JPS6052150B2 - Method for producing photochrome compound - Google Patents

Description

[Detailed description of the invention] The present invention relates to new photochrome compounds.

Photochrome compounds have been known for a long time,
Treatment with one wavelength or range of wavelengths causes a color change, and the original color is restored under the influence of heat or light of another wavelength or range of wavelengths. According to the present invention, the general formula and [wherein A is oxygen or]NR4 (wherein, A is oxygen or)
R4 represents hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an aralkyl group having 7 to 9 carbon atoms, an aryl group having 6 to 147 carbon atoms, and one or may be substituted with more than one halogen or alkoxy group of 1 to 20 carbon atoms, and alternatively represents an alkaryl group of 7 to 22 carbon atoms; R1 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an allyl group having 6 to 1 hydrogen atoms; R2 and R3 are the same or different alkyl groups having 1 to 2 hydrogen atoms; or one of R2 and R3 is hydrogen and the other is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 1 jealousy atoms; X is hydrogen and 1 to 20 carbon atoms; an alkyl group of 6 to 1 aryl group or 7 to 1
an aralkyl group having 2 carbon atoms; each Y is the same or different and is hydrogen, or a halogen atom, an alkyl or alkoxy group having 1 to 20 carbon atoms, or 6 to 14 J! J. The present invention relates to a photochrome compound having an aryl group or an aryloxy group with a prime number of atoms.

When R1, R2, R3, R4, X or Y represents an alkyl group, for example, a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, isobutyl group, secondary monobutyl group, Tertiary monobutyl group, secondary monoamyl group, tertiary monoamyl group, n-hexyl group,
normal hebutyl group, tertiary monooctyl group, nonyl group,
A normal-udecyl group, a normal-undecyl group, a normal-dodecyl group, a normal-pentadecyl group, a normal-hexadecyl group, or a normal-octade;sil group.

When R1, R2, R3, R4, X or Y represents an aryl group, it can be, for example, a phenyl group or a naphthyl group.

When R4 represents a cycloalkyl group, it can be, for example, a cyclopentyl group or a cyclohexyl group.

When R4 is an aralkyl group, it can be, for example, a benzyl group, an α-methylbenzyl group, or an α,α-dimethylbenzyl group. When 3R4 is alkaryl, for example, methylphenyl group, ethylphenyl group, isopropylphenyl group, tertiary butylphenyl group, secondary butylphenyl group, amyl phenyl group, n-dodecylphenyl group or 2,4-dimethyl 3
It can be a phenyl group. When Y represents an alkoxy group, it can be, for example, a methoxy group, an ethoxy group, a propoxy group or a butroxy group.

When Y is an aryloxy group, it can be, for example, a phenoxy group or a naphthoxy group.

Specific examples of the compounds of the present invention include the following compounds.

(However, X is O or S) (However, x is O or S) (However, R is a benzyl group) (However, X is O or S) (However, in the formula, X is 0 or S and ξ Ar is "2" ] The compound of the present invention is an aldehyde or ton having the formula ゛un- or "Cho-ichi-" , // \\ (wherein B..Rl, X and Y are as defined above). and the formula (wherein R2 and R3 are as defined above, and R5 is an alcohol residue) are converted into a stop (StObbe).
) by condensation, hydrolyzing the resulting half ester to form a diacid, and then reacting the resulting diacid with an acid chloride to give a product of formula 1 or where A is oxygen. .

The stop condensation can be performed by refluxing the reagents in tertiary-butanol containing potassium tertiary-butoxide when harsh conditions are required, or in anhydrous ether, benzene, or toluene when milder conditions are required. Use sodium hydride.

The product of this stage of the reaction is the half ester, R5
is hydrogen. Next, it is converted into di-acid by hydrolysis, for example, by boiling with an aqueous potassium hydroxide solution. The diacid is then subjected to a dehydration reaction involving heating with an acid chloride to form an anhydride. Preferably, use acetyl chloride. The compounds of formula 1 or in which A is oxygen thus prepared are:
Equimolar proportions of anhydride and primary amine R4N117 can be heated to convert compounds in which A is '-NR4 to form the corresponding half-amide.

This half-amide is then heated with an acid chloride or acid anhydride such as acetyl chloride or acetic anhydride to form the desired compound. The reaction with the amine can be carried out in an organic solvent such as ethanol or benzene, if desired. An alternative method for preparing compounds of formula 1 where A is ':-NR4 is to react the half ester of the stop condensation with compound i having the formula to form the corresponding succinic acid monoamide (succinamic acid).

Toesaw COOR5 becomes CONHR4. This is then dehydrated by reaction with an acid chloride such as acetyl chloride. The compounds of the present invention have improved photochrome properties compared to known photochrome compounds.

These have increased photosensitivity and reactivity. This is in part because the photocolored material is less absorbent and less likely to act as an internal filter for the wavelengths used to promote photocoloring. This photocolored intermediate has a broad and strong long wavelength absorption band, which is believed to result from the heteroatom B in the heterocyclic ring system. Improvements in the lateral layer are observed in compounds of formula 1 where the group X is other than hydrogen and in compounds of formula. The photochromic intermediates of such compounds are thermally stable and do not fatigue in the same way that known photochrome compounds do.
Thermal ring opening is believed to be prevented by steric hindrance between X and R3, and x does not migrate to another position. To effect the coloring process, the compound is irradiated in the near ultraviolet region, ie 366 or 404 nm, and the photoreversal process takes place in the visible spectrum. In this case, the optimal condition is 514
For example, an argon ion laser is used with green light at 550 nm. The compounds of the present invention exhibit the following properties.

1 In some cases, it shows slow photochemical reversal60
At wavelengths below 0r1m, reading is possible with almost no decomposition.

2 Shows excellent thermal stability.

3 shows a high quantum yield conversion to a colored body.

4 Photochemical degradation products do not interfere with photochromicity.

The compounds of the invention are suitable for a wide variety of uses.

It can be used for information storage, holographic recording, telecopying devices using laser technology and information display screens. The invention is illustrated in the following examples, in which parts are by weight.

Example 1 (E)- and (Z)-α-2,5-dimethyl-3
- furylethylidene (isopropylidene) succinic anhydride 3-acetyl-2,5-dimethylfuran (7 parts) and diethyl isopropylidene succinate (W part),
Sodium hydride (5 parts) is added to a suspension containing benzene (10 parts by weight).

When the reaction is complete, a small amount of ethanol is added to decompose the excess sodium hydride, the solvent is distilled off, and the residue is acidified with hydrochloric acid. The liberated half-ester (8 parts) is hydrolyzed with 10% ethanolic potassium hydroxide and the diacid is precipitated using hydrochloric acid. Dry acid (1 part) was dissolved in acetyl chloride (5 parts).
0 parts by volume) and leave at room temperature to dissolve all the acid. The solvent was distilled off, and the (E) and (Z) monoisomers were separated. Fractional crystallization from chloroform and petroleum ether gives pale yellow crystals. The melting points are 126-127 degrees Celsius and 158-159 degrees Celsius, respectively. Cl becomes purple when irradiated with 366 nm light. The color returns to its original color when exposed to white light. Example 2 2-benzyl-3-acetylbenzofuran is used as a reactant instead of 3-acetyl-2,5-dimethylfuran.

Pale yellow needle-like (Z)-1α-2-benzyl-3-benzofurylethylidene (isopropylidene) succinic anhydride is obtained. When reconsolidated from petroleum ether and irradiated with a melting point of 178-180 degrees CO366 rlm, it becomes red. The color returns with white light. Example 3 Example 1 is repeated using 3-acetyl-2,5-dimethylphen in the reaction instead of 3-acetyl-2,5-dimethylfuran.

(Z)-α-2,5-dimethyl-3-thienylethylidene (isopropylidene) succinic anhydride is obtained. Almost colorless crystal, melting point 155 to 156 degrees CO366nn
When irradiated with l, it becomes deep red. White light returns the color to its original state.
Example 4 Example 1 is repeated using diethyl (E)-piperonylidene succinate 9 as the reactant instead of diethyl isopropylidene succinate.

Dry diacid (1 part) is combined with acetic anhydride (1 part by volume) and left at room temperature for about 0.5 hour. (Z)-α-2,5-dimethyl-3-furylethylidene-(E)-piperonylidene succinic anhydride is obtained as orange-yellow crystals. Melting point: 134-135 degrees C (from chloroform/petroleum ether). It becomes red when irradiated with 366 nm.

White light returns the color to its original state. Example 5 3-acetyl instead of 2,5-dimethylfuran
Example 4 is repeated using acetyl-2,5-dimethylthiophene as the reactant.

A colorless product of (Z)-α-2,5-dimethyl-3-thienylethylidene-(E)-piperonylidene succinic acid is obtained. Pale yellow crystals. Melting point 149-150 degrees C (from chloroform/petroleum ether). When irradiated with 366 nm, the color becomes red.

The color returns with white light. Example 6 Example 1 is repeated using 3-acetyl-2-methylfuran instead of 3-acetyl-2,5-dimethylfuran.

(E)-α-2-methyl-3-furylethylidene-(isopropylidene) succinic anhydride is obtained. Pale yellow needle crystals, melting point 102-103°C (from petroleum ether).
When irradiated at 366r1m, the color becomes red.

White light returns the color to its original state. Example 7 (Z)-α-2,5-diphenyl-3-furylethylidene (isopropylidene)-succinic anhydride 3-acetyl-2,5-diphenylfuran (1 part) and diethylisopropylidene-succinate (1 part) ), potassium 3
Add monobutoxide (1 part) to a solution containing tertiary butanol (2 parts by weight).

Once the reaction is complete, the procedure described in Example 1 is repeated. Obtain (Z) monoanhydride as pale yellow crystals. It is reconsolidated from ethanol and irradiated with a melting point of 150 degrees CO366 rlm to turn reddish blue. White light returns the color to its original state. Example 8 Example 1 is repeated using diethyldiphenylmethylene succinate instead of diethylisopropylidene succinate.

(Z)-α-2,5-dimethyl-3-furylethylidene (diphenylmethylene)-succinic anhydride is obtained. Bright red acicular shape, re-solidified from ethanol, melting point 188-190 degrees, becomes deep red when irradiated with CO366 nm. The color returns with white light. Example 9 Using diethyl 2-butenylidene succinate in place of diethyl isopropylidene succinate Example 1
Repeat.

Recrystallized from petroleum ether as colorless cubic crystals (E)-α-
2,5-dimethyl-3-furylethylidene (Z)-2-
Obtain butenyldensuccinic anhydride. It becomes red when irradiated with 366 nm.

White light and color returns. Example 10 (E,E)-benzylidene-3-thienylidene succinic acid Preparation of colorless thiophene-3
-aldehyde (5 parts) and diethyl (E)-benzylidene succinate (2 parts) are added to a solution containing potassium (2 parts) in tertiary monobutanol (7 parts by volume) and 0.
Heat to 80 degrees C for 5A.

A half ester (6 parts) is obtained by working up in a conventional manner, which is hydrolyzed with 10% ethanolic potassium hydroxide and hydrochloric acid is added to precipitate the diacid. Dry diacid (1 part) is boiled with acetyl chloride (20 parts by volume) for 0.5 hour. Distill the solvent (
E, E) The monoisomer is crystallized from ethanol to obtain yellow prism crystals. Melting point 181 to 182 degrees CO366nm
When exposed to light, it turns bright red. The color returns when exposed to white light. Example 11 (Z)-α-2,5 described in Example 1 in toluene (3 parts by weight)
-dimethyl-3-furyl ethylidene (isopropylidene). Citric acid anhydride and p-anisidine (1 part) in 11
Heat to 0 degrees C'8 north.

The solvent was distilled off, and the remaining succinamic acid was dissolved in acetyl chloride (1 part) and left at room temperature for 1 hour. The solvent was distilled off, and (E)-α-2,5-dimethyl-3-furylethylidene (isopropylidene)-N-p-methoxyphenylsuccinimide was crystallized from ethanol. Pale yellow prism. Melting point 175-176 degrees CO sunlight or 3
When irradiated with light at 6611 m, it turns red. Return to normal with white light. Example 12 (Z)-α-2,5- described in Example 3 in toluene (marked 1)
Dimethyl-3-thienylethyldene (isopropylidene succinic anhydride (5 parts) and aniline (2 parts) at 110%
Heat for 2 hours at ℃.

Petroleum ether is added to separate the precipitated succinic acid. dry acid (
1 part) in a 1:1 mixture of acetyl chloride and ether (10 parts by weight) and left at room temperature for 1 hour. The solvent was distilled off and the residue was crystallized from ether-petroleum ether to obtain (Z)-α-2,5-dimethyl-3-thienylethylidene (isopropylidene)-N-phenylsuccinimide. Almost colorless needle crystals. Melting point 131-133
It turns purple when irradiated with a wavelength of 366 rlm of CO. Return to normal with white light. Of course, the above description is merely illustrative and does not limit the scope of the invention.

Next, aspects of the present invention and related matters will be listed. (1)3
5. The method of claim 1, wherein the StObbe condensation is carried out by refluxing the reactants in tertiary butal containing tertiary butoxide. (2) A patent claim in which equimolar amounts of the produced anhydride and a primary amine of the formula R4NH2 are heated to form the corresponding half-amide, and this is heated with an acid chloride or an acid anhydride, and A is NR4. The method according to the claims or item (1) above, which includes producing a product according to the scope of the claims.

(3) Half-ester product of StObbe condensation and formula R4N
A patent comprising reacting a compound with HMgBr to the corresponding succinamine acid and reacting this with an acid chloride to the claimed product in which A is NR4. The method described in the claims or item (1) above.

(4) A method for producing a compound according to the claims that substantially corresponds to any of those described in the specification.

(5) A device containing a photochrome compound produced by the method described in any of the above items. (6) Information storage;
The device according to item (6) above, which is suitable for holographic recording, telecopying or displaying information.

Claims (1)

[Claims] 1 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents hydrogen, an alkyl group, or an aryl group,
B represents oxygen or sulfur, X represents hydrogen or an alkyl, aryl or aralkyl group, Y are the same or different,
hydrogen, halogen, alkyl, aryl, alkoxy and aryloxy groups) and the formula ▲ has a mathematical formula, chemical formula, table, etc. ▼ (where R^1 is an alcohol residue, R^2 and R^3 are the same or different and represent an alkyl, aryl or aralkyl group, or one of R^2 and R^3 represents hydrogen and the other represents an alkyl, aryl or aralkyl group ) with an ester of a succinic acid derivative having the following properties by stop condensation, hydrolyzing the resulting half ester to form a di-acid, and then heating the resulting di-acid and an acid chloride. , General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R,
R^2, R^3, B, X and Y are as defined above). 2 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents hydrogen or an alkyl or aryl group,
B represents oxygen or sulfur, X represents hydrogen or an alkyl, aryl or aralkyl group, Y are the same or different,
hydrogen, halogen, alkyl, aryl, alkoxy and aryloxy groups) and the formula ▲ has a mathematical formula, chemical formula, table, etc. ▼ (where R^1 is an alcohol residue, R^2 and R^3 are the same or different and represent an alkyl, aryl or aralkyl group, or one of R^2 and R^3 represents hydrogen and the other represents an alkyl, aryl or aralkyl group ) is condensed with an ester of a succinic acid derivative having a succinic acid derivative by stop condensation, the resulting half ester is hydrolyzed to form a di-acid, and the resulting di-acid and an acid chloride are then heated to form a General formula: ▲Mathematical formula, chemical formula,
There are tables, etc. ▼ (I) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R,
R^2, R^3, B, X and Y are as defined above) in equimolar proportions of the formula R^4NH_2
(wherein R^4 represents a hydrogen, alkyl, aryl or aralkyl group) with a primary amine to form the corresponding half-amide, and heating this half-acid with an acid chloride or an acid anhydride. General formula consisting of: ▲Mathematical formula, chemical formula,
There are tables, etc. ▼ (III) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) (In the formula, R,
R^2, R^3, B, X, Y and R^4 are as defined above). 3 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents hydrogen or an alkyl or aryl group,
B represents oxygen or sulfur, X represents hydrogen or an alkyl, aryl or aralkyl group, Y is the same or different,
hydrogen, halogen, alkyl, aryl, alkoxy and aryloxy groups) with the formula ▲ mathematical formula, chemical formula, table, etc. ▼ (wherein R^1 is an alcohol residue, R^2 and R^3 are the same or different and represent an alkyl, aryl or aralkyl group, or one of R^2 and R^3 represents hydrogen and the other represents an alkyl, aryl or aralkyl group ) is condensed with an ester of a succinic acid derivative having the formula R^4 by Stobb condensation.
The general formula consists of reacting a compound of NHMgBr (wherein R^4 represents hydrogen, alkyl, aryl or aralkyl) to form the corresponding succinamic acid, which is then reacted with an acid chloride: ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼ (III) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) (In the formula, R,
R^2, R^3R^4, B, X and Y are as defined above).