JPH05196976A - Organic nonlinear optical element - Google Patents

Abstract

PURPOSE:To provide the org. nonlinear optical material which exhibits excellent nonlinearity and can efficiently generate double waves. CONSTITUTION:This org. nonlinear optical material consists of the ether deriv., sulfide deriv. or sulfone deriv. expressed by formula: Az-Y-Ar (where Az denotes a substd. or unsubstd. electron-donating heterocyclic group or an arom. hydrocarbon group or an arom. heterocyclic group substd. by the electron-donating heterocyclic group. Ar denotes the substd. or unsubstd. electron-withdrawing heterocyclic group or the arom. hydrocarbon group or arom. heterocyclic group substd. by the electron-withdrawing heterocyclic group. Y denotes an oxy group (-O-), thio group (-S-) or sulfonyl group (-SO2-)).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel organic nonlinear optical material.

[0002]

2. Description of the Related Art Non-linear optical effects are used to modulate the wavelength, phase and amplitude of laser light in high frequency generation, optical switching, light mixing, etc., and play an important role in information processing using light.

Conventionally, inorganic compound crystals have been mainly used as a nonlinear optical material exhibiting a nonlinear optical effect. However, the nonlinear optical effect of these inorganic compound crystals was not sufficient. On the other hand, in recent years, many organic compounds have been found which have a much larger nonlinear optical constant than inorganic compound crystals and have excellent durability against optical damage.

Regarding these organic nonlinear optical materials,
For example, D.I. J. Williams et al. "Nonline
ar Optical Properties of
Organic and Polymeric Mat
initials "(American Chemical
Society, 1983) and D.W. S. Cheml
a's “Nonlinear Optical Pro”
parties of Organic Molecule
es and Crystals "(Academic
Press, inc. 1987).
The feature of the molecular structure of the organic nonlinear optical material mentioned here is that an electron-donating functional group and an electron-withdrawing functional group are bonded to both ends of a π-electron system such as a benzene ring.

However, the above-described organic nonlinear optical material having a molecular structure is likely to have a centrosymmetric structure during crystallization due to the presence of an electric dipole in the ground state, and the large nonlinearity exhibited by one molecule is the whole crystal. However, there was a problem that they were easily offset. If a π-electron system having a large spatial spread is used, the nonlinearity increases, but the absorption wavelength region (absorption band) of the molecule itself shifts to the bathochromic side (long wavelength side). As a result, there is a problem in that the light transmittance in the blue wavelength region is lowered, the efficient generation of the harmonic wave is hindered, and the deterioration of the molecule itself is promoted. From such a thing,
There is a strong demand for an organic nonlinear optical material that has excellent nonlinearity and has an absorption band of the molecule itself on the short wavelength side.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic non-linear optical material which exhibits excellent non-linearity and can efficiently generate a harmonic wave.

[0007]

The organic nonlinear optical material of the present invention has the general formula Az-Y-Ar (1).

(In the formula, Az represents a substituted or unsubstituted electron-donating heterocyclic group, or an aromatic hydrocarbon group or aromatic heterocyclic group substituted by the electron-donating heterocyclic group, and Ar is Ar. Represents a substituted or unsubstituted electron-withdrawing heterocyclic group, or an aromatic hydrocarbon group or aromatic heterocyclic group substituted with an electron-withdrawing characteristic group, Y
Represents an oxy group (—O—), a thio group (—S—) or a sulfonyl group (—SO ₂ —). ) Is represented by an ether derivative, a sulfide derivative or a sulfone derivative.

In the above general formula (1), Az is an electron-donating heterocyclic group which may be unsubstituted or substituted, or an aromatic double hydrocarbon group or an aromatic group substituted by this electron-donating heterocyclic group. It is a heterocyclic group. Specific examples of the electron-donating heterocyclic group include a pyrrole ring group, an indole ring group, a pyrazole ring group, an indazole ring group, an imidazole ring group, a benzimidazole ring group, 1,2,3-
Triazole ring group, 1,2,4-triazole ring group, tetrazole ring group, pyrrolidine ring group, pyrroline ring group, indoline ring group, piperidine ring group, dihydropyridine ring group,
Tetrahydropyridine ring group, tetrahydroquinoline ring group, tetrahydroisokyrin ring group, julolidine ring group,
Acridan ring group, pyrazoline ring group, imidazoline ring group,
Imidazolidine ring group, piperazine ring group, dihydrophenazine ring group, oxazolidine ring group, oxazine ring group, phorforine ring group, phenoxazine ring group, thiazolidine ring group,
Examples thereof include a benzothiazoline ring group, a thiazine ring group, a phenothiazine ring group, a benzodioxole ring group, and a benzodioxane ring group. Further, in the present invention, such an electron-donating heterocyclic group is preferably an electron-donating aromatic heterocyclic group from the viewpoint of broadening the π-electron conjugated system of the molecule itself.

In the general formula (1), the electron-donating heterocyclic group as described above may be substituted with the substituents exemplified below. For example, di-substituted amino group (dimethylamino group, diethylamino group, dibutylamino group, ethylmethylamino group, butylmethylamino group, diamylamino group, dibenzylamino group, diphenethylamino group,
Diphenylamino group, ditolylamino group, dixylylamino group, methylphenylamino group, benzylmethylamino group, etc., mono-substituted amino group (methylamino group, ethylamino group, propylamino group, isopropylamino group, tert-butylamino group) , Anilino group, anisidino group, phenetidino group, toluidino group, xylidino group,
Pyridylamino group, thiazolylamino group, benzylamino group, benzylideneamino group, etc., cyclic amino group (pyrrolidino group, piperidino group, piperazino group, morpholino group, 1-pyrrolyl group, 1-pyrazolyl group, 1-imidazolyl group, 1-triazolyl Group), acylamino group (formylamino group, acetylamino group, benzoylamino group, cinnamoylamino group, pyridinecarbonylamino group, trifluoroacetylamino group, etc.), sulfonylamino group (mesylamino group, ethylsulfonylamino group, phenyl) Sulfonylamino group, pyridylsulfonylamino group, tosylamino group, taurylamino group, trifluoromethylsulfonylamino group, sulfamoylamino group, methylsulfamoylamino group, sulfanylamino group, acetyl Rufanylamino group, etc.), ammonio group (trimethylammonio group, ethyldimethylammonio group, dimethylphenylammonio group, pyridinio group, quinolinio group, etc.), amino group, hydroxyamino group, ureido group, semicarbazide group, carbazide group ,
Di-substituted hydrazino groups (dimethylhydrazino group, diphenylhydrazino group, methylphenylhydrazino group, etc.),
Mono-substituted hydrazino groups (methylhydrazino group, phenylhydrazino group, pyridylhydrazino group, benzylidenehydrazino group, etc.), hydrazino groups, azo groups (phenylazo group, pyridylazo group, thiazolylazo group, etc.), azoxy group, amidino group, Cyano group, cyanato group, thiocyanato group, nitro group, nitroso group, oxy group (methoxy group, ethoxy group, propoxy group, butoxy group, hydroxyethoxy group, phenoxy group, naphthoxy group, pyridyloxy group, thiazolyloxy group, acetoxy group, etc. ),
Hydroxy group, thio group (methylthio group, ethylthio group,
Phenylthio group, pyridylthio group, thiazolylthio group, etc.), mercapto group, halogen group (fluoro group, chloro group, bromo group, iodo group), carboxyl group and salts thereof, oxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group) Group, pyridyloxycarbonyl group, etc.), aminocarbonyl group (carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, pyridylcarbamoyl group, carbazoyl group, allofanoyl group, oxamoyl group, succinamoyl group, etc.), thiocarboxyl group and salts thereof, dithio Carboxyl group and its salt, thiocarbonyl group (methoxythiocarbonyl group, methylthiocarbonyl group, methylthiothiocarbonyl group, etc.), acyl group (formyl group, acetyl group, propionyl , Acryloyl group, benzoyl group, cinnamoyl group, pyridinecarbonyl group, thiazolecarbonyl group, trifluoroacetyl group, etc.), thioacyl group (thioformyl group, thioacetyl group, thiobenzoyl group, pyridinethiocarbonyl group, etc.), sulfinic acid group and its Salt, sulfonic acid group and salt thereof, sulfinyl group (methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, etc.), sulfonyl group (mesyl group, ethylsulfonyl group, phenylsulfonyl group,
Pyridylsulfonyl group, tosyl group, tauryl group, trifluoromethylsulfonyl group, sulfamoyl group, methylsulfamoyl group, sulfanilyl group, acetylsulfanilyl group, etc., oxysulfonyl group (methoxysulfonyl group, ethoxysulfonyl group, phenoxysulfonyl group) Group, acetaminophenoxysulfonyl group, pyridyloxysulfonyl group, etc., thiosulfonyl group (methylthiosulfonyl group, ethylthiosulfonyl group, phenylthiosulfonyl group, acetaminophenylthiosulfonyl group, pyridylthiosulfonyl group, etc.), aminosulfonyl group (Sulfamoyl group, methylsulfamoyl group,
Dimethylsulfamoyl group, ethylsulfamoyl group,
Diethylsulfamoyl group, phenylsulfamoyl group, acetaminophenylsulfamoyl group, pyridylsulfamoyl group, etc.), halogenated alkyl groups (chloromethyl group, bromomethyl group, fluoromethyl group, dichloromethyl group, dibromomethyl group) Group, difluoromethyl group, trifluoromethyl group, pentafluoroethyl group,
Heptafluoropropyl group, etc.), hydrocarbon group (alkyl group, aryl group, alkenyl group, alkynyl group, etc.), heterocyclic group, organosilicon group (silyl group, disilanyl group, trimethylsilyl group, triphenylsilyl group, etc.)
And so on.

Further, in the general formula (1), when Az is an aromatic hydrocarbon group or an aromatic heterocyclic group substituted by an electron-donating heterocyclic group, such aromatic hydrocarbon group and aromatic hydrocarbon group Specific examples of the heterocyclic group include the following.

Examples of the aromatic hydrocarbon group include a benzene ring group, a naphthalene ring group, an anthracene ring group, a phenanthrene ring group, a tetralin ring group, an azulene ring group, a biphenylene ring group, an acenaphthylene ring group, an acenaphthene ring group and a fluorene ring group. Group, triphenylene ring group, pyrene ring group, chrysene ring group, picene ring group, perylene ring group, benzopyrene ring group, rubicene ring group, coronene ring group, ovalen ring group, indene ring group, pentalene ring group, heptalene ring group, Indacene ring group, phenalene ring group, fluoranthene ring group, acephenanthrylene ring group, aceanthrylene ring group, naphthacene ring group, preaden ring group, pentaphene ring group, pentacene ring group, tetraphenylene ring group, hexaphene ring group ,
Examples thereof include a hexacene ring group, a trinaphthylene ring group, a heptaphene ring group, a heptacene ring group, and a pyrantrene ring group.

Examples of the aromatic heterocyclic group include a pyrrole ring group, an indole ring group, an isoindole ring group, a carbazole ring group, a furan ring group, a coumarone ring group, an isobenzofuran ring group, a dibenzofuran ring group, a thiophene ring group, Benzothiophene ring group, dibenzothiophene ring group, pyrazole ring group, indazole ring group, imidazole ring group, benzimidazole ring group, naphthimidazole ring group, oxazole ring group, benzoxazole ring group, naphthoxazole ring group, isoxazole ring group , Benzoisoxazole ring group, thiazole ring group, benzothiazole ring group, naphthothiazole ring group, isothiazole ring group, benzisothiazole ring group, triazole ring group, benzotriazole ring group, oxadiazole ring group, thiadiazole ring group , Benzoxadiazo Ring group, a benzothiadiazole ring group,
Tetrazole ring group, purine ring group, pyridine ring group, quinoline ring group, isoquinoline ring group, acridine ring group, phenanthridine ring group, benzoquinoline ring group, naphthoquinoline ring group, naphthyridine ring group, phenanthroline ring group, pyridazine ring group , Pyrimidine ring group, pyrazine ring group, phthalazine ring group, quinoxaline ring group, quinazoline ring group, cinnoline ring group, phenazine ring group, perimidine ring group, triazine ring group, tetrazine ring group, pteridine ring group, benzoxazine ring group, Phenoxazine ring group, benzothiazine ring group, phenothiazine ring group, oxadiazine ring group, benzodioxole ring group, benzodioxane ring group, benzodithiol ring group, benzodithiane ring group, pyran ring group, chromene ring group, xanthene ring group, Selenazole ring group, benzoselenazole ring group, naphtho Renazoru ring, tellurazole ring, a benzotellurazole ring group.

Further, a substituent other than the electron-donating heterocyclic group may be further introduced into the above-mentioned aromatic hydrocarbon group or aromatic heterocyclic group. Are those exemplified as the substituent of the electron-donating heterocyclic group.

In the above general formula (1), Ar is an electron-withdrawing heterocyclic group which may be unsubstituted or substituted,
Alternatively, it is an aromatic hydrocarbon group or aromatic heterocyclic group substituted with an electron-withdrawing characteristic group. Specific examples of the electron-withdrawing heterocyclic group include an oxazole ring group, a benzoxazole ring group, a naphthoxazole ring group, an isoxazole ring group, a benzisoxazole ring group, a thiazole ring group, a benzothiazole ring group, and a naphtho group. Thiazole ring group, isothiazole ring group, benzisothiazole ring group,
Pyridine ring group, quinoline ring group, isoquinoline ring group, acridine ring group, phenanthridine ring group, benzoquinoline ring group, naphthoquinoline ring group, naphthyridine ring group, phenanthroline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group , Phthalazine ring group, quinoxaline ring group, quinazoline ring group, cinnoline ring group, phenazine ring group, triazine ring group, tetrazine ring group, pteridine ring group, selenazole ring group, benzoselenazole ring group, naphthoselenazole ring group, tellurazole Examples thereof include a ring group and a benzoterrazole ring group. Further, in the present invention, π possessed by the molecule itself
From the viewpoint of broadening the electron conjugated system, such an electron-withdrawing heterocyclic group is preferably an electron-withdrawing aromatic heterocyclic group. Further, the electron-withdrawing heterocyclic group may have a substituent introduced as described above, and examples of such a substituent include those exemplified as the substituents of the electron-donating heterocyclic group. ..

Further, in the general formula (1), when Ar is an aromatic hydrocarbon group or an aromatic heterocyclic group substituted with an electron-withdrawing characteristic group, the electron-withdrawing characteristic group may be, for example, nitro. Group, nitroso group, cyano group, cyanato group, thiocyanato group, halogen group (fluoro group, chloro group, bromo group, iodo group), carboxyl group and salts thereof, oxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group, phenoxy group) Carbonyl group, pyridyloxycarbonyl group, etc.), aminocarbonyl group (eg, carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, pyridylcarbamoyl group, carbazoyl group, allofanoyl group, oxamoyl group, succinamoyl group, etc.), thiocarboxyl group and salts thereof. , Dithioka Bokishiru group and a salt thereof, a thiocarbonyl group (e.g., methoxy thiocarbonyl group, methylthio group, methyl thio thiocarbonyl group),
Acyl group (for example, formyl group, acetyl group, propionyl group, acryloyl group, benzoyl group, cinnamoyl group, pyridinecarbonyl group, thiazolecarbonyl group,
Trifluoroacetyl group, etc.), thioacyl group (eg thioformyl group, thioacetyl group, thiobenzoyl group,
Pyridinethiocarbonyl group etc.), sulfinic acid group and its salt, sulfonic acid group and its salt, sulfinyl group (eg methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group etc.), sulfonyl group (eg mesyl group, ethylsulfonyl group, Phenylsulfonyl group,
Pyridylsulfonyl group, tosyl group, tauryl group, trifluoromethylsulfonyl group, sulfamoyl group, methylsulfamoyl group, sulfanilyl group, acetylsulfanilyl group, etc., oxysulfonyl group (eg methoxysulfonyl group, ethoxysulfonyl group, phenoxy group) Sulfonyl group, acetaminophenoxysulfonyl group, pyridyloxysulfonyl group, etc., thiosulfonyl group (eg, methylthiosulfonyl group, ethylthiosulfonyl group, phenylthiosulfonyl group, acetaminophenylthiosulfonyl group, pyridylthiosulfonyl group, etc.), amino A sulfonyl group (eg, a sulfamoyl group,
Methylsulfamoyl group, dimethylsulfamoyl group,
Ethylsulfamoyl group, diethylsulfamoyl group,
Phenylsulfamoyl group, acetaminophenylsulfamoyl group, pyridylsulfamoyl group, etc., halogenated alkyl groups (eg chloromethyl group, bromomethyl group, fluoromethyl group, dichloromethyl group, dibromomethyl group, difluoromethyl group) , Trifluoromethyl group, bentafluoroethyl group, heptafluoropropyl group and the like). Among these, a nitro group is exemplified as a particularly preferable electron-withdrawing characteristic group.

As the aromatic hydrocarbon group and aromatic heterocyclic group to which such an electron-withdrawing characteristic group is introduced, the aromatic hydrocarbon group and aromatic group to which an electron-donating heterocyclic group is introduced in Az are used. Examples of the group heterocyclic group include those mentioned above. In the general formula (1), Y, oxy group (-O-), a thio group (-S-) or sulfonyl group - is (-SO _2).

[0018]

The ether derivative represented by the general formula (1),
The sulfide derivative and the sulfone derivative have a light absorption band on the short wavelength side and have excellent light transmittance even in the blue wavelength region. Furthermore, these ether derivatives, sulfide derivatives and sulfone derivatives have oxy groups (-
O-), thio group (-S-) or sulfonyl group (-SO
₂₋ ), the Az group and the Ar group have a Λ-type conformation, that is, the conjugate planes of the two are bent. Therefore, these derivatives are likely to stack in one direction and crystallize easily. Therefore, the non-linearity is not canceled by the centrosymmetric structure, and excellent non-linearity is secured.

Further, the oxygen atom or sulfur atom of the oxy group, the thio group or the sulfonyl group forms a π-electron conjugated system with the aryl group or heteroaryl group in the Az group and the Ar group in a wide range, and further the Az group. And Ar
Due to the strong electron donating property and electron withdrawing property of the groups, the polarization due to the resonance effect (mesomeric polarization) is increased, and the nonlinearity at the molecular level is improved. Therefore, the organic nonlinear optical material represented by the general formula (1) exhibits excellent nonlinearity.

[0020]

EXAMPLES The present invention will now be described in more detail with reference to examples. (A) Synthesis examples of ether derivative, sulfide derivative and sulfone derivative

[Synthesis Example 1] Synthesis of 2- (4-nitrophenylthio) pyrrole (Compound 1) 2.4 ml (2.3 g, 34.6 mmol) of pyrrole was sampled in an Erlenmeyer flask, and 1,4- Mix with 50 ml dioxane. 5.7 g (30.1 mmol) of 4-nitrobenzenesulfenyl chloride with stirring
Was added, and 6.0 ml of triethylamine (4.4 g, 4 g
3.0 mmol) little by little. After stirring for 1 hour at room temperature, the reaction solution is concentrated under reduced pressure, and the residue is dried under vacuum. After dissolving in a small amount of ethanol, 400 ml of water is added dropwise to this solution, and the precipitated crude crystals are collected by suction filtration and washed well with a large amount of water. The crude crystal was dried in vacuum and then recrystallized from a solvent such as ethanol or toluene to obtain the target compound 1. Yield: 4.2 g (19.1 mmol) [yield: 63%] Elemental analysis (molecular _{formula: C 10 H 8 N 2 O} 2 S, molecular weight: 220.246) Carbon Hydrogen Nitrogen Sulfur Calculated 54.53% 3. 66% 12.72% 14.56% Analytical value 54.33% 3.69% 12.61% 14.79%

Synthesis Example 2 Synthesis of 2- (2-nitrophenylthio) pyrrole (Compound 2) Instead of 4-nitrobenzenesulfenyl chloride,
2-Nitrobenzenesulfenyl chloride 5.7 g (3
Target compound 2 was synthesized by the same method as in Synthesis Example 1 except that 0.1 mmol) was used. Yield: 3.4 g (15.4 mmol) [yield: 51%] Elemental analysis (molecular _{formula: C 10 H 8 N 2 O} 2 S, molecular weight: 220.246) Carbon Hydrogen Nitrogen Sulfur Calculated 54.53% 3. 66% 12.72% 14.56% Analytical value 54.25% 3.62% 12.85% 14.69% [Synthesis example 3] 2- (2,4-dinitrophenylthio)
Synthesis of pyrrole (compound 3)

In place of 4-nitrobenzenesulfenyl chloride, 7.0 g (29.8 mmol) of 2,4-dinitrobenzenesulfenyl chloride was used, except that
The target compound 3 was synthesized in the same manner as in Synthesis Example 1. Yield: 5.7 g (21.5 mmol) [Yield: 72%] Elemental analysis (molecular formula: C ₁₀ H ₇ N ₃ O ₄ S, molecular weight: 265.243) Carbon hydrogen hydrogen nitrogen sulfur calculated value 45.28% 2. 66% 15.84% 12.09% Analytical value 45.41% 2.60% 16.01% 11.97% [Synthesis Example 4] Synthesis of 3- (4-nitrophenylthio) indole (Compound 4) Pyrrole Instead of, indole 4.0g (34.1m
Compound 4 of interest was synthesized by the same method as in Synthesis Example 1 except that (mol) was used. Yield: 5.5 g (20.3 mmol) [yield: 68%] Elemental analysis (molecular _{formula: C 14 H 10 N 2 O} 2 S, molecular weight: 270.306) Carbon Hydrogen Nitrogen Sulfur Calculated 62.21% 3. 73% 10.36% 11.86% Analytical value 61.94% 3.80% 10.25% 12.10% [Synthesis example 5] Synthesis of 3- (2-nitrophenylthio) indole (Compound 5)

4.0 g (34.1 mmol) of indole
And 2-nitrobenzenesulfenyl chloride 5.7g
Using (30.1 mmol) and in the same manner as in Synthesis Example 1, the target compound 5 was synthesized. Yield: 4.4 g (16.3 mmol) [Yield: 54%] Elemental analysis (molecular formula: C ₁₄ H ₁₀ N ₂ O ₂ S, molecular weight: 270.306) Carbon hydrogen hydrogen nitrogen sulfur calculated value 62.21% 3. 73% 10.36% 11.86% Analytical value 62.42% 3.77% 10.24% 11.93% [Synthesis example 6] 3- (2,4-dinitrophenylthio)
Synthesis of indole (compound 6)

4.0 g (34.1 mmol) of indole
And 2,4-dinitrobenzenesulfenyl chloride (7.0 g, 29.8 mmol) were used to synthesize the target compound 6 in the same manner as in Synthesis Example 1. Yield: 7.0 g (22.2 mmol) [Yield: 74%] Elemental analysis (molecular formula: C ₁₄ H ₉ N ₃ O ₄ S, molecular weight: 315.303) Carbon hydrogen hydrogen nitrogen sulfur calculated value 53.33% 2. 88% 13.33% 10.17% Analytical value 53.20% 2.96% 13.12% 10.15% [Synthesis example 7] 2- (5-nitro-2-pyridylthio)
Synthesis of benzimidazole (Compound 7)

2-mercaptobenzimidazole 4.5
g (30.0 mmol), sodium hydroxide 1.4 g
(35.0 mmol) is dissolved in 30 ml of ethanol,
To this, 4.8 g of 2-chloro-5-nitropyridine (3
0.3 mmol) is added little by little, and the mixture is heated and stirred for 3 hours. After allowing to cool, 2.0 g of ammonium chloride (3
(400 mmol) is added dropwise to 400 ml of dissolved water to precipitate crude crystals. The crude crystals were collected by suction filtration (washed well with water), dried in vacuum, then ethanol,
Recrystallization from a solvent such as toluene gave the target compound 7. Yield: 6.4 g (23.5 mmol) [Yield: 78%] Elemental analysis (molecular formula: C ₁₂ H ₈ N ₄ O ₂ S, molecular weight: 272.282) Carbon hydrogen hydrogen nitrogen sulfur calculated value 52.93% 2. 96% 20.58% 11.77% Analytical value 52.94% 2.91% 20.21% 11.79% [Synthesis example 8] Synthesis of 2- (4-nitrophenylthio) benzimidazole (Compound 8)

Instead of 2-chloro-5-nitropyridine, 4.7 g of 1-chloro-4-nitrobenzene (29.
Compound 8 of interest was synthesized by the same method as in Synthesis Example 7 except that 8 mmol) was used. Yield: 5.1 g (18.8 mmol) [yield: 63%] Elemental analysis (molecular _{formula: C 13 H 9 N 3 O} 2 S, molecular weight: 271.294) Carbon Hydrogen Nitrogen Sulfur Calculated 57.55% 3. 34% 15.49% 11.82% Analytical value 57.59% 3.32% 15.32% 11.84% [Synthesis Example 9] Synthesis of 2- (2-nitrophenylthio) benzimidazole (Compound 9)

Instead of 2-chloro-5-nitropyridine, 4.7 g of 1-chloro-4-nitrobenzene (29.
8 mmol) was used to synthesize the target compound 9 in the same manner as in Synthesis Example 7. Yield: 4.8 g (17.7 mmol) [Yield: 59%] Elemental analysis (molecular formula: C ₁₃ H ₉ N ₃ O ₂ S, molecular weight: 271.294) Carbon hydrogen hydrogen nitrogen sulfur calculated value 57.55% 3. 34% 15.49% 11.82% Analytical value 57.41% 3.30% 15.57% 11.87% [Synthesis example 10] 2- (2,4-dinitrophenylthio) benzimidazole (Compound 10) Synthesis of

3.1 g of 1-chloro-2,4-dinitrobenzene instead of 2-chloro-5-nitropyridine
Target compound 10 was synthesized by the same method as in Synthesis Example 7 except that (30.1 mmol) was used. Yield: 7.8 g (24.7 mmol) [Yield: 82%] Elemental analysis (molecular formula: C ₁₃ H ₈ N ₄ O ₄ S, molecular weight: 316.291) Carbon hydrogen hydrogen nitrogen sulfur calculated value 49.37% 2. 55% 17.71% 10.14% Analytical value 49.24% 2.48% 17.80% 10.18% [Synthesis example 11] of 2- (5-nitro-2-pyridylthio) imidazole (Compound 11) Synthesis

Instead of 2-mercaptobenzimidazole, 3.0 g of 2-mercaptoimidazole (30.0
Compound 11 of interest was synthesized by the same method as in Synthesis Example 7 except that (mmol) was used. Yield: 4.7 g (21.2 mmol) [yield: 71%] Elemental analysis (molecular _{formula: C 8 H 6 N 4 O} 2 S, molecular weight: 222.222) Carbon Hydrogen Nitrogen Sulfur Calculated 43.24% 2. 72% 25.21% 14.43% Analytical value 42.98% 2.81% 25.13% 14.61% [Synthesis Example 12] of 2- (2,4-dinitrophenylthio) imidazole (Compound 12) Synthesis

2-mercaptoimidazole 3.0 g (3
0.0 mmol) and 6.1 g (30.1 mmol) of 1-chloro-2,4-dinitrobenzene, and a synthesis example 7
Compound 12 of interest was synthesized by a method similar to. Yield: 6.1 g (22.9 mmol) [Yield: 76%] Elemental analysis (molecular formula: C ₉ H ₆ N ₄ O ₄ S, molecular weight: 266.231) Carbon hydrogen hydrogen nitrogen sulfur calculated value 40.60% 2. 27% 21.04% 12.04% Analytical value 40.41% 2.31% 20.94% 12.24% [Synthesis Example 13] Synthesis of 1- (4-nitrophenylthio) benzimidazole (Compound 13) Instead of pyrrole, 4.0 g of benzimidazole (3
Compound 13 of interest was synthesized by the same method as in Synthesis Example 1 except that 3.9 mmol) was used. Yield: 4.6 g (17.0 mmol) [yield: 56%] Elemental analysis (molecular formula: C ₁₃ H ₉ N ₃ O ₂ S, molecular weight: 271.294) Carbon hydrogen Nitrogen Sulfur calculated value 57.55% 3. 34% 15.49% 11.82% Analytical value 57.96% 3.30% 15.40% 11.75% [Synthesis Example 14] Synthesis of 1- (2-nitrophenylthio) benzimidazole (Compound 14)

Benzimidazole 4.0 g (33.9 m)
mol) and 2-nitrobenzenesulfenyl chloride (5.7 g, 30.1 mmol) were used to synthesize the target compound 14 in the same manner as in Synthesis Example 1. Yield: 3.9 g (14.4 mmol) [yield: 48%] Elemental analysis (molecular _{formula: C 13 H 9 N 3 O} 2 S, molecular weight: 271.294) Carbon Hydrogen Nitrogen Sulfur Calculated 57.55% 3. 34% 15.49% 11.82% Analytical value 57.76% 3.38% 15.46% 11.72% [Synthesis example 15] 1- (2,4-dinitrophenylthio) benzimidazole (Compound 15) Synthesis of

Benzimidazole 4.0 g (33.9 m)
mol) and 7.0 g (29.8 mmol) of 2,4-dinitrobenzenesulfenyl chloride, and Synthesis Example 1
Compound 15 of interest was synthesized by a method similar to. Yield: 6.8 g (21.5 mmol) [Yield: 72%] Elemental analysis (molecular formula: C ₁₃ H ₈ N ₄ O ₄ S, molecular weight: 316.291) Carbon hydrogen hydrogen nitrogen sulfur calculated value 49.37% 2. 55% 17.71% 10.14% Analytical value 49.01% 2.59% 17.83% 10.33% [Synthesis example 16] of 4-nitro-4'-piperidinodiphenyl sulfide (compound 16) Synthesis

7.4 g (30.0 mmol) of 4-amino-4'-nitrodiphenyl sulfide and 4.0 ml (6.8 g, 29.4 mmol) of 1,5-dibromopentane.
Into an Erlenmeyer flask and add 20 m of toluene.
Mix with l. 5.0 g (36.2 mmol) of anhydrous carbonic acid
Is added with stirring, and the mixture is heated with stirring for 24 hours. After cooling down,
The reaction solution is concentrated under reduced pressure, the residue is dissolved in a small amount of ethanol, 400 ml of water is added dropwise to this solution, and the precipitated crude crystals are collected by suction filtration and washed well with a large amount of water. The crude crystals were dried in vacuum and then recrystallized from a solvent such as ethanol or toluene to obtain the target compound 16. Yield: 4.6 g (14.6 mmol) [yield: 50%] Elemental analysis (molecular _{formula: C 17 H 18 N 2 O} 2 S, molecular weight: 314.403) Carbon Hydrogen Nitrogen Sulfur Calculated 64.94% 5. 77% 8.91% 10.20% Analytical value 65.20% 5.84% 8.73% 10.00% [Synthesis example 17] 4-nitro-4 '-(1-pyrrolyl)
Synthesis of diphenyl sulfide (Compound 17)

4-amino-4'-nitrodiphenyl sulfide (6.9 g, 28.0 mmol) and 2,5-dimethoxytetrahydrofuran (4.0 ml, 4.1 g, 30.
(9 mmol) and 40 ml of acetic acid are collected in an Erlenmeyer flask and heated under reflux for 1 hour. After allowing to cool, 400 ml of water is added dropwise to the reaction solution, and the precipitated crude crystals are collected by suction filtration and washed well with a large amount of water. The crude crystal was dried in vacuum and then recrystallized from a solvent such as ethanol or toluene to obtain the target compound 17. Yield: 6.6 g (22.3 mmol) [Yield: 80%] Elemental analysis (molecular formula: C ₁₆ H ₁₂ N ₂ O ₂ S, molecular weight: 296.344) Carbon hydrogen hydrogen nitrogen sulfur calculated value 64.85% 4. 08% 9.45% 10.82% Analytical value 64.74% 4.04% 9.58% 11.00% [Synthesis Example 18] 9- (2,4-dinitrophenylthio) julolidine (Compound 18) Synthesis

6.2 g (35.8 mmo) of julolidine
1) is collected in an Erlenmeyer flask and mixed with 100 ml of ethylene chloride. 7.0 g (29.8 mmol) of 2,4-dinitrobenzenesulfenyl chloride are added with stirring and the solution is heated to 65-70 ° C. Anhydrous tin tetrachloride (15.6 g, 59.9 mmol) was added little by little over 5 minutes, and the mixture was heated with stirring for 2 hours. After standing to cool, the reaction solution (ethylene chloride solution) was added with a 0.1 M hydrochloric acid aqueous solution 200 m
It is washed once with 1 and twice with 200 ml of pure water by a solvent extraction operation. After dehydration with anhydrous sodium sulfate, the mixture is treated with activated carbon and suction filtered through a Celite bed, and the filtrate is concentrated under reduced pressure. The precipitated crude crystals were recrystallized from a solvent such as ethanol and toluene to obtain the target compound 18. Yield: 9.4 g (25.3 mmol) [yield: 85% Elemental analysis (molecular _{formula: C 18 H 17 N 3 O} 4 S, molecular weight: 371.411) Carbon Hydrogen Nitrogen Sulfur Calculated 58.21% 4. 61% 11.31% 8.63% Analytical value 58.34% 4.56% 11.38% 8.64% [Synthesis example 19] Synthesis of 9- (4-nitrophenylthio) julolidine (Compound 18)

Except that 5.7 g (30.1 mmol) of 4-nitrobenzenesulfenyl chloride was used in place of 2,4-dinitrobenzenesulfenyl chloride.
The target compound 19 was synthesized in the same manner as in Synthesis Example 18. Yield: 5.9 g (18.1 mmol) [Yield: 60%] Elemental analysis (molecular formula: C ₁₈ H ₁₈ N ₂ O ₂ S, molecular weight: 326.414) Carbon hydrogen hydrogen nitrogen sulfur calculated value 66.23% 5. 56% 8.58% 9.82% Analytical value 66.05% 5.61% 8.47% 9.95% [Synthesis example 20] of 2,4-dinitro-4'-morpholinodiphenyl sulfide (compound 20) Synthesis

The target compound 20 was prepared in the same manner as in Synthesis Example 18 except that 5.9 g (36.1 mmol) of 4-phenylmorpholine was used instead of julolidine.
Was synthesized. Yield: 7.5 g (20.8 mmol) [Yield: 70%] Elemental analysis (molecular formula: C ₁₆ H ₁₅ N ₃ O ₅ S, molecular weight: 361.372) Carbon hydrogen hydrogen nitrogen sulfur calculated value 53.18% 4. 18% 11.63% 8.87% Analytical value 53.03% 4.25% 11.76% 8.78% [Synthesis example 21] 5- (2,4-dinitrophenylthio) -1,3-benzo Synthesis of dioxole (compound 21)

Instead of julolidine, 4.2 ml of 1,3-benzodioxole (4.5 g, 36.6 mmo)
By the same method as in Synthesis Example 18 except that l) was used,
The target compound 21 was synthesized. Yield: 6.2 g (19.4 mmol) [Yield: 65%] Elemental analysis (molecular formula: C ₁₃ H ₈ N ₂ O ₆ S, molecular weight: 320.275) Carbon hydrogen hydrogen nitrogen sulfur calculated value 48.75% 2. 52% 8.75% 10.01% Analytical value 48.92% 2.54% 8.65% 9.95% [Synthesis example 22] 6- (2,4-dinitrophenylthio) -1,4-benzo Synthesis of dioxane (Compound 22)

Instead of julolidine, 4.3 ml of 1,4-benzodioxane (4.9 g, 36.1 mmol)
Target compound 22 was synthesized by the same method as in Synthesis Example 18 except that was used. Yield: 7.5 g (22.4 mmol) [Yield: 75%] Elemental analysis (molecular formula: C ₁₄ H ₁₀ N ₂ O ₆ S, molecular weight: 334.302) Carbon hydrogen hydrogen nitrogen sulfur calculated value 50.30% 3. 02% 8.38% 9.59% Analytical value 50.44% 2.98% 8.22% 9.71% [Synthesis example 23] 2- (2,4-dinitrophenylthio) furan (Compound 23) Synthesis

Furan 2.6 m instead of julolidine
Compound 23 of interest was synthesized by the same method as in Synthesis Example 18 except that 1 (2.4 g, 35.7 mmol) was used. Yield: 5.4 g (20.3 mmol) [Yield: 68%] Elemental analysis (molecular formula: C ₁₀ H ₆ N ₂ O ₅ S, molecular weight: 266.227) Carbon hydrogen hydrogen nitrogen sulfur calculated value 45.11% 2. 27% 10.52% 12.04% Analytical value 45.25% 2.20% 10.50% 11.98% [Synthesis Example 24] of 2- (2,4-dinitrophenylthio) thiophene (Compound 24) Synthesis

Instead of julolidine, thiophene 2.
The target compound 24 was prepared in the same manner as in Synthesis Example 18 except that 9 ml (3.0 g, 36.2 mmol) was used.
Was synthesized. Yield: 4.6 g (16.3 mmol) [yield: 55%] Elemental analysis (molecular _{formula: C 10 H 6 N 2 O} 4 S 2, molecular weight: 282.288) Carbon Hydrogen Nitrogen Sulfur Calculated 42.55% 2 .14% 9.92% 22.71% Analytical value 42.69% 2.16% 9.78% 22.64% [Synthesis example 25] 4-nitro-4 '-(1-pyrrolyl)
Synthesis of diphenyl sulfone (Compound 25)

By the same method as in Synthesis Example 17, except that 7.8 g (28.0 mmol) of 4-amino-4'-nitrodiphenyl sulfone was used instead of 4-amino-4'-nitrodiphenyl sulfide. Target compound 25
Was synthesized. Yield: 6.6 g (20.1 mmol) [Yield: 72%] Elemental analysis (molecular formula: C ₁₆ H ₁₂ N ₂ O ₄ S, molecular weight: 328.342) Carbon hydrogen hydrogen nitrogen sulfur calculated value 58.53% 3. 68% 8.53% 9.76% Analytical value 58.36% 3.76% 8.40% 9.88% [Synthesis example 26] 5- (4-nitrophenylsulfonyl) -2- (1-pyrrolyl) Thiazole (Compound 26)
Synthesis of

Instead of 4-amino-4'-nitrodiphenyl sulfide, 8.0 g (28.0 mmo) of 2-amino-5- (4-nitrophenylsulfonyl) thiazole.
By the same method as in Synthesis Example 17 except that l) was used,
Compound 26 of interest was synthesized. Yield: 7.1 g (21.2 mmol) [yield: 76%] Elemental analysis (molecular _{formula: C 13 H 9 N 3 O} 4 S 2, molecular weight: 335.352) Carbon Hydrogen Nitrogen Sulfur Calculated 46.56% 2 0.71% 12.53% 19.12% Analytical value 46.78% 2.77% 12.40% 18.98% [Synthesis example 27] of 4-nitro-4'-piperidinodiphenyl ether (compound 27) Synthesis

By the same method as in Synthesis Example 16 except that 6.9 g (30.0 mmol) of 4-amino-4'-nitrodiphenyl ether was used in place of 4-amino-4'-nitrodiphenyl sulfide, Compound of 27
Was synthesized. Yield: 4.0 g (13.4 mmol) [Yield: 46%] Elemental analysis (molecular formula: C ₁₇ H ₁₈ N ₂ O ₃ , molecular weight: 298.342) Carbon hydrogen Nitrogen calculated value 68.44% 6.08% 9.39% Analytical value 68.01% 6.02% 9.52% [Synthesis example 28] 4-nitro-4 '-(1-pyrrolyl)
Synthesis of diphenyl ether (Compound 28)

By the same method as in Synthesis Example 17, except that 6.4 g (27.8 mmol) of 4-amino-4′-nitrodiphenyl ether was used instead of 4-amino-4′-nitrodiphenyl sulfide, Compound 28
Was synthesized. Yield: 5.2 g (18.6 mmol) [Yield: 67%] Elemental analysis (molecular formula: C ₁₆ H ₁₂ N ₂ O ₃ , molecular weight: 280.283) Carbon hydrogen Hydrogen calculated value 68.56% 4.32% 9.99% Analytical value 68.74% 4.24% 10.15% [Synthesis example 29] Synthesis of 5- (5-nitro-2-pyridyloxy) -1,3-benzodioxole (compound 29)

3.5 g (25.3 mmol) of sesamol (3,4-methylenedioxyphenol) and 1.3 g (32.5 mmol) of sodium hydroxide were dissolved in 40 ml of dimethyl sulfoxide and stirred at 80 ° C. for 1 hour. 2-chloro-5-nitropyridine 4.8 g (3
0.3 mmol) is added little by little, and the mixture is heated with stirring at 100 ° C. for 8 hours. After allowing to cool, 200 ml of ethyl acetate is added to the reaction solution, and unnecessary substances are removed by suction filtration. The filtrate is 0.2
200 ml of M sodium hydroxide aqueous solution once, pure water 20
Wash with 0 ml twice by solvent extraction procedure. After dehydration with anhydrous sodium sulfate, the mixture is treated with activated carbon and suction filtered through a Celite bed, and the filtrate is concentrated under reduced pressure. The precipitated crude crystals were recrystallized from a solvent such as ethanol and toluene to obtain the target compound 29. Yield: 4.0 g (15.4 mmol) [Yield: 61%] Elemental analysis (molecular formula: C ₁₂ H ₈ N ₂ O ₅ S, molecular weight: 260.205) Carbon hydrogen Nitrogen calculated value 55.39% 3.10 % 10.77% Analytical value 55.64% 3.17% 10.60% [Synthesis example 30] 5- (2,4-dinitrophenoxy)
Synthesis of -1,3-benzodioxole (Compound 30)

6.1 g of 1-chloro-2,4-dinitrobenzene instead of 2-chloro-5-nitropyridine
The target compound 30 was synthesized by the same method as in Synthesis Example 29 except that (30.1 mmol) was used. Yield: 5.6 g (18.4 mmol) [yield: 73%] Elemental analysis (molecular _{formula: C 13 H 8 N 2 O} 7, Molecular weight: 304.214) Carbon Hydrogen Nitrogen Calculated 51.33% 2.65% 9.21% Analytical value 51.10% 2.63% 9.33% (B) Measurement of nonlinear optical characteristics

Compounds 1 to 30 obtained in Synthesis Examples 1 to 30
, Ether derivatives, sulfide derivatives, and sulfone derivatives, and urea (Comparative Example 1), 2-methyl-4-nitroaniline (MNA) (Comparative Example 2) as comparative examples, and organic non-linear optical materials. Similar compounds 4-amino-4'-nitrodiphenyl sulfide (Comparative Example 3), 4-amino-4'-nitrodiphenyl ether (Comparative Example 4), 4,4'-sulfonylbisaniline (Comparative Example 5), 4 , 4'-Sulfonylbisphenol (Comparative Example 6), N- (2,4-dinitrophenyl) -p-toluidine (Comparative Example 7) and N- (2,4-
Second-order nonlinear optical characteristics of dinitrophenyl) -m-toluidine (Comparative Example 8) were examined by a so-called powder method. That is, the crystal powder of each compound was crushed in an agate mortar, a powder having a particle size of 100 to 150 μm was prepared by a sieve, and the powder was sandwiched between slide glasses to obtain a measurement sample. For these measurement samples, Nd-Y
The fundamental wave of the AG laser (wavelength = 1.064 μm) was irradiated, and the intensity of the second harmonic (SHG) component in the reflected light was measured. The results of normalizing the second harmonic intensity of each sample with the second harmonic intensity of the urea (Comparative Example 1) powder are shown in Tables 1 to 10.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

[0053]

[Table 4]

[0054]

[Table 5]

[0055]

[Table 6]

[0056]

[Table 7]

[0057]

[Table 8]

[0058]

[Table 9]

[0059]

[Table 10]

As is clear from Tables 1 to 10, the ether derivative, the sulfide derivative and the sulfone derivative of Examples 1 to 30 produced several times to 30 times more SHG than the urea of Comparative Example 1. It can be confirmed that they have excellent nonlinearity.

Further, Examples 6, 17, 21, 25, 28
Of the ether derivative, the sulfide derivative and the sulfone derivative of Comparative Example 2, and the MNA of Comparative Example 2 and the sulfide derivative of Comparative Example 3 in a 0.001M ethanol solution-
The result of measuring the ultraviolet transmission spectrum is shown in FIG.

As is clear from FIG. 1, Examples 6 and 1
The ether derivatives, sulfide derivatives and sulfone derivatives of 7,21,25,28 have light absorption bands on the shorter wavelength side than the MNA of Comparative Example 2 and the sulfide derivative of Comparative Example 3, and transmit light even in the blue wavelength region. It can be confirmed that the rate is high. Further, other than these, the ether derivative of the present embodiment,
Regarding the sulfide derivative and the sulfone derivative, 0.
When the visible-ultraviolet transmission spectrum of the 001M ethanol solution was measured, the light absorption band was similarly present on the shorter wavelength side than the MNA of Comparative Example 2 and the sulfide derivative of Comparative Example 3. From this, it is understood that the ether derivative, the sulfide derivative and the sulfone derivative of the present invention have good light transmittance in the visible region.

[0063]

As described in detail above, the organic nonlinear optical material of the present invention can be synthesized very easily, has a high blue light transmittance on the short wavelength side for light absorption, and has excellent nonlinear optical characteristics. , Can efficiently generate harmonics. Therefore, the organic nonlinear optical material of the present invention has a remarkable effect that it can be applied to the field of optoelectronics that utilizes nonlinear phenomena such as high-speed optical shutter including high frequency generation and optical bistable elements.

[Brief description of drawings]

FIG. 1 is a sixth embodiment of the present invention.
Of the ether derivative, the sulfide derivative and the sulfone derivative of Comparative Example 2, and the MNA of Comparative Example 2 and the sulfide derivative of Comparative Example 3 in a 0.001M ethanol solution-
It is an ultraviolet transmission spectrum figure.

Claims (1)

[Claims] 1. Az-Y-Ar (1) (wherein Az represents a substituted or unsubstituted electron-donating heterocyclic group, or an aromatic carbon group substituted by the electron-donating heterocyclic group). Represents a hydrogen group or an aromatic heterocyclic group, and Ar represents a substituted or unsubstituted electron withdrawing heterocyclic group, or an aromatic hydrocarbon group or an aromatic heterocyclic group substituted with an electron withdrawing characteristic group. Y is an oxy group (-O-), thio (-S-) or sulfonyl group - ether derivatives represented by showing a), (-SO _2).
An organic nonlinear optical material comprising a sulfide derivative or a sulfone derivative.