JPH0833562B2 - Non-linear optical material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a nonlinear optical material comprising a chalcone derivative.

<Prior art and its problems> A non-linear optical material refers to a material having a so-called non-linear optical effect in which the induced polarization of electrons induced by the electric field of light in a substance causes a non-linear response to the electric field. , Which is generally caused by a quadratic term or more represented by the following equation.

P = κ ⁽¹⁾ E + κ ⁽²⁾ E ・ E + κ ⁽³⁾ E ・ E ・ E + ……
κ ⁽ⁿ⁾ E · n (where P is the polarizability of the substance, E is the electric field, and κ _(n) is the n-th order nonlinear susceptibility.) Especially the second harmonic generation using the second-order effect According to a phenomenon known as (SHG), the incident light becomes a light wave having a frequency twice as high as the second harmonic, and the refractive index changes depending on the voltage. It is known that various optical processes such as wavelength conversion, signal processing, laser light modulation, etc. can be performed, and they are extremely useful.

Conventional non-linear optical materials include KH ₂ PO ₄ (KDP), LiNbO ₃ , N
Inorganic crystals such as H ₄ H ₂ PO ₄ (ADP) have been used, but single crystals with high optical purity are very expensive and deliquescent, which makes them inconvenient to handle, and nonlinear susceptibility is also high. There were problems such as not being very expensive. On the other hand, organic crystals such as urea and aniline compounds have been announced as nonlinear optical materials since the usefulness of organic materials was suggested at the 1983 American Chemical Society symposium. However, these organic compounds do not yet exhibit a satisfactory non-linear effect, and those exhibiting a relatively high non-linear effect show that the light absorption edge of the compound itself has shifted considerably to the long wavelength side and the operating wavelength range is It has the drawback of being extremely limited.

<Object of the Invention> An object of the present invention is to provide a non-linear optical material composed of a chalcone derivative, which has excellent transparency and transparency and exhibits an extremely high non-linear effect.

<Means for Solving Problems> According to the present invention, the general formula (In the formula, R represents a halogen atom, a hydroxyl group, a nitro group, an amino group, a dimethylamino group, a phenyl group, a cyano group, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 22 carbon atoms, and (n is 1 ~ 19, m represents an integer of 0 to 5.) In the formula, A is A non-linear optical material comprising a chalcone derivative represented by

 Hereinafter, the present invention will be described in more detail.

General formula used in the present invention In the formula, R represents a halogen atom, a hydroxyl group, a nitro group, an amino group, a dimethylamino group, a phenyl group, a cyano group, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 22 carbon atoms, and n is 1 to 1 The integer of 19 and m represent the integer of 0-5.
When n is 20 or more, the production becomes difficult, so that it cannot be used. Further, when R is an alkyl group having 19 or more carbon atoms or an alkoxy group having 23 or more carbon atoms, it is difficult to manufacture and cannot be used. Furthermore, A in the general formula (I) is Represents

In the present invention, as the method for producing the chalcone derivative which is the nonlinear optical material of the general formula (I), the above A is In the case of acetophenone or R of the general formula (I)
Acetophenone with Substituents and Carbon Number
4-alkyloxybenzaldehyde having 2 to 20 alkyl groups, and A is In this case, benzaldehyde or a benzaldehyde having a substituent corresponding to the R moiety of the general formula (I) and 4-alkyloxyacetophenone having an alkyl group having 2 to 20 carbon atoms are used to form a basic catalyst or an acidic catalyst. It can be obtained by a condensation reaction in the presence.
As the basic catalyst, for example, sodium hydroxide, potassium hydroxide or various quaternary ammonium salts can be used, and as the acidic catalyst, for example, boron trifluoride, phosphorus oxychloride, boron trifluoride can be used. Etherate or the like can be used. During the reaction, if necessary, it is preferable to carry out the reaction for 30 minutes to 25 hours in the temperature range of 0 ° C to 50 ° C using an appropriate solvent, for example, alcohols such as methanol and ethanol. During the reaction, the reaction temperature is 50 ° C.
When it is higher, various side reactions due to heat occur, and when it is lower than 0 ° C, the reaction time becomes extremely long.

Examples of the chalcone derivative represented by the general formula (I) obtained by the present invention include 4-octadecyloxychalcone, 4-octadecyloxy-4′-chlorochalcone, 4-octadecyloxy-4′-bromochalcone, and 4-octadecyloxy-4′-bromochalcone. -Octadecyloxy-4'-hydroxychalcone, 4-octadecyloxy-4'-nitrochalcone, 4-octadecyloxy-4'-aminochalcone,
4-octadecyloxy-4'-dimethylaminochalcone, 4-octadecyloxy-4'-methylchalcone,
4-octadecyloxy-4'-ethylchalcone, 4-
Octadecyloxy-4'-butylchalcone, 4-octadecyloxy-4'-methoxychalcone, 4-octadecyloxy-4'-ethoxychalcone, 4-octadecyloxy-4'-butoxychalcone, 4-octadecyloxy-3'- Chlorochalcone, 4-octadecyloxy-3'-bromochalcone, 4-octadecyloxy-3'-hydroxychalcone, 4-octadecyloxy-3'-nitrochalcone, 4-octadecyloxy-
3'-aminochalcone, 4-octadecyloxy-3 '
-Dimethylaminochalcone, 4-octadecyloxy-
3'-methylchalcone, 4-octadecyloxy-3 '
-Ethyl chalcone, 4-octadecyloxy-3'-butyl chalcone, 4-octadecyloxy-3'-methoxy chalcone, 4-octadecyloxy-3'-ethoxy chalcone, 4-octadecyloxy-3'-butoxy chalcone, 4 ' -Octadecyloxychalcone, 4-chloro-4'-octadecyloxychalcone, 4-bromo-
4'-octadecyloxychalcone, 4-hydroxy-
4'-octadecyloxychalcone, 4-nitro-4 '
-Octadecyloxychalcone, 4-amino-4'-octadecyloxychalcone, 4-dimethylamino-4 '
-Octadecyloxychalcone, 4-methyl-4'-octadecyloxychalcone, 4-ethyl-4'-octadecyloxychalcone, 4-butyl-4'-octadecyloxychalcone, 4-methoxy-4'-octadecyloxychalcone, 4 -Ethoxy-4'-octadecyloxychalcone, 4-butoxy-4'-octadecyloxychalcone, 3-chloro-4'-octadecyloxychalcone, 3-bromo-4'-octadecyloxychalcone, 3-hydroxy-4'- Octadecyloxychalcone, 3-nitro-4'-octadecyloxychalcone,
3-amino-4'-octadecyloxychalcone, 3-
Dimethylamino-4'-octadecyloxychalcone,
3-Methyl-4'-octadecyloxychalcone, 3-
Ethyl-4'-octadecyloxychalcone, 3-butyl-4'-octadecyloxychalcone, 3-methoxy-4'-octadecyloxychalcone, 3-ethoxy-
4'-octadecyloxychalcone, 3-butoxy-
Preferable examples include 4'-octadecyloxychalcone.

<Effect of the Invention> The chalcone derivative represented by the general formula (I) of the present invention is
It has a very high nonlinear effect. Further, since it has extremely high transparency to visible light having a wavelength of 400 nm or more and is excellent in transparency, it can be used for various optical treatment materials.

<Examples> The present invention will be described in more detail with reference to Examples and Comparative Examples.

Example 1 50 ml of dehydrated ethanol was poured into a 100 ml flask, 1.27 g (0.055 mol) of sodium metal was placed therein, and a calcium chloride tube was attached to the flask to stir the mixture so that water content would not enter the flask to obtain sodium ethoxide. Hydroxybenzaldehyde in 100 ml stainless pressure resistant tube
6.10 g (0.05 mol) and octadecyl chloride 14.43 g (0.
(05 mol) and the above sodium ethoxide ethanol solution were added, and the mixture was sealed, shaken at 120 ° C., and reacted for 15 hours. After completion of the reaction, the product was extracted with benzene, acidified with dilute hydrochloric acid, neutralized by washing with water, and concentrated and dried to obtain a crude product. This crude product was separated and fractionated with an open column of silica gel-chloroform (4
The octadecyloxybenzaldehyde Rf = 0.75) was repeated twice to obtain 11.03 g of 4-octadecyloxybenzaldehyde as a waxy product. The yield was 59%.

Next, this 4-octadecyloxybenzaldehyde 3.
74g (0.01mol) and 4-hydroxyacetophenone 1.36g
(0.01 mol) was placed in a reaction vessel together with 30 ml of ethanol and stirred at 50 ° C. to completely dissolve the reaction product. In this reactor, 1 g of 40% sodium hydroxide aqueous solution and ethanol 10
After dropping the mixed solution of ml, keep the reaction temperature at 20 ℃,
Allowed to react for hours. Then, 20 ml of 0.5N hydrochloric acid aqueous solution was added and stirred to stop the reaction, the precipitated solid was filtered, and the obtained solid was washed several times with water and dried.

When this crude product was recrystallized with an ethanol solvent, 4
3.29 g of purified octadecyloxy-4'-hydroxychalcone was obtained. The yield was 67%. FIG. 1 shows the light absorption spectrum of the purified 4-octadecyloxy-4'-hydroxychalcone.

Example 2 3.74 g (0.01 mol) of 4-octadecyloxybenzaldehyde and 1.50 g (0.01 mol) of 4'-methoxyacetophenone obtained in the same manner as in Example 1 were put in a reaction vessel together with 30 ml of ethanol and stirred at 50 ° C for reaction. After completely dissolving the product, put 40% aqueous sodium hydroxide in the reactor.
A mixed solution of 1 g and 10 ml of ethanol was added dropwise. After completion of the dropping, the temperature was kept at 25 ° C. and the reaction was performed for 10 hours. Then 0.
The reaction was stopped by adding 20 ml of 5N hydrochloric acid aqueous solution and stirring. The precipitated solid was filtered, the obtained solid was washed several times with water and dried.

When this crude product was recrystallized with an ethanol solvent, 4
-Octadecyloxy-4'-methoxychalcone purified product
0.36 g was obtained. The yield was 70%.

Example 3 3.74 g (0.01 mol) of 4-octadecyloxybenzaldehyde and 1.63 g (0.01 mol) of 4'-dimethylaminoacetophenone obtained in the same manner as in Example 1 were placed in a reaction vessel together with 40 ml of ethanol and stirred at 70 ° C. The reaction was completely dissolved. After a mixed solution of 1 g of 40% sodium hydroxide aqueous solution and 10 ml of ethanol was dropped into this reactor, the temperature was kept at 30 ° C. and the reaction was carried out for 6 hours. Then, 50 ml of water was added and stirred, the precipitated solid was filtered, the obtained solid was washed with water several times and dried.

The crude product was recrystallized from a mixed solvent of ethanol / chloroform = 7/3 to give 4-octadecyloxy-4 '.
-1.93 g of a purified product of dimethylaminochalcone was obtained. Yield 3
It was 7%.

Example 4 4-Octadecyloxybenzaldehyde (3.74 g, 0.01 mol) and 4'-nitroacetophenone (1.65 g, 0.01 mol) obtained in the same manner as in Example 1 were placed in a reaction vessel together with 40 ml of ethanol and stirred at 70 to 90 ° C. The reaction was allowed to dissolve completely. 40% sodium hydroxide solution in this reactor
After dropping a mixed solution of 1 g and 10 ml of ethanol, increase the temperature to 30
The temperature was kept at 0 ° C and the reaction was carried out for 12 hours. Then, 20 ml of 0.5N hydrochloric acid aqueous solution was added and stirred to stop the reaction. The precipitated solid was filtered, the obtained solid was washed with water several times and dried.

When this crude product was recrystallized with an ethanol solvent, 4
-Octadecyloxy-4'-nitrochalcone purified product 2.
I got 78g. The yield was 53%.

Example 5 50 ml of dehydrated ethanol was poured into a 100 ml flask, 1.27 g (0.055 mol) of metallic sodium was placed therein, and a calcium chloride tube was attached to the mixture to stir the mixture so that water did not enter the flask, to obtain sodium ethoxide. Hydroxyacetophenone in a 100 ml stainless pressure resistant tube.
80 g (0.05 mol) and octadecyl chloride 14.43 g (0.05
mol) to which the above sodium ethoxide ethanol solution was added, and the mixture was sealed and shaken at 120 ° C. to carry out the reaction for 50 hours. After completion of the reaction, the product was extracted with benzene, washed repeatedly with diluted hydrochloric acid and water, and then concentrated and dried to obtain a crude product. When this crude product was recrystallized with an ethanol solvent, 4'-octadecyloxyacetophenone purified product 16.04 g
I got The yield was 83%.

Next, this 4'-octadecyloxyacetophenone 3.
88g (0.01mol) and 4-dimethylaminobenzaldehyde
1.49 g (0.01 mol) was put into a reaction vessel together with 40 ml of ethanol and stirred at 60 to 80 ° C to completely dissolve the reaction product. Into this reactor, a mixed solution of 1 g of 40% sodium hydroxide aqueous solution and 10 ml of ethanol was dropped, and then the temperature was kept at 20 ° C. and the reaction was carried out for 8 hours. Then, 50 ml of water was added and stirred, the precipitated solid was filtered, the obtained solid was washed with water several times and dried.

When this crude product was recrystallized with an ethanol solvent, 4
3.40 g of a purified product of -dimethylamino-4'-octadecyloxychalcone was obtained. The yield was 66%.

Example 6 3.88 g (0.01 mol) of 4'-octadecyloxyacetophenone obtained in the same manner as in Example 5 and 1.65 g (0.01 mol) of 4-nitrobenzaldehyde were placed in a reaction vessel together with 40 ml of ethanol at 70 to 90 ° C. The reaction was allowed to stir and completely dissolved. After dropping a mixed solution of 1 g of 40% aqueous sodium hydroxide solution and 10 ml of ethanol into this reactor, the temperature was raised.
The temperature was maintained at 25 ° C and the reaction was carried out for 20 hours. Then, 20 ml of 0.5N hydrochloric acid aqueous solution was added and stirred to stop the reaction. The precipitated solid was filtered, the obtained solid was washed with water several times and dried.

When this crude product was recrystallized with an ethanol solvent, 4
-Nitro-4'-octadecyloxychalcone purified product0.
20 g were obtained. The yield was 4%.

Example 7 3.88 g (0.01 mol) of 4'-octadecyloxyacetophenone obtained in the same manner as in Example 5 and 1.36 g (0.01 mol) of 4-methoxybenzaldehyde were placed in a reaction vessel together with 30 ml of ethanol at 50 to 80 ° C. The mixture was stirred and the reaction product was completely dissolved. A mixed solution of 1 g of 40% aqueous sodium hydroxide solution and 10 ml of ethanol was dropped into this reactor, and then the temperature was kept at 20 ° C. and the reaction was carried out for 6 hours. Then, 20 ml of 0.5N hydrochloric acid aqueous solution was added and stirred to stop the reaction. The precipitated solid was filtered, the obtained solid was washed with water several times and dried.

When this crude product was recrystallized with an ethanol solvent, 4
-Methoxy-4'-octadecyloxychalcone purified product
I got 2.4g. The yield was 47%.

Example 8 4.88 g (0.01 mol) of 4'-octadecyloxyacetophenone obtained in the same manner as in Example 5 and 1.31 g (0.01 mol) of 4-cyanobenzaldehyde were placed in a reaction vessel together with 30 ml of ethanol and stirred at 40 ° C. The reaction was completely dissolved. Into this reactor, a mixed solution of 1 g of 40% sodium hydroxide aqueous solution and 10 ml of ethanol was dropped, and then the temperature was kept at 30 ° C. and the reaction was carried out for 8 hours. Then add 50 ml of water and stir,
The precipitated solid was filtered, the obtained solid was washed with water several times and dried.

The crude product was recrystallized with a mixed solvent of ethanol / benzene = 6/4 to obtain 2.80 g of a purified product of 4-cyano-4′-octadecyloxychalcone. The yield was 56%.

Example 9 3.74 g (0.01 mol) of 4-octadecyloxybenzaldehyde obtained in the same manner as in Example 1 and acetophenone 1.20
When g (0.01 mol) was charged, reacted and purified in the same manner as in Example 2, 3.32 g of a purified 4-octadecyloxychalcone was obtained. The yield was 70%.

Example 10 3.88 g (0.01 mol) of 4'-octadecyloxyacetophenone obtained in the same manner as in Example 5 and benzuraldehyde
Charge 1.06 g (0.01 mol) according to Example 6, react,
Purification was carried out in the same manner to obtain 3.1 g of a purified 4'-octadecyloxychalcone. The yield was 65%.

Example 11 According to Example 2, 4-octadecyloxybenzaldehyde (3.74 g, 0.01 mol) and 3'-methoxyacetophenone (1.50 g, 0.01 mol) obtained in the same manner as in Example 1 were charged, reacted and purified in the same manner. As a result, 3.52 g of a purified product of 4-octadecyloxy-3'-methoxychalcone was obtained. The yield was 70%.

Example 12 3.74 g (0.01 mol) of 4-octadecyloxybenzaldehyde and 1.99 g (0.01 mol) of 3'-bromoacetophenone obtained in the same manner as in Example 1 were charged, reacted and purified in the same manner as in Example 2. As a result, 3.61 g of a purified product of 4-octadecyloxy-3'-bromochalcone was obtained. The yield was 65%.

Example 13 According to Example 6, 4'-octadecyloxyacetophenone (3.88 g, 0.01 mol) and 3-ethoxybenzaldehyde (1.51 g, 0.01 mol) obtained in the same manner as in Example 5 were charged, reacted and purified in the same manner. As a result, 3.61 g of a purified product of 3-ethoxy-4'-octadecyloxychalcone was obtained. The yield was 67%.

Example 14 According to Example 6, 4'-octadecyloxyacetophenone (3.88 g, 0.01 mol) and 3-chlorobenzaldehyde (1.41 g, 0.01 mol) obtained in the same manner as in Example 5 were charged, reacted and purified in the same manner. On the spot, 3-chloro-
3.86 g of a purified 4'-octadecyloxychalcone was obtained. The yield was 73%.

Example 15 The second harmonic generation (SHG) of the chalcone derivatives synthesized in Examples 1 to 14 and the chalcone derivative synthesized by the same method was measured. The measuring method is 50-1 diameter
A 50 μm granulated sample was sandwiched between slide glasses, and this sample was pulse-irradiated with a Qd-switched Nd-YAG laser (wavelength 1064 nm) for 15 nsec to detect the second harmonic generated from the sample. Similarly, granular urea was used as the standard sample, and the SHG intensity ratio of the sample when the SHG intensity of urea was set to 1 was determined. This measurement method is well known to those skilled in the art, and for example, Journal of Applied Physics 36, No. 8, page 3798-
See page 3813, 1968.

The SH of the chalcone derivative of the present invention measured by the above method
The G intensity ratio is shown in Table-1.

Comparative Example 1 A light absorption spectrum was measured using 2-methyl-4-nitroaniline, which is a known nonlinear optical material. The results are shown in Fig. 1.

As is clear from FIG. 1, it shows almost 100% transmittance for visible light having a wavelength of 400 nm or more, and is substantially transparent. On the other hand, the known non-linear optical material, 2-methyl-4-nitroaniline, absorbs visible light having a wavelength of 500 nm or less and does not transmit it.

[Brief description of drawings]

FIG. 1 is a graph showing the light absorption spectrum of the nonlinear optical material of the present invention and the light absorption spectrum of a known nonlinear optical material.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Godo Irukayama 1-9-7-203 Ninomiya Yatabe-cho, Tsukuba-gun, Ibaraki Prefecture

Claims (1)

[Claims] 1. A general formula (In the formula, R represents a halogen atom, a hydroxyl group, a nitro group, an amino group, a dimethylamino group, a phenyl group, a cyano group, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 22 carbon atoms, and n is 1 to 1 19 is an integer, m is an integer of 0 to 5.) In the formula, A is A nonlinear optical material composed of a chalcone derivative represented by.