JPH03112982A - Benzalacetophenone and nonlinear optical material - Google Patents

Abstract

NEW MATERIAL:1-[2-(5-Bromothienyl)]-3-(4'-substituted phenyl)-propen-3-one of the formula (R is OCH3, NH2, NO2, Cl or Br). EXAMPLE:1-[2-(5-Bromothienyl)]-3-(4'-methoxyphenyl)propen-3-one. USE:A nonlinear optical material, an intermediate of medicines, a photosensitizer, etc. Excellent in transmission properties and transparency. PREPARATION:With 2-bromothiophene-5-carboxyaldehyde, respectively 4'- methoxyacetophenone, 4'-aminoacetophenone, 4'-nitroacetophenone, 4'- chloroacetophenone or 4'-bromoacetophenone is reacted in the presence of a basic catalyst (e.g. sodium hydroxide) or an acid catalyst (e.g. boron trifluoride) using a solvent such as methanol or ethanol as necessary preferably at 0-50 deg.C for 30min.-50hrs.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to benzalacetophenone and nonlinear optical materials.

<Prior Art> A nonlinear optical material is a material that has a so-called nonlinear optical effect, in which the induced polarization of electrons induced by the electric field of light in a substance produces a nonlinear response to the electric field.
Generally, it is caused by a second-order term or higher as shown by the following formula.

P = to (I'E+ (2) E-E+ '3) E-E-E
+...+(n)E-n (where P is the polarizability of the material, E is the electric field, and ni(ri) is the n-th nonlinear susceptibility.

) 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, and depending on the voltage, Since the refractive index changes, this phenomenon can be used to perform various optical processes such as wavelength conversion, signal processing, and modulation of laser light, and is known to be extremely useful.

KH, PO4 (KDP) are conventional nonlinear optical materials.
, LiNbO3, NH4H2PO4 (ADP), and other inorganic crystals have been used, but single crystals with high optical purity are very expensive, are deliquescent and are inconvenient to handle, and have low nonlinear susceptibility. There were problems such as the fact that it was not expensive. Since the usefulness of organic materials was suggested at the 1983 American Chemical Society Symposium,
urea.

Organic crystals such as aniline compounds have been announced as nonlinear optical materials. However, these organic compounds have not yet shown a fully satisfactory nonlinear effect, and those that show a relatively high nonlinear effect have their own optical absorption edges shifted considerably toward longer wavelengths, making it difficult to use wavelength ranges. The drawback is that it is extremely limited.

<Problems to be Solved by the Invention> An object of the present invention is to provide a novel compound that can be used in nonlinear optical materials, pharmaceutical intermediates, photosensitizers, and the like.

Another object of the present invention is to have excellent transparency and permeability, and to exhibit an extremely high nonlinear effect. An object of the present invention is to provide a nonlinear optical material made of benzalacetophenone with a specific structure.

<Means for Solving the Problems> According to the present invention, the following structural formula (I) (wherein R is OCH, NH, No, (l or Br
Provided is a benzalacetophenone represented by

Further, according to the present invention, there is provided a nonlinear optical material comprising benzalacetophenone represented by the general formula (I).

The present invention will be explained in more detail below.

The benzalacetophenone of the present invention has the following general formula (I)
The benzalacetophenone represented by the general formula (I), in which R represents OCH□, NH2, No□, CQ or Br, is 1-(2-(5-bromothienyl) )-3-
(4'-methoxyphenyl)propen-3-one, l-
(2-(5-bromothienyl))-3-(4'-aminophenyl)propen-3-one, 1-(2-(5-bromothienyl))-3-(4'-nitrophenyl)propene -3-one, 1-(2-(5-bromothienyl)
)-3-(4'-chlorophenyl)propen-3-one, 1-(2-(5-bromothienyl))-3-(4'
-bromophenyl)propen-3-one.

In the present invention, to produce benzalacetophenone represented by the general formula (I), for example, 2-bromothiophene-5-carboxaldehyde and 4'-
It can be obtained by carrying out a dehydration condensation reaction of methoxyacetophenone, 4'-aminoacetophenone, 4'-nitroacetophenone, 4'-chloroacetophenone or 4'-bromoacetophenone in the presence of a basic or acidic catalyst. 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 etherate can be used. etc. can be used. More specifically, the 2-bromothiophene-5-carboxaldehyde and the specific acetophenone are mixed in the presence of the catalyst, if necessary, using an appropriate solvent such as an alcohol such as methanol or ethanol, Preferably 0℃~5
The benzalacetophenone of the present invention can be obtained by carrying out the 5011RJ7 reaction within a temperature range of 0°C for 30 minutes. When the reaction temperature is higher than 50°C, various side reactions occur due to heat, and when the reaction temperature is lower than 0°C, the reaction time becomes extremely long, which is unfavorable.

The benzalacetophenone of the present invention can be used as a nonlinear optical material as it is or after being purified by a known method.

<Effects of the Invention> The specific benzalacetophenone of the present invention exhibits an extremely high nonlinear optical effect. In addition, it exhibits extremely high transmittance to visible light having a wavelength of 400 nm or more and has excellent transparency, so it can be used for various optical purposes.

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

Disaster, 2-bromothiophene-5-carboxaldehyde 1.
91 g (0.01 mon) and 1.50 g (0.01 mo III) of 54'-methoxyacetophenone were charged into a reaction vessel together with 20 mQ of ethanol, and heated at 25°C.
While stirring, a mixed solution of 1 g of 40 wt % aqueous sodium hydroxide solution and 10 - ethanol was added dropwise. After completion of the dropwise addition, the reaction was carried out at 25°C for 24 hours. 0 after reaction.
After terminating the reaction by adding 20 mQ of a 5N aqueous hydrochloric acid solution, the precipitated solid was filtered, and the obtained solid was washed several times with distilled water and dried.

When the obtained crude product was recrystallized from ethanol solvent, 1-(2-(5-bromothienyl))-3-(4'-
Purified product of methoxyphenyl)propen-3-one 2.8
7g was obtained. The yield was 89%. Also, the melting point is 140
．． The temperature was 8°C. The elemental analysis values are shown below.

Elemental analysis value (C,, H, □S B r 02) CH
S Br Calculated value (%) 52.03 3.43 9.92 24.
72 Actual value (%) 51.45 3.3Q 9.70
25.10 Furthermore, the measurement results of the 1H-NMR spectrum are shown in FIG. 1, and the light transmission spectrum is shown in FIG. 2, respectively.

15 times, then the starting material acetophenone was converted into 4'-aminoacetophenone (Example 2), 4'-nitroacetophenone (Example 3), 4'-chloroacetophenone (Example 4), or 4'-chloroacetophenone (Example 4). '-Bromoacetophenone (Example 5)
Compounds of Examples 2 to 5 shown below were synthesized in the same manner as in Example 1 except that . The results are shown below.

Him1-(2-(5-bromothienyl))-3-(4'-
The melting point of the aminophenyl)propen-3-one compound is 1
The temperature was 71.2°C. Elemental analysis values are shown below.

Elemental analysis value (C,, Hl, N S Bro) CHN
S Br Calculated value σ) 50,66 3.27 4.54 10.4
0 25.93 length ■ straight α) 50.18 3,42
4.30 10.91 25.17'H-NMR
The spectrum measurement results are shown in Figure 3.

Compound A obtained in step 3 1-(2-(5-bromothienyl))-3-(4'
-nitrophenyl)propen-3-one compound had a melting point of 166.5°C. The elemental analysis values are shown below.

Elemental analysis value (C,,H,N S Br O,)CH
N S Br Calculated value C%) 46,17 2.38 4.14 9.4
8 23.63 Actual straight a (%) 46,89 2,21 4
．． ．． 02 9,82 23. 15 Also, the measurement results of the 1H-NMR spectrum are shown in FIG.

The melting point of the hexamer-1-(2-(5-bromothienyl))-3-(4'-chlorophenyl)propen-3-one compound prepared in step 4 is 13
The temperature was 1.0°C. The elemental analysis values are shown below.

Elemental analysis value (C1, H, S CQ Br ○) CH
S CQ Br Calculated value α) 47.66 2.46 9.79 10.8
2 24.39 卽M σ) 46.11 2.32
9.15 10.24 24.85 Also, 1H-NM
The measurement results of the R spectrum are shown in FIG.

Him1-(2-(5-bromothienyl))-3-(4'-
The melting point of the bromophenyl)flopen-3-one compound is 1
The temperature was 47.5°C. The elemental analysis values are shown below.

Elemental analysis value (C□, H, SBr ○) CHS
Br Calculated value C%) 41.96 2.17 8.62 42.
95 chicken straight σ) 41.35 2.13 8.79
42.08 In addition, the measurement results of H-NMR spectra are shown in Figure 6.9 Second harmonic generation (SH) of the compounds obtained in Examples 1 to 5
G) was measured. Measurement method is diameter 50~150μ
A granulated sample of 500 m in diameter was sandwiched between slide glasses, and this sample was heated with a Nd"YAG laser (wavelength 1010 nm) equipped with a Q switch.
Pulse irradiation of 15n see was performed using 64n, 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 well known to those skilled in the art, and for example, reference may be made to Journal of Applied Physics, Vol. 36, No. 8, pp. 3798-3813, 1968.

Table 1 shows the SHG intensity ratio of benzalacetophenone of the present invention measured by the above method.

The light absorption spectrum was measured using 2-methyl-4-nitroaniline, which is a well-known nonlinear optical material. It exhibits a transmittance of almost 100% and is substantially transparent. On the other hand, 2-methyl-4-nitroaniline, which is a known nonlinear optical material, has a wavelength of 500 nm.
The following visible light is absorbed and does not pass through.

[Brief explanation of the drawings] Figure 1 shows the "I-I-N" of the compound obtained in Example 1.
A chart showing the MR spectrum, FIG. 2 is a chart showing the light absorption spectrum of the compound and a light absorption spectrum of a known nonlinear optical material, and FIG. 3 is a chart showing the MR spectrum of the compound obtained in Example 2. A chart showing the NMR spectrum, FIG. 4 is the 1H spectrum of the compound obtained in Example 3.
-Chart showing NMR spectra, FIG. 5 is Example 4
Figure 6 is a chart showing the H-NMR spectrum of the compound obtained in Example 5.
It is a chart showing an R spectrum. Figure 2 i-reverse length (nrn)

Claims (1)

[Claims] 1) Represented by the following structural formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) (In the formula, R represents OCH_3, NH_2, NO_2, Cl or Br) Benzalacetophenone. 2) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the formula, R represents OCH_3, NH_2, NO_2, Cl or Br) A nonlinear compound consisting of benzalacetophenone optical materials.