JPH06751B2 - Asymmetric diorefin compound - Google Patents

Description

The present invention relates to a group of novel asymmetric diolefin compounds having a heteroaromatic ring.

The substance of the present invention is useful as a fluorescent substance having a hydrophobic group and a hydrophilic group or as an asymmetric and rigid photoreactive agent.

[Conventional technology]

Heretofore, various substances having photoreactivity have been known, but an asymmetric and rigid substance having a hydrophobic group and a hydrophilic group in the molecule like the substance of the present invention has not been known.

[Means for solving problems]

The present inventors have earnestly studied the photoreactivity of various substances, and found out that a group of asymmetric compounds of the present invention have photoreactivity in a crystalline state and in a solution, and arrived at the present invention.

The novel substance of the present invention is an asymmetric diolefin compound represented by the following general formula.

[X and Y represent the following pairs.

(-CN, -COOR), (-CN, -CN), (-CN, ), (H, However, R: H or an alkyl group is shown. ] These substances are synthesized by the synthetic route shown below.

[However, X and Y are the same as above.

A represents a condensing agent such as acetic acid-acetic anhydride, benzoic anhydride or ZnCl ₂ .

B represents a base such as pyridine, piperidine and KOH. ] 4- [2- (4-formylphenyl) ethenyl] pyridine obtained in the reaction 1) The novel substance of the present invention can be easily obtained by reacting the substance represented by The reaction is carried out in a solvent such as methanol, ethanol or n-butyl alcohol at room temperature for 6 to 24 hours.
Just go on time. This reaction involves pyridine, piperidine, KO
It is promoted by the coexistence of a base such as H.

〔The invention's effect〕

The substance of the present invention reacts with light to form a cyclobutane ring, and has a reversible reactivity that is cleaved by light of another wavelength to return to the original state. Utilizing this property, it is useful as a reversible photoreactive agent and photocrosslinking agent. Particularly useful for Langmuir-Brodgett film utilizing the photoreactivity of the cumulative film by utilizing the property of the substance of the present invention that is asymmetric, rigid, and has a hydrophilic group and a hydrophobic group. Is. In addition, the compound of the present invention having —COOR can be introduced into the polymer side chain as a photosensitive unit.

Further, since it is a fluorescent substance itself, it is also useful as a photoreactive and rigid fluorescent substance for analysis, measurement and reagent.

〔Example〕

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example-1 Synthesis of 4- [2- (4-formylphenyl) ethenyl] pyridine 1.00 g (4.78 mmol) {synthesized according to the method of Ichimura et al., K. Ich
imura and S. Watanabe, J.Polym.Sci.Polym.Chem.Ed. 20 ,
1420 (1982)} in 50 ml of methanol, and then 35 ml of 0.710 g (7.17 mmol) of methyl α-cyanoacetate in this solution.
The solution diluted with methanol of was added and stirred at room temperature for 6 hours. After the reaction, the precipitated crystals were separated by filtration and vacuum dried.
Further, this crystal was recrystallized from methanol to obtain a pale yellow needle crystal.

Table 1 shows the yield and properties.

Example-2 Synthesis of 4- [2- (4-formylphenyl) ethenyl] pyridine 1.00 g (4.78 mmol) and malononitrile 0.470 g (7.11 mmol)
Was dissolved in 80 ml of ethanol and stirred at room temperature for 6 hours.
After the reaction, the precipitated crystals were separated by filtration, washed with a small amount of cold ethanol, and dried under vacuum. Further, this crystal was recrystallized from ethanol to obtain a yellow-green needle crystal.

Table 1 shows the yield and properties.

Example-3 Synthesis of 4- [2- (4-formylphenyl) ethenyl] pyridine (1.00 g, 4.78 mmol) was dissolved in 40 ml of ethanol, and 0.839 g (7.17 mmol) of benzyl cyanide was diluted with 20 ml of ethanol. The solution was added. Then 5 as catalyst
A drop of 35% aqueous potassium hydroxide solution was added, and the mixture was stirred at room temperature for 8 hours. After the reaction, the precipitated crystals were separated by filtration, washed with water and cold ethanol, and vacuum dried. Further, the crude crystals were recrystallized from ethanol to obtain yellowish green scale-like crystals.

Table 1 shows the yield and properties.

Example-4 Synthesis of 4- [2- (4-formylphenyl) ethenyl] pyridine (1.00 g, 4.78 mmol) was dissolved in 60 ml of ethanol, and 0.861 g (7.17 mmol) of acetophenone was diluted with 40 ml of ethanol. added. Then 10 as catalyst
A drop of 35% aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 8 hours. After the reaction, the precipitated crystals were separated by filtration, washed with water and cold ethanol, and vacuum dried. Further, the crude crystals were recrystallized from ethanol to obtain pale yellow crystals.

Table 1 shows the yield and properties.

Example-5 Synthesis of 4- [2- (4-formylphenyl) ethenyl] pyridine 1.00 g (4.78 mmol) was dissolved in 50 ml of n-butyl alcohol, then 1.06 g (7.17 mmol) of α-cyanoacetic acid n was added to this solution. A solution obtained by diluting -butyl with 30 ml of n-butyl alcohol was added, and the mixture was stirred at room temperature for 24 hours. After the reaction, the precipitated crystals were separated by filtration and vacuum dried. Furthermore, this crystal is n
Recrystallization from butyl alcohol gave yellowish green plate crystals.

Table 1 shows the yield and properties.

Photoreactivity in crystalline state The photoreactivity in the crystalline state was investigated for the substances synthesized as described above. The photoreactivity was determined by a change in IR spectrum when irradiated with a 100V high-pressure mercury lamp through a Pyrex filter at room temperature.

++: Very high reactivity +: High reactivity Δ: Low reactivity −: Stable to light The results are shown in Table 2.

The substances of Examples 1 to 5 emitted fluorescent light when irradiated with ultraviolet rays and reacted with the irradiation of a high pressure mercury lamp.

Further, all the substances of Examples 1 to 5 exhibited photoreactivity in solution.

Claims (1)

[Claims] 1. An asymmetric diolefin compound represented by the following general formula. [X and Y represent the following pairs. (-CN, -COOR), (-CN, -CN), (-CN, ), (H, However, R shows H or an alkyl group. ]