JP3302733B2 - Organic nonlinear optical material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organic nonlinear optical material.

[0002]

2. Description of the Related Art The nonlinear optical effect is used for modulating the wavelength, phase and amplitude of laser light in harmonic generation, optical switching, optical mixing and the like, and plays 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 effects of these inorganic compound crystals were not sufficient. On the other hand, in recent years, many organic compounds having a much larger nonlinear optical constant than inorganic compound crystals and having excellent durability against optical damage have been found.

With respect to these organic nonlinear optical materials,
For example, D. J. "Nonlin" by Williams et al.
ear Optical Properties of
Organic and Polymeric Ma
terials "(American Chemica
l Society, 1983) ”and D.I. S. Che
mla et al., “Nonlinear Optical
Propertiesof Organic Mole
cures and Crystals "(Acade
mic 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 organic nonlinear optical material having the above-mentioned molecular structure tends to have a centrally symmetric structure during crystallization due to the presence of an electric dipole in the ground state, and the large nonlinearity exhibited by one molecule causes the entire crystal. There was a problem that was easily offset. When a π-electron system having a large spatial spread is used, the nonlinearity increases, but the absorption wavelength range (absorption band) of the molecule itself shifts to the deep color side (longer wavelength side). As a result, there is a problem that light transmittance in a blue wavelength range is reduced, and efficient generation of harmonics is prevented, and deterioration of molecules themselves is promoted. From such a thing,
There is a strong demand for an organic nonlinear optical material having excellent nonlinearity and having 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 nonlinear optical material which exhibits excellent nonlinearity and can efficiently generate harmonics.

[0007]

The organic nonlinear optical material of the present invention has the following general formula (3):

Embedded image (Wherein, R ₄ represents a substituted or unsubstituted aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group, alicyclic hydrocarbon group or hydrogen atom. Ar represents a substituted or unsubstituted group. Represents an aromatic hydrocarbon group or an aromatic heterocyclic group substituted by an electron-withdrawing heterocyclic group or an electron-withdrawing characteristic group, and φ represents a pyridine-type nuclear nitrogen atom (-N = And a nitrogen-containing aromatic heterocyclic group having a bond at a nuclear carbon atom adjacent to the nuclear nitrogen atom.

Embedded image (Wherein, = Z- is, = C (R ₅₎ - or = N
And two adjacent Zs may be condensed. X represents an O atom, an S atom, or an NR ₃ group. R ₃
And R ₅ are an unsubstituted aromatic hydrocarbon group, a heterocyclic group,
It represents an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or a hydrogen atom. )) A hydrazone derivative represented by the following formula: Examples of the organic nonlinear optical material according to the present invention include those shown in Examples 16 to 30 in Tables 4 and 5.

[0008]

[0009]

[0010]

[0011]

R ₁ in the above formulas (1) and (2)
R ₄ in to R ₃ and (3) is a substituted or unsubstituted aromatic hydrocarbon group, a heterocyclic group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or a hydrogen atom. Hereinafter, R
_The unsubstituted aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group and alicyclic hydrocarbon group introduced as _{1 to} R ₄ will be described.

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, triphenylene ring group, pyrene ring group, chrysene ring group, picene ring group, perylene ring group, benzopyrene ring group, rubicene ring group, coronene ring group, ovalene 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, pleiaden ring group, pentaphene ring group, pentacene ring group, tetraphenylene ring group, hexaphene ring group ,
Examples include a hexacene ring group, a trinaphthylene ring group, a heptaphen ring group, a heptacene ring group, and a pyranthrene ring group.

As the heterocyclic group, for example, a pyrrole ring group,
Pyrroline 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, cumarone 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, 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, Benzoisoxazole Ring group, thiazole ring group, thiazoline ring group, thiazolidine ring group, benzothiazole ring group, benzothiazoline ring group, naphthothiazole ring group, isothiazole ring group, benzoisothiazole 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, dithiane ring group, benzodithiane ring group, pyran ring group, chromene ring group, xanthene ring group, oxane ring group, chroman ring group, isochroman ring group, Examples 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 benzotellurazole ring group.

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

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

As R ₄ in the above formula (3), those having little steric hindrance are preferred, and a hydrogen atom or a lower alkyl group (eg, a methyl group, an ethyl group, a propyl group, etc.) is particularly preferred.

An aromatic hydrocarbon group introduced as R _{1 to} R _{4 in the} above formulas (1), (2) and (3);
The heterocyclic group, aliphatic hydrocarbon group or alicyclic hydrocarbon group may be substituted with the substituents exemplified below. For example, disubstituted amino groups (for example, dimethylamino group, diethylamino group, dibutylamino group, ethylmethylamino group, butylmethylamino group, diamylamino group, dibenzylamino group, diphenethylamino group, diphenylamino group, ditolylamino group, Silylamino group, methylphenylamino group, benzylmethylamino group, etc., monosubstituted amino group (for example, methylamino group, ethylamino group, propylamino group, isopropylamino group, ter
t-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), sulfonylamino group (eg, mesylamino group, ethylsulfonylamino group, phenylsulfonylamino group, pyridylsulfonylamino group, tosylamino group, taurylamino group, trifluoromethylsulfonylamino group, sulfamoylamino group, methylsulfamoyl An amino group, a sulfanylamino group, an acetylsulfanylamino group, an ammonium group (for example, a trimethylammonio group, an ethyldimethylammonio group, a dimethylphenylammonio group,
Pyridinio group, quinolinio group, etc.), amino group, oxyamino group (for example, methoxyamino group, ethoxyamino group, phenoxyamino group, pyridyloxyamino group, etc.), hydroxyamino group, ureido group, semicarbazide group, carbazide group, disubstitution Hydrazino groups (eg, dimethylhydrazino group, diphenylhydrazino group, methylphenylhydrazino group, etc.), mono-substituted hydrazino groups (eg, methylhydrazino group, phenylhydrazino group, pyridylhydrazino group, benzylidenehydrazino group, etc.),
Hydrazino group, azo group (eg, phenylazo group, pyridylazo group, thiazolylazo group, etc.), azoxy group, amidino group, cyano group, cyanato group, thiocyanato group, nitro group, nitroso group, oxy group (eg, methoxy group, ethoxy group, propoxy group) 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 (for example, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, pyridyloxycarbonyl group, etc.), amino Carbonyl group (for example, carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, pyridylcarbamoyl group, carbazoyl group, allophanoyl group, oxamoyl group, succinamoyl group, etc.), thiocarboxyl group and salts thereof, dithiocarboxyl group and salts thereof, thiocarbonyl group (For example, a methoxythiocarbonyl group, a methylthiocarbonyl group,
A methylthiothiocarbonyl group, an acyl group (eg, formyl group, acetyl group, propionyl group, acryloyl group, benzoyl group, cinnamoyl group, pyridinecarbonyl group, thiazolecarbonyl group, trifluoroacetyl group, etc.), a 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 (for example, methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, etc.), sulfonyl group ( For example, mesyl group, ethylsulfonyl group, phenylsulfonyl group, pyridylsulfonyl group, tosyl group, tauryl group, trifluoromethylsulfonyl group, sulfamoyl group, methylsulfamoyl group,
Sulfanyl group, acetylsulfanyl group, etc.),
Oxysulfonyl group (for example, methoxysulfonyl group, ethoxysulfonyl group, phenoxysulfonyl group, acetaminophenoxysulfonyl group, pyridyloxysulfonyl group, etc.), thiosulfonyl group (for example, methylthiosulfonyl group, ethylthiosulfonyl group, phenylthiosulfonyl group, acetoacetate) Aminophenylthiosulfonyl group,
A pyridylthiosulfonyl group, an aminosulfonyl group (for example, a sulfamoyl group, a methylsulfamoyl group,
Dimethylsulfamoyl group, ethylsulfamoyl group,
A diethylsulfamoyl group, a phenylsulfamoyl group, an acetaminophenylsulfamoyl group, a pyridylsulfamoyl group, etc., a halogenated alkyl group (for example, chloromethyl group, bromomethyl group, fluoromethyl group, dichloromethyl group, dibromo Methyl group, difluoromethyl group, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, etc., hydrocarbon group (eg, alkyl group, aryl group, alkenyl group, alkynyl group, etc.), heterocyclic group, organosilicon group (For example, a silyl group, a disilanyl group, a trimethylsilyl group, a triphenylsilyl group, and the like).

In the above formulas (1), (2) and (3), Ar represents an aromatic hydrocarbon group or an aromatic group substituted by a substituted or unsubstituted electron-withdrawing heterocyclic group or an electron-withdrawing characteristic group. Group heterocyclic group.

Examples of the unsubstituted electron-withdrawing heterocyclic group introduced as Ar include an oxazole ring group, a benzoxazole ring group, a naphthooxazole ring group, an isoxazole ring group, a benzoisoxazole ring group, a thiazole ring group, Benzothiazole ring group, benzothiazoline ring group,
Naphthothiazole ring group, isothiazole ring group, benzoisothiazole 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, Examples include a naphthoselenazole ring group, a tellurazole ring group, and a benzotellurazole ring group. Further, these electron-withdrawing heterocyclic groups may be substituted with the substituents exemplified in the description of R _{1 to} R ₄ .

Examples of the aromatic hydrocarbon group or aromatic heterocyclic group substituted by the electron-withdrawing characteristic group introduced as Ar include the following unsubstituted aromatic hydrocarbon groups or aromatic heterocyclic groups. And those substituted with various electron-withdrawing characteristic groups shown in the following.

As the aromatic hydrocarbon group substituted by the electron-withdrawing characteristic group, those exemplified in the description of R _{1 to} R ₄ can be mentioned. Examples of the aromatic heterocyclic group substituted with an electron-withdrawing characteristic group include, for example, a pyrrole ring group, an indole ring group, an isoindole ring group, a carbazole ring group, a furan ring group, a cumarone ring group, an isobenzofuran ring group, Dibenzofuran ring group, 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, naphtho Oxazole ring group, isoxazole ring group, benzoisoxazole ring group, thiazole ring group, benzothiazole ring group, naphthothiazole ring group, isothiazole ring group, benzoisothiazole ring group, triazole ring group, benzotriazole ring group, oxa Diazole ring group, thiadiazole ring group Benzo oxadiazole ring group, a benzothiadiazole ring group, a 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, naphthoselenazole ring group, Rurazoru ring group, such as benzotellurazole ring group.

The electron-withdrawing characteristic groups to be introduced into these aromatic hydrocarbon groups or aromatic heterocyclic groups include nitro groups, nitroso groups, cyano groups, cyanato groups, thiocyanato groups, halogen groups (fluoro groups, chloro groups, etc.). Group, bromo group, iodo group), carboxyl group and salts thereof, oxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl 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, dithiocarboxyl group and salts thereof, thiocarbonyl group (for example, methoxythiocarbonyl group, Thiocarbonyl group, methylthio such thiocarbonyl group), an acyl group (e.g. formyl group, acetyl group, propionyl group, acryloyl group, benzoyl group, cinnamoyl group, a pyridine group,
Thiazole carbonyl group, trifluoroacetyl group, etc.), thioacyl group (eg, thioformyl group, thioacetyl group, thiobenzoyl group, pyridinethiocarbonyl group, etc.), sulfinic acid group and salts thereof, sulfonic acid group and salts thereof, sulfinyl group (eg, Methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, etc.), sulfonyl group (for example, mesyl group, ethylsulfonyl group, phenylsulfonyl group, pyridylsulfonyl group,
A tosyl group, a tauryl group, a trifluoromethylsulfonyl group, a sulfamoyl group, a methylsulfamoyl group, a sulfanyl group, an acetylsulfanyl group, an oxysulfonyl group (for example, a methoxysulfonyl group, an ethoxysulfonyl group, a phenoxysulfonyl group, Aminophenoxysulfonyl group, pyridyloxysulfonyl group, etc.), thiosulfonyl group (eg, methylthiosulfonyl group, ethylthiosulfonyl group, phenylthiosulfonyl group, acetaminophenylthiosulfonyl group, pyridylthiosulfonyl group, etc.), aminosulfonyl group (eg, Sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, phenylsulfamoyl, acetaminophen A sulfamoyl group, pyridyl etc. Jill sulfamoyl group), a halogenated alkyl group (such as chloromethyl group, bromomethyl group, fluoromethyl group, dichloromethyl group, dibromomethyl group, a difluoromethyl group, a trifluoromethyl group, pentafluoroethyl group,
A heptafluoropropyl group).

In the above formula (3), Ar is a strong electron-withdrawing characteristic group such as a nitro group, which replaces an electron-withdrawing position of an aromatic hydrocarbon group or an aromatic heterocyclic group. Substituted aromatic hydrocarbon group or electron-withdrawing substituted aromatic heterocyclic group (for example, 5-nitro-2-
Pyridyl group, 4-nitrophenyl group, 2,4-dinitrophenyl group, etc.) are particularly preferred.

In the formula (3), φ represents a substituted or unsubstituted nitrogen-containing nitrogen atom having a pyridine type nuclear nitrogen atom (-N =) and having a bond at a nuclear carbon atom adjacent to the nuclear nitrogen atom. It is an aromatic heterocyclic group. A specific structural formula of such φ is shown in [Formula 7] below.

[0026]

Embedded image

(Wherein, = Z- is ＣC (R ₅ )
-Or = N-. Note that two adjacent Z
May be fused. X represents an O atom, an S atom, or an NR ₃ group. R ₃ and R ₅ represent an unsubstituted aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group, alicyclic hydrocarbon group or hydrogen atom. )

Examples of the unsubstituted nitrogen-containing aromatic heterocyclic group introduced as φ include 2-pyridyl, 2-quinolyl, 1-isoquinolyl, 3-isoquinolyl,
Phenanthridyl group, 1,10-phenanthrylone-2
-Yl group, 3-pyridazinyl group, 1-phthalazinyl group,
3-cinnolinyl group, 2-pyrimidinyl group, 4-pyrimidinyl group, 2-quinazolinyl group, 4-quinazolinyl group,
2-pyrazinyl group, 2-quinoxalinyl group, 1,3,5
-Triazin-2-yl group, 1,2,4,5-tetrazin-3-yl group, 2-imidazolyl group, 4-imidazolyl group, 2-benzimidazolyl group, 2-naphthymidazolyl group, 3-pyrazolyl group, 3 -Indazolyl group, 2-
Oxazolyl group, 4-oxazolyl group, 2-benzoxazolyl group, 2-naphthooxazolyl group, 3-isoxazolyl group, 3-benzoisoxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 2- Benzothiazolyl group, 2-naphthothiazolyl group, 2-selenazolyl group, 2
-Benzoselenazolyl group, 2-tellrazolyl group, 2-benzotellrazolyl group, 1,2,3-triazole-4-
Yl group, 1,2,4-triazol-3-yl group, 1,
2,4-triazol-5-yl group, 1,2,3,5-
And a tetrazol-4-yl group. Further, these nitrogen-containing aromatic heterocyclic groups may be substituted with the substituents exemplified in the description of R _{1 to} R ₄ .

In the above equation (3), φ is:
It is preferable that the chemical species protonated to the pyridine type nuclear nitrogen atom (-N =) have an acid dissociation constant pKa between 1 and 10. More specifically, a 2-pyridyl group, 2-
Quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 6-phenanthridyl group, 3-pyridazinyl group, 1
-Phthalazinyl group, 3-cinnolinyl group, 2-pyrimidinyl group, 4-pyrimidinyl group, 2-quinazolinyl group, 4
-Quinazolinyl group, 2-pyrazinyl group, 2-quinoxalinyl group, 2-imidazolyl group, 4-imidazolyl group, 2
-Benzimidazolyl group, 3-pyrazolyl group, 3-indazolyl group, 2-thiazolyl group, 4-thiazolyl group, 2
-A benzothiazolyl group is particularly preferred.

The azomethine derivatives represented by the formulas (1) and (2) according to the present invention can be obtained by converting a carbonyl compound such as an aldehyde into an acyl hydrazide,
It is easily synthesized by dehydration condensation with a hydrazide compound such as thioacyl hydrazide or amidrazone.

The hydrazone derivative represented by the formula (3) according to the present invention is obtained by dehydrating and condensing a carbonyl compound such as an aldehyde with an N-aryl (or heteroaryl) hydrazine compound in the presence of an acid catalyst such as acetic acid. It is easily synthesized.

[0032]

The azomethine derivative represented by the general formulas (1) and (2) is a compound having an electron-withdrawing substituent (an aromatic hydrocarbon substituted with an electron-withdrawing heterocyclic group or an electron-withdrawing characteristic group) as an Ar group. Group or aromatic heterocyclic group), the polarization by the resonance effect (mesomeric polarization)
And the nonlinearity at the molecular level is improved. In addition, since the compound has a hydrogen bonding substituent in its molecular skeleton, a non-centrosymmetric crystal structure can be easily formed by intermolecular hydrogen bonding, and excellent nonlinearity is ensured. Further, the light absorption band of the azomethine derivative exists on the short wavelength side. As a result, the organic nonlinear optical material comprising the azomethine derivative exhibits excellent nonlinearity, has good light transmittance in a blue wavelength region, and can efficiently generate harmonics.

Similarly, the hydrazone derivative represented by the general formula (3) is an imino group (—NH) in the hydrazone skeleton.
-) Acts as an electron-donating group, and an electron-withdrawing substituent (an aromatic hydrocarbon group or an aromatic heterocyclic group substituted by an electron-withdrawing heterocyclic group or an electron-withdrawing characteristic group) as an Ar group. , Polarization due to the resonance effect (mesomeric polarization) increases, and nonlinearity at the molecular level is improved. Further, the imino group (-NH
A stable intermolecular hydrogen bond is formed between the hydrogen atom of-) and the azomethine-type nitrogen atom (= N-) in the hydrazone skeleton and the pyridine-type nuclear nitrogen atom (= N-) of the nitrogen-containing aromatic heterocyclic group φ. Since it is formed, it is easy to take a crystal structure having a non-centrosymmetric structure, and excellent non-linearity is secured. Further, the light absorption band of the hydrazone derivative exists on the short wavelength side, and the organic nonlinear optical material composed of the hydrazone derivative exhibits excellent nonlinearity. Moreover, the melting point is high due to stable intermolecular hydrogen bonding, and the problem of heat resistance, which has been a drawback of conventional organic nonlinear optical materials, can be overcome.

[0034]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. (A) Synthesis example of azomethine derivative [Synthesis example 1] Synthesis of 4-nitrobenzaldehyde acetylhydrazone (compound 1)

1.5 g of acetohydrazide (20 mmol
l), 3.3 g of 4-nitrobenzaldehyde (22 mm
ol) and 1.0 ml (17.5 mmol) of acetic acid are dissolved in 50 ml of ethanol and heated under reflux for 2 hours. After allowing to cool, the mixture is concentrated under reduced pressure, and the precipitated crude crystals are thoroughly washed with water.
The crude crystals were collected by suction filtration and recrystallized from a solvent such as ethanol or tetrahydrofuran to obtain the desired compound 1. Yield: 3.2 g (15.4 mmol) [Yield: 77%] Elemental analysis (molecular formula: C ₉ H ₉ N ₃ O ₃ , molecular weight: 20)
7.189) [Synthesis Example 2] Synthesis of 2-nitrobenzaldehyde acetylhydrazone (compound 2)

Instead of 4-nitrobenzaldehyde,
3.3 g (22 mmol) of 2-nitrobenzaldehyde
Compound 2 was obtained in the same manner as in Synthesis Example 1 except that was used. Yield: 3.0 g (14.5 mmol) [Yield: 72%] Elemental analysis (molecular formula: C ₉ H ₉ N ₃ O ₃ , molecular weight: 20)
7.189) [Synthesis Example 3] Synthesis of 4-cyanobenzaldehyde acetylhydrazone (compound 3)

Instead of 4-nitrobenzaldehyde,
2.9 g (22 mmol) of 4-cyanobenzaldehyde
Compound 3 was obtained in the same manner as in Synthesis Example 1 except that was used. Yield: 2.7 g (14.4 mmol) [Yield: 72%] Elemental analysis (molecular formula: C ₁₀ H ₉ N ₃ O, molecular weight: 187.
202) [Synthesis Example 4] Synthesis of 4- (methoxycarbonyl) benzaldehyde acetylhydrazone (compound 4)

Instead of 4-nitrobenzaldehyde,
3.6 g (22 mmol) of methyl 4-formylbenzoate
Compound 4 was obtained in the same manner as in Synthesis Example 1 except that was used. Yield: 2.5 g (11.4 mmol) [Yield: 57%] Elemental analysis (molecular formula: C ₁₁ H ₁₂ N ₂ O ₃ , molecular weight: 22)
0.228) [Synthesis Example 5] Synthesis of 5-nitro-2-furaldehyde acetylhydrazone (compound 5)

Instead of 4-nitrobenzaldehyde,
5-nitro-2-furaldehyde 3.1 (22 mmol
Except using l), the desired compound 5 was obtained in the same manner as in Synthesis Example 1. Yield: 3.0 g (15.2 mmol) [Yield: 76%] Elemental analysis (molecular formula: C ₇ H ₇ N ₃ O ₄ , molecular weight: 19)
7.150) [Synthesis Example 6] Synthesis of 5-nitrothiophene-2-carboxaldehyde acetylhydrazone (compound 6)

Instead of 4-nitrobenzaldehyde,
5-nitrothiophene-2-carboxaldehyde3.
Except that 4 g (22 mmol) was used, the target compound 6 was obtained in the same manner as in Synthesis Example 1. Yield: 3.6 g (16.9 mmol) [Yield: 84%] Elemental analysis (molecular formula: C ₇ H ₇ N ₃ O ₃ S, molecular weight: 21)
3.211) Carbon Hydrogen Nitrogen Sulfur Calculated 39.43% 3.31% 19.71% 15.04% Analyzed 39.33% 3.37% 19.47% 15.13% [Synthesis Example 7] 4 Synthesis of nitrobenzaldehyde benzoyl hydrazone (compound 7) Instead of acetohydrazide, benzohydrazide 2.7
Except using g (20 mmol), the target compound 7 was obtained in the same manner as in Synthesis Example 1. Yield: 4.4 g (16.3 mmol) [Yield: 82%] Elemental analysis (molecular formula: C ₁₄ H ₁₁ N ₃ O ₃ , molecular weight: 26)
9.260) [Synthesis Example 8] Synthesis of 4-nitrobenzaldehyde nicotinoylhydrazone (compound 8) Instead of acetohydrazide, nicotinohydrazide
Except that 8 g (20 mmol) was used, the target compound 8 was obtained in the same manner as in Synthesis Example 1. Yield: 4.0 g (14.8 mmol) [Yield: 74%] Elemental analysis (molecular formula: C ₁₃ H ₁₀ N ₄ O ₃ , molecular weight: 27)
0.248) [Synthesis Example 9] Synthesis of 4-nitrobenzaldehyde picolinoylhydrazone (compound 9) Instead of acetohydrazide, picolinohydrazide
Except that 8 g (20 mmol) was used, the target compound 9 was obtained in the same manner as in Synthesis Example 1. Yield: 4.4 g (16.3 mmol) [Yield: 81%] Elemental analysis (molecular formula: C ₁₃ H ₁₀ N ₄ O ₃ , molecular weight: 27)
0.248) Synthesis Example 10 Synthesis of 5-nitrothiophene-2-carboxaldehyde picolinoylhydrazone (Compound 10)

2.8 g of picolino hydrazide (20 mm
Using l) and 3.4 g (22 mmol) of 5-nitrothiophene-2-carboxaldehyde, the target compound 10 was obtained in the same manner as in Synthesis Example 1. Yield: 4.6 g (16.7 mmol) [Yield: 83%] Elemental analysis (molecular formula: C ₁₁ H ₈ N ₄ O ₃ S, molecular weight: 27)
6.270) Carbon Hydrogen Nitrogen Sulfur Calculated 47.82% 2.92% 20.28% 11.60% Analytical 47.77% 2.94% 20.17% 11.65% [Synthesis Example 11] 4 -Synthesis of nitrobenzaldehyde thiobenzoylhydrazone (compound 11)

The desired compound 11 was obtained in the same manner as in Synthesis Example 1 except that 3.0 g (20 mmol) of thiobenzoyl hydrazide was used instead of acetohydrazide. Yield: 4.3 g (15.1 mmol) [Yield: 75%] Elemental analysis (molecular formula: C ₁₄ H ₁₁ N ₃ O ₂ S, molecular weight: 28)
5.321) Carbon Hydrogen Nitrogen Sulfur Calculated 58.94% 3.89% 14.73% 11.24% Analytical 59.23% 3.72% 14.70% 11.20% [Synthesis Example 12] 5 Of -Nitro-2-furaldehyde thiobenzoylhydrazone (Compound 12)

Thiobenzohydrazide 3.0 g (20 mm
ol) and 3.1 g of 5-nitro-2-furaldehyde
(22 mmol), and the target compound 12 was obtained in the same manner as in Synthesis Example 1. Yield: 3.9 g (14.2 mmol) [Yield: 71%] Elemental analysis (molecular formula: C ₁₂ H ₉ N ₃ O ₃ S, molecular weight: 27)
5.282) Carbon Hydrogen Nitrogen Sulfur Calculated 52.36% 3.30% 15.26% 11.65% Analytical 52.17% 3.29% 15.55% 11.67% [Synthesis Example 13] 5 Of -Nitrothiophene-2-carboxaldehyde thiobenzoylhydrazone (Compound 13)

Thiobenzohydrazide 3.0 g (20 mm
ol) and 3.4 g (22 mmol) of 5-nitrothiophene-2-carboxaldehyde to obtain the target compound 13 in the same manner as in Synthesis Example 1. Yield: 4.5 g (15.4 mmol) [Yield: 77%] Elemental analysis (molecular formula: C ₁₂ H ₉ N ₃ O ₂ S ₂ , molecular weight: 2)
91.343) Carbon Hydrogen Nitrogen Sulfur Calculated 49.47% 3.11% 14.42% 22.01% Analytical 49.10% 3.00% 14.59% 22.24% [Synthesis Example 14] 4 -Synthesis of nitrobenzaldehyde acetamidrazone (compound 14)

2.5 g of ethyl acetamidoate (hydrochloride)
(20 mmol), 3.3 g (22 mmol) of 4-nitrobenzaldehyde hydrazone, triethylamine 2.
8 ml (2.0 g, 20 mmol) of ethanol 20 m
and heat to reflux for 30 minutes. After allowing to cool, the mixture is concentrated under reduced pressure, and the precipitated crude crystals are thoroughly washed with water. The crude crystals were collected by suction filtration and recrystallized from a solvent such as ethanol or tetrahydrofuran to obtain the desired compound 14. Yield: 3.3 g (16.0 mmol) [Yield: 80%] Elemental analysis (molecular formula: C ₉ H ₁₀ N ₄ O ₂ , molecular weight: 20)
6.205) [Synthesis Example 15] Synthesis of 5-nitrothiophene-2-carboxaldehyde acetamidrazone (compound 15)

The desired compound 1 was prepared in the same manner as in Synthesis Example 14, except that 3.4 g (20 mmol) of 5-nitrothiophene-2-carboxaldehyde hydrazone was used instead of 4-nitrobenzaldehyde hydrazone.
5 was obtained. Yield: 3.1 g (14.6 mmol) [Yield: 73%] Elemental analysis (molecular formula: C ₇ H ₈ N ₄ O ₂ S, molecular weight: 21)
2.227) Carbon Hydrogen Nitrogen Sulfur Calculated 39.62% 3.80% 26.40% 15.11% Analytical 39.76% 3.70% 26.26% 15.00% Compounds 1 to 15 or more Are shown in Tables 1 to 3. (B) Synthesis Example of Hydrazone Derivative [Synthesis Example 16] 2-pyridylcarboxaldehyde-4
Of nitrophenylhydrazone (compound 16)

3.1 g of 4-nitrophenylhydrazine
(20 mmol) and 2.0 ml (2.25 g, 21.0 mmol) of 2-pyridinecarboxaldehyde were dissolved in 50 ml of ethanol, and 1 ml of acetic acid (17.5 mm) was dissolved.
ol) and heat to reflux for 2 hours. After standing to cool, the precipitated crude crystals were collected by suction filtration, and the crude crystals were recrystallized from a solvent such as ethanol or 1,4-dioxane.
Was obtained. In Table 4, the compounds are specified by displaying the structural formulas of the introduced Ar and φ, and the chemical composition formula and the molecular weight are also described.
Table 7 shows the yield, elemental analysis results, and melting point. Synthesis of compounds 17-36

Compounds 17 to 36 shown in Tables 4 to 6 were synthesized in the same manner as in Synthesis Example 16 using the corresponding hydrazine compounds and aldehyde compounds to obtain the desired compounds. In addition, compounds 31 to 3 in Table 6
6 (Comparative Examples 3 to 8) are similar to the hydrazone derivative according to the present invention, but do not have a nitrogen-containing aromatic heterocyclic group φ introduced therein and are compounds outside the scope of the present invention. Tables 7 and 8 also show the yield, elemental analysis results, and melting point of these compounds. (C) Measurement of nonlinear optical characteristics

Examples 1 to 15 show azomethine derivatives of compounds 1 to 15 and Examples 16 to 30 show compound 1
6 to 30 hydrazone derivatives, urea as Comparative Example 1, MNA (2-methyl-4-nitroaniline) as Comparative Example 2 and Compound 31 which is a compound similar to the hydrazone derivative according to the present invention as Comparative Examples 3 to 8 The second-order nonlinear optical characteristics of the hydrazone derivatives Nos. To 36 were evaluated by a so-called powder method. That is, the crystal powder of each compound is pulverized in an agate mortar, and the particle size is reduced to 100 by a sieve.
A powder having a size between 150 μm and 150 μm was prepared, and the powder sandwiched between slide glasses was used as a measurement sample. For these measurement samples, the fundamental wave of Nd-YAG laser (wavelength =
1.064 μm), and the second harmonic (S
HG) The strength of the component was measured. The results obtained by 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 3 for Examples 1 to 15 and Comparative Examples 1 and 2. Examples 16 to 30 and Comparative Examples 1 to 8 are also shown in Tables 7 and 8, respectively.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

[0053]

[Table 4]

[0054]

[Table 5]

[0055]

[Table 6]

[0056]

[Table 7]

[0057]

[Table 8]

As is clear from Tables 1 to 3, Example 1
It can be confirmed that the azomethine derivatives of Nos. 1 to 15 generate SHG about several times to about twenty and several times that of the urea of Comparative Example 1, which indicates that they have excellent nonlinearity.

As is clear from Tables 7 and 8, the hydrazone derivatives of Examples 16 to 30 are more than ten to several tens times the hydrazone derivatives of Comparative Examples 3 to 8 and the urea of Comparative Example 1. It can be confirmed that a degree of SHG has been generated,
It turns out that it has excellent nonlinearity. Moreover, the hydrazone derivatives of Examples 16 to 30 have a very high melting point of 240 to 320 ° C as an organic compound, and are much more heat-resistant than the urea of Comparative Example 1 and the MNA of Comparative Example 2 which are conventionally used. It turns out that it is excellent.

Further, the azomethine derivatives of Examples 1, 3 and 10 and the MNA of Comparative Example 2 were 0.00
FIG. 1 shows the result of measuring the visible-ultraviolet transmission spectrum of the 1M ethanol solution.

As is clear from FIG. 1, the azomethine derivatives of Examples 1, 3 and 10 have a shorter light absorption band than the MNA of Comparative Example 2 and have a light transmittance even in the blue wavelength region. Can be confirmed to be high. Further, when the visible-ultraviolet transmission spectrum of a 0.001 M ethanol solution of the azomethine derivative and the hydrazone derivative of this example other than these was measured, the light absorption band was similarly MN.
A existed on the shorter wavelength side than A. This indicates that the azomethine derivative and the hydrazone derivative according to the present invention have good light transmittance in the visible region.

[0062]

As described in detail above, the organic nonlinear optical material of the present invention can be synthesized very easily, has high light transmittance on the short wavelength side, high blue light transmittance, 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 utilizing nonlinear phenomena such as high-speed optical shutters such as generation of harmonics and optical bistable elements.

[Brief description of the drawings]

FIG. 1 shows the azomethine derivatives of Examples 1, 3 and 10 of the present invention and the MNA of Comparative Example 2 with 0.001 M
It is a visible-ultraviolet transmission spectrum figure of an ethanol solution.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G02F 1/29-7/00

Claims (2)

(57) [Claims] 1. The following general formula (3): (Wherein, R ₄ represents a substituted or unsubstituted aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group, alicyclic hydrocarbon group or hydrogen atom. Ar represents a substituted or unsubstituted group. .φ, under illustrating an electron-withdrawing heterocyclic group, or an aromatic substituted with electron-withdrawing properties hydrocarbon group or an aromatic heterocyclic group
A pyridine-type nuclear nitrogen atom (-N =) represented by the chemical formula
And a nitrogen-containing aromatic heterocyclic group having a bond at a nuclear carbon atom adjacent to the nuclear nitrogen atom . Embedded image (Wherein, = Z- is, = C (R ₅₎ - or = N
And two Zs adjacent to each other may be fused
No. X represents an O atom, an S atom, or an NR ₃ group. R ₃
And R ₅ are an unsubstituted aromatic hydrocarbon group, a heterocyclic group,
Aliphatic hydrocarbon group, alicyclic hydrocarbon group or hydrogen atom
Show. An organic nonlinear optical material comprising a hydrazone derivative represented by the formula (1 ) . 2. In the above general formula (3), Ar is the following chemical formula: Wherein φ in the general formula (3) is the following chemical formula: The organic nonlinear optical material according to claim 1, wherein the organic nonlinear optical material is selected from the group consisting of: