JP2737717B2 - Organic nonlinear optical material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic nonlinear optical material used for optical information processing and optical communication.

[0002]

2. Description of the Related Art Wavelength conversion elements, optical modulators, optical switches, and optical logic gates are realized by using nonlinear optical phenomena that produce various effects such as harmonic generation, sum frequency generation, Kerr effect, and Pockels effect. Various functional elements such as basic elements for realizing an optical computer such as optical transistors can be provided.

Conventionally, as nonlinear optical materials, inorganic materials and semiconductor materials such as potassium dihydrogen phosphate (KDP), lithium niobate (LiNbO ₃ ), and gallium arsenide (GaAs) have been mainly developed.

However, in recent years, an organic material having excellent nonlinear optical performance and an extremely fast light response speed has been discovered as compared with those materials, and since then, organic nonlinear optical elements using the organic material have been actively developed. Was.

As examples of such organic nonlinear optical materials, paranitroaniline (pNA), 2-methyl-4-
Nitroaniline (MNA) (ACS Symposium Ser.)
ies), 233, 1 (1983)) and 4- (N, N
-Dimethylamino) -3-acetamidonitrobenzene (DAN) (Applied Physics Letters (Ap
pl. Phys. Lett. ), 51 (19), 148
4 (1987)).

[0006]

However, the pNA
Such a compound has a large non-linearity as a molecule, but has a central symmetry due to a large dipole-dipole interaction between molecules in a crystal, and does not exhibit second harmonic generation (SHG).

[0007] MNA, DAN and the like form non-centrosymmetric crystals and have large nonlinearity.
The absorption edge of visible absorption is 530 nm for MNA and 4 for DAN.
Semiconductor laser light (λ = 700 nm to 100 nm)
(0 nm) in the transmission type, there is a problem that the conversion efficiency is reduced due to the re-absorption of the second harmonic by the compound itself, the compound is deteriorated, and the like. Compounds aimed at generating second harmonics at shorter wavelengths include 3,5-dimethyl-1- (4-
Nitrophenyl) pyrazole (DMNP) (CMC Co., Ltd. “New Organic Nonlinear Optical Material I” No. 76-
81 (1991)), the absorption edge of DMNP is 402 nm, and it can be used as a material for blue light conversion, but is not suitable for ultraviolet light conversion.

An object of the present invention is to provide an organic nonlinear optical material which solves the above-mentioned problems and has a large nonlinearity even at a crystal level and which can generate a second harmonic in an ultraviolet light region. To provide.

[0009]

According to the present invention, there is provided an organic compound having an absorption edge on the short wavelength side, that is, a compound represented by the following general formula (1):
An organic nonlinear optical material comprising the amide derivative, imide derivative, thioamide derivative, and thiourethane derivative represented by (5).

[0010]

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In the above compounds, R ^{1 to} R ¹⁷ represent hydrogen or an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, and an aryl group having 6 to 12 carbon atoms (where R ^{6 to} R ^17). Except when is hydrogen) . The substituent R may be substituted with one or more alkyl groups having 1 to 4 carbon atoms or halogen elements such as fluorine, chlorine and bromine. Further, the alkyl groups and halogen elements on R ^{1 to} R ¹⁷ and R may be the same or different.

An alkyl group represented by R, an aralkyl group,
Representative examples of the aryl group include, but are not limited to, groups represented by the following chemical formula.

[0013]

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[0014]

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The organic nonlinear optical material comprising the amide derivative, imide derivative, thioamide derivative and thiourethane derivative according to the present invention has a melting point of around 100 ° C. or 1 ° C.
It is not less than 00 ° C., is thermally stable, and has excellent weather resistance.

The compound of the present invention has a large SHG activity due to having a polar amide structure in the molecule. Further, the compounds (3), (4) and (5) have a large SHG activity by replacing oxygen atoms of the carbonyl group and urethane group with sulfur atoms.

Furthermore, since the compound of the present invention does not contain a large conjugated system in the molecule, the absorption edge becomes 370 nm or less,
Blue conversion or ultraviolet light conversion becomes possible.

The organic compound of the present invention can be easily synthesized using a commercially available organic compound, and can be sufficiently used industrially.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The contents of the present invention will be described in detail with examples.

[0020]

Embodiment 1

[0021]

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5.0 g of diisopropylamine was placed in a three-necked flask equipped with a reflux condenser, a nitrogen inlet tube, and a dropping funnel.
(49 mmol), 5.5 g of triethylamine (55 m
mol) and 50 ml of chloroform, and the mixture was stirred at room temperature under a nitrogen atmosphere. 9.2 g (55 mmol) of chloroform 10 in benzoylformyl chloride was added to the dropping funnel.
ml solution was added and dropped over 20 minutes. After stirring for 1 hour at room temperature, 100 ml of water was gently added to terminate the reaction. After extraction with chloroform and drying, the solvent was distilled off under reduced pressure to obtain crude crystals. After recrystallization from ethanol, N, N-diisopropylbenzoylformamide 1
0.5 g (92% yield) was obtained.

The melting point was 105-107 ° C., and the absorption edge in acetonitrile solution was 371.0 nm.

Elemental analysis value CH N Theoretical value 72.06% 8.21% 6.01% Actual value value 72.1 8.4 5.9 ¹ H-NMR spectrum (CDCl ₃ ) δ 1.18 (ppm) (6H, d, J = 6.6Hz , CH 3 × 2) 1.59 (6H, d, J = 7.0Hz, CH 3 × 2) 3.60 (1H, sep, J = 7.0Hz, CH ) 3.70 (1H, sep, J = 6.6 Hz, CH) 7.5-7.7 (3H, m,, Ph) 7.9-8.0 (2H, m,, Ph) Infrared absorption The spectrum ν _max. 1690 cm ⁻¹ SHG intensity was measured by a powder method, and the light source was LD.
Laser-excited Nd: YLF laser (wavelength 1047n)
m), a sample crushed to 50 μm or less with a mortar was used, and had a strength 10 times that of urea.

Table 1 shows the SHG intensity of the YLF laser (wavelength: 1047 nm) and the absorption edge wavelength in an acetonitrile solution for the amide compound synthesized in the same manner.

[0026]

Embodiment 2

[0027]

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In a three-necked flask equipped with a reflux condenser, a nitrogen inlet tube, and a dropping funnel, 5.0 g (22 mmol) of N-phenyl-2-chlorobenzamide, 2.2 g (22 mmol) of triethylamine, and 30 ml of chloroform were put, and a nitrogen atmosphere was added. The mixture was stirred at room temperature. A solution of 2.3 g (22 mmol) of methacrylic acid chloride in 10 ml of chloroform was added to the dropping funnel and added dropwise over 20 minutes. After stirring for 1 hour at room temperature, 100 ml of water was gently added to terminate the reaction. After extracting with chloroform and drying,
The solvent was distilled off under reduced pressure to obtain a crude crystal. The crystal was recrystallized from ethanol to obtain 6.0 g of N-phenyl-N- (2-chlorobenzoyl) methacrylamide (yield: 93%).

The melting point was 73-74 ° C., and the absorption edge in acetonitrile solution was 307.0 nm.

Elemental analysis value CH N Theoretical value 68.21% 4.72% 4.68% Observed value 68.1 4.8 4.7 ¹ H-NMR spectrum (CDCl ₃ ) δ 1.77 (ppm) (3H, d, J = 1.1Hz , CH 3) 5.44 (1H, d, J = 1.1Hz, CH) 5.74 (1H, s,, CH) 7.2-7.5 (9H , M,, Ph) Infrared absorption spectrum ν _max. 1670 cm ⁻¹ 1620 SHG intensity was measured in the same manner as in Example 1 and had an intensity 20 times that of urea.

Table 2 shows the SHG intensity of a YLF laser (wavelength: 1047 nm) and the absorption edge wavelength in an acetonitrile solution of the imide compound synthesized in the same manner.

[0032]

Embodiment 3

[0033]

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In a three-necked flask equipped with a reflux condenser, a nitrogen inlet tube, and a dropping funnel, 2.5 g (17 mmol) of N-isopropylbenzylamine and 1.7 g of triethylamine.
(17 mmol) and 30 ml of chloroform were added and stirred at room temperature under a nitrogen atmosphere. To the dropping funnel, 2.00 g (17 mmol) of chigyl chloride in 10 m of chloroform.
1 solution was added and added dropwise over 20 minutes. After stirring for 1 hour at room temperature, 100 ml of water was gently added to terminate the reaction. After extraction with chloroform and drying, the solvent was distilled off under reduced pressure to obtain crude crystals. The crystal was recrystallized from ethanol to obtain 3.7 g (yield: 95%) of N-isopropyl-N-benzylthimilamide.

[0035]

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In a recovery flask equipped with a reflux condenser, N-
3.7 g of isopropyl-N-benzylthimilamide
(16 mmol), 0.73 g (3.3 mm) of phosphorus pentasulfide
ol) and dissolve in 50 mL of anhydrous xylene. Heat to reflux with stirring for 1 hour. After extraction with toluene and drying, the solvent was distilled off under reduced pressure to obtain a crude crystal. The crystals were recrystallized from ethanol to obtain 3.2 g (yield: 80%) of N-isopropyl-N-benzylthiothimilamide.

The melting point was 111-113 ° C., and the absorption edge in acetonitrile solution was 319.0 nm.

Elemental analysis value CH N Theoretical value 72.83% 8.56% 5.67% Observed value 72.8 8.6 5.4 ¹ H-NMR spectrum (CDCl ₃ ) δ 1.16 (ppm) (6H, d, J = 6.9Hz , CH 3 × 2) 1.71 (3H, d, q, J = 6.9Hz, 1.7Hz, CH 3) 2.05 (3H, m,, CH 3 ) 4.68 (1H, sep, J = 6.9Hz, CH) 5.27 (2H, s,, CH 2) 5.26-5.28 (1H, m,, CH) 7.3-7. 5 (5H, m ,, Ph) ¹³ C-NMR spectrum (CDCl ₃ ) δ 14.1 (q), 21.6 (q), 23.1
(Q), 48.6 (t), 55.0 (d), 119.
7 (t), 126.8 (d), 128.3 (d), 13
7.2 (s), 139.0 (s), 203.8 (s) Measurement of infrared absorption spectrum ν _max. 1650 cm ^-1 SHG intensity was performed in the same manner as in Example 1, and was 10 times stronger than urea. It had.

Table 3 shows the SHG intensity of a YLF laser (wavelength: 1047 nm) and the absorption edge wavelength in an acetonitrile solution for the thioamide compound synthesized in the same manner.

[0040]

Embodiment 4

[0041]

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In a three-necked flask equipped with a reflux condenser and a nitrogen inlet tube, 3.0 g (23 mmol) of benzyl isocyanate was placed.
l), 2.5 g (23 mmol) of thiophenol are added and dissolved with 50 ml of dimethylformamide. 0.1 g of triethylamine was added, and the mixture was added at room temperature under nitrogen atmosphere.
Stirred for hours. After extraction with dichloromethane and drying, the solvent was distilled off under reduced pressure, and S-phenylbenzylcarbamate was used.
8 g were obtained.

[0043]

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In a three-necked flask equipped with a reflux condenser, a nitrogen introducing tube, and a dropping funnel, 3.00 g (12.3 mmol) of S-phenylbenzylcarbamate, 1.24 g (12.3 mmol) of triethylamine, and 30 m of chloroform.
and stirred at room temperature under a nitrogen atmosphere. 2.10 g (12.3 m) of benzoylformyl chloride was added to the dropping funnel.
mol.) in 10 ml of chloroform was added dropwise over 20 minutes. After stirring for 1 hour at room temperature, 100 ml of water was gently added to terminate the reaction. After extraction with chloroform and drying, the solvent was distilled off under reduced pressure to obtain crude crystals. Recrystallization with ethanol gave S-phenyl N-
(Benzoylformyl) benzyl carbamate 4.13
g (yield 90%) was obtained.

The melting point was 106-107 ° C., and the absorption edge in acetonitrile solution was 304 nm.

Elemental analysis value CH N Theoretical value 70.38% 4.57% 3.73% Observed value 70.5 4.4 3.8 ¹ H-NMR spectrum (CDCl ₃ ) δ 5.22 (ppm) _{(2H, s, CH 2)} 7.24-7.56 (13H, m, benzene ring) 7.80-7.82 (2H, m, benzene ring) ¹³ C-NMR spectrum (CDCl ₃₎ δ 46. 9 (t), 125.1-135.3 (m),
168.7 (s), 171.5 (s), 186.6
(S) Infrared absorption spectrum ν _max. 1690 cm ^-1 1710 SHG intensity was measured in the same manner as in Example 1 and had ten times the intensity of urea.

Table 4 shows the SHG intensity of the YLF laser (wavelength 1047 nm) and the absorption edge wavelength in an ethanol solution of the thiourethane compound synthesized in the same manner.

[0048]

Embodiment 5

[0049]

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In a three-necked flask equipped with a reflux condenser and a nitrogen inlet tube, 5.0 g (37 mm) of phenylisothiocyanate was placed.
ol), 4.3 g (40 mmol) of benzyl alcohol
And dissolve in 50 ml of dimethylformamide.
0.1 g of triethylamine was added, and the mixture was stirred at room temperature for 1 hour under a nitrogen atmosphere. After extraction with dichloromethane and drying, the solvent was distilled off under reduced pressure to obtain 8.5 g of O-benzylphenylthiocarbamate.

[0051]

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In a three-necked flask equipped with a reflux condenser, a nitrogen inlet tube and a dropping funnel, 5.0 g (21 mmol) of O-benzylphenylthiocarbamate, 2.3 g (23 mmol) of triethylamine and 50 ml of chloroform were put. Stir at room temperature. A solution of 3.2 g (23 mmol) of benzoyl chloride in 10 ml of chloroform was added to the dropping funnel and dropped over 20 minutes. After stirring for 1 hour at room temperature, 100 ml of water was gently added to terminate the reaction. After extraction with chloroform and drying, the solvent was distilled off under reduced pressure to obtain crude crystals. Recrystallization from ethanol gave 6.9 g of O-benzyl N-benzoylphenylthiocarbamate (95% yield).

The absorption edge in acetonitrile solution was 369.
nm.

Elemental analysis value CHN Theoretical value 72.60% 4.94% 4.03% Found 72.5 4.8 4.2 ¹ H-NMR spectrum (CDCl ₃ ) δ 5.33 (ppm) _{(2H, s, CH 2)} 7.3-8.0 (15H, m, benzene ring) measurement of infrared absorption spectrum ν _max. 1700cm ^-1 1710 SHG intensity were performed in the same manner as in example 1, the urea It had 20 times the strength.

Table 5 shows the SHG intensity of the YLF laser (wavelength: 1047 nm) and the absorption edge wavelength in an ethanol solution of the thiourethane compound synthesized in the same manner.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

[Table 4]

[0060]

[Table 5]

[0061]

According to the present invention, it is possible to provide an organic nonlinear optical material capable of generating a second harmonic in the ultraviolet light region in a transmission type and having a large optical nonlinearity.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07C 333/10 C07C 333/10 (72) Inventor Shoji Watanabe 1-33 Yayoimachi, Inage-ku, Chiba-shi, Chiba Chiba University (72) Inventor Riki Fujita 1-33 Yayoimachi, Inage-ku, Chiba-shi Chiba University (56) References JP-A-7-225402 (JP, A) JP-A-5-11291 (JP, A) JP-A-7- 168222 (JP, A)

Claims (5)

(57) [Claims] 1. An organic nonlinear optical material comprising an amide derivative represented by the following general formula (1). Embedded image (Wherein R ¹ , R ² , and R ³ represent hydrogen or an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, and an aryl group having 6 to 12 carbon atoms.
May be substituted with one or more alkyl groups having 1 to 4 carbon atoms or halogen elements. Also, R ¹ , R ² ,
R ³ may be the same or different. ) 2. An organic nonlinear optical material comprising an imide derivative represented by the following general formula (2). Embedded image (Wherein, R ^4, R ^5, R ⁷ represents hydrogen or an alkyl group having from 1 to 6 carbon atoms, an aralkyl group having a carbon number of 7 to 11, are shown. R ⁶ is an aryl group having carbon number of 6 12 Charcoal
An alkyl group having a prime number of 1 to 6 and an alkyl group having a carbon number of 7 to 11
It represents an aralkyl group or an aryl group having 6 to 12 carbon atoms .
The substituent R may be substituted with one or more alkyl groups having 1 to 4 carbon atoms or halogen elements. Also, R
⁴ , R ⁵ , R ⁶ , and R ⁷ may be the same or different. ) 3. An organic nonlinear optical material comprising a thioamide derivative represented by the following general formula (3). Embedded image (Wherein, R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ represent hydrogen or an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, and an aryl group having 6 to 12 carbon atoms. the substituent R alkyl group having 1 to 4 carbon atoms, halogen element may have one or more substituents. Moreover, R ^8, R
⁹ , R ¹⁰ and R ¹¹ may be the same or different. ) 4. An organic nonlinear optical material comprising a thiourethane derivative represented by the following general formula (4). Embedded image (Wherein, R ¹² , R ¹³ and R ¹⁴ represent hydrogen or an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, and an aryl group having 6 to 12 carbon atoms.
May be substituted with one or more alkyl groups having 1 to 4 carbon atoms or halogen elements. R ¹² , R ¹³ ,
R ¹⁴ may be the same or different. ) 5. An organic nonlinear optical material comprising a thiourethane derivative represented by the following general formula (5). Embedded image (Wherein, R ¹⁵ , R ¹⁶ , and R ¹⁷ represent hydrogen or an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, and an aryl group having 6 to 12 carbon atoms.
May be substituted with one or more alkyl groups having 1 to 4 carbon atoms or halogen elements. R ¹⁵ , R ¹⁶ ,
R ¹⁷ may be the same or different. )