JP3256744B2 - Oxymethyl crowned spirobenzopyran - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel compound, oxymethyl crowned spirobenzopyran.

[0002]

2. Description of the Related Art Various photochromic compounds including diazobenzene have been studied as light-sensitive devices from the viewpoint of photo-functional materials. Spirobenzopyran, which opens a spiro ring according to the following formula upon irradiation with UV light and isomerizes to a merocyanine compound, is also one of the photochromic compounds, and its application to photofunctional materials has been widely studied.

[0003]

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[0004]

An object of the present invention is to provide a novel compound useful as, for example, an optically functional material.

[0005]

Means for Solving the Problems The present inventors have developed a novel compound, oxymethyl crowned spirobenzopyran of a specific structure, which has not been described in the literature, and a method of selecting an alkali metal ion that reflects the size of the crown ring with respect to an alkali metal ion. It has been found that the compound is an ion-sensitive photochromic compound exhibiting the property.

That is, the present invention provides the following oxymethyl crowned spirobenzopyran. 1. General formula (I)

[0007]

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Wherein R is a hydrogen atom or a C 1-20
And n is an integer of 0 to 5). Oxymethyl crowned spirobenzopyran. 2. 2. The oxymethyl crowned spirobenzopyran according to item 1, wherein in the general formula (I), R is a lower alkyl group, and n is an integer of 1 to 3. 3. In the above general formula (I), R is a methyl group;
Item 2. The oxymethyl crowned spirobenzopyran according to Item 1, wherein n is 1. 4. In the above general formula (I), R is a methyl group;
Item 2. The oxymethyl crowned spirobenzopyran according to Item 1, wherein n is 2. 5. In the above general formula (I), R is a methyl group;
Item 2. The oxymethyl crowned spirobenzopyran according to Item 1, wherein n is 3. 6. Item 6. An optical functional material containing the oxymethyl crowned spirobenzopyran according to any one of Items 1 to 5.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The oxymethyl crowned spirobenzopyran of the present invention is a novel compound which has not been described in the literature and has the general formula (I)

[0010]

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Wherein R is a hydrogen atom or a C 1-20
And n represents an integer of 0 to 5. ).

The compound of the present invention isomerizes into a merocyanine compound by irradiation with UV light, and has an absorption wavelength of about 560 nm,
A compound having a large absorption spectrum in a long wavelength region having a molar extinction coefficient ε of about 20,000 and having very advantageous physical properties as an optical functional material. Furthermore, the oxymethyl crowned spirobenzopyran of the present invention is a photochromic compound having ion sensitivity, exhibits selectivity reflecting the size of a crown ring to an alkali metal ion, and a crown ring and an alkali metal ion. Has a characteristic that the molar extinction coefficient decreases and the merocyanine formed by irradiation with UV light is remarkably stabilized.

In the compound represented by the general formula (I), the alkyl group represented by R is a linear or branched alkyl group having 1 to 20 carbon atoms, and preferably has 1 to 20 carbon atoms. About 1 to 6 lower alkyl groups. Such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,
Examples include undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and the like.

In the general formula (I), n is from 0 to 5
And preferably an integer of 1 to 3.

Hereinafter, a method for producing the compound of the present invention will be described.

First, according to the following reaction formula, a known compound, 3-chloromethyl-5-nitrosalicylaldehyde of the general formula (II), and a known compound, 1-alkyl-3,3- By reacting with dimethyl-2-methyleneindoline, chloromethylspirobenzopyran represented by the general formula (IV) is synthesized.

[0017]

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(In the general formulas (III) and (IV), R is the same as described above.) This reaction is carried out using ethanol, tetrahydrofuran (TH
F), organic solvents such as dioxane, preferably dehydrated THF
Can be carried out in 1-alkyl-3, relative to 1 mol of 3-chloromethyl-5-nitrosalicylic aldehyde.
3-Trimethyl-2-methyleneindoline may be reacted in an amount of about 0.5 to 2 mol, preferably about an equimolar amount. The reaction can be performed in an inert atmosphere such as a nitrogen atmosphere, and the reaction temperature may be about 0 to 100 ° C, preferably about 70 to 80 ° C. The reaction time is usually 2
It may be about 6 hours.

Then, according to the following reaction formula, the obtained chloromethylspirobenzopyran of the general formula (IV) is reacted with a hydroxymethyl crown ether of the general formula (V), which is a known compound, to obtain the desired compound. An oxymethyl crowned spirobenzopyran represented by the general formula (I) can be obtained.

[0020]

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This reaction is carried out by using a basic compound such as lithium hydroxide, potassium hydroxide, sodium carbonate and sodium hydride as a catalyst, preferably sodium hydroxide in powder form, and using an organic solvent such as THF and dioxane. , Preferably in dehydrated THF.

The reaction ratio of the hydroxymethyl crown ether of the general formula (V) to the chloromethyl spirobenzopyran of the general formula (IV) is at least about 1 mol, preferably 3 to 6 mol, per mol of the former. It may be about the degree. The amount of the catalyst used may be about 7 to 15 mol, preferably about 10 mol, per 1 mol of chloromethylspirobenzopyran. The reaction temperature may be about 0 to 80 ° C., preferably about room temperature, and the reaction time may be about 1 to 2 hours.

The compound of the present invention thus obtained can be easily isolated and purified from the reaction mixture according to commonly used separation and purification means.

The oxymethyl crowned spirobenzopyran of the present invention is a photochromic compound having a property that a spiro ring is opened by UV light irradiation and isomerized into a merocyanine compound. Shows selectivity reflecting the size of the ring, by coexisting alkali metal ions,
It will exhibit absorption characteristics according to the type of alkali metal ion. The compound of the present invention can be effectively used as an optical functional material such as an ion-selective colorimetric reagent and an ion-sensitive optical storage element by utilizing such characteristics.

[0025]

The compound of the present invention exhibits selectivity for the alkali metal ion reflecting the size of the crown ring.
It is a so-called ion-sensitive photochromic compound,
It is a compound useful as an optical functional material.

[0026]

The present invention will be described below in more detail with reference to production examples and examples. Production Example 1 Synthesis of chloromethylspirobenzopyran 1.08 g of 3-chloromethyl-5-nitrosalicylaldehyde in a three-necked flask (300 ml) under a nitrogen atmosphere.
(5 mmol) and 90 ml of dehydrated THF were added and stirred at room temperature. Then, 0.87 g (5 mmol) of 1,3,3-trimethyl-2-methyleneindoline was added to dehydrated THF1.
The solution dissolved in 0 ml was added, and the mixture was heated under reflux for 4 hours. The reaction solution obtained is allowed to cool, and the following formula

[0027]

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There was obtained chloromethylspirobenzopyran represented by the following formula (yield: 40%). Example 1 Spirobenzopyranoxymethyl 12 Crown 4 (SB
Synthesis of P-OM12C4) In a three-necked flask (300 ml), 20 ml of a THF solution of chloromethylspirobenzopyran (1 mmol) obtained in Production Example 1 and 618 of hydroxymethyl 12 crown 4 were added.
mg (3 mmol) and stirred at room temperature. To this, 360 mg (9 mmol) of powdered NaOH was added, and 1
Stirred for hours. Acetic acid (540 mg, 9 mmol)
After stirring for 1 minute, 100 ml of chloroform and 100 ml of water were added, and the chloroform layer was separated. The chloroform layer was distilled off, and SPC-O in which R = methyl and n = 1 in the above general formula (I) by GPC.
M12C4 was obtained as a reddish purple liquid. Yield (total from the synthesis reaction of chloromethyl spirobenzopyran): 40% ¹ H-NMR (CDCl ₃ ) δ: 1.20 (3H, s, −
_{CH 3), 1.27 (3H,} s, -CH 3), 2.70
(3H, s, -N-CH 3), 3.4~3.8 (17
_{H, m, -OCH 2 -,} - OCH =), 4.29 (2
_{H, q, Ph-CH 2} -), 5.86 (1H, d, = C
H-), 6.53 (1H, d, ArH), 6.87 (1
H, t, ArH), 6.93 (1H, d, = CH-),
7.07 (1H, d, ArH), 7.18 (1H, t,
ArH), 7.94 (1H, s, ArH), 8.16
(1H, s, ArH) Example 2 Spirobenzopyranoxymethyl 15 Crown 5 (SB
Synthesis of P-OM15C5) Instead of hydroxymethyl 12 crown 4 used in Example 1, 750 mg of hydroxymethyl 15 crown 5 was used.
In the same manner as in Example 1 except that (3 mmol) was used, SBP-OM15C5 in which R = methyl and n = 2 in the general formula (I) was obtained. Yield (total from synthesis reaction of chloromethyl spirobenzopyran): 27% ¹ H-NMR (CDCl ₃ ) δ: 1.19 (3H, s, −
_{CH 3), 1.27 (3H,} s, -CH 3), 2.69
(3H, s, -N-CH 3), 3.4~3.8 (21
_{H, m, -OCH 2 -,} - OCH =), 4.29 (2
_{H, q, Ph-CH 2} -), 5.86 (1H, d, = C
H-), 6.53 (1H, d, ArH), 6.86 (1
H, t, ArH), 6.93 (1H, d, = CH-),
7.07 (1H, d, ArH), 7.18 (1H, t,
ArH), 7.93 (1H, s, ArH), 8.18
(1H, s, ArH) Example 3 Spirobenzopyranoxymethyl 18 Crown 6 (SB
Synthesis of P-OM18C6) Instead of hydroxymethyl 12 crown 4 used in Example 1, 882 mg of hydroxymethyl 18 crown 6 was used.
(3 mmol) except that it was used in the same manner as in Example 1,
In the above general formula (I), SBP-OM18C6 in which R = methyl and n = 3 was obtained. Yield (total from the synthesis reaction of chloromethyl spirobenzopyran): 16% ¹ H-NMR; (CDCl ₃ ) δ: 1.20 (3H, s,
_{-CH 3), 1.28 (3H,} s, -CH 3), 2.70
(3H, s, -N-CH 3), 3.4~3.8 (25
_{H, m, -OCH 2 -,} - OCH =), 4.30 (2
_{H, s, Ph-CH 2} -), 5.86 (1H, d, = C
H-), 6.54 (1H, d, ArH), 6.87 (1
H, t, ArH), 6.93 (1H, d, = CH-),
7.07 (1H, d, ArH), 7.18 (1H, t,
ArH), 7.94 (1H, s, ArH), 8.18
(1H, s, ArH) Experiment 1 A 1 × 10 ⁻⁴ M acetonitrile solution of SBP-OM12C4 obtained in Example 1 was prepared, and lithium perchlorate, sodium perchlorate or The absorption spectrum of the solution to which potassium perchlorate was added to a concentration of 1 × 10 ⁻⁴ M was measured. FIG. 1 shows the measurement results.

As is apparent from FIG. 1, the solution containing sodium ions and the solution containing potassium ions gave almost the same absorption spectrum as the blank solution in which these ions did not exist. It was confirmed that the ring had not opened. On the other hand, in the lithium ion solution, it was found that some spiro rings were opened due to complex formation between lithium ions and crown ether. Experiment 2 A 1 × 10 ⁻⁴ M acetonitrile solution of SBP-OM12C4 obtained in Example 1 was prepared, and this solution and this solution were further concentrated with lithium perchlorate, sodium perchlorate or potassium perchlorate. The solution added to 1 × 10 ⁻⁴ M was irradiated with 365 nm UV light for 3 minutes. The absorption spectra for these solutions are shown in FIG.

As is apparent from FIG. 2, the spiro ring is opened in all the solutions, and the blank, sodium ion-containing solution and potassium ion-containing solution obtain an absorption spectrum having an absorption at about 560 nm. As a result, an absorption spectrum having an absorption at 525 nm was obtained. From this result, while the absorption shifted to the shorter wavelength side due to the interaction between the crown ring and the lithium ion,
It was recognized that the molar extinction coefficient tended to decrease as the contribution of complex formation with the crown ring increased in the order of potassium, sodium, and lithium ions. Experiment 3 A 1 × 10 ⁻⁴ M acetonitrile solution of SBP-OM15C5 obtained in Example 2 was prepared, and this solution and this solution were further concentrated with lithium perchlorate, sodium perchlorate or potassium perchlorate. The solution added to 1 × 10 ⁻⁴ M was irradiated with 365 nm UV light for 3 minutes. The absorption spectra for these solutions are shown in FIG.

As is evident from FIG. 3, the spiro ring was opened in all the solutions and the corresponding absorption spectra were given. Above all, in a system in which sodium ions are present, while absorption appears on the shortest wavelength side, suggesting complex formation with sodium ions, the same tendency as in Experiment 2 in which the molar extinction coefficient is reduced was recognized. Experiment 4 A 1 × 10 ⁻⁴ M acetonitrile solution of SBP-OM18C6 obtained in Example 3 was prepared, and this solution and this solution were further concentrated with lithium perchlorate, sodium perchlorate or potassium perchlorate. The solution added to 1 × 10 ⁻⁴ M was irradiated with 365 nm UV light for 3 minutes,
The absorption spectrum was measured. As a result, SBP-OM1
Although the degree of selectivity was lower than when 2C4 was used, the expression of a photochromic function reflecting the ion selectivity of the crown with respect to lithium ions was observed. Experiment 5 1 of SBP-OM12C4 prepared in the same manner as in Experiment 1
1 × 10 ⁻⁴ M for a × 10 ⁻⁴ M acetonitrile solution
The change in the photochromic function in the presence and absence of lithium ions was examined by measuring the change over time in the absorption at 525 nm after irradiating with 365 nm UV light for 3 minutes. FIG. 4 shows the results.

From these results, it was found that the spiro ring was reformed within 30 minutes in the blank solution containing no lithium ion, whereas the spiro ring was regenerated much slower in the lithium ion solution. It can be seen that ring-opened merocyanine is stabilized by complex formation of the ring and lithium ions. Experiment 6 Experiment 5 was performed using SBP-OM15C5 obtained in Example 2.
The time-dependent change of the photochromic function in the presence and absence of lithium ions was determined in the same manner as in. FIG. 5 shows the results.

From these results, although the spiro ring re-formation rate in the lithium ion solution was lower than that in the blank solution containing no lithium ion, SBP-OM12C4
Since the spiro ring re-formation rate is much higher than that of the lithium ion solution, it can be confirmed that the complex formation between the crown ring and the ion greatly contributes to the stabilization of merocyanine.

From the results of the above experiments, it can be confirmed that the oxymethyl crown spirobenzopyran of the present invention is an ion-sensitive photochromic molecule reflecting the ion selectivity of the crown ring.

[Brief description of the drawings]

FIG. 1 is a graph showing an absorption spectrum in Experiment 1.

FIG. 2 is a graph showing an absorption spectrum after UV light irradiation in Experiment 2.

FIG. 3 is a graph showing an absorption spectrum after UV light irradiation in Experiment 3.

FIG. 4 is a graph showing a temporal change in an absorption spectrum after UV light irradiation in Experiment 5.

FIG. 5 is a graph showing a temporal change in an absorption spectrum after UV light irradiation in Experiment 6.

Claims (6)

(57) [Claims] 1. A compound of the general formula (I) (Wherein, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and n is an integer of 0 to 5) oxymethyl crowned spirobenzopyran. 2. The oxymethyl crowned spirobenzopyran according to claim 1, wherein in the general formula (I), R is a lower alkyl group and n is an integer of 1 to 3. 3. The oxymethyl crowned spirobenzopyran according to claim 1, wherein in the general formula (I), R is a methyl group and n is 1. 4. The oxymethyl crowned spirobenzopyran according to claim 1, wherein in the general formula (I), R is a methyl group and n is 2. 5. The oxymethyl crowned spirobenzopyran according to claim 1, wherein in the general formula (I), R is a methyl group and n is 3. 6. An optically functional material containing the oxymethyl crowned spirobenzopyran according to claim 1.