JPH0534744A - Nonlinear optical element - Google Patents

Abstract

(57) [Summary] [Structure] The nonlinear optical element of the present invention has the following general formula: [In the formula, Ar is an aromatic group or a heteroaromatic group, and R is an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 8 carbon atoms, an aralkyl group having 7 to 9 carbon atoms, or formula:
X'SCH _2- (X 'represents a group represented by a benzyl group or an alkyl group having 1 to 4 carbon atoms) and / or the compound is chemically bonded to a polymer matrix. It consists of a polymer compound. [Effect] The nonlinear optical element of the present invention is remarkably excellent in transparency, stability and crystallinity as compared with the organic compound used as a conventional nonlinear optical element, and can be easily and stably oriented and dispersed in a matrix. It consists of organic compounds.
Therefore, it is industrially highly practical and can be suitably used as a wavelength conversion element or the like.

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 crystals with no center of symmetry and shows great non-linear optical characteristics, but it is difficult to obtain large single crystals with excellent stability, and orientation dispersion is performed so that there is no center of symmetry in the matrix. There is a problem that it is difficult to do so, and further, there is 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 symmetry center exhibiting a second-order nonlinear optical characteristic or a structure in which a matrix has an orientationally dispersed structure that does not have a symmetry center. An object is to provide a non-linear optical element made of an organic compound having excellent properties.

[0006]

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

[Chemical 2] [In the formula, X, Y, and Z are carbon atoms, oxygen atoms,
Representing a sulfur atom or a nitrogen atom, other atoms other than the oxygen atom may have a hydrogen atom or a monovalent or divalent substituent, and Ar is an aromatic group or a heteroaromatic group. And may have a substituent on its ring] (hereinafter, referred to as “specific compound”) and / or a polymer compound in which the specific compound is chemically bonded to a polymer matrix. A non-linear optical element is provided.

That is, as is clear from the above general formula (1), the specific compound constituting the nonlinear optical element of the present invention is
It has a basic structure in which a heterocycle is bonded to Ar. Examples of this heterocycle include various ones, which are shown below by classifying them according to the types of each atom of X, Y and Z.

[0008]

The X, Y and Z atoms constituting a part of this heterocycle may have a hydrogen atom or a monovalent or divalent substituent, and the monovalent substituent may be an alkyl group, alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, an acyl group, a carboxyl group, a carbamoyl group, an amino group and the general formula _(2): X'SCH 2 - (wherein, X 'is a benzyl group or a 1 to 4 carbon atoms Group, which represents an alkyl group of). Examples of the alkyl group here include a methyl group, an ethyl group, a propyl group, a cyclopropyl group, a butyl group, a cyclobutyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a heptyl group, a cycloheptyl group, an octyl group, and a cyclo group. Examples thereof include those having 1 to 20 carbon atoms such as octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group and eicosyl group. Examples of the alkenyl group include those having 2 to 20 carbon atoms such as vinyl group, allyl group, butenyl group, hexenyl group, hexadecenyl group, butadienyl group, hexadecadienyl group, pentadienyl group and cyclopentadienyl group. You can Examples of the alkynyl group include those having 2 to 16 carbon atoms such as an ethynyl group, a propargyl group, a butynyl group and a hexadecynyl group. Examples of the aryl group include those having 6 to 22 carbon atoms such as phenyl group, biphenyl group and naphthyl group. Examples of the amino group include a methylamino group, a dimethylamino group, a benzylamino group, a t-butoxycarbonylamino group, and a benzyloxycarbonylamino group, in addition to the amino group. Further, examples of the group represented by the general formula (2) include a (methylthio) methyl group and a (benzylthio) methyl group.

Examples of the divalent substituent that the X, Y and Z atoms can have include an alkylidene group, an alkenylidene group, an imino group, an oxo group and a thioxo group. Here, as the alkylidene group, for example, a methylene group, an ethylidene group, a propylidene group, a butylidene group, a pentylidene group, a hexylidene group,
Examples thereof include those having 1 to 20 carbon atoms such as an octylidene group, a decylidene group, a dodecylidene group, a tetradecylidene group, a hexadecylidene group, an octadecylidene group, and an eicosylidene group. Examples of the alkenylidene group include those having 1 to 20 carbon atoms such as vinylidene group, propenylidene group, butenylidene group, and hexenylidene group. Examples of the alkynylidene group include those having 3 to 16 carbon atoms such as propynylidene group, butynylidene group, and hexadecynylidene group.

The above-mentioned monovalent or divalent substituent may have, for example, a part or all of its hydrogen atoms substituted, and examples of such a substituent include an alkyl group such as a methyl group and an ethyl group. Group; alkenyl group such as vinyl group, allyl group; alkynyl group such as ethynyl group, aryl group such as phenyl group, naphthyl group, quinolyl group; aralkyl group such as benzyl group, phenethyl group; fluorine, chlorine,
Halogen atom such as bromine and iodine; Alkoxy group such as methoxy group, ethoxy group, benzyloxy group and methoxybenzyloxy group; Aryloxy group such as phenyloxy group and nitrophenyloxy group; Amino group, dimethylamino group, t- Amino group such as butoxycarbonylamino group, benzyloxycarbonylamino group, nitroguanidino group, toluenesulfonylguanidino group; alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group; t-butylthio group, benzylthio group And other alkylthio groups; imidazolyl groups such as benzylimidazolyl group and benzyloxyimidazolyl group; hydroxyl group; cyano group; carboxyl group; nitro group.

In the present invention, a preferable example of the above-mentioned heterocycle is a 2-oxazolidinone ring (X = oxygen atom, Y = carbon atom, Z = carbon atom), and particularly a carbon atom (Z) at the 4-position. In addition, an alkyl group having 1 to 7 carbon atoms and an aryl group having 6 to 8 carbon atoms (for example, a phenyl group, o-, m-
Or a p-tolyl group, etc.), an aralkyl group having 7 to 9 carbon atoms (eg, benzyl group, phenylethyl group, etc.) and a group represented by the formula (2) (eg, (methylthio) methyl group,
Those to which a substituent such as (benzylthio) methyl group and the like is bonded are 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 group, a perfluoroalkylcarbonyl group, a perfluoroalkyl group. Electron-withdrawing groups such as groups, and amino groups, monoalkylamino groups,
Examples thereof include electron donating groups such as a dialkylamino group, an alkylcarbonylamino group, a perfluoroalkylcarbonylamino group, a hydroxyl group, an alkoxy group, an aryloxy group, an alkyl group and a halogen. These are a combination of two or more kinds, It may be substituted on the aromatic or heteroaromatic ring.

Specific examples of the aromatic group having such a substituent include, for example, 2-nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group, 2,4-dinitrophenyl group and 2-cyano. Phenyl group, 3-cyanophenyl group, 4-cyanophenyl group, 2,4-dicyanophenyl group, 3-methoxycarbonyl group, 4-methoxycarbonyl group, 3-ethoxycarbonyl group, 4-ethoxycarbonyl group, 2-acetyl Phenyl group, 3-acetylphenyl group, 4-acetylphenyl group, 4-trifluoroacetylphenyl group, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 5-fluoro -2,4-dinitrophenyl group, 2-acetylamino-4-nitrophenyl group, 2-trif Oroacetylamino-4-nitrophenyl group, 2-dimethylamino-4-nitrophenyl group, 2- (t-butoxycarbonyl) amino-4-nitrophenyl group, 2- (benzyloxycarbonyl) amino-4-nitrophenyl group Group, 4-acetylamino-3-
Nitrophenyl group, 4-trifluoroacetylamino-
3-nitrophenyl group, 4-dimethylamino-3-nitrophenyl group, 4- (t-butoxycarbonyl) amino-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-nitrophenyl group, 2-
Methoxy-5-nitrophenyl group, 4-methoxy-5-
Nitrophenyl group, 3-fluoro-4-nitrophenyl group, 3-fluoro-6-nitrophenyl group, 4-nitro-1-naphthyl group, 5-nitro-1-naphthyl group, 6-
Nitro-1-naphthyl group, 7-nitro-1-naphthyl group, 8-nitro-1-naphthyl group, 4-nitro-2-naphthyl group, 5-nitro-2-naphthyl group, 6-nitro-
2-naphthyl group, 7-nitro-2-naphthyl group, 8-nitro-2-naphthyl group, 1-azulenyl group, 2-azulenyl group and the like can be mentioned.

Similarly, specific examples of the heteroaromatic group having a substituent include a 3-nitro-2-pyridinyl group,
4-nitro-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-nitro-5-imidazolyl group, 1-methyl-5-nitro-4-imidazolyl group, 5-nitro-2
-Pyrimidinyl group etc. can be mentioned.

In the present invention, particularly preferred Ar is a dinitrophenyl group, a 2-acetylamino-4-nitrophenyl group, a nitro-2-pyridinyl group or a 4-nitrophenyl group. Particularly in the case of a dinitrophenyl group and a 2-acetylamino-4-nitrophenyl group, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 8 carbon atoms is added to the atom (Z) at the 4-position of the above-mentioned heterocycle. It is preferred that the groups are attached. When Ar is a nitro-2-pyridinyl group, at the 4-position atom (Z) of the heterocycle described above, an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 9 carbon atoms or the above formula (2 It is preferred that the group represented by) is bonded.

In the present invention, specific examples of the specific compound represented by the above general formula (1) include those represented by the following formula.

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10] [In the Formula, Ac represents a CH ₃ CO group]

Production of Specific Compound The specific compound of the present invention has the following formula (2) Ar-NH-Z-Y-XH (2) [wherein R, X, Y, Z and Ar are as described above]. A compound represented by (hereinafter, “N-substituted amino alcohol”)
That is) can be produced by cyclization. Hereinafter, typical methods of cyclization reaction of N-substituted amino alcohol (in formula (2), X = 0 and Y = Z = CHR) will be described.

Method using phosgene: Phosgene is introduced into a solution of N-substituted amino alcohol and reacted to obtain a specific compound. The reaction temperature at this time is -20 to 110 ° C. The solvent used in this reaction is not particularly limited as long as it is inert to the reaction, and various solvents can be used. Specific examples include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers and the like. Of these, preferred are hexane, benzene, toluene, dichloromethane,
Chloroform, tetrahydrofuran, diethyl ether and the like. Phosgene used in the reaction is, for example, a method of decomposing carbon tetrachloride with fuming sulfuric acid and a method of decomposing trichloromethyl chloroformate with activated carbon (edited by the Chemical Society of Japan,
"New Experimental Chemistry Course", Vol. 19, p. 245; see Maruzen (1978)). The amount of phosgene used is usually in large excess with respect to the N-substituted amino alcohol. As a method of introducing the generated phosgene into the reaction system, a method of bubbling in the reaction system in a gaseous state, a method of dropping after cooling and aggregating into a liquid, and a method of dissolving the generated phosgene in the solvent described above A dropping method or the like can be used. Further, this reaction may be carried out in the presence of a base, and examples of the base used in this case include sodium methoxide, sodium ethoxide, sodium carbonate, potassium carbonate, triethylamine, pyridine and the like. The amount of the base used is usually 0.05 to 10 with respect to 1 mol of the N-substituted amino alcohol.
It is a mole.

Method using disubstituted carbonate: A disubstituted carbonate is introduced into a solution of an N-substituted aminoalcohol and reacted to obtain a specific compound. The reaction temperature at this time is -20 to 110 ° C. In this reaction, dimethyl carbonate, diethyl carbonate, diphenyl carbonate and the like are usually preferably used as the disubstituted carbonate. The amount of the disubstituted carbonate used is N
-A stoichiometrically equivalent amount or excess amount relative to 1 mol of the substituted amino alcohol, usually 1 to 2 mol. The solvent used in this reaction is not particularly limited as long as it is inert to the reaction, and various solvents can be used. Specific examples include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, sulfoxides, amides and the like. Of these, preferred are dichloromethane, chloroform, tetrahydrofuran, diethyl ether and the like.
This reaction is preferably carried out in the presence of a base, and as the base used in that case, sodium methoxide, sodium ethoxide, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium acetate, triethylamine. , Pyridine and the like can be exemplified. The amount of the base used is usually 0.05 to 1 mol with respect to 1 mol of the N-substituted amino alcohol.

Method using chloroformic acid ester; Chloroformate is introduced into a solution of N-substituted amino alcohol and reacted to obtain a specific compound. The reaction temperature at this time is -20 to 110 ° C. Examples of the chloroformate to be used include methyl chloroformate, ethyl chloroformate, phenyl chloroformate and the like. The amount of chloroformic acid ester used is a stoichiometric equivalent amount or an excess amount with respect to 1 mol of the N-substituted aminoalcohol, and usually 1 to
2 mol. The solvent used in this reaction is not particularly limited as long as it is inert to the reaction, and various solvents can be used. Specific examples include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons,
Examples thereof include ethers, sulfoxides and amides. Of these, preferred are dichloromethane, chloroform, tetrahydrofuran, diethyl ether and the like. This reaction is preferably carried out in the presence of a base, and as the base used at that time,
Examples thereof include sodium methoxide, sodium ethoxide, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium acetate, triethylamine, pyridine and the like. The amount of base used is usually N
-0.05 to 1 mol per mol of the substituted amino alcohol.

Method using 1,1'-carbonyldiimidazole;1,1'-carbonyldiimidazole is introduced into a solution of N-substituted aminoalcohol and reacted to obtain a specific compound. The reaction temperature at this time is -20 to 110 ° C. The solvent used in this reaction is not particularly limited as long as it is inert to the reaction, and various solvents can be used. Specific examples include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers and the like. Of these, preferred are hexane, benzene, toluene, dichloromethane, chloroform, tetrahydrofuran, diethyl ether and the like. The amount of 1,1′-carbonyldiimidazole used is N-
It is a stoichiometrically equivalent amount or an excess amount relative to 1 mol of the substituted amino alcohol, and is usually 1 to 2 mol. This reaction may be carried out in the presence of a base, and examples of the base used in this case include sodium methoxide, sodium ethoxide, sodium carbonate, potassium carbonate, triethylamine, pyridine and the like. The amount of the base used is usually 1 mol of N-substituted amino alcohol.
It is 0.05-1 mol. Further, in the above, 1,1'-carbonylbisimidazole is used instead of 1,1'-carbonyldiimidazole.
(2-methylimidazole) or 1,1'-carbonyldi-
The specific compound can be similarly obtained by using 1,2,4-triazole.

Further, in the present invention, in addition to the N-substituted amino alcohol represented by the formula (3), for example, N-
(Aromatic or heteroaromatic) -2-hydroxyethanoic acid amide (hereinafter referred to as "N-substituted hydroxyethanoic acid amide"), 3- (aromatic or heteroaromatic) amino-4-hydroxybutanoic acid or 2- (Aromatic or heteroaromatic) amino-4-hydroxybutanoic acid (these are simply referred to as “hydroxybutanoic acid”), or N- (aromatic or heteroaromatic) amino acid (hereinafter,
By using "N-substituted amino acid"), the specific compound of the present invention can be synthesized. Hereinafter, these methods will be briefly described.

Method utilizing reaction of N-substituted hydroxyethanoic acid amide with aldehyde or ketone; 1,3-oxazolidine is obtained by reacting N-substituted hydroxyethanoic acid amide with aldehyde or ketone in the presence of an acid or dehydration condensing agent By using -4-one, the specific compound of the present invention can be obtained. The reaction temperature at this time is -20 to 11
It is 0 ° C. The solvent used in this reaction is not particularly limited as long as it is inert to the reaction, and various solvents can be used. Specific examples include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons,
Ethers and the like can be mentioned. Of these, preferred are benzene, toluene and the like. Examples of the aldehyde used include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde,
Examples include isobutyraldehyde, benzaldehyde, anisaldehyde, nicotinaldehyde, cyclohexanecarbaldehyde and the like. Examples of the ketone used include acetone, ethyl methyl ketone, diethyl ketone, acetophenone, propiophenone, benzyl methyl ketone and the like. The amount of the aldehyde or ketone to be used is stoichiometrically equivalent or in excess with respect to 1 mol of the N-substituted hydroxyethanoic acid amide, and is usually 1 to 5 mol.

Method using hydroxybutanoic acid; 3-
By cyclizing (aromatic or heteroaromatic) amino-4-hydroxybutanoic acid or 2- (aromatic or heteroaromatic) amino-4-hydroxybutanoic acid into a lactone, the specific compound of the present invention can be obtained. can get. This cyclization reaction can be easily carried out by heating the hydroxybutanoic acid in a suitable solvent. The reaction temperature at this time is 50 to 145 ° C. The solvent used in this reaction is not particularly limited as long as it is inert to the reaction, and various solvents can be used. Specific examples include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers and the like.
Of these, preferred are benzene, toluene,
Examples include xylene, N, N'-dimethylformamide, dimethyl sulfoxide and the like.

Method using N-substituted amino acid: A specific compound is obtained as N-carboxyanhydride by introducing thionyl chloride, phosphorus pentachloride or phosgene into a solution of N-substituted amino acid. The reaction temperature at this time is −20 to 110 ° C.
Is. The solvent used in this reaction is not particularly limited as long as it is inert to the reaction, and various solvents can be used. Specific examples include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers and the like. Of these, preferred are dioxane, tetrahydrofuran and the like.
The amount of thionyl chloride, phosphorus pentachloride or phosgene used is stoichiometrically equivalent or in excess with respect to 1 mol of the N-substituted amino acid, and usually 1 to 5 mol.

The N-substituted amino alcohol, N-substituted hydroxyethanoic acid amide, hydroxybutanoic acid and N-substituted amino acid used for synthesizing the above-mentioned specific compound can be respectively synthesized by the following methods.

Synthesis of N-Substituted Amino Alcohol In the following, an α-amino acid having a substituent corresponding to R in the general formula (1) at the α-position is simply 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 simply referred to as "substituted amino alcohol", and an α-amino acid ester having a substituent corresponding to the above R at the α-position Is referred to as "substituted amino acid ester". Furthermore, an epoxide having a substituent corresponding to the above R on the ring is referred to as a "substituted epoxide".

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 the amino group is then converted to an aromatic group or a hetero group. A method of modifying with an aromatic 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
Chemistry ", Willy, New York, 1984). This borane reduction method does not cause racemization during the reduction reaction,
It is effectively applied to the reduction of optically active substituted amino acids. Examples of the substituted amino acid to which the borane reduction method is applied include homoalanine, norvaline, leucine, isoleucine, tert-leucine, norleucine, phenylglycine, S-methylcysteine, S-benzylcysteine and the like. In this case, as the borane reagent,
Borane-dimethyl sulfide complex, borane-pyridine complex, borane-dimethylamine complex, borane-diethylamine complex, borane-t-butylamine complex, borane-tetrahydrofuran complex, borane-morpholine complex, borane-ether complex, diborane, etc. are used. be able to. Among these, preferred are borane-dimethyl sulfide complex, borane-ether complex and diborane. The amount of the borane reagent used is stoichiometrically equivalent or excessive with respect to 1 mol of the substituted amino acid, and 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 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 are used. , Halogenated hydrocarbons, ethers and the like. Particularly suitable are tetrahydrofuran, diethyl ether and toluene.

As a means for modifying the amino group of the substituted aminoalcohol obtained by the above reduction reaction with an aromatic group or a heteroaromatic group, a derivative having a leaving group on the aromatic or heteroaromatic ring is used. A method of reacting with a substituted amino alcohol can be mentioned. Examples of the leaving group on the aromatic or heteroaromatic ring include a fluoro group, a chloro group, a bromo group, an iodo group, a p-toluenesulfonyloxy group, a methanesulfonyloxy group and a trifluoromethanesulfonyloxy group. It is possible,
Particularly, a chloro group and a trifluoromethanesulfonyloxy group are preferable. The amount of the derivative having a leaving group used is stoichiometrically equal to or excess of 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
2.5 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. 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 give D-, L-, or DL.
A method of modifying the amino group with an aromatic group or a heteroaromatic group after forming a substituted amino alcohol. 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 methyl ester and ethyl ester of the substituted amino acid exemplified in Production Method 1. Aluminum hydride In the reduction method, the reducing agent used is aluminum hydride, lithium aluminum hydride, sodium aluminum hydride, magnesium aluminum hydride, lithium dimethoxyaluminum hydride, lithium trimethoxyaluminum hydride, tris (t-butoxy) hydride. ) Aluminum, sodium bis (2-methoxyethoxy) aluminum hydride, 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 against substituted amino acid ester 1 mol
Used in a proportion of 0.5-10 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.
Is. 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,
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 of 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 adopted. it can. For the reduction of the N- (aromatic or heteroaromatic) amino acid ester thus obtained, the reduction method such as the aluminum hydride reduction method, the borohydride reduction method or the hydrogenation method mentioned in the production method 2 is adopted. be able to.

Production Method 4; A method in which a substituted epoxide is opened with an aromatic or heteroaromatic amine derivative to give a substituted amino alcohol. Examples of the substituted epoxide used here include propylene oxide, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyoctane, 2,3-epoxypropylbenzene, Examples thereof include butadiene monoxide and styrene oxide. In addition, examples of the aromatic or heteroaromatic amine derivative used here include aromatic or heteroaromatic amines, aromatic or heteroaromatic trimethylsilylamine, lithium aromatic or heteroaromatic amide, and the like. be able to. The amount of these derivatives used is usually 1 to 20 mol per mol of the substituted 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, etc. used is
It is usually 1 to 100 mol per mol of the substituted 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. The reaction temperature is usually 0 to 10
It is 0 ° C. This method is advantageous in that the desired N-substituted amino alcohol can be obtained particularly in one step.

Synthesis of N-Substituted Hydroxyethanoic Acid Amide The N-substituted hydroxyethanoic acid amide is synthesized by activating the carboxyl group of hydroxyethanoic acid and then reacting it with an aromatic amine or a heteroaromatic amine. You can Examples of the method for activating the carboxyl group of hydroxyethanoic acid include a method of reacting with a chlorinating agent such as thionyl chloride, oxalyl chloride, phosphorus trichloride, a method of reacting with a condensing agent such as dicyclohexylcarbodiimide, and the like. . The amount of the chlorinating agent or condensing agent used is stoichiometrically equivalent to or in excess with respect to hydroxyethanoic acid, and preferably 1 to 2 mol. Examples of aromatic amines include 4-nitroaniline 2,4-dinitroaniline, 4-cyanoaniline,
2,4-dicyanoaniline, 4-methoxycarbonylaniline and the like can be mentioned. Examples of the heteroaromatic amine include 5-nitro-2-aminopyridine,
Examples thereof include 5-cyano-2-aminopyridine, 6-nitro-2-aminoquinoline, 4-nitro-2-aminothiophene and the like. The amount of the aromatic amine or heteroaromatic amine used is stoichiometrically equivalent to or in excess with respect to hydroxyethanoic acid, and preferably 1 to 2 mol. The reaction temperature is usually 0 to 150 ° C, and
The reaction is carried out in the presence of solvent. Examples of this solvent include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers and the like. Particularly preferably used are diethyl ether, dibutyl ether and tetrahydrofuran. is there.

Synthesis of Hydroxybutanoic Acid Hydroxybutanoic acid can be synthesized, for example, by the following method. A method of modifying an amino group of a 3-amino-4-hydroxybutanoic acid derivative or a 4-amino-2-hydroxybutanoic acid derivative with an aromatic group or a heteroaromatic group. Examples of this method include a method of reacting a derivative having a leaving group on an aromatic or heteroaromatic ring with a 3-amino-4-hydroxybutanoic acid derivative or a 4-amino-2-hydroxybutanoic acid derivative. it can. Examples of the leaving group 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, and a chloro group and a trifluoro group are particularly preferable. A methanesulfonyloxy group is preferred. The amount of the aromatic derivative or heteroaromatic derivative having such a leaving group used is stoichiometrically equivalent or in excess, 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. Examples of the base include inorganic bases, tertiary amines, pyridines, and the like, and particularly preferably used are triethylamine, pyridine, and potassium carbonate. The amount of the base used is usually 3-amino-4-hydroxybutanoic acid derivative or 4-amino-2
The stoichiometrically equivalent amount or excess amount relative to the hydroxybutanoic acid derivative, preferably 1 to 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, and amides, and particularly preferably used are dimethyl sulfoxide, N-methylpyrrolidone and N, N-dimethylformamide.

Synthesis of N -Substituted Amino Acid The N-substituted amino acid is obtained by substituting the method of modifying the amino group of the substituted amino alcohol shown in the above-mentioned production method 1 of N-substituted amino alcohol with an aromatic group or a heteroaromatic group. It can be easily synthesized by applying to amino acids.

Production of Crystals The specific compound represented by the general formula (1) obtained as described above is 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. Further, 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 an antireflection coating can be provided by the method disclosed in Japanese Patent Publication No. 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 physically orienting the electrically coupled ones by using an external electric field, it is possible to manufacture 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 in a solvent and mixed 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. between the functional group of the compound represented by the general formula (1) and the functional group of the polymer matrix. It is also possible to cause the reaction of 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, epoxy resin, and phenol resin. be able to.

[0044]

EXAMPLES Example 1 3- (5-Nitro-2-pyridinyl) -4-methyl-2
-Synthesis of oxazolidinone Alanine (30 g) was dissolved in anhydrous tetrahydrofuran (150 g), boron trifluoride ethyl ether (35.0 g) was added thereto, and the mixture was stirred at 60 ° C for 1 hour under a dry nitrogen atmosphere.
To this solution, 36.3 g 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. Next, 150 g of 6N sodium hydroxide aqueous solution was added to stop the reaction, and the product was extracted with tetrahydrofuran. After that, 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 18.1 g of alaninol. 18.1 g of the alaninol thus obtained was mixed with 29.3 g of triethylamine and N 2.
Dissolved in 80 ml of methyl-2-pyrrolidone. Then
5-nitro-2-chloropyridine (42.2 g) was added to N-methyl-
The solution prepared above was added dropwise to a solution dissolved in 100 ml of 2-pyrrolidone, and reacted at room temperature for 12 hours. After adding a 2N hydrochloric acid aqueous solution to adjust the pH of the reaction solution to around 4, 500 g of water was added to the reaction solution, 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 ethyl acetate (volume ratio = 5: 1) as a developing solvent, and the recovered yellow solid was recrystallized using ethyl acetate. 2- (5-nitro-2-pyridinyl) amino-1-
40.0 g of propanol was obtained. 2- (5-
Nitro-2-pyridinyl) amino-1-propanol 4
A solution prepared by dissolving 0.0 g in 100 g of tetrahydrofuran was stirred under ice cooling, and trichloromethyl chloroformate was added.
The phosgene generated by the reaction between 44.2 g and activated carbon was cooled and liquefied, and then added dropwise. After reacting for 15 minutes, 300 g of saturated aqueous sodium hydrogen carbonate solution was added, and the product was extracted with ethyl acetate. The obtained residue was purified by silica gel column chromatography using dichloromethane as a developing solvent, and the collected pale yellow solid was recrystallized with ethyl acetate to give colorless columnar crystals 3
Obtained 3.6 g. This one has an infrared absorption spectrum (Fig. 1
3) and the nuclear magnetic resonance spectrum (shown in FIG. 2), 3- (5-nitro-2-pyridinyl) -4-methyl-
It was identified as 2-oxazolidinone.

Example 2 3- (5-Nitro-2-pyridinyl) -4-ethyl-2
Synthesis of Oxazolidinone In Example 1, homoalanine 30.3 was used instead of 30 g of alanine.
g, the amount of boron trifluoride ethyl ether used
Homoalaninol 2 was prepared in the same manner as in Example 1 except that the amount of the dimethyl sulfide solution of 30.5 g and 10 M borane-dimethyl sulfide complex used was 32.3 g.
0.0 g was obtained. The obtained homoalaninol (20.0 g) was dissolved in triethylamine (27.3 g) and N-methyl-2-pyrrolidone (80 ml). Then, the solution prepared above was added dropwise to a solution prepared by dissolving 39.1 g of 5-nitro-2-chloropyridine in 100 ml of N-methyl-2-pyrrolidone, and reacted at room temperature for 12 hours. After that, 2N hydrochloric acid aqueous solution was added to adjust the pH of the reaction solution to around 4, then 500 g of water was added to the reaction solution, and the product was extracted with ethyl acetate. After drying over anhydrous magnesium sulfate, the solvent was removed. The obtained residue was purified by silica gel column chromatography using a mixed solvent of dichloromethane and ethyl acetate (volume ratio = 5: 1) as a developing solvent, and the recovered yellow solid substance was recrystallized using ethyl acetate. 2- (5-nitro-2-
37.6 g of pyridinyl) amino-1-butanol was obtained. 37.6 g of 2- (5-nitro-2-pyridinyl) amino-1-butanol obtained above was added to 150 g of tetrahydrofuran.
The solution dissolved in was stirred under ice-cooling, and phosgene generated by the reaction between 38.7 g of trichloromethyl chloroformate and activated carbon was cooled and liquefied was added dropwise. After reacting for 15 minutes, saturated aqueous sodium hydrogen carbonate solution
300 g was added and the product was extracted with ethyl acetate. The obtained residue was purified by silica gel column chromatography using dichloromethane as a developing solvent, and the recovered pale yellow solid was recrystallized with ethyl acetate to obtain 32.8 g of colorless plate crystals. This was identified as 3- (5-nitro-2-pyridinyl) -4-ethyl-2-oxazolidinone from the infrared absorption spectrum (shown in FIG. 3) and the nuclear magnetic resonance spectrum (shown in FIG. 4).

Example 3 3- (5-Nitro-2-pyridinyl) -4-isopropyi
Synthesis of ru-2-oxazolidinone In Example 1, 32.4 g of valine was used instead of 30 g of alanine, and the amount of boron trifluoride ethyl ether used was 28.7.
g, and except that the amount of the 10 M borane-dimethyl sulfide complex dimethyl sulfide solution used was 29.8 g,
The same operation as in Example 1 was performed to obtain 20 g of valinol.
20 g of the obtained valinol was dissolved in 23.6 g of triethylamine and 80 ml of N-methyl-2-pyrrolidone. Then, the solution prepared above was added dropwise to a solution prepared by dissolving 33.8 g of 5-nitro-2-chloropyridine in 100 ml of N-methyl-2-pyrrolidone, and reacted at room temperature for 12 hours. After that, 2N hydrochloric acid aqueous solution was added to adjust the pH of the reaction solution to around 4, then 500 g of water was added to the reaction solution, and the product was extracted with ethyl acetate. After drying over anhydrous magnesium sulfate, the solvent was removed. The obtained residue was purified by silica gel column chromatography using a mixed solvent of dichloromethane and ethyl acetate (volume ratio = 5: 1) as a developing solvent, and the recovered yellow solid was recrystallized using ethyl acetate. 2- (5-nitro-2-pyridinyl) amino-3-
34.8 g of methyl-1-butanol was obtained. 150 g of tetrahydrofuran was added to 34.8 g of 2- (5-nitro-2-pyridinyl) amino-3-methyl-1-butanol obtained above.
When the solution dissolved in was stirred under ice cooling, phosgene generated by the reaction between 33.6 g of trichloromethyl chloroformate and activated carbon was cooled and liquefied was added dropwise. After reacting for 15 minutes, saturated aqueous sodium hydrogen carbonate solution
300 g was added and the product was extracted with ethyl acetate. The obtained residue was purified by silica gel column chromatography using dichloromethane as a developing solvent, and the collected pale yellow solid was recrystallized with ethyl acetate to obtain 31.1 g of colorless columnar crystals. This was identified as 3- (5-nitro-2-pyridinyl) -4-isopropyl-2-oxazolidinone from the infrared absorption spectrum (shown in FIG. 5) and the nuclear magnetic resonance spectrum (shown in FIG. 6).

Example 4 3- (5-Nitro-2-pyridinyl) -4-isobutyl
Synthesis of 2-oxazolidinone In Example 1, 32.0 g of leucine was used instead of 30 g of alanine, and the amount of boron trifluoride ethyl ether used was 25.5 g.
g, and except that the amount of the 10 M borane-dimethyl sulfide complex dimethyl sulfide solution used was 26.5 g,
The same operation as in Example 1 was carried out to obtain 20 g of leucinol. 20 g of the obtained leucinol was added to triethylamine 2
It was dissolved in 0.7 g and 80 ml of N-methyl-2-pyrrolidone. Then, the solution prepared above was added dropwise to a solution prepared by dissolving 29.8 g of 5-nitro-2-chloropyridine in 100 ml of N-methyl-2-pyrrolidone, and reacted at room temperature for 12 hours. After that, the pH of the reaction solution was adjusted by adding a 2N hydrochloric acid aqueous solution.
Was adjusted to about 4, then 500 g of water was added to the reaction solution, the product was extracted with ethyl acetate, the organic layer was washed with water and then with saturated saline, and dried over anhydrous magnesium sulfate.
The solvent was removed. The obtained residue was purified by silica gel column chromatography using a mixed solvent of dichloromethane and ethyl acetate (volume ratio = 5: 1) as a developing solvent, and the recovered yellow solid was recrystallized using ethyl acetate. 29.2 g of 2- (5-nitro-2-pyridinyl) amino-4-methyl-1-pentanol was obtained. A solution of 29.2 g of 2- (5-nitro-2-pyridinyl) amino-4-methyl-1-pentanol obtained above in 150 g of tetrahydrofuran was stirred under ice cooling, and trichloromethyl chloroformate 26.6 was added. The phosgene generated by the reaction of g with activated carbon was cooled and liquefied and added dropwise. After reacting for 15 minutes, 300 g of saturated aqueous sodium hydrogen carbonate solution was added, and the product was extracted with ethyl acetate. The obtained residue was purified by silica gel column chromatography using dichloromethane as a developing solvent,
The recovered pale yellow solid was recrystallized from ethyl acetate to obtain 25.9 g of colorless plate crystals. This compound was analyzed by infrared absorption spectrum (shown in FIG. 7) and nuclear magnetic resonance spectrum (shown in FIG. 8) from 3- (5-nitro-).
2-Pyridinyl) -4-isobutyl-2-oxazolidinone.

Example 5 3- (5-Nitro-2-pyridinyl) -4-sec-butyl
Synthesis of Le-2-oxazolidinone In Example 4, isoleucine 3 was used instead of leucine 32.0 g.
The same operation as in Example 4 was carried out except that 2.0 g was used to obtain 20 g isoleucinol. 20 g of the resulting isoleucinol was dissolved in 20.7 g of triethylamine and 80 ml of N-methyl-2-pyrrolidone. Then, the solution prepared above was added dropwise to a solution prepared by dissolving 29.8 g of 5-nitro-2-chloropyridine in 100 ml of N-methyl-2-pyrrolidone, and reacted at room temperature for 12 hours. After that, 2N hydrochloric acid aqueous solution was added to adjust the pH of the reaction solution to around 4, then 500 g of water was added to the reaction solution, and the product was extracted with ethyl acetate. After drying over anhydrous magnesium sulfate, the solvent was removed. The obtained residue was subjected to silica gel column chromatography to obtain a mixed solvent of dichloromethane and ethyl acetate (volume ratio = 5:
2) was purified by using 1) as a developing solvent, and the recovered yellow solid was recrystallized with ethyl acetate to give 2-
(5-Nitro-2-pyridinyl) amino-3-methyl-
31.6 g of 1-pentanol was obtained. 2-obtained above
(5-Nitro-2-pyridinyl) amino-3-methyl-
A solution obtained by dissolving 31.6 g of 1-pentanol in 150 g of tetrahydrofuran was stirred under ice-cooling, and phosgene generated by the reaction of 28.8 g of trichloromethyl chloroformate with activated carbon was cooled and liquefied was added dropwise. And
After reacting for 15 minutes, saturated aqueous sodium hydrogen carbonate solution 3
00 g was added and the product was extracted with ethyl acetate. The obtained residue was purified by silica gel column chromatography using dichloromethane as a developing solvent, and the collected pale yellow solid was recrystallized with ethyl acetate to obtain 27.4 g of colorless plate crystals. This was identified as 3- (5-nitro-2-pyridinyl) -4-sec-butyl-2-oxazolidinone by infrared absorption spectrum (shown in FIG. 9) and nuclear magnetic resonance spectrum (shown in FIG. 10). It was

Example 6 3- (5-Nitro-2-pyridinyl) -4-phenyl-
Synthesis of 2-oxazolidinone In Example 1, 31.5 g of α-phenylglycine was used in place of 30 g of alanine, the amount of boron trifluoride ethyl ether used was 22.1 g, and a solution of 10 M borane-dimethyl sulfide complex in dimethyl sulfide was used. The same operation as in Example 1 was carried out except that the amount used was 23.0 g to obtain 20 g of α-phenylglycinol. 20 g of the obtained α-phenylglycinol was dissolved in 17.7 g of triethylamine and 80 ml of N-methyl-2-pyrrolidone. Then, the solution prepared above was added dropwise to a solution prepared by dissolving 25.4 g of 5-nitro-2-chloropyridine in 100 ml of N-methyl-2-pyrrolidone, and reacted at room temperature for 12 hours. Then 2N
After adding hydrochloric acid aqueous solution to bring the pH of the reaction solution to around 4,
Water (500 g) was added to the reaction solution, the product was extracted with ethyl acetate, 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 subjected to silica gel column chromatography to obtain a mixed solvent of dichloromethane and ethyl acetate (volume ratio = 5:
2) was purified by using 1) as a developing solvent, and the recovered yellow solid was recrystallized with ethyl acetate to give 2-
22.6 g of (5-nitro-2-pyridinyl) amino-2-phenyl-1-ethanol was obtained. 2-obtained above
(5-Nitro-2-pyridinyl) amino-2-phenyl-1-ethanol 22.6 g was dissolved in 150 g of tetrahydrofuran, and the solution was stirred under ice cooling. The cooled phosgene was liquefied and added dropwise. And
After reacting for 15 minutes, saturated aqueous sodium hydrogen carbonate solution 3
00 g was added and the product was extracted with ethyl acetate. The obtained residue was purified by silica gel column chromatography using dichloromethane as a developing solvent, and the recovered pale yellow solid was recrystallized using ethyl acetate to obtain 18.8 g of colorless plate crystals. This was identified as 3- (5-nitro-2-pyridinyl) -4-phenyl-2-oxazolidinone from the infrared absorption spectrum (shown in FIG. 11) and the nuclear magnetic resonance spectrum (shown in FIG. 12).

Example 7 3- (5-Nitro-2-pyridinyl) -4-benzyl-
Synthesis of 2-oxazolidinone In Example 1, phenylalanine was used instead of 30 g of alanine.
The same operation as in Example 1 was performed except that 31.2 g was used, the amount of boron trifluoride ethyl ether used was 20.0 g, and the amount of the 10 M borane-dimethyl sulfide complex dimethyl sulfide solution used was 20.7 g. 20 g of phenylalaninol was obtained. 20 g of the obtained phenylalaninol
Was dissolved in 16.1 g of triethylamine and 80 ml of N-methyl-2-pyrrolidone. Next, 23.1 g of 5-nitro-2-chloropyridine was added to N-methyl-2-pyrrolidone 100
The solution prepared above was added dropwise to the solution dissolved in ml, and the mixture was reacted at room temperature for 12 hours. After adding 2N aqueous hydrochloric acid solution to adjust the pH of the reaction solution to around 4, 500 g of water was added to the reaction solution, the product was extracted with ethyl acetate, and the organic layer was washed with water and then with saturated saline solution. After drying with magnesium sulfate, the solvent was removed. The obtained residue was purified by silica gel column chromatography using a mixed solvent of dichloromethane and ethyl acetate (volume ratio = 5: 1) as a developing solvent, and the recovered yellow solid substance was recrystallized using ethyl acetate. 2- (5-nitro-2-
Pyridinyl) amino-2-phenyl-1-propanol
27.9 g was obtained. 2- (5-nitro-2-obtained above
Pyridinyl) amino-2-phenyl-1-propanol
A solution prepared by dissolving 27.9 g in 150 g of tetrahydrofuran was stirred under ice cooling, and trichloromethyl chloroformate was added.
Phosgene generated by the reaction between 22.2 g and activated carbon was cooled and liquefied and added dropwise. After reacting for 15 minutes, 300 g of saturated aqueous sodium hydrogen carbonate solution was added, and the product was extracted with ethyl acetate. The obtained residue was purified by silica gel column chromatography using dichloromethane as a developing solvent, and the recovered pale yellow solid was recrystallized with ethyl acetate to give colorless needle crystals 2
5.1 g was obtained. This has an infrared absorption spectrum (Fig. 13
It was identified as 3- (5-nitro-2-pyridinyl) -4-benzyl-2-oxazolidinone from the magnetic resonance spectrum (shown in FIG. 14) and the nuclear magnetic resonance spectrum (shown in FIG. 14).

Example 8 3- (5-Nitro-2-pyridinyl) -4-benzylthio
Synthesis of Omethyl-2-oxazolidinone In Example 1, 30.6 g of S-benzyl cysteine was used in place of 30 g of alanine, the amount of boron trifluoride ethyl ether used was 15.4 g, and dimethyl sulfide of 10M borane-dimethyl sulfide complex was used. Use amount of solution is 16.0g
20 g of S-benzyl cysteinol was obtained by performing the same operation as in Example 1 except that. 20 g of the obtained S-benzyl cysteinol was dissolved in 12.3 g of triethylamine and 80 ml of N-methyl-2-pyrrolidone. Then, 17.7 g of 5-nitro-2-chloropyridine was added to N-methyl-
The solution prepared above was added dropwise to a solution dissolved in 100 ml of 2-pyrrolidone, and reacted at room temperature for 12 hours. After adding 2N aqueous hydrochloric acid solution to adjust the pH of the reaction solution to around 4, 500 g of water was added to the reaction solution, the product was extracted with ethyl acetate, and the organic layer was washed with water and then with saturated saline solution. After drying with magnesium sulfate, the solvent was removed. The obtained residue was subjected to silica gel column chromatography to obtain a mixed solvent of dichloromethane and ethyl acetate (volume ratio = 5:
2) was purified by using 1) as a developing solvent, and the recovered yellow solid was recrystallized with ethyl acetate to give 2-
29.6 g of (5-nitro-2-pyridinyl) amino-3-benzylthio-1-propanol was obtained. A solution prepared by dissolving 29.6 g of 2- (5-nitro-2-pyridinyl) amino-3-benzylthio-1-propanol obtained above in 150 g of tetrahydrofuran was stirred under ice cooling,
The phosgene generated by the reaction of 20.2 g of trichloromethyl chloroformate with activated carbon was cooled and liquefied and added dropwise. After reacting for 15 minutes, 300 g of saturated aqueous sodium hydrogen carbonate solution was added, and the product was extracted with ethyl acetate. The obtained residue was purified by silica gel column chromatography using dichloromethane as a developing solvent, and the recovered pale yellow solid was recrystallized with ethyl acetate to obtain 23.8 g of colorless plate crystals. This compound was identified by 3- (5-nitro-2) from the infrared absorption spectrum (shown in FIG. 15) and the nuclear magnetic resonance spectrum (shown in FIG. 16).
-Pyridinyl) -4-benzylthiomethyl-2-oxazolidinone.

Example 9 3- (2-Acetylamino-4-nitrophenyl) -4
-Methyl-2-oxazolidinone synthesis 2-acetylamino-4-nitrofluorobenzene 40.6
A solution was prepared by dissolving 150 g of dimethyl sulfoxide in 150 g. A solution prepared by dissolving 15.4 g of alaninol obtained in the same manner as in Example 1 in 100 g of dimethyl sulfoxide was added dropwise to this solution over 1 hour. After reacting for 12 hours at room temperature, 1000 g of water was added to the reaction solution, and the product was extracted with ethyl acetate. Then, the organic layer was washed with water and then with saturated saline and dried over anhydrous magnesium sulfate,
The solvent was removed. The obtained residue was purified by silica gel column chromatography using a mixed solvent of dichloromethane and ethyl acetate (volume ratio = 2: 1) as a developing solvent, and the collected yellow solid was further recrystallized using ethyl acetate. 39.9 g of 2- (2-acetylamino-4-nitrophenyl) amino-1-propanol was obtained. A solution prepared by dissolving 39.9 g of 2- (2-acetylamino-4-nitrophenyl) amino-1-propanol obtained above in 100 g of tetrahydrofuran was stirred under ice cooling, and 34.8 g of trichloromethyl chloroformate was added. The phosgene generated by the reaction with activated carbon was cooled and liquefied and added dropwise. Then, after reacting for 15 minutes, 300 g of a saturated sodium hydrogen carbonate aqueous solution was added, and the product was extracted with ethyl acetate. The obtained residue was purified by silica gel column chromatography using a mixed solvent of dichloromethane and ethyl acetate (volume ratio = 10: 1) as a developing solvent, and the recovered pale yellow solid was further recrystallized using ethyl acetate. 25.7 g of pale yellow columnar crystals were obtained. This was identified as 3- (2-acetylamino-4-nitrophenyl) -4-methyl-2-oxazolidinone by infrared absorption spectrum (shown in FIG. 18) and nuclear magnetic resonance spectrum (shown in FIG. 18). It was

Example 10 3- (2,4-Dinitrophenyl) -4-methyl-2-oxy
Synthesis of Sazolidinone 20.4 g of alaninol synthesized in the same manner as in Example 1 was added to 50
It was dissolved in 100 g of a wt% ethanol aqueous solution. To this solution were added sodium hydrogen carbonate (45.7 g) and then 2,4-dinitrofluorobenzene (50.6 g), and the mixture was reacted at room temperature for 4 hours. Next, ethanol was distilled off under reduced pressure, concentrated hydrochloric acid was added dropwise to adjust the pH of the reaction solution to 2, and the product was extracted with ethyl acetate. Then, the organic layer was washed with saturated aqueous sodium hydrogen carbonate and then saturated brine, dried over anhydrous calcium carbonate, and the solvent was removed. The obtained residue was purified by silica gel column chromatography using a mixed solvent of dichloromethane and ethyl acetate (volume ratio = 5: 1) as a developing solvent, and the recovered yellow solid was recrystallized using ethyl acetate. 48.8 g of 2- (2,4-dinitrophenyl) amino-1-propanol was obtained. A solution prepared by dissolving 48.8 g of 2- (2,4-dinitrophenyl) amino-1-propanol obtained above in 150 g of tetrahydrofuran was stirred under ice-cooling, and the reaction of 44.0 g of trichloromethyl chloroformate with activated carbon was performed. What was liquefied by cooling the phosgene generated by was added dropwise. Then, after reacting for 15 minutes, 300 g of saturated sodium hydrogen carbonate aqueous solution was added,
The product was extracted with ethyl acetate. The obtained residue was purified by silica gel column chromatography using dichloromethane as a developing solvent, and the recovered pale yellow solid was recrystallized using ethyl acetate to obtain 38.9 g of pale yellow columnar crystals. This compound was analyzed by infrared absorption spectrum (shown in FIG. 19) and nuclear magnetic resonance spectrum (shown in FIG. 20) to be 3- (2,4-dinitrophenyl) -4-methyl-
It was identified as 2-oxazolidinone.

Example 11 3- (2-Acetylamino-4-nitrophenyl) -4
Synthesis of -isobutyl-2-oxazolidinone Leucinol 20 was carried out in the same manner as in Example 1 except that 30 g of leucine was used instead of 25 g of alanine.
g was obtained. 20 g of this leucinol was added to triethylamine 2
It was dissolved in 9.3 g and 80 ml N-methyl-2-pyrrolidone. To this solution, 40.4 g of 2-acetylamino-4-nitrofluorobenzene was added to N-methyl-2-pyrrolidone 1
The solution was added dropwise to a solution dissolved in 00 ml and stirred at room temperature for 12 hours.
Then, 2N aqueous hydrochloric acid solution was added to bring the pH of the reaction solution to around 4, then 500 g of water was added, and the purified 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 ethyl acetate (volume ratio = 5: 1) as a developing solvent, and the recovered yellow solid was recrystallized using ethyl acetate. 2- (2-acetylamino-4-nitrophenyl)
35.4 g of amino-4-methyl-1-pentanol was obtained.
2- (2-Acetylamino-4-nitrophenyl) amino-4-methyl-1-pentanol obtained above 35.4
g of tetrahydrofuran in 150 g was stirred under ice-cooling, and trichloromethyl chloroformate 44.2 was added.
The phosgene generated by the reaction of g with activated carbon was cooled and liquefied and added dropwise. Then, after reacting for 15 minutes, 300 g of a saturated sodium hydrogen carbonate aqueous solution was added, and the product was extracted with ethyl acetate. The obtained residue was purified by silica gel column chromatography using dichloromethane as a developing solvent, and the recovered pale yellow solid was recrystallized with ethyl acetate to give colorless columnar crystals 31.5.
g was obtained. This product is 3 from infrared absorption spectrum (shown in FIG. 21) and nuclear magnetic resonance spectrum (shown in FIG. 22).
-(2-Acetylamino-4-nitrophenyl) -4-
Identified as isobutyl-2-oxazolidinone.

Example 12 3- (2,4-Dinitrophenyl) -4-isobutyl-2-
Synthesis of Oxazolidinone The procedure of Example 9 was repeated except that 38.0 g of 2,4-dinitrofluorobenzene was used instead of 40.4 g of 2-acetylamino-4-nitrofluorobenzene in Example 9, and 2- (2 33.9 g of 4,4-dinitrophenyl) amino-4-methyl-1-pentanol was obtained. This 2- (2,4-dinitrophenyl) amino-4-methyl-1-pentanol
After reacting 33.9 g with phosgene in the same manner as in Example 9, purification was performed by column chromatography and recrystallization in the same manner to obtain 29.8 g of pale yellow plate crystals. This was identified as 3- (2,4-dinitrophenyl) -4-isobutyl-2-oxazolidinone from the infrared absorption spectrum (shown in FIG. 23) and the nuclear magnetic resonance spectrum (shown in FIG. 24).

Example 13 3- (2-Acetylamino-4-nitrophenyl) -4
Synthesis of -benzyl-2-oxazolidinone In Example 1, instead of 25 g of alanine, phenylalanine
The same operation as in Example 1 was carried out except that 27 g was used to obtain 20.0 g of phenylalaninol. 20.0 g of this phenylalaninol was dissolved in 16.1 g of triethylamine and 80 ml of N-methyl-2-pyrrolidone. This solution is
32.2 g of acetylamino-4-nitrofluorobenzene was added dropwise to a solution of 100 ml of N-methyl-2-pyrrolidone, and the mixture was stirred at room temperature for 12 hours. Then, 2N aqueous hydrochloric acid solution was added to bring the pH of the reaction solution to around 4, then 500 g of water was added, and the purified 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 ethyl acetate (volume ratio = 5: 1) as a developing solvent, and the recovered yellow solid was recrystallized using ethyl acetate. 33.5 g of 2- (2-acetylamino-4-nitrophenyl) amino-3-phenyl-1-propanol was obtained. 2-obtained above
(2-Acetylamino-4-nitrophenyl) amino-
A solution prepared by dissolving 33.5 g of 3-phenyl-1-propanol in 150 g of tetrahydrofuran was stirred under ice cooling, and phosgene generated by the reaction of 22.2 g of trichloromethyl chloroformate with activated carbon was cooled and liquefied. Was dripped. After reacting for 15 minutes, 300 g of saturated aqueous sodium hydrogen carbonate solution was added, and the product was extracted with ethyl acetate.
The obtained residue was purified by silica gel column chromatography using dichloromethane as a developing solvent, and the recovered pale yellow solid was recrystallized with ethyl acetate to obtain 22.8 g of colorless needle crystals. This product was identified as 3- (2-acetylamino-4) by infrared absorption spectrum (shown in FIG. 25) and nuclear magnetic resonance spectrum (shown in FIG. 26).
-Nitrophenyl) -4-benzyl-2-oxazolidinone.

Example 14 3- (2,4-Dinitrophenyl) -4-benzyl-2-o
Synthesis of Xazolidinone The procedure of Example 9 was repeated except that 30.3 g of 2,4-dinitrofluorobenzene was used instead of 40.4 g of 2-acetylamino-4-nitrofluorobenzene in Example 9, and 2 -(2,4-Dinitrophenyl) amino-3
31.7 g of -phenyl-1-propanol was obtained. This 2-
(2,4-Dinitrophenyl) amino-3-phenyl-1-
After reacting 31.7 g of propanol with phosgene in the same manner as in Example 9, purification was carried out in the same manner by column chromatography and recrystallization, and pale yellow plate crystals 25.2
g was obtained. This product has 3 from the infrared absorption spectrum (shown in FIG. 27) and the nuclear magnetic resonance spectrum (shown in FIG. 28).
Identified as-(2,4-dinitrophenyl) -4-benzyl-2-oxazolidinone.

Example 15 3- (4-Nitrophenyl) -4-methyl-2-oxa
Synthesis of Zolidinone 30 g of alaninol synthesized in the same manner as in Example 1 and 55.2 g of anhydrous potassium carbonate were suspended in 200 g of dimethyl sulfoxide, and 66.6 mL of 6-concentration p-fluoronitrobenzene / dimethyl sulfoxide solvent was added to the suspension.
The reaction was carried out for 24 hours. The reaction solution was poured into 3000 g of water, and the formed precipitate was separated by filtration, washed with water and dried to obtain 76.4 g of N- (4-nitrophenyl) alaninol. N-obtained above
A solution prepared by dissolving 76.4 g of (4-nitrophenyl) alaninol in 500 g of tetrahydrofuran was stirred under ice-cooling, and a liquefied product of horgen generated by the reaction between 154 g of trichloromethyl chloroformate and activated carbon was cooled and added dropwise. Then, after reacting for 30 minutes, 500 g of a saturated sodium hydrogen carbonate aqueous solution was added, and the mixture was extracted with ethyl acetate. The obtained residue was purified by silica gel column chromatography using dichloromethane as a developing solvent, and the recovered colorless solid was recrystallized using dichloromethane to obtain 54.8 g of colorless plate crystals. This was identified as 3- (4-nitrophenyl) -4-methyl-2-oxazolidinone from the infrared absorption spectrum (shown in FIG. 29) and the nuclear magnetic resonance spectrum (shown in FIG. 30).

Example 16 3- (4-Nitrophenyl) -4-benzyl-2-oxy
Synthesis of Sazolidinone By the same procedure as in Example 1 except that 35 g of phenylalanine was used instead of alanine in Example 1, 28.3 g of phenylalaninol was obtained. This phenylalaninol 28.3
g in the place of alaninol of Example 15, and the same operation as in Example 15 is performed below. The colorless solid obtained is recrystallized from dichloromethane to give colorless columnar crystals.
40.9 g was obtained. This has an infrared absorption spectrum (Fig. 31
It was identified as 3- (4-nitrophenyl) -4-benzyl-2-oxazolidinone from the NMR spectrum and the nuclear magnetic resonance spectrum (shown in FIG. 32).

Example 17 3- (4-Nitrophenyl) -4-isopropyl-2-
Synthesis of oxazolidinone By the same procedure as in Example 1 except that 30 g of valine was used instead of alanine in Example 1, 24.3 g of valinol was obtained. 24.3 g of this valinol was reacted instead of alaninol of Example 15, and the same operation as in Example 15 was performed below, and the colorless solid substance obtained was recrystallized from dichloromethane to give 47.7 g of colorless plate crystals. Obtained. This one is
It was identified as 3- (4-nitrophenyl) -4-isopropyl-2-oxazolidinone from the infrared absorption spectrum (shown in FIG. 33) and the nuclear magnetic resonance spectrum (shown in FIG. 34).

Experimental Example 1 Each of the compounds obtained in Examples 1 to 14 had a particle size of about 1
What was made into powder of 00 μm was filled between the glass substrates, and this was filled with Nd: YAG laser (wavelength 1.064 μm, energy 3
50 mJ / pulse) was irradiated and the intensity of the second harmonic generated from each sample was observed. The intensity of these second harmonics was equivalent to the intensity of the second harmonic of 2-methyl-4-nitroaniline which was recently known.

Experimental Example 2 3- (5-Nitro-2-pyridinyl) -4-methyl-2-oxazolidinone obtained in Example 1 was placed in a test tube, and the tube was sealed under a reduced pressure of 20 mTorr. One end
By heating to 70 ° C., colorless needle-like crystals (0.5 mm × 1.0 mm × 10 mm) were deposited on the inner wall of the test tube which was not heated. This needle crystal was confirmed to be a single crystal by a polarization microscope. Using this crystal as a seed crystal, 3- (5-nitro-2-
When crystals were grown from a solution of pyridinyl) -4-methyl-2-oxazolidinone in ethyl acetate, 10 days later,
A single crystal of 5 mm × 5 mm × 15 mm could be obtained. This crystal had neither hygroscopicity nor sublimation property, and no change was observed even after standing at 60 ° C. and 60% humidity for 2 months.

Experimental Example 3 The 3- (5-nitro-2-pyridinyl) -4-ethyl-2-oxazolidinone obtained in Example 2 was placed in a test tube, and the tube was sealed under a reduced pressure of 20 mTorr. One end
By heating to 50 ° C., colorless needle crystals (0.2 mm × 0.5 mm × 7 mm) were observed to deposit on the inner wall of the test tube which was not heated. This needle crystal was confirmed to be a single crystal by a polarization microscope. Using this crystal as a seed crystal, 3- (5-nitro-2-
When crystal growth was performed from a solution of pyridinyl) -4-ethyl-2-oxazolidinone in ethyl acetate, 10 days later,
A single crystal of 2 mm × 5 mm × 10 mm could be obtained. This crystal had neither hygroscopicity nor sublimation property, and no change was observed even after standing at 60 ° C. and 60% humidity for 2 months.

Experimental Example 4 3- (5-Nitro-2-pyridinyl) -4-isopropyl-2-oxazolidinone obtained in Example 3 was placed in a test tube, and the tube was sealed under a reduced pressure of 20 mTorr. By heating one end to 177 ° C, precipitation of colorless columnar crystals (0.5 mm × 0.5 mm × 2 mm) was observed on the unheated inner wall of the test tube. This columnar crystal was confirmed to be a single crystal by a polarization microscope. When this crystal was used as a seed crystal and crystal growth was performed from an acetone solution of 3- (5-nitro-2-pyridinyl) -4-isopropyl-2-oxazolidinone,
After 10 days, a single crystal of 3 mm × 5 mm × 10 mm could be obtained. This crystal is not hygroscopic and sublimable,
No change was observed after being left for 2 months in% humidity.

Experimental Example 5 The 3- (5-nitro-2-pyridinyl) -4-isobutyl-2-oxazolidinone obtained in Example 4 was placed in a test tube, and the tube was sealed under a reduced pressure of 20 mTorr. By heating one end to 145 ° C, precipitation of colorless columnar crystals (1.0 mm × 1.0 mm × 3 mm) was observed on the unheated inner wall of the test tube. This columnar crystal was confirmed to be a single crystal by a polarization microscope. Using this crystal as a seed crystal, 3- (5-nitro-
When crystals were grown from a 2-pyridinyl) -4-isobutyl-2-oxazolidinoneacetone solution, after 10 days, single crystals of 3 mm × 5 mm × 10 mm could be obtained. This crystal had neither hygroscopicity nor sublimation property, and no change was observed even after standing at 60 ° C. and 60% humidity for 2 months.

Experimental Example 6 The 3- (5-nitro-2-pyridinyl) -4-sec-butyl-2-oxazolidinone obtained in Example 5 was placed in a test tube, sealed under a reduced pressure of 20 mTorr, and tested. By heating one end of the tube to 134 ° C, precipitation of colorless plate crystals (0.1 mm x 2.0 mm x 3 mm) was observed on the unheated inner wall of the test tube. This plate crystal was confirmed to be a single crystal by a polarization microscope. Using this crystal as a seed crystal, 3- (5-nitro-
When crystals were grown from a solution of 2-pyridinyl) -4-sec-butyl-2-oxazolidinone in ethyl acetate, 10
After a day, a 0.5 mm × 5 mm × 5 mm single crystal could be obtained. This crystal is not hygroscopic and sublimable,
No change was observed after being left for 2 months in% humidity.

Experimental Example 7 The 3- (5-nitro-2-pyridinyl) -4-phenyl-2-oxazolidinone obtained in Example 6 was placed in a test tube, and the tube was sealed under a reduced pressure of 20 mTorr. One end
By heating to 145 ° C, precipitation of colorless needles (0.2 mm × 0.2 mm × 7 mm) was observed on the unheated inner wall of the test tube. This needle crystal was confirmed to be a single crystal by a polarization microscope. Using this crystal as a seed crystal, 3- (5-nitro-2)
When crystals were grown from a solution of -pyridinyl) -4-phenyl-2-oxazolidinone in ethyl acetate, after 10 days, single crystals of 2 mm x 2 mm x 15 mm could be obtained. This crystal had neither hygroscopicity nor sublimation property, and no change was observed even after standing at 60 ° C. and 60% humidity for 2 months.

Experimental Example 8 The 3- (5-nitro-2-pyridinyl) -4-benzyl-2-oxazolidinone obtained in Example 7 was placed in a test tube, and the tube was sealed under a reduced pressure of 20 mTorr. One end
By heating to 135 ° C., precipitation of colorless plate crystals (0.2 mm × 2.0 mm × 4.0 mm) was observed on the unheated inner wall of the test tube. This plate crystal was confirmed to be a single crystal by a polarization microscope. Using this crystal as a seed crystal, 3- (5-nitro-
Crystal growth was carried out from a solution of 2-pyridinyl) -4-benzyl-2-oxazolidinone in ethyl acetate, and after 10 days, a 0.5 mm × 5 mm × 6 mm single crystal could be obtained. This crystal is not hygroscopic and sublimable,
No change was observed after being left for 2 months in% humidity.

Experimental Example 9 3- (5-Nitro-2-pyridinyl) -4-benzylthiomethyl-2-oxazolidinone obtained in Example 8 was placed in a test tube, sealed under a reduced pressure of 20 mTorr, and tested. By heating one end of the tube to 90 ° C, colorless plate-like crystals (0.2 mm × 2.0 mm × 4.0 m) are formed on the unheated inner wall of the test tube.
The precipitation of m) was observed. This plate crystal was confirmed to be a single crystal by a polarization microscope. This crystal is used as a seed crystal and 3- (5
When crystals were grown from a solution of -nitro-2-pyridinyl) -4-benzylthiomethyl-2-oxazolidinone in ethyl acetate, 0.4 mm x 5 mm x 6 mm single crystals could be obtained after 10 days. This crystal had neither hygroscopicity nor sublimation property, and no change was observed even after standing at 60 ° C. and 60% humidity for 2 months.

Experimental Example 10 3- (2-Acetylamino-4-nitrophenyl) -4-methyl-2-oxazolidinone obtained in Example 9 was placed in a test tube, sealed under a reduced pressure of 20 mTorr, and tested. By heating one end of the tube to 135 ° C, colorless needles (0.2 mm × 0.2 mm) will form on the inner wall of the unheated part of the test tube.
X5 mm) was observed. This needle crystal was confirmed to be a single crystal by a polarization microscope. Using this crystal as a seed crystal, 3-
Crystal growth was carried out from a solution of (2-acetylamino-4-nitrophenyl) -4-methyl-2-oxazolidinone in ethyl acetate. After 10 days, a single crystal of 5 mm × 7 mm × 10 mm could be obtained. This crystal had neither hygroscopicity nor sublimation property, and no change was observed even after standing at 60 ° C. and 60% humidity for 2 months.

Experimental Example 11 3- (2,4-dinitrophenyl) -4 obtained in Example 10
-Methyl-2-oxazolidinone was placed in a test tube, sealed under a reduced pressure of 20 mTorr, and one end of the test tube was heated to 120 ° C to give a pale yellow columnar crystal ( 0.5 mm × 0.5 mm × 2 mm) was observed. This columnar crystal was confirmed to be a single crystal by a polarization microscope. When this crystal was used as a seed crystal and crystal growth was performed from an acetone solution of 3- (2,4-dinitrophenyl) -4-methyl-2-oxazolidinone, after 10 days, 5 mm ×
A single crystal of 7 mm × 10 mm could be obtained. This crystal is
It had neither hygroscopicity nor sublimation, and did not show any change even after standing for 2 months at 60 ° C and 60% humidity.

Experimental Example 12 3- (2-acetylamino-4-nitrophenyl) -4-isobutyl-2-oxazolidinone obtained in Example 11 was placed in a test tube, sealed under a reduced pressure of 20 mTorr, and tested. By heating one end of the tube to 135 ° C, colorless columnar crystals (0.2 mm ×
0.2 mm x 2 mm) was observed. This columnar crystal was confirmed to be a single crystal by a polarization microscope. Using this crystal as a seed crystal, 3- (2-acetylamino-4-nitrophenyl)-
Crystal growth was performed from an acetone solution of 4-isobutyl-2-oxazolidinone, and after 10 days, 2 mm × 3 mm ×
A 10 mm single crystal could be obtained. This crystal had neither hygroscopicity nor sublimation property, and no change was observed even after standing at 60 ° C. and 60% humidity for 2 months.

Experimental Example 13 3- (2,4-dinitrophenyl) -4 obtained in Example 12
Take isobutyl-2-oxazolidinone in a test tube,
Seal the tube under a reduced pressure of 20 mTorr and put one end of the test tube at 105 ° C.
By heating to 0 ° C, precipitation of pale yellow plate crystals (0.1 mm × 1.0 mm × 1 mm) was observed on the inner wall of the unheated part of the test tube. This plate crystal was confirmed to be a single crystal by a polarization microscope. When this crystal was used as a seed crystal and crystal growth was performed from a solution of 3- (2,4-dinitrophenyl) -4-isobutyl-2-oxazolidinone in ethyl acetate, 10 days later, a 0.5 mm × 5 mm × 5 mm single crystal was obtained. I was able to get
This crystal had neither hygroscopicity nor sublimation property, and no change was observed even after standing at 60 ° C. and 60% humidity for 2 months.

Experimental Example 14 3- (2-acetylamino-4-nitrophenyl) -4-benzyl-2-oxazolidinone obtained in Example 13 was placed in a test tube, sealed under a reduced pressure of 20 mTorr, and tested. By heating one end of the tube to 150 ° C, the pale yellow needles (0.2 mm ×
0.2 mm × 5 mm) was observed. This needle crystal was confirmed to be a single crystal by a polarization microscope. Using this crystal as a seed crystal, 3- (2-acetylamino-4-nitrophenyl)-
Crystal growth was carried out from a solution of 4-benzyl-2-oxazolidinone in ethyl acetate, and after 10 days, 2 mm × 2 mm ×
A 10 mm single crystal could be obtained. This crystal had neither hygroscopicity nor sublimation property, and no change was observed even after standing at 60 ° C. and 60% humidity for 2 months.

Experimental Example 15 3- (2,4-dinitrophenyl) -4 obtained in Example 14
-Add benzyl-2-oxazolidinone to a test tube and
By sealing the tube under a reduced pressure of millitorr and heating one end of the test tube to 125 ° C, precipitation of pale yellow plate crystals (0.2 mm × 1.0 mm × 1 mm) was deposited on the inner wall of the unheated part of the test tube. saw. This plate crystal was confirmed to be a single crystal by a polarization microscope. When this crystal was used as a seed crystal and crystal growth was performed from a solution of 3- (2,4-dinitrophenyl) -4-benzyl-2-oxazolidinone in ethyl acetate, 10 days later,
A single crystal of 0.5 mm × 5 mm × 6 mm could be obtained. This crystal had neither hygroscopicity nor sublimation property, and no change was observed even after standing at 60 ° C. and 60% humidity for 2 months.

Experimental Example 16 3- (4-nitrophenyl) -4-obtained in Example 15
Take methyl-2-oxazolidinone in a test tube, seal the tube under a reduced pressure of 20 mTorr, and heat one end of the test tube to 135 ° C to give colorless needles (0.3 mm X 0.3 mm x 2.5 mm) was observed. This needle crystal was confirmed to be a single crystal by a polarization microscope.
Using this crystal as a seed crystal, 3- (4-nitrophenyl)-
Crystal growth was performed from a solution of 4-methyl-2-oxazolidinone in dichloromethane. After 10 days, 1.5 mm ×
A single crystal of 5.5 mm x 11 mm could be obtained. This crystal had neither hygroscopicity nor sublimation property, and no change was observed even after standing at 60 ° C. and 60% humidity for 2 months.

Experimental Example 17 3- (4-nitrophenyl) -4-obtained in Example 16
Take benzyl-2-oxazolidinone in a test tube, seal the tube under a reduced pressure of 20 mTorr, and heat one end of the test tube to 165 ° C to give colorless needles (0.2 mm X 0.2 mm x 1.8 mm) was observed.
This needle crystal was confirmed to be a single crystal by a polarization microscope. When this crystal was used as a seed crystal and crystal growth was performed from a dichloromethane solution of 3- (4-nitrophenyl) -4-benzyl-2-oxazolidinone, after 4 days, 5.
A single crystal of 5 mm x 5.5 mm x 11 mm could be obtained. This crystal had neither hygroscopicity nor sublimation property, and no change was observed even after standing at 60 ° C. and 60% humidity for 2 months.

Experimental Example 18 3- (4-nitrophenyl) -4-obtained in Example 15
Take isopropyl-2-oxazolidinone in a test tube,
Seal the tube under a reduced pressure of 20 mTorr and put one end of the test tube at 115 ° C.
By heating to above, precipitation of colorless needle crystals (0.3 mm × 0.3 mm × 1.9 mm) was observed on the unheated inner wall of the test tube. This needle crystal was confirmed to be a single crystal by a polarization microscope. When this crystal was used as a seed crystal and crystal growth was performed from a dichloromethane solution of 3- (4-nitrophenyl) -4-isopropyl-2-oxazolidinone, after 10 days, a 0.8 mm × 4.6 mm × 8.2 mm single crystal was obtained. I was able to get it. This crystal is not hygroscopic and sublimable, 60 ℃, 60%
No change was observed even after left for 2 months under humidity.

[0079]

INDUSTRIAL APPLICABILITY The non-linear optical element of the present invention is remarkably excellent in optical transparency, stability, crystallinity and the like as compared with conventional organic compounds used for non-linear optics, and easily and stably in a matrix. It is composed of an organic compound that can be oriented and dispersed. Therefore, it is industrially highly practical and can be suitably used as a wavelength conversion element or the like.

[Brief description of drawings]

FIG. 1 is a diagram showing an infrared absorption spectrum of 3- (5-nitro-2-pyridinyl) -4-methyl-2-oxazolidinone of the present invention produced in Example 1.

FIG. 2 is a diagram showing a nuclear magnetic resonance spectrum of 3- (5-nitro-2-pyridinyl) -4-methyl-2-oxazolidinone of the present invention produced in Example 1.

FIG. 3 is a diagram showing an infrared absorption spectrum of 3- (5-nitro-2-pyridinyl) -4-ethyl-2-oxazolidinone of the present invention produced in Example 2.

FIG. 4 is a diagram showing a nuclear magnetic resonance spectrum of 3- (5-nitro-2-pyridinyl) -4-ethyl-2-oxazolidinone of the present invention produced in Example 2.

FIG. 5 is a diagram showing an infrared absorption spectrum of 3- (5-nitro-2-pyridinyl) -4-isopropyl-2-oxazolidinone of the present invention produced in Example 3.

FIG. 6 is a diagram showing a nuclear magnetic resonance spectrum of 3- (5-nitro-2-pyridinyl) -4-isopropyl-2-oxazolidinone of the present invention produced in Example 3.

FIG. 7 is a graph showing an infrared absorption spectrum of 3- (5-nitro-2-pyridinyl) -4-isobutyl-2-oxazolidinone of the present invention produced in Example 4.

FIG. 8 is a diagram showing a nuclear magnetic resonance spectrum of 3- (5-nitro-2-pyridinyl) -4-isobutyl-2-oxazolidinone of the present invention produced in Example 4.

FIG. 9 is a diagram showing an infrared absorption spectrum of 3- (5-nitro-2-pyridinyl) -4-sec-butyl-2-oxazolidinone of the present invention produced in Example 5.

FIG. 10 is a diagram showing a nuclear magnetic resonance spectrum of 3- (5-nitro-2-pyridinyl) -4-sec-butyl-2-oxazolidinone of the present invention produced in Example 5.

11 is a view showing an infrared absorption spectrum of 3- (5-nitro-2-pyridinyl) -4-phenyl-2-oxazolidinone of the present invention produced in Example 6. FIG.

FIG. 12 is a diagram showing a nuclear magnetic resonance spectrum of 3- (5-nitro-2-pyridinyl) -4-phenyl-2-oxazolidinone of the present invention produced in Example 6.

13 is a diagram showing an infrared absorption spectrum of 3- (5-nitro-2-pyridinyl) -4-benzyl-2-oxazolidinone of the present invention produced in Example 7. FIG.

FIG. 14 is a diagram showing a nuclear magnetic resonance spectrum of 3- (5-nitro-2-pyridinyl) -4-benzyl-2-oxazolidinone of the present invention produced in Example 7.

FIG. 15: 3- (5-Nitro-2-pyridinyl) -4-benzylthiomethyl-2 of the present invention prepared in Example 8.
-A diagram showing an infrared absorption spectrum of oxazolidinone.

FIG. 16: 3- (5-Nitro-2-pyridinyl) -4-benzylthiomethyl-2 of the present invention prepared in Example 8
-A diagram showing a nuclear magnetic resonance spectrum of oxazolidinone.

FIG. 17: 3- (2-Acetylamino-4-nitrophenyl) -4-methyl-2 of the present invention prepared in Example 9
-A diagram showing an infrared absorption spectrum of oxazolidinone.

FIG. 18: 3- (2-Acetylamino-4-nitrophenyl) -4-methyl-2 of the present invention prepared in Example 9
-A diagram showing a nuclear magnetic resonance spectrum of oxazolidinone.

FIG. 19 shows the 3- (2 of the present invention produced in Example 10;
The figure which shows the infrared absorption spectrum of 4-dinitrophenyl) -4-methyl-2-oxazolidinone.

FIG. 20 shows the 3- (2 of the present invention produced in Example 10;
The figure which shows the nuclear magnetic resonance spectrum of 4-dinitrophenyl) -4-methyl-2-oxazolidinone.

FIG. 21: 3- (2- of the present invention produced in Example 11
The figure which shows the infrared absorption spectrum of acetylamino-4-nitrophenyl) -4-isobutyl-2-oxazolidinone.

FIG. 22 shows 3- (2- of the present invention produced in Example 11;
The figure which shows the nuclear magnetic resonance spectrum of acetylamino-4-nitrophenyl) -4-isobutyl-2-oxazolidinone.

FIG. 23 shows the 3- (2 of the present invention produced in Example 12;
The figure which shows the infrared absorption spectrum of 4-dinitrophenyl) -4-isobutyl-2-oxazolidinone.

FIG. 24 shows the 3- (2 of the present invention produced in Example 12;
The figure which shows the nuclear magnetic resonance spectrum of 4-dinitrophenyl) -4-isobutyl-2-oxazolidinone.

FIG. 25 shows 3- (2- of the present invention produced in Example 13
The figure which shows the infrared absorption spectrum of acetylamino-4-nitrophenyl) -4-benzyl-2-oxazolidinone.

FIG. 26 shows the 3- (2- of the present invention produced in Example 13;
The figure which shows the nuclear magnetic resonance spectrum of acetylamino-4-nitrophenyl) -4-benzyl-2-oxazolidinone.

FIG. 27 shows the 3- (2 of the present invention produced in Example 14;
The figure which shows the infrared absorption spectrum of 4-dinitrophenyl) -4-benzyl-2-oxazolidinone.

28 is a graph of 3- (2) of the present invention produced in Example 14. FIG.
The figure which shows the nuclear magnetic resonance spectrum of 4-dinitrophenyl) -4-benzyl-2-oxazolidinone.

FIG. 29 shows 3- (4-) of the present invention produced in Example 15.
The figure which shows the infrared absorption spectrum of nitrophenyl) -4-methyl-2-oxazolidinone.

FIG. 30 shows 3- (4-) of the present invention produced in Example 15.
The figure which shows the nuclear magnetic resonance spectrum of nitrophenyl) -4-methyl-2-oxazolidinone.

FIG. 31 shows the 3- (4-of the present invention produced in Example 16;
The figure which shows the infrared absorption spectrum of nitrophenyl) -4-benzyl-2-oxazolidinone.

32 is a 3- (4-) of the present invention produced in Example 16;
The figure which shows the nuclear magnetic resonance spectrum of nitrophenyl) -4-benzyl-2-oxazolidinone.

FIG. 33 shows 3- (4-) of the present invention produced in Example 17.
The figure which shows the infrared absorption spectrum of nitrophenyl) -4-isopropyl-2-oxazolidinone.

34 is a 3- (4-) of the present invention produced in Example 17. FIG.
The figure which shows the nuclear magnetic resonance spectrum of nitrophenyl) -4-isopropyl-2-oxazolidinone.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C07D 401/04 8829-4C 413/04 213 8829-4C

Claims (1)

[Claims] [Claim 1] The following general formula (1): [In the formula, X, Y and Z each represent a carbon atom, an oxygen atom, a sulfur atom or a nitrogen atom, and the other atoms except the oxygen atom have a hydrogen atom or a monovalent or divalent substituent. Ar represents an aromatic group or a heteroaromatic group, which may have a substituent on its ring] and / or the compound is a chemical compound in the polymer matrix. Non-linear optical element consisting of chemically bonded polymer compounds.