JPH0368540A - New malondialdehyde compound - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a novel malondialdehyde compound used in various devices in the field of optoelectronics. It is unknown and is a new compound.

(Problems to be Solved by the Invention) The compound of the present invention represented by the above structural formula (1) can be used in various devices (e.g., electro-optical devices,
It is useful as a material suitable for second harmonic generation devices, piezoelectric devices, waveguides and semiconductors, particularly devices in which films or layer arrangements or assemblies are used as constituent elements.

The malondialdehyde compound (1) of the present invention can be produced by various methods. A specific example thereof is shown in the reaction scheme below.

(Reaction Scheme 2) (Reaction Scheme 1) (2) / Hx (3) The reaction shown in the above Reaction Scheme 1.2 can be carried out using known methods such as G, M, Coppola et al.
cycle, Chem, 11.51 (1974)
It can be carried out according to the method described in . More specifically, using an excess amount of phosphorus oxychloride and dimethylformamide (DMF) with respect to compound (2) (DMF also serves as a solvent), after reacting at a temperature range of about 20 to 80 ° C. , subjected to sodium hydroxide treatment (reaction scheme 1)
.

The compound (1) of the present invention can be synthesized by reacting the compound (3) obtained above with sodium hydroxide in a temperature range of about 20 to 100°C and then treating with hydrochloric acid ( Reaction Scheme) The reaction solvent may be any solvent as long as it is inert to the reaction components.For example, in the case of Reaction Scheme 1, amine solvents such as DMF and triethylamine are preferred. In the case of reaction scheme 2, methanol,
Alcohol solvents such as ethanol are preferred.

In the case of Reaction Scheme 1, the reaction molar ratio is 1.0 to 10.0 times the mole of phosphorus oxychloride and O to 12.0 times the mole of DMFL per 1 mole of compound (2). 5
．． 0 to 7.0 and 6.0 to 8.0 times the mole are preferable, and in the case of reaction scheme 2, the sodium hydroxide is preferably 1.0 to 5.0 times the mole per mole of the product (3). In particular, 1.1 to 1.5 times the mole is preferred. Furthermore, in order to make the reaction proceed smoothly, it is preferred to add water. The amount added is such that the weight percent of sodium hydroxide is 15 to 30%. Good rank.

In the case of Reaction Scheme 1, the reaction temperature is 25 to 100°C, preferably 60 to 80°C, and in the case of Reaction Scheme 2, 50 to 100°C is used, particularly 70 to 80°C. 80°C is preferred.

The appropriate reaction time is 3 to 20 hours in any case.

When using ethanol as a solvent, the reaction method is to drop an aqueous sodium hydroxide solution into a solution of compound (3) dissolved in ethanol, but it can also be added at the same time.6 After the reaction is complete, ethanol is distilled off. After cooling with ice water, the mixture is separated in a furnace to obtain the sodium salt of compound (1). The sodium salt is dissolved in water, treated with hydrochloric acid, and the resulting precipitate is filtered to obtain crude crystals of the desired compound (1).

As the purification method, conventional separation means such as recrystallization method and column chromatography method are used, but sublimation method is preferable.

(Example) Hereinafter, the present invention will be explained in more detail by giving examples of the production of the compounds of the present invention as Examples and examples of the usefulness thereof as Reference Examples.

Synthesis Example 2 - Synthesis of (3-nitrophenyl)malondialdehyde Dimethylformamide (81 g, 1.1 mall) was added to phosphorus oxychloride (138 g, 0.9 mol) with stirring.
``Dropped slowly so as not to exceed C. After dropping,
After stirring for 5 minutes, 3-nitrophenyl acetic acid (54,
3g, 0, 3 mail・Dimethylformamide 15
The 0mt' solution was slowly added dropwise to the 0 reaction mixture, which was then stirred and heated at 70°C for 118 hours. After heating, the temperature was returned to room temperature, and the reaction mixture was poured into 1.25 kg of ice. The reaction system was made neutral with anhydrous potassium carbonate, and then 50
Made strong base with 300-400% sodium hydroxide.

At this time, the temperature of the reaction mixture should not exceed 50'C. After the generation of diethylamine was completed, the reaction mixture was cooled with ice water, and the resulting precipitate was filtered out. The precipitate was thoroughly washed with water, dried, and then recrystallized with methanol to obtain an intermediate (yield: 71%).

The intermediate (19.3 g, O, 1 mol) was dissolved in 150% ethanol and then 25% aqueous sodium hydroxide solution 150% was added. Thereafter, the reaction mixture was heated at 80° C. for 3 hours. After completion of the reaction, ethanol was distilled off, and the reaction mixture was cooled with ice water. The sodium salt of the product that precipitates? Each house was washed thoroughly with methylene chloride. After drying, the sodium salt of the product was dissolved in water and made acidic by adding 6N hydrochloric acid. Product (1)? The product was separated and recrystallized with methanol and then purified by sublimation to obtain the desired product as white crystals with m and p of 122-124°C (yield 52%).

As shown in Figure 1, the IR spectrum (KB,) of compound (1) shows an absorption originating from the OH group at 3550 cm-';
Absorption derived from aldehyde group at 2650.1630 cm-', absorption derived from N Oa group at 1535.1350 cm-', 1130.890.760.730 cm-'
Absorption derived from m-substituted aromatic ring, 1600.800c
In addition to absorptions derived from trisubstituted vinyl bonds appearing at m''', 2900 to 3100.1490, l 43
Strong absorption also appears at 0.1270.

'H-NMR spectrum of compound (1) (CDC13
), as shown in Figure 2, there is a broad peak at 14.5 ppm originating from the proton of the OH group, and a single peak originating from the aldehyde group and the proton of -C=C-H (
Compound (1) has an intramolecular hydrogen bond in the solution as shown in the figure below, so Ha and Hb are equivalent) is 8.7 p
At pm, there is a multi-bullet peak originating from the aromatic ring.
It appears in the range of 1 to 8.4 ppm, and each integral value is 1:2.
It is consistent with +4.

In addition, the mass spectrum and elemental analysis are m/e493 (molecular weight of compound (1); 1931° elemental analysis value measured value C56,02, H3,65, N 7.23.0
33.10 Calculated value C55, 96, H3, 63, N 7
．． 25.033.16, the structure of compound (1) was proved from the very good match.

Reference Example 1 Regarding the compounds of the present invention shown in Table 1, second harmonic generation (SHG) was measured using the method of S. K. Kurtz et al.
J. Appl. Phys., 39.3798).

Nd: YAG laser (Spectra
A powder sample filled in a glass cell is irradiated with a 1.064 μ ray from a YAG laser DCR-3 manufactured by Physics (peak output 110 MW), and the generated green light is separated using a filter (532 nm) and photoelectron intensification is performed. Detected with double tube. The harmonic conversion efficiency is calculated as a relative value using urea as a standard, and the results are shown in Table 1.
Shown below.

As shown in Table 1, 2- or 4-nitrophenylmalondialdehyde, which is a known substance, has almost the same SHG activity as urea, but 3-nitrophenylmalondialdehyde, a product of the present invention, is suitable for nonlinear optical elements. It can be seen that it is excellent.

[Brief Description of the Drawings] Figure 1 shows the infrared absorption spectrum (I) of the compound of the present invention.
R) Figure 2 is a proton nuclear magnetic resonance spectrum (H-NMR) diagram of the compound of the present invention.

Claims (1)

[Claims] Structural formula (1) ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ A novel malondialdehyde compound represented by