JPH0380231A - Nonlinear optical material - Google Patents

Abstract

PURPOSE:To provide the above material with which a large nonlinear susceptibility can be expected as intramolecular resonance can be induced by incorporating a specific 1, 3-diketone deriv. into this material. CONSTITUTION:The 1, 3-diketone deriv. expressed by formula I is incorporated into this material. In the formula I, R<a> may be different or the same and the org. substituent selected from an amino group, substd. amino group substd. with a group having 1 to 12C, cyclic amino group, alkyl group, etc.; n denotes the number thereof and is 1 to 5; R<b> is the org. substitutent same as R<a>; m denotes the number thereof an is 0 to 5. Rings A, B denote an arom. hydrocarbon group or heteroarom. group. The 1, 3-diketone deriv. is the equil. stte of a keto form and enol form and biases largely to the enol form. The resonance effect by the interaction of charge transfer is increased in this way and the nonlinear optical sensitivity is increased.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a nonlinear optical material used for optical information, optical communication, etc., and more particularly to an organic nonlinear optical material comprising a 1°3-diketone derivative. . For example, it can be used in wavelength conversion elements for semiconductor lasers, measuring instruments, information transmission through optical fibers, and the like.

(Prior Art) Laser light has monochromatic, directional, and coherent properties, so it exerts specific interactions with substances.

This interaction is known as a nonlinear optical effect, and causes phenomena such as harmonic generation, Kerr effect, optical mixing, and IJ book width. In particular, second-order and third-order nonlinear optical effects can be expected to have a relatively large nonlinear susceptibility, so information processing,
It can be applied to optical communications, etc.

Conventionally, KDP (KH2PO4) was used as a nonlinear optical material.
= ADP (NH4R3PO4)L i Inorganic materials such as NbO3 have been used and applied to some measuring instruments. However, it is difficult to obtain high-purity single crystals, they are expensive, they have poor light damage resistance, they are deliquescent, and their nonlinear optical susceptibility is low, making it difficult to apply them to light-related applications. .

In recent years, since it has been discovered that organic materials have superior nonlinear optical effects compared to inorganic materials, organic materials, which have a high degree of freedom in molecular design, have attracted attention. In particular, 2
-π such as methyl-4-nitro-aniline
C-T (Charge-Trans
It has been thought that large nonlinear susceptibility can be expected because fer) type organic compounds induce large molecular hyperpolarizability.

However, the crystal structure of organic compounds is determined by intermolecular interactions, ie, intermolecular forces such as hydrogen bonds and van der Waals interactions. In the case of C-T type molecules having strong electron-withdrawing substituents and electron-donating substituents as described above, strong dipole-dipole interactions between molecules work to stabilize the crystal, that is, bimolecular dipoles. It is easy to form a crystal structure in which the children cancel each other out. Such a crystal structure is a centrosymmetric crystal as a molecular assembly, and is therefore nonlinearly optically inactive.

Therefore, the following method is used as a means of disrupting the central symmetry of such a crystal structure. In other words, substituents with large hydrogen bonding properties that can control molecular orientation such as hydroxyl groups, carboxyl groups, and amino groups, bulky substituents that can significantly change the molecular structure due to steric hindrance, and optical activities such as amino acids or amino acid derivatives. In addition to substituents (D or monomer), methods of inducing non-centrosymmetric properties have been implemented by conjugation, such as complexes with clathrate compounds.

Further, the following points are necessary and sufficient conditions for the application of the second-order nonlinear optical material as a nonlinear optical element.

■ Extremely high nonlinear optical susceptibility ■ Fast optical response speed ■ Excellent laser light transparency ■ Light damage resistance ■ Phase matching ■ Crystallinity (possibility of single crystal growth, etc.) ■ Mechanical strength ■ Processing ■ Chemically stable, such as moisture resistance [Phase] Difficult to sublimate (problem to be solved by the invention) High hyperpolarizability, achieved by introducing hydrogen-bonding substituents and optically active substituents NP without central symmetry
In the case of C-T type compounds such as P and molecules with long π-electron conjugation, large second-order nonlinear susceptibility can be expected, but they have drawbacks such as lack of transparency. Therefore, there was a drawback that the usable wavelength range was limited.

(Means for Solving the Problems) The present invention was carried out to solve the above problems, and provides an organic compound that has a large nonlinear optical susceptibility and is excellent in transparency and properties. .

In order to achieve the above object, the present invention has the following configuration. That is, the present invention provides 1 represented by the following general formula [1]
, a 3-diketone derivative.

(In the formula, Ra may be different or the same, and may include an amino group, a substituted amino group substituted with a group having 1 to 12 carbon atoms, a cyclic amino group, an alkyl group, a halogen-substituted alkyl group, an alkoxy group, a halogen-substituted alkoxy group) , is an organic substituent selected from mercaptoalkoxy groups, n indicates its number and is 1 to 5, Rh is the same organic substituent as R', and m indicates its number and is O to 5. be.

Rings A and B represent an aromatic hydrocarbon group or a heteroaromatic group. ).

The 1,3-diketone derivative of the present invention is in an equilibrium state between the keto type and the enol type, and is largely biased toward the enol type. (Formula [2]) Keto type Enol type This intramolecular enol hydroxyl group is SHG in the crystal state
It has the characteristics of a functional organic substituent (orientation control group) that induces non-centrosymmetric properties, which is a sufficient condition for activity, and also has an electron-donating group and an electron-withdrawing group in the molecule. Therefore, optical nonlinearity can be increased. Introducing an electron-donating group at the ortho-position or the rose-position of the aromatic ring is particularly effective because the resonance effect due to charge transfer interaction becomes larger.

In the present invention, in addition to the organic substituent R''+R'', other substituents may be appropriately introduced as necessary to finely adjust the performance of the compound of the present invention.

Other substituents referred to in the present invention include amino, monomethylamino, monoethylamino, dimethylamino, diethylamino, n-butylamino, t-
Ami7 groups such as butylamino groups, m-shaped amino groups such as piperidino, pyrrolidino, and morpholino, normal alkyl groups having 1 to 12 carbon atoms, alkyl groups such as t-butyl groups, alkyl groups containing optically active carbon, carbon A normal alkoxy group having a number of 1 to 12, a t-butoxy group, an alkoxy group containing an optically active carbon, a mercapto normal alkoxy group having a carbon number of 1 to 12, an alkoxy group such as a t-thiobutoxy group, a mercapto containing an optically active carbon. In addition to alkoxy groups, hydroxy groups, mercapto groups, and halogens can be used, and as electron-withdrawing groups, nitro groups, cyano groups,
Trifluoromethyl groups, isocyanate groups, sulfonyl groups, carboxyl groups, carboxylic acid ester groups, acetylamino groups, halogens, and the like can be used.

The aromatic hydrocarbon group and heteroaromatic ring referred to in the present invention are a benzene ring, a naphthalene ring, an anthracene ring, a biphenyl ring, a terphenyl ring, a thiazole ring, a furan ring, a thiophene ring, a pyrrole ring, a pyridine ring, a pyrimidine ring, and a pyrazine ring. ring, pyridazine ring, triazine ring, tetrazine ring, etc. can be used.

As a method for synthesizing the organic nonlinear optical material of the present invention.

For example, equations (3) and (4) can be considered.

In the following margins, that is, in formula (3), the chalcone compound can be synthesized by (a) a process for synthesizing a chalcone compound by a Thalisen-Schmidt dehydration condensation reaction, (b) a process for bromination, and (C) a process for methoxylation and then demethylation. (In the Φ formula (a)
Synthesis process of benzoylacetone (b) It can be synthesized by a reaction process between a benzoic acid ester and a benzoylacetone derivative.

(Example) Hereinafter, the present invention will be explained in more detail according to Examples.
The present invention is not limited to these examples.

Second harmonic generation (SHG) is measured using the powder method (S).
Kurz, T, T, PerrY+, LL3798 (
1988)). The light source used for measurement was Nd
; YAG laser, fundamental wavelength 10B4nw+
A powder sample is irradiated with a laser beam of
32 nm) was detected using a spectrometer.

A schematic diagram of the second harmonic generator is shown in FIG.

The powder samples used were toluene (a) and ethyl acetate (b).
, acetone (C), ethanol (d), hexane (e)
, purified by recrystallization with methanol (f) was used.

300 +wR-EtOH20011 in Ronas flask
Add 1Q and 6.46g of 4-methoxyacetophenone (
43,081 mM) was added and completely dissolved.

After adding 40ml of NaOH aqueous solution (1,72g/H20, 7.97ml of p-bromobenzaldehyde at room temperature
g (43,081 mM)/EtOH solution was added dropwise little by little. The deposited precipitate was collected under reduced pressure and mixed with 50 l of distilled water.
After thoroughly washing with IIQ three times, it was dried by heating under reduced pressure. The obtained chalcone compound was purified by silica gel column chromatography.

Yield was 13.2g (97%). This product was recrystallized from ethanol. The product was confirmed using nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy.

10 g of chalcone compound (31,5
457mM) was suspended in carbon disulfide and cooled (
0° C.) 1.7 cc of bromine solution was added dropwise little by little. After reacting at 0°C for 3 hours, returning to room temperature and reacting at 25°C for 1 hour, the reaction mixture was collected under reduced pressure and washed with MeOH. 14.0 g (yield: 93%) of the obtained crude white crystals was purified by column chromatography using a toluene developing solvent, and then purified by recrystallization using a solvent.

The compound was confirmed using nuclear magnetic resonance spectrum and infrared absorption spectrum.

Soranaku LL The dibrome compound to, og (20,9
843mM) in EtONa/EtOH solution (Na/Et
After heating and refluxing for 2 hours, the mixture was returned to room temperature, 3.5w of concentrated hydrochloric acid and Q were added, and the mixture was heated and refluxed for 30 minutes. After the temperature was returned to room temperature, the precipitated crude crystals were collected under reduced pressure. This 1,3-
8.5 g (yield: 93%) of the crude crystals of the diketone derivative was purified by column chromatography using activated alumina/silica gel, and then purified by recrystallization using various solvents. The compound was confirmed using nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy.

When the SHG intensity of the obtained 1,3-diketone derivative (Nal) was measured by the above method, it was 35.0 (acetone), 23.0 (EtOH), and 19.0 with respect to urea.
5 (toluene), 2.4-(ethyl acetate), 23.2
It was possible to confirm the generation of SHG (n-hexane).

4-Mercaptomethylacetophenone CB (0.241 mM) was placed in a 500 wiQ-ronas flask, and 300 mQ of EtOH was added to completely dissolve it. At room temperature, NaOH aqueous solution (NaOH2, 4g/
H2050mR) was added thereto, and 8.2g (60.241mM) of p-methoxybenzaldehyde was added dropwise little by little. 16.6 g (yield: 97%) of the precipitated precipitate was collected under reduced pressure, washed four times with 50 raQ of distilled water, and purified by recrystallization with hexane. The compound was confirmed using nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy.

15.0g of chalcone compound obtained in step (A)
2,817 mM) was dissolved in 100 J of carbon disulfide, and 5 mQ of bromine was added dropwise little by little at 3°C under a nitrogen stream. 3
After reacting at 5°C to 5°C for 2 hours, the temperature was returned to room temperature (26°C) and the reaction was continued for 1 hour. Distilled water 100 waQ and H2
CQ, 270111! Add 3 with CH2CQ250J
Extracted twice.

The CH2CL2 extract solution was dried over anhydrous magnesium sulfate.

After removing CH2 (1!2) and anhydrous magnesium sulfate, 22.4 g of white crystals (yield 96%) were obtained. The obtained compound was thoroughly dried and then used in the next reaction. Confirmation of the compound was performed using nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy.

20 g (45,045
(mM) under a nitrogen stream with NaOCH3/C prepared in advance.
H30H (Na; 2,072 g/CH30H30
0+all) solution, and heated under reflux for 2 hours. After the temperature was returned to room temperature, 7 Wfl of concentrated hydrochloric acid was added, and the mixture was further heated under reflux for 1 hour. The reaction solution was cooled to 5°C, and the precipitated crystals were collected under reduced pressure. The obtained crude crystals (white) were purified by column chromatography using toluene as a developing solvent (12
．． After 9 g (yield: 96%), recrystallization purification was performed using various solvents.

When the SHG intensity of the compound M2 was measured by the same method as in Example 1, it was found to be 28.3 (Toluene),
32.6 (ethyl acetate), 11.1 (EtOH)
, 17.8 (acetone), 5.3 (hexane) SH
G activity could be confirmed.

1-1-3-Chloro-4-methoxyacetic acid phenone 10g (5
4,2152mM) was added to a 500wxQ-ronas flask and dissolved in 400mM EtOH (!).

NaOH aqueous solution (NaO
H; 2.18g/H20; After adding 30+ml, 4
-methoxybenzaldehyde 7.38g (54,21
52mM) E tOH solution was added dropwise. After reacting at room temperature for 3 hours, the precipitated cream-colored crystals were collected under reduced pressure and purified by column chromatography using CH20g2 as a developing solvent to obtain 13.8 g (yield: 89%) of cream-colored crystals. The product was further purified by recrystallization using hexane, dried under reduced pressure under heat, and then used as it was in the next reaction.

The compound was confirmed using nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy.

12.0 g of chalcone compound obtained in step (A) (3
9,6759mM) with 150% carbon disulfide under nitrogen stream,
After cooling to 3-5° C., bromine 4.5- was added dropwise. 2.5 hours at 3-5℃, 1 at room temperature (about 26℃)
After stirring for an hour, the crystals were separated under reduced pressure and added to cold M e OH.
After washing with
g (91%) was obtained.

The compound was confirmed using nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy.

15.4 g (33,3
008mM) prepared in advance
H2OH solution (Na; 1.53g/400m
Q CH30H) and heated under reflux for 2 hours. After 2 hours, the temperature was returned to room temperature, 6 mQ of concentrated hydrochloric acid was added, and the mixture was further heated under reflux for 1 hour.
After adding m+(! and stirring for 20 minutes, CH2Cl22501
Extracted 4 times using 1 (!).

The CH2CQ2 extraction solution was dried over anhydrous magnesium sulfate and the solvent was removed to obtain 11.3 g of crude crystals.

This was purified by column chromatography using toluene as a developing solvent to obtain 9.7 g (92%) of white crystals.

This was recrystallized and purified using various solvents.

The SHG intensity of the obtained recrystallized purified Na3 was measured in the same manner as in Example 1, and the SHG intensity was 2.6 (To 1u
ene), 5.7 (ethyl acetate), 1.9 (EtO
H) SHG activity of 7.1 (hexane) could be confirmed.

3-Bromo-4-methoxyacetophenone 10g (4
3,8881mM) was placed in a 300 vsQ-ronas flask, and EtOH 300- was added to completely dissolve it.

NaOH aqueous solution (NaOH; t, 75 g/HaO; 3
After adding 0 mN), an EtOH solution of 7.2 g (43,8881 mM) of 2,4-dichlorobenzaldehyde was added dropwise. . After stirring for 3 hours at room temperature, the precipitated crystals were collected under reduced pressure. Furthermore, column chromatography purification was performed using toluene as a developing solvent, and 15.7 g (yield 94%)
Cream-colored crystals were obtained. This was dried by heating under reduced pressure and used as it was in the next reaction.

The compound was confirmed using nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy.

14.0 g (38.4 g) of the chalcone compound obtained in step (A)
583mM) was placed in a 300-trilo flask, and carbon disulfide was added to form a suspension. After cooling to 3 to 5°C under a nitrogen atmosphere, 5 yaQ of bromine was added dropwise little by little. 3-5
After reacting at ℃ for 2 hours and at room temperature for 1 hour, the crystals were collected under reduced pressure. After washing the crystals with hexane, M e OH
The product was recrystallized and purified to obtain 18.11 g (yield 91%) of white plate-like crystals.

18.0 g (33,088 g) of dibrome compound obtained in step (B)
2mM) was added in advance to a prepared NaOMe/MeOH solution (Nano, 76g/EtOH400weff) and heated under reflux for 3 hours. After returning the temperature to room temperature, concentrated hydrochloric acid 8- was added and the mixture was further heated under reflux for 1 hour. After confirming the end point of the reaction by thin layer chromatography, distilled water
w+R and CH2CN210011 (!) were added and stirred for 1 hour.

After extracting three times with CH2CN27011 (!), it was dried with anhydrous magnesium sulfate. The desiccant and solvent were removed, and 1
4.8 g of crude crystals were obtained. This was purified by column chromatography using Toluene as a solvent, and 12.4 g (yield: 9
4%) of cream-colored crystals were obtained. This was recrystallized and purified using various organic solvents and used as a sample for SHG intensity measurement.

Compound 4 was confirmed by nuclear magnetic resonance spectrum and infrared absorption spectrum.

When the SHG intensity of the various crystals obtained was measured, 3
7.8 (Toluene) 21.1 (Ethyl acetate)
, 19.5 (EtOH), 18.0 (MeOH),
The SHG activity of 24.4 (Acetone) could be confirmed.

The following synthesis was carried out in the same manner as in Examples 1 to 4, and Examples 1 to 4 were synthesized in the same manner as in Examples 1 to 4.
SHG was measured in the same manner as in 4. The results are shown in Tables 1-4.

1-(4-methoxyphenyl)-3-(4-chlorophenyl)-1,3-diketone (Nl15, Example 5), 1
-(4-methoxyphenyl)-3-(3-bromo-4-
Mercaptomethylphenyl)-1,3-diketone (Na
p, Example 6), 1-(4-methoxyphenyl)-3-
(3-chloro-4-mercaptophenyl)-1,3-diketone (positive 7. Example 7), 1-(4-methoxyphenyl)-3-(3-bromo-4-methoxyphenyl)-1
,3 diketone (N18. Example 8), 1-(4-methoxyphenyl)-3-(3-fluoro-4-methoxyphenyl)-1,3 diketone (N[19° Example 9), 1-
(4-mercabutomethylphenyl)-3-(4-(N,
N-dimethylamino)phenyl)-1,3 diketone (Nl
110. Example 10), 1-(3-chloro-4-methoxyphenyl)-3-(3,4-dimethoxyphenyl)-
1,3 diketone (N[Lil, Example 11).

4-((S)-(-)-2-methyl-1 derived from optically active (S)-(-)-2-methyl-1-butanol)
-butoxy)acetophenone 10.0g (48,54
38mM) was dissolved in EtOH300ymQ, and NaO
H aqueous solution (NaOH; 1,94 g/H2040
va9) was added. Then, 3.82 g of 4-chlorobenzaldehyde E (4B, 5435 mM) was added dropwise at room temperature. After stirring at room temperature for 4 hours, the precipitated crystals were collected under reduced pressure and thoroughly washed with distilled water to give cream-colored crystals with a concentration of 14.8
g (93%) was obtained.

After sufficient heating and drying under reduced pressure, it was used in the next reaction.

The compound was confirmed using nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy.

14.0 g of chalcone compound obtained in step (a) (4
2,8244 mM) was suspended in 300 IIQ of carbon disulfide, and after cooling to 3 to 5°C under a nitrogen stream, 7 mQ of bromine was added dropwise little by little. After stirring at 3 to 5°C for 3 hours and at room temperature (25°C) for 1 hour, the crystals were collected under reduced pressure and thoroughly washed with hexane. The obtained crystals were purified by recrystallization with hechitin,
19.8 g (yield 94%) of white flocculent crystals were obtained.

The obtained crystals were thoroughly dried by heating under reduced pressure and used in the next reaction.19.0 g of dibrome (38,8
985mM) was prepared in advance in NaOMe/MeOH (
Na: 0.9 g/M e was added to the OH400va (1) solution and heated under reflux for 3 hours. After returning to room temperature, concentrated hydrochloric acid 121Q was added and heated under reflux for 1 hour. Distilled water 8
After adding 0 wxQ and CH2 (1!2100-) and stirring for 30 minutes, the mixture was extracted four times with CH2CQ2501112. After drying over anhydrous magnesium sulfate, the desiccant and solvent were removed to obtain yellow crude crystals. Purified by column chromatography as a developing solvent to obtain 13.0 g of white crystals.
(yield 97%). This was recrystallized with various organic solvents.
It was used as a sample for SHG intensity measurement.

Compound? ! 112 was confirmed using nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy.

SHG intensity measurements of samples prepared with various solvents showed 30.1 (Toluene), 40.3 (Ethyl acetate), 9.1 (EtOH), 8.8 (Me
OH), 20.8 (Acetone), and 30.0 (Hexane) SHG activities could be confirmed.

Note that the optically active 4-((S)-(-) used in this example
Compounds such as -2-methyl-1-butoxy)acetophenone can be obtained by the synthesis method of the following formula [5] or [6].

Margin below Real” 1 left Uni 1 4-((2s) derived from L-inleucine.

3s)-2-chloro-3-methyl-1-butoxy)acetophenone Log (39,3004mM) at 300+
Completely dissolve in QEtOH and add NaOH aqueous solution (NaOH
; 1.57 g/HzO; 30 mQ) was added. Next, 5.35 g of p-methoxybenzaldehyde (39,3
A 382 mM) EtOH solution was added dropwise. After reacting at room temperature for 3 hours, the precipitated crystals were collected under reduced pressure and thoroughly washed with distilled water.

After drying under heat under reduced pressure, column chromatography purification was performed using Toluene as a developing solvent to obtain 13.2 g (yield: 94%) of cream-colored crystals.

After recrystallizing and purifying the crystals with EtOH and thoroughly drying them,
It was used directly in the next reaction.

13.0 g (38,5 g) of the chalcone derivative obtained in step (a)
733mM) was added to 200.9ml of carbon disulfide solution to form a suspension solution. The mixture was cooled to 3 to 5°C under a nitrogen stream, and bromine 7- was added dropwise little by little. 2 hours at 3-5℃, room temperature (26℃)
After stirring for 1 hour, add 100mR/CH2 of distilled water.
It was poured into a mixed solution of CQ2100wrQ and stirred for 1 hour.

After extraction with CH2CQ250-3 times and drying with anhydrous magnesium sulfate, the desiccant and solvent were removed to obtain crude crystals.

The crystals were purified by column chromatography using Toluene as a solvent and recrystallized with EtOH to produce 18.8 g of white crystals (
97%) of dibrome compound was obtained. The compound was confirmed using nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy.

18.0 g (33,8
NaOCH3/CH30 prepared in advance (059mM)
H(Na; 1.56g/CH30H; 300+v
<') and heated under reflux for 3 hours. The temperature was returned to room temperature, 8 mQ of concentrated hydrochloric acid was added, and the mixture was heated under reflux for 1 hour. Return to room temperature and add 501g of distilled water and C (!280111!)
After stirring for a minute, the mixture was extracted three times with CH2CQ250- and dried over anhydrous magnesium sulfate. The drying agent and solvent were removed to obtain yellow crude crystals. This was purified by column chromatography using Toluene as a developing solvent to give 12.5g (yield 95%).
White crystals m13 were obtained.

The obtained crystals were purified by recrystallization using various organic solvents and used as samples for SHG intensity measurement.

When the SHG intensity of each recrystallized purified product was measured according to the above, the results were 37.7 (To 1uene) and 28.2 (
ethyl acetate), 29.0 (Acetone).

~ The following synthesis was performed in the same manner as Examples 12 and 13 to obtain Example 1.
SHG was measured in the same manner as in 2-13. The results are shown in Tables 1-4.

1-C4-((-)-2-methylbutoxy)phenyl)-3-(4-bromophenyl)-1,3-diketone (N1114. Example 14), 1-[:4-((-)-
2-methylbutoxy)phenyl]-3-(3-bromo-
4-methoxyphenyl)-1゜3-diketone (N111
5. Example 15), 1-[4-((-)-2-methylbutoxy)phenyl-3-phenyl-1,3-diketone (NIllB, Example 16), 1-(4-((-)-
2-methylbutoxy)phenyl)-3-(3-fluoro-4-ethoxyphenyl-1,3-diketone (N117)
．． Example 17), 1-[3-chloro-4-((-)-2
-methylbutoxy)phenyl)-3-(2,8-dichlorophenyl)-1,3-diketone (N118, Example 1
8), 1-[3-bromo-4-((-)-2-methylmercaptobutoxy)phenyl)-3-(3,5-dimethoxyphenyl)-1,3-diketone (Na19. Example 19), 1-[3-fluoro-4-((-)-2-methylbutoxy)phenyl] -3-(3-chloro-4-
Mercaptomethoxyphenyl-1,3-diketone (NI
L20, Example 20), 1-[2-chloro-4-((-
)-2-methylmercaptobutquin) phenyl)-3-
(2,6-dimethoxyphenyl)-1,3-diketone (
Na21. Example 21), 1-1-((-)-2-methylbutoxy)phenyl]-3-(3-chloro-4-ethoxyphenyl)=1,3-diketone (Nn22. Example 22), 1- (2-((-)-2-methylbutoxy)phenyl]-3-(3,5-dimethoxyphenyl)-1,
3-diketone (Na23.Example 23), 1-(:4-
((2s,3s)-2-chloro-3-methyl-1-pentyloxy)phenyl)-3-(3-10rho-4-methoxyphenyl)-1,3-diketone (Example 24)
4) ,1-[4-((2s.

3s) -2-bromo-3-methyl-1-pentyloxy)phenyl)-3-(4-mercaptomethoxyphenyl)-1,3-diketone (Na25. Example 25), 1
-[:4- ((2s)-2-chloro-3-methyl-1
-butoxy)phenyl]-3-(2,4-dichlorophenyl)-1,3-diketone (Na2B, Example 2B)
, 1-(3-((2s)-2-fluoro-3-methyl-butoxy)phenyl]-3-(4-(N,N-dimethylamino)phenyl)-1,3-diketone(Na27
．． Example 27), 1-(3((2s)-2-chloro-
3-mercaptomethoxy-1-propyloxy)phenyl)-3-(3-bromo-4-methoxyphenyl)-1
, 3-diketone (m28. Example 28), 1- (4-
<(2s)-2-bromo-3-mercaptomethoxy-1-propyloxy)phenyl]-3-(3-fluoro-4-ethoxyphenyl)-1,3-diketone
9. Example 29), 1-(((2s)-2-chloro-5
-methoxy-1-pentyloxy)phenyl]-3-(
3,4-dimethoxyphenyl)-1,3-diketone (N
a30゜Example 30), 1-C((2s)-2-bromo-5-methoxy-1-pentyloxy)phenyl]-3
-(3-fluoro-4-ethoxyphenyl)-1,3-
diketone (Nn31. Example 31), l-C(3-(2
s)-2-chloro-4-mercaptomethyl-1-butoxy)phenyl)-3-(2゜6-dichlorophenyl)-
1,3-diketone (Na32, Example 32), 1-(
((2s)-2-bromo-4-mercaptomethyl-l-
butoxy)phenyl)-3-(2,4-dimethoxyphenyl)-1,3-diketone [33, Example 33) Table 1 Table 2 Table 3 Table 4 (Effects of the invention) The compound of the present invention is a keto type There is an equilibrium relationship between the enol type and the enol type, but the content of the structurally stable enol type is large, resulting in a widely expanded π-electron conjugated structure. Therefore, by providing an it substituent with an appropriate dipole moment, intramolecular resonance can be induced, and a large nonlinear susceptibility can be expected.

Furthermore, since it has an intramolecular enolic hydroxyl group, this acts as a molecular orientation control group and can change the bulk structure.

That is, it is an effective functional substituent that can induce a non-centrosymmetric structure necessary for SHG activity.

Furthermore, compared to CT type molecules such as MNA, the compound of the present invention does not have absorption in the long wavelength region, so that the compound is less likely to deteriorate due to absorption of the second harmonic.

The compound of the present invention has a high melting point, low sublimation property, and low water absorption, so it has excellent storage stability. It also has extremely high nonlinear susceptibility and excellent laser resistance. can be provided. Therefore, it is effective for optical information and optical communications including wavelength conversion elements for semiconductor lasers.

[Brief explanation of drawings]

FIG. 1: UV spectrum of compound Nf15 FIG. 2 is a schematic diagram showing a second high-frequency wave generator used in an example of the present invention. 1; Q switch Nd: YAG laser-2: 108
4 nm laser mirror 3 Shutter 4; Sample (powder) 5 Condensing lens 6; Infrared cut filter 7 Polychromator 8 Multi-channel photodiode 9° MCPD drive circuit

Claims (1)

[Claims] (1) A nonlinear optical material characterized by containing a 1,3-diketone derivative represented by the following general formula [1]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [1] (In the formula, R^2 may be different or the same, and is an amino group, a substituted amino group substituted with a group having 1 to 12 carbon atoms, a cyclic amino group, An organic substituent selected from an alkyl group, a halogen-substituted alkyl group, an alkoxy group, a halogen-substituted alkoxy group, and a mercaptoalkoxy group, where n indicates the number and is 1 to 5, and R^b is R^a and They are the same organic substituent, and m indicates the number and is 0 to 5. Rings A and B indicate an aromatic hydrocarbon group or a heteroaromatic group.)