JP3461981B2 - Organic nonlinear optical material - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel organic nonlinear optical material.

[0002]

2. Description of the Related Art Nonlinear optical effects are used for modulating 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 much larger nonlinear optical constants 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, in the case of a π-electron system organic nonlinear optical material having a large spatial spread, the nonlinearity increases, but the absorption wavelength region (absorption band) of the molecule itself shifts to the bathochromic side (long wavelength side). Tend. As a result, there is a problem that the light transmittance in the blue wavelength region is lowered, the efficient generation of a harmonic wave is prevented, and the deterioration of the molecule itself is promoted.
In addition, the organic nonlinear optical material having such a molecular structure is
Due to the existence of the electric dipole in the ground state, there is a problem that a centrally symmetric structure is likely to be formed during crystallization, and the large nonlinearity shown by one molecule is easily canceled out as a whole crystal.

[0006]

As described above, the conventional organic nonlinear optical material is still insufficient in the light transmittance in the blue wavelength range and the nonlinearity of the crystal as a whole.
It is strongly desired to develop an organic nonlinear optical material that has excellent nonlinearity and has an absorption band of the molecule itself on the low wavelength side. Therefore, 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 following general formula (1).

[0008]

[Chemical 2] (In the formula, R ⁰ represents a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group.

X is -CH = CH-, -CH = N-,-
N = CH -, - N = N -, - O -, - S -, - SO 2 -
Or a single bond is shown. φ represents a substituted or unsubstituted aromatic hydrocarbon group or aromatic heterocyclic group.

R ^{1 to} R ⁴ are each a substituted or unsubstituted aliphatic hydrocarbon group, hydroxy group, alkoxy group,
A thio group, an alkylthio group, a carboxyl group, an oxycarbonyl group, a halogen atom or a hydrogen atom is shown.

N is an integer of 0 to 2. ) Represented by 4
-Pyridone derivative. A particularly preferred embodiment of the present invention is R in the general formula (1).
^An organic nonlinear optical material in which ⁰ is a substituted or unsubstituted electron-withdrawing heterocyclic group, or an aromatic hydrocarbon group or aromatic heterocyclic group substituted with an electron-withdrawing characteristic group.

R ⁰ in the above general formula (1) is a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group. An unsubstituted aliphatic hydrocarbon group, an alicyclic hydrocarbon group, introduced as R ⁰ ,
Examples of the aromatic hydrocarbon group and the heterocyclic group are shown below.

Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, tert-pentyl group, isopentyl group. , Neopentyl group, hexyl group, isohexyl group,
Heptyl group, octyl group, nonyl group, decyl group, vinyl group, allyl group, isopropenyl group, propenyl group, methallyl group, crotyl group, butenyl group, pentenyl group, butadienyl group, ethynyl group, propynyl group, butynyl group,
Examples include a pentynyl group.

Examples of the alicyclic hydrocarbon group are cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group,
Examples thereof include a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a cyclopentadienyl group and a cyclohexadienyl group.

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 heterocyclic group include a pyrrole ring group,
Pyroline ring group, pyrrolidine ring group, indole ring group, isoindole ring group, indoline ring group, isoindoline ring group, indolizine ring group, carbazole ring group, carboline ring group, furan ring group, oxolane ring group, coumarone ring group , Coumaran ring group, isobenzofuran ring group, phthalane ring group, dibenzofuran ring group, thiophene ring group, thiolane ring group, benzothiophene ring group, dibenzothiophene ring group, pyrazole ring group, pyrazoline ring group, indazole ring group, imidazole ring group Group, imidazoline ring group, imidazolidine ring group,
Benzimidazole ring group, benzimidazoline ring group, naphthimidazole ring group, oxazole ring group, oxazoline ring group, oxazolidine ring group, benzoxazole ring group, benzoxazoline ring group, naphthoxazole ring group, isoxazole ring group, benzisoxazole Ring group, thiazole ring group, thiazoline ring group, thiazolidine ring group, benzothiazole ring group, benzothiazoline ring group, naphthothiazole ring group, isothiazole ring group, benzisothiazole ring group, triazole ring group, benzotriazole ring group, Oxadiazole ring group, thiadiazole ring group,
Benzoxadiazole ring group, benzothiadiazole ring group, tetrazole ring group, purine ring group, pyridine ring group, piperidine 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, piperazine 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, oxazine ring group, benzoxazine ring group, phenoxazine ring group, thiazine ring group, benzothiazine ring group, phenothiazine ring group, oxadiazine ring group, thiadiazine ring group, dioxolane Ring group, benzodioxole ring group, di Xan ring group, benzodioxane ring group, dithiolane ring group, benzodithiol ring group, dithian ring group, benzodithian ring group, pyran ring group, chromene ring group, xanthene ring group, oxane ring group, chroman ring group, isochroman ring group, Examples thereof include a trioxane ring group, a thiane ring group, a trithiane ring group, a morpholine ring group, a quinuclidine ring group, a selenazole ring group, a benzoselenazole ring group, a naphthoselenazole ring group, a tellurazole ring group, and a benzotelrazole ring group.

In the above general formula (1), the aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group introduced as R ⁰ is substituted with the substituents exemplified below. It may have been done. 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 groups (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., heterocyclic amino group (pyrrolidino group, piperidino group, piperazino group, morpholino group, 1-pyrrolyl group, 1-pyrazolyl group, 1-imidazolyl group, 1-triazolyl group, etc.),
Acylamino group (formylamino group, acetylamino group, benzoylamino group, cinnamoylamino group, pyridinecarbonylamino group, trifluoroacetylamino group, etc.), sulfonylamino group (mesylamino group, ethylsulfonylamino group, phenylsulfonylamino group,
Pyridylsulfonylamino group, tosylamino group, taurylamino group, trifluoromethylsulfonylamino group,
Sulfamoylamino group, methylsulfamoylamino group, sulfanylamino group, acetylsulfanylamino group, etc.), ammonio group (trimethylammonio group,
Ethyldimethylammonio group, dimethylphenylammonio group, pyridinio group, quinolinio group, etc.), amino group, oxyamino group, (methoxyamino group, ethoxyamino group, phenoxyamino group, pyridyloxyamino group, etc.), hydroxyamino group , Ureido group, semicarbazide group, carbazide group, disubstituted hydrazino group (dimethylhydrazino group, diphenylhydrazino group, methylphenylhydrazino group, etc.), monosubstituted hydrazino group (methylhydrazino group, phenylhydrazino group, pyridylhydra group Dino group, benzylidene hydrazino group, etc.), hydrazino group, azo group (phenylazo group, pyridylazo group, thiazolylazo group, etc.), azoquin group, amidino group, cyano group, cyanato group, thiocyanato group, nitro group, nitroso group, oxy group (Metoki 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, pyridyloxycarbonyl) Group), aminocarbonyl group (carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, pyridylcarbamoyl group, carbazoyl group, allofanoyl group, oxamoyl group, succinamoyl group, etc.), thiocal Alkoxy group and a salt thereof, dithiocarboxyl group and a salt thereof, a thiocarbonyl group (methoxy thiocarbonyl group, methylthio group, methyl thio thiocarbonyl group),
Acyl group (formyl group, acetyl group, propionyl group,
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 salts thereof , Sulfonic acid groups and salts thereof, sulfinyl groups (methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, etc.), sulfonyl groups (mesyl group, ethylsulfonyl group, phenylsulfonyl group, pyridylsulfonyl group, tosyl group, tauryl group, triaryl group Fluoromethylsulfonyl group, sulfamoyl group, methylsulfamoyl group, sulfanylyl group, acetylsulfanylyl group, etc., oxysulfonyl group (methoxysulfonyl group, ethoxysulfonyl group, phenoxy) Rufonyl 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, difluoromethyl group, trifluoromethyl group, pentafluoroethyl group, heptafluor Propyl group and the like), a hydrocarbon group (an alkyl group, an aryl group, an alkenyl group, an alkynyl group), a heterocyclic group, an organosilicon group (silyl group, Jishiraniru group, a trimethylsilyl group,
Triphenylsilyl group, etc.) and the like.

Further, as described above, as R ⁰ in the above general formula (1), among these, a substituted or unsubstituted electron-withdrawing heterocyclic group or an aromatic hydrocarbon substituted with an electron-withdrawing characteristic group is particularly preferable. It is preferably a group or an aromatic heterocyclic group. Examples of the unsubstituted electron-withdrawing heterocyclic group introduced as R ⁰ include, for example, an oxazole ring group, a benzoxazole ring group, a naphthoxazole ring group, an isoxazole ring group, a benzisoxazole ring group, and a thiazole ring group. A benzothiazole ring group,
Naphthothiazole 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 , A phenanthroline ring group, a 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, Examples thereof include naphthoselenazole ring group, tellurazole ring group, and benzoterrazole ring group. In the present invention, such an electron-withdrawing heterocyclic group is preferably an electron-withdrawing aromatic heterocyclic group from the viewpoint of making the π-electron conjugated system of the molecule itself wide. In addition, the electron-withdrawing heterocyclic group may be substituted with a substituent as described above, and as the substituent here, R ⁰ is the above-mentioned aliphatic hydrocarbon group, alicyclic hydrocarbon group or aromatic group. The same as in the case of a group hydrocarbon group or a heterocyclic group can be mentioned.

On the other hand, when an aromatic hydrocarbon group or an aromatic heterocyclic group substituted with an electron-withdrawing characteristic group is introduced as R ⁰ , the electron-withdrawing characteristic group is, for example, a nitro group or a 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 (methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, pyridyloxy Carbonyl group), aminocarbonyl group (carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group,
Pyridylcarbamoyl group, carbazoyl group, allofanoyl group, oxamoyl group, succinamoyl group, etc.),
Thiocarboxyl group and its salt, dithiocarboxyl group and its salt, thiocarbonyl group (methoxythiocarbonyl group, methylthiocarbonyl group, methylthiothiocarbonyl group, etc.), acyl group (formyl group, acetyl group, propionyl group, 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 salts thereof, sulfonic acid group And salts thereof, sulfinyl groups (methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, etc.), sulfonyl groups (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,
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) Group, pyridylsulfamoyl group, etc., halogenated alkyl group (chloromethyl group, bromomethyl group, fluoromethyl group, dichloromethyl group, dibromomethyl group, difluoromethyl group, trifluoromethyl group, pentafluoroethyl group, heptafluoro Propyl group, etc.) and the like.

Examples of the aromatic hydrocarbon group to which such an electron-withdrawing characteristic group is introduced include those exemplified above. Examples of the aromatic heterocyclic group include a pyrrole ring group and an indole ring group. , Isoindole ring group, carbazole ring group, furan ring group, coumarone ring group, isobenzofuran ring group, dibenzofuran ring group, thiophene ring group, benzothiophene ring group, dibenzothiophene ring group, pyrazole ring group, indazole ring group, imidazole ring group Ring group, benzimidazole ring group, naphthimidazole ring group, oxazole ring group, benzoxazole ring group, naphthoxazole ring group, isoxazole ring group, benzisoxazole ring group, thiazole ring group, benzothiazole ring group, naphthothiazole ring group Group, isothiazole ring group, benzisothiazole ring group, triazo Le ring, benzotriazole ring group, an oxadiazole ring group, a thiadiazole ring group, a benzo oxadiazole 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.

X in the general formula (1) is -CH =
CH-, -CH = N-, -N = CH-, -N = N-,-
O -, - S -, - it is or a single bond - SO _2. In the general formula (1), φ is a substituted or unsubstituted aromatic hydrocarbon group or aromatic heterocyclic group, and an aromatic hydrocarbon group or aromatic group that can be introduced as R ⁰ in the general formula (1). Divalent ones having the same structure as the heterocyclic group can be mentioned. Further, the aromatic hydrocarbon group and aromatic heterocyclic group may be substituted with a substituent, and examples of the substituent here include those exemplified as the substituent of R ⁰ in the general formula (1). To be

R ^{1 to} R ⁴ in the above general formula, which may be the same or different, are each a substituted or unsubstituted aliphatic hydrocarbon group, a hydroxy group, an alkoxy group, a thio group, an alkylthio group, It is a carboxyl group, an oxycarbonyl group, a halogen atom or a hydrogen atom, examples of which are given below. For example, unsubstituted aliphatic hydrocarbon group (methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, vinyl group, allyl group, etc.), fluorine substitution Aliphatic hydrocarbon group (trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, undecafluoropentyl group, etc.), hydroxy group, alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group) Group, pentyloxy group, etc.), thio group, alkylthio group (methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, etc.), carboxyl group, oxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group,
A propoxycarbonyl group, a butoxycarbonyl group, a phenoxycarbonyl group, etc.), a halogen atom (fluoro group, chloro group, bromo group, iodo group), a hydrogen atom and the like. In the present invention, among these, a lower alkyl group (methyl group, ethyl group, propyl group, etc.) having a small steric hindrance, a hydroxy group, a halogen atom or a hydrogen atom is particularly preferable.

The 4-pyridone derivative according to the present invention is a method of dehydrating and condensing a 4-pyrone compound with an amine compound, and a keridonic acid compound (4-pyrone-2,6-
Dicarboxylic acid compound) is dehydrated and condensed to give a keridamic acid compound (4-pyridone-2,6-dicarboxylic acid compound) which is decarboxylated by heating, or a 4-pyridinol compound is condensed with a halogenated aromatic compound. It is easily synthesized by the method.

The 4-pyridone derivative represented by the above general formula (1) as described above has a light absorption band on the short wavelength side and has good light transmittance even in the blue wavelength region. Further, this 4-pyridone derivative is polarized by the resonance effect (mesomeric polarization) due to the fact that the 4-position carbonyl group of the 4-pyridone ring and the 1-position nuclear nitrogen atom have electron withdrawing and electron donating properties, respectively. And the non-linearity at the molecular level is improved.

Further, in such a 4-pyridone derivative, as R ⁰ in the above general formula (1), a substituted or unsubstituted electron-withdrawing heterocyclic group, or an aromatic hydrocarbon group substituted with an electron-withdrawing characteristic group, or When the aromatic heterocyclic group is introduced, it is based on the polarization due to the resonance effect between the electron-withdrawing functional group and the nuclear nitrogen atom at the 1-position of the 4-pyridone ring having an electron-donating property, and at the molecular level, Non-linearity is further improved. Moreover, at this time, a dipole moment is induced from the nuclear nitrogen atom at the 1-position of the 4-pyridone ring toward the electron-withdrawing functional group, resulting in 4-
In the pyridone ring, the dipole moment in the direction from the nuclear nitrogen atom at the 1st position to the carbonyl group at the 4th position is offset, and the dipole moment of the entire molecule is reduced. Therefore, it is possible to suppress the formation of a centrally symmetric structure during crystallization, and to secure extremely excellent nonlinearity.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. First, a synthesis example of the 4-pyridone derivative used in the examples of the present invention will be shown. [Synthesis Example 1] Synthesis of N- (4-nitrophenyl) -4-pyridone (Compound 1) 4-pyridinol 3.80 g (39.96 mmol),
5.64 g of 1-fluoro-4-nitrobenzene (39.
96 mmol) and anhydrous potassium carbonate 6.08 g (43.
99 mmol) and 50 ml of dimethyl sulfoxide were collected in a flask and heated and stirred at 150 ° C. for 6 hours. After allowing to cool, 500 ml of water was added dropwise to the reaction solution, and the precipitated crude crystals were collected by suction filtration and washed well with water.
Then, the crude crystals were dried in vacuum and then recrystallized from a hot ethanol solution to obtain the target compound 1. -Yield: 7.78 g (35.99 mmol) [Yield: 9
0%] IR spectrum (measurement method: KBr method) 1645 cm ^-1 (CO of carbonyl group of 4-pyridone ring)
Stretching vibration) 1530 cm ^-1 (antisymmetric stretching vibration of a nitro group) 1350 cm ^-1 (symmetrical stretching vibration of nitro groups) elemental analysis (molecular _{formula: C 11 H 8 N 2 O} 3, molecular weight: 216.196) Carbon Hydrogen Nitrogen Calculated value 61.1% 3.7% 13.0% Analytical value 60.9% 3.8% 12.9% [Synthesis example 2] of N- (4-cyanophenyl) -4-pyridone (Compound 2) Instead of synthetic 1-fluoro-4-nitrobenzene, 4-fluorobenzonitrile 4.84 g (39.96 mmo
Target compound 2 was obtained in the same manner as in Synthesis Example 1 except that 1) was used. -Yield: 5.90 g (30.07 mmol) [Yield: 7
5%] IR spectrum (measurement method: KBr method) 1640 cm ^-1 (CO of carbonyl group of 4-pyridone ring)
Stretching vibration) 2230 cm ^-1 (CN stretching vibration of nitrile group) -Elemental analysis (molecular formula: C ₁₂ H ₈ N ₂ O, molecular weight: 196.209) Carbon / hydrogen / nitrogen calculated value 73.5% 4.1% 14.3 % Analytical value 73.6% 4.0% 14.2% [Synthesis example 3] N- (5-nitro-2-pyridyl) -4-
Synthesis of Pyridone (Compound 3) Instead of 1-fluoro-4-nitrobenzene, 6.34 g (39.99 mm) of 2-chloro-5-nitropyridine.
ol) was used, and the target compound 3 was obtained by the same method as in Synthesis Example 1 except that the heating temperature during the reaction was 100 ° C. -Yield: 7.52 g (34.63 mmol) [Yield: 8
7%] IR spectrum (measurement method: KBr method) 1645 cm ^-1 (CO of carbonyl group of 4-pyridone ring)
Stretching vibration) antisymmetric stretching vibration of 1530 cm ^-1 (nitro group) 1350 cm ^-1 (symmetrical stretching vibration of nitro groups) elemental analysis (molecular _{formula: C 10 H 7 N 3 O} 3, molecular weight: 217.184) Carbon Hydrogen Nitrogen Calculated value 55.3% 3.3% 19.4% Analytical value 55.5% 3.2% 19.3% [Synthesis example 4] N- (4'-nitrobiphenyl-4-yl) -4-pyridone Synthesis of (Compound 4) 4-amino-4'-nitrobiphenyl 4.28 g (1
9.98 mmol) and 3.68 g (19.9 g) of keridonic acid.
(9 mmol) and 200 ml of diglyme were collected in a flask, heated and stirred at 100 ° C. for 2 hours, and further heated and refluxed for 2 hours. After allowing to cool, the reaction solution was concentrated under reduced pressure, 500 ml of water was added dropwise to the residue, and the precipitated crude crystals were collected by suction filtration and washed well with water. Then, the crude crystals were dried in vacuum and then recrystallized from hot ethanol to obtain the target compound 4. -Yield: 4.20 g (14.37 mmol) [Yield: 7
2%] IR spectrum (measurement method: KBr method) 1635 cm ^-1 (CO of carbonyl group of 4-pyridone ring)
Stretching vibration) 1530 cm ^-1 (antisymmetric stretching vibration of a nitro group) 1350 cm ^-1 (symmetrical stretching vibration of nitro groups) elemental analysis (molecular _{formula: C 17 H 12 N 2 O} 3, molecular weight: 292.294) Carbon Hydrogen Nitrogen Calculated value 69.9% 4.1% 9.6% Analytical value 69.8% 4.2% 9.6% [Synthesis example 5] N- [4- (4-nitrophenylazo) phenyl] -4- Synthesis of Pyridone (Compound 5) 4- (4-Nitrophenylazo) aniline [trade name: Disperse Orange 3] 4.84 g (19.98 mmo)
l), γ-pyrone (1.92 g, 19.98 mmol) and dioxane (200 ml) were collected in a flask and heated under reflux for 2 hours. After allowing to cool, the reaction solution was concentrated under reduced pressure, and the residue was mixed with water 5
00 ml was added dropwise, and the precipitated crude crystals were collected by suction filtration and washed well with water. Then, the crude crystals were dried in vacuum and then recrystallized from hot ethanol to obtain the target compound 5. -Yield: 3.52 g (10.99 mmol) [Yield: 5
5%] IR spectrum (measurement method: KBr method) 1640 cm ^-1 (CO of carbonyl group of 4-pyridone ring)
Stretching vibration) 1530 cm ^-1 (antisymmetric stretching vibration of a nitro group) 1350 cm ^-1 (symmetrical stretching vibration of nitro groups) elemental analysis (molecular _{formula: C 17 H 12 N 4 O} 3, molecular weight: 320.308) Carbon Hydrogen Nitrogen Calculated value 63.8% 3.8% 17.5% Analytical value 63.7% 3.8% 17.5% [Synthesis Example 6] Synthesis of N- (4-pyridyl) -4-pyridone (Compound 6) Instead of 4-amino-4'-nitrobiphenyl, 4-
Target compound 6 was obtained in the same manner as in Synthesis Example 4 except that 1.90 g (20.19 mmol) of aminopyridine was used. -Yield: 2.70 g (15.68 mmol) [Yield: 7
8%] IR spectrum (measurement method: KBr method) 1645 cm ^-1 (CO of carbonyl group of 4-pyridone ring)
Stretching vibration) Elementary analysis (molecular _{formula: C 10 H 8 N 2 O} , molecular weight: 172.187) Carbon Hydrogen Nitrogen Calculated 69.8% 4.7% 19.3% analysis 69.7% 4.6% 19.3% [Synthesis Example 7] N-phenyl-4-pyridone (Compound 7)
In the same manner as in Synthesis Example 4, except that 1.90 g (20.40 mmol) of aniline was used instead of 4-amino-4′-nitrobiphenyl, the target compound 7 was obtained. -Yield: 2.80 g (16.36 mmol) [Yield: 8
2%]-IR spectrum (measurement method: KBr method) 1650 cm ^-1 (CO of carbonyl group of 4-pyridone ring)
Stretching vibration) Elemental analysis (molecular formula: C ₁₁ H ₉ NO, molecular weight: 171.199) Carbon, hydrogen, nitrogen Calculated value 77.2% 5.3% 8.2% Analytical value 77.3% 5.3% 8. 1%

[0027]

EXAMPLES As Examples 1 to 7, 4-pyridone derivatives of compounds 1 to 7 obtained in Synthesis Examples 1 to 7, urea as Comparative Example 1 and MNA (2-methyl-4-nitroaniline as Comparative Example 2) ), The electronic state of each molecule was calculated by MOPAC, which is a general-purpose molecular orbital calculation method (the MNDO-PM3 method was used as the calculation method), and the secondary molecule hyperpolarizability β was calculated. Table 2 shows the value of βxxx which is the maximum component of β. Here, as the MOPAC program, "M
OPAC Ver. 6 ”is used, and β is Kurtz-Stewart-Diet built in the MOPAC.
By the er method, the heat of formation of the molecule and the dipole moment were numerically differentiated by the electric field. At this time, as the calculation coordinates, those obtained by converting the calculated values of the optimum conformation by the MNDO-PM3 method so that the center of gravity of the molecule coincides with the origin and the principal axis of inertia coincides with the x axis are used. However, this MOPA
The hyperpolarizability obtained by the calculation method incorporated in C corresponds to the hyperpolarizability when the frequency of the incident electric field = 0.

As is clear from Table 1, the 4-pyridone derivatives of Examples 1 to 7 have 50 to 50% of the urea of Comparative Example 1.
About 240 times (1.3 to 6 with respect to the MNA of Comparative Example 2).
It had a secondary molecule hyperpolarizability β of 8 times. This β is
It is an indicator of the second-order nonlinearity at the molecular level, and a compound having a larger β exhibits a large second-order nonlinearity at the molecular level. Therefore, it can be seen that the 4-pyridone derivative according to the present invention has a large quadratic nonlinearity at the molecular level.

On the other hand, with respect to the 4-pyridone derivatives of Examples 1 to 7 and MNA of Comparative Example 2, the visible-ultraviolet transmission spectra of 0.001M ethanol solutions were measured and the results are shown in FIG. From FIG. 1, it can be seen that the 4-pyridone derivatives of Examples 1 to 7 all have a light absorption band on the shorter wavelength side than the MNA of Comparative Example 2 and have a high light transmittance even in the blue wavelength region. . Therefore, it can be confirmed that the 4-pyridone derivative according to the present invention has good light transmittance in the visible region.

Next, with respect to the 4-pyridone derivatives of Examples 1 to 7 and the MNA of Comparative Example 2, the concentration dependence of the dielectric constant and the refractive index of the 1,4-dioxane solutions at 25 ° C. was measured to obtain the dipole. The moment μ was calculated. The results are shown in Table 1.
Also described in. Further, the secondary non-linear optical characteristics of the 4-pyridone derivatives of Examples 1 to 7, urea of Comparative Example 1 and MNA of Comparative Example 2 were examined by a so-called powder method. That is,
The crystal powder of each compound was pulverized in an agate mortar, and 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 sample for measurement. These measurement samples were irradiated with the fundamental wave of Nd-YAG laser (wavelength = 1.064 µm), 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 also shown in Table 1. As shown in Table 1, in the 4-pyridone derivatives of Examples 1 to 6 in which an electron-withdrawing functional group was introduced at one end, the dipole moment μ of the entire molecule was small, and the non-linearity was particularly excellent as the entire crystal. Have sex.

[0031]

[Table 1]

[0032]

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 nonlinearity.
The harmonic wave can be efficiently generated. 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 generation of harmonics and optical bistable elements.

[Brief description of drawings]

FIG. 1 is a visible-ultraviolet transmission spectrum of a 0.001M ethanol solution of 4-pyridone derivatives of Examples 1 to 7 and MNA of Comparative Example 2.

Claims (2)

(57) [Claims] 1. The following general formula (1): (In the formula, R ⁰ represents a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group.
X is -CH = CH-, -CH = N-, -N = CH-,
-N = N -, - O - , - S -, - shows a single bond or - SO _2. φ represents a substituted or unsubstituted aromatic hydrocarbon group or aromatic heterocyclic group. R ^{1 to} R ⁴ are each a substituted or unsubstituted aliphatic hydrocarbon group, a hydroxy group,
It represents an alkoxy group, a thio group, an alkylthio group, a carboxyl group, an oxycarbonyl group, a halogen atom or a hydrogen atom. n shows the integer of 0-2. ) An organic nonlinear optical material characterized by comprising a 4-pyridone derivative represented by 2. R ⁰ in the general formula (1) is a substituted or unsubstituted electron-withdrawing heterocyclic group, or an aromatic hydrocarbon group or aromatic heterocyclic group substituted with an electron-withdrawing characteristic group. The organic nonlinear optical material according to claim 1, wherein the organic nonlinear optical material is present.