JP2023077408A - Hydroxyanilide compound, and production method of the same - Google Patents

Abstract

To provide a hydroxyanilide compound useful for a production raw material of a liquid crystal polymer, and an efficient production method of the same.SOLUTION: A dihydroxyanilide compound is represented by the following formula (1), and has a purity measured by gas chromatography of 85% or more. A production method of a dihydroxyanilide compound represented by the formula (1) includes reacting a specific carboxylic acid chloride, and an amine having a specific hydroxyl group or a salt thereof using an alkali metal hydrogen carbonate in a mixed solvent of a cyclic ether and water. In the formula, R1 is an alkyl group, a ring A and a ring B are independently a ring having an atom selected from the group consisting of C, N, O, and S as a ring-constituting atom selected from the group consisting of a cycloalkane, a monocyclic aromatic ring, a polycyclic aromatic ring, and a condensed aromatic ring, where these rings may have substituent groups, and n is 0 or 1.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a hydroxyanilide compound useful as a raw material monomer for liquid crystal polymers and a method for producing the same.

In general, liquid crystal polymers (LCPs), typified by liquid crystal polyesters, are excellent in heat resistance and chemical resistance, but are inferior in transparency and solvent solubility to amorphous polymers. In order to suitably use LCP as a polymer material, especially as an optical polymer, it was necessary to control the degree of crystallinity and improve transparency and solvent solubility.

By using a dihydroxyanilide compound as a diol monomer, an optical polymer having excellent solvent solubility and transparency can be produced (see, for example, Patent Document 1).

Methods for producing dihydroxyanilide compounds include, for example, hydroxycarboxylic acid chlorides in which the hydroxy group is protected by a protective group such as a methyl group or an acetyl group, and hydroxycarboxylic acid chlorides in which the hydroxy group is protected by a protective group such as a methyl group or an acetyl group A method is known in which aminophenols are condensed and then deprotected in the final step (for example, Patent Document 2).

In Non-Patent Document 1, salicylic acid chloride prepared from salicylic acid and thionyl chloride is reacted with 4-aminophenol in the presence of triethylamine, and the desired 2-hydroxy-N-(4) is purified by silica gel column chromatography. -Hydroxyphenyl)benzamide is described in a yield of 71%.

Non-Patent Document 2 describes a method of condensing salicylic acid and 2-aminophenol in the presence of a condensing agent and purifying the resulting product by silica gel column chromatography to obtain the desired product with a yield of 69%.

Non-Patent Document 3 describes a method of reacting 4-hydroxybenzoic acid chloride prepared from 4-hydroxybenzoic acid and thionyl chloride with 4-aminophenol to obtain the desired product in a yield of 63%.

Non-Patent Document 4 describes a method of reacting 4-hydroxybenzoic acid chloride prepared from 4-hydroxybenzoic acid and oxalyl chloride with 4-aminophenol to obtain the desired product in a yield of 53%.

Non-Patent Document 5 describes a method of obtaining the desired product by condensing 3-hydroxybenzoic acid or 4-hydroxybenzoic acid and 3-aminophenol or 4-aminophenol in the presence of a condensing agent. However, the target compounds obtained by the methods described in Non-Patent Documents 1 to 5 have a hydrogen atom on the amide bond nitrogen atom and are different from the target compounds of the present invention.

WO2021/167074 A1 Patent No. 4320089

Journal of Pharmaceutical, Chemical and Biological Sciences, 2015, Vol. 3, No. 2, pp. 122-131 Bioorganic & Medicinal Chemistry, 2007, Vol. 15, No. 12, pp. 4113-4124 European Journal of Medicinal Chemistry, 2016, 117, 269-282 Chinese Journal of Chemistry 2003, Vol. 21, No. 11, pp. 1494-1496 Journal of Enzyme Inhibition and Medicinal Chemistry, 2013, Vol. 28, No. 1, pp. 148-152

As described above, dihydroxyanilide compounds include hydroxycarboxylic acid chlorides in which the hydroxy group is protected by a protective group such as a methyl group or an acetyl group, and aminophenols in which the hydroxy group is protected by a protective group such as a methyl group or an acetyl group. It is produced by condensing a group and deprotecting in the final step. However, this method cannot be said to be industrially advantageous in that a deprotection step is required.

In addition, when hydroxycarboxylic acid chlorides and aminophenols are directly condensed using a condensing agent or the like, by-production of compounds having an ester bond or compounds derived from the condensing agent cannot be avoided, and high-purity dihydroxy In order to obtain an anilide compound, high-cost purification is required, which is not economical.

Under such circumstances, the present inventors focused on carboxylic acid chlorides and hydroxyl-containing amines as raw materials for dihydroxyanilide compounds. Further, the present inventors conducted studies with the object of condensing these raw materials by a simple technique and providing a highly pure and highly yielded dihydroxyanilide compound and a method for producing the same.

As a result of intensive studies to solve the above problems, the present inventors have found that a carboxylic acid chloride and an amine (or a salt thereof) having a hydroxy group are mixed in the presence of an inexpensive alkali metal hydrogen carbonate to form a cyclic It was found that a dihydroxyanilide compound with high purity and high yield can be produced without using a protecting group by carrying out the reaction in a mixed solvent of ether and water. The present invention has been proposed based on these findings, and specifically has the following configurations.
[1]
A dihydroxyanilide compound represented by the following formula (1), having a purity of 85% or higher as measured by gas chromatography.

[Wherein, ring A and ring B each independently have a ring-constituting atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, a cycloalkane, a monocyclic aromatic ring, represents a ring selected from the group consisting of polycyclic aromatic rings and condensed aromatic rings, and these cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings and condensed aromatic rings have substituents; may be
R ¹ represents an alkyl group having 1 to 20 carbon atoms.
n represents 0 or 1; ]
[2]
The dihydroxyanilide compound according to [1], wherein ring A and ring B are each independently a ring selected from a cyclohexane ring and a benzene ring.
[3]
A carboxylic acid chloride represented by the following formula (2) and an amine having a hydroxyl group represented by the following formula (3) or a salt thereof are reacted in a mixed solvent of a cyclic ether and water using an alkali metal hydrogen carbonate. A method for producing a dihydroxyanilide compound represented by the following formula (1), characterized by:

[In the formula, R represents a hydroxy group or a chlorocarbonyl group. Ring A is selected from cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings and condensed aromatic rings having ring-constituting atoms selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. A ring selected from the group consisting of cycloalkane, monocyclic aromatic ring, polycyclic aromatic ring and condensed aromatic ring may have a substituent. ]

[In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms. Ring B is selected from cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings and condensed aromatic rings having ring-constituting atoms selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. A ring selected from the group consisting of cycloalkane, monocyclic aromatic ring, polycyclic aromatic ring and condensed aromatic ring may have a substituent. ]

[Wherein, ring A and ring B each independently have a ring-constituting atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, a cycloalkane, a monocyclic aromatic ring, represents a ring selected from the group consisting of polycyclic aromatic rings and condensed aromatic rings, and these cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings and condensed aromatic rings have substituents; may be
R ¹ represents an alkyl group having 1 to 20 carbon atoms.
n represents 0 or 1; ]
[4]
The method for producing a dihydroxyanilide compound according to [3], wherein the alkali metal hydrogen carbonate is sodium hydrogen carbonate or potassium hydrogen carbonate.
[5]
The method for producing a dihydroxyanilide compound according to [3] or [4], wherein the cyclic ether is tetrahydrofuran or 1,4-dioxane.
[6]
The mixture containing the dihydroxyanilide compound represented by the formula (1) is purified by washing with one or more selected from the group consisting of water, basic aqueous solution, acidic aqueous solution and organic solvent, and 85% or more (gas chromatography The method for producing a dihydroxyanilide compound according to any one of [3] to [5], comprising the step of isolating the compound of formula (1) with a purity of 1000 nm.
[7]
The method for producing a dihydroxyanilide compound according to any one of [3] to [6], wherein R ¹ in formula (1) is an alkyl group having 1 to 12 carbon atoms.
[8]
a group in which ring A and ring B each independently comprise an optionally substituted cyclohexane ring, an optionally substituted benzene ring, an optionally substituted naphthalene ring and an optionally substituted biphenyl ring; The method for producing a hydroxyanilide compound according to any one of [3] to [7], wherein the ring is selected from
[9]
A polymer containing a repeating unit represented by the following formula (4).

[Wherein, ring A and ring B each independently have a ring-constituting atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, a cycloalkane, a monocyclic aromatic ring, represents a ring selected from the group consisting of polycyclic aromatic rings and condensed aromatic rings, and these cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings and condensed aromatic rings have substituents; may be
L is a cycloalkane, a monocyclic aromatic ring, a polycyclic aromatic ring and a condensed aromatic ring in which the ring-constituting atoms are atoms selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms; represents a ring selected from the group or an optionally substituted alkyl chain having 1 to 20 carbon atoms; These cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings, condensed aromatic rings, and alkyl chains may have substituents.
R ¹ represents an alkyl group having 1 to 20 carbon atoms.
n represents 0 or 1; ]
[10]
An optical film comprising the polymer according to [9].

An optical film composed of a liquid crystal polymer synthesized using the dihydroxyanilide compound of the present invention exhibits high transparency. In addition, a dihydroxyanilide compound useful as a raw material for producing a liquid crystal polymer can be produced with high purity and high yield.

The present invention will be described in detail below. Although the constituent elements described below may be described based on representative embodiments and specific examples, the present invention is not limited to such embodiments. In addition, the numerical range represented by using "from" in this specification means the range which includes the numerical value described before and behind "from" as a lower limit and an upper limit.

The present invention is a compound represented by the general formula (1) having a purity of 85% or more as measured by gas chromatography (hereinafter sometimes referred to as the dihydroxyanilide compound of the present invention).

In formula (1), ring A and ring B are each independently a cycloalkane or monocyclic aromatic ring having atoms selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms as ring-constituting atoms. represents a ring selected from the group consisting of a ring, a polycyclic aromatic ring and a condensed aromatic ring, and these cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings and condensed aromatic rings each have a substituent may have. R ¹ represents an alkyl group having 1 to 20 carbon atoms. n represents 0 or 1;

In formula (1), R ¹ represents an alkyl group having 1 to 20 carbon atoms, and examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group. , sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, Octadecyl group, nonadecyl group, icosyl group, etc., among them, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, etc. are preferred, and particularly preferably A methyl group, an ethyl group, a pentyl group, a hexyl group, and the like.

In formula (1), ring A is a cycloalkane, monocyclic aromatic ring, polycyclic aromatic ring and ring-constituting atoms selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. represents a ring selected from the group consisting of condensed aromatic rings, and these cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings and condensed aromatic rings may have a substituent.

Here, the substituents in the cycloalkane, monocyclic aromatic ring, polycyclic aromatic ring and condensed aromatic ring include an alkyl group having 1 to 8 carbon atoms, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, Examples thereof include acyl groups having 2 to 4 carbon atoms.

Examples of alkyl groups having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, An octyl group and the like can be mentioned.

Halogen atoms include, for example, fluorine, chlorine, bromine and iodine atoms.

The alkoxy group having 1 to 4 carbon atoms includes, for example, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group and the like.

Examples of acyl groups having 2 to 4 carbon atoms include acetyl group, propionyl group and butyryl group.

Examples of cycloalkanes which may have substituents and which have atoms selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms in ring A as ring-constituting atoms include, for example, cyclohexane, vinyl cyclohexyl, decalin and the like.

The optionally substituted monocyclic aromatic ring having ring atoms selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom in ring A includes, for example, benzene and pyridine. , pyrazine, pyrimidine, pyridazine, furan, pyrrole, imidazole, thiophene, pyrazole, oxazole, isoxazole, thiazole, triazole and the like.

The polycyclic aromatic ring optionally having substituent(s) having ring-constituting atoms selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom in ring A includes, for example, biphenyl, ter phenyl, bipyridine, bithiophene, bifuran and the like.

The optionally substituted condensed aromatic ring having a ring-constituting atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom in ring A includes, for example, naphthalene, anthracene, , phenanthrene, quinoline, benzofuran, benzimidazole, benzothiophene, indole, indazole, benzoxazole, benzothiazole, benzotriazole and the like.

As the ring A, from the viewpoint of easy availability, a cycloalkane or an optionally substituted cycloalkane having a ring-constituting atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom A monocyclic aromatic ring having a ring-constituting atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is preferred, and a benzene ring or a cyclohexane ring is particularly preferred.

In formula (1), ring B is a cycloalkane, monocyclic aromatic ring, polycyclic aromatic ring and ring-constituting atoms selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms and sulfur atoms. represents a ring selected from the group consisting of condensed aromatic rings, and these cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings and condensed aromatic rings may have a substituent.

Specific examples of the ring B include those similar to those of the ring A. A monocyclic aromatic ring having a ring-constituting atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. is preferred, and a benzene ring is particularly preferred.

A preferable example of the dihydroxyanilide compound represented by the general formula (1) is a dihydroxyanilide compound represented by the following chemical formula (1').

In formula (1′), ring A, R ¹ and n are synonymous with ring A, R ¹ and n in formula (1), respectively.

Specific examples of the dihydroxyanilide compound represented by the general formula (1) include dihydroxyanilide compounds represented by the following chemical formulas (1-1-1) to (1-6-5).

Among these (1-1-1) to (1-6-5), preferably (1-1-1) to (1-1-24), (1-1-91) to (1-1- 105), (1-2-1) to (1-2-20), etc., and particularly preferably (1-1-1) to (1-1-24), (1-1-91), ( 1-1-94) to (1-1-104).

The dihydroxyanilide compound of the present invention has a purity measured by gas chromatography of 85% or higher, preferably 90% or higher, more preferably 95% or higher, particularly preferably 99% or higher.

In the method for producing a dihydroxyanilide compound represented by formula (1) of the present invention, a carboxylic acid chloride represented by formula (2) and an amine having a hydroxyl group represented by formula (3) or a salt thereof are combined with an alkali A method of reacting with a mixed solvent of cyclic ether and water using a metal hydrogen carbonate, or a hydroxycarboxylic acid chloride in which the hydroxy group is protected with a protecting group such as an alkyl group, and a hydroxy group with a protecting group such as an alkyl group. A method of condensing a protected aminophenol and deprotecting it with boron tribromide, aluminum trichloride or the like in the final step can be exemplified. The method comprises reacting a carboxylic acid chloride represented by the formula (2) with an amine having a hydroxyl group represented by the formula (3) or a salt thereof using an alkali metal hydrogen carbonate in a mixed solvent of a cyclic ether and water. A preferred method is described below.

In formula (2), R represents a hydroxy group or a chlorocarbonyl group.

In formula (2), ring A has the same definition as ring A in formula (1).

In formula (3), R ¹ and ring B have the same meanings as R ¹ and ring B in formula (1) above.

In formula (1), n represents 0 or 1. n is 0 when R in formula (2) is a hydroxy group, and n is 1 when R in formula (2) is a chlorocarbonyl group.

Specific examples of the carboxylic acid chloride represented by formula (2) include structures represented by the following chemical formulas (2-1-1) to (2-5-1).

Among the chemical formulas (2-1-1) to (2-5-1), preferably (2-1-1) to (2-1-11), (2-4-1), (2-5- 1) and the like, and particularly preferably (2-1-1), (2-4-1), (2-5-1) and the like.

Carboxylic acid chlorides of formula (2) are known or can be readily prepared according to methods known in the literature. Moreover, you may use a commercial item.

In one embodiment of the present invention, since the amine having a hydroxyl group represented by formula (3) contains an amino group, part or all of it may be a salt with an inorganic acid or an organic acid. The type of salt is not particularly limited, and examples include hydrochloride, hydrobromide, perchlorate, silicate, tetrafluoroborate, hexafluorophosphate, sulfate, nitrate, and phosphoric acid. Inorganic acid salts such as salts, organic acid salts such as acetate, citrate, fumarate, maleate, trifluoromethanesulfonate, trifluoroacetate, benzoate, and p-toluenesulfonate. Inorganic acid salts are preferable, and hydrochlorides or sulfates are more preferable because they are inexpensive.

As specific amines having a hydroxyl group represented by formula (3) or salts thereof, structures represented by the following chemical formulas (3-1-1) to (3C-3-15) can be exemplified.

Among the chemical formulas (3-1-1) to (3C-2-5), preferably (3-1-1) to (3-1-5), (3S-1-1) to (3S-1-5 ), (3C-1-1) to (3C-1-5), (3-3-1) to (3-3-15), etc., and particularly preferably (3-1-1) to (3 -1-5), (3S-1-1) to (3S-1-5), (3-3-1) to (3-3-15), and so on.

Hydroxyl-containing amines of formula (3) or salts thereof are known or can be readily prepared according to methods known in the literature. Moreover, you may use a commercial item.

In the production method of the present invention, the ratio of the carboxylic acid chloride represented by formula (2) and the hydroxy group-containing amine or salt thereof represented by formula (3) is, when n is 0, the molar ratio of the formula Carboxylic acid chloride represented by (2): amine having a hydroxyl group represented by formula (3) or a salt thereof = 1:0.9 to 1:1.1 is preferable, and when n is 1, the formula ( Carboxylic acid chloride represented by 2): amine having a hydroxyl group represented by formula (3) or a salt thereof is preferably 1:1.9 to 1:2.1.

In the present invention, it is essential to use an alkali metal hydrogen carbonate as a base in order to suppress by-products such as ester compounds.

The alkali metal hydrogen carbonate is not particularly limited as long as it has the ability to neutralize the acid in the reaction system. Examples thereof include sodium hydrogen carbonate, potassium hydrogen carbonate, calcium hydrogen carbonate, cesium hydrogen carbonate, etc. Among them, Sodium hydrogencarbonate or potassium hydrogencarbonate is preferred because it suppresses esterification, is inexpensive, and is less harmful to the human body.

The amount of alkali metal hydrogen carbonate that can be used is 2 to 8 molar equivalents or more relative to 1 molar equivalent of formula (3) when formula (3) is a salt of an amine having a hydroxy group. Preferably, when formula (3) is an amine having a hydroxy group, it is preferably used in an amount of 1 to 8 molar equivalents relative to 1 molar equivalent of formula (3).

The alkali metal hydrogencarbonate may be used as a solid such as granules, granules, or powder. Aqueous solutions thereof can also be used, and the concentration is not particularly limited.

Cyclic ethers used in this reaction include, for example, tetrahydrofuran (THF), 1,4-dioxane, 1,3-dioxolane and the like. THF or 1,4-dioxane is preferred because it is easy to remove by distillation, is inexpensive, and is less harmful to the human body.

Here, the mixing ratio of the mixed solvent of the cyclic ether and water used in the production method of the present invention is not particularly limited as long as the reaction proceeds, and the volume ratio of the cyclic ether and water is preferably 10:1. to 1:10, more preferably 3:1 to 1:3.

The reaction temperature in the production method of the present invention is preferably −30° C. or higher and 50° C. or lower, particularly preferably 0° C. or higher and 40° C. or lower, and the reaction time is preferably 5 minutes or longer and 24 hours or shorter.

A mixture containing a dihydroxyanilide compound obtained by the production method of the present invention may be purified to a suitable degree of purity. Purification methods include washing, column chromatography, reprecipitation, recrystallization, and the like. Purification by washing or reprecipitation is preferable because the amount of organic solvent used is small, and purification by washing is more preferable because it is inexpensive.

In the washing, one or more selected from the group consisting of water, an acidic aqueous solution, a basic aqueous solution, and an organic solvent can be used. By performing the washing, the above formula ( The compound of 1) can be isolated.

The purity of the compound produced by the production method of the present invention can be measured by gas chromatography, high performance liquid chromatography, NMR or the like. Measurement by gas chromatography or high-performance liquid chromatography is preferable, and measurement by gas chromatography is particularly preferable, because it is simple and highly sensitive.

The washing with water, acidic aqueous solution, or basic aqueous solution may be performed on a solution of the crude dihydroxyanilide compound, for example, an ethyl acetate solution of the crude dihydroxyanilide compound. Alternatively, the solid of the crude dihydroxyanilide compound may be washed directly.

The washing with an organic solvent may be performed on the crude dihydroxyanilide compound.

The acidic aqueous solution used for washing is not particularly limited as long as it can remove the by-product having an amino group as a salt, and examples thereof include hydrochloric acid, sulfuric acid aqueous solution, and citric acid aqueous solution. An aqueous solution of hydrochloric acid or sulfuric acid is preferred because it is inexpensive.

The basic aqueous solution used for washing is not particularly limited as long as it can remove the by-product having a carboxyl group as a salt. , sodium acetate aqueous solution. A sodium bicarbonate aqueous solution or a sodium hydroxide aqueous solution is preferable in that it is inexpensive.

The organic solvent used for washing is not particularly limited as long as it can remove by-products. Examples include alcohol solvents such as methanol, ethanol and isopropyl alcohol, nitrile solvents such as acetonitrile, methyl acetate, ethyl acetate, Examples include ester solvents such as butyl acetate, hydrocarbon solvents such as pentane, hexane, and octane, and ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Methanol, ethanol, ethyl acetate, or acetonitrile is preferable because it is inexpensive and can efficiently remove by-products.

In the production method of the present invention, since an alkali metal hydrogen carbonate is used as a base, the amount of the ester formed by condensing the phenolic hydroxy group and the carboxy group is extremely small, and the dihydroxyanilide compound is produced with high purity and high yield. Obtainable.

Next, the polymer of the present invention will be explained.

The polymer of the present invention is a polymer containing repeating units represented by the following formula (4).

[Wherein, ring A and ring B each independently have a ring-constituting atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, a cycloalkane, a monocyclic aromatic ring, represents a ring selected from the group consisting of polycyclic aromatic rings and condensed aromatic rings, and these cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings and condensed aromatic rings have substituents; may be
L is a cycloalkane, a monocyclic aromatic ring, a polycyclic aromatic ring and a condensed aromatic ring in which the ring-constituting atoms are atoms selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms; represents a ring selected from the group or an optionally substituted alkyl chain having 1 to 20 carbon atoms; These cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings, condensed aromatic rings, and alkyl chains may have substituents.
R ¹ represents an alkyl group having 1 to 20 carbon atoms.
n represents 0 or 1; ]
In formula (4), R ¹ represents an alkyl group having 1 to 20 carbon atoms, and examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group. , sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, Octadecyl group, nonadecyl group, icosyl group, etc., among them, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, etc. are preferred, and particularly preferably A methyl group, an ethyl group, a pentyl group, a hexyl group, and the like.

In formula (4), ring A is a cycloalkane, monocyclic aromatic ring, polycyclic aromatic ring and ring-constituting atoms selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. represents a ring selected from the group consisting of condensed aromatic rings, and these cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings and condensed aromatic rings may have a substituent.

Here, the substituents in the cycloalkane, monocyclic aromatic ring, polycyclic aromatic ring and condensed aromatic ring include an alkyl group having 1 to 8 carbon atoms, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, Examples thereof include acyl groups having 2 to 4 carbon atoms.

Examples of alkyl groups having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, An octyl group and the like can be mentioned.

Halogen atoms include, for example, fluorine, chlorine, bromine and iodine atoms.

The alkoxy group having 1 to 4 carbon atoms includes, for example, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group and the like.

Examples of acyl groups having 2 to 4 carbon atoms include acetyl group, propionyl group and butyryl group.

Examples of cycloalkanes which may have substituents and which have atoms selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms in ring A as ring-constituting atoms include, for example, cyclohexane, vinyl cyclohexyl, decalin and the like.

The optionally substituted monocyclic aromatic ring having ring atoms selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom in ring A includes, for example, benzene and pyridine. , pyrazine, pyrimidine, pyridazine, furan, pyrrole, imidazole, thiophene, pyrazole, oxazole, isoxazole, thiazole, triazole and the like.

The polycyclic aromatic ring optionally having substituent(s) having ring-constituting atoms selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom in ring A includes, for example, biphenyl, ter phenyl, bipyridine, bithiophene, bifuran and the like.

The optionally substituted condensed aromatic ring having a ring-constituting atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom in ring A includes, for example, naphthalene, anthracene, , phenanthrene, quinoline, benzofuran, benzimidazole, benzothiophene, indole, indazole, benzoxazole, benzothiazole, benzotriazole and the like.

As the ring A, from the viewpoint of easy availability, a cycloalkane or an optionally substituted cycloalkane having a ring-constituting atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom A monocyclic aromatic ring having a ring-constituting atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom is preferred, and a benzene ring or a cyclohexane ring is particularly preferred.

In formula (4), ring B is a cycloalkane, monocyclic aromatic ring, polycyclic aromatic ring and ring-constituting atoms selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. represents a ring selected from the group consisting of condensed aromatic rings, and these cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings and condensed aromatic rings may have a substituent.

Specific examples of the ring B include those similar to those of the ring A. A monocyclic aromatic ring having a ring-constituting atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. is preferred, and a benzene ring is particularly preferred.

In formula (4), L is a cycloalkane, a monocyclic aromatic ring, a polycyclic aromatic ring and a condensed represents a ring selected from the group consisting of cyclic aromatic rings or an optionally substituted alkyl chain having 1 to 20 carbon atoms; These cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings, condensed aromatic rings, and alkyl chains may have substituents.

Specific cycloalkanes which may have substituents and whose ring-constituting atoms are atoms selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms in L include, for example, cyclohexane and bicyclohexyl. , decalin and the like.

The optionally substituted monocyclic aromatic ring having a ring-constituting atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom in L includes, for example, benzene, pyridine, pyrazine, pyrimidine, pyridazine, furan, pyrrole, imidazole, thiophene, pyrazole, oxazole, isoxazole, thiazole, triazole and the like.

The optionally substituted polycyclic aromatic ring having ring-constituting atoms selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom in L includes, for example, biphenyl, terphenyl , bipyridine, bithiophene, bifuran, and the like.

Examples of the condensed aromatic ring optionally having substituent(s) having ring-constituting atoms selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom in L include naphthalene, anthracene, phenanthrene, quinoline, benzofuran, benzimidazole, benzothiophene, indole, indazole, benzoxazole, benzothiazole, benzotriazole and the like.

Among these, L is preferably benzene, cyclohexane, biphenyl, or an alkyl chain having 1 to 8 carbon atoms, and particularly preferably benzene, cyclohexane, or the like.

Specific examples of polymers containing repeating units represented by formula (4) include the following polymers (4-1-1-1) to (4-2-1-11).

Among these, (4-1-1-1) to (4-1-1-3), (4-1-2-1) to (4-1-2-3), (4-1-3- 1) to (4-1-20-2), (4-2-1-1) to (4-2-1-3) and the like are preferable, and particularly preferably (4-1-1-1) to ( 4-1-1-3), etc.

The polymer containing a repeating unit represented by the formula (4) of the present invention may contain a repeating unit other than the repeating unit represented by the formula (4), and the repeating unit other than the repeating unit represented by the formula (4) Examples of repeating units include structures represented by the following chemical formulas (L'1) to (L'14).

The polymer of the present invention may contain at least one or more surfactants in order to reduce film thickness unevenness when forming an optical film. Surfactants that can be included include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoro Alkylethylene oxide derivatives, polyethylene glycol derivatives, alkylammonium salts, fluoroalkylammonium salts and the like can be mentioned, and fluorine-containing surfactants are particularly preferred.

As a method for producing the polymer of the present invention, the dihydroxyanilide compound represented by the formula (1) is polymerized with a raw material composition containing at least one selected from the group consisting of dicarboxylic acid dichloride and dicarboxylic acid. be able to.

Examples of dicarboxylic acids include aliphatic polycarboxylic acids (specifically, saturated polycarboxylic acids having 2 to 20 carbon atoms such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and sebacic acid). acid, maleic acid, fumaric acid, unsaturated polycarboxylic acids such as itaconic acid), alicyclic polycarboxylic acids (cyclobutanedicarboxylic acid, trans-1,4-cyclohexanedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid acid, etc.), aromatic polycarboxylic acids (terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-oxybis (benzoic acid), 2,5-furandicarboxylic acid, etc.) is mentioned.

Examples of the dicarboxylic acid dichloride include saturated carboxylic acid dichlorides having 2 to 20 carbon atoms such as oxalic acid dichloride, malonic acid dichloride, succinic acid dichloride, glutaric acid dichloride, adipic acid dichloride, and sebacic acid dichloride; fumaric acid dichloride; Aliphatic carboxylic acids such as unsaturated polycarboxylic acid dichloride such as itaconic acid dichloride, cyclobutanedicarboxylic acid dichloride, cyclopentanedicarboxylic acid dichloride, trans-1,4-cyclohexanedicarboxylic acid dichloride, cis-1,4-cyclohexanedicarboxylic acid dichloride, etc. Aromatic compounds such as acid dichloride, terephthalic acid dichloride, isophthalic acid dichloride, orthophthalic acid dichloride, 4,4′-biphenyldicarboxylic acid dichloride, 4,4′-oxybis(benzoic acid chloride), 2,5-furandicarboxylic acid dichloride, etc. carboxylic acid and the like.

In the method for producing a polymer of the present invention, a polyhydric hydroxy compound may be used for the purpose of adjusting the physical properties of the polymer produced.

Examples of polyhydric hydroxy compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 1,2-propylene glycol, 1,4-butanediol, 2,2-butanediol, 2,3-butanediol, 2,4-dimethyl-2,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 2-methyl-1,3-propane diol, 3-methyl-1,5-heptanediol, cyclopentanediol, cyclohexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, hydroquinone, Tetramethylhydroquinone, 4,4'-dihydroxybiphenyl, benzenedimethanol, vanillyl alcohol, furandimethanol, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-(1,3-dimethylbutylidene) diphenol, 6,6'-dihydroxy-4,4,4',4',7,7'-hexamethyl-2,2'-spirobichroman, tricyclodecanedimethanol, 2,2'-dihydroxydiphenyl ether, 4,4'-methylenebis(2,6-dimethylphenol), 3,3',5,5'-tetramethylbiphenyl-4,4'-diol, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2 -butene-1,4-diol, 2,2-diisobutyl-1,3-propanediol, bis[4-(2-hydroxyethoxy)phenyl]sulfone, 2,2,4,4-tetramethyl-1,3 -cyclobutanediol, 1,4-bis(3-hydroxyphenoxy)benzene, 4,4'-bicyclohexanol, bis(4-hydroxy-3-methylphenyl)sulfide, 2,2-diisoamyl-1,3-propanediol , 4,4′-dihydroxydiphenylmethane, dihydroxynaphthalene, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfone, 1,4-benzenedimethanol, 3,9- Bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 4,4′-biphenyldimethanol, 1,3-bis(hexafluoro- α-hydroxyisopropyl)benzene, 3,6-dihydroxybenzonorbornane, 2-benzyloxy-1,3-propanediol, 4,4′-dihydroxybenzophenone, 4,4′-dihydroxydiphenyl ether, 9,9-bis(4 -hydroxyphenyl)fluorene, 1,8-bis(hydroxymethyl)anthracene, 1,4-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, α,α'-bis(4-hydroxy-3 ,5-dimethylphenyl)-1,4-diisopropylbenzene, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2′-methylenebis(4-methylphenol), 1,3- Bis(4-hydroxyphenoxy)benzene, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 2,2-bis(4-hydroxy-3 -methylphenyl)propane, 2,2'-dihydroxybenzophenone, 2,2'-bis(hydroxymethyl)diphenyl ether, 7,7'-dihydroxy-4,4,4',4'-tetramethyl-2,2' -spirobichroman, 1,4-bis(hydroxymethyl)-2,3,5,6-tetramethylbenzene, 4,4'-ethylidenebisphenol, cyclohexanedimethanol, polyethylene glycol, 1,3-adamantanediol, 1 -hydroxy-3-(hydroxymethyl)adamantane, 2,7-dihydroxy-9H-fluoren-9-one, divalent hydroxy compounds such as polyethylene glycol of various molecular weights, glycerin, trimethylolpropane, triethanolamine, 2 , 3,4,4′-Tetrahydroxybenzophenone, 1,2,3-butanetriol, trivalent hydroxy compounds such as 2,6-bis(hydroxymethyl)-4-methylphenol, tetravalent compounds such as pentaerythritol Hydroxy compounds, and other polyvalent hydroxy compounds include various sugars.

The polymerization method is not particularly limited, and includes polymerization methods known in the art, such as interfacial polymerization and solution polymerization.

As the interfacial polymerization method, for example, a method of performing interfacial polymerization in a water-organic solvent two-layer system can be mentioned.

When performing interfacial polymerization in a water-organic solvent two-layer system, it is preferable to use a phase transfer catalyst and a base for the purpose of promoting the reaction.

Phase transfer catalysts include, for example, benzyltriethylammonium chloride, benzyltriethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetraamylammonium chloride, tetraamylammonium bromide, tetraheptylammonium chloride, tetraheptylammonium bromide, dimethyldipal Ammonium salts such as mythylammonium chloride and dimethyldipalmitylammonium bromide, tetraethylphosphonium chloride, tetraethylphosphonium bromide, tributylhexylphosphonium chloride, tributylhexylphosphonium bromide, tetra-n-octylphosphonium chloride, tetra-n-octylphosphonium bromide, tributyl - Phosphonium salts such as n-octylphosphonium chloride, tributyl-n-octylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, and the like.

Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrides such as sodium hydride; Alkali metal alkoxides and tetrabutylammonium hydroxide can be exemplified.

The reaction temperature of the interfacial polymerization is preferably −30° C. or higher and 50° C. or lower, particularly preferably 0° C. or higher and 40° C. or lower, and the reaction time is preferably 30 minutes or longer and 24 hours or shorter.

As the organic solvent used for interfacial polymerization, any organic solvent can be used as long as it does not harm the reaction. , aromatic solvents such as toluene, xylene, chlorobenzene and dichlorobenzene, and halogen solvents such as dichloromethane, chloroform and carbon tetrachloride. These solvents may be used singly or as a mixture of two or more at any ratio.

The solution polymerization method includes a method using a condensing agent in an organic solvent.

As the organic solvent used in the solution polymerization method, any organic solvent can be used as long as it does not harm the reaction. Aromatic solvents such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene and pyridine; halogen solvents such as dichloromethane, chloroform and carbon tetrachloride; amide solvents such as dimethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone. , ethyl acetate, and butyl acetate. These solvents may be used singly or as a mixture of two or more at any ratio.

Condensing agents used in the solution polymerization method include, for example, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride, N ,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, bis(2,6-diisopropylphenyl)carbodiimide, bis(trimethylsilyl)carbodiimide, 1-cyclohexyl-3-(2-morpholinoethyl)carbodiimide-p-toluenesulfo nate, N,N'-di-tert-butylcarbodiimide, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide methiodide, among these, 1-[3-(dimethyl Amino)propyl]-3-ethylcarbodiimide, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride, N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide are preferred. Two or more of these ester bond-forming condensing agents may be used.

The reaction temperature in the solution polymerization method is preferably −30° C. or higher and 50° C. or lower, particularly preferably 0° C. or higher and 40° C. or lower, and the reaction time is preferably 30 minutes or longer and 24 hours or shorter.

The polymers of the invention can be used as optical films.

The method for producing the optical film of the present invention is not particularly limited, and examples thereof include methods such as a melt film-forming method and a solution casting method.

The melt film-forming method specifically includes a melt extrusion method using a T-die, a calendar molding method, a hot press method, a co-extrusion method, a co-melting method, a multilayer extrusion method, an inflation molding method, and the like, and is not particularly limited.

The solution casting method is a method in which a solution of a polymer dissolved in a solvent (hereinafter referred to as "casting dope") is cast on a support substrate, and then the solvent is removed by heating or the like to obtain a film. At that time, as a method for casting the dope for casting onto the supporting substrate, a spin coating method, a T-die method, a doctor blade method, a bar coater method, a roll coater method, a lip coater method, or the like is used. Particularly industrially, the most common method is to continuously extrude the dope for casting from a die onto a belt-shaped or drum-shaped support substrate. Examples of supporting substrates that can be used include glass substrates, metal substrates such as stainless steel and ferrotype, and films such as polyethylene terephthalate.

A polymer containing repeating units represented by formula (4) has high solubility in organic solvents, and an optical film made of this polymer has high transparency and is suitable for optical applications. This is presumed to be due to the following mechanism.

In the polymer containing repeating units represented by formula (4) of the present invention, the ring structures are connected by N-alkylamide bonds, and when the rings connected by N-alkylamide bonds are aromatic rings In addition, it can adopt a cis conformation. This introduces a dynamic bending structure into the polymer chain and reduces crystallinity. Crystallization is also inhibited by substituents on the nitrogen.

Formation of cis-steric structure by N-alkylbenzanilide is a universal phenomenon in low-molecular-weight compounds, as reported in previous reports (YAKUGAKU ZASSHI, 2001, 121, 117-129.).

That is, in the present invention, the above phenomenon is applied to polymers.

2 shows the results of gas chromatography of the dihydroxyanilide compound obtained in Example 1. FIG.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention should not be construed as being limited to these examples.
<Heat treatment>
The film was heat-treated using a thermostat safety oven with a safety door (manufactured by ESPEC, trade name: SPH-202).
<Film thickness measurement>
The thickness of the film was measured using a spectroscopic ellipsometer (manufactured by JA Woollam, trade name: RC2-U).
<Haze/YI value>
The haze and YI (yellow index) value of the film were measured with a spectroscopic haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name: SH7000).
<Gas chromatography purity>
The purity of the synthesized compound was measured by gas chromatography (manufactured by Shimadzu Corporation, trade name: GC-2025) (area percentage method).
(Gas chromatography measurement conditions)
・ Column: TC-1 (30 m, 0.25 mm ID, 1.00 μm, manufactured by GL Sciences)
・Vaporization chamber temperature: 300°C
・Column temperature: 50°C-20°C/min-300°C (10-30 min)
・Detector (FID) temperature: 300°C
・Sample concentration: 1 wt% methanol solution ・Injection volume: 1 μL
・Split ratio: 30:1
・Carrier gas: Nitrogen, linear velocity 35.2 cm/sec
[Example 1]

A mixture of 4-hydroxybenzoic acid (40.1 g, 290 mmol), thionyl chloride (276 g, 2.32 mol) and N,N-dimethylformamide (21.2 mg, 290 μmol) was heated under reflux and stirred for 1 hour. By distilling off thionyl, 4-hydroxybenzoic acid chloride was obtained. The obtained 4-hydroxybenzoic acid chloride was made into a THF (350 mL) solution, and the whole amount was used for the next reaction.

Under a nitrogen atmosphere, a mixture of p-methylaminophenol sulfate (50.0 g, 290 mmol), water (350 mL), and THF (350 mL) was stirred under ice cooling, and sodium hydrogen carbonate (122 g, 1.45 mol) was added. Add over 5 minutes. Subsequently, the THF solution of 4-hydroxybenzoyl chloride prepared above was added dropwise over 5 minutes. After the dropwise addition, the mixture was stirred for 15 hours while gradually raising the temperature to room temperature, and then THF was distilled off under reduced pressure. The resulting solid was collected by filtration, washed with water (1 L), then washed with 2M hydrochloric acid (600 mL) and acetonitrile (200 mL) to give a white solid (yield: 44.3 g, yield: 62.7%). As a compound (1-1-1) was obtained. ¹ H-NMR (400 MHz, (CD ₃ ) ₂ SO): δ 9.97-9.22 (br, 2H), 7.03 (d, J = 8.7 Hz, 2H), 6.86 (d, J = 8.7Hz, 2H), 6.58 (d, J = 8.7Hz, 2H), 6.50 (d, J = 8.7Hz, 2H), 3.20 (s, 3H)
The purity of the obtained 4-hydroxy-N-(4-hydroxyphenyl)-N-methylbenzamide (1-1-1) was measured by gas chromatography (Fig. 1). The purity was 98% (retention time: 27.916) by method. Further, it was confirmed from mass spectrum analysis that the substance with a retention time of 15.367 was an impurity derived from p-methylaminophenol.

[Example 2]

A mixture of vanillic acid (5.0 g, 29.7 mmol), thionyl chloride (28.3 g, 238 mol) and N,N-dimethylformamide (2.17 mg, 29.7 μmol) was heated under reflux and stirred for 1 hour, By distilling off thionyl chloride, vanillyl chloride was obtained. The obtained vanillic acid chloride was used as a THF (35 mL) solution, and the whole amount was used for the next reaction.

Under a nitrogen atmosphere, sodium hydrogen carbonate (12.5 g , 149 mol) was added over 5 minutes. Subsequently, the THF solution of vanillyl chloride prepared above was added dropwise over 5 minutes. After the dropwise addition, the mixture was stirred for 15 hours while gradually raising the temperature to room temperature, and then THF was distilled off under reduced pressure. The obtained mixture was extracted with ethyl acetate (50 mL×3), and the organic layer was washed with 2M hydrochloric acid (200 mL) and water (200 mL), and dried over anhydrous sodium sulfate. The resulting organic layer was concentrated under reduced pressure to obtain compound (1-1-6) as a white solid (yield: 4.90 g, yield: 60%). ¹ H-NMR (400 MHz, (CD ₃ ) ₂ SO): δ 9.60-9.09 (br, 2H), 6.90-6.84 (m, 2H), 6.70-6.62 (m , 2H), 6.60-6.54 (m, 2H), 6.52 (m, 1H), 3.51 (s, 3H), 3.22 (s, 3H).
The purity of the obtained (1-1-6) was measured by gas chromatography and found to be 97% (retention time: 17.711) by area percentage method.
[Example 3]

After cooling 4′-hydroxyacetanilide (3.85 g, 25.5 mmol) with ice under a nitrogen atmosphere, a 1 mmol/L borane-THF complex THF solution (100 mL, 100 mmol) was slowly added. After heating the reaction system to room temperature, it was heated and stirred at 60° C. for 24 hours. After completion of the reaction, the mixture was cooled in an ice bath, and methanol (21 mL) was added over 5 minutes. After water (100 mL) was added to the resulting reaction mixture, THF was distilled off using an evaporator, followed by extraction with dichloromethane (100 mL×3). The obtained organic layer was dried over sodium sulfate and then concentrated under reduced pressure. The resulting composition was purified by silica gel column chromatography (ethyl acetate/hexane = 61/39 vol%) to give 4-(ethylamino)phenol as a brown solid (yield: 2.07 g, yield: 59%). got
¹ H-NMR (400 MHz, CDCl ₃ : δ 6.69 (d, J=8.9 Hz, 2H), 6.53 (d, J=8.9 Hz, 2H), 3.09 (q, J=7. 2 Hz, 2 H), 1.22 (t, J=7.2 Hz, 3 H).
A mixture of 4-hydroxybenzoic acid (2.01 g, 29.7 mmol), thionyl chloride (13.9 g, 117 mmol) and N,N-dimethylformamide (1.07 mg, 14.6 μmol) was heated under reflux and stirred for 1 hour. After that, 4-hydroxybenzoic acid chloride was obtained by distilling off thionyl chloride. The obtained 4-hydroxybenzoic acid chloride was made into a THF (13 mL) solution, and the entire amount was used for the next reaction.

Under a nitrogen atmosphere, sodium hydrogen carbonate (6.12 g, 72 .9 mmol) was added over 5 minutes. Subsequently, the THF solution of 4-hydroxybenzoyl chloride prepared above was added dropwise over 5 minutes. After the dropwise addition, the mixture was stirred for 15 hours while gradually raising the temperature to room temperature, and then THF was distilled off under reduced pressure. The resulting mixture was extracted with ethyl acetate (50 mL×3), and the organic layer was washed with 2N hydrochloric acid (100 mL×2) and water (100 mL), and dried over anhydrous sodium sulfate. The resulting organic layer was concentrated under reduced pressure to obtain compound (1-1-2) as a white solid (yield: 1.99 g, yield: 53%).
¹ H-NMR (400 MHz, (CD ₃ ) ₂ SO): δ 8.85-10.12 (2H), 7.02 (d, J = 8.7 Hz, 2H), 6.83 (d, J = 8 .7Hz, 2H), 6.59 (d, J = 8.7Hz, 2H), 6.49 (d, J = 8.7Hz, 2H), 3.70 (q, J = 7.2Hz, 2H) , 1.01(t, J=7.2 Hz, 3H).
The purity of the obtained (1-1-2) was measured by gas chromatography and found to be 96% (retention time: 17.199) by area percentage method.
[Example 4]

Under a nitrogen atmosphere, a mixture of p-(methylamino)phenol sulfate (8.65 g, 35.0 mmol), water (45 mL), and THF (45 mL) was ice-cooled, then sodium hydrogen carbonate (29.4 g, 350 mmol). was added over 5 minutes. Subsequently, a solution of terephthaloyl chloride (7.11 g, 35.0 mmol) in THF (45 mL) was added dropwise over 5 minutes. After the dropwise addition was completed, the mixture was stirred at the same temperature for 1 hour, and then THF was distilled off under reduced pressure. The resulting solid was washed with methanol (200 mL) and water (200 mL) to obtain compound (1-2-1) as a white solid (yield: 10.3 g, yield: 78%). ¹ H-NMR (400 MHz, (CD ₃ ) ₂ SO): δ 9.55-9.28 (br, 2H), 6.98 (s, 4H), 6.87-6.67 (m, 4H), 6.58-6.49 (m, 4H), 3.20 (s, 6H).
[Example 5]

Under a nitrogen atmosphere, a mixture of p-(methylamino)phenol sulfate (8.65 g, 25.1 mmol), water (50 mL), and THF (50 mL) was ice-cooled, and then sodium hydrogen carbonate (20.1 g, 239 mmol). was added over 5 minutes. Subsequently, a solution of 1,4-cyclohexanedicarboxylic acid chloride (5.00 g, 23.9 mmol) in THF (45 mL) was added dropwise over 5 minutes. After the dropwise addition was completed, the mixture was stirred at the same temperature for 1 hour, and then THF was distilled off under reduced pressure. The resulting solid was washed with 2M hydrochloric acid (100 mL) and methanol (100 mL) to obtain compound (1-3-1) as a white solid (yield: 4.94 g, yield: 56%). ¹ H-NMR (400 MHz, (CD ₃ ) ₂ SO): δ 9.87-9.50 (br, 2H), 7.03 (d, J = 8.7 Hz, 4H), 6.77 (d, J = 8.7 Hz, 4H), 3.80 (s, 6H), 2.10-1.91 (m, 2H), 1.55-1.37 (m, 4H), 1.11-0.87 (m, 4H).
[Example 6]

Under an argon atmosphere, a mixture of 4-hydroxybenzoic acid (4.42 g, 32.0 mmol), toluene (30 mL), thionyl chloride (19.0 mL, 260 mmol) and N,N-dimethylformamide (catalytic amount) was refluxed for 3 hours. Boiled. Volatile components were distilled off and azeotroped with toluene (3×30 mL) to obtain 4-hydroxybenzoyl chloride. The obtained 4-hydroxybenzoic acid chloride was made into a tetrahydrofuran (30 mL) solution, and the entire amount was used for the next reaction.

Under an argon atmosphere, 4-(propylamino)phenol hydrochloride (5.00 g, 26.6 mmol) and sodium hydrogen carbonate (6.72 g, 80.0 mmol) were suspended in a mixed solvent of tetrahydrofuran (25 mL)/water (25 mL). muddy. Under ice-cooling, the tetrahydrofuran solution of 4-hydroxybenzoic acid chloride prepared earlier was slowly added, and the mixture was warmed to room temperature and stirred overnight. The solvent was evaporated under reduced pressure, water (100 mL) was added to the residue and extracted with ethyl acetate (3×100 mL). The combined organic layers were combined with saturated aqueous sodium bicarbonate (2 x 100 mL), 2M hydrochloric acid (2 x 100 mL) and saturated brine (100 mL).
L), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. After the residue was purified by silica gel column chromatography, the obtained solid was slurry-washed in diethyl ether (50 mL). The filtered solid was recrystallized from a mixed solvent of acetone/hexane to give 4-hydroxy-N-(4-hydroxyphenyl)-N-propylbenzamide (1-1-4) as a white solid (yield: 3.0%). 00 g, yield: 42%). 1H-NMR (400 MHz, (CD ₃ ) ₂ SO): δ 9.69 (brs, 1H), 9.46 (brs, 1H), 7.10-7.00 (m, 2H), 6.92-6 .82 (m, 2H), 6.67-6.58 (m, 2H), 6.57-6.48 (m, 2H), 3.71-3.63 (m, 2H), 1.48 (sext, J=7.4 Hz, 2H), 0.84 (t, J=7.4 Hz, 3H).
The purity of the obtained (1-1-4) was measured by gas chromatography and found to be 95.8% (retention time: 18.127) by area percentage method.
[Example 7]

A mixture of 4-hydroxybenzoic acid (2.00 g, 14.5 mmol), toluene (14 mL), thionyl chloride (8.75 mL, 120 mmol) and N,N-dimethylformamide (catalytic amount) was refluxed for 2 hours under an argon atmosphere. Boiled. Volatile components were distilled off and azeotroped with toluene (3×15 mL) to give 4-hydroxybenzoyl chloride. The obtained 4-hydroxybenzoic acid chloride was made into a tetrahydrofuran (14 mL) solution, and the whole amount was used for the next reaction.

Under an argon atmosphere, 4-(butylamino)phenol hydrochloride (2.42 g, 12.0 mmol) and sodium hydrogen carbonate (3.02 g, 36.0 mmol) were suspended in a mixed solvent of tetrahydrofuran (13 mL)/water (13 mL). muddy. Under ice-cooling, the tetrahydrofuran solution of 4-hydroxybenzoic acid chloride prepared earlier was slowly added, and the mixture was warmed to room temperature and stirred overnight. The solvent was evaporated under reduced pressure, water (50 mL) was added to the residue and extracted with ethyl acetate (3×50 mL). The combined organic layers were washed with saturated aqueous sodium bicarbonate solution (2×60 mL), 2M hydrochloric acid (2×60 mL) and saturated brine (60 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. After the residue is purified by silica gel column chromatography, the obtained solid is recrystallized from a mixed solvent of ethyl acetate/hexane to give N-butyl-4-hydroxy-N-(4-hydroxyphenyl)benzamide (1- 1-5) was obtained as a white solid (yield: 1.89 g, yield: 55%). 1H-NMR (400 MHz, (CD ₃ ) ₂ SO): δ 9.68 (brs, 1H), 9.47 (brs, 1H), 7.10-7.00 (m, 2H), 6.91-6 .81 (m, 2H), 6.67-6.58 (m, 2H), 6.57-6.47 (m, 2H), 3.70 (t, J=7.5Hz, 2H), 1 .50-1.38 (m, 2H), 1.48 (sext, J=7.4Hz, 2H), 0.85 (t, J=7.4Hz, 3H).
The purity of the obtained (1-1-5) was measured by gas chromatography and found to be 96% (retention time: 19.327) by area percentage method.
[Example 8]

Under an argon atmosphere, a mixture of 4-hydroxybenzoic acid (3.32 g, 24.1 mmol), toluene (24 mL), thionyl chloride (14.0 mL, 193 mmol) and N,N-dimethylformamide (catalytic amount) was refluxed for 3 hours. Boiled. Volatile components were distilled off and azeotroped with toluene (3×15 mL) to give 4-hydroxybenzoyl chloride. The obtained 4-hydroxybenzoic acid chloride was made into a tetrahydrofuran (24 mL) solution, and the entire amount was used for the next reaction.

Under an argon atmosphere, 4-(isobutylamino)phenol hydrochloride (4.04 g, 20.0 mmol) and sodium hydrogen carbonate (5.05 g, 60.1 mmol) were suspended in a mixed solvent of tetrahydrofuran (23 mL)/water (23 mL). muddy. Under ice-cooling, the tetrahydrofuran solution of 4-hydroxybenzoic acid chloride prepared earlier was slowly added, and the mixture was warmed to room temperature and stirred overnight. The solvent was evaporated under reduced pressure, water (80 mL) was added to the residue and extracted with ethyl acetate (3×80 mL). The combined organic layers were washed with saturated aqueous sodium bicarbonate solution (2×100 mL), 2M hydrochloric acid (2×100 mL) and saturated brine (100 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. After the residue was purified by silica gel column chromatography, the resulting solid was slurry-washed in diethyl ether (30 mL). The filtered solid was recrystallized from a mixed solvent of acetone/hexane to give 4-hydroxy-N-(4-hydroxyphenyl)-N-isobutylbenzamide (1-1-91) as an off-white solid (yield: 3. 22 g, yield: 56%). 1H-NMR (400 MHz, (CD ₃ ) ₂ SO): δ 9.67 (brs, 1H), 9.46 (brs, 1H), 7.08-6.99 (m, 2H), 6.93-6 .84 (m, 2H), 6.65-6.57 (m, 2H), 6.56-6.48 (m, 2H), 3.60 (d, J=7.4Hz, 2H), 1 .83-1.67 (m, 1H), 0.87 (d, J=6.8Hz, 6H).
The purity of the obtained (1-1-91) was measured by gas chromatography and found to be 97% (retention time: 18.601) by area percentage method.
[Example 9]

Under an argon atmosphere, a mixture of 4-hydroxybenzoic acid (4.00 g, 29.0 mmol), toluene (28 mL), thionyl chloride (17.0 mL, 233 mmol) and N,N-dimethylformamide (catalytic amount) was refluxed for 3 hours. Boiled. Volatile components were distilled off and azeotroped with toluene (3×15 mL) to give 4-hydroxybenzoyl chloride. The obtained 4-hydroxybenzoyl chloride was made into a tetrahydrofuran (28 mL) solution, and the whole amount was used for the next reaction.

Under an argon atmosphere, 4-(pentylamino)phenol (4.32 g, 24.1 mmol) and sodium hydrogen carbonate (4.04 g, 48.1 mmol) were suspended in a mixed solvent of tetrahydrofuran (26 mL)/water (26 mL). . Under ice-cooling, the tetrahydrofuran solution of 4-hydroxybenzoic acid chloride prepared earlier was slowly added, and the mixture was warmed to room temperature and stirred overnight. The solvent was evaporated under reduced pressure, water (80 mL) was added to the residue and extracted with ethyl acetate (3×80 mL). The combined organic layers were washed with saturated aqueous sodium bicarbonate solution (2×100 mL), 2M hydrochloric acid (2×100 mL) and saturated brine (100 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. After the residue was purified by silica gel column chromatography, the resulting solid was slurry-washed in diethyl ether (40 mL) to give 4-hydroxy-N-(4-hydroxyphenyl)-N-pentylbenzamide (1-1 -94) was obtained as an off-white solid (yield: 2.75 g, yield: 29%). 1H-NMR (400 MHz, (CD ₃ ) ₂ SO): δ 9.68 (brs, 1H), 9.46 (brs, 1H), 7.10-7.00 (m, 2H), 6.91-6 .81 (m, 2H), 6.67-6.58 (m, 2H), 6.56-6.48 (m, 2H), 3.69 (t, J=7.5Hz, 2H), 1 .52-1.40 (m, 2H), 1.32-1.17 (m, 4H), 0.83 (t, J=6.9Hz, 3H).
The purity of the obtained (1-1-94) was measured by gas chromatography and found to be 97% (retention time: 20.878) by area percentage method.
[Example 10]

Under an argon atmosphere, a mixture of 4-hydroxybenzoic acid (2.32 g, 16.8 mmol), toluene (17 mL), thionyl chloride (10.0 mL, 138 mmol) and N,N-dimethylformamide (catalytic amount) was refluxed for 2 hours. Boiled. Volatile components were distilled off and azeotroped with toluene (3×15 mL) to give 4-hydroxybenzoyl chloride. The obtained 4-hydroxybenzoyl chloride was made into a tetrahydrofuran (16 mL) solution, and the entire amount was used for the next reaction.

Under an argon atmosphere, 4-[(3-methylbutyl)amino]phenol hydrochloride (3.04 g, 14.1 mmol) and sodium bicarbonate (3.54 g, 42.2 mmol) were mixed with tetrahydrofuran (15 mL)/water (15 mL). Suspended in a mixed solvent. Under ice-cooling, the tetrahydrofuran solution of 4-hydroxybenzoic acid chloride prepared earlier was slowly added, and the mixture was warmed to room temperature and stirred overnight. The solvent was evaporated under reduced pressure, water (50 mL) was added to the residue and extracted with ethyl acetate (3×50 mL). The combined organic layers were washed with saturated aqueous sodium bicarbonate solution (2×75 mL), 2M hydrochloric acid (2×75 mL) and saturated brine (75 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. After purification of the residue by silica gel column chromatography, the resulting solid was slurry-washed in diethyl ether (25 mL) to give 4-hydroxy-N-(4-hydroxyphenyl)-N-(3-methylbutyl)benzamide. (1-1-95) was obtained as an off-white solid (yield: 2.90 g, yield: 69%). 1H-NMR (400 MHz, (CD ₃ ) ₂ SO): δ 9.68 (brs, 1H), 9.46 (brs, 1H), 7.09-7.00 (m, 2H), 6.91-6 .82 (m, 2H), 6.67-6.58 (m, 2H), 6.57-6.48 (m, 2H), 3.78-3.68 (m, 2H), 1.54 (nonet, J=6.6Hz, 1H), 1.41-1.31 (m, 2H), 0.85 (d, J=6.6Hz, 6H).
The purity of the obtained (1-1-95) was measured by gas chromatography and found to be 96% (retention time: 20.046) by area percentage method.
[Example 11]

Under an argon atmosphere, a mixture of 4-hydroxybenzoic acid (3.32 g, 24.0 mmol), toluene (24 mL), thionyl chloride (14.0 mL, 193 mmol) and N,N-dimethylformamide (catalytic amount) was refluxed for 2 hours. Boiled. Volatile components were distilled off and azeotroped with toluene (3×15 mL) to give 4-hydroxybenzoyl chloride. The obtained 4-hydroxybenzoic acid chloride was made into a tetrahydrofuran (23 mL) solution, and the entire amount was used for the next reaction.

Under an argon atmosphere, 4-(hexylamino)phenol (4.14 g, 20.0 mmol) and sodium hydrogen carbonate (3.37 g, 40.1 mmol) were suspended in a mixed solvent of tetrahydrofuran (22 mL)/water (22 mL). . Under ice-cooling, the tetrahydrofuran solution of 4-hydroxybenzoic acid chloride prepared earlier was slowly added, and the mixture was warmed to room temperature and stirred overnight. The solvent was evaporated under reduced pressure, water (70 mL) was added to the residue and extracted with ethyl acetate (3×70 mL). The combined organic layer was washed with saturated aqueous sodium hydrogencarbonate solution (100 mL), 2M hydrochloric acid (100 mL) and saturated brine (100 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was dissolved in methanol (60 mL), activated carbon (0.65 g) was added, and the mixture was stirred for 4 hours and then filtered through celite. The filtrate was concentrated under reduced pressure, the residue was purified by silica gel column chromatography, and the resulting solid was slurry-washed in toluene (25 mL) to give N-hexyl-4-hydroxy-N-(4- An off-white solid (yield: 5.06 g, yield: 81%) of hydroxyphenyl)benzamide (1-1-98) was obtained. 1H-NMR (400 MHz, (CD ₃ ) ₂ SO): δ 9.68 (brs, 1H), 9.46 (brs, 1H), 7.09-7.00 (m, 2H), 6.90-6 .82 (m, 2H), 6.66-6.58 (m, 2H), 6.57-6.47 (m, 2H), 3.69 (t, J=7.5Hz, 2H), 1 .53-1.38 (m, 2H), 1.32-1.14 (m, 6H), 0.88-0.79 (m, 3H).
The purity of the obtained (1-1-98) was measured by gas chromatography and found to be 94% (retention time: 22.817) by area percentage method.
[Example 12]

Under an argon atmosphere, a mixture of 4-hydroxybenzoic acid (2.49 g, 18.0 mmol), toluene (18 mL), thionyl chloride (10.5 mL, 145 mmol) and N,N-dimethylformamide (catalytic amount) was refluxed for 1 hour. Boiled. Volatile components were distilled off and azeotroped with toluene (3×15 mL) to give 4-hydroxybenzoyl chloride. The obtained 4-hydroxybenzoyl chloride was made into a tetrahydrofuran (18 mL) solution, and the whole amount was used for the next reaction.

Under an argon atmosphere, 4-(dodecylamino)phenol (4.16 g, 15.0 mmol) and sodium hydrogen carbonate (2.52 g, 30.0 mmol) were suspended in a mixed solvent of tetrahydrofuran (17 mL)/water (17 mL). . After slowly adding the previously prepared tetrahydrofuran solution of 4-hydroxybenzoic acid chloride under ice-cooling, the mixture was warmed to room temperature and stirred for 4 hours. The solvent was evaporated under reduced pressure, water (50 mL) was added to the residue and extracted with ethyl acetate (3×50 mL). The combined organic layers were washed with saturated aqueous sodium hydrogencarbonate solution (80 mL), 2M hydrochloric acid (80 mL) and saturated brine (80 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was dissolved in methanol (50 mL), a solution of sodium hydroxide (1.21 g, 30.3 mmol) in water (10 mL) was added, and the mixture was stirred at room temperature for 1 hour and then concentrated under reduced pressure. Water (35 mL) was added to the residue, the pH was adjusted to 1 with concentrated hydrochloric acid, and extracted with ethyl acetate (3×50 mL). The combined organic layers were washed with saturated aqueous sodium hydrogencarbonate solution (100 mL) and saturated brine (100 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. After the residue was purified by silica gel column chromatography, the resulting solid was slurry-washed in a mixed solvent of toluene (15 mL)/hexane (15 mL) to give N-dodecyl-4-hydroxy-N-(4-hydroxy An off-white solid of phenyl)benzamide (1-1-104) was obtained (yield: 4.74 g, yield: 80%). 1H-NMR (400 MHz, (CD ₃ ) ₂ SO): δ 9.69 (brs, 1H), 9.47 (brs, 1H), 7.10-7.00 (m, 2H), 6.92-6 .80 (m, 2H), 6.68-6.58 (m, 2H), 6.58-6.48 (m, 2H), 3.69 (t, J=7.5Hz, 2H), 1 .53-1.36 (m, 2H), 1.34-1.12 (m, 18H), 0.85 (t, J=6.8Hz, 3H).
The purity of the obtained (1-1-104) was measured by gas chromatography and found to be 85% (retention time: 48.180) by area percentage method.
[Example 13]

Under an argon atmosphere, 4-hydroxy-N-(4-hydroxyphenyl)benzamide (2.21 g, 9.66 mmol) was dissolved in N,N-dimethylformamide (45 mL). Under ice-cooling, 55% sodium hydride (1.69 g, 38.7 mmol) and 2-iodopropane (7.70 mL, 77.5 mmol) were sequentially added, heated to 60° C. and stirred for 4 hours. The reaction mixture was cooled, 55% sodium hydride (0.853 g, 19.5 mmol) and 2-iodopropane (4.80 mL, 48.3 mmol) were added sequentially and stirred at 60° C. for a further 5 hours. Water (135 mL) was added to the reaction mixture and extracted with ethyl acetate (2×100 mL). The combined organic layers were washed with water (3×100 mL) and saturated brine (100 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.

Under an argon atmosphere, the residue was dissolved in N,N-dimethylformamide (45 mL). Under ice-cooling, 55% sodium hydride (1.27 g, 29.0 mmol) and 2-iodopropane (7.70 mL, 77.5 mmol) were sequentially added, heated to 60° C. and stirred for 4 hours. The reaction mixture was cooled, 55% sodium hydride (0.865 g, 19.8 mmol) and 2-iodopropane (4.80 mL, 48.3 mmol) were added sequentially and stirred at 60° C. for an additional 4 hours. Water (135 mL) was added to the reaction mixture, and the mixture was extracted with a mixed solvent of hexane/ethyl acetate (1:1, 2×100 mL). The combined organic layers were washed with water (3×100 mL) and saturated brine (100 mL), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Hexane (50 mL) was added to the residue and ice-cooled, and the precipitated solid was removed by filtration. The filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to give a pale yellow oil of 4-isopropoxy-N-(4-isopropoxyphenyl)-N-isopropylbenzamide (yield: 2. 22 g, yield: 64%). 1H-NMR (400 MHz, CDCl ₃ ): δ 7.24-7.13 (m, 2H), 6.95-6.85 (m, 2H), 6.77-6.67 (m, 2H), 6 .66-6.55 (m, 2H), 5.06 (brm, 1H), 4.46 (sept, J=6.0Hz, 2H), 1.29 (d, J=6.0Hz, 6H) , 1.26 (d, J=6.0 Hz, 6H), 1.16 (d, J=6.8 Hz, 6H).
Under an argon atmosphere, 4-isopropoxy-N-(4-isopropoxyphenyl)-N-isopropylbenzamide (2.22 g, 6.23 mmol) was dissolved in dichloromethane (25 mL). Pulverized aluminum chloride (2.23 g, 16.7 mmol) was added thereto, and the mixture was stirred at room temperature for 7 hours. Add crushed aluminum chloride (1.10 g, 8.25 mmol) and dichloromethane (10 mL) to the reaction mixture and stir at room temperature for an additional hour. The reaction mixture was diluted with saturated aqueous ammonium chloride solution (70 mL), a small amount of 2M hydrochloric acid was added to dissolve insoluble matter, and then extracted with ethyl acetate (3×70 mL). The combined organic layers were washed with saturated brine (100 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography, and the obtained solid was recrystallized from a mixed solvent of 2-propanol/hexane to give 4-hydroxy-N-(4-hydroxyphenyl)-N-isopropylbenzamide (1- 1-3) was obtained as a white solid (yield: 0.747 g, yield: 44%). 1H-NMR (400 MHz, (CD ₃ ) ₂ SO): δ 9.62 (brs, 1H), 9.51 (brs, 1H), 7.09-6.99 (m, 2H), 6.89-6 .81 (m, 2H), 6.67-6.58 (m, 2H), 6.56-6.46 (m, 2H), 4.82 (brm, 1H), 1.05 (d, J = 6.7Hz, 6H).
The purity of the obtained (1-1-3) was measured by gas chromatography and found to be 97% (retention time: 17.593) by area percentage method.
[Example 14]

Under an argon atmosphere, a mixture of 4-hydroxybenzoic acid (2.28 g, 16.5 mmol), toluene (17 mL), thionyl chloride (9.60 mL, 132 mmol) and N,N-dimethylformamide (catalytic amount) was refluxed for 1 hour. Boiled. Volatile components were distilled off and azeotroped with toluene (3×15 mL) to give 4-hydroxybenzoyl chloride. The obtained 4-hydroxybenzoyl chloride was made into a tetrahydrofuran (18 mL) solution, and the whole amount was used for the next reaction.

Under an argon atmosphere, 4-(octylamino)phenol (3.32 g, 15.0 mmol) and sodium hydrogen carbonate (2.52 g, 30.0 mmol) were suspended in a mixed solvent of tetrahydrofuran (17 mL)/water (17 mL). . After slowly adding the previously prepared tetrahydrofuran solution of 4-hydroxybenzoic acid chloride under ice-cooling, the mixture was warmed to room temperature and stirred for 18 hours. The solvent was evaporated under reduced pressure, water (50 mL) was added to the residue and extracted with ethyl acetate (3×50 mL). The combined organic layers were washed with saturated aqueous sodium hydrogencarbonate solution (75 mL), 2M hydrochloric acid (75 mL) and saturated brine (75 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was dissolved in methanol (40 mL), activated carbon (0.42 g) was added, and the mixture was stirred for 1 hour and then filtered through celite. The filtrate was concentrated under reduced pressure, the residue was purified by silica gel column chromatography, and the obtained solid was slurry-washed in a mixed solvent of toluene (20 mL)/hexane (20 mL) to give 4-hydroxy-N An off-white solid of -(4-hydroxyphenyl)-N-octylbenzamide (1-1-100) (yield: 2.85 g, yield: 56%) was obtained. 1H-NMR (400 MHz, (CD ₃ ) ₂ SO): δ 9.69 (brs, 1H), 9.49 (brs, 1H), 7.09-7.00 (m, 2H), 6.91-6 .81 (m, 2H), 6.66-6.58 (m, 2H), 6.58-6.48 (m, 2H), 3.69 (t, J=7.5Hz, 2H), 1 .52-1.35 (m, 2H), 1.33-1.13 (m, 10H), 0.84 (t, J=6.9Hz, 3H).
The purity of the obtained (1-1-100) was measured by gas chromatography and found to be 90% (retention time: 28.199) by area percentage method.
[Example 15]

Under an argon atmosphere, a mixture of 4-hydroxybenzoic acid (2.49 g, 18.0 mmol), toluene (18 mL), thionyl chloride (10.5 mL, 145 mmol) and N,N-dimethylformamide (catalytic amount) was refluxed for 1 hour. Boiled. Volatile components were distilled off and azeotroped with toluene (3×15 mL) to give 4-hydroxybenzoyl chloride. The obtained 4-hydroxybenzoyl chloride was made into a tetrahydrofuran (18 mL) solution, and the whole amount was used for the next reaction.

Under an argon atmosphere, 4-(decylamino)phenol (3.74 g, 15.0 mmol) and sodium hydrogen carbonate (2.52 g, 30.0 mmol) were suspended in a mixed solvent of tetrahydrofuran (17 mL)/water (17 mL). Under ice-cooling, the tetrahydrofuran solution of 4-hydroxybenzoic acid chloride prepared earlier was slowly added, and the mixture was warmed to room temperature and stirred for 2 hours. The solvent was evaporated under reduced pressure, water (50 mL) was added to the residue and extracted with ethyl acetate (3×50 mL). The combined organic layers were washed with saturated aqueous sodium hydrogencarbonate solution (80 mL), 2M hydrochloric acid (80 mL) and saturated brine (80 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was dissolved in methanol (60 mL), activated carbon (0.60 g) was added, and the mixture was stirred for 1 hour and then filtered through celite. The filtrate was concentrated under reduced pressure, the residue was purified by silica gel column chromatography, and the resulting solid was slurry-washed in a mixed solvent of toluene (15 mL)/hexane (15 mL) to obtain N-decyl-4. -Hydroxy-N-(4-hydroxyphenyl)benzamide (1-1-102) was obtained as an off-white solid (yield: 3.32 g, yield: 60%). 1H-NMR (400 MHz, (CD ₃ ) ₂ SO): δ 9.69 (brs, 1H), 9.47 (brs, 1H), 7.09-6.99 (m, 2H), 6.90-6 .81 (m, 2H), 6.66-6.58 (m, 2H), 6.57-6.48 (m, 2H), 3.69 (t, J=7.5Hz, 2H), 1 .52-1.36 (m, 2H), 1.34-1.13 (m, 14H), 0.85 (t, J=6.8Hz, 3H).
The purity of the obtained (1-1-102) was measured by gas chromatography and found to be 92% (retention time: 36.101) by area percentage method.
[Polymer Example 1]

20 ml of ion-exchanged water was placed in a 200 mL three-necked flask equipped with a dropping funnel, and compound (1-1-1) synthesized in Example 1 (973 mg, 4.00 mmol) and sodium hydroxide (320 mg, 8.00 mmol). was dissolved and stirred. A 2% tetrabutylammonium bromide aqueous solution (1.6 mL) was added as a catalyst, and the inside of the apparatus was sufficiently replaced with nitrogen.

A solution prepared by dissolving trans-1,4-cyclohexanedicarboxylic acid dichloride (0.836 g, 4.00 mmol) in 20 mL of chloroform was placed in a dropping funnel and gently added dropwise.

After the dropwise addition was completed, the mixture was vigorously stirred at room temperature for 3 hours to effect interfacial polymerization. The solution after the reaction was poured into methanol, and the precipitate was separated by filtration, washed with methanol, and dried in vacuo to obtain 1.35 g of a white solid of polymer P1 at a yield of 89%. Polymer P1 was soluble in 1,1,1,3,3,3-hexafluoro-2-propanol and chloroform.

6.0% by weight of polymer P1 was dissolved in 94.0% by weight of 1,1,1,3,3,3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 3000 rpm for 60 seconds, and dried in an oven at 150° C. for 30 minutes to obtain a film (thickness: 1 μm). The obtained film had a haze % of 0.12 and a YI of 0.23, and was excellent in transparency.
[Polymer Example 2]

Under a nitrogen stream, the compound (1-1-6) (1.57 g, 5.80 mmol) obtained in Synthesis Example 2 and trans-1,4-cyclohexanedicarboxylic acid (1.00 g, 5.80 mmol) were placed in a reaction vessel. After the addition, pyridine (6.3 mL) was added as a solvent and stirred at 30°C for 30 minutes. Subsequently, after adding diisopropylcarbodiimide (1.61 g, 12.8 mmol) as a condensing agent, the mixture was stirred at 30° C. for 3 hours. After stirring, the mixture in the system was added to methanol (300 mL). The resulting viscous substance was washed with methanol (100 mL) by decantation, and then vigorously stirred in water (200 mL) to obtain a white powder. After washing with methanol and water, it was vacuum-dried to obtain 1.11 g of polymer P2 (yield: 47%). Polymer P2 was soluble in 1,1,1,3,3,3-hexafluoro-2-propanol and chloroform.

6.0% by weight of polymer P2 was dissolved in 94.0% by weight of 1,1,1,3,3,3-hexafluoro-2-propanol. This was cast on a quartz glass substrate, spin-coated at 3000 rpm for 60 seconds, and dried in an oven at 60° C. for 30 minutes to obtain a film (thickness: 1 μm). The obtained film had a haze % of 0.03 and a YI of 0.46, and was excellent in transparency.
[Polymer Example 3]

Under a nitrogen stream, the compound (1-1-6) (1.57 g, 5.80 mmol) obtained in Synthesis Example 2 and terephthalic acid (964 mg, 5.80 mmol) were added to a reaction vessel, and pyridine (8 .8 mL) was added and stirred at 30° C. for 30 minutes. Subsequently, after adding diisopropylcarbodiimide (1.61 g, 12.8 mmol) as a condensing agent, the mixture was stirred at 30° C. for 3 hours. After stirring, the mixture in the system was added to methanol (300 mL). The resulting solid was washed with methanol and water, and then vacuum-dried to obtain 0.55 g of polymer P3 (yield: 23%).

Claims (10)

A dihydroxyanilide compound represented by the following formula (1), having a purity of 85% or higher as measured by gas chromatography.

[Wherein, ring A and ring B each independently have a ring-constituting atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, a cycloalkane, a monocyclic aromatic ring, represents a ring selected from the group consisting of polycyclic aromatic rings and condensed aromatic rings, and these cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings and condensed aromatic rings have substituents; may be
R ¹ represents an alkyl group having 1 to 20 carbon atoms.
n represents 0 or 1; ] 2. The dihydroxyanilide compound according to claim 1, wherein ring A and ring B are each independently a ring selected from a cyclohexane ring and a benzene ring. A carboxylic acid chloride represented by the following formula (2) and an amine having a hydroxyl group represented by the following formula (3) or a salt thereof are reacted in a mixed solvent of a cyclic ether and water using an alkali metal hydrogen carbonate. A method for producing a dihydroxyanilide compound represented by the following formula (1), characterized by:

[In the formula, R represents a hydroxy group or a chlorocarbonyl group. Ring A is selected from cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings and condensed aromatic rings having ring-constituting atoms selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. A ring selected from the group consisting of cycloalkane, monocyclic aromatic ring, polycyclic aromatic ring and condensed aromatic ring may have a substituent. ]

[In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms. Ring B is selected from cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings and condensed aromatic rings having ring-constituting atoms selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. A ring selected from the group consisting of cycloalkane, monocyclic aromatic ring, polycyclic aromatic ring and condensed aromatic ring may have a substituent. ]

[Wherein, ring A and ring B each independently have a ring-constituting atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, a cycloalkane, a monocyclic aromatic ring, represents a ring selected from the group consisting of polycyclic aromatic rings and condensed aromatic rings, and these cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings and condensed aromatic rings have substituents; may be
R ¹ represents an alkyl group having 1 to 20 carbon atoms.
n represents 0 or 1; ] 4. The method for producing a dihydroxyanilide compound according to claim 3, wherein the alkali metal hydrogencarbonate is sodium hydrogencarbonate or potassium hydrogencarbonate. 4. The method for producing a dihydroxyanilide compound according to claim 3, wherein the cyclic ether is tetrahydrofuran or 1,4-dioxane. The mixture containing the dihydroxyanilide compound represented by the formula (1) is purified by washing with one or more selected from the group consisting of water, basic aqueous solution, acidic aqueous solution and organic solvent, and 85% or more (gas chromatography 4. The process for producing a dihydroxyanilide compound according to claim 3, comprising the step of isolating the compound of formula (1) with a graphic purity. 7. The method for producing a dihydroxyanilide compound according to any one of claims 3 to 6, wherein ^R1 in formula (1) is an alkyl group having 1 to 20 carbon atoms. a group in which ring A and ring B each independently comprise an optionally substituted cyclohexane ring, an optionally substituted benzene ring, an optionally substituted naphthalene ring and an optionally substituted biphenyl ring; 8. The method for producing a dihydroxyanilide compound according to claim 7, wherein the ring is selected from A polymer containing a repeating unit represented by the following formula (4).

[Wherein, ring A and ring B each independently have a ring-constituting atom selected from the group consisting of a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, a cycloalkane, a monocyclic aromatic ring, represents a ring selected from the group consisting of polycyclic aromatic rings and condensed aromatic rings, and these cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings and condensed aromatic rings have substituents; may be
L is a cycloalkane, a monocyclic aromatic ring, a polycyclic aromatic ring and a condensed aromatic ring in which the ring-constituting atoms are atoms selected from the group consisting of carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms; represents a ring selected from the group or an optionally substituted alkyl chain having 1 to 20 carbon atoms; These cycloalkanes, monocyclic aromatic rings, polycyclic aromatic rings, condensed aromatic rings, and alkyl chains may have substituents.
R ¹ represents an alkyl group having 1 to 20 carbon atoms.
n represents 0 or 1; ] An optical film comprising the polymer according to claim 9 .

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