JPH11149099A - Compound having pyridyl group, betaine compound, polymer and high molecular nonlinear optical material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer with a betaine compd. having a high β-value introduced at high density into a high molecular side chain via covalent bonds by using a specified compd. having a pyridyl. group. SOLUTION: A compd. having a pyriclyl group represented by the formula is used. In the formula, A is H or acyl, Q is a single bond, O, S or SO2 , (m) is an integer of 0-10, (p) is an integer of 0 or 1, and in the case of m=0 or p=0, Q is a single bond. A compd. with a diamine component chemically bonded using such a betaine compd. as a polymerizing group is synthesized. A high molecular nonlinear optical material comprising a polymer obtd. using this diamine compd. as a monomer has superior secondary nonlinear optical intensity as well as satisfactory moldability. Since the optical material is a glassy (non- crystalline) polymer, unlike a crystalline polymer the optical, material is less liable to scatter light and is excellent in transparency.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel betaine compound and a precursor compound thereof, a polymer derived from the betaine compound, and a polymer nonlinear optical material comprising the polymer. That is, the present invention relates to a polymer material exhibiting good second-order nonlinear optical characteristics and a raw material compound thereof.

[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 and 4-
Nitroaniline, 2-methyl-4-nitroaniline (MN
A) It has been found that organic compounds such as 4- (N, N-dimethylamino) -4'-nitrostilbene (DANS) have relatively high molecular polarizabilities and consequently exhibit some nonlinear optical properties. Research and development of various organic nonlinear optical materials have been actively conducted. 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. In addition, when the material is made into an element, not only a method using a single crystal but also various methods such as an evaporation method, an LB film, a liquid crystal, or a dispersion in a polymer matrix can be considered. doing. (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
Year) etc.)

However, conventional organic nonlinear optical materials do not necessarily exhibit high secondary molecular polarizabilities (β values), and are resistant to organic compounds having a π-electron conjugated system for the purpose of expressing large β values. Organic compounds having an electron-donating group and a strong electron-accepting group are difficult to crystallize, and even if crystals can be formed, a centrally symmetric structure is formed during crystallization due to the presence of an electric dipole in the ground state. It is easy to remove, and the large nonlinearity exhibited by one molecule is easily offset as a whole crystal. Also, when dispersed and used in a polymer matrix, it is easy to take a centrally symmetric structure, so that the second harmonic intensity decreases. There was a problem that it was remarkable. 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.

On the other hand, the inventors of the present invention have excellent secondary molecular polarizability (β value), can be dispersed in a polymer matrix, and have a short absorption wavelength end, that is, a fundamental wave or a generated wave. As a result of studying for the purpose of obtaining a new nonlinear optical material that does not easily cause the absorption of the harmonics,
It has already been found that a betaine compound having a specific structure exhibits a high second-order molecular polarizability (β value), and that a certain degree of second harmonic can be generated by dispersing the compound in a polymer matrix. However, although the obtained betaine compound shows a high β value, the solubility of the betaine compound is low in a system in which the compound is dispersed in a polymer matrix. Because the introduction rate is limited and the effect of electric field orientation is difficult to appear due to strong association,
The second harmonic as high as expected from the β value was not generated. Therefore, in order to obtain a polymer in which a betaine compound is introduced into a polymer side chain via a covalent bond, an addition polymerization monomer having a betaine residue and a polymer thereof have been reported by the present inventors. (N. Nemoto et al., J. Mater. Chem., 7th.
Vol., P.1389-1393 (1997)) However, the polymerizability of the obtained addition-polymerizable monomer was low, and the introduction rate of betaine component in the polymer was limited.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to obtain a polymer in which a betaine compound having a high β value is introduced into a polymer side chain at a high density via a covalent bond, and a raw material compound thereof. .

[0007]

Means for Solving the Problems The present inventors have made intensive studies to obtain the above-mentioned raw material compounds. As a result, a compound obtained by chemically bonding a diamine component as a polymer group to a betaine compound having a specific structure can be synthesized, or a polymer can be easily obtained by polyaddition or polycondensation using the compound as a raw material. The present inventors have found that the obtained polymer exhibits good second-order nonlinear optical characteristics, and have reached the present invention.

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

[0009]

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Wherein A is a hydrogen atom or an acyl group;
Is a single bond, an oxygen atom, a sulfur atom or a group represented by SO ₂ , m is an integer of 0 to 10, and p is an integer of 0 or 1. However, when m is 0 or p is 0, Q is a single bond. A) a compound having a pyridyl group represented by the following general formula (II) derived from the compound:

[0011]

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Wherein A is a hydrogen atom or an acyl group;
Is a single bond, an oxygen atom, a sulfur atom or a group represented by SO ₂ ; Y is a nitrogen atom or a carbon atom having a substituent R;
Is a single bond or a methylene group, R ¹ and R ² are a hydrogen atom,
A lower alkyl group or a carbon atom to which each is bonded may form an aromatic ring, or may have a substituent on the aromatic ring, m is an integer of 0 to 10;
Is an integer of 0 or 1. However, when m is 0 or p is 0, Q is a single bond. R is a hydrogen atom, a lower alkyl group or a phenyl group. A) a betaine compound represented by the following general formula (III) in a repeating unit derived from the betaine compound:

[0013]

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(Wherein Q is a single bond, an oxygen atom, a sulfur atom or a group represented by SO ₂ , Y is a nitrogen atom or a carbon atom having a substituent R, Z is a single bond or a methylene group, R is
¹ and R ² may form an aromatic ring together with a hydrogen atom, a lower alkyl group or a carbon atom to which each is bonded, or may have a substituent on the aromatic ring;
R ³ may form an imide ring together with a hydrogen atom or one of the bonds, m is an integer of 0 to 10, and p is an integer of 0 or 1. However, when m is 0 or p is 0, Q is a single bond. R is a hydrogen atom,
It is a lower alkyl group or a phenyl group. The present invention relates to a polymer containing at least 1 mol% of a repeating unit containing a structural unit represented by the formula (1) and having a weight average molecular weight of 2,000 or more, and a polymer nonlinear optical material comprising the polymer.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The above general formulas (I) and (II)
Among them, as the acyl group represented by A, those which are stably present in the reaction using these compounds and which can be removed without damaging other sites in the elimination reaction are selected. Acyl groups meeting this requirement include acetyl, chloroacetyl, trichloroacetyl, trifluoroacetyl, phenylacetyl, propionyl, 3-phenylpropionyl, butyryl, heptanoyl, hexanoyl, isobutyryl, Examples thereof include a valeryl group, an isovaleryl group, a pivaloyl group, a cyclohexanecarbonyl group and a benzoyl group.

In the above general formulas (II) and (III),
As the lower alkyl group represented by R ¹ , R ² and R,
Examples thereof include those having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group.
The aromatic ring formed integrally with the carbon atom to which each of R ¹ and R ² is bonded includes a benzene ring,
Examples of the naphthalene ring, anthracene ring, and phenanthrene ring can be given. The substituents which may be substituted on these aromatic rings include a halogen atom, 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 lower alkyl group having 1 to 6 carbon atoms such as hexyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group,
Examples thereof include a lower alkoxy group having 1 to 6 carbon atoms such as a sec-butoxy group, a tert-butoxy group, a pentyloxy group, and a hexyloxy group, a phenyl group, a cyano group, and a nitro group.

Among the compounds having a pyridyl group represented by the general formula (I) of the present invention wherein p is 0 and A is a hydrogen atom, for example, the following general formula (IV)

[0018]

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(Wherein m is an integer of 0 to 10), and a pyridyl compound represented by the following general formula (V)

[0020]

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(Wherein X ¹ is a hydroxyl group or a halogen atom other than fluorine) by an esterification reaction with dinitrobenzoic acid or its halide represented by the following general formula (VI):

[0022]

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(Wherein m is an integer of 0 to 10), and can be produced by synthesizing a dinitro compound, and then reducing the nitro group of the compound by a known method. Some of the pyridyl compounds represented by the general formula (IV) used herein are commercially available, and those not commercially available can be easily produced by a known method. The amino group of the thus-obtained compound having a pyridyl group represented by the general formula (I), wherein p is 0 and A is a hydrogen atom, is converted to a compound known in the literature (for example, "Protective Groups"). in Organic Synthesis ", Jo
hn Wiley & Sons, New York, 1981, p.349-357)
A compound having p of 0 and A being an acyl group among the compounds having a pyridyl group represented by the general formula (I) can be synthesized by the acylation.

On the other hand, among the compounds having a pyridyl group represented by the general formula (I) of the present invention, those in which p is 1 and A is an acyl group can be produced, for example, by the following synthesis method. Can be. That is, the following general formula (VII)

[0025]

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(Wherein Q is a group represented by a single bond, an oxygen atom, a sulfur atom or SO ₂ , X is a halogen atom other than fluorine, and m is an integer of 0 to 10. In this case, Q is a single bond.) And a dinitrobenzoic acid or a halide thereof represented by the general formula (V) by an esterification reaction with the compound represented by the following general formula (V)
III)

[0027]

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(Wherein Q is a group represented by a single bond, an oxygen atom, a sulfur atom or SO ₂ , X is a halogen atom other than fluorine, and m is an integer of 0 to 10. In this case, Q is a single bond), and then the nitro group of this compound is reduced by a known method to obtain the following general formula (IX)

[0029]

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(Wherein Q is a group represented by a single bond, an oxygen atom, a sulfur atom or SO ₂ , X is a halogen atom other than fluorine, and m is an integer of 0 to 10. In this case, Q is a single bond.) After synthesizing a diamine compound represented by the following formula (V):

[0031]

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Wherein A ¹ is an acyl group, Q is a single bond, a group represented by an oxygen atom, a sulfur atom or SO ₂ , X is a halogen atom other than fluorine, and m is an integer of 0-10. However, when m is 0, Q is a single bond.) The compound represented by the general formula (I) is synthesized by a so-called Heck reaction of this compound with 4-vinylpyridine. Among the compounds having a pyridyl group, those in which p is 1 and A is an acyl group can be produced. Reagents and conditions used for the Heck reaction are described in detail in known literature. (For example, Richard F. Heck, "Pa
lladium Reagents in Organic Syntheses ", Academic P
ress (1985); DWBruce et al., Liquid Crystals, 3rd.
Vol. P. 385 (1988), etc.) Note that some of the compounds represented by the general formula (VII) used herein are commercially available, and those not commercially available are described later. It can be produced through a known reaction as shown in the examples. When the amino group of the diamine compound represented by the general formula (IX) is acylated, a method known in the literature (for example, "Protective Groups in Organic Sy
nthesis ", John Wiley & Sons, New York, 1981, p.3
49-357) is available.

Further, among the compounds having a pyridyl group represented by the general formula (I), those in which A is a hydrogen atom,
Among the compounds having a pyridyl group represented by the general formula (I), when A is an acyl group, the acyl group can be converted by a known method (for example, "Protective Groups in Organic Synthesiology").
s ", John Wiley & Sons, New York, 1981, p.349-357
).

The compound having a pyridyl group represented by the above general formula (I) obtained by the above method and having A as an acyl group is used as a precursor,
Among the betaine compounds represented by I), those wherein A is an acyl group can be produced. That is, a stilbazole compound represented by the general formula (I) in which A is an acyl group and a stilbazole compound represented by the following general formula (XI)

[0035]

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(Wherein X is a halogen atom other than fluorine,
Y is a nitrogen atom or a carbon atom having a substituent R; Z is a single bond or a methylene group; R ¹ and R ² are a hydrogen atom, a lower alkyl group or a carbon atom to which each is bonded to form an aromatic ring; It may be formed, and may have a substituent on the aromatic ring. R is a hydrogen atom, a lower alkyl group or a phenyl group. With a compound represented by the following general formula (XII)

[0037]

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(Where A ¹ is an acyl group, Q is a single bond, a group represented by an oxygen atom, a sulfur atom or SO ₂ , X is a halogen atom other than fluorine, Y is a nitrogen atom or a substituent R Carbon atom, Z is a single bond or a methylene group, R ¹ and R ² may be a hydrogen atom, a lower alkyl group or a carbon atom to which each is bonded to form an aromatic ring; Which may have a substituent on
Is an integer of 0 to 10, and p is an integer of 0 or 1. However, when m is 0 or p is 0, Q is a single bond. R is a hydrogen atom, a lower alkyl group or a phenyl group. By synthesizing the quaternary salt compound represented by the formula (1) and further reacting the compound with a base, the betaine compound represented by the general formula (II) wherein A is an acyl group can be produced.

Some of the compounds represented by the general formula (XI) used here are known compounds which are already commercially available, and other compounds can be synthesized by known methods. . (See, for example, D. Harrison et al., Jou
rnal of Chemical Society, p.2930 (1963) etc.)

The reaction between the stilbazole compound represented by the general formula (I) wherein A is an acyl group and the compound represented by the general formula (XI) is carried out without a solvent or in an organic solvent. The reaction suitably proceeds under heating at about 50 ° C to 150 ° C. When performed in an organic solvent, alcohol, chloroform, dichloromethane, acetone, tetrahydrofuran (THF), N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), N, N-
An organic solvent such as dimethylacetamide is preferably used. Further, among the betaine compounds represented by the general formula (II), the compounds represented by the general formula (XII)
As a base used for leading to an acyl group, ammonia, lithium hydroxide, potassium hydroxide, sodium hydroxide, aluminum hydroxide, potassium carbonate,
Inorganic bases such as sodium carbonate, potassium acetate, sodium acetate, and sodium phosphate are preferably used, and generally, the reaction proceeds suitably by the action of an aqueous solution thereof. (For reaction conditions, see, for example, E. Alcalde et al.,
Advances in Heterocyclic Chemistry, Vol. 60, p. 197
(1994); Journal of Organic Chemistry, Volume 52,
p.5009 (1987), etc.) However, this reaction can be carried out without isolating the quaternary salt compound represented by the general formula (XII), without isolating the stilbazole compound represented by the general formula (I). The reaction may be carried out by adding an aqueous solution of the above-mentioned inorganic base, following the reaction of the compound represented by A with an acyl group with the compound represented by the general formula (XI).

Among the betaine compounds represented by the general formula (II), those in which A is a hydrogen atom are those represented by the general formula (I)
Among the betaine compounds represented by I), those in which A is an acyl group can be converted to an acyl group by a known method (for example, “Protective
Groups in Organic Synthesis ", John Wiley & Sons, N
ew York, 1981, p. 349-357). As a method preferably used, among the betaine compounds represented by the general formula (II), those in which A is an acyl group include, for example, ammonia, lithium hydroxide, potassium hydroxide, sodium hydroxide, and aluminum hydroxide. , Potassium carbonate, sodium carbonate, potassium acetate, sodium acetate, sodium phosphate and the like. Also in this case, A of the stilbazole compounds represented by the general formula (I) can be used without isolating a betaine compound represented by the general formula (II) in which A is an acyl group. Following or simultaneously with the reaction for deriving the betaine compound represented by formula (II) from the acyl group to the betaine compound represented by the general formula (II), an aqueous solution of the above-mentioned basic substance is added. It is also possible to carry out.

Among the betaine compounds represented by the general formula (II) of the present invention obtained by the above-described production method, those in which A is a hydrogen atom (hereinafter referred to as "diamine compound of the present invention"). By performing a polycondensation or polyaddition reaction with a known dicarboxylic acid and a derivative thereof, a tetracarboxylic dianhydride or a diisocyanate compound as a raw material monomer, the compound represented by the general formula (III) is contained in a repeating unit. A polymer containing at least 1 mol% of a repeating unit containing a structural unit (hereinafter, referred to as “polymer of the present invention”) can be produced. In the above polycondensation or polyaddition reaction, a polyamide having an amide bond in the main chain skeleton can be obtained by using a dicarboxylic acid and a derivative thereof, and a polyamic acid is obtained by using a tetracarboxylic dianhydride, followed by a chemical treatment or When an imidization reaction is performed by heat treatment, a polyimide having an imide bond in the main chain skeleton is obtained, and when a diisocyanate compound is used, a polyurea having a urea bond in the main chain skeleton is obtained. This polycondensation or polyaddition reaction is carried out by a method known in the literature (for example, JA
Moore, "Macromolecular Synthesis", John Wiley &
Sons, New York, 1997, edited by SR Sandler, W. Karo,
"Polymer Syntheses", Academic Press, Inc., Bosto
n, 1992, etc.). In the polycondensation or polyaddition reaction, a known diamine compound other than the diamine compound of the present invention may be mixed and used.

The dicarboxylic acids and derivatives thereof used herein are represented by the following general formula (XIII)

[0044]

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Wherein A ¹ is a dicarboxylic acid 2
X ² is a hydroxyl group, a halogen atom or an alkoxy group. ). Therefore, the repeating unit of the polyamide obtained in this case, that is, the repeating unit containing the structural unit represented by the general formula (III) in the polymer of the present invention is represented by the following general formula (XIV)

[0046]

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Wherein A ¹ is a dicarboxylic acid 2
A valence organic group, Q is a single bond, an oxygen atom, a sulfur atom or S
A group represented by O ₂ , Y is a nitrogen atom or a carbon atom having a substituent R, Z is a single bond or a methylene group, R ¹ and R ² are a hydrogen atom, a lower alkyl group or a carbon atom to which each is bonded. And an aromatic ring may be formed integrally, and a substituent may be present on the aromatic ring.
P is an integer of 0 or 1; However,
When m is 0 or p is 0, Q is a single bond. R is a hydrogen atom, a lower alkyl group or a phenyl group. ). Specific examples of the dicarboxylic acid represented by the general formula (XIII) and derivatives thereof include terephthalic acid, isophthalic acid,
2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 1,6-anthracenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, oxalic acid, fumaric acid, maleic acid, Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10
-Dicarboxylic acids such as decanedicarboxylic acid and the like, and acid halides and alkylesters thereof, and the like, and a mixture of two or more kinds thereof can also be used.

The tetracarboxylic dianhydride has the following general formula (XV)

[0049]

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(Wherein A ² is a tetravalent organic group constituting a tetracarboxylic acid). Therefore, the repeating unit of the polyimide obtained in this case, that is, the repeating unit containing the structural unit represented by the general formula (III) in the polymer of the present invention is represented by the following general formula (XVI)

[0051]

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(Where A ² is a tetravalent organic group constituting a tetracarboxylic acid, Q is a single bond, a group represented by an oxygen atom, a sulfur atom or SO ₂ , Y is a nitrogen atom or a substituent R) A carbon atom, Z is a single bond or a methylene group, R ¹ and R ² may form an aromatic ring together with a hydrogen atom, a lower alkyl group or a carbon atom to which each is bonded; May have a substituent on the ring;
Is an integer of 0 to 10, and p is an integer of 0 or 1. However, when m is 0 or p is 0, Q is a single bond. R is a hydrogen atom, a lower alkyl group or a phenyl group. ). Specific examples of the tetracarboxylic dianhydride represented by the general formula (XV) include, for example, pyromellitic dianhydride,
2,3,6,7 naphthalenetetracarboxylic dianhydride, 1,2,5,
6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,5,6- Anthracenetetracarboxylic dianhydride, 3,3 ', 4,4'diphenyltetracarboxylic dianhydride, bis (3,4 dicarboxyphenyl) ether dianhydride, 3,3', 4,4 ' -Benzophenonetetracarboxylic dianhydride, bis (3,4 dicarboxyphenyl) sulfone dianhydride, bis (3,4 dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4 dicarboxy) Phenyl) propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4 dicarboxyphenyl) Dimethylsilane dianhydride, bis (3,4 dicarboxyphenyl) diphenylsilane dianhydride, 2,3,5,6-pi Lysine tetracarboxylic dianhydride, 2,6-bis (3,4-dicarboxyphenoxy)
Pyridine dianhydride, cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic tetracarboxylic acid There are dianhydrides and the like, and a mixture of two or more thereof can also be used.

Further, the diisocyanate compound has the following general formula (XVII)

[0054]

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(Wherein A ³ is a divalent organic group constituting a diisocyanate compound). Therefore,
The polyurea repeating unit obtained in this case, that is, the repeating unit containing the structural unit represented by the general formula (III) in the polymer of the present invention is represented by the following general formula (XVI)
II)

[0056]

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(Where A ³ is a divalent organic group constituting a diisocyanate compound, Q is a single bond, a group represented by an oxygen atom, a sulfur atom or SO ₂ , Y is a nitrogen atom or a substituent R And Z is a single bond or a methylene group;
R ¹ and R ² may form an aromatic ring together with a hydrogen atom, a lower alkyl group or a carbon atom to which each is bonded, and may have a substituent on the aromatic ring; m is an integer of 0 to 10, and p is an integer of 0 or 1. However, when m is 0 or p is 0, Q is a single bond. R is a hydrogen atom, a lower alkyl group or a phenyl group. ). Specific examples of the diisocyanate compound represented by the general formula (XVII) include 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-xylylene diisocyanate, 1,3 -Xylylene diisocyanate, 2,4-toluylene diisocyanate, 2,5-toluylene diisocyanate, 4,4'-biphenylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-
Diphenylmethane diisocyanate, 4,4 '-(2,2-diphenylpropane) diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate And a mixture of two or more thereof.

In the above-mentioned polycondensation or polyaddition reaction, when a known diamine compound other than the diamine compound of the present invention is mixed and used, known diamine compounds include 1,4-phenylenediamine and 1-phenylenediamine. , 3-Phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,
4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 4,4'-
Diaminodiphenyl ether, 2,2-bis (4-aminophenyl) propane, 4,4′-diaminodiphenylsulfone,
4,4'-diaminobenzophenone, 1,4-bis (4-aminophenyl) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 2 , 2-Bis [4- (4-aminophenoxy) phenyl]
Propane, bis (4-aminocyclohexyl) methane, piperazine, 2-methylpiperazine, ethylenediamine,
3-diaminopropane, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, and the like, and a mixture of two or more thereof can be used. Can also be used. However, when these diamine compounds are used, they are mixed and used so that the amount of the diamine compound of the present invention is 1 mol% or more, more preferably 5 mol% or more, based on the total amount of the diamine.

The weight average molecular weight of the polymer of the present invention is 2,0
It is preferably at least 00, and more preferably at least 5,000 in view of film forming properties and stability as a nonlinear optical material.
Molecular weight is determined by gel permeation chromatography,
It is measured by a known method such as a vapor pressure measurement method, an osmotic pressure method, a light scattering method, and a viscosity method.

When the polymer of the present invention is used as a polymer nonlinear optical material, for example, the polymer may be chloroform, dichloromethane, dichloroethane, benzene, toluene, xylene, dimethoxyethane, dioxane, acetonitrile, THF, NMP, DMF , DMSO, dimethylacetamide, dissolved in an organic solvent such as pyridine, a glass substrate by a method such as spin coating or casting,
On a substrate such as an ITO vapor-deposited substrate or a silicon wafer, a film is formed so that the film thickness is preferably 0.1 to 10 μm, and after drying, it is preferable to hold the film at a temperature near the glass transition temperature of the polymer. The target material can be obtained by performing a poling treatment at a voltage of 1 kV / cm or more to orient the betaine residue in the side chain. When the polymer of the present invention is polyimide or polyurea, by-products are not generally generated in the polymerization reaction, so that the solution obtained by mixing the corresponding monomer compounds is used as it is on the substrate by spin coating or casting. It is possible to form a film.

[0061]

The polymer nonlinear optical material comprising the polymer of the present invention obtained by using the diamine compound of the present invention as a monomer has good moldability and excellent secondary nonlinear optical strength. In addition, since it is a glassy (amorphous) polymer, it is a material having little light scattering and excellent transparency seen in a crystalline polymer. Therefore, it is useful as a material for a light control device such as a wavelength conversion element, a waveguide, an optical shutter, an optical switch, an optical polarization element, and a phase modulation element utilizing a nonlinear optical effect, a nonlinear optical device, and an electro-optical device.

[0062]

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

Reference Example 1

[0064]

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2.40 g (60.0 mmol, 60% in oil) of sodium hydride was placed in a 200 ml three-necked flask, and the system was purged with argon and washed with hexane. 30 ml of dry DMF was added, and under ice cooling, 14.18 g (75.0 mmol) of 4-bromothiophenol dissolved in 10 ml of dry DMF was added dropwise, and the mixture was further stirred at room temperature for 1 hour. This is 3-
7.09 g (75.0 mmol) of chloro-1-propanol were added dropwise.
After stirring at room temperature for 2 hours, DMF was removed under reduced pressure. Ethyl acetate was added to the residue, and the solution was washed with water. Anhydrous sodium sulfate was added to the organic layer to dry it. After concentrating the solution, ethyl acetate / hexane (volume ratio 9/1 → 5
Purification by silica gel column chromatography using (/ 1) as an eluent gave 4- (3-hydroxypropylthio) bromobenzene (1) as a colorless liquid in a yield of 17.65 g (95.0%).

¹ H NMR (90 MHz, CDCl ₃ , δ / ppm): 1.41
(t, J = 5.5 Hz, 1H), 1.88 (quintet, J = 7.0 Hz, 2H),
3.02 (t, J = 7.0 Hz, 2H), 3.77 (dt, J = 5.5, 7.0 Hz, 2
H), 7.19 (dt, J = 2.2, 8.8 Hz, 2H), 7.41 (dt, J = 2.2,
8.8 Hz, 2H). IR (neat, cm ^-1 ): 3345 (-OH), 3130, 2935, 2880, 189
0, 1630, 1565, 1475, 1435, 1385, 1350, 1290, 1265,
1215, 1180, 1150, 1090, 1070, 1050, 1005, 905, 81
0, 730 ,. 510, 480. Mass (m / e): 248 (M ⁺ +2), 246 (M +), 203, 201 (Br-Ph-
^{_{S-CH 2 +), 190}} , 188, 149, 136, 134 (Ph-SC 2 H 4 +), 122
(Ph-S-CH ₂ ⁺ ), 109 (Ph-SH), 108 (Ph-S ⁺ ), 82,75, 69,
65, 63, 58, 45 ( + C 2 H 4 OH), 31 (+ CH 2 OH).

Under an argon atmosphere, 12.20 g (49.4 mmol) of (1) obtained in the above reaction and 7.14 g of triethylamine were obtained.
(70.0 mmol) was added with 40 ml of dry THF to form a solution. To this solution was added 13.66 g (59.2 mmol) of 3,5-dinitrobenzoic acid chloride dissolved in 20 ml of dry THF.
Stirred for hours. The reaction solution was filtered, and the filtrate was evaporated under reduced pressure. The residue was recrystallized from methanol to give 3- (4-bromophenyl) thio-1-propyl 3,5-dinitrobenzoate (2) as 20.75 g (95.3 g). %) As yellow crystals.

[0068]¹H NMR (400MHz, CDCl_Three, δ / ppm): 2.16
(quintet, J = 6.6 Hz, 2H), 3.07 (t, J = 6.9 Hz, 2H),
4.57 (t, J = 6.3 Hz, 2H), 7.24 (dt, J = 2.0, 8.6 Hz, 2
H), 7.41 (dt, J = 2.0, 8.6 Hz, 2H), 9.14 (d, J = 2.15 H
z, 2H), 9.24 (t, J = 2.15 Hz, 1H) .IR (KBr, cm^-1): 3115, 3095, 2985, 2960, 2930, 289
5, 2875, 2850, 1730 (-C = O), 1630, 1595, 1540, 147
5, 1435, 1380, 1345, 1300, 1275, 1165, 1115, 1085,
 1070, 1005, 995, 935, 925, 900, 880, 865, 840, 82
0, 770, 730, 715,635, 595, 570, 520, 495, 480, 44
5, 420. Mass (m / e): 442 (M⁺+2), 440 (M⁺), 412, 410, 253 [M
⁺-(-S-Ph-Br)], 230 [(M ⁺+2)-((O_TwoN)_TwoPhCOO)], 228 [M⁺
-((O_TwoN)_TwoPhCOO)], 203, 201 (⁺CH_Two-S-Ph-Br), 195 [(O_Two
N)_TwoPhCO⁺], 183, 165, 149, 134, 122, 108, 91, 75, 6
3, 41, 28. Elemental analysis results (C₁₆H₁₃N_TwoO₆SBr, FW 441.3) Calculated: C 43.55% H 2.97% N 6.35% S 7.27%
Br 18.11% Found: C 43.66% H 2.88% N 6.38% S 7.21%
Br 18.17%

13.24 g of the compound (2) obtained by the above reaction
(30.0 mmol), 150 ml of acetic acid and 17.01 g of 30% aqueous hydrogen peroxide (1
After stirring the solution containing 50 mmol) under reflux for 3 hours, the reaction solution was poured into 500 ml of a saturated aqueous solution of sodium hydrogen carbonate. Furthermore, after adding sodium hydrogen carbonate and neutralizing, 1000 ml of water was added. The generated precipitate was collected by filtration. The obtained precipitate is purified by recrystallization from a mixed solvent of acetone and methanol, and 3- (4-bromophenyl)
Sulfonyl-1-propyl 3,5-dinitrobenzoate (3) was obtained as colorless crystals in a yield of 12.81 g (90.1%).

[0070]¹H NMR (400MHz, CDCl_Three, δ / ppm): 2.25-
2.35 (m, 2H), 3.2-3.3 (m, 2H), 4.57 (t, J = 6.4 Hz, 2
H), 7.75 (dt, J = 2.0, 8.7 Hz, 2H), 7.82 (dt, J = 2.0,
 8.7 Hz, 2H), 9.12 (d, J = 2.13 Hz, 2H), 9.25 (t, J =
2.13 Hz, 1H). IR (KBr, cm^-1): 3095, 2960, 2930, 2860, 1725 (-C =
O), 1630, 1575, 1545, 1510, 1470, 1460, 1440, 143
0, 1410, 1390, 1350, 1315, 1285, 1270, 1230, 1210,
 1175, 1145, 1085, 1070, 1040, 1020, 945, 920, 88
5, 840, 825, 800, 775, 760, 730, 720, 620, 595, 57
0, 555, 515, 485, 455, 425. Mass (m / e): 474 (M⁺+2), 472 (M⁺), 442, 440, 414, 4
12, 279 [(M⁺+2)-((O_TwoN) _TwoPhCO)], 277 [M⁺-((O_TwoN)_TwoPhC
O)], 263 [(M⁺+2)-((O_TwoN)_TwoPhCOO)], 261 [M⁺-((O_TwoN)_TwoPh
COO)], 253 [M⁺-(-SO_Two-Ph-Br)], 230, 221, 219 (⁺SO_Two-
Ph-Br), 205, 203 (⁺SO-Ph-Br), 195 [(O_TwoN)_TwoPhCO⁺], 17
9, 165, 157, 155 (⁺Ph-Br), 103, 91, 75, 63, 41, 2
8. Elemental analysis results (C₁₆H₁₃N_TwoO₈SBr, FW 473.3) Calculated: C 40.61% H 2.77% N 5.92% S 6.77%
Br 16.88% Found: C 40.70% H 2.69% N 5.90% S 6.73%
Br 16.68%

SnCl ₂ .2H ₂ O (22.57 g, 100 mmol) was placed in a 500 ml eggplant flask, 50 ml of ethanol was added, and the mixture was stirred at 60 ° C. To this solution, compound (3) (4.733 g, 10.0 mmol) dissolved in 50 ml of THF was added. Further, sodium borohydride (0.755 g, 20.0 mmol) dissolved in 50 ml of ethanol was added, and the mixture was stirred at 70 ° C for 2 hours. After the reaction solution was concentrated under reduced pressure, an ethyl acetate solution was obtained. The ethyl acetate was washed sequentially with a 0.5N aqueous sodium hydroxide solution, a saturated aqueous ammonium chloride solution, and a saturated aqueous sodium chloride solution. The organic layer was dried over anhydrous sodium sulfate, and then the solution was concentrated under reduced pressure. Hexane residue
Purification by silica gel column chromatography using an ethyl acetate mixed solvent (volume ratio of 1: 3) as an eluent gave 3- (4-bromophenyl) sulfonyl-1-propyl 3,5-diaminobenzoate (4) in 3.840. g (92.9%) yielded as a pale yellow solid.

¹ H NMR (400 MHz, CDCl ₃ , δ / ppm): 2.1-2.
2 (m, 2H), 3.2-3.3 (m, 2H), 3.65-3.75 (br, 4H), 4.
32 (t, J = 6.1 Hz, 2H), 6.19 (t, J = 2.1 Hz, 1H), 6.70
(d, J = 2.1 Hz, 2H), 7.72 (dt, J = 2.0, 8.7 Hz, 2H),
7.79 (dt, J = 2.0, 8.7 Hz, 2H) .IR (KBr, cm ^-1 ): 3450, 3370, 3230, 3085, 3025, 296
0, 1710, 1620, 1600, 1575, 1470, 1390, 1365, 1315,
1275, 1240, 1195, 1145, 1110, 1085, 1075, 1010, 9
55, 850, 825, 790, 770, 750, 720, 710, 680, 615, 5
65, 555, 540, 520.Mass (m / e): 414 (M ⁺ +2), 412 (M ⁺ ), 263 [(M ⁺ +2)-((H ₂
N) ₂ PhCOO)], 261 [M ⁺ -((H ₂ N) ₂ PhCOO)], 221, 219 ( ⁺ SO ₂
-Ph-Br), 205, 203 ( ⁺ SO-Ph-Br), 193, 157, 155 ( ⁺ Ph-B
r), 135 [(H ₂ N) ₂ PhCO ⁺ ], 108, 80, 67, 53, 41, 28.

3.520 g of the compound (4) obtained by the above reaction
(8.52 mmol) and 0.122 g of 4- (dimethylamino) pyridine
(1.0 mmol) was added with 20 ml of dry THF to form a solution. To this solution, 5.367 g (25.56 mmol) of trifluoroacetic anhydride dissolved in 20 ml of dry THF was added, and the mixture was stirred for 1 hour. The reaction solution was poured into 200 ml of an aqueous saturated sodium hydrogen carbonate solution, and extracted with ethyl acetate. After dehydrating the organic layer with anhydrous sodium sulfate, the solution was concentrated under reduced pressure. The residue was purified by silica gel column chromatography using a mixed solvent of hexane / ethyl acetate (volume ratio: 1: 1) as an eluent, and recrystallized from a mixed solvent of chloroform / ethyl acetate to give 3- (4-bromophenyl) sulfonyl-1. -Propyl3,5-
Bis (trifluoroacetamido) benzoate (5)
It was obtained as pale yellow crystals in a yield of 4.734 g (91.8%).

¹ H NMR (400 MHz, CDCl ₃ , δ / ppm): 2.2-2.
3 (m, 2H), 3.25-3.35 (m, 2H), 4.43 (t, J = 6.1 Hz, 2
H), 7.73 (dt, J = 2.0, 8.7 Hz, 2H), 7.82 (dt, J = 2.0,
8.7 Hz, 2H), 8.06 (d, J = 2.0 Hz, 2H), 8.22-8.28 (b
r, 2H), 8.31 (t, J = 2.0 Hz, 1H) .IR (KBr, cm ^-1 ): 3370, 3350, 3295, 3185, 3125, 296
5, 2920, 1730, 1705, 1615, 1570, 1460, 1385, 1380,
1330, 1310, 1290, 1255, 1245, 1220, 1195, 1155, 1
085, 1070, 1010, 900, 880, 825, 805, 775, 765, 74
0, 725, 675, 640,615, 570, 525, 530, 510, 485, 45
0, 420.Mass (m / e): 606 (M ⁺ +2), 604 (M ⁺ ), 385 [(F ₃ CCONH) ₂ P
hCOO (CH ₂ ) ₃ ⁺ ], 344 [(F ₃ CCONH) ₂ PhCOOH], 327 [(F ₃ CCO
NH) ₂ PhCO ⁺ ], 299 [(F ₃ CCONH) ₂ Ph ⁺ ], 279, 263 [(M ⁺ +2)-
((F ₃ CCONH) ₂ PhCOO)], 261 [M ⁺ -((F ₃ CCONH) ₂ PhCOO)], 22
1, 219 ( ⁺ SO ₂ -Ph-Br), 205, 203 ( ⁺ SO-Ph-Br), 187, 15
^{7, 155 (+ Ph-Br} ), 76, 41. Elemental analysis _{(C 20 H 15 N 2 O} 6 SBrF 6, FW 605.3) Calculated: C 39.69% H 2.50% N 4.63% Found: C 39.82% H 2.39% N 4.55%

Embodiment 1

[0076]

Embedded image

7.263 g of compound (5) obtained in Reference Example 1 (1
2.0 mmol), 4-vinylpyridine 1.682 g (16.0 mmol), triethylamine 1.619 g (16.0 mmol), palladium (II) acetate 0.13
5 g (0.60 mmol) and 12 ml of acetonitrile were mixed, and the system was degassed. This mixture was refluxed for 60 hours under an argon atmosphere. After cooling, the reaction mixture was poured into 500 ml of water, and the generated precipitate was collected by filtration. Hexane residue
After purification by silica gel column chromatography using an ethyl acetate mixed solvent (1: 2 by volume) as an eluent, recrystallization from an acetone / chloroform mixed solvent
3- {4- [2- (4-pyridyl) ethenyl] phenyl} sulfonyl-1
-Propyl 3,5-bis (trifluoroacetamido) benzoate (6) was obtained as colorless crystals in a yield of 5.191 g (68.7%).

[0078]¹H NMR (400 MHz, (CD_Three)_Two(SO, δ / ppm): 2.
0-2.1 (m, 2H), 3.5-3.6 (m, 2H), 4.34 (t, J = 6.4 Hz,
 2H), 7.45 (d, J = 16.4 Hz, 1H), 7.60 (d, J = 6.0 Hz,
2H), 7.64 (d, J = 16.4 Hz, 1H), 7.90 (d, J = 8.5 Hz, 2
H), 7.95 (d, J = 8.5 Hz, 2H), 8.11 (d, J = 1.9 Hz, 2H),
 8.50 (t, J = 2.0 Hz, 1H), 8.59 (d, J = 6.0 Hz, 2H), 1
1.59 (s, 2H). IR (KBr, cm^-1): 3510, 3425, 3285, 3105, 3050, 303
0, 2925, 2900, 2850, 1730, 1660, 1620, 1600, 1550,
 1535, 1515, 1500, 1460, 1440, 1425, 1410, 1365, 1
325, 1305, 1285, 1260, 1240, 1215, 1195, 1150, 114
5, 1085, 1075, 1005, 975, 935, 890, 850, 830, 805,
 790, 765, 750, 740, 705, 675, 660, 635, 620, 590,
 565, 550, 530, 500, 480, 460, 440. Mass (m / e): 629 (M⁺), 581, 560 (M⁺-CF_Three), 512, 385
[(F_ThreeCCONH)_TwoPhCOO (CH_Two)_Three ⁺], 327 [(F_ThreeCCONH)_TwoPhCO⁺], 2
99 [(F_ThreeCCONH)_TwoPh⁺], 279, 257, 231, 229, 213,196, 1
80, 168, 152, 127, 115, 69 (CF_Three ⁺), 41. Elemental analysis results (C₂₇H_{twenty one}N_ThreeO₆science fiction₆, FW 629.5) Calculated: C 51.51% H 3.36% N 6.67% Actual: C 51.49% H 3.17% N 6.63%

Embodiment 2

[0080]

Embedded image

Under an argon atmosphere, 10 ml of 1-butanol was added to 0.381 g (2.50 mmol) of 2-chlorobenzimidazole and 1.574 g (2.50 mmol) of the stilbazole compound (6) obtained in Example 1, and added at 48 ° C. Stirred for hours. After allowing the reaction mixture to cool, it was poured into 50 ml of acetone, and the formed precipitate was collected by filtration. 100 ml of methanol, 50 ml of THF and 25 ml of aqueous ammonia were added to the precipitate, and the mixture was added at 40 ° C
For 24 hours. The resulting precipitate was collected by filtration and recrystallized from a mixed solvent of THF and methanol to give 2- [4- (2- {4- [3- (3,5-diaminobenzoyloxy) propyl-1-sulfonyl]. [Phenyl} ethenyl) pyridinio] benzimidazolate (7) was obtained as red-brown crystals in a yield of 0.245 g (17.7%).

¹ H NMR (400 MHz, (CD ₃ ) ₂ SO, δ / ppm): 1.
9-2.0 (m, 2H), 3.45-3.55 (m, 2H), 4.21 (t, J = 6.4 H
z, 2H), 4.9-5.1 (br, 4H), 6.03 (t, J = 2.1 Hz, 1H),
6.41 (d, 2H, J = 2.1 Hz), 6.9-7.0 (m, 2H), 7.45-7.55
(m, 2H), 7.80 (d, J = 16.3 Hz, 1H), 8.0-8.1 (m, 2
H), 8.13 (d, J = 16.4 Hz, 1H), 8.30 (d, J = 7.0 Hz, 2
H), 9.90 (d, J = 7.0 Hz, 2H) .IR (KBr, cm ^-1 ): 3590, 3445, 3350, 3225, 3130, 308
0, 3050, 1715, 1620, 1565, 1500, 1470, 1400, 1365,
1320, 1305, 1275, 1240, 1195, 1140, 1120, 1090, 1
010, 995, 975, 950, 910, 890, 850, 810, 770, 755,
710, 685, 655, 625, 595, 570, 545, 525.Mass (SIMS, m / e): 554 (M ⁺ +1), 460, 307, 289, 242,
176, 155, 120, 79, 41.

Reference Example 2

[0084]

Embedded image

17.30 g (100 mmol) of 4-bromophenol, 3-bromophenol
200 ml of acetone was added to 10.40 g (110 mmol) of chloro-1-propanol, 27.64 g (200 mmol) of anhydrous potassium carbonate and 5 g of potassium iodide, and the mixture was refluxed for 72 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. Ethyl acetate was added to the residue, and the mixture was washed with an aqueous sodium hydroxide solution. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography using a mixed solvent of hexane and ethyl acetate (volume ratio of 1: 2 → 2: 1) as an eluent to give 17.640 g. 4- (3-Hydroxy-1-propyloxy) bromobenzene (8) was obtained as a colorless liquid in a yield of (76.3%).

¹ H NMR (90 MHz, CDCl ₃ , δ / ppm): 1.5-1.8
(br, 1H), 2.03 (quintet, J = 6.2 Hz, 2H), 3.8-4.0
(m, 2H), 4.08 (t, J = 6.2 Hz, 2H), 6.78 (dd, J = 2.3,
9.0 Hz, 2H), 7.37 (dd, J = 2.3, 9.0 Hz, 2H) .IR (KBr, cm ^-1 ): 3360, 3095, 3060, 2950, 2985, 187
5, 1590, 1575, 1490, 1470, 1440, 1420, 1390, 1285,
1245, 1175, 1100, 1060, 1000, 955, 870, 820,730,
695, 640, 600, 505.

Under an argon atmosphere, 40 ml of dry THF was added to 11.555 g (50.0 mmol) of the compound (8) obtained above and 7.14 g (70.0 mmol) of triethylamine to form a solution. To this solution, 13.834 g (60.0 mmol) of 3,5-dinitrobenzoic acid chloride dissolved in 60 ml of dry THF was added, and the mixture was stirred at room temperature for 1 hour. After the reaction solution was filtered and the filtrate was distilled off under reduced pressure, the residue was recrystallized from ethyl acetate.
3- (4-Bromophenyl) oxy-1-propyl 3,5-dinitrobenzoate (9) was obtained as pale yellow crystals in a yield of 20.457 g (96.2%).

¹ H NMR (400 MHz, CDCl ₃ , δ / ppm): 2.33
(quintet, J = 6.1 Hz, 2H), 4.1-4.5 (m, 2H), 4.66 (t,
J = 6.4 Hz, 2H), 6.79 (dt, J = 2.3, 9.0 Hz, 2H), 7.37
(dt, J = 2.0, 8.6 Hz, 2H), 9.15 (d, J = 2.15 Hz, 2H),
9.23 (t, J = 2.15 Hz, 1H) .IR (KBr, cm ^-1 ): 3105, 2980, 2960, 2930, 2895, 282
0, 1895, 1875, 1840, 1730 (-C = O), 1685, 1645, 162
5, 1590, 1580, 1540, 1495, 1480, 1460, 1420, 1390,
1345, 1300, 1280, 1240, 1175, 1140, 1110, 1075, 1
030, 1005, 980, 920, 890, 835, 775, 720, 640, 510,
485, 440. Mass (m / e): 426 (M ⁺ +2), 424 (M ⁺ ), 396, 394, 253 [M
⁺ -(-O-Ph-Br)], 237, 232, 230, 223, 207, 195 [(O ₂ N)
₂ PhCO ⁺ ], 193, 174, 172 (HO-Ph-Br), 167, 149,135, 1
19, 107, 91, 75, 63, 41, 28. Elemental analysis (C ₁₆ H ₁₃ N ₂ O ₇ Br, FW 425.2) Calculated: C 45.20% H 3.08% N 6.59% Br 18.79
% Found: C 45.30% H 2.85% N 6.42% Br 18.83
%

Put SnCl ₂ .2H ₂ O (56.41 g, 250 mmol) in a 500 ml eggplant flask, add 100 ml of ethanol, and add
And stirred. Compound (9) (10.630 g, 25.0 mmol) dissolved in 100 ml of THF was added to this solution. Further, sodium borohydride (1.889 g, 50.0 mmol) dissolved in 100 ml of ethanol was added, and the mixture was stirred at 70 ° C. for 1 hour. After the reaction solution was concentrated under reduced pressure, an ethyl acetate solution was obtained. The ethyl acetate was washed with a 0.5N aqueous solution of sodium hydroxide, a saturated aqueous solution of ammonium chloride, and a saturated aqueous solution of sodium chloride in that order. The organic layer was dried over anhydrous sodium sulfate, and the solution was concentrated under reduced pressure. The residue was purified by silica gel column chromatography using a hexane / ethyl acetate mixed solvent (volume ratio 1: 2) as an eluent, and then recrystallized from a hexane / ethyl acetate mixed solvent to give 3- (4-bromophenyl). 7.831 g (85.8 g) of oxy-1-propyl 3,5-diaminobenzoate (10)
%) As pale yellow crystals.

¹ H NMR (400 MHz, CDCl ₃ , δ / ppm): 2.22
(quintet, J = 6.2 Hz, 2H), 3.6-3.7 (br, 4H), 4.08
(t, J = 6.2 Hz, 2H), 4.45 (t, J = 6.2 Hz, 2H), 6.19
(t, J = 2.1 Hz, 1H), 6.76 (d, J = 2.1 Hz, 2H), 6.79 (d
t, J = 2.3, 9.0 Hz, 2H), 7.37 (dt, J = 2.3, 9.0 Hz, 2
H) .IR (KBr, cm ^-1 ): 3450, 3425, 3345, 3300, 3200, 308
0, 3060, 3040, 2990, 2960, 2890, 1715, 1625, 1600,
1580, 1495, 1475, 1460, 1440, 1390, 1360, 1320, 1
305, 1290, 1235, 1195, 1180, 1130, 1115, 1095, 107
5, 1060, 1035, 1000, 950, 910, 875, 850, 825, 765,
750, 670, 640, 600, 585, 530, 510, 440, 420. Mass (m / e): 366 (M ⁺ +2), 364 (M ⁺ ), 284, 282, 193, 1
74, 172 (HO-Ph-Br), 152 [(H ₂ N) ₂ PhCOOH], 135 [(H ₂ N)
₂ PhCO ⁺ ], 107 [(H ₂ N) ₂ Ph ⁺ ], 93, 80, 65, 53, 41, 28. Elemental analysis result (C ₁₆ H ₁₇ N ₂ O ₃ Br, FW 365.2) Calculated value: C 52.62% H 4.69% N 7.67% Found: C 52.59% H 4.55% N 7.56%

Compound (10) obtained by the above reaction 7.35
0 g (20.1 mmol) and 0.122 g of 4- (dimethylamino) pyridine
(1.0 mmol) was added with 20 ml of dry THF to form a solution. To this solution, 12.68 g (30.2 mmol) of trifluoroacetic anhydride dissolved in 20 ml of dry THF was added, and the mixture was stirred for 1 hour. After adding 50 ml of methanol to the reaction solution, the solution was concentrated under reduced pressure. The residue was mixed with a mixed solvent of hexane and ethyl acetate (volume ratio 1: 1).
Purification by silica gel column chromatography using 2) as an eluent and recrystallization from a mixed solvent of hexane and ethyl acetate gave 3- (4-bromophenyl) oxy-1-propyl 3,5-bis (trifluoroacetamido) benzoate. (11) was obtained as pale yellow crystals in a yield of 10.876 g (97.0%).

¹ H NMR (400 MHz, CDCl ₃ , δ / ppm): 2.29
(quintet, J = 6.2 Hz, 2H), 4.10 (t, J = 6.0 Hz, 2H),
4.55 (t, J = 6.3 Hz, 2H), 6.79 (dt, J = 2.3, 8.9 Hz, 2
H), 7.37 (dt, J = 2.3, 8.9 Hz, 2H), 8.07 (d, J = 2.0 H
z, 2H), 8.14-8.22 (br, 2H), 8.31 (t, J = 2.0 Hz, 1
H) .IR (KBr, cm ^-1 ): 3355, 3275, 3175, 3100, 2930, 288
5, 1740, 1710, 1620, 1595, 1565, 1510, 1495, 1470,
1460, 1445, 1400, 1385, 1365, 1330, 1285, 1260, 1
240, 1180, 1160, 1130, 1070, 1060, 1000, 985, 975,
935, 920, 895, 875, 820. 800, 775, 740, 675, 645,
610, 550, 525, 500. Mass (m / e): 558 (M ⁺ +2), 556 (M ⁺ ), 385 [(F ₃ CCONH) ₂ P
hCOO (CH ₂ ) ₃ ⁺ ], 327 [(F ₃ CCONH) ₂ PhCO ⁺ ], 299 [(F ₃ CCON
H) ₂ Ph ⁺ ], 279, 257, 174, 172 (HO-Ph-Br), 69 (CF ₃ ⁺ ),
63, 41, 28. Elemental analysis _{(C 20 H 15 N 2 O} 5 BrF 6, FW 557.2) Calculated: C 43.11% H 2.71% N 5.03% Found: C 42.87% H 2.49% N 4.88%

Embodiment 3

[0094]

Embedded image

6.686 g of the compound (11) obtained in Reference Example 2
(12.0 mmol), 4-vinylpyridine 1.893 g (18.0 mmol), triethylamine 1.822 g (18.0 mmol), palladium (II) acetate 0.
135 g (0.60 mmol), 0.314 g of triphenylphosphine (1.20 m
mol) and 12 ml of DMF, and the system was degassed. The mixture was stirred at 100 ° C. under an argon atmosphere for 48 hours. After cooling, the reaction mixture was poured into 500 ml of water, and the generated precipitate was collected by filtration. The residue was purified by silica gel column chromatography using a hexane / ethyl acetate mixed solvent (volume ratio 1: 2) as an eluent,
When recrystallized from a mixed solvent of acetone and chloroform, 3- {4
-[2- (4-Pyridyl) ethenyl] phenyl} oxy-1-propyl 3,5-bis (trifluoroacetamido) benzoate (12) was obtained as pale yellow crystals in a yield of 2.246 g (32.2%).

¹ H NMR (400 MHz, (CD ₃ ) ₂ SO, δ / ppm): 2.
21 (quintet, J = 6.2 Hz, 2H), 4.19 (t, J = 6.2 Hz, 2
H), 4.46 (t, J = 6.2 Hz, 2H), 7.00 (d, J = 8.7 Hz, 2
H), 7.08 (d, J = 16.4 Hz, 1H), 7.48 (d, J = 16.4 Hz, 1
H), 7.51 (d, J = 6.1 Hz, 2H), 7.59 (d, J = 8.7 Hz, 2H),
8.17 (d, J = 2.0 Hz, 2H), 8.48-8.52 (m, 3H), 11.60
(s, 2H). IR (KBr, cm ^-1 ): 3495, 3435, 3275, 3115, 3035, 299
0, 2955, 2920, 2850, 1740, 1600, 1575, 1515, 1460,
1440, 1425, 1390, 1365, 1330, 1300, 1280, 1225, 1
190, 1160, 1055, 995, 960, 925, 890, 875, 830, 79
0, 765, 735, 705,685, 670, 630, 610, 585, 560, 54
0, 520, 505, 485, 465, 450, 420.Mass (m / e): 581 (M ⁺ ), 562 (M ⁺ -F), 512 (M ⁺ -CF ₃ ), 51
2, 385 [(F ₃ CCONH) ₂ PhCOO (CH ₂ ) ₃ ⁺ ], 327 [(F ₃ CCONH) ₂ Ph
CO ⁺ ], 299 [(F ₃ CCONH) ₂ Ph ⁺ ], 279, 257, 229, 213, 19
7, 180, 168, 152, 127, 115, 100, 84, 69 (CF ₃ ⁺ ), 4
1. Elemental analysis results (C ₂₇ H ₂₁ N ₃ O ₅ F ₆ , FW 581.4) Calculated: C 55.78% H 3.64% N 7.23% Found: C 55.47% H 3.40% N 7.09%

Embodiment 4

[0098]

Embedded image

Under an argon atmosphere, 10 ml of 1-butanol was added to 1.454 g (2.50 mmol) of the compound (12) obtained in Example 3, and the mixture was stirred at 100 ° C. for 48 hours. After allowing the reaction mixture to cool, it was poured into 50 ml of acetone, and the formed precipitate was collected by filtration. 50 ml of methanol, 50 ml of T
After adding HF and 5 ml of aqueous ammonia, 500 ml of water were added. The generated precipitate was collected by filtration. The precipitate is mixed with chloroform / methanol (volume ratio: 10: 1)
The origin component was removed by silica gel column chromatography using a mixed solvent of chloroform / methanol (volume ratio: 10: 1) as an eluent. Further, the obtained effluent solution was concentrated, and 10 ml of methanol, 10
To the mixture were added THF (10 ml) and aqueous ammonia (10 ml), followed by stirring at 40 ° C. for 24 hours. After collecting the generated precipitate by filtration, recrystallization from a THF / methanol mixed solvent
2- [4- (2- {4- [3- (3,5-diaminobenzoyloxy) propyl
1-Oxy] phenyl} ethenyl) pyridinio] benzimidazolate (13) was obtained as red-brown crystals in a yield of 0.629 g (49.7%).

¹ H NMR (400 MHz, (CD ₃ ) ₂ SO, δ / ppm): 2.
16 (quintet, J = 6.3 Hz, 2H), 4.19 (t, J = 6.32 Hz, 2
H), 4.34 (t, J = 6.2 Hz, 2H), 4.9-5.1 (br, 4H), 6.03
(t, J = 2.0 Hz, 1H), 6.46 (d, J = 2.1 Hz, 2H), 6.9-7.
0 (m, 2H), 7.09 (d, J = 8.8 Hz, 2H), 7.4-7.5 (m, 3H),
7.76 (d, J = 8.8 Hz, 2H), 8.01 (d, J = 16.3 Hz, 1H),
8.18 (d, J = 7.1 Hz, 2H), 9.78 (d, J = 7.1 Hz, 2H) .IR (KBr, cm ^-1 ): 3425, 3360, 3230, 3050, 2950, 262
5, 1700, 1610, 1595, 1570, 1515, 1470, 1425, 1395,
1365, 1330, 1310, 1300, 1245, 1195, 1175, 1140, 1
115, 1040, 1000, 990, 965, 900, 875, 840, 810, 77
0, 745, 715, 680,620, 590, 540, 445, 415. Mass (SIMS, m / e): 506 (M ⁺ +1), 460, 391, 371, 307,
289, 238, 212.

Reference Example 3

[0102]

Embedded image

2.88 g (120 mmol) of sodium hydride in 200 ml
Was placed in a three-necked flask, and the system was set to an argon atmosphere, and then washed with hexane. 40 mL of dry DMF was added, and 18.91 g (100 mmol) of 4-bromothiophenol dissolved in 20 mL of dry DMF was added dropwise under ice cooling, followed by stirring at room temperature for 1 hour. 13.67 g (100 mmol) of 6-chloro-1-hexyl alcohol further dissolved in 20 mL of dry DMF
And stirred at room temperature for 2 hours.
The MF was removed. Ethyl acetate was added to the residue, and the solution was washed with an aqueous sodium hydrogen carbonate solution. The organic layer was dried over anhydrous sodium sulfate, concentrated, and recrystallized from ethyl acetate to give 4- (6-hydroxy-1-hexylthio) bromobenzene (14) as white crystals in a yield of 25.4 g (87.9%). Was done.

¹ H NMR (500 MHz, CDCl ₃ , δ / ppm): 1.20
(t, J = 5.3 Hz, 1H), 1.34-1.72 (m, 8H), 2.90 (t, J =
7.3 Hz, 2H), 3.64 (dt, J = 5.3, 6.6 Hz, 2H), 7.18 (d
t, J = 1.9, 8.5 Hz, 2H), 7.39 (dt, J = 1.9, 8.5 Hz, 2
H) .IR (KBr, cm ^-1 ): 3290, 2930, 2895, 2860, 1475, 146
5, 1430, 1400, 1390, 1305, 1260, 1240, 1220, 1185,
1160, 1110, 1095, 1070, 1055, 1035, 1005, 985, 87
0, 825, 800, 790, 750, 735, 500, 480, 435. Mass (m / e): 290 (M ⁺ +2), 288 (M ⁺ ), 203 ( ⁺ CH ₂ S-Ph-B
r + 2), 201 ( ⁺ CH ₂ S-Ph-Br), 190 (HS-Ph-Br + 2), 188 (HS
-Ph-Br), 135, 122, 108, 82, 69, 55, 41, 39, 31, 28. Elemental analysis (C ₁₂ H ₁₇ OSBr, FW 289.23) Calculated: C 49.83% H 5.92% S 11.08 % Actual value: C 50.25% H 5.87% S 11.14%

Under an argon atmosphere, 50 ml of dry THF was added to 15.23 g (52.7 mmol) of the compound (14) obtained in the above reaction and 7.46 g (73.8 mmol) of triethylamine to form a solution. To this solution, 14.58 g (63.3 mmol) of 3,5-dinitrobenzoic acid chloride dissolved in 70 ml of dry THF was added, and the mixture was stirred at room temperature for 1 hour. The reaction solution was filtered, and the filtrate was evaporated under reduced pressure.The residue was recrystallized from methanol to give 6- (4
-Bromophenyl) thio-1-hexyl 3,5-dinitrobenzoate (15) was obtained as yellow crystals in a yield of 25.03 g (98.3%).

¹ H NMR (500 MHz, CDCl ₃ , δ / ppm): 1.43-
1.87 (m, 8H), 2.92 (t, J = 7.2 Hz, 2H), 4.45 (t, J =
6.7 Hz, 2H), 7.18 (dt, J = 2.0, 8.5 Hz, 2H), 7.39 (d
t, J = 2.0, 8.5 Hz, 2H), 9.15 (d, J = 2.1 Hz, 2H), 9.2
3 (t, J = 2.1 Hz, 1H). IR (KBr, cm ^-1 ): 3090, 2960, 2930, 2860, 1725, 163
0, 1595, 1545, 1475, 1435, 1385, 1340, 1275, 1170,
1090, 1070, 1025, 1005, 990, 920, 820, 775,820, 5
10, 485, 445. Mass (m / e): 484 (M ⁺ +2), 482 (M ⁺ ), 454 (M ⁺ -NO + 2),
452 (M ⁺ -NO), 290 (HO- (CH ₂ ) ₆ S-Ph-Br + 2), 288 (HO- (CH
₂ ) ₆ S-Ph-Br + 2), 203 ( ⁺ -CH ₂ S-Ph-Br + 2), 201 ( ⁺ CH ₂ S-Ph
-Br), 195 ((NO ₂ ) ₂ C ₆ H ₃ CO ⁺ ), 190 (HS-Ph-Br + 2), 188
(HS-Ph-Br), 165,149, 135, 122, 109, 82, 75, 55, 4
3, 41, 28. Elemental analysis (C ₁₉ H ₁₉ N ₂ O ₆ SBr, FW 483.33) Calculated: C 47.22% H 3.96% N 5.80% S 6.63% Found: C 47.48% H 3.70% N 5.78% S 6.57%

Compound (15) 23.4 obtained by the above reaction
8 g (48.6 mmol), acetic acid 200 ml and 30% -hydrogen peroxide solution 13.8
After stirring the solution obtained by mixing 3 g (122 mmol) under reflux for 2 hours, the reaction solution was poured into 500 ml of a saturated aqueous solution of sodium hydrogen carbonate. Furthermore, after adding sodium hydrogen carbonate and neutralizing, 1000 ml of water was added. The generated precipitate was collected by filtration. The obtained precipitate was purified by recrystallization from a mixed solvent of acetone / methanol to give 22.18 g (88.6%) of 6- (4-bromophenyl) sulfonyl-1-hexyl 3,5-dinitrobenzoate (16). To obtain white crystals.

¹ H NMR (500 MHz, CDCl ₃ , δ / ppm): 1.43-
1.87 (m, 8H), 3.09 (dt, J = 5.7, 7.9Hz, 2H), 4.43
(t, J = 6.7 Hz, 2H), 7.73 (dt, J = 2.0, 8.7 Hz, 2H),
7.78 (dt, J = 2.0, 8.7 Hz, 2H), 9.15 (d, J = 2.1 Hz, 2
H), 9.23 (t, J = 2.1 Hz, 1H) .IR (KBr, cm ^-1 ): 3440, 3100, 2935, 2865, 1725, 1685
1630, 1595, 1575, 1550, 1510, 1475, 1460, 1415, 1
390, 1340, 1300, 1280, 1245, 1175, 1165, 1145, 108
5, 1070, 1030, 1010, 970, 915, 835, 750, 720, 680,
670, 640, 610,520, 415. Mass (m / e): 516 (M ⁺ +2), 514 (M ⁺ ), 499, 497, 486
(M ⁺ -NO + 2), 484 (M ⁺ -NO), 321 ( ⁺ O- (CH ₂ ) ₆ SO ₂ -Ph-Br + 2),
319 ( ⁺ O- (CH ₂ ) ₆ SO ₂ -Ph-Br), 304 (CH ₂ = CH (CH ₂ ) ₄ SO ₂ -Ph
-Br + 2), 302 (CH ₂ = CH (CH ₂ ) ₄ SO ₂ -Ph-Br + 2), 249, 247, 2
36, 234, 223, 221, 213, 205, 203, 195 ((NO ₂ ) ₂ C ₆ H ₃ C
O ⁺ ), 179, 165 ((NO ₂ ) ₂ C ₆ H ₃ CO ⁺ -NO), 157 ( ⁺ Ph-Br + 2), 1
55 ( ⁺ Ph-Br), 103, 82, 75, 67, 55, 41, 29. Elemental analysis (C ₁₉ H ₁₉ N ₂ O ₈ SBr, FW 515.33) Calculated: C 44.28% H 3.72% N 5.44 % S 6.22% Found: C 44.33% H 3.67% N 5.31% S 6.19%

Put SnCl ₂ .2H ₂ O (56.41 g, 250 mmol) in a 500 ml eggplant flask, add 125 ml of ethanol, and add
And stirred. To this solution, compound (16) (12.88 g, 25.0 mmol) dissolved in 125 ml of THF was added. Further, sodium borohydride (1.89 g, 50.0 mmol) dissolved in 125 ml of ethanol was added, and the mixture was stirred at 70 ° C for 3 hours. After the reaction solution was concentrated under reduced pressure, an ethyl acetate solution was obtained. The ethyl acetate was washed with a 0.5N aqueous solution of sodium hydroxide, a saturated aqueous solution of ammonium chloride, and a saturated aqueous solution of sodium chloride in that order. The organic layer was dried over anhydrous sodium sulfate, and the solution was concentrated under reduced pressure. The residue was purified by recrystallization from ethyl acetate to give 6- (4-bromophenyl) sulfonyl-1-hexyl 3,5-diaminobenzoate (17) as pale yellow crystals in a yield of 10.46 g (91.9%). Was.

¹ H NMR (500 MHz, CDCl ₃ , δ / ppm): 1.35-
1.78 (m, 8H), 3.09 (dt, J = 5.7, 7.9Hz, 2H), 3.70 (B
r, 4H), 4.23 (t, J = 6.4 Hz, 2H), 6.19 (t, J = 2.1 Hz,
1H), 6.76 (d, J = 2.1 Hz, 2H), 7.72 (dt, J = 2.0, 6.8
Hz, 2H), 7.77 (dt, J = 2.0,6.8 Hz, 2H) .IR (KBr, cm ^-1 ): 3475, 3375, 3323, 3095, 2955, 293
5, 2870, 1700, 1600, 1570, 1475, 1390, 1365, 1315,
1300, 1255, 1245, 1210, 1195, 1140, 1085, 1070, 1
010, 990, 890, 835, 790, 780, 730, 700, 680, 615,
565, 550, 520, 410. Mass (m / e): 456 (M ⁺ +2), 454 (M ⁺ ), 376, 235, 221,
207, 152 ((NH ₂ ) ₂ C ₆ H ₃ COOH), 135 ((NH ₂ ) ₂ C ₆ H ₃ CO ⁺ ), 8
0, 55, 41, 29. Elemental analysis (C ₁₉ H ₂₃ N ₂ O ₄ SBr, FW 455.37) Calculated: C 50.12% H 5.09% N 6.15% S 7.04% Found: C 50.26% H 4.87% N 6.17% S 6.87%

Compound (17) obtained by the above reaction 9.06
g (19.9 mmol) was added with 40 ml of dry THF to form a solution. To this solution was added 16.7 g (79.6 mmol) of trifluoroacetic anhydride dissolved in 20 ml of dry THF, and the mixture was stirred for 1 hour. The reaction solution was poured into 200 ml of an aqueous saturated sodium hydrogen carbonate solution, and extracted with ethyl acetate. After dehydrating the organic layer with anhydrous sodium sulfate, the solution was concentrated under reduced pressure. The residue was purified by silica gel column chromatography using a mixed solvent of hexane and ethyl acetate (volume ratio: 1: 1) as an eluent, and recrystallized from a mixed solvent of chloroform and ethyl acetate to give 6- (4-bromophenyl) sulfonyl-1. -Hexyl 3,5-
Bis (trifluoroacetamido) benzoate (18)
Was obtained as pale yellow crystals in a yield of 12.60 g (97.8%).

¹ H NMR (500 MHz, CDCl ₃ , δ / ppm): 1.35-
1.85 (m, 8H), 3.14 (t, J = 7.5 Hz, 2H), 4.36 (t, J =
5.9 Hz, 2H), 7.73 (dt, J = 2.0, 6.7 Hz, 2H), 7.77 (d
t, J = 2.0, 6.7 Hz, 2H), 8.07 (d, J = 2.0 Hz, 2H), 8.4
0 (Br, 2H), 8.44 (t, J = 2.0 Hz, 1H) .IR (KBr, cm ^-1 ): 3430, 3325, 3185, 2125, 2940, 286
5, 1730, 1615, 1575, 1460, 1390, 1325, 1305, 1275,
1255, 1245, 1220, 1190, 1155, 1085, 1070, 1010, 8
85, 825, 770, 740, 705, 675, 640, 615, 560, 535, 4
60.Mass (m / e): 648 (M ⁺ +2), 646 (M ⁺ ), 568, 344 ((NHCO
CF ₃ ) ₂ C ₆ H ₃ COOH ⁺ ), 327 ((NHCOCF ₃ ) ₂ C ₆ H ₃ CO ⁺ ), 299 ((NH
COCF ₃ ) ₂ C ₆ H ₃ ⁺ ), 279, 275, 257, 223, 221, 203,201, 1
57 ( ⁺ Ph-Br + 2), 155 ( ⁺ Ph-Br), 82, 69, 67, 55, 41, 2
8, 17. Elemental analysis (C ₂₃ H ₂₁ N ₂ O ₆ SBrF ₆ , FW 647.38) Calculated: C 42.67% H 3.27% N 4.33% Found: C 42.71% H 3.11% N 4.39%

Embodiment 5

[0114]

Embedded image

7.12 g of the compound (18) obtained in Reference Example 3
(11.0 mmol), 1.73 g (16.5 mmol) of 4-vinylpyridine, 1.67 g (16.5 mmol) of triethylamine, palladium (II) acetate
0.123 g (0.55 mmol) and 15 ml of acetonitrile were mixed, and the system was degassed. This mixture is placed under an argon atmosphere.
Refluxed for 72 hours. After cooling, the reaction mixture was poured into 500 ml of water, and the generated precipitate was collected by filtration. The residue was purified by silica gel column chromatography using a mixed solvent of hexane / ethyl acetate (volume ratio 1: 2) as an eluent, and recrystallized from a mixed solvent of acetone / chloroform to give 6- {4- [2- (4-pyridyl). ) Ethenyl] phenyl} sulfonyl-1-hexyl 3,5-bis (trifluoroacetamido) benzoate (19) was obtained as white crystals in a yield of 5.43 g (73.6%).

¹ H NMR (500 MHz, CDCl ₃ , δ / ppm): 1.48-
1.88 (m, 8H), 3.17 (t, J = 7.4 Hz, 2H), 4.36 (t, J =
5.9 Hz, 2H), 7.17 (d, J = 16.4 Hz, 1H), 7.33 (d, J = 1
6.4, 1H), 7.40 (dd, J = 1.2, 6.0 Hz, 2H), 7.72 (d, J
= 8.4 Hz, 2H), 7.91 (d, J = 8.4Hz, 2H), 8.09 (d, J = 2.
0 Hz, 2H), 8.45 (t, J = 2.0 Hz, 1H), 8.58 (Br, 2H),
8.64 (dd, J = 1.2, 6.0 Hz, 2H). IR (KBr, cm ^-1 ): 3275, 3180, 3110, 2995, 2935, 285
5, 1715, 1600, 1575, 1510, 1460, 1440, 1415, 1330,
1305, 1280, 1230, 1210, 1190, 1165, 1140, 1085, 1
035, 1015, 995, 975, 935, 915, 875, 850, 830, 800,
765, 740, 725, 705, 670, 640, 615, 590, 50, 520,
495, 450.Mass (m / e): 671 (M ⁺ ), 652, 602 (M ⁺ -CF ₃ ), 327 ((NH
COCF ₃ ) ₂ C ₆ H ₃ CO ⁺ ), 299 ((NHCOCF ₃ ) ₂ C ₆ H ₃ ⁺ ), 257, 246,
229, 196, 180 ( ⁺ Ph-CH = CH-Py), 152. Elemental analysis (C ₃₀ H ₂₇ N ₃ O ₆ SF ₆ , FW 671.61) Calculated: C 53.65% H 4.05% N 6.26% Found : C 53.41% H 3.91% N 6.21% Example 6

[0117]

Embedded image

In an argon atmosphere, 15 ml of 1-butanol was added to 0.575 g (3.77 mmol) of 2-chlorobenzimidazole and 2.53 g (3.77 mmol) of the compound (19) obtained in Example 5, and the mixture was added at 100 ° C. for 60 hours. Stirred. After allowing the reaction mixture to cool, it was poured into 100 ml of acetone, and the generated precipitate was collected by filtration. 100 ml of methanol, 50 ml of THF and 25 ml of aqueous ammonia were added to the precipitate, and at 40 ° C.
Stirred for hours. The resulting precipitate was collected by filtration, and recrystallized from a mixed solvent of THF and methanol to give 2- [4
-(2- {4- [6- (3,5-diaminobenzoyloxy) hexyl-1-
Sulfonyl] phenyl} ethenyl) pyridinio] benzimidazolate (20) was obtained as reddish brown crystals in a yield of 0.281 g (12.7%).

¹ H NMR (500 MHz, CDCl ₃ , δ / ppm): 1.35-
1.85 (m, 8H), 3.15 (t, J = 7.8 Hz, 2H), 3.70 (br, 4
H), 4.18 (t, J = 6.5 Hz, 2H), 6.16 (t, J = 2.1 Hz, 1
H), 6.73 (d, J = 2.1 Hz, 2H), 7.17 (q, J = 3.1 Hz, 2H),
7.27 (d, J = 16.3 Hz, 1H), 7.62 (d, J = 16.3 Hz, 1H),
7.70 (q, J = 3.1 Hz, 2H), 7.80 (d, J = 8.3 Hz, 2H), 7.
86 (d, J = 7.0 Hz, 2H), 8.00 (d, J = 8.3 Hz, 2H), 9.95
(d, J = 7.0 Hz, 2H). IR (KBr, cm ^-1 ): 3435, 3370, 3225, 3125, 3085, 305
0, 2930, 2855, 1705, 1620, 1600, 1565, 1545, 1500,
1470, 1395, 1365, 1305, 1270, 1240, 1195, 1140, 1
115, 1085, 1005, 990, 970, 930, 850, 810, 770, 75
0, 725, 710, 680,655, 625, 595, 570, 530, 495. Mass (m / e): 596 (SIMS, M ⁺ +1), 252, 209, 183, 174,
149, 133, 105, 90, 79, 63, 43, 31.

Reference Example 4

[0121]

Embedded image

17.30 g (100 mmol) of 4-bromophenol, 6-
200 mL of acetone was added to 15.03 g (110 mmol) of chloro-1-hexyl alcohol, 27.64 g (200 mmol) of anhydrous potassium carbonate and 5 g of potassium iodide, and the mixture was refluxed for 72 hours. The reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. Ethyl acetate was added to the residue, and the mixture was washed with an aqueous sodium hydroxide solution. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure,
Purification by silica gel chromatography using a mixed solvent of ethyl acetate (volume ratio 1: 4 → 1: 2) as an eluent gave 26.58 g of 4- (6-hydroxy-1-hexyloxy) bromobenzene (21) (97.3%). ) Yielded as a colorless liquid.

¹ H NMR (500 MHz, CDCl ₃ , δ / ppm): 1.28
(t, J = 4.7 Hz, 1H), 1.36-1.55 (m, 4H), 1.56-1.63
(m, 2H), 1.76-1.82 (m, 2H), 3.64-3.68 (m, 2H), 3.9
2 (t, J = 6.5 Hz, 2H), 6.77 (dt, J = 2.1, 9.0 Hz, 2H),
7.36 (dt, J = 2.1, 9.0 Hz, 2H) .IR (neet, cm ^-1 ): 3340, 2935, 2860, 1590, 1575, 149
0, 1470, 1435, 1385, 1285, 1245, 1170, 1100, 1070,
1055, 1020, 1005, 820, 730, 640, 600, 505. Mass (m / e): 274 (M ⁺ +2), 272 (M ⁺ ), 187 ( ⁺ CH ₂ O-Ph-B
r + 2), 185 ( ⁺ CH ₂ O-Ph-Br), 174 (HO-Ph-Br + 2), 172 (HO
-Ph-Br), 157, 155, 145, 143, 93, 83, 67, 55, 41, 3
9, 31, 28.

Under an argon atmosphere, 50 ml of dry THF was added to 16.62 g (60.8 mmol) of the compound (21) obtained above and 8.61 g (85.1 mmol) of triethylamine to form a solution. To this solution, 14.86 g (73.0 mmol) of 3,5-dinitrobenzoic acid chloride dissolved in 70 ml of dry THF was added, and the mixture was stirred at room temperature for 1 hour. The reaction solution was filtered, the filtrate was concentrated under reduced pressure, and the residue was recrystallized from a mixed solvent of methanol and ethyl acetate to give 6- (4-bromophenyl) oxy-1-hexyl 3,5-dinitrobenzoate (22). 19.36g (73.2
%) As white crystals.

¹ H NMR (500 MHz, CDCl ₃ , δ / ppm): 1.50-
1.61 (m, 4H), 1.89-1.91 (m, 4H), 3.94 (t, J = 6.3 H
z, 2H), 4.47 (t, J = 6.7 Hz, 2H), 6.76 (dt, J = 2.0,
8.9Hz, 2H), 7.34 (dt, J = 2.0, 8.9 Hz, 2H), 9.15 (d,
J = 2.1 Hz, 2H), 9.23 (t, J = 2.1Hz, 1H) .IR (KBr, cm ^-1 ): 3090, 2945, 2010, 2895, 2870, 173
0, 1630, 1590, 1575, 1545, 1490, 1470, 1390, 1340,
1290, 1275, 1245, 1170, 1115, 1100, 1075, 1040, 1
005, 960, 925, 840, 825, 795, 775, 725, 670, 640,
510, 475, 430. Mass (m / e): 468 (M ⁺ +2), 466 (M ⁺ ), 438 (M ⁺ -NO + 2),
436 (M ⁺ -NO), 408 (M ⁺ -2NO + 2), 406 (M ⁺ -2NO), 274 (HO
-(CH ₂ ) ₆ O-Ph-Br + 2), 272 (HO- (CH ₂ ) ₆ O-Ph-Br), 195 ((N
O ₂ ) ₂ C ₆ H ₃ CO ⁺ ), 183, 174 (HO-Ph-Br + 2), 172 (HO-Ph-B
r), 165 ((NO ₂ ) ₂ C ₆ H ₃ CO ⁺ -NO), 157 ( ⁺ Ph-Br + 2), 155 ( ⁺
Ph-Br), 149, 119, 103, 93, 91, 83, 75, 67, 55, 41,
28. Elemental analysis (C ₁₉ H ₁₉ N ₂ O ₇ Br, FW 467.27) Calculated: C 48.84% H 4.10% N 6.00% Found: C 48.72% H 3.88% N 5.99%

Put SnCl ₂ .2H ₂ O (90.26 g, 400 mmol) in a 500 ml eggplant flask, add 200 ml of ethanol, and add 70 ° C.
And stirred. To this solution, 18.69 g (40.0 mmol) of the compound (22) dissolved in 200 ml of THF was added. Further, 3.03 g (80.0 mmol) of sodium borohydride dissolved in 100 ml of ethanol was added, and the mixture was stirred at 70 ° C for 3 hours. After the reaction solution was concentrated under reduced pressure, an ethyl acetate solution was obtained. The solution is washed with a 0.5N aqueous solution of sodium hydroxide, a saturated aqueous solution of ammonium chloride, and a saturated aqueous solution of sodium chloride in that order. Purified by silica gel chromatography using 1: 1 → 1: 2) as an eluent. Further, recrystallization from ethyl acetate gave 14.95 g (91.8%) of 6- (4-bromophenyl) oxy-1-hexyl 3,5-diaminobenzoate (23).
In the form of white crystals.

¹ H NMR (500 MHz, CDCl ₃ , δ / ppm): 1.46-
1.58 (m, 4H), 1.76-1.84 (m, 4H), 3.69 (Br, 4H), 3.
93 (t, J = 6.4 Hz, 2H), 4.28 (t, J = 6.6 Hz, 2H), 6.20
(t, J = 2.0 Hz, 1H), 6.77 (dt, J = 2.2, 9.0 Hz, 2H),
6.78 (d, J = 2.0 Hz, 2H), 7.36 (dt, J = 2.2, 9.0 Hz, 2
H) .IR (KBr, cm ^-1 ): 3430, 3325, 3210, 3055, 2935, 291
0, 2850, 1715, 1625, 1605, 1590, 1490, 1470, 1430,
1385, 1350, 1305, 1285, 1235, 1190, 1170, 1100, 1
070, 1040, 990, 955, 930, 860, 850, 825, 800, 765,
725, 675, 645, 600, 530, 505, 470. Mass (m / e): 408 (M ⁺ +2), 406 (M ⁺ ), 355, 327, 295,
281, 270, 235, 221, 207, 174 (HO-Ph-Br + 2), 172 (HO
-Ph-Br), 152 ((NH ₂ ) ₂ C ₆ H ₃ COOH), 135 ((NH ₂ ) ₂ C ₆ H ₃ C
O ⁺ ), 108, 80, 73, 67, 55, 41, 29. Elemental analysis (C ₁₉ H ₂₃ N ₂ O ₃ Br, FW 407.31) Calculated: C 56.03% H 5.69% N 6.88% Found: C 56.09% H 5.51% N 6.81%

Compound (23) 2.44 obtained by the above reaction
10 ml of dry THF was added to g (6.00 mmol) to form a solution. To this solution was added 2.77 g (13.2 mmol) of trifluoroacetic anhydride dissolved in 10 ml of dry THF, and the mixture was stirred for 1 hour. Pour the reaction solution into 50 ml of saturated aqueous sodium bicarbonate,
Extracted with ethyl acetate. After dehydrating the organic layer with anhydrous sodium sulfate, the solution was concentrated under reduced pressure. Hexane residue
After purification by silica gel column chromatography using an ethyl acetate mixed solvent (4: 1 by volume) as an eluent, recrystallization from a methylene chloride / hexane mixed solvent
6- (4-bromophenyl) oxy-1-hexyl 3,5-bis (trifluoroacetamido) benzoate (24) was 3.51 g (9
(7.6%) as white crystals.

¹ H NMR (500 MHz, CDCl ₃ , δ / ppm): 1.50-
1.58 (m, 4H), 1.77-1.86 (m, 4H), 3.94 (t, J = 6.4 H
z, 2H), 4.37 (t, J = 6.6 Hz, 2H), 6.76 (dt, J = 2.1,
9.0 Hz, 2H), 7.34 (dt, J = 2.1, 9.0 Hz, 2H), 8.05 (B
r, 2H), 8.07 (d, J = 2.0 Hz, 2H), 8.30 (t, J = 2.0 Hz,
1H) .IR (KBr, cm ^-1 ): 3345, 3280, 3180, 3100, 2990, 294
5, 2865, 1740, 1710, 1620, 1570, 1490, 1475, 1455,
1390, 1325, 1285, 1260, 1245, 1215, 1190, 1170, 1
135, 1070, 1055, 1040, 995, 970, 925, 895, 880, 82
0, 770, 740, 675,640, 610, 595, 540, 505. Mass (m / e): 600 (M ⁺ +2), 598 (M ⁺ ), 344 ((NHCOCF ₃ ) ₂
C ₆ H ₃ COOH), 327 ((NHCOCF ₃ ) ₂ C ₆ H ₃ CO ⁺ ), 299 ((NHCOCF ₃ )
₂ C ₆ H ₃ ⁺ ), 279, 275, 257, 229, 203, 201, 174 (HO-Ph-
Br + 2), 172 (HO -Ph-Br), 83, 69, 67, 55, 41, 28. Elemental analysis _{(C 23 H 21 N 2 O} 5 BrF 6, FW 599.32) Calculated: C 46.09% H 3.53% N 4.67% Found: C 46.16% H 3.36% N 4.62%

Embodiment 7

[0131]

Embedded image

5.99 g of compound (24) obtained in Reference Example 4
(10.0 mmol), 1.58 g (15.0 mmol) of 4-vinylpyridine, 1.52 g (15.0 mmol) of triethylamine, palladium acetate (I
I) 0.112 g (0.50 mmol), triphenylphosphine 0.262
g (1.00 mmol) and 10 ml of DMF were mixed, and the system was degassed. This mixture was refluxed for 72 hours under an argon atmosphere.
After cooling, the reaction mixture was poured into 500 ml of water, and the generated precipitate was collected by filtration. The residue was purified by silica gel column chromatography using a mixed solvent of hexane / ethyl acetate (volume ratio 1: 2) as an eluent, and recrystallized from a mixed solvent of acetone / chloroform to give 6- {4- [2- (4
-Pyridyl) ethenyl] phenyl} oxy-1-hexyl3,5-
Bis (trifluoroacetamido) benzoate (2
5) was obtained as white crystals in a yield of 1.81 g (29.1%).

¹ H NMR (500 MHz, CDCl ₃ , δ / ppm): 1.48-
1.62 (m, 4H), 1.77-1.89 (m, 4H), 4.01 (t, J = 6.4 H
z, 2H), 4.38 (t, J = 6.7 Hz, 2H), 6.88 (d, J = 16.1 H
z, 1H), 6.89 (d, J = 8.9 Hz, 2H), 7.25 (d, J = 16.1 Hz,
1H), 7.34 (d, J = 6.1 Hz, 2H), 7.62 (d, J = 8.9 Hz, 2
H), 8.08 (d, J = 2.0 Hz, 2H), 8.09 (Br, 2H), 8.31
(t, J = 2.0 Hz, 1H), 8.55 (dd, J = 1.2, 6.1 Hz, 2H) .IR (KBr, cm ^-1 ): 3280, 3105, 3035, 2945, 2860, 173
0, 1705, 1595, 1575, 1510, 1460, 1440, 1420, 1390,
1360, 1330, 1305, 1255, 1230, 1190, 1160, 1145, 1
070, 1040, 1015, 995, 970, 930, 900, 875, 830, 79
5, 770, 735, 675,640, 615, 575, 545, 530, 510. Mass (m / e): 623 (M +), 604, 554 (M + -CF 3), 327 ((NH
COCF ₃ ) ₂ C ₆ H ₃ CO ⁺ ), 299 ((NHCOCF ₃ ) ₂ C ₆ H ₃ ⁺ ), 257, 197
(HO-Ph-CH = CH-Py), 180 ( ⁺ Ph-CH = CH-Py), 168, 152, 8
3, 55, 41. Elemental analysis _{(C 30 H 27 N 3 O} 5 F 6, FW 623.55) Calculated: C 57.79% H 4.36% N 6.74% Found: C 57.85% H 4.58% N 6.25%

Embodiment 8

[0135]

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Under an argon atmosphere, 7 ml of 1-butanol was added to 0.271 g (1.77 mmol) of 2-chlorobenzimidazole and 1.106 g (1.77 mmol) of the compound (25) obtained in Example 7, and the mixture was heated at 100 ° C. for 24 hours. Stirred. After allowing the reaction mixture to cool, it was poured into 100 ml of acetone, and the generated precipitate was collected by filtration. 100 ml of methanol, 50 ml of THF and 25 ml of aqueous ammonia were added to the precipitate, and at 40 ° C.
Stirred for hours. The resulting precipitate was collected by filtration, and recrystallized from a mixed solvent of THF and methanol to give 2- [4
-(2- {4- [6- (3,5-diaminobenzoyloxy) hexyl-1-
[Oxy] phenyl} ethenyl) pyridinio] benzimidazolate (26) was obtained as red-brown crystals in a yield of 0.676 g (69.7%).

¹ H NMR (500 MHz, CDCl ₃ , δ / ppm): 1.45-
1.70 (m, 4H), 1.76-1.89 (m, 4H), 3.67 (br, 4H), 4.
05 (t, J = 6.4 Hz, 2H), 4.29 (t, J = 6.6 Hz, 2H), 6.20
(t, J = 2.0 Hz, 1H), 6.78 (d, J = 2.1 Hz, 2H), 6.97
(d, J = 8.7 Hz, 2H), 7.03 (d, J = 16.1 Hz, 1H), 7.16
(q, J = 3.1 Hz, 2H), 7.59 (d, J = 8.7 Hz, 2H), 7.62
(d, J = 16.1 Hz, 1H), 7.70 (q, J = 3.1 Hz, 2H), 7.80
(d, J = 7.1 Hz, 2H), 9.85 (d, J = 7.1 Hz, 2H) .IR (KBr, cm ^-1 ): 3430, 3345, 3225, 3130, 3050, 293
5, 2860, 1700, 1595, 1570, 1510, 1470, 1425, 1395,
1365, 1330, 1310, 1300, 1255, 1195, 1170, 1115, 1
060, 1030, 1005, 970, 875, 840, 810, 770, 750, 68
0, 625, 595, 540. Mass (m / e): 596 (SIMS, M ⁺ +1), 252, 209, 183, 174,
149, 133, 105, 90, 79, 63, 43, 31.

Embodiments 9 and 10

[0139]

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The argon gas obtained in Example 2 was
50.2 mg (0.091 mmol) of the tine compound (7) in 0.5 ml of NMP
After dissolving and cooling to 0 ° C.,
Dissolve 15.2 mg (0.091 mmol) of isocyanate in 0.5 ml of NMP
The solution was added and stirred at 0 ° C. for 2 hours. Next, this anti
The reaction solution was poured into 200 ml of methanol, and the resulting precipitate was removed.
It is separated by filtration, dried, dissolved again in NMP, and excess methanol
When reprecipitation was repeated in the above formula, the above structural formula (P1)
25.3 mg of the indicated polymer were obtained. Weight average of the obtained polymer
The average molecular weight was measured by a light scattering method using NMP as a solvent.
However, 1.5x10 ^FourMet. Of polymer (P1)¹H-NM
The R spectrum is shown below. Also, it is determined by DSC measurement.
The glass transition temperature of the polymer (P1)
Was.

¹ H NMR (400 MHz, (CD ₃ ) ₂ SO, δ / ppm): 1.
1-1.3 (m, 4H), 1.4-1.6 (m, 4H), 2.1-2.3 (m, 2H),
3.0-3.2 (m, 4H), 4.1-4.3 (m, 2H), 4.3-4.5 (m, 2H),
6.0-6.1 (m, 2H), 6.7-6.8 (m, 2H), 6.9-7.0 (m, 2
H), 7.0-7.1 (m, 2H), 7.4-7.6 (m, 3H), 7.7-7.8 (m,
2H), 7.9-8.1 (m, 1H), 8.1-8.2 (m, 2H), 8.3-8.4 (m,
2H), 9.7-9.8 (m, 2H).

In the above polymerization reaction, 345 mg (0.682 mmol) of the betaine compound (13) obtained in Example 4 and 115 mg (0.682 mmol) of hexamethylenediamine were each added with NM.
The same reaction and purification by reprecipitation were performed using a solution dissolved in 3.4 ml of P to obtain 152 mg of a polymer represented by the above structural formula (P2). The weight average molecular weight of the obtained polymer was measured by a light scattering method using NMP as a solvent and found to be 2.1 × 10 ⁴ . ¹ H-NMR of polymer (P2)
The spectrum is shown below. The glass transition temperature of the polymer (P2) determined by DSC measurement was about 160 ° C.

¹ H NMR (400 MHz, (CD ₃ ) ₂ SO, δ / ppm): 1.
2-1.3 (m, 4H), 1.4-1.5 (m, 4H), 2.1-2.3 (m, 2H),
3.0-3.1 (m, 4H), 4.1-4.2 (m, 2H), 4.4-4.5 (m, 2H),
6.0-6.1 (m, 2H), 6.7-6.8 (m, 2H), 6.9-7.0 (m, 2
H), 7.0-7.1 (m, 2H), 7.4-7.6 (m, 3H), 7.7-7.8 (m,
2H), 7.9-8.1 (m, 1H), 8.1-8.2 (m, 2H), 8.3-8.4 (m,
2H), 9.7-9.8 (m, 2H).

Embodiments 11 and 12

[0145]

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Under an argon atmosphere, 55.3 mg (0.100 mmol) of the betaine compound (7) obtained in Example 2 and 34.9 mg (0.300 mmol) of hexamethylenediamine were dissolved in 2.0 ml of THF, and the solution was cooled to 0 ° C. A solution of 67.3 mg (0.400 mmol) of hexamethylene diisocyanate dissolved in 2.0 ml of THF was added to the solution, and the mixture was stirred at 0 ° C. for 1 hour. Next, the reaction solution was poured into 400 ml of methanol, and the resulting precipitate was separated by filtration and dried to obtain 90 mg of a random copolymer represented by the above structural formula (P3). When the weight average molecular weight of the obtained polymer was measured by a light scattering method using NMP as a solvent, it was 1.8 × 10 ⁴ . In addition, the polymer (P3) ¹ H-
The composition ratio x / y of both components determined from the NMR spectrum is 25/75
Met. Further, the polymer (P
The glass transition temperature of 3) was about 115 ° C.

In the above polymerization reaction, the betaine compound (13) 5 obtained in Example 4 was used instead of the compound (7).
Except that 0.6 mg (0.100 mmol) was used, the reaction and purification by reprecipitation were performed in exactly the same manner.
90 mg of a copolymer represented by 4) was obtained. When the weight average molecular weight of the obtained polymer was measured by a light scattering method using NMP as a solvent, it was 2.5 × 10 ⁴ . The polymer (P
The composition ratio x / y of both components determined from the ¹ H-NMR spectrum of 4) was 25/75. The glass transition temperature of the polymer (P4) determined by DSC measurement was about 110 ° C.

Example 13 The polymer (P4) obtained in Example 8 was dissolved in DMF to prepare a 1% by weight solution, which was applied on a glass substrate heated to 60 ° C., and the solvent was evaporated. A thin film was formed. An ultraviolet-visible absorption spectrum was measured using the obtained substrate, and the maximum absorption wavelength and the absorption edge wavelength of the thin film were determined to be 438 nm and 600 nm, respectively. next,
Place this board on an aluminum hot plate,
The temperature was raised to 160 ° C. 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 20 minutes or more to align the betaine residue in the side chain, and then cooled to room temperature while continuing corona charging.

Next, the maker fringe method (J. Jerphagno
n et al., J. Appl. Phys. Vol. 41, p. 1667 (1970)), the second harmonic (SH wave) generated from the 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. Similarly, for a y-cut quartz crystal having a thickness of 1 mm, S
H waves were detected. From the measurement results were calculated y- d ₁₁ value of cut quartz crystals (0.46 pm / V) as a reference, the second-order nonlinear optical constant d ₃₃ value of the thin film obtained by curve fitting using the least square method However, it showed a value of 4.6 pm / V.

Embodiment 14

[0151]

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Compound (13) obtained in Example 4 and
Equimolar amounts of 2,4-toluylene diisocyanate were mixed with each other, and dried DMF was added thereto under an argon atmosphere to a concentration of 5% by weight to form a solution. This was stirred at room temperature for about 1 hour to prepare a solution of the polymer represented by the above (P-5). The resulting solution was applied on a glass substrate, and then heated to 140 ° C. to evaporate the solvent, and corona-charged with a tungsten needle at a charging voltage of 10 kV from above 2.5 cm to form a thin film. This state was maintained for 20 minutes or more to align the betaine residue in the side chain, and then cooled to room temperature while continuing corona charging. Next, calculation of second-order nonlinear optical constant d ₃₃ value of the thin film to detect the SH wave generated similarly by the manufacturer fringe method as in Example 13, 2.4P
The value of m / V was shown.

Embodiments 15 and 16

[0154]

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Compound (13) obtained in Example 4, piperazine and 2,4-toluylene diisocyanate (TD
I) were mixed with each other so as to have a molar ratio shown in Table 1,
Dry DM to a concentration of 5% by weight under argon atmosphere
F was added to make a solution. This was stirred at room temperature for about 1 hour to produce a solution of the copolymer represented by the above (P-6). The resulting solution was applied on a glass substrate, and then heated to 140 ° C. to evaporate the solvent, and corona-charged with a tungsten needle at a charging voltage of 10 kV from above 2.5 cm to form a thin film. This state was maintained for 20 minutes or more to align the betaine residue in the side chain, and then cooled to room temperature while continuing corona charging. Next, calculation of second-order nonlinear optical constant d ₃₃ value of the thin film to detect the SH wave generated similarly by the manufacturer fringe method as in Example 13 showed a value according to Table 1, respectively.

[0156]

TABLE 1 ───────────────────────── molar ratio d ₃₃ value numbers of the examples charged monomers (13) / piperazine / TDI (pm / V) {15 1/2 1/2 2.5 16 1/3/4 3.8} ─────────────────────

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08G 18/32 C08G 18/32 B 18/38 18/38 Z 69/26 69/26 69/42 69/42 73/00 73 / 00 73/10 73/10

Claims (4)

[Claims] 1. A compound represented by the following general formula (I) (Where A is a hydrogen atom or an acyl group, Q is a single bond, an oxygen atom, a sulfur atom or a group represented by SO ₂ , m is 0 to
An integer of 10 and p is an integer of 0 or 1. Where m
Is 0 or p is 0, Q is a single bond. The compound which has a pyridyl group represented by). 2. The following general formula (II): (Where A is a hydrogen atom or an acyl group, Q is a single bond, an oxygen atom, a sulfur atom or a group represented by SO ₂ , Y is a nitrogen atom or a carbon atom having a substituent R, Z is a single bond or methylene The group, R ¹ and R ² may form an aromatic ring together with a hydrogen atom, a lower alkyl group or a carbon atom to which each is bonded, and may have a substituent on the aromatic ring. Good, m is an integer from 0 to 10, p is 0 or 1.
Is an integer. However, when m is 0 or p is 0, Q is a single bond. R is a hydrogen atom, a lower alkyl group or a phenyl group. A betaine compound represented by). 3. A compound represented by the following general formula (II)
I) (Wherein Q is a single bond, an oxygen atom, a sulfur atom or SO ₂
Y is a nitrogen atom or a carbon atom having a substituent R, Z is a single bond or a methylene group, R ¹ and R ² are a hydrogen atom, a lower alkyl group or a carbon atom to which each is bonded. May form an aromatic ring, or may have a substituent on the aromatic ring, and R ³ may form an imide ring integrally with a hydrogen atom or one bond. , M is an integer of 0 to 10, and p is an integer of 0 or 1. However, when m is 0 or p is 0, Q is a single bond. R is a hydrogen atom, a lower alkyl group or a phenyl group. A) a polymer containing at least 1 mol% of a repeating unit containing a structural unit represented by formula (1) and having a weight average molecular weight of 2,000 or more 4. A compound represented by the following general formula (II)
I) (Wherein Q is a single bond, an oxygen atom, a sulfur atom or SO ₂
Y is a nitrogen atom or a carbon atom having a substituent R, Z is a single bond or a methylene group, R ¹ and R ² are a hydrogen atom, a lower alkyl group or a carbon atom to which each is bonded. May form an aromatic ring, or may have a substituent on the aromatic ring, and R ³ may form an imide ring integrally with a hydrogen atom or one bond. , M is an integer of 0 to 10, and p is an integer of 0 or 1. However, when m is 0 or p is 0, Q is a single bond. R is a hydrogen atom, a lower alkyl group or a phenyl group. A) a polymer non-linear optical material comprising a polymer containing at least 1 mol% of a repeating unit containing a structural unit represented by formula (1) and having a weight average molecular weight of 2,000 or more.