JPH02183227A - Organic nonlinear optical material - Google Patents

Abstract

PURPOSE:To inexpensively synthesize a large single crystal which has the high activity of second harmonic wave generation (SHG), is stable at room temp., and has the absorption existing in a short wavelength region by using a specific N-phenyl maleamic acid deriv. CONSTITUTION:The org. nonlinear optical material is constituted by using the N-phenyl maleamic acid deriv. expressed by the formula I. This N-phenyl maleamic acid deriv. can be obtd. by bringing maleic acid anhydride and various aniline derivatives into reaction. In the formula I, R denotes a halogen atom, 1 to 6C alkyl group, 1 to 6C alkoxy group or nitro group; n is 1 to 5 integer. The material for the stock of nonlinear optical devices, etc., which has the high SHG intensity and the high nonlinear optical characteristic, is thermally stable and can be easily grown to the large single crystal is inexpensively obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an organic nonlinear optical material, and more particularly, to a compound having an organic nonlinear optical effect composed of an N-phenylmaleamic acid derivative.

(Prior art) Nonlinear optical materials are materials that exhibit nonlinear response of second order or higher under the strong electric field of laser light, and their phenomena include wavelength conversion, amplification, modulation, shortening of pulses, switching, and memory self-control. Because it provides numerous device functions, it is attracting attention as a core material for optoelectronics and optical computers.

Research and development has focused on inorganic derivatives and semiconductors such as potassium dihydrogen phosphate and lithium niobate.

Recently, organic compounds such as urea, 2-methyl-4-nitroaniline, methyl-(2,4-dinitrophenyl)-aminopropanate, and 3-methyl-4-nitropyridine-1-oxide No. 92870, Japanese Unexamined Patent Publication No. 1983
-94333) was found to exhibit a nonlinear response that far exceeds that of conventional inorganic compounds, and research and development of organic nonlinear optical materials is attracting attention.

(Problem to be solved by the invention a) Some organic crystals have a figure of merit η (72=d"/n", d: NLO constant, n:
refractive index). The photoresponse speed is on the order of femtoseconds, which is much faster than inorganic crystals because lattice vibrations are not involved, and it is also recognized that the threshold for photodamage is large. However, (2) Second harmonic generation (hereinafter referred to as SHG) does not occur in crystals with a center of symmetry as an even-order feature; (2) In order to improve the nonlinear optical effect,
If the second-order supramolecular polarizability β is designed to be large, the absorption will extend to a long wavelength region, making it unsuitable for practical use. Also, centrally symmetric crystals are likely to be produced (3) or large single crystals may be produced. In particular, the fact that there are a lot of ugly things is a big problem.

The object of the present invention is to have a single crystal with no center of symmetry, which has high SHG activity, is stable at room temperature, has absorption in a short wavelength range, and has a large single crystal size. The object of the present invention is to provide an organic nonlinear optical material that can be synthesized at low cost.

(Means for Solving the Problems) The present invention relates to the following general formula: (wherein R is a halogen atom, an alkyl group having I to 6 carbon atoms,
Represents an alkoxy group having 1 to 6 carbon atoms or a nitro group,
It is an organic nonlinear optical material made of an N-phenylmaleamic acid derivative represented by (n is an integer of 1 to 5).

In the present invention, the N-phenylmaleamic acid derivative can be obtained by reacting maleic anhydride with various aniline derivatives. During the reaction, an appropriate solvent such as an ether solvent such as tetrahydrofuran (THF) or a BTX-based solvent such as xylene can be used as necessary, and the reaction time is 20 minutes at a temperature of 0°C to 140°C.
Preferably, the reaction is carried out for a period of time. During the reaction, if the reaction temperature is higher than 140°C, maleimide will be formed due to thermal dehydration, and if it is lower than 0°C, the reaction time will be longer.

Preferred aniline derivatives used in the synthesis in the present invention include chloroaniline, dichloroaniline, trichloroaniline, fluoroaniline, difluoroaniline, trifluoroaniline, tetrafluoroaniline, methylaniline, propylaniline, butylaniline, methoxyaniline, ethoxyaniline. , propoxyaniline, butoxyaniline, nitroaniline and the like.

Examples of the N-phenylmaleamic acid derivative represented by the general formula (r) used in the present invention include N-(4-methoxyphenyl)maleamic acid, N-(4-ethoxyphenyl)maleamic acid, N-(4- chlorophenyl) maleamic acid, N-(2,4-dichlorophenyl) maleamic acid, N-(4-fluorophenyl) maleamic acid, N-(2-fluorophenyl) maleamic acid,
N-(2,4-difluorophenyl)maleamic acid,
N-(2,4,6-)lifluorophenyl) maleamic acid, N-(2,3,5,6-titrafluorophenyl) maleamic acid, N・-(2゜3.4.5.6- Pentafluorophenyl) maleamic acid, N-(4-nitrophenyl) maleamic acid, N-(4-methylphenyl) maleamic fi, N-(4-ethylphenyl) maleamic acid, N-(4-propylphenyl) maleamic acid etc.

Among these, N-(alkoxyphenyl)maleamic acid and phenylmaleamic acid substituted with 1 to 3 fluorines have a high SHG and are preferred as nonlinear optical materials.

The N-phenylmaleamic acid derivative according to the present invention can be used with an Nd-YAG laser (wavelength 1064
The second harmonic is generated by irradiation at the n-end), and green light of 1/2 wavelength (532 nm) of the incident light is produced.

This is due to the fact that the N-phenylmaleamic acid derivative according to the present invention is a single crystal without a symmetry center.
This shows G activity. Moreover, it is thermally stable,
Moreover, it can be easily grown into a large single crystal.

(Effects of the Invention) The organic nonlinear optical material made of the N-phenylmaleamic acid derivative according to the present invention has a high 580 intensity, high nonlinear optical properties, is thermally stable, and can easily grow into a large single crystal. can be obtained at a lower cost than conventional products. Therefore, it is useful as a material for wavelength conversion elements, optical switches, etc., optical control devices, nonlinear optical devices, etc. that utilize nonlinear optical response.

(Examples) Hereinafter, the present invention will be explained in more detail based on Examples and Comparative Examples.

Example 1 5.39 g (0,055 mol) of maleic anhydride was dissolved in about 100 d of THF and stirred at room temperature.
-Ethoxyaniline (p-phenetidine) 6.85g
(0.05 mol) was added dropwise. Cool the container on ice and continue stirring. After a few minutes, a precipitate forms. The product was filtered, washed several times, and then dried to obtain 9.05 g of N-(4-ethoxyphenyl)maleamic acid [4-ethoxymaleaanilic acid]. The yield was 92%. Moreover, the melting point (decomposition temperature) was 186-187°C.

The results of mass spectrometry and 'H-NMR are shown below.

Mass spectrometry (m/z) M” (235) 100.0 M +1 (236) 14.1M +2 (2
37) 1.7'H-NMR (TMS/DMS
O-d, )61.3'''1.4 (tri, 3H
-PHOCllzCjjl) 3.9~4.1 (Q, 2
11. -PHOCjjlCH3) 6.2~6.6 (d
d, 211. -CB=C1i-)6.8~7.6 (
dd, 41(,-CaL-)10.4(wid
e, IH, -COOH)SHG measurement is performed using N-(4-
Ethoxyphenyl) maleamic acid with a particle size of 60 to 1O〇- was sandwiched between slide glasses, and a Q-switched Nd-YAG laser (wavelength 1064n+*,
10nsec pulse) irradiation. Second harmonics scattered from the sample were detected. As a standard sample, a urea compound having the same particle size was used, and the relative intensity was determined when the 580 intensity of the urea compound was taken as 1.

When the 580 intensity of the sample was measured by the above method, it was confirmed that the 580 intensity was 7 times that of urea.

Example 2 5.39 g (0,055 mof) of maleic anhydride was dissolved in about 100 d of THF and stirred at room temperature.
6.90 g (0.05 mol) of nitroaniline is added dropwise. Cool the container with water and continue stirring. After a few minutes, a precipitate forms.

The product was filtered and washed several times, then dried to yield 9.05 g of N.
-(4-nitrophenyl)mareamic M (4-nitromaleaanilisocic acid) was obtained.The yield was 82%.The melting point (decomposition temperature) was 198-199°C.

The results of mass spectrometry and 'H-NMR are shown below.

Mass spectrometry (+m/z) M″″ (236) 100.0 M + 1 (237) 12.2M + 2
(23B) 1.7' H-N M R (TNS
/DMSO-d h )66.3-6.6 (dd,
2H, -CH=CH-)7.8-8.3 (dd,
4H,-Cal(4,-)10.8 (wid
e, IH, -COO) l) N by the method of Example 1
When the strength of -(4-nitrophenyl)maleamic acid was measured, it was confirmed that the strength was 580, which was 1.5 times that of urea.

Example 3 5.88 g of maleic anhydride (approximately 100 g of 0.06 mole
5.55 g (0.05 mol) of 4-fluoroaniline was added dropwise to the solution while stirring at room temperature. Cool the container on ice and continue stirring. After a few minutes, a precipitate forms.

The product was filtered, washed several times and dried to yield 9.46 g of N.
-(4-fluorophenyl)maleamic acid [4-fluoromaleanilic acid] was obtained. The yield was 98%. Moreover, the melting point (decomposition temperature) was 208 to 210°C.

The results of mass spectrometry and 'H-NMR are shown below.

Mass spectrometry (m/z) M” (209) 100.0 M + 1 (210) 11.6M + 2
(211) 1.2'H-NMR (TMS/
Mouth MSOd 6) 66.2~6.5 (dd,
2H, -C1=CH~)7.0~7.7 (m, 4H
, -C4H6-)10.4 (wide, IH,
-COOH) When the 380 intensity of N-(4-fluorophenyl)maleamic acid was measured by the method of Example 1, it was confirmed that the SHO intensity was 9 times that of urea.

Example 4 5.88 g (0.06 mol) of maleic anhydride was added to about 1
00- in THF, and 5.55 g (0.05 mol) of 2-fluoroaniline was added dropwise while stirring at room temperature. Cool the container on ice and continue stirring. After a few minutes, a precipitate forms.

The product was filtered, washed several times, and then dried to obtain N-(2fluorophenyl)maleamic acid [2-fluoromaleanilinic acid]. The yield was 34%. Moreover, the melting point (decomposition temperature) was 147 to 148°C.

The results of mass spectrometry and 'H-NMR are shown below.

Mass spectrometry (m/z) M” (209) 100.0M + 1
(210) 11.7M + 2 (211
) 1.11 H-NMR (TMS/D
MSO-d! )66.2~6.7 (q,
2H, -C1l=CH-)7.2-8.0 (m,
4H, -C6L, -)12.0 (wide,
LH, -COO) I) N-(2-
When the 380 intensity of fluorophenyl)maleamic acid was measured, it was confirmed that the 380 intensity was 14 times that of urea.

Example 5 2.16 g (<0.022 mol) of maleic anhydride was dissolved in about 50 rsl of THF and stirred at room temperature.
4-difluoroaniline 2.58g (0.02mol)
drip. Cool the container on ice and continue stirring. After a few minutes,
A precipitate forms.

The product was filtered, washed several times and dried to yield 3.04 g of N.
-(2,4-difluorophenyl)maleamic acid [2
, 4-difluoromaleanilic acid] 3.04 g was obtained. The yield was 67%. Also, the melting point (decomposition temperature) is 1
The temperature was 93-194°C.

The results of mass spectrometry and 'H-NMR are shown below.

Mass spectrometry (m/z) M4 (227) 100.0 M + 1 (228) 11.7 M +2 (
229) 1.2'H-NMR(TMS
/DMSO-d & )66.2~6.6 (dd,
2H, -CH=CH-)7.0~8.0 (m, 3H
, -CaHs-)10.2 (wide, IH,
-COOH) When the 380 intensity of N-(2,4-difluorophenyl)maleamic acid was measured by the method of Example 1, it was confirmed that the 5L (G intensity) was 8 times that of urea.

Example 6 2.16 g (0,022 mol) of maleic anhydride was dissolved in about 50% THF and mixed with 2.4.
6-1 Lifluoroaniline 2.94g (0.02mol
) to drip. Cool the container with water and continue stirring. After several tens of minutes, a precipitate forms.

The product was filtered and washed several times, then dried to a concentration of 1.338 N-
(2,4,61-lifluorophenyl)maleamic acid (2,4,6-t-lifluoromaleanilic acid)1.
33g was obtained. The yield was 27%.

Moreover, the melting point (decomposition temperature) was 166-167°C.

The results of mass spectrometry and 'H-NMR are shown below.

Mass spectrometry (m/z) M” (245) 100.0 M + 1 (246) 11.7M + 2
(247) 1.2'H-NMR(TMS
/DMSO-db)66.3~6.6 (dd,
211. -C1l=CH-) )7.1~7.3 (m
, 2H, -CJz-)10.1 (svideo,
IH, -COOH) N-(2, -COOH) by the method of Example 1
38 of 4,6-)lifluorophenyl)maleamic acid
When the 0 intensity was measured, it was confirmed that the 380 intensity was 9 times that of urea.

Example 7 2.16 g (0,022 mol) of maleic anhydride was dissolved in about 59 ml of THF and mixed with stirring at room temperature.
, 5.6-titrafluoroaniline 3.30 g (0,0
2 mol) was added dropwise. Cool the container on ice and continue stirring. After several tens of minutes, a precipitate forms.

The product was filtered, washed several times and dried to yield 3.60 g of N-
(2,3,5,6-titrafluorophenyl)maleamic acid [2,3,5,6-titrafluorophenylmaleanic acid] was obtained. The yield was 68%. Moreover, the melting point (decomposition temperature) was 118 to 120°C.

The results of mass spectrometry and 'H-NMR are shown below.

Mass spectrometry (m/z) M” (263) 100.0 M + 1 (264) 11.7M + 2
<265) 1.1' H-NMR(TMS
/DMSO-d6)66.3~6.6 (dd,
211. -CH=CH-)'')7.5~7.6 (m
, IFI, -C6H-)10.07 (wid
e, IFl, -COOII) N-(2,3,5,6-titrafluorophenyl) by the method of Example 1
When the 386 strength of maleamic acid was measured, it was confirmed that the 386 strength was twice that of urea.

Example 8 2.16 g (0,022 mol) of maleic anhydride was dissolved in about 50-0 THF and stirred at room temperature. 3
．． 4.5゜6-pentafluoroaniline 3.66g (
0.02 mol) dropwise. Cool the container on ice and continue stirring. After several tens of minutes, a precipitate forms.

The product was filtered, washed several times and dried to yield 1.63 g of N
-(2,3,4,5,6-pentafluorophenyl)maleamic acid (2,3,4,5,6pentafluoromaleanilic acid) was obtained. The yield was 29%. Also, the melting point (Decomposition temperature) was 108-110°C.

The results of mass spectrometry and 'H-NMR are shown below.

Mass spectrometry (m/z) M' (281) 100.0 M + 1 (282) 11.7M +2
(283) 1.2' H-NMR(T
MS/DMSO-d, )66.3~6.5 (
dd, 2H, -C)I=CH-)) When the 386 intensity of N-(2,3,4,5゜6-pentafluorophenyl)maleamic acid was measured by the method of Example 1, it was found that We were able to confirm 386 intensity, which is four times as strong.

Comparative Example 1 5.88 g (0.06 mol) of maleic anhydride was added to about 10
Aniline 4.0- is dissolved in THF and stirred at room temperature.
Add 65 g (0.05 mol) dropwise. Cool the container on ice,
Continue stirring. After a few minutes, a precipitate forms.

The product was filtered, washed several times, and then dried to obtain N-phenylmaleamic acid.

The yield was 97%.

The results of mass spectrometry are shown below.

Mass spectrometry (m/z) M” (191) 100.0 M + 1 (192) 11.8
M + 2 (193) 1.2 When the SHO intensity of N-phenylmaleamic acid was measured by the method of Example 1, SHG could not be detected.

Comparative Example 2 5.88 g (0.06 mol) of maleic anhydride was added to about 1
00d in THF and stirred at room temperature.
, N-dimethylamino)aniline 8.20 g (0.05
mol) dropwise. Cool the container on ice and continue stirring.

After a few minutes, a precipitate forms.

The product was filtered, washed several times and then dried to give N-(4-(
N'',N'-dimethylamino)phenylcomaleamic acid (4-(N,N-dimethylamino)phenylmaleamic acid) was obtained. The yield was 91%.

The results of mass spectrometry are shown below.

Mass spectrometry (m/z) M” (234) 100.0 M + 1 (235) 14.4M + 2
(236) 1.5 N-(
When the 380 intensity of 4-(N',N'-dimethylamino)phenylcomaleamic acid was measured, no SHG could be detected.

Patent applicant: Miya 1) Naoya Kiyoshi Kurao Nippon Oil & Fats Co., Ltd.

Claims (1)

[Claims] The following general formula: ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R is a halogen atom, an alkyl group having 1 to 6 carbon atoms,
Represents an alkoxy group having 1 to 6 carbon atoms or a nitro group,
An organic nonlinear optical material comprising an N-phenylmaleamic acid derivative represented by (n is an integer of 1 to 5).