JPH04212937A - Nonlinear optical material - Google Patents

Abstract

PURPOSE:To obtain a nonlinear optical material of presenting a high nonlinear optical effect with excellence in permeability and transparency of blue color light by forming of a specific 1-(3'-thienyl)-3-phenyl propene-1-on derivative. CONSTITUTION:A material is formed of a 1-(3'-thienyl)-3-phenyl propene-1-on derivative represented by a formula I. In the formula I, R represents a methyl group and an chlorine atom or a bromine atom. As the 1-(3'-thienyl)-3-phenyl propene-1-on derivative, 1-(3'-thienyl)-3-(4''-methylphenyl)propene-1-on or the like is listed. In order to manufacture this derivative, for instance, corresponding 1mol benzaldehyde derivative and 1mol 3-acetylthiophene are processed by dewatering condensation reaction or the like for 2 to 6 hours at a 0 deg.C to 50 deg.C reaction temperature by preferably using a solvent of methanol or the like under presence of basic catalyst of sodium hydroxide or the like.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION The present invention relates to nonlinear optical materials comprising 1-(3'-thienyl)-3-phenylpropen-1-one derivatives.

0002

[Prior Art] A nonlinear optical material refers to a material that has a so-called nonlinear optical effect, in which induced polarization of electrons induced by the electric field of light in a substance produces a nonlinear response to the electric field. This is caused by a quadratic term or more as shown by the following equation 1.

[Math 1]

In particular, according to a phenomenon known as second harmonic generation (SHG) that utilizes the second-order effect, incident light becomes a second harmonic, a light wave with twice the frequency, or Since the refractive index changes depending on the voltage, this phenomenon can be used to perform various optical processing such as wavelength conversion, signal processing, and laser light modulation, and is known to be extremely useful. There is.

KH2PO is a conventional nonlinear optical material.
4 (KDP), LiNbO3, NH4H2PO4 (AD
Inorganic crystals such as P) have been used, but single crystals with high optical purity are extremely expensive, are deliquescent and inconvenient to handle, and have low nonlinear susceptibility. There's a problem.

On the other hand, since the usefulness of organic materials was suggested at the 1983 American Chemical Society Symposium, organic crystals such as urea and aniline compounds have been announced as nonlinear optical materials. However, the above-mentioned organic compounds do not yet exhibit a fully satisfactory nonlinear optical effect, and those that exhibit a relatively high nonlinear optical effect have a light absorption edge of the compound itself that is considerably shifted toward the long wavelength side, which limits the wavelength range in which it can be used. The disadvantage is that it is extremely limited.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a nonlinear optical material that has excellent blue light transmittance and transparency and exhibits an extremely high nonlinear optical effect.

[0007]

[Means for Solving the Problems] According to the present invention, 1-(3'-thienyl )-3-Phenylpropen-1-one derivatives are provided.

[Case 2]

The present invention will be explained in more detail below.

1-(3) used in the nonlinear optical material of the present invention
'-thienyl)-3-phenylpropen-1-one derivatives are specifically listed as 1-(3'-thienyl)-3-
(4″-methylphenyl)propen-1-one, 1-(
3′-thienyl)-3-(4″-chlorophenyl)propen-1-one, 1-(3′-thienyl)-3-(4″
-Bromophenyl)propen-1-one, 1-(3'-
thienyl)-3-(4″-nitrophenyl)propene-
1-on.

To produce the 1-(3'-thienyl)-3-phenylpropen-1-one derivative, for example, 1 mole of the corresponding benzaldehyde derivative and 1 mole of 3-acetylthiophene are mixed with sodium hydroxide and hydroxide. In the presence of a basic catalyst such as potassium or a quaternary ammonium salt, preferably using a solvent such as an alcohol such as methanol or ethanol, a dehydration condensation reaction is carried out at a reaction temperature of 0°C to 50°C for 2 to 6 hours. Obtainable. The reaction temperature is 5
If the temperature is higher than 0°C, a large amount of products due to side reactions will be produced, and if the temperature is lower than 0°C, the reaction will take a long time, which is not economically preferable.

The nonlinear optical material of the present invention has the above-mentioned 1-(3
'-Thienyl)-3-phenylpropen-1-one derivative can be obtained as it is or by purifying it by a known method such as recrystallization.

0012

Effects of the Invention The nonlinear optical material of the present invention has a specific 1-
Since it is composed of a (3'-thienyl)-3-phenylpropen-1-one derivative, it exhibits an extremely high nonlinear optical effect. In addition, it exhibits extremely high transmittance to visible light with a wavelength of 400 nm or more and has excellent transparency, so it can be used for various optical purposes.

[0013]

EXAMPLES The present invention will be explained in more detail with reference to Synthesis Examples, Examples and Comparative Examples.

[0014]

[Synthesis example 1] 1.90 g of 4-methylbenzaldehyde (
0.016 mol) and 3-acetylthiophene 2.0
0 g (0.016 mol) and 10 ml of ethanol were placed in a reaction vessel, and 10 ml of a 10 wt % aqueous sodium hydroxide solution was added dropwise while stirring at 0°C. After the dripping is finished,
The reaction was carried out at 25° C. for 4 hours, and the precipitated solid was washed several times with distilled water and then dried to obtain a crude crystal. The obtained crude crystals were then recrystallized using tetrahydrofuran to obtain 2.67 g (yield 74%) of a product. Analysis result 1-(3'-thienyl)-3-(4''
-methylphenyl)propen-1-one (melting point 120.
0°C).

[0015]

[Synthesis Examples 2 to 4] 4-methylbenzaldehyde was replaced with 4-chlorobenzaldehyde (Synthesis Example 2), 4-bromobenzaldehyde (Synthesis Example 3), and 4-nitrobenzaldehyde (Synthesis Example 4), and tetrahydrofuran was replaced with acetone: 1-(3'-thienyl)-3-(4''-chlorophenyl)propene-1 was prepared in the same manner as in Synthesis Example 1 except that the mixed solvent was replaced with ethanol = 2:1 (volume ratio).
-one (melting point 127.7°C) in 72% yield (Synthesis Example 2)
), 1-(3′-thienyl)-3-(4″-bromophenyl)propen-1-one (melting point 136.1°C) was
With a yield of 1% (Synthesis Example 3), 1-(3'-thienyl)-
3-(4″-nitrophenyl)propen-1-one (melting point 191.4°C) was obtained in a yield of 47% (Synthesis Example 4).

[0016]

Example 1 Second harmonic generation (hereinafter referred to as SHG intensity) of the compounds obtained in Synthesis Examples 1 to 4 was measured. The measurement method is to sandwich a granulated sample with a diameter of 106 to 150 μm between slate glasses, and then attach a Q-switched Nd+
-10ns by YAG laser (wavelength 1064nm)
EC pulse irradiation was performed, and the second harmonic generated from the sample was detected. Similarly, granulated urea was used as a standard sample, and the SHG intensity ratio of the sample was determined when the SHG intensity of urea was set to 1. This measurement method is a method known to those skilled in the art, and is described, for example, in Journal of Applied Physics, Vol. 36, No. 8, pp. 3798-38.
13, 1968 may be referred to. Also,
A 0.1 mmol/l ethanol solution of each of the above compounds was prepared, and absorption spectra were also measured. S.H.G.
Intensity, maximum absorption wavelength (λmax) and absorption edge wavelength (λc
Table 1 shows the values of ut off).

[0017]

[Comparative Example 1] Same as Example 1 except that urea, KDP, 1-(3'-thienyl)-3-phenylpropen-1-one and 4-nitro-2-methylaniline shown in Table 1 were used. Each measurement was performed using The results are shown in Table 1.

[Table 1]

Claims (1)

[Claims] Claim 1: 1-(3'-thienyl)-3-phenylpropen-1-one represented by the following general formula 1 (wherein R represents a methyl group, a nitro group, a chlorine atom or a bromine atom) Nonlinear optical materials made of derivatives. [Chemical formula 1]