JPH0656771A - Organic compound single crystal and its production - Google Patents

Abstract

PURPOSE:To efficiently obtain the single crystal having short cut-off wavelengths, excellent in nonlinear optical characteristics, and useful for wavelength-converting elements, etc., by crystallizing out a specific compound from a solution comprising the compound and a solvent. CONSTITUTION:A compound of formula I [X, Y and Z are each C, O, S, N; Ar is a (substituted)aromatic group] such as a compound of formula II, is crystallized out from its solution using a solvent such as acetone to obtain this single crystal having a pair or more of substantially mutually parallel and optically smooth surfaces. The compound of formula I has a solubility of 1-50g/100g of the solvent at 25 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic compound single crystal which can be applied to an optoelectro element used for a wavelength conversion element and the like and a method for producing the same.

[0002]

_2. Description of the Related Art Conventionally, inorganic dielectrics such as KH ₂ PO ₄ , LiNbO ₃ and (NH ₄ ) H ₂ PO _{4 made of} inorganic compounds have been known as nonlinear optical crystals. It has been put to practical use as a material. However, recently, DAN (2-dimethylamino-5-nitroacetanilide), POM (3-methyl-4-nitropyridine-1-oxide) has been found to have greater nonlinear optical properties than these inorganic ferroelectrics. Non-linear optical crystals made of such organic compounds have come to be known. As a method for producing an organic compound single crystal, a vapor phase method, a melt method and a solution method are mainly known.
Among them, the solution method is suitable for obtaining a good quality single crystal having a size of several mm or more, because the crystal growth conditions are relatively mild. The solution method includes a solvent evaporation method and a slow cooling method. In both methods, it is necessary to dissolve a compound constituting a crystal in a solvent to prepare a saturated solution of the compound and obtain a relatively large single crystal. According to the above, a seed crystal is introduced into the saturated solution, and then precipitation of the dissolved compound is promoted by evaporation of the solvent or slow cooling to obtain a single crystal.

[0003]

In general, a nonlinear optical crystal of an organic compound is superior to that of an inorganic compound in nonlinear optical characteristics, but has a strong electron-donating group or electron-withdrawing group. Since it is a crystal of an organic compound having an electron system as a skeleton, its cutoff wavelength is on the long wavelength side as compared with a crystal of an inorganic compound. For example, the above DA
The cutoff wavelength of N is 500 nm, and in the case of POM it is 4
It is 50 nm. Therefore, these crystals cannot be used as a wavelength conversion element for blue laser light. Therefore, for use as a wavelength conversion element for blue laser light, there is a strong demand for a nonlinear optical crystal having not only high nonlinear optical characteristics but also a cutoff on the shorter wavelength side. As described above, the solution method is suitable as a method for producing a relatively large organic compound single crystal, but the quality and external shape of the obtained single crystal are greatly affected by the solvent used. Therefore, an object of the present invention is to solve the above problems,
An object of the present invention is to provide an organic compound single crystal having high nonlinear optical characteristics and having a cutoff on the short wavelength side. Further, it is possible to improve the drawbacks of the conventional solution method, to efficiently obtain the organic compound single crystal as an optically high quality single crystal, and to obtain a single crystal having a required crystal habit. It is to provide a manufacturing method that can.

[0004]

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

[Chemical 2] [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 may represent an aromatic group and may have a substituent on its ring] (hereinafter, referred to as a specific compound), and are substantially parallel to each other. An organic compound single crystal having a pair of optically smooth surfaces is provided.

The specific compound constituting the organic compound single crystal of the present invention has a basic structure in which a heterocycle is bonded to the group Ar, as is clear from the above general formula (1). Examples of this heterocycle include various ones, which are shown below by classifying them according to the types of the X, Y and Z atoms.

[0006]

The X, Y and Z atoms forming a part of this heterocycle may have a hydrogen atom or a monovalent or divalent substituent, and the monovalent substituent is 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 benzyl or 1 carbon atoms 4 represents an alkyl group)
The group represented by can be exemplified. Here, as the alkyl group, for example, a methyl group, an ethyl group, a propyl group,
Cyclopropyl group, butyl group, cyclobutyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, cycloheptyl group, octyl group, cyclooctyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group And those having 1 to 20 carbon atoms such as 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. be able to. 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 a phenyl group, a biphenyl group,
Examples thereof include those having 6 to 22 carbon atoms such as 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. Furthermore, the general formula
Examples of the group represented by (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 ones 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 vinylidene group, propenylidene group, butenylidene group,
Examples thereof include those having 1 to 20 carbon atoms such as a 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 and the like.

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. An alkyl group having 1 to 7 carbon atoms,
An aryl group having 6 to 8 carbon atoms (eg, phenyl group, o
-, M- or p-tolyl group, etc.), an aralkyl group having 7 to 9 carbon atoms (for example, benzyl group, phenylethyl group, etc.) and a group represented by the formula (2) (for example, (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), the aromatic group of Ar may be a carbocyclic aromatic group or a heterocyclic aromatic group. As the carbocyclic aromatic group, a phenyl group,
Examples thereof include a naphthyl group and an azulenyl group, and examples of the heterocyclic aromatic group include a pyridinyl group, a quinolyl group, an isoquinolyl group, a thienyl group, a furyl group, a pyrrolyl group, an imidazolyl group, and a pyrimidinyl group. can do. These aromatic groups may have a substituent on the ring, and as the substituent, for example, a nitro group, a cyano group, an alkoxycarbonyl group, an alkylcarbonyl group, a perfluoroalkylcarbonyl group, Electron withdrawing groups such as perfluoroalkyl groups, amino groups, monoalkylamino groups, dialkylamino groups, alkylcarbonylamino groups, perfluoroalkylcarbonylamino groups, hydroxyl groups, alkoxy groups, aryloxy groups, alkyl groups, halogens, etc. The electron-donating group can be mentioned. These are a combination of two or more kinds,
It may be substituted on the aromatic ring of the aromatic group.

Specific examples of the carbocyclic aromatic group having such a substituent include a 2-nitrophenyl group,
3-nitrophenyl group, 4-nitrophenyl group, 2,4-
Dinitrophenyl group, 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group, 2,4-dicyanophenyl group, 3-methoxycarbonyl group, 4-methoxycarbonyl group, 3-ethoxycarbonyl group, 4- Ethoxycarbonyl group, 2-acetylphenyl group, 3-acetylphenyl group, 4-acetylphenyl group, 4-trifluoroacetylphenyl group, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoro Methylphenyl group, 5-fluoro-2,4-dinitrophenyl group, 2-acetylamino-4-nitrophenyl group, 2-trifluoroacetylamino-4-nitrophenyl group, 2-dimethylamino-4-nitrophenyl group , 2- (t-butoxycarbonyl) amino-4-nitrophenyl group, 2- Benzyloxycarbonyl) amino-4-nitrophenyl group, 4-acetylamino-3-
Nitrophenyl group, 4-trifluoroacetylamino-
3-nitrophenyl group, 4-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 heterocyclic aromatic group having a substituent include a 3-nitro-2-pyridinyl group, a 4-nitro-2-pyridinyl group and a 5-nitro-2- group.
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 and 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 a carbon atom having 6 to 8 carbon atoms is added to the atom (Z) at the 4-position of the heterocycle described above. It is preferable that the aryl group of is bonded. When Ar is a nitro-2-pyridinyl group, an alkyl group having 1 to 7 carbon atoms, an aryl group having 6 to 9 carbon atoms, or the above formula is added to the atom (Z) at the 4-position of the heterocycle described above. It is preferable that the group represented by (2) 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]

In the present invention, particularly preferable compounds are 3- (5-nitro-2-pyridinyl) -4-methyl-2-oxazolidinone and 3- (5-nitro-2-pyridinyl) -4-ethyl-. 2-oxazolidinone, 3-
(5-Nitro-2-pyridinyl) -4-isopropyl-
2-oxazolidinone, 3- (5-nitro-2-pyridinyl) -4-isobutyl-2-oxazolidinone, 3-
(5-Nitro-2-pyridinyl) -4-sec-butyl-
2-oxazolidinone, 3- (5-nitro-2-pyridinyl) -4-phenyl-2-oxazolidinone, 3-
(5-Nitro-2-pyridinyl) -4-benzyl-2-
Examples thereof include compounds having a 2-oxazolidinone ring having a pyridinyl ring as an aromatic group, such as oxazolidinone and 3- (5-nitro-2-pyridinyl) -4-benzylthiomethyl-2-oxazolidinone.

Crystal habit of single crystal and optical smoothness and its surface The organic compound single crystal of the present invention has one or more pairs of surfaces which are substantially parallel to each other and optically smooth. Therefore, it is suitable for use as a wavelength conversion element or the like. Here, the pair of surfaces being “substantially parallel to each other and optically smooth” means that the surfaces allow light to be incident, propagated, reflected or emitted with low loss. More specifically, it means that when light is incident on one of the two parallel surfaces, the light is emitted from the other surface with a transmittance of 60% or more. Such substantially parallel and optically smooth surfaces may be surfaces naturally formed by a vapor phase method or a solution method, or surfaces obtained by crystal processing such as cutting, cleavage, and polishing. Good.
The area of such a surface needs to be larger than the diameter of the irradiated laser light, and is, for example, 1.5 times or more, preferably 5 times or more the diameter of the laser light. Specifically, an area of 1.5 × 1.5 (mm ² ) is desired, but 5 × 5 (mm
² ) The following is sufficient.

Production of Specific Compound The specific compound constituting the organic compound single crystal of the present invention is represented by the following formula (2) Ar—NH—Z—Y—XH (2) [wherein R, X, Y, Z and Ar is as described above] (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, 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 into 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 that 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 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 this time, 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 relative 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 the base used at that time is
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 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 base used is usually 1 mol of N-substituted amino alcohol
It is 0.05 to 1 mol. Further, in the above, 1,1'-carbonylbis (2-methylimidazole) or 1,1'-carbonyldi-1,2,4-triazole may be used instead of 1,1'-carbonyldiimidazole, The specific compound can be obtained in the same manner.

In addition to the N-substituted amino alcohol represented by the above formula (3), for example, N- (aromatic or heteroaromatic) -2-hydroxyethaneamide (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" A specific compound can be synthesized by using “hydroxybutanoic acid”) or N- (aromatic or heteroaromatic) amino acid (hereinafter referred to as “N-substituted amino acid”). Hereinafter, these methods will be briefly described.

A method utilizing the reaction of N-substituted hydroxyethanoic acid amide with an aldehyde or ketone; 1,3-oxazolidine is obtained by reacting N-substituted hydroxyethanoic acid amide with an aldehyde or ketone in the presence of an acid or a dehydration condensation agent. By using -4-one, a specific compound can be obtained. 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 benzene, toluene and the like. Examples of the aldehyde used include formaldehyde, acetaldehyde,
Examples include propionaldehyde, butyraldehyde, 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 can be mentioned. The amount of the aldehyde or ketone used is stoichiometrically equivalent or in excess with respect to 1 mol of the N-substituted hydroxyethanoic acid amide,
Usually, it is 1 to 5 mol.

Method using hydroxybutanoic acid; 3-
The specific compound is obtained by cyclizing (aromatic or heteroaromatic) amino-4-hydroxybutanoic acid or 2- (aromatic or heteroaromatic) amino-4-hydroxybutanoic acid into a lactone. 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. Among these, preferred are benzene, toluene, 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 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 a "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 then the amino group is converted to an aromatic group or a hetero group. A method of modifying with an aromatic group. In this method, as a method for reducing the carboxyl group of the substituted amino acid, a borane reduction method using a borane reagent can be mentioned (M. Hudlicky, "Reductionsin Organic
Chemistry ", Willy, New York, 1984). This borane reduction method is effectively applied to the reduction of optically active substituted amino acids without racemization during the reduction reaction. Examples of amino acids include homoalanine, norvaline, leucine, isoleucine, tert-leucine, norleucine, phenylglycine, S-methylcysteine, S-benzylcysteine, etc. In this case, the borane reagent is borane-dimethylsulfide. A complex, borane-pyridine complex, borane-dimethylamine complex, borane-diethylamine complex, borane-t-butylamine complex, borane-tetrahydrofuran complex, borane-morpholine complex, borane-ether complex, diborane and the like can be used. Of these, the preferred one is , Borane-dimethyl sulfide complex, borane-ether complex, and diborane. The amount of the borane reagent used is stoichiometrically equivalent or in excess with respect to 1 mol of the substituted amino acid, and preferably 1 to 2 mol. Is.

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

As a means for modifying the amino group of the substituted amino alcohol obtained by the above reduction reaction with an aromatic group or a heteroaromatic group, 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. In particular, a chloro group and a trifluoromethanesulfonyloxy group are preferable. The amount of the derivative having a leaving group used is stoichiometrically equivalent to or more than 1 mol of the substituted amino alcohol, and preferably 1 to 2 mol.

In order to complete this reaction, it is desirable to carry out the reaction in the presence of a base. As this base,
Examples thereof include inorganic bases, tertiary amines, pyridines and the like, and particularly preferably used are triethylamine, pyridine and potassium carbonate. The amount of the base used is usually a stoichiometrically equivalent amount or excess amount relative to 1 mol of the substituted amino alcohol, and 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 this 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 an aluminum hydride reduction method, a borohydride reduction method and a hydrogenation method (M. Hud-licky, "Reductions
In Organic Chemistry ", Willy, New York, 1984). Examples of the substituted amino acid ester to which these methods are applied include the methyl ester and ethyl ester of the substituted amino acid exemplified in Production Method 1. 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, hydrogenated bis (2
-Methoxyethoxy) aluminum sodium, diisobutylaluminum hydride and the like can be mentioned, and among these, lithium aluminum hydride and dimethoxyaluminum hydride are preferable. These reducing agents are usually used in a proportion of 0.5 to 10 mol per mol of the substituted amino acid ester. The reduction reaction in this case is usually performed in a solvent. The solvent used is
There is no particular limitation as long as it is inert to the reduction reaction, and various types can be used, and specifically, aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, ethers, etc. Can be mentioned. Tetrahydrofuran, diethyl ether and toluene are particularly preferably used. The temperature of the reduction reaction is usually -20 to 110.
℃. 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 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, Raney nickel, copper chromite, zinc chromite,
Rhenium oxide, palladium, etc. are used. The amount of these catalysts used is usually 0.00002 to 0.02 mol per mol of the substituted amino acid ester. This reduction reaction is usually
It is carried out in a solvent. Examples of this solvent include aliphatic or aromatic hydrocarbons, esters, carboxylic acids, ethers, alcohols, ketones and the like. Particularly preferably used are methanol and ethanol. Further, this reduction reaction can be carried out under a hydrogen gas atmosphere at normal pressure, or can also be carried out by forcibly inserting hydrogen gas under pressure using an autoclave. The temperature of this reduction reaction is usually 0 to 30.
It is 0 ° C. As a method for modifying the amino group of the substituted amino alcohol obtained by the above-mentioned reduction reaction with an aromatic group or a heteroaromatic group, the method described in Production Method 1 can be adopted.

Production method 3; a method of modifying the amino group of a D-, L-, or DL-substituted amino acid ester with an aromatic group or a heteroaromatic group, and then reducing the ester group. As a method of modifying the amino group with an aromatic group or a heteroaromatic group, a method of modifying the amino group of the substituted aminoalcohol mentioned in the production method 1 with an aromatic group or a heteroaromatic group can be 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, the hydrogenation method and the like 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. Examples of the aromatic or heteroaromatic amine derivative used here include aromatic or heteroaromatic amines, aromatic or heteroaromatic trimethylsilylamines, lithium aromatic or heteroaromatic amides, 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, or 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 to be used is not particularly limited as long as it is inert to the reaction, and various ones can be used. Examples thereof include system or aromatic hydrocarbons, halogenated hydrocarbons, ethers, alcohols, ketones, sulfoxides and amides. Particularly preferably used are diethyl ether, dimethyl sulfoxide, N-methylpyrrolidone and N, N-dimethylformamide. The reaction temperature is usually 0
~ 100 ° C. This method is particularly useful in one stage
It is advantageous in that a substituted amino alcohol can be obtained.

Synthesis of N-Substituted Hydroxyethanoic Acid Amide N-substituted hydroxyethanoic acid amide is synthesized by a method of activating the carboxyl group of hydroxyethanoic acid and then reacting with aromatic amine or 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, and 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 particularly, a chloro group and a trifluoro group. A methanesulfonyloxy group is preferred. The amount of the aromatic 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 this 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
-Stoichiometrically equivalent 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 this solvent include aromatic hydrocarbons, halogenated hydrocarbons, ethers, alcohols, ketones, sulfoxides, and amides. 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 it to amino acids.

Production of Single Crystal of Specific Compound The organic compound single crystal of the present invention is prepared from the above-obtained specific compound represented by the general formula (1) by a known vapor phase method described below. It can be manufactured by any of the melting method and the solution method. When using the gas phase method,
For example, a single crystal can be easily obtained by a sealing tube method in which a specific compound is packed in a glass test tube and the test tube is sealed.
Further, a thin film single crystal can be obtained by a method of laminating molecules of a specific compound on a certain substrate, that is, a so-called epitaxial method. When the melting method is used, a normal freezing method, a zone melting method or the like can be appropriately selected. Further, it is possible to crystallize into a fiber by using a glass capillary. In the case of the solution method, first, a specific compound is dissolved in a solvent to prepare a saturated solution of the compound, and then evaporation of the solvent or cooling to promote precipitation of the dissolved specific compound to obtain a single crystal. At this time, the length of the longest part of the target single crystal is 2-3 mm.
When the amount is not more than the level, it is generally unnecessary to introduce a seed crystal, but when a relatively large single crystal exceeding this is obtained, the seed crystal is generally introduced into the saturated solution and grown as a single crystal. More specifically, a saturated solution is prepared from a specific compound and a solvent at a specific temperature, and after standing for about 1 day or more to confirm that crystals do not precipitate, one seed crystal is introduced into the saturated solution. . The saturated solution used here is, for example, added such that the specific compound is about 30% in excess of the saturated concentration at the specific temperature when the specific compound is dissolved in the solvent, and the temperature is raised once to completely dissolve the temperature. Gradually lower and keep constant at the specified temperature. Then, precipitation and precipitation of the specific compound occur from the solution. After 24 hours or more have elapsed from the precipitation, the supernatant was filtered off from the solution and transferred to a single crystal growth vessel for use. The seed crystal may be suspended in the solution with a platinum wire or the like, or may be placed on the bottom of the growth container or on the substrate arranged in the growth container. Then 1-3
After further standing for a day to observe the state of the seed crystal and confirming that it slightly dissolves or does not change, the solvent is evaporated or the solution is cooled to promote the precipitation of the specific compound dissolved in the solution, and the seed crystal Grow. The growth vessel used in the solution method is preferably a vessel capable of controlling the temperature of the contained solution, for example, a double-bottomed glass or metal having a jacket portion capable of flowing a temperature-controlled circulating liquid. A flask is mentioned. The seed crystal is prepared, for example, as follows. Put the solvent used for crystal growth in the flask and add the specific compound so that it will be about 10 to 30% over the saturation concentration at room temperature, raise the temperature once to completely dissolve it, and then gradually lower the temperature to room temperature. Leave it at. Usually, seed crystals with a size of about 1 mm × 3 mm are formed in the flask after about 3 to 7 days. Solution Method Improvement 1 As a result of studying a solvent used for the purpose of increasing the efficiency of production of an organic compound single crystal by the solution method, the present inventors have found that the use of a solvent having a specific solubility is advantageous. I found it. That is, according to the present invention, there is a step of crystallizing a specific compound from a solution containing the specific compound, in a so-called solution method, the solvent used in the solution, the solubility of the specific compound at 25 ℃ solvent 1 to 50 per 100g
There is provided a method for producing an organic compound single crystal, which is a solvent of which the amount is preferably g, preferably 10 to 35 g. When a solvent having such a specific solubility is used, the precipitation of the specific compound dissolved in the solution can be easily controlled, and a high quality single crystal can be obtained at an appropriate rate. This is because if the solubility is too high, the rate at which the molecules are supplied to the crystal surface exceeds the rate at which the molecules are trapped on the surface of the single crystal, and the unit cell shift is likely to occur. Because it will be late. Examples of organic solvents that can be used in this method include ketones, ethers, esters, aliphatic hydrocarbons, aromatic compounds, halogenated hydrocarbons, alcohols, sulfur compounds, and nitrogen compounds. For example, the solvent may be selected so as to have a predetermined solubility for each desired specific compound. The solvent may be one kind alone or a mixed solvent composed of two or more kinds. Explaining the solvent more specifically, the ketones include acetone, methyl ethyl ketone, 2-pentanone, and 3
-Pentanone, 2-hexanone, 2-heptanone, acetophenone, cyclohexanone, etc. are illustrated. Examples of ethers include diethyl ether, dipropyl ether, dioxane, tetrahydrohydrolane, diisobutyl ether, dibutyl ether, diisopropyl ether and the like. Examples of the esters include ethyl formate, isopropyl formate, butyl formate, isobutyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, diethyl carbonate and the like. Examples of the aliphatic hydrocarbons include normal pentane, normal hexane, normal heptane, normal octane, 2-methylbutane, cyclohexane and methylcyclohexane. Examples of aromatic hydrocarbons include benzene, toluene, xylene, anisole, phenol, cumene, ethylbenzene and the like. Halogenated hydrocarbons include dichloromethane, chloroform, carbon tetrachloride,
Examples include 1,1-dichloroethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, trichloroethylene, tetraethylene, 1,2-dibromoethane, bromobenzene and the like. As alcohols, methanol,
Ethanol, 1-propanol, 2-propanol, 1
-Butanol, 2-butanol, 1-pentanol, isobutyl alcohol, 2-methoxyethanol, cyclohexanol and the like are exemplified. As the sulfur-containing solvent,
Examples include dimethyl sulfoxide and the like. Acetonitrile etc. are illustrated as a nitrogen-containing solvent. When the above solvent is used alone, among these, acetone, methyl ethyl ketone, acetophenone, diethyl ether, dioxane, tetrahydrofuran, ethyl formate, methyl acetate, ethyl acetate, benzene, toluene, dichloromethane, 1,1-dichloroethane. 1,2-dichloroethane, methanol, ethanol and the like are preferable. Also, 2
When a mixed solvent composed of two kinds of solvents is used, preferred combinations include ketones and esters, ketones and halogenated hydrocarbons, ketones and aromatic hydrocarbons, ketones and alcohols, halogenated compounds. Examples thereof include hydrocarbons and esters, halogenated hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbons and alcohols, esters and aromatic hydrocarbons, esters and alcohols, and the like. More specifically, acetone and ethyl acetate, acetone and dichloromethane, acetone and 1,2-dichloroethane, acetone and benzene, acetone and ethanol, ethyl acetate and benzene, ethyl acetate and dichloromethane, ethyl acetate and 1,2-dichloroethane, Examples include combinations of ethyl acetate and ethanol, benzene and dichloromethane, benzene and 1,2-dichloroethane, dichloromethane and ethanol, 1,2-dichloroethane and ethanol, and the like. As a mixed solvent composed of three kinds of solvents, ketones, esters and halogenated hydrocarbons, ketones, esters and aromatic compounds, ketones and halogenated hydrocarbons and aromatic compounds, esters And a combination of halogenated hydrocarbons and aromatic compounds. Among these, preferred combinations are acetone, ethyl acetate and dichloromethane, acetone and ethyl acetate and 1,2-dichloroethane, acetone and ethyl acetate and benzene, acetone and dichloromethane and benzene, acetone and 1,2-dichloroethane and benzene, and ethyl acetate. And dichloromethane and benzene, ethyl acetate and 1,2-dichloroethane and benzene. When a mixed solvent composed of two or more kinds of solvents is used, the content of any constituent solvent in the solvent composition is preferably 1% by volume or more, and more preferably 10% by volume or more. Improved Solution Method In the two- solution method, the crystal habit of a single crystal is determined by the solvent used. The inventors of the present invention, when using a mixed solvent composed of two or more kinds of solvents satisfying a specific condition when carrying out the solution method, have a thickness and have a shape suitable for processing when used in a wavelength conversion element or the like. It was found that an organic compound single crystal was obtained. That is, according to the present invention, there is a step of crystallizing a specific compound from a solution containing the specific compound, in the method for producing a single crystal of the specific compound, the solvent used in the solution, as a solvent alone Provided is a method for producing an organic compound single crystal, which is a mixed solvent of two or more kinds of solvents having different crystal habits when used. The crystal habit here means the outer shape of the crystal. Preferred examples of combinations of two or more solvents used in the above method include ketones and esters, ketones and halogenated hydrocarbons, ketones and aromatic hydrocarbons, halogenated hydrocarbons and esters. And halogenated hydrocarbons and aromatic hydrocarbons, esters and aromatic hydrocarbons, and the like. Particularly suitable solvent combinations include, for example, acetone and ethyl acetate, acetone and dichloromethane, acetone and 1,2-dichloroethane, acetone and benzene, ethyl acetate and benzene, dichloromethane and ethyl acetate, 1,2-
Examples include dichloroethane and ethyl acetate, 1,2-dichloroethane and benzene, and dichloromethane and benzene.
The mixing ratio when combining two or more solvents is preferably 5% by volume or more, and more preferably 20% by volume or more, in the proportion of any constituent solvent.

The crystal obtained as described above can be suitably used as a nonlinear optical element. On this occasion,
A part or the whole of the crystal surface may be coated and protected. As the coating material used for this purpose, inorganic compounds such as glass, polycarbonate, polymethylmethacrylate, polypropylene, cellulose acetate, polystyrene, acrylonitrile-polystyrene copolymer,
Examples thereof include organic compounds such as polyethylene glycol bisallyl carbonate, polyvinyl alcohol, polyethylene terephthalate, polyvinyl chloride, polysulfone and polyimide. Further, for the purpose of matching the refractive index, the crystal can be used by immersing it in a medium inert to the surface of the crystal, such as liquid paraffin, various silicone oils, and fluorinated oils. Furthermore, on the surface of the crystal,
For example, U.S. Pat. No. 3,330,681, Japanese Patent Publication No. Sho 56-1548.
No. 1, JP-A-58-670701, JP-B-55-40631
A film phase such as an antireflection coating can be provided by the method disclosed in Japanese Patent Publication No. The entire crystal may be cooled or heated with an inert medium or the like before use. As this inert medium, various silicone oils,
Fluorine type oil etc. can be mentioned.

[0043]

EXAMPLES Synthesis Example 1 3- (5-Nitro-2-pyridinyl) -4-methyl-2
-Synthesis of oxazolidinone 30 g of alanine was dissolved in 150 g of anhydrous tetrahydrofuran, 35.0 g of boron trifluoride ethyl ether was added thereto, and the mixture was stirred at 60 ° C for 1 hour in 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. Then, 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 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 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, 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 collected 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.
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 recovered pale yellow solid was recrystallized with ethyl acetate to give 33.6 g of crystal powder.
Got This product shows 3 from the infrared absorption spectrum (shown in FIG. 1) and the nuclear magnetic resonance spectrum (shown in FIG. 2).
-(5-Nitro-2-pyridinyl) -4-methyl-2-
It was identified as oxazolidinone.

Synthesis Example 2 3- (5-Nitro-2-pyridinyl) -4-ethyl-2
-Synthesis of oxazolidinone In Synthesis Example 1, homoalanine 30.3 was used instead of 30 g of alanine.
g, and the amount of boron trifluoride ethyl ether used
Homoalaninol 2 was prepared in the same manner as in Synthesis Example 1 except that the amount of the dimethyl sulfide solution of 30.5 g and the 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, the product was extracted with ethyl acetate, and the organic layer was washed with water and then saturated saline solution. 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 collected yellow solid 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.
When the solution dissolved in was stirred under ice cooling, phosgene generated by the reaction of 38.7 g of trichloromethyl chloroformate with 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 crystal powder. This compound was identified as 3- (5-nitro-2-pyridinyl)-by infrared absorption spectrum (shown in FIG. 3) and nuclear magnetic resonance spectrum (shown in FIG. 4).
It was identified as 4-ethyl-2-oxazolidinone.

Synthesis Example 3 3- (5-Nitro-2-pyridinyl) -4-isopropyi
Synthesis of Le-2-oxazolidinone In Synthesis Example 1, valin 32.4 g was used in place of alanine 30 g, 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 Synthesis 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, the product was extracted with ethyl acetate, and the organic layer was washed with water and then saturated saline solution. 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 further 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 recovered pale yellow solid was recrystallized using ethyl acetate to obtain 31.1 g of crystal powder. This compound was identified as 3- (5-nitro-2-pyridinyl)-by infrared absorption spectrum (shown in FIG. 5) and nuclear magnetic resonance spectrum (shown in FIG. 6).
It was identified as 4-isopropyl-2-oxazolidinone.

Synthesis Example 4 3- (5-Nitro-2-pyridinyl) -4-isobutyl
Synthesis of 2-oxazolidinone In Synthesis 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 the amount of the 10 M borane-dimethyl sulfide complex dimethyl sulfide solution used was 26.5 g,
The same operation as in Synthesis 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, 2N hydrochloric acid aqueous solution is added to adjust the pH of the reaction solution.
After adjusting the ratio to around 4, 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 further 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 crystal powder. This product was identified by 3- (5-nitro-2) from the infrared absorption spectrum (shown in FIG. 7) and the nuclear magnetic resonance spectrum (shown in FIG. 8).
-Pyridinyl) -4-isobutyl-2-oxazolidinone.

Synthesis Example 5 3- (5-Nitro-2-pyridinyl) -4-sec-butyl
Synthesis of ru-2-oxazolidinone In Synthesis Example 4, isoleucine 3 was used instead of leucine 32.0 g.
20 g of isoleucinol was obtained by performing the same operation as in Synthesis Example 4 except that 2.0 g was used. 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. Then 2N
After adding hydrochloric acid aqueous solution to adjust 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 collected 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 prepared 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 recovered pale yellow solid was recrystallized using ethyl acetate to obtain 27.4 g of crystal powder. This product has an infrared absorption spectrum (shown in Fig. 9) and a nuclear magnetic resonance spectrum (Fig.
10-) to 3- (5-nitro-2-pyridinyl)-
It was identified as 4-sec-butyl-2-oxazolidinone.

Synthesis Example 6 3- (5-nitro-2-pyridinyl) -4-phenyl-
Synthesis of 2-oxazolidinone In Synthesis Example 1, α-phenylglycine 31.5 g was used instead of alanine 30 g, boron trifluoride ethyl ether was used in an amount of 22.1 g, and a 10 M borane-dimethyl sulfide complex in a dimethyl sulfide solution was used. 20 g of α-phenylglycinol was obtained by the same procedure as in Synthesis Example 1, except that the amount used was 23.0 g. 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 adjust 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 collected 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) dissolved in 150 g of tetrahydrofuran was stirred under ice-cooling, and then generated by the reaction of trichloromethyl chloroformate (18.9 g) with activated carbon. The phosgene thus cooled 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 with ethyl acetate to obtain 18.8 g of crystal powder. This shows the infrared absorption spectrum (shown in Fig. 11) and nuclear magnetic resonance spectrum (Fig.
12-) to 3- (5-nitro-2-pyridinyl)-
It was identified as 4-phenyl-2-oxazolidinone.

Synthesis Example 7 3- (5-Nitro-2-pyridinyl) -4-benzyl-
Synthesis of 2-oxazolidinone In Synthesis Example 1, phenylalanine was used instead of 30 g of alanine.
The same operation as in Synthesis 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 reacted at room temperature for 12 hours. After adding 2N hydrochloric acid aqueous solution to bring 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 over 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 collected yellow solid 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 25.1 g of crystalline powder.
Got This product has 3 spectra from infrared absorption spectrum (shown in FIG. 13) and nuclear magnetic resonance spectrum (shown in FIG. 14).
-(5-Nitro-2-pyridinyl) -4-benzyl-2
-Identified as oxazolidinone.

Synthesis Example 8 3- (5-Nitro-2-pyridinyl) -4-benzylthio
Synthesis of Omethyl-2-oxazolidinone In Synthesis 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 the dimethyl sulfide of 10M borane-dimethyl sulfide complex was used. The amount of solution used is 16.0g
20 g of S-benzyl cysteinol was obtained by performing the same operation as in Synthesis 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 hydrochloric acid aqueous solution to bring 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 over 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 collected 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 of 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 between 20.2 g of trichloromethyl chloroformate and activated carbon was cooled and liquefied was 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 obtain 23.8 g of crystal powder. It was identified as 3- (5-nitro-2-pyridinyl) -4-benzylthiomethyl-2-oxazolidinone by infrared absorption spectrum (shown in FIG. 15) and nuclear magnetic resonance spectrum (shown in FIG. 16). It was

Example 1 3- (5-Nitro-2-pyridinyl) -4-isopropyi
Production of Single Crystal of Lu-2-oxazolidinone by Gas Phase Method As shown in FIG.
As a result, 0.24 g of 3- (5-nitro-2-pyridinyl) -4-isopropyl-2-oxazolidinone (abbreviated as IPNPO) obtained in Synthesis Example 3 was added. After replacing the inside of the test tube with nitrogen, the upper end 3 was sealed with a burner while depressurizing.
The test tube 1 was set up on the mantle heater 4, and a heat insulating material 5 such as glass wool was filled in the gap. When the outer wall of the test tube was measured with a thermocouple 6 and kept at 120 ° C. for 3 days, a large number of needle-shaped crystals 7 were obtained on the inner wall of the test tube. The crystal is up to
It was 10 mm x 1 mm x 0.1 mm. By observing under a polarizing microscope, it has a pair of surfaces parallel to each other with a size of 10 mm x 1 mm,
It was confirmed to be a good quality single crystal having a good transmittance of 75%. Example 2 3- (5-Nitro-2-pyridinyl) -4-isobutyl
Single Crystal Production of 2-Oxazolidinone by Gas Phase Method Starting Material Compound 3- (5-nitro-2) obtained in Synthesis Example 4
-Pyridinyl) -4-isobutyl-2-oxazolidinone (abbreviated as IBNPO hereinafter) to 0.1 g, 120
A single crystal was produced in the same manner as in Example 1 except that the heat retention time at ° C was changed to 4 days. Many acicular crystals were obtained on the inner wall of the test tube. The maximum crystal size is 7 mm x 1 mm x 0.1 mm
Met. It was confirmed by observation under a polarization microscope that the single crystal had a pair of planes having a size of 7 mm × 1 mm parallel to each other and had a good transmittance of 70%.

Example 3 3- (5-Nitro-2-pyridinyl) -4-isobutyl
-2-Crystal Production by Oxazolidinone by Melting Method As shown in FIG. 18, a glass tube 9 having a length of about 25 m, an outer diameter of 15 mm, an inner diameter of 12 mm and a thin end drawn into a capillary shape, and the capillary tip 8 being sealed Synthesis example 4 as sample 10
2.3 g of IBNPO obtained in the above was added. The IBNPO in the glass tube 9 was heated at 130 ° C. to be melted, the inside was replaced with nitrogen, and the tip portion 11 opposite to the capillary side 10 was sealed with a burner while depressurizing. I in a glass tube at room temperature
After the BNPO was solidified, it was suspended in a glass Bridgman furnace 12 shown in FIG. In this furnace, heater 15
As a result, a part having a temperature higher than the melting point of IBNPO by about 3 ° C. and a part having a lower temperature are distributed in a band shape. The tip 8 on the capillary side of the glass tube 9 was adjusted to the height of the highest temperature part of the Bridgman furnace, and after confirming that the IBNPO inside the capillary had melted, the glass tube was lowered at a speed of 3.2 cm / day.
Two days later, the descent was stopped and the glass tube was pulled up. Cut the glass tube with a diamond saw and take out the IBNPO solid,
Cleavage parallel to the (201) plane, 12 mm × 10 mm × 3 mm
A good size crystal was obtained. It was confirmed by observation under a polarizing microscope that the single crystal had a pair of planes parallel to each other and had a size of 10 mm × 3 mm, and had good transparency.

Example 4 Production of Crystals of IPNPO by Solution Method First, 5 g of sufficiently purified IPNPO powder obtained in Synthesis Example 3 and 50 ml of sufficiently purified ethyl acetate were placed in a flask, and the temperature of this solution was 40 ° C. The IPNPO was completely dissolved. When the solubility of IPNPO in ethyl acetate at 25 ° C. was measured, it was 2.1 g / 100 g. Next, the temperature of the solution was lowered to 25 ° C. to precipitate IPNPO, and the supernatant of the precipitation solution was filtered with a filter and transferred to the glass growth container 16 shown in FIG. Glass growth container 16 shown in FIG.
Is equipped with a jacket 18 through which liquid can flow as shown by arrows 18a and 18b so that the temperature of the liquid 17 contained in the container can be controlled, and a glass lid 19 is put on during use. You can The above-mentioned supernatant liquid (liquid 17) transferred to this growth container 16 was heated to 40 ° C. and kept for 1 hour or more to completely dissolve the crystalline embryo, and then lowered to 25 ° C. and kept at the temperature for 1 day. A flake-shaped seed crystal 20 having a size of about 1 mm × 2 mm was put into this solution 17 to start crystal growth. By lowering the temperature at a rate of about 0.1 ° C. per day, precipitation of IPNPO in the solution was promoted and seed crystals were grown. After 10 days, a 10 mm × 3 mm × 0.5 mm colorless and transparent single crystal of very good quality was obtained. This is a size and shape that can be sufficiently processed such as cutting and polishing. It was confirmed by observation under a polarizing microscope that the single crystal had a pair of planes parallel to each other and had a size of 10 mm × 3 mm, and had good transparency.

Example 5 Production of Crystals of IBNPO by Solution Method First, 10 g of the fully purified IBNPO powder obtained in Synthesis Example 4 and 25 ml of sufficiently purified acetone and 25 ml of 1,2-dichloroethane were mixed in a flask. The temperature of this solution was raised to 40 ° C. to completely dissolve IBNPO. I
When the solubility of BNPO in the mixed solvent at 25 ° C. was measured, it was 16 g / 100 g solvent. Next, the temperature of the obtained solution was lowered to 25 ° C. to precipitate IBNPO, and the supernatant of the precipitated solution was filtered with a filter and transferred to the glass growth container 16 shown in FIG. The supernatant (liquid 17) transferred to the growth vessel 16 was heated to 40 ° C. and kept for 1 hour or more to completely dissolve the crystal embryos, then lowered to 25 ° C. and kept at that temperature for 1 day. Next, a seed crystal 20 having a size of about 1 mm × 1.5 mm was put into the solution 17 to start crystal growth. As in Example 4, the temperature of the solution was lowered at a rate of about 0.1 ° C./day to promote precipitation in the solution to grow a seed crystal. After 25 days, 12 mm × 7 mm ×
A 1.5 mm colorless and transparent single crystal was obtained. This is a size and shape that can be sufficiently processed such as cutting and polishing. When observed under a polarizing microscope, the size of
It was confirmed to be a good quality single crystal having a pair of surfaces of mm × 7 mm and having good transparency. Example 6 Crystal Production by Solution Method A single crystal was produced by a solution method in the same manner as in Example 4 except that any one of the specific compounds obtained in Synthesis Examples 1, 2, and 5 to 8 was used as a starting material. . Each of the obtained single crystals had a pair of substantially parallel and optically smooth surfaces, and had a size and shape sufficient for processing such as cutting and polishing.

Experimental Example 1 X-ray Structural Analysis of IPNPO Crystals and IBNPO Crystals When the needle crystals obtained in Examples 1 and 2 were analyzed by 4-axis X-ray analysis, the IPNPO crystals were found to have space group P
2 ₁ : Lattice constant is a = 5.552Å, b = 9.905Å, c = 1
The values were 0.749Å, Z = 2 and β = 102 °. Also, IBN
The PO crystal has a space group P2 ₁ : lattice constant a = 5.232Å,
b = 10.130Å, c = 12.571Å, Z = 2, β = 100 °. It was found that each of the single crystals has a non-centrosymmetric structure and has a possibility of exhibiting second-order nonlinear characteristics.

Experimental Example 2 FIG. 20 shows the transmission spectrum in the direction perpendicular to the (201) plane of the IBNPO crystal obtained by the melting method in Example 3.
Further, FIG. 21 shows the transmission spectrum of the IBNPO crystal obtained by the solution method in Example 5 in the direction perpendicular to the (201) plane. It can be seen from FIGS. 20 and 21 that the IBNPO crystal has a high transmittance and the cutoff wavelength is around 400 nm.

Experimental Example 3 The IBNPO crystal 20 obtained in Example 5 is shown in FIG. As is clear from FIG. 22, this crystal 20 has a pair of (201) planes parallel to each other. With Nd: YAG laser
As shown in Fig. 22, when the 1.064 μm laser light 21 is incident on the line perpendicular to the (201) plane at 43.6 °, a strong green light 22 of the type-1 phase-matched second harmonic wave 0.532 μm is obtained. I was able to. The emission angle was 45.8 ° with respect to a straight line perpendicular to the (201) plane. From Experimental Examples 2 and 3 and this Experimental Example, it was found that the IBNPO crystal has a pair of planes that are parallel to each other and are sufficiently smooth optically, and that they have excellent nonlinear characteristics.

[0058]

Industrial Applicability The organic compound single crystal of the present invention has high nonlinear optical characteristics and has a shorter cutoff wavelength than conventional organic nonlinear optical crystals. Further, since it has one or more pairs of optically smooth surfaces, it is suitable for manufacturing, for example, a wavelength conversion element. Further, according to the method for producing an organic compound single crystal of the present invention, an optically good single crystal can be efficiently obtained. Further, it is possible to easily manufacture a single crystal having a crystal habit that is advantageous for manufacturing a wavelength conversion element and the like.

[Brief description of drawings]

FIG. 1 shows 3- (5-nitro-2-) produced in Synthesis Example 1.
The figure which shows the infrared absorption spectrum of pyridinyl) -4-methyl-2-oxazolidinone.

FIG. 2 shows 3- (5-nitro-2-) produced in Synthesis Example 1.
The figure which shows the nuclear magnetic resonance spectrum of pyridinyl) -4-methyl-2-oxazolidinone.

FIG. 3 is the 3- (5-nitro-2-prepared in Synthesis Example 2.
The figure which shows the infrared absorption spectrum of pyridinyl) -4-ethyl-2-oxazolidinone.

FIG. 4 shows 3- (5-nitro-2-) produced in Synthesis Example 2.
The figure which shows the nuclear magnetic resonance spectrum of pyridinyl) -4-ethyl-2-oxazolidinone.

FIG. 5: 3- (5-nitro-2- produced in Synthesis Example 3
The figure which shows the infrared absorption spectrum of pyridinyl) -4-isopropyl-2-oxazolidinone.

FIG. 6 3- (5-nitro-2- produced in Synthesis Example 3
The figure which shows the nuclear magnetic resonance spectrum of pyridinyl) -4-isopropyl-2-oxazolidinone.

FIG. 7: 3- (5-nitro-2- produced in Synthesis Example 4
The figure which shows the infrared absorption spectrum of pyridinyl) -4-isobutyl-2-oxazolidinone.

FIG. 8: 3- (5-nitro-2-produced in Synthesis Example 4
The figure which shows the nuclear magnetic resonance spectrum of pyridinyl) -4-isobutyl-2-oxazolidinone.

9: 3- (5-nitro-2- produced in Synthesis Example 5 FIG.
The figure which shows the infrared absorption spectrum of pyridinyl) -4- sec-butyl-2-oxazolidinone.

FIG. 10: 3- (5-nitro-2 produced in Synthesis Example 5
The figure which shows the nuclear magnetic resonance spectrum of -pyridinyl) -4- sec-butyl-2-oxazolidinone.

FIG. 11: 3- (5-nitro-2 produced in Synthesis Example 6
The figure which shows the infrared absorption spectrum of -pyridinyl) -4-phenyl-2-oxazolidinone.

12: 3- (5-nitro-2 produced in Synthesis Example 6 FIG.
The figure which shows the nuclear magnetic resonance spectrum of -pyridinyl) -4-phenyl-2-oxazolidinone.

FIG. 13: 3- (5-nitro-2 produced in Synthesis Example 7
The figure which shows the infrared absorption spectrum of -pyridinyl) -4-benzyl-2-oxazolidinone.

FIG. 14: 3- (5-nitro-2 produced in Synthesis Example 7
The figure which shows the nuclear magnetic resonance spectrum of -pyridinyl) -4-benzyl-2-oxazolidinone.

15: 3- (5-nitro-2 produced in Synthesis Example 8 FIG.
The figure which shows the infrared absorption spectrum of -pyridinyl) -4-benzylthiomethyl-2-oxazolidinone.

FIG. 16: 3- (5-nitro-2 produced in Synthesis Example 8
The figure which shows the nuclear magnetic resonance spectrum of -pyridinyl) -4-benzylthiomethyl-2-oxazolidinone.

FIG. 17 is a conceptual diagram showing in vertical section the crystal manufacturing apparatus by the vapor phase method used in Examples 1 and 2.

FIG. 18 is a conceptual diagram showing a longitudinal section of a Bridgman furnace, which is a crystal production apparatus by a melting method used in Example 3.

FIG. 19 is a conceptual diagram showing a longitudinal section of a glass growth container for crystal production by the solution method used in Example 4.

FIG. 20: IBNPO of the present invention measured in Experimental Example 2
The figure which shows the transmission spectrum of a single crystal.

FIG. 21: IBNPO of the present invention measured in Experimental Example 2
The figure which shows the transmission spectrum of a single crystal.

FIG. 22: IBNPO of the present invention measured in Experimental Example 3
The figure which shows the 2nd harmonic generation when 1.064μm laser beam is incident on the single crystal.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07D 413/04 8829-4C C09K 9/02 Z 7188-4H G02F 1/35 504 8106-2K

Claims (3)

[Claims] 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 may represent an aromatic group and may have a substituent on its ring], and are substantially parallel to each other and have an optically smooth surface. An organic compound single crystal having one or more pairs. 2. The method for producing an organic compound single crystal according to claim 1, which has a step of crystallizing the compound according to claim 1 from a solution containing the compound, wherein the solvent used in the solution is A method for producing a single crystal of an organic compound, wherein the solubility of the compound at 25 ° C. is 1 to 50 g per 100 g of the solvent. 3. A method for producing an organic compound single crystal according to claim 1, comprising a step of crystallizing the compound according to claim 1 from a solution containing the compound, wherein the solvent used in the solution is A method for producing an organic compound single crystal, which is a mixed solvent of two or more kinds of solvents having different crystal habits when the crystals are used alone as a solvent.