JP2579796B2 - Thioindico derivatives - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel photochromic thioindigo derivative having a fluorescent functional substituent.

(Prior Art) Thioindigos are known as photochromic compounds. That is, it is known as a compound that can be interconverted into a trans form and a cis form by photoisomerization.

However, thioindigos that can reversibly change the fluorescence wavelength in response to photostimulation utilizing the above-described photochromism are not known. Compounds having such a function can be expected to be applied to optical switches, optical memories, displays, and the like.

(Problems to be Solved by the Invention) The present invention provides a novel photochromic thioindigo capable of reversibly changing the fluorescence wavelength in response to an optical signal by utilizing the fact that the photochromic site exhibits a structural change due to photoisomerization. It is intended to provide a derivative.

(Means for Solving the Problems) The present invention is a thioindigo derivative represented by the following general formula (I) or (II).

(However, in the above general formulas (I) and (II), X ¹ and X ² may be the same or different, respectively.
-, - CONH -, - OCO -, - NHCO -, - O -, - CH 2 O
—, —CO— and —CH ₂ —, wherein R ¹ and R ² are pyrene, anthracene, phenanthrene, naphthalene, benzo [a] anthracene, naphthacene, perylene, triphenylene, chrysene, benzo [c] Selected from phenanthrene, coronene, methylnaphthalene, fluoronaphthalene, bromonaphthalene, chlornaphthalene, iodonaphthalene, nitronaphthalene, aminonaphthalene, dimethylaminonaphthalene, cyanonaphthalene, aminobenzene, dimethylaminobenzene, nitrobenzene, cyanobenzene and dicyanobenzene Represents a group. (R ¹ and R ² may be the same as each other.) Specific examples of the thioindigo derivative of the present invention include dipyrenylthioindigo-7,7′-dicarboxylic acid amide and dianthranylthioindigo-7,7 ′. -Carboxylic acid amide, dianthranithiothiodigo-7,7'-carboxylic acid ester, thioindigo-7-carboxylic acid pyrenylamide-7'-carboxylic acid-p-nitrophenylamide, thioindigo-7-carboxylic acid anthranilamide-7 '
Trans- and cis-forms such as -carboxylic acid-p-nitrophenylamide, thioindigo-7-carboxylic acid anthranilamide-7'-carboxylic acid dicyanophenyl ester.

The thioindigo derivative of the present invention can be produced from a carboxylic acid compound, hydroxy compound, amino compound or chloromethyl compound substituted at the corresponding position of the thioindigo skeleton. That is, X ¹ or X ^{2 in} the general formula (I) is -COO- or -C
In the case of ONH-, thioindigocarboxylic acid and R ¹ and R ²
Is obtained by a condensation reaction with a hydroxy compound or an amino compound. When X ¹ or X ² is —OCO— or —NHCO—, it can be obtained by a condensation reaction of a hydroxy or amino thioindigo with a carboxylic acid, acid anhydride or acid chloride of R ¹ and R ² . When X ¹ or X ² is —O—, it is obtained by a condensation reaction of the hydroxy form of thioindigo with the hydroxy form or halogen form of R ¹ and R ² . When X ¹ or X ² is —CH ₂ O—, it is obtained by a condensation reaction between a chloromethyl form of thioindigo and a hydroxy form of R ¹ and R ² . When X ¹ or X ² is —CO— and —CH ₂ —, the carboxylic acid chloride of thioindigo is acylated with R ¹ and R ² by a Friedel-Crafts reaction to obtain a —CO— form, which is further reduced. it is possible to obtain the body - -CH ₂ by.

In the above production method, a mixture of a trans-cis form of the thioindigo derivative is generally obtained (in many cases, an excess of the trans form), but the mixture is obtained as a corresponding trans form or cis form by irradiation with light of a specific wavelength. be able to.

(Example) Example 1 Thioindigo-7,7'-dicarboxylic acid 180 mg (0.6 mmo
l) was refluxed with excess thionyl chloride for 3 hours. Excess thionyl chloride was distilled off under reduced pressure, and aminopyrene 250 mg (1.1
5 mmol), benzene (30 ml) and pyridine (20 ml) were added, and the mixture was refluxed for 2 hours and allowed to stand for 5 days. The benzene and pyridine were distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 17 mg of a trans-cis mixture of dipyrenylthioindigo-7,7'-dicarboxylic acid diamide (abbreviated as DPTI). . Further, 64 mg of a by-product of a trans-cis mixture of thioindigo-7-carboxylic acid pyrenylamide-7'-carboxylic acid was obtained.

The properties of the DPTI obtained above were as follows.

Dark red crystal mp 172-174 ° C IR spectrum (cm ^-1 ) (KBr tablet) 1720,1660,1600,1530,1280,1120,1030,840 UV (CHCl ₃ ) λmax (nm) 540,490,345 NMR (CDCl ₃ ) δppm 7.36 (brod, Ar-H) The DPTI mixture obtained above was dissolved in chloroform, and
Irradiated with 0 nm light. This reduced the absorption band at λmax 490 nm and increased the absorption band at 540 nm. It was confirmed that the cis form in the mixture was converted to the trans form by this light irradiation.

Next, 55 to the chloroform solution of the trans form obtained above was added.
When irradiated with 0 nm light, λmax 540 nm decreased and λmax 490 n
m absorption band increased. By this light irradiation, cis-DPTI
Was obtained.

Example 2 64 mg of the by-product thioindigo-7-carboxylic acid pyrenylamide-7'-carboxylic acid obtained in Example 1 was dissolved in 50 ml of anhydrous methylene chloride, 31 mg of N, N'-dicyclohexylcarbodiimide was added, and the mixture was stirred for 15 minutes. did. To this solution, 21 mg of p-nitroaniline was added and reacted at room temperature for 1 hour. This solution was added to 200 ml of cold water to separate the organic layer,
After washing with dilute hydrochloric acid and saturated aqueous sodium hydrogen carbonate, the extract was dried over sodium sulfate, and methylene chloride was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain thioindigo-7.
-Carboxylic acid pyrenylamide-7'-carboxylic acid-p-
2 mg of a trans-cis mixture of nitrophenylamide was obtained.

The properties of the above product were as follows.

Dark red crystal IR spectrum (cm ^-1 ) (KBr tablet) 1720,1660,1540,1350,1300,1100,850 UV (CHCl ₃ ) λmax (nm) 533,490,346,330 The above product was dissolved in chloroform and irradiated with 480 nm light. . As a result, the absorption band at λmax 490 nm is reduced and λmax533
The nm absorption band increased. It was confirmed that the cis form in the mixture was converted to the trans form by this light irradiation. Next, when the chloroform solution of this trans form was irradiated with light at 540 nm, the absorption band at λmax 533 nm decreased and the absorption band at λmax 490 nm increased. It was confirmed that a cis-isomer was obtained by this light irradiation.

Example 3 Thioindigo-7,7'-dicarboxylic acid 300 mg (1 mmol)
Was refluxed with excess thionyl chloride for 3 hours. Excess thionyl chloride was distilled off under reduced pressure, and 10 ml of hexamethylphosphoric triamide and 773 mg of 2-aminoanthracene (4 mmo
l) was added and reacted at room temperature overnight. Cool the reaction mixture to cold water 5
0 ml and extracted with methylene chloride. Methylene chloride and hexamethylphosphoric triamide were distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain a trans-cis mixture of dianthranylthioindigo-7,7'-dicarboxylic acid amide (20 mg).

The properties of the above product were as follows.

Dark red crystal IR spectrum (cm ^-1 ) (KBr tablet) 1720,1660,1520,1300,845 UV (CHCl ₃ ) λmax (nm) 540,490,330 The above product was dissolved in chloroform and irradiated with 480 nm light. As a result, the absorption band at λmax 490 nm is reduced and λmax540
The nm absorption band increased. It was confirmed that the cis form in the mixture was converted to the trans form by this light irradiation. Next, when the chloroform solution of the trans form was irradiated with 550 nm light, the absorption band at λmax 540 nm decreased and the absorption band at λmax 490 nm increased. It was confirmed that a cis-isomer was obtained by this light irradiation.

(Effect of the Invention) The thioindigo derivative of the present invention is a novel compound having both a thioindigo skeleton having photochromic transcis photoisomerization and a substituent having a fluorescent function,
Useful as a wavelength conversion material.

Claims (1)

(57) [Claims] 1. A thioindigo derivative represented by the following general formula (I) or (II). (However, in the above general formulas (I) and (II), X ¹ and X ² may be the same or different, respectively.
-, - CONH -, - OCO -, - NHCO -, - O -, - CH 2 O
—, —CO— and —CH ₂ —, wherein R ¹ and R ² are pyrene, anthracene, phenanthrene, naphthalene, benzo [a] anthracene, naphthacene, perylene, triphenylene, chrysene, benzo [c] Selected from phenanthrene, coronene, methylnaphthalene, fluoronaphthalene, bromonaphthalene, chlornaphthalene, iodonaphthalene, nitronaphthalene, aminonaphthalene, cyanonaphthalene, dimethylaminonaphthalene, nitrobenzene, cyanobenzene, aminobenzene, dimethylaminobenzene and dicyanobenzene Represents a group. R ¹ and R ² may be the same as each other)