JP3345476B2 - 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. Williams et al., “Nonlinear Op
tical Properties of Organic and Polymeric Material
s "(American Chemical Society, 1983);
S. Chemla et al., “Nonlinear Optical Properti
es of Organic Molecules and Crystals ”(Academic P
ress, 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 comprises an α, β-unsaturated ketone derivative represented by the following general formula (1) or an amide derivative represented by the following general formula (2). It is characterized by the following.

[0008]

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[0009]

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R ₁ and R ₂ in the general formula (1) and R _{3 to} R ₆ in the general formula (2) each represent a substituted or unsubstituted aromatic hydrocarbon group, heterocyclic group, or aliphatic hydrocarbon group. , An alicyclic hydrocarbon group or a hydrogen atom. Here, the unsubstituted aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group and alicyclic hydrocarbon group introduced as R _{1 to} R ₆ are exemplified below.

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 restored ring 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 , Claman 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, Naphthymidazole 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, preteridine 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, Oxane 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 a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group,
Examples thereof include a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a cyclopentadienyl group, and a cyclohexadienyl group.

R _{1 to} R ₆ in the general formulas (1) and (2) are preferably those having little steric hindrance, and include a hydrogen atom or a lower alkyl group (for example, a methyl group, an ethyl group, a propyl group). Etc.) are particularly preferred.

The above general formulas (1) and (2)
In the above, the aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group or alicyclic hydrocarbon group introduced as R _{1 to} R ₆ may be substituted with the following substituents.
For example, di-substituted amino group (dimethylamino group, diethylamino group, dibutylamino group, ethylmethylamino group,
Butylmethylamino, diamylamino, dibenzylamino, diphenethylamino, diphenylamino, ditolylamino, dixylylamino, methylphenylamino, benzylmethylamino, etc.), mono-substituted amino (methylamino , Ethylamino group, propylamino 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-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, sulfanylamino group, acetylsulfanylamino group, etc.), ammonium group (trimethyl Nmonio group, ethyl dimethyl ammonio group, dimethylphenyl ammonio group, pyridinio group, etc. quinolinio group), an amino group, an oxy amino 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, methylphenyl Hydrazino group), mono-substituted hydrazino group (methylhydrazino group, phenylhydrazino group, pyridylhydrazino group, benzylidenehydrazino group, etc.), hydrazino group, azo group (phenylazo group, pyridialazo group, thiazolylazo group, etc.), Azoxy, amidino, cyano, cyanato, thiocyanato, nitro, nitroso, oxy (methoxy, ethoxy, propoxy, butoxy, hydroxyethoxy, phenoxy, naphthoxy, pyridyloxy, Cheer A hydroxy group, a thio group (a methylthio group, an ethylthio group, a phenylthio group, a pyridylthio group, a thiazolylthio group, etc.), a mercapto group, a halogen group (a fluoro group, a chloro group, a bromo group, an iodo group), Carboxyl group and its salt, oxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, pyridyloxycarbonyl group, etc.), aminocarbonyl group (carbamoyl group, methylcarbomoyl group, phenylcarbamoyl group, pyridylcarbamoyl group, carbazoyl Group, allophanoyl group, oxamoyl group, succinamoyl group, etc.), thiocarboxyl group and its salt, dithiocarboxyl group and its salt, thiocarbonyl group (methoxythiocarbonyl group, methylthioca Carbonyl, methylthiothiocarbonyl, etc.), acyl (formyl, acetyl, propionyl, acryloyl, benzoyl, cinnamoyl, pyridinecarbonyl, thiazolecarbonyl, trifluoroacetyl, etc.), thioacyl (thioformyl) Group, thioacetyl group, thiobenzoyl group, pyridinethiocarbonyl group, etc.), sulfinic acid group and its salt, sulfonic acid group and its salt, sulfinyl group (methylsulfinyl group, ethylsulfenyl group, phenylsulfinyl group, etc.), sulfonyl group (Mesyl group, ethylsulfonyl group,
Phenylsulfonyl group, pyridylsulfonyl group, tosyl group, tauryl group, trifluoromethylsulfonyl group, sulfanyl group, acetylsulfanylyl group, etc.), oxysulfonyl group (methoxysulfonyl group, ethoxysulfonyl group, phenoxysulfonyl group, acetaminophenoxy) Sulfonyl group, pyridyloxysulfonyl group, etc.), thiosulfonyl group (methylthiosulfonyl group, ethylthiosulfonyl group, phenylthiosulfonyl group, acetaminophenylthiosulfonyl group, pyridylthiosulfonyl group, etc.), aminosulfonyl group (sulfamoyl group, methyl Sulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, phenylsulfamoyl, acetaminophenylsulfamoyl , Pyridylsulfamoyl group, etc.), halogenated alkyl groups (chloromethyl group, bromomethyl group, fluoromethyl group, dichloromethyl group, dibromomethyl group, difluoromethyl group, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl Group), hydrocarbon group (alkyl group, aryl group, alkenyl group, alkynyl group, etc.), heterocyclic group, organosilicon group (silyl group, disilanyl group, trimethylsilyl group,
Triphenylsilyl group, etc.).

Az in the general formula (1) is a substituted or unsubstituted electron-donating nitrogen-containing aromatic heterocyclic group having a pyrrole-type nuclear nitrogen atom (-NH-) bonded to a hydrogen atom. That is, Az particularly has an unsubstituted imino group in the skeleton constituting the aromatic heterocyclic structure.

The unsubstituted electron-donating nitrogen-containing aromatic heterocyclic group introduced as Az includes, for example, a pyrrole ring group,
Indole ring group, pyrazole ring group, indazole ring group,
Imidazole ring group, benzimidazole ring group, 1,2,2
Examples thereof include a 3-triazole ring group, a 1,2,4-triazole ring group, and a tetrazole ring group. Further, a substituent may be introduced into these electron-donating nitrogen-containing aromatic heterocyclic groups as described above. Examples of such a substituent include those represented by the general formulas (1) and (2). R in
Examples of the substituent of _{1 to} R ₆ include those exemplified. As Az in the general formula (1), a pyrrole ring group, an indole ring group, a pyrazole ring group, an imidazole ring group, and a benzimidazole ring group are particularly preferable.

In the general formulas (1) and (2), φ has a pyridine type nuclear nitrogen atom (-N =);
And a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group having a bond at a nuclear carbon atom adjacent to the nuclear nitrogen atom.
The structural formula of φ is shown below.

[0020]

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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 ₆ .

In the above general formulas (1) and (2), φ is a value in which the acid dissociation constant pKa of the chemical species protonated to the pyridine type nitrogen atom (-N =) is 1 to 10. Are preferred. More specifically, 2-pyridyl group, 2-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 6-phenathridyl group, 3-pyridazinyl group, 1-phthalazinyl group, 3-cinnolinyl group, 2-pyrimidinyl group A 4-pyrimidinyl group, a 2-quinazolinyl group, a 4-quinazolinyl group, a 2-pyrazinyl group, a 2-quinoxalinyl group, a 2-imidazolyl group, a 4-imidazolyl group, a 2-benzimidazolyl group,
Particularly preferred are a 3-pyrazolyl group, a 3-indazolyl group, a 2-thiazolyl group, a 4-thiazolyl group, a 2-benzothiazolyl group and the like.

[0023] Ar in the general formula (2), the electron withdrawing properties substituted aromatic hydrocarbon group by group, aromatic heterocyclic group, or they are a single bond, -CR ₃ = CR ₄ -,
_{-CR 5 = N -, - N} = N -, - polycyclic aromatic group formed by binding O- or -S- in such π via a bond that will not cut the electron conjugated system. Examples of the aromatic hydrocarbon group and the aromatic heterocyclic group include those exemplified in the description of R _{1 to} R ₆ . Further, these aromatic hydrocarbon group, aromatic heterocyclic group and polycyclic aromatic group may be further substituted with the substituents exemplified in the description of R _{1 to} R ₆ .

The electron-withdrawing characteristic groups introduced into these aromatic hydrocarbon groups, aromatic heterocyclic groups or polycyclic aromatic groups include nitro groups, nitroso groups, cyano groups, cyanato groups, thiocyanato groups, halogens, and the like. Groups (fluoro group, chloro group, bromo group, iodo group), carboxyl group and salts thereof, oxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group,
A pyridyloxycarbonyl group, an aminocarbonyl group (eg, a carbamoyl group, a methylcarbomoyl group, a phenylcarbamoyl group, a pyridylcarbamoyl group, a carbazoyl group, an allofanoyl group, an oxamoyl group, an succinamoyl group), a thiocarboxyl group and a salt thereof, Carboxyl group and its salt, thiocarbonyl group (for example, methoxythiocarbonyl group, methylthiocarbonyl group, methylthiothiocarbonyl group, etc.), acyl group (for example, formyl group, acetyl group, propionyl group,
Acryloyl group, benzoyl group, cinnamoyl group, pyridinecarbonyl group, thiazolecarbonyl group, trifluoroacetyl group, etc., thioacyl group (eg, thioformyl group, thioacetyl group, thiobenzoyl group, pyridinethiocarbonyl group, etc.), sulfinic acid group and the like Salts, sulfonic acid groups and salts thereof, sulfinyl groups (eg, methylsulfinyl group, ethylsulfenyl group, phenylsulfinyl group, etc.), sulfonyl groups (eg, mesyl group, ethylsulfonyl group, phenylsulfonyl group, pyridylsulfonyl group, tosyl group, Tauryl group, trifluoromethylsulfonyl group, sulfamoyl group, methylsulfamoyl group, sulfanyl group, acetylsulfanylyl group, etc.), oxysulfonyl group (for example, methoxysulfonyl group, ethoxy Cis-sulfonyl group, phenoxysulfonyl group, acetaminophenoxysulfonyl group, pyridyloxysulfonyl group, etc., thiosulfonyl group (for example, methylthiosulfonyl group, ethylthiosulfonyl group, phenylthiosulfonyl group, acetoaminophenylthiosulfonyl group, pyridylthiosulfonyl Group),
Aminosulfonyl group (for example, sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, phenylsulfamoyl group, acetaminophenylsulfamoyl group, pyridylsulfamoyl group) Group), halogenated alkyl groups (for example, chloromethyl group, bromomethyl group,
Fluoromethyl, dichloromethyl, dibromomethyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, etc.)
And the like.

The α, β-unsaturated ketone derivative according to the present invention is easily synthesized by dehydrating a carbonyl compound such as an aldehyde to an acylheteroaryl compound in the presence of a base catalyst such as sodium hydroxide.

The amide derivative according to the present invention is easily synthesized by, for example, dehydrating and condensing an aromatic amine compound with a carboxylic acid compound in the presence of a condensing agent such as dicyclohexylcarbodiimide in a methylene chloride solvent.

[0027]

The α, β-unsaturated ketone derivative according to the present invention comprises:
Due to the fact that the carbonyl group (> C = 0) and the Az group in the general formula (1) have an electron-withdrawing property and an electron-donating property, respectively, polarization due to a resonance effect (mesomeric polarization)
And the nonlinearity at the molecular level is improved. Also,
A hydrogen atom bonded to a pyrrole-type nuclear nitrogen atom (-NH-) in the Az group, an oxygen atom of the carbonyl group (> C = 0) and a pyridine-type nuclear nitrogen atom (-N =) in the φ group. Since a stable intermolecular hydrogen bond is formed during the reaction, a non-centrosymmetric crystal structure can be easily formed and excellent nonlinear optical characteristics can be secured.

Further, the light absorption band of the α, β-unsaturated ketone derivative exists on the short wavelength side, and the organic nonlinear optical material composed of the α, β-unsaturated ketone derivative exhibits excellent nonlinearity. In addition, the melting point is high due to stable intermolecular hydrogen bonding, and the problem of heat resistance which has been a drawback of the conventional organic nonlinear optical material can be overcome.

Similarly, the amide derivative according to the present invention is characterized by the Ar group and the acylamino group (-N
Since H-CO-) has an electron-withdrawing property and an electron-donating property, polarization (mesomeric polarization) due to the resonance effect increases, and nonlinearity at the molecular level improves.
Further, since a stable intermolecular hydrogen bond is formed between the hydrogen atom of the acylamino group (—NH—CO—) and the oxygen atom and the pyridine type nitrogen atom (—N =) in the φ group, A non-centrosymmetric crystal structure is easily obtained, and excellent nonlinear optical characteristics are secured.

Further, the light absorption band of the amide derivative exists on the short wavelength side. As a result, the organic nonlinear optical material comprising the amide derivative exhibits excellent nonlinearity, has good light transmittance in a blue wavelength region, and can efficiently generate harmonics.

[0031]

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 of α, β-unsaturated ketone derivative First, 3- (3-indolyl) -1- (2-pyridyl) propenone shown as Compound 1 in Table 1 was synthesized as described below.

That is, 4.3 g (29.6 mmol) of 3-indolecarbaldehyde and 3.5 ml (3.78 g, 31.2 mmol) of 2-acetylpyridine are dissolved in 60 ml of ethanol, and 50% (13.5N) water is added. 6 ml (81.0 mmol) of an aqueous potassium oxide solution is added little by little, and the mixture is stirred at room temperature for one day. Acetic acid (17.
5N) 500 ml of water containing 10 ml is added little by little with stirring and left overnight. The precipitated crude crystals were collected by suction filtration, and recrystallized from a solvent such as ethanol or acetone to obtain the intended compound 1. In Table 1, the compounds were specified by displaying the structural formulas of R ₁ , R ₂ , Az and φ introduced, and the chemical composition formula and molecular weight of the compounds were also described. Table 2 shows the yield and the results of elemental analysis of the obtained compound.

Further, Compounds 2 to 11 shown in Table 1 were synthesized in the same manner as in Compound 1 using the corresponding aldehyde compound and acylheteroaryl compound or acylaryl compound to obtain a target compound. Compounds 9 to 11 in Table 1 (Comparative Examples 1 to 3)
Although similar to the α, β-unsaturated ketone derivative according to the present invention, the compound is outside the scope of the present invention because the nitrogen-containing aromatic heterocyclic group φ described above is not introduced. Table 2 similarly shows the yields and the results of elemental analysis for these compounds.

(B) Synthesis of Amide Derivative First, 4-nitro-N-
(2-Pyridinecarbonyl) aniline was synthesized as shown below.

That is, 4.50 g of 4-nitroaniline
(32.6 mmol) was dissolved in 100 ml of methylene chloride, and cooled to 0 ° C. or lower.
l (3.36 g) are added with stirring. 2 in this solution
-Pyridine carboxylic acid 3.70 g (30.1 mmol)
And 100 ml of a methylene chloride solution containing 6.80 g (33.0 mmol) of dicyclohexylcarbodiimide cooled to 0 ° C., and the mixture is reacted at 0 ° C. for 1 hour and then at room temperature for 5 hours. After the reaction, the insoluble N, N'-dicyclohexylurea is removed by suction filtration, washed sufficiently with methylene chloride, and the filtrate is treated with activated carbon. Then
After removing activated carbon by filtration through a celite bed with suction, the filtrate was concentrated under reduced pressure, and the precipitated crude crystals were recrystallized from a hot ethanol solvent to obtain the desired compound 12. The chemical composition formula and molecular weight of the obtained compound are also shown in Table 3,
Table 4 shows the yield and the results of elemental analysis.

Compounds 13 to 21 shown in Table 3 were also synthesized in the same manner as Compound 12 using the corresponding aromatic amine compound and carboxylic acid compound.
The desired compound was obtained. Compounds 19 to 2 in Table 3
Compound No. 1 (Comparative Examples 5 to 7) is similar to the amide derivative according to the present invention, but does not incorporate the nitrogen-containing aromatic heterocyclic group φ described above, and is a compound outside the scope of the present invention. Table 4 similarly shows the yields and the results of elemental analysis for these compounds.

(C) Measurement of Nonlinear Optical Properties Compounds 1 to 8 which are α, β-unsaturated ketone derivatives according to the present invention as Examples 1 to 8 and compounds which are similar compounds thereof as Comparative Examples 1 to 3 For 9 to 11 and Comparative Example 4, for urea, the electronic state of each molecule is calculated by MOPAC which is a general-purpose molecular orbital calculation method (using the MNDO-PM3 method as the calculation method), and the secondary molecular hyperpolarizability β is calculated. did. Table 2 shows values of β _XXX which is the maximum component of β. Here, as the MOPAC program,
"PC MOPAC" manufactured by Toray System Center Co., Ltd.
/ 386 Ver. 6 ”and β is the Kurtz-Stewart-Diet built into MOPAC.
The er method was used to numerically differentiate the heat of formation and the bithermal moment of a molecule by an electric field. At this time, the calculated coordinates used were those obtained by converting the calculated values of the optimal conformation by the MNDO-PM3 method such that the center of gravity of the molecule coincided with the origin and the principal axis of inertia coincided with the x-axis. However, this MOPA
The hyperpolarizability obtained by the calculation method incorporating C corresponds to the hyperpolarizability when the frequency of the incident electric field = 0.

As is clear from Table 2, the α, β-unsaturated ketone derivatives of Examples 1 to 8 have a secondary molecular hyperpolarizability β of about 70 to 140 times that of the urea of Comparative Example 4. Was. This β is an index of the second-order nonlinearity at the molecular level, and a compound having a larger β shows a large second-order nonlinearity at the molecular level. Therefore, it is understood that the α, β-unsaturated ketone derivative according to the present invention has large second-order nonlinearity at a molecular level.

Next, the α, β-unsaturated ketone derivatives of Examples 1 to 8 and the α, β-unsaturated ketone derivatives of Comparative Examples 1 to 3, and the compounds 12 to 18 as Examples 9 to 15
Amide derivatives and compounds 19- as Comparative Examples 5-7
Amide derivative of No. 21, urea of Comparative Example 4, 4-nitroaniline as Comparative Example 8, and MNA as Comparative Example 9
(2-Methyl-4-nitroaniline) was examined for its second-order nonlinear optical characteristics by the 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 formed by sieving, and the powder sandwiched between slide glasses was used as a measurement sample. The sample for measurement is irradiated with a fundamental wave (wavelength = 1.64 μm) of an Nd-YAG laser, and the second harmonic intensity in the reflected light is specified by the second harmonic intensity of the urea (Comparative Example 4) powder. The results are shown in Tables 2 and 4.

As is clear from Table 2, the α, β-unsaturated ketone derivatives of Examples 1 to 8 are the same as those of Comparative Examples 1 to 3.
-Relative to the unsaturated ketone derivative and the urea of Comparative Example 4,
SHG was generated several times to several tens times, and it was confirmed that the crystal had excellent secondary nonlinear optical characteristics even in a crystalline state.

As apparent from Table 4, Examples 9 to 1 were used.
The amide derivative of No. 5 generates SHG about ten times or more to several tens times that of the amide derivatives of Comparative Examples 5 to 7 and the urea of Comparative Example 4 and the 4-nitroaniline of Comparative Example 8,
It was confirmed that the crystalline state had excellent second-order nonlinear optical characteristics.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

Furthermore, the α, β-unsaturated ketone derivatives of Examples 1 and 6, the amide derivatives of Examples 11, 13 and 15, and the MNA of Comparative Example 9 were 0.001
The result of measuring the visible-ultraviolet transmission spectrum of the M ethanol solution is shown in FIG. As is apparent from FIG. 1, the α, β-unsaturated ketone derivatives of Examples 1 and 6, and the amide derivatives of Examples 11, 13 and 15 were obtained by using the MNA of Comparative Example 9 widely known as an organic nonlinear optical material. compared to,
It can be confirmed that the light absorption band exists on the short wavelength side and the light transmittance is high even in the blue wavelength region. Further, for the α, β-unsaturated ketone derivative and amide derivative of this example other than these, the visible-ultraviolet transmission spectrum of a 0.001 M ethanol solution was measured.
It was present on the shorter wavelength side than NA. This indicates that the α, β-unsaturated ketone derivative and the amide derivative according to the present invention have good light transmittance in the visible region.

[0047]

As described in detail above, the organic nonlinear optical material of the present invention can be synthesized very easily, has a high light absorption and a high transmittance of blue light on the short wavelength side, and has excellent nonlinearity.
The harmonic can be generated efficiently. 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 0.001M of the α, β-unsaturated ketone derivatives of Examples 1 and 6 of the present invention, the amide derivatives of Examples 11, 13 and 15, and the MNA of Comparative Example 9.
It is a visible-ultraviolet transmission spectrum figure of an ethanol solution.

Claims (1)

(57) [Claims] An α, β-unsaturated ketone derivative represented by the following general formula (1): Or an amide derivative represented by the following general formula (2): An organic nonlinear optical material, comprising: