014]

[Chemical 9]

Is optionally substituted 2
A divalent aromatic hydrocarbon group or a divalent unsaturated heterocyclic group R ₁ is a monovalent hydrocarbon group or a monovalent heterocyclic group which may have a substituent, respectively.

[0016]

[Chemical 10]

Are optionally substituted 7
- nonylidene group or bicyclo [3.3.1] 9-nonylidene group X represents an oxygen atom group> N-R _{2 group> N-A 1 -B 1 -} (A 2) m - (B 2) n -R ₃ group> shows the N-a ₃ -A ₄ or a group> N-a ₃ -R ₄ (wherein, R ₂ represents a hydrogen atom, an alkyl group or an aryl group, a _1, a ₂ and a ₃ are the same Or, differently, an alkylene group, an alkylidene group, a cycloalkylene group or an alkylcycloalkane-diyl group, B ₁ and B
₂ is the same or different,

[0018]

[Chemical 11]

M and n each independently represent 0 or 1, but when m is 0, n is 0. R ₃ is an optionally substituted alkyl group, naphthyl group or A naphthylalkyl group, A ₄ is a naphthyl group which may have a substituent, and R ₄ is a halogen atom, a cyano group or a nitro group)}.

In the above general formula [I] of the present invention,

[0021]

[Chemical 12]

The group (1) is an aromatic hydrocarbon group or an unsaturated heterocyclic group, and these groups may have at most 5, preferably up to 3 substituents. The aromatic hydrocarbon group has 6 to 20 carbon atoms, preferably 6 to 20 carbon atoms.
The aromatic hydrocarbon ring has 14 rings, and examples of the ring forming the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring,
Examples include a fenanthrene ring.

As the unsaturated heterocyclic group, a 5-membered or 6-membered monocyclic heterocyclic group containing at least one hetero atom such as a nitrogen atom, an oxygen atom and a sulfur atom, or a benzene group thereof. A fused heterocyclic group in the form of a fused ring or cyclohexene ring is shown. The ring forming such a heterocyclic group is, for example, a nitrogen-containing heterocycle such as a pyrrole ring, a pyridine ring, a quinoline ring or an isoquinoline ring;
Oxygen-containing heterocycles such as furan ring, benzofuran ring and pyran ring; and sulfur-containing heterocycles such as thiophene ring and benzothiophene ring.

As mentioned above,

[0025]

[Chemical 13]

The aromatic hydrocarbon group or unsaturated heterocyclic group represented by may contain at most 5, preferably up to 3 substituents. Examples of such substituents are halogen atoms such as fluorine, chlorine, bromine and iodine; 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. Group; lower alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, t-butyl group; trifluoromethyl group; halogenated lower alkyl having 1 to 3 halogen atoms such as 2-chloroethyl group Group; lower alkoxy group having 1 to 4 carbon atoms such as methoxy group, ethoxy group and t-butoxy group; aryl group having 6 to 10 carbon atoms such as phenyl group, naphthyl group and toluyl group; phenoxy group, 1-naphthoxy group Carbon number 6 ~
14 aryloxy group; aralkyl group having 7 to 15 carbon atoms such as benzyl group, phenylethyl group and phenylpropyl group; aralkoxy group having 7 to 15 carbon atoms such as benzyloxy group and phenylpropoxy group and 1 to 10 carbon atoms Four
And an alkylthio group. These substituents may be the same or different and the position is not particularly limited.

Above

[0028]

[Chemical 14]

Is a halogen atom, a nitro group, a cyano group,
Amino group, C1-C4 alkylthio group, C1-C1
A divalent aromatic hydrocarbon group or divalent group which may be substituted in each case by at least one atom or group selected from the group consisting of a C4 alkyl group and a C1-4 alkoxy group. The unsaturated heterocyclic group is preferably.

In addition, the above

[0031]

[Chemical 15]

Has 6 to 14 carbon atoms which may be substituted in each case by 1 to 3 of the above-mentioned substituents.
An aryl group or a 5-membered or 6-membered monocyclic heterocyclic group containing one nitrogen atom, an oxygen atom and a sulfur atom, or a condensed heterocyclic group in which a benzene ring or a cyclohexene ring is condensed with the heterocyclic group. Is more preferable.

Further above

[0034]

[Chemical 16]

Is a divalent benzene ring, a 5-membered or 6-membered monocyclic heterocycle containing one heteroatom, or a condensed heterocycle in which a benzene ring or a cyclohexene ring is condensed with this heterocycle. Those are preferable. These benzene rings,
In the monocyclic heterocycle or the condensed heterocycle, the above-mentioned substituent is 1
It is also a preferable embodiment that one containing 2 to 2 is also included.

R ₁ in the general formula [I] is a monovalent hydrocarbon group which may have a substituent or 1
It is a valent heterocyclic group.

The hydrocarbon group of R ₁ is aliphatic,
It may be either an alicyclic or aromatic hydrocarbon, but specific examples thereof include 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group and butyl group, preferably 1 to 6 carbon atoms.
Alkyl group of phenyl group, toluyl group, xylyl group,
An aryl group having 6 to 14 carbon atoms such as naphthyl group; an aralkyl group having an alkylene group having 1 to 10 carbon atoms, preferably 1 to 4 such as benzyl group, phenylethyl group, phenylpropyl group and phenylbutyl group is preferable. . As the heterocyclic group for R ₁ , 1 to 3 at least one kind of hetero atom such as nitrogen atom, oxygen atom and sulfur atom,
Preferred is a 5- or 6-membered monocyclic heterocyclic group containing 1 or 2 or a condensed heterocyclic group in which benzene is condensed thereto. Specific examples of such a heterocyclic group include

[0038]

[Chemical 17]

In addition to the examples of the unsaturated heterocyclic group explained in the definition of, saturated piperidine ring, piperazine ring,
Examples thereof include saturated heterocyclic groups such as morpholine ring, pyrrozirine ring, indoline ring and chroman ring.

The above-mentioned hydrocarbon group or heterocyclic group for R ₁ may have a substituent, in particular. Such substituents are at most 5 relative to the hydrocarbon or heterocyclic group.
It is preferable to contain up to 3, preferably up to 3, and specific examples of the substituent include the above.

[0041]

[Chemical 18]

The same substituents as those described above can be exemplified.

Preferred as R ₁ is a halogen atom, an alkyl group having 1 to 4 carbon atoms which may be substituted with an alkoxy group having 1 to 4 carbon atoms, or a halogen atom or an alkyl group having 1 to 4 carbon atoms. An aryl group having 6 to 10 carbon atoms which may be substituted with an alkoxy group; or a 5-membered or 6-membered monocyclic heterocyclic ring containing 1 to 3, particularly 1 nitrogen, oxygen and sulfur atoms A cyclic group or a condensed heterocyclic group in which a benzene ring is condensed with the heterocyclic group, particularly a monocyclic heterocyclic group.

Further particularly preferred as R ₁ is
An alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

In the above general formula [I] of the present invention,

[0046]

[Chemical 19]

Is optionally substituted 7
-Norbornylidene group or bicyclo [3.3.1]
It means a 9-nonylidene group. Here, the 7-norbornylidene group has the following formula

[0048]

[Chemical 20]

## STR6 ## Also, bicyclo [3.3.1]
The 9-nonylidene group is represented by the following formula.

[0050]

[Chemical 21]

In the above formula, 7-
Norbornylidene group and bicyclo [3.3.1] 9-
It shows a skeleton structure of a nonylidene group. Even if they are the same norbornylidene group or bicyclo [3.3.1] nonylidene group, when the carbon atom having a bond is not at the specific position represented by the above formula, the obtained compound is
The photochromic compound does not have a sufficient fading rate. In these 7-norbornylidene group or bicyclo [3.3.1] 9-nonylidene group, the hydrogen atom in the above formula may be substituted with a substituent, and the number thereof may be one or more. When it has a substituent, its type, number and position are arbitrarily selected depending on the purpose and use. When it has a plurality of substituents, it may be the same or different.

The substituent of the above 7-norbornylidene group or bicyclo [3.3.1] 9-nonylidene group is
For example, hydroxy group; alkylamino group having 1 to 4 carbon atoms such as methylamino group and diethylamino group; 1 to 1 carbon atoms such as methoxy group, ethoxy group and tert-butoxy group.
An alkoxy group of 4; a carbon number of 7 to 1 such as benzyloxy group
5 aralkoxy group; phenoxy group, 1-naphthoxy group, etc., aryloxy group having 6 to 14 carbon atoms; methyl group, ethyl group, lower alkyl group having 1 to 4 carbon atoms, such as t-butyl group; fluorine, chlorine, Halogen atom such as silicon; cyano group; carboxyl group; carbon number such as ethoxycarbonyl 2
Alkoxycarbonyl group having 10 to 10; halogen-substituted alkyl group having 1 or 2 carbon atoms such as trifluoromethyl group; nitro group; aryl group having 6 to 10 carbon atoms such as phenyl group and toluyl group, phenylethyl group, phenylpropyl group And aralkyl groups having 7 to 9 carbon atoms.

Preferred examples of these substituents include a halogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms,
An alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aralkyl group having 7 to 9 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

In the above general formula [I] of the present invention, X is an oxygen atom (-0), a group> N-R ₂ , and a group> NA _{1.
-B 1 - (A 2) m} - (B 2) n -R 3, group> N-A ₃ -A ₄
Or a group> N-A ₃ -R _4.

In the general formula [I],

[0056]

[Chemical formula 22]

[0057] Even may 7- norbornylidene group or bicyclo substituted [3.3.1] 9-nonylidene a group and X is a _{group> N-A 1 -B 1 -} (A 2) m -(B
_{2) n} -R _3, group> N-A ₃ -A ₄ or a group> N-A ₃ -
R _4, in particular group> N-A ₃ -R ₄ or a group> N-A ₁ -B ₁ -
_{(A 2) m - (B} 2) n -R 3 ( where, R ₃ is a halogen atom,
1-3 selected from the group consisting of a cyano group and a nitro group
1 to 10 carbon atoms which may be substituted with one atom or group
From the viewpoint of durability of photochromic property of the obtained compound.

X in the general formula [I] is the above group> N-
A ₁ -B _1- (A ₂ ) _m- (B ₂ ) _n -R ₃ is a naphthyl group or a naphthylalkyl group, and the group> N-A ₃
In the case of -A ₄ , the number of main chain atoms sandwiched between the naphthyl group represented by R ₃ or R ₄ and the imide group (> N-) is 3
It is preferable that the number is in the range of from 7 to 7, because a compound excellent in durability of photochromic action can be obtained.

Next, R ₂ , R ₃ , R ₄ , and
The definitions of A ₁ , A ₂ , A ₃ , A ₄ , B ₁ , B ₂ , m and n will be described in detail.

R ₂ represents a hydrogen atom, an alkyl group or aryl, and examples of the alkyl group include a methyl group,
Examples thereof include ethyl group, propyl group, n-, iso- or ter-butyl group, pentyl group, hexyl group, octyl group and decyl group. Among them, those having 1 to 20 carbon atoms, Those having 1 to 10 are preferable. Examples of the aryl group include those having 6 to 10 carbon atoms such as phenyl group, tolyl group and naphthyl group.

A ₁ , A ₂ and A ₃ may be the same as or different from each other and may be an alkylene group, an alkylidene group, a cycloalkylene group or an alkylcycloalkane-diyl group. Specific examples thereof include, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a trimethylene group, a tetramethylene group, a 2,2-dimethyltrimethylene group and the like having 1 to 1 carbon atoms.
10 alkylene group; alkylidene group having 2 to 10 carbon atoms such as ethylidene group, propylidene group or isopropylidene group; cycloalkylene group having 3 to 10 carbon atoms such as cyclohexylene group; 2-methylcyclohexane-α,
1-diyl group

[0062]

[Chemical formula 23]

4-methylcyclohexane-α, 1-diyl group

[0064]

[Chemical formula 24]

Examples thereof include alkylcycloalkane-diyl groups having 6 to 10 carbon atoms. As A ₁ and A ₂ , particularly, an alkylene group having 1 to 6 carbon atoms, an alkylidene group having 2 to 6 carbon atoms, a cycloalkylene group having 3 to 6 carbon atoms,
An alkylcycloalkane-diyl group having 6 to 7 carbon atoms is preferable.

B ₁ and B ₂ may be the same as or different from each other, and are selected from the seven bonding groups of the following group.

[0067]

[Chemical 25]

M and n each independently represent 0 or 1, but when 0 is represented,-(A ₂ ) _m -or-(B
₂ ) _n- means a bond. Further, when m is 0, n is also 0.

R ₃ represents an alkyl group which may have a substituent, a naphthyl group or a naphthylalkyl group which may have a substituent. The number of carbon atoms of the above alkyl group is not particularly limited, but is preferably 1 to 10 and the number of carbon atoms of the alkyl group of the naphthylalkyl group is preferably 1 to 4.

The substituent of each of the above groups is not particularly limited, but the alkyl group may be substituted with 1 to 3 atoms or groups selected from the group consisting of a halogen atom, a cyano group and a nitro group. Well, the naphthyl group or naphthylalkyl group is a halogen atom, a cyano atom, a nitro group, an alkylamino group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms.
May be substituted with 1 to 3 atoms or groups selected from the group consisting of an alkyl group and an alkoxy group having 1 to 3 carbon atoms. As the alkyl group represented by R ₃ above,
The same alkyl groups as those exemplified for R ₂ can be used. Examples of the naphthylalkyl group include naphthylmethyl group, naphthylethyl group, naphthylpropyl group and naphthylbutyl group.

A ₄ represents a naphthyl group which may have a substituent. The kind of the substituent is not particularly limited, but the naphthyl group is a halogen atom, a cyano group, a nitro group, an alkylamino group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms. It may be substituted with 1 to 3 atoms or groups selected from the group consisting of:
R ₄ represents a halogen atom, a cyano group or a nitro group.

In the above definitions of R ₃ and A ₄ , the halogen atom may be fluorine, chlorine or bromine.

In the present invention, the compounds represented by the above general formula [I] which can be preferably used include the following compounds.

(1) 6,7-Dihydrido-N-methoxycarbonylmethyl-4-methylspirobenzo [5,6-
b] Thiophenedicarboximide-7,7′-bicyclo [2.2.1] heptane (2) N-cyanomethyl-6,7-dihydrido-4-methylspirobenzo [5,6-b] thiophenedicarboximide -7,7'-bicyclo [2.2.1] heptane (3) 2-Bromo-6,7-dihydrido-4-methyl-
N- (β-naphthylethyl) spirobenzo [5,6-
b] Thiophenedicarboximido-7,9′-bicyclo [3.3.1] nonane (4) 2-bromo-6,7-dihydrido-4-methylspirobenzo [5,6-b] thiophenedicarboxane Hydride-7,9'-bicyclo [3.3.1] nonane (5) N-chloromethyl-3-methoxy-6-methyl-
8,9-Dihydridospirodibenzo [5,6-b: d]
Thiophenedicarboximide-7,7'-bicyclo]
[2.2.1] Heptane (6) N-acetonyl-6,7-dihydride-2,4-
Diphenylspirobenzo [5,6-b] thiophenedicarboximide-7,7'-bicyclo [2,2,1] heptane (7) 1'-chloro-N- (3-oxobutyl-2-yl) -6 , 7-Dihydrido-4-phenylspirobenzo [5,6-b] thiophenedicarboximide-7,
7'-bicyclo [2.2.1] heptane (8) N-cyanomethoxymethyl-1 ', 4'-dichloro-4,5-dihydrido-7-methylspirobenzo [6,5-b] thiophenedicarboxy Imide-7,
7'-bicyclo [2.2.1] heptane (9) N- (5-cyano-3,3-dimethyl-2-oxopentyl) -7,8-dihydrido-1'-methoxy-
5-Methylspirodibenzo [5,6-b: d] furandicarboximido-7,7'-bicyclo [2.2.1]
Heptane (10) N- (N-methyl-3-oxohexyl)-
6,7-Dihydrido-1,1 ', 4-trimethylspiroindole-7,7'-bicyclo [2.2.1] heptane (11) N- (2-methylcyanoethyl) -1'-butyl-3, 4-dihydrido-5,7-dimethoxy-1-phenylspironaphthalene dicarboximide-4,7 ′
-Bicyclo [2.2.1] heptane (12) N-cyanomethyl-6,7-dihydrido-4-
Methyl spirobenzo [5,6-b] thiophene dicarboximide-7,7'-bicyclo [2.2.1] heptane (13) 1-phenyl-3,4-dihydrido-5,7-
Dimethoxy-N- (α-naphthylmethyl) spironaphthalene dicarboximide-7,7′-bicyclo [2.
2.1] Heptane (14) 3,4-dihydrido-1-methyl-N- (β-
Naphthylmethyl) spirodibenzo [5,6-b: d] thiophenedicarboximide-7,7'-bicyclo [2.2.1] heptane (15) 2-bromo-3,4-dihydrido-7-methylspiro Benzo [6,5-b] thiophenedicarboxyanhydride-4,9-bicyclo [3.3.1] nonane (16) 7,8-dihydrido-9-ethyl-3,3 ',
5-Trimethylcarbazoldicarboxyanhydride-8,9'-bicyclo [3.3.1] nonane (1
7) 8,9-dihydrido-N- (p-methylphenyl)
-6-Methylspirodibenzo [5,6-b: d] thiophenedicarboximide-7,9'-bicyclo [3.
3.1] Nonane (18) N-ethyl-3,4-dihydrido-1-methyl-5,6,7-trimethoxyspironaphthalene dicarboximide-4,9'-bicyclo [3.3.1] nonane (19) 6,7-Dihydrido-4- (2-furyl) -2
-Methyl-5'-phenylspirobenzo [5,6-b]
Thiophenedicarboxyanhydride-7,9'-
Bicyclo [3.3.1] nonane The compound represented by the above general formula [I] of the present invention generally exists as a pale yellow solid at room temperature, and is generally represented by the following (a) to (c). By a means, it can be confirmed that it is a compound of the general formula [I].

(A) Proton nuclear magnetic resonance spectrum ( ¹
The type and number of protons present in the molecule can be known by measuring (H-NMR). That is,
Aromatic proton-based peaks around δ7-8 ppm, broad peaks based on protons derived from 7-norbornylidene group or bicyclo [3.3.1] 9-nonylidene group at δ1.2-2.5 ppm, δ1 .2-4.
When R ₁ is an alkyl group, a peak based on the alkyl group appears near 0 ppm. 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
It is possible to know the type of carbon present in the molecule by measuring -NMR). A 7-norbornylidene group or bicyclo [3.3.
1] Peak derived from carbon of 9-nonylidene group, δ15
When R ₁ is an alkyl group at about 35 ppm, a peak due to the carbon of the alkyl group, δ 110 to 150 ppm at the peak of carbon of an aromatic hydrocarbon group or an unsaturated heterocyclic group, at δ 160 to 170 ppm around> C A peak based on the carbon at = 0 appears.

The compound of the general formula [I] of the present invention may be produced by any method, and the type of the production method is not limited. However, although preferred and representative methods are described below, the present invention is not limited to these methods.

Process A: This process A comprises the following general formula [II]

[0080]

[Chemical formula 26]

(In the formula

[0082]

[Chemical 27]

[0083]

[Chemical 28]

And R ₁ are the same as defined in the above general formula [I]), or the compound represented by the above general formula [II] and the following general formula [III-a], [III-b], [III-c] or [III-
d], H ₂ N-R ₂ [III-a] _{H 2 N-A 1 -B 1} - (A 2) m - (B 2) n -R 3 [III-b] H ₂ N-A ₃ - A ₄ [III-c] H ₂ N-A ₃ -R ₄ [III-d] (In the formula, R ₂ , R ₃ , R ₄ , A ₁ , A ₂ , A ₃ , A ₄ , B ₁ , B.
₂ , m and n are the same as defined in the above general formula [I], and are reacted with an amine compound and then cyclized.

[0085]

[Chemical 29]

(In the formula

[0087]

[Chemical 30]

[0088]

[Chemical 31]

R ₁ and X are the same as defined in the above general formula [I]).

In this process A, the above general formula [I
By subjecting the acid anhydride of I] to the cyclization reaction, a compound in which X in the general formula [I] in the present invention corresponds to an oxygen atom can be obtained. Further, by reacting the acid anhydride of the general formula [II] with the amine compound of the above [III-a] to [III-d] and then performing a cyclization reaction, X has an imide ring other than an oxygen atom. The compound of general formula [I] which is the object of the present invention can be obtained.

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.

In the case where the acid anhydride of the general formula [II] is directly cyclized, or when the acid anhydride and the amine compound are reacted and then cyclized, the cyclization reaction in any case is performed under the same conditions. It can be carried out. For this cyclization reaction, for example, a method of heating to a temperature of 160 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 , Sb
Cl 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 [II]
When the acid anhydride of the above is reacted with the amine compound of the general formulas [III-a] to [III-d], the reaction ratio is adopted from a wide range, but in general, the molar ratio is 1:10 to 10 :.
A range of 1, preferably 1: 5 to 5: 1 is suitable.

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 performed with a dehydrating agent such as acetyl chloride or acetic anhydride, and the cyclization reaction of the obtained compound is performed under the above-mentioned conditions to obtain the compound [I] of the present invention. You can

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]

[0097]

[Chemical 32]

(In the formula

[0099]

[Chemical 33]

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]

[0101]

[Chemical 34]

(In the formula

[0103]

[Chemical 35]

Is the same as defined in the above general formula [I], and R ₅ and R ₆ 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 the formula (1) to a condensation reaction and performing the treatment described below.

In the condensation reaction, the reaction ratio of the carbonyl compound of the general formula [IIa] and the succinic acid diester derivative of the general formula [IIb] may be in a wide range, but is generally in a molar ratio of 1:10. 10: 1, preferably 1: 5
Is in the range of 5: 1. The reaction is usually performed in the range of 0 ° C to 110 ° C, preferably 10 ° C to 100 ° C. Also,
The reaction is suitably carried out using a solvent, and as the solvent, an aprotic solvent is desirable, and examples thereof include:
Examples thereof include benzene, diethyl ether, toluene and tetrahydrofuran.

This condensation reaction is generally carried out in the presence of a condensing agent such as sodium hydride, t-butoxide and sodium ethylate. The condensing agent is usually 0.1 to 1 mol per mol of the carbonyl compound of the general formula [IIa].
Used in the range of 10 moles.

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 can be converted to an acid anhydride according to a method known per se to obtain the acid anhydride of the above-mentioned general formula [II]. The reaction to make an acid anhydride is
This is carried out by using a well-known reagent such as acetic anhydride and acetyl chloride.

Process B: This process B comprises the following general formula [IV]

[0110]

[Chemical 36]

(In the formula

[0112]

[Chemical 37]

[0113]

[Chemical 38]

And R ₁ are the same as defined in the above general formula [I]) with an imide compound reacted with an alkali metal, and then the following general formulas [Va], [Vb],
[V-c] or [V-d] Br-R ₂ [V-a] _{Br-A 1 -B 1 - (} A 2) m - (B 2) n -R 3 [V-b] Br-A ₃ -A ₄ [V-c] Br-A ₃ -R ₄ [V-d] (wherein _{R 2, R 3, R 4} , A 1, A 2, A 3, A 4, B 1, B
₂ , m and n are the same as defined in the above general formula [I]) and are reacted with a bromine compound represented by the following general formula [I].

[0115]

[Chemical Formula 39]

(In the formula

[0117]

[Chemical 40]

[0118]

[Chemical 41]

R ₁ and X are the same as defined in the above general formula [I]. However, X is selected from the group excluding the case where it is an oxygen atom from the definition of the general formula [I]. ) Is a method for producing the compound.

As the alkali metal used in the process B, metal sodium, metal potassium, metal lithium, etc. are used. The reaction ratio of the alkali metal is generally 1.0 to 1 mol of the compound represented by the above general formula [IV].
It is selected from the range of 10 mol. The above general formula [V-
a] to [V-d], the reaction ratio of the bromine compound is
Generally, it is preferable to select from the range of 0.5 to 10 mol per 1 mol of the compound corresponding to [IV] obtained by reacting with an alkali metal.

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 compounds of the above-mentioned general formula [I] of the present invention can be obtained by any of the above-mentioned processes A and B or by modification thereof.

The compound of the above-mentioned general formula [I] in the present invention has a photochromic action by itself and is excellent in its durability. However, when combined with an ultraviolet stabilizer, the durability of the photochromic action is improved. Is further improved. Therefore, when the compound [I] of the present invention is put to practical use, it may be used in combination with a known ultraviolet stabilizer.

The 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 compound represented by the general formula [I] is dissolved in such a solvent, the solvent is generally almost colorless and transparent, and it develops a color when exposed to sunlight or ultraviolet rays, and quickly returns to the original colorless state when the light is blocked. It exhibits a reversible photochromic effect. The photochromic action in the compound of the general formula [I] occurs in the polymer solid matrix, and the reversible speed is on the order of seconds. The high molecular polymer forming the target high molecular matrix may be any one in which the compound represented by the general formula [I] of the present invention is uniformly dispersed. Optically preferably, for example, polyacrylic acid is used. Methyl, ethyl polyacrylate, polymethyl methacrylate, polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethyl methacrylate), polydimethylsiloxane, polycarbonate, poly (allyl diglycol carbonate) Polymers such as, or polymers obtained by copolymerizing monomers as raw materials of these polymers or copolymerizing these monomers with other monomers are preferably used. The molecular weight of the high molecular weight polymer is not particularly limited, but is usually 500 to 50.
It is selected from the range of 10,000.

The amount of the compound of the general formula [I] of the present invention dispersed in the above-mentioned high molecular weight polymer is generally 0.001 to 70 parts by weight, based on 100 parts by weight of the high molecular weight polymer.
Preferably 0.005 to 30 parts by weight, particularly preferably 0.00
It is in the range of 1 to 15 parts by weight. Further, when the above-mentioned UV stabilizer is used as a mixture in the high molecular weight polymer, the amount thereof is preferably maintained within the range of the compounding ratio of the compound of the general formula [I] and the UV stabilizer.

The photochromic action of the compound of the general formula [I] of the present invention is excellent in durability as compared with the conventionally known fulgide compound, and the fading speed from the colored type to the colorless type is further improved.

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, printing photosensitive materials, cathode ray tube recording materials, laser photosensitive materials, 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. For example, when it is used for a photochromic lens, it is not particularly limited as long as it is a method capable of obtaining uniform dimming performance, and if it is specifically exemplified, a polymer film obtained by uniformly dispersing the photochromic material of the present invention. Is sandwiched in the lens, or this compound is used as a solvent in, for example, silicone oil to produce 150 to 200
There is a method of impregnating the lens surface at 10 ° C. for 10 to 60 minutes and then coating the surface with a curable substance to form a photochromic lens. Further, there is also a method in which the polymer film is applied to the lens surface and the surface is coated with a curable substance to form a photochromic lens. Furthermore, the photochromic compound of the present invention can be previously dispersed in a monomer capable of forming an organic lens and then polymerized and cured to form a photochromic lens.

[0128]

INDUSTRIAL APPLICABILITY The compound represented by the general formula [I] of the present invention is hardly affected by the kind of the polymer solid matrix and exhibits stable colorless in a general state. When it is exposed to ultraviolet rays, it develops color immediately, and when it is stopped from ultraviolet rays, it discolors at a faster rate than conventionally known fulgide compounds. Further, the durability against such discoloration is also good and extremely useful.

[0129]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

Example 1 3.0 g (0.01 mol) of 3-thienylethylidene-7-norbornylidene succinic anhydride of the following formula

[0131]

[Chemical 42]

And glycine-methyl ester 1 of the formula
7.8 g (0.02 mol)

[0133]

[Chemical 43]

Was dissolved in toluene, and 50 was added under a nitrogen atmosphere.
Heated at ° C 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 6 hours to be transferred to the following fulgimide compound (1). This compound was purified by chromatography on silica gel using benzene and ether as eluents, 25 as pale yellow needles from chloroform and hexane.
% Yield. The elemental analysis value of this compound is C6
4.31%, H5.67%, N3.72%, O17.4%,
S8.62%, which is the calculated value for C ₂ O H ₂₁ O ₄ NS C 64.67%, H 5.66%, N 3.77%,
It was in excellent agreement with O17.2% and S8.65%. Also, when the Pronton nuclear magnetic resonance spectrum (Fig. 1) was measured, a peak of 2H due to an aromatic proton near δ 7.0 to 8.0 ppm, and> C-CH _{3 at} δ 2.7 ppm.
3H peak due to bound protons, around δ 3.7 ppm

[0135]

[Chemical 44]

3H peak based on the proton of the bound methyl group, δ 1.2 to 2.5 ppm at 10 H based on the proton of the 7-norbornylidene group, δ 3 to 5 ppm at 1
-5 3 based on rearranged protons and> N-CH ₂ -bonds
An H peak was shown.

Furthermore, ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C
-NMR), the peak due to the carbon of 7-norbornylidene group and the carbon of the methylene chain was around δ27-70 ppm, the peak due to the carbon of methyl group was around δ15.6 ppm, and the carbon of thiophene ring was around δ110-160 ppm. Based on the peak, near δ160-170ppm>
A peak based on the carbon of the C = O bond appears.

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

[0139]

[Chemical formula 45]

Example 2 3.0 g (0.01 mol) of a fulgimide compound of the following formula

[0141]

[Chemical formula 46]

Dissolved in tetrahydrofuran, and reacted with 1 g of metallic potassium at room temperature to obtain imide potassium 2.7 of the following formula.

[0143]

[Chemical 47]

This and bromoacetonitrile of the following formula 1.
The following fulgimide compound (2) was obtained by reacting ₂ g (0.01 mol) of BrCH ₂ CN in dimethylformamide. This compound was purified by chromatography on silica gel using chloroform and hexane as eluents and was obtained as pale yellow crystals from hexane in 55% yield. The elemental analysis value of this compound is C67.41%, H5.30%, N
8.31%, O 9.49%, S 9.48%, C ₁₉
C67.44% is calculated values for _{H 18 N 2 O 2 S,} H
Very good agreement was obtained with 5.32%, N 8.28%, O 9.46% and S 9.49%. In addition, the proton nuclear magnetic resonance spectrum was measured, and it was found that the peak of 2H due to the proton of the thiophene ring at δ 7.0 to 7.5 ppm was δ 4.5 ppm.
2H peak due to protons of> N-CH ₂ CN bond, 1H peak due to 1-5 rearranged protons around δ 3.7 ppm, 3H peak due to protons with —CH ₃ bond near δ 2.7 ppm , -CH ₂ near Deruta1.3～2.5Ppm - showed peaks of 12H of protons based on protons and 7-norbornylidene group bonds.

Furthermore, ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C
-NMR), a peak based on the carbon of the 7-norbornylidene group was found around δ27-70 ppm, δ1.
A peak based on the carbon of the methyl group at 5.6 ppm, δ1
A peak due to carbon of the thiophene ring appears in the vicinity of 10 to 160 ppm, and a peak due to carbon of> C = O bond appears in the vicinity of 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.

[0147]

[Chemical 48]

Example 3

[0149]

[Chemical 49]

4.1 g (0.01 m) of the above-mentioned fulgide compound
ol) and 3.5 g of 2-naphthylethylamine of the following formula
(0.02 mol)

[0151]

[Chemical 50]

Is dissolved in toluene, and 50 is dissolved in a nitrogen atmosphere.
Heated at ° C 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 6 hours to be rearranged to the following fulgide compound (3). This compound was purified by chromatography on silica gel using benzene and ether as eluents and was obtained in 22% yield as yellow needle crystals from chloroform and hexane. The elemental analysis value of this compound is C66.
51%, H5.32%, Br14.23%, N2.52%,
O 5.70%, S 5.71%, C ₃₁ H ₃₀ BrNO ₂
Calculated value for S C66.43%, H5.36
%, Br 14.27%, N 2.50%, O 5.71%, S
Very good agreement with 5.73%. Also, the proton nuclear magnetic resonance spectrum was measured and found to be δ 7.0-8.0 pp
A peak of 8H based on aromatic protons near m, 1-5 rearranged protons near δ 3.8 ppm and> N-
3H peak due to CH ₂ -proton, δ2.7 ppm
The peak of 3H based on the proton of the> C—CH ₃ bond is in the vicinity, and the proton of the —CH ₂ — bond and the bicyclo [3.3.1] 9-nonylidene are in the vicinity of δ1.3 to 2.5 ppm.
A peak at 8H appears.

Furthermore, ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C
-NMR), a peak due to the carbon of the bicyclo [3.3.1] 9-nonylidene group and the carbon of the methylene chain was observed at δ27 to 52 ppm, a peak due to the carbon of the methyl group at δ15.6 ppm, δ110. A peak due to the carbon of the thiophene ring and the carbon of the naphthalene ring appears at about 160 ppm, and a peak due to the carbon of the> C = O bond appears at about 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.

[0154]

[Chemical 51]

Example 4 In place of 2-naphthylethylamine of Example 3, NH ₃
A fulgimide compound having the following structural formula was obtained in the same manner as in Example 3 except that was used.

[0156]

[Chemical 52]

6 g (0.015 mol) of this compound was dissolved in tetrahydrofuran and metallic sodium was reacted at room temperature to obtain 5 g of sodium imide represented by the following formula.

[0158]

[Chemical 53]

This and the following 2-naphthoxyacetic acid-2-bromoethyl ester

[0160]

[Chemical 54]

By reacting 2 g (0.01 mol) in dimethylformamide, the following fulgimide compound (4) was obtained. This compound was purified by chromatography on silica gel using chloroform and hexane as eluents and was obtained as yellow needle crystals from hexane in 50% yield. The elemental analysis values of this compound are C62.62%, H4.89%, Br12.54%, N
2.19%, a O12.70%, C ₃₃ H ₃₁ BrNO
Calculated value of ₅ S, C62.56%, H4.90%, B
Very good agreement was obtained with r 12.62%, N 2.21%, and O 12.64. Also, the proton nuclear magnetic resonance spectrum was measured, and it was found that the peak of 8H due to the aromatic protons at δ 7.0 to 8.0 ppm, δ 3.0 to 5.0 ppm.
A peak of 7H due to a proton based on a —CH ₂ — bond and a proton rearranged by 1-5, near −2.7 ppm
3H peak due to CH ₃ bond, δ 1.0 to 2.2 ppm based on bicyclo [3.3.1] 9-nonylidene group 14
An H peak was shown.

Furthermore, ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C
-NMR), a peak based on the carbon of the bicyclo [3.3.1] 9-nonylidene group and the carbon of the methylene chain was observed at about δ27 to 52 ppm, a peak based on the carbon of the methyl group at about δ15.6 ppm, and δ110 to 160 ppm. A peak due to the carbon of the thiophene ring and a carbon of the naphthalene ring appears in the vicinity, and a peak due to the carbon of the> C = O bond appears near δ160 to 170 ppm.

From the above results, it was confirmed that the isolated product was a fulgimide compound (4) represented by the following structural formula.

[0164]

[Chemical 55]

Example 5 3.0 g (0.01 mol) of 3-thienylethylidene-7-norbornylidene succinic anhydride of the following formula

[0166]

[Chemical 56]

And 2-aminobutyric acid-2-naphthylethyl ester of the following formula: 2.1 g (0.02 mol)

[0168]

[Chemical 57]

Was dissolved in toluene, and 50 was added under a nitrogen atmosphere.
Heated at ° C 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 6 hours to be transferred to the following fulgimide compound (5). This compound was purified by chromatography on silica gel using benzene and ether as eluents, 29% as yellow needle crystals from chloroform and hexane.
It was obtained with a yield of. The elemental analysis value of this compound is C73.
48%, H6.09%, N2.61%, O11.90%,
A S5.92%, C73.46% is calculated values for _{C 33 H 33 O 4 NS,} H6.12%, N2.60%, O
Very good agreement with 11.87% and S5.95%. Also, when the proton nuclear magnetic resonance spectrum was measured,
A peak of 9H due to aromatic protons around δ 7.0 to 8.0 ppm, a peak of 3H due to protons of> C-CH ₃ bond at δ 2.7 ppm, and -CH ₂ -CH _{3 at} δ 0.8 to 1.2 ppm. 3H based on the proton of the attached methyl group
Peak of 12H based on the -CH ₂ -bond and the proton of the 7-norbornylidene group at δ 1.2 to 2.5 ppm,
δ3~5ppm 1-5 dislocation protons and -CH ₂ - and a peak of 7H based on binding.

Furthermore, ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C
-NMR), a peak due to the carbon of the 7-norbornylidene group and the carbon of the methylene chain near δ27 to 52 ppm, a peak due to the carbon of the methyl group at δ15.6 ppm, and a carbon of the thiophene ring near δ110 to 160 ppm. And peaks based on carbon of naphthalene ring, δ160-
A peak based on carbon of> C = O bond appears around 170 ppm.

From the above results, it was confirmed that the isolated product was a fulgimide compound (5) represented by the following structural formula.

[0172]

[Chemical 58]

Example 6 3.0 g (0.01 mol) of a fulgimide compound of the following formula

[0174]

[Chemical 59]

Was dissolved in tetrahydrofuran, and 1 g of potassium metal was reacted with it at room temperature to obtain 2.6 g of imide potassium having the following formula.

[0176]

[Chemical 60]

This and the following formula: 1-naphthylethyl 5-bromovalerate 1.8 (0.01 mol)

[0178]

[Chemical formula 61]

The following fulgimide compound (6) was obtained by reacting with dimethylformamide. This compound was purified by chromatography on silica gel using chloroform and hexane as eluents and was obtained in 59% yield as yellow crystals from hexane.
The elemental analysis value of this compound is C73.55%, H6.36
%, N 2.56%, O 11.71%, S 6.17%, which is the calculated value for C ₃₄ H ₃₅ NO ₄ S. C73.7
7%, H6.33%, N2.53%, O11.57%, S
Very good agreement with 5.80%. Also, the proton nuclear magnetic resonance spectrum was measured and found to be δ 7.0-8.0 pp
A peak of 9H due to aromatic protons around m, around δ4.4ppm

[0180]

[Chemical formula 62]

2H peak due to binding protons, δ
1-5 rearranged protons around 3.7 ppm and> N-CH ₂
-3H peak due to bound protons, δ 2.7 ppm
A 3H peak due to the proton of the —CH ₃ bond in the vicinity,
A peak at 18H of -CH ₂ -bonded protons and a proton based on a 7-norbornylidene group was shown at δ of about 1.3 to 2.5 ppm.

Furthermore, ¹³ C-nuclear magnetic resonance spectrum ( ¹³ C
-NMR), a peak due to the carbon of the 7-norbornylidene group and the carbon of the methylene chain near δ27 to 52 ppm, a peak due to the carbon of the methyl group near δ15.6 ppm, and a carbon of the thiophene ring near δ110 to 160 ppm. And peaks based on carbon of naphthalene ring, δ160
A peak due to carbon of> C = O bond appears at about 170 ppm.

From the above results, it was confirmed that the isolated product was a fulgimide compound (6) represented by the following structural formula.

[0184]

[Chemical formula 63]

Example 7 10 g of 5-bromo-3-acetylthiophene (0.04)
9 mol) and 18.7 g (0.064 mo) of diethyl bicyclo [3.3.1] 9-nonylidene succinate of the following formula:
l)

[0186]

[Chemical 64]

A solution of and was dissolved in 200 cc of toluene was prepared. Then, 5 g of sodium hydride and 2 parts of toluene
The above toluene solution was dropped into a solution dispersed in 00 cc under a nitrogen stream over 3 hours so that the liquid temperature was 0 ° C. or lower. After the completion of the dropping, the liquid temperature was kept as it was at 0 ° C. or lower and the mixture was vigorously stirred for 10 hours. 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 11.3 g of a fulgide compound was obtained.

[0188]

[Chemical 65]

The obtained compound was refluxed in o-dichlorobenzene for 8 hours to be transferred to the following fulgide compound (7).

[0190]

[Chemical formula 66]

This compound was used as a benzene-eluent as an eluent.
For chromatography on silica gel
More purified, yellow needle from chloroform and hexane
It was obtained as a crystal in a yield of 37%. Origin of this compound
Elemental analysis values are C55.11%, H4.63%, S7.91
% And Br 19.52%, C₁₉H₁₉O₃SBr
Calculated values for C56.02%, H4.67%,
Excellent agreement between S 7.89% and Br 19.63%
did. Also, the proton nuclear magnetic resonance spectrum was measured.
However, due to the proton of the thiophene ring around δ7.2 ppm,
1H peak, 1-5 dislocation around δ4.0ppm 1
H peak,> C-CH near δ2.6 ppm ₃Join Pro
3H peak based on ton, around δ1.2-2.5ppm
To the proton of the bicyclo [3.3.1] 9-nonylidene group
It showed a broad peak at 14H.

Furthermore, the ¹³ C-nuclear magnetic resonance spectrum ( ¹³
C-NMR), the peak due to the carbon of the bicyclo [3.3.1] 9-nonylidene group was around δ27 to 52 ppm, the peak due to the carbon of the methyl group was around δ15.6 ppm, and around δ110 to 160 ppm. Peak due to carbon of thiophene ring, C = around δ160-170 ppm
A peak based on the O-bonded carbon appears.

From the above results, it was confirmed that the isolated product was the compound represented by the above structural formula (7).

Example 8 Various fulgide compounds or fulgimide compounds were synthesized from the raw materials shown in Table 1 in the same manner as in Examples 1 to 7.

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 7, and the results of structural formula (8) to The compound represented by (100) was confirmed. Table 2 shows the elemental analysis value of this compound, the calculated value obtained from the structural formula of each compound, and the characteristic absorption of the infrared absorption spectrum.

[0196]

[Table 1]

[0197]

[Table 2]

[0198]

[Table 3]

[0199]

[Table 4]

[0200]

[Table 5]

[0201]

[Table 6]

[0202]

[Table 7]

[0203]

[Table 8]

[0204]

[Table 9]

[0205]

[Table 10]

[0206]

[Table 11]

[0207]

[Table 12]

[0208]

[Table 13]

[0209]

[Table 14]

[0210]

[Table 15]

[0211]

[Table 16]

[0212]

[Table 17]

[0213]

[Table 18]

[0214]

[Table 19]

[0215]

[Table 20]

[0216]

[Table 21]

[0217]

[Table 22]

[0218]

[Table 23]

[0219]

[Table 24]

[0220]

[Table 25]

[0221]

[Table 26]

[0222]

[Table 27]

[0223]

[Table 28]

[0224]

[Table 29]

[0225]

[Table 30]

[0226]

[Table 31]

[0227]

[Table 32]

[0228]

[Table 33]

[0229]

[Table 34]

[0230]

[Table 35]

[0231]

[Table 36]

[0232]

[Table 37]

[0233]

[Table 38]

Example 9 0.5 parts by weight of the compound represented by the formulas (1) to (100) prepared in Examples 1 to 8 was added to polymethylmethacrylate 1
The solvent was dispersed in 0 part by weight and 100 parts by weight of benzene to prepare a cast film on a slide glass (11.2 × 3.7 cm). The thickness of this film is 0.1m
It was set to m. This photochromic film has a xenon long life fade meter FAL-25AX-HC (output: 2.5k.
w., light source: xenon long life arc lamp)
Xenon light is radiated with the initial color density (absorbance),
Maximum absorption wavelength (λmax) and JIS L0843, J
The fatigue life (T1 / 2) was measured according to ISB 7754.

T1 / 2 is defined as the time required for the color density to decay to half the initial value when the film is irradiated with the film meter.

Further, the fading speed of the cast film prepared in the same manner as above was determined as follows. The cast film has a mercury lamp SHL-100 made by Toshiba Corporation.
Was irradiated at 20 ° C. ± 1 ° C. and a distance of 10 cm for 60 seconds. After that, the irradiation was stopped and the spectrophotometer 22 manufactured by Hitachi, Ltd. was used.
The fading rate was determined by the change in the absorbance of the cast film measured using 0A. The fading rate is as follows: after the light irradiation for 60 seconds, the absorbance of the above cast film is {(the absorbance of the cast film at the maximum absorption wavelength immediately after the light irradiation for 60 seconds)-(the absorbance of the unexposed cast film at the maximum absorption wavelength). } It was expressed by the time required to decrease to 1/2. The results are shown in Table 3. For comparison, films were similarly prepared for the compounds represented by the following (X), (Y) and (Z), and the fatigue life and discoloration rate were measured.

[0237]

[Chemical formula 67]

[0238]

[Chemical 68]

[0239]

[Chemical 69]

[0240]

[Table 39]

[0241]

[Table 40]

[0242]

[Table 41]

[0243]

[Table 42]

[Brief description of drawings]

FIG. 1 is a chart of ¹ H-nuclear magnetic resonance spectrum of the compound obtained in Example 1.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07D 307/92 471/04 102 7602-4C 487/04 137 7019-4C 491/052 7019-4C 491 / 107 7019-4C 493/04 101 A 9165-4C C09K 9/02 B 7188-4H

Claims (2)

[Claims] 1. The following general formula (I): {In the formula Is a divalent aromatic hydrocarbon group which may have a substituent or a divalent unsaturated heterocyclic group R ₁ may be a monovalent hydrocarbon group which may have a substituent, or Monovalent heterocyclic group Are optionally substituted 7-norbornylidene groups or bicyclo [3.3.1] 9-nonylidene groups X are oxygen atom groups> N—R ₂ groups> N—A ₁ —B ₁ — _{(a 2) m - (B} 2) n -R 3 group> shows the n-a ₃ -A ₄ or a group> n-a ₃ -R ₄ (wherein, R ₂ represents a hydrogen atom, an alkyl group or an aryl The groups, A ₁ , A ₂ and A ₃ are the same or different and are an alkylene group, an alkylidene group, a cycloalkylene group or an alkylcycloalkane-diyl group, B ₁ and B
₂ are the same or different, m and n each independently represent 0 or 1,
When m is 0, n is 0. R ₃ is an optionally substituted alkyl group, naphthyl group or naphthylalkyl group, A ₄ is an optionally substituted naphthyl group , R ₄ represents a halogen atom, a cyano group or a nitro group)}. 2. A photochromic material comprising the compound according to claim 1.