JPH03215477A - Compound having asymmetric carbon atom and nonlinear optical material composed thereof - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (Ar is phenyl substituted with electron-donative group; R is alkyl having asymmetric C such as group of formula II). EXAMPLE:5-(4-Methoxybenzylidene)-N-(1-phenylethyl)-2,4-oxazolidinedione. USE:Useful as a nonlinear optical material, especially a wavelength-converting material. Useful also as a bistable optical element, a light modulation element, a phase-conjugate optical element, etc. PREPARATION:The compound of formula I can be produced by the Knoevenagel reaction of a benzaldehyde derivative and a 3-alkyloxazolidine-2,4-dione in the presence of a catalyst (e.g. metallic sodium) in a solvent (e.g. toluene) at -100 to +100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a 5-henjilinoxazolidine-2,4-sion derivative having an asymmetric carbon atom and a nonlinear optical material using the same.

(Prior Art) In recent years, nonlinear optical materials--materials with nonlinearity between polarization and electric field that appear when a strong optical electric field such as laser light is applied have attracted attention.

Such materials are generally known as nonlinear optical materials and are described in detail in, for example: ``Nonlinear Optical Properties of Organic Materials and Materials'' ACS Symposium Series 233 edited by Debinot G.A. Williams (American Chemical Society 1988)
3 years) ``Nonlinear Optical P
properties of organic and
ACS
SYMPOSIUM SERIES2 3
3 David J. Williams
kyA (American Chemical Soc.
iety. ``Nonlinear Optical Properties of Organic Molecules and Crystals'', supervised by Masao Kato and Hachiro Nakanishi (CMC, published in 1985) Volumes 1 and 2, D.M. Shumura and G.I.
Published by Press, 1987) r ”Nonlinear
Optical Properties ofOrg
anic molecules and crystals
ls' vol 1 and 2 D. S. Che
mla and j. Zyss & W (8ca
(Published by Desic Press). One of the applications of nonlinear optical materials is second harmonic generation (SHO) based on second-order nonlinear effects and wavelength switching devices using sum and difference frequencies.

Those that have been used practically so far are inorganic velourites represented by lithium niobate. However, recently, π with electron-donating and electron-withdrawing groups has been developed.
Electronically conjugated organic compounds greatly exceed the aforementioned inorganic materials.
It has become known that it has various properties as a nonlinear optical material. In order to form higher-performance nonlinear optical materials, it is necessary to arrange compounds with high nonlinear susceptibility in the molecular state so as not to cause inversion symmetry. It is known that compounds with long π-electron conjugated chains are useful for expressing high nonlinear susceptibility, which is one of these, and are variously described in the above-mentioned literature, but in these compounds, As is obvious, the maximum absorption wavelength becomes longer, leading to a decrease in the transmittance of blue light, for example, and hindering the generation of blue light as the second harmonic.
This also occurs in p-nitroaniline derivatives, and the fact that the transmittance of the wavelength has a large influence on the efficiency of second harmonic generation is described in Alain Azema et al., Bros. 400 volumes, new
Optical Materianorezu (Alain Az4m
a (th author, Procedures of SPIE
, Volume 400, Now Optial Mate
This is clear from Figure 4, p. 186 of Rials) + (1983).

Therefore, the emergence of nonlinear optical materials with high transmittance for blue light is desired. Conventionally, attempts have been made to replace the carbon atom in the Hensen nucleus of nitroaniline with a nitrogen atom, but satisfactory results have not always been obtained.

In addition, the present applicant has disclosed a better method in Japanese Patent Laid-Open No. 62
-210430 and JP-A-62-210432. However, as mentioned earlier, in order to be useful as a second-order nonlinear optical material, performance in the molecular state alone is insufficient, and it is essential that the molecular arrangement in the aggregate state has no inversion symmetry. be. However, currently it is extremely difficult to predict the molecular arrangement, and the probability of its existence among all organic compounds is not high. This means that the large nonlinear optical susceptibility (β
) and high blue light transmittance, 5-henzylidene oxazolidine-2,4-dione derivatives are no exception. A useful method for eliminating inversion symmetry in the molecular arrangement in crystals is the introduction of asymmetric carbon atoms. However, 5-penzyl 1 with asymmetric carbon atoms
Oxazolidine-2,4-dione derivatives are not yet known.

(Problem B to be solved by the invention) Therefore, the first object of the present invention is to
-Hendylideneoxazolidine-2.4-dione derivatives are provided, and a second purpose is to provide nonlinear optical materials comprising 5-henzylideneoxazolidine-2.4-dione derivatives having an asymmetric carbon atom. There is a particular thing.

(Means for Solving the Problems) As a result of extensive studies, the present inventors found the following general formula (1
) has been found to be able to achieve the objects of the present invention. General formula (1) 0 U In the formula, Ar represents a phenyl group substituted with an electron donating group, and R represents an alkyl group having an asymmetric carbon atom.

Note that the electron-donating group refers to a substituent having a negative Hamment's σt value.

Here, σtomi refers to "Structure-Activity Relationships of Drugs - Guidelines for Drug Design and Mechanism Research" 96-lo3u published by Nankoi-sha and Colvin. Hansch (Corwin 011ans
ch), Amberd Leo (Albert-Leo)
Author, Substitute Constance
Correlation Analysis in Chemistry
and Biology J (SubstiLucnL
Constants for correlation
n^analysis in Chemistry
and Biology) 6 9 ~ l 6
page l John Wiley & Sons
(Iley and Sons).

The method for measuring σp is [Chemical Review J (Che+*
ical Reviews), Volume 17, 125-l
36 (1935).

Preferred substituents include, for example, dimethylamino group, amino group, acetylamino group, methoxy group, ethoxy group, phenoxy group, methylthio group, ethylthio group, methyl group,
Examples include phenyl group, fluoro group, chloro group, bromo group, and iodo group. Among these, methoxy, ethoxy, methylthio, and ethylthio groups are preferred.

The alkyl group R having an asymmetric carbon atom is, for example, represented by the general formula (n
) can be expressed as

General formula (II) P' -{-M-}i- C-R'R# In the formula, M represents methylene or gesilF-converted methylene. n represents O or a positive integer. n is preferably a small number, particularly preferably 0. R' and R''R# each independently represent a hydrogen atom, an alkyl group, an aryl group, a halogen atom, a hydroxy group, a carboxy group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group , an amino group, an azilamino group, a carbamoyl group, a sulfamoyl group, a sulfo group, a sulfonyl group, etc. However, R', R', R
- are never the same as each other, R', R', R''
A hydrogen atom, an alkyl group, or an aryl group is preferable, and one represented by formula (a) is particularly preferable.

The position of the asymmetric carbon atom contained in R is oxazolidine-
The closer it is to the nitrogen atom of 2,4-dione, the more preferable it is, and the one represented by formula (a) is particularly preferable.

C11, Specific examples of the compounds of the present invention are shown below.

1. 0 0 Cllgo These compounds can be obtained by Knoevenagel reaction of henzaldehyde derivatives with 3-alkyloxazzuridine-2,4-diones. As the solvent, alcohols, polymers, nitriles, amides, etc. can be used, and as the catalyst, acids or bases can be used.

The reaction temperature can be carried out in the range of -100°C to too°C, preferably in the range of -78°C to 50°C.

(Example) Next, the present invention will be explained in detail based on examples.

Example 1 Synthesis of Compound 5 1) Synthesis of N-(1-phenylethyl)-2,4-oxazolidine sion To a 100 m eggplant-shaped flask were added 401 toluene and 2.7 g (26 smol) of ethyl glycolate.
Stir with a magnetic cooler and add (-)-1 phenylethyl isocyanate 3. 8g (26mol)
iDrop slowly. After stirring for a while after dropping, add a catalytic amount of small pieces of metallic sodium, attach a corrugated tube cooler and a drying tube, and leave at room temperature until the metallic sodium disappears (2
4 hours) Stir. After the reaction is completed, the toluene layer is poured into water, taken out and dried over magnesium sulfate, and the solvent is distilled off under reduced pressure. The product on the remaining oil was distilled under reduced pressure (bp=
1 2 8℃/Q. 3Peng Hg) L,N-(1-phenylethyl)-24-oxazolidinedione 1.67g
(8.14 l) was obtained in a yield of 31%.

2) Synthesis of Compound 5 A thermometer, a condenser condenser, a drying tube, and a Laher septum were attached to a 100 d three-necked flask, and 20% of dry tetrahydrofuran and 0.0% of dry diisobutyramine were added under a nitrogen atmosphere.
Add 80ae (5,7■01) and cool to -78°C. After adding 3.6 d (5.8 mm) of n-butyllithium (1.6 M) in hexane and stirring for 30 minutes, 1.0 ml of N-(1-phenylethyl)-2.4-oxazolidine ion was added. A solution of 4.81 mol of g (4.81 mol) dissolved in 1'5 of dry tetrahydrofuran was heated to -60°C~-
Add at a temperature of 50°C. After stirring for 10 min, 4-mel
・Kinhenzal Yhydro 0. 5 9 g (4.
3 mmol) to 5 d of dry tetrahye 1 mouthful of furan? Add the diluted liquid and stir until it reaches room temperature (lhr).
Furthermore, Pl luenesulfonyl chloride 1. 3 7
g (7.2 mol) to dry tetrahydrofuran 5 ta1? Did you tolerate it? Yong? Add soy sauce and leave overnight. Thereafter, the reaction solution is poured into a solution of saturated ammonium chloride aqueous solution and several drops of hydrochloric acid, extracted with ethyl acetate, dried over magnesium sulfate, and then the solvent is distilled off under reduced pressure. The obtained oily product was purified by preparative thin-layer silica gel chromatography (developing solvent: n-hexane:methylene chloride-I:2) and recrystallized from methanol to obtain 5-(4-methoxybenzylian). )N-(1-phenylethyl)-2.4-oxazolidinedione 0.13
g (0.40 of seagulls) was obtained in a yield of 9.3%.

Other derivatives can also be synthesized according to this method. The melting points and NMR chemical shifts of the compounds are shown in Tables I and below.

Table 1 1) 'It-NMR 8 (pp set) (CDCl 3):
7.60-7.20 (Peng.7+1) 5.44 (g.IH), 3. 97 (S. 3H), 3.98 (5.311). 1.92 (d.3H) (d.lll), 6.62 (S.LH), 6.
04 (S.2H), 5.44 (g.IH). 1
．． 93 (d.3H) 3) C21+SS 7.70-7.2
0 (m.9H). 6.68 (8.111), 5.
45 (g.111), 3.01 (g.211),
1.93 (d.3H), 1.37 (t.311) 4) CH3S 7.70-7.15 (
m. 9H), 6.70 (S.IH), 5.46 (
g. lH), 2.53 (S.3H), 1.93
(d.311)5) CI+,0 7.
'7Hd. 2+1), 7.60~7.25(m.5H
), 6.95 (d.2H), 6.72 (S.l
H), 5.45 (g.III), 3.86 (S.
3H). 1.93 (d.3H) Next, it is shown that the compound of the present invention is useful as a nonlinear optical material. Example 2 Measurement of second harmonic generation was carried out by S.K. Kurz (SJ.K.
urLz), T.T.Peri-(T,T.Per
ry), Journal of Abright Physics (J. Appl. Phys.) 3 9, 379
This was carried out on the powder of the compound of the present invention according to the method described on page 8 (published in 1968). Measurements were performed using the equipment shown in Figure 1. That is, the measurement was performed using pulsed YAG laser light (λ=1.064 μm,
Beam diameter! ;lmφ, peak power 'i 1 0. Mw
/c+*2) was used as the fundamental wave, and the intensity of its second harmonic was measured using the evaluation device shown in FIG. The measurement was performed by relative comparison with the intensity of the second harmonic of urea. In addition, when the intensity was weak, visual observation was performed. In particular, the fundamental wave 2
In order to distinguish between the second harmonic and the light emitted by photon absorption (mainly yellow and red light), a spectrometer was installed to measure only the second harmonic. Furthermore, in powder method measurements, it is important to judge whether the material has nonlinearity, and the intensity ratio is a reference value for the magnitude of nonlinearity. The results are shown in Table 2. Table 2 OCL As is clear from the above-mentioned Example 2, the amorphous optical material of the present invention is particularly useful as a material for wavelength conversion. However, the use of the nonlinear optical material of the present invention is not limited to wavelength conversion elements, but it can be used for any element that utilizes nonlinear optical effects. Specific examples of devices in which the nonlinear optical material of the present invention can be used include optical bistable devices (optical storage devices,
Examples include optical pulse wavelength control elements, optical limiters, differential amplification elements, optical transistors, A/D conversion elements, optical logic elements, optical multi-vibration devices, optical Frisopf circuits, etc.), optical modulation elements, and phase conjugate optical elements. It will be done.

The compounds of the invention may be used, for example, in powder form, in the form of molecular inclusions in host lattices (polymers, packaging compounds, solid bodies, liquid crystals), in the form of gtN deposited on supports (such as Langmeer-Progento membranes, etc.). ), single crystal form, solution form, etc., and can be used as a nonlinear optical material in various forms.

Furthermore, the compound of the present invention can also be used in the form of a pendant bonded to borimer, boridiacetylene, or the like.

For details on these methods, see D. above. J Jilli
It is described in the works of the au edition.

[Brief explanation of drawings]

Figure 1 shows the powder method measuring device, and the numbers in the figure indicate the following. ■ : T53 end sample 2 : Fundamental zero wave Kanoto filter 3 Bispectrometer 4 : Photomultiplier 5 : Amplifier (+1) : Wavelength l. 064pm 02). 0. 532μm

Claims (4)

[Claims] (1) A compound having an asymmetric carbon atom represented by the following general formula (I). General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, Ar represents a phenyl group substituted with an electron donating group, and R represents an alkyl group having an asymmetric carbon atom. (2) A nonlinear optical material comprising the compound according to claim (1). (3) A compound in claim (1), wherein R is represented by formula (a). Formula (a) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (4) A nonlinear optical material comprising the compound according to claim (3).