JPH06128234A - Compound having asymmetric carbon atom and non-linear optical material composed of the compound - Google Patents

Abstract

PURPOSE:To provide a 5-benzylideneazolidine-2,4-dione derivative having asymmetric carbon atom on a benzene ring site and suitable for various elements utilizing nonlinear optical effect. CONSTITUTION:The compound of formula (R is alkyl having asymmetric C atom; X is O, S or NR<2>; Y is O, S or NR<3>; Z is O, S or NR<4>; R<1> to R<4> are H, alkyl or aryl). The compound can be produced by the Knoevenagel reaction of a benzaldehyde derivative with an azolidine-2,4-dione derivative. The nonlinear optical material composed of the compound is especially useful as a material for converting the wavelength of laser light and usable also as a bistable optical element, light modulation element and phase-conjugated optical element.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-linear optical material suitable for use in various elements such as wavelength conversion elements that utilize non-linear optical effects, and a light wavelength conversion method using the same.

[0002]

2. Description of the Related Art In recent years, a material having a non-linear optical material-a non-linearity between a polarization and an electric field, which appears when a strong optical electric field such as laser light is applied, has been attracting attention.

Such materials are generally known as non-linear optical materials and are described in detail in, for example, the following. “Nonlinear Optical Properties of Organic and Polymeric Materials” ACS Symposium Series 23
3 Edited by David Jay Williams (American Society of Chemistry, 1983) "" Nonlinear Optical Properties
of Organic and Polymeric Material "ACS SYMPOSIUM SE
Edited by RIES 233 David J. Williams (American Chemical
Society, 1983) "," Organic Nonlinear Optical Materials ", supervised by Masao Kato and Hachiro Nakanishi (MCC, 1)
1985, "Nonlinear Optical Properties of Organic Molecule's and.
"Crystals" Volumes 1 and 2, edited by DS Smura and Jay This (Academic Press, 1987) "Nonlinear Optical Properties of O"
rganic Molecules and Crystals "vol1 and 2 DS
Edited by Chemla and J. Zyss (Academic Press).

One of the applications of the nonlinear optical material is the second harmonic generation (SHG) based on the second-order nonlinear effect and the wavelength conversion device using the sum frequency and the difference frequency. So far, those which have been practically used are inorganic perovskites represented by lithium niobate. However, recently, it has become known that a π-electron conjugated organic compound having an electron-donating group and an electron-withdrawing group has various performances as a nonlinear optical material, which greatly exceeds the above-mentioned inorganic substances. .

For the formation of higher performance nonlinear optical materials,
It is necessary to arrange compounds having high nonlinear susceptibility in the molecular state so as not to generate inversion symmetry. It is known that a compound having a long π-electron conjugated chain is useful for the expression of a high non-linear susceptibility, which is one of them, and various compounds are described in the above-mentioned documents. Obviously, the maximum absorption wavelength becomes longer, and the transmittance of blue light decreases, for example, which hinders the generation of blue light as the second harmonic. This also occurs in the p-nitroaniline derivative, and the fact that the transmittance of the wavelength has a great influence on the efficiency of the second harmonic generation is explained by Alain Azema et al., Proceedings of SPII, 40.
Volume 0, New Optical Materials (Alain Az
ema et al., Proceedings of SPIE, Volume 400, Now Opti
eal Materials), (1983) page 186, FIG.

Therefore, the advent of a nonlinear optical material having a high transmittance for blue light is desired. Conventionally, replacement of carbon atoms in the benzene nucleus of nitroaniline with nitrogen atoms has been studied, but satisfactory results have not necessarily been obtained. In addition, the applicant of the better method,
JP-A-62-210430 and JP-A-62-210
It was disclosed in Japanese Patent No. 432.

Further, JP-A-62-59934, JP-A-63-23136, JP-A-63-26638, JP-B-63-31768, JP-A-63-163827,
JP-A-63-146025, JP-A-63-85526
No. 63-239427, JP-A 1-1005.
21, JP-A-64-56425, JP-A-1-102.
529, JP-A-1-102530, JP-A 1-23
Many materials are disclosed in Japanese Patent No. 7625, Japanese Patent Laid-Open No. 1-207724, and the like.

However, as described above, in order to be useful as a second-order nonlinear optical material, the performance in the molecular state alone is insufficient, and the molecular arrangement in the aggregated state has no inversion symmetry. Is mandatory. However, at present, it is extremely difficult to predict the molecular arrangement, and the existence probability in all organic compounds is not high.

This is not an exception even in the case of a 5-benzylidene azolidine-2,4-dione derivative having a large nonlinear optical susceptibility (β) in the molecular state and a high blue light transmittance. A useful method for eliminating the inversion symmetry in the molecular arrangement in the crystal is the introduction of an asymmetric carbon atom. However, 5-benzylidene azolidine-2,4-having an asymmetric carbon atom at the benzene ring site
Dione derivatives are not known yet.

[0010]

Therefore, the first object of the present invention is to provide a 5-benzylidene azolidine-2,4-dione derivative having an asymmetric carbon atom at the benzene ring site. The purpose of is to have 5 asymmetric carbon atoms
-To provide a non-linear optical material comprising a benzylidene azolidine-2,4-dione derivative. A third object is to provide a method that utilizes the responsivity regarding the conversion of the optical wavelength among the non-linear responsivities.

[0011]

As a result of intensive studies, the present inventors have found that the compound represented by the following general formula (I) can achieve the object of the present invention. General formula (I)

[0012]

[Chemical 3]

The alkyl group R having an asymmetric carbon atom can be represented by, for example, the general formula (II). General formula (II)

[0014]

[Chemical 4]

In the formula, M represents methylene or gem-substituted methylene. n represents 0 or a positive integer. n is particularly preferably 1. R ', R "and R"' are each independently 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 acylamino group,
It represents a carbamoyl group, a sulfamoyl group, a sulfo group, a sulfonyl group and the like. However, R ', R ", and R"' are not the same as each other. R ', R ", and R"' are preferably a hydrogen atom, an alkyl group, or an aryl group, and particularly preferably those represented by formula (a). Formula (a)

[0016]

[Chemical 5]

X represents an oxygen atom, a sulfur atom, or = N-R ^2, and an oxygen atom is particularly preferable. Y represents an oxygen atom, a sulfur atom, = N-R ^3, in particular an oxygen atom. Z
Represents an oxygen atom, a sulfur atom, or = NR ^4, and an oxygen atom is particularly preferable. R ¹ , R ² , R ³ and R ⁴ are hydrogen atoms,
It represents an alkyl group or an aryl group, and examples of the alkyl group include a methyl group, an ethyl group and a propyl group, and those having 3 or less carbon atoms are particularly preferable. As an aryl group,
Examples thereof include a phenyl group and a tolyl group, and those having 7 or less carbon atoms are particularly preferable.

Specific examples of the compounds of the present invention are shown below, but the scope of the present invention is not limited to these.

[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

[Chemical 8]

These compounds can be obtained by the Knoevenagel reaction of a benzaldehyde derivative with an azolidine-2,4-dione derivative. As the solvent, alcohols, ethers, nitriles,
Amides and the like can be used, and an acid or a base can be used as a catalyst. Reaction temperature is -100 ℃
Can be carried out in the range of up to 150 ° C, preferably -78.
It is in the range of ℃ to 100 ℃.

[0023]

EXAMPLES Next, the present invention will be explained in detail based on examples, but the present invention is not limited to these. Example 1 Synthesis of Compound 1 1) Synthesis of (S) -2-methyl-1-butyl-p-toluenesulfonate (S) -2-Methyl-1-butanol 19.1 g (0.2
2 mol) and tosyl chloride 41.9 g (0.22 mol)
Was placed in a three-necked flask and 31.6 g (0.40 mol) of pyridine was added while keeping the temperature of the reaction solution below 0 ° C under ice cooling.
Was added dropwise, and the mixture was stirred as it was for 3 hours. Next, concentrated hydrochloric acid 40 ml
A solution of 80 ml of water and 80 ml of water was added dropwise, and the mixture was extracted with methylene chloride. After drying over magnesium sulfate, methylene chloride was distilled off to obtain the desired product. Yield 52g (98% yield)

2) Synthesis of p-[(S) -2-methyl-1-butoxy] benzaldehyde (S) -2-methyl-1-butyl-p-toluenesulfonate 52 g (0.22 mol), p-hydroxy Benzaldehyde 26g (0.22mol), sodium hydroxide 1
To 0.3 g (0.26 mol), 100 ml of N, N-dimethylformamide was added, and the mixture was heated with stirring at 100 ° C. for 3 hours. After cooling to room temperature, water was poured into the reaction mixture, extracted with ethyl acetate, and then purified by silica gel column chromatography (eluent ethyl acetate / n-hexane = 1/4) to obtain the desired product. Yield 32g (Yield 78%)

3) Synthesis of compound 1 p-[(S) -2-methyl-1-butoxy] benzaldehyde 9.6 g (0.05 mol), 3-methyl-thiazolidine-2,4-dione 6.6 g (0 (0.05 mol) and 30 ml of ethanol was added to 1 drop of piperidine, and the mixture was heated under reflux for 5 hours. After allowing to cool to room temperature, the precipitated crystals were collected by filtration and recrystallized with ethanol to obtain the desired product. Yield 10g (Yield 65%) Melting point 101 ° C

¹ H-NMR

[0027]

[Chemical 9]

[0028] _{δppm Jin Hz (CDCl 3) 0.97} (t, J = 8,3H, H a) 1.02 (d, J = 7,3H, H e) 1.28 (m, 1H, H b ) 1.57 (m, 1H, H b) 1.90 (m, 1H, H c) 3.24 (s, 3H, N-CH 3) 3.80 (dd, Jgem = 6, Jvic = 2, 1H, H
^d ) 3.87 (dd, Jgem = 6, Jvic = 1,1H, H
^d ) 6.99 (d, J = 10,2H, 1,2-H) 7.48 (d, J = 10,2H, 3,4-H) 7.89 (s, 1H, -CH =) UV-spectrum (in ethanol) λmax = 346 nm Elemental analysis value CHN calculated value 62.93 6.27 4.59 Measured value 62.93 6.24 4.58

Example 2 Synthesis of Compound 2 Synthesis was carried out in the same manner as in Compound 1.

¹ H-NMR

[0031]

[Chemical 10]

[0032] _{δppm Jin Hz (CDCl 3) 0.97} (t, J = 8,3H, H a) 1.02 (d, J = 7,3H, H e) 1.28 (m, 1H, H b ) 1.57 (m, 1H, H b) 1.90 (m, 1H, H c) 3.80 (dd, Jgem = 6, Jvic = 2,1H, H
^d ) 3.87 (dd, Jgem = 6, Jvic = 1,1H, H
^d ) 6.99 (d, J = 10,2H, 1,2-H) 7.48 (d, J = 10,2H, 3,4-H) 7.73 (s, 1H, -CH =) 8.58 (br, 1H, N-H) UV-spectrum (in ethanol) λmax = 344nm Melting point 150 ° C Elemental analysis value CHN Calculated value 61.84 5.88 4.81 Measured value 61.71 5.84 4.74

Example 3 Synthesis of Compound 3 Synthesis was carried out in the same manner as in Compound 1.

¹ H-NMR

[0035]

[Chemical 11]

[0036] _{δppm Jin Hz (CDCl 3) 0.97} (t, J = 8,3H, H a) 1.02 (d, J = 7,2H, H e) 1.27 (m, 1H, H b ) 1.28 (t, J = 8,3H , H g) 1.60 (m, 1H, H b) 1.88 (m, 1H, H c) 3.80 (dd, Jgem = 6, Jvic = 2,1H, H
^{d) 3.85 (q, J =} 8,3H, H f) 6.99 (d, J = 10,2H, 1,2-H) 7.48 (d, J = 10,2H, 3,4 -H) 7.88 (s, 1H, -CH =) UV-spectrum (in ethanol) λmax = 347 nm Melting point 83 ° C Elemental analysis value CHN calculated value 63.92 6.63 4.39 Measured value 63.74 6.63 4.32

Example 4 Synthesis of Compound 8 Synthesis was carried out in the same manner as in Compound 1.

¹ H-NMR

[0039]

[Chemical 12]

[0040] _{δppm Jin Hz (CDCl 3) 0.97} (t, J = 8,3H, H a) 1.00 (d, J = 7,2H) 1.28 (m, 1H, H b) 1. 90 (m, 1H, H ^c ) 3.82 (dd, Jgem = 6, Jvic = 2, 1H, H
^d ) 3.88 (dd, Jgem = 6, Jvic = 1,1H, H
^d ) 7.01 (d, J = 10,2H, 1,2-H) 7.50 (d, J = 10,2H, 3,4-H) 8.78 (br, 1H, N-H) UV-spectrum (in ethanol) λ max = 368 nm Melting point 155 ° C. Elemental analysis value C H N calculated value 61.84 5.88 4.81 Measured value 61.76 5.86 4.81

Example 5 Synthesis of Compound 13 1) Synthesis of 5- [4-{(S) -2-methyl-1-butoxy} benzylidene] -2-methylthiooxazolin-4-one Compound 7.2 g above (0.025 mol), 3.4 g (0.025 mol) of potassium carbonate and 1 part of acetonitrile
Add 00 ml and stir at room temperature with stirring methyl iodide 3.
5 g (0.025 mol) was added dropwise, and further 30 at room temperature.
Stir for minutes. After completion of the reaction, the reaction mixture was poured into 1 liter of water, the precipitated crude crystals were collected by filtration and recrystallized with isopropanol to obtain the desired product. Yield 7.0 g (92% yield)

2) Synthesis of compound 13 5- [4-{(S) -2-methyl-1-butoxy} above
12% and 87 ml of hydrochloric acid were added to 7.0 g (0.023 mol) of benzylidene] -2-methylthiooxazolin-4-one, and the mixture was heated with stirring at 50 ° C. for 30 minutes. After the reaction was completed, the precipitated crystals were collected by filtration and recrystallized with isopropanol to obtain the desired product. Yield 4.0 g (yield 63%) Melting point 133 ° C. UV-spectrum (in ethanol) λmax = 324 nm ¹ H-NMR

[0043]

[Chemical 13]

[0044] _{δppm Jin Hz (CDCl 3) 0.98} (t, J = 8,3H, H a) 1.01 (d, J = 7,3H, H e) 1.28 (m, 1H, H b ) 1.58 (m, 1H, H b) 1.88 (m, 1H, H c) 3.81 (dd, Jgem = 6, Jvic = 2,1H, H
^d ) 3.88 (dd, Jgem = 6, Jvic = 1,1H, H
^d ) 6.77 (s, 1H, -CH =) 6.95 (d, J = 10,2H, 1,2-H) 7.71 (d, J = 10,2H, 3,4-H) 8.67 (br, 1H, N-H) Elemental analysis value CHN calculated value 65.44 6.22 5.09 measured value 64.99 6.20 5.16

Example 6 Synthesis of Compound 14 2.1 g (7.6 mmol) of Compound 13 above, 1.1 g (7.6 mmol) of potassium carbonate, 1.3 g of methyl iodide.
20 ml of acetonitrile was added to (9.2 mmol) and the mixture was heated under reflux for 2 hours. After completion of the reaction, the reaction mixture was poured into 1 liter of water, the precipitated crude crystals were collected by filtration and recrystallized with isopropanol to obtain the desired product. Yield 1.5 g (68% yield) Melting point 105 ° C. UV-spectrum (in ethanol) λmax = 327 nm ¹ H-NMR

[0046]

[Chemical 14]

[0047] _{δppm Jin Hz (CDCl 3) 0.98} (t, J = 8,3H, H a) 1.05 (d, J = 7,3H, H e) 1.30 (m, 1H, H b ) 1.60 (m, 1H, H b) 1.88 (m, 1H, H c) 3.20 (s, 3H, N-CH 3) 3.81 (dd, Jgem = 6, Jvic = 2, 1H, H
^d ) 3.88 (dd, Jgem = 6, Jvic = 1,1H, H
^d ) 6.78 (s, 1H, -CH =) 6.95 (d, J = 10,2H, 1,2-H) 7.70 (d, J = 10,2H, 3,4-H) Elemental analysis value C H N calculated value 66.42 6.62 4.84 measured value 66.28 6.58 4.94

As will be apparent from the examples described below, the nonlinear optical material of the present invention is particularly useful as a material for converting the wavelength of laser light. However, the application of the nonlinear optical material of the present invention is not limited to the wavelength conversion element, and it can be used for any element as long as it utilizes the nonlinear optical effect. As specific examples of the element in which the nonlinear optical material of the present invention can be used, in addition to the wavelength conversion element, an optical bistable element (optical storage element, optical pulse waveform control element, optical limiter, differential amplification element, optical transistor, A
/ D conversion element, optical logic element, optical multivibrator,
(Optical flip-flop circuit, etc.), optical modulator, phase conjugate optical element, etc. The compounds of the present invention are, for example, in the form of powders, host lattices (polymers, inclusion compounds, solid solutions,
It is used as a nonlinear optical material in various forms such as the form of inclusion of molecules in liquid crystal), the form of thin layer deposited on a support (Langmere-jet film, etc.), the form of single crystal, the form of solution, etc. be able to.

The compound of the present invention can also be used in the form of a pendant linked to a polymer, polydiacetylene or the like. Details of these methods are described in, for example, the work of the above-mentioned William (DJ Williams).
Examples of the laser light source used as the fundamental wave include those shown in Table 1. The wavelength of the fundamental wave is not limited except for the influence of absorption of the material. This is due to the fact that Laser & Optonics (Laser & Opt
ronics) p. 59 (published in November 1987).

[0050]

[Table 1]

Next, it will be shown that the compound of the present invention is useful as a nonlinear optical material.

Example 7 The measurement of the second harmonic generation was carried out by SK Kurt.
z), by TTPerry, Journal of Applied Physics (J.Appl.Phy)
s.) 39, page 3798 (published in 1968) according to the method described in the present invention. The measurement was performed by the apparatus shown in FIG.

That is, in the measurement, a pulsed YAG laser beam (λ = 1.064 μm, beam diameter ≈1 mmφ, peak power ≈10 Mw / cm ² ) was used as the fundamental wave, and the measurement was performed using the evaluation device shown in FIG. The intensity of two harmonics was measured. The measurement was performed by relative comparison with the intensity of the second harmonic of urea. When the strength was weak, visual observation was performed. In particular,
Light emission due to two-photon absorption of the fundamental wave (mainly yellow and red light emission)
In order to distinguish between the second harmonic and the
Only harmonics are measured. Further, the measurement by the powder method is mainly for judging the presence or absence of non-linearity of the substance, and the intensity ratio is a reference value of the magnitude of non-linearity. The results are shown in Table 2.

[0054]

[Table 2]

[0055]

[Chemical 15]

[0056]

From the examples, the compounds of the present invention are
It is active and becomes an excellent blue SHG element. Further, it can be used as a wavelength conversion element by the method described below. 1. Single crystal of the above compound in the core of the fiber,
It is possible to create a wavelength conversion element using glass as a clad material and input YAG laser light to generate the second harmonic. Further, as another method, it is possible to generate a second harmonic wave by forming a waveguide type wavelength conversion element in the same manner. As the phase matching method at this time, the Thierenkov radiation method is used. However, the present invention is not limited to these, and waveguide-guided phase matching is also possible. The wavelength converted wave is not limited to the second harmonic, but is also used for generating the third harmonic, sum and difference frequencies.

2. Next, the above compound can be made into a single crystal, a bulk single crystal can be cut out therefrom, and YAG laser light can be input to generate the second harmonic thereof. Angle phase matching is used as the phase matching method at this time. These bulk single crystals can be used not only outside the cavity of the laser but also inside the cavity of a solid-state laser such as an LD-excited solid-state laser to improve the wavelength conversion efficiency. Further, the wavelength conversion efficiency can be improved also by disposing it in the resonator of the external resonator type LD. Bridgman method, solvent evaporation and the like are used for the above single crystallization. The wavelength-converted wave is not limited to the second harmonic, but is also used for generating the third harmonic and the sum difference frequency.

[Brief description of drawings]

FIG. 1 shows a measuring apparatus of a powder method.

[Explanation of symbols]

 1 powder sample 2 fundamental wave cut filter 3 spectroscope 4 photomal 5 amplifier 6 wavelength 1.064 μm 7 0.532 μm

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C07D 277/36 277/40 277/42 G02F 1/35 504 9316-2K 1/37 9316-2K

Claims (5)

[Claims] 1. A compound having an asymmetric carbon atom represented by the following general formula (I). General formula (I) 2. A non-linear optical material comprising the compound according to claim 1. 3. A compound according to claim 1, wherein R is represented by formula (a). Formula (a): 4. A non-linear optical material comprising the compound according to claim 3. 5. A method of converting a light wavelength using the organic nonlinear optical material according to claim 2 or 4 as a nonlinear optical material when converting a light wavelength using a laser beam and a nonlinear optical material. .