JPH08245627A - Bridged spiropyran compound - Google Patents

Abstract

PURPOSE: To obtain the subject compound having a spiropyran skeleton in which specific positions are bridged with a lower alkylene group, excellent in heat stability and photo responsibility and useful for an optical recording material. CONSTITUTION: This is a compound expressed by formula I (R<1> to R<4> are each H, a lower alkyl, an aryl, an aralkyl, a lower alkoxy, a hydroxymethyl, carboxyl, a halogen, an amide, an amino, cyano, a trihalomethyl or nitro; R<5> and R<6> are each H, a lower alkyl, an aryl, an aralkyl, a halogen, cyano or nitro; X is O or S; Y is a lower alkylene). For example, 1,8'-(4-butanoic acid methylene)-3,3'-dimethyl-6'-nitrospiro[(2'H)-1'-benzopyran-2,2'-indoli ne]. Further, an objective compound is preferably obtained e.g. by subjecting an indoline derivative of formula II to a condensation reaction with a 3-chloromethyl-5- nitrosalicyl aldehyde derivative of formula III and passing through processes including a reaction of the obtained intermediate with silver nitrate, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel crosslinked spiropyran compound.

[0002]

2. Description of the Related Art With the remarkable development of information-related equipment such as computers and the development of recording media with a large capacity, there is a growing interest in optical memories with extremely high recording densities. An optical memory is one in which a laser light is irradiated to induce a thermal reaction or a photoreaction in the memory, and a signal is recorded by the resulting change in physical properties.

Recently, compounds showing photochromism (hereinafter referred to as "photochromic compounds") have been used as materials for optical memories.
It has been attempted to apply a mixture of). Photochromism is a phenomenon in which light energy or heat energy reversibly changes between two states with different absorption spectra (coloring species and decoloring species), and spiropyran derivatives are the most typical organic compounds showing this phenomenon. well known. Specific examples of such derivatives include, for example, "Photochromism" by GH Brown (Photochromism, John W).
iley & Sons, Inc. 1971). The spiropyran derivative undergoes structural conversion as shown in the following reaction formula and exhibits photochromism.

[0004]

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[In the formula, X represents an oxygen atom or a sulfur atom. That is, the decoloring species of the spiropyran derivative has the structure of A in the above reaction formula, and by irradiating it with ultraviolet light, structural conversion occurs to form a ring-opening type structure (coloring species) of B and develop color ( J. Am. Chem. Soc., 112, 89.
77 (1990), Chem. Lett. , 1991,
1873).

However, when a conventional spiropyran derivative is used as an optical recording material, it has a drawback that the color-developing species lacks thermal stability even in an organic solvent or in a resin and immediately returns to a decolorizing species. is there. Further, the conventional spiropyran derivative has a drawback that its responsiveness is insufficient even when it is irradiated with ultraviolet light, and that structural conversion hardly occurs.

[0007] In order to eliminate such drawbacks of the spiropyran derivative, attempts have conventionally been made to control the electronic state of the color-forming species of B by introducing various functional groups onto the spiropyran skeleton of the spiropyran derivative. We haven't achieved enough results.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems of the prior art, the present inventor has found that thermal stability and light stability can be improved by crosslinking a specific site of the spiropyran skeleton with a lower alkylene group. We succeeded in obtaining a novel spiropyran compound with excellent responsiveness, and completed the present invention here.

That is, the present invention has the general formula

[0010]

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[Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group, a lower alkoxy group, a hydroxymethyl group, a carboxyl group or a halogen atom. An atom, an amino group, an amide group, a cyano group, a trihalomethyl group or a nitro group is shown. R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group, a halogen atom, a cyano group or a nitro group. X represents an oxygen atom or a sulfur atom. Y represents a lower alkylene group. ] It concerns on the bridge | crosslinking spiropyran compound represented by these.

In the above general formula (1), R ^{1 to} R ⁶
As the aryl group represented by, for example, a phenyl group,
Examples thereof include a naphthyl group, and a phenyl group is preferable. Further, on the aromatic ring of these groups, a linear or branched alkyl group having about 1 to 4 carbon atoms, a linear or branched alkoxy group having about 1 to 4 carbon atoms, chlorine, bromine, iodine, etc. The halogen atom, the nitro group or the like may be substituted with one kind or two or more kinds.

The aralkyl group represented by R ^{1 to} R ⁶ includes, for example, a benzyl group, a 1-phenethyl group, a 2-phenethyl group, a 3-phenylpropyl group, a 4-phenylbutyl group and the like, whose alkyl moiety has 1 carbon atom. A phenylalkyl group which is a straight-chain or branched-chain alkyl having about 4 to 4 carbon atoms, and a straight-chain or branched-chain alkyl group having about 1 to 4 carbon atoms and about 1 to 4 carbon atoms on the phenyl ring One or more kinds of linear or branched alkoxy groups, halogen atoms such as chlorine, bromine and iodine, and nitro groups may be substituted.

The lower alkyl group represented by R ^{1 to} R ⁶ includes, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, Examples thereof include linear or branched alkyl groups having about 1 to 6 carbon atoms such as n-pentyl group and n-hexyl group.

Examples of the halogen atom represented by R ^{1 to} R ⁶ include chlorine, bromine, iodine and the like.

Examples of the lower alkoxy group represented by R ^{1 to} R ⁴ include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, s
Examples thereof include linear or branched alkoxy groups having about 1 to 5 carbon atoms such as ec-butoxy group, tert-butoxy group and n-pentyloxy group.

The lower alkylene group represented by Y is
For example, methylene group, ethylene group, trimethylene group, 1
-A straight chain having about 1 to 6 carbon atoms such as methylethylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethylethylene group, pentamethylene group, hexamethylene group or the like. A branched alkylene group, preferably a linear or branched alkylene group having about 1 to 4 carbon atoms can be mentioned.

The spiropyran compound of the present invention represented by the above general formula (1) (hereinafter referred to as "spiropyran compound (1)") is dissolved in an appropriate solvent and then colored by irradiation with ultraviolet light, and gradually colored at room temperature. It shows photochromism that fades. Further, the maximum absorption wavelength at the time of coloring is in a short wavelength region as compared with the conventional compound having the same functional group.

The spiropyran compound (1) can be used as various optical materials such as a high density optical recording material, an optical filter, an image forming material, an optical filter, a photosensitive material and a non-linear optical material, and the dynamics of light energy. It is also expected to be used in the field of energy conversion materials.

The spiropyran compound (1) of the present invention is a novel compound which has not been described in the literature. For example, as shown in the following reaction formula-1, the indoline derivative represented by the general formula (2) (hereinafter referred to as "indoline derivative (2 ) ”) And a 3-chloromethyl-5-nitrosalicylaldehyde derivative represented by the general formula (3) (hereinafter referred to as“ salicylaldehyde derivative (3) ”) are subjected to a condensation reaction to be represented by the general formula (4). To produce a spiropyran derivative (hereinafter referred to as "spiropyran derivative (4)"), and to react the resulting spiropyran derivative (4) with silver nitrate.

[0021]

[Chemical 4]

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , X and Y are the same as above. The condensation reaction between the indoline derivative (2) and the salicylaldehyde derivative (3) is usually performed in a solvent. The condensation reaction is preferably carried out with stirring. The solvent used here is not particularly limited as long as it is inert to the condensation reaction and can dissolve the indoline derivative (2) and the salicylaldehyde derivative (3), and examples thereof include acetonitrile, methanol, ethanol, isopropanol. , Butanol, ether, tetrahydrofuran, chloroform, methylene chloride, benzene, toluene, ethyl acetate, methyl ethyl ketone, acetone, formamide,
Examples thereof include dimethylformamide, dimethylsulfoxide, and a mixed solvent of two or more of these. The use ratio of the indoline derivative (2) and the salicylaldehyde derivative (3) is not particularly limited and can be appropriately selected from a wide range, but it is usually about equimolar amount. The condensation reaction is usually carried out at room temperature, but when a raw material compound having low reactivity is used, it may be carried out under appropriate heating.

The reaction between the spiropyran derivative (4) obtained by the above condensation reaction and silver nitrate is usually carried out in the same organic solvent as that used in the above condensation reaction. This reaction is also preferably carried out with stirring. The use ratios of the spiropyran derivative (4) and silver nitrate are not particularly limited and can be appropriately selected from a wide range, but usually 0.5 to 0.5 mol of silver nitrate per mol of the spiropyran derivative (4).
About 5 mol, preferably about 1 to 2 mol may be used. The reaction temperature may be around room temperature.

The spiropyran compound (1) of the present invention thus obtained can be easily isolated and purified from the reaction mixture by a conventional separation and purification means.

The indoline derivative (2), which is the starting compound for the spiropyran compound (1) of the present invention, is

[0026]

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[In the formula, R ¹ , R ² , R ³ , R ⁴ and Y are the same as defined above. Z ⁻ represents a halogen ion or an aryl sulfonate ion. ] It is manufactured by making a base react with the indolenium salt derivative (henceforth "indolenium salt derivative (5)") represented by these. As the base, any known base can be used regardless of whether it is an inorganic base or an organic base. In this case, an organic base such as piperidine or pyridine can be preferably used. The amount of the base used is not particularly limited and can be appropriately selected from a wide range, but it is usually preferable to be equal to or more than the amount of the indolenium salt derivative (5).

The indolenium salt derivative (5) can be prepared, for example, according to Helv. Chim. Acta, 23, 2471 (19
40), JP-A-58-58654, JP-A-62-
No. 232461, JP-A No. 62-21780,
It can be easily produced according to the method described in JP-A-63-267783.

A compound (3a) in which X is an oxygen atom in the aldehyde derivative (3) which is the other starting material compound.
Is, for example, according to the method described in JP-A-2-289580,

[0030]

[Chemical 6]

[In the formula, R ⁵ and R ⁶ are the same as defined above. ] It manufactures by making the 5-nitro salicyl aldehyde derivative represented by this and chloromethyl methyl ether react.

The compound (3b) in which X is a sulfur atom in the general formula (3) is disclosed in, for example, JP-A-60-5438.
It can be manufactured according to a known method described in Japanese Patent No. An example thereof is shown in Reaction Formula-2 below.

[0033]

[Chemical 7]

[In the formula, R ⁵ and R ⁶ are the same as defined above. That is, according to the reaction formula-2, the 2-nitrosalicylaldehyde derivative represented by the general formula (6a) is reacted with N, N-dimethylthiocarbamoyl chloride to obtain the 2-O- represented by the general formula (7). (N, N-dimethylthiocarbamoyl)
2-S-represented by the general formula (8) is obtained by obtaining -5-nitrobenzaldehyde and then subjecting it to heat isomerization.
(N, N-Dimethylthiocarbamoyl) -5-nitrobenzaldehyde is obtained, and by subjecting this to alkali hydrolysis, a 5-nitrosalicylaldehyde derivative represented by the general formula (6b) is produced. Compound (3b) is produced by reacting this compound with chloromethyl methyl ether in the same manner as above.

The spiropyran compound (1) of the present invention can be used as an optical material by mixing one kind or two or more kinds thereof with a suitable matrix material such as resin and organic solvent. The matrix resin used at this time is not particularly limited as long as the spiropyran compound (1) of the present invention is uniformly dispersed therein. Specific examples of the matrix resin include polymethacrylic acid, polyacrylic acid, C ₁ -C ₈ alkyl ester of polymethacrylic acid, C ₁ -C ₈ alkyl ester of polyacrylic acid, polyacrylonitrile, polyacrylic acid amide, and poly N. ，
N-dimethyl acrylamide, polyvinyl acetate, polystyrene, poly α-methyl styrene, polyvinyl toluene, polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyethylene oxide, nylon, polyurethane, various polyolefins, ethyl cellulose Etc. can be mentioned. At this time, the blending amount of the spiropyran compound (1) of the present invention is not particularly limited and can be appropriately selected from a wide range, but is usually about 0.01 to 30% by weight of the total amount of the spiropyran compound (1) and the resin, preferably Is about 0.1 to 15% by weight. When the spiropyran compound (1) of the present invention is mixed with a resin or an organic solvent, various additives which have been conventionally used in compositions for optical materials can be added as long as the characteristics thereof are not impaired.

The resin composition containing the spiropyran compound (1) of the present invention may be molded into a desired shape as it is,
In addition, for example, it may be coated on a suitable substrate such as metal, ceramics, plastic, and paper. The coating can be performed by various methods such as a spin coating method, a spray method, a dipping method, a flow coating method and a bar coating method. A transparent protective coating may be coated on the coating made of the resin composition containing the spiropyran compound (1) of the present invention.

Further, the spiropyran compound (1) of the present invention
The optical material containing can be encapsulated according to a known method or can be used by enclosing it in a suitable container. The capsules can be used in admixture with resins and other matrix materials.

[0038]

According to the present invention, a novel spiropyran compound having excellent photoresponsiveness and thermal stability is provided.

[0039]

EXAMPLES The present invention will be specifically described below with reference to Reference Examples, Examples and Test Examples.

Reference Example 1 Synthesis of 3-chloromethyl-5-nitrosalicylaldehyde 2.42 g of 5-nitrosalicylaldehyde was suspended in 20 ml of chloromethyl methyl ether, and 7.97 g of aluminum chloride was added while cooling with an ice bath. It was After stirring at room temperature for 10 minutes, it was heated at 60 ° C. for 1 hour. The reaction solution was poured into 100 ml of ice water while cooling with an ice bath, and the resulting yellow precipitate was filtered off. The obtained precipitate was recrystallized from 330 ml of hexane to obtain 2.49 g of yellow needle crystals. The obtained crystal was 3-chloromethyl-5-nitrosalicylaldehyde, and the yield was 80%.

¹ H-NHR (60 MHz, CDC
l ₃ ): δ ppm; 4.7 (s, 2H, —CH ₂ C
l), 8.5 (s, 2H, ArH), 10.0 (s, 1
H, -CHO), 12.1 (s, 1H, -OH).

Reference Example 2 Synthesis of 1- (4-butanoic acid ethyl) -2,3,3-trimethylindolenium iodide 2,3,3-trimethylindolenin 2.64 g and 4
-4.02 g of ethyl iodobutanoate in chloroform 1
It was dissolved in 7 ml and heated and stirred in a sealed tube at 100 ° C. for 129 hours. The resulting red solution was concentrated and the residue was washed with acetone 30
It was washed 10 times with a mixed solvent of 10 ml of hexane and 10 ml of hexane. The resulting purple precipitate was separated by filtration and vacuum dried to obtain 1.85 g of purple powder 1- (4-ethyl 4-butanoate) -2,3,3-trimethylindolenium iodide with a yield of 28%.

¹ H-NHR (400 MHz, D ₂ O):
δppm; 1.23 (t, 3H, CH ₂ CH ₃ ), 1.
_{63 (s, 6H, CH 3} ), 2.25 (m, 2H, -C
_{H 2 -), 2.71 (t} , 2H, -CH 2 CO 2 -),
_{3.17 (s, 3H, -CH 3} ), 4.09 (t, 2
_{H, -CO 2 CH 2 -)} , 4.83 (t, 2H, NCH
_2- ), 7.59 (m, 3H, ArH), 7.98
(D, 1H, ArH).

Reference Example 3 Synthesis of 1-carboxypropyl-2,3,3-trimethylindolenium iodide 0.512 g of 1- (ethyl 4-butanoate) -2,3,3-trimethylindolenium iodide was added to 12 ml of tetrahydrofuran and 12 ml of tetrahydrofuran. It was dissolved in a mixed solvent of 4 ml of methylene chloride, 8 ml of 6N hydrochloric acid was added, and the mixture was stirred at room temperature for 5 hours. After 8 ml of distilled water and 4 ml of methylene chloride were added and stirred, the aqueous layer was separated and washed with 4 ml of methyl chloride three times and 4 ml of diethyl ether. The aqueous layer was concentrated, and the obtained red solid was washed 3 times with 1 ml of acetone and then vacuum dried,
0.291 g of 1-carboxypropyl-2,3,3-trimethylindolenium iodide as ocher powder was obtained with a yield of 61%.

¹ H-NHR (400 MHz, D ₂ O):
δppm; 1.27 (s, 6H, CH ₃ ), 1.96
_{(M, 2H, -CH 2 -} ), 2.34 (t, 2H, -C
_{H 2 CO 2 -), 3.34} (s, 3H, -CH 3),
_{4.22 (t, 2H, NCH 2} -), 7.34 (m, 2
H, ArH), 7.44 (t, 1H, ArH), 7.5
1 (t, 1H, ArH).

Example 1 Synthesis of 1,8 '-(methylene 4-butanoate) -3,3-dimethyl-6'-nitrospiro [(2'H) -1'-benzopyran-2,2'-indoline] 1-Carboxypropyl-2,3,3-trimethylindolenium iodide (0.0506 g) was dissolved in acetonitrile (3 ml), and piperidine 0.0115 was added at 0 ° C.
g was added dropwise. After stirring at room temperature for 2 hours, the solvent was evaporated and 1 ml of acetone was added to a solution of 15 ml of diethyl ether.
Dropped in. The white precipitate formed was filtered off, and the solvent in the obtained filtrate was distilled off at room temperature to give 1-carboxypropyl-2-methylene-3,3-dimethylindolenin 0.0.
343 g were obtained.

Then, in a dark place, this was dissolved in 5 ml of acetone, 0.0292 g of 3-chloromethyl-5-nitrosalicylaldehyde was added, the mixture was stirred at room temperature for 10 hours, 15 ml of diethyl ether was added, and 2 ml of distilled water was added. The organic layer obtained by washing was dried over anhydrous sodium sulfate. After distilling off the solvent in a dark place, the residue was dissolved in 20 ml of diethyl ether, and 0.0158 g of silver nitrate was added to 1 m of acetonitrile.
The solution dissolved in 1 was added and stirred at room temperature for 3 hours. The mixture was filtered through Celite in the dark, and the solvent in the obtained filtrate was evaporated to give red tar 1,8 ′-(methylene 4-butanoate) -3,
3-Dimethyl-6'-nitrospiro [(2'H) -1 '
-Benzopyran-2,2'-indoline] 0.0420
g was obtained with a yield of 76%.

¹ H-NHR (400 MHz, CDC
l ₃ ): δppm; 1.20 (s, 3H, CH ₃ ),
1.31 (s, 3H, CH ₃ ), 1.87 (s, m, 2
_{H, -CH 2 -), 2.18} (t, 2H, -CH 2 CO
_{2 -), 3.17 (t,} 2H, NCH 2), 5.23
_{(Dd, 2H, -CO 2 CH} 2 -), 5.95 (d, 1
H, vinyl), 6.62 (d, 1H, ArH), 6.9
0 (d, 1H, ArH), 6.93 (d, 1H, vinyl), 7.07 (t, 1H, ArH), 7.17 (t,
1H, ArH), 8.03 (d, 1H, ArH), 8.
09 (d, 1H, ArH).

Test Example 1 The 1-position-8'-position cross-linked spiropyran compound obtained in Example 1 was dissolved in chloroform at a rate of 0.0675 g / liter, and a 500 W ultrahigh pressure mercury lamp was used in this solution to obtain a wavelength of 350 nm. It was colored red when irradiated with ultraviolet light in the vicinity. The maximum absorption wavelength (λmax) in chloroform is 5
68 nm, molar extinction coefficient (ε) is 5350 M ⁻¹ cm ⁻¹ ,
Half-life (τ 1/2) of colored state at 30 ° C is 3.24.
The irradiation time of the ultraviolet light required to obtain the maximum colored state was 60 seconds. This colored solution immediately returned to the original yellow color upon irradiation with visible light of 500 nm or more.

A spiropyran compound having no cross-linking moiety represented by the following chemical structural formula was dissolved in chloroform in the same manner as above, and its various properties were examined. The maximum absorption wavelength (λma)
x) is 580 nm, molar extinction coefficient (ε) is 13500M
^-1 cm ^-1 , half-life of colored state at 30 ℃ (τ 1/2)
Was 1.56 minutes, and the irradiation time of ultraviolet light required to obtain the maximum colored state was 120 seconds.

[0051]

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From the above results, the stability of the colored state is doubled (30 ° C.) by forming the cross-linking portion, and the irradiation time of the ultraviolet light necessary for obtaining the maximum colored state is shortened to 1/2. I understand that

Claims (1)

[Claims] 1. A general formula: [Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a lower alkyl group, an aryl group, an aralkyl group, a lower alkoxy group, a hydroxymethyl group, a carboxyl group, a halogen atom or an amino group. Represents a group, an amide group, a cyano group, a trihalomethyl group or a nitro group. R ⁵ and R
⁶ is the same or different, a hydrogen atom, a lower alkyl group,
An aryl group, an aralkyl group, a halogen atom, a cyano group or a nitro group is shown. X represents an oxygen atom or a sulfur atom.
Y represents a lower alkylene group. ] The spiropyran compound represented by these.