JPH0551379A - Dicyanoethylene derivative - Google Patents

Abstract

PURPOSE:To obtain the subject new compound capable of providing optical recording materials changing color by irradiation with light, returning to the original properties by irradiation with light at other wavelengths and capable of performing reversible recording in a photon mode. CONSTITUTION:A compound expressed by formula I [A and B are not same and A 18 formula II (R<1> is alkyl, halogen, etc.; R<2> and R<3> are H, alkyl, etc.; X is O, S, etc.; B is formula III (R<5> is alkyl, halogen, etc.; R<6> and R<7> are H, alkyl, etc.; Y us O, S, etc.), etc.], e.g. an indolyl-benzothienyldicyanoethylene derivative expressed by formula IV. The compound expressed by formula I is obtained by respectively starting from a compound expressed by formula V, producing an intermediate (A) expressed by formula VI and starting from a compound expressed by formula VII, producing an intermediate (B) expressed by formula VIII and then reacting the resultant intermediates (A) with (B).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel dicyanoethylene derivative having an asymmetric structure, and more specifically, it is cyclized by irradiation with light at the 1-position and 2-position to form a cyclohexadiene ring to change its optical properties. The present invention relates to a dicyanoethylene derivative having a unique asymmetric heterocycle.

[0002]

2. Description of the Related Art In recent years, much research has been conducted on the use of photochromic compounds as optical recording materials. In order to use the photochromic compound as an optical recording material, it is necessary to satisfy the following conditions.

Provide semiconductor laser sensitivity.
That is, the absorption wavelength of the colored species (closed ring) is 650 nm or more. Must have a non-destructive read function. Records are thermally stable. Excellent repeatability. Have high sensitivity.

The present inventor has previously proposed the following bisindole compound as a photochromic compound which has improved the above-mentioned semiconductor laser sensitivity and repeated durability of the above problems.

[0005]

[Chemical 2]

As other photochromic compounds,
The following dibenzothiophene compounds have also been proposed.

[0007]

[Chemical 3]

[0008]

Among the above photochromic compounds, the bisindole-based compound [A] has a problem that the thermal stability of recording is poor, which is particularly important in recording materials.

On the other hand, the dibenzothiophene compound [B] is excellent in the thermal stability of recording, but has a problem in that the absorption wavelength of the color-forming species (closed ring) is short and the semiconductor laser sensitivity is low.

An object of the present invention is to solve the above-mentioned conventional problems and to provide a photochromic compound satisfying particularly important required properties for an optical recording material.

[0011]

That is, the gist of the present invention is as follows.
It exists in the dicyanoethylene derivative represented by the following general formula [I].

[0012]

[Chemical 4]

(In the general formula [I], A and B do not represent the same substituent, and A is a substituent [i] or [ii] (in the substituents [i] and [ii], R ¹ Represents an alkyl group, an alkoxy group, a halogen atom or a trifluoromethyl group, and R ² and R ³ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a trifluoromethyl group, a cyano group or a substituted group. Represents an optionally substituted aryl group, or R ² and R ³
And may be linked to each other to form an optionally substituted carbocycle or an optionally substituted heterocycle. X is -O -, - S- or -NR ⁴ - (R ⁴ represents a hydrogen atom, an alkyl group which may be substituted, an optionally substituted aryl group or an optionally substituted cycloalkyl group ) Is represented. ), And B is a substituent [iii
Or [iv] (in the substituents [iii] and [iv], R ⁵ represents an alkyl group, an alkoxy group, a halogen atom or a trifluoromethyl group, and R ⁶ and R ⁷ are each independently a hydrogen atom or an alkyl group. A group, an alkoxy group, a halogen atom, a trifluoromethyl group, a cyano group or an optionally substituted aryl group, or R ⁶
And R ⁷ may be linked to each other to form an optionally substituted carbocycle or an optionally substituted heterocycle. Y is -O -, - S- or -NR ⁸ - (R ⁸ represents a hydrogen atom, an alkyl group which may be substituted, an optionally substituted aryl group or an optionally substituted cycloalkyl group Represents)) represents. )

The present invention will be described in detail below. In the dicyanoethylene derivative of the general formula [I], examples of the heterocyclic residue represented by A include those represented by the following formulas (1) to (6).

[0015]

[Chemical 5]

Here, R ¹ is a methyl group, an ethyl group or n-
Propyl group, iso-propyl group, n-butyl group, te
C1-C6 alkyl group such as rt-butyl group; C1-C6 alkoxy group such as methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group; fluorine atom, chlorine An atom, a bromine atom, a halogen atom such as an iodine atom; or a trifluoromethyl group,
R ² and R ³ are each independently a hydrogen atom; a methyl group, an ethyl group, an n-propyl group, an iso-propyl group,
an alkyl group having 1 to 6 carbon atoms such as n-butyl group and tert-butyl group; an alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, iso-propoxy group and n-butoxy group A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a trifluoromethyl group; a cyano group; or a lower alkyl group, a lower alkoxy group, a lower alkylamino group, a lower dialkylamino group,
C6, such as phenyl, tolyl, and naphthyl groups, which may be substituted with amino groups, halogen atoms, cyano groups, etc.
Represents an aryl group of 12 to 12, or R ² and R ³ are connected to each other to form a carbon ring such as an alkylene ring, a benzene ring, or a naphthalene ring having 3 to 5 carbon atoms, or a pyridine ring, a pyrazine ring,
It forms a heterocycle such as a pyrimidine ring, a pyridazine ring, a pyran ring, a furan ring and a thiophene ring. R ⁴ is a hydrogen atom; each of which may have a substituent such as a halogen atom, a lower alkoxy group, a hydroxyl group, a cyano group, an amino group and a nitro group, an ethyl group, an n-propyl group, i
an alkyl group having 1 to 6 carbon atoms such as so-propyl group, n-butyl group, tert-butyl group; an aryl group having 6 to 12 carbon atoms such as phenyl group, tolyl group, naphthyl group; or cyclopropyl group, cyclobutyl Represents a cycloalkyl group having 3 to 8 carbon atoms such as a group, a cyclopentyl group and a cyclohexyl group.

Examples of the heterocyclic residue represented by B include those represented by the following formulas (7) to (12).

[0018]

[Chemical 6]

Here, R ⁵ has the same meaning as defined for the substituent of R ¹ , and R ⁶ and R ⁷ are the same as R ² and R ³ ,
R ⁸ has the same meaning as defined for the substituent of R ⁴ .

In the heterocyclic residue represented by A or B, when R ² and R ³ , R ⁶ and R ⁷ are linked to form a carbocycle or a heterocycle, specifically, a benzofuran ring, When forming a benzothiophene ring, an indole ring, a benzoxazole ring, a benzothiazole ring, an indazole ring, etc., the ring may have one or more substituents. Examples of such a substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; hydroxyl group; methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group and the like having 1 to 6 carbon atoms. Alkyl group; methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group and other alkoxy groups having 1 to 6 carbon atoms; cyano group; nitro group; methoxycarbonyl group, ethoxycarbonyl group, n- Propoxycarbonyl group, i
C2-C7 alkoxycarbonyl group such as so-propoxycarbonyl group; C1-C6 haloalkyl group such as trifluoromethyl group; C6-C12 aryl group such as phenyl group, tolyl group and naphthyl group A cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group; aryloxycarbonyl group having 7 to 13 carbon atoms such as phenoxycarbonyl group, naphthyloxycarbonyl group; methylaminocarbonyl group , C2-7 monoalkylaminocarbonyl groups such as ethylaminocarbonyl group and propylaminocarbonyl group; N, N-dimethylaminocarbonyl group, N, N-diethylaminocarbonyl group, N, N-methylethylaminocarbonyl group Etc. C3-C9 dialkylaminocar Alkenyl group; an acetyl group, propionyloxy group, butyryloxy group, an alkylcarbonyloxy group having 2 to 8 carbon atoms such as iso-butyryloxy group;
Arylcarbonyloxy group having 7 to 13 carbon atoms such as benzoyloxy group, toluoyloxy group and naphthoyloxy group; 6 carbon atoms such as phenoxy group and naphthyloxy group
12 aryloxy groups; alkoxycarbonyloxy groups having 2 to 8 carbon atoms such as methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, and iso-propoxycarbonyloxy group;
Examples thereof include aryloxycarbonyloxy groups having 7 to 13 carbon atoms such as phenoxycarbonyloxy group and naphthyloxycarbonyloxy group.

In the present invention, a compound in which one of the heterocyclic residues represented by A or B is an indole ring and the other is a benzothiophene ring, a thiophene ring, a thiazole ring or an oxazole ring is preferable.

Among the dicyanoethylene derivatives according to the present invention, for example, the indolyl-benzothienyldicyanoethylene derivative can be easily produced according to the following reaction formula.

[0023]

[Chemical 7]

[0024]

[Chemical 8]

[0025]

[Chemical 9]

That is, after synthesizing the intermediates represented by the above structural formulas (a) and (b), the compounds (a) and (b) are condensed to give an indolyl-benzothienyldicyanoethylene derivative [IIIA]. Can be obtained. The condensation reaction of the compounds (a) and (b) can be carried out by subjecting these cyanomethyl derivatives to condensation reaction in water-organic solvent in the presence of a phase transfer catalyst in an alkaline manner,
A dicyanoethylene derivative [IIIA] is produced.

The organic solvent used in the condensation reaction of the compounds (a) and (b) is preferably a halogen-based solvent such as dichloromethane, chloroform, carbon tetrachloride, tetrachloroethane and the like. Examples of the phase transfer catalyst include tetrabutylammonium bromide, tetrabutylammonium iodide, triethylbenzylammonium chloride and the like. Examples of the alkaline agent used include sodium hydroxide and potassium hydroxide. The reaction temperature for condensation is preferably from room temperature to 100 ° C, particularly preferably 40 to 50 ° C.

When the dicyanoethylene derivative of the present invention is irradiated with light, the heterocyclic ring W and the heterocyclic ring W ′ are cyclized to form a cyclohexadiene ring, as shown in the following formula:
To [IA '] cause a structural change to cause a color change. Further, this colored state can be reversibly restored to the original state by a photoreaction.

[0029]

[Chemical 10]

Specifically, for example, an indolylbenzothienyldicyanoethene derivative represented by the following formula [IIB] undergoes a structural change as shown below when irradiated with an argon ion laser beam having a wavelength of 488 nm. The structure becomes as shown in [IIB '] and changes from yellow to purple. Further, since this purple colored state has an absorption wavelength extending to the semiconductor laser region, it can be reversibly returned to the original state as shown by the following formula by irradiating with a semiconductor laser beam of 780 nm.

[0031]

[Chemical 11]

In particular, the ethylene derivative according to the present invention is thermally stable in both the ring-opened state [IA] and the colored state (ring-closed state) [IA '], and is thermochromic even when heated at a high temperature for a long time. No reaction (thermal coloring reaction) is shown, the colored state is stable, no fading reaction is shown, and both states are well maintained. Further, in the case where an indole ring is present on one side of the carbon of ethylene bond, the above ring opening-coloring by ring closing-
It has good durability against repeated erasing and is very useful as a reversible optical recording material.

[0033]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Example 1 An indolyl-benzothienyldicyanoethylene derivative (compound [IIIA]) was synthesized according to the above reaction formula.

(1) Synthesis of Compound (a) (1) -Synthesis of Compound 2 20 ml of DMSO (dimethyl sulfoxide) was ice-cooled and 1.6 g of 60% by weight NaH was added to the ice-cooled DMSO.
The mixture was placed in the flask, heated to 30 ° C., and stirred overnight until hydrogen bubbling disappeared. Next, 2-methylindole (compound
1 ) 2.62 g (0.02 mol) was added to this ice-cooled mixture and heated to 30 ° C. to completely dissolve it. Then, 11.6 g of methyl iodide was slowly added dropwise while cooling with an ice bath, and stirring was continued for about 1 hour. 16 of this reaction solution
When poured into 0 ml of water and stirred well, a pale yellow solid was formed. This was extracted with benzene and dried to obtain a pale yellow solid 1,2-dimethylindole (Compound 2 ) (yield: 90%, boiling point: 76 to 79 ° C / 2 mmHg).

(1) -Synthesis of Compound 3 36 ml of a mixture of 25 wt% dimethylamine aqueous solution and 40 ml of glacial acetic acid was cooled to 5 ° C. in an ice bath. 1 for this
5 ml of 46 wt% formaldehyde aqueous solution was added, and the mixture was cooled to 5 ° C in the same manner. After cooling, 26.2 g of compound 2 was added dropwise. A white solid was formed each time it was dropped. The mixture was slowly stirred until homogeneous and left at room temperature overnight. Then, it was poured into an aqueous solution of 40 g of sodium hydroxide / 400 ml, extracted with ether, washed with water and dried.
After distilling off the solvent, distillation was carried out to obtain compound 3 (boiling point: 105 ° C./2 mmHg).

(1) -Synthesis of Compound 4 9.1 g of Compound 3 was dissolved in 40 ml of absolute ethanol. While cooling this mixed solution, 7.8 g of methyl iodide was added dropwise. It was left to stand at room temperature for 1 hour to form crystals.
Then, the reaction was completed by leaving it at 0 ° C. overnight. The solid formed was collected, washed twice with absolute ethanol and then three times with anhydrous ether to give a white solid compound.
4 was obtained (yield: 90%).

(1) -Synthesis of compound (a) 17.2 g of compound in 10 g NaCN / 100 ml water.
4 was added, and the mixture was heated under reflux for 2 hours to separate an oil layer. The mixture was cooled, extracted with ether, washed with water, dried and evaporated. The product was subjected to column treatment, and the obtained solid was recrystallized from an ether-n-hexane mixed solution (ether: n-hexane = 1: 1) to give 3-cyanomethyl-1,2-
-Dimethylindole (compound (a)) was obtained (yield:
40-70%).

[0039] (2) Synthesis of Compound (b) (2) - Synthesis benzothiophene compound 6 (Compound 6) 33 g (0.25 mol)
Was dissolved in 150 ml of dry tetrahydrofuran (THF). After cooling this to -30 ° C, 0.37 ml of n-butyllithium (hexane solution) was added dropwise and stirred for 1 hour. After standing at room temperature for about 1 hour, the mixture was cooled again to -10 to 0 ° C and 100 g of dry THF was added with 53 g of methyl iodide (.
What melt | dissolved (37 mol) was dripped. After stirring at -10 to 0 ° C for about 1 hour, the mixture was left at room temperature overnight. Then, after adding water, the product was extracted with ether, dried and then ethanol-
Recrystallized with water to give 2-methylbenzothiophene (compound
6 ) was obtained (yield: 80%).

(2) -Synthesis of Compound 7 2 g of Compound 6 was dissolved in 260 ml of 1,2-dichloroethane, 33 g of chloromethyl ether was added thereto, and 50 mg of zinc chloride was added as a catalyst. After reacting for 30 minutes to 2 hours, an extraction operation is performed with water-chloroform,
The organic layer was evaporated to obtain 2.4 g of 3-chloromethyl-2-methylbenzothiophene (Compound 7 ) (yield: 90).
%).

(2) -Synthesis of Compound (b) 1.42 g of Compound 7 was dissolved in 10 ml of Bunsen, and 30 mg of tetra-n-butylammonium bromide and 2.5 g of sodium cyanide were dissolved in 10 ml of an aqueous solution. Was added, and the mixture was vigorously stirred while heating to 60 ° C. for 2 to 3 hours. After completion of the reaction, extraction with benzene was performed, and the organic layer was dried and purified by silica gel chromatography to obtain 1.0
7 g of 3-cyanomethyl-2-methylbenzothiophene (compound (b)) was obtained (yield: 74%).

(3) Synthesis of Compound [III A] 1.012 g (0.0055 mol) of compound (a) and 1.028 g (0.0055 mol) of compound (b) were added to 1.58 ml of carbon tetrachloride and 1 part of benzene. It was dissolved in 0.58 ml, 0.14 g of tetrabutylammonium bromide was added thereto, and the mixture was heated to 40 ° C. Further, 2.18 ml of an aqueous NaOH solution (50% by weight) was added dropwise over 30 minutes. The product was poured into water, extracted with chloroform, dried, and the solvent was distilled off, followed by benzene column chromatography and fractionation by liquid chromatography to obtain a compound [IIIA] having the following physical properties (yield: : 10%).

Physical property mass spectrum: 367 (M ⁺ ) λ max of opened ring: 420 nm λ max of closed ring: 544 nm

Examples 2 to 15 By the method according to Example 1, the compounds shown in Table 1 were synthesized. When each compound was irradiated with ultraviolet light in a benzene solution, the color tone shown in Table 1 was developed.

[0045]

[Table 1]

Example 16 (1) Synthesis Example 1 was repeated except that 1.8 g of 2,3,5-trimethyl-4-methylcyanothiophene was used instead of 2.0 g of the compound (b). Synthesis was carried out to obtain a compound [IIA] having the following physical properties (2).

[0047]

[Chemical formula 12]

(2) Physical property values Mass spectrum: 345 (M ⁺ ) λmax of open ring: 412 nm λmax of closed ring: 549 nm

Examples 17 to 28 By the method according to Example 1, the compounds shown in Tables 2 and 3 were synthesized. When each compound was irradiated with ultraviolet light in a benzene solution, the color tone shown in Table 2 and Table 3 was developed.

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

INDUSTRIAL APPLICABILITY The dicyanoethylene derivative of the present invention has a property of undergoing a color change upon irradiation with light and returning to its original state when irradiated with light of another wavelength, and therefore, it is possible to perform reversible recording with high characteristics in the photon mode. Since it is possible to provide a photochromic compound suitable for a possible optical recording material, it is industrially very useful.

Front page continuation (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03C 1/73 503 8910-2H // C09K 9/02 B 8930-4H

Claims (1)

[Claims] 1. A dicyanoethylene derivative represented by the following general formula [I]. [Chemical 1] (In the general formula [I], A and B do not represent the same substituent, and A is a substituent [i] or [ii] (in the substituents [i] and [ii], R ¹ is an alkyl group. ,
Represents an alkoxy group, a halogen atom or a trifluoromethyl group, and R ² and R ³ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a trifluoromethyl group, a cyano group or an optionally substituted aryl. It may represent a group, or R ² and R ³ may be linked to each other to form an optionally substituted carbocycle or an optionally substituted heterocycle. X is -O-, -S
— Or —NR ⁴ — (R ⁴ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted cycloalkyl group)
Represents. And B is a substituent [iii] or [i
v] (in the substituents [iii] and [iv], R ⁵ represents an alkyl group, an alkoxy group, a halogen atom or a trifluoromethyl group, and R ⁶ and R ⁷ are each independently a hydrogen atom, an alkyl group, an alkoxy group. Represents a group, a halogen atom, a trifluoromethyl group, a cyano group or an optionally substituted aryl group, or represents an optionally substituted carbocycle or a substituted R ⁶ and R ^7. May form a heterocycle, Y is-
O -, - S- or -NR ⁸ - (R ⁸ is a hydrogen atom or a optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted cycloalkyl group) represent a .. ) Is represented. )