JPH0967324A - Benzoic acid ester derivative, aromatic polyamide and nonlinear optical material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new derivative having a specific substituent, capable of easily forming a single crystal having excellent nonlinear optical characteristics as a whole and a short absorption wavelength edge and giving a new low-molecular organic nonlinear optical material. SOLUTION: The objective derivative is expressed by formula I (X<1> and X<2> are each nitro or amino; Y<1> is a 1-12C hydrocarbon group; R<1> is H, a lower alkyl or together with Y<1> and bonding N atom form a ring; A<1> is H, an electron accepting group or a π-conjugated substituent containing an electron accepting group), e.g. 2-(N-methylanilino)ethyl 3,5-dinitrobenzoate. The objective derivative can be produced e.g. by the condensation reaction of a dinitrobenzoic acid or a dinitrobenzoyl halide of formula II (X is OH or a halogen) with an alcohol compound of formula III.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low molecular weight compound and a high molecular weight compound exhibiting a good second-order nonlinear optical effect, a nonlinear optical material comprising them, and a monomer thereof. More specifically, a novel benzoic acid derivative having a dye molecule, a low-molecular nonlinear optical material comprising the derivative, and the derivative synthesized as a monomer or a precursor thereof, containing two or more dye molecules in high density in a repeating unit. The present invention relates to a novel aromatic polyamide compound and a polymer nonlinear optical material comprising the polyamide compound.

[0002]

2. Description of the Related Art In recent years, as a new element in the field of optoelectronics, a search for a material for realizing a nonlinear optical element has been widely researched. In general, a nonlinear optical material is a material that exhibits a nonlinear response proportional to the square of the electric field of light or a power higher than that, and has various effects such as optical harmonic generation, optical rectification, optical mixing, optical parametric amplification, and Pockels effect. It is a new material that is known to bring about.

Conventionally, nonlinear optical materials include KH ₂ PO ₄ ,
Crystals of inorganic compounds such as NH ₄ H ₂ PO ₄ , LiNbO ₃ , KNbO ₃ , and LiIO ₃ have been used. However, recently, urea, p-nitroaniline, 2-methyl-4-nitroaniline (MNA),
-(N, N-dimethylamino) -4'-nitrostilbene (DAN
It has been found that organic compounds (dye) such as S) exhibit excellent nonlinear optical characteristics as compared with the above-mentioned inorganic compounds, and various organic nonlinear optical materials have been actively researched and developed.
The feature of the molecular structure of the organic nonlinear optical material known so far is that an electron donating group and an electron accepting group are bonded to both ends of a π-electron molecule such as a benzene ring. In addition, organic nonlinear optical materials do not involve lattice vibration with respect to optical response because the origin of nonlinearity is π electrons in the molecule, and therefore have a faster response and a larger nonlinear optical constant than inorganic materials. It is possible to combine those having different absorption wavelength regions. (For example, edited by Masao Kato and Hachiro Nakanishi, "Organic Nonlinear Optical Materials", CMC (1985
Year); edited by The Chemical Society of Japan, "Organic Materials for Nonlinear Optics", Institute of Press (1992); Seth R. Marder et al., "Materials for Nonlinear Optics", ACS Symposiu
m Series 455, American Chemical Society, (1991)
Etc.)

On the other hand, organic polymer-based nonlinear optical materials which are advantageous in terms of processing and size increase have been studied. That is, an organic compound having a large nonlinear optical property (hereinafter,
(Called non-linear molecule) is mixed and dispersed in the polymer material, or the non-linear molecule is chemically bonded to the polymer main chain by covalent bond to prepare a film in which the non-linear molecule is uniformly dispersed in the polymer matrix, Further, a voltage is applied to perform an electric field orientation treatment (hereinafter referred to as "poling") to orient the non-linear molecules in one direction, resulting in a high overall 2
Attempts have been made to obtain large materials with the following non-linear optical properties. (For example, DM Burland et al., "Second-Or
der Nonlinearity in Poled-Polymer Systems ", Chemic
al Reviews, Volume 94, p.31-75 (1994) etc.)

[0005]

However, an organic compound having a strong electron-donating group and a strong electron-accepting group is introduced into an organic compound having a π-electron conjugated system for the purpose of exerting a large nonlinear optical effect. However, even if a crystal is formed, it is easy to have a centrosymmetric structure due to the existence of an electric dipole in the ground state, and the large non-linearity shown by one molecule is easily canceled out by the crystal as a whole. there were. The nonlinearity increases by increasing the conjugate length of the π electrons, but the absorption wavelength band of the molecule itself shifts to the longer wavelength side, and as a result, the output of the fundamental wave and the generated harmonics is reduced due to absorption. Such a problem occurred.

Therefore, a first object of the present invention is to easily form a single crystal and to have excellent non-linear optical characteristics in the entire crystal.
Another object of the present invention is to provide a new low molecular weight organic nonlinear optical material having a short absorption wavelength edge, that is, it is difficult to cause absorption of a fundamental wave and generated harmonics.

On the other hand, in the above-mentioned polymer system, it is known that the nonlinear optical characteristics tend to increase in proportion to the content of the nonlinear molecule. When a high concentration of non-linear molecules is contained in a non-linear optical material, the mechanical strength of the film is reduced, light transmission is lost, and it becomes difficult to orient all the non-linear molecules by poling, resulting in high non-linearity. There was a problem that the optical characteristics were not expressed. In addition, even if the nonlinear molecules are oriented immediately after poling to exhibit high nonlinear optical characteristics, there is a problem in terms of stability in long-term use because the nonlinear optical strength decreases due to orientation relaxation due to the glass transition of the polymer material. It was On the other hand, a method using three-dimensional cross-linking has been studied for the purpose of suppressing the relaxation of orientation, but when cross-linking is performed, it is insoluble in a solvent, which is disadvantageous in terms of moldability.

Therefore, the second object of the present invention is to create a polymer compound which chemically bonds non-linear molecules with high density and stability as much as possible, is soluble in a solvent, and has a high glass transition temperature. It is an object of the present invention to provide a polymer nonlinear optical material having nonlinear optical characteristics, excellent workability, and less likely to cause strength reduction due to orientation relaxation.

[0009]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies in order to obtain a low molecular weight and high molecular weight nonlinear optical material having the above-mentioned characteristics. As a result, it is possible to synthesize a novel dinitrobenzoic acid ester derivative having a specific substituent, and a part of the dinitrobenzoic acid ester derivative exhibits a good nonlinear optical effect and a single crystal can be easily formed. It is also possible to synthesize a novel diaminobenzoic acid ester derivative by using the dinitrobenzoic acid ester derivative as a precursor, and having a short absorption wavelength end. Polyamide having a high glass transition temperature which contains two or more non-linear molecules in a repeating unit at a high density and has an aromatic ring in the main chain by polycondensation using a phthalate derivative containing one or more of What is obtained is that the polyamide is soluble in a solvent, Process that the exhibited higher second-order nonlinear optical effect subjecting, moreover found that the orientation relaxation is excellent in hardly occurs long-term stability, have reached the present invention.

That is, the present invention is represented by the following general formula (I)

[0011]

[Chemical 7]

(Wherein X ¹ and X ² are nitro groups or amino groups, Y ¹ is a linear or branched hydrocarbon chain having 1 to 12 carbon atoms, R ¹ is a hydrogen atom, a lower alkyl group, Alternatively, Y ¹ and the nitrogen atom to which it is bonded may together form a ring, and A ¹ is a hydrogen atom, an electron-accepting group, or a π-conjugated system substituent containing an electron-accepting group. Benzoic acid ester derivative represented by the following general formula (II)

[0013]

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(Wherein Y ¹ is a linear or branched hydrocarbon chain having 1 to 12 carbon atoms, R ¹ is a hydrogen atom, a lower alkyl group, or Y ¹ and a nitrogen atom to be bonded together. A ¹ is a hydrogen atom, an electron-accepting group, or a π-conjugated substituent containing an electron-accepting group, and is composed of a dinitrobenzoate derivative represented by Non-linear optical material whose relative second harmonic intensity generated by the same fundamental input wave is 10 ^-3 or more when the second harmonic intensity generated from urea is 1 with the laser light of 1 as the fundamental input wave, The repeating unit has the following general formula (III)

[0015]

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(In the formula, R ² and R ³ may be the same or different, and a hydrogen atom or the following general formula (IV)

[0017]

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The substituent represented by the formula, m is an integer of 0 or 1, Y ¹ , Y ² and Y ³ may be the same or different, and a linear or branched hydrocarbon chain having 1 to 12 carbon atoms. , R
¹ , R ⁴ and R ⁵ may be the same or different and each is a hydrogen atom, a lower alkyl group, or Y ¹ , Y ² or Y ^{3 respectively.}
And a nitrogen atom to which it is bonded may together form a ring, and A ² , A ³ and A ⁴ may be the same or different and are an electron-accepting group or a π-conjugated system substituent containing an electron-accepting group. Is. And an aromatic polyamide having a weight average molecular weight of 1,000 or more, and a polymer nonlinear optical material comprising the aromatic polyamide.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION R in the general formulas (I) to (IV)
^{As the} lower alkyl group represented by ¹ , R ⁴ and R ⁵ ,
Examples thereof include an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group. Further, R ¹ , R ⁴ and R ⁵ are each Y ¹ ,
Examples of the ring formed integrally with the hydrocarbon chain represented by Y ² or Y ³ and the bonding nitrogen atom include an aziridine ring, an azetidine ring, a pyrrolidine ring, a pyrroline ring and a piperidine ring.

In the general formulas (I) to (IV), A ¹ , A ² ,
Examples of the electron accepting group represented by A ³ and A ⁴ include a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group, a haloalkoxycarbonyl group, an alkylsulfonyl group, a haloalkylsulfonyl group, an arylsulfonyl group and an alkoxysulfonyl group. Group, haloalkoxysulfonyl group, alkylsulfinyl group, haloalkylsulfinyl group, arylsulfinyl group, alkoxysulfinyl group, haloalkoxysulfinyl group, formyl group, acyl group, haloacyl group, perfluoroalkyl group such as trifluoromethyl group , 2-cyanovinyl group,
2,2-dicyanovinyl group, tricyanovinyl group, 2-nitrovinyl group, 2,2-dinitrovinyl group, 2,2-di (alkoxycarbonyl) vinyl group, 2-cyano-2- (alkoxycarbonyl) vinyl group Examples thereof include a 2-cyano-2- (alkoxysulfonyl) vinyl group and a 2-cyano-2- (alkylsulfonyl) vinyl group. The acyl group includes an alkanoyl group and an aroyl group, and the former may be substituted with a halogen atom, particularly a fluorine atom. Further, the above aryl group may be substituted with a halogen atom, a nitro group, a cyano group, or any other group exemplified above. In addition, as a halogen atom as a substituent, a fluorine atom is generally preferable from the viewpoint of stability. Further, as the π-conjugated system substituent containing an electron-accepting group also represented by A ¹ , A ² , A ³ and A ⁴ ,

[0021]

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(In the formula, A ⁵ is an electron-accepting group.) And the like. Here, examples of the electron-accepting group represented by A ⁵ include the substituents exemplified above.

The benzoic acid ester derivative represented by the general formula (I) of the present invention can be produced, for example, by the following synthetic method. That is, in the benzoic acid ester derivative represented by the general formula (I), a compound in which the substituents X ¹ and X ² are nitro groups (the general formula (I
(Same as the compound represented by I)), the following general formula (V)

[0024]

[Chemical 12]

(Wherein, X is a hydroxyl group or a halogen atom) and dinitrobenzoic acid or a dinitrobenzoic acid halide represented by the following general formula (VI)

[0026]

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(In the formula, Y ¹ is a linear or branched hydrocarbon chain having 1 to 12 carbon atoms, R ¹ is a hydrogen atom, a lower alkyl group, or Y ¹ and a nitrogen atom to be bonded together. May form a ring, and A ¹ is a hydrogen atom, an electron-accepting group, or a π-conjugated system substituent containing an electron-accepting group. Is synthesized.

In the dinitrobenzoic acid or dinitrobenzoic acid halide represented by the general formula (V) used for producing the dinitrobenzoic acid ester derivative of the present invention, the substitution position of the dinitro group is 2 on the benzene ring. , 3rd, 2,4th, 2,5th, 2,6th, 3,4th, 3,5
Although the position is mentioned, the 3,5 position is most preferable from the viewpoint of easiness of synthesis and availability of raw materials. Further, a part of the alcohol compound represented by the general formula (VI) is a known compound, and can be synthesized by the method described in the corresponding literature. (Eg RE Parker, Ad
vances in Fluorine Chemistry, Volume 3, p.63-91 (1963
Year); J. Zyss et al., Journal of Chemical Physics, No. 81.
Volume, p. 4160-4167 (1984); DR Robello, Journal
of Polymer Science, Part A: Polymer Chemistry, No. 28
Volume, p.1 (1990); G. S'heeren et al., Die Makromolekular
e Chemie, Volume 194, p.1733-1744 (1993);
Even if the compound represented by the general formula (VI) is not the compound described in the literature, it is synthesized by the method described in the literature, for example, by the method shown in Reference Examples 4 to 8 later. it can.

The rest represented by the general formula (II)
Substituent A of fragrance ester derivatives ¹Is an electron-accepting group
Or π-conjugated substituents containing electron-accepting groups
The benzoic acid ester represented by the general formula (II)
Substituent A in the derivative¹A compound in which is a hydrogen atom
Without synthesizing the phenyl group, and using an known method to
Introducing a π-conjugated system substituent containing a capacitive or electron-accepting group
Can be manufactured by
10-13).

The rest represented by the general formula (I) of the present invention
Substituent X in fragrance ester derivatives ¹And X²Is nitro
A compound which is a group represented by the general formula (II)
Of certain dinitrobenzoic acid ester derivatives
The compound has a good quadratic non-linearity, as will be described later in the Examples.
A single crystal form that exhibits a linear optical effect and has good crystallinity.
It has the characteristics that it is easy to produce and the absorption wavelength edge is short,
Useful as a practical low molecular weight organic nonlinear optical material
You.

On the other hand, among the benzoic acid ester derivatives represented by the general formula (I), the compounds in which the substituents X ¹ and X ² are amino groups are, for example, the general formula (II) synthesized by the above method. ) It is obtained by reducing the nitro group of the compound represented by. This reduction reaction includes diborane, lithium borohydride, sodium borohydride, lithium aluminum hydride, sodium aluminum hydride,
The reaction proceeds easily by reacting with a commonly used reducing agent such as sodium dialkoxy aluminum hydride and sodium diethyl aluminum hydride. In this case, the reaction suitably proceeds by performing the reaction in the presence of a catalyst such as tin chloride. Further, in addition to the above, by carrying out catalytic reduction using a metal such as nickel, platinum, palladium, or rhodium in a hydrogen gas atmosphere as a catalyst, the precursor represented by the general formula (II) can be converted to the general formula (I). Of the benzoic acid ester derivatives shown, it is also possible to synthesize a compound in which the substituents X ¹ and X ² are amino groups. It is desirable to carry out any reaction in a solvent, and any solvent may be used so long as it does not participate in the reaction, and examples thereof include alcohol, tetrahydrofuran, dimethoxyethane, dioxane, benzene and toluene. The reaction temperature is −100 ° C. to 150 ° C., preferably −50 ° C.
It can be performed in the range of 100 ° C. Further, when the introduced non-linear molecule is decomposed or modified by the above reduction reaction, diaminobenzoic acid having an amino group protected or a derivative thereof and an alcohol compound represented by the general formula (VI) are used. After subjecting to a known condensation reaction,
Also by deprotection, a compound in which the substituents X ¹ and X ^{2 of the} benzoic acid ester derivative represented by the general formula (I) are amino groups can be obtained.

Among the benzoic acid ester derivatives represented by the general formula (I) obtained by the above-mentioned production method, a compound in which the substituents X ¹ and X ² are amino groups is used as a monomer, and the repeating unit of the present invention is The aromatic polyamide represented by the general formula (III) can be produced. That is, a compound of the benzoic acid ester derivative represented by the general formula (I) in which the substituents X ¹ and X ² are amino groups, and, for example, the following general formula (VII)

[0033]

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(In the formula, R ² and R ³ may be the same or different and each is a hydrogen atom or a substituent represented by the general formula (IV), m is an integer of 0 or 1, and Y ² is 1 having a carbon number. ~ 1
2 straight or branched hydrocarbon chain, R ⁴ may form a ring together with a hydrogen atom, a lower alkyl group or Y ² and the nitrogen atom to which it is bonded, and A ³ represents an electron accepting group. A π-conjugated system substituent containing a group or an electron-accepting group. ) And a phthalic acid derivative represented by
It can be synthesized by carrying out a polycondensation reaction. The polycondensation reaction preferably proceeds in the presence of a condensing agent, and examples of the condensing agent used here include (PhO) ₃ P, (PhO) PCl ₂ , and PhPOCl.
_{2, (C 3 H 7)} 3 P (O) O, POCl 3, SOCl 2 / Et 3 N, Ph 3 P / C 2 Cl 6, Si
Examples include Cl ₄ , Me ₂ SiCl _{2, and the} like. Further, this reaction is preferably carried out in an organic solvent, and an aprotic polar solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone is preferably used. The reaction temperature in this condensation reaction is preferably from room temperature to about 250 ° C. from the viewpoint of the stability of the monomer.

The above-mentioned general formula (VII) used in the present invention
The phthalic acid derivative represented by is a compound previously found by the present inventors (Proceedings of the 43rd Symposium on Macromolecules, p. 2235-2236).
(1994), etc.) and can be produced, for example, by the synthetic method shown below. That is, the following general formula (VIII)

[0036]

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A hydroxyphthalic acid diester represented by the formula (wherein R is a lower alkyl group) and the following general formula (IX)

[0038]

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(In the formula, Z is a hydroxyl group or a leaving group, R is²Oh
And R^ThreeMay be the same or different, hydrogen atom or
A substituent represented by the general formula (IV), m is 0 or 1
Integer, Y ²Is a straight or branched chain having 1 to 12 carbon atoms
Hydrocarbon chain, R^FourIs a hydrogen atom, a lower alkyl group, or
Y²And together with the bonding nitrogen atom form a ring
May be A^ThreeIs an electron-accepting group or an electron-accepting group
It is a π-conjugated system substituent containing. ) With a compound represented by
By the condensation reaction, the following general formula (X)

[0040]

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(Wherein R is a lower alkyl group, R ² and R ³ may be the same or different, a hydrogen atom or a substituent represented by the general formula (IV), m is an integer of 0 or 1, and Y is ² is a linear or branched hydrocarbon chain having 1 to 12 carbon atoms, R ⁴ is a hydrogen atom, a lower alkyl group, or Y ²
And a nitrogen atom to be bonded may form a ring together with A ³ , and A ³ is an electron-accepting group or a π-conjugated system substituent containing an electron-accepting group. ) A phthalic acid diester derivative represented by the formula (1) is synthesized, and the phthalic acid diester derivative is further synthesized, for example, with lithium hydroxide, potassium hydroxide, sodium hydroxide, aluminum hydroxide, potassium carbonate,
It can be easily obtained by hydrolysis in the presence of a basic substance such as sodium carbonate, potassium acetate, sodium acetate or sodium phosphate. The leaving group represented by Z in the compound represented by the general formula (IX) is a chlorine atom,
Examples thereof include halogen atoms such as bromine atom and iodine atom, methanesulfonyloxy group, sulfonyloxy group such as p-toluenesulfonyloxy group and the like.

The above condensation reaction preferably proceeds in the presence of a suitable condensing agent. The condensing agent used varies depending on the substituent represented by Z of the compound represented by the general formula (IX). However, when Z is a hydroxyl group, the reaction is performed by using diethylazodicarboxylate and triphenylphosphine. Is known to proceed favorably.
(For example, O. Mitsunobu, Synthesis, 1981, p.1-2.
8 (1981), etc.) On the other hand, when Z is a leaving group, lithium hydroxide, potassium hydroxide, sodium hydroxide, aluminum hydroxide, potassium carbonate, sodium carbonate, potassium acetate, sodium acetate, phosphoric acid Basic substances such as sodium, sodium hydride, calcium hydride, pyridine, triethylamine, N, N-dimethylaniline are preferably used as the condensing agent, but it is preferable to use a weak basic substance among the above basic substances. More preferable. This reaction is preferably performed in an organic solvent, and any solvent may be used as long as it dissolves the raw materials and does not participate in the reaction.For example, hexane, cyclohexane, chloroform, dichloromethane, dichloroethane, benzene, toluene, Examples thereof include xylene, acetone, methyl ethyl ketone, tetrahydrofuran, dimethoxyethane, dioxane, acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like. The reaction proceeds normally preferably in a temperature range from room temperature to 100 ° C.

The above-mentioned general formula (VII) used as a raw material
Examples of the hydroxyphthalic acid diester represented by I) include dimethyl 3-hydroxyphthalate, dimethyl 4-hydroxyphthalate, diethyl 3-hydroxyphthalate, diethyl 4-hydroxyphthalate, dimethyl 4-hydroxyisophthalate and 5- Dimethyl hydroxyisophthalate, diethyl 4-hydroxyisophthalate, diethyl 5-hydroxyisophthalate, dipropyl 4-hydroxyisophthalate, dipropyl 5-hydroxyisophthalate, dimethyl 2-hydroxyterephthalate, diethyl 2-hydroxyterephthalate,
Examples thereof include dipropyl 2-hydroxyterephthalate, dibutyl 2-hydroxyterephthalate, dipentyl 2-hydroxyterephthalate, and dihexyl 2-hydroxyterephthalate.

Further, some of the compounds represented by the general formula (IX) are known compounds, and can be synthesized by the method described in the corresponding literature. (For example, RE Parker, Advances in Fluorine Chemistry,
Volume 3, p.63-91 (1963); J. Zyss et al., Journal of Ch.
emical Physics, Vol. 81, p. 4160-4167 (1984); G.
S'heeren et al., Die Makromolekulare Chemie, Volume 194,
p.1733-1744 (1993); see Japanese Patent Laid-Open No. 3-100008, etc.) Incidentally, even if the compound represented by the general formula (V) is not the compound described in the literature, the method described in the literature is referred to. For example, it can be synthesized by the method shown in Reference Example later.

The repeating unit obtained by the above-mentioned production method is represented by the general formula (III), and the aromatic polyamide has a weight average molecular weight of 1,000 or more, preferably 5,000 or more. Is preferable in terms of stability. The molecular weight is measured by a known method such as gel permeation chromatography, vapor pressure measuring method, osmotic pressure method, light scattering method, and viscosity method.

When the aromatic polyamide of the present invention is used as a polymer nonlinear optical material, for example, the polyamide is used as chloroform, dichloromethane, dichloroethane, benzene, toluene, xylene, tetrahydrofuran, dimethoxyethane, dioxane, acetonitrile, dimethylformamide, Dissolved in an organic solvent such as dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, etc., the film thickness on the substrate such as a glass substrate, an ITO vapor deposition substrate or a silicon wafer by a method such as a spin coating method or a casting method is preferably 0. After being formed into a film having a thickness of 1 to 10 μm and dried, a poling treatment is preferably performed at a voltage of 1 kV / cm or more while maintaining the temperature near the glass transition temperature of the polyamide, and a side chain dye molecule (non-linear molecule). To orient Material to obtain the objective by.

The polymer nonlinear optical material of the present invention has a main chain skeleton made of an aromatic polyamide, is soluble in a solvent, and has a high density of dye molecules (nonlinear molecules) in its side chains. It has processability and excellent second-order nonlinear optical intensity, and has a high glass transition temperature and a small decrease in intensity due to orientational relaxation, and is excellent in stability. In addition, since it is a glassy (amorphous) polymer, it is a material excellent in transparency with less light scattering found in crystalline polymers.
Therefore, a wavelength conversion element utilizing the nonlinear optical effect,
It is useful as a material for optical control devices such as waveguides, optical shutters, optical switches, optical polarization elements, and phase modulation elements, nonlinear optical devices, and electro-optical devices.

Hereinafter, the present invention will be described in more detail with reference to Examples and Examples. However, it goes without saying that the present invention is not limited to these.

[0049]

【Example】

Reference Examples 1 to 3

[0051]

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The alcohol derivatives represented by the structural formulas (1), (2) and (3) are combined with N-methylaniline and
Using 3-chloropropanol, 4-chlorobutanol or 6-chlorohexanol as raw materials, the method described in the literature (DR Robello, Journal of Polymer Science, P
art A: Polymer Chemistry, Vol. 28, p.1 (1990)). In addition, it was confirmed from the ¹ H-NMR spectrum shown below that the product had the above structure.

Compound (1): Yield; 70% ¹ H-NMR, δ (CDCl ₃ , ppm): 1.6-2.1 (m, 3H), 2.92 (s,
3H), 3.44 (t, J = 6.0Hz, 2H), 3.78 (t, J = 6.0Hz, 2H),
6.6-6.9 (m, 3H), 7.1-7.4 (m, 2H).

Compound (2): Yield; 15% ¹ H-NMR, δ (CDCl ₃ , ppm): 1.5-1.9 (m, 5H), 2.88 (s,
3H), 3.28 (t, J = 5.9Hz, 2H), 3.57 (t, J = 5.9Hz, 2H),
6.6-6.9 (m, 3H), 7.1-7.4 (m, 2H).

Compound (3): Yield; 83% ¹ H-NMR, δ (CDCl ₃ , ppm): 1.1-1.8 (m, 9H), 2.89 (s,
3H), 3.29 (t, J = 5.9Hz, 2H), 3.59 (t, J = 5.9Hz, 2H),
6.5-6.8 (m, 3H), 7.1-7.4 (m, 2H).

Reference Examples 4 to 6

[0057]

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N-methylethanolamine 0.520 g (6.92 m
mol), a known method (AE Feiring, Journal of Fluorin
e Chemistry, Volume 24, p.191 (1984) and Journal of
the American Chemical Society, Volume 112, p.7083 (19
(90)), and added (4 ml) of (4-fluorophenyl) perfluorooctylsulfone (4.00 g, 6.92 mmol) and anhydrous potassium carbonate (1.06 g, 7.70 mmol) to the mixture, and added 3 ml of dry DMSO for 12 hours at 100 ° C. It was stirred. The reaction mixture was poured into 300 ml of water, and the formed precipitate was collected by filtration. The crude product was purified by recrystallization from methanol. As a result, 2- [4- (perfluorooctylsulfonyl)-having the structural formula represented by the above (4) was obtained.
N-methylanilino] ethanol 3.92 g (yield: 90%) was obtained as white crystals. The fact that the product has the above structure shows that ¹ H-NMR, IR spectrum, and Mas described below.
Confirmed from s-spectrum and elemental analysis.

¹ H-NMR, δ (CDCl ₃ , ppm): 1.65 (t, J = 5.1
Hz, 1H), 3.15 (s, 3H), 3.64 (t, J = 5.3Hz, 2H), 3.87
(t, J = 5.3Hz, 2H), 6.81 (d, J = 9.2Hz, 2H), 7.77 (d,
J = 9.2Hz, 2H). IR (cm ^-1 ): 3580 (-OH), 3430, 2950, 2900, 2875, 159
0, 1550, 1520, 1495, 1460, 1440, 1390, 1370, 1350,
1310, 1240, 1210, 1160, 1120, 1110, 1080, 1070, 9
90, 970, 940, 905, 860, 820, 805, 760, 740, 710, 6
80, 660, 620, 605, 580, 550, 505. Mass (m / e): 633 (M ⁺ ), 214 (M ⁺ -(C ₈ F ₁₇ )), 169 (CF ₃ (C
F ₂ ) ₂ ⁺ ), 150 (M ⁺ -(SO ₂ C ₈ F ₁₇ )), 119 (CF ₃ CF ₂ ⁺ ), 69 (CF
₃ ⁺ ). Elemental analysis (C ₁₇ H ₁₂ NSO ₃ F ₁₇ , molecular weight 633.3) Calculated C: 32.24%, H: 1.91%, N: 2.21%. Found C: 32.18%, H: 1.65%, N: 1.99%.

In this reaction, commercially available 4-fluorobenzonitrile and 4-fluoroacetophenone were used in place of (4-fluorophenyl) perfluorooctyl sulfone, and the same operation as above was carried out to obtain the compound represented by the above structural formula. (5) and (6) were synthesized respectively. The yield, spectral analysis result and elemental analysis result of the obtained compound are shown below.

Compound (5): Yield: 79% ¹ H-NMR, δ (CDCl ₃ , ppm): 1.60 (t, J = 5.7Hz, 1H), 3.0
7 (s, 3H), 3.57 (t, J = 5.2Hz, 2H), 3.82 (t, J = 5.5H
z, 2H), 6.71 (d, J = 9.0Hz, 2H), 7.45 (d, J = 9.0Hz, 2
H). IR (cm ^-1 ): 3400, 2920, 2870, 2210 (-CN), 1610, 152
0, 1460, 1440, 1390, 1360, 1270, 1230, 1210, 1180,
1120, 1050, 820, 540. Mass (m / e): 176 (M ⁺ ), 157, 145 (NC-Ph-N (CH ₃ ) CH ₂ ⁺ ),
129, 116, 102 ( ⁺ Ph-CN), 75, 51, 42, 31. Elemental analysis (C ₁₀ H ₁₂ N ₂ O, molecular weight 176.2) Calculated value C: 68.16%, H: 6.86%, N: 15.90% Actual value C: 68.34%, H: 6.94%, N: 15.98%.

Compound (6): Yield: 52% ¹ H-NMR, δ (CDCl ₃ , ppm): 1.74 (t, J = 5.4Hz, 1H), 2.4
9 (s, 3H), 3.09 (s, 3H), 3.59 (t, J = 5.1Hz, 2H), 3.
83 (t, J = 5.3Hz, 2H), 6.71 (d, J = 9.0Hz, 2H), 7.85
(d, J = 9.0Hz, 2H). IR (cm ^-1 ): 3360, 2930, 2880, 1640 (-C = O), 1550, 15
30, 1470, 1420, 1380,1330, 1300, 1230, 1200, 1080,
1050, 1000, 960, 820, 790, 660, 590, 580,540, 50
0. Mass (m / e): 193 (M ⁺ ), 178 (M ⁺ -CH ₃ ), 162 (M ⁺ -(CH ₂ O
H)), 119 ( ⁺ PhCOCH ₃ ), 91, 77, 43 (CH ₃ CO ⁺ ). Elemental analysis (C ₁₁ H ₁₅ NO ₂ , molecular weight 193.2) Calculated C: 68.37%, H: 7.82%, N 7.25 Actual value C: 68.34%, H: 7.97%, N 7.16%.

Reference Examples 7 and 8

[0064]

Embedded image

4-aminobenzonitrile 10.0 g (84.7 mmo
l) was dissolved in a mixture of 40 ml of sulfuric acid and 120 ml of water under ice cooling. Sodium nitrite dissolved in 10 ml of water was added to this solution.
7.01 g (101.6 mmol) was added dropwise over 30 minutes. 2- (N-methylanilino) ethanol 9.22 g (127.1 m
(mol) was added dropwise over 30 minutes under ice cooling. Further, this reaction solution was stirred at room temperature for 1 hour and then neutralized with sodium hydrogen carbonate to produce a reddish brown precipitate. This precipitate was collected by filtration, washed with water, and then purified by recrystallization from methanol. As a result, 11.6 g (yield: 49%) of 2- [4- (4-cyanophenylazo) -N-methylanilino] ethanol having the structural formula represented by the above (7) was obtained as dark red crystals. The structure of the product was confirmed by ¹ H-NMR, IR spectrum and elemental analysis shown below.

¹ H-NMR, δ (CDCl ₃ , ppm): 1.77 (t, J = 5.5
Hz, 1H), 3.14 (s, 3H), 3.63 (t, J = 5.2Hz, 2H), 3.85
(t, J = 5.2Hz, 2H), 6.80 (d, J = 9.2Hz, 2H), 7.6-8.2
(m, 6H). IR (cm ^-1 ): 3500, 2920, 2225 (-CN), 1600, 1555, 152
0, 1440, 1420, 1375, 1345, 1315, 1260, 1215, 1145,
1105, 1070, 1045, 975, 845, 830, 555, 510. Elemental analysis (C ₁₆ H ₁₆ N _4O , molecular weight 280.3) Calculated C: 68.55%, H: 5.75%, N 19.99%. Found C: 68.71 %, H: 5.78%, N 20.07%.

In this reaction, 6- (N-methylanilino) -1-hexanol obtained in Reference Example 3 was used in place of 2- (N-methylanilino) ethanol, and the same operation as above was carried out. 6- [4-represented by formula (8)
(4-Cyanophenylazo) -N-methylanilino] -1-hexanol was synthesized. The structure of the product was confirmed by ¹ H-NMR, IR spectrum and elemental analysis shown below.

¹ H-NMR, δ (CDCl ₃ , ppm): 1.2-1.9 (m, 9
H), 3.08 (s, 3H), 3.44 (t, J = 6.0Hz, 2H), 3.65 (t, J
= 6.0Hz, 2H), 6.72 (d, J = 9.2Hz, 2H), 7.6-8.2 (m, 6
H). IR (cm ^-1 ): 3455, 2925, 2220, 1600, 1560, 1520, 146
0, 1420, 1385, 1350, 1310, 1260, 1220, 1140, 1080,
1050, 965, 850, 825, 555. Elemental analysis (C ₂₀ H ₂₄ N ₄ O, molecular weight 336.4) Calculated value C: 71.40%, H: 7.19%, N: 16.65%. Measured value C: 71.46%, H: 7.18%, N: 16.68%.

Examples 1, 2

[0070]

[Chemical 21]

5.05 g (25.0 mmol) of 3,5-dinitrobenzoic acid
And commercially available 2- (N-methylanilino) ethanol 11.34 g
(75.0.0 mmo) was dissolved in 40 ml dry dichloromethane. In this solution, 4- (N, N-dimethylamino) pyridine 0.25
g (2.0 mmol) and 1,3-dicyclohexylcarbodiimide (DCC) 5.70 g (27.5 mmol) were added, and the mixture was stirred at room temperature for 12 hours. The produced solid was removed by filtration, dichloromethane and saturated aqueous sodium hydrogen carbonate solution were added, and the organic layer was separated. After the organic layer was dehydrated with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The residue was purified by recrystallization from acetone. as a result,
2- (N-methylanilino) represented by the structural formula (9) above
Ethyl 3,5-dinitrobenzoate 7.98 g (Yield: 97%)
Was obtained as brown crystals. In addition, the fact that the product has the above structure shows the following ¹ H-NMR, IR spectrum, M
It was confirmed by an ass spectrum and elemental analysis.

¹ H-NMR, δ (CDCl ₃ , ppm): 3.02 (s, 3H),
3.80 (t, J = 5.7Hz, 2H), 4.64 (t, J = 5.7Hz, 2H), 6.5-
6.9 (m, 3H), 7.0-7.3 (m, 2H), 8.98 (d, J = 2.0Hz, 2
H), 9.15 (t, J = 2.0Hz, 1H). IR (cm ^-1 ): 3110, 3080, 2965, 1740 (-C = O), 1630, 16
00, 1545 (asymmetric stretching of -NO ₂ ), 1505, 14
60, 1370, 1345 (symmetric stretching of -NO ₂ ), 127
5, 1220, 1195, 1165, 1150, 1075, 990, 925, 750, 72
0, 695. Mass (m / e): 345 (M ⁺ ), 195 ((O ₂ N) ₂ PhCO ⁺ ), 149, 120
(Ph-N (CH ₃ ) CH ₂ ⁺ ), 105,77 (Ph ⁺ ), 43, 28. Elemental analysis (C ₁₆ H ₁₅ N ₃ O ₆ , molecular weight 345.3) Calculated C: 55.65%, H: 4.38 %, N: 12.17% .Actual value C: 55.58%, H: 4.40%, N: 12.22%.

In this reaction, 6- (N-methylanilino) -1-hexanol (3) obtained in Reference Example 3 was used in place of 2- (N-methylanilino) ethanol, and the same operation as above was carried out. Then, 6- (N-methylanilino) hexyl 3,5-dinitrobenzoate represented by the structural formula (10) above was obtained as brown crystals. The product has the above structure was confirmed by ¹ H-NMR, IR spectrum, Mass spectrum and elemental analysis shown below. (Yield: 85%)

¹ H-NMR, δ (CDCl ₃ , ppm): 1.2-1.8 (m, 8
H), 2.91 (s, 3H), 3.31 (t, J = 6.3Hz, 2H), 4.45 (t, J
= 6.5Hz, 2H), 6.6-6.9 (m, 3H), 7.1-7.4 (m, 2H), 9.1
2 (d, J = 2.0Hz, 2H), 9.19 (t, J = 2.0Hz, 1H). IR (cm ^-1 ): 3110, 2930, 1730 (-C = O), 1630, 1595, 15
40 (asymmetric stretching of -NO ₂ ), 1505, 1460, 13
45 (symmetric stretching of -NO ₂ ), 1280, 1230, 116
5, 1075, 990, 920, 750, 720, 695. Mass (m / e): 401 (M ⁺ ), 195 ((O ₂ N) ₂ PhCO ⁺ ), 149, 120
(Ph-N (CH ₃ ) CH ₂ ⁺ ), 105,77 (Ph ⁺ ). Elemental analysis (C ₂₀ H ₂₃ N ₃ O ₆ , molecular weight 401.4) Calculated C: 55.65%, H: 4.38%, N: 12.17% .Actual value C: 55.58%, H: 4.40%, N: 12.22%.

Examples 3 to 9

[0076]

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8.05 g (40.0 mmol) 3,5-dinitrobenzoic acid
Under argon atmosphere, 20 ml of thionyl chloride was added, and the mixture was refluxed overnight. After cooling, excess thionyl chloride was distilled off under reduced pressure, and 20 ml of dry THF was added to the residue. To this THF solution were added 6.61 g (40.0 mmol) of compound (1) obtained in Reference Example 1 dissolved in 50 ml of dry THF and 5.10 g (50.0 mmol) of dry triethylamine, and the mixture was stirred at room temperature for 3 hours. Then, the reaction mixture was poured into 300 ml of saturated aqueous sodium hydrogen carbonate solution. This mixture was extracted with chloroform (20 ml X 6), the organic layer was dried over anhydrous sodium sulfate, and the solution was concentrated under reduced pressure. The residue was made into a chloroform solution and then purified by silica gel chromatography. Furthermore, as a result of recrystallization from ethyl acetate, 12.93 g of 3- (N-methylanilino) propyl 3,5-dinitrobenzoate represented by the structural formula (11) above was obtained.
(Yield: 90%) was obtained as brown crystals. The product has the above structure was confirmed by ¹ H-NMR, IR spectrum, Mass spectrum and elemental analysis shown below.

¹ H-NMR, δ (CDCl ₃ , ppm): 2.1-2.3 (m, 2
H), 2.97 (s, 3H), 3.53 (t, J = 6.8Hz, 2H), 4.52 (t, J
= 6.4Hz, 2H), 6.6-6.9 (m, 3H), 7.1-7.4 (m, 2H), 9.1
2 (d, J = 2.0Hz, 2H), 9.19 (t, J = 2.0Hz, 1H). IR (cm ^-1 ): 3110, 2970, 2895, 2830, 1730 (-C = O), 16
30, 1600, 1545 (asymmetric stretching of -NO ₂ ), 15
05, 1460, 1375, 1340 (symmetric stretching of -N
O ₂ ), 1280, 1245, 1225, 1200, 1170, 1130, 1075, 103
0, 990, 945, 915,885, 830, 755, 720, 695, 635, 58
0, 515. Mass (m / e): 359 (M ⁺ ), 195 ((O ₂ N) ₂ PhCO ⁺ ), 149, 120
(Ph-N (CH ₃ ) CH ₂ ⁺ ), 105,77 (Ph ⁺ ), 43, 28. Elemental analysis (C ₁₇ H ₁₇ N ₃ O ₆ , molecular weight 359.3) Calculated value C: 56.82%, H: 4.77 %, N: 11.69% .Actual value C: 56.67%, H: 4.69%, N: 11.58%.

Further, instead of the compound (1) in this reaction, the compound (3) obtained in Reference Examples 3 to 8,
Using (4), (5), (6), (7), and (8), the same operation as described above is performed, and the above structural formula (1
The 3,5-dinitrobenzoic acid ester derivatives represented by 2), (13), (14), (15), (16) and (17) were respectively synthesized. The yield, spectral analysis result and elemental analysis result of the obtained compound are shown below.

Compound (12): Yield: 91% ¹ H-NMR, δ (CDCl ₃ , ppm): 1.6-2.1 (m, 4H), 2.95 (s,
3H), 3.40 (t, J = 6.4Hz, 2H), 4.48 (t, J = 6.4Hz, 2H),
6.6-6.9 (m, 3H), 7.1-7.4 (m, 2H), 9.12 (d, J = 2.0Hz,
2H), 9.21 (d, J = 2.0Hz, 1H). IR (cm ^-1 ): 3115, 2995, 2965, 2945, 2925, 2830, 172
0 (-C = O), 1630, 1595,1545 (asymmetric stretching o
f -NO ₂ ), 1505, 1470, 1345 (symmetric stretching of
-NO ₂ ), 1290, 1275, 1250, 1210, 1190, 1165, 1115,
1095, 1070, 1035, 995, 965, 920, 885, 870, 845, 81
0, 755, 730, 720, 695, 635, 520, 505. Mass (m / e): 373 (M ⁺ ), 195 ((O ₂ N) ₂ PhCO ⁺ ), 149, 120
(Ph-N (CH ₃ ) CH ₂ ⁺ ), 105,77 (Ph ⁺ ), 43, 28. Elemental analysis (C ₁₈ H ₁₉ N ₃ O ₆ , molecular weight 373.4) Calculated value C: 57.91%, H: 5.13 %, N: 11.25% .Actual value C: 58.01%, H: 5.07%, N: 11.13%.

Compound (13): Yield: 86% ¹ H-NMR, δ (CDCl ₃ , ppm): 3.21 (s, 3H), 3.95 (t, J =
5.9Hz, 2H), 4.70 (t, J = 5.9Hz, 2H), 6.87 (d, J = 9.5H
z, 2H), 7.77 (d, J = 9.5Hz, 2H), 9.05 (d, J = 2.0Hz, 2
H), 9.21 (t, J = 2.0Hz, 1H). IR (cm ^-1 ): 3105, 2970, 1735 (-C = O), 1630, 1595, 15
45 (asymmetric stretching of -NO ₂ ), 1520, 1460, 13
90, 1350 (symmetric stretching of -NO ₂ ), 1330, 128
0, 1240, 1205, 1155, 1115, 1085, 995, 930, 825, 77
5, 725, 685, 655, 605, 585, 550, 520. Mass (m / e): 827 (M ⁺ ), 808 (M ⁺ -F), 602 (CF ₃ (CF ₂ ) ₈ SO
₂ Ph-N (CH ₃ ) CH ₂ ⁺ ), 408 (M ⁺ -(C ₈ F ₁₇ )), 344 (M ⁺ -(SO ₂ C ₈ F)
₁₇ )), 195 ((O ₂ N) ₂ PhCO ⁺ ), 169 (CF ₃ (CF ₂ ) ₂ ⁺ ), 149, 13
1, 119 (CF ₃ CF ₂ ⁺ or Ph-N (CH ₃ ) CH ₂ ⁺ ), 105, 91, 75, 69
(CF3 ⁺ ), 42. Elemental analysis (C ₂₄ H ₁₄ N ₃ SO ₈ F ₁₇ , molecular weight 827.4) Calculated C: 34.84%, H: 1.71%, N: 5.08%. Measured C: 34.76%, H: 1.53%, N: 4.87%.

Compound (14): Yield: 93% ¹ H-NMR, δ (CDCl ₃ , ppm): 3.12 (s, 3H), 3.87 (t, J =
5.9Hz, 2H), 4.67 (t, J = 5.8Hz, 2H), 6.76 (d, J = 9.2H
z, 2H), 7.48 (d, J = 9.2Hz, 2H), 9.04 (d, J = 2.0Hz, 2
H), 9.22 (t, J = 2.0Hz, 1H). IR (cm ^-1 ): 3080, 2980, 2920, 2220 (-CN), 1730 (-C =
O), 1630, 1610, 1540 (asymmetric stretching of -NO
₂ ), 1520, 1460, 1390, 1340 (symmetric stretching o
f -NO ₂ ), 1280, 1220, 1170, 1150, 1100, 1080, 980,
960, 920, 900, 830, 770, 720, 680, 580. Mass (m / e): 370 (M ⁺ ), 195 ((O ₂ N) ₂ PhCO ⁺ ), 149, 145
(NC-Ph-N (CH ₃ ) CH ₂ ⁺ ), 129, 102 ( ⁺ Ph-CN), 91, 75, 42,
28. Elemental analysis (C ₁₇ H ₁₄ N ₄ O ₆ , molecular weight 370.3) Calculated value C: 55.14%, H: 3.81%, N: 15.13%. Measured value C: 55.36%, H: 3.77%, N: 15.22% .

Compound (15): Yield: 95% ¹ H-NMR, δ (CDCl ₃ , ppm): 2.48 (s, 3H), 3.14 (s, 3)
H), 3.90 (t, J = 5.6Hz, 2H), 4.67 (t, J = 5.4Hz, 2H),
6.76 (d, J = 9.2Hz, 2H), 7.84 (d, J = 9.2Hz, 2H), 9.01
(d, J = 2.0Hz, 2H), 9.18 (t, J = 2.0Hz, 1H). IR (cm ^-1 ): 3060, 2960, 2860, 1730 (esteric -C = O),
1660 (-C = O), 1630, 1600, 1540 (asymmetric stretchi
ng of -NO ₂ ), 1500, 1460, 1430, 1380, 1340 (symmetr
ic stretching of -NO ₂ ), 1280, 1220, 1190, 1170, 11
00, 1080, 1000, 980, 960, 920, 900, 830, 770, 720,
680, 560. Mass (m / e): 387 (M ⁺ ), 372 (M ⁺ -(CH ₃ )), 268 (M ⁺ -(PhC
OCH ₃ )), 195 ((O ₂ N) ₂ PhCO ⁺ ), 162 (CH ₃ CO-Ph-N (CH ₃ ) CH ₂
⁺ ), 132, 119 ( ⁺ PhCOCH ₃ ), 91, 75, 43 (CH ₃ CO ⁺ ). Elemental analysis (C ₁₈ H ₁₇ N ₃ O ₇ , molecular weight 387.3) Calculated C: 55.81%, H: 4.42% , N: 10.85% .Actual value C: 55.67%, H: 4.22%, N: 10.78%.

Compound (16): Yield: 93% ¹ H-NMR, δ (CDCl ₃ , ppm): 3.18 (s, 3H), 3.94 (t, J =
5.6Hz, 2H), 4.71 (t, J = 5.6Hz, 2H), 6.84 (d, J = 9.2H
z, 2H), 7.6-8.1 (m, 6H), 8.98 (d, J = 2.0Hz, 2H), 9.
08 (t, J = 2.0Hz, 1H). IR (cm ^-1 ): 3100, 2220 (-CN), 1730 (-C = O), 1600, 15
45 (asymmetric stretching of -NO ₂ ), 1520, 1460 (w),
1420, 1380, 1345 (symmetric stretching of -NO ₂ ),
1310, 1275, 1200, 1160, 1135, 1075, 1000, 935, 84
5, 830, 770, 725, 565.Mass (m / e): 474 (M ⁺ ), 249 (M ⁺ -(CH ₂ (CH ₃ ) NPhN = NPhC
N)), 195 ((O ₂ N) ₂ PhCO ⁺ ), 132, 119, 91, 75, 43. Elemental analysis (C ₂₃ H ₁₈ N ₆ O ₆ , molecular weight 474.4) Calculated C: 58.23%, H: 3.82%, N: 17.71% .Actual value C: 58.30%, H: 3.83%, N: 17.52%.

Compound (17): Yield: 78% ¹ H-NMR, δ (CDCl ₃ , ppm): 1.2-2.0 (m, 8H), 3.09 (s,
3H), 3.47 (t, J = 6.7Hz, 2H), 4.45 (t, J = 6.5Hz, 2H),
6.72 (d, J = 9.2Hz, 2H), 7.6-8.1 (m, 6H), 9.12 (d, J
= 2.0Hz, 2H), 9.17 (t, J = 2.0Hz, 1H). IR (cm ^-1 ): 3100, 3065, 2940, 2225 (-CN), 1725 (-C =
O), 1600, 1545 (asymmetric stretching of -NO ₂ ), 15
20, 1460, 1420, 1380, 1345 (symmetric stretching o
f -NO ₂ ), 1295, 1280, 1195, 1160, 1140, 1080, 995,
965, 920, 845, 815, 775, 725, 555. Mass (m / e): 530 (M ⁺ ), 249 (M ⁺ -(CH ₂ (CH ₃ ) NPhN = NPhC
N)), 195 ((O ₂ N) ₂ PhCO ⁺ ), 119, 102, 91, 75, 41. Elemental analysis (C ₂₇ H ₂₆ N ₆ O ₆ , molecular weight 530.5) Calculated C: 61.13%, H: 4.94%, N 15.84% .Actual value C: 61.46%, H: 4.96%, N 15.75%.

Examples 10 and 11

[0087]

Embedded image

3.37 g (22.0 mmol) of phosphoryl chloride was added dropwise over 10 minutes to 10 ml of dry DMF distilled over calcium hydride under cooling with an ice bath under an argon atmosphere.
Furthermore, the mixture was stirred under ice cooling for 2 hours. Then 100 ml of dry DM
6.90 g of the compound (9) obtained in Example 1 dissolved in F
(18.5 mmol) was added dropwise, and the mixture was stirred at 90 ° C for 3 hours.
The reaction solution was cooled to room temperature and then poured into 300 ml of saturated aqueous sodium hydrogen carbonate solution. The solution was extracted with dichloromethane (20 ml X 5), the organic layer was dried over anhydrous sodium sulfate, and then the solution was concentrated under reduced pressure. The residue was purified by silica gel column chromatography using dichloromethane as an eluent, and the solvent was evaporated under reduced pressure. By recrystallizing the residue from acetone, 5.68 g (yield: 76%) of 2- (4-formyl-N-methylanilino) ethyl 3,5-dinitrobenzoate of the structural formula represented by the above (18) was obtained as yellow crystals. Obtained. The product has the above structure was confirmed by ¹ H-NMR, IR spectrum, Mass spectrum and elemental analysis shown below.

¹ H-NMR, δ (CDCl ₃ , ppm): 3.17 (s, 3H),
3.92 (t, J = 5.7Hz, 2H), 4.68 (t, J = 5.7Hz, 2H), 6.82
(d, J = 8.8Hz, 2H), 7.72 (d, J = 8.8Hz, 2H), 9.02 (d,
J = 2.0Hz, 2H), 9.18 (t, J = 2.0Hz, 1H), 9.72 (s, 1
H). IR (cm ^-1 ): 3105, 2900, 1730 (esteric -C = O), 1670
(aldehydic -C = O), 1595,1545 (asymmetric stretching
of -NO ₂ ), 1460, 1385, 1350 (symmetric stretching
of -NO ₂ ), 1280, 1245, 1170, 1080, 1005, 920, 820,
770, 720, 600, 515. Mass (m / e): 373 (M ⁺ ), 195 ((O ₂ N) ₂ PhCO ⁺ ), 161, 148
(OHC-Ph-N (CH ₃ ) CH ₂ ⁺ ), 132, 75, 42. Elemental analysis (C ₁₇ H ₁₅ N ₃ O ₇ , molecular weight 373.3) Calculated C: 54.69%, H: 4.05%, N: 11.26% .Actual value C: 54.94%, H: 4.10%, N: 11.41%.

Further, in this reaction, the compound (10) obtained in Example 2 was used in place of the compound (9), and the completely same operation as the above was carried out to obtain 6- represented by the above structural formula (19). (4-formyl-N-methylanilino) hexyl
3,5-Dinitrobenzoate was obtained as yellow crystals (yield: 54%). The product has the above structure was confirmed by ¹ H-NMR, IR spectrum, Mass spectrum and elemental analysis shown below.

¹ H-NMR, δ (CDCl ₃ , ppm): 1.3-2.2 (m, 8
H), 3.06 (s, 3H), 3.92 (t, J = 7.0Hz, 2H), 4.46 (t, J
= 6.5Hz, 2H), 6.67 (d, J = 9.0Hz, 2H), 7.68 (d, J = 9.0
Hz, 2H), 9.12 (d, J = 2.0Hz, 2H), 9.19 (t, J = 2.0Hz,
1H), 9.69 (s, 1H). IR (cm ^-1 ): 3110, 2940, 2860, 1730 (esteric -C = O),
1680 (aldehydic -C = O), 1595, 1540 (asymmetric str
etching of -NO ₂ ), 1460, 1385, 1340 (symmetric stre
tching of -NO ₂ ), 1290, 1250, 1170, 1070, 995, 920,
825, 770, 720,590, 515. Mass (m / e): 430 (M ⁺ +1), 253, 195 ((O ₂ N) ₂ PhCO ⁺ ), 14
8 (OHC-Ph-N (CH ₃ ) CH ₂ ⁺ ), 132, 77, 43. Elemental analysis (C ₂₁ H ₂₃ N ₃ O ₇ , molecular weight 429.4) Calculated C: 58.74%, H: 5.40%, N 9.79% .Actual value C: 58.67%, H: 5.52%, N 9.63%.

Examples 12 and 13

[0093]

Embedded image

Compound (18) 2.24 obtained in Example 10
40 ml of ethanol / THF (volume ratio to g (6.00 mmol))
2/1) was added and heated to reflux to form a uniform solution. Malononitrile 3.96 g (60.0 mmo)
l) was added, and a few drops of 0.1 mol / L-sodium hydroxide aqueous solution was added as a catalyst. Further, when heated and refluxed for 16 hours, an orange solid was precipitated. After cooling to room temperature,
The orange solid was collected by filtration and recrystallized from chloroform to obtain the compound of the structural formula (20) above.
2- [4- (2,2-dicyanovinyl) -N-methylanilino] ethyl
2.11 g (yield: 84%) of 3,5-dinitrobenzoate was obtained as reddish brown crystals. The fact that the product has the above-mentioned structure is shown below by ¹ H-NMR, IR spectrum, Mass.
Confirmed by spectrum and elemental analysis.

¹ H-NMR, δ (CDCl ₃ , ppm): 3.21 (s, 3H),
3.95 (t, J = 5.7Hz, 2H), 4.68 (t, J = 5.7Hz, 2H), 6.83
(d, J = 9.0Hz, 2H), 7.49 (s, 1H), 7.83 (d, J = 9.0Hz,
2H), 9.02 (d, J = 2.0Hz, 2H), 9.21 (t, J = 2.0 Hz, 1
H). IR (cm ^-1 ): 3105, 2920, 2220 (-CN), 1740 (-C = O), 16
10, 1565, 1540 (asymmetric stretching of -NO ₂ ), 15
20, 1460, 1440, 1395, 1345 (symmetric stretching o
f -NO ₂ ), 1270, 1195, 1165, 1140, 1080, 1010, 935,
815, 775, 725, 610, 575, 520. Mass (m / e): 422 (M ⁺ +1), 373, 196 ((NC) ₂ C = CH-Ph-N (C
H ₃ ) CH ₂ ⁺ ), 195 ((O ₂ N) ₂ PhCO ⁺ ), 161, 148, 132, 77, 4
7, 43, 35. Elemental analysis (C ₂₀ H ₁₅ N ₅ O ₆ , molecular weight 421.4) Calculated value C: 57.01%, H: 3.59%, N: 16.62%. Measured value C: 56.83%, H: 3.46%, N: 16.60%.

In this reaction, the compound (19) obtained in Example 11 was used in place of the compound (18), and the completely same operation as the above was carried out.
6- [4- (2,2-dicyanovinyl) -N-methylanilino] hexyl 3,5-dinitrobenzoate represented by 1) was obtained as reddish brown crystals (yield: 81%). The product has the above structure was confirmed by ¹ H-NMR, IR spectrum, Mass spectrum and elemental analysis shown below.

¹ H-NMR, δ (CDCl ₃ , ppm): 1.2-2.1 (m, 8
H), 3.10 (s, 3H), 3.47 (t, J = 6.6Hz, 2H), 4.46 (t, J
= 6.6Hz, 2H), 6.68 (d, J = 9.1Hz, 2H), 7.45 (s, 1H),
7.80 (d, J = 9.1Hz, 2H), 9.14 (d, J = 2.0Hz, 2H), 9.20
(t, J = 2.0Hz, 1H). IR (cm ^-1 ): 3080, 2940, 2220 (-CN), 1725 (-C = O), 16
05, 1560, 1543 (asymmetric stretching of -NO ₂ ), 15
20, 1465, 1395, 1345 (symmetric stretching of -N
O ₂ ), 1280, 1185, 1165, 1080, 965, 920, 825, 775, 7
25, 605, 585, 530. Mass (m / e): 477 (M ⁺ ), 429, 196 ((NC) ₂ C = CH-Ph-N (C
H ₃ ) CH ₂ ⁺ ), 195 ((O ₂ N) ₂ PhCO ⁺ ), 148, 132, 75, 43. Elemental analysis (C ₂₄ H ₂₃ N ₅ O ₆ , molecular weight 477.5) Calculated C: 60.37%, H: 4.86%, N: 14.67%. Actual value C: 60.48%, H: 5.01%, N: 14.41%.

Example 14 Nonlinear optical measurement

3,5-Dinitrobenzoic acid ester derivatives (9) and (1 obtained in Examples 1, 4, 9, 12 and 13)
Each of 2), (17), (20) and (21) was made into a uniform particle state using an agate mortar and sandwiched between slide glasses. Using these samples, the 2nd harmonic (S) generated from 3,5-dinitrobenzoic acid ester derivative
H wave) was measured. Using an Nd: YAG laser (1064nm) with uniform polarization as the incident fundamental wave, the generated 532nm SH wave was collected by a lens, then introduced into a spectroscope through an optical fiber and detected by a photomultiplier.
Wave intensity was integrated with a box car. SH that is generated from urea is used as the standard sample.
The relative SH wave intensity was calculated with the wave intensity of 1. Table 1 shows the results. Further, all of the above compounds had good crystallinity, and it was possible to easily form a single crystal by an ordinary recrystallization method.

[0100]

[Table 1]

On the other hand, Examples 2, 3, 8, 10 and 11
3,5-dinitrobenzoic acid ester derivative (1
0), (11), (16), (18) and (for 19) also performs the same measurements were determined relative SH wave intensity SH wave intensity generated from urea as 1, both 10 ^{- The} value was smaller than ³ , and the second-order nonlinear optical effect of these compounds was very small.

Examples 15 to 17

[0103]

Embedded image

3.31 g of the compound (13) obtained in Example 5
(4.00 mmol) and SnCl ₂ · 2H ₂ O 9.03 g of (40.0 mmol) 50
0.303 g (8.00 mmol) sodium borohydride in 50 ml ethanol
Was added and the mixture was stirred at 60 ° C. for 3 hours. After the solvent was distilled off under reduced pressure, ethyl acetate and saturated aqueous sodium hydrogen carbonate solution were added to the residue, and the organic layer was separated. After dehydrating the organic layer with anhydrous sodium sulfate, the solution was concentrated under reduced pressure. After purification by silica gel column chromatography,
Purified by recrystallization from ethyl acetate,
2.50 g (yield: 81%) of 2- [4- (perfluorooctylsulfonyl) -N-methyl-4-anilino] ethyl 3,5-diaminobenzoate of the structural formula represented by 2) was obtained as white crystals. The fact that the product has the above structure is shown below.
^It was confirmed by ¹ H-NMR, IR spectrum, Mass spectrum and elemental analysis.

¹ H-NMR δ (CDCl ₃ + DMSO-d ₆ , ppm): 3.18
(s, 3H), 3.8-4.2 (m, 6H), 4.46 (t, J = 5.7Hz, 2H),
6.22 (t, J = 2.2Hz, 1H), 6.62 (d, J = 2.2Hz, 2H), 6.89
(d, J = 9.3Hz, 2H), 7.78 (d, J = 9.3Hz, 2H). IR (cm ^-1 ): 3375 (-NH ₂ ), 2955, 1715 (-C = O), 1595, 1
535, 1520, 1465, 1390, 1355, 1235, 1215, 1155, 112
0, 1085, 1030, 995, 955, 900, 855, 820, 770,745, 7
10, 650, 630, 585, 555, 530. Mass (m / e): 767 (M ⁺ ), 602, 348 (M ⁺ -(C ₈ F ₁₇ )), 284
(M ⁺ -(SO ₂ C ₈ F ₁₇ )), 196, 179, 169 (CF ₃ (CF ₂ ) ₂ ⁺ ), 152,
119 (CF ₃ CF ₂ ⁺ or Ph-N (CH ₃ ) CH ₂ ⁺ ), 107, 91, 69 (C
. F ₃ ⁺⁾ Elemental analysis _{(C 24 H 18 N 3 SO} 4 F 17, molecular weight 767.5) Calculated C: 37.56%, H: 2.36 %, N: 5.48% Found C:. 37.58%, H: 2.16% , N: 5.41%.

Further, instead of the compound (13) in this reaction, the compound (14) obtained in Examples 6 and 7 was used.
Using (15) and (15), the same operation as described above is performed, and the structure represented by the above structural formulas (23) and (24)
5-Diaminobenzoic acid ester derivatives were synthesized respectively. The yield of the obtained compound and the spectrum analysis result are shown below.

Compound (23); Yield: 83% ¹ H-NMR δ (CDCl ₃ , ppm): 3.07 (s, 3H), 3.6-3.7 (m, 4)
H), 3.75 (t, J = 5.9Hz, 2H), 4.43 (t, J = 5.9Hz, 2H),
6.17 (t, J = 2.1Hz, 1H), 6.63 (d, J = 2.1Hz, 2H), 6.73
(d, J = 9.2Hz, 2H), 7.47 (d, J = 9.2Hz, 2H). IR (cm ^-1 ): 3470 (-NH ₂ ), 3435 (-NH ₂ ), 3370, 3220, 2
950, 2920, 2210 (-CN), 1710 (-C = O), 1610, 1525, 146
5, 1435, 1390, 1350, 1235, 1200, 1180, 1135, 1115,
1075, 1050, 1030, 1005, 990, 950, 855, 815, 770,
680, 610, 545,520. Mass (m / e): 310 (M ⁺ ), 158 (NC-Ph-N (CH ₃ ) CH = CH ₂ ⁺ ), 1
52 ((NH ₂ ) ₂ Ph-COOH ⁺ ), 145 (NC-Ph-N (CH ₃ ) CH ₂ ⁺ ), 129,
107, 102 ( ⁺ Ph-CN), 80, 53, 42.

Compound (24); Yield: 74% ¹ H-NMR δ (CDCl ₃ + DMSO-d ₆ , ppm): 2.48 (s, 3H), 3.12
(s, 3H), 3.81 (t, J = 5.7Hz, 2H), 4.0-4.3 (m, 4H),
4.42 (t, J = 5.7Hz, 2H), 6.17 (t, J = 2.2Hz, 1H), 6.57
(d, J = 2.2Hz, 2H), 6.76 (d, J = 9.0Hz, 2H), 7.84 (d,
J = 9.0Hz, 2H). IR (cm ^-1 ): 3420 (-NH ₂ ), 3325 (-NH ₂ ), 2920, 1705 (-
C = O), 1645, 1600, 1550, 1525, 1460, 1430, 1380, 13
50, 1320, 1290, 1240, 1195, 1135, 1115, 1070, 103
2, 1005, 950, 850, 820, 770, 590, 520, 495. Mass (m / e): 327 (M ⁺ ), 175 (CH ₃ CO-Ph-N (CH ₃ ) CH = C
H ₂ ⁺ ), 162 (CH ₃ CO-Ph-N (CH ₃ ) CH ₂ ⁺ ), 152 ((NH ₂ ) ₂ Ph-COO
H ⁺ ), 132, 119 ( ⁺ Ph-COCH ₃ ), 107, 80, 42, 28.

Reference Examples 9 and 10

[0110]

[Chemical formula 26]

The compound (4) obtained in Reference Example 4 (1.267 g, 2.00 mmol), dimethyl 5-hydroxyisophthalate (0.631 g, 3.00 mmol) and triphenylphosphine (0.631 g, 2.40 mmol) were dried under an argon gas atmosphere. Tetrahydrofuran (THF) (10 ml) was added to form a uniform solution, which was then cooled with ice. 0.51 g (3.0 mmol) of diethyl azodicarboxylate (DEAD) dissolved in dry THF was added dropwise under ice cooling. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour.
After evaporating the solvent under reduced pressure, the residue was purified by silica gel chromatography and further recrystallized from acetone / methanol. As a result, (25) above
1.53 g (yield: 93%) of dimethyl 5- {2- [4- (perfluorooctylsulfonyl) -N-methylanilino] ethoxy} isophthalate having the structural formula represented by was obtained as white crystals. Incidentally, the fact that the product has the above structure is shown by ¹ H-
Confirmed from NMR, IR and Mass spectra and elemental analysis.

[0112]¹H-NMR, δ (CDCl_Three, ppm): 3.22 (s, 3H),
3.8-4.1 (m, 2H), 3.93 (s, 6H), 4.2-4.4 (m, 2H), 6.
83 (d, J = 9.2Hz, 2H), 7.71 (d, J = 1.1Hz, 2H), 7.82
(d, J = 9.2Hz, 2H), 8.29 (s, 1H). IR (cm^-1): 2965, 2950, 2930, 1720 (-C = O), 1595, 15
20, 1510, 1480, 1455, 1430, 1365, 1335, 1315, 1250,
 1230, 1195, 1155, 1120, 1105, 1070, 1030,1015, 10
05, 990, 965, 900, 885, 860, 805, 780, 755, 720, 6
95, 670, 625,580, 495, 460. Mass (m / e): 825 (M⁺), 616 (⁺CH₂CH₂N (CH_Three) -Ph-SO₂C₈F
₁₇), 406 (M⁺-(C₈F₁₇)), 342 (M⁺-(SO₂C₈F₁₇)), 179, 16
9 (CF_Three(CF₂)₂ ⁺), 119 (CF_ThreeCF₂ ⁺ or Ph-N (CH_Three) CH ₂ ⁺), 6
9 (CF_Three ⁺). Elemental analysis (C₂₇H₂₀NSO₇F₁₇, Molecular weight 825.5) Calculated value C: 39.28%, H: 2.44%, N: 1.70%. Actual value C: 39.34%, H: 2.26%, N: 1.47%.

The compound (25) thus obtained was 1.00 g (1.2
1 mmol) and 0.242 g (6.00 mmol) of sodium hydroxide
9 ml of methanol / THF / water (volume ratio 1/1/1)
Was dissolved in the solution and heated under reflux for 3 hours. Hydrochloric acid was added to the reaction mixture for neutralization, and the precipitated white solid was collected by filtration and washed with water. The white solid was purified by recrystallization from acetone / water. As a result, the above (2
0.819 g (yield: 85%) of 5- {2- [4- (perfluorooctylsulfonyl) -N-methylanilino] ethoxy} isophthalic acid represented by the structural formula 7) was obtained as white crystals. Incidentally, the fact that the product has the above structure is shown by ¹ H-
Confirmed from NMR, IR and Mass spectra and elemental analysis.

¹ H-NMR δ (CDCl ₃ + DMSO-d ₆ , ppm): 3.23
(s, 3H), 3.8-4.1 (m, 2H), 4.2-4.5 (m, 2H), 6.87
(d, J = 9.2 Hz, 2H), 7.5-8.0 (m, 4H), 8.29 (s, 1H). IR (cm ^-1 ): 3445 (-OH), 3005, 2955, 1705 (-C = O ), 15
95, 1550, 1520, 1465, 1390, 1355, 1330, 1245, 1215,
1155, 1120, 1085, 1065, 995, 945, 910, 860, 825,
760, 745, 725, 789, 750, 695, 660, 630, 585, 555,
525. Mass (m / e): 797 (M ⁺ ), 778 (M ⁺ -F), 602, 169 (CF ₃ (CF
₂ ) ₂ ⁺ ), 119 (CF ₃ CF ₂ ⁺ ), 105, 91, 69 (CF ₃ ⁺ ). Elemental analysis (C ₂₅ H ₁₆ NSO ₇ F ₁₇ , molecular weight 797.4) Calculated C: 37.66%, H: 2.02%, N: 1.77% .Actual value C: 37.42%, H: 1.78%, N: 1.68%.

In the above reaction, the compound (5) obtained in Reference Example 5 was used in place of the compound (4), and the completely same operation as the above was carried out to obtain the compound represented by the structural formula (26). 5- [2- (4-Cyano-]-[2- (4-cyano-N-methylanilino) ethoxy] isophthalate dimethyl (white crystal, yield: 84%) represented by the above structural formula (28) N
-Methylanilino) ethoxy] isophthalic acid was obtained as white crystals. (Yield: 100%) It was confirmed by ¹ H-NMR, IR spectrum, Mass spectrum and elemental analysis shown below that these products had the above structures.

Compound (26); ¹ H-NMR, δ (CDCl ₃ , ppm): 3.13 (s, 3H), 3.83 (t, J =
5.1Hz, 2H), 3.93 (s, 6H), 4.24 (t, J = 5.1Hz, 2H),
6.77 (d, J = 9.2Hz, 2H), 7.49 (d, J = 9.2Hz, 2H), 7.70
(d, J = 1.1Hz, 2H), 8.28 (s, 1H). IR (cm ^-1 ): 3065, 2950, 2850, 2210 (-CN), 1730 (-C =
O), 1605, 1525, 1435, 1390, 1345, 1320, 1250, 1185,
1140, 1120, 1060, 1020, 1005, 935, 910, 885, 820,
785, 765, 720, 670, 650, 545, 510. Mass (m / e): 368 (M ⁺ ), 337 (M ⁺ -OCH ₃ ), 238, 224, 210
((CH ₃ OOC) ₂ Ph-COOH ⁺ ), 179, 159 (NC-Ph-N (CH ₃ ) CH ₂ C
H ₂ ⁺ ), 151, 145 (NC-Ph-N (CH ₃ ) CH ₂ ⁺ ), 129, 102 ( ⁺ Ph-C
N), 83, 63, 43, 28. Elemental analysis (C ₂₀ H ₂₀ N ₂ O ₅ , molecular weight 368.4) Calculated C: 65.19%, H: 5.48%, N: 7.61%. Measured C: 64.95%, H: 5.35%, N: 7.55%.

Compound (28); ¹ H-NMR, δ (CDCl ₃₊ DMSO-d ₆ , ppm): 3.13 (s, 3H), 3.86
(t, J = 5.2Hz, 2H), 4.25 (t, J = 5.2Hz, 2H), 6.75 (d,
J = 9.0Hz, 2H), 7.47 (d, J = 9.0Hz, 2H), 7.67 (d, J =
1.1Hz, 2H), 8.27 (s, 1H). IR (cm ^-1 ): 3435, 2910, 2640, 2210 (-CN), 1700 (-C =
O), 1605, 1525, 1460, 1435, 1385, 1360, 1330, 1310,
1275, 1205, 1180, 1130, 1105, 1060, 1020,995, 97
5, 910, 885, 815, 760, 740, 690, 665, 595, 545, 45
0. Mass (m / e): 340 (M ⁺ ), 182 ((HOOC) ₂ Ph-OH ⁺ ), 158 (NC
-Ph-N (CH ₃ ) CH = CH ₂ ⁺ ), 145 (NC-Ph-N (CH ₃ ) CH ₂ ⁺ ), 129, 1
02 ( ⁺ Ph-CN), 91, 42, 28. Elemental analysis (C ₁₈ H ₁₆ N ₂ O ₅ , molecular weight 340.3) Calculated value C: 63.52%, H: 4.74%, N: 8.23%. Measured value C: 63.56%, H: 4.61%, N: 8.14%.

Examples 18 to 22

[0119]

Embedded image

3,5-diamino obtained in Examples 15 to 17
Benzoic acid ester derivative and obtained in Reference Examples 9 and 10
Combinations of different isophthalic acid derivatives listed in Table 2
It was weighed to obtain an equimolar amount (2 mmol). Weighed
Add 3 ml of thionyl chloride to the isophthalic acid derivative and add 3
The mixture was heated under reflux for an hour. After the reaction, remove excess thionyl chloride.
Evaporate under reduced pressure and dry 2 ml of N-methyl-2-pyrrolidone (N
MP). On the other hand, under argon gas atmosphere, weigh
2 ml of dried 3,5-diaminobenzoate derivative
Dissolved in NMP. While keeping this solution at -78 ° C,
The dry NMP solution of isophthalic acid derivative prepared in
Thereafter, the polycondensation reaction was carried out by stirring at 60 ° C. for 1 hour. Next
Then, the reaction solution was poured into 400 ml of methanol to precipitate the polymer.
I'm sorry. The polymer obtained at the end is (P1)-(P
In the case of 3) 2 ml of THF, (P4) and (P4)
In the case of 5), it was dissolved in 2 ml of N, N-dimethylformamide,
After filtering this solution, pour it into 400 ml of methanol and
Was allowed to settle. Finally, the polymer obtained was filtered off.
Let dry. As a result, the above structures (P1) to (P5)
The respective polyamides obtained were obtained. Incidentally, those
The chemical structure is shown below ¹1 H-NMR and IR spectrum
I confirmed from Le. Light scattering method for the obtained polyamide
Determine the weight average molecular weight by using a differential scanning calorimeter
The glass transition temperature was measured. Table 2 shows the results. So
As a result, both polyamides have a high glass transition temperature.
And a polymer with excellent thermal stability that is stable up to 300 ° C
I found out.

Polyamide (P1); ¹ H-NMR, δ (CDCl ₃ + DMSO-d ₆ , ppm): 3.1-3.4 (6H), 3.6-
4.0 (4H), 4.2-4.6 (4H), 6.8-7.0 (4H), 7.0-7.2 (2
H), 7.4-7.6 (2H), 7.6-7.8 (5H), 7.9-8.1 (1H), 10.3-
10.7 (2H). IR (cm ^-1 ): 3100, 2960, 1720 (-C = O), 1675, 1595, 15
45, 1520, 1450, 1390, 1360, 1340, 1250, 1225, 1160,
1130, 1110, 1085, 1060, 1040, 1000, 965, 885, 86
0, 820, 780, 740 710, 680, 650, 630, 580, 550, 53
0.

Polyamide (P2); ¹ H-NMR, δ (CDCl ₃ + DMSO-d ₆ , ppm): 3.0-3.4 (6H), 3.7-
4.1 (4H), 4.3-4.6 (4H), 6.7-6.9 (2H), 6.9-7.1 (2
H), 7.3-7.5 (2H), 7.6-7.9 (4H), 8.1-8.3 (2H), 8.3-
8.4 (1H), 8.6-8.7 (1H), 10.3-10.7 (2H). IR (cm ^-1 ): 3120, 3960, 2925, 2215 (-CN), 1720 (-C =
O), 1670, 1605, 1595, 1545, 1525, 1450, 1390, 1360,
1340, 1305, 1250, 1215, 1180, 1160, 1130, 1110, 10
85, 1060, 1000, 970, 890, 820, 765, 745, 710, 685,
650, 630, 590, 550 530.

Polyamide (P3); ¹ H-NMR, δ (CDCl ₃ + DMSO-d ₆ , ppm): 3.0-3.4 (6H), 3.7-
4.1 (4H), 4.2-4.7 (4H), 6.7-6.9 (2H), 6.9-7.1 (2
H), 7.4-7.5 (2H), 7.6-7.9 (4H), 8.1-8.4 (3H), 8.6-
8.8 (1H), 10.3-10.7 (2H). IR (cm ^-1 ): 3130, 2970, 2940, 2215 (-CN), 1720 (-C =
O), 1675, 1610, 1595,1550, 1525, 1450, 1385, 1355,
1250, 1215, 1180, 1155, 1125, 1110, 1085,1055, 10
00, 970, 880, 820, 765, 745, 705, 690, 650, 630, 5
85, 550.

Polyamide (P4); ¹ H-NMR, δ (CDCl ₃ + DMSO-d ₆ , ppm): 3.0-3.4 (6H), 3.6-
4.0 (4H), 4.1-4.7 (4H), 6.8-7.0 (4H), 7.4-7.6 (4
H), 7.6-7.9 (2H), 8.0-8.4 (3H), 8.5-8.8 (1H), 10.0-
10.7 (2H). IR (cm ^-1 ): 3110, 2925, 2215 (-CN), 1720 (-C = O), 16
75, 1605, 1545, 1525, 1450, 1385, 1330, 1310, 1220,
1180, 1055, 1005, 880, 820, 765, 670, 545,430.

Polyamide (P5); ¹ H-NMR, δ (CDCl ₃ + DMSO-d ₆ , ppm): 2.3-2.5 (3H), 3.0-
3.4 (6H), 3.7-4.1 (4H), 4.2-4.6 (4H), 6.6-7.0 (4
H), 7.6-7.9 (4H), 8.1-8.4 (3H), 8.6-8.8 (1H), 10.0-
10.7 (2H). IR (cm ^-1 ): 3190, 2955, 1725 (-C = O), 1660, 1595, 15
50, 1525, 1450, 1385, 1360, 1330, 1295, 1240, 1215,
1155, 1125, 1115, 1080, 1060, 1000, 960, 885, 82
0, 765, 745, 705, 680, 650, 555.

[0126]

[Table 2]

───────────────────────────────── Example The weight average glass transition number using the iso used in the polyamide Compound number Phthalic acid Diamine Molecular weight Temperature (℃) ───────────────────────────────── 18 (P1) (27) (22) 8.17x10 ³ > 300 19 (P2) (27) (23) 6.41x10 ⁴ 157 20 (P3) (28) (22) 2.83x10 ⁴ 165 21 (P4) (28) (23) 3.50x10 ⁴ 167 22 (P5) (27) (24) 2.21x10 ⁴ 157 ──────────────────────────────────

Example 23 Linear and nonlinear optical measurements

The polyamides (P2) and (P3) obtained in Examples 19 and 20 were dissolved in THF to give 5% by weight.
Make a solution and put it on a quartz glass substrate at 2000 per minute
Each polyamide thin film was obtained by spin coating at a rotation speed of rotation. Next, the ultraviolet absorption spectrum was measured using these substrates, and the maximum absorption wavelength and the absorption edge wavelength of these polyamides were obtained.
The results are shown in Table 3. As can be seen from the table, it was found that these polyamides have a short absorption edge wavelength and therefore are materials having good transparency in the visible light region.

Further, the polyamides (P2) and (P3)
Was dissolved in THF to prepare a 10 wt% solution, which was spin-coated on a glass substrate at a rotation speed of 1000 rotations per minute to obtain polyamide thin films. next,
These substrates were placed on a hot plate made of aluminum and heated to near the glass transition temperature of each polyamide.
Table 3 shows the temperature rise (corona charging temperature) for each polyamide. Corona charging was performed from above 2.5 cm using a tungsten needle at a charging voltage of 10 kV. This state was maintained for at least 20 minutes to orient the dye moiety in the side chain, and then cooled while continuing corona charging to bring the polyamide to a glassy state.

Next, the maker fringe method (J. Jerphagno
n et al., Journal of Applied Physics, Volume 41, p.16.
67 (1970)), the second harmonic (SH wave) generated from the polyamide thin film subjected to the electric field orientation treatment was measured. As the incident fundamental wave, a 532 nm SH wave was detected using an Nd: YAG laser (1064 nm) having a uniform polarization plane. A typical maker fringe pattern is shown in FIG. Also, the film thickness
SH waves generated by the maker fringe method were also detected for a 1 mm y-cut quartz crystal. From these measurement results, the second-order nonlinear optical constant d ₃₃ value of each polyamide was calculated by curve fitting using the least-squares method with reference to the d ₁₁ value (0.5 pm / V) of the y-cut quartz crystal. . Table 3 shows the results. Further, it was confirmed that the d ₃₃ value shown here was not changed at all even when these polyamide thin films were allowed to stand at room temperature for about 1 month and then measured.

[0132]

[Table 3] ────────────────────────────────── polyamide maximum absorption wavelength absorption edge wavelength corona charging temperature d ₃₃ value Compound number (nm) (nm) (℃) (pm / V) ──────────────────────────────── ── (P2) 306 372 1908 (P3) 305 443 200 14 ─────────────────────────────────────

[Brief description of drawings]

1 is a graph showing a maker fringe pattern of a thin film produced from the polyamide obtained in Example 20. FIG.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 4, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0066

[Correction method] Change

[Correction contents]

¹ H-NMR, δ (CDCl ₃ , ppm): 1.77 (t, J = 5.5
Hz, 1H), 3.14 (s, 3H), 3.63 (t, J = 5.2Hz, 2H), 3.85
(t, J = 5.2Hz, 2H), 6.80 (d, J = 9.2Hz, 2H), 7.6-8.2
(m, 6H). IR (cm ^-1 ): 3500, 2920, 2225 (-CN), 1600, 1555, 152
0, 1440, 1420, 1375, 1345, 1315, 1260, 1215, 1145,
1105, 1070, 1045, 975, 845, 830, 555, 510. Elemental analysis (C ₁₆ H ₁₆ N ₂ O , molecular weight 280.3) Calculated C: 68.55%, H: 5.75%, N 19.99%. Measured C: 68.71%, H: 5.78%, N 20.07%.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0081

[Correction method] Change

[Correction contents]

Compound (13): Yield: 86% ¹ H-NMR, δ (CDCl ₃ , ppm): 3.21 (s, 3H), 3.95 (t, J =
5.9Hz, 2H), 4.70 (t, J = 5.9Hz, 2H), 6.87 (d, J = 9.5H
z, 2H), 7.77 (d, J = 9.5Hz, 2H), 9.05 (d, J = 2.0Hz, 2
H), 9.21 (t, J = 2.0Hz, 1H). IR (cm ^-1 ): 3105, 2970, 1735 (-C = O), 1630, 1595, 15
45 (asymmetric stretching of -NO ₂ ), 1520, 1460, 13
90, 1350 (symmetric stretching of -NO ₂ ), 1330, 128
0, 1240, 1205, 1155, 1115, 1085, 995, 930, 825, 77
5, 725, 685, 655, 605, 585, 550, 520. Mass (m / e): 827 (M ⁺ ), 808 (M ⁺ -F), 602 (CF ₃ (CF ₂ ) ₇ SO
₂ Ph-N (CH ₃ ) CH ₂ ⁺ ), 408 (M ⁺ -(C ₈ F ₁₇ )), 344 (M ⁺ -(SO ₂ C ₈ F)
₁₇ )), 195 ((O ₂ N) ₂ PhCO ⁺ ), 169 (CF ₃ (CF ₂ ) ₂ ⁺ ), 149, 13
1, 119 (CF ₃ CF ₂ ⁺ or Ph-N (CH ₃ ) CH ₂ ⁺ ), 105, 91, 75, 69
(CF3 ⁺ ), 42. Elemental analysis (C ₂₄ H ₁₄ N ₃ SO ₈ F ₁₇ , molecular weight 827.4) Calculated C: 34.84%, H: 1.71%, N: 5.08%. Measured C: 34.76%, H: 1.53%, N: 4.87%.

Claims (4)

[Claims] 1. A compound represented by the following general formula (I) (In the formula, X ¹ and X ² are a nitro group or an amino group, Y ¹
Is a linear or branched hydrocarbon chain having 1 to 12 carbon atoms, R ¹ may be a hydrogen atom, a lower alkyl group, or Y ¹ and a nitrogen atom to be bonded to form a ring. , A ¹ is a hydrogen atom, an electron-accepting group, or a π-conjugated system substituent containing an electron-accepting group. ) A benzoic acid ester derivative represented by: 2. The following general formula (II): (In the formula, Y ¹ is a linear or branched hydrocarbon chain having 1 to 12 carbon atoms, R ¹ is a hydrogen atom, a lower alkyl group, or Y ¹ and a nitrogen atom to be bonded together form a ring. A ¹ is a hydrogen atom, an electron-accepting group, or a π-conjugated substituent containing an electron-accepting group, and is composed of a dinitrobenzoate derivative represented by
Generated from urea using the laser beam of
A non-linear optical material in which the relative second harmonic intensity generated by the same fundamental input wave when the intensity of the second harmonic is 1 is 10 ⁻³ or more. 3. The repeating unit has the following general formula (III): (In the formula, R ² and R ³ may be the same or different and each is a hydrogen atom or the following general formula (IV): And m is an integer of 0 or 1, Y ¹ , Y ² and Y ³ may be the same or different and have 1 to 12 carbon atoms.
A straight or branched hydrocarbon chain of R ¹ , R ⁴ and R
⁵ may be the same or different, and may form a ring together with a hydrogen atom, a lower alkyl group, or Y ¹ , Y ² or Y ³ and the nitrogen atom to which they are bonded, A ² ,
A ³ and A ⁴ may be the same or different and each is an electron-accepting group or a π-conjugated substituent containing an electron-accepting group. ) And having a weight average molecular weight of 1,000 or more. 4. The repeating unit has the following general formula (III): (In the formula, R ² and R ³ may be the same or different and each is a hydrogen atom or the following general formula (IV): And m is an integer of 0 or 1, Y ¹ , Y ² and Y ³ may be the same or different and have 1 to 12 carbon atoms.
A straight or branched hydrocarbon chain of R ¹ , R ⁴ and R
⁵ may be the same or different, and may form a ring together with a hydrogen atom, a lower alkyl group, or Y ¹ , Y ² or Y ³ and the nitrogen atom to which they are bonded, A ² ,
A ³ and A ⁴ may be the same or different and each is an electron-accepting group or a π-conjugated substituent containing an electron-accepting group. ), And a polymer nonlinear optical material composed of an aromatic polyamide having a weight average molecular weight of 1,000 or more.