JPH0635014A - Organic nonlinear optical material - Google Patents

Abstract

PURPOSE:To provide an org. nonlinear optical material which has excellent nonlinearity and can efficiently generate harmonic waves. CONSTITUTION:This material consists of a compd. expressed by formula I or its tautomerism expressed by formula II which is an azomethyne deriv., or hydrazone deriv. expressed by formula III. In formulae. X is O atom, S atom or NR3 group. R1-R4-0 are substd. or unsubstd. aromatic hydrocarbon groups. heterocyclic groups, aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, or hydrogen atoms. Ar is an electron withdrawing heterocyclic group, or an aromatic hydrocarbon group or aromatic heterocyclic group with substitution of electron withdrawing groups phi is a substd. or unsubstd. nitrogen-contg. aromatic heterocyclic group having pyridine-type nucleus nitrogen atom and has a bond with nucleus carbon atom adjacent to the nucleus nitrogen atom.

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 Nonlinear optical effects are used for modulation of wavelength, phase and amplitude of laser light in harmonic generation, optical switching, optical 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 that 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., "" Nonlin
ear Optical Properties of
Organic and Polymeric Ma
terials "(American Chemica
l Society, 1983) ", D.I. S. Che
mla et al., "" Nonlinear Optical
Properties of 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 above-mentioned organic nonlinear optical material having a molecular structure tends 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 causes However, there was a problem that they were easily offset. If a π-electron system with 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 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. 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 following general formula (1).

[0008]

[Chemical 4] Or the following general formula (2) which is a tautomer of this compound

[0009]

[Chemical 5] (In the formula, X is an O atom, an S atom, or NR ₃
Indicates a group. R _{1 to} R ₃ represent a substituted or unsubstituted aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group, alicyclic hydrocarbon group or hydrogen atom. 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. ) Or an azomethine derivative represented by the following general formula (3)

[0010]

[Chemical 6] (However, in the formula, R ₄ has the same meaning as R _{1 to} R ₃ and Ar has the same meaning as Ar.

Φ is a pyridine type nuclear nitrogen atom (-N =)
And a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group having a bond to a nuclear carbon atom adjacent to the nuclear nitrogen atom. ) Is represented by a hydrazone derivative. X in the above formulas (1) and (2) is an O atom, an S atom, or an NR ₃ group.

R ₁ in the equations (1) and (2)
To R ₃ and R ₄ in the formula (3) are a substituted or unsubstituted aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group, alicyclic hydrocarbon group or hydrogen atom. Below, 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. 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 trioxane ring group, thiane ring group, trithiane ring group, morpholine ring group, quinuclidine ring group, selenazole ring group, benzoselenazole ring group, naphthoselenazole ring group, tellurazole ring group, and benzotelrazole ring group.

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, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclopentadiene group. Examples thereof include an enyl group and a cyclohexadienyl group.

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

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, a di-substituted amino group (for example, dimethylamino group, diethylamino group, dibutylamino group, ethylmethylamino group, butylmethylamino group, diamylamino group, dibenzylamino group, diphenethylamino group, diphenylamino group, ditolylamino group, diquinoyl group Silylamino group, methylphenylamino group, benzylmethylamino group, etc., mono-substituted amino group (eg 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) Groups), sulfonylamino groups (eg, mesylamino group, ethylsulfonylamino group, phenylsulfonylamino group, pyridylsulfonylamino group, tosylamino group, taurylamino group, trifluoromethylsulfonylamino group, sulfamoylamino group, methylsulfamoyl) Amino group, sulfanylamino group, acetylsulfanylamino group, etc., ammonio group (eg, trimethylammonio group, ethyldimethylammonio group, dimethylphenylammonio group,
Pyridinio group, quinolinio group, etc.), amino group, oxyamino group (eg methoxyamino group, ethoxyamino group, phenoxyamino group, pyridyloxyamino group etc.), hydroxyamino group, ureido group, semicarbazide group, carbazide group, di-substituted Hydrazino group (for example, dimethylhydrazino group, diphenylhydrazino group, methylphenylhydrazino group, etc.), mono-substituted hydrazino group (for example, 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 (eg, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, pyridyloxycarbonyl group, etc.), amino Carbonyl 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, a methoxythiocarbonyl group, a methylthiocarbonyl group,
Methylthiothiocarbonyl group etc.), acyl group (eg 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 (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,
Sulfanilyl group, acetylsulfanylyl group, etc.),
Oxysulfonyl group (eg methoxysulfonyl group, ethoxysulfonyl group, phenoxysulfonyl group, acetaminophenoxysulfonyl group, pyridyloxysulfonyl group, etc.), thiosulfonyl group (eg methylthiosulfonyl group, ethylthiosulfonyl group, phenylthiosulfonyl group, acetoacetate Aminophenylthiosulfonyl group,
Pyridylthiosulfonyl group), aminosulfonyl group (eg 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, 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, etc.) and the like.

Ar in the above formulas (1), (2) and (3) is an aromatic hydrocarbon group or an aromatic group substituted with a substituted or unsubstituted electron withdrawing heterocyclic group or an electron withdrawing characteristic group. It is a group heterocyclic group.

The unsubstituted electron-withdrawing heterocyclic group introduced as Ar includes, for example, an oxazole ring group, a benzoxazole ring group, a naphthoxazole ring group, an isoxazole ring group, a benzisoxazole ring group, a thiazole ring group, Benzothiazole ring group, benzothiazoline 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. Moreover, these electron-withdrawing heterocyclic groups may be substituted with the substituents exemplified in the description of R _{1 to} R ₄ .

As the aromatic hydrocarbon group or aromatic heterocyclic group substituted by an electron-withdrawing characteristic group introduced as Ar, the following unsubstituted aromatic hydrocarbon group or aromatic heterocyclic group is shown below. Examples thereof include those substituted with various electron-withdrawing characteristic groups shown in.

Examples of the aromatic hydrocarbon group substituted with the electron-withdrawing characteristic group include those exemplified in the description of R _{1 to} R ₄ . Examples of the aromatic heterocyclic group substituted with an electron-withdrawing characteristic 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, 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, benzisoxazole ring group, thiazole ring group, benzothiazole ring group, naphthothiazole ring group, isothiazole ring group, benzisothiazole 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.

As the electron-withdrawing characteristic group introduced into these aromatic hydrocarbon groups or aromatic heterocyclic groups, nitro group, nitroso group, cyano group, cyanato group, thiocyanato group, halogen group (fluoro group, chloro group 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, succiamomoyl group, etc.), thiocarboxyl group and its salt, dithiocarboxyl group and its salt, 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 its salt, sulfonic acid group and its salt, sulfinyl group (eg 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, sulfanilyl group, acetylsulfanylyl group, etc.), oxysulfonyl group (eg methoxysulfonyl group, ethoxysulfonyl group, phenoxysulfonyl group, acetoacetate Aminophenoxysulfonyl group, pyridyloxysulfonyl group etc.), thiosulfonyl group (eg methylthiosulfonyl group, ethylthiosulfonyl group, phenylthiosulfonyl group, acetaminophenylthiosulfonyl group, pyridylthiosulfonyl group etc.), aminosulfonyl group (eg Sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, phenylsulfamoyl group, acetaminophenyl group 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,
Heptafluoropropyl group) and the like.

As Ar in the above formula (3), a strong electron-withdrawing characteristic group such as a nitro group is substituted for an electron-resonable position of the aromatic hydrocarbon group or the aromatic heterocyclic group, and the electron-withdrawing group is substituted. -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 and the like) are particularly preferable.

Φ in the above formula (3) is a substituted or unsubstituted nitrogen-containing nitrogen atom having a pyridine type nuclear nitrogen atom (-N =) and having a bond to 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 [Chemical Formula 7] below.

[0026]

[Chemical 7]

(However, in the formula, = Z- is = C (R ₅ ).
-Or = N-. Two Zs adjacent to each other
May be condensed. X represents an O atom, an S atom, or an NR ₃ group. R ₃ and R ₅ have the same meanings as R _{1 to} R ₄ and represent a substituted or 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 group, 2-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 6-
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-naphthoimidazolyl group, 3-pyrazolyl group, 3 -Indazolyl group, 2-
Oxazolyl group, 4-oxazolyl group, 2-benzoxazolyl group, 2-naphthoxazolyl group, 3-isoxazolyl group, 3-benzisoxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 2- Benzothiazolyl group, 2-naphthothiazolyl group, 2-selenazolyl group, 2
-Benzoselenazolyl group, 2-terrazolyl group, 2-benzoterrazolyl 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-
Examples thereof include a tetrazol-4-yl group. Moreover, these nitrogen-containing aromatic heterocyclic groups may be substituted with the substituents exemplified in the description of R _{1 to} R ₄ .

Incidentally, as φ in the equation (3),
It is preferable that the acid dissociation constant pKa of the chemical species protonated to the pyridine-type nuclear nitrogen atom (-N =) is between 1 and 10. More specifically, 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 and the like are particularly preferable.

The azomethine derivative represented by the formulas (1) and (2) according to the present invention is obtained by reacting a carbonyl compound such as an aldehyde with an acyl hydrazide under an acid catalyst such as acetic acid.
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 dehydration condensation of a carbonyl compound such as aldehyde with an N-aryl (or heteroaryl) hydrazine compound in the presence of an acid catalyst such as acetic acid. Easily synthesized.

[0032]

The azomethine derivative represented by the above general formulas (1) and (2) is an aromatic hydrocarbon substituted with an electron-withdrawing substituent (electron-withdrawing heterocyclic group or electron-withdrawing characteristic group) as an Ar group. Group or aromatic heterocyclic group), the polarization due to resonance effect (mesomeric polarization)
, And the non-linearity at the molecular level is improved. Further, since it has a hydrogen-bonding substituent in its molecular skeleton, it is easy to have a non-centrosymmetric crystal structure due to intermolecular hydrogen bonding, and excellent non-linearity is secured. Furthermore, the light absorption band of the azomethine derivative exists on the short wavelength side. As a result, the organic non-linear optical material made of this azomethine derivative exhibits excellent non-linearity, has good light transmittance in the blue wavelength range, and can efficiently generate a harmonic wave.

Similarly, the hydrazone derivative represented by the general formula (3) has an imino group (--NH) in the hydrazone skeleton.
-) Acts as an electron-donating group, and has an electron-withdrawing substituent as an Ar group (an aromatic hydrocarbon group or an aromatic heterocyclic group substituted with an electron-withdrawing heterocyclic group or an electron-withdrawing characteristic group). By introducing, the polarization due to the resonance effect (mesomeric polarization) is increased, and the nonlinearity at the molecular level is improved. In addition, the imino group (-NH
-) 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 have a stable intermolecular hydrogen bond. Since it is formed, it is easy to have a non-centrosymmetric crystal structure, and excellent nonlinearity is secured. Further, the light absorption band of the hydrazone derivative exists on the short wavelength side, and the organic nonlinear optical material made of this hydrazone derivative exhibits excellent nonlinearity. Moreover, the melting point is high due to the stable intermolecular hydrogen bond, and the problem of heat resistance, which has been a drawback of the conventional organic nonlinear optical material, can be overcome.

[0034]

EXAMPLES The present invention will now 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 mmo
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 the mixture is heated under reflux for 2 hours. After allowing to cool, it is concentrated under reduced pressure, and the precipitated crude crystals are thoroughly washed with water.
The crude crystal was collected by suction filtration and recrystallized from a solvent such as ethanol or tetrahydrofuran to obtain the target 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,
2-nitrobenzaldehyde 3.3 g (22 mmol)
Target 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,
4-cyanobenzaldehyde 2.9 g (22 mmol)
Target compound 3 was obtained by the same method 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,
Methyl 4-formylbenzoate 3.6 g (22 mmol)
Target 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 mmo
Target compound 5 was obtained by the same method as in Synthesis Example 1 except that 1) was used. 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-carboxaldehyde 3.
Target compound 6 was obtained in the same manner as in Synthesis Example 1 except that 4 g (22 mmol) was used. 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 nitrogen sulfur calculated value 39.43% 3.31% 19.71% 15.04% analysis value 39.33% 3.37% 19.47% 15.13% [Synthesis example 7] 4 Synthesis of nitrobenzaldehyde benzoylhydrazone (Compound 7) Benzhydrazide 2.7 instead of acetohydrazide
Target compound 7 was obtained in the same manner as in Synthesis Example 1 except that g (20 mmol) was used. 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 2.
Target compound 8 was obtained in the same manner as in Synthesis Example 1 except that 8 g (20 mmol) was used. 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 2.
Target compound 9 was obtained in the same manner as in Synthesis Example 1 except that 8 g (20 mmol) was used. 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 mmo
Using 1) and 5-nitrothiophene-2-carboxaldehyde (3.4 g, 22 mmol), the target compound 10 was obtained by the same method 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 value 47.82% 2.92% 20.28% 11.60% Analytical value 47.77% 2.94% 20.17% 11.65% [Synthesis example 11] 4 -Nitrobenzaldehyde Thiobenzoylhydrazone (Compound 11) Synthesis

The target compound 11 was obtained in the same manner as in Synthesis Example 1 except that 3.0 g (20 mmol) of thiobenzoylhydrazide 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 hydrogen nitrogen sulfur calculated value 58.94% 3.89% 14.73% 11.24% analytical value 59.23% 3.72% 14.70% 11.20% [Synthesis example 12] 5 Of 2-nitro-2-furaldehyde thiobenzoylhydrazone (Compound 12)

Thiobenzohydrazide 3.0 g (20 mm
ol) and 3.1 g of 5-nitro-2-furaldehyde.
The target compound 12 was obtained by the same method as in Synthesis Example 1 using (22 mmol). 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 hydrogen nitrogen sulfur calculated value 52.36% 3.30% 15.26% 11.65% analytical value 52.17% 3.29% 15.55% 11.67% [Synthesis example 13] 5 Of 2-nitrothiophene-2-carboxaldehyde thiobenzoylhydrazone (Compound 13)

Thiobenzohydrazide 3.0 g (20 mm
Ol) and 5-nitrothiophene-2-carboxaldehyde (3.4 g, 22 mmol) were obtained in the same manner as in Synthesis Example 1 to obtain the target compound 13. 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 value 49.47% 3.11% 14.42% 22.01% Analytical value 49.10% 3.00% 14.59% 22.24% [Synthesis example 14] 4 -Synthesis of nitrobenzaldehyde acetamidrazone (compound 14)

2.5 g of ethyl acetamidate (hydrochloride)
(20 mmol), 4-nitrobenzaldehyde hydrazone 3.3 g (22 mmol), triethylamine 2.
8 ml (2.0 g, 20 mmol) of ethanol 20 m
Dissolve in 1 and heat to reflux for 30 minutes. After allowing to cool, it is concentrated under reduced pressure, and the precipitated crude crystals are thoroughly washed with water. The crude crystal was collected by suction filtration and recrystallized from a solvent such as ethanol or tetrahydrofuran to obtain the target 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 target 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 in place of 4-nitrobenzaldehyde hydrazone.
Got 5. 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 nitrogen sulfur calculated value 39.62% 3.80% 26.40% 15.11% analytical value 39.76% 3.70% 26.26% 15.00% or more of compounds 1 to 15 The structural formulas of are shown in Tables 1 to 3. (B) Synthesis Example of Hydrazone Derivative [Synthesis Example 16] 2-Pyridylcarboxaldehyde-4
-Synthesis of nitrophenylhydrazone (Compound 16)

3.1 g of 4-nitrophenylhydrazine
(20 mmol) and 2-pyridinecarboxaldehyde 2.0 ml (2.25 g, 21.0 mmol) were dissolved in ethanol 50 ml, and acetic acid 1 ml (17.5 mm).
ol) is added and the mixture is heated under reflux for 2 hours. After allowing 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.
The target compound 16 shown in was obtained. In Table 4, the compounds are specified by displaying the structural formulas of introduced Ar and φ, and the chemical composition formula and the molecular weight are also shown.
Table 7 shows yields, elemental analysis results, and melting points. Synthesis of compounds 17-36

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

Azomethine derivatives of compounds 1 to 15 as Examples 1 to 15 and compound 1 to Examples 16 to 30
6 to 30, and 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 of ~ 36 were evaluated by the so-called powder method. That is, the crystal powder of each compound was crushed in an agate mortar and sieved to a particle size of 100.
A powder having a particle size of ˜150 μm was prepared, and the powder was sandwiched between slide glasses to obtain a measurement sample. The fundamental wave of the Nd-YAG laser (wavelength =
1.064 μm), and the second harmonic (S
The intensity of the (HG) 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 Table 7 and Table 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. 15 to 15 generate SHG several times to twenty times more than that of the urea of Comparative Example 1, and it is understood that they have excellent nonlinearity.

Further, as is clear from Tables 7 and 8, the hydrazone derivatives of Examples 16 to 30 were more than ten times to several tens times the hydrazone derivatives of Comparative Examples 3 to 8 and urea of Comparative Example 1. It can be confirmed that some SHG is generated,
It can be seen 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 conventionally used urea of Comparative Example 1 and MNA of Comparative Example 2. It can be seen that it has excellent properties.

Further, with respect to the azomethine derivatives of Examples 1, 3 and 10 and MNA of Comparative Example 2, 0.00
The result of measuring the visible-ultraviolet transmission spectrum of the 1M ethanol solution is shown in FIG.

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

[0062]

As described above in detail, the organic nonlinear optical material of the present invention can be synthesized very easily, has a high absorption of blue light on the short wavelength side of 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 generation of harmonics and optical bistable elements.

[Brief description of drawings]

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

Claims (1)

[Claims] 1. The following general formula (1): Alternatively, a tautomer of this compound represented by the following general formula (2): (In the formula, X is an O atom, an S atom, or NR ₃
Indicates a group. R _{1 to} R ₃ represent a substituted or unsubstituted aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group, alicyclic hydrocarbon group or hydrogen atom. 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. ) Or an azomethine derivative represented by the following general formula (3): (In the formula, R ₄ has the same meaning as R _{1 to} R ₃ and Ar has the same meaning as Ar. Φ has a pyridine-type nuclear nitrogen atom (-N =) and has the nuclear nitrogen atom. Represents a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group having a bond to a nuclear carbon atom adjacent to, and an organic non-linear optical material.