JPH0545688A - Nonlinear optical element - Google Patents

Abstract

PURPOSE:To obtain a nonlinear optical element practically useful for industry comprising an org. compd. which has extremely excellent optical transparency, stability, crystallinity, etc., and can be easily and stably oriented and dispersed in a matrix compared to an org. compd. conventionally used as a material for a nonlinear optical element. CONSTITUTION:This nonlinear optical element consists of a compd. expressed by formula I. In formula, R is an alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, acyl group, carboxyl group, carbamoil group, benzylthiomethyl group, or alkylthiomethyl group, X is a hydroxyl group, alkoxy group or aralkyloxy group, Ar is an aromatic group, (e.g. 2,4-dinitrophenyl, 4-nitrophenyl, etc.,) or heteroaromatic group (e.g. 5-nitro-2-pyridyl, 3-nitropyridyl, etc).

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 ferroelectrics 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, and some of them are It has been put to practical use as a conversion material. On the other hand, as a material having large nonlinear optical characteristics as compared with these inorganic ferroelectrics,
Recently, 2-methyl-4-nitroaniline, 3-methyl-
Non-linear optical materials made of organic compounds such as 4-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-mentioned structure or to disperse the crystals in the matrix in an oriented manner, and the obtained crystals or structures obtained by the orientation dispersion in the matrix have low hygroscopicity and sublimability. It is required to be stable, have excellent optical transparency in terms of device function, and have a large nonlinear optical constant.

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 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, and the hygroscopicity and sublimability are low and the optical property is stable. An object of the present invention is to provide a nonlinear optical element made of an organic compound having excellent transparency.

[0006]

According to the present invention, the following general formula (1):

[Chemical 2] [Wherein R represents an unsubstituted or substituted alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, acyl group, carboxyl group, carbamoyl group or formula (2):
YSCH ₂ — (Y is a benzyl group or an alkyl group having 1 to 4 carbon atoms), X is a hydroxyl group, an alkoxy group or an aralkyloxy group, and Ar is an aromatic group or a heteroaromatic group. A compound represented by an aromatic group and optionally having a substituent on its ring] (hereinafter, referred to as “specific compound”) and / or a specific compound chemically bound to the polymer matrix A non-linear optical element made of a polymer compound is provided.

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 20 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 of R include ethynyl, propargyl, 2-butynyl, 2-methyl-3-butynyl, 4-hexadecynyl and the like having 2 to 16 carbon atoms. 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 a benzyl group and a phenethyl group. Examples of the acyl group of R include formyl, acetyl, benzoyl, cinnamoyl and the like. Also,
Formula (2): YSCH _2- (Y is a benzyl group or a carbon number of 1 to
Examples of the group represented by (alkyl group of 4) include (methylthio) methyl group, (benzylthio) methyl group, (n-propylthio) methyl group and the like. Further, each of the groups described above has a part of its hydrogen atom,
For example, it may be substituted with a halogen atom such as a chlorine atom, a bromine atom, a fluorine atom, an alkoxy group such as a methoxy group, an aryl group such as a phenyl group, or an acylamino group such as an acetylamino group. In the present invention, R in the general formula (1) is preferably an alkyl group (especially having 2 to 7 carbon atoms), an aryl group (especially a phenyl group, o-, m- or p-) among the above. And a group represented by the above formula (2).

In the general formula (1), among the hydroxyl group, alkoxy group and aralkyloxy group represented by X, examples of the alkoxy group include methoxy group and ethoxy group, and the aralkyloxy group includes A benzyloxy group can be mentioned. In the present invention, a hydroxyl group is particularly preferable.

Further, in the general formula (1), examples of the aromatic group of Ar include phenyl group, naphthyl group and azulenyl group, and examples of the heteroaromatic group include pyridinyl group and quinolyl group. Examples thereof include a group, an isoquinolyl group, a thienyl group, a furyl group, a pyrrolyl group, an imidazolyl group and a pyrimidinyl group. These groups may have a substituent on the ring, and examples of the substituent include a nitro group, a cyano group, an alkoxycarbonyl group, an alkylcarbonyl, a perfluoroalkylcarbonyl group, a perfluoroalkyl group and the like. Electron-withdrawing groups and electron-donating groups such as amino groups, monoalkylamino groups, dialkylamino groups, alkylcarbonylamino groups, perfluoroalkylcarbonylamino groups, hydroxyl groups, alkoxy groups, aryloxy groups, alkyl groups, halogens, etc. And these may be substituted on the aromatic ring or the heteroaromatic ring in a combination of two or more kinds.

Specific examples of such an aromatic group include:
2-nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group, 2,4-dinitrophenyl group, 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group, 2,4-dicyanophenyl group Group, 3-methoxycarbonyl group, 4-methoxycarbonyl group, 3-ethoxycarbonyl group, 4-ethoxycarbonyl group, 2-acetylphenyl group, 3-acetylphenyl group, 4-acetylphenyl group, 4-trifluoroacetylphenyl Base, 2-
Trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 5
-Fluoro-2,4-dinitrophenyl group, 2-acetylamino-4-nitrophenyl group, 2-trifluoroacetylamino-4-nitrophenyl group, 2-dimethylamino-4-nitrophenyl group, 2- (t -Butoxycarbonyl) amino-4-nitrophenyl group, 2- (benzyloxycarbonyl) amino-4-nitrophenyl group, 4
-Acetylamino-3-nitrophenyl group, 4-trifluoroacetylamino-3-nitrophenyl group, 4-
(Benzyloxycarbonyl) amino-3-nitrophenyl group, 4-acetylamino-2-nitrophenyl group,
4-trifluoroacetylamino-2-nitrophenyl group, 4-dimethylamino-2-nitrophenyl group, 4-
(T-Butoxycarbonyl) amino-2-nitrophenyl group, 4- (benzyloxycarbonyl) amino-2-
Examples thereof include a nitrophenyl group, a 2-methoxy-5-nitrophenyl group, a 4-methoxy-5-nitrophenyl group, a 3-fluoro-4-nitrophenyl group and a 3-fluoro-6-nitrophenyl group.

Similarly, specific examples of the heteroaromatic group include 3-nitro-2-pyridinyl group and 4-nitro- group.
2-pyridinyl group, 5-nitro-2-pyridinyl group, 6
-Nitro-2-pyridinyl group, 3-cyano-2-pyridinyl group, 4-cyano-2-pyridinyl group, 5-cyano-
2-pyridinyl group, 6-cyano-2-pyridinyl group, 3,
4-dicyano-2-pyridinyl group, 4-amino-5-nitro-2-pyridinyl group, 4-nitro-2-quinolyl group, 5-nitro-2-quinolyl group, 6-nitro-2-quinolyl group, 8 -Nitro-2-quinolyl group, 4-nitro-
1-isoquinolyl group, 5-nitro-1-isoquinolyl group, 6-nitro-1-isoquinolyl group, 8-nitro-1
-Isoquinolyl group, 4-methyl-1-isoquinolyl group,
3-nitro-2-thienyl group, 4-nitro-2-thienyl group, 5-nitro-2-thienyl group, 2-nitro-3-
Thienyl group, 3-chloro-2-thienyl group, 3-nitro-2-furyl group, 4-nitro-2-furyl group, 5-nitro-2-furyl group, 2-nitro-3-furyl group, 3- Chloro-2-furyl group, 3-nitro-2-pyrrolyl group, 4
-Nitro-2-pyrrolyl group, 5-nitro-2-pyrrolyl group, 1-methyl-2-imidazolyl group, 1-methyl-4
Examples thereof include -nitro-5-imidazolyl group, 1-methyl-5-nitro-4-imidazolyl group, 5-nitro-2-pyrimidinyl group and the like.

In the present invention, particularly preferable Ar is a nitro-2-pyridinyl group. In the present invention, specific examples of the specific compound represented by the above general formula (1) include:
For example, one represented by the following formula can be exemplified.
In these formulas, Me represents a methyl group, Ph represents a phenyl group, and Bn represents a benzyl group.

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical formula 12]

[Chemical 13]

[Chemical 14]

Method for Synthesizing Specific Compound The specific compound represented by the above general formula (1) has the following formula, for example, when X in the above general formula (1) is a hydroxyl group, that is, an aminoethanol derivative. Can be synthesized by the method. In the following, R in the general formula (1)
An α-amino acid having a substituent corresponding to α at the α-position is referred to as a “substituted amino acid”, and a 2-aminoethanol derivative having a substituent corresponding to the above R at the 2-position is referred to as a “substituted amino alcohol”.

Production Method 1; 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 converted to an aromatic group or A method of modifying with a heteroaromatic 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, "Reductionsin Organic C
(See hemistry ", Willy, New York, 1984). This borane reduction method is effectively applied to the reduction of optically active substituted amino acids without racemization during 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, borane-pyridine complex, borane-dimethylamine complex, borane-diethylamine complex, borane-t-butylamine complex, borane-tetrahydrofuran complex, borane-morpholine complex, borane-ether complex, diborane and the like can be used. Of these, the preferred one is Borane-dimethyl sulfide complex, borane-ether complex and diborane are used.The amount of the borane reagent used is stoichiometrically equivalent to or more than 1 mol of the substituted amino acid, preferably 1 to 2 mol. is there.

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 aromatic group or a heteroaromatic group include aromatic derivatives or heteroaromatics having a leaving group on the ring. A method of reacting a derivative with the substituted amino alcohol can be mentioned. Examples of the leaving group on this ring include a fluoro group, a chloro group,
Examples thereof include a bromo group, an iodo group, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, and a trifluoromethanesulfonyloxy group, and a chloro group and a trifluoromethanesulfonyloxy group are particularly preferable. The amount of the aromatic derivative or heteroaromatic derivative having such a leaving group to be used is stoichiometrically equal to or more than 1 mol of the substituted amino alcohol, and preferably 1 to 2 mol.

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

Production method 2; D-, L-, or DL-substituted amino acid ester is reduced to a D-, L-, or DL-substituted amino alcohol, and then the amino group is converted to an aromatic group or a heteroaromatic group. Method of modifying with an aromatic group. In the above, examples of the method for reducing the substituted amino acid ester include aluminum hydride reduction method, borohydride reduction method, hydrogenation method and the like (M. Hud-licky, "Reductions
in Organic Chemistry ", Willy, New York, 1984).
.. 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, as a reducing agent to be used,
Aluminum hydride, lithium aluminum hydride, sodium aluminum hydride, magnesium aluminum hydride, lithium dimethoxyaluminum hydride, lithium trimethoxyaluminum hydride, tris hydride hydride
Examples thereof include (t-butoxy) aluminum, sodium bis (2-methoxyethoxy) aluminum hydride, and diisobutylaluminum hydride. Among these, lithium aluminum hydride and lithium dimethoxyaluminum hydride are preferable. These reducing agents are usually used in an amount of 0.5 per mol of the substituted amino acid ester.
Used in proportions of up to 10 moles. The reduction reaction in this case is
Usually, it is carried out 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. Particularly preferably used is
Tetrahydrofuran, diethyl ether, toluene. The temperature of the reduction reaction is usually -20 to 110 ° C. In this aluminum hydride reduction method,
In addition to the substituted amino acid ester, a substituted amino acid ester hydrochloride can be used as a starting material.

In the borohydride reduction method, as a reducing agent to be used, lithium borohydride, sodium borohydride, calcium borohydride, zinc borohydride,
Examples thereof include lithium triethylborohydride, sodium triethylborohydride, sodium trimethoxyborohydride, and the like, and sodium borohydride and lithium borohydride are preferably used. These reducing agents are usually used in a proportion of 0.5 to 20 mol per mol of the substituted amino acid ester. 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. System or aromatic hydrocarbons, halogenated hydrocarbons, ethers,
Examples thereof include 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, as a catalyst, 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 for modifying the amino group of the substituted amino alcohol obtained by the above-mentioned reduction reaction with an aromatic group or a heteroaromatic group, the method described in Production Method 1 can be adopted.

Production method 3; a method of modifying the amino group of a D-, L- or DL-substituted amino acid ester with an aromatic group or a heteroaromatic group and then reducing the ester group. As a method of modifying the amino group with an aromatic group or a heteroaromatic group, a method of modifying the amino group of the substituted aminoalcohol mentioned in the production method 1 with an aromatic group or a heteroaromatic group can be used. Can be adopted. The N- (aromatic) amino acid ester or N- (heteroaromatic) amino acid ester thus obtained is reduced by the aluminum hydride reduction method, the borohydride reduction method, the hydrogenation method, etc. described in the production method 2. Can be adopted.

Production method 4; A method in which an epoxide is opened with an aromatic amine derivative or a heteroaromatic amine 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. Examples thereof include monoxide and styrene oxide. In addition to the aromatic amine, examples of the aromatic amine derivative used here include aromatic trimethylsilylamine, lithium aromatic amide, and the like. Examples of the heteroaromatic amine derivative used here include N- (trimethylsilyl) heteroaromatic amine and lithium heteroaromatic amide, in addition to the heteroaromatic amine. The amount of these 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. This method is advantageous in that the desired aminoethanol derivative can be obtained particularly in one step.

Production method 5: Of the specific compounds represented by the above general formula (1), X is an alkoxy group in the general formula (1),
And the compound which is an aralkyloxy group, the hydroxyl group of the aminoethanol derivative obtained in the above production methods 1 to 4 is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, or a benzyl group or 2-phenyl group. It can be synthesized by protecting with an aralkyl group such as an ethyl group, a 1-naphthylmethyl group or a 2-naphthylmethyl group. (TWGreen, "Protective Groups in Organic
See Syn-thesis ", Willy, Newyork, 1981).
Examples of the reagent used include halides having a corresponding alkyl group, p-toluenesulfonyl ester, methanesulfonyl ester, trifluoromethanesulfonyl ester and the like and halides having a corresponding aralkyl group, p-toluenesulfonyl ester, methanesulfonyl ester, Examples thereof include trifluoromethanesulfonyl ester. The amount of the reagent used is stoichiometrically equivalent to or excess of 1 mol of the aminoethanol derivative, preferably 1 to 2 mol. It is desirable to carry out the reaction in the presence of a base. 3 as a base
Examples thereof include primary amines and pyridines, and particularly preferably used are sodium hydride, triethylamine, diisopropylethylamine and pyridine. The amount of the base used is stoichiometrically equivalent to or excess of 1 mol of aminoethanol, preferably 1
~ 5 moles. The reaction is usually performed in a solvent at 0 to 55 ° C. The solvent used is not particularly limited as long as it is inert to the reaction, and various solvents can be used. Specifically, aliphatic or aromatic hydrocarbons, halogen Examples of the hydrocarbon include ethers, amides and the like. Particularly preferred are tetrahydrofuran, diethyl ether, N, N-dimethylformamide. When protecting with a t-butyl group, a method in which isobutylene is allowed to act in the presence of a catalytic amount of acid can be used. As the acid used,
Sulfuric acid, hydrochloric acid, p-toluenesulfonic acid and the like can be mentioned. The reaction is usually performed in a solvent at -20 to 50 ° C. The solvent used is not particularly limited as long as it is inert to the reaction, and various solvents can be used. Specifically, aliphatic or aromatic hydrocarbons, halogen Chemical hydrocarbons, ethers and the like can be mentioned, but particularly preferable ones are dichloromethane and diethyl ether.

Production of Crystals The specific compound represented by the general formula (1) obtained as described above is used in a commonly used method, for example, a recrystallization method such as a cooling method or a slow evaporation method, a sublimation method or a zone method. A single crystal can be obtained by a method such as a melting method. The solvent used for growing the single crystal by the recrystallization method can be appropriately selected according to the specific compound to be the single crystal, and for example, ethyl acetate, ethanol, methanol, acetone, dichloromethane, chloroform, carbon tetrachloride, etc. And organic solvents, and mixed solvents of the above-mentioned solvents with hexane, toluene or benzene. 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.

Production of Nonlinear Optical Element The crystal obtained as described above can be suitably used as a nonlinear optical element. At this time, a part or the whole of the 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,
Examples thereof include polyimide. Further, for the purpose of matching the refractive index, the crystal can be used by immersing it in a medium inert to the surface of the crystal, such as liquid paraffin, various silicone oils, and fluorinated oils. Furthermore, on the surface of the crystal, for example, US Pat. No. 3,330,681, Japanese Patent Publication
56-15481, JP-A-58-670701, JP-B-55
A coating layer such as a non-reflective coating can be provided by the method disclosed in JP-A-40631. The entire crystal may be cooled or heated with an inert medium or the like. Examples of this inert medium include various silicone oils and fluorine-based oils.

Further, the specific compound represented by the general formula (1) is dispersed in a polymer matrix in a microcrystalline state, molecularly dispersed in the polymer matrix, or directly dispersed in the polymer matrix. By mechanically bonding the materials, they are oriented by utilizing an external electric field, so that they can be manufactured as an element exhibiting SHG characteristics or an electrochemical effect. As a method of dispersing in a polymer matrix, for example, a compound represented by the general formula (1) and a polymer serving as a matrix are dissolved and mixed in a solvent and then the solvent is removed, and both are melted and mixed. And a method of polymerizing a monomer in the presence of the compound by a polymerization initiator, heating, light irradiation or the like to form a polymer serving as a matrix. In these cases, if necessary, an acid, a base, a metal, or the like is allowed to coexist, and exchange, condensation, addition, etc. are performed between the functional group of the compound represented by the general formula (1) and the functional group of the polymer matrix. Can be caused to form a chemical bond.
Examples of the polymer matrix 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.

[0027]

EXAMPLES Example 1 4-Methyl-2- (5-nitro-2-pyridinyl) ami
Synthesis of No-1-pentanol (a) Reduction of carboxyl group; 50 g of 2-amino-4-methylpentanoic acid was dissolved in 250 g of anhydrous tetrahydrofuran, and 59.5 g of boron trifluoride ethyl ether was added thereto, and a dry nitrogen atmosphere was added. Stirring was carried out below at 60 ° C. for 1 hour.
To this solution, 41.9 ml of a 10 M borane-dimethyl sulfide complex in dimethyl sulfide was added dropwise over 30 minutes, and the mixture was reacted under heating under reflux for 2 hours. Then, the reaction was stopped by adding 300 ml of 6N aqueous sodium hydroxide solution, 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 using ethyl acetate as a developing solvent, and 2-amino-4-methyl-
40.8 g of 1-pentanol was obtained.

(B) Modification of amino group with 5-nitro-2-pyridinyl group; 5-nitro-2-chloropyridine 60.7
g of N-methylpyrrolidone in 300 g was stirred at room temperature, and the 2-amino-
A solution prepared by dissolving 40.8 g of 4-methyl-1-pentanol and 42.3 g of triethylamine in 150 g of N-methylpyrrolidone was added dropwise over 1 hour. After reacting for 12 hours at room temperature, 400 ml of 5 wt% hydrochloric acid aqueous solution and 1000 ml of water were added to the reaction mixture
ml was added and the product was extracted with ethyl acetate. Then, the organic layer was washed with water and then with saturated saline, dried over anhydrous magnesium sulfate, and then the solvent was removed. The obtained residue was purified by silica gel column chromatography using a mixed solvent of dichloromethane and hexane (volume ratio = 5: 1) as a developing solvent, and the collected yellow solid was recrystallized with ethyl acetate to give a thin solid. Yellow needles
54.7 g was obtained. This needle crystal has an infrared absorption spectrum (shown in FIG. 1) and a nuclear magnetic resonance spectrum (shown in FIG. 2).
Was identified as 4-methyl-2- (5-nitro-2-pyridinyl) amino-1-pentanol (hereinafter referred to as compound A). The melting point of compound A was 120.0 ° C. Furthermore, compound A was heated to 120 ° C. at 20 mtorr to give pale yellow needles (0.5 mm × 1.0 mm).
mm × 10 mm) could be easily obtained. This needle is
It was confirmed to be a single crystal by a polarization microscope. When this crystal was used as a seed crystal and crystal growth was carried out from an ethyl acetate solution of compound A, after 10 days, 5.5 mm × 4.5 mm × 10 mm
Was obtained. The crystals were neither hygroscopic nor sublimable, and were stable at room temperature and pressure for 100 days.

Example 2 2- (5-nitro-2-pyridinyl) amino-2-phen
Synthesis of Nylethanol The procedure of Example 1 was repeated except that 50 g of 2-amino-2-phenylethanoic acid was used in place of 2-amino-4-methylpentanoic acid in Example 1, and a light yellow color was obtained. 45.3 g of plate crystals were obtained. This plate crystal was analyzed by infrared absorption spectrum (shown in FIG. 3) and nuclear magnetic resonance spectrum (shown in FIG. 4) to give 2- (5-nitro-2-pyridinyl) amino-2-phenylethanol (hereinafter referred to as compound). (Referred to as B). Further, the plate crystal of the compound B has neither hygroscopicity nor sublimation property, and was left for 30 days at room temperature and atmospheric pressure, but no modification was observed.

Example 3 3-Methyl-2- (5-nitro-2-pyridinyl) ami
Synthesis of No-1-pentanol The same operation as in Example 1 was performed except that 50 g of 3-methyl-2-aminopentanoic acid was used instead of 2-amino-4-methylpentanoic acid in Example 1. 52.8 g of pale yellow needles were obtained. This acicular crystal shows 3-methyl-2- (5-nitro-2-pyridinyl) amino-1-pentanol by infrared absorption spectrum (shown in FIG. 5) and nuclear magnetic resonance spectrum (shown in FIG. 6). (Hereinafter referred to as compound C). Further, the needle-like crystals of Compound C were neither hygroscopic nor sublimable, and were left to stand at room temperature and atmospheric pressure for 30 days, but no modification was observed.

Example 4 2- (5-Nitro-2-pyridinyl) amino-1-buta
Synthesis of Nool In the same manner as in Example 1 except that 59 g of 2-aminobutanoic acid was used instead of 2-amino-4-methylpentanoic acid, 65.5 g of pale yellow needles were obtained. Obtained. This needle crystal has an infrared absorption spectrum (shown in FIG. 7).
And the nuclear magnetic resonance spectrum (shown in FIG. 8)
It was identified as-(5-nitro-2-pyridinyl) amino-1-butanol (hereinafter referred to as compound D). Further, the needle-like crystals of the compound D were neither hygroscopic nor sublimable, and were allowed to stand at room temperature and atmospheric pressure for 30 days, but no modification was observed.

Example 5 3-Methyl-2- (5-nitro-2-pyridinyl) ami
Synthesis of No-1-butanol The procedure of Example 1 was repeated except that 50 g of 3-methyl-2-aminobutanoic acid was used instead of 2-amino-4-methylpentanoic acid in Example 1 to obtain a thin solution. Yellow needles
67.2 g was obtained. This needle crystal has an infrared absorption spectrum (shown in FIG. 9) and a nuclear magnetic resonance spectrum (shown in FIG. 10).
Was identified as 3-methyl-2- (5-nitro-2-pyridinyl) amino-1-butanol (hereinafter referred to as compound E). Further, the needle-like crystals of compound E were neither hygroscopic nor sublimable, and were left to stand at room temperature and atmospheric pressure for 30 days, but no modification was observed.

Example 6 2- (5-Nitro-2-pyridinyl) amino-1-pro
Panol Synthesis In the same manner as in Example 1 except that 50 g of 2-aminopropanoic acid was used in place of 2-amino-4-methylpentanoic acid in Example 1, 140.2 g of pale yellow needles were obtained. Obtained. This needle crystal has an infrared absorption spectrum (shown in Fig. 11).
And the nuclear magnetic resonance spectrum (shown in FIG. 12)
It was identified as-(5-nitro-2-pyridinyl) amino-1-propanol (hereinafter referred to as compound F). Also,
The needle-like crystals of compound F were neither hygroscopic nor sublimable, and were left to stand at room temperature and atmospheric pressure for 30 days, but no modification was observed.

Example 7 2- (5-Nitro-2-pyridinyl) amino-3-phen
Synthesis of Nyl-1-propanol The same operation as in Example 1 was carried out except that 50 g of 2-amino-3-phenylpropanoic acid was used in place of 2-amino-4-methylpentanoic acid in Example 1. 59.8 g of pale yellow needles were obtained. This needle crystal was confirmed by infrared absorption spectrum (shown in FIG. 13) and nuclear magnetic resonance spectrum (shown in FIG. 14) to be 2- (5-nitro-2-pyridinyl) amino-3-phenyl-1-propanol ( Hereinafter, compound G
It is identified as). In addition, the needle-like crystals of compound G are
It was not hygroscopic and sublimable, and was left for 30 days at room temperature and pressure, but no denaturation was observed.

Example 8 3-Benzylthio-2- (5-nitro-2-pyridini)
1) Synthesis of amino-1-propanol As in Example 1, except that 50 g of 3-benzylthio-2-amino-3-phenylpropanoic acid was used in place of 2-amino-4-methylpentanoic acid in Example 1. The same operation is performed and 3-benzylthio-2- (5-nitro-2-pyridinyl) amino-1-propanol (hereinafter referred to as compound H
37.8 g of light yellow needles of It is shown in the infrared absorption spectrum of needle crystals of compound H (shown in FIG. 15). Further, the needle-like crystals of the compound H were neither hygroscopic nor sublimable, and were left to stand at room temperature and atmospheric pressure for 30 days, but no modification was observed.

Test Example 1 Each of the compounds obtained in Examples 1 to 4 and 9 was made into a powder having a particle size of about 100 μm, which was filled between glass substrates, and this was 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 observed SHG intensity is shown in Table 1 below in comparison with that of 2-methyl-4-nitroaniline.

[0037]

Table 1 Specific compounds SHG relative intensities Compound A 1.0 Compound B 0.7 Compound C 0.5 Compound D 0.8 Compound H 1.0

[0038]

INDUSTRIAL APPLICABILITY The nonlinear optical element of the present invention is remarkably excellent in optical transparency, stability, crystallinity and the like as compared with the organic compound used as a conventional nonlinear optical element and is easily stable in a matrix. It is composed of an organic compound that can be oriented and dispersed. Therefore, it is industrially highly practical.

[Brief description of drawings]

FIG. 1 is a diagram showing an infrared absorption spectrum of compound A obtained in Example 1.

FIG. 2 is a diagram showing a nuclear magnetic resonance spectrum of the compound A.

FIG. 3 is a diagram showing an infrared absorption spectrum of compound B obtained in Example 2.

FIG. 4 is a diagram showing a nuclear magnetic resonance spectrum of the compound B.

FIG. 5 is a view showing an infrared absorption spectrum of compound C obtained in Example 3.

FIG. 6 is a diagram showing a nuclear magnetic resonance spectrum of the compound C.

FIG. 7 is a diagram showing an infrared absorption spectrum of compound D obtained in Example 4.

FIG. 8 is a diagram showing a nuclear magnetic resonance spectrum of the compound D.

FIG. 9 is a diagram showing an infrared absorption spectrum of compound E obtained in Example 5.

FIG. 10 is a diagram showing a nuclear magnetic resonance spectrum of the compound E.

FIG. 11 is a diagram showing an infrared absorption spectrum of the compound F obtained in Example 6.

FIG. 12 is a diagram showing a nuclear magnetic resonance spectrum of the compound F.

FIG. 13 is a diagram showing an infrared absorption spectrum of the compound G obtained in Example 7.

FIG. 14 is a diagram showing a nuclear magnetic resonance spectrum of the compound G.

FIG. 15 is a diagram showing an infrared absorption spectrum of the compound H obtained in Example 8.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C07C 217/48 6742-4H 229/22 8930-4H 237/06 7106-4H 271/12 6917-4H 323/25 7419-4H C07D 213/74 6701-4C C08F 8/00 MFV 8016-4J

Claims (1)

[Claims] 1. The following general formula (1): [Wherein R is an unsubstituted or substituted alkyl group, alkenyl group, alkynyl group, aryl group, aralkyl group, acyl group, carboxyl group, carbamoyl group or the formula: YS
CH ₂ — (Y is a benzyl group or an alkyl group having 1 to 4 carbon atoms), X is a hydroxyl group, an alkoxy group or an aralkyloxy group, and Ar is an aromatic group or a heteroaromatic group. A non-linear optical element comprising a compound represented by an aromatic group and optionally having a substituent on its ring] and / or a polymer compound in which the compound is chemically bonded to a polymer matrix.