JPH1036338A - Aromatic dicarboxylic acid and diamine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound which can create a macromolecular compound chemically bonding nonlinear molecules stably, soluble in solvents, having high glass transition temperature and gives a macromolecular nonlinear optical material having excellent nonlinear optical characteristics and excellent processability and stability. SOLUTION: This compound is represented by formula I (R is H, a lower alkyl; Y<1> and Y<2> are each N, CH; R<1> and R<2> are each a 1-20C alkyl or may be incorporated together with the bonding N atoms to form a ring; p is 1-6; m is 0, 1) and by formula II, typically 5- 3-[4-(N, N-dihexylamino) phenylsulfonyl]propoxy}isophthalic acid. The compound of formula I is prepared by the condensation reaction of a hydroxyphthalic diester of formula III (R is a lower alkyl) with an alcohol of formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel aromatic dicarboxylic acid compound and aromatic diamine compound which are intermediates for producing polyamides exhibiting good second-order nonlinear optical effects.

[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
Organic compounds (dyes) such as S) have been found to exhibit excellent nonlinear optical properties, and various organic nonlinear optical materials have been actively studied for development. 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, Masao Kato and Hachiro Nakanishi, "Organic Nonlinear Optical Materials", CMC (1985); The Chemical Society of Japan,
"Organic Materials for Nonlinear Optics", Academic Press, 1992; Seth R. Marder et al., "Materials for Non
linear Optics ", ACS Symposium Series 455, American
Chemical Society, (1991) etc.)

However, it is difficult to produce a large single crystal with the above-mentioned low molecular weight organic compound, so that the size cannot be increased and the optical path length cannot be obtained. Even if a large crystal is formed, the existence of an electric dipole in the ground state exists. Therefore, there is a problem that a centrally symmetric structure is easily formed upon crystallization, and large nonlinearity exhibited by one molecule is easily offset as a whole crystal. Therefore,
Organic polymer-based nonlinear optical materials that are advantageous in terms of processing and upsizing have been studied. That is, an organic compound having a large nonlinear optical property (hereinafter, referred to as a nonlinear molecule) is mixed and dispersed in a polymer material, or the nonlinear molecule is chemically bonded to the polymer main chain by a covalent bond to increase the nonlinear molecule. A film uniformly dispersed in a molecular matrix is prepared, and a voltage is applied to the film to perform an electric field alignment treatment (hereinafter referred to as poling) to orient the nonlinear molecules in one direction, thereby obtaining a high second-order nonlinear optical characteristic as a whole. Attempts have been made to obtain large materials that have. (For example,
DM Burland et al., "Second-Order Nonlinearity in Pol
ed-Polymer Systems ", Chemical Reviews, Vol. 94, p.3
1-75 (1994) etc.)

[0005]

In such a polymer system, it is known that the nonlinear optical characteristic tends to increase in proportion to the content of the nonlinear molecule. However, when a nonlinear molecule is contained in a high concentration in a conventional dispersion type or chemical bond type polymer nonlinear optical material,
Problems such as a decrease in the mechanical strength of the film, loss of light transmission, and difficulty in orienting all the nonlinear molecules due to poling resulted in the absence of high nonlinear optical characteristics. Also, even if the nonlinear molecules are oriented immediately after poling and exhibit high nonlinear optical properties, there is a problem in terms of stability in long-term use due to a decrease in nonlinear optical intensity due to orientation relaxation based on the glass transition or the like of the polymer material. 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.

Accordingly, an object of the present invention is to create a polymer compound which is stable in a chemical bond with a nonlinear molecule, is soluble in a solvent and has a high glass transition temperature. An object of the present invention is to provide a polymer nonlinear optical material excellent in stability and stability.

[0007]

Means for Solving the Problems The present inventors have made intensive studies to obtain a polymer nonlinear optical material having the above-mentioned characteristics. As a result, they have found that it is possible to synthesize a novel dicarboxylic acid compound and a diamine compound having a nonlinear molecule, and further obtain a polyamide having a high glass transition temperature by performing polycondensation using the compound as a monomer. The polyamide was found to be soluble in a solvent and to exhibit a high second-order nonlinear optical effect by subjecting the resulting film to a poling treatment, and thus reached the present invention.

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

[0009]

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(Wherein, R is a hydrogen atom or a lower alkyl group, Y ¹ and Y ² are each independently a nitrogen atom or a group represented by CH, R ¹ and R ² are each independently a straight chain having 1 to 20 carbon atoms.) Or a branched alkyl group or a bonded nitrogen atom to form a ring, p is an integer of 1 to 6, and m is an integer of 0 or 1.) Aromatic dicarboxylic acid compound represented by the following general formula (II):

[0011]

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Wherein Y ¹ and Y ² are each independently a nitrogen atom or a group represented by CH, and R ¹ and R ² are each independently a group having 1 carbon atom.
Up to 20 linear or branched alkyl groups or a combined nitrogen atom to form a ring;
p is an integer of 1 to 6, and m is an integer of 0 or 1. )).

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The lower alkyl group represented by R in the general formula (I) is an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group. , A sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group.

In formulas (I) and (II), the linear or branched alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² is a methyl group, an ethyl group, a propyl group, Isopropyl group, butyl group, sec-butyl group, tert
-Butyl, pentyl, 2-methylpentyl, hexyl, heptyl, octyl, nonyl, decyl,
An undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group or an icosyl group can be exemplified, in which case R ¹ and R ² may be the same or different. Examples of the ring formed integrally with the nitrogen atom to which R ¹ and R ² are bonded include an aziridine ring, an azetidine ring, a pyrrolidine ring, a pyrroline ring, and a piperidine ring.

The aromatic dicarboxylic acid compound represented by the general formula (I) of the present invention can be produced, for example, by the following synthesis method. That is, the following general formula (III)

[0016]

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(Wherein R is a lower alkyl group), and a hydroxyphthalic acid diester compound represented by the following general formula (IV):

[0018]

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(Wherein, Y ¹ and Y ² are each independently a nitrogen atom or a group represented by CH, and R ¹ and R ² are each independently a group having 1 carbon atom.
Up to 20 linear or branched alkyl groups or a combined nitrogen atom to form a ring;
p is an integer of 1 to 6, and m is an integer of 0 or 1. By the condensation reaction with the alcohol compound represented by the formula (1), an aromatic dicarboxylic acid compound represented by the general formula (I) wherein R is a lower alkyl group is obtained. Further, among the aromatic dicarboxylic acid compounds represented by the general formula (I), R
Is a hydrogen atom, among the aromatic dicarboxylic acid compounds represented by the general formula (I) obtained by the above reaction, those in which R is a lower alkyl group, for example, lithium hydroxide, potassium hydroxide, water It can be easily obtained by hydrolysis in the presence of a basic substance such as sodium oxide, aluminum hydroxide, potassium carbonate, sodium carbonate, potassium acetate, sodium acetate and sodium phosphate.

The above condensation reaction suitably proceeds in the presence of a suitable condensing agent. It is known that the reaction suitably proceeds by using diethyl azodicarboxylate and triphenylphosphine as the condensing agent to be used. (Eg, O. Mitsunobu, Synthesis, 1st
981, pp. 1-28 (1981), etc.) These condensing agents are used in an amount of 0.1 to 0.1 with respect to the compound represented by the general formula (III).
It is preferable to use in a range of 10 equivalents. 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 general formula (II) used as a raw material
Examples of the hydroxyphthalic acid diester compound represented by I) include dimethyl 3-hydroxyphthalate, dimethyl 4-hydroxyphthalate, diethyl 3-hydroxyphthalate,
Diethyl hydroxyphthalate, dimethyl 4-hydroxyisophthalate, dimethyl 5-hydroxyisophthalate, diethyl 4-hydroxyisophthalate, diethyl 5-hydroxyisophthalate, dipropyl 4-hydroxyisophthalate,
Dipropyl 5-hydroxyisophthalate, dimethyl 2-hydroxyterephthalate, diethyl 2-hydroxyterephthalate, dipropyl 2-hydroxyterephthalate, dibutyl 2-hydroxyterephthalate, dipentyl 2-hydroxyterephthalate, dihexyl 2-hydroxyterephthalate, etc. Examples can be given.

On the other hand, the aromatic diamine compound represented by the general formula (II) can be produced, for example, by the following synthesis method. That is, the following general formula (V)

[0023]

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(Wherein X ¹ is a hydroxyl group or a halogen atom) by a condensation reaction of dinitrobenzoic acid or a dinitrobenzoic halide represented by the general formula (IV) with an alcohol compound represented by the general formula (IV). The following general formula (V
I)

[0025]

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(Wherein Y ¹ and Y ² are each independently a nitrogen atom or a group represented by CH, and R ¹ and R ² are each independently a group having 1 carbon atom.
Up to 20 linear or branched alkyl groups or a combined nitrogen atom to form a ring;
p is an integer of 1 to 6, and m is an integer of 0 or 1. ) Is first synthesized, and then the nitro group of the dinitro compound represented by the general formula (VI) is reduced to produce the aromatic diamine compound represented by the general formula (II). can do.

In the dinitrobenzoic acid or dinitrobenzoic acid halide represented by the general formula (V) used herein, the dinitro group may be substituted at 2,3-position, 2,4-position, 2,2-position on the benzene ring. 5th, 2nd, 6th, 3rd, 4th, 3,
The 5th position is exemplified, but the 3rd and 5th positions are most preferred in view of easiness of synthesis and availability of raw materials.

In the above condensation reaction, when dinitrobenzoic acid in which X ^{1 in the} formula (V) is a hydroxyl group is used, the reaction generally proceeds suitably in the presence of a condensing agent. As a condensing agent used at that time, mineral acids such as hydrochloric acid and sulfuric acid, aromatic sulfonic acids such as tosylic acid, Lewis acids such as boron trifluoride-diethyl ether complex, trifluoroacetic anhydride, dicyclohexylcarbodiimide, N-
Examples thereof include an alkylpyridinium salt, triphenylphosphine, and polyphosphate. In this case, the reaction proceeds preferably within a range of room temperature to 100 ° C. On the other hand, in the above condensation reaction, when dinitrobenzoic acid halide in which X ^{1 in the} general formula (V) is a halogen atom is used, hydrogen halide is generated, and thus triethylamine, N, N- The reaction suitably proceeds when the reaction is performed in the presence of an organic base such as dimethylaniline or pyridine. In this case, 0 ° C
Performing at a relatively low temperature of about to room temperature is preferable from the viewpoint of suppressing a side reaction. All of these reactions are preferably performed in an organic solvent.Examples of the organic solvent used here include hexane, heptane, diethyl ether, ethyl acetate, benzene, toluene, xylene, chloroform, dichloromethane, dichloroethane, carbon tetrachloride, Acetone, tetrahydrofuran and the like are preferably used,
It is not limited to these.

The reduction reaction of the nitro group is carried out by using a commonly used reducing agent such as diborane, lithium borohydride, sodium borohydride, sodium aluminum hydride, sodium dialkoxyaluminum hydride and sodium diethylaluminum hydride. It proceeds easily by reacting. In this case, the reaction suitably proceeds by performing the reaction in the presence of a catalyst such as tin chloride. In addition, by performing catalytic reduction using a metal such as nickel, platinum, palladium, and rhodium as a catalyst in a hydrogen gas atmosphere, the dinitro compound represented by the general formula (VI) can be converted to a compound represented by the general formula (II). It is also possible to synthesize the aromatic diamine compound represented. It is desirable to carry out any of the reactions in a solvent, and any solvent may be used as long as it does not participate in the reaction.
Tetrahydrofuran, dimethoxyethane, dioxane,
Benzene, toluene and the like can be exemplified. The reaction temperature is -100 ° C to 150 ° C, preferably -50 ° C to 10 ° C.
It can be carried out in the range of 0 ° C.

In the above process for producing the compounds represented by the general formulas (I) and (II), the alcohol compound represented by the general formula (IV), which is used as a common raw material, is prepared, for example, by the following method: Can be manufactured. That is, among the alcohol compounds represented by the general formula (IV), the compound wherein m is 0 is obtained by reacting 4-fluorothiophenol with a base such as sodium hydride or potassium hydride, and then reacting the compound with the general formula; Y (CH ₂ ) _p OH (in the formula, Y is a halogen atom other than fluorine, and p is an integer of 1 to 6.)
And then introducing an appropriate protecting group into the hydroxyl group and further reacting with an oxidizing agent such as hydrogen peroxide to obtain a compound represented by the following general formula (VII):

[0031]

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Wherein A ¹ is a protecting group for a hydroxyl group, and p is 1 to
6 is an integer. ) Is synthesized. And, this compound and the following general formula (VIII)

[0033]

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(Wherein R ¹ and R ² independently represent a carbon number of 1 to
It may form a ring together with 20 linear or branched alkyl groups or a bonded nitrogen atom. )
With an amine compound represented by the following formula (IX):

[0035]

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(Where A¹Is a protecting group for a hydroxyl group, R¹and
R^TwoIs independently a linear or branched alkyl group having 1 to 20 carbon atoms.
Together with the alkyl group or the attached nitrogen atom
A ring may be formed, and p is an integer of 1 to 6. )
After obtaining a compound of formula ¹Preservation of the hydroxyl group represented by
It can be synthesized by removing a protecting group. (Reaction conditions, etc.
Refers to Reference Example 1 below)

A in formulas (VII) and (IX)
^{As the} hydroxyl-protecting group represented by ¹ , those which are stably present in the above reaction and can be removed without damaging other sites in the deprotection reaction are selected. Hydroxyl protecting groups that meet this requirement include formyl, acetyl, trichloroacetyl, trifluoroacetyl,
Benzoyl group, p-methoxybenzoyl group, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, p-methoxybenzyloxycarbonyl group, p-
Acyl group such as nitrobenzyloxycarbonyl group, lower alkoxy group such as methoxymethyl group, ethoxymethyl group, 2-methoxyethoxymethyl group or lower alkoxyalkoxy group substituted alkyl group, benzyl group, p-methylbenzyl group, m-ethyl Benzyl, p-methoxybenzyl, p-nitrobenzyl, m-chlorobenzyl, o, p-
Dimethoxybenzyl group, benzhydryl group, di- (p-methoxyphenyl) methyl group, lower alkyl group such as trityl group, lower alkoxy group, nitro group, substituted or unsubstituted arylmethyl group having a substituent such as a halogen atom,
Tetrahydropyranyl group, tetrahydrofuranyl group, 1,
Cyclic ether residues such as 4-dioxan-2-yl group, trimethylsilyl group, t-butyldimethylsilyl group, silyl groups such as t-butyldiphenylsilyl group and the like are exemplified, and preferably an acyl group is used. . The hydroxyl-protecting group can be prepared by a known method (for example, “Protective Groups in
Organic Synthesis ", John Wiley & Sons, New York, 1
981, p. 10-85) to the corresponding precursor compound, and from the compound represented by the general formula (IX) to the alcohol compound represented by the general formula (IV). The removal of the protecting group for derivation is performed by a known method depending on the type of the protecting group used here.
(For example, "Protective Groups in Organic Synthesi
s ", John Wiley & Sons, New York, 1981, p.10-85
reference)

On the other hand, among the alcohol compounds represented by the general formula (IV), the compound wherein m is 1 is represented by the following general formula (X)

[0039]

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Wherein A ² is a protecting group for a hydrogen atom or a hydroxyl group, X ² is an amino group or a formyl group, and p is an integer of 1 to 6, and a compound represented by the following general formula (X
I)

[0041]

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(Wherein R ¹ and R ^{2 each} independently have 1 to 1 carbon atoms)
20 may form a ring together with a linear or branched alkyl group or a bonding nitrogen atom;
³ is a hydrogen atom, an amino group, a formyl group or a methyl group. )) And the like. That is, the general formula (I
In the case of synthesizing a compound in which both Y ¹ and Y ^{2 in} V) are nitrogen atoms (a compound in which Y ¹ ＹY ² represents an azo bond), the compound represented by the general formula (X) in which X ² is an amino group Is obtained by diazotizing the compound represented by the formula (I) and then coupling the compound with the compound represented by the formula (XI) wherein X ³ is a hydrogen atom. Further, Y ¹ in the general formula (IV)
Is a group represented by a nitrogen atom and Y ² is a group represented by CH or a compound wherein Y ¹ is a group represented by CH and Y ² is a nitrogen atom (Y ¹ = Y ² is a group represented by an imino bond. In the case of synthesizing a compound represented by the general formula (X) wherein X ² is an amino group and a compound represented by the general formula (XI) wherein X ³ is a formyl group, Alternatively, it can be obtained by coupling a compound represented by the general formula (X) wherein X ² is a formyl group with a compound represented by the general formula (XI) wherein X ³ is an amino group. Further, both Y ¹ and Y ² in the general formula (IV) are C
When synthesizing a compound that is a group represented by H (a compound in which Y ¹ = Y ² represents a carbon-carbon double bond), the compound is represented by the above general formula (X) in which X ² is a formyl group. Compound and X ³
Is a methyl group and a compound represented by the general formula (XI) is coupled by a method such as Heck reaction. The general formula (X) used here
The compound represented by is 4-aminothiophenol or
It can be produced by a method similar to the method for synthesizing the compound represented by the general formula (VII) using 4-formylthiophenol or the like as a starting material. (For example, Reference Example 2 shown later
reference)

An aromatic polyamide can be produced by using the aromatic dicarboxylic acid compound represented by the general formula (I) and the aromatic diamine compound represented by the general formula (II) of the present invention as monomers. is there. That is, an aromatic dicarboxylic acid compound represented by the general formula (I), an aromatic diamine compound represented by the general formula (II), and an aromatic dicarboxylic acid compound represented by the general formula (I) are known. , Or a known aromatic dicarboxylic acid compound and an aromatic diamine compound represented by the general formula (II) are mixed in equimolar amounts, respectively, and a polycondensation reaction can be performed. . Although the polycondensation reaction proceeds suitably presence of a condensing agent, the condensing agent used _{herein, (PhO) 3 P, (} PhO) PCl 2, PhPOCl 2, (C
_{3 H 7) 3 P (O} ) O, POCl 3, SOCl 2 / Et 3 N, Ph 3 P / C 2 Cl 6, SiCl 4,
Me ₂ SiCl _{2 and the} like can be exemplified. This reaction is preferably performed in an organic solvent, dimethylformamide, dimethylacetamide, dimethylsulfoxide,
An aprotic polar solvent such as 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 weight average molecular weight of the aromatic polyamide thus obtained is preferably 5,000 or more from the viewpoints of film forming properties and stability as a nonlinear optical material. The molecular weight is measured by a known method such as gel permeation chromatography, vapor pressure measurement, osmotic pressure, light scattering, and viscosity.

When the aromatic polyamide obtained by using each compound of the present invention as a monomer is used as a polymer nonlinear optical material, for example, the polyamide may be chloroform, dichloromethane, dichloroethane, benzene, toluene, xylene, tetrahydrofuran, dimethoxyethane. , Dioxane, acetonitrile, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-
It is dissolved in an organic solvent such as methylpyrrolidone, and is manufactured on a substrate such as a glass substrate, an ITO vapor-deposited substrate or a silicon wafer by a method such as spin coating or casting so that the film thickness is preferably 0.1 to 10 μm. After the film is dried, the poling treatment is preferably performed at a voltage of preferably 1 kV / cm or more while maintaining the temperature near the glass transition temperature of the polyamide to orient the side chain dye molecules (non-linear molecules). The material is obtained.

[0045]

The polymer nonlinear optical material comprising an aromatic polyamide obtained by using the compound of the present invention as a monomer,
Since the main chain skeleton is made of aromatic polyamide and is soluble in a solvent, it has good moldability and excellent secondary nonlinear optical intensity, and has a high glass transition temperature and a decrease in strength due to orientation relaxation. Small and excellent in stability. In addition, since it is a glassy (amorphous) polymer,
It is a material with 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.

[0046]

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

Reference Example 1

[0048]

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3.20 g (80.0 mmol, 60% in mineral 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
Add 10 ml of dry DMF and add 10 ml of dry D under ice-cooling.
6.78 g of 4-fluorothiophenol dissolved in MF (5
2.9 mmol) was added dropwise, and the mixture was further stirred at room temperature for 1 hour. 5.00 g (52.9 mmol) of 3-chloro-1-propanol
Was added dropwise. After stirring at room temperature for 2 hours, D
The MF was removed. Ethyl acetate was added to the residue, and this solution was washed with water and a saturated aqueous solution of sodium chloride in this order. The organic layer was dried by adding anhydrous sodium sulfate, and the solution was concentrated. Purification by silica gel chromatography using chloroform / methanol (volume ratio: 40: 1) as an eluent gave 3-[(4-fluorophenyl) thio] propan-1-ol represented by the above structural formula (2). Obtained as a colorless liquid in a yield of 9.02 g (92%). Incidentally, the fact that the product has the above structure is shown by ¹ H-NMR, IR and Mas shown below.
It was confirmed from the s spectrum.

¹ H NMR (CDCl ₃ , δ / ppm): 1.54 (s, 1H),
1.85 (dt, 2H, J = 6.4, 7.2 Hz), 2.99 (t, 2H, J = 7.2 H
z), 3.76 (t, 2H, J = 6.4 Hz), 7.0-7.3 (m, 2H), 7.9-
8.2 (m, 2H) .IR (cm ^-1 ): 3360 (-OH), 2935, 2880, 1590, 1490, 14
40, 1395, 1225, 1155,1090, 1050, 1010, 910, 825, 6
30.Mass (m / e): 186 (M ⁺ ), 167, 155, 153, 141 (F-Ph-S
CH ₂ ⁺ ), 128 (F-Ph-SH), 108, 95 (F-Ph ⁺ ), 83, 69, 57,
45, 31.

The compound (1) obtained here was 1.860 g (10.
To 0 mmol) was added 10 ml of acetic anhydride and 0.061 g (0.5 mmol) of 4- (N, N-dimethylamino) pyridine, and the mixture was stirred at room temperature for 1 hour. The reaction solution was poured into 200 ml of a saturated aqueous sodium hydrogen carbonate solution. Furthermore, after neutralization with sodium hydrogen carbonate, extraction was performed using ethyl acetate. After dehydrating the organic layer with anhydrous sodium sulfate, the solvent was removed under reduced pressure. Purification by silica gel chromatography using chloroform / methanol (volume ratio 100: 1) as an eluent gave 2.170 g of 3-[(4-fluorophenyl) thio] propyl acetate represented by the above structural formula (2) ( 95%) as a colorless liquid. Incidentally, the fact that the product has the above structure is shown by ¹ H-
Confirmed from NMR, IR and Mass spectra.

¹ H NMR (CDCl ₃ , δ / ppm): 1.8-2.1 (m, 2
H), 2.03 (s, 3H), 2.92 (t, 2H, J = 7.2 Hz), 4.16
(t, 2H, J = 6.3 Hz), 6.9-7.2 (m, 2H), 7.3-7.6 (m,
2H) .IR (cm ^-1 ): 3065, 2960, 1740 (-C = O), 1590, 1490, 1
440, 1385, 1365, 1240, 1155, 1090, 1040, 950, 830,
630, 605, 515. Mass (m / e): 228 (M ⁺ ), 168 (F-Ph-S-CH ₂ -CH = CH ₂ ), 1
53, 141 (F-Ph-S ⁺ = CH ₂ ), 128 (F-Ph-SH), 127 (F-Ph-
_{^{S +), 101 (CH 3}} COO (CH 2) 3 +), 83, 73 (CH 3 COO (CH 2) 2 +), 4
3 (CH ₃ CO ⁺ ).

The compound (2) thus obtained, 2.170 g (9.5
To 1 mmol) was added 25 ml of acetic anhydride and 3.40 g (30.0 mmol) of a 30% aqueous hydrogen peroxide solution, and the mixture was refluxed for 2 hours. The reaction solution was poured into 200 ml of a saturated aqueous solution of sodium hydrogen carbonate, neutralized with sodium hydrogen carbonate, and extracted with ethyl acetate. After dehydrating the organic layer with anhydrous sodium sulfate, the solvent was removed under reduced pressure. Purification by silica gel chromatography using chloroform / methanol (volume ratio 50: 1) as an eluent gave 3-[(4-fluorophenyl) acetic acid represented by the above structural formula (3).
Sulfonyl] propyl was obtained as a colorless liquid in a yield of 2.034 g (82%). The structure of the product was confirmed by ¹ H-NMR, IR and Mass spectra shown below.

¹ H NMR (CDCl ₃ , δ / ppm): 1.9-2.3 (m, 3
H), 2.03 (s, 3H), 3.1-3.4 (m, 2H), 4.13 (t, 2H, J =
6.4 Hz), 7.2-7.5 (m, 2H), 7.9-8.2 (m, 2H) .IR (cm ^-1 ): 3105, 3075, 2965, 1740 (-C = O), 1590, 1
495, 1445, 1405, 1385,1370, 1320, 1290, 1240 (-SO ₂
-), 1175, 1145, 1090, 1040, 950, 900, 845,820, 78
0, 730, 695, 675, 635, 605, 570, 525. Mass (m / e): 217 (M ⁺ -CH ₃ CO), 200, 187 (F-Ph-SO ₂ CH
₂ CH ₂ ⁺ ), 161, 159 (F-Ph-SO ₂ ⁺ ) 143, 101, 95 (F-Ph ⁺ ),
75, 43 (CH ₃ CO ⁺ ); [CI]: 261 (M ⁺ +1).

5.206 g of the compound (3) obtained here (20.
0 mmol), 2.764 g (20.0 mmol) of anhydrous potassium carbonate and 4.078 g (22.0 mmol) of dihexylamine were added with 5 ml of dry dimethyl sulfoxide, and the mixture was stirred at 150 ° C for 3 hours. Pour the reaction mixture into 300 ml of water,
Extracted with ethyl acetate. Further, after the organic layer is washed with a saturated aqueous sodium chloride solution, anhydrous sodium sulfate is added to the organic layer and dried. The solution is concentrated, and the acetic acid 3- {4-[(N, N-Dihexyl) amino] phenylsulfonyl} propyl was obtained. further,
1.60 g of sodium hydroxide (40.
0 mmol) and 20 ml of water, 20 ml of methanol, 20 m
l of THF was added and refluxed for 1 hour. After evaporating the solvent under reduced pressure, chloroform and water were added to the residue, and the organic layer was separated. Add anhydrous sodium sulfate to the organic layer and dry,
After concentrating this solution, it was purified and isolated by silica gel column chromatography using hexane / ethyl acetate (volume ratio: 1: 1) as an eluent, and 3- {4- [represented by the above structural formula (5) was obtained. 5.200 g (61%) of (N, N-dihexyl) amino] phenylsulfonyl} propan-1-ol
In the yield. The structure of the product was confirmed by ¹ H-NMR, IR and Mass spectra shown below.

Compound (4):¹H NMR (CDCl_Three, δ / ppm):
0.90 (t, 6H, J = 5.4 Hz), 1.1-1.8 (m, 16H), 1.9-2.3
(m, 5H), 3.0-3.6 (m, 6H), 4.11 (t, 2H, J = 6.2 Hz),
 6.62 (t, 2H, J = 9.0 Hz), 7.64 (t, 2H, J = 9.0 Hz) .IR (cm^-1): 2960, 2930, 2860, 1740 (-C = O), 1595, 15
55, 1515, 1465, 1405,1370, 1310, 1240 (-SO_Two-), 117
0, 1135, 1040, 995, 950, 865, 815, 795, 725, 700,
665, 635, 605, 570, 535. Mass (m / e): 213, 184, 170, 156, 142, 128, 114, 1
00, 83, 72, 57, 43 (CH _ThreeCO⁺), 28; [CI]: 426 (M⁺+1).

Compound (5): ¹ H NMR (CDCl ₃ , δ / ppm):
0.90 (t, 6H, J = 5.4 Hz), 1.1-2.1 (m, 17H), 2.1-2.3
(m, 2H), 3.0-3.6 (m, 6H), 3.6-3.9 (m, 2H), 6.62
(t, 2H, J = 9.0 Hz), 7.64 (t, 2H, J = 9.0 Hz) .IR (cm ^-1 ): 3500 (-OH), 2960, 2930, 2860, 1595, 15
55, 1515, 1465, 1405,1370, 1300, 1255, 1210, 1135,
1095, 1065, 1000, 905, 815, 800, 725, 700,665, 56
5, 535. Mass (m / e): 312 (M ⁺ -C ₅ H ₁₁ ), 224, 212, 198, 185,
170, 156, 142, 128, 114, 83, 72, 44, 43, 30; [CI]:
384 (M ⁺ +1).

Embodiment 1

[0059]

Embedded image

1.534 g of the compound (5) obtained in Reference Example 1
 (4.00 mmol), dimethyl 5-hydroxyisophthalate 1.
261 g (6.00 mmol) and triphenylphosphine 1.2
Mix 61 g (4.80 mmol), and add argon atmosphere in the reaction system.
And To this mixture was added 30 ml of dry THF.
Solution, and then at room temperature diethyl azodicarbo
Add 1.02 g (6.00 mmol) of xylate and stir for 1 hour.
went. After evaporating the solvent under reduced pressure, hexane / acetic acid
Silica gel with chill (2: 1 by volume) as the eluent
Purified by column chromatography and further purified by methanol
Purified by recrystallization from toluene. As a result,
5- {3- [4- (N, N-dihexylamino) represented by the structural formula (6)
)) Phenylsulfonyl] propoxy} isophthalic acid
Chill was obtained in a yield of 1.290 g (56%). The product is
The above structure is shown below ¹H-NMR, I
It was confirmed from R, Mass spectrum and elemental analysis.

¹ H-NMR, δ (CDCl ₃ , ppm): 0.90 (t, 6H, J
= 5.4 Hz), 1.2-2.1 (m, 16H), 2.1-2.5 (m, 2H), 3.0-
3.5 (m, 6H), 3.93 (s, 6H), 4.11 (t, 2H, J = 5.9 H
z), 6.62 (t, 2H, J = 9.0 Hz), 7.66 (t, 2H, J = 9.0 Hz),
7.68 (d, 2H, J = 1.3 Hz), 8.26 (t, 1H, J = 1.3 Hz) .IR (cm ^-1 ): 2955, 2930, 2855, 1725 (-C = O), 1595, 15
55, 1520, 1480, 1455,1435, 1410, 1345, 1315, 1300,
1270, 1240, 1175, 1140, 1115, 1090, 1060,1045, 10
10, 945, 925, 905, 885, 870, 825, 760, 720, 670, 6
40, 560, 535. Mass (m / e): 575 (M ⁺ ), 544 (M ⁺ -OCH ₃ ), 504 (M ⁺ -C
_{5 H 11), 434, 388} , 354, 312 (HO- (CH 2) 3 -SO 2 -Ph-N- (C 6 H
^{_{13) CH 2 +), 284}} , 210 (HO-Ph- (COOCH 3) 2), 189, 168,11
9, 105, 55, 43. Elemental analysis (C ₃₁ H ₄₅ NSO _7, molecular weight 575.8) Calculated C: 64.67% H: 7.88% N: 2.43% S: 5.57
% Actual value C: 64.50% H: 7.91% N: 2.37% S: 5.56
%

Further, the compound (6) 1.10 obtained here was obtained.
0 g (1.91 mmol) per 20 ml of methanol / THF
0.382 g (9.55 mmol) of sodium hydroxide dissolved in water / water (1: 1: 1 by volume) was added, and the mixture was refluxed for 1 hour. 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 / hexane to give 5- {3- [4- (N, N-dihexylamino) phenylsulfonyl] propoxy} isophthalic acid represented by the above structural formula (7). Obtained quantitatively (1.05 g). The structure of the product was confirmed by ¹ H-NMR, IR and Mass spectra shown below.

¹ H-NMR, δ (CDCl ₃ , ppm): 0.90 (m, 6H),
1.2-2.1 (m, 16H), 2.1-2.5 (m, 2H), 3.0-3.5 (m, 6H),
4.0-4.2 (m, 2H), 6.63 (t, 2H, J = 9.0 Hz), 7.65 (t,
2H, J = 9.0 Hz), 7.57 (m, 2H), 8.23 (m, 1H) .IR (cm ^-1 ): 3400 (-OH), 3090, 2955, 2930, 2860, 170
0 (-C = O), 1595, 1555,1515, 1465, 1405, 1370, 1305,
1275, 1210, 1170, 1130, 1090, 1045, 995, 980, 91
0, 885, 815, 760, 725, 690, 665, 560, 530.Mass (m / e): 547 (M ⁺ ), 476, 432, 406, 374, 210, 18
9, 168, 152, 112, 43, 28.

Embodiment 2

[0065]

Embedded image

Under an argon atmosphere, 0.902 g (3.91 mmol) of 3,5-dinitrobenzoic acid chloride was dissolved in 10 ml of dry tetrahydrofuran (THF). 1.25 g (3.26 mmol) of the compound (5) dissolved in 20 ml of dry THF was added to this solution.
l) and 0.408 g (4.00 mmol) of dry triethylamine were added, and the mixture was stirred at room temperature for 1 hour. Then, the reaction mixture was poured into 50 ml of saturated aqueous sodium hydrogen carbonate solution. The mixture was extracted with chloroform, the organic layer was dehydrated with sodium sulfate, and the solution was concentrated under reduced pressure. Purification by silica gel column chromatography using chloroform / ethyl acetate (volume ratio: 4: 1) as an eluent, followed by purification by recrystallization from ethanol, gave the 3,5-formula represented by the above structural formula (8). Dinitrobenzoic acid
3- [4- (N, N-dihexylamino) phenylsulfonyl] propyl was quantitatively obtained (1.883 g). Incidentally, the fact that the product has the above structure is shown below by ¹ H-NMR, IR,
It was confirmed from Mass spectrum and elemental analysis.

[0067]¹H-NMR, δ (CDCl_Three, ppm): 0.90 (t, 6H, J
= 5.4 Hz), 1.1-2.1 (m, 16H), 2.1-2.5 (m, 2H), 3.0-
3.5 (m, 6H), 4.55 (t, 2H, J = 6.4 Hz), 6.63 (t, 2
H, J = 9.0Hz), 7.65 (t, 2H, J = 9.0 Hz), 9.10 (d, 2H,
J = 2.0 Hz), 9.22 (t, 1H, J = 2.0Hz) .IR (cm^-1): 3110, 2950, 2930, 2855, 1735 (-C = O), 16
30, 1595, 1545 (-NO_Two), 1515, 1465, 1410, 1345 (-NO
_Two), 1285, 1235, 1180, 1155, 1135, 1090, 1075, 105
0, 995, 930, 915, 860, 820, 790, 775, 720, 640, 57
0, 530. Mass (m / e): 577 (M⁺), 506 (M⁺-C_FiveH₁₁), 476, 436, 40
6, 383 (HO- (CH_Two)_Three-SO_Two-Ph-N- (C₆H₁₃)_Two), 354 (HO- (C
H_Two)_Three-SO_Two-Ph-N- (C₆H₁₃) C_FourH₈ ⁺), 312 (HO- (CH_Two)_Three-SO _Two-Ph
-N- (C₆H₁₃) CH_Two ⁺), 195 ((O_TwoN)_Two-Ph-CO⁺), 179, 165, 14
9, 135, 119, 105, 91, 75, 55, 43. Elemental analysis (C₂₈H₃₉N_ThreeSO₈, Molecular weight 577.7) Calculated C: 58.22% H: 6.80% N: 7.27% S: 5.55
% Actual value C: 58.17% H: 6.89% N: 7.16% S: 5.61
%

The compound (8) obtained here was 1.733 g (3.0
0 mmol) in 20 ml of THF, and SnCl ₂ .2H ₂ O 6.7 dissolved in 20 ml of ethanol under an argon atmosphere.
The solution was added to 71 g (30.0 mmol) and kept at 60 ° C to form a solution. To this solution, 0.226 g (6.00 mmol) of sodium borohydride dissolved in 20 ml of ethanol was added, and the mixture was stirred at 60 ° C for 3 hours. After evaporating the solvent under reduced pressure, 1000 ml of ice-cooled 0.5 N aqueous sodium hydroxide solution and ethyl acetate 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. Purification by silica gel column chromatography using ethyl acetate / hexane (volume ratio: 3: 1) as an eluent, followed by purification by recrystallization from ethanol, gave 3,5-diamino represented by the above structural formula (9). Benzoic acid 3- [4-
(N, N-dihexylamino) phenylsulfonyl] propyl was obtained as pale yellow crystals in a yield of 1.180 g (76%). Incidentally, the fact that the product has the above structure is shown by ¹ H-
It was confirmed from NMR, IR, Mass spectrum and elemental analysis.

[0069]¹H-NMR, δ (CDCl_Three, ppm): 0.90 (t, 6H, J
= 5.4 Hz), 1.1-2.1 (m, 16H), 2.1-2.5 (m, 2H), 3.0-
3.5 (m, 6H), 3.5-3.8 (bs, 4H), 4.30 (t, 2H, J = 6.2
 Hz), 6.18 (t, 1H, J = 2.0 Hz), 6.61 (t, 2H, J = 9.0 H
z), 6.72 (d, 2H, J = 2.0 Hz), 7.65 (t, 2H, J = 9.0 H
z) .IR (cm^-1): 3425 (-NH_Two), 3360 (-NH_Two), 3340 (-NH_Two),
3220, 2955, 2930, 2860, 1705 (-C = O), 1645, 1595, 1
560, 1510, 1470, 1440, 1400, 1390, 1370, 1350, 131
0, 1280, 1260, 1235, 1190, 1130, 1100, 1090, 1080,
 1065, 1020, 995, 955, 905, 880, 855, 820, 790, 76
5, 740, 725, 675, 590, 565, 530. Mass (m / e): 517 (M⁺), 446 (M⁺-C_FiveH₁₁), 376, 312 (H
O- (CH_Two)_Three-SO_Two-Ph-N- (C₆H ₁₃) CH_Two ⁺), 188, 152 ((H_TwoN)_Two-P
h-COOH), 135, 107, 79, 43. Elemental analysis (C₂₈H₄₃N_ThreeSO_Four, Molecular weight 517.7) Calculated C: 64.96% H: 8.37% N: 8.12% S: 6.19
% Actual value C: 64.75% H: 8.42% N: 8.03% S: 6.19
%

Reference Example 2

[0071]

Embedded image

1.92 g of sodium hydride (48.0 mmol, 60
% in mineral oil) in a 200 ml three-necked flask,
After the system was set to an argon atmosphere, the system was washed with hexane. 20 ml of dry DMF was added, and 5.01 g of 4-aminothiophenol dissolved in 5 ml of dry DMF under ice cooling.
(40.0 mmol) was added dropwise, and the mixture was further stirred at room temperature for 1 hour. 3-chloro-1- dissolved in 5 ml of dry DMF was added thereto.
3.78 g (40.0 mmol) of propanol were added dropwise. After stirring at room temperature for 2 hours, 5 ml of water was added, and DMF was added under reduced pressure.
Was removed. Ethyl acetate was added to the residue to form a solution, which was filtered using celite, and then concentrated. Under reduced pressure,
After drying and adding 15 ml of acetic anhydride and 0.122 g (1.00 mmol) of 4- (N, N-dimethylamino) pyridine to the residue and stirring at room temperature, the reaction solution was poured into 300 ml of a saturated aqueous solution of sodium hydrogen carbonate. The solution was extracted with ethyl acetate, the organic layer was dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography using hexane / ethyl acetate (volume ratio 2: 1) as an eluent to give 4- (3-acetoxypropylthio) acetanilide represented by the above structural formula (10) in pale yellow. The crystals were obtained in a yield of 7.55 g (70.6%). The structure of the product was confirmed by ¹ H-NMR, IR and Mass spectra shown below.

¹ H NMR (400 MHz, CDCl ₃ , δ / ppm): 1.7-2.0
(m, 2H), 2.08 (s, 3H), 2.20 (s, 3H), 2.98 (t, J =
6.2 Hz, 2H), 4.22 (t, J = 6.2 Hz, 2H), 7.2-7.7 (m, 5
H) .IR (cm ^-1 ): 3310, 3180, 3105, 3045, 2960, 1735 (est
eric -C = O), 1670 (-C = Oof amide), 1595, 1530, 1495,
1435, 1395, 1370, 1315, 1290, 1245, 1180,1095, 10
35, 960, 825, 710, 635, 605, 585, 515. Mass (m / e): 267 (M +), 225, 207, 180, 165, 138, 124,
101, 94, 73, 43.

The compound (10) obtained here, 9.06 g (3
3.9 mmol), 80 ml of acetic acid and 11.53 g of 30% hydrogen peroxide solution
(101.7 mmol) was stirred under reflux for 1 hour, and the reaction solution was poured into 300 ml of a saturated aqueous sodium hydrogen carbonate solution. The solution was extracted with chloroform, the organic layer was dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography using chloroform / methanol (volume ratio 80: 1 → 50: 1) as an eluent to give 4- (3-acetoxypropylsulfonyl) acetanilide represented by the above structural formula (11). Was obtained as a white solid in a yield of 6.94 g (68.4%). The structure of the product was confirmed by ¹ H-NMR, IR and Mass spectra shown below.

¹ H NMR (400 MHz, CDCl ₃ , δ / ppm): 2.0-2.
1 (m, 2H), 2.03 (s, 3H), 2.24 (s, 3H), 3.1-3.2 (m,
2H), 4.12 (t, J = 6.2 Hz, 2H), 7.48 (s, br, 1H), 7.7
3 (d, J = 8.7 Hz, 2H), 7.86 (dt, J = 2.0, 8.7 Hz, 2H) .IR (cm ^-1 ): 3335, 3290, 3195, 3115, 3055, 2965, 290
5, 1725 (esteric -C = O), 1695 (-C = O of amide), 165
5, 1590, 1530, 1500, 1400, 1370, 1320, 1305,1260,
1170, 1140, 1090, 1065, 1040, 1010, 955, 905, 875,
855, 780, 750,710, 700, 635, 590, 575, 530, 515,
450.Mass (m / e): 299 (M ⁺ ), 257 (M ⁺ -(CH ₃ CO)), 240, 226,
214, 198, 175, 156, 140, 134, 101, 94, 65, 43.

The compound (11) obtained here was 4.52 g (1
5.1 mmol) and 2.14 g (53.5 mmol) of sodium hydroxide
Was dissolved in 30 ml of methanol / water (1: 1 by volume), and the mixture was heated under reflux for 3 hours. After allowing to cool, the mixture was extracted with chloroform, the organic layer was dehydrated with anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was recrystallized from ethyl acetate to give 2.32 g (71.5%) of 4- (3-hydroxypropylsulfonyl) aniline represented by the above structural formula (12).
In the form of white crystals. Incidentally, the fact that the product has the above-mentioned structure was confirmed by ¹ H-NMR, IR and M shown below.
It was confirmed from the ass spectrum.

¹ H NMR (400 MHz, CDCl ₃ , δ / ppm): 1.67
(t, J = 5.5 Hz, 1H), 1.9-2.0 (m, 2H), 3.1-3.2 (m, 2
H), 3.74 (q, J = 5.8 Hz, 2H), 4.20 (s, br, 2H), 6.72
(dt, J = 2.0, 8.7 Hz, 2H), 7.67 (dt, J = 2.0, 8.7 Hz,
2H) .IR (cm ^-1 ): 3385, 3220, 3055, 2965, 2945, 2920, 287
5, 1640, 1600, 1575, 1500, 1485, 1450, 1435, 1415,
1385, 1340, 1295, 1260, 1230, 1180, 1155, 1135, 1
085, 1045, 1010, 850, 790, 745, 720, 650, 560, 53
5, 500, 475. Mass (m / e): 215 (M ⁺ ), 171, 156, 140, 122, 108, 93,
80, 65.

2.132 g of the compound (12) obtained here (9.
90 mmol), 10 ml of concentrated hydrochloric acid and 20 ml of water were added, and the mixture was cooled with ice. Sodium nitrite 0.82 dissolved in 10 ml of water in this mixture
0 g (11.9 mmol) was added and stirred for 30 minutes. N, N-dimethylaniline dissolved in 10 ml of methanol in this reaction solution
1.32 g (10.9 mmol) were added. Further, the mixture was neutralized by adding an aqueous solution of sodium hydroxide under ice-cooling, and stirred for 1 hour. Then, 400 ml of water was added, and the resulting precipitate was collected by filtration. The precipitate is dissolved in a mixed solvent of chloroform and ethyl acetate (4: 1 by volume), purified by silica gel column chromatography using a mixed solvent of chloroform and ethyl acetate (4: 1 by volume) as an eluent, and then re-dissolved from methanol. When crystallized, 3-
{4- [4- (N, N-dimethylamino) phenylazo] phenyl} sulfonyl-1-propanol was obtained in a yield of 2.52 g (73.2%). Incidentally, the fact that the product has the above-mentioned structure means that the following ¹ H-NMR spectrum, IR spectrum, Mass
It was confirmed from the spectrum.

¹ H NMR (400 MHz, CDCl ₃ , δ / ppm): 1.60
(t, J = 5.5 Hz, 1H), 2.0-2.1 (m, 2H), 3.13 (s, 6H),
3.25-3.35 (m, 2H), 3.76 (q, J = 5.8 Hz, 2H), 6.77 (d
t, J = 3.2, 9.2 Hz, 2H), 7.91 (dt, J = 3.2, 9.2 Hz, 2
H), 7.67 (dt, J = 2.0, 8.7 Hz, 2H), 7.90-8.05 (m, 4
H) .IR (cm ^-1 ): 3510 (-OH), 2930, 2895, 2820, 1605, 152
0, 1445, 1420, 1390, 1365, 1310, 1290, 1255, 1230,
1190, 1160, 1130, 1100, 1080, 1070, 1050, 1025, 9
95, 945, 900, 845, 820, 785, 750, 725, 705, 675, 6
40, 605, 576, 555, 540, 495, 480. Mass (m / e): 347 (M ⁺ ), 224, 148, 136, 120, 105, 91,
77, 60, 42, 28.

Embodiment 3

[0081]

Embedded image

Under an argon gas atmosphere, 2.20 g (6.34 mmol) of the compound (13) obtained in Reference Example 2, 2.00 g (9.51 mmol) of dimethyl 5-hydroxyisophthalate and 1.996 g (7.61 mmol) of triphenylphosphine were dried. After adding 70 ml of tetrahydrofuran (THF) to make a homogeneous solution, the mixture was ice-cooled. Under ice cooling, 1.62 g (9.51 mmol) of diethyl azodicarboxylate dissolved in dry THF was added dropwise.
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 recrystallization from acetone / methanol. As a result, the above structural formula (1)
3.22 g (94.2%) of dimethyl 5- (3- {4- [4- (N, N-dimethylamino) phenylazo] phenyl} sulfonyl-1-propyloxy) isophthalate of the structural formula represented by 4) Obtained in yield as red-orange crystals. The structure of the product was confirmed by ¹ H-NMR, IR, Mass spectrum and elemental analysis shown below.

¹ H NMR (400 MHz, CDCl ₃ , δ / ppm): 2.25-2.
35 (m, 2H), 3.13 (s, 6H), 3.3-3.4 (m, 2H), 3.92 (s,
6H), 4.13 (t, J = 6.2 Hz, 2H), 6.77 (dt, J = 3.2, 9.2
Hz, 2H), 7.67 (d, J = 1.4 Hz, 2H), 7.91 (dt, J = 3.2,
9.2 Hz, 2H), 7.95 (dt, J = 2.0, 8.7 Hz, 2H), 8.02 (d
t, J = 2.0, 8.7 Hz, 2H), 8.27 (t, J = 1.4 Hz, 1H) .IR (cm ^-1 ): 2995, 2950, 2925, 2820, 1720 (-C = O), 16
05, 1560, 1520, 1460,1440, 1420, 1390, 1365, 1340,
1315, 1250, 1160, 1150, 1130, 1100, 1075,1045, 10
00, 945, 910, 870, 845, 825, 795, 775, 760, 720, 6
90, 670, 635,605, 555, 540, 520, 500. Mass (m / e): 539 (M +), 480 (M + - (COOCH 3)), 407, 376,
223, 210, 198, 179, 165, 148, 136, 120, 105, 92,
77, 65, 41.

Further, the compound (14) obtained here was obtained from 2.
70 g (5.00 mmol) and sodium hydroxide 1.20 g (30.0
mmol) in 100 ml of methanol / THF / water (volume ratio)
1: 2: 2), and heated under reflux for 3 hours. After hydrochloric acid was added to the reaction mixture to neutralize it, the precipitated reddish brown solid was collected by filtration and washed with water. The red-brown solid was purified by recrystallization from THF / water. As a result, the 5- (3- {4- [4- (N, N-
Dimethylamino) phenylazo] phenyl} sulfonyl-1-
Propyloxy) isophthalic acid was obtained as red-orange crystals in a yield of 2.40 g (93.9%). Incidentally, the fact that the product has the above-mentioned structure was confirmed by ¹ H-NMR, IR and Mas shown below.
Confirmed from s-spectrum and elemental analysis.

¹ H NMR (400 MHz, (CD ₃ ) ₂ SO, δ / ppm): 2.0
-2.1 (m, 2H), 3.10 (s, 6H), 3.5-3.6 (m, 2H), 4.15
(t, J = 6.2 Hz, 2H), 6.87 (d, J = 9.2 Hz, 2H), 7.61
(d, J = 1.4 Hz, 2H), 7.85 (d, J = 9.2 Hz, 2H), 7.94
(d, J = 9.2 Hz, 2H), 8.0-8.1 (m, 3H), 13.25-13.35 (b
r, 2H) .IR (cm ^-1 ): 3495 (-OH), 2955, 2925, 2860, 2665, 259
5, 2540, 1715, 1695, 1600, 1590, 1550, 1525, 1460,
1440, 1420, 1370, 1305, 1280, 1260, 1250, 1220, 1
165, 1155, 1130, 1080, 1060, 1040, 980, 945, 915,
890, 840, 825, 775, 760, 735, 730, 690, 665, 640,
605, 590, 550, 520, 500, 450, 435.Mass (m / e): 511 (M ⁺ ), 393, 379, 347, 294, 280, 26
6, 254, 240, 224, 198,182, 156, 136, 122, 107, 93,
80, 65, 52, 39.

Reference Example 3

[0087]

Embedded image

5.33 g of N-methylethanolamine (70.9 mm
ol), 10.00 g (70.9 mmol) of 4-fluoronitrobenzene
To a mixture of 12.75 g (92.2 mmol) of anhydrous potassium carbonate and 10 ml of dry dimethyl sulfoxide (DMSO).
Stirred at C for 12 hours. The reaction mixture was poured into 300 ml of water, and the resulting precipitate was collected by filtration and purified by recrystallization from methanol. As a result, 10.9 g (yield: 78%) of 2- (4-nitro-N-methylanilino) ethanol represented by the above formula (16) was obtained as yellow 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): 1.82 (t, J = 5.2
Hz, 1H), 3.14 (s, 3H), 3.62 (t, J = 5.0Hz, 2H), 3.
86 (t, J = 5.2Hz, 2H), 6.66 (d, J = 9.5Hz, 2H), 8.07
(d, J = 9.5Hz, 2H). IR (cm ^-1 ): 3445, 2950, 2920, 1595, 1520 (-NO ₂ ), 1
480, 1385, 1300 (-NO ₂ ), 1235, 1205, 1120, 1065, 10
00, 975, 955, 905, 835, 795, 750, 700, 635,550, 49
5. Elemental analysis (C ₉ H ₁₂ N ₂ O ₃ , molecular weight 196.2): Calculated C: 55.09% H: 6.16% N: 14.28% Found C: 55.23% H: 6.25% N: 14.24%

The obtained compound (16) 1.96 g (1
0.0 mmol), 2.52 g of dimethyl 5-hydroxyisophthalate
(12.0 mmol) and 3.16 g of triphenylphosphine (1
2.0 mmol) in an atmosphere of argon gas under dry TH
After adding 30 ml of F to make a uniform solution, the mixture was ice-cooled. Under ice-cooling, 2.04 g (12.0 mmol) of diethyl azodicarboxylate (DEAD) dissolved in dry THF was added dropwise. 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 recrystallization from methanol. As a result, 3.54 g (yield: 91%) of dimethyl 5- [2- (4-nitro-N-methylanilino) ethoxy] isophthalate of the structural formula represented by the above (17) was obtained as yellow crystals. The structure of the product was confirmed by ¹ H-NMR, IR, Mass spectrum and elemental analysis shown below.

¹ H NMR, δ (CDCl ₃ , ppm): 3.20 (s, 3H),
3.8-4.1 (m, 2H), 3.93 (s, 6H), 4.27 (t, J = 5.1Hz,
2H), 6.70 (d, J = 9.5Hz, 2H), 7.70 (d, J = 1.1Hz, 2H),
8.14 (d, J = 9.5Hz, 2H), 8.28 (s, 1H) .IR (cm ^-1 ): 2950, 2920, 2850, 1720 (-C = O), 1600, 15
40, 1520 (-NO ₂ ), 1480,1460, 1440, 1340 (-NO ₂ ), 131
0, 1250, 1230, 1120, 1070, 1010, 940, 880,820, 76
0, 720, 540.Mass (m / e): 388 (M ⁺ ), 277, 201, 179, 119 (Ph-N (C
H ₃ ) CH ₂ ⁺ ), 102, 91, 77 (Ph ⁺ ), 62, 51, 28, 18.Elemental analysis (C ₁₉ H ₂₀ N ₂ O ₇ , molecular weight 388.4): Calculated C: 58.76% H: 5.19% N: 7.21% Found C: 58.83% H: 5.01% N: 7.17%

Further, 1.18 g of the obtained compound (17)
(3.04 mmol) and 0.608 g of sodium hydroxide (15.2 m
mol) was dissolved in a mixed solvent of 10 ml of methanol and 50 ml of THF, and the mixture was heated under reflux for 3 hours. After cooling to room temperature and neutralizing by adding hydrochloric acid to the reaction mixture, the precipitated yellow solid was collected by filtration and washed with water. The obtained yellow solid was purified by recrystallization from methanol. As a result, 5- [2- (4-nitro) of the structural formula represented by the above (18)
0.918 g (yield: 84%) of -N-methylanilino) ethoxy] isophthalic acid was obtained as yellow crystals. The structure of the product was confirmed by ¹ H-NMR, IR and Mass spectra shown below.

¹ H NMR, δ (CDCl ₃ + DMSO-d ₆ , ppm): 3.20
(s, 3H), 3.8-4.1 (m, 2H), 4.23 (t, J = 5.5Hz, 2H), 6.
73 (d, J = 9.5Hz, 2H), 7.70 (d, J = 1.1Hz, 2H), 8.10
(d, J = 9.5Hz, 2H), 8.28 (s, 1H) .IR (cm ^-1 ): 3420 (-OH), 3090, 2930, 1700 (-C = O), 16
00, 1580, 1450, 1420,1380, 1340 (-NO ₂ ), 1310, 121
0, 1140, 1100, 1060, 980, 910, 860, 820, 760, 730,
540.Mass (m / e): 360 (M ⁺ ), 330, 371, 239, 182, 165, 13
5, 119, 106, 91, 81, 77 (Ph ⁺ ), 55, 39, 29, 18.

Example of use

[0095]

Embedded image

3,5-diaminobenzoic acid obtained in Example 2
3- [4- (N, N-dihexylamino) phenylsulfonyl] propyl (9) and 5- [2- (4-nitro-N-
[Methylanilino) ethoxy] isophthalic acid (18) was weighed so as to have an equimolar amount (2 mmol). 2 ml of thionyl chloride was added to the weighed compound (18), and the mixture was heated under reflux for 3 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure, and 2 ml of dry 1-methylpyrrolidin-2-one (N
MP). Separately, the weighed compound (9) was dissolved in 2 ml of dry NMP under an argon gas atmosphere. While maintaining the solution at -78 ° C, the solution of the isophthalic acid derivative prepared above was added, and then a condensation polymerization reaction was performed at 40 ° C for 5 minutes. Next, the reaction solution was poured into 400 ml of methanol to precipitate the polymer. Finally, the polymer obtained is
After dissolving in THF, the solution was filtered and poured into 400 ml of methanol to precipitate the polymer. Finally, the obtained polymer was separated by filtration and dried. As a result, a polyamide represented by the above structure (PA-1) was obtained at a yield of 55%. The chemical structure is shown by ¹ H-NMR shown below.
And from the IR spectrum.

¹ H NMR, δ (CDCl ₃ + DMSO-d ₆ , ppm): 0.8
-0.9 (m, 6H), 1.2-1.4 (m, 16H), 1.5-1.6 (m, 4H),
2.1-2.3 (m, 2H), 3.1-3.3 (m, 5H), 3.8-4.1 (m, 2H),
4.2-4.5 (m, 4H), 6.5-6.8 (m, 4H), 7.5-8.4 (m, 9
H), 8.7-8.8 (m, 1H), 10.0-10.4 (bs, 2H) .IR (cm ^-1 ): 3085, 2930, 2855, 1720 (-C = O), 1680, 15
95, 1550, 1515, 1450, 1310, 1230, 1180, 1130, 1110,
1090, 1060, 995, 885, 820, 795, 765, 750,695, 53
Five.

The weight average molecular weight of polyamide (PA-1) was determined by a light scattering method using polystyrene as a reference substance, the glass transition temperature was measured by a differential scanning calorimeter, and the softening point was determined by thermal stress strain measurement. . The results are shown below. As a result, it was found that PA-1 was a polymer having a high glass transition temperature and a softening point and having excellent thermal stability.

Weight average molecular weight: 48000 Glass transition temperature: 118 ° C. Softening point: 131 ° C.

Polyamide (PA-1) was dissolved in THF to give 1
A 0% by weight solution was prepared and spin-coated on a quartz glass substrate at a rotation speed of 2000 rotations per minute to obtain a polyamide thin film. Next, by using this substrate, an ultraviolet-visible absorption spectrum was measured to determine a maximum absorption wavelength and an absorption edge wavelength of these polyamides. The results are shown below.

Maximum absorption wavelength: 394 nm Absorption edge wavelength: 490 nm

Further, a polyamide (PA-1) was dissolved in THF to prepare a 10% by weight solution, and this was spin-coated on a glass substrate at a rotation speed of 2,000 revolutions per minute to obtain a polyamide thin film.

Next, the substrate was placed on an aluminum hot plate and heated to 130 ° 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 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., J. Appl. Phys. Vol. 41, p. 1667 (1970)), the second harmonic (SH wave) generated from the polyamide thin film subjected to the electric field orientation treatment was measured. The incident fundamental wave is
Using a polarized Nd: YAG laser (1064 nm), 53
A 2 nm SH wave was detected. In addition, a 1 mm-thick y-cut quartz crystal is similarly generated by the maker fringe method.
SH wave was detected. A typical maker fringe pattern is shown in FIG. From these measurements, the y- d ₁₁ value of cut quartz crystals (0.46 pm / V) to a reference, to calculate the second-order nonlinear optical constant d ₃₃ value of each of the polyamide by curve fitting using the least square method Where 6.0 pm
The value of / V is shown.

[Brief description of the drawings]

FIG. 1 is a graph showing a maker fringe pattern of a thin film produced from polyamide (PA-1).

Claims (2)

[Claims] 1. A compound represented by the following general formula (I) (Wherein, R is a hydrogen atom or a lower alkyl group, Y ¹ and Y ² are each independently a nitrogen atom or a group represented by CH, and R ¹ and R ² are each independently a C 1-20 linear or branched group. May form a ring together with the alkyl group or a nitrogen atom bonded thereto, wherein p is an integer of 1 to 6, and m is an integer of 0 or 1.) Dicarboxylic acid compounds. 2. The following general formula (II): (Wherein Y ¹ and Y ² are each independently a group represented by a nitrogen atom or CH, R ¹ and R ² are each independently a linear or branched alkyl group having 1 to 20 carbon atoms, or An aromatic diamine compound represented by the following formula: p may be an integer of 1 to 6, and m is an integer of 0 or 1.