JPS62255460A - Diphenyldiacetylene derivative - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [one of R1 and R2 is nitro and the other is H; either one of R1'-R3' is -NHCO-(CH2)n-CO2H (n is 6-18) and the others are H]. EXAMPLE:2-(4-(3-Nitrophenyl)-1,3-butadiynyl)phenylcarbamoylnonadecanoic acid. USE:Useful as a monomer of diacetylene compound for forming a nonlinear optical material, a photo-sensitive material or a polymeric semiconductor material. It is polymerizable in solid phase and can form a built-up film. It has an asymmetric structure and high electronic effect. PREPARATION:The compound of formula I can be produced by carrying out asymmetric coupling of bromoethynylnitrobenzene of formula II with an ethynylaniline of formula III and reacting the resultant compound of formula I (one of R1'-R3' is amino and the others are H) with an alkyldicarboxylic acid monochloride of formula IV in the presence of an amine.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to diphenyl diacetylene derivatives, specifically,
The present invention relates to a diphenyl diacetylene derivative that has solid polymerizability, can be formed into a cumulative film, is structurally asymmetric, and has a substituent conjugated with ancenalene tripolymerization.

The diphenyl diacetylene derivative according to the present invention has solid phase polymerizability and can be used as a nonlinear optical material, a four-optical material, and a molecular semiconductor crystal.

[Conventional technology]

In recent years, research has been actively conducted on diacetylenes, which are monomers for forming nonlinear optical materials, photosensitive materials, semi-tetratram crystals, and the like.

In order to form nonlinear optical materials, photosensitive materials, commercial molecular semi-animal crystals, etc., it is necessary that the diacetylene compound has solid phase polymerizability, and it is necessary to obtain commercial performance devices with oriented molecules. Therefore, it is important to be able to form a cumulative film. In addition, in order to improve the nonlinear optical effect as a nonlinear optical material, as is well known, the monomer is structurally asymmetric, and the ball chain and side chain are conjugated, so that the electronic effect can be improved. It needs to be big.

It has been known that some compounds among diacetylenes represented by the general formula % have homopolymerizability.

[Problem that the invention seeks to solve]

There is currently a demand for diacetylenes that have solid phase polymerizability, can be formed into cumulative films, are structurally asymmetric, and have substituents conjugated with diacetylene triple bonds. , friI The diphenyl diacetylenes having known solid phase polymerizability described above have the general formula fi+, R,
Since the diacetylene moiety has the same substituent at both ends like =Rb, forming a symmetrical molecule, an even-order nonlinear optical effect occurs (unexpected).

Moreover, most of them have a structure in which the conjugation between a and M and the diacetylene moiety is broken. In a polymer in which the chain-side chain conjugation is broken in this manner, the electronic effects of the substituents R1 and R2 are almost eliminated, and any substituents tend to exhibit similar properties.

On the other hand, in the diacetylene compound represented by the general formula (1) in which the substituted 5R and Rh are aromatic, the crystalline polymer formed is conjugated with the triple bond in the formula (1). are expected to have excellent electronic properties, but most of these diacetylenes do not impair homopolymerizability.

diphenyl diacetylene with an acetylamino group at each ortho or meta position of the two phenyl groups; 4-;2. 5-;3, (There are some products that have solid phase polymerizability, such as those with a trifluoromethyl group at the j-position, but these cannot be formed into a cumulative Mi film, and each molecule is Since it has a symmetrical structure, even-order nonlinear optical effects do not occur.

As mentioned above, it has solid phase polymerizability and can be formed into a cumulative film, and is structurally asymmetric and has an aromatic substituent conjugated with a diacetylene triple bond, so it has an electronic effect. Large diacetylenic compounds are currently in greatest demand.

[Means to solve the problem]

The present inventor has discovered that it has solid phase polymerizability and can be formed into a cumulative film, and that it is structurally asymmetric and the substituent is an aromatic group conjugated with a diacetylene triple bond, thereby producing an electronic effect. The present invention was achieved as a result of various studies aimed at obtaining a tt-form of diacetylenes with a large .

That is, the present invention is represented by a general formula, in which either one of R1 and R2 is a nitro group,
The remainder is hydrogen, and any one of R: ~P- is -NHCO-4CHz)T-COtH (however, nm 6
~18) are diphenyl diacetylene derivatives in which the remainder is hydrogen.

[For production]

First, the most important point in the present invention is that the diphenyl diacetylene derivative according to the present invention has solid phase polymerizability and can be formed into a cumulative film, so that it can be used as a high-performance nonlinear optical material, a photosensitive material, and a photosensitive material. It can form polymer semiconductor crystals, and it is structurally asymmetric, and the substituent is an aromatic group that is conjugated with a diacetylene triple bond, resulting in a large electronic effect, resulting in nonlinear optical effects. This is a big point.

Further, the diphenylacetylene derivative according to the present invention has a nitro group which is an electron-withdrawing group and an electron-donating group.
The presence of the C0zll group results in large molecular polarization, and as a result, a large nonlinear optical effect can be expected, making it extremely advantageous when applied as a nonlinear optical material.

Next, a method for synthesizing diphenyl diacetylene derivative 4 according to the present invention will be described.

The diphenyl diacetylene derivatives of the present invention are all new compounds not yet described in literature, and are combined with bromoethynylnitrobenzene represented by IH (where either one of Rt and Rt is a nitro group and the remainder is hydrogen).
C1 to the diphenyl diacetylene derivative obtained by asymmetric coupling of ethynylaniline represented by Rz R+ H)l (where one of RI' to R, 1 is an amino group and the rest is hydrogen) -C→
It can be produced by reacting an alkyldicarboxylic acid monochloride represented by C1ot +r-C-0H (where n = 6 to 1B) in the presence of an amine.

The above asymmetric coupling reaction was performed under various reaction conditions.
However, in both cases the catalytic action of the copper salt is required. Specifically, after adding an amine aqueous solution and copper chloride (11) to ethynylaniline solution 78, the asymmetric coupling reaction proceeds by slowly adding bromoethynylnitrobenzene while stirring.

As the solvent, polar solvents such as methanol, ethanol, tetrahydrofuran, dimethylformamide, and dimethylacetamide are preferred. As the amine aqueous solution, an ethylamine aqueous solution is used, but other amine aqueous solutions can also be used. The wA(I) chloride is used in an amount of 1 to 50...o1% based on ethynylaniline.

This reaction is carried out under an inert gas atmosphere such as argon or nitrogen.
The temperature is 0 to 50℃, and in some cases 1i (I+
In order to prevent oxidation of ions, stirring is continued for several hours to 1 to 2 days while adding an appropriate amount of hydroxylamine hydrochloride.

After the end of the reaction, the solvent was distilled off from the reaction mixture, and diluted hydrochloric acid water was added. Neutralize and dilute with 8 liquid and extract 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 diphenyl diacetylene derivative represented by formula (5) is purified by silica gel column chromatography. The diphenyl diacetylene derivative represented by the formula (5) obtained as zero-order or red crystals is dissolved in a solvent such as dimethylformamide or dimethylacetamide, and in the presence of an amine, the diphenyl diacetylene derivative represented by the formula (4) is dissolved. Add the alkyl dicarboxylic acid monochloride and stir under pressure for 10 to 24 hours. By distilling off the solvent from the reaction mixture and purifying it by silica gel column chromatography, diphenyl diacetylene derivative 4 represented by general formula (2) is obtained as pale yellow crystals.

〔Example〕

Next, the present invention will be explained with reference to Examples, Application Examples, and Reference Examples.

Example 1 Atmosphere, copper chloride m 50+mg ethylamine 7
Dissolve in 10 ml of 0% aqueous solution, add 2-ethynylaniline 930B mixed with 5 ml of dimethylacetamide, and stir at room temperature for 30 minutes. here 3
-(1-bromoethynyl)nitrobenzene 18001I
A solution of Ig in 5 ml of dimethylacetamide was added dropwise over about 5 hours, followed by stirring at room temperature for 12 hours.

(If it turns green due to the formation of 14OO chloride,
゛ Add ethylamine hydrochloride and reduce. ) The solvent was distilled off from the reaction mixture, and 200 ml of normal aqueous hydrochloric acid solution was added.
Neutralize, dilute, and extract three times with 150 ml of ether. After drying the organic layer with sodium sulfate, the solvent was distilled off, and 1-(3-
nitrophenyl)-4=(2-aminophenyl)-1,
3-830 butadiin houses were obtained. This substance was yellow crystal. Next obtained diacetylene compound soo mg
was dissolved in 20 ml of dimethylformamide, to which were added Qml of triethylamine and 750+ mg of eicosanniic acid monochloride, and the mixture was refluxed for 12 hours. The mixture is air-cooled to room temperature, the solvent is distilled off, and the mixture is diluted with dilute hydrochloric acid until it becomes acidic.

After extracting three times with chloroform 100n+1 and drying the organic layer with sodium sulfate, the solvent was distilled off and purified by silica gel column chromatography developed with a mixed solvent of chloroform and ethyl acetate.
230n+g of 3-nitrophenyl)-1°3-butacyinyl)phenylcarbamoylnonadecane InI was obtained. This substance was a pale yellow crystal. Elemental analysis value (C,, I (,, N, 0.) Calculated value (
%) ; C73,69, H7,90, N 4.77 Actual value (%); C73,92, H7,75, N 4.
86 Example 2 Under an Ar atmosphere, 51)++ g of copper chloride was dissolved in 1 liter of a 70% aqueous solution of ethylamine, and 3-ethynylaniline 93 (lllg) was dissolved in dimethylacetamide 5*.
Add the solution dissolved in 1 and stir at room temperature for 30 minutes. Furthermore, 3-(bromoethynyl)nitrobenzene 1800
A solution of 7 mg in 5 ml of cymenal acetamide was poured over 6 hours and stirred at room temperature for 12 hours. By the same operation as in Example 1, 1230 mg of 1-(3-nitrophenyl)-4-(3-aminophenyl)-1,3-butadiyne was obtained. This substance is a yellow crystal with a melting point of 17.
The temperature was 1-172°C. Next, 500g of the obtained diacetylene compound was dissolved in 20g of dimethylacetamide, 101g of triethylamine and 750n+g of eicosanniic acid monochloride were added thereto, and
Heat and stir at ℃. Hereinafter, by the same operation as in Example 1, 3-(4-(3-nitrophenyl)-1,3-butacyinyl)phenylcarbamoylnonadecanoic acid 320+
mg was obtained.

This substance was pale yellow crystal.

Elemental analysis value (as C1hH4hNzos) Calculated value (%
); C73,69, H7,90, N 4.77 Actual value (%): C73,41, H8,10, N 5.0
1 Example 3 Under an Ar atmosphere, 50 mg of W chloride (Il) was dissolved in 70% ethylamine aqueous solution 101, to which was added 930+ g of 4-ethynylaniline dissolved in dimethylacetamide 51, and stirred at room temperature for 30 minutes.Furthermore, 3 1800 mg of (bromoethynyl)nitrobenzene dissolved in 5 Ill of oxymethylacetamide was added dropwise over 6 hours and stirred at room temperature for 12 hours. 4-(4-
950 mg of (aminophenyl)-1,3-butadiine was obtained. This product was prepared by adding 500 g of the diacetylene compound obtained as orange crystals to 20 m of dimethylacetamide.
10 g of triethylamine and 750 mg of eicosanniic acid monochloride were added thereto, and the mixture was heated and stirred at 120° C. for 12 hours.

By the same operation as in Example 1, 4- (4-(3
280 mg of -nitrophenyl)-1,3-butacyinyl)phenylcarbamoylnonadecanoic acid was obtained.

This substance was pale yellow crystal.

Elemental analysis 41t CC5hHaJtOs) Calculated value (%); C73,69, H7,90, N 4.7?
Actual η1Hii (%); C73,51, H8
, 15□N 4.62 Example 4 Static atmosphere, copper chloride [1150 mg to ethylamine 70
% aqueous solution, to which a solution of 930s+g of 2-ethynylaniline dissolved in 5n+I dimethylacetamide was added, and the mixture was stirred at room temperature for 30 minutes. 4 more
A solution of 1800+ g of -(bromoethynyl)nitrobenzene dissolved in 5 ml of dimethylacetamide was added dropwise over 6 hours, and the mixture was stirred at room temperature for 12 hours. Hereinafter, by the same operation as in Example 1, 1-(4-nitrophenyl)-4-(
2-aminophenyl)-1,3-butadiyne 1080+
I got ag. This substance was an orange crystal. Next, 500 mg of the obtained diacetylene compound was dissolved in 20 Ill of dimethylacetamide, and triethylamine 10+
sl, add eicosanniic acid monochloride 750B,
Heat and stir at 130° C. for 15 hours.

Hereinafter, by the same operation as in Example 1, 2-(4-(4-
310 vag of (nitrophenyl)-1,3-butacyinyl)phenylcarbamoylnonadecanoic acid were obtained.

This substance was pale yellow crystal.

Elemental analysis value (as C3JtJzO-) in total 3 [Id
! (%); C73,69, H7,90, N4.77 Actual value (%); C73,50, H8,05, N4.9
8 Example 5 Under Ar atmosphere, ifI+ chloride 5On+g was dissolved in ethylamine 70% water>8M10ml, and 3-ethynylaniline 930II+g was dissolved in dimethylacetamide 5ml.
1 and stirred at room temperature for 30 minutes. In addition, 180 kg of 4-(bromoethynyl)nitrobenzene
A solution of 5 ml of dimethylacetamide was added dropwise over 6 hours, and the mixture was stirred at room temperature for 12 hours. Example 1 below
By the same operation as above, 1-(4-nitrophenyl)-4
-(3-aminophenyl)-1,3-butadiyne 113
0 mg was obtained. This substance was yellow crystal. Next, 500 mg of the obtained diacetylene compound was dissolved in 20 ml of dimethylacetamide, and 10 ml of triethylamine was added.
, 750III g of eicosanniic acid monochloride were added, and the mixture was heated and stirred at 130° C. for 15 hours.

Hereinafter, by the same operation as in Example 1, 3- (4-(4
-Nitrophenyl)-1,3-butacyinyl)phenylcarbamoylnonadecanoic acid 300I1gG obtained.

This substance was pale yellow crystal.

Elemental analysis value (as Ozbl14JhOs) Calculated value (%
); C73,69, H7,90, N 4.77 Real A
(su(+ff(%);c73.88.H7,69,N4
．． 73 Example 6 Ar atmosphere F1 A4[+ chloride 50 mg is dissolved in ethylamine 70% aqueous solution 101, 4-ethynylaniline 930a+g dissolved in dimethylacetamide 5 ml is added thereto, and the mixture is stirred for 30 minutes at room temperature. Furthermore 4-
1800 mg of (bromoethynyl)nitrobenzene dissolved in methylacetamide 51 was added dropwise over 8 hours, and the mixture was stirred at room temperature for 12 hours. Hereinafter, by the same operation as in Example 1, 1-(4-nitrophenyl)-4-(4-
920 mg of (aminophenyl)-1,3-butadiyne was obtained. This substance was a red crystal. Next, 500 mg of the obtained diacetylene compound was added to 20 m of dimethylacetamide.
To this, add 10 m+1 triethylamine and 750 a+g eicosanniic acid monochloride.
Heat and stir at 130°C for an hour.

Hereinafter, by the same operation as in Example 1, 4- (4-(4
-Nitrophenyl)-1,3-butacyinyl)phenylcarbamoylnonadecane M 220+mg was obtained.

This substance was yellow crystal.

Elemental analysis value (as CibHabNtOs) Calculated value (%
); C73,69, H7,90, N 4.77 Actual value (%); C73,64, H8,11, N 5.0
7 Example 7 1-(3-nitrophenyl)-4-( obtained in Example 2)
3-aminophenyl)-1,3-phtadiyne 500m
g was dissolved in 20 ml of dimethylacetamide, 101 g of triethylamine and 490 ffig of azelaic acid monochloride were added thereto, and the mixture was stirred at room temperature for 5 hours. Thereafter, 220 mg of 3-(4-(3nitrophenyl)-1,3-butacyinyl)phenylcarbamoyl octanoic acid was obtained by the same operation as in Example 1. This substance was pale yellow crystal.

Elemental analysis value (as CzsH□autos) Calculated value (%
); C69,44, H5,59, N 6.48 fruit/
I! I(+σ (%); C69,18, H5-
80, N 6.42 [Application Example] Next, a method for producing a cumulative film of the compound of the present invention will be explained according to the attached drawings. Figure 1 shows one of the devices for producing a cumulative film.
A perspective view showing an example, and FIG. 2 is a side sectional view thereof, in which an aqueous solution containing a metal salt, such as a cadmium chloride aqueous solution, is filled in a water tank l with a frame 2 arranged inside, and the surface is sufficiently covered with the aqueous solution containing a metal salt. The cleaned glass substrate 11 is held by the support arm 12 and immersed in the glass so that the plane of the glass is perpendicular to the water surface.

Next, the compound of the present invention is dissolved and developed in a volatile solvent such as chloroform on the water surface, and then the solvent is completely evaporated.

Next, it comes into sliding contact with the left and right sides of the frame 2, and slides i5.
A first layer of monomolecular film is formed on the glass surface when the glass substrate is pulled up while applying a predetermined surface pressure by the float 3 which is applied with tensile force by the weight 4 through the 0-order pulled glass. After sufficiently drying the substrate, it is lowered while applying surface pressure in the same manner, and a second layer is further accumulated on the previously formed monomolecular film. In this way, by repeating the upward and downward movement of the glass substrate, a cumulative monomolecular film having the same component composition can be obtained.

6 in the figure is a magnet attached to the float, and the action of this pair of magnets 7 moves the float 6 to its original position.

According to the above method, a cumulative film was formed using the apparatus shown in the attached drawings.

That is, a glass substrate whose surface is sufficiently clean and hydrophilic is immersed in a lXl0-''M cadmium chloride aqueous solution so that the glass plane and the water surface are perpendicular. The obtained chloroform solution of 3-(4-(3-nitrophenyl)-1,3-butacyinyl)phenylcarbamoylnonadecanoic acid, 1XIO-'M is spread on the water surface.

After completely evaporating the chloroform, the surface pressure was increased for 20 days.
The glass substrate that had been immersed in the water was raised perpendicularly to the water surface at a rate of 0.7 cm/win. After sufficiently drying the pulled up substrate, 1. Oc+w/si
Lower it with n. By repeating this rising and falling operation, 3-(4-(3-nitrophenyl)-1,
A cumulative film of 3-phthacyinyl)phenylcarbamoylnonadecanoic acid was obtained.

For the derivatives obtained in other Examples, cumulative films were obtained by the same operation.

(Reference Example) Reference Example 1 Each sample of the compound of the present invention in powder form was vacuum sealed in a glass tube and irradiated with cobalt 60 gamma rays at a dose of 50 MRAD to undergo solid phase polymerization.After opening the package, tetrahydrofuran The results are shown in the 0-dimensional table, in which the polymerization yield was determined from the weight of the insoluble polymer, for those in which the number of carbon atoms in the alkyl chain was n=18.

(d) Substitution position of u group) (Substitution position of 7miF group)
(%)Rose Para 60
It is clear that both compounds have considerable solid phase polymerizability. It was also found that compounds with other carbon chain lengths exhibit considerable polymerizability.

Reference Example 2 The compound of the present invention was formed into a cumulative film, and its solid phase polymerizability was observed. When 11 layers of each compound were accumulated using the method shown in the application example and irradiated with UV light (Xe lamp, 500 W) for 5 hours to perform solid phase polymerization, a blue-colored polymer heterolaminar film was obtained. is 630 according to the visible absorption spectrum.
This was confirmed by the fact that the absorption near nm increased in proportion to the irradiation time.

〔Effect of the invention〕

As shown in the above example, the diphenyl diacetylene derivative according to the present invention is structurally asymmetric, and has a nonlinear optical effect because the substituent is an aromatic group conjugated with a diacetylene triple bond. In addition, as shown in the reference examples and application examples above, it has solid phase polymerizability and can be formed into a cumulative film, making it easy to make high-performance devices. It is suitable as a diacetylene monomer for forming materials.

The cumulative film of the diphenyl diacetylene derivative according to the present invention can be applied to high-performance devices, especially as a nonlinear optical material in which the molecular orientation is reflected in its performance.

[Brief explanation of drawings]

FIG. 1 is a perspective view showing an example of an apparatus for producing a cumulative film, and FIG. 2 is a side sectional view thereof. In the figure, 1 is the water tank, 2 is the frame, 3 is the float, 4 is the weight, lO
is a liquid level, and 11 is a glass substrate.

Claims (1)

[Claims] (1) It is represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, where one of R_1 and R_2 is a nitro group, the rest is hydrogen, and any one of R_1' to R_3' is - NHCO-(CH_2)-_nCO_2
A diphenyl diacetylene derivative in which H (where n=6 to 18) and the remainder being hydrogen.