JPH0460099B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel cyclobutane derivative useful for image forming materials etc. by light irradiation. More specifically, the present invention relates to a novel cyclobutane derivative obtained by dimerizing 4-(3-oxo-3-phenyl-1-propenyl)benzoic acid (hereinafter abbreviated as OPPB) or its ethyl ester through a phototobochemical process. [Prior Art and Problems] The present inventors have discovered that OPPB derivatives can be dimerized in high yield by photoreaction in a crystalline state. At this time, two types of structures represented by () and ()' below, which have different symmetries, can be taken. (However, _R1 :

[Formula] R ₂ :

[Means for solving problems]

As a result of intensive studies on the method for producing the ( ) type compound, the present inventors discovered that the ( ) type compound can be obtained in high yield by photodimerization of OPPB or its ethyl ester, leading to the present invention. (Interestingly, methyl, propyl, butyl, etc. esters of OPPB give the ()′ form). That is, the present invention provides a bifunctional cyclobutane derivative represented by the above formula (). [Function] The compound represented by the above formula () of the present invention is
It can be obtained by irradiating OPPB or its ethyl ester in a crystalline state with light. Irradiation is usually carried out by dispersing raw material crystal powder in water or water containing a surfactant and irradiating it with light from a high-pressure mercury lamp, but is not limited to this method. It may be irradiated with
Furthermore, the light source is not limited to a high-pressure mercury lamp. A polyamide compound having the following structure () or () can be obtained by polycondensing the compound () or ()' of the present invention with a diamine. (However, R ₁ is

[Formula], A is a residue obtained by removing one active hydrogen from two amino groups of a primary or secondary diamine) The diamine residue according to the present invention may be saturated or unsaturated. It's okay to be saturated. Alternatively, it may be a mixture of two or more types of diamine residues. An example is shown below. −HN(CH ₂ ) ₂ −NH−, −HN−(CH ₂ ) ₆ −NH−,

【formula】

Films obtained from these polyamides have a photocleavable cyclobutane ring and a benzoyl group, which is a sensitizing group, and therefore have high photosensitivity. That is, it can be used as a photosensitive film by utilizing the molecular weight reduction and generation of colored substances due to light irradiation. The polyamide of the present invention can be obtained by a conventional method for obtaining polyamide from dicarboxylic acid or its ester and diamine. For example, the reaction of a dithiol ester obtained by reaction with 2-mercaptobenzothiazole with a diamine is a preferred method because the reaction proceeds under mild conditions. [Examples and Effects] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. Example 1 (Synthesis of OPPB) Caustic soda aqueous solution (12.8gNaOH/ _112mlH2O )
19.2 g of acetophenone and 16 ml of ethanol were added to the solution, and a solution of 25 g of terephthalaldehydic acid dissolved in 80 ml of DMF was added to the same solution while maintaining the temperature at 20 to 30°C, and the mixture was kept at the same temperature for an additional 3 hours. After the reaction is complete, add hydrochloric acid to the reaction solution to make OPPB.
(crude yield 94.9%). Example 2 (Synthesis of OPPB ethyl ester) 23 g of OPPB was dissolved in 700 ml of ethanol and refluxed for 3 to 4 hours while passing hydrogen chloride gas. The reaction solution was concentrated to obtain yellow crystals of OPPB ethyl ester with a yield of 84.5%. Recrystallization from n-hexane gave purified crystals. Example 3 (Synthesis of ()-type OPPB dimer) 5.0 g of OPPB, which was pulverized in an agate pot, was dispersed in 400 ml of water to which 1 drop of surfactant NIKKOL-10FF was added, and nitrogen was added while thoroughly stirring with a stirrer. Internal irradiation was performed using a 100W high-pressure mercury lamp equipped with a Pyrex filter for 50 hours at room temperature under a gas stream. After the reaction, the solid was filtered out, washed with glacial acetic acid and water in that order, and recrystallized from acetonitrile to give 2.8g.
Needle-shaped crystals were obtained. mp250−253.5℃, yield
It was 56%. Example 4 (Synthesis of () type OPPB ethyl ester dimer) OPPB ethyl ester was irradiated with light in the same manner as in Example 3. After 2.5 hours of irradiation, separate the solids and
After washing with ether, it was recrystallized from ethanol. 94
The dimer was obtained with a yield of %. Reference example 1 (Synthesis of ( ) type polyamide) Add 50 ml of thionyl chloride and 1 drop of pyridine as a catalyst to 5.20 g (10.3 mmole) of OPPB dimer,
Refluxed for an hour. Then, after removing excess thionyl chloride, it was dissolved in 80 ml of tetrahydrofuran (THF), and further 2.26 g of triethylamine was added.
(22.4 mmole) was added. 3.45 g (20.6 mmole) of 2-mercaptobenzothiazole was dissolved in 80 ml of THF, and while stirring at room temperature, the previously prepared TEF solution of acid chloride was added dropwise, and the mixture was reacted for 2.0 hours.
After the reaction, it was poured into 300ml of water. The product was then separated and thoroughly washed with acetone to obtain 6.06 g (7.55 mmole) of pearlescent powder. Yield 73%.
This crude product was recrystallized from methylene chloride to obtain pearl-colored fine needle-shaped crystals. 120.3 mg (1.035 mmole) of hexamethylene diamine (HMDA) was dissolved in 2.0 ml of N-methylpyrrolidone (NMP), then 831.3 mg
(1.035 mmole) of dithiol ester was added and stirred at room temperature. The monomer gradually dissolved with exotherm, and the solution became viscous. 125ml after 25 hours
The precipitated polymer was poured into a 1% aqueous solution of sodium carbonate, and the precipitated polymer was filtered out, washed with water, hot water, and methanol in this order, and dried under vacuum. Yield 0.60g (99%),
ηinh was 0.27. This polyamide is insoluble in methanol and acetone, and sparingly soluble in chloroform.
Soluble in aprotic polar solvents such as NMP, DMF, and HMPA. Also, NMP or 1,1,
Films can be cast from 1,3,3,3-hexafluoro-2-propanol. Reference Example 2 (Synthesis of ( ) type polyamide) A dimer (3.00 g) obtained by irradiating light from OPPB methyl ester and recrystallizing it from methanol in the same manner as in Example 4 was mixed with formic acid (146 g) and concentrated sulfuric acid (3.12 g). )During,
110-120℃ for 3 hours at 90-100℃ under nitrogen flow
The mixture was heated and stirred for 7 hours. After the reaction, formic acid insoluble matter was filtered off, washed with water, and dried under vacuum to obtain a hydrolyzed dimer.
Yield 94%. Then, polycondensation was performed with hexamethylene diamine in the same manner as in Reference Example 1 to obtain a polyamide (yield: 96
%). This polymer was dissolved in N-methyl-2-pyrrolidone or 1,1,1,3,3,3-hexafluoro-2-propanol, deposited on a glass plate, and dried to obtain a film. This was irradiated with light from a 100W high-pressure mercury lamp for 4 hours to obtain a colored image.

Claims (1)

[Claims] 1. A bifunctional cyclobutane derivative represented by the following formula (). [However; R ₁ is [Formula] R ₂ is [Formula] R ₃ is -COOH or its ester] 2 Photodimerizing 4-(3-oxo-3-phenyl-1-propenyl)benzoic acid or its ethyl ester A method for producing a cyclobutane derivative represented by the following formula (), characterized by: [However; R ₁ is [Formula] R ₂ is [Formula] R ₃ is -COOH or its ester]