JP2997078B2 - Photoresponsive crown ether derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel crown ether derivative. More specifically, the present invention relates to a novel photochromic crown ether derivative that can be used as an ion adsorbing / desorbing material, an ion transporting material, or a catalyst for various reactions.

[0002]

2. Description of the Related Art It is well known that crown ethers have useful and unique properties, and their applications to isotope separation, ion transport, amino acid separation, catalysis, etc. are being studied. Attempts have also been made to bind a compound exhibiting photochromism to crown ether and control the function of the crown ether with light. For example, anthracene residues [Tetrahedron Lett. , 21 P. 5
41 (1980)], an azobenzene residue [J. Ame
r. Chem. Soc. 103 p. 111 (198
1)], a spirobenzopyran residue [Bull. Che
m. Soc. Jpn. , 59 p. 1953 (198
6)] and crown ether derivatives having a dihydroindolizine residue (West German Patent Application Publication No. 3823496). These photochromic compounds are reversibly changed to isomers having different absorption spectra by the action of light without changing the molecular weight, so that the function of the crown ether can be controlled by light.

[0003] However, in the photochromic crown ethers reported so far, one of the two isomers is unstable, and practically returns to the stable isomer naturally in a dark place. There was a problem.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the conventional problems and to provide a reversible photochromic crown ether derivative in which both of the two isomers are thermally stable.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, by introducing a specific diarylethene residue into crown ether,
They have found that the object can be achieved, and have completed the present invention based on this finding. That is, the present invention provides a photoresponsive crown ether derivative having a diarylethene residue represented by the following general formula (I) in the following [Chemical Formula 3].

[0006]

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Wherein A and B are aryl groups represented by the following formula

[0008]

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(Where R ¹ and R ² are an alkyl group, an alkoxy group, a fluorinated alkyl group, an amino group, a cyano group or a halogen atom, and R ³ , R ⁴ , R ⁵ and R ⁶ are a hydrogen atom, an alkyl Groups, alkoxy groups, fluorinated alkyl groups, amino groups, cyano groups or halogen atoms, and Y is an oxygen atom, a sulfur atom or an alkyl-substituted imino),
X represents an ethylene group, a trimethylene group, or-(CH ₂ CH ₂ O
) _n CH ₂ CH ₂ — group (where n is an integer of 1 to 4)
It is. Hereinafter, the present invention will be described in detail.

The photoresponsive crown ether derivative of the present invention is represented by the above general formula (I), and the aryl groups A and B may be the same or different. R ^{1 to} R ⁶
As the alkyl group represented by, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
sec-butyl group, n-pentyl group, n-hexyl group,
linear or branched having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, such as an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-decyl group, an n-dodecyl group, and an n-stearyl group. Alkyl group.

Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, n-pentyloxy, n-hexyloxy and n-heptyloxy. Group, n
Examples thereof include an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, such as -octyloxy group and n-decyloxy group.

Examples of the fluorinated alkyl group include the above-mentioned alkyl groups in which some or all of the hydrogen atoms have been replaced with fluorine atoms, for example, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro. —I-propyl group and the like. Examples of the amino group include an NH ₂ group and a hydrogen atom substituted with an alkyl group having 1 to 6 carbon atoms, such as a methylamino group, a dimethylamino group, an ethylamino group, and a diethylamino group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group of the alkyl-substituted imino represented by Y is a C1 to C6 alkyl group such as a methyl group or an ethyl group.
Are preferred. The compounds of the present invention include, for example,
Reaction of 1,2-diaryl-1,2-di (2-hydroxyethoxy) ethene represented by the general formula (II) in the following [Chemical Formula 5] with glycol ditosylate represented by the general formula (III) Wherein A,
B and X are as described above).

[0014]

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The above reaction is carried out by heating in a solvent in the presence of a strong base. Strong bases include NaH, LiOH, Na
OH or the like can be suitably used. As the solvent, an ordinary aprotic solvent can be used, and particularly preferable solvents include ether solvents such as diethyl ether, tetrahydrofuran, and dioxane.

The crown ether derivative having a diarylethene residue of the present invention has a wavelength of, for example, 200 to 400.
Irradiation with light of nm causes a structural change as shown in the following [Chemical formula 6] to change to a closed-ring form (IV). This closed form (IV) can be reversibly restored by a photoreaction.

[0017]

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When the aryl groups A and B are represented by the following general formula,

[0019]

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The above ring closure reaction and ring opening reaction are represented by the following [Chemical formula 8]. That is, in the ring closure reaction, a cyclohesadiene ring is formed.

[0021]

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The crown ether derivative of the present invention is thermally stable in both the ring-opened state (I) and the ring-closed state (IV), and both states are favorably maintained. Further, by the ring closure of (I), the planarity of the portion represented by the following [Chemical Formula 9] constituting the crown ether is lost, and the crown ether skeleton is distorted.

[0023]

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Along with this, functions specific to crown ethers, such as metal ion desorption ability, ion transport ability, and catalytic ability, change. That is, the function of the crown ether can be reversibly and stably controlled by light.

[0025]

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

[0026]

[Reference Example] 1,2-di (2,3,5-trimethyl-4-)
Preparation of thienyl) -1,2-di (2-hydroxyethoxy) ethene 16.5 g of 2,3,5-trimethylthiophene (0.1
Stannic chloride (37 g, 0.14 mol) in a benzene 80 ml solution containing acetic anhydride (16 mol, 0.16 mol).
mol) is added dropwise at 0 ° C.
After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. The reaction solution was poured into ice water, and the benzene layer was separated. The aqueous layer was extracted three times with 50 ml each of benzene. Combine the benzene layers, dilute hydrochloric acid,
After washing with water and a saturated saline solution and drying, benzene was distilled off.
The crude product is distilled under reduced pressure (bp 83 to 85 ° C./2 mmHg)
As a result, 21 g (yield 95%) of an acetyl derivative shown in the following [Chemical Formula 10] was obtained.

[0027]

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9.0 g (80 mmol) of selenium dioxide was dissolved in 50 ml of dioxane and 2.5 ml of water at 60 ° C., and 13.5 g (80 mmol) of the acetyl compound (1) was obtained.
Was added and the mixture was heated under reflux for 5 hours. The reaction mixture was cooled to room temperature, the precipitate was filtered, and the solvent was distilled off under reduced pressure. The crude product was distilled under reduced pressure (bp 95 to 100 ° C./1 mmHg), and 6.5 g of a glyoxyloyl compound represented by the following chemical formula 11 was obtained.
(44% yield).

[0029]

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2,3,5-trimethylthiophene 6.6
g (52 mmol) in benzene 50 ml solution, stannic chloride 23 g (87 mmol) in benzene 50 m
The solution was added dropwise at 0 ° C. Benzene 30 containing 8 g (43 mmol) of the glyoxyloyl compound (2) in this solution
ml solution was slowly added dropwise at 0 ° C. After the dropwise addition, the mixture was stirred at 0 ° C. for 2 hours, and then returned to room temperature. The reaction solution was poured into dilute hydrochloric acid containing ice, and the organic layer was separated. The aqueous layer was extracted three times with 50 ml each of ether. The organic layers were combined, washed with water and saturated saline, dried, and the solvent was distilled off. The crude product was purified by silica gel column chromatography (hexane, ether) to obtain 7.5 g (yield 57%) of thienoin represented by the following [Chemical formula 12].

[0031]

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9.2 g (30 mm) of the above thienoin (3)
ol) and 18 g (60 mmol) of 2- (2-tetrahydropyranyl) oxyethyl tosylate and 0.7 g (3 mmol) of benzyltriethylammonium chloride
In a solution of dioxane containing 30 ml of solid NaOH4.
8 g (120 ml) and added at 80 ° C. under a nitrogen atmosphere.
Stirred for hours. Water was added to the reaction mixture and extracted three times with 50 ml each of ether. The ether layer was washed with water, dried and concentrated under reduced pressure. 20 ml of methanol and 0.2 g of p-toluenesulfonic acid were added to the residue, and the mixture was heated under reflux for 30 minutes.
Neutralize the reaction with 0.5N NaOH solution, 50 ml each
Extracted three times with ether. The ether layer was washed with water and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (chloroform: acetone = 9: 1), and 1,2-di (2,3,5-trimethyl-4-thienyl) -1, 7.2 g (60% yield) of 2-di (2-hydroxyethoxy) ethene was obtained.

[0033]

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¹ H-NMR (CDCl ₃ ) δ: 1.77 (6H, s, Ar—CH ₃ ) , 2.05
(6H, s, Ar-CH 3), 2.18 (6H, s, A
_{r-CH 3), 3.48~3.80 (} 10H, m, -O
CH ₂ CH ₂ O—, —OH) mass spectrum (m / Z) 396 (M ⁺ )

[0035]

Example 1 0.96 g (60% oil) of sodium hydride was washed several times with hexane in a nitrogen atmosphere,
0 ml of tetrahydrofuran was added, and the mixture was heated under reflux. To this solution, 0.92 g (2.3 mmol) of 1,2-di (2,3,5-trimethyl-4-thienyl) -1,2-di (2-hydroxyethoxy) ethene and triethylene glycol ditosylate 1 A solution of 0.06 g (2.3 mmol) in 100 ml of tetrahydrofuran was slowly added dropwise. After the dropwise addition, the mixture was heated under reflux for 40 hours. After the reaction, a small amount of diluted hydrochloric acid was added to the reaction solution to make it acidic, and the precipitate was separated by filtration. The filtrate was concentrated under reduced pressure, and water and dichloromethane were added to the obtained residue and extracted three times. The organic layer was washed with water, dried and concentrated. The residue was purified by silica gel chromatography (hexane: ethyl acetate = 1: 1, 5% triethylamine) to obtain a crown ether derivative represented by the following chemical formula (yield: 36%).

[0036]

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¹ H-NMR (CDCl ₃ ) δ: 1.78 (6H, s, Ar—CH ₃ ), 2.05
(6H, s, Ar-CH 3), 2.17 (6H, s, A
_{r-CH 3), 3.60~3.78 (} 20H, m, -O
CH ₂ CH ₂ O—) Mass spectrum (m / Z) 510 (M ⁺ ) A solution obtained by dissolving the compound (5) in 1,2-dichloroethane is sealed in a 1 cm × 1 cm × 4 cm glass cell. When this was irradiated with light of 313 nm, it was colored, and its absorption spectrum changed from that shown by the broken line to that shown by the solid line in FIG. That is,
As shown in [5], the compound (5) was changed to a closed-ring form (6) by irradiation with light of 313 nm.

[0038]

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This ring isomer is extremely stable thermally,
No change in the absorption spectrum was observed even after heating at 0 ° C for 12 hours or more. Next, 436 nm was added to the glass cell.
When the light was irradiated, the absorption spectrum returned to the original absorption spectrum shown by the broken line in FIG. The extraction experiment of metal ions using the ring-opened body (5) and the ring-closed body (6) was performed as follows. 1,2-containing 1.0 × 10 ⁻² M of compound (5) or (6) in 5.0 ml of an aqueous solution containing 2.0 × 10 ⁻⁵ M of picric acid and 1.0 × 10 ⁻² M of metal nitrate After adding 5.0 ml of a dichloroethane solution and shaking for 30 minutes, the absorbance of picrate in the aqueous layer was measured. For K ⁺ ions, 18.5% in (5) and 6.5 in (6)
% Was extracted. A similar tendency was observed with Na ⁺ ions.

[0040]

Example 2 1,2-Di (2,3,5-trimethyl-4)
-Thienyl) -1,2-di (2-hydroxyethoxy)
1.55 g (3.9 mmol) of ethene, LiOH.H ₂
O 0.2 g (4.8 mmol) and NaOH 0.0
Tetrahydrofuran 30 containing 6 g (1.6 mmol)
0 ml of the suspension was refluxed for 1 hour under a nitrogen atmosphere, and then, while refluxing, trimethylene glycol ditosylate.
A tetrahydrofuran solution containing 1.5 g (3.9 mmol) was slowly added dropwise. After refluxing the reaction mixture for 96 hours, the solvent was distilled off, 30 ml of water was added, and the mixture was extracted three times with 30 ml of chloroform each. The organic layer was dried and concentrated under reduced pressure, and the residue was purified by silica gel chromatography (hexane: ethyl acetate = 2: 1, 0.1% triethylamine) to obtain a crown ether derivative represented by the following chemical formula 16 (yield). 22%).

[0041]

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¹ H-NMR (CDCl ₃ ) δ: 1.79 (6H, s, Ar—CH ₃ ), 2.08
(6H, s, Ar-CH 3), 2.20 (6H, s, A
_{r-CH 3), 1.8~2.2 (} 2H, q, -CH
_{2 -), 3.64 (8H,} m, OCH 2), 3.82
(4H, t, = C-OCH ₂ ) Mass spectrum (m / Z) 436 (M ⁺ ) As shown in the following [Chemical formula 17], the compound (7) is thermally reacted with light similarly to the compound (5). It was converted to a very stable closed-ring form (8).

[0043]

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The compounds (7) and (8) were measured for metal ion extractability in the same manner as in Example 1. The extractability of Li ⁺ ion was 7.1 % in the ring-opened product (7),
In the closed ring form (8), the content was 0.2 %.

[0045]

The crown ether derivative having a diarylethene residue according to the present invention is a novel compound and a compound exhibiting good photochromism. That is, the crown ether derivative of the present invention can take two structures reversibly by light, and both structures are thermally stable. Therefore, the compounds of the present invention are extremely useful as ion-adsorbing / desorbing materials, ion-transporting materials, and catalysts for chemical reactions, whose functions can be controlled by light.

[Brief description of the drawings]

FIG. 1 is an absorption spectrum diagram of a crown ether compound (5) produced in Example 1 in a 1,2-dichloroethane solution.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07D 407/04 307 C07D 407/04 307 407/14 307 407/14 307 409/04 323 409/04 323 409/14 323 409 / 14 323 495/14 495/14 A C09K 3/00 108 C09K 3/00 108B 108D 9/02 9/02 B (56) References Tetrahedron Letters (1981), 22 (14), pages 1319-1322. Org. Chem. (1985), 50 (25), pages 5151-5156 Chemistry Letters (1982), (6), pages 781-784 (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 323/00-323/06 C07D 405/00-405/14 C07D 407/00-407/14 C07D 409/00-409/14 C09K 9/02 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A photoresponsive crown ether derivative having a diarylethene residue represented by the following general formula (I) in the following [Chemical Formula 1]. Embedded image Wherein A and B are aryl groups represented by the following [Chemical Formula 2]. (Where R ¹ and R ² are an alkyl group, an alkoxy group, a fluorinated alkyl group, an amino group, a cyano group or a halogen atom, and R ³ , R ⁴ , R ⁵ and R ⁶ are a hydrogen atom, an alkyl group, an alkoxy group, Group, a fluorinated alkyl group, an amino group, a cyano group or a halogen atom, Y is an oxygen atom, a sulfur atom or an alkyl-substituted imino), X is an ethylene group, a trimethylene group, or — (CH ₂ CH ₂ O) ) _n CH ₂ CH ₂ −
(Where n is an integer of 1 to 4). ]