JP2835099B2 - Organic nonlinear optical material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to a novel organic nonlinear optical material.

(Prior Art) Communication and information processing using light as an information carrier are fundamental technologies for the development of an information society. In optical communication and optical information processing, a technique for controlling the wavelength, amplitude, and phase of laser light, such as harmonic generation, optical switching, and optical mixing, is indispensable. In order to perform such light control at high speed, it is advantageous to use the nonlinear optical effect of a substance. Until now, inorganic crystals have been used as nonlinear optical materials, but the nonlinear optical effects of these inorganic crystals have not been sufficient. On the other hand, in recent years, many organic compounds having a much larger nonlinear optical constant than inorganic crystals and having excellent durability against light damage have been found. Regarding these organic nonlinear optical materials, for example, DJ Williams et al., “Non-lin
ear Optical Properties of Organic and Polymeric Ma
terials ", (American Chemical Society, 1983). The molecular structural features of the organic nonlinear optical materials mentioned here include electron-donating functional groups at both ends of a π-electron system such as a benzene ring. The point is that an electron-accepting functional group is bonded.

However, the organic nonlinear optical material having such a molecular structure has a centrally symmetric structure upon crystallization due to the presence of the electric dipole in the ground state, and the large nonlinearity exhibited by one molecule is easily offset as a whole crystal. There was a problem. Also, if the spatial extent of the π electron system is expanded,
Although the nonlinearity increases, on the other hand, the absorption band of the molecule itself overlaps with the wavelength of the fundamental wave or the overtone, thereby causing an effect that efficient generation of the overtone is prevented.

(Problem to be Solved by the Invention) The present invention has been made in order to solve the above-mentioned problem, and provides an organic nonlinear optical material which exhibits excellent nonlinearity and can efficiently generate harmonics. With the goal.

[Constitution of the Invention] (Means for Solving the Problems) The organic nonlinear optical material of the present invention has the general formula (I) (Wherein, in the formula (I), Z ₁ is O atom, S atom, Se atom, Te atom, SO ₂ group or NR ₁
Represents a group.

Z ₂ represents an N atom or a CR ₂ group.

Y represents an O atom, an S atom or an NR ₃ group.

The case where Z ₁ is an O atom, Z ₂ is an N atom, and Y is an O atom is excluded.

X represents a CR ₄ R ₅ group, an NR ₆ group, an O atom or an S atom.

R, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ may be the same or different and are an unsubstituted or substituted heterocyclic group, aromatic hydrocarbon group, aliphatic hydrocarbon Represents a group or an alicyclic hydrocarbon group, a characteristic group, or an H atom. Incidentally, it may form a hydrocarbon ring or heterocyclic ring in R ₄ and R _5. ) Characterized by comprising a heterocyclic compound represented by the following formula:

In the general formula (I), the heterocyclic compound serving as the basic skeleton determined by the combination of Z ₁ , Z ₂ and Y includes:
For example, 5-thiazolone, 5-imidazolone, 5-thiazolone-1,1-dioxide, 3H-furan-2-one, 3H-thiophen-2-one, 3H-pyrrol-2-one, 3-thiophen-2-one A heterocyclic ketone compound such as -1,1-dioxide (shown in A to H in Table 1); a heterocyclic thioketone compound in which the O atom of the carbonyl group of the compound is replaced with an S atom; Heterocyclic Schiff compounds in which atoms are substituted with NR ₃ groups are mentioned.

In the general formula (I), examples of the unsubstituted heterocyclic group, aromatic hydrocarbon group, aliphatic hydrocarbon group, and alicyclic hydrocarbon group introduced as R and R _{1 to} R ₆ are shown below.

As the heterocyclic group, for example, a pyrrole ring group, a pyrroline ring group, a pyrrolidine ring group, an indole ring group, an indole ring group, an indoline ring group, an isoindoline ring group, an indolizine ring group, a carbazole ring group, a 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, naphthoimidazole ring group, oxazole ring group, oxazoline ring group, oxazoline ring group, benzoxazole ring group, benzoxazolidine 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, benzooxadiazole ring group, benzothiadiazole ring group, tetrazole ring group, purine ring group, pyridine ring group, piperidine ring group, quinoline ring Group, a Quinoline 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, benzooxole ring group, dioxane ring group, benzodioxane ring group,
Dithiosolan ring group, benzodithiosol 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, trioxane ring group, thiane ring group, Examples thereof include a triatin 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.

As the aromatic hydrocarbon group, for example, phenyl group, naphthyl group, anthryl group, phenanthryl group, tetralinyl group, azulenyl group, biphenylenyl group, acenaphthylenyl group, acenaphthenyl group, fluorenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, picenyl group ,
Perylenyl group, benzopyrenyl group, rubicenyl group, coronenyl group, ovalenyl group, indenyl group, pentalenyl group, heptalenyl group i, indacenyl group, phenalenyl group, fluoranthenyl group, acephenanthrenyl group,
Aceanthrenyl, naphthacenyl, preyadenyl, pentaphenyl, pentacenyl, tetraphenylenyl, hexaphenyl, hexacenyl, trinaphthenyl, heptaphenyl, heptaenyl,
And a pyranthrenyl group.

As the aliphatic hydrocarbon group, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, t
ert-pentyl group, isopentyl group, neopentyl group,
Hexyl group, isohexyl group, heptyl group, octyl group i, nonyl group, decyl group, vinyl group, allyl group, isopropenyl group, propenyl group, methallyl group, crotyl group,
Ethynyl group, propynyl group, butenyl group, butynyl group,
Examples include a pentenyl group, a pentynyl group, and a butadienyl group.

Examples of the alicyclic hydrocarbon group include, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclopentadienyl group , Cyclohexadienyl group and the like.

In the general formula (I), the characteristic groups introduced as R and R _{1 to} R ₆ are exemplified below. For example, di-substituted amino groups (dimethylamino group, diethylamino group, dibutylamino group, ethylmethylamino group, butylmethylamino group,
Diamylamino group, dibenzylamino group, diphenethylamino group, diphenylamino group, ditolylamino group, dixylylamino group, methylphenylamino group, benzylmethylamino group, etc.), mono-substituted amino group (methylamino group, ethylamino group, Propylamino group, isopropylamino group, tert-butylamino group, anilino group, anisidino group, phenetidino group, toluidino group, xyridino group, pyridylamino group, thiazolylamino group, benzylamino group, benzylideneamino group, etc., cyclic amino group (pyrrolidino group) 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, cinnamo Ylamino group, pyridinecarbonylamino group, trifluoroacetylamino group, etc.)
Amino group (trimethylamino group, ethyldimethylamino group, dimethylphenylamino group, etc.), amino group, hydroxyamino group, ureido group, semicarbazide group, carbazide group, disubstituted hydrazino group (dimethylhydrazino group, diphenylhydrazino group, Methylphenylhydrazino group, etc., mono-substituted hydrazino group (methylhydrazino group, phenylhydrazino group, pyridylhydrazino group, benzylidenehydrazino group, etc.), hydrazino group, azo group (phenylazo group, pyridylazo group, thiazolylazo group, etc.) ), Azoxy group, amidino group, aminocarbonyl group (carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, pyridylcarbamoyl group, carbazoyl group, allophanoyl group, oxamoyl group, succinamoyl group, etc.), shea Group, cyanato group, thiocyanato group, nitro group, nitroso group, oxy group (methoxy group, ethoxy group, propoxy group, butoxy group, hydroxyethoxy group, phenoxy group, naphthoxy group, pyridyloxy group, thiazolyloxy group, acetoxy group, etc.) , Hydroxy group, thio group (methylthio group, ethylthio group, phenylthio group, pyridylthio group, thiazolylthio group, etc.),
Mercapto group, halogen group (fluoro group, chloro group, bromo group, iodo group), carboxyl group and its salt, oxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, pyridyloxycarbonyl group, etc.), thiocarboxyl Group, dithiocarboxyl group, thiocarbonyl group (methoxythiocarbonyl group, methylthiocarbonyl group, methylthiothiocarbonyl group, etc.), acyl group (formyl group, acetyl group, propionyl group, acryloyl group, benzoyl group, cinnamoyl group, pyridinecarbonyl group , Thiazolecarbonyl, trifluoroacetyl, etc.), thioacyl (thioformyl, thioacetyl, thiobenzoyl, pyridinethiocarbonyl, etc.), sulfonic acid, sulfinyl (methyl Rufiniru group, ethylsulfinyl group, phenylsulfinyl group), a sulfonyl group (mesyl group, ethylsulfonyl group, phenylsulfonyl group,
Pyridylsulfonyl group, tosyl group, tauryl group, trifluoromethylsulfonyl group, sulfamoyl group, methylsulfamoyl group, sulfanyl group, acetylsulfanylyl group, etc.), hydrogen silicide group (silyl group, disilanyl group, trimethylsilyl group, Triphenylsilyl group, etc.).

In the general formula (I), the hydrocarbon ring and the hetero ring which may be formed by R ₄ and R ₅ are exemplified below. For example,
Cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclopentadiene, cyclohexadiene, indane, indene, tetralin, fluorene, ontron, oxane, thioxane, piperidine and the like. .

In the general formula (I), R, a heterocyclic group, an aromatic hydrocarbon group, an aliphatic hydrocarbon group introduced as R _{1 to} R ₆ ,
The alicyclic hydrocarbon group and the hydrocarbon ring which may be formed by R ₄ and R _5, and the heterocyclic ring, the groups exemplified as unsubstituted as described above are the characteristic groups described above, and the hydrocarbon group. (Alkyl, aryl, alkenyl, alkynyl, etc.),
It may be substituted by a heterocyclic group or the like.

Specific examples of the introduced substituent R in the general formula (I) are shown in R1 to R80 in Table 2.

Further, specific examples of the introduced substituent X in the general formula (I) are shown in Tables X1 to X160.

The heterocyclic compound represented by the general formula (I) can be easily synthesized by a dehydration condensation reaction between a compound such as a heterocyclic ketone having an active methylene group and a carbonyl compound or an isonitroso compound.

(Example) Hereinafter, an example of the present invention will be described.

First, a synthesis example of a typical heterocyclic compound used as the organic nonlinear optical material according to the present invention will be described below. In Tables 4 to 6, the synthesized compounds are represented by a basic skeleton (indicated by a symbol in Table 1), R (indicated by a chemical formula, an abbreviation or name of a chemical formula, and a symbol in Table 2). , And X (X is
When represented by CR ₄ R ₅ , it is represented by a combination of the chemical formulas of R ₄ and R ₅ , abbreviations or names of the chemical formulas and the symbols in Table 3).

Synthesis Example 1 (5-thiazolone derivative) 5-thiazolone compound or N-thioacylglycine 33
mmol, aldehyde 30 mmol, and anhydrous sodium acetate 2.5
(30 mmol) or 2.5 g (30 mmol) of anhydrous sodium hydrogen carbonate
To the mixture was added 10 ml (106 mmol) of acetic anhydride, and the mixture was heated with stirring at 100 ° C. for 1 hour, and then stirred at room temperature for 4 to 5 hours. After cooling, the reaction solution was poured into water, and the precipitated crystals were collected by filtration and washed with water. The crude crystals were recrystallized twice with acetic acid, ethanol, etc. to obtain the target compound. Table 4 shows the melting points of the compounds.

Synthesis Example 2 (5-imidazolone derivative) 5-imidazolone compound 33 mmol, aldehyde 30 mmol,
And 1.0 ml (10 mmol) of piperidine were dissolved in 20 ml of toluene or ethanol, and the mixture was heated and stirred at 70 ° C. for 5 hours. After cooling, the reaction solution was concentrated under reduced pressure, and the obtained residue was recrystallized twice with acetic acid, ethanol, and the like, to obtain a target compound. Fifth
The table shows the melting point of each compound.

Synthesis Example 3 (3H-furan-2-one derivative) 33 mmol of β-acylpropionic acid, 30 mmol of aldehyde,
And 2.5 g (30 mmol) of anhydrous sodium acetate or 2.5 g (30 mmol) of anhydrous sodium bicarbonate in 10 ml (106 mmol) of acetic anhydride.
l), and the mixture is heated and stirred at 100 ° C. for 1 hour.
Stir for 5 hours. After cooling, the reaction solution was poured into water, and the precipitated crystals were collected by filtration and washed with water. The crude crystals were recrystallized twice with acetic acid, ethanol, etc. to obtain the target compound. Table 6 shows the melting points of the respective compounds.

Using powder samples of the 5-thiazolone derivative, the 5-imidazolone derivative, and the 3H-furan-2-one derivative obtained in the synthesis cooling 1 to 3, the secondary nonlinear optical characteristics of these compounds 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 10 by a sieve.
The thickness was adjusted to 0 to 150 μm, and this was sandwiched between slide glasses to obtain a measurement sample. For these measurement samples, Nd
-Irradiate the fundamental wave (wavelength = 1.064 µm) of the YAG laser,
The intensity of the second harmonic in the reflected light was measured. A high purity urea powder was used as a reference sample, and the second harmonic intensity of each sample was normalized by the second harmonic intensity of the urea powder. Table 7 shows the measurement results. Table 7 also shows the absorption maximum wavelength of visible-ultraviolet light absorption in the solution state of each sample.

[Effect of the Invention] As described in detail above, the organic nonlinear optical material of the present invention is
It can be synthesized very easily, the light absorption is relatively short wavelength,
And it has excellent nonlinear optical characteristics. And the organic nonlinear optical material of the present invention shows a large nonlinear optical effect,
In addition, since harmonics can be generated efficiently, it 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.

Claims (1)

(57) [Claims] 1. The compound of the general formula (I) (Wherein, in the formula (I), Z ₁ represents an O atom, S atom, Se atom, Te atom, SO ₂ group or NR ₁ group. Z ₂ represents an N atom or CR ₂ group. Y is an O atom , S atom or NR ₃ group, excluding the case where Z ₁ is an O atom, Z ₂ is an N atom, and Y is an O atom, X is CR ₄ R ₅ group, NR ₆ group, O atom or S R, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ may be the same or different and are an unsubstituted or substituted heterocyclic group, an aromatic hydrocarbon group, Represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, a characteristic group, or an H atom, wherein R ₄ and R ₅ may form a hydrocarbon ring or a heterocyclic ring.) An organic nonlinear optical material, comprising a cyclic compound.