JPH0250102B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a diacetylene compound having solid phase polymerizability. Specifically, the present invention relates to a diacetylene compound having solid phase polymerizability. This invention relates to a diacetylene compound having phase polymerizability. Since the diacetylene compound according to the present invention has solid phase polymerizability, it can be used as a functional material for nonlinear optical materials, photosensitive materials, polymer semiconductor crystals, and the like. [Prior Art] In recent years, diacetylene compounds have been actively researched as monomers for forming nonlinear optical materials, photosensitive materials, polymer semiconductor crystals, and the like. In order to form nonlinear optical materials, photosensitive materials, polymer semiconductor crystals, etc., it is necessary that the monomer of the diacetylene compound has solid phase polymerizability. In addition, in order to obtain high-performance nonlinear optical materials and polymer semiconductor crystals, it is necessary that main chain-side chain conjugation provides a large electronic effect. It has been known that some diacetylene compounds represented by the general formula Ra-C≡C-C≡C-Rb (1) have solid phase polymerizability. [Problems to be Solved by the Invention] Diacetylene compounds that have solid phase polymerizability and can be conjugated between the main chain and the side chain are currently in high demand. Most of the diacetylene compounds have a structure in which the conjugation between the polydiacetylene main chain and the side chain substituent is broken. In a polymer in which the main chain-side chain conjugation is broken in this way, the electronic effect of the substituents is almost eliminated, and any substituents tend to exhibit similar properties. On the other hand, when the diacetylene moiety is directly substituted with an aromatic ring, the resulting crystalline polymer is expected to have excellent electrical properties due to the expansion of conjugation. Most acetylene compounds do not exhibit solid phase polymerizability. As mentioned above, diacetylene compounds which have solid phase polymerizability and have a large electronic effect due to the substituent being capable of conjugating with a diacetylene triple bond are currently in greatest demand. [Means for Solving the Problem] The present inventor obtains a diacetylene compound that has solid phase polymerizability and has a large electronic effect by having a substituent that can be conjugated with a diacetylene triple bond. As a result of various studies, we have arrived at the present invention. That is, the present invention has the following general formula: , where n is an integer from 0 to 20, and R is
One or two selected from an unsubstituted alkyl group having 4 to 10 carbon atoms, an unsubstituted phenyl group, and a phenyl group substituted with a nitro group, an amide group, or a substituent containing a nitro group and an amide group. It is a diacetylene compound having solid phase polymerizability, which is any substituent containing at least one type of group. [Function] First, the most important point in the present invention is that the diacetylene compound according to the present invention has solid phase polymerizability, so that it is difficult to form nonlinear optical materials, photosensitive materials, and polymer semiconductor crystals. I can do it, and also.
The substituent can be conjugated with a diacetylene triple bond, resulting in a large electronic effect and a large nonlinear optical effect. In the present invention, when the substituent R is a group having an aromatic group or a group containing a nitro group, an amide group, etc., the main chain-side chain conjugation extends to both sides with the main chain in between. Since a diacetylene compound can be obtained, even greater electrical effects can be obtained. The polymer crystal obtained by solid-phase polymerization of the diacetylene compound according to the present invention is soluble in polar solvents such as dimethylformamide and dimethylacetamide, so it can be used as a cast film when producing functional materials. can also be used. Next, a method for synthesizing a diacetylene compound according to the present invention will be described. The diacetylene compounds of the present invention are all new compounds that have not been published in any literature, and are bromoethynyl derivatives represented by the formula R-C≡C-Br (2) (wherein R has 4 to 10 carbon atoms). Substitution containing one or more groups selected from an unsubstituted alkyl group, an unsubstituted phenyl group, and a phenyl group substituted with a nitro group, an amide group, or a substituent containing a nitro group and an amide group. ) and 3-ethynylaniline are asymmetrically coupled. formula (However, R can be any of an unsubstituted alkyl group having 4 to 10 carbon atoms, an unsubstituted phenyl group, a nitro group, an amide group, or a phenyl group substituted with a substituent containing a nitro group and an amide group. ) The diphenyl diacetylene derivative represented by the formula (However, n is an integer of 0 to 20.) It can be produced by reacting dicaronic acid dichloride represented by the following in the presence of an amine. The above asymmetric coupling reaction can be carried out under various reaction conditions, but in all cases requires the catalytic action of a copper salt. Specifically, after adding an amine aqueous solution and copper chloride () to a solution of 3-ethynylaniline, a bromoethynyl derivative represented by formula (2) is slowly added while stirring to initiate an asymmetric coupling reaction. progresses. As the solvent, polar solvents such as methanol, ethanol, tetrahydrofuran, dimethylformamide, and dimethylacetamide are preferred. Ethylamine aqueous solution is generally used as the amine aqueous solution, but other amine aqueous solutions can also be used. Copper chloride () is used in an amount of 1 to 50 mol% based on ethynylaniline. This reaction is carried out under an inert gas atmosphere such as argon or nitrogen at a temperature of 0 to 50°C. This is done by continuing stirring for an hour to 12 days. After the reaction is completed, the solvent is distilled off from the reaction mixture, the mixture is neutralized and diluted with a dilute aqueous hydrochloric acid solution, and extracted with a solvent such as ether or benzene. This solution is dehydrated by adding a desiccant such as sodium sulfate or magnesium sulfate, the desiccant and solvent are removed, and the diacetylene compound represented by formula (3) is purified by silica gel column chromatography. is obtained as white to yellow crystals. The formula obtained next
Dissolve the diphenyl diacetylene derivative represented by (4) in a solvent such as dimethylformamide or dimethylacetamide, add dicarboxylic acid chloride represented by formula (4) in the presence of an amine, and stir at room temperature for 3 to 15 hours. . After distilling off the solvent from the reaction mixture, the diacetylene compound according to the present invention is obtained as white to yellow crystals by purification by silica gel column chromatography or recrystallization. [Example] Next, the present invention will be explained in detail with reference to Examples and Reference Examples. Example 1 Under an argon atmosphere, 50 mg of copper chloride () was dissolved in 10 ml of 70% ethylamine aqueous solution, and 930 mg of 3-ethynylaniline was dissolved in 5 ml of dimethylacetamide.
Add the solution dissolved in and stir at room temperature for 30 minutes. A solution of 1800 mg of 3-(1-bromoethynyl)nitrobenzene dissolved in 5 ml of dimethylacetamide was added dropwise over about 6 hours, followed by stirring at room temperature for 12 hours. (If the solution turns green due to the formation of copper chloride () during the process, add an appropriate amount of hydroxylamine hydrochloride to reduce it.) The solvent is distilled off from the reaction mixture, neutralized with 200 ml of 1N aqueous hydrochloric acid solution, and diluted. and extracted three times with 150 ml of ether.
After drying the organic layer with sodium sulfate, the solvent was distilled off, and 950 mg of 1-(3-nitrophenyl)-4-(3-aminophenyl)-butadiin was obtained by separating and purifying it by silica gel column chromatography using benzene as a developing solvent. I got it. This substance was yellow crystal. Next, 500 mg of the obtained diacetylene compound was dissolved in 60 ml of pyridine, and 450 mg of eicosanedioic acid dichloride was added thereto.
Stir for an hour and dilute with 200ml of methanol.
The precipitated solid was filtered and recrystallized with a mixed solvent of chloroform-tetrahydrofuran (1:1) to obtain 520 mg of eicosandi(3-(4-(3-nitrophenyl)butadiynyl)anilide).
I got it. This substance was pale yellowish white crystals. As elemental analysis value (C ₅₂ H ₅₄ N ₄ O ₆ ) Calculated value (%); C75.16 H6.55 N6.74 Actual value (%); C75.40 H6.83 N6.59 Example 2 Example 1 1-(3-nitrophenyl)-4 obtained in
-(3-aminophenyl)-1,3-butadiyne
500 mg was dissolved in 50 ml of pyridine, 260 mg of decanedioic acid dichloride was added thereto, and the mixture was stirred at room temperature for 5 hours.
This was poured into 200 ml of water, extracted 3 times with 100 ml of ethyl acetate, the organic layer was dried over magnesium sulfate and concentrated, and the precipitated solid was recrystallized from ethyl acetate. ) butadiinyl) anilide) 380 mg was obtained. This substance was pale yellow crystals. As elemental analysis value (C ₄₂ H ₃₄ N ₄ O ₆ ) Calculated value (%); C73.03 H4.96 N8.11 Actual value (%); C73.21 H5.15 N8.03 Example 3 Example 1 1-(3-nitrophenyl)-4 obtained in
-(3-aminophenyl)-1,3-butadiyne
Dissolve 500 mg in 50 ml of pyridine, add 190 mg of hexanedioic acid dichloride, stir at room temperature for 4 hours, pour this into 200 ml of water, and dissolve with 100 ml of ethyl acetate.
After extraction, the organic layer was dried over magnesium sulfate, concentrated, and the precipitated solid was recrystallized from chloroform to yield 330 mg of hexanedi(3-(4-(3-nitrophenyl)butadiynyl)anilide).
I got it. This substance was pale yellowish white crystals. As elemental analysis value (C ₃₈ H ₂₆ N ₄ O ₆ ) Calculated value (%); C71.93 H4.11 N8.83 Actual value (%); C71.75 H4.32 N8.88 Example 4 Under argon atmosphere , 50 mg of copper chloride () was dissolved in 10 ml of 70% ethylamine aqueous solution, and 600 mg of 3-ethynylaniline was dissolved in 5 ml of dimethylacetamide.
Add the solution dissolved in and stir at room temperature for 10 minutes. 1100 mg of β-bromoethynylbenzene was added dropwise thereto over about 3 hours, followed by stirring at room temperature for 8 hours. Thereafter, by the same operation as in Example 1, 1-phenyl-4
580 mg of -(3-aminophenyl)butadiine was obtained. This substance was a white crystal. Next, 300 mg of the obtained diacetylene compound was dissolved in 30 ml of pyridine, 270 mg of eicosanedioic acid diclide was added thereto, stirred at room temperature for 4 hours, and poured into 200 ml of water.
Extracted twice with 100 ml of ethyl acetate, dried the organic layer over magnesium sulfate, concentrated, and recrystallized with chloroform to obtain eicosandi (3-(4)
-phenyl)butadiynylanilide) was obtained. This substance was a white crystal. As elemental analysis value (C ₅₂ H ₅₆ N ₂ O ₂ ) Calculated value (%); C84.28 H7.62 N3.78 Actual value (%); C84.44 H7.81 N3.65 Example 5 Under argon atmosphere , 50 mg of copper chloride () was dissolved in 10 ml of 70% ethylamine aqueous solution, and 600 mg of 3-ethynylaniline was dissolved in 5 ml of dimethylacetamide.
Add the solution dissolved in and stir at room temperature for 20 minutes. Here 3-(bromoethynyl)acetanilide 1480
mg was added dropwise over about 5 hours, and then stirred at room temperature for 8 hours. Thereafter, by the same operation as in Example 1, 1-(3
860 mg of -acetylaminophenyl)-4-(3-aminophenyl)butadiine was obtained. This substance was a white crystal. Next, 400 mg of the obtained diacetylene compound was dissolved in 50 ml of pyridine, 380 mg of eicosanedioic acid dichloride was added thereto, and the mixture was stirred at room temperature for 6 hours, poured into 300 ml of water, and 150 ml of ethyl acetate was added.
The organic layer was extracted three times with
450 mg of (4-(3-acetylaminophenyl)butadiynyl)anilide was obtained. This substance was a white crystal. As elemental analysis value (C ₅₆ H ₆₂ N ₄ O ₄ ) Calculated value (%); C78.66 H7.31 N6.55 Actual value (%); C78.40 H7.21 N6.43 Example 6 Under argon atmosphere , 50 mg of copper chloride () was dissolved in 10 ml of 70% ethylamine aqueous solution, and 600 mg of 3-ethynylaniline was dissolved in 5 ml of dimethylacetamide.
Add the solution dissolved in and stir at room temperature for 20 minutes. 1,100 mg of 1-bromo-1-octyne was added dropwise over about 6 hours, followed by stirring at room temperature for 12 hours. Thereafter, by the same operation as in Example 1, 1-hexyl-4-
500 mg of (3-aminophenyl)butadiine was obtained.
This substance was a white crystal. Next, 300 mg of the obtained diacetylene compound was dissolved in 30 ml of pyridine,
250 mg of hexadecanedioic acid dichloride was added thereto, stirred at room temperature for 5 hours, and then the same procedure as in Example 3 was performed to prepare hexadecanedi(3-(undec-1, 3
-diynyl)anilide) 370 mg was obtained. This substance was a white crystal. As elemental analysis value (C ₃₈ H ₄₇ N ₂ O ₂ ) Calculated value (%); C80.95 H8.40 N4.97 Actual value (%); C80.72 H8.69 N5.03 [Reference example] Powder Each sample of the compound of the present invention was vacuum-sealed in a glass tube and exposed to cobalt-60 gamma rays.
Solid state polymerization was carried out by irradiating with a dose of 300 MRad. After opening, the polymerization yield was determined from the weight of the tetrahydrofuran-insoluble polymer. The following table shows the polymerization yields of the diacetylene compounds obtained in Examples 1 to 6.

【table】

〔Effect of the invention〕

The diacetylene compound according to the present invention has a large nonlinear optical effect because the substituent can be conjugated with a diacetylene triple bond, as shown in the above-mentioned Example, and as shown in the above-mentioned Reference Example, the diacetylene compound has a strong nonlinear optical effect. Due to its phase polymerizability, it is suitable as a polydiacetylene monomer for forming nonlinear optical materials, photosensitive materials, and polymeric semiconductor materials.

Claims (1)

[Claims] 1. General formula , where n is an integer of 0 to 20, and R is an unsubstituted alkyl group having 4 to 10 carbon atoms, an unsubstituted phenyl group, a nitro group or an amide group, or a nitro group and an amide group. A diacetylene compound having solid phase polymerizability, which is any phenyl group substituted with a substituent containing.