JPH0580375A - Organic nonlinear optical element - Google Patents

Abstract

PURPOSE:To provide a stable org. nonlinear optical element low in moisture absorptivity and sublimability and excellent in optical transparency by using a specified org. compd. CONSTITUTION:This org. nonlinear optical element consists of a compd. shown by formula or a high molecular compd. obtained by joining the compd. to a polymeric material (in the formula, R is alkyl, alkenyl, alkinyl, aryl or aralkyl, Ar is an aromatic ring or heterocyclic ring, and X is a halogen atom). The SHG of this element is almost equivalent to that of the nonlinear optical element using 2-methyl-4-nitroaniline, and further a large single crystal having no center of symmetry exhibiting a secondary nonlinear optical characteristic or a structure having no center of symmetry in the matrix, oriented and dispersed is easily obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to the second harmonic and the third harmonic.
The present invention relates to an organic nonlinear optical element used for generation of harmonics, light mixing, light modulation, optical parametric oscillation, optical switch, and the like.

[0002]

_2. Description of the Related Art Conventionally, inorganic ferroelectric materials such as KH ₂ PO ₄ , LiNbO ₃ , and (NH ₄ ) H ₂ PO ₄ have been known as nonlinear optical materials made of inorganic compounds. It has been put to practical use as a conversion material. On the other hand, recently, 2-methyl-4-nitroaniline and 3-methyl-4 have been proposed as those having large nonlinear optical characteristics as compared with these inorganic ferroelectrics.
Non-linear optical materials made of organic compounds such as -nitropyridine-1-oxide have been known.

[0003]

Generally, in order for an optical material made of an organic compound to exhibit a second-order nonlinear optical characteristic, the molecule itself has a structure not having mirror symmetry, and at the time of crystallizing the molecule. It is necessary to be able to construct a crystal structure that does not have a mirror-symmetrical center of symmetry, or to be able to orient so that the molecules do not have a mirror-symmetrical center of symmetry when dispersed in a matrix. Furthermore, in practice, it is easy to produce crystals having the above structure or to disperse the crystals in the matrix in an oriented manner, and the resulting crystal or the structure obtained by the orientation dispersion in the matrix has low hygroscopicity and sublimability. It is required to be stable and have excellent optical transparency in terms of device function.

However, the above-mentioned 2-methyl-4-nitroaniline and 3-methyl-4-nitropyridine-
1-Oxide produces a crystal that does not have a center of symmetry and exhibits great nonlinear optical characteristics, but it is difficult to obtain a large single crystal with excellent stability, and orientation dispersion is performed so that the matrix does not have a center of symmetry. There is a problem that it is difficult to make it, and further, a problem that optical transparency is low.

Therefore, the present invention solves the above problems,
It is possible to easily obtain a large single crystal that does not have a center of symmetry exhibiting second-order nonlinear optical characteristics, or a structure in which the matrix is oriented and dispersed so as not to have a center of symmetry. It is an object of the present invention to provide a non-linear optical element having an organic compound having excellent optical transparency.

[0006]

The organic nonlinear optical element of the present invention has the following general formula (1):

[Chemical 2] [In the formula, R represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or an aralkyl group, Ar represents an aromatic ring or a heteroaromatic ring, and these R and Ar may have a substituent. , X represents a halogen atom] (hereinafter referred to as “specific compound”) and /
Alternatively, it is characterized by comprising a polymer compound in which a specific compound is bound to a polymer matrix.

In the above specific compound, examples of the alkyl group represented by R in the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Isobutyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, isohexyl group, neohexyl group, n-octyl group, n-decyl group, n-dodecyl group,
Examples thereof include those having 1 to 22 carbon atoms such as n-tetradecyl group, n-hexadecyl group, n-octadecyl group, and n-eicosyl group. As the alkenyl group for R,
For example, vinyl group, allyl group, 2-butenyl group, 3-butenyl group, 3-methyl-2-butenyl group, 2-methyl-3
Examples include -butenyl group, 2-methyl-2-butenyl group, 7-hexadecenyl group, 1,3-butadienyl group, 7,10-hexadecadienyl group and the like having 2 to 20 carbon atoms. Examples of the alkynyl group represented by R include an ethynyl group, a propargyl group, a 2-butynyl group, and a 2-methyl-3 group.
-Butynyl group, 4-hexadecynyl group and the like having 2 to 16 carbon atoms
You can list the following. Examples of the aryl group of R include those having 6 to 22 carbon atoms such as phenyl group, tolyl group, xylyl group, biphenyl group and naphthyl group. Examples of the aralkyl group of R include those having 7 to 23 carbon atoms such as benzyl group, phenylethyl group, 1-naphthylmethyl group and 2-naphthylmethyl group. In the present invention, each group of R described above may have a substituent, for example, a methoxy group, an ethoxy group, a benzyloxy group, a methoxybenzyloxyl group, a t-butyldimethylsilyloxy group,
Alkoxy groups such as benzylidene dioxy group and isopropylidenedioxy group, aryloxy groups such as phenyloxy group and dinitrophenyloxy group, t-butoxycarbonylamino group, benzyloxycarbonylamino group, nitroguanidino group, toluenesulfonylguanidino group And other amino groups, benzylimidazole group, benzyloxymethylimidazole group, t-butoxycarbonyl group, benzylthio group, t-butylthio group and the like. Examples of the aromatic ring and heteroaromatic ring of Ar include a phenyl group, a naphthyl group, a pyridinyl group and a quinolyl group. In the present invention, each group of Ar described above may have a substituent,
For example, a nitro group, a cyano group, a methoxycarbonyl group, an ethoxycarbonyl group, a benzyloxycarbonyl group, a formyl group, an acetyl group, a substituent having a value of the substituent constant σp in the Hammett rule of 0.2 or more, and an amino group,
Monoalkylamino group, dialkylamino group, acylamino group, hydroxyl group, alkoxy group, methylenedioxy group,
Examples of the substituent include a substituent having a value of the substituent constant σp of less than 0.2 in Hammett's rule such as an alkyl group and a halogen, and a substituent having a value of the substituent constant σp of 0.2 or more is preferable. Further, the number of these substituents may be plural, and the respective substituents in this case may be the same or different.

In the present invention, preferred examples of the specific compound include, for example, 1-chloro-2- (4-nitrophenyl).
Aminopropane, 1-chloro-2- (4-nitrophenyl) aminobutane, 1-chloro-2- (4-nitrophenyl) amino-3-methylbutane, 1-chloro-2-
(4-nitrophenyl) amino-3-methylpentane,
1-chloro-2- (4-nitrophenyl) amino-4-
Methyl pentane, 1-chloro-2- (4-nitrophenyl) amino-2-phenylethane, 1-chloro-2-
(4-Nitrophenyl) amino-3-phenylpropane, 1-chloro-2- (4-nitrophenyl) amino-
4-phenylbutane, 1-chloro-2- (4-nitrophenyl) amino-3-benzylthiopropane, 1-chloro-2- (2,4-dinitrophenyl) aminopropane, 1-chloro-2- (2 , 4-Dinitrophenyl) aminobutane, 1-chloro-2- (2,4-dinitrophenyl) amino-3-methylbutane, 1-chloro-2-
(2,4-Dinitrophenyl) amino-3-methylpentane, 1-chloro-2- (2,4-dinitrophenyl)
Amino-4-methylpentane, 1-chloro-2- (2,
4-dinitrophenyl) amino-2-phenylethane,
1-chloro-2- (2,4-dinitrophenyl) amino-3-phenylpropane, 1-chloro-2- (2,4-
Dinitrophenyl) amino-4-phenylbutane, 1-
Chloro-2- (2,4-dinitrophenyl) amino-3
-Benzylthiopropane, 1-chloro-2- (4-cyanophenyl) aminopropane, 1-chloro-2- (4-
Cyanophenyl) aminobutane, 1-chloro-2- (4
-Cyanophenyl) amino-3-methylbutane, 1-chloro-2- (4-cyanophenyl) amino-3-methylpentane, 1-chloro-2- (4-cyanophenyl) amino-4-methylpentane, 1- Chloro-2- (4-cyanophenyl) amino-2-phenylethane, 1-chloro-2- (4-cyanophenyl) amino-3-phenylpropane, 1-chloro-2- (4-cyanophenyl) amino- 4-phenylbutane, 1-chloro-2- (4-cyanophenyl) amino-3-benzylthiopropane, 1
-Chloro-2- (5-nitro-2-pyridinyl) aminopropane, 1-chloro-2- (5-nitro-2-pyridinyl) aminobutane, 1-chloro-2- (5-nitro-
2-pyridinyl) amino-3-methylbutane, 1-chloro-2- (5-nitro-2-pyridinyl) amino-3-
Methyl pentane, 1-chloro-2- (5-nitro-2-
Pyridinyl) amino-4-methylpentane, 1-chloro-2- (5-nitro-2-pyridinyl) amino-2-phenylethane, 1-chloro-2- (5-nitro-2-pyridinyl) amino-3- Examples include phenylpropane, 1-chloro-2- (5-nitro-2-pyridinyl) amino-4-phenylbutane, 1-chloro-2- (5-nitro-2-pyridinyl) amino-3-benzylthiopropane and the like. be able to.

Method for Synthesizing Specific Compound The specific compound described above can be synthesized , for example, by substituting a halogen atom for the hydroxyl group of a 2- (aryl) aminoethanol derivative (RC Larock "Compreh.
expensive Organic Transformations ", VCH Pubishers In
c., USA, 1989, p.353-363). In this synthetic method, when the hydroxyl group is substituted with a fluorine atom, for example, diethylaminosulfur trifluoride, a combination of tetrabutylammonium fluoride and methanesulfonic acid fluoride, a combination of tetrabutylammonium fluoride and p-toluenesulfonic acid fluoride. A combination, a combination of methanesulfonyl chloride and potassium fluoride, a combination of sulfur tetrafluoride and hydrofluoric acid, and the like can be used. When substituting a chlorine atom for a hydroxyl group, for example, trichloromethyl chloroformate, a combination of triphenylphosphine and N-chlorosuccinimide, a combination of triphenylphosphine and carbon tetrachloride, a combination of phosphorus trichloride and dimethylformamide. Combinations of phosphorus oxychloride, phosphorus pentachloride, thionyl chloride and the like can be used. When the hydroxyl group is replaced with a bromine atom, for example, phosphorus tribromide,
Phosphorus pentabromide, a combination of triphenylphosphite and bromine, a combination of triphenylphosphine and N-bromosuccinimide, a combination of triphenylphosphine and carbon tetrabromide, thionyl bromide, trimethylsilane bromide, etc. Can be used. Furthermore, when substituting the iodine atom for the hydroxyl group, for example, a combination of potassium iodide and phosphoric acid, a combination of triphenylphosphine, iodine, and imidazole, a combination of trimethylsilane chloride and sodium iodide, and the like can be used. it can.

Furthermore, the 2- (aryl) aminoethanol derivatives to be halogen-substituted as described above are
It can be synthesized by the production method of 4. In the following, an α-amino acid having a substituent corresponding to R in the general formula (1) at the α position is referred to as a “substituted amino acid”, and a 2-amino acid having a substituent corresponding to the above R at the 2 position.
The aminoethanol derivative is referred to as “substituted aminoalcohol”.

Production method 1; A method in which the carboxyl group of a D-, L- or DL-substituted amino acid is reduced to a D-, L- or DL-substituted amino alcohol, and then the amino group is modified with an aryl group. In this method, the method for reducing the carboxyl group of the substituted amino acid may be a borane reduction method using a borane reagent (M. Hudlicky, "Reductions in Organic
Chemistry ", Willy, New York, 1984). This borane reduction method is effectively applied to the reduction of a substituted amino acid having optical activity without racemization occurring in the reduction reaction. Examples of amino acids include homoalanine, norvaline, leucine, isoleucine, tert-leucine, norleucine, phenylglycine, S-methylcysteine, S-benzylcysteine, etc. In this case, the borane reagent is borane-dimethylsulfide. A complex, a borane-pyridine complex, a borane-dimethylamine complex, a borane-diethylamine complex, a borane-t-butylamine complex, a borane-tetrahydrofuran complex, a borane-morpholine complex, a borane-diethylether complex, and diborane can be used. Preferred of these Those are borane-dimethyl sulfide complex, borane-ether complex and diborane, and the amount of the borane reagent used is a stoichiometrically equivalent amount or an excess amount relative to 1 mol of the substituted amino acid, preferably 1 to 2 mol.

The reduction reaction is carried out using boron trifluoride diethyl ether, trimethyl borate, aluminum trichloride,
It is preferably carried out in the presence of a Lewis acid such as titanium tetrachloride, and particularly preferably in the presence of boron trifluoride diethyl ether (see US Pat. No. 3,935,280). In this case, the amount of the Lewis acid used is stoichiometrically equivalent or excessive with respect to 1 mol of the substituted amino acid, and preferably 1 to 2 mol. The temperature of the reduction reaction is usually 0 to 110 ° C. It is desirable that this reduction reaction be performed in an inert gas atmosphere such as dry nitrogen gas or dry argon gas. The reduction reaction is usually performed in a solvent. The solvent used is not particularly limited as long as it is inert to the reduction reaction, and various solvents can be used. Specifically, aliphatic or aromatic hydrocarbons are used. , Halogenated hydrocarbons, ethers and the like. Particularly suitable are tetrahydrofuran, diethyl ether and toluene.

Means for modifying the amino group of the substituted amino alcohol obtained by the above reduction reaction with an aryl group include a method of reacting a derivative having a leaving group on the aryl ring with the substituted amino alcohol. it can. Examples of the leaving group on the aryl ring include a fluoro group, a chloro group, a bromo group, an iodo group, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, and the like. Groups and trifluoromethanesulfonyloxy groups are preferred. The amount of the derivative having a leaving group on the aryl ring used is stoichiometrically equal to or excess of 1 mol of the substituted amino alcohol, and preferably 1 to 2 mol.

The reaction temperature is usually 0 to 100 ° C., and the reaction is carried out in the presence of a solvent. As this solvent,
Aromatic hydrocarbons, halogenated hydrocarbons, ethers, alcohols, ketones, sulfoxides, amides and the like can be exemplified, and particularly preferably used are dimethyl sulfoxide and N-methylpyrrolidone. And N, N-dimethylformamide. In order to complete this reaction, it is desirable to carry out the reaction in the presence of a base. Examples of this base include inorganic bases, tertiary aminos, pyridines, and the like, and particularly preferably used are triethylamine, pyridine, and potassium carbonate. The amount of the base used is usually a stoichiometrically equivalent amount or excess amount with respect to 1 mol of the substituted amino alcohol, and preferably 1 to 1.5 mol.

Production method 2: A method of reducing a D-, L- or DL-substituted amino acid ester to obtain a D-, L- or DL-substituted amino alcohol, and then modifying the amino group with an aryl group. In the above, as the reduction method of the substituted amino acid ester, aluminum hydride reduction method, borohydride reduction method,
The hydrogenation method can be mentioned (M. Hudlicky, "Red
uctions in Organic Chemistry ", Willy, New York, 19
84). Examples of the substituted amino acid ester to which these methods are applied include the methyl ester and ethyl ester of the substituted amino acid exemplified in Production Method 1.
In the aluminum hydride reduction method, examples of the reducing agent used include aluminum hydride, lithium aluminum hydride, sodium aluminum hydride, magnesium aluminum hydride, lithium dimethoxyaluminum hydride, lithium trimethoxyaluminum hydride, and tris (t -Butoxy) aluminum lithium, bis (2-methoxyethoxy) aluminum hydride sodium, diisobutylaluminum hydride and the like can be mentioned, and among these, lithium aluminum hydride and lithium dimethoxyaluminum hydride are preferable. These reducing agents are usually substituted amino acid ester 1
It is used in a proportion of 0.5 to 10 mol per mol. The reduction reaction in this case is usually performed in a solvent. The solvent used is not particularly limited as long as it is inert to the reduction reaction, and various solvents can be used. Specifically, aliphatic or aromatic hydrocarbons and halogenated hydrocarbons can be used. Examples thereof include ethers and ethers. Tetrahydrofuran, diethyl ether and toluene are particularly preferably used. The temperature of the reduction reaction is usually -20 to 110 ° C. In addition, in this aluminum hydride reduction method, a substituted amino acid ester hydrochloride may be used as a starting material in addition to the substituted amino acid ester.

In the borohydride reduction method, as a reducing agent to be used, lithium borohydride, sodium borohydride, calcium borohydride, zinc borohydride, lithium triethylborohydride, sodium triethylborohydride, trihydroborohydride are used. Examples thereof include sodium methoxyborohydride, and sodium borohydride and lithium borohydride are preferably used. These reducing agents are usually used for 1 mol of the substituted amino acid ester.
Used in a proportion of 0.5 to 20 mol. The reduction reaction in this case is also usually carried out in a solvent, and the solvent to be used is not particularly limited as long as it is inert to the reaction, and various ones can be used. Examples thereof include system or aromatic hydrocarbons, halogenated hydrocarbons, ethers and alcohols. Tetrahydrofuran, diethyl ether and toluene are particularly preferably used. The temperature of this reduction reaction is usually -20 to 110 ° C. Also in this borohydride reduction method, a substituted amino acid ester hydrochloride can be used as a starting material in addition to the substituted amino acid ester.

In the hydrogenation method, Raney nickel, copper chromite, zinc chromite,
Rhenium oxide, palladium, etc. are used. The amount of these catalysts used is usually 0.00002 to 0.02 mol per mol of the substituted amino acid ester. This reduction reaction is usually
It is carried out in a solvent. Examples of this solvent include aliphatic or aromatic hydrocarbons, esters, carboxylic acids, ethers, alcohols, ketones and the like. Particularly preferably used are methanol and ethanol. Further, this reduction reaction can be carried out under a hydrogen gas atmosphere at normal pressure, or can also be carried out by forcibly inserting hydrogen gas under pressure using an autoclave. The temperature of this reduction reaction is usually 0 to 30.
It is 0 ° C. As a method of modifying the amino group of the substituted amino alcohol obtained by the above-mentioned reduction reaction with an aryl group, the method described in Production Method 1 can be adopted.

Production method 3; The amino group of the D-, L- or DL-substituted amino acid ester is modified with an aryl group to give N.
-(Aryl) amino acid ester and then reducing the ester group. As a method of modifying the amino group with an aryl group, the method of modifying the amino group of the substituted amino alcohol described in Production Method 1 with an aryl group can be adopted. For the reduction of the N- (aryl) amino acid ester thus obtained, a reduction method such as the aluminum hydride reduction method, the borohydride reduction method, or the hydrogenation method described in Production Method 2 can be adopted.

Production Method 4; A method in which an epoxide is ring-opened with an arylamine derivative to give a substituted amino alcohol.
Examples of the epoxide used here include propylene oxide, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyoctane, 2,3-epoxypropylbenzene and butadiene. A monoxide etc. can be illustrated. Further, as the arylamine derivative used here, in addition to the arylamine, aryls trimethylsilylamine, lithium arylamide and the like can be exemplified. The amount of these arylamine derivatives used is usually 1 to 20 mol per 1 mol of epoxide. This reaction can be promoted by allowing alumina, titanium tetraisopropoxide and the like to be present in the reaction system. At this time, the amount of alumina, titanium tetraisopropoxide or the like used is usually 1 to 100 mol per mol of the epoxide. This reaction is usually carried out in a solvent, and the solvent used is not particularly limited as long as it is inert to the reaction, and various solvents can be used. Examples thereof include system or aromatic hydrocarbons, halogenated hydrocarbons, ethers, alcohols, ketones, sulfoxides, amides and the like. Particularly preferably used are diethyl ether, dimethylsulfoxide, N-methylpyrrolidone and N, N-dimethylformamide. Also, this reaction temperature is usually
It is 0 to 100 ° C.

Production of Single Crystal The specific compound obtained as described above is obtained by a conventional method, for example, a recrystallization method such as a cooling method or a slow evaporation method, a sublimation method, a zone melting method or the like. It can be a crystal. The solvent used for growing the single crystal by the recrystallization method can be appropriately selected according to the compound to be the single crystal, for example, ethyl acetate, methyl acetate, ethanol, methanol, isopropanol, acetone, methyl ethyl ketone, methyl. Isopropyl ketone, N, N-dimethylformamide, N,
Organic solvents such as N-dimethylacetamide, N-methylpyrrolidone, diethyl ether, tetrahydrofuran, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, pentane, hexane, toluene, xylene and benzene, and mixtures of two or more of the above solvents. Can be mentioned. Further, it is also possible to crystallize into a fiber shape by using a glass capillary, and as a crystallization method at this time, a zone melting method can be used.

Manufacture of Nonlinear Optical Element The single crystal obtained as described above can be suitably used as a nonlinear optical element. At this time, a part or the whole of the single crystal surface may be covered and protected. Coating materials used for this purpose include glass, polycarbonate, polymethylmethacrylate, polypropylene, cellulose acetate, polystyrene, acrylonitrile-polystyrene copolymer, polyethylene glycol bisallyl carbonate, polyvinyl alcohol, polyethylene terephthalate, polyvinyl chloride. , Polysulfone, polyimide and the like. Further, for the purpose of matching the refractive index, the single crystal can be used by immersing it in a medium inert to the surface of the single crystal, such as liquid paraffin, various silicone oils, and fluorine-based oils. Further, the surface of the single crystal is not exposed by the method disclosed in, for example, U.S. Pat. No. 3,330,681, Japanese Patent Publication No. 56-15481, Japanese Unexamined Patent Publication No. 58-670701, and Japanese Patent Publication No. 55-40631. It is also possible to provide a coating layer such as a reflective coating. Alternatively, the entire single crystal may be cooled or heated with an inert medium or the like before use. As this inert medium,
Examples include various silicone oils and fluorine-based oils.

Further, a specific compound is dispersed in a polymer matrix in a fine single crystal state, or is dispersed in a polymer matrix in a molecular form or directly bound to the polymer matrix to form an external electric field. It is possible to manufacture it as a non-linear optical element exhibiting SHG characteristics or an electrochemical effect by orienting it by utilizing. Examples of the material of the polymer matrix and the main chain of the chemical bond used in this case include polyacrylate, polymethacrylate, polystyrene, polymethylstyrene, polyethylene oxide, polyvinyl acetate, polycarbonate, polyacetal, polyphenylene oxide, polyethylene terephthalate, An epoxy resin, a phenol resin, etc. can be mentioned.

[0023]

EXAMPLES Synthesis Example 1 (S) -1-chloro-2- (4-nitrophenyl) ami
Synthesis of Nopropane (a) Reduction of carboxyl group; (S) -2-aminopropanoic acid 10.1 g is dissolved in anhydrous tetrahydrofuran 50 g,
To this, 17.7 g of boron trifluoride ethyl ether was added, and the mixture was stirred at room temperature for 1 hour. 11.7 g of borane-dimethyl sulfide complex was added dropwise to this solution over 30 minutes, and the mixture was reacted at room temperature for 2 hours. Then, 60 g of a 6N sodium hydroxide aqueous solution was added to stop the reaction, and the product was extracted with ethyl ether. Then, the organic layer was dried over anhydrous potassium carbonate, the solvent was removed, and the residue was purified by silica gel column chromatography to obtain (S) -2.
8.50 g of -amino-1-propanol are obtained.

(B) Arylation of amino group: To a solution of 8.50 g of (S) -2-amino-1-propanol obtained above in 100 g of dimethyl sulfoxide, 16.0 g of p-fluoronitrobenzene was added, The reaction was carried out at 50 ° C for 4 hours. 50 g of 2N hydrochloric acid aqueous solution was added to this reaction solution and washed with ethyl ether. Then, the aqueous layer was made basic with 2N sodium hydroxide aqueous solution, and the product was extracted with ethyl ether, and the organic layer was further dried over anhydrous potassium carbonate. After drying with, the solvent was removed. The residue is purified by silica gel column chromatography, (S) -2- (4-
12.2 g of nitrophenyl) amino-1-propanol were obtained.

(C) Chlorination; 12.2 g of the above (S) -2- (4-nitrophenyl) amino-1-propanol was dissolved in 100 g of toluene, and 18.5 g of trichloromethyl chloroformate (phosgene dimer) was dissolved. The mixture was added dropwise and stirred at room temperature for 1 hour. Then, saturated aqueous sodium hydrogen carbonate was added, extraction was performed with ethyl acetate, the organic layer was dried over anhydrous potassium carbonate, and then the solvent was removed. The residue was purified by silica gel column chromatography, (S) -1-chloro-
8.75 g of 2- (4-nitrophenyl) aminopropane was obtained. The identification of this compound was carried out by a nuclear magnetic resonance spectrum,
It was performed by infrared absorption spectrum and mass spectrometry.

Synthesis Example 2 (S) -1-chloro-2- (4-nitrophenyl) ami
Synthesis of No-3-methylbutane The same operation as in Synthesis Example 1 was performed except that (S) -2-amino-3-methylbutanoic acid was used instead of (S) -2-aminopropanoic acid in Synthesis Example 1. , (S) -1-chloro-2- (4-nitrophenyl) amino-3-methylbutane were obtained.

Synthesis Example 3 (2S, 3S) -1-chloro-2- (4-nitropheni)
Synthesis of amino-3-methylpentane Synthesis Example 1 except that (2S, 3S) -2-amino-3-methylpentanoic acid was used in place of (S) -2-aminopropanoic acid in Synthesis Example 1. Perform the same operation as in (2
S, 3S) -1-Chloro-2- (4-nitrophenyl)
Amino-3-methylpentane was obtained.

Synthesis Example 4 (S) -1-chloro-2- (4-nitrophenyl) ami
Synthesis of No-3-phenylpropane The same operation as in Synthesis Example 1 except that (S) -2-amino-3-phenylpropanoic acid was used in place of (S) -2-aminopropanoic acid in Synthesis Example 1. (S) -1-
Chloro-2- (4-nitrophenyl) amino-3-phenylpropane was obtained.

Synthesis Example 5 (S) -1-chloro-2- (4-nitrophenyl) ami
Synthesis of no-3-phenylpropane (S) -2-amino-synthesized in the same manner as in Synthesis Example 1.
1-Propanol was dissolved in a 50% by weight aqueous ethanol solution, sodium hydrogencarbonate and then 2,4-dinitrofluorobenzene were added thereto, and the mixture was reacted for 12 hours. Water was added to this reaction solution, and extraction was further performed with ethyl acetate.
The organic layer was dried over anhydrous potassium carbonate and then the solvent was removed. The residue is purified by silica gel column chromatography, (S) -2- (2,4-dinitrophenyl)
Aminopropanol was obtained. This was dissolved in toluene, trichloromethyl chloroformate (phosgene dimer) was added dropwise, and the mixture was stirred at room temperature for 1 hour. Then, saturated aqueous sodium hydrogen carbonate was added, extraction was performed with ethyl acetate, the organic layer was dried over anhydrous potassium carbonate, and then the solvent was removed.
The residue was purified by silica gel column chromatography to obtain (S) -1-chloro-2- (2,4-dinitrophenyl) aminopropane.

Synthesis Example 6 (S) -1-chloro-2- (2,4-dinitropheni)
Synthesis of (l) amino-3-methylbutane (S) -2-amino-synthesized in the same manner as in Synthesis Example 2.
By reacting 3-methyl-1-butanol in the same manner as in Synthesis Example 5, (S) -1-chloro-2- (2,4-
Dinitrophenyl) amino-3-methylbutane was obtained.

Synthesis Example 7 (2S, 3S) -1-chloro-2- (2,4-dinitro)
Synthesis of (phenyl) amino-3-methylpentane (S) -2-amino-synthesized in the same manner as in Synthesis Example 3.
By reacting 3-methyl-1-pentanol in the same manner as in Synthesis Example 5, (S) -1-chloro-2- (2,4
-Dinitrophenyl) amino-3-methylpentane was obtained.

Synthesis Example 8 (S) -1-chloro-2- (2,4-dinitrophenyl)
Le) Synthesis of amino-3-phenylpropane (S) -2-amino-synthesized in the same manner as in Synthesis Example 4.
By reacting 3-phenyl-1-propanol in the same manner as in Synthesis Example 5, (S) -1-chloro-2- (2,2)
4-dinitrophenyl) amino-3-phenylpropane was obtained.

Experimental Example 1 Each of the compounds obtained in Synthesis Examples 1 to 8 had a particle size of 100 μm.
It is made into powder of about m, and it is filled between glass substrates, and this is filled with Nd: YAG laser (wavelength 1.064 μm, energy
It was irradiated with 350 mJ / pulse and the generated SHG characteristics were observed. The SHG intensity is shown in Table 1 in comparison with that of 2-methyl-4-nitroaniline.

[0034]

[Table 1]

[0035]

The organic nonlinear optical element of the present invention is SHG.
The characteristics are equivalent to those of a non-linear optical element using 2-methyl-4-nitroaniline, and a large single crystal having no center of symmetry showing a second-order non-linear optical characteristic or a matrix having no center of symmetry is orientation-dispersed. The structure can be easily obtained, and the organic compound has low hygroscopicity and sublimation property and excellent optical transparency, and can be suitably used as a nonlinear optical element.

Claims (1)

[Claims] 1. The following general formula (1): [In the formula, R represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or an aralkyl group, Ar represents an aromatic ring or a heteroaromatic ring, and these R and Ar may have a substituent. , X represents a halogen atom] and / or a polymer compound in which the compound is bonded to a polymer matrix.