JPH01226835A - Photochromic compound - Google Patents

Abstract

NEW MATERIAL:A compound of formulas I and II (ring A is formula III-VI; X is O, S, NR11; R11 is H, alkyl, allyl, aryl; R1 is each group in R11, alkoxy, allyloxy, aralkyl, aryloxy, NH2; R2-R10 are each group in R11, CF3, CN, NO2, alkoxycarbonyl, COOH, acyl, CONH2 where at least one of R3-R6 is a group other than the groups in R11; Y is each group in R1-R10 except CF3). EXAMPLE:1,3-Bisdicyanovinyl-2-(2,5-dimethyl-3-thienylvinylidene)indane. USE:A photochromic compound which is improved in long wavelength sensitivity and enables nondestructive reading, thus being suitably used in optical recording, optical storage material, copying material, photosensitive material for printing, optical filter, display material or the like. PREPARATION:A compound of formula VII is subjected to the Knoevenagel reaction to give the compounds of formulas I-II.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] This invention relates to photochromic compounds used in optical recording, optical storage, copying media, etc.

[Prior Art] Widely known photochromic compounds of this type include, for example, azobenzene compounds, spiropyran compounds, and fulgide compounds.

These photochromic compounds have the property that when they are irradiated with light having a certain wavelength, their structure changes, and when they are further irradiated with light of a certain wavelength, they return to the original compound. Therefore, by utilizing these properties, it becomes possible to optically read and optically write, and it can be used as various optical recording, optical storage, copying media, etc.

By the way, when used as such an optical recording medium, the following properties are required.

(1) Good repeat durability. (Repetition of recording and erasing) (2) Good thermal stability in the dark. (Preservation of color development/decolorization state) (3) Good long wavelength sensitivity. (Compatibility with semiconductor devices) (4) Records can be read out non-destructively. (Non-destructive reading) [Problem to be solved by the invention] However, conventional azobenzene compounds, spiropyran compounds, fulgide compounds, etc. all have the above-mentioned (
It is not possible to satisfy all conditions 1) to 4).
In particular, there is no known device that enables non-destructive reading under condition (4).

Normally, when performing optical recording, writing is performed by first irradiating light of a certain wavelength to change the structure into a structure having a maximum absorption wavelength in a different wavelength range. Furthermore, during erasing, the material is irradiated with light in the same wavelength range as this maximum absorption wavelength to restore the original compound. Conventionally, when reading a record, the record has been read by a method of irradiating weak light with a wavelength slightly longer than this maximum absorption wavelength.

However, with conventional photochromic compounds, the erasure wavelength band is wide and very close to the wavelength of the light used for reading, so even if the light irradiated during reading is weak, the number of readings can be reduced. The problem was that over time, the data gradually disappeared and was eventually destroyed.

Furthermore, there are few conventional compounds that have good sensitivity to long wavelengths, making it difficult to use semiconductor lasers with long wavelengths of about 780 to 850 ni.

The present invention aims to solve the above-mentioned problems and provide a photochromic compound that can be read out non-destructively and has good sensitivity to long wavelengths.

[Means for Solving the Problems] In the present invention, a novel indane-based compound was synthesized to improve long wavelength sensitivity and enable non-destructive readout.

That is, the photochromic compound of the present invention is represented by the following general formula (1) or (II).

[In the formula, R1 represents hydrogen, an alkyl group, an alkoxy group, an allyl group, an allyloxy group, an aralkyl group, an aryl group, an aryloxy group, an amino group, and R2, R3, R4,
R3, R,, R7, R8, R8 and R10 each represent hydrogen, an alkyl group, an allyl group, an aryl group, a trifluoromethyl group, a cyano group, a nitro group, an alkoxycarbonyl group, a carboxyl group, an acyl group, or a carbamoyl group. , and in the general formula (r), R8, R4, R3,
At least I or more of R6 is a trifluoromethyl group, a cyano group, a nitro group, an alkoxycarbonyl group,
It represents one or more selected from carboxyl group, acyl group, and carbamoyl group, and the ring is represented by the following general formulas (DI), (IV), (■), (Vl) (in the formula, X represents oxygen, sulfur, N-R11 (R8 represents hydrogen, alkyl group, allyl group, or aryl group), and Y represents hydrogen, alkyl group, amino group, allyl group, aryl group, alkoxy group, or allyloxy group. , aryloxy group, aralkyl group,
Indicates an acyl group, a cyano group, a nitro group, an alkoxycarbonyl group, a carboxyl group, and a carbamoyl group. ) is shown.

] As shown in FIG. 1, the photochromic compound of the present invention is synthesized from an indan-1,3-dione derivative represented by the following general formula (■), and can be synthesized by Knoevenagel reaction.

[In the formula, R7, R8, R8, R1° are general formula (I), (
It is the same as the substituent in II). ] The photochromic compound thus obtained and having the structural formula of the above formula (1) or (II) has photochromic properties as shown in the following formula (■). Next (■
) Formula is a formula explaining the photochromic property of the compound shown in formula (1). When this compound (I) is irradiated with visible light, the ring closes to form (1)°.

[In the formula, R3, R2, R5, R4, R6, R1, R1,
R8, Rs s Rlo, and A are the same as the substituents in general formula (1). ] Due to this property, recording can be performed by irradiating compound (1) with visible light. As a result, it changes into a closed ring body (1)' having a maximum absorption wavelength in the near-infrared region of wavelengths 700 to 800 n-. Even if this closed ring form (I)° is irradiated with near-infrared rays in the above wavelength range, it will not undergo any structural changes and will not return to its original open ring form (1). However, if it is irradiated with ultraviolet light or It has the property of returning to its original open ring form (1) when heated.

In other words, for such compounds, recording can be performed by irradiating visible light, and erasing can be performed by irradiating the resulting closed ring compound (■)° with ultraviolet rays or heating it. be able to. Also, closed ring body (1)
Taking advantage of the fact that the structure does not change at all even when irradiated with near-infrared rays, reading can be performed by irradiating near-infrared rays. This makes it possible to perform reading using light (near infrared) at a wavelength different from that used for photochromism (ultraviolet and visible light), making it possible to perform non-destructive reading, which was previously impossible.
Even after repeated readings, the data can be read without being erased or destroyed. Moreover, the above-mentioned closed ring body (
Since the maximum absorption wavelength of I) is in the semiconductor laser wavelength region, the compatibility with semiconductor lasers is also good.

Because of these properties, this compound can be used for optical reading and writing using semiconductor lasers, and is useful for optical recording, optical storage materials, copying materials, photoreceptors for printing, optical filters, It can be suitably used as a display material, etc.

[Example] (Example 1) Synthesis of 1.3-bisdicyanovinyl-2-(2,5-dimethyl-3-thienylvinylidene) indane (A) (1) Intermediate raw material 1.3-bisdicyanovinyl indane (
B) Synthesis of indane-1,3-dione 229 and malononitrile 29
9 was dissolved in 250xQ ethyl alcohol, and 30 g of sodium acetate was added while stirring at room temperature. After refluxing for 5 hours, the resulting solid was filtered off to obtain 35 g of compound (B) (melting point: 263-266°C, decomposed).

(2) Synthesis of Compound (A) 2.79 of Compound (B) and 150zQ of acetic anhydride were kept at 60°C, and 2.0g of 2.5-dimethyl-3-formylthiophene was added thereto. After stirring for 1 hour, the resulting crystals were filtered and compound (A) (melting point 244-250°C 1 decomposition)
obtained 1.09.

Table 1 shows the identification results of this indane compound by NMR spectrum.

(Example 2) 1.3-bisdicyanovinyl-2-(4-formyl-1
, 2,5-trimethyl-3-pyrylbinylidene) indane (C) Synthesis of 3.4-diformyl-1,2,5-trimethyl while keeping 1.89 of compound (B) and 75xQ of acetic anhydride at 60°C. 1.4 g of pyrrole was added. After stirring for 1.5 hours,
Acetic anhydride was distilled off and purified by column chromatography (developing solvent: ethyl acetate) to obtain compound (C) (melting point 2
16-217°C 2 decomposition) was obtained.

(Example 3) Synthesis of 2-(4-acetyl-!,2,5-trimethyl-3-pyrylbinylidene)-1,3-bisdicyanovinylindane (D) (1) Intermediate raw material 1,3-bisdicyano Vinyl-2-(1
, 2,5-)dimethyl-3-pyrylbinylidene) indane (E) Synthesis of 3-formyl-1,2,5-trimethylpyrrole while keeping compound (B) 1.19 and acetic anhydride 40xQ at 60°C. 0.8g was added. After stirring for 1.5 hours, the resulting crystals were filtered to obtain compound (E) (melting point 259-262°C).
0.539 was obtained.

(2) Synthesis of title compound (D) To a mixture of 1.09 of compound (E), 0.339 of acetic anhydride, and 50xQ of carbon disulfide, 0.737 of anhydrous tin chloride was added, and acetylation was carried out by Friedel-Crach reaction. went.

The reaction product was separated and purified by column chromatography (developing solvent: ethyl acetate/chloroform), and the compound (
1011 g of D) (melting point 207-210°C) was obtained.

(Example 4) Synthesis of 3-dicyanovinyl-2-(2,5-dimethyl-3-thienylvinylidene)indan-3-one (F) (1) Intermediate raw material 3-dicyanovinylindane! -On (G) synthesis indane-! , 3-dione 259 and malononitrile 23
189 ml of sodium acetate was added to 285 ml of ethyl alcohol and 285 ml of ethyl alcohol while stirring at room temperature.

After continued stirring for 40 minutes, 570i of water (7 and 6N hydrochloric acid were added to adjust the pH to 1, and the resulting solid was filtered out. After washing with water, it was recrystallized from acetic acid to obtain compound (G) 299 (melting point 230~ 233°C) was obtained.

(2) Synthesis of Title Compound (F) 8.09 of Compound (G) was dissolved in 4001 g of ethyl alcohol while hot, and 6.89 of 2,5-dimethyl-3-formylthiophene was added while stirring. The resulting crystals were filtered to obtain compound (F) 12.69 (melting point 212-215
°C) was obtained.

(Example 5) Synthesis of 1.3-bisdicyanovinyl-2-(2,3-dimethoxybenzylidene)indane (H) Compound (B) 1
．． 89 and acetic anhydride 751 at 60℃, 2.3
-1.79 g of dimethoxybenzaldehyde was added and stirred for 3 hours. The formed crystals were filtered and 0.349 compound (
H) (melting point 173-175°C) was obtained.

(Example 6) Synthesis of 1.3-bisdicyanovinyl-2-(2,5-dimethoxybenzylidene)indane (1) 2. of Example 5.
Compound (I
) (melting point 184-186°C) was obtained.

(Example 7) Synthesis Example 5 of 1.3-bisdicyanovinyl-2-(2,3,4-trimethoxybenzylidene)indane (J)
2.3-dimethoxybenzaldehyde of 2.3.4-
Compound (J) (melting point 199-204°C) was prepared in the same manner except that trimethoxybenzaldehyde was used.
Obtained.

(Example 8) Synthesis Example 5 of 1.3-bisdicyanovinyl-2-(2,4,5-trimethoxybenzylidene)indane (K)
2.3-dimethoxybenzaldehyde of 2.4.5-
In the same manner except that trimethoxybenzaldehyde was used, compound (K) (melting point 248-252°C) was converted to 2.79°C.
Obtained.

(Example 9) Synthesis of 1.3-bisdicyanovinyl-2-(2,3-dimethyl-4-methoxybenzylidene)indan (L) 2.3-dimethoxybenzaldehyde of Example 5 was converted into 2,
Compound (L) (melting point 291-295
℃) was obtained at 0.89.

(Example 10) Synthesis of 1.3-bisdicyanovinyl-2-(2,6-dimethyl-4-methoxybenzylidene)indane (M) 2.3-dimethoxybenzaldehyde of Example 5 was mixed with 2.
Compound (M) (melting point 295-300
℃) was obtained.

[Test Example (Photochromism) Each of the compounds obtained in Examples 1 to 10 was dissolved in methylene chloride to prepare a solution of IXI (I' of/Q). -3200) to measure the absorption spectrum of this solution.

Next, light near the maximum absorption wavelength (λa+ax) in the visible region was irradiated, and changes in the spectrum were measured.

Thereafter, based on the newly appeared absorption spectrum, the return reaction was confirmed by irradiating it with light of a wavelength corresponding to the absorption wavelength in the ultraviolet region or by leaving it in a dark place at room temperature.

The maximum absorption wavelength of the original open ring form of each compound, the wavelength of visible light irradiated to it, the maximum absorption wavelength of the resulting closed ring form, and the reaction from the closed ring form to the original open ring form. The methods are summarized and the results are shown in Table 2.

Here, the light used for light irradiation was obtained by combining a 300W xenon lamp UXL-300D-0 manufactured by Ushio Inc. and a 250W ultra-high pressure mercury lamp USH-250D manufactured by the same company with a colored glass filter or an interference filter manufactured by Toshiba. I used something similar.

(Hereafter, margin) Table 2 (Non-destructive read) Compounds A, C, and D obtained in Examples 1 to 4.

Changes in the absorption spectrum at F are shown in FIGS. 2 to 5, respectively.

After visible light (VIS) irradiation, light with a wavelength corresponding to the generated absorption in the near-infrared region was irradiated, but no change was observed in the spectrum. (The compound obtained in Example 4 has 5
The other compounds were irradiated with near-infrared light of 50n- or more, and 600n* or more. ) From this, it became clear that reading could be performed non-destructively by near-infrared irradiation.

(Long wavelength absorption) As shown in Figures 2 to 4, closed ring compounds have absorption in the wavelength range of 700 to 800 nm, which is similar to the wavelength of currently used semiconductor lasers (780 to 850 nm).
It is clear that it is sensitive to this wavelength and can be read out at this wavelength.

[Effects of the Invention] As explained above, since the photochromic compound of the present invention utilizes a novel indane-based compound, no structural change occurs upon reading.
It is not destroyed even after repeated readings, and non-destructive reading, which was previously impossible, becomes possible. It also has very good compatibility with semiconductor lasers, and can perform optical reading and writing using semiconductor lasers.

[Brief explanation of the drawing]

FIG. 1 shows a synthetic scheme showing an example of the method for synthesizing the photochromic compound of the present invention, and FIGS. 2 to 5 show the following:
1 is a graph showing absorption spectra when each of the compounds synthesized in Examples 1 to 4 of the present invention is irradiated with light.

Claims (2)

[Claims] (1) General formula (I), ▲Mathematical formula, chemical formula, table, etc.▼(I) [In the formula, R_1 is hydrogen, alkyl group, alkoxy group, allyl group, allyloxy group, aralkyl group, aryl group,
Indicates an aryloxy group, an amino group, R_2, R_3,
R_4, R_5, R_6, R_7, R_8, R_9 and R_1_0 are hydrogen, alkyl group, allyl group,
Aryl group, trifluoromethyl group, cyano group, nitro group, alkoxycarbonyl group, carboxyl group, acyl group, carbamoyl group, and R_3, R_4, R_
5, at least one or more of R_6 represents one or more selected from trifluoromethyl group, cyano group, nitro group, alkoxycarbonyl group, carboxyl group, acyl group, and carbamoyl group, Ring A has the following general formulas (III), (IV), (V), (VI), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VI) (In the formula, X is oxygen, sulfur, N-R_1_1 (R_1_1
represents hydrogen, an alkyl group, an allyl group, or an aryl group. )
, Y is hydrogen, an alkyl group, an amino group, an allyl group,
Indicates an aryl group, an alkoxy group, an allyloxy group, an aryloxy group, an aralkyl group, an acyl group, a cyano group, a nitro group, an alkoxycarbonyl group, a carboxyl group, and a carbamoyl group. ) is shown. ] A photochromic compound represented by (2) General formula, ▲Mathematical formula, chemical formula, table, etc.▼(II) [In the formula, R_1 is hydrogen, an alkyl group, an alkoxy group, an allyl group, an allyloxy group, an aralkyl group, an aryl group,
Indicates an aryloxy group, an amino group, R_2, R_3,
R_4, R_5, R_6, R_7, R_8, R_9 and R_1_0 are hydrogen, alkyl group, allyl group,
It represents an aryl group, a trifluoromethyl group, a cyano group, a nitro group, an alkoxycarbonyl group, a carboxyl group, an acyl group, and a carbamoyl group, and ring A is represented by the following general formula (III
), (IV), (V), (VI), ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III)▲There are mathematical formulas, chemical formulas, tables, etc.▼
(IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VI) (In the formula, X is oxygen, sulfur, N-R_1_1 (R_1_1
represents hydrogen, an alkyl group, an allyl group, or an aryl group. )
, Y is hydrogen, an alkyl group, an amino group, an allyl group,
Indicates an aryl group, an alkoxy group, an allyloxy group, an aryloxy group, an aralkyl group, an acyl group, a cyano group, a nitro group, an alkoxycarbonyl group, a carboxyl group, and a carbamoyl group. ) is shown. ] A photochromic compound represented by